# 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

®

## Perfluoro octanoi c Acid (PFOA) Site Related Environmental Assessment Program 3M Decatur, Alabama Site
Quarterly Status Report October 1 , 2011 to December 31 , 20 1 1

Prepared for 

### 3M Company and Dyneon LLC
By 

### WESTON SOLUTIONS, INC. West Ch ester, Pennsylvania 19380 W.O. No. 02181.129. 1 1 8 .0001J: \ FOLDERS.0 - 9 \ 3M - DECAT\ Phase 3 Work Plan \ 4Q11 Status Report\ 4Q11 Status Report.doc 1/30/2012 

### i 

## TABLE OF CONTENTS Section Page 1. BACKGROUND ................................ ................................ ................................ ............ 1 - 1 2. SUMMARY OF ACTIVITIE S ................................ ................................ ..................... 2 - 1



## ATTACHMENTS Attachment Title 1 GROUNDW ATER SAMPLING TECHNICAL PROGRESS R EPORT 2 VEGETATIVE UPTAKE ST UDY TECHNICAL PROGRESS REPORTJ: \ FOLDERS.0 - 9 \ 3M - DECAT\ Phase 3 Work Plan \ 4Q11 Status Report\ 4Q11 Status Report.doc 1/30/2012 

### 1
- 1 

## 1. BACKGROUND In accordance with the Phase 3 Work Plan for Sampling Environmental Media ( WESTON, 200 9 ) and the Memorandum of Understanding ( MOU ) ( 3M, 2004) with EPA , 3M and Dyneon LLC are undertaking a Perfluorooctanoic Acid (PFOA) Site
Related Environmental Monitoring and Assessment Program at their Decatur, Alabama , plant. Per the agreement between EPA and 3M, t his report represents the status report of this effort as required by the MOU for the October 1 , 20 1 1 through December 31 , 2011 time period. For brevity, and following previous convention, this report will be referred to as the December 31 , 20 11 Quarterly Status Report .J: \ FOLDERS.0 - 9 \ 3M - DECAT\ Phase 3 Work Plan \ 4Q11 Status Report\ 4Q11 Status Report.doc 1/30/2012 

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- 1 

## 2. SUMMARY OF ACTIVITIE S The Phase 2 Wo rk Plan and MOU were finalized on October 25, 2004 . Phase 2 of the monitoring program h as 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 u nder Phase 3 . It covers the October 1 , 201 1 to December 31 , 201 1 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 prov ide 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 non
MOU information will also be described a nd provided in the se quarterly status reports. Details on activities completed during this reporting period are as follows: Groundwater Sampling Technical Progress

• 

### Off
- site well sampling and construction

– G roundwater samples were collected in September 20 11 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 prov ided 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 S eptember 30 , 2011 Quarterly Status Report . The September 2011 m onitoring of groundwater in the chemica l 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 the se groundwater samples has been finalized and data are prov ided in the Groundwater Sampling Technical Progress Report (Attachment 1).J: \ FOLDERS.0 - 9 \ 3M - DECAT\ Phase 3 Work Plan \ 4Q11 Status Report\ 4Q11 Status Report.doc 1/30/2012 

### 2
- 2 Groundwater sampling was performed between December 8, 2011 and December 14 , 2011 at 2 7 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 m onitoring 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

– R outine monitoring of watering and ventilation system s 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 a ctivities 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 an d 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 wo rk 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 .J: \ FOLDERS.0 - 9 \ 3M - DECAT\ Phase 3 Work Plan \ 4Q11 Status Report\ 4Q11 Status Report.doc 1/30/2012 

## ATTACHMENT 1 GROUNDWATER SAMPLING TECHNICAL PROGRESS R EPORT OCTOBER 1, 201 1 – DEC EM BER 3 1 , 2011J: \ FOLDERS.0 - 9 \ 3M - DECAT\ Phase 3 Work Plan \ 4Q11 Status Report\ 4Q11 Status Report.doc 1/30/2012 

### 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 201 1 and summarize the results of analyses for PFOA . Anal ytical d ata packages for Interim Report 22 and Interim Report 23 are provided in Appendi ces A and B . Full analytical data packages , including raw data, chromatograms and correspondence , are provided in the Raw Data Appe ndix to this quarterly status report. OFF - SITE ACTIVITIES Off - site 610 Series Well Cluster C onstruction and Sampling Two n ew Phase 3 monitoring wells located approximately 1 mile to the southeast of the 3M Decatur facilit y were installed in August 2011 and sampled in September 2011 as describ ed in the S eptember 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 - S ite 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 m onitoring of groundwater in the chemical plant and closed landfill area is a component of t he Remedial Action Agreement Program being executed by 3M under the ADEM NPDES program and is not a MOU
- related activity. Monitoring locations included 1 7 individual wells and the combined groundwater discharge from the maintenance pumping wells at the clo sed 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 extracti on wells sample GRS04. A nalytical 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 g roundwater 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. Dat a 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, e pikarst 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 2 7 monitoring wells in the Former Sludge Incorporation Area (FSIA). Two of the m onitoring 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 3 M 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 HwyBeltline 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 0 200 Feet 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.xls331S

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 0 225 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 220L 49.8 

### 222R 366 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]J: \ FOLDERS.0 - 9 \ 3M - DECAT\ Phase 3 Work Plan \ 4Q11 Status Report\ 4Q11 Status Report.doc 1/30/2012 

## APPENDIX A TO ATTACH MENT 1 GLP10 - 01 - 01 INTERIM REPORT 22 The full data package, including raw data, is provided in the Raw Data Appendi x .J: \ FOLDERS.0 - 9 \ 3M - DECAT\ Phase 3 Work Plan \ 4Q11 Status Report\ 4Q11 Status Report.doc 1/30/2012 

## 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 ; Interi m Repor t 2 3 Analysi s of PFO

A i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1 

# 3 M

GLP10-01-01 . Interi m Repor t 23 : Analysi s o f PFO A i n Groundwate r Sample s Collecte d a t

th e Off-Sit e 61 0 Well s i n Decatur . A L i n Septembe r 201 1 Stud y Titl e Analysi s o f Perfluorooctanoi c Aci d (PFOA ) I n Groundwater , Soi l an d Sedimen t fo rth e 3 M Decatu rPhas e 3 Site-Relate d Monitorin g Progra m Dat a Requiremen t EPA TSC A Goo d Laborator yPractic e Standard s 4 0 CF R Par t 79 2 Stud y Directo r Jaisimh a Kesar i P.E. , DE E Westo n Solutions , Inc
. 140 0 Westo n Wa y Westchester , P

A 1938 0 Phone : 610-701-376 1 Autho r Susa n Wol f 3 M Environmenta l Laborator y Interi m Repor t Completio n Dat e

Dat e o f signin g Performin g Laborator y 3 M Environmenta l Healt h an d Safet yOperation s Environmenta l Laborator

y 3 M Center , BId g 260-05-N-1 7 S t Paul , M N 5514 4 Projec t Identificatio n GLP10-01-01-2 3 Tota l Numbe r o f Page s

44

ACCREDITE D Testin g Cer t #2052.0 1

TTi e testin g reported herei n mee t th e requirements of ISO/IE C 17025-200 5 "Genera l Requirement

s fo rth e Competenc

e o f Testin g an d Calibratio n Laboratories" , i n accordanc e wit h th e A2L. A Certificate #2052.01
. Testin g tha t complie s wit h thi s Internationa l Standar d als o operat e i n accordanc

e wit h IS O 9001:2000
.

Pag e 1 of 4 4GLP10-01-01 ; Interi m Repor t 2 3 Analysi s o f PFOA i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1

Thi s pag e has bee n reserve d for specifi c countr

y requirements .

Pag e 2 o f 44GLP10-01-01 ; Interi m Repor t 2 3 Analysi s o f PFOA i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1



### GL P COMPLIANC E STATEMEN T Repor t Title : GLP10-01-01 , Interi m Repor t 23
. Analysi s of PFO

A i n Groundwate rSample s Collecte d a t th e off-Sit e 61 0 Well s i n Decatur , A L i n Septembe r201 1 Study : Analysi s o

f Perfluorooctanoi c Aci d (PFOA ) i n Groundwater , Soi l an d Sedimen t fo rth e 3 M Decatu rPhas e 3 Site-Relate d Monitorin g Program
. Thi s analytica l phas e wa s conducte d i n complianc e wit h Toxi c Substance s Contro l Ac t (TSCA ) Goo d Laborator yPractice (GLP ) Standards , 4 0 CF R 792 , wit h th e exception s liste d below :

• Thes e are environmenta l sample s where there i s n o specifi c tes t substance , n o specifi c tes t syste m an d n o dosin g o

f a tes t system . • Th e reference substance s hav e no t bee n characterize d unde rth e GLP s an d th e stabilit yunde r storag e condition s a

t th e tes t sit e hav

e no t bee n determine d unde rGLPs
. 

# 1 Gar yHohensiein , Spoyiso rRepresentative Date

Jaisimh a Kesari , P.E. , DEE , Stud yDirecto r/ Date

Pag e 3 o f 4 4GLP10-01-01 ; Interi m Repor t 2 3 Analysi s of PFOA i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1



### QUALIT Y ASSURANC E STATEMEN T Repor t Title : GLP10-01-01 , Interi m Repor t 23
. Analysi s o

f PFO A i n Groundwate rSample s Collecte d a t th e Off-Sit e 61 0 Well s i n Decatur , A L i n Septembe r201 1 Study : Analysi s of Perfluorooctanoi c Aci d (PFOA ) i n Groundwater , Soi l an d Sedimen t fo rth e 3 M Decatu rPhas e 3 Site-Relate d Monitorin g Program
. Thi s repor

t an d th e accompanyin g dat a were audite d b yth e 3 M Environmenta l Laborator yQualit y Assuranc e Uni t (QAU) , a s indicate d below
. Th e finding s were reporte d t o th e principa l analytica l investigato r(P.A.I.) , laborator ymanagemen t an d stud ydirector
.
inspectio n Date s Phas e Dat e Reporte d t o inspectio n Date s Phas e Testin g Facilit y Managemen t Stud yDirecto r 9/6/1 1 In-Phas e Sampl e Preparatio n 10/11/1 1 10/11/1 1 10/13-10/14/1 1 Dat a an d Repor

t 10/31/1 1 10/31/1 1

QA U Repre^ntativ e Date

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A i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1



### TABL E O F CONTENT S GL P Complianc e Statemen t 3 Qualit yAssuranc e Statemen t 4 Tabl e of Contents 5 List o f Table s 6 1 Stud yInfonnatio n 7 2 Summar

y8 3 Introductio n 8 4 Test & Contro l Substance s 9 5 Reference Substance s 9 6 Test Syste m 1 0 7 Metho d Summar

y1 0 7. 1 Method s 1 0 7. 2 Sampl e Collectio n 1 0 7. 3 Sampl e Preparatio n 1 0 7. 4 Analysi s 1 0 8 Analytica l Result s 1 1 8^ 1 Calibratio n 1 1 8. 2 Syste m Suitabilit y1 2 8. 3 Limi t of Quantitatio n (LOQ ) 1 2 8. 4 Continuin g Calibratio n 1 2 8. 5 Blank

s 1 2 8. 6 La b Contro l Spike s (LCSs ) 1 2 8. 7 Analytica l Metho d Uncertaint y1 3 8. 8 Fiel d Matri xSpike s (FMS ) 1 3

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9 Data Summar

yan d Discussio n 1 4 1 0 Conclusio n 1 6 1 1 Data/Sampl e Retentio n 1 6 1 2 Attachment s 1 6 1 3 Signature s 1 7 

### LIS T O F TABLE S Tabl e 1
. Summarize d PFO A Results (Off-Sit e 61 0 Wells , Septembe r2011 ) 8 Tabl e 2
. Sampl e Descriptio n Ke yCod e 1 0 Tabl e 3
. Instrumen t Parameter s 1 1 Tabl e 4
. Liqui d Chromatograph yCondition s .1 1 Tables
. Mas s Transition s 1 1 Tabl e 6
. Limi t of Quantitatio n (LOQ ) 1 2 Tabl e 7
. Laborator

yContro l Spik

e Recover

y1 3 Tabl e 8
. Analytica l Metho d Uncertaint y1 3 Tabl e 9
. Fiel d Matri xSpike Level s 1 4 Tabl e 10
. DA L G W 6 1 O S 11092 1 1 5 Tabl e 11
. DA L G W 61O L 11092 1 1 5 Tabl e 12
. Tri p Blan k

11092 1 1 5

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A i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1

1 Study

Information Sponso r 3 M Compan y Sponso r Representativ e Gar yHohenstei n 3 M EH S Operation s 3 M Buildin g 224-5W-0 3 Sain t Paul , M N 55144-100 0 Phone:(651)737-357 0 Stud y Directo r Jaisimh a Kesari , P.E. , DE E Westo n Solutions , Inc
. Westchester , P

A 1938 0 Phone : (610 ) 701-376 1 Fax : (610)701-740 1 j
. kesari@westonsolutions.co m Stud y Locatio n Testing Facility 3 M EH S Operation s 3 M Environmenta l Laborator y Buildin g 260-5N-1 7 St
. Paul , M N 55144 Stud y Personne l Willia m K

. Reagen , Ph.D. , 3 M Laborator yManage r Clesto n Lange , Ph.D. , Principa l Analytica l Investigator , (clanqe@mmm.com) ; phon e (651)-733-986 0 Susa n Wolf , 3 M Analys t Chelsi e Grochow , Analys t Kevi n Eich , Analys t Kell yUkes , Analys t Jonatha n Steege , Analys t Stud y Date s Stud yInitiation : Marc h 8 , 201 0 Interi m Repor

t 2 3 Experimenta l Termination : Octobe r7,201 1 Interi m Repor

t Completion : Date o

f Interi m Repor

t Signin g Locatio n o

f Archive s Al l origina l raw dat a an d th e analytica l repor t have bee n archive d at th e 3 M Environmenta l Laborator yaccordin g t o 4 0 CF R Par t 792
. Th e tes t substanc e an d analytica l referenc e standar d reserv e sample s ar e archive d a t th e 3 M Environmenta l Laborator yaccordin g t o 4 0 CF R Par t 79 2

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### 2 Summary Th e 3 M Environmenta l Laborator yreceive d groundwate rsample s fro m tw o differen t well s locate d a t th e Off-Sit e 61 0 Well s i n Decatur , AL
. A tota l o f eleve n sampl e bottle s were receive d a t th e 3 M Environmenta l Laborator

yfo rperfluorooctanoat e (PFOA ) analysi s an d include d duplicat e groundwate r sample s fro m eac h samplin g location
. Sample s als o include d tw o fiel d matri xspik e (FMS ) sample s fo r eac h locatio n an d on e tri p blan k containin g Milli-Q TM wate ran d appropriat e tri p blan k spikes
. Th e groundwate rsample s an d tri p blank s were receive d fro m Westo n personne l o n Octobe r6 , 2011
. Al l of th e sample s were prepare d an d analyze d fo rPFO A followin g 3 M Environmenta l Laborator yMetho d ETS-8-044. 0 unde r3 M projec t GLP10-01-01-23
. Th e averag e measure d PFO A concentration s ar

e summarize d i n Tabl e 1
. Th e tri p blan k wa s below th e lowe rlimi t of quantitatio n (LLOQ ) o f 0.024 0 ng/mL , indicatin g adequat e contro l of sampl e contaminatio n durin g shippin g an d sampl e collection
. Th e analytica l uncertaint

ywa s estimate d a

t 100±12%
. Tabl e 1 . Summarize d PFO A Result s (Off-Sit e 61 0 Wells , Septembe r 2011 )

3 M LIM S I D Sampl e Descriptio n PFO A Concentratio n (ng/mL ) GLP10-01-01-023-00 1 DA L G W 61OS-0-11092 1 1,0 1 GLP10-01-01-023-00 2 DA L GW610S-DB-11092 1 1.3 1 Average 1.1 6 YoRPD Sample/Sample

Dup 26(1 ) GLP10-01-01-023-00 5 DALGW610L-0-11092 1 3.5 5 GLP10-01-01-023-00 6 DA L G W 61OL-DB-11092 1 3.7 6 Average 3.6 6 %RPD Sample/Sample

Dup 5. 7 GLP10-01-01-023-00 9 DAL-GW-TRIP01- 1 <0.024 0 Th e analytica l uncertaint

yfo rPFO A wa s estimate d a

t 100+12%
. (1 ) Th e relative percen t differenc e (RPD ) di d no t meet metho d acceptance criteri a ofs20%
. 

### 3 Introduction Thi s analytica l stud ywa s conducte d as par t of th e Phas e 3 Environmenta l Monitorin g an d Assessmen t Progra m fo rth e 3 M facilitylocate d i n Decatur , Alabama
. Th e objective o f th e overal l progra m i s t o gai n infonnatio n regardin g concentration s of perfluorooctanoat e (PFOA ) i n variou s environmenta l medi a suc h as groundwater , soil s an d sediment s that are associate d wit h an d nea rth e Decatu rfacility
. Thi s analytica l stud ywa s conducte d t o analyz e groun d wate rsample s collecte d fro m tw o Off-Sit e 61 0 well s locate d i n Decatur , A L fo rPFO A i n a n effor

t t o characteriz e regiona l groundwate rconditions
. Th e 3 M Environmenta l Laborator yprepare d sampl e bottle s (25 0 m L high-densit ypolyethylene ) whic h were shippe d t o Decatur , A L Westo n personne l prio rt o fiel d sampling
. Sampl e bottl e set s fo reac h groundwate rsamplin g locatio n include d a fiel d sample , fiel d sampl e duplicate , an d tw o fiel d spik e samples
. Eac h empt

ycontaine rfo rgroundwate rsampling s wa s marke d wit h a "fil l t o here " lin e t o produce a fina l sampl e volum e o f 20 0 mL
. Container

s designate d fo rfiel d matri xsample s were fortifie d wit h a n appropriat e matri xspike solutio n containin g PFO A prio rt o bein g sen t t o th e fiel d fo rsampl e collection
. Al l sampl e bottle s include d th e additio n o f "Ca-PFO A (interna l standard ) a t a nomina l

Pag e 6 of 4 4GLP10-01-01 ; Interi m Repor t 2 3 Analysi s of PFO

A i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1

wit h a n appropriat e matri xspik e solutio n containin g PFO A prio rt o bein g sen t t o th e fiel d fo rsampl e collection
. Al l sampl e bottle s include d th e additio n of "Cs-PFO A (intema l standard ) a t a nomina l concentratio n of 1 ng/mL , an d ^^C4-PF0 A (surrogat e standard ) a

t a nomina l concentratio n o f 0. 1 ng/mL
. Se e sectio n 8. 8 o f th e repor

t fo rfiel d matri xspike levels
. Th e "C4-PFO A surrogat e standar d wa s inadvertentl yno

t include d i n th e analysi s o f th e samples
. Sample s wer e prepare d an d analyze d accordin g t o th e procedur e define d i n 3 M Environmenta l Laborator ymetho d ETS-8-044. 0 "Metho d o f Analysi s fo rth e Detemninatio n o f Perfluorinate d Compound s i n Wate rb

yLC/MS/MS ; Direc

t Injectio n Analysis"
. Th e us e of a n intema l standar d wa s use d t o ai d i n th e dat a qualit yobjectives
. Tabl e 1 summarize s th e averag e PFO A concentratio n fo rth e duplicat e groundwate rsample s collecte d an d th e tri p blan k

sample
. Table s 10-1 2 summariz e th e individua l sampl e results an d th e associate d FM S recoveries
. Al l results fo rth e qualit ycontro l sample s prepare d an d analyze d wit h th e sample s ar e reporte d an d discusse d elsewher e i n thi s report . 4 Test & Control

Substances There wa s no

t a tes t substanc e o rcontro l substance s i n th e classi c sens e of a GL P study
. Thi s stud y wa s purel yanalytica l i n nature . 

### 5 Reference

Substances Th e analytica l reference substance s use d fo rthi s stud yare liste d below
.

Referenc e Substanc e PFO A (Linear ) PFO A (Linea r+ Branched ) "Cg-PFO A Chemica l Nam e Perfluorooctanoat e Perfluorooctanoat e Perfluorooctanoat e Chemica l Formul a C7F15COO H C7F15COO H ^^C8HFi50 2 Identifie r CA S #335-67- 1 CA S #95328-99- 7 CAS#MPFC-C-051 1 Us e Targe t Analyt e Referenc e Standar d Targe t Analyt e Referenc e Standar d Intema l Standar d Sourc e Oakwoo d Product s Wellingto n Wellingto n Expiration Dat e 01/17/201 8 03/17/201 4 05/25/201 4 Storag e Condition s Froze n Froze n Froze n Chemica l Lo t Numbe r 344 0 TPFOA031 1 MPFC-C-051 1 TOR Numbe r TCR07-004 1 TCR11-000 9 TCR11-001 6 Physica l Descriptio n Powde r Liqui d Liqui d Purit y 99.1 % 98.3 % NA'^ * (1 ) Compoun

d is par t o f a custom mixtur

e o f mass-labele

d perfluorinate

d c»mpound

s a t a concentration o

f 5. 0 pg/mL
.

Pag e 9 o f 4 4Tabl e 2 . Sampl e Descriptio n Ke y Code . GLP10-01-01 ; Interi m Repor t 2 3 Analysi s of PFOA i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1

Strin g Numbe r Strin g Descripto r Exampl e Example DAL-GW- 610S-LS-110921 1 Sample Location DAL= Decatur, Alabama 2 Sample Type GW= Groundwater 3 Well ID Example: DAL610 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 Metho d Analysi s fo ral l analyte s wa s complete d followin g 3 M Environmenta l Laborator ymetho d ETS-8-044. 0 "Metho d of Analysi s fo rth e Determinatio n of Perfluorinate d Compound s I n Wate rb yHig h Performance Liqui d Chromatography/Mas s Spectrometr yDirec t Injeiitio n Analysis"
. 7. 2 Sampl e Collectio n Sample s were collecte d i n 25 0 m L Nalgene TM (high-densit ypolyethylene ) bottle s prepare d a t th e 3 M Environmenta l Laboratory
. Sampl e bottle s associate d wit h GLP10-01-01-2 3 were retume d t o th e laborator ya t ambien t condition s o n Octobe r6 , 2011
. Sample s were store d refrigerate d a t th e laborator

y afte rreceipt
. A se t of laborator yprepare d Tri p Blan k

an d Tri p Blan k

fiel d matri xspike s were sen t wit h th e se t of sampl e collectio n bottles
. 

### 7. 3 Sampl e Preparatio n Sample s were prepare d byremovin g a n aliquot o f th e wel l mixe d sampl e an d placin g i t i n a n autovia l fo r analysis
. Durin g th e preparatio n o f th e laborator ycontro l samples , a n aliquot of a separat e intema l standar d spikin g solutio n wa s adde d t o th e laborator ycontro l sample s (nomina l concentratio n of 1 ng/mL)
. Th e sample s bottle s were spike d wit h a n interna l standar d mi xa t a nomina l concentratio n of 1 ng/m L prio rt o bein g sen t t o th e fiel d fo rsampl e collection
. 7. 4 Analysi s Al l stud y samples an d qualit

y contro l samples wer

e analyze d fo r PFO A usin g hig h performanc e liqui d chromatography

/ tande m mas s spectrometr y (HPLC/MS/MS) . Detaile d instmmen

t parameters , th

e liqui d chromatograph

y gradien t program , an d th e specifi c mas s transition s analyzed ar e describe

d i n the ra wdat a har d copie s place d i n th e fina l dat

a packet , an d ar

e briefl y describe

d belo wi n Tabl e 3 , Tabl e 4 an d Tabl e 5 .

Pag e 1 0 of 4 4Tabl e 3 . Instrumen t Parameters . GLP10-01-01 ; Interi m Repor t 2 3 Analysi s o f PFO A i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1

Instrumen t Nam e ETS Kiri < Analytica l Metho d Followe d ETS-8-044. 0 Analysi s Dat e 10/6/201 1 Liqui d Ctiromatograpl i Agilen t 1200 Guar d colum n Betasi l C1 8 (4. 6 m m X 10 0 mm) , 5 n Analytica l colum n Betasi l CI S (4. 6 mm X 10 0 mm) , 5 u Injectio n Volum e 2 5 n L Mas s Spectromete r Applie d Biosystem s AP I 550 0 Io n Sourc e Turb o Spra y Electrod e Turb o io n electrod e Polarit y Negativ e Softwar e Analyst 1.5. 2 Tabl e 4 . Liqui d Chromatograph y Conditions . ste p Total

Time Flow

Rate Percen M Percent B Number (min) (pUmin) (2 mM ammonium

acetate) (MethanoO 10/6/201 1 Analysi s 0 0. 0 75 0 97. 0 3. 0 ' 1 2. 0 75 0 97. 0 3. 0 2 14. 5 75 0 5. 0 95. 0 3 15. 5 75 0 5. 0 95. 0 4 16. 5 75 0 97. 0 3. 0 5 20. 0 75 0 97. 0 3. 0 Tabl e 5 . Mas s Transitions .

Analyte Mass Transition Q1/Q3 Intemal Standard Mass

Transition Q1/Q3 PFOA 413/369 t'CJ-PFOA 421/376 413/219 413/169 Dwel l tim e wa s 3 0 mse c fo reac h transition
. Th e individua l transition s wer e summe d t o produce a "tota l Io n chromatogram " (TIC) , whic h was use d fo rquantitation
. 

### 8 Analytical

Results 8. 1 Calibratio n Sample s were analyze d usin g a stabl e isotop e intema l standar d calibratio n curve . Calibratio n standard s were prepare d b

yspikin g know n amounts o f th e stoc k

solutio n containin g PFO

A (referenc e standar

d containin g bot h linea ran d branche d isomers ) into a laboratory-prepare d syntheti c groundwate r containin g calciu m an d magnesium
. A separat e interna l standar d spikin g solutio n wa s prepare d an d a n aliquot wa s adde d a

t th e sam e leve l t o al l calibratio n standard s an d laborator ycontro l sample s a

t a nomina l concentratio n of 1 ng/mL
. A calibratio n curve rangin g fro m approximatel y0.02 5 ng/m L t o 2 5 ng/m L wa s prepared
.

Pag e 1 1 of 4 4GLP10-01-01 ; Interi m Repor t 2 3 Analysi s o f PFOA i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1

A quadratic , 1/

xweighted , calibratio n curve o f th e standar

d pea k area/pea k

are a ratio s wa s use d t o fi t th e dat a fo reac h analyte
. Th e dat a were no t force d throug h zero durin g th e fittin g process . Calculatin g th e standar

d concentration s usin g th e pea k area / pea k are a ratio s an d th e resultan t calibratio n curve confimned accurac

yof eac h curve point
. Eac h curve poin t wa s quantitate d usin g th e overal l calibratio n curve an d reviewe d fo raccuracy . Metho d calibratio n accurac

yrequirements of 10 0 ±25 % (10 0 ±30 % fo rth e lowes t curve point ) were me

t fo r PFOA
. Th e correlatio n coefficien t (r ) wa s greate rtha n 0.99 5 fo rPFOA
. 8. 2 Syste m Suitabilit y A calibratio n standar

d wa s analyze d fou rtime s a t th e beginnin g of th e analytica l sequence t o demonstrat e overal l syste m suitability
. Th e acceptance criteri a of les s tha n o requa l t o 5 % relative standar d deviatio n (RSD ) fo rpea k are a an d retentio n tim e criteri a of les s tha n o requa l t o 2 % RS D wa s me t fo rPFOA
. 

### 8. 3 Limi t o

f Quantitatio n (LOQ ) Th e LO Q fo

r thi s analysi s i s th e lowes t non-zer o calibratio n standar

d i n the curv

e tha t meet s linearit y an d accurac

y requirement

s an d fo r whic h th e area count

s ar e a t leas t twic e thos e o f th e appropriat

e blanks . Th e nominal LO Q fo r PFO A ca n b

e found i n Tabl e 6 . Tabl e 6 . Limi t o

f Quantitatio n (LOQ) . Analysis Date PFOA

ng/mL 10/6/1 1 0.024 0 8. 4 Continuin g Calibratio n Durin g th e cours e of eac h analytica l sequence , continuin g calibratio n verificatio n sample s (CCVs ) were analyze d t o confim n that th e instrumen t respons e an d th e initia l calibratio n curve were stil l i n control
. Al l CCVs me t metho d criteri a of 100 % ±25 % fo rPFOA
. 

### 8. 5 Blank s Two type s of blank

s were prepare d an d analyze d wit h th e samples : procedura l blank s an d tri p blanks
. Procedura l blan k

results were reviewe d an d use d t o evaluat e metho d perfomnanc e t o detemnin e th e LOQ fo rPFOA
. Tri p blank s reflec t th e shippin g an d sampl e collectio n conditon s th e sampl e bottle s an d sample s experience
. 8. 6 La b Contro l Spike s (LCSs ) Low , mid , an d high-leve l la b contro l spike s were prepare d an d analyze d i n triplicat e wit h eac h preparatio n set . LCS s were prepare d b yspikin g know n amounts of th e analyt e into 1 0 m L of laborator y Mill i Q wate ro rsyntheti c groundwater , t o produce th e desire d concentration
. Th e spike d wate rsample s were the n analyze d i n th e sam e manne ra s th e samples
. Th e metho d acceptance criteria , averag e of LC S a t eac h leve l shoul d b e withi n 100 % ±20 % wit h a n RS D <20% , were met fo rth e PFOA
. Th e followin g calculation s were use d t o generat e dat a i n Tabl e 7 fo rlaborator ycontro l spikes : i^or , . o Calculate d Concentratio n LC S Percen t Recover

y= * 100 % Spik e Concentratio n LCS % RS D = standar d deviatio n LC S replicate s . ^

averag e LC S recover

y

Pag e 1 2 o f 4 4Tabl e 7
. Laborator yContro l Spik e Recovery
. GLP10-01-01 ; Interi m Repor t 2 3 Analysi s of PFOA i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1

ETS-8-044. 0 Analyze d 10/6/201 1 Linear + Branched

PFOA
Lab ID Spiked

Concentration (ng/mL) Calculated

Concentration (ng/mL) YoRecovery LCS-111006- 1 0.19 0 0.18 6 97. 8 LCS-111006- 2 0.19 0 0.17 7 93. 0 LCS-111006- 3 0.19 0 0.18 7 98. 2 Averag e ±%RS D 96.3 % ±3.0 % LCS-111006- 4 1.9 0 1.9 6 10 3 LCS-111006- 5 1.9 0 1.9 6 10 3 LCS-111006- 6 1.9 0 1.9 4 10 2 Averag e ±%RS O 103 % ±0.56 % LCS-111006- 7 9.5 2 9.6 6 10 1 LCS-111006- 8 9.5 2 9.4 4 99. 1 LCS-111006- 9 9.5 2 9.4 9 99. 6 Averag e ±%RS D 99.9 % ±0.99 % 8. 7 Analytica l Metho d Uncertaint y Analytica l uncertaint

yi s base d o n historica l Q C dat a that i s contro l charte d an d use d t o evaluat e metho d accurac

yan d precision
. Th e metho d uncertaint yi s calculate d followin g ETS-12-012.2
. Th e standar d deviatio n i s calculate d fo rth e set o f accurac yresults (i n % ) obtaine d fo rth e Q C samples
. Th e expande d uncertaint

yi s calculate d b

ymultiplyin g th e standar

d deviatio n b

ya facto rof 2 , whic h con-espond s t o a confidenc e leve l o f 95%
. Tabl e 8
. Analytica l Metho d Uncertainty
. Analyt e Metho d Standar d Deviatio n Metho d Uncertaint y PFO A ETS-8-044. 0 6.1 9 ±12 % 8. 8 Fiel d Matri x Spike s (FMS ) Lo w an d hig h fiel d matri xspike s were collecte d a t eac h samplin g poin t t o verif ythat th e analytica l metho d i s applicabl e t o th e collecte d matrix
. Fiel d matri xspike s were generate d byaddin g a measure d volum e of fiel d sampl e t o a containe rspike d b yth e laborator

ywit h PFO

A (referenc e standar

d containin g primaril ylinea rPFOA

) prio rt o shippin g sampl e container s fo rsampl e collection
. Fiel d matri xspik e recoverie s withi n metho d acceptanc e criteri a o f 100±30 % confin n that "unknown " components i n th e sampl e matri xd o no

t significantl yinterfere wit h th e extractio n an d analysi s o f th e analyte s o f interest
. Fiel d matri xspike concentration s must b e 50 % of th e sampl e concentratio n t o b e considere d a n appropriat e fiel d spike
. Fiel d matri xspike s are presente d i n sectio n 9 of thi s report .

Pag e 1 3 o f 4 4GLP10-01-01 ; Interi m Repor t 2 3 Analysi s of PFOA i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1

Tabl e 9
. Fiel d Matri xSpik e Levels
. Samplin g Locatio n Spik e Leve l PFOA , ng/m L 6 1 OS , 6 1 O

L an d Tri p Blan k Lo w 0.25 0 6 1 OS , 6 1 O

L an d Tri p Blan k Hig h 1.0 0

^ . . „ „ (Sampl

e Concentratio

n o f FMS-Averag e Concentration : FieldSampl e & FieldSampl

e Dup. ) ^ , .„. , FM S Recover y = -^ ^ —* 100 % Spik e Concentrato

n 

### 9
. Dat a Summar yan d D/sci/ss/on i

- -

_.iii
. Th e table s below summariz e th e sampl e results an d fiel d matri xspik e recoverie s fo rth e samplin g location s a s wel l a s th e Tri p Blanks
. Results an d averag e value s are rounde d t o thre e significan t figure s accordin g t o EP

A roundin g rules
. Becaus e o f rounding , value s ma

yvar yslightl yfro m thos e liste d i n th e ra

w data
. Fiel d matri xspike recoverie s meetin g th e metho d acceptance criteri a of ±30% , demonstrat e tha t th e metho d wa s appropriat e fo rth e give n matri xan d thei rrespective quantitative ranges . DA L G W 6 1 O

L 11092 1 - Th e hig h fiel d matri xspik e a t 1 ng/m L wa s les s tha n 50 % of th e PFO A concentratio n i n th e sampl e an d woul d nomiall yno t b e calculated
. However , sinc e th e "C4-PFO A surrogat e (whic h wa s adde d t o th e samples ) wa s inadvertentl yomitte d fro m th e analysis , th e fiel d matri xspik

e recover ywa s calculate d an d foun d t o b e 84.5%
.

Pag e 1 4 of 4 4Tabl e 10 . DA L G W 6 1 O S 11092 1 GLP10-01-01 ; Interi m Repor t 2 3 Analysi s of PFO A i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1

PFOA Concentration 3M LIMS ID Description (ng/mL) YoRecovery GLP10-01-01-23-00 1 DA L G W 6108-0-11092 1 1.0 1 N A GLP10-01-01-23-00 2 DA L GW610S-DB-11092 1 1.3 1 N A GLP1CKI1-01-23-00 3 DA L GW610S-LS-11092 1 1.3 2 N C GLP10-01-01-23-00 4 DALGW610S-HS-11092 1 2.2 7 11 1

Average Concentration

(ng/mL)

± %RPD 1.16ng/mL±26%'^^ NA = No t Applicabl e NC=No t Calculated
. Th e sampl e concentratio n I s greate rtha n 2xth e spik e level
. (1 ) Th e relative percen t differenc e (RPD ) di d no t meet metho d acceptance criteri a of s20%
. Tabl e 11 . DA L G W 6 1 O L 11092 1 PFOA Concentration 3MUMSID Description (ng/mL) %Recovery GLP10-01-01-23-00 5 DA L G W 61OL-0-11092 1 3.5 5 N A GLP10-01-01-23-00 6 DA L G W 61OL-DB-11092 1 3,7 6 N A GLP10-01-01-23-00 7 DA L G W 61OL-LS-11092 1 3.5 6 N C GLP10-01-01-23-00 8 DA L GW610L-HS-11092 1 4.5 0 84. 5

Average Concentration

(ng/mL)

± YoRPD 3.66 ng/mL±5.r/o NA = No t Applicabl e NC=No t Calculated
. Th e sampl e concentratio n I s greate rtha n 2xth e spik e level
. (1 ) Th e hig h fiel d matri xspike a t 1 ng/m L wa s les s tha n 50 % of th e PFO A concentratio n i n th e sample
. However , since th e "C v PFO A surrogat e (whic h wa s adde d t o th e samples ) was inadvertentl yomitte d fro m th e analysis , th e fiel d matri xspik e recover ywa s calculated
. Tabl e 12 . Tri p Blan k

11092 1 PFOA 3M LIMS ID Descrrptfo n Concentration (ng/mL) YoRecovery GLP10-01-01-23-00 9 DALGWTRIP01-0-11092 1 <0.024 0 N A GLP10-01-01-23-01 0 DA L GWTRIP01 - LS-11092 1 0.22 8 91. 2 GLP10-01-01-23-01 1 DA L GWTRIP01-HS-11092 1 1.0 5 10 5 N A = No t Applicabl e

Pag e 1 5 of 4 4GLP10-01-01 ; Interi m Repor t 2 3 Analysi s of PFO

A i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1

10 Conclusion Laborator ycontro l spike s an d fiel d matri xspike s were use d t o determin e th e analytica l metho d accurac yan d precisio n fo rPFOA
. Analysi s wa s successfull ycomplete d followin g 3 M Environmenta l Laborator ymetho d ETS-8-044. 0 describe d herein
. 11 Data/Sample

Retention Al l remainin g sample s an d associate d projec t dat a (hardcopyan d electronic) wil l b e archive d accordin g t o 3 M Environmenta l Laborator ystandar d operatin g procedures
. 12 Attachments Attachmen t A : Protoco l Amendmen t 2 3 (Genera l Projec t Outline ) Attachmen t B : Representative Chromatogram s an d Calibratio n Curve s Attachmen t C : Analytica l Metho d - ETS-8-044. 0 Attachmen t D : Metho d Deviatio n

Pag e 1 6 o f 4 4GLP10-01-01 ; Interi m Repor t 2 3 Analysi s o f PFOA i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1



### 13 Signatures

Clesto n Lange , Ph.D. , 3

M Principa l Analytica l Investigato r / Dat

e 

# •^^^y^i^^^

^^^^^// William K . Reagen , Ph.D. , 3M Environmenta l Laborator y Manager Dat e 

# f 6 Gar y Hoher^steiny3M Sponso r Representativ e Dat e

Jaisimh a K^ari , Stud

y Director / Dat e

Pag e 1 7 o

f 4 4GLP10-01-01 ; Interi m Repor t 2 3 Analysi s of PFOA i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1


### ATTACHMEN T A : PROTOCO L AMENDMEN T

Pag e 1 8 o f 4 4GLP10-01-01 ; Interi m Repor t 2 3 Analysi s of PFOA i n Groundwate rSample s Analytical

ProtocomPmm''''"''''°'' Amendment

23


### Study Title Analysi s o f Perfluorooctanoi c Aci d (PFOA ) i n Groundwater , Soi l an d Sedimen t fo rth e

3 M Decatu rPhas e 3 Site-Relate d Monitorin g Progra m

PROTOCO L AMENDMEN T NO . 2 3

Amendment

Date: Septembe r14 , 201 1 Performing

Laboratory 3 M Environmental , Health , an d SafetyOperation s

S M Environmenta l Laborator y Buildin g 260-5N-1 7 Maplewood , M N 55144-100 0 Laboratory

Project Identification GLP10-01-0 1 Sampling

Event Off-Sit e 61 0 Well s

Pag e 1 o f 6 Pag e 1 9 of 4 4GLP10-01-01 ; Interi m Repor t 2 3 Analysi s of PFO

A i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1 Analytical

Protocol:

GLP10-01-01 Amendment

23 Thi s amendmen t modifie s th e followin g portio n o f protocol : "Analysi s o f Perfluorooctanoi c Aci d (PFOA ) i n Groundwater , Soi l an d Sedimen t fo rth e

3 M Decatu rPhas e 3 Site-Relate d Monitorin g Program "

PROTOCOLREADS: N o change s t o th e vvordin g of th e protoco l ar e required
.

AMEND TO READ: N o Change s t o th e wordin g of th e protoco l ar e required
. Thi s amendmen t onl yaddresse s an d documents , th e additio n o f th e Genera l Project Outlin e (GPO ) fo rth e collectio n an d analysi s o f groundwate rsample s a s par t of th e 3 M Decatu rPhas e 3 Progra m fo rPFO A (GLP10-01-01)
. Th e anticipate d sampl e collectio n wil l occu raroun d th e timefram e o f th e wee k o f Septembe r19
. 2011
. Th e groundwate rsample s fo rthi s samplin g even t wil l b e entere d int o th e 3 M Environmenta l Laborator yLIM S a s projec t GLP10-01-01-2 3 an d reporte d a s interi m repor t GL P 10-01-01-23 , (reflectin g stud yGLP10-01-0 1 an d amendmen t -23)
.

Reason: Th e reaso n fo rthi s amendmen t i s t o documen t th e Genera l Project Outlin e (GPO ) whic h describe s th e anticipat e groundwate rsampl e collectio n even t fo rtw o ne w v^^ell s locate d a t a n off-sit e location
. Th e GP O i s thre e page s i n lengt h an d include d a s attache d t o thi s amendmen t form
.

Pag e 2 o f 6 Pag e 2 0 o f 4 4GLP10-01-01 ; Interi m Repor t 2 3 Analysi s of PFOA i n Groundwate rSample s ! Off-Sit e 61 0 Wells ; Septembe r201 1 i Analytical

Protocol:

GLP10-01-01 Amendment

23



### Amendmen t Approva l

Gar yHohenstein , Sponso rRepresentative Date

Date Clesto n C
. Lange , Principa l Analytica l Investigato r

Willia m Reagen , EH S Opn s Envil-onmenta l La b Managemen t Dat e



# mm Jaisimh a Kesa n P.E. , DEE , Stud yDirecto r I Date/

Pag e 3 o f 6 Pag e 2 1 o f 4 4GLP10-01-01 ; Interi m Repor t 2 3 Analysi s o f PFOA i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1 Analytical

Protocol:

GLP10-01-01 Amendment

23 

### 3 M Environmenta l Healt h & SafetyOperations , Environmenta l Laborator y Genera l Projec t Outlin e To , From : cc :
Date : Subject : Gar

yHohenstein , 3 M EHS&Opn s Susa n Wolf , 3 M EHS&Opns ; Environmenta l La b Willia m Reagen , 3 M EHS&Opns ; Environmenta l La b Cleston.Lange , 3 M EHS&Opns ; Environmenta l La b Ja i Kesari , Westo n Solution s Septembers , 201 1 Analysi s o f Perfluorooctanoi c Aci d (PFOA ) i n GroOndwater , Soi l an d Sedimen t fo rth e 3iV l Decatu rPhas e 3 Site-Relate d Monitorin g Prograni ; GL P Interi m Repor t 23 ; Off-Sit e 61 0 Well s 

### 1 Genera l Projec t Informatio n
3 M Sponso rRspresentativ e Gar yHohenstei n 3 M EH S Operation s 3iV I Buildin g 224-5W-0 3 Sain t Paul
. M N 55144-iOO O Phone : (651 ) 737-357 0 aahohensfeinfflmmm.co m 3 M Environmenta l Laborator yManagemen t Willia m K
. Reage n 3IV I EH S Opns , Environmenta l Laborator y 260-5N-1 7 65 1 733-973 9 Contact s wkreaaeni5)mmm.co m Principa l Analytica l Investigato r Clesto n Lang e ; 3 M EH S Opns , Environmenta l Laborator y 260-5N-1 7 65 1 733-986 0 colanae(S>mmn i co m Samplin g Coordinato r Timoth yFrina k vyestp n Solution s Timoth y.frinaktawestonsolutions.coi n Phone : {334)-332-912 3 La b Reques t Numbe r GLP10-01-01-2 3 Si xDigi t Departmen t Numbe r Dep t #530711 , Project #002267444 9 Projec t Schedule/Test.Date s Samplin g schedule d fo rth e wee k o f Septembe r19 , 201 1 All verbal and written correspondence

will be directed to Gary Hohenstein

and Jai Kesari.
Pag

e 4 o f 6 Pag e 2 2 o f 4 4GLP10-01-01 ; Interi m Repor t 2 3 Analysi s o f PFOA i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1 Analytical

Protocol:

GLP10-01-01 Amendment

23 

### 2 Backgroun d Informatio n an d Projec t Objective(s ) Th e 3 M EH S Operation s Laborator y(3 M Environmenta l Lab ) wil l receiv e an d analyz e groundwate r sample s collecte d fro m tw o samplin g location s fo rPerfluorooctanoi c Aci d (PFOA ) fro m ne w well s locate d off-site
. Analyse s wil l b e conducte d unde rth e GL P requirement s o f EP A TSC A Goo d Laborator yPractic e Standard s 4 0 CF R 792
. Groundwate rsample s wil l b e collecte d b yWesto n Solution s personnelth e wee k o f Septembe r19 , 2011
. Th e 3 M Environmenta l Laborator ywil l prepar e th e sampl e bottle s wit h al l require d spike s t o ensur e tha t result s fo rPFOA ar e o f a know n precisio n an d accuracy . Th e fina l repor t wil l b e submitte d t o Gar y Hohenstei n an d Ja i Kesar i upo n completio n unde rinteri m repor t GLP10-01-01-23
. 

### 3 Projec t Schedul e Sampl e collectio n bottle s wil l b e prepare d b y3 M Environmenta l Laborator yfo rsamplin g th e wee k

of Septembe r 14 , 2011
. Sampl e bottle s wil l be shippe d i n cooler s overnigh t t o 3 M Decatu rfo rarriva l o n Friday , Septembe r 16 , 2011
. Sampl e bottle s shoul d be stoi-ed refrigerate d on-sit e unti l sampl e collection
. Marti n Smit h \

V\lest6r \ Traile r 3 M Decatu rPlan t 140 0 Stat e Docks Roa d Decatur , Alabam a 3560 1 

### 4 Tes t Parameiters Th e targete d limi t of quantitatio n wil l b e 0.02 5 ng/m L (ppb ) fo rPFOA
. Two samplin g location s have bee n specified
. Se e attachmen t A fo ra list of th e samplin g location s that wil l b e collecte d fo rthi s samplin g event . Fo reac h samplin g location , a tota l o f fou rsampl e bottle s wil l b e collecte d (sample , sampl e duplicate , lo w fiel d matri xspike , an d hig h fiel d matri xspike)
. Th e "fil l t o here " lin e o n eac h 25 0 m L Nalgen e bottl e wil l b e 20 0 mL
. On e se t of tri p blank s consistin g of reagent-grad e wate ra s wel l tri p blan k spike s wil l b e prepare d at th e 3 M Environmenta l Laborator yan d sen t t o th e samplin g locatio n wit h th e othe r bottles
. Al l sampl e bottle s wil l includ e th e additio n of "Cg-PFQ A (interna l standard ) at a nomina l concentratio n o f 1 ng/mL
. Al l sampl e bottle s wil l als o includ e th e additio n of "C4-PFO A (sun-ogat e spike ) a

t a nomina l concentratio n of 0. 1 ng/mL
. Th e tabl e belo w list s th e matri xspike level s that wil l b e prepared
. Wel l No
. Sampl e Leve l Spik e Cone
. (ng/mL ) 6 1 O S andei.O R Low 0.2 5 6 1 O S andei.O R Hig h 1, 0 Tri p Blan k Lo w 0.2 5 Tri p Blan k Hiq h 1. 0

Pag e 5 o f 6 Pag e 2 3 o f 4 4GLP10-01-01 ; Interi m Repor t 2 3 Analysi s o f PFOA i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1 Analytical

Protocol:

GLP10-01-01 Amendment

23

5 Tes t Method s Sample s wil l b e prepare d an d analyze d b yLC/MS/M S following : ETS-8-044. 0 "Determinatio n of Perfluorinate d Compound s I n Wate rb yHig h Perfonnanc e Liqui d Chromatography/Mas s Spectrometr yDirec t Injectio n Analysis"
. Alternately , sample s ma yb e analyze d b

yET S 8-154. 3 "Detemninatio n o f Perfluorinate d Acids , Alcohols , Amides , an d Sulfonate s I n Wate rB ySoli d Phas e Extractio n an d Hig h Perfomnanc e Liqui d Chromatography/Mas s Spectrometry"
. Th e data qualit

yobjective s fo rthes e studie s ar e quantitative result s fo rth e targe t analyte s wit h a n analytica l accurac yo f 100±30%
. Fiel d matri xspike s not yieldin g recoverie s withi n 100±30 % wil l be addresse d i n th e repor t an d th e fina l accurac

ystatemen t ma

yb e adjuste d accordingly
. Wher e ajsplicable , sample s wil l be analyze d agains t a n interna l standar d calibratio n curve. . Eac h curve poin t wil l contai n isotopicallyTlabele d peffluorocarboxyli c acid s an d perfluorosulfoni c acid s a t a nomina l concentratio n o f 1 ng/mL
. Th e calibratio n curv e wil l be generate d b ytakin g th e rati o of th e standar d pea k are a count s ove rth e interna l standar

d pea k are a count s t o fi t th e dat a fo reac h analyte
. 6 Reportin g Requirement s Fo reac h samplin g location , th e repor t wil l contai n th e result s fo rth e sarnple , sampl e duplicate , ari d th e fiel d matri xspikes
. Tri p blan k an d tri p blan k

spike s wil l b e reporte d fo rth e samplin g even t a s wil l an y equipment/rinseat e blank s prepare d i n th e field ; Laborator ycontro l spike s of reagen t wate rprepare d a t th e tim e o f sampl e extractio n wil l als o b e reporte d an d use d t o evaluat e th e overal l metho d accurac yan d precision
. Metho d blank

s o f reagen t wate rprepare d at th e tim e of sampl e extractio n wil l b e use d t o deterhiin e th e metho d detectio n limit
. Fo rthos e samplin g location s where th e fiel d matri xspike leve l wa s no t appropriate , du e t o highe rtha n expecte d analyt e concentrations , a laborator ymatri xspike ma

yb e prepare d an d wil l b e include d i n th e fina l report .

Pag e 6 o f 6 Pag e 2 4 of 4 4GLP10-01-01 ; Interi m Repor t 2 3 Analysi s of PFOA i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1


### ATTACHMEN T B : REPRESENTATIV E SAMPL E CHROMATOGRAM S AN D CALIBRATIO N CURVE(S )

Pag e 2 5 of 4 4Result s Name : kiiioo6a.]GatP10-01-01 ; Interi m Report2 3 Analysi s of PFO A i n Groundwate rSample s Off-Sit e 51 0 Wells ; Septembe r201 1

Proc . Alg f Nols? . par e Base . Sub .

Smoothin g Wl e R T Window : Expecte d RT :

.306+00 5 cp a 

# I SatT^jl * N»im : •k11100e«0ie " Sirrpl ' ID ; "1 1 003-4(M - Rto : "k l P« k Nirr* : •13C8PFOA-IS(IS) " Misif.i) : -421.000078.00 0 Di " Cotmwnt : "1. 0 no/m L F

C il d I n Synth
. VJatt f 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 5000.0 0 0.0 0 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*a k Nam* : 'l3C8PFOA-IS(IS} - Mau(«s) : ComrTwnt : 'Metho d Bbnk " Annotatton ; * " Sample Index: 23



# I San ^

Nam*:'kl l 1006*024 " SarrpI * ID:-GLP10-O1-O1-23-OO1 ' Psa k Nam* : '13C8PFOArtS(tS) ' MaM(**) : '421.000/376.00 0 Da ' Comm*nt : "DAL-GVM l 0S-O- " Annotatton : " Sampl e Index ; 2 4

iiii : Specif y ParaniBt c

.35e*O0 5 cp a

14. 8 15. 0 15. 1 15. 2 15. 3 15. 4 15. 5 Dat a printe d b yST

W Printin g Time : 3:23:5 8 P M 15. 6 15. 7 15. 8 16. 2 16. 3 16. 4 16. 5 16. 6 16. 7 16. 8 Pag e 1 o f 4Result s Name I 

# I Sampl*Nim*:-k111O06«D35 - Sanv>l * ID:'GLP1(K)l-01-23-00S - Fk ; P*a k Nam* : "ISCSPFOAr^SOS) ' Ma»s(*«) ; •421.000/376.00 0 Da Comment : -DAL-GW-TRIPOI-O - Annotation: " Sampl e Index : 3 5 Sampl e Type : Unknow n 1.0 0 Acq
. Da t

.thin g Width : iRelativ e Rl : 15. 0 mi n 

# I Sanvt * Nam*:'k1110063041 * Sampt * ID:'LCS-111006-1 ' Fil«:'k11100ea.v>if r P*a k 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 ; Interi m Report2 3 Analysi s of PFOA i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1

S. S 16. 0 T1m*.m» i 

# I SampI * Name : 'k111006a044 ' Sampl * ID : 'LCS-11100&4 ' Fl * Pas k Nam* : '13C8PFOMS(IS) ' Mass(«s) : *421.000/376.00 0 Da * Comment : "2pp b LCS ' Arnotalion; " Saiqile Index:

AA

R T Windcw : 

# I Sanpl*Nam*:'kni006a04 rSampl*ID:-LCS-111006- rRle : Pea k Name : •13C«PFOA^S0S> • Mass(es) ; "421.000376.00 0 Da ' Comment : "1 0 pp b LCS ' Annotation : ~ Snmpl e Index : 47 Snmpl e Type : Q C Concentration : 0.99 t ng/m L Calculate dCone : N/ A Acq . Date : 10/7/201 1

Smoothin g Wid i R T Window :

.34e-0O 5 cp a

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? ? o f 4 4 16. 6 16. 7 16. 8 Dat aprinte db y ST W Printin g Time : 3:23:5 9 P M Pag e 2 o f 4Result s Name : kiiioo6a.<]^10-01-01 ; Interi m Report2 3 Analysi s of PFO A i n Groundwate rSample s

Dat aprinte db y ST W Printin g Time : 3:23:5 9 P M Pag e 3 o f 4*ETS-Kir k Result s Name ; 

# I SanvUName:'k111006a03S ' Sanfil * ID:"GLPlO-01-01-23-009 ' Fi*:'k111006a.vJ r P** k Name : 'PBDA ' Maw{*s) : "413.00tV369.00 0 Da,413.000/218.00 0 Da,413.000/169.00 0 Da ' Comment : 'OAL-GW-TRIPOI-O ^ Annotation : - Sampl e Index : 3 5 Sampl e Type : Unknow n Acq . Tims : 3:0^:0 3 A M Modified : Ye a Pioc . Alqorithm : Specif y Parame t Noia e Peccentage : 5 0 Base . Sub . Window : 1.0 0 mi r Psak-Spllt. Factor: A Repor tLarges tPeak : Ye s Min
. Pea k

Height : 0.0 0 c p

. Pea k
Us e Relativ t Int . Type : 0.0 0

Valle y 15. 7 1175 3 c c 2.56e+00 3

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- rFile:'kll1006a.vi( r Pea k Nam* : 'PFOA ' MtM(e«) : •413.000«e9.00 0 Da.413.000/219.00 0 Da.413.000/169.00 0 Da " Commen t '0.2pp b LCS ' Annotation : * * Sampl
. kiiioo6a.<5fepio-01-01 ; Interi m Repor t 2 3 Analysi s o f PFO A i n Groundwate rSample s

Sampl e Type : O C

Lhm ; Spacif yPatome t



# I Sarr^>leName:"k111006a044 ' Serrpl * ID:'LCS-111006-4 ' Fl*:'klll006a.wi r P*a k Name : "PFOA " Mass(es) : '413.000/369.00 0 Da.413.000/219.00 0 D a ,413.000/169.00 0 Da Comment : '2pf> b LCS ' Annotation: " Sampl e Index : 4 4 Sampl e Type : Q C Concen tra tion : 1.9 0 ng/m L Calculate d Cone : 1.S 5 ng/m L "0/7/201 1 Acq
. 6:1 '

. Algocith r

. Sub . Win i 

# I SBnvleName:-k111006a04 rSampl e ID:'LCS-lHOOe- rFile:-klllOOea.intf r P*« k Name:'PFOA ' MaM(et):'413.000i'3e9.00 0 Da,413.000/219.0O0Da,413.000/169.00 0 Di ' Commen t '1 0 pp b LCS ' Annotation:' " Sampl e Index : 47

Specif y Pa i

. : 5 0 .w : 1.0 0 Proc . Algcr l Peak-Split . Repor tLargea tI Min . Pea k Heigh t Min . Pea k Widt h

Int . Type : Manua l Rstantio n Tlm- i : 15. 7 Area : 1075327 2 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 , mi n 15. 9 18. 0 18. 1 16. 2 16. 3 16.4 Dat a printe d b yST W Printin g Time : 3:23:5 9 P MGLP10-01-01 ; Interi m Repor t 2 3 Analysi s of PFO A i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1 Result s Name : klll006a.rd b

Dat a printe d b yST W Printin g Time : 3:18:2 9 P M Pag e 1 o f 1 Pag e 3 0 o f 4 4GLP10-01-01 ; Interi m Repor t 2 3 Analysi s of PFOA i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1


### ATTACHMEN T C : ANALYTICA L METHOD(S )

Pag e 3 1 o f 4 4GLP10-01-01 ; Interi m Repor t 2 3 Analysi s o f PFOA i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1


# 3IV I Envvmonmenta l Laborator y

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 Effectiv e Date : Q y1 ^ /<3" ?
Approve d By :

Willia m K

. Reagen , Laborator

yManage rDat e

ETS-8-044. 0 Pag e 1 of 1 1 Metho d of Analysi s fo rth e Determinatio n o f Perfluorinate d Compound s i n Wate rbyLC/MS/MS ; Direct Injectio n Analysi s Pag e 3 2 o f 4 4GLP10-01-01 ; Interi m Repor t 2 3 Analysi s of PFOA i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1

1 Scop e an d Applicatio n Thi s metho d i s t o b e use d t o quantif yPerfluorobutanoi c Aci d (PFBA) , Perfluoropentanoi c Aci d (PFPeA) , PerfluorohexanoicAci d (PFHA) , Perfluoroheptanoi c Aci d (PFHpA) , Perfluorooctanoi c Aci d (PFOA) , Perfluorononanoi c Aci d (PFNA) , Perfluorodecanoi c Aci d (PFDA) , Perfluoroundecanoi c Aci d (PFUnA) , Perfluorododecanoi c Aci d (PFDoA) , Perfiuorobutanesulfonat e (PFBS) , Perfluorohexanesulfonat e (PFHS) , an d Perfluorooctanesulfonat e (PFOS ) b yHig h Performance Liqui d Chromatograph ycouple d t o a tande m Mas s Spectrometri c Detecto r(LC/MS/MS ) i n clea n wate rsamples
. Wate rsample s containin g heav y particulat e ma

yrequir e preparatio n b

ya n alternat e metho d suc h a s ETS-8-15 4 "Detemninatio n of Perfluorinate d Acids , Alcohols , Amides , an d Sulfonate s I n Wate rB ySoli d Phas e Extractio n an d Hig h Performance Liqui d Chromatography/Mas s Spectrometry"
. Thi s metho d i s considere d a performance-base d method
. Data i s considere d acceptabl e a s lon g a s th e define d Q C element s are satisfied
. Sampl e collectio n i s no

t covere d under thi s analytica l procedure . 2 Metho d Summar y Clea n aqueou s sample s are analyze d b ydirec t injectio n usin g LC/MS/MS
. Sample s containin g heav y particulat e ma

yno t b e suitabl e fo ranalysi s b ythi s method
. Sample s containin g suspende d particulat e shoul d b e centrifug e prio rt o removin g a sampl e aliquot , o rfiltered
. Thi s i s a performance-base d method
. Metho d accurac yi s determine d fo reac h sampl e se t usin g multipl e laborator ycontro l spike s a

t multipl e concentrations
. Thi s metho d als o require s that th e precisio n an d accurac yfo reac h sampl e b e determine d usin g fiel d matri xspike s t o verif ythat th e metho d i s applicabl e t o eac h sampl e matrix
. Sampl e result s fo rspike s outsid e of 70 % t o 130% , ma yb e flagge d a s suc h (wit h expande d accurac

ystatements) , o rwil l no

t b e reporte d du e t o non-complian t qualit ycontro l samples
. Fortificatio n level s fo rfiel d matri xspike s an d fo rlaborator ymatri xspike s shoul d b e a t least 50 % of th e endogenou s leve l an d les s tha n 1 0 time s th e endogenou s leve l t o b e use d t o determin e th e statemen t of accurac yfo ranalytica l results
. 3 Definition s 3. 1 Calibratio n Standar d A solutio n prepare d b

yspikin g a know n volum e of th e Workin g Standar d (WS ) int o a predetermine d amoun t of AST M Typ e I , HPLC grad e water , o rothe rsuitabl e water , an d analyze d accordin g t o thi s method
. Calibratio n standard s are use d t o calibrat e th e instrumen t respons e wit h respec t t o analyt e concentration
. 3. 2 Laborator y Duplicat e Sampl e (LDS , o r La b Dup ) A laborator

yduplicat e sampl e i s a separat e aliquot of a sampl e take n i n th e analytica l laborator ythat i s analyze d separatel ywit h identica l procedures
. Analysi s of LDS s compare d t o that of th e firs t aliquot give a measur e of th e precisio n associate d wit h laborator yprocedures , bu t no

t wit h sampl e collection , preservation , o rstorag e procedures
. 

### 3. 3 Fiel d Blan k

(FB)/Tri p Blan k AST M Typ e I , HPLC grad e water , o rothe rsuitabl e water , place d i n a sampl e containe ri n th e laborator y an d treate d a s a sampl e i n al l respects , includin g exposur e t o samplin g sit e conditions , storage , preservatio n an d al l analytica l procedures
. Th e purpos e o f th e F B i s t o determin e i f tes t substance s o r othe rinterference s are presen t i n th e fiel d environment
. Thi s sampl e i s als o referre d t o as a Tri p Blank
. ETS-8-044. 0 Pag e 2 o f 1 1 Metho d of Analysi s fo rth e Determinatio n o f Perfluorinate d Compound s i n Wate rb yLC/MS/MS ; Direct Injectio n Analysi s Pag e 3 3 of 4 4GLP10-01-01 ; Interi m Repor t 2 3 Analysi s of PFOA i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1 

### 3. 4 Fiel d Duplicat e Sampl e (FDS , Fiel d Dup) A sampl e collecte d i n duplicat e a t th e sam e tim e fro m th e sam e locatio n a s th e sample
. Th e FD S i s handle d unde ridentica l circumstance s an d treate d exactl yth e sam e throughou t fiel d an d laborator y procedures
. Analysi s o

f th e FDS.compare d t o that o f th e firs t sampl e give s a measur e of th e precisio n associate d wit h sampl e collection ; preservatio n an d storage , a s wel l a s wit h laborator yprocedures
. 3. 5 Fiel d Matri x Spik e (FIVIS ) A sampl e t o whic h know n quantitie s o f th e targe t analyte s are adde d t o th e sampl e bottl e i n th e laborator y befor e th e bottle s are sen t t o th e fiel d fo rcollectio n o f aqueou s samples
. A known , specifi c volum e of sampl e must b e adde d t o th e sampl e containe rwithou t rinsing
. Thi s ma yb e accomplishe d b

ymakin g a "fil l t o thi s level " lin e o n th e outsid e o f th e sampl e container
. Th e FM S shoul d b e spike d betwee n approximatel y50 % an d 1 0 time s th e expecte d analyt e concentratio n i n th e sample
. I f th e expecte d rang e of analyt e concentration s i s unknown , multipl e spike s a t varyin g level s ma

yb e prepare d t o increas e th e likelihoo d that a spike a

t a n appropriat e leve l i s made
. Th e FM S i s analyze d t o ascertai n i f an ymatri x effects , interferences , o rstabilit yissue s ma

ycomplicat e th e interpretatio n of th e sampl e analysis
. 

### 3. 6 Tri p Blan k

Spik e (Fiel d Spik e Contro l Sample , FSCS ) A n aliquot of AST M Typ e I , HPLC grad e water , o rothe rsuitabl e water , t o whic h know n quantitie s of th e targe t analyte s are adde d i n th e laborator yprio rt o th e shipmen t of th e collectio n bottles
. Th e FSC S i s extracte d an d analyze d exactl ylik e a stud ysampl e t o hel p determin e i f th e metho d i s i n contro l an d whethe ra los s of analyt e coul d b e attribute d t o holdin g time , sampl e storag e and/o rshipmen t issues
. A lo w an d hig h FSC S are appropriat e whe n expecte d sampl e concentration s are no t know n o rma

yvary . A t least on e separate , un-spike d sampl e must b e take n at th e sam e tim e an d plac e a s eac h FMS
. 

### 3. 7 Laboratory Contro l Sampl e (LCS ) A n aliquot o

f contro l matri xt o whic h know n quantitie s of th e targe t analyte s are adde d i n th e laborator ya t th e tim e of sampl e extraction
. A t leas t tw o level s are included , on e generall ya t th e lo w en d of th e calibratio n curve an d on e nea rth e mi d t o uppe rrang e of th e curve . Th e LCS s are extracte d an d analyze d exactl ylik e a laborator

ysampl e t o determin e whethe rth e metho d i s i n control
. LCS s shoul d b e prepare d eac h da ysample s are extracted
. 3. 8 Laborator y Matri x Spik e (LMS ) A laborator

ymatri xspik

e i s a n aliquot of a sampl e t o whic h know n quantitie s of targe t analyte s are adde d i n th e laboratory
. Th e LM S i s analyze d exactl ylik e a laborator

ysampl e t o determin e whethe rth e sampl e matri xcontribute s bia s t o th e analytica l results
. Th e endogenou s concentration s of th e analyte s i n th e sampl e matri xmust b e determine d i n a separat e aliquot an d th e measure d value s i n th e LM S correcte d fo rthes e concentrations
. LMS s are optiona l fo ranalysi s of aqueou s samples
. 3. 9 Laborator y Sampl e A portio n o raliquot of a sampl e receive d fro m th e fiel d fo rtesting
. 3.1 0 Limi t o f Quantitatio n (LOQ ) Th e lowe rlimi t of quantitatio n (LLOQ ) fo ra datase t i s th e lowest concentratio n that ca n b e reliabl y quantitate d withi n th e specifie d limit s of precisio n an d accurac ydurin g routin e operatin g conditions
. T o simplif ydat a reporting , th e LLO Q i s generall yselecte d a s th e lowest non-zer o standar d i n th e calibratio n curve that meets metho d criteria
. Sampl e LLOQ s are matrix-dependent
. Th e uppe rlimi t of quantitatio n (ULOQ ) fo ra datase t i s th e highest concentratio n that ca n b e reliabl y quantitate d withi n th e specifie d limits of precisio n an d accurac ydurin g routin e operatin g conditions
. Th e highest standar

d i n th e calibratio n curve that meets metho d criteri a i s define d a s th e ULOQ
. ETS-8-044. 0 Pag e 3 of 1 1 Metho d of Analysi s fo rth e Determinatio n of Perfluorinate d Compound s i n Wate rb yLC/MS/MS ; Direct Injectio n Analysi s Pag e 3 4 of 4 4GLP10-01-01 ; Interi m Repor t 2 3 Analysi s of PFOA i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1
3.1 1 Metho d Blan k A n aliquot of contro l matri xthat i s treate d exactl ylik e a laborator

ysampl e includin g exposur e t o al l glassware , equipment , solvents , an d reagents that ar e use d wit h othe rlaborator ysamples
. Th e metho d blan k i s use d t o determin e i f tes t substance s o rothe rinterference s are presen t i n th e laborator y environment , th e reagents , o rth e apparatus . 3.1 2 Sampl e A sampl e i s a n aliquot remove d fro m a large rquantit yof materia l intende d t o represen t th e origina l source material
. 3.1 3 Stoc k

Standar d Solutio n (SSS ) A concentrate d solutio n o f a single-analyt e prepare d i n th e laborator ywit h a n assaye d referenc e compound
. 

### 3.1 4 Surrogat e A compoun d simila ri n chemica l compositio n an d behavio rt o th e targe t analyte(s) , bu t i s no t normall y foun d i n th e sample(s)
. A surrogat e compoun d i s typicall ya targe t analyt e wit h a t least on e ato m containin g a n isotopically-labele d substitution
. I f used , surrogate(s ) ar e adde d t o al l sample s an d qualit y contro l samples
. Surrogate(s ) ar e adde d t o quantitativel yevaluat e th e entire analytica l procedur e includin g sampl e collection , preparation , an d analysis
. Inclusio n of a sun"ogat e analyt e i s a n optiona l qualit ycontro l measur

e an d i s NO

T required
. 

### 3.1 5 Workin g Standar d (WS ) A solutio n o f severa l analyte s prepare d i n th e laborator yfro m SSS s an d dilute d a s neede d t o prepar e calibratio n standard s an d othe rrequire d analyt e solutions
. 4 Warning s an d Caution s 4. 1 Healt h an d Safet y Th e acut e an d chroni c toxicit yof th e standard s fo rthi s metho d have no t bee n precisel ydetermined ; however , eac h shoul d b e treate d a s a potentia l healt h hazard
. Th e analyst shoul d wea rgloves , a la b coat , an d safet

yglasse s t o preven t exposure t o chemical s that migh t b e present . Th e laborator

yi s responsibl e fo rmaintainin g a saf e wor k environmen t an d a curren t awarenes s o f loca l regulation s regardin g th e handlin g of th e chemical s use d i n thi s method
. A reference fil e of materia l safet y dat a sheet s (MSDS ) shoul d b e availabl e t o al l personne l involve d i n thes e analyses
. 4. 2 Caution s Th e analyst must b e familia rwit h th e laborator yequipmen t an d potentia l hazard s including , bu t no t limite d to , th e us e of solvents , pressurize d ga s an d solven t lines , hig h voltage , an d vacuu m systems . Refe rt o th e appropriat e equipmen t procedure o roperato rmanua l fo radditiona l informatio n an d cautions
. 5 Interference s Durin g sampl e preparatio n an d analysis , majo rpotentia l contaminan t source s are reagents an d glassware
. Al l material s use d i n th e analyse s shal l b e demonstrate d t o b e fre e fro m interference s unde r condition s of analysi s b

yrunnin g metho d blanks
.

ETS-8-044. 0 Pag e 4 o f 1 1 Metho d o f Analysi s fo rth e Determinatio n o f Perfluorinate d Compound s i n Wate rb yLC/MS/MS ; Direct Injectio n Analysi s Pag e 3 5 o f 4 4GLP10-01-01 ; Interi m Repor t 2 3 Analysi s o f PFOA i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1
Part s an d supplie s that contai n Teflon ® shoul d b e avoide d o rminimize d du e t o th e possibilit yof interference and/o rcontamination
. Thes e ma yinclude , bu t ar e no

t limite d to : was h bottles
. Teflon ® line d caps , autovia l caps , HPL C parts , etc . Th e us e of disposabl e micropipette s o rpipette s t o aliquot standar d solution s i s recommende d t o mak e calibratio n standard s an d matri xspikes
. 6 Instrumentation , Supplies , an d Equipmen t 6. 1 Instrumentatio n an d Equipmen t A hig h performanc e liqui d chromatograp h capabl e o f pumpin g u p t o tw o solvent s an d equippe d wit h a variabl e volum e injecto rcapabl e of injectin g 5-10 0 p L connecte d t o a tande m Mas s Spectromete r (LC/MS/MS)
. I Analytica l balance capabl e of readin g t o 0.000 1 g A devic e t o collec

t ra w dat a fo rpea k

integratio n an d quantitatio n 15-m L an d 50-m L disposabl e polypropylen e centrifug e tubes
. Ga s tigh t syringes , 25pL , 50pL , lOOpL , 250pL , 500pL , lOOOpL
. 1 m L plasti c HPLC autovial
. Disposabl e pipettes , polypropylen e o rglas s a s appropriat e Centrifug e capabl e of spinnin g 15-m L an d 50-m L polypropylen e tube s a t 300 0 rpm . 6. 2 Chromatographi c Syste m Guar d Column : Pris m RP , 4. 6 m m x5 0 mm , 5 p m Analytica l Column : Betasi l C18,4. 6 m m x10 0 mm , 5 \^ m Temperature : 10° C Mobil e Phas e (A) : 2 m M Ammoniu m Acetat e i n Wate r Mobil e Phas e (B) : Methano l Gradien t Program : Flow Rat e

Tim e (min ) % A % B (mL/min ) 0. 0 9 7 3 1. 0 0. 5 9 7 3 1. 0 11. 0 5 9 5 1. 0 13. 5 5 9 5 1. 0 13. 6 9 7 3 1. 0 17. 0 9 7 3 1. 0 Injectio n Volume : 10 0 |JL
. Quantitation : Pea k

Are a - quadrati c curve fit , 1/ xweighted
. RunTime : ~ 17minutes
. Th e previou s informatio n i s intende d a s a guide ; alternat e condition s an d equipmen t ma yb e use d provide d tha t dat a qualityobjective s ar e met . ETS-8-044. 0 Pag e 5 o f 1 1 Metho d o f Analysi s fo rth e Determinatio n o f Perfluorinate d Compound s i n Wate rb yLC/MS/MS ; Direct Injectio n Analysi s Pag e 3 6 of 4 4GLP10-01-01 ; Interi m Repor t 2 3 Analysi s o f PFOA i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1 

### 6. 3 MS/M S Syste m 6.3. 1 Mode : Electrospra yNegativ e ion , MR M mode , monitorin g th e followin g transitions : Analyt e Transitio n Monitore d PFBA 213 ^ 16 9 PFPeA 263^21 9 PFH A 313^26 9 an d 313^11 9 PFHp A 36 3 ^ 319 , 36 3 ^

16 9 an d 36 3 ^

11 9 PFOA 41 3 ^

369 , 41 3 ^

21 9 an d 41 3 ^

16 9 PFN A 46 3 419 , 46 3 16 9 an d 46 3 - > 21 9 PFD A 51 3 ^

469 , 51 3 ^

21 9 an d 51 3 ^

26 9 PFUn A 56 3 ^ 519 , 56 3 ^

26 9 an d 56 3 -^21 9 PFDoA 61 3 569 , 61 3 - > 16 9 an d 61 3 ^ 31 9 PFB S 29 9 ^ 8 0 an d 29 9 9 9 PFH S 39 9 8 0 an d 39 9 9 9 PFO S 49 9 - > 80 , 49 9 - » 9 9 an d 49 9 ^ 13 0 Multipl e transition s fo rmonitorin g th e analyte s i s a n option , a s summin g multipl e transition s ma yprovid e quantitatio n of isomers tha t more closel ymatche s NM R dat a an d ma yhav e th e adde d benefi t o f increase d sensitivity
. Th e us e o f on e daughte rio n i s acceptabl e i f metho d sensitivit yi s achieved , provide d tha t retentio n tim e criteri a ar e me t t o assur e adequat e specificity
. Th e previou s informatio

n i s intende

d a s a guide , alternat

e instnjment

s an d equipmen

t ma y b e used . 

### 7 Reagent s an d Standard s 7. 1 Chemical s Wate r- Milli-Q , HPLC grade , o rothe rsuitabl yappropriat e source s Methano l - HPLC grad e Ammoniu m Acetat e - A.C.S
. Reagen t Grad e 

### 7. 2 Standard s Perfluorobutanoi c Aci d (PFBA - C 4 acid) ; Oakwoo d Products , In c Perfluoropentanoi c Aci d (PFPeA - C 5 acid , als o know n a s NFPA , nonafluoropentanoi c acid) ; Alf a Aesa r PerfluorohexanoicAci d (PFHA-C 6 acid) ; Oakwoo d Products , In c Perfluoroheptanoi c Aci d (PFHpA - C 7 acid , als o know n a s TDHA , tridecafluoroheptanoi c acid) ; Oakwoo d Products , In c Perfluorooctanoi c Aci d (PF0A-C 8 acid) ; 3 M Perfluorononanoi c Aci d (PFNA-C 9 acid) ; Oakwoo d Products , In c Perfluorodecanoi c Aci d (PFDA-C1 0 acid) ; Oakwoo d Products , In c Perfluoroundecanoi c Aci d (PFUnA-C1 1 acid) ; Oakwoo d Products , In c Perfluorododecanoi c Aci d (PFDoA-C1 2 acid) ; Oakwoo d Products , In c Perfiuorobutanesulfonat e (PFB S - C 4 sulfonate) ; 3 M Perfluorohexanesulfonat e (PFH S - C 6 sulfonate) ; 3 M Perfluorooctanesulfonat e (PFO S - C 8 sulfonate) ; 3 M ETS-8-044. 0 Pag e 6 o f 1 1 Metho d of Analysi s fo rth e Determinatio n o f Perfluorinate d Compound s i n Wate rbyLC/MS/MS ; Direc t Injectio n Analysi s Pag e 3 7 o f 4 4GLP10-01-01 ; Interi m Repor t 2 3 Analysi s of PFO

A i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1
Th e previou s informatio n i s intende d a s a guide
. Reagent s an d standard s fro m alternat e source s ma yb e used
. 7. 3 Reagen t Preparatio n 2 m M Ammoniu m acetat e solutio n (Analysis)—^Weig h 0. 3 g of Ammoniu m acetat e an d dissolve i n 2. 0 L of reagen t water . Note : Alternativ e volume s ma yb e prepare d a s lon g a s th e ratio s of th e solven t t o solut e ratio s are maintained
. 

### 7. 4 Stoc k

Standar d Solutio n (SSS ) an d Workin g Standar d Solutio n Preparatio n Th e followin g standar

d preparatio n procedur

e serve s a s a n example
. Weighe d amounts an d fina l volume s ma yb e change d t o sui t th e need s of a particula rstudy
. Fo rexample , p L volume s ma yb e spike d into volumetri c flask s whe n dilutin g stoc k

solution s t o appropriat e levels
. 10 0 [iglm L targe t analyt e SSSs—^Weig h ou t 1 0 m g o f analytica l standar

d (correcte d fo rpercen t sal t an d purit yan d dilut e t o lOOm L wit h methano l o rothe rsuitabl e solvent , i n a lOOm L volumetri c flask
. Transfe rt o a 125m L LDP E bottl e o rothe rsuitabl e container
. Prepar e a separat e solutio n fo reac h analyte
. Expiratio n date s an d storag e condition s of stoc k solution s shoul d b e assigne d i n accordance wit h laborator ystandar d operatin g procedure
. A n exampl e of purit yan d sal t con-ectio n i s give n below fo rPFOS
.

, , molecula rweigh t o f anio n sal t correctio n facto r= moclecula rweigh t o f sal t 49 9 PFO S (K+)sal t correctio n facto r= —= 0.927 5 53 8 1 0 m g CsFiySOa'K

" wit h purit

y90 % = 8.35m g CsFiySOa" (1 0 mg*0.90*0.9275=8.3 5 mg ) 5 pg/m L (500 0 ng/mL ) mixe d workin g standard—Ad d 0.5m L eac h of th e 100pg/m L SSS s t o a 10m L volumetri c flas k an d brin g u p t o volum e wit h solvent
. 25 0 ng/m L mixe d workin g standard—Ad d 1.25m L o f th e 5 pg/m L -mixe d worthin g standar d solutio n t o a 25m L volumetri c flas k

an d brin g u p t o volum e wit h solvent
. 12 5 ng/m L mixe d standard—Ad d 625p L of th e 5 pg/mL-mixe d worthin g standar d solutio n t o a 25m L volumetri c flas k an d brin g u p t o volum e wit h solvent
. Storag e Conditions—Stor e al l SSS s an d workin g standard s i n accordanc e wit h laborator ystandar d operatin g procedur e o ri n a refrigerato ra

t 4°±2° C fo ra maximu m perio d of 6 month s fro m th e dat e o f preparation
.

ETS-8-044. 0 Pag e 7 o f 1 1 Metho d o f Analysi s fo rth e Determinatio n o f Perfluorinate d Compound s i n Wate rbyLC/MS/MS ; Direct Injectio n Analysi s Pag e 3 8 o f 4 4GLP10-01-01 ; Interi m Repor t 2 3 Analysi s of PFOA i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1

7. 5 Calibratio n Standard s Usin g th e wori<in g standard s describe d above , prepare calibratio n solution s i n AST M Typ e I water , HPLC water , o r othe rsuitabl e water , usin g th e followin g tabl e a s a guideline
. Note : Volume s of wate ran d wori<in g standard s ma y b e adjuste d t o meet th e dat a qualit yobjective s addresse d i n th e genera l projec t outline
. Calibratio n level s othe r tha n thos e liste d below ca n b e prepare d a s 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 12 5 1 0 5 0 0.02 5 12 5 1 5 5 0 0.037 5 12 5 2 0 5 0 0.05 0 12 5 3 0 5 0 0.07 5 25 0 2 0 5 0 0.10 0 25 0 5 0 5 0 0.25 0 25 0 10 0 5 0 0.50 0 25 0 20 0 5 0 1.0 0 500 0 2 5 5 0 2.5 0 500 0 5 0 5 0 5.0 0 500 0 10 0 5 0 10. 0 8 Sampl e Handlin g 8. 1 Wate r Sampl e Preparatio n Thi s metho d i s applicabl e t o clea n wate rsamples
. Sample s containin g heav yparticulat e ma

yno t b e suitabl e fo r analysi s b

ythi s method
. Sample s containin g suspende d particulat e shoul d b e centrifug e prio rt o removin g a sampl e aliquot , o rfiltered
. Thoroughl ymi xsampl e befor e removin g a n aliquot an d placin g i n a labele d plasti c autovial
. Plasti c i s preferre d ove rth e us e of glas s autovials , t o preven t th e possibl yof fluorochemica l stickin g t o th e glass
. Dilut e sample , i f necessary , wit h AST M Typ e I , HPLC water , o rothe rsuitabl e water . Prepar e metho d Q C sample s an d multipl e metho d blank s an d aliquot into labele d plasti c autovials
. Prepar e a t least fiv e metho d blanks
. 

### 9 Sampl e Analysi s - LC/MS/M S Analyz e th e standar

d curv e prio rt o eac h set of samples
. Th e standar d curve ma

yb e plotte d usin g a linea rfit , weighte d 1/

xo runweighted , o rb

yquadrati c fi l (

y= ax ^ + b x+ c) , weighte d 1/

xo runweighted , usin g suitabl e software
. Th e calibratio n curve s ma yinclud e bu t shoul d no

t b e force d throug h zero . Th e mathematica l metho d use d t o calculat e th e calibratio n curv e shoul d b e applie d consistentl ythroughou t a study
. An ychang e shoul d b e thoroughl ydocumente d i n th e ra w data
. Hig h and/o rlo

w points ma

yb e exclude d fro m th e calibratio n curve s t o provid e a bette rfi t ove rth e rang e appropriat e t o th e dat a o rbecaus e the ydi d no t meet th e pre-determine d acceptanc e criteria
. Low-leve l curv e points shoul d als o b e exclude d i f thei rare a count s are no t a t least twic e that of th e metho d and/o rsolven t blanks
. Th e coefficien t o f detemninatio n (r^ ) valu e fo rth e calibratio n curve must b e greate rtha n o requa l t o 0.990
. Eac h poin t i n th e curv e must b e withi n ±25 % of th e theoretica l concentratio n wit h th e exceptio n of th e LLOQ , whic h ma y ETS-8-044. 0 Pag e 8 o f 1 1 Metho d of Analysi s fo rth e Determinatio n o f Perfluorinate d Compound s i n Wate rbyLC/MS/MS ; Direct Injectio n Analysi s Pag e 3 9 of 4 4GLP10-01-01 ; Interi m Repor t 2 3 Analysi s o f PFOA i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1
b e withi n ±30%
. Justificatio n fo rexclusio n of calibratio n curve points wil l b e note d i n th e ra w data
. A minimu m of 6 points wil l b e use d t o construc t th e calibratio n curve . I f th e calibratio n curve doe s no t meet acceptance criteria , perfor m routin e maintenance o rprepare a ne w standar d curve (i f necessary) an d reanalyze
. Continuin g calibratio n verification s (CCV) are analyze d t o verif yth e accurac

yo f th e calibratio n curve . Analyz e a mid-rang e calibratio n standard , on e of th e sam e standard s use d t o constmc t th e calibratio n curve , a

t a minimu m afte rever ytent h sample , no

t includin g solven t blanks , wit h a minimu m of on e pe rsampl e set . Calibratio n verificatio n injection s mus t b e withi n ±25 % t o b e considere d acceptable
. Th e calibratio n curve an d th e last passin g CCV wil l the n bracket acceptabl e samples
. Multipl e CCV level s ma yb e used
. Sample s containin g analyte s that are quantitate d above th e concentratio n of th e highest standar d i n th e curve shoul d b e furthe rdilute d an d reanalyzed
. 

### 1 0 Quality Contro l 10. 1 Dat a Quality Objective s Thi s metho d an d require d qualit ycontro l sample s i s designe d t o generat e dat a accurat e t o ±30 % wit h a targete d LOQ of 0.02 5 ng/mL
. An ydeviation s fro m th e qualit ycontro l measure s spelle d ou t belo w wil l b e documente d i n th e ra w dat a an d footnote d i n th e fina l report . 10. 2 Metho d Blank s Metho d blank

s must b e prepare d wit h eac h analysi s batch
. At least fiv e metho d blank s must b e prepared
. Metho d blank

s ma yb e injecte d multipl e times , bu t n o mor e tha n 3 injection s shoul d b e remove d fro m a singl e metho d blank
. At a minimum , metho d blank s are analyze d prio rt o instrumen t calibration , prio rt o th e analysi s o f CCV samples , an d a

t th e en d of th e analytica l mn . Th e mea n are a coun t fo reac h analyt e i n th e metho d blank s must b e les s tha n 50 % of th e are a coun t of th e LOQ standard
. Th e standar

d deviatio n o

f th e are a count s of thes e metho d blank s shoul d b e calculate d an d reported
. I f th e mea n are a count s of th e metho d blank s excee d 50 % of th e LOQ standard , the n th e LOQ must b e raise d t o th e firs t standar

d leve l i n th e curve that meets criteria , o ralternatively , th e metho d blank s must b e evaluate d statisticall yt o detemnin e outliers , o rtechnica l justificatio n t o eliminat e on e o rmor e result s shoul d b e made
. 10. 3 Sampl e Replicate s Sample s duplicate s are collecte d i n th e field
. Th e relative percen t difference , RPD , shoul d b e reported
. RP D result s greate rtha n 20 % wil l b e flagge d i n th e report , bu t wil l no t b e exclude d fro m reporting
. Th e requiremen t fo r replicate s exclude s fiel d blanks
. 

### 10. 4 Surrogat e Spike s Surrogat e spike s are no

t require d bu t ma

yb e use d o n projec

t specifi c requirements
. 

### 10. 5 La b Contro l Sampl e Triplicat e la b contro l spike s at a minimu m of tw o differen t concentration s are t o b e prepare d wit h eac h preparatio n batch
. Lo w la b contro l spike s shoul d b e prepare d a t concentration s i n th e rang e of fiv e t o te n time s highe rtha n th e targete d LOQ an d hig h la b contro l spike s shoul d b e prepare d a t concentration s nea rth e mid-poin t of th e curve . Th e relative standar

d deviatio n of th e contro l spike s evaluate d independentl ya t eac h concentratio n leve l mus t b e les s tha n o requa l t o 20 % an d th e averag e recover ymus t b e 80-120%
. I f th e above criteri a are no t met , th e entire se t o f sample s shoul d b e re-injecte d o rre-prepare d a s appropriate
.

ETS-8-044. 0 Pag e 9 o f 1 1 Metho d o f Analysi s fo rth e Determinatio n o f Perfluorinate d Compound s i n Wate rb yLC/MS/MS ; Direct Injectio n Analysi s Pag e 4 0 of 4 4GLP10-01-01 ; Interi m Repor t 2 3 Analysi s o f PFOA i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1
10. 6 Fiel d Matri x Spike s / La b Matri x Spike s Recoverie s of fiel d matri xspike s an d laborator ymatri xspike s are anticipate d t o b e betwee n 70 % an d 130 % of th e fortifie d levels
. Sampl e result s fo rspike s outsid e of 70 % t o 130% , ma yb e flagge d a s suc h (wit h expande d accurac ystatements) , o rwil l no

t b e reporte d du e t o non-complian t qualit ycontro l samples
. Th e targete d fortificatio n level s shoul d b e a t least 50 % of th e endogenou s leve l an d les s tha n 1 0 time s th e endogenou s leve l t o b e use d withou t justificatio n t o determin e th e statemen t of accurac yfo ranalytica l results
. Th e averag e of th e sampl e an d th e fiel d duplicat e shoul d b e use d t o calculat e th e recovery . 1 1 Dat a Analysi s an d Calculation s Us e th e followin g equatio n t o calculat e th e amoun t of analyt e foun d (i n ng/mL , base d o n pea k area ) usin g th e standar d curve (linea rregressio n parameters ) generate d b ya n appropriat e software program :

. , . , . , , , , (Pea k Area-Intercept )
_ _ Analyt e foun d (ng/mL ) = -^ ^ —xD F Slop e D F = facto rb

ywhic h th e fina l volum e wa s diluted , i f necessary . Fo rsample s fortifie d wit h know n amounts of analyt e prio rt o extraction , us e th e followin g equatio n t o calculat e th e percen t recovery . Recover y- ^"^'^^

^ foun d (ng/mL ) - Averag e analyt e foun d i n sarnpl e (ng/mL ) ^ ^ Analyt e adde d (ng/mL ) 

### 1 2 Method Performanc e An ymetho d perfonnanc e parameter s that are no

t achieve d must b e considere d i n th e evaluatio n o f th e data
. Nonconformance t o an yspecifie d parameter s must b e describe d an d discusse d i f th e Technica l Manage r(non GL P study) o rStud yDirecto r(GL P study) choose s t o repor t th e data
. I f criteri a liste d i n thi s metho d performanc e sectio n are no t met , maintenance ma

yb e perfomned o n th e syste m an d sample s reanalyzed , o rothe raction s take n a s appropriate
. Documen t al l action s i n th e ra w data
. I f dat a are t o b e reporte d whe n perfomnanc e criteri a have no

t bee n met , th e dat a mus t b e footnote d o n table s an d discusse d i n th e tex

t of th e report . 12. 1 Syste m Suitabilit y Syste m Suitabilit

ystandard s are no

t a require d componen t of thi s method
. I f require d b yprotoco l o rb

yth e technica l manager , a minimu m o f thre e syste m suitabilit ysample s are injecte d a

t th e beginnin g of eac h analytica l m n prio rt o th e calibratio n curve . Typicall ythes e sample s are a t a concentratio n nea rth e mi d leve l o f th e calibratio n curv e an d ar e repeate d injection s fro m on e autosample rvial
. Th e syste m suitabilit yinjection s mus

t hav e are a count s wit h a n RS D of <5 % an d a retentio n tim e RS D o f 22 % t o b e compliant
. 12. 2 Quantitatio n Calibratio n Curve : Th e coefficien t of detenninatio n (r^ ) valu e fo rth e calibratio n curv e mus t b e greate rtha n o r equa l t o 0.990
. Eac h poin t i n th e curve must b e withi n ±25 % of th e theoretica l concentratio n wit h th e exceptio n o f th e LLOQ , whic h ma

yb e withi n ±30%
. CCV Performance : Th e calibratio n standard s that ar e intersperse d throughou t th e analytica l sequence are evaluate d a s continuin g calibratio n verification s i n additio n t o bein g par t of th e calibratio n curve . Th e accurac yof eac h curve poin t mus

t b e withi n 25 % of th e theoretica l valu e (withi n 30 % fo rlowes t curve point)
. Sample s that are brackete d b

yCCVs no

t meetin g thes e criteri a must b e reanalyzed
.

ETS-8-044. 0 Pag e 1 0 of 1 1 Metho d of Analysi s fo rth e Determinatio n of Perfluorinate d Compound s i n Wate rb yLC/MS/MS ; Direc

t Injectio n Analysi s Pag e 4 1 o f 4 4GLP10-01-01 ; Interi m Repor t 2 3 Analysi s o f PFOA i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1
Demonstratio n o f Specificity : Specificit yi s demonstrate d b

ychromatographi c retentio n tim e (withi n 4 % of standard ) an d th e mas s spectra l respons e of uniqu e ions
. 

### 12. 3 Sensitivit y Th e targete d limi t of quantitatio n fo ral l analyte s i s 0.02 5 ng/mL
. Th e LOQ fo ran yspecifi c analyt e ma yvar y dependin g o n th e evaluatio n of appropriat e blank s an d th e accurac

yof th e low-leve l calibratio n curve points
. Refe r t o Sectio n 1 0 fo radditiona l details
. 12. 4 Accurac y Thi s metho d an d require d qualit ycontro l sample s are designe d t o generat e dat a that ar e accurat e t o +/-30%
. Sectio n 1 0 contain s additiona l informatio n regardin g th e require d accurac yof laborator

ycontro l spikes , fiel d matri x spike s an d laborator

ymatri xspikes
. 12. 5 Precisio n Sample s shoul d b e collecte d i n duplicat e i n th e field
. Th e relative percen t difference , RPD , shoul d b e reported
. RP D result s greate rtha n 20 % wil l b e flagge d i n th e report , bu t wil l no t b e exclude d fro m reporting
. Th e requiremen t fo rreplicate s exclude s fiel d blank s o rrinse blanks
. Sectio n 1 0 contain s additiona l informatio n regardin g th e require d precisio n of laborator ycontro l spikes
. 

### 1 3 Pollutio n Preventio n an d Wast e Managemen t Wast e generate d whe n perfonnin g thi s metho d wil l b e dispose d of appropriately
. Th e origina l sample s wil l b e archive d a

t th e 3 M Environmenta l Laborator yi n accordanc e wit h interna l procedures
. 1 4 Record s Eac h dat a packag e generate d fo ra stud ymus t includ e al l supportin g informatio n fo rreconstructio n o f th e data
. Informatio n fo rth e dat a packag e must include , bu t i s no t limite d t o th e followin g items : stud yo rprojec t number , sampl e an d standar

d pre p sheets/records , instmmen t m n lo g (instmmen t batc h records , instmmen t acquisitio n method , summar

ypages) , instmmen t results files , chromatograms , calibratio n curves , an d dat a calculations
. 

### 1 5 Affecte d Document s None
. 

### 1 6 Revision s Revisio n Numbe rSummar yo f Change s

ETS-8-044. 0 Pag e 1 1 o f 1 1 Metho d of Analysi s fo rth e Determinatio n o f Perfluorinate d Compound s i n Wate rb yLC/MS/MS ; Direct Injectio n Analysi s Pag e 4 2 of 4 4GLP10-01-01 ; Interi m Repor t 2 3 Analysi s o f PFOA i n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1


### ATTACHMEN T D : DEVIATION(S )

Pag e 4 3 o f 4 4GLP10-01-01 ; Interi m Repor t 23 Analysi s o f PFO A I n Groundwate rSample

s Off-Site 61 0 Wells ; Septembe r201 1 

### /. Identification stud y / Project No
. GLP10-01-01-2 3 Date(s ) o f Occurrence : k111006 a Documen t Number : ETS-8-044. 0 Deviatio n typ e • SO P (Chec k one ) • Protoco l • Equipmen t Procedur e 0 • GP O • Metho d Other : //
. Descriptio n (attac h extr a page s a s needed ) • Metho d Requirements : 1
. RP D withi n ±20 % (sectio n 10.3)
. 2
. Th e targete d fortificatio n leve l shoul d b e at leas t 50 % o f th e endogenou s sampl e concentratio n (sectio n 10.6)
. Actua l procedure/process : 1
. Samplin g locatio n DAL-GW - 6 1 O S ha d a n RP D o f 26 % fo rPFOA
. 2
. Th e hig h fiel d matri xspik e a t 1 ng/m L fo rsamplin g locatio n DA L GW610 L wa s les s tha n 50 % o f th e PFO A concentratio n i n th e sample
. However , sinc e th e ^^C4-PF0A surrogat e (whic h wa s adde d t o th e samples ) wa s inadvertentl yomitte d fro m th e analysis , th e fiel d matri xspik e recover ywa s calculate d an d foun d t o b e 84.5%
. /// . Actions Taken (such as amendment

issued, SOP

revision, etc.) Correctiv e Actio n ( • Ye s 0 No

) Reference : Acceptabilit y o f tin e nonconformin g work : 1
. Th e PFO A RP D fo rsamplin g locatio n DA L G W 6 1 O L wil l b e flagge d i n th e fina l report . 2
. Th e recover

yo f th e hig h fiel d matri xspik e fo rsamplin g locatio n DL A G W 6 1 O

L wil l b e reporte d an d flagge d t o indicat e tha t th e spik e leve l wa s outsid e th e targete d fortificatio n range . Actions : • Haltin g o f Wor k • Clien t Notificatio n • Wor k Recal l • Withholdin g o f Repor t 0 Other : Deviation s wil l b e note d I n fina l report . Project Lead/PA I Approval : Date : Stud y Directo r(i f GLP) : Sponso rApprova l (fo rGL P protoco l deviations) : N A Technica l Reviewe r(optional) : N A Date : N A Laborator

y Departmen t Manage rApproval : Date :

IV. Authorization

to Resume

Work Where haltin g o f wor k

occurred , resumptio n o f wor k mus t firs t b e approve d b yLaboratoryManagemen t Laborator

y Departmen t Manage rApproval : NA Date : N A Deviation

No. (assigned

by Study Director

or Team Leader at the end of study or project)

Pag e 4 4 o f 4 4J: \ FOLDERS.0 - 9 \ 3M - DECAT\ Phase 3 Work Plan \ 4Q11 Status Report\ 4Q11 Status Report.doc 1/30/2012 

## ATTACHMENT 2 VEGETATIVE UPTAKE ST UDY TECHNICAL PROGRESS R EPORT OCTOBER 1, 2011 – DEC EMBER 3 1 , 2011J: \ FOLDERS.0 - 9 \ 3M - DECAT\ Phase 3 Work Plan \ 4Q11 Status Report\ 4Q11 Status Report.doc 1/30/2012 

### 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, r outine monitoring of the watering and venti lation system s and plant growth has been performed at the Athens, Alabama nurse ry site where the vegetative uptake study is being conducted. W eeding, thinning, and pest control a ctivities 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 in to 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 gree nhouse ventilation and a screen was affixed to the exhaust fan to maximize retention . O n December 7 , 2011 , turnip greens samples were collected by harvesting individual leaves from plants using stainless steel sciss ors. 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, dat e 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 c ollection 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 - h arvest 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 i n hilling the potato plants. The pre
- planting soil (initial) composite samples and the post
harvest turnip green soil (final) samples were shipped to the 3M EnvironmentalJ: \ FOLDERS.0 - 9 \ 3M - DECAT\ Phase 3 Work Plan \ 4Q11 Status Report\ 4Q11 Status Report.doc 1/30/2012 

### 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 f ruits 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 compo site 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 anal ysis. 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 ha ve lagged behind the other crops because of slow sprouting of the second sowing of seed potato . H arvest and sampling of potatoes, collection of the post
- harvest final potato soil samples and completion of vegetative uptake study field activities are expect ed to occur late in the first quarter of 2012. Photographs of the test facility and crops are shown in Figures 1 through 4 .J: \ FOLDERS.0
- 9 \ 3M
- DECAT \Phase 3 Work Plan \ 4Q11 Status Report\ 4Q11 Status Report.doc 1/30/2012 

### Figure 1 Turnip Green Plant

October 13, 2011J: \ FOLDERS.0
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### Figure 2 Tomato Section December 31, 2011J: \ FOLDERS.0
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- DECAT \Phase 3 Work Plan \ 4Q11 Status Report\ 4Q11 Status Report.doc 1/30/2012 

### Figure 3 Large Potato Plant December 31, 2011J: \ FOLDERS.0
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- DECAT \Phase 3 Work Plan \ 4Q11 Status Report\ 4Q11 Status Report.doc 1/30/2012 

### Figure 4 Late Sprouting Potatoes December 31, 2011