GLP10-01-01 . Interi m Repor t 27 : Analysi s o fPFO A i n Surfac e Wate r Sample s Collecte d a t Ber t Jeffrie s Landfil l i n Decatur . A L i n Februar y 201 2 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 Wes t Chester , 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 St . Paul , M N 55144 Projec t Identificatio n GLPlO-01-01-2 7 Tota l Numbe r o fPage s

6 1 ^CTTT^ —\

Th e testin g reported herei n mee t th e requirement

s o f ANSI/ISO/lE C 17025:200 5 "Genera l ^^m j 1 Requirement s fo rth e Competenc

e o f Testin g an d Calibratio n Laboratories" , i n accordanc e wit h ^^V ^ ^^ ^ / th e A2L

ATestin g Certificate # 2052.01 . Testin g tha t complies wit h thi s Intemationa l Standar d i7rT'>'-=- 3 also meet s principle s of IS

O 9001:2000 . IACCREPITEP I Testin g Cer t #2052.0 1Thi s pag e has bee n reserve d fo rspecifi ccountr yrequirements .

Pag e 2 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFOAi n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2



### GL P COMPLIANC E STATEMEN T Repor t Title : GLPl0-01-01 , Interi m Repor t 27 . Analysi s of PFO

Ai n Surface Wate rSample s Collecte d a t Ber t Jeffrie s Landfil l i n Decatur , A L i n Februar y201 2 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 wa s conducte d i n compliance wit h Toxi cSubstance s Contro l Ac t (TSCA ) Goo d Laborator yPractice (GLP ) Standards , 4 0 CF R 792 , wit h th e exception s liste d below :

• Thes e are environmenta l sample s where there i s n o specifi ctest substance , n o specifi ctes t 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 determine d unde rGLPs .

Gar yHohenstein , Sponso rRepresentative Date



# 1

Jaisimh a Kesari.'P.E. , DEE , StudyDirecto r' Date

Pag e 3 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFO Ai n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2



### QUALIT YASSURANC E STATEMEN T Repor t Title : GLP10-01-01 , Interi m Repor t 27 . Analysi s of PFO

Ai n Surface Wate rSample s Collecte d a t Ber t Jeffrie s Landfil l i n Decatur , A L i n Februar y201 2 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 findings were reporte d t o th e principa l analytica l investigato r(P.A.I.) , laborator ymanagemen t an d stud ydirector . Dat e Reporte d t o Inspectio n Date s Phas e Testin g Facilit y Stud yDirecto r Managemen t Stud yDirecto r 3/30/1 2 an d 4/2/1 2 Dat a an d Repor

t 4/9/1 2 4/6/1 2



### QA U Repres^ c

itative Date

Pag e 4 o f 6 1

### TABL E O F CONTENT S GL P Complianc e Statemen t 3 Qualit yAssuranc e Statemen t 4 Tabl e o f Content s 5 Lis t o f Table s 6 1 Stud yinfomiatio n 7 2 Summar y8 3 Introduction... . 9 4 Tes t & Contro l Substance s 9 5 Referenc e Substance s 1 0 6 Tes t Syste m 1 0 7 Metho d Summar y1 7. 1 Method s : 1 7. 2 Sampl e Collectio n 1 7. 3 Sa m pi e Preparatio n 1 7. 4 Analysi s 1 8 Analytica l Result s 1 2 8. 1 Calibratio n 1 2 8. 2 Syste m Suitabilit y1 2 8. 3 Limi t o f Quantitatio n (LOQ ) 1 3 8. 4 Continuin g Calibratio n 1 3 8. 5 Blank s 1 3 8. 6 La b Contro l Spike s (LCSs ) 1 3 8. 7 /Analytica l Metho d Uncertaint y1 4 8. 8 Fiel d Matri xSpike s (FMS ) 1 4

Pag e 5 o f 6 19 Data Summar yan d Discussio n 1 5 1 0 Conclusio n 1 8 1 1 Data/Sampl e Retentio n 1 8 1 2 Attachments 1 8 1 3 Signature s 1 9 

### LIS TO F TABLE S

Tabl e 1 . Summarize d PFO AResults (Jeffrie s Landfil l Site , Februar y2012 ) 8 Tabl e 2 . Sampl e Descriptio n Ke yCod e 1 0 Tabl e 3 . Instrumen t Parameter s 1 1 Tabl e 4 . Liqui d Chromatograph yCondition s 1 2 Tabl e 5 . Mass Transition s 1 2 Tabl e 6 . Limi t o

f Quantitatio n (LOQ ) 1 3 Tabl e 7 . Laborator

yContro l Spik

e Recover

y1 4 Tables . Analytica l Metho d Uncertaint y1 4 Tabl e 9 . Fiel d Matri xSpik e Level s 1 5 Tabl e 10 . JPA L S

W ET0 1 12022 8 1 6 Tabl e 11 . JPA L S

W ET02 12022 8 1 6 Tabl e 12 . JPA L S

W ET03 12022 8 1 6 Tabl e 13 . JPA L S

W ET04 12022 8 1 7 Tabl e 14 . Tri p Blan k

12022 8 1 7

Pag e 6 o f 6 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 Laboratory Buildin g 260-5N-1 7 St . Paul , M N 5514 4 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(5)mmm.com) : phon e (651)-733-986 0 Susa n Wolf , 3 M Analys t Chelsi e Grochow , Analys t Kevi n Eich , Analys t Kell yUkes , Analys t Jonatha n Steege , Analys t Stud y Date s Stud yInitiation : Marc h 8,201 0 Interi m Report 2 7 Experimenta l Tennination : Marc h 7,201 2 Interi m Report Completion : Dat e o f Interi m Repor t Signin g Locatio n o fArchive s Al l origina l ra wdat a an d th e analytica l repor t hav e bee n archive d a t th e 3 M Environmenta l Laborator yaccordin g t o 4 0 CF R Par t 792 . Th e tes t substanc e an d analytica l referenc e standar d reserv e sample s ar e archive d a t th e 3 M Environmenta l Laborator yaccordin g t o 4 0 CF R Par t 79 2

Pag e 7 o f 6 1

### 2

Summary Th e 3 M Environmenta l Laborator yreceive d surface wate rsample s fro m fou rdifferen t location s locate d a t Jeffrie s Landfil l i n Decatur , AL . Atota l of ninetee n sampl e bottle s were receive d a t th e 3 M Environmenta l Laborator

yfo rperfluorooctanoat e (PFOA ) analysi s an d include d duplicat e surface wate r sample s an d two field matri xspik e (FMS ) sample s fro m eac h samplin g location . Aset of tri p blan k samples ; singl e tri p blan k containin g Milli-Q TM wate ran d two tri p blan k spikes , were include d wit h th e sampl e bottles . /\1 1 sample s wer e logge d into th e laborator yinformatio n managemen t syste m (LIMS ) unde rprojec

t GLPlO-01-01-27 . Th e surface wate rsample s an d tri p blank s were receive d fro m Westo n personne l o n Marc h 2 , 2012 . Ai\ o f th e sample s were prepare d an d analyze d fo rPFO Aan d th e sun^ogat e recover ystandar d ^^C4-PF0A , followin g 3 M Environmenta l Laborator yMetho d ETS-8-044.1 . Th e averag e measure d PFO Aconcentration s are summarize d i n Tabl e 1 . Th e tri p blan k was belo w th e lowe rlimi t of quantitatio n (LLOQ ) o f 0.0240 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 analytica l uncertaint ywas estimate d a

t 100±17% . Tabl e 1 . Summarize d PFO A Result s (Jeffrie s Landfil l Site , February 2012 )

3M LIM S I D Sampl e Descriptio n PFO A Concentratio n (ng/mL) GLP l 0-01-01-027-00 5 JP/M.-SW-ET0 1 -0-12022 8 <0.024 0 GLP l 0-01-01-027-00 6 JPAL-SW-ET0 1 -DB-12022 8 <0.024 0 Average <0.024

0 VoRPD Sample/Sample

Dup N A GLP l 0-01-01-027-00 9 JPAL-SW-ET02-0-12022 8 <0.024 0 GLP l 0-01-01-027-01 0 JPAL-SW-ET02-DB-12022 8 <0.024 0 Average <0.024

0 %RPD Sample/Sample

Dup N A GLP l 0-01-01-027-01 3 JPAL-SW-ET03-0-12022 8 0.11 4 GLP l 0-01-01-027-01 4 JPAL-SW-ET03-DB-12022 8 0.11 0 Average 0.11 2 %RPD Sample/Sarrtple

Dup 3. 6 GLP l 0-01-01-027-01 7 JP/M.-SW-ET04-0-12022 8 0.0644 GLP l 0-01-01-027-01 8 JPAL-SW-ET04-DB-12022 8 0.070 9 Av^erage 0.067

7 %RPD Sample/Sample

Dup 9. 6 GLP l 0-01-01-027-02 5 JPAL-SW-TRIP1-0-12022 8 <0.024 0 N A= No t Applicabl e Th e analytica l metho d uncertaint yfo rPFO Ai s +17% .

Pag e 8 o f 6 1

### 3

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

ylocate d i n Decatur , Alabama . Th e objective o f th e overal l progra m i s t o gai n infomnatio n regardin g concentration s of perfluorooctanoat e (PFOA ) i n variou s environmenta l medi a suc h a s groundwater , soil s an d sediments that ar e associate d wit h an d nea rth e Decatu rfacility . Thi s analytica l stud ywa s conducte d t o analyz e surface wate rsample s collecte d fro m fou rlocation s nea r Jeffrie s Landfil l i n Decatur , A L fo rPFOA . 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 field sampling . Sampl e bottl e sets fo reac h samplin g locatio n include d a field sample , field sampl e duplicate , an d two field spik e samples . Eac h empt ycontaine rfo rsampling s was mari<e d wit h a 'iii l t o here " lin e t o produce a final sampl e volum e of 20 0 mL . Container

s designate d fo rfield matri xsample s were fortifie d wflth a n appropriat e matri xspik e solutio n containin g PFO

Aprio rt o bein g sen t t o th e field fo rsampl e collection . M sampl e bottle s include d th e additio n of ^^Ce-PFO A(interna l standard ) a

t a nomina l concentratio n of 1 ng/mL , an d "C4 - PFO A(surrogat e recover

ystandard ) a t a nomina l concentratio n of 0. 1 ng/mL . Se e sectio n 8. 8 of th e repor t fo rfield matri xspik

e 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 Determinatio n of Perfluorinate d Compound s i n Wate rb

yLC/MS/MS ; Direc

t Injectio n /Analysis" . Th e us e o f a n interna l standar

d was use d t o ai d i n th e data qualit yobjectives . Tabl e 1 summarize s th e averag e PFO Aconcentratio n fo rth e duplicat e surface wate rsample s collecte d an d th e tri p blan k sample . Table s 10-1 4 summariz e th e individua l sampl e results an d th e associate d FM S recoveries . /Al l results fo rth e qualit ycontro l sample s prepare d an d analyze d wit h th e sample s ar

e reporte d an d discusse d elsewher e i n thi s report . 

### 4 Test & Control Substances There was no

t a tes t 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 .

Pag e 9 o f 6 1

### 5

Reference

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

(LInear+Branched ) "C4-PFO A "Ce-PFO A "Ctf-PFO A Chemica l Nam e Perfluorooctanoat e Perfluorooctanoat e Perfluorooctanoat e Perfluorooctanoat e Chemica l Fotmul a C7F15COO H ''C4HF15O 2 ''C8HF15O 2 ^^C8HFl50 2 Identifie r CA S #95328-99- 7 MPFO A MPFC-C-051 1 MPFC-C-011 2 Us e Targe t /Analyt e Referenc e Standar d Surrogat e Intema l Standar d Intema l Standar d Sourc e Wellingto n Wellingto n Wellingto n Wellingto n Expiratio n Dat e 03/17/201 4 12/07/201 3 05/25/201 4 01/24/201 5 Storag e Condition s Froze n Froze n Froze n Froze n Chemica l Lo t Numbe r TPFOA031 1 MPFOA121 0 05241 1 01231 2 TC R Numbe r TCR11-0009 , TCR11-004 2 TCR11-000 1 TCR11-001 6 TCR12-000 4 Physica l Descriptio n Liqui d Liqui d Liqui d Liqui d Purit y 98.3 % >98 % NA<^ > NA<^ > (1) Compound

is part of a custom mixture of mass-lak)eled

perfluorinated

compounds

at a concentration

of 5.0 \i9lmL. 

### 6 Test System There was no

t a tes t syste m fo rthi s stud yi n th e classi csens e o f a GL P study . Thi s stud ywas conducte d fo ranalysi s o f surface wate rsample s collecte d fi-om th e Jeffrie s propert ylocate d nea r Decatur , A L b

yWesto n Solutions , Inc . personnel . Sample s fo rthi s stud yar e "rea l worid " environmenta l samples . Tabl e 2 . Sampl e Descriptio n Ke yCode . strin g Numbe r Strin g Descripto r Exampl e Example JPAL-SW-ET01-O-120228 1 Sample Location JPAL= Jeffries Property, Alabama 2 Sample Type SW= Surfyce Water 3 Well ID Example: ET01 ET=Eastern

tributary

to Mallard Creek 4 Sampling Date 120228- February

28, 2012 5 Sample Type 0=primary sample DB=dupllcate

sample LS = low spike HS = high spike

Pag e 1 0 o f 6 1

### 7

Method

Summary 7. 1 Method /Analysi s fo ral l analyte s was complete d followin g 3 M Environmenta l Laborator ymetho d 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" . 

### 7. 2 Sampl e Collectio n Sample s were collecte d i n 25 0 m L Nalgene^ ^ (high-densit

ypolyethylene ) bottle s prepare d a t th e 3 M Environmenta l Laboratory . Sampl e bottle s associate d wit h GLPlO-01-01-2 7 were retume d t o th e laborator ya t ambien t condition s o n Marc h 2 , 2012 . Sample s were store d refrigerate d a t th e laborator

y afte rreceipt . Aset o

f laborator

yprepare d Tri p Blan k

an d Tri p Blan k

field matri xspike s were sen t wit h th e set o f sampl e collecfio n bottles . 

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

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

y control sample

s wer e analyzed for PFO A usin g hig h perfomnanc e liqui d chromatography

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

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 final dat

a packet , an d ar

e briefl y describe

d belo wi n Tabl e 3 , Tabl e 4 an d Tabl e 5 . Tabl e 3 . Instrumen t Parameters . Instrumen t Nam e ETS Ginge r Analytica l Metho d Followe d ETS-8-044. 1 Analysi s Dat e 3/6/1 2 Liqui d Chromatograp h Agilen t 1100 Guar d colum n Betasi i C1 8 (4. 6 m m X10 0 mm) , 5 n Analytica l colum n Betasi l C1 8 (4. 6 m m X10 0 mm) , 5 u Injectio n Volum e 2 5 n L Mas s Spectromete r Applie d Biosystem s AP I 500 0 Io n Sourc e Turix ) Spra y Electrod e Turb o Io n electrod e Polarit y Negativ e Softwar e Analyst 1.4. 2

Pag e 1 1 o f 6 1Tabl e 4 . Liqui d Chromatograph y Conditions . Ste p Total

Time Flow

Rate Percent A PercentB Number (min) (/JJmin) (2 mM ammonium

acetate) (MethanoO ETS-8-044. 1 Analysi s 0 0. 0 75 0 97. 0 3. 0 1 2. 0 75 0 97. 0 3. 0 2 14. 5 75 0 5. 0 95. 0 3 15. 5 75 0 5. 0 95. 0 4 16. 5 75 0 97. 0 3. 0 5 20. 0 75 0 97. 0 3. 0 Tabl e 5 . Mas s Transitions .

Analyte Mass Transition Q1/Q3 Internal Standard Mass

Transition Q1/Q3 PFOA 413/369 ["CJ-PFOA 421/376

413/219 413/169 fCil-PFOA 417/372 ["CsI-PFOA 421/376 Dwel l tim e was 5 0 mse cfo reac h transition . Th e Individua l transition s wer e summe d t o produce a "tota l io n chromatogram " (TIC) , whic h wa s use d fo rquantitation . 

### 8 Analytical

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

yspikin g know n amounts o f th e stoc k

solutio n containin g PFO

A(reference standar

d containin g bot h linea ran d branche d isomers ) into a laboratory-prepare d synthefi cgroundwate r containin g calciu m an d magnesium . Aseparate intema l standar d spikin g solutio n was prepare d an d a n aliquot was adde d a

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

t a nomina l concentratio n of 1 ng/mL . Acalibratio n curve rangin g fro m approximatel y0.02 5 ng/m L t o 10 0 ng/m L (0.02 5 ng/m L t o 1 0 ng/m L fo r^^C4-PF0 Asurrogate ) was prepared . Aquadratic , 1/ xweighted , calibratio n curve of th e standar d pea k area/pea k

are a ratio s was use d t o fit th e data fo reac h analyte . Th e data were no

t force d throug h zer

o durin g th e fitting process . Calculatin g th e standar d concentration s usin g th e pea k area / pea k are a ratio s an d th e resultan t calibratio n curve confimie d accurac yof eac h curve point . Eac h curve poin t was 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 10 0 ±25 % (10 0 ±30 % fo rth e lowest curve point ) were met fo r PFO Aan d analytes . 13 ,

C4-PFO Asurrogate . Th e correlatio n coefficien t (r) was greate rtha n 0.99 5 fo rbot h 

### 8. 2 Syste m Suitability 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 was met fo rPFO

Aan d C4-PFO

Asun-ogate .

Pag e 1 2 o f 6 1GLP10-01-01 ; interi m Repor t 2 7 Analysi s o f PFO Ai n Surfac e Wate r Ber t Jeffrie s Landfli i - Februar y201 2

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 and 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 PFO A ca n b e found i n Tabl e 6 . Tabl e 6 . Limi t o

fQuantitatio n (LOQ) . Analysis Date PFOA

ng/mL 3/6/1 2 0.024 0 

### 8. 4 Continuin g Calibratio n Durin g th e cours e of eac h analytica l sequence , continuin g calibratio n verificatio n sample s (CC\/s ) 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 of 100 % ±25 % fo rPFO Aan d "C4-PFO Asurrogate . 

### 8. 5 Blank s Two type s o

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

results were reviewe d an d use d t o evaluat e metho d performance t o detennin e th e LOQ . Tri p blank

s refiec t th e shippin g an d sampl e collectio n conditon s th e sampl e bottle s an d sample s experience . 8. 6 La b Contro l Spike s (LCSs ) Low , mid , an d hig h la b contro l spike s were prepare d fo rth e targe t analyte s an d analyze d i n triplicate , whil e onl ylo

wan d hig h la b contro l spike s were prepare d fo rth e "C4-PFO Asurrogate . LCS s were prepare d b

yspikin g know n amounts of th e analyt e into 1 0 m L o f syntheti cgroundwate rt o produce th e desire d concentration . Th e spike d wate rsample s were the n analyze d i n th e sam e manne ra s th e samples . Th e metho d acceptance criteria , averag e of LC S a t eac h leve l shoul d b e withi n 100 % ±20 % wit h a n RS D <20% , were me t fo rbot h PFO

Aan d "C4-PFO Asurrogate . Th e followin g calculation s were use d t o generat e data i n Tabl e 7 fo rlaborator ycontro l spikes :

, n . „ Calculated Concentration,.,.,.„ , LC S Percent Recover

y= 100 % Spik e Concentratio n LCS % RS D = "^^"^^^

^ ^^P'"^^*^ " M00 % averag e LC

S recover y

Pag e 1 3 o f 6 1Tabl e 7 . Laborator yContro l Spik e Recovery . ETS-8-044. 1 Analyze d 3/6/1 2 PFOA(Linear + Branched) "C4-PFOAsurrogate Spiked Concentration Calculated

Concentration Spiked Concentration Calculated

Concentration Lab ID (ng/mL) (ng/mL) VoRecovery (ng/mL) (ng/mL) %Recovery LCS-120306- 1 0.19 0 0.162 85. 5 0.19 8 0.22 9 11 6 LCS-120306- 2 0.19 0 0.16 6 87. 6 0.19 8 0.22 3 11 2 LCS-120306- 3 0.19 0 0.164 86. 1 0.19 8 0.21 9 11 0 Averag e ±%RS D 86.4% ±1.3 % 113% ±2.7 % LCS-120306^ 1.9 0 1.8

8 99. 1 1.9 8 2.2 4 11 3 LCS-120306- 5 1.9 0 1.9

6 103 1.9 8 2.3 1 11 6 LCS-120306- 6 1.9 0 1.8

6 97. 9 1.9 8 2.3 3 11 8 Averag e ±%RS D 100 % ±2.7 % 116% ±2.2 % LCS-120306- 7 19. 0 18. 0 95. 0 N A NA NA LCS-120306- 8 19. 0 17. 8 93. 8 N A N A N A LCS-120306- 9 19. 0 16. 9 89. 1 N A N A N A Averag e ±%RS D 92.6 % ±3.4 % N A NA= No t Applicabl e 

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

yi s base d o n historica l Q C 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 of accurac yresults (i n % ) obtaine d fo rth e Q C samples . Th e expande d uncertaint

yi s calculate d b

ymultiplyin g th e standar

d deviatio n b

ya facto ro

f 2 , whic h con-espond s t o a confidence leve l of 95% . Tabl e 8 . Analytica l Metho d Uncertainty . Analyt e Metho d Standar d Deviatio n Metho d Uncertaint y PFO A ETS-8-044. 1 8.6 8 ±17 % 

### 8. 8 Fiel d IVIatrix Spike s (FMS ) Lo wan d hig h field matri xspike s wer e collecte d a

t eac h samplin g poin t t o verif ythat th e analytica l metho d i s applicabl e t o th e collecte d matrix . Fiel d matri xspike s were generate d byaddin g a measure d volum e of field sampl e t o a containe rspike d b yth e laborator

ywit h PFO

A(reference standar

d containin g bot h linea ran d branche d isomers ) prio rt o shippin g sampl e container s fo rsampl e collection . Fiel d matri xspik

e recoverie s witiii n metho d acceptance criteri a of 100±30 % confim n tha t "unknown " components i n th e sampl e matri xd o no t significanti yinterfer

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

f interest . Fiel d matri xspike concentration s must b e 50 % of th e sampl e concentratio n t o b e considere d a n appropriat e field spike . Fiel d matri xspike s ar e presente d i n sectio n 9 o f thi s report .

Pag e 1 4 o f 6 1GLP l 0-01-01 ; interi m Repor t 27 Analysi s o f PFO Ai n Surfac

e Wate r Ber t Jeffries Landfil l - Februar

y201 2

Tabl e 9 . Fiel d Matri x Spik e Levels . Samplin g Locatio n Spik e Leve l PFOA , ng/m L Al l Location s an d Tri p Blan k Lo w 099 8 Al l Location s an d Tri p Blan k Hig h 9.9 8 FMSRecove _( Sampl e Concentratio n of FM S - Averag e Concentration : Fiel d Sampl e & Fiel d Sampl e Dup.) , ^QQ ^ Spik e Concentrato n 

### 8. 9 Data Summary an d Discussio n Th e table s belo wsummariz e th e sampl e result s an d field matri xspik e recoverie s fo rth e samplin g location s a s wel l a s th e Tri p Blanks . Result s an d averag e value s ar e rounde d t o thre e significan t figures accordin g t o EP Aroundin g rules . Becaus e o f rounding , value s ma yvar yslightl yfro m thos e liste d i n th e ra wdata . Fiel d matri xspik e recoverie s meetin g th e metho d acceptanc e criteria o f ±30% , demonstrat e tha t th e metho d wa s appropriat e fo rth e give n matri xan d thei rrespectiv e quantitativ e ranges .

Page 1 5 o f 6 1Tabl e 10 . JPALSWET0 1 12022 8 PFOA "C4PFOA Concentration 3M LIMS ID Description (ng/mL) VoRecovery VoRecovery GLP l 0-01-01-27-00 5 J PAL-SW-ET01-0-12022 8 <0.024 0 N A 11 1 GLP l 0-01-01-27-00 6 J PAL-SW-ET0 1 -DB-12022 8 <0.024 0 N A 10 8 GLP l 0-01-01-27-00 7 JPAL-SW-ET01-LS-12022 8 0.95 0 95. 2 11 0 GLP l 0-01-01-27-00 8 J PAL-SW-ET0 1 -HS-12022 8 9.4 4 94. 6 11 8 Average Concentration

(ng/mL)

± %RPD/RSD <0.0240 ng/mL 112%±3.9°/o NA= No t Applicabl e Tabl e 11 . JPA L S WET0 2 12022 8 PFOA "C4PFO A Concentration 3M LIMS ID Description (ng/mL) VoRecovery VoRecovery GLP l 0-01-01-27-00 9 JPAL-SW-ET02-0-12022 8 <0.024 0 N A 10 9 GLP l 0-01-01-27-01 0 JPAL-SW-ET02-DB-12022 8 <0.024 0 N A 11 5 GLP l 0-01-01-27-01 1 JPAL-SW-ET02-LS-12022 8 0.93 8 94. 0 10 6 GLP10-01-01-27-01 2 JPAL-SW-ET02-HS-12022 8 9.0 2 90. 4 11 1 Average Concentration

(ng/mL)

± VoRPD/RSD <0.0240 ng/mL 110%±3.4% NA= No t Applicabl e Tabl e 12 . JPA L S WET0 3 12022 8 PFOA "C4PFOA Concentration 3M LIMS ID Description (ng/mL) VoRecovery VoRecovery GLP l 0-01-01-27-01 3 JPAL-SW-ET03-0-12022 8 0.11 4 N A 10 7 GLP10-01-01-27-01 4 J PAL-SW-ET03-DB-12022 8 0.11 0 N A 10 8 GLP10-01-01-27-01 5 JPAL-SW-ET03-LS-12022 8 1.1 0 99. 0 11 0 GLP10-01-01-27-01 6 J PAL-SW-ET03-HS-12022 8 9.3 7 92. 8 11 0 Average Concentration

(ng/mL)

± VoRPD/RSD 0.112 ng/mL±3.6% 109%± 1.4% NA= No t Applicabl e

Pag e 1 6 o f 6 1Tabl e 13 . JPA L S WET0 4 12022 8 PFOA "C4PFO A Concentration 3M LIMS ID Description (ng/mL) VoRecovery VoRecovery GLP10-01-01-27-01 7 JPAL-SW-ET04-0-12022 8 0.064 4 N A 11 2 GLP10-01-01-27-01 8 JPAL-SW-ET04-DB-12022 8 0.070 9 N A 11 1 GLP l 0-01-01-27-01 9 JPAL-SW-ET04-LS-12022 8 1.0 2 95. 4 11 1 GLP l 0-01-01-27-02 0 JPAL-SW-ET04-HS-12022 8 8.9 6 89. 1 10 9 Average Concentration

(ng/mL)

± VoRPD/RSD 0.0677ng/mL±9.6% 111%±1.1% NA= No t /Applicabl e Tabl e 14 . Tri p Blan k

12022 8 PFOA "C4PFOA 3M LIMS ID Description Concentration (ng/mL) VoRecovery %Recovery GLP l 0-01-01-27-02 5 JPAL-SW-TR1P 1 -0-12022 8 <0.024 0 N A 10 1 GLP l 0-01-01-27-02 6 JPAL-SW-TR1P1-LS-12022 8 0.95 5 95. 7 11 8 GLP l 0-01-01-27-02 7 JPAL-SW-TRIP1-HS-12022 8 9.1 6 91. 8 11 2 NA= No t Applicabl e

Pag e 1 7 o f 6 1

### 9

Conclusion Laborator ycontro l spike s an d field matri xspike s were use d t o determin e th e analytica l metiio d accurac yan d precisio n fo rPFOA . /Analysi s was successfull ycomplete d followin g 3 M Environmenta l Laborator ymetiio d ETS-8-044. 1 describe d herein . 

### 10 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 . 

### 11 Attactiments Attachmen t A : Protoco l /Amendment 2 7 (Genera l Projec t Outiine ) Attachmen t B : Representative Chromatogram s an d Calibratio n Curve s Attachmen t C : Analytica l Metho d - ETS-8-044. 1

Pag e 1 8 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFOAi n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2



### 12 Signatures

Clesto n Lange , Ph.D. , 3 M Principa l Analytica l Investigato rDat e

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

Gar yHohen^ein , 3 M Sponso rRepresentative Date

Jaisimh a Kesari , Stud yDirecto rDate

Pag e 1 9 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFO AI n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2


### ATTACHMEN TA : PROTOCO L AMENDMEN T

Pag e 2 0 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFOAi n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2 Analytical

Protocol:

GLP10-01-01 Amendment

27 

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

31V 1 Decatu rPhas e 3 Site-Relate d Monitorin g Progran n
PROTOCO L AMENDMEN TNO . 27

Amendment

Date: Februar y21 , 201 2 Performing

Laboratory

\ 3 M Environmental , Health , an d SafetyOperation s

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

Project Identification GLPlO-01-01-2 7 i Sampling

Event \ j 

### Ber t Jeffrie s Landfil l -Surfec e Wate rSamplin g

Pag e 1 o f 6
Pag e 2 1 o f 6 1GLP l 0-01-01 ; interi m Repor t 2 7 Analysi s o f PFOAi n Surfac e Wate r Ber t Jeffrie s Landfll l - Februar y201 2 Analytical

Protocol:

GLP10-01-01 I Amendment 27 

### Thi s amendmen t modifie s th e followin g portio n ofprotocol : ! "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 "

PBOTOCOi. READS: N o change s t o th e wordin g o f th e protoco l ar e required .
AMEN D T O READ : i 

### i i N o change s t o th e wordin g o f th e protoco l ar e required . Thi s amendnrien t onl yaddresse s an d document s th e additio n o f th e Genera l Project Outlin e (GPO ) fo rth e collectio n an d analysi s o f groundwate rsample s a t Decatur , AL , an d conducte d a s par t o f th e 3 M Decatu rPhas e 3 Prdgra m fo rPFOA(GLP l 0-01-01) . Samplin g activitie s at an d nea rth e Ber t Jeffrie s landfil l ar e schedule d jfo rth e wee k o f Februar

y27 , 201 2 an d wil l consis t o f 6 paire d surfac e wate ran d sedimen t samples . Thi s protoco l amendmen t addresse s th e samplin g an d analysi s o f th e surfac e wate rsamples . Surfac e wate rsample s collecte d unde rthi s samplin g even t wil l b e entere d int o th e 3 M Environmenta l Laborator yLiM S a s project GLPlO-01-01-2 7 an d reporte d a s interi m repor t GLPlO-01-01-27 , (reflectin g stud yGLP10-01-0 1 an d amendmen t -27) . Reason : | f 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 anticipate d surfac e wate rsampl e collectio n even t t o b e conducte d a t an d nea rth e Ber t Jeffrie s landfil l i n Lawrenc e County, . AL . ! Th e GP O i s thre e page s i n lengt h an d include d as attache d t o thi s amendmen t forni .

Pag e 2 o f 6
Pag e 2 2 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFO Ai n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2 Analytical

Protocol:

GLP1Q-01-01 I Amendment 27

Amendmen t Approva l 

# 21 . /2 , Gar yHohenstein , Sponso rRepresentative Dat e

Dat e Clesto n C . Lange , Principal/Analytica l Investigato r

Willia m Reagen , EH S Opn s Environmenta l La b Managemen t

Jaisimh a Kesar

f P.E. , DEE , Stud yDirecto r Date 

# 7h

Page 3 o

f 6
Pag e 2 3 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFO Ai n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2 Analytical

Protocol:

GLP10-01-01 Amendment

27 

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

yHohenstein , 3 M EHS&Opn s From : Susa n Wolf , 3 M EHS&Opns ; Environmenta l La b I cc : VWIlia

m Reagen , 3 M EHS&Opns ; Environmenta l La b Ja i Kesari , Westo n Solution s Charle s Young , Westo n Solution s ' • Date : Febmar

y21,201 2 , Subject : Analysi s o f Perfluorooctanoi cAci d (PFOA ) i n Groundwater , Soi l an d Sedimen t fo rttie 3 M

Decatu rPhas e 3 Site-Relate d Monitorin g Program ; GL P Interi m Repor t 2 7 - Ber

t Jeffrie s Landfill ; Surfac e Wate rsamplin g th e wee k o f Febmar

y27 i 2012 . 

### 1 Genera l Projec t Informatio n

Contact s 3 M Sponso rRepresentativ e Gar yHohenstei n j 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 | QahohensteirnSmmm.co m | 3 M Environmenta l Laborator yManagemen t Willia m K. Reage n ! 3 M EH S Opns, Environmenta l Laboratory 260-5N-1 7 65 1 733-973 9 wkreaoeniamnfim.co m Principa l Analytica l Investigato r Clesto n Lang e i 3 M EH S Opns , Environmenta l Laboratory 260-5N-1 7 i 65 1 733-986 0 \ eclanae(S)mnnm.co m j Samplin g Coordinato r! Timoth yFrina k

! Westo n Solution s | Timothv.frinak(SwBstonsolution3.co m Phone : (334)-332-912 3 | La b Reques t Numbe r GLP10J)1^1.2 7 Si xDigi t Departmen t Numbe r Dep t #530711 , Pixjjec t #002267444 9 Projec t Schedule/Tes t Date s Tentativel yschedule d fo rth e wee k o f February27 , 2012 . All v$rl)al and written correspondence

will bs directed to Gary Hohenstein

and Jai Kesari.

Pag e 4 o f 6

Pag e 2 4 o f 6 1GLP l 0-01-01 ; Interi m Repor t 27 Analysi s o f PFO Ai n Surfac

e Wate r Ber t Jeffries Landfil l - Februar

y201 2 Analytical

Protocol:

GLP10-01-01 I Amendment 27 

### 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 surfac e wate r sample s collecte d fro m si x(6 ) location s a t an d nea rth e Ber t Jeffrie s landfill . Surfac e wate rsample s wil l b e collecte d b

yWeston . Th e 3 M Environmenta l Laborator ywil l prepar e th e sampl e bottles . Sample s wil l b e analyze d fo rPerfluorooctanoi cAci d (PFOA) . Analyse s wil l b e conclucte d unde rth e GL P requirement s o f EP ATSC AGoo d Laborator yPractic e Standard s 4 0 CF R 792 . 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-01-01-27 . 

# I 3 Projec t Schedul e j 

## i Sampl e collectio n bottle s wil l b e prepare d b yth e 3 M Environmenta l Laboratory . Sampl e bottle s wil l b e shippe d i n cooler s overnigh t t o 3 M Decatu rfo raniva l b yFriday , Februar

y24 , 2012 . 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 I 140 0 Stat e Docks Roa d | Decatur , Alabam a 3560 1 i 

### ! 4 Tes t Parameter s I Th e targete d limi t o f quantitatio n wil l b e 0.02 5 ng/m L (ppb ) fo rPFOA . Atota l o f six,samplin g location s hav e bee n specified . Fo reac h samplin g location , a tota l o f lou rsampl e bottle s wil l be collecte d (sample , sampl e duplicate , low-leve l fiel d matri xspike , ari d high-leve l fiel d matri xspike) . Th e "fil l t o here " lin e o n eac h 25 0 m L Nalgen e bottl e wil l b e 20 0 mL . On e se t o f trj p blanks consistin g o f reagent-grad e vrater , a low-leve l tri p blan k spike , an d a high-leve l tri p blan k spike vwl l b e prepare d a t ttie 3 M Environmenta l Laborator yan d sen t t o th e samplin g locatio n wit h th e othe rbottles . N o previou s dat a o n fluonxhemicals i n groundwater , surfac e wate ro rsedimen t medi a exist fo rth e site . Th e taw fiel d matri xspike wil l b e prepare d at 1 ng/m L an d th e hig h fiel d matri xspike at 1 0 ng/mL . Al l sampl e bottle s vwl l includ e th e additio n o f "Cg-PFO A(intema l standard ) at a nomina l concentratio n o f 1 ng/m L an d "C4-PFO A(surrogat e recover ystandard ) a t a nomina l conceritratio n o f 0. 1 ng/mL . T o ai d i n sampl e collection , a non-spike d 1 - L sampl e bottl e wil l b e provide d fo reac h samplin g location . Sampl e collectio n wil l consis t o f direct immersion . Aliquot s wil l b e decante d fro m th e collectio n bottl e t o th e primary , duplicat e an d matri xspik e botties . N o rinseat e blan k wil l b e collected . 

### 5 Tes t Method s Sample s wil l b e prepare d an d analyze d b yLC/MS/WI S followin g ETS-8-044. 1 "Metho d o f Analysi s fo rth e Detenriinatio n o f Perfiuorinate d Compound s I n Wate rb yHig h Performance Liqui d Chromatography/Mas s Spectrometr

yDirec t injectio n Analysis" . Altemately , sample s ma yb e analyze d b

yET S 8-154, 3 "Determinatio n of Perfluorinate d Acids , Alcohols , /\mides , an d Sulfonate s I n Wate rB ySoli d Phas e Extractio n an d Hig h Performance Liqui d Chromatography/Mas s Spectrometry , Wher e applicable , sample s wil l b e analyze d against a n intema l standar d calibratio n cun/e . Eac h curve poin t wil l contai n isotopioally-labele d PFOAat a nomina l concentratio n o f 1 ng/mL. ; Th e calibrafio n curve wil l b e Pag e 5 o f 6 Page 2 5 o f 6 1GLP l 0-01-01; Interi m Repor t 2 7 Analysi s o f PFO Ai n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2 Analytical

Protocol:

GLP10-01-01 Amendment

27 generate d b

ytakin g th e rati o o f th e standar d pea k are a count s ove rth e intema l standard pea k are a count s t o fi t th e data fo reac h analyte . | Laborator ycontro l sample s prepare d wit h th e sample s must have a n averag e recover ywithi n 100±20 % an d a RS D s20% . Th e dat a qualit yobjective fo rthi s stud yi s quantitative results fo rth e targe t 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 b e addresse d i n th e repor

t an d th e fina l accurac

ystatemen t ma

yb e adjuste d accordingly . 

### 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 th e tw o fiel d matri xspikes . Tri p blan k

an d tri p blan k

spike s wil l b e reporte d fo rth e samplin g even t Laborator ycontnD l spike s o f reagen t wate rprepare d at th e tim e o f sampl e extractio n wil l alsoib e reporte d an d use d t o evaluat e th e overal l metho d accurac

yan d precision . Mettio d blank s o f reagen t wate rprepare d at th e tim e o f sampl e preparatio n wil l b e use d t o detennin e ttne metho d detectio n limi t Fo rthos e samplin g location s where th e fiel d matri xspik

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

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

Pag e 6 o f 6
Pag e 2 6 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFO Ai n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2


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

Pag e 2 7 o f6 1GLP l 0-01-01 ; Interi m Repor t 2 7 Analysi s o f PFO Ai n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2 Ginge r AG0133050 9 Result s Name : gl20306a.rd b

4 0 4 5 5 0 55 Analyt e Cone . /

I S Cone . Dat a printe d b yKJ

U Printin g Time : 1:17:1 8 P M Printin g Date : Monday , Marc h 12 , 201 2 Pag e 1 o f 1
Pag e 2 8 o f 61GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFOAi n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2 Ginge r AG0133050 9 Result s Name : gl20306a.rd b

Dat a printe d b yKJ

U Printin g Time : 1:17:3 9 P M Printin g Date : Monday , Marc h 12 , 201 2 Pag e 1 o f 1
Pag e 2 9 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFO Ai n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2 Ginge r AG0133050 9 Result s Name : gl20306a.rd b

Dat a printe d b

yST W Printin g Time : 8:14:2 5 A M Printin g Date : Wednesday , Apri l 1 1 Pag e 3 0 o f 6 1GLP l 0-01-01 ; Interi m Repor t 2 7 Analysi s o f PFOAi n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2 Ginge r AG0133050 9 Result s Name : gl20306a.rd b

Dat a printe d b yST W Printin g Time : 8:14:2 5 A M Printin g Date : Wednesday , Apri l 11 , 201 2 Pag e 2 o f 9 Pag e 3 1 o f 6 1GLP l 0-01-01; Interi m Repor t 2 7 Analysi s o f PFO Ai n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2 Ginge r AG0133050 9 Result s Name : gl20306a.rd b

Dat a printe d b yST W Printin g Time : 8:14:2 6 A M Printin g Date : Wednesday , Apri l 11 , Pag e 3 o f 9
Pag e 32 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFOAi n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2 Ginge r AG0133050 9 Result s Name : gl20306a.rd b 

# I Sampt e Name . •g1203068014 - Sampl e ID , "11012-6-6 - Fte ' •al20306a.wi r pM k Name : "laCflPFOA-ISIIS) - Mass(Bs) , -421.0/376. 0 Comment . ng/m L F C St d m SynBi . WalBi ' AnnolaUon * Sanpl e Index : 1 4 Sappl e Type : Standac d Concentration ; 1.0 0 ng/ia L Calculate d Cone : N/ A Acq . Date : 3/6/201 2 Acq . Time t 7:38:0 6 P M
Hin . Paa k Height : Min . Pea k width ; melliQua r 0.0 0 c 0.0 0 : ip c 30. 0 ;

Height : Star t Ti c En d lim e Valle y

i : 15. 5 97586 0 CO I 3.12e*00 5 15. 3 I Sampte Name'•9l20306a02 rSampl e ID . •12001-160 - F»6,-91203068.wi r • P«akNan> e •13C8PFOA-IS<IS) - Mass(es),-421.0/376. 0 I Commen L "Malho d Blank - Aruiotaiion . " Sampl e Index : 2 7 Sampl e Type : Unknow n Concentration ; 1.0 0 ng/nl . Calculate dCone : tl/ A Acq . Date : 3/7/201 2

Min . Pea

k Height : Kin . Pea

k Hidth : Smoothin g Width : R T WlndOM . ExpecCe dRT : Use Relativ e RT ;
Height : Star t 1 En dTi r



# I Sampl a Name : -g120306a028 ' Sampl e ID ' TCS-120306-1 - Fie : -g120306a.wi r Pea k Name : -13C8PFOA-IS(IS} ' Ma££(es) . '421.0/376. 0 Comment . "OJpp b LCS " Annotatio n " Sampl e In

< mpl B Typ e Concentiatlo n 0.9 9 Calculate dCone ; N Acq . Date : 3/7/ . Acq . Tine ; 12: 3 Modified : Hin . Pea

k Height
Min . Pea

k width : O

C

.telliQua t 0.0 0 I 0.0 0 !

Valle y 15. 5 79565 5 c c Star t 1 En dTi p 

# I Sampte Name : *g120306a031 " Sampl a ID ' •LCS-120306^ - Ftte ' "01203063 . PeakNam e -13C8PFOA-IS(IS) ' Mass(BS):"421.0/376. 0 Commen t "Zpp b LCS ' AnnotaSon: "

Modified : ETDC . Algorithm : 1 Mm . Pea

k Height : Hin . Pea

k Hldth : Smoothin g width : R T Mindo» : Expecte dRT : telliCua n - IQ A O.O O cp s 0.0 0 se c

Height : Star t T J EndTim t 2.79e'00 5

Dat a printe d b yST W Printin g Time : 8:14:2 6 A M Printin g Date : Wednesday , Apri l Pag e 4 o f Pag e 3 3 o f 6 1GLP l 0-01-01 ; Interi m Repor t 2 7 Analysi s o f PFOAi n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2 Ginge r flG01330509 Result s Name : gl20306a.rd b

Dat a printe d b yST W Printin g Time : 8:14:2 6 A M Printin g Date : Wednesday , Apri l 1 1 Pag e Pag e 34 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFO AI n Surt'ace Wate r Ber t Jeffrie s Landfil l - Februar y201 2 Ginge r AG0133050 9 Result s Name : gl20306a.rd b ! Samp4eNam e •g120306a053 " Sampte ID . •GLPlO-01-01-27-009 ' F»e:'91203063.wi r PeakNanw*l3C8PFOA-IS(IS) ' Mass(M) . "421.0/376, 0 Comnnant •JPAL-SW-ET02-0 ' Annotation , ~

. Algorithm : Pea k Height : Pea k Width .

2.32e*00 5



# I Sampl e Name : 'g120306a060 - Sampl e ID ; "GLP l 0-01-01-27-015 " Fie : "fl120306a.wit r Pea k Name : •13C8PFOA-IS(IS) - Mass{as ) '421.0/376. 0 Comment : 'JPAL-SW-ETOS-LS * Annotation' " Sampl e Index : 6 0 Sanpl e Type : Concentration ; Calculate dCon e

Ptoc . Algo l Min . Pea

k Heigh t Min . e^a k

H . Snoothin g H . Expecte dBT

Height ; 1.0 0 ng/m L N/ A 2.40 5 3/7/201 2 2.3e 5 2.2e S IntelliQua n - IQA 2.1e S : 0.0 0 cp s 0.0 0 se c 2.0e 5 3 point s 1.9e 5 15. 5 mi n I.Be S N o 1.7B 5 Valle y 15. 5 mi n 1.6e S 6549 5 count s I.Se S 15. 3 mi n 1.4e S 1.3e S £ • 1.2e 5Inteti! l.le S I.OeS 9.0e 4 8.0O 4 7.0e 4 6.0e 4 5.0e 4 4.0e4 3.0e 4 2.0* 4 1.0e 4 0. 0 Dat a printe d b yST W Printin g Time : 8:14:2 7 A M Printin g Date : Wednesday , Apri l 11 , 201 2 Pag e Pag e 3 5 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFOAi n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2 Ginge r AG0133050 9 Result s Name : gl20306a.rd b

I I Sampl e Name"g1203D6a014 ' Sampl e ID : '11012-6-6 - Flo : -g120306a.wj r Pea k Name:'PFOA - Massfes ) '413.0/369. 0 amu,413.0/219. 0 amu,413.0/169. 0 amu * I I Commam : "OJ S ng/tri L F C std I n Synlh . Water

* AnnotaUor : 0.24 0 0.27 1 t/6/201 2



# I 

# - Pea k Name'-PFOA
- Masses) . •413.0ra69. 0 a i Comnrwnf

•0.2ppb LCS
- Anrtotabo n " Sampl e Index : 2 6 Sampl e Type ; O C Concentration ; 0.19 0 ng / Calculate dCone : 0.1& 2 ng / Acq . Date : 3/7/201 2 Modified . R T Hindov ; Expecte dRT : Us e Relativ e RT . 15. 0 15. 5 16. 0 16. 5 17. 0 17. 5 327 1 338 0 348 9 359 8 370 7 381 6 Tlrt>e, rrt n 

# I Sampte Name : •gl20306a02T - Sampte ID'-12001-160 ' Fla'•a120306a.wi r Pea k Name : 'PFOA ' UBSs(et ) "413.0/369. 0 amu,413.0/219. 0 emu,413.0/169. 0 a i Commen t 'Metho d Blank ' Annotation- " Sanpl e Index : 2 7

Proc . Algorithm :

Hin . Pea

k Height : Min . Peak

Midth : Smoochin g width : Us e Relatii . Bas e T o Eas e

I Sampte Name--Bl20306aO28 " Sampt e ID . •LCS-120306- TRte:'9120306a.wif T 

# I Sampt e Name - -g120306a031 ' Sampte ID - 'LCS-120306-4 ' Fite : 'g120306a.wi( r PeakNam e 'PFOA ' Uass(e£)-'413.0/369.0amu,413.0/2190amu.413.0/16g.0amu ' Commen t *2pp b LCS ' Annotatioo ' ~ ;ampl e Index : 3 1

14J S 

### _7v _ Calculate dCone : Acq . Date . Acq . Time
7.5e5 7.0e5 6.5e5 e.0e5 5.5e5 5.0e5 '

S 3,5e5
- 30e5 ' 2.5e5
- 2.0e5 '

Dat a printe d b yST W Printin g Time : 8:14:2 7 A M Printin g Date : Wednesday , Apri l 11 , 201 2 15. 0 15. 5 16. 0 16. 5 17. 0 17. 5 327 1 338 0 348 9 359 8 370 7 381 6 

# 1 15.8 8 

# A . Pag e 7 o f

9 Pag e 3 6 o f 6 1GLP l 0-01-01 ; Interi m Repor t 2 7 Analysi s o f PFO Ai n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2

** * Ginge r AG0133050 9 Result s Name : gl20306a.rd b

I Sampte Nam e 'g1203DGa034 - Sampte 10 : TCS-12D306-7 * Fla''g120306a.wii r

5.0e6 ' 4.ee6 '

3.8e6 3.6e6 3.4e6 3.2e6 3.0e6 2.ee 6 2.6fl6 2.4e6 2.2e6 2.0e 6 1.8e 6 1.6e 6

8.0e 5 6.0e5 - 4.005 2X)t,5- 153 ^

346 9 3598 

# I Sampte Name . -91203068041 ' Sampte 1 0 -GLP l 0-01-01-27-025 " Fite . 'g120306a.wi r Pea k Nam e -PFOA ' Massfes) . '413.0/369. 0 amu,413.0/219. 0 amu.413.0/169. 0 amu ' Commen t "JPAL-SW-TRIPI- C Annoialio n " Sanpl e Index : 1 1 Sanpl e Type : Unknow n

nthra ; IntelliOu a

Smoothin g Wi

c B T Window : Expecte d RT :

I Sampl e Nam e •g12O306aO45 ' Sampt e I D "GLP l 0-01-01-27-005 ' Fite:'g120306a.wi r I Sampte Name : •g120306a04 rSampte ID : •GLP1CKI1-O1-27-026 " Peak Name:-PFOA-

Mass<es)

'413.0/369.0

armi,413.0/219.0

amu, I Comment:'JPAL-SW-TRIPI-LS' Annotation

~ Concentiatlon ; Calculate d Cone : Acq . Date ; Pea k Name : 'PFOA ' Mass(es) ' "413,0/369. 0 a i • Comment-JPAL-SW-ETOI-O - Annotation: ' Sampl e Index : 4 5 Sampl e Type ; Unknow n 3.ee 5 3.6a 5 3.4e 5 3.2a S 3,0e 5 2.8e 5 2.Se 5 2/4e 5 2.2* 5 2.0o5
-

1.285
- 1.0e5
- Pro c Algo i Nois e Pere c Base . Sub . Windo H Peak-Split . Facto i Pepor t Larg > Hin . Pea k Heigh t Min . Pea k Width ;

Peak :

Dat a printe d b yST W Printin g Time : 8:14:2 7 A M Printin g Date : Wednesday , Apri l 11 , Pag e Pag e 3 7 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFOAi n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2 Ginge r AG0133050 9 Result s Name : gl20306a.rd b

• Sampte Nam e -9l20306a053 - Sampt e ID'*GLP10-01-Ol-27-009 ' F<e : '9l20306a.wi r B Pea k Name ' 'PFOA ' Mass(B5) : '413.0/369. 0 amu,413.0/219, O amu,413.0/169.0amu ' I I Comma m 'JPAL-SW-eT02-0 ' /Annotation.' " Sampl e Index : 5 3 Sacapl e Type : Unknow n Coneentratton ; IJ/ A Calculate dCone : 0.0025 6 ng/m L5 Acq . Date : 3/7/ZOl Z Ac qTime : 9-24;0 9 A M

! . Sub . t-Spll i Facto i Hin . Pea

k Height ; Min . Pea

k Midth : Smoothin g Nidth : R T Window : i BT :

7.33e»O0 3 cp s

15.4 8



# 1) I Sampte Name'*g12D30&a058 ' Sampte I D 'GLP10-01-01-27-013 " Fite ' '9l20306a.wi r 

### I Pea k Nam e 'PFOA ' Mass(es) : '413.0/369. 0 ar Commen t "JPAL-SW-ETOS-O " Annotation : * • Sampl e Index ; 5 8 Sampl e Type : Unknow n Calculate dCone : O.I H ng/m L Acq . Date : 3/7/201 2

r : 15. 5 19521 9 c

c i.Bie-t-DQ t 1 5 2 j,413.0/219. 0 emu,413.0/ 1 G9. 0 a i

13. 0 13. 5 14. 0 14. 5 15. 0 15. 5 16. 0 16. 5 283 5 2944 305 3 316 2 327 1 ^ 338 0 348 9 359 8 

# I SampteNam e 'g120306a060 " Sampt e ID:'GLP10-01-01-27-O15 ' Rle:-9l20306a,w1f r Pea k Name ' 'PFDA ' Mass{es) - "413,0/369. 0 amu,413,0/219. 0 amu,413.0/169, 0 amu ' Comment ' 'JPAL-SW-ET03-LS - Annotation : ~ ampl e Index : 60 3.B«5
- 3.6e5 ' 3.4* 5 3.2e5
- ZXS«5
- 2£o 5 2.6e5
- 2.4e5
- 2.20 5 2.0e5
- lJe5
- 1.6e5
- Modified : R T Window : Expecte dRT ;
Height : Star t Ti n EndTime : I Sampl e Name-'Bl20306a066 ' Sampt e I D 'GL P 10^)1-01-27-017 ' Fite'•Bl20306a.wif r Sampl e Type Base . Sub . Window : Peak-Split , Factor : Repor t Larges t Pea l Hin . Pea k Height : Smoothin g R T Window : Expecte d I

I 15.8

7 

# i l

Dat a printe d b yST W Printin g Time : 8:14:2 8 A M Printin g Date : Wednesday , Apri l 11 , 201 2 Pag e 9 o f 9 Pag e 3 8 o f 6 1GLP l 0-01-01 ; Interi m Repor t 2 7 Analysi s o f PFO Ai n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2 

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

Pag e 3 9 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFOAi n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2



# 3 M Environmeiita l Laborator y f\/fethod 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 : /

//?// / Approve d By :

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

ETS-8-044. 1 Pag e 1 o f 2 2 Method 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 4 0 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFOAi n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2


### 1 Scop e an d Applicatio n Thi s metho d describe s th e direc t injectio n analysi s o

f perfluorinate d compound s (PFCs ) fro m wate rmatrice s usin g high-perfomianc 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 i sulfonamide s an d perfluorinate d alky I acid s (PFAAs ) suc h as 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 altemat e metho d suc h a s ETS-8-15 4 "Detenninatio n of Perfluorinate d Acids , Alcohols , Amides , an d Sulfonate s I n Wate rB ySoli d Phas e Extractio n an d Hig h Performance Liqui d Chromatography/Mas s Spectrometry" . Th e metho d i s applicabl e t o bot h extema l standar d an d intema l standar

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

(CASRN) PFB A(C 4 Acid ) Perfluorobutanoi caci d 375-22- 4 PFPeA(0 5 Acid ) Perfluoropentanoi caci d 2706-90- 3 PFHx A(0 6 Acid ) Perfluorohexanoi caci d 307-24- 4 PFHp A(0 7 Acid ) Perfluoroheptanoi 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(01 0 Acid ) Perfluorodecanoi caci d 335-76- 2 PFUn A(Oi l Acid ) Perfluoroundecanoi caci d 2058-94- 8 PFDoA(01 2 Acid ) Perfluorododecanoi caci 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 ) Perfluorohexanesulfoni 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 o f thi s method . Metho d Flexibilit

y- Thi s i s a perfomiance-base d metho d an d ma yb e generall yapplie d t o th e determinatio 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 of sample s ar e 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 pennitte d 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 perfomnanc e o rt o meet dat a qualit

y objective s fo rth e study . I n al l case s wher e metho d modification s are implemented , th e batc h

' Th e metho di s supporte

db y validatio n 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 contro l 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. ) FD A 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 Anne x I I(Par t A , sectio n 4 ) an dAnne x II I (Par t A,section 5 ) o f

Directive 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 rbyLC/MS/MS ; Direc t Injectio n Analysi s Pag e 4 1 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFOAi n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2 analytica l QC s (sectio n 9 ) must 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 Method Summary Wate rsample s are analyze d a s 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

ynot 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 , HPLC 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 perfluorocarboxyli cacid s (PFCAs ) are reporte d a s 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 targe t 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 of stud ysample s tha t 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 instmmen 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 predetennine 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 instrumen t respons e wit h respec t t o analyt e concentration . 

### 3. 4 Laboratory 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 that o f 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 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 4 2 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFOAi n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2
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 a s a sampl e i n ai 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 determin 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 referre d 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 of 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 , as 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 targe t 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 of 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 of 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 Spike (TBMS ) A n aliquot o

f AST M Typ e I , HPL

C grad e water , o rothe rsuitabl e water , t o whic h know n quantitie s of 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 of th e collectio n bottles . Th e TBM S i s analyze d exactl ylik e a stud ysampl e t o hel p detemnin 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 ar e 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 intema l standard(s ) are stabl e isotop e labele d version s o f 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 intema l standar d i s use d fo rcalibration . Surrogat e IS s are applie d whe n stabl e isotop e IS s o f targe t analyte s are unavailable . Asun-ogat 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 interna 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 target 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 least thre e level s (tw

o level s fo rSRSs ) i n triplicat e ar e 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 detennin 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 of a sampl e t o whic h know n quantitie s of targe t analytes , IS s an d SRS s (whe n applicable ) ar e adde d i n th e laboratory . Th e LM S i s analyze d exactl ylik e a laborator

ysampl e t o determin e whethe rth e sampl e matri xcontribute s bias t o th e analytica l results . Th e endogenou s concentration s of th e analyte s i n th e sampl e matri x must b e determine d i n a separat e aliquot an d th e measure d value s i n th e LM S correcte d fo 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 rbyLC/MS/MS ; Direc t Injectio n Analysi s Pag e 4 3 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFOAi n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2
3.1 2 Laborator y Sampl e Aportio n o raliquot o

f a sampl e receive d fro m th e fiel d fo rtesting . 3.1 3 Limi t o fQuantitatio 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 tha t ca n b e reliabl yquantitate d withi n th e specifie d limit s o f 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 tha t meets metho d acceptance criteria . Th e LLOQ fo reac h target analyt e i s establishe d fo reac h analysi s batc h as th e lowest calibratio n standar d wit h are a counts a

t least twic e tha

t of th e averag e are a counts o f th e procedura l blanks . Th e uppe rlimi t o

f quantitatio n (ULOQ ) fo ra n analytica l batc h i s th e highest concentratio n tha t ca n b e reliabl yquantitate d withi n th e specifie d limits o f 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 a s th e ULOQ . 3.1 4 Method/Procedura l Blan k A n aliquot of contro l matri xthat i s treate d exactl ylik e a laborator

ysampl e includin g exposur e t o al l glassware , equipment , solvents , an d reagents that are use d wit h othe rlaborator y samples . Th e metho d blan k i s use d t o detennin 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 yof materia l intende d t o represen t th e origina l sourc e 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 intema l standar

d fo rquantitation . Sun-ogat e IS s are use d whe n isotopicall ylabele d counterparts of th e targe t analyt e are 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 a s a n interna l standard , that i s adde d t o eac h sampl e an d appropriat e Q C sampl e as a mean s t o evaluat e th e metho d performance fo ra chemica l clas s of compound s (e.g. , PFSAs , PFCAs) . 3.1 9 Workin g Standar d (WS ) Asolutio n o

f severa l analyte s prepare d i n th e laborator yfro m SSS s an d dilute d a s neede d t o prepar e calibratio n standard s an d othe rrequire d analyt e solutions . 4 Warning s an d Caution s 4. 1 Healt h an d Safet y Th e acut e an d chroni ctoxicit 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 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 4 4 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFOAi n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2 Th e laborator

yi s responsibl e fo rmaintainin g a saf e wor k environmen t an d a curren t awarenes s of loca l regulation s regardin g th e handlin g of th e chemical s use d i n thi s method . Areference fil e of materia l safet 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 of 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 infomnatio 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 interi'erence s unde rcondition s of analysi s byrunnin 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 , HPLC parts , etc . Th e us e of disposabl e micropipette s o rpipette s t o aliquot standar d solution s i s recommende d t o mak e calibratio n standard s an d matri xspikes . 6 Instrumentation , Supplies , an d 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 , as 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 : D o 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 HPLC autovial s Disposabl e pipettes , polypropylen e o rglas s a s appropriat e Centrifug e capabl e o

f 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 perfomnanc

e ma yb e achieve d usin g chemical s obtaine d fro m othe rsuppliers . D o 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 of 2 2 Metho d o f 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 4 5 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFO Ai n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2 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 9 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 ) PFTriDA , 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-isotopicallylabele d Perfluorooctanesulfonat e (SRS ) PFUnA[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 -''XdPFDA , [1,2,3,4,5,6, 7 -"CyjPFUnA , [1, 2 -^^CJPFDoA , [1,2,3-^^CsjPFHS , [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 . Alternatively , individua l stabl e isotop e IS s ca n b e use d t o prepar e 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 o f Ammoniu m acetat e an d dissolve i n 2. 0 L o

f reagen t water . Syntheti cGroundwate r(containin g 2 5 pp m C a an d Mg ) - Weig h 0.6 1 g of Calciu m Acetat e an d 0.92 g o

f Magnesiu m Acetat e an d dissolve i n 6. 0 L of reagen t water . Note : Alternative volume s ma yb e prepare d a s lon g as th e ratio s o f th e solven t t o solut e ratio s ar e maintained .
ETS-8-044. 1 Pag e 7 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 4 6 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFO Ai n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2
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 flnal volume s ma

yb e change d t o sui t th e need s o f a particula rstudy . Fo rexample , p 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 \iglm 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 , aci d [ETS-4-031 ] 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 125 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 con-ectio n i s give n belowfo r PFOS .

, , molecula rweigh t of anio n sal t correctio n facto r= =

moclecula rweigh t of sal t

49 9 PFO S (K^ ^ )sal t correctio n facto r= —= 0.927 5

. 53 8 1 0 m g CsFiySOsK

* wit h purit

y90 % = 8.35 m g CsFuSOa"(1 0 mg*0.90*0.9275=8.3 5 mg ) 1 0 \iglm L (10,00 0 ng/mL ) mixe d workin g standard—Ad d 5. 0 m L eac h of th e 100 pg/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 (jg/m L (1,00 0 ng/mL ) mixe d workin g standard—Ad d 0. 5 m L o f th e 100 pg/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 |jg/m L (10 0 ng/mL ) mixe d standard—Ad d 0.05 m L of th e 100 pg/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 worthin g standard s i n accordance wit h laborator y standar d operatin g procedur

e o ri n a refrigerato ra

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

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

e calibratio n solution s i n AST M Typ e I water , HPL C water , othe r suitabl e water , o ra mixtur e o f solven t an d wate rusin g th e infomnatio n i n Tabl e 2 a s a guideline . Note : Volume s of wate ro rwater/solven t mixture s an d wori<in 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 belo wca n b e prepare d a s needed . Fo rth e quantitatio n o

f PFO Aan d PFOS , reference material s of certifle d mixe d linea ran d branche d isome rare prefen-ed . Altemately , reference material s o f 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 SurTt>gat e Recover

yStandard (SRS ) Fo rI S calibration , stabl e isotop e interna 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 hav e 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 nassessmen

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 nb e foundi n3 M repor

t Ell-0560 . ETS-8-044. 1 Pag e 8 o f 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 4 7 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFO Ai n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2 concentratio n of th e intema 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 concentratio n of th e interna l standar d spikin g solutio n i s typicall y2 pg/mL . Aseparat e zer o 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 solutio 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 flnal calibratio n curve must consist o f a t leas t si x calibratio 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 interna l standar

d an d sun-ogat

e standard . Tabl e 1 lists recommende d stabl e isotop e interna l standard s fo rsevera l PFS Aan d PFC

A targe t 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 , ri,2,3,4,5,6,7,8,9-^^C9]PFNA , [1,2,3,4,5, 6 -^^CeJPFDA , [1,2,3,4,5,6, 7 -^XyjPFUnA , [1, 2 - ^^C2]PFDoA , [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]FOSA (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 solution . Alternative source s of certifle d stabl e isotop e labele d targe t analyte s are applicable . Alternatively , 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 targe t 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 entire project/study . Note : som e o f th e compound s liste d beloware 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 , surrogat e isotopicall ylabele d PFCA s are use d fo rPFCAs , an d sun-ogat e isotopicall ylabele d PFSA s are use d fo rPFSAs . Tabl e 2 provide s example s o f 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 of 2 2 Metho d o f 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 4 8 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFO Ai n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2 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 n Labs

(Mi x o r Individual ) "C4-Perfluoropentanoi

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

S fo r PFPe A Wellingto n Labs

(Mi x o r Individual ) "C2-Perfluorohexanoi

c acid [l,2-"C2]PFHx A I S fo r PFHx A Wellingto n Lab s

(Mi x o r Individual ) "C4-Perfluoroheptanoi

c aci d [l,2,3,4-"C4]PFHp A I S fo r PFHp A Wellingto n Labs

(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 n Labs (Mi x o r Individual ) "Cg-Perfluorononanoi

c aci d [!,2,3,4,5,6,7,8,9-"C,]PFN A I S fo r PFN A Wellingto n Labs

(Mi x o r Individual ) "Ce-Perfluorodecanoi

c acid [1,2,3,4,5,6-"C6]PFD A I S fo r PFD A Wellingto n Labs

(Mi x o r Individual ) "C7-Perfluoroundecanoi

c aci d [1,2,3,4,5,6, 7 -"ClPFUn A I S fo r PFUn A Wellingto n Labs

(Mi x o r Individual ) "C2-Perfluorododecanoi

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

A Wellingto n Labs (Mi x o r Individual ) "Oi-AmmoniumPerfluorobutan e sulfonat e ["02]PFB S I S fo r PFB S RT I Intemationa l (Individual ) "C3-Ammoniu

mPerfluorohexan

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

(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 n Labs (Mi x o r Individual ) "Cg-Perfluorooctanesulfonamid e [l,2,3,4,5,6,7,8-"C8]FOS A I S fo r FOSA Wellingto n Lab s (mix )

RT I Intemationa

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 aci d [1, 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 dC8 Wellingto n

ETS-8-044. 1 Pag e 1 0 of 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 4 9 o f 6 1GLP l 0-01-01 ; Interi m Repor t 2 7 Analysi s o f PFOAi n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2

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

ofWS.tig/mL Volume of WS.fd. Volume

of IS (2 fjg/mL), fd. Concentration of Surrogate, fig/mL Volume of Surrogate, /jL Volume of ASTM Type 1 Water, or other suitable solvent mL 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 curve poin t 0.1 0 4 0 5 0 0.2 0 2 0 10 0 0.0 5 ng/m L curve poin t 0.1 0 5 0 5 0 0.2 0 2 5 10 0 0. 1 ng/m L curve poin t 0.1 0 10 0 5 0 0.2 0 5 0 10 0 0.2 5 ng/m L curve poin t 0.1 0 25 0 5 0 0.2 0 12 5 • 10 0 0. 5 ng/m L curve poin t 1. 0 5 0 5 0 0.2 0 25 0 10 0 1 ng/m L curve poin t 1. 0 10 0 5 0 0.2 0 50 0 10 0 2. 5 ng/m L curve 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 curve poin t 10. 0 10 0 5 0 10. 0 10 0 10 0 25. 0 ng/m L curve poin t 10. 0 25 0 5 0 10. 0 N A 10 0 50. 0 ng/m L curve 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 curve poin t 10. 0 100 0 5 0 10. 0 N A 10 0 N/ A- No t Applicabl e (1 ) Sample s requirin g analysi s fo rPFUnA , PFDoA , PFTrDA , an d FOS Asfioul d b e analyze d agains t a calibratio n curv e prepare d i n 1: 1 syntheti cgroundwater:MeOH .

ETS-8-044. 1 Pag e 1 1 o f 2 2 Metho d o f 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 0 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFO Ai n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2 

### 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 xspike an d target 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 ar e use d fo rth e sampl e collectio n containers . (Volume s o

f th e bottle s ma

yvar ydependin g o n ho

wmuc h sampl e i s require d t o meet data qualit yobjectives. ) Sampl e collectio n volume s are projec t specifi can d base d o n data qualit yobjectives . Th e Nalgen e bottle s d o no t requir e an ypretreatmen t prio rt o use . Typically , placemen t o f 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 a s 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 Note t o Fil e o ro n a sampl e preparatio n wori^shee t an d shoul d includ e th e followin g infomiation : dat e prepared , tota l numbe ro f bottle s prepared , numbe ro f sampl e sites , th e standard'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 infomnatio 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 Q C sampl e t o whic h know n quantitie s of appropriat e target 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 are 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 o f targe t analyt e FM S samples . Sampl e quantitie s are detennine 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 spike a t a n appropriat e leve l i s made . Typicall ya lo

wan d a hig h target analyt e spike are prepare d fo reac h samplin g location . 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 bia s 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 solutio n i s adde d t o th e empt ybottl e prio rt o sampling . Th e volum e o

f spik e 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 of th e appropriat e targe t analytes , ISs , an d SRSs . Th e target analyt e matri x spikin g solutio n i s ofte n th e sam e a s 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 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 1 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFOAi n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2
50 0 n L of a 0. 1 ixg/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 Recovery Standar d I f analysi s of 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 of 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

yintema l standar

d (IS ) i s include d i n th e projec t objective , a n appropriat e volum e of interna 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 intema l standar

d a t a final desire d spik

e concentratio n o

f 1 ng/mL . Fo rth e tri p blank , th e SR S spike 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 are 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

wdata 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 . At a minimum , metho d blank s ar e analyze d prio rt o instrumen t calibration , prio rt o th e analysi s of CC V samples , afte rever y1 0 sampl e injecfions , an d a t th e en d of th e analytica l njn . Th e mea n are a coun t o rare a ratio s whe n usin g intema 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 o

f th e are a counts , o rare a ratio s whe n usin g interna l standar d calibration , 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 calibrafion , of th e metho d blank s excee d 50 % of th e LOQ standard , the n th e LO Q 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 220 % RP D criteri a are flagged an d reporte d as outsid e of Q C 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 of target 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 are prepare d fo reac h sampl e an d analyze d t o detemnin e th e matri xeffec t o n spike recover

yefficienc yo f 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 time s th e endogenou s concentratio n o r approximatel y4-1 0 time s th e LOQ concentratio n of eac h target 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 2 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFO Ai n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2
La b matri xspik

e 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 % o f 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 ar e reporte d a s NR , where N R i s deflne d as "No

t Reportable " dat a 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 o

f 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 concentratio 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 % o

f th e uppe rLOQ . Fo reac h target 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 rtarge t 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 o

f 9 ) of LC S sample s ar

e withi n 20 % of thei rrespective nomina l valu e (33 % o f th e QC 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 flagged as outsid e metho d acceptance criteria . Al l LC S sample s wil l b e contro l charte d as pe rETS-4-026 . I f th e averag e recover yof on e o

f th e spikin g level s exceede d th e analytica l metho d uncertaint yas detemnined 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 % of th e LC S sample s fai l t o meet metho d acceptance criteria , th e dat a 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 preferred . 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 ) o f 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 determin e th e matri xeffec t an d sampl e holdin g tim e o n th e spik

e recover yof eac h target 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 quantifie s o f appropriat e targe t analyte s are adde d t o th e sampl e bottl e i n th e laborator

ybefore th e bottle s are sen t t o th e field. Typicall ya lo wan 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 targe t 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 % of th e expecte d valu e o rcoul d no t b e assesse d becaus e th e FM S (target analyte ) wa s 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 targe t 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 fiagged 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 dat a ar e 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 sinc e th e most appropriat e spike leve l passed . ETS-8-044. 1 Pag e 1 4 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 3 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFOAi n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2 3 . ) I f th e targe t analyt e FM S recoverie s are outsid e of th e ±30 % acceptance rang e bu t a t leas t 3 0 acceptabl e historica l reportabl e FM S sampl e results ar e available , th e dat a 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 dat a wit h FM S recover youtsid e o

f ±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 criteri a wit h a n expande d uncertainty . 5 . ) I f FM S recover

yi s outsid e of ±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 of 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 of 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 of 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 of th e FMS , ISs , an d SR S tm e values . Th e averag e o

f th e sampl e an d th e field duplicat e shoul d b e use d t o calculat e th e 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 . • Dilut e 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 detennin 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 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 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 rI S quantitation , stabl e isotop e interna l standard s of 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 instruments a s wel l a s 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 are fo rillustrative purpose s only . Equivalen t perfomianc 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 perfomnanc

e that meets th e requirements o f thi s metho d i s th e responsibilit yo f 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 o f Analysi s fo rth e Determinatio n o f Perfluorinate d Compound s i n Wate rbyLC/MS/MS ; Direct Injectio n Analysi s Pag e 5 4 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFOAi n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2 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 : Turia

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 rWindow s 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 , 5n m o r2. 1 m m x5 0 mm , 5|xm) ma yb e attache d on-lin e afte rth e purg e valv e an d befor e th e sampl e injectio n por t t o retar d an d separat e an yresidu e contaminants that ma

yb e i n th e mobil e phas e and/o rHPLC system . HPLC Column : Betasi l C18,4.6m m x100mm , 5\i m (ThennoElectro n Corporation ) Colum n Temperature : 35° C Injectio n Volume : 5p L Mobil e Phas e (A) : 2m M Ammoniu m Acetat e i n AST M Typ

e I wate r (Se e 7.3

) Mobil e Phas e (B) : Methanol Tabl e 3 . Liqui d Chromatograph y Gradien t Program . step Number 7ota/

Time (min) Flow

Rate (ftUmin) Percent A (2 mM ammonium acetate) Percent B (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 ar

e met . I t ma yb e necessar

yt o adjust th e HPLC gradien t i n orde rt o optimiz e instrumen t perfomiance . 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 C I 8 etc. ) ma yb e used .

ETS-8-044. 1 Pag e 1 6 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 5 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFO Ai n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2 Tabl e 4 Suggeste d MR M Transition s fo r Targe t Analytes , Surrogates , an d Interna l Standard s

Analyte Analyte Description Mass Transition 01 (amu) Mass Transition

OS (amu) PFB A (C 4 Acid ) Targe t 21 3 16 9 PFPe A (C 5 Acid ) Targe t 26 3 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 (Oi l Acid ) Targe t 56 3 519,269,21 9 PFDo A (01 2 Acid ) Targe t 61 3 569 , 169,31 9 PFT A (CI 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 299 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 [1,2,3,4,5-"CslPFPe

A I S fo r PFPe A 268 22 3 [l,2-''C2lPFHx A I S fo r PFHx A 31 5 270 [1,2,3,4
- "C4IPFHP

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 37 6 [ 1,2,3,4,5,6,7,8,9-"CIPFN A I

S fo r PFN A 472 42 7 [1,2,3,4,5,6-"CsJPFDA I S fo r PFD A 51 9 47 4 [1,2,3,4,5,6,7-"CTlPFUn

A I

S fo r PFUn A 570 52 5 [l,2-"C2lPFDo A I S fo r PFDo A an dPFT A 61 5 570 ['^OJIPFB 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
- "CilPFO S I S fo r PFO S 50

3 8

0 [l,2,3,4,5,6,7,8-"C8lF0S A I S fo r FOS A 50

7 8

0 [l,2,3,4-"C4lPF0 A Surrogat e (C4-C 8 Acids ) 41 7 372 [1,2,3,4
- "C4]PFO

S Surrogate(Sulfonates , FOSA ) 50

3 8

0 [l,2-"C2]PFUn A Sun-ogat 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 tha t retentio n tim e criteri a ar e me t t o assure adequat e specificity . Whil e th e daughte rion s ma yb e chose n a

t th e discretio n of th e analyst , mass transitio n 9 9 i s suggeste d fo rPFOS . Quantitatio 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 of 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 o f 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

yintema l standar

d o rextema 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 intema l standar d calibratio n doe s no t meet calibratio n acceptance criteria , externa 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 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 5 6 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFOAi n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2 Tabl e 4 Suggeste d MR M 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 26 3 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 (C I 1 Acid ) Targe t 56 3 519,269,21 9 PFDo A (CI 2 Acid ) Targe t 61 3 569 , 169,31 9 PFT A (CI 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 49 9 80 , 99 , 13 0 [1,2,3,4-"C4IPFB A I S fo r PFB A 21 7 17 2 [1,2,3,4,5-"CslPFPe

A I S fo r PFPe A 268 22 3 [l,2-"C2lPFHx A I S fo r PFHx A 31 5 270 [1,2,3,4
- ''C4IPFHP

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 [1, 2 -"C2IPFD0

A I S fo r PFDo A an dPFT A 61 5 57 0 ['*02lPFB 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
- "CilPFO S I S fo r PFO S 50

3 8

0 [1,2,3,4,5,6,7,8-"CslFOS A I S fo r FOSA 50 7 8

0 [l,2,3,4-"C4lPFO A Sun-ogat e (C4-C 8 Acids ) 41 7 372 [1,2,3,4-"C41PF0 S Sun-ogate(SuIfonates , 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 tha t retentio n tim e criteri a ar e me t t o assure adequat e specificity . Whil e th e daughte rion s ma yb e chose n a

t th e discretio n of th e analyst , mass transitio n 9 9 i s suggeste d fo rPFOS . Quantitatio 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 of 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 , as lon g as 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 calibratio n doe s no t meet calibratio n acceptance criteria , externa l calibratio n ca n b e applied . Se e Tabl e 1 fo r ETS-8-044. 1 Pag e 1 7 of 2 2 Metho d o f 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 6 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFO Ai n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2 recommende d applicatio n o f 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 calibratio n curve shoul d b e applie d consistentl ythroughou t a study . An ychang e shoul d b e thoroughl ydocumente d i n th e ra wdata . Hig h and/o rlo

wpoints ma

yb e exclude d fro m th e calibratio n curve s t o provid e a bette 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-detennine 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 rati o i f quantitatin g b yIS ) are no

t a t least twic e that of 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 detenninatio 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 coefllcien t (r) of 0.995) . Eac h poin t i n th e curve must b e withi n ±25 % of th e theoretica l concentratio n wit h th e exceptio n of th e LLOQ , whic h ma 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 , perfon n routin e maintenance o rprepare 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 verification s (CCV) are 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 of th e sam e standard s use d t o construc t th e calibratio n curve , at 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 must b e withi n ±25 % t o b e considere d acceptable . Th e calibratio n curve an d th e las t passin g CC V 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 of 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 , 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 of th e calibratio n curve an d ar

e repeate d injection s fro m on e autosample rvial . I t i s suggeste d that th e syste m suitabilit yinjection s hav

e are a counts o rare a ratio s whe n usin g interna l standar d calibration , wit h a target RS D o f <5 % an d a targe t retentio n tim e RS D o f <2% . There i s n o define d acceptabilit ylimi t o n thes e results a s 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 rtim e 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- 1 OOpL ) of eac h standard , analytica l sampl e an d blan k into th e instrumen t (unles s a n on-instrumen t sampl e dilutio n i s desired) . Sample s containin g analyte s that are quantitate d above th e concentratio n o f 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 of 2 2 Metho d of Analysi s fo rth e Determinatio n of Perfluorinate d Compound s i n Wate rbyLC/MS/MS ; Direct Injectio n Analysi s Pag e 5 7 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFOAi n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2 

### 1 2 Data Analysi s an d Calculation s Th e chromatograph yanalysi s softwar e 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 yo f th e LC S usin g th e followin g equation : LC S Concentratio

n (— ) LCS % recover

y = * 100 % n g 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 - ^"^'y*® foun d (ng/mL ) - Averag e analyt e foun d i n sampl e (ng/mL ) ^ . | Q Q Analyt e adde d (ng/mL ) 1 3 Analysi s Batc h Metho d Performanc e Criteri a An ymetho d perfomnanc

e 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 performance sectio n are no t met , maintenance ma

yb e perfonne 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 data are t o b e reporte d whe n perfomianc 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 o f th e report . 13. 1 Syste m Suitabilit y - Analysi s Batc h Aminimu m of 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 . 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 hav

e are a counts wit h a targe t RS D o f ^5 % an d a targe t retentio n tim e RS D of 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 m n o rtim e period . An yeffec t o f syste m suitabilit

yi s incorporate d i n th e QC 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 o f determinatio n (r^

) valu e fo rth e calibratio n curve mus t b e greate rtha n o r equa l t o 0.99 0 correspondin g t o a con-elatio 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 Performance : Th e calibratio n standard s that are intersperse d throughou t th e analytica l sequence are evaluate d as continuin g calibratio n verification s i n additio n t o bein g par t o f th e calibratio n curve . Th e accurac y ETS-8-044. 1 Pag e 1 9 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 8 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFOAi n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2

o f eac h curve poin t must b e withi n 25 % of th e theoretica l valu e (withi n 30 % fo rlowest 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 lowes t 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 least 2X that o

f th e averag e are a counts fo ral l prepare d procedura l blank(s) . B ydefinition , th e measure d valu e of th e LLOQ 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 o f uniqu e ions . 13. 3 Blank s - Method/Procedura l Blank s an d Tri p Mettiod/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 . At a minimum , metho d blank s ar e analyze d prio rt o instmmen t calibration , prio r t o th e analysi s of CC V samples , afte rever y1 0 sampl e injections , an d a t th e en d of th e analytica l run . 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 Biank : 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 are 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 of 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 yof a spikin g leve l fall s outsid e metho d acceptance , bu t a t leas t 67 % ( 6 ou t o f 9 ) of LC S sample s ar

e withi n 20 % of thei rrespective nomina l valu e (33 % of th e QC 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 . A H LC S sample s wil l b e contro l charte d as pe rETS-12-012 . 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

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 of 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 ) o f 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 target 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 fiagge d 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 a s NR , where N R i s define d a s "No t Reportable " dat a 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 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 detemnined 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 INTERNATIONALANS/ISO/IE D STANDAR

D 1702 5 referenc e (GUM , Guid

e t o th e Expressio

n o f Uncertaint y i nMeasurement) . 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 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 5 9 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFOAi n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2

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 of Uncertaint

yi n Measurement) an d describe d i n ETS-12-012 . At least thirt ydat a points ar

e require d fo r detenninin 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 most recen t fiftydat a points are use d fo rdetemninin g th e metho d uncertainty . Whe n les s tha n thirt

yLC 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 data 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 detemnined as withi n 100±20% . Analysi s batc h sampl e dat a wit h FM S recover youtsid e o

f ±30 % bu t withi n ±50 % o f th e expecte d valu e are flagged an d reporte d as outsid e of Q C acceptance criteri a wit h expande d uncertainties . Data wit h FM 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 as "No t Reportable " dat a 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 fiagged 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 Aare preferred . Quantitatio n i s perfoime d b yintegratin g th e linea ran d branche d isomer s together . Altemately , 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 of 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/PFO A TBMS s ma

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

f quantitatio n ca n b e perfomned 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 ar e 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 of PFOA/PFOS . Thi s ensure s that th e concentratio n detecte d i s withi n th e a rang e of th e calibratio 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 of PFOS/PFO

A o rlinea rplu s branche d isomer s of PFOS/PFOA . 1 4 Pollutio n Preventio n an d Wast e Managemen t Wast e generate d whe n perfomnin 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 interna 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 Results."d.)Adams , T.M. , "A2L A Guid e fo r th e Estimatio

n o f Measuremen

t Uncertaint

y i n Testing" , Jul

y 2002 . ETS-8-044. 1 Pag e 2 1 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 6 0 o f 6 1GLP10-01-01 ; Interi m Repor t 2 7 Analysi s o f PFOAi n Surfac e Wate r Ber t Jeffrie s Landfil l - Februar y201 2

1 5 Record s Eac h dat a packag e generate d fo ra stud ymust includ e al l supportin g infomnatio n fo rreconstmctio n of th e data . Infomnatio 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 , instmmen t ru n lo g (instmmen t batc h records , instmmen t acquisitio n method , summar ypages) , instrumen t results files, chromatograms , calibratio n curves , an d data calculations . 1 6 Affecte d Document s None . 1 7 Revision s Revisio n Numbe rSummar vo f 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 Handling)

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 Method 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 detennination

of analytical

method uncertainty

and quantitation

of PFOA/PFOS. 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 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 6 1 o f 6 1