Document XRY216G475DQgda97GpaJgppw
ORIGINAL
DOES NOT CONTAIN CBI
3M Environmental, Health and Safety Operations
3M Center, Building 0224-05-W-03 St. Paul, MN 55144-1000
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Certified Mail
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July 5, 2012 Document Processing Center EPA East - Room 6428 Attn: Section 8(e) Office of Pollution Prevention and Toxics, U.S. EPA 1200 Pennsylvania Avenue NW Washington, DC 20460-0001
NO CBI
Re: TSCA 8(e) Substantial Risk Notice: Sulfonate-based and Carboxylic-based Fluorochemicals, Docket 8EHQ-0598-373 - Results from Analysis of Sediments, Surface Water and Groundwater in the Decatur, Alabama Area
Dear Sir or Madam:
3M is submitting this notice to supplement its previous submissions on sulfonate and carboxylic-based fluorochemicals. More specifically, the data contained in this submittal have been generated as part of a site-related environmental assessment for fluorochemicals that 3M hisaps errefcoernmtliyngrefcoerivitesd3tMheDeenccalotusre,dAflianbalamanaamlytaincaulfarcetpuorritnsgafnadcisliutmy.mAarsypfairgtuoref sthfiosresfafomrpt,li3nMg activities conducted at a regional landfill that previously operated in the vicinity of our Decatur manufacturing facility and also from the wastewater treatment plant area at our Decatur site (due to the size of some of the files pertaining to this submittal, they have been placed on a CD for the reader's convenience):
Regional Landfill
3M recently completed sampling and analytical efforts pertaining to samples of sediments, surface water and groundwater collected at a former disposal site commonly referred to as the former Bert Jeffries landfill. Figure 1, attached, depicts the general location of this site. Figure 2, also attached, illustrates the sample locations at the site itself. It should be noted that the sediment sampling locations, while not specifically referenced on the figure, correspond identically to the surface water sampling points. Furthermore, the monitoring well designations "MWxR" and "MWxL" refer to shallow (residuum) and limestone bedrock water-bearing units, respectively.
The analytical reports summarizing and documenting the data for the referenced sampling efforts are attached and identified as follows:
GLP10-01-01 Interim Report 26: Analysis for PFOA in Sediments Collected from the Jeffries Property in February 2012
GLP10-01-01, Interim Report 27: Analysis of PFOA in Surface Water Samples Collected at Bert Jeffries Landfill in Decatur, AL in February 2012
GLP 10-01-01 Interim Report 31: Analysis of PFOA in Groundwater Samples Collected at Off-Site Wells on Bert Jeffries Property in Decatur, AL in April 2012
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Page 2 of 3
GLP10-01-02 Interim Report 25: Analysis of PFOS, PFHS and PFBS in Sediments Collected from the Jeffries Property
GLP10-01-02; Interim Report 26 - Analysis of PFBS, PFHS, and PFOS in Surface Water Samples Collected at Bert Jeffries Landfill in Decatur, AL in February 2012
GGrLoPu1n0d-w01a-t0er2;SaImntperleims CRoelpleocrtted30at- OAfnf-aSlyitseisWoeflPlsFoBnSB, PerFtHJSef,farineds PPrFoOpSeritny in Decatur, AL in April 2012
While some of the data has been summarized on Figure 2, it should be noted that the complete data set is contained within the attached analytical reports. 3M Decatur Wastewater Treatment Plant (WWTP! Area On-site groundwater monitoring was recently expanded through the construction and sampling of six (6) temporary monitoring wells in and around the 3M Decatur wastewater treatment plant area. These sampling locations are depicted on Figure 3, attached, and all represent groundwater from the shallow (residuum) water-bearing unit at the site. The analytical reports summarizing and documenting the data for the referenced sampling efforts are attached and identified as follows:
GLP10-01-01, Interim Report 32: Analysis for PFOA in Groundwater Samples from New On-Site Wells - Adjacent to the 3M Decatur Wastewater Treatment Plant (WWTP) April 2012
GLP 10-01-02, Interim Report 31: Analysis for PFBS, PFHS, and PFOS in Groundwater Samples from New On-Site Wells - Adjacent to the 3M Decatur Wastewater Treatment Plant (WWTP) April 2012
While some of the data has been summarized on Figure 3, it should be noted that the complete data set is contained within the attached analytical reports. While 3M does not believe that any of these data taken alone or cumulatively meet the "substantial risk" reporting threshold, we nevertheless recognize the ongoing work by U.S. EPA to assess fluorochemical exposure pathways. Therefore, we are placing these results in the 8(e) docket as a supplement to previous submissions. If you have any questions, please contact Deanna Luebker at 651-737-1374 or diluebker@mmm.com. Sincerely,
Vice President Environmental, Health and Safety Operations
Page 3 of 3
List of Attachments: Figure 1 - Regional Map Figure 2 - Former Bert Jeffries Landfill Figure 3 - 3M Decatur, AL Wastewater Treatment Plant Area GLP10-01-01, Interim Report 26 GLP10-01-01, Interim Report 27 GLP 10-01-01, Interim Report 31 GLP 10-01-01, Interim Report 32 GLP10-01-02, Interim Report 25 GLP10-01-02, Interim Report 26 GGLLPP1100--0011--0022,, IInntteerriimm RReeppoorrtt 3310 cc: Glenda Dean, ADEM
PFOA and PFOS concentrations are the averages of primary and duplicate sample analytical results In ng/mL (ppb)
Legend
| Property Line A rea o f Suspected W aste Disposal
^ A bandoned M onitoring W ells Existing M onitoring W ells New M onitoring W ells
Surface W ater Sam plng Locations
0 100 200 Feet
Ma
File Y\3MDectMXDtBertJeffrles landfill PFOA.PFOS SW.mxd, 5/30/2C12 1042:41 AM, ricksc
N ^
Figure 1 F orm er B ert Jeffries Landfill Groundw ater and Surface W ater A verage P F O A and P F O S Concentrations
April 2 0 1 2
Decatur, AL
Legend
Existing M onitoring Wells Temporary M onitoring Wells (TW)
Temporary Piezometer (PZ)
N-aPnoFdtOedAupalincdatPeFsOamS pcloenacneanltyrtaitciaolnrseasurelttshienanvge/rmagLes(popfbp)rimary
221_5_________1_1_2__._5_________O| F eet
TOgSaB
File Y\3MDec\MXD\WWTPJocs_PFOA_PFOS mxd, 5/30/2012 1045 14AM, ricksc
N
T,/C k x
Figure 2 W a stew ater T reatm ent Plant A rea G roundw ater A verage P F O A and
P F O S Concentrations April 2 0 1 2
Decatur, AL
Legend: I I Facility Boundary
Landfill
9,000 4,500
0 Feet
^ --^ n a y iU B D ,
File: \\Fsfed01\TIG\3MDec\MXD\Phase3 landfills mxd, 26-Mar-09 16:15, ricksc
N
s
F igure 1 R e g io n a l L a n d f i l l Map
Decatur, AL
GLP10-01-02 Interim Report 25: Analysis of PFOS. PFHS and PFBS in Sediments Collected from the Jeffries Property
Study Title
3M Environm ental Laboratory A nalytical Protocol G L P 10 -0 1 -0 2 : Analysis o f Perfluorooctane Sulfonate (P F O S ), Perfluorohexane S ulfonate (P F H S ) and Perfluorobutane S ulfonate (P F B S ) in G roundw ater, Soil and S edim ent fo r the 3M D ecatur P hase 3 S ite-R elated Monitoring Program
Data Requirement
E P A T S C A G ood L aboratory P ractice S tand ard s 4 0 C F R P art 7 9 2
Study Director
Jaisim ha K esari P .E ., D EE W eston Solutions, Inc. 1400 W eston W ay
W est C hester, PA 19380 Phone: 610-701-3761
Principal Analytical Investigator
C leston C . Lange, P h.D . 3M Environm ental Laboratory
Interim Report Completion Date
Upon Signing
Performing Laboratory
3M Environmental Health and Safety Operations Environmental Laboratory
3M Center, Bldg 260-05-N -17 S t Paul, MN 55144
Project Identification
G L P 10-01-02-25
Total Num ber o f Pages 24
Study: G LP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collected from the Jeffries Property
This page has been reserved for specific country requirem ents.
Page 2 of 24
Study: G LP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collected from the Jeffries Property
G L P C o m p lia n c e S tatem ent
R e p o rt T itle : G L P 1 0 -0 1 -0 2 Interim R eport 25: Analysis fo r P FO S , P FH S and P FB S in Sedim ents Collected from the Jeffries Property. 3M Environm ental Laboratory A nalytical Protocol G L P -1 0 0 1 -0 2 : Analysis o f Perfluorcoctane S ulfonate (P F O S ), Perfluorohexane S ulfonate (P F H S ) and P erfluorobutane Sulfonate (P F B S ) in G roundw ater, Soil and S edim ent for the 3M D ecatur Phase 3 S ite-R elated M onitoring Program .
This analytical phase w as conducted in com pliance with T oxic Substances C ontrol A ct (T S C A ) G ood Laboratory Practice (G L P ) Standards, 4 0 C FR 7 9 2 , with th e exceptions listed b elo w :
Exceptions to GLP compliance:
T h e referen ce substances w ere not all characterized under G LPs. B ecause th ese are environm ental sam ples and the study analytical in nature only, there w as
no specific test substance o r control substance for this study.
Page 3 of 24
Study: G LP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collected from the Jeffries Property
Q u a l it y A s s u r a n c e S tatem ent
Report Title: G L P 10-01-02 Interim R eport 25: Analysis fo r PFO S , P FH S and PFB S in
Sedim ents C ollected from the Jeffries Property. 3M Environm ental Laboratory A nalytical Protocol G L P -1 0 -0 1 -0 2 : Analysis o f Perfluorooctane Sulfonate (P F O S ), Perfluorohexane S ulfonate (P F H S ) and Perfluorobutane Sulfonate (P F B S ) in G roundw ater, Soil and S edim ent for th e 3M D ecatur P hase 3 S ite-R elated Monitoring Program .
This interim analytical report and the accom panying data w ere audited by the 3M Environm ental Laboratory Q uality Assurance U nit (Q A U ), as indicated below. T he findings w ere reported to the principal investigator (P .I.), laboratory m anagem ent and study director.
Study Inspection Datos
6 /7 /2 0 1 2 -6 /8 /2 0 1 2
Phase
Interim Report and D ata
P.l. 6 /8 /20 1 2
Data Reported to
Study Director Management
Study Director
6 /1 3 /2 0 1 2
6 /1 3 /2 0 1 2
Q AU Representative
' 9/ ' z
'D a te
Page 4 of 24
Study: G LP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collected from the Jeffries Property
Ta b le o f C o n ten ts
G LP Com pliance Statem ent.................................................................................................................................. 3 Quality Assurance S tatem ent................................................................................................................................4 Table o f C ontents.....................................................................................................................................................5 List of Tables.............................................................................................................................................................. 6 1 Study Inform ation............................................................................................................................................. 7 2 S um m ary............................................................................................................................................................8 3 Introduction........................................................................................................................................................ 9 4 Test, Control and R eference Substances................................................................................................. 10 5 TestS ystem ..................................................................................................................................................... 11 6 Method Sum m ary........................................................................................................................................... 11
6.1 M ethods............................................................................................................................................. 11 6.2 Sam ple R eceip t................................................................................................................................ 11 6.3 Sam ple Preparation......................................................................................................................... 12 6.4 Percent Soil Moisture Determination......................................................................................13 6.5 LC /M S/M S Analysis......................................................................................................................... 13 7 Analytical R esults........................................................................................................................................... 14 7.1 C alibration........................................................................................................................................... 14
7 2 Limits o f Quantitation (L O Q s ).........................................................................................................16
7.3 Continuing C alibration..................................................................................................................... 16 7 .4 Blanks..................................................................................................................................................16 7 .5 Laboratory Control Spikes (L C S s )................................................................................................ 16 7.6 Laboratory M atrix Spikes (L M S s )................................................................................................. 18 7 .7 Percent Moisture D eterm inations................................................................................................. 18 7 .8 Individual Analytical Sam ple R esults............................................................................................19
Page 5 of 24
Study: GLP10-01-02, Interim Report 25 Analysis for PFO S, PFHS & PFBS in Sediments Collected from the Jeffries Property
8 Conclusion.......................................................................................................................................................22 9 Data/Sample Retention........................................................................................................................ 23 10 List o f Attachm ents........................................................................................................................................ 23 11 Signatures...................................................................................................................................................... 2 3
L is t o f Ta b l e s
Table 1. Results for Jeffries Property S edim ents.............................................................................................. 8 Table 2 . LM S Recovery for Jeffries Property Sedim ents................................................................................. 9 Table 4 . Instrum ent Inform ation........................................................................................................................... 13 Table 5. Gradient Liquid Chrom atography Conditions (E T S -8-053)............................................................ 14 Table 6 . M ass Transitions..................................................................................................................................... 14 Table 7. P FO S CaNbration Sum m ary................................................................................................................. 15 Table 8 . P FH S Calibration Sum m ary................................................................................................................. 15 Table 9 . PFBS CaSbration S um m ary................................................................................................................. 15 Table 10. LCS Results (P FO S , linear + branched isom er)............................................................................ 17 Table 11. LCS Results (P FH S , linear + branched isom er)............................................................................ 17 Table 12. LCS Results (P F B S )............................................................................................................................ 17 Table 13. Analytical Method Uncertainties........................................................................................................ 18 Table 14. Percent Moistures for Jeffries Properly Sedim ents....................................................................... 19 Table 15. Individual P FO S Results for Jeffries Property Sedim ents........................................................... 19 Table 16. Individual P FH S Results for Jeffries Property Sedim ents............................................................ 20 Table 17. Individual PFBS Results for Jeffries Property Sedim ents............................................................ 21
Page 6 of 24
Study: G LP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collected from the Jeffries Property
1 Study Information
Sponsor
3M Company
Sponsor Representative
G ary A . H ohenstein Environm ental M anager S pecial Projects, E H S O perations Bldg 2 2 4 -5 W -0 3 S t. P aul, M N 5 5 1 4 4 Phone: (651) 737-3570 aahohenstein@ m m m .com
Study Director
Jaisim ha K esari, P .E ., D E E W eston Solutions, Inc. 1400 W eston W ay W est Chester, PA 19380
Study Analytical Testing Facility
3M E H S O perations Environm ental Laboratory Building 2 6 0 -5 N -1 7 S t. Paul, M N 5 5 1 4 4
Study Personnel (3M Environmental Laboratory)
C leston C . Lange, P h .D ., Principal Analytical Investigator W illiam K. R eagen , P h .D ., Laboratory M anager Patrick K enney, Laboratory Technician (P a c e A nalytical, Professional S ervices) M arlene H eying, Laboratory Technician (P ace A nalytical, Professional S ervices)
Study Dates
Study Initiation: M arch 0 8 ,2 0 1 0 Interim A nalytical Initiation: M arch 1 2 ,2 0 1 2 Interim A nalytical Com pletion: M ay 2 9 ,2 0 1 2 Interim R eport C om pletion: Upon final Signatures
Location of Archives
A ll original raw data and analytical reports have been archived a t the 3M Environm ental Laboratory according to 4 0 C F R P art 7 9 2 . T h e test substance and analytical reference standard reserve sam ples are archived a t the 3M Environm ental Laboratory according to 4 0 C FR Part 792.
Page 7 of 24
Study: G LP10-01-02, Interim Report 25 Analysis for PFO S, PFHS & PFBS in Sediments Collected from the Jeffries Property
2 Summary
This interim report provides th e P F O S , P F H S and PFB S concentration results fo r five sedim ent sam ples collected in M arch 2 0 1 2 a t the Jeffries property in northern A labam a. In addition, one travel blank (trip blank), containing b etw een 10-25 gram s o f control soil in a sam ple bottle, accom panied th e sam ple bottles to and from the site and w as also analyzed fo r quality control purposes. S am ples w ere logged into th e 3M Environm ental Laboratory inform ation m anagem ent system (L IM S ) under project G L P 10 -0 1 -0 1 -2 6 and cross referenced to this project G L P 1 0 -0 1 -0 2 -2 5 fo r additional fluorochem ical sulfonates analysis. Four aliquots o f sam ple w ere rem oved from each sam ple bottle and accurately w eighed fo r extraction. T h e first and second aliquot served as analytical sam ple and duplicate analytical sam ple. T h e third and fourth aliquots w ere fortified with nom inal 2 0 .0 and 2 0 0 ng each o f P F O S (lin ear isom er), P F H S (lin ear isom er) and P FB S as a low and high laboratory m atrix spike (L M S ), respectively. T h ree aliquots o f the trip blank w ere taken , with th e third prepared as a single LM S that w as fortified with nom inal 1 .0 0 ng each o f P FO S (lin ear isom er), P F H S (lin ear isom er) and P FB S . S am ples w ere extracted and analyzed p er m ethod E T S 8 -0 5 3 by liquid chrom atography with triple quadrapole m ass spectrom etric detection (L C /M S /M S ). T h e LM S recovery results provided a m easure o f th e d ata accuracy. T h e relative percent difference (R P D ) o f the duplicate analytical sam ple results w as used to assess th e data precision. T he percent m oisture o f each soil w as also determ ined as part o f the study. T he P F O S , P F H S and P FB S concentrations are
sum m arized in Table 1. T he P F O S , P FH S and PFB S recoveries from the LM S sam ples a re sum m arized in Table 2. T h e average data accuracy and standard deviation determ ined from LM S results w as 107% +
7 .9 % fo r P F O S , 105% + 7 .2 % fo r P F H S and 106% + 5 .2 % fo r P FB S . T h e analytical m ethod uncertainty (9 5 % C l) w as determ ined a t + 7 .3 % fo r P F O S , + 10% fo r P FH S and + 12% fo r P FB S .
Table 1. Results for Jeffries Property Sediments
3M U M S ID M
Sam ple ID
Average C oncentration (nia/g; dry)
PFOS
PFHS
PFBS
G L P 10-01-01-26-001
JP A L S D T R IP l 0 0 0 0 0
BLQ
BLQ
BLQ
G L P 10-01-01-26-002
JPA LSD ET010 0 0 0 0
3 .9 5
BLQ
BLQ
G L P 10-01-01-26-003
JPALSDET02 0 0000
8 .5 9
BLQ
BLQ
G L P 10-01-01-26-004
JPALSDET02DB0000
1 0 .0
BLQ
BLQ
G L P 10-01-01-26-005
JPALSDET03 0 0000
1 2 .1
BLQ
BLQ
G L P 10-01-01-26-006
JPALSDET04 0 0000
2 3 .8
BLQ
BLQ
All LMS recovery results were within acceptance criteria of 100 30%
Average concentration o f duplcale analytical result reported; RPDs of dupicates were less than 10% The analytical method uncertainty was determined from LCS results at + 1 2 % for PFBS, 10% for PFHS and + 7.2% for PFOS
Concentration values are shown at 3 significant figures, but more precise data was used for data calculations.
BLQ; analyte response was lower than the analyte response o f the lowest standard (LLOQ) which was the nominal 0.500 ng
calibration standard fl.e. less than nominal 0.50 no/a)
Page 8 of 24
Study: GLP10-01-02, Interim Report 25 Analysis for PFO S, PFHS & PFBS in Sediments Collected from the Jeffries Property
T a b le 2 . L M S R e c o v e ry fo r J e ffrie s P ro p e rty S e d im e n ts
3M LIMS ID w
Sam ple ID
G L P 10-01-01-26-001 Low GL P 10-01-0 1 -2 6 -0 0 2 Low G L P 1 0 -0 1 -0 1 -2 6 -0 0 2 High G L P 10-01-01-26-003 Low G L P 10-01-0 1 -2 6 -0 0 3 High G L P 10-01-01-26-004 Low G L P 1 0 -0 1 -0 1 -2 6 -0 0 4 High G L P 10-01-01-26-005 Low G L P 1 0 -0 1 -0 1 -2 6 -0 0 5 High G L P 10-01-01-26-006 Low G L P 1 0 -0 1 -0 1 -2 6 -0 0 6 High
J P A L S D T R IP l 0 0 0 0 0 LMS JPAL SD E T 0 1 0 0 0 0 0 LM S Low JPAL SD E T 0 1 0 0 0 0 0 LM S High JPAL SD ET02 0 0 0 0 0 LMS Low JPAL SD ET02 0 0 0 0 0 LMS High JPAL SD ET02 DB 0 0 0 0 LM S Low JPAL SD ET02 DB 0 0 0 0 LM S High JPAL SD ET03 0 0 0 0 0 LMS Low JPAL SD ET03 0 0 0 0 0 LM S High JPAL SD ET04 0 0 0 0 0 LMS Low JPAL SD ET04 0 0 0 0 0 LM S High A verage Recovery S ta n d a rd D e v ia tio n RSD
LMS Recovery (% )
PFOS
PFHS
PFBS
130%
125%
105%
102% 103% 104%
105% 103% 102%
114% 103% 110%
104%
105%
103%
105%
100%
105%
104%
103%
9 8 .5%
111%
105%
108%
108%
107%
104%
105%
108%
115%
104%
9 7 .0%
101%
107%
105%
106%
7 .9 %
7 .2 %
5 .2 %
7 .4 %
6.8%
4 .9 %
LMSs were fortified with PFOS, PFHS and PFBS (linear isomers only) at nominal 20.0 ng (low) and 200 ng (high). The LMS for (he trip blank was fortified at nominal 1.0 ng each o f PFOS, PFHS and PFBS Recovery values are shown at 3 significant figures, but more precise data was used for data calculations.
3 Introduction
T h e soil analyses results reported herein w ere conducted as part o f th e P hase 3 Environm ental Monitoring and A ssessm ent Program fo r th e 3M facility located in D ecatur, A labam a. T h e objective o f the overall program is to gain inform ation regarding concentrations o f perfluorooctane sulfonate (P F O S ), perfluorohexane sulfonate (P F H S ) and perfluorobutane sulfonate (P F B S ) in various environm ental m edia such as groundw ater, soils and sedim ents th at are associated w ith and near th e D ecatur facility. R eported herein a re the results from analysis o f sedim ents collected from the Jeffries property. T h e sam ples w ere collected by W eston Solutions, Inc. personnel in February 2 0 1 2 and shipped to the 3M Environm ental Laboratory fo r quantitative analysis o f P F O S , P F H S and PFB S . O n e soil travel blank (trip blank) accom panied th e sam ple bottles to the site, during collection and during sam ples shipm ent and w as analyzed to evalu ate fo r any potential contam ination o f sam ples during th e sam ple shipm ent and collection period.
This report describes the sam ple shipm ent, receipt, extraction and quantitative L C /M S /M S analysis procedures conducted to r determ ination o f P F O S , P FH S and PFB S in the sedim ent sam ples that w ere received. Additionally, included in this report are the assessm ent o f the analytical precision and accuracy fo r th e reported P F O S , P FH S and P FB S concentration results based on duplicate analytical sam ple results and laboratory m atrix spike (L M S ) recovery results, respectively. T he recovery results fo r a stable isotope labeled 13C4-P F O S surrogate recovery standard (S R S ) th at w as added to each soil aliquot prior to extraction, and the determ ined percent m oisture content o f each soil, a re also included herein.
Page 9 of 24
Study: G LP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collected from the Jeffries Property
4 Test, Control and Reference Substances
This study does not have a test substance in th e classic sense o f a G L P study because this study w as purely analytical in nature. T h e reference and control substances a re listed in T a b le 3. I T a b le 3. R eferen ce S ub stan ces
R e fe re n c e ID C h em ic a l N am e
C h em ic a l F o rm u la Use S o u rc e E x p ira tio n D ate S to ra g e C o n d itio n s
C h em ic a l L o t N u m b er TCR Num ber P h y s ica l D e s c rip tio n P u rity
R e fe re n c e ID
C h em ic a l N am e C h em ic a l F o rm u la Use S o u rc e E x p ira tio n D ate S to ra g e C o n d itio n s C h em ic a l L o t N u m b er TCR Num ber P h y s ica l D e s c rip tio n P u rity
PFO S [lineari
PFO S (linear + b ra n ch e d )
PFHS lineari
n-P erfluorooctane-1Sutfbnate Potassium S alt
Perfluorooctane Sulfonate Potassium S alt
rvP erfluorohexane-1-sulfonate Sodium S alt
n-C eFizSQ sK
CsF it SOs K
n -C aF uS O sN a
R eference Standard for Calibration and LM Ss
R eference Standard for LC Ss
R eference S tandard for C alib ratio n and LM S s
W ellington Laboratories
3M
W eK nglon Laboratories
1 0 /1 8 /1 8
1 2 /1 4 /1 6
3125/18
Frozen
Frozen
F ro ze n
LPFO SK B M 06
171
LPFH xSA M 06
T C R 08-0001-1/1
T C R -696
T C R 08-0018-1/1
C rys ta llin e
W h ite P ow der
C rys ta llin e
98%
8 6 .4 %
>98%
PFH S (linear + branched'!
n -F e rilu o ro h e x a n e -1 sulfonate Potassium S alt
n-C sFiaSO sK
PFBS (p redom inantly linear-
P erflu orob utane-1 -su lfo n ate P o tassiu m S a lt
rv-C-rFaSCb K
' C4 -PFOS
[1 ,2 ,3 .4 -13C 4^3erfluotooctane1-Sulfonate Sodium S alt
,3C 4 ,2C 4F ,7S Q 3 N a
R eference Standard for LCSs
3M
R e fere n c e S tan d ard fo r All PFBS
3M
S u rro g a te W ellington Laboratories
2 /1 2/1 7
F ro ze n NB 120067-69
T C R -083 W h ite Pow der
9 8.6%
1 /1 0 /1 7
Frozen 101
T C R -121 W h ite P o w der
9 6 .7 %
9 /8 /2 0 1 3
Frozen M PFOS0910 TC R 10-0044-2/9 Liquid; M ethanol solution
>98% w
Page 10 of 24
Study: G LP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collected from the Jeffries Property
R e fe re n c e ID
C h em ic a l N am e C h em ic a l F o rm u la Use S ource
C b- P F O S
[13CeTPeriluorooctane-1 Sulfonate Sodium S alt
13C8 F i7S 0 3 N a
Internal Standard fo r PFOS
W ellington Laboratories
C b- P F H S
[13C 3)-P erflu oroh exane-1 S u lfo n ate S odium S a lt 13C 312C 3 F i3 S 0 3 N a
In tern al S tan d ard fo r P F H S
W ellin g to n L ab orato ries
O.-PFBS
[1802}-Perfluorobutane-1 Sutfonate Am m onium S ait
C *F#Sm Q2180 NH
Internai Standard fo r PFB S
R T I International
E xp ira tio n D a te
9 /2 8 /2 0 1 3
9 /2 8 /2 0 1 3
3 /9 /1 5
S to ra g e C o n d itio n s
-2 0 'C
-2 0 `C
-2 0 'C
C h em ic a l L o t N u m b er
092310
092310
1 1 5 4 6 -1 0 7 -2
TCR Num ber
TC R 10 -0 0 4 8 -3 /1 6 ,4 /1 6
T C R 10 -0 0 4 8 -3 /1 6 , 4 /1 6
TC R -1042
P h y s ica l D e s c rip tio n
Liquid; M ethanol solution
Liquid; M ethanol solution
Liquid; M ethanol solution
P u rity
>98% w
>98% w
>99% w
[a] T h e co m m ercially provided m a te ria l w a s a m ethan ol solutions and la b e le d w ith a w eig h t/vo lu m e concentration p urity v a lu e . H o w ever, th e con centration o f fu rth e r dilutions w as b ased on th e ce rtifie d con centration o f th e stock m a te ria l.
5 Test System
T h ere w as not a test system fo r this study in th e classic sense o f a G LP study. This study w as conducted fo r analysis o f sedim ents collected from th e Jeffries property th at is located in N orthern A labam a. S am ples fo r this study a re "real world" environm ental sam ples.
6 Method Summary
6.1 Methods
The sam ple extractions and quantitative LC/MS/MS analyses w ere perform ed following method E TS -8-053.0. The results reported herein w ere obtained from analytical run j120507b. Tw o analytical runs w ere conducted as o 120312a and o 120313a, but result not used due to Q C results that did not m eet method acceptance criteria.
6.2 Sample Receipt
O n February 2 1 ,2 0 1 2 seven em pty 250-m L H O P E N algeneTM sam ple bottles, and one travel blank (trip b lank) containing approxim ately 1 0 -2 5 gram s o f a control soil T C R -4 5 5 , w ere sen t from th e 3M Environm ental Laboratory to W eston Solutions, Inc. field personnel fo r collection o f sedim ents from th e property known as th e Jeffries Property, form erly the B ert Jeffries landfill. Following the sam ple
Page 11 of 24
Study: G LP10-01-02, Interim Report 25 Analysis for PFO S, PFHS & PFBS in Sediments Collected from the Jeffries Property
collections by W eston Solutions, Inc. personnel, five sedim ent-filled sam ple bottles and th e trip blank w ere returned in th e bottles to the 3M Environm ental Laboratory fo r quantitative analysis o f P FO S , P FH S and P FB S . T h e sam ples w ere received with sam ple chains o f custody num bers 152 9 0 on March 0 2 ,2 0 1 2 .
Soil sam ples from A labam a a re regulated and th e sedim ents fo r this study w ere shipped in accordance with U S D A /A P H IS soil perm it num ber P 3 3 0 -0 9 -0 0 1 2 5 .
Sam ple nom enclature follows the form JPAL-SD-ET-xxxx w here the first string defines the Jeffries Property Alabam a (JPAL), the second string defines the sam ple m edia (Le., S D = sedim ent SB -fie ld sam ple duplicate), the third string defines the site location (E T = eastern tributary), the fourth string defines the field sam ple (1 ,2 ,3 ... or DB = duplicate field sam ple) .T h e fourth string defines the sedim ent sampling depth (0000 = 0 ft to 0 .5 ft interval).
6.3 Sample Preparation
Each s o l or sedim ent extraction involved rem oval of a 1 cubic centim eter (1 cc; 1 m L) aliquot o f field sam ple (typically ~ 1 gram ) from each sam ple bottle using a fixed volume 1 cc spoon, transferring it to a 15 mL conical centrifuge tube, followed by accurate weight determination of the aliquot on a 5-place balance. Then, nominal 3.0 rig o f internal standard (IS; nominal 3.0 ng) and 3.0ng o f surrogate recovery standard (S R S ) was added to each soil aliquot and a known quantity o f P FO S (Knear isom er), PFH S (linear isom er) and PFBS was added to each LM S. Then each was extracted by addition o f 8 mL of a 4:1 acetonitrflew ater solution followed by sonication for 1 to 2 hours followed by centrtfugation to rem ove solids. T he supernatant from each was then transferred to an autovial for analysis. An accurately measured volume o f each supernatant was analyzed by LC/M S/M S.
During preparation, each sam ple and quality control sam ple received nominal 3 .0 ng o f a stable isotope labeled 13C4-P FO S surrogate recovery standard (S R S ). Although not included as part o f the data accuracy assessm ent for this study, S R S recovery determinations w ere included as part o f an ongoing method validation aspect for S R S behavior in environmental soil and sedim ent sam ples for potential future applications. The S R S was quantified from a S R S calibration curve constructed from analysis of calibration standards prepared from the SRS in calibration standards. The S R S recovery w as determ ined based on the calculated concentration o f SRS from the analysis and recovery o f SR S from each sam ple is included in T ab les 1 5 ,1 6 and 17 but was not used for evaluation o f data accuracy for this study and is otherwise excluded from the discussions in the report
Each analytical sam ple was prepared in duplicate for analysis o f PFO S, P FH S and PFBS in the sam ple. Additionally, a third and/or fourth replicate was weighed out and used to prepare LMSs. T he LM S results w ere used for determination of data accuracy. R PD o f dupficate sam ples results was used for determ ination o f data precision. Appropriate LM S levels are considered those that are within 0.5-tim es to 10-tim es the m easured endogenous anatyte level in the equivalent non-fortified soil/sedim ent sam ple, and the fortification o f 2 0 ng and 200 ng was sufficient in a t least one o f the LM Ss to be considered appropriate for determination o f the data accuracy for PFO S, but was greater than 10-tim es the PFBS and PFH S endogenous levels which were less than the LLO Q (B LQ ) in all samples.
Calibration standards w ere prepared by spiking known quantities o f PFO S (in e a r isom er), PFH S (linear isom er), PFBS and 13C4-P F O S into 1-cubic centim eter (1 cc, 1 m L) aliquots o f 3M Environmental Laboratory control soil TC R -455. The nominal m ass o f 1 cc o f control s o l T C R -455 is 1.0 gram (dry), therefore, the nominal calibration standard range prepared and analyzed was 0 .2 0 0 ng/g to 500 ng/g.
Laboratory control spike (LC S ) sam ples w ere prepared with each sam ple preparation batch; prepared a t three levels (nominal 3.00 ng/g, 30.0 ng/g and 300 ng/g) and each level in tripicate. The LCSs were prepared using control soil TC R -455, sam e as calibration standards, and w ere fortified with P FO S (m ixed In e a r + branched isom ers), P FH S (m ixed linear + branched isom ers) and PFB S. The LC S results were used to estim ate the analytical method uncertainty.
Page 12 of 24
Study: G LP10-01-02, Interim Report 25 Analysis for PFO S, PFHS & PFBS in Sediments Collected from the Jeffries Property
6.4 Percent Soil Moisture Determination
The percent moisture of sedim ent sam ples was determ ined by gravim etric analysis. Dry weights w ere determ ined from separate weighings than the sam ple aliquot weighings used for extractions. To determ ine the percent moisture, duplicate aliquots of each soil sam ple w ere rem oved and the accurate "w e f weight determ ined for each. Each aliquot was then dried a t >100X2 until no further mass loss occurred from w ater evaporation, at which tim e the accurate dry sam ple weights w ere determ ined. The difference in m ass, attributed to w ater evaporation, was used to calculate the percent moisture o f the original sam ple. The averaged percent moisture result for each was then used to report the P FO S, P FH S and PFBS concentration on a dry weight basis.
6.5 LC/MS/MS Analysis
T he analysis o f sam ple extracts fo r P F O S , P FH S and P FB S w as perform ed by L C /M S /M S as described in m ethod E T S -8 -0 5 3 .0 . T h e relative percent difference (R P D ) o f duplicate prepared sam ple results w as used as a m easure o f the analytical precision. T h e determ ined recovery o f fortified P F O S , P F H S and P FB S from LM S sam ples w as used as a m easure o f analytical accuracy. S urrogate recoveries a re reported in T a b le s 1 5 ,1 6 an d 17, but w ere not used for evaluating analyte recovery fo r this study. T h e surrogate data w as collected as part o f an on-going evaluation o f surrogate recovery from environm ental field sam ples fo r supporting a m ethod validation o f E T S -8 -0 5 3 .
Details o f the specific instrument param eters, the liquid chromatography gradient program, and the specific m ass transitions analyzed are detailed in the raw data, and are briefly described below in T ab le 4 , T ab le 5 and T able 6.
Table 4. Instrument Information
Instru m en t N am e A n alytical M ethod ID Liquid C hro m atog raph G uard colum n E xtraction colum n A n alytical colum n Injection V o lum e M ass S p ectro m eter Io n S o urce P o larity S o ftw are
E TS -Jonas (i) E T S -8 -0 5 3 .0 A g ilen t 1 1 0 0 w ith B in ary Pum p P re-A u tosam p ler; Prism R P (2.1 x 5 0 m m , 5 urn) O a s is H LB (3 x 2 0 m m . 2 5 u ): 3 0 C B etasil C 1 8 (2.1 x 1 0 0 m m . 5 u )
25 uL API 5000 T u rbo lo n S p ray N eg ative A n alyst 1 .4 .2
Page 13 of 24
J_ ' '_JLI " "' 'T ? ' F I TP 'I--- -- T T T W I
Study: G L P 1 0 -0 1 -0 2 , Interim R eport 2 5 Analysis fo r P F O S , P FH S & P FB S in Sedim ents C ollected from th e Jeffries Property
T a b le 5 . G ra d ie n t L iq u id C h ro m a to g ra p h y C o n d itio n s (E T S -8 -0 5 3 )
S te p N um ber
T o ta l T im e [m in ]
1 0.0 2 3.0 3 3.5 4 17.0 5 17.5 6 19.5 7 20.0 8 23.0
F lo w R a te [m U m in ]
0.400 0.400 0.400 0.400 0.400 0.400 0.400 0.400
P e rc e n t A [2 m m A q u e o u s A m m o n iu m A c e ta te l
97.0 97.0 70.0 40.0 10.0 10.0 97.0 97.0
P e rc e n t B [A c e to n itrile ]
3.0 3.0 30.0 60.0 90.0 90.0 3.0 3.0
Table 6. Mass Transitions
A n a h /te PFB S
18Q2- P F B S ( IS )
M a s s T ra n s itio n s M o n ito re d 299>99, 299>80 303>84
P FH S
13C3- P F H S ( IS )
399>99. 399>80 402>80
PFO S
499>130, 499>99, 499>80
13C b- P F O S ( IS )
S 07>80
13C 4- P F O S ( S u r r o g a te )
503>80
N o te : M u ltip le m a s s tra n s itio n s a re s u m m e d to g iv e th e In s tru m e n t re s p o n s e fo r th a t anaM e.
7 Analytical Results
C oncentration values are rounded to three significant figures according to E P A rounding rules. B ecause o f rounding som e calculated values m ay vary slightly from those found in th e raw d ata. S am ples w ith R P D s fo r duplicate results o f less than 50 % and LM S results m eeting th e m ethod criterion o f within 100 30% dem onstrated th a t the m ethod w as appropriate fo r those sam ples and w ere reported w ithout footnotes in results tables. T he nom inal 2 0 .0 ng and 2 0 0 ng fortified quantities o f P F O S , P FH S and P FB S into LM Ss fo r field sam ples w ere a t an appropriate level fo r evaluating sam ple-specific analyte recoveries fo r P F O S . R esults fo r P F H S and P FB S w ere all less than the LLO Q (B L Q ) and therefore LM S fortifications w ere g reater than 10-tim es th e endogenous level m easured in the sam ples.
7.1 Calibration
A set o f calibration standards w ere prepared by spiking varying known quantities of P FO S (linear), PFH S (linear), PFBS and surrogate (13C rP F O S ), and a fixed quantity o f stable isotope labeled internal standards, into one cubic centim eter (1 cc, 1 m L) aliquots o f 3M Environmental Laboratory control soil T C R -455 (nominal soil m ass of 1.0 g/m L). A total o f twelve (1 2 ) calibration standards w ere prepared as a s e t The prepared standards w ere fortified from nominal 0 .2 0 0 ng to 500 ng h i 1 cubic centim eter of
Page 14 of 24
Study: G LP10-01-02, Interim Report 25 Analysis for PFO S, PFHS & PFBS in Sediments Collected from the Jeffries Property
control soil T C R -455; equivalent to nominal 0.200 ng/g to 500 ng/g in soil T C R -455. Following analysis of the calibration standards, the concentration o f each standard was plotted against the m easured
analyte /IS peak area ratio. A quadratic equation with 1lx weighting was used to fit the data for each
analyte. Calibration curves w ere not forced through zero. Determining the standard concentration using the resultant calibration curve and comparing to the known concentration confirmed accuracy o f each curve point a t within 100 3 0 % (+ 3 5 % a t the LLO Q ). The correlation coefficient (r) was greater than 0 .9 9 9 for all calibration curves, and the coefficient of determination (r2) was greater than 0.990. Calibration results for PFO S, P FH S and PFBS are sum m arized in T a b le 7, T a b le 8 and T ab le 9, respectively.
Because soil and sedim ent weights can vary significantly for a 1 c c (1 m L) field sam ple, depending on composition and moisture content, the instalm ent response was calibrated for the known concentrations of target analytes based on the m ass quantity o f reference substance added to a 1 ccsoil (1 mL)
calibration standard prior to extraction (e.g. calibrated in this study for a range o f 0 .500 ng to 500 ng
P FO S , P FH S and PFBS; the 0 .2 0 0 ng standard was excluded). Because a 1cc aliquot of control soil T C R -455 weighs nominally 1.0 gram (dry weight) and has less than 5% moisture content, the nominal concentration range of the calibration was essentially 0.200 ng/g to 500 ng/g. However, because sam ple soil aliquots m ay weigh m ore than 1.0 gram and contain significant moisture, the determ ined concentrations during the analysis on an ng per sam ple aliquot basis from the calibration curve and then adjusted for the accurate determ ined weight and percent moisture so they could be reported on a ng/g (dry weight) basis.
T a b le 7. P FO S C a lib ra tio n S um m ary
ARunnalytical
STO 1
STD 2
STD 3
STD*
STD 5
STD 6
PFOS (n ti STD 7
STDS
STD 9 STD 10 STD 11 STD 12
r
Actual 0.199 0.499 0.748 0.997 2.49 4.99 9.97 24.9 49.9 99.7 199 499 N/A
slll007a excluded 0.478 0.791 0.888 2.51 5.42 10.1 24.5 50.6 98.9 199 499 0.9999
Recovery N/A 95.8% 106% 89.1% 101% 109% 101% 98.4% 101% 99.2% 100% 100% N/A
T a b le 8 . PFH S C a lib ra tio n S um m ary
ARunnalytical
STD 1
STD 2
STD 3
STD*
A ctua l
0.200 0.500 0.750 1.00
sll1007a excluded 0.473 0.801 0.908
Recovery N/A 94.6% 107% 90.8%
STDS
2.50
2.41 96.4%
W HS (nJ
STD 6
STD 7
STDS
5.00 10.0 25.0
5.57 9.95 26.2
111% 99.5% 105%
STD 9
50.0
47.5 95.0%
STD 10
100 99.9 99.9%
STD 11
200 201 101%
STD 12
500
500 100%
r
N/A 0.9998 N/A
T a b le 9. P FB S C a lib ra tio n S um m ary
ARunnalytical
A ctual
W BS(ng)
STD 1
STD 2
STD 3
STD*
STDS
STD 6
STD 7
STD 8 STD 9 STD 10 STD 11 STD 12
0.200 0.500 0.750 1.00 2.50 5.00 10.0 25.0 50.0 100 200 500
r N/A
sll1007a excluded 0.415 0.773 0.944 2.54 5.90 9.76 25.5 51.5 97.7 199 501 0.9998
Recovery N/A 83.0% 103% 94.4% 102% 118% 97.6% 102% 103% 97.7% 99.5% 100% N/A
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Study: G LP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collected from the Jeffries Property
7.2 Limits of Quantitation (LOQs)
The lower limit o f quantitation (LLO Q ) was the lowest non-zero calibration standard in the curve that m et the linearity and accuracy requirem ent for a low standard (1 0 0 + 35% ) and for which the area counts were a t least twice that o f the average response determ ined for the method blank injected just prior to the calibration standards. The LLO Q for this study was the nominal 0.500 ng cafibration standard (nominal 0.500 ng/g in s o l T C R -455) for PFO S, P FH S and PFB S. All sam ple analyte responses less than the response o f the 0.500 ng calibration standard w ere reported as BLQ (below the limits of quantitation). The upper limit o f quantitation (U LO Q ) was the nominal 500 ng calibration standard.
7.3 Continuing Calibration
During the course o f each analysis, continuing calibration verifications (C C V s) w ere perform ed by regular injection of a mid-level calibration standard after approxim ately every 15th sam ple injected in the analytical run. T he back calculated concentration results w ere used to confirm that the instrument response and the initial calibration curve w ere still in control. All C C Vs flanking reported data m et the method criteria of 100% 30% accuracy.
7.4 Blanks
Three types o f blanks w ere analyzed during this analysis: method blanks w ere prepared with blank matrix soil T C R -455 and w ere spiked with IS and surrogate; travel blanks (trip blanks) prepared from aliquots o f s o l T C R -455 sealed in s am ple bottle that accompanied the bottle order to and from the sampling site; and solvent blanks containing extraction solvent The different blank results w ere reviewed to evaluate potential contamination during shipment, and to evaluate method perform ance param eters such as injector carry over and to establish the LLOQ. All blanks w ere below the LLOQ (B L Q )
7.5 Laboratory Control Spikes (LCSs)
Laboratory control spikes w ere prepared by spiking know quantities o f P FO S (linear + branched), P FH S (linear + branched) and PFBS into 1 cc aliquots o f s o i TC R -455, fortified a t nominal 3 .0 ng and 30 ng and 300 ng levels, with each level prepared in triplicate. The results of the LC S analyses and calculation of analyte m easurem ent accuracies (percent recovery) for PFO S, PFH S and PFBS are shown in T ab le 10, T a b le 11 and T a b le 12 respectively. The analytical method uncertainty calculated from LCS results is shown in T ab le 13.
L C S R e c o v e ry = (P e te n n in e d C o n c e n tra tio p o f L C S ) * 10oo/0 S p ik e C o n c e n tra tio n
Study: GLP10-01-02, Interim Report 25 Analysis for PFO S, PFHS & PFBS in Sediments Collected from the Jeffries Property
Table 10. LCS Results (PFOS, linear + branched isomer)
Sample ID
3.00 LCS
PFOS Recovery 30.0 LCS
300 LCS
114%
109%
118%
LCSs (j120507b)
112%
109%
117%
108%
114%
113%
Average Recovery Std Dev.
111% 2.9%
111% 3.1%
116% 2.8%
RSD
2.6%
2.8%
2.4%
Nominal LCS concentrations w ere 3.00 ng/g. 30.0 ng/g and 300 ng/g of PFOS (linear + branched isomers), each prepared and analyzed in triplicate.______________________________________________________________________________________________
Table 11. LCS Results (PFHS, linear + branched isomer)
Sample ID
PFHS Recovery
3.00 LCS
30.0 LCS
300 LCS
118%
109%
108%
LCSs (120507b)
116%
107%
113%
103%
107%
105%
Average Recovery
113%
108%
109%
Std Dev.
8.3%
1.1%
3.9%
RSD
7.4%
0.99%
3.5%
Nominal LCS concentrations were 3.00 ng/g. 30.0 ng/g and 300 ng/g of PFHS (In e a r + branched isomers), each prepared and analyzed in triplicate.______________________________________________________________________________________________
Table 12. LCS Results (PFBS)
Sample ID
LCSs (120507b)
Average Recovery Std Dev. RSD
3.00 LCS 116% 117% 113% 116% 2.1% 1.8%
PFBS Recovery
30.0 LCS 106% 114% 109% 110% 4.2% 3.8%
300 LCS 98.3% 112% 106% 106% 7.0% 6.6%
Nominal LCS concentrations were 3.00 ng/g. 30.0 ng/g and 300 ng/g of PFBS, each prepared and analyzed in triplicate.
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Study: G LP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collected from the Jeffries Property
T a b le 13. A n a ly tic a l M eth o d U n c e rta in tie s
S a m p le ID
3 .0 0 LCSs
3 0 .0 LCSs
300 LCSs A verage R ecovery S td D ev. RSD M eth o d U n c e rta in ty (2 x S td . D e v .); 95% C l
7.6 Laboratory Matrix Spikes (LMSs)
PFOS 114% 112% 109% 109% 109% 115% 119% 118% 113% 113% 3 .7 % 3 .3 % 7 .3 %
LC S R esults
PFHS 118% 116% 103% 109% 107% 107% 108% 113% 105% 110% 5 .1 % 4 .7% 10%
PFBS 116% 117% 113% 106% 114% 109% 9 8 .3 % 112% 106% 110% 6 .1 % 5 .5 % 12%
Laboratory matrix spikes (LM S s) w ere generated by adding a known quantity o f PFO S (n ear), PFH S (linear) and PFBS to an aliquot o f sedim ent sam ple, and then preparing the sam ple the sam e as non spiked sam ples. Spikes for this study, LM Ss w ere spiked at levels that w ere appropriate for the endogenous analyte levels in the soils, determ ined from screening analysis and fortified with the target analytes from 0.5-tim es to 10-tim es the endogenous analyte levels determ ined in the soil/sedim ent sam ples during the range finding analysis. T he LM S method acceptance criterion of within 100 3 0 % w ere m et for a l LM S recoveries. The LMS recovery results a re sum m arized in T ab le 2. T he nominal 2 0 .0 ng and 200 rig fortified quantities o f P FO S , P FH S and PFB S into LMSs for field sam ples were a t an appropriate level for evaluating sam ple-specific analyte recoveries for P FO S . Results for P FH S and PFBS w ere a l less than the LLO Q (B LQ ) and therefore LM S fortifications w ere greater than 10-tim es the endogenous level m easured in the sam ples. The PFO S, P FH S and PFBS recovery calculations for LM Ss used the following equation:
L M S R eco very -- ^ ctorm *ne^ C o n c e n tra tio n o f L M S --D e term in e d C o n c e n tra tio n o f F ie ld S am p le) * jqqo/ S p ik e C o n c e n tra tio n
7.7 Percent Moisture Determinations
The percent moisture w as determ ined for each soil sam ple. Duplicate aliquots o f each w ere taken and accurately weighed to determ ine the "wet" w eight Then each aliquot was dried a t > 1 0 0 0 until no further loss in m ass occurred (foe to w ater evaporation, after which the dry weight was accurately determ ined. The average percent moisture and R P D o f the duplicate determinations fo r each soil are reported in T a b le 14. T he percent moisture was calculated by the folow ing equation:
(O rig in a l S o il W e t M a s s - D rie d S o il M ass) P ercent M o is tu re = ------------------------------------------------------------- *100%
O rig in a lS o il W e t M ass
Page 18 of 24
Study: G LP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collected from the Jeffries Property
T a b le 14. P e rc e n t M o is tu re s fo r J e ffrie s P ro p e rty S ed im en ts
L IM S ID
S am ple ID
A verage Percent M oisture (w /w )w
G L P 10-01-01-26-001
J P A L S D T R IP l 0 0 0 0 0
2 .7%
G L P 10-01-01-26-002
JPAL SD E T 0 1 0 0 0 0 0
28%
G L P 10-01-01-26-003
JPALSDET02 0 0000
30%
G L P 10-01-01-26-004
JPALSDET02 DB 0 0 0 0
30%
G L P 10-01-01-2 6 -0 0 5
JPAL SD ET03 0 0 0 0 0
40%
G L P 10-01-01-2 6 -0 0 6
JPAL S D E T 0 4 0 0 0 0 0
61%
[a] Percent moisture determined for duplicate sample aliquots taken from each sample bottle
R elative Percent D ifference w 2 .5 % 0 .7 8% 1 .5 %
0 .7 8% 3 .6 % 0 .0 9 6 %
7.8 Individual Analytical Sample Results
The individual analytical sam ple results for PFO S, P FH S and PFBS concentrations are shown in T ab le 15, T a b le 16 and T ab le 17, respectively.
T a b le 15 . In d iv id u a l P FO S R e s u lts fo r J e ffrie s P ro p e rty S ed im en ts
Sample Description
G L P 10-01-01-21-001 G L P 10-01-01-21-001 Dup G L P 10-01-01-21-001 LMS
G L P 10-01-01-21-002 G L P 10-01-01-21-002 Dup G L P 10-01-01-21-002 Low LMS G L P 1 0 -0 1 -0 1 -2 1 -0 0 2 High LMS
G L P 10-01-01-21-003 G L P 10-01-01-21-003 Dup G L P 10-01-01-21-003 Low LMS G L P 1 0 -0 1 -0 1 -2 1 -0 0 3 High LMS
G L P 10-01-01-26-004 G L P 1 0-01-01-26-004 Dup
Surrogate (u C-PFOS)
Recovery
109% 110% 105% 101% 103% 102%
104% 106% 110% 107%
103% 106% 104%
LMS Spike C o ncentration
(ng/g; dry w eight)
N /A
1 .0 4
N /A
1 4 .6 143
N /A
1 5 .0 151
N /A
M easured PFOS C o ncentration
(ng/g; dry w eight)
BLQ
BLQ
LMS Recovery
N /A
Average PFOS C o n cen tratio n (ng/g; dry w t.) and RPD (%)
BLQ
1 .3 5
130%
N /A
3 .8 1 4 .0 9 1 8 .8 152
N /A 102% 103% W
3 .9 5 7 .0 %
8 .9 9 8 .2 0
N /A
8 .5 9
2 4 .1 166
104% 104% W
9 .1%
9 .8 1 0 .2
N /A
1 0 .0
Page 19 of 24
Study: G LP10-01-02, Interim Report 25 Analysis for PFO S, PFHS & PFBS in Sediments Collected from the Jeffries Property
Table 15. Individual PFOS Results for Jeffries Property Sediments
Sample Description
G L P 10-01-01-26-004 Low LMS G L P 1 0 -0 1 -0 1 -2 6 -0 0 4 High LMS
Surrogate (u C-PFOS) Recovery
105%
105%
LMS Spike C o ncentration
(ng/g; dry w eight)
1 6 .6
152
M easured PFOS C o n c e n tra tio n
(ng/g; dry w eight)
2 7 .5
168
LMS Recovery
105% 104% W
Average PFOS Concentration (ng/g; dry w t.) and RPD (%)
3 .6 %
G LP 10-01-01-21-005 G L P 10-01-01-21-005 Dup
104% 106%
N /A
1 1 .9 1 2 .2
N /A
1 2 .1
G L P 10-01-01-21-005 Low LMS G L P 1 0 -0 1 -0 1 -2 1 -0 0 5 High LMS
104% 104%
1 9 .6 198
3 3 .8 227
111% 108% W
2 .9 %
G L P 10-01-01-21-006 G L P 10-01-01-21-006 Dup
104% 102%
N /A
2 3 .5 2 4 .1
N /A
2 3 .8
G L P 10-01-01-21-006 Low LMS G L P 1 0 -0 1 -0 1 -2 1 -0 0 6 High LMS
106% 104%
3 5 .8 380
6 1 .4 418
105% 104%
2 .5 %
N/A; not applicable BLQ; analyte response was low er than the analyte response o f the LLOQ which was nom inal 0.500 ng/g low standard, [a] LMS fortification level was greater than 10-times the endogenous analyte level.
Table 16. Individual PFHS Results for Jeffries Property Sediments
Sample Description
G L P 10-01-01-21-001 G L P 10-01-01-21-001 Dup G L P 10-01-01-21-001 LMS
G L P 10-01-01-21-002 G L P 10-01-01-21-002 Dup G LP 10-01-0 1 -2 1 -0 0 2 Low LMS G L P 1 0 -0 1 -0 1 -2 1 -0 0 2 High LMS
G L P 10-01-01-21-003 G L P 10-01-01-21-003 Dup G L P 10-01-01-21-003 Low LMS G L P 1 0 -0 1 -0 1 -2 1 -0 0 3 High LMS
Surrogate (u G-PFOS) Recovery
109% 110% 105% 101% 103% 102% 104% 106% 110% 107% 103%
LMS Spike C o n cen tratio n
(ng/g; dry w eight)
N /A
1 .0 4
N /A
1 4 .6 144
N /A
1 5 .1 151
Measured PFHS C o n cen tratio n
(ng/g; dry w eight)
BLQ
BLQ
LMS Recovery
N /A
Average PFHS C o n cen tratio n (ng/g; dry w t) and RPD (%)
BLQ
1 .3 0
125%
N /A
BLQ BLQ
N /A
BLQ
1 5 .3 148
105% w 103% W
N /A
BLQ BLQ
N /A
BLQ
1 5 .4 158
102% w 105% W
N /A
Page 20 of 24
Study: G LP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collected from the Jeffries Property
Table 16. Individual PFHS Results for Jeffries Property Sediments
Sample Description
G L P 10-01-01-26-004 G L P 10-01 -01 -2 6 -0 0 4 Dup
Surrogate (u C-PFOS)
Recovery
106%
104%
LMS Spike C o n c e n tra tio n
(ng/g; dry w eight)
N /A
Measured PFHS C o n c e n tra tio n
(ng/g; dry w eight)
BLQ
BLQ
LMS Recovery
N /A
Average PFHS C o n cen tratio n (ng/g; dry w t.) and RPD (%)
BLQ
G L P 10-01-01-26-004 Low LMS G L P 1 0 -0 1 -0 1 -2 6 -0 0 4 High LMS
105% 105%
1 6 .7 153
1 6 .7 157
1 0 0 % 1,1 103% W
N /A
G L P 10-01-01-21-005 G L P 10-01-01-21-005 Dup
104% 106%
N /A
BLQ BLQ
N /A
BLQ
G L P 10-01-01-21-005 Low LMS G L P 1 0 -0 1 -0 1 -2 1 -0 0 5 High LMS
104% 104%
1 9 .7 199
2 0 .7 212
105% W 107% w
N /A
G L P 10-01-01-21-006 G L P 10-01-01-21-006 Dup
104% 102%
N /A
BLQ BLQ
N /A
BLQ
G LP 10-01-0 1 -2 1 -0 0 6 Low LMS G L P 1 0 -0 1 -0 1 -2 1 -0 0 6 High LMS
106% 104%
3 6 .0 382
3 8 .7 371
108% w 9 7 .0% w
N /A
N/A; not applicable BLQ; analyte response was lower than the analyte response o f the LLOQ which was nominal 0.500 ng/g low standard. [a] LMS fortification level was too low relative to the endogenous analyte level to make an accurate determ ination of recovery.
Table 17. Individual PFBS Results for Jeffries Property Sediments
Sam ple Description
G L P 10-01-01-21-001 G L P 10-01-01-2 1 -0 0 1 Dup G L P 10-01-01-21-001 LMS G L P 10-01-01-21-002 G L P 10-01-01-21-002 Dup G L P 10-01-01-21-002 Low LMS G L P 1 0 -0 1 -0 1 -2 1 -0 0 2 High LMS G L P 10-01-01-21-003 G L P 10-01-01-21-003 Dup G L P 10-01-01-21-003 Low LMS
Surrogate ( 1sC -P FO S )
Recovery
109% 110% 105% 101% 103% 102% 104%
106% 110% 107%
LMS Spike Concentration
(ng/g; dry w eigh t)
N /A
1 .0 4
N /A
1 4 .6 144
N /A
1 5 .1
Measured PFBS Concentration (ng/g; dry weight)
BLQ
BLQ
LMS Recovery
N /A
Average PFBS Concentration (ng/g; dry w t) and RPD (% )
BLQ
1 .0 9
105%
N /A
BLQ BLQ
N /A
BLQ
1 6 .6 148
114% w 103% w
N /A
BLQ BLQ
N /A
BLQ
1 6 .6
1 1 0 % 1,1
N /A
Page 21 of 24
Study: G LP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collected from the Jeffries Property
T a b le 17. In d iv id u a l P FB S R e s u lts fo r J e ffrie s P ro p e rty S ed im en ts
Sample Description G L P 1 0 -0 1 -0 1 -2 1 -0 0 3 High LMS
Surrogate (13C*-PFO S)
Recovery
103%
LMS Spike Concentration
(ng/g: dry weight)
151
Measured PFBS Concentration (ng/g; dry weight)
148
LMS Recovery
103% w
Average PFBS Concentration
(ng/g; <ky w t) and RPD (% )
G L P 10-01-01-26-004 G L P 10-01-01-26-004 Dup
106% 104%
N /A
BLQ BLQ
N /A
BLQ
G L P 10-01-01-26-004 Low LMS G L P 1 0 -0 1 -0 1 -2 6 -0 0 4 High LMS
105% 105%
1 6 .7 153
1 7 .4 150
105% w 9 8 .5 % w
N /A
G L P 10-01-01-21-005 G L P 10-01-01-21-005 Dup
104% 106%
N /A
BLQ BLQ
N /A
BLQ
G L P 10-01-01-21-005 Low LMS G L P 1 0 -0 1 -0 1 -2 1 -0 0 5 High LMS
104% 104%
1 9 .7 199
2 1 .2 206
108% W 104% w
N /A
G L P 10-01-01-21-006 G L P 10-01-01-21-006 Dup
104% 102%
N /A
BLQ BLQ
N /A
BLQ
G L P 10-01-01-21-006 Low LMS G L P 1 0 -0 1 -0 1 -2 1 -0 0 6 High LMS
106% 104%
3 6 .0 382
4 1 .4 384
115% w 101% w
N /A
N/A; not applicable BLQ; analyte response was lower than the analyte response of the LLOQ which was nominal 0.500 ng/g low standard.
8 Conclusion
Sedim ents collected from th e Jeffries Property in M arch 2 0 1 2 w ere successfully analyzed fo r P FO S , P FH S and PFB S following 3M Environm ental Laboratory m ethod E T S -8 -0 5 3 .0 and conducted a s 3M study G LP 10 -0 1 -0 2 -2 5 . T h e averag e P F O S , P FH S and P FB S concentration results fo r the soil sam ples are sum m arized in T a b le 1 and th e LM S recoveries a re sum m arized in T a b le 2 . T he individual analytical sam ple results are shown in T a b le 1 5 , T a b le 16, and T a b le 1 7 fo r P F O S , P FH S and P FB S , respectively. T h e soil trip blank th at accom panied th e sam ple bottles to th e site and then accom panied sam ples back to th e laboratory w as sufficiently devoid o f P F O S , P FH S and PFB S , indicating th at no contam ination o f th e sam ples occurred during sam ple shipm ent o r sam ple to the laboratory. T h e P FH S and P FB S levels in the sam ples w ere all less than th e 0 .5 ng/g calibration standard th at defined th e low er lim it o f quantitation. T he P F O S concentrations in th e sedim ent sam ples ranged from 3 .9 5 ng/g to 2 3 .8 ng/g.
T he d ata accuracy w as within 100 + 30% and the data precision w as excellen t with R P D s less than
10%.
T he analytical m ethod uncertainties (9 5 % C l) w ere determ ined by statistical exam ination o f the LCS results fo r P F O S , P F H S and P FB S and w ere + 7 .3 % fo r P F O S , + 10% fo r P FH S and + 12% for P FB S , respectively, a t the 95% confidence interval (9 5 % C l).
Page 22 of 24
Study: G LP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collected from the Jeffries Property
9 Data/Sample Retention
All associated project data (hardcopy and electronic) will be archived as project G LP10-01 -02-25 according to 3M Environmental Laboratory standard operating procedures. The percent moisture raw data was determ ined for the samples as part of study G LP10-01-01-26 and that raw data are archived with that interim study data packet and report.
10 List of Attachments
Attachment A: Preparation Forms, Raw Data and Chromatograms
11 Signatures
Report Approval:
C leston C . Lange, p u .d ., Principal A nalytical Investigator
D ate
W illiam K. R eagen , P h.D ., 3M Environm ental Laboratory M anagem ent
r
fG ary A. Hohenstein, Sponsor R epresentative
Jaisim ha K esari,
.
D a te
D ate
2^ D ate
Page 23 of 24
Study: G LP10-01-02, Interim Report 25 Analysis for PFO S, PFHS & PFBS in Sediments Collected from the Jeffries Property
Attachment A Preparation Forms, Raw Data and Chromatograms
Page 24 of 24
GLP10-01-01 Interim Report 26: Analysis for PFOA in Sediments Collected from the Jeffries Property in February 2012
Study Title
3M Environm ental Laboratory Analytical Protocol G L P 1 0 -0 1 -0 1 : Analysis o f Perfluorooctanoic Acid (P F O A ) in G roundw ater, Soil and S edim ent fo r th e 3M D ecatu r P hase 3 S ite-R elated
M onitoring Program
Data Requirement
E P A T S C A G ood Laboratory P ractice S tand ard s 4 0 C F R P a rt 7 9 2
Study Director
Jaisim ha K esari P .E ., D EE W eston Solutions, Inc. 1400 W eston W ay
W est Chester, PA 19380 Phone: 610-701-3761
Principal Analytical Investigator
C leston C . Lange, P h.D . 3M Environm ental Laboratory
Interim Report Completion Date
Upon Signing
Performing Laboratory
3M Environmental Health and Safety Operations Environmental Laboratory
3M Center, Bldg 260-05-N -17 S t Paul, MN 55144
Project Identification
G L P 10-01-01-26
Total Num ber o f Pages 19
I 11 I li IIl mu lini NMI 11J 1 lllill IJ J lB IL ll III i _ ju __i li nini in u m i ji i n h
Study: G L P 1 0 -0 1 -0 1 , Interim R eport 2 6 Analysis fo r P FO A in Sedim ents C ollected from th e Jeffries Property, Feb. 201 2
This page has been reserved fo r specific country requirem ents.
Page 2 of 19
Study: G LP10-01-01, Interim Report 26 Analysis for PFOA in Sediments Collected from the Jeffries Property, Feb. 2012
R e p o rt T itle : G L P 10-01-01 Interim R eport 26: A nalysis fo r P FO A in S edim ents C ollected from the Jeffries Property in February 2 0 1 2 . 3M Environm ental Laboratory A nalytical Protocol G L P 1 0 0 1 -0 1 : Analysis o f Perfluorooctanoic Acid (P F O A ) in G roundw ater, Soil and S edim en t fo r the 3M D ecatur P hase 3 S ite-R elated M onitoring Program .
T his analytical p hase w as conducted in com pliance with Toxic Substances C ontrol A ct (T S C A ) G ood Laboratory P ractice (G L P ) Standards. 4 0 C F R 7 9 2 , w ith th e exceptions listed b elo w :
Exceptions to GLP compliance:
Test, control and reference substances w ere not all characterized under GLPs.
Samples environmental samples, there was no dosing and no specific tost substance for this study.
Page 3 of 19
Study: G LP10-01-01, Interim Report 26 Analysis for PFOA in Sediments Collected from the Jeffries Property, Feb. 2012
R e p o rt TiU e: G L P 10-01-01 Interim R eport 26: Analysis for P FO A in S edim ents C ollected from the Jeffries Property in February 2012. 3M Environm ental Laboratory A nalytical Protocol G L P 1 0 01-01: Analysis o f P erfluorooctanoicA cid (P F O A ) in Groundw ater, Soil and S edim en t fo r the 3M D ecatur Phase 3 S ite-R elated M onitoring Program .
This interim study report and the accom panying d ata w ere audited by the 3M Environm ental Laboratory Q uality A ssurance U nit (Q A U ), as indicated below. T h e findings w ere reported to the principal investigator (P .I.), laboratory m anagem ent and study director.
Study Inspection Dates
4 /3 /2 0 1 2 - 4 /5 /20 1 2
1
&
Interim Report and D ata
P.l. 4 /9 1 2 0 1 2
Data Reported to
Study Director Management
Study Director
4 /1 0 /2 0 1 2
4 /1 0 /2 0 1 2
QAU
D ate
Page 4 of 19
Study: G LP10-01-01, Interim Report 26 Analysis for PFOA in Sediments Collected from the Jeffries Property, Feb. 2012
G LP Com pliance Statem ent.................................... Quality Assurance S tatem ent................................. Table o f C ontents...................................................... List of Tables............................................................... 1 Study Inform ation............................................... 2 S um m ary............................................................. 3 Introduction.......................................................... 4 T e s t Control and R eference Substances..... 5 Test System ......................................................... 6 Method Sum m ary...............................................
6.1 M ethods.................................................
6 2 Sam ple R eceip t....................................
6.3 Sam ple Preparation............................. 6.4 Percent Soil Moisture Determination 6.5 LC /M S /M S Analysis............................. 7 Analytical R esults............................................... 7.1 C alibration.............................................
7 2 Limits o f Quantitation (L O Q s )...........
7 .3 Continuing C alibration......................... 7 .4 Blanks..................................................... 7 .5 Laboratory Control Spikes (L C S s ).... 7 .6 Laboratory Matrix Spikes (L M S s )..... 7 .7 Percent Moisture D eterm inations..... 7 .8 Individual Sam ple R esults..................
Page 5 of 19
m s*
..3 ..4 ..5 ..6 ..7 ..8 ..9 ..9
10 10 10 10 10
11 11
13 13 14 14 14 14 15 16 16
.........................................................................................r W l l t f I iMIH-- III!IIP
Study: G L P 1 0 -0 1 -0 1 , Interim R eport 2 6 Analysis fo r P FO A in S edim ents Collected from th e Jeffries Property, Feb. 2 0 1 2 8 Conclusion.......................................................................................................................................................17 9 Data/Sam ple Retention.................................................................................................................................17 10 List o f Attachm ents.........................................................................................................................................17 11 Signatures........................................................................................................................................................ 18
Table 1. P FO A Results for Sedim ents from Jeffries Property, February 2 0 1 2 ..........................................8 Table 2 . LM S PFO A Recovery Results for Sedim ents from Jeffries Property, February 2 0 1 2 .............. 8 Table 3. Reference Substances.......................................................................................................................... 9 Table 4 . Instrument Information......................................................................................................................... 12 Table 5. Gradient Liquid Chrom atography Conditions (E T S -8-053)...........................................................12 Table 6 . Mass Transitions................................................................................................................................... 12 Table 7 . PFO A Calibration Sum m ary (CaHbrated with linear P F O A )........................................................ 13 Table 8 . LCS R esults...........................................................................................................................................15 Table 10. Percent Moistures for Jeffries Property Sedim ents, February 2 0 1 2 ...................................... 16 T a b le 1 1 . Individual PFO A Results for Jeffries Property Sedim ents, February 2 0 1 2 ............................16
Page 6 of 19
Study: G LP10-01-01, Interim Report 26 Analysis for PFOA in Sediments Collected from the Jeffries Property, Feb. 2012
Sponsor
3M Company
Sponsor Representative
G ary A . Hohenstein Environm ental M anager S pecial Projects, E H S O perations Bldg 2 2 4 -5 W -0 3 S t. Paul, M N 551 4 4 Phone: (651) 737-3570 aahohenstein@ m m m .com
Study Director
Jaisim ha K esari, P .E ., D E E W eston Solutions, Inc. 1400 W eston W ay W est Chester, PA 19380
Study Analytical Testing Facility
3M E H S O perations Environm ental Laboratory Building 2 6 0 -5 N -1 7 S t P aul, M N 551 4 4
Study Personnel (3M Environmental Laboratory)
C leston C . Lange, P h .D ., Principal Analytical Investigator W illiam K. R eagen, P h .D ., Laboratory M anager Patrick K enney, Laboratory Technician (P ace A nalytical, Professional S ervices) M arlene H eying, Laboratory Technician (P ace A nalytical, Professional S ervices)
Study Dates
Study Initiation: M arch 0 8 ,2 0 1 0 Interim A nalytical Initiation: M arch 0 2 ,2 0 1 2 Interim A nalytical Com pletion: M arch 2 3 ,2 0 1 2 Interim R eport C om pletion: Upon final Signatures
Location of Archives
A ll original raw d ata and analytical reports have been archived a t the 3M Environm ental Laboratory according to 4 0 C F R P art 7 9 2 . T h e test substance and analytical reference standard reserve sam ples are archived a t the 3M Environm ental Laboratory according to 4 0 C FR Part 792.
Page 7 of 19
Study: G LP10-01-01, Interim Report 26 Analysis for PFOA in Sediments Collected from the Jeffries Property, Feb. 2012
This interim report provides th e P FO A concentration results fo r five sedim ents collected from the Jeffries property (B ert Jeffries Landfill) located in Northern A labam a. O n e travel blank (trip blank), containing approxim ately 1 0 -2 5 gram s o f control soil in a sam ple bottle, accom panied th e sam ple bottles to and from the collection site and w as also analyzed. Sam ples w ere received on M arch 0 2 ,2 0 1 2 and logged into the 3M Environm ental Laboratory electronic LIM S system under project G L P 1 0 -0 1 -0 1 -2 6 . Prior to extraction, sedim ents w ere aliquoted from each sam ple bottle in triplicate into extraction vessels and accurately w eighed. T h e first and second aliquot served as analytical sam ple and duplicate sam ple. T he third replicate o f each w as fortified with nom inal 2 .0 0 ng o f P FO A as a laboratory m atrix spike (L M S ). A single LM S fo r th e trip blank w as also prepared and fortified with nom inal 1.00 ng o f P FO A . E ach aliquot w as extracted and analyzed p er m ethod E T S -8 -0 5 3 by liquid chrom atography with triple quadrapole m ass spectrom etric detection (L C /M S /M S ). T h e P FO A recovery results from LM Ss provided a m easure o f sam ple-specific accuracy fo r th e results. T h e relative percent difference (R P D ) o f th e duplicate sam ple results w as used to assess th e analytical precision o f the sam ple results. T h e percent m oisture o f each soil w as also determ ined as part o f th e study and results reported on a dry sedim ent w eight basis. T he
P FO A concentrations and R P D s a re sum m arized in T a b le 1. T h e LM S fortification concentrations and recoveries fo r P FO A a re sum m arized in T a b le 2.
Table 1. PFOA Results for Sediments from Jeffries Property, February 2012
3 M U M S ID
G L P 10-01-01-26-001 G L P 10-01-01-26-002 G L P 10-01-01-26-003 G L P 10-01-01-26-004 G L P 10-01-01-26-005 G L P 10-01-01-26-006
S a m p le ID
J P A L S D T R IP 10 0 0 0 0 JPA LSD ET010 0 0 0 0 JPALSDET02 0 0000 JPALSD ET02 D B 0000 JPALSDET03 0 0000 JPALSD ET04 0 0 0 0 0
Avg. PFOA C o n c e n tra tio n (n g /g ;
d ry w e ig h t) BLQ 0 .6 2 9 0 .6 7 1 0 .8 1 9 1 .0 6 2 .3 9
R e la tiv e P ercen t D iffe re n c e
NA 14% 23% 42% 1 .4 % 11%
BLQ; The integrated peak area response for PFO A in the sample was below the PFO A peak area response for the lowest standard that was used to construct the caHbration curve (< nominal 0.200 ng/g). NA; not applicable
Table 2. LMS PFOA Recovery Results for Sediments from Jeffries Property, February 2012
3 M U M S ID
S am p le ID
PFO A Spike C o n c e n tra tio n (n g /g ; d ry w e ig h t)
PFOA Recovery (D a ta Accuracy)
G L P 10-01-01-26-001 LMS
JPAL SD T R IP 1 0 0 0 0 0 , LMS 1 .0 0 ng
0 .9 8 0
8 9 .6%
G L P 10-01-01-26-002 LMS
JPAL SD E T 0 1 0 0 0 0 0 , LMS 2 .0 0 ng
1 .3 8
9 2 .5%
G L P 10-01-01-26-003 LMS
JPAL SD ET02 0 0 0 0 0 , LMS 2 .0 0 ng
1 .6 7
8 9 .3%
G L P 10-01-01-26-004 LMS G L P 10-01-01-26-005 LMS
JPAL SD ET02 DB 0 0 0 0 , LMS 2 .0 0 ng JPAL SD ET04 0 0 0 0 0 , LMS 2 .0 0 ng
1 .4 5 2 .1 3
8 5 .0% 9 1 .8%
G L P 10-01-01-26-006 LMS
JPAL SD T R IP 1 0 0 0 0 0 , LMS 2 .0 0 ng
3 .3 4
101%
[a] Samples with an endogenous PFOA level o f BLQ were treeted as a concentration o f zero to calculate recovery.
Page 8 of 19
Study: G LP10-01-01, Interim Report 26 Analysis for PFOA in Sediments Collected from the Jeffries Property, Feb. 2012
lin O W C M M
T he analyses reported herein w ere conducted as part o f th e P hase 3 Environm ental Monitoring and A ssessm ent Program fo r th e 3M facility located in D ecatur, A labam a. T h e objective o f th e overall program is to gain inform ation regarding concentrations o f periluorooctanoate (P F O A ) in various environm ental m edia such a s groundw ater, soils and sedim ents th at are associated with and near th e D ecatur facility. R eported herein a re th e results from analysis o f sedim ents collected from the Jeffries property. T h e sam ples w ere collected by W eston Solutions, Inc. personnel in February 2 0 1 2 and shipped to the 3M Environm ental Laboratory fo r quantitative analysis o f P FO A . O n e soil travel blank (trip b lank) accom panied the sam ple bottles to th e site, during collection and during sam ples shipm ent and w as analyzed to evaluate fo r any potential contam ination o f sam ples during the sam ple shipm ent and collection period.
This report describes th e sam ple shipm ent, receipt, extraction and quantitative L C /M S /M S analysis procedures conducted for determ ination o f P FO A in th e soils fo r project G L P 1 0 -0 1 -0 1 -2 6 . A dditionally, included in this report a re the assessm ent o f th e analytical precision and accuracy fo r the reported P FO A concentration results, th e recovery results for a stable isotope labeled 13C 4-P F O A surrogate recovery standard (S R S ) th at w as added to each soil aliquot prior to extraction, and the determ ined percent m oisture content o f each soil.
U 0 fH r O l a n a Im W M tC S < H IW D H 1 C 9 8
<.
This study does not have a test substance in th e classic sense o f a G LP study because this study w as purely analytical in nature. T h e analytical reference substances a re listed in T a b le 3.
T a b le 3. R fren c S ub stan ces
T est Substance
P F O A (lin ear isom er), fre e acid
Technical P F O A (lin ear + branched isom ers), am m onium salt
13C 4-PFO A
,3C e-PFO A
Use
Calibration & LM Ss
LCSs
S u rro g a te
Internal Standard
Source
Oakwood
3M
W ein g to n Labs
W ellington Labs
Expiration D ate S torage Conditions C hem ical Lot
J a n .1 7 ,2018 Frozen 3440
Feb. 2 7 ,2 0 1 7 Frozen 332
Dec. 0 7 ,2 0 1 3 Frozen
M PFOA1210
M ay 2 4 ,2 0 1 4 Frozen 052411
TC R Num ber Physical Description
T C R 07-0041-1/1 Powder
T C R -123 W h ite Pow der
T C R 1 1 -0 0 0 1 -11 /1 4 M ethanol Solution m
T C R 1 1-0 0 1 6 -13 /1 7 & T C R 1 1 -0 0 1 6 -14 /1 7
M ethanol S o lu tio n "
Purity
9 9 .6%
95%
>98%
>98%
[a] S table isotope labeled m aterials a re typically provided a s m ethanol solutions by the com m ercial vendor and a re treated as 100% pure; the vendor's reported m ethanol stock concentration is used for calculating concentrations o f diluted standards m ade from them .
Page 9 of 19
fi H T T P M i r. _I i I 'B!?11 vw,m
1
I
Study: G L P 1 0 -0 1 -0 1 , Interim R eport 26 Analysis fo r P FO A in Sedim ents C ollected from th e Jeffries Property, Feb. 2 0 1 2
5 Test System - ^
T h ere w as not a test system fo r this study in th e classic sense o f a G LP study. This study was conducted fo r analysis o f sedim ents collected from the Jeffries property th at is located in Northern A labam a. S am ples fo r this study a re ` real world* environm ental sam ples.
M atfiodSummary
-
na
6.1 Methods
The sam ple (tractions and quantitative LC /M S/M S analyses w ere performed following validated method E TS -8-053.0. Two analytical batches w ere prepared for this study as o120309c and o120316a. The result for the trip blank was reported from batch o120309c and results for field sam ples w ere reported from run 120316a.
6.2 Sample Receipt
O n February 2 1 ,2 0 1 2 seven em pty 250-m L H D P E N algeneTM sam ple bottles, and one travel blank (trip b lank) containing approxim ately 1 0 -2 5 gram s o f a control soil T C R -4 5 5 , w ere sen t from th e 3M Environm ental Laboratory to W eston Solutions, Inc. field personnel fo r collection o f sedim ents from the property known as th e B ert Jeffries landfill. Following th e sam ple collections by W eston Solutions, Inc. personnel, five sedim ent-filled sam ple bottles and the trip blank w ere returned in the bottles to th e 3M Environm ental Laboratory fo r quantitative analysis o f P FO A . T h e sam ples w ere received with sam ple chains o f custody num bers 15290 on M arch 0 2 ,2 0 1 2 .
Soil sam ples from A labam a a re regulated and the sedim ents fo r this study w ere shipped in accordance with U S D A /A P H IS soil perm it num ber P 3 3 0 -0 9 -0 0 1 2 5 .
Sam ple nom enclature follows the form JPAL-SD-ET-xxxx where the first string defines the Jeffries Property Alabam a (JPAL), the second string defines the sam ple m edia (i.e., S D = sedim ent SB -fie ld sam ple duplicate), the third string defines the site location (E T = eastern tributary), the fourth string defines the field sam ple (1 ,2 ,3 ... or DB = duplicate field s a m p le ). The fourth string defines the sedim ent sampling depth (0000 = 0 ft to 0 .5 ft interval).
6.3 Sample Preparation
Sam ple preparation was conducted as two analytical batches, o120309c and o 120316a. T he first batch was prepared with LM Ss fortified a t 2 0 and 200 ng of PFO A, which was later determ ined to be too high for a proper evaluation o f PFO A recovery from the sediments which contained much lower P FO A levels. The trip blank was prepared with a 1 ng P FO A LM S and was reported from that batch. The sam ples were prepared a second tim e as o120316 a with a 2 ng fortified LM S for each sam ple, and the sam ple results reported from that batch.
Each sofl or sedim ent extraction involved rem oval o f a 1 cubic centim eter (1 cc; 1 m L) aliquot o f field sam ple (typically- 1 gram ) from each sam ple bottle using a fixed volume 1 cc spoon, transferring it to a 15 mL conical centrifuge tube, followed by accurate weight determination of the aliquot on a 5-place balance. Then, nominal 3.0 ng o f internal standard (IS; nominal 3.0 ng) and 3.0ng o f surrogate recovery standard (S R S ) was added to each soil aliquot and a known quantity o f PFO A was added to each LM S. Then each was extracted by addition o f 8 mL o f a 4:1 acetonitrilew ater solution followed by sonication for 1 to 2 hours followed by centrifugation to rem ove solids. T h e supernatant from each w as then transferred to an autovfel
Page 10 of 19
Study: G LP10-01-01, Interim Report 26 Analysis for PFOA in Sediments Collected from the Jeffries Property, Feb. 2012
for analysis. An accurately m easured volume o f each supernatant was analyzed by LC /M S/M S.
During preparation, each sam ple additionally received nominal 3 .0 ng o f a stable isotope labeled surrogate recovery standard (S R S ) as 1iC<-PFOA. Although not included as part o f the data accuracy assessm ent for this study, S R S recovery determ inations w ere included as part o f an ongoing method validation aspect for S R S behavior in environmental soil sam ples for potential future applications. The S R S was quantified from a S R S calibration curve constructed from analysis o f calibration standards prepared from the S R S in calibration standards. The S R S recovery w as determ ined based on the calculated concentration o f SR S from the analysis and recovery o f S R S from each sam ple is included in T a b le 10, but was not used for evaluation o f data accuracy for this study and is otherwise excluded from the discussions in the report
Each analytical sam ple was prepared in duplicate for analysis of PFO A in the sam ple. Additionally, a third and/or fourth replicate was weighed out and used to prepare LMSs. The LM S results w ere used for determ ination of data accuracy. R PD of duplicate sam ples results was used for determ ination of data precision. Appropriate LM S levels are considered those that are within 0.5-tim es to 10-tim es the m easured endogenous P FO A level in the equivalent non-fortified soil/sedim ent sam ple.
Calibration standards w ere prepared by spiking known quantities of PFO A (linear isom er) into 1-cubic centim eter (1 cc, 1 m L) aliquots o f 3M Environmental Laboratory control soil TC R -455. The nominal m ass of 1 cc o f control soil T C R -455 is 1.0 gram (dry), therefore, the nominal calibration standard range prepared and analyzed was 0 .2 0 0 ng/g to 500 ng/g.
Laboratory control spike (LC S ) sam ples w ere prepared with each sam ple preparation batch; prepared at three levels (nom inal 3 .0 0 ng/g, 3 0 .0 ng/g and 300 ng/g) and each level in triplicate. T he LCSs were prepared using control soil T C R -455, s a n e as calibration standards, and w ere fortified with technical P FO A (inear-r-branched isom er). The LCS results w ere used to estim ate the analytical method uncertainty.
6 .4 P e rc e n t S o il M o is tu re D e te rm in a tio n
The percent moisture o f sedim ents and soils w ere used to calculate the dry weight o f the w et so l and sedim ent sam ples weighed during sam ple preparations for P FO A analysis, and was determ ined by gravim etric analysis. Dry weights w ere determ ined for separate weighings than the weighings used for P FO A extraction and analysis procedures. T o determ ine the percent moisture, duplicate aliquots o f each soil sam ple w ere rem oved and the accurate "wet" weight determ ined for each. A l aliquots w ere dried a t > 1 0 0 0 until no further m ass loss occurred from w ale r evaporation, a t which tim e the accurate dried weights w ere determ ined. T he difference in m ass, attributed to w ater evaporation, was used to calculate the percent moisture o f the original s o l. The averaged percent moisture result for each was then used to calculate the soil P FO A concentration on a dry weight basis, and is reported for each sam ple in T a b le 9.
6.5 LC/MS/MS Analysis
T h e L C /M S /M S analysis w as perform ed as described in m ethod E T S -8 -0 5 3 .0
T h e relative percent d ifference (R P D ) o f th e duplicate sam ple results w as used as a m easure o f the analytical precision. T he determ ined recovery o f fortified P FO A from th e LM S sam ples w as used as a m easure o f sam ple-specific analytical accuracy. R ecovery o f the surrogate (13C4-P F O A ) is included within this report in T a b le 10 as an indirect m easure o f analytical data accuracy, and is not considered in the accuracy assessm ent fo r this study and is only included as part o f an on-going m ethod validation aspect in which surrogate recovery behavior is being evaluated in "real world* environm ental sam ptes fo r possible future applications.
Details o f the specific instrument param eters, the liquid chromatography gradient program, and the specific m ass transitions analyzed are detailed in the raw data, and are briefly described below in T a b le 4 , T a b le 5 and T able 6.
Page 11 o f 19
...Jl... .. 1.111:4 i H L
J: i i. lui i.il .il.y i i L ui
Study. G L P 1 0 -0 1 -0 1 , Interim R eport 2 6 Analysis fo r P FO A in Sedim ents C ollected from th e Jeffries Property, Feb. 2 0 1 2
Table 4. Instrument Information
Instru m en t N am e A n alytical M ethod ID L iau id C h ro m atoaraD h G uard colum n E xtraction colum n A n alytical colum n In jection V o lum e M ass S p ectro m eter Ion S o urce P o larity S o ftw are
E T S -O llie E T S -8 -0 5 3 .0 A a ile n t 1 1 0 0 w ith B in ary P um p P re-A u tosam p ler; P rism R P (2 .1 x 5 0 m m . 5 u ) O asis H LB (3 x 2 0 m m . 2 5 u ): 3 0 C B etasil C 1 8 (2.1 x 1 0 0 m m . 5 u )
25 uL API 4000 Turbo lo n S p ray N eg ative A n alyst 1 .4 .2
Table 5. Gradient Liquid Chromatography Conditions (ETS-8-053)
S to p N um ber
T o ta l T im e [m in j
1 0 .0 2 3 .0 3 3 .5 4 1 7 .0 5 1 7 .5 6 1 9 .5 7 2 0 .0 8 2 3 .0
F lo w R a te [m U m in ]
0 .4 0 0 0 .4 0 0 0 .4 0 0 0 .4 0 0 0 .4 0 0 0 .4 0 0 0 .4 0 0 0 .4 0 0
P e rc e n t A [2 m m A q u eo u s A m m o n iu m A c e ta te ]
9 7 .0 9 7 .0 7 0 .0 4 0 .0 1 0 .0 1 0 .0 9 7 .0 9 7 .0
P e rc e n t B [ A c e to n itrile ]
3 .0 3 .0 3 0 .0 6 0 .0 9 0 .0 9 0 .0 3 .0 3 .0
Table 6. Mass Transitions
A n a ly te PFO A
13C 4- P F O A ( S u r r o g a t e )
M a s s T ra n s itio n s M o n ito re d 413>169, 413>219, 413>369 417>169, 417>219, 417>372
13C g -P F O A ( IS )
421>172, 421>223, 421>376
N o te : M u ltip le m a s s tra n s itio n s a re s u m m e d to g iv e th e in s tru m e n t re s p o n s e fo r th a t anaM e.
Page 12 of 19
Study: G LP10-01-01, Interim Report 26 Analysis for PFOA in Sediments Collected from the Jeffries Property, Feb. 2012
7 Analytical R-- uHs
All results are rounded to th ree significant figures according to E P A rounding rules. B ecause o f rounding, values m ay vary slightly from those found in the raw d ata. All results w ere calculated from accurate values in th e raw d ata. Laboratory m atrix spikes (L M S ) m eeting the m ethod acceptance criteria o f 100 3 0 % , dem onstrate that th e m ethod w as appropriate.
7.1 C a lib ra tio n
Calibration standards w ere prepared by spiking varying known quantities o f PFO A (linear isom er) and surrogate, and a fixed quantity o f internal standard, into separate 1-cubic centim eter (1 cc, 1 m L) aliquots of 3M Environmental Laboratory m atrix s o l T C R -455 (nominal 1.0 gram per m L). A total o f twelve (1 2 ) soil m atrix calibration standards ranging from nominal PFO A concentration 0 .2 0 0 ng/g to 5 0 0 ng/g w ere prepared and analyzed. Following the analysis of calibration standards, the nominal concentration o f each standard was plotted versus the m easured analyte peak area/IS peak area response ratio. A quadratic equation with 1/x weighting was used to fit the calibration response data. Calibration curves w ere not forced through zero. Calculating the determ ined standard concentration using the resultant calibration curve and comparing to the known concentration confirmed accuracy o f each curve point within 100 3 0 % (+ 35% a t the LLO Q ). The correlation coefficient (r) was greater than 0.996, and coefficient of determ ination (r2) w as greater than 0.990. Calibration results for PFO A are sum m arized in T ab le 7.
Because soil weights vary significantly for a 1 cc (1 m L) soil sam ple, depending on soil type and moisture content the instrument response was calibrated for the known concentrations o f PFO A based on the m ass
quantity o f PFO A added to each 1 cc soil calibration standard prior to extraction (e.g. calibrated in this
study for a range o f 0 .2 0 0 ng/g to 2 0 0 ng/g PFO A). Because a 1cc aliquot o f control soil T C R -455 weighs approximately 1.0 gram (dry weight) and has less than 5% moisture content the nominal concentration range o f the calibration was essentially 0 .2 0 0 ng/g to 200 ng/g. However, because the sam ple so ls and sediments can vary in moisture content composition and density, 1 cc aliquots o f field soil and sedim ent sam ples typically weigh m ore o r less than 1.0 gram . Therefore, the final m easured results from the analysis w ere adjusted for the accurate determ ined dry weight o f the 1 cc sam ple aliquot that was extracted.
T a b le 7. P FO A C a lib ra tio n S um m ary (C a lib ra te d w ith lin e a r P FO A )
A n a ly tic a l Run
A c tu a l Cone.
0120309c
STD 1
0 .2 0 0
STD 2
0 .5 0 0
excluded 0.342
STD 3
0 .7 5 0
STD 4
1 .0 0
0.651 1.01
STD 5
2 .5 0
2 .7 8
P F O A (ng >W STD STD STD
67 8
5 .0 0
9 .9 9
2 5 .0
5.13 11.9 27.2
STD 9
5 0 .0
5 3 .5
STD 10
100
101
STD 11
200
183
STD 12
500
512
r
N /A
0 .9 9 8 4
0120316a
0 .1 6 6
0.511 0.763 0.911 2.62
5.45 10.4
26.3
5 1 .7
9 6 .8
198
502
0 .9 9 9 8
Average (ng)
0 .1 6 6
0.427 0.707 0.961 2.70
5.29 11.2
2 6 .8
5 2 .6
9 8 .9
191
507 0 .9 9 9 1
Avg. Recovery
_______
83.0%
85.3%
94.3%
9 6 .1 %
108% 106% 112% 107% 105% 98.9% 95.3% 101%
NA
NA; not applicable [a] PFO A concentrations are nominal ng/g (dry soil w t) concentration based on a nominal mass o f 1.0 gram (dry w t.) for each 1 cubic centimeter o t control soil used to prepare each calibration standard.
Page 13 of 19
Study: G LP10-01-01, Interim Report 26 Analysis for PFOA in Sediments Collected from the Jeffries Property, Feb. 2012
7.2 Limits of Quantitation (LOQs)
The lower limit o f quantitation (LLO Q ) w as the lowest non-zero calibration standard in the curve that m et linearity and accuracy requirem ents (100 + 35% ) and for which the area counts w ere a t least 2 X that o f the average response determ ined from the method blanks. The LLO Q for analytical run o120309c, from which the trip blank result was reported, was nominal 0.500 ng/g calibration standard. T he LLO Q for analytical batch o120316a, from which the study sam ple results w ere reported, was nominal 0 .2 0 0 ng/g. Ail sam ple analyte responses less than the response of the 0.200 ng/g calibration standard w ere reported as BLQ (below the limits o f quantitation).
7 .3 C o n tin u in g C a lib ra tio n
During the course o f each analysis, continuing calibration verifications (C C V s) was performed by regular injection o f a m id-level cafibration standard after approximately every 15 sam ples in the analytical run. The back calculated concentration results for PFO A from C C Vs w ere used to confirm that the instrument response and the initial calibration curve w ere still in control. A l C C V s flanking reported P FO A data m et the method criteria o f 100% 30% accuracy, except for in o120309c w here one of the C C V s for PFO A was a t 131% and the P FO A result for the trip blank in that run reported with a method deviation.
7 .4 B lan ks
Three types o f blanks w ere analyzed during this analysis: solvent blanks; and method blanks, which were prepared with blank matrix s o l T C R -455 and w ere spiked with IS and surrogate; and travel blanks (trip blanks) prepared from aliquots o f s o l T C R -455 contained in sealed sam ple bottles that accom panied the bottle order to Decatur, AL and the colection site, a id returned with the sam ple shipment back to 3M Environmental Laboratory. The different blanks results w ere reviewed to evaluate potential contamination during shipm ent and sampling, to evaluate method perform ance param eters such as injector carry over and also to establish the LLO Q and the perform ance o f the blanks w ere considered in the reporting o f all results.
7 .5 L ab o rato ry C o n tro l S p ikes (L C S s)
Laboratory control spikes w ere prepared by spiking known quantities o f P FO A (linear + branched isomers) into 1 cc aliquots o f s o l TC R -455, fortified with nominal 3 .0 ng, 30 ng and 300 ng P FO A (linear + branched isom er). T he lin ear+ branched isom er quantitation using a linear PFO A calibration curve provided a m easure o f accuracy in quantifying the sum o f potential In e a r + branched P FO A isomers that are commonly associated with environmental sam ples. Each LCS level was prepared in triplicate. The
averaged results o f the LCS analyses are shown in T ab le 8 and calculated analytical method uncertainty is shown in T a b le 9 . T he method acceptance criteria of 100 30% was m et for all LCSs. The LCS recoveries w ere calculated usfog the following equation:
LCS
Recovery
=
(Determined Concentration o Spike Concentration
f
LCS)
100%
Page 14 of 19
Study: G LP10-01-01, Interim Report 26 Analysis for PFOA in Sediments Collected from the Jeffries Property, Feb. 2012
Table 8. LCS Results
S a m p le ID
LCSs (o l2 0 3 0 9 c )
LCSs (o l2 0 3 1 6 a ) A verage R ecovery S td D ev. RSD O v e ra ll A verag e
3 .0 0 ng LCS 11496 9 7 .0 9 6 108% 8 9 .7% 9 7 .0% 9 5 .3%
100% 9 .1 % 9 .1 %
PFOA R ecovery
3 0 .0 n g LCS 114% 108% 110% 9 3 .7% 9 3 .7% 8 8 .3% 101% 10% 10%
102%
3 0 0 n g LCS 129% 104% 107% 102% 9 5 .0% 9 6 .3%
106% 12% 12%
O v e ra ll S td . D ev.
10%
O v e ra ll RSD
10%
M e th o d U n c e rta in ty (9596 C l) = 2 x S td D e v . a ll le v e ls
21%
LCS c o n c e n tra tio n s w e re 3 .0 0 ng, 3 0 .0 ng an d 3 0 0 ng o f PFOA (lin e a r + b ran ch ed isom ers) add ed to each n o m in al 1
g ram o f c o n tro l soil used to p re p a re th e LCSs (1 cc o f soil T C R -455 e q u a l to n o m in al 1 .0 g ram ; d ry w e ig h t)._________
7.6 Laboratory Matrix Spikes (LMSs)
Laboratory matrix spikes (LM S s) w ere generated by spiking a known quantity o f PFO A (linear) to an aliquot of each soil/sedim ent sam ple and then preparing the sam ple the sam e as regular non-fortified sam ples. For this study, LM Ss w are prepared for each field sam ple a t 2 0 and 2 0 0 ng PFO A as a low LM S and high LM S, respectively, in run o120309c. However, those LM S levels w ere too high and sam ples re-prepared in o 120316a with LM Ss fortified with 2 ng PFO A. O ne LMS was prepared for the trip blank and fortified with nominal 1.00 ng PFO A in run o120309c and was reported from that run. T he LM S recoveries for P FO A are shown in T a b le 2. The method acceptance criteria of 100 3 0 % was m et for all LM Ss. The P FO A recovery calculations for LM S sam ples used the following equation:
LMS
Recovery
=
(Determined
Concentration
o
f
LMS - Determined Concentration Spike Concentration
o
f
Field
Sample)
,,
100%
Page 15 of 19
Study: G LP10-01-01, Interim Report 26 Analysis for PFOA in Sediments Collected from the Jeffries Property, Feb. 2012
7.7 Percent Moisture Determinations
The percent moisture was determined in duplicatefor each soil sample. For each replicate, a sample aliquot is accurately weighed to determine the "wet"weight. Then the aliquot is dried at > 100C until no further loss in mass occurs (due to water evaporation), and then the dryweight is accurately determined. The average percent moisture and RPD of the duplicate determinations for each is reported in Table 10. The percent moisture was calculated bythe following equation:
_Percent .M.o.isture = -(--Orig-i-n-a-l--SO--o-ri-il-gW-i-n-ea--tl-SM--o-ai-l-s-Ws----eD-t-rM-i-e-a-ds--sS--o-i-l--M--a--s-s)- * 100%.
Table 10. Percent Moistures for Jeffries Property Sediments, February 2012
LIMS ID
Sample ID
Average Percent Moisture (w/w)w
G L P 10-01-01-26-001
J P A L S D T R IP l 0 0 0 0 0
2 .7 2%
G L P 10-01-01-26-002
JPA LSD ET010 0 0 0 0
28%
G L P 10-01-01-2 6 -0 0 3
JPAL SO ET02 0 0 0 0 0
30%
G L P 10-01-01-26-004
JPAL SO E702 DB 0 0 0 0
30%
G L P 10-01-01-26-005
JPAL S D E T 03 0 0 0 0 0
40%
G L P 10-01-01-2 6 -0 0 6
JPAL S D E T 0 4 0 0 0 0 0
61%
[a] Percent m oisture determ ined fo r duplicate sam ples o f soil/sedinvent taken from each sam ple bottle
Relative Percent Difference w
2 .5 % 0 .7 8% 1 .5 % 0 .7 8% 3 .6 % 0 .0 96 %
7.8 Individual Sample Results The individual sample concentration results are shown in Table 11.
Table 11. Individual PFOA Results for Jeffries Property Sediments, February 2012
Sample Description
J P A L S D T R IP l 0 0 0 0 0 JPAL SD T R IP 1 0 0 0 0 0 D u p licate J P A L S D T R IP l0 0 0 0 0 L M S [e| JPAL S D E T 0 1 0 0 0 0 0 JPALSD E T 0 1 0 0 0 0 0 D u p licate JPAL S D E T 0 1 0 0 0 0 0 LMS JPAL S D E T 02 0 0 0 0 0 JPAL SD ET02 0 0 0 0 0 D u p licate JPAL S D E 702 0 0 0 0 0 LMS JPAL S D E T 02 DB 0 0 0 0
Sunegate ( 1sC -P FO A ) R e co very"
101% 113% 113% 9 8 .2% 103% 9 4 .5% 109% 106% 9 7 .2% 9 6 .2%
LMS Spike Concentration
(ng/g; dry w eigh t)
NA
0 .9 8 0
NA
1 .3 8
NA
1 .6 7 NA
M easured PFOA
Concentration (ng/g; dry w eigh t) BLQ BLQ
0 .8 7 8
0 .6 7 1 0 .5 8 6
1 .9 1
0 .5 9 2
0 .7 4 9 2 .1 6
0 .9 9 0
LMS Recovery
(D a ta A c c u ra c y)"
NA
8 9 .6%
NA
9 2 .5%
NA
8 9 .3% NA
Average PFOA Concentration (ng/g; dry w t) and
RPD (Data Precision)
BLQ
NA
0 .6 2 9
14%
0 .6 7 1
23% 0 .8 1 9
Page 16 of 19
Study: G LP10-01-01, Interim Report 26 Analysis for PFOA in Sediments Collected from the Jeffries Property, Feb. 2012
T a b le 11. In d iv id u a l P F O A R e s u lts fo r J e ffrie s P ro p e rty S e d im e n ts , F e b ru a ry 2012
Sample Description
Surrogate
( 13C 4-P FO A ) RecoveryTM
LMS Spice Concentration
(ng/g; dry weight)
Measured PFOA
Concentration (ng/g: dry w eigh t)
LMS Recovery
(D a ta Accuracy)TM
Average PFOA Concentration
(ng/g; dry wL) and RPD (Data
Precision)
JPAL SD ET02 DB 0 0 0 0 D u p lic a te
9 4 .5%
0 .6 4 9
JPAL SD ET02 DB 0 0 0 0 LMS
104%
1 .4 5
2 .0 5
8 5 .0%
42%
JPAL S D E T 03 0 0 0 0 0
109%
1 .0 7
NA NA
JPAL SD ET03 0 0 0 0 0 D u p lic a te
104%
1 .0 5
1 .0 6
JPAL S D E T 03 0 0 0 0 0 LMS
101%
2 .1 3
3 .0 2
9 1 .8%
1 .4 %
JPAL S D E T 04 0 0 0 0 0
100%
2 .2 5
NA NA
JPAL SD ET04 0 0 0 0 0 D u p licate
108%
2 .5 3
2 .3 9
JPAL S D E T 04 0 0 0 0 0 LMS
104%
3 .3 4
5 .7 6
101%
11%
NA; Not applicable
BLQ; Below the lower limit o f quantitation
[a] Surrogate recovery determined for samples fortified with 3.0 ng o f 1sC-PFOA and quantified from a 1*C-PFQA cap tatio n curve,
[bj LMSs prepared using PFOA (In e a r isomer). Tel Values below the LLOQ (BLQ) were treated as a concentration o f zero for LMS recovery calculations_________________________
Analysis o f the sedim ents collected from the Jeffries property w as successfully com pleted following 3M Environm ental Laboratory m ethod E T S -8 -0 5 3 .0 and conducted as 3M study G L P 1 0 -0 1 -0 1 -2 6 . T h e averag e P FO A concentration results fo r th e sam ples and trip blank a re sum m arized in T a b le 1 and associated LM S recoveries a re sum m arized in T a b le 2 . T h e P FO A results fo r each individual analytical sam ple replicate used fo r reporting are provided in T a b le 10. A ll sam ple results w ere reported with LM S recoveries within 100 + 15% , and duplicate results gave R P D s o f less than 5 0 % . T h e travel blank th a t accom panied the sam ple bottles shipm ents w as below the low lim it o f quantitation (B LQ , less than nom inal 0 .5 0 0 ng/g), indicating th ere w asn't any contam ination o f sam ples during sam ple shipm ent, storage and preparation fo r analysis.
AH s o l sam ples and associated project data (hardcopy and electronic) will be archived as project G LP 1001-01-26 according to 3M Environmental Laboratory standard operating procedures.
19 t h f if A ttTfam frts
A ttach m en t A : Preparation Form s, R aw D ata and Chrom atograms
Page 17 of 19
Study: G LP10-01-01, Interim Report 26 Analysis for PFOA in Sediments Collected from the Jeffries Property, Feb. 2012
Report Approval:
C leston C . Lange, P h .D ., Principal A nalytical Investigator
a te
Study: G LP10-01-01, Interim Report 26 Analysis for PFOA in Sediments Collected from the Jeffries Property, Feb. 2012
Attachment A Preparation Forms, Raw Data and Chromatograms
Page 19 of 19
Si
QLP10-01-01. Interim Report 27: Analysis of PFOA In Surface Water Sample Collected at Bert Jeffries Landfill in Decatur. AL in February 2012
Study Title
A nalysis o f Perfluorooctanoic Acid (P F O A ) in G roundw ater, S oil and S edim ent for th e 3M D ecatur P h ase 3 S ite-R elated M onitoring Program
Data Requirement
E P A T S C A G ood Laboratory P ractice S tandards 4 0 C F R P art 7 92
Study Director
Jaishmha K esari P .E ., D EE W eston Solutions, Inc. 1400 W eston W ay
W est C hester, PA 19380 Phone: 610-701-3761
Author
Susan Wolf 3M Environm ental Laboratory
Interim Report Completion Date
D ate o f signing
Performing Laboratory
3M Environmental Health and Safety Operations Environmental Laboratory
3M C enter, Bldg 260-0S -N -17 St. Paul, MN 55144
Prpiect Identification
G L P 10-01-01-27
.
Total Number of Pages
61
The testing ported herein meet the requirements of ANSiASO/lEC 17025:2005 "General Requirements far the Competence of Testing end Calibration Laboratories", in accordance with the A2LA Teeting Certificate #2052.01. Testing that ccmpOee with this international Standard ateomeets principlesof009001:2000.
Testing Cert #2052.01
L . il'in n u m i niiiiimnmniin
mil!m u
iiiBiiiimimi ih i [ ni. u
This page has been reserved for specific country requirements.
Page 2 of61
GLP10-01-01; Interim Report 27 Analysis of PFOA In Surface Water Bert Jeffries Landfill February 2012
G L P C o m plia n c e Statem ent
Report Title: GLP 10-01-01, interim Report 27. Analysis of PFO A in Surface W ater Samples Collected at Bert Jeffries Landfill in Decatur, AL in February 2012
Study: Analysis of Perfluorooctanoic Acid (PFOA) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program.
This analytical phase was conducted in compliance with Toxic Substances Control Act (TSCA) Good Laboratory Practice (G LP) Standards, 4 0 C FR 792. with the exceptions listed below:
These are environmental samples where there is no specific test substance, no specific test
system and no dosing of a test system.
.
The reference substances have not been characterized under the GLPs and the stability under
storage conditions a t the test site have not been determined under GLPs.
D a te
Page 3 of 61
GLP10-01-01; Interim Report 27 Analysis of PFOA in Surface Water Bert Jeffries Landfill - February 2012
Q u a lity A ssu r a n c e S tatem ent
Report Title: G LP10-01-01, Interim Report 27. Analysis of PFO A in Surface W ater Samples Collected at Bert Jeffries Landfill in Decatur, AL in February 2012
Study: Analysis of Perfluorooctanoic Acid (PFOA) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program.
This report and the accompanying data were audited by the 3M Environmental Laboratory Quality Assurance Unit (QAU), as indicated below. The findings were reported to the principal analytical investigator (P A I.), laboratory management and study director.
Inspection Dates
3/30/12 and 4/2/12
Phase
Data and Report
DatoRerated to
Testing Facility Management
Study Director
4/9/12
4/6/12
QAU Ri
D ate
ix
Table of C ontents
GLP Compliance Statem ent............................................................................................................................. 3 Quality Assurance Statem ent.......................................................................................................................... 4 Table of Contents................................................................................................................................................5 List of T a b les....................................................................................................................................................... 6 1 Study Information........................................................................................................................................ 7 2 Sum m ary...................................................................................................................................................... 8 3 Introduction...................................................................................................................................................9 4 Test & Control Substances.....................................................................................................................,, 9 5 Reference Substances.............................................................................................................................10 6 Test S ystem ............................................................................................................................................... 10 7 Method Sum m ary..................................................................................................................................... 11
7.1 M ethods..........................................................'......................................................................... 11 7.2 Sample Collection.................................................................................................................... 11 7.3 Sample Preparation................................................................................................................. 11 7.4 Analysis..................................................................................................................................... 11 8 Analytical Results...................................................................................................................................... 12 8.1 Calibration................................................................................................................................. 12 8.2 System Suitability.................................................................................................................... 12 8.3 Limit of Quantitation (L O Q ).................................................................................................... 13 8.4 Continuing Calibration.............................................................................................................13 8.5 Blanks.........................................................................................................................................13 8.6 Lab Control Spikes (L C S s ).................................................................................................... 13 8.7 Analytical Method Uncertainty...............................................................................................14 8.8 Field Matrix Spikes (F M S )...................................................................................................... 14
PageSofSl
9 Data Summary and Discussion............................................................................................................. 15 10 Conclusion..................................................................................................................................................18 11 Data/Sam ple Retention........................................................................................................................... 18 12 Attachm ents.............................................................................................................................................. 18 13 Signatures..................................................................................................................................................19
Lis t o f Tables
Table 1. Summarized PFO A Results (Jeffries Landfill Site, February 2012)
8
Table 2. Sample Description Key Code.................................................................................10
Table 3. Instrument Parameters..............................................................................................11
Table 4. Liquid Chromatography Conditions.........................................................................12
Table 5. Mass Transitions........................................................................................................ 12
Table 6. Limit of Quantitation (LO Q )......................................................................................13
Table 7. Laboratory Control Spike R ecovery...................................................................... 14
Table 8. Analytical Method Uncertainty.................................................................................14
Table 9. Reid Matrix Spike Levels..........................................................................................15
Table 10. JPAL SW E T 0 1 120228......................................................................................... 16
Table 11. JPAL SW E T 0 2 120228......................................................................................... 16
Table 12. JPAL SW E T 0 3 120228..........................................................................
16
Table 13. JPAL SW E T 0 4 120228......................................................................................... 17
Table 14. Trip Blank 120228................................................................................................... 17
Pag*6 ofSl
1 Study Inform ation
Sponsor
3M Company
Sponsor Representative
Gary Hohenstein 3M EHS Operations 3M Bidding 224-5W -03 Saint Paul, MN 55144-1000 P h o n e :(6 5 1 )7 3 7 -3 5 7 0
Study Director
Jaisimha Kesari, P .E , DEE W eston Solutions, Inc. W est Chester, PA 19380 P h o n e :(6 1 0 )7 0 1 -3 7 6 1 F a x :(6 1 0 )7 0 1 -7 4 0 1 j.kesari@ w estonsolutions.com
Study Location
Testing Facility
3M EHS Operations 3M Environmental Laboratory Bidding 260-5N -17 S t Paul, MN 55144
Study Personnel
W illiam K. R eagen, P h.D ., 3M Laboratory M anager Cleston Lange, Ph.D., Principal Analytical Investigator, (danoe@ mmm.com1: phone (651)-733-9860 Susan Wolf, 3M Analyst C helsie Grochow, Analyst Kevin Eich, Analyst Kelly U kes, Analyst Jonathan S teege, Analyst
Study Dates
Study Initiation: March 8 ,2 0 1 0 Interim Report 27 Experimental Termination: March 7 ,2 0 1 2 Interim Report Completion: Date of Interim Report Signing
Location of Archives
All original raw data and th e analytical report have been archived a t the 3M Environm ental Laboratory according to 4 0 C FR Part 792. The test substance and analytical reference standard reserve sam ples are archived at the 3M Environm ental Laboratory according to 4 0 C FR P art 792
P a g e 7 o f0 1
2 Summary
The 3M Environmental Laboratory received surface water samples from four different locations located at Jeffries LandfRI in Decatur, A L A total of nineteen sample bottles were received at the 3M Environmental Laboratory for perfluorooctanoate (PFOA) analysis and included duplicate surface water 'samples and two field matrix spike (FM S ) samples from each sampling location. A set of trip blank samples; single trip blank containing MilB-QTM water and two trip blank spikes, were included with the sample bottles. All samples were logged into the laboratory information management system (U M S ) under project G LP10-01-01-27. The surface water samples and trip blanks were received from Weston personnel on March 2 ,2 0 1 2 . AH of the samples were prepared and analyzed for PFOA and the surrogate recovery standard 13C4-PFO A, following 3M Environmental Laboratory Method ETS-8-044.1.
The average measured PFOA concentrations are summarized in T able 1. The trip blank was below the lower limit of quantitation (LLOQ) of 0.0240 ng/mL, indicating adequate control of sample contamination during shipping and sample collection. The analytical uncertainty was estimated at 100*17% .
Table 1. Summarized PFOA Results (Jeffries Landfill Site, February 2012)
3MUMSK)
GLP10-01-01-027-005 GLP10-01-01-027-006
GLP10-01-01-027-009 GLP10-01-01-027-010
GLP1001-01-027-013 GLP10 0 1 0 1 0 2 7 0 1 4
GLP10 0 1 0 1 0 2 7 0 1 7 GLP10 0 1 0 1 0 2 7 0 1 8
GLP10 0 1 0 1 0 2 7 0 2 5
Sample Description
JPAL-SW-ET010-120228 JPAL-SW-ET01-DB-120228
Average
%RPD Sam plu/Sam ph Dup
JPAL-SW-ET02O-120228 JPAL-SW-ET02-DB-120228
Average
%RPD Sam pte/Sam ple Dup
JPAL-SW-ET03-0-120228 JPAL-SW-ET03-DB-120228
Average
%RPD Sam ple/Sam ple Dup
JPAL-SW-ET04-0-120228 JPAL-SW-ET04-DB-120228
Average
%RPD Sam pfa/Sam ph Dup
JPAL-SW-TRIP1-0-120228
PFOA Concentration
(ng/mL)
<0.0240 <0.0240 <0.0240
NA
<0.0240 <0.0240 <0.0240
NA
0.114
0 .1 1 0
0 .1 1 2
3.6 0.0644 0.0709 0.0677
9.6 <0.0240
N A s Not Applicable The analytical method uncertainty for PFOA is 17%.
PageSofSI
3 Introduction
This analytical study was conducted as part of the Phase 3 Environmental Monitoring and Assessment Program for the 3M facility located in Decatur, Alabama. The objective erf the overall program is to gain information regarding concentrations of perfluorooctanoate (PFOA) in various environmental media such as groundwater, soils and sediments that are associated wtlh and near the Decatur faciity. This analytical study was conducted to analyze surface water samples colected from four locations near Jeffries Landfill in Decatur, AL for PFOA. The 3M Environmental Laboratory prepared sample bottles (250 mL high-density polyethylene) which were shipped to Decatur, AL Weston personnel prior to field sampling. Sample bottle sets tor each sampling location included a field sample, field sample duplicate, and two field spike samples. Each empty container for sam pings was marked with a "fill to here' in e to produce a final sample volume of 200 m L Containers designated for field matrix samples were fortified with an appropriate matrix spike solution containing PFO A prior to befog sent to the field for sample colection. All sample bottles included the addition of l3Cs-PFOA (internal standard) at a nominal concentration of 1 ng/mL, and 13C<PFOA (surrogate recovery standard) a t a nominal concentration of 0.1 ng/m L See section 8.8 o f the report for field matrix spike levels. Samples were prepared and analyzed according to the procedure defined in 3M Environmental Laboratory method ETS-8-044.1 "Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/M S/M S; Direct Injection Analysis' . The use of an internal standard was used to aid in the data quality objectives. T able 1 summarizes the average PFO A concentration for the duplicate surface water samples colected and the trip blank sample. Tables 10-14 summarize the individual sample results and the associated FM S recoveries. All results for the quality control samples prepared and analyzed with the samples are reported and discussed elsewhere in this report.
4 Tost & Control Substancos
There was not a test substance or control substances in the classic sense of a GLP study. This study was purely analytical in nature.
Page 9 of 61
5 Reference Substances
The analytical reference substances used for this study are listed below.
Substance Chemical Name Chemical Formula Identifier
Use
Source Expiration Date Storage Concilions Chemical Lot Number
TCR Number
Physical Description Purity
PFOA (LinearBranched) Perfluorooctanoate
C7 F15COOH
CAS # 95328-99-7 Target Analyte
Reference Standard Welington
03/17/2014
Frozen
TPFOA0311 TCR11-0009, TCR11-0042
Liquid
08.3%
"C rm M Perfluorooctanoate
13C4HFis02 MPFOA Surrogate
Welington 12/07/2013
Frozen MPFOA1210
TCR11-0001 Liquid >98%
'H ^ T O A Perfluorooctanoate
13CeHF150 2 MPFC-C-0511 internal Standard
WeWngton 05/25/2014
Frozen 052411
TCR11-0016 Liquid N A 0)
'V r o ii Perfluorooctanoate
1sC#HF, 0 2 MPFC-C-0112 Internal Standard
WeMngton 01/24/2015
Frozen 012312
TCR12-0004
Liquid NATM
(1) Compound is part of a custom mixture of mass-labeled perfluorinated compounds al a concentration of 5.0
6 Test System
There was not a test system for this study in the classic sense of a GLP study. This study was conducted for analysis of surface water samples collected from the Jeffries property located near Decatur, AL by Weston Solutions, Inc. personnel. Samples for this study are "real worlcf environmental samples.
Table 2. Sample Description Key Code.
Strina Number
E x a m p le 1
2
3
4 3
Strina Descrfoter
Examole
J P A l-S W -E T T H -0 -1 2 0 2 2 8
S a m o li L o c a tio n
J P A L " J e ltH e a P ro o e rty . A la b a m a
S a m p le T w o
S W * S u rfa c e W a ter
W e tV
E x a m p le : E T 0 1
E T " E a s te rn trib u ta ry to M aO ard C ro o k
S a m o o m D a ta
1 2 0 2 2 8 -F e b ru a ry 2 8 ,2 0 1 2
S a m p le T yp o
0 *p r1 m a ry s a m p le
D B *d u p 8 c a ta s a m p le L S = lo w a p lk a
H S -h ta h a p O c e
PagelOofSl
7 Method Summary
7.1 Method
Analysis for aH analytes was completed following 3M Environmental Laboratory method ETS-8-044.1 "Method of Analysis for the Determination of Perfiuorinated Compounds In W ater by High Performance Liquid Chromatography/Mass Spectrometry Direct Injection Analysis*.
7.2 Sample Collection
Samples were collected in 250 mL NalgeneTM (high-density polyethylene) bottles prepared at the 3M Environmental Laboratory. Sample bottles associated with G LP10-01-01-27 were returned to the laboratory at ambient conditions on March 2 ,2 0 1 2 . Samples were stored refrigerated at the laboratory after receipt. A set of laboratory prepared Trip Blank and Trip Blank Held matrix spikes were sent with the set of sample collection bottles.
7.3 Sample Preparation
Samples were prepared by removing an aliquot of the well mixed sample and placing it in an autovial for analysis.
During the preparation of the laboratory control samples, an aliquot of a separate internal standard spking solution was added to the laboratory control samples (nominal concentration of 1 ng/mL). The samples bottles were spiked with an internal standard mix at a nominal concentration of 1 ng/mL prior to being sent to the field for sample colection.
7.4 Analysis
All study samples and quality control samples were analyzed for PFO A using high performance liquid chromatography/tandem mass spectrometry (HPLC/M S/M S). D etaled instrument parameters, the liquid chromatography gradient program, and the specific mass transitions analyzed are described in the raw data hard copies placed in the final data packet, and are briefly described below in T able 3, T able 4 and Table 5.
T ab le 3 . In stru m en t P aram eters.
Instrument Name Analytical Method Followed Analysis Date Liquid Chromatograph Guard column Analytical column InjectionVolume Mass Spectrometer Ion Source Electrode Polarity Software
ETS Ginger ETS-8-044.1
3/6/12 Autant 1100 Betas C18(4.6 mmX 100 mm). 5u Betas! C18(4.6 mmX 100 mm). Su
25 uL Aoofied BlosvstsmsAPI 5000
Turbo Spray Turbo ion electrode
Negative Analyst 1.4.2
Page 11 of 61
Table 4. Liquid Chromatography Conditions.
Step
Number
TotalTim (min)
0 0.0 1 2.0 2 14.5 3 15.5 4 16.5 5 20.0
no--w-- fm v
(jjjmln)
PanantA Cl mU ammoniumacato*)
ETS-8-044.1 Analvals
750 97.0
750 97.0
750 5.0
750 5.0
750 97.0
750 97.0
PmttntB
/IM b in o O
3.0 3.0 95.0 95.0 3.0 3.0
Table 5. Mass Transitions.
Anatyta PFOA rCrhPFOA__
Mm # TrnnNfrn 01/03 413/360
413/219 413/16 417/372
MarnaiStandard t 'C+PFOA f 'CJ-PFOA
Uaaa Transition 01/03
421/376
421/376
Dwal time was 50 msec tor each transition. The individual transitionB ware summed to produce a '`total ion chromatogram* (TIC), which was used for quantitatian.
8 Analytical Results
8.1 Calibration
Samples were analyzed using a stable isotope internal standard calibration curve. Calibration standards were prepared by spiking known amounts of the stock solution containing PFOA (reference standard containing both linear and branched isomers) Into a laboratory-prepared synthetic groundwater containing calcium and magnesium. A separate internal standard spiking solution was prepared and an aliquot was added at the sam e level to aN calibration standards and laboratory control samples at a nominal concentration of 1 ng/m L A calibration curve ranging from approximately 0.025 ng/mL to 100 ng/mL (0.025 ng/mL to 10 ng/mL for 13C4-PFO A surrogate) was prepared. A quadratic, 1/x weighted, calibration curve of the standard peak area/peak area ratios was used to fit the data for each analyte. The data were not forced through zero during the fitting process. Calculating the standard concentrations using the peak area/ peak area ratios and the resultant calibration curve confirmed accuracy of each curve point.
Each curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method calibration accuracy requirements of 100 25% (100 30% for the lowest curve point) were m et for PFOA and 13C4-PFO A surrogate. The correlation coefficient (r) was greater than 0.995 for both analytes.
8.2 System Suitability
A caibration standard was analyzed four times at the beginning of the analytical sequence to demonstrate overaH system suitability. The acceptance criteria o f less than or equal to 5% relative standard deviation (R SD ) for peak area and retention time criteria of less than or equal to 2% RSD was m et for PFO A and ^C ^P FO A surrogate.
Page 12 of 61
GLP10-01-01; Interim Report 27 Analysis of PFOA In Surface water Bert Jeffries LandM February 2012
8.3 Limit of Quantitation (LOQ)
The LOQ for this analysis is the lowest non-zero calibration standard in the curve that m eets linearity and accuracy requirements and for which the area counts are at least twice those of the appropriate
blanks. The nominal LOQ for PFOA can be found in T able 6.
T ab le 6 . L im it o f Q u an titation (LO Q ).
Analysis Data 3/6/12
PFOA no/mL
0.0240
8.4 Continuing Calibration
During the course of each analytical sequence, continuing calibration verification samples (CCVs) were analyzed to confirm that the instrument response and the initial calibration curve were still in control. All CCVs m et method criteria of 100% 25% for PFOA and 13C-PFQA surrogate.
8.5 Blanks
Two types of blanks w ere prepared and analyzed with the samples: procedural blanks and trip blanks. Procedural blank results w ere reviewed and used to evaluate method performance to determine the LOQ. Trip blanks reflect the shipping and sample collection conditons the sample bottles and samples experience.
8.6 Lab Control Spikos (LCSs)
Low, mid, and high lab control spikes w ere prepared for the target analytes and analyzed in triplicate, while only low and high lab control spikes were prepared for the 13C4-PFOA surrogate. LCSs were prepared by spicing known amounts o f the analyte into 1 0 m L o f synthetic groundwater to produce the desired concentration. The spiked w ater samples w ere then analyzed in the same manner as the samples. The method acceptance criteria, average of LCS at each level should be within 100% 2 0 % with an R SD 20% , were met for both PFOA and 13C4-P FO A surrogate.
The following calculations were used to generate data in T able 7 for laboratory control spikes:
LCS Percent Recovery = Calculated Concentration Spike Concentration
LCS%RSD =standard deviation LCS r e p B c a te s .j^ average LCS recovery
Page 13 of 61
Table 7. Laboratory Control Spike Recovery.
ETS-8-044.1 Analyzed 3/6/12
Lab ID
PFOA (U m a r+ Branched)
u CrPFOA surrogate
Spiked Concentration
(nofw L)
Calculated Concentration
(no/m L)
Spiked
Calculated
Concentration Concentration
%Recoverv (ngAnL)
(nofntQ
% R ecovery
LCS-120306-1 LCS-120306-2 LCS-120306-3 Average %RSD
0.190 0.190 0.190
0.162 0.166 0.164 86.4% 1.3%
85.5 87.6
8 6 .1
0.198 0.198 0.198
0.229 0.223 0.219 113% 2.7%
116
112 110
LCS-120306-4 LCS-120306-5 LCS-120306-6 Average % RSD
1.90 1.90 1.90
1 .8 8
1.96
1 .8 6
100% 2.7%
99.1 103 97.9
1.98 2.24 1.98 2.31 1.98 2.33
116% 2 .2 %
113 116 118
LCS-120306-7 LCS-120306-8 LCS-120306-9
19.0 19.0 19.0
18.0 95.0 NA 17.8 93.8 NA 18.9 89.1 NA
NA NA NA NA NA NA
Average %RSD
92.6% 3 4 %
NA
N A = N ot Applicable
8.7 Analytical Method Uncertainty
Analytical uncertainty is based on historical QC data that is control charted and used to evaluate method accuracy and precision. The method uncertainty is calculated following E TS-12-012.2. The standard deviation is calculated for the set of accuracy results (in % ) obtained for the Q C samples. The expended uncertainty is calculated by multiplying the standard deviation by a factor of 2, which corresponds to a confidence level o f 95%.
Table 8. Analytical Method Uncertainty.
Analyte PFOA
iMMOafVlliOn Qrl
ETS-8-044.1
Standard Deviation
8 .6 8
Method Uncertainty
17%
8.8 Field Matrix Spikes (FMS)
Low and high field matrix spikes were collected at each sampling point to verify that the analytical method is applicable to the collected matrix. Field matrix spites were generated by adding a measured volume of field sample to a container spited by the laboratory with PFOA (reference standard containing both linear and branched isomers) prior to shipping sample containers for sample collection. Field matrix spike recoveries within method acceptance criteria of 10030% confirm that "unknown" components in the sample matrix do not significantly interfere with the extraction and analysis of the analytes of interest Field matrix spike concentrations must be 50% o f the sample concentration to be considered an appropriate field spike. Field matrix spikes are presented in section 9 of this report
Page 14 of 61
GLP10-01-01 ; Interim Report 27 Analysis of PFOA in Surface Water Beit Jeffries Landfill February 2012
Table 9. Field Matrix Spike Levels.
S am plin g L ocatio n All Locations and Trip Blank
S p ike Laval Low High
PFO A , n g/m L 0 .998 9 .9 8
F M S R am verv ( Sam ple Concentration of FM S - Average Concentration : Field Sam ple & Field Sam ple P u p .). 100%
~ Spike Concentraton
8.9 Data Summary and Discussion
The tables below summarize the sample results and field matrix spike recoveries for the sampling locations as well as the Trip Blanks. Results and average values are rounded to three significant figures according to EPA rounding rules. Because of rounding, values may vary slightly from those listed in the raw data. Field matrix spike recoveries meeting the method acceptance criteria of 30% , demonstrate that the method was appropriate for the given matrix and their respective quantitative
ranges.
Page 15 of 61
Table 10. JPAL SW ET01 120228
3M U M S ID
Description
G L P 100101-27005 GLP10 0 1 0 1 -2 7 -0 0 6
JPA L-S W -ET01-0-120228 JPA L-SW -ET01-D B -120228
G L P 10 -0 1 -0 1 -2 7 -0 0 7
JPAL-SW -E T 01-LS -120228
G LP10 0 1 -0 1 -2 7 -0 0 8
JPA L-SW -ET01-H S-120228
Average Concentration (nafm U t %RPDfR$D
NA-NotAppBcaUe
Table 11. JPAL SW ET02 120228
3M LltOSID
Description
G L P 1001-01-27-009
JPAL-SW -ET02O -120228
G LP 1001-01-27-01 GLP1001 -0 1 -27 0 1 1
JPA L-SW -ET02-D B -120228 JPAL-SW -ET02-LS-120228
GLP10 0 1 0 1 -2 7 0 1 2
JPAL-SW -T02-H S-120228
A verage Concentration (nafmU %RPDfRSD
NA = Not Applicatila
Table 12. JPAL SW ET03 120228
3HLM SID
Dsolation
GLP10 0 1 0 1 -2 7 0 1 3
JPA L-SW -ET03O -120228
G L P 100101-27014
JPA L-SW -ET03-D B -120228
G L P 100101-27015
JPAL-SW -ET03-LS-120228
GLP10 0 1 0 1 -2 7 0 1 6
JPAL-SW -ET03-HS-120228
A verage Concentration InofmL) %RPD/RSD
NA= Not Applicable
PFOA
" CPFOA
Concentration
(nafmU %Recovery X A w oM rv
< 0 .0 2 4 0
NA
111
< 0 .0 2 4 0
NA
108
0 .9 5 0
9 5 .2
110
9 .4 4
9 4 .6
<0.0240nafn.
118
112% ti9%
PFOA
13C4 PFOA
Concentration (nolmL) '/Recovery %Recoyerv
< 0 .0 2 4 0
NA
< 0 .0 2 4 0
NA
0 .9 3 8
9 4 .0
9 .0 2
9 0 .4
<0.0240 no/mL
109 115 106 111
110% 1 3.4%
PFOA
13C4 PFOA
Concentration (ng/mL) %Recovery %Recoverv
0 .1 1 4
NA
0 .1 1 0
NA
1.10
9 9 .0
9 .3 7
9 2 .8
0.112 nofmLt 3.0%
107 108 110 110
100% 1 1.4%
Table 13. JPAL SW E T 04120228
M U M S ID
D e s c rip tio n
G L P 10 -0 1 -0 1 -2 7 -0 1 7
JPA L-S W -ET04-0-120228
G LP 10-01-01-27-018
JPA L-SW -ET04-DB-120228
G LP 10 -0 1 -0 1 -2 7 -0 1 9
JPA L-SW -ET04-LS-120228
G LP 10 -0 1 -0 1 -2 7 -0 2 0
JPA L-SW -ET04-H S-120228
A v e ra g e C o n c e n tra tio n (n a /m L ) 1 % R P D /R S D
N A = No Applicable
Table 14. Trip Blank 120228
M U M S ID
G L P 10 -0 1 -0 1 -2 7 -0 2 5 G L P 10 -0 1 -0 1 -2 7 -0 2 6 G L P 10 -0 1 -0 1 -2 7 -0 2 7
IMA* NoApplicable
D e s c rip tio n
JPAL-SW -TRIP1-0-120228 JPAL-SW -TR IP1-LS-120228 JPA L-SW -TR IP1-H S-120228
PFO A
13c , p f o a
C o n c e n tra tio n
(n g /m L )
^R ecovery
0 .0 6 4 4
NA
0 .0 7 0 9
NA
1 .0 2 8 .9 6
9 5 .4 89.1
0 .0 6 7 7 n p /m L 2 .6 %
% R e c o v e ry
112 111 111 109
1 1 1 % 1 .1 %
PFO A
C o n c e n tra tio n (n o rin L )
% R e c o v e rv
< 0 .0 2 4 0
NA
0 .9 5 5
9 5 .7
9 .1 6
9 1 .8
13C t P F O A
% R e c o v e rv
101 118 112
Page 17 of61
9 Conclusion
Laboratory control spikes and field matrix spites were used to determine the analytical method accuracy and precision for PFOA. Analysis was successfully completed following 3M Environmental Laboratory method ETS-8-044.1 described herein.
10 Data/Sample Retention
All remaining samples and associated project data (hardcopy and electronic) will be archived according to 3M Environmental Laboratory standard operating procedures.
11 Attachments
Attachment A: Protocol Amendment 27 (General Project Outline) Attachment B: Representative Chromatograms and Calibration Curves Attachment C: Analytical Method - ETS-8-044.1
Page 18of81
GLP10-01-01; Interim Report 27 Analysis of PFOA In Surface Water Bert Jeffries LandfM - February 2012
12 Signatures
Cleston Lange, Ph.D., 3M Principal Analytical Investigator
d t LZ& Z-
D a te
W illiam K. Reagen, Ph.D., 3M Environmental Laboratory M anager
G ary Hohenstein. 3M Sponsor Representative
kh u
Jaisimha Kesari, Study Director
D ate
tz
D ate
M n >"
D ate
Page 1S of61
Attachment A: Protocol A mendment
GLP10-01-01; Interim Report 27 Analysis of PFOA in Surface Water Beit Jeffries LandM February 2012
Page 20 of 61
InGLP10-01-01; Interim Report 27
Analysis of PFOA Surface Water Bert Jeffries LandfM - February 2012
AnalyticalProtocol: GLP10-01-01 ' Amendment 27
Study Title
,
i
Analysis of Perfluorooctanoic Acid (PFOA) in Groundwater, Soil and Sediment for the
3M Decatur Phase 3 Site-Related Monitoring Program
PROTOCOLAMENDMENTNOl 27 1 I
jAmendment Date:
February 21,2012 !
|Performing Laboratory
3M Environmental, Health, and Safety Operations 3M Environmental Laboratory Building 20O-5N-17 Maplewood, MN 55144-1000
i
Laboratory Prefect Identification
GLP10-01-01-27
Sampling Event
ji
I
j
j
Bert Jeffries Landfill -Surface W ater Sampling
i
i i
Page 1 of 8 Page 21 o f6 i
GLP10-01-01; Interim Report 27 Analysis of PFOA in Surface Water Bert Jeffries Landfill - February 2012
AnalyticalProtocol: GLP10-01-01 : Amendment27
This amendment modifies the following portion of protocol:
I
"Analysis of Perfluorooctanoic Acid (PFOA) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program"
PROTOCOL READS:
N o changes to th e w ording o f th e protocol a re required.
Amendtor e a p ;
j
ii
j
i N o changes to th e w ording o f th e protocol a re required. T his am endm ent only add resses and docum ents th e addition o f th e G en eral Project O utline (G P O ) fo r th e collection and analysis o f groundw ater sam ples a t D ecatur, AL, and conducted a s part o f th e 3M D ecatu r P h ase 3 Program fo r P F O A (G L P 1 0 -0 1 -0 1 ). Sam pling activities a t and n ea r the B ert Jeffries landfill a re scheduled for th e w e e k o f F ebruary 2 7 ,2 0 1 2 and w ill consist o f 6 paired surface w ater and sedim en t sam ples. This protocol am endm ent addresses the sam pling and analysis o f th e surface w a te r sam ples. S urface w ater sam ples collected under this sam pling event w ill be entered into th e 3M Environm ental Laboratory L IM S as project G LP 10 -0 1 -0 1 -2 7 and reported as interim report G L P 1 0 -0 1 -0 1 -2 7 . (reflecting study G LP 10 -0 1 -0 1 and am endm ent -2 7 ).
T h e reason fo r this am endm ent is to docum ent th e G en eral P roject O u tlin e (G P O ) w hich describes the
anticipated surface w a te r sam ple co lectio n even t to be conducted a t and n e a r th e B ert Jeffries landfill in
Law rence C ounty, A L
'
T he G P O is three pages In length and included as attached to this am endm ent form .
\
Page 2 of6
I
Page 22 of 61
GLP10-01-01; Interim Report 2 7 Analysis of PFOA in Surface W ater Bert Jeffries Landfill February 2012
AnalyticalProtocol: GLP10-01-01 ' Amendment27
Amendment Approval
! i* u
Gary I henseah,l| Sponsor Representative
h
Cteston C. Lange, PrincipalAnalytical Investigator
y ,x
Data
zj ^ L]Z J ) 2 -
D a te
Page 3 of 9 Page 23 of 61
GLP10-01-01; Interim Report 27 Analysis of PFOA in Surface water Bert Jeffries Landfill - February 2012
l
AnalyticalProtocol: GUP10-Q1-01 Amendment27
3M E nviro n m en tal H e a lth & S a fe ty O p eratio n s, E nviro n m en tal L ab o rato ry
General Project Outline ;
To: G ary Hohenstein, 3M EHS&O pns
;
From :
Susan W oif, 3M EHS&Opns; Environmental Lab
:
c c : W M am Reagan, 3M EHS&Opns; Environm ental Lab
J a Kesari, W eston Solutions
.
Charlee Young, W eston Solutions
'
D ate:
February 2 1 ,2 0 1 2
,
S u b je c t:
A nalysis o f Perfluorooctanoic A d d (P F O A ) in G roundw ater, S o il and S edim ent fo r th e 3M
D ecatu r P h ase 3 S ite-R elated M onitoring Program ; G L P Interim R epo rt 2 7 - B e it Jeffries
Landfill; S u rface W a ter sam pling th e w eek o f February 27; 2 0 1 2 .
'
1 General Project Information
C o n ta cts
I
3M Sponeor Representative
Gary Hahentlein
|
3M EH S Operatane
3M BuMlnp 224-5W-03 1
Saint Paul, MN 55144-1000
Phono: (651) 737-3570 !
aahohenotelnAimwn .com |
3M Environm ental Laboratory MBnagemant
WMam K. Reagan
!
3M EH S Opm . Environmental Laboratory
260-5N-17
Principal Analytical Investigator
Cleston Lange
!
3M EH S O pra, Environmental Laboratory
260-SN-17
I
e s i 733-geso
;
s s b o a tira m s a m
;
Sam pling Coordinator Timothy Frinak Weston Solutions
! I
\
Lab Request Number 81a D igit Departm ent Num ber Project SohadulafToat Detoe
GLPKW H-01-a7
;
Dept #330711, Project #0022674449
Tentatively scheduled for the week of February 27.2018.
All ventaiand wten correspondent willbe directed to Gary Hohenstein and Jai Kesari.
Page 4 of 6 Page 24 of 61
GLP10-01-01; Interim Report 27 Analysis of PFOA in Surface Water Bert Jeffries Landfill - February 2012
I.
AnalyticalProtocol: GLP10-01-01 ! Amendment27
2 Background Information and Project Objective) :
The 3M EHS Operations Laboratory (3M Environmental Lab) will receive and analyze surface water samples collected from six (6 ) locations at and near the Bert Jeffries landfill. Surface water samples will be collected by Weston. The 3M Environmental Laboratory will prepare the sample bottles. Samples wfil be analyzed for Perfluorooctanolc Add (PFOA). Analyses will be conducted under the GLP requirements of EPA TSCA Good Laboratory Practice Standards 40 CFR 792.
The final report will be submitted to Gary Hohenstein and Jai Kesari upon completion under interim report GLP10-01-01-27.
3 Project Schedule
Sample collection bottles will be prepared by the 3M Environmental Laboratory. Sample bottlesw il beehipped in coolers overnight to 3M Decatur for arrival by Friday, February 24,2012. Sample bottles should be stored refrigerated on-ste until sample collection.
Martin Smith \ Weston Trailer 3M Decatur Plant 1400 State Docks Road
.Decatur, Alabama 36601
4 Test Parameters
I j
.i
!
The targeted limitof quantitation wifi be 0.026 ngfrnL (ppb) for PFOA [
i A total of six,samping locations have been specified. For each sampling location, a total offoursample bodies wH be collected (sample, sample duplicate, low-level field matrix spite, arid high-levelfield matrix spike). The TO to here" ine on each 250 mL Naigene bottle win be 200 mL One set of trip blanks consisting of reagent-grade water, a low-level trip blank spike, and a high-level trip blank spice w il be prepared at the 3M Environmental Laboratory and sent to the sampling location with the other bottles. No previous data on fiuofochemicals in groundwater, surfacs water or sediment media exist forthe site. The low fietd matrix spike will be prepared at 1 ngfmL and the high field matrix spike at 10 ng/mL.
All sample bottles w i include the addition of ,3C*-PFOA (Internal standard) at a nominal concentration of 1 ng/mL and ^CrPFQA (surrogate recovery standard) at a nominal concentration of 0.1 ng/mL.
To aid in sample collection, a non-aptked 1-L sample bottle w il be provided for each sampling location. Sample collection will consist of direct immersion. Aliquots will be decanted from the collection bottle to the primary, duplicate and matrix spike bottles. No rinseate blank will be collected.
5 Test Methods
Samples wM be prepared and analyzed by LC/MS/MS following ETS-6-044.1 ` Method ofAnalysis for the Determination of Perfluorinated Compounds In Water by High Performance Liquid Chromatography/Mass Spectrometry Direct injection Analysis'. Alternately, samples may be analyzed by ETS 8-154.3 `Determination of Perfluorinated Acids. Alcohols, Amides, and Sulfonates In Water By Solid Phase Extraction and High Performance Liquid Chromatogrephy/Mess Spectrometry. Where applicable, samples will be analyzed against an internal standard calibration curve. Each curve pointwfil contain ieotoploalty-labeted PFOA at a nominal concentration of 1 ng/mL.! The calibration curve w i be
I
> Paga 5 of 6
Page 26 of 61
L .iL .i.l . .__.I...liil Jl...
inhim yiiiiiiHMii-- iiiiiiiniiiiiinii luii .11
GLP10-01-01; Interim Report 27 Analysis of PFOA In Surface Water Bert Jeffries Larxffll February 2012
AnalyticalProtocol: QLP10-01-01
| A m endm ent 27
!
generated by taking the rat of the standard peak area counts w a r the internal standard peak area counts to It
the data for each analyte.
]
Laboratory oontrol samples prepared with the samples musthave an average recovery within 10020% and a RSDs20%, The data quality objective for this study is quantitative result? for the target analytes wifo an analytical accuracy of 10030%. Field matrix spikes notyielding recoveries within 10030% will be addressed in the report and the final accuracy statement may be adjusted acoonSngly.
6 Reporting RequirementsI*
For each sampfing location, the reportwffl contain the results for the sample, sample dupbcata, and the two field matrix spikes. Trip blank and trip blank spikes will be reported for the sarripling event Laboratory control spikes erfreagentwater prepared at the time of sample extraction wttl also be reported and used to evaluate the overall method accuracy and precision. Method blanks of reagent water prepared at the time of sample preparation will be used to determine the method detection Kmk. For those sampling locations where the field
matrix spike level was not appropriate due to higher than expectedanalyte concentrations, a target analyte
laboratory matrix spike may be prepared and will be included in the final report.
I I
I Page 6 of 6
Page 26 of 61
GLP10-01-01; Interim Report 27 Analysis of PFOA in Surface Water Bert Jeffries Landfil February 2012
Atta c h m en t B: R epr esen ta tive Sa m p l e C h r o m a to g r a m s a n d C a lib r a tio n C u r ve(s )
Page 27 of 61
** Cinger A001330509
GLP10-01-01; Interim Report 27 Analysis of PFOA in Surface Water Bert Jeffries LandM - February 2012
Results Nane? gl20306a.rdb
Printing Date; Monday March 12 2012
Page 28 of 61
* Ginger AGM3S0509
GLP10-01-01; Interim Report 27 Analysis of PFOA in Surface water Bert Jeffries Landfff February 2012
Results Base: gl20206a.rdb
Printing Pater Monday, March 12, 2012
Page 29 of 61
Ginger AG01330509
GLP10-01-01; Interim Report 27 Analysis of PFOA in Surface water Bert Jeffries Landfill - February 2012
Rult$ Nam: 9120306a.tdb
Printing Dat: ttednesday, April 11, 2012
Page 30 of 61
*** Ginger AG01330509
GLP10-01-01; Interim Report 27 Analysis of PFOA In Surface w ater Bert Jeffries LandU - February 2012
Results Naee: gl20306a.rdb
Printing Date; Nednesdsy, April 11, 2012
Page 31 of61
*** Glnr AGO 1330509
GLP10-01-01; Interim Report 27 Analysis of PFOA in Surface Water Bert Jeffries LandfiB - February 2012
Results Nane: gl 20306a.rdb
Printing Date: Wednesday, April 11, 2012
Page 32 of 61
Ginger AG0133050
GLP10-01-01; Interim Report 27 Analysis of PFOA in Surface Water Bert Jeffries Land - February 2012
Result M e m ; 9120306a.rdb
PriDtinq Dace: Htdnesdey, April ll , 2012
Page 33 of 61
*** Ginger AG01330509
GLP10-01-01; Interim Report 27 Analysis of PFOA in Surface Water Bert Jeffries LandfiM - February 2012
Results Name; gl20306s.rdb
Printing Date: Wednesday, April 11, 2012
Page 34 of61
*" Ginger AGOl33050
GLP10-01-01; Interim Report 27 Analysis of PFOA in Surface Water Bert Jeffries Landfill - February 2012
Rffitiltff Naia: 9120306a. rdb
P r in tin g D at: Wednesday, A p ril 11 2012
Page 3S of 61
*** Ginger AGO1330509
GLP10-01-01; Interim Report 27 Analysis of PFOA in Surface water Bert Jeffries LandW - February 2012
Result Nane: gl20306a.rdb
Printing Date: Wednesday, April 11, 2012
Page 36 of 61
** Ginger AG01330S0
GLP10-01-01; Interim Report 27 Analysis of PFQA in Surface Water Bert Jeffries LandfiS - February 2012
Results (fast: gl20306*.rdb
Printing Date: tfedneaday, April 11 2012
Page 37 of61
*** Ginger AG01330S09
GLP10-01-01; Interim Report 27 Analysis of PFOA in Surface Water Bert Jeffries Landfill - February 2012
Results Name: gl20306a.rdb
Printing Date: Wednesday, April 11, 2012
Page 38 of 61
Atta c h m en t C : A n a lytic a l M e t h o d s )
GLP10-01-01; Interim Report 27 Analysis of PFOA in Surface Water Bert Jeffries Landfill - February 2012
Page 39 of 61
GLP10-01-01; Interim Report 27 Analysis of PFOA in Surface Water Bert Jeffries landfll - February 2012
3MEnvironmental Laboratory
Method
Method o f Analysis for the Determination o f Perfluorinatad Compounds In Water by LC/MS/MS; Direct Injection Analysis Method Number: ETS~8444.1 Adoption Date: 4/12/07 Effective Date: i l j u (l
Approved By:
WifHam K. Reagen, Technical Director, Environmental Laboratory
9 /J C /lf 3 o / /
Date
ETS-8-044.1
Page 1 of 22
Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct
Injection Analysis
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GLP10-01-01; Interim Report 27 Analysis of PFOA in Surface Water Bert Jeffries Landfill - February 2012
1 Scope and Application
This method describes the direct injection analysis of perfluorinated compounds (PFCs) from water matrices using high-performance liquid chromatography tandem mass spectrometry (HPLC/M S/M S). The method is generally applicable but not limited to the measurement of perfluoroalkyl sulfonamides and perfluorinated alkyl acids (PFAAs) such as perfluorosulfonic acids (PFSAs) and perfluorocarboxylic adds (PFCAs) (Table 1). W ater samples containing heavy particulate m ay require preparation by an alternate method such as E TS -8-154 ` Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrom etry. The method is applicable to both external standard and internal standard cafibration*1.
Table 1. Representative Target Analytes
A c ro n y m
PFB A (C 4A dd) PFPeA (C5 Add) PFHxA <C6 Add) PFHpA (C7 Add) PFOA (C 8 Acid) PFNA (C9 Add) PFD A (C 10 Add) PFUnA(C11 Add) PFDoA (C 12A dd) PFTrDA (C13 Add) PFBS (0 4 Sulfonate) P FH S (C 6 Sulfonate) PFO S (C 8 Sulfonate) FBSA (C 4 Sulfonamide FOSA (C8 Suffonamtde)
A n a ly ta
Periluorobutanoic add Perfluoropentanok: add Periluorohexanoie add Perfluoroheptanoic add Periluorooctanoic acid Periluorononanoic add Perfluorodecanoic add Periluoroundecanoic add Perfluofododecanoic add Periluorotridecanolc add Periluorobutanesulfonk: add Perlluorohexanesulfonic add Perfiuorooctanesutfonlc add Perfluorobutanesutfonamide Pefluorooctanesulfonamide
C h im ic a ! A b s tr a c t S e rv ic e s R e g is try N u m b e r (C A S R N )
375-22-4 2706-90-3 307-24-4 375-85-9 335-67-1 375-95-1 335-76-2 2058-94-6 307-55-1 72629-94-8 375-73-5 355-46-4 1763-23-1 30334-69-1 754-91-6
The Minimum Reporting Level (M RL) is the Limit of Quantitation (LOQ ) that m eets Data Quality Objectives (DQ O s) that are developed based on the intended use of this method.
Method Flexibility - This is a performance-based method and m ay be generally applied to the determination of perfluorinated compounds in water matrices when analysis batch quality control (Q C ) criteria are met2. Each set of samples are prepared in an analysis batch with calibration standards, LCSs, blanks, and continuing calibration check standards analyzed on the sam e instalment during a time period that begins and ends with the analysis of the appropriate continuing calibration check standards. The laboratory is permitted to modify the LC column, mobile phase composition, LC conditions, and M S/M S conditions. Method modifications should be considered to improve method performance or to m eet data quality objectives for the study. In all cases where method modifications are implemented, the batch
' The method'is supported by validation with internal standard calibration for C4-C13 PFCAs, C4, C6, and C8 PFSAs, and C8 periluoroalkane sulfonamide in laboratory control samples under 3M method validation El 1-0667. (1MMPGeeauttrhhitdooAadd,nssVceoecaftlfiiAoodrnnaeta5islo)ytansob"ifs,liDbsinh.i)riSenEucgPtpimApvoeeMrt9th1eoot/dfh4Po1Qd4ieC,-3Sr3CeA7gr,iNitsaeCtnrridaOatci/bo3.a)n0sE2eD9uda/r9otoa9npReraeae.vn)q.FuC4Dior(eAm1m1mMe/0insa7tsys/i0of20on0)r:.0AG1,nu"nidGeaxuniIcdIea(nfPocarertGfAoer,nIsenerdacuttiisnotgrnya4,n)BdainoRadenpAaolnyrnttiiencxgalIII
ETS-8-044.1
Page 2 of 22
Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS;
Direct Injection Analysis
Page 41 of 61
QLP10-01-01; Intrim Report 27 Analysis of PFOA in Surface Water Bert Jeffries LandlM February 2012
aearnn iaw vlyw tniacwaml Q C s.re a v v v (sectiona . v9j )i m le euasv vtabvAev com pleted and Dass Q C1 ia v ia v v a ^w v a i ava a^a a a ^Ap ^evv a
lmi|jsk ojJsj|tAiaa TIgruounHii llkiGA aJhnisaielkyrtiicAJasll oIsaat4ea 4ni ajkgrueh t4oa oWae mr^epa aosf^tea cJ.
2 Method Summary
o ta riaiv^VA v^e ia a w i w a
a 1a a3v)e aiaf
W ater s a rn ie s are analyzed as neat aaueous sam ole o r as solvent diluted aaueous sam olesv v a b b a a i i ^v a i a ^aa^va^v v s i aa am pw ^ z a p v a w apha a w ^w re ve%s i^revAAwaA a^^aea a ia a iv a vap v i ia
v ^a i a% v a H % a M a a a v i v l w a a ^A v b ia a^^eaa a iB A ^ v e A
by direct injection using LC/M S/M S. Samples containing heavy particulate may not be
suitable for analysis by this method. Samples containing suspended particulate should be
centrifuged or fBtered prior to removing a sample aliquot or diluting with solvent. The water
sample is mixed well prior to removing an aliquot or diluting, if necessary, with A STM Type I
water, HPLC water, other suitable water, or solvent (methanol).
Quantitation is bv stable isotooe internal standard calibration in laboratory reaaent water All
perfluorinated compounds (PFCs) target analyte concentrations of perfluorosulfonic acids (PFSAs) and perfluorocarboxyfic acids (PFCAs) are reported as anions and corrected for their salt or free acid forms. Alternatively, quantitation m ay be performed by external standard calibration.
T1 h1 iisi ^a is aw oi weirfi ^of tmi 1 1 i eannce-based m1 i ee wthi ow d* . Mn iewthi ow d vu1nnc^ ew ri ithahiinntvy fova ari each1 tl eaurmaev ti easn^ae livy wte wis determined for each analytical batch using multiple laboratory control spikes at multiple concentrations. This method also requires that the precision and accuracy for each sample be determined using field matrix spikes to verify that the method is applicable to each sample matrix.
Calibration standards for PFUnA, PFDoA, PFTrDA, and FOSA have been found to be unstable for more than 2 days in 100% water. Samples requiring analysis for these compounds by this method should be diluted 1:1 with methanol and analyzed against a calibration curve prepared in 1:1 synthetic groundwaterMeOH.
3 Definitions
3.1 Analysis Batch
Am Wset oV If WstuWdTv WsalmI IDB rieI Ws t%hi VaWtI Wa rVer Ior lrVeol nal rl Wed wf f liMthV cV IaH PlivbA rl AaNtiUoVnI V vsitlal inI WdaI %rdH sP | AlalbWoIrvaMtUorrt yV WcolnI UtroV Il samples, and procedural blanks, and analyzed on the s a n e instrument during a tim e period that begins and ends with the analysis of the appropriate continuing calibration check
3.2 Analytical Sample
A portion of a laboratory sample prepared for analysis.
3.3 Calibration Standard
A solution prepared by spiking a known volume o f the Working Standard (W S) into a predetermined amount of A STM Type I, HPLC grade water, or other suitable water (i.e. matrix water), and analyzed according to this method. Calibration standards are used to calibrate the instrument response with respect to analyte concentration.
3.4 Laboratory Duplicate Sample (LDS, or Lab Dup)
A laboratory duplicate sample is a separate aliquot of a sample taken in the analytical laboratory that is analyzed separately with identical procedures. Analysis of LDSs compared to that of the first aliquot give a measure of the precision associated with laboratory procedures, but not with sample collection, preservation, or storage procedures.
ETS-8-044.1
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Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS;
Direct Injection Analysis
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GLP10-01-01; Interim Report 27 Analysis of PFOA In Surface Water Bert Jeffries Landfill - February 2012
3.5 Field Blank (FB)/Trip Blank (TB)
A STM Type I, HPLC grade water, or other suitable water, placed in a sample container in the laboratory and treated as a sample in all respects, including exposure to sampling site conditions, storage, preservation and all analytical procedures. The purpose of the TB is to determine if test substances or other interferences are present in the field environm ent This sample is also referred to as a Trip Blank.
3.6 Field Duplicate Sample (FDS, Field Dup)
A sam ple colected in duplicate at the sam e tim e from the sam e location as the sample. The FDS is handled under identical circumstances and treated exactly the sam e throughout field and laboratory procedures. Analysis of the FD S compared to that of the first sample gives a measure of the precision associated with sample collection, preservation and storage, as w e l as with laboratory procedures.
3.7 Field Matrix Spike (FMS)
A sam ple to which known quantities of the target analytes, ISs and SRSs are added to the sample bottle in the laboratory before the bottles are sent to the field for collection of aqueous samples. A known, specific volume of sample must be added to toe sample container without rinsing. This may be accomplished by making a "fil to this level" line on the outside of the sample container. The FM S is analyzed to ascertain if any matrix effects, interferences, or stability issues m ay complicate the interpretation o f the sample analysis.
3.8 Trip Blank Matrix Spike (TBMS)
An aliquot of A STM Type I, HPLC grade water, or other suitable water, to which known quantities of the target analytes, ISs and SRSs are added in the laboratory prior to toe shipment of the collection bottles. The TBM S is analyzed exactly Ik e a study sample to help determine if the method is in control and whether a loss of analyte or analytical bias could be attributed to sample holding time, sample storage and/or shipment issues. A low and high TBM S are appropriate when expected sample concentrations are not known or m ay vary.
3.9 Internal Standard (IS)
A compound added to each study sample, calibration standard, laboratory control samples, and procedural blanks at a consistent level (typically around 1 ng/mL). The internal standard(s) are stable isotope labeled versions of the target analytes. The area count ra t of the target analyte to the internal standard is used for calforation. Surrogate ISs are applied when stable isotope ISs of target analytes are unavailable. A surrogate IS is not necessarily
a stable isotope labeled version of the target analyte, but is treated as an internal standard for quantitation.
3.10 Laboratory Control Sample (LCS)
An aliquot of control matrix to which known quantities of the target analytes, ISs and SRSs (when applicable) are added in the laboratory at the tin e when samples are aliquotted. At least three levels (two levels for SRSs) in triplicate are included, one generaly at toe low end of toe calibration curve and one near toe mid range and the upper end of the curve. The LCSs are analyzed exactly tike a laboratory sample to determine whether the stability of the standards. LCSs should be prepared each day samples are aliquoted.
3.11 Laboratory Matrix Spike (LMS)
A laboratory matrix spike is an aliquot of a sample to which known quantities of target analytes, ISs and SRSs (when applicable) are added in the laboratory. The LMS is analyzed exactly Ik e a laboratory sample to determine whether the sample matrix contributes bias to the analytical results. The endogenous concentrations o f the analytes in the sample matrix must be determined in a separate aliquot and the measured values in the LMS corrected for these concentrations. LMSs are optional for analysis of aqueous samples.
ETS-8-044.1
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Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS;
Direct Injection Analysis
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1
GLP10-01-01; Interim Report 27 Analysis of p f o a in Surface water Bart Jeffries LandM - February 2012
3.12 Laboratory Sample
A portion or aliquot of a sample received from the field for testing.
3.13 Limit of Quantitation (LOQ) '
The lower limit of quantitation (LLOQ) for an analytical batch is the lowest concentration that can be reliably quantitated within the specified limits of precision and accuracy. The LLOQ is generally selected as the lowest non-zero standard in the calibration curve that meets method acceptance criteria The LLOQ for each target analyte is established for each analysis batch as the lowest calibration standard with area counts at least twice that o f the average area counts of the procedural blanks.
The upper limit of quantitation (ULOQ) for an analytical batch is the highest concentration that can be reliably quantitated within the specified limits of precision and accuracy. The highest standard in the calfcration curve that meets method acceptance criteria is defined as the
ULOQ.
3.14 Method/Procedural Blank
An aliquot o f control matrix that is treated exactly Ik e a laboratory sam ple including exposure to all glassware, equipment, solvents, and reagents that are used with other laboratory samples. The method blank is used to determine if test substances or other interferences are present in the laboratory environment, the reagents, or the apparatus.
3.15 Sample
A sample is an aliquot removed from a larger quantity of material intended to represent the original source material.
3.16 Stock Standard Solution (SSS)
A concentrated solution of a single-analyte prepared in the laboratory with an assayed
reference compound.
.
3.17 Surrogate Internal Standard
An IS that is not necessarily a stable isotopicatty labeled target analyte, but is treated as an internal standard for quantitation. Surrogate ISs are used when isatopicaHy labeled counterparts of the target analyte are not commercially or readily available.
3.18 Surrogate Recovery Standard (SRS)
An isotopicalty labeled standard, not used as an internal standard, that is added to each
sample and appropriate Q C sample as a means to evaluate the method performance for a chemical class of compounds (e.g., PFSAs, PFGAs).
3.19 Working Standard (WS)
A solution of several analytes prepared in the laboratory from SSSs and diluted as needed to prepare calibration standards and other required analyte solutions.
4 Warnings and Cautions
4.1 Health and Safety
The acute and chronic toxicity of the standards for this method have not been precisely determined; however, each should be treated as a potential health hazard. The analyst should w ear gloves, a lab coaL and safety glasses to prevent exposure to chemicals that might be present.
ETS-8-044.1
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Method of Analysis for the Determination of Perflubrinated Compounds in W ater by LC/MS/MS;
Direct Injection Analysis
Pan* 44 of 61
GLP10-01-01; Interim Report 27 Analysis of PFOA in Surface Water
Bert Jeffries Landfill - February 2012
The laboratory is responsible for maintaining a safe work environment and a current awareness of local regulations regarding the handling of the chemicals used in this method. A reference file of material safety data sheets (M SD S) should be available to all personnel involved in these analyses.
4.2 Cautions
The analyst must be fam iliar with the laboratory equipment and potential hazards including, but not limited to, the use of solvents, pressurized gas and solvent ines, high voltage, and vacuum systems. R efer to the appropriate equipment procedure or operator manual for additional information and cautions.
5 Interferences
During sam ple preparation and analysis, major potential contaminant sources are reagents and glassware. All materials used in the analyses shall be demonstrated to be free from interferences under conditions of analysis by running method blanks.
Parts and supplies that contain Teflon should be avoided or minimized due to the possibility of interference and/or contamination. These may include, but are not limited to: wash bottles, Teflon lined caps, autovial caps, HPLC parts, etc.
The use o f disposable micropipettes or pipettes to aliquot standard solutions is recommended to m ake calibration standards and matrix spires.
6 instrumentation, Supplies, and Materials
6.1 Instrumentation
Analytical balance capable of reading to 0.0001g H PLC M S /M S or HPLC/M S system, as described in Section 10.
6.2 Supplies and Materials
Sam ple collection bottles-- HDPE (e.g., NalgeneTM ) wide-mouth bottles with screw cap. Note: Do not use fluorinated or Teflon bottles or lined caps. Coolers or boxes for sam ple shipment. 15-m L and 50-m L disposable polypropylene centrifuge tubes. Class A pipettes and volumetric flasks, various. 2 mL HPLC autovials Disposable pipettes, polypropylene or glass as appropriate Centrifuge capable of spinning 15-m L and 50-m L polypropylene tubes at 3000 rpm.
7 Reagents and Standards_________________________________________
N ote: Suppliers and catalog numbers are for illustrative purposes only. Equivalent performance may be achieved using chemicals obtained from other suppliers. Do not use a lesser grade of chemical than those listed.
7.1 Chemicals
W ater - Milli-Q, HPLC grade, or other suitably appropriate sources
Calcium Acetate - A.C.S. Reagent Grade
ETS-8-044.1
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Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS;
Direct Injection Analysis
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GLP10-01-01; Interim Report 27 Analysis of PFOA in Surface Water Bert Jeffries LandSfl - February 2012
Magnesium Acetate - A .C .S. Reagent Grade Methanol - HPLC grade Ammonium Acetate - A .C.S. Reagent Grade
7.2 Representative Target Analytes, ISs, and SRSs
PFBA, Heptafluorobutyric A dd, (C4 Perfluorinated Add) PFPeA, Nonafluoropentanoic Add (C$ Perfluorinated A dd) PFHxA, Perfluorohexanoic Acid (Cs Perfluorinated A dd) PFHpA, Tridecafluoroheptanoic A dd, (C7 Perfluorinated A dd) PFOA, Ammonium perfluorooctanoate, (C8 Perfluorinated A dd) PFNA, Heptadecafluorononanoic Add, (Co Perfluorinated Acid) PFDA, Nonadecafluorodecanoic A dd (C 10 Perfluorinated A dd) PFUnA, Perfluoroundecanoic A dd, (C ,, Perfluorinated A dd) PFDoA, Perfluorododecanoic A dd, (C12 Perfluorinated A dd) PFTrDA, Perfluorotridecanoic A dd, (C 13 Perfluorinated A dd) FBSA, Perfluorobutanesultonamide FOSA, PerfluoroodanesuIfonytamide PFBS, Potassium Perfluorobutanesulfbnate PFHS, Perfluorohexanesulfbnate PFO S, Potassium perfluorooctanesulfbnate PFO A [1 ,2 ,3 ,4 -13C], 13C-isotopically labeled perfluorooctanoic ad d (SRS) PFO S [1,2, 3 ,4 -13C], 13C-isotopicalty labeled Perfluorooctanesufonate (SR S) PFUnA [1,2-13C], 13C2-isotopicaly labeled Perfluoroundecanoic acid (SRS)
A custom mix of ISs in a methanolic solution containing ([1.2 ,3 ,4 -1^C4]PFBA. [12 -
13C JPFH xA, [1.2,3,4,5,6,7,8-13CJPFO A, [1,2,3,4,5,6,7,8,9-<3Ca|PFNA, [1,2 -X J P F D A ,
[1,2,3,4,5,6.7 - GrJPFUnA, [12 -C J P F D o A , [1 2.3 - l3Ca]PFHS. [1 Z 3 ,4 ,5 ,6 ,7 .8 -13CgJPFOS,
and [1,2 ,3 4 ,5 ,6 ,7 ,8 -13C aPFO SA (Wefc'ngton Laboratories, Guelph, O N) in combination with added ([1,2 ,3 ,4 ,5 -13C5}PFPeA, ([1 ,2 ,3 ,4 -n C4]PFHpA, and [^O JPFB S can be used to prepare a stock IS solution. Alternatively, individual stable isotope ISs can be used to prepare a stock IS mixture. Other ISs can be applied.
7.3 Reagent Preparation
2 m M Ammonium acetate solution (Analysis)--W eigh 0 .3 g of Ammonium acetate and dissolve in 2.0 L of reagent water. Synthetic Groundwater (containing 25 ppm C a and Mg) - W eigh 0.61 g of Caldum Acetate and 0.92 g of Magnesium Acetate and dissolve in 6 .0 L of reagent water. Note: Alternative volumes m ay be prepared as long as the ratios of the solvent to solute ratios are maintained.
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AnaGlyLsPis10o-f0P1F-0O1A; inInteSriumrfaRceepWorat t2e7r
Bert Jeffries Landfill - February 2012
7.4 Stock Standard Solution (SSS) and Working Standard Solution
Preparation
,
The following standard preparation procedure serves as an example. W eighed amounts and
final volumes may be changed to suit the needs of a particular study. For example, pL
Igygjgvolumes m ay be spiked into volumetric flasks when diluting stock solutions to appropriate
100 pg/m L target an alyte SSSs-- Weigh out 10 mg of analytical standard (corrected for percentsalt, acid[ETS-4-031] andpurity) and dilute to 100 mL with methanol or other
suitable solvent, in a 100 m L volumetric flask. Transfer to a 125 mL LDPE bottle or other suitable container. Prepare a separate solution for each analyte. Expiration dates and storage conditions of stock solutions should be assigned in accordance with laboratory standard operating procedure. An example o f purity and salt correction is given below for PFOS.
m olecular w eight of anion salt correction factor =
m oclecular weight of salt
P FO S (K + )saH correction factor = ^ = 0 .9275
10 mg C8F ,7S0 3'K >with purity 90% = 8.35 mg CsF itSOT (10 m g*0.90*0.9275=8.35 mg)
10 pg/m L (10,000 ng/m L) m ixed w orking standard--Add 5.0 mL each of the 100 pg/mL SSSs to a 50 mL volumetric flask and bring up to volume with ad ven t
1 pg/m L (1,000 ng/m L) m ixed w orking standard--Add 0.5 mL of the 100 pg/mL SSSs to a 50 mL volumetric flask and bring up to volume with solvent.
0.1 pg/m L (100 ng/m L) m ixed standard-- Add 0.05 mL of the 100 pg/mL SSSs to a 50 mL volumetric flask and bring up to volume with solvent.
Storage C on d itio n--Store all SSSs and working standards in accordance with laboratory standard operating procedure or in a refrigerator at 42C for a maximum period of 6 months from the date of preparation.
7.5 Calibration Standards
Calibration can tie performed by IS or external calibration. Using the working standards described above, prepare calibration solutions in ASTM Type I water, HPLC water, other suitable water, or a mixture of solvent and water using the information in Table 2 as a guideline. Note: Volumes of water or water/solvent mixtures and working standards may be adjusted to m eet the data quaKty objectives addressed in the general project outline. Calibration levels other than those fisted below can be prepared as needed.
For the quantitation of PFOA and PFOS, reference materials of certified mixed linear and branched isomer are preferred. Alternately, reference materials of primarily linear isomers of PFOA and/or PFO S m ay be used, however, when quantitating with predominantly linear reference standards, additional LCS samples containing both linear and branched isomers of PFOA and PFO S are requited3.
7.5.1 Internal Standard (tS) and Surrogate Recovery Standard (SRS)
For IS calibration, stable isotope internal standards of each target analyte or appropriate surrogate ISs should be spiked at the sam e level in all calibration standards. Once the calibration standards have been prepared as stated above in Section 7.5, all cafibration standards are spiked with a separate internal standard spiking solution. Typicaly the
' A report summarizing an assessment o f the use o f reference standards containing certified linear and branched isomers o f PFOA/PFOS can be found in 3M report E11-0560.
.
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concentration of the internal standard is consistent with the internal standard concentration expected in the samples being prepared, usually 1 ng/mL. The concentration of the interna) standard spiking solution is typically 2 pg/mL. A separate zero point or method blank is typicaly prepared at the sam e time as the calibration standards, using the sam e solution used to prepare the standards (ASTM Type I water, HPLC water, other suitable water, or a solvent/water mixture), and is spired with the internal standard a t the sam e concentration as the calibration curve, typically at 1 ng/m L
If the samples being anaizyed were pre-spiked with SRSs, the calibration curve prepared in Section 7 .5 is spiked with a separate SRS spiring solution. Typically, the sample bottles are spiked with a SRS at 0.1 ng/m L The final calibration curve must consist of at least six calibration points after analysis. The following table provides an exam ple of spire concentrations and volumes used to achieve a multi-point extracted calibration curve with internal standard and surrogate standard.
Table 1 lists recommended stable isotope internal standards for several PFSA and PFCA target compounds. A custom mix o f isotopicaHy labeled target analytes in a methanolic solution containing ([1,2,3,4 -1sC4]PFBA, [1,2 -X J P F H x A , [1,2.3,4,5,6.7,8 -13CalPFOA, [1,2,3,4,5,6,7,8,S^ ydP FN A , [1,2,3,4,5,6 -13Ca]PFDA, [1,2,3,4,5,6 ,7 -^CdPFU nA, [1,2 "C JP FD oA , [1,2,3-l3Ca]PFHS, [1,2,3,4,5,6,7,8-13Ca]PFOS, and [1,2,3,4,5,6,7.8-13C JFO SA (Wellington Laboratories, Guelph, O N) in combination with added ([1,2,3,4,5-13Cs|PFPeA, 1,2,3,4-13CJPFHpA, and [^O JPFB S can be used to prepare a stock IS solution. Alternative sources o f certified stable isotope labeled target analytes are applicable. Alternatively, individual stable isotope ISs can be used to prepare a stock IS mixture. The table below lists the recommended stable isotope ISs and SRSs applied in the method. Other stable isotope ISs and SRSs of target analytes not Ksted in the table m ay be used if supported by validation and/or analysis batch Q C s meeting method acceptance criteria (e.g., [13C2]-PFOA). The sam e internal standard should be used for a given analyte throughout the entire prpject/study. Note: some of the compounds listed below are appropriate to use as surrogate ISs when a stable isotope IS of a target analyte is not available. Generally, surrogate isotopically labeled PFCAs are used for PFCAs, and surrogate isotopically labeled PFSAs are used for PFSAs.
Table 2 provides examples of spike concentrations and volumes used to achieve a multi-point calibration curve with ISs and SRSs.
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Table 1. Stable Isotope PFCAs and PFSAs used for ISs and SRSs
CompoundName
Synonym orAcronym
15C-Perfluorobutanoic acid 13C-Perfluoropentanoic acid
[U ,3 ,4 -IJC ,]P FB A [ lA 3 ,4 (S-Cj]PFPeA
1JC r Perfluorohexanoic acid 1'CrPerfluoroheptanoic acid ,3CrPerfluorooctanoic acid
[ U - uCJPFH xA (1,2,3,4 -'3C*]PFHpA [l,2,3,4,5,6,7,8-l,C ,]P FO A
13CrPerfluorononanoic acid 15Ci-Perfluorodecanoic acid
(U 3 ,4 ,5 ,6 ,7 .8 ,9 -'3C ,]P F N A [1,3 ,4 ,5 ,6 -'` Q IP F D A
1'C r Perfluoroundecanoic acid
[ W ,4 ^ ,6 ,7 - llC TjPFU nA
"CrPerfluorododecanoic acid
[ U - ,JCj}PFD oA
" O r Ammonium Perfluorobutane sulfonate [" O JP F B S
"CrAm m onium Perfluorohexane sulfonate [ U .3 - l3Cj]PFH S
" C r Sodium Perfluorooctane sulfonate
[l,2,3,4,S,6,7,8-l3C.]PFO S
"CrPerfluorooctanesulfbnam ide 13CrPerfluorooctanoic acid
[1,2.3,4,5,6,7.8-IJC .]FQ S A [1 A 3,4-I3C4]PF0A
AnalyticalPurpose
IS fo rP F B A IS for PFPeA
IS for PFH xA IS for PFH pA IS for P FO A and [ 1 ^ ,4 ,JC .]P F O A IS for P FN A IS for P FD A
IS for PFU nA
IS fo rP F D o A , *PFTA ISforP FB S IS for PFHS IS for PFO S and P F O S [U ^ ,4 " C .], IS for F O S A
SRS fo ra li PFCAs: C4-C8
RSoeuferrceenceStandard
W ellington Labs (M ix or Individuai) W ellington Labs (M ix or Individuai)
W ellington Labs (M ix or Individuai) W ellington Labs (M ix or Individuai) W ellington Labs (M ix or Individuai) W ellington Labs (M ix or Individuai) W ellington Labs (M ix or Individuai) W ellington Labs (M ix or Individuai) W ellington Labs (M ix or Individuai) R TI Internationa) (Individuai) W ellington Labs (M ix or Individuai) W ellington Labs (M ix or Individuai) W ellington Labs (mix) RTI International (Individuai)
W ellington
"CrPerSuoroundccanoic acid
|1,2 -,JCj]P FU nA
SRS fo ra li P F C A sC 9 -C 1 3 W ellington
"CrPerfluorooctane sulfonate
[l,2 ,3 ,4 -l3C]PFOS
SRS fo ra li PFSAs: C4, C 6 ,a n d C 8
W ellington
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Trills 2. Example Preparation of Calibration Curve with ISs and SRSs
S a m p le D e s c rip tio n
0.025 n g/m l curve point 0.030 ng/mL curve point 0.04 ngAnL curve point 0.05 ngAnL curve point
0 .1 ng/m l. curve point 0.25 ngAnL curve point 0.5 ng/mL curve point
1 ng/mL curve point 2.5 ng/mL curve point 5.0 ng/mL curve point 10.0 ng/mL curve point 25.0 ng/mL curve point 50.0 ngAnL curve point 75.0 ngAnL curve point 100 ng/mL curve point
C o n c e n tra tio n o fW S ,ttg /m L
0 .1 0 0 .1 0 0 .1 0 0 .1 0 0 .1 0 0 .1 0
1 .0 1 .0 1 0 .0 1 0 .0 1 0 .0 1 0 .0 1 0 .0 1 0 .0 1 0 .0
V o lu m e o f w s .fi.
25 30 40 50
100
250 50
100
25 50
100
250 500 750
1000
V o iu m a o fIS (2 ttg /m L ),fjL
50 50 50 50 50 50 50 50 50 50 50 50 50 50 50
ConeeniraffcMi o f
S u rro g a te , fig /m L
0 .2 0 0 .2 0 0 .2 0 0 .2 0 0 .2 0 0 .2 0 0 .2 0 0 .2 0 1 0 .0 1 0 .0 1 0 .0 1 0 .0 1 0 .0 1 0 .0 1 0 .0
V o lu m e o f S u rro g a te , fd .
12.5 15
20
25 50 125 250 500 25 50
100
NA NA NA NA
V o lu m e o f A S T M T y p e 1 W a te r, o r o th e r s u ita b le s o lv e n tm , m L
100 100 100 100 100
; 100
100 100 100 100 100 100 100 100 100
N /A -N o t Applicable (1) Samples requiring analysis for PFUnA. PFDoA. PFTrOA, and FOSA should be analyzed against a calibration curve prepared in 1:1 synthetic groundwater:MeOH.
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8 Sample Collection and Bottle Preparation
Sample collection bottles are prepared by 3 M Environmental Laboratory (or subcontract supplier) personnel for shioment a t ambient tem oerature to the collection site. Tvoicaltv. four seoarate collection bottles are associated with a single collection site: sample, field duplicate sample, low field matrix spike, and high field matrix spike. Alternatively, the sample and field duplicate sample m ay contain SRSs in lieu of additional target analyte low field matrix spike and target analyte high field matrix sp ite samples. Depending on the scope of the project, additional replicates of the field sample and field matrix spikes m ay be added. Also, it is not uncommon for additional mid-level field matrix spikes to be collected if the expected sample concentrations are buly unknown or could span a large concentration range.
High-density polyethylene (H DPE) wide-mouth Nalgene bottles are used for the sample collection containers. (Volumes of the bottles may vary depending on how much sample is required to m eet data quality objectives.) Sample collection volumes are project specific and based on data quality objectives. The Nalgene bottles do not require any pretreatment prior to use. Typically, placement of a sample bottle volumetric "fill to here* line is done by using a sample bottle marker template. Altamatively, bottles may be weighed prior to bottle preparation and weighed again after samples have been collected.
FAwIIWIWf I Vt lW^ ^m hVoWi'IIvdhAb f v d w%MW1V I^f NlRMhfVAI wkvKlWtof iInI rii f ^ Iwi^ IiInIWfr^l l%dnre% rl iM^v v WasiaA sm aimVn nr l wlef InfAHIVdI gMal ri otte W V iknF iinirM^n ov f IWloWwV VfIiVeIlMd matrix spke, high field matrix spike, sample/SRS field matrix spike, field duplicate sam pie/SRS field matrix spike, trip blank, or trip blank matrix spke. If each location has different designated spike levels, the label should also clearly indicate the sample location designation. Generally, a set of bottles for a given collection sWitWe WarVe |Dp lrVe|or l MarWed t%hVWelnV MoVrof ^ul |DF Vedl f tIoV Maev tlhWelr MinV fcFlaWsWtVicF VbFaVAaHsv fI oW r VoIrMaVaAVnIMizAaAttiloV InVaMMl VDwurIor WosWes* VFWor WeaVcIhV MsaA mI I VoVlWe collection event, at least one set of trip blank and trip blank matrix spkes are prepared.
Bottle preparation should be documented in a Note to File or on a sample preparation worksheet and should include the following information: date prepared, total number of bottles prepared, number of sample sites, the standard'identification numbers and sp ke volumes used to prepare spiked bottles, the `fit to here* volume, and any other pertinent information needed for reconsfoictibility of the data. The Note to File will be included in the final data package for the project
Samples are collected in the field and shipped to the laboratory at ambient temperature.
8.1 Field Matrix Spike Sample (FMS)
Field matrix sp ke samples are a requirement of the method. A FM S sample is defined as a Q C sample to which known quantities of appropriate target analytes are added to the sample bottle in the field or in the laboratory before the bottles are sent to the field. The sample and field duplicate sample m ay contain appropriate SRSs in lieu of target analyte FM S samples. Sample quantities are determined voiumetricalty or gravimetricaHy. A known, specific volume or weight of sample is added to the sample container without rinsing. Volumetric sample measurements m ay be acquired by a laboratory applied "fill to this level* line on the outside of the sample container. Target analyte FM S samples should be spiked at approximately 0.5-10 times the expected analyte concentration in the sample. If the expected range of analyte concentrations is unknown, multiple spkes at varying levels m ay be prepared to increase the likelihood that a sp ke at an appropriate level is made. Typically a low and a high target analyte spike are prepared for each sampling location. In those instances w here SRSs are to be used to lieu o f target analyte FM S samples, the sample and field duplicate sample are spiked at approximately 2-5 tim es the target LOQ. The FM S is analyzed to ascertain if matrix effects or sam ple holding time contributes bias to the analytical results. For the sample bottles designated for matrix spikes, an appropriate volume of matrix spiking solution is added to the empty bottle prior to sampling. The volume of spike solution added should produce the desired final concentration of target analytes once the bottle is filled with sample to the "fill to here line*. The matrix spking solutions) should be prepared in a suitable solvent and contain all of the appropriate target analytes, ISs, and SRSs. The target analyte matrix spiking solution is often the sam e as the working standards used to create the cafbration standards. An exam ple of a bottle sp ke is given below.
` Fill to here* volume = 200 mL (A 250 mL Nalgene bottle is used)
Desired Field S p k e Concentration = 0.25 ng/mL
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500 of a 0.1 ng/mL spring solution (containing the target analytes) is added to the bottle and the bottle cap promptly sealed.
8.2 Internal Standard and Surrogate Recovery Standard
If analysis of a surrogate recovery standard (SR S) is included in the project objectives, an appropriate volume of a surrogate standard solution is added to all the bottles priorto sampling and SPE. Typically sample bottles are spiked with surrogate recovery standards at a final desired spike concentration of 0.1 ng/m L
If quantitation by internal standard (IS ) is included in the project objective, an appropriate volume of internal standard solution is added to a l the bottles prior to sampling and SPE. Typically sample bottles are spiked with internal standard at a final desired spike concentration of 1 ng/mL.
For the trip blank, the SR S sp ke and IS spke is added to toe bottle and then ASTM Type I w ater (HPLC grade reagent water or other suitable w ater may used) is added to the "fitt to here- line. The bottle is capped and sealing tape may be placed around the outer edge of the cap. Trip blank matrix spkes are prepared by adding the appropriate volume erftarget analyte spiking solution, IS , and SRS spiking solutions and filling the bottle to the desired volume with the appropriate water and capping and sealing the cap.
9 Quality Control and Data Quality Objectives
9.1 Data Quality Objectives
This method and required quality control samples is designed to generate data accurate to 30% with a targeted LOQ o f0.025 ng/mL. Any deviations from the quality control measures spelled out below will be documented in the raw data and footnoted in the tria l report
9.2 Method/Procedural Blanks
The method/procedurai blank is zero point calibration standard (which includes ISs) analyzed in a regular basis with each analysis batch. At a minimum, method blanks are analyzed prior to instalment calibration, prior to the analysis o f C C V samples, after every 10 sample injections, and at the end of the analytical run.
The mean area count or area ratios when using internal standard calibration, for each analyte in the method blanks must be less than 50% of the area count counts or area ratios when using internal standard calibration, of the LOQ standard. The standard deviation of the area counts, or area ratios when using internal standard calibration, o f these method blanks should be calculated. A specific % RSD acceptance criteria is not specified but is assessed on an analytical batch basis. If the mean area counts or area ratios when using internal standard calibration, of the method blanks exceed 50% of the LOQ standard, then the LOQ must be raised to the first standard level in the curve that meets criteria. Method blanks m ay be eliminated if technical justification can be provided (e.g. the procedural blank was analyzed after an unexpectedly high level sample). If any procedural blanks are removed from the LOQ determination, document in the raw data and report as appropriate. Laboratory Sample R eplicates/Field Duplicate Sample
Typically, samples are collected in duplicates in the field. The relative percent difference (R PD ) of duplicate samples should be 2 0 % for the precision of sample preparation and analysis to be considered in control. Replicate samples not meeting the 20% RPD criteria are flagged and reported as outside o f QC acceptance cncena.
9.3 Laboratory Matrix Spikes (LMSs)
LMSs m ay be performed in lieu of FMSs if FM Ss have previously been performed for toe sample matrix. Additionally, LMSs may be performed in lieu of FMSs for a sample matrix if the FM S levels were not appropriate for determining sp ke recoveries relative to endogenous levels of target analytes and appropriate SRSs. Generally, each sample location represents a different sample and sample matrix. LMSs are prepared for each sample and analyzed to determine the matrix effect on sp ke recovery efficiency of each target analyte and appropriate SRSs. LMSs should be prepared at a minimum of one level and in duplicate. LMS concentrations should be prepared at approximately 0.5-10 times the endogenous concentration or approximately 4 -1 0 times the LOQ concentration of each target analyte.
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Lab matrix spike recoveries should foil within 3 0 % of expected values. Sam ple data with LMS recovery outside of 30% but wthin 50% of the expected value are flagged and reported as outside of Q C acceptance criteria. Data with LMS recovery outside of 50% of the expected value are reported as NR, where N R is defined as "Not Reportable' data outside of QC acceptance criteria.
9.4 Lab Control Sample
Lab control spikes are prepared for each analysis batch to determ ine method accuracy and precision. LCSs should be prepared a t three levels in triplicate for each target analyte and at a minimum of two levels in triplicate for appropriate SRSs. Low lab control spikes should be prepared at a concentration in the range of
approximately four to ten times higher than the targeted lower LOQ. the mid lab control spates should be
prepared at a concentration near the mid-point of the calibration curve and the high lab control spikes at approximately 80% of the upper LOQ. For each target analyte and SRSs, the percent relative standard deviation (method precision) for each control spike level must be less than or equal to 2 0 % and the average recovery (method accuracy) for each control spike level must be 80-120% . Sample data for target analytes outside of the laboratory control spike acceptance criteria will be handled as follows:
If the average recovery of a spiking level foils outside method acceptance, but at least 67% (6 out of 9 ) of LCS samples are within 2 0 % of their respective nominal value (33% of the QC samples, not all replicates at the sam e concentration, m ay be outside 2 0 % of nominal value), the average recovery will be flagged as outside method acceptance criteria All LCS samples will be control charted as per ETS-4-026. If the average recovery of one of the spiking levels exceeded the analytical method uncertainty as determined by ETS-120 1 2 , that analytical batch uncertainty will be expanded for that particular study.
If more than 67% of the LCS samples foil to m eet method acceptance criteria, the data will not be reported.
Calibration standards consisting of mixed branched and linear isomer PFO S/PFOA are preferred. However, for PFO S/PFQ A target analytes, if the calibration standards are comprised of predominantly linear isomers only, at least one level of triplicate LCSs should be prepared using PFOS/PFOA which contains a mix of linear and branched isomers. These LCSs will be used to demonstrate quantitative equivalency (or quantitative bias) of the isomeric mix when using a predominantly linear standard for calibration. The mixed linear and branched isomer PFO S/PFOA LCSs recoveries should foil within 30% of expected values. Alternatively, in lieu of mixed branched and linear isomer PFO S/PFO A LCSs, mixed branched and linear isomer PFO S/PFOA TBM Ss m ay be applied to demonstrate method accuracy and precision.
9.5 Field Matrix Spikes (FMSs) / Surrogate Recovery Standards (SRSs)
FMSs are prepared for each sampling location and analyzed to determ ine the matrix effect and sample holding tim e on the spike recovery of each target analyte and/or appropriate SRS. Generally, each sample location represents a different sample and sample matrix.
FM Ss are Q C samples to which known quantities of appropriate target analytes are added to the sample battle in the laboratory before the bottles are sent to the field. Typically a low and a high target analyte FM S are prepared for each sampling location. The sample and field duplicate sample m ay contain appropriate SRSs in lieu of target analyte low field matrix sp ke and target analyte high field matrix spike samples.
Fiekl matrix sp ke method acceptance criteria are recoveries within 30% of the expected value. If FMS recovery (target analyte or SR S spike) is outside of 30% of the expected value or could not be assessed because the FM S (target analyte) was spiked at an inappropriate level, the sample result is repotted as follows:
1. ) If target analyte FM S recovery could not be assessed because the FMS*s were at an inappropriate level, then Laboratory Matrix Spikes (LM S) may be substituted. If LMS recoveries are within 30% the data are reportable and flagged to indicate that the FM S spikes levels were inappropriate.
2. ) If multiple target analyte FMS's were prepared on a sample and the closest FM S level to the reported sample meets the 30% acceptance criteria but addlional FMS's are outside the 30% acceptance range, the data are reportable and flagged to indicate that while there were foiling FM S's, the uncertainty will not be expanded since the most appropriate spike level passed.
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3. ) If the target analyte FM S recoveries are outside of the 30% acceptance range but a t least 30 acceptable historical reportable FM S sample results are available, the data may be reported but flagged with an expanded uncertainty and as not meeting FM S criteria
4. ) Sample data with FMS recovery outside of 30% but within 50% o f the expected value are flagged and reported as outside of Q C acceptance criteria with an expanded uncertainty.
5. ) If FM S recovery is outside of 50% , the sample result is reported as NR, where NR is defined as "Not Reportable' due to noncompliant Q C results.
The targeted fortification levels should be at least 50% of the endogenous level a id less than 10 tim es the endogenous level to be used without justification to determine the statement of accuracy for analytical results.
Note: It is possible for bottles utilized for Field Matrix Spike samples to be under-filed or over-filied during sample colection. Since this scenario will effect the actual concentration of the FM S sam ple (surrogate and internal standard concentrations will also be effected, fused), it is important that any obvious under-filing or over-filing rtf sample bottles be documented in the data package and taken into account in the FM S, ISs, or SRSs recovery calculations. Samples over-filed or underfilled by more than 10% w il be require recalculation of the FM S, ISs, and SRS true values.
The average of the sample and the field duplicate should be used to calculate the recovery.
10 Procedures
10.1 Water Sample Preparation
This method is applicable to water samples. Samples containing heavy particulate m ay not be suitable for analysis by this method. Samples containing suspended particulate should be centrifuge prior to removing a ' sample aliquot, or filtered.
Thoroughly mix sample before removing an aliquot and placing in a labeled autovial.
Dilute sample, if necessary, with ASTM Type I water, HPLC water, other suitable water, or solvent (m ethanol).
Lab control spikes are prepared for each analysis batch to determine method accuracy and precision. LCSs should be prepared at three levels in triplicate for each target analyte and at a minimum of two levels in triplicate for appropriate SRSs. Low lab control spikes should be prepared at a concentration in the range of approximately four to ten times higher than the targeted lower LOQ, the mid lab control spikes should be prepared at a concentration near the mid-point of the cafibration curve and the high lab control spikes at approximately 80% of the upper LOQ. For IS quantitation, stable isotope internal standards of each target analyte or appropriate surrogate ISs should be spiked at the sam e level as the samples bong analyzed, in all LCSs.
If LCSs are being prepared using synthetic groundwater, allow the LCSs samples to equiKbrate for a minimum of 4 hours before alquoting for analysis or diluting with solvent (methanol)-
11 Sample Analysis - LC/MS/MS
_____ '____________
11.1 Instrument Setup
Note: In this example, an Applied Biosystems Sciex A PI 400 0 (API 5000 or A PI 5500) Tandem Mass Spectrometer (LC/M S/M S) is used. Other brands/modete of LC/M S/M S instruments as well as single quadrupote mass spectrometers (LC /M S) m ay be used as long as the method acceptance criteria are m et Brand names, suppliers, part numbers, and models are for illustrative purposes only. Equivalent performance m ay be achieved using apparatus and materials other than those specified here, but demonstration of equivalent performance that meets the requirements o f this method is the responsibility of the laboratory. The operator must optimize and document the equipment and settings used.
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Establish the LC/M S/M S system and operating conditions equivalent to the following: Mass Spec: Applied Biosystems A PI 4000, A PI 5000, or A PI 5500
Ion Source: Turbo Ion Spray (ABS)
Mode: Electrospray Negative
Scan Type: M RM (Multiple Reaction Monitoring) . Com puter Dell OHM
Software: Windows 2000 or Windows X P , Analyst 1.42 or higher versions
HPLC: Agilent Series 1100,1200, or 1290
Agilent Quaternary Pump
Agilent Vacuum Degasser
Agilent Autosampler
'
Agilent Column Oven
.
Note: One or more C 18 HPLC analytical columns (2.1 mm x 100 mm, 5pm or 2.1 mm x 50 mm, 5jim ) may be attached on-Nne alter the purge valve and before the sample injection port to retard and separate any residue contaminants that may be in the mobile phase and/or HPLC system.
HPLC Column: Betasll C 18,4.6m m x 100mm, 5nm (ThermoElectron Corporation)
Column Temperature: 35C
Injection Volume: 5pL
Mobile Phase (A): 2m M Ammonium Acetate in ASTM Type I water (S ee 7.3) Mobile Phase (B): Methanol
Table 3. Liquid Chromatography Gradient Program.
Stmn Number
0 1 2
3 4 5
Total Him (min}
0 2 .0
14.5 15.5 16.5
2 0 .0
Flow Rata QdJmln)
750 750 750 750 750 750
ForantA (2 mM ammonium
acatata)
97.0 7.0
5.0 5.0 97.0 97.0
Partant B (Methanol)
3.0 3.0 95.0 95.0 3.0 3.0
Note: Other HPLC gradients m ay be used as long as the method criteria and project data quality objectives are m et
It may be necessary to adjust the HPLC gradient in order to optimize instrument performance. Columns with different dimensions (e.g. 2.1m m x 30mm ) and columns from different manufacturers (Keystone Betas! C18 etc.) may be used.
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Analysis
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GLP10-01-01; Interim Report 27 Analysis of PFOA in Surface water Bert Jeffries Landfill - February 2012
Table 4 Suggested MRM Transitions for Target Analytes, Surrogates, and Internal Standards
Analyte
P FB A (C4 Acid) PFPeA iC S Acid) P FH xA (C6 A cid) PFHdA (C 7 A cid) P FO A CCS A cid)
P FN A (C9 A cid) P FD A (CIO A cid) P F U n A fC ll A cid) P FD oA (C 1 2 A cid) P FTA (C 1 3 A cid) F B S A (C 4 Sulfonamide) FO S A (C8 Sulfonamide) P FB S (C 4 Sulfonate) P FH S (C 6 Sulfonate) PFOS (C8 Sulfonate) [12.3.4 -''O IP F B A [12.3.4.5 -" C ilP F P eA [12 -'' C ilP F H x A [1 22 ,4 - ,JC ,]P FH p A [1 2 .3 .4 2 .6 .7 .8 -mC ,1 P F O A [12.3.4.S.6.7.8.9-l,C4lPFN A [12,3,42,6 -UQ ]P F D A [12.3,4.5.6.7 -"C jlP F U n A [12 -" C jIPFDoA ["O jIPFBS [1 2 ,3 -', C ,1 P FH S [1 22 .4 - " G 1PFO S [122,42,6.7,8- uC)FOSA [1 2 2 .4 -,JC4lPFO A [1 22 .4 - UC1PF0S [12 -"C iIP FU n A
Anatyte Description
Tarnet Tarnet Tarnet Tarnet Tarnet
Tarnet Target Tarnet Tarnet Tarnet Tarnet Tarnet Tarnet Target Target IS for P FB A IS for PFPeA IS for P FH xA IS for PFH dA IS for P FO A IS for P FN A IS for P FD A ISforPFU nA IS for PFD oA and P FTA ISforPFB S IS for PFHS IS for PFOS IS for FO SA Surrosate (C4-C8 Acids) Siarocate(Sulfonatcs. FO SA) Surrogate (C9-C13 Acids)
Mass Transition Ol (amu)
213 263 313 363 413 463
513 563 613 663 298 498 299 399 499 217 268 315 367 421 472 519 570 615 303 402 503 507 417 503 565
Mass TrastMaa SfaaaO
169 219 269.119 319.169 3 6 9 .2 1 9 .1 6 9 4 1 9 ,1 6 9 ,2 1 9
4 6 9 .2 6 9 .2 1 9 5 1 9 .2 6 9 .2 1 9 569.169.319 6 1 9 ,3 6 9 .3 1 9
78 78 9 9 .8 0 9 9 .8 0 80.99. 130 172 223 270 322 376 427 474 525 S70 84 80 80 80 372 80 520
Multiple transitions for monitoring the analytes is an option. The use of one daughter ion is acceptable if data sensitivity and selectivity is achieved and provided that retention tim e criteria are met to assure adequate specificity. W hile the daughter ions may be chosen at the discretion of the analyst, mass transition 99 is suggested for PFO S. Quantitation may be performed using the total ion chromatogram fTIC , or summed M RMs) for a given analyte. For example, the PFO A TIC would sum all three o f the monitored transitions. Use of the suggested primary ion is recommended. Retention times m ay vary slightly, on a day-to-day basis, depending on the batch of mobile phase and the gradient, column, guard cotumn(s) used etc. Drift in retention times is acceptable within an analytical run, as long as the drift continues through the entire analysis and the standards are interspersed throughout the analytical run.
11.2 Calibration Curve
Quantitation is by internal standard or external standard calibration. Caltoration standards may be prepared in ASTM Type I, HPLC water, other suitable water, or a solvent/water mixture. If internal standard calibration does not m eet calibration acceptance criteria, external calibration can be applied. S ee Table 1 for
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Analysis
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GLP10-01-01; Interim Report 27 Analysis of PFOA in Surface water Bert Jeffries LandIM - February 2012
Table 4 Suggested MRM Transitions for Target Analytes, Surrogates, and Internal Standards
Analyte
P F B A (C4 A cid) PFPeA (C5 A cid) P FH x A (C 6 Acid) P F H p A (C 7 A cid) P FO A fC8 A cid)
P FN A (C9 A cid) P FD A (CIO Acid) P F U n A ( C ll A cid) P FD o A (C 1 2 A cid) P F T A (C 1 3 A cid) F B S A (C4 Sulfonamide) F O S A CC8 Sulfonamide) PFBS (C4 Sulfonate) PFHS (C6 Sulfonate) PFOS (C8 Sulfonate) fl.2 .3 .4 -''C.1PFBA f U J .4 .5 -"G lP F P e A f U - '^ lP F H x A fU .3 ,4 - ' Q lP FH pA [ U A 4 A 6 ,7 ,8 - 1JC ,]P FO A [1A3,4,5,6,7,8,9-IIC ,]P FN A fl.2,3.4.5,6 -"C ilP F D A rU .3 .4 .5 .6 .7 -l5C ,lP F U n A
f U -" C 1IPFD0A
f'fo ilP F B S [I A 3 -UC JP F H S I U J .4 - ,3C1PF0S 11.2.3.4.S.6.7.8- '' C tlF O S A f U J .4 - ,JC ,lP F O A iu .3 .4 - ,5c .i p f o s r u -'' C ilP F U n A
Analyte Description
Target Target Target Target Target
Target Target Target Target Target Target Target Target Target Target IS for P FB A IS for PFPeA IS for PFH xA IS for PFH pA IS for P FO A IS for P FN A IS for P FD A IS for PFU nA IS for P FD oA and P F T A IS for PFBS IS for PFHS IS for PFOS IS for FO S A Surrogate (C4-C8 Acids) SurrogatefSulfonates. FO S A ) Surrogate (C9-C13 Acids)
Mats Transition 0 ! (atm)
213 263 313 363 413 463
SI3 S63 613 663 298 498 299 399 499 217 268 315 367 421 472 519 570 615 303 402 503 507 417 503 565
Mass Transition Q3(amu)
169 219 269.119 319.169 3 6 9 .2 1 9 .1 6 9 4 1 9 ,1 6 9 ,2 1 9
4 6 9 .2 6 9 .2 1 9 5 1 9 ,2 6 9 .2 1 9 5 6 9 .1 6 9 .3 1 9 6 1 9 .3 6 9 .3 1 9
78 78 99.80 99,80 8 0 .9 9 .1 3 0 172 223 270 322 376 427 474 525 570 84 80 80 80 372 80 520
Multiple transitions for monitoring the analytes is an option. The use of one daughter ion is acceptable if data sensitivity and selectivity is achieved and provided that retention time criteria are met to assure adequate specificity. W hile the daughter ions may be chosen at the discretion of the analyst, mass transition 99 is suggested for PFO S. Quantitation may be performed using the total ion chromatogram (TIC , or summed M RM s) for a given analyte. For example, the PFOA T IC w x ild sum all three of the monitored transitions. Use of the suggested primary ion is recommended. Retention times may vary slightly, on a day-to-day basis, depending on the batch of mobile phase and the gradient, column, guard column(s) used etc. Drift in retention tim es is acceptable within an analytical run, as long as the drift continues through the entire analysis and the standards are interspersed throughout the analytical run.
11.2 Calibration Curve
Quantitation is by internal standard or external standard caforation. Calibration standards may be prepared in ASTM Type I, HPLC water, other suitable water, or a solvent/water mixture. If internal standard calibration does not m eet calibration acceptance criteria, external calibration can be applied. S ee Table 1 for
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Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection
Analysis
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GLP10-01-01; Interim Report 27 Analysis of PFOA in Surface water Beit Jeffries Landfll - February 2012
recommended application of available internal standards. Quantitation of PFOA and PFO S is by summed analyte-specific mass transitions.
Analyze the standard curve prior to each set of samples. If internal standards were added to the calibration standards area ratios are used to generate the calibration curve. The standard curve may be plotted using a linear regression (y = mx + b), weighted 1Acor unweighted, or by quadratic fit (y = ax2 + bx + c), weighted 1Acor unweighted, using suitable software. The mathematical method used to calculate the calibration curve should be applied consistently throughout a study. Any change should be thoroughly documented in the raw data.
High and/or low points may be excluded from the calibration curves to provide a better fit over the range appropriate to the data or because they did not m eet the pre-detenmined acceptance criteria. Low-level curve points should also be excluded if their area counts (or area ratio if quantitating by IS ) are not at least twice that of the average area counts (or area ratio if quantitating by IS) of method and/or solvent blanks. The coefficient of determination (r2) value for the calibration curve must be greater than or equal to 0.990 (or a correlation coefficient (r) of 0.995). Each posit in the curve must be within 25% of the theoretical concentration with the exception of the LLOQ, which may be within 30% . Justification for exclusion o f calibration curve points will be noted in the raw data. A minimum of 6 points will be used to construct the calibration curve.
If the calibration curve does not m eet acceptance criteria, perform routine maintenance or prepare a new standard curve (if necessary) and reanalyze.
11.3 Continuing Calibration Verification (CCV)
Continuing calibration verifications (C C V) are analyzed to verify the accuracy of the calibration curve. Analyze a mid-range calibration standard, one of the sam e standards used to construct the calibration curve, at a minimum after every tenth sample, not including solvent blanks, with a minimum of one per sample s e t Calibration verification injections must be within 25% to be considered acceptable. The calibration curve and the last passing C C V will then bracket acceptable samples. Multiple C C V levels may be used. Samples must be bracketed by passing CCVs or the calibration curve and a passing C C V to be reportable.
11.4 System Suitability
A minimum of three system suitability samples should be injected at the beginning of each analytical run, prior to the analysis of the calibration curve. Typicaly these samples are at a concentration near the mid-level o f the cafibration curve and are repeated injections from one autosampler vial. It is suggested that the system suitability injections have area counts or area ratios when using internal standard calibration, wfth a target RSD of 5% and a target retention time RSD of 22% . There is no defined acceptability limit on these results as the % RSD value is dependent on the number of M RM transitions being monitored in the LC/M S/M S run or time period. Ultimately, any effects on these parameters for the System Suitability samples w il also be evident on all standards and Q C samples analyzed as p art of the analysis batch. Any effect of system suitabiSty is incorporated within QC acceptance criteria.4
11.5 Sample Analysis and QCs
For each analysis batch, the instrument analysis run sequence should include an initial calibration curve, samples, FDSs, interspersed blanks, interspersed CCVs, appropriate Q Cs (i.e., LCSs, LMSs, FMSs, TBMSs, and TBs), and a final C CV or calbration curve bracketing samples and appropriate QCs
Inject the sam e volume (behween 5 - 1 0OpL) o f each standard, analytical sample and blank into the instrument (unless an on-instrument sample dilution is desired).
Samples containing analytes that are quantitated above the concentration of the highest standard in the curve
should be further diluted and reanalyzed.
4 3M Environmental Laboratory study E08-0096 evaluated the effect on these results as a function o f the number o f M R M s being monitored.
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Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection
Analysis
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GLP10-01-01 ; Interim Report 27 Analysis of PFOA in Surface Water Bert Jeffries LandN February 2012
12 Data Analysis and Calculations
The chromatography analysis software w il typically calculate the amount of target analyte in the sample extracts using the established c aixatio n curve. Calculate the percent recovery of the LCS using the following equation:
LCS%recovery ---L--C--S--C--o-n--c-e-n--tr-a--ti-o--n--mtr 100% Spike Concentration
Calculate the percent recovery of the LMS using the foHcwing equation:
LMS % recovery -
LMS Concentration (-S -) - Concentration o f Sam ple mL
Spike Concentration (-3 -) mL
mL
100%
For samples fortified with known amounts of analyte prior to extraction, use the following equation to calculate the percent recovery.
Total analyte found (ng/m L) - Average anaiyte found in sam ple (ng/m L)
Recovery =
x 100
Analyte added (ng/m L)
13 Analysis Batch Method Performance Criteria
Any method performance parameters that are not achieved must be considered in the evaluation of the data. Nonconformance to any specified parameters must be described and discussed in the final report if the Technical M anager (non-GLP study) or Study Director (G LP study) chooses to report the data.
If criteria listed in this method performance section are not met, maintenance m ay be performed on the system and samples reanalyzed, or other actions taken as appropriate. Document all actions in the raw date.
If date are to be reported when performance criteria have not been met, the date must be footnoted on tables and discussed in the text of the report.
13.1 System Suitability - Analysis Batch
A minimum of three system suitability samples should be injected at the beginning of each analytical run. These samples are run prior to the calibration curve. It is suggested that the system suitability injections have area counts with a target R SD of 5% and a target retention tim e RSD of 2%. There is no defined acceptability limit on these results as the % RSDs are dependent on the number of MRM transitions being monitored in the LC/M S/M S run or tim e period. Any effect of system suitability is incorporated in the QC acceptance criteria.
13.2 Calibration and Limit of Quantitation (LOQ) - Analysis Batch
C alibration C urve: The coefficient of determination (r2) value for the calibration curve must be greater than or equal to 0.990 corresponding to a correlation coefficient (r) = 0.995. Each point in the curve must be within 25% of foe theoretical concentration with the exception of the LLOQ, which may be within 30% .
C C V Perform ance: The calibration standards that are interspersed throughout the analytical sequence are evaluated as continuing calibration verifications in addition to being part of toe calibration curve. The accuracy
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of each curve point must be within 25% of the theoretical value (within 30% for lowest curve point). Samples that are bracketed by C CVs not meeting these criteria must be reanalyzed.
Lim its o f Q uantitation (LO Q ): The lower LOQ (LLOQ) is the lowest non-zero active standard in the caMxation curve; the peak area of the LLOQ must be at least 2X that of the average area counts for all prepared procedural blank(s). By definition, the measured value of the LLOQ must be within 30% of the theoretical value.
Dem onstration o f S pecificity: Specificity is demonstrated by chromatographic retention tim e (within 4% of standard) and the mass spectral response of unique ions.
13.3 Blanks - Method/Procedural Blanks and Trip
M ethod/Procedural Blanks: Multiple procedural blanks should be interspersed throughout the analysis batch and the analytical sequence. A t a minimum, method blanks are analyzed prior to instrument caftxation, prior to the analysis o f C C V samples, after every 10 sample Sections, and at the end ofthe analytical run.
The mean area counts (or area ratios when using IS caHbration) for each analyte must be less than 50% of the area count of the LOQ standard, tf the area counts of the procedural blanks exceed 50% of the LOQ standard, then the LOQ must be raised to the first standard level that meets criteria.
T rip B lank: A trip blank of ASTM Type I water (or lab equivalent) is prepared in a sample container in the laboratory and treated as a sample, including exposure to shipping, sampling site conditions, storage, preservation and all analytical procedures. The trip blanks results for each analyte are included with the reported sample results.
13.4 Data Accuracy and Precision - Analysis Batch
Lab C ontrol S p ires: The average recovery at each LCS level for each target analyte and appropriate SRS should be within 80-120% and the percent relative standard deviation of the recoveries must be less than or equal to 2 0 % . If the average recovery of a spiking level falls outside method acceptance, but at least 67% (6 out of 9) of LCS samples are within 20% of their respective nominal value (33% of the QC samples, not all replicates at the sam e concentration, may be outside 2 0 % of nominal value), the average recovery will be flagged as outside method acceptance criteria All LCS samples will be control charted as per ETS-12-012. If the average recovery of one o f the spicing levels exceeded the analytical method uncertainty as determined by ETS-12-012, that analytical batch uncertainty will be expanded for that particular study. The average recovery at each LCS level for mixed branched/Knear isomer PFOA and PFO S should be within 70-130% and the percent relative standard deviation of the recoveries must be less than or equal to 2 0 %.
Field D uplicates: The relative percent difference (R PD ) of duplicate samples should be less than 20% for the precision of sample preparation and analysis to be considered in control. Replicate samples not meeting the 20% RPD criteria are flagged and reported as outside of Q C acceptance criteria.
Field M atrix Spikes: FMS acceptance criteria are recoveries within 30% of the expected value for each target analyte and appropriate SRS. Sample data with FM S recovery outside of 30% but within 50% of the expected value are flagged and reported as outside of Q C acceptance criteria. Date with FM S recovery outside of 50% of the expected value are reported as NR, where NR is defined a s 'N o t Reportable* data outside of QC acceptance criteria. If FMS recovery could not be assessed because FM Ss were at an inappropriate level, then Laboratory Matrix Spikes (LMSs) m ay be substituted. If LM S recoveries are within 30% for each target analyte and SRSs the data are reportable but flagged as not meeting the FMS method acceptance criteria.
13.5 Analytical Method Uncertainty
Analytical method uncertainty for each target analyte and SRS is determined with control charted historical analysis batch LCS data foe the method and reported with each analysis batch.5 Uncertainty determinations
"5UQMnuceeatrnhttaoiifdnytuiynngicneUrMtnaceienarsttyuaribenamtsyeeidnnto)A.nnMIaNleyTtthEicoRadlNaMAppeTalIisOcuaNrteiAomnLednAet,mN" SoSn/eIscStoOrna/td1eEdEDdinitSiEoTTnA;SNE-1Dd2iAt-o0Rr1sD2:,Sc1.i7Lt0i.nR2g5. rrEeeflfeleirsreeonnncc,eeMs:(G.a.UR) EMosUs, lRGeAiuniC,daHentEdoMAth/.CeWIETxiAlpliCraemsGssiuo.indeo,f b.)Georgian, Thomas, "Estimation of Laboratory Analytical Uncertainty Using Laboratory Control Samples," Environmental Testing &
E TS -8-044.1
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Method o f Analysis fo r the Determ ination o f Perfluorinated Compounds in W ater by LC /M S /M S ; Direct Injection
A n alysis
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GLP10-01-01 ; Interim Repori 27 Analysis of PFOA in Surface Water Bert Jeffries Landfill - February 2012
are based on INTERNATIO NAL A N S/ISO /IED STANDARD 17025 reference (G UM , Guide to the Expression of Uncertainty in Measurement) and described in ETS-12-012. A t least thirty data points are required for determinino analytical method uncertainty The method uncertainty is defined as 2 x the standard deviation of the percent recoveries of the pooled lab control spires. W hile all LCS data points are control charted, only the most recent fifty data points are used for determining the method uncertainty.
W hen l^ s than thirty LCS data points have been generated fo ra given analyte, the analysis batch LCSs are used to determine the data uncertainty. If FMSs m eet the 30% recovery criteria at a level appropriate to the endogenous level, and the LCS m eet the 20% recovery criteria, then the uncertainty of the data is determined as within 1 0 0 2 0 % .
Analysis batch sample data with FM S recovery outside of 30% but within 50% of the expected value are flagged and reported as outside of Q C acceptance criteria with expanded uncertainties. Data with FM S recovery outside of 50% of the expected value are reported as NR, where NR is defined as "Not Reportable* data outside of Q C acceptance criteria. If FM S recovery could not be assessed because FM Ss were at an inappropriate level, then Laboratory Matrix Spikes (LM Ss) m ay be substituted. If LMS recoveries are within 30% for each target analyte and appropriate SRSs the data are reportable but flagged as not meeting the FM S method acceptance criteria with uncertainties of 30% . If FM S do not m eet the 30% recovery criteria, aMnSSdM hPMistettoe rlrSic^aMSl FP PMW%Sv dHMaPP%tHapP does Pnlort e x is t the aMnSSaSMlSy^s%tiSc^aMSl uPIncertMaMiSSnStWy SisM ertv aMlSu0aMte^d^e HortPnP aM s^HaMmSPPoMMtPe^te-MbFvT -1e^^aSmP ole basis the data may be reported with expanded uncertainty and are flagged.
13.6 Quantitation of PFOA/PFOS - Analysis Batch
Calibration standards consisting of mixed branched and linear isomer PFO S/PFOA are preferred. Quantitation is performed by integrating the linear and branched isomers together. Alternately, the linear and branched isomers can be intearated seoaratelv. aodvina the aoorooriats true value to each calibration curve point for each isomer. The LCS and samples are then quantitated by integrating the linear and branched isomers separately (requires separate analytical results files) and quantitating the resulting peak against the near or branched calbration curve. The results from both integrations are then summed to produce the final result. Integrating the linear and branched isomers separately m ay be helpful for those samples where the hnear/branched ratios do not closely match those of the reference standards.
However, for PFO S/PFO A target analytes, if the calbration standards are comprised of predominantly linear isomers only the method requires the addition of LCSs o f mixed branched/linear isomer P FO S /P FO A The purpose o f including these LCSs is to demonstrate quantitative equivalency (or quantitative bias) of the isomeric mix when using a predominantly linear PFOS or PFOA standard for calibration. Alternatively, in lieu of mixed branched and linear isomer PFO S/PFOA LCSs, mixed branched and linear isomer PFOS<PFOA TBM Ss m ay be applied to demonstrate method accuracy and precision.
An alternate method of quantitation can be performed whereby only the linear isomer of PFO S/PFOA is integrated and used for generating the calibration curve. The LCS and samples are then quantitated by integrating the linear and branched isomers separately (requires separate analytical results files) and quantitating the resulting peak against the in e a r calibration curve. The results from both integrations are then summed to produce the final result Integrating the linear and branched isomers separately reduces the oncolumn concentration for those samples that contain both linear and branched isomers of PFOA/PFOS. This ensures that the concentration detected is within the a range of the calibration cures that is comparable regardless of whether the calibration curve was generated using predominantly finear isomers of PFO S/PFOA or linear plus branched isomers of PFOS/PFOA.
14 Pollution Prevention and Waste Management
W aste generated when performing this method win be disposed of appropriately. The original samples will be archived at the 3M Environmental Laboratory in accordance with internal procedures.
AEMvneaaallsuyuasrtieisnm,gNeanontvdUemEncxbeperrrt/eaDsisneitcnyegminthbTeeerUs2tn0icn0eg0r".t,aciJ.nu)tTlyyaoy2lf0oN0r2,I.SBT.NM. eaansdurCeEm.enKtuRyeasttu,lNts.I"SdT.)TAedcahmnsic,aTl.NMo.,te"A122L97A,1G9u9i4deEdfoitriothne: "EGstuiimdaetliionnesoffor
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Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection
Analysis
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i
GLP10-01-01; Interim Report 27 Analysis of PFOA in Surface Water
Bert Jeffries Landfil - February 2012
15 Records
Each data package generated for a study must include all supporting information for reconstruction of the data. Information for the data package must include, but is not limited to the following items: study or project number, sample and standard prep sheets/records, instrument run log (instrument batch records, instalment acquisition method, summary pages), instrument results files, chromatograms, calibration curves, and data calculations.
16 Affected Documents
None.
17 Revisions1*
R evisio n N um ber
1
Sum m ary o f Changes
Section 1. Included the use ofinternal standard calibration by this method. Section 2. Included the use ofinternal standard calibration by this method. Included the use ofa solvent/watermixture 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 instrumentparameters to section 10 ofthe method. Section 7. Updated reference standards to include internal standards and surrogates. Changed concentration levels for waking standards and included the use ofinternal standards and surrogates. Section 8. Inserted a new section on sample bottle preparation. Section 9 Quality Control. This section was previously section 10 in ETS-8-044.0. Updated QC criteria to be consistent with method ETS-8-154.4. Section 10 Procedures. This section was previously section 8 (Sample Handling) in ETS-8044.0. Added detail regarding the preparation ofLCSs. 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 instrumentparameters. Section 12 Data Analysis and Calculations. This section was previously section 11 in ETS8-044.0. 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 ofanalytical method uncertainty and quantitation of PFOA/PFOS. Section 14 Pollution Prevention. This section was previously section 13 in ETS-8-044.0. Section 15 Records. This section was previously section 14 in ETS-8-044.0. Section 16 Affected Documents. This section was previously section 15 in ETS-8-044.0. Section 17 Revisions. This section was previously section 16 in ETS-8-044.0.
ETS-8-044.1
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Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection
Analysis
Page 61 of 61
!
*4
^ (= 7 ^
^SBWiWH
-
V \'}
GLP10-01-02; Interim Report 26 - Analysis of PFBS. PFHS. and PFOS In Surface Water Sample Collected at Bert Jeffries Landfill in Decatur. AL in February 2012
,n
lu ^
6:08
Study Title
Analysis of Perfluorooctane Sulfonate (PFO S), Perfluorohexane Sulfonate (P FH S ) and
Perftuorobutane Sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3
Site-Related Monitoring Program
Data Requirement
EPA T S C A Good Laboratory Practice Standards 4 0 C FR P art 792
Study Director
Jaisim ha Kesari P .E ., D EE W eston Solutions, Inc. 1400 W eston W ay
W est Chester, PA 19380 Phone: 610-701-3761
Author
Susan W olf 3M Environm ental Laboratory
Interim Report Completion Date
D ate of signing
Performing Laboratory
3M Environmental Health and Safety Operations Environmental Laboratory
3M Center, Bldg 260-05-N -17 S t Paul, MN 55144
Project Identification
G LP10-01-02-26
Total Number of Pages
77
Tlw tasting raportsd heroin mast ths rsquiramsnts of AN8MSOAEC 170252005 "General Requirements for the Competence of Teetlng and Calibration Laboratories", Inaccordance withthe A2LA Testing Certificata f
m 2052.01. Tastine thatoompHaswHhthisInternationalStandardalso meetsprinciplesofB O 9001:2000.
Testing Cert 2052.01
This page has been reserved for specific country requirements.
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ABneratlGyJesUifsfPro1ie0fs-P0LF1aB-n0Sd2,f;iPIlnFtHeFreSimb,rauRnaedrpyPo2Fr0tO21S26 GLP Co m pu a n c e S tatem ent
Report TBe: Interim Report 26 Analysis of PFBS, PFH S, and PFO S in Surface W ater Samples Collected at Bert Jeffries Landfill in Decatur, AL in February 2012 Study: Analysis of Perfluorooctane Sulfonate (PFO S). Perfluorohexane Sulfonate (PFHS) and Perfluorobutane Sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program. This analytical phase was conducted in compliance with Toxic Substances Control Act (TSGA) Good Laboratory Practice (G LP) Standards, 40 C FR 792. with the exceptions listed below:
These are environmental samples where there is no specific test substance, no specific test system and no dosing of a test system.
The reference substances have not been characterized under the GLPs and the stability under storage conditions at foe test site have not been determined under GLPs.
Page 3 of77
GLP10-01-02; Interim Report 26 Analysis of PFBS, PFHS, end PFOS Bert Jeffries LandtW - February 2012
Q u a lity A ssu r a n c e Statem ent
Report Title: Interim Report 26 - Analysis of PFBS, PFHS, and PFO S in Surface W ater Samples
Collected at Bert Jeffries Landfill in Decatur, AL in February 2012
Study: Analysis of Perfluorooctane Sulfonate (PFO S), Perfluorohexane Sulfonate (PFH S) and Perfluorobutane Sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program.
This analytical phase was audited by the 3M Environmental Laboratory Quality Assurance Unit (QAU), as indicated in the following table. The findings ware repotted to the principal investigator (P .I.), laboratory management and study director.
In sp e ctio n Dates 4 /2 /1 2 -4 /3 /1 2
Phase Data and Report
D ate Re<ported to
T e stin g F a c lity M anagem ent
S tu d y D ire cto r
4/9/12
4/6/12
QAU
H - /J L
D a te
Ta b le o f Co ntents
G LP Compliance S tatem ent.............................................................................................................................3
Quality Assurance Statem ent........................................................................................................................... 4
Table of Contents................................................................................................................................................ 5
List of T ab les....................................................................................................................................................... 6
1 Study Information........................................................................................................................................ 7
2 Sum m ary..............................................
8
3 Introduction................................................................................................................................................... 9
4 Test & Control Substances....................................................................................................................... 9
5 Reference Substances.............................................................................................................................10
6 Test System ............................................................................................................................................... 11
7 Method Sum m ary......................................................................................................................................12
7.1 M ethods.....................................................................................................................................12
7.2 Sam ple Collection.................................................................................................................... 12
7.3 Sample Preparation................................................................................................................. 12
7.4 Analysis..................................................................................................................................... 12
8 Analytical Results...................................................................................................................................... 13
8.1 Calibration................................................................................................................................. 13
8.2 System Suitability.................................................................................................................... 14
8.3 Limit of Quantitation (L O Q ).................................................................................................... 14
8.4 Continuing Calibration.............................................................................................................14
8.5 Blanks.........................................................................................................................................14
8 .6 Lab Control Spikes (L C S s)..................
14
8.7 Analytical Method Uncertainty............................................................................................... 16
8.9 Field Matrix Spikes (F M S )........................................................................................................16
Page5of77
g Data Summary and Discussion..................................................................................................... 16 10 Conclusion................................................................................................................................................. 20 11 Data/Sam pte Retention.......:................................................................................................................. 20 12 Attachm ents..............................................................................................................................................20 13 Signatures................................................................................................................................................. 21
U s t o f Tables
Table 1. Summarized PFBS, PFHS, and PFO S Results (Jeffries Landfill Site, Feb 2012)......8 Table 2. Sample Description Key Code.......................................................................................... 11 Table 3. Instrument Parameters.............................................. i....................................................... 12 Table 4. Liquid Chromatography Condidons..................................................................................13 Table 5. Mass Transitions................................................................................................................. 13 Table 6 . Limit of Quantitation (LO Q )................................................................................................14 Table 7. Laboratory Control Spike R ecovery................................................................................15 Table 8 . Analytical Uncertainty........................................................................................................ 16 Table 9. Field Matrix Spice Levels...................................................................................................16 Table 10. JPAL SW ET01 120228................................................................................................... 17 Table 11. JPAL S W E T 0 2 120228................................................................................................... 17 Table 12. JPAL SW E T 0 3 120228................................................................................................... 18 Table 13. JPAL SW E T 0 4 120228................................................................................................... 18 Table 14. Trip Blank 1 2 0 2 2 8 ........................................................................................................... 19
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1 Study information
Sponsor
3M Company
Sponsor Representative
Gary Hohenstein 3M EHS Operations 3M Building 224-5W -03 Saint Paul, MN 55144-1000 Phone: (651) 737-3570
Study Director
Jaisimha Kesari, P.E., DEE Weston Solutions, Inc. W est Chester, PA 19360 P h o n e :(6 1 0 )7 0 1 -3 7 6 1 F a x :(6 1 0 )7 0 1 -7 4 0 1 j.Kesari@westonsolutions.com
Study Location
Testing Facility
3M EHS Operations 3M Environmental Laboratory Building 260-5N -17 S t Paul, MN 55144
Study Personnel
W illiam K. R eagen, P h.D ., 3M Laboratory M anager
Cleston Lange, Ph.D., Principal Analytical Investigator, ldanoe@ mmm.com1: phone (651}-733-9860
Susan W olf, 3M Analyst
C helsie Grochow, Analyst
Kevin Eich, Analyst
Kelly Ukes, Analyst
Jonathan S teege, Analyst
Study Dates
Study Initiation: March 8 ,2 0 1 0 Interim 26 Experimental Termination: March 14,2 0 1 2 Interim Report Completion: Date of Interim Report Signing
Location of Archives
All original raw data and the analytical report have been archived a t the 3M Environmental Laboratory according to 4 0 C FR P art 792. The test substance and analytical reference standard reserve sam ples are archived a t the 3M Environm ental Laboratory according to 4 0 C FR P art 792
Page 7 of77
2 Summary
The 3M Environmental Laboratory received surface water samples from four different locations located at Jeffries Landfill in Decatur, AL. A total of nineteen sample bottles were received at the 3M Environmental Laboratory for perfluorooctane sulfonate (PFO S), perfluorohexane sulfonate (PFHS) and perfluorobutane sulfonate (PFBS), and included duplicate surface water samples and two field matrix spike (FM S ) samples from each sampling location. A set of trip blank samples; single trip blank containing MINi-QTM water and two trip blank spikes, were included with the sample bottles. All samples were logged into the laboratory information management system (LIM S) under project G LP10-01-0226. The surface water samples and trip blanks were received from Weston personnel on March 2, 2012. All of the samples were prepared and analyzed for PFBS, PFH S, PFO S, and the surrogate recovery standard 13C4-PFO S, following 3M Environmental Laboratory Method ETS-8-044.1.
The average measured PFBS, PFHS, and PFO S concentrations are summarized in Table 1. The trip
blank sample was below the lower limit of quantitation (LLOQ ) for alt analytes, indicating adequate control of sample contamination during shipping and sample collections. The analytical method uncertainties associated with the reported results are: PFBS 22% , PFHS + 1 9 % and PFO S + 1 5 % .
Table 1. Summarized PFBS, PFHS, and PFOS Results (Jeffries Landfill Site, Feb 2012).
3M U M SID G LP10-01-02-026-005 G LP10-01 -02-026-006
G LP 10 -0 1 -0 2 -0 2 6 0 0 9 GLP16 0 1 -0 2 0 2 6 0 1 0
GLP16 0 1 0 2 0 2 6 0 1 3 GLP16 0 1 0 2 0 2 6 0 1 4
GLP10 0 1 0 2 0 2 6 0 1 7 GLP16 0 1 0 2 0 2 6 0 1 8
GLP16 0 1 0 2 0 2 6 0 2 5
Sample Description JP A L -S W -E T 010-120228 JPAL-SW -ET01 -D B -120228
Average
J tR P D S a m p ie /S a m p le D u p
J PA L-SW -ET02-0-120228 JPA L-SW -ET02-D B -120228
A v e ra g e % R P D S a m p ie /S a m p le D u p
JPA L-S W -ET03O -120228 JPAL-SW -ET03-DB-120228
A v e ra g e % R P D S a m p ie /S a m p le D u p
JPA L-SW -ET04-0-120228 JPA L-S W -ET04-D B -120228
A v e ra g e % R P D S a m p ie /S a m p le D u p
| JPA L-S W -TR IP 1O -120228
PFBS Concentration
(ng/mL) 0 .0345 0 .0 3 6 2 0.0354
4.8
< 0 .0 2 5 0 < 0 .0 2 5 0 <0.0250
NA
< 0 .0 2 5 0 < 0 .0 2 5 0 <0.0250
NA
< 0 .0 2 5 0 < 0 .0 2 5 0 <0.0250
NA <0.0250
PFHS Concentration
(ng/tnL) < 0 .0 2 5 0 < 0 .0 2 5 0 <0.0250
NA
< 0 .0 2 5 0 < 0 .0 2 5 0 <0.0250
NA
< 0 .0 2 5 0 0 .0 2 5 2 0.0252 NATM
< 0 .0 2 5 0 < 0 .0 2 5 0 <0.0250
NA <0.0250
_ PFOS Concentration
(ng/mL) 0 .0 3 0 2 0 .0 3 0 2 0.0302
0.0
0.0661 0 .0 5 9 3 0.0627
11
0 .3 0 3 0 .3 0 3 0.303
0.0
0 .1 6 6 0 .1 5 9 0.163
4.3 <0.0232
NA = Not Applicable
The analytical method uncertainties assodated with th e reported results are: PFBS 2 2% , PFH S 19 % , and PFOS 15% .
(1 ) A sam ple/sam pie duplicale RPO could not be determ ined since the concentration for the primary sam ple was BLOQ for PFH S.
3 Introduction
This analytical study was conducted as part of the Phase 3 Environmental Monitoring and Assessment Program for the 3M facility located in Decatur, Alabama. The objective of the overall program is to gain information regarding concentrations of perfluorooctane sulfonate (PFO S), perfluorohexane sulfonate (PFH S) and perfluorobutane sulfonate (PFBS), in various environmental media such as groundwater, soils and sediments that are associated with and near the Decatur facility. This analytical study was conducted to analyze surface water samples collected from four locations a t or near Jeffries Landfill in Decatur, AL for PFBS, PFH S, and PFOS in an effort to characterize surface water conditions. The 3M Environmental Laboratory prepared sample containers (250 mL high-density polyethylene bottles) which were shipped to Decatur, AL Weston personnel prior to field sampling. Sample containers for each sampling location included a field sample, field sample duplicate, and two field matrix spike samples. Each empty container was marked with a "fill to here* line to produce a final sample volume o f 200 m L Containers designated for field matrix samples were fortified with an appropriate matrix spike solution containing PFBS (linear isomer), PFHS (linear isomer), and PFO S (linear and branched isomers) prior to being sent to the field for sample colection. All sample bottles included the addition of 18Or PFBS, 13C3-PFHS, and 13C-PFOS (internal standard) a t a nominal concentration o f 1 ng/mL. All sample bottles also included the addition o f13C-PFOS (surrogate recovery standard) at a nominal concentration of 0.1 ng/mL. See section 8 .8 of the report for field matrix spike levels. Samples were prepared and analyzed according to the procedure defined in 3M Environmental Laboratory method ETS-8-044.1 "Method of Analysis for the Determination of Perfluorinated Compounds In W ater by LC/MS/MS; Direct Injection Analysis''. The use of internal standards was used to aid in the data quality objectives. T able 1 summarizes the average PFBS, PFHS, and PFO S concentrations for the duplicate surface water samples collected and the trip blank sample. Tables 10-14 summarize the individual sample results and the associated field matrix spike recoveries. All results for the quality control samples prepared and analyzed with the samples are reported and discussed elsewhere in this report
4 Test & Control Substances
There was not a test substance or control substances in the classic sense of a GLP study. This study was purely analytical in nature.
Page 9 of77
5 Reference Substances
Chem ical Nam e
Chem ical Formula Identifier
Use Source Expiration Date Storage Conditions Chem ical Lot Num ber TC R Number Physical Description Purity
mn
(prifcHnhM HiUy Itn s a r) Potassium
Perlluorobutane sulfonate C 4F9S O 3K
NA Target Analyte Reference
Standard 3M
0 1 /1 0 /2 0 1 7
Frozen
4 1 -2 6 0 0 -8 4 4 2 -5 T C R -1 2 1
W hite Powder
9 6 .7 %
"ostras
[18Oj}-Amm onium Perfiuorebutanesulionate
CiF^OzJO-NlV
NA
Internal Standard
RT1 International 0 3 /0 9 /2 0 1 5 Frozen 1 1 5 4 6 -1 0 7 -2
T C R -1044, TC R -1040 Liquid >99%
R ifflfM IO C S llb tlt llM
Chem ical Nam e Chem ical Formula Identifier Use Source Expiration Date Storage Conditions Chem ical Lot Num ber TCR Number Physical Description Purity
PFHS (L in ea r) Sodium Perfluotohexane sulfonate C sF iaS O a'N a*
L -P F H X S Target Analyte Reference
Standard W eK ngton 0 3 /2 5 /2 0 1 8
Frozen
LPFHXSAM08 TC R 08-0018
Crystalline
100%
"C rF F M *
Sodium Perfluorohexanesulfonate
13C 3 12C 3 F i3S 0 3 'N a * M PFC -C -0511
Internal Standard
W ellington 0 5 /2 5 /2 0 1 4
Frozen M PFC -C -0511 T C R 11-0016
Liquid 5 pig/rnL<1>
"C rP FH S Sodium
Perfluorohexanesulfonate 13C 312C 3F 13S 0 3'N a * M PFC -C -0112
Internal Standard
W ellington 0 1 /2 4 /2 0 1 5
Frozen M P F C -C -0112 TC R 12-0004
Liquid S irg /M . 01
(1) Custom mixture ofSevan mage labotad ( a C ) pertluoroafcytcartooxyfk:adds, two mass labeled (13C) peffluoroalkylsdfonat** and on mass-labelsd (C ) pedluoro-1-actanesulfonamide.
Page 10 of77
Chem ical Nam e
Chem ical Formula Identifier Use Source Expiration Date Storage Conditions Chem ical Lot Num ber TC R Number Physical Description Purity
pros
(Linear + Branched) Potassium
Perfluorooctane sulfonate
C 1JF17S O 3 K *
Br-PFO SK
Target Analyte Reference Standard
W ellington
0 3 /1 7 /2 0 1 4 ; 1 2 /0 1 /2 0 1 4
Frozen
brPFO SK0708; b rP F O S K im T C R 11-0010; T C R 11-0041
Liquid
9 9 .9 %
"C r+ros Sodium
Perfluorooctane sulfonate
13C412C4F17S03'Na*
MPFOS Surrogate W efflngton
0 9 /0 8 /2 0 1 3
Frozen M PFO S0910
TC R 10-0044-7/9
Liquid >98%
,1Cr PFOS Sodium
Perfluoruoctane sulfonate
^ C s F ^ O s T ia * M PFC-C-0511
Internal Standard W ellington 0 6 /2 5 /2 0 1 4
Frozen M P F C -O 0511
T C R 11-0016
Liquid 5M g /m L (,)
(1) Custom mixture ofSevan mass-labeled (13C) pertuoroakytaartxwyfc adds, two mass labeled (C ) perfluoroaMsutfonates and one mass-labeled (,aC) perftuoro-1-octanesulfonariide
iaCrPPOS Sodium
Perfluorooctane sulfonate
^CaFuSOaNa*
M P F C C -0112
Internal Standard W eH ngton 0 1 /2 4 /2 0 1 6
Frozen
M PFC -C -0112
T C R 1 2 -0 0 0 4
Liquid 5 pg/m L(1>
6 Test System
The test systems for this study are surface water samples collected from wells located in Decatur, AL
by W eston Solutions, Inc. personnel. Samples for this study are ` real world' samples, not dosed with a specific lot of test substance.
Table 2. Sample Description Key Code.
String Number Exempte
1 2 3
4 5
Strino Deecriptor
Example
J P A L -S W -E T 01 -0 -1 2 0 2 2 8 S a n to la L o c a tio n S a m p le T v p a
J P A L mJ a m e s Property. A la b a m a S W S u rfa c e W a te r
W eSD
E x a m p le : E T 0 1
S am pB n a D a te
S a m p le Type
E T -E a s te r n trib u ta ry to M a tta rti C re e k 1 2 0 2 2 8 - F eb ru ary 2$. 2012 0 " p rim a ry a m p le
D B d u p lic a ta s a m p le
L S m lo w tp lk e
H S - N a h s p ik e
Page 11 of 77
i
7 Method Summary
7.1 Method
Analysis for all analytes was completed following 3M Environmental Laboratory method ETS-8-044.1 "Method of Analysis for the Determination ofPerfluorinated Compounds In W ater by High Performance Liquid Chromatography/Mass Spectrometry Direct Injection Analysis*.
7.2 Sample Collection
Samples were collected in 250 mL NalgeneTM (high-density polyethylene) bottles prepared at the 3M Environmental Laboratory. Sample bottles associated with G LP10-01-02-26 were returned to the laboratory at ambient conditions on March 2 ,2 0 1 2 . Samples were stored refrigerated at the laboratory after receipt A set of laboratory prepared Trip Blank and Trip Blank field matrix spikes were sent with the sample collection bottles.
7.3 Sample Preparation
Samples were prepared by removing an aliquot of the well mixed sample and placing it in an autovial for analysis.
During the preparation of the laboratory control samples, an aliquot of a separate internal standard spiking solution was added to the laboratory control samples (nominal concentration of 1 ng/mL). The samples bottles were spiked with an internal standard mix at a nominal concentration of 1 ng/mL prior to being sent to the field for sample collection
7.4 Analysis
All study samples and quality control samples were analyzed for PFBS, PFHS, and PFO S using high performance liquid chromatography/ tandem mass spectrometry (H PLC /M S/M S). Detailed instrument parameters, the liquid chromatography gradient program, and the specific mass transitions analyzed are described in the raw data hard copies placed in the final data packet, and are briefly described below.
Table 3. Instrument Parameters.
Instrument Name Analytical Method Followed Analyst* Date Liquid Chromatograph Guard column Analytical column Injection Volum M u s SM droflM ter Ion Source Electrode Polarity Software
E T S G in o er ETS-8-044.1 3 /7 /1 2 - PFBS and PFHS Anient 1100 Betas! C18 (4.6 mm X 100 mm). 5u Betas! C18 (4.6 mm X 100 mm). 5u
25 uL Aodied BiosystamsAPI 5000
Turbo Stray Turbo ion electrode
Neoative Analyst 1.42
ETS McCoy ETS-8-044.1 3/13/12-P F O S Anient 1290 Betas! C18 (4.6 mm X 100 mm). 5u Betas! C18 (4.6 mm X 100 mm), 5u
50 uL Aonlied Bioevstems API 5500
Turbo Scray Turbo ion electrode
Neoative Analyst 1.52
Page 12 of 77
Table 4. Liquid Chrom atography C onditions.
*M>JT Num ber
Total Tim * (m in)
0 1 2
3 4 5 Sbo M em ber
0.0 ' 2.0 14.5 15.5 16.5 20.0 Total Tim (m in)
0 0.0 1 2.0 2 14.5 3 15.5 4 16.5 5 20.0
Flow Rata (jM Jm ln)
PeccantA (2 mM arm onium acetate)
ETS-8-044.1 Analyzed 3/7/12
750 97.0 750 97.0
750 5.0
750 5.0
750
750 Flow Rate (fi/m in )
97.0
97.0 P erce n tA
(5 mM ammonium acetate: 0.01% acetic add)
ETS-8-044.1 Analyzed 3/13/12 750 97.0 750 97.0 750 5.0 750 5.0 750 97.0 750 97.0
P erce n tB (m ethanol)
3.0 3.0 95.0 95.0 3.0 3.0 P erce n tB (a c e to n itrile )
3.0 3.0 95.0 95.0 3.0 3.0
Table 5. Mass Transitions.
A n alyte PFBS PFHS
PFOS f ' CJ-PFOS
Mass Transition Q 1/Q 3
200(80 290(90 300(00 300(00 490/80 400(00 400/130 603(80
R eferen ce M aterial Structure
Linear
L in e a r
L in e a r Branched
U near
M an ad Standard fO J -P F B S fC J -P F H S { ` CJ-PFOS f ' CJ-PFOS
Mass Transition C1/Q 3 303/84 402/80
507/80 607/00
Dwell tin e was 50 msec for each transition. The individual transitions were summed to produce a total ion chromatogram' (TIC), which was used forquantitation.
8 Analytical Results
8.1 Calibration
Samples were analyzed using a stable isotope internal standard calibration curve. Calibration standards were prepared by spiking known amounts of the stock solution containing the target analytes into a laboratory-prepared synthetic groundwater containing calcium and magnesium. A separate internal
standard spiking solution w as prepared and an aliquot was added at the sam e level to a l calibration standards and laboratory control samples a t a nominal concentration of 1 ng/mL. A calibration curve ranging from approximately 0.025 ng/mL to 100 ng/mL (0.025 ng/mL to 10 ng/mL for 13C4-PFO S surrogate) was prepared. The reference standard used for the calibration standards for PFOS contained both linear and branched isomers.
Page i3 o f7 7
A quadratic, 1/x weighted, calibration curve of the standard peak area/peak area ratios was used to fit the data for each analyte. The data were not forced through zero during the fitting process. Calculating the standard concentrations using the peak area/peak area ratios and the resultant calibration curve confirmed accuracy of each curve point
Each curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method calibration accuracy requirements of 10025% (10030% for the lowest curve point) were m et for all analytes. The correlation coefficient (r) was greater than 0.995 for PFBS, PFH S, PFO S, and 13C4-PFOS.
8.2 System Suitability
A calibration standard was analyzed four times at the beginning of each analytical sequence to demonstrate overall system suitability. The acceptance criteria o f less than or equal to 5% relative standard deviation (R SD ) for peak area and retention tim e criteria of less than or equal to 2% RSD was m et for PFBS, PFHS, PFO S, a id 13C4-PFO S.
8.3 Limit of Quantitation (LOQ)
The LOQ for this analysis is the lowest non-zero cafibration standard in the curve that meets linearity and accuracy requirements and for which the area counts or area ratio are at least twice those o f the appropriate blanks. The LOQ for all analytes can be found in Table 6 .
Table 6. Limit of Quantitation (LOQ).
PFBS L O Q .n o /n A .
0 .0 2 5 0
PFHS L O Q , n o /m L
0 .0 2 5 0
PFO S L O Q .n o /n A
0 .0 2 3 2
8.4 Continuing Calibration
During the course of each analytical sequence, continuing calibration verification samples (CCVs) were analyzed to confirm that the instrument response and the initial calibration curve were still in control. All CCVs met method criteria of 100% 25% for PFBS, PFHS, PFO S. and 13C4-PFOS.
8.5 Blanks
Two types of blanks were prepared and analyzed with the samples: procedural blanks and trip blanks. Procedural blank results were reviewed and used to evaluate method performance to determine the LOQ. Trip blanks reflect the shipping and sample collection conditons the sample bottles and samples experience.
8.6 Lab Control Spikes (LCSs)
Low, mid, and high lab control spikes were prepared for the target analytes and analyzed in triplicate, while only low and high lab control spikes were prepared for the 13C4-PFO S surrogate. LCSs were prepared by spiking known amounts of the analyte into synthetic groundwater to produce the desired concentration. The spiked water samples were then prepared and analyzed in the sam e manner as the
samples. The method acceptance criteria, average of LCS at each level should be within 100% 20%
with an RSD 20% , was m et for aU analytes.
The (blowing calculations were used to generate data in Table 7 for laboratory control spikes.
100LCS PercentRecovery = Calculated Concentration
%
Spike Concentration
LCS% RSD - Standard dw lalion. " W * * * 100% average LCS recovery
Page 14 of 77
Table 7. Laboratory Control Spike Recovery.
ETS-8-044.1 Analyzed 3/7/12
L a b ID
S p ik e d C o n c e n tra tio n
(n o /m L I
PFBS
C a lc u la te d C o n c e n tra tio n
(n o /m U
^R ecovery
S p ik e d C o n c e n tra tio n
(n g /m L )
L C S -1 2 0 3 0 6 -1 L C S -1 2 0 3 0 6 -2 L C S -12 0 3 0 6 -3 A verage % R S D
0 .1 9 8 0 .1 % 0 .198
0 .209 0 .2 0 9 0 .2 0 7 105% 0.95%
105 106 104
0 .198 0 .198 0 .198
L C S -12 0 3 0 6 -4 L C S -12 0 3 0 6 -5 L C S -12 0 3 0 6 -6 A verage % R S D
1.98 1 .9 8 1 .9 8
2 .1 7 2 .1 9 2 .0 9 109% 2 .4 %
110 111
106
1 .9 8 1 .9 8 1 .9 8
L C S -1 2 0 3 0 6 -7 L C S -12 0 3 0 6 -8 L C S -1 2 0 3 0 6 -9 A verage % RSD
1 9 .9 1 9 .9 1 9 .9
1 8 .9 18.1 1 9 .8 95.3% 4 .5 %
95.1 91.1 9 9 .6
1 9 .8 1 9 .8 19.8
PFH S C a lc u la te d C o n c e n tra tio n
In o /m L )
0.191 0 .182 0 .185 9 3 .8% 2 A %
2 .0 8 1.92 1.94 100% 4 .3 %
1 8 .5 18.1 1 9 .2 93 .9% 3 .0 %
^R ecovery 9 6 .3 9 1 .8 9 3 .3
105 97.1 9 8 .0
9 3 .5 9 1 .3 9 6 .9
ETS-8-044.1 Analyzed 3/13/12
P F O S (L in e a r * B ra n c h e d )
1 iC * -P F O $ s u r ro g a te
L a b ID
S p ik e d C o n c e n tra tio n
(n o tn & i
C a lc u la te d C o n c e n tra tio n
fn o A n L )
^R ecovery
S p ik e d C o n c e n tra tio n
(n o /m U
C a lc u la te d C o n c e n tra tio n
(n o /m U
^R ecovery
L C S -1 2 0 3 0 6 -1 L C S -1 2 0 3 0 6 -2 LC S -12 0 3 0 6 -3 A verage % RSD
0 .1 8 4 0 .184 0 .184
0 .178 0 .170 0 .1 7 0 94.1% 2 .7 %
9 7 .0 9 2 .6 9 2 .6
0 .1 8 9 0 .169 0 .189
0 .2 2 1
0.2 15 0.2 25 1 1 7 % 2 .2 %
117 114 119
LC S -12 0 3 0 6 -4 LC S -12 0 3 0 6 -5 L C S -1 2 0 3 0 6 -6 A verage % R S O
1 .8 4 1 .8 4 1 .8 4
1 .7 6 1 .7 2 1.71 94.0% 1 .5 %
9 5 .6 9 3 .6 9 2 .9
1 .8 9 1 .8 9 1 .8 9
2 .2 1
2 .1 4 2 .1 4 1 1 4 % 2 j0%
117 113 113
L C S -12 0 3 0 6 -7 LC S -12 0 3 0 6 -8 LC S -12 0 3 0 6 -9 A verage % R SD
1 8 .4 1 8 .4 1 8 .4
17.1 16.6 1 7 .4 92.5% 2 .1 %
9 2 .8 9 0 .4 9 4 .3
NA NA NA
NA NA NA NA
NA NA NA
N A > Noi Applicable
Page 15 of 77
GLP10-01-02; Interim Report 26 Analysis of PFBS, PFHS, and PFOS Bert Jeffries LandfNI - February 2012
8.7 Analytical Method Uncertainty
Analytical uncertainty is based on historical Q C data that is control charted and used to evaluate method accuracy and precision. The method uncertainty is calculated following E TS -12-0122. The standard deviation is calculated for the set of accuracy results (in % ) obtained for the Q C samples. The expanded uncertainty is calculated by multiplying the standard deviation by a factor o f 2 , which corresponds to a confidence level of 95%.
Table 8. Analytical Uncertainty.
A n alyte PFBS PFHS PFOS
S tand ard D eviatio n
1 0 .8
9 .4 2 7 .6 0
M ethod U ncertainty 2 2 % 19% 15%
8.8 Field Matrix Spikes (FMS)
Low, mid, and high field matrix spikes (FM S ) w ere collected at each sampling point to verify that the analytical method is applicable to the collected matrix. Field matrix spikes w ere generated by adding a measured volume o f field sample to a container spiked by the laboratory with PFBS (linear), PFHS (inear), and PFO S (linearr-branched) prior to shipping sample containers for sample cotection. Field matrix spike recoveries within method acceptance criteria of 10030% confirm that ` unknown' components in the sample matrix do not significantly interfere with the extraction and analysis of the analytes of interest. Field matrix spike concentrations must be 50% of the sample concentration to be considered an appropriate field spike. Field matrix spkes are presented in section 9 of this report.
Table 9. Field Matrix Spike Levels.
S am pling Location
S p ik e Level
All locations and Trip Blank
Low Htah
PFBS, n g faiL
1 .0 0
1 0 .0
PFHS, n g/m L
0 .9 9 6 9 .9 8
PFOS, n g/m L
0 .9 2 8 9 .2 8
FM S Recovery ( Sam ple Concentration o f F M S -A v e ra g e Concentration:Field Sam ple & Field Sam ple Pup.) 100% Spike Concentrator)
9 Data Summary and Discussion
The tables below summarize the sample results and field matrix sp ke recoveries for the sampling locations as well as the Trip Blank. Results and average values are rounded to three significant figures according to EPA rounding rules. Because of rounding, values m ay vary slightly from those listed in the raw data. Field matrix spike recoveries meeting the method acceptance criteria of 30% , demonstrate that the method was appropriate for the given matrix and their respective quantitative ranges.
Page 16 of 77
Table 10. JPAL SW ET01 120228
3M U M S ID
Descrtotion
GLP10-01-02-26-005 JPAL-SW-ET01-0-120228 GLP10-01-02-26-006 JPAL-SW-ET01-OB-120228 GLP10-01-02-26-007 JPAL-SW-ET01-LS-120228 QLP10-01-02-26-008 JPAL-SW-ET01-HS-120228
A ven a Conce.ntntion (no/m L) t %RPD
NM NotA ppicable
PFBS
PFHS
PFOS
C o ncentn tio n
(ngAnL)
%Recovery
0.0345 0.0362
1.08 10.4
NA NA 104 104
0.0354 nafinL 4.8%
C o ncentntion % R ecovery
<0.0250
NA
<0.0250
NA
0.946
94.8
8.62 86.4
<0.0250na/m L
C o ncentn tio n
(na/m
%Recoverv
0.0302 0.0302 0.863
NA NA 89.7
8.38 90.0
0.0302n aM L i 0.0%
1sC<PFOS
X lk c o iw y 109 102 110 110
108% 13%
Table 11. JPAL SW ET02 120228
3M U M S ID
Descrtotion
GLP10-01-Q2-26-009 JPAL-SW-E702-0-120228 GLP10-01-02-26-010 JPAL-SW-ET02-OB-120228 GLP10-01-02-26-011 JPAL-SW-ET02-LS-120228
C3LP10-01-Q2-26-012 JPAL-SW-ET02-HS-120228
A ven ae Concentration (no/m t %RPD
N A = N A p p *ca b le
PFBS
C o ncentntion
(na/m L)
% Recoverv
<0.0250
NA
<0.0250
NA
1.08 108
9.63 96.3
<0.6250 na/mL
PFHS
C o n cen tn tio n
(na/m L)
X R teo m y
<0.0250 <0.0250
NA NA
1.030
103
8.640
86.6
<0.0250na/m L
PFOS
C o ncentn tio n
<0*nU
%Recavery
0.0661
NA
0.0593
NA
0.924
92.8
8.45 90.4
0.0827 nafm L 11%
13C4 PFOS
%Rocovery 107 106 109 107
107% 1.2%
Page 17of 77
Table 12. JPAL SW ET03120228
PFB S
PFH S
PFO S
**C tP F O S
3 M U M S ID
D e s c r ip tio n
G L P 10-01-02-26-013 JPAL-SW -ET03-0-120228 G LP10-01-02-26-014 JPA L-SW -ET03-D 6-120228 G L P 10-01-02-26-015 JPAL-SW -ET03-LS-120228 G LP10-01-02-26-016 JPAL-SW -ET03-H S-120228
A v e ra g e C o n c e n tra tio n (n a /m L ) 1 % R P D
C o n c e n tra tio n (n a /M J
% R e c o v e rv
< 0 .0 2 5 0 < 0 .0 2 5 0
1 .0 5
NA NA 105
9 .1 4
9 1 .4
< 0 .0 2 5 0 n o A n L
C o n c e n tra tio n fn o A n L )
% R e c o v e ry
<0.0250 0.0252 0.992 8.820
NA NA 96.9 88.1
0 .0 2 5 2 n o A n L m
C o n c e n tra tio n (n g to U
XM cnw y
0 .3 0 3
NA
0 .3 0 3 1 .1 3
NA 89.1
8 .7 2
9 0 .7
0 .3 0 3 n n tm L 0 .0 %
'A R a c o v e r y
109 109 103 106
1 0 7 % 2 .7 %
NA = Not Appicable (1) A sampte/sampte duplicate RPD could not be detemnined since the concentration ofthe primaiysample was BLOQ for PFHS.
Table 13. JPAL SW ET04 120228
3 M U U S ID
D e s c r ip tio n
G LP10-01-02-26-017 JPAL-SW -ET04-0-120228 G LP10-01-02-26-018 JPAL-SW -ET04-DB-120228 G LP10 -0 1 -0 2 -2 6 0 1 9 JPA L-SW -ET04-LS-120228 G LP10 0 1 -0 2 -2 6 0 2 0 JPAL-SW -ET04-HS-120228
A v e ra g e C o n c e n tr a tio n (n g A n L ) % R P D
NA = Not Applicable
PFB S
PFH S
PFO S
13C , P F O S
C o n c e n tra tio n (n o /m L )
% R e c o v e rv
< 0 .0 2 5 0
NA
< 0 .0 2 5 0 1.14 10.6
NA 114 106
< 0 .0 2 5 0 n g fm L
C o n c e n tra tio n (n g /M J
% R e c o v e rv
<0.0250 <0.0250
0.931 8.45
NA NA 9 3 .3 8 4 .7
0 .0 2 5 0 n o A n L
C o n c e n tra tio n (n o /m U
% R e c o v e ry
0 .1 6 6 0 .1 5 9 1 .0 3 8 .4 7
NA NA 9 3 .5 8 9 .5
0 .1 6 3 n g /m L t 4 .3 %
'/R e c o v e r y
113 109 110 105
1 0 9 % 3 .2 %
Page 18 of 77
Table 14. Trip Blank 120228
3 M U M S ID
D e s c rto tio n
GLP10-01-02-26-025 JPAL-SW -TRIP1-0-120228 GLP10-01-02-26-026 JPAL-SW -TRIP1-LS-12Q 228 G LP 10-01-02-26-027 JPA L-S W -TR IP 1-H S-120228
P FB S
PFH S
PFO S
C o n c e n tra tio n ( n g /m L )
< 0.0250 1 .0 6 9 .3 2
% R e c o v e ry
NA 106 932
C o n c e n tra tio n (n g A n Q
< 0 .0 2 5 0 0 .9 4 7 9.21
XRgcow y NA 9 4 .9 9 2 .3
C o n c e n tra tio n (n o /h tL )
< 0 .0 2 3 2 0 .8 09 8 .0 7
^R ecovery NA 872 8 7 .0
n C 4PFO S
X fk c o w ry 108 109 107
NA = Not Applicable
Page 19 of 77
10 Conclusion
Laboratory control spikes and field matrix spikes were used to determine the analytical method accuracy and precision for PFBS, PFHS, and PFO S. Analysis was successfully completed following 3M Environmental Laboratory method ETS-S-044.1 described herein.
11 Data/Sample Retention
All remaining samples and associated project data (hardcopy and electronic) will be archived according to 3M Environmental Laboratory standard operating procedures.
12 Attachments
Attachment A: Protocol Amendment 26 (General Project Outline) Attachment B: Representative Chromatograms and Calibration Curves Attachment C: Analytical Method-ETS-8-044.1
Page 20 of77
GLP10-01-02; Interim Report 26 ABneaitlyJseifsfroiefsPLFaBnSd.fiPl F- HFeSb. raunadryP2F0O1S2
13 Signatures
Cleston Lange, Ph.D., 3M Principal Analytical Investigator
Z0J2-
D ate
Page 21 of77
Attachment A: Protocol A mendment
GLP10-01-02; Interim Report 26 Analysis of PFBS, PFHS, and PFOS Bert Jeffries Landfill - February 2012
Page 22 of 77
GLP10-01-02; Interim Report 26 Analysis of PFBS, PFHS, and PFOS Beit Jeffries Landfill - February 2012
Analytical Protocol: GLP10-01-02 Amendment 26
Study Title
Analysis o f Perfluorooctane Sulfonate (P F O S ), Perfluorohexane Sulfonate (P F H S ) and Perfluorobutane sulfonate (P F B S ) in Groundw ater, Soil and Sedim ent fo r th e 3M D ecatur Phase 3 S ite-R elated M onitoring Program
PROTOCOL AMENDMENT NO. 26
Amendment Date:
February 2 1 ,2 0 1 2
Performing Laboratory
3M Environm ental, Health, and S afety O perations 3M Environm ental Laboratory Building 2 60 -5 N -1 7 M aplewood, M N 5 5 1 4 4 -1 0 0 0
Laboratory Project Identification
G LP 10-01-02-28
Sampling Event
B ert Jeffries Landfill -S u rfa c e W a te r Sam pling
Page 1 of 6
Page 23 of 77
GLP10-01-02; Interim Report 26 Analysis of PFBS, PFHS, and PFOS Beit Jeffries LandfiN February 2012
Analytic*! Protocol: GLP10-01-02 Amendment 26
This amendment modifies the following portion of protocol:
"Analysis o f P F O S , P F H S and PFB S in Groundw ater, Soil and S edim ent for the 3M D ecatur Phase 3 S ite-R elated M onitoring Program"
PROTOCOLMADS:
N o changes to th e w ording o f th e protocol a re required.
AMN0TORAD:
No changes to th e w ording o f th e protocol are required. This am endm ent only addresses and docum ents the addition o f th e G eneral Project O utline (G P O ) for th e collection and analysis o f groundw ater sam ples from D ecatur, AL, and conducted a s part o f th e 3M D ecatu r P hase 3 Program fo r P F O S , P F H S and P F B S (G LP 10 -0 1 -0 2 ). Sam pling activities a t and n ea r th e B ert Jeffries landfill a re scheduled fo r th e w eek o f February 2 7 ,2 0 1 2 and w ill consist o f 6 paired surface w a te r and sedim ent sam ples. T h is protocol am endm ent addresses th e sam p ln g and analysis o f th e surface w a te r sam ples. S urface w a te r sam ples collected under this sam pling e v e n t w ill b e entered into the 3M Environm ental Laboratory L IM S a s project G LP 10 -0 1 -0 2 -2 6 and reported as interim report G L P 1 0 -0 1 -0 2 -2 6 (reflecting study G L P 1 0 -0 1 -0 2 and am endm ent -26).
T h e reason for this am endm ent Is to docum ent th e G en eral P roject O utline (G P O ) w hich d escribes the anticipated surface w ater sam ple collection e v e n t to b e conducted a t and n e a r th e B ert Jeffries landfill in Law rence C ounty, A L T he G P O is three pages in length and Included as attached to this am endm ent form .
Page 2 of 6
Page 24 of 77
GLP10-01-02; Interim Report 20 Analysis of PF8S, PFHS, and PFOS Bert Jeffries Landfill - February 2012
AnalyticalProtocol: GLP10-01-02 Amendment 26
Amendment Approval
Page 3 of 6
Page 25 of77
GLP10-01-02; Interim Report 26 Analysis of PFBS, PFHS, and PFOS Bert Jeffries Landfill - February 2012
AnalyticalProtocol: GLP10-01-02 Amendment 26
3M Environmental Health & Safety Operations, Environmental Laboratory
General Project Outline
To: G ary Hohenstein, 3M EHS&O pns
From :
Susan W olf, 3M EHS&Opns: Environmental Lab
cc: W Hiam Reagan, 3M EHS&Opns; Environm ental Lab
Jai Kesari, W eston Solutions Charles Young, W eston Solutions
D ate:
February 2 1 ,2 0 1 2
S u b je c t:
A nalysis o f P erflu oroo dan e S ulfonate (P F O S ), Perfluorohiaxane S ulfonate (P F H S ) and Perfluorobutane sulfonate (P F B S ) in G roundw ater, S oil and S edim ent fo r th e 3M D ecatu r P hase 3 S ite-R elated M onitoring Program ; G LP Interim R eport 2 6 - B ert Jeffries Landfill; S urface W a te r sam pling th e w e e k o f F ebruary 2 7 ,2 0 1 2 .
1 Generai Project Information
Contacts
3M SponsorRepresentative Gaiy Hohenstein 3MEHS Operations 3M Bonding 224-SW-03 Saint Paul, MN 5514*1000 Phone:(651)737-3570 QahohensteinQtnmin.com
3M Environmental Laboratory Management Wiliam K. Reagan 3M EHS Qpne, Environmental Laboratory Z60-6N-17
Principal Analytical Imraetigater Cleeton Lange 3M EHS Opre, Environmental Laboratory 260-6N-17
Lab Request Number Six Dialt Department Number Prqfect SchaduleATest Dates
Sampling Coordinator IbnothyFifnak Weston Solutions Hmothv.frinakgheaetaneolutiona.com Phene: <334V332123 .
QLP10-0142-26
Dept #530711, Project 0030674448 . Tentatively aeheduM forthe week of Ftbtuary 27,2012.
All verbal andwritten correspondence wBIbe directed to GaryHohenstein.
Page 4 of 6 Page 26 of 77
GLP10-01-02; Interim Report 20 Analysis of PFBS. PFHS. and PFOS Bert Jeffries Landfill February 2012
Analytical Protocol: GLP10-01-02 Amendment26
2 Background information and Project Objective(s)
T h e 3M E H S O perations Laboratory (3 M Environm ental Lab ) w ill receive and a n a ly ze surface w ater sam ples collected from six (6 ) locations a t and n e a r th e B ert Jeffries landfill. S u rface w a te r sam ples w ill b e collected by W esto n . T h e 3M Environm ental Laboratory w ill prepare th e sam p le bodies: S am ples w ill b e analyzed fo r P erftuorooctane S ulfonate (P F O S ), Perfluorohexane S ulfonate (P F H S ) and Perfluorobutane S ulfonate (P F B S ). A nalyses w ill be conducted u nder th e G L P requirem ents o f EPA T S C A G ood Laboratory P ractice Standards 4 0 C F R 792. T h e fin al rep ort w ill be subm itted to G ary Hohenstein and Jai K esari upon com pletion u n d er interim report G L P 10-01-02-26.
3 Project Schedule
Sam ple collection bottles will b e prepared by the 3M Environm ental Laboratory. Sam ple bottles wH be shipped in coolers overnight to 3M Decatur fo r arrival by Friday, February 2 4 ,2 0 1 2 . Sam ple bottles should b e stored refrigerated o n -a te until sam ple collection.
M artin Sm ith \ W eston T ra ile r 3M D ecatu r P la n t 1400 S tate D ocks Road D ecatur, A labam a 3 5 601
4 Test Parameters
T he targeted lim t o f quantitation anil be 0 .0 2 5 n g /m L (ppb) for PFB S, P F H S , and PFO S . A total of six sampling locations have been specified. For each sampling location, a total o f four sam ple bottles wW b e collected (sam ple, sam ple duplicate, low-level field m atrix spike, and high-level field m atrix s p ite ). T h e TUI to here* in e on each 2 5 0 m L N alg en e bottle wffl be 2 0 0 m L O n e set o f trip blanks consisting o f reagent-grade w ater, a low-level trip blank spike, and a high-level trip blank spike will be prepared a t th e 3M Environm ental Laboratory and sent to th e sampling location w fih the other bottles. N o previous data on fluorochem icals to groundwater, surface w ater o r sedim ent m edia exist far the site. T h e towfiekJ m atrix s p ite will b e prepared a t 1 ng/m L and th e high field m atrix spike a t 10 ng/mL. All sam ple bottles w il include the addition o f "O i-P F B S . ,sC rP F H S . and *C rP F O S , (internal standards) a t a nominal concentration o f 1 ng/m L. AR sam ple bottles will also include the attritio n o f " G rP F O S (surrogate recovery standard) a t a nominal concentration o f 0.1 ng/mL. T o aid in sam ple collection, a non-spiked 1-L sam ple b o ttle w ill be provided fo r each sam pling location. Sam ple collection w ill consist o f d irect im m ersion. A liquots w ill be decan ted from th e collection bottle to the prim ary, d uplicate and m atrix spike bottles. N o rtoseate blank w ill b e collected.
Page 8 of 5
Page 27 of 77
J___ X
GLP10-01-02; Interim Report 26 Analysis of PFBS, PFHS. and PFOS Bert Jeffries Landfil - February 2012
Analytical Protocol: GLP10-01-02 Amendment 26
S Test Methods
Sam ples will be prepared and analyzed by LC /M S /M S folowing ETS -8-044.1 "M ethod o f Analysis for the Determination o f Perifuorinatod Compounds In W a ter by High Perform ance Liquid Chrom alography/M ass Spectrom etry Direct Injection Analysis' . Alternately, sam ples m ay be analyzed by E T S 8 -1 5 4 .3 ` Determ ination o f Perfluorinated Acids, Alcohols, Am ides, and Sulfonates In W a ter By Solid Phase Extraction and High Perform ance Liquid Chrom atogiaphy/M ass Spectrometry*. W here applicable, sam ples wtil be analyzed against an internal standard calibration curve. Each curve point w i contain isotopicalty-iabeled PFB S, PFH S . and PFO S a t a nom inal concentration o f 1 ngftnL T h e c a fc ra fo n curve will be generated by taking the ratio o f the standard peak area counts o ver th e internal standard peak area counts to fit the d ata for each analyte. Laboratory control sam ples prepared with the sam ples m ust have an average recovery within 1 0 0 2 0 % a n d a R SD S20% . T h e d ata quality objective for this study is quantitative results fo r the target analytes with an analytical accuracy o f 10030% . Field m atrix spikes not yielding recoveries within 10Q 30% w ill be addressed in the report and the final accuracy statem ent m ay be adjusted accordingly.
6 Reporting Roquiremonls__________________________________________
FOr each sampfing location, the report vdHcontain the results for the sam ple, sam ple dupficato, and the tw o field matrix spires. Trip blank and trfo blank spikes wifi be reported fo r the sam ping e v e n t Laboratory control spikes o f reagent w ater prepared at the rim e o f sam ple extraction w il also be reported and used to evaluate the overall method accuracy and precisian. M ethod blanks o f reagent w ater prepared a t th e tim e o f sam ple extraction w il be used to determ ine the method detection lim it For those sampling locations w here the field m atrix s p ite level was not appropriate due to higher than expected analyte concentrations, a target analyte laboratory m atrix s p ite m ay be prepared and will be included in the final report
Page.8 of 6
Page 28 of 77
GLP10-01-02; Interim Report 26 Analysis of PFBS. PFHS, and PFOS Bert Jeflfies LandfM - February 2012
Atta c h m en t B : R ep r es en ta tiv e Sa m p l e C h r o m ato g ram s a n d C a lib r a tio n C u r ve(s )
. Page 29 of 77
STS*McCoy
GLP10-01-02; Interim Report 26 Analysis of PFBS, PFHS, and PFOS Bert Jeffries LandfHI - February 2012
Results Mane: acl203l3a.rdb
Printing Date: Wednesday# April 11# 2012
Page 30 of 77
*ETS-HeCoy
GLP10-01-02; Interim Report 26 Analysis of RFBS, PFHS. and PFOS Bert Jetfries Lande - February 2012
Results Nase: nc!20313a.rdb
Printing Date: Wednesday, April 11, 2012
Page 31 of 77
*** Ginger AGOL330509
GLP10-01-02; Interim Report 26 Analysis of PFBS. PFHS, and PFOS Bert Jeffries Landfill - February 2012
Results Name: gl20307a*rdb
Printing Date: Wednesday, April 11, 2012
Page 32 of 77
** Ginger AG01330509
GLP10-01-02; Interim Report 26 Analysis of PFBS. PFHS, and PFOS Bert Jeffries Landfil - February 2012
Results Name: gl20307a.rdb
' Analyte Area / IS Area
Printing Tine: 12:24:26 PM Printing Date: Wednesday, April 11, 2012
Page 33 of77
ETS-HcCoy
6LP10-01-02; Interim Report 26 Analysts of PFBS, PFHS, and PFOS Bert Jeffries Landfill - February 2012
Results Name: nct203l3a.rdb
Printing Date: Wednesday, April 11, 2012
Page 34 of 77
*ETS-McCoy
GLP10-01-02; Interim Report 26 Analysis of PFBS, PFHS, and PFOS Bert Jeffries Landfill - February 2012
Results H a m : mcl20313a,rdb
Printing Date: Wednesday, April 11, 2012
Page 35 of 77
ETS-McCoy
GLP10-01-02; Interim Report 26 Analysis of PFBS. PFHS, and PFOS Bert Jeffries Landfill February 2012
Results Naae: acl20313a.rdb
Printing Date: Wednesday, April 11/ 2012
Page 36 of 77
ETS-McCoy
GLP10-01-02; Interim Report 26 Analysis of PFBS. PFHS. and PFOS Bert Jeffries Landfll - February 2012
Results Ns; ncl203l3a.rdb
2012Printing Date: Wednesday, April 11
Page 37 of 77
*ETS-MeCoy
GLP10-01-02; Interim Report 26 Analysis of PFBS. PFHS, and PFOS Bert Jeffries LandfHI - February 2012
Results Nans ncl20313a.rdb
Printing Pats: tfsdnsaday, April 11, 2012
Page 38 of 77
ETS-Hecoy
GLP10-01-02; Interim Report 26 Analysis of PFBS, PFHS, and PFOS Bert Jeffries LandfM February 2012
Results Neme; mcl20313a.rdb
Printing Dat: Wednesday, April 11, 2012
Page 39 of 77
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Page 40 of 77
ETS-MCCoy
GLP10-01-02; Interim Report 26 Analysis of PFBS. PFHS, and PFOS
Bert Jeffries LandIII February 2012
Results Name: nci203l3a.rdb
D a t a p r i n t e d b y STtf Printing Tiae: 11:34:46 AH
Printing Date: Wednesday, April 11 2012
Page 6 of 9
Page 41 of77
ETS-McCoy
GLP10-01-02; Interim Report 26 Analysis of PFBS. PFHS, and PFOS Beit Jeffries landfill - February 2012
Resulta Naae: mclZ03t3a.rdb
Printing Date: Wednesday, April 11, 2012
Page 42 of 77
** Ginger AG01330509
GLP10-01-02; Interim Report 26 Analysis of PFBS, PFHS, and PFOS Bert Jeffries Landtil February 2012
Results Nane: gl20307a.rdb
Printing Date; Wednesday April 11, 2012
Page 43 of 77
*** Ginger AGO1330509
GLP10-01-02; Interim Report 26 Analysis of PFBS, PFHS, and PFOS Bert Jeffries Landfill February 2012
Results Name: gl20307a.rdb
Printing Date: Mednesday, April 11, 2012
Page 44 of 77
* Ginger AGO)330509
GLP10-01-02; Interim Report 26 Analysis of PFBS, PFHS, and PFOS Bert Jeffries Landfill - February 2012
Results Name: gl20307a.rdb
Printing Date Wednesday, April 11 2012
Page 45 of 77
Ginger AG013J0309
GLP10-01-02; Interim Report 26 Analysis of PFBS, PFHS, and PFOS Bert Jeffries Landfill - February 2012
Results Nane; gl2030la.rdb
Printing Tine: 12:30:11 PM Printing Date: Wednesday* April 11, 2012
Page 46 of 77
*** Girxjer AGO 1330509
GLP10-01-02; Interim Report 26 Analysis of PFBS, PFHS, and PFOS Bert Jeffries LandfiM Februaiy 2012
Results Kane: gl20307a.rdb
Printing Date: Wednesday, April 11, 2012
Page 47 of 77
*** Ginger AG01330509
GLP10-01-02; Interim Report 26 Analysis of PFBS, PFHS, and PFOS Bert Jeffries Landfill - February 2012
Results Wane: gl20307a.rdb
Printing Tine: 12:30:12 PM
2012Printing Date: Wednesday, April 11
Page 48 of 77
*** Gingsr AG01330S09
GLP10-01-02; Interim Report 26 Analysis of PFBS. PFHS, and PFOS Bert Jeffries Landfill - February 2012
Results NsstS: Ql2030^s.cdb
Printing Data: Wednesday, April II, 2012
Page 49 of 77
** Ginger AG01330509
GLP10-01-02; Interim Report 26 Analysis of PFBS. PFHS, and PFOS Bert Jeffries Landfill - February 2012
Results Name: 9120307m.rdb
Printing Date: Wednesday, April 11, 2012
Page 50 of 77
G ing.r AG01330509
GLP10-01-02; Interim Report 26 Analysis of PFBS. PFHS. and PFOS Bert Jeffries Landfil - February 2012
Results Name: 9120307a.rdb
Printing Date: Wednesday, April 11, 2012
Page 51 of 77
*** Ginger AG01330509
GLP10-01-02; Interim Report 26 Analysis of PFBS, PFHS, and PFOS Bert Jeffries Landfill - February 2012
Result* Name: 9120307a.rdb
Printing Date: Wednesday, April 11 2012
Page 52 of 77
** Ginger M301330509
GLP10-01-02; Interim Report 26 Analysis of PFBS. PFHS, and PFOS Bert Jeffries LandfW - February 2012
Results Ram: gl20307a.rdb
Printing Tine: 12:30:13 PM
2012Printing Date: Wednesday, April 11
Page 53 of 77
*** Ginger AG01330509
GLP10-01-02; Interim Report 26 Analysis of PFBS, PFHS, and PFOS Bert Jeffries Landfill - February 2012
Results Nane: gl20307a.rdb
Printing Oat Wednesday, April 11 2012
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Atta c h m e n t C : A n a lytic a l M eth o d (s )
GLP10-01-02; Interim Report 26 Analysis of PFBS, PFHS, and PFOS Bert Jeffries Landfill - February 2012
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3MEnvironmental Laboratory
Method Method o fAnalysis for the Determination o f Pertiuorinated Compounds in Water
by LC/MS/MS; Direct injection Analysis Method Number: ETS4M44.1 Adoption Date: 4/12/07 Effective Data: / l / f / U
Approved By.
W iliam K. Reagan, Technical Director, Environmental Laboratory
J A r y is 3 0 / /
D ate
ETS-8-044.1
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Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct
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1 Scope and Application
This method describes the direct injection analysis of perfkiorinated compounds (PFCs) from water matrices using high-performance liquid chromatography tandem mass spectrometry (H PLC /M S/M S). The method is generally applicable but not limited to the measurement of perfluoroalkyt sulfonamides and perfluorinated alkyl acids (PFAAs) such as perfluorosulfonic acids (PFSAs) and perfluorocarboxylic acids (PFGAs) (Table 1). W ater samples containing heavy particulate may require preparation by an alternate method such as ETS -8-154 "Determination o f Perfluorinated Acids, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry*. The method is applicable to both external standard and internal standard calibration1.
Table 1. Representative Target Analytes
A cro n ym
PFBA (C4 Add) PFPeA (C5 Acid) PFHxA (C6 Acid) PFHpA (C7 Add) PFOA (C8 Add) PFNA (C 9 Add) PFDA (C10 Add) PFUnA (C11 Add) PFDoA (C12 Add) PFTrDA (C13 Add) PFBS (C4 Sulfonate) PFHS (C 6 Sulfonate) PFOS (C 8 Sulfonate) FBSA (C4 Sulfonamide FOSA (C 8 Sulfonamide)
Am M o
Perfluorobutanoic add Periluoropentanoic add Periluorohexanoie add Perfluoroheptanolc add Perfluorooctanoic add Periluorononanoic add Periluorodecanoic add Perfiuoroundecandc add Perfiuorododecanolc add Periluorotridecanoic add Periluorobutanesulfonic add Periluorohexanesulfonic add Periluorooctanesutfonic add Perfluorobutanesulfonamide Pefluorooctanesulfonamlde
C h em tcM l A b s tra c t Sendees
R e g is try N u m b o r (C A S R N i
375-22-4 2706-90-3 307-24-4 375-85-9 335-67-1 375-95-1 335-78-2 2056-94-8 307-55-1 72629-94-8 375-73-5 355-46-4 1763-23-1 30334-69-1 754-91-6
The Minimum Reporting Level (M RL) is the Limit of Quantitation (LO Q ) that m eets Data Quality Objectives (D Q O s) that are developed based on the intended use of this method.
Method Flexibility - This is a performance-based method and may be generally applied to the determination of perfluorinated compounds in water matrices when analysis batch quality control (Q C ) criteria are met12. Each set of samples are prepared in an analysis batch with calibration standards, LCSs, blanks, and continuing calibration check standards analyzed on the sam e instrument during a tim e period that begins and ends with the analysis of the appropriate continuing calibration check standards. The laboratory is permitted to modify the LC column, mobile phase composition, LC conditions, and MS/M S conditions. Method modifications should be considered to improve method performance or to m eet data quality objectives for the study. In all cases where method modifications are implemented, the batch
1T h e m ethod is supported b y va lid a tio n w ith internal standard calibration fo r C 4 -C 1 3 P F C A s , C 4 , C 6 , and C 8 P F S A s , and C 8 perflu oroalkan e su lfonam ide in lab oratoiy con trol sam ples under 3 M m ethod validation E l 1-0667.
2G u id an ce fo r estab lish in g m ethod Q C C rite ria based on a.) F D A M a y 2001, " G u id a n ce fo r Indushy, B io a n a ly tica l M ethod V a lid a tio n " , b .) E P A M eth od 537, and c.) European C om m ission : G u id an ce fo r G enerating and R eporting M eth ods o f A n a ly s is in Support o f Pre-registration D ata Requirem ents fo r A n n ex II (Part A , section 4 ) and A n n ex 111 (Part A ,se ctio n 5) o f D ire c tiv e 91/414, SA N CO /3029/99 rev. 4 (11/07/00).
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analytical QCs (section 9) must be compieteci and pass Q C acceptance criteria (section 13) if the data from the analytical batch era to be reported.
2 Method Summary_____________________
_______
W ater samples are analyzed as neat aqueous sample or as solvent diluted aqueous samples by direct injection using LC/M S/M S. Samples containing heavy particulate may not be suitable for analysis by this method. Samples containing suspended particulate should be centrifuged or filtered prior to removing a sample aliquot or diluting with solvent The water sample is mixed well prior to removing an aliquot or diluting, if necessary, with ASTM Type I water, HPLC water, other suitable water, or solvent (methanol).
Quantitation is by stable isotope internal standard calibration in laboratory reagent water. All perfluorinated compounds (PFCs) target analyte concentrations of perfluorosulfonic acids (PFSAs) and perfluorocarboxySc adds (PFCAs) are reported as anions and corrected for their salt or free acid forms. Alternatively, quantitation may be performed by denial standard calibration.
This is a performance-based method. Method uncertainty for each target analyte is determined for each analytical batch using multiple laboratory control spikes at multiple concentrations. This method also requires that the precision and accuracy for each sample be determined using field matrix spikes to verify that the method is applicable to each sample matrix.
Calibration standards for PFUnA, PFDoA, PFTrDA, and FOSA have been found to be unstable for more than 2 days in 100% water. Samples requiring analysis for these compounds by this method should be diluted 1:1 with methanol and analyzed against a calibration curve prepared in 1:1 synthetic groundwaterMeOH.
3 Definitions
3.1 Analysis Batch
A set o f study samples that are prepared with calbration standards, laboratory control samples, and procedural blanks, and analyzed on the sam e instrument during a time period that begins and ends with the analysis of the appropriate continuing calibration check standards.
3.2 Analytical Sample
A portion of a laboratory sample prepared for analysis.
3.3 Calibration Standard
A solution prepared by spiking a known volume of the Working Standard (W S) into a predetermined amount of ASTM Type I, HPLC grade water, or other suitable water (i.e. matrix water), and analyzed according to this method. Calbration standards are used to calibrate the instrument response with respect to analyte concentration
3.4 Laboratory Duplicate Sample (LDS, or Lab Dup)
A laboratory duplicate sample is a separate aliquot of a sample taken In the analytical laboratory that is analyzed separately with identical procedures. Analysis of LDSs compared to that of the first aliquot give a measure of the precision associated with laboratory procedures, but not with sample collection, preservation, or storage procedures.
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3.5 Field Blank (FB)/Trip Blank (TB)
A STM Type I, HPLC grade water, or other suitable water, placed in a sample container in the laboratory and treated as a sample in a l respects, including exposure to sam plng site conditions, storage, preservation and all analytical procedures. The purpose o f the TB is to determine if test substances or other interferences are present in the field environm ent This
sample is also referred to as a Trip Blank.
3.6 Field Duplicate Sample (FDS, Field Dup)
A sample collected in duplicate at the sam e tim e from the sam e location as the sample. The FDS is handled under Identical circumstances and treated exactly the sam e throughout field and laboratory procedures. Analysis of the FD S compared to that of the first sample gives a measure o f the precision associated with sample colection, preservation and storage, as wen as with laboratory procedures.
3.7 Field Matrix Spike (FMS)
A sam ple to which known quantities of the target analytes, ISs and SRSs are added to the sample bottle in the laboratory before the bottles are sent to the field for collection of aqueous samples. A known, specific volume of sample must be added to the sample container without rinsing. This m ay be accomplished by making a H I to this level' line on the outside of the sample container. The FM S is analyzed to ascertain if any matrix effects, interferences, or stability issues m ay complicate the interpretation o f the sample analysis.
3.8 Trip Blank Matrix Spike (TBMS)
An aliquot of ASTM Type I, HPLC grade water, or other suitable water, to which known quantities of the target analytes, ISs and SRSs are added in the laboratory prior to the shipment o f the collection bottles. The TBM S is analyzed exactly like a study sample to help determine if the method is in control and whether a loss of analyte or analytical bias could be attributed to sample holding time, sample storage and/or shipment issues. A low and high TBM S are appropriate when expected sample concentrations are not known or m ay vary.
3.9 Internal Standard (IS)
A compound added to each study sample, calibration standard, laboratory control samples, and procedural blanks a t a consistent level (typically around 1 ng/mL). The internal standard(s) are stable isotope labeled versions of the target analytes. The area count ratio of the target analyte to the internal standard is used for calibration. Surrogate ISs are applied when stable isotope ISs of target analytes are unavailable. A surrogate IS is not necessarily a stable isotope labeled version o f the target analyte, but is treated as an internal standard for quantitation.
3.10 Laboratory Control Sample (LCS)
An aliquot of control matrix to which known quantities of the target analytes, ISs and SRSs (when applicable) are added in the laboratory at the tim e when samples are aliquotted. At least three levels (two levels for SRSs) in triplicate are included, one generally at the low end of the calibration curve and one near the mid range and the upper end of the curve. The LCSs are analyzed exactly lice a laboratory sample to determine whether the stability o f the standards. LCSs should be prepared each day samples are aliquoted.
3.11 Laboratory Matrix Spike (LMS)
A laboratory matrix spike is an aliquot of a sample to which known quantities of target analytes, ISs and SRSs (when applicable) are added in the laboratory. The LMS is analyzed exactly like a laboratory sample to determine whether the sample matrix contributes bias to the analytical results. The endogenous concentrations of the analytes in the sample matrix must be determined in a separate aliquot and the measured values in the LMS corrected for these concentrations. LMSs are optional for analyse of aqueous samples.
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3.12 Laboratory Sample
A portion or aliquot of a sample received from the field for testing.
3.13 Limit of Quantitation (LOQ)
The lower limit of quantitation (LLOQ) for an analytical batch is the lowest concentration that can be reliably quantitated within the specified limits of precision and accuracy. The LLOQ is generally selected as the lowest non-zero standard in the calibration curve that meets method acceptance criteria. The LLOQ for each target analyte is established for each analysis batch as the lowest calibration standard with area counts at least twice that of the average area counts of the procedural blanks.
The upper limit of quantitation (ULOQ) for an analytical batch is the highest concentration that can be reliably quantitated within the specified limits of precision and accuracy. The highest standard in the calibration curve that m eets method acceptance criteria is defined as the ULOQ.
3.14 Method/Procedural Blank
An aliquot o f control matrix that is treated exactly ik e a laboratory sample including exposure to all glassware, equipment, solvents, and reagents that are used with other laboratory samples. The method blank is used to determine if test substances or other interferences are present in the laboratory environment, the reagents, or the apparatus.
3.15 Sample
A sample is an aliquot removed from a larger quantity of material intended to represent the original source material.
3.16 Stock Standard Solution (SSS)
A concentrated solution of a single-analyte prepared to the laboratory with an assayed reference compound.
3.17 Surrogate Internal Standard
An IS that is not necessarily a stable isotopically labeled target analyte, but is treated as an internal standard for quantitation. Surrogate ISs are used when isotopicaly labeled counterparts of the target analyte are not commercially or readily available.
3.18 Surrogate Recovery Standard (SRS)
An isotopically labeled standard, not used as an internal standard, that is added to each sample and appropriate QC sample as a means to evaluate the method performance for a chemical class of compounds (e.g., PFSAs, PFCAs).
3.19 Working Standard (WS)
A solution of several analytes prepared to the laboratory from SSSs and diluted as needed to prepare calibration standards and other required analyte solutions.
4 Warnings and Cautions
4.1 Health and Safety
The acute and chronic toxidty of the standards for this method have not been precisely determined; however, each should be treated as a potential health hazard. The analyst should w ear gloves, a lab coat, and safety glasses to prevent exposure to chemicals that might be present.
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Direct Injection Analysis
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The laboratory is responsible for maintaining a safe work environment and a current awareness of local regulations regarding the handling of the chemicals used in this method. A reference file of material safety data sheets (M SD S) should be available to aR personnel involved in these analyses.
4.2 Cautions
The analyst must be familiar with the laboratory equipment and potential hazards including, but not limited to, the use of solvents, pressurized gas and solvent lines, high voltage, and vacuum systems. R efer to the appropriate equipment procedure or operator manual for additional information and cautions.
5 Interferences
During sam ple preparation and analysis, major potential contaminant sources are reagents and glassware. All materials used in the analyses shal be demonstrated to be free from interferences under conditions of analysis by running method blanks.
Parts and supplies that contain Teflon should be avoided or minimized due to the possibility of interference and/or contamination. These may include, but are not limited to: wash bottles, Teflon* lined caps, autovial caps, HPLC parts, etc.
The use of disposable micropipettes or pipettes to aliquot standard solutions is recommended to m ake calibration standards and matrix spites.
6 Instrumentation, Supplies, and Materials____
6.1 Instrumentation
Analytical balance capable of reading to 0 .0 0 0 1 g HPLC/M S/M S or HPLC/M S system, as described in Section 10.
6.2 Supplies and Materials
Sample colection bottles-- HDPE (e.g., NalgeneTM ) wide-mouth bottles with screw cap. N ote: Do not use fluorinated or Teflon bottles or lined caps. Coolers or boxes for sample shipment. 15-m L and 50-m L disposable polypropylene centrifuge tubes. Class A pipettes and volumetric flasks, various. 2 mL HPLC autovials Disposable pipettes, polypropylene or glass as appropriate Centrifuge capable of spinning 15-m L and 50-m L polypropylene tubes at 3000 rpm.
7 Reagents and Standards
N ote: Suppliers and catalog numbers are for illustrative purposes only. Equivalent performance may be achieved using chemicals obtained from other suppliers. Do not use a lesser grade of chemical than those listed.
7.1 Chemicals
W ater - Milli-Q, HPLC grade, or other suitably appropriate sources
Calcium Acetate - A .C .S, Reagent Grade
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Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS;
Direct Injection Analysis
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i r 'w r i -- --
mu
11 i n i m : : : i . i 111 l . i i _
GLP10-01-02; Interim Report 26 Analysis of PFBS, PFHS, and PFOS Beit Jeffries Landfil Februaiy 2012
Magnesium Acetate - A.C.S. Reagent Grade Methanol - HPLC grade Ammonium Acetate - A C .S . Reagent Grade
7.2 Representative Target Analytes, ISs, and SRSs
PFBA, Heptafluorobutyric Acid, {C4 Perfluorinated A dd)
PFPeA, Nonafluoropentanoic A dd (C5 Perfluorinated A dd) PFHxA, Perfluorohexanoic A dd (Ce Perfluorinated Acid)
PFHpA, Tridecafluoroheptanoic Acid, (Or Perfluorinated Acid)
PFOA, Ammonium perfluorooctanoate, (C 8 Perfluorinated A dd)
PFNA, Heptadecafluorononanoic Acid, (Co Perfluorinated A dd) PFDA, Nonadecafiuorodecanoic A dd (C 10 Perfluorinated Acid) PFUnA, Peifluoroundecanoic Add, (C r Perfluorinated A dd) PFDoA, Perfluorododecanoic Add, (C 12 Perfluorinated A dd) PFTrDA, Perfluorotridecanoic Acid, (C 13 Perfluorinated A dd) FBSA, Perfluorobutanesulfbnamide FOSA, Perfluorooctanesulfonyiamide PFBS, Potassium Perfluorobutanesulfonate PFHS, PerfluorohexanesuKbnate PFOS, Potassium perfluorooctanesulfbnate PFOA [1 ,2 ,3 ,4 -13C], 13C4-isotopically labeled perfluorooctanoic acid (SR S) PFO S [1 ,2 ,3 ,4 -13C], 1*C4-isotopically labeled Perfluorooctanesulfbnate (SRS) PFUnA [1,2-13C], 13Cr (SOtopically labeled Perfluoroundecanoic add (SRS)
A custom mix of ISs in a methanoiic solution containing ([1.2,3,4-13C4]PFBA. [1,2 ^C JPFH xA , [1.2,3,4,5,6,7,8-13CalPFOA, [1,2,3,4.5,6,7,8,9-^C yP FN A , [1,2 -^ C J P F D A [1,2,3,4,5,6 ,7 -13C7]PFUnA, [1,2 -l3C 2]PFDoA, [1,2,3 -^CaJPFHS, [1 A S .e j.& ^ C g lP F O S , and [1,2.3.4,5,6,7,8-13Ca]PFOSA (Wellington Laboratories, Guelph, O N ) in combination with added {[1,2,3,4,5-13C yPFPeA, ([1,2,3,4-iaC JPFH pA and [^O JPFB S can be used to prepare a stock IS solution. Alternatively, individual stable isotope ISs can be used to prepare a stock IS mixture. Other ISs can be applied.
7.3 Reagent Preparation
2 mM Ammonium acetate solution (Analysis)--W eigh 0 .3 g of Ammonium acetate and dissolve in 2.0 L of reagent water. Synthetic Groundwater (containing 25 ppm C a and Mg) - Weigh 0.61 g of Calcium Acetate and 0.92 g of Magnesium Acetate and dissolve in 6.0 L of reagent water. Note: Alternative volumes may be prepared as long as the ratios of the solvent to solute ratios are maintained.
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7.4 Stock Standard Solution (SSS) and Working Standard Solution Preparation
The following standard preparation procedure serves as an example. Weighed amounts and final volumes may be changed to suit the needs of a particular study. For example, pL volumes m ay be spiked into volumetric flasks when diluting stock solutions to appropriate levels.
100 pg/m L target an alyte SSSs-- W eigh out 10 mg of analytical standard (conectad for percentsalt, add [ETS-4-031] and purity) and dilute to 100 mL with methanol or other
suitable solvent in a 100 mL volumetric flask. Transfer to a 125 mL LDPE bottle or other suitable container. Prepare a separate solution for each analyte. Expiration dates and storage conditions of stock solutions should be assigned in accordance with laboratory standard operating procedure. An exam ple of purity and salt correction is given below for PFOS.
salt correction factor * m olecular w eight o f anion
m oclecular weight o f salt
PFO S (K + )salt correction factor = -- -- = 0 .9 2 7 5 9wO
10 mg CaFtiSOaK* with purity 90% = 8.35 mg CeFuSOs" (10 m g*0.90*0.9275=8.35 mg)
10 pg/m L (10,000 ng/m L) m ixed w orking standard-- Add 5.0 mL each of the 100 pg/mL SSSs to a 50 mL volumetric flask and bring up to volume with solvent.
1 pg/m L (1,000 ng/m L) m ixed w orking standard-- Add 0.5 m L o f the 100 pg/mL SSSs to a 50 mL volumetric flask and bring up to volume with solvent.
0.1 pg/m L (100 ng/m L) m ixed standard--Add 0.05 mL of the 100 pg/mL SSSs to a 50 mL volumetric flask and bring up to volume with solvent.
S torage C onditions-- Store all SSSs and working standards in accordance with laboratory standard operating procedure or in a refrigerator at 42C for a maximum period of 6 months from the date of preparation.
7.5 Calibration Standards
Calibration can be performed by IS or external calibration. Using the working standards described above, prepare calibration solutions in ASTM Type I water, HPLC water, other suitable water, or a mixture of solvent and water using the information in Table 2 as a guideline. Note: Volumes of water or water/solvent mixtures and working standards may be adjusted to m eet the data quality objectives addressed in the general project outline. Calibration levels other than those listed below can be prepared as needed.
For the quantitation of PFOA and PFO S, reference materials erf certified mixed linear and branched isomer are preferred. Alternately, reference materials of primarily linear isomers of PFO A and/or PFO S may be used, however, when quantitating with predominantly linear reference standards, additional LCS samples containing both linear and branched isomers of PFOA and PFO S are required3.
7.5.1 Internal Standard (IS) and Surrogate RecoveryStandard (SRS)
For IS calibration, stable isotope internal standards of each target analyte or appropriate surrogate ISs should be spiked at the sam e level in all calibration standards. Once the cassation standards have been prepared as stated above in Section 7.5, all calibration standards are spiked with a separate internal standard spiking solution. Typicaly the5
5A report summarizing on assessment o f the use o f reference standards containing certified linear and branched isomers o f PFOA/PFOS can be found in 3M report E l 1-0560.
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concentration of the internal standard is consistent with the internal standard concentration expected in the samples being prepared, usually 1 ng/m L The concentration of the internal standard spiking solution is typically 2 pg/mL. A separate zero point or method blank is typically prepared at the sam e time as the calbration standards, using the sam e solution used to prepare the standards (ASTM Type I water, HPLC water, other suitable water, or a solvent/water mixture), and is spked with the internal standard at the sam e concentration as the calibration curve, typically at 1 ng/m L
If the samples being analzyed were pre-spiked with SRSs, the calibration curve prepared in Section 7.5 is spiked with a separate SRS spiking solution. Typically, the sample bottles are spiked with a SRS at 0.1 ng/mL. The final calibration curve must consist of at least six calbration points after analysis. The following table provides an exam ple o f spke concentrations and volumes used to achieve a multi-point extracted calbration curve with internal standard and surrogate standard.
Table 1 fists recommended stable isotope internal standards for several PFSA and PFCA target compounds. A custom mix of isotopicaj^ labeled target analytes in a methanolic
,2 ,,,w - *CJFO SA (Wellington Laboratories, Guelph, O N) in combination with added ([1,2,3,4,5-l3Ca|PFPaA, (11,2,3,4-13C4]PFHpA, and [ieO jjPFB S can be used to prepare a stock IS solution. Alternative sources of certified stable isotope labeled target analytes are applicable. Alternatively, individual stable isotope ISs can be used to prepare a stock IS mixture. The table below lists the recommended stable isotope ISs and SRSs applied in the method. Other stable isotope ISs and SRSs o f target analytes not listed in the table may be used if supported by validation and/or analysis batch QCs meeting method acceptance criteria (e.g., [o jJ -P F O A ). The sam e internal standard should be used for a given analyte throughout the entire project/study. Note: some of the compounds Ksted below are appropriate to use as surrogate ISs when a stable isotope IS of a target analyte is not available. Generally, surrogate isotopicaily labeled PFCAs are used for PFCAs, and surrogate isotopically labeled PFSAs are used for PFSAs.
Table 2 provides examples of spike concentrations and volumes used to achieve a multi-point calibration curve with ISs and SRSs.
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Table 1. Stable Isotope PFCAs and PFSAs used for ISs and SRSs
CompoundName
Synonym orAcronym
l3C 4-Perfluorobutanoic acid
l5C 4-Perfluoropentanoic acid
[1 A 3 ,4 .',C ,]P FB A [l,2 ,3 ,4 ,5 -l3C j)P F P e A
>3CrPerfluorohexanoic acid 13C-Perfluoroheptanoic acid l3C r Periluorooctanoic acid
[ U - uC,]P FH xA [IA 3 .4 -" C.]P FH pA [1,2,3,4.5.6,7,8- "C tJP FO A
IJCrPeriluorononanoic acid 1'C-Perfluorodecanoic acid
[ 1,2,3,4,5,6,7,8,9-IJC ,]P FN A [1,2,3,4,5,6 - l3Q JP F D A
''CrPerfluoroiuidecanoic acid
[1,2,3,4,5,6,7 -IJC ,]P FU n A
13C r Perfluorododecanoic acid
[1,2 -,JCj]PFD oA
1'O rAm m onium Perfluorobutane sulfonate (" O j]PFBS
,5C r Ammonium Perfluorohexane sulfonate [l,2 ,3 -uCj]PFH S
13CrSodium Perfluorooctane sulfonate
[U ,3,4,5,6,7,8-13C,]PFO S
1!C-Perfluorooctanesulfonamide ,!C r Periluorooctanoic acid
[1,2,3,4,5,6,7,8-l3C i)FO S A [1.2,3,4-,3C ,]P FO A
AnnfyticaJPurpose
IS for P FB A IS for PFPeA
IS for PFH xA IS for PFH pA IS for P FO A and [1,2,3,4 "CJPFO A IS fo rP F N A IS for P FD A
ISforP FU nA
IS fo rP FD o A , *PFTA ISforPFB S IS for PFHS IS for P FO S and PFO S[l,2,3,4 ,3C J ,
IS for F O S A
SRS for aU PFCAs: C4-C8
SRotuftrrctenctStandard
W ellington Labs
(M ix or Individual)
W ellington Labs
(M ix or Individual)
W ellington Labs (M ix or Individual)
W ellington Labs
(M ix or Individual)
W ellington Labs
(M ix or Individual)
W ellington Labs
(M ix or Individual)
W ellington Labs
(M ix or Individual)
W ellington Labs
(M ix or Individual)
W ellington Labs
(M ix or Individual)
R TI International (Individual)
W ellington Labs
(M ix or Individual)
W ellington Labs
'
(M ix or Individual)
W ellington Labs (mix)
RTI International (Individual)
W ellington
''CrPerfluoroundecanoic acid 1'CrPerfluorooctane sulfonate
[1,2 -l3Ci]P FU n A [l,2,3,4-l3C 4]PFOS
SRS for all P FC A s C 9 -C I3 W ellington
SRS for afl PFSAs: C4, C6, and C8
W ellington
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Table 2. Example Preparation of Calibration Curve with ISs and SRSs
S a m p to in s c rip tio n
0.025 ngMiL cuve point 0.030 ngftnL curve point 0.04 ng/mL curve point 0.05 ng/mL curve point
0.1 ng/mL curve point 0.25 ng/mL cuve point 0.5 ng/mL cuve point
1 ng/mL cuve point 2.5 ng/mL cuve point 5.0 ng/mL curve point 10.0 ng/mL cuve point 25.0 ngAnL cuve point 50.0 ng/mL cuve point 75.0 ng/mL cuve point 100 ng/mL cuve point
ConceftfnMfon
o fW S .p g J m L
V o lu m e o f W S .p L
V o lu m e o f IS (2 p g fm L ),p L
0.10 0.10 0.10 0.10 0.10 0.10 1.0 1.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0
25 30 40 50 100 250 50 100 25 50 100 250 500 750 1000
50 50 50 50 50 50 50 50 50 50 50 50 50 50 50
C o n e o n tm U o n o f S u rro g a te , p g /m L
0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 10.0 10.0 10.0 10.0 10.0 10.0 10.0
V o lu m e o f S u rro g a te , /J .
12.5 15 20 25 50 125 250 500 25 50 100 NA NA NA NA
V o lu m e o fA S T M T y p e 1 W a te r, o r o ttie r s u ita b le s o lv e n tm , m L
100 100 100 100 100 100 100 100 100 100 100 100 100 100 100
N /A - Not Applicable (1) Samples requiring analysis for PFUnA, PFDoA, PFTrOA, and FOSA should be analyzed against a cattrration curve prepared in 1:1 synthetic groundwaterMeOH.
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8 Sample Collection and Bottle Preparation
Sample collection bottles are prepared by 3 M Environmental Laboratory (or subcontract supplier) personnel for shipment at ambient temperature to the collection site. Typically, four separate collection bottles are associated with a single collection site: sample, field duplicate sample, low field matrix spike, and high field matrix spike. Alternatively, the sample and field duplicate sample may contain SRSs in lieu of additional target analyte low field matrix spike and target analyte high field matrix spike samples. Depending on the scope of the project, additional replicates of the field sample and field matrix spikes may be added. Also, it is not uncommon for additional mid-level field matrix spires to be collected if the expected sample concentrations are truly unknown or could span a large concentration range.
High-density polyethylene (H D PE) wide-mouth Nalgene bottles are used for the sample collection containers. (Volumes o f the bottles may vary depending on how much sample is required to m eet data quality objectives.) Sample collection volumes are project specific and based on data quality objectives. The Nalgene bottles do not require any pratreatment prior to use. Typically, placement of a sample bottle volumetric Till to here* line is done by using a sample bottle marker template. Alternatively, bottles m ay be weighed prior to bottle preparation and weighed again after samples have been collected.
A l bottles should be clearly labeled to indicate its intended use as a sample, field sample duplicate, low field matrix spike, high field matrix spike, sample/SRS field matrix spike, field duplicate sam ple/SRS field matrix spike, trip blank, or trip blank matrix spike. If each location has different designated spike levels, the label should also clearly indicate the sample location designation. Generally, a set o f bottles for a given collection VsViteWaairl we Iovlraenoai lrev adi tahlea ln aMrloWuakDrweMd tWonafVeUthIwelr iInI I DalBlaPsPUtiVc abMaMas9 floa lr Worl MgaWnViMzMaMtiVoaani VaaWl aDaulryoWosaevsi VF%orrl eVaSIcVhII as^aMImVlolrllev collection event, at least one set of trip blank and trip blank matrix spikes are prepared.
Bottle preparation should be documented in a Note to File or on a sample preparation worksheet and should inI i VclIuWda Ve tBhPaae--fIoWlHloVw* MinwaSa i*n* lfl ol r lrmI l aa Wtioln '* dV HaatMe DraeaSoaaaalrWeMdf total nIMuImI llbifWe-r oa alf abVoWttlev sa PoalrVeWoVaBIraewdf InBuaP#mI IWbweVr aoalf sam11Daalwe asTitveWWsj tMhlaea standard identification numbers and spike volumes used to prepare spiked bottles, the Till to here' volume, and any other pertinent information needed for reconstructibility of the data. The Note to File will be included in the final data package for the project.
Samples are collected in the field and shipped to the laboratory at ambient temperature.
8.1 Field Matrix Spike Sample (FMS)
F eld matrix spike samples are a requirement of the method. A FMS sample is defined as a QC sample to which known quantities of appropriate target analytes are added to the sample bottle in the field or in the laboratory before the bottles are sent to the field. The sample and field duplicate sample may contain appropriate SRSs in lieu of target analyte FM S samples. Sample quantities are determined volumetrically or gravimetricaily. A known, specific volume or weight of sample is added to the sample container without rinsing. Volumetric sample measurements may be acquired by a laboratory applied Till to this level" line on the outside of the sample container. Target analyte FM S samples should be spiked at approximately 0.5-10 times the expected analyte concentration in the sample. If the expected range of analyte concentrations is unknown, multiple spikes a t varying levels may be prepared to increase the likelihood that a spike at an appropriate level is made. Typically a low and a high target analyte spike are prepared for each sampling location. In those instances where SRSs are to be used in lieu of target analyte FM S samples, the sample and field duplicate sample are spiked at approximately 2-5 times the target LOQ. The FM S is analyzed to ascertain if matrix effects or samole hddina time contributes bias to the analytical results For the samole bottles deskmated for matrix spires, an appropriate volume of matrix spiking solution is added to toe empty bottle prior to sampling. The volume of spike solution added should produce the desired final concentration of target analytes once the bottle is filled with sample to the T il to here line*. The matrix spiking solution(s) should be prepared in a suitable solvent and contain all of toe appropriate target analytes, ISs, and SRSs. The target analyte matrix spiking solution is often the sam e as toe working standards used to create the calibration standards. An example o f a bottle spike is given below.
` Fill to here' volume = 200 mL (A 250 mL Nalgene bottle is used)
Desired Field Spike Concentration = 0.25 ng/mL
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500 pL of a 0.1 pg/mL spicing solution (containing the target analytes) is added to the bottle and the bottle cap promptly sealed.
8.2 Internal Standard and Surrogate Recovery Standard
If analysis of a surrogate recovery standard (SR S) is included in the project objectives, an appropriate volume of a surrogate standard solution is added to a l the bottles prior to sampling and SPE. Typically sample bottles are spiked with surrogate recovery standards at a final desired spice concentration o f 0.1 ng/mL.
If quantitation by internal standard (IS ) is included in the project objective, an appropriate volume of internal standard solution is added to a l the bottles prior to sampling and SPE. Typically sample bottles are spiked with internal standard at a final desired spike concentration of 1 ng/mL.
For the trip blank, the SR S spike and IS spike is added to the bottle and then ASTM Type I water (HPLC grade reagent water or other suitable water may used) is added to the "fil to here' line. The bottle is capped and sealing tape m ay be placed around the outer edge of the cap. Trip blank matrix spikes are prepared by adding the appropriate volume of target analyte spiking solution, IS, and SRS spiking solutions and fitting the bottle to the desired volume with the appropriate water and capping and sealing the cap.
9 Quality Control and Data Quality Objectives
9.1 Data Quality Objectives
This method and required quality control sam ples' designed to generate data accurate to 30% with a targeted LOQ of 0.025 ng/mL. Any deviations from the quality control measures spelled out below will be documented in the raw data and footnoted in the final report.
9.2 Method/Procedural Blanks
The method/procedural blank is zero point calibration standard (which includes ISs) analyzed in a regular basis with each analysis batch. At a minimum, method blanks are analyzed prior to instrument calibration, prior to the analysis of C C V samples, after every 10 sample injections, and at the end of the analytical run.
The mean area count or area ratios when using internal standard calibration, for each analyte in the method blanks must be less than 50% of the area count counts or area ratios when using internal standard calibration, of the LOQ standard. The standard deviation of the area counts, or area ratios when using internal standard calibration, of these method blanks should be calculated. A specific % R SD acceptance criteria is not specified but is assessed on an analytical batch basis. If the mean area counts or area ratios when using internal standard calibration, of the method blanks exceed 50% of the LOQ standard, then the LOQ must be raised to the first standard level in the curve teat meets criteria. Method blanks m ay be eliminated if technical justification can be provided (e.g. the procedural blank was analyzed after an unexpectedly high level sample). If any procedural blanks are removed from the LOQ determination, document in the raw data and report as appropriate. Laboratory Sam ple R eplicates/Field Duplicate Sample
Typically, samples are collected in duplicates in the field. The relative percent difference (R PD ) of duplicate samples should be 2 0 % for the precision of sample preparation and analysis to be considered in control. Replicate samples not meeting the 20% RPD criteria are flagged and reported as outside of Q C acceptance
9.3 Laboratory Matrix Spikes (LMSs)
LMSs m ay be performed in lieu of FMSs if FM Ss have previously been performed for the sample m atrix Additionally, LMSs may be performed in lieu of FMSs for a sample matrix if the FM S levels were not appropriate for determining spike recoveries relative to endogenous levels of target analytes and appropriate SRSs. Generally, each sample location represents a different sample and sample matrix. LMSs are prepared for each sample and analyzed to determine the matrix effect on spice recovery efficiency of each target analyte and appropriate SRSs. LMSs should be prepared at a minimum of one level and in duplicate. LMS concentrations should be prepared at approximately 0.5-10 tim es the endogenous concentration or approximately 4 -10 times the LOQ concentration of each target analyte.
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Lab matrix sp ke recoveries should fall within 30% of expected values. Sample data with LMS recovery outside of 30% but within 50% o f the expected value are flagged and reported as outside of Q C acceptance criteria. Data with LMS recovery outside of 50% of the expected value are reported as NR, where NR is defined as ` Not Reportable' data outside of QC acceptance criteria.
9.4 Lab Control Sample
Lab control sp kes are prepared for each analysis batch to determine method accuracy and precision. LCSs
should be prepared at three levels in triplicate for each target analyte and at a minimum of two levels in
triplicate for appropriate SRSs. Low lab control spikes should be prepared a t a concentration in the range of
approximately four to ten times higher than the targeted lower LOQ, the mid lab control spikes should be
prepared at a concentration near the mid-point of the caltoration curve and the high lab control spikes at
approximately 80% of the upper LOQ. For each target analyte and SRSs, the percent relative standard
deviation (method precision) for each control spike level must be less than or equal to 2 0 % and the average
recovery (method accuracy) for each control spike level must be 80-120% . Sam ple data tor target analytes
outside of the laboratory control spike acceptance criteria wifl be handled as follows:
.
If the average recovery of a spiking level falls outside method acceptance, but at least 67% (6 out of 9 ) o f LCS samples are within 20% o f their respective nominal value (33% of the Q C samples, not all replicates at the same concentration, m ay be outside 2 0 % of nominal value), the average recovery will be flagged as outside method acceptance criteria. All LCS samples will be control charted as per ETS-4-026. If the average recovery of one of the spiking levels exceeded the analytical method uncertainty as determined by E TS -120 1 2 , that analytical batch uncertainty will be expanded tor that particular study.
If more than 67% o f the LCS samples fail to m eet method acceptance criteria, the data will not be repotted.
CaHbration standards consisting of mixed branched and in ear isomer PFO S/PFOA are preferred. However, for PFO S/PFO A target analytes, if the calibration standards are comprised of predominantly linear isomers only, at least one level of triplicate LCSs should be prepared using PFO S/PFO A which contains a mix of linear and branched isomers. These LCSs w il be used to demonstrate quantitative equivalency (or quantitative bias) of the isomeric mix when using a predominantly linear standard for calibration. The mixed linear and branched
isomer PFO S/PFOA LCSs recoveries should fall within 30% of expected values. Alternatively, in lieu of mixed branched and linear isomer PFO S/PFO A LCSs, mixed branched and linear isomer PFO S/PFOA TBM Ss m ay be applied to demonstrate method accuracy and precision.
9.5 Field Matrix Spikes (FMSs) / Surrogate Recovery Standards (SRSs)
FMSs are prepared for each sampling location and analyzed to determine the matrix effect and sample holding time on the sp ke recovery of each target analyte and/or appropriate SRS. Generally, each sample location represents a different sample and sample matrix.
FMSs are QC samples to which known quantities o f appropriate target analytes are added to the sample bottle in the laboratory before the bottles are sent to the field. Typically a low and a high target analyte FM S are prepared for each sampling location. The sample and field duplicate sample may contain appropriate SRSs in lieu of target analyte low field matrix spike and target analyte high field matrix spke samples.
Field matrix spike method acceptance criteria are recoveries within 30% of the expected value. If FM S recovery (target analyte or SRS sp ke) is outside of 30% of the expected value or could not be assessed because the FM S (target analyte) was spiked at an inappropriate level, the sample result is reported as (blows:
1. ) If target analyte FM S recovery could not be assessed because the FMS's were at an inappropriate level, then Laboratory Matrix Spikes (LMS) m ay be substituted. If LMS recoveries are within 30% the data are reportable and flagged to indicate that the FM S spikes levels were inappropriate.
2. ) If multiple target analyte FMS's w ere prepared on a sample and the closest FM S level to the reported sample m eets the 30% acceptance criteria but additional FMS's are outside the 30% acceptance range, the data are reportable and flagged to indicate that while there were failing FMS's, the uncertainty will not be expanded since the most appropriate spike level passed.
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3. ) If the target analyte FM S recoveries are outside of the 30% acceptance range but at least 30 acceptable historical reportable FM S sample results are available, the data may be reported but flagged with an expanded uncertainty and as not meeting FM S criteria
4. ) Sample data with FM S recovery outside of 30% but within 50% of the expected value are flagged and reported as outside of Q C acceptance criteria with an expanded uncertainty.
5. ) If FM S recovery is outside of 50% , the sample result is reported as NR, where NR is defined as ` Not Reportable' due to noncompliant Q C results.
The targeted fortification levels should be at least 50% of the endogenous level and less than 10 times the endogenous level to be used without justification to determine the statement of accuracy for analytical results.
Note: It is possible for bottles utiized for Field Matrix S pire samples to be under-filled or over-filled during sample collection. Since this scenario will effect the actual concentration of the FMS sample (surrogate and internal standard concentrations will also be effected, if used), it is important that any obvious underfilling or over-filling of sample bottles be documented in the data package and taken into account in the FM S, ISs, or SRSs recovery calculations. Samples over-filed or under-filled by more than 10% w il be require recalculation of the FM S, ISs, and SRS true values.
The average of the sample and the field duplicate should be used to calculate the recovery.
10 Procedures
10.1 Water Sample Preparation
This method is applicable to water samples. Samples containing heavy particulate may not be suitable for analysis by this method. Samples containing suspended particulate should be centrifuge prior to removing a sample aliquot, or tittered.
Thoroughly mix sample before removing an aliquot and placing in a labeled autovial.
Dilute sample, if necessary, with A STM Type I water, HPLC water, other suitable water, or solvent (m ethanol).
Lab control spikes are prepared for each analysis batch to determine method accuracy and precision. LCSs should be prepared at three levels in triplicate for each target analyte and at a minimum of two levels in triplicate for appropriate SRSs. Low lab control spikes should be prepared at a concentration in the range o f approximately four to ten times higher than the targeted lower LOQ, the mid lab control spikes should be prepared at a concentration near the mid-point of the calibration curve and the high lab control spikes at approximately 80% of the upper LOQ. For IS quantitation, stable isotope internal standards of each target analyte or appropriate surrogate ISs should be spiked at the sam e level as the samples being analyzed, in all LCSs.
If LCSs are being prepared using synthetic groundwater, allow the LCSs samples to equilibrate for a minimum of 4 hours before aliquoting for analysis or diluting with solvent (methanol).
11 Sample Analysis - LC/MS/MS
11.1 Instrument Setup
N ote: In this example, an Applied Biosystems Sciex A PI 4000 (API 5000 or API 5500) Tandem Mass Spectrometer (LC/M S/M S) is used. Other brands/models of LC/M S/M S instruments as well as stogie quadrupole mass spectrometers (LC/M S) may be used as long as the method acceptance criteria are met. Brand names, suppliers, part numbers, and models are for illustrative purposes only. Equivalent performance m ay be achieved using apparatus and materials other than those specified here, but demonstration of equivalent performance that meets the requirements of this method is the responsibility of the laboratory. The operator must optimize and document the equipment and settings used.
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Establish the LC/M S/M S system and operating conditions equivalent to the following: Mass Spec: Applied Biosystems API 4000, A PI 5000, or API 5500 Ion Source: Turbo Ion Spray (ABS) Mode: Electrospray Negative Scan Type: M R M (Multiple Reaction Monitoring) Com puter D ellD H M Software: Windows 2000 or Windows X P, Analyst 1.4.2 or higher versions HPLC: Agilent Series 1100,1200, or 1290 Agilent Quaternary Pump Agilent Vacuum Degasser Agilent Autosampler Agilent Column Oven Note: One or more C 18 HPLC analytical columns (2.1 mm x 100 mm, 5pm or 2.1 mm x 50 mm, 5pm) may be attached on-line after the purge valve and before the sample injection port to retard and separate any residue contaminants that may be in the mobile phase and/or HPLC system. HPLC Column: Betasil C 18,4.6m m x 100mm, 5pm (ThermoElectron Corporation) Column Temperature: 35` C Injection Volume: 5pL Mobile Phase (A): 2m M Ammonium Acetate in ASTM Type I water (S ee 7.3) Mobile Phase (B): Methanol
Table 3. Liquid Chromatography Gradient Program.
step
N um ber
0
1
2 3
4
5
T o ta l T im (m in )
F lo w R a ta Q d J m ln )
0 2.0 14.5 15.5 16.5 20.0
750 750 750 750 . 750 750
P ercen t A ( 2 m U a m m o n iu m
a c e ta te )
97.0 97.0 5.0 5.0 97.0 97.0
P ercen t B (M e tb a n o l)
3.0 3.0 95.0 95.0 3.0 3.0
Note: Other HPLC gradients may be used as long as the method criteria and project data quality objectives are m et
It may be necessary to adjust the HPLC gradient in order to optimize instrument performance. Columns with different dimensions (e.g. 2 .1 mm x 30mm ) and columns from different manufacturers (Keystone Betasil C18 etc.) m ay be used.
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Table 4 Suggested MRM Transitions for Target Analytes, Surrogates, and Internal Standards
Analyte
P FB A (C4 A cid) PFPeA (C5 Acid) P FH xA (C6 Acid) PFHdA (C 7 A cid) P FO A (C8 A cid)
P FN A (C9 Acid) P FD A (CIO A cid) P F U n A fC ll A cid) P FD oA (C12 A cid) P F T A (C I3 Acid) FB S A fC4 Sulfonamide) F O S A (C8 Sulfonamide) PFBS (C4 Sulfonate) PFHS (C6 Sulfonate) PFOS (C8 Sulfonate) r 1.2.3,4- IJC ,1 P F B A rU .3 .4 ,5 -C )lP FP e A I U - iiC 21PFHxA IU .3 .4 - ''C IP F H dA IU .3.4.5.6.7.8-1,C ,1P F0A 11_2.3.4.5,6.7.8.9-'JC1PFNA 112.3.4.5.6- " a iP F D A r 12.3.4.5.6.7 -"C ilP F U n A 112 -''C ilP F D o A ("O ilP F B S il.2 .3 -uC ,lP FH S f 12.3.4- I}C,1PF0S 112.3.4,5.6.7.8-llC ilF O S A [12.3,4-,JC .]P FO A (12,3.4- l5C ,lP FO S (12 -uC ilP F U n A
Analyte Description
Target Target Target Target Target
Target Target Target Target Target Target Target Target Target Target IS for P F B A IS for PFPeA IS for P FH xA IS for PFH dA IS for P FO A IS for P FN A IS for P FD A IS for PFU nA IS for PFD oA and P FTA IS for PFBS IS for PFHS IS for PFOS IS for FO S A Surrogate (C4-C8 Acide) SunogatefSulfonates. FO SA) Surrogate (C9-C13 Acide)
Mass Transition Qi famni
213 263 313 363 413 463
5)3 563 613 663 298 498 299 399 499 217 268 315 367 421 472 519 570 615 303 402 503 507 417 503 565
Mass Transition 03 (omul
169 219 269.119 319.169 369.219.169 419,169,219
4 6 9 .2 6 9 .2 1 9 5 1 9 .2 6 9 .2 1 9 5 6 9 .1 6 9 .3 1 9 6 1 9 .3 6 9 .3 1 9
78 78 9 9 .8 0 9 9 ,8 0 8 0 .9 9 .1 3 0 172 223 270 322 376 427 474 525 570 84 80 80 80 372 80 520
Multiple transitions for monitoring the analytes is an option. The use of one daughter ion is acceptable if data sensitivity and selectivity is achieved and provided that retention time criteria are met to assure adequate specificity. W hile the daughter ions may be chosen at the discretion of the analyst, mass transition 99 is suggested for PFO S. Quantitation m ay be performed using the total ion chromatogram (TIC , or summed M RMs) for a given analyte. For example, the PFOA TIC would sum all three o f the monitored transitions. Use of the suggested primary ion is recommended. Retention times may vary slightly, on a day-to-day basis, depending on the batch of mobile phase and the gradient, column, guard colum ns) used etc. Drift in retention times is acceptable within an analytical run, as long as the drift continues through the entire analysis and the standards are interspersed throughout the analytical run.
11.2 Calibration Curve
Quantitation is by internal standard or external standard calibration. Calibration standards m ay be prepared in A STM Type I, HPLC water, other suitable water, or a solvent/water mixture. If internal standard calibration does not m eet calibration acceptance criteria, external calibration can be applied. See Table 1 for
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recommended application of available internal standards. Quantitation o f PFOA and PFO S is by summed analyte-specific mass transitions.
Analyze the standard curve prior to each set of samples. If internal standards were added to the calibration
standards area ratios are used to aenerate the calibration curve. The standard curve mav be lotted usino ababams sbb^uisp baba bsbbbabas pbabsbaba
dbab^^baba baa babab bbab babba as pba b^bbbsbbab bpbbbbab b babab w ba a p sba babnas ^babas ba b^bas w ba b sba w baba ba^babbaaba bababb ppm ba
linear regression (y m x + b), weighted 1/x or unweighted, or by quadratic fit (y = ax2 + bx + c), weighted 1/x or
unweighted, using suitable software. The mathematical method used to calculate the calibration curve should
be applied consistently throughout a study. Any change should be thoroughly documented in the raw data.
High and/or low points may be excluded from the calforation curves to provide a better fit over the range appropriate to the data or because they did not m eet the pre-determined acceptance criteria. Low-level curve points should also be excluded if their area counts (or area ratio if quantitating by IS) are not at least twice that of the average area counts (or area ratio if quantitating by IS) of method and/or solvent blanks. The coefficient of determination (r2) value for the calibration curve must be greater than or equal to 0.990 (or a correlation coefficient (r) of 0.995). Each point in the curve must be within 25% of the theoretical concentration with the exception of the LLOQ, which may be within 30% . Justification for exclusion of calibration curve points w il be noted in the raw data. A minimum of 6 points will be used to construct the calibration curve.
If the calibration curve does not m eet acceptance criteria, perform routine maintenance or prepare a new standard curve (if necessary) and reanalyze.
11.3 Continuing Calibration Verification (CCV)
Continuing calibration verifications (C C V) are analyzed to verify the accuracy ofthe calibration curve. Analyze a mid-range calibration standard, one of the sam e standards used to construct the calibration curve, at a minimum after every tenth sample, not including solvent blanks, with a minimum of one per sample s e t Calibration verification injections must be within J25% to be considered acceptable. The calibration curve and the last passing C C V will then bracket acceptable samples. Multiple C C V levels may be used. Samples must be bracketed by passing CCVs or the calibration curve and a passing C C V to be reportable.
11.4 System Suitability
A minimum of three system suitability samples should be injected at the beginning of each analytical run, prior to the analysis of the calibration curve. Typically these samples are a t a concentration near the mid-level of the vcaaa ilwibwrba^wtisobabns curvebabab v ba andbab bba wa ri bea reoeatadababab^bsbbbaba sisnmjbeabcabtbiboabnmsa f r--boabma a onebap sba autosam olerbababb^b^aab bbaapbap vw iwaili . It is suoaested th at th e systemi % sba babasabababab^ aba bb bbab bs bba ba wbabba. * p suitability injections have area counts or area ratios when using internal standard calibration, with a target RSD of 5% and a target retention time RSD of 2% . There is no defined acceptability limit on these results as the % RSD value is dependent on the number of MRM transitions being monitored in the LC/M S/M S run or time period. Ultimately, any effects on these parameters for the System Suitability samples will also be evident on all standards and QC samples analyzed as p art of the analysis batch. Any effect of system suitability Is incorporated within QC acceptance criteria.
11.5 Sample Analysis and QCs
For each analysis batch, the instrument analysis run sequence should include an initial calibration cures, samples, FDSs, interspersed blanks, interspersed CCVs, appropriate Q C s (i.e., LCSs, LMSs, FMSs, TBMSs, and TBs), end a final C C V or calibration curve bracketing samples and appropriate QCs
Inject the sam e volume (between 5 - 1 0OpL) of each standard, analytical sample and blank into the instrument (unless an on-instrument sample dilution is desired).
SB^^aABmBPoJA^tBeABsA cB^BoABnBtBaB^Ain#MiBnBBaA aB^HnHahfIvWtB&B^BsA tBhBBaBAtB Sa^ArBeA BaAuB^aBAnS&itated BaAbBABoAvTMBeA tBPhSBaA conBcB^AeAVnBtBrSBaABtii--oBAPn--oBASf tBShSBaA hBBSkBAiBhBBaABsAtB bsaBtaamBnBdB^^aEAPrBdA BiBnB tBBh^BaA BcABuASrvWBeA should be further diluted and reanalyzed.
*3M Environmental Laboratory study E08-0096 evaluated the effect on these results as a function o f the number o f M R M s being monitored.
ETS-8-044.1
Page 18 of 22
Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection
Analysis
Page 73 of 77
l A i __ LI -ju t a __ 1_L iiM __ k
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12 Data Analysis and Calculations
The chromatography analysis software will typically calculate the amount of target analyte in the sample extracts using the established calibration curve. Calculate the percent recovery of the LCS using the following equation:
LCS%recovery---L--C--S--C--o-n--c-e-n--tr-a--ti-o-n--- ffik_*ioo%
Spike Concentration
Calculate the percent recovery of the LMS using the following equation:
(-- )L M S C oncentration
- C o n cen tratio n o f S a m p le (-^7 -)
L M S % re co v e ry - ___________________ m L
mL
S p ik e C on cen tration (-^7 -) mL
100%
For samples fortified with known amounts of analyte prior to extraction, use the following equation to calculate the percent recovery.
Total analyte found (ng/m L) - A verage analyte found in sam ple (ng/m L) ^
eC0V81^ ~
Analyte added (ng/m L)
*
13 Analysis Batch Method Performance Criteria
Any method performance parameters that are not achieved must be considered in the evaluation of the d ata Nonconformance to any specified parameters must be described a id discussed in the final report if the Technical M anager (non-GLP study) or Study Director (G LP study) chooses to report the data.
If criteria listed in this method performance section are not m e t maintenance m ay be performed on the system and samples reanalyzed, or other actions taken as appropriate. Document all actions in the raw data.
If data are to be reported when performance criteria have not been m e t the data must be footnoted on tables and discussed in the text of the report.
. 13.1 System Suitability - Analysis Batch
A minimum of three system suitability samples should be injected at the beginning of each analytical run. These samples are run prior to the calibration curve. K is suggested that the system suitablity injections have area counts with a target R SD of s5% and a target retention tim e RSD of f i% . There is no defined acceptability limit on these results as the % RSDs are dependent on the number of M RM transitions being monitored in the LC/M S/M S run or tim e period. Any effect of system suitability is incorporated in the QC acceptance criteria.
13.2 Calibration and Limit of Quantitation (LOQ) - Analysis Batch
C alibration C urve: The coefficient of determination (r2) value for the calibration curve must be greater than or equal to 0.990 corresponding to a correlation coefficient (r) = 0.995. Each point in the curve must be within 25% of the theoretical concentration with the exception o f the LLOQ, which may be within 30% .
C C V Perform ance: The calibration standards that are interspersed throughout the analytical sequence are
evaluated as continuing calibration verifications in addition to being part o f the calibration curve. The accuracy
ETS-8-044.1
Page 19 of 22
Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection
Analysis
Page 74 of77
ABenratlGJyeLsfiPsfr1oie0fs-P0LF1aB-n0Sd2f.;ilPIlnF-tHeFreSimb,rauRnaedrpyPo2Fr0tO21S26
o f each curve point must be within 25% of the theoretical value (within 30% for lowest curve point). Samples that are bracketed by C C Vs not meeting these criteria must be reanalyzed.
Lim its o f Q uantitation (LO Q ): The lower LOQ (LLOQ ) is the lowest non-zero active standard in the caibration curve; the peak area of the LLOQ must be at least 2X that of the average area counts for all prepared procedural blank(s). By definition, the measured value of the LLOQ must be within 30% of the theoretical value.
D em onstration o f S pecificity: Specificity is demonstrated by chromatographic retention time (within 4% of standard) and the mass spectral response o f unique ions.
13.3 Blanks - Method/Procedural Blanks and Trip
M ethod/Procedural B lanks: Multiple procedural blanks should be interspersed throughout the analysis batch and the analytical sequence. At a minimum, method blanks are analyzed prior to instrument caUbration, prior to the analysis of C C V samples, after every 10 sample injections, and at the end of the analytical run.
The mean area counts (or area ratios when using IS caibration) for each analyte must be less than 50% of the area count of the LOQ standard. If the area counts of the procedural blanks exceed 50% of the LOQ standard, then the LOQ must be raised to the first standard level that meets criteria.
T rip B lank: A trip blank of ASTM Type I water (or lab equivalent) is prepared in a sample container in the laboratory and treated as a sample, including exposure to shipping, sampling site conditions, storage, preservation and all analytical procedures. The trip blanks results for each analyte are included with the reported sample results.
13.4 Data Accuracy and Precision - Analysis Batch
Lab C ontrol Spikes: The average recovery at each LCS level for each target analyte and appropriate SRS should be within 80-120% and the percent relative standard deviation of the recoveries must be less than or equal to 20% . If the average recovery of a spiking level falls outside method acceptance, but at least 67% (6 out of 9) of LCS samples are within 20% of their respective nominal value (33% of the Q C samples, not all replicates at the sam e concentration, may be outside 20% of nominal value), the average recovery will be flagged as outside method acceptance criteria. All LCS samples will be control charted as per ETS-12-012. If the average recovery of one of foe spiking levels exceeded the analytical method uncertainty as determined by E TS -12-012, that analytical batch uncertainty will be expanded for that particular study. The average recovery at each LCS level for mixed branched/linear isomer PFO A and PFO S should be within 70-130% and the percent relative standard deviation of the recoveries must be less than or equal to 20% .
Field D uplicates: The relative percent difference (R PD ) of duplicate samples should be less than 20% for the precision of sam ple preparation and analysis to be considered in control Replicate samples not meeting the 20% RPD criteria are flagged and reported as outside of Q C acceptance criteria.
Field M atrix Spikes: FM S acceptance criteria are recoveries wthin 30% of the expected value for each target analyte and appropriate SRS. Sample data with FM S recovery outside of 30% but within 50% of the expected value are flagged and reported as outside of Q C acceptance criteria. Data with FM S recovery outside o f 50% of the expected value are reported as NR, where NR is defined as ` Not Reportable* data outside of Q C acceptance criteria. If FM S recovery could not be assessed because FM Ss were at an inappropriate level, then Laboratory Matrix Spikes (LMSs) m ay be substituted. If LM S recoveries are within 30% for each target analyte and SRSs the data are reportable but flagged as not meeting the FM S method acceptance criteria.
13.5 Analytical Method Uncertainty
Analytical method uncertainty for each target analyte and SRS is determined with control charted historical analysis batch LCS data for the method and reported with each analysis batch.5 Uncertainty determinations
5 Method uncertainty based on INTERNATIONAL ANS/ISO/IED STANDARD 17025 reference (GUM, Guide to the Expression of Uncertainty in Measurement). Method application demonstrated in ETS-12-012, citing references: a.) EURACHEM/CITAC Guide, "bQ.)Guaenotrigfytainng, TUhnocmeratsa,in"tEystiinmAantiaolnytoicfaLlaMboeraastuorreymAennat,l"ytSiceacloUndncEedrittaiionnt;yEUdsiitnogrs:LSab.Lo.rRat.orEyllCisoonnt,rMol.SaRmopsslelesi,n",EannvdirAo.nmWeinlltiaalmTse.sting &
ETS-8-044.1
Page 20 of 22
Method of Analysis for foe Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection
Analysis
Page 75 of77
G LP10-01-02; Interim Report 26 A n a lysis of P F B S , P F H S , and P F O S Bart Jeffries Landfill - February 2012
are based on INTERNATIONAL A N S/ISO /IED STANDARD 17025 reference (GUM , Guide to the Expression of Uncertainty in Measurement) and described in ETS-12-012. At least thirty data points are required for determining analytical method uncertainty. The method uncertainty is defined as 2x the standard deviation of the percent recoveries of the pooled tab control spikes. W hile all LCS data points are control charted, only the most recent fifty data points are used for determining the method uncertainty.
W hen less than thirty LCS data points have been generated for a given analyte, the analysis batch LCSs are used to determine the data uncertainty. If FMSs m eet the 30% recovery criteria at a level appropriate to the endogenous level, and the LCS m eet the 20% recovery criteria, then the uncertainty of the data is determined as within 10Q20%.
Analysis batch sam ple data with FM S recovery outside of 30% but within 50% of the expected value are flagged and reported as outside of QC acceptance criteria with expanded uncertainties. Data with FM S recovery outside of 50% o f the expected value are reported as NR, where N R is defined as "N et Reportable' data outside of Q C acceptance criteria If FM S recovery could not be assessed because FM Ss were at an inappropriate level, then Laboratory Matrix Spikes (LMSs) m ay be substituted. If LMS recoveries are within 30% for each target analyte and appropriate SRSs the data are reportable but flagged as not meeting the FM S method acceptance criteria with uncertainties of 30% . If FM S do not m eet the 30% recovery criteria, and historical FM S data does not exist, the analytical uncertainty is evaluated on a sample-by-sample basis, the data may be reported with expanded uncertainty and are flagged.
13.6 Quantitation of PFOA/PFOS - Analysis Batch
Calibration standards consisting of mixed branched and linear isomer PFO S/PFOA are preferred. Quantitation is performed by integrating the linear and branched isomers together. Alternately, the linear and branched isomers can be integrated separately, applying the appropriate true value to each calbration curve point for each isomer. The LCS and samples are then quantitated by integrating the linear and branched isomers separately (requires separate analytical results files) and quantitating the resulting peak against the linear or branched calbration curve. The results from both integrations are then summed to produce the final result Integrating the linear and branched isomers separately may be helpful for those samples where the linear/branched ratios do not closely match those of foe reference standards.
However, for PFO S/PFOA target analytes, if the calibration standards are comprised of predominantly linear isomers only the method requires the addition of LCSs of mixed branched/linear isomer PFOS/PFOA. The purpose of including these LCSs is to demonstrate quantitative equivalency (or quantitative bias) o f the isomeric mix when using a predominantly linear PFO S or PFOA standard for calibration. Alternatively, in lieu of mixed branched and linear isomer PFO S/PFOA LCSs, mixed branched and linear isomer PFO S/PFOA TBM Ss may be applied to demonstrate method accuracy and precision.
An alternate method of quantitation can be performed whereby only the linear isomer of PFO S/PFOA is integrated and used for generating the calibration curve. The LCS and samples are then quantitated by integrating the linear and branched isomers separately (requires separate analytical results files) and quantitating the resulting peak against the linear cafibration curve. The results from both integrations are then summed to produce the final result Integrating the linear and branched isomers separately reduces the oncolumn concentration for those samples that contain both linear and branched isomers of PFOA/PFOS. This ensures that the concentration detected is within the a range of the calibration curve that is comparable regardless of whether the calibration curve was generated using predominantly linear isomers of PFO S/PFOA or linear plus branched isomers of PFO S/PFO A
14 Pollution Prevention and Waste Management
W aste generated when performing this method will be disposed of appropriately. The original samples w il be archived at the 3M Environmental Laboratory in accordance with internal procedures.
AEMvneaaallsuyuasritesinm, gNeaonnvtdeUmEnbcxeeprrrt/eaDsinseitcnyegminthbTeereUs2tn0icn0eg0r".t,acJi.nu)Ttlyyaoy2lf0oN0r2,I.BST.NM. eaansdurCeEm.enKtuRyeasttu,lNtsI."SdT.)TAedcahmnsic,aTl.NMo.,te"A1229L7A,1G9u9i4deEdfoitriothn:e"EGstuimidaetliionnesoffor
E TS -8-044.1
Page 21 of 22
ABenratlGyJesLfisPfr1oie0fs-P0LF1aS-n0Sd2f,;ilPIlnF-tHeFreSimb, rauRnaderpyPo2Fr0tO21S02
15 Records
Each data package generated for a study must include all supporting Information for reconstruction of the data.
Information for the data package must include, but is not limited to the following items: study or project
number, sample and Stamford prep sheets/records, instrument run log (instrument batch records, instrument
acquisition method, summaiy pages), instrument results files, chromatograms, calibration curves, and data
calculations.
..
16 Affected Documents
None.
17 Revisions1*
Revision N um ber
1
Sum m ary of Changes
Section 1. Included the use ofinternal 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 forPFUnA, PFDoA, PFTrDA, and FOSA. Section 3. Added definitions for internal standard, surrogate internal standard, and surrogate recovery standard. Section d.Removed the details regarding the instrumentparameters to section 10 ofthe
method. Section 7. Updated reference standards to include internai 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 sectbn was previously section 10 in ETS-8-044.0. Updated QC criteria to be consistent with method ETS-8-154.4. Section 10 Procedures. This section was previously section 8 (Sample Handling) in ETS-8044.0. Added detail regarding the preparation of LCSs. Included the use ofmethanol as a dilution solvent. Section 11 Sample Analysis. This section was previously section 10 in ETS-8-044.0. Included the details regarding the instrumentparameters. Section 12 Data Analysis and Calculations. This section was previously section 11 in ETS8-044.0. Removed the equation for calculating the analytes concentration, indicating that this is done by the instrument software. Section 13 Method Performance. This section was previously section 12 in ETS-8-044.0. Updated QC criteria to be consistent with ETS-8-154.4. Added information on the detennination ofanalytical method uncertainty and quantitation ofPFOA/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 of 22
Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection
Analysis
Page 77 of77
G L P 1 0 -0 1 -0 2 : In te rim R e p o rt 3 0 - A n a ly s is o f P F B S . P F H S . a n d P F O S in G ro u n d w a te r S a m p le s C o lle c te d a t O ff-S ite W e lls o n B e rt J e ffrie s P ro p e rty in D e c a tu r. A L in A p ril 2 0 1 2
S tu d y T itle
Analysis of Perfluorooctane Sulfonate (P F O S ), Perfluorohexane Sulfonate (P F H S ) and Perfluorobutane Sulfonate (P F B S ) in Groundwater, Soil and Sedim ent for the 3M D ecatur Phase 3
Site-Related Monitoring Program
D ata R eq u irem en t E P A T S C A Good Laboratory Practice Standards 4 0 C F R P art 792
S tu d y D ire c to r Jaisim ha K esari P .E ., D E E
W eston Solutions, Inc. 1400 W eston W ay
W est C hester, PA 19380 Phone: 610-701-3761
A uthor Susan W o lf 3M Environm ental Laboratory
In te rim R e p o rt C o m p le tio n D ate D ate o f signing
P e rfo rm in g L a b o ra to ry 3M Environmental Health and Safety Operations
Environmental Laboratory 3M Center, Bldg 260-05-N -17
S t Paul, M N 55144
Project Identification
G LP 10-01-02-30
T otal N um ber o f Pages
112
A C C il
i The te stin g reported herein m eet the requirem ents o f ANSI/tSOflEC 17025:2005 "G eneral Requirem ents fo r
' th e Com petence o f Testing end C alibration Laboratories'1, In accordance w ith the A2LA Testing C e rtifica te <
DJ 2062.01. Testing th a t compSes w ith th is International Standard also m eets p rin cip le s o f ISO 9001:2000.
T e s tin g C e rt #2052.01
i
I I kla u n n i
__ i : i I m b j u t
G LP 10 -0 1 -0 2; Interim R eport 30 A n a ly sis o f P F B S , P F H S , a n d P F O S in G rou ndw ater S a m p le s
B ert Je ffrie s Property - A p ril 2012
This page has been reserved for specific country requirem ents.
Page 2 of 112
Analysis ofPFBS. PFHS, andBGPerLFtPOJe1Sf0f-ri0nie1Gs-0Pr2or;uoInpndeterwtryiamt-eArRSperapimlo2rp0tl13e02s
G L P C o m plian ce S tatement
Report Title: Interim Report 30 - Analysis of PFBS, PFHS, and PFO S in Groundwater Samples Collected at Off-Site W e is on B eit Jeffries Property in Decatur, AL in April 2012. Study: Analysis of Perfiuorooctane Sulfonate (PFO S), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane Sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program. This analytical phase was conducted in compliance with Toxic Substances Control Act (TSCA) Good Laboratory Practice (G LP) Standards, 40 C FR 792, with the exceptions listed below:
These are environmental samples where there is no specific test substance, no specific test system and no dosing of a test system.
The reference substances have not been characterized under the GLPs and the stability under storage conditions at the test site have not been determined under GLPs.
Page 3 of 112
GLP10-01-02; Interim Report 30 Analysis of PFBS, PFHS, and PFOS in Groundwater Sample*
Beit Jeffries Property April 2012
Q u ality A ssu r a n c e Statem ent
Report Title: Interim Report 30 - Analysis of PFBS, PFHS, and PFO S in Groundwater Samples Collected at Off-Site Weds on Bert Jeffries Property in Decatur, AL in April 2012.
Study: Analysis of Perfluorooctane Sulfonate (PFO S), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane Sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program.
This analytical phase was audited by the 3M Environmental Laboratory Quality Assurance Unit (QAU), as indicated in the following table. The findings were reported to the principal investigator (P .I.), laboratory management and study director.
In sp e ctio n D ate* 4/27/12,4/30/12
Data and Report
DateReportedto
T e stin g FacMHy M anagem ent
Study Director
5/1/12
5/1/12
Page 4 of 112
GLP10-01-02; Interim Report 30 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples
Bert Jeffries Property - April 2012
Table of C ontents
G LP Com pliance Statem ent.................................................................................................................................. 3 Q uality Assurance Statem ent................................................................................................................................4 Table of C ontents.....................................................................................................................................................5 List o f T a b le s ............................................................................................................................................................ 6 1 Study Inform ation............................................................................................................................................. 8 2 S um m ary........................................................................................................................................................... 9 3 Introduction...................................................................................................................................................... 10 4 Test & Control S ubstances......................................................................................................................... 11 5 R eference Substances................................................................................................................................. 11 6 Test S y s te m ....................................................................................................................................................13 7 Method S um m ary..........................................................................................................................................13
7.1 M ethods.........................................................................................................................................13
7 2 Sam ple Collection......................................................................................................................... 13
7.3 Sam ple Preparation.....................................................................................................................13 7.4 Analysis..........................................................................................................................................13 8 Analytical R esults........................................................................................................................................... 15 8.1 C alibration..................................................................................................................................... 15 8 .2 System Suitability........................................................................................................................ 15 8 .3 Limit o f Quantitation (L O Q )........................................................................................................15 8.4 Continuing C alibration................................................................................................................ 15 8 .5 Blanks............................................................................................................................................. 15 8 .6 Lab Control S p k e s (L C S s )........................................................................................................16 8.7 Analytical Method U ncertainty.................................................................................................. 18 8 .9 Field M atrix Spikes (F M S )...........................................................................................................18
Page 5 of 112
JTT7P
TFg m iUtf
1VDKUB
GLP10-01-02; Interim Report 30 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples
Bert Jeffries Properly - April 2012
9 D ata Sum m ary and D iscussion................................................................................................................. 18 10 Conclusion.......................................................................................................................................................28 11 D ata/Sam ple R etention............................................................................................................................... 28 12 A ttachm ents................................................................................................................................................... 2 8 13 S ignatures...................................................................................................................................................... 2 9
Lis t o f Ta b les
Table 1. Sum m arized PFB S, PFH S, and P FO S Results (B ert Jeffries Property, April 2012). ..1 0 Table 2. Sam ple Description Key Code..................................................................................................13 Table 3. Instrum ent Param eters............................................................................................................... 14 Table 4 . Liquid Chroma tography Conditions..........................................................................................14 Table 5. M ass Transitions..........................................................................................................................14 Table 6. Limit o f Quantitation (L O Q ).......................................................................................................15 Table 7. Laboratory Control S p k e R ecovery.........................................................................................17 Table 8. Analytical U ncertainty.................................................................................................................18 Table 9 . Field M atrix S p k e Levels........................................................................................................... 18 Table 10. JPAL G W M W 1 R 120405........................................................................................................20 Table 11. JPAL G W M W 3 R 12 0 4 0 5 ........................................................................................................20 Table 12. JPAL G W M W 4 R 12 0 4 0 5 ........................................................................................................21 Table 13. JPAL G W M W 4 L 120405........................................................................................................ 21 Table 14. JPAL G W M W 5 R 12 0 4 0 5 ........................................................................................................22 Table 15. JPAL G W M W 5 L 120405........................................................................................................ 22 Table 16. JPAL G W M W 6 R 12 0 4 0 5 ........................................................................................................23 Table 17. JPAL G W M W 6 L 120405........................................................................................................ 23 Table 18. JPAL G W M W 7 R 120405....................................................................................................... 24 Table 19. JPAL G W M W 8 R 120405........................................................................................................24 Table 20. JPAL G W M W 9 R 12 0 4 0 5 ........................................................................................................2 5
Page 6 cf 112
GLP10-01-02; Interim Report 30 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples
Bert Jeffries Property - April 2012 Table 21 . JPAL G W M W 9 L 120405........................................................................................................ 25 Table 22. JPAL G W M W 1 0 R 120405..................................................................................................... 2 6 Table 23 . JPAL G W M W 1 1 L 1 2 0 4 0 5 ......................................................................................................2 6 Table 24 . Rinseate Blank............................................................................................................................27 Table 25 . Trip B lank.....................................................................................................................................27
Page 7 of 112
IU I III i n II II
1
GLP10-01-02; Interim Report 30 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples
Bert Jeffries Property - April 2012
1
1 Stiidy Information
Sponsor
3M Company
Sponsor Representative
G ary Hohenstein 3M EHS Operations 3M Building 224-5W -03 Saint Paul, M N 55144-1000 P ho n e:(651)737-3570
Study Director
Jaisim ha Kesari, P .E ., D EE W eston Solutions, Inc. W estchester, PA 19380 P hone:(610)701-3761 Fax: (610)701-7401 j.kesari@ westonsokrtions.corn
Study Location
Testing Facility
3M E H S Operations 3M Environmental Laboratofy Building 260-5N -17 S t Paul, M N 55144
Study Personnel
W illiam K. R eagen, P h .D ., 3M Laboratory M anager
Cleston Lange, Ph.D ., Principal Analytical Investigator, fctewKie@mmm.com1: phone (651)-733-9860
Susan W olf, 3M Analyst C helsie Grochow , A nalyst Kevin Eich, A nalyst K elly U kes, Analyst
Study Dates
Study Initiation: M arch 8 ,2 0 1 0 Interim 3 0 Experimental Termination: April 2 6 ,2 0 1 2 Interim Report Completion: D ate o f Interim Report Signing
Location of Archives
A ll original raw d ata and th e analytical report h ave been archived a t th e 3 M Environm ental Laboratory according to 4 0 C F R P art 7 9 2 . T h e test substance and analytical referen ce standard reserve sam ples a re archived a t th e 3M Environm ental Laboratory according to 4 0 C F R P art 7 9 2 .
Page 8 of 112
GLP10-01-02; Interim Report 30 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples
Bert Jeffries Property - April 2012
2 Summary
T he 3M Environmental Laboratory prepared sam ple containers for fourteen locations on the Bert Jeffries property. A total o f forty-five sam ple bottles w ere received a t the 3M Environmental Laboratory for perfluorobutane sulfonate (P FB S ), perfluorobutane sulfonate (P FB S ), perfluorooctane sulfonate (P F O S ) analysis from W eston personnel on April 9 ,2 0 1 2 . All sam ples w ere logged into the laboratory information m anagem ent system (LIM S ) under project G LP10-01-02-30. For each sampling location, a field sam ple, field duplicate sam ple and field m atrix sp ire (F M S ) sam ple w ere collected. Sam ples also included a trip blank containing Milli-QTM w ater and an appropriate trip blank spike. A single equipm ent rinseate blank was also collected. T he equipm ent rinseate blank did not have FM S sam ples prepared fo r determination o f PFO A recovery. All sam ple bottles w ere fortified with internal standards and surrogate recovery standard 13C4-P F O S prior to sam ple collection. A# o f the sam ples w ere prepared and analyzed for PFB S, P FH S , P FO S , and the surrogate recovery standard 13C *-P F O S following 3M Environmental Laboratory Method E T S -8-044.1. T h e average m easured P FB S , P FH S , and P FO S concentrations are sum m arized in T a b le 1. T h e trip blank sam ple w as below the lower limit o f quantitation (LLO Q ) for all analytes, indicating adequate control o f sam ple contamination during shipping and sam ple collections. T he analytical method uncertainties associated with the reported results are: P FB S + 1 3 % , P FH S + 14% and P FO S + 1 8 % .
Page 9 of 112
GLP10-01-02; Interim Report 30 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples
Bert Jeffries Property - April 2012
Table 1. Summarized PFBS, PFHS, and PFOS Results (Beit Jeffries Property, April 2012).
S a m p lin g L o c a tio n
JPAL GW M W 1R 120405 JPAL G W M W 3 R 120405 JPAL G W M W 4 R 120405 JPAL G W M W 4L 120405 JPAL G W M W 5R 120405 JPAL G W M W 5L 120405 JPAL G W M W 6R 120405 JPAL G W M W 6L 120405 JPAL G W M W 7R 120405 JPAL GW M W 8R 120405 JPAL G W M W 9R 120405 JPAL G W M W 9L 120405 JPAL G W M W 10R 120405 JPAL G W M W 11L 120405 Trip Blanks (M M -Q TM W ater) G LP10 -0 1 -0 2 -3 0 Equipm ent tfnseate blank: JPAL G W M W 3R
PFBS A vg. Cone.
(n g ftn L ) % RPD 0 .1 1 3 *2 .7 % 1 .7 9 * 0.56% 0 .1 8 9 * 0.5 3% 0 .0 7 7 2 * 3.2% 0 .0 4 0 2 *0 .7 5 % 0 2 6 3 2.7% 0 .3 3 4 *1 .5 % 0 .0 5 5 1 *0 .9 1 % 0 .5 3 6 *0 .7 5 % 0 .0 5 0 8 * 6.3%
< 0 .02 5 0 < 0.0250 0 .0 5 7 9 *8 .1 % < 0.0250 < 0 .02 5 0
< 0 .02 5 0
PFHS A vg. Cone.
(n g ftn L ) % RPD 0 .8 6 1 *1 .0 % 8 .7 3 * 7 2 % 4 .8 8 *3 .1 % 0 2 0 5 *4 .4 % 0 .1 2 8 *8 .6 % 0 .4 00 * 0 2 5 % 1 .0 6 *5 .7 % 0 .0 9 5 2 * 0 .6 3% 1 .8 7 *1 .1 % 0 .1 2 8 *5 .5 % 0 .0 6 5 0 *1 .1 %
< 0 .02 5 0 0 2 6 4 *4 2 % 0 .0 8 8 6 *7 .6 %
< 0 .02 5 0
<00250
PFO S A vg. Cone.
(n g ftn L ) % RPD 1 .6 1 *1 .9 % 9 .7 0 *3 .5 % 5 0 1 *2 2 % 0 .3 4 8 * 0.5 7% 0 .1 2 8 *4 .7 % 2 0 7 *6 .8 % 7 .9 1 *0 0 8 % 0 .3 7 2 *3 .5 % 2 2 .5 *2 2 % 0 .4 1 0 *6 .6 % 0 .0 6 2 0 *1 0 % 0 .0 4 2 5 *0 .7 1 % 0 2 3 8 *5 .0 % 0 .4 9 6 *6 .5 %
< 0 .02 3 2
<0232
T l analysed m eto d uncertaMes associated wite * reported restSs are: PFBS 13%, PFHS 14 %, and PFOS 18%.
3 Introduction
This analytical study w as conducted as part of the F'hase 3 Environmental Monitoring and Assessm ent Program lo r the 3M fiacity located in Decatur, Alabam a. The objective o f the overall program is to gain information regarding concentrations o f perfluorooctane sulfonate (P F O S ), perfluorohexane sulfonate (P F H S ) and perfluorobutane sulfonate (P FB S ), in various environmental m erfa such as groundwater, soBs and sedim ents that are associated with and near the D ecatur facBty. This analytical study w as conducted to analyze ground w ater sam ples collected from fourteen locations from off-site w ells near Jeffries Landfill in Decatur, AL for PFBS, P FH S , and P FO S in an effort to characterize regional groundwater concfitions.
T he 3M Environmental Laboratory prepared sam ple containers (250 mL high-density polyethylene bottles) which w ere shipped to Decatur, AL W eston personnel prior to field sam ping. Sam ple containers for each sam ping location included a field sam ple, field sam ple duplicate, and one field matrix spice sam ple. Each em pty container w as m arked with a "fill to here" line to produce a final sam ple volume o f 200 mL. Containers designated for field matrix sam ples w ere fortified with an appropriate matrix sp ire solution containing PFB S (linear isom er), PFH S (linear isom er), and PFO S (linear and branched isom ers) prior to being sent to the field for sam ple collection. All sam ple bottles included the addition o f " O rP F B S , 13C yP F H S , and 13Ce-PFO S (internal standard) a t a nominal
Page 10 of 112
GLP10-01-02; Interim Report 30 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples
Bert Jeffries Property - April 2012
concentration o f 1 ng/m L. All sam ple bottles also included the addition o f13C4-P F O S (surrogate recovery standard) a t a nom inal concentration o f 0.1 ng/m L. S ee section 8 .8 o f the report for field matrix spice levels.
Sam ples w ere prepared and analyzed according to the procedure defined in 3M Environmental Laboratory method E TS -8-044.1 "Method o f Analysis for the Determination o f Perfluorinated Compounds In W ater by LC/M S/M S; Direct Injection Analysis". T he use o f internal standards was used to aid in the data quality objectives.
T ab le 1 sum m arizes the average PFB S, P FH S , and P FO S concentrations for the duplicate surface w ater sam ples collected and the trip blank sam ple. T ab les 10-25 sum m arize the individual sam ple results and the associated field matrix spike recoveries. All results for the quality control sam ples prepared and analyzed with the sam ples are reported and discussed elsew here in this report
4 Test & Control Substances
There w as not a test substance or control substances in the classic sense o f a G LP study. This study w as purely analytical in nature.
5 Reference Substances
R e fe re n ce S u b sta n ce
C hem ical N am e Chem ical Form ula Id e n tifie r
Use Source Expiration D ate Storage Concilions Chem ical Lot Num ber TC R Number Physical Description P u tty
PFBS (p re d o m in a n tly lin e a r)
Potassium Pertluorobutane sulfonate
C 4 F9 S 0 3X t
NA T arg et A nalyte R eference
Standard 3M
0 1 /1 0 1 2 0 1 7
Frozen
4 1 -2 6 0 0 -8 4 4 2 -5 T C R -121
W h ite Pow der
9 6 .7 %
"O fP F B S
[wQ zH A m m onium P erflu orob utanesu N O nate
C 4 F 9 S [180 2 j0 -N H 4 * NA
Internal Standard
RT1 International 0 3 /09 /2 0 1 5 Frozen 1 1 5 4 6 -1 0 7 -2
T C R -1024, T C R -1040 Liquid >99%
P a g e 1 1 o f1 1 2
GLP10-01-02; Interim Report 30 Analysts of PFBS, PFHS, and PFOS in Groundwater Samples
Bert Jeffries Property - April 2012
Chem ical N am e
Chem ical Form ula IdentM er
Use
Source Expiration D ate Storage Condtttons Chem ical Lot Num ber TCR Number Physical Description Purity
PFHS (L in e a r) Sodium Perfluorohexane sulfonate C 6 F 13S 0 3`N a +
L-P FH X S T arg et A nalyte R eference
S ta n d a rd W eln g to n 03/25 /2 0 1 8
F ro z e n
LPFH XSA M 08
T C R 08-0018 C rystallne
100%
" C *-P F H S
Sorflum P e rflu o ro h e x an e s u N b n a te
13C 3 12C 3 F 13S 0 3 T ta + M P F C -C -0112
Internal Standard
W e ln g to n 01/24 /2 0 1 5
F ro z e n M P F C -C -0112 TC R 12-0004
1IrfiM 5 p g A n L (1>
R 0 0B ro n co
Chem ical N am e
Chem ical Form ula Identflter Use Source E v ira tio n D ate Storage Concilions Chem ical Lot Num ber TC R Number Physical Description Purity
PFOS (L in e a r + B ran ched )
Potassium P e rflu o ro o c ta n e
sulfonate
C 8 F 1tS 0 3X *
PFOS (L in e a r + B ran ched )
Potassium Perfluorooctane
sulfonate
c 8 f 17s o 3x +
B r-P FO SK
T arg et Analyte R eference Standard
W e ln g to n
CAS # 2 7 95 -3 9 -3
F M S R eference S ta n d a rd
Sigm a Aldrich
12 /01 /2 0 1 4
0 2 /04 /2 0 1 4
F ro z e n brPFO SK 1111
Am bient 1424328V
T C R 1 1-0041
T C R 11-0028
Liquid
W hite Pow der
99 .9%
9 9 .7%
" ty w s
S o d iu m Perfluorooctane
sulfonate 13C 4 12C 4 F i7S 0 3 N a +
M PFO S Surrogate Recovery
S ta n d a rd W eln g to n 0 9 /08 /2 0 1 3
F ro z e n M PFOS0910 T C R 10-0044
Liquid
>98%
"C^PFO S
Sorflum Perfluorooctane
sulfonate 13C 8F17S 0 3 -N a +
M P F C -C -0112
Internal Standard
W eln g to n 0 1 /24 /2 0 1 5
F ro ze n M P F C -C -0112 T C R 12-0004
Liquid 5p g /h ftL (1>
(1) Custom mixture of seven mass-labeled (^)pertucroafcytcartxw yfc adds, two mass labeled O^C) periluaroakylsijltonatos and one mass-labeled (C ) perfluoro 1-octanesuttonemde
Page 12 of 112
GLP10-01-02; IntBrim Report 30 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples
Bert Jeffries Property - April 2012
6 Test System
T h e test system s for this study are groundwater sam ples collected from welts located in Decatur, AL by W eston Solutions, Inc. personnel. Sam ples for this study are "real w o rk f sam ples, not dosed with a specific lot o f test substance.
T a b le 2 . S a m p le D e s c rip tio n K ey C od e.
S tring Num ber Bom b 1 2 3 4
5 6
S tring D escriptor
| Exam ple
JPAL-GW-MW1R-0-120405
Sample Location
JPAL= Jeffries Property. Alabama
Sample Tw o
GW= Ground W ater
W eiIdentifier
E xam ple:MW 1R
W ei Level
R = Residuum shalow water-bearing zone
L = Bedrock water-bearing zone
S = Eplkarstrndde water-bearina zone
Sam ptingD ate
120405- A pril 5. 2012
Sample Type
0=pnmary sample
DB=dupticate sample
FMS = Field M atrix Satire
7 Method Summary
7.1 Method
Analysis for all analytes was completed following 3M Environmental Laboratory method ETS -8-044.1 "Method o f Analysis for the Determ ination o f Perfluorinated Compounds In W ater by High Perform ance Liquid Chrom atography/M ass Spectrom etry D irect Injection Analysis''.
7.2 Sample Collection
Sam ples w ere collected in 2 5 0 mL NalgeneTM (high-density polyethylene) bottles prepared a t Ih e 3M Environmental Laboratory. Sam ple bottles associated with G L P 10-01-02-30 w ere returned to the laboratory a t am bient conditions on April 9 ,2 0 1 2 . Sam ples w ere stored refrigerated a t the laboratory after receipt A set o f laboratory prepared Trip Blank and Trip Blank field matrix spires w ere sent with the sam ple collection bottles.
7.3 Sample Preparation
Sam ples w ere prepared by removing an aliquot o f the w ell mixed sam ple and placing it in an autovial for analysis.
During the preparation o f the laboratory control sam ples, an aliquot o f a separate internal standard spiking solution w as added to the laboratory control sam ples (nominal concentration o f 1 ng/m L). The sam ple bottles w ere spiked with an internal standard mix a t a nominal concentration o f 1 ng/m L prior to being sent to th e field for sam ple collection.
7.4 Analysis
AH study sam ples and quality control sam ples w ere analyzed for PFB S, P FH S , and P FO S using high perform ance liquid chromatography/ tandem m ass spectrometry (H P LC /M S /M S ). Detailed instrument param eters, the liquid chroma tography gradient program, and the specific m ass transitions analyzed are
Page 13 of 112
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1
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GLP10-01-02; Interim Report 30 Analysts o f PFBS, PFHS, and PFOS in Groundwater Samples
Bert Jeffries Property - April 2012
described in the raw data hard copies placed in the final data packet, and are briefly described below in T a b le 3, T a b le 4 and T a b le 5..
Table 3. Instrument Parameters.
Instrum ent Nam Analytical M ethod Followed Analysis D a le Liquid Chrom atograph G uard column Analytical colum n Infection Volum e M ass Spectrom eter Ion Source E le c tro d e P o la rity Softw are
ETS B uster ETS-8-044.1
4/23/12 AotontHOO Betas! C18 (4.6 mm X 100 mm). 5n Betas! C18 (4.6 mm X 100 mm). 5u
50 uL Aceied Bnsystems API 4000
Tnbo Spray Turbo ion electrode
N e g ates Analyst 1 4 2
Table 4. Liquid Chromatography Conditions.
Step Number
Total Time (nUn)
0 0 .0
1 2 .0 2 14.5 3 15.5 4 165 5 2 0 .0
How Rale QiJmln)
PercentA (2 mMammonium acetate)
ET5-8-044.1
750 97.0
750 97.0 750 5.0 750 5.0 750 97.0 750 97.0
PementB (methanol)
35 35 95.0 955 35 35
Table 5. Mass Transitions.
Analyte PFBS PFHS
PFOS [" CJ-PFOS
M ass Transition Q1/Q3
Tsano
eSMKWM9A9 399/00 399/99 499/90 499/99 499/130 503/00
Reference materia1 Structure
Unemr
Unear
U near* Branched
Unoar
Internal Standard (*0P FB S f 'CJ-PFHS [CJ-PFOS lCJ-PFOS
w m i inmwnon 0 1 /0 3 30304 402/90
507/90 507/00
Dwel timewas 50 msecter each transfer. The KteidualtoansfeonswBtB summedto producea "total ion chromatogram'(TIC), Wictiwas usedforquantitation.
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Analysis of PFBS, PFHS, andBGePrLFtPOJe1Sf0l-ri0nie1Gs-0Pr2or;uoInpndetewrtryiamt-eArRSperapilmo2rp0tl31e02s
8 Analytical Results
8.1 Calibration
Sam ples w ere analyzed using a stable isotope internal standard calixation curve. Calibration standards w ere prepared by spiking known am ounts o f the stock solution containing the target analytes into a laboratory-prepared synthetic groundwater containing calcium and m agnesium . A separate internal standard spiking solution w as prepared and an aliquot w as added a t the sam e level to all calixation standards and laboratory control sam ples a t a nominal concentration o f 1 n g/m L A calixation curve ranging from approxim ately 0 .0 2 5 ngfrnL to 2 5 ng/m L (0.025 ng/mL to 10 ng/m L for 13C4-P FO S surrogate) w as analyzed. The reference standard used for the calixatian standards for PFO S contained both linear and branched isomers. A quadratic, 1/x weighted, calibration curve o f the standard peak area/peak area ratios was used to fit the data for each analyte. The data w ere not forced through zero during the fitting process. Calculating the standard concentrations using the peak area/peak area ratios and the resultant calibration curve confirmed accuracy o f each curve point
Each curve point w as quantitated using the overall calixation curve and reviewed for accuracy. Method calibration accuracy requirem ents of 10025% (10030% for the lowest curve point) w ere m et for all analytes. T he correlation coefficient (r) w as greater than 0.995 for PFB S, P FH S , P FO S , and 13C4-P FO S .
8.2 System Suitability
A calibration standard w as analyzed four tim es a t the beginning o f each analytical sequence to dem onstrate overall system suitability. T he acceptance criteria of less than or equal to 5% relative standard deviation (R S D ) for peak area and retention tim e criteria o f less than or equal to 2% R SD w as m et for PFB S, P FH S , P FO S , and 13C4-P FO S .
8.3 Limit of Quantitation (LOQ)
T he LOQ for this analysis is the lowest non-zero calibration standard in the ctxve that m eets linearity and accuracy requirem ents and for which the area counts or area ratio are a t least tw ice those of the appropriate blanks. The LO Q for all analytes can be found in Table 6.
T a b le 6 . L im it o f Q u a n tita tio n (L O Q ).
A n a ly s is D a te
4 /2 3 /1 2
PFB S LO Q , ngAnL
0 .0 2 5 0
PFH S LO Q , ngAnL
0 .0 25 0
PFO S L O Q , n g /m L
0 .0 2 3 2
8.4 Continuing Calibration
During the course o f each analytical sequence, continuing calixation verification sam ples (C C V s) w ere analyzed to contain that the instrum ent response and the initial calibration curve w ere still in control. All C C V s m et method criteria o f 100% 25% for PFB S, P FH S , PFO S, and 13C4-P FO S .
8.5 Blanks
Three types o f blanks w ere prepared and analyzed with the samples: procedural blanks, trip blanks, and equipm ent rinseate blanks. Procedural blank results w ere reviewed and used to evaluate method perform ance and to determ ine the LOQ . Trip blanks reflect the shipping and sam ple collection conditons the sam ple bottles and sam ples experience. Equipm ent rinseate blanks are aqueous sam ples that reflect the efficiency o f equipm ent cleaning in the field between different sam ple collections to ensure no cross contamination o f sam ples from the equipment.
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Analysis ofPFBS, PFHS, andBGePrLFtPOJe1Sf0l-ni0ne1Gs-0Pr2or;uoInpndeterwtryiamt-eArRSperapimlo2rp0tl31e02s
8.6 Lab Control Spikes (LCSs)
Low, mid, and high lab control sp ites w ere prepared for the target analytes and analyzed in triplicate, w h le only low and high lab control spikes w ere prepared for the 13C4-P F O S surrogate. LCSs w ere prepared by spiking known am ounts of the analyte into synthetic groundwater to produce the desired concentration. T he sp ited w ater sam ples w ere then prepared and analyzed in the sam e m anner as the sam ples. T he method acceptance criteria, average o f LCS a t each level should be within 100% 2 0 % with an R SD 20% , w ere m et for a l analytes.
T h e folow ing calculations w ere used to generate data in T a b le 7 for laboratory control spices.
LCS Percent Recovery = Calculated Concentration Spike Concentration
LCS% RSD = s?q^
d8 ^
L(^ f8 Pic a te s -l0 0 %
average LCS recovery
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Analysis of PFBS, PFHS, andBGePrLFtPOJe1Sf0f-rm0ie1Gs-0Pr2or;uoInpndeterwtryiamt-eArRSperapimlo2rp0tl13e20s
Table 7. Laboratory Control Spike Recovery.
ETS-8-044.1 Analyzed 4/23/12
PFB S
L a b ID
S p ik e d C o n c e n tra tio n
(n g /tn L )
C a lc u la te d C o n c e n tra tio n
(n g /m L )
K fte c o v a ry
S p ik e d C o n c e n tra tio n
(n g /tn L )
L C S -1 2 0 4 1 6 -1 L C S -120416-2 L C S -120416-3 A ve ra g e % RSO
0 .1 98 0 .1 98 0 .1 98
0203 0216 0222
108% 4 .8 %
102
109
112
0 .198 0 .1 98 0 .1 98
L C S -120416-4 LC S -120416-5 LC S -120416-6 A ve ra g e % R S D
1 .9 8 1 .9 8 1 .9 8
2 .1 3 2 .1 6
2 .1 0
108% 1 4 %
108 109 106
1 .9 8 1 .9 8 1 .9 8
LC S -120416-7 LCS-120 4 16 -8 L C S -120416-9 A ve ra g e % R S D
9 .9 4 9 .9 4 9 .9 4
9 .8 3 9 .5 8 9.41 9 6 .7% 2 .2 %
9 8 .9 9 6 .4 9 4 .7
9 .9 2 9 .9 2 9 .9 2
PFH S C a lc u la te d C o n c e n tra tio n
(n g /tn L )
0 .2 0 1
0 .2 1 0
0 .2 15 105% 2 .9 %
2 .1 0
2 .3 0
2 .2 1
111% 4%
1 0 .0
9 .1 6 9 .3 9 9 6 .0 % 4 .7 %
H R a e c w e rv 102
106 108
106 116
112
101
9 2 .3 9 4 .7
ETS-8-044.1 Analyzed 4/23/12
L a b ID
P F O S (L in e a r * B ra n c h e d )
13C r P F O S s u r r o g a t e
S p ik e d C o n c e n tra tio n
(n g /m L )
C a lc u la te d C o n c e n tra tio n
(n g /tn L )
H R e c e v e ry
S p ik e d C o n c e n tra tio n
(n g /m L )
C a lc u la te d C o n c e n tra tio n
(n g /m L )
K R e co va ry
LC S-120416-1 L C S -120416-2 L C S -120416-3 A ve ra g e % RSD
0 .1 84 0 .1 84 0 .1 84
0 .1 79 0 .1 98 0 .1 9 9 104% 5 .7 %
9 7 .3 107 108
0 .189 0 .189 0 .189
0 .2 0 2
0 .199 0 .193 105% 2 .4 %
107 105
102
L C S -120416-4 L C S -120416-5 L C S -120416-6 A ve ra g e % R S D
1 .8 4 1 .8 4 1 .8 4
1 .8 4 1.91 1 .9 5 1 0 3 % 3 .1 %
9 9 .8 104 106
1 .8 9 1 .8 9 1 .8 9
1.91 1 .9 9
2 .0 1
104% 2.5%
101
105 106
LC S -120416-7 LC S -120416-8 LC S -120416-9 A ve ra g e % R S D
9 .2 2 9 .2 2 9 .2 2
9 .1 6 8 .7 8 8 .5 9 95.9% 3.2%
9 9 .3 9 5 .3 9 3 .2
NA NA NA
NA NA NA NA
NA NA NA
NA = Not Appicable
Page 17 of 112
Il 1 .III. HL___ -- L J _____ I J___ . . 1
- 1_
---------------- 1
Analysis of PFBS, PFHS, andBGePrLFtPJOe1Sf0f-ri0nie1Gs-0Pr2or;uoInpndeterwtryiamt-eArRSperapilmo2rp0tl31e20s
8.7 Analytical Method Uncertainty
Analytical uncertainty is based on historical Q C data that is control charted and used to evaluate method accuracy and precision. T h e method uncertainty is calculated following E TS -12 -0 1 2 2 . T he standard deviation is calculated for the set o f accuracy results (in % ) obtained for the Q C samples. The expanded uncertainty is calculated by multiplying the standard deviation by a factor o f 2, which corresponds to a confidence level o f 95% .
T a b le 8 . A n a ly tic a l U n c e rta in ty .
A n aly te PFBS PFHS PFOS
S ta n d a rd D e v ia tio n 6 .4 2 7 .0 0 9 .1 0
M eth o d U n ce rta in ty 113% 114% 118%
8.8 Field Matrix Spikes (FMS)
Low, mid, and high field matrix sp ites (FM S ) w ere collected at each sampling p o rt to verify that the analytical method is appficable to the collected matrix. Field matrix spikes w ere generated by adding a m easured volume o f field sam ple to a container spited by the laboratory with PFBS (linear), PFH S (linear), and P FO S (linear + branched) prior to shipping sam ple containers for sam ple colection. Field matrix sp ire recoveries w itfm method acceptance criteria o f 10030% confirm that "unknown" components in the sam ple matrix do not significantly interfere with the extraction and analysis o f the analytes o f interest Field matrix spice concentrations m ust be 50% o f the sam ple concentration to be considered an appropriate field spike. Field matrix sp ites are presented in section 9 o f this report
T a b le 9 . F ie ld M a trix S p ik e L e v e ls .
S a m p lin g L o catio n AH Locations and Trip Blank
PFBS, ngftn L
2 .0 0
PFHS, n g lriiL
2 .0 0
PFOS, n g /m L
2 .0 0
FM SR
_( Sam ple Concentration o f F M S -A v e ra g e Concentration : Field Sam ple & Field Sam ple P u p .). Spike C oncentratoli
9 Data Sum m ary and Discussion
T he tables below sum m arize the sam ple results and field matrix sp ire recoveries for the sampling locations as well as the Trip Blank. Results and average values are rounded to three significant figures according to E PA rounding rules. Because o f rounding, values m ay vary slightly from those isted in the
raw data. Field m atrix s p ite recoveries m eeting the method acceptance criteria o f 30% , dem onstrate
that the method w as appropriate for the given matrix and their respective quantitative ranges.
JP A L G W M W 3 R 120405; The field matrix sp ire level w as not appropriate as com pared to the PFH S and P FO S concentrations in the sam ples. However, the 13C4-P F O S surrogate recovery added to all sam ple bottles m et method acceptance criteria.
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Analysis of PFBS, PFHS, andBGePrLFtPOJ1eS0ff-ri0ni1eG-sQPr2or;uoInpndeterwtryiamt-eArRSperapilmo2rp0tl31e02s
JP A L G W M W 4 R 120405; T h e field m atrix spike level w as not appropriate as compared to th e P FH S a id P FO S concentrations in the sam ples. However, the 13C rP F O S surrogate recovery added to all sam ple bottles m et method acceptance criteria. JP A L G W M W 6 R 120405; T h e field m atrix spike level w as not appropriate as com pared to the PFO S concentration in the sam ples. However, the 13C4-P F 0 S surrogate recovery added to all sam ple bottles m et method acceptance criteria. JP A L G W M W 7 R 120405; T h e field m atrix spike level w as not appropriate as compared to the P FO S concentration in the sam ples. However, the l3C4-P FO S surrogate recovery added to a l sam ple bottles m et method acceptance criteria.
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Analysis of PFBS, PFHS, andBGePrLFtPOJe1Sf0f-ri0nie1Gs-0Pr2or;uoInpndeterwtryiamt-eArRSperapimlo2rp0tl13e20s
Table 10. JPAL GW M W 1R 120405
PFB S
PFH S
PFO S
" C rP F O S
M I M S ID
D e s c rip tio n
G L P 10-01-02-30-001 J P A L -G W -M /V 1R -0-12 0 4 0 5
G L P 10 -0 1 -0 2 -3 0 -00 2 J P A L-G W 4A /V 1R -D B -12 0 4 05
G L P 10 0 1 0 2 -3 0 0 0 3 JP A L -G W -M W 1R -F M S -120405
A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D /% R S D
C o n c e n tra tio n (n g /m L )
% R e c o v e ry
0 .114
0 .1 1 1
2 .4 8
NA NA 118
0 .1 1 3 n g /m L 2 .7 %
C o n c e n tra tio n (n g /m l)
% K e c o v e ry
0865 0 .856 3.31
NA NA
122
0 .8 6 1 n o /m L H .0 %
C o n c e n tra tio n (n g /m L )
% F e c o v e ry
1 .6 2
NA
1 .5 9
NA
4 .0 5
122
1 .6 1 n g /m L 1 1 .9 %
% R e c a v e ry
958 9 9 .3
110 1 0 2 % 1 7 .2 %
N A *N otA ppcatte
T a b le 11. JPAL G W M W 3 R 120405
PFB S
PFHS
PFO S
13C r P F O S
M I M S ID
D e s c rip tio n
G L P 10-01-02-30-004 JP A L -G W -W V 3R -0-120405 G L P 10-01 -0 2 -3 0 -00 5 JP A L -G W -M W 3R -D B -12 0 405
G L P 1 0 0 1 0 2 -3 0 0 0 6 JP A L -G W -M W 3R -F M S -120405
A v e ra g e C o n c e n tra tio n (n g /m L ) l % R P D /% R S D
C o n c e n tra tio n (n g /m L )
% R e c o v e rv
1 .7 8 1 .7 9 3 .6 3
NA NA 9 2 .3
1 .7 9 n g A n L 0 .5 6 %
C o n c e n tra tio n (n g /m L )
% R e c o v e ry
9 .0 4 8.41
1 0 .2
NA NA NC
8 .7 3 n g /m L 1 7 .2 %
C o n c e n tra tio n (n g /m L )
% R e c o v e rv
% R e c o v e rv
9 .5 3
NA
9 .8 7
NA
1 0 .9
NC
9 .7 0 n g A n L t 3 .5 %
9 7 .8 104
8 8 .1 9 6 .7 % 8 .4 %
N A " Not Applicable N C " Nat Calculated; the sample concentration is greaterthan 2x the gpfce level.
Page 20 of 112
Analysis of PFBS, PFHS, andBGPerLFtPOJe1Sf0f-ri0nie1Gs-0rP2or;uoInpndeterwtryiamt-eArRSperapimlo2rp0tl13e20s
Table 12. JPAL GW M W 4R 120405
PFB S
PFH S
PFO S
13C r P F O S
3 M U M S ID
D e s c rip tio n
G LP 10-01-02-30-007 J P A L-G W -M W 4R -0-12 0 4 0 5
G LP 10-01-02-30-008 JP A L-G W -M W 4R -D B -12 0 4 05
G LP 10-01-02-30-009 JP A L -G W -M W 4R -F M S -120405
A v e r a a e C o n c e n tra tio n (n g /m L ) % R P D /% R S D
C o n c e n tra tio n (n g /m L )
% R e c o v e ry
0 .1 8 8
NA
0 .1 8 9
NA
215
9 8 .1
0 .1 S 9 n o /m L 0 .5 3 %
C o n c e n tra tio n (n g /m L )
% R e c o v e ry
4 .9 5 4 .8 0 6 .6 5
NA NA NC
4 .8 8 n o /m L 3 1 %
C o n c e n tra tio n (n o /m L )
% R e c o v e ry
% R e c c v e ry
5 .8 7 5 .7 4 7 .8 5
NA 93.1 NA 9 3 2 N C 98.1
5 .8 1 n o /m L 2 .2 %
9 4 .8 % 3 .0 %
NA-NotAppKcable NC * Not CakaJatad; thesample concentration is greaterthan2x the spin level.
T a b le 13. JP A L G W M W 4L 120405
PFBS
PFH S
PFO S
13C r P F O S
3 M U M S /D
D e s c rip tio n
G LP 104)1-02-30-010 JP A L -G W -M W 4L-0-120405 G LP 10-01-02-30-011 JP A L -G W -M W 4L-D B -120405 G LP 10-01-02-30-012 JP A L -G W -M W 4L-F M S -120405
A v e ra a e C o n c e n tra tio n (n o fm L ) % R P D f% R S D
C o n c e n tra tio n (n o /m L )
% R e c o v e ry
0 .0 7 5 9 0 .0 7 8 4
205
NA NA 9 8 .6
0 .0 7 7 2 n o A n L i 3 .2 %
C o n c e n tra tio n (n o /m L )
% R e c o v e ry
0200
0209 215
NA NA 9 7 .3
0 .2 0 5 n o /m L 4 4 %
C o n c e n tra tio n (n o /m L )
% R e c o v e ry
% R e c o v e ry
0 .3 47
NA
0 .3 4 9
NA
221
93.1
0 .3 4 8 n o /m L 0 .5 7 %
9 7 .1 9 3 .6 9 1 .8
9 4 2 % 2 .8 %
N A = N o tA p p ic a b le
Page 21 of 112
Analysis of PFBS, PFHS, andBGePrLFtPOJe1Sf0f-rin0ie1Gs-0Pr2or;uoInpndetewrtryiamt-eArRSperapilmo2rp0tl13e20s
Table 14. JPAL GW M W 5R 120405
PFB S
PFH S
PFO S
n C rP F O S
3M LM S D
D e s c rip tio n
G LP 10-01-0 2 -3 0 -0 1 3 JP A L -G W -M /V 5R -0-120405 G LP 10-0 1 -0 2 -3 0 -01 4 JP A L-G W -M W 5R -D B -12 0 405
G L P 10 -0 1 -0 2 -3 0 -0 1 5 JPAL-G W -M W V5R-FM S-120405
A v e ra g e C o n c e n tra tio n (n o fm L ) t % R P D f% R S D
C o n c e n tra tio n (n o fm L )
% R e c o v e ry
0 .0400 0 .0403
2 .0 3
NA NA 9 9 .5
0 .0 4 0 2 n o fm L 0 .7 5 %
C o n c e n tra tio n (n o fm L )
% R e c o v e ry
0 .133
0 .1 2 2
2 .1 4
NA NA
101
0 .1 2 8 n a ftn L t 8 8 %
C o n c e n tra tio n (n g im L )
% R e c o v e ry
% R e c o v e ry
0 .1 2 5 0 .1 3 1 1 .9 9
NA NA 93.1
9 6 .9 9 8 .4
101
0 .1 2 8 n o fm L 1 4 .7 %
9 8 .9 % i 2 4 %
N A * NotAppicable
T a b le 15. JP A L G W M W 5 L 120405
PFB S
PFH S
PFO S
" CrP F O S
3M LM S D
D e s c rip tio n
G LP 10 0 1 -0 2 -3 0 0 1 6 JP A L -G W -M W 5L-0-120405
G L P 10 0 1 -0 2 -3 0 0 1 7 JP A L -G W -M W 5L-D B -120405
G L P 10 0 1 0 2 -3 0 -0 1 8 JP A L-G W -M W 5L-F M S -120405
A v e ra g e C o n c e n tra tio n (n o fm L ) % R P D f% R S D
C o n c e n tra tio n (n a fm U
% R e c o v e rv
0259
NA
0266
NA
223
9 8 .4
0 2 6 3 n & m L 2 .7 %
C o n c e n tra tio n (n a fm U
% R e c o v e rv
0 .3 99
NA
0 .400
NA
2 .3 3
9 6 .5
0 .4 0 0 n o fm L 0 .2 5 %
C o n c e n tra tio n (n o fm L )
% R e c o v e rv
2 .1 4
2 .0 0
4 .0 0
NA NA 9 6 .5
2 .0 7 n o fm L 8 8 %
% R e c o v e rv
107 952 9 9 .6
100% 8 8 %
N A * NotAppicable
Page 22 of 112
Analysis of PFBS, PFHS, andBGePrLFtPOJe1Sf0f-ri0nie1Gs-0rP2or;uonIpndeterwtryiamt-eArRSperapimlo2rp0tl13e20s
Table 16. JPAL GW M W 6R 120405
PFB S
PFHS
PFO S
n C rP F O S
3 M L M S ID
D e s c rip tio n
G LP 10-01-02-30-019 JP A L -G W -M W 6R -0-120405 G LP 10-01-02-30-020 JP A L-G W -M W 6R -D B -12 0 405 G LP 10 0 1 -0 2 -3 0 0 2 1 JP A L -G W -M W 6R -F M S -120405
A v e r a g e C o n c e n tra tio n (n g /m L ) 1 % R P D /% R S D
C o n c e n tra tio n (n g A n L )
% R e c o v e ry
0 .3 3 6
NA
0 .3 3 1
NA
231
9 8 .8
0 .3 3 4 n g /m L 1 .5 %
C o n c e n tra tio n ( n g /m L )
% R e c o v e ry
1 .0 9 1 .0 3 3 .0 2
NA NA 9 8 .0
f .0 6 n g /m L 1 5 .7 %
C o n c e n tra tio n ( n g /m L )
% R e c c v e ry
% R e c o v e ry
7 .8 9
NA
7 .9 2
NA
9 .4 7
NC
7 .9 1 n g /m L 0 .3 8 %
101
9 7 .1 9 6 .9
9 8 .3 % 2 J %
N A * NotAppfcaWe N C * NotCalculated; thesampleconcentrationisgreaterthan2x the spite leveL
T a b le 17. JPA L G W M W 6L 120405
PFB S
PFH S
PFO S
n C t-P F O S
3 M L M S ID
D e s c rip tio n
G LP 10 0 1 -0 2 -3 0 0 2 2 JP A L -G W -M W 6LO -120405
G LP 10 0 1 -0 2 -3 0 0 2 3 JP A L -G W -M W 6L-D B -120405
G LP 10 0 1 0 2 -3 0 0 2 4 J P A L -G W -M W 6L-F M S -120405
A v e r a g e C o n c e n tra tio n (n o fn A .) i % R P D /% R S D
C o n c e n tra tio n (n g A n L )
% R e c o v e rv
0 .0 5 4 8
NA
0 .0 5 5 3
NA
200
972
0 .0 5 5 1 n o fm L 0 .9 1 %
C o n c e n tra tio n (n g /m L )
% R e c o v e ry
0 .0 94 9 0 .0 95 5
2 .0 4
NA NA 9 7 .2
0 M S 2 n g A n L 0 .6 3 %
C o n c e n tra tio n (n g /m L )
% R e c o v e ry
% R e c o v e ry
0 .365
NA
0 .378
NA
221
9 1 .9
0 2 7 2 n g /m L 1 3 .5 %
101
9 7 .8 8 8 .3 9 5 6 % 62%
NA=NctAppfcaMe
Page 23 of 112
Analysis of PFBS, PFHS, andBGPerLFtPOJe1Sf0f-ir0nie1Gs-0rP2or;uonIpndetwertryiamt-eArRSperapimlo2rp0tl13e20s
Table 18. JPAL GW M W 7R 120405
PFB S
PFHS
PFO S
n C fP F O S
3M U M S D
D e s c rip tio n
G L P 10-01-02-30-025 JP A L -G W -M W 7R -0-120405 G LP 10-01-02 -3 0 -0 2 6 JP A L -G W -M W 7R -D B -120405 G LP 10-01-02-30-027 J P A L-G W -M W 7R -FM S -120405
A verag e C o n c e n tr a tio n ( r & m L ) l % R P D /% R S D
C o n c e n tra tio n (n o /tn L )
^R ecovery
0 .5 3 4
NA
0 .538
NA
2 .4 9
9 7 .7
0 .5 3 6 n o /m L 0 .7 5 %
C o n c e n tra tio n ( n g /m L )
% R e c o v e ry
1 .8 8 1 .8 6
3 .6 8
NA NA 9 0 .5
1 .8 7 n o /m L 1 .1 %
C o n c e n tra tio n (n o /m U
% R e c o v e ry
% R e c o v e ry
2 2 .7
NA 9 4 .7
2 2 .2
NA 9 1 .9
N R (1) N C 9 6 .4
2 2 .5 n o rin L 2 .2 %
9 4 .4 % 2 4 %
NA-NotAppIcabie NC NotCalcuiatsd; the sample concentration isgreaterthan2x the pfcelsvsi. (1) NR Not Reported; sampieconcentrationeMceededthecafcration range of23.2 ng/mLfor PFOS.
T a b le 19. JP A L G W M W 8 R 120405
PFB S
PFHS
PFO S
13C r P F O S
3M LM S 8J
D e s c rip tio n
G L P 10 0 1 -0 2 -3 0 -0 2 8 JP A L -G W -M W 8R -0-120405 G LP 10 -01-02-30-029 JP A L-G W -M W 8R -D B -120405
G LP 10 -0 1 -0 2 -3 0 -03 0 J P A L -G W 4A /V 8R -F M S -120405
A verag e C o n c e n tr a tio n (n o /m L ) % R P D /% R S D
C o n c e n tra tio n (n o fm U
^R ecovery
0 .0 49 2
NA
0 .0524
NA
1 .9 3
9 4 .0
0 .0 5 0 8 n o /m L 1 8 .3 %
C o n c e n tra tio n (n o /m L )
% R e c a v e ry
0 .1 2 4
NA
0 .1 3 1
NA
2 .0 6
9 6 .6
0 .1 2 8 n o /m L 1 5 .5 9 6
C o n c e n tra tio n (n g /m L )
% R e c o v e rv
0 .3 9 6
NA
0 .4 23
NA
2 .3 0
9 4 .5
0 4 1 0 n o /m L 1 6 .6 %
^R eco very 9 1 .7 9 4 .6 9 4 .7
9 1 7 % 1 .8 9 6
NANotApptatte
Page 24 of 112
Analysis of PFBS, PFHS, andBGPerLFtPOJe1Sf0f-ri0nie1Gs-0rP2or;uoInpndeterwtryiamt-eArRSperapimlo2rp0tl13e20s
Table 20. JPAL GW M W 9R 120405
PFBS
PFH S
PFO S
n C rP F O S
3 M U M S ID
D e s c rip tio n
G L P 10-01-02-30-031 JP A L -G W -M W 9R -0-120405
G L P 10-01-02-30-032 JP A L-G W -M W 9R -D B -120405
G LP1 O O i -02-30-033 JP A L -G W -M W 9R -F M S -120405
A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D /% R S D
C o n c e n tra tio n (n g /m L )
% R e c o v e ry
< 0 .0 2 5 0
< 0 .0 2 5 0
NA NA
2 .0 1
101
< 0 .0 2 5 0 n o /m L
C o n c e n tra tio n (n g /m L )
% R e c o v e ry
0 .0 6 5 3
NA
0 .0 6 4 6
NA
2 .1 4
104
0 .0 6 5 0 n o /m L 1 1 .1 %
C o n c e n tra tio n (n g /m L )
% R e c o v e ry
% R e c o v e ry
0 .0 6 5 2
NA
0 .0 5 8 8
NA
1 .8 4
889
0 .0 6 2 0 n g /m L 1 1 0 %
9 6 .0 9 7 .6 9 4 .9 9 6 .2 % 1 4 %
NA-NotAppfcafale
T a b le 21. JPA L G W M W 9 L 120405
PFB S
PFH S
PFO S
**C rP F O S
S U L IM S ID
D e s c rip tio n
G L P 10-01-02-30-034 JP A L -G W -M W 9L-0-12 0405
G L P 10-01-02-30-035 JP A L -G W -M W 9L-D B -120405 G LP 10-01-02-30-036 JP A L-G W -M W 9L-F M S -120405
A v e r a g e C o n c e n tra tio n (n g /m L ) 1 % R P D /% R S D
C o n c e n tra tio n (n g /m L )
% R e c o v e ry
< 0 .0 2 5 0 < 0 .0 2 5 0
NA NA
1 .9 4
9 7 .0
< 0 .0 2 5 0 n o /m L
C o n c e n tra tio n (n o /m L )
% R e c o v e ry
< 0 .02 5 0
NA
0 .0 2 5 0
NA
1 .9 9
9 9 .5
< 0 .0 2 5 0 n o /m L
C o n c e n tra tio n (n g /m L )
% R e c o v e ry
0 .0 4 2 3
NA
0 .0 4 2 6
NA
1.81
884
0 .0 4 2 5 n o /m L 0 .7 1 %
% R e c o v e ry
9 0 .6 9 4 .4 9 1 .1
9 2 0 % 2 .2 %
NA*NotAppfcaHe
Page 25 of 112
Analysis of PFBS, PFHS, andBGPerLFtPOJe1Sf0l-fin0ie1Gs-0Pr2or;uonIpndetwretryiamt-eArRpSerapilmo2rp0tl13e20s
Table 22. JPAL GW MW10R 120405
3M LM S D
D e s c rip tio n
GLP10-01-02-30-037 JPAL-GWMW1OR-0-120405
GLP10-01-02-30-038 GLP10-01-02-30-006
JPAL-GVWA/V10R-DB-120405 JPAL-GW-MA/1OR-FMS-120406
A v e ra g e C o n c e n tra tio n (n o A n U % R P D /% R S D
N A -N otA ppicable
PFB S
PFHS
PFO S
ttC rP F O S
C o n c e n tra tio n (rta /m U
% R e c o v e rv
0 .0602
NA
0 .0 55 5 2 .0 5
NA 9 9 .6
0 .0 5 7 9 n a /m L 8 .1 %
C o n c e n tra tio n (n tm )
% R e c o v e ry
0 .269
NA
0258
220
NA 9 6 .8
0 .2 5 4 n o /m L t 4 .2 %
C o n c e n tra tio n (n g fm L )
% R e c o v e ry
0 .2 3 2
NA
0 .2 4 4
NA
2 .1 3
9 4 .6
0 2 3 8 n o fm L 1 5 .0 %
% R e c o v e ry
9 3 .8 9 4 .8 9 7 .6 9514% 2 .1 %
T a b le 23. JP A L G W M W 1 1 L 120405
3M LM S D
D e s c rip tio n
GLP10-OI02-30-040 JPAL-G W 4W 11LO -120405
GLP100102-30-041 JPAL-GW 4W 11L-OB-120405
GLP10O102-30-042 JPAL-GW44W11L-FMS-120405
A v e ra g e C o n c e n tra tio n ( n m L ) 1 % R P D /% R S D
N A N o tA p p lc a b le
PFB S
PFHS
PFO S
13G r P F O S
C o n c e n tra tio n (n g /m U
% R e c o v e ry
< 0 .02 5 0 < 0.0250
2 .0 3
NA NA
102
< 0 .0 2 5 0 n o /m L
C o n c e n tra tio n (n o /m U
% R e c o v e ry
0 .0 91 9
NA
0 .0 65 2
NA
2 .1 6
104
0 .0 8 8 6 n g A n L 1 7 .6 %
C o n c e n tra tio n (n g fm L )
X R e c o v e rv
% R e c o v e ry
0 .5 1 2
NA
0 .4 8 0
NA
2 .4 6
9 8 .2
0 .4 9 6 n o fm L 1 6 .5 %
8 6 .6
9 8 .5
100
95L0% 1 7 .7 %
Page 26 of 112
Analysis of PFBS, PFHS, andBGePrLFtPOJe1Sf0f-ri0nie1Gs-0Pr2or;uoInpndeterwtryiamt-eArRSperapimlo2rp0tl13e20s
Table 24. Rinseats Blank
PFB S
PFH S
PFO S
n C rP F O S
3 M U M S ID
D e s c rip tio n
G L P 1 0 -0 1 -02-30-043 JP A L -G W -M W 3R -R B -12 0 4 05
C o n c e n tra tio n (n g fm L )
< 0 .02 5 0
C o n c e n tra tio n (n o /m U
< 0 .0 2 5 0
C o n c e n tra tio n ( n o fm L )
< 0 .02 3 2
V o R e c o v e ry
9 2 .1
N A > NotAppicable
T a b le 25 . T rip B la n k
3 M U M S ID
GLP10-01-02-30-044 GLP10-01-02-30045
D e s c rip tio n
JPAL-G W -TR IP01-O 120316 JPA L-G W -TR IP01-FM S-120316
N A -N otA p picable
PFB S
PFH S
PFO S
C o n c e n tra tio n (n g /m U
< 0 .02 5 0 ZOO
V o R e c o v e ry
NA
C o n c e n tra tio n (n o /m U
< 0 .02 5 0
100
2 .0 0
V o R e c o v e ry
NA
100
C o n c e n tra tio n (n o /m L )
< 0 .0 2 3 2 1.82
V o R e c o v e ry
NA 9 1 .0
13C r P F O S
V o R e c o v e ry
9 2 .8 9 7 .5
Page 27 of 112
Analysis of PFBS, PFHS, andBGePrLFtPOJe1Sf0l-ri0nie1Gs-0Pr2or;uoInpndeterwtryiamt-eArRSperaipmlo2p0tl31e20s
10 Conclusion
Laboratory control sp ites and field matrix sp ite s w ere used to determ ine the analytical method accuracy and precision for PFB S, PFH S , and P FO S. Analysis w as successfully com pleted following 3M Environmental Laboratory method E TS -8-044.1 described herein.
11 Data/Sample Retention
A l rem aning sam ples and associated project data (hardcopy and electronic) w il be archived accordng to 3M Environmental Laboratory standard operating procedures.
12 Attachm ents
Attachm ent A: Protocol Am endm ent 30 (G eneral Project Outline) Attachm ent B: Representative Chrom atogram s and C albration Curves Attachm ent C: Analytical M ethod-ETS-&-044.1
Page 28 of 112
Analysis ofPFBS, PFHS, andBGePrLFtPOJe1Sf0f-ri0nie1Gs-0Pr2or;uoinpndeterwtryiamt-eArRSperapimlo2rp0tl13e20s
13 Signatures
Cieston Lange, Ph.D., 3M Principal Analytical Investigator
$ h k )i
D ate
William K. Reagen, Ph D ., 3M Environmental Laboratory Department Manager
D ate
Page 29 of 112
Analysis of PFBS, PFHS, andBGePrLFtPOJe1Sf0f-ri0nie1Gs-0Pr2or;uoInpndetrwetryant-ieArRSperapimlo2rp0tl31e02s
Attachment A: Protocol A mendment
Page 30 of 112
GLP10-01-02; Interim Report 30 Analysis o f PFBS, PFHS, and PFOS in Groundwater Samples
B eit Jeffries Property - April 2012
Analytical Protocol: GLP10-01-02 Amendment 30
Study Title Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and
Perfluorobutane sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program
PROTOCOL AMENDMENT NO. 30
Am endm ent Date: March 2 2 ,2 0 12
Perform ing Laboratory 3M Environmental, Health, and Safety Operations
3M Environmental Laboratory Building 260-5N-17
Maplewood, MN 55144-1000
Laboratory P roject Identification G L P 10 -0 1 -0 2
Sam pling Event Off-Site Wells - Bert Jeffries Property
Page 1 of 6
Page 31 of 112
i HH'wwrm' m i 11'\m m m e?e j
1
GLP10-01-02; Interim Report 30 Analysis o f PFBS, PFHS, and PFOS in Groundwater Samples
Bert Jeffries Property - April 2012
Analytical Protocol: GLP10-01-02 Amendment 30
This amendment modifies the following portion o f protocol:
"Analysis of PFOS, PFHS and PFBS in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program"
Protocol reads:
No changes to th e w ording o f the protocol a re required.
AMEND TOread:
No changes to the w ording o f the protocol are required. T his am endm ent only addresses and docum ents the addition o f th e G en eral Project O utline (G P O ) fo r the collection and analysis o f groundw ater sam ples as part o f the 3M D ecatur P hase 3 Program fo r P FO S , P FH S and P FB S (G L P 1 0 -0 1 -0 2 ). T h e anticipated sam ple collection w ill occur around th e tim efram e o f the w e e k o f M arch26, 2 0 1 2 . T h e groundw ater sam ples for this sam pling even t w ill b e entered into th e 3M Environm ental Laboratory L IM S as project
G LP10-01-02-30 and reported as interim report GLP10-01-02-30, (reflecting study GLP10-01-02 and am endm ent -30).
Reason:
T h e reason for this am endm ent is to docum ent the G en eral P roject O utline (G P O ) which describes the anticipate groundw ater sam ple collection even t fo r fourteen off-site w ells a t th e B ert Jeffries Property. The G P O is three pages in length and included as attached to this am endm ent form.
Page 2 of 6
Page 32 of 112
G LP10-01-02; Interim Report 30 Analysis o f PFBS, PFHS, and PFO S in Groundwater Samples
Bert Jeffries Property - April 2012
Analytical Protocol: GLP10-01-02 Amendment 30
Amendment Approval
<5 y x-
Page 3 of 6 Page 33 oM 12
G LP10-01-02; Interim Report 30 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples
Bert Jeffiries Property - April 2012
Analytical Protocol: GLP10-01-02 Amendment 30
d lH
Environmental Health & Safety Operations, Environmental Laboratory General Project Outline
To: From : cc:
D a te: S u b ject:
Gary Hohenstein, 3M EHS&Opns
Susan W olf, 3M EHS&Opns; Environmental Lab W illiam R eagen, 3M EHS&Opns; Environmental Lab
Cleston Lange, 3M EHS&Opns; Environmental Lab
Jai Kesari, W eston Solutions
March 2 2 ,2 0 1 2
A nalysis o f Perfluorooctane S ulfonate (P F O S ), Perfluorohexane S ulfonate (P F H S ) and P erfluorobutane sulfonate (P F B S ) in G roundw ater, S oil and S edim en t fo r th e 3M D ecatur P hase 3 S ite-R elated M onitoring Program ; G LP Interim R eport 30; O ff-S ite W ells - B ert Jeffries Property
1 General Project Information
C o n tacts
Lab Request Number Six D ig it D epartm ent Num ber Project Schedule/Test D ates
3M Sponsor R epresentative Gary Hohenstein 3M EHS Operations 3M Building 224-5W -03 Saint Paul, MN 55144-1000 P hone:(651)737-3570 aahohensteinrem m m .com
3M Environm ental Laboratory M anagem ent W iliam K. Reagen 3M EHS Opns, Environmental Laboratory 260-5N -17 651 733-9739 wkreaoeneSmmm.com
Principal A nalytical Investigator Cleston Lange 3M EHS Opns, Environmental Laboratory 2 6 0 -5 N -1 7 651 733-9860 cdanoelQimmm.com
Sam pling C oordinator Timothy Frinak Weston Solutions Tim othv.frinakffiw estonsolutions.com Phone: (334)-332-9123
G LR10-01-02-30
Dept #530711, Project #0022674449
Sampling scheduled for the week o f March 2 6 ,2 0 1 2
A // verbal and written correspondence will be directed to Gary Hohenstein.
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Analytical Protocd?Gfrlo-01-02 Amendment 30
2 Background Information and Project O bjectives)
T h e 3M E H S O perations Laboratory (3 M Environm ental Lab) w ill receive and an alyze groundw ater sam ples collected from fourteen sam pling locations fo r Perfluorobutanesulfonate (P F B S ), P erfluorohexanesulfonate (P F H S ), and Perfluonooctanesulfbnate (P F O S ) from w ells located on the B ert Jeffries Property. A nalyses w ill be conducted under the G LP requirem ents o f E P A T S C A G ood Laboratory P ractice Standards 4 0 C FR 792. G roundw ater sam ples w ill be collected by W eston Solutions personnel th e w eek o f M arch 2 6 ,2 0 1 2 . The 3M Environm ental Laboratory w ill prepare the sam ple bottles with a i required spikes to ensure th a t results for P FB S , P FH S , and P FO S a re o f a known precision and accuracy. T h e fin al report win be subm itted to G ary H ohenstein and Jai K esari upon com pletion under interim report G L P 1 0 -0 1 -0 2 -3 0 .
3 Project Schedule
Sam ple collection bottles will be prepared by 3M Environmental Laboratory for sampling the w eek of March 26, 2012. Sam ple bottles will be shipped in coolers overnight to 3M D ecatur for arrival on Friday, March 2 3 ,2 0 1 2 . Sam ple bottles should be stored refrigerated on-site until sam ple collection. M artin Sm ith \ W eston T railer 3M D ecatur P lant 1400 S tate Docks Road D ecatur, A labam a 35601
4 Test Parameters
T he targeted limit of quantitation will be 0.025 n g /m L (ppb) for PFBS, PFH S, and PFO S.
Fourteen sampling locations have been specified. F a each sampling location, a total of three sam ple bottles will be collected (sam ple, sam ple duplicate and 2 ng/m L field matrix spike). T h e "fill to here" line on each 250 mL Nalgene bottle will be 200 m L. O ne set o f trip blanks consisting of reagent-grade w ater as w ell as a trip blank spike at 2 ng/m L will be prepared at the 3M Environmental Laboratory and sent to the sampling location with the other bottles. A ll sam ple bottles will include the addition of 1*O r PFBS, 1Or P FH S , and 13Cs-PFOS (internal standard) at a nom inal concentration of 1 ng/mL All sam ple bottles will also include the addition o f 3C 4-P FO S (surrogate spike) a t a nominal concentration of 0.1 ng/mL. O ne additional bottle will b e prepared to be used f a the preparation o f the equipment rinseate blank. A 500-m L bottle of laboratory reagent w ater will be sent with the sam ple bottles to be used to generate the rinseate blank sam ple.
5 Test Methods
Sam ples will be prepared and analyzed by LC /M S/M S following E T S -8 -0 4 4 .1 ` Method of Analysis for the Determination o f Perfluorinated Compounds In W ater by LC/M S/M S; D irect Injection Analysis". The data q ualty objectives for these studies are quantitative results for the target analytes with an analytical accuracy o f 10030% . Field matrix spikes not yielding recoveries within 10030% will be addressed in the report and the final accuracy statem ent m ay be adjusted accordingly. W here applicable, sam ples will be analyzed against an internal standard calibration curve. Each curve point will contain isotopicaily-labeted perfluorocarboxylic acids and perfluorosulfbnic acids a t a nom inal concentration of 1 ng/mL. The calibration curve will be generated by taking the ratio o f the standard p eak area counts over the internal standard peak area counts to fit the data for each analyte.
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Analytical Protocol: GLP10-u1^02 Amendment 30
6 Reporting Requirements
For each sampling location, the report will contain the results for the sample, sam ple duplicate, and field matrix spike Trip blank and trip blank spike will be reported for the sam ping event as will any equipm ent/rinseate blanks prepared in the field. Laboratory control spikes o f reagent w ater prepared a t the tim e of sam ple extraction will also be reported and used to evaluate the overall method accuracy and precision. Method blanks o f reagent w ater prepared at the tim e of sam ple extraction will be used to determ ine the method detection lim it
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Atta c h m e n t B: R e p r e s e n ta tiv e S a m p l e C h r o m a to g r a m s a n d C a lib r a tio n C u r v e (s )
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Workstation: ETSBUSTER
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Atta c h m e n t C : A n a ly tic a l M e t h o d (s )
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3M Environmental Laboratory
Method
Method o f Analysis for the Determination o f Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis
Method Number: ETS-8-044.1
,Adoption Date: 4/12/07
Effective Date: / 1 ''I ' / i (
Approved By:
W illiam K. R eagen, Technical D irector, Environm ental Laboratory
J s U C /i/ S t o j/
D ate
E T S -8 0 4 4 .1
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Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct
Injection Analysis
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1 Scope and Application
This method describes the direct injection analysis of perfluorinated compounds (PFC s) from w ater m atrices using high-performance liquid chromatography tandem mass spectrometry (HPLC/M S/M S). The method is generafly applicable but not lanited to the m easurement of perfluoroalkyl sulfonamides and perfluorinated alkyl adds (PFAAs) such as perfluorosulfonic adds (PFSAs) and perfluorocarboxyfic adds (PFCAs) (Table 1). W ater samples containing heavy particulate may require preparation by an alternate method such as ETS-8-154 "Determination of Perfluorinated Adds, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry". The method is applicable to both external standard and internal standard calixatio n 1.
T ab le 1. R ep resen tative T arg e t A n alytes
A c ro n y m
PFB A (C 4 A rid) PFPeA (C 5 A rid) PFHxA (C 6 A rid) PFHpA (C 7 A rid) PFOA (C 8 A rid) P F N A (C 9A rid ) PFDA (C 10 A rid) PFUnA(C11 A rid) PFDoA (C 12 A rid) PFTrDA (C 13 Acid) PFBS (0 4 Sulfonate) PFHS (C 6 Sulfonate) PFOS (C 8 Sulfonate) FBSA (C 4 Sulfonamide FOSA (C 8 Sulfonamide)
A n a ly te
Perfluorobutanoic add Perfluoropentanoic arid Petfluorohexanoic arid Pertkiorotieptanoic arid Periluorooctanoic acid Perfluorononanoic arid Perfluorodecanoic arid Perduoroundecanoic arid Perfluorododecanoic arid Perihiorotridecanoic arid Petfluorotxjtanesulfonic arid Petfluorohexanesuifonic arid Perfluorooctanesulfonic arid Pertkiorobutanesirifonam ide PefluorooctanesuNonamide
C h e m ic a l A b s tr a c t S e rv ic e R e g ia try N u m b e r (C A S R N )
375-22-4 2706-90-3 307-24-4 375-85-9 335-67-1 37595-1 335752 2 0 5 5 9 4 -8 3 0 7 -5 5 1 72629-94-8 375755 355454 1765251 3 0 3 3 4 -6 5 1 7 5 4 -9 1 -6
The Minimum Reporting Level (M R L) is the Limit of Quantitation (LO Q ) that m eets Data Quality Objectives (DQ O s) that are developed based on the intended use of this method.
Method Flexibility - This is a performance-based method and m ay be generally applied to the determination of perfluorinated compounds in water m atrices when analysis batch quality control (Q C ) criteria are m et12. Each set of samples are prepared in an analysis batch with calibration standards, LCSs, blanks, and continuing calibration check standards analyzed on the sam e instrument during a tim e period that begins and ends with the analysis of the appropriate continuing calibration check standards. The laboratory is permitted to m odfy the LC column, mobile phase composition, LC conditions, and M S/M S conditions. Method modifications should be considered to improve method perform ance or to m eet data quality objectives for the study. In all cases where method mocfifications are implemented, the batch
a1nHdieCm8 petehroflduoisrosaulpkpaonretesdulbfoynvaamlididaetiionnlwabiothraitnotreyrncaolnsttraonldsaarmd pclaelsiburnadtieorn3fMormC4e-thCo1d3vPaFliCdaAtiso,nCE4.llC-066. a6n7d. C8 PFSAs, 2Guidance for establishing method QC Criteria based on a.) FDA M ay 2001, "Guidance for Industry, Bioanalytical MM eetthhooddsVoaflAidnatailoyns"is, bin.)SEuPpApoMrteotfhPodre5-r3e7g,iastnrdatcio.)nEDuarotapReaenquCioremmmenistssiofonr: AGnunideaxnIcEe(fPoarrGt Aen. seeracttiinogn a4n)danRdepAonrntienxgin (Part A,section 5) o f Directive 91/414, SANCO/3029/99 rev. 4 (11/07/00).
E T S -8 -0 4 4 .1
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Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/M S;
Direct Injection Analysis
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analytical QCs (section 9 ) must be completed and pass QC acceptance arteria (section 13) if the data from the analytical batch are to be reported.
2 Method Summary
W ater samples are analyzed as neat aqueous sample or as solvent diluted aqueous samples by direct injection using LC/M S/M S. Sam ples containing heavy particulate m ay not be suitable for analysis by this method. Samples contatoing suspended particulate should be centrifuged or titered prior to removing a sample aliquot or diluting with solvent The water sam ple is mixed w ell prior to removing an aliquot or diuting, if necessary, with ASTM Type I water, HPLC w ater, other suitable w ater, or solvent (m ethanol).
Quantitation is by stable isotope internal standard calibration in laboratory reagent water. All perfluorinated compounds (PFC s) target analyte concentrations of perfluorosuHbnic adds (PFSAs) and perfluorocarboxylic adds (PFCAs) are reported as anions and corrected for their salt or free add form s. Alternatively, quantitation may be performed by external standard calibration.
This is a perform ance-based method. Method uncertainty tor each target analyte is determ ined for each analytical batch using multiple laboratory control spires at multiple concentrations. This method also requires that the precision and accuracy for each sam ple be determ ined using field m atrix spikes to verify that the method is applicable to each sample m atrix.
Calibration standards for PFUnA, PFDoA, PFTrDA, and FOSA have been found to be unstable for m ore than 2 days in 100% w ater. Sam ples requiring analysis for these compounds by this method should be diluted 1:1 with methanol and analyzed against a calibration curve prepared n 1:1 synthetic groundw aterM eO H
3 Definitions
3.1 Analysis Batch
A set of study sam ples that are prepared with calbration standards, laboratory control samples, and procedural blanks, and analyzed on the sam e instrument during a tim e period that begins and ends with the analysis of the appropriate continuing calibration check standards.
3.2 Analytical Sample
A portion of a laboratory sam ple prepared for analysis.
3.3 Calibration Standard
A solution prepared by spiring a known volume of the W orking Standard (W S ) into a predeterm ined amount o f ASTM Type I, HPLC grade w ater, or other suitable w ater (i.e. matrix w ater), and analyzed accortfing to this method. Calibration standards are used to calibrate the instrument response with respect to analyte concentration.
3.4 Laboratory Duplicate Sample (LDS, or Lab Dup)
A laboratory duplicate sam ple is a separate aliquot of a sam ple taken in the analytical laboratory that is analyzed separately with identical procedures. Analysis of LDSs compared to that of the first aliquot give a m easure of the precision associated with laboratory procedures, but not with sam ple collection, preservation, or storage procedures.
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3.5 Field Blank (FB)/Trip Blank (TB)
ASTM Type I, HPLC grade w ater, or other suitable water, placed in a sam ple container in the laboratory and treated as a sam ple in all respects, including exposure to sampfing site conditions, storage, preservation and all analytical procedures. The purpose o fthe TB is to determ ine if test substances or other interferences are present in the field environm ent This sam ple is also referred to as a Trip Blank.
3.6 Field Duplicate Sample (FDS, Field Dup)
A sam ple collected in duplicate a t the sam e tim e from the sam e location as the sam ple. The FDS is handed under identical circumstances and treated exactly the sam e throughout field and laboratory procedures. Analysis o f the FDS compared to that o f the first sam ple gives a m easure o f the precision associated with sam ple collection, preservation told storage, as w el as with laboratory procedures.
3.7 Field Matrix Spike (FMS)
A sam ple to which known quantities of the target analytes, ISs and SRSs are added to the sam ple bottle in the laboratory before the bottles are sent to the field for coflection o f aqueous samples. A known, specific volume o f sample must be added to the sam ple container without rinsing. This may be accomplished by making a T9 to this leveT in e on the outside of the sam ple container. The FMS is analyzed to ascertain if any m atrix effects, interferences, or stabiity issues may com plicate the interpretation of the sam ple analysis.
3.8 Trip Blank Matrix Spike (TBMS)
An aliquot o f ASTM Type I, HPLC grade w ater, or other suitable w ater, to which known quantities of the target analytes, ISs and SRSs are added in the laboratory prior to the shipment o f the collection bottles. The TBMS is analyzed exactly fike a study sam ple to help determ ine if the method is in control and whether a loss of analyte or analytical bias could be attributed to sam ple holding tim e, sample storage and/or shipment issues. A low and high TBMS are appropriate when expected sample concentrations are not known or m ay vary.
3.9 Internal Standard (IS)
A compound added to each study sam ple, captation standard, laboratory control sam ples, and procedural blanks a t a consistent level (typically around 1 ng/m L). The internal standard(s) are stable isotope labeled versions of the target analytes. The area count ra t of the target analyte to the internal standard is used for calibration. Surrogate ISs are applied when stable isotope ISs of target analytes are unavailable. A surrogate IS is not necessarily a stable isotope labeled version of the target analyte, but is treated as an internal standard for
quantitation.
3.10 Laboratory Control Sample (LCS)
An aliquot o f control m atrix to which known quantities of the target analytes, ISs and SRSs (when applicable) are added in the laboratory at the tim e when sam ples are atiquotted. At least three levels (two levels for SRSs) in triplicate are included, one generally a t the low end o fthe calibration curve and one near the mid range and the upper end o f the curve. The LCSs are analyzed exactly like a laboratory sam ple to determ ine w hether the stabiity o f the standards. LCSs should be prepared each day sam ples are aliquoted.
3.11 Laboratory Matrix Spike (LMS)
A laboratory m atrix spike is an aliquot of a sam ple to which known quantities o f target analytes, ISs and SRSs (when applicable) are added to the laboratory. The LMS is analyzed exactly like a laboratory sam ple to determ ine whether the sample m atrix contributes bias to the analytical results. The endogenous concentrations of the analytes in the sam ple matrix must be determ ined in a separate akquot and the measured values'm the LMS corrected for these concentrations. LMSs are optional for analysis of aqueous sam ples.
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3.12 Laboratory Sample
A portion or aliquot of a sam ple received from the field for testing.
3.13 Limit of Quantitation (LOQ)
The lower lim it of quantitation (LLO Q) for an analytical batch is the lowest concentration that can be reliably quantitated within the specified lim its o f precision and accuracy. The LLOQ is generally selected as the lowest non-zero standard in the calibration curve that m eets method acceptance criteria. The LLOQ for each target analyte is established for each analysis batch as the lowest calixation standard with area counts at least twice that o f the average area counts of the procedural blanks.
The upper lim it of quantitation (ULO Q ) for an analytical batch is the highest concentration that can be reliably quantitated within the specified lim its o f precision and accuracy. The highest standard in the calibration curve that m eets method acceptance criteria is defined as the ULOQ.
3.14 Method/Procedural Blank
An aliquot o f control m atrix that is treated exactly Ik e a laboratory sam ple including exposure to all glassware, equipm ent, solvents, and reagents that are used with other laboratory sam ples. The method blank is used to determ ine if test substances or other interferences are present in the laboratory environment, the reagents, or the apparatus.
3.15 Sample
A sam ple is an aliquot removed from a larger quantity of m aterial intended to represent the original source m aterial.
3.16 Stock Standard Solution (SSS)
A concentrated solution of a single-analyte prepared in the laboratory with an assayed reference compound.
3.17 Surrogate Internal Standard
An IS that is not necessarily a stable isotopically labeled target analyte, but is treated as an internal standard for quantitation. Surrogate ISs are used when isotopicaly labeled counterparts of the target analyte are not commercially or readily available.
3.18 Surrogate Recovery Standard (SRS)
An isotopically labeled standard, not used as an internal standard, that is added to each sample and appropriate Q C sam ple as a means to evaluate the method performance for a chemical class of compounds (e.g ., PFSAs, PFCAs).
3.19 Working Standard (WS)
A solution o f several analytes prepared in the laboratory from SSSs and cffluted as needed to prepare calibration standards and other required analyte solutions.
4 Warnings and Cautions
4.1 Health and Safety
The acute and chronic toxicity of the standards for this method have not been precisely determined; however, each should be treated as a potential health hazard. The analyst should w ear gloves, a lab coat, and safety glasses to prevent exposure to chem icals that might be present
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The laboratory is responsife for maintaining a safe work environment and a current awareness of local regulations regarding the handling of the chemicals used in this method. A reference fie of m aterial safety data sheets (M SDS) should be available to all personnel involved in these analyses.
4.2 Cautions
The analyst must be fam iliar with the laboratory equipment and potential hazards including, but not lim ited to, the use of solvents, pressurized gas and solvent lines, high voltage, and vacuum systems. Refer to the appropriate equipment procedure or operator manual for additional information and cautions.
5 interferences
During sam ple preparation and analysis, m ajor potential contaminant sources are reagents and glassware. All m aterials used in the analyses shall be demonstrated to be free from interferences under conditions o f analysis by running method blanks.
Parts and supplies that contain Teflon should be avoided or minimized due to the possibility o f interference and/or contamination. These may include, but are not lim ited to: wash bottles, Teflon lined caps, autovial caps, HPLC parts, etc.
The use of disposable micropipettes or pipettes to aliquot standard solutions is recommended to m ake calibration standards and m atrix spires.
6 Instrumentation, Supplies, and Materials
_______________
6.1 Instrumentation
Analytical balance capable of reading to 0.0001g HPLC/M S/M S or HPLC/M S system, as described in Section 10.
6.2 Supplies and Materials
Sam ple collection bottles-- HDPE (e.g ., NalgeneTM ) wide-mouth bodes with screw cap. N ote: Do not use fluorinated or Teflon bottles or fried caps. Coolers or boxes for sam ple shipm ent 15-m L and 50-m L disposable polypropylene centrifuge tubes. Class A pipettes and volum etric flasks, various. 2 mL HPLC autovials Disposable pipettes, polypropylene or glass as appropriate Centrifuge capable of spinning 15-m L and 50-m L polypropylene tubes at 3000 rpm.
7 Reagents and S t a n d a r d s ________________________________
N ote: Suppliers and catalog numbers are for illustrative purposes only. Equivalent performance may be achieved using chemicals obtained from other suppliers. Do not use a lesser grade of chemical than those listed.
7.1 Chemicals
W ater - M H-Q , HPLC grade, or other suitably appropriate sources
Calcium Acetate - A .C .S. Reagent Grade
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Magnesium Acetate - A .C .S. Reagent Grade Methanol - HPLC grade Ammonium Acetate - A .C .S. Reagent Grade
7.2 Representative Target Analytes, ISs, and SRSs
PFBA, Heptafluorobutyric Acid, (C4 Perfluorinated A dd) PFPeA, Nonafluoropentanoic Add (Cs Perfluorinated A dd) PFHxA, Perfluorohexanoic Add (C6 Perfluorinated A dd) PFHpA, Tridecafluoroheptanoic A dd, (C 7 Perfluorinated A dd) PFOA, Ammonium perfluorooctanoate, (Cs Perfluorinated A dd) PFNA, Heptadecafluorononanoic Add, (Cg Perfluorinated A dd) PFDA, Nonadecafluorodecanoic Add (C 10 Perfluorinated A dd) PFUnA, Perfluoroundecanoic A dd, (C n Perfluorinated A dd) PFDoA, Perfluorododecanoic A dd, (C 12 Perfluorinated A dd) PFTrDA, Perfluorotridecanoic Add, (C 13 Perfluorinated A dd) FBSA, Perfluorobutanesulfonamide FOSA, Perfluorooctanesulfbnylamide PFBS, Potassium Perfluorobutanesulfbnate PFHS, PerfluorohexanesuHbnate PFOS, Potassium perfluorooctanesulfonate PFOA [1 ,2 ,3 ,4 -13C ], 13C4-isotopically labeled perfluorooctanoic add (SR S) PFOS [1 ,2 ,3 ,4 -13C ], 13C4-isotopically labeled Perfluorooctanesulfonate (SR S) PFUnA [1,2 -13C ], 13C2-isotopically labeled Perfluoroundecanoic add (SR S) A custom mix of ISs in a m ethanolic solution containing ([1 .2 ,3 ,4-13C JPFBAJ1 ,2 13(yP F H xA , [1,2 ,3 ,4,5,6 ,7 ,8 -13Ca]PFOA, [1,2 ,3 ,4,5,6 ,7 ,8,9-l3CyPFNA, [1,2 -C J P F D A , [1 ,2 ,3 ,4 ,5 ,6 ,7 -l3C7]PFUnA, [U -^ C jjP F D o A , [1 ,2 ,3 -l3CaPFHS, [U ,3 ,4 ,5 ,6 ,7 ,8 -13CalPFOS, a id [1,2 ,3 ,4,5,6 ,7 ,8-13C^PFO SA (W ellington Laboratories, Guelph, O N ) in combination with added ([1 ,2 ,3,4,5 -13Cs]PFPeA, ([I^ .S .^ ^ C JP F H p A , and [^O JPFB S can be used to prepare a stock IS solution. Alternatively, individual stable isotope ISs can be used to prepare a stock IS mixture. Other ISs can be applied.
7.3 Reagent Preparation
2 mM Ammonium acetate solution (Analysis)--W eigh 0.3 g o f Ammonium acetate and dissolve in 2.0 L of reagent w ater. Synthetic Groundwater (containing 25 ppm Ca and M g) - W eigh 0.61 g of Caldum Acetate and 0.92 g of Magnesium Acetate and dissolve in 6.0 L of reagent w ater. Note: Alternative volumes may be prepared as long as the ratios o fthe solvent to solute ratios are maintained.
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7.4 Stock Standard Solution (SSS) and Working Standard Solution Preparation
The following standard preparation procedure serves as an exam ple. W eighed amounts and final volumes m ay be changed to suit the needs of a particular study. For exam ple, pL volumes m ay be spiked into volumetric flasks when diluting stock solutions to appropriate levels.
100 pg/m L targ et analyte SSSs-- W eigh out 10 mg of analytical standard (corrected for percentsalt, acidETS-4~031]andpurity) and dilute to 100 mL with methanol or other
suitable solvent in a 100 mL volum etric flask. Transfer to a 125 mL LDPE bottle or other statable container. Prepare a separate solution tor each analyte. Expiration dates and storage concfitions of stock solutions should be assigned in accordance with laboratory standard operating procedure. An exam ple of purity and salt correction is given below for PFOS.
,, ,, . . m olecular w eight o f anion salt correction factor = --------------------- - ----------------
m odecular w eight o f salt
JQQ
PFO S (K + )salt correction factor =
= 0.9275
10 mg CsFuSOalC with purity 90% = 8.35 mg C aF^SO f (10 m g*0.90*0.9275=8.35 mg)
10 pg/m L (10,000 ng/m L) m ixed w orking standard--Add 5.0 mL each of the 100 pg/mL SSSs to a 50 mL volumetric flask and bring up to volume with solvent
1 pg/m L (1,000 ng/m L) m ixed w orking standard--Add 0.5 mL of the 100 pg/mL SSSs to a 50 mL volumetric flask and bring up to volume with solvent.
0.1 pg/tnL (100 ng/m L) m ixed standard--Add 0.05 mL of the 100 pg/mL SSSs to a 50 mL volumetric flask and bring up to volume with solvent
Storage C onditions-- Store all SSSs and working standards in accordance with laboratory standard operating procedure or in a refrigerator at 42C for a maximum period of 6 months from the date of preparation.
7.5 Calibration Standards
Calibration can be performed by IS or external calibration. Using the working standards described above, prepare calibration solutions in ASTM Type I w ater, HPLC w ater, other suitable w ater, or a mixture of solvent and w ater using the information in Table 2 as a guideine. Note: Volumes o fw ater or w ater/solvent mixtures and working standards m ay be adjusted to m eet the data quafty objectives addressed in the general project outline. Calibration levels other than those listed below can be prepared as needed.
For the quantitation of PFOA and PFOS, reference m aterials of certified mixed linear and branched isomer are preferred. Alternately, reference m aterials of prim arily in ear isomers of PFOA and/or PFOS may be used, however, when quantitating with predominantly linear reference standards, additional LCS sam ples containing both linear and branched isomers of PFOA and PFOS are required3.
7.5.1 Internal Standard (IS ) and Surrogate Recovery Standard (SRS)
For IS caforation, stable isotope internal standards of each target analyte or appropriate surrogate ISs should be spiked a t the sam e level in all calibration standards. Once the calibration standards have been prepared as stated above in Section 7.5, all calibration standards are spked with a separate internal standard spiking solution. Typicafly the
3 A n p ^ rt iw n ow iyw p iwi
rrf~th^ i w r clatw U rrlc
rtytiO rA ,*1 h re n rh i-d raw m rr o f
P FO A /FFO S can be found m 3M report E l1-0560
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concentration o f th e internal standard is consistent w ith th e internal standard concentration expected in th e sam ples being prepared, usually 1 ng/m L. T he concentration o f th e internal standard spiking solution is typically 2 pg/m L. A separate zero point or m ethod blank is typically prepared a t th e sam e tim e as the caBbration standards, using th e sam e solution used to prepare the standards (A S TM Type I w ater, H PLC w ater, oth er suitable w ater, o r a solvent/w ater m ixture), and is spiked w ith th e internal standard a t th e sam e concentration as th e calibration curve, typically a t 1 ng/m L.
If the sam ples being analzyed w ere pre-spiked w ith S R S s, th e calibration curve prepared in Section 7 .5 is s p ite d w ith a separate SR S sp itin g solution. T yp icaly, th e sam ple bottles a re s p ite d w ith a S R S a t 0.1 ng/m L. T he fin al calibration curve m ust consist o f a t least six calibration points afte r analysis. T he follow ing tab le provides an exam ple o f s p ite concentrations and volum es used to achieve a m ulti-point extracted calibration curve w ith internal standard and surrogate standard.
T able 1 lists recom m ended stable isotope internal standards fo r several PFS A and PFC A target com pounds. A custom m ix o f isotopicaly labeled targ et analytes in a m ethanolic solution containing ([1 ,2 ,3 ,4 -13C JP FB A , [1 ,2 -C J P F H x A , [1 ,2 ,3 ,4 ,5 ,6 ,7 ,8 -13Q JP FO A , [U ,3 ,4 ,5 ,6 ,7 ,8 ,9 -1SQ JP FN A , [1 ,2 ,3 ,4 ,5 ,6 - 13Ce]PFDA, [1 ,2 ,3 ,4 ,5 ,6 ,7 -l3C7]P FU nA . [1 ,2 "c y P F D o A , [1 ,2 ,3 -13C :JP FH S , [1 ,2 ,3 ,4 ,5 ,6 ,7 ,8 -13C aP F O S , and [U ,3 ,4 ,5 ,6 ,7 .8 -13Q JFO SA (W ellington Laboratories, G uelph, O N ) in com bination w ith added ([1 ,2 ,3 ,4 ,5 -l3C jP F P e A , ([1 ,2 ,3 ,4 -13C JP FH pA , and [^O JP F B S can be used to prepare a stock IS solution. A lternative sources o f certified stable isotope labeled targ et analytes a re applicable. A lternatively, individual stable isotope IS s can be used to prepare a stock IS m ixture. The tab le below lists th e recom m ended stable isotope IS s and S R S s applied in th e m ethod. O ther stable isotope IS s and S R S s o f target analytes not listed in th e tab le m ay be used if supported by validation an d/o r analysis batch Q C s m eeting m ethod acceptance criteria (e .g ., ['X J -P F O A ). T he sam e internal standard should be used fo r a given analyte throughout the en tire prpject/study. N ote: som e o f th e com pounds listed below are appropriate to use as surrogate IS s w hen a stable isotope IS o f a targ et an alyte is not availab le. G enerally, surrogate isotopicaly labeled PFC A s are used fo r PFC A s, and surrogate isotopically labeled PFSA s are used fo r PFSA s.
Table 2 provides exam ples o f sp k e concentrations and volum es used to achieve a m ulti-point calibration curve w ith IS s and SR Ss.
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Table 1. Stable Isotope PFCAs and PFSAs used for ISs and SRSs
CompoundName I3C4-Plluuiubulanoic acid 13C4-Perfhion>petitanoic add 13C2-Perfhiorohexaiioic acid >3C4-Perfiuorolieptanoic add 13Ct-Peifluorooctanoic acid l]r f lWliinmiMMiMf add 13Cf-Po&cn)dccaaotc aod 13C7-Peifluoroundccano acid 13C2-PerfluoiDdodecanoic add 3Ir^-AmifionifTi Parflnnsnliiiiane sulfonate 13C3-Ammonium Paflm diw anc sulfonate t3Cf-Sodiam Perfluorooctanc sulfonate
^Cr-Perfhiorooctanoic add 13C2-Perfluotoundecanoic add 13Cr-Perfluorooctane sulfonate
Synonym orAcronym [133,4-UC]PFBA [1,2JA S -^C jJP F P tA [U -"C2]PF&A [1,2,3,4-L,C4JPFHpA [133,4,5,6,7,8-uC,]PFOA [133,4,5,6,7,8,9-I3CJPFNA [1,23,4,5,6 -UCJPFDA [133,4,5,6,7 -"CjPTUiiA [1.2 -"CJPFDoA [" OjJPFBS [1 3 3 -`3C3JPFHS [133,4,5,6,7,8-uCJPFOS
[133,4,5,6,7,8-uQ|FOSA [133,4-uC,JPFOA [1 3 -uCJ]PFttiA [1,2,3,4-13C4JPFOS
AnalyticalPurpose IS fr PFBA ISforPFPeA ISforPFHxA IS forPFHpA I"SCfroJPrFPOFOAA and [133,4 IS forPFNA IS forPFDA
ISforPFUnA IS for PFDoA, *PFTA IS forPPBS IS for PFHS IPSFfOorSP[F1O33S,a4n13dC4], IS forFOSA
SRS for aUPFCAs: C4-C8
RSoeuferrceence Standard Wellington Labs (Mix orIndividual) Wellington Labi (Mix orIndividual) Wellington Lab (Mix orfodavidnal) Wellington Labs (Mix orIndividual) Wellington Lab* (Mix orIndividual) W ellington Labs (Mix or Individual) Wellington Labs (Mix orIndividual) Wellington Labs (Mix orIndividual) Wellington Labs (Mix orIndividual) R(InHdiIvnidteumalr)aaal Wellington Labs (Mix orIndividual) Wellington Labs (Mix or Individual) Wellington Labs(mix) R(InTdIiIvnitdeurnala)tional Wellington
SRS for allPFCAs C9-C13 Wellington
CSR6S,afnodrCal8lPFSAs: C4. Wellington
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Table 2. Example Preparation of Calibration Curve with ISs and SRSs
Sample Description
0.025 ng/mL curve point 0.030 ng/mL curve point 0.04 ng/mL curve point 0.05 ng/mL curve point
0.1 ng/mL curve point 0.25 ng/mL curve point 0 .5 ng/mL curve point
1 ng/mL curve point 2 .5 ng/mL curve point 5 .0 ng/mL curve point 10.0 ng/mL curve point 25.0 ng/mL curve point 50.0 ng/mL curve point 75.0 ng/mL curve point 100 ng/mL curve point
Concentration Volume of VolumeofIS of WS, pgfmL WS.pL (2pg/mQ.pL
0 .1 0 0 .1 0 0 .1 0 0 .1 0 0 .1 0 0 .1 0 1 .0 1 .0 1 0 .0 1 0 .0 1 0 .0 1 0 .0 1 0 .0
mo
1 0 .0
25 30 40 50
100
250 50
100
25 50
100
250 500 750
1000
50 50 50 50 50 50 50 50 50 50 50 50 50 50 50
Concentration of Surrogate, pgfmL
0 .2 0 0 .2 0 0 .2 0 0 .2 0 0 .2 0 0 .2 0 0 .2 0 0 .2 0 1 0 .0 1 0 .0 1 0 .0 1 0 .0 1 0 .0 1 0 .0 1 0 .0
Volume of Surrogate, pL
1 2 .5 15
20
25 50 125 250 500 25 50
100
NA NA NA NA
Volume ofASTM Type1Water, or othersuitablesolventn, m i
100 100 100 100 100 100 100 100 100 100 100 100 100 100 100
N /A - Not Applicable (1) Samples requiring analysis for PFUnA, PFDoA, PFTrDA, and FOSA should be analyzed against a caibration curve prepared in 1:1 synthetic groundwaterMeOH.
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8 Sample Collection and Bottle Preparation
S am ple collection bottles a re prepared by 3M Environm ental Laboratory (o r subcontract su p p ler) personnel fo r shipm ent a t am bient tem perature to th e collection site. Typically, four separate collection bottles are associated w ith a single collection site: sam ple, field duplicate sam ple, low field m atrix spike, and high field m atrix spice. A lternatively, th e sam ple and field duplicate sam ple m ay contain S R S s in ie u o f additional target analyte low field m atrix spice and targ et an alyte high field m atrix spice sam ples. Depending on th e scope o f th e project, additional replicates o f th e field sam ple and field m atrix spices m ay be added. A lso, it is not uncomm on fo r additional m id-level field m atrix spices to be collected if th e expected sam ple concentrations are truly unknown o r could span a large concentration range.
H igh-density polyethylene (H D P E ) w ide-m outh N algene bottles are used fo r th e sam ple coflection containers. (Volum es o f th e bottles m ay vary depencfing on how m uch sam ple is required to m eet data quality objectives.) Sam ple collection volum es are project specific and based on d ata quality objectives. T h e N algene bottles do not require any pretreatm ent prior to use. Typically, placem ent o f a sam ple bottle volum etric T 9 to here' line is done by using a sam ple bottle m arker tem plate. A lternatively, bottles m ay be w eighed prior to bottle preparation and w eighed again afte r sam ples have been collected.
A l bottles should be clearly labeled to indicate its intended use as a sam ple, field sam ple duplicate, low field m atrix spice, high field m atrix spike, sam ple/S R S field m atrix spice, field duplicate sam ple/S R S field m atrix spike, trip blank, o r trip blank m atrix spice. If each location has different designated spike levels, th e label should also clearly indicate th e sam ple location designation. G enerally, a set o f bottles fo r a given collection site are prepared then grouped together in plastic bags fo r organizational purposes. For each sam ple collection event, a t least one set o f trip blank and trip blank m atrix spices are prepared.
B ottle preparation should be docum ented in a N ote to F ile or on a sam ple preparation w orksheet and should include th e foflow ing inform ation: d ate prepared, to tal num ber o f bottles prepared, num ber o f sam ple sites, the standard identification num bers a id spice volum es used to prepare spiced bottles, th e TM to here' volum e, and any oth er pertinent inform ation needed fo r reconstructibiity o f th e d ata. T h e N ote to F ie wB be included in th e final data package fo r th e p ro ject
Sam ples a re collected in th e field and shipped to th e laboratory a t am bient tem perature.
8.1 Field Matrix Spike Sample (FMS)
Field m atrix spike sam ples a re a requirem ent o f the m ethod. A FM S sam ple is defined as a Q C sam ple to which known quantities o f appropriate targ et analytes a re added to th e sam ple bottle in th e field o r in the laboratory before th e bottles a re sent to th e fie ld . T he sam ple and field duplicate sam ple m ay co n tari appropriate S R S s in fieu o f targ et analyte FM S sam ples. Sam ple quantities a re determ ined volum etrically or gravim etricaily. A known, specific volum e o r w eight o f sam ple is added to th e sam ple container w ithout rinsing. Volum etric sam pte m easurem ents m ay be acquired by a laboratory applied T il to this level" fine on the outside o f th e sam ple container. T arg et analyte FM S sam ples should be spiked a t approxim ately 0 .5 -1 0 tim es th e expected analyte concentration in th e sam ple. If th e expected range o f analyte concentrations is unknown, m ultiple spikes a t varying levels m ay be prepared to increase th e likefihood th at a spice a t an appropriate level is m ade. Typically a low and a high targ et analyte spice a re prepared fo r each sam pling location. In those instances w here S R S s are to be used in lieu o f target analyte FM S sam ptes, th e sam ple and field duplicate sam ple a re spiked a t approxim ately 2 -5 tim es th e target LO Q . T he FM S is analyzed to ascertain if m atrix effects o r sam ple holding tim e contributes bias to th e analytical results. For th e sam ple bottles designated fo r m atrix spices, an appropriate volum e o f m atrix spicing solution is added to th e em pty bottle prior to sam pfing. T he volum e o f spice solution added should produce th e desired final concentration o f targ et analytes once the bottle is file d w ith sam ple to th e T 9 to h ere line' . T he m atrix spicing solution(s) should be prepared in a suitable solvent and contain a i o f th e appropria te targ et analytes, IS s, and S R S s. T h e targ et analyte m atrix spiking solution is often th e sam e as th e working standards used to create th e catibration standards. An exam ple o f a bottle spice is given below .
"F 9 to here' volum e = 200 m L (A 2 5 0 m L N algene bottle is used)
D esired Field S pice Concentration = 0 2 5 ng/m L
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500 pL o f a 0.1 pg/m L s p rin g solution (containing th e target an alytes) is added to th e bottle and th e bottle cap prom ptly sealed .
8.2 Internal Standard and Surrogate Recovery Standard
If analysis o f a surrogate recovery standard (S R S ) is included in the project objectives, an appropriate volum e o f a surrogate standard solution is added to a ll the bottles prior to sam pling and S P E . Typically sam ple bottles are spiced w ith surrogate recovery standards a t a final desired s p ire concentration o f 0.1 ng/m L.
If quantitation by internal standard (IS ) is included in th e project objective, an appropriate volum e o f internal standard solution is added to a ll th e bottles prior to sam pling and S P E . Typically sam ple bottles are spiked w ith internal standard a t a fin al desired s p k e concentration o f 1 ng/m L.
For th e trip blank, th e S R S spike and IS spice is added to the bottle and then A STM Type I w ater (H P LC grade reagent w ater o r other suitable w ater m ay used) is added to th e m to here' lin e. T h e botUe is capped and sealing tap e m ay be placed around th e outer edge o f th e cap. T rip blank m atrix spices a re prepared by adding th e appropriate volum e o f targ et analyte spiking solution, IS , and S R S spicing solutions and fillin g th e bottle to th e desired volum e w ith th e appropriate w ater and capping and seafing th e cap.
9 Quality Control and Data Quality Objectives
9.1 Data Quality Objectives
This m ethod a id required quality control sam ples is designed to generate data accurate to 30% w ith a targeted LO Q o f 0 .0 2 5 n g/m L A ny deviations from th e quality control m easures spelled out below w ill be docum ented in th e raw data and footnoted in the final rep o rt
9.2 Method/Procedural Blanks
T he m ethod/procedural blank is zero point calibration standard (w hich includes IS s ) analyzed in a regular basis w ith each analysis batch. A t a m inim um , m ethod blanks are analyzed prior to instrum ent calibration, prior to th e analysis o f C C V sam ples, a fte r every 10 sam ple injections, and a t th e end o f th e analytical o n .
T h e m ean area count o r area ratios w hen using internal standard calibration, fo r each an alyte in th e m ethod blanks m ust be less than 50% o f th e area count co u rts o r area ratios w hen using internal standard calibration, o f th e LO Q standard. T h e standard deviation o f the area counts, o r area ratios w hen using internal standard calibration, o f th ese m ethod blanks should be calculated. A specific % R SD acceptance criteria is not specified but is assessed on an analytical batch basis. If th e m ean area counts or area ratios w hen using internal standard calibration, o f th e m ethod blanks exceed 50% o f th e LO Q standard, then th e LO Q m ust be raised to th e fast standard level in th e curve th at m eets criteria. M ethod blanks m ay be elim inated if technical justification can be provided (e .g . th e procedural blank w as analyzed a fte r an unexpectedly high level sam ple). If any procedural blanks a re rem oved from th e LO Q determ ination, docum ent in the raw d ata and report as appropriate. Laboratory S am ple R e p lic a te s /F ie ld D uplicate Sam ple
Typically, sam ples are coflected in duplicates in th e fie ld . T h e relative percent difference (R P D ) o f duplicate sam ples should be s20% fo r th e precision o f sam ple preparation and analysis to be considered in control. R eplicate sam ples not m eeting th e <20% R PD criteria a re flagged and reported as outside o f Q C acceptance criteria.
9.3 Laboratory Matrix Spikes (LMSs)
LM Ss m ay be perform ed in lieu o f FM Ss if FM Ss have previously been perform ed fo r th e sam ple m atrix. A dditionally, LM Ss m ay b e perform ed in lieu o f FM Ss fo r a sam ple m atiix if th e FM S levels w ere not appropriate fo r determ ining spike recoveries relative to endogenous levels o f targ et analytes and appropriate S R S s. G enerally, each sam ple location represents a d ifferen t sam ple and sam ple m atrix. LM Ss a re prepared fo r each sam ple and analyzed to determ ine th e m atrix effect on spice recovery efficiency o f each targ et analyte and appropriate S R S s. LM Ss should be prepared a t a minim um o f one level and in diqblicate. LM S concentrations should be prepared a t approxim ately 0 .5 -1 0 tim es the endogenous concentration or approxim ately 4 -1 0 tim es th e LO Q concentration o f each targ et analyte.
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Lab m atrix s p k e recoveries should fafl w ithin 30% o f expected values. Sam ple d ata w ith LM S recovery outside o f 30% but w ithin 50% o f the expected value are flagged and reported as outside o f Q C acceptance criteria. D ata w ith LM S recovery outside o f 50% o f th e expected value a re reported as N R , w here N R is defined as "N ot R eportable'' d ata outside o f Q C acceptance criteria.
9.4 Lab Control Sample
Lab control sp kes a re prepared fo r each analysis batch to determ ine m ethod accuracy and precision. LCSs should b e prepared a t th ree levels in tripficate fo r each target analyte and a t a m inim um o f tw o levels in trp fc a te fo r approp riate S R S s. Low lab control sp ite s should be prepared a t a concentration in th e range o f approxim ately four to ten tim es higher th a t th e targeted low er LO Q , th e m id lab control s p ite s should be prepared a t a concentration n ear th e m id-point o f th e caib ratio n curve and th e high lab control spices a t approxim ately 80% o f the upper LO Q . For each target analyte and S R S s, th e percent relative standard deviation (m ethod precision) fo r each control s p ite level m ust be less than o r equal to 20% and th e average recovery (m ethod accuracy) fo r each control spike level m ust b e 80-120% . Sam ple d ata fo r targ et analytes outside o f th e laboratory control s p ite acceptance criteria w il be handed as follow s:
If th e average recovery o f a sp itin g level fa lls outside m ethod acceptance, but a t least 67% (6 out o f 9 ) o f LCS sam ples are w ithin 20% o f th eir respective nom inal value (33% o f the Q C sam ples, not alrep S cates a t the sam e concentration, m ay be outside 20% o f nom inal valu e), th e average recovery w ill be flagged as outside m ethod acceptance criteria. A ll LC S sam ples wH be control charted as p er E T S 4-Q 26. If th e average recovery o f one o f th e spiking levels exceeded th e analytical m ethod uncertainty as determ ined by E TS -12 012, th at analytical batch uncertainty w il b e expanded fo r th at particular study.
If m ore than 67% o f th e LC S sam ples fa i to m eet m ethod acceptance criteria, the d ata w i not be reported.
CaHbration standards consisting o f m ixed branched and finear isom er P FO S /P FO A a re preferred. H ow ever, fo r P FO S /P FO A targ et analytes, if th e c a lix a tio n standards are com prised o f predom inantly lin ear isom ers only, a t least one level o f trip licate LCSs should be prepared using P FO S /P FO A which contains a m ix o f linear and branched isom ers. These LCSs w ill be used to dem onstrate quantitative equivalency (o r quantitative bias) o f th e isom eric m ix when using a predom inantly lin ear standard fo r c a lx a tio n . T h e m ixed in e a r and branched isom er P FO S /P FO A LCSs recoveries should fa ll w ithin 3 0 % o f expected values. A lternatively, in lieu o f m ixed branched and lin ear isom er P FO S /P FO A LCSs, m ixed branched and lin ear isom er PFO S /P FO A TB M Ss m ay be ap p ied to dem onstrate m ethod accuracy and precision.
9.5 Field Matrix Spikes (FMSs) / Surrogate Recovery Standards (SRSs)
FM Ss are prepared fo r each sam ping location and analyzed to determ ine th e m atrix effect and sam ple holding tim e on the s p ite recovery o f each targ et an alyte and/or appropriate S R S . G enerally, each sam ple location represents a cffferent sam ple and sam ple m atrix.
FM Ss a re Q C sam ples to which known quantities o f appropriate targ et analytes a re added to th e sam ple bottle in th e laboratory before th e bottles are sent to th e field . Typically a low and a high targ et analyte FM S are prepared fo r each sam pling location. T he sam ple and field duplicate sam ple m ay contain appropriate S R S s in ie u o f targ et analyte tow fieto m atrix s p k e and targ et analyte high field m atrix sp k e sam ples.
Field m atrix spice m ethod acceptance criteria a re recoveries w ithin 30% o f th e expected valu e. If FM S recovery (targ et analyte or S R S spice) is outside o f 30% o f th e expected valu e o r could not be assessed because th e FM S (targ et an alyte) w as spiked a t an inappropriate level, th e sam ple result is reported as follow s:
1 . ) If target analyte FM S recovery could not be assessed because th e FM S 's w ere a t an inappropriate level, then Laboratory M atrix S p ires (L M S ) m ay be substituted. If LM S recoveries a re w ithin 30% th e d ata are reportable and flagged to in d kate th at th e FM S sp ires levels w ere inappropria te.
2 . ) If m ultiple targ et analyte FM S 's w ere prepared on a sam ple and th e closest FM S level to th e reported sam ple m eets th e 30% acceptance criteria but addftonal FM S 's are outside th e 30% acceptance range, the data a re reportable and flagged to rx fic a te th at w hile th ere w ere failing FM S 's , th e uncertainty w il not be expanded since th e m ost appropriate s p k e level passed.
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3 . ) If the targ et an alyte FM S recoveries a re outside o f the 30% acceptance range but a t least 3 0 acceptable historical reportable FM S sam ple results are availab le, th e data m ay be reported but flagged w ith an expanded uncertainty and as not m eeting FM S criteria.
4 . ) Sam ple data w ith FM S recovery outside o f 30% but w ithin 50% o f th e expected value a re flagged and reported as outside o f Q C acceptance criteria w ith an expanded uncertainty.
5 . ) If FM S recovery is outside o f 50% , th e sam ple result is reported as N R , w here N R is defined as "N ot R eportable" due to noncom pliant Q C results.
T he targeted fortification levels should be a t least 50% o f the endogenous level and less than 10 tim es the endogenous level to be used w ithoutjustification to determ ine th e statem ent o f accuracy fo r analytical results.
N ote: It is possible fo r bottles utikzed fo r Field M atrix S pike sam ples to be u nd er-filed o r o ver-filed during sam ple co lectio n. S ince this scenario w ill effect th e actual concentration o f th e FM S sam ple (surrogate and internal standard concentrations w il also be effected , if used), it is im portant th at any obvious u nd er-filing or over-fining o f sam ple bottles be docum ented in th e d ata package a id taken into account in th e FM S , IS s, o r S R S s recovery calculations. Sam ples o v e rfille d o r u n d er-filed by m ore than 10% w il be require recalculation o f th e FM S , IS s, and S R S true values.
T he average o f th e sam ple and the field duplicate should be used to calculate th e recovery.
10 Procedures
10.1 W ater Sample Preparation
This m ethod is applicable to w ater sam ples. Sam ples containing heavy particulate m ay not be suitable fo r analysis by this m ethod. Sam ples containing suspended particulate should be centrifuge prior to rem oving a sam ple aliquot, o r fite re d .
Thoroughly m ix sam ple before rem oving an aliquot and placing in a labeled autovial.
D ilute sam ple, if necessary, w ith A STM Type I w ater, H PLC w ater, other suitable w ater, o r solvent (m ethanol).
Lab control spices a re prepared fo r each analysis batch to determ ine m ethod accuracy and precision. LCSs should be prepared a t th ree levels in trip licate fo r each targ et analyte and a t a m inim um o f tw o levels in trip licate fo r appropriate S R S s. Low lab control spfces should be prepared a t a concentration in the range o f approxim ately four to ten tim es higher than th e targeted low er LO Q , th e m id lab control spikes should be prepared a t a concentration n ear th e m id-point o f the calibration curve and th e high lab control spikes a t approxim ately 80% o f th e upper LO Q . For IS quantitation, stable isotope internal standards o f each targ et analyte o r appropriate surrogate IS s should be spiked a t th e sam e level as the sam ples being analyzed, in a ll LC Ss.
If LCSs a re being prepared using synthetic groundw ater, a lo w th e LCSs sam ples to eq id ib rate fo r a m inim um o f 4 hours before afiquoting fo r analysis o r diluting w ith solvent (m ethanol).
11 Sample Analysis - LC/MS/MS
11.1 Instrument Setup
N o te: In this exam ple, an A pplied Biosystem s S d ex A P I 4 0 0 0 (A P I 500 0 o r A P I 5 5 0 0 ) Tandem M ass Spectrom eter (L C /M S /M S ) is used. O ther brands/m odels o f LC /M S /M S instrum ents as w e l as single quadrupole m ass spectrom eters (L C /M S ) m ay be used as long as th e m ethod acceptance criteria a re m et. Brand nam es, suppliers, part num bers, and m odels are fo r illustrative purposes only. Equivalent perform ance m ay be achieved using apparatus and m aterials other than those specified here, but dem onstration o f equivalent perform ance th at m eets th e requirem ents o f this m ethod is th e responsibility o f th e laboratory. The operator m ust optim ize and docum ent th e equipm ent avid settings used.
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Establish the LC /M S /M S system and operating conditions equivalent to th e follow ing: M ass Spec: A pplied Biosystem s A P I 4 0 0 0 , A P I 5 0 0 0 , o r A P I 5500 Ion Source: Turbo Ion S pray (A B S ) M ode: Electrospray N egative Scan Type: M R M (M ultiple R eaction M onitoring) C om puter. D e l DHM Softw are: W indow s 200 0 o r W indows X P , A nalyst 1 .4 2 o r higher versions HPLC: A gilent S eries 1100,1200, o r 1290 A gilent Q uaternary Pum p A gilent Vacuum D egasser A gilent A utosam pler A gilent Colum n O ven N o te: O ne o r m ore C 18 H PLC analytical colum ns (2.1 mm x 100 m m , 5pm o r 2 1 mm x 50 m m , 5pm ) m ay be attached o n-line a fte r th e purge valve and before th e sam ple injection port to retard and separate any residue contam inants th at m ay be in th e m o b ie phase and/or H PLC system . HPLC Colum n: B etasil C 18,4.6m m x 100m m , 5pm (Therm oEJectron C orporation) Colum n Tem perature: 35C Injection Volum e: 5pL M obile P hase (A ): 2m M Am m onium A cetate in A STM Type I w ater (S e e 7 .3 ) M obile P hase (B ): M ethanol
T a b le 3 . L iq u id C h ro m a to g ra p h y G ra d ie n t P ro g ra m .
Step Number
Total Time (min)
00
1 2 .0
2 14.5 3 15.5 4 16.5 5 2 0 .0
Flow Rate (jMJmln)
750 750 750 750 750 750
PercentA (2 mlSammonium
acetate)
97.0 97.0 5.0 5.0 9 7 .0 9 7 .0
Percent B (Methanol)
3 .0 3 .0 95.0 95.0 3.0 3.0
N ote: O ther H PLC gradients m ay be used as long as th e m ethod criteria and project d ata quality objectives are m et
K m ay be necessary to ac^ust th e H PLC gradient in order to optim ize instrum ent perform ance. Colum ns w ith e ffe re n t efim ensions (e .g . 21m m x 30m m ) and colum ns from different m anufacturers (K eystone B etasil C 18 e tc .) m ay be used.
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T a b le 4 S u g g e s te d M R M T ra n s itio n s fo r T a rg e t A n a ly te s , S u rro g a te s , a n d In te rn a l S ta n d a rd s
Analyte PFBA C4 Acid) PFPeA (C5 Acid) PFHxA (C6 Acid) PFHpA (C7 Acid) PFOA (C8 Acid) PFNA(C9 Acid) PFDA (CIO Acid) PFUnA (Cl 1Add) PFDoA (0 2 Add) PFTA(C13 Acid) FBSA (C4 Sulfonamide) POSA (C8 Sulfonamide) PFBS (C4 Sulfonate) PFHS (06 Sulfonate) PFOS (C8 Sulfonate) [1.2,3,4 "CJPFBA rU .3.4.5 -uCslPFPeA [12 -i3C2]PFHxA [1,2,3.4- 13G,]PFHpA [1,2,3,4.5,6.7,8-uCdPFOA [1.2,3,4.5.6,7.8,9-uClPfNA [1,22,4,5,6 -13C]PFDA [122,4.5.6,7 -13C7]PFUoA [12 -"CilPFDoA [1*OJPFBS [1.2.3-13Cj1PFHS [1 2 ,3 .4 -`H IP P O S [122.4.5.6.7.8-uC,]POSA [U .3.4-uClPFOA [122.4-" CilPPOS fl2 -13C,lPFUnA
Analyte Description
Tarnet Tarnet Tarnet Target Target Target Target Target Target Target Target Target Target Target Target IS forPFBA IS for PFPeA IS fbrPFHxA ISforPFHnA IS for PFOA ISforPFNA IS for PFDA IS for PFUnA IS for PFDoA and PFTA IS for PFBS IS for PFHS IS for PFOS ISforFOSA Smrosate (C4-C8 Acida) SuxrogateCSulfonates, POSA) Surrogate (C9-C13 Acida)
Mass Transition O l (amu) 213 263 313 363 413 463 513 563 613 663 298 498 299 399 499 217 268 315 367 421 472 519 570 615 303 402 503 507 417 503 565
Mass Transition 03 (amu) 169 219 269.119 319.169 369,219.169
419,169,219 469.269.219 519,269,219 569.169.319 619,369.319
78 78 99,80 99,80 80,99,130 172 223 270 322 376 427 474 525 570 84 80 80 80 372 80 520
M ultiple transitions fo r m onitoring th e analytes is an option. T h e use o f one daughter ion is acceptable if data sensitivity and selectivity is achieved and provided th at retention tim e criteria a re m et to assure adequate specificity. W h ie th e daughter ions m ay be chosen a t th e discretion o f th e analyst, m ass transition 9 9 is suggested fo r P FO S . Q uantitation m ay be perform ed using the to tal ion chrom atogram (T IC , o r sum m ed M R M s) fo r a given an aiyte. For exam ple, th e PFO A T IC would sum aH three o f th e m onitored transitions. Use o f th e suggested prim ary ion is recom m ended. R etention tim es m ay vary slightly, on a day-to-day basis, depending on th e batch o f m o b ie phase and th e gradient, colum n, guard colum n(s) used etc. D rift in retention tim es is acceptable w ithin an analytical run, as long as the d rift continues through th e e n tie analysis and the standards are interspersed throughout th e analytical run.
11.2 Calibration Curve
Q uantitation is by internal standard o r external standard calibration. C alibration standards m ay be prepared in A STM Type I, H PLC w ater, other suitable w ater, o ra solvent/w ater m ixture. If internal standard calibration does not m eet calibration acceptance criteria, external calibration can be applied. S ee T able 1 fo r
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recom m ended application o f available internal standards. Q uantitation o f PFO A and P FO S is by sum m ed analyte-specific m ass transitions.
A nalyze th e standard curve prior to each se t o f sam ples. If internal standards w ere added to th e calibration standards area ratios are used to generate th e c a lix a tio n curve. T h e standard curve m ay b e plotted using a lin ear regression (y = m x + b ), w eighted 1/x o r unw eighted, o r by quadratic fit (y = ax2 + bx + c ), w eighted 1 /x o r unw eighted, using suitable softw are. T h e m athem atical m ethod used to calculate th e c a lix a tio n curve should be applied consistently throughout a study. Any change should be thoroughly docum ented in th e raw data.
High and/or low points m ay b e excluded from the calibration curves to provide a b etter fit over th e range appropriate to th e d ata o r because they did not m eet th e pre-determ ined acceptance criteria. Low -level curve points should also be excluded if th eir area counts (o r area ratio if quantitating by IS ) are not a t least tw ice th at o f th e average area counts (o r area ratio if quantitating by IS ) o f m ethod and/or solvent blanks. T h e coefficient o f determ ination (r2) value fo r th e calibration crave m ust be g reater than o r equal to 0 .9 9 0 (o r a correlation coefficient (r) o f 0 .9 9 5 ). Each point in th e curve m ust be w ithin 25% erfth e theoretical concentration w ith the exception o f th e LLO Q , which m ay be w ithin 30% . Justification fo r exclusion o f cafibration curve points w ill be noted in th e raw d ata. A m inim um o f 6 points w il be used to construct th e caH xation curve.
If th e ca lix a tio n curve does not m eet acceptance criteria, perform routine m aintenance or prepare a new standard curve (if necessary) and reanalyze.
11.3 Continuing Calibration Verification (CCV)
Continuing cafibration verifications (C C V ) a re analyzed to verify th e accuracy o f th e calibration curve. A nalyze a m id-range c a lix a tio n standard, one o f th e sam e standards used to construct th e c a lix a tio n curve, a t a m inim um a fte r every tenth sam ple, not including solvent blanks, w ith a m inim um o f one per sam ple s e t C aflbration verification injections m ust be w ithin 25% to be considered acceptable. T h e cafibration curve and th e last passing C C V w ill then bracket acceptable sam ples. M ultiple C C V levels m ay b e used. Sam ples m ust be bracketed by passing C C V s o r th e calibration curve and a passing C C V to be reportable.
11.4 System Suitability
A m inim um o f th ree system suitability sam ples should be injected a t th e beginning o f each analytical run, prior to th e analysis o f th e cafibration curve. Typically these sam ples are a t a concentration n ear th e m id-level o f the c a lix a tio n curve and are repeated injections from one autosam pler v ia l. It is suggested th at th e system suitabifity S ectio n s have area counts o r area ratios when using internal standard calibration, w ith a targ et R SD o f <5% and a targ et retention tim e R SD o f <2% . T here is no defined a c c e p ta b ly lim it on these results as th e % R SD value is dependent on th e num ber o f M RM transitions being m onitored in th e LC /M S /M S run o r tim e period. U ltim ately, any effects on these param eters fo r th e System S u itab iity sam ples w ill also b e evident on all standards and Q C sam ples analyzed as p a rt o f th e analysis batch. Any effect o f system su itab iity is incorporated w ithin Q C acceptance criteria.4
11.5 Sample Analysis and QCs
For each analysis batch, th e instrum ent analysis run sequence should include an in itial c a lix a tio n curve, sam ples, FD S s, interspersed blanks, interspersed C C V s, appropriate Q C s (i.e ., LC Ss, LM Ss, FM S s, TB M Ss, and T B s), and a fin al C C V o r c a lix a tio n curve bracketing sam ples and appropriate Q C s
Iryect th e sam e volum e (betw een 5 - 100pL) o f each standard, analytical sam ple and blank into th e instrum ent (unless an on-instrum ent sam ple dilution is desired).
Sam ples containing analytes th at are quantitated above th e concentration o f th e highest standard in the curve
should b e further d iu ted and reanalyzed.
4 F jT w m.iinnlji1 1 A n n tn fy druW K fljU K W i p c lm ilw i tlw r f f r r t i th fftf rrm lte i i fim rtu w o f (tw im n A ff n fM B M i h ftn g m n niln m i
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A nalysis
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Bert Jeffries Property - April 2012
12 Data Analysis and Calculations
T he chroma tography analysts softw are w il typically calculate th e am ount o f targ et an alyte in th e sam ple extracts using th e established caHbration curve.
C alculate th e percent recovery o f the LCS using th e foflowing equation:
LCS C oncentration (-58-)
LC
S
%
re
c
o
v
ery
=
-------------------------------" Spike C oncentration
nLg_
*
io
o
%
tn l.
C alculate th e percent recovery o f the LM S using th e follow ing equation:
LM S Concentration (-^ ~ ) - Concentration o f Sam ple (-5 ? -) LM S % recovery = ___________________ mL___________________________ mL
HQ
Spike Concentration (---- ) mL
100%
For sam ples fortified w ith known am ounts o f analyte prior to extraction, use th e follow ing equation to calculate th e percent recovery.
T o ta l a n a ly te found (n g /m L ) - A verag e a n a ly te found in sam ple (n g /m L )
R ecovery =
x 1 Q0
A n alyte added (n g /m L )
13 Analysis Batch Method Performance Criteria
A ny m ethod perform ance param eters th at are not achieved m ust be considered in th e evaluation o f th e data. Nonconform ance to any specified param eters m ust be described and discussed in th e fin al report if the Technical M anager (non-G LP study) o r Study D irector (G LP study) chooses to report th e d ata.
If criteria listed in this m ethod perform ance section a re not m et, m aintenance m ay be perform ed on th e system and sam ples reanalyzed, o r other actions taken as appropriate. D o cu m en tal actions in th e raw d ata.
If data a re to be reported w hen perform ance criteria have not been m et, th e data m ust be footnoted on tables and discussed in th e te x t o f th e rep o rt
13.1 System Suitability - Analysis Batch
A m inim um o f th ree system su itab iity sam ples should be injected a t th e beginning o f each analytical rm . These sam ples a re run prior to th e calibration curve. It is suggested th at the system su itab iity injections have area counts w ith a targ et R SD o f 5% and a targ et retention tim e R SD o f S2% . T here is no defined acceptability lim it on these results as th e % R SD s are dependent on th e num ber o f M RM transitions being m onitored in th e LC /M S /M S run o r tim e period. Any effect o f system suitability is incorporated in th e Q C acceptance criteria.
13.2 Calibration and Limit of Quantitation (LOQ) - Analysis Batch
C a lib ra tio n C u rve: T he coefficient o f determ ination (r2) value fo r th e calibration curve m ust be g reater than or equal to 0 .9 9 0 corresponding to a correlation coefficient (r) = 0 .9 9 5 . Each point in th e curve m ust be w ithin 25% o f th e theoretical concentration w ith th e exception o f the LLO Q , w hich m ay be w ithin 30% .
C C V P erfo rm an ce: T h e calibration standards th at a re interspersed throughout th e analytical sequence are evaluated as continuing calibration verifications in addition to being p art o f th e caHbration curve. T h e accuracy
E T S -8 -0 4 4 .1
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Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/M S/M S; Direct Injection
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o f each curve point m ust be w ithin 25% o f th e theoretical value (w ithin 30% fo r low est curve point). Sam ples th at are bracketed by C C V s not m eeting these criteria m ust be reanalyzed.
L im its o f Q u a n tita tio n (L O Q ): T he low er LO Q (LLO Q ) is th e low est non-zero active standard in th e calibration curve; th e peak area o f th e LLO Q m ust be a t least 2X th at o f th e average area counts fo r a l prepared procedural blan k(s). By definition, th e m easured value o f th e LLO Q m ust be w ithin 30% o f the theoretical valu e.
D em o n stratio n o f S p e c ific ity : Specificity is dem onstrated by chrom atographic retention tim e (w ithin 4% o f standard) and th e m ass spectral response o f unique ions.
13.3 Blanks - Method/Procedural Blanks and Trip
M eth o d /P ro ced u ral B lan ks: M ultiple procedural blanks should be interspersed throughout th e analysis batch and th e analytical sequence. A t a m inirriurn, m ethod blanks are analyzed prior to instrum ent c a lx a tio n , prior to th e analysis o f C C V sam ples, afte r every 10 sam ple injections, and a t th e end o f th e analytical run.
T h e m ean area counts (o r area ratios when using IS calb ratio n ) fo r each analyte m ust be less than 50% o f the area count o f th e LO Q standard. If th e area counts o f th e procedural blanks exceed 50% o f th e LO Q standard, then th e LO Q m ust be raised to th e firs t standard level th at m eets criteria.
T rip B lan k: A trip blank o f A STM Type I w ater (o r lab equivalent) is prepared in a sam ple container in th e laboratory and treated as a sam ple, inducting exposure to shipping, sam pfing site conditions, storage, preservation and a ll analytical procedures. T h e trip blanks results fo r each analyte are included w ith th e reported sam ple results.
13.4 Data Accuracy and Precision - Analysis Batch
L ab C o n tro l S p ikes: T he average recovery a t each LC S level fo r each targ et analyte and appropriate SR S should b e w ithin 80-120% and th e percent relative standard deviation o f th e recoveries m ust be less than or equal to 20% . if th e average recovery o f a spidng level fa ls outside m ethod acceptance, but a t least 67% (6 out o f 9 ) o f LCS sam ples a te w ithin 20% o f th eir respective nom inal value (33% o f th e Q C sam ples, not all replicates a t th e sam e concentration, m ay be outside 20% o f nom inal valu e), th e averag e recovery w i be flagged as outside m ethod acceptance criteria. Afl LC S sam ples w ill b e control charted as p er E T S -12-012. If th e average recovery o f one o f th e spiking levels exceeded th e analytical m ethod uncertainty as determ ined by E T S -12-012, th at analytical batch uncertainty w fl be expanded fo rth a t particular study. T h e average recovery a te a c h LC S level fo r m ixed bran ched /in ear isom er PFO A and P FO S should be w ithin 70-130% and the percent relative standard deviation o f th e recoveries m ust be less than o r equal to 20% .
F ie ld D u p lic a te s : T h e relative percent cfifference (R P D ) o f duplicate sam ples should be less tfia n 20% fo r th e precision o f sam ple preparation and analysis to be considered in control. R epficate sam ples not m eeting th e 20% R PD criteria a re flagged and reported as outside o f Q C acceptance c rite ria
F ie ld M a trix S p ikes: FM S acceptance criteria are recoveries w ithin 30% o f th e expected value fo r each targ et analyte and appropriate S R S . Sam ple data w ith FM S recovery outside o f 30% but wfthin 50% o f the expected value a re flagged and reported as outside o f Q C acceptance criteria. D ata w ith FM S recovery outside o f 50% o f th e expected value a re reported as N R , w here N R is defined as "N ot R eportable' data outside o f Q C acceptance criteria. If FM S recovery could not b e assessed because FM Ss w ere a t an inappropriate level, then Laboratory M atrix S pices (LM S s) m ay be substituted. If LM S recoveries are w ithin 30% fo r each targ et analyte and S R S s th e data are reportable but flagged as not m eeting th e FM S m ethod acceptance criteria.
13.5 Analytical Method Uncertainty
A nalytical m ethod uncertainty fo r each targ et analyte and SR S is determ ined w ith control charted historical analysis batch LC S d ata fo r th e m ethod and reported w ith each analysis batch.5 U ncertainty determ inations
5 M ethod uncertainty based on INTERNATIONAL ANS/ISO/IED STANDARD 17025 reference (GUM, Guide to the Expression of Uncertainty in M easurement). M ethod application demonstrated in ETS-12-012, citing references: a.) EURACHEM/CLTAC Guide, "Quantifying Uncertainty in Analytical M easurement," Second Edition; Editors: S.LJL Ellison, M. Rosslein, and A. W illiams. b.)Georgian, Thomas, "Estimation o fLaboratory Analytical Uncertainty Using Laboratory Control Samples." Environmental Testing &
E T S -8 -0 4 4 .1
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Bert Jeffries Property - April 2012
are based on IN TER N A TIO N A L A N S/ISO /1ED STA N D A R D 17025 reference (G U M , G uide to th e Expression o f U ncertainty in M easurem ent) and described in E T S -12-012. A t least thirty data points a re required fo r determ ining analytical m ethod uncertainty. T h e m ethod uncertainty is defined as 2x th e standard deviation o f th e p e r a it recoveries o f th e pooled lab control s p ite s . W hile a ll LC S d ata points are control charted, only the m ost recent fifty d ata points are used fo r determ ining th e m ethod uncertainty.
W hen less than thirty LC S d ata points have been generated fo r a given an alyte, th e analysis batch LC Ss are used to determ ine th e data uncertainty. If FM Ss m eet th e 30% recovery criteria a t a level appropriate to the endogenous level, and th e LC S m eet th e 20% recovery criteria, then th e uncertainty o f th e data is determ ined as w ithin 10020% .
A nalysis batch sam ple d ata w ith FM S recovery outside o f 30% but w ithin 50% o f th e expected value are flagged and reported as outside o f Q C acceptance criteria w ith expanded uncertainties. D ata w ith FM S recovery outside o f 50% o f th e expected value are reported as N R , w here N R is defined as "N ot R eportable" data outside o f Q C acceptance criteria. If FM S recovery could not be assessed because FM Ss w ere a t an inappropriate level, then Laboratory M atrix Spikes (LM S s) m ay be substituted. If LM S recoveries are w ithin 30% fo r each targ et analyte and appropriate SR Ss th e data are reportable but flagged as not m eeting the FM S m ethod acceptance criteria w ith uncertainties o f 30% . If FM S do not m eet th e 30% recovery criteria, and historical FM S data does not e x is t th e analytical uncertainty is evaluated on a sam ple-by-sam ple basis, the d ata m ay be reported w ith expanded uncertainty and a re flagged.
13.6 Quantitation of PFOA/PFOS - Analysis Batch
C alb ration standards consisting o f m ixed branched and In e a r isom er P FO S /P FO A a re preferred. Q uantitation is perform ed by integrating th e lin ear and branched isom ers together. A lternately, th e lin ear and branched isom ers can be integrated separately, applying th e appropriate true valu e to each c a lx a tio n curve point fo r each isom er. T he LCS and sam ples are then quantitated by integrating th e lin ear and branched isom ers separately (requires separate analytical results file s ) and quantitating th e resulting peak against the lin ear or branched calb ratio n curve. T h e results from both integrations are then sum m ed to produce th e final result. Integrating th e lin ear and branched isom ers separately m ay be h e lp fii fo r those sam ples w here the Knear/branched ratios do not closely m atch those o f th e reference standards.
H ow ever, fo r P FO S /P FO A targ et analytes, if th e calibration standards are com prised o f predom inantly linear isom ers only th e m ethod requires th e addition o f LCSs o f m ixed branched/linear isom er P FO S /P FO A . The purpose o f including these LC Ss is to dem onstrate quantitative equivalency (o r quantitative b ias) o f the isom eric m ix w hen using a predom inantly lin ear PFO S o r PFO A standard fo r calb ratio n . A lternatively, in Beu o f m ixed branched and lin ear isom er P FO S /P FO A LC Ss, m ixed branched and lin ear isom er P FO S /P FO A TB M Ss m ay be applied to dem onstrate m ethod accuracy and precision.
An altern ate m ethod o f quantitation can be perform ed w hereby only th e lin ear isom er o f P FO S /P FO A is integrated and used fo r generating th e calibration curve. T he LCS and sam ples are then quantitated by integrating th e lin ear and branched isom ers separately (requires separate analytical results file s ) and quantitating th e resulting peak against th e lin ear calibration curve. T h e results from both integrations are then sum m ed to produce th e fin al re s u lt Integrating th e linear and branched isom ers separately reduces th e oncolum n concentration fo r those sam ples th at contain both lin ear and branched isom ers o f P FO A /P FO S . This ensures th at th e concentration detected is w ithin th e a range o f th e calb ratio n curve th at is com parable regardless o f w hether th e calibration curve w as generated using predom inantly linear isom ers o f P FO S /P FO A or lin ear plus branched isom ers o f P FO S /P FO A .
14 Pollution Prevention and Waste Management
W aste generated w hen perform ing this m ethod w ill be disposed o f appropriately. T h e original sam ples w ill be archived a t th e 3M Environm ental Laboratory in accordance w ith internal procedures.
MAEvneaaallsuyuasrtieisnm,gNeanontvdUemEnxcbeperrrt/eaDsisneiotnyegmindbiTecerUs2tn0inc0ge0r".t,acJi.n)uTtlyyaoy2lf0oN0r2,IBS. T.NM. eaansduCreEm.eKntuRyeasttu,lNtsI."SdT.)TAedcahmnsic, aTl.NMo.,te"A122L97A,1G9u9i4deEdfoitriodnie: "EGstuimidaetliionnesoffor
E T S -8 -0 4 4 .1
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Analysis
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GLP10-01-02; Interim Report 30 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples
Bert Jeffries Property - April 2012
15 Records
Each d ata package generated fo r a study m ust include a ll supporting inform ation fo r reconstruction o f th e data. Inform ation fo r th e data package m ust indude, but is not lim ited to th e follow ing item s: study o r project num ber, sam ple and standard prep sheets/records, Instrum ent run log (instrum ent batch records, instrum ent acquisition m ethod, sum m ary pages), instrum ent results file s , chrom atogram s, calibration curves, and d ata c a lc u la tio n s .
16 Affected Documents
N one.
17 Revisions1*
R evision Num ber
1
Sum m ary o f C hanges
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 sotvent/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 internal standards and surrogates. Changed concentration levels for working standards and included the use of internal standards and surrogates. Section 8. Inserted a new section on sample bottle preparation. Section 9 Quality Control. This section was previously section 10 in ETS-8-044.0. Updated QC criteria to be consistent with method ETS-8-154.4. Section 10 Procedures. This section was previously section 8 (Sample Handling) in ETS-8044.0. Added detail regarding the preparation ofLCSs. 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 in ETS8-044.0. 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 PFOA/PFOS. Section 14 Pollution Prevention. This section was previously section 13 in ETS-8-044.0. Section 15 Records. This section was previously section 14 in ETS-8-044.0. Section 16 Affected Documents. This section was previously section 15 in ETS-8-044.0. Section 17 Revisions. This section was previously section 16 in ETS-8-044.0.
E T S -8 -0 4 4 .1
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Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/M S/M S; Direct Injection
Analysis
Page 112 of112
GLP10-01-02. Interim Report 31: Analysis of PFBS. PFHS. and PFOS in Groundwater Samples from New On-Site Wells - Adjacent to the 3M Decatur Wastewater Treatment Plant
(WWTP1 April 2012
Study Title
A nalysis o f Perfluorooctane Sulfonate (P F O S ), Perfluorohexane Sulfonate (P F H S ) and Perfluorobutane S ulfonate (P F B S ) in G roundw ater, S oil and Sedim ent fo r th e 3M D ecatur P hase 3
S ite-R elated M onitoring Program
Data Requirement
E P A T S C A G ood Laboratory P ractice S tandards 4 0 C F R P a rt 7 9 2
Study Director
Jaisim ha K esari P .E ., D E E W eston S olutions, In c. 1400 W eston W ay
W est C h ester, PA 19380 Phone: 6 1 0 -7 0 1 -3 7 6 1
Author
Susan W o lf 3M E nvironm ental Laboratory
Interim Report Completion Date
D ate o f signing
Performing Laboratory
3M Environm ental H ealth and S afety O perations Environm ental Laboratory
3M C enter, Bldg 2 6 0 -0 5 -N -1 7 S t P aul, M N 55144
Project Identification
G LP 10 -0 1 -0 2 -3 1
Total Number of Pages
89
The tasting reported herein meet the requirements of ANSI/tSQflEC 17026:2006 "General Requirements for the Competence ofTesting and Calibration Laboratories", Inaccordance with the A2LA Testing Certificate# 2062.01. Testing thatcompfleswith this InternationalStendard also meets principles otISO9001:2000.
Testing Cert #2052.01
GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-Sile WWTP WeNs - April 2012 This page has been reserved fo r specific country requrem ents.
Page 2 o f89
GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-Site WWTP Wells - April 2012
G L P C o m plia n c e Statement
Report Title: G LP 10-01-02, Interim Report 31: Analysis o f PFBS, PFH S, and PFO S in Groundwater Sam ples from N ew O n-S ite W ells - Adjacent to the 3M D ecatur W astew ater Treatm ent Plant (W W TP) April 2012. Study: Analysis o f Perfluorooctane Sulfonate (P FO S ), Perfluorohexane Sulfonate (P FH S ) and Perfluorobutane Sulfonate (PFB S) in Groundwater, Soil and Sedim ent fo r the 3M D ecatur Phase 3 Site-R elated Monitoring Program . This analytical phase was conducted in com piance w ith Toxic Substances Control A ct (TSC A ) Good Laboratory Practice (G LP ) Standards, 40 C FR 702, with the exceptions listed below:
These are environm ental sam ples w here there is no specific test substance, no specific test system and no dosing o f a test system .
The reference substances have not been characterized under the GLPs and the stability under storage conditions at th e test site have not been determ ined under GLPs.
Page 3 of 89
GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS In Groundwater
New On-Site WWTP Wells - Apr! 2012
Q u a lity A ssu r a n c e Statement
Report Title: G LP 10-01-02, Interim Report 31: Analysis o f PFBS, PFH S, and PFO S in Groundwater Sam ples from New O n-S ite W eis - Adjacent to the 3M D ecatur W astew ater Treatm ent Plant (W W TP) April 2012.
Study: Analysis o f Peifluorooctane Sulfonate (P FO S ), Periluorohexane Sulfonate (P FH S ) and Peifluorobutane Sulfonate (PFB S) m Groundwater, Soil and Sedim ent for the 3M D ecatur Phase 3 S ite-R elated Monitoring Program .
This analytical phase w as audited by the 3M Environm ental Laboratory Q uality Assurance U nit (Q AU ), as indicated in the following table. The findings w ere reported to the principal investigator (P .I.), laboratory m anagem ent and study director.
Insp ectio n D ates 4 /2 6-2 7 /1 2 ,5 /1 /1 2
Phase D ata and Report
D ate R ported to
T estin g F acility M anagem ent
S tu d y D irecto r
5 /4 /1 2
5 /4 /1 2
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GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-Site WWTP W eis - April 2012
Ta b le of C o ntents
G LP C om pliance S tatem ent.................................................................................................................................. 3 Q u ality A ssurance S tatem ent................................................................................................................................4 T ab le o f C ontents.....................................................................................................................................................5 List o f T a b le s ............................................................................................................................................................ 6 1 Study Inform ation............................................................................................................................................. 7 2 S um m ary........................................................................................................................................................... 8 3 Introduction........................................................................................................................................................ 8 4 T est & C ontrol S ub stan ces........................................................................................................................... 9 5 R eference S ubstances................................................................................................................................. 10 6 T est S y s te m ....................................................................................................................................................11 7 M ethod S um m ary..........................................................................................................................................11
7.1 M eth o d ...........................................................................................................................................11 7 .2 Sam ple C ollection........................................................................................................................ 11 7 .3 S am ple P reparation.....................................................................................................................11 7 .4 A nalysis..........................................................................................................................................12 8 A nalytical R esults........................................................................................................................................... 13 8.1 C alib ratio n ..................................................................................................................................... 13 8 .2 System S u ita b ility ........................................................................................................................ 13 8 .3 Lim it o f Q uantitation (L O Q )........................................................................................................13 8 .4 Continuing C alib ratio n ................................................................................................................ 13 8 .5 B lanks............................................................................................................................................. 14 8 .6 Lab C ontrol S p kes (L C S s )....................................................................................................... 14 8 .7 A nalytical M ethod U ncertain ty.................................................................................................. 17 8 .8 Field M atrix S pikes (F M S )..........................................................................................................17
P a g e 5 o f8 9
GLP10-01-02; Interim Repot 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-Site WWTP WeHs April 2012
8 .9 Lab M atrix Spikes (L M S )............................................................................................................17 9 D ata Sum m ary and D iscussion................................................................................................................. 18 10 C onclusion...................................................................................................................................................... 2 3 11 D ata/S am ple R eten tio n .............................................................................................................................. 23 12 A ttachm ents................................................................................................................................................... 2 3 13 S ig n atu res...................................................................................................................................................... 24
Lis t o f Ta bles
Table 1. Sum m arized P FB S , P FH S , and PFO S R esults (R esiduum M onitoring W e is )................... 8 T a b le 2 . Sam ple D escription Key C ode......................................................................................................11 Table 3 . Instrum ent P aram eters................................................................................................................... 12 Table 4 . Liquid Chrom atography C onditions............................................................................................. 12 T able 5 . M ass Transitions..............................................................................................................................12 T a b le 6 . Lim it o f Q uantitation (L O Q )............................................................................................................ 13 Table 7 . Laboratory Control S p ite R ecovery.............................................................................................14 T able 8 . A nalytical U n certain ty.....................................................................................................................17 T able 9 . Field M atrix S p k e Levels............................................................................................................... 17 Table 10. DAL GW 7 W 1 R 1 2 0 4 0 5 .............................................................................................................. 19 T able 11. D AL GW T W 2 R 1 2 0 4 0 5 .............................................................................................................. 19 Table 12. DAL G W T W 3 R 120405 ............................................................................................................. 2 0 Table 13. DAL G W T W 4 R 1 2 0 4 0 5 .............................................................................................................. 20 Table 14. DAL G W T W 5 R 1 2 0 4 0 5 ............................................................................................................. 21 Table 15. DAL G W T W 6 R 1 2 0 4 0 5 .............................................................................................................. 21 Table 16. DAL GW TR IP01 1 2 0 4 0 5 ............................................................................................................ 22 Table 17. R inseate B lank................................................................................................................................22
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GLP10-01-02; IntBrim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-Site WWTP W efls-April 2012
1 Study Inform ation
Sponsor 3M Com pany S p o n s o r R e p re s e n ta tiv e G ary Hohenstein 3M EH S O perations 3M Building 224-5W -03 S aint P aul, M N 55144-1000 P h o n e :(6 5 1 )7 3 7 -3 5 7 0
S tu d y D ire c to r Jaisim ha K esari, P .E ., D EE W eston Solutions, Inc. W e s tc h e s te r, PA 19380 P h o n e :(6 1 0 )7 0 1 -3 7 6 1 F a x :(6 1 0 )7 0 1 -7 4 0 1 j.kesari@ w estonsolutions.com S tu d y L o c a tio n
Testing Facility
3M EH S O perations 3M Environm ental Laboratory Building 260 -5 N -1 7 S t P aul, M N 55144 S tu d y P e rs o n n e l W illiam K . R eag en , P h .D ., 3M Laboratory M an ag er C leston Lange, P h .D ., P rincipal A nalytical Investigator, fdatae@ m m m .com 1: phone (651 >733-9860 Susan W o lf, 3M A nalyst C h elsie G rochow , A nalyst K elly U kes, A nalyst S tu d y D a te s Study Initiation: M arch 8 ,2 0 1 0 Interim 31 Experim ental Term ination: A pril 2 8 ,2 0 1 2 Interim R eport Com pletion: D ate o f Interim R eport Signing L o c a tio n o f A rc h iv e s A ll o rig in al raw d ata and th e an a ly tic a l rep o rt h ave b een arch ived a t th e 3M E nvironm ental Laboratory according to 4 0 C F R P a rt 7 9 2 . T h e te s t substance and an alytical referen ce standard reserve sam ples a re arch ived a t th e 3M E nvironm ental Laboratory according to 4 0 C FR P a rt 7 92
Page 7 erf89
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Jl
1i
GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS m Groundwater
New On-Site WWTP W eis - April 2012
2 Summary
T h e 3M Environm ental Laboratory received groundw ater sam ples from six new on-site tem porary residuum m onitoring w ells in th e vicinity o f the 3M D ecatur facility W astew ater Treatm ent P lant (W W TP ) in D ecatur, A L A to tal o f tw enty-eight sam ple bottles w ere received a t th e 3M Environm ental Laboratory fo r perfluorooctane sulfonate (P F O S ), perfluorohexane sulfonate (P F H S ) and perfluorobutane sulfonate (P F B S ), and included duplicate groundw ater sam ples and tw o field m atrix s p ite (F M S ) sam ples from each sam pfing location. Sam ples also included one trip blank containing MilH-QTM w ater and appropriate trip blank s p ite s and one equipm ent rinseate blank. T h e equipm ent rinseate blank did not have FM S sam ples prepared fo r determ ination o f P FO S , PFH S and PFBS recovery. A ll sam ples w ere logged into the laboratory inform ation m anagem ent system (L IM S ) under project G LP10 -0 1 -0 2 -3 1 . T h e groundw ater sam ples and trip blanks w ere received from W eston personnel on A pril 9 ,2 0 1 2 . A ll o f th e sam ples w ere prepared and analyzed fo r PFB S , P FH S , and P FO S follow ing 3M Environm ental Laboratory M ethod E T S -8-044.1 ` M ethod o f A nalysis fo r the D eterm ination o f Perfluorinated Com pounds in W ater by LC /M S /M S ; D irect Injection A nalysis' .
T h e average m easured PFB S , P FH S , and PFO S concentrations a re sum m arized in T a b le 1 . T he trip blank sam ple w as below th e low er lim it o f quantitation (LLO Q ) fo r all analytes, indicating adequate control o f sam ple contam ination during shipping and sam ple collections. T h e analytical m ethod uncertainties associated w ith th e reported results are: PFB S + 1 2 % , PFH S + 1 2 % and P FO S + 35% .
T a b le 1 . S u m m arized P F B S , P F H S , a n d P FO S R e s u lts (R e s id u u m M o n ito rin g W e lls , A p ril
2012).
S a m p lin g L o catio n
DAL GW TW 1R 120405 DAL G W T W 2 R 120405 DAL G W T W 3 R 120405 DAL G W T W 4 R 120405 DAL G W T W 5 R 120405 DAL G W T W 6 R 120405 DAL G W TW 3R R inseate Blank DAL-G W -TRIP01 Blank
PFBS
PFHS
PFOS
A vg. Cone. (n g friiL ) R PD
Avg. Cone. (n g /m L ) R PD
Avg. Cone. (n g /m L ) R PD
3 3 .8 0 .3 0 %
5 7 .3 2 .1 %
2 9 .0 9 .0 %
117 5 .1 %
579 5 .5 %
1090 17%
304 7 .6 % 184 4 .9 % 522 4 .4 %
1310 15% 19.1 1 .0 % 4 3 .0 1 .6 %
3660 17% 247 2 .4 % 696 2.3%
156 0 .6 4 %
4 6 .7 5 .6 %
281 4 .6 %
<0250
<0250
<0232
_____ <0.250_____ _____ < 0 2 5 0 _____ _____ < 0 2 3 2 _____
The analytical method uncertainties associated with the reported results are: PFBS 12%, PFHS 12%, and PFOS 35% .
3 Introduction
This analytical study w as conducted as part o f th e Phase 3 Environm ental M onitoring and A ssessm ent Program fo r th e 3M fa d ty located in D ecatur, A labam a. T h e objective o f th e overall program is to gain inform ation regarding concentrations o f perfluorooctane sulfonate (P F O S ), perfluorohexane sulfonate (P F H S ) and perfluorobutane sulfonate (P F B S ), in various environm ental m ecfia such as groundw ater, soils and sedim ents th at are associated w ith and near th e D ecatur fa d fity . This analytical study w as conducted to analyze groundw ater sam ples collected from six new tem porary on-site residuum
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m onitoring w ells located adjacent to th e 3M D ecatur W W TP fo r P FO S , P FH S and PFB S in an effo rt to characterize regional groundw ater conditions. T h e 3M Environm ental Laboratory prepared sam ple containers (2 5 0 m L high-density polyethylene bottles) which w ere shipped to D ecatur, A L W eston personnel prior to field sam pling. Sam ple containers fo r each sam pling location included a field sam ple, field sam ple duplicate, and tw o field m atrix sp k e sam ples. Each em pty container w as m arked w ith a "fill to here" line to produce a final sam ple volum e o f 200 m L. C ontainers designated fo r field m atrix sam ples w ere fortified w ith an appropriate m atrix sp k e solution containing PFB S (lin ear isom er), PFH S (lin ear isom er), and PFO S (lin ear and branched isom ers) prior to being sent to th e field fo r sam ple collection. A ll sam ple bottles included the addition o f 18C>2-P FB S , 13C yP F H S , and 13Cb-P FO S (internal standard) a t a nom inal concentration o f 1 ng/m L and 13C4-P FO S (surrogate recovery standard) a t a nom inal concentration o f 0.1 ng/m L. D ue to the level o f PFB S, P FH S , and P FO S detected in th e sam ples, neither the internal standards nor th e surrogate recovery standard w as utilized during sam ple analysis. Laboratory m atrix spikes w ere prepared fo r sam pling locations T W 2, T W 3, T W 4, T W 5, and TW 6 since th e field m atrix spike levels w ere not appropriate fo r these sam pling locations fo r a t least one o f th e targ et analytes. S ee section 8 .9 o f the report fo r laboratory m atrix spfice levels. S ee section 8 .8 o f th e report fo r field m atrix spfce levels. S ee section 8 .9 o f th e report fo r laboratory m atrix spike levels. Sam ples w ere prepared and analyzed according to th e procedure defined in 3M Environm ental Laboratory m ethod E T S -8-044.1 ` M ethod o f A nalysis fo r the D eterm ination o f Perfluorinated Com pounds In W ater by LC /M S /M S ; D irect Injection A nalysis". T a b le 1 sum m arizes th e averag e PFB S , P FH S , and PFO S concentrations fo r th e duplicate surface w ater sam ples collected and th e trip blank sam ple. T ab les 10-17 sum m arize th e individual sam ple results and th e associated field m atrix spike recoveries. A ll results fo r th e quality control sam ples prepared and analyzed w ith th e sam ples a re reported and cfiscussed elsew here in this rep o rt
4 Test & Control Substances
T h ere w as not a test substance or control substances in th e classic sense o f a G LP study. This study w as purely analytical in nature.
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5 Reference Substances
R e fe re n ce S u b sta n ce
Chem ical N am e
Chem ical Form ula id e n tifie r
Use
Source Expiration D a le S torage Concilions Chem ical Lot N um ber TC R Number Physical Description Purity
PFBS (L in e a r) Potassium Perfluorobutane sulfonate
C 4 F9 S 0 3X t
NA T arg et A nalyte R eference
S ta n d a rd 3M
0 1 /10 /2 0 1 7
Frozen
PFHS (L in e a r) S o du m Pertluorohexane sulfonate
C 6 F 13S 0 3-N a+
L-P FH X S T a g e t Analyte R eference Standard
W oBngton
03/25 /2 0 1 8
Frozen
4 1 -2 6 0 0 -8 4 4 2 -5
LPFH XSA M 08
T C R -121 W hite Pow der
9 6.7%
TC R Q 8-0018 C rystaM n e 100%
R e fe re n ce S u b sta n ce
Chem ical N am e
Chem ical Form ula Id e n tifie r
Use
Source Expiration D ate Storage CondHtons Chem ical Lot N um ber TC R Number Physical Description Purity
PFOS (L in e a r + B ra n ch e d ) Potassium Periluorooctane
sulfonate
C a F i/S Q fK *
B r-P FO SK T arget Analyte Reference
S ta n d a rd W eHngton
03/17 /2 0 1 4 ; 12/01/2014
F ro ze n brPFO SK 0708; b tP F O S K 1111 T C R 1 1-0010; T C R 1 1-0041
Liquid
99 .9%
PFOS (lin e a r + B ra n ch e d )
Potassium Perfluorooctane sulfonate
C bF it S O sK * C A S # 2795-39-3
F M S R eference Standard
Sigm a-Aldrich 02/04 /2 0 1 4 Am bient
1424328V
T C R 1 1-0028 W hite Pow der
9 9 .7%
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6 Test System
T h e test system s fo r this study are groundw ater sam ples collected from w ells located in D ecatur, A L by W eston Solutions, Inc. personnel. S am ples fo r this study are "real w orld" sam ples, not dosed w ith a specific lo t o f test substance.
T a b le 2 . S a m p le D e s c rip tio n K ey C o d e .
String Number
E x a m p le 1 2 3 4
5
String Descriptor
Example
D A L -G W -T W 1 R -0 -1 2 0 4 0 5
S a m p le L o c a tio n
D A L * D e c a tu r. A la b a m a
S a m p le T y p e
G W -G ro u n d W a te r
M UTO
E x a m p le : T W 1 R
S a m p le T y p e
O ^ rlm a r y s a m p le
D B ^ iu p lic a te s a m p le
L S - lo w s p ik e
H S -h lo h s p ik e
S a m p lin a D a te
1 2 0 4 0 5 -A p r S . 2 0 1 2
7 Method Summary
7.1 Method
A nalysis fo r all analytes w as com pleted follow ing 3M Environm ental Laboratory m ethod E TS -8-044.1 "M ethod o f A nalysis fo r the D eterm ination o f Perfluorinated Com pounds In W ater by H igh Perform ance Liquid C hrom atography/M ass Spectrom etry D irect Injection A nalysis".
7.2 Sample Collection
Sam ples w ere collected in 2 5 0 m L NalgeneTM (high-density polyethylene) bottles prepared a t th e 3M Environm ental Laboratory. S am ple bottles associated w ith G LP10-01-Q 2-31 w ere returned to th e laboratory a t am bient conditions on A pril 9 ,2 0 1 2 . Sam ples w ere stored refrigerated a t th e laboratory after receipt. A set o f laboratory prepared Trip Blank and T ip Blank field m atrix sp ires w ere sen t w ith th e sam ple collection bottles.
7.3 Sample Preparation
A ll sam ples w ere in itially diluted 1:10 by diluting 1 mL o f a w ell m ixed sam ple w ith 9 m L erf Midi Q w ater avid analyzed on 4 /1 3 /1 2 .
S am ping locations T W 2, T W 3, T W 4, T W 5, and TW 6 w ere re-analyzed and included the preparation o f a laboraotry m atrix s p ire w ith each sam ple s e t Location TW 2R w as diluted 1:50 by diluting 0 .2 m L o f th e w ell m ixed sam ple w ith 9 .8 m L o f Midi Q w ater and included a 1000 ppb LM S fo r PFH S and P FO S . Location TW 3R w as diluted 1:100 by diluting 0.1 m L o f th e w ell m ixed sam ple w ith 9 .9 m L o fM lliQ w ater and included a 2000 ppb LM S and 5000ppb LM S fo r PFB S , P FH S , id P FO S . Locations TW 4R , TW 5R and TW 6R w ere diluted 1:10 by diluting 1 .0 m L o f th e w ell m ixed sam ple w ith 9 .0 m L o fM lliQ w ater. Location TW 4R included a 200 ppb LM S fo r P FO S . Location T W 5R included a 500 ppb LM S fo r PFB S and P FO S . Location TW 6R included a 2 0 0 ppb LM S fo r P FO S .
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7.4 Analysis
A ll study sam ples and quality control sam ples w ere analyzed fo r PFB S , P FH S , and P FO S using high perform ance liquid chrom atography/ tandem m ass spectrom etry (H P LC /M S /M S ). D e ta ie d instrum ent param eters, th e liquid chrom atography gradient program , and the specific m ass transitions analyzed are described in th e raw data hard copies placed in th e final data packet, and are b riefly described below .
Table 3. Instrument Parameters.
Instrument Name Analytical Method Foiow ed Analysis Dale Liquid Chromatograph Guard column Analytical column Injection Volume Maas Spectrometer Ion Source Electrode Polarity Software
ETS Ginger ETS-8-044.1
4/13/12 A o fen tH O O Betas! C18 (4.6 mm X 100 m m l 5u Betas! C18 (4.6 mm X 100 mm). 5g
2 o r1 0 u L Appied Biosystems API 5000
T urt Spray Turbo ion electrode
Negative Analyst 1.42
Table 4. Liquid Chromatography Conditions.
ETS Buster ETS-8-044.1 4/16/12.4/27/12 A d ten tH O O Betas! C18 (4.6 mm X 100 mm). 5u Betas! C18 (4.6 mm X 100 mm). 5p
2 o r1 0 u L Appied Bnsystems API 4000
Turbo Spray Tub o ion electrode
N eg ate Analyst 1 .4 2
Step
N um ber
Tots/ Time
(m in )
0 0 .0
1 2 .0
2 14.5 3 15.5 4 165 5 2 0 .0
H ow Rate
(f J m tn )
P e rc e n tA (2 m M a m m o n iu m a c e ta te )
ETS-8044.1
750 97.0 750 97.0
750 5.0 750 5.0 750 97.0 750 97.0
P e rc e n tB tm o m a n o o
3.0 3.0 95.0 95.0 3.0 3.0
Table 5. Mass Transitions.
A n a ly te PFB S PFH S PFO S
M a s s T ra n s itio n 0 1 /0 3 2 9 9 /9 0 2 9 9 /9 9 3 9 9 /9 0 3 9 9 /9 9 49990 4 9 9 /9 9
4 9 9 /1 3 0
R e fe re n c e M a te ria l S tru c tu re U noar
U near
U n e a r B ra n c h e d
DwbI tm e was 50 or 75 msec for each transition. The irriMdual transitions were summed to produce a Total ion chromatogram' (TIC), w tid i was used tor quantitation
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8 Analytical Results
8.1 Calibration
Sam ples w ere analyzed against an external standard calibration curve. C alibration standards w ere prepared by spiking known am ounts o f th e stock solution containing P FB S , P FH S , P FO S (reference standard fo r P FO S containing both lin ear and branched isom ers) into M ili Q w ater. Standards ranging from 0 .0 2 5 0 ng/m L to 100 ng/m L (nom inal) w ere analyzed . Low and or high curve points m ay have been disabled to m eet m ethod criteria. A quadratic, 1/x w eighted, calibration curve o f th e peak area counts w as used to fit the data fo r each an alyte. The data w ere not forced through zero during th e fitting process. C alculating th e standard concentrations using th e peak area confirm ed accuracy o f each curve p o in t Each curve point w as quantitated using th e overall calibration curve and review ed fo r accuracy. M ethod calibration accuracy requirem ents o f 10025% (1 0030% fo r the low est curve point) w ere m et fo r a ll analytes. T h e correlation coefficient (r) w as g reater than 0 .9 9 5 fo r all analytes. Each curve point w as quantitated using th e overall calibration curve and review ed fo r accuracy. M ethod calibration accuracy requirem ents o f 10025% (10030% fo r th e low est curve point) w ere m et fo r a ll analytes. T he correlation coefficient (r) w as greater than 0 .9 9 5 fo r PFB S, P FH S and P FO S fo r each analysis.
8.2 System Suitability
A calibration standard w as analyzed four tim es a t th e beginning o f each analytical sequence to dem onstrate overall system suitability. T h e acceptance criteria o f less than o r equal to 5% relative standard deviation (R S D ) fo r peak area and retention tim e criteria o f less than o r equal to 2% R SD w as m et fo r PFB S , P FH S and P FO S fo r each analysis.
8.3 Limit of Quantitation (LOQ)
T h e LO Q fo r th is analysis is th e low est non-zero calibration standard in th e curve th at m eets linearity and accuracy requirem ents and fo r which th e area counts o r area ratio a re a t least tw ice those o f th e appropriate blanks. The LO Q fo r a ll analytes can be found in T able 6.
T a b le 6 . L im it o f Q u a n tita tio n (L O Q ).
A n a ly s is D a te
4 /1 3 /1 2 4 /1 6 /1 2
4 /2 7/1 2 NA = Not Appfcabte
D ilu tio n F a c to r
10 50 10 50 100 10 50 100 250
P FB S L O Q , n o /m L
0 .2 5 0 1 .2 5 0 .2 50 1 .2 5 2 .5 0 10.0 5 0 .0 100 250
PFH S L O Q , n g /m L
0250 1 .2 5 0250 1 .2 5 2 .5 0 9 .9 8 4 9 .9 9 9 .8 250
PFO S L O Q , n q /m L
NA NA 0232 1 .1 6 2 .3 2 9 .2 8 4 6 .4 9 2 .8 232
8.4 Continuing Calibration
During th e course o f each analytical sequence, continuing calibration verification sam ples (C C V s) w ere analyzed to confirm th at th e instrum ent response and th e initial calibration curve w ere still in control. All C C V s m et m ethod criteria o f 100% 25% fo r PFB S , P FH S and P FO S fo r each analysis.
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8.5 Blanks
T h ree types o f blanks w ere prepared and analyzed w ith th e sam ples: m ethod procedural blanks, a trip blank, and an equipm ent rinseate blank. M ethod procedural blank results w ere review ed and used to evalu ate m ethod perform ance and to determ ine th e LO Q fo r PFB S , PFH S and P FO S . T h e trip blank reflects th e shipping and sam ple codecfion conditions th e sam ple bottles and sam ples experience. The equipm ent rinseate blank is an aqueous sam ple th at reflect th e efficiency o f equipm ent cleaning in th e field betw een d ifferen t sam ple collections and are proof o f no cross contam ination o f sam ples from the
equipm ent
8.6 Lab Control Spikes (LCSs)
Low , m id, and high lab control spikes w ere prepared fo r th e targ et analytes and analyzed in trip licate. LCSs w ere prepared by sp itin g known am ounts o f th e analyte into M iK-Q w ater to produce th e desired concentration. T he spiced w ater sam ples w ere then prepared and analyzed in th e sam e m anner as th e
sam ples. T he m ethod acceptance criteria, average o f LCS a t each level should be w ithin 100% 20%
w ith an R SD 20% , w as m et fo r a ll analytes except fo r th e low level LC Ss fo r P FO S analyzed on 4 /1 6 /1 2 which had an average recovery o f 75.2% . A l LC S sam ples w ere used in th e determ ination o f th e analytical m ethod uncertainty on section 8 .7 . A m ethod deviation is included in A ttachm ent D .
T h e follow ing calculations w ere used to generate data in Table 7 fo r laboratory control sp kes.
LCS
Percent
Recovery
=
Calcutatod Concentration Spike Concentration
100%
LCS%RSD = St^ averdaegWeaL^CS^reCcSovree,r*yg ^ 1 0 0 %
T ab le 7. Laboratory C ontrol S pike R ecovery.
ETS-8044.1 Analyzed 4/13/12
L ab ID
S p ik e d C o n c e n tr a tio n
(n g /m L )
P FB S
C a lc u la te d C o n c e n tr a tio n
(n g /tn L i
% R e c o v e ry
LC S-120411-1 LC S -120411-2 LCS-120 4 11 -3 A veraae % RSD
0 .498 0 .498 0 .4 98
0 .479 0 /466 0 .4 76 9 5 .2 % 1.4%
9 6 .2 9 3 .7 9 5 .6
LC S -120411-4 L C S -120411-5 LCS-12Q 411-6 A verage % RSD
4 .9 8 4 .9 8 4 .9 8
4 .6 9
A T!
4 .7 1 9 4 .8 % 0 .9 4 %
94.1 9 5 .8 9 4 .5
L C S -120411-7 L C S -1 2 0 4 1 1 -8 L C S -120411-9 A verage % R S D
2 9 .9 2 9 .9 2 9 .9
N A 1 N A (1) N A (1> NA
N A (1) N A (1) N A (1>
NA = Not Appicatte (1) LCS s p ie d concentration exceeded tt c a ta s ta i range. (2) LCS <Sdnot meet acceptance criteria of 100 20% .
S p ik e d
(n g /m L )
0 .497 0 .497 0 .4 97
4 .9 7 4 .9 7 4 .9 7
2 9 .9 2 9 .9 2 9 .9
PFH S C a lc u la te d
(n g /m L )
0 .4 72 0 .4 64 0 .4 69 9 4 .2% 0 .9 1 % 4 .7 3 4 .7 6 4 .6 9 9 5 .1 % 0 4 9 % N A 1 N A (,) N A (1) NA
% R e c e v e ry
9 5 .0 9 3 .3 9 4 .3
9 5 .2 9 5 .7 9 4 .4
N A (1) N A (1) N A <1>
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T a b le 7 c o n tin u e d . L a b o ra to ry C o n tro l S p ik e R e c o v e ry .
ETS-8-044.1 Analyzed 4/16/12
PFB S
PFH S
L a b ID
S p ik e d C o n c e n tr a tio n
fn g /tn L )
C a lc u la te d C o n c e n tr a tio n
(n g A m L )
% R e c o v e rv
S p ttre d C o n c e n tr a tio n
(n g A n L )
C a lc u la te d C o n c e n tr a tio n
f iv m j
LC S-120411-1 LC S -120411-2 L C S -120411-3 A verage % R SD
0 .4 98 0 .4 98 0 .496
0 .5 05 0 .5 1 1 0 .5 00 1 0 1 % 1 .5 %
101 103 100
0 .497 0 .497 0 .4 97
0 .489 0 .4 9 1 0 .4 93 9 8 .8 % 0 /4 2 %
L C S -120411-4 L C S -120411-5 L C S -120411-6 A verage % R SD
4 .9 8 4 .9 8 4 .9 8
5 .1 2 5 .1 9 4 .9 5 102% 2 /4 %
103 104 9 9 .4
4 .9 7 4 .9 7 4 .9 7
4 .9 6 4 .7 9 4 .9 5 9 8 .6 % 1 .9 %
L C S -120411-7 L C S -120411-8 L C S -120411-9 A verage % R SD
2 9 .9 2 9 .9 2 9 .9
2 9 .3 2 8 .8 2 9 .0 9 7 .1% 0 .8 8 %
9 8 .0 9 6 .3 9 7 .0
2 9 .9 2 9 .9 2 9 .9
2 7 .0 2 7 .7 2 8 .3 9 2 .5 % 2.4%
% R e c o v e rv
9 8 .3 9 8 .9 99.1 .
9 9 .7 9 6 .4 9 9 .6
9 0 .3 9 2 .5 9 4 .8
ETS-8-044.1 Analyzed 4/16/12
P F O S (L in e a r a n d B ra n c h e d )
L a b ID
S p O rn d C o n c e n tr a tio n
(n g /m L )
C a lc u la te d C o n c e n tr a tio n
(n o /m L )
% R e c o v e ry
LC S-120411-1 LC S -120411-2 LC S -120411-3 A verage % R SD
0 .4 62 0 .4 62 0 .462
0 .3 48 0 .3 5 1 0 .3 44 7 5 .2% 0 .9 3 %
7 5 .3 7 5 .9 7 4 .5
L C S -120411-4 LC S -120411-5 L C S -120411-6 A verage % R SD
4 .6 2 4 .6 2 4 .6 2
420 4 .1 7 426 9 1 2 % 1 .1 %
9 1 .0 9 0 .3 922
L C S -120411-7 L C S -120411-8 L C S -120411-9 A verage % R SD
2 7 .8 2 7 .8 2 7 .8
2 6 .5 2 5 .8 2 6 .8 9 4 8 % 1 .9 %
9 5 .2 9 2 .8 9 6 .3
NA = Not Applicable
(1) LCS spiked concentration exceeded the cafebrabon range (2) LCS dd not meet acceptance criteria o f 100 20%.
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T a b le 7 c o n tin u e d . L a b o ra to ry C o n tro l S p ik e R e c o v e ry .
ETS-8-044.1 Analyzed 4/27/12
L a b ID
SpKoe d C o n c e n tr a tio n
(n g A n L )
PFB S C a lc u la te d
(n g A n L )
L C S -1 2 0 4 2 6 -1 LCS-120 4 26 -2 LC S-120426-3 A verage % R S O
LCS-120 4 26 -4 LCS-12 0 4 26 -6 LCS-12 0 4 26 -6 A verage % R SD
4 .9 8 4 .9 8 4 .9 8
20.0 20.0 20.0
4 .9 5 5 .0 9 5 .3 0 103% 3 .7 %
1 8 .6 1 8 .5 1 8 .2 9 2 .1% 1 .3 %
LCS-12 0 4 26 -7 LCS-12 0 4 26 -8 L C S -120426-9 A verage % R SD
4 9 .8 4 9 .8 4 9 .8
5 0 .4 4 7 .5 4 7 .1 9 7 .0% 3 .6 %
% R e c o v e ry
S p ik e d C o n c e n tr a tio n
(n g A n L )
9 9 .5 102 107
4 .9 7 4 .9 7 4 .9 7
9 3 .0 9 2 .6 9 0 .8
1 9 .9 1 9 .9 1 9 .9
101 9 5 .4 9 4 .6
4 9 .7 4 9 .7 4 9 .7
PFH S C a lc u la te d C o n c e n tr a tio n
(n g A n L )
4 .8 5 5 .0 0 5 .1 2 101% 2 .7 % 1 7 .7 1 8 .5 1 8 .8 9 2 .2% 3 .3 %
4 9 .1 4 6 .6 4 7 .0 9 5 .7% 2 .8 %
% R e c o v e tv
9 7 .6 101 103
88.8 93.1 9 4 .6
9 8 .8 9 3 .7 9 4 .6
ETS-8-044.1 Anatvzed 4/27/12
P F O S (U n e a r a n d B ra n c h e d )
L a b ID
S p ik e d C o n c e n tr a tio n
(n g A n L )
C a lc u la te d C o n c e n tr a tio n
(n g A n L )
% R e c o v e ry
L C S -1 2 0 4 2 6 -1 LCS-12 0 4 26 -2 LCS-120 4 26 -3
4 .6 2 4 .6 2 4 .6 2
4 .2 6 4 .0 2 4^1
92.1 8 7 .0 91.1
A verage % R SD
9 0 .1% 3 .0 %
LC S-120426-4 LCS-12 0 4 26 -5 LCS-12 0 4 26 -6 A verage % RSD
1 8 .5 1 8 .5 1 8 .5
1 5 .7 1 6 .6 1 6 .8 8 8 .4 % 3 .4 %
8 5 .0 8 9 .6 9 0 .6
LCS-12 0 4 26 -7 LCS-120 4 26 -8 L C S -120426-9 A verage % RSD
4 6 .2 4 6 .2 4 6 .2
4 6 .3 4 3 .8 4 3 .5 9 6 J % 3 .3 %
100 9 4 .9 94.1
N A =N o t AppicaMe
(1) LCS spited concentraion exceeded 9 caBraion range. (2) LCSdkt not meet acceptance criteria of 100 20% .
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GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-Site WWTP Weds - April 2012
8.7 Analytical Method Uncertainty
A nalytical uncertainty is based on historical Q C d ata th a t is control charted and used to evaluate m ethod accuracy arid precision. T h e m ethod uncertainty is calculated follow ing E TS -12 -0 1 2 .2 . T h e standard deviation is calculated fo r th e se t o f accuracy results (in % ) obtained fo r th e Q C sam ples. The expanded uncertainty is calculated by m ultiplying th e standard deviation by a factor o f 2 , which corresponds to a confidence level o f 95% .
T a b le 8 . A n a ly tic a l U n c e rta in ty .
A n aly te PFBS PFHS PFOS
S ta n d a rd D eviatio n 5 .9 1 5 .8 8 1 7 .6
M eth o d U n ce rta in ty 12% 12% 35%
8.8 Field Matrix Spikes (FMS)
Low , m id, and high field m atrix spikes (F M S ) w ere collected a t each sam pling point to verify th at th e analytical m ethod is applicable to the collected m atrix. Field m atrix spikes w ere generated by adding a m easured volum e o f field sam ple to a container sp ired by the laboratory w ith PFB S (lin e a r), PFH S (lin ea r), and P FO S (lin ear and branched) prior to shipping sam ple containers fo r sam ple collection. Field m atrix spice recoveries w ithin m ethod acceptance criteria o f 10030% confirm th at "unknown" com ponents in th e sam ple m atrix do not significantly interfere w ith th e extraction and analysis o f the analytes o f interest. Field m atrix spike concentrations m ust be 50% o f th e sam ple concentration to be considered an appropriate field spike. Field m atrix spices are presented in section 9 o f this rep o rt
T a b le 9 . F ie ld M a trix S p ik e L e v e ls .
S a m p lin g L o catio n
S p ik e L evel
A ll locations and Trip Blank
Low High
PFBS, n g /m L
10 100
PFHS, n g /m L
9 .9 8 9 9 .8
PFOS, n g /m L
9 .9 8 9 9 .8
( FM S Recovery =
Sam ple Concentration o f F M S - A verage
Concentration : Field Sam ple & Field Sam ple P u p .), 100%
Spike Concentratori
8.9 Lab Matrix Spikes (LMS)
D ue to th e high levels o f P FB S , P FH S , and/or PFO S detected in sam pling locations T W 2, T W 3, TW 4, T W 5, and T W 6, th e FM S spike levels w ere not appropriate fo r a t least one o f th e analytes. Therefore, laboratory m atrix spices (LM S ) sam ples w ere prepared to verify th at th e analytical m ethod is applicable to th e collected m atrix. Laboratory m atrix spices w ere generated by adding a m easured volum e o f PFB S , P FH S , and P FO S (referen ce standard containing both lin ear and branched isom ers) to an afiquot o f th e prim ary sam ple. S ince aril sam ples required dilution prior to sam ple analysis, th e laboratory m atrix spike added w as based on th e on-coium n instrum ent concentration.
Sam pling locationTW 2; the prim ary sam ple (G LP 10 -0 1 -0 2 -3 1 -0 0 5 ) w as diluted 1:50, to which 2 0 ng/m L (nom inal) o f targ et analytes w ere added fo r a LM S concentration o f approxim ately 1000 ng/m L
Sam pling location TW 3; th e prim ary sam ple (G LP 10 -0 1 -0 2 -3 1 -0 0 9 ) w as diluted 1:100, to which th e low LM S had 2 0 ng/m L (n o m rtal) o f target analytes added fo r a LM S concentration o f approxim ately 2000 ng/m L, and th e high LM S had 50 ng/m L (nom inal) o f target analytes added fo r a LM S concentration o f approxim ately 500 0 ng/m L.
Page 17 of 89
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.1
GLP10-01-02; Intrim Report 31 Analysis o f PFBS, PFHS, and PFOS m Groundwater
New On-Site W W TP W e is - April 2012
Sam pling location TW 4; th e prim ary sam ple (G LP 10 -0 1 -0 2 -3 1 -0 1 3 ) w as diluted 1:10, to which 2 0 ng/m L (nom inal) o f targ et analytes w ere added fo r a LM S concentration o f approxim ately 2 0 0 n g/m L
Sam pling location TW 5; the prim ary sam ple (G LP 10 -0 1 -0 2 -3 1 -0 1 7 ) w as diluted 1:50, to which 10 ng/m L (nom inal) o f targ et analytes w ere added fo r a LM S concentration o f approxim ately 500 n g/m L
Sam pling location TW O; the prim ary sam ple (G LP 10-01 -01 -3 2 -0 1 7 ) w as diluted 1:10, to which 2 0 ng/m L (nom inal) o f targ et analytes w ere added fo r a LM S concentration o f approxim ately 2 0 0 rg/mL.
Lab m atrix s p ire recoveries w ithin m ethod acceptance criteria o f 10030% confirm th at "unknown" com ponents in th e sam ple m atrix do not skyiificantly interfere w ith th e extraction and analysis o f the analytes o f in terest Lab m atrix spike concentrations m ust be 50% o f th e sam ple concentration to be considered an appropriate field spike. Lab m atrix sp ires are presented in section 9 o f this rep o rt
T h e follow ing calculation w as used to calculate th e lab m atrix s p ire recovery in Section 9 o f th e rep o rt
LM S Recovery ( Sam ple Concentration o f LM S - A verage Concentration : Fietd Sam ple & Fietd Sam ple Pup .) t 100%
Spike Concentratori
9 Data Sum m ary and Discussion
T h e tab les below sum m arize th e sam ple results and field o r lab m atrix s p ire recoveries fo r th e sam pling locations as w ell as th e Trip B lank. R esults and average values are rounded to three significant figures according to EPA rounding rules. B ecause o f roundng, values m ay vary slightly from those listed in th e raw d ata. Field m atrix s p ire and lab m atrix spike recoveries m eeting th e m ethod acceptance criteria o f 30% , dem onstrate th at th e m ethod w as appropriate fo r th e given m atrix and th eir respective quantitative ranges.
D A L G W T W 1 R 120405; T h e recovery o f the high field m atix s p ire fo r P FO S w as 6 5.8% . S ince the analytical m ethod uncertainty w as calculated a t 35% fo r P FO S , no further adjustm ent to th e analytical uncertainty is needed fo r DAL G W TW 1R .
Page 18 of 80
GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-Site WWTP Wells - April 2012
T ab le 10. DAL G W T W 1 R 120405
PFB S
PFH S
PFO S
3 M L IM S ID
D e s c r ip tio n
G L P 10-01-02-31-001 D A L -G W -T W 1R -0-120405 G LP 10-01-02-31-002 D A L -G W -T W 1R -D B -120405 G LP10-01-Q 2-3 1 -0 0 3 D A L -G W -T W 1R -L S -120405
G LP 10-01-02-31 -0 0 4 D A L -G W -T W 1R -H S -120405
A v e r a g e C o n c e n tr a tio n (n g /m L ) 1 % R P D
C o n c e n tr a tio n (n g /m L )
% R e c o v e ry
3 3 .8 3 3 .7 4 2 .8 120
NA NA NC 8 6 .3
3 3 .8 n g to tL 0 .3 0 %
C o n c e n tr a tio n (n g /m L )
" /R e c o v e ry
5 6 .7 5 7 .9 6 3 .3 147
NA NA NC 8 9 .9
5 7 .3 n g /m L 2 .1
C o n c e n tr a tio n (n g /m L )
" / R e c o v e ry
211
3 0 .3 3 5 .4
NA NA NC
9 4 .7
6 5 .8 m
2 9 .0 n g A n L t 9 .0 %
N A = Not Appficable NC = Not Calculatod; the sample concentration is greater than 2x the spite level. Samples analyzed using a 1:10 cMufon factor PFBS and PFHS reported from 4/13/12 analysis. PFOS reeuls reported from 4/16/12 analysis. (1) FMS recovery did not meet acceptance criteria
T a b le 1 1 . D A L G W T W 2 R 1 2 0 4 0 5
PFB S
PFH S
PFO S
3 M L IM S ID
D e s c r ip tio n
G LP 10-01-Q 2-31-005
D A L -G W -T W 2R -0-120405
G LP 10-01-02-31-006 G LP 10-01-02-31-007
D A L -G W -T W 2R -D B -120405 D A L -G W -T W 2R -L S -120405
G LP 10-01-02-31-008
D A L -G W -T W 2R -H S -120405
G L P 10-01-02-31-005:1000P D b L M S D A L -G W -T W 2R -0-LM S
A v e r a g e C o n c e n tr a tio n (n g /m L ) t % R P D
C o n c e n tr a tio n
C o n c e n tr a tio n
(n g /m t)
" /R e c o v e ry
(n g /m L )
" /R e c o v e ry
120 NA 563
NA
114 NA 595
NA
125 N C N A (1) N A 0' 2 1 7 100 N A (1> N A (1>
N A (1)
N A `1>
1520
9 4 .5
1 1 7 n g /m L 1 5 .1 %
5 7 9 n g /m L 1 5 .5 %
C o n c e n tr a tio n (n g /m U
V n R e c o v e ry
995 NA
1180 N A < 1>
NA N A (1)
N A < 1> 2020
N A (1) 101
1 0 9 0 n g /m L 1 7 %
N A = NotAppfcatte NC = Not Calcultrtod-, the sample concentration Is greater than 2x the spite level Samples analyzed on 4/13/12 far PFBS using a 1:10 diudon factor), arid on 4/27/12 fr>r PFHS and PFOS using a 1:50 cBuHonfactor. (1) Sample not analyzed for this analyte due to Inappropriate spite level.
Page 18 of 89
G LP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New O n-Site W W TP W alls - April 2012
Table 12. DAL GW T W 3 R 120405
PFB S
PFHS
PFO S
M U M S ID
D e s c rip tio n
G LP 10-01-Q 2-31-009
D A L -G W -T W 3R -0-12 0 4 0 5
G LP 10-01-02-31-010
Q A L-G W -TW 3R -D B -12 0 4 05
G L P 10-01-02-31-011
D A L -G W -T W 3R -L S -12 0 405
G L P 10-01- 2-31-012
D A L-G W -TW 3R -H S -120405
G L P 10-01-02-31-009; 2000p p b LM S D A L -G W -T W 3R -0-LM S
G L P 1 0 -0 1 -Q 2 -3 1 -0 0 9 :5 0 0 0 ra b LM S Q A L -G W -TW 3R -0-LM S
A verag e C o n c e n tr a tio n ( n g A n L ) % R P D
C o n c e n tra tio n
C o n c e n tra tio n
(n g A n L )
% R e c o v e ry
(n g trriL )
Y o R e c o v e ry
292 NA 1210
NA
315 NATM N A (,)
NA N A (1> N A (1>
1410 NATM NATM
NA NATM NATM
2280
9 6 .8
4960
9 3 .5
3 0 4 n g fm L 7 .6 %
3160
9 3 .0
5940
932
1 3 1 0 n g A n L 15%
C o n c e n tra tio n (n g A n L )
% R e covery
3340 3970 NATM NATM 5240 8480
NA NA NATM NATM 8 5 .7 104
3660ngA nL17%
N A -N o t Appicable Samples analyzed on 4/27/12 using a 1:100 (flution factor SOOOppb IM S analyzed using a 1:250dlution factor. (1) Sample not analynd tierthis analyte due to Inappropriate spfce level.
Table 13. DAL GW TW 4R 120405
PFB S
PFH S
PFO S
3 M U M S ID
D e s c rip tio n
G L P 10-01-02-31-013 G LP K W 1-02-31-014 G LP 10-01-02-31-015 G L P 10-01-02-31-016 G LP 10-01-02-31-013; 200p p b L M S
D A L -G W -T W 4R -0-12 0 4 0 5 D A L -G W -T W 4R -D B -12 0 406 D A L -G W -T W 4R -L S -120405 D A L -G W -T W 4R -H S -12 0 4 05 D A L -G W -T W 4R -0-LM S
A verag e C o n c e n tr a tio n (n g A n L ) 1 % R P D
C o n c e n tra tio n
C o n c e n tra tio n
(n g A n U
Y o R e c o v e ry
(n g /m U
Y o R e c o v e ry
179 NA 19.0
NA
188 NA 1 9 2
NA
NATM 278
NATM 9 4 .5
282 102
912 83.1
NATM
NATM
NATM
NATM
1 8 4 n g /m L 4 .9 %
1 9 .1 n g /m L 1 1 .0 %
C o n c e n tra tio n (ngA nL)
% R e c o v e ry
244 250 NATM NATM 450
NA NA NATM NATM 110
2 4 7 n g /m L 2 .4 %
N A x Not Appfcable Samples analyzed on 4/16/12 for PFBS using a 1:50 dlution factor and on 4/27/12 for PFHS and PFOS using a 1:10 cHudon factor.
(1) Sample not n a ly n d for tNs analyte due to inappropriate spite level
Page 20 of 89
GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-Site WWTP Walls - April 2012
Table 14. DAL GW T W 5 R 120405
PFB S
PFHS
PFO S
m u m id
D e s c rip tio n
G LP 10-01-02-31-017
D A L -G W -T W S R -0-120405
G LP 10-01-02-31-018
D A L-G W -TW 5R -D B -12 0 405
G LP 10-01-02-31-019
D A L-G W -T W 5R -L S -120405
G L P 10-01-02-31-020
D A L -G W -T W 5R -H S -120405
G L P 1 0 01 -0 2 -3 1 -01 7 :5 00 p o b LM S D A L -G W -T W 5R -0-LM S
A v e ra g e C o n c e n tra tio n (n g /m L ) 1 % R P D
C o n c e n tra tio n
C o n c e n tra tio n
(n g /m L )
% R e c o v e rv
(n g /m L )
% R e c o v e ry
533 NA 510 NA
N A (1)
N A (1)
N A (1>
N A < 1)
988 9 3 .3
522 n g /m L 1 4 A %
4 3 .3
NA
4 2 .6
NA
5 1 .1
NC
136 9 32
N A (1>
N A (1>
4 3 .0 n g /m L 1 1 .6 %
C o n c e n tra tio n (n g /m L )
% R e c o v e ry
704 688 N A < 1>
NA NA N A < 1)
N A (1) 696
N A (1) 9 1 .4
6 9 6 n g /riiL 2 .3 %
NA = NotApplicable N C Not Calculated; the sample concentration la greater than 2x the aplte level Samples analyzed on 4/27/12 for PFBS and PFOS usk? a 1:50cSiution factor and on 4/13/12 for PFHS using a 1:10 dlulion factor. (1) Sample not analyzed for this analyte due to inappropriate spire level.
Table 15. DAL GW TW 6R120405
PFB Sm
PFH Sa
PFO Sm
m um id
D e s c rip tio n
G L P 10-01-02-31-021
D A L -G W -T W 6R -0-120405
G LP 10-01-02-31 -0 2 2 G L P 10-01-02-31-023
D A L-G W -TW 6R -D B -12 0 405 D A L -G W -T W 6R -L S -120405
G L P 1001-02-31-024 G LP 10-01-02-31-021:200po b LM S
D A L -G W -T W 6R -H S -12 0405 D A L -G W -T W 6R -0-LM S
A v e ra g e C o n c e n tra tio n (n g /m U 1 % R P D
C o n c e n tra tio n
C o n c e n tra tio n
( n g /m L )
% R e c o v e rv
(n g /m L )
% R e c o v e ry
156 155 NA<1) 238 N A (1)
NA NA N A (1) 8 2 .5 N A <1>
4 8 .0 4 5 .4 5 4 .6 131 N A (1)
NA NA NC 8 4 .5 N A (1>
1 S 6 n g /m L 1 0 .6 4 %
4 6 .7 n g /m L 1 5 .6 %
C o n c e n tra tio n (n g /m L )
Y o R e c o v e tv
287 274 N A `1) N A (1)
NA NA N A (1) N A (1)
4 5 6 9 4 .0
2 8 1 n g /m L 1 4 .6 %
N A NotAppRcable NC = Not Calculated: the sample concentration Is greater than 2x the apfce leveL Samples analyzed on 4/27/12 for PFBS and PFOS using a 1:50 dfcition factor and on 4/13/12 for PFHS uaing a 1:10 dlution factor. (1) Sample not analyzed for this anatyte due to inappropriate spke level.
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GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-Site W W TP W ells - April 2012
Table 16. DAL GW TRIP01 120405
PFB S
PFH S
PFO S
3M LM S D
D e s c rip tio n
G L P 1 0 -0 1 -0 2 -3 1 -0 2 6 D A L-G W -TR IP 01-0 -1 2 0 4 0 5 G L P 1 0-01-02-3 1 -0 2 7 D A L -G W -T H IP 01-L S -12040S G L P 1 0 -0 1 -0 2 -3 1 -0 2 8 D A L -G W -T R IP 01-H S -120405
C o n c e n tra tio n (n g /m L )
< 0.250 8.51 9 2 .0
% R e c o v e rv
NA 85.1 9 2 .0
C o n c e n tra tio n (n g /m L )
0 .2 5 0 8 .6 0 8 8 .4
X R e c o v e ry
NA 862 88.6
C o n c e n tra tio n (n g /m L )
0232 6 .9 6 70.1
% R e c o v e rv
NA 6 9 .7 702
N A * NdtAppIcaUe Samples analyzed forPFBS and PFHS on 4/13/12 and on 4/16/12 for PFOS using a 1:10 dM ion factor.
Table 17. Rineeate Blank
3 M L M S ID
D e s c rip tio n
G L P 10-01-Q 2-31-028 D A L -G W -T W 3R -R B -120405
PFB S
PFH S
PFO S
C o n c e n tra tio n C o n c e n tra tio n C o n c e n tra tio n
(n g /m l)
(n g /m L )
(n g /m L )
0250
0 .2 5 0
0232
Samples analyzed forPFBS and PFHS on 4/13/12 and on 4/16/12 for PFOS using a 1:10 caution factor.
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GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-Site WWTP W eis - April 2012
10 Conclusion
Laboratory control sp ites, field matrix spikes, and lab matrix spires w ere used to determ ine the analytical method accuracy and precision for PFBS, P FH S , and P FO S . Analysis w as successfully completed following 3M Environmental Laboratory method E TS -8-044.1 desorbed herein.
11 Data/Sample Retention
AD rem aining sam ples and associated project data (hardcopy and electronic) will be archived according to 3M Environmental Laboratory standard operating procedures.
12 Attachments
Attachm ent A: Protocol Am endm ent 31 (G eneral Project Outline) Attachm ent B: Representative Chrom atogram s and Calibration Curves Attachm ent C: Analytical M ethod-ETS-8-044.1 Attachm ent D: Method Deviation
Page 23 of 89
GLP10-01-02; Interim Report 31 Analysis ofPFBS, PFHS, and PFOS In Groundwater
New On-Site WWTP Weils - April 2012
13 Signatures
Cleston Lange, Ph.D., 3M Principal Analytical Investigator
Date
W liam K. Reagen, Ph.D., 3M Environmental Laboratory Department Manager
D a te
Page 24 of SS
GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-Site WWTP W eis - April 2012
Attachment A: Protocol A mendment
Page 25 of 89
imi! I r i m i i f hi
inmiiiiiniiiiiiii
I li, il
GLP10-01-02; interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
A n Jim
Amendment 31
S tudy Title Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and
Perfluorobutane sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program
PROTOCOL AMENDMENT NO. 31
Am endm ent Date: March 28, 2012
Perform ing Laboratory 3M Environmental, Health, and Safety Operations
3M Environmental Laboratory Building 260-5N-17
Maplewood, MN 55144-1000
Laboratory P roject identification G L P 10-01-02
Sam pling Event New On-Site Wells - Adjacent to 3M Decatur W W TP
Page 1 of 6 Page 26 of 89
GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
Amendment 31
This amendment modifies the following portion of protocol:
"Analysis of PFOS, PFHS and PFBS in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program"
Protocol reads: No changes to to e wording o f toe protocol a re required.
Amend to read:
No changes to the wording o f th e protocol a re required. This am endm ent only addresses and docum ents
the addition o f th e G en eral P roject O utline (G P O ) fo r th e collection and analysis o f groundw ater sam ples
as part o f the 3M D ecatu r P hase 3 Program fo r P FO S , P FH S and PFBS (G L P 1 0 -0 1 -0 2 ). T h e anticipated
sam ple collection w ill occur around th e tim efram e o f the w eek o f April 2 ,2 0 1 2 . T h e groundw ater sam ples for this sam pling e v e n t w ill b e entered into the 3M Environm ental Laboratory L IM S as project G L P 1 0 -0 1 02-31 and reported a s interim report G L P 1 0 -0 1 -0 2 -3 1 , (reflecting study G L P 1 0 -0 1 -0 2 and am endm ent 3 1 ).
T h e reason fo r this am endm ent is to docum ent th e G eneral Project O utline (G P O ) w hich describes the anticipate groundw ater sam p le collection even t for six new on-site tem porary residuum m onitoring w ells in th e vicinity o f th e W a s te w a te r T reatm en t P lant (W W T P ) a t th e 3M D ecatu r facility. T he G PO is three pages in length and included as attached to this am endm ent form .
Page 2 of 6 Page 27 of 89
GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
Amendment Approval
Amendment 31
Page 3 o f6 Page 28 of 89
GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New O n-Site W W TP W e is - April 2012
Analytical Protocol: GLP10-01-02 Amendment 31
Environmental Health & Safety Operations, Environmental Laboratory G eneral Project O utline
To: G ary Hohenstein, 3M EHS&Opns
From : cc:
Susan W olf, 3M EHS&Opns; Environmental Lab W illiam R eagan, 3M EHS&Opns; Environmental Lab
Cleston Lange, 3M EHS&Opns; Environmental Lab
Jai Kesari, W eston Solutions
D ate:
March 22, 2012
S u b je c t
A nalysis o f P erfluorooctane S ulfonate (P F O S ), Perfluorohexane S ulfonate (P F H S ) and P erfluorobutane sulfonate (P F B S ) in G roundw ater, Soil and S edim en t fo r the 3M D ecatur P hase 3 S ite -R e la te d M onitoring Program ; G L P Interim R eport 31; N ew O n -S ite W ells A djacent to th e 3M D ecatu r W astew ater Treatm ent P lant (W W T P )
1 General Project Information
C ontacts
Lab Request Number Six D ig it D epartm ent Num ber Project Sehodule/Test Dates
3M Sponsor R epresentative Gary Hohenstein 3M EHS Operations 3M Building 224-5W -03 Saint Paul. M N 55144-1000 Phone: (651) 737-3570 aahohensteinO m m m .com
3M Environm ental Laboratory M anagem ent William K. Reagan 3M EHS Opns, Environmental Laboratory 2 6 0 -5 N -1 7 651 733-9739 w kreaaenO m m m .com
Principal A nalytical Investigator Cleston Lange 3M EHS Opns, Environmental Laboratory 2 6 0 -5 N -1 7 651 733-9860 cclanaeO m m rrt.com
Sam pling C oordinator Timothy Frinak Weston Solutions Timothv.frinak@we8 tonsolutions.oom Phone: (334)-332-9123
G LP10-01-02-31
Dept #530711, Project #0022674449
Sampling scheduled for the week o f April 2 ,2 0 1 2
All verbaI and written correspondence will be directed to Gary Hohenstein.
Page 4 of 6 Page 29 of 89
Analysts of PFBS, PFGHLSP,1a0n-0d1P-0F2O; SInitnenGmroRunedpwota3te1r
Amendment 31
2 Background Information and Project Objective(s)
T h e 3M E H S O perations Laboratory (3M E nvronm ental Lab) w ill receive and a n a ly ze groundw ater sam ples collected from six new tem porary on-site residuum m onitoring w ells located ad jacen t to the 3M D ecatu r W W T P for P erfluorobutanesulfbnate (P F B S ), P erfluorohexanesulfonate (P F H S ), and P erfluorooctanesulfonate (P F O S ). A nalyses will b e conducted under th e G LP requirem ents o f E P A TS C A G ood Laboratory Practice Standards 4 0 C F R 792.
G roundw ater sam ples w ill be collected by W eston Solutions personnel th e w e e k o f A pril 2, 2012. T h e 3M Environm ental Laboratory will prepare the sam ple bottles w ith all required spikes to en sure that results for P FB S , P FH S , and P F O S a re o f a known precision and accuracy. T h e final report w ill be subm itted to G ary H ohenstein and Jai K esari upon com pletion under interim report G L P 10 -0 1 -0 2 -3 1 .
3 Project Schedule
________
_____________
Sam ple collection bottles will be prepared by 3M Environmental Laboratory fo rsam p in g the w eek o f April 2, 2012. Sam ple bottles will be shipped in coolers overnight to 3M D ecatur for arrival on Friday, March 3 0 ,2 0 1 2 . Sam ple bottles should be stored refrigerated on-site until sample collection.
M artin Sm ith \ W eston T ra ile r 3M D ecatur P lant 1400 S tate Docks Road D ecatur, A labam a 35601
4 Test Parameters
The targeted limit o f quantitation will b e 0 .0 2 5 n g /m L (ppb) for PFBS, PFH S, and PFO S.
Six sampling locations have been specified; TW 1R , TW 2R , TW 3R , TW 4R , TW 5R , and TW 6R . These are new wells with no historical sampling values for estimating field matrix spike levels, however, information received from W eston indicates that locations T W 3R , T W 4R and potentially T W 5R , are expected to have higher concentrations based on the expected groundwater gradients in the area o f these w ells and field observations. Given the limited information on expected levels, a t each sampling location, a total o f four sam ple bottles will be collected (sam ple, sam ple duplicate low field m atrix spike and high field matrix spike). The low field matrix sp ke w il be prepared at 10 ng/m L and the high field matrix spike will be prepared a t 100 n g /m L The "fill to here" line on each 250 mL Nalgene bottle will be 200 mL. O ne set of trip blanks consisting of reagent-grade w ater as well as a low and high trip blank spike will be prepared a t the 3M Environmental Laboratory and sent to the sampling location with the other bottles. All sam ple bottles w tl include the addition o f ,80 rP F B S , 18C>2-P F H S , and 13C8PFO S (internal standard) a t a nominal concentration of 1 ng/m L All sam ple bottles will also include the addition of 13C 4-P F O S (surrogate spike) a t a nominal concentration o f 0.1 ng/mL. O ne additional bottle w il be prepared to be used for the preparation o f the equipm ent rinseate blank. A 500-m L bottle of laboratory reagent w ater w il be sent with the sam ple bottles to be used to generate the rinseate blank sam ple.
5 Test Methods
Sam ples will be prepared and analyzed by LC /M S /M S following E TS -8-044.1 "Method of Analysis for the Determination o f Perfluorinated Com pounds In W ater by LC/M S/M S; Direct Injection Analysis".
The data quality objectives for these studies are quantitative results for the target analytes with an analytical accuracy o f 10030% . Field matrix spikes not yielding recoveries within 10030% w il be addressed in the report and the final accuracy statem ent m ay be adjusted accordingly.
W here applicable, sam ples w il be analyzed against an internal standard calibration curve. Each curve point will contain isotopically-labeled perfluorocarboxylc acids and perfluorosulfonic acids at a nom inal concentration of 1
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G LP 10 -0 1 -0 2; Interim R eport 31 A n a ly sis o f P F B S , P F H S , a n d P F O S in G roundw ater
AnMSm W m MW
Amendment 31
ng/rnL. T h e calibration curve will be generated by taking the ratio of tee standard peak area counts over tee internal standard peak area counts to fit tee data for each analyte.
6 Reporting Requirements
For each sampling location, the report will contain the results fo r the sam ple, sam ple duplicate, and field matrix spike. Trip blank and trip blank spike will be reported for the sampling event a s will any equipm ent/rinseate blanks prepared in the field. Laboratory control spikes o f reagent w ater prepared a t the tim e o f sam ple extraction will also be reported and used to evaluate tee overall method accuracy and precision. Method blanks o f reagent w ater prepared at tee tim e o f sam ple extraction will be used to determ ine the method detection lim it
Page 6 of 6
Page 31 of89
Analysis of PFNBeSw, POFGnH-LSSPi,t1ea0Wn-0dW1P-0TF2PO;WSIniteneirsGim-roARupenrpidlow2r0ta13te12r
At ta c h m e n t B : R e p r e s e n t a tiv e S a m p l e C h r o m a to g r a m s a n d C a u b r a tio n C u r v e(s )
Page 32 of80
*** Ginger AG0I330509
Analysis of PFNBeSw, POFGnH-LSSPi,t1ea0Wn-0dW1P-0TF2PO;WSIntieenlrliGsm-rAoRupenrpidlow2r0ta13te12r
Results Name: g!20413a.rdb
Printing Date: Monday April 16 2012
Page 33 of 86
** Ginger AG01330509
Analysis of PFNBeSw, POFGnHL-SSPt,1ea0Wn-0dW1P-0TF2PO;WSIntiaenlrlisGm-roARupenrpidlow2r0ta13te12r
Results Name: gl20413a.rdb
Printing Oste: Monday, April 1$, 2012
Page 34 of 89
** Ginger AG01330509
Analysis of PFNBeSw, POFGnH-LSSP*,1ea0Wn-0dW1P-0TF2PO;WSIntieenlrlGism-rAoRupenrpidlow2r0ta13te12r
Results Name: g!20413a.rdb
D a t a p r i n t e d b y STff Printing Time: 11:15:42 AM Printing Date: Wednesday May 09 2012
Page 1 of 9
Page 35 of89
*** Ginger RG01330509
Analysis of PFNBeSw, POFGnHL-SSPt,1ea0Wn-0dW1P-0TF2PO;WSIntieenlrlisGm-rAoRupenrpidlow2r0ta13te12r
R e s u l t s Name: gl20413a.r<tt)
Page 36 of 89
*** Ginger AG01330509
Analysis of PFNBeSw, POFGnH-LSSPi,t1ea0Wn-0dW1P-0TF2PO;WSIntienelrlGsim-roARupenrpidlow2r0ta1t3e21r
Results Name: g!20413a.rdb
Printing Date: Wednesday, May 09, 2012
Page 37 of89
*** Ginger AG01330509
Analysis of PFNBeSw, POFGnH-LSSPi,t1ea0Wn-d0W1P-0TF2PO;WSIntieenlrlisGm-rAoRupenrpidlow2r0ta13te12r
Results Name: gl20413a.rdb
Printing Bate: Wednesday, May 09, 2012
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*** Ginger AG01330509
Analysis of PFNBeSw, POFGnH-LSSMP,1ea0Wn-0dW1P-0TF2PO;WSInIteenlrlisGm-roARupenrpidlow2r0ta13te12r
Results Name: g!20413a.rdb
Printing Date: Wednesday, May 09, 2012
Page 39 of68
*** Ginger AG01330509
Printing Tine: 11:15:43 AM
Printing Date: Wednesday, May 09, 2012
Analysis of PFNBeSw, POFGnH-LSSPf,t1ea0Wn-0dW1P-0TF2PO;WSIntiaenlrliGsm-rAoRupenrpidlow2r0ta13te12r
Results Name: gl20413a.rdb
k
Page 40 of 80
*** Ginger AG01330509
Analysis of PFNBeSw, OPFGnH-LSSPi,t1ea0Wn-0dW1P-0TF2PO;WSIntieenlrliGsm-rAoRupenrpidlow2r0ta13te12r
Results Name: gl20413a.r<lb
Printing Date: Wednesday, Nay 09, 2012
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*** Ginger AG01330509
Analysis of PFNBeSw, POFGnHL-SSPt,1ea0Wn-0dW1P-0TF2PO;WSInitenelrlisGm-roARupenrpidlow2r0ta13te12r
Results Name: gl204L3a.rdb
Page 42 of 89
*** Ginger AG013305G9
Analysis of PFNBeSw, POFGnH-LSSPi,t1ea0Wn-0dW1P-0TF2PO;WSIntieenlrlisGm-rAoRupenrpidlow2r0ta13te12r
Results Name: g!20413a.rdb
Printing Time: 11:15:44 AM Printing Date: Wednesday, May 09, 2012
Page 43 of89
Workstation: ETSBUSTER
Analysis of PFNBeSw, POFGnH-LSSPi,t1ea0Wn-0dW1P-0TF2PO;WSIntieenlrliGsm-roARupenrpidlow2r0ta13te12r
Batch Name: bl20416a.dab
Printing Time: 2:17:59 PM Printing Date: Wednesday April 19 2012
Page 44 of89
Workstation : ETS80STER
Analysis of PFNBeSw, POFGnH-LSSPi,t1ea0nW-0d1WP-0TF2PO;WSIntieenlrliGsm-roARupenrpidlow2r0ta13te12r
Batch Mama: b!20416a.dab
Page 45 of89
*** Buster J2930203 P r i n t i n g Date: W e d n e s d a y , M a y 09, 2012
Analysis of PFNBeSw, POFGnH-LSSPi,t1ea0Wn-0dW1P-0TF2PO;WSIntieenlrlisGm-roARupenrpidlow2r0ta1t3e12r
m*
I
r
iL I
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*** Buster J2930203
GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-Site VVWTP W elb - April 2012
Printing Time: 11:27:17 AM Printing Date: Wednesday, May 09, 2012
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*** Buster J2930203
GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-Site WWTP Wells - April 2012
P r i n t i n g Date: Wednesday, Hay 09, 2012
*** Buster J2930203
GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-Site WWTP Wells - April 2012
Printing Date: Wednesday, H a y 09, 2012
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*** Buster J2930203
GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-Ske WWTP Wells - April 2012
Printing Time! 11:28:38 AM P r i n t i n g Date: K e d n e s d a y ( May 09, 2012
Page 2 o f 3
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* * * Buster J2930203 P r i nting Date: Wednesday, M a y 09, 2012
GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-Site WWTP Wells - April 2012
Page 3 of 3
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Korkstation: ETSBUSTER
GLP1G-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-Sfte WWTP Wells - April 2012
Batch Name: bl20427a.dab
Printing Tine: 2:04:20 PM Printing Date: Monday, April 30, 2012
Page 52 of 88
Korkstation: ETSBUSTER
GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-Ste WWTP Wells - April 2012
Batch Name: b!20427a.dab
Printing Time: 2:03:53 PM Printing Date: Monday April 30 2012
Page 53 of 88
Workstation: ETSBUSTER
GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-Site WWTP Wells - April 2012
Batch Name: bl20427a.dab
Printing Tine: 2:04:06 PM Printing Date: Monday April 30 2012
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** B u s t e r J2930203
GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-Site WWTP Wells - April 2012
P r i n t i n g Date: Wednesday, May 09, 2012
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*** Buster J2930203
GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PROS in Groundwater
New On-Site WWTP Walls -April 2012
Printing Date: Wednesday, Hay 09, 2012
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*** Buster J2930203
Printing Time: 11:31:04 AH Printing Date: Wednesday, Hay 09, 2012
GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-Site WWTP Wells - April 2012
Page 3 of 3
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*** Buster J293Q203
GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-Site WWTP Walls - April 2012
P r i n t i n g Date: Wednesday, May 09, 2012
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*** Buster J2930203
GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-Site WWTP Wells - April 2012
Printing Date: Wednesday, May 09, 2012
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*** Buster J2930203
GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-Site WWTP Wells -April 2012
Printing Time: 11:33:49 AM P r i n t i n g Date: Wednesday, May 09, 2012
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*** Buster J2930203
GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New O n-Ste WWTP Wells - April 2012
Printing Time: 11:33:49 AM Printing Date: Wednesday, Hay 09, 2012
Page 4 of 4
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*** Buater J2930203
GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-Site WWTP Wells - April 2012
Printing Time: 11:32:19 AM P r i n t i n g Date: Wednesday, May 09, 2012
Page 1 of 3
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*** Buster J2930203
GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-SKe WWTP Wells - April 2012
Printing Time: 11:32:19 AM Printing Date: Wednesday, M a y 09, 2012
Page 2 of 3
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* Buster J2930203
GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-Site WWTP Wells - April 2012
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GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-Site WWTP W eis - April 2012
Atta c h m e n t C : A n a ly tic a l M e th o d (s )
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GLP10-01-Q2; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-Site WWTP Wes - April 2012
3M Environmental Laboratory
Method
Method o f Analysis for the Determination o f Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis
Method Number: ETS-8-044.1
,Adoption Date: 4/12/07
Effective Date: / 1
Approved By: W illiam K. R eagen, Technical D irector, Environm ental Laboratory
J / J a\/ o J /
D ate
E T S -8 0 4 4 .1
Page 1 of 22
Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct
Injection Analysis
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GLP10-01-02; IrrtBfim Repot 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-Site WWTP W eis - April 2012
1 Scope and Application
This m ethod describes th e direct injection analysis o f perfluorinated com pounds (P F C s) from w ater m atrices using high-perform ance liquid chrom atography tandem m ass spectrom etry (H P LC /M S /M S ). T h e m ethod is generally applicable but not lim ited to the m easurem ent o f perfluoroattcyl sulfonam ides and perfluorinated alkyl ad d s (P FA A s) such as perftuorosuifonic ad d s (P FS A s) and perfiuorocarboxytic ad d s (P FC A s) (T ab le 1 ). W ater sam ples containing heavy particulate m ay require preparation by an altern ate m ethod such as E T S -8-154 ` D eterm ination o f P erfluorinated A dds, Alcohols, A m ides, and S ulfonates In W ater By Solid Phase Extraction and High Perform ance Liquid C hrom atography/M ass S pectro m etry. The m ethod is applicable to both external standard and internal standard calibration*1.
T a b le 1 . R e p re s e n ta tiv e T a rg e t A n a ly te s
A c ro n y m
PFB A (C 4 A rid) PFPaA (C 5 A rid ) PFHxA (C 6 A rid) PFHpA (C 7 Acid) PFOA (C 8 A rid ) P F N A (C 9A rid ) PFDA (C 10 A rid) PFUnA (C11 A rid) PFDoA (C 12 A rid) PFTiDA (C 13 Acid) PFBS (C 4 Sulfonate) PFHS (C 6 Sulfonate) PFOS (C 8 Sulfonate) FBSA (C 4 Sulfonamide FOSA (C 8 Sulfonamide)
A n a ly te
Perfluorobutanoic add P erfh w ro p en tan o icad d Petfluorohexanoic arid Pertluoroheptanoic arid Petfluorooctanoic add Pertkiorononanoic add Petfluorodecanoic arid Peifluoroundecanoic arid Petfluorododecanoic arid Pertluorotridecanoic arid Perduorobutanesutfonic acid Pertluorohaxanesulfonic arid Perfluoroodanesulfonic arid PerDuorobutanesulfonanide Pefluorooctanesulfonamide
C h e m ic a l A b stract S e r v ic e s
R e g is try N u m b e r IC A S R N )
3 7 5 -2 2 -4 2706-90-3 3 0 7 -2 4 -4 3 7 5 6 5 -9 3 3 5 6 7 -1 375951 335752 2055946 3 0 7 -5 5 1 72629946 375736 3 5 5 4 6 -4 1763231 3 0 3 3 4 -6 5 1 7 5 4 -9 1 6
T he M inim um Reporting Level (M R L) is th e Lim it o f Q uantitation (L O Q ) th at m eets D ata Q uality O bjectives (D Q O s) th at a re developed based on th e intended use o f this m ethod.
M ethod Flexibility - This is a perform ance-based m ethod and m ay be g enerally applied to the determ ination o f perfluorinated com pounds in w ater m atrices w hen analysis batch quality control (Q C ) criteria are m et2. Each set o f sam ples are prepared in an analysis batch w ith calibration standards, LC Ss, blanks, and continuing calibration check standards analyzed on th e sam e instrum ent during a tim e period th at begins and ends w ith th e analysis o f th e appropriate continuing calibration check standards. T he laboratory is perm itted to m odfy th e LC colum n, m obile phase com position, LC conditions, and M S /M S conditions. M ethod m odifications should be considered to im prove m ethod perform ance or to m eet data quality objectives fo r th e study. In a ll cases w here m ethod m ocifications are im plem ented, th e batch
a1nHdieCm8 petehroflduoisrosaulpkpaonretesdulbfoynvaamlididaetiionnlawbiothraitnotreyrncaolnsttraonldsaarmd pclaelsiburnadtieorn3fMormC4e-thCo1d3vPaFliCdaAtiso,nCE4.llC-066. a6n7d. C8 PFSAs, 1MM(PGeaeuttrhhtidooAaddsnssVceoearftfliAioodrnnaeta5islo)ytansob"ifs,liDbisnh.i)riSenEcugPtpimAvpeoeMrt9ht1eoo/td4hf Po1Q4drCe,5-Sr3CeA7gr,iNitaseCtnrridaOatic/bo3.a)n0sE2De9uda/r9oota9npReraeae.vn)q.FuC4Dior(eAm1m1mMe/0nias7tsys/i0of20on0)r:.0AG1,nu"niGdeaxuniIcdIea(nfPocarerGtfAoer,nIsenerdacuttiisnotgnrya4,n)BdainoRdaenApaonlyrnttieincxgaIlQ
E T S -8 -0 4 4 .1
Page 2 of 22
Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/M S/M S;
Direct Injection Analysis
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GLP10-01-02; Interim Report 31 Analysis of PFBS, PFHS, and PFOS in Groundwater
New On-Site WWTP Wefls Apni 2012
analytical Q C s (section 9 ) m ust be com pleted and pass Q C acceptance criteria (section 13 ) if th e d ata from th e analytical batch are to be reported.
2 Method Summary
W ater sam ples are analyzed as n eat aqueous sam ple o r as solvent diluted aqueous sam ples by direct injection using LC /M S /M S . Sam ptes containing heavy particulate m ay not be suitable fo r analysis by this m ethod. Sam ples containing suspended particulate should be centrifuged o r tite re d prior to rem oving a sam ple aliquot o r diluting w ith so lven t T h e w ater sam ple is m ixed w ell prior to rem oving an aliquot or diluting, if necessary, w ith A STM Type I w ater, H PLC w ater, other suitable w ater, or solvent (m ethanol).
Q uantitation is by stable isotope internal standard calirratio n in laboratory reagent w ater. A ll perfluorinated com pounds (P F C s) target analyte concentrations o f perfluorosulfonic acids (P FS A s) and perfluorocarboxylic ad d s (P FC A s) a re reported as anions and corrected for th eir salt o r fle e a d d form s. A ttem ativety, quantitation m ay be perform ed by external standard calibration.
This is a perform ance-based m ethod. M ethod uncertainty fo r each targ et analyte is determ ined fo r each analytical batch using m ultiple laboratory control s p ite s a t m ultiple concentrations. This m ethod also requires th at th e precision and accuracy fo r each sam ple be determ ined using field m atrix spikes to verify th at th e m ethod is applicable to each sam ple m atrix. C alibration standards fo r PFU nA , PFD oA , P FTrD A , and FO SA have been found to be unstable fo r m ore than 2 days n 100% w ater. Sam ptes requiring analysis fo r these com pounds by th is m ethod should be d lu ted 1:1 w ith m ethanol and analyzed against a calibration c u n prepared in 1:1 synthetic groundw aterM eO H .
3 Definitions
3.1 Analysis Batch
A set o f study sam ples th at a re prepared w ith catibration standards, laboratory control sam ples, and procedural blanks, and analyzed on th e sam e instrum ent during a tim e period th at begins and ends w ith th e analysis o f th e appropriate continuing cafibration check standards.
3.2 Analytical Sample
A portion o f a laboratory sam ple prepared fo r analysis.
3.3 Calibration Standard
A solution prepared by spicing a known volum e o f th e W orking S tandard (W S ) into a predeterm ined am ount o f A STM Type I, H PLC grade w ater, o r other suitable w ater (i.e . m atrix w ater), and analyzed accordng to th is m ethod. C a tx a tio n standards a re used to calibrate th e instrum ent response w ith respect to analyte concentration.
3.4 Laboratory Duplicate Sample (LDS, or Lab Dup)
A laboratory duplicate sam ple is a separate aliquot o f a sam ple taken in D ie analytical laboratory th at is analyzed separately w ith identical procedures. A nalysis o f LDSs com pared to th at o f th e firs t afiquot g ive a m easure o f th e precision associated w ith laboratory procedures, but not w ith sam ple collection, preservation, o r storage procedures.
E T S -8 -0 4 4 .1
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Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/M S;
Direct Injection Analysis
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New On-Site WWTP Wes - April 2012
3.5 Field Blank (FB)/Trlp Blank (TB)
A STM Type I, HPLC grade w ater, or other suitable w ater, placed in a sam ple container in th e laboratory and treated as a sam ple in a ll respects, including exposure to sam pling site conditions, storage, preservation a id a ll analytical procedures. T he purpose o f th e TB is to determ ine if te s t substances or other interferences are present in th e field environm ent. This sam ple is also referred to as a T rip B lank.
3.6 Field Duplicate Sample (FDS, Field Dup)
A sam ple collected in duplicate a t th e sam e tim e from th e sam e location as th e sam ple. T he FD S is handled under identical circum stances and treated exactly th e s a n e throughout field and laboratory procedures. A nalysis o f th e FD S com pared to th at o f th e firs t sam ple gives a m easure o f th e precision associated w ith sam ple collection, preservation and storage, as w e l as w ith laboratory procedures.
3.7 Field Matrix Spike (FMS)
A sam ple to which known quantities o f th e targ et analytes, IS s and SR Ss are added to th e sam ple bottle in th e laboratory before th e bottles are sent to th e field fo r collection o f aqueous sam ples. A known, specific w lu m e o f sam ple m ust be added to th e sam ple container w ithout rinsing. This m ay be accom plished by m aking a "f i to th is level" line on th e outside o f th e sam ple container. T h e FM S is analyzed to ascertain if any m atrix effects, interferences, or stability issues m ay com plicate th e interpretation o f th e sam ple analysis.
3.8 Trip Blank Matrix Spike (TBMS)
An aliquot o f A STM Type I, H PLC grade w ater, or other suitable w ater, to which known quantities o f th e targ et analytes, IS s and SR Ss are added in th e laboratory prior to th e shipm ent o f th e collection bottles. T he TB M S is analyzed exactly like a study sam ple to help determ ine if th e m ethod is in control and w hether a loss o f analyte o r analytical bias could be attributed to sam ple holding tim e, sam ple storage and/or shipm ent issues. A low and high TB M S are appropriate w hen expected sam ple concentrations are not known o r m ay vary.
3.9 Internal Standard (IS)
A com pound added to each study sam ple, calibration standard, laboratory control sam ples, and procedural blanks a t a consistent level (typically around 1 ng/m L). T he internal standard(s) are stable isotope labeled versions o f th e targ et analytes. T h e area count ratio o f the targ et an alyte to the internal standard is used fo r calb ratio n . Surrogate IS s are applied w hen stab le isotope IS s o f target analytes are unavailable. A surrogate IS is not necessariy a stable isotope labeled version o f th e targ et analyte, but is treated as an internal standard fo r q u a n tita tio n .
3.10 Laboratory Control Sample (LCS)
An aliquot o f control m atrix to which known quantities o f the targ et analytes, IS s and SR S s (w hen applicable) are added in th e laboratory a t th e tim e when sam ples are aliquotted. A t least th ree levels (tw o levels fo r S R S s) in tip lic a te are included, one generally a t th e low end o f the calibration curve and one n ear th e m id range and the upper end o f th e c tave. The LC Ss are analyzed exactly like a laboratory sam ple to determ ine w hether th e stability o f the standards. LCSs should be prepared each day sam ples a re aliquoted.
3.11 Laboratory Matrix Spike (LMS)
A laboratory m atrix spike is an aliquot o f a sam ple to which known quantities o f target analytes, IS s and S R S s (w hen applicable) are added in th e laboratory. T h e LM S is analyzed exactly Ik e a laboratory sam ple to determ ine w hether th e sam ple m atrix contributes bias to th e analytical results. T h e endogenous concentrations o f th e analytes in th e sam ple m atrix m ust be determ ined in a separate aliquot and th e m easured values in th e LM S corrected fo r these concentrations. LM Ss are optional fo r analysis o f aqueous sam ples.
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3.12 Laboratory Sample
A portion o r aliquot o f a sam ple received from the field fo r testing.
3.13 Limit of Quantitation (LOQ)
T h e low er lim it o f quantitation (LLO Q ) fo r an analytical batch is th e low est concentration that can be reliably quantitated w ithin th e specified lim its o f precision and accuracy. T h e LLO Q is generally selected as the low est non-zero standard in th e cafibration curve th at m eets m ethod acceptance criteria. T h e LLO Q fo r each targ et analyte is established fo r each analysis batch as the low est catibration standard w ith area counts a t least tw ice th at o f th e average area counts o f th e procedural blanks.
T h e upper lim it o f quantitation (U LO Q ) fo r an analytical batch is th e highest concentration th at can be reliably quantitated w ithin th e specified lim its o f precision and accuracy. T h e highest standard in th e c a lix a tio n curve th at m eets m ethod acceptance criteria is defined as th e U LO Q .
3.14 Method/Procedural Blank
An aliquot o f control m atrix th at is treated exactly tike a laboratory sam ple including exposure to a ll glassw are, equipm ent, solvents, and reagents th at are used w ith other laboratory sam ples. T h e m ethod blank is used to determ ine if te s t substances o r other interferences are present in th e laboratory environm ent, the reagents, o r th e apparatus.
3.15 Sample
A sam ple is an aliquot rem oved from a larger quantity o f m aterial intended to represent the original source m aterial.
3.16 Stock Standard Solution (SSS)
A concentrated solution o f a single-analyte prepared in th e laboratory w ith an assayed reference com pound.
3.17 Surrogate Internal Standard
An IS th at is not necessarily a stable isotopically labeled targ et analyte, but is treated as an internal standard fo r quantitation. Surrogate IS s are used w hen iso to p icaly labeled counterparts o f th e targ et analyte are n ot com m erciaSy o r readily a v a ia b ie .
3.18 Surrogate Recovery Standard (SRS)
An isotopically labeled standard, not used as an internal standard, th at is added to each sam ple and appropriate Q C sam ple as a m eans to evalu ate Ih e m ethod perform ance fo r a chem ical d ass o f com pounds (e .g ., PFSA s, PFC A s).
3.19 Working Standard (WS)
A solution o f several analytes prepared in th e laboratory from S S S s and cSuted as needed to prepare calibration standards and other required analyte solutions.
4 Warnings and Cautions
4.1 Health and Safety
T he acute and chronic toxicity o f th e standards fo r this m ethod have not been precisely determ ined; how ever, each should be treated as a potential health h azard. T he analyst should w ear gloves, a lab coat, and safety glasses to prevent exposure to chem icals th at m ight be p resen t
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T he laboratory is responstole fo r m aintaining a safe w ork environm ent and a current aw areness o f local regulations regarding th e handling o f th e chem icals used in th is m ethod. A reference file o f m aterial safety data sheets (M S D S ) should be availab le to a ll personnel involved in th ese analyses.
4.2 Cautions
T he analyst m ust be fam iliar w ith th e laboratory equipm ent and potential hazards including, but not lim ited to , th e use o f solvents, pressurized gas and solvent lines, high voltage, and vacuum system s. R efer to th e appropriate equipm ent procedure o r operator m anual fo r additional inform ation and cautions.
5 Interferences
During sam ple preparation and analysis, m ajor potential contam inant sources a re reagents and glassw are. A ll m aterials used in th e analyses shall be dem onstrated to be fre e from interferences under conditions o f analysis by running m ethod blanks.
P a ls and supplies th at contain Teflon should be avoided o r m inim ized due to th e possibility o f interference and/or contam ination. These m ay include, but are not lim ited to: w ash bottles, T e flo n * lined caps, autovial caps, H PLC parts, etc.
T he use o f disposable m icropipettes or pipettes to aliquot standard solutions is recom m ended to m ake calibration standards and m atrix spikes.
6 Instrumentation, Supplies, and Materials
6.1 Instrumentation
A nalytical balance capable o f reading to 0 .0001g H P LC /M S /M S o r H PLC /M S system , as described in Section 10.
6.2 Supplies and Materials
Sam ple collection bottles-- H D P E (e .g ., N algeneTM ) w ide-m outh bottles w ith screw cap. N o te: D o not use fluorinated or Teflon bottles o r lined caps. C oolers o r boxes fo r sam ple shipm ent. 15-m L and 50-m L disposable polypropylene centrifuge tubes. C lass A pipettes and volum etric flasks, various. 2 m L H PLC autoviaIs D isposable pipettes, polypropylene or glass as appropriate C entrifuge capable o f spiraling 15-m L and 50-m L polypropylene tubes a t 3000 rpm .
7 Reagents and Standards
N o te: Suppliers and catalog num bers a re fo r H ustrative purposes only. Equivalent perform ance m ay be achieved using chem icals obtained from other suppliers. D o not use a lesser grade o f chem ical than those listed.
7.1 Chemicals
W ater - M ilB-Q, H PLC grade, or other suitably appropriate sources
Calcium A cetate - A .C .S . R eagent G rade
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M agnesium A cetate - A .C .S . R eagent G rade M ethanol - H PLC grade Am m onium A cetate - A .C .S . R eagent G rade
7.2 Representative Target Analytes, ISs, and SRSs
PFB A , H eptafiuorobutyric A d d , (C 4 Perfluorinated A dd ) P FP eA , N onafluoropentanoic A dd (Cs Perfluorinated A d d ) PFH xA , Perfluorohexanoic A dd (Cg Perfluorinated A d d ) PFH pA, Tridecafluoroheptanoic A dd , (C 7 Perfluorinated A d d ) PFO A , Am m onium perfluorooctanoate, (Cs Perfluorinated A dd ) PFN A , H eptadecafluorononanoic A dd , (Cg Perfluorinated A dd ) PFD A , Nonadecafluorodecanoic A dd (C 10 Perfluorinated A d d ) PFU nA , Perfluoroundecanoic A dd , (C n Perfluorinated A dd ) PFD oA, Perfluorododecanoic A dd , (C 12 Perfluorinated A d d ) PFTrD A , Perfluorotridecanoic A dd , (C 13 Perfluorinated A dd ) FBSA, Perfluorobutanesulfbnam ide FO SA , Perfluorooctanesulfbnylam ide PFB S , Potassium Perfluorobutanesulfonate P FH S , Perfluorohexanesulfonate P FO S , Potassium perfluorooctanesulfbnate
PFO A [1 z 3 ,4-13q , 13C risotoptcafly labeled perfluorooctanoic ad d (S R S )
PFO S [1 ,2 ,3 ,4 -13C ], 13C4-isotopicaBy labeled PerfluorooctanesuNbnate (S R S ) PFU nA [1 ,2 -13C ], 13C2-isotopically labeled Perfluoroundecanoic ad d (S R S )
A custom m ix o f IS s in a m ethandic solution containing ([1 .2 ,3 ,4 -X J P F B A J 1 2 -
.................................. ,, . . . -
....
. . _________ ______ CaJPFOS,
and [1 ,2 ,3 ,4 ,5 ,6 ,7 ,8 -13C aP FO S A (W elfington Laboratories, G uelph, O N ) in com bination w ith
added a i,2 ,3 ,4 ,5 -13(y P F P e A , ([1 2 ,3 ,4 -n C JPFH pA , and [" O JP FB S can be used to prepare
a stock IS solution. A lternatively, incfividual stable isotope IS s can b e used to prepare a stock
IS m ixture.
O ther IS s can be applied.
7.3 Reagent Preparation
2 m M Am m onium acetate solution (A nalysis)--W eigh 0 .3 g o f Am m onium acetate and dissolve in 2 .0 L o f reagent w ater.
Synthetic G roundw ater (containing 2 5 ppm C a and M g) - W eigh 0.61 g o f Cakaum A cetate and 0 .9 2 g o f M agnesium A cetate and dissolve in 6 .0 L o f reagent w ater.
N ote: A lternative volum es m ay be prepared as long as th e ratios o f th e solvent to solute ratios are m aintained.
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7.4 Stock Standard Solution (SSS) and Working Standard Solution Preparation
T he follow ing standard preparation procedure serves as an cam ple. W eighed am ounts and final volum es m ay be changed to suit th e needs o f a particular study. For exam ple, pL volum es m ay be spiked into volum etric flasks when diluting stock solutions to appropriate levels.
100 pg/m L ta rg e t a n a ly te SSSs-- W eigh out 10 mg o f analytical standard (corrected for percentsalt, acid [ETS-4-031] and purity) and dilute to 100 m L with m ethanol or other
suitable solvent, in a 100 m L volum etric flask. Transfer to a 125 m LLD P E bottle or other suitable container. P repare a separate solution fo r each analyte. Expiration dates and storage conditions o f stock solutions should be assigned in accordance w ith laboratory standard operating procedure. An cam ple o f purity and salt correction is given below fo r PFO S.
u i __ m o lecu lar w eig ht o f anion s a lt correction fa c to r = ---------------------- - -------------- --
m oclecular w eig h t o f salt
499 P FO S (K + )s a lt correction fa c to r = -- - = 0 .9 2 7 5
j Ou
10 m g C sFi/SO sK * w ith purity 90% = 8 .3 5 m g CdFnSQf (1 0 m g *0.90*0.9275= 8.35 m g)
10 p g /m L (1 0 ,0 0 0 n g /m L ) m ixed w o rkin g stan d ard -- Add 5 .0 m L each erfth e 100 pg/m L S SS s to a 50 m L volum etric flask and bring up to volum e w ith solvent.
1 p g/m L (1 ,0 0 0 n g /m L ) m ixed w o rkin g stan d ard -- Add 0 .5 m L erfthe 100 pg/m L S SS s to a 5 0 m L volum etric flask and bring up to volum e w ith solvent.
0.1 p g/m L (1 0 0 n g /m L ) m ixed stan d ard -- Add 0 .0 5 m L o f th e 100 pg/m L S S S s to a 50 m L volum etric flask and bring up to volum e w ith solvent.
S to rag e C o n d itio n s-- S tore a ll SSS s and working standards in accordance w ith laboratory standard operating procedure or in a refrigerator a t 4 2 C fo r a m axim um period o f 6 m onths from th e d ate o f preparation.
7.5 Calibration Standards
C alibration can be perform ed by IS o r external calibration. Using th e w orking standards described above, prepare calibration solutions in A STM Type I w ater, H PLC w ater, other suitable w ater, o r a m ixture o f solvent and w ater using th e inform ation in T ab le 2 as a guideline. N ote: Volum es o f w ater o r w ater/solvent m ixtures and working standards m ay be adjusted to m eet th e data quality objectives addressed in the general project outline. C alibration levels other than those listed below can b e prepared as needed.
For th e quantitation o f PFO A a id P FO S , reference m aterials o f certified m ixed lin ear and branched isom er a e preferred. A lternately, reference m aterials o f prim arily lin ear isom ers o f PFO A and/or P FO S m ay be used, how ever, w hen quantitating w ith predom inantly linear reference standards, additional LC S sam ples containing both lin ear and branched isom ers o f
PFO A and PFO S are required3.
7.5.1 in tern al S tandard (IS ) and S urrogate R ecovery S tandard (S R S)
For IS calibration, stable isotope internal standards o f each targ et analyte o r appropriate surrogate IS s should be spiked a t th e sam e level in a ll calibration standards. O nce the calibration standards have been prepared as stated above in Section 7 .5 , a ll calibration standards are spiked w ith a separate internal standard spiking solution. Typically th e
3PFAOrAep/PoFrtOBSBcimanMbnezmfoguanndainss3rMssmrempotrotfEthl 1e-u0s5e60o.freference standards containing certified Imear and branchedisomers of
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concentration o f th e internal standard is consistent w ith th e internal standard concentration expected in th e sam ples being prepared, usually 1 ng/m L. The concentration o f th e internal standard spicing solution is typically 2 pg/m L. A separate zero point o r m ethod blank is typically prepared a t the sam e tim e as the calibration standards, using th e sam e solution used to prepare th e standards (A STM Type I w ater, H PLC w ater, other suitable w ater, o r a soivent/w ater m ixture), and is spiked w ith th e internal standard a t th e sam e concentration as th e calibration curve, typically a t 1 ng/m L.
If th e sam ples being analzyed w ere pre-spiked w ith S R S s, th e cafibration curve prepared in Section 7 .5 is sp ired w ith a separate S R S sp itin g solution. Typically, th e sam ple bottles are spiked w ith a S R S a t 0.1 ng/m L. T he fin al calibration curve m ust consist o f a t least six calibration points after analysis. T he follow ing tab le provides an exam ple o f s p ire concentrations and volum es used to achieve a m ulti-point extracted cafbration curve w ith internal standard and surrogate standard.
T able 1 lists recom m ended stable isotope internal standards fo r several PFSA and PFC A target com pounds. A custom m ix o f isotopicaljy labeled targ et analytes in a m ethanolic solution containing ([1 ,2 ,3 ,4 -13C ,,]P FB A [U -^ Q J P F H x A , [1 ,2 ,3 ,4 ,5 ,6 ,7 ,8 -13Ca)PFO A, [1 ,2 ,3 ,4 ,5 ,6 ,7 ,8 ,9 -^ C J P F N A , [1 ,2 ,3 ,4 ,5 ,6 -^CgJPFDA, [1 ,2 ,3 ,4 ,5 ,6 ,7 -lSC7]P FU nA , [1 ,2 "c y P F D o A , [1 ,2 ,3 -l3C a|PFH S, [1 ,2 ,3 ,4 ,5 ,6 ,7 ,8 -13C 8jPFO S, and [1 ,2 ,3 ,4 ,5 ,6 ,7 ,8 -i3C aIFO SA (W ellington Laboratories, G uelph, O N ) in com bination w ith added ([1 ,2 ,3 ,4 ,5 -13Cs]PFPeA , ([1 ,2 ,3 ,4 -13C 4]PFH pA and [1OJPFBS can be used to prepare a stock IS solution. A lternative sources o f certified stable isotope labeled targ et analytes are appScable. A lternatively, individual stable isotope IS s can be used to prepare a stock IS m ixture. T he tab le below lists the recom m ended stable isotope IS s and S R S s applied in th e m ethod. O ther stable isotope IS s and S R S s o f targ et analytes not listed to th e tab le m ay b e used if supported by validation and/or analysis batch Q C s m eeting m ethod acceptance criteria (e.g ,, [13C2]-P F O A ). T h e sam e internal standard should be used fo r a given analyte throughout the en tire prqject/study. N ote: som e o f th e com pounds listed below a re appropriate to use as surrogate IS s when a stable isotope IS o f a target analyte is not availab le. G enerally, surrogate isotopically labeled PFC A s are used fo r PFC A s, and surrogate isotopicaily labeled PFSA s are used fo r PFSA s.
Table 2 provides exam ples o f spice concentrations and volum es used to achieve a m ulti-potot calibration curve w ith IS s and SR Ss.
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T a b le 1 . S ta b le Is o to p e P FC A s a n d P F S A s u sed fo r IS s a n d S R S s
CompoundName
Synonym orAcronym
^CVPerfhiorobutaiioic acid l3Ci-Perfluoropenlanoic a d d
[1 JU ,4 -UC]PFBA [l^ JA -^ C s JP F P e A
13C-Perfhiorohexanoic a d d 13C 4-Perfluoroheptanoic a d d 13Cf-Perfluorooctanoic acid
[1,2 -uC J P F H x A [1,2,3,4-uC 4]P FH pA [l,2,3,4,5,6,7,8-liC J P F O A
13C-Perfluoranananoic acid 13C 4-Perfhioiodecanoic a d d
13C 7-Perfluoroundecanoic acid
[1^ 3,4,5,6,7,8^ -^ CjIP FN A [1,2,3,4,5,6 -UC,JPFDA [1,2,3,4,5,6,7 -uC 7JPFU nA
13Ci-Pafluocododecanotc a d d
[1,2 -" C J P F D o A
" Ch-Am m om um Perfiuocobutane sulfonate [" O jIP FB S
13f y Am monium Perfluorohexane sulfonate [ ^ - " C JP F H S
I3Cj-Sodium Perfluorooctane sulfonate
[l,2,3,4,5,6,7,8-u C JP F O S
13C r Peifluo!Ooctaziesulfbnaniide 13C-Peifiuo<uoctanoic a d d
[1,2,3,4,5,6,7,8-u C jJFO S A [l,2 ,3 ,4-uC 4JP FO A
AnalyticalPurpose
IS fo rP F B A IS fb rP FP e A
IS fb rP F H x A
IS fo rP F H p A IS fo r P F O A and [1,2,3,4 " CJPFO A IS for P F N A IS fo rP F D A IS fo rP F U n A
IS for PFD oA , * P FTA IS for PFB S IS for PFH S IS for PFO S and p f o s [i a 3 .4 " c y . IS for F O S A
SR S fo r a ll P FC A s: C4-C8
RSoeuferrceenceStandard
W ellington Labs (M ix o r Individual) W ellington Labs (M ix o r Individual) W ellington Labs (M ix o r Individual) W ellington Labs (M ix o r Individan W ellington Labs (M ix o r Individual) W ellington Labs (M ix o r Individual) W ellington Labs (M ix o r Individual) W ellington Labs (M ix o r Individual) W ellington Labs (M ix o r Individual) R H International (Individual) W ellington Labs (M ix or Individual) W ellington Labs (M ix o r Individual) W ellington Labs (m ix) R T I International (Individual)
W ellington
13C 2-Perfluoram decanoic acid
[1,2 -" C J P F U n A
SR S for a ll P F C A s C9-C13 W ellington
I3Ct-Perfluorooctane sulfonate
[1,2,3,4-u C 4]PFO S
SR S for a ll P FS A s: C 4 , C6, andC8
W ellington
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T a b le 2 . E xam p le P re p a ra tio n o f C a lib ra tio n C u rv e w ith IS s an d S R S s
Sam ple Description
0.025 ng/mL curve point 0.030 ng/mL curve point 0.04 ng/mL curve point 0.05 ng/mL curve point
0.1 ng/mL curve point 0.25 ng/mL curve point 0.5 ng/knLcurve point
1 ng/mL curve point 2.5 ng/mL curve point 5.0 ng/mL curve point 10.0 ng/mL curve point 25.0 ng/mL curve point 50.0 ng/mL curve point 75.0 ng/mL curve point 100 ng/mL curve point
C oncentration o f IMS, pg/m L
0.10 0.10 0.10 0.10 0.10 0.10 1.0 1.0
iao
100 10.0 100 10.0 100 10.0
Volum e o f W S.pL
25 30 40 50 100 250 50 100 25 50 100 250 500 750 1000
V olum e o f IS (2 PBA n Q .fi.
50 50 50 50 50 50 50 50 50 50 50 50 50 50 50
Concentration o f Surrogate, pg/m L
0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 10.0 10.0 10.0 10.0 10.0 10.0 10.0
Volum e o f Surrogate, ftL
12.5 15 20 25 50 125 250 500 25 50 100 NA NA NA NA
Volum e o fA S T M Type 1 W ater, o r o th e r suitab le s o lv e n tn , mL
100 100 100 100 100 100 100 100 100 100 100 100 100 100 100
NfA-Not Applicable (1) Samples requiring analysis for PFUnA, PFOoA, PFTiDA, and FOSA should be analyzed against a calibration curve prepared in 1:1 syntheticgroundwaterMeOH.
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8 Sample Collection and Bottle Preparation
Sam ple collection bottles a re prepared by 3M Environm ental Laboratory (o r subcontract suppSer) personnel fo r shipm ent a t am bient tem perature to th e collection site. Typically, four sep arate collection bottles are associated w ith a stogie collection site: sam ple, field duplicate sam ple, low field m atrix spike, and high field m atrix s p ite . A lternatively, th e sam ple and field duplicate sam ple m ay contain S R S s in lieu o f additional target analyte low field m atrix s p ite and target an alyte high field m atrix s p ite sam ples. Depending on th e scope o f th e project, additional replicates o f the field sam ple and field m atrix spikes m ay be added. A lso, it is not uncomm on fo r additional m id-level field m atrix spikes to be collected if th e expected sam ple concentrations are truly unknown o r could span a large concentration range.
H igh-density polyethylene (H D P E ) vride-m outh N algene bottles are used fo r th e sam ple collection containers. (Volum es o f th e bottles m ay vary depending on how m uch sam ple is required to m eet data quality objectives.) S am ple collection volum es are project specific and based on d ata quality objectives. T he N algene bottles do not require any pretreatm ent prior to use. Typically, placem ent o f a sam ple bottle volum etric H I to here" line is done by using a sam ple bottle m arker tem plate. A lternatively, bottles m ay be w eighed prior to bottle preparation and w eighed again a fte r sam ples have been collected.
A l bottles should b e d e a rly labeled to indicate its intended use as a sam ple, field sam ple duplicate, low field m atrix s p ire , high field m atrix s p ire , sam ple/S R S field m atrix s p ire , field duplicate sam ple/S R S field m atrix spike, trip blank, o r trip blank m atrix s p ire . If each location has different designated spike levels, th e label should also clearly incficate th e sam ple location designation. G enerally, a set o f bottles fo r a given collection site are prepared then grouped together in plastic bags fo r organizational purposes. For each sam ple collection even t, a t least one set o f tip blank and tip blank m atrix sp ires are prepared.
B ottle preparation should be docum ented in a N ote to F ile or on a sam ple preparation w orksheet and should include th e follow ing inform ation: d ate prepared, to tal num ber o f bottles prepared, num ber o f sam ple sites, the standard identification num bers and spike volum es used to prepare s p ired bottles, th e "fil to here" volum e, and any other pertinent inform ation needed fo r reconstrudibility o f th e d ata. T h e N ote to F ie w ill be included in th e fin al data package fo r th e p ro ject
Sam ples are collected in th e field and shipped to th e laboratory a t am bient tem perature.
8.1 Field Matrix Spike Sample (FMS)
Field m atrix spike sam ples are a requirem ent o f the m ethod. A FM S sam ple is defined as a Q C sam ple to which known quantities o f appropriate targ et analytes are added to th e sam ple bottle in th e field o r in the laboratory before th e bottles are sent to th e field . T he sam ple and field duplicate sam ple m ay contain appropriate S R S s in fieu o f targ et analyte FM S sam ples. Sam ple quantities a re determ toed volum etricaly o r gravim etrically. A know n, specific volum e o r w eight o f sam ple is added to th e sam ple container w ithout rinsing. V olum etric sam ple m easurem ents m ay be acquired by a laboratory applied "fill to this level" Kne on the outside o f th e sam ple container. T arg et analyte FM S sam ples should be spiked a t approxim ately 0 .5 -1 0 tim es th e expected analyte concentration in th e sam ple. If th e expected range o f an alyte concentrations is unknown, m ultiple spikes a t varying levels m ay be prepared to increase th e Ikeflhood th at a s p ite a t an appropriate level is m ade. Typically a low and a high targ et analyte s p ite are prepared fo r each sam pling location. In those instances w here S R S s are to be used in lieu o f targ et analyte FM S sam ples, th e sam ple and field duplicate sam ple a re spiked a t approxim ately 2 -5 tim es the targ et LO Q . T h e FM S is analyzed to ascertain if m atrix effects o r sam ple holding tim e contributes bias to th e analytical results. For th e sam ple bottles designated to r m atrix s p ite s , an appropriate volum e o f m atrix sp itin g solution is added to th e em pty bottle prior to sam pling. T h e volum e o f spice solution added should produce th e desired final concentration o f target analytes once the bottle is filled w ith sam ple to th e "fill to h ere line". T h e m atrix spidng solution(s) should be prepared in a suitable solvent and contain afl o f th e apfxopriate targ et analytes, IS s, and S R S s. T h e targ et an alyte m atrix spiking solution is often th e sam e as the working standards used to create the calibration standards. An exam ple o f a bottle s p k e is given below .
"Fill to here' volum e = 2 0 0 m l. (A 250 m L N algene bottle is used)
D esired Field S pike C oncentration = 0 .2 5 ng/m L
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500 nL o f a 0.1 p g/m Lspiang solution (containing th e targ et analytes) is added to th e bottle and th e bottle cap prom ptly seeded.
8.2 Internal Standard and Surrogate Recovery Standard
tf analysis o f a surrogate recovery standard (S R S ) is inducted in th e project objectives, an appropriate volum e o f a surrogate standard solution is added to a ll th e bottles prior to sam pling and S P E . Typically sam ple bottles are s p ite d w ith surrogate recovery standards a t a final desired s p ite concentration o f 0.1 ng/m L.
If quantitation by interna! standard (IS ) is included in th e project objective, an appropriate volum e o f internal standard solution is added to a l th e bottles prior to sam pling and S P E . Typically sam ple bottles a re sp ited w ith internal standard a t a fin a l desired s p ite concentration o f 1 n g/m L
For the trip blank, th e S R S s p ite and IS s p ite is added to the bottle and then A STM Type I w ater (H P LC grade reagent w ater o r other suitable w ater m ay used) is added to th e TH to here* lin e. T h e bottle is capped and sealing tap e m ay be placed around th e outer edge o f th e cap. T rip blank m atrix s p ite s are prepared by acking th e appropriate volum e o f targ et analyte sp itin g solution, IS , and S R S sp itin g solutions and fiin g th e bottle to th e desired volum e w ith th e appropriate w ater and capping and seain g th e cap.
9 Quality Control and Data Quality Objectives
9.1 Data Quality Objectives
This m ethod and required quality control sam ples is designed to generate data accurate to 30% w ith a targeted LO Q o f 0 .0 2 5 ng/m L A ny deviations from th e quality control m easures spelled out below w il be docum ented in th e raw data and footnoted in th e final re p o rt
9.2 Method/Procedural Blanks
T he m ethod/procedurai blank is zero point calibration standard (w hich includes IS s) analyzed in a regular basis w ith each analysis batch. A t a m inim um , m ethod blanks are analyzed prior to instrum ent caK ratio n , prior to th e analysts o f C C V sam ples, a fte r every 10 sam ple injections, and a t th e end o f th e analytical run.
T he m ean area count o r area ratios when using internal standard calibration, fo r each an alyte in the m ethod
blanks m ust be less than 50% o f th e area count counts o r area ratios w hen using interna! standard catibration, o f th e LO Q standard. T h e standard deviation o f th e area counts, or area ratios Yriien using internal standard caltoration, o f these m ethod blanks should be calculated. A specific % R SD acceptance criteria is not specified but is assessed on an analytical batch basis. If th e m ean area counts o r area ratios w hen using internal standard calibration, o f the m ethod blanks exceed 50% o f the LO Q standard, then th e LO Q m ust be raised to th e firs t standard level in th e curve th at m eets criteria. M ethod blanks m ay be elim inated if technical justification can be provided (e .g . th e procedural blank w as analyzed a fter an unexpected^ high level sam ple). If any procedural blanks a re rem oved from th e LO Q determ ination, docum ent in the raw d ata and report as appropriate. Laboratory S am ple R e p lic a te s /F ie ld D uplicate Sam ple
Typically, sam ples a te collected in duplicates in th e fie ld . T h e relative percent difference (R P D ) o f duplicate sam ples should be 20% fo r th e precision o f sam ple preparation and analysis to b e considered in control. R eplicate sam ples not m eeting th e ^20% R PD criteria are flagged and reported as outside o f Q C acceptance c rite ria .
9.3 Laboratory Matrix Spikes (LMSs)
LM Ss m ay be perform ed in lieu o f FM Ss if FM Ss have previously been perform ed fo r th e sam ple m atrix. AdcStionally, LM Ss m ay be perform ed in lieu o f FM Ss fo r a sam ple m atrix if th e FM S levels w ere not appropriate fo r determ ining spice recoveries relative to endogenous levels o f targ et analytes and appropriate S R S s. G e n eraly, each sam ple location represents a different sam ple and sam ple m atrix. LM Ss are prepared fo r each sam ple and analyzed to determ ine th e m atrix effect on s p k e recovery efficiency o f each targ et analyte and appropriate S R S s. LM Ss should be prepared a t a m inim um o f one level and in d u p lcate. LM S
concentrations should be prepared ai approxim ately 0 .5 -1 0 tim es the endogenous concentration or
approxim ately 4 -1 0 tim es th e LO Q concentration o f each targ et analyte.
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Lab m atrix s p k e recoveries should fa ll w ithin 30% o f expected values. Sam ple d ata w ith LM S recovery outside o f 30% but w ithin 50% o f the expected value are flagged and reported as outside o f Q C acceptance criteria. D ata w ith LM S recovery outside o f 50% o f th e expected value are reported as N R , w here N R is defined as ` N ot R eportable" d ata outside o f Q C acceptance criteria.
9.4 Lab Control Sample
Lab control s p ite s ave prepared fo r each analysis batch to determ ine m ethod accuracy and precision. LCSs should b e prepared a t th ree levels fo trip licate fo r each target analyte and a t a m inim um o f tw o levels in triplicate fo r appropriate S R S s. Low lab control spikes should be prepared a t a concentration in th e range o f approxim ately four to ten tim es higher than th e targeted low er LO Q , th e m id lab control s p ite s should be prepared a t a concentration near the m id-point o f the calibration curve and th e high lab control spikes a t approxim ately 80% o f the upper LO Q . For each targ et an alyte and S R S s, th e percent relative standard deviation (m ethod precision) fo r each control s p ire level m ust be less than or equal to 20% and th e average recovery (m ethod accuracy) fo r each control spike level m ust be 80-120% . Sam ple d ata fo r targ et analytes outside o f th e laboratory control spike acceptance criteria win be handled as follow s:
If th e average recovery o f a spiking level fa lls outside m ethod acceptance, but a t least 67% (6 out o f 9 ) o f LCS sam ples a re w ithin 20% erfth eir respective nom inal valu e (33% o f th e Q C sam ples, not a l replicates a t the sam e concentration, m ay be outside 20% o f nom inal valu e), th e average recovery w ill be flagged as outside m ethod acceptance criteria. A ll LCS sam ples w ill be control charted as p er E T S -4-026. If th e average recovery o f one o f th e spiking levels exceeded th e analytical m ethod uncertainty as determ ined by E T S -12012, th at analytical batch uncertainty w ill b e expanded fo r th at particular study.
If m ore than 67% o f the LCS sam ples fa il to m eet m ethod acceptance criteria, th e d ata w ill not be reported.
C alforation standards consisting o f m ixed branched and lin ear isom er P FO S /P FO A are preferred. H ow ever, fo r P FO S /P FO A targ et analytes, if th e catibration standards are com prised o f predom inantly lin ear isom ers only, a t least one level o f trip licate LCSs should be prepared using P FO S /P FO A w hich contains a m ix o f linear and branched isom ers. These LCSs w ill be used to dem onstrate quantitative equivalency (o r quantitative bias) o f th e isom eric m ix when using a predom inantly linear standard fo r calforation. T h e m ixed lin ear and branched isom er P FO S /P FO A LC Ss recoveries should fe ll w ithin 3 0 % o f expected values. A lternatively, in lieu o f m ixed branched and lin ear isom er P FO S /P FO A LCSs, m ixed branched and lin ear isom er PFO S /P FO A TB M Ss m ay be applied to dem onstrate m ethod accuracy and precision.
9.5 Field Matrix Spikes (FMSs) / Surrogate Recovery Standards (SRSs)
FM Ss a re prepared fo r each sam pling location and analyzed to determ ine th e m atrix effect a id sam ple holding tim e on the spice recovery o f each targ et an alyte and/or appropriate S R S . G enerally, each sam ple location represents a A fferen t sam ple a id sam ple m atrix.
FM Ss a re Q C sam ples to which known quantities o f appropriate targ et analytes a re added to th e sam ple bottle in the laboratory before th e bottles are sent to th e field . T yp icaly a low and a high targ et analyte FM S are prepared fo r each sam pling location. T he sam ple and field duplicate sam ple m ay contain appropriate S R S s in lieu o f targ et analyte low field m atrix spike and targ et analyte high field m atrix s p ite sam ples.
Field m atrix spike m ethod acceptance criteria are recoveries w ithin 30% o f th e expected value. If FM S
recovery (targ et analyte or S R S spike) is outside o f 30% o f the expected value o r could not be assessed because th e FM S (targ et an alyte) w as spiked a t an inappropriate level, th e sam ple result is reported as follow s:
1 . ) If target analyte FM S recovery could not be assessed because th e FM S 's w ere a t an inappropriate level, then Laboratory M atrix Spices (L M S ) m ay be substituted. If LM S recoveries are w ithin 30% th e data are reportable and flagged to indicate th at the FM S spikes levels w ere inappropriate.
2 . ) If m ultiple targ et analyte FM S 's w ere prepared on a sam ple and th e closest FM S level to th e reported sam ple m eets th e 30% acceptance criteria but additional FM S 's are outside th e 30% acceptance range, th e data are reportable and flagged to indicate th at w hile th ere w ere failing FM S 's, th e uncertainty w ill not be expanded since th e m ost appropriate spice level passed.
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3 . ) If the target an alyte FM S recoveries are outside o f the 30% acceptance range but a t least 3 0 acceptable historical reportable FM S sam ple results a re available, th e data m ay be reported but flagged w ith an expanded uncertainty and as not m eeting FM S criteria.
4 . ) Sam ple d ata w ith FM S recovery outside o f 30% but w ithin 50% o f th e expected value are flagged and reported as outside o f Q C acceptance criteria w ith an expanded uncertainty.
5 . ) If FM S recovery is outside o f 50% , th e sam ple result is reported as N R , w here N R is defined as "N ot R eportable" due to noncom pliant Q C results.
T he targeted fortification levels should be a t least 50% o f th e endogenous level and less than 10 tim es the endogenous level to be used w ithoutjustification to determ ine th e statem ent o f accuracy fo r analytical results.
N ote: It is posstoie fo r bottles utilized fo r Field M atrix S pike sam ples to be under-filled o r o ver-ffled during sam ple c o le d io n . S ince this scenario w il effect th e actual concentration o f th e FM S sam ple (surrogate and internal standard concentrations w il also be effected , if used), it is im portant th at any obvious under-filling or over-filling o f sam ple bottles be docum ented in th e d ata package and taken into account in th e FM S , IS s, o r S R S s recovery calculations. Sam ples o v er-filed o r u n d er-filed by m ore than 10% w i b e require recalculation o f th e FM S , IS s, and SR S tru e values.
T he average o f th e sam ple and th e field duplicate should be used to calculate th e recovery.
10 Procedures
10.1 W ater Sample Preparation
This m ethod is applicable to w ater sam ples. Sam ples containing heavy particulate m ay not be suitable fo r analysis by this m ethod. Sam ples containing suspended particulate should be centrifuge prior to rem oving a sam ple aliquot, o r ftte re d .
Thoroughly m ix sam ple before rem oving an aliquot and placing in a labeled autovial.
D iu te sam ple, if necessary, w ith A STM Type I w ater, H PLC w ater, other suitable w ater, o r solvent (m ethanol).
Lab control s p ite s a re prepared fo r each analysis batch to determ ine m ethod accuracy and precision. LCSs should be prepared a t three levels in tripficate fo r each targ et analyte and a t a m inim um o f tw o levels in triplicate fo r appropriate S R S s. Low lab control s p ite s should be prepared a t a concentration in the range o f approxim ately four to ten tim es higher than th e targeted low er LO Q , th e m id lab control s p ite s should be prepared a t a concentration near the m id-point o f th e c a lix a tio n curve and th e high lab control s p ite s a t approxim ately 80% o f th e upper LO Q . For IS quantitation, stable isotope internal standards o f each targ et analyte o r appropriate surrogate IS s should be spiked a t th e sam e level as the sam ples being analyzed, in aH LC Ss.
If LCSs are being prepared using synthetic groundw ater, a lo w th e LC Ss sam ples to e q u iix a te fo r a m inim um o f 4 hours before ^quoting fo r analysis o r d iu tin g w ith solvent (m ethanol).
11 Sample Analysis - LC/MS/MS
11.1 Instrument Setup
N o te: In this exam ple, an A pplied Biosystem s S d ex A P I 4 0 0 0 (A P I 500 0 or A P I 5 5 0 0 ) Tandem M ass Spectrom eter (L C /M S /M S ) is used. O ther brands/m odels o f LC /M S /M S instrum ents as w e l as single quadrupole m ass spectrom eters (L C /M S ) m ay be used as long as th e m ethod acceptance criteria are m e t Brand nam es, su pp iers, p art num bers, and m odels are fo r illustrative purposes only. Equivalent perform ance m ay be achieved using apparatus and m aterials other than those specified here, but dem onstration o f equivalent perform ance th at m eets th e requirem ents o f this m ethod is th e responsibility o f th e laboratory. The operator m ust optim ize and docum ent th e equipm ent and settings used.
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Establish the LC /M S /M S system and operating conditions equivalent to th e follow ing: M ass Spec: A pplied Biosystem s A P I 4 0 0 0 , A P I 5 0 0 0 , o r A P I 5500 Ion Source: T in t Ion S pray (A B S ) M ode: Electrospray N egative Scan Type: M R M (M ultiple R eaction M onitoring) Com puter: D efl DHM Softw are: W indow s 200 0 o r W indows X P , A nalyst 1 .4 .2 o r higher versions HPLC : A gilent S eries 1 1 0 0,1200, or 1290 A gilent Q uaternary Pum p A g le n t Vacuum D egasser A gilent Autosam pler A gilent Colum n O ven N o te: O ne o r m ore C 18 H PLC analytical colum ns (2.1 mm x 100 m m , 5pm o r 2.1 mm x 50 m m , 5pm ) m ay be attached on-line a fter th e purge valve and before th e sam ple injection port to retard and separate any residue contam inants th a t m ay be in th e m obile phase and/or H PLC system . H PLC Colum n: B etasil C 18,4.6m m x 100m m , 5pm (Therm oElectron C orporation) Colum n Tem perature: 35C Injection Volum e: 5pL M obile P hase (A ): 2m M Am m onium A cetate in A STM Type I w ater (S e e 7 .3 ) M obile P hase (B ): M ethanol
T a b le 3 . L iq u id C h ro m a to g ra p h y G ra d ie n t P ro g ra m .
S te p Num ber
0 1 2 3 4 5
Total Tim e (m in)
0 2.0 14.5 15.5 16.5 20.0
F low R ate (fM Jm in)
750 750 750 750 750 750
Percent A (2 mJWam m onium
acetate)
97.0 97.0 5.0 5.0 97.0 97.0
P e rc e n ts (M ethanol)
3.0 3.0 95.0 95.0 3.0 3.0
N ote: O ther H PLC gradients m ay be used as long as th e m ethod criteria and project d ata quality objectives are m et
It m ay be necessary to adjust th e H PLC gradient in order to optim ize instrum ent perform ance. Colum ns w ith d ifferent dim ensions (e .g . 2.1m m x 30m m ) and colum ns from different m anufacturers (K eystone B etasil C 18 e tc .) m ay be used.
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T a b le 4 S u g g e s te d M R M T ra n s itio n s fo r T a rg e t A n a ly te s , S u rro g a te s , a n d In te rn a l S ta n d a rd s
Analyte PFBA(C4 Add) PFPeA(C5 Add) PFHxA (C6 Add) PFHpA (C7 Acid) PFOA (C8 Acid) PFNA(C9 Acid) PFDA (CIO Acid) PFUnA(Cll Add) PFDoA (C12 Add) PFTAC13 Add)
PFBS (C4 Sulfonate) PFHS (C6 Sulfonate) PFOS (C8 Sulfonate) [U .3,4 -l3C4]PFBA rU.3.4.5 -uC,lPFPeA [U -"CJPFHxA TU.3.4- "CclPFHpA [U .3 .4 ^.6 ,7 .8 -uC]PFOA rU J.4 J.6 .7 .8 .9 -uC,lPFNA [U.3.4.5.6 -l3C,IPFDA [U.3.4.5.6.7 -lJC,]PFUnA ru -13c,ipfdoa [" OjIPFBS r U J - uC3]PFHS rU .3,4- uC4]PFOS rU 3 .4 J.6 .7 .8 -uC.lFOSA rU .3.4-uC4]PFOA [U .3,4- 1JC]PFOS iU -13C,lPFUnA
A nalyte Description
Target Target Target Target Target Target Target Target Target Target Target Target Target Target Target IS forPFBA IS for PFPeA IS forPFHxA IS for PFHpA IS for PFOA IS forPFNA IS for PFDA IS for PFUnA IS for PFDoA and PFTA IS for PFBS IS forPFHS IS forPFOS ISforFOSA Surrogate (C4-C8 Adda) Surrogate!Sulfonates, FOSA) Surrogate (C9-C13 Adda)
Mass Transition 01 (ttmu) 213 263 313 363 413 463 513 563 613 663 298 498 299 399 499 2X7 268 315 367 421 472 519 570 615 303 402 503 507 417 503 565
Mass Transition Q3 (amu) 169 219 269.119 319.169 369.219.169 419.169.219 469.269.219 519.269.219 569.169.319 619.369.319 78 78 99,80 99.80 8 0 .9 9 .1 3 0 172 223 270 322 376 427 474 525 570 84 80 80 80 372 80 520
M ultiple transitions fo r m onitoring th e analytes is an option. T h e use o f one daughter ion is acceptable if data sensitivity and selectivity is achieved and provided th at retention tim e criteria a re m et to assure adequate specificity. W N te th e daughter ions m ay be chosen a t th e discretion o f th e analyst, m ass transition 9 9 is suggested fo r P FO S . Q uantitation m ay be petform ed using th e to tal ion chrom atogram (T IC , o r sum m ed M R M s) fo r a given an alyte. For exam ple, th e P FO A T IC would sum a l th ree o f th e m onitored transitions. U se o f th e suggested prim ary ion is recom m ended. R etention tim es m ay vary slightly, on a day-to-day basis, depending on th e batch o f m obile phase and th e g rad ien t colum n, guard colum n(s) used etc. D rift in retention tim es is acceptable w ithin an analytical run, as long as th e d rift continues through th e en tire analysis and the standards are interspersed throughout th e analytical run.
11.2 Calibration Curve
Q uantitation is by internal standard o r external standard calibration. Cafibration standards m ay be prepared in A STM Type I, H PLC w ater, other suitable w ater, o r a solvent/w ater m ixture, ft internal standard c a lix a tio n does not m eet calibration acceptance criteria, external calibration can be applied. S ee T ab le 1 fo r
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recom m ended application o f available internal standards. Q uantitation o f PFO A and P FO S is by sum m ed analyte-specific m ass transitions.
A nalyze th e standard curve prior to each se t o f sam ples. If internal standards w ere added to th e c a lixatio n standards area ratios a re used to generate th e calibration curve. T h e standard curve m ay be plotted using a lin ear regression (y = m x + b ), w eighted 1Aco r unw eighted, or by quadratic fit (y = ax2 + bx + c ), w eighted 1Acor unw eighted, using suitable softw are. T h e m athem atical m ethod used to calculate th e calibration curve should be applied consistently throughout a study. Any change s h o tid be thoroughly docum ented in th e raw d ata.
High and/or low points m ay be excluded from the calibration curves to provide a b etter fit over th e range appropriate to th e data o r because they did not m eet Ih e pre-determ ined acceptance criteria. Low -level curve points should also be excluded if th eir a re a counts (o r area ra t if quantitating by IS ) a re not a t least tw ice th at o f th e average area counts ( a area ra t if quantitating by IS ) o f m ethod and/or solvent blanks. T h e coefficient o f determ ination (r2) value fo r th e calibration curve m ust be g reater than o r equal to 0 .9 9 0 (o r a correlation coefficient (r) o f 0 .9 9 5 ). Each point in th e curve m ust be w ithin 25% o f th e theoretical concentration w ith the exception o f th e LLO Q , which m ay be w ithin 30% . Justification fo r exclusion o f calibration curve points w ill be noted in th e raw d ata. A m inim um o f 6 points w ill be used to construct th e calibration curve.
If th e calibration curve does not m eet acceptance criteria, perform routine m aintenance or prepare a new standard curve (if necessary) and reanalyze.
11.3 Continuing Calibration Verification (CCV)
Continuing catibration verifications (C C V ) are analyzed to verify th e accuracy o f th e c a lix a tio n curve. A nalyze a m id-range c a lix a tio n standard, one o f th e sam e standards used to construct th e c a lix a tio n curve, a t a m inim um a fte r every tenth sam ple, not including solvent blanks, w ith a m inim um o f one p er sam ple s e t C alix a tio n verification injections m ust be w ithin 25% to be considered acceptable. T h e c a lix a tio n curve and th e last passing C C V w ill then bracket acceptable sam ples. M ultiple C C V levels m ay b e used. S am ples m ust be bracketed by passing C C V s o r th e calibration curve and a passing C C V to be reportable.
11.4 System Suitability
A m inim um o f th ree system su itab iity sam ples should be injected a t th e beginning o f each analytical run, prior to th e analysis o f th e calibration curve. Typically these sam ples are a t a concentration near th e m id-level o f the calibration curve and are repeated Sections from one autosam pler via l. It is suggested th at th e system suitability injections have area counts o r area ratios w hen using internal standard calibration, w ith a targ et R SD o f s5% and a targ et retention tim e R SD o f s2% . There is no defined acceptability lim it on these results as th e % R SD value is dependent on th e num ber o f M RM transitions being m onitored in th e LC /M S /M S run o r tim e period. U ltim ately, any effects on these param eters fo r th e System S u itab iity sam ples w ill also be evident on aril standards and Q C sam ples analyzed as p a rt o f th e analysis batch. A ny effect o f system su itab iity is incorporated w ithin Q C acceptance criteria.4
11.5 Sample Analysis and QCs
For each analysis batch, th e instrum ent analysis run sequence should include an initial calibration curve, sam ples, FD S s, interspersed blanks, interspersed C C V s, appropriate Q C s (i.e ., LC Ss, LM Ss, FM S s, TB M Ss, and T B s), and a fin al C C V o r calibration curve bracketing sam ples a id appropriate Q C s
Inject th e sam e volum e (betw een 5 -1 0OpL) o f each standard, analytical sam ple and blank into th e instrum ent (unless an on-instrum ent sam ple dilution is desired).
Sam ples containing analytes th at are quantitated above th e concentration o f the highest standard in th e curve should be fu rther diluted and reanalyzed.
43M Environmental Laboratory study E08-0096 evaluated the effect on these results as a function ofdie number ofMRMs bong oomtooed.
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12 Data Analysis and Calculations
T he chrom atography analysts softw are w il typically calculate th e am ount o f targ et an alyte in th e sam ple extracts using the established catibration curve. C alculate th e percent recovery o f th e LCS using th e folow ing equation:
LCS%recovery =-S-L-pC-i-kS-e--CC--oo-n-n-cc-ee-n-n-tt-rra-a-tt-iio-o-nn--(-*m^U1K0-l.)0%
C alculate th e percent recovery o f th e LM S using th e follow ing equation:
LM S Concentration ( - ^ - ) - Concentration o f Sam ple ( - ^ - ) LM S % recovery = ___________________ mL___________________________ mL
Spike Concentration ( - ^ - ) mL
100%
For sam ples fortified w ith known am ounts o f analyte prior to extraction, use th e follow ing equation to calculate th e percent recovery.
R ecovery _ T o ta l an a|Yte found (n g /m L ) - A verag e an alyte found in sam ple (n g /m L ) ^ A nalyte added (n g /m L )
13 Analysis Batch Method Performance Criteria
Any m ethod perform ance param eters th at are not achieved m ust be considered in th e evaluation o f th e data. Nonconform ance to any specified param eters m ust be described and discussed in th e fin al report if th e Technical M anager (non-G LP study) o r Study D irector (G LP study) chooses to report th e d ata.
If criteria listed in this m ethod perform ance section are not m et, m aintenance m ay b e perform ed on th e system and sam ples reanalyzed, o r other actions taken as appropriate. D o cu m en tal actions in th e raw data.
If data a re to be reported w hen perform ance criteria have not been m et, th e data m ust be footnoted on tables and discussed in th e text o f th e rep o rt
13.1 System Suitability - Analysis Batch
A m inim um o f th ree system suitability sam ples should be injected a t th e beginning o f each analytical run. These sam ples are run prior to th e calb ratio n curve. It is suggested th at th e system suitability injections have area counts w ith a target R SD o f 5% and a targ et retention tim e R SD o f S2% . T here is no defined acceptability lim it on these results as the % R SD s are dependent on th e num ber o f M R M transitions being m onitored in th e LC /M S /M S run or tim e period. A ny effect o f system su itab iity is incorporated in th e Q C acceptance criteria.
13.2 Calibration and Limit of Quantitation (LOQ) - Analysis Batch
C a lib ra tio n C u rve: T he coefficient o f determ ination (r2) value fo r th e calibration curve m ust be g reater than or equal to 0 .9 9 0 corresponding to a correlation coefficient (r) = 0 .9 9 5 . Each point in th e curve m ust be w ithin 25% o f th e theoretical concentration w ith th e exception o f th e LLO Q , which m ay b e w ithin 30% .
C C V P erfo rm an ce: T he calibration standards th at are interspersed throughout th e analytical sequence are evaluated as continuing catibration verifications in addition to being p art o f th e caB xation curve. T h e accuracy
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o f each curve point m ust be w ithin 25% o f th e theoretical value (w ithin 30% fo r low est curve point). Sam ples th at are bracketed by C C V s not m eeting these criteria m ust be reanalyzed.
L im its o f Q u a n tita tio n (L O Q ): T h e low er LO Q (LLO Q ) is th e low est non-zero active standard in the calibration curve; th e peak area o f th e LLO Q m ust be a t least 2X th at o f th e average area counts to r all prepared procedural blan k(s). By definition, th e m easured value o f the LLO Q m ust be w ithin 30% o f the theoretical valu e.
D em o n stratio n o f S p e c ific ity : Specificity is dem onstrated by chrom atographic retention tim e (w ithin 4% o f standard) and th e m ass spectral response o f unique ions.
13.3 Blanks - Method/Procedural Blanks and Trip
M eth o d /P ro ced u ral B lan ks: M ultiple procedural blanks should be interspersed throughout th e analysis batch and th e analytical sequence. A t a m inim um , m ethod blanks are analyzed prior to instrum ent calibration, prior to th e analysis o f C C V sam ples, afte r every 10 sam ple injections, and a t th e end o f th e analytical run.
T h e m ean area counts (o r area ratios w hen using IS calibration) fo r each analyte m ust b e less than 50% o f the area count o f th e LO Q standard. If th e area counts o f th e procedural blanks exceed 50% o f th e LO Q standard, then th e LO Q m ust be raised to th e first standard level th at m eets criteria.
T rip B lan k: A trip blank o f A STM Type I w aiter (o r lab equivalent) is prepared in a sam ple container in th e laboratory and treated as a sam ple, including exposure to shipping, sam pling site conditions, storage, preservation and a ll analytical procedures. T he trip blanks results fo r each analyte a re inducted w ith th e reported sam ple results.
13.4 Data Accuracy and Precision - Analysis Batch
Lab C o n tro l S p ikes: T h e average recovery a t each LC S level fo r each target an alyte and appropriate SR S should b e w ithin 80-120% and th e percent relative standard deviation o f th e recoveries m ust be less than or equal to 20% . If th e average recovery o f a spiring level falls outside m ethod acceptance, but a t least 67% (6 out o f 9 ) o f LC S sam ples a re w ithin 20% o f th eir respective nom inal value (33% o f the Q C sam ples, not all replicates a t th e sam e concentration, m ay be outside 20% o f nom inal valu e), th e averag e recovery w fll be flagged as outside m ethod acceptance criteria. A ll LC S sam ples w ill be control charted as per E T S -12-012. If th e average recovery o f one o f th e spiking levels exceeded th e analytical m ethod uncertainty as determ ined by E T S -12-012, th at analytical batch uncertainty w it be expanded fo r th at particular study. T he average recovery a t each LC S level fo r m ixed branched/linear isom er PFO A and P FO S should be w ithin 70-130% and the percent relative standard deviation o f th e recoveries m ust be less than or equal to 20% .
F ie ld D u p lic a te s : The relative percent difference (R P D ) o f duplicate sam ples should be less than 20% fo r th e precision o f sam ple preparation and analysis to be considered in control. R eplicate sam ples not m eeting the 20% R PD criteria are flagged and reported as outside o f Q C acceptance criteria.
F ie ld M a trix S p ikes: FM S acceptance criteria are recoveries w ithin 30% o f th e expected value fo r each targ et analyte and appropriate S R S . Sam ple data w ith FM S recovery outside o f 30% but w ithin 50% o f the expected valu e a re flagged and reported as outside o f Q C acceptance criteria. D ata w ith FM S recovery outside o f 50% o f the expected value are reported as N R , w here N R is defined as "N ot Reportable" data outside o f Q C acceptance criteria. If FM S recovery could not be assessed because FM Ss w ere a t an inappropriate level, then Laboratory M atrix Spikes (LM S s) m ay be substituted. If LM S recoveries a re w ithin 30% fo r each targ et analyte and S R S s th e data are reportable but flagged as not m eeting th e FM S m ethod acceptance criteria.
13.5 Analytical Method Uncertainty
A nalytical m ethod uncertainty fo r each targ et analyte and SR S is determ ined w ith control charted historical analysis batch LC S data fo r th e m ethod and reported w ith each analysis batch.5 U ncertainty determ inations
5 M ethod uncertainty based on INTERNATIONAL ANS/ISO/IED STANDARD 17025 reference (GUM, Guide to the Expression of Uncertainty in M easurement). M ethod application demonstrated in ETS-12-012, citing references: a.) EURACHEM/CITAC Guide. "Quantifying Uncertainty in Analytical M easurement," Second Edition; Editors: S.L.R. Ellison, M. Rosslein, and A. W illiams. b.)Georgian, Thomas, "Estim ation o f Laboratory Analytical Uncertainty Using Laboratory Control Samples," Environmental Testing &
E T S -8 -0 4 4 .1
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are based on IN TER N A TIO N A L A N S /IS O /IE D STA N D A R D 17025 reference (G U M , G uide to th e Expression o f U ncertainty in M easurem ent) and described in E TS -12 -0 1 2 . A t least thirty data points are required fo r determ ining analytical m ethod uncertainty. T h e m ethod uncertainty is defined as 2x th e standard deviation o f the percent recoveries o f th e pooled lab control s p ite s . W hile a ll LC S d ata points are control charted, only the m ost recent fifty d ata posits are used fo r determ ining th e m ethod uncertainty.
W hen less than thirty LCS d ata points have been generated fo r a given an alyte, th e analysis batch LC Ss are used to determ ine th e data uncertainty. If FM Ss m eet th e 30% recovery criteria a t a level appropriate to the endogenous level, and th e LC S m eet the 20% recovery criteria, then th e uncertainty o f th e data is determ ined as w ithai 10020% .
A nalysis batch sam ple data w ith FM S recovery outside erf30% but w ithin 50% o f th e expected valu e are flagged and reported as outside o f Q C acceptance criteria w ith expanded uncertainties. D ata w ith FM S recovery outside o f 50% o f th e expected value are reported as N R , w here N R is defined as ` N ot R eportable' data outside o f Q C acceptance criteria. If FM S recovery could not be assessed because FM Ss w ere a t an inappropriate level, then Laboratory M atrix S pikes (LM S s) m ay be substituted. If LM S recoveries a re w ithin 30% fo r each targ et analyte and appropriate S R S s th e data are reportable but flagged as not m eeting the FM S m ethod acceptance criteria w ith uncertainties o f 30% . If FM S do not m eet th e 30% recovery criteria, and historical FM S d ata does not exist, th e analytical uncertainty is evaluated on a sam ple-by-sam ple basis, th e d ata m ay be repotted w ith expanded uncertainty and a re flagged.
13.6 Quantitation of PFOA/PFOS - Analysis Batch
C alibration standards consisting o f m ixed branched and lin ear isom er P FO S /P FO A a re preferred. Q uantitation is perform ed by integrating th e lin ear and branched isom ers together. A lternately, th e lin ear and branched isom ers can be integrated separately, applying th e appropriate true value to each caHsration curve point fo r each isom er. T he LCS and sam ples are then quantitated by integrating th e tin e a ' and branched isom ers separately (requires separate analytical results tie s ) and quantitating th e resulting peak a g a n s t the lin ear or branched calibration curve. T he results from both integrations a re then sum m ed to produce th e final re s u lt Integrating th e lin ear and branched isom ers separately m ay be helpfU fo r those sam ples w here th e linear/branched ratios do not closely m atch those o f the reference standards.
H ow ever, fo r P FO S /P FO A targ et analytes, if th e caSbration standards a re com prised o f predom inantly linear isom ers only th e m ethod requires th e addition o f LCSs o f m ixed branched/linear isom er P FO S /P FO A . The purpose o f including these LC Ss is to dem onstrate quantitative equivalency (o r quantitative bias) o f th e isom eric m ix w hen using a predom inantly linear P FO S or PFO A standard fo r calibration. A lternatively, in le u o f m ixed branched and lin ear isom er P FO S /P FO A LC Ss, m ixed branched and lin ear isom er PFO S /P FO A TB M Ss m ay be appfied to dem onstrate m ethod accuracy and precision.
An altern ate m ethod o f quantitation can be perform ed w hereby only th e lin ear isom er o f P FO S /P FO A is integrated and used fo r generating th e calibration curve. T he LC S and sam ples a re then quantitated by integrating th e lin ear and branched isom ers separately (requires separate analytical results tie s ) and quantitating th e resulting peak against th e n e a r calibration curve. T h e results from both integrations are then sum m ed to produce th e final re s u lt Integrating th e in e a r and branched isom ers separately reduces th e oncolum n concentration fo r those sam ples th at contain both linear and branched isom ers o f P FO A /P FO S . This ensures th at th e concentration detected is w ithin th e a range o f the caib ratio n curve th at is com parable regardless o f w hether th e calibration curve w as generated using predom inantly Snear isom ers o f P FO S /P FO A or lin ear plus branched isom ers o f P FO S /P FO A .
14 Pollution Prevention and Waste Management
W aste generated w hen perform ing this m ethod w ill be disposed o f appropriately. T h e o rijjn a l sam ples w ill be archived a t th e 3M Environm ental Laboratory in accordance w ith internal procedures.
Analysis, Novcmber/Dccember 2000. c.)Taylor, B.N. and CE. Kuyatt, NIST Technical Note 1297,1994 Edition: `Guidelines for Evaluating and Expressing the Uncertainty o fNIST M easurement Results."d.)Adams, T.M ., "A2LA Guide for the Estim ation of M easurement Uncertainty in Testing", July 2002.
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15 Records
Each d ata package generated fo r a study m ust include a ll supporting inform ation fo r reconstruction o f the data. Inform ation fo r th e data package m ust indude, but is not lim ited to th e follow ing item s: study o r project num ber, sam ple a id standard prep sheets/fecords, instrum ent run log (instrum ent batch records, instrum ent acquisition m ethod, sum m ary pages), instrum ent results files, chrom atogram s, calibration curves, and data c a lc u la tio n s .
16 Affected Documents
N one.
17 Revisions1*
R evision Num ber
1
S um m ary o f C hanges
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 internal 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 w as previously section 10 in ETS-8-044.0. Updated QC criteria to be consistent with method ETS-8-154.4. Section 10 Procedures. This section was previously section 8 (Sample Handling) in ETS-8044.0. Added detail regarding the preparation ofLCSs. 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 w as previously section 11 in ETS8-044.0. 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 ofPFOA/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.
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Record of Deviation/Nonconformance
S tudy / P ro ject N o. G LP 10 -0 1 -0 2 -3 1
1. Identification
D a te (s ) o f O ccurrence: 4 /1 6 /1 2
D ocum ent N um ber: E T S -8 -0 4 4 .1
D eviation typ e
(Check o ne)
SOP
E quipm ent P rocedure 0 M ethod
P rotocol
GPO
O th e r
II. Description (attach extra pages as needed)
M e th o d R e q u ire m e n ts : 1 . L C S reco very w ithin 2 0 % (section 1 3 .4 ). 2 . F M S reco very w ith in 3 0 % (section 1 3 .4 ).
A c tu a l p ro c e d u re /p ro c e s s : 1. T h e low s e t o f L C S s had a n a v e ra g e reco very o f 7 5 .2 % fo r P F O S . 2 . T h e sam pling location D A L G W T W 1 R H S had a P F O S F M S reco very o f 6 5 .8 % .
III. Actions Taken
_______________________________ (such as amendment Issued, S O P revision, e tc .)_________________________________ C o rre c tiv e A c tio n ( Y e s 0 N o ) R e fe re n c e :
A c c e p ta b ility o f th e n o n c o n fo rm in g w o rk : 1 . T h e n on -co m p iian t L C S s w ill b e flag g ed in th e fin a l rep ort. A ll L C S s w e re used in th e d eterm ination o f th e a n a ly tica l m etho d u n certain ty. S in ce th e % b ias w a s less th a n th e c a lcu la te d m etho d u ncertain ty fo r P F O S o f 3 5 % , th e m ethod u ncertain ty d o es not n eed to b e expan ded fu rth er.
2 . T h e sam p ling location w ith a F M S reco very o utsid e m ethod ac c ep tan c e c rite ria w ill b e flag g e d in th e rep ort. S in c e th e a n a ly tica l m ethod u ncertainty w as calcu lated a t 3 5 % , th e u ncertainty fo r D A L G W T W 1 R d oes n o t n eed to b e expanded fu rth er.
A ctions: H alting o f W o rk C lie n t N otificatio n W o rk R ecall W ithholding o f R eport 0 O th er. Deviations will be noted in final report.
P ro je c t L e a d /P A I A p p ro v a l:
D a te :
S tu d y D ire c to r (if G L P ):
S p o n s o r A p p ro v a l (fo r G L P p ro to c o l d e v ia tio n s ): N A T e c h n ic a l R e v ie w e r (o p tio n a l): N A
D a te :
D a te : N A D a te : N A
L a b o ra to ry D e p a rtm e n t M a n a g e r A p p ro v a l:
D a te :
IV. A uthorization to Resum e W ork
When halting of work occurred, resumption of work must first be approved by Laboratory Management
L a b o ra to ry D e p a rtm e n t M a n a g e r A p p ro vai: N A
D a te : N A
Deviation N o ._______________
(assigned by Study D irector o r Team Leader a t the end o f study o r project)
E T S -4 -0 0 8 .7
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D ocum entation o f D eviation s and C ontrol o f N onconform ing T esting
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a
G LP 10-01-01. in terim R ep o rt 31: A n alysis o f PFO A in G roundw ater Sam ples C ollected at O ff-S ite W ells on B ert Jeffries P rop erty in D ecatur. A L in A p ril 2012
Study T itle
A n alysis o f P erilu o ro o ctan o lc A d d (P F O A ) in G ro un dw ater, S oli and S e d im e n t f r th e 3 M D e c a tu r P h a s e 3 S ite -R e la te d M onitoring Program
D ata R equirem ent
E P A T S C A G ood L ab orato ry P ra c tic e S tan d ard s 4 0 C F R P a rt 7 9 2
S tu d y D irector
Jaisim h a K esari P .E ., D E E W esto n Solutions, Inc. 1 4 0 0 W esto n W a y
W est C hester, PA 19380 Phone: 610-701-3761
A uthor
Susan W o lf 3 M E n viro nm ental Laboratory
Interim R eport C om pletion D ate
D a te o f signing
Perform ing Laboratory
3M Environm ental Health and S afety O perations Environm ental Laboratory
3 M C enter. Bldg 2 6 0 -0 5 -N -1 7 S t Paul. M N 5 5 1 44
Project Identification
G L P 10-01-01-31
Total Num ber o f Pages
75
The testing reported herein meet the requirements of ANSU80AEC 17025:2006 "General Requirements for the Competence of Testing and Calibration Laboratories", in accordance with the A2LA Testing Certificate # 2062.01. Testing that complies with this international Standard also meets principles of ISO >001:2000.
Testin g C ert #2052.01
GLP10-01-01; Interim Repot 31 Analysis of PFOA in Groundwater Samples
Bert Jeffries Property - April 2012 This page has been reserved for specific country requirements.
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GLP10-01-01; Interim Report 31 Analysis of PFOA In Groundwater Samples
Bert Jeffries Property April 2012
GLP C o m p lia n c e S tatem ent
Report Title: G LP10-01-01, Interim Report 31. Analysis o f PFO A in Groundwater Sam ples Collected a t the O ff-S ite W ells on Bert Jefferies property in D ecatur, AL in April 2012. Study: Analysis o f Perfluorooctano'c A dd (PFO A ) in Groundwater, Soil and Sedim ent fo r th e 3M D ecatur Phase 3 Site-R elated Monitoring Program . This analytical phase w as conducted in com pliance with Toxic Substances Control A ct (TS C A ) Good Laboratory Practice (G LP) Standards, 4 0 C FR 792, with th e exceptions listed below:
These are environm ental sam ples w here there is no specific test substance, no specific test system and no dosing o f a test system .
The reference substances have not been characterized under the GLPs and the stability under storage conditions at the test site have not been determ ined under GLPs.
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' Bert Jeffries Property-April 2012
Q u a lity A ssu r a n c e Statem ent
Report Tide: G LP 10-01-01, Interim Report 31. Analysis of PFOA in Groundwater Sam ples Collected a t the O ff-S ite W ells on Bert Jeffries property in D ecatur, AL in April 2012.
Study: Analysis o f Perfluorooctanoic Acid (PFO A ) in Groundwater, S o l and Sedim ent fo r the 3M
Decatur Phase 3 Site-R elated Monitoring Program .
'
This report and the accompanying data w ere audited by th e 3M Environm ental Laboratory Q uality Assurance U nit (Q A U ), as indicated below. The findings w ere reported to the principal analytical investigator (P A L ), laboratory m anagem ent and study director.
In sp e ctio n D ates 4/25/12 -4 /2 6 /1 2
Phase D ata and Report
D ata R eported to
T e stin g F a cility M anaoam ent
S tu d y D ire c to r
5 /1 /1 2
5 /1 /1 2
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Table o f C o ntents
G LP C om pliance S tatem ent..................................................................................................................................3 Q uality A ssurance S tatem ent............................................................................................................................... 4 T able o f C on ten ts.....................................................................................................................................................5 List o f Tab les............................................................................................................................................................. 6 1 Study Inform ation.............................................................................................................................................8 2 S um m ary........................................................................................................................................................... 9 3 Introduction......................................................................................................................................................10 4 T est & C ontrol Substances.......................................................................................................................... 10 5 R eference S ubstances.................................................................................................................................11 6 T est S ystem .....................................................................................................................................................12 7 M ethod Sum m ary...........................................................................................................................................12
7.1 M ethods..........................................................................................................................................12
7 2 S am ple C ollection.........................................................................................................................12
7 .3 S am ple P reparation.....................................................................................................................12 7 .4 A nalysis..........................................................................................................................................12 8 A nalytical R esults...........................................................................................................................................14 8.1 C alib ratio n ..................................................................................................................................... 14 8 .2 System S uitability......................................................................................................................... 14 8 .3 Lim it o f Q uantitation (L O Q )....................................................................................................... 14 8 .4 C ontinuing C alib ratio n ................................................................................................................ 14 8 .5 B lanks............................................................................................................................................. 14 8 .6 Lab C ontrol S pikes (L C S s).........................................................................................................15 8 .7 A nalytical M ethod U ncertainty................................................................................................... 16 8 .8 Field M atrix S pikes (F M S )..........................................................................................................16
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9 D ata Sum m ary and Discussion.................................................................................................................. 16 10 C onclusion...................................................................................................................................................... 22 11 D ata/S am ple R eten tio n ............................................................................................................................... 22 12 A ttachm ents.................................................................................................................................................... 22 13 S ignatures....................................................................................................................................................... 23
Lis t o f Ta b l e s
T able 1. Sum m arized PFO A R esults (B ert Jeffries Properly, A pril 2 0 1 2 ).............................................. 9
T able 2. Sam ple D escription Key C ode....................................................................................................... 12
Table 3 . Instrum ent Param eters.....................................................................................................................13 T able 4 . Liquid Chrom atography C onditions............................................................................................... 13 T able 5 . M ass Transitions............................................................................................................................... 13 Table 6 . Lim it o f Q uantitation (L O Q )............................................................................................................. 14 T able 7 . Laboratory C ontrol S pike R ecovery.............................................................................................. 15 Table 8 . A nalytical M ethod U ncertainty........................................................................................................ 16 Table 9 . Field M atrix S pice Levels................................................................................................................. 16 T able 10. JPAL G W M W 1 R 1 2 0 4 0 5 ........................................................................................................... 17 T able 11. JPAL G W M W 3R 1 2 0 4 0 5 ........................................................................................................... 17 Table 12. JPAL G W M W 4 R 1 2 0 4 0 5 ........................................................................................................... 17 T able 13. JPAL G W M W 4L 12 0 4 0 5 ............................................................................................................ 18 T able 14. JPAL G W M W 5R 1 2 0 4 0 5 ........................................................................................................... 18 Table 15. JPAL G W M W 5 L 120405............................................................................................................. 18 T able 16. JPAL G W M W 6R 1 2 0 4 0 5 ............................................................................................................ 19 T able 17. JPAL G W M W 6 L 120405............................................................................................................. 19 T able 18. JPAL G W M W 7R 1 2 0 4 0 5 ............................................................................................................ 19 T able 19. JPAL G W M W 8R 1 2 0 4 0 5 ............................................................................................................ 20 Table 2 0 . JPAL G W M W 9 R 1 2 0 4 0 5 ............................................................................................................ 20
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Bert Jeffries Property - Apri 2012 Table 2 1 . JPAL G W M W 9 L 120405............................................................................................................. 20 Table 2 2 . JPA L G W M W 1 0 R 1 2 0 4 0 5 ..........................................................................................................21 Table 2 3 . JPAL G W M W 11L 120405...........................................................................................................21 Table 2 4 . JPAL G W M W 3R RB 12 0 4 0 5 ......................................................................................................21 Table 2 5 . JPAL G W T R IP 120316 ............................................................................................................... 21
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1 Study Inform ation
Sponsor 3M Com pany Sponsor R epresentative G ary Hohenstein 3M EH S O perations 3M Building 224-5W -03 S aint P aul, M N 55144-1000 P h o n e :(6 5 1 )7 3 7 -3 5 7 0
Study D irector Jaisim ha K esari, P .E ., D EE W eston Solutions, Inc. W est C hester, PA 19380 P h o n e:(6 1 0 )7 0 1 -3 7 6 1 F a x :(6 1 0 )7 0 1 -7 4 0 1 j.kesari@ w estonsolutions.oom Study Location
Testing Facility
3M EH S O perations 3M Environm ental Laboratory Building 260-5N -17 S t P aul, M N 55144 Study Personnel W illiam K . R eag en , P h .D ., 3M Laboratory M an ag er
C leston Lange, P h .D ., Principal A nalytical Investigator, lclaioe@ m m m .com ): phone (651 >-733-9860
Susan W o lf, 3M A nalyst C h elsie G rochow , A nalyst K evin E ich , A nalyst K elly U kes, A nalyst Jonathan S te e g e , A nalyst Study Dates Study Initiation: M arch 8 ,2 0 1 0 Interim R eport 31 E xperin en tal Term ination: A pril 2 1 ,2 0 1 2 Interim R eport Com pletion: D ate o f Interim R eport Signing Location o f A rchives
A ll o rig in al raw d ata and th e an alytical rep o rt h ave b een archived a t th e 3M E nvironm ental Laboratory according to 4 0 C FR P a rt 7 9 2 . T h e te s t substance and an alytical re feren ce standard reserve sam ples a re arch ived a t th e 3M E nvironm ental Laboratory according to 4 0 C F R P a rt 7 9 2
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Bert Jeffries Property - April 2D12
2 Sum mary
T h e 3M Environm ental Laboratory prepared sam ple containers fo r fourteen locations on th e B ert Jeffries property. A to tal o f fo rty-five sam ple bottles w ere received a t th e 3M Environm ental Laboratory fo r perfluorooctanoate (P F O A ) analysis from W eston personnel on A pril 9 ,2 0 1 2 . A ll sam ples w ere logged into th e laboratory inform ation m anagem ent system (U M S ) under project G L P 10-01-01-31.
For each sam pling location, a field sam ple, field duplicate sam ple and field m atrix s p ire (F M S ) sam ple w ere collected. Sam ples also included a trip blank containing M illi-Q TM w ater and an appropriate trip blank s p ire . A single equipm ent rinseate blank w as also collected. T h e equipm ent rinseate blank did not have FM S sam ples prepared fo r determ ination o f PFO A recovery. A ll sam ple bottles w ere fortified w ith internal standard 13C a-PFO A and surrogate recovery standard l3C -PFO A prior to sam ple collection. AH o f th e sam ples w ere prepared and analyzed fo r PFO A and th e surrogate recovery standard 13C *-P FO A , follow ing 3M Environm ental Laboratory M ethod E T S -8 -0 4 4 .1 . W here applicable, sam ples w ere analyzed against an internal standard calibration curve.
T h e average m easured PFO A concentrations a re sum m arized in T a b le 1 . T he trip blank and equipm ent blank sam ples w ere below th e low er lim it o f quantitation (L L O Q ) o f 0 .0 2 4 0 ngfrnL, indicating adequate control o f sam ple contam ination during shipping and sam ple collection. T h e analytical uncertainty fo r PFO A w as estim ated a t 17% .
T a b le 1 . S u m m a rize d P F O A R e s u lts (B e rt J e ffrie s P ro p e rty , A p ril 2 0 1 2 )
A vg. PFOA
R e la tiv e
S am p le ID
C o n cen tratio n
P ercen t
(n g /m L )(1)
D iffe re n c e
JPAL GW M W 1R 120405
1.61 5.6%
JPAL GW M W 3R 120405
7 .8 8
0 .6 3 %
JP A LG W M W 4R 120405
2 .2 4
1.3%
JPAL G W M W 4L 120405
0 .1 6 2
2 .5 %
JPAL GW M W 5R 120405
0 .1 7 4
3 .4 %
JPAL GW M W 5L 120405
0 .8 6 2
4 .8 %
JPAL GW M W 6R 120405
2 .8 6
0 .7 0 %
JPAL GW M W 6L 120405
0203
3 .5 %
JP A LG W M W 7R 120405
826
2 .7 %
JPAL G W M W 8R 120405
0 .3 0 7
1.6%
JPAL GW M W 9R 120405
0 .1 2 4
0 .8 1 %
JPAL G W M W 9L 120405
0 .0248
NATM
JPAL G W M W 10R 120405
0 .5 0 7
2 .6 %
JPAL GW M W 11L 120405
0 .2 9 0
8 .3 %
Trip Blanks (M ilH-QTM W ater)
0 .0 2 4 0
NA
G L P 10-01-01-31 Equipm ent rinseate blank: JPALG W M W 3R
0 .0 2 4 0
NA
NA: not applicable
T h e analytical m ethod uncertainty analyzed by Internal calibration for P FO A is + 17% .
(1 ) A R P D value could not be calculated due to one o f the sam ple replicates having a P F O A result BLOQ.
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: nun iiiuiiii.ii.iu i i i un ill
G LP10-01-01; Interim Report 31 Analysis o f PFOA in Groundwater Samples
Bert Jeffries Property - April 2012
3 Introduction
This analytical study w as conducted as part o f th e Phase 3 Environm ental M onitoring and Assessm ent Program fo r th e 3M facility located in D ecatur, A labam a. T h e objective o f th e overall program is to gain inform ation regarding concentrations o f perfluorooctanoate (P F O A ) in various environm ental m edia such as groundw ater, soils and sedrnents th at are associated w ith and near th e D ecatur facility. This analytical study w as conducted to analyze ground w ater sam ples collected from fo u te e n locations from O ff-S ite W ells on th e B ert Jefferies property in D ecatur, A L fo r PFO A.
T h e 3M Environm ental Laboratory prepared sam ple bottles (2 5 0 m L high-density polyethylene) which w ere shipped to D ecatur, AL W eston personnel prior to field sam pfing. Sam ple bottle sets fo r each sam pfing location included a field sam ple, field sam ple dupficate, and one field spike sam ple. Each em pty container fo r sam pling w as m arked w ith a "fill to here" line to produce a final sam ple volum e o f 200 m L. C ontainers designated fo r field m atrix sam ples w ere fortified w ith an appropriate m atrix spice solution containing PFO A prior to being sent to th e field fo r sam ple co lectio n. A ll sam ple bottles included th e addition o f 13C e-PFO A (interna! standard) a t a nom inal concentration o f 1 n g /riiL and 13C4PFO A (surrogate recovery standard) a t a nom inal concentration o f 0.1 ng/m L. S ee section 8 .8 o f the report fo r field m atrix spice levels.
Sam ples w ere prepared and analyzed according to th e procedure defined in 3M Environm ental Laboratory m ethod E TS -8-044.1 ` M ethod o f A nalysis fo r the D eterm ination o f Perfluorinated Com pounds in W ater by LC /M S /M S ; D irect Injection A nalysis". T h e use o f an internal standard w as used to aid in th e data quality objectives.
T a b le 1 sum m arizes th e average PFO A concentration fo r th e duplicate surface w ater sam ples collected and th e trip blank sam ple. T a b le s 1 0 -2 5 sum m arize the individual sam ple results and the associated FM S recoveries. A ll results fo r th e quality control sam ples prepared and analyzed w ith th e sam ples are reported and discussed elsew here in this rep o rt
4 Tesi & Control Substances
T here w as not a te s t substance o r control substances in th e classic sense o f a G LP study. This study w as purely analytical in nature.
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Bert Jeffries Property - April 2012
5 Reference Substances
T h e analytical reference substances used fo r this study are listed below .
R e fe re n ce S u b sta n ce
Chem ical N am e Chem ical Form ula Id e n tifie r
Use
Source Expiration D ate Storage Conditions Chem ical Lot N um ber TC R Number
PFOA (U near + B ra n ch e ct) P e rflu o ro o d a n o a te
CtF ,5C O O H
CAS # 9 5328-99-7 T arg e t Analyte R eference S ta n d a rd W ettrg to n
03/17 /2 0 1 4
F ro z e n
PFOA (U m a r* B ranched Perfiuorooctanoate
C tF 15C O O C A S # 335-67-1
F M S R eference S ta n d a rd
Sigm a Aldrich 07/27 /2 0 1 6 Am bient
C ^P FO A
P e rflu o ro o d a n o a te 1 3 C 4H F 1 5 Q2 M PFO A
S u rro g a te
W eUngton 1 2 /07 /2 0 1 3
Frozen
TPFOA0311
M KBD4574V
M PFOA1210
T C R 1 1-0009, T C R 11-0042
T C R 11-0029
T C R 1 1-0001
"C rfP F O A
P e rflu o ro o d a n o a te 13C 8 H F ,s0 2
M P F C -C -0112
Internal Standard
W eHngton 01/24 /2 0 1 5
Frozen 012312
TC R 12-0004
Physical Description
Liquid
Powder
Liquid
Liquid
Purity
9 8.3%
9 6 .8 %
>98%
N A (1>
(1) Compound is part of a custom mixtLre of mass-labeled perfluomated compounds at a concentration of 5 0 pgftnL
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Bert Jeffries Property - April 2012
6 Test System
T h e w as not a te s t system fo r this study in th e classic sense o f a G LP study. This study w as conducted fo r analysis o f surface w ater sam ples collected from th e Jeffries property located near D ecatur, AL by W eston Solutions, Inc. personnel. Sam ples fo r this study a re ` real w orld" environm ental sam ples.
T a b le 2 . S a m p le D e s c rip tio n K e y C o d e .
String Number
E x a m p le 1 2 3 4
5
0
Siring Descriptor
Example
J P A L G W M W 1 R 4 -1 2 0 4 0 5
S a m p le L o c a tio n
J P A L - J e tM e a P ro p e rty , A la b a m a
S a m p le Type
ta t-rn wom
juie- n- u. Mn-o-r
G W * G ro u n d W a te r E x a m p le : M W IR
W etLevel
R m R e s id u u m s h a lto w w a to r-b o v in g z o n *
L Dodocfc im lorfrffaffng tw w S - E o tta n t a d d ite w a tu r-b o a h n a to n e
S a m p tn a D a te
1 3 0 4 0 5 - A p r il & 20 1 2
S a m p le T y p e
0 -p rlm a ry s a m p le
D B ~ d u p tc a te s a m p le F M S ~ F ie ld M a trix S p ik e
7 M ethod Sum mary
7.1 Method
A nalysis fo r aH analytes w as com pleted follow ing 3M Environm ental Laboratory m ethod E TS -8-044.1 "M ethod o f Analysts fo r the D eterm ination o f Perfluorinated Com pounds In W ater by H igh Perform ance Liquid Chrom atography/M ass Spectrom etry D irect Injection A nalysis*.
7.2 Sample Collection
Sam ples w ere co lected in 2 5 0 m L N algeneTM (high-density polyethylene) bottles prepared a t th e 3M Environm ental Laboratory. S am ple bottles associated w ith G LP 10-01-01-31 w ere returned to the laboratory a t am bient conditions on A pril 9 ,2 0 1 2 . Sam ples w ere stored refrigerated a t th e laboratory after rec e ip t A set o f laboratory p rep aed Trip Blank and T rip Blank field m atrix spices w ere sent with th e set o f sam ple collection bottles.
7.3 Sample Preparation
Sam ples w ere p re p a e d by rem oving an aliquot o f th e w ell m ixed sam ple and placing it in an autovial fo r a n a ly s is .
During th e preparation o f th e laboratory control sam ples, an aliquot o f a separate internal standard spiking solution w as added to th e laboratory control sam ples (nom inal concentration o f 1 ng/m L). T he sam ples bottles w ere spiked w ith an internal standard m ix a t a nom inal concentration o f 1 ng/m L prior to being sent to th e field fo r sam ple collection.
7.4 Analysis
A ll study sam ples and quality control sam ples w ere analyzed fo r PFO A using high perform ance iq u d chrom atography/ tandem m ass spectrom etry (H P LC /M S /M S ). D etaled instrum ent param eters, the liquid chrom atography gradient program , and th e specific m ass transitions analyzed a re described in the
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Bert Jeffries Property - April 2012
raw data hard copies placed in th e fin al data packet, avid a re briefly described below in T a b le 3 , T a b le 4 and T a b le 5.
T a b le 3 . In s tru m e n t P a ra m e te rs .
Instrum ent Name Analytical M ethod Followed Analysis Date Liquid Chromatograph Guard column Analytical column Injection Volume Msas Spectrometer Ion Source Electrode Polarity Software
ETS Buster ETS-8-044.1
4/18/12 Anient 1100 Belasi C18 (4.6 mm X 100 mm). 5u Belasi C18 (4.6 mm X 100 mm). 5u
50 mL Aopied Biosvstems A H 4000
T u ri Spray Tubo km electrode
Neoative Analyst 1.4.2
T ab le 4. Liquid C hrom atography C onditions.
S te p Num ber
T o ta l T im e (m in )
0 0 .0
1 2 .0
2 14.5 3 15.5 4 16.5 5 2 0 .0
F lo w R a te O i/n d n )
P ercen tA
( 2 m a m m o n iu m acetate)
ETS-8-044.1 Analysis
750 97.0
750 97.0
750 5.0
750 5.0
750 97.0
750 97.0
P ercents
(M e th a n o l)
3.0 3.0 95.0 95.0 3.0 3.0
T able 5. M ass Transitio n s.
A n a ly te PFO A
lC .h P F O A
Mess T ra n s itio n
0 1 /0 3
4 1 3 /369
413019 4 1 3 /1 9 9 4 1 7 /3 7 2
In te rn a l S ta n d a rd ( " C J -P F O A F C J -P F O A
Mass T ra n s itio n 0 1 /0 3
4 2 1 /3 7 6
421/376
Dwel time was 50 msec for each transition The mdwidual transitions were sunned to produce a Total ion chromatoyam" (TIC), which was used tor quantitation
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GLP10-01-01; Interim Report 31 Analysis erf PFOA in Groundwater Samples
Bert Jeffries Property - April 2012
8 A nalytical Results
8.1 Calibration
Sam ples w ere analyzed using a stable isotope internal standard calibration curve. C alibration standards
w ere prepared by spiking known am ounts o f th e stock solution containing P FO A (reference standard containing both lin ear and branched isom ers) into a laboratory-prepared synthetic groundw ater containing calcium and magnesium . A separate internal standard spiking solution w as prepared and an aliquot w as added a t th e sam e level to a ll calibration standards and laboratory control sam ples a t a nom inal concentration o f 1 ng/m L. A calibration curve ranging from approxim ately 0 .0 2 5 ng/m L to 25 ng/m L (0 .0 2 5 ng/m L to 10 ng/m L fo r 13C4-P FO A surrogate) w as prepared. A quadratic, 1/x w eighted, calibration curve o f th e standard peak area ratios w as used to fit the d ata fo r e x h an alyte. T h e data w ere not forced through zero during th e fitting process. C alculating th e standard concentrations using th e peak a re a / peak area ratios and th e resultant calibration curve confirm ed accuracy o f each curve p o in t
Each curve point w as quantitated using to e o v e ra l calibration curve and review ed fo r accuracy. M ethod caHwation accuracy requirem ents o f 100 25% (1 0 0 31% fo r the low est curve point) w ere m et fo r PFO A and 13C rP F O A surrogate. T h e correlation coefficient (r) w as g reater than 0 .9 9 5 fo r both
8.2 System Suitability
A calibration standard w as analyzed four tones a t th e beginning o f th e analytical sequence to dem onstrate overall system suitabifity. T h e acceptance criteria o f less than or equal to 5% relative standard deviation (R S D ) fo r peak a rra and retention tim e criteria c f less than o r equal to 2% R SD w as m et fo r P FO A and ^ C rP F O A surrogate.
8.3 Limit of Quantitation (LOQ)
T h e LO Q fo r th is analysis is th e low est non-zero calibration standard in th e curve th a t m eets Knearity and accuracy requirem ents and fo r which to e a re a counts are a t least tw ice those o f th e appropriate blanks. T h e nom inal LOQ fo r PFO A can be found in T a b le 6 .
T a b le 6 . L im it o f Q u a n tita tio n (L O Q ).
A n a ly s is D a te
4 /1 6 /1 2
PFO A n g /m L
0 .0 24 0
8.4 Continuing Calibration
During th e course o f each analytical sequence, continuing calibration verification sam ples (C C V s) w ere analyzed to confirm th at th e instrum ent response and th e initial calibration curve w ere still in control. A il C C Vs m et m ethod criteria o f 100% 25% fo r PFO A and 13C<-PFO A surrogate.
8.5 Blanks
T hree types o f blanks w ere prepared and analyzed w ith th e sam ples: procedural blanks, trip blanks, and equipm ent rinseate blanks. Procedural blank results w ere review ed and used to evalu ate m ethod
perform ance and to determ ine to e LO Q fo r P FO A . T rip blanks reflect to e shipping and sam ple collection concfitons th e sam ple bottles and sam ples experience. Equipm ent rinseate blanks a re aqueous sam ples th at reflect the efficiency o f equipm ent cleaning in th e field betw een d ifferen t sam ple collections to ensure no cross contam ination erf sam ples from th e equipm ent.
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GLP10-01-01; Interim Report 31 Analysis of PFOA in Groundwater Samples
Bert Jeffries Property - April 2012
8.6 Lab Control Spikes (LCSs)
Low , m id, and high lab control spikes w ere prepared fo r th e target analytes and analyzed in trip licate, w h ie only low and high lab control spikes w ere prepared fo r th e 13C4-P F O A surrogate. LCSs w ere prepared by spiking known am ounts o f th e analyte into 10 m L o f synthetic groundw ater to produce the desired concentration. T h e spiked w ater sam ples w ere then analyzed in th e sam e m anner as th e sam ples. T h e m ethod acceptance criteria, average o f LC S a t each level should be w ithin 100% 20% w ith an R SD s20% , w ere m et fo r both P FO A and 13C4-P F O A surrogate.
T h e foBowing calculations w ere used to generate data in T a b le 7 fo r laboratory control spikes:
L C S P ercen t R eco very = C alcu lated C o ncentration 100%
S p ik e C o ncentration
L C S % R S D = ^ a n d a fd d 9 v ia ti0 n L C S fe p llc a te S *1 0 0 % averag e LC S recovery
T able 7. L ab o rato ry C ontrol S pike R ecovery.
ETS-8-0441 Analyzed 4/16/12
PFOA {L in e a r+ B ra n c h e d )
13C r P F O A s u n r o o a t e
L a b ID
S p ik e d C o n c e n tra tio n
(n g /m L )
C a lc u la te d C o n c e n tra tio n
(n g A n L )
S p ik e d
C o n c e n tra tio n
% R e c o v e ry
(n g /m L )
C a lc u la te d C o n c e n tra tio n
tn g /m L )
X R ecovery
LC S -120416-1 LC S-120416-2 L C S -120416-3 A verage % R SD
0 .1 90 0 .190 0 .1 90
0 .1 86 0 .1 95 0 .1 97 102% 3 .3 %
9 7 .7 103 104
0 .1 98 0 .198 0 .1 98
0 .2 0 7
0 .2 1 2
0 .2 1 6 107% 2 4 %
104 107 109
L C S -120416-4 L C S -120416-5 L C S -120416-6 A verage % R SD
1 .9 0 1 .9 0 1 .9 0
1 .9 4 1 .9 7
2 .0 0
104% 1 .5 %
102
104 105
1 .9 8 1 .9 8 1 .9 8
2 .0 6
2 .1 0 2 .1 2
106% 1 4 %
104 106 107
L C S -120416-7 LC S-120416-8 LC S-120416-9 A verage % R SD
9 .5 2 9 .5 2 9 .5 2
8 .8 5 8 .6 2 8 .8 0 9 2 .0 % 1 .4 %
9 3 .0 9 0 .5 9 2 .4
NA NA NA
NA NA NA NA
NA NA NA
NA = Not applicable
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GLP10-01-01; Interim Report 31 Analysis of PFOA in Groundwater Samples
Bert Jeffries Property-April 2012
8.7 Analytical Method Uncertainty
A nalytical uncertainty is based on historical Q C d ata th at is control charted and used to evaluate m ethod accuracy and precision. T h e m ethod uncertainty is calculated foflow ing E TS -12 -0 1 2 .2 . The standard deviation is calculated fo r th e se t o f accuracy resuits (in % ) obtained fo r the Q C sam ples. T he expanded uncertainty is calculated by m ultiplying th e standard deviation by a factor o f 2 , which corresponds to a confidence level o f 95% .
T a b le 8 . A n a ly tic a l M eth o d U n c e rta in ty .
A n aly te PFOA
M ethod E T S -8-044.1
S ta n d a rd D eviatio n 8 .4 7
M ethod U n c e rta in ty
17%
8.8 Field Matrix Spikes (FMS)
A single field m atrix spike w as collected a t each sam pling point to verify th at th e analytical m ethod is
applicable to th e collected m atrix. T he field m atrix spice w as generated by adding a m easured volum e o f field sam ple to a container spiced by th e laboratory w ith PFO A (reference standard containing both lin ear and branched isom ers) prior to shipping sam pie containers fo r sam ple collection. Field m atrix spike recoveries w ithin m ethod acceptance criteria o f 10030% confirm th at "unknown' com ponents in th e sam ple m atrix do not significantly interfere w ith th e extraction a id analysis o f th e an d ytes o f in terest Field m atrix spice concentrations m ust be 50% o f the sam ple concentration to be considered an appropriate field spike. Field m atrix spikes a re presented in section 9 o f this rep o rt
T a b le 9 . F ie ld M a trix S p ik e L e v e ls .
S am p fln g L ocatio n A il Locations and Trip Blank
P FO A , ngftn L 2.00
I~M*j Rocoironr ^ S a n p te Concentration o f F M S -A v e ra g e C oncentration: R a id S a m p le s Field Sam ple P u p .) 100% Spike Concentratori
8.9 Data Summary and Discussion
T h e tables below sum m arize th e sam ple results and field m atrix spice recoveries fo r th e sam pfing locations as w ell as th e equipm ent rinseate and trip blank sam ples. R esults and average values are rounded to th ree significant figures according to EPA rounding rules. B ecause o f rouncfing, values m ay vary slightly from those listed in th e raw d ata. FiekJ m atrix spice recoveries m eeting th e m ethod acceptance criteria o f 30% , dem onstrate th at th e m ethod w as appropriate fo r th e given m atrix and th eir respective quantitative ranges.
JP A L G W M W 3 R 120405; T h e field m atrix spice level w as not appropriate as com pared to the PFO A concentration in th e sam ple. H ow ever, th e 13C-PFO A surrogate recovery added to a i sam ple bottles m et m ethod acceptance criteria.
JP A L G W M W 7 R 120405; T h e field m atrix spice level w as not appropriate as com pared to th e PFO A concentration in th e sam ple. H ow ever, th e 13C4-P FO A surrogate recovery added to a l sam ple bottles m et m ethod acceptance criteria.
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Bert Jeffries Property - April 2012
Table 10. JPAL GW M W 1R 120405
3 M U M S ID
D e s c rip tio n
G LP10-01-01-31-001 GLP10 0 1 -0 1 -31 -0 0 2 G LP 10-01-01-31 -0 0 3
JP A L -G W -M W 1R -0-120405 JPA L-G W -M W 1R -D B -12 0 405 JP A L -G W -M W 1R -F M S -120405
A v e ra g e C o n c e n tra tio n (n g A n L ) X R P O R S D
N A =NatAppfcaUe
PFO A
13C r f * F O A
C o n c e n tra tio n
fn g A n L )
% R e c e v e ry
1 .5 6 1 .6 5 4 .0 9
NA NA 124
1 .6 1 n g A n L 5 .6 %
% R ecovery
96.1 101 110
1 0 3 * * 7 .0 %
T a b le 1 1 . J P A L G W M W 3 R 12 0 4 0 5
3 M U M S ID
D e s c rip tio n
G LP 10 -0 1 -0 1 -3 1 -0 0 4 G LP10-01-01-31-005 G LP10-01-01-31-006
JP A L -G W -M W 3R -0-120405 JPA L-G W -M W 3R -D B -12 0 405 JP A L -G W -M W 3R -F M S -12 0 405
A v e ra g e C o n c e n tra tio n ( n g /m L ) % R P 0 tR S D
PFO A
13c <-p f o a
C o n c e n tra tio n (n g O n L )
% R e c o v e rv
^R ecovery
7 .9 0 N A 9 8 .6 7 .8 5 NA 94.1 9 .2 3 NC 9 6 .8
7 .8 8 n g A n L 0 .6 3 %
9 6 .5% 2 .4 %
N A = N o tA p p ic a b le NC= Not Calculated; the sample concentration is greaterthan 2x the spite level
T a b le 1 2 . J P A L G W M W 4 R 12 0 4 05
3M U U S D
D e s c rip tio n
G LP 10 -0 1 -0 1 -3 1 -0 0 7 G LP10-01-01-31-008
JP A L-G W -M W 4R -0-120405 JPA L-G W -M W 4R -D B -12 0 405
G LP10-01-01-31-009
JP A L -G W -K M /4R -F M S -12 0 4 05
A verag e C o n c e n tra tio n (n g A n L ) % R P D 7 R S D
N A =N o t Apptcable
PFO A
13c + p f o a
C o n c e n tra tio n
(n g A n L )
% R e c o v e rv
2 .2 2 225 421
NA NA 9 8 .8
2 2 4 n g A n L 1 .3 %
% R ecovery 972 9 8 .7 104
1 0 0 % 3 .7 %
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Bert Jeffries Property - April 2012
Table 13. JPAL GW M W 4L120405
M U M S ID
D e s c rip tio n
GLP10 0 1 -0 1 -31 -0 1 0
JP A L-G W -M W 4L-0-120405
GLP10 01-01-31-011
JP A L-G W -M W 4L-D B -120405
G L P 100101-31012
JP A L -G W -M W 4L-FM S -120405
A verag e C o n c e n tra tio n (n g fm L ) % R P D /R S D
NA = Not Apptcabte
PFO A
13c + p f o a
C o n c e n tra tio n fn g /m L )
% R e c e v e ry
0 .164 0 .160 2.11
NA NA 9 7 .4
0 .1 6 2 n o /m L Z 5 %
^R ecovery
104 100 100 101% 2A %
T a b le 1 4 . J P A L G W M W 5 R 1 2 0 4 0 5
3M U M SK 3
D e s c rip tio n
GLP10 0 1 0 1 -3 1 0 1 3
JPA L-G W -M I/V 5R O -120405
GLP10 0 1 0 1 -3 1 0 1 4 GLP10 0 1 0 1 -3 1 0 1 5
JP A L-G W -W V 5R -D B -120405 JPA L-G W -N N V5R -FM S-12 0 4 05
A v e ra g e C o n c e n tr a tio n frig ftn U H R P D IR S D
N A =N o t Appfecabie
PFO A
13C t - P F O A
C o n c e n tra tio n
(n o /m L )
^R ecovery
% R e c ovary
0 .1 7 1 0 .177 2 .0 8
NA NA 9 5 .3
0 .1 7 4 n o * n L 3 A %
9 8 .7 101 9 9 .6 9 9 .8 % 1 .3 %
T a b le 1 5 . J P A L G W M W 5 L 12 0 4 0 5
3M U M S D
D e s c rip tio n
GLP10 0 1 0 1 -3 1 0 1 6 GLP10 0 1 0 1 -3 1 0 1 7 GLP10 0 1 0 1 -3 1 0 1 8
JPA L-G W 4A /V 5L-0-12 0 4 05 JPA L-G W -M W 5L-O B -12 0 4 0 5 JP A L -G W -M /V 5L-F M S -12 0 4 05
A verag e C o n c e n tra tio n fn g A n U % R P D /R S D
N A = N o tA p p fica N e
PFO A
13C r P F O A
C o n c e n tra tio n
(n g /m L )
% R e c o vary
^ R eco very
0 .882 0 .8 4 1 2 .7 1
NA NA 9 2 .4
98A 9 5 .1 972
0 .8 6 2 n o fa lL 4 J %
9 6 .9 % 1 .7 %
Page 18 of 75
GLP10-01-01; Interim Report 31 Analysis of PFOA in Groundwater Samples
Bert Jeflnes Property-April 2012
Table 16. JPAL GW M W 6R 120405
3 M U M S ID
D e s c rip tio n
G LP10-01-01-31-019 G LP 10-01-01-31-Q 20 G LP 10-01-01-31-021
JP A L -G W -M W 6R -0-120405 JP A L-G W -M W 6R -D B -120405 JP A L -G W -M W 6R -F M S -12 0 405
A verag e C o n c e n tra tio n ( n a t o t i) % R P D /K S D
NA = Not Appicable
PFO A
13C r P F O A
C o n c e n tra tio n
(n a to ti.)
^R ecovery
^R ecovery
2 .8 7 2 .8 5 4 .6 2
NA NA 88.0
96.1 9 7 .6 9 7 .3
Z 8 6 n g to tL iO .7 0 %
9 7 .0 % 0 .8 2 %
T a b le 1 7 . J P A L G W M W 6 L 12 0 4 0 5
3M U M SB 3
D e s c rip tio n
G LP10-01-01-31-022 G LP10-01-01-31-023 GLP10 0 1 -0 1 -31 -0 2 4
JP A L -G W -M W 6L-0-120405 JP A L-G W -M W 6L-D B -12 0405 JP A L-G W -M W 6L-FM S -12 0405
A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D /R S D
NA=Not Appicable
PFOA
13C t P F O A
C o n c e n tra tio n
(n a to iL )
^R ecovery
^R ecovery
0206
0 .199 2 .1 4
NA NA 9 6 .9
9 7 .4 9 4 .0 100
0 .2 0 3 n a to li. 3 .5 %
9 7 .2 % 3 .2 %
T a b le 1 8 . J P A L G W M W 7 R 1 2 0 4 0 5
PFO A
13C r P F O A
3 M U M S ID
D e s c rip tio n
G LP10-01-01-31-025 G LP10-01-01-31-026 G LP10-01-01-31-027
JP A L -G W -M W 7R -0-120405 JPA L-G W -M W 7R -D B -12 0 405 JP A L -G W -M W 7R -F M S -12 0 405
A verag e C o n c e n tra tio n (n g /m L ) % R P D /R S D
C o n c e n tra tio n (n g to tL )
% R e c o v e rv
M R ecovery
8 .3 7 N A 102 8 .1 5 N A 9 5 .9 9 .8 5 N C 9 5 .8
8 .2 6 n g /m L Z 7 %
9 8 .0 % 3 .8 %
NA = NotAppicable NC= Not Calculated; the sample concentration Is greaterthan 2x the spice level
Page 19 of 75
GLP10-01-01; Interim Report 31 Analysis of PFOA in Groundwater Samples
Beri Jeffries Property - Aprii 2012
Table 19. JPAL GW MW8R 120405
3M U M S B
D e s c rip O o n
G LP10-01-01-31-028 G LP10-01-01-31-029 G LP 10-01-01-31-030
JP A L -G W -M W 8R -0-120405 JP A L -G W -M /V 8R -D B -12 0 4 05 JPAL-G W -KA/V8R-FM S-12 0 4 05
A v e n a * C o n c e n tn to n (n g /m L ) % R P D /R S D
NA = NotAppfcable
PFO A
n C *JP F O A
C o n c e n tn to n (n g /m L )
% R e c o v e rv
% R e c o v e ry
0 .304 0 .309 2.22
HA HA
9 5 .7
94.1 9 8 .7 9 8 .4
0 .3 0 7 n & m L 1 .6 %
9 7 .1 % 2 J %
T a b le 2 0 . JP A L G W M W 9 R 1 2 0 4 0 5
3M U M S D
D e s c rtp O o n
G LP 10 0 1 -0 1 -3 1 -0 3 1 G LP10-01-01-31-032 GLP1001-0 1 -31 -0 3 3
JPA L-G W -M W 9R -0-12 0 4 05 JP A L-G W -M W 9R -D B -12 0 405 JP A L-G W -M W 9R -FM S -12 0 405
A v e n a e C o n c e n tn to n ( n g /M .) i % R P D /R S D
N A = N o tA p p ic a U e
PFO A
n C *P F O A
C o n c e n tn to n (n a /m L )
% R e c o v e rv
0 .123 0 .124 2.01
HA HA
9 4 .3
% R eoovenf
9 4 .6 9 6 .5 9 4 .6
0 .1 2 4 n g /m L 0 .8 1 %
9 5 .2 % 1 .2 %
T a b le 2 1 . J P A L G W M W 9 L 1 2 0 4 0 5
3M U M S D
D e s c rtp O o n
G L P 10 -0 1 -0 1 -3 1 -0 3 4 GLP10 0 1 -0 1 -31 -0 3 5 GLP10 0 1 -0 1 -31 -0 3 6
JP A L-G W -M W 9L-0-12 0 405 JPA L-G W -M W 9L-D B -120405 JPA L-G W -M W 9L-FM S-12 0 4 05
A v e n g e C o n c e n tn to n (n g ftrtL ) % R P D /R S D
NA = NotAppicaHe
PFO A
n C rP F O A
C o n c e n tn to n (n g /m L )
% R e c o v e rv
% R e c o v e rv
0 .0 24 8 < 0 .02 4 0
1 .8 7
HA HA
9 2 .3
9 7 .8 9 8 .8 9 7 .1
0 .0 2 4 8 n g /m L
9 7 .9 % 0 .8 7 %
Page 20 of 75
GLP10-01-01; Interim Report 31 Analysis of PFOA in Groundwater Samples
Bert Jeffries Property - April 2012
Table 22. JPAL GW M W 10R 120405
3M LM S D
D e s c rip tio n
G LP10-01-01-31-037 G L P 10 -0 1 -0 1 -3 1 -0 3 8 GLP1001-0 1 -31 -0 3 9
JP A L -G W -M W 10R -0-120405 JP A L -G W -M W 10R -D B -120405 JP A L -G W -M W 10R -F M S -120405
A verag e C o n c e n tra tio n (n g /m L ) % R P Q (R S D
NA=Not Applicable
PFO A
n C *P F O A
C o n c e n tra tio n
(n g /m L )
X R ecovery
X R ecovery
0 .513 0 .500 2 .3 7
NA NA 9 3 .2
982 9 2 .4 9 3 .3
0 .5 0 7 n g /m L 2 .6%
9 4 .6 X 1 3 .3 X
T a b le 2 3 . J P A L G W M W 1 1 L 12 0 4 0 5
3M UM SJD
D e s c rip tio n
G L P 1001-01-31-040 G LP10 01-01-31-041 G L P 10 -0 1 -0 1 -3 1 -0 4 2
JP A L-G W -M W 11L-0-120405 JP A L-G W -M W 11L-D B -12 0 405 JP A L-G W -M W 11L-FM S -120405
A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D /R S D
PFO A
13C r P F O A
C o n c e n tra tio n
(n g /m U
X R ecovery
X R ecovery
0 .302
NA
0278
NA
2 .1 9
9 5 .0
0 .2 9 0 n g /m L 1 & 3 X
9 8 .8 9 7 .5 9 9 .0
9 8 .4 % 0 .8 3 %
NA = NotAppicaUe
T a b le 2 4 . JP A L G W M W 3R R B 12 0 4 0 5
3M U M S K )
G LP10-01-01-31-043
D e s c rip tio n
JP A L -G W -M /V 3R -R B -120405
PFO A
C o n c e n tra tio n (n g /tn L )
< 0 .02 4 0
13c * p f o a
R e c o v e ry
9 7 .8
T a b le 2 5 . JP A L G W T R IP 1 2 0 3 1 6
3M U M S K )
G LP10-01-01-31-044 GLP10 0 1 -0 1 -31 -0 4 5
NA =N otA ppicaH e
D e s c rip tio n
JP A L -G W -T R IP 01-0-120316 JPA L-G W -TR IP01 -F M S -1 2 0 3 16
PFO A
13C * - P F O A
C o n c e n tra tio n
(n o /m L )
X R ecovery
< 0 .02 4 0 1 .9 2
NA 9 6 .0
X R ecovery 9 8 .0 9 4 .9
Page 21 of 75
GLP10-01-01; interim Report 31 Analysis of PFOA in Groundwater Samples
Bert Jeffries Property - April 2012
9 Conclusion
Laboratory control sp ires and field m atrix sp ires w ere used to determ ine th e analytical m ethod accuracy and precision fo r PFO A . A nalysis w as successfully com pleted follow ing 3M Environm ental Laboratory m ethod E T S -8-044.1 described herein.
10 Data/Sam ple Retention
AJ rem aining sam ples and associated project data (hardcopy and electronic) w ill be archived according to 3M Environm ental Laboratory standard operating procedures.
11 Attachm ents
A ttachm ent A : Protocol Am endm ent 31 (G eneral P roject O utline) A ttachm ent B: R epresentative Chrom atogram s and C alibration Curves A ttachm ent C : A nalytical M ethod - E TS -8-044.1
Page 22 of 75
G IP10-01-01; Interim Report 31 Analysis of PFQA in Groundwater Samples
Bert Jeffries Property - April 2012
a12 Signatures . Clesion Lange, P h.D ., 3M Principal A nalytical Investigator
D ate
W iKam K. R eagen, P h.D ., 3M Environm ental Laboratory M anager
D ate
Page 23 of 75
Attachment A : Protocol A m endment
GLP10-01-01; Interim Repot 31 Analysis of PFOA in Groundwater Samples
Bert Jeffries Property - April 2012
Page 24 of 75
GLP10-01-01; Interim Report 31 Analysis of PFOA in Groundwater Samples
r-April 2012
Amendment 31
Study Title Analysis of Perfluorooctanoic Add (PFOA) in Groundwater, Soil and Sediment for the
3M Decatur Phase 3 Site-Related Monitoring Program
PROTOCOL AMENDMENT NO. 31
Am endm ent Date: March 22, 2012
Perform ing Laboratory 3M Environmental, Health, and Safety Operations
3M Environmental Laboratory Building 260-5N-17
Maplewood, MN 55144-1000
Laboratory P roject Identification GLP10-01-01
Sam pling Event Off-Site Wells - Bert Jeffries Property
Pagel of 6 Page 25 of 75
GLP10-01-01; Interim R ep o t 31
20,2Analysis of PFOA in Groundwater Samples
M alylksl P r o t o g f S & f f m i Amendment 31
This amendment modifies the following portion of protocol: "Analysis of Perfluorooctanoic Acid (PFOA) in Groundwater, Soil and Sediment for the
3M Decatur Phase 3 Site-Related Monitoring Program"
Protocol reads: No changes to the wording of the protocol are required. Amend to read: No changes to the wording of the protocol a re required. This am endm ent only addresses and docum ents the addition o f th e G en eral Project O utline (G P O ) for the collection and analysis o f groundw ater sam ples as part o f the 3M D ecatu r P hase 3 Program for P FO A (G LP 10-01 -0 1 ). T h e anticipated sam ple collection w ill occur around th e tim efram e o f th e w eek of M arch 2 6 ,2 0 1 2 . T h e groundw ater sam ples for this sam pling even t w ill b e entered into th e 3M Environm ental Laboratory L IM S as project G L P 10-01-01-31 and reported as interim report G L P 1 0 -0 1 -0 1 -3 1 , (reflecting study G L P 10-01-01 and am endm ent -3 1 ).
Reason: T he reason for this am endm ent is to docum ent the G eneral Project O utline (G P O ) which describes the anticipate groundw ater sam ple collection even t for fourteen off-site w ells a t th e Bert Jeffries Property. The G PO is three pages in length and included as attached to this am endm ent form.
Page 2 of 6 Page 26 of 75
GLP10-01-01; Interim Report 31 Analysis of PFOA in Groundwater Samples
-April 2012
Amendment 31
Amendment Approval
-------
W iliam Reagen, EHS Opns Environmental Lab M anagem ent
(A '
Jaisimha Kesari P .E ., D EE, Study Director
D ate
3 mDate\ ^
Page 3 o f 6
Page 27 of75
J I I _ 1.M 1B K .1J W : b u h I. l i n a i .
GLP10-01-01; Interim Report 31
Protjsmsm, 20,2Analysis of PFOA in Groundwater Samples -^ Amendment 31
Environmental Health & Safety Operations, Environmental Laboratory General Project Outline
To: From : cc:
D a te : S u b je c t:
G ary Hohenstein, 3M EHS&Opns
Susan W olf, 3M EHS&Opns; Environmental Lab W illiam R eagen, 3M EHS&Opns; Environmental Lab Cleston Lange, 3M EHS&Opns; Environmental Lab
Jai Kesari, W eston Solutions March 2 2 ,2 0 1 2 A nalysis o f Perfluorooctanoic Acid (P F O A ) in G roundw ater, S oil and S edim ent fo r the 3M D ecatur P hase 3 S ite-R elated M onitoring Program ; G LP Interim R eport 31; O ff-S ite W eils B ert Jeffries Property
1 General Project Information
C ontacts
Lab Request Num ber S ix D ig it Departm ent Num ber Project Schedule/Teet Dates
3M Sponsor Representative Gary Hohenstein 3M EHS Operations 3M Building 224-5W -03 Saint Paul, M N 55144-1000 Phone: (651) 737-3570 qahohensteinO m m m .com
3M Environm ental Laboratory M anagem ent William K. Reagen 3M EHS Opns, Environmental Laboratory 2 6 0 -5 N -1 7 651 733-9739 wkreaaenraimmm.com
P rincipal A nalytical investigator Cleston Lange 3M EHS Opns, Environmental Laboratory 2 6 0 -5 N -1 7 651 733-9860 cdanae@ mmm.com
Sam pling C oordinator Timothy Frmak Weston Solutions Tim othv.frinak@ w estonsolutions.com Phone: (334)-332-9123
QLP10-01 -01-31
Dept #530711, Project #0022674449
Sampling scheduled for the week o f March 2 6 ,2 0 1 2
All verbal and written correspondence will be directed to Gary Hohenstein and Jai Kesari.
Page 4 o f 6 Page 28 of 75
GLP10-01-01; Interim Report 31 Analysis o f PFOA in Groundwater Samples
April 2012
Amendment 31
2 Background Information and Project Objective(s)
The 3M E H S O perations Laboratory (3M Environm ental Lab) w ill receive and an alyze groundw ater sam ples collected from fourteen sam pling locations fo r Perfluorooctanoic A cid (P F O A ) from w ells located on th e B ert Jeffries property. A nalyses will b e conducted under the G L P requirem ents o f E PA T S C A Good Laboratory P ractice S tandards 4 0 C FR 792. G roundw ater sam ples w ill be collected by W eston Solutions personnel th e w eek o f M arch 2 6 . 2 0 1 2 . The 3M Environm ental Laboratory w ill prepare th e sam ple bottles with all required spikes to ensure that results for P FO A a re of a known precision and accuracy. T h e final report w ill be subm itted to G ary H ohenstein and Jai K esari upon com pletion under interim report G L P 1 0 -0 1 -0 1 -3 1 .
3 Project Schedule
Sam ple collection bottles will be prepared by 3M Environmental Laboratory for sampling the w eek of March 26, 2012. Sam ple bottles will be shipped in coolers overnight to 3M Decatur for arrival on Friday, March 2 3 ,2 0 1 2 . Sam ple bottles should be stored refrigerated on-site until sam ple collection. M artin Sm ith \ W eston T railer 3M D ecatur P lant 1400 S tate Docks Road D ecatur, A labam a 35601
4 Tost Parameters
The targeted limit of quantitation will be 0.025 ng/mL (ppb) for P FO A
Fourteen sampling locations have been specified. For each sampling location, a total o f three sam ple bottles will be collected (sam ple, sam ple duplicate and 2 ng/mL field matrix spike). T h e "fill to here" line on each 250 mL Nalgene bottle will be 200 mL. O ne set o f trip blanks consisting o f reagent-grade w ater as well as a trip blank spike a t 2 ng/m L will be prepared at the 3M Environmental Laboratory and sent to the sampKng location with the other bottles. All sam ple bottles will include the addition of 13C8-P FO A (internal standard) at a nominal concentration of 1 ng/mL. All sam ple bottles will also include the addition o f 13G ,-P F O A (surrogate spike) at a nominal concentration of 0.1 n g/m L O ne additional bottle will be prepared to be used fo r the preparation o f the equipm ent rinseate blank. A 500-m L bottle of laboratory reagent w ater will be sent with the sam ple bottles to be used to generate the rinseate blank sample.
5 Test Methods
Sam ples will be prepared and analyzed by LC /M S/M S following E TS -6-044.1 "Method o f Analysis for the Determination of Perfluorinated Compounds In W ater by LC/M S/M S; D irect Injection Analysis". The data quality objectives for these studies are quantitative results for the target analytes with an analytical accuracy of 10030% . Field matrix spikes not yielding recoveries within 10030% will be addressed in the report and the final accuracy statem ent m ay be adjusted accordingly. W here applicable, sam ples will be analyzed against an internal standard calibration curve. Each cuive point will contain isotopically-labeled perfluorocarboxylic adds and perfluorosuttonic ad d s a t a nom inal concentration of 1 ng/mL. The calibration curve will be generated by taking the ratio of the standard peak area counts over the internal standard peak area counts to fit the data for each analyte.
Page5of 6
Page 29 of 75
| rv " r"* rr"
* m f - i uw*v"' "'TTnr,
G LP1W )1-01; Interim Report 31 Analysis o f P F O A in Groundwater Samples
Analytical Protocol?
April 2012
Amendment 31
6 Reporting Requirements
For each sampling location, the report will contain the results for the sample, sam ple duplicate, and field matrix spike. Trip blank and trip blank spike will be reported for the sampling event as will any equipm ent/rinseate blanks prepared in the field. Laboratory control spikes of reagent w ater prepared a t the tim e of sam ple extraction will also be reported and used to evaluate the overall method accuracy and precision. Method blanks o f reagent w ater prepared at the tim e of sam ple extraction will be used to determ ine the method detection fim il
Page 6 of 6 Page 30 of 75
GLP10-01-01; Intarim Report 31 Analysis of PFOA in Groundwater Samples
Bert Jeffries Property - April 2012
A t t a c h m e n t B : R e p r e s e n t a t iv e S a m p l e C h r o m a t o g r a m s a n d C a l ib r a t io n C u r v e (s )
Page 31 of 75
Workstation: ETSBUSTER
GLP10-01-01; Interim Report 31 Analysis of PFQA in Groundwater Samples
Bert Jeflfies Property - April 2012
Batch Name: ,bl20418a.dab
Printing Tine: 12:45:05 PM Printing Date: Monday, April 23, 2012
Page 32 of 75
Workstation: ETSBDSTER
GLP10-01-01; Interim Report 31 Analysis of PFQA In Groundwater Samples
Bert Jeffries Property - April >12
Batch Name: b!20418a.dab
Printing Time: 12:44:49 PM Printing Date: Monday, April 23, 2012
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GLP10-01-01; Interim Report 31 Analysis of PFOA in Groundwater Samples
Bert Jeffries Property - April 2012
Batch Name: b!204l8a.dab
Printing Time: 1:01:30 PM Printing Date: Thursday, May 03 2012
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Bert Jeffries Property -April 2012
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Bert Jeffries Property - April 2012
Batch Name: b!204l8a.dab
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Bert Jeffries Properly - April 2012
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Bert Jeffries Property - April 2012
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Bert Jeffries Property - April 2012
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Bert Jeffries Property -April 2012
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P a g e 7 of 19
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Bert Jeffries Property - April 2012
Batch Name*. b!20418a.dab
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Bert Jeflfies Property - April 2012
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A t t a c h m e n t C : A n a l y t ic a l M e t h o d (s )
GLP10-01-01; Interim Report 31 Analysis of PFOA in Groundwater Samples
Bert Jeffries Property - April 2012
Page 53 of 75
..........IllIill! I M il l Hil I . 11! 1 Li 1111111111111Hi111 1J--Llill 111
GLP10-01-01; Interim Report 31 Analysis of PFOA in Groundwater Samples
Bert Jeffries Property - April 2012
3M Environmental Laboratory
M ethod Method o f Analysis for die Determination o f Perfluorinated Compounds in Water
by LC/MS/MS; Direct Injection Analysis M ethod Num ber: ETS-8-044.1 Adoption Date: 4/12/07 , Effective Date: / i j f / i i
Approved By:
W iliam K. Reagen, Technical Director, Environmental Laboratory
Y / J cris O / / Data
ETS-8-344.1
Page 1 of 22
Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct
Injection A nalysis
Page 54 of 75
GLP10-01-01; Interim Report 31 Analysis of PFOA in Groundwater Samples
Bert Jeffries Property - April 2012
1 Scope and Application
This method describes the direct injection analysis of perfluorinated compounds (P FC s) from w ater m atrices using high-performance liquid chromatography tandem m ass spectrometry (H P LC /M S /M S ). T h e method is generally applicable but not limited to the m easurem ent of perfluoroafcyl sulfonamides and perfluorinated alkyl ad ds (PFAA s) such as perfluorosulfbnic ad ds (PFSA s) and perfluorocarboxyiic ad ds (P FC A s) (Table 1). W ater sam ples containing heavy particulate m ay require preparation by an alternate method such as E TS -8-154 ` Determ ination of Perfluorinated A dds, Alcohols, Am ides, and Sulfonates In W ater By Solid Phase Extraction and High Perform ance Liquid Chrom atography/M ass Spectrometry". The method is applicable to both external standard and ritem al standard calibration1.
T a b le 1. R e p re s en tativ e T a rg e t A n alytes
A cro n ym
PFBA (C 4 A dd) PFPaA (C 5 A rid) PFHxA (C 6 A rid) PFHpA (C 7 A rid) PFOA (C 8 A rid) P F N A (C 9A rid ) PFOA (C 10 A rid ) PFUnA (C11 A rid) PFDoA (C 12 A rid) PFTiDA (C 13 Acid) PFBS (C 4 Sulfonate) PFHS (C 6 Sulfonate) P F O S (C 8 Sulfonate) FBSA (C 4 Sulfonamide FOSA (C 8 Sulfonamide)
A n a ly te
Perfluorobutanoic arid Peifluoropentanoic arid Perfluorohexanoic acid Perfluoroheptanotc arid Perthmooctenoic arid Petfluorononanoic arid Perfluorodecanoic acid Perffooroundecartoic add Petfluorododecanoic arid Pertkjorotridecanoic arid Perffoorobutanesulfonic acid Perfluorohexanesiifonic acid Periluoroodanesuffonic arid PerfluorobutenesuHbnamide Pefluorooctanesulfonamide
C h e m ic a l A b s tr a c t S e rv ic e s R e g is try N u m b e r (C A S R N )
375-22-4 2 7 0 6 -9 0 -3 307-24-4 3 7 5 -8 5 -9 335-67-1 375-95-1 3 3 5 -7 6 -2 2 0 5 6 -9 4 -8 307-55-1 72629-94-8 3 7 5 -7 3 -5 3 5 5 -4 6 4 1763-23-1 30334-69-1 7 5 4 -9 1 -6
The Minimum Reporting Level (M R L) is the Limit o f Quantitation (LO Q ) that m eets Data Quality Objectives (D Q O s) that are developed based on the intended use o f this method.
Method Flexibility - This is a perform ance-based method and m ay be generally applied to the determ ination o f perfluorinated compounds in w ater m atrices when analysis batch quality control (Q C ) criteria are m et12. Each set o f sam ples are prepared in an analysis batch with calibration standards, LCSs, blanks, and continuing calibration check standards analyzed on the sam e nstrunent during a tim e period that begins and ends with the analysis o f the appropriate continuing calibration check standards. T he laboratory is permitted to m odfy the LC column, mobile phase composition, LC conditions, and M S /M S condrtions. Method modifications should be considered to improve method perform ance or to m eet data quality objectives for the study. In all cases where method modifications are im plem ented, the batch
1The method is supported by validation with internal standard calibration for C4-C13 PFCAs, C4, C6. and C8 FFSAs, and C8 perfluaroalkane sulfonamide in laboratory control samples under 3M method validation E ll-0667. M2MGeeutthhidooaddnsVcoeafflAiodrnaeatisloytansbi''sl,ibisnh.)iSnEugPpmApoeMrthteootdhf PoQdrCe5-r3Ce7gr,iitasetnrriadatcibo.a)nsEeDudarootanpReaae.n)qFuCDiroeAmmmMeniastssyiof2on0r:0AG1,nu"nidGeaxunIicdIea(nfPocarerGtfAoer,nIsenerdacuttiisnotgnrya4,n)BdainoRdaenApaolnyrnttiiencxgaHl I (Part A,section 5) o f Directive 91/414, SANCO/3029/99 rev. 4 (11/07/00).
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analytical Q C s (section 9 ) m ust be completed and pass Q C acceptance criteria (section 13) if the data from the analytical batch are to be reported.
2 Method Summary
W ater sam ples are analyzed as neat aqueous sam ple or as solvent diluted aqueous sam ples by direct injection using LC /M S /M S . Sam ples containing heavy particulate m ay not be suitable for analysis by this method. Sam ples containing suspended particulate should be centrifuged or titered prior to removing a sam ple aliquot or diluting with solvent T he w ater sam ple is m ixed well prior to removing an aliquot or dluting, if necessary, with A S TM Type I w ater, H PLC w ater, other suitable w ater, or solvent (m ethanol). Quantitation is by stable isotope internal standard calibration in laboratory reagent w ater. All perftuorinated compounds (P FC s) target analyte concentrations o f perfluorosulfonic adds (P F S A s)an d perfkjorocarboxyiic ad ds (P FC A s) are reported as anions and corrected for their salt o r free ad d form s. Alternatively, quantitation m ay be perform ed by externa! standard calibration.
This is a perform ance-based method. Method uncertainty for each target analyte is determ ined for each analytical batch using multiple laboratory control spikes a t multfole concentrations. This method also requires that the precision and accuracy for each sam ple be determ ined using field matrix spikes to verify that the method is applicable to each sam ple m alrix. Caiforation standards fo r PFUnA, PFDoA, PFTrOA, and FO SA have been found to be unstable for m ore than 2 days in 100% w ater. Sam ples requiring analysis for these compounds by this method should be diu ted 1:1 with methanol and analyzed against a caiforation curve prepared in 1:1 synthetic groundw aterM eO H.
3 Definitions
3.1 Analysis Batch
A set o f study sam ples that are prepared with caiforation standards, laboratory control sam ples, and procedural blanks, and analyzed on the sam e instrument during a tim e period that begins and ends with the analysis o f the appropriate continutog caiforation check standards.
3.2 Analytical Sample
A portion o f a laboratory sam ple prepared for analysis.
3.3 Calibration Standard
A solution prepared by spicing a known volum e o f the W orking Standard (W S ) into a predeterm ined am ount o f A STM Type I, H PLC grade w ater, or other suitable w ater (i.e. matrix w ater), and analyzed accordng to this method. Calibration standards are used to calforate the instrument response with respect to analyte concentration.
3.4 Laboratory Duplicate Sample (LDS, or Lab Dup)
A laboratory duplicate sam ple is a separate aliquot o f a sam ple taken in the analytical laboratory th at is analyzed separately with identical procedures. Analysis o f LDSs compared to that o f the first afiquot give a m easure o f the precision associated with laboratory procedures, but not with sam ple collection, preservation, or storage procedures.
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3.5 Field Blank (FB)/Trip Blank (TB)
A STM Type I, H PLC spade w ater, o r other suitable w ater, placed in a sam ple container in the laboratory and treated as a sam ple in a ll respects, including exposure to sam pling site conditions, storage, preservation and a ll analytical procedures. T he purpose o f th e TB is to determ ine if test substances or other interferences are present in th e field environm ent. This sam ple is also referred to as a T rip Blank.
3.6 Field Duplicate Sample (FDS, Field Dup)
A sam ple collected in duplicate a t th e s a n e tin e from th e sam e location as th e sam ple. T he FD S is handled under identical circum stances and treated exactly th e s a n e throughout field and laboratory procedures. A nalysis o f th e FD S com pared to th at o f th e firs t sam ple gives a m easure o f th e precision associated w ith sam ple coflection, preservation and storage, as w ell as w ith laboratory procedures.
3.7 Field Matrix Spike (FMS)
A sam ple to which known quantities o f th e targ et analytes, IS s and SR Ss a re added to th e sam ple bottle in th e laboratory before the bottles are sent to th e field fo r collection o f aqueous sam ples. A known, specific volum e o f sam ple m ust be added to th e sam ple container w ithout rinsing. This m ay be accom plished by m aking a T ito this level" line on th e outside o f th e sam ple container. T h e FM S is analyzed to ascertain if any m atrix effects, interferences, o r stability issues m ay com plicate th e interpretation o f th e sam ple analysis.
3.8 Trip Blank Matrix Spike (TBMS)
An aliquot o f A STM Type I, H PLC grade w ater, or other suitable w ater, to which known quantities o f the targ et analytes, IS s and SR Ss are added in th e laboratory prior to th e shipm ent o f th e collection bottles. T he TB M S is analyzed exactly Ik e a study sam ple to help determ ine if th e m ethod is in control and w hether a loss o f analyte o r analytical bias could be attributed to sam ple holding tim e, sam ple storage and/or shipm ent issues. A low and high TB M S are appropriate w hen expected sam ple concentrations are not known or m ay vary.
3.9 Internal Standard (IS)
A com pound added to each study sam ple, calibration standard, laboratory control sam ples, and procedural blanks a t a consistent level (typically around 1 ng/m L). T he internal standardfs) a re stable isotope labeled versions o f th e targ et analytes. T h e area count ratio o f th e targ et an alyte to th e internal standard is used fo r calibration. Surrogate IS s are applied when stable isotope IS s o f targ et analytes are unavailable. A surrogate IS is not necessarily a stable isotope labeled version o f th e targ et analyte, but is treated as an internal standard fo r q u a n tita tio n .
3.10 Laboratory Control Sample (LCS)
An aliquot o f control m atrix to which known quantities o fth e targ et analytes, IS s and SR Ss (w hen applicable) are added in th e laboratory a t th e tone when sam ples a re aliquotted. A t least th ree levels (tw o levels fo r S R S s) in triplicate are included, one generally a t th e tow end o f the calibration curve and one n ear th e m id range and th e upper end o f th e curve. The LC Ss a re analyzed exactly like a laboratory sam ple to determ ine w hether th e stability o f the standards. LCSs should be prepared each day sam ples a re aliquoted.
3.11 Laboratory Matrix Spike (LMS)
A laboratory m atrix spike is an aliquot o f a sam ple to which known quantities o f target analytes, IS s and S R S s (w hen applicable) are added in th e laboratory. T he LM S is analyzed exactly like a laboratory sam ple to determ ine w hether th e sam ple m atrix contributes bias to th e analytical results. T he endogenous concentrations o f th e analytes in th e sam ple m atrix m ust be determ ined in a sep arate aliquot and th e m easured values in the LM S corrected fo r these concentrations. LM Ss are optional fo r analysis o f aqueous sam ples.
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3.12 Laboratory Sample
A portion o r aliquot o f a sam ple received from the field fo r testing.
3.13 Limit of Quantitation (LOQ)
T h e low er lim it o f quantitation (LLO Q ) fo r an analytical batch is th e low est concentration that can be reliably quantitated w ithin th e specified lim its o f precision and accuracy. T h e LLO Q is generally selected as th e low est non-zero standard in th e calibration curve th at m eets m ethod acceptance criteria. T h e LLO Q fo r each targ et analyte is established fo r each analysis batch as the low est calb ratio n standard w ith area counts a t least tw ice th at o f th e average area counts o f th e procedural blanks.
T h e upper lim it o f quantitation (U L O Q ) fo r an analytical batch is th e highest concentration th at can be reliably quantitated w ithin th e specified lim its o f precision and accuracy. T h e highest standard in th e c a lix a tio n curve th at m eets m ethod acceptance criteria is defined as th e U LO Q .
3.14 Method/Procedural Blank
An aliquot o f control m atrix th at is treated exactly fike a laboratory sam ple including exposure to a ll glassw are, equipm ent, solvents, and reagents th at are used w ith other laboratory sam ples. T h e m ethod blank is used to determ ine if te s t substances o r other interferences are present in th e laboratory environm ent, the reagents, or th e apparatus.
3.15 Sample
A sam ple is an aliquot rem oved from a larger quantity o f m aterial intended to represent the original source m aterial.
3.16 Stock Standard Solution (SSS)
A concentrated solution o f a single-analyte prepared in th e laboratory w ith an assayed reference com pound.
3.17 Surrogate Internal Standard
An IS th at is not necessarily a stable isotopically labeled targ et analyte, but is treated as an internal standard fo r quantitation. Surrogate IS s are used w hen isotopicaiy labeled counterparts o fth e target analyte are not com m ercially o r readily a v a ia b le .
3.18 Surrogate Recovery Standard (SRS)
An isotopicaily labeled standard, not used as an internal standard, th at is added to each sam ple and appropriate Q C sam ple as a m eans to evalu ate th e m ethod perform ance fo r a chem ical class o f com pounds (e .g ., PFSA s, PFC A s).
3.19 Working Standard (WS)
A solution o f several analytes prepared in th e laboratory from S S S s and diluted as needed to prepare cafibration standards and other required analyte solutions.
4 Warnings and Cautions
___ _____ ______
4.1 Health and Safety
T h e acute and chronic toxicity o f the standards fo r this m ethod have not been precisely determ ined; how ever, each should be treated as a potential health hazard. T he analyst should w ear gloves, a lab co at, and safety glasses to prevent exposure to chem icals th at m ight b e p resen t
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T he laboratory is responsbie fo r m aintaining a safe w ork environm ent and a current aw areness o f local regulations regarding th e handling o f the chem icals used in this m ethod. A reference file o f m aterial safety d ata sheets (M S D S ) should be availab le to a ll personnel involved in these analyses.
4.2 Cautions
T he analyst m ust be fam iliar w ith th e laboratory equipm ent and potential hazards including, but not lim ited to , th e use o f solvents, pressurized gas and solvent lin es, high voltage, and vacuum system s. R efer to th e appropriate equipm ent procedure o r operator m anual fo r additional inform ation and cautions.
5 Interferences
During sam ple preparation and analysis, m ajor potential contam inant sources are reagents and glassw are. A ll m aterials used in th e analyses shall be dem onstrated to be fre e from interferences under conditions o f analysis by running m ethod blanks.
P arts and supplies th at contain Teflon should be avoided o r m inim ized due to th e possibility o f interference and/or contam ination. These m ay include, but are not lim ited to: w ash bottles, Teflon lined caps, autovial caps, H PLC parts, etc.
T h e use o f disposable m icropipettes or pipettes to aliquot standard solutions is recom m ended to m ake calibration standards and m atrix spikes.
6 Instrumentation, Supplies, and Materials
6.1 Instrumentation
A nalytical balance capable o f reading to 0.0001g H P LC /M S /M S or H PLC /M S system , as described in Section 10.
6.2 Supplies and Materials
S am ple collection bottles-- H D P E (e .g ., N algeneTM ) w ide-m outh bottles w ith screw cap. N o te: D o not use fluorinated o r Teflo n bottles o r Ikied caps. C oolers o r boxes fo r sam ple shipm ent. 15-m L and 50-m L disposable polypropylene centrifuge tubes. C lass A pipettes and volum etric flasks, various. 2 m L H PLC autovials Disposable pipettes, polypropylene or glass as appropriate C entrifuge capable o f spinning 15-m L and 50-m L polypropylene tubes a t 3000 rpm .
7 Reagents and Standards
N o te: Suppliers and catalog num bers a re fo r illustrative purposes only. Equivalent perform ance m ay be achieved using chem icals obtained from other suppliers. D o not use a lesser grade o f chem ical than those listed.
7.1 Chemicals
W ater - M ilB-Q, H PLC g rad e, or other suitably appropriate sources
Calcium A cetate - A .C .S . R eagent G rade
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M agnesium A cetate - A .C .S . R eagent G rade M ethanol - H PLC grade Am m onium A cetate - A .C .S . R eagent G rade
7.2 Representative Target Analytes, ISs, and SRSs
PFB A , H eptafluorobutyric A d d , (C 4 Perfluorinated A dd ) P FP eA , Nonafluoropentanoic A dd (Cs Perfluorinated A d d ) PFH xA , Perfluorohexanoic A dd (Ce Perfluorinated A dd ) PFH pA , Tridecafluoroheptanoic A dd, (C 7 Perfluorinated A dd ) PFO A , Am m onium perfluoroodanoate, (Cs Perfluorinated A dd ) PFN A , H eptadecafluorononanoic A dd , (Cg Perfluorinated A dd) PFD A , N onadecafluorodecanoic A dd (C 10 Perfluorinated A dd ) PFU nA , Perfluoroundecanoic A dd , (C n Perfluorinated A d d ) PFD oA , Perfluorododecanoic A dd , (C i2 Perfluorinated A dd ) PFTrO A , Perfluorotridecanoic A dd , (C 13 Perfluorinated A dd ) FBSA , Perfluorobutanesutfonam ide FO SA , Perfluorooctanesulfonyiam ide PFB S, Potassium PerfluorobutanesuHbnate P FH S , Perfluorohexanesulfbnate P FO S , Potassium perfluoroodanesulfonate
P FO A [1 X 3 ,4 -13C ], 13C4-isotopically labeled perfluorooctanoic ad d (S R S ) P FO S [1 X 3 ,4 -13C ], 13C4-isotDpicaHy labeled PerfluorooctanesuHbnate (S R S )
PFU nA [1 ,2 -13C ], 13C2-isotopically labeled Perfluoroundecanoic ad d (S R S ) A custom m ix o f IS s in a m ethanolic solution containing ([1 ,2 ,3 ,4 -^G JP FB A ,J1,2 -
__________________ _ . . .
^ .................
.,
........................... C dP FO S ,
and [1 ,2 ,3 ,4 ,5 ,6 ,7 ,8 -13C aP FO S A (W elfington Laboratories, G uelph, O N ) in com bination with
added a i,2 ,3 ,4 ,5 -13C s]PFPeA , ([1 ^ ,3 ,4 -n C4p F H p A , and [^O JP F B S can be used to prepare
a stock IS solution. A lternatively, individual stable isotope iS s can be used to prepare a stock
IS m ixture.
O ther IS s can be applied.
7.3 Reagent Preparation
2 m M Am m onium acetate solution (A nalysis)--W eigh 0 .3 g o f Am m onium acetate and d ssolve in 2 .0 L o f reagent w ater.
Synthetic G roundw ater (containing 2 5 ppm C a and M g) -W e ig h 0.61 g o f Calcium A cetate and 0 .9 2 g o f M agnesium A cetate and dissolve in 6 .0 L o f reagent w ater.
N ote: A lternative volum es m ay be prepared as long as th e ratios o f th e solvent to solute ratios a re m aintained.
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7.4 Stock Standard Solution (SSS) and Working Standard Solution Preparation
T h e follow ing standard preparation procedure serves as an exam ple. W eighed am ounts and final volum es m ay be changed to suit th e needs o f a particular study. For exam ple, pL volum es m ay be spiked into volum etric flasks w hen dilutHig stock solutions to appropriate levels.
100 pg/m L ta rg e t a n a ly te SSSs-- W eigh out 10 mg o f analytical standard (corrected for percent salt, acid [ETS-4-031] and purity) and dilute to 100 m L w ith m ethanol o r other
suitable solvent, in a 100 m L volum etric flask. Transfer to a 125 m L LDPE bottle o r other suitable container. P repare a separate solution fo r each analyte. Expiration dates and storage conditions o f stock solutions should be assigned in accordance w ith laboratory standard operating procedure. An exam ple o f purity and salt correction is given below fo r PFO S.
..
,, ,__ .
m o lecu lar w eig h t o f anion
s a lt correction fa c to r = ---------------------- * ----------------
m o clecu lar w eig h t o f s a lt
go
P FO S (K + )s a lt correction fa c to r =
= 0 .9 2 7 5
10 m g C sF^SO aX* w ith purity 90% = 8 .3 5 mg CfFnSQf (1 0 m g *0.90*0.9275= 8.35 m g)
10 p g /m L (1 0 ,0 0 0 n g /m L ) m ixed w o rkin g stan d ard -- Add 5 .0 m L each o f th e 100 pg/m L S S S s to a 5 0 m L volum etric flask and bring up to volum e w ith solvent.
1 p g/m L (1 ,0 0 0 n g /m L ) m ixed w o rkin g stan d ard -- Add 0 .5 m L o fth e 100 pg/m L SSS s to a 5 0 m L volum etric flask and bring up to volum e w ith solvent.
0.1 p g /m L (1 0 0 n g /m L ) m ixed s tan d ard -- Add 0 .0 5 m L o f th e 100 pg/m L S S S s to a 5 0 m L volum etric flask and bring up to volum e w ith so lven t
S to ra g e C o n d itio n s-- S tore a ll S SS s and working standards in accordance w ith laboratory standard operating procedure or in a refrigerator a t 4 2 C fo r a m axim um period o f 6 m onths from th e d ate o f preparation.
7.5 Calibration Standards
C alibration c a r be perform ed by IS o r external calibration. Using th e working standards described above, prepare calibration solutions in A STM Type I w ater, H PLC w ater, other suitable w ater, or a m ixture o f solvent and w ater using th e inform alion in Table 2 as a guideline. N ote: Volum es o f w ater o r w ater/solvent m ixtures and working standards m ay be adjusted to m eet th e data quality objectives addressed in the general project outline. C alb ration levels other than those listed below can b e prepared as needed.
For the quantitation o f PFO A and P FO S , reference m aterials o f certified m ixed lin ear and branched isom er w e preferred. A lternately, reference m aterials o f prim arily linear isom ers o f PFO A an d/o r P FO S m ay be used, how ever, when quantitating w ith predom inantly linear reference standards, additional LC S sam ples containing both lin ear and branched isom ers o f P FO A and P FO S are required3.
7.5.1 In tern al S tandard (IS ) and S urrogate R ecovery S tandard (S R S )
For IS calibration, stable isotope internal standards o f each targ et an alyte o r appropriate surrogate IS s should be spiked a t th e sam e level in a ll calibration standards. O nce the calibration standards have been prepared as stated above in Section 7 .5 , a ll calibration standards a re spiked w ith a separate internal standard spiking solution. Typically th e
3PFAOnA-p/PorFtOnSmcnarnurbi^eifnogumndi m 3M reponrtfEthllr-l0ie5^6o0f.rrfrrm rr m ivW rk ranC nrnig rfrh fin d tin ier imd hnrv-hnH
nf
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concentration o f th e internal standard is consistent w ith th e internal standard concentration expected in th e sam ples being prepared, usually 1 n g/m L The concentration o f the internal standard spicing solution is typically 2 pg/m L. A separate zero point or m ethod blank is typically prepared a t th e sam e tim e as th e calibration standards, using th e sam e solution used to prepare th e standards (A STM Type I w ater, H PLC w ater, other suitable w ater, o r a solvent/w ater m ixture), and is spiced w ith th e internal standard a t th e sam e concentration as th e (V ib ratio n curve, typically a t 1 ng/m L.
If th e sam ples being analzyed w ere pre-spiked w ith S R S s, th e calibration curve prepared in Section 7 .5 is spiced w ith a separate S R S spicing solution. Typically, th e sam ple bottles are spiked w ith a S R S a t 0.1 ng/m L. The final calibration curve m ust consist o f a t least six calibration points after analysis. T he follow ing tab le provides an exam ple o f spice concentrations and volum es used to achieve a m ulti-point extracted calibration curve w ith internal standard and surrogate standard.
T able 1 Bsts recom m ended stable isotope internal standards fo r several PFSA and PFC A targ et com pounds. A custom m ix o f isotopicaly labeled targ et analytes in a m ethanolic solution containing ([1 2 ,3 ,4 -13C JP FB A , [U -C J P F H x A , [1 ,2 ,3 ,4 ,5 ,6 .7 ,8 -13Ca|PFO A , [1 Z 3 ,4 ,5 ,6 ,7 ,8 ,& ^ C y P F N A , [1 ,2 ,3 ,4 ,5 ,6 -13C d P fDA, [1 ,2 ,3 ,4 ,5 ,6 ,7 -l3C7]P F U n A ,[1 ,2 "C zP F D o A , [1 ,2 ,3 -13C yP F H S , [1 2 ,3 ,4 ,5 ,6 ,7 ,8 -13Cb]P FO S , and [1 2 ,3 ,4 ,5 ,6 ,7 .8 -" C alFO SA (W elington Laboratories, G uelph, O N ) in com bination w ith added ([1 2 ,3 ,4 ,5 -13Cs]PFPeA , ([1 ,2 ,3 ,4 -13C JP FH pA , and [18O JP FB S can be used to prepare a stock IS solution. A lternative sources o f certified stable isotope labeled targ et analytes are appficable. A lternatively, incividual stable isotope IS s can be used to prepare a stock IS m ixture. The tab le below lists th e recom m ended stab le isotope IS s and SR Ss applied in th e m ethod. O ther stable isotope IS s and S R S s o f targ et analytes not fisted in th e tab le m ay be used if supported by validation and/or analysis batch Q C s m eeting m ethod acceptance criteria (e .g ., [13C 2}-P FO A ). T he sam e internal standard should be used fix a given analyte throughout the en tire project/study. N ote: som e o f th e com pounds listed below are a ppropriate to use as surrogate IS s w hen a stable isotope IS o f a targ et analyte is not availab le. G enerally, surrogate isotopically labeled PFC A s are used fo r PFC A s, and surrogate isotopicaily labeled PFSA s a re used fo r PFSA s.
T able 2 provides exam ples o f spice concentrations and volum es used to achieve a m ulti-point calibration curve w ith IS s and SR Ss.
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T a b le 1 . S ta b le Is o to p e P FC A s an d P FS A s u sed fo r IS s a n d S R S s
CompoundNome I3C4-Fafinan>biitaiioic acid 13C4 -Perfluoiopentnotc acid ^CrPafiuorohexmoic add 13C4-Perfhioroheptanoic acid 13Ct-Pexfluarooctanoic acid ^Cs-PerfhiorojKMimoic acid 13C-Pcrfhiorodccanoic acid 13C7-Perfhiaroundecanaic acid "CrPetfluotododecanoic acid "02-Ammomum PerSuorobutane sulfonate 13C]-Ammoniuiu Perffuoioficxanc sulfonate I3Cr Sodium Perfluorooctane sulfonate
>3Ct-Petfluorooctanesulfonamide 13C4-Perfluuiuoclanoic add 13C2-Perfluoroundecanoic acid 13Ci-Perfhiorooctane sulfonate
Synonym orAcronym [Ii3 ,4 -UC]PFBA [l,2,3,4,5-uC5JPFPeA [U -'kyPFH xA [1,2,3,4-uC]PFHpA [1,2.3,4,5,6,7.8-13C,]PF0A [1,2,3,4,5,6,7,8,9-UCJPFNA [1,23,4,5,6-"CJPFDA [1.2,3,4,5,6.7 "CiJPFUnA [ ^ - "CjIPFDoA [" OiJPFBS [1,2J-uCjP*FHS [1,2,3,4,5,6,7.8-13C,JPF0S
[l,23,4,5,6,7,8-IJC*]FOSA [U ,3,4-13CJPFOA [ U - uC2PFUiiA [l,2,3,4-13C<JPFOS
AnalyticalPurpose IS forPFBA IS forPFPeA IS forPFHxA
ISforPFHpA IuSCf,o]PrFPOFOAA and [1.2.3.4 IS foePENA IS forPFDA IS forPFUnA IS for PFDoA, *PFTA IS forPFBS IS forPFHS IPSFfOoSrPflF,2O,3S,4an"dC J.
IS forFOSA
SRS forall PFCAs: C4-C8
RSoeuferrceenceStandard Wellington Labs (Mix or Individual) Wellington Labs (Mix or Individual) Wellington Lab (Mix orIndividual) Wellington Labs (Mix orIndividual') Wellington Labs (Mix or Individual) Wellington Labs (Mix orIndividual) Wellington Labs (Mix orIndividual) Wellington Labs (Mix orIndividual) Wellington Labs (Mix or Individual) R(InTdIiIvnitdeurnala)tional W ellington Labs (Mix orIndividual) Wellington Labs (Mix or Individual) Wellington Labs (mix) R(InTdIiIvnitdeurnala)tional Wellington
SRS for all PFCAs C9-C13 Wellington
CSR6S,afnodrCal8l PFSAs: C4, Wellington
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Direct Injection Analysis
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G LP10-01-01; Interim Report 31 Analysis of PFQA in Groundwater Sam ples
Bert Jeffries Property - April 2012
Table 2. Example Preparation of Calibration Curve with ISa and SRSs
S a m p le D e s c rip tio n
0.025 ng/mL curve point 0 .030 ngAnL curve point 0.04 ngAnL curve point 0.05 ngAnL curve point
0.1 ngAnL curve point 0.25 ngAnL curve point 0 .5 ngAnL curve point
1 ngAnL curve point 2 .5 ngAnL curve point 5 .0 ngAnL curve point 10.0 ngAnL curve point 25.0 ngAnL curve point 50.0 ngAnL curve point 75.0 ngAnL curve point 100 ngAnL curve point
C o n c e n tra tio n
o f M S, p g /m L
0 .1 0 0 .1 0 0 .1 0 0 .1 0 0 .1 0 0 .1 0 1 .0 1 .0
iao
10.0 10.0 10.0 10.0 10.0 10.0
Volum e o f
W S .p L
V o lu m e o f IS (2 p g A n Q ,p L
25 50
30 50
40 50
50 50
100 50
250 50
50 50
100 50
25 50
50 50
100 50
250 50
500 50
750 50
1000
50
C o n c e n tra tio n o f S u rro g a te , p g /m L
0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 10.0 10.0 10.0 10.0 10.0 10.0 10.0
V o lu m e o f S u rro g a te , p L
12.5 15 20 25 50 125 250 500 25 50 100 NA NA NA NA
V o lu m e o fA S T M T y p e 1 W a te r, o r o th e r s u ita b le s o lv e n tm , m L
100 100 100 100 100 100 100 100 100 100 100 100 100 100 100
N /A - Not Applicable (1) Samples requiring analysis for PFUnA, PFDoA, PFTrOA, and FOSA should be analyzed against a calbration curve prepared in 1:1 synthetic groundwaterMeOH.
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8 Sample Collection and Bottle Preparation
Sam ple collection bottles a re prepared by 3M Environm ental Laboratory (o r subcontract su p p ler) personnel fo r shipm ent a t am bient tem perature to th e collection site. Typically, four separate collection bottles are associated w ith a single collection site: sam ple, field duplicate sam ple, low field m atrix spike, and high field m atrix s p ire . A lternatively, th e sam ple and field duplicate sam ple m ay contain S R S s in lieu o f additional target analyte low field m atrix spjke a id targ et an alyte high field m atrix spike sam ples. D epending on th e scope o f th e project, additional replicates o f th e field sam ple and field m atrix spikes m ay be added. A lso, it is not uncomm on fo r additional m id-level field m atrix spikes to be collected if th e expected sam ple concentrations are truly unknown o r could span a large concentration range.
H igh-density polyethylene (H D P E ) w ide-m outh N algene bottles are used fo r th e sam ple collection containers. (Volum es o f th e bottles m ay vary depending on how m uch sam ple is required to m eet data quafity objectives.) S am ple coflection volum es a re project specific and based on data quality objectives. T h e N algene bottles do not require any pretreatm ent prior to use. Typically, placem ent o f a sam ple bottle volum etric "fin to here" line is done by using a sam ple bottle m arker tem plate. A lternatively, bottles m ay be w eighed prior to bottle preparation and w eighed again a fte r sam ples have been collected.
A l bottles should be clearly labeled to indicate its intended use as a sam ple, field sam ple duplicate, low field m atrix spice, high field m atrix spike, sam ple/S R S field m atrix spice, field duplicate sam ple/S R S field m atrix spike, trip blank, o r trip blank m atrix spice. If each location has cfifferent designated spike levels, th e label should also clearly incicate th e sam ple location designation. G enerally, a set o f bottles fo r a given collection site are prepared then grouped together in plastic bags fo r organizational purposes. For each sam ple collection e v e n t a t least one set o f trip blank and trip blank m atrix spices are prepared.
B ottle preparation should be docum ented in a N ote to F ile o r on a sam ple preparation w orksheet and should include th e follow ing inform ation: d ate prepared, to tal num ber o f bottles prepared, num ber o f sam ple sites, the standard identification num bers and spike volum es used to prepare spiced bottles, th e "fii to here" volum e, and any other pertinent inform ation needed fo r reconstructtoility o f th e d ata. T h e N ote to F ie w ill be included in the final data package fo r th e p ro ject
Sam ples a re collected in th e field and shipped to th e laboratory a t am bient tem perature.
8.1 Field Matrix Spike Sample (FMS)
Field m atrix spike sam ples are a requirem ent o f th e m ethod. A FM S sam ple is defined as a Q C sam ple to which known quantities o f appropriate targ et analytes are added to th e sam ple bottle in th e field o r in the laboratory before th e bottles a re sent to th e fie ld . T h e sam ple and field duplicate sam ple m ay contain appropriate S R S s in lieu o f targ et analyte FM S sam ples. Sam ple quantities a re determ ined volum etrically or gravim etrically. A known, specific volum e o r w eight o f sam ple is added to th e sam ple container w ithout rinsing. Volum etric sam ple m easurem ents m ay be acquired by a laboratory applied "fill to this level" Bne on the outside o f th e sam ple container. T arg et analyte FM S sam ples should be spiked a t approxim ately 0 .5 -1 0 tim es th e expected analyte concentration in th e sam ple. If th e expected range o f analyte concentrations is unknown, m ultiple spikes a t varying levels m ay be prepared to increase th e likefihood th at a spice a t an appropriate level is m ade. T yp icaiy a low and a high targ et analyte spike a re prepared fo r each sam pling location. In those instances w here S R S s are to be used in lieu o f target analyte FM S sam ples, the sam ple and field duplicate sam ple a re spiked a t approxim ately 2 -5 tim es th e targ et LO Q . T h e FM S is analyzed to ascertain if m atrix effects o r sam ple holding tim e contributes bias to th e analytical results. For th e sam ple bottles designated fo r m atrix spices, an appropriate volum e o f m atrix spicing solution is added to th e em pty bottle prior to sam pling. T he volum e o f spice solution added should produce th e desired final concentration o f targ et analytes once the bottle is file d w ith sam ple to th e "fill to here line' . T he m atrix spfcing solution(s) should be prepared in a suitable solvent and contain a l o f th e appropriate targ et analytes, IS s, a id S R S s. T h e targ et an alyte m atrix spiking solution is often th e sam e as th e working standards used to create the cafibration standards. An exam ple o f a bottle spice is given below .
"FBI to here' volum e = 200 m L (A 2 5 0 m L N algene bottle is used)
D esired Field S pike Concentration = 0 .2 5 ng/m L
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Bert Jeflries Property - April 2012
500 o f a 0.1 pg/m LspIdng solution (containing th e targ et an alytes) is added to Ih e bottle and th e bottle cap prom ptly sealed.
8.2 Internal Standard and Surrogate Recovery Standard
If analysis o f a surrogate recovery standard (S R S ) is included in th e project objectives, an appropriate volum e o f a surrogate standard solution is added to all th e bottles prior to sam pling and S P E . Typically sam ple bottles are spiced w ith surrogate recovery standards a t a final desired spice concentration o f 0.1 ng/m L.
If quantitation by internal standard (IS ) is inducted in th e project objective, an appropriate volum e o f internal standard solution is added to a l th e bottles prior to sam pling and S P E . Typically sam ple bottles a re spiced w ith internal standard a t a fin al desired spice concentration o f 1 ng/m L.
For th e trip blank, th e S R S spice and IS spice is added to the bottle and then A STM Type I w ater (H P LC grade reagent w ater o r other suitable w ater m ay used) is added to th e TB to here* lin e. T h e bottle is capped and sealing tap e m ay be placed around th e outer edge o f th e cap. T rip blank m atrix spices are prepared by adcfng th e appropriate volum e o f targ et analyte spicing solution, IS , and S R S spicing solutions and filin g th e bottle to th e desired volum e w ith th e appropriate w ater and capping and sealing th e cap.
9 Quality Control and Data Quality Objectives_________________________________
9.1 Data Quality Objectives
This m ethod and required quality control sam ples is designed to generate d ata accurate to 30% w ith a targeted LO Q o f 0 .0 2 5 n g/m L A ny deviations from th e q u a ity control m easures spelled out below w il be docum ented in th e raw data and footnoted in th e final rep o rt
9.2 Method/Procedural Blanks
T h e m ethod/procedurai blank is zero point c a lix a tio n standard (w hich includes IS s) analyzed in a regular basis w ith each analysis batch. A t a m inim um , m ethod blanks are analyzed prior to instrum ent c a lix a tio n , prior to th e analysis o f C C V sam ples, a fte r every 10 sam ple injections, and a t th e end o f th e analytical run.
T he m ean area count or area ratios when using internal standard c a lix a tio n , fo r each an alyte in the m ethod blanks m ust be less than 50% o f th e area count counts o r area ratios w hen using internal standard caB xation, o f th e LO Q standard. T he standard deviation o f th e area counts, or area ratios w hen using internal standard c a lix a tio n , o f these m ethod blanks should be calculated. A specific % R S D acceptance criteria is not specified but is assessed on an analytical batch basis. If th e m ean area counts o r area ratios w hen using internal standard c a p ta tio n , o f th e m ethod blanks exceed 50% o f the LO Q standard, then th e LO Q m ust be raised to th e first standard level in th e curve th at m eets criteria. M ethod blanks m ay b e elim inated if technical justification can be provided (e .g . th e procedural blank w as analyzed a fte r an unexpectedly high level sam ple). If any procedural blanks a re rem oved from th e LO Q determ ination, docum ent in th e raw d ata and report as appropriate. Laboratory S am ple R e p lic a te s /F ie ld D uplicate Sam ple
Typically, sam ples a re collected in duplicates in th e fie ld . T h e relative percent difference (R P D ) o f duplicate sam ples should be <20% fo r th e precision o f sam ple preparation and analysis to be considered in control. R eplicate sam ples not m eeting th e s20% R PD criteria a re flagged and reported as outside o f Q C acceptance c rite ria .
9.3 Laboratory Matrix Spikes (LMSs)
LM Ss m ay be perform ed in lieu o f FM Ss if FM Ss have previously been perform ed fo r th e sam ple m atrix. A ddttionally, LM Ss m ay be perform ed in fieu o f FM Ss fo r a sam ple m atrix if th e FM S levels w ere not appropriate fo r determ ining s p ire recoveries relative to endogenous levels o f target analytes and appropriate S R S s. G en eraly, each sam ple location represents a d ifferen t sam ple and sam ple m atrix. LM Ss are prepared fo r each sam ple and analyzed to determ ine the m atrix effect on spice recovery efficiency o f each targ et analyte and appropriate S R S s. LM Ss should be prepared a t a m inim um o f one level and in dupficate. LM S concentrations should be prepared a t approxim ately 0 .5 -1 0 tim es the endogenous concentration or approxim ately 4 -1 0 tim es th e LO Q concentration o f each targ et analyte.
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Bert Jeffries Property-April 2012
Lab m atrix spice recoveries should fa ll w ithin 30% o f expected values. Sam ple d ata w ith LM S recovery outside o f 30% but w ithin 50% o f th e expected value are flagged and reported as outside o f Q C acceptance criteria. D ata w ith LM S recovery outside o f 50% o f the expected value are reported as N R , w here N R is defined as "N ot R eportable" d ata outside o f Q C acceptance criteria.
9.4 Lab Control Sample
Lab control s p ite s a re prepared fo r each analysis batch to determ ine m ethod accuracy and precision. LCSs should be prepared a t th ree levels in trip licate fo r each target analyte and a t a m inim um o f tw o levels in triplicate fo r appropriate S R S s. Low lab control spikes should be prepared a t a concentration in th e range o f approxim ately four to ten tim es higher than th e targeted low er LO Q , th e m id lab control spices should be prepared a t a concentration near the m id-point o f th e calibration curve and th e high lab control spikes a t approxim ately 80% o f the upper LO Q . For each target analyte and S R S s, th e percent relative standard deviation (m ethod precision) fo r each control spice level m ust be less than or equal to 20% and th e average recovery (m ethod accuracy) fo r each control spike level m ust be 80-120% . Sam ple d ata fo r targ et analytes outside o f th e laboratory control spike acceptance criteria w ifl be handled as follow s:
If th e average recovery o f a spiking level falls outside m ethod acceptance, but a t least 67% (6 out o f 9 ) o f LCS sam ples are w ithin 20% o f th eir respective nom inal valu e (33% o f th e Q C sam ples, not a ll replicates a t the sam e concentration, m ay b e outside 20% o f nom inal valu e), th e average recovery w ill be flagged as outside m ethod acceptance criteria. A ll LCS sam ples w ill be control charted as p er E T S -4-026. If th e average recovery o f one o f the spiking levels exceeded th e analytical m ethod uncertainty as determ ined by E T S -12012, th at analytical batch uncertainty w ill b e expanded fo r th at p artcu la' study.
If m ore than 67% o f the LC S sam ples fa i to m eet m ethod acceptance criteria, th e d ata w ill not be reported.
CaHbration standards consisting o f m ixed branched and lin ear isom er P FO S /P FO A a re preferred. H ow ever, fo r P FO S /P FO A target analytes, if th e calforation standards are com prised o f predom inantly linear isom ers only, at least one level o f trip licate LCSs should be prepared using P FO S /P FO A which contains a m ix o f linear and branched isom ers. These LCSs w ill be used to dem onstrate quantitative equivalency (o r quantitative bias) o f th e isom eric m ix w hen using a predom inantly lin ear standard fo r c a lx a tio n . T h e m ixed lin ear and branched isom er P FO S /P FO A LC Ss recoveries should fa ll w ithin 30% o f expected values. A lternatively, in lieu o f m ixed branched and lin ear isom er P FO S /P FO A LCSs, m ixed branched and lin ear isom er PFO S /P FO A TB M Ss m ay be applied to dem onstrate m ethod accuracy and precision.
9.5 Field Matrix Spikes (FMSs) / Surrogate Recovery Standards (SRSs)
FM Ss a re prepared fo r each sam pling location and analyzed to determ ine th e m atrix effect and sam ple holding tim e on th e spice recovery o f each targ et an alyte and/or appropriate S R S . G enerally, each sam ple location represents a d ifferent sam ple and sam ple m atrix.
FM Ss are Q C sam ples to which known quantities o f appropriate targ et analytes a re added to th e sam ple bottle in th e laboratory before th e bottles are sent to th e fie ld . T yp icaly a low and a high targ et analyte FM S are prepared fo r each sam pling location. T he sam ple and field duplicate sam ple m ay contain appropriate S R S s 8i ie u o f targ et an alyte low field m atrix spike and targ et analyte high field m atrix spice sam ples.
Field m atrix spike m ethod acceptance criteria are recoveries w ithin 30% o f th e expected value. If FM S recovery (targ et analyte or S R S spike) is outside o f 30% o f the expected value o r could not be assessed because th e FM S (targ et an alyte) w as spiked a t an inappropriate level, th e sam ple result is reported as follow s:
1 . ) If targ et an alyte FM S recovery could not be assessed because th e FM S 's w ere a t an inappropriate level, then Laboratory M atrix S pices (L M S ) m ay be substituted. If LM S recoveries a re w ithin 30% th e data are reportable and flagged to indicate th at the FM S spikes levels w ere inappropriate.
2 . ) If m ultipie targ et analyte FM S 's w ere prepared on a sam ple and th e closest FM S level to th e reported sam ple m eets th e 30% acceptance criteria but additional FM S 's are outside th e 30% acceptance range, th e d ala a re reportable and flagged to indicate th at w hile th ere w ere failing FM S 's, th e uncertainty w il not be expanded since th e m ost appropriate spike level passed.
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Bert Jeffries Property April 2012
3 . ) If the targ et an alyte FM S recoveries are outside o f the 30% acceptance range but a t least 30 acceptable historical reportable FM S sam ple results are availab le, th e data m ay be reported but flagged w ith an expanded uncertainty and as not m eeting FM S criteria.
4 . ) Sam ple data w ith FM S recovery outside o f 30% but w ithin 50% o f th e expected value a re flagged and reported as outside o f Q C acceptance criteria w ith an expanded uncertainty.
5 . ) If FM S recovery is outside o f 50% , th e sam ple result is reported as N R , w here N R is defined as "N ot R eportable" due to noncom pliant Q C results.
T he targeted fortification levels should be a t least 50% o f the endogenous level and less than 10 tim es the endogenous level to b e used w ithoutjustification to determ ine th e statem ent o f accuracy fo r analytical results.
N ote: It is possible fo r bottles ut&zed fo r Field M atrix S pike sam ples to be u nd er-filed o r over-flHed during sam ple co lectio n. Since this scenario w ll effect th e actual concentration o f th e FM S sam ple (su ro g ate and internal standard concentrations w il also be effected , if used), it is im portant th at any obvious under-filing or over-filling o f sam ple bottles be docum ented in th e data package and taken toto account h th e FM S , IS s, o r SR Ss recovery calculations. Sam ples over-filled o r under-filled by m ore than 10% w fl be require recalculation o f th e FM S , IS s, and S R S tru e values.
T he average o f th e sam ple and th e field dupficate should be used to calculate th e recovery.
10 Procedures
10.1 W ater Sample Preparation
This m ethod is applicable to w ater sam ples. Sam ples containing heavy particulate m ay not be suitable to r analysis by this m ethod. Sam ples containing suspended particulate should be centrifuge prior to rem oving a sam ple aliquot, o r fite re d .
Thoroughly m ix sam ple before rem oving an aliquot and placing in a labeled autovial.
D iu te sam ple, if necessary, w ith A STM Type I w ater, H PLC w ater, other suitable w ater, o r solvent (m ethanol).
Lab control spices a re prepared fo r each analysis batch to determ ine m ethod accuracy and precision. LCSs should be prepared a t th ree levels in tripficate fo r each targ et analyte and a t a m inim um o f two levels in trip licate fo r appropriate S R S s. Low lab control spices should be prepared a t a concentration in th e range o f approxim ately four to ten tim es higher than th e targeted low er LO Q , th e m id lab control spices should be prepared a t a concentration near the m id-point o f th e caH iration curve and th e high lab control spices a t approxim ately 80% o f th e upper LO Q . For IS quantitation, stable isotope internal standards o f each targ et analyte o r appropriate surrogate IS s should b e spiked a t th e sam e level as the sam ples being analyzed, in a l LC Ss.
If LCSs are being prepared using synthetic groundw ater, a lo w th e LCSs sam ples to e q u lix a te fo r a m inim um o f 4 hours before aliquoting fo r analysis o r diluting w ith solvent (m ethanol).
11 Sample Analysis - LC/MS/MS
11.1 Instrument Setup
N o te: In this exam ple, an A pplied Biosystem s S d ex A P I 4 0 0 0 (A P I 5000 or A P I 5 5 0 0 ) Tandem M ass Spectrom eter (L C /M S /M S ) is used. O ther brands/m odels o f LC /M S /M S instrum ents as w e l as single quadm poie m ass spectrom eters (L C /M S ) m ay be used as long as th e m ethod acceptance criteria are m et. Brand nam es, su pp iers, part num bers, and m odels are fo r illustrative purposes only. Equivalent perform ance m ay be achieved using apparatus and m aterials other than those specified h ere, but dem onstration o f equivalent perform ance th at m eets th e requirem ents o f this m ethod is th e responsibility o f th e laboratory. The operator m ust optim ize and docum ent th e equipm ent and settings used.
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Establish th e LC /M S /M S system and operating conditions equivalent to th e follow ing: M ass Spec: A pplied Biosystem s A P I 4 0 0 0 , A P I 5 0 0 0 , or A P I 5500 Ion Source: Turbo Ion S pray (A B S ) M ode: Electrospray N egative Scan Type: M R M (M ultiple R eaction M onitoring) Com puter: D e l DHM Softw are: W indow s 200 0 o r W indow s X P , A nalyst 1 .4 .2 or higher versions HPLC : A gilent S eries 1 1 0 0,1200, or 1290 A gilent Q uaternary Pum p A gilent Vacuum D egasser A gilent Autosam pler A gilent Colum n O ven N o te: O ne o r m ore C 18 H PLC analytical colum ns (2.1 mm x 100 m m , 5pm o r 2.1 mm x 50 m m , 5pm ) m ay be attached on-line a fter th e purge valve and before th e sam ple injection port to retard and separate any residue contam inants th a t m ay be in th e m obile phase and/or H PLC system . H PLC Colum n: B etasil C 1 8 ,4 .6 m m x 100m m , 5pm (Therm oElectron C orporation) Colum n Tem perature: 35C Injection Volum e: 5pL M obile P hase (A ): 2m M Am m onium A cetate in A STM Type I w ater (S e e 7 .3 ) M obile P hase (B ): M ethanol
T a b le 3 . L iq u id C h ro m a to g ra p h y G ra d ie n t P ro g ra m .
S te p Num ber
0 1 2 3 4 5
Total Time (m in)
0 20 14.5 15.5 16.5 2 0 .0
F lo w R ate (fU m in )
750 750 750 750 750 750
Percent A (2 m M am m onium
a c e ta te )
9 7 .0 9 7 .0 5 .0 5 .0 97.0 9 7 .0
Percent B (M ethanol)
3 .0 3 .0 95.0 95.0 3 .0 3 .0
N ote: O ther H PLC gradients m ay be used as long as th e m ethod criteria and project d ata quality objectives are m et
It m ay be necessary to adjust th e H PLC gradient in order to optim ize instrum ent perform ance. Colum ns w ith different dim ensions (e .g . 2.1m m x 30m m ) and colum ns from d ifferent m anufacturers (K eystone B etasil C 18 e tc .) m ay be used.
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Bert Jeffries Property - April 2012
T a b le 4 S u g g e s te d M R M T ra n s itio n s fo r T a rg e t A n a ly te s , S u rro g a te s , a n d In te rn a l S ta n d a rd s
Analyte PFBA (C4 Acid) PFPeA (C5 Add) PFHxA (C6 Acid) PFHpA (C7 Acid) PFOA (C8 Acid) PFNA (C9 Acid) PFDA (CIO Acid) P F U nA fC llA dd) PFDoA (C12 Add) PFTA(C13 Acid)
POSA C8 Sulfonamide) PFBS (C4 Sulfonate) PFHS (C6 Sulfonate) PFOS (C8 Sulfonate) rU .3,4 -1JG,]PFBA W 23A 5 -uC,lPFPeA TU "CilPFHxA ru.3.4 - uClPFHi>A [1_2.3,4,5,6.7,8-uCj]PFOA [1,2,3,4,5.6,7.8.9-uC,]PFNA [U.3,4,5,6 -13C6]PFDA [1,2,3,4.5,6,7 -" CjffFUnA 12 -uC,lPFDoA [" OJPFBS ^ "CjIPFHS TU3.4- "CJPFOS rii3 .4 ^ .6 .7 .8 -nC1FOSA [U J.4 -uC4]WOA ru,3,4 - 1JC4lPFOS [U -^lP F U n A _____________
Analyte Description
Target Target Target Target Target Target Target Target Target Target Target Target Target Target Target IS forPFBA IS for PFPeA IS forPFHxA IS foe PFHpA IS fix PFOA IS fix PFNA IS fix PFDA IS for PFUnA IS fix PFDoA and PFTA IS fix PFBS ISforPFHS IS fix PFOS IS for FOSA Surrogate CC4-C8 Adds) SunogatefSulfonates, FOSA) Surrogate (C9-C13 Adds)
Mass Transition 01 (amu) 213 263 313 363 413 463 513 563 613 663 298 498 299 399 499 217 268 315 367 421 472 519 570 615 303 402 503 507 417 503 565
Mass Transition Qi (amu) 169 219 269.119 319.169 369.219.169 419.169.219 469.269.219 519.269,219 569.169.319 619.369.319 78 78 99.80 99.80 80.99.130 172 223 270 322 376 427 474 525 570 84 80 80 80 372 80 520
M ultiple transitions fo r m onitoring th e analytes is an option. T h e use o f one daughter ion is acceptable if data sensitivity and selectivity is achieved and provided th at retention tim e criteria a re m et to assure adequate specificity. W h ie th e daughter ions m ay be chosen a t th e discretion o f th e analyst, m ass transition 9 9 is suggested fo r P FO S . Q uantitation m ay be perform ed using th e to tal ion chrom atogram (T IC , o r sum m ed M R M s) fo r a given an alyte. For exam ple, th e PFO A T IC would sum a ll th ree o f th e m onitored transitions. U se o f th e suggested prim ary ion is recom m ended. R etention tim es m ay vary slightly, on a day-to-day basis, depending on th e batch o f m o b ie phase and th e g rad ien t colum n, guard colum n(s) used etc. D rift in retention tim es is acceptable w ithin an analytical run, as long as th e d rift continues through th e en tire analysis and the standards are interspersed throughout th e analytical run.
11.2 Calibration Curve
Q uantitation is by internal standard o r external standard calibration. C alibration standards m ay be prepared in A STM Type I, H PLC w ater, other suitable w ater, or a solvent/w ater m ixture. If internal standard calibration does not m eet calibration acceptance criteria, external calibration can be applied. S ee T ab le 1 fo r
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Analysis ofGPLFPO1A0-in01G-0r1o;uInndtewriamterRSeapmorptl3e1s
Bert Jeffries Property - April 2012
recom m ended application o f availab le internal standards. Q uantitation o f PFO A and P FO S is by sum m ed analyte-specific m ass transitions.
A nalyze th e standard curve prior to each set o f sam ples. If internal standards w ere added to th e calforation standards area ratios a re used to generate th e calibration curve. T h e standard curve m ay be plotted using a lin ear regression (y = m x + b ), w eighted 1/x o r unw eighted, o r by quadratic fit (y = ax2 + bx + c ), w eighted 1Acor unw eighted, using suitable softw are. T h e m athem atical m ethod used to calculate th e calibration curve should be applied consistently throughout a study. A ny change should be thoroughly docum ented in th e raw data.
High and/or low points m ay be excluded from the calibration c u v e s to provide a b etter fit over th e range appropriate to th e date o r because they did not m eet th e pre-determ ined acceptance criteria. Low -level curve points should also be excluded if th eir area counts (o r area ratio if quantitating by IS ) are not a t least tw ice th at o f th e averag e area counts (o r area ratio if quantitating by IS ) o f m ethod and/or solvent blanks. T he coefficient o f determ ination (r2) value fo r th e calibration curve m ust be greater than o r equal to 0 .9 9 0 (o r a correlation coefficient (r) o f 0 .9 9 5 ). Each point in th e curve m ust be w ithin 25% o f th e theoretical concentration w ith the exception o f th e LLO Q , which m ay be w ithin 30% . Justification fo r exclusion o f calibration curve points w ill be noted in th e raw d ata. A m inim um o f 6 points w ill be used to construct th e calibration curve.
If th e calbration curve does not m eet acceptance criteria, perform routine m aintenance or prepare a new standard curve (if necessary) and reanalyze.
11.3 Continuing Calibration Verification (CCV)
Continuing calibration verifications (C C V ) are analyzed to verify th e accuracy o f th e calibration curve. A nalyze a m id-range calibration standard, one o f th e sam e standards used to construct th e calibration curve, a t a m inim um a fte r every tenth sam ple, not including solvent blanks, w ith a m inim um o f one p er sam ple s e t CaNbration verification injections m ust be w ithin 25% to be considered acceptable. T h e calfcratkxi curve and th e last passing C C V w ill then bracket acceptable sam ples. M ultiple C C V levels m ay b e used. Sam ples m ust be bracketed by passing C C V s o r th e calibration curve and a passing C C V to be reportable.
11.4 System Suitability
A m inim um o f th ree system suitability sam ples should be injected a t th e beginning o f each analytical run, prior to th e analysis erf the calibration curve. Typically these sam ples are a t a concentration near th e m id-level o f the calibration curve and are repeated Sections from one autosam pler v ia l. It is suggested th at th e system suitability injections have area counts o r area ratios w hen using internal standard calibration, w ith a targ et R SD o f s5% and a targ et retention tim e R SD o f 52% . There is no defined acceptability lim it on these results as the % R SD value is dependent on th e num ber o f M RM transitions being m onitored in the LC /M S /M S run o r tim e period. U ltim ately, any effects on these param eters fo r the System S uitability sam ples w ill also b e evident on all standards and Q C sam ples analyzed as p a l o f th e analysis batch. Any effect o f system su itab iity is incorporated w ithin Q C acceptance criteria.4
11.5 Sample Analysis and QCs
For each analysis batch, th e instrum ent analysis run sequence should include an in itial calibration curve, sam ples, FD S s, interspersed blanks, interspersed C C V s, appropriate Q C s (i.e ., LC Ss, LM Ss, FM S s, TB M Ss, and T B s), and a fin al C C V o r calibration curve bracketing sam ples and appropriate Q C s
In ject th e s a n e volum e (betw een 5 -1 OOpL) o f each standard, analytical sam ple and blank into th e h stru n e n t (unless an on-instrum ent sam ple diu tion is desired).
Sam ples containing analytes th at are quantitated above th e concentration o f th e highest standard in th e curve should b e fu rther d iu ted and reanalyzed.
43M Environmental Laboratory study E08-0096 evaluated the effect onthese remits is a function ofthe numberofMRMsbeing monitored,
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12 Data Analysis and Calculations
T h e chroma tography analysis softw are w il typically calculate th e am ount o f targ et an alyte in th e sam ple extracts using th e established calbration c u v e . C alculate th e percent recovery o f th e LCS using th e follow ing equation:
LCS C oncentration LCS% recovery = --------------------------------* 100%
Spike Concentration tnT.
C alculate th e percent recovery o f the LM S using th e follow ing equation:
LM S Concentration ( - ^ - ) - Concentration o f Sam ple ( - ^ - ) LM S % recovery = ___________________ mL___________________________ mL * 100%
Spike Concentration ( - ^ - ) mL
For sam ples fortified w ith known am ounts o f analyte prior to extraction, use th e follow ing equation to calculate th e percent recovery.
R ecovery T o ta l a n a ly te
(n g ftn L ) - A verag e a n a ly te found in sam p le (n g /m L ) ^ A nalyte added (n g /m L )
13 Analysis Batch Method Performance Criteria
A ny m ethod perform ance param eters th at are not achieved m ust be considered in th e evaluation o f th e data. Nonconform ance to any specified param eters m ust be described and discussed in th e fin al report if the Technical M anager (non-G LP study) o r Study D irector (G LP study) chooses to report th e data.
If criteria listed in this m ethod perform ance section are not m et, m aintenance m ay be perform ed on th e system and sam ples reanalyzed, or other actions taken as appropriate. D o cu m en tal actions in th e raw data.
If data a re to be reported w hen perform ance criteria have not been m et, th e data m ust be footnoted on tables and discussed in th e text o f th e rep o rt
13.1 System Suitability - Analysis Batch
A m inim um o f th ree system su itab iity sam ples should be injected a t th e beginning o f each analytical run. These sam ples are run prior to th e calb ratio n curve. It is suggested th at th e system suitability injections have area counts w ith a targ et R SD o f 5% and a targ et retention tim e R SD o f 2% . T here is no defined acceptability lim it on these results as the % R SD s are dependent on th e num ber o f M R M transitions being m onitored in th e LC /M S /M S run or tim e period. A ny effect o f system suitability is incorporated in th e Q C acceptance criteria.
13.2 Calibration and Limit of Quantitation (LOQ) - Analysis Batch
C a lib ra tio n C u rve: T he coefficient o f determ ination (r2) value fo r th e calibration c u n m ust be g reater than or equal to 0 .9 9 0 corresponding to a correlation coefficient (r) = 0 .9 9 5 . Each point in th e curve m ust be w ithin 25% o f th e theoretical concentration w ith th e exception o f the LLO Q , which m ay be w ithin 30% .
C C V P erfo rm an ce: T h e calibration standards th at are interspersed throughout th e analytical sequence are evaluated as continuing calb ratio n verifications in addition to being part o f th e c a lix a tio n curve. T h e accuracy
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o f each curve point m ust be w ithin 25% erfth e theoretical value (w ithin 30% fo r low est curve point). Sam ples th at are bracketed by C C V s not m eeting these criteria m ust be reanalyzed.
L im its o f Q u a n tita tio n (L O Q ): T he low er LO Q (LLO Q ) is th e low est non-zero active standard in th e calforation curve; th e peak a re a o f th e LLO Q m ust be a t least 2X th at o f th e average area counts fo r a l prepared procedural b lan k(s). By definition, th e m easured value o f th e LLO Q m ust be w ithin 30% o f the theoretical value.
D em o n stratio n o f S p e c ific ity : S pecificity is dem onstrated by chrom atographic retention tim e (w ithin 4% o f standard) and th e m ass spectral response o f unique ions.
13.3 Blanks - Method/Procedural Blanks and Trip
M eth o d /P ro ced u ral B lan ks: M ultiple procedural blanks should be interspersed throughout the analysis batch and th e analytical sequence. A t a m inim um , m ethod blanks are analyzed prior to instrum ent calibration, prior to th e analysis o f C C V sam ples, afte r every 10 sam ple injections, and a t th e end o f th e analytical run.
T he m ean area counts (o r area ratios w hen using IS calibration) fo r each analyte m ust be less than 50% o f th e area count o f the LO Q standard. If th e area counts o f th e procedural blanks exceed 50% o f th e LO Q standard, then th e LO Q m ust be raised to th e fast standard level th at m eets criteria.
T rip B lan k: A trip blank o f A STM Type I w ater (o r lab equivalent) is prepared in a sam ple container in th e laboratory a id treated as a sam ple, including exposure to shipping, sam pling site conditions, storage, preservation and a ll analytical procedures. T he trip blanks results fo r each analyte a re included w ith th e reported sam ple results.
13.4 Data Accuracy and Precision - Analysis Batch
L ab C o n tro l S p ikes: T h e average recovery a t each LC S level fo r each target an alyte and appropriate SR S should be w ithin 80-120% and th e percent relative standard deviation o f th e recoveries m ust be less than or equal to 20% . If th e average recovery o f a spiring level fa lls outside m ethod acceptance, but a t least 67% (6 out o f 9 ) o f LC S sam ples a re w ithin 20% o f th eir respective nom inal value (33% o f the Q C sam ples, not all replicates a t th e sam e concentration, m ay be outside 20% o f nom inal valu e), th e averag e recovery w il be flagged as outside m ethod acceptance criteria. A ll LCS sam ples w ill be control charted as per E T S -12-012. If th e average recovery o f one o f th e spiking levels exceeded th e analytical m ethod uncertainty as determ ined by E T S -12-012, th at analytical batch uncertainty w il be expanded fo r th at particular study. T he average recovery a t each LC S level fo r m ixed branched/linear isom er PFO A and P FO S should be w ithin 70-130% and the percent relative standard deviation o f th e recoveries m ust be less than or equal to 20% .
F ie ld D u p lic a te s : T he relative percent cSfference (R P D ) o f duplicate sam ples should be less than 20% fo r th e precision o f sam ple preparation id analysis to be considered in control. R eplicate sam ples not m eeting th e 20% R PD criteria are flagged and reported as outside o f Q C acceptance criteria.
F ie ld M a trix S p ikes: FM S acceptance criteria are recoveries w ithin 30% o f th e expected value fo r each targ et analyte and appropriate S R S . Sam ple d ata w ith FM S recovery outside o f 30% but w ithin 50% o f th e expected valu e a re flagged and reported as outside o f Q C acceptance criteria. D ata w ith FM S recovery outside o f 50% o f the expected value are reported as N R , w here N R is defined as "N ot R eportable" data outside o f Q C acceptance criteria. If FM S recovery could not be assessed because FM Ss w ere a t an inappropriate level, then Laboratory M atrix S pikes (LM S s) m ay be substituted. If LM S recoveries a re w ith n 30% fo r each targ et analyte and S R S s th e data a re reportable but flagged as not m eeting th e FM S m ethod acceptance criteria.
13.5 Analytical Method Uncertainty
A nalytical m ethod uncertainty fo r each targ et analyte and SR S is determ ined w ith control charted historical analysis batch LC S d ata fo r the m ethod and reported w ith each analysis batch.5 U ncertainty determ inations
5 M ethod uncertainty based on INTERNATIONAL ANS/ISO/IED STANDARD 17025 reference (GUM, Guide to the Expression of Uncertainty in M easurement). M ethod application demonstrated in ETS-12-012, citing references: a.) EURACHEM/CITAC Guide, "Quantifying Uncertainty in Analytical M easurement." Second Edition; Editors: S.L.R. Ellison, M. Rosslein, and A. W illiams. b.jGcorgian, Thomas, "Estim ation o f Laboratory Analytical Uncertainty Using Laboratory Control Samples," Environmental Testing &
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are based on IN TER N A TIO N A L A N S /IS O /IE D STA N D A R D 17025 reference (G U M , G uide to th e Expression o f U ncertainty h i M easurem ent) and described in E T S -12-012. A t least th irty data points are required fo r determ Biing analytical m ethod uncertainty. T h e m ethod uncertainty is defined as 2x th e standard deviation o f th e percent recoveries o f th e pooled lab control s p ite s . W hile a ll LC S d ata points are control charted, only the m ost recent fifty d ata points are used fo r determ ining th e m ethod uncertainty.
W hen less than th irty LCS d ata points have been generated fo r a given an alyte, the analysis batch LC Ss are used to determ ine th e data uncertainty. If FM Ss m eet th e 30% recovery criteria a t a level appropriate to the endogenous level, and th e LC S m eet the 20% recovery criteria, then th e uncertainty o f th e data is determ ined as w ithin 10020% .
A nalysis batch sam ple data w ith FM S recovery outside o f 30% but w ithin 50% o f th e expected value are flagged and reported as outside o f Q C acceptance criteria w ith expanded uncertainties. D ata w ith FM S recovery outside o f 50% o f th e expected value a re reported as N R , w here N R is defined as "N ot R eportable" data outside o f Q C acceptance criteria. If FM S recovery could not be assessed because FM Ss w ere a t an inappropriate level, then Laboratory M atrix S pices (LM S s) m ay be substituted. If LM S recoveries a re w ithin 30% fo r each targ et analyte and appropriate S R S s th e data are reportable but flagged as not m eeting the FM S m ethod acceptance criteria w ith uncertainties o f 30% . If FM S do not m eet th e 30% recovery criteria, and historical FM S data does not exist, th e analytical uncertainty is evaluated on a sam ple-by-sam ple basis, the d ata m ay be reported w ith expanded uncertainty and are flagged.
13.6 Quantitation of PFOA/PFOS - Analysis Batch
C alibration standards consisting o f m ixed branched and n e a r isom er P FO S /P FO A a re preferred. Q uantitation is perform ed by integrating th e lin ear and branched isom ers together. A lternately, th e lin ear and branched isom ers can be integrated separately, applying th e appropriate true value to each cafcratio n curve point fo r each isom er. T he LCS and sam ples are then quantitated by integrating th e lin ear and branched isom ers separately (requires separate analytical results tie s ) and quantitating th e resulting peak against th e lin ear o r branched calbrabon curve. T he results from both integrations are then sum m ed to produce th e final re s u lt Integrating th e Knear and branched isom ers separately m ay be helpful fo r those sam ples w here th e linear/branched ratios do not closely m atch those o f th e reference standards.
H ow ever, to r P FO S /P FO A targ et analytes, if th e calibration standards a re com prised o f predom inantly linear isom ers only th e m ethod requires th e addition o f LCSs o f m ixed branched/linear isom er P FO S /P F O A The purpose o f including these LCSs is to dem onstrate quantitative equivalency (o r quantitative b ias) o f the isom eric m ix w hen using a predom inantly in e a r PFO S or PFO A standard fo r caNbration. A lternatively, in lieu o f m ixed branched and linear isom er P FO S /P FO A LCSs, m ixed branched and lin ear isom er PFO S /P FO A TB M Ss m ay be appfied to dem onstrate m ethod accuracy and precision.
An altern ate m ethod o f quantitation can be perform ed w hereby only th e lin ear isom er o f P FO S /P FO A is integrated and used fo r generating th e calibration curve. T he LC S and sam ples are then quantitated by integrating th e lin ear and branched isom ers separately (requires separate analytical results fifes) and quantitating th e resulting peak against th e in e a r calibration curve. T h e re s lits from both integrations a re then sum m ed to produce th e fin al re s u lt Integrating th e fciear and branched isom ers separately reduces th e oncolum n concentration fo r those sam ples th at contain both lin ear and branched isom ers o f P FO A /P FO S . This ensures th at th e concentration detected is w ithin th e a range o f th e caEbration curve th at is com parable regarcfless o f w hether th e calibration curve w as generated using predom inantly linear isom ers o f PFO S /P FO A or lin ear plus branched isom ers o f P FO S /P FO A .
14 Pollution Prevention and Waste Management
W aste generated w hen perform ing this m ethod w ill be disposed erfappropriate ly . T h e original sam ples w ill be archived a t the 3M Environm ental Laboratory in accordance w ith internal procedures.
AEMvneaaallsuyuasrtieisnm, gNeanontvdUemEnxcbepcrrrt/eaDsisncictnycgmindbiTecerUs2tn0inc0ge0r".t,acJi.nu)Ttlyyaoy2lf0oN0r2,ISB. T.NM. eaansduCreEm.eKntuRyeasttu,lNtsI."S<TLT)Aedcahmnsic, aTl.NMo.,te"A1229L7A,1G99u4idEe dfoitriodnie: "EGstuimidaetliionnesoffor
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15 Records
Each d ata package generated fo r a study m ust include a ll supporting inform ation fo r reconstruction o f the data. Inform ation fo r th e data package m ust include, but is not lim ited to th e follow ing item s: study o r project num ber, sam ple and standard prep sheets/records, instrum ent run log (instrum ent batch records, instrum ent acquisition m ethod, sum m ary pages), instrum ent results tile s , chrom atogram s, calibration curves, and data calculations.
16 Affected Documents
N one.
17 Revisions1*
R evision Num ber
1
Sum m ary o f C hanges
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 sotventfwater mixture when analyzing for PFUnA, PFDoA, PFTrDA, and FOSA. Section 3. Added definitions for internal standard, surrogate internal standard, and surrogate recowry standard. Section 6.Removed the details regarding the instrument parameters to section 10 of the method. Section 7. Updated reference standards to include internal 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 10in ETS-8-O44.0. Updated QC criteria to be consistent with method ETS-8-154.4. Section 10 Procedures. This section was previously section 8 (Sample Handling) in ETS-8044.0. 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 D ata Analysis and Calculations. This section was previously section 11 in ETS8-044.0. 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 PFOA/PFOS. Section 14 Pollution Prevention. This section was previously section 13 in ETS-8-044.0. Section 15 Records. This section was previously section 14 in ETS-8-044.0. Section 16 Affected Documents. This section was previously section 15 in ETS-8-044.0. Section 17 Revisions. This section was previously section 16 in ETS-8-044.0.
E TS -8-044.1
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G L P 1 0 -0 1 -0 1 . In te rim R e p o rt 3 2 : A n a ly s is o f P FO A in G ro u n d w a te r S a m p le s fro m N ew O n S ite W e lls - A d ja c e n t to th e 3M D e c a tu r W a s te w a te r T re a tm e n t P la n t (W W T P ) A p ril 2 0 1 2
S tu d y T itle
A n alysis o f P erflu oroo ctan oic A d d (P F O A ) in G ro un dw ater, S o il and S ed im en t fo r th e 3 M D e c a tu r P h a s e 3 S ite -R e la te d M onitoring P rogram
D a ta R e q u ire m e n t E P A T S C A G ood L ab orato ry P ra c tic e S tan d ard s 4 0 C F R P a rt 7 9 2
S tu d y D ire c to r Jaisim h a K esari P .E ., D E E
W esto n S olutions, Inc. 1 4 0 0 W esto n W a y
W e s tc h e s te r, PA 19380 Phone: 6 10-701-3761
A u th o r Susan W o lf 3 M E n viro nm ental L aboratory
In te rim R e p o rt C o m p le tio n D a te D a te o f s ib lin g
P e rfo rm in g L a b o ra to ry 3M Environm ental Health and S afety O perations
Environm ental Laboratory 3M C enter, Bldg 2 6 0 -0 5 -N -1 7
S t. Paul, M N 5 5 144
P ro je c t Id e n tific a tio n G L P 10-01-01-32
T o ta l N um ber o f P ages 58
The te stin g reported herein m eet the requirem ent* o f ANSI/tSO/lEC 170262006 " General R equirem ents fo r th e Com petence o f Testing end C alibration Laboratories", in accordance w ith the A2LA Testing C ertificate # 2052.01. Testing th a t com plies w ith th is International Standard also m eets p rin cip le s o f ISO 9001:2000.
T e s tin g C e rt # 2 0 5 2 .0 1
GLP10-01-01; Intenm Report 32 Analysis of Groundwater Samples New On-Sile WWTP Weds - April 2012 This page has been reserved fo r specific country requirem ents.
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GLP10-01-01; Interim Report 32 Analysis of Groundwater Samples New On-Site WWTP Wells Apr! 2012
G L P C o m p l ia n c e S ta t e m e n t
Repent Title: G LP 10-01-01, Interim Report 32; Analysis o f PFO A in Groundwater Sam ples from New O n-S ite W ells - Adjacent to the 3M D ecatur W astew ater Treatm ent Plant (W W TP) A pril 2012. Study: Analysis o f Perfluorooctanoic A dd (PFO A ) in Groundwater, Soil and Sedim ent fo r the 3M D ecatur Phase 3 S ite-R elated Monitoring Program . This analytical phase w as conducted in com pliance with Toxic Substances Control Act (TSC A ) Good Laboratory Practice (G LP ) Standards, 4 0 C FR 792, with the exceptions listed below.
These are environm ental sam ples w here there is no specific test substance, no specific test system and no dosing o f a test system .
The reference substances have not been characterized undertheG LP s and the stability under storage conditions a t th e test site have not been determ ined under GLPs.
Page 3 of 58
,i
GLP10-01-01; Interim Report 32 Analysis of Groundwater Samples New OrvSite WWTP Weds - April 2012
Q u a l it y A s s u r a n c e S t a t e m e n t
Report Title: G LP 10-01-01, Interim Report 32; Analysis o f PFOA In Groundwater Sam ples from New O n-Site W e lls -A d ja c e n t to the 3M D ecatur W astew ater Treatm ent Plant (W W TP) April 2012.
Study: Analysis of Peifluorooctanoic A dd (PFO A ) in Groundwater, Soil and Sedim ent for th e 3M D ecatur Phase 3 Site-R elated Monitoring Program .
This report and the accompanying data w ere audited by the 3M Environm ental Laboratory Q uality Assurance Unit (Q A U ), as indicated below. The findings w ere reported to the principal analytical investigator (P A I.), laboratory m anagem ent and study director.
Insp ectio n D ates 4/20/12
Phase Data and Report
Date Reported to
Testing Facility Management
Study D irector
4/26/12
4/26/12
D ate
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GLP10-01-01; Interim Report 32 Analysis of Groundwater Samples New On-Site WWTP WeBs April 2012
Table of C ontents
G LP C om pliance S tatem ent.................................................................................................................................. 3 Q u ality A ssurance S tatem ent................................................................................................................................4 T ab le o f C ontents.....................................................................................................................................................5 List o f T a b le s ............................................................................................................................................................ 6 1 Study Inform ation............................................................................................................................................. 7 2 S um m ary........................................................................................................................................................... 8 3 Introduction........................................................................................................................................................ 8 4 T est & C ontrol S ub stan ces........................................................................................................................... 9 5 R eference S ubstances................................................................................................................................... 9 6 T e s tS y s te m ....................................................................................................................................................10 7 M ethod S um m ary..........................................................................................................................................10
7.1 M eth o d ........................................................................................................................................... 10
7 2 S am ple C ollection......................................................................................................................... 10
7 .3 Sam ple P reparation.....................................................................................................................10 7 .4 A nalysis..........................................................................................................................................10 8 A nalytical R esults........................................................................................................................................... 11 8.1 C alfcratio n ..................................................................................................................................... 11
8 2 System S u itab ility......................................................................................................................... 12
8 .3 U n it o f Q uantitation (L O Q )........................................................................................................12 8 .4 C ontinuing C alib ratio n ................................................................................................................ 12 8 .5 B lanks............................................................................................................................................. 12 8 .6 Lab C ontrol S p ite s (L C S s )........................................................................................................13 8 .7 A nalytical M ethod U ncertain ty.................................................................................................. 14 8 .8 Field M atrix S pikes (F M S )..........................................................................................................14
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8 .9 Laboratory M atrix S pike (L M S )................................................................................................15
8 .1 0
D ata Sum m ary and D iscussion...............................................................................................15
9 C onclusion.......................................................................................................................................................18
10 D ata/S am ple R eten tio n ................................................................................................................................18
11 A ttach m en ts................................................................................................................................................... 18 12 S ig n atu res.......................................................................................................................................................19
L is t o f Ta b l e s
T ab le 1. Sum m arized PFO A R esults (Residuum M onitoring W e is , A pril 2 0 1 2 ).......................................8 T ab le 2 . Sam ple D escription Key C ode............................................................................................................10 T able 3 . Instrum ent P aram eters........................................................................................................................ 11 T a b le 4 . Liquid Chrom atography CondMons................................................................................................... 11 T ab le 5 . M ass Transitions................................................................................................................................... 11 T ab le 6 . Lim it o f Q uantitation (L O Q )................................................................................................................. 12 T able 7 . Laboratory C ontrol S p ite R ecovery.................................................................................................. 13 T able 8 . A nalytical M ethod U ncertainty............................................................................................................14 T able 9 . Field M atrix S p ite Levels.....................................................................................................................15 T ab le 10. DAL G W T W 1 R 120405...................................................................................................................16 T ab le 11. DAL G W T W 2 R 120405...................................................................................................................16 T ab le 12. DAL G W T W 3 R 120405...................................................................................................................16 T ab le 13. DAL G W T W 4 R 120405...................................................................................................................17 T ab le 14. DAL G W T W 5 R 120405...................................................................................................................17 T able 15. DAL G W T W 6 R 120405....................................................................................................................17 T able 16. DAL G W TR IP 01 120405..................................................................................................................18 T ab le 17. R inseate B lank.................................................................................................................................... 18
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GLP10-01-01; Interim Repot 32 Analysis of Groundwater Samples New On-Site WWTP WeMs - April 2012
1 Study Inform ation
Sponsor 3M Com pany S p o n s o r R e p re s e n ta tiv e G ary Hohenstein 3M EH S O perations 3M Building 224-5W -03 S a n t P aul, M N 55144-1000 P h o n e :(6 5 1 )7 3 7 -3 5 7 0
S tu d y D ire c to r Jaisnnha K esari, P .E ., D EE W eston Solutions, Inc. W est C hester, PA 19380 P h o n e :(6 1 0 )7 0 1 -3 7 6 1 F a x :(6 1 0 )7 0 1 -7 4 0 1 jJcesari@ w estonsolutions.com S tu d y L o c a tio n
Testing Facility
3M EH S O perations 3M Environm ental Laboratory Building 260-5N -17 S t P aul, M N 55144 S tu d y P e rs o n n e l W illiam K . R eag en , P h .D ., 3M Laboratory M anager C leston Lange, P h .D ., P rincipal A nalytical Investigator, idanoe@ m m m .com 1: phone (651 )-73 3 -9 8 6 0 Susan W o lf, 3M A nalyst C h elsie G rochow , A nalyst K evin E ich , A nalyst K elly U kes, A nalyst S tu d y D a te s Study Initiation: M arch 8 ,2 0 1 0 Interim R eport 32 Experim ental Term ination: A pril 1 4 ,2 0 1 2 Interim R eport C om pletion: D ate o f Interim R eport Signing L o c a tio n o f A rc h iv e s
A ll o rig in al raw d a ta and th e an alytical re p o rt h ave b een arch ived a t th e 3M E nvironm ental Laboratory according to 4 0 C FR P a rt 7 9 2 . T h e te s t substance and an alytical referen ce standard reserve sam ples a re arch ived a t th e 3M E nvironm ental Laboratory according to 4 0 C FR P a rt 7 9 2
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GLP10-01-01; Interim Report 32 Analysis of Groundwater Samples New On-Site WWTP Wells - April 2012
2 Summary
T h e 3M Environm ental Laboratory received groundw ater sam ples from six new on-site tem porary residuum m onitoring w ells in th e vicinity o f th e 3M D ecatur fa c iity W astew ater T reatm ent P lant (W W TP ) in D ecatur, A L. A to tal o f tw enty-eight sam ple bottles w ere received a t th e 3M Environm ental Laboratory fo r perfluorooctanoate (P F O A ) analysis and included duplicate groundw ater sam ples and tw o field m atrix s p ite (F M S ) sam ples from each sam pling location. Sam ples also included one trip blank containing M iR-QTM w ater and appropriate trip blank spices and one equipm ent rinseate blank. T he equipm ent rinseate blank did not have FM S sam ples prepared fo r determ ination o f PFO A recovery. A ll sam ples w ere logged into th e laboratory inform ation m anagem ent system (U M S ) under project G LP10 -0 1 -0 1 -3 2 . T h e groundw ater sam ples and trip blanks w ere received from W eston personnel on A p rl 9 ,2 0 1 2 . A ll o f the sam ples w ere prepared and analyzed fo r PFO A follow ing 3M Environm ental Laboratory M ethod E TS -8-044.1 "M ethod o f A nalysis fo r the D eterm ination o f Perfluorinated Com pounds in W ater by LC /M S /M S ; D irect Injection A nalysis".
T he average m easured PFO A concentrations a re sum m arized in T a b le 1 . T h e trip blank w as below th e low er lim it o f quantitation (LLO Q ) o f0 .0 2 4 0 ng/m L, indicating adequate control o f sam ple contam ination durfog shipping and sam ple collection. T h e analytical uncertainty w as estim ated a t 23% .
T a b le 1 . S u m m a rize d P FO A R e s u lts (R e s id u u m M o n ito rin g W e lls , A p ril 2 0 1 2 )
S am p le ID
A vg. PFOA C o n cen tratio n
(n g /m L )
DAL GW T W 1R 120405 DAL GW T W 2R 120405
103 1070
DAL G W TW 3R 120405
2260
DAL GW T W 4R 120405 DAL GW T W 5R 120405 DAL GW T W 6R 120405
107 369 238
DAL G W T W 3R R inseate Blank D A L-G W -TR IP01 Blank NA; not applicable
< 0 .2 4 0 < 0 .2 4 0
T he analytical uncertainty fo r PFO A w as estim ated a t + 23% .
R e la tiv e P ercen t D iffe re n c e
1 .9 6 .6 13 28 6 .8 0 .4 2 N /A N /A
3 Introduction
This analytical study w as conducted as part o f th e Phase 3 Environm ental M onitoring and Assessm ent Program fo r th e 3M fa d ity located in D ecatur, A labam a. T h e objective o f th e overall program is to gain inform ation regarding concentrations o f perfluorooctanoate (P F O A ) in various environm ental m ed a such as groundw ater, soils and seefim ents th at are associated w ith and n ear th e D ecatur fa d ity . This analytical study w as conducted to analyze groundw ater sam ples collected from six new tem porary on site residuum m onitoring w ells located adjacent to th e 3M D ecatur W W TP fo r PFO A in an effo rt to characterize regional groundw ater conditions.
T h e 3M Envvonm ental Laboratory prepared sam ple bottles (2 5 0 m L high-density polyethylene) which w ere shipped to D ecatur, AL W eston personnel prior to field sam pling. S am ple bottle sets fo r each groundw ater sam pling location included a fie ld sam ple, field sam ple duplicate, and tw o field s p ite sam ples. Each em pty container fo r groundw ater sam plings w as m arked w ith a H I to here" line to
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produce a fin al sam ple volum e o f 200 m L. C ontainers designated fo r field m atrix sam ples w ere fortified w ith an appropriate m atrix spike solution containing PFO A prior to being sent to th e field fo r sam ple collection. A ll sam ple bottles included th e addition o f 13Cs-PFO A (internal standard) a t a nom inal concentration o f 1 ng/m L and 13C4-P FO A (surrogate recovery standard) a t a nom inal concentration o f 0.1 ng/m L. D ue to th e level o f PFO A d eted ed in th e sam ples, neither th e internal standard nor the surrogate recovery standard w as utilized during sam ple analysis. Laboratory m atrix spices w ere prepared fo r sam pling locations T W 2, T W 3, T W 5, and TW 6 since th e field m atrix spice levels w ere not appropriate fo r these four sam pling locations. S ee section 8 .8 o f th e report fo r field m atrix spice levels. S ee section 8 .9 o f th e report fo r laboratory m atrix spice levels.
Sam ples w ere prepared and analyzed according to th e procedure d e file d in 3M Environm ental Laboratory m ethod E TS -8-044.1 ` M ethod o f A nalysis fo r the D eterm ination erf Perfluorinated Com pounds in W ater by LC /M S /M S ; D irect Injection A nalysis".
T a b le 1 sum m arizes th e average PFO A concentration fo r the duplicate ground w ater sam ples collected, and fo r th e trip blank and aqueous rtoseate blank sam ple. T a b le s 10-17 sum m arize th e individual sam ple results a id th e associated FM S o r LM S recoveries. A ll results fo r th e quality control sam ples prepared and analyzed w ith th e sam ples are reported and discussed elsew here in this rep o rt
4 Test & Control Substances
T here w as not a te s t substance o r control substances in th e classic sense o f a G LP study. This study w as purely analytical in nature.
5 Reference Substances
T h e analytical reference substances used fo r this study a re listed below .
R e fe re n ce S u b sta n ce Chem ical N am e Chem ical Form ula id e n tifie r
Use
Source Expiration D ate S torage Condtttons Chem ical Lot N um ber TC R Number Physical Description Purity
PFOA (L in e a ri B ra n ch e d ) P erfluoroodanoate
C 7F 15C O O H
CAS # 9 5 32 8 -9 9 -7 T arg et Analyte
R eference Standard W ellington
03/17 /2 0 1 4 F ro z e n
TPFQ A 0311 T C R 1 1-0042
Liquid 98 .3%
PFOA (L in e a r* B ra n ch e d ) Perfluorooctanoate
C g H FisO z C A S #335-67-1 F M S R eference
S ta n d a rd Sigm a-Aidrich
7 /2 7/2 0 1 6 Frozen
M K B D 4574V 7 C R 1 1-0029
Powder 9 6 .8%
'fV P F O A
P e rflu o ro o c ta n o a te " CsH F is O
M P FC -C -0511 Internal Standard
W eBngton 05/25 /2 0 1 4
F ro ze n 052411 T C R 11-0016 Liquid
N A <1>
"C rP F O A
Perfluorooctanoate 13C8H F15Oj
M P F C -C -0112 Internal Standard
W eBngton 01/24 /2 0 1 5
Frozen 012312 TC R 12-0 0 0 4 Liquid
N A (1)
(1) Compound sp arici a custom rrrxlijre of masslatoeied perfluorineied compounds at a concentration of 5 0 pgfrnL.
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New On-Site WWTP W eis - April 2012
6 Test System
T here w as not a te s t system fo r this study in th e classic sense o f a G LP study. This study w as conducted fo r analysis o f ground w ater sam ples collected from w ells located in D ecatur, A L by W eston Solutions, Inc. personnel. Sam ples fo r this study are "real w o rk f environm ental sam ples.
T a b le 2 . S a m p le D e s c rip tio n K e y C o d e .
Siring Number
E x a m p le 1
2
3 4
5
String Descriptor
Example
D A L -G W -T W 1 R -0 -1 2 0 4 0 5
S a m p le L o c a tio n
S a m p le T y p e
HUD
D A L " D e c a tu r. A la b a m a G W -G ro u n d W a te r E x a m p le : T W 1 R
Sampang Data
1 2 0 4 0 5 - A p rM S . 2 0 1 2
S a m p le T y p e
0 -p rim a ry s a m p le D B -d u p B c a te s a m p le L S " lo w s p ik e
H S -h io h s p B
7 Method Sum mary
7.1 Method
A nalysis fo r a l analytes w as com pleted follow ing 3M Environm ental Laboratory m ethod E TS -8-044.1 "M ethod o f A nalysis fo r th e D eterm ination o f Perfluorinated Com pounds In W ater by H igh Perform ance Liquid C hrom atography/M ass Spectrom etry D irect Injection A nalysis".
7.2 Sample Collection
Sam ples w ere collected in 2 5 0 m L N algeneTM (high-density polyethylene) bottles prepared a t th e 3M Environm ental Laboratory. S am ple bottles associated w ith G L P 10-01-01-32 w ere returned to the laboratory a t am bient conditions on A pril 9 ,2 0 1 2 . Sam ples w ere stored refrigerated a t th e laboratory a fte r re c e ip t A set o f laboratory prepared Trip Blank and T rip Blank field m atrix spices w ere sent w ith th e s e t o f sam ple collection bottles.
7.3 Sample Preparation
A l sam ples w ere in itially diluted 1:10 by diluting 1 m L o f a w ell m ixed sam ple w ith 9 m L o f MiHi Q w ater and analyzed on 4 /1 2 /1 2 .
Sam pling locations T W 2, T W 3, T W 5, and T W 6 w ere re-analyzed on 4 /2 6 /1 2 , and included the preparation o f a laboratory m atrix spice w ith each sam ple s e t Location TW 2R w as diluted 1:50 by
diluting 0 2 m L o f th e w ell m ixed sam ple w ith 9 .8 m L o f M 9i Q w ater, and included a 1000 ppb LM S.
Location TW 3R w as d lu ted 1:100 by diluting 0.1 m L o f th e w ell m ixed sam ple w ith 9 .9 m L o f M iliQ w ater, and included a 2000 ppb LM S. Locations TW 5R and T W 6R w ere (flu te d 1:10 by diluting 1 .0 mL o f th e w ell m ixed sam ple w ith 9 .0 m L o f M il Q w ater, and included a 2 0 0 ppb LM S.
7.4 Analysis
A l study sam ples and quality control sam ples w ere analyzed fo r PFO A using high perform ance fiquid chrom atography/ tandem m ass spectrom etry (H P LC /M S /M S ). D etaied instrum ent param eters, the liquid chrom atography gradtent program , and th e specific m ass transitions analyzed a re described r i th e
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raw data hard copies placed in th e fin al data packet, and are briefly described below in T a b le 3 , T a b le 4 and T a b le 5.
T a b le 3 . In s tru m e n t P a ra m e te rs .
Instrument Name Analytical Method Followed Analysis Date Liquid Chromatograph
Guard column Analytical column Injection Volume M in Spectrometer Ion Source rciie. cn ul i on oa e. Polarity Software
ETS Ginoer ETS-8-044.1
4/12/12 AdentHOO Belasi C18 (4.6 mm X 100 mm). 5u Belasi C18 (4.6 mmX 100 mml 5u
10 uL Aooied BbsvstemsAPI 5000
Turi Spray Turin kmelediode
Negative Analyst 1.4.2
ETS Buster ETSWM4.1
4/26/12 AotentHOO Betas! C18 (4.6 mmX 100 mm). 5u Belasi C18 (4.6 mmX 100 mm). 5u
5|iL Appled BiosvstBmsAH 4000
Turin Spray Turboion electrode
Neaativs Analyst 1.4.2
T a b le 4 . L iq u id C h ro m a to g ra p h y C o n d itio n s .
Step Number
0 1 2 3 4 5
Total Time (min)
0.0 2.0 14.5 15.5 16.5 20.0
Flow Rate toJmln)
PercentA (2 m ammonium acetate)
ETS-8-044.1 Analysis
730 97.0
750 97.0
750 5.0
750 5.0
reo 97.0
750 97.0
Percents IMotfunofl
3.0 3.0 95.0 95.0 3.0 3.0
T a b le 5 . M ass T ra n s itio n s .
A n a ly te
M a s s T ra n s itio n Q 1 /Q 3
R e fe re n c e M a te ria l S tru c tu re
4 1 3 /3 6 9
PFO A
4 1 3 /2 1 9
U n e a r+ B ra n c h e d
413H 69
D w e l tim e w as 5 0 (4 /1 2 /1 2 ) o r 100 (4 /2 6 /1 2 ) m sec fo r each transition. T h e individual transitions w are sum m ed to produce a "total Ion chrom atogram * (T IC ), which w as used fo r quantitation.
8 A nalytical Results
8.1 Calibration
Sam ples w ere analyzed against an externa) standard calibration curve. C alb ration standards w ere prepared by spiking known am ounts o f th e stock solution containing P FO A (referen ce standard containing both lin ear and branched isom ers) into Midi Q w ater. S tandards ranging from 0 .0 2 5 0 ng/m L to 100 ng/m L (nom inal) w ere analyzed on 4 /1 2 /1 2 w hile only standards ranging from 1 .0 ng/m L to 100
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ng/m L (nom inal) w ere analyzed on 4 /2 6 /1 2 . A quadratic, 1/x w eighted, calb ratio n curve o f th e peak area counts w as used to lit th e data fo r each analyte. T h e data w ere not forced through zero during th e fitting process. C alculating th e standard concentrations using th e peak area confirm ed accuracy o f each curve p o in t Each curve point w as quantitated using the overall calibration curve and review ed for accuracy. M ethod calibration accuracy requirem ents o f 10025% (10030% fo r the low est curve point) w ere m et fo r a ll analytes. The correlation coefficient (r) w as g reater than 0 .9 9 5 fo r PFO A fo r both the 4 /1 2 /1 2 and 4 /2 6 /1 2 analysis.
8.2 System Suitability
A caftxatio n standard w as analyzed four tim es a t th e beginning o f th e analytical sequence to dem onstrate overall system su itab iity. T h e acceptance criteria o f less than o r equal to 5% relative standard deviation (R S D ) fo r peak area and retention tim e criteria o f less than o r equal to 2% R SD w as m et fo r PFO A fo r both th e 4 /1 2 /1 2 and 4 /2 6 /1 2 analysis.
8.3 Limit of Quantitation (LOQ)
T h e LO Q fo r th is analysis is th e low est non-zero c a lx a tio n standard in th e curve th a t m eets in earity and accuracy requirem ents and fo r which th e area counts are a t least tw ice those o f th e appropriate blanks. T he nom inal LO Q fo r PFO A can be found in T a b le 6.
T a b le 6 . L im it o f Q u a n tita tio n (L O Q ).
A n a ly s is D a te
mm2
4 /2 6 /1 2
PFO A n g /m L
0240 ^ 120 9 .5 8 4 7 .9 w 9 5 .8
(1 ) A 1:10 (Button factor w as a p p le d to LO Q . (2 ) A 1:50 (Button factor w as a p p le d to LO Q . (3 ) A 1:10 d u S o n factor w as a p p le d to LO Q . (4 ) A 1:5 0 (Hutton factor w as a p p le d to LO Q (5 ) A 1:100 cHutlon factor w as applied to L O a
8.4 Continuing Calibration
During th e course o f each analytical sequence, continuing calb ratio n verification sam ples (C C V s) w ere analyzed to confim i th at the tostrum ent response and th e in itial calibration curve w ere stifl in control. A ll C C V s m et m ethod criteria o f 100% 25% fo r P FO A fo r both th e 4 /1 2 /1 2 and 4 /2 6 /1 2 analysis.
8.5 Blanks
T hree types o f blanks w ere prepared and analyzed w ith th e sam ples: m ethod procedural blanks, a trip blank, and an equipm ent rinseate blank. M ethod procedural blank results w ere review ed and used to evaluate m ethod perform ance and to determ ine the LO Q fo r PFO A . T he tip blank reflects the shipping and sam ple collection conditions th e sam ple bottles and sam ples experience. T h e equipm ent rinseate blank is an aqueous sam ple th at reflect th e efficiency o f equipm ent cleaning in the field betw een dffierent sam ple co lectio ns and are proof o f no cross contam ination o f sam ples from th e equipm ent
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8.6 Lab Control Spikes (LCSs)
Low , m id, and high lab control spikes w ere prepared fo r th e PFO A and analyzed in trip licate. LCSs w ere prepared by spiking known am ounts o f PFO A into 10 m L o f M illi-Q w ater to produce th e desired concentration. T h e sp ked w ater sam ples w ere then analyzed ki the sam e m anner as th e sam ples. The m ethod acceptance criteria, average o f LCS a t each level should be w ithin 100% 20% w ith an R SD <20% , w ere m et fo r PFO A .
T h e folow ing calculations w ere used to generate data in T a b le 7 fo r laboratory control spices:
10LCS Percent R e * , - 5 ^ ^ 5 2 ^ * 1 2 2 Spike Concentration
LCS%RSD - standart^deviationLCSreplicates 100% average LCS recovery
T a b le 7 . L a b o ra to ry C o n tro l S p ik e R e c o v e ry .
ETS-8-044.1 Analyzed 4/12/12
L a b ID
P F O A (L in e a r+ B ra n c h e d )
S p fte d
C o n c e n tra tio n (n g /m L )
C a ic u ta te d C o n c e n tra tio n
(n g /m L )
% R e c o v e rv
L C S -120411-1 L C S -120411-2 L C S -120411-3 A verage % R SD
0 .4 7 7 0 .4 77 0 .4 77
0 .4 35 0 .4 44 0 .4 52 9 3 .0 % 1 .9 %
9 1 .2 9 3 .2 9 4 .7
L C S -120411-4 L C S -120411-5 L C S -120411-6 A verage % R S D L C S -120411-7 L C S -120411-8 L C S -120411-9 A verage % R SD
4 .7 7 4 .7 7 4 .7 7
2 8 .7 2 8 .7 2 8 .7
4 .5 6 4 .7 0 4 .6 1 9 6 .9 % 1 .5 % 2 5 .3 2 4 .9 2 5 .7 8 8 .2 % 1 .5 %
9 5 .5 9 8 .4 9 6 .7
88.1 8 6 .9 8 9 .5
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GLP10-01-01; Interim Report 32 Analysis of Groundwater Samples New On-Site WWTP Weis - April 2012
T a b le 7 co n tin u e d . L ab o ra to ry C o n tro l S p ik e R ecovery.
EJS-8-044.1 Analyzed 4/26/12
Lab ID
PFOA (L in e a r* Branched!
Spiced C o ncentration
fngAnL)
Calculated Concentration
(ng/mL)
%Recoverv
LC S-120426-1 LC S-120426-2 LC S-120426-3 Average %RSD
4 .7 7 4 .7 7 4 .7 7
4 .3 6 4 .3 5 4 .3 3 9 1 .1 % 0 .4 0 %
9 1 .4 9 1 .2 9 0 .7
LC S-120426-4 LC S-120426-5 LC S-120426-6 Average %RSD LC S-120426-7 LC S-120426-8 LC S-120426-9 Average %RSD
1 9 .1 19.1 1 9 .1
4 7 .7 4 7 .7 4 7 .7
1 5 .5 1 5 .6 1 5 .8 8 1 .9 % 0 .7 5 % 4 2 .4 3 9 .9 3 9 .7 8 5 .3 % 3 .7 %
8 1 .4 8 1 .8 8 2 .6
8 8 .9 8 3 .6 8 3 .3
8.7 Analytical Method Uncertainty
Analytical uncertainty is based on historical Q C data that is control charted and used to evaluate method accuracy and precision. The method uncertainty is calculated following E TS -12 -0 1 2 2 . T he standard deviation is calculated for the set o f accuracy results (in % ) obtained for the Q C samples. T he expanded uncertainty is calculated by multiplying the standard deviation by a factor o f 2, which corresponds to a confidence level o f 95% .
T a b le 8 . A n a ly tic a l M etho d U n c e rta in ty .
Analyte PFOA
Method E T S -8-044.1
Standard Deviation 1 1 .3
Method Uncertainty
23%
8.8 Field Matrix Spikes (FMS)
Low and high field matrix spikes w ere collected a t each sampling point to verify that the analytical method is appicable to the collected m atrix. Field matrix spikes w ere generated by adding a m easured volume of field sam ple to a container spiked by the laboratory with PFO A (reference standard containing both linear and branched isom ers) prior to shipping sam ple containers for sam ple collection. Field matrix spice recoveries within method acceptance criteria o f 10030% confirm that "unknown" components in the sam ple matrix do not significantly interfere with the extraction and analysis o f the analytes o f interest Field matrix spike concentrations m ust be 50% o f the sam ple concentration to be considered an appropriate field spike. Field matrix spices are presented in section 9 o f this report
Page 14 of 58
Il GLP10-01-01; Interim Report 32 Analysis of Groundwater Samples
New On-Site WWTP We8s -April 2012
Table 9. Field M atrix Spike Levels.
S a m p lin g L o catio n All Locations and Trip Blank
S p ik e L evel Low H ig h
P F O A , n g /m L 10 100
T he following calculation w as used to calculate the field matrix spike recovery in Section 9 of the report
( FM S Recovery =
Sam ple Concentration o f F M S -A v e ra g e
C oncentration: Field Sam pie & Field Sam ple P u p .), 100%
Spike Concentraton
8.9 Laboratory Matrix Spike (LMS)
D ue Id the high level of P FO A detected in sampling locations TW 2, T W 3, TW 5, and T W 6, the FM S spike levels w ere not appropriate and laboratory matrix spikes (LM S ) sam ples w ere prepared to verify that the analytical method is applicable to the collected matrix. Laboratory matrix spices w ere generated by adding a m easured volume o f PFO A (reference standard containing both linear and branched isom ers) to an aliquot o f the prim ary sam ple. Since all sam ples required dilution prior to sam ple analysis, the laboratory m atrix spice added w as based on the on-column instrument concentration.
Sampling location TW 2; the prim ary sam ple (G LP10-01-01-32-005) w as diluted 1:50, to which 19.1 ng/fnL o f PFO A w as added for a LM S concentration o f 9 5 6 ng/mL.
Sampling location TW 3; the prim ary sam ple (G LP 10-01-01-32-009) w as diluted 1:100, to which 19.1 ng/rnL of P FO A w as added for a LM S concentration o f 1912 ng/rnL.
Sampling location TW 5; the prim ary sam ple (G LP 10-01-01-32-017) w as diluted 1:10, to which 19.1 ng/m L o f P FO A w as added for a LM S concentration o f 191 ng/mL.
Sampling location TW 6; the prim ary sam ple (G LP 10-01-01-32-017) w as diluted 1:10, to which 19.2 ng/m L o f PFO A w as added for a LM S concentration o f 191 ng/mL.
Lab matrix spice recoveries within method acceptance criteria o f 10030% confirm that ` unknown' components in the sam ple matrix do not significantly interfere with the extraction and analysis o f the analytes o f interest Lab matrix spike concentrations m ust be 50% o f the sam ple concentration to be considered an appropriate field spike. Lab m atrix spices are presented in section 9 of this report.
T he following calculation w as used to calculate the lab matrix spike recovery in Section 9 o f the report
( LM S Recovery =
Sam ple C oncentration o f LM S -
A v e ra g e
Concentration : R eid Sam ple & Field Sam ple P u p .) 100%
Spike Concentraton
9 Data Sum m ary an d Discussion
T he tables below sum m arize the sam ple results and field or lab matrix spice recoveries for the sampling locations as well as the Trip Blanks. Results and average values are rounded to three significant figures according to E PA rounding rules. Because o f rounding, values m ay vary slightly from those listed in the raw data. Field matrix spice recoveries meeting the method acceptance criteria o f 30% , dem onstrate that the method w as appropriate for the given matrix and their respective quantitative ranges.
Page 15 of 58
L U Il M i l -- H M H U I ... ! -- I. Ill I .__ LL i ll 1 U iMil lllIU ilU lll I II lili IL
GLP10-01-01; Interim Report 32 Analysis of Groundwater Samples New On-Site WWTP W eis-April 2012
Table 10. DAL GW TW 1R120405
3MUKSD
Description
G LP10-01-01-32-001
D A L -G W -T W 1R -0-12 0 405
G LP 10 -0 1 -0 1 -3 2 -0 0 2
D A L -G W -7W 1R -O B -120405
G LP10-01-01-32-003
D A L-G W -TW 1R -LS -12 0 405
G LP10-01-01-32-004
D A L -G W -T W 1R -H S -12 0 405
Average Concentration (ng/mL) %RPD
PFOA
Concentration
(ng/mL)
%Recovery
102 NA 104 NA 108 NC 182 7 9 .0
103ngAnL1.9H
NA=Not Appicabie NC = NotCalculated; tie sampleconcenfraBon isgreaterthan 2x the spicelevel Samplesanalyzed on4/12/12 usinga 1:10 cflutionfactor
Table 11. DAL GW TW 2R120405
3M U M S D
Description
G LP10-01-01-32-005
D A L -G W -T W 2R -0-12 0 405
G LP10-01-01-32-006
D A L-G W -TW 2R -D B -12 0 405
G LP10 -0 1 -0 1 -3 2 -00 5 LM S; 9 5 6 ppb D A L -G W -TW 2R -0-LM S
Average Concentration (ng/mL) %RPD
NA=NotAppicabie Samplesanalyzed on4/26/12 usinga 1:50 dfciionfactor
Table 12. DAL GW TW 3R120405
PFOA
Concentration (ng/mL)
% R ecovery
1030
NA
1100
NA
1820
7 9 .0
1C70ng/mL 6/6%
3M U M S ID
Description
GLP10 0 1 -0 1 -32 -0 0 9
D A L-G W -TW 3R O -120405
G LP10-01-01-32-010
D A L-G W -TW 3R -D B -12 0 405
G LP10 0 1 0 1 -3 2 -0 0 9 LM S: 1912 DDb D A L -G W -T W 3R O -L M S
Average Concentration (ng/mL) t %RPD
NA = NotAppicabie Samplesanalyzed on4/26/12 usinga 1:100 cautionfactor.
PFOA
Concentration (ng/mL)
^ R eco very
2110
NA
2400
NA
3680
7 4 .5
2260ngAnL13%
Page 16 of 58
GLP10-01-01; Interim Report 32 Analysis of Groundwater Samples
New On-Site WWTP W eis - April 2012
Table 13. DAL GW T W 4R 120405
PFOA
M U M S ID
Description
GLP1001-0 1 -32 -0 1 3
D A L -G W -T W 4R -0-12 0 4 05
GLP10 0 1 0 1 -3 2 0 1 4
D A L-G W -TW 4R -D B -120405
GLP10 0 1 0 1 -3 2 0 1 5
D A L -G W -T W 4R -L S -120405
GLP10 0 1 0 1 -3 2 0 1 6
D A L -G W -T W 4R -H S -120405
A ve ra g e Concentration (ng/mL) K R P D
C o n c e n tra tio n
(ng/mL)
96R e c o v e ry
105 NA 108 NA 114 NC 184 7 7 .5
107ng/lnLZ8%
NA = NotApptcable NO = NotCaicidatBd;the sample concentration isgreaterthan 2xthe spto level. Samplesanalyzed an 4/12/12 usinga 1:10<Su6onfactor.
Table 14. DAL GW TW 5R120405
M U M S ID
Description
G L P 1 0 01 0 1 -32 0 1 7
D A L -G W -T W 5R -0-12 0 4 05
G L P 1 0 01 0 1 -32 0 1 8
D A L-G W -TW 5R -D B -12 0 405
G LP 10 0 1 0 1 -3 2 0 1 7 LM S; 191 ppb D A L -G W -T W 5R -0-LM S
A v e ra g e Concentration (ng/mL) %RPD
NA = NotAppicabte Samplesanalyzed on 4/26/12 usinga 1:10 tfluBonfactor.
Table 15. DAL GW TW 6R120405
PFOA
Concentration (ng/tnL)
^R ecovery
381 NA 356 NA 5 15 7 6 .7
369 ng/tnL 6.8%
M U M S ID
Description
GLP10 0 1 0 1 -3 2 0 2 1
D A L-G W -T W 6R -0-120405
GLP10 0 1 0 1 -3 2 0 2 2
D A L -G W -T W 6R -D B -120405
G LP 10 0 1 0 1 -3 2 0 2 1 LM S; 191 ppb D A L -G W -T W 6R -0-LM S
Average Concentration (ng/mL) %RPD/RSD
NA=Not Applicable Samplesanalyzed on 4/12/12 usinga 1:10 tflufionfactor.
PFOA
Concentration (ng/mL)
KRecovery
238 NA 237 NA 387 7 8 .3
238 ng/tnL 0.42%
Page 17 of 56
GLP10-01-01; Interim Report 32 Analysis of Groundwater Samples New On-Site WWTP W eis - April 2012
Table 16. DAL GW TRIP01 120405
3MUMSD
G LP10-01-01-32-026 G LP10-01-01-32-027 G LP10-01-01-32-028
Description
D A L -G W -T R IP 01-0-1 2 0 4 0 5 D A L-G W -TR IP01 -L S -12 0 4 05 D A L -G W -T R IP 01-H S -12 0 4 0 5
PFOA
Concentration
fngAMJ
X R ecovsry
<0240
NA
8 .8 0
8 8 .0
9 0 .5
9 0 .5
NA = NotAppicable
NC = NotCalculalBd;the sampleconcentration isgreaterthan 2xthe spke level Samplesanalyzed on4/12/12 usng a 1:10 (Subontartar.
T a b le 17. R in s e a te B lan k
3MUMSD
G LP10-01-01-32-025
Description
D A L-G W -TW 3R -R B -12 0 4 05
NA = NotAppficable Samplesanalyzed on4/12112 usinga 1:10 cBulionfactor.
9 Conclusion
PFOA
Concentration
(ng/mL)
% R ecovery
<0240
NA
Laboratory control spires and field matrix spices w ere used to determ ine the analytical method accuracy and precision for P F O A Analysis w as successively completed foiow ing 3M Environmental Laboratory method E TS -8-044.1 described herein.
10 Data/Sam ple Retention
A l rem aning sam ples and associated project data (hardcopy and electronic) w il be archived accordng to 3M Environmental Laboratory standard operating procedures.
11 Attachm ents
Attachm ent A: Protocol Am endm ent 32 (G eneral Project Outline) Attachm ent B: Representative Chroma tograms and Calibration Curves Attachm ent C: Analytical Method - ETS -8-044.1
Page 18 of 58
12 Signatures
GLP10-01-01: Interim Report 32 Analysis ofGroundwater Samples New On-Site WWTP Wells - April 2012
Cleston Lange, Ph D ., 3M Principal Analytical Investigator
D a le
Page 19 of S8
Attachment A: Protocol A m endment
GLP10-01-01; Interim Report 32 Analysis of Groundwater Samples New On-Site WWTP Wefls April 2012
Page 20 of 58
Analytical M
GLP10-01-01; Interim Report 32 Analysis of Groundwater Samples
M W
Amendment 32
:2012
Study Title Analysis of Perfluorooctanoic Acid (PFOA) in Groundwater, Soil and Sediment for the
3M Decatur Phase 3 Site-Related Monitoring Program
PROTOCOL AMENDMENT NO. 32
A m endm ent Dato: March 28,2012
Perform ing Laboratory 3M Environmental, Health, and Safety Operations
3M Environmental Laboratory Building 260-5N-17
Maplewood, MN 55144-1000
Laboratory Project Identification GLP10-01-01
Sam pling E vent
New On-Site Wells - Adjacent to 3M Decatur W W TP
Page 1 of 6 Page 21 of 58
3 T T ...................
^ M m a u a in T im iW* i f H M -
GLP10-01-01; Interim Report 32 Analysis of Groundwater Samples
Analytical p / S S ^ S i m m "^ 3012 Amendment 32
This amendment modifies the following portion of protocol:
"Analysis of Perfluorooctanoic Acid (PFOA) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program"
Protocol h e m s :
N o c h a n g e s to th e w o rd in g o f th e p ro to c o l a re required.
Amend to read:
No changes to the wording o f the protocol a re required. T his am endm ent only ad dresses and docum ents the addition o f the G en eral P ro ject O utline (G P O ) for the collection and analysis o f groundw ater sam ples as part of th e 3M D ecatu r P hase 3 Program fo r P FO A (G L P 1 0 -0 1 -0 1 ). T h e anticipated sam ple collection w ill occur around the tim efram e o f th e w eek o f April 2 ,2 0 1 2 . T h e groundw ater sam ples fo r this sam pling event will be entered into th e 3M Environm ental Laboratory LIM S as project G L P 10-01 -0 1 -3 2 and reported a s interim report G L P 1 0 -0 1 -0 1 -3 2 , (reflecting study G L P 1 0 -0 1 -0 1 and am endm ent -3 2 ).
Reason:
T he reason fo r this am endm ent is to docum ent the G en eral Project O utline (G P O ) which describes the anticipate groundw ater sam ple collection event fo r six new on-site tem porary residuum m onitoring w ells in the vicinity o f th e W astew ater T reatm en t P lan t (W W T P ) a t th e 3M D ecatur facility. The G P O is three pages in length and included as attached to this am endm ent form.
Page 2 of 6 Page 22 of 58
GLP10-01-01; Interim Report 32 Analysis of Groundwater Samples
Amendment 32
Amendment Approval
Page 3 of 6 Page 23 of 58
I it li
__l-u. . ... _
1
G LP 10 -0 1 -0 1; Interim R e p o t 32 A n a ly sis o f G rou ndw ater S a m p le s N ew O n -S ite W W T P W e is - A p ril 2012
Analytical Protocol: GLP10-01-01 Amendment 32
Environmental Health & Safety Operations, Environmental Laboratory General Project Outline
To: From : cc:
D a te : S u b je c t:
G ary Hohenstein, 3M EHS&Opns
Susan W olf, 3M EHS&Opns; Environmental Lab W illiam R eagen, 3M EHS&Opns; Environmental Lab Cleston Lange, 3M EHS&Opns; Environmental Lab
Jai Kesari, W eston Solutions
March 2 8 .2 0 1 2
A nalysis o f Perfluorooctanoic Acid (P F O A ) in G roundw ater, S oil and S edim ent fo r the 3M D ecatur P hase 3 S ite-R elated M onitoring Program ; G LP Interim R eport 32; N ew O n-S ite W ells - A djacent to th e 3M D ecatu r W astew ater T reatm en t P lan t (W W T P )
1 General Project Information
C on tacts
Lab Request Num ber S ix D ig it D epartm ent N u m b e r P ro je ct S ch e d u ta fT e st D atas
3M S p o n s o r R e p re se n ta tiv e G a ry H ohenstein 3M E H S O p erations 3M Building 224-5W -C3 S ain t P a u l, M N 55144-1000 Ph one: (651) 737-3570 aah oh en stein l9m m m .com
3M E n viro n m e n ta l L a b o ra to ry M a n a g e m e n t W illiam K . R eag en 3M E H S O p n s, Environm ental Laboratory 2 6 0 -5 N -1 7 651 733-9739 w kreaoem am m m .com
P rin c ip a l A n a ly tic a l In vestig a to r C le sto n Lan ge 3M E H S O p n s, Environm ental Laboratory 2 6 0 -5 N -1 7 651 733-9860 ccla n a eiam m m .com
S a m p lin g C o o rd in a to r Tim othy Frin ak W eston S olution s T im othv.frin akiaw estonsolu tions.com Phone: (334)-332-9123
G L P 1 0-01-01-32
Dept #530711, Project #0022674449
Sam plin g sch ed u led for the w eek o f A p ril 2 ,2 0 1 2
All verbal and written correspondence will be directed to Gary Hohenstein and Jai Kesari.
Page 4 o f6 Page 24 of 58
G LP 10 -0 1 -0 1; Intsrim R eport 32 A n a ly sis o f G rou ndw ater S a m p le s N ew O n -S ite W W T P W e is - A p ril 2012
Analytical Protocol: GLP10-01-01 Amendment 32
2 Background Information and Project O bjective^)
T h e 3M E H S O perations Laboratory (3M Environm ental Lab) w ill receive and a n a ly ze groundw ater sam ples collected from six new tem porary on-site residuum m onitoring w ells located ad jacen t to th e 3M D ecatu r W W T P fo r P erfluorooctanoic Acid (P F O A ). A nalyses w ill b e conducted u nd er th e G LP requirem ents o f E P A T S C A G ood Laboratory P ractice S tandards 4 0 C F R 792. G roundw ater sam ples w ill be collected by W eston Solutions personnel th e w e e k o f A pril 2, 2 0 1 2 . T h e 3M Environm ental Laboratory w ill prepare th e sam ple bottles w ith all required spikes to en sure that results for P FO A a re o f a known precision and accuracy. T h e final report win be subm itted to G ary H ohenstein and Jai K esari upon com pletion under interim report G LP 1 0 -0 1 -0 1 -3 2 .
3 Project Schedule
Sam ple colection bottles will be prepared by 3M Environmental Laboratory for sampling the w eek of April 2, 2012. Sam ple bottles will be shipped in coolers overnight to 3M D ecatur for arrival on Friday, March 3 0 ,2 0 1 2 . Sam ple bottles should be stored refrigerated on-site until sam ple collection.
M artin Sm ith \ W esto n T ra ile r 3M D ecatur P lant 1400 S tate Docks Road D ecatur, A labam a 35601
4 Test Parameters
The targeted limit o f quantitation will be 0 .0 2 5 n g /m L (ppb) for PFO A.
Six sampling locations have been specified; TW 1R , TW 2R , TW 3R , TW 4R , T W 5R , and T W 6R . These are new wells with no historical sam pling values for estimating field m atrix spike levels, however, Information received from W eston indicates that locations T W 3R , T W 4R and potentially T W 5R , are expected to have higher concentrations based on the expected groundwater gradients in the area of these w ells and field observations. Given the limited information on expected levels, at each sampling location, a total of four sam ple bottles will be collected (sam ple, sam ple duplicate low field matrix spike and high field m atrix spike). T he low field m atrix spike will be prepared at 10 ng/m L and the high field matrix spike will be prepared a t 100 ng/m L. T h e m i to here" line on each 250 mL N aigene bottle will be 2 0 0 mL. O ne set o f trip blanks consisting of reagent-grade w ater as well as a low and high trip blank spike w il be prepared a t the 3M Environmental Laboratory and sent to the sampling location with the other bottles. All sam ple bottles will include the addition of 13Cg-PFOA (internal standard) at a nominal concentration of 1 ng/m L. All sam ple bottles will also include the addition o f 13C 4-P FO A (surrogate spike) at a nominal concentration of 0.1 ng/mL. O ne additional bottle will b e prepared to be used for the preparation o f the equipm ent rinseate blank. A 500-m L bottle o f laboratory reagent w ater will be sent with the sam ple bottles to be used to generate the rinseate blank sample.
S Test Methods
Sam ples will be prepared and analyzed by LC /M S /M S following E TS -8-044.1 "Method of Analysis for the Determination o f Perfluorinated Com pounds In W ater by LC/M S/M S; Direct Injection Analysis".
The data quality objectives for these studies are quantitative results for the target analytes with an analytical accuracy of 10030% . Field matrix spikes not yielding recoveries within 10030% will be addressed in the report and the final accuracy statem ent m ay be adjusted accordingly. W here applicable, sam ples will be analyzed against an internal standard calibration curve. Each curve point will contain isotopically-labeled perfluorocarboxylic adds and perfluorosulfonic ad d s at a nom inal concentration o f 1 ng/mL. The calibration curve w il be generated by taking the ratio of the standard peak area counts over the internal standard peak area counts to fit the data tor each analyte.
Page 5 of 6
Page 25 of 58
n n r i i nil hiin litui 11ili i _il J i . l I,. . null ill i
J i 1 I , lillii. ,iu i,U .li.ill i i 111 .,1
G LP 10 -0 1 -0 1; Interim R eport 32
A n a ly sis o f G rou ndw ater S a m p le s
N ew O n -S ite W W T P W e is - A p ril 2012
Analytical Protocol: GLP10-01-01 Amendment 32
6 Reporting Requirements
For each sampling location, the report will contain the results for the sam ple, sam ple duplicate, and field matrix spike. Trip blank and trip blank spike will be reported for the sampling event as will any equipm ent/rinseate blanks prepared in the field. Laboratory control spikes of reagent w ater prepared a t the tim e of sam ple extraction will also be reported and used to evaluate the overall method accuracy and precision. Method blanks o f reagent w ater prepared a t the tim e of sam ple extraction will be used to determ ine the method detection lim it
Page 6 of 6 Page 26 of 58
GLP10-01-01; Interim Report 32 Analysis of Groundwater Samples New On-Site WWTP W eis - April 2012
At ta c h m e n t B : R e p r e s e n t a tiv e S a m p l e C h r o m a to g r a m s a n d C a l ib r a tio n C u r v e (s )
Page 27 of 58
*** Ginger AG01330509
GLP10-01-01; Interim Report 32 Analysis of Groundwater Samples New On-SRe WWTP Walls - April 2012
Results Name: g!20412a.rdb
Printing Date: Monday* April 16, 2012
Page 28 of 58
*** Ginger AG01330509
GLP10-01-01; Interim Report 32 Analysis of Groundwater Samples New On-Ske WWTP Wells - April 2012
Results Name: g!20412a.rdb
Printing Date: Monday, April 30, 2012
Page 29 of 58
*** Ginger S.G01330509
GLP10-01-01; interim Report 32 Analysis of Groundwater Samples New On-Site WWTP Wells - April 2012
Results Name: g!20412a.rdb
Data printed by STM
Printing Time: 12:31:23 PM
Printing Date: Monday, April 30, 2012
Page 2 of 3
Page 30 of 58
** Ginger AG01330509
GLP10-01-01; Interim Report 32 Analysis of Groundwater Samples New On-SKe WWTP Wells - April 2012
Results Name: gl20412a.rdb
Printing Time: 12:31:24 PM Printing Date: Monday, April 30, 2012
Page 31 of 58
Workstation: ETSBUSTER
GLP10-01-01; Interim Report 32 Analysis of Groundwater Samples New On-Site WWTP Walls - April 2012
Batch Name: b!20426a.dab
Printing Time: 11:50:40 AM Printing Date: Monday* April 30 2012
Page 32 of 58
*** Bustsr J2930203
GLP10-01-01; Interim Report 32 Analysis of Groundwater Samples New On-Site WWTP Wells - April 2012
Batch Name: b!2026a.dab
Printing Time: 12:37:04 PM Printing Date: Monday, April 30, 2012
Page 33 of 58
*** Buster J2930203
GLP10-01-01; Interim Report 32 Analysis of Groundwater Samples New On-Site WWTP Walls - April 2012
Batch Name: bl20426a.dab
Printing Date: Monday April 30 2012
Page 34 of 58
** Buster J2930203
GLP10-01-01; Interim Report 32 Analysis of Groundwater Samples New On-Site WWTP Wells - April 2012
Batch Name: b!20426a.dab
Page 35 of 58
I iB i l l Mi ii minmu-- ini mwiii hi hi ___l-l _--ljl______
i j l i. ________ .
GLP10-01-01; Interim Report 32 Analysis of Groundwater Samples New On-Sile WWTP W eis - April 2012
At ta c h m e n t C : A n a ly tic a l M e th o d (s )
Page 36 of 58
GLP10-01-01; lirterim Report 32 Analysis of Groundwater Samples New On-Site WWTP W eis - April 2012
3M Environmental Laboratory
M ethod Method o f Analysis for the Determination o f Perfluorinated Compounds in Water
by LC/MS/MS; Direct Injection Analysis Method Number: ETS-8-044.1 Adoption Date: 4/12/07 , Effective Date: / i / f / n
Approved By: William K. Reagen, Technical Director, Environmental Laboratory
J / J C / i / 3t O / /
Date
ETS-8-D44.1
Page 1 of 22
Method of Analysis forthe Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct
Injection Analysis
Page 37 of 58
Il i Ili Ballili IIIIIMUMIH
GLP10-01-01; Interim Repot 32 Analysis of Groundwater Samples New On-Site WWTP Weds - April 2012
1 Scope and Application
This method describes the direct injection analysis of perfkxxinated compounds (P FC s) from w ater m atrices using high-performance liquid chromatography tandem m ass spectrometry (H P LC /M S/M S ). The method is generally applicable but not limited to the m easurem ent of perfluoroalkyl sulfonamides and perfluorinated alkyl ad ds (PFAA s) such as perfluorosuMbnic ad d s (PFSA s) and perfluorocarboxyfic adds (PFC A s) (Table 1). W ater sam ples containing heavy particulate m ay require preparation by an alternate method such as E TS -8-154 "Determination o f Perfluorinated A dds, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Perform ance Liquid Chrom atography/M ass Spectrometry". The method is applicable to both external standard and internal standard calibration1.
T a b le 1. R e p re s en tativ e T a rg e t A n a ly te s
A c ro n y m
P FB A (C 4A dd) P FP eA (C 5 A rid) PFHxA (C 6 A rid) PFHpA (C 7 A rid) PFQA (C 8 A rid) PFNA (C 9 A rid) PFDA (C 10 A rid) PFUnA (C 11 A rid) PFDoA (C12 A rid) P F TrD A (C 13A rid ) P FB S (C 4 Sulfonate) PFHS (C 6 SUfonate) P F O S (C 8 Sulfonate) FBSA (C 4 Sultonanide FOSA (C 8 Sulfonamide)
A n a ly te
Peifluorcbulanoic arid PerfluorDpefTtanoic arid Perfluorohexanoic arid Perfluoroheptanoic arid Petfluorooctanoic arid Peffluorononanoic arid Perfluorodecanoic arid PerRuoroundecanoic arid Peifluorododecanoic arid Peffluorobidecanoic arid Perfluorobtdanesulfonic arid Perfluorohexanesulfonic arid Peffluorooctanesutfanic arid PorfluofobutanesuRonamtde Pefluorooctanesulfonamide
C h e m ic a l A b s tr a c t S e rv ic e s
R eg istry N u m b e r (C A S R N )
375-22-4 2706-90-3 3 0 7 -2 4 4 375-85-9 335-67-1 375-95-1 3 3 5 -7 6 -2 2058-94-8 307-55-1 72629-94-8 375-73-5 355464 1763-23-1 30334-69-1 7 5 4 -9 1 -6
T he Minimum Reporting Level (M R L) is the Limit o f Quantitation (LO Q ) that m eets Data Q uality Objectives (D Q O s) that are developed based on the intended use o f this method.
Method Flexibility - This is a perform ance-based method and m ay be generally applied to the determ ination o f perfluorinated compounds in w ater m atrices when analysis batch quality control (Q C ) criteria are m et12. Each set o f sam ples are prepared in an analysis batch with calibration standards, LCSs, blanks, and continuing calibration check standards analyzed on the sam e instrument during a tim e period that begins and ends with the analysis of the appropriate continuing calibration check standards. T he laboratory is permitted to modtfy the LC column, mobile phase composition, LC conditions, and M S /M S conditions. Method modifications should be considered to improve method perform ance or to m eet data quality objectives for the study. In all cases w here method mocfifications are im plem ented, the batch
a1nHdieCm8 petchroflduoisrosaulpkpaonretesdulbfoynvaamlididaetiionnlawbiothraitnotreyrncaolnsttraonldsaarmdpclaelsiburnadtieorn3fMormC4et-hCo1d3vPaFliCdaAtiso,nCE4,lC1-60.6a6n7d. C8 PFSAs, 2MMGeeutthhidooaddnsVcoeafflAiodrnaetaisloytansb"is,libisnh.)iSnEugPpmApoeMrtht eootdfhPoQdrCe5-r3Ce7gr,iitasetnrridaatcibo.a)nsEDeudarootanpReaae.n)qFuCDioremAmmMenisatsysiof2on0r:0AG1 ,nu"nidGeaxunIicdIea(nfPocarerGtfAoer,nIsenerdacuttiisnotgnrya4,n)BdainoRadenpAaolnyrnttiiencxgaml (Part A,section 5) o fDirective 91/414, SANCO/3029/99 rev. 4 (11/07/00).
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analytical Q C s (section 9 ) must be completed and pass Q C acceptance criteria (section 13) if the data from the analytical batch are to be reported.
2 Method Summary
W ater sam ples are analyzed as neat aqueous sam ple or as solvent diluted aqueous sam ples by direct injection using LC /M S /M S . Sam ples containing heavy particulate m ay not be suitable for analysis by this method. Sam ples containing suspended particulate should be centrifuged o r fttered prior to removing a sam ple aliquot or cfiluting with solvent The w ater sam ple is m ixed well prior to removing an aliquot or diuting, if necessary, with A STM Type I water, H PLC w ater, other suitable w ater, or solvent (m ethanol).
Quantitation is by stable isotope internal standard calibration in laboratory reagent water. All perfluorinated compounds (P FC s) target analyte concentrations o f perfluorosulfbnic adds (PFSA s) and perfluorocarboxyiic ad d s (P FC A s) are reported as anions and corrected for their salt or free ad d form s. Alternatively, quantitation m ay be performed by external standard calibration.
This is a perform ance-based method. Method uncertainty for each target analyte is determ ined for each analytical batch using multiple laboratory control spikes at multiple concentrations. This method also requires that the precision id accuracy for each sam ple be determ ined usarg field matrix spikes to verify that the method is applicable to each sam ple m atrix.
Calibration standards for PFUnA, PFDoA, PFTrD A , and FO SA have been found to be unstable for m ore than 2 days in 100% water. Sam ples requiring analysis for these compounds by this method should be diluted 1:1 with methanol and analyzed against a calibration curve prepared In 1:1 synthetic groundwater.M eOH.
3 Definitions
3.1 Analysis Batch
A set o f study sam ples that are prepared with calbration standards, laboratory control sam ples, and procedural blanks, and analyzed on the sam e instrument during a tim e period that begins and ends with the analysis o f the appropriate continuing calibration check standards.
3.2 Analytical Sample
A portion o f a laboratory sam ple prepared for analysis.
3.3 Calibration Standard
A solution prepared by spiring a known volume o f the W orking Standard (W S ) into a predeterm ined am ount o f A STM Type I, HPLC grade w ater, or other suitable w ater (i.e. matrix w ater), and analyzed according to this method. Calibration standards are used to calibrate the instrument response with respect to analyte concentration.
3.4 Laboratory Duplicate Sample (LDS, or Lab Dup)
A laboratory duplicate sam ple is a separate aliquot o f a sam ple taken in the analytical laboratory th at is analyzed separately with identical procedures. Analysis o f LDSs compared to that of the first aliquot give a m easure o f the precision associated with laboratory procedures, but not with sam ple collection, preservation, or storage procedures.
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3.5 Field Blank (FB)/Trip Blank (TB)
A STM Type I, HPLC grade w ater, or other suitable water, placed in a sam ple container in the
laboratory and treated as a sam ple in all respects, including exposure to sampfing site conditions, storage, preservation and all analytical procedures. T he purpose o f the TB is to
determ ine i test substances or other interferences are present in the field environment. This
sam ple is also referred to as a Trip Blank.
3.6 Field Duplicate Sample (FDS, Field Dup)
A sam ple collected in duplicate a t the s a n e tone from the sam e location as the sam ple. The FD S is handted under identical circumstances and treated exactly the sam e throughout field and laboratory procedures. Analysis o f the FD S com pared to that o f the first sam ple gives a m easure o f the precision associated with sam ple collection, preservation and storage, as w e l as with laboratory procedures.
3.7 Field Matrix Spike (FMS)
A sam ple to which known quantities o f the target analytes, ISs and SR Ss are added to the sam ple bottle in the laboratory before the bottles are sent to the field for collection o f aqueous sam ples. A known, specific volume o f sam ple must be added to the sam ple container withoiA rinsing. This m ay be accomplished by making a TB to this leveT line on the outside o f the sam ple container. T he FM S is analyzed to ascertain if any m atrix effects, interferences, or stability issues m ay complicate the interpretation o f the sam ple analysis.
3.8 Trip Blank Matrix Spike (TBMS)
An aliquot o f A S TM Type I, HPLC grade w ater, or other suitable w ater, to which known quantities o f the target analytes, ISs and SR Ss are added in the laboratory prior to the shipm ent o f the collection bottles. T he TBM S is analyzed exactly lice a study sam ple to help determ ine if the method is in control and w hether a loss of analyte or analytical bias could be attributed to sam ple hokfing tim e, sam ple storage and/or shipment issues. A lo w and high TB M S are appropriate when expected sam ple concentrations are not known or m ay vary.
3.9 Internal Standard (IS)
A compound added to each study sam ple, caHxation standard, laboratory control sam ples, and procedural blanks a t a consistent level (typically around 1 ng/m L). T he internal standard(s) are stable isotope labeled versions o f the target analytes. T h e area count ratio of the target analyte to the internal standard is used for calibration. Surrogate ISs are appfied when stable isotope IS s o f target analytes are unavailable. A surrogate IS is not necessarily a stable isotope labeled version o f Ih e target analyte, but is treated as an internal standard for quantitation.
3.10 Laboratory Control Sample (LCS)
An aliquot o f control matrix to which krxrwn quantities o f the target analytes, ISs and SR Ss (when applicable) are added in the laboratory a t the tim e when sam ples are aliquotted. At least three levels (two levels for S R S s) in triplicate are included, one generally a t the low end o f the c a ix a tio n curve and one near the mid range and the upper end o f the curve. The LCSs are analyzed exactly like a laboratory sam ple to determ ine w hether the stabiity o f the standards. LCSs should be prepared each day sam ples are aliquoted.
3.11 Laboratory Matrix Spike (LMS)
A laboratory matrix spice is an aliquot o f a sam ple to which known quantities o f target
analytes, ISs and S R S s (w hen applicable) are added in the laboratory. The LM S is analyzed exactly Ik e a laboratory sam ple to determ ine whether the sam ple m atrix contributes bias to the analytical results. T h e endogenous concentrations o f the analytes in the sam ple matrix must be determined in a separate afiquot and the m easured values in the LM S corrected for these concentrations. LM Ss are optional for analysis o f aqueous sam ples.
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3.12 Laboratory Sample
A portion or aliquot o f a sam ple received from the field for testing.
3.13 Limit of Quantitation (LOQ)
The lower limit of quantitation (LLO Q ) for an analytical batch is the lowest concentration that can be reliably quantitated within the specified limits o f precision and accuracy. T h e LLOQ is generally selected as the lowest non-zero standard in the calibration curve that m eets method acceptance criteria. The LLOQ for each target analyte is established for each analysis batch as the lowest calbration standard with area counts at least tw ice that o f the average area counts o f the procedural blanks.
The upper limit of quantitation (U LO Q ) for an analytical batch is the highest concentration that can be reliably quantitated within the specified limits o f precision and accuracy. T h e highest standard in the calibration curve that m eets method acceptance criteria is defined as the ULOQ.
3.14 Method/Procedural Blank
An aliquot o f control matrix that is treated exactly Ik e a laboratory sam ple including exposure to all glassware, equipm ent solvents, and reagents that are used with other laboratory sam ples. T he method blank is used to determ ine if test substances or other interferences are present in the laboratory environment, the reagents, or the apparatus.
3.15 Sample
A sam ple is an aliquot rem oved from a larger quantity o f m aterial intended to represent the original source material.
3.16 Stock Standard Solution (SSS)
A concentrated solution o f a single-analyte prepared in the laboratory with an assayed reference compound.
3.17 Surrogate Internal Standard
An IS that is not necessarily a stable isotopically labeled target analyte, but is treated as an internal standard for quantitation. Surrogate ISs are used when isotopically labeled counterparts o f the target analyte are not commercially or readily available.
3.18 Surrogate Recovery Standard (SRS)
An isotopically labeled standard, not used as an internal standard, that is added to each sam ple and appropriate Q C sam ple as a m eans to evaluate the method perform ance for a chemical class of compounds (e.g., PFSAs, PFCAs).
3.19 Working Standard (WS)
A solution o f several analytes prepared in the laboratory from S SS s and diluted as needed to prepare calibration standards and other required analyte solutions.
4 Warnings and Cautions
4.1 Health and Safety
The acute and chronic toxicity of the standards for this method have not been precisely determ ined; however, each should be treated as a potential health hazard. T he analyst should w ear gloves, a lab c o a t and safety glasses to prevent exposure to chem icals that might be present.
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The laboratory is responstole for maintaining a safe work environm ent and a current awareness o f local regulations regarding the handling o f the chem icals used in this method. A reference fle o f m aterial safety data sheets (M S D S ) should be available to all personnel involved in these analyses.
4.2 Cautions
The analyst m ust be fam iliar with the laboratory equipm ent and potential hazards including, but not limited to, the use of solvents, pressurized gas and solvent in e s , high voltage, and vacuum systems. R efer to the appropriate equipm ent procedure or operator m anual for additional information and cautions.
5 Interferences
During sam ple preparation and analysis, m ajor potential contaminant sources are reagents and glassware. All m aterials used in the analyses shall be demonstrated to be free from interferences under conditions o f analysis by running method blanks.
Parts and supplies that contain Teflon should be avoided or minimized due to the possibility o f interference and/or contamination. T hese m ay include, but are not limited to: wash bodies, Teflo n * lined caps, autovial caps, HPLC parts, etc.
T he use o f disposable micropipettes or pipettes to aliquot standard solutions is recomm ended to m ake calibration standards and matrix spires.
6 Instrumentation, Supplies, and Materials
6.1 Instrumentation
Analytical balance capable of reacfing to 0.0001g H PLC /M S /M S or H PLC /M S system, as described in Section 10.
6.2 Supplies and Materials
Sam ple collection bottles-- H D P E (e.g., N algeneTM ) wide-mouth bottles with screw cap. N ote: Do not use fluorinated or Teflon bottles or Hned caps. Coolers or boxes for sam ple shipm ent 15-m L and 50-m L disposable polypropylene centrifuge tubes. Class A pipettes and volumetric flasks, various. 2 mL HPLC autovials Disposable pipettes, polypropylene or glass as appropriate Centrifuge capable o f spinning 15-m L and 50-m L polypropylene tubes a t 3000 rpm.
7 Reagents and Standards
N ote: Suppliers and catalog numbers are for illustrative purposes only. Equivalent perform ance m ay be achieved using chemicals obtained from other suppliers. D o not use a lesser grade o f chemical than those listed.
7.1 Chemicals
W a te r-M K -Q , H PLC grade, or other suitably appropriate sources
Calcium A cetate - A .C .S . Reagent G rade
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Magnesium Acetate - A .C .S . R eagent Grade Methanol - HPLC grade Ammonium Acetate - A .C .S . Reagent G rade
7.2 Representative Target Analytes, ISs, and SRSs
PFBA, Heptafluorobutyric Acid, (C4 Perfluorinated A dd )
PFPeA , Nonafluoropentanoic A dd (Cs Perfluorinated A dd )
PFHxA, Perfluorohexanoic A dd (Ce Perfluorinated A dd )
PFHpA, Tridecafluoroheptanoic A dd, (C7Perfluorinated A dd ) PFO A, Ammonium perfluorooctanoate, (Ca Perfluorinated A dd )
PFN A , Heptadecafluorononanoic A dd, (Cg Perfluorinated A dd)
PFDA, Nonadecafluorodecanoic A dd (C10Perfluorinated A dd)
PFUnA, Perfluoroundecanoic A dd, (C n Perfluorinated A dd )
PFDoA, Periluorododecanoic A dd, (C12Perfluorinated A dd) PFTrD A , Perfluorotridecanoic A dd, (C13Perfluorinated A dd)
FBSA, Perfluorobutanesulfbnamide FO SA, Perfluorooctanesulfonylamide PFB S, Potassium PerfluorobutanesuHbnate P FH S , Perfluorohexanesulfbnate P FO S, Potassium perfluoroodanesulfbnate P FO A [1 ,2 ,3 ,4 -13C], 13C4-isotopically labeled perfluorooctanoic ad d (S R S )
P FO S [12 , 3 ,4 -13C], 13C4-isotopically labeled Perfluorooctanesutfonate (S R S )
PFU nA [1,2-13C ], 13C2-isotopically labeled Perfluoroundecanoic a d d (S R S )
JPFDA,
....................................... . . .
-
. . . . ^ ................ ... . . '"CaJPFOS,
and [1,2 ,3 ,4 ,5 ,6 ,7 ,8 - CaJPFOSA(W ellington Laboratories, Guelph, O N ) in combination with
added a i,2 ,3 ,4 ,5 -13Cs]PFPeA, ([1 ,2 ,3 ,4 -n C4]P F H p A and [^ O JP F B S can be used to prepare
a stock IS solution. Alternatively, individual stable isotope ISs can b e used to prepare a stock
IS mixture.
O ther ISs can be applied.
7.3 Reagent Preparation
2 m M Ammonium acetate solution (Analysis)--W eigh 0 .3 g o f Ammonium acetate and dissolve in 2 .0 L of reagent water.
Synthetic Groundwater (containing 2 5 ppm C a and M g) - W eigh 0.61 g o f Caldum Acetate and 0 .9 2 g o f Magnesium Acetate and dissolve in 6 .0 L o f reagent water.
Note: Alternative volum es m ay be prepared as long as the ratios o f the solvent to solute ratios are m aintained.
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7.4 Stock Standard Solution (SSS) and Working Standard Solution Preparation
T he following standard preparation procedure serves as an exam ple. W eighed amounts and final volum es m ay be changed to suit the needs of a particular study. For exam ple, pL volum es m ay be spiked into volumetric flasks when cfiluting stock solutions to appropriate levels.
100 pg/m L ta rg e t an alyte SSSs W eigh out 10 mg erf analytical standard (corrected for percent salt, acid ETS-4-031] and purity) and (flu te to 100 m L with methanol or other
suitable solvent, in a 100 m L volumetric flask. Transfer to a 125 m L L D P E bottle o r other suitable container. Prepare a separate solution for each analyte. Expiration dates and storage condtions of stock solutions should be assigned in accordance with laboratory standard operating procedure. An exam ple o f purity and salt correction is given below for PFOS.
,__t m olecular w eight o f anion salt correction factor = ------- --- ------ =-- -- --- --
m o d ecular w eig ht o f salt
499 P F O S (K + )salt correction factor = -- = 0 .9 2 7 5
538
10 mg CaF^SOaX* with purity 90% = 8 .3 5 mg C ^n S O f (10 m g*0.90*0.9275=8.35 m g)
10 pgfm L (10,000 ngfm L) m ixed w o rkin g stan d ard --Add 5.0 m L each o f the 100 pg/m L S SS s to a 5 0 m L volumetric flask and bring up to volum e with solvent
1 pg/m L (1 ,0 0 0 ngfm L) m ixed w o rkin g stan d ard --A dd 0 .5 mL o f the 100 pgfoiL S SS s to a 50 mL volumetric flask and bring up to volume with solvent
0.1 pgfhiL (1 0 0 ngfm L) m ured stan d ard --Add 0 .0 5 m L o f the 100 pg/m L S SSs to a 50 mL volumetric flask and bring up to volume with solvent
S to rag e C onditions-- Store all S SS s and w orkrig standards in accordance with laboratory standard operating procedure or in a refrigerator a t 42C for a maximum period o f 6 months from the date o f preparation.
7.5 Calibration Standards
Calibration can be performed by IS or external calibration. Using the working standards described above, prepare calixation solutions in A STM Type I w ater, H PLC w ater, other suitable water, o r a mixture o f solvent and w ater using the informa tion in Table 2 as a guideline. Note: Volum es o f w ater o r water/soivent m ixtures and working standards m ay be adjusted to m eet the data quality objectives addressed in the general project outline. C alixatio n levels other than those listed below can b e prepared as needed.
For the quantitation o f PFO A and P FO S , reference m aterials of certified mixed linear and branched isom er ate preferred. Alternately, reference m aterials of prim arily n ear isomers of P FO A and/or PFO S m ay be used, however, when quantitating with predom inantly linear reference standards, additional LCS sam ples containing both linear and branched isomers o f P FO A and P FO S a te required3.
7 5 .1 Internal Standard (IS ) and Surrogate Recovery Standard (SR S)
For IS calibration, stable isotope internal standards of each target analyte o r appropriate surrogate ISs should be spiced a t the sam e level in a l calixation standards. O nce the calibration standards have been prepared as stated above in Section 7.5, all calixation standards are spired with a separate internal standard spiking solution. Typically the
1 A rty n rf tm ranM iTinp n
n f th r n tf n f Tr jr r m r r sta n d a rd s r m tim n iip rfrtjfia d h n r r n d h ra irh r d i i m m o f
PFOA/PFOS canbe found m 3M report El14)560.
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concentration o f the internal standard is consistent with the internal standard concentration expected in the sam ples being prepared, usually 1 n g/m L The concentration o f the internal standard spiking solution is typically 2 pg/mL. A separate zero point or method blank is typically prepared a t the sam e tim e as the calibration standards, using the sam e solution used to prepare the standards (A S TM Type I w ater, H PLC w ater, other suitable w ater, or a solvent/water m ixture), and is spired with the internal standard a t th e sam e concentration as the calibration curve, typically a t 1 ng/mL.
If the sam ples being analzyed w ere pre-spiked with S R S s, the calibration curve prepared in Section 7 .5 is spired with a separate S R S spiking solution. Typically, the sam ple bottles are spiked with a S R S a t 0.1 ng/m L. The final calibration curve m ust consist o f a t least six calibration points after analysis. T he following table provides an exam ple o f sp ire concentrations and volum es used to achieve a multi-point extracted calibration curve with internal standard and surrogate standard.
Table 1 lists recom m ended stable isotope internal standards for several PFS A and PFC A target compounds. A custom mix of isotopically labeled target analytes in a methanolic solution containing ([1 ,2 ,3 ,4 -13C JPFB A , [1 ,2 -X J P F H x A , [1,2,3,4,5,6,7,8 -13Ca[PFOA, [1 A 3 ,4 ,5 ,6 ,7 ,8,9-" Cg]PFNA, [1,2,3,4,5,6 - 13C d F fDA, [1 ,2,3,4,5,6,7 - 1iC7]PFUnA , [1,2 "Q JP F D o A , [ U ,3 - l3CalPFHS, [1 ,2 ,3 ,4 ,5 ,6 ,7 ,8 -13CalPFO S, and [1 ,2 ,3 ,4 ,5 ,6 ,7 ,8 -l3Ca]FOSA (W ellington Laboratories, Guelph, O N ) in combination with added ([1,2 ,3 ,4 ,5 -13Cs]PFPeA, ([1,2,3,4-13G |]PFH pA , and [1sO JP FB S can be used to prepare a stock IS solution. Alternative sources o f certified stable isotope labeled target analytes are appicable. Alternatively, individual stable isotope ISs can be used to prepare a stock IS m ixture. The table below lists the recomm ended stable isotope ISs and S R S s applied in the method. O ther stable isotope ISs and S R S s o f target analytes not listed to the table m ay be used if supported by validation and/or analysis batch Q C s meeting method acceptance criteria (e.g., [13C J-P FO A ). The sam e internal standard should be used for a given analyte throughout the entire prpject/study. Note: som e o f the compounds listed below are appropriate to use as surrogate ISs when a stable isotope IS o f a target analyte is not available. Generally, surrogate isotopically labeled PFC A s are used for PFCAs, and surrogate isotopically labeled PFSAs are used for PFSAs.
Table 2 provides exam ples o f sp ire concentrations and volum es used to achieve a multi-point calibration curve with ISs and SRSs.
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Table 1. Stable Isotope PFCAs and PFSAs used for ISs and SRSs
CompoundName `^CU-PerfluotolniUnmc acid 13C4-Perfluoropentanoic >od ^Ci-Peifiuofohexanoic acid ^Cf-PerfhioiDheptanaic acid 13C,-Peiflnarooctanaic add ^Cf-Perflnorontmanoic add ^CVPeifluotodecanoic aad 13C-rPcrfluoroundecanQ(c acid l*C2-Perfluotpdodccanotc acid
A m m ontim i P et lliiimifcenm p ilfim ete 13Ct-SodtuoiPerfluorooctane snMonalc
13C4-Perfhiorooctanoic aad 13C2-PgfluoKxmdecMioic nod I3Ct-Peifliiorooc1xne inlfonatr
Synonym orAcronym [133,4-UC4JPFBA [ ^ - "CjJPFPfeA [1,2 -"CJPFHxA [1,2,3,4-uC,JPFIfoA [1A3,4,5,6,7,8-uCIPFOA [1^3,4,5,6,7,8^-UC#PTNA [1 3 3 ,4 ,5 ,6 -" CsJPFDA [1,23,4,5,6,7 -13C7]PFUnA [13 -"CJPFDoA [`ChJPFBS [1.23-13C3jPFHS [133,4,5,6,7,8-uC,JPFOS
[133,4,5,6,7,8-uCtJFOSA [1,23,4-13C,JPFOA [ U - uC2JPFIiA [133,4-uC4JPFOS
AnalyticalPurpose IS forPEBA ISforPFPeA IS forPFHxA ISforPFHpA IuSCf4oJPrFPOFOAA and [133,4 IS fi PENA IS for PEDA IS for PFUnA IS forPFDoA, *PFTA IS forPFBS IS forPFHS IPSFfOorSP[FUO3S,4an"dC J,
IS forFOSA
SRS for all PFCAs: C4-C8
SRoeuferrceenceStandard Wellington Labs (Mix Individual) Wellington Labs (Mix Individual) Wellington Labs (Mix orIndividual) Wellington Labs (Mix orIndividual) Wellington Labs (Mix orIndividual) Wellington Labs (Mix or Individual) Wellington Labs (Mix orIndividual) Wellington Labs (Mix orIndividual) Wellington Labs (Mix or Individual) R(In.HdiIvnitdernaantional Wellington Labs (Mix or Individual) Wellington Labs (Mix or Individan Wdbnglon Labs 0nix) RH International (IhdividuaD Wellington
SRS forall PFCAs C9-C13 Wellington
CSR6,SafnodrCal8l PFSAs: C4, Wellington
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Table 2. Example Preparation of Calibration Curve with ISs and SRSs
S am ple Description
0 .025 ng/mL curve point 0 .030 ng/mL curve point 0.04 ng/mL curve point 0.05 ng/mL curve point
0.1 ng/mL curve point 0 .2 5 ng/mL curve point 0 .5 ng/mL curve point
1 ng/mL curve point 2 .5 ng/mL curve point 5 .0 ng/mL curve point 10.0 ng/mL curve point 2 5 .0 ng/mL curve point 50.0 ng/mL curve point 75.0 ng/mL curve point 100 ng/mL curve point
C o n c e n tra tio n o f IMS, pg/m L
0.10 0.10 0.10 0.10 0.10 0.10 1.0 1.0 10.0 10.0 10.0 10.0 10.0 mo 10.0
Volum e o f IMS, pL
25 30 40 50 100 250 50 100 25 50 100 250 500 750 1000
Volum e o f IS (2 pg/m L), pL
50 50 50 50 50 50 50 50 50 50 50 50 50 50 50
C oncentration o f Surrogate, pg/m L
0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 10.0 10.0 10.0 10.0 10.0 10.0 10.0
Volum e o f Surrogate, pL
1 2 .5 15 20 25 50 125 250 500 25 50 100 NA NA NA NA
Volum e o fA S T M Type 1 Water, or o th e r suitable s o lv e n tn , mL
100 100 100 100 100 100 100 100 100 100 100 100 100 100 100
N /A - Not Applicable (1) Samples requiring analysis for PFUnA, PFDoA, PFTrOA, and FOSA should be analyzed against a caibration curve prepared in 1:1 synthetic groundwaterMeOH.
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8 Sample Collection and Bottle Preparation
S am ple collection bottles are prepared by 3M Environm ental Laboratory (o r subcontract supplier) personnel fo r shipm ent a t am bient tem perature to th e collection site. Typically, four separate collection bottles are associated w ith a single cofiection site: sam ple, field duplicate sam ple, low field m atrix spike, and high field m atrix s p ite . A lternatively, th e sam ple and field duplicate sam ple m ay contain S R S s in lieu o f additional target analyte tow field m atrix spice and target an alyte high field m atrix spike sam ples. Depending on th e scope o f th e project, additional replicates o f th e field sam ple and field m atrix spikes m ay be added. A lso, it is not uncomm on fo r additional m id-level field m atrix spikes to be collected if th e expected sam ple concentrations are truly unknown o r could span a large concentration range.
H igh-density polyethylene (H D P E ) w ide-m outh N algene bottles are used fo r th e sam ple collection containers. (Volum es o f th e bottles m ay vary depending on how m uch sam ple is required to m eet data quality objectives.) Sam ple coflection volum es a re project specific and based on d ata quality objectives. T h e N algene bottles do not require any pretreatm ent prior to use. Typically, placem ent o f a sam ple bottle volum etric "fifi to here' line is done by using a sam ple bottle m arker tem plate. A lternatively, bottles m ay be w eighed prior to bottle preparation and w eighed again a fter sam ples have been collected.
A l bottles should b e clearly labeled to indicate its intended use as a sam ple, field sam ple duplicate, low field m atrix spice, high field m atrix spice, sam ple/S R S field m atrix spice, field duplicate sam ple/S R S field m atrix spice, trip blank, o r trip blank m atrix spice. If each location has different designated spike levels, th e label should also d e a rly indicate th e sam ple location designation. GeneraBy, a set o f bottles fo r a given collection site are prepared then grouped together in plastic bags fo r organizational purposes. For each sam ple collection event, a t least one set o f trip blank and trip blank m atrix spices a re prepared.
B ottle preparation should be docum ented in a N ote to F ile o r on a sam ple preparation w orksheet and should include th e follow ing inform ation: d ate prepared, to tal num ber o f bottles prepared, num ber o f sam ple sites, the standard identification num bers and spike volum es used to prepare spiced bottles, th e T il to h e re ' volum e, and any other pertinent inform ation needed fo r reco n stru cfibity o f th e d ata. T h e N ote to F ie w 8 be included in the tria l d ata package fo r th e p ro ject
Sam ples a re collected in th e field and shipped to th e laboratory a t am bient tem perature.
8.1 Field Matrix Spike Sample (FMS)
Field m atrix spice sam ples a re a requirem ent o f th e m ethod. A FM S sam ple is defined as a Q C sam ple to which known quantities o f appropriate targ et analytes are added to th e sam ple bottle in th e field o r in th e laboratory before th e bottles are sent to th e fie ld . The sam ple and field duplicate sam ple m ay contain appropriate S R S s in fieu o f targ et analyte FM S sam ples. Sam ple quantities a re determ ined voium etricaly or gravrnetricaSy. A known, specific volum e o r w eight o f sam ple is added to th e sam ple container w ithout rinsing. Volum etric sam ple m easurem ents m ay be acquired by a laboratory applied TH to this leveT fine on the outside o f th e sam ple container. T arg et analyte FM S sam ples should b e spiced a t approxim ately 0 .5 -1 0 tim es th e expected analyte concentration in th e sam ple. If th e expected range o f analyte concentrations is unknown, m ultiple spikes a t varying levels m ay be prepared to increase th e licefihood th at a spice a t an appropriate level is m ade. T yp icaly a low and a high targ et analyte spike are prepared fo r each sam pling location. In those instances w here S R S s are to be used in lieu o f target analyte FM S sam ples, th e sam ple and field duplicate sam ple are spiced a t approxim ately 2 -5 tim es th e target LO Q . T he FM S is analyzed to ascertain if m atrix effects o r sam ple holding tim e contributes bias to th e analytical results. For th e sam ple bottles designated fo r m atrix spices, an appropriate volum e o f m atrix spicing solution is added to th e em pty bottle prior to sam pting. T h e v o lu n e o f spice solution added should produce th e d e s ie d final concentration o f targ et analytes once the bottle is filled w ith sam ple to th e TH to here lin e*. T h e m atrix spicing solution(s) should be prepared in a suitable solvent and contain a l o f th e appropriate targ et analytes, IS s, and S R S s. T h e targ et analyte m atrix spiking solution is often th e sam e as th e working standards used to create th e cafibration standards. An exam ple o f a bottle spice is given below .
"F ll to here' volum e = 200 m L (A 2 5 0 m L N algene bottle is used)
D esired Field S pice Concentration = 0 2 5 ng/m L
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500 pL o f a 0.1 pg/m L sp itin g solution (containing th e targ et an alytes) is added to th e bottle and th e bottle cap prom ptly sealed.
8.2 Internal Standard and Surrogate Recovery Standard
If analysis o f a surrogate recovery standard (S R S ) is included in the project objectives, an appropriate volum e o f a surrogate standard solution is added to a ll the bottles prior to sam pling and S P E . Typically sam ple bottles are sp ked w ith surrogate recovery standards a t a final desired s p k e concentration o f 0.1 ng/m L.
If quantitation by internal standard (IS ) is included in th e project objective, an appropriate volum e o f internal standard solution is added to a ll th e bottles prior to sam pling and S P E . Typically sam ple bottles are spiked w ith internal standard a t a fin al desired s p k e concentration o f 1 ng/m L.
For the trip blank, the S R S s p ite and IS spike is added to th e bottle and then A STM Type I w ater (H P LC grade reagent w ater o r other suitable w ater m ay used) is added to th e "fill to here" lin e. T h e bottle is capped and sealing tap e m ay be placed so u n d th e outer edge o f th e cap. T rip blank m atrix s p ite s are prepared by adcfing th e appropriate volum e o f targ et analyte spiking solution, IS , and S R S sp itin g solutions and filling th e bottle to th e desired volum e w ith th e appropriate w ater and capping and sealing th e cap.
9 Quality Control and Data Quality Objectives
9.1 Data Quality Objectives
This m ethod and required quality control sam ples is designed to generate d ata accurate to 30% w ith a targeted LO Q o f 0 .0 2 5 n g/m L A ny deviations from th e quality control m easures spelled out below w ill be docum ented in th e raw data and footnoted in th e final rep o rt
9.2 Method/Procedural Blanks
T h e m ethod/procedural blank is zero point calibration standard (w hich includes IS s) analyzed in a regular basis w ith each analysis batch. A t a m inim um , m ethod blanks are analyzed prior to instrum ent calibration, prior to th e analysis o f C C V sam ples, a fte r every 10 sam ple injections, and a t th e end o f th e analytical run.
T h e m ean area count or area ratios w hen using internal standard calibration, fo r each an alyte in th e m ethod blanks m ust be less than 50% o f th e area count counts o r area ratios w hen using internal standard calibration, o f th e LO Q standard. T h e standard deviation o f the area counts, o r area ratios w hen using internal standard calibration, o f these m ethod blanks should be calculated. A specific % R S D acceptance criteria is not specified but is assessed on an analytical batch basis. If th e m ean area counts o r area ratios w hen using internal standard calibration, o f th e m ethod blanks exceed 50% o f the LO Q standard, then th e LO Q m ust be raised to th e first standard level in th e curve th at m eets criteria. M ethod blanks m ay be elim inated if technical justification can be provided (e .g . th e procedural blank w as analyzed a fte r an unexpectedly high level sam ple). If any procedural blanks a re rem oved from th e LO Q determ ination, docum ent in the raw data and report as appropriate. Laboratory S am ple R eplicates / Field D uplicate Sam ple
Typically, sam ples a re collected in duplicates in th e fie ld . T h e relative percent difference (R P D ) o f duplicate sam ples should be S20% fo r th e precision o f sam ple preparation a id analysis to be considered in control. R eplicate sam ples not m eeting th e s20% R PD criteria are flagged and reported as outside o f Q C acceptance c rite ria .
9.3 Laboratory Matrix Spikes (LMSs)
LM Ss m ay be perform ed in lieu o f FM Ss if FM Ss have previously been perform ed fo r th e sam ple m atrix. A dditionally, LM Ss m ay be perform ed in lieu o f FM Ss fo r a sam ple m atrix if th e FM S levels w ere not appropriate fo r determ hing s p k e recoveries relative to endogenous levels o f targ et analytes a id appropriate S R S s. G enerally, each sam ple location represents a d ifferen t sam ple and sam ple m atrix. LM Ss are prepared fo r each sam ple and analyzed to determ ine th e m atrix effect on s p ire recovery efficiency o f each targ et analyte and appropriate S R S s. LM Ss should be prepared a t a m inim um o f one level and in duplicate. LM S concentrations should be prepared a t approxim ately 0 .5 -1 0 tim es the endogenous concentration or approxim ately 4 -1 0 tim es th e LO Q concentration o f each target analyte.
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Lab m atrix spice recoveries should fafl w ithin 30% o f expected values. Sam ple data w ith LM S recovery outside o f 30% but w ithin 50% o f the expected value are flagged and reported as outside erf Q C acceptance criteria. D ata w ith LM S recovery outside o f 50% o f th e expected value a re reported as N R , w here N R is defined as "N ot R eportable" d ata outside o f Q C acceptance criteria.
9.4 Lab Control Sample
Lab control spices are prepared fo r each analysis batch to determ ine m ethod accuracy and precision. LCSs should b e prepared a t th ree levels in tripficate fo r each target analyte and a t a m inim um o f tw o levels in trip licate fo r appropriate S R S s. Low lab control spikes should be prepared a t a concentration in th e range o f approxim ately four to ten tim es higher than th e targeted low er LO Q , th e m id lab control spices should be prepared a t a concentration n ear th e m id-point o f the calibration curve and th e high lab control spikes a t approxim ately 80% o f the upper LO Q . For each target an alyte and S R S s, th e percent relative standard deviation (m ethod precision) fo r each control spice level m ust be less than o r equal to 20% and th e average recovery (m ethod accuracy) fo r each control spike level m ust be 80-120% . Sam ple d ata fo r target analytes outside o f th e laboratory control spice acceptance criteria w ill be handled as follow s:
If th e average recovery o f a sp itin g level fa lls outside m ethod acceptance, but a t least 67% (6 out o f 9 ) o f LCS sam ples a re w ithin 20% o f th eir respective n o m ra l value (33% o f the Q C sam ples, not a i replicates a t the sam e concentration, m ay be outside 20% o f nom inal valu e), th e average recovery win b e flagged as outside m ethod acceptance c rite ria A i LCS sam ples w ill be control charted as p er E T S -4-026. If th e average recovery o f one o f th e spicing levels exceeded th e analytical m ethod uncertainty as determ ined by E T S -12012, th at analytical batch in c e rta in ty w ill b e expanded fo r th at particular study.
If m ore than 67% o f th e LCS sam ples fa i to m eet m ethod acceptance criteria, th e d ata w i not be reported.
C alforation standards consisting o f m ixed branched and lin ear isom er P FO S /P FO A a re preferred. H ow ever, fo r P FO S /P FO A targ et analytes, if th e calibration standards are com prised o f predom inantly lin ear isom ers only, a t least one level o f trip licate LCSs should be prepared using P FO S /P FO A which contains a m ix o f linear and branched isom ers. These LCSs w ill be used to dem onstrate quantitative equivalency (o r quantitative bias) o f th e isom eric m ix when using a predom inantly linear standard fo r calibration. T h e m ixed lin ear and branched isom er P FO S /P FO A LCSs recoveries should fo il w ithin 30% o f expected values. A lternatively, in lieu o f m ixed branched and lin ear isom er P FO S /P FO A LC Ss, m ixed branched and lin ear isom er P FO S /P FO A TB M Ss m ay be applied to dem onstrate m ethod accuracy and precision.
9.5 Field Matrix Spikes (FMSs) / Surrogate Recovery Standards (SRSs)
FM Ss are prepared fo r each sam pling location and analyzed to determ ine th e m atrix effect and sam ple holding tim e on th e s p ite recovery o f each targ et an alyte and/or appropriate S R S . G enerally, each sam ple location represents a efifferent sam ple and sam ple m atrix.
FM Ss are Q C sam ples to which known quantities o f appropriate targ et analytes a re added to th e sam ple bottle in th e laboratory before th e bottles are sent to th e field . T yp icaly a low and a high targ et analyte FM S are prepared fo r each sam pling location. T he sam ple and field duplicate sam ple m ay contain appropriate S R S s in ie u o f targ et an alyte tow fiekt m atrix spice and targ et analyte high field m atrix spice sam ples.
Field m atrix s p ite m ethod acceptance criteria a re recoveries w ithin 30% o f th e expected value. If FM S recovery (targ et analyte o r S R S s p ite ) is outside o f 30% o f th e expected value or could not be assessed because th e FM S (targ et an alyte) w as s p ite d a t an inappropriate level, th e sam ple result is reported as follow s:
1 . ) If targ et analyte FM S recovery could not be assessed because th e F M S s w ere a t an inappropriate level, then Laboratory M atrix S p ite s (L M S ) m ay be substituted. If LM S recoveries are w ithin 30% th e data are reportable and flagged to indicate th at th e FM S spikes levels w ere inappropriate.
2 . ) If m ultiple targ et analyte FM S 's w ere prepared on a sam ple and th e closest FM S level to th e reported sam ple m eets th e 30% acceptance criteria but additional FM S 's are outside th e 30% acceptance range, the data are reportable and flagged to incficate th at w hile th ere w ere failing FM S 's , th e uncertainty w il not be expanded since th e m ost appropriate spice level passed.
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3 . ) tf the targ et analyte FM S recoveries are outside o f the 30% acceptance range but a t least 30 acceptable historical reportable FM S sam ple results a re availab le, th e data m ay be reported but flagged w ith an expanded uncertainty and as not m eeting FM S criteria.
4 . ) Sam ple d ata w ith FM S recovery outside o f 30% but w ithin 50% o f the expected value a re flagged and reported as outside o f Q C acceptance criteria w ith an expanded uncertainty.
5 . ) If FM S recovery is outside o f 50% , th e sam ple result is reported as N R , w here N R is defined as ` N ot Reportable" due to noncom pliant Q C results.
T he targeted fortification levels should be a t least 50% o f the endogenous level and less than 10 tim es the endogenous level to be used w ithout justification to determ ine th e statem ent o f accuracy fo r analytical results.
N ote: It is possible fo r bottles utilized fo r Field M atrix S pike sam ples to be u nd er-filed o r over-filled dum g sam ple collection. S ince this scenario w ill effect th e actual concentration o f th e FM S sam ple (surrogate and internal standard concentrations w ll also be effected , if used), it is Im portant th at any obvious under-filling or over-filling o f sam ple bottles be docum ented in th e d ata package a id taken into account in th e FM S , IS s, or S R S s recovery calculations. Sam ples over-filled or under-filled by m ore than 10% w ill be require recalculation o f th e FM S , IS s, and S R S true values.
T he average o f th e sam ple and the field duplicate should be used to calculate th e recovery.
10 Procedures
10.1 W ater Sample Preparation
This m ethod is applicable to w ater sam ples. Sam ples containing heavy particulate m ay not be suitable fo r analysis by this m ethod. Sam ples containing suspended particulate should be centrifuge prior to rem oving a sam ple aliquot, o r filtered .
Thoroughly m ix sam ple before rem oving an aliquot and placing in a labeled autovial.
D ilute sam ple, if necessary, w ith A STM Type I w ater, H PLC w ater, other suitable w ater, o r solvent (m ethanol).
Lab control s p ite s are prepared fo r each analysis batch to determ ine m ethod accuracy and precision. LCSs should be prepared a t th ree levels in trip licate fo r each targ et analyte and a t a m inim um o f tw o levels in trip licate fo r appropriate S R S s. Low lab control spikes should be prepared a t a concentration in the range o f approxim ately four to ten tim es higher than th e targeted low er LO Q , the m id lab control spikes should be prepared a t a concentration n ear the m id-point o f th e calibration curve and th e high lab control spikes a t approxim ately 80% o f th e upper LO Q . For IS quantitation, stable isotope internal standards o f each target analyte o r appropriate surrogate IS s should be spiked a t th e sam e level as the sam ples being analyzed, in a ll LCSs.
If LC Ss a re being prepared using synthetic groundw ater, allow th e LCSs sam ples to eq u iib rate fo r a m inim um o f 4 hours before aliquoting fo r analysts o r diluting w ith solvent (m ethanol).
11 Sample Analysis - LC/MS/MS
11.1 Instrument Setup
N o te: In this exam ple, an A pplied Biosystem s S d ex A P I 4 0 0 0 (A P I 5000 o r A P I 5 5 0 0 ) Tandem M ass
WeiSpectrom eter (L C /M S /M S ) is used. O ther brands/m odels o f LC /M S /M S instrum ents as as single
quadrupole m ass spectrom eters (L C /M S ) m ay be used as long as th e m ethod acceptance criteria are m e t Brand nam es, suppliers, part num bers, and m odels are fo r illustrative purposes only. Equivalent perform ance m ay be achieved using apparatus and m aterials other than those specified here, but dem onstration o f q u iv a la it perform ance th at m eets th e requirem ents o f this m ethod is the responsibility o f the laboratory. The operator m ust optim ize and docum ent the equipm ent and settings used.
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Establish the LC /M S /M S system and operating concftions equivalent to th e follow ing: M ass Spec: A pplied Biosystem s A P I 4 0 0 0 , A P I 5000, o r A P I 5500 Ion Source: Turbo Ion S pray (A B S ) M ode: E ledrospray N egative Scan Type: M RM (M ultiple R eaction M onitoring) C om puter D e i DHM Softw are: W indow s 2 000 o r W indows X P , A nalyst 1 .4 2 or higher versions HPLC: A gilent S eries 1100,1200, o r 1290 A gilent Q uaternary Pum p A gilent Vacuum D egasser A gilent A utosam pler A gilent Colum n O ven N o te: O ne o r m ore C 18 H PLC analytical colum ns (2.1 mm x 100 m m , 5pm o r Z 1 mm x 50 m m , 5pm ) m ay be attached on-line a fter th e purge valve and before th e sam ple injection port to retard and separate any residue contam inants th a t m ay be in th e m o b ie phase and/or H PLC system . HPLC Colum n: B etasil C 18,4.6m m x 100m m , 5pm (Therm oElectron C orporation) Colum n Tem perature: 35C Injection Volum e: 5pL M obile P hase (A ): 2m M Am m onium A cetate in A STM Type I w ater (S e e 7 .3 ) M obile P hase (B ): M ethanol
T a b le 3 . L iq u id C h ro m a to g ra p h y G ra d ie n t P ro g ra m .
S te p N um ber
0
1 2 3 4 5
T o ta l T im e (m in )
0 2.0 14.5 15.5 16.5 20.0
B o w Rate
(j J m ln )
750 750 750 750 750 750
P e rc en t A (2 m M a m m o n iu m
a c e ta te )
97.0 9 7 .0 5.0 5.0 9 7 .0 9 7 .0
P ercen ts
(M e th a n o l)
3 .0 3 .0 95.0 95.0 3.0 3.0
N ote: O ther H PLC gradients m ay be used as long as th e m ethod criteria and project d ata quality objectives are m et
It m ay be necessary to adjust th e H PLC gradient in order to optim ize instrum ent perform ance. Colum ns w ith different dm ensions (e .g . 2.1m m x 30m m ) and colum ns from different m anufacturers (K eystone B etasil C 18 e tc .) m ay be used.
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T a b le 4 S u g g e s te d M R M T ra n s itio n s fo r T a rg e t A n a ly te s , S u rro g a te s , a n d In te rn a l S ta n d a rd s
Analyte
P F B A (C 4 A cid) PFPeA (C5 A d d ) PFH xA (C 6 A dd) P F H p A (C7 A cid ) P F O A (C8 A cid)
P F N A (C 9 A cid) P F D A (CIO A cid ) P F U n A ( C ll A d d ) PFDoA (0 2 Add) PFTA(C13 A dd) I S S A (C 4 Sulfonamide) F O S A (C8 Sulfonamide) P F B S (C4 Sulfonate) P FH S (C 6 Sulfonate) P FO S (C8 Sulfonate) [1 ,2 3 ,4 -" C J P F B A U 3 .4 .5 -u C ,lP F P e A [ U -" C d P FH sA [1 .2 ,3 ,4 -u C ]P F H p A [U ,3 ,4 ,5 ,6 ,7 ,8 -uC tlP F O A [1 ,2 3 ,4 ,5 ,6.7.8.9-u C ]P F N A [1 3 3 ,4 ,5 ,6 -UC*]PFD A [133 ,4 ,5 ,6,7 -u C ,]P F U n A n .2 -13C,1P FD oA [" O JP F B S [1 3 3 -b C,1PFH S [1 3 3 ,4 -uC ,]P FO S [13,3,4,5,6,7,8-uC i]F O S A [1 3 3 ,4 -d C4]PFO A [1 3 3 ,4 -u C]PFOS [1 3 -1JC ,lP F U n A
Analyte Description
Target Target Target Targe* Target
Target Target Target Target Target Target Target Target Target Target IS for P F B A IS fo r PFPeA IS fo rP F H x A IS for P FH p A IS for P F O A IS for P F N A IS for P F D A IS fo rP F U n A IS fo r P F D o A and P F T A IS for PFB S IS for PFH S IS for PFO S IS fo r F O S A S o n o n te (C4-C8 A d ds) Surrogate{Sulfonates, F O S A ) Surrogate (C9-C13 A d d s)
Mass Transition Q1 fornai
213 263 313 363 413 463
513 563 613 663 298 498 299 399 499 217 268 315 367 421 472 519 570 615 303 402 503 507 417 503 565
Mass Transition 03 fornai
169 219 2 6 9 ,1 1 9 3 1 9 ,1 6 9 3 6 9 ,2 1 9 .1 6 9 4 1 9 ,1 6 9 ,2 1 9
4 6 9 .2 6 9 .2 1 9 5 1 9 ,2 6 9 ,2 1 9 5 6 9 .1 6 9 .3 1 9 6 1 9 ,3 6 9 ,3 1 9
78 78 9 9 ,8 0 99 .8 0 80 .9 9 .1 3 0 172 223 270 322 376 427 474 525 570 84 80 80 80 372 80 520
M ultiple transitions fo r m onitoring th e analytes is an option. T h e use o f one daughter ion is acceptable if data sensitivity and selectivity is achieved and provided th at retention tim e criteria are m et to assure adequate specificity. W M e the daughter ions m ay be chosen a t th e discretion o f th e analyst, m ass transition 99 is suggested fo r P FO S . Q uantitation m ay be perform ed using the to tal ion chrom atogram (T IC , o r sum m ed M R M s) fo r a given analyte. For exam ple, th e PFO A T IC would sum a ll th ree o f th e m onitored transitions. U se o f th e suggested prim ary ion is recom m ended. R etention tim es m ay vary slightly, on a day-to-day basis, depending on th e batch o f m o b ie phase and th e gradient, colum n, guard colum n(s) used etc. D rift in retention tim es is acceptable w ithin an analytical ru i, as long as th e d rift continues through th e en tire analysis and the standards are interspersed throughout th e analytical run.
11.2 Calibration Curve
Q uantitation is by internal standard or external standard calibration. C alibration standards m ay be prepared in A STM Type I, H PLC w ater, other suitable w ater, o ra solvent/w ater m ixture. If internal standard calibration does not m eet calibration acceptance criteria, external calibration can be applied. S ee Table 1 fo r
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recom m ended application o f availab le internal standards. Q uantitation o f PFO A and P FO S is by sum m ed analyte-specific m ass transitions.
A nalyze th e standard curve prior to each s e t o f sam ples. If internal standards w ere added to th e calibration standards area ratios a re used to generate th e c a lix a tic r curve. T h e standard c u n m ay be plotted using a lin ear regression (y = m x + b ), w eighted 1/x o r unw eighted, o r by quadratic fit (y = ax2 + bx + c ), w eighted 1/x or unw eighted, using suitable softw are. T h e m athem atical m ethod used to calculate th e c a lix a tio n curve should be applied consistently throughout a study. A ny change should be thoroughly docum ented in th e raw d ata.
High and/or low points m ay be excluded from th e calibration curves to provide a b etter fit over th e range appropriate to th e data o r because they did not m eet th e pre-determ ined acceptance criteria. Low -level curve points should also be excluded if th eir area counts (o r area ratio if quantitating by IS ) a re not a t least tw ice that o f th e average area counts (o r area ratio if quantitating by IS ) o f m ethod and/or solvent blanks. T h e coefficient o f determ ination (r2) value fo r th e calibration curve m ust be g reater than o r equal to 0 .9 9 0 (o r a correlation coefficient (r) o f 0 .9 9 5 ). Each point in th e curve m ust be w ithin 25% erfth e theoretical concentration w ith the exception o f th e LLO Q , which m ay be w ithin 30% . Justification fo r exclusion o f calibration curve points w ill be noted in th e raw d ata. A m inim um o f 6 points w ii b e used to construct th e c a lix a tio n curve.
If th e caBbration curve does not m eet acceptance criteria, perform routine m aintenance or prepare a new standard curve (if necessary) and reanalyze.
11.3 Continuing Calibration Verification (CCV)
Continuing calibration verifications (C C V ) are analyzed to verify th e accuracy o f th e catibration curve. A nalyze a m id-range calibration standard, one o f th e sam e standards used to construct the c a lix a tio n curve, a t a m inim um a fte r every tenth sam ple, not including solvent blanks, w ith a m inim um o f one p er sam ple seL C alix a tio n verification injections m ust be w ithin 25% to be considered acceptable. T h e c a lix a tio n curve and th e last passing C C V wB then bracket acceptable sam ples. M ultiple C C V levels m ay b e used. Sam ples m ust be bracketed by passing C C V s o r th e calibration c u n and a passing C C V to be reportable.
11.4 System Suitability
A m inim um o f th ree system su itab lity sam ples should be injected a t th e beginning o f each analytical run, prior to th e analysis o f th e cafibration curve. T yp icaly these sam ples are a t a concentration near th e m id-level o f the c a lix a tio n curve and are repeated iryections from one autosam pler v ia l. It is suggested th at th e system suitability Sections have area counts o r area ratios when using internal standard calibration, w ith a targ et RSD o f 5% and a targ et retention tim e R SD o f <2% . T here is no defined a c c e p ta b ly lim it on these results as the % R SD value is dependent on th e num ber o f M R M transitions being m onitored in the LC /M S /M S run o r tim e period. U ltim ately, any effects on these param eters fo r th e System S u itab lity sam ples w ill also be evident on all standards and Q C sam ples analyzed as p a rt o f th e analysis bateh. A ny effect o f system su itab lity is incorporated w ithin Q C acceptance criteria.4
11.5 Sample Analysis and QCs
For each analysis batch, th e instrum ent analysis run sequence shoidd include an in itial c a lix a tio n curve, sam ples, FD S s, interspersed blanks, interspersed C C V s, appropriate Q C s (i.e ,, LC Ss, LM Ss, FM Ss, TB M Ss, and T B s), and a fin al C C V o r c a lix a tio n curve bracketing sam ples and appropriate Q C s
Irqect th e sam e volum e (betw een 5 - 1 0OpL) o f each standard, analytical sam ple and blank into th e instrum ent (unless an on-instrum ent sam ple d lu tion is d esired).
Sam ples containing analytes th at a re quantitated above th e concentration o f th e highest standard in th e curve should be fu rther diluted and reanalyzed.
4 tM Fninnu m m u l TjK rw ilm y
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12 Data Analysis and Calculations
T h e chrom atography analysis softw are w ill typically calculate th e am ount o f target analyte in th e sam ple extracts using th e established calibration curve. C alculate th e percent recovery o f th e LCS using th e follow ing equation:
LCS% recovery = --L-C--S---C--o-n--c-e-n--t-ra--t-io--n-- *100% Spike Concentration mT.
C alculate th e percent recovery o f the LM S using th e follow ing equation:
LM S Concentration ( - ^ - ) - Concentration o f Sam ple ( - ^ - ) LM S % recovery = ___________________ mL___________________________ mL
Spike Concentration ( - ^ - ) mL
100%
For sam ples fo rtified w ith kncw n am ounts o f analyte prior to extraction, use th e M o w in g equation to calculate th e percent recovery.
R ecovery _ T o ta l a n a ly te found (n g /m L ) - A verag e a n a ly te found in sam ple (n g /m L )^ ^^ A nalyte added (n g /m L )
13 Analysis Batch Method Performance Criteria
A ny m ethod perform ance param eters th at are not achieved m ust be considered in th e evaluation o f th e data. Nonconform ance to any specified param eters m ust be described and discussed in th e fin al report if th e Technical M anager (non-G LP study) or Study D irector (G LP study) chooses to report th e d ata.
If criteria listed in th is m ethod perform ance section are not m et, m aintenance m ay be perform ed on th e system and sam ples reanalyzed, o r other actions taken as appropriate. D o cu m en tal actions in th e raw d ata.
If data are to be reported w hen perform ance criteria have not been m et, th e data m ust be footnoted on tables and discussed in th e te x t o f th e report.
13.1 System Suitability - Analysis Batch
A m inim um o f th ree system suitability sam ples should be injected a t th e beginning o f each analytical run. These sam ples a re run prior to th e calibration curve. It is suggested th at th e system suitability injections have area counts w ith a target R SD o f <5% and a target retention tim e R SD o f 52% . T here is no defined acceptability lim it on these results as th e % R SD s are dependent on th e num ber o f M RM transitions being m onitored in th e LC /M S /M S run o r tim e period. Any effect o f system suitability is incorporated in th e Q C acceptance criteria.
13.2 Calibration and Limit of Quantitation (LOQ) - Analysis Batch
C a lib ra tio n C u rve: T he coefficient o f determ ination (r2) value fo r th e calibration curve m ust be g reater than or equal to 0 .9 9 0 corresponding to a correlation coefficient (r) = 0 .9 9 5 . Each point in th e curve m ust be w ithin 25% o f th e theoretical concentration w ith th e exception o f the LLO Q , which m ay be w ithin 30% .
C C V P erfo rm an ce: T h e calibration standards th at a re interspersed throughout th e analytical sequence are evaluated as continuing calibration verifications in addition to being p art o f th e calb ratio n curve. T h e accuracy
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o f each curve point m ust be w ithin 25% o f th e theoretical value (w ithin 30% fo r low est c u v e point). Sam ples th at are bracketed by C C V s not m eeting these criteria m ust be reanalyzed.
L im its o f Q u a n tita tio n (L O Q ): T he low er LO Q (LLO Q ) is th e low est non-zero active standard in th e calibration curve; th e peak a re a o f th e LLO Q m ust be a t least 2X th at o f th e average area counts fo r a l prepared procedural blan k(s). By definition, th e m easured value o f th e LLO Q m ust be w ith n 30% o f the theoretical value.
D em o n stratio n o f S p e c ific ity : S pecificity is dem onstrated by chrom atographic retention tim e (w ithin 4% o f standard) and th e m ass spectral response o f unique ions.
13.3 Blanks - Method/Procedural Blanks and Trip
M eth o d /P ro ced u ral B lan ks: M ultiple procedural blanks should be interspersed throughout th e analysis batch and th e analytical sequence. A t a m inim um , m ethod blanks a re analyzed prior to instrum ent caB xation, prior to th e analysis o f C C V sam ples, a fter every 10 sam ple injections, and a t th e end o f th e analytical run.
T h e m ean area counts (o r area ratios w hen using IS cafibration) fo r each analyte m ust be less than 50% o f the area count o f th e LO Q standard. If th e area counts o f th e procedural blanks exceed 50% o f th e LO Q standard, then th e LO Q m ust be raised to th e firs t standard level th at m eets criteria.
T rip B lan k: A trip blank o f A STM Type I w ater (o r lab equivalent) is prepared in a sam ple container in th e laboratory and treated as a sam ple, including exposure to shipptog, sam pfing site conditions, storage, preservation and a ll analytical procedures. T h e trip blanks results fo r each analyte a re included w ith th e reported sam ple results.
13.4 Data Accuracy and Precision - Analysis Batch
L ab C o n tro l S p ikes: T he average recovery a t each LC S level fo r each target analyte and appropriate SR S should be w ithin 80-120% and th e percent relative standard deviation o f th e recoveries m ust be less than or equal to 20% . If th e average recovery o f a spicing level fa lls outside m ethod acceptance, but a t least 67% (6 out o f 9 ) o f LC S sam ples a re w ithin 20% o f th eir respective nom inal value (33% o f th e Q C sam ples, not all replicates a t th e sam e concentration, m ay be outside 20% o f nom inal valu e), th e average recovery w ill be flagged as outside m ethod acceptance criteria. A ll LCS sam ples w ill be control charted as p er E T S -12-012. If th e average recovery o f one o f th e spiking levels exceeded th e analytical m ethod uncertainty as determ ined by E T S -12-012, th at analytical batch uncertainty w i be expanded fo r th at particular study. T h e average recovery a t each LC S level fo r m ixed b ran ched /in ear isom er PFO A and PFO S should be w ithin 70-130% and th e percent relative standard deviation o f th e recoveries m ust be less than o r equal to 20% .
F ie ld D u p lic a te s : T he relative percent difference (R P D ) o f duplicate sam ples should be less than 20% fo r the precision o f sam ple preparation and analysis to be considered in control. R eplicate sam ples not m eeting the 20% R PD criteria a re flagged and reported as outside o f Q C acceptance c rite ria
F ie ld M a trix S p ikes: FM S acceptance criteria are recoveries w ithin 30% o f th e expected value fo r each targ et analyte and appropriate S R S . Sam ple data w ith FM S recovery outside o f 30% but w ithin 50% o f th e expected value a re flagged and reported as outside o f Q C acceptance criteria. D ata w ith FM S recovery outside o f 50% o f the expected value are reported as N R , w here N R is defined as "N ot R eportable' data outside o f Q C acceptance criteria. If FM S recovery could not be assessed because FM Ss w ere a t an inappropriate level, then Laboratory M atrix Spikes (LM S s) m ay be substituted. If LM S recoveries a re w ithin 30% fo r each targ et analyte and S R S s th e data are reportable but flagged as not m eeting th e FM S m ethod acceptance criteria.
13.5 Analytical Method Uncertainty
A nalytical m ethod uncertainty fo r each targ et analyte and S R S is determ ined w ith control charted historical analysis batch LC S d ata to r the m ethod and reported w ith each analysis batch.5 U ncertainty determ inations
5 M ethod uncertainty based on INTERNATIONAL ANS/ISO/IED STANDARD 17025 reference (GUM, Guide to die Expression of Uncertainty in Measurement). M ethod application demonstrated in ETS-12-012, citing references: a ) EURACHEM/CITAC Guide, b"Q.)Guaenotrigfyiainng, TUhnocmeartsa,i"nEtystiinmAatnioalnytoicfaLlaMboeraastuorreymAennat,l"ytSiceacloUndnEcedrittaioinnt;yEUdsiitnogrsL: Sab.LoJrLatoEryllCisoonnt,rMol.SaRmospslleesi.n",EannvdirAonmWeinlltiaalmTse.sting &
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are based on IN TER N A TIO N A L A N S /IS O /IE D STA N D A R D 17025 reference (G U M , G uide to to e Expression o f U ncertainty in M easurem ent) and described in E T S -12-012. A t least thirty data points are required fo r determ ining analytical m ethod uncertainty. T he m ethod uncertainty is defined as 2x th e standard deviation o f th e percent recoveries o f to e pooled lab control s p ite s . W hile a ll LC S d ata points are control charted, only the m ost recent fifty d ata points are used fo r determ ining th e m ethod uncertainty.
W hen less than thirty LCS data points have been generated fo r a given an alyte, th e analysis batch LC Ss are used to determ ine th e data uncertainty. If FM Ss m eet th e 30% recovery criteria a t a level appropriate to th e endogenous level, and th e LC S m eet to e 20% recovery criteria, then th e uncertainty o f th e data is determ ined as w ithin 10020% .
A nalysis batch sam ple d ata w ith FM S recovery outside o f 30% but w ithin 50% o f th e expected value are flagged and reported as outside o f Q C acceptance criteria w ith expanded uncertainties. D ata w ith FM S recovery outside o f 50% o f the expected value are reported as N R , w here N R is defined as ' N ot R eportable' data outside o f Q C acceptance criteria. If FM S recovery could not be assessed because FM Ss w ere a t an inappropriate level, then Laboratory M atrix Spikes (LM S s) m ay be substituted. If LM S recoveries a re w ithin 30% fo r each targ et analyte and appropriate SR Ss th e data are reportable but flagged as not m eeting th e FM S m ethod acceptance criteria w ith in certain ties o f 30% . If FM S do not m eet th e 30% recovery criteria, and historical FM S data does not exist, th e analytical uncertainty is evaluated on a sam ple-bysam ple basis, th e d ata m ay be reported w ith expanded uncertainty and a re flagged.
13.6 Quantitation of PFOA/PFOS - Analysis Batch
C alb ration standards consisting o f m ixed branched and lin ear isom er P FO S /P FO A a re preferred. Q uantitation is perform ed by integrating th e lin ear and branched isom ers together. A lternately, th e linear and branched isom ers can b e integrated separately, applying the appropriate true value to each calibration curve point fo r each isom er. T he LCS and sam ples are then quantitated by integrating to e lin ear and branched isom ers separately (requires sep arate analytical results file s ) and quantitating th e resulting peak against the lin ear or branched calb ratio n curve. T he results from both integrations are then sum m ed to produce th e final re s u lt Integrating th e lin ear and branched isom ers separately m ay be helpful fo r those sam ples w here the linear/branched ratios do not closely m atch those o f th e reference standards.
H ow ever, fo r P FO S /P FO A targ et analytes, if th e calibration standards are com prised o f predom inantly linear isom ers only th e m ethod requires th e addition o f LCSs o f m ixed branched/linear isom er P FO S /P FO A . The purpose o f including these LC Ss is to dem onstrate quantitative equivalency (o r quantitative b ias) o f th e isom eric m ix w hen using a predom inantly lin ear PFO S o r PFO A standard fo r calb ratio n . A lternatively, in feu o f m ixed branched and lin ear isom er P FO S /P FO A LC Ss, m ixed branched and lin ear isom er P FO S /P FO A TB M Ss m ay be appfied to dem onstrate m ethod accuracy and precision.
An altern ate m ethod o f quantitation can be perform ed w hereby only th e lin ear isom er o f P FO S /P FO A is integrated and used fo r generating th e calibration curve. T he LC S and sam ples are then quantitated by integrating th e lin ear and branched isom ers separately (requires separate analytical results fife s ) and quantitating th e resulting peak against th e linear calibration curve. T he resists from both integrations are then sum m ed to produce th e fin al re s u lt Integrating th e linear and branched isom ers separately reduces th e oncolum n concentration fo r those sam ples th at contani both lin ear and branched isom ers o f P FO A /P FO S . This ensures th at th e concentration detected is w ithin th e a range o f the calb ratio n curve th at is com parable regarcfless o f w hether th e calibration curve w as generated using predom inantly linear isom ers o f P FO S /P FO A o r lin ear plus branched isom ers o f P FO S /P FO A .
14 Pollution Prevention and Waste Management
W aste generated w hen perform ing this m ethod w ill be disposed o f appropriately. T h e originai sam ples w ill be archived a t toe 3M Environm ental Laboratory in accordance w ith internal procedures.
MAEvneaaallsuyuasrtieisnm,gNeanontvdUemEnxcbeperrrt/eaDsisncitcnycgminthbTecerUs2tn0inc0ge0r".t,acJi.nu)Ttlyyaoy2!f0oN0r2,IB.ST.NM. eaansduCreEm.eKntuRyeasttu,lNtsI."S<TLT)Aedcahinnsic, aTl.NMo.,te"A122L97A,1G9u9i4dEe dfoitriothne: "EGstuimidaetliionnesoffor
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15 Records
Each d ata package generated fo r a study m ust include aH supporting inform ation fo r reconstruction o f th e d ata. Inform ation fo r th e data package m ust include, but is not lim ited to th e follow ing item s: study o r project num ber, sam ple and standard prep sheets/fecords, instrum ent run log (instrum ent batch records, instrum ent acquisition m ethod, sum m ary pages), instrum ent results files, chrom atogram s, calixab o n curves, and data calculations.
16 Affected Documents
N one.
17 Revisions
R evision Num ber
1
Sum m ary o f C hanoes
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 sotvent/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 tire details regarding tire instrumentparameters to section 10 of the method. Section 7. Updated reference standards to include internal standards and surrogates. Changed concentration levels for working standards and included the use of internal standards and surrogates. Section 8. Inserted a new section on sample bottle preparation. Section 9 Quality Control. This section was previously section 10 in ETS-8-044.0. Updated QC criteria to be consistent with method ETS-8-154.4. Section 10 Procedures. This section was previously section 8 (Sample Handling) in ETS-8044.0. Added detail regarding the preparation ofLCSs. 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 in ETS8-044.0. 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 PFOA/PFOS. Section 14 Pollution Prevention. This section was previously section 13 in ETS-8-044.0. Section 15 Records. This section was previously section 14 in ETS-8-044.0. Section 16 Affected Documents. This section w as previously section 15 in ETS-8-044.0. Section 17 Rvisons. This section was previously section 16 in ETS-8-044.0.
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