GLP10-01-01 ; Interi m Repor t 2 3 Analysi s of PFO

Ai 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 cAci 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 EPATSC AGoo 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 Way Westchester , P

A1938 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 55144 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. ACertificate #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 .

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Thi s page 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 PFOAi 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

Ai 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 cAci 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 compliance wit h Toxi cSubstance 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 ctes t substance , n o specifi ctes 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 PFOAi n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1



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

f PFO Ai 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 cAci 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

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

Ai 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

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

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 TO F TABLE S Tabl e 1 . Summarize d PFO AResults (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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Ai 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

A1938 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 rawdat 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

Pag e 7 o f 4 4GLP10-01-01 ; Interi m Repor t 2 3 Analysi s o f PFO Ai n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1



### 2 Summary Th e 3 M Environmenta l Laborator yreceive d groundwate rsample s fro m two differen t well s locate d a t th e Off-Sit e 61 0 Well s i n Decatur , AL . Atota 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 two 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 Afollowin 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 Aconcentration s ar

e summarize d i n Tabl e 1 . Th e tri p blan k wa s belowth 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 Awas 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 sediments 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 two Off-Sit e 61 0 well s locate d i n Decatur , A L fo rPFO Ai 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 sets 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 Aprio 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

Ai 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 Aprio 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 Asurrogat e standar d wa s inadvertentl yno

t include d i n th e analysi s o f th e samples . Sample s were 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 data qualit yobjectives . Tabl e 1 summarize s th e averag e PFO Aconcentratio 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 substance o rcontro l substance s i n th e classi csens 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 PFOAi 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 . Aset 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 set 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 control 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 the specifi c mas s transitions analyzed ar e describe

d i n the ra wdat a har d copie s place d i n the 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 Ai 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 cfo 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 cgroundwate r containin g calciu m an d magnesium . Aseparat 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 . Acalibratio 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 PFOAi n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1

Aquadratic , 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 Acalibratio 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 the 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 the area count

s ar e a t leas t twic e thos e o f the 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 cgroundwater , 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 = standard 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 PFOAi 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 of 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 of 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 wan 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 acceptance criteri a of 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 of th e analyte s of 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 PFOAi 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 belowsummariz 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

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

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

wdata . 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 Ai 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 difference (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 Aconcentratio n i n th e sample . However , since th e "C v PFO Asurrogat 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

Ai 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 PFOAi 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 Investigator / 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 PFOAi n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1 

### ATTACHMEN TA : PROTOCO L AMENDMEN T

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

ProtocomPmm''''"''''°'' Amendment

23 

### Study Title Analysi s o f Perfluorooctanoi cAci 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 TNO . 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

Ai 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 cAci 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 are required .

AMEND TO READ: N o Change s t o th e wordin g of th e protoco l are 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 project 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 wv^^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 PFOAi 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 PFOAi 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 cAci 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 PFOAi 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 cAci d (PFOA ) fro m newwell s locate d off-site . Analyse s wil l b e conducte d unde rth e GL P requirement s o f EP ATSC AGoo 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 rPFOAar 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 Afo 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 wfiel 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 wlist 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 PFOAi 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 against a n interna l standar d calibratio n curve. . Eac h curve poin t wil l contai n isotopicallyTlabele d peffluorocarboxyli cacid s an d perfluorosulfoni cacid 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 counts ove rth e interna l standar

d pea k are a counts 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 results 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 not 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 PFOAi n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1 

### ATTACHMEN TB : 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 Ai 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 I6.00* 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 ParaniBtc

.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 PFOAi 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 Ai 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 Paramet 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 Ai 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 . Wini 

# 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

. : 50 .w : 1.0 0 Proc . Algcr l Peak-Split . Repor tLargea tI Min . Peak Heigh t Min . Peak Width

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 Ai 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 PFOAi n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1 

### ATTACHMEN TC : ANALYTICA L METHOD(S )

Pag e 3 1 o f 4 4GLP10-01-01 ; Interi m Repor t 2 3 Analysi s o f PFOAi 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 PFOAi 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 cAci d (PFBA) , Perfluoropentanoi cAci d (PFPeA) , PerfluorohexanoicAci d (PFHA) , Perfluoroheptanoi cAci d (PFHpA) , Perfluorooctanoi cAci d (PFOA) , Perfluorononanoi cAci d (PFNA) , Perfluorodecanoi cAci d (PFDA) , Perfluoroundecanoi cAci d (PFUnA) , Perfluorododecanoi cAci 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 cDetecto 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 elements 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 set 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 results 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 Asolutio 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 ) Alaborator

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 PFOAi 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) Asampl 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 ) Asampl 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 . Aknown , specifi cvolum 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

Spike (Fiel d Spike 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 wan 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 wen 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 ) Alaborator

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 Aportio 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 limits 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 PFOAi 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 Asampl 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 ) Aconcentrate d solutio n o f a single-analyt e prepare d i n th e laborator ywit h a n assaye d reference compound . 

### 3.1 4 Surrogat e Acompoun 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) . Asurrogat 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 ) are 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 ) Asolutio 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 ctoxicit 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 . Areference 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 PFOAi n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1 Parts 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 are 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 Ahig h performance liqui d chromatograp h capabl e o f pumpin g u p t o two solvents 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 Adevic e t o collec

t ra wdat 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 . Gas tigh t syringes , 25pL , 50pL , lOOpL , 250pL , 500pL , lOOOpL . 1 m L plasti cHPLC 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 : FlowRat 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 ccurve 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 are 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 PFOAi 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 PFHpA 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 PFDA 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 sensitivityi s achieved , provide d tha t retentio n tim e criteri a ar e met 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 cAci d (PFBA- C 4 acid) ; Oakwoo d Products , In c Perfluoropentanoi cAci d (PFPeA- C 5 acid , als o know n a s NFPA , nonafluoropentanoi cacid) ; Alf a Aesa r PerfluorohexanoicAci d (PFHA-C 6 acid) ; Oakwoo d Products , In c Perfluoroheptanoi cAci d (PFHpA- C 7 acid , als o know n a s TDHA , tridecafluoroheptanoi cacid) ; Oakwoo d Products , In c Perfluorooctanoi cAci d (PF0A-C 8 acid) ; 3 M Perfluorononanoi cAci d (PFNA-C 9 acid) ; Oakwoo d Products , In c Perfluorodecanoi cAci d (PFDA-C1 0 acid) ; Oakwoo d Products , In c Perfluoroundecanoi cAci d (PFUnA-C1 1 acid) ; Oakwoo d Products , In c Perfluorododecanoi cAci 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

Ai 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 cflask 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 cflask . 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 belowfo 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 cflas 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 PFOAi 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 data 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 belowca 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 cautovial . Plasti ci 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 QC sample s an d multipl e metho d blank s an d aliquot into labele d plasti cautovials . 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 curve 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 cfi 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 curve 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 wdata . Hig h and/o rlo

wpoints 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 theydi d no t meet th e pre-determine d acceptance criteria . Low-leve l curv e points shoul d als o b e exclude d i f thei rare a counts 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 curve 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 PFOAi 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 wdata . Aminimu 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 wstandar 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 Data 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 wwil l b e documente d i n th e ra wdat 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 counts 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 results 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 results 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 crequirements . 

### 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 wla 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 set 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 PFOAi 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 results 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 performance 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 wdata . 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 curve an d are repeate d injection s fro m on e autosample rvial . Th e syste m suitabilit yinjection s mus

t hav e are a counts 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 are 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 PFOAi 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 cretentio 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 canalyt 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 results 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 accordance wit h interna l procedures . 1 4 Record s Eac h data 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 PFOAi n Groundwate rSample s Off-Sit e 61 0 Wells ; Septembe r201 1 

### ATTACHMEN TD : DEVIATION(S )

Pag e 4 3 o f 4 4GLP10-01-01 ; Interi m Repor t 23 Analysi s o f PFO AI 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 PFOAconcentratio n i n th e sample . However , sinc e th e ^^C4-PF0Asurrogat 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 yo f tin e nonconformin g work : 1 . Th e PFOARP 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 AG 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 yDirecto 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

yDepartmen 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

yDepartmen 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 4