GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFO Ai n Groundwate r Decatur, AL - Decembe r201 1

GLP10-01-01 . Interi m Repor t 24 : Analysi s o fPFO A I n Groundwate r Sample s Collecte d a t th e Forme r Sludg e Incorporatio n Are a (FSIA ) locate d i n Decatur . AL . i n Decembe 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 Maplewood , M N 5514 4 Projec t Identificatio n GLPlO-01-01-2 4 Tota l Numbe r o fPage s

7 0
The testin g reported herei n mee t th e requirement

s of ANSI/

iSO/lE C 17025:200

5 "Genera i Requirement

s fo rth e Competenc

e of Testin g an d Calibratio n Laboratories" , i n accordanc e wit h th e A2L ATestin g Certificate # 2052.01
. Testin g tha t complie s wit h thi s Intemationei l Standar d ais o meet s principle s of IS

O 9001:2000
. Testin g Cer t #2052.0 1

Page 1 o f 7 0GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFOAi n Groundwate r Decatur , A L - Decembe r201 1

Thi s pag e ha

s bee n reserve d fo rspecifi ccountr yrequirements
.

Pag e 2 o f 7 0GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFOAi n Groundwate r Decatur , A L - Decembe r201 1



### GL P COMPLIANC E STATEMEN T Repor t Title : GLP I 0-01-01 , Interi m Repor t 24
. Analysi s o

f PFO Ai n Groundwate rSample s Collecte d a t th e Fomne rSludg e Incorporatio n Are a (FSIA ) a t Decatur , AL , i n Decembe 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 analytica l phas e was 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 ctest syste m an d n o dosin g of 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 test sit e hav

e no t bee n detennine d unde rGLPs
.

Gar yHohe/isteif

W Sponso rRepresentative Date

Jaisimh a I^Cesari , P.E. , DEE , StudyDirecto r- ' 'Dat e

Pag e 3 o f 7 0.GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFO AI n Groundwate r Decatur , A L - Decembe r201 1



### QUALIT YASSURANC E STATEMEN T Repor t Title : GLPI0-01-01 , Interi m Repor t 24
. Analysi s of PFO

Ai n Groundwate rSample s Collecte d a t th e Fonne rSludg e Incorporatio n Are a (FSIA) a t Decatur , AL , i n Decembe 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 repor

t an d th e accompanyin g data were audite d b yth e 3 M Environmenta l Laborator yQualit y Assurance Uni t (QAU) , a s indicate d below
. Th e finding s were reporte d t o th e principa l investigato r (P.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 1/9/2012-1/12/201 2 Dat a / Interi m Repor

t 1/24/201 2 1/24/201 2



### QA U Repre|g6fe{iv e Date

Pag e 4 o f 7 0GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFO Ai n Groundwate r Decatur , A L - Decembe r201 1



### TABL E O F CONTENT S GL P Compliance Statemen t 3 Qualit yAssuranc e Statemen t 4 Tabl e of Contents 5 List of Table s 6 1 Stud yInformatio n 8 2 Summar

y9 3 Introductio n • . 1 0 4 Tes t & Contro l Substance s ••• • 1 1 5 Reference Substance s 1 1 6 Test Syste m 1 2 7 Metho d Summar

y1 2 7. 1 Method s 1 2 7. 2 Sampl e Collectio n 1 2 7. 3 Sampl e Preparatio n 1 2 7. 4 Analysi s 1 2 8 Analytica l Res u It

s 1 3 8. 1 Calibratio n 1 3 8. 2 Syste m Suitabilit y1 4 8. 3 Limi t of Quantitatio n (LOQ ) 1 4 8. 4 Continuin g Calibratio n -1 4 8. 5 Blank

s 1 4 8. 6 La b Contro l Spike s (LCSs ) ••1 4 8. 7 • Analytica l Metho d Uncertaint y1 5 8. 8 Fiel d Matri xSpike s (FMS ) 1 5

Pag e 5 o f 7 0GLP I 0-01-01; Interi m Repor t 2 4 Analysi s o f PFO Ai n Groundwate r Decatur , A L - Decembe r201 1

9 Data Summar

yan d Discussio n 1 6 1 0 Conclusion.. : 2 5 1 1 Data/Sampl e Retentio n 2 5 1 2 /attachments 2 5 1 3 Signature s 2 6 

### LIS TO F TABLE S Tabl e 1
. Summarize d PFO AResults (FSI AGroundwater , Decatur , AL , Decembe r2011 ) 1 0 Tabl e 2
. Instalmen t Parameter s .....1 3 Tabl e 3
. Liqui d Chromatograph yCondition s 1 3 Tabl e 4
. Mass Transition s 1 3 Tabl e 5 . Limi t of Quantitatio n (LOQ ) 1 4 Tabl e 6
. Laborator

yContro l Spik

e Recover

y1 5 Tabl e 7 . Analytica l Metho d Uncertaint y1 5 Tabl e 8
. Fiel d Matri xSpike Level s 1 6 Tabl e 9
. DA L G W 130 R 11120 8 1 7 Tabl e 10
. DA L G W 130 S 11120 8 1 7 Tabl e 11
. DA L G W 130 L 11120 8 1 7 Tabl e 12
. DA L G W 131 R 11121 4 1 7 Tabl e 13
. DALG W 131 S 11121 4 1 8 Tabl e 14
. DA L G W 131L11121 4 1 8 Tabl e 15
. DA L G W 133 R 11121 4 1 8 Tabl e 16
. DALG W 133 S 11121 4 1 8 Table17
. DA L G W 133 L 11121 4 ;.1 9 Tabl e 18
. DALG W 134 R 11120 9 ^..1 9 Tabl e 19
. DA L G W 134 S 11120 9 1 9 Tabl e 20
. DALG W 134 L 11120 9 ' 2 0

Pag e 6 o f 7 0GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFO Ai n Groundwate r Decatur , A L - Decembe r201 1

Tabl e 21
. DA L G W 135 R 11121 4 2 0 Table22
. DALG W 135 S 11121 4 2 0 Table23
. DA L G W 135 L 11121 4 2 0 Tabl e 24
. DA L G W 136 S 11121 3 2 1 Tabl e 25
. DA L G W 136 L 11121 3 2 1 Table26
. DALG W 137 S 11120 9 2 1 Tabl e 27
. DA L G W 137 L 11120 9 2 1 Tabl e 28
. DA L G W 138 R 11121 4 2 2 Tabl e 29
. DA L G W 138 S 11121 4 2 2 Tabl e 30
. DA L G W 138L11121 4 2 2 Tabl e 31
. DA L G W 140 R 11121 3 2 2 Table32
. DALG W 141 R 111214.
. 2 3 Tabl e 33
. DA L G W 142 R 11121 3 2 3 Tabl e 34
. DA L G W 143 R 11120 9 2 3 Table35
. DALG W 144 R 11121 3 2 3 Tabl e 36
. Tri p Blan k

1 2 4 Tabl e 37
. Rinseat e Blank s 2 4

Pag e 7 o f 7 0GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFO Ai n Groundwate r Decatur , A L - Decembe r201 1



### 1 Study

Information Sponso r 3 M Compan y Sponso rRepresentativ 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 Maplewood , M N 5510 6 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(a:)mmm.com) : phon e (65 1 )-733-986 0 Susa n Wolf , 3 M Analyst Chelsi e Grochow , Analys t Kell yUkes , Analys t Stud y Date s Stud yInitiation : Marc h 8,201 0 Interi m Repor

t 1 8 Experimenta l Tennination : Januar y2 , 201 2 Interi m Repor

t Completion : Dat e of Interi m Repor t Signin g Locatio n o

fArchive s Al l origina l rawdat a an d th e analytica l repor t hav e 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 standard resen/ e sample s are archive d at th e 3 M Environmenta l Laborator yaccordin g t o 4 0 CF R Par t 79 2

Pag e 8 o f 7 0GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFOAi n Groundwate r Decatur , A L - Decembe r201 1

Th e 3 M Environmenta l Laborator yreceive d groundwate rsample s fro m well s locate d a t th e Fonne r Sludg e Incorporatio n Are a (FSIA) i n Decatur , AL , representin g twenty-seve n differen t samplin g locations
. Atota l o

f eighty-eigh t sampl e bottle s were receive d a t th e 3 M Environmenta l Laborator yfo r perfluorooctanoat e (PFOA ) analysis , an d include d duplicat e groundwate rsample s fro m eac h samplin g location
. Sample s als o include d on e fiel d matri xspik e (FMS ) sampl e fo reac h location , on e tri p blan k set containin g Milli-Q TM wate ran d appropriat e tri p blan k spikes , an d two equipmen t rinseate blanks
. Th e equipmen t rinseate blank s di d no t hav e FM S sample s prepare d fo rdetenninatio n of PFO A recovery . Th e groundwate rsamples , tri p blanks , an d two equipmen t rinseate blank s were receive d fro m Westo n personne l o n Decembe r20 , 2011
. Al l o f th e sample s were prepare d an d analyze d fo r PFO Afollowin g 3 M Environmenta l Laborator yMetho d ETS-8-044. 1 unde r3 M projec t GLP10-01-01 - 24
. Man yo

f th e groundwate rsample s require d dilutio n t o attai n PFO Aconcentration s withi n th e rang e o f th e curve , i n som e instance s u p t o 100-fol d dilutio n were required
. Th e averag e measure d PFO A concentration s ar

e summarize d i n Tabl e 1
. Th e equipmen t rinseate blank s an d tri p blan k

wer e belo w th e lowe rlimi t of quantitatio n (LLOQ ) o f 0.028 7 ng/mL , indicatin g adequat e contro l o f sampl e contaminatio n durin g shippin g an d sampl e collection
. Th e PFO Aconcentratio n results fo ral l groundwater

s range d ove rfou rorder

s of magnitud e fro m 0.34 1 ng/m L t o 321 0 ng/mL
. Th e analytica l uncertaint ywa s estimate d a

t ±19%
.

Pag e 9 o f 7 0GLPI0-01-01 ; Interi m Repor t 2 4 Analysi s of PFOAI n Groundwate r Decatur , A L - Decembe r201 1

Tabl e 1 . Summarize d PFO A Result s (FSI A Groundwater , Decatur , AL , Decembe r 2011 ) Avg . PFO A Relativ e Sampl e I D Concentratio n Percen t (ng/mL ) Differenc e DA L GW130 R 11120 8 78 3 1.8 % DA L GW130 S 11120 8 14 5 3.5 % DA L GW130 L 11120 8 58. 0 2.8 % DA L GW131 R 11121 4 143 0 0.70 % DA L GW131 S 11121 4 22. 7 0.44 % DA L GW131 L 11121 4 77. 5 0.77 % DA L GW133 R 11121 4 64. 4 20 % DA L GW133 S 11121 4 29 2 2.7 % DA L GW133 L 11121 4 27 5 1.5 % DALGW134R11120 9 208 0 [a ] 1.4 % DA L GW134 S 11120 9 12. 5 1.6 % DA L GW134L11120 9 51 8 0.0 % DA L GW135 R 11121 4 321 0 0.0 % DA L GW135 S 11121 4 18. 9 3.2 % DA L GW135 L 11121 4 17 2 4.7 % DA L GW136 S 11121 3 54. 7 1.5 % DA L GW136 L 11121 3 64. 4 1.7 % DA L GW137 S 11120 9 0.34 1 2 1 % [b ] DALG W 137 L 11120 9 0.36 3 4.7 % DA L GW138 R 11121 4 25 1 0.80 % DA L GW138 S 11121 4 12 3 1.6 % DA L GW138 L 11121 4 0.47 3 14 % DA L GW140 R 11121 3 11 3 0.89 % DALG W 141 R 11121 4 1.4 5 4.1 % DA L GW142 R 11121 3 51. 7 0.58 % DALGW143R11120 9 12. 9 0.78 % DA L GW144 R 11121 3 61. 4 1.3 % Tri p Blank s (Milli-Q TM Water ) < 0.028 7 N/ A GLPlO-01-01-2 4 Equipmen t rinseate blanks : DA L G W 140 R an d DA L G W 133 L < 0.028 7 N/ A N/A : no t applicabl e Th e analytica l uncertaint

yfo rPFO Awas estimate d a

t +19%
. [a ] Th e analytica l uncertaint yha s bee n expande d t o + 37%
. [b ] Sample/sampl e duplicat e RP D di d no t meet acceptance criteri a of <20%
. 

### 3 Introduction Thi s analytica l stud ywas conducte d as par t o f th e Phas e 3 Environmenta l Monitorin g an d Assessmen t Progra m fo rth e 3 M facilit

ylocate d i n Decatur , Alabama
. Th e objective o f th e overal l progra m i s t o gai n infoimatio n regardin g concentration s o f perfluorooctanoat e (PFOA ) i n variou s environmenta l medi a suc h as groundwater , soil s an d sediments tha t are associate d wit h an d nea rth e Decatu rfacility
. Thi s analytica l stud ywas conducte d t o analyz e groun d wate rsample s collecte d fro m variou s well s locate d a t th e Fonne rSludg e Incorporatio n Are a (FSIA ) i n Decatur , A L fo rPFO

Ai n a n effor

t t o characteriz e regiona l groundwate rconditions
.

Pag e 1 0 o f 7 0GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFOAi n Groundwate r Decatur , A L - Decembe r201 1

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 a fiel d spike sample
. 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 of 20 0 mL
. Container s designate d fo rfiel d matri xsample s were fortifie d wit h a h 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
. Se e sectio n 8. 8 o

f th e repor

t fo rfiel d matri xspike levels
. 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. 1 "Metho d o f Analysi s fo rth e Detenninatio n of Perfluorinate d Compound s i n Wate rb

yHig h Performance Liqui d Chromatography/Mas s Spectrometr yDirec t Injectio n Analysis"
. Tabl e 1 summarize s th e averag e PFO Aconcentration s fo rth e duplicat e groundwate rsample s collected , th e tri p blank , an d equipmen t rinseate blan k samples
. Table s 9-3 7 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 are reporte d an d discusse d elsewhere i n thi s report . 

### 4 Test &-Control,Substances There wa s no

t a test substance o rcontro l substance s i n th e classi csens e o f a GL P study
. Thi s stud y was 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

(Branche d an d Linea r isomers ) PFO A (Branche d an d Linea r isomers ) Chemica l Nam e Perfluorooctanoate Perfluorooctanoate Chemica l Formul a C7F15COO H C7F15COO H Identifie r CAS #95328-99- 7 Ammoniu m Sal t CAS #335-67- 1 Us e Target Analyt e Reference Standar d FM S Reference Standar d Source Wellingto n Sigma Pidnch Expiratio n Date 03/17/201 4 07/27/201 6 Storag e Condition s Froze n /\mbien t Chemica l Lo

t Numbe r TPFOA031 1 MKBD4574V TC R Numbe r TCR11-000 9 TCR11-002 9 Physica l Descriptio n Liqui d Powde r Purit y NA<^ > 96.8 % (1 ) Reference standar

d a t a concentratio n of 5 0 ±2. 5 |jg/m L

Pag e 1 1 o f 7 0GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFO AI n Groundwate r Decatur , A L - Decembe r201 1



### 6 Tesf System There wa s no

t a tes t syste m fo rthi s stud yi n th e classi csens e of a GL P study
. Thi s stud ywas conducte d fo ranalysi s of groun d wate rsample s collecte d fro m well s locate d i n Decatur , A L b yWesto n Solutions , Inc
. personnel
. Sample s fo rthi s stud yar e "rea l worid " environmenta l samples
. Sampl e Descriptio n Key Code . strin g Numbe r Strin g Descripto r Exampl e Example DALGW 131R 0111214 1 Sample Location DAL= Decatur, Alabama 2 Well ID Example: 131 3 Well Level R = Residuum

shallow water-bearing

zone L= Bedrock water-bearing

zone S = Epikarst middle water-bearing

zone 4 Sampling Date 111214-December 14,2011 5 Sample Type 0=primary sample DB=duplicate

sample FMS = Field Matrix Spike 

### 7 Method

Summary 7. 1 Method s Analysi s fo ral l analyte s wa s complete d followin g 3 M Environmenta l Laborator ymetho d ETS-8-044. 1 "Metho d of Analysi s fo rth e Detemninatio n of Perfluorinate d Compound s I n Wate rb yHig h Perfomianc e Liqui d Chromatography/Mas s Spectrometr yDirec t Injectio 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 GLP10-0 1 -0 1 -2 4 were returne d t o th e laborator ya t ambien t condition s o n Decembe r20 , 2011
. Sample s were store d refrigerate d a t th e laborator yafte rreceipt
. Aset o

f 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 sampl e collectio n bottles
. 

### 7. 3 Sampl e Preparatio n Sample s were prepare d b yremovin 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
. Sample s that require d dilutio n were prepare d b ydilution s Im L sampl e wit h 9 mLs of Milli- Q wate r (dilutio n 1:10)
. Sample s that require d dilutio n were prepare d b ydilutin g ImLo f sampl e wit h 9 mLs of Mill i Q wate r(dilutio n 1:10)
. Sample s requirin g a 1:100 dilutio n were prepare d b ydilutin g 0. 1 m L o

f sampl e wit h 9. 9 mL

s o f Milli Q water . 

### 7. 4 Analysi s Al l stud y samples an d qualit

y control samples wer

e analyzed for PFO A usin g hig h performanc e liqui d chromatography

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

t parameters , the liqui d chromatograph

y gradien t program , an d the specifi c mas s transitions analyze d ar e describe

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

a packet , and ar

e briefl y describe

d belo wi n Tabl e 2 , Tabl e 3 an d Tabl e 4 .
Pag e 1 2 o f 7 0GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFOAi n Groundwate r Decatur , A L - Decembe r201 1

Tabl e 2 . Instrumen t Parameters . Instrumen t Name ET S Buste r Analytica l Metho

d Followe d ETS-8-044. 1 Analysi s Dat

e 12/30/11-1/2/1 2 Liqui d Chromatograp h Agilen t 1100 Guar d colum n Pris m R P (2. 1 m m X 5 0 mm) , 5 n Analytica l colum n Betasi l C1 8 (2. 1 m m X 100 mm) , 5 n Injectio n Volum e 1 0 n L iVIas s Spectromete r Applie d Biosystem s AP I 400 0 Io n Sourc e Turt o Spra y Electrod e Turt3 0 io n electrod e Polarit y Negativ e Softwar e Analyst 1.4. 2 Tabl e 3 . Liqui d Chromatograph y Conditions . step Total

Time Flow

Rate Percent A Percent B Number (min) (^min) (2 mM ammonium

acetate) (MethanoO ETS-8-044. 1 Analysi s 0 0. 0 30 0 97. 0 3. 0 1 2. 0 30 0 97. 0 3. 0 2 14. 5 30 0 5.0 95. 0 3 15. 5 30 0 5.0 95. 0 4 16. 5 30 0 97. 0 3. 0 5 20. 0 30 0 97. 0 3. 0 Tabl e 4 . Mas s Transitions .

Analyte Mass Transition Q1/Q3 PFOA 413/369 413/219 413/169 Dwel l tim e wa s 100 mse cfo reac h transition
. Th e individua l transition s were 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 Al l samples wer

e analyzed agains

t a n externa l standar

d calibratio n curve . Calibratio n standard s wer e prepare d b y spikin g know

n amount s o f the stock

solution containin g PFO A int o laboratory-Mill i Q water. A total o f fifteen spike

d standard s ranging fro

m 0.025 ng/m L t

o 10 0 ng/m L (nominal

) wer e prepare d an d analzyed . A quadratic , 1/ xweighted , calibration curv e o f the pea k

are a count

s was use

d t o fi t the dat a fo r PFOA . Th e dat

a wer e no t force d throug h zer

o during th e fitting process . Calculatin g the standar d concentration s usin g the pea k area confirme

d accurac y o feac h curv

e point .

Pag e 1 3 o f70GLP I 0-01-01; Interi m Repor t 2 4 Analysi s o f PFO AI n Groundwate r Decatur , A L - Decembe r201 1

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 o

f 100±25 % (100±30 % fo rth e lowest curve point) were met . Th e conelatio 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 met fo rPFOA
. 8. 3 Limi t o fQuantitatio n (LOQ ) Th e LO Q for thi s analysi s i s the lowes t non-zer o calibration standar

d i n the curv

e tha t meet s linearit y an d accurac

y requirement

s an d for which 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 for al l analyte s ca n b e found i n Tabl e 5 . Tabl e 5 . Limi t o

fQuantitatio n (LOQ) . Analysis Date(s} PFOA

LOQ, ng/mL 12/30/1 1 0.028 7 8. 4 Continuin g Calibratio n Durin g th e cours e o

f eac h analytica l sequence , continuin g calibratio n verificatio n sample s (CCVs ) were analyze d t o confir m that th e instrumen t respons e an d th e initia l calibratio n curve were stil l i n control
. Al l CCV s met metho d criteri a o

f 100 % ±25 % fo rPFOA
. 8. 5 Blank s Thre e type s o

f blank s were prepare d an d analyze d wit h th e samples : procedura l blanks , tri p blanks , an d equipmen t rinseate blanks
. Procedura l blan k results were reviewe d an d use d t o evaluat e metho d performance an d t o detennin 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
. Equipmen t rinseate blank s are aqueou s sample s that reflec

t th e efficienc

yo f equipmen t cleanin g i n th e fiel d betwee n differen t sampl e collection s t o ensure n o cros s contaminatio n of sample s fro m th e equipment
. 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 o f 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 o f LCS 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 rPFOA
. Al l LC S sample s were use d i n th e detenninatio n of metho d uncertaint yi n sectio n 8.7
. Th e followin g calculation s were use d t o generat e dat a i n Tabl e 6 fo rlaborator ycontro l spikes :

, „ „ „ . 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 . ^ Q^^ ^ averag e LC S recover

y

Pag e 1 4 o f 7 0GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFOAi n Groundwate r Decatur , A L - Decembe r201 1

Tabl e 6 . Laboratory Contro l Spike Recovery . ETS-8-044. 1 Analyze d 12/30/1 1 PFOA(Branched and Linear isomers)
Lab ID Spiked

Concentration (ng/mL) Calculated

Concentration (ng/mL) YoRecovery LCS-111221 ^ 0.47 7 0.50 4 10 6 LCS-111221- 5 0.47 7 0.51 5 10 8 LCS-111221- 6 0.47 7 0.511 10 7 Averag e ±%RS D 107 % ±0.93 % LCS-111221- 7 4.7 7 5.3 5 11 2 LCS-111221- 8 4.7 7 5.3 7 11 3 LCS-111221- 9 4.7 7 5.3 7 11 3 Averag e ±%RS D 113 % ±0.51 % LCS-111221-1 0 28. 7 21. 1 73. 5 LCS-111221-1 1 28. 7 24. 0 83. 8 LCS-111221-1 2 28. 7 24. 4 84. 9 Averag e ±%RS D 80.7 % ±7.8 % 

### 8. 7 Analytica l Method Uncertainty Analytica l uncertaint

yi s base d o n historica l QC data 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 QC samples
. Th e metho d uncertaint

yi s calculate d b

ymultiplyin g th e standar

d deviatio n b

ya facto ro

f 2 , whic h correspond s t o a confidence leve l o f 95%
. Tabl e 7 . Analytica l Method Uncertainty . Analyt e Metho d Standar d Deviatio n Metho d Uncertaint y PFO A ETS-8-044. 1 9.7 4 ±19 % 

### 8. 8 Fiel d Matri x Spike s (FMS ) Afiel d matri xspike wa s 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 b yaddin g a measure d volum e o f fiel d sampl e t o a containe rspike d b yth e laborator

ywit h th e target analyte s 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 o f 100±30 % confir m that "unknown " components i n th e sampl e matri xd o no t significantl yinterfer

e wit h th e extractio n an d analysi s o

f th e analyte s o

f interest
. Fiel d matri xspik e concentration s mus

t b e 50 % o

f th e sampl e concentratio n t o b e considere d a n appropriat e fiel d spike
. Fiel d matri xspike s ar e presente d i n sectio n 9 o

f thi s report .

Pag e 1 5 o f 7 0GLP10-01-01 ; Interi m Repor t 2 4 Analysi s of PFOAi n Groundwate r Decatur , A L - Decembe r201 1

Tabl e 8 . Fiel d Matri x Spike Levels . Samplin g Locatio n (Wel l ID ) Spik e Leve l PFOA , ng/m L 136R , 137R , 137S , 137L , 138L , 141 R FM S 0.974 131S , 134S , 135S , 143 R FM S 19. 5 130L , 142R , 144 R FM S 48. 7 130S , 131L , 133R , 136S , 136L , 140 R FM S 97. 4 133S , 133L , 135L , 138R , 138 S FM S 195 130R , 134L , CW26C , CW26 L FM S 48 7 131R , 134R , 135 R FM S 195 0 Tri p Blan k Lo w 0.974 Tri p Blan k Mi d 19. 5 Tri p Blan k Mid-Hig h 97. 4 Tri p Blan k Hig h 48 7

(Sampl e Concentratio

n o f FM S - Averag

e Concentratio

n : Fiel dSampl e & Fiel dSampl e Dup. ) , „„„ , FM S Recover y = J-^ * 100 % Spik e Concentrato

n 

## 9 Dats0ummaiy^h ^

Discussio n ,'l;\'..;.Jv- l •^g-;:'-'-- ! 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 as wel l as th e Tri p Blank s an d rinseate blanks
. Results an d averag e value s ar e 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 y fro 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 o f ±30% , demonstrat e tha t th e metho d was appropriat e fo rth e give n matri xan d thei rrespective quantitative ranges . DA L G W 134R11120 9 - Th e PFO AFM S recover

ywas 62.8%
. Base d o n th e recover yo f th e FM S sample , th e metho d uncertaint yfo rthi s sampl e was expande d t o ±37%
.

Pag e 1 6 o f 7 0Tables . DA L G W130 R 111208

N A= No t Applicabl e Sample s dilute d 1:10

0 Tabl e 10 . DA L G W1 SOS 111208

NA= No t Applicabl e Sample s dilute d 1:1 0 Tabl e 11 . DA L G W1 SO L 11120 8

N A= No t Applicabl e Sample s dilute d 1:1 0 Tabl e 12 . DA L G W1S1 R 11121 4

NA= No t Applicabl e Sample s dilute d 1:10

0 GLP I 0-01-01 ; Interi m Repor t 2 4 Analysi s o f PFO Ai n Groundwate r Decatur , A L - Decembe r201 1

PFOA Concentration 3M LIMS ID Description (ng/mL) YoRecovery GLP10-01-01-24-00 1 DAL-GW-130R-0-11120 8 79 0 NA GLP10-01-01-24-00 2 DAL-GW-130R-DB-11120 8 77 6 N A GLP I 0-01-01-24-00 3 DAL-GW-130R-FMS-11120 8 1170 79. 5

Average Concentration

(ng/mL) ± %RPD 783 ng/mL±1.8%

PFOA Concentration 3M LIMS ID Description (ng/mL) %Recovery GLP10-01-01-24-00 4 DAL-GW-130S-0-11120 8 142 NA GLP10-01-01-24-00 5 DAL-GW-130S-DB-11120 8 147 NA GLP10-01-01-24-00 6 DAL-GW-130S-FMS-11120 8 21 5 72. 4

Average Concentration

(ng/mL) ± %RPD 145 ng/mL±3.5%

PFOA Concentration 3M LIMS ID Description (ng/mL) YoRecovery GLP I 0-01-01-24-00 7 DAL-GW-130L-0-11120 8 57. 2 NA GLP10-01-01-24-00 8 DAL-GW-130L-DB-11120 8 58. 8 NA GLP10-01-01-24-00 9 DAL-GW-130L-FMS-11120 8 100 86. 2

Average Concentration

(ng/mL) ± %RPD 58.0 ng/mL±2.8%

PFOA Concentration 3M LIMS ID Description (ng/mL) YoRecovery GLP10-01-01-24-01 0 DAL-GW-13 1 R-0-11121 4 142 0 NA GLP I 0-01-01-24-01 1 DAL-GW-131R-DB-11121 4 1430 NA GLP I 0-01-01-24-01 2 DAL-GW-13 1 R-FMS-11121 4 282 0 71. 5

Average Concentration

(ng/mL) ± YoRPD 1430 ng/mL±0.70%

Pag e 1. 7 o f 7 0Tabl e IS . DA L G WISI S 11121 4

N A= No t Applicabl e Sample s dilute d 1:1 0 Tabl e 14 . DA L G W1S1 L 11121 4

NA = No t Applicabl e Sample s dilute d 1:1 0 Tabl e 15 . DA L G W1S3 R 11121 4

NA= No t Applicabl e Sample s dilute d 1:1 0 Tabl e 16 . DA L G W1 SS S 11121 4

NA= No t Applicabl e Sample s dilute d 1:1 0 GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFO AI n Groundwate r Decatur , A L - Decembe r201 1

PFOA Concentration 3M LIMS ID Description (ng/mL) YoRecovery GLP I 0-01-01-24-01 3 DAL-GW-131S-0-11121 4 22.7 NA GLP10-01-01-24-01 4 DAL-GW-131S-DB-11121 4 22. 6 NA GLP I 0-01-01-24-01 5 DAL-GW-13 1 S-FMS-11121 4 39. 7 87. 5

Average Concentration

(ng/mL) ± YoRPD 22.7ng/mL±0.44Yo

PFOA Concentration 3M LIMS ID Description (ng/mL) YoRecovery GLP I 0-01-01-24-01 6 DAL-GW-131L-0-11121 4 77. 8 NA GLP10-01-01-24-01 7 DAL-GW-131L-DB-11121 4 77. 2 NA GLP I 0-01-01-24-01 8 DAL-GW-13 1 L-FMS-11121 4 158 82. 6

Average Concentration

(ng/mL) ± YoRPD 77.5ng/mL±0.77Yo

PFOA Concentration 3M LIMS ID Description (ng/mL) YoRecovery GLP10-01-01-24-01 9 DAL-GW-133R-0-11121 4 70. 8 NA GLP10-01-01-24-02 0 DAL-GW-133R-DB-11121 4 57. 9 NA GLP10-01-01-24-02 1 DAL-GW-133R-FMS-11121 4 13 4 71. 5 Average Concentration

(ng/mL) ± YoRPD 64.4 ng/mL±20Yo

PFOA Concentration 3M LIMS ID Description (ng/mL) YoRecovery GLP I 0-01-01-24-02 2 DAL-GW-133S-0-11121 4 29 6 NA GLP I 0-01-01-24-02 3 DAL-GW-133S-DB-11121 4 28 8 NA GLP10-01-01-24-02 4 DAL-GW-133S-FMS-11121 4 50 8 11 1

Average Concentration

(ng/mL) ± YoRPD 292 ng/mL±2.7Yo

Pag e 1 8 o f 7 0Tabl e 17 . DA L G W1 SS L 11121 4

N A= No t Applicabl e Sample s dilute d 1:1 0 Tabl e 18 . DA L G W1S4 R 111209

NA = No t Applicabl e Sample s dilute d 1:10

0 (1 ) FM S di d no

t mee t acceptance criteri a of 100 ±30%
. (2 ) Metho d uncertaint

yhas bee n expande d t o ±37%
. Tabl e 19 . DA L G W1S4 S 111209 GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFOAi n Groundwate r Decatur , A L - Decembe r201 1

PFOA Concentration 3M LIMS ID Description (ng/mL) YoRecovery GLP10-01-01-24-02 5 DAL-GW-133L-0-11121 4 27 7 NA GLP I 0-01-01-24-02 6 DAL-GW-133L-DB-11121 4 27 3 NA GLP I 0-01-01-24-02 7 DAL-GW-133L-FMS-11121 4 46 7 98. 6

Average Concentration

(ng/mL) ± YoRPD 275 ng/mL±1.5Yo

PFOA 3M LIMS ID Description Concentration (ng/mL) YoRecovery GLP10-01-01-24-02 8 GLP I 0-01-01-24-02 9 GLP10-01-01-24-03 0 DAL-GW-134R-0-11120 9 DAL-GW-134R-DB-11120 9 DAL-GW-134R-FMS-11120 9 206 0 209 0 330 0 NA

NA 62. 8 Average Concentration

(ng/mL) ± YoRPD 2080 ng/mL±1.4%'^

PFOA Concentration 3M LIMS ID Description (ng/mL) YoRecovery GLP I 0-01-01-24-03 1 DAL-GW-134S-0-11120 9 12. 6 N A GLP I 0-01-01-24-032 DAL-GW-134S-DB-11120 9 . 12. 4 NA GLP10-01-01-24-03 3 DAL-GW-134S-FMS-11120 9 26. 3 70. 8

Average Concentration

(ng/mL) ± YoRPD 12.5 ng/mL±1.6% NA= No t Applicabl e

Pag e 1 9 o f 7 0Tabl e 20 . DALG W1S4 L 11120 9

NA= No t Applicabl e Sample s dilute d 1:10

0 Tabl e 21
. DA L G W 1S5 R 11121 4

NA= No t Applicabl e Sample s dilute d 1:10

0 Tabl e 22 . DA L G W1S5 S 11121 4

NA= No t Applicabl e Tabl e 2S . DA L G W1 SS L 11121 4

NA = No t Applicabl e Sample s dilute d 1:1 0 GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFO Ai n Groundwate r Decatur , A L - Decembe r201 1

PFOA Concentration 3M LIMS ID Description (ng/mL) YoRecovery GLP10-01-01-24-034 DAL-GW-134L-0-11120 9 51 8 NA GLP10-01-01-24-03 5 DAL-GW-134L-DB-11120 9 51 8 NA GLP I 0-01-01-24-03 6 DAL-GW-134L-FMS-11120 9 92 7 84. 0

Average Concentration

(ng/mL) ± YoRPD 518ng/mL±0.0Yo

PFOA Concentration 3M LIMS ID Description (ng/mL) YoRecovery GLP10-01-01-24-03 7 DAL-GW-135R-0-11121 4 321 0 NA GLP10-01-01-24-03 8 DAL-GW-135R-DB-11121 4 321 0 . NA GLP I 0-01-01-24-03 9 DAL-GW-135R-FMS-11121 4 457 0 69. 7

Average Concentration

(ng/mL) ± YoRPD 3210 ng/mL±0.0%

PFOA Concentration 3M LIMS ID Description (ng/mL) YoRecovery GLP I 0-01-01-24-04 0 DAL-GW-135S-0-11121 4 18. 6 NA GLP10-01-01-24-04 1 DAL-GW-135S-DB-11121 4 19. 2 NA GLP10-01-01-24-042 DAL-GW-135S-FMS-11121 4
. 32. 7 70. 8

Average Concentration

(ng/mL) ± YoRPD 18.9 ng/mL±3.2Yo

PFO A Concerrtration 3M LIMS ID Description (ng/mL) YoRecovery GLP10-01-01-24-04 3 DAL-GW-135L-0-11121 4 176 NA GLP10-01-01-24-044 DAL-GW-135L-DB-11121 4 168 NA GLP I 0-01-01-24-04 5 DAL-GW-135L-FMS-11121 4 31 7 74. 4

Average Concentration

(ng/mL) ± YoRPD 172ng/mL±4.7%

Pag e 2 0 o f 7 0Tabl e 24 . DA L G W1S6 S 11121 S

NA = No t Applicabl e Sample s dilute d 1:1 0 Tabl e 25 . DA L G W1S6 L 11121 3

N A= No t Applicabl e Sample s dilute d 1:1 0 Tabl e 26 . DA L G W137 S 111209

NA = No t Applicabl e (1 ) RP D di

d no t mee t acceptanc

e criteria o

f S20% . Tabl e 27 . DA L G W1S7 L 11120 9 GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFOAi n Groundwate r Decatur , A L - Decembe r201 1

PFO A Concentration 3M LIMS ID Description (ng/mL) YoRecovery GLP10-01-01-24-04 9 DAL-GW-136S-0-11121 3 55. 1 NA GLP I 0-01-01-24-05 0 DAL-GW-136S-DB-11121 3 54. 3 NA GLP10-01-01-24-05 1 DAL-GW-136S-FMS-11121 3 140 87. 6

Average Concentration

(ng/mL) ± YoRPD 54.7ng/mL±1.5Yo

PFO A Concerrtration 3M LIMS ID Description (ng/mL) YoRecovery GLP10-01-01-24-05 2 DAL-GW-136L-0-11121 3 64. 9 NA GLP I 0-01-01-24-05 3 DAL-GW-136L-DB-11121 3 63. 8 N A GLP I 0-01-01-24-05 4 DAL-GW-136L-FMS-11121 3 153 91. 0

Average Concentration

(ng/mL) ± YoRPD 64. 4 ng/m L ±17 %

• PFO A Concerrtration 3M LIMS ID Description (ng/mL) YoRecovery GLP10-01-01-24-05 8 DAL-GW-137S-0-11120 9 0.37 6 NA GLP10-01-01-24-05 9 DAL-GW-137S-DB-11120 9 0.30 6 NA GLP I 0-01-01-24-06 0 DAL-GW-137S-FMS-11120 9 1.1 4 82. 0

Average Concentration

(ng/mL) ± YoRPD 0.34* ng/mL± 21%,

PFO A Concentration 3M LIMS ID Description (ng/mL) YoRecovery GLP10-01-01-24-06 1 DAL-GW-137L-0-11120 9 0.37 1 NA GLP I 0-01-01-24-06 2 DAL-GW-137L-DB-11120 9 0.35 4 NA GLP I 0-01-01-24-06 3 DAL-GW-137L-FMS-11120 9 1.3 6 10

2 Average Concentration

(ng/mL) ± YoRPD 0.363 ng/mL±4.7% NA= No t Applicabl e

Pag e 2 1 o f 7 0GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFO AI n Groundwate r Decatur , A L - Decembe r201 1

Tabl e 28 . DA L G W1S8 R 11121 4 PFO A Concerrtration 3M LIMS ID Description (ng/mL) YoRecovery GLP10-01-01-24-06 4 DAL-GW-138R-0-11121 4 25 2 NA GLP10-01-01-24-06 5 DAL-GW-138R-DB-11121 4 25 0 NA GLP I 0-01-01-24-06 6 DAL-GW-138R-FMS-11121 4 39 7 74. 9

Average Concentration

(ng/mL) ± YoRPD 251 ng/mL±0.80% NA= No t Applicabl e Sample s dilute d 1:1 0 Tabl e 29 . DA L G W138 S 11121 4 PFOA Concentration 3M LIMS ID Description (ng/mL) YoRecovery GLP10-01-01-24-06 7 DAL-GW-138S-0-11121 4 12 2 NA GLP I 0-01-01-24-06 8 DAL-GW-138S-DB-11121 4 124 NA GLP10-01-01-24-06 9 DAL-GW-138S-FMS-11121 4 28 1 81. 1

Average Concentration

(ng/mL) ± YoRPD 123 ng/mL± 1.6%, N A= No t Applicabl e Sample s dilute d 1:1 0 Tabl e SO . DA L G W1S8 L 11121 4 PFO A Concentration 3M LIMS ID Description (ng/mL) YoRecovery GLP I 0-01-01-24-07 0 DAL-GW-138L-C-11121 4 0.50 5 NA GLP10-01-01-24-07 1 DAL-GW-138L-DBr11121 4 0.44 0 NA GLP I 0-01-01-24-072 DAL-GW-138L-FMS-11121 4 1.4 5 100 Average Concentration

(ng/mL) ± YoRPD 0.473 ng/mL± 14%, NA= No t Applicabl e Tabl e SI . DA L G W140 R 11121 3 PFOA Concentration 3M LIMS ID Description (ng/mL) YoRecovery GLP I 0-01-01-24-07 3 DAL-GW-140R-0-11121 3 11 3 NA GLP10-01-01-24-074 DAL-GW-140R-DB-11121 3 11 2 N A GLP10-01-01-24-07 5 DAL-GW-140R-FMS-11121 3 199 88. 8

Average Concentration

(ng/mL) ± YoRPD 113 ng/mL±0.89Yo N A= No t Applicabl e Sample s dilute d 1:1 0

Pag e 2 2 o f 7 0Tabl e 32 . DA L G W141 R 11121 4

NA= No t Applicabl e Tabl e SS . DA L G W142 R 11121 S

N A= No t Applicabl e Sample s dilute d 1:1 0 Tabl e 34 . DA L G W14S R 111209

N A= No t Applicabl e Sample s dilute d 1:1 0 Tabl e 35 . DA L G W144 R 11121 3

N A= No t Applicabl e Sample s dilute d 1:1 0 GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFOAi n Groundwate r Decatur , A L - Decembe r201 1

PFO A Concerrtration 3M LIMS ID Description (ng/mL) YoRecovery GLP I 0-01-01-24-07 6 DAL-GW-14 1 R-0-11121 4 1.4 8 NA GLP I 0-01-01-24-07 7 DAL-GW-141R-DB-11121 4 1.4 2 NA GLP I 0-01-01-24-07 8 DAL-GW-14 1 R-FMS-11121 4 2.42 99. 6

Average Concentration

(ng/mL) ± YoRPD 1.45 ng/mL±4.1Yo

PFOA Concentration 3M LIMS ID Description (ng/mL) YoRecovery GLP10-01-01-24-07 9 DAL-GW-142R-0-11121 3 51. 8 NA GLP10-01-01-24-08 0 DAL-GW-142R-DB-11121 3 51. 5 NA GLP I 0-01-01-24-08 1 DAL-GW-142R-FMS-11121 3 • 96. 1 91. 3

Average Concentration

(ng/mL) ± YoRPD 51.7 ng/mL±0.58%,

PFO A Concerrtration 3M LIMS ID Description (ng/mL) YoRecovery GLP10-01-01-24-08 2 DAL-GW-143R-0-11120 9 12. 8 NA GLP I 0-01-01-24-08 3 DAL-GW-143R-DB-11120 9 12. 9 NA GLP10-01-01-24-08 4 DAL-GW-143R-FMS-11120 9 32. 1 98. 8

Average Concentration

(ng/mL) ± YoRPD 12.9 ng/mL±0.78%,

PFO A Concentration 3M LIMS ID Description (ng/mL) YoRecovery GLP10-01-01-24-08 5 DAL-GW-144R-0-11121 3 61. 8 , NA GLP I 0-01-01-24-08 6 DAL-GW-144R-DB-11121 3 61. 0 NA GLP10-01-01-24-08 7 DAL-GW-144R-FMS-11121 3 107 93. 6

Average Concentration

(ng/mL) ± YoRPD 61.4 ng/mL±1.3Yo

Pag e 2 3 o f 7 0Tabl e 36 . Tri p Blan k 1

NA= No t Applicabl e Sampl e GLP I 0-01-01-24-09 7 dilute d 1:1 0 Sampl e GLP10-01-02-24-09 8 dilute d 1:10 0 Tabl e 37 . Rinseat e Blank s GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFO Ai n Groundwate r Decatur , A L - Decembe r201 1

PFO A Concerrtration 3M LIMS ID Description (ng/mL) YoRecovery GLP I 0-01-01-24-09 4 DAL-GW-TRIP01- 0 <0.028 7 NA GLP10-01-01-24-09 5 DAL-GW-TRIP01-L S 0.95 0 97. 5 GLP10-01-01-24-09 6 DAL-GW-TRIPOl-M S 17. 1 87. 8 GLP I 0-01-01-24-09 7 DAL-GW-TRIP01-MH S 89. 4 91. 8 GLP I 0-01-01-24-09 8 DAL-GW-TR1P01-H S 45 0 92. 4

PFO A 3M LIMS ID Description Concerrtration (ng/mL) YoRecovery GLP10-01-01-24-09 9 GLP I 0-01-01-24-10 0 DAL-GW-140R-RB-11121 3 DAL-GW-133L-RB-11121 4 <0.028 7 <0.028 7 NA

NA NA= No t Applicabl e

Pag e 2 4 o f 7 0GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFOAi n Groundwate r Decatur , A L - Decembe r201 1



### 10 Conclusion Laborator ycontro l spike s an d fiel d matri xspike s were use d t o detennin e th e analytica l metho d accurac yan d precisio n fo rPFOA
. Analysi s was successfull ycomplete d followin g 3 M Environmenta l Laborator ymetho d ETS-8-044. 1 describe d herein
. 

### 11 Data/Sample

Retention Al l remainin g sample s an d associate d projec t data (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 4 (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. 1 Attachmen t D : Metho d Deviatio n

Pag e 2 5 o f 7 0GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFOAi n Groundwate r Decatur , A L - Decembe r201 1



### 13 Signatures

Clesto n Lange , Ph.D. , 3 M Principa l Analytica l Investigato r f Date

Willia m K
. Reagen , Ph.D. , 3 M Environmenta l Laborator yManage r Date

Gar yHohensftein^ M Sponso rRepresentative Date

Jaisimh a Kesan , Stud yDirecto r 'Dat e

Pag e 2 6 o f 7 0GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFO Ai n Groundwate r Decatur , A L - Decembe r201 1


### ATTACHMEN TA : PROTOCO L AMENDMEN T

Pag e 2 7 o f 7 0GLP10-01-01; Interim Report 24 Analysis of PFOAin Groundwater Decatur. AL-

December

2011 Analytical

Protocol:

GLPIO-01-01 Amendment

24


### 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 4

Amendment

Date: Decembe r1 , 201 1 Performing

Laboratory 3 M Environmental , Health , an d Safet yOperation s

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

Project Identification GLPIO-01-0 1 Sampling

Event Forme rSludg e Incorporatio n Are a (FSIA ) Groundwate r

Pag e 1 o f 7 Pag e 2 8 o f 7 0GLPIO-01-01; Interim Report 24 Analysis of PFOAin Groundwater Decatur, AL-

December

2011 Analytical

Protocol:

GLP10-01-01 Amendment

24. 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 wordin g of th e protoco l are required
.
AMEND TO READ: N o change s t o th e wordin g o f th e protoco l are required
. Thi s amendmen t onl yaddresse s an d document s th e additio n of th e Genera l Project Outlin e (GPO ) fo rth e collectio n an d analysi s o f groundwate rsample s a t Decatur , AL , an d conducte d a s par t of th e 3 M Decatu rPhas e 3 Progra m fo rPFOA(GLPIO-01-01)
. Th e anticipate d sampl e collectio n wil l occu raroun d th e timefram e durin g th e wee k o f Decembe r5 , 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 y LIM S a s projec

t GLPlO-01-01-2 4 an d reporte d a s interi m repor t GLP10-01-G1-24 , (reflectin g stud y GLP10-01-0 1 an d amendment-24)
.
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 t o b e conducte d fo rth e 3 M Decatur
. A L facility
. Th e GP O i s fou rpage s i n lengt h an d include d as attache d t o thi s amendmen t form
.

Pag e 2 of 7 Pag e 2 9 o f 7 0GLPIO-01-01; Interim Report 24 Analysis of PFOAin

Groundwater Decatur, AL-, December 2011 Analytical

Protocol:

GLFlO-Ul-or Amendment

24 

### Amendmen t Approva l 

# 0
. Gar yHohenstein , Sponso rRepresentative Dat e

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

# ]zo. Date


### S2 /P^CXC^// Willia m Reagen , BH S Opn s Environmenta l La b Managemen t

Jaisimh a Kesar i P.E. , DEE
. StudyDirecto r Date 

# Ml I Dat e

Pag e 3 of 7

Pag e 3 0 o f 7 0GLPIO-01-01; Interim Report 24 Analysis of PFOAIn Groundwater Decatur, AL-

December

2011 Analytical

Protocol:

GLPIO-01-01 Amendment

24 

### Environmenta l Healt h & SafetyOperations , Environmenta l Laborator y Genera l Projec t Outlin e To : Gar

yHohenstein , 3 M EHS&Opn s From : Susa n Wol f 3 M EHS&Opns ; Environmenta l La b cc : Willia m Reagen , 3 M EHS&Opns ; Environmenta l La b Clesto n Lange , 3 M EHS&Opns ; Environmenta l La b Ja i Kesari , Westo n Solution s Date : Decembe r1 , 201 1 Subject : 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 ; GL P Interi m Repor t 2 4 - Forme rSludg e Incorporatio n Are a (FSIA ) Groundwate r- Decembe r201 1 Samplin g 1 Genera l Projec t Informatio n
3 M Sponso rRepresentativ 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 Qahohenst8in(S;mmm.co m 3 M Environmenta l Laborator yManagemen t Willia m K
. Reage n 3IV 1 EH S Opns , Environmenta l Laborator y 260-5N-1 7 65 1 733-973 9 Contact s wkreaaenffSmmm.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 cclanQe®mmm.co m Samplin g Coordinato r Timoth yFrina k Westo n Solution s Timothv.frinak@wesionsolutions.co m Phone : (334)-332-912 3 La b Reques t Numbe r GLP10-01-01-2 4 Si xDigi t Departmen t Numbe r Dept #530711
. Project #002267444 9 Projec t Schedule/Tes t Date s Samplin g schedule d fo rth e wee k o f Decembe r5 , 201 1 All verbal and written correspondence

will be directed to Gary l-iohenstein.

Pag e 4 o f 7 Pag e 3 1 o f 7 0GLPIO-01-01; Interim Report 24 Analysis of PFOAin

Groundwater Decatur, AL-

December

2011 Analytical

Protocol:

GLPIO-01-01 Amendment

24 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 twenty-seve n groundwate rwell s fo rPerfluorooctanoi cAci d (PFOA ) fro m th e Forme rSludg e Incorporatio n Are a (FSIA)
. Analyse s wil l b e conducte d unde rth e GL P requirement s of EP ATSC AGoo d Laborator yPractic e Standard s 4 0 CF R 792
. Groundwate rsample s fro m Decatur , A L wil l b e collecte d b yWesto n Solution s personne l th e wee k o f Decembe r5 , 2011
. Th e 3 M Environmenta l Laborator ywil l prepare th e sampl e bottle s wit h al l require d spike s t o ensur e tha t result s fo rPFOAare of a know n precisio n an d accuracy . Th e fina l repor t wil l b e submitte d t o Gar

yHohenstei n an d Ja i Kesar i upo n completio n unde rinteri m repor t GLPlO-01-01-24
. 

### 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 Decembe r 5 , 2011
. Sampl e bottle s wil l b e shippe d i n cooler s t o 3 M Decatu rfo rarriva l b yMonday , Decembe r5 , 2011
. Sampl e bottle s shoul d b e store d refrigerate d on-sit e unti l sampl e collection
. Marti n Smit h \

Westo n Traile r 3 M Decatu rPlan t 140 0 Stat e Dock

s Roa d Decatur , Alabam a 3560 1 4 Tes t Parameter s Th e targete d limi t of quantitatio n wil l b e 0.02 5 ng/m L (ppb ) fo rPFOA
. Atota l o f thirty-on e samplin g location s hav e bee n specified
. Fo reac h samplin g location , a sample , sampl e duplicat e an d fiel d matri xspik e wil l be collected
. Tabl e 1 indicate s th e wel l I D an d correspondin g fiel d spik e level
. 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 sets o f tri p blank

s consistin g o

f reagent-grad e water , a low-leve l tri p blan k spike , mid-leve l fiel d spike , mid-hig h fiel d spike , an d a high-leve l tri p blan k spik e wil l b e prepare d a

t th e 3 M Environmenta l Laborator yan d sen t t o th e samplin g locatio n wit h th e othe rbottles
. Base d o n previou s samplin g o f th e FSI A(GLP10-01-01-07 , GLP10-01-01-011
. an d GLP10-01-01-18) , mor e tha n hal f o

f th e sampl e location s ar e expecte d t o have PFO Alevel s greate rtha n 10 0 ng/mL
. To ai d i n th e quantitatio n o

f samplin g location s wit h PFO Alevel s at expecte d concentration s of <5 0 ng/mL , sampl e bottle s wil l contai n th e additio n o f interna l standar

d ^^Cs-PFO

Aan d "C^-PFO Asurrogate.^^Th e tri p blan k sample , tri p blan k lo wan d mi d spike s wil l als o includ e th e additio n o f interna l standar

d Cg-PFO

Aan d C^-PFO

A surrogate . Two additiona l bottle s wil l b e prepare d t o b e use d fo rth e preparatio n of th e equipmen t rinseate blank s an d wil l ais o contai n th e additio n of interna l standar d ''^Cg-PFO

Aan d '^C4-PF0 Asurrogate . A1- L bottl e o f laborator

yreagen t wate rwil l b e provide d t o b e use d t o collec t th e rinseate blanks
.

Pag e 5 of 7 Pag e 3 2 o f 7 0GLPIO-01-01; Interim Report 24 Analysis of PFOAin Groundwater Decatur, AL-

December

2011 Analytical

Protocol:

GLPIO-01-01 Amendment

24 Tabl e 1 . Samplin g Location s an d Fiel d Matri x Spike levels . Set # Wel l No . Spik e Cone
. (ng/mL ) 1 * 136R , 137R , 137S , 137L , 138L , 141 R 1. 0 2 * 131S,134S,135S , 143 R 2 0 3 * 130L , 142R,144 R 5 0 4 130S , 131L , 133R , 136S , 136L
. 140 R 10 0 5 133S , 133L , 135L , 138R , 138 S 20 0 6 130R , 134L , CW26C , CW26 L 50 0 7 131R,134R,135 R 200 0 Tri p Blan k 1 * 20 * Tri p Blan k 10 0 Tri p Blan k 50 0 Sampl e bottle s wil l contai n '-"Cs-PFO Ainterna l standar

d an d C4-PFO

Asurrogate . 5 Tes t Method s Sample s wil l b e prepare d an d analyze d b yLC/MS/M S followin g ETS-8-044. 1 "Metho d o f 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 Injectio n Analysis"
. Th e data qualit yobjective s fo rthes e studie s ar e quantitative results fo r th e target analyte s wit h a n analytica l accurac yo f 100±30%
. Fiel d matri xspike s no t yieldin g recoverie s withi n 100±30 % wil l be addresse d i n th e repor t an d th e final accurac

ystatemen t ma

yb e adjuste d accordingly
. Base d o n th e results fro m previousl ycollecte d sample s fro m th e FSIA , most samplin g location s wil l requir e dilutio n wit h laborator yreagen t wate rprio rt o sampl e analysi s b yETS-8-044.1
. 

### 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 sample , sampl e duplicate , an d field matri x spike
. 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 yequipment/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 of sampl e preparatio 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 a t th e tim e o

f sampl e preparatio n wil l b e use d t o determin e th e metho d detectio n limit
. Fo rthos e samplin g location s wher e th e fiel d matri xspik

e leve l wa s not appropriate , du e t o highe ro rlowe rtha n expecte d analyt e concentrations , a laborator ymatri xspike ma

yb e prepare d an d include d i n th e fina l report . 7 Emai l Correspondenc e Attachmen t A : Samplin g Bottl e Request

Pag e 6 o f 7 Pag e 3 3 o f 7 0GLP10-01-01; Interim Report 24 Analysis of PFOAin Groundwater Decatur. AL-

December

2011 Analytical

Protocol:

GLPiO-01-01 Amendment

24 Attachmen t A

"4 ^ 

### Bottle reques

t for 4t hquarte r 201 1 FSI A wel l samplin

g Young , Charles 1'. '7 lo:stwoli(@mnim.co

m 11/29/201 1 03:1 0 P

M Cc:"Frinak, Timoth

y R." , "Smith , Martin " Froin : "Young , Charles T. " <Charlcs.Young@WestonSolutions.com > Sue : Ti m Frina k

an d Marti n Smit h are settin g u p fo rgroundwate rsamplin g commencin g next wee k at th e followin g Forme rSludg e Incorporatio n Are a monitorin g wells :

130 R 133 L 136 S 140 R 130 S 134 R 136 L 141 R 130 L 134 S 137 R 142 R 131 R 134 L 137 S 143 R 131 S 135 R 137 L 144 R 131 L 135 S 138 R CW26 C 133 R 135 L 138 S CW26 L 133 S 136 R 138 L Ca n yo u prepare a bottl e se t fo rshipmen t t o Marti n Smith' s attentio n a t Decatu rwit h arriva l b yTuesday , Decembe r6 , 2011 ? A s wit h eariie rrounds , analysi s wil l b e performe d unde rGLPIO-01-0 1 an d GLPIO 01-02
. Du e t o th e relativel ylowG W level s a t th e site , som e o f th e abov e well s ma yb e dr yan d therefor e wil l no t b e sampled
. Marti n wil l retur n an yunuse d bottl e set s shoul d som e o f th e location s hav e insufficien t wate r fo rsampling
. Thanks , Charii e Charle s T . Youn g Technica l Directo r Westo n Solutions , Inc . 140 0 Westo n Way (5-2 ) Wes t Chester , P

A 1938 0 (610 ) 701-378 7 Fax (610 ) 701-340 1 

### CONFIDENTIALITY : Thi s email an dattachment

s ma y contai n infomiatio nwhic hi s confidentia

l an dproprietary . Disclosur

e o r us e o f an y suc hconfidentia

l o r proprietar

y inlbrmationwithout

th e writtenpermissio

n o f Westo n Solutions , Inc . i s strictly prohibited . I f yo u receive dthi s emai

l i nerror, pleas

e notif y th e sende r b y retur n e-mai l an ddelet e thi s emai

l fro m you r system. 'Fhim

k you .

Pag e 7 o f 7 Pag e 3 4 o f 7 0GLPIO-01-01 ; Interi m Repor t 2 4 Analysi s o f PFO Ai n Groundwate r Decatur , A L - Decembe r201 1


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

Pag e 3 5 o f 7 0GLPIO-01-01 ; Interi m Repor t 2 4 Analysi s o f PFO Ai n Groundwate r Decatur , A L - Decembe r201 1 workstation : ETSBUSTE R Batc h Name : blll230b.da b b111230b.rd b (PFOA) : "Quadratic " Regressio n (" 1 / x " weighting) : y= -5.83e+00 3 x'' 2 + 1.15e+00 6 x+ 2.92e+00 4 ( r= 0.9982 ) 6.5e7 - 6.0e7 5.5e 7 5.0e7 4.5e7 4.0e 7 I3.5e7 

### 8 S 3.0e7 < 2.5e7 2.0e7 1.5e 7 1.0e 7 5.0e 6

1 0 1 5 2 5 3 0 3 5 4 0 45 5 0 5 5 Concentration , ng/m L 6 0 6 5 7 0 7 5 8 0 8 5 9 0 9 5 *Dat a worke d up b yKJ U Printin g Time : 10:25:4 7 A M Printin g Date : Wednesday , Januar y04 , 201 2 Pag e 1 o f 1
Pag e 3 6 o f 7 0GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFOAi n Groundwate r Decatur , A L - Decembe r201 1

Buste r J293020 3 Batc h Name : blll230b.da b



# I SarTvloNamo''b111230b029 " Sampl e ID'TCS-11122M - F»B : T)111230b.wif r Pea k Naine
. TFOA " Massfes } -413.0/369. 0 amu,413.0/219. 0 amu.413.Q'169. 0 am u Comment
. "O-Sppb LCS " Annotation- " Sampl e Index ^ 2 9 

# I Sampt e Name : •b111230b032 - Sampte ID:'LCS-111221-7 " Fite ' •b111230b.¥rt r Pea k Name
. 'PFOA " Masa(«s) : "413.0/369. 0 amu.413.0/21 9 Oamu,413.0/169. 0 am u Commen L "Spp b LCS " Annotatk m " Sample Index: 32 Sampl e Type
R T Window : Expecte d BT : Us e Relativ e E O.SO A 12/31/2 ( 1:22:2 4

Hanua l [ . 14. 9 60949 8 C I Calculate d Cone ; 5.3 5 ng/ra L Acq . Date : 12/31/201 1 1.3e6
- Acq . Tioe : 2:25:4 0 A H Hodified: ies ^.2B6• R T Hindow : 30. 0 se c Expecte d BT : IS. O oi n 1.1»6
- os e Relativ e BT : , Int . Type : Hanua l i.0e6
- RetenCio n Time : 14. 9 mi n Area : 603849 0 count s 9.5e5
- En d Time ; 15. 1 mi n S.5eS
8.0e 5 7.5e5 § • 7.0e5
- #6.5«S ' I6.0e 5 5.5e5 5.0e5
- 4.5e5 ' 4.De5 ' 3.5e 5 3.0e 5 2.585
- 2.0e5
- 1.5e 5 I.OeS
5.0e4
- 15. 2 15. 4 14. 6 14. 8 15. 0 Dat a printe d b yST W Printin g Time : 3:08:5 3 P M Printin g Date : Wednesday , Januar y25 , Pag e 1 o f 9
Pag e 3 7 o f 7 0GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFOAi n Groundwate r Decatur , A L - Decembe r201 1

Buste r J293020 3 Batc h Name : blll230b.da b

Modified : R T Window : Expecte dRT : 

# I SampteNartia''b111230b036 " Sampte ID , •LCS-111221.10 - F Poa k Nam* ' "PFOA " Mass(es ) "413.0/369. 0 arT»j,413.0/219. 0 ar Commeni - "30pp b LCS " Annotation
. ~ Sampl e Index : 3 5 Sampl e Type ; Q C 4J)ee
3.ee6 ' 3.6rt
3.4e6
- 3.2ae < 3.0e6
- 2.8e6
- 2.6B6
- 2.4e 6 2.2ee 2.0e 6

8.0e5 - 6.0aS 4,0e5 < 2.0e5 - I SampteNam 9 "b111230bO42 - Sampl o ID:•GLPlO-01-01-24-099 " File'•b111230bwi r :ampl aType ; :alculate dCo i
Hodified : R T Window : 2.1e 4 2.0e 4

SOOO. C sooo c 7000. C 600DC 50DD. C 4000. C 300 0 C 2000.0 - 1000. 0

I Sampte Name''b111230bO43 ' Pea k Name , "PFOA " Mass(es) - "413.0/369. 0 a i • Commeni : •DAL-GW-133L-RB- " ArwKrtatwn
. " Sampl e Index : 4 3 Sanpl e Type
- Unknow n Concentration : M/ A Calculate dCone : < 0

Us e Relatl i Int
. Typo : l a ID : -GLP1&/)1-O1-24-100 ' Fde ' t l 11230b.wi r

2.1e4 2.0e 4 1.9e 4 13e4 < 1.7e 4

8000 0 7000. 0 6000 0 5000. 0 4000. 0 3000. 0 2000. 0 1000, 0 0. 0 

# I Sampto Name ' "b111230bO46 " Sampte ID : 'GLP10-01-01-24-096 ' Fite ' •b111230b.wi r Paa k Name ; -pFOA " Mass{es) : '413.0/369. 0 amu,4130/219. 0 amu,413.0/169. 0 amu ' Commen L "DAL-GW-TRIP01-MS- " Afinotatjon. " Sartipl aIndex : < 6
3.806
- 3.6* 6 3.4ee 3.2e 6 3.0e 6 2.8ee 2.6ee 2.4ee 2.2e 6 2.0e 6 Height : Stai t Tiit K En dTine : 1806759 3 < 3.9Se*a0 6 14. 7 15. 1

B.0e5
- e.0e5
- 4.0e5
-

Dat a printe d b yST W Printin g Time : 3:08:5 3 P M Printin g Date : Wednesday , Januar y25 , Pag e 2 o f 9
Pag e 3 8 o f 7 0GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFOAi n Groundwate r Decatur , A L - Decembe r201 1

Buste r J293020 3 Batc h Name : blll230b.da b

• Sampte Name-'b111230bO49 " Sampte ID''GLP10-01-01-24-001 ' Fie'*b111230b.wi r I Pea k Name'-PFOA ' Mass(es ) '413.0/369. 0 amu,413.0/219. 0 amu,413.0/169. 0 amu " I Commen r"DAL-GW-iaOR-O- " Annotation-" ' Sampl e Index ; 4 9 Sampl e Type ; Unknow n Concentration : H/ A Calculate d Cone : 790 . ng/n L Acq . Date ; 12/31/201 1 Acq . Time : e;24;2 5 A M 1 [ SampieName.'b111230b056 ' Sampte I D "GLPI0^01-01-24-004 " Fito:'bin230t),»tf r Sanipl B Typo
Calculate dC

c Acq . Date : Hodified : R T Hindow ; iu,413.0/219. 0 amu,413.0/169. 0 a i

2.BeB
2.ee 6 24e6
- 2.2e6
- 2.0e6
-

a 1 i 1.<e6 -

B.0e5
- 6.0e 5 4.0e 5 2.De5
-

I Sampte Name'"bill230bO59 ' Sampte ID : •GLP1tW11-01-24-O0 rFite : "blllZSOb.wi r Pea k Name : TFOA ' Mass{es) : "413.0/369. 0 ar • Commen i "DAL-GW-130L-0- " Annotation
. " Sampl e Index ; 5 9

Modified : R T Hindow : Expecte dRT ; 1,413.0/219. 0 amu,413.0/169. 0 amu " I Sampte Name : *b1112306062 " Sampte ID:'GLP10-01-01-24-010 ' Fite'•bni230b.wrt r

9.5« 5 9.0e5

7.5e5 7.0e5 e.5e5 6.0e5 5.5e5 5.0e5

3.5e5 3.0o5 2£e 5 2.0e5 Hod l R T W latlv e RT : iu,413.0/219. 0 amu.413.0/169.0a i

3.0e 6 2.ea e 2.ee e 2.4e 6 2.2ee 2.0e 6

8.0e5 6.0e5 >

Dat a printe d b yST W Printin g Time : 3:08:5 4 P M Printin g Date : Wednesday , Januar y25 , Pag e 3 o f 9
Pag e 3 9 o f 7 0GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFO Ai n Groundwate r Decatur , A L - Decembe r201 1

* * Buste r J293020 3 Batc h Name : blll230b.da b

• Sampte Name
. •ti111230t)069 ' Sampte ID : ' < I Pea k Name , 'PFOA " Mass(e5) - -413.D/369. ( 1 Commeni , "DAL-^SW-13ISO- " Annotation' " Sample Type; Unk i H / A 5.405 5.2a 5 5.0e5 43a 5 4.6e 5 4/4e 5 4Je 5 4.0e 5 3.8« 5 3.6e5 3.4* 5 3.2e5 3.0e5 2.3e 5 2.6e 5 2>te 5 2.2o 5 2.0e 5

8.0e 4 6.0e 4 I SampteName
. •b111230b072 ' Sampt e ID,'GLP10-01-01-24.016 " Fite'*b111230b,wif r

. . . iu,413.0/219.0Bmu,413,0/169. 0

Acq
. Tlrae :

I t . Type : •tentio n T : jlgtic : 1.5o6
- 1.4e6

9.0e5
- 8.0e5
- 7.0o 5 6.0e 5 5.0e 5 4.005
- 3.0e 5 2.0e 5 I.Oe S

I Sampt e Name
. 'b111230I:>082 ' Sampte ID : "GLP10-01-01-24-022 " Fite ' •b111230b.wi r 

# I Sampte Name:'bin230b075 " Sampte ID'' ( Poa k Name : "PFOA " Mass(os ) "413.0/359. 0 Comn>ent
. "DAL-GW-133R-0- * Annotation ' ~ Sampl e Index ; 7 5

1.4e e iJe 6 1.2e 6 1.1e 6 1.0e 6

5.0e5
- tJ0« 5 3,0eS
2Xle 5 Pea k Name
. 'PFOA ' Mass(os) : '413.0/369.0 1 • Commen t "DAL-GW-ISaS-O- * Annolation: " Sampl e Type ; Unknow n

Hodified : R T Window : Expecte d RT ;

En d Tine : 4.0e 6 3.ee 6 3.6e 6 3.4e e 3.2e 6 3.0e 6 2.ee e 2.6e 6 2.4e 6 2.2e 6 2.0e 6

8.0e5
- 6.0e5
- 4.DeS
2.0e 5 14. 6 U 3 15. 0 15 ^ 15. 4 15. 6 15. 8 16. i Dat a printe d b yST W Printin g Time : 3:08:5 4 P M Printin g Date : Wednesday , Januar y25 , 201 2 Pag e 4 o f 9
Pag e 4 0 o f 7 0GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFO Ai n Groundwate r Decatur , A L - Decembe r201 1

** * Buste r J293020 3 Batc hName : blll230b.da b

Sampt e ID : 'GLP10-01-01-24-025 ' Fie . "b111230b.*i r

0/219. 0 amu,413.0/169. 0 amu R T Kindow ;

Star t T : EndTimt 4.ea6
- 4.dee
4.2e6
- 4,0e6 ' 3.ee6
- 3.6e6
- 3 4ee
3.2e6
- 3,0e6 > 2.ee6
- 2.6e 6 2.4e S 2.2e6
- 2.0* 6 1.ee6

1.2a 6 1.0e6 > 8.0e5
- B.Oe S 4.0aS
2.0eS > 

# I Sampt e Name ' •b111230b088 ' Sampt e ID
- "GLP I 0-01-01-24-028 " Fito . "b111230b. w Pea k Name : "PFOA ' Ma*s(es)"413Xin59.0amu.4i3.0/219.0amu,413.0/169.0amii ' Comment : 'DAL-GW-WR-O- ' Annotation
- - Sampl e Index
- 8 8 2060 . n

q 12/31/201 1 10:06:5 3 P

H

Height : Star t Time . En dTime : 3.ee 6 3.6e 6 3.4e6
- 3.2e6
- 3.0e6 ' 2.6e6
- 2.6e6
- 2.4e6
- 2.2e 6 2.006
- 1.8e6 '

1.0o6
- 8.0e 5 6.0e5
- 4.005
- 2.085
-
I SampteNamo:"b111230b095 " Sampte ID : •CLP1O-01-0l-24-O3 rFto'"b111230b.wrf r I Sampte Name'"b111230bO98 " Sampte I D 'GLP I 0-01-01-24-034 - Fite:*b111230b.wii r

concentration : ti/ A jg^ . Calculate dCone : 12. 6 ng/ro L Acq . Date ; 1/1/201 2 2.5e6
- 12;3.:39A K Modified : Ye a2.3* 6 R T Hindow ; 30. 0 se c Expecte dRT : IS. O mi n 2.2e6
- °" •" 2.M Int . Type ; Hanua l 20o6
- Retentio n Time : 14. 9 mi n Area : 1363052 8 count s 1.9e6
- Height ; 2.63e*00 6 cp s .. . Star t Time : 14. 5 mi n End Time: Ib.l min , 7^. Height : Star t 1 En dTi n 518 . 1/1/201 2 1:37:5 9 J

.17e-t00 6 cp s 1.15e 6 1.10e 6 1.05e 6 1.00e 6 9.50e 5 9.00e5
- 8.50e 5 8.00e 5 T.50e5
- 7.00e 5
« 6.50e 5 S ^ e.OOe

S I5.50e 5 5.00e 5 4.50e 5 4.00e 5 3.50o 5 3.00« 5 2.50e 5 2.00e 5 1.50B 5 1.00e 5 5.00e 4 0.0 0 Dat a printe d b yST W Printin g Time : 3:08:5 4 P M Printin g Date : Wednesday , Januar y25 , 201 2 Pag e 5 o f 9
Pag e 4 1 o f 7 0GLP10-01-01 ; Interi m Repor t 2 4 Analysi s of PFO Ai n Groundwate r Decatur , A L - Decembe r201 1

Buste r J293020 3 Batc h Name : blll230b.da b 

# r SampteName , •b111230t>101 ' Sampte ID:'GLP10-01-01-24-037 " Fie
. "b111230b.wif r Pea k Name : 'PFOA ' Mass{es) : '413.0/369. 0 amu.413.0/219. 0 amu,413.0/169. 0 amu ' Commeni
. •DAL-GW-135R-0- ' Annotatio n ~ 5.2e6 S0e6 43e6 4.6e6 4.4e6 4.2e6 4j0e6 3.6e 6 ZAe t 3.2e 6 3.0e 6 2.e« 6 2.6e 6 2.4e 6 2.2e6 2.O0 6 1.60 6 1.ee6 1.4e6 1.206 1.0e6 e.0e 5 6.0e 5 4.0e 5 2.0« 5 

# I Sampte Name , -ti111230b108 ' Sampt e ID:'GLPKKI1-O1-24-O40 ' Fite "b111230b.wir r Pea k Name : 'PFOA ' Mass{es ) '413.0/369, 0 amu,413.0/219. 0 amu.413,0/169. 0 Comman L 'DAL-GW-135S^>- " /^nrwtalion
. -

Us e Relati ^ Int . Type :

I SampteName''b111230b114 ' Sampte ID ; •GLP1CMJ1-01-24-O49 ' nte:'b111230b.wtf r I SamptoName''b111230b111 ' Sampte I D 'GL P 10-01-01-24-043 " Fle-"b111230b. w Pea k Name- -FTOA " Mass(os) - "413.0/369. 0 a r • Comment : "DAL-GW-135L-ft- " Arinotatki n " Sampl e Index : 11 1 Sampl e Type ; Unknow n Concentration : K/ A Calculate d Cone : 176 . ng/m L Acq . Date : 1/1/201 2

Expecte d R l Us e Relati ^ Int . Type : Height : Star t Time : En d Time : j,413.0/219. 0 amu.413.0' ! 69. 0 a i

3.2e6 3.0e e 2£e 6 2.60 6 2.4e 6 2.20 6 2.0e 6

e.0o 5 e.0e 5 4.0e S Pea k Name'"PFOA " Mass(os ) "413.0/369. 0 • Commen L "DAL-GW-136S-(V " Annolation, " Sampl e Index ' 11 4

Hodified : R T Window : Expecte d RT : Us e Relativ e
Height : Star t T : En d Tin .

Dat a printe d b yST W Printin g Time : 3:08:5 4 P M Printin g Date : Wednesday , Januar y25 , Pag e 6 o f 9
Pag e 4 2 o f 7 0GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFOAi n Groundwate r Decatur , A L - Decembe r201 1
Buste r J293020 3 Batc hName : blll230b.da b

I SampteName
. t)11i230b12 rSampt e ID:'GLP10-01-01-24-052 " Flo,•b11l230b. w I Pea k Name : "PFOA " Mass(es ) '413.0/369. 0 amu,413.0/219. 0 amu,413.0/169. 0 amu ' I Comment.-DAL-GW-ISSL-O- ' Annotation: - Sampl e Type : Unknow n Calculate dCone : 64. 9

le
- U. 9 oii r 727557 2 count s l,50e*00 6 op s 14. 5 tni r

15. 2 15. 4 15. 6 I SampteNamo:-b111230bl24 " Sampte ID.'GLP10-01-01-24-05e ' Fite:T>ni230b.wi r PeakName"PFOA ' Massfes ) -413.0/369.0a i • Comman L 'DAL-CW-137S-0- " Annotation , ' Sampl e Index ; 12 4 Sampl e Type : Unknow n Calculate dCone ; 0.37 6 ng/ra L Acq . Date : 1/1/201 2 Acq , Tlrae : 10:47:1 2 A H Modified : le s 11,413.0/219. 0 emu.413.0/169. 0 amu *



# I Sampt o Name-"b111230b127 " Sampt e ID.'GLP10-01-01-24-08 rFie'"b11l230b.wif r Pea k Name : "PFOA " Mass(es) ' "413.0/369. 0 amu,413.0/219. 0 amu.413.0/169. 0 amu " Commeni
. "DAL-GW-nZL-O- " Annotation : ~ Sampl e Index : 12 7 Sampl e Typ e Unknown Acq
. Date - 0.37 1 1/1/20 1 ng/m L 

# I SampleNam e "b111230b134 " Sampte ID : "GLP10-O1-O1-24^J64 " Fite'"blimOb. w Pea k Name : 'PFOA ' Mass(os)
. "413.0/369. 0 amu,413.0/219. 0 amu,413.0/169. 0 amu " Commeni : 'D/y.-GW- l 38R-I> ' Annotation. " Sampl e Index , 13 4 Sampl e Typo ; Unknow n Calculate d Cone : 252 . ng/mL Acq . Date : 1/1/201 2

Dat a printe d b yST W Printin g Time : 3:08:5 4 P M Printin g Date : Wednesday , Januar y25 , 201 2 Pag e 7 o f 9
Pag e 4 3 o f 7 0GLPIO-01-01 : Interi m Repor t 2 4 Analysi s o f PFOAi n Groundwate r Decatur , A L - Decembe r201 1

Buste r J293020 3 Batc h Name : blll230b.da b 

# I SampteNam e •b111230b13 rSampte ID.'GLP1CM)1-01-24-06 rFlo'"b111230b.wlf r Pea k Name : "PFOA " M3Ss(os) '413.0^69. 0 amu.413.0^219. 0 amu,413.0/169. 0 emu " Commen i •DAL-GW.135S-0- " AnnoUtion,' " 2,4e6 - 2.3o 6 2.2a6 - 2. 1 e6 - 2.0e6 - 1,9e6 - 1,ee 6 1.7e 6 1.6e6 - 15e6 - 1.4e6 - 1.3e 6 1.2e 6 1.1e6 -
9.0a5 B.0e5 - 7.0e5 6.0e5 - 5.0e5 4 JU S 3.0e5 2.0e5 - 

# I SampteNamB:'b111230b140 ' Samptel D t Pea k Name : TFOA " M3ss{es) : "413.0/369. 0 Commen t "DAL-GW-138L-0- * Annotatio n "

0.50 5 1/1/201 2 4 24:4 0 P

h

Int . Type ; Retentio n ] Height : 1.20e5 - I.ISeS I.IOeS 1.05o5 - 1.00e 5 9.50e4 - 9.00o4 - 8.50e4 - 8.00e4 - 7.5004 -

, 7.00e4 - ^ 6.5004 - I 6.00o4 -
= 5.50o4 - 5.00e4 - 4.50e4 - 4.00e4 - 3.50e4 - 3.00o4 - 2.50e 4 2.0De4 - 1.50o4 - 1.00e4 - 5000.00 - 0.00 - 

# I SampteName'"b111230[)14 rSamptel D 'GLPIOOI-01-24-073 " Fllo:"b111230b.wi r Pea k Name : 'PFOA - Mass(es ) -413.0/369.03010.413.0/219. 0 amu,413.0/169. 0 amu " Comment
. DAL-GW-140R-0- " Annotation - ~ Sampl e Index : 14 7 2.3e6 - 2.2e6 2.186 - Modi f R T Wl i Us e Relativ e RT ; N o 1.aoti1.ee S 1.T06 - 1 6e 6 1.5e6- 1.4e6 - 

# I SampteNam e "b111230b150 ' SamptelD:" ! Pea k Name ' 'PFOA ' Mass(os ) "413.0/369. 0 Commen L "D/y.-GW-UIR-O- ' Annotation." " Sampl e Index - 15 0

2.35e+00 6 ep s

9.0e5 6.0e5 7.0o5 - 6.0e5 5.005 - 4.0e5 - 3.085 - 2.0e5 1.0e5 -
Dat a printe d b yST W Printin g Time : 3:08:5 4 P M Printin g Date : Wednesday , Januar y25 , Pag e 8 o f 9
Pag e 4 4 o f 7 0GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFO Ai n Groundwate r Decatur , A L - Decembe r201 1

** * Buste r J293020 3 Batc h Name : blll230b.da b 

# I Sampte Name , 'b l 11230b153 ' Sampte ID Pea k Name , 'PFOA ' Mass(es) - '413.0/369. 0 Comment , 'DAL-.<3W-142R-0- " Annotation ' - Sampl e Index ; 15 3 Sampl e Type : Unknow n Concentration : N/ A Calculate dCone : 51. 8 ng/m L Acq . Date ; 1/1/201 2 Modified : R T Window : Expecte dRT : 1.15e6
- I.IOee
1.05e6
- I.00e6
- 9.50e5
- 9.00e5
- 8.50o5
- 8.00e 5 7.50e5
- 7.00o5
- 6.50e 5 6.00e5
- 5.50o 5 5.00e5
- 4.50e 5 4.00e5
- 3.50e5
- 3.00e5
- 2.50e5
- 2.00a5
- 1.50e 5 1.00e5
- 5.00*4
- 0.0 0 Manua l ! • 14. 9 ni n 149242 3 count s 3.02e-'O0 5 cp s 

## ( Sampl e Name
. "b111230b160 " Sampt e ID , "GLP10-01-01-24-082 " Fite - "b111230 b w Pea k Name : "PFOA " Mass(e5j "413.0/369. 0 amii,413,0/219, 0 omu.413.0/169. 0 amu " Commen L •DAL-GW-143R-&. " Annotation , Sampl e Index : 16 0 Sampl e Type : Unknow n Concentration ; H/ A30* 5 Calculate d Cone , 12. 8 n<[/n L Acq , Date : 1/1/201 2 Acq , Tine ; 11:26:5 2 P M 2,8e 5 Modified ; le a R T Window ; 30. 0 se c 2 6e 5 Expecte dRT : 15. 0 ni n Us e Relativ e RT : tl o 2.4e 5 2.2e 5 Belqlit : Star t Time : 14. 7 ni n En dTine : 15. 1 i=i n2.0e 5

1.4o5
- 1.2e5
- 1.0e5
- e.0»4
- 6.0* 4 • 4.0e4
- 2.0e4 ' 

# I Sampl e Name : 'b l 11230bl63 ' Sampte ID;" ' Pea k Name : "PFOA " Massfes ) "413.0/369. 0 Comment- "DAL-GW-14 4 R-0- ' Annotation: "

Height : Star t Ti l EndTim e 693752 5 eou r 1.3e8 ' 1.28 6

9.5e 5 9.0e 5 B.5e5 B.0e5 7.5e5 7.0e5 6.Se5 6.08 5 5.5e5 5.0e5
- 4.5e 5 4.0e5
- 3.5e 5 3.0e5 2.5e 5 2.0e 5 13e 5

14. 6 14. 6 15. 0 15. 2 15. 4 15. 6 15. 8 16. 0 Dat a printe d b yST W Printin g Time : 3:08:5 5 P M Printin g Date : Wednesday , Januar y25 , 201 2 Pag e 9 o f 9
Pag e 4 5 o f 7 0GLPIO-01-01 ; Interi m Repor t 2 4 Analysi s o f PFOAi n Groundwate r Decatur , A L - Decembe r201 1


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

Pag e 4 6 o f 7 0GLPIO-01-01 ; Interi m Repor t 2 4 Analysi s o f PFOAi n Groundwate r Decatur , A L - Decembe r201 1



# 3 M Eiwironmenta l Laboratory

Method Method of Analysis

for the Determination

of Perfluorinated

Compounds

in Water by LC/MS/MS;

Direct Injection

Analysis Method Number:

ETS-8-044.1 Adoption

Date: 4/12/07 Effectiv e Date : ///f// / Approve d By ;

Willia m K
. Reagen , Technica l Director , Environnnenta l Laborator yDat e

ETS-8-044. 1 Pag e 1 o f 2 2 Method o f Analysi s fo rth e Determinatio n o f Perfluorinate d Compound s i n Wate rb yLC/MS/MS ; Direc

t Injectio n Analysi s Pag e 4 7 o f 7 0GLPIO-01-01 ; Interi m Repor t 2 4 Analysi s o f PFO Ai n Groundwate r Decatur , A L - Decembe r201 1


### 1 Scop e an d Applicatio n Thi s metho d describe s th e direc t injectio n analysi s of perfluorinate d compound s (PFCs ) fro m wate rmatrice s usin g high-perfomnanc e liqui d chromatograph ytande m mas s spectrometr y (HPLC/MS/MS)
. Th e metho d i s generall yapplicabl e bu t no t limite d t o th e measuremen t o f perfluoroalky l sulfonamide s an d perfluorinate d alky I acid s (PFAAs ) suc h a s perfluorosulfoni c acid s (PFSAs ) an d perfluorocarboxyli cacid s (PFCAs ) (Tabl e 1) , Wate rsample s containin g heav yparticulat e ma

yrequir e preparatio n b

ya n alternat e metho d suc h a s ETS-8-15 4 "Detenninatio 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 Perfonnance Liqui d Chromatography/Mas s Spectrometry"
. Th e metho d i s applicabl e t o bot h externa l standar d an d interna l standar

d calibratio n V Tabl e 1 . Representativ e Targe t Analyte s Acronym Analyte Chemical Abstract Services Registry Number

(CASRN) PFB A(0 4 Acid ) Perfluorobutanoi caci d 375-22- 4 PFPeA(0 5 Acid ) Perfluoropentanoi cad d 2706-90- 3 PFHx A(0 6 Acid ) Perfluorotiexanoi caci d 307-24- 4 PFHp A(0 7 Acid ) Perfluorotieptanoi caci d 375-85- 9 PFO A(0 8 Acid ) Perfluorooctanoi caci d 335-67- 1 PFN A(0 9 Acid ) Perfluorononanoi caci d 375-95- 1 PFD A(CI O Acid ) Perfluorodecanoi caci d 335-76- 2 PFUn A(Oi l Acid ) Perfluoroundecanoi caci d 2058-94- 8 PFDo A(01 2 Acid ) Perfluorododecanoi cad d 307-55- 1 PFTrD A(01 3 Acid ) Perfluorotridecanoi caci d 72629-94- 8 PFB S (0 4 Sulfonate ) Perfluorobutanesulfoni caci d 375-73- 5 PFH S (0 6 Sulfonate ) Perfluorofiexanesulfoni caci d 355-46- 4 PFO S (0 8 Sulfonate ) Perfluorooctanesulfoni caci d 1763-23- 1 FBS A(0 4 Sulfonamid e Perfluorobutanesulfonamid e 30334-69- 1 FOS A(0 8 Sulfonamide ) Pefluorooctanesulfonamid e 754-91- 6 Th e Minimu m Reportin g Leve l (MRL ) i s th e Limi t o

f Quantitatio n (LOQ ) that meets Data Qualit yObjective s (DQOs ) tha

t are develope d base d o n th e intende d us e of thi s method
. Metho d Flexibilit

y- Thi s i s a perfonnance-base d metho d an d ma yb e generall yapplie d t o th e detenninatio n of perfluorinate d compound s i n wate rmatrice s whe n analysi s batc h qualit y contro l (QC ) criteri a ar

e met^ . Eac h set o

f sample s are prepare d i n a n analysi s batc h wit h calibratio n standards , LCSs , blanks , an d continuin g calibratio n chec k standard s analyze d o n th e sam e instrumen t durin g a tim e perio d that begin s an d end s wit h th e analysi s of th e appropriat e continuin g calibratio n chec k standards
. Th e laborator yi s pemnitted t o modif

yth e L C column , mobil e phas e composition , L C conditions , an d MS/M S conditions
. Metho d modification s shoul d b e considere d t o improve metho d perfonnanc e o rt o meet dat a qualit y objective s fo rth e study
. I n al l case s where metho d modification s are implemented , th e batc h

' Th e metho di s supporte

db y validation wit

hintema l standar dcalibration fo r

C4-C1 3 PFCAs , C4 , C6 , an dC 8 PFSAs , an dC8 perfluoroalkan

e sulfonamid

e i nlaborator

y control sample

s unde r 3 M metho

dvalidation E l 1-0667 . ^ Guidanc e fo r establishin

g metho dQ C Criteri abase

do na. ) FDA Ma

y 2001 , "Guidanc

e fo r Industry , Bioanalytica

l MethodValidation" , b. ) EP A Method537 , an

dc. ) Europea

n Commission : Guidanc

e fo r Generatin

g an dReportin

g Method s o f Analysi s i nSuppor

t o f Pre-registratio

n Dat aRequirement

s fo r Arme x I I(Par t A , sectio n 4 ) an dAnne x II I (Par t A,section 5 ) o f

Directiv e 91/414 , SANCO/3029/99 rev . 4 (11/07/00) . ETS-8-044. 1 Pag e 2 of 2 2 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 8 o f 7 0GLPIO-01-01 ; Interi m Repor t 2 4 Analysi s o f PFO Ai n Groundwate r Decatur , A L - Decembe r201 1 analytica l QC s (sectio n 9 ) mus t b e complete d an d pas s Q C acceptance criteri a (sectio n 13) i f th e dat a fro m th e analytica l batc h are t o b e reported
. 2 Metho d Summar y Wate rsample s are analyze d as nea t aqueou s sampl e o ra s solven t dilute d aqueou s sample s b ydirec t injectio n usin g LC/MS/MS
. Sample s containin g heav yparticulat 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 centrifuge d o rfiltere d prio rt o removin g a sampl e aliquot o rdilutin g wit h solvent
. Th e wate r sampl e i s mixe d wel l prio rt o removin g a n aliquot o rdiluting , i f necessary , wit h AST M Typ e I water , HPL

C water , othe rsuitabl e water , o rsolven t (methanol)
. Quantitatio n i s b

ystabl e isotop e interna l standar d calibratio n i n laborator

yreagen t water . Al l perfluorinate d compound s (PFCs ) targe t analyt e concentration s of perfluorosulfoni cacid s (PFSAs ) an d perfluorocariDoxyli cacid s (PFCAs ) are reporte d as anion s an d correcte d fo r thei rsal t o rfre e aci d fomns
. Altematively , quantitatio n ma yb e perfonne d b

yextema l standar d calibration
. Thi s i s a perfomnance-base d method
. Metho d uncertaint yfo reac h target analyt e i s detennine d fo reac h analytica l batc h 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 detennine 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
. Calibratio n standard s fo rPFUnA , PFDoA , PFTrDA , an d FOS Ahav e bee n foun d t o b e unstabl e fo rmor

e tha n 2 days i n 100 % water . Sample s requirin g analysi s fo rthes e compound s b

ythi s metho d shoul d b e dilute d 1: 1 wit h methano l an d analyze d against a calibratio n curve prepare d i n 1: 1 syntheti cgroundwaterMeOH
. 3 Definition s 3. 1 Analysi s Batc h Aset o f stud ysample s that are prepare d wit h calibratio n standards , laborator ycontro l samples , an d procedura l blanks , an d analyze d o n th e sam e instrumen t durin g a tim e perio d that begin s an d end s wit h th e analysi s o f th e appropriat e continuin g calibratio n chec k standards
. 3. 2 Analytica l Sampl e Aportio n o

f a laborator

ysampl e prepare d fo ranalysis
. 3. 3 Calibratio n Standar d Asolutio n prepare d b

yspikin g a know n volum e of th e Workin g Standar d (WS ) into a predetermine d amoun t of AST M Typ e I , HPLC grad e water , o rothe rsuitabl e wate r(i.e
. matri xwater) , an d analyze d accordin g t o thi s method
. Calibratio n standard s ar e use d t o calibrat e th e instmmen t respons e wit h respec t t o analyt e concentration
. 3. 4 Laborator y Duplicat e Sampl e (LDS , o r La b Dup ) Alaborator

yduplicat e sampl e i s a separat e aliquot o f 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 o f LDS s compare d t o tha t of th e firs t aliquot give a measur e o f th e precisio n associate d wit h laborator y procedures , bu t no

t wit h sampl e collection , preservation , o rstorag e procedures
.
ETS-8-044. 1 Pag e 3 o f 2 2 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 9 o f 7 0GLPIO-01-01 ; Interi m Repor t 2 4 Analysi s o f PFO Ai n Groundwate r Decatur , A L - Decembe r201 1
3. 5 Fiel d Blan k

(FB)/Tri p Blan k

(TB ) AST M Typ e I , HPL

C grad e water , o rothe rsuitabl e water , place d i n a sampl e containe ri n th e laborator yan d treate d as 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 of th e T B i s t o detemnin e i f test substance s o rothe rinterference s are presen t i n th e fiel d environment
. Thi s sampl e i s als o refen-ed t o a s a Tri p Blank
. 

### 3. 6 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

yprocedures
. Analysi s o f th e FD S compare d t o that of th e firs t sampl e give s a measur e o f th e precisio n associate d wit h sampl e collection , preservatio n an d storage , a s wel l as wit h laborator

yprocedures
. 3. 7 Fiel d Matri x Spik e (FMS ) Asampl e t o whic h know n quantitie s o f th e target analytes , IS s an d SRS s ar e adde d t o th e sampl e bottl e i n th e laborator ybefor 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 r withou 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 i s analyze d t o ascertai n i f an ymatri xeffects , interferences , o rstabilit yissue s ma

ycomplicat e th e interpretatio n of th e sampl e analysis
. 3. 8 Tri p Blan k

Matri x Spik e (TBMS ) 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 o

f th e targe t analytes , IS s an d SRS s are adde d i n th e laborator yprio rt o th e shipmen t o

f th e collectio n bottles
. Th e TBM S i s analyze d exactl ylik e a stud ysampl e t o hel p detennin e i f th e metho d i s i n contro l an d whethe ra los s of analyt e o ranalytica l bias coul d b e attribute d t o sampl e holdin g time , sampl e storag e and/o rshipmen t issues
. Alo wan d hig h TBM S are appropriat e whe n expecte d sampl e concentration s are no t know n o rma

yvary . 

### 3. 9 Interna l Standar d (IS ) Acompoun d adde d t o eac h stud ysample , calibratio n standard , laborator ycontro l samples , an d procedura l blank

s a t a consisten t leve l (typicall yaroun d 1 ng/mL)
. Th e interna l stanclard(s ) ar

e stabl e isotop e labele d version s of th e targe t analytes
. Th e are a coun t rati o o f th e targe t analyt e t o th e interna l standar d i s use d fo rcalibration
. Surrogate IS s are applie d whe n stabl e isotop e IS s of targe t analyte s are unavailable
. Asurrogat e I S i s no t necessaril y a stabl e isotop e labele d versio n o f th e target analyte , bu t i s treate d as a n intema l standar d fo r quantitation
. 3.1 0 Laborator y Contro l Sampl e (LCS ) A n aliquot of contro l matri xt o whic h know n quantitie s o f th e targe t analytes , IS s an d SRS s (whe n applicable ) are adde d i n th e laborator ya t th e tim e whe n sample s are aliquotted
. At leas t thre e level s (two level s fo rSRSs ) i n triplicat e are included , on e generall ya t th e lo wen d o f th e calibratio n curve an d on e nea rth e mi d rang e an d th e uppe ren d of th e curve . Th e LCS s are analyze d exactl ylike a laborator ysampl e t o detemnin e whethe rth e stabilit yof th e standards
. LCS s shoul d b e prepare d eac h da ysample s are aliquoted
. 3.1 1 Laborator y Matri x Spik e (LMS ) Alaborator

ymatri xspike i s a n aliquot o f a sampl e t o whic h know n quantitie s o f target analytes , IS s an d SRS s (whe n applicable ) 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 detemnin e whethe rth e sampl e matri xcontribute s bias t o th e analytica l results
. Th e endogenou s concentration s o f th e analyte s i n th e sampl e matri x mus t b e detennine d i n a separat e aliquot an d th e measure d value s i n th e LM S con-ected fo r thes e concentrations
. LMS s are optiona l fo ranalysi s of aqueou s samples
. ETS-8-044. 1 Pag e 4 of 2 2 Metho d o f 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 5 0 o f 7 0GLPIO-01-01 ; Interi m Repor t 2 4 Analysi s o f PFOAi n Groundwate r Decatur , A L - Decembe r201 1 

### 3.1 2 Laboratory Sampl e Aportio n o raliquot of a sampl e receive d fro m th e fiel d fo rtesting
. 

### 3.1 3 Limi t ofQuantitatio n (LOQ ) Th e lowe rlimi t of quantitatio n (LLOQ ) fo ra n analytica l batc h i s th e lowest concentratio n that ca n b e reliabl yquantitate d withi n th e specifie d limits of precisio n an d accuracy . Th e LLOQ 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 acceptance criteria
. Th e LLO Q fo reac h targe t analyt e i s establishe d fo reac h analysi s batc h a s th e lowest calibratio n standar d wit h are a counts a

t least twic e that of th e averag e are a counts o f th e procedura l blanks
. Th e uppe rlimi t of quantitatio n (ULOQ ) fo ra n analytica l batc h i s th e highest concentratio n that ca n b e reliabl yquantitate d withi n th e specifie d limits of precisio n an d accuracy . Th e highest standar d i n th e calibratio n curve that meets metho d acceptance criteri a i s define d as th e ULOQ
. 3.1 4 Method/Procedura l Blan k A n aliquot of contro l matri xtha t 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 are use d wit h othe rlaborator y samples
. Th e metho d blan k i s use d t o determin e i f test substance s o rothe rinterference s are presen t i n th e laborator

yenvironment , th e reagents , o rth e apparatus . 3.1 5 Sampl e Asampl e i s a n aliquot remove d fro m a large rquantit yo f materia l intende d t o represen t th e origina l source material
. 3.1 6 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 7 Surrogat e Interna l Standar d A n I S that i s no

t necessaril ya stabl e isotopicall ylabele d targe t analyte , bu t i s treate d a s a n interna l standar

d fo rquantitation
. Surrogat e IS s are use d whe n isotopicall ylabele d counterparts of th e target analyt e ar e no t commerciall yo rreadil yavailable
. 3.1 8 Surrogat e Recover y Standar d (SRS ) A n isotopicall ylabele d standard , no t use d as a n interna l standard , that i s adde d t o eac h sampl e an d appropriat e QC sampl e a s a mean s t o evaluat e th e metho d perfomnanc e fo ra chemica l clas s of compound s (e.g. , PFSAs , PFCAs)
. 3.1 9 Workin g Standar d (WS ) Asolutio n of 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 Safety Th e acut e an d chroni ctoxicit yo f th e standard s fo rthi s metho d hav e no t bee n precisel y detennined ; 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 exposur e t o chemical s that migh t b e present . ETS-8-044. 1 Pag e 5 of 2 2 Metho d o f 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 5 1 o f 7 0GLPIO-01-01 ; Interi m Repor t 2 4 Analysi s o f PFOAi n Groundwate r Decatur , A L - Decembe r201 1
Th e laborator

yi s responsibl e fo rmaintainin g a saf e wori < environmen t an d a cun-ent awarenes s o

f loca l regulation s regardin g th e handlin g o f th e chemical s use d i n thi s method
. Areference fil e of materia l safet ydata sheets (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 o

f solvents , pressurize d gas an d solven t lines , hig h voltage , an d vacuu m systems . Refe rt o th e appropriat e equipmen t procedur e o roperato rmanua l fo r additiona l infonnatio 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 rcondition s o f analysi s b

yrunnin g metho d blanks
. 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 y of 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 o

f 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 Material s 6. 1 Instrumentatio n Analytica l balance capabl e of readin g t o 0.000 1 g HPLC/MS/M S o rHPLC/M S system , a s describe d i n Sectio n 10
. 

### 6. 2 Supplie s an d Material s Sampl e collectio n bottles—HDP E (e.g. , NalgeneTM ) wide-mout h bottle s wit h screwcap . Note : Do no

t us e fluorinate d o rTeflon® bottle s o rline d caps . Cooler s o rboxe s fo rsampl e shipment
. 15-m L an d 50-m L disposabl e polypropylen e centrifug e tubes
. Clas s Apipette s an d volumetri cflasks , various
. 2 m L HPL

C autovial s 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 . 

### 7 Reagent s an d Standard s Note : Supplier

s an d catalo g number

s are fo rillustrative purpose s only
. Equivalen t perforrnance ma

yb e achieve d usin g chemical s obtaine d fro m othe rsuppliers
. Do no t us e a lesse rgrad e of chemica l tha n thos e listed
. 

### 7. 1 Chemical s Wate r- Milli-Q , HPLC grade , o rothe rsuitabl yappropriat e source s Calciu m Acetat e - A.C.S
. Reagen t Grad e ETS-8-044. 1 Pag e 6 o f 2 2 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 5 2 o f 7 0GLPIO-01-01 ; Interi m Repor t 2 4 Analysi s o f PFOAi n Groundwate r Decatur , A L - Decembe r201 1 Magnesiu m Acetat e - A.C.S
. Reagen t Grad e Methano l - HPLC grad e Ammoniu m Acetat e - A.C.S
. Reagen t Grad e 7. 2 Representativ e Targe t Analytes , ISs , an d SRS s PFBA , Heptafluorobutyri cAcid , (C 4 Perfluorinate d Acid ) PFPeA , Nonafluoropentanoi cAci d (C 5 Perfluorinate d Acid ) PFHxA , Perfluorohexanoi cAci d (C e Perfluorinate d Acid ) PFHpA , Tridecafluoroheptanoi cAcid , (C 7 Perfluorinate d Acid ) PFOA , Ammoniu m perfluorooctanoate , (C s Perfluorinate d Acid ) PFNA , Heptadecafluorononanoi cAcid , (C g Perfluorinate d Acid ) PFDA ; Nonadecafluorodecanoi cAci d (C1 0 Perfluorinate d Acid ) PFUnA , Perfluoroundecanoi cAcid , (C n Perfluorinate d Acid ) PFDoA , Perfluorododecanoi cAcid , (C1 2 Perfluorinate d Acid ) PFTrDA , Perfluorotridecanoi cAcid , (C1 3 Perfluorinate d Acid ) FBSA , Perfluorobutanesulfonamid e FOSA , Perfluorooctanesulfonylamid e PFBS , Potassiu m Perfluorobutanesulfonat e PFHS , Perfluorohexanesulfonat e PFOS , Potassiu m perfluorooctanesulfonat e PFO A[1,2 , 3,4-"C] , "C4-isotopicall ylabele d perfluorooctanoi caci d (SRS ) PFO S [1,2 , 3,4-"C] , "C4-isotopicall ylabele d Perfluorooctanesulfonat e (SRS ) PFUn A[1,2-"C] , "C2-isotopicall ylabele d Perfluoroundecanoi caci d (SRS ) Acusto m mi xof IS s i n a methanoli csolutio n containin g ([1,2,3,4-^^C4]PFBA , [1, 2 - "CJPFHxA , [1,2,3,4,5,6,7,8-"C8]PFOA , [1,2,3,4,5,6, 7 8,9-"C9]PFNA , [1, 2 -^^CJPFDA , [1,2,3,4,5,6,7-"CyjPFUnA , [1, 2 -"CJPFDoA , [1,2,3-^XajPFHS , [1,2,3,4,5,6,7,8-"C8]PFOS , an d [1,2,3,4,5,6,7,8-"C8]PFOS A(Wellinqto n Laboratories , Guelph , ON ) i n combinatio n wit h adde d ([1,2,3,4,5-"C5]PFPeA , ([1,2,3,4-X4]PFHpA , an d [^^OJPFB S ca n b e use d t o prepar e a stoc k I S solution
. Altematively , individua l stabl e isotop e IS s ca n b e use d t o prepare a stoc k I S mixture
. Othe rIS s ca n b e applied
. 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 . Syntheti cGroundwate r(containin g 2 5 pp m C a an d Mg ) - Weig h 0.6 1 g o f Calciu m Acetat e an d 0.92 g of Magnesiu m Acetat e an d dissolve i n 6. 0 L o f reagen t water . Note : Alternative volume s ma yb e prepare d a s lon g a s th e ratio s o f th e solven t t o solut e ratio s are maintained
.
ETS-8-044. 1 Pag e 7 o f 2 2 Metho d of Analysi s fo rth e Determinatio n of Perfluorinate d Compound s i n Wate rbyLC/MS/MS ; Direc t Injectio n Analysi s Pag e 5 3 o f 7 0GLPIO-01-01 ; Interi m Repor t 2 4 Analysi s o f PFO Ai n Groundwate r Decatur , A L - Decembe r201 1 

### 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 as a n example
. Weighe d amounts an d final volume s ma

yb e change d t o sui t th e need s o f a particula rstudy
. Fo rexample , \i L volume s ma

yb e spike d into volumetri cflasks whe n dilutin g stoc k solution s t o appropriat e levels
. 10 0 MQ/m L targe t analyt e SSSs—Weig h ou t 1 0 m g of analytica l standar d (correcte d fo r percen t salt , acid[ETS-4^31 ] an d purity ) an d dilut e t o 100 m L wit h methano l o rothe r suitabl e solvent , i n a 100 m L volumetri cflask. Transfe rt o a 12 5 m L LDP E bottl e o rothe r suitabl e container
. Prepar e a separat e solutio n fo reac h analyte
. Expiratio n date s an d storag e condition s o

f stoc k solution s shoul d b e assigne d i n accordance wit h laborator y standar d operatin g procedure
. A n exampl e of purit yan d sal t correctio n i s give n belowfo r PFOS
. ^

. , , 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 C8F17SO3K

* wit h purit

y90 % = 8.35 m g C8F17SO3'(1 0 mg*0.90*0.9275=8.3 5 mg ) 1 0 |jg/m L (10,00 0 ng/mL ) mixe d workin g standard—Ad d 5. 0 m L eac h o f th e 100 |jg/m L SSS s t o a 5 0 m L volumetri cflask an d brin g u p t o volum e wit h solvent
. 1 pg/m L (1,00 0 ng/mL ) mixe d worlcin g standard—Ad d 0. 5 m L o f th e 100 |jg/m L SSS s t o a 5 0 m L volumetri cflask

an d brin g u p t o volum e wit h solvent
. 0. 1 \iglm L (10 0 ng/mL ) mixe d standard—Ad d 0.05 m L of th e 100 ijg/m L SSS s t o a 5 0 m L volumetri cflask

an d brin g u p t o volum e wit h solvent
. Storag e Conditions—Stor e al l SSS s an d wori<in g standard s i n accordance wit h laborator y standar d operatin g procedur

e o ri n a refrigerato ra

t 4°db2° C fo ra maximu m perio d of 6 month s fro m th e dat e of preparation
. 

### 7. 5 Calibratio n Standard s Calibratio n ca n b e perfonne d b yI S o rexterna l calibration
. Usin g th e wori<in g standard s describe d above , prepar

e calibratio n solution s i n AST M Typ e I water , HPLC water , othe r suitabl e water , o ra mixture o f solven t an d wate rusin g th e infonnatio n i n Tabl e 2 a s a guideline
. Note : Volume s of wate ro rwater/solven t mixture s an d worthin g standard s ma yb 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 rtha n thos e liste d belowca n b e prepare d as needed
. Fo rth e quantitatio n o

f PFO Aan d PFOS , reference material s o f certifie d mixe d linea ran d branche d isome rar

e preferred
. Altemately , reference material s of primaril ylinea risomer s o f PFO Aand/o rPFO S ma

yb e used , however , whe n quantitatin g wit h predominantl ylinea r reference standards , additiona l LC S sample s containin g bot h linea ran d branche d isomer s o f PFO Aan d PFO S are required ^ 7.5. 1 interna l Standard (IS ) an d Surrogat e Recover yStandard (SRS ) Fo rI S calibration , stabl e isotop e intema l standard s o f eac h targe t analyt e o rappropriat e surrogat e IS s shoul d b e spike d a t th e sam e leve l i n al l calibratio n standards
. Once th e calibratio n standard s have bee n prepare d a s state d above i n Sectio n 7.5 , al l calibratio n standard s are spike d wit h a separat e intema l standar d spikin g solution
. Typicall yth e A repor t summarizin

g a n assessmen

t o f th e us e o f referenc e standard

s containing certifie dlinea r an dbranche disomer s o f PFOA/PFO

S ca n b e foundi n 3 M repor

t E l 1-0560. ETS-8-044. 1 Pag e 8 o f 2 2 Metho d o f 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 5 4 o f 7 0GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFO Ai n Groundwate r Decatur , A L - Decembe r201 1
concentratio n of th e interna l standar d i s consisten t wit h th e intema l standar d concentratio n expecte d i n th e sample s bein g prepared , usuall y1 ng/mL
. Th e concentrafio n o f th e intema l standar d spikin g solutio n i s typicall y2 ijg/mL
. Aseparat e zero poin t o rmetho d blan k i s typicall yprepare d a

t th e sam e tim e a s th e calibratio n standards , usin g th e sam e solufio n use d t o prepar

e th e standard s (AST M Typ e I water , HPLC water , othe rsuitabl e water , o ra solvent/wate rmixture) , an d i s spike d wit h th e interna l standar d a t th e sam e concentratio n a s th e calibratio n curve , typicall ya t 1 ng/mL
. I f th e sample s bein g analzye d were pre-spike d wit h SRSs , th e calibratio n curve prepare d i n Sectio n 7. 5 i s spike d wit h a separat e SR S spikin g solution
. Typically , th e sampl e bottle s are spike d wit h a SR S a

t 0. 1 ng/mL
. Th e final calibratio n curve must consist of a t least si x calibrafio n points afte ranalysis
. Th e followin g tabl e provide s a n exampl e of spik e concentration s an d volume s use d t o achieve a multi-poin t extracte d calibratio n curve wit h intema l standar

d an d sun'ogate standard
. Tabl e 1 lists recommende d stabl e isotop e intema l standard s fo rsevera l PFS Aan d PFC

A target compounds
. Acusto m mi xof isotopicall ylabele d targe t analyte s i n a methanoli c solutio n containin g ([1,2,3,4-^^C4]PFBA , [1, 2 -^^CJPFHxA , [1,2,3,4,5, 6 7,8-^^C8]PFOA , [1,2,3,4,5,6,7,8,9-^^C9]PFNA , [1,2,3,4,5, 6 -^^CeJPFDA , [1,2,3,4,5,6, 7 -"CyjPFUnA , [1, 2 - ^^CJPFDoA , [1,2,3-"C3]PFHS , [1,2,3,4,5,6,7,8-"C8]PFOS , an d [1,2,3,4,5,6,7,8-"C8]FOS A (Wellingto n Laboratories , Guelph , ON ) i n combinatio n wit h adde d ([1,2,3,4,5-"C5]PFPeA , ([1,2,3,4-"C4]PFHpA , an d [^^OJPFB S ca n b e use d t o prepar e a stoc k I S solufion
. Alternafive source s o

f certifie d stabl e isotop e labele d targe t analyte s ar e applicable
. Altematively , individua l stabl e isotop e IS s ca n b e use d t o prepar e a stoc k I S mixture
. Th e tabl e belowlists th e recommende d stabl e isotop e IS s an d SRS s applie d i n th e method
. Othe rstabl e isotop e IS s an d SRS s of target analyte s no t liste d i n th e tabl e ma

yb e use d i f supporte d b

yvalidatio n and/o ranalysi s batc h QC s meetin g metho d acceptance criteri a (e.g. , ["CJ-PFOA)
. Th e sam e interna l standar d shoul d b e use d fo ra give n analyt e throughou t th e entir e project/study
. Note : som e o f th e compound s liste d belo ware appropriat e t o us e a s surrogat e IS s whe n a stabl e isotop e I S of a targe t analyt e i s no t available
. Generally , sun'ogate isotopicall ylabele d PFCA s ar e use d fo rPFCAs , an d surrogat e isotopicall ylabele d PFSA s are use d fo rPFSAs
. Tabl e 2 provide s example s of spik e concentration s an d volume s use d t o achieve a multi-poin t calibratio n curve wit h IS s an d SRSs
.

ETS-8-044. 1 Pag e 9 o f 2 2 Metho d o f 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 5 5 o f 7 0GLPIO-01-01 ; Interi m Repor t 2 4 Analysi s o f PFOAi n Groundwate r Decatur , A L - Decembe r201 1
Tabl e 1 . Stabl e isotop e PFCA s an d PFSA s use d fo r IS s an d SRS s
Compound

Name Synonym orAcronym Analytical Purpose Reference Standard

Source "C4-Perfluorobutanoic aci d [1,2,3,4-"C4]PFB A I S fo r PFB A Wellingto nLabs

(Mi x o r Individual ) "C4-Perfluoropentanoi

c acid [l,2,3,4,5-"C5]PFPe A I

S fo r PFPe A Wellingto nLabs

(Mi x o r Individual ) "C2-Perfluorohexanoi

c aci d [1, 2 -"CzlPFHxA I S fo r PFHx A Wellingto nLabs

(Mi x o r Individual ) "C4-Perfluoroheptanoi

c acid [1,2,3,4-"C4]PFHp A I

S fo r PFHp A Wellingto nLabs

(Mi x o r Individual ) "Cg-Perfluorooctanoic acid [l,2,3,4,5,6,7,8-"C8]PFOA I S fo r PFO A an d[1,2,3, 4 "C4]PF0A Wellingto nLabs (Mi x o r Individual ) "CrPerfluorononanoi c aci d [1,2,3,4,5,6,7,8,9-"CJPFN A I S fo r PFN A Wellingto nLabs

(Mi x o r Individual ) "C6-Perfluorodecanoi

c acid [1,2,3,4,5,6-"aiPFD A I S fo r PFD A Wellingto nLab s

(Mi x o r Individual ) "C7-Perfluoroundecanoi

c acid [1,2,3,4,5,6,7-"ClPFUn A I S fo r PFUn A Wellingto nLabs

(Mi x o r Individual ) '^Ca-Perfluorododecanoi

c acid [l,2-"C2]PFDo A I S fo r PFDoA , *PFT

A Wellingto nLabs (Mi x o r Individual ) "02-AmmoniumPerfluorobutan e sulfonat e ["OzlPFB S I S fo r PFB S RT I Internationa l (Individual ) "Cs-Ammoniu

mPerfluorohexan

e sulfonat e [1,2,3-"C3]PFHS I S fo r PFH S Wellingto nLabs

(Mi x o r Individual ) "Cg-Sodiu mPerfluorooctan

e sulfonat e [l,2,3,4,5,6,7,8-"C8]PFO S I S fo r PFO S an d PFOS[l,2,3, 4 "C4] , Wellingto nLabs (Mi x o r Individual ) "Cs-Perfluorooctanesulfonamid e [l,2,3,4,5,6,7,8-"C8]FOS A I S fo r FOSA Wellingto nLabs (mix )

RT I Internationa

l (Individual ) ''C4-Perfluorooctanoic acid [l,2,3,4-"C4]PFO A SR S fo r al l PFCAs : C4-C 8 Wellingto n "C2-Perfluoroundecanoi

c acid [l,2-"C2]PFUn A SR S fo r al l PFCA s C9-C1 3 Wellingto n "Cg-Perfluorooctan

e sulfonat e [l,2,3,4-"C4]PFO S SR S fo r al l PFSAs : C4 , C6 , an dC 8 Wellingto n

ETS-8-044. 1 Pag e 1 0 of 2 2 Metho d o f 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 5 6 o f 7 0GLPIO-01-01 ; Interi m Repor t 2 4 Analysi s o f PFOAi n Groundwate r Decatur , A L - Decembe r201 1

Tabl e 2 . Exampl e Preparatio n o fCalibratio n Curv e wit h IS s an d SRS s Sample Description Concentration

ofWS,pg/mL Volume of WS.pL Volume

of IS (2pg/mL),fjL Concentration of Surrogate, pg/mL Volume of Surrogate, /d. Volume of ASTM Type 1 Water, or other suitable solventmL 0.02 5 ng/m L curv e poin t 0.1 0 2 5 5 0 0.2 0 12. 5 10 0 0.03 0 ng/m L curv e poin t 0.1 0 3 0 5 0 0.2 0 1 5 10 0 0.0 4 ng/m L curv e poin t 0.1 0 4 0 5 0 0.2 0 2 0 10 0 0.0 5 ng/m L curv e poin t 0.1 0 5 0 5 0 0.2 0 2 5 10 0 0. 1 ng/m L curv e poin t 0.1 0 10 0 5 0 0.2 0 5 0 10 0 0.2 5 ng/m L curv e poin t 0.1 0 25 0 5 0 0.2 0 12 5 10 0 0. 5 ng/m L curv e poin t 1. 0 5 0 5 0 0.2 0 25 0 10 0 1 ng/m L curv e poin t 1. 0 10 0 5 0 0.2 0 50 0 10 0 2. 5 ng/m L curv e poin t 10. 0 2 5 5 0 10. 0 2 5 10 0 5. 0 ng/m L curv e poin t 10. 0 5 0 5 0 10. 0 5 0 10 0 10. 0 ng/m L curv e poin t 10. 0 10 0 5 0 10. 0 10 0 10 0 25. 0 ng/m L curv e poin t 10. 0 25 0 5 0 10. 0 N A 10 0 50. 0 ng/m L curv e poin t 10. 0 50 0 5 0 10. 0 N A 10 0 75. 0 ng/m L curve poin t 10. 0 75 0 5 0 10. 0 N A 10 0 10 0 ng/m L curv e poin t 10. 0 100 0 5 0 10. 0 N A 10 0 N/ A- Not Applicabl e (1 ) Sample s requirin g analysi s fo rPFUnA , PFDoA , PFTrDA , an d FOSAshoul d b e analyze d agains t a calibratio n curv e prepare d i n 1: 1 synttieti cgroundwater:MeOH
.

ETS-8-044. 1 Pag e 1 1 o f2 2 Metho d o fAnalysi s for th e Determinatio n o fPerfluorinate

d Compound s i n Wate r b y LC/MS/MS ; Direc

t injectio n Analysi s Pag e 5 7 of 7 0GLPIO-01-01 ; Interi m Repor t 2 4 Analysi s o f PFOAi n Groundwate r Decatur , A L - Decembe r201 1


### 8 Sampl e Collectio n an d Bottl e Preparatio n Sampl e collectio n bottle s are prepare d b y3 M Environmenta l Laborator y(o rsubcontrac

t supplier ) personne l fo r shipmen t a

t ambien t temperature t o th e collectio n site
. Typically , fou rseparat e collectio n bottle s are associate d wit h a singl e collectio n site : sample , field duplicat e sample , lo wfield matri xspike , an d hig h field matri xspike
. Alternatively , th e sampl e an d field duplicat e sampl e ma ycontai n SRS s i n lie u of additiona l targe t analyt e lo wfield matri xspik

e an d targe t analyt e hig h field matri xspik e samples
. Dependin g o n th e scop e of th e project , additiona l replicate s of th e field sampl e an d field matri xspike s ma yb e added
. Also , i t i s no t uncommo n fo radditiona l mid-leve l field matri xspike s t o b e collecte d i f th e expecte d sampl e concentration s are trul yunknow n o rcoul d spa n a larg e concentratio n range . High-densit

ypolyethylen e (HDPE ) wide-mout h Nalgen e bottle s are use d fo rth e sampl e collecfio n containers
. (Volume s of th e bottle s ma yvar ydependin g o n ho

wmuc h sampl e i s require d t o meet dat a qualit yobjectives. ) Sampl e collecfio n volume s are projec t specifi can d base d o n dat a qualit yobjectives
. Th e Nalgen e bottle s d o no t requir e an ypretreatmen t prio rt o use . Typically , placemen t of a sampl e bottl e volumetri c"fil l t o here " lin e i s don e b yusin g a sampl e bottl e marke rtemplate
. Alternatively , bottle s ma yb e weighe d prio rt o bottl e preparatio n an d weighe d agai n afte rsample s hav e bee n collected
. Al l bottle s shoul d b e cleari ylabele d t o indicat e its intende d us e as a sample , field sampl e duplicate , lo wfield matri xspike , hig h field matri xspike , sample/SR S field matri xspike , field duplicat e sample/SR S field matri x spike , tri p blank , o rtri p blan k matri xspike
. I f eac h locatio n ha s differen t designate d spik e levels , th e labe l shoul d als o cleari yindicat e th e sampl e locatio n designation
. Generally , a set of bottle s fo ra give n collectio n sit e are prepare d the n groupe d togethe ri n plasti cbag s fo rorganizationa l purposes . Fo reac h sampl e collectio n event , a

t least on e set of tri p blan k an d tri p blan k

matri xspike s are prepared
. Bottl e preparatio n shoul d b e documente d i n a Not e t o Fil e o ro n a sampl e preparafio n wori^sheet an d shoul d includ e th e followin g infonnation : dat e prepared , tota l numbe ro f bottle s prepared , numbe ro f sampl e sites , th e standar d identificatio n number

s an d spike volume s use d t o prepar e spike d bottles , th e "fil l t o here " volume , an d an yothe rpertinen t informatio n neede d fo rreconstructibilit yo f th e data
. Th e Note t o Fil e wil l b e include d i n th e final data packag e fo rth e project
. Sample s are collecte d i n th e field an d shippe d t o th e laborator ya t ambien t temperature . 8. 1 Fiel d Matri x Spik e Sampl e (FMS ) Fiel d matri xspike sample s are a requiremen t of th e method
. AFM S sampl e i s define d a s a QC sampl e t o whic h know n quantitie s of appropriat e targe t analyte s are adde d t o th e sampl e bottl e i n th e field o ri n th e laborator ybefor e th e bottle s ar

e sen t t o th e field. Th e sampl e an d field duplicat e sampl e ma ycontai n appropriat e SRS s i n lie u of targe t analyt e FM S samples
. Sampl e quantitie s are determine d volumetricall yo r gravimetrically
. Aknown , specifi cvolum e o rweigh t of sampl e i s adde d t o th e sampl e containe rwithou t rinsing. Volumetri csampl e measurements ma yb e acquire d b

ya laborator

yapplie d "fil l t o thi s level " lin e o n th e outsid e of th e sampl e container
. Target analyt e FM S sample s shoul d b e spike d a t approximatel y0.5-1 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 spik e a t a n appropriat e leve l i s made
. Typicall ya lo

wan d a hig h target analyt e spik e are prepare d fo reac h samplin g locafion
. I n thos e instance s where SRS s ar e t o b e use d i n lie u of targe t analyt e FM S samples , th e sampl e an d field duplicat e sampl e are spike d a

t approximatel y2- 5 time s th e targe t LOQ
. Th e FM S i s analyze d t o ascertai n i f matri x effect s o rsampl e holdin g tim e contribute s bias t o th e analytica l results
. Fo rth e sampl e bottle s designate d fo r matri xspikes , a n appropriat e volum e of matri xspikin g solufio n i s adde d t o th e empt ybottl e prio rt o sampling
. Th e volum e of spike solutio n adde d shoul d produce th e desire d final concentratio n of targe t analyte s once th e bottl e i s filled wit h sampl e t o th e "fil l t o her e line"
. Th e matri xspikin g solution(s ) shoul d b e prepare d i n a suitabl e solven t an d contai n al l o f th e appropriat e targe t analytes , ISs , an d SRSs
. Th e targe t analyt e matri x spikin g solutio n i s ofte n th e sam e as th e workin g standard s use d t o creat e th e calibratio n standards
. A n exampl e of a bottl e spike i s give n below
. "Fil l t o here " volum e = 20 0 m L ( A25 0 m L Nalgen e bottl e i s used ) Desire d Fiel d Spik

e Concentratio n = 0.2 5 ng/m L ETS-8-044. 1 Pag e 1 2 of 2 2 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 5 8 o f 7 0GLPIO-01-01 ; Interi m Repor t 2 4 Analysi s o f PFOAi n Groundwate r Decatur , A L - Decembe r201 1
50 0 p.L of a 0. 1 ng/m L spikin g solutio n (containin g th e targe t analytes ) i s adde d t o th e bottl e an d th e bottl e ca p promptl ysealed
. 8. 2 Interna l Standar d an d Surrogat e Recover y Standar d I f analysi s o

f a sun-ogat

e recover ystandar d (SRS ) i s include d i n th e projec t objectives , a n appropriat e volum e o f a sun-ogat

e standar d solutio n i s adde d t o al l th e bottle s prio rt o samplin g an d SPE
. Typicall ysampl e bottle s are spike d wit h sun-ogat

e recover ystandard s a

t a final desire d spike concentratio n of 0. 1 ng/mL
. I f quantitatio n b

yinterna l standar

d (IS ) i s include d i n th e projec t objective , a n appropriat e volum e o f intema l standar d solutio n i s adde d t o al l th e bottle s prio rt o samplin g an d SPE
. Typicall ysampl e bottle s ar e spike d wit h interna l standar

d a t a final desire d spike concentrafio n o f 1 ng/mL
. Fo rth e tri p blank , th e SR S spik e an d I S spik

e i s adde d t o th e bottl e an d the n AST M Typ e I wate r(HPLC grad e reagen t wate ro rothe rsuitabl e wate rma yused ) i s adde d t o th e "fil l t o here " line
. Th e bottl e i s cappe d an d sealin g tap e ma

yb e place d aroun d th e oute redg e o f th e cap . Tri p blan k

matri xspike s ar

e prepare d b

yaddin g th e appropriat e volum e of target analyt e spikin g solution , IS , an d SR S spikin g solution s an d filling th e bottl e t o th e desire d volum e wit h th e appropriat e wate ran d cappin g an d sealin g th e cap . 9 Qualit y Contro l an d Dat a Qualit y Objective s 9. 1 Dat a Qualit y 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 belowwil l b e documente d i n th e ra

wdat a an d footnote d i n th e final report . 9. 2 Method/Procedura l Blank s Th e method/procedura l blan k i s zer o poin t calibratio n standar d (whic h include s ISs ) analyze d i n a regula rbasi s wit h eac h analysi s batch
. A t a minimum , metho d blank s ar e analyze d prio rt o instmmen t calibration , prio rt o th e analysi s o

f CCV samples , afte rever y1 0 sampl e injections , an d a t th e en d o

f th e analytica l mn . Th e mea n are a coun t o rare a ratio s whe n usin g interna l standar d calibration , 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 count s o rare a ratio s whe n usin g interna l standar d calibration , of th e LOQ standard
. Th e standar d deviatio n of th e are a counts , o rare a ratio s whe n usin g interna l standar d calibrafion , of thes e metho d blank s shoul d b e calculated
. Aspecifi c%RS D acceptance criteri a i s no t specifie d bu t i s assesse d o n a n analytica l batc h basis
. I f th e mea n are a counts o rare a ratio s whe n usin g interna l standar d calibration , 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 first standar

d leve l i n th e curve that meets criteria
. Metho d blank s ma yb e eliminate d i f technica l justificatio n ca n b e provide d (e.g
. th e procedura l blan k wa s analyze d afte ra n unexpectedl yhig h leve l sample)
. I f an yprocedura l blank

s are remove d fro m th e LOQ determination , documen t i n th e ra wdat a an d repor

t a s appropriate
. Laborator

ySampl e Replicate s /

Fiel d Duplicat e Sampl e Typically , sample s are collecte d i n duplicate s i n th e field. Th e relative percen t differenc e (RPD ) of duplicat e sample s shoul d b e ^20 % fo rth e precisio n of sampl e preparatio n an d analysi s t o b e considere d i n control
. Replicat e sample s no

t meetin g th e ^20 % RP D criteri a are flagge d an d reporte d as outsid e o f QC acceptance criteria
. 9. 3 Laborator y Matri x Spike s (LMSs ) LMS s ma yb e perfonne d i n lie u o

f FMS s i f FMS s have previousl ybee n performe d fo rth e sampl e matrix
. Additionally , LMS s ma

yb e performe d i n lie u o

f FMS s fo ra sampl e matri xi f th e FM S level s were no t appropriat e fo rdetemninin g spike recoverie s relative t o endogenou s level s o f targe t analyte s an d appropriat e SRSs
. Generally , eac h sampl e locatio n represents a differen t sampl e an d sampl e matrix
. LMS s ar e prepare d fo reac h sampl e an d analyze d t o detennin e th e matri xeffec t o n spik e recover yefficienc yof eac h targe t analyt e an d appropriat e SRSs
. LMS s shoul d b e prepare d a t a minimu m o

f on e leve l an d i n duplicate
. LM S concentration s shoul d b e prepare d a t approximatel y0.5-1 0 fimes th e endogenou s concentratio n o r approximatel y4-1 0 time s th e LOQ concentratio n of eac h targe t analyte
. ETS-8-044. 1 Pag e 1 3 of 2 2 Metho d o f Analysi s fo rth e Determinatio n o f Perfluorinate d Compound s i n Wate rb yLC/MS/MS ; Direc

t Injectio n Analysi s Pag e 5 9 o f 7 0GLPIO-01-01 ; Interi m Repor t 2 4 Analysi s o f PFOAi n Groundwate r Decatur , A L - Decembe r201 1
La b matri xspike recoverie s shoul d fal l withi n ±30 % of expecte d values
. Sampl e dat a wit h LM S recover y outsid e of ±30 % bu t withi n ±50 % of th e expecte d valu e are flagged an d reporte d a s outsid e o f Q C acceptance criteria
. Data wit h LM S recover youtsid e of ±50 % of th e expecte d valu e are reporte d a s NR , where N R i s define d a s "No

t Reportable " data outsid e of Q C acceptance criteria
. 9. 4 La b Contro l Sampl e La b contro l spike s are prepare d fo reac h analysi s batc h t o determin e metho d accurac yan d precision
. LCS s shoul d b e prepare d a

t thre e level s i n triplicat e fo reac h targe t analyt e an d a t a minimu m of two level s i n triplicat e fo rappropriat e SRSs
. Lo wla b contro l spike s shoul d b e prepare d a t a concentratio n i n th e rang e of approximatel yfou rt o te n time s highe rtha n th e targete d lowe rLOQ , th e mi d la b contro l spike s shoul d b e prepare d a

t a concentrafio n nea rth e mid-poin t of th e calibratio n curve an d th e hig h la b contro l spike s a t approximatel y80 % of th e uppe rLOQ
. Fo reac h targe t analyt e an d SRSs , th e percen t relative standar d deviatio n (metho d precision ) fo reac h contro l spike leve l must b e les s tha n o requa l t o 20 % an d th e averag e recover y(metho d accuracy) fo reac h contro l spike leve l must b e 80-120%
. Sampl e dat a fo rtarget analyte s outsid e of th e laborator

ycontro l spik

e acceptance criteri a wil l b e handle d a s follows : I f th e averag e recover

yo f a spikin g leve l fall s outsid e metho d acceptance , bu t a t leas t 67 % ( 6 ou t of 9 ) o

f LC S sample s ar

e withi n 20 % of thei rrespective nomina l valu e (33 % of th e Q C samples , no t al l replicate s a

t th e sam e concentration , ma

yb e outsid e 20 % o

f nomina l value) , th e averag e recover ywil l b e flagged a s outsid e metho d acceptance criteria
. Al l LC S sample s wil l b e contro l charte d a s pe rETS-4-026
. I f th e averag e recover yo f on e o

f th e spikin g level s exceede d th e analytica l metho d uncertaint ya s detennine d b

yETS-12 - 012 , that analytica l batc h uncertaint ywil l b e expande d fo rthat particula rstudy
. I f mor e tha n 67 % o f th e LC S sample s fai l t o meet metho d acceptance criteria , th e data wil l no t b e reported
. Calibratio n standard s consistin g of mixe d branche d an d linea risome rPFOS/PFO Aare prefen-ed
. However , fo rPFOS/PFO

Atarge t analytes , i f th e calibratio n standard s are comprise d of predominantl ylinea risomer s only , a t least on e leve l o

f triplicat e LCS s shoul d b e prepare d usin g PFOS/PFO Awhic h contain s a mi xo f linea r an d branche d isomers
. Thes e LCS s wil l b e use d t o demonstrat e quantitative equivalenc y(o rquantitative bias ) of th e isomeri cmi xwhe n usin g a predominantl ylinea rstandar d fo rcalibration
. Th e mixe d linea ran d branche d isome rPFOS/PFO

ALCS s recoverie s shoul d fal l withi n ±30 % of expecte d values
. Alternatively , i n lie u of mixe d branche d an d linea risome rPFOS/PFO ALCSs , mixe d branche d an d linea risome rPFOS/PFO A TBMS s ma

yb e applie d t o demonstrat e metho d accurac yan d precision
. 9. 5 Fiel d Matri x Spike s (FMSs ) / Surrogat e Recover y Standard s (SRSs ) FMS s are prepare d fo reac h samplin g locatio n an d analyze d t o detennin e th e matri xeffec t an d sampl e holdin g tim e o n th e spike recover yo f eac h targe t analyt e and/o rappropriat e SRS
. Generally , eac h sampl e locatio n represents a differen t sampl e an d sampl e matrix
. FMS s ar e Q C sample s t o whic h know n quantitie s of appropriat e targe t analyte s are adde d t o th e sampl e bottl e i n th e laborator

ybefor e th e bottle s are sen t t o th e field. Typicall ya lowan d a hig h targe t analyt e FM S are prepare d fo reac h samplin g location
. Th e sampl e an d field duplicat e sampl e ma ycontai n appropriat e SRS s i n lie u of target analyt e lo

wfield matri xspik

e an d targe t analyt e hig h field matri xspik e samples
. Fiel d matri xspike metho d acceptance criteri a ar e recoverie s withi n ±30 % o f th e expecte d value
. I f FM S recover y(target analyt e o rSR S spike ) i s outsid e o f ±30 % o f th e expecte d valu e o rcoul d no t b e assesse d becaus e th e FM S (target analyte ) was spike d a t a n inappropriat e level , th e sampl e resul t i s reporte d a s follows : 1
. ) I f target analyt e FM S recover ycoul d no

t b e assesse d becaus e th e FMS' s were a t a n inappropriat e level , the n Laborator

yMatri xSpike s (LMS ) ma yb e substituted
. I f LM S recoverie s ar e withi n ±30 % th e dat a ar e reportabl e an d flagged t o indicat e that th e FM S spike s level s were inappropriate
. 2
. ) I f multipl e targe t analyt e FMS' s were prepare d o n a sampl e an d th e closest FM S leve l t o th e reporte d sampl e meets th e ±30 % acceptance criteri a bu t additiona l FMS' s are outsid e th e ±30 % acceptance range , th e data are reportabl e an d flagged t o indicat e that whil e there were failin g FMS's , th e uncertaint ywil l no t b e expande d since th e most appropriat e spike leve l passed
. ETS-8-044. 1 Pag e 1 4 of 2 2 Metho d of Analysi s fo rth e Determinatio n o f Perfluorinate d Compound s i n Wate rb yLC/MS/MS ; Direc

t Injectio n Analysi s Pag e 6 0 o f 7 0GLPIO-01-01 ; Interi m Repor t 2 4 Analysi s o f PFOAi n Groundwate r Decatur , A L - Decembe r201 1
3
. ) I f th e targe t analyt e FM S recoverie s are outsid e o f th e ±30 % acceptance rang e bu t at leas t 3 0 acceptabl e historica l reportabl e FM S sampl e results are available , th e data ma yb e reporte d bu t flagged wit h a n expande d uncertaint yan d a s no

t meetin g FM S criteria
. 4
. ) Sampl e data wit h FM S recover youtsid e of ±30 % bu t withi n ±50 % of th e expecte d valu e are flagged an d reporte d a s outsid e of Q C acceptance criteri a wit h a n expande d uncertainty
. 5 . ) I f FM S recover

yi s outsid e o

f ±50% , th e sampl e resul t i s reporte d a s NR , where N R i s define d a s "No t Reportable " du e t o noncomplian t Q C results
. Th e targete d fortificatio n level s shoul d b e a t leas t 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 o f accurac yfo ranalytica l results
. Note : I t i s possibl e fo rbottle s utilize d fo rFiel d Matri xSpik e sample s t o b e under-fille d o rover-fille d durin g sampl e collection
. Since thi s scenari o wil l effec t th e actua l concentratio n o f th e FM S sampl e (sun-ogat e an d interna l standar

d concentration s wil l als o b e effected , i f used) , i t i s importan t that an yobviou s under-fillin g o r over-fillin g o

f sampl e bottle s b e documente d i n th e dat a packag e an d take n into accoun t i n th e FMS , ISs , o r SRS s recover

ycalculations
. Sample s over-fille d o runder-fille d b ymor e tha n 10 % wil l b e requir

e recalculatio n o f th e FMS , ISs , an d SR S tm e values
. Th e averag e o

f the sampl e an d the field duplicat e shoul d b

e use d t o calculat e the recovery. 

### 1 0 Procedure s 10. 1 Wate r Sampl e Preparatio n Thi s metho d i s applicabl e t o wate rsamples
. Sample s containin g heav yparticulat e ma

ynot 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 autovial
. • Dilute sample , i f necessary , wit h AST M Typ e I water , HPLC water , othe rsuitabl e water , o rsolven t (methanol)
. • La b contro l spike s are prepare d fo reac h analysi s batc h t o detemnin e metho d accurac yan d precision
. LCS s shoul d b e prepare d a t thre e level s i n triplicat e fo reac h targe t analyt e an d a t a minimu m of two level s i n triplicat e fo rappropriat e SRSs
. Lo wla b contro l spike s shoul d b e prepare d a t a concentrafio n i n th e rang e o

f approximatel yfou rt o te n time s highe rtha n th e targete d lowe rLOQ , th e mi d la b contro l spike s shoul d b e prepare d a t a concentratio n nea rth e mid-poin t o f th e calibratio n curve an d th e hig h la b contro l spike s a

t approximatel y80 % o

f th e uppe rLOQ
. Fo rI S quantitation , stabl e isotop e intema l standard s o

f eac h targe t analyt e o rappropriat e sun-ogat e IS s shoul d b e spike d a

t th e sam e leve l as th e sample s bein g analyzed , i n al l LCSs
. • I f LCS s are bein g prepare d usin g syntheti cgroundwater , allowth e LCS s sample s t o equilibrat e fo ra minimu m of 4 hour

s befor e aliquotin g fo ranalysi s o rdilutin g wit h solven t (methanol)
. 1 1 Sampl e Analysi s - LC/MS/M S 11. 1 Instrumen t Setu p Note : I n thi s example , a n Applie d Biosystem s SciexAP I 400 0 (AP I 500 0 o rAP I 5500 ) Tande m Mass Spectromete r(LC/MS/MS ) i s used
. Othe rbrands/model s o f LC/MS/M S instmments as wel l as singl e quadrupol e mas s spectrometer s (LC/MS ) ma

yb e use d a s lon g a s th e metho d acceptance criteri a are met . Bran d names , suppliers , par t numbers , an d model s ar e fo rillustrafive purpose s only
. Equivalen t perfonnanc e ma yb e achieve d usin g apparatu s an d material s othe rtha n thos e specifie d here , bu t demonstratio n of equivalen t perfonnanc e tha t meets th e requirements of thi s metho d i s th e responsibilit yof th e laboratory
. Th e operato rmust optimiz e an d documen t th e equipmen t an d setting s used
. ETS-8-044. 1 Pag e 1 5 o f 2 2 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 6 1 o f 7 0GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFO Ai n Groundwate r Decatur , A L - Decembe r201 1
Establis h th e LC/MS/M S syste m an d operatin g condition s equivalen t t o th e following : Mass Spec : Applie d Biosystem s AP I 4000 , AP I 5000 , o rAP I 550 0 Io n Source : Turb o Io n Spra y(ABS ) Mode : Electrospra

yNegative Sca n Type : MR M (Multipl e Reactio n Monitoring ) Computer : Del l DH M Software : Windows 200 0 o rWindows XP , Analyst 1.4. 2 o rhighe rversion s HPLC : Agilen t Serie s 1100,1200 , o r129 0 Agilen t Quatemar

yPum p Agilen t Vacuu m Degasse r Agilen t Autosample r Agilen t Colum n Ove n Note : On e o rmor

e C1 8 HPLC analytica l column s (2. 1 m m x100 mm , 5|x m o r2. 1 m m x5 0 mm , 5|xm) mayb e attache d on-lin e afte rth e purg e valve an d befor e th e sampl e injectio n por t t o retar d an d separat e an yresidu e contaminants tha

t ma yb e i n th e mobil e phas e and/o rHPLC system . HPLC Column : Betasi l C18,4.6m m x100mm , 5n m (ThemnoElectro n Corporafion ) Colum n Temperature : 35° C Injectio n Volume : 5|J L Mobil e Phas e (A) : 2m M Ammoniu m Acetat e i n AST M Type I water (Se e 7.3 ) Mobil e Phas e (B) : Methanol Tabl e 3 . Liqui d Chromatograph y Gradien t Program . Step Number Total

Time (min) Flow

Rate (ftUmin) Percent A (2 mM ammonium acetate) PercentB (Methanol) 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 Note : Othe rHPLC gradients ma yb e use d a s lon g a s th e metho d criteri a an d projec t dat a qualit

yobjective s are met . I t ma yb e necessar

yt o adjust th e HPLC gradien t i n orde rt o optimiz e instmmen t performance
. Column s wit h differen t dimension s (e.g
. 2.1m m x30mm ) an d column s fro m differen t manufacturer s (Keyston e Betasi l C1 8 etc. ) ma yb e used
.

ETS-8-044. 1 Pag e 1 6 o f 2 2 Metho d of Analysi s fo rth e Determinatio n of Perfluorinate d Compound s i n Wate rbyLC/MS/MS ; Direc t Injectio n Analysi s Pag e 6 2 o f 7 0GLPIO-01-01 ; Interi m Repor t 2 4 Analysi s o f PFOAi n Groundwate r Decatur , A L - Decembe r201 1
Tabl e 4 Suggeste d IVIRiV I Transition s fo r Targe t Analytes , Surrogates , an d interna l Standard s Analyte Analyte Description Mass Transition Ql (amu) Mass Transition

Q3 (amu) PFB A (C 4 Acid ) Targe t 21 3 16 9 PFPe A (C 5 Acid ) Targe t 263 21 9 PFHx A (C 6 Acid ) Targe t 31 3 269 , 11 9 PFHp A (C7 Acid ) Targe t 36 3 319 , 16 9 PFO A (C 8 Acid ) Targe t 41 3 369,219,16 9 PFN A (C9 Acid ) Targe t 46 3 419 , 169,21 9 PFD A (CIO Acid ) Targe t 51 3 469,269,21 9 PFUn A (C1 1 Acid ) Targe t 56 3 519.269,21 9 PFDo A (C1 2 Acid ) Targe t 61 3 569 , 169,31 9 PFT A (01 3 Acid ) Targe t 66 3 619 , 369,31 9 FBS A (C 4 Sulfonamide) Targe t 29 8 7 8 FOSA (C 8 Sulfonamide) Targe t 49 8 7 8 PFB S (C 4 Sulfonate) Targe t 29 9 99 , 8 0 PFH S (C 6 Sulfonate) Targe t 39 9 99,8 0 PFO S (C 8 Sulfonate) Targe t 499 80 , 99 , 13 0 [1,2,3,4-"C4IPFB A I S fo r PFB A 21 7 17 2 r 1,2,3,4,5-"CslPFPe

A I S fo r PFPe A 268 22 3 fl,2-"C2lPFHx A I S fo r PFHx A 31 5 270 [1,2,3,4
- "CilPFHp A I S fo r PFHp A 36

7 32

2 [l,2,3,4,5,6,7,8-"C8lPFO A I S fo r PFO A 42 1 376 [1,2,3,4,5,6,7,8,9-"CIPFNA I S fo r PFN A 472 42 7 [1,2,3,4,5, 6 -"CfilPFD A I S fo r PFD A 51 9 47 4 [1,2,3,4,5,6,7-"ClPFUn A I S fo r PFUn A 570 52 5 fl,2-"C2lPFDo A I S fo r PFDo A an dPFT A 61 5 57 0 ["O2IPFB S I S fo r PFB S 30 3 8

4 [l,2,3-"C3lPFH S I S fo r PFH S 40

2 8

0 [1,2,3,4
- "C4IPFOS I S fo r PFO S 50

3 8

0 [l,2,3,4,5,6,7,8-"C8lFOS A I S fo r FOSA 50 7 8

0 [l,2,3,4-"C4lPFO A Surrogat e (C4-C 8 Acids ) 41 7 372 [1,2,3,4-"C4IPFO S Surrogate(Sulfonates , FOSA ) 50

3 8

0 [l,2-"C2lPFUn A Surrogat e (C9-C1 3 Acids ) 56 5 52

0 Multipl e transition s fo rmonitorin g th e analyte s i s a n option
. Th e us e o f on e daughte rio n i s acceptabl e i f data sensitivit yan d selectivit

yi s achieve d an d provide d that retentio n fime criteri a are met t o assur e adequat e specificity
. Whil e th e daughte rion s ma yb e chose n a

t th e discretio n o

f th e analyst , mas s transitio n 9 9 i s suggeste d fo rPFOS
. Quantitafio n ma yb e perfonne d usin g th e tota l io n chromatogra m (TIC , o rsumme d MRMs) fo ra give n analyte
. Fo rexample , th e PFO ATI C woul d su m al l thre e of th e monitore d transitions
. Us e o f th e suggeste d primar

yio n i s recommended
. Retentio n time s ma yvar yslightly , o n a day-to-da

ybasis , dependin g o n th e batc h of mobil e phas e an d th e gradient , column , guar d column(s ) use d etc . Drif t i n retentio n time s i s acceptabl e withi n a n analytica l run , a s lon g a s th e drif t continue s throug h th e entire analysi s an d th e standard s are intersperse d throughou t th e analytica l run . 11. 2 Calibratio n Curv e Quantitatio n i s b

yinterna l standar

d o rexterna l standar

d calibration
. Calibratio n standard s ma yb e prepare d i n AST M Typ e I , HPLC water , othe rsuitabl e water , o ra solvent/wate rmixture
. I f interna l standar d calibrafio n doe s no t meet calibratio n acceptance criteria , extema l calibratio n ca n b e applied
. Se e Tabl e 1 fo r ETS-8-044. 1 Pag e 1 7 o f 2 2 Metho d of Analysi s fo rth e Determinatio n of Perfluorinate d Compound s i n Wate rbyLC/MS/MS ; Direc t Injectio n Analysi s Pag e 6 3 o f 7 0GLPIO-01-01 ; Interi m Repor t 2 4 Analysi s o f PFOAi n Groundwate r Decatur , A L - Decembe r201 1
recommende d applicatio n of availabl e interna l standards
. Quantitatio n of PFO Aan d PFO S i s b

ysumme d analyte-specifi cmas s transitions
. Analyz e th e standar

d curve prio rt o eac h set o f samples
. I f interna l standard s were adde d t o th e calibratio n standard s are a ratio s are use d t o generat e th e calibratio n curve . Th e standar d curve ma

yb e plotte d usin g a linea rregressio n (

y= m x+ b) , weighte d 1/

xo runweighted , o rb

yquadrati cfit (

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

xo r unweighted , usin g suitabl e software
. Th e mathematica l metho d use d t o calculat e th e calibrafio 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 rfit 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 curve points shoul d als o b e exclude d i f thei rare a counts (o rare a rafi o i f quantitatin g b yIS ) are no

t a t least twic e that o f th e averag e are a counts (o rare a rati o i f quantitatin g b yIS ) of metho d and/o rsolven t blanks
. Th e coefficien t of detemninatio n (r^

) valu e fo rth e calibratio n curve must b e greate rtha n o requa l t o 0.99 0 (o ra con-elatio n coefficien t (r) of 0.995)
. Eac h poin t i n th e curve must b e withi n ±25 % o f 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%
. Justificatio n fo rexclusio n of calibratio n curve points wil l b e note d i n th e ra

wdata
. Aminimu m o

f 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 rprepar e a ne w standar d curve (i f necessary

) an d reanalyze
. 11. 3 Continuin g Calibratio n Verificatio n (CCV ) Continuin g calibratio n verificafion s (CCV ) ar e analyze d t o verif

yth e accurac

yof th e calibratio n curve . Analyz e a mid-rang e calibratio n standard , on e o f th e sam e standard s use d t o construc 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 o f 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 must b e brackete d b

ypassin g CCVs o rth e calibratio n curve an d a passin g CCV t o b e reportable
. 11. 4 Syste m Suitabilit y Aminimu m o

f thre e syste m suitabilit

ysample s shoul d b e injecte d a t th e beginnin g o

f eac h analytica l mn , prio r t o th e analysi s of th e calibratio n curve . Typicall ythes e sample s are a t a concentratio n nea rth e mid-leve l o f th e calibrafio n curve an d are repeate d injection s fro m on e autosample rvial
. I t i s suggeste d that th e syste m suitabilit yinjection s have are a counts o rare a ratio s whe n usin g intema l standar d calibration , wit h a targe t RS D o f S5% an d a targe t retentio n tim e RS D o f 22%
. There i s n o define d acceptabilit ylimi t o n thes e results as th e %RS D valu e i s dependen t o n th e numbe ro f MR M transition s bein g monitore d i n th e LC/MS/M S ru n o rfime period
. Ultimately , an yeffect s o n thes e parameter s fo rth e Syste m Suitabilit ysample s wil l als o b e eviden t o n al l standard s an d Q C sample s analyze d a s part o f th e analysi s batch
. An yeffec t o f syste m suitabilit

yi s incorporate d withi n QC acceptance criteria
. 

### 11. 5 Sampl e Analysi s an d QC s Fo reac h analysi s batch , th e instrumen t analysi s ru n sequence shoul d includ e a n initia l calibratio n curve , samples , FDSs , intersperse d blanks , intersperse d CCVs , appropriat e QC s (i.e. , LCSs , LMSs , FMSs , TBMSs , an d TBs) , an d a final CCV o rcalibratio n curve bracketin g sample s an d appropriat e QC s Injec t th e sam e volum e (betwee n 5 -100\A. ) o f eac h standard , analytica l sampl e an d blan k int o th e instrumen t (unles s a n on-instrumen t sampl e dilutio n i s desired)
. Sample s containin g analyte s tha t 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
.

* 3 M Environmenta

l Laborator

y stud y E08-009 6 evaluate

dth e effec t o n thes e result s a s afunctio n o f

th e numbe r o f MRM s bein

g monitored . ETS-8-044. 1 Pag e 1 8 o f 2 2 Metho d of Analysi s fo rth e Determinatio n of Perfluorinate d Compound s i n Wate rbyLC/MS/MS ; Direc t Injectio n Analysi s Pag e 6 4 o f 7 0GLPIO-01-01 ; Interi m Repor t 2 4 Analysi s o f PFO Ai n Groundwate r Decatur , A L - Decembe r201 1

1 2 Dat a Analysi s an d Calculation s Th e chromatograph yanalysi s software wil l typicall ycalculat e th e amoun t of target analyt e i n th e sampl e extracts usin g th e establishe d calibratio n curve . Calculat e th e percen t recover yof th e LC S usin g th e followin g equation : LC S Concentratio

n (— ) LCS % recover

y = S^^ ^ * 100 % Spik e Concentratio

n (—^ ) m L Calculat e th e percen t recover yo f th e LM S usin g th e followin g equation :
LMS Concentration

(-^) - Concentration

of Sample (-^^) LM S % recovery= ^ * 100 % Spik e Concentratio n (-^^ )

m L Fo rsample s fortifie d wit h know n amounts o f analyt e prio rt o extraction , us e th e followin g equatio n t o calculat e th e percen t recovery . Recov e _analyt e foun d (ng/mL ) - Averag e analyt e foun d i n sampl e (ng/mL ) ^ Analyt e adde d (ng/mL ) 1 3 Analysi s Batc h Metho d Performanc e Criteri a An ymetho d performance parameter s that are no

t achieve d must b e considere d i n th e evaluatio n of th e data
. Nonconfonnance t o an yspecifie d parameter s must b e describe d an d discusse d i n th e final repor t 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 perfomnanc e sectio n are no

t met , maintenance ma

yb e peri'orme d 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 ar e t o b e reporte d whe n perfomnanc e criteri a hav

e no t bee n met , th e dat a must b e footnote d o n table s an d discusse d i n th e tex

t of th e report . 13. 1 Syste m Suitabilit y - Analysi s Batc h Aminimu m o

f thre e syste m suitabilit

ysample s shoul d b e injecte d a t th e beginnin g of eac h analytica l run . Thes e sample s are ru n prio rt o th e calibratio n curve . I t i s suggeste d that th e syste m suitabilit yinjection s have are a counts wit h a targe t RS D o f ^5 % an d a targe t retentio n tim e RS D o f S2%
. There i s n o define d acceptabilit

ylimi t o n thes e results a s th e %RSD s are dependen t o n th e numbe rof MR M transition s bein g monitore d i n th e LC/MS/M S nj n o rtim e period
. An yeffec t of syste m suitabilit

yi s incorporate d i n th e Q C acceptance criteria
. 13. 2 Calibratio n an d Limi t o f Quantitatio n (LOQ ) - Analysi s Batc h Calibratio n Curve : Th e coefficien t of determinatio n (r^ ) valu e fo rth e calibrafio n curve must b e greate rtha n o r equa l t o 0.99 0 correspondin g t o a correlatio n coefficien t (r ) = 0.995
. Eac h poin t i n th e curve must b e withi n ±25 % o f th e theoretica l concentratio n wit h th e exceptio n of th e LLOQ , whic h ma yb e withi n ±30%
. CCV Perfomriance : Th e calibratio n standard s that are intersperse d throughou t th e analytica l sequence ar e evaluate d as 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 y ETS-8-044. 1 Pag e 1 9 of 2 2 Metho d of Analysi s fo rth e Determinatio n o f Perfluorinate d Compound s i n Wate rb yLC/MS/MS ; Direc

t Injectio n Analysi s Pag e 6 5 o f 7 0GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFO Ai n Groundwate r Decatur , A L - Decembe r201 1

o f eac h curve poin t must 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
. Limit s o f Quantitatio n (LOQ) : Th e lowe rLOQ (LLOQ ) i s th e lowest non-zer o active standar

d i n th e calibratio n curve ; th e pea k are a of th e LLOQ must b e a t leas t 2 X that of th e averag e are a counts fo ral l prepare d procedura l blank(s)
. B ydefinition , th e measure d valu e o f th e LLO Q must b e withi n 30 % of th e theoretica l value
. 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
. 13. 3 Blank s - Method/Procedura l Blank s an d Tri p IVIethod/Procedura l Blanks : Multipl e procedura l blank s shoul d b e intersperse d throughou t th e analysi s batc h an d th e analytica l sequence . A t a minimum , metho d blank s are analyze d prio rt o instmmen t calibration , prio r t o th e analysi s of CCV samples , afte rever y1 0 sampl e injections , an d a t th e en d o

f th e analytica l ain
. Th e mea n are a counts (o rare a ratio s whe n usin g I S calibration ) fo reac h analyt e must b e les s tha n 50 % o f th e are a coun t o

f th e LOQ standard
. I f th e are a counts of th e procedura l blank s excee d 50 % o

f th e LOQ standard , the n th e LOQ must b e raise d t o th e first standar d leve l that meets criteria
. Tri p Blank : Atri p blan k

of AST M Typ e I wate r(o rla b equivalent) i s prepare d i n a sampl e containe ri n th e laborator yan d treate d a s a sample , includin g exposur e t o shipping , samplin g sit e conditions , storage , preservatio n an d al l analytica l procedures
. Th e tri p blank s results fo reac h analyt e ar e include d wit h th e reporte d sampl e results
. 13. 4 Dat a Accurac y an d Precisio n - Analysi s Batc h La b Contro l Spikes : Th e averag e recover ya t eac h LC S leve l fo reac h targe t analyt e an d appropriat e SR S shoul d b e withi n 80-120 % an d th e percen t relative standar d deviatio n o

f th e recoverie s mus

t b e les s tha n o r equa l t o 20%
. I f th e averag e recover yo f a spikin g leve l fall s outsid e metho d acceptance , bu t a t least 67 % ( 6 ou t o f 9 ) of LC S sample s are withi n 20 % of thei rrespective nomina l valu e (33 % o f th e Q C samples , no

t al l replicate s a

t th e sam e concentration , ma yb e outsid e 20 % of nomina l value) , th e averag e recover ywil l b e fiagged a s outsid e metho d acceptance criteria
. Al l LC S sample s wil l b e contro l charte d a s pe rETS-12-012
. I f th e averag e recover

yof on e of th e spikin g level s exceede d th e analytica l metho d uncertaint ya s detennine d b

y ETS-12-012 , that analytica l batc h uncertaint ywil l b e expande d fo rthat particula rstudy
. Th e averag e recover y a t eac h LC S leve l fo rmixe d branched/linea risome rPFO Aan d PFO S shoul d b e withi n 70-130 % an d th e percen t relative standar

d deviatio n o

f th e recoverie s must b e les s tha n o requa l t o 20%
. Fiel d Duplicates : Th e relative percen t differenc e (RPD ) of duplicat e sample s shoul d b e les s tha n 20 % fo rth e precisio n of sampl e preparatio n an d analysi s t o b e considere d i n control
. Replicat e sample s no t meetin g th e 20 % RP D criteri a are flagged an d reporte d as outsid e of Q C acceptance criteria
. Fiel d Matri xSpikes : FM S acceptance criteri a are recoverie s withi n ±30 % o f th e expecte d valu e fo reac h targe t analyt e an d appropriat e SRS
. Sampl e data wit h FM S recover youtsid e of ±30 % bu t withi n ±50 % of th e expecte d valu e are flagged an d reporte d a s outsid e of Q C acceptance criteria
. Data wit h FM S recover y outsid e of ±50 % o

f th e expecte d valu e are reporte d as NR , where N R i s define d as "Not Reportable " data outsid e of QC acceptance criteria
. I f FM S recover ycoul d no

t b e assesse d becaus e FMS s were a t a n inappropriat e level , the n Laborator yMatri xSpike s (LMSs ) ma yb e substituted
. I f LM S recoverie s are withi n ±30 % fo reac h targe t analyt e an d SRS s th e data are reportabl e bu t flagged a s no t meetin g th e FM S metho d acceptance criteria
. 13. 5 Analytica l Metho d Uncertaint y Analytica l metho d uncertaint yfo reac h targe t analyt e an d SR S i s detennine d wit h contro l charte d historica l analysi s batc h LC S dat a fo rth e metho d an d reporte d wit h eac h analysi s batch
. ^ Uncertaint

ydetennination s

^ Methoduncertaint

y base do n INTERNATIONALANSASO/IE D STANDAR

D 1702 5 referenc e (GUM , Guid

e t o th e Expressio

n o f Uncertaint y i n Measurement) . Methodapplication demonstrate di nETS-12-012 , citin g references : a. ) EURACHEM/CITAC Guide , "Quantifyin g Uncertaint

y i n Analytica

l Measurement, " Secon

dEdition ; Editors : S.L.R . Ellison , M . Rosslein , an dA . Williams . b.)Georgian , Thomas , "Estimation o f Laborator y Analytica

l Uncertaint

y Using Laborator

y Contro l Samples, " Environmenta l Testin g & ETS-8-044. 1 Pag e 2 0 of 2 2 Metho d o f Analysi s fo rth e Determinatio n of Perfluorinate d Compound s i n Wate rbyLC/MS/MS ; Direc t Injectio n Analysi s Pag e 6 6 o f 7 0GLPIO-01-01 ; Interi m Repor t 2 4 Analysi s o f PFOAi n Groundwate r Decatur , A L - Decembe r201 1

ar e base d o n INTERNATIONA L ANS/ISO/IE D STANDAR D 1702 5 reference (GUM , Guid e t o th e Expressio n o f Uncertaint

yi n Measurement) an d describe d i n ETS-12-012
. At least thirt ydat a points are require d fo r detemninin g analytica l metho d uncertainty
. Th e metho d uncertaint yi s define d as 2 xth e standar d deviatio n of th e percen t recoverie s of th e poole d la b contro l spikes
. Whil e al l LC S dat a points are contro l charted , onl yth e mos t recen t fiftydat a points are use d fo rdetemninin g th e metho d uncertainty
. Whe n les s tha n thirtyLC S dat a points hav e bee n generate d fo ra give n analyte , th e analysi s batc h LCS s are use d t o detennin e th e dat a uncertainty
. I f FMS s meet th e ±30 % recover ycriteri a a

t a leve l appropriat e t o th e endogenou s level , an d th e LC S meet th e ±20 % recover ycriteria , the n th e uncertaint yof th e dat a i s detennine d a s withi n 100±20%
. Analysi s batc h sampl e dat a wit h FM S recover youtsid e of ±30 % bu t withi n ±50 % o f th e expecte d valu e are flagged an d reporte d a s outsid e o f Q C acceptance criteri a wit h expande d uncertainties
. Data wit h FM S recover youtsid e of ±50 % o

f th e expecte d valu e are reporte d a s NR , where N R i s define d a s "No t Reportable " data outsid e of Q C acceptance criteria
. I f FM S recover ycoul d no

t b e assesse d becaus e FMS s were a t a n inappropriat e level , the n Laborator yMatri xSpike s (LMSs ) ma yb e substituted
. I f LM S recoverie s ar e withi n ±30 % fo reac h targe t analyt e an d appropriat e SRS s th e dat a are reportabl e bu t flagged a s no t meetin g th e FM S metho d acceptance criteri a wit h uncertaintie s o f ±30%
. I f FM S d o no

t meet th e ±30 % recover

ycriteria , an d historica l FM S dat a doe s no t exist , th e analytica l uncertaint yi s evaluate d o n a sample-by-sampl e basis , th e dat a ma

yb e reporte d wit h expande d uncertaint yan d are flagged. 13. 6 Quantitatio n o f PFOA/PFO S - Analysi s Batc h Calibratio n standard s consistin g of mixe d branche d an d linea risome rPFOS/PFO Aar e prefen-ed
. Quantitatio n i s perfonne d b yintegratin g th e linea ran d branche d isomer s together
. Alternately , th e linea ran d branche d isomer

s ca n b e integrate d separately , applyin g th e appropriat e tm e valu e t o eac h calibratio n curve poin t fo reac h isomer
. Th e LC S an d sample s are the n quantitate d b yintegratin g th e linea ran d branche d isomer s separatel y(require s separat e analytica l results files) an d quantitatin g th e resultin g pea k against th e linea ro rbranche d calibratio n curve . Th e results fro m bot h integration s are the n summe d t o produce th e final result
. Integratin g th e linea ran d branche d isomer s separatel yma

yb e helpfu l fo rthos e sample s where th e linear/branche d ratio s d o no t closel ymatc h thos e of th e reference standards
. However , fo rPFOS/PFO

Atarge t analytes , i f th e calibratio n standard s ar e comprise d of predominantl ylinea r isomer s onl yth e metho d require s th e additio n of LCS s of mixe d branched/linea risome rPFOS/PFOA
. Th e purpos e o

f includin g thes e LCS s i s t o demonstrat e quantitative equivalenc y(o rquantitative bias ) of th e isomeri cmi xwhe n usin g a predominantl ylinea rPFO S o rPFO Astandar d fo rcalibration
. Altematively , i n lie u o f mixe d branche d an d linea risome rPFOS/PFO ALCSs , mixe d branche d an d linea risome rPFOS/PFOA TBMS s ma

yb e applie d t o demonstrat e metho d accurac yan d precision
. A n alternat e metho d o

f quantitatio n ca n b e performe d wherebyonl yth e linea risome rof PFOS/PFO Ai s integrate d an d use d fo rgeneratin g th e calibratio n curve . Th e LC S an d sample s are the n quantitate d b y integratin g th e linea ran d branche d isomer s separatel y(require s separat e analytica l results files) an d quantitatin g th e resultin g pea k against th e linea rcalibratio n curve . Th e results fro m bot h integration s are the n summe d t o produce th e final result
. Integratin g th e linea ran d branche d isomer s separatel yreduce s th e on colum n concentratio n fo rthos e sample s that contai n bot h linea ran d branche d isomer s o f PFOA/PFOS
. Thi s ensure s that th e concentratio n detecte d i s withi n th e a rang e o f th e calibrafio n curve that i s comparabl e regardles s o

f whethe rth e calibratio n curve wa s generate d usin g predominantl ylinea risomer s o f PFOS/PFO

A o rlinea rplu s branche d isomer s o f PFOS/PFOA
. 1 4 Pollutio n Preventio n an d Wast e Managemen t Wast e generate d whe n performin g thi s metho d wil l b e dispose d o f 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 intema l procedures
. Analysis , November/Decembe r 2000 . c.)Taylor, B.N . an dCE . Kuyatt , NIS T Technica l Not e 1297 , 199

4 Edition : "Guideline s fo r Evaluatin g an dExpressin

g th e Uncertaint

y o f NIS T Measuremen

t Resuhs."d.)Adams , T.M. , "A2L A Guid e fo r th e Estimation o f Measuremen

t Uncertaint

y i n Testing" , Jul

y 2002 . ETS-8-044. 1 Pag e 2 1 of 2 2 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 6 7 o f 7 0GLPIO-01-01 ; Interi m Repor t 24
. Analysi s o f PFO Ai n Groundwate r Decatur , A L - Decembe r201 1

1 5 Record s Eac h dat a packag e generate d fo ra stud ymust includ e al l supportin g informatio n fo rreconstructio n of th e data
. Informatio n fo rth e data 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 , instrumen t ru n lo g (instrumen t batc h records , instalmen t acquisitio n method , summar ypages) , instrumen t results files, chromatograms , calibratio n curves , an d dat a calculations
. 1 6 Affecte d Document s None. 1 7 Revision s Revisio n Numbe rSummar vof Change s 1 Section

1. included

the use of internal standard

calibration

by this method. Section 2. included

the use of internal standard

calibration

by this method. Included

the use of a solvent/water

mixture when analyzing

for PFUnA, PFDoA, PFTrDA, and FOSA.
. Section 3. Added

definitions

for internal standard, surrogate

internal standard, and surrogate

recovery

standard. Section 6. Removed

the details regarding

the instrument

parameters

to section 10 of the method. Section 7. Updated

reference

standards

to include intemal standards

and surrogates. Changed concentration

levels for working standards

and included the use of internal standards

and surrogates. Section 8. inserted

a new section on sample bottle preparation. Section 9 Quality Control. This

section was previously

section 10 in ETS-8-044.0. Updated QC criteria to be consistent

with method ETS-8-154.4. Section 10 Procedures. This

section was previously

section 8 (Sample l-landiing)

in ETS-8- 044.0. Added

detail regarding

the preparation

of LCSs. Included

the use of methanol

as a dilution solvent. Section 11 Sample

Analysis. This

section was previously

section 10 in ETS-8-044.0. included the details regarding

the instrument

parameters. Section 12 Data Analysis and Calculations. This

section was previously

section 11 inETS8-044.0. Removed

the equation

for calculating

the analytes concentration, indicating that this is done by the instrument

software. Section 13 h/iethod Performance. This

section was previously

section 12 in ETS-8-044.0. Updated QC criteria to be consistent

with ETS-8-154.4. Added

information

on the determination

of analytical

method uncertainty

and quantitation

of PFO/VPFOS. Section 14 Pollution

Prevention. This

section was previously

section 13 in ETS-8-044.0. Section 15 Records. This

section was previously

section 14 in ETS-8-044.0. ' '. • • Section 16 Affected Documents. This

section was previously

section 15 in ETS-8-044.0. Section 17 Revisions. This

section was previously

section 16 in ETS-8-044.0.

ETS-8-044. 1 Pag e 2 2 o f 2 2 Metho d of Analysi s fo rth e Determinatio n of Perfluorinate d Compound s i n Wate rbyLC/MS/MS ; Direc t Injectio n Analysi s Pag e 6 8 o f 7 0GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFO Ai n Groundwate r Decatur , A L - Decembe r201 1


### ATTACHMEN TD : DEVIATION(S )

Pag e 6 9 o f 7 0GLP10-01-01 ; Interi m Repor t 2 4 Analysi s o f PFO Ai n Groundwate r Decatur , AL - Decembe r201 1 

### RECOR D O F DEVIATION/NONCONFORMANC E

/, Identification stud y/ Projec t No
. GLP10-01-01-2 4 Date(s ) o f Occurrence : 12/30/1 1 (b111230b ) Documen t Number : ETS-8-044. 1 Deviatio n typ e • SO P (Chec k one ) • Protoco l • Equipmen t Procedur e 0 Metho d • GP O • Other : //. Description

(attach

extra pages as needed) 

### Metho d Requirements : 1
. FM S recoverie s withi n 100 % ±30%
. 2
. RP D value s <20%
. 

### Actua l procedure/process : 1 , DA L G W 134 R FM S recover ywa s 62.8%
. 2
. DALGW137SRPDwas21%
.

///
. Actions

Taken

(such as amendment

issued, SOP

revision, etc.) 

### Correctiv e Actio n ( • Ye s 0 No ) Reference : Acceptabilit yo f th e nonconformin g work : 1
. Th e non-complian t FM S wil l b e fiagge d i n th e final report . Th e metho d uncertaint ywil l b e expande d fo rPFO At o ±37forDALGW134R
. 2
. Th e non-complian t RP D fo rDA L G W 137 S wil l b e note d i n th e final report . Actions : • Haltin g o f Wor k • Clien t Notificatio n • Wor k Recal l • Withholdin g o f Repor t IZ I Other : Deviation s wil l b e note d i n final report . Projec t Lead/PA I Approval : Susan^Wol f Stud yDirecto r(i f GLP) : Sponso rApprova l (fo rGL P protoco l deviations) : N A 

### Date : M A Technica l Reviewe r(optional) : N A Date : N A Laborator yDepartnnen t Manage rApproval : Date : IV. Authorization

to Resume

Work Where halting of work occurred, resumption

of work must first be approved

by Laboratory

Management Laborator yDepartmen t IVIanage rApproval : N A Date : N A Deviation

No. (assigned

by Study Director

or Team Leader at the end of study or project)

ETS-4-008. 7 Documentatio n o f Deviation s an d Contro l o f Nonconformin g Testin g Page 7 0 o f 7 0