Document GK5O5X8NBYnB2aq4ebYRDjBE4
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Analytical Report: FACT GEN-050 LlMS E01-0096
Analytical Laboratory Repott Title
Determination of PFOS, PFOSA, and PFOA Levels in
- Surface Water Samples from Port St. Lucie, FL Revision 1 06/11/01
Data Requirement
Not Applicable
Author
3M Environmental Laboratory
Report Completion Date
At signing
Performing Laboratory
3M Environmental Laboratory Building 2-3E-09,935 Bush Avenue
St. Paul, MN 55106
Project ldentification
Analytical Report: FACT GEN-050
3M LlMS NO.E01-0096
Total Number of Pages
41
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Analytical Report: FACT GEN-050
LlMS E01-0096
Table of Contents
Introduction and Purpose .................................................................................................. 5 Sampling Plan .............................................................................................................. 5 Sample Collection and Analysis.................................................................................... 5
Specimen Receipt and Maintenance................................................................................. 5 Chemical Characterization of the Reference Materials...................................................... 6 Method Summaries ........................................................................................................... 7
3M EnvironmentalLaboratory....................................................................................... 7 Preparatory and Analytical Method .......................................................................... 7 Analytical Equipment ............................................................................................... 8
Data Quality ObjectivesKriteria and Data Integrity ........................................................... 9 Data Summary. Analyses. and Results ............................................................................. 9
Summary of Quality Control Analyses Results.............................................................. 9 Statement of Data Quality ............................................................................................ 10 Summary of Sample Results ........................................................................................ 10 Statistical Methods and Calculations................................................................................. 11 Statement of Conclusion................................................................................................... 11 Appendix A: Extractionand Analytical Method .................................................................. 12
ETS-8-154.0 "Determination of PerfluorooctaneSulfonate (PFOS), Perfluorooctane sulfonylamide (PFOSA) and Perfhrooctanoate (POAA) in Water by Liquid-Solid Extractionand High-Performance Liquid Chromatography/TandemMass Spectrometry
(HPLC/MSMS)" .................................................................................................................. 13 Appendix 6:Data Summary Tables .................................................................................. 30 Appendix C: Data Spreadsheets........................................................................................ 31 Appendix D: Example Calculations.................................................................................... 34
Appendix E: Interim Certificates of Analysis ...................................................................... 35 Appendix F: Report Signature Page.................................................................................. 41
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Analytical Report: FACT GEN-050 LlMS E01-0096
List of Tables
Table 1. Characterization of the Analytical Reference Materials in Study GEN-050 ..........6
Table 2. Target Ions Monitored in GEN-050..................................................................... 8
Table 3. LOQ in the Analyses of Extracts.......................................................................... 9 Table 4. Port St. Lucie Resample January 24. 2001 Sample Results for GEN-050...........30
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Laboratory Personnel and Contributors
Analytical Report: FACT GEN-050 Ll-096
Principal Analytical Investigator Kris Hansen, Ph.D. 3M Environmental Lab Bldg. 2-3E-09 St. Paul, MN 55133
Laboratory Management Dale Bacon 3M Environmental Lab
Bldg. 2-3E-09
St. Paul, MN 55133
Analytical Chemistry Laboratory
Extraction and Analyses 3M Environmental Laboratory BuiIding 2-3E-09 935 Bush Avenue St. Paul, MN 55106
3M Laboratory Contributing Personnel
Lisa A. Clemen Harold 0. Johnson Ognjenka Krupljanin* Thomas P. Wagner*
*Contract lab professionalserviceemployees
Location of Archives
All original raw data and analytical summary have been archived at the 3M Environmental Laboratory.
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3M 1:nvironmental Laboratory Study
Introduction and Purpose
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LIMS E01-0096
The purpose of the study is to determine the levels of PFOS, PFOSA, and PFOA in samples of
surface water collected from three ponds in Port St. Lucie, FL. This is the third sampling event
for Site I and the first sampling event for Site II and Site Ill.
Sampling Plan
Water samples were collected from three separate surface water bodies in Port St. Lucie,FL. Site
I has been sampled on two previous occasions, in July 1999 (sample collection by Battelle) and in
July 2000 (sample collection by PACE Analytical). This study presents results from the third sampling event at Site I and the first sampling events at both Site II and Site Ill. Please see PACE Analytical report archived with this report, for details on sample collection.
Sample Collection and Analysis Eight water samples were collected (5 from Site I, 2 from Site II,and 1from Site Ill), along with 2 field blanks, 2 field spike controls samples (FSCS), and six field matrix spikes (FNIS). Additionally, a single field duplicate sample was collected at both Site I and Site II.,
After collection, all samples were immediately stored on ice and were shipped to the 3M EnvironmentalLab on ice.
All water samples and QC were prepared for analysis using solid phase extraction. Sample extractswere analyzed using high-pressure liquid chromatography-electrospray/tandemmass spectrometry (HPLC-ESMSMS) in the multiple response mode. All analytes were quantitated by external calibration using an extracted curve. Analytical details are included in this report.
Specimen Receipt and Maintenance
On January 29, 2001, the 3M Environmental Laboratory received water specimens collected on January 24, 2001. All specimens were received cold on ice and were immediately transferred to refrigerated storage at 4C k5"C.
Bottled water used in the analyses performed was obtained from, Kandiyohi Premium Drinking Water from Premium Waters, Inc hninneapolis MN.
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Chemical Characterization of the Reference Materials
Table 1. Characterizationof the Analytical Reference Materials in Study
GEN-050
I Material
KPFOS'
PFOSA
APFO~ I
Cas Number Chemical Formula Molecular Weight source Expiration Date
2795393 CsFi7SQl<*
537.9 3M S eChemicels
mimi
754-918 CsFi7SOzNH2
498.9 3M Specialtv Chemicals
oimiiio
382526-1 C7FisCqNb+
430.9
3M Specialtv chemicals
imimi
I Chemical Lot Number I
Physical Dagcription Puritv
UflkKMl WhiipCMidar
97.9%
I
L-15709
I
332
I
LightYel~Waxysdii
whipovder
TBD
95.0
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Method Summaries
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Following is a brief description of the method used during this analytical study by the 3M Environmental Laboratory. A copy of the method used in this study is located in Appendix A.
3M Environmental Laboratory
PREPARATORYANDANALYTICALMETHOD
0 ETS-8454.0"Determinationof Perfluorooctane Sulfonate (PFOS), Perfluorooctane
sulfonylamide (PFOSA) and Perflurooctanoate (POAA) in Water by Liquid-Solid Extraction and High-Performance Liquid ChromatographyflandemMass Spectrometry (HPLC/MSMS)"
A 40 mL aliquot of each water samples was extracted using C18 solid phase extraction (SPE) cartridges. The target analytes are eluted from the cartridge using 5 mL of methanol. Separation, identification, and quantitation are accomplished using HPLC-ESMSMS in multiple response monitoring.
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Analytical Report: FACT GEN-050 LlMS E01-0096
ANALYTICALEQUIPMENT The analytical equipment settings used in this analysis are presented below:
Liquid Chromatograph: Hewlett-Packard@Series 1100 Liquid Chromatograph system
Analytical column: Keystone@BetasiP Cs2x50 mm (5pm) Column temperature: 35OC
Mobile phase components: Component A: 2mM ammonium acetate Component B: methanol
Flow rate: 300 pUmin Injection volume: 15 pL Solvent Gradient: 14.0 minutes
Time (minutes) 0.0 0.4
1.o
7.0
7.5
9.0 9.5 14.0
%B 40% 40% 90% 90% 100% 100% 40% 40%
Mass Spectrometer: Micromass@API/Mass Spectrometer Ultima Ill" Triple Quadrupole system Software: Mass Lynx" 3.4
Cone Voltage: 30-60 V Collision Gas Energy: 25-45 eV
Mode: Electrospray Negative Source Block Temperature: 15OoCk1OC Electrode: Z-spray Analysis Type: Multiple Reaction Monitoring (MRM)
Table 2. Target ions Monitored in GEN-050
F & t Analyte I PrimaryIon (mu) I Prodvctlon( i u q
~~
PFOS
499.0
PFOSA
I PFOA I
498.0 413.0
169.0
I
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Data Quality ObjectivedCriteria and Data Integrity
The following data quality objectives (DQOs) were indicatedfor the methods followed in this study:
Linearity: The coefficient of determination (r2)equal to or greater than 0.980 Limits of Quantitation (LOQ): The LOQ is equal to the lowest acceptable standard in the calibration curve. Acceptable Spike Recoveries: 70-130% Demonstration of Specificity: Specificity to be demonstrated by chromatographic retention time and daughter ion characterization.
Data Summary, Analyses, and Results
Data quality objectives for the analyses of this study were met with the exceptions noted in this report.
Analyte
Method LOQ
PFOS
10 pg/mL
I
PFOA
I
25 pg/mL
I
PFOSA
1opg/mL
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Precision, Extraction: Precisionwas determined by triplicate extraction and analysis of a
single water sample and was reproducible to within +/-lo%.
Precision, Collection: Precision with respect to sample collection was determined by analysis of duplicate samples collected at Site I and at Site II; results were reproducible to within +/-20%.
Field Matrix Spikes: During sample collection, six FMS were prepared by spiking water
samples at concentrations ranging from 200 ppt to 5 ppb. With one exception, all FMS were within +/-30% of expected levels. One PFOS FMS at 1 ppb was recovered at only 48%. Two
other PFOS FMSs prepared at this same level were recovered satisfactorily.
Laboratory Prepared Matrix Spikes: In the lab, eight matrix spikes were prepared by spiking one of three water samples are either 100 ppt, 250 ppt, or 5 ppb prior to extraction. All lab-prepared matrix spikes recoveries were within +/-30% of expected values.
Statement of Data Quality
It is not possible to verify true recovery of endogenous analyte from tissues without radio-labeled reference material. The only measurement of accuracy available at this time, matrix spike analyses, indicates that the data are quantitative to +/-30%.
Summary of Sample Results
Site I: Samples collected from different locations at Site I show close agreement with respect to PFOS levels. The average concentration of PFOS is just over 1.5 ng/mL. PFOA levels determined in samples collected form Site I showed much more dramatic variation, ranging from c 0.025 ng/mL to over 0.250 ng/mL. Four of the five samples showed close agreement with respect to PFOSA (just over 0.025 ng/mL); one sample was determined to contain PFOSA at 0.299 ng/mL.
The relatively high levels of the target analytes in the Site I samples are consistent with
results from previous sampling events. Site I is located very near a large marina and there is
evidence of drainage from the marina into Site I. Additionally, there is an active culvert that
feeds into Site I; the source of the water passing through the culvert is unknown. Either the
marina or the culvert may be the source of the fluorinated compounds. Additional information, including a detailed description and photographs of Site I and surrounding areas can be found in the Pace Analytical report that describes the sample collection.
Site II: Both PFOS and PFOA were detected in one of the two samples collected at Site II.
PFOSA was not detected above the limit of quantitation in Site II samples.
-
Site 111: Only PFOA was detected above the limit of quantitatioii in the Site Ill sample. PFOA
was determined to be present at 0.042 ng/mL.
Although some fluorochemcials were detected in both Site II arid Site Ill, the levels are more characteristic with fluorochemical levels observed in other bodiles of surface water across the Southeastern United States. The levels in Site II and Site Ill are dramatically lower than those in Site I and indicate that there is not widespread distribution of: high levels of fluorochemical surfactants in this area of Port St. Lucie, FL. Detailed sample data tables are presented in Appendices D and E.
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Statistical Methods and Calculations
Statistical methods were limited to the calculation of means, standard deviations, and spike recoveries (as detailed in the method).
Statement of Conclusion
The results of this analytical study confirm the results of previous sampling events at Site I. Relatively high levels of PFOS, PFOA, and PFOSA were found in the surface water labeled Site I. These relatively high levels were not mirrored in Site II and Site Ill,bodies of surface water located near to Site I,and indicatethat the distributionof relatively high levels of fluorochemicals is not widespread.
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Appendix A: Extraction and Analytical Method
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This appendix includes the following methods:
ETS-8-154.0 "Determinationof PerfluorooctaneSulfonate (PFOS), Perfluorooctane sulfonylamide (PFOSA) and Pemurooctanoate (POAA) in Water by LiquidSolid Extraction and High-PerformanceLiquid Chromatography/Tandem Mass Spectrometry(HPLC/MSMS)"
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3M ENVIRONMENTLAALBORATORY
METHOD
DETERMINATIOOFNPERnUOROQCrANE SULFONATE(PFOS), PERPLUORWCTANE SULFONYLAMIDE (PFOSA), AND PERPLUOROoCrANOATE@ O M ) IN WATERBY LIQUID-
SOLIDEXTRACTIAONND HIGH-PERFORMANLCIEQUICDEIROMATOGRAPEY/TAMNDASESM
SPECL~OMET(HRPYLC/Ms/Ms)
Method Number: El3-8-154.0
Author: KristenJ. H a n s d m l d 0.Johnson
Revision Date:
ApprovedBy:William K.Reagen, KentR.Lmdstrom
WilliamK.Reagen, Laboratory Management
A-4- &
Kristen J. Hamen, Ph.D., Group Leader
-
Kent R. Lintistrom. Technical Reviewer
Date
bY/sa/m Date
bJlurlcl0
' Dke
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Determinationof PFOS, PFOSA, POAA in Water by Liquid-SolidExtraction and LC/Ms/MS
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1.o SCOPE AND APPLICATION
1.1 This method provides collection, extraction, and analytical procedures for the determination of Perfluorooctanesulfonate(PFOS),PerfluomoctaneSulfonylamide (PFOSA),and Perfluorooctanoate (POAA) in groundwater, surfacewater, and drinking
water samples.
1.2 This method was prepared according to the EPA document, "Guidelines and Format for Methods to be Proposed at 40 CFR Part 136or Part 141"(see Reference 18.1), and is based in part on the report "Method of Analysis for the Detemlination of Perfluorooctane
sulfonate(PFOS),Perfluomoctane sulfonylamide (PFOSA),and Perfluorooctanoate (POAA)in Water" (see Reference 18.2).
- 2.0 SUMMARYOF METEOD
2.1 Water samples are collected from a site of interest and shipped cold to an analytical facility. PFOS, PFOSA, and POAA &e extractedfi-om4OmL water samplesusing CIS
solid phase extraction(SPE) cartridges. The compounds are eluted h m the C,,cartridge,
using methanol. Separation, identification, and measurement are accomplished by high-
performance liquid chromatography/tandemmass spectrometry (HPLC/MS/MS) analysis
using multiple response monitoring 0.
The concentrationof each identified component is measuredby comparingthe MS response of the quantitationionproduced by that compoundto the MS response of the quantitation ion produced by the same compound in an extracted calibration standard
(external standard).
- 3.0 DEFINITIONS
3.1 Analytical Sampl-A
portion of an extractedLaboratorysampleprepared for analysis.
3.2 Calibration Standard-A solutionprepared h m the Working Standard(WS) and extracted according to this method. The calibration standard solutions aro used to
calibratethe instrumentresponsewithrespect to analyteconcentration.
3 3 Duplicate Sample @S)-A separate aliquotof a sample, taken in the analytical laboratory and analyzedseparatelywith identical procedures. lbalysis of DSs compared
to that of the firstaliquot give a measure of the precision associated with laboratory procedures, but not with samplecollection, preservation,or stcmge procedures.
3.4 Field Blank Control Sample (FB)-Type I water placed in a sample container in the laboratory and treated as a samplein all respects, includingexposureto samplingsite conditions, storage, preservation and all analyticalprocedures. The purpose of the FB is to determine if test substancesor other interferencesare present in the field environment.
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3.5 Field Duplicate O ) - A samplecollected in duplicateat the same time as the sample and placed under identical circumstances and treated exactly the: same throughout field and laboratory procedures. Analysis of FD compared to that of the first sample gives a measure of the precision associatedwith sample collection, preservation and storage, as well as with laboratory procedures.
3.6 Field Matrix Spike (FMS)-A sample collected in duplicateto which known quantities
of the target analytes are added in the field at the time of sample collection. The F M S shouldbe spiked at approximately50-150% of the expected analyte concentration in the sample. The F M S is analyzed to ascertainif any matrix effects,interferences,or stability
issues may complicatethe interpretationof the sample analysis.
3.7 Field Spike Control Sample (FSCS)-An aliquot of type I water to which known quantitiesof the target analytes are added in the field at the time of sample collection(at an appropriateconcentrationto be determinedby the project lend). The FSCS is extracted and analyzed exactly like a sampleto determinewhether a loss of analyte could be attributed to sample storage and/or shipment.
3.8 Laboratory Control Sample &CS)-An aliquot of type I water to which known quantities of the target aualytes are added in the laboratory. Two levels are included, one at the LOQ (approx. 25Pg/mL), the other at a concentrationof approx. 100-250Pglmt or another concentrationto be determinedby the project lead. The LCS is extracted and analyzed exactly like a laboratory sampleto determinewhether the methodology is in control, and whether the laboratory is capable of making accurate measurements at the required method detection limit and higher.
3.9 Laboratory Sample-A portion of a samplereceived fiom the field for testing.
3.10 Limit of Detection &OD)-The lowest concentration of an andyte that can be measured and reported with 99% confidencethat the analyte concentrationis greater than zero. The
LOD can be determinedin several ways, including signal-to-noiseratio and statistical
calculations.
3.11 Limit of Quantitation (LOQ)--The lowest concentration (LILOQ) or highest concentration (ULOQ) that can be reliably achieved within the specified limits of precision and accuracy during routine operating conditions.
Note: The UOQ is generally 5-10 times the LOD. For many analytes, the LLOQ analyte . concentrationis selected as the lowest non-zerostandard in the caliibrationcurve.However,it
may be nominally chosenwithin these statedguidelinesto simplifjrdatareporting. Sample LLOQs are matrix-dependent.
3.12 Matrix Spike (MS)-An aliquot of a sample, to which known quantities of target analytes are added in the laboratory. The MS is extracted and analyzed exactly like a laboratory sample to determinewhetherthe samplematrix contributesbias to the analytical results. The background concentrations of the analytes in the sample matrix must be determined in a separate aliquot and the measured values in the MS corrected for background concentrations.
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3.13 Method Blank-An aliquot of type I water that is treated exactly like a laboratory sample including exposure to all glassware, equipment, solvents, reagents, internal standards, and surrogates that are used with other laboratory samples. The method blank is used to determine if test substancesor other interferences are present in the laboratory environment, the reagents, or the apparatus.
3.14 Method Detection Limit (MDL) Determination-One of s e v d processes thatmay be used to establish a LOD value. The statisticallycalculated minimumamount of an analyte that can be measured with 99% confidence that the reported value is greater than zero.
This term is usually associated with the EPA definition in 40 CFR Part 136 Appendix B.
3.15 Sampl+A sample is a small portion collected fiom a larger quantity of material intended to representthe original sourcematerial.
3.16 Spiking Stock Standard (SSS)-A prepare the working standard.
solutionprepared h m stack standards used to
3.17 Stock Standard (SS)-A concentrated solution of a single analyteprepared in the laboratorywith an assayed referencecompound.
3.18 Working Standard (WS)-A solution of several analytes prepared in the laboratory !?om SSs and diluted as needed to prepare calibration standards and other required analyte solutions.
4.0 WARNINGS AND CAUTIONS
__~-
~
~
~
~~
~
4.1 Health and Safety Warnings 4.1.1 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.
4.1.2 Unknown samples may containhigh concentrationsof volatiletoxic compounds. Samplecontainers shouldbe opened in a hood and handled with gloves to
prevent exposure. 4.1.3 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 referencefile of material safety data sheets (MSDS)
should be available to all personnel involved in these analyses.
5.0 INTERFERENCES
5.1 During extraction and analysis, major potential contaminant sources are reagents and
liquid-solid extraction devices.
5.2 All materials used in the analysesshall be demonstratedto be free !?ominterferences under conditions of analysis by running method blanks.
5.3 Teflon* containingmaterials (e.g. caps, wash bottles) contain.fluordcompoundswhich may cause interferences and should not be used during collection, storage, extraction, or analysis of the samples.
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6.0 EQUIPMENSTU,PPLIEASN,D MATERIALS
Note: Brand names, suppliers,and part numbers are for illustrativepurposesonly. Equivalent performance may be achieved using apparatus and materials other than those specified here, but demonstrationof equivalentperformancethat meets the requirementsof thismethod is the responsibility of the laboratory.
6.1 Sampling Equipment
6.1.1 Sample collection bottles-LDPE (e.g., NaIgeneTM)narrow-mouthbottles with
screw cap.
Note: Do not use Teflonbottles or Teflonlined caps. 6.1.2 Coolers for sample shipment 6.13 Ice for sample shipment. 6.1.4 Bottles must be lot-certifiedto be fke of artifactsby nlnningMethod blanks
according to this method.
6.2 Laboratory Equipment (Extraction and Analytical) 6.2.1 Balance, analytical (display at least O.OOOIg), Mettler.
6.2.2 Vacuum pump, Bfichi. 6.2.3 Visiprep vacuum manifold, Supelco.
6.2.4 Sep PakVac 6cc(Ig) tCl8cartridges(part # WAT 036795),Waters. 6.2.5 5omL disposable polypropylene centrifuge tubes, VWR.
6.2.6 15mL disposable polypropylene centrifuge tubes, VWR. 6.2.7 Disposablemicropipettes(50-100pL, 100-200pL), Drummond. 6.2.8 Class A pipettes and volumetric flasks, various. 6.2.9 Hypercarb dropin guard column (4mm) (part # 844017-400), Keystone. 6.2.10 Stand-alonedrop-in guard cartridgeholder, Keystone,, 6.2.11 125mL LDPE narrow-mouth bottles, Nalgene. 6.2.12 HPLC pump (LClOAD), Shimadzu. 6.2.13 2mL clear HPLC vial kit (cat # 5181-3400), Hewlett Packard. 6.2.14 Standard lab equipment (graduated cylinders, disposable tubes, etc.), various. 6.2.15 LC/MS/MS and HPLC systems. as describedin section 10.1.
6.3 Equipment Notes
6.3.1 In order to avoid contamination, the use of disposable labware is highly
recommended (tubes,pipettes, etc.). 6.3.2 Teflon or Teflon-lined containersor equipment,including Teflon-lined HPLC
vials or caps for the HPLC auto sampler must not be used. 6.3.3 Type I water used during the sample and standard extraction should be filtered
through a Hypercarb guard column using a HPLC pump. This water is referred to as "filteredtype I w a t d , hereafter in this report.
6.3.4 It is necessary to check the solvents (methanol) for the presence of contaminants (especially POAA) by LC/MS/MS prior to use. Certain lot numbers have been found to be unsuitable for use.
6.3.5 Use disposable micropipettesor pipettesto aliquot standard solutionsto make calibration standards and matrix spikes.
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7.0 REAGENTS AND STANDARDS
Note: Suppliersand catalognumbersare for illustrativepurposes only. Equivalentperformance may be achievedusing chemicalsobtained from other suppliers.Do not use a lesser grade of chemical than those listed.
7.1 Chemicals
7.1.1 Methanol (MeOH), HPLC grade, JT Baker,CatalogNo. JT9093-2. 7.1.2 Ammonium Acetate, Reagent grade, Sigma-Aldrich, Catalog No. A-7330. 7.13 Water, type I, prepared in-house. 7.1.4 Sodium Thiosulfate, Reagent grade, JT Baker.
7.2 Standards
7.2.1 Potassium perfluomoctane sulfonate (see Attachment A, Figure 1).
7.2.2 Perfluomoctanesulfonylamide(see AttachmentA, Figure2). 7.2.3 Ammonium perfluorooctanoate(see AttachmentA, Figure 3).
7 3 Reagent Preparation 7.3.1 250mglmL sodium thiosulfate solution @xtraction)-Dissolve 25g of sodium thiosulfate in lOOmL reagent water. 73.2 40% methanol (Extraction)-Measure 40omL methanol and adjust the volume to 1.OL with reagent water.
73.3 l O O m M ammonium acetate solution (Analysis)-Weigh 7.71g of ammonium acetate and dissolvein 1.OL of reagent water. Dilutethe 1O O m M solutionby a factor of 50 to make the 2mM ammonium acetate solutionused for mobile phase
A.
Note: Alternative volumes may be prepared as long as the ratios af the solvent to solute ratios are maintained.
7.4 Spiking Stock Standard (SSS) Preparation 7.4.1 100pglmLeach PFOS, PFOSA, and POAA SSSs--Weigh out lOmg of analytical standard(correctedfor percent salt and puxily-i.e., 10mg C$,,SO,K purity 90% = 8.35mg C,F,,SO,-) and dilute to lOOmL with methanol in a lOOmL volumetric flask.Transfer to a 125mLLDPE bottle. Prepare a separate solution for each analyte. Store solutions in a refrigerator at 4"*2?"Cfor a maximum period of 6 months from the date of preparation.
7.4.2 lpg/mL mixed S S C A d d 1.OmL each of the lOOpg/mL SSSs (from 7.4.1) to a 1OomL volumetric flask and bring up to volume with methanol.
7.4.3 O.lpg/mL mixed SSS-Add 1 0 . W of the l.Opg/mL-m.ixed solution(from 7.4.2) to a lOOmL volumetric flask and bring up to volume with methanol.
7.4.4 O.Olpg/mL mixed SSS-Add 1 0 . W of the O.lpg/mL-mixed solution(from 7.4.3)to a lOOmL volumetricflask and bring up to ,volumewith methanol.
7.4.5 Storage Conditions-Store all SSSs in a refiigerator in 125mLLDPE bottles at 4"*2"C for a maximum period of 3 months h m the date of preparation.
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7.5 Calibration Standards
7.5.1 lOOpg/mLeach PFOS,PFOSA,and POAA stock standard solutions-Weigh
out lOmg of analytical standard (corrected for percent salt and purity) and dilute to lOOmL withmethanol in a 10- volumetric flask. Transfer to a 1 2 5 d LDPE bottle. Prepare a separate solution for each analyte. Store solutions in a refigerator at 4OS0C for a maximum period of 6 months fiom the date of
preparation.
7.5.2 lpg/mL Working Standard-Add l.0mL each of the lOOpg/mL SS solutions (from7.5.1) to a l 0 W volumetric flask and bring up to volume with methanol.
7.53 O.lpg/mL Working Standard -Add 1 O . W of the 1.OpglmLmixed solution
(fiom 7.5.2) to a lOOmL volumetric flask and bring up to volume with methanol.
7.5.4 O.Olpg/mL Working Standard -Add 1O.OmLof the O.lpg/mLmixed solution
(from7.5.3) to a lOOmLvolumetric flask and bring up to volumewith methanol. 7.5.5 Storage Conditions43tore all WSs in a ref3gerator (in 125mLLDPE bottles)
at 4OaoCfor a maximum period of 3 months from the date of preparation. 7.5.6 Calibration Standard-Prepare a minimum of five calibration solutions in
filtered type I water according to the following table:
Concenbation ofWs,ClglmL
0.0
Volume of Final Calibration Standard
WS,pL
Volume, mL
0
40
0.010
100
40
0.010
200
40
0.010
400
40
0.10
100
40
0.10
200
40
0.10
300
40
0.10
400
40
1 May bc prepared to extend the range beyond 5OOPg/aL.
2 May be prepared to extend the range beyond 750PghL.
Find Concentrationof Calibration Standard, PglmL,
0 . 25
50 100 250 500 7501
10002
Note: The absolutevolumesof the standardsmay be varied by the analyst as long as the correct proportions of soluteto solventare maintained.
7.5.7 The standards are processed throughthe extractionprocedure (Section9.0),
identicalto the laboratorysamples. The extracted concentrationof the calibration standard is equal to 8X the initial concentration, due ?Dthe concentrationof the standard during the extraction process. 7.5.8 Storage Conditiondtore all extracted calibration standards in 15mL polypropylene tubes at 4'*2"C, for a maximum period of two weeks fiom the date of preparation.
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8.0 SAMPLCEOLLECTIONP,RESERVATIAONND STORAGE
Note: Sampling equipment, including automatic samplers, must be free of Teflon tubing, gaskets, and other parts that may leach interferinganalytesinto the water sample.Automatic samplers that composite samples over time should use refrigerated polypropylene sample containersif possible. Samplebottles shouldnot be rinsedbefore sample collection.
8.1 Tap Water--Open the tap and allow the system to flush until the water temperature (15"AlO"C) has stabilized (usually about two minutes). Adjust the flow to about S O W m i n and collect samples h m the flowing stream.
8.2 Ground Water-Purge the well of standingwater using a pump or a bailer. Collect the sample directly from the pump or h m the bailer.
8.3 Surface Water-When samplingh m an open body of water, fill the sample container
withwater h m a representativearea.
8.4 Sample Dechlorination--All samples should be iced or refigerated at 4"*2"C and kept in the dark h m the time of collectionuntil extraction.Residual chlorineshould be reduced by adding 200pL of a 25OmglmLsodiumthiosulfate solution to eachwater
sample, FB,and FSCS (whichmay be placed in eachbottle before leaving for the
sampling site.).
8.5 Holding Time
Results of the tbdstorage study of all target analytes showed
that the three compounds are stable for 14days in water sampleswhen the samples are
dechlorinated and stored as described in section 8.4 (see also reference 18.3). Therefore,
laboratory samplesmust be extracted within 14days and the extracts analyzed within 30
days of sample collection. If the HT exceeds 14 days, great care is used when evaluating
field spikesto avoid misrepresentationof the sample concentnition.
8.6 Field Blanks 8.6.1 Process a Field Blank Control Sample (FB) along With each sample set (samples collected fromthe same general sample site at approximately the same time). At
the laboratory,prior to sample collection,fill a samplecontainerwith filtered type I water, seal, and ship the FB to the sampling site along with the empty
sample contain-. Return the FB to the laboratory with the filled sample bottles.
8.6.2 When sodium thiosulfate is added to samples, use the same procedure to preserve
the FB.
8.7 Field Duplicates 8.7.1 Collect a Field Duplicate (FD) for every ten (10) samples collected or per each
sampling set, if less than 10 samples are collected. 8.7.2 SeparateF D s must be collected for each type of water sample (ground, tap, etc.)
collected. 8.7.3 Collect the FD immediately after the sample.
8.7.4 Preserve, store and ship FD using the same procedures as used for the samples.
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8.8 Field Spike Control Sample (FSCS) 8.8.1 A Field Spike Control Sample (FSCS) must be prepared for each sample shipment. If multiple coolers are used to ship a set of samples, each cooler must
contain a FSCS. 8.8.2 At the laboratory, fill a sample containexwith 100mL of type I water. Seal and
ship to the samplingsite along 6 t h the empty sample:containers and FBs. 8.83 When sodium thiosulfate is added to samples, use the same procedure to add the
same amounts to the FSCS. 8.8.4 Seal and gently invert the FSCS to mix. Store and ship the FSCS using the same
procedures as used for the samples.
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9.0 EXTRACTIOPNROCEDURE
9.1 Extraction Scheme 9.1.1 Allow samples to equilibrate to room temperature. Thoroughly mix samples by gently inverting the sample bottle.
9.1.2 Measure 4omL of sample into 5OmL polypropylenecentrifbgetubes (Spikethe QC and Matrix spikes as required*, replace lid and mix well).
Note: * Samplesmay need to be prescreenedto determinean appropriatematrix spike level
(typically 50-150% of sample concentration).
9.1.3 Condition the C,, SPE cartridges (lg, 6mL) by passing lomL methanol followed
by 5mL filtered type I water (-2drop/sec). Do not let column run dry.
Note: For the following steps,maintain a -ldrop/sec flowrate. Do not allow the column to nm dry at any time.
9.1.4 Load the analytical sample onto the C,, SPE cartridge. Discard eluate. 9.1.5 Wash with -5mL 40% methanol in water. Discard eluate.
9.1.6 Elute with -5mL 100%methanol. Collect 5 d o f eluate into graduated 15mL
polypropylenecentrifuge tubes. This is the target elution &tion (finalvolume =
5mL).
9.1.7 Analyze a portion of the target elution &tion eluent using negative electrospray
+ HPLC/MS/MS (Section 10.2).
Note: Samplesare concentratedby a factorof eight duringthe extraction;Initial Vol =4OmL
Final Vol. = 5mL.
9.1.8 Samples are stable at room temperature for at least 24 hours. Analytical samples may be stored in a refrigerator at 4"*2"C until analysis.
9.1.9 Standardization of C,, SPE columns-Ifpoor recoveries are observed, it may
be necessary to standardize the CISSPE columns in the followingmannerbefore
analyzing samples. 9.1.9.1 Use a standard with an analyteconcentrationbetween 1000 and 4000
Pg/mL. Follow the extraction scheme as outlined from steps 9.1.1 to 9.1.6, except, collect the eluate f k t i o n separately (a.pprox..SmL), as well as the target elution hction.
9.1.9.2 After step 9.1.6,collect a post-elutionfiaction by, eluting with a n
9.1.9.3
9.1.9.4 9.1.9.5
additional 5mL of 100%methanol.
Analyze all three fractionsby HPLC/MS/MS. If the target h t i o n contains a minimumof 85% of the respective analytes, it may be
considered acceptable. If the wash contains significant standard (>15%), either the wash volume
or percentage of MeOH should be decreased. If the post-elution fraction contains significant standard (>15%), the target
elution volume should be increased.
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10.0 CALIBRATIOANND STANDARDIZAT(AIONNALYTICASLETUP)
Note: Other instruments may be used and the equipment and conditions may be very different as long as the method criteria are met. The operator must optimize and document the equipment and settingsused
10.1 Establish the LC/MS/MS systemand operatingconditionsequivalentto the following: Mass Spec: Micromass Quattro Ultima (Micromass)
Interface: Electrospray (Micromass) Mode: ElectrosprayNegative, MultipleResponse Monitoring(h4R.M) Harvatd infusion pump (Harvard Instruments), for tuning Computer COMPAQ Professional Workstation AP200 Softwate: Windows NT, MassLynx 3.3 HPLC: HewlettPackard (HP) Series 1100 HP Quat Pump HP Vacuum Degasser HP Autosampler
HP Column oven
Note: A 4 x lOmm Hrpercarb dropinguard cartridge(Keystone,part # 844017-400) is attached on-line after the purge valve and before the sample injectorportto trap any residue contaminants that may be in the mobile phase andor HPLC system.
HPLC Column: Genesis C,(Jones Chromatography), 2Ilmm x 5 0 m ,4 p
Column Temperature: 35C Injection Volume: 15pL,
Mobile Phase (A): 2mM AmmoniumAcetate in filtered type I water (See7.3.1)
MobilePhase @ MeIt) ha:nol
HPLC Gradient Program:
Time, Percent Mobile
min
Phase A
0.0
60
0.4
60
1.o
10
7.0
10
7.5
0
9.0
0
9.5
60
13.5
60
14.0
60
Percent Mobile Phase B
40 40
90 90 100 100
40 40 40
FIow Rate, mL/min
0.3 0.3
0.3 0.3 0.3 0.4 0.4 0.4 0.3
Note: Other HPLC gradients may be used as long as the method criteria are met.
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It may be necessary to adjust the HPLC gradient in order to optimize instrument performance. Columnswith different dimensions(e.g. 2 . l m x 3Omm) and columns from different manufacturers (Keystone Betasil C,, etc.) may be used.
I Ions Monitored: I Analyte Primary
Ion
Product Ion
PFOSA
413.0 499.0 498.0
169.0 78.0
Approximate Retention Time
5.8
Other product ions may be chosen at the discretionof the andyst, althoughd z 99is suggested for PFOS.Use of the suggested primary ion is recommended. Retentiontimes may vaiy slightly, on a day-to-day basis, depending on the batch of mobile phase etc. Drift in retention times is acceptablewithin an analytical run,as long as the drift continuesthroughthe entire analysis and the standardsare interspersed throughoutthe analyticalrun.
10.2 Tune File Parameters 10.2.1 The following values are provided as an example. Actual values may vary from instrument to instrument. Also,these valuesmay be changed b m time to time in order to optimize for greatest sensitivity.
PFOSA
0.2-0.4 0.2-0.4
0.2-0.4
Collision Energy, eV
Cone, V
30-60
Capillary Hexapole 1 Ape- 1 Hexapole 2 Source Block Temp. Desolvation Temp.
Set
2.563.5kV 0.5v 0.2v 0.8V
100-1 5ooc
250400C
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AnaIyzer LMRes 1 HMRes 1 Energy 1 Entrance
Exit LMRes2 HMRes2
mergY2
Multiplier
Set
12.0-15.OV 12.0-15.OV
0.7V -2v 1v 1l.OV 11.ov
1 .ov
650V
Gas Flows Cone Gas Desolvation
Set
150Lk 700LA1r
Pressures Gas Cell
Set 3.0-3mbar
11.0 ANALYTICAQLUALITYCONTROL
11.1 Analytical results of the FB,FMS, FD,and FSCS shouldbe evaluated at the conclusion
of the study to help interpret the data quality of samples data. Analytical results for these controYduplicate samples must be reported with the sample data
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12.0 ANALYTICAL PROCEDURE
12.1 Sample Analysis 12.1.1 Set up analysis sample queue. 12.1.2 Inject the same aliquot (between 5-25pL) of each standard, analytical sample,
recovery, control etc. into the LC/MS/MS system. 12.1.3 All samples showing a response for one or more analytes above the response of
the highest, active calibration curve level must be diluted and reanalyzed.
12.2 Calibration Curve 12.2.1 Startingwith the standard of lowest concentration,inject the same size aliquot (between 10-25pL) ofeach extractedcalibration standardaccording to Section
12.1 and tabulate the response (peakheight or area) versus the concentrationin the standard. Use linear standard curves for quantitation generated for each analyteby linearregressionwith l/x weightingof peak area versus calibration
standard concentration.The correlationcoefficient[r) for the calibrationcurves
must be 20.990 (r%O.980). If calibration results fall outside these limits, then appropriate steps must be taken to adjust instrument operation and the standards
reanalyzed.
12.2.2 Carve-The measured value for eachcurve point must be within f 30% of theoretical values when curve is evaluated over a range appropriate to the data. High or low points may be deactivatedto achievethese criteria, but an acceptable curve must contain at least five active curve points.
12.2.3 Continuing Curve Verification (CCV)-Mid- and Xow-level calibration checks should be analyzed every 5-10 injections. The analyte level measured in the CCVs should be withinf 30% oftheoretical values. IfCCVs fall outside of this range, data collected subsequentto the last passing CCV should not be used.
Only data collectedbetween acceptableCCVs or the initial c-e can be used.
13.0 DATAANALYSIASND CALCULATIONS
~~
~~
~
~
~~
13.1 Calculate the analytical sample (extract) concentrationfiom the standard curve using the
following equation:
ExtractConcentration,pg/mL=(Peakarea.-intercept) (sllope)
13.2 Calculate the percent recovery of the FSCS using the following equation:
13.3 Calculate the percent recovery of the MSs using the following equation:
MS%rec. =(MS conc.,Pg/mL-SampleConc:.,Pg/mL) oo
(Conc.added,Pg/mL)
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14.0 METHODPERFORMANPCAERAMETERS
Note: Any method performance parametersthat are not achieved must be considered in the evaluation of the data.Nonconformance to any specifiedparametersmust be describedand discussed in any reporting of the data.
14.1 Linearity-Linear standard curves for quantitation generated for each analyte by linear regression with l/x weighting of peak area versus calibrationstandard concentration.n e correlation coefficient(r) for the calibrationcurves must be 20.990 (320.980).
14.2 Calibration Curve Standards-The measured value for each curve point must be within f 30% of theoretical values when curve is evaluated over a range appropriate to the data.
High or low points may be deactivatedto achievethese criteria, but an acceptablecurve
must contain at least five active curve points.
14.3 CCV Performance--Mid and low level calibration checks to be analyzed every 5-10 injections. The analyte level measured in the CCVs should be within f 30% of theoretical values. If CCVs fall outside of this range, data collectedsubsequentto the last passing CCV should not be used. Only data collectedbetween acceptableCCVscan be used.
14.4 Limit of Detection @O,DT-)he
lowest calibration standard with a peak area at least 2X
the peak areaof the extractionblank that canbe measured at a concentrationgreater than
zero.
14.5 Limits of Quantitation (L0Q)-The lower LOQ (LLOQ) is the lowest non-zero active standard in the calibration curve; the peak area of the LLOQ must be at least 2X that of the extraction blank. By definition, the measured value of the LLOQ must be within 30%
of the theoretical value.
14.6 Matrix Spikes-Matrix spike percentrecoveriesmust be within f30% of the spiked concentration.
14.7 Solvent Blanks, Method Blanks,and Matrix BIanbValues must be below the lowest non-zeroactive standard in the calibrationcurve. Matrix blanks are considered compliant if no test substance is detected above the LOD for that analyte.
14.8 Reprodocibillty-Reproducibilityofthe method is defined by the results ofthe matrix
spikes and matrix spike duplicates. The MSMSD should be reproducibleto within 20%.
14.9 Use of Confirmatory Methods-None
14.10 Demonstration of Specificity4pecificity is demonstrated by chromatographic retention time (within3% of standard)and the mass spectralresponseof unique product ions generated h m a characteristicprimary ion.
14.11
Documentation . 14.11.1 If criteria listed in this method performance section are not met, maintenance
may be performed on the system and samples reanalyzed, or other actions taken as determined by the analyst. Document all actionsin the appropriatelogbook.
14.11.2 If data are to be reported when performance criteria have not been met, the data must be footnoted on tables and discussed in the text of the report.
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15.0 POLLUTIONPREVENTION AND WMTE M A C E M E N T
15.1 Sample extract waste and flammablesolventis discarded in high BTU containers, and
glass pipette waste is discarded in broken glass containers located in the laboratory,
16.0 RECORDS
16.1 Each page generated for a study must have the followingidormation included, either in the header or hand-written on the page: study or project number, acquisition method,
integration method, sample name, extraction date, dilution factor (if applicable), and analyst.
16.2 Print the tune page, sample list, and acquisitionmethod h m MassLynx to include in the appropriatestudy folder. Copy these pages and tape into the instrumentrun log.
16.3 Plot the calibrationcurves as describedin this method, then print these graphs and store in the study folder.
16.4 Print data integrationsummary, integrationmethod, and chromatograms,from MassLynx, and store in the study folder.
16.5 Summarizedata using suitable software(MS Excel 97) and store in'thestudy folder.
16.6 Back up electronic data to appropriatemedium.Record in studynotebook the file name and location of backup electronic data.
17.0 ATTACHMENTS 17.1 Attachment A: Figures-Fluomhemid Compounds
18.0 REFERENCES
18.1 "Guidelines and Format for Methods to be Proposed at 40 CFR Part 136 or Part 141",
U.S.EnvironmentalProtectionAgency, Office ofScienceand Technology Office of
Water, Washington,D.C.Draft 1996.
18.2 `Method of Analysis for the Determinationof Perfluorooctanesmonate (PFOS), Perfluorooctanesulfonylamide(PFOSA),and Perfluorooctanoate(POAA) in Water", E. Wickremesinhe and J. Flaherty, Study Number 023-002, Centre Analytical Laboratories, Inc., State College, Pennsylvania, January 2000.
18.3 Validationreport for the ``Method of Analysis for the Determinationof Perfluorooctane
sulfonate (PFOS),Perfluorooctane sulfonylamide(PFOSA),and Perfluorooctanoate
(POAA) in Water", E. Wickremesinhe and J. Flaherty, StudyElumber 023-002, Centre Analytical Laboratories,Inc., State College,Pennsylvania,(Approvalpending)
19.0 REVISIONS
Revision Number.
Reason For Revision
Revision
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Figure I:PFOS
Chemical Name =
Molecular ion
=
0
I
Perfluomoctane sulfonate 499 (C,FI7SO,-)
Note: Standardsare made from the salt,potassium perflwrooctanesulfonate [C8F17S03KIym/w 538.
Figure 2: PFOSA
Chemical Name =
Molecular ion
=
R
Perfluorooctane sulfonylamide 498 ( C ~ ~ I ~ S O ~ N & )
0
PFOSA
Figure 3: POAA
Chemical Name =
Molecular ion
=
Perfluorooctanoate 413 (C7Fl,COO-)
POAA
Note: Standardsare madefrom the salt, ammonium perfluorooctanoate [C7FyjCOOW], m/w431
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Attachment A: ETS-8-154.0
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Appendix B: Data Summary Tables
Analytical Report: FACT GEN-050 LlMS E01-0096
Table 4. Port St. Lucie Resample January 24,2001 Sample Resultsfor GEN-050
Sample Number and Description
I site I
E00-0096-19527 E00-0096-19541 E00-0096-19545 E00-0096-19549 E00-0096-19553
East south west
I North
Cuh/ert Discharge
PFOS ng/mL
1.60 1.54 1.59
1.78 1.38
PFOA ng/mL <O.O250A 0.123 0.107 0.397
0.081
PFOSA nglmL 0.0283 0.0238 0.02~ 58.. 0.299'
0.0363
Site II
I site 111
I
I
It is not possibleto verify true recoveryof endogenous anarytefrom sampleswithout radio-labeled
referencematerial.The only measurementof accuracyavailable at this time, matrixspike studies,
indicate that the data quantitative to &io%.
Averages are calculatedwith the value of LOQ assignedto samples reportedat <LOQ.
A = No Limit of Detection(LOD) determinedfor this analysis. L W L O D is the same concentration and is equal to the following:
LOQ= 0.0100ngml for PFOSt? PFOSA
LOQ= 0.0250ng/mLfor PFOA.
Not included in calculation of site averaae.
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Appendix C: Data Spreadsheets
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PORT SI', LUClE REsAMPLeiJANUARY 24,2001
E.+.aL. AdyA
OZSZOIOK OIYol HOj. P m l IiOJ (Ruby)
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PORT ST. LUUE RESAMPLEJANUARY ?A, 2001
WlOK
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Analytical Report: FACT GEN-050 LlMS E01-0096
Appendix D: Example Calculations
Formula Used for Water Analyses in Study FACT GEN-050
AR @g/mL)x FV (mL) x 1.Ong = Reported Concentration (ng/mL)
IV(mL) 1ooopg
Calculation Used for PFOS Concentrationin E00-0096-19527
12797 pg/mL x 5 mL x 1.0 ng = 1.60 ng/mL 40mL lOOOpg
AR- Analytical result from MassLynx summary
IV- Initial Volume of H20 Extracted FV- Final Volume of Extract
Formula Used for Spike RecoveryAnalyses in Study FACT GEN-050
( RCspikd (ngh&) - R L i k d (ng/mL)) X 100% = % Recovery
SL (ng/mL)
Calculation Used for E00-0096-19535p(Site I)
(2.49 ng/mL - 1.58 nglmL) x 100% = 91% 1 .O ng/mL
a Average concentrationof all Site I samples used for RCmspikd.
RC- Reported Concentration
SL- Spike Level
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Appendix E: Interim Certificates of Analysis
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Analytical Report: FACT GEN-050
LlMS E01-0096
Centre Analytical Laboratories, Inc.
. 3048 Research Drive
State College, PA 16801
f".
Phone: (814)231-8032 Fax: (814) 2!31-1253or (814)231-1580
INTERIM CERXTFICATE OF ANALYSIS
Revkion 1(Sn/OO)
Centre Analytical Laboratories COA Reference #: 023-021
3M Product: PFOS,Primary Standard
Test Control Reference #: TCR00017-46
Purity: 97.9%
1. O.O06wtJ-% 5. <0.001 wt./wt.%
2. Fluoride 3. Bromide ' 4. Nitrate
5. Nilrite
1. co.1d W t . %
2. <O.lWtlwt.%
COA023-021
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Analytical Report: FACT GEN-050
LlMS E01-0096
a\ Analytical Inc, C m t w
Laboratories,
3048 Research Drive
State College, PA 16801
fl
Phone: (814) 231-8032 Fax: (814) 231-1253 or (814) 231-1580
liVTERIM CERTIFICATE OF ANALYSIS
Centre Analytical Laboratories COA Reference #: 023-021
. Date of Last Analysis: 08131/00 Expiration Date: 08l31/01 .
StorageConditions: Frozcn.SIOC
Re-assessment Date: 08/31/01
,P%
\
- 'Purity = 100% (sumofmctal impurities, 1.226% +LC/MS impurities,
0.14%+InorganicFluoride, 0.60%+NMRImpurity, 0.13%).
- Total impurity firom all tests =2.09%
hrrity = 100% 2.09% 97.9%
2Potassiumis expected in this.salt form and isthereforenot considered ani m p w i ~ .
'Sulfur in the sample appearsto be convertedto so4 and hence detected using the
inorganic anion method conditions. The anion result agrees well with the sulfiu determinationin the elemental analysis,lendingconfidence to this interpretation. Based on the results, the SO4 is not considered an impurity.
%A HFBA
NFPA PFPA
Trifluoroacetic acid Heptafluorobutyric acid
Nonofluoropentanoic acid Pentafluoropropanoic acid
sTheoreticalvalue calculations based on the empirical formula,CtlF17SO3X' (MW438).
This work was conducted under EPA Good Laboratory Practice Standards(40CFR 160).
COAO23-021
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Centre Analytical Labaratorks, Inc.
&c..xfp.or P&p,l, 3048 ResearchDrive
State College, PA 16801
(814) 231-1580
r'
Centre Analytical Laboratories COG Reference #: 023-021
LCIMS Purity Profile:
c5
C6 e7 Total .
Note: The C7 value was calculated Using the average response factors from the C6 and C8 standard cuwes.
- ?
Prepared By:
COAO23-021
3M Environmental Laboratory
9//b/co Date
Date
al Laboratories .
Page 3 Of 3
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Analytical Report: FACT GEN-050 LIMS E014096
Phone: (814) 231-8032
State College, PA 16801 Fax: (814)231-1253 or (814)231-1580
1. Carbon-
1. TheoreticalValue=22.:3%
2. Hydrogen .
2. Theoretical Value = 0.935%
3. Nitrogen
3. Theoretical Value = 3.25%
4. sulfur
. 4. TheoreticalValue =0%
5. Fluorine
5. Theol.etical Value = 66.1%
Ammonium Analysis'
Ion SelectiveElectrode
Theoretical Value = 4.1 IB%
,n.
1. 18.9 wt.fwt.% 2. 1.27wt.M.% 3. 3.76 wt.fwt.% 4. 4.38 wt.fw-L% 5. 62.1 wt.lwt.%
2.94 WtJwt. %
COA023034.doc 3M Environmental Laboratory
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3M Environmental Laboratory Study
Analytical Report: FACT GEN-050
a\ LlMS E014096 Centre Analytical Laboratorks, Inc. 3P0h4on8e+:k(e81a4rc) 2h3D1r-8iv0e32 Fax: (814) :231S-1ta2t5e3Coor l(l8e1g4e), P2A311-16588001
n
f
RvTjERllM CERITFICAIE OF ANALYSIS
CentreAnalyticalLaboratoriesCOA Reference #: 023-034
Date of Last Analysis: 10/31/00
Expiration Date: 10/31/01
StorageConditions: -10 "C
Re-assessment Date: 10/31/01
'Purity = 100%- (totalmetal impurities, 0.002%+ TotalN M R impurities,0.36+Total
LCMS impurities,4.68 %)
- Total impurity from all tests =: 5.042% Purity = 100% 5.042% = 95.0%
TFA
Trifluoroacetic acid
HFBA Heptafluorobutyric acid
NFPA
Nduoropentanoic acid
- t
' PFPA
Pentafluoropropanoic acid
'Theoretical value calculationsbased on the empirical formula, Cfi&$hH,$+) ( M W 4 3 1.1)
ThisWork was conducted underEPA Good LaboratoryPractice SItandards(40 CFR 160).
LCMS Purity Profile:
Peak# RetentionTime(min) Mass@) Identity
1
12.144
269.0 C6
2
13.533
331.319 FtJC7
Area
205859 9033129
%Area
0.87 3.81
Prepared By:
n/JIo
Date
Reviewed By:
/&nFlahexly
J
Date
LaboratoryManager,Centre AnalyticalLaboratories
3M EnvironmentalLaboratory
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3M Environmental Laboratory Study
Appendix F: Report Signature Page
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Analytical Report: FACT GEN-050 LlMS E01-0096
Kristen J. Hansen, Ph.D., Principal Analytical Investigator
06 / l z / O /
Date
3M EnvironmentalLaboratory
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