GLP10-01-02 : Interi m Repor t 2 6 - Analysi s o

fPFBS . PFHS . an d PFO S i n Surfac e Wate r Sample s Collecte d a

t Bert Jeffrie s Landfil l i n Decatur . A L i n February 201 2

Stud y Titl e Analysi s o

fPerfluorooctan e Sulfonate (PFOS) , Perfluorohexan e Sulfonat e (PFHS ) an d Perfluorobutan e Sulfonat e (PFBS ) 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 Data 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 Wa y Wes t Chester , PA1938 0 Phone : 610-701-376 1 Autho r Susa n Wol f 3 M Environmenta l Laborator y Interi m Repor

t Completio n Date Dat e ofsignin g Performin g Laboratory 3 M Environmenta l Healt h an d Safet yOperation s Environmenta l Laborator

y 3 M Center , BId g 260-05-N-1 7 S t Paul , M N 55144 Project Identificatio n GLP10-01-02-2 6 Tota l Numbe r o

fPage s 7 7 

# mm

Th e testin g reporte d herei n mee t th e requirement s o fANSI/ISO/lE C 17025:200 5 "Genera l Requirement s fo r
, T^ . th e Competenc e o f Testin g an d Calibratio n Laboratories", I n accordanc e wit h th e A2LATestin g Certificat e # |ACCREPlf¥D l 2052.01 . Testin g tha t compile s wit h thi s Internationa l Standar d als o meet s principle s o fIS O 9001:2000 . Testin g Cert #2052.0 1Thi s pag e has bee n reserve d fo rspecifi ccountr yrequirements
.

Pag e 2 of 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o fPFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2



### GL P COMPLIANC E STATEMEN T Repor t Title : Interi m Repor

t 2 6 - Analysi s o

fPFBS , PFHS , an d PFO S i 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

fPerfluorooctan e Sulfonat e (PFOS) , Perfluorohexan e Sulfonat e (PFHS ) an d Perfluorobutan e Sulfonat e (PFBS ) 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 specifl ctest syste m an d n o dosin g ofa 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
. % / Gary ' Hohe||^steinySponso rRepresentative Date

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

Pag e 3 o f7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2



### QUALIT YASSURANC E STATEMEN T Repor t Title : Interi m Repor

t 2 6 - Analysi s o

fPFBS , PFHS , an d PFO S i n Surface Wate rSample s Collecte d a

t Ber t Jeffrie s Landfll l i n Decatur , A L i n Febaiar y201 2 Study : Analysi s ofPerfluorooctan e Sulfonat e (PFOS) , Perfluorohexan e Sulfonat e (PFHS ) an d Perfluorobutan e Sulfonat e (PFBS ) 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 audite d b yth e 3 M Environmenta l Laborator yQualit yAssurance Uni t (QAU) , a s indicate d i n th e followin g table
. Th e findings were reporte d t o th e principa l investigato r(P.I.) , laborator ymanagemen t an d stud ydirector
.
Inspectio n Date s Phas e Dat e R e 3orte d t o Inspectio n Date s Phas e Testin g Facilit y Managemen t Stud yDirecto r 4/2/12-4/3/1 2 Dat a an d Repor

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

QA U Represeraative Date

Pag e 4 o f 7 7

### 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 Introductio n 9 4 Tes t & Contro l Substance s 9 5 Referenc e Substance s 1 0 6 Tes t Syste m 1 1 7 Metho d Summar y1 2 7. 1 Method s 1 2 7. 2 Sampl e Collectio n 1 2 7. 3 Sampl e Preparatio n 1 2 7. 4 /^alysi s 1 2 8 Analytica l Result s 1 3 8. 1 Calibratio n 1 3 8. 2 Syste m Suitabilit y1 4 8. 3 Limi t o fQuantitatio n (LOQ ) 1 4 8. 4 Continuin g Calibratio n 1 4 8. 5 Blank s 1 4 8. 6 La b Contro l Spike s (LCSs ) 1 4 8. 7 Analytica l Metho d Uncertaint y1 6 8. 9 Fiel d Matri xSpike s (FMS ) 1 6

Pag e 5 o f 7 7

### 9 Data Summar yan d Discussio n 1 6 1 0 Conclusio n 2 0 1 1 Data/Sampl e Retentio n ' 2 0 1 2 /attachments 2 0 1 3 Signature s 2 1 LIS TO F TABLE S Tabl e 1 . Summarize d PFBS , PFHS , an d PFO S Results (Jeffrie s Landfil l Site , Fe b 2012 ) 8 Tabl e 2 . Sampl e Descriptio n Ke yCod e 1 1 Tabl e 3 . Instrumen t Parameter s 1 2 Tabl e 4 . Liqui d Chromatograph yCondition s 1 3 Tabl e 5 . Mass Transition s 1 3 Tabl e 6 . Limi t o

fQuantitatio n (LOQ ) 1 4 Tabl e 7 . Laborator

yContro l Spik

e Recover

y1 5 Tabl e 8 . Analytica l Uncertaint y1 6 Tabl e 9 . Fiel d Matri xSpik e Level s 1 6 Tabl e 10 . JPA L S

WET0 1 12022 8 1 7 Tabl e 11 . JPA L S

WET02 12022 8 1 7 Tabl e 12 . JPA L S

WET0 3 12022 8 1 8 Tabl e 13 . JPA L S

WET04 12022 8 1 8 Tabl e 14 . Tri p Blan k

12022 8 1 9

Pag e 6 o f7 7

### 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 , (clange(S).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 2 6 Experimenta l Termination : Marc h 14 , 201 2 Interi m Report Completion : Dat e o fInteri m Report 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 f7 7

### 2

Summary Th e 3 M Environmenta l Laboratoryreceive d surfac e wate rsample s fro m fou rdifferen t location s locate d a t Jefl'rie s Landfil l i n Decatur , AL
. Atota l o f ninetee n sampl e bottles wer e receive d a t th e 3 M Environmenta l Laboratoryfo rperfiuorooctan e sulfonat e (PFOS) , perfluorohexan e sulfonat e (PFHS ) an d perfluorobutan e sulfonat e (PFBS) , an d include d duplicat e surfac e wate rsample s an d tw o field matri xspik e (FMS ) sample s fro m eac h samplin g location
. Ase t o f tri p blan k samples ; singl e tri p blan k containin g Milli-Q TM wate ran d tw o tri p blan k spikes , wer e include d wit h th e sampl e bottles
. /Al l sample s wer e logge d int o th e laboratoryinformatio n managemen t syste m (LIMS ) unde rprojec t GLP10-01-02 - 26 . Th e surfac e wate rsample s an d tri p blank s wer e receive d fro m Westo n personne l o n Marc h 2 , 2012 . /M l o fth e sample s wer e prepare d an d analyze d fo rPFBS , PFHS , PFOS , an d th e surrogat e recoverystandar d ^^C4-PF0S , followin g 3 M Environmenta l LaboratoryMetho d ETS-8-044.1
. Th e averag e measure d PFBS , PFHS , an d PFO S concentration s ar e summarize d i n Tabl e 1 . Th e tri p blan k sampl e wa s belo wth e lowe rlimi t o fquantitatio n (LLOQ ) fo ral l analytes , indicatin g adequat e contro l o fsampl e contaminatio n durin g shippin g an d sampl e collections
. Th e analytica l metho d uncertaintie s associate d wit h tiie reporte d result s are : PFB S + 22% , PFH S + 19 % an d PFO S + 15% . Tabl e 1 . Summarize d PFBS , PFHS , an d PFO S Result s (Jeffrie s Landfil l Site , Fe b 2012) .
3 M LIM S I D Sampl e Descriptio n PFB S Concentratio n (ng/mL ) PFH S

Concentratio n (ng/mL ) PFO S

Concentratio n (ng/mL ) GLP10-01-02-026-00 5 JPAL-SW-ET01-0-12022 8 0.0345 <0.025 0 0.030 2 GLP10-01-02-026-00 6 JPAL-SW-ET01-DB-12022 8 0.0362 <0.025 0 0.0302 Average 0.035 4 <0.025 0 0.0302 %RPD Sample/Sample

Dup 4. 8 N A 0. 0 GLP10-01-02-026-00 9 JPAL-SW-ET02-0-12022 8 <0.025 0 <0.025 0 0.066 1 GLP10-01-02-026-01 0 JPAL-SW-ET02-DB-12022 8 <0.025 0 <0.025 0 0.059 3 Average <0.025 0 <0.025 0 0.062 7 %RPD Sample/Sample

Dup N A N A 1 1 GLP10-01-02-026-01 3 JPAL-SW-ET03-0-12022 8 <0.025 0 <0.025 0 0.303 GLP10-01-02-026-01 4 JPAL-SW-ET03-DB-12022 8 <0.025 0 0.0252 0.30 3 Average <0.025 0 0.025 2 0.30 3 %RPD Sample/Sample

Dup N A NA'^ ' 0. 0 GLP10-01-02-026-01 7 JPAL-SW-ET04-0-12022 8 <0.025 0 <0.025 0 0.16 6 GLP10-01-02-026-01 8 JPAL-SW-ET04-DB-12022 8 <0.025 0 <0.025 0 0.15 9 Average <0.025 0 <0.025 0 0.163 %RPD Sample/Sample

Dup N A N A 4. 3 GLP10-01-02-026-02 5 JPAL-SW-TRIP1-0-12022 8 <0.025 0 <0.025 0 <0.0232 NA= No t Applicabl e Th e analytica l metho d uncertaintie s associate d wit h th e reporte d results are : PFB S ±22% , PFH S ±1 9 % , an d PFO S ±15% . (1 ) Asample/sampl e duplicate RP D coul d no t be determine d since th e concentratio n fo rth e primar ysampl e wa s BLO Q fo rPFHS
.

Page 8 o f 7 7

### 3

Introduction Thi s analytica l stud ywas conducte d a s par t o fth 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 fth e overal l progra m i s t o gai n infomiatio n regardin g concenti-ation s o fperfluorooctan e sulfonat e (PFOS) , perfluorohexan e sulfonat e (PFHS ) an d perfluorobutan e sulfonat e (PFBS) , 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 a t o rnea rJeffrie s Landfil l i n Decatur , A L fo rPFBS , PFHS , an d PFO S i n a n effor t t o characteriz e surface wate rconditions
. Th e 3 M Environmenta l Laborator yprepare d sampl e container s (25 0 m L high-densit

ypolyethylen e botties ) whic h were shippe d t o Decatur , A L Westo n personne l prio rt o field sampling
. Sampl e container s fo reac h samplin g locatio n include d a field sample , fiel d sampl e duplicate , an d two field matri xspik

e samples
. Eac h empt

ycontaine rwas mari<e

d wit h a "fil l t o here " lin e t o produce a final sampl e volum e of20 0 mL
. Container s designate d fo rfield matii xsample s were fortifie d wit h a n appropriat e matri xspik

e solutio n containin g PFB S (linea risomer) , PFH S (linea risomer) , an d PFO S (linea ran d branche d isomers ) prio rt o bein g sen t t o th e field fo rsampl e collection
. /M l sampl e bottle s include d th e additio n of^^Oz-PFBS , ''^Ca-PFHS , an d ^^Cg-PFO S (intema l standard ) at a nomina l concentratio n of1 ng/mL
. Al l sampl e bottle s als o include d th e additio n o f"C4-PFO S (surtogat e recover ystandard ) a

t a nomina l concentratio n o f0. 1 ng/mL
. Se e sectio n 8. 8 o fth 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 ymetiio d ETS-8-044. 1 "Metho d of/Analysi s fo rth e Detenninatio n ofPerfiuorinate d Compound s I n Wate rb

yLC/MS/MS ; Direc

t Injectio n Analysis"
. Th e us e ofinterna l standard s wa s use d t o ai d i n th e data qualit yobjectives
. Tabl e 1 summarize s th e averag e PFBS , PFHS , an d PFO S concenti-ation s 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 field matri xspik e 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 tills repor

t 

### 4 Test & Control Substances There wa s not a test substance o rcontro l substance s i n th e classi csens e o fa GL P study
. Thi s stud y wa s purel yanalytica l i n nature .

Pag e 9 o f7 7

### 5

Reference

Substances

Referenc e Substanc e PFB S (predominantl y linear ) "O2-PFB S Chemica l Nam e Potassiu m Perfluorobutan e sulfonat e f*02]-Ammoniu m Perfluorobutanesulfonat e Chemica l Formul a C4F9SO3X " C4F9S['*02]0-NH / Identifie r N A N A Us e Targe t Analyt e Referenc e Standar d Intema l Standar d Sourc e 3 M RT I Intemationa l Expiratio n Dat e 01/10/201 7 03/09/201 5 Storag e Condition s Froze n Froze n Chemica l Lo t Numbe r 41-2600-8442- 5 11546-107- 2 TC R Numbe r TCR-12 1 TCR-1044,TCR-104 0 Physica l Descriptio n Whit e Powde r Liqui d Purit y 96.7 % >99 %
Referenc e Substanc e PFH S (Linear ) "C3-PFH S "C3-PFH S Chemica l Nam e Sodiu m Perfluorohexan e sulfonat e Sodiu m Perfluorohexanesulfonat e Sodiu m Perfluorohexanesulfonat e Chemica l Formul a CgFisSOs'Na ^ ''Cs^'CsFiaSOs-Na ' "Ca^'CaFiaSOs-Na ' Identifie r L-PFHX S MPFC-C-051 1 MPFC-C-011 2 Us e Targe t Analyt e Referenc e Standar d Intema l Standar d Intema l Standan j Sourc e Wellingto n Wellingto n Wellingto n Expiratio n Dat e 03/25/201 8 05/25/201 4 01/24/201 5 Storag e Condition s Froze n Froze n Froze n Chemica l Lo t Numbe r LPFHxSAMO S MPFC-C-051 1 MPFC-C-011 2 TC R Numbe r TCR08-001 8 TCR11-001 6 TCR12-000 4 Physica l Descriptio n Crystallin e Liqui d Liqui d Purit y 100 % 5|jg/mL<^ ' 5|jg/mL<^ ' (1 ) Custo m mixtur

e o fseve n mass-labele d ("C ) perfluoroalkylcarboxyll cacids , two mas s labele d ("C ) perfluoroalkylsulfonate s an d on e mass-labele d ("C ) perfluoro-1-octanesulfonamide
.

Pag e 1 0 o f 7 7Referenc e Substanc e PFO S

(Linea r+ Branched ) "C4-PFO S "Ca-PFO S "Ca-PFO S Chemica l Nam e Potassiu m Perfluorooctan e sulfonat e Sodiu m

Perfluorooctan e sulfonat e Sodiu m Perfluorooctan e sulfonat e Sodiu m Perfluorooctan e sulfonat e Chemica l Formul a CsF-iySO s K ^^C4^^C4Fi7S03'Na ^ ^^C8Fi7S03"Na " Identifie r Br-PFOS K MPFO S 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 03/17/2014 ; 12/01/201 4 09/08/201 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 brPFOSK0708 ; brPFOSKi m MPFOS091 0 MPFC-C-051 1 MPFC-C-011 2 TC R Numbe r TCR11-0010 ; TCR11-004 1 TCR10-0044-7/ 9 TCR11-001 6 TCR12-000 4 Physica l Descriptio n Liqui d Liqui d Liqui d Liqui d Purit y 99.9 % >98 % 5|jg/mL'^ ' Spg/mL'^ ' (1 ) Custo m mixtur

e of seve n mass-labele d ("C ) perfluoroalkylcarboxyli cacids , two mass labele d ( C ) perfluoroalkylsulfonate s an d on e mass-labele d ("C ) perfluoro-1-octanesulfonamide
. 

### 6 Test System Th e test system s fo rthi s stud yar e surface wate rsample s collecte d fro m well s locate d i n Decatur , A L b yWesto n Solutions , Inc
. personnel
. Sample s fo rthi s stud yar e "rea l world " samples , no t dose d wit h a specifi clot o

f tes t substance
. Tabl e 2 . Sampl e Descriptio n Ke y Code . strin g Numbe r Strin g Descripto r Exampl e Example JPAL-SW-ET01-0-120228 1 Sample Location JPAL= Jeffries Property, Alabama 2 Sample Type SW

= Surface 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 = duplicate

sample LS" low spike HS = high spike

Pag e 1 1 o f 7 7

### 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 ofAnalysi s fo rth e Determinatio n ofPerfiuorinate d Compound s I n Wate rb yHig h Perfomnanc

e Liqui d Chromatography/Mas s Spectrometr yDirec t Injectio n Analysis"
. 

### 7. 2 Sampl e Collectio n Sample s were collecte d i n 25 0 m L Nalgene TM (high-densit ypolyethylene ) bottle s prepare d a t th e 3 M Environmenta l Laboratory
. Sampl e bottle s associate d wit h GLP10-01-02-2 6 were retume d t o tiie 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
. Ase t o

flaborator

yprepare d Tri p Blan k

an d Tri p Blan k

field matri xspike s were sen t wit h th e sampl e collectio n bottles
. 

### 7. 3 Sampl e Preparatio n Sample s were prepare d byremovin g a n aliquot o fth e wel l mixe d sampl e an d placin g i t i n a n autovia l fo r analysis
. Durin g tiie preparatio n ofth e laborator ycontro l samples , a n aliquot ofa separat e intema l standar d spikin g solutio n wa s adde d t o th e laborator ycontro l sample s (nomina l concentratio n of1 ng/mL)
. Th e sample s bottle s were spike d witi i a n intema l standar d mi xa t a nomina l concentratio n of1 ng/m L prio rt o bein g sen t t o th e field fo rsampl e collectio n 7. 4 Analysi s Al l stud ysample s an d qualit ycontro l sample s were analyze d fo rPFBS , PFHS , an d PFO S usin g hig h perfomianc e liqui d chromatography / tande m mass spedrometi y(HPLC/MS/MS)
. Detaile d instnjmen t parameters , th e liqui d chromatograph ygradien t program , an d tiie specifi cmas s ti-ansitions analyze d ar e describe d i n th e ra

wdat a har

d copie s place d i n th e final data packet , an d ar e briefi ydescribe d below
. Tabl e 3 . Instrumen t Parameters . Instrumen t Nam e ETS Ginge r ETS McCo y Analytica l Metho d Followe d ETS-8-044. 1 ETS-8-044. 1 Analysi s Dat e 3/7/12-PFB S an d PFH S 3/13/12-PFO S Liqui d Chromatograp h Agilen t 1100 Agilen t 1290 Guar d colum n Betasi l C I 8 (4. 6 m m X10 0 mm) , 5 n Betasi l C I 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 n Betasi l C1 8 (4. 6 m m X10 0 mm) , 5| x Injectio n Volum e 2 5 n L 50 n L Mas s Spectromete r Applie d Biosystem s AP I 500 0 Applie d Biosystem s AP I 550 0 Io n Sourc e Turb o Spra y Turb o Spra y Electrod e Turb o io n electrod e Turb o io n electrod e Polarit y Negativ e Negativ e Softwar e Analyst 1.4. 2 Analyst 1.5. 2

Pag e 1 2 o f7 7Tabl e 4 . Liqui d Chromatograph y Conditions . step Total

Time Flow

Rate Percent A PercentB Number (min) (juUmin) (2 mM ammonium

acetate) (methanoO ETS-8-044. 1 Analyze d 3/7/1 2 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 Ste p Total

Time Flow

Rate Percent A Percen t S Number (mIn) (fdJmin) (5 mM ammonium

acetate: (acetonitrile) 0.01%acetic

acid) ETS-8-044. 1 Analyze d 3/13/1 2 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 Reference

Material Structure intemal Standard Mass Transition Q1/Q3 PFBS 299/80

299/99 Linear t'OJ-PFBS 303/84 PFHS 399/80

399/99 Linear rcj-PFHS 402/80 PFOS 499/80

499/99 499/130 Linear + Branched t'CsI-PFOS 507/80 C'CJ-PFOS 503/80 Linear rcJ-PFOS 507/80 Dwel l tim e wa s 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 was use d fo rquantitation
. 

### 8 Analytical

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

yspikin g know n amounts o fth e stoc k

solutio n containin g th e targe t analyte s into a laboratory-prepare d syntheti cgroundwate rcontainin g calciu m an d magnesium
. Aseparate intema l standar d spikin g solutio n wa s prepare d an d a n aliquot wa s adde d a t tiie sam e leve l t o al l calibratio n standard s an d laborator

yconti"o l sample s a

t a nomina l concentratio n of1 ng/mL
. Acalibratio n curve rangin g fro m approximatel y0.02 5 ng/m L t o 100 ng/m L (0.02 5 ng/m L t o 1 0 ng/m L fo r^^C4-PF0 S sun-ogate) was prepared
. Th e reference standar d use d fo rth e calibratio n standard s fo rPFO S containe d bot h linea ran d branche d isomers
.

Pag e 1 3 o f 7 7Aquadratic , 1/ xweighted , calibratio n curve o ftiie standar

d pea k area/pea k

are a ratio s wa s 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 fittin g process . Calculatin g th e standar

d concentration s usin g tiie pea k area/pea k

are a ratio s an d tiie resultan t calibratio n curve confimie d accurac

yo feac 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

f100±25 % (100±30 % fo rth e lowest curve point) were met fo ral l analytes
. Th e comelatio n coefficien t (r) was greate rtha n 0.99 5 fo rPFBS , PFHS , PFOS , an d ^^C4-PF0S
. 

### 8. 2 Syste m Suitability Acalibratio n standar

d wa s analyze d fou rtimes a t th e beginnin g o

feac h analytica l sequence t o demonstrat e overal l syste m suitability
. Th e acceptance criteri a ofles 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 ofles s tha n o requa l t o 2 % RS D was me t fo rPFBS , PFHS , PFOS , an d ^^C4-PF0S
. 

### 8. 3 Limi t o

fQuantitatio n (LOQ ) Th e LOQ fo rthi s analysi s i s th e lowest non-zer o calibratio n standar

d i n th e curve that meets linearit y an d accurac

yrequirements an d fo rwhic h th e are a counts o rare a rati o ar e a t least twic e thos e ofth e appropriat e blanks
. Th e LO Q fo ral l analyte s ca n b e foun d i n Tabl e 6 . Tabl e 6 . Limi t o fQuantitatio n (LOQ)
. PFBS LOQ, ng/mL PFHS

LOQ, ng/mL PFOS

LOQ, ng/mL 0.025 0 0.025 0 0.0232 

### 8. 4 Continuin g Calibratio n Durin g th e cours e ofeac h analytica l sequence , continuin g calibratio n verificatio n sample s (CCVs ) were analyze d t o confim n that th e instiumen t respons e an d th e initia l calibratio n curve wer e stil l i n control
. Al l CCV s met metho d criteri a o

f100 % ±25 % fo rPFBS , PFHS , PFOS , an d ^^C4-PF0S
. 

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

s were prepare d an d analyze d wit h tiie samples : procedura l blank s an d tiip blanks
. Procedura l blan k

results were reviewe d an d use d t o evaluat e metiio d perfomianc e t o determin e tiie LOQ
. Tri p blank

s reflec t th e shippin g an d sampl e collectio n conditon s th e sampl e bottle s an d sample s experience
. 

### 8. 6 La b Contro l Spike s (LCSs ) Low , mid , an d 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-PF0 S sun-ogate . LCS s were prepare d byspikin g know n amounts o fth e analyt e into syntiieti cgroundwate rt o produce th e desire d concentration
. Th e spike d wate rsample s were the n prepare d an d analyze d i n th e sam e manne ras th e samples
. Th e metho d acceptance criteria , averag e o fLC S a t eac h leve l shoul d b e withi n 100 % ±20 % wit h a n RS D <20% , was met fo ral l analytes
. Th e followin g calculation s were use d t o generat e data i n Tabl e 7 fo rlaborator yconti"o l spikes
. 1 r > »r > Calculate d Concentratio n , . .„„ , LC S Percen t Recover

y= * 100 % Spike Concentratio n LCS%RS D = standard deviationlCSreplicate s .^^^y ^

averag e LC S recover

y

Pag e 1 4 o f 7 7Tabl e 7 . Laboratory Contro l Spike Recovery . ETS-8-044. 1 Analyze d 3/7/1 2 PFB S PFHS Spiked Concentration Calculated

Concentration Spiked Concentration Calculated

Concentration Lab ID (ng/mL) (ng/mL) 'ARecovery (ng/mL) (ng/mL) VoRecovery LCS-120306- 1 0.19 8 0.20 9 10 5 0.19 8 0.191 96. 3 LCS-120306- 2 0.19 8 0.20 9 10 6 0.19 8 0.18 2 91. 8 LCS-120306- 3 0.19 8 0.20 7 10 4 0.19 8 0.18 5 93. 3 Averag e ±%RS D 105 % ±0.95 % 93.8 % ±2.4 % LCS-120306- 4 1.9 8 2.1 7 11 0 1.9 8 2.0 8 10 5 LCS-120306- 5 1.9 8 2.1 9 11 1 1.9 8 1.9 2 97. 1 LCS-120306- 6 1.9 8 2.0 9 10 6 1.9 8 1.9 4 98. 0 Averag e ±%RS D 109 % ±2.4 % 100 % ±4.3 % LCS-120306- 7 19. 9 18. 9 95. 1 19. 8 18. 5 93. 5 LCS-120306- 8 19. 9 18. 1 91. 1 19. 8 18. 1 91. 3 LCS-120306- 9 19. 9 19. 8 99. 6 19. 8 19. 2 96. 9 Averag e ±%RS D 95.3 % ±4.5 % 93.9 % ±3.0 % ETS-8-044. 1 Analyze d 3/13/1 2 PFOS (Linear + Branclied) C4-PFOS surrogab Spiked Concentration Calculated

Concentration Spiked Concentration Calculated

Concentration Lab ID (ng/mL) (ng/mL) VoRecovery (ng/mL) (ng/mL) "ARecovery LCS-120306- 1 0.18 4 0.17 8 97. 0 0.18 9 0.221 11 7 LCS-120306- 2 0.18 4 0.17 0 92. 6 0.18 9 0.21 5 11 4 LCS-120306- 3 0.18 4 0.17 0 92. 6 0.18 9 0.22 5 11 9 Averag e ±%RS D 94.1 % ±2.7 % 117 % ±2.2 % LCS-120306- 4 1.8 4 1.7 6 95. 6 1.8 9 2.2 1 11 7 LCS-120306- 5 1.8 4 1.7 2 93. 6 1.8 9 2.1 4 11 3 LCS-120306- 6 1.8 4 1.7 1 92. 9 1.8 9 2.1 4 11 3 Averag e ±%RS D 94.0 % ±1.5 % 114 % ±2.0 % LCS-120306- 7 18. 4 17. 1 92. 8 N A N A N A LCS-120306- 8 18. 4 16. 6 90. 4 N A N A N A LCS-120306- 9 18. 4 17. 4 94. 3 N A N A N A Averag e ±%RS D 92.5 % ±2.1 % N A NA= No t Applicabl e

Pag e 1 5 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2

8. 7 Analytica l Metho d Uncertaint y Analytica l uncertaint

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

yan d precision
. Th e metho d uncertaint yi s calculate d followin g ETS-12-012.2
. Th e standar d deviatio n i s calculate d fo rth e set o faccurac 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 rof2 , whic h con-espond s t o a confidence leve l of 95% . Tabl e 8 . Analytica l Uncertainty
. Analyt e Standar d Deviatio n Metho d Uncertaint y PFB S 10. 8 ±22 % PFH S 9.4 2 ±19 % ' PFO S 7.6 0 ±15 % 8. 8 Fiel d Matri xSpike s (FMS ) Low , mid , an d hig h field matri xspike s (FMS ) were collecte d a t eac h samplin g poin t t o verif ythat th e analytica l metho d i s applicabl e t o th e collecte d matrix
. Fiel d matri xspike s were generate d b yaddin g a measure d volum e offiel d sampl e t o a containe rspike d b yth e laborator

ywit h PFB S (linear) , PFH S (linear) , an d PFO S (linear+branched ) prio rt o shippin g sampl e container s fo rsampl e collection
. Fiel d matri xspik

e recoverie s withi n metho d acceptance criteri a of 100±30 % confir m that "unknown " components i n th e sampl e matri xd o no t significantl yinterfer

e wit h th e extractio n an d analysi s ofth e analyte s of interest
. Fiel d matri xspike concentration s must b e 50 % o fth e sampl e concentratio n t o b e considere d a n appropriat e field spike
. Fiel d matri xspike s are presente d i n sectio n 9 ofthi s report . Tabl e 9 . Fiel d Matri xSpik e Levels
. Samplin g Locatio n Spik e Leve l PFBS , ng/m L PFHS ,

ng/m L PFOS ,

ng/m L Al l location s an d Tri p Blan k Lo w 1.0

0 0.99 8 0.92 8 Al l location s an d Tri p Blan k Hig h 10. 0 9.9 8 9.2 8 FM S Recover yJ Sampl e Concentratio n o f FM S - Averag e Concentration : Fiel d Sampl e & Fiel d Sampl e Dup. ) • .,QQO / Spik e Concentrato n

d Data Summary

and Discussion Th e table s belowsummariz e th e sampl e results an d field matri xspik e recoverie s fo rth e samplin g location s a s wel l as th e Tri p Blank
. Results an d averag e value s are 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 xspike recoverie s meetin g th e metho d acceptance criteri a o f ±30% , demonstrat e that th e metho d was appropriat e fo rth e give n matri xan d thei rrespective quantitative ranges .

Pag e 1 6 o f 7 7Tabl e 10 . JPA L S WET0 1 12022 8 PFB S PFH S PFO S "C4PFOS Concentration Concentration Concentration 3M LIMS ID Description (ng/mL) "ARecovery (ng/mL) 'ARecovery (ng/mL) "ARecovery "ARecovery GLP10-01-02-26-00 5 JPAL-SW-ET01-0-12022 8 0.034 5 N A <0.025 0 N A 0.030 2 N A 10 9 GLP10-01-02-26-00 6 JPAL-SW-ET01-DB-12022 8 0.036 2 N A <0.025 0 N A 0.030 2 N A 10 2 GLP10-01-02-26-00 7 JPAL-SW-ET01-LS-12022 8 1.0 8 10 4 0.94 6 94. 8 0.86 3 89. 7 11 0 GLP10-01-02-26-00 8 JPAL-SW-ET01-HS-12022 8 10. 4 10 4 8.6 2 86. 4 8.3 8 90. 0 11 0 Average Concentration

(ng/mL)

± %RPD 0.0354 ng/mL±4.8% <0.0250 ng/mL 0.0302 ng/mL±0.0% 10S"A±3.3"A NA= No t Applicabl e Tabl e 11 . JPA L S WET0 2 12022 8 PFB S PFH S PFO S "C4PFO S Concentration Concentration Concentration 3M LIMS ID Description (ng/mL) "ARecovery (ng/mL) VoRecovery (ng/mL) "ARecovery "ARecovery GLP10-01-02-26-00 9 JPAL-SW-ET02-0-12022 8 <0.025 0 N A <0.025 0 N A 0.066 1 N A 10 7 GLP10-01-02-26-01 0 JPAL-SW-ET02-DB-12022 8 <0.025 0 N A <0.025 0 N A 0.059 3 N A 10 6 GLP10-01-02-26-01 1 JPAL-SW-ET02-LS-12022 8 1.0 8 10 8 1.03 0 10 3 0.92 4 92. 8 10 9 GLP10-01-02-26-01 2 JPAL-SW-ET02-HS-12022 8 9.6 3 96. 3 8.64 0 86. 6 8.4 5 90. 4 10 7 Average Concentration

(ng/mL)

± "ARPD <0.0250 ng/mL <0.0250 ng/mL 0.0627 ng/mL±11"A 107%± 1.2"A NA= No t Applicabl e

Pag e 1 7 o f7 7Tabl e 12 . JPA L S WET0 3 12022 8 PFB S PFH S PFO S "C4PFO S Concentration Concentration Concentration 3MLiMSiD Description (ng/mL) "ARecovery (ng/mL) VoRecovery (ng/mL) "ARecovery "ARecovery GLP10-01-02-26-01 3 JPAL-SW-ET03-0-12022 8 <0.025 0 N A <0.025 0 N A 0.30 3 N A 10 9 GLP10-01-02-26-01 4 JPAL-SW-ET03-DB-12022 8 <0.025 0 N A 0.025 2 N A 0.30 3 NA 10 9 GLP10-01-02-26-01 5 JPAL-SW-ET03-LS-12022 8 1.0 5 105 0.99 2 96. 9 1.1 3 89. 1 103 GLP10-01-02-26-01 6 JPAL-SW-ET03-HS-12022 8 9.1 4 91. 4 8.82 0 88. 1 8.72 90. 7 106 Average Concentration

(ng/mL) ± "ARPD <0.0250 ng/mL 0.0252 ng/mU^' 0.30 3 ng/m L ±0.0

% 707

% ±2.7 % NA= Not Applicabl e (1 ) A sample/sampl e duplicat e RP D could no

t t> e determine

d since the concentration o fth e primar y sampl e was BLO Q fo

rPFHS . Tabl e 13 . JPA L S WET0 4 12022 8 PFB S PFH S PFO S "C4PFO S Concentration Concentration Concentration 3M LIMS ID Description (ng/mL) "ARecovery (ng/mL) %Recovery (ng/mL) "ARecovery "ARecovery GLP10-01-02-26-01 7 JPAL-SW-ET04-0-12022 8 <0.025 0 N A <0.025 0 NA 0.16 6 N A 11 3 GLP10-01-02-26-01 8 JPAL-SW-ET04-DB-12022 8 <0.025 0 NA <0.025 0 NA 0.15 9 N A 10 9 GLP10-01-02-26-01 9 JPAL-SW-ET04-LS-12022 8 1.1 4 11 4 0.93 1 93. 3 1.0 3 93. 5 11 0 GLP10-01-02-26-02 0 JPAL-SW-ET04-HS-12022 8 10. 6 10 6 8.4 5 84. 7 8.4 7 89. 5 10 5 Average Concentration

(ng/mL) ± "ARPD <0.0250 ng/mL <0.0250 ng/mL 0.163 ng/mL±4.3"A 109'A±3.2"A N A= No t Applicabl e

Pag e 1 8 o f 7 7Tabl e 14 . Tri p Blan k 12022 8 PFB S PFH S PFO S "C4PFOS 3M LIMS ID Description Concentration (ng/mL) %Recovery Concentration (ng/mL) "ARecovery Concentration (ng/mL) "ARecovery "ARecovery GLP10-01-02-26-02 5 JPAL-SW-TRIP 1 -0-12022 8 <0.025 0 N A <0.025 0 N A <0.0232 N A 108 GLP10-01-02-26-02 6 JPAL-SW-TRIP 1 -LS-12022 8 1.0 6 106 0.94 7 94. 9 0.80 9 87. 2 10 9 GLP10-01-02-26-02 7 JPAL-SW-TRIP 1 -HS-12022 8 9.32 93. 2 9.2 1 92. 3 8.0 7 87. 0 107 NA= Not /Applicabl e

Pag e 1 9 o f 7 7

### 10

Conclusion Laborator yconti-o l spike s an d field mati-ixspike s were use d t o determin e th e analytica l metiio d accurac yan d precisio n fo rPFBS , PFHS , an d PFOS
. Analysi s was successfull ycomplete d followin g 3 M Environmenta l Laborator ymetho d ETS-8-044. 1 describe d herein
. 

### 11 Data/Sample

Retention Al l remainin g sample s an d associate d projec t data (hardcopyan d electi-onic ) wil l b e archive d accordin g t o 3 M Environmenta l Laborator ystandar d operatin g procedures
. 

### 12 Attachments Attachmen t A : Protoco l Amendmen t 2 6 (Genera l Projec t Outiine ) Attachmen t B : Representative Chromatogram s an d Calibratio n Curve s Attachmen t C : Analytica l Method-ETS-8-044. 1

Pag e 2 0 o f 7 7

### 13

Signatures GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2

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

Willia m K
. Reagen , Ph.D. , 3 M Environmenta l Laborator yDepartmen t Manage rDate 

# t Gar yHbhenatein , Siponso rRepresentative Date



# Jk/rti

' Date Jaisimh a Kesari , Stud yDirecto r

Pag e 2 1 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2


### ATTACHMEN TA : PROTOCO L AMENDMEN T

Pag e 2 2 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o fPFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2
Analytical

Protocol:

GLP10-01-02 Amendment

26 

### Study Title Analysi s o f Perfluorooctan e Sulfonat e (PFOS) , Perfluorohexan e Sulfonat e (PFHS ) an d Perfluorobutan e sulfonat e (PFBS ) i n Groundwater , Soi l an d Sedimen t fo rth e 3 M

Decatu rPhas e 3 Site-Relate d Monitorin g Progra m
PROTOCO L AMENDMEN TNO . 2 6

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
Laborator yProjec t Identificatio n GLP10-01-02-2 6 Sampling

Event Ber t Jeffrie s Landfil l -Surfac e Wate rSamplin g

Page 1 o f6
Pag e 2 3 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2 Analytical

Protocol:

GLP10-01-02 Amendment

26 

### Thi s amendmen t modifie s tiie followin g portio n ofprotocol : "Analysi s o fPFOS , PFH S an d PFB S i n Groundwater , Soi l an d Sedimen t fo rth e 3 M

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

PROTOCOLFISADS: N o change s t o th e wordin g o f th e protoco l ar e required
.

AMEND TO READ: N o change s t o th e wordin g o fth e protoco l are required
. Thi s amendmen t onl yaddresse s an d document s th e additio n o fth e Genera l Project Outlin e (GPO ) fo rth e collectio n an d analysi s o f groundwate rsample s fro m Decatur , AL , an d conducte d a s par t o f th e 3 M Decatu rPhas e 3 Prograi n fo rPFOS , PFH S an d PFB S (GLP10-01-02)
. Samplin g activitie s at an d nea rth e Ber t Jeffrie s landfil l ar e schedule d fo rth e wee k o f Februar y27 , 201 2 an d wil l consis t of 6 paire d surfac e wate ran d sedimen t samples
. Thi s protocol
. 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 GLP10-01-02-2 6 an d reporte d a s interi m repor t GLP10-01-02-2 6 (reflectin g stud yGLP10-01-0 2 an d amendmen t -26)
.
Reason: Th e reaso n fo rthi s amendmen t i s t o documen t th e Genera l Project Outlin e (GPO ) whic h describe s th e anticipate d surfac e wate rsampl e collectio n even t t o b e conducte d at 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 tills amendmen t form
.

Pag e 2 o f 6
Pag e 2 4 o f 7 7

### Amendmen t Approva l GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o fPFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2 Analytical

Protocol:

GLP10-01-02 Amendment

26



### '71 Gar yHohenstein , Sponso rRepresentative Dat e

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

Willia m Reagen , EM S Opn s Environmenta l La b Managemen t Dat e

Dat e

Pag e 3 o f6

Pag e 2 5 o f7 7GLP10-01-02 ; Interi m Repor t 26 Analysi s o f PFBS , PFHS , an d PFO

S Ber t Jeffries Landfil l - Februar

y201 2 Analytical

Protocol:

GLP10-01-02 Amendment

26 Environmenta l Healt h & Safet y Operations , Environmenta l Laborator y Genera l Projec t Outlin e To : Gar

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

y21,201 2 Subject : Analysi s o f Perfluorooctan e Sulfonat e (PFOS) , Perfluorohexan e Sulfonat e (PFHS ) an d

Perfluorobutan e sulfonat e (PFBS ) i n Groundwater , Soi l an d Sedimen t fo rtiie 3 M Decatu r Phas e 3 Site-Relate d Monitorin g Program ; GL P Interi m Repor t 2 6 - Ber

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

y27 , 2012 . 1 Genera l Projec t Informatio n
3 M Sponso rRepresentativ e GaryHohenstei n 3 M EH S Operation s 3 M Buildin g 224-5W-03 Sain t Paul , M N 55144^100 0 Phone : (651)737-357 0 aahohensteinffimmmico m 3 M Environmenta l Laborator yn/lanagenien t Willia m K
. Reage n 3 M EH S Opns, Environmenta l Latioratory 260-5N-1 7 Contact s 65 1 733-973 9 wkreaaen@mmm.co m Principa l Analytica l Investigato r Clesto n Lang e 3 M EH S Opns, Environmeiita l Laboratoi y 260-5N-1 7 65 1 733-986 0 cclanae@mmm.co m Samplin g Coortllnato r Timoth yFrina k Westo n Solution s Timothv.frinakffiwestonsoluiion8,cQ m Phone : (334).332-912 3 La b Reques t Numbe r qLP10-01-02-2 6 Si xDigi t Departmen t Numbe r Oep t #530711 , Project #002267444 9 Projec t Schedule/Tes t Date s Tentativel yschedule d fo rth e wee Ko f Febaiar y27,2Q12
. AH verbal end written correspondence

will be directed to Gary Hohenstein.

Page 4 o f 6 Page 26 o f 7 7GLP10-01-02 ; Interi m Repor t 26 Analysi s o fPFBS , PFHS , an d PFO

S Ber t Jeffries Landfil l - Februar

y201 2 Analytical

Protocol:

GLP10-Q1-02 Amendment

26 

### 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
. Surtac 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 rPerfluorooctan e Sulfonat e (PFOS) , Perfluorohexan e Sulfonat e (PFHS ) an d Perfluorobutan e Sulfonat e (PFBS)
. Analyse s wil l b e conducte d unde rth e GL P requirement s o f EPA TSC AGoo d Laborator

yPractic e Standard s 4 0 CF R 792 . Th e final 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 GLP10-01-02-26
. 

### 3 Projec t Schedul e 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 , Febmar

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 140 0 Stat e Docks Roa d Decatur , Alabam a 3560 1 

### 4 Tes t Parameter s Th e targete d limi t o fquantitatio n wil l b e 0.02 5 ng/m L (ppb ) fo rPFBS , PFHS , an d PFOS
. Atota l of si xsamplin g location s have bee n specified
. Fo reac h samplin g location , a tota l o f fou rsampl e bottle s wil l b e collecte d (sample , sampl e duplicate , low-leve l field matri xspike , an d high-leve l field matri xspike)
. Th e lil 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 tri p blank s consistin g o f reagent-grad e water , a low-leve l tri p blan k spike , an d a high-leve l tri p blan k spik e wil l b e prepare d at th e 3 M Environmenta l Laborator yan d sen t t o th e samplin g locatio n wit h th e othe rbottles
. N o previou s data o n fluorochemicals i n groundwater , surfac e wate ro rsedimen t medi a exist fo rth e site
. Th e lowfield matri xspike wil l b e prepare d at 1 ng/m L an d th e hig h field matri xspike at 1 0 ng/mL
. Al l sampl e bottle s wil l Includ e th e additio n of^*OrPFBS , "CrPFHS , an d "Cs-PFOS
. nntema l standards ) a t a nomina l concentratio n of 1 ng/mL
. M sampl e bottle s wil l als o Includ e th e additb n o f ^ C4-PFO S (sun-ogate recover ystandard ) at a nomina l concentratio 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 fdirect 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 bottles
. N o rinseat e blan k wil l b e collected
.

Pag e 5 o f6 Page 27 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o fPFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2 Analytical

Protocol:

GLP10-01-02 Amendment

26 

### S Tes t Method s Sample s wil l b e prepare d an d analyze d b yLC/MS/M S followin g ETS-8-044. 1 "Metho d o f Analysi s fo rth e Detenninatio n ofPerfiuorinate d Compound s I n Wate rb yHig h Perfomnanc

e Liqui d ChnDmatography/Mass Spectrometr

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

yET S 8-154. 3 "Detemiinatio n of Perfiuorinate d Acids , Alcohols , Amides , an d Sulfonate s I n Wate rB ySoli d Phas e Extractio n an d Hig h Perfomianc e Liqui d Chromatography/Mas s Spectrometry " Wher e applicable , sample s wil l b e analyze d against a n intema l standard calibratio n cun/e
. Eac h cun/ e poin t wil l contai n isotopically-labele d PFBS , PFHS , an d PFO S at a nomina l cxjncentratio n o f 1 ng/mL
. Th e calibratio n cun/ e wil l be generate d b

ytakin g th e rati o of th e standar d pea k are a count s ove rth e intema l standard pea k are a count s t o fit th e dat a fo reac h analyte
. Laborator ycontro l sample s prepare d wit h th e sample s must hav e 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

yof 100+30% . Fiel d matri xspike s not yieldin g recoverie s withi n 100+30 % wil l b e addresse d i n th e repor

t an d th e final 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 field 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 event . Laborator ycontro l spike s of reagen t wate rprepare d at th e tim e ofsampl e extractio n wil l als o b e reporte d an d use d t o evaluat e th e overal l metho d accurac

yan d precision
. Metho d blank s of reagen t wate rprepare d at th e tim e of sampl e extractio n wil l b e use d t o determin e th e metho d detectio n limi t Fo rthos e samplin g location s where th e field matri xspike leve l vras not appropriat e du e t o highe rtha n expecte d analyt e concentrations , a targe t analyt e laborator ymatri xspik

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

Page. e o f 6
Pag e 2 8 o f7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S 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 9 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2

*ETS-McCo

y Result s Name : mcl20313a.rd b

4. 0 4. 5 5. 0 5. 5 6. 0 Analyt e Cone
. /

I S Cone
. Dat a printe d b yST

W Printin g Time : 11:30:3 2 A M Printin g Date : Wednesday , Apri l 11 , 201 2 Pag e 1 o f 1

Pag e 3 0 of 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2

*ETS-McCo y Result s Name : mcl20313a.rd b

0. 0 1. 0 2. 0 3. 0 4. 0 5. 0 6. 0 7. 0 8. 0 9. 0 10. 0 11. 0 12. 0 13. 0 14. 0 15. 0 16. 0 17. 0 18. 0 19. 0 20. 0 21. 0 22. 0 23. 0 24. 0 Analyt e Cone
. /

I S Cone
. Dat a printe d b yST W Printin g Time : 11:31:5 5 A M Printin g Date : Wednesday , Apri l 11 , 201 2 Pag e 1 o f 1

Pag e 3 1 o f7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2 Ginge r AG0133050 9 Result s Name : gl20307a.rd b

4 5 5 0 5 5 6 0 Analyt e Cone
. /

I S Cone
. Dat a printe d b yST W Printin g Time : 12:26:0 8 P M Printin g Date : Wednesday , Apri l 11 , 201 2 Pag e 1 o f 1
Pag e 3 2 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2 Ginge r AG0133050 9 Result s Name : gl20307a.rd b

Dat a printe d b yST W Printin g Time : 12:24:2 6 P M Printin g Date : Wednesday , Apri l 11 , 201 2 Pag e 1 o f 1
Pag e 3 3 o f7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2

*ETS-McCo y Result s Name : mcl20313a.rd b

Dat a printe d b yST W Printin g Time : 11:34:4 6 A M Printin g Date : Wednesday , Apri l 11 , 201 2 Pag e 1 o f

Pag e 3 4 o f7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2

*ETS-McCo y Result s Name : mcl20313a.rd b
I I Sampl e Name ' -n:ic120313a033 ' Sampl e ID : -LC&-12O306- rFie ' PeakName'-13C4PFOS-Surr * Mats(es)'-503.000/80.00 0 Da ' I I Comnwi t •20pp b LCS ' Annotetten ' -

Smoothin g Kldth ; 

# I Sampl e Name ' 'mc12O313a040 " Sampl e ID ; 'GLP11V01-02-27-025 ' File ' •mc120313a.wtf r Pea k Name ' -13C4PFOS-Sun - Mass(M} : '503.000/80.00 0 Da ' Comment ; "JPAL-SW-TRIPI-O " Anrwtatoo; " Sampl e Index : 40 Sampl e Type : Unknow n Concentration
. It/ A1 10B4 ' Calculate dCone : 0.10 3 ng/m L Acq . Date : 3/14/201 2 1.05e4
- Acq . Time : 3:31:3 4 A M 1.0064 - Hodl f led : ti e

- H Q II I 9500.00
-

9000.00
- 8500.00
- 8000.00
- 7500.00
- 7000.0 0 6500.00
- Retentlo n Time : 13. 3 nl n g 6000.00
- Height : 1.12e-f00 4 cp s ^5500.00
- Stat t Time : 13. 2 nl n g EndTime
- 13. < mi n c 5000.00
- 4500.00
- 4000.00 : 3500.00
- 3000.00
- 2600.00
- 2000.00
- 1500.00
- 1000.00 - 500.00- i 0.00 - Ittim ; Specif y I

Bas e T o Bos



# I Sampl e Nam e •mc120313aO41 " Sampl e ID ; •GLP10-01-02-27-026 - Fi e 'mcl2031Sa.wif T Pea k Name
. -13C4PF0S-SurT - MaM(ea) - '503.000/80.00 0 Da ' Commen I 'JPAL-SW-TRIPI-LS - Annolallon'* * Sampl e Type : Unknow n Concentration : H/A Calcuiater f

Cone : 0.10 4 ng/m L1.1064
- Acq . Date : 3/14/201 2 iftfj j Acq . Time
- 3:52-4 B A M I.K>»4
- 1.00e 4

- M Q Ti l 9500.0 0

9000.00 8500.00 ' 8000.00
-
" 7500.00 '

7000.00
- 6500.00 ' & 6000.00
- KLii . Pea . Window : 1.0 0

1 . Factor : 2 rgea t Peak ; Ye a iight : 0.0 0 Pea k Width : R T V Us e Felativ i Int . Type : Retentio n T : Area : Height : 13. 3 Ye s 'alle y I 5500.00 ' 1 5000.00 - 4500.00 - 4000.00 - 3500.00 - 3000.00 - 2500.00 - 2000.00 - 1500.00 - 1000.00 - 500.00 - 

# I Sampl e Name : 'mc l 20313a044 ' Sampl e ID
. "GLP10-01-02-27-005 ' pMkNam a •13C4PFOS-Sufi ' Mass(es).'503.000/80.000Da ' CkHnmant ; "JPAL-SW-ETOI-O " Annotation
. ~ Sampl e Index : 4 4 Sampl e Type : Unknow n Concentration : II/ A Calculated Cone: 0.104 ng/mL Acq . Date : 3/14/201 2 Acq . Time : 4:56:3 2 A M Pioc . Algorithm : Specif yParameter :

Pea k Width :

Bas e T o Bas e

13. 3 mi n 237E 0 count s 6.31e'0O 3 cp s

Dat a printe d b yST W Printin g Time : 11:34:4 6 A M Printin g Date : Wednesday , Apri l 11 , Pag e 2 o f 9

Pag e 3 5 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2

*ETS-McCo

y Result s Name : mcl20313a.rd b 

# r Sampl e Name ; 'mc l 20313a052 ' Sampl e ID
. •GLP1O-O1-O2-2T-O09 ' Pea k Name ; '13C4PFOS-Sun ' Mass(©s) - -503.000/80.00 0 Da ' Conrirrwnl ' 'JPAL-SW-ET02-0 ' Annotation : ~

Smoothin g Ki d Expecte dRT :
Height : Star t Ti f En dTime
5.98et00 3 cp s

4. 5 15. 0 15. 5 I SampleNarr * •mc120313a054 - SamptelD:'GLP1CH)1-02-27-011 " RIo"•mcl20313a.wi r Peal;Nan » '13C4PFOS-Sun * Massfes ) '503.000/80.00 0 Da ' I Commen t •JPAL-SW-ET02-LS " Annotation. "

nthra : Specif y Par i

Area : Height : 13 .

2195 7

11. 0 11. 5 12. 0 12. 5 13 0 13. 5 14. 0 14. 5 15. 0 15. 5 

# I Sampl e Nam e •mc120313a057 - Sampl e ID
. •GLP1D-01-02-27-013 - Fie ; •n>c120313a.wff r Pea k Name ; •13C4PFOS-SurT- Mass(es) : -503.000/80.00 0 Da " Comrrken l •JPAL-SW-ET03-O ' /Vinotation : " " sampl e Index : 5 7 Sampl e Type : Unknow n Concentration: ll/A t Calculate dCone
- 0.10 4 ng/m L Acq . Date : 3/14/201 2 Acq . Tine
- 9-32:3 7 A M i Proc . Algorithm ; Sp i Nois e Percentage : Base . Su

b Windo w 

# I SampteNam e -mcl20313a065 " Sampl e ID;•GLP1O-01-02-27.O17 ' Rte'•mc120313a
. Pea k Name
. -13C4PFOS-Sun - Mass(es)
. "503,000/80.00 0 Da ' Commen I •JPAL-SW-ET04-0 " Annotation - ~ Sampl e Index : 6 5 Sampl e Type : Unknoia n Concentration : ll/ A Calculate d Conc t 0.10 8 nq/ra L

Specif y Par

j )w : 1.0 0 Peak-Split . Factor : Repor t Larges t

Peak ; Hln . Pea

k Height : Hin . Pea

k Width : SmoQthin g Width : R T Window :

14. 5 15. 0 15. 5 Dat a printe d b

yST W Printin g Time : 11:34:4 6 A M Printin g Date : Wednesday , Apri l 11 , Pag e 3 o f 9

Pag e 3 6 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2

*ETS-McCo

y Result s Name : mcl20313a.rd b

Dat a printe d b yST

W Printin g Time ; 11:34:4 6 A M Printin g Date : Wednesday , Apri l 11 , 201 2 Pag e

Pag e 3 7 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS
. PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2

*ETS-McCo y Result s Name : mcl20313a.rd b 

# J Sample

Name' •mc120313a033-

Sample ID;'LCS-120306-r

Fie: -mcl 203130.wifT Peak Mama; "ISCaPFOS-ISpS)-

MaM(es);

-507.000/80.000

Da' CortWTwnt;

*20ppb LCS- AnrmtaUon, ~ I Sampl e Name;'mc120313a040 " Sampl e 10 : •GLP10-01-02-27-025 " File , "mcl2031aa.wi T PeakNamo'-13C8PFOS-IS(IS) - M8w(es) , •507.00(V80.000Da I Commen t "JPAL-SW-TRIPI-O - Annotalxwi. -

Proc . Algorithm : IntelliOua n - Min . Pea k Height : 0.0 0 cp s Hin . Pea k Width : 0.0 0 se c

n g Width : 3 pol l R T Window : 30. 0 se t Expecte d RT :

• RT : 13. 3 32169 2 c

< e . B2e*004



# I Sampl e Nam e -mcl20313o04 rSampl e ID ; "G L P I 0-01-02-27-026 " Pea k Nan>e ' •13C8PFOS-IS{IS) ' MaM(es) ; '507.000/BO.OO O Da ' Commen l -JPAL-SW-TRIPI-LS - AnnolaUon - " Sampl e Type : Unknow n
lodified : Ptoc . Algorithm : Intel1lO i Min . Pea kHeight : 0.0 0 Min . Pea kWidth : 0.0 0 Smoothin g Width : 3 R T Windov : 30. 0 Expecte d RT : 13. ^ ! Rela l • RT : 1( 0

13.5tain 

## ( Sampl e Name
. •mc120313a044 " Sampl e ID : -GLP l 0.01-02-27-005 - RIe ; -mc120313a . Pea k Name
. -13C8PFO&JS(IS) - Mass(es) : -507.000^80.00 0 Da Comment
. -JPAL-SW-ETOI-O - Annotation ; - Sampl e Index : 1 4

Height : Star tTi l En d Tin e

Dat a printe d b yST W Printin g Time : 11:34:4 6 A M Printin g Date : Wednesday , Apri l 11 , 201 2 Pag e 5 o f

Pag e 3 8 o f 7 7GLP l 0-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2

*ETS-McCo y Result s Name : mcl20313a.rd b

Dat a printe d b yST W Printin g Time : 11:34:4 6 A M Printin g Date : Wednesday , Apri l 11 , Pag e 6 o f 9

Pag e 39 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2

*ETS-McCo y Result s Name ; incl20313 a. rd b 

# I Sampl e Name ' 'mc l 20313a015 * Sampl e ID , -11012- W Flo ' -mc120313a . Pea k Name ; "P f OS " Mass{es) : MgS.OOOraO.OO O Da.499.000/99.00 0 Da,499.000/130.00 0 Da * Commen i -0.2 5 n^m l F C st d n Sjnth
. Water* Arewtatton ; ~ Sampl e Inden : 1 5 Sanpl e Type : Standar d Concentration : 0.23 2 ng/m L Calculat e ng/m L

roc . AlgotiChni : Specif y Par i ise . Sub . Window
- 1.0 0 lak-Spllt . Factor ; S •por t Larges t

Peak : Ye a In . Pea k Kelgtit : 0.0 0 i n . Pea k Kldth : 0.0 0 :ioothln g Width : 3

Retentio n Tine : 13. 3 Area : 7207 1 co i Height : 1.42e*00 4 Star t Time ; 12. 8 EndTime : 13. S 

# I SampteNam e "mc l 20313a026 " Sampl e ID
. •12001-150 - Fil e "mc l 20313 a .wt T Pea k Nam e "PFOS - Mass(es) ' M99.0O0/80.0O 0 Da,499.000/99.00 0 Da,499.000/130.00 0 Da Commen t 'MeitMy l Blank : Annotation
. ~ Sanpl e Index : 2 6 Sampl e Type : Unkno- n



## [ Sampl e Name ; -rT>c120313a02 rSampl e ID - TCS-120306-1 - Fie : 'mc120313a
. wifT Pea k Name ' 'PFOS * Mass(es) : '499.000/BO.OO O Da.499.000/99.00 0 Da.499.000/130.00 0 Da ' Conmeol ' '0.2pp b LCS - AnmUIton : ~

Modified : Proc . Mgorlthm : S y Nois e Percentage : Base . Sub , Hindow : Peak-Split . Factor . Repoc t Larges t

Pea l Min . Pea

k Height : Min . Pea

k Width : R T V

Ftne . mt n Dat a printe d b yST W Printin g Time : 11:34:4 6 A M Printin g Date : Wednesday , Apri l 11 , Pag e

Pag e 4 0 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s of PFBS
. PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2

*ETS-McCo y Result s Name : mcl20313a.rd b 

# B Ssmpt e Name
. -mcl20313a033 ' Sampl e ID ; -LCS-120306- rFi e -mc l 20313a.wi r Pea k Name
. 'PFOS ' Mass(es) : -499.0DO/B0.0O 0 Da,499.000/99.00 0 Da,499.000/130.00 0 Da ' Commerit
. -20pp b LCS - Annotation
. ~ Sainpl e Index : 3 3 Sampl e Type . Q C Concentration : 19. 4 ng/m L Calculate d Cone : 17. 1 ng/ra L Acq . Date : 3/14/201 2 Ac q Time : 1:02:5 7 A M Modified : Ye s

Smoothin g Width ; Expecte d RT : 

# I Sampte Name , -mc l 20313a040 - Samp4 e ID ; -GLP l 0<H-02-27-025 - FOe' "mc l 20313a.wt T Pea k Name ' 'PFOS * Massfes) ' '499.000/BO.OO O Da,499.000/99.00 0 Da,499.000/130.00 0 Da ' Comment'JPAL-SW-TRlPl-0 - Annotattofi" -

Algorithni : Spe f l e Sub . Windox : ik-Split . Factor : >ortLarges tPea ) 1 . Pea kHeight : 1 . PeakWidth : lOthln g Width : Window : lecte d RT : ) Rela l Type : • RT :

1 4 5 15. 0 

# I Sampl e Name
. *nr)Cl20313aO41 ' Sampl e ID - 'GLP l 001-02-27-026 ' Fi e Pea k Name
. 'PFOS ' Mass{es) ; -499.000/80.00 0 Da,499.00Q/99.00 0 Da,4 ! CommenI , 'JPAL-SW-TRIPI-LS - Annotalion ; ~ Saaipl e Index : 4 1 Sampl e Type : Unknow n

Date : 3/14 / Time : 3:52 : 0 9 ng/m L

:hir : Specif yParamet e

Pea k Height : Pea k Width : ithin g Width : 9.5e 4 9.0e 4 e.5o 4 e.0e 4 7.5e 4 7.0»4 - e.5e 4 e.0e4 - 5.5w J 5.0» 4 4.5»4 - 4.0e4 - 3.5e 4 3.0e4 - 2.5e 4 20e 4 1.5e4- 

# i I Sampl e Name;'mc120313a044 ' Sampl e ID-'GLPHW>1-02-27-005 ' Rl e "mc l 20313a.w W Pea k Name ; 'PFOS * Mass{es) ' •499.000/80.00 0 Da,499.000/99.00 0 Da,499.000/130.00 0 Da ' I Comment"JPAL-SW-ETOl-O - Annotation: "

Window :

:s e Relati i
n t Type : .etentio n 1 eight :

Dat a printe d b yST W Printin g Time : 11:34:4 6 A M Printin g Date : Wednesday , Apri l 11 , Pag e

Pag e 4 1 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2

*ETS-McCo y Result s Name : incl20313 a. rd b
I I Sampl e Nam e •mc120313a052 ' Sampte ID
. •GLI'10-01-02-27-009 * Flo:'mclZOSlSa.wtf T Pea k Nam e 'PFOS ' Mass(es):'499.000/80.00 0 Da,499.000/99.00 0 Da,499.000/130.00 0 Da * I I Commen t •JPAL-SWCT02-0 ' AnnotaUo n " : Type : .ate dCon

e Algorithm : Spe

c Peak-Split . Facto r Repor t Larges t

Peal Hin . Pea

k Height : Hin . Pea

k Width
R T Window : Expecte dRT :
Retent K Area . Height : f y Par £ 5 0 1.0 0 

## ( SampleNam e "mcl20313a054 ' SampteID;"GLPl(Ml-02-27011 ' Rle''mc1203l3a
. Pea k Name : 'PFOS ' Massfos) ; '499.000/80.00 0 Da,499.000^9.00 0 •a.499.000/130.00 0 Comnnent : 'JPAL-SW-HT02-I-S " Annotation. " Sampl e Index : 5 4 Sampl e Type : Unknow n Concentration ; ll/ A Calculate dCone : 0.92 4 ng/m L Acq . Date : 3/14/201 2 Acq . Time : Bi2B:5 5 A M , Ptoc . Algorithm : Spec Nois e Percentage : Base . Sub . Window : Peak-Split . Factor : Min . Pea

k Height :

Int . Type : Retentio n 1 Area : Height : 13. 2

27ei« B c

c 5.49e-t00 4 12. 7

15. 0 15. 5 Sampl e Nam e •mc120313a057 ' Sampl e ID:'GLP10-01-02-27-013 ' Fi e •mc120313a.wif r Pea k Nam e 'PFOS ' Mass(e*) : '499.000/60.00 0 Da,499.000/99.00 0 Da,499.000/130.00 0 Da ' Commen I 'JPAL-SW-ETOa- C Annotatto n - Sampl e Index ; 5 7 Calculate d Cone : 0.30 3 Acq . Date : 3/14/201 2 Acq . Time : 9:32:3 7 A M 

## ( Sampl e Nam e 'mc120313aO65 ' Sampl e ID : 'GLP l 0-01-02-27-017 ' Rle
. 'mcl20313 a vtifT Pea k Nam e 'PFOS ' Mass(es ) '499.000/80.00 0 Da,499.000/99.00 0 Da,499.000/130.00 0 Da Commen t "JPAL-SW-ET04-0 ' Annotation , ~ Sampl e Type ; tjnknow n Concentration : ll/ A Calculate dCone : 0,l£ e ng/n L Acq . Date : 3/14/201 2 8500
- Acq . Time
- 12:22:3 2 P H 8000 - 7SM . 7000
- Proc . Algorithm : Specif y Pa n Hois e Percentage : 5 0 Base . Sub . Window : 1.0 0 Min . Pea

k Height : Min . Pea

k Width : Smoothin g Width : 5500 ' 5000 ' 4SO 0 4000 -

11. 0 11. 5 12. 0 12. 5 13. 0 13. 5 Time , m m Dat a printe d b yST

W Printin g Time : 11:34:4 6 A M Printin g Date : Wednesday , Apri l 11 , 201 2 Pag e 9 o f 9

Pag e 4 2 o f 7 7GLP l 0-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2 Ginge r AG0133050 9 Result s Name : gl20307a.rd b

• Sample Name : 'o120307o014 ' Sampl e ID.'11012-6-6 ' Fie ; 'a120307a . Pea kNam e 'ISCSPFHS-ISOS rMass<es) . '402.0^0. 0 am i " Commen t"0.2 5 n^'m L F C st d m Synth. Watei - Annoialio n Sampl e Index : 14 ilate d Cone . 9;35:1 9 P M Led : Hin . PeakHeight : Min . Peakwidth : Smoothin g Width : R T Window : Expecte d RT : Us e Relativ e RT ; 0.0 0 J 3 0 0 

# I SampteName •gl20307a02 rSample ID,'12001 . Pea kName : '13C3PFHS-IS{IS) ' M3M(es) : '402, " Comman t'Metho d Blank" Annotation: " Sacapl e Index : 2 7 Sampl e Type ; Unknow n Concentration ; 0.94 5 ng/m L Calculate d Cone : ll/ A Acq . Date ; 3/8/201 2 Acq . Tine ; 2:00:2 4 A M
Hin . Pea kHeight ; Hln . Pea kwidth . Smoothin g width '



# I Sampt

e Name ' '91203073028 ' Sampt e ID : •LCS-120306- rFite ' •g120307a.wi r Pea kName-'13C3PFHS-IS{IS) ' Mass(es):'402.0/80. 0 Comment; •0.2pp

b LCS ' Annotatkin. " Sampl e Index : 2 6 Saopl e Type : Q C Concentration ; 0.93 7 ng/mL Calculate d Cone - N/ A Acq . Date ; 3/B/201 2 Acq . Tine ; 2.21:3 4 A H Modified ; Proc . Algorithm : Min . Pea k Height : Hin . Pea k Width ; Smoothin g Width : R T Window
Expec t Us e Rt ! RT :

2.56etO0 5 cp s 

# I Sample Name : *g12O307aO31 ' Sampt e ID : 'LCS-120306-4 ' Fie . 'a120307a.wtr PeakName , '13C3PFHS-IS(tS) ' Mass(ai) ' "402.0/80. 0 Commen I •2pp b LCS ' Annotalian: " Sampl e Index : 31

ic . Algorithm : ] I . PeakHeight : I . Pea kWidth : lOthin g Width ; Window : lecte d RT : It . Type . 86643 2 c c 2.47e»O0 5 14. 7

Dat a printe d b yST W Printin g Time : 12:30:1 1 P M Printin g Date : Wednesday , Apri l 11 , 201 2 Pag e 1 o f 1 2 1438 148 8 T1n>e, mi n
Pag e 4 3 o f 7 7GLP l 0-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2 Ginge r AG0133050 9 Result s Name : gl20307a.rd b 

# r Samf* , Name , •g120307a034 - Sampte ID ' TCS-120306- rfU - •g120307a.w r Paa k Name : •13C3PFHS.1S(IS) - Mass{8S)'•402. r Commam
. "20pp b LCS ' Annolatio n -

Dat a printe d b yST W Printin g Time : 12:30:1 1 P M Printin g Date : Wednesday , Apri l 11 , Pag e 2 o f 1 2
Pag e 4 4 o f7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS
. PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2 Ginge r AG0133050 9 Result s Name : gl20307a.rd b 

# I Sampl e Nam e '9l20307a046 ' Sampl e I D 'GLP1041-02 - Pea k Nam e '13C3PFHS4S(IS) ' Mass(es) , '402.0/60. 0 Comment ; 'JPAL-SW-ET01-D8 ' Annotation. " Sampl e Type : Unknow n

H m . Pea

k Height : Min . Pea

k Width : Snoothin g width : Expecte dRT : !- . 14. 9

88420 1 c

c 2.66e+00 5 14. 7 15. 2 

# I Sampte Name : 'g120307a053 ' Sampte I D 'GLP l 0-01-02-27-009 ' F.le , •gl20307a.wi r Pea k Name , '13C3PFHS-IS(IS) - MaM(es ) '402.0/80. 0 a i ~ Commen t •JPAL-SW-eT02.0 - Annotation : " Sampl e Index : 5 3 Sampl e Type : Unknow n Concentration : 0.9 4 5 ng/m L Calculate dCone : ll/ A Acq . Date : 3/8/201 2 Acq . Time : 11:11:1 0 A M 2.6e 5

Height ; Star t Ti l En dTin e

1240 12S 9 

# I Sampte Name:'a120307a05e ' Sampta 10 : •GLP1lW)1-02-27-013 ' F* e 'g120307a.wtf r Pea k Nam e MSCSPFHS-IStiS) ' Mass{es) : '402.0/80. 0 Comment : 'JPAL-SW-ETOS-O " Annotation
. " sanpl e lnde« ; S S Saopl e Type : Unknow n Acq . Time ; 12:57:1 1 P H Modified : Ye s Pro c Algorithm : IntelliQua n - ] Min . Pea k Height ; 0.0 0 cp s Hln . Pea k Width ; 0.0 0 se c SnoQthin g width : 3 point ; R T K 30. 0 Expecte d l Us e Relativ e BT . H o Int . Type : Valle y Retentio n Time ; 14. S roin Atea : 96287 B count s Height ; 2.89e»00 5 cp s 

# I Sampt e Nart w•g120307a066 ' Sampl e ID : 'GLP10-01-02-27-0i rFito : '81203073
. Pea k Name - -13C3PFHS-B{IS) ' Mas»(es) , -402.0/80. 0 Cocranenl : 'JPAL-SW-ET04-0 ' Annotation. " Sampl e Index ; 6 6 impl e Type : Con e Calcula i 0.94 5 11/ A Acq . Time ' 3:46:4 6 I Modified : Ye s Ptoc . Algorithm ; IntelliQ i Min . Pea k Height ; 0.0 0 Min . Pea k width : 0.0 0 Smoothin g Width : 3 BT Window : 30. 0 Expecte d RT : 14. 9

! RT : W

o Valle y : : 14. 8 m m 94272 9 count s 2.896*00 5 cp s 14. 7 mi n 15. 2 mi n

Dat a printe d b yST W Printin g Time : 12:30:1 1 P M Printin g Date : Wednesday , Apri l 11 , 201 2 Pag e 3 o f 1 2
Pag e 4 5 of 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2 Ginge r AG0133050 9 Result s Name : gl20307a.rd b

Sampte Name : •gl20307a014 ' SamplelD.'11012-6-6 ' Fie:'g120307a.wi r PeakNam e '13CBPFOS-tSpS) ' M3ss(as ) '507.0/80.0ami T Comment : "0.2 5 n^'m L F C st d m Synth
. Wate rAnnotation : ~ sampl e Index . 1 4 Sampl e Type : Scandac d Concentration : 0.96 0 ng/m L Calculate d Cone : N/ A Acq . Date : 3/7/201 2 Acq . Time : 9:25:1 9 P M Modified : Ye s Proc . Algorithm : IntelliQua n - IQf i Min . Pea k Height ; 0.0 0 cp s Min . Pea k width : O.O O se c Snoothin g Width ; 3 point s R T Window : 30. 0 se c Expecte dRT ; 15. 9 mi n Us e Relativ e RT ; H o Int . Type : Valle y

5 . Gle->00 4 Sampt e Name ' •g120307a027 ' Sampl e ID : '12001-160 ' fie - •g120307a.wif r I Pea k Name : '13C8PFOS-lS(IS rM3ss(es)
. '507.0/80. 0 a r Comment'MattMxlBlank " Annotation, ' Sampl e Index : 2 7 Sampl e Type : Unknow n Concentration ; 0.96 0 ng/m L Calculate dCone : N/ A e.0o4
- 7.5o4 7.0o4
- 6.5o4
- 6.0e4 5.5e 4 5.0e 4 I
^ 4.0e4 S S 3.5 M 3.0e4 ' 2.5e 4 2.0e 4 1.5e4
- 1.0e4
- 5000.0
- Modified ; Ye s Proc . Algorithm ; IntelliQu ; Min . Pea k Height : 0.0 0 Min . Pea k Width ; 0.0 0 Snoothin g width ; 3 f R T Window : 30. 0 Expecte d RT ; Us e Relativ e BT :
Heiglit ; Star t 1 En d Ti n

133 9 138 8 

# I Sampte Name : •gl20307aO28 " Sampl e ID ' •LCS-120306- rFie : -a120307a.iM r Pea k Name ' '13C8PFOS-IS{IS) - Mass(»s) ' •507.0/00. 0 ami T Comment* '0.2pp b LCS " Annotation : ~

Modified ; 2 8 Q C 0 . 95 1 N/f t 3/B/201 2 2:21:3 4 ftM Ye s IntelliQua r Min . Pea

k Height : 0.0 0 Min . Pea

k Width : 0.0 0 Snoothin g width : 3 R T Mindow ; 30. 0 

# I Sampt e Name : •Bl20307a031 ' Sampte ID ' •LCS-12030S-4 ' Fie - 'g120307a.wir r Pea k Nam e 'ISCePFOS-ISflS) ' Mass(es)''507.0/60. 0 Commen t '2pp b LCS " Annotatio n ~ Sampl e Index : 3 1 Sampl e Type ' Q C Concentiatlon ; 0.9S 1 ng/m L Calculate dCone : H/f i Acq . Date : 3/S/201 2 Acq . Time : 3:25:1 1 A M

Us e Belativ t Int . Type ; Valle y

25243 7 C

I

1537 158 7 Time , mi n Dat a printe d b yST W Printin g Time : 12:30:1 1 P M Printin g Date : Wednesday , Apri l 11 , 201 2 Pag e 4 o f 1 2
Pag e 4 6 o f7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2 Ginge r AG0133050 9 Result s Name : gl20307a.rd b

Pea k Height : Pea k Width ; Jthin g Width : 0.0 0

0.0 0 3 30. 0 H Sampte Name;'g120307a034 ' Saniplel D •LCS-120306- rFie * •g120307a.wi r PeakNam e •13C8PFOS-tS{lS) ' Mass(es ) '507.0^0. 0 amu ' I I CommenL'20ppbLCS * Annotation. " g.0e4 ' 8.5e 4 8.0e 4 7.5o4 - 7.0e4 - 6.5e 4 6.0e 4 5.5e4 ' 5.0e4 ' 4.5o 4 4.0e 4 3.5*4 - 3.0e4 - 2.5«>4' 2.0e4 '
1.0e4 5000.0 - 133 9 138 8 143 8 

# I Sampte Name ' 'g1203D7a041 ' Pea k Name ' 'nCBPFOS-ISdS r Comnfien t 'JPAL-SW-TRIPI-O " Sampl e Index : 4 1 Sampl e Type : Unknow n Concentration ; 0.96 0 Sampte I D 'GLP10-01-02 - Mass(es) : '507.0/80. 0 Annotation. "

0.0 0 3 30. 0 Smoothin g Wi

c R T Window : Expecte dRT : Us e Relativ e Int . Type ; Valle y Retentio n Time : 15. 8 Atea : 73926 4 c i



# I Sampte Nam e •a120307aO42 - Sampte ID : 'GLP l ^01-02-27-026 ' Fie ' 'g12O307a.wif r Pea k Nam * 'ISCSPFOS-ISOS) ' Mass{os) , '507.0/80. 0 amu " Comment:'JPAL-SW-TRIPI-LS ' Annotation: " Sampl e Index ; 4 2 Sampl e Type : Unknow n Concentration ; 0.96 0 ng/m L calculate dCone
- N/ A Acq . Date : 3/8/201 2 Acq . Time . 7:18:1 1 A M Proc . Algorithm ; IntelliQua n- I Min . Pea

k Height ; 0.0 0 cp s Hin . Pea

k Width ; 0.0 0 se c Smoothin g width ; 3 point s

Height . Star t 1 En dTi D 

# I Sampte Name ' 'g120307a045 ' Sampte ID , "GLP10-01-02-27-005 ' Fite ' •g120307a.wrf r P«akNam*''13C8PFOS-IS(IS) ' Mass(*a),'507. f Commen t "JPAL-SW-ETOI-O ' /Annotation. '

Modified : Min . Pea k Height ; Min . Pea k Width ;

Dat a printe d b yST W Printin g Time : 12:30:1 1 P M Printin g Date : Wednesday , Apri l 11 , Pag e 5 o f 1 2
Pag e 4 7 o f7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2 Ginge r AG0133050 9 Result s Name : gl20307a.rd b

I Sampte Nam e 'g12O307BO46 " Sampte ID,'GLP1CM)l-02-27-006 ' FN'"g120307B.wi r Pea k Name : "ISCePFOS-ISOS) ' Massfes)
. '507.0/80. 0 ami T J Commen t 'JPAL-SW-ETOI-OB ' AnnoUlion : -

Proc . Algorithm : Kin . Pea k Height : Win , Pea k Width ; Smoothin g Width ; R T Mindow :

Height : Star t T : En d Tim . Valle y

• : 15. 8 mi n 324S1 0 count s 1.04e«OO S cp s 

# I SampteName
. 'g120307B053 ' Pea k Name
. '13C8PFOS-IS(IS) ' Commen L 'JPAL-SW/-ET02-0 ' Sampl e Index : 5 3 Sampl e Type ; Unknow n Con < Cal l Sampt e ID - "GLP l 04)1-02-27-009 - Fit e 'g1203078. w Mass<as) ' '507.0/30. 0 amu ' Annotation ; — 1.96 0

Proc . Algorithm ; : Min . Pea k width : Smoothin g Width ; B T Window : e d RT ; Rela l
Height ; En dTine ; i BT ; itelliOu a O.O O J F 30. 0 15. 9 ll o Valle ' 15. i 37204 6 l.lOeS
1.05e5
- LOOeS
9.50e4
- 9.00e4 ' a.50e4
- 8.00e4 ' 7.50*4
- 7.00e 4 6.50» 4 6.00*4
- ES.50»4 ' i I5.00*4 ' 4.50*4
- 4.00*4
- 3.50*4
- 3.00*4
- 2.50e4
- 2.00*4
- 1.50*4
- 1.00*4
- 5000.00
- 0.0 0 

# I Sampte Nam e 'a120307a058 " Sampte ID ' 'GL P 10-01-02-27-013 ' Fte ' 'g120307a
. wlfT Pea k Name : "laCSPFOS-ISOS) ' Masa(*s ) '507.0/80. 0 Commen t 'JPAL-SW-ET03-0 ' Annolallo n - Sampl e Index : 5 S Sampl e Type ; Unknow n Concentration : 0.96 0 ng/m L Calculate dCone ; K/ A Acq . Date ; 3/S/201 2 Acq . Time : 12:57:1 1 P M Modified ; Ye s Proc . Algorithm ; IntelliCua n - IQA Min . Pea

k Height : 0.0 0 cp s Hin . Pea

k Width ; 0.0 0 se c

Height : Star t Ti l En dTin e 

# I Sampt e Name ' 'gl20307a066 ' Sampt e I D "GLP l 0-01-02-27-0i rFito ' •g120307a.wif r PeakName.'13CePF0S-IS(IS) ' Mass(es ) '507.0/80. 0 Commen t *JPAL-SW-ET04-0 ' Annotation
. ~

Modified : ^e s Proc . Algorithm : IntelliQua n - Min . Pea k Height ; 0.0 0 cp : Min , Pea k Width ; 0.0 0 se t Smoothin g Widt h3 pol r R T Window ; 30. 0 se c

( BT . 15. 9

ll o

Dat a printe d b yST W Printin g Time : 12:30:1 2 P M Printin g Date : Wednesday , Apri l 11 , Pag e 6 o f 1 2
Pag e 4 8 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2 Ginge r AG0133050 9 Result s Name : gl20307a.rd b 

# I Sampt e Nam* : •9l20307a014 * Sampt e ID.'11012-&6 ' Fie.'g120307a.wif r Pea k Name : *PFBS ' Masses ) '299.0/99. 0 amu,299.0/80.0a r~ ComoMnt : "Oa s ng/m L F C std I n Synth
. Wate TAnnotation : ~ Sampl e Index ; 1 4 .25 0 Sampl e Type ; Calculate d Cone : 1.28 5 3/7 /

Peak-Split . Factor ' Repor tLarges tPea ) Min . Pea kHeight : Mm . Pea kwidth ; 1.15e 5 1.10*5 1.05e 5 1.00e 5 9.50*4 9.00* 4 8.50e 4 s 8.00*4 7.50*4 7.00*4 6.50*4 ^ 6.00*4 I5.60e4 - ^ 5.00*4 4.50*4 ' 4.00e4 - 3.50*4- 3.0De 4 2.S0e 4 2.00*4 ' 1.50e4- 1.00s4 ' 5000.00 ' 0.00- 109 1 114 1 

# I Sampt e Nsme , 'gl20307a027 ' Sampt e ID : '12001-160 ' Fla ' -g120307a.wif r Pea k Name
. 'PFBS ' Mass(es) : "299.0/99. 0 amu,299.CV80. 0 amu * Comment : -Metho d Blan W Annotation : - Sampl e Index : 2 7



# I Sampt e Name - •gl2O307aO28 ' Sampt e ID ' -105-120306-1 ' Fie : 'gl20307a.wt r Pea k Nam*'-PFBS - Maaa(es):'299.0/99. 0 amu.299.0iW. O ' Comment : *0.2pp b LCS - Annotation : ~ Sampl e Type : Q C Calculate d Co i

: Height : : Width . [ Width :

Height : Star t1 En d Ti n Valle y 13. 4 32522 6 c c 9.25et00 4 13. 3 13. 6 

# I Sampte Name : 'g12O307aO31 ' Sampte ID ' 'LCS-120306-4 ' Pea k Name
. -PFBS " Mass(es) : -299.0/99. 0 amu,299 . Commen t -2pp b LCS * Annotation ' ~ Sampl e Index : 3 1 Sanpl e Type ; Q C Concentration : 1.9 8 ng/mL Calculate d Cone : 2.1 7 ng/mL Acq . Date ; 3/B/201 2 Acq . Time : 3.25:1 1 A M
Nois < Pe n Und o Peak-Spilt . Repor t Larg < Hin . Pea k H

< Min . Pea k widt h Smoothin g width : R T Hindow ; Expecte d RT : Us e Relativ e RT . Int . Type : :elli(;ua r 5 0 1.0 0

320336 B co l 8.72e-'00 5 13. 3

Dat a printe d b yST W Printin g Time : 12:30:1 2 P M Printin g Date : Wednesday , Apri l 11 , 201 2 Pag e 7 o f 1 2
Pag e 4 9 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2 Ginge r AG0133050 9 Result s Name : gl20307a.rd b

I I SampteName'*g120307B034 ' Sampte ID , •LCS-120306- r I Pea k Nam*''PFBS ' Mass(es ) '299.0/99. 0 amu,299.0«(0. 0 I I Comment'"20ppbLCS ' Annotation: " Saopl e Typ e Concenttat l Calculate d Acq . Date ;

Nois e Percentage : Base . Sub . Hindo w Peak-Split . FactO ] PeakHeight ; 

# I Sampte Name - 'gl20307o041 ' Sampte ID
. 'GLPl0-01-02-27-025 ' FOe , •gl20307a.w« r Pea k Name : -PFBS ' Mass{BS) ' '299.0/99. 0 amu,299.0/B0. O amu ' Comment : 'JPAL-SW-TRIPl- C Annotatton: " Sampl e Index : 4 1

Smoothin g width : R T Window : Expecte d RT ;
Height : Star tTi n En d Time :



# I Sampte Name ' •gl20307a042 ' Sampte ID ' 'GL P 10^1-02-27-026 " Fie : -9l203Q7a.wif r Pea k Name : TFBS ' MaM(es) : •299.0ra9. 0 amu,299.)V80. 0 Comment : 'JPAL-SW-TRIPI-LS ' Annotation: "

ic tLarges tF ( PeakHeight ; PeakWidth : 

# I Sampt e Name : •gt20307a045 ' Sampte ID : 'GLP10-01-02-27-005 ' Fite ' •3l20307a.wt r Pea k Nam* ' TFBS ' Masa(as} ' "299.0/99. 0 amu,299.0/30. ~ Comment'JPAL-SW-ETOI- C Annotation : " Sampl e Index ; 45 Sampl e Type - Unknow n tion ; ll/ A d Cone : 0.034 5 2.0* 4 Acq . Time : S Modified ; Proc , Algorithm : ] Base . Sub . window : -Split . Facto i Repo . n . Pea kI

Height : Star tTi r En d Time . •ight :

^» ' Dat a printe d b yST W Printin g Time : 12:30:1 2 P M Printin g Date : Wednesday , Apri l 11 , Pag e Pag e 5 0 o f7 7GLP l 0-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2 Ginge r AG0133050 9 Result s Name : gl20307a.rd b

Dat a printe d b yST

W Printin g Time : 12:30:1 2 P M Printin g Date : Wednesday , Apri l 11 , 201 2 Pag e 9 o f 1 2
Pag e 5 1 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2 Ginge r AG0133050 9 Result s Name : gl20307a.rd b 

# I Sampt e Name , '9l20307a014 ' Sampte ID - '11012-6-6 ' Fie
. •g120307a.w( r Pea k Name : 'PFHS " Mass(es) ' -399.0/99. 0 amu,399.0/80. 0 amu ' Comment
. "0.2 5 nglm l F C std I n Synth
. Water* Annotatio n

Valle y • : 14. 9 38628 4 c c Height : Star t Ti l En dTim e

124 0 Sampt e Nam e "9l20307aO27 " Sampte ID''12001-160 - Fl a •9l20307a.wif r Pea k Nam e 'PFHS ' Mass(es) : '399.0/99. 0 amu,399.0/80. " I Commam : 'Mettw d Blank ' AnnotatKm " Sampl e Index . Sampl e Type : ll/ A Acq . Tine : 3/8/2012 2;0l):24 f L K 900 0
Mod i fled : l l o mtelli O a n - 13 A eoo o Hln . Pea k

Width : Smoothin g Width ; 0.0 0 3 point s 750 0

Us e Relativ e RT : 14. 9 m i n 700 0

Retentio n Time : Valle y 14. 9 m i n 600 0 Height . 1.06et00 3 14. 8 roin 550 0 E n dTime : 14. 9 rain § 500 0Intensity.

350 0 300 0 2500 2000 150 0 100 0 500 0 

# I Sampte Namo:'g120307a028 ' Sampte ID : •LCS-120306-1' Fite:' g 120307a . Pea k Name
. -PFHS " Mass(as ) '399.0/99. 0 ' Comment.'0.2ppbLCS * Annotation: " sampl e Index : 2 B Sampl e Type ' Q C 1.19 1 Acq . Da l

I . Pea k Height ' I . Pea k Width : lOthin g Width .

Valle y

: : 14. 9 27655 S c c 

# I Sampt e Name-'91203073031 ' Sampte ID''LCS-120306-4 ' File:'gl20307a.wi( r Pea k Name-•PFHS ' Mas5{es) , •399.0/99. 0 a n Commen t •2ppt i LCS ' Annotation ' " Sampl e Type ; Concentration : 1.9 8 ng/mL Calculate d Cone ; 2.0 6 ng/n L Acq , Date : 3/8/ZOl Z Acq . Tine : 3:25:1 1 A M liCua n - IQA

Valle y : : 14- 9 300831 9 C (

Dat a printe d b yST W Printin g Time : 12:30:1 3 P M Printin g Date : Wednesday , Apri l 11 , Pag e 1 0 o f 1 2
Pag e 5 2 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS
. PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2 Ginge r AG0133050 9 Result s Name : gl20307a.rd b

Sampte Name
. 'gl20307aO4 rSampte ID - 'GLPlCH)l-02 - Pea k Nam e •PFHS " Mass(es) ' '399.0/99. 0 am u Commen t •JPAL-SW-TRIP1-0 ' Armoiatioo' ~ Sampl e Index : 4 1 Sampl e Type : Unknow n Concentration : H/ A

Valle y 14. 9 254 5 C(

124 0 

# I Sampte Name : 'g1203D7a042 ' Pea k Nam e "PFHS " Massfes ) Commen t 'JPAL-SW-TRIPI-LS ' S.imple Index ; 4 2 Sarople Type : Unknow n Concentration : N/ A Calculate d Con e Sampt e ID : 'GLP10-01-02 - •399.0/99. 0 am u Anr>otation ,
Acq . Tlm ( Pro cAlgorithm Mln . PeakHeight : 1/2012 8:11 M

lin g Width : 3

itelliQu a 0.0 0 0.0 0 Expecte d RT ; Us e Relativ e Int . Type : Retentio n T m Height : 

# I Sampte Name : 'g120307aa45 " Sampte ID : 'GLP l 0-01-02-27-005 ' Pea k Name , 'PFHS ' Massfes) - '399.0/99. 0 amu,399.0/80. 0 Commen L 'JPAL-SW.fTOI-O ' Annotation: ' Sampl e Index ' 45 Sampl e Type - Calo i Le d Cone : 0.0096 5

:e ; 3/8/Z01 2 l e : 8:21:42 ! ng/m L
Modified : Expecte d RT Us e Relativ e Int . Type : Retentio n Ti n Height :

Dat a printe d b yST W Printin g Time : 12:30:1 3 P M Printin g Date : Wednesday , Apri l 11 , Pag e 1 1 o f 1 2
Pag e 5 3 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2 Ginge r AG0133050 9 Result s Name : gl20307a.rd b 

# I Sampt e Name : •g120307aO46 ' Sampte ID
. 'GLP10-01-02-27-006 ' Flo : 'g120307a.wrf r Pea k Name ' "PFHS " Ma*s(es) - -399.0^99. 0 amu.399.0/80. 0 amu * Comment ' •JPW.-SW-ETOI-OB " Annoialion: " Sampl e Type : Unknow n Concentration : N/ A Calculate d Cone ; 0.011 0 ng , Acq . Date : 3/8/201 2 Acq . Time Modiiied . R T WindowExpecte d RT . 950 0 900 0 850 0 800 0 750 0 700 0

550 0 500 0 4500 4000 350 0 300 0 250 0 200 0 150 0 100 0 17.30s ^ 

# I Sampte Name : 'g120307o053 " Sampte ID* "GLP l 0-01-02-27-009 ' Fite , 'g120307a.wi r Pea k Name ' TFHS ' Mas5(as) : *399.0/99. 0 am u ,399.0/80. 0 amu ' Cotrenem
. 'JPAL-SW-eT02-0 - AnnotaUo n " Sampl e Index : 5 3 sampl e Type ; Con e ll/ A i Cone : 0.0070 8 ng/m L

Height : Star tT ; En d Ti m 900 0

750 0 700 0

550 0 500 0 ^ 45O 0 1 400 0 350 0 300 0 250 0 2D0 0 1500 1000 

# I Sampt e Name ; 'gl2O307aOS8 ' Sampte ID : 'GLPKM l 1-02-27-013 ' Fie ' 'Bl20307a.wif r Pea k Name.'PFHS - Mass(es):'399.0/99. 0 amu,399.0/80. 0 Comment
. 'JPAL-SW-ETOS-O ' Annotatto n "

I t . Type : ttentio n 1 1.23e-«00 4 14. 6 14. 9 Sampte Name : •g120307a066 " Sampte ID - 'GLPlO-01-02-27-017 ' Fite : •g120307 a wi r Pea k Name ' 'PFHS ' Mass(es) : -399.0/99. 0 am u ,399.0/80. 0 amu ' Commefi t 'JPAL-SW-ET04-0 " AnnotaUon
. ~ sampl e Index ; 66 Sampl e Type ; Calculate d Cone :

Height; Start T: End Tim 1.00e 4 9500.00 9000.0 0 8500.00 8000.00 7500.00 7000.00 6500.00 6000.00 g 5500.0 0
^ 5000.0

0 i E 4500.0 0 4000.0 0 M00.00
- 3000.0 0 2500.0 0 2000.0 0 1500.0 0 1000.0 0 500.0 0 0.0 0 Dat a printe d b yST W Printin g Time : 12:30:1 3 P M Printin g Date : Wednesday , Apri l 11 , 201 2 Pag e 1 2 o f 1 2 143 8 146 6

Pag e 5 4 o f7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2


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

Pag e 5 5 o f 7 7GLP l 0-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2



# 3 M Environmenta l Laborator y

Metiiod Method of Analysis

for the Determination

of Perfiuorinated

Compounds

in Water by LC/MS/MS;

Direct Injection

Analysis Method Number:

ETS-8-044.1 Adoption

Date: 4/12/07 Effectiv e Date : /



# l/f// / Approve d By :

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

ETS-8-044. 1 Pag e 1 of2 2 Method ofAnalysi s fo rth e Determinatio n o fPerfiuorinate d Compound s i n Wate rb yLC/MS/MS ; Direc

t Injectio n Analysi s Pag e 5 6 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S 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

fperfiuorinate 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 of perfluoroalky i sulfonamide s an d perfiuorinate 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 alternat e metho d suc h a s ETS-8-15 4 "Deteiminatio n ofPerfiuorinate 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 externa l standar d an d interna l standar

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

(CASRN) PFBA(0 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 PFHpA(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 PFDA(OIOAcid ) Perfluorodecanoi caci d 335-76- 2 PFUnA(01 1 Acid ) Periluoroundecanoi caci d 2058-94- 8 PFDo A(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 ofQuantitatio n (LOQ ) that meets Data Qualit yObjective s (DQOs ) that ar e develope d base d o n th e intende d us e ofthi s method
. Metho d Flexibilit

y- Thi s i s a perfomnance-base d metho d an d ma yb e generall yapplie d t o th e detenninatio n of perfiuorinate d compound s i n wate rmatrice s whe n analysi s batc h qualit y contro l (QC ) criteri a are met^ . Eac h set o fsample s are prepare d i n a n analysi s batc h wit h calibratio n standards , LCSs , blanks , an d continuin g calibratio n chec k standard s analyze d o n th e sam e instmmen t durin g a tim e perio d that begin s an d end s wit h th e analysi s ofth e appropriat e continuin g calibratio n chec k standards
. Th e laborator yi s permitte 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 perfomianc e o rt o meet data qualit y objective s fo rth e study
. I n al l case s where metho d modification s are implemented , th e batc h

' Th e metho di s supporte

db y validationwit

hintema l standar dcalibrationfo r

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

e sulfonamid

e i nlaborator

y control sample

s unde r 3 M metho

dvalidationE l 1-0667 . ^ Guidanc e fo r establishin

g metho dQ C Criteri abase

do na. ) FD AMa

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 o f2 2 Metho d of Analysi s fo rth e Determinatio n ofPerfiuorinate d Compound s i n Wate rb yLC/MS/MS ; Direc t Injectio n Analysi s Pag e 5 7 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S 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 Metho d Summar y 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

yno t b e suitabl e fo ranalysi s b

ythi s method
. Sample s containin g suspende d particulat e shoul d b e centrifuge d o rfiltere d prio rt o removin g a sampl e aliquot o rdilutin g wit h solvent
. Th e wate r sampl e i s mixe d wel l prio rt o removin g a n aliquot o rdiluting , i fnecessary , 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 intema l standar d calibratio n i n laborator

yreagen t water . Al l perfiuorinate d compound s (PFCs ) target analyt e concentration s o fperfluorosulfoni 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
. Aiternatively , quantitatio n ma yb e perfonne d b

yexterna l standar d calibration
. Thi s i s a peri'omiance-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 ofstud ysample s that are prepare d wit h calibratio n standards , laborator ycontro l samples , an d procedura l blanks , an d analyze d o n th e sam e instrumen t durin g a tim e perio d that begin s an d end s wit h th e analysi s ofth e appropriat e continuin g calibratio n chec k standards
. 3. 2 Analytica l Sampl e Aportio n ofa 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 ofth e Workin g Standar d (WS ) into a predetennine d amoun t ofAST 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 are use d t o calibrat e th e instrumen t respons e wit h respec t t o analyt e concentration
. 3. 4 Laborator y Duplicat e Sampl e (LDS , o r La b Dup ) Alaborator

yduplicat e sampl e i s a separat e aliquot ofa 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 fLDS s compare d t o tha t ofth e firs t aliquot give a measur e ofth e precisio n associate d wit h laborator y procedures , bu t no

t wit h sampl e collection , preservation , o rstorag e procedures
.
ETS-8-044. 1 Pag e 3 o f2 2 Metho d ofAnalysi s fo rth e Determinatio n o fPerfiuorinate d Compound s i n Wate rbyLC/MS/MS ; Direc t Injectio n Analysi s Pag e 5 8 o f 7 7GLP l 0-01-02 ; Interi m Repor t 2 6 Analysi s o fPFBS , PFHS , an d PFO S 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 al l respects , includin g exposur e t o samplin g sit e conditions , storage , preservatio n an d al l analytica l procedures
. Th e purpos e ofth e T B i s t o detennin e i ftest substance s o rothe rinterference s are presen t i n th e fiel d environment
. Thi s sampl e i s als o refen-ed t o as 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 as 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 ofth e FD S compare d t o that ofth e firs t sampl e give s a measur e ofth e precisio n associate d wit h sampl e collection , preservatio n an d storage , as wel l a s wit h laborator

yprocedures
. 3. 7 Fiel d Matri x Spik e (FMS ) Asampl e t o whic h know n quantitie s ofth e targe t analytes , IS s an d SRS s are adde d t o th e sampl e bottl e i n th e laborator ybefor e th e bottle s are sen t t o th e field fo rcollectio n ofaqueou s sarhples
. Aknown , specifi cvolum e ofsampl e must b e adde d t o th e sampl e containe r withou t rinsing. Thi s ma

yb e accomplishe d b

ymakin g a "fil l t o thi s level " lin e o n th e outsid e o f th e sampl e container
. Th e FM S i s analyze d t o ascertai n i fan ymatri xeffects , interferences , o rstabilit yissue s ma

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

Matri x Spik e (TBMS ) A n aliquot ofAST M Typ e I , HPLC grad e water , o rothe rsuitabl e water , t o whic h know n quantitie s o

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

yvary . 

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

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

e stabl e isotop e labele d version s ofth e target analytes
. Th e are a coun t rati o o f th e target analyt e t o th e interna l standar d i s use d fo rcalibration
. Surrogate IS s are applie d whe n stabl e isotop e IS s o ftarge 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 ofth e targe t analyte , bu t i s treate d a s a n interna l standar d fo r quantitation
. 3.1 0 Laborator y Contro l Sampl e (LCS ) A n aliquot o

f contro l matri xt o whic h know n quantitie s ofth 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 leas t thre e level s (two level s fo rSRSs ) i n triplicat e ar e included , on e generall ya t th e lo wen d ofth e calibratio n curve an d on e nea rth e mi d rang e an d th e uppe ren d ofth e curve . Th e LCS s ar e analyze d exactl ylike a laborator ysampl e t o detennin e whethe rth e stabilit yofth 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 ofa sampl e t o whic h know n quantitie s o ftarge t analytes , IS s an d SRS s (whe n applicable ) are adde d i n th e laboratory
. Th e LM S i s analyze d exactl ylik e a laborator

ysampl e t o determin e whethe rth e sampl e matri xcontribute s bia s t o th e analytica l results
. Th e endogenou s concentration s ofth e analyte s i n th e sampl e matri x must b e detennine d i n a separat e aliquot an d th e measure d value s i n th e LM S con^ecte d fo r thes e concentrations
. LMS s are optiona l fo ranalysi s o faqueou s samples
. ETS-8-044. 1 Pag e 4 of2 2 Metho d o fAnalysi s fo rth e Determinatio n o fPerfiuorinate d Compound s i n Wate rbyLC/MS/MS ; Direc t Injectio n Analysi s Pag e 5 9 o f 7 7GLP l 0-01-02 ; Interi m Repor t 2 6 Analysi s o fPFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2
3.1 2 Laborator y Sampl e Aportio n o raliquot ofa sampl e receive d fro m th e field fo rtesting
. 3.1 3 Limi t o fQuantitatio n (LOQ ) Th e lowe rlimi t ofquantitatio n (LLOQ ) fo ra n analytica l batc h i s th e lowes t concentratio n that ca n b e reliabl yquantitate d withi n th e specifie d limits o fprecisio 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 a s th e lowes

t calibratio n standar

d wit h are a counts a

t least twic e that ofth e averag e are a counts of th e procedura l blanks
. Th e uppe rlimi t o

fquantitatio 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 fprecisio 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 ofcontro 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 detemnin e i ftes t substance s o rothe rinterference s are presen t i n th e laborator

yenvironment , th e reagents , o rth e apparatus . 3.1 5 Sampl e Asampl e i s a n aliquot remove d fro m a large rquantit yo fmateria l intende d t o represen t th e origina l source material
. 3.1 6 Stoc k

Standar d Solutio n (SSS ) Aconcentrate d solutio n o fa single-analyt e prepare d i n th e laborator ywit h a n assaye d reference compound
. 3.1 7 Surrogat e Interna l Standar d A n I S that i s no

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

d fo rquantitation
. 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 as a n interna l standard , that i s adde d t o eac h sampl e an d appropriat e QC sampl e a s a mean s t o evaluat e th e metho d peri'onnance fo ra chemica l clas s ofcompound s (e.g. , PFSAs , PFCAs)
. 3.1 9 Workin g Standar d (WS ) Asolutio n of severa l analyte s prepare d i n th e laborator yfro m SSS s an d dilute d a s neede d t o prepar e calibratio n standard s an d othe rrequire d analyt e solutions
. 4 Warning s an d Caution s 

### 4. 1 Healt h an d Safety Th e acut e an d chroni ctoxicit yo f th e standard s fo rthi s metho d hav e no t bee n precisel y detennined ; however , eac h shoul d b e treate d a s a potentia l healt h hazard
. Th e analyst shoul d wea rgloves , a la b coat , an d safet yglasse s t o preven t exposur e t o chemical s that migh t b e present . ETS-8-044. 1 Pag e 5 of2 2 Metho d ofAnalysi s fo rth e Determinatio n o fPerfiuorinate d Compound s i n Wate rbyLC/MS/MS ; Direc t Injectio n Analysi s Pag e 6 0 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o fPFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2
Th e laborator

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

floca l regulation s regardin g th e handlin g ofth e chemical s use d i n thi s method
. Areference file ofmateria l safet ydat a 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 ofsolvents , 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 informatio n an d cautions
. 5 Interference s Durin g sampl e preparatio n an d analysis , majo rpotenfia l contaminan t source s are reagents an d glassware
. Al l material s use d i n th e analyse s shal l b e demonstrate d t o b e fre e fro m interference s unde rcondition s ofanalysi s b yrunnin g metho d blanks
. Parts an d supplie s that contai n Teflon® shoul d b e avoide d o rminimize d du e t o th e possibilit y o finterference 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 ofdisposabl 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 o freadin g t o 0.000 1 g HPLC/MS/M S o rHPLC/M S system , a s describe d i n Sectio n 10 . 6. 2 Supplie s an d Material s Sampl e collectio n bottles—HOP E (e.g. , NalgeneTM ) wide-mout h bottle s wit h screwcap . Note : D o no

t us e fluorinated 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

fspinnin 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 perfomianc 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 o f2 2 Metho d o f Analysi s fo rth e Determinatio n o fPerfiuorinate d Compound s i n Wate rb yLC/MS/MS ; Direc t Injectio n Analysi s Pag e 6 1 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S 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 Perfiuorinate 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-isotopicall ylabele d Perfluorooctanesulfonat e (SRS ) PFUn A[1,2-"C] , "Cz-isotopicall ylabele d Perfluoroundecanoi caci d (SRS ) Acusto m mi xofIS s i n a methanoli csolutio n containin g ([1,2,3,4-"C4]PFBA , [1, 2 - "CzjPFHxA , [1,2,3,4,5,6,7,8-"C8lPFOA , [1,2,3,4,5,6, 7 8,9-"C9]PFNA , [1, 2 -^^CJPFDA , [1,2,3,4,5,6,7-"C7]PFUnA , [1,2-XJPFDoA , [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 combinafio n wit h adde d ([1,2,3,4,5-^CdPFPeA , ([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 prepare a stoc k I S mixture
. Othe rIS s ca n b e applied
. 

### 7. 3 Reagen t Preparatio n 2 m M Ammoniu m acetat e solutio n (Analysis)—Weig h 0. 3 g o f Ammoniu m acetat e an d dissolve i n 2. 0 L o

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

fMagnesiu m Acetat e an d dissolve i n 6. 0 L o freagen t water . Note : Altemative volume s ma yb e prepare d a s lon g as th e ratio s o fth e solven t t o solut e ratio s are maintained
.
ETS-8-044. 1 Pag e 7 of2 2 Metho d ofAnalysi s fo rth e Determinatio n ofPerfluorinate d Compound s i n Wate rbyLC/MS/MS ; Direc t Injectio n Analysi s Pag e 6 2 o f7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S 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 a s 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 fa particula rstudy
. Fo rexample , |J L volume s ma

yb e spike d into volumetri cflasks whe n dilutin g stoc k solution s t o appropriat e levels
. 100 (jg/m L targe t analyt e SSSs—Weig h ou t 1 0 m g ofanalytica l standar d (correcte d fo r percen t salt , acid[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 12 5 m L LDP E bottl e o rothe r suitabl e container
. Prepar e a separat e solutio n fo reac h analyte
. Expiratio n date s an d storag e condition s o

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

, , molecula rweigh t o f anio n sal t correctio n facto r= moclecula rweigh t o f sal t 49 9 PFO S (K- ^ )sal t correctio n facto r= —= 0.927 5 53 8 1 0 m g C8F17SO3K

* wit h purit

y90 % = 8.35 m g C8F17SO3"(1 0 mg*0.90*0.9275=8.3 5 mg ) 1 0 \jglm L (10,00 0 ng/mL ) mixe d workin g standard—Ad d 5. 0 m L eac h o fth e 100 |jg/m L SSS s t o a 5 0 m L volumetri cflask an d brin g u p t o volum e wit h solvent
. 1 |jg/m L (1,00 0 ng/mL ) mixe d workin g standard—Ad d 0. 5 m L ofth e 100 \jglm 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 ofth e 100 |jg/m L SSS s t o a 5 0 m L volumetri cflask

an d brin g u p t o volum e wit h solvent
. 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 of6 month s fro m th e dat e o

f preparation
. 

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

e calibratio n solution s i n AST M Typ e I water , HPLC water , othe r suitabl e water , o ra mixture o fsolven t an d wate rusin g th e informatio n i n Tabl e 2 a s a guideline
. Note : Volume s o fwate 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
. Calibrafio n level s othe rtha n thos e liste d belowca n b e prepare d a s needed
. Fo rth e quantitatio n of PFO Aan d PFOS , reference material s ofcertifie d mixe d linea ran d branche d isome rare prefen-ed
. Alternately , reference material s of primaril ylinea risomer s of 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 Intema l Standard (IS ) an d Surrxigat e Recover yStandart l (SRS) Fo rI S calibration , stabl e isotop e interna l standard s ofeac h targe t analyt e o rappropriat e surrogat e IS s shoul d b e spike d a t th e sam e leve l i n al l calibratio n standards
. Once th e calibratio n standard s have bee n prepare d a s state d above i n Sectio n 7.5 , al l calibratio n standard s are spike d wit h a separat e interna l standar d spikin g solution
. Typicall yth e

' Arepor t summarizin

g a n assessmen

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

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

S ca n b e foundi n 3 M repor

t E l 1-0560. ETS-8-044. 1 Pag e 8 o f 2 2 Metho d ofAnalysi 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 3 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2
concentratio n ofth 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 o fth e intema l standar d spikin g solutio n i s typicall y2 [iglmL
. Aseparat e zero poin t o rmetho d blan k i s typicall yprepare d a

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

e th e standard s (AST M Typ e I water , HPLC water , othe rsuitabl e water , o ra solvent/wate rmixture) , an d i s spike d wit h th e interna l standar d a t th e sam e concentratio n a s th e calibratio n curve , typicall ya t 1 ng/mL
. I fth 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 ar e spike d wit h a SR S a

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

d an d sun-ogat

e standard
. Tabl e 1 lists recommende d stabl e isotop e intema l standard s fo rsevera l PFS Aan d PFCA targe t compounds
. Acusto m mi xofisotopicall ylabele d targe t analyte s i n a methanoli c solutio n containin g ([1,2,3,4-"C4]PFBA , [1, 2 -^XJPFHxA , [1,2,3,4,5, 6 7,8-"C8]PFOA , [1,2,3,4,5,6,7,8,9-^^C9]PFNA , [1,2,3,4,5, 6 -"CeJPFDA , [1,2,3,4,5,6, 7 -^^C7]PFUnA , [1, 2 - ^^CJPFDoA , [1,2,3-"C3]PFHS , [1,2,3,4,5,6,7,8-"C8]PFOS , an d [1,2,3,4,5,6,7,8-"C8]FOS A (Wellingto n Laboratories , Guelph , ON ) i n combinatio n wit h adde d ([1,2,3,4,5-"C5]PFPeA , ([1,2,3,4-"C4]PFHpA , an d [^^OJPFB S ca n b e use d t o prepare a stoc k I S solution
. Alternative source s o

fcertifie 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 oftarge t analyte s no t liste d i n th e tabl e ma

yb e use d i f supporte d byvalidatio n and/o ranalysi s batc h QC s meetin g metho d acceptance criteri a (e.g. , [^^CJ-PFOA)
. Th e sam e intema 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 fth 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 o fa 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 fspik e concentrafion 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 of2 2 Metho d ofAnalysi s fo rth e Determinatio n o fPerfluorinate d Compound s i n Wate rbyLC/MS/MS ; Direc t Injectio n Analysi s Pag e 6 4 o f7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S 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 acid [1,2,3,4-"C4]PFB A I S fo r PFB A Wellingto nLabs

(Mi x o r Individual ) "C4-Perfluoropentanoi

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

S fo r PFPe A Wellingto nLabs

(Mi x o r Individual ) "C2-Perfluorohexanoi

c aci d [l,2-"C2]PFHx A I S fo r PFHx A Wellingto nLab s

(Mi x o r Individual ) "C4-Perfluoroheptanoi

c acid [l,2,3,4-"C4]PFHp A I S fo r PFHp A Wellingto nLabs

(Mi x o r Individual ) "Cs-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 nLab s (Mi x o r Individual ) "CrPerfluorononanoi c acid [1,2,3,4,5, 6 J,8,9-"C9]PFN A I S fo r PFN A Wellingto nLabs

(Mi x o r Individual ) "C6-Perfluorodecanoi

c acid [1,2,3,4,5, 6 -"CslPFD A I S fo r PFD A Wellingto nLabs

(Mi x o r Individual ) "C7-Perfluoroundecanoi

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

(Mi x o r Individual ) "Ci-Perfluorododecanoic acid [1, 2 -"C2]PFDo A I

S fo r PFDoA , *PFT

A Wellingto nLabs (Mi x o r Individual ) '*02-Ammoniu

mPerfluorobutan

e sulfonat e ["OjJPFB S I S fo r PFB S RT I Intemationa l (Individual ) "Cj-iAmmoniumPerfluorohexan e sulfonat e [1,2,3-"C3]PFHS I S fo r PFH S Wellingto nLabs

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

e sulfonat e [l,2,3,4,5,6,7,8-"C8]PFO S I S fo r PFO S an d PFOS[l,2,3, 4 ''€4] , WellingtonLabs (Mi x o r Individual ) "Cg-Perfluorooctanesulfonamid e [l,2,3,4,5,6,7,8-"Cg]FOS A I S fo r FOSA Wellingto nLab 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 Wellington "Cj-Perfluoroundecanoic aci d [!,2-"C2]PFUnA 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 ; 04 , €6 , an d0 8 Wellingto n

ETS-8-044. 1 Pag e 1 0 of 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 6 5 o f 7 7GLP l 0-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2

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

ofWS,pg/mL Volume of WS,/JL Volume

of IS (2 fjg/mL),/d. Concentration of Surrogate, yg/mL Volume of Surrogate, /d. 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 curv e 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 curv e poin t 1. 0 5 0 5 0 0.2 0 25 0 10 0 1 ng/m L curv e poin t 1. 0 10 0 5 0 0.2 0 50 0 10 0 2. 5 ng/m L curv e poin t 10. 0 2 5 5 0 10. 0 2 5 10 0 5. 0 ng/m L curv e poin t 10. 0 5 0 5 0 10. 0 5 0 10 0 10. 0 ng/m L cun/

e poin t 10. 0 10 0 5 0 10. 0 10 0 10 0 25. 0 ng/m L cun/

e 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- Not Applicabl e (1 ) Sample s requirin g analysi s fo rPFUnA , PFDoA , PFTrDA , an d FOS Ashoul 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 f2 2 Metho d o fAnalysi s fo rth e Determinatio n ofPerfluorinate d Compound s i n Wate rb yLC/MS/MS ; Direc

t Injectio n Analysi s Pag e 6 6 o f 7 7GLP l 0-01-02 ; Interi m Repor t 2 6 Analysi s o fPFBS , PFHS , an d PFO S 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 by3 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 collecfio 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
. Altematively , th e sampl e an d field duplicat e sampl e ma ycontai n SRS s i n lie u o

fadditiona l targe t analyt e lo wfield matri xspik

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

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

wmuc h sampl e i s require d t o meet data qualit yobjectives. ) Sampl e collectio n volume s are projec t specifi can d base d o n dat a qualit yobjectives
. Th e Nalgen e bottle s d o no t requir e an ypretreatmen t prio rt o use . Typically , placemen t o fa 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 mari<e rtemplate
. Alternatively , bottle s ma yb e weighe d prio rt o bottl e preparafio 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 use as a sample , field sampl e duplicate , lo wfield matri xspike , hig h field matri xspike , sample/SR S field matri xspike , field duplicat e sample/SR S field matri x spike , tri p blank , o rtri p blan k matri xspike
. I feac 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 ofbottle 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 oftri p blan k an d tri p blan k

matri xspike s are prepared
. Bottl e preparatio n shoul d b e documente d i n a Not e t o Fil e o ro n a sampl e preparatio n wori<shee t an d shoul d includ e th e followin g information : dat e prepared , tota l numbe rofbottle s prepared , numbe ro fsampl e sites , th e standar d identificatio n number

s an d spike volume s use d t o prepar e spike d bottles , th e "fil l t o here " volume , an d an yothe rpertinen t infonnafio n neede d fo rreconstructibilit yo fth 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 ofth e method
. AFM S sampl e i s define d as a QC sampl e t o whic h know n quantitie s ofappropriat e targe t analyte s are adde d t o th e sampl e bottl e i n th e field o ri n th e laborator ybefor e th e bottle s 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 oftarge t analyt e FM S samples
. Sampl e quantitie s are determine d volumetricall yo r gravimetrically
. Aknown , specifi cvolum e o rweigh t ofsampl 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 o fth 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 fth e expecte d rang e ofanalyt 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 oftarge t analyt e FM S samples , th e sampl e an d field duplicat e sampl e ar e 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 fmatri x effects o rsampl e holdin g tim e contribute s bias t o th e analytica l results
. Fo rth e sampl e bottle s designate d fo r matri xspikes , a n appropriat e volum e ofmatri xspikin g solutio n i s adde d t o th e empt ybottl e prio rt o sampling
. Th e volum e o

fspik e solutio n adde d shoul d produce th e desire d final concentratio n o ftarge t analyte s onc e 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 ofth e appropriat e targe t analytes , ISs , an d SRSs
. Th e targe t analyt e matri x spikin g solutio n i s ofte n th e sam e as th e workin g standard s use d t o creat e th e calibratio n standards
. A n exampl e of a bottl e spike i s give n below
. "Fil l t o here " volum e = 20 0 m L ( A25 0 m L Nalgen e bottl e i s used ) Desire d Fiel d Spik

e Concentratio n = 0.2 5 ng/m L ETS-8-044. 1 Pag e 1 2 o f2 2 Metho d o fAnalysi s fo rth e Determinatio n o fPerfluorinate d Compound s i n Wate rb yLC/MS/MS ; Direc

t Injectio n Analysi s Pag e 6 7 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2
50 0 [i L of a 0. 1 (ig/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 fanalysi s o

fa surrogat e recover

ystandar d (SRS ) i s include d i n th e projec t objectives , a n appropriat e volum e o fa 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 surrogat e recover ystandard s a

t a final desire d spike concentratio n of0. 1 ng/mL
. I fquantitatio n b

yintema l standar

d (IS ) i s include d i n th e projec t objective , a n appropriat e volum e o fintema 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 are spike d wit h interna l standar

d a t a final desire d spike concentrafio n o f1 ng/mL
. Fo rth e tri p blank , th e SR S spik e an d I S spik

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

yb e place d aroun d th e oute redg e ofth e cap . Tri p blan k matri xspike s are prepare d b yaddin g th e appropriat e volum e oftarget 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 data accurat e t o ±30 % wit h a targete d LOQ of0.02 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
. A t a minimum , metho d blank s are analyze d prio rt o instmmen t calibration , prio rt o th e analysi s o

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

fth e analytica l mn . Th e mea n are a coun t o rare a ratio s whe n usin g interna l standar d calibration , fo reac h analyt e i n th e metho d blank s must b e les s tha n 50 % ofth e are a coun t counts o rare a ratio s whe n usin g interna l standar d calibration , ofth e LOQ standard
. Th e standar d deviatio n o

fth e are a counts , o rare a ratio s whe n usin g intema l standar d calibration , ofthes 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 fth e mea n are a counts o rare a ratio s whe n usin g intema l standar d calibration , ofth e metho d blank s excee d 50 % ofth e LOQ standard , the n th e LOQ must b e raise d t o th e first standar

d leve l i n th e curve that meets criteria
. Metho d blank s ma yb e eliminate d i ftechnica 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 fan 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 ) ofduplicat e sample s shoul d b e ^20 % fo rth e precisio n o fsampl 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 a s outsid e o fQ C acceptance criteria
. 9. 3 Laborator y Matri x Spike s (LMSs ) LMS s ma yb e performe d i n lie u o

fFMS s i fFMS s have previousl ybee n perfonne d fo rth e sampl e matrix
. Additionally , LMS s ma

yb e performe d i n lie u o

fFMS s fo ra sampl e matri xi fth e FM S level s were no t appropriat e fo rdetenninin g spike recoverie s relative t o endogenou s level s o ftarget 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 determin e th e matri xeffec t o n spik e recover yefficienc yofeac h target analyt e an d appropriat e SRSs
. LMS s shoul d b e prepare d at a minimu m o fon 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 ofeac h target analyte
. ETS-8-044. 1 Pag e 1 3 o f2 2 Metho d o fAnalysi s fo rth e Determinatio n ofPerfluorinate d Compound s i n Wate rb yLC/MS/MS ; Direc

t Injectio n Analysi s Pag e 6 8 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o fPFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2
La b matri xspik

e recoverie s shoul d fal l withi n ±30 % o fexpecte d values
. Sampl e dat a wit h LM S recover y outsid e of±30 % bu t withi n ±50 % ofth e expecte d valu e ar e fiagged an d reporte d as outsid e ofQ C acceptance criteria
. Data wit h LM S recover youtsid e o

f±50 % o fth e expecte d valu e ar e reporte d a s NR , where N R i s define d a s "Not Reportable " dat a outsid e ofQ 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 detemnin e metho d accurac yan d precision
. LCS s shoul d b e prepare d a

t thre e level s i n triplicat e fo reac h targe t analyt e an d a t a minimu m oftwo 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 ofth e calibratio n curve an d th e hig h la b contro l spike s a t approximatel y80 % ofth e uppe rLOQ
. Fo reac h targe t analyt e an d SRSs , th e percen t relative standar d deviatio n (metho d precision ) fo reac h contro l spike leve l must b e les s tha n o requa l t o 20 % an d th e averag e recover y(metho d accuracy) fo reac h contro l spik e leve l must b e 80-120%)
. Sampl e dat a fo rtarge t analyte s outsid e ofth e laborator

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

yofa spikin g leve l fall s outsid e metho d acceptance , bu t a t leas t 67 % ( 6 ou t of9 ) ofLC S sample s ar

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

t th e sam e concentration , ma

yb e outsid e 20%

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

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

yETS-12 - 012 , that analytica l batc h uncertaint ywil l b e expande d fo rthat particula rstudy
. I fmor e tha n 67 % ofth 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 ofmixe d branche d an d linea risome rPFOS/PFO Aare preferred
. However , fo rPFOS/PFO

Atarge t analytes , i fth e calibratio n standard s are comprise d ofpredominantl ylinea risomer s only , a t least on e leve l oftriplicat e LCS s shoul d b e prepare d usin g PFOS/PFO Awhic h contain s a mi xo flinea 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 fth 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 % o fexpecte d values
. Alternatively , i n lie u of mixe d branche d an d linea risome rPFOS/PFO ALCSs , mixe d branche d an d linea risome rPFOS/PFO A TBMS s ma

yb e applie d t o demonstrat e metho d accurac yan d precision
. 9. 5 Fiel d Matri x Spike s (FMSs ) / Surrogat e Recover y Standard s (SRSs ) FMS s are prepare d fo reac h samplin g locatio n an d analyze d t o detennin e th e matri xeffec t an d sampl e holdin g tim e o n th e spike recover yofeac 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 are QC sample s t o whic h know n quantitie s ofappropriat e target analyte s are adde d t o th e sampl e bottl e i n th e laborator

ybefor e th e bottle s are sen t t o th e field. Typicall ya 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 oftarge t analyt e lo

wfield matri xspike an d targe t analyt e hig h field matri xspik e samples
. Fiel d matri xspike metho d acceptance criteri a are recoverie s withi n ±30 % ofth e expecte d value
. I fFM S recover y(target analyt e o rSR S spike ) i s outsid e o f±30 % o fth e expecte d valu e o rcoul d no t b e assesse d becaus e th e FM S (target analyte ) was spike d a t a n inappropriat e level , th e sampl e resul t i s reporte d a s follows : 1 . ) I f 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 fLM S recoverie s are withi n ±30 % th e dat a ar e reportabl e an d flagged t o indicat e that th e FM S spike s level s were inappropriate
. 2 . ) I fmultipl 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% i acceptance range , th e dat a are reportabl e an d flagged t o indicat e that whil e there were failin g FMS's , th e uncertaint ywil l no t b e expande d sinc e th e most appropriat e spike leve l passed
. ETS-8-044. 1 Pag e 1 4 o f2 2 Metho d o fAnalysi s fo rth e Determinatio n o fPerfluorinate d Compound s i n Wate rb yLC/MS/MS ; Direc

t Injectio n Analysi s Pag e 6 9 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2
3 . ) I fth e targe t analyt e FM S recoverie s are outsid e ofth 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 data ma

yb e reporte d bu t flagged wit h a n expande d uncertaint yan d a s no

t meetin g FM S criteria
. 4 . ) Sampl e data wit h FM S recover youtsid e o

f±30 % bu t withi n ±50 % o fth e expecte d valu e ar

e flagged an d reporte d a s outsid e o

fQ C acceptance criteri a wit h a n expande d uncertainty
. 5 . ) I fFM S recover

yi s outsid e of±50% , th e sampl e resul t i s reporte d as NR , where N R i s define d as "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 least 50 % o

fth 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 detemnin e th e statemen t ofaccurac yfo ranalytica l results
. Note : I t i s possibl e fo rbottle s utilize d fo rFiel d Matri xSpik e sample s t o b e under-fille d o rover-fille d durin g sampl e collection
. Since thi s scenari o wil l effec t th e actua l concentratio n o fth e FM S sampl e (sun-ogat e an d intema l standar

d concentration s wil l als o b e effected , i fused) , i t i s importan t that an yobviou s under-fillin g o r over-fillin g ofsampl e bottle s b e documente d i n th e dat a packag e an d take n into accoun t i n th e FMS , ISs , o r SRS s recover

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

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

fth 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 fnecessary , 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 target analyt e an d a t a minimu m oftwo level s i n triplicat e fo rappropriat e SRSs
. Lo wla b contro l spike s shoul d b e prepare d a t a concentrafio n i n th e rang e ofapproximatel 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 ofth e calibratio n curve an d th e hig h la b contro l spike s a

t approximatel y80 % o

fth e uppe rLOQ
. Fo rI S quantitation , stabl e isotop e intema l standard s ofeac 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 fLCS s are bein g prepare d usin g syntheti cgroundwater , allowth e LCS s sample s t o equilibrat e fo ra minimu m of4 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 fLC/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 as 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 performance 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 ofthi s metho d i s th e responsibilit yofth 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 f2 2 Metho d o fAnalysi s fo rth e Determinatio n o fPerfluorinate d Compound s i n Wate rb yLC/MS/MS ; Direc

t Injectio n Analysi s Pag e 7 0 o f7 7GLP l 0-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S 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 rWindows XP , Analyst 1.4. 2 o rhighe rversion s HPLC : Agilen t Serie s 1100,1200 , o r129 0 Agilen t Quaternar

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

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

Time (min) Flow

Rate (/iUrnin) 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 as lon g as th e metho d criteri a an d projec t dat a qualit

yobjective s are met . I t ma yb e necessar

yt o adjust th e HPLC gradien t i n orde rt o optimiz e 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 C1 8 etc. ) ma yb e used
.

ETS-8-044. 1 Pag e 1 6 o f2 2 Metho d ofAnalysi s fo rth e Determinatio n ofPerfluorinate d Compound s i n Wate rbyLC/MS/MS ; Direc t Injectio n Analysi s Pag e 7 1 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2
Tabl e 4 Suggeste d MRIV I Transition s fo r Targe t Analytes , Surrogates , an d Interna l Standard s Analyte Analyte Description Mass Transition 01 (amu) Mass Transition

03 (amu) PFB A (0 4 Acid ) Targe t 21 3 16 9 PFPe A (0 5 Acid ) Targe t 26 3 21 9 PFHx A (0 6 Acid ) Targe t 31 3 269,11 9 PFHp A (0 7 Acid ) Targe t 36 3 319 , 16 9 PFO A (0 8 Acid ) Targe t 41 3 369,219 , 16 9 PFN A (0 9 Acid ) Targe t 463 419 , 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 PFTA(C1 3 Acid ) Targe t 66 3 619 , 369,31 9 FBSA (0 4 Sulfonamide) Targe t 29 8 7 8 FOSA (0 8 Sulfonamide) Targe t 49 8 7 8 PFB S (0 4 Sulfonate) Targe t 299 99 , 8 0 PFH S (0 6 Sulfonate) Targe t 39 9 99 , 8 0 PFO S (0 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 r 1,2,3,4,5-''CslPFPe

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

A I S fo r PFHp A 36

7 32

2 [1,2,3,4,5,6,7,8-"CslPFOA I S fo r PFO A 42 1 37 6 [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-"CslPFD A 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 57

0 52

5 [l,2-"C2lPFDo A I S fo r PFDo A an dPFT A 61 5 570 ["O2IPFB S I S fo r PFB S 30 3 8

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

2 8

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

3 8

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

0 [l,2,3,4-"C4lPF0 A Surrogat e (04-0 8 Acids ) 41 7 372 [1,2,3,4
- "C4IPFOS Surrogate(Sulfonates , FOSA ) 50

3 8

0 [l,2-"C2]PFUn A Surrogat e (09-01 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 ofon e daughte rio n i s acceptabl e i fdat a 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 ofth e analyst , mas s transitio n 9 9 i s suggeste d fo rPFOS
. Quantitatio n ma yb e performe 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 ofth e monitore d transitions
. Us e ofth 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 fmobil 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 njn , a s lon g as th e drif t confinue s throug h th e enfire 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 finterna l standar d calibratio n doe s no t meet calibratio n acceptance criteria , extema l calibratio n ca n b e applied
. Se e Tabl e 1 fo r ETS-8-044. 1 Pag e 1 7 o f2 2 Metho d ofAnalysi s fo rth e Determinatio n ofPerfluorinate d Compound s i n Wate rbyLC/MS/MS ; Direc t Injectio n Analysi s Pag e 7 2 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2
recommende d applicatio n o f availabl e intema 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 ofsamples
. I f interna l standard s were adde d t o th e calibratio n standard s are a rafio 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 ^ + b x+ 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 rlowpoints 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-detemnined acceptance criteria
. Low-leve l curve points shoul d als o b e exclude d i fthei rare a counts (o rare a rati o i f quantitatin g b yIS ) are no

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

) valu e fo rth e calibratio n curve must b e greate rtha n o requa l t o 0.99 0 (o ra con-elatio n coefficien t (r

) of 0.995)
. Eac h poin t i n th e curve must b e withi n ±25 % o fth e theoretica l concentratio n wit h th e excepfio n of th e LLOQ , whic h ma yb e withi n ±30% . Justificatio n fo rexclusio n ofcalibratio n curve points wil l b e note d i n th e ra

wdata
. Aminimu m o

f6 points wil l b e use d t o construc t th e calibratio n curve . I fth e calibratio n curve doe s no t meet acceptance criteria , perfom n routin e maintenance o rprepar e a ne w standar d curve (i f necessary

) an d reanalyze
. 11. 3 Continuin g Calibratio n Verificatio n (CCV ) Continuin g calibratio n verification s (CCV) are analyze d t o verif yth e accurac

yofth e calibrafio n curve . Analyz e a mid-rang e calibratio n standard , on e o fth e sam e standard s use d t o construc t th e calibratio n curve , a

t a minimu m afte rever

ytent h sample , no

t includin g solven t blanks , wit h a minimu m ofon e pe rsampl e set . Calibrafio n verificafio n injection s mus t b e withi n +25%

) t o b e considere d acceptable
. Th e calibratio n curve an d th e las t passin g CCV wil l the n bracket acceptabl e samples
. Multipl e CCV level s ma yb e used
. Sample s must b e brackete d b

ypassin g CCVs o rth e calibratio n curve an d a passin g CCV t o b e reportable
. 11. 4 Syste m Suitabilit y Aminimu m ofthre e syste m suitabilit ysample s shoul d b e injecte d a t th e beginnin g o

f eac h analytica l mn , prio r t o th e analysi s ofth e calibratio n curve . Typicall ythes e sample s are a t a concentratio n nea rth e mid-leve l o fth e calibratio n curve an d are repeate d injection s fro m on e autosample rvial
. I t i s suggeste d that th e syste m suitabilit yinjection s hav

e are a counts o rare a ratio s whe n usin g interna l standar d calibration , wit h a targe t RS D of<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 LCIMSM 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 QC sample s analyze d a s part o fth e analysi s batch
. An yeffec t o fsyste 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 00|JL ) ofeac 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 tha t are quantitate d above th e concentratio n ofth 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 on thes e result s a s aflinctio no f

th e numbe r o f MRM s bein

g monitored . ETS-8-044. 1 Pag e 1 8 o f 2 2 Metho d 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 7 3 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2


### 1 2 Data Analysi s an d Calculation s Th e chromatograph yanalysi s software wil l typicall ycalculat e th e amoun t o ftarge t 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 fth e LC S usin g th e followin g equation : LC S Concentratio

n (— ) LCS % recover

y = * 100 % n e Spik e Concentratio

n (—^ ) m L Calculat e th e percen t recover yofth 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 fanalyt e prio rt o extraction , use th e followin g equatio n t o calculat e th e percen t recovery .

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

### 1 3 Analysi s Batc h Method Performanc e Criteri a An ymetho d performance parameter s that are no

t achieve d must b e considere d i n th e evaluatio n o fth e data
. Nonconformance t o an yspecifie d parameter s must b e describe d an d discusse d i n th e final repor t i fth 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 fcriteri a liste d i n thi s metho d perfomnanc e 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 as appropriate
. Documen t al l action s i n th e ra wdata
. I fdat a are t o b e reporte d whe n performance criteri a hav e no t bee n met , th e data must b e footnote d o n table s an d discusse d i n th e tex

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

f thre e syste m suitabilit

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

feac h analytica l njn
. Thes e sample s are ru n prio rt o th e calibratio n curve . I t i s suggeste d that th e syste m suitabilit yinjection s have are a counts wit h a targe t RS D o f<5 % an d a targe t retentio n tim e RS D o f<2% . 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 ro fMR M transition s bein g monitore d i n th e LC/MS/M S ru n o rtim e period
. An yeffec t o fsyste 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 fdetenninatio 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 con-espondin g t o a correlatio n coefficien t (r ) = 0.995 . Eac h poin t i n th e curve must b e withi n ±25% ) ofth e theoretica l concentratio n wit h th e exceptio n ofth 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 ofth 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 of Perfluorinate d Compound s i n Wate rbyLC/MS/MS ; Direc t Injectio n Analysi s Pag e 7 4 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2

ofeac h curve poin t must b e withi n 25 % ofth e theoretica l valu e (withi n 30 % fo rlowes t curve point)
. Sample s that are brackete d b

yCCVs no

t meetin g thes e criteri a must b e reanalyzed
. Limit s o f Quantitatio n (LOQ) : Th e lowe rLOQ (LLOQ ) i s th e lowest non-zer o active standar

d i n th e calibratio n curve ; th e pea k are a o fth e LLOQ must b e a

t least 2 X that ofth e averag e are a counts fo ral l prepare d procedura l blank(s)
. B ydefinition , th e measure d valu e ofth e LLOQ must b e withi n 30 % ofth e theoretica l value
. Demonstratio n o f Specificity : Specificit yi s demonstrate d b

ychromatographi cretentio n tim e (withi n 4 % o f standard ) an d th e mas s spectra l respons e of uniqu e ions
. 13. 3 Blank s - Method/Procedura l Blank s an d Tri p H/lethod/Procedura i 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 are analyze d prio rt o instmmen t calibration , prio r t o th e analysi s of CCV samples , afte rever y1 0 sampl e injections , an d a t th e en d ofth 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 % ofth e are a coun t ofth e LOQ standard
. I f th e are a counts o fth e procedura l blank

s excee d 50 % ofth e LOQ standard , the n th e LOQ must b e raise d t o th e first standar d leve l that meets criteria
. Tri p Blank : Atri p blan k

ofAST 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 target analyt e an d appropriat e SR S shoul d b e withi n 80-120% ) an d th e percen t relative standar d deviatio n o

fth e recoverie s mus

t b e les s tha n o r equa l t o 20% . I fth e averag e recover yo fa 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 are withi n 20% o ofthei rrespective nomina l valu e [33 % ofth e Q C samples , no t al l replicate s a

t th e sam e concentration , ma yb e outsid e 20 % o

f nomina l value) , th e averag e recover ywil l b e flagged as outsid e metho d acceptance criteria
. Al l LC S sample s wil l b e contro l charte d a s pe rETS-12-012
. I f th e averag e recover

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

fth e expecte d valu e ar

e reporte d as NR , where N R i s define d a s "Not 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 dat a are reportabl e bu t fiagged a s no t meetin g th e FM S metho d acceptance criteria
. 13. 5 Analytica l Metho d Uncertaint y Analytica l metho d uncertaint yfo reac h targe t analyt e an d SR S i s detennine d wit h contro l charte d historica l analysi s batc h LC S data 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 nAnalytica

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 Control 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 rbyLC/MS/MS ; Direc t Injectio n Analysi s Pag e 7 5 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o f PFBS , PFHS , an d PFO S Ber t Jeffrie s Landfil l - Februar y201 2

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

yi n Measurement) an d describe d i n ETS-12-012
. A t least thirt

ydata points are require d fo r detemninin g analytica l metho d uncertainty
. Th e metho d uncertaint yi s define d a s 2xth e standar d deviatio n of th e percen t recoverie s ofth e poole d la b contro l spikes
. Whil e al l LC S data points are contro l charted , onl yth e most recen t fiftydat a points are use d fo rdeterminin g th e metho d uncertainty
. When less than thirty LCS

data points have been generated for a given analyte, the

analysis batch LCSs are used to detennine

the data uncertainty. If

FMSs meet the ±30%recovery

criteria at

a level appropriate

to the endogenous

level, and

the LCS meet the ±20%recovery

criteria, then

the uncertainty

of the data is determined as within ^00±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 fth e expecte d valu e are flagged an d reporte d a s outsid e o f Q C acceptance criteri a wit h expande d uncertainties
. Data wit h FM S recover youtsid e of ±50 % ofth e expecte d valu e are reporte d a s NR , where N R i s define d a s "Not 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 target analyt e an d appropriat e SRS s th e dat a ar e reportabl e bu t flagged as 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/PFOAare prefen-ed
. Quantitatio n i s perfomned b yintegratin g th e linea ran d branche d isomer s together
. Alternately , th e linea ran d branche d isomer

s ca n b e integrate d separately , applyin g th e appropriat e tru 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 o

fth e reference standards
. However , fo rPFOS/PFOAtarge t analytes , i fth e calibratio n standard s are comprise d of predominanti ylinea r isomer s onl yth e metho d require s th e additio n of LCS s of mixe d branched/linea risome rPFOS/PFOA
. Th e purpos e o

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

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

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

fwhethe 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 o f PFOS/PFOA
. 1 4 Pollutio n Preventio n an d Wast e Managemen t Wast e generate d whe n performin g thi s metho d wil l b e dispose d of appropriately
. Th e origina l sample s wil l b e archive d a

t th e 3 M Environmenta l Laborator yi n accordance wit h intema l procedures
. Analysis , November/Decembe r 2000 . c.)Taylor, B.N . an dCE . Kuyatt , NIS T Technica l Not e 1297,1994 Edition ; "Guideline s fo r Evaluating an

dExpressin

g th e Uncertaint

y o f NIS T Measuremen

t Results."d.)Adams , T.M. , "A2L AGuid e fo r th e Estimation o f Measuremen

t Uncertaint

y i n Testing" , Jul

y 2002 . ETS-8-044. 1 Pag e 2 1 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 ; Direct Injectio n Analysi s Pag e 7 6 o f 7 7GLP10-01-02 ; Interi m Repor t 2 6 Analysi s o fPFBS , PFHS , an d PFO S 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 informatio n fo rreconstnjctio n ofth e data
. Infomnatio n fo rth e dat a packag e must include , bu t i s no t limite d t o th e followin g items : stud yo rprojec t number , sampl e an d stand_ar d pre p sheets/records , instrumen t ru n lo g (instrumen t batc h records , instrumen t acquisitio n method , summar ypages) , instmmen 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 fChange 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 chteria 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 determination

of analytical

method uncertainty

and quantitation

of PFOfi^/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 Page 22 0^22 Metho d o fAnalysi s fo rth e Determinatio n o fPerfluorinate d Compound s i n Wate rbyLC/MS/MS ; Direct Injectio n Analysi s Pag e 7 7 o f 7 7