Document 2JQOkBdzNj6p25omg8bMYdY75
INTERIM REPORT #26 - Analysis of Groundwater SamDles
STUDY TITLE Analysis of Perfluorobutanesulfonate(PFBS), Perfluorohexanesulfonate(PFHS), and
Perfluorooctanesulfonate(PFOS) in Water, Soil, Sediment, Fish, Clams, Vegetation, Small Mammal Liver and Small Mammal Serum Using LCMSMS for the 3M Decatur
Monitoring Program
DATA REQUIREMENTS EPA TSCA Good Laboratory Practice Standards 40 CFR 792
STUDY DIRECTOR Jaisimha Kesari P.E., DEE
Weston Solutions, Inc. 1400 Weston Way
West Chester, PA 19380 Phone: 610-701-3761
INTERIM REPORT COMPLETION DATE January 9,2007
PERFORMING LABORATORY Exygen Research
3058 Research Drive State College, PA 16801
Phone: 814-272-1039
STUDY SPONSOR 3M Company
3M Building 0236-01-B-10 St. Paul, MN 55144 Phone: 651-733-6374
PROJECT Protocol Number: PO001131 Exygen Study Number: PO001131
Total Pages: 118
Interim Report #26 - Analysis of Groundwater Samples
Exygen StudyNo.: POOOl131
GOOD LABORATORY PRACTICE COMPLIANCE STATEMENT
Exygen StudyNumber POOOl 131, entitled "Analysis of Perfluorobutanesulfonate(PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil, Sediment, Fish, Clams, Vegetation, Small Mammal Liver and Small Mammal Serum Using LC/MS/MS for the 3M Decatur Monitoring Program," conducted for 3M Company, is being performed in compliance with EPA TSCA Good Laboratory Practice Standards 40 CFR 792 by Exygen Research.
1
Chas Simons I '
Principal hvestigidr Exygen Research
Jaisimha Kesari P.E., DEE Study Director Weston Solutions, Inc.
Michael A. S p
Sponsor Rep esentative
3M Company
Date Date
Exygen Research
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Interim Report #26 - Analysis of Groundwater Samples
Exygen Study No.: POOOl 131
OUALITY ASSURANCE STATEMENT
Exygen Research's Quality Assurance Unit reviewed Exygen Study Number POOOl 131, entitled, "Analysis of Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil, Sediment, Fish, Clams, Vegetation, Small Mammal Liver and Small Mammal Serum Using LCMSMS for the 3M Decatur Monitoring Program". All reviewed phases' were inspected for conduct according to Exygen Research's Standard Operating Procedures, the Study Protocol, and all applicable Good Laboratory Practice Standards. All findings were reported to the Exygen Principal Investigator and Management and to the Study Director.
Phase
Date Inspected
Date Reported to Date Reported to
Principal
Exygen Date Reported to
Investigator Management Study Director
45. Interim Report and Raw Data Review
12/28,29/06
01/09/07
01/09/07
0 1/09/07
1Note: All in-lab inspections will be documented in the QA statement for the final analytical report at the conclusion of the study. This QA statement involves only the review of the interim report and associated raw data.
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Interim Report #26 - Analysis of Groundwater Samples
Exygen Study No.: POOOl 131
CERTIFICATION OF AUTHENTICITY
This interim report, for Exygen Study Number POOOl 131, is a true and complete representationof the raw data.
Submitted by:
Exygen Research 3058 Research Drive State College, PA 16801 (814) 272-1039
Principal Investigator,Exygen:
Date Operations Manager Exygen Research
Exygen Research Facility Management:
/ &hard A. G
Executive Dir
W r Analytical Sciences
Exygen Research
Study Directgp, Weston Solutions, Inc.
Date' Weston Solutions, Inc.
Sponsor Representative, 3M Company:
Michael A. SantHo Director of RegulatoryAffairs
Exygen Research
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Interim Report #26 - Analysis of Groundwater Samples
Exygen StudyNo.: PO001131
STUDY IDENTIFICATION
Analysis of Perfluorobutanesulfonate(PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate(PFOS) in Water, Soil, Sediment, Fish, Clams, Vegetation, Small Mammal Liver and Small Mammal Serum Using LC/MS/MS for the 3M Decatur
Monitoring Program
PROTOCOL NUMBER:
POOOl 131
EXYGEN STUDY NUMBER: POOOl 131
TYPE OF STUDY:
Residue
SAMPLE MATRIX:
Ground Water
TEST SUBSTANCE:
Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate(PFHS), and Perfluorooctanesulfonate (PFOS)
SPONSOR:
3M Company 3M Building 0236-01-B-10 St. Paul, MN 55144
STUDY DIRECTOR:
Jaisimha Kesari P.E., DEE Weston Solutions, Inc. 1400 Weston Way West Chester, PA 19380
STUDY MONITOR:
Michael A. Santoro 3M Company 3M Building 0236-01-B-10 St. Paul, MN 55144
PERFORMING LABORATORY:
Exygen Research 3058 Research Drive State College, PA 16801
ANALYTICAL PHASE TIMETABLE:
Study Initiation Date:
11/05/04
Interim Analytical Start Date:
11/24/06
Interim Analytical Termination Date: 12/06/06
Interim Report Completion Date: 01/09/07
Exygen Research
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Interim Report #26 - Analysis of Groundwater Samples
Exygen Study No.: PO001131
PROJECT PERSONNEL
The Study Director for this project is Jaisimha Kesari at Weston Solutions, Inc. The following personnel from Exygen Research were associated with various phases of this interim portion of the study:
Name Chas Simons John Flaherty Karen Risha Amy Sheehan Mark Ammennan Mindy Cressley Ellen Dashem Chrissy Edwards Krista Gallant
Title
Operations Manager Vice President
Laboratory Supervisor Associate Scientist Sample Custodian Technician Technician Technician Technician
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Interim Report #26 . Analysis of Groundwater Samples
Exygen StudyNo .. PO001131
TABLE OF CONTENTS
Pane
TITLE PAGE ....................................................................................................................... 1
GOOD LABORATORY PRACTICE COMPLIANCE STATEMENT.............................. 2
QUALITY ASSURANCE STATEMENT .......................................................................... 3
CERTIFICATION OF AUTHENTICITY ........................................................................... 4
STUDY IDENTIFICATION................................................................................................ 5
PROJECT PERSONNEL..................................................................................................... 6
TABLE OF CONTENTS ..................................................................................................... 7
LIST OF TABLES ............................................................................................................... 8
LIST OF FIGURES.............................................................................................................. 9
LIST OF APPENDICES .................................................................................................... 10
1.0 SUMMARY................................................................................................................ 11
2.0 OBJECTIVE ............................................................................................................... 11
3.0 INTRODUCTION....................................................................................................... 11
4.0 ANALYTICAL TEST SAMPLES.............................................................................. 11
5.0 REFERENCE MATERIAL ........................................................................................ 12
6.0 DESCRIPTION OF ANALYTICAL METHOD ........................................................ 13
6.1 Extraction Procedure ................................................................................................ 13
6.2 Preparationof Standardsand Fortification Solutions............................................... 13
66..34 CInhsrtroummaetongt rSaepnhsyit..i.v....i.t.y...............................................................................................................................................................................................
14 14
6.5 Descriptionof LC/MS/MS Instrument and Operating Conditions........................... 14
6.6 Quantitationand Example Calculation..................................................................... 15
7.0 EXPERIMENTAL DESIGN ...................................................................................... 16
8.0 RESULTS ................................................................................................................... 17 9.0 CONCLUSIONS......................................................................................................... 17 10.0 RETENTION OF DATA AND SAMPLES ............................................................. 17
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Table I.
Table II.
LIST OF TABLES
Pane Summary of PFBS, PFHS and PFOS in Groundwater Samples..................... 19
Matrix Spike Recovery of PFBS, PFHS and PFOS in Groundwater
Samples.......................................................................................................... .20
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Figure 1.
LIST OF FIGURES
F&g
Typical Extracted Calibration Curve for PFBS in Reagent Water .................22
Figure 2. Extracted Standards of PFBS in Reagent Water, 0 ng/L and 25 ng/L,
Respectively................................................................................................... .23
Figure 3. PFBS in Reagent Water, 50 ng/L Fortified Reagent Spk A, and
500 ng/L Fortified Reagent Spk B, Respectively ........................................... 24
Figure 4. Figure 5.
Chromatogram Representing a Groundwater Sample Analyzed for PFBS
(Exygen ID: C0222027, Data Set: 112406C)................................................. 25
Typical Extracted CalibrationCurve for PFHS in Reagent Water .................26
Figure 6. Extracted Standards of PFHS in Reagent Water, 0 ng/L and 25 ng/L,
Respectively................................................................................................... .27
Figure 7. PFHS in Reagent Water, 50 ng/L Fortified Reagent Spk A, and
500 ng/L Fortified Reagent Spk B, Respectively ........................................... 28
Figure 8. Figure 9.
Chromatogram Representing a Groundwater Sample Analyzed for PFHS
(Exygen ID: C0222027, Data Set: 112406C)................................................. 29 Typical Extracted Calibration Curve for PFOS in Reagent Water ................3.0
Figure 10. Extracted Standards of PFOS in Reagent Water, 0 ng/L and 25 ng/L,
Respectively................................................................................................... .31
Figure 11. PFOS in Reagent Water, 50 ng/L Fortified Reagent Spk A, and
500 ng/L Fortified Reagent Spk B, Respectively ........................................... 32
Figure 12. Chromatogram Representing a Groundwater Sample Analyzed for PFOS
(Exygen ID: C0222023, Data Set: 112406C) ................................................. 33
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Exygen StudyNo.:POOOl131
LIST OF APPENDICES Pane
Appendix A Study Protocol POOOl 131 (Exygen StudyNo. POOOl 131) with Analytical Method VOOOl780, Protocol Amendments, and
Deviations ............,....,........................................................,.......................34
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1.0 SUMMARY
Exygen Research extracted and analyzed groundwater samples for the determination of perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (PFHS), and perfluorooctanesulfonate (PFOS) according to Exygen Method VOOO1780 (Appendix A).
The limit of quantitation (LOQ) for PFBS, PFHS and PFOS in ground water was 25 ngL.
Analytical results for the analysis of PFBS, PFHS and PFOS found in groundwater samples are summarized in Table I, Due to quality control failures, PFBS results for two samples are not reported (NR). Fortificationrecoveries for PFBS, PFHS and PFOS in the
groundwater samples are detailed in Table 11. The average percent recoveries k standard
deviations for PFBS, PFHS, PFOS in the groundwater samples were 102 k 4%, 100 k lo%, and 103 k 7%, respectively.
2.0 OBJECTIVE
The objective of the analytical part of this study was to determine levels of perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (PFHS), and perfluorooctanesulfonate (PFOS) in ground water according to Protocol POOOl 131 (Appendix A).
3.0 INTRODUCTION
This report details the results of the analysis for the determination of PFBS, PFHS, and
PFOS in groundwater using the analytical methods entitled, "V0001780: Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Water by
L C M S M S."
The study was initiated on November 05, 2004, when the study director signed protocol number POOOl 131. The analytical start date for this interim report was November 24, 2006, and the analytical termination date for this interim report was December 6,2006.
4.0 ANALYTICAL TEST SAMPLES
Eleven groundwater samples (Exygen ID C0222023 - C0222033) were received on wet
ice on November 21,2006 fiom Tim Frinak at Weston Solutions, Inc. Eight groundwater samples represented two groundwater sampling sites and associated field quality control samples. Three water samples represented one trip blank and two trip blank spikes. All samples were logged in by Exygen personnel and placed in refrigerated storage.
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Sample log-in and chain of custody information is located in the raw data package associated with this interim report. Storage records will be kept at Exygen Research.
5.0 REFERENCE MATERIAL
The analytical standards, PFBS (SP0008058) and PFHS (SP0008057), were supplied by 3M. PFBS (SP0008058) was received fkom 3M at Exygen on September 6,2006. PFHS (SP0008057) was received fkom 3M at Exygen on September 5, 2006. The analytical standard PFOS (SP0002694) was purchased fi-om Fluka Corporation and was received at Exygen on April 23,2003.
The available information for the reference materials is listed below. PFBS and PFHS were stored frozen and PFOS was stored refiigerated.
Compound Exvnen Inventory No.
PFBS
SP0008058
- Lot #
2
Purity C%)
97.3
PFHS
SP0008057
NB-120067-69 98.6
PFOS
SP0002694
430180-1
101.2
The molecular structures of PFBS, PFHS and PFOS are given below:
Expiration Date 01I17/07
10118/07 1013 1/07
PFBS
Chemical Name: Perfluorobutanesulfonate Molecular Weight: 338 supplied as the potassium salt (C4FgS03X3
Transitions Monitored: 299 + 99
Structure:
PFHS Chemical Name: Perfluorohexanesulfonate Molecular Weight: 438 supplied as the potassium salt (C6F13SO3K>
Transitions Monitored: 399 + 80
Structure:
F
F
F
-
F-\/\/\,
so3
F F F
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)
InterimReport #26 -Analysis of Groundwater Samples
Exygen Study No.:PO001131
PFOS
Chemical Name: Perfluorooctanesulfonate Molecular Weight: 538 supplied as the potassium salt ( C B F ~ + ~ O ~ X + )
Transitions Monitored: 499 -+ 80
Structure:
F F F F
6.0 DESCRIPTION OF ANALYTICAL METHOD
The analytical method "V0001780: Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Water by LC/MS/MS" was used for the groundwater samples in this study.
6.1. Extraction Procedure
A 40 mL aliquot of the water sample was used for the extraction procedure. After fortification of appropriate samples, the samples were loaded onto a c18 SPE cartridge conditioned with 10 mL of methanol and 5 mL of water. The eluate was discarded. Approximately five milliliters of methanol was added to the cartridge. Five milliliters of eluate was collected into a graduated 15 mL polypropylene centrifuge tube. Each sample was analyzed by LC/MS/MS electrospray.
6.2 Preparation of Standards and Fortification Solutions
A mixed stock standard solution of PFBS, PFHS and PFOS was prepared as specified in Exygen method V0001780. The stock standard solution was prepared at a concentration of 10,000 pg/mL by dissolving 1.O g of each of the standards(corrected for purity and salt content, if necessary) in methanol. From these solutions, a 1000 pg/mL fortification standard solution was prepared by taking 10 mL of each stock and bringing the volume up to 100 mL with acetonitrile. By taking 10 mL of the 1000 p g / d fortification standard and bringing the volume up to 100 mL with acetonitrile, a 100 pg/mL fortification standard was prepared. By taking 10 mL of the 100 pg/mL fortification standard and bringing the volume up to 100 mL with acetonitrile, a 10 pg/mL fortification standard was prepared. By taking 10 mL of the 10 pg/mL fortification standard and bringing the volume up to 100 mL with acetonitrile, a 1.0 pg/mL fortification standard was prepared. By taking 10 mL of the 1.0 pg/mL fortification standard and bringing the volume up to 100 mL with acetonitrile, a 0.1 pg/mL
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fortification standard was prepared. By taking 10 mL of the 0.1 pg/mL fortification standard and bringing the volume up to 100 mL with acetonitrile, a 0.01 pg/mL fortification standard was prepared.
A set of standards containing PFBS, PFHS and PFOS were prepared in water and processed through the extraction procedure, identical to samples. The following concentrationswere prepared:
Conc. of Fort Fort
Solution Volume
(ng/mL)'
(pL)
0
0
10
100
10
200
10
400
100
100
100
200
100
400
of PFBS, PFHS and PFOS
Volume of Fortified Sample
(mL)
40 40 40 40 40 40 40
Final Conc. of Calibration Std.
(neJL) 0 25 50 100
250 500 1000
The stock stored in
* standard solution and
a refrigerator (4"
all fort-fication anb 2C) when not in
calibration standard sold ons were use. Documentation of standard
preparation is located in the raw data package associated with this interim report.
6.3 Chromatography
Quantificationof PFBS, PFHS and PFOS was accomplished by LCNSIMS electrospray. The retention times of PFBS, PFHS and PFOS were -0.5 mins, -8.5 mins, and -11.1 mins, respectively. Peaks above the LOQ were not detected in any of the reagent blank samples corresponding to the analyte retention time.
6.4 Instrument Sensitivity
The smallest standard amount injected during the chromatographic run had a
concentration of 25 ng/L of PFBS, PFHS and PFOS.
6.5 Description of L C N S N S Instrument and Operating Conditions
Instrument: Interface: Computer: Software:
API 4000Biomolecular Mass Analyzer
Turbo Ion Spray Liquid Introduction Interface DELL OptiPlex GX400 Windows NT, Analyst 1.4.1
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HPLC:
Hewlett Packard (HP) Series 1100
HP Quat Pump
HP Vacuum Degasser
HP Autosampler
HP Column Oven
HPLC Column: Thenno Fluophase RP, 50 mm x 2.1 mm
Column Temp.: -30" C
Injection Vol.: 15 pL
Mobile Phase (A): 2 mM Ammonium Acetate in water
Mobile Phase (3): Methanol
Time (min)
%A
0.0
65
35
1.o
65
35
8.0
25
75
10.0
25
75
11.0
65
35
18.0
65
35
Total run time: -18 min Flow Rate: 0.3 mL/min Ions monitored:
Analvte
PFBS PFHS PFOS
Mode
negative negative negative
Transition
Monitored
299 + 99
399 -+ 80
499 -+ 80
Approximate Retention Time
(min) -0.5 min. -8.5 min. -1 1.1 min.
6.6 Quantitation and Example Calculation
Fifteen microliters of sample or calibration standard were injected into the LC/MS/MS. The peak area was measured and the standard curve was generated (using l/x fit weighted linear regression) by Analyst software using seven concentrations of standards. The
concentration was determined fkom the following equations.
Equation 1 calculated the amount of analyte found (in ng/L, based on peak area) using the standard curve (linear regression parameters) generated by the Analyst software program.
Equation 1:
Analyte found (ng/L) = (Peak area - intercat) x DF
slope
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Where: DF =Dilution Factor, factor by which the final volume was diluted, if necessary.
For samples fortified with known amounts of PFBS, PFHS and PFOS prior to extraction, Equation 2 was used to calculate the percent recovery.
Equation 2: Recovery (%) =
[analyte found ( n a ) - analyte in control (nn/L)) x 100%
amount added (ng/L)
An example of a calculation using an actual sample follows (calculation is for PFHS only):
Ground water sample Exygen ID: C0222023 Spk C (Set: 112406C), fortified at 250 ng/L with PFHS where:
peak area
-
intercept
-
slope
-
dilution factor
-
ng/L PFHS added (fort level) =
amt in corresponding sample =
5 1377 0.000296 154 1 250 75.5 (Set: 112406C)
From equation 1: Analyte found (ng/L)
From equation 2:
YORecovery
= 151377 - 0.0002961 x 1
154 = 334ngL
= (334 ng/L - 75.5 n e ) x 100%
250 ng/L
= 103%
NOTE: Numbers may differ slightly from raw data due to rounding.
7.0 EXPERIMENTAL DESIGN
For samples designated as field matrix spikes, PFBS, PFHS, and PFOS were added at a known concentration to the bottles in the laboratory before being shipped to the field. The samples were filled to a 200 mL volumetric fill line in the field.
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The samples were extracted in one set. The set included one reagent blank, two reagent blanks fortified at known concentrations. The set also contained two sample sites and the field blank and the field blank spikes collected for the groundwater samples. For each site, a sample, a field duplicate and two-matrix field spikes were collected. For each site, a laboratory duplicate and two laboratory matrix spikes were also extracted.
8.0 RESULTS
Analytical results and assessed accuracies for the analysis of PFBS, PFHS and PFOS
found in groundwater samples are summarized in Table I. Accuracies were assessed for each sample by reviewing the individual quality control results obtained for each sample site. In most cases, there were two laboratory and two field spike recovery results available for each sample site that were used to assess the accuracy. In instances of failed laboratory or field spikes, recoveries associated with other spikes were used to assess sample accuracy. Quantitative results were obtained for all samples and analytes except for PFBS in two groundwater samples that are not reported (NR) due to quality control failures.
Fortification recoveries for PFBS, PFHS, and PFOS in groundwater samples are detailed in Table 11. The average percent recoveries k standard deviations for PFBS, PFHS, PFOS in ground water samples were 102&4%, 100f10%,and 103f7%, respectively.
9.0 CONCLUSIONS
Except as noted above, the groundwater samples were successfblly extracted and analyzed for PFBS, PFHS and PFOS according to analytical method V0001780.
10.0 RETENTION OF DATAAND SAMPLES
All original paper data generated by Exygen Research that pertains to this interim report will be shipped to the study director. This does not include facility-specificraw data such
as instrument or temperature logs. Exact copies of all raw data, as well as a signed copy
of the final analytical report and all original facility-specific raw data, will be retained in the Exygen Research archives for the period of time specified in EPA TSCA Good Laboratory Practice Standards40 CFR 792.
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TABLES
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Table I.
Summary of PFBS, PFHS and PFOS in Groundwater Samples
DAL-GW-TRIP-0-061117
C4 Sulfonate PFBS
Portluorobuhnesulfonate
Analyte Found
Assessed Accuracy
(nW
(+&
NR NR NR
NR NR NR
ND
30
C6 Sulfonate PFHS
Pemuorohexanesutfonste
Analyte
Assessed
Found
men)
Accuracy
(*I- X)
75.5
30
83.3
30
83.3
30
764
30
754
30
778
30
ND
30
C8 Sulfonate PFOS
Po~uorooctrnerulfonrts
Analyte Found (nglL)
Assessed
Accuracy
(+I-%)
i
602
30
604
30
61 1
30
9270
30
7540
30
10800
30
ND
30
`Laboratory Duplicate ND = Not detectedat or abovethe Limit of Quantitation(LOQ) of 25 ngk. NR = Not reported due to quality control failures.
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Table 11. Matrix Spike Recovery of PFBS, PFHS and PFOS in Groundwater Samples
Sample Ducrlptlon
DAL-GW-RESWO1-0-061117 (Cop202.Y splr C. 260 ndl. lab Wlm)
DAL-GW-RESWO1-0-081117 (c0222023Spk D. Woo n#L L.bSpllm)
DAL-OW-RESWOl-LS-061117
(m03.6 ppb rpuU)
DAL-GW-RESW01-HS-061117 (Comoq6 ppb R*d WW
DAL-QW-RESW02-0-061117 (cazponSplr E. 260 ndl. L.bSPK.)
DAL-GW-RESW02-0-061117 (COmonSpk F. SOW nghL.b 8)piW
DAL-GW-RESW02-LS-061117 (Cop20a. 0.25 ppb FbldWL.)
DAL-GW-RESWOZ-HS-061117
(Cop20SO. 6 ppb fldd WplL.)
DAL-GW-TRIP-LS-061117 (c02220Y.0.24 ppbFbldW m )
DAL-OW-TRIP-HS-061117 (Cop2oU. 6 ppb FWd Splpllu)
250 5000 250 5000
250 5Ooo 250 5Ooo 250
5MH)
C4 Sulfonate PFBS
CB Sulfonate PFHS
h t Found Amount
In Sample Recovered Recoveq
(nglL)
(ng/L)
(%)
C8 SulfonatePFOS
bmtFound Amount
In Sample Recovered Recovery
(ngL)
(nglL)
(K)
NR
NR
NR
75.5
335
104
NR
NR
NR
NR
NR
NR
75.5
4940
97
602
5850
105
NR
NR
NR
75.5
374
119
NR
NR
NR
NR
NR
NR
75.5
4790
94
802
8040
109
NR
NR
NR
764
920
9270
10900
NR
NR
NR
764
5240
90
9270
14300
101
NR
NR
NR
764
969
9270
7660
NR
NR
NR
764
5130
87
9270
13800
91
ND
247
99
ND
264
108
ND
260
104
ND
5210
104
ND
5040
101
ND
5410
108
Avange: 102 St8nd8rdhvi8tlon: 4
Avmge: 100 Stmdu4 D.vl8tlon: 10
'Sample residue axceeds the splking level signilicanuy; therefore, an accurate WCQWY value cannot be cslculpted NO = Not detected at (x above the Limitof Quanutation (LOQ) of 25 qh.
NR Not reported due to quality wntml fallurea.
Not.: Slna thb summ8ry t8Ma 8howS roundodrUuI(.. ncovrryV8lws myV8rysllghtly horn the V8luw Inthe n w at..
Avenge: 105 Shndmrd D.vlatlon: 7
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FIGURES
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Figure 1. Typical Extracted Calibration Curve for PFBS in Reagent Water
112400CR P7l30.1131 Wat.rR1sr.v2.rdb(PF8SF"Lin.a~ R i q r e s i o n C I /~wwciqhtln~):y=86.x1+367(1=0.W25)
8.3.4 8.0.4 7.6.4 7.0.4 0.5.4 6.014 6.5.4 6.0.4
c u)
=c0 Ej 4.514
0
- 0
es 4.0.4
4 3.5.4 3.014 2.614 2.04 1.5.4
Concentration. n@mL
*
--T
lo00
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Figure 2. Extracted Standards of PFBS in Reagent Water, 0 ng/L and 25 ng/L, Respectively
IXC772406-0 -Pf8S(Standard)H L ) / ) l O a r # -campic 7 of %from 772406Cwiff @cak not found) 11 .a1
20
6l
16
-- I O
e 6
0
1
2
3
4
5
6
7
8
0 10 11 12 13 14 I S 16 17
I Time. min XCl12416.1. PFBS (Standard)2W.OtT2.0 rmu. sample 2 o f 3 4 from 1 1 2 ~ C . W i f t AI~J:2636 counts Height 1.77a+002 cps RT: 0.542 min
0.64 150.
Time. min
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Figure 3. PFBS in Reagent Water, 50 ng/L Fortified Reagent Spk A, and 500 ng/L Fortified Reagent Spk B, Respectively
I - Reagent Contra# PfBS m k r o w r ] 29LOi9SOarrru -rirnrp#e $of 34frorrr 772406CwitT Qcak rot found]
UJ
n
0
l
e
J?!
- c
1 2 3 4 5 6 7 0 8 10 11 12 13 14 15 18 17
Time. min
1 - Reagent SpkA- PFBS (aC)2f3Q.O#QQe.Oamu sample 10 of 34from 112406C.wiff
Area: 5307 counis Height: 3.07c+O02 cps RT: 0.550 min
I - - - - -
- -__ Time, mi? _- _ I
Reagent Spk B PFBS (OC)298.0100.0 .mu sample 1 1 of 34from 11240(1C.wiff
Area: 64418 oounis Height: 4.ORe+003 cps RT: 0.547 min
9UI
0.55
11
c111
-c c
1
-
1
-
1
-
1
-
.
-
1
-
1
-
1
-
1
1 2 3 4 5 0 7 8 0 10 I 1 12 13 1 4 15 10 17
Time, min
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Figure 4.
Chromatogram Representing a Groundwater Sample Analyzed for PFBS (Exygen ID: C0222027, Data Set:
112406C)
Timr, min
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Figure 5. Typical Extracted Calibration Curve for PFHS in Reagent Water
- 1.215
- 1.015
- 9.014
8.0~4-
7.0e4-
- 0 . 0 ~ 4
5.0~4-
- 4 . 0 ~ 4
0
100
200
300
400
500
800
700
800
000
1000
Concentration. ngtL
Exygen Research
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Exygen StudyNo.: PO001131
Figure 6. Extracted Standards of PFHS in Reagent Water, 0 ng/L
and 25 ngL, Respectively
XC1124I)B-0 - PFHS (Standdrd)398.0180.0 amu - sample 1 uf 28 from 112400CR.vuiff
(peak notfound)
0.80
10.21
jjUI
3.0
P
u
2.0
- c
Ea,
1.0
0 .o
1 2 3 4 5 8 7 8 0 10 11 12 13 1 4 15 10 17
- Time, min
XC7724Of-7 P F H S - & 3~9 ~9 . ~ 1 0m i - s a m p j e 2 of29 mrrr 77246k#?.wi#- -
Are#: 3924couats migkt: 7.63e+002cps UT:I58rrria
150 -
m::
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Exygen StudyNo.: PO001131
Figure 7. PFHS in Reagent Water, 50 ng/L Fortified Reagent Spk A, and 500 ng/L Fortified Reagent Spk B, Respectively
I - Re8gsrt Control PFHS mkrowr] 399.0/810 umu -rumple 9 of Wfmm 772406Cwifi @Q8kr o t fbund)
-u1
n
0.46
0
!
7.84
12.17
13"' 14.67 15.95
c
J!!
0.0'
c
I 2 3 4 5 e 7 e Q IO 11 12 13 14 15 16 17
A- Reagent Spk PFHS (OC)389.0180.0
amu -
sample
Time, min -10 of 34from 1124OOC.wiff
_- II
Area: 7505 oountr Height:2.QOe+OO2cps RT: RBI min
6.111
I - - Time. min ~~~ ReagentS p k i PFHS(QC)398.0180 0 amu r&ple 11 of 34from 11240BC.wiff Area: 75578 counts Height: 2.g2e+003 ops FIT: 0.81 rnin
0
Pc 2mo:
ru
--
__
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Exygen StudyNo.: PO001131
Figure 8.
Chromatogram Representing a Groundwater Sample Analyzed for PFHS (Exygen ID: C0222027, Data Set:
112406C)
5000 4600 4000 3500 3000 2m 2000 1500 1000
500 0
Time, rnin
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Exygen StudyNo.: PO001131
Figure 9. Typical Extracted Calibration Curve for PFOS in Reagent Water
a 112400C P780-1131 Water Res.rdb [PFOS):"Linea? Rmgresion 1`1 i 9 weighting): y = 122 x + 4.831-006(r= O.WB7)
Concentration, nglL
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Exygen StudyNo.: PO001131
Figure 10. Extracted Standards of PFOS in Reagent Water, 0 n g L and 25 ngL, Respectively
- XC112406-0 PFOS p t u ~ d s r d9)9Lo18aU.MY 9c.L rot found]
-8unrple 1of34frorrr 172406Gwiff
11.07
u)
8.0
8 e.0
icG" 4.0
cc (D
2.0
0.o i i 3 4 S e i t i d io ii ii i i 14 15 i e ii
1 - Time,_min
-
X C l l Z 4 ! M - l . PFOS (Strndrrd)498.0/80.(1 amu sample 5%34from IW401)C.vuiff
A r e x 2 8 1 8 counts Height: 1.3Be+002 cps RT: 11.1 rnin
8u) 1 0 0 -
.4s-
u)
- 50-
c c
0 - . 1 . I . - I . I . I . I . I . I .-,
Time, min
-.
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Exygen StudyNo.: PO001131
Figure 11. PFOS in Reagent Water, 50 ng/L Fortified Reagent Spk A, and 500 ng/L Fortified Reagent Spk B, Respectively
-& 100'
I
cu) I,
Time, min
I
"I
Reagent SpkA- PFOS [QC)4QQ.OMO.O am< -sample 10 of 34from 112400C.wiff
Area: 6039 counts Height: 3.21e+002 cps RT: 11.1 min
c
gln
P
11.10
0
a,
Time, min
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Figure 12. ChromatogramRepresenting a Groundwater Sample Analyzed for PFOS (Exygen ID: C0222023, Data Set: 112406C)
q1.11
Time, min
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Exygen StudyNo.:PO001131
APPENDIX A
Study Protocol PO001131
(Exygen Study No. P0001131) with Analytical Methods,
Protocol Amendments, and Deviations
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Exygen StudyNo.: PO001131
ExygenRotocolNumber PO00113I
STUDY PROTOCOL
Study Title: Analysis of Perfluorobutanesulfonate(PFBS),
Perfluorohexanesulfonate(PFHS), and
Perfluorooctanesulfonate (PFOS)in Water, Soil, Sediment,
Fish, Clams, Vegetation, Small Mammal Liver and Small
Mammal Serum Using LC/MS/MS or the 3M Decatur
Monitoring Program
Exygen Protocol Number: PO001131
Performinn Laboratorv:
Exygen Research
3058 Research Drive
State College, PA 16801
Phone: (814) 272-1039
$DonsOI RmSmtative:
Michael A. Santom Director of Regulatory Affairs
3M Building 0236-01-B-10
St. Paul, MN 55144 Phone: (651) 733-6374
Exygen Research
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Exygen Study No.:PO001131
Exygen Protocol Number:PO00I 131
c4
DISTRIBUTION:
1) Jaishha Kesd, StudyDirector,Weston Solutions 2) John M. Flaherty,Principal Investigator,Exygen Research 3) Michael A. Santoro, Sponsor Representative, 3M Company 4) Exygen Research Quality Assurance Unit
Exygen Research
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Exygen StudyNo.: POOOl 131
Exygen Protocol Number: Po001 131
,P-
PROTOCOL APPROVAL
Study Title: Analysisof Perfluorobutanesulfonate(PFBS),Perfluorohexanesulfonate (PFHS), and Pduomtantsulfonate (PFOS) in Water, Soil, Sediment. Fish, Clams, Vegetation, Small Mammal Livers and Small Mammal Serum Using LC/MS/MS for the 3M Decatur Monitoring Program
Exygen Protocol Number: POOOl 131
APPROVALS
Weston Solutions
.-
Michael A. Spfitoro, Sponsor Representative 3M Compdy
John M. FlAerty, k c i p a l Investigator
/ Exygen Research
A Date
Exygen Research
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Exygen Study No.: PO001131
ExygenProtocol Number: WOO1 131
TABLE OF CONTENTS
TITLE PAGE ........................................................................................................
................................ 1
DISTRIBUTION...............................................
PROTOCOLAPPROVAL........................................................................................................... ....................3 TABLE OF CONTENTS........................................................... .................................................. 4
INTRODUCTION............................................._................................................................ ..........5 TESTMATERIALS ................................................................................................ ............................ ............5
OBJECTIVE ..................................................................................................................................................... 6
TESTING FACILITY,................. .............,................................,..........................
STUDYDIRECTOR.......................................................................................................
SPONSOR REPRESENTATIVE..............................
.........*.....................*.........
PRINCIPALINVESTIGATOR........................................................................................................................ 7
PROPOSED EXPERIMENTAL START AND TERMINATION DATES ..................................................... 7
IDENTIFICATION AND JUSTIFICATION OF THE TEST SYSTEM ......................................................... 8
SAMPLE PROCUREMENT, RECEIPT AND RETENTION ......................................................................... 8
SAMPLEIDENTIFICATION............................................................. ............................................................. 9
ANALYTICALPROCEDURESUMMARY.................................................................................................. 9
VERIFICATION OF ANALYTICALPROCEDURE...................................................................................... 9 METHODFOR CONTROLOF B U S..................................................... ..*......................... *...........*........1I
STATISTICAL METHODS ............................................................................................................................. I 1
GLP STATEMENT...........................................................................................................................
..1 1
REPORT ..............................................................................................................................................I..1.......... SAFETY AND HEALTH.......................................................................................................... ...................... I2
AMENDMENTSTOPROTOCOL.................................................................................................................. 13
DATA RECORD KEEPING ............................................................................... 13
QUALITYASSURANCE............................................................................... ...............................................14
RETENTION OF DATA AND ARG-
........................................................................
APPENDIX I. ANALYTICALMETHODS......................................................................
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Exygen StudyNo.: PO001131
Exygen Protocol Numbcr: PO00113I
The purpose of this study is to perfonn analysis for perfluorobutanesulfonate (PFBS), perfluorohexantsulfonate (PFHS) and perfluorooctanesulfonate (PFOS)in water, soil, sediment, fish, clams, vegetation, small mammal livers and small mammal s m using L.C/MS/MS for the 3M Decatur Monitoring Program.
The study will be audited for compliance with EPA TSCA Good Laboratory Practice Standards 40 CFR 792 by the Quality Assurance Unit of Exygen Research.
TEST MATERIALS
The test materials are perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (PFHS)and perfluorooctanesulfonate(PFOS)and are all supplied by 3M.
PFBS
Chemical Name: Pduombutanesulfonate MolecularWeight: 338 supplied as the potassium salt (C&SO,X+) LotNumber: 101 Purity: 96.7%
TransitionsMonitored: 299 -+ 99
ShUCtlUC:
PFHS ChemicalName: Pduorohexanesulfonate Molecular Weight 438 supplied asthe potassium salt (Cfi13S03-K') Lot Number: SE036
Purity: 98.6%
Transitions Monitored 399 + 80
structure:
503'
FFF
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Exygen StudyNo.: POOOl 131
Exygm Protocol Number: POOOl 131
PFOS Chemical Name: Perfluorooctanesulfonate Molecular Weight: 538 supplied as the potassium salt (CsFdO3X') Lot Number 217 Purity: 86.9% Transitions Monitored: 499 3 99 struchue:
OBJECTIVE
The purpose of this study is to perform analysis for perfluorobutanesulfonate
(PFBS), pduorohexancsulfonate (PFHS) and pduorooctanesulfonate
(PFOS) in water, soil, sediment, fish, clams, vegetation, small mammal livers
and small mammal serum for the 3M Decatur Monitoring Program using the
c.4
current versions of the following Exygen analytical methods:
V0001780 V0001781: V0001782: V0001783: V0001784 V0001785: V0001786:
"Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Water by LCIMSIMS" "Method of Analysis for the Determination of Perfluorooclanoic Acid (PFOA) in Soil by LC/MS/MS" "Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Sedimentby LCIMSIMS" `Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Fish and Clams by LCMS/MS" "Method of Analysis for the Detennination of Pcrfluorooctanoic Acid (PFOA)in Vegetationby LC/MS/MS" "Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Small Mammal Liver by LCIMSIMS" "Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Small Mammal Serum by LC/MS/MS'
TESTING FACILITY
Exygm Research 3058 Research Drive State College, PA 16801 Phone: (814)272-1039
Page 6of 65
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Exygen Study No.:PO001131
- STUDY DIRECTOR
JaisimhaKesari P.E., DEE Weston Solutions,Inc. 1400Weston Way West Chester, PA 19380 Phone: (610) 701-3761 Fa:(610)701-7401 j .kesar@westonsolutions.com
Exygcn Protocol Number: PO001131
SPONSOR REPRESENTATIVE
Michael A. Santoro
3M Company Director of Regulatory Affairs 3M Building 0236-01-B-10 St. Paul, MN 55144 Phone: (651)733-6374
c4
PRINCIPAL INVESTIGATOR
John M. Flaherty Exygen Research 3058 Research Drive State College, PA 16801 Phone: (814)272-1039
john.flahcrty@exygen.com
PROPOSEDEXPERIMENTALSTARTAND TERMINATION DATES
It is proposed that the analytical portion of this study be conducted from October 01,2004 to December 31.2005. The actual experimental start and termination dates will be included in the final report.
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ExyganProtocol Number: PO001131
F
IDENTIF'ICAT'ION AND JUSTIFICATION OF THE TEST SYSTEM
The following are the test systems for this study: 0 Water (groundwaterand surfacewater) Soil 0 Sediment Fish Clams Vegetation SmallMammalLiver SmallMammalSerum
The samples will be collected by Weston Solutions. The control samples will be purchased and prepared by the testing facility. Purchase and processing details for the control samples will be included in the final report associated with this study.
The test systems were chosen to access the environmental impact of PFBS, PFHS and PFOS in the Decatur, Alabama area.
F
SAMPLEPROCUREMENT,RECEIPTAND RETENTION
Water, soil, sediment, fish, clapl, vegetation, small mammal liver and small mammal serum samples will be received at Exygen directly from Weston Solutions. The details of sampleprocurementfor this study are outlined in the 3M work plan entitled "Phase 2 Work Plan for Sampling Environmental Media." The number and types of samples collected will vary depending availability in the field. The total number of samples received and analyzed for each matrix will be documented in the final report associated with this study.
Water, soil, and sediment samples will be used as received without further processing at Exygen. These samples will be stored refrigerated at ZoC-8"C. Fish, clam, vegetation and small mammal liver samples will be processed according to the appropriate analytical method (see Appendix I). These samples will be stored frozen at 5 -1OOC. Small mammal whole blood samples will be centrihgedin the field at the time of collection and the serum fraction will be used for the study. Small mammal serum will be stored
frozen at s -1oOC.
The receipt and processing of the samples will be documented in the final report and raw data associatedwith the study.
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Exygen Rotocol Number: PO00 I 13 1
P-
SAMPLE IDENTIFlCATION
Prior to analysis, each sample will be assigned a laboratory sample reference number. The reference number will be unique and will distinguish each laboratory sample that is processed throughout the analytical procedure. Chromatographic data will be identified by the laboratory sample reference number.
Sample storage conditions and locations will be documented throughout the study.
ANALYTICAL PROCEDURE SUM!MARY
References: V0001780 V0001781: V0001782: V0001783: VOOOI784: VOOO1785: VO001786:
"Method of Analysis for the Determination of PertluorooCranoic
Acid (PFOA)in Water by LCIMSIMS"
"Method of Analysis for the Determination of Pduorooctanoic
Acid (PFOA) in Soil by LCIMSIMS"
"Method of Analysis for the Determination of Perfluorooctanoic
Acid (PFOA) inStdimant by LC/MS/MS" "Method of Analysis for the Determination of Perfluorooctanoic
Acid (PFOA)in Fish and Clamsby LC/MS/MS" "Method of Analysis for the Determination of Pduorooctanoic Acid (PFOA) in Vegetation by LC/MS/MS" "Method of Analysis for the Determination of Perfluorooctanoic
Acid (PFOA)inSmallMammal Liver by LCIMSIMS' "Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA)inSmallMammal Serum by LCMSIMS"
The above methods use analytical conditions capable of separating the isomers of PFBS, PFHS and PFOS. The final report will include the isomers summed into total PFBS, total PFHS, and total PFOS found.
A laboratory control sample will be used for the preparation of fortified control samples. The test substance will be made into solutions as per the method, and added to the matrices via a micropipette.
For water sampling, Exygen will supply one bottle per sample collected. The
c4
bottles will be SO0 mL. prtclcancd Sci/Spec Premier wide mouth HDPE
bottles. These bottles have been routinely used for fluomchemical sample
~
..
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Exygen Protocol Number:PO001 13 1
F
collection at the testing facility and have been shown to be fiee of PFBS,
PFHS and PFOS. Sampleswill be added to each container to a volumetric fill
line at 200 mL. A field duplicate, a low field spike and a high field spike of
each sample will be collected. The low and high field spike bottles will
contain PFBS, PFHS and PFOS aa well as perfluomtanoic acid (PFOA) and
1.2-13C perfluorooctanoic acid (''C PFOA). PFOA and "C PFOA are
included in the solutions used to spike the samples. The results for PFOA and
I3C PFOA will not be reported in this study. Exygen will supply one field
blank (control water) and two field blank spikes (control water fortified with
PFBS, PFHS and PFOS at a low and high level) for every twenty samples
collected. At the testing facility, each water sample (excluding field
duplicates and field spikes) will be extract4 in duplicate and will also be
fortified at a low and high concentration with PFBS, PFHS and PFOS and
processed through the described procedure to determine method accuracy and
to check for bias.
For soil, sediment,clams. and vegetation, Exygcn will supply one 500 mL precleaned ScVSpec Premier wide mouth HDPE bottle per sample collected or a zip-seal bag. All containershags used for sample collection will be shipped to the sample location. Samples will be added to each container or bag in the field. At the testing facility, each sample will be extracted in duplicate and will also be fortified at a known concentration with PFBS, PFHS and PFOS at
both a low and high level and processed through the described procedure to determine method accuracy and to check for bias.
For small mammal liver, Exygen will supply a 50 mL polypropylene centrifbge tube. For small mammal serum, Exygcn will supply a collection kit for each sample containing s m separator tubes (red top), vacutainers. needle holders and needles, transfer pipettes, and polypropylene tubes. At the twting facility, each liver and s m sample will be extracted in duplicate and will also be fortified at a knownconcentrationwith PFBS, PFHS and PFOS at both a low and high level and processed through the described procedure to
determine method accuracy and to check for bias.
Exygen Research
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Exygen StudyNo.: PO001131
n
f4
Exyga Protocol Number: Wool 131
Recoveries are anticipated to be between 70% and 130% of the fortified levels; however, the exact precision and accuracy will be determined by the analysis of the quality control samples described above. A statement of accuracywill be included in the finalreport.
METHQD FOR CONTROL OF BJAS
Control of bias will be addressed by taking representativesub-samples from a homogeneous mixture of each matrix from untreated control samples, and by andping at least two levels of fortifications.
STATISTICAL MET3ODS
Statistics will be limited to those specified in the subject methods and to the calculation of average recoverits, as applicable.
GLP STATEMENT
All aspects of this study shall be performed and reported in compliance with EPA TSCA Good Laboratory Practice Standards 40 CFR 792. The final report or data package (supplied to the Sponsor) shall contain a statement that the study was conducted in compliance with current and applicable GLP standards and will outline any deviations in the study from those standards. This statement will be signed by the Study Director and Sponsor Representative.
REPORT
A h a l report will be pnparcd by the principal investigatoror their designee at the conclusion of the study. The report will include, but will not be limited to, the following:
The name and address of the Study Director, Sponsor Representative, and of the testing facility.
A statement of GLP compliance (any related documentation, such as chainsf-custody rccords, must be in the study records).
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Exygen StudyNo.: PO001131
Exygen Protocol Number: PO001 13 1
The signed and dated statement by the Exygen Research Quality Assurance Unit regarding dates of study inspections and dates findings were reported to the Study Director and Management.
A description of the exact analytical conditions employed in the study. If the subject method was followed exactly, it is necessary to include only a copy of the analytical method. Any modifications to this method will be incorporated into the report. If the method is photo-reduced, the project number andpage number must be includedon each page.
Descriptionof the instrumentationused and operatingconditions.
All results from all seb analyzed. Control and fortified samples will be identified and the data table will include sample number and fortification level.
Representative chromatograms for each analyte in each matrix, including
chromatogramsof a standard and a control sample, and a chromatogramat a fortification level. The location of the analyte peaks will be clearly identified in all chromatograms.
All circumstances that may have affected the quality or integrity of the
F-
data will be documented in the report.
Locations where raw data and the final report are to be archived.
Additions or comtions to the final report shall be in the form of an amendment signed by the Study Director. The amendment shall clearly identify that part of the report that is being altered and the reasons for the alterations. The amendment will be signed and dated by the Study Director and the Sponsor Representative.
All applicable r#luirementsfor reporting of study results as per 40 CFR
792.185.
SAFETY AND HEALTH
Laboratory personnel will practice good sanitation and health habits
Every reasonable precaution shall be taken to prevent inadvertent exposure of personnel and the environment to the test or reference substance(s).
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Exygen StudyNo.: PO001131
ExyeenProtocolNumber: PO001131
AMENDMENTS TO PROTOCOL
All significant changes to the analytical protocol outlined here will be expressed in writing, signed and dated by the Study Director and Sponsor Representative. Amendments usually will be issued prior to initiation of study plan change. However, when a change is required without sufficient time for the issue of a written amendment, that change may be effected verbally with supporting documentation signed and dated by the Study Director and followed with a written amendment as soon as possible. In this case, the effective date of the written amendment will be the date of the documented change. Copies ofthe signed amendmentswill be appended to all distributed study plan copies. The original amendment will be maintained with the original study plan. Any deviations from the study plan or from the analytical method as provided will be documented and reported promptly to the Sponsor Representative.
DATA RECORD KEEPING
Records to be maintained include the following (as appropriate):
Sampletracking sheet@) Samplem i p t records, storage history, and chains of custody History and preparation of standards (stock, fortification, calibration) Description of any modificationsto the method Instrument run sheets,bench-sheetsor logs Analytical data tables All chromatographicand instrumentalconditions Sample extraction and analysis dates A completelistingof studypersonnel. signaturesand initials Chronologicalpresentationof all studycompondence Any other documentationnecessary for the reconstruction ofthe study
Chromatograms-All chromatogramswill contain the following:
0 Sample identification, injection date, arrow or other indication of the area
of interest, and injection number correspondingto the run.
Additionally, fortifications will include the amount of analyte added and the sample number of the sample that was fortified. Analytical standard chromatograms will additionally include the concentration(e.g.. pg/mL).
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Exygen StudyNo.:PO001131
Exygn Protocol Numbcr: PO001131
P-
ASpart of the documentationthe following sheets will be included in each analytical set: a run sheet listing the samples to be run in the set. and an instrument conditions sheet describing the instrument type and operating
conditions.
QUALITY ASSURANCE
The QA Unit ofExygen Research will inspect the study at intervals adequate to assure compliance with GLP's, and will report the fmdings of audits to the
StudyDirector, ExygenManagement,and the SponsorRepresentative.
RETENTION OF DATA AM)ARCHIVING
All hard copy raw data, including, but not limited to, the original chromatograms, worksheets, correspondence, and results shall be included with the data package submitted to the Study Director. These will be archived with the original study plan, amendments, final report, and all pertinent informationh r n the Sponsor.
The testing facility shall keep all electronic raw data and any instrument. equipment, and storage logs for the period of time specified in 40 CFR 792.195. An exact copy of the materials submitted to the study director will alsobe kept at ExygenResearch.
Exygen will obtain permission from the study director before discarding or
returning samples.
Exygen Research
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Exygen StudyNo.: PO001131
Exygen Protocol Number:PO001131
APPENDIX I
ANALYTICAL METHODS
V0001780 V0001781: V0001782: V0001783: V0001784: V0001785: V0001786:
"Method of Analysis for the Dete-rmination of Perfluorooctanoic Acid (PFOA) in Waterby LCIMSIMS" "Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Soil by LCIMSIMS" ``Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Sedimentby LC/MS/MS" "Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Fish and Clams by LC/MS/MS" "Method of Analysis for the Detumination of Perfluorooctanoic Acid (PFOA)in Vegetationby LC/Ms/Ms" "Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Small Mammal Liver by LC/MS/MS" "Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Small Mammal Serum by LC/MS/MS"
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Exygen Study No.:PO001 131
Exygen Protocol Number: PO00I131
ANAJ.YTICALME"HOD MahodN W V0001780
Paul Coaaollv
I
Exygen Research
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Exygen ProtocolNumber: PO001131
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6.0
7.0 8.0
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Exyfienprotocol Number: Po001131
(rw 9.1.2 A IO
fo#tiidutMnrduriCn,ofPFOA ir propvod by brinyiny IO
mL oftbo 100 p g h L lolution10 I volume of IO0 with nrrhnol
in I 12s mL LDPE botcb.
9.1.3 A 1.0pmL fOrti5don solution ofPFOA is prop.rod by bringing 10
mL of lb IO p#mL lolutionto I Gnat voluma of 100 with mcthrvll in
a 125 mL LDPEboPlo.
9.I.4 A 0.1p#mL hm'dutionsohuionof PFOA is PIOpMdby bringing 10
mLoftbo 1.0 p#n& rolutbn(0I h l volumo of I00with mhnol in I 125 mL LDPEboaIo.
9.13 A 0.01 p@ forcificuim lolutionof FTOA h proparod by bringing
10 mL of mC 0.1 p&L solution to a f i ~ lvolumc of 100 with
m d u d in I 12s mL LDPE bonk.
9.1.6 Tbc mock md foniflationlohtio~mto b o d ins refrigerator11 ~pp~oxlarts4ly% ud mCublo for Imaximum period of 6 months
ha0 tlm *toof prqmlion.
IO
100
40
10
m
40
IO
400
40
100
100
40
IM
25
50
xcmnddwz
loo
xctnmddyy-3
250
XCmmddyy.4
-
~
-
.
Exygen Research
Page 19 of 4s
Page 53 of 118
Interim Report #26 - Analysis of Groundwater Samples
Exygen Study No.:PO001131
Exygen F'romol Number:PO001131
12.0 w
y
12.1
12.2 12.3
12.4
. -.
Exygen Research
Page 20 of65 . .
Page54of 118
Interim Report #26 - Analysis of Groundwater Samples
Exygen StudyNo.: POOO1131
Exygen Protocol Number: POOOI 13I
rh
13.1 13.2 13.3
13.4
13.5 13.6 14.0 C a k U h t h
Exygen Research
Page 2I of 65
Page 55 of 118
Jnterim Report #26 - Analysis of Groundwater Samples
Exygen Study No.:PO001131
ExygenprotocolNumbcr: PO001131
Exygen Research
Page 56 of 118
Interim Report #26 - Analysis of Groundwater Samples
Exygen Study No.:PO001131
Exygm Protocol Number: PO001 13 1
AMI^ TawPlcilii
exyscD3058 RorsuchDrive Swo Collep, PA 16801
. -
.-
Exygen Research
Page 23 of 6S --
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Interim Report #26 - Analysis of GroundwaterSamples
~~
Exygen StudyNo.: PO001131
Exygcn ProtocolNumber: PO001131
3.12 SPE
&fold.
5.13 Ubwn&b.lh.
Exygen Research
Page 24 of 65 .
Page 58 of 118
~~
Interim Report #26 -Analysis of GroundwaterSamples
Exygen StudyNo.: PO001131
Exygenprotocol Number PO001131
5.14 W r L t - h - . 5.1 5 Cmbiliqoaplblc of lpirniry SO mLpolypmpyloocNbea u SO00rpm.
6.0 czrOml(op.phicS~m
Exygen Research
Page 59 of 118
Interim Report #26 - Analysis of Groundwater Samples
Exygen StudyNo.: PO001131
Exygen Rotocol Number: PO001 131
9.0 st.ndudPmp-
9.1 Sbaddsmcwpolri6cUionSoltllioD
9.1.1 Roppo8~wlutionof-100pgbLofPFOAbyweighiny 10ms
ofd r r i f . l Icndnd (conrccod hpurity) ud dilula to I 0 0 mL with
mabnolin a 12SmLLDPEbatla
9.1.2 A 10pJmL fonifioltioaColutiOno fPFOA iiprop.red by brinyiny I I1
mL of dm 100p&h~Lalution to L final volume of I00 with mcrhanol
(rm ina 125mLLDPE M e .
9.1.3 A 1.0
fortifiutionwlulionofPFOA u PrCpMdby bringiny IO
mL of tbo 10pg/mL wlution to a find volumeof 100 with mrhmlir~
L 1U mL LOPEbottle.
9.1.4 A 0.1 pJmL rOnitk*imwhpiDnof PFOA u
by bringing I O
mLofpl01.0&nLwluim to 8 flnrl volume of 100with mdunol in
a 123mLLDPE boltlo.
9.13 A 0.01 p$mL f&iIiC*oa mlurion of PFOA ir pr4purd by btineincr
. 10 mL of the 0.1
rolution to a 5n.l volume of 100 with
d i n8 125mL LDPEW.
9.1.6 Ttw no* ad lortiflucionwlut#luw to k aomd in a rofrigoruor (11
qpoxlnukly 4.C ud am N b l o for a nuximum paid of 6 months
mlmh&ofprop~.
9.2 SI.ldudC*Solutoa
9.2.1 9.2.2
Lc/MsmdS cdbmioa amdmnla M p q r r e d in HPLC water The cllibntion amdud# w pmcollod through L o axtnction procedure. iddcrltormpla.
Tha folk+ u a typical aumplo: additional oonconlrations may be
prqmrdu-
-.--
Exygen Research
Page 26 of 65
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Interim Report #26 - Analysis of GroundwaterSamples
Exygen StudyNo.: PO001131
Exygen Protocol Numbcr: PO001 13 I
swc 9.2.3 A m tundud lolution (ro8gmt blank)
aofluldub .xmcuQ.
with uch
92.4
d l cxnwcd ulibncion N a d d a in 1 5 4 polypropylenelubes
It 2.C to 6*C, up to two w&.
92.5 Manu0volumr mdcorrooslhrtioruof atanduda may k prepucd as
nssded.
10.0 Bltsh S d Q
10.1 E.eh b d of~umplm atnctcd (typically 20 or l a ) muu include u least OIK 10.gl~c at h d (mcvlDd b*dc usins 5 mL of mcthlaol) md two reagent CCotmL brcifisd M b W l Q*IwIIlIL(IWl (Lb Conlml l p h ) IO VCflfy
pocodunlncowyhBtthokteb 10.2 b q u i r m a ~ftw~ Cold rad lrbontorydupliulcc rad apikn will k specified
in the purlity uaaneopkn h l h t pjcct.
11.1 112 11.3 11.4
11.5 11.6 11.7 11.8
11.9
12.0 -y
Exygen Research
Page 27 of 65
- . .. .. . .--
Page 61 of 118
~~
Interim Report #26 - Analysis of Groundwater Samples
Exygen Study No.: PO001131
12.4 12.5
13.1 133 13.3 13.4 13.) 13.6
Exygen Research
Page 28 of 6s ...
Page 62 of 118
Interim Report #26 - Analysis of Groundwater Samples
Exygen StudyNo.:PO001131
Exygen Protocol Numbcr: PO001131
14.0 Clln*tbru
14.3 UMIhfnllowiag oqdm la mmm the .mount of PFOA found in ne/L lo
nuh @pb).
l ~ p lwsripht (5 0)
14.4 UM tbo folbwing qurlion to &late the mow1 of PKlA found in pph bucdaldrycwripbr.
PFOA fouud@pb)dry wdghl- PFOA found (ppb) x [loOK I total mlidr(%)]
P-
-
Exygen Research
Page 29 o/ 6J
..
Page 63 of 118
Interim Report #26 - Analysis of Groundwater Samples
~-
Exygen StudyNo.:PO001131
Exygcn Rotocol Number: pooOl13 1
ANALYTICAL METHOD
M O ( b 0 d m . vm1782
Agpovod By:
Exygen Research
TotllPaga: 7
Page 30 of 63
- _.- _-
Page 64 of 118
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Exygen StudyNo.: PO001131
Exygen Protocol Number: PO001 13 1
- ,
F
Exygen Research
Page 31 of 65
Page 65 of 118
-
~~
Interim Report #26 - Analysis of Groundwater Samples
Exygen Study No.:PO001131
ExygenProtocolNumber: WOO1 131
F
e l m llrrs~
M W N e Voa)l711
1 1 ANALYTICALMETHOD
Mahod of M y a hfor IhoDarmdnubnofPDmuorooctmic Acid (PFOA) in S d i m m by
LclMsmdS
6.0
7.0 8.0
Exygen Research
Page 32 of 6s
--
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Interim Report #26 -Analysis of GroundwaterSamples
Exygen StudyNo.: PO001131
ExygmProtocol Number:PO001 131
=m=-
Mrtlvd Nvlllba vooo1111
1 1 ANALYTICALMETHOD
MethodofAnrly*rIm tho D*ocminuiw of Pufluotuocundc Acid (PFOA) in Sedimml by
Lc/Ms/Ms
9.1 SedPdStodJFatihcrtiooSclutioa
9.1.1
a llock rdutboof -100 p m of PFOA by woighin) I O m i
ofllulylicdluldrd(conacdforpurity).oddilu~IO~~OmL with
-1
in 1 125-IOL LDPE bouk.
9.12 A 10p w br~iticuionsolulioaof PFOAia PnpMdby bringing IU
mL of b 100 jIm solutioll Io a fkul volume Of 100 with rnhmol
in a 125 mL LDPE bottb.
9.1.3 A 1.0 p w Gmifidon ~Ol~tiOofnPFOA is plcpvcd by bringinp IO
mL of tlw 10~&IL solotionto a find volume of 100with mcthlnol in
a 125 mL LDPB bonk 9.1.4 AO.lw/mL@d5CUtOII MI* of PFOA is plcplrsdby bringin) 10
I O L d t b r I . O p g / m L l o l u t i a , 0 a ~ v o l v w o f100withmclhrnolin
a 125 mL LDPE bonk.
9.1.5 A 0.01 p J m L Mfiati011solvtion of PFOA in PrOpuDdby bringing
10 mL of Ihc 0.1 p#mL solution Io a 6nd volume of 100 with
udwdh a 125 mL LDPE boule. 9.1.6 Tlu mck ud EortitiatimsolutionrPO Io be Mnd ina nfdgwuor 81
spmximwly 4.C and PO #Idlafor a mubnumpaid of 6 months
lrrm tbr datn of prclpmtion.
93 S ~ c d b m l b n s O l ~
92.1 Lc(hds/Ms& i a a nrdrbmFspMdin mahnolvia dilution
0fbO.l ~iortllic.tknsoluIioa
9.23 The followin#ia 8 typical a m p l e : lddiliarrl Unrcntntionr may be
pmurcdnneulul.
Find
ofFoailk&ea Vo*nm solutim(llprmL1 (mL)
WWdm (mu
conC~nmlion (WnlL)
I00
10
1.M ..
10.0
100
5
100
5.0
100
2
100
20
10
10
IM
I .o
5
10
100
0.5
Exygen Research
.I__
Page 33 of 65
Page 67 of 118
Interim Report #26 - Analysis of Groundwater Samples
Exygen StudyNo.: PO001131
Exygen ProtocolNumber: PO00113I
11.1 11.2 11.3 11.4 113 11.6
11.7 11.11 11.9 11.10 11.11 11.12 11.13
F-
- .
. __
Exygen Research
_. -
Page 34 of 6s
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Interim Report #26 - Analysis of GroundwaterSamples
Exygen StudyNo.: PO001131
Exygen Protocol Number: Po001 13 I
12.0 Qlmrmmsrrphy 12.1 I22 12.3
12.4 12.5 13.1 13.1 13.3
13.4
13.5
Exygen Research
Page 35 of 65
Page 69 of 118
Interim Report #26 - Analysis of GroundwaterSamples
Exygen StudyNo.: PO001131
Exygen Protocol Number: PO001131
.__ ... Exygen Research
Page 36 of65
Page 70 of 118
Interim Report #26 --Analysis of Groundwater Samples
Exygen Study No.:PO001131
Exygen Protocol Number PO001131
Exygen Research
Page 37 of65
Page 71 of 118
Interim Report #26 - Analysis of Groundwater Samples
Exygen Study No.:PO001 131
Exygen Protocol Numbcr: PO001 13 1
Exygen Research
Page 38 qf 65
Page 72 of 118
~
~~
Interim Report #26 - Analysis of Groundwater Samples
Exygen Study No.:PO001131
Exygm Protocol Number: WOO1131
ww-
MnW N d r VMo1781
I I ANALYTICALMETHOD MahDdof Anrlydifwcbc Dmamhbmof P e r h m W m o i c Acid (PFOA) in Fish and
ClpalbyLclMSlMs
5.4 5.5 5.6 5.7 5.8 5.9
5.10 5.11 5.12 5.13 5.14 5.15 5.16
6.0 Q r o m l l O ~ S ~
6.1 Aollyr*.l column:Pluc@uc RP (KoyltOM Scicali5c).2.1 mm x 50 nun. 511
(Ph? 82505452130) 6.2 Tanpplturs:30% 6.3 MobiloPlum (A) : 2 mMAmmonium Acdltoin Warn 6.4 Mobilopbu(B) : Mahnol 6.5 OndiClltMp:
Y mdmu 0.0
1.0
65
8.0
25
20.0
25
a23
65
plow Rue
UwhiuI
35
0.3
35
0.3 '
75
0.3
75
0.3
35
0.3
6.6 6.7
injljocrim Volumo: Quntit*oa: POJ;
15 A
-pL (M
m cx
t
be iDerrusd IO u much u 50 # mul ~tuuludcalibrationcurve.
L
)
6.8 RunTim: -23minum.
The r b o v r d i t i o n s u s in(cmd0du8gurds ndmay boclunsod in order OI
optimlu Um HPLC-.I
Exygen Research
Page 39 0165 . .~_.
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~~
Interim Report #26 - Analysis of Groundwater Samples
Exygen StudyNo.: POOO1131
E x y p ProtocolNumber: POOO113I
8.0 h p u u i o n o f S o l u ~ 8.1 MobilePhvD
8.1.1 2 mM d m aceate In rnta is prop.rcd by adding 0.154 p of
analOnhwu(atolWOrn0f~.
8.2 % ~ s o b r r i o m
8.2.1 2% Ilcaldf ridhMch.clol i s m by diuolving 2 8 of ueorbic
acid in 100 mLofmeUunol. 82.2 30% Dimahyldi&b&lns in toluao is pnp.rsd by bringing 3 mL
ofdimabyld*hbrodlne lo L tind volumoof I O mL with toluene.
Altanrtovohrmarmybcprrpnd.
9.0 SuadrdPrcprUb 9.1 Stmdud StoclrlpOnifi~iOSooh*on
9.1.1 Pqwe L aock mhulonof-100 #Jml. of PPOA by woighiny IO my
of uulytimlmrdd(corroctd for purity) rd dilute to I00 mL with mclhurolina l Z h L LDPEbottle.
9.12 A 1.0 rJmL rorrif*ltimlolutiOnof PFOA is p r c p d by brindny 1
mL of (bo 100 p w mlution to a Bnrlv a h o of 100 with mnhrnol In. 125 mL LDPE W.
9.1.3 A 0.1 pg4uL hrtiflacioowlutkm of PPOA & pnpuodby bringinn 10
mLoftJu1.0~g/mLwlutionb~fuulvolume1o0f0wilhmttunolin
L l2S m L L D P E W .
9.1.4 A 0.01
fortiifidonmhrtiomof PFOA is propvcd by bringing
10 mL of (bo 0.1 p#mL rdvtba to a firul volume of 100 with
lwlunoIh a I d mL LDPE ban*.
9.1.5 l b ltodr mdWidE.tjolllolutiam y.to bo cored in a rohigarUor11
lppmximuoly 4.C md M &IC for a maximum parid of 6 months
frmn bd.trof PIqmIiolY.
Exygen Research
Page 40 of 65
_--.-
Page 74 of 118
Interim Report #26 -Analysis of GroundwaterSamples
Exygen StudyNo.: PO001131
Exygen Rotocol Number: PO001 13 I
Exygen Research
Page 41 of 65
Page 75 of 118
Interim Report #26 - Analysis of Groundwater Samples
Exygen StudyNo.: PO001131
Exygca Protocol Number:PO00113I
12.0 c a u m u w @ y 12.1 12.2 12.3
12.4
Exygen Research
Page 42 of 65 ....
Page 76 of 118
Interim Report #26 -- Analysis of GroundwaterSamples
Exygen StudyNo.: PO001131
Exygen Protocol Number: PO001 131
L ' b3=-
w&d~.lakrv~~~ini
* ANALYIICALMETHOD
Mabod ofA d y x b far mC Daennimtimlof prtlumDocuMic Acid (PFOA) in Fish and ClaubyLcIMSIMs
DF - frtocby wbich Ibc find volum~w u diluted. if ncccuuy
Page 43 of65
Exygen Research
Page 77 of 118
Interim Report #26 -- Analysis of Groundwater Samples
Exygen Study No.:PO001131
Exygcn Protocol Number: Po001 13 1
.
Exygen Research
Page 44 of65
.-
Page 78 of 118
InterimReport #26 --Analysis of Groundwater Samples
Exygen StudyNo.:PO001131
ExygonPmtocolNumber: POOO1131.
ANALYTICAL MBTHOD
MdhcdNmbor: VOOOllU
__ .. . __.
. _.
Exygen Research
Page 45 0163
Page 79 of 118
Interim Report #26 - Analysis of Groundwater Samples
Exygen StudyNo.: PO001131
ExygcnProtoc0l Numbcr: pooOl I3 1
3.1 3.2
3.3
Exygen Research
Page 46 of 6s
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Interim Report #26 - Analysis of Groundwater Samples
Exygen Study No.:PO001131
r.
ExygcnProtocolNumbcr: PO001131
5.4 5.5 5.6
5.7 5.8 5.9 5.10 5.n
5.12 5.13 5.14 5.15
6.0 Ckon~-Syltom
6.1 ~ ~ ~ l ~ F l w ~ R P ( K c y l t o r r S c i c n ( i f i mc )m.x2J.O1mm.5p ( P M 12505-052130)
6.1 TompcnRuo: 3W 6.3 Mobile phw (A) : 2 mM knmcailm,AcUUc in Weka 6.4 Mobibpbus(B): MMhmol 6.5 ansinrhwn:
FktWR4W
Y Y P 0.0
1 .o
65
35
0.1
8.0
25
75
0.3
20.0
25
75
0.3
22.5
65
35
0.3
- 6.6 &tjalimVohmm I 5 p L ( w b e i d to nmvch Y SO pL).
6.7 Qwnlitatioa Pak A m aQryl nradpd ulibntioncurve. 6.8 RunTimr:-Umlau(r
IholbovocordiliolvM L*ndodY I plidcmdmy be &gad in ordor to
OplimLOtbeHPLcryNm
. .
Page 47 of 65
--
Exygen Research
Page 81 of 118
Interim Report #26 - Analysis of Groundwater Samples
Exygen Study No.:PO001131
Exygen Protocol Number: PO001 13 I
Ibrb0wumdili.a~am inadodY r plido md m y bo changed in order to OptimLC theMSMS r)*rm.
+ 9.1.1
IUwk mlutionof-100 pJmL of PFOA by weighing 10my
of yvlvticll NDdrd(mnwtod for purity) ud diluto to I00 mL with
&I in I 12s.m~mpeb e . 9.1.2 A 1.0 rJmL fordtlutimrohaion of PPOA u pnp.nd by brinainy I
OILof cbc I00 ppsmL mlutionto I find volume of I00 with mcchnol
in I123mL LDPE book.
9.1.3 A 0.1 p#iuL fo~lill& polutioaof PFOA is pcpmdby bringing 10
. mIoftb0 1.0p~colutiontorfuulvolvmoof100withmcthmlin
I 123 mL LDPB b".tlle. 9.1.4 A 0.01 pJmL lorpBatlonmlution of PFOA is plcpmd by bringin8
10 mL of ths 0.1 p#mL Idution to I h l volume of 100 with
llmknolin a 12s `?LLDPB ban*.
9.13 ~~d~
mlutioluam to bo scaod in1I O f I i ~ 0r1
appumWy4T d ucmbk for r nuximum p&d of 6 months
fmm mc duc ofpnpurcion
9.2 S t . l d u d ~ S o l u t i o r m
9.2.1 LcRdslMSulibntiw Uy.aop.nd in mahvlolvir dilution oftbo 1.0pJmL bDnitiutioamlutim
P . p 4 "I -
Page 48 of 6S -
Exygen Research
Page 82 of 118
Interim Report #26 - Analysis of Groundwater Samples
Exygen Study No.:PO001131
Exygea ProtocolNumber: PO00I 131
Exygen Research
Page 49 of 6S . _.
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Interim Report #26 -- Analysis of GroundwaterSamples
~~
~~
Exygen StudyNo.:PO001131
ExygenProtocolNumkr: PO001131
12.1 123 12.3
11.4
11.5
13.1 l%mubpmmu( dov rpuk o f a bu- ion u 369 m u lirma ~ M I I
of 413 IIIY. Ih 413 m u puslr cmrpmd.to Iho PFOA anion. while Ihc dm@lcrbn (369mu) rqmnoUw lor ofcubon dioxide.
..
. ......
Exygen Research
Page 50 of 65
Page 84 of 118
Interim Report #26 - Analysis of Groundwater Samples
~-
Exygen Study No.:PO001131
Exygen Protocol Number: PO001 13 I
14.0 CllcuLtiau
-.
Exygen Research
Page 51 of 65
Page 85 of 118
Interim Report #26 - Analysis of Groundwater Samples
Exygen Study No.:PO001131
ExygenProtocol Number: PO001I 3 I
ANALYTICAL. METHOD
MdwdNwnbm VooOl785
Appmvod By: Paul CDnnOllv
LA4
IO\U/O~ Dsk
L Dnta
--
I_-.-
-.
Exygen Research
Page 52 of 65
Page 86 of 118
~~
Interim Report #26 -- Analysis of GroundwaterSamples
Exygen StudyNo.: PO001131
Exygen Protocol Number: PO001 13 1
Exygen Research
Page 53 of 65
Page 87 of 118
Interim Report #26 -- Analysis of GroundwaterSamples
Exygen StudyNo.: PO001131
ExygenProtowlNunlbcr:POOOl131
5.9 5.10 5.1 I
5.12
- % ? 0.0
1 .o
65
1.0
25
10.0
25
22.5
65
FloWRuc
Y Y 35
0.3
75
0.3
75
0.1
35
0.1
6.6 6.7 6.8
- - h i d o V~o~lum6: I S pL (can k imwdto u much u 50 pL).
QumriWioll: P aArr ~QII~ICllibntioa C W e . Run T h 23 minaw.
Tholbovo ondiliMLpaadsdu a*
OprimiuthcHPu:~.
ud mry be ChalgOd inorder to
.. . .
Exygen Research
.._...
Page J4 of 65
Page 88 of 118
Interim Report #26 - Analysis of Groundwater Samples
Exygen Study No.: PO001131
Exygm Protocol Number: Wool 13 1
~~
8.0 Ropvltiarrofsolu(ioar 8.1 Mobilrphvr
8.1.1 2 mM d m a m in wmta u PrOpMd by dding 0.154 g ol' d u n axtaw to loo0mLof water.
Allt?nuc voluma may be p.purd.
9.0 SmavdRDprntion
9.1 Scodod s(ocwpati<im Wuriw 9.1.1 Ropm1 mock solution of-100 pg'mLof PFOA by weighing IO ing of uvlyticllamdud(corroaod lapurity) ud dilute to I00 mL wilh nuc)unolin 1 12s-IIILL- DPEW e . 9.1.1 A 1.0 pg/mL for~idodonmlulionof PFOA u p m p d by bnnging I mL oftb 100p J m L mlution lo a Gnrl volume of 100 with &no1
m i121mL LDPE W e . 9.1.3 A 0.1 &mL tntitlcnion mlutionof PFOA u pmpuod by bringing IO
mLofllv 1.O~mlulionloaruulwlumeofIOOwilhmerholin L I25 mL LDPE bo&. 9.1.4 llvltooLIDd fontficaion~luloM ~ Cbealorodin irchipa.tor .( qpxinutdy 4.C uul M nblc for nuximum pori& of 6 months %omlhc drtoofpup~m.
9.2 S t u d a l ~ S o ~ o m
92.1 LCIMSIMSdbntionnrmdpdrmp q w d in mollmnol via dilution oftbr 0.1 p a MEcation mhuioll.
9.2.2 TbO l o w is a typical example: d d i W conconmtionrmay be
p.oprod=-
w
FilU1
ofFacillc&m Vdumr
blIllian(oJmL) (mL)
100
5 .o
DiluDdW
(Id)
100
Coaccnmtion (ndmL)
5.0
100
2.0
I00
2.0
100
1 .o
100
I .a
5.0
IO
I00
0,s
1.0
IO
100
03
1.0
IO
I00
0.1
92.3 SM B UlibmhW in 125-mLLDPE numw-mouth bllleo
2y: lo6.C. up to aixmooc)~.
9.2.4 A-I
vohunoc U!d coIIcQlb.tiOM O f SImdUdW mly be PrCplICd U
noakd.
Page 55 of 65
Exygen Research
Page 89 of 118
Interim Report #26 - Analysis of Groundwater Samples
Exygen Study No.: PO001131
Exygen Protocol Number: PO001131
11.1
11.2 11.3 11.4 11.5 11.6 11.7 11.8 11.9 11.10 11.11
12.1
123 12.3
124
PDgs 5 o n
.. .
Page 56 of 65
Exygen Research
Page 90 of 118
Interim Report #26 - Analysis of GroundwaterSamples
Exygen StudyNo.: PO001131
Exygen ProtocolNumber: PO001131
13.1 13.2 13.3
13.4 13.5 13.6
14.1
Exygen Research
Page 57 of65
Page 91 of 118
Interim Report #26 - Analysis of Groundwater Samples
Exygen Study No.:PO001131
Exygen Rotocol Number: Wool 131
Exygen Research
Page 58 of 65
Page 92 of 118
Interim Report #26 - Analysis of Groundwater Samples
Exygen Study No.:PO001131
Exygcn RotocolNumber: Po001131
ANALYTICAL METHOD M * b o d N m k VooO1786
- ,
Exygen Research
_.. ._ _ ..-.
Page 59 of 65
Page 93 of 118
Interim Report #26 --Analysis of Groundwater Samples
Exygen Study No.:PO001131
Exygen Rotocol Nunrber: PO001 13 1
rh
Exygen Research
Page 60 of6S
Page 94 of 118
Interim Report #26 - Analysis of Groundwater Samples
Exygen Study No.:PO001131
Exygen Protocol Number: PO001 I3 I
m-
MlkdNvpbnVMW17Yb
L I MALYTICAL METHOD McUmd of Anrlyis (br tbcDacnnidw of P a r h m o m m i c Acid (PFOA) in Smdl
M u m u l Strum by LCMMYMS
Iim 0.0 hinIy
I .o
65
8.0
25
20.0
25
22.5
65
Y - 0.3
35
0.3
75
0.3
75
0.3
35
0.3
7.1 Mod.: ElccbwpmyN ~ v MoRM d e , monitoring413 -+ 369 m/z for
mA.
n# above d t i o r u ma int~dalu pi&ud may bo Churgcd in ordn lo
0phiZOUL.MSMSlydaa
Exygen Research
Page 61 of 6s
Page 95 of 118
Interim Report #26 --Analysis of GroundwaterSamples
Exygen StudyNo.: PO001131
Exygen Protocol Number: PO001 13 1
9.1 S m d d SmdJpDlcidcdonSolution
9.1.1 Plqvo L #bxk lolutionof -100 p#mL of PPOA by weighing IO mg
o f u u I m smdd (oorroetodlop purily) uld dilute to 100 mL uidi
A I inL IZS-mL LDPE bonk.
9.13 A 1.0 p#mL Mtldonmlutiw of PFOA is prepared by bringing I
mLof h100 pun& solution to a 6nal volume of la0 with mcthnol
in8 125 mL. LDPE W e .
9.1.3 A 0.1 pl/mL fmliburiotllolwion of PWA ia prceuad by bringiny IU
mtoftlw 1.0 p#mLlolutim (0L 5 d vohuao of 100with nvlhrnol in
L 125 mL LDPEbocuo.
9.1.4 Tbe
f d h ! i o a lolutiauaa to bestored in a nlligmorat
gpourmtoly 4.C d M ltlblafor L muhum period of 6 month,
flmnchodnoofpvrpdm
9.2 S m d u d c . l i b n i i o n S o ~
9.2.1 Lc/MGIMsulibdoa amduvh M prqwod in methanol via dilunon ofrnc 0.1 jt#IllL hlifiutiw solution.
93.2 'Ibr foilowing L a cypial example: d d i t i d caumkuiolu may be popuoduaaodd.
Find
dFmilh.tion V o h
Diluz.dto
Coacmmtioa
SOhlioa~nJd) (mL1
(mL1
(nJmL)
100
5.0
100
5.0
100
2.0
loo
2.0
100
1 .o
IW
I .o
s.0
IO
I00
0.5
2.0
10
100
0.1
I .o
10
IC4
0.1
9.2.3 StDn 111alibntiaa #tmdudain 125-mL LDPE naow-mouth bottler
m PC to6.C, upbh monthr.
9.2.4 Auautcvolunos adconccllmtionrof mndmhmay be prepared 1u
Modcd.
10.0 BltchSrnUp
Exygen Research
Page 62 of 65 .-
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Interim Report #26 - Analysis of Groundwater Samples
~~
~~~
Exygen StudyNo.: PO001131
Exygen Pmtocol Number: PO001131
11.0 SmnpleBXmbkm 11.1
11.2 11.3 11.4 11.5 11.6 11.7 11.8 11.9 11.10 11.11
12.0 ClnormtDBphy 12.1
12.2 12.3
12.4
12.5
Exygen Research
Page 63of 6s
Page 97 of 118
Interim Report #26 - Analysis of Groundwater Samples
~
Exygen Study No.:PO001131
lkygen Protocol Number pooOl131
14.1 14.2 - .
Exygen Research
Page 64 of 65
Page 98 of 118
~
~~
Interim Report #26 --Analysis of Groundwater Samples
Exygen Study No.:PO001131
Exygen Research
Page 65 of 65
.
. ...
Page 99 of 118
Interim Report #26 --Analysis of GroundwaterSamples
Exygen Study No.: PO001131
RESEARCH
3058 Research Drive Phone: 814-272-1039 State College, PA 16801 Fax: 814-231-1580
PROTOCOLAMENDMENT
Amendment N u m b e r : L Effective Date: 01/19/05 Exygen Study Number: PO001131 Client Study Number:
Page Iof I
DESCRIPTIONOF AMENDED SECTION 1) Analytical ProcedureSummary V0001780:Sedion 9.1 2) Verification of Analytical Procedure
None
AMENDED TO
1) Add to Section 9.1: Section 9.1.6. Alternate weights of standards may be used to
preparealternate concentrationsof stock solutionsas n e e s a y . Alternate levels of
fortifcation solutions may also be prepared.
2) Low and highspiking levels of the analytesfor each matrix may be altered depending
on sample size available for extraction and/or to cover analyte concentrations expected in the samples.
RATIONALE 1) Higherconcentrationsof standards needto be preparedin order to spike the sample bottles at higher levels. 2) The sample size available for small mammal liver and serum was smaller than expected. Spiking at the pre-determined levels in the protocol puts the spiked
concentrationlower than the detedionlimit. Also, the anawe levels in the ground Water samples are expectedto greatly exceed the predeterminedspiking levels listed inthe protocol. When the levels in the samples greatly exceed the spiking levels, an accurate recoveryvalue cannot be calculatedfor the QC sample. Higherspiking levels in the bottleswill cover the analyteconcentrationsexpected in the water samples.
IMPACT ON STUDY The LOQ is 100ng/g for a 0.1 g sampleof small mammalliver and is 1000 ng/mL for a 0.01 mL sample of small mammalserum. Higher levels of spiking for the water samples will ensure thaf more QC recovery data can be used.
ISpins rSlgiiture (if q G j )
-
LIBRARY ID:wooo1226-6
Datd I
Exygen QAU Review &lf
.ADMINISTRATIVEFORM
Exygen Research
Page 100 of 118
Interim Report #26 - Analysis of Groundwater Samples
Exygen Study No.:PO001131
t w eRnESEA 'RCH
3058 Research Drive
Phone: 814-272-1039
State College, PA 16801 Fax: 814-231-1580
Amendment Number:
Effective Date:
Exygen Study Number
PROTOCOL AMENDMENT 2
03107l05 PO001131 Client Study Number:
Pagalof1 None
OESCRIPTION OF AMENDED SECTION
1) Report, page 11 of 65 2) Test Materials, page 6 of 65: PFOS transition monitored 499 -> 99.
/WENDED TO 1) Instead of one final report, interim reports will be issued. 2) PFOS transition monitored may also be 499 -> 80. ,
RATIONALE
1) Due to the excessive sizes of'the data sets,interim reports will be issuedto allow the client to receive data in a timelierwanw manno- od& 4W 2) The API 4000 LCIMWMS systems detect the 499 -> 80 PFOS transition with greater sensitivity than the 499 -> 99 transition.
IMPACT ON STUDY
1) The client will be able to receive and review the data more quickly.
2) The 499 -> 80 transition can be detected with greater sensitivity; therefore, giving better chromatography.
A
3kb5 &A+ Date
Date
8 -*-os
Exygen QAU Review A%!J, r%3lo6b
LIBRARY IO:V0001226-8
ADMINISTRATIVE FORM
Exygen Research
Page 101 of 118
Interim Report #26 --Analysis of Groundwater Samples
Exygen StudyNo.:PO001131
NL.1.2e05 8:-
~~
m.774 p.3
30% ResemhDrive P h c : 8142724039 State Colhge, PA 16801 Fu! 814-2314560
Amendment Number:
Eflecthro Ddcc
'
Exyoen Study Number
PROTOCOL AMENDMENT
3 0711BK16
P1131 Client Study Number:
Pagelart
NA.
Exygen Research
Page 102 of 118
Interim Report #26 - Analysis of Groundwater Samples
*
Exygen Study No.:PO001131
t
.-
be pmpmd and a d d .
'\
: 0
t
-.
t t
uMl&~=
RECEIVED TIME Nw.23. 5 : 4 m
mwmmwoRM PRINT T I K N0V.P. S:41PPl
Exygen Research
Page 103 of 118
Interim Report #26 --Analysis of GroundwaterSamples
Exygen Study No.: PO001131
I
--
I
Exygen Research
Page 104 of 118
Interim Report #26 -Analysis of Groundwater Samples
Exygen Study No.:PO001131
Exygen Research
.
I
I . ....--
Page 105 of 118
Interim Report #26 --Analysis of Groundwater Samples
Exygen Study No.:PO001 131
t no EARCH
3058 Research Drive Phone: 814-272:1039 State College, PA 1 6 m Fa: 814-231-1580
Amendment Number.
PROTOCOL AMENDMENT 6
Pqldl
EffectbeDate:
0317106
..
w e n Study Number PO001131 Client Study Number:
NA
- p
DEOSE ON
Appendir I, Analytical MeethodvooOf782
4himEuQ
As perdent request h p l e s in loginL a 2 6 tha;have been the spdnsor win be m-exiractedu hthe fobwing method:
I'
I
for re-extradknby
Olrecf tnjoctlonMethod: Beforethe samples amweighed for the extraction. they am
mixad thoroughly by vigorously shakingthe container. A onsgram parlionof sediment is weighed intoa 15mililiicentrifuge tube for the extraction. Ten milliliters of 1%
acetic add in methand is added to each sample. The samples are then shaken by hand, Mrtexed, and sonicated for thirty minutis. The samples are them mnlrifuged for -10 minutes at -3000 rpm. Each sample is analyzed by LCIMSIMS electmpray.
More usable data will be obtainedby Ging anailematemethod. WACX 0N STUDY
Exygen Research
Page 106 of 118
Interim Report #26 -- Analysis of Groundwater Samples
Exygen Study No.:POOOl 131
RESEARCH
3058 Research Drive Phone: 814-272-1039 State College, PA 16801 Fax: 814-231-1580
Amendment Number: Effective Date: Exygen Study Number
PROTOCOL AMENDMENT 8
07/06/06 POOOl 131 Client Study Number:
Page 1of 1 NA
DESCRIPTIONOF AMENDED SECTION
Appendix I, Analytical Method V0001782.
AMENDED TQ
As per diint request, sediment samples re-taggedfor re-extractionby the sponsor will be re-extracted using the following method:
Direct lnlection Method: Before the samples are weighed for the extraction. they are
mixed thoroughly by Vigorously shaking the container. A one-gram portion of sediment is weighed into a lbmilliliter centrifuge tube for the extraction. Ten millilitersof 1%
acetic acid in methanolis added to each sample. The samples are then shaken by
hand, vortexed, and sonicated for thirty minutes. The samples are then centrifuged for
-10 minutes at -3000 rpm. Each sample is analyzed by LC/MS/MS electrospray.
RATIONALE More usable data will be obtained by using an alternate method.
IMPACT ON STUDY No negative impact on study.
Exyeen Management Signaturn Sponsor Signature (Irequired)
-~ LIBRARY ID: vo001226-e
Date
Date
Exygen QAU & InitlDate
I7 h p k
ADMINISTSTRATIM FORM
Exygen Research
Page 107 of 118
Interim Report #26 - Analysis of Groundwater Samples
CHEM or-ii-zoo6
Exygen Study No.: PO001131
1, And;tld ~ i i l :o.. o*.1 7 l K
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Exygen Research
Page 108 of 118
Interim Report #26 -- Analysis of Groundwater Samples
01-OB-ZOO7 '03:19m F r p r M S M S#UTIONS
Exygen StudyNo.:PO001131
RECEIKD TIP JFFI. 8 . 4:-
Pf?INT TIME JFYJ. 8. 4rB4PM
Exygen Research
Page 109of 118
Interim Report #26 --Analysis of Groundwater Samples
Exygen StudyNo.:PO001131
w
en
RESEARCH
rio.377 P.2
3058 m a r c h orfw Phone: 8 i ~ n - i o 3 9 State Colkge, PA 16801 Fax: 814-231-1580
DEVIATION FORM
Login#:
NA
Contaiir# :
NA
Lot#:
NA
of Dlvlation;
#%%on
pertainsto all ron and sedment amplea lnrlyredfor pemnt solid8 before01/07/05.
- - - - x a. No blanksor dupliarko ware run a6 nquired by section9.3.
b. Somesample weQhls ermed the allowableram (> ?On).
c8UW:
Propantion mbir lnrtrwnent
Cliant Requrrt
OW
kBm& Them hask e n no negathre impact on the study. AI ofthe p w m t sdM values thatweredotmined luringthe time period In questiona n conaideredvalid, althoughthe SOP WBI not f c l h d . Inthe
uwly mrlredwnkn ofthe SOP blanksand duplicute8 am no longer required. Also, In the new SOP, hr slowable amount of m p l r to be used is c 20 g. All ofthesamples In qumtim Inthis devintkn mlghed lessthen 20 g. The technfdanenalydngthe samples for percentsolids WBS fd[awng the
1Wpfoc@durebefore It waa fofmdlya p p d .
4 new yersbn $the SOP has brm Issued and approved (Moao4273).
- L l W Y IDvoo016408 .
Date
t Sponsor Rsprerentative
Date
N# Sponsor Management
Datr
ADMINISTRATIVE FORM
Exygen Research
Page 110of 118
Interim Report #26 - Analysis of Groundwater Samples
Exygen StudyNo.:PO001131
N0.m P.3
3058 Research O M Phane: 814-272-1039 State College, PA 16801 Fax: 814-231-1580
DEVIATION FORM
of Divlrtbn;
The prollcol states that control and foltifiedcontrol rarnplerof eachmatrlxwill be analyzsd; howevws
control dun was not oblalned. Fishwas Wed as the wntml fwthe rnaryfls of theseak darn
samples.
LIBRARY ID:M O O 1 5 4 0 8
Exygen Research
ADMINISl'RATiVE FORM
Page 1 1 1 of 118
Interim Report #26 --Analysis of Groundwater Samples
Exygen Study No.:PO001131
No.377 P.4
3058 Research Drive Phone: 814-272-1039
State College, PA 16801 Fax: 814-231-1580
LOgbrP:
NA
Container#:
NA
.Lot#:
NA
- - - X RE544 fiduenm) urd to make SI21148Xpind-m03i)LB104. SUI 14 w usedtoCriImlZOd
glaaawaropreparedfor the fish Owtmtion tmm 12/27/04 through 01/07/05.
Cause:
preparation __ Analysis
In&urnent
Client Request
Other
IBlRaa No negative impacton the study. Toluenewas used only as a rdwntfor the Qlasswmpreparation.
Dimethyldichlorosilane,M iis the coatingagent,wm not expired.
comothra Da'mtion issued.
-IBRARy ID:Moo16406
Exygen Research
AOMNlSrrUTM FORM
Page112of118
Interim Report #26 .- Analysis of Groundwater Samples
Exygen Study No.:PO001131
Research Me
RESEARCH
DEVIATION FORM
P h m : 814-272-1039
Logh#:
Uw#8191 Contabtor#:
NA
Lot#:
NA
Sumnnrv o f a t l o n :
I'hethreesedimant samplesin~8191(C0172892-C0172(1M)wam~lnaliycodrsctdusingtha wdimenl methodVW01782. Poor mcwaries were obtain& for PFOS, PFOAand "C PFOA Baceuseof W, lha sludy sponsofrepwdedthe u8a of an altematlveexhctlonf a thew
compounds,ae follow:
Dim3 InJoctlon Mothod: BeforeIheremplar wanweighed for lhaextrPdion. theyware mlrced horoughlyby @wwJy shaking the unlainw. A a n e ~ s mportion d radimentwas WhOdintoI 15mlllibcanltihgo tubs for he extradion. Ten mllifitersof 1% acetic acid h melhnd wa6 added 10 wch mpb.The rampkr wera than shaken by hand, vortexed. and sonicrledfor thrty mhutes. me simples were then cenltifugedfor -10 minutea et -3OOO rpm. Each s m p b was anaiyzadby .CIMSIMS el8droopray.
Jsing thia methodaocep(abk dala was obtainedfor PFOS, but the rrcoverbafor PFOA and "C 'FOA were stillpoor. Another alternative methodwas then ad for PFOA and "C P F o k as folkwr:
UtrmrUvr SPE Method fhe samples that ware prepared h 1%acetic udd for the direct hjectbn nemod WOW used for n* EXhCUUl. Five mS%lafSof sach m p b we8 diquotd ht0 8 W-IllL mlpfq+fene csnlrlfuuo tubsand the vohm was taken ro40r n w~ith water. l l w rampla were then mtrihqpdfor -10 minuterat -sa00 rpm. me supematantwas then loaded onto a Ca SPE cenridge mditbnad wiIh 10 mL of meJhsndand 5 mL d water. The &ale was discarded. Approximatelyflva nllllten of methanol was added to the arcridge. Five rnaliatenof eluatewe5 collscld .hto a jraduabd 1smL p-surtrilgo tubs. Each umphwas analyzedby LCMSIMS -Y.
hu8o: - - Preparetlon Analysis -lmtrumt -Ctlent Requart 2Other
Mom usabledata was cblahad.
2 .
Exygen Research
Page 113 of 118
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Interim Report #26 --Analysis of Groundwater Samples
Exygen StudyNo.:PO001131
Exygen Research
Page 114 of 118
~~~~~
~
~~
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Interim Report #26 - Analysis of Groundwater Samples
Exygen Study No.:PO001131
EHS OPNS ENVlRONMENTAL LAB
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Page 115 of 118
Interim Report #26 .- Analysis of Groundwater Samples
Exygen StudyNo.: PO001131
EHS OPNS ENVIRONHENTAL LAB
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Exygen Research
Page 116 of 118
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Interim Report #26 - Analysis of Groundwater Samples
Exygen StudyNo.:PO001131
EHS OPNS ENVIRONNENTAL LAB
07/11/06 ' I 1 :468.:07/07N0:681
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Page 117 of 118
Interim Report #26 .- Analysis of Groundwater Samples
Exygen StudyNo.:PO001131
I
uBIcIRv~womcID.1
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REEIVEDTIME JAN. 8. 4 : m
. PRINTTII*E Jffl. 8. 4:84R1
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Exygen Research
Page 118 of 118