Document mqYay0zNOGLVQjGmOYj4pMGEg
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Analytical Report: FACT GEN-050 LIMS E01-0096
Analytical Laboratory Report Title
Determination of PFOS, PFOSA, and PFOA Levels in Surface W ater 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 Identification
Analytical Report: FACT G EN-050 3M LIMS No. E01-0096
Total Number of Pages
41
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Table of Contents
Analytical Report: FACT GEN-050 LIMS E01-0096
Introduction and Purpose...................................................................................................................5 Sampling P la n ................................................................................................................................. 5 Sample Collection and Analysis.................................................................................................. 5
Specimen Receipt and Maintenance.............................................................................................. 5
Chemical Characterization of the Reference Materials...............................................................6
Method Sum m aries............................................................................................................................. 7 3M Environmental Laboratory......................................................................................................7 Preparatory and Analytical M ethod...................................................................................... 7 Analytical Equipm ent............................................................................................................... 8
Data Quality Objectives/Criteria and Data Integrity.................................................................... 9
Data Summary, Analyses, and Results..........................................................................................9 Summary of Quality Control Analyses Results........................................................................ 9 Statement of Data Q uality............................................................................................................10 Summary of Sample Results....................................................................................................... 10
Statistical Methods and Calculations.............................................................................................. 11
Statement of Conclusion.................................................................................................................... 11
Appendix A: Extraction and Analytical M ethod................................................ ............................12
ETS-8-154.0 "Determination of Perfluorooctane Sulfonate (PFOS), Perfluorooctane sulfonylamide (PFOSA) and Perflurooctanoate (POAA) in W ater by Liquid-Solid Extraction and High-Performance Liquid Chromatography/Tandem Mass Spectrometry (HPLC/M SM S)" .................................................................................................................................... 13
Appendix B: Data Summary T a b le s ............................................................................................... 30
Appendix C: Data Spreadsheets..................................................................................................... 31
Appendix D: Example Calculations..................................................................................................34
Appendix E: Interim Certificates of Analysis................................................................................. 35
Appendix F: Report Signature P ag e ............................................................................................... 41
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Analytical Report: FACT GEN-050 LIMS E01-0096
List of Tables
Table 1. Characterization of the Analytical Reference Materials in Study G E N -0 5 0 ............6 Table 2. Target Ions Monitored in G E N -050.................................................................................8 Table 3. LOQ in the Analyses of Extracts...................................................................................... 9 Table 4. Port St. Lucie Resample January 24, 2001 SampleResults for G E N -050............30
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Laboratory Personnel and Contributors
Analytical Report; F A C T G E N -0 5 0 -------------------------- U M S E 0 1 -0 0 9 6
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 Building 2-3E-09 935 Bush Avenue St. Paul, MN 55106
3M Laboratory Contributing Personnel
Lisa A. Clemen Harold O. Johnson Ognjenka Krupljanin* Thomas P. W agner*
'Contract lab professional service employees
Location of Archives
All original raw data and analytical summary have been archived at the 3M Environmental Laboratory.
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Introduction and Purpose
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Analytical Report: FACT GEN-050 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 III.
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 III. 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 1 from Site III), along with 2 field blanks, 2 field spike controls samples (FSCS), and six field matrix spikes (FMS). 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 Environmental Lab on ice.
All water samples and QC were prepared for analysis using solid phase extraction. Sample extracts were analyzed using high-pressure liquid chromatography-electrospray/tandem mass 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 5C.
Bottled water used in the analyses performed was obtained from Kandiyohi Premium Drinking W ater from Premium Waters, Inc Minneapolis MN.
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Analytical Report: FACT GEN-050 LIMS E01-0096
Chemical Characterization of the Reference Materials
Table 1. Characterization of the Analytical Reference Materials in Study GEN-050
M aterial Identification
KPFOS*
Potassium Perfluorooctanesullbnate
PFOSA
Perfluoroctanesulfonylamide
APFOb
Ammonium Perfluorooctonoate
Cas Number
2795-39-3
754-91-6
3825-26-1
Chemical Formula Molecular Weight
CsFuSOjK* 537.9
C8Fi 7S02NH2 498.9
C7F i5CX)2'NH4* 430.9
Source
3 M Specialty C hem icals
3M Specialty C hem icals
Expiration Date
0 8 /3 1 /0 1
0 1 /0 1 /1 0
Storage Conditions
A m bient tem perature
A m bient tem perature
Chemical Lot Number
Unknown
L -1 5 7 0 9
Physical Description
W h ite powder
Light Yellow W axy Solid
Purity
9 7 .9 %
TBD
* The target analyte is PFOS (Perfluorooctanesulfonate), C8Fi 7SOs b The target analyte is PFOA (Perfluorooctanoate), OFisCOj". TBD-To Be Determined
3M Specialty C hem icals 1 0 /3 1 /0 1
A m bient tem perature 332
W h ite pow der 9 5.0
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Method Summaries
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Analytical Report: FACT GEN-050 LIMS E01-0096
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.
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Preparatory and Analytical Method
ETS-8-154.0 "Determination of Perfluorooctane Sulfonate (PFOS), Perfluorooctane sulfonylamide (PFOSA) and Perflurooctanoate (POAA) in W ater by Liquid-Solid Extraction and High-Performance Liquid Chromatography/Tandem Mass Spectrometry (HPLC/M SM S)"
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: FA C T G E N -050 LIM S E 0 1-0096
Analytical Equipment
The analytical equipment settings used in this analysis are presented below:
Liquid Chrom atograph: Hewlett-Packard9 Series 1100 Liquid Chromatograph system Analytical column: Keystone BetasilTM C8 2x50 mm (5 pm) Column temperature: 35C Mobile phase components:
Component A: 2mM ammonium acetate Component B: methanol Flow rate: 300 pL/min Injection volume: 15 pL Solvent Gradient: 14.0 minutes
Time (minutes) %B
0.0 40%
0.4 40%
1.0 90%
7.0 90%
7.5 100%
9.0 100%
9.5 40%
14.0
40%
Mass Spectrom eter: Micromass API/Mass Spectrometer Ultima IITM Triple Quadrupole system Software: Mass LynxTM 3.4
Cone Voltage: 30-60 V Collision Gas Energy: 2 5 -4 5 eV Mode: Electrospray Negative Source Block Temperature: 150C 10C Electrode: Z-spray Analysis Type: Multiple Reaction Monitoring (MRM)
Table 2. Target ions Monitored in GEN-050
Target Analyte
Primary Ion (a m u )
Product Ion (a m u )
PFOS
499.0
99.0
PFOSA
498.0
78.0
PFOA
413.0
169.0
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Data Quality Objectives/Criteria and Data Integrity
The following data quality objectives (DQOs) were indicated for 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% Dem onstration 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.
Summary of Quality Control Analyses Results
Linearity: The coefficient of determination (r2) of the standard curve was > 0.981.
Calibration Standards: Quantitation of the target analytes was based on 1/X weighted linear regression analysis of two extracted matrix curves bracketing each group of samples. High or low points on the curve may have been deactivated to provide a better linear fit over the curve range most appropriate to the data. Low curve points with peak areas less than two times that of the extraction blanks were deactivated to disqualify a data range that may have been significantly affected by background levels of the analyte. Quantitation of each analyte was based on the response of one specific product ion using the multiple response-monitoring mode of the instrument (see Appendix C, Analytical Methods).
Limits of Quantitation (LOQ): The LOQ is equal to the lowest acceptable standard in the calibration curve (defined as a standard within 30% of the theoretical value), and is at least two times the analyte peak area detected in the extraction blanks.
Table 3. LOQ in the Analyses of Extracts
Analyte
Method LOQ
PFOS
10pg/mL
PFOA
25 pg/mL
PFOSA
10 pg/mL
Blanks: All field blanks (n=2) and extraction blanks (n=4) were below the lower limit of quantitation for the compounds of interest.
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Precision, Extraction: Precision was determined by triplicate extraction and analysis of a single water sample and was reproducible to within +/-10%.
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 M atrix 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 M atrix 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.
Statem ent 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 < 0.025 ng/mL to over 0.250 ng/mL. Four of the five samples showed close agreement with respect to PFOSA O'ust 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 l 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 III: Only PFOA was detected above the limit of quantitation in the Site III sample. PFOA was determined to be present at 0.042 ng/mL.
Although some fluorochemcials were detected in both Site II and Site III, the levels are more characteristic with fluorochemical levels observed in other bodies of surface water across the southeastern United States. The levels in Site II and Site III 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 III, bodies of surface water located near to Site I, and indicate that the distribution of 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 "Determination of Perfluorooctane Sulfonate (PFOS), Perfluorooctane sulfonylamide (PFOSA) and Perflurooctanoate (POAA) in Water by Liquid-Solid Extraction and High-Performance Liquid Chromatography/Tandem Mass Spectrometry (HPLC/MSMS)"
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3M Environmental Laboratory
Method
Determination of P erfluorooctane sulfonate (PFOS), Perfluorooctane SULFONYLAMIDE (PFOSA), ANDPERFLUOROOCTANOATE (POAA) INWATER BYLlQUIDSolid E xtraction and H igh-Performance Liquid Chromatography/Tandem Mass
Spectrometry (HPLC/MS/MS)
Method Number: ETS-8-154.0
Adoption Date: C ^ jz ^ / looq
Author: Kristen J. Hansen/Harold O. Johnson
Revision Date:
Approved By: William K. Reagen, Kent R. Lindstrom
William K. Reagen, Laboratory Management
Date
4*^ tb s Kristen J Hansen, Ph.D,, Group Leader
Kent R. Lindstrom, Technical Reviewer
/ 0V Date
________ o n h lm ___________________ Date
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3M Environmental Laboratory Study___________________________________________________________ Analytical Report: FACT GEN-050 LIMS E01-0096
1.0 Scope and Application
1.1 This method provides collection, extraction, and analytical procedures for the determination of Perfluorooctane sulfonate (PFOS), Perfluorooctane Sulfonylamide (PFOSA), and Perfluorooctanoate (POAA) in groundwater, surface water, 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 136 or Part 141" (see Reference 18.1), and is based in part on the report "Method of Analysis for the Determination o f Perfluorooctane sulfonate (PFOS), Perfluorooctane sulfonylamide (PFOSA), and Perfluorooctanoate (POAA) in Water" (see Reference 18.2).
2.0 Summary of Method______________________________
2.1 Water samples are collected from a site o f interest and shipped cold to an analytical facility. PFOS, PFOSA, and POAA are extracted from 40mL water samples using C,, solid phase extraction (SPE) cartridges. The compounds are eluted from the C,8cartridge, using methanol. Separation, identification, and measurement are accomplished by high performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS) analysis using multiple response monitoring (MRM).
The concentration of each identified component is measured by comparing the MS response o f the quantitation ion produced by that compound to the MS response o f the quantitation ion produced by the same compound in an extracted calibration standard (external standard).
3.0 Definitions_______________________________________
3.1 A nalytical Sample--A portion of an extracted Laboratory sample prepared for analysis. 3.2 C alibration Standard--A solution prepared from the Working Standard (WS) and
extracted according to this method. The calibration standard solutions are used to calibrate the instrument response with respect to analyte concentration. 3.3 D uplicate Sample (DS)--A separate aliquot o f a sample, taken in the analytical laboratory and analyzed separately with identical procedures. Analysis of DSs compared to that of the first aliquot give a measure of the precision associated with laboratory procedures, but not with sample collection, preservation, or storage procedures. 3.4 Field Blank Control Sample (FB)--Type I water placed in a sample container in the laboratory and treated as a sample in all respects, including exposure to sampling site conditions, storage, preservation and all analytical procedures. The purpose of the FB is to determine if test substances or other interferences are present in the field environment.
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3.5 Field Duplicate (FD)--A sample collected in duplicate at 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 o f the first sample gives a measure of the precision associated with sample collection, preservation and storage, as well as with laboratory procedures.
3.6 Field M atrix Spike (FMS)--A sample collected in duplicate to which known quantities of the target analytes are added in the field at the time of sample collection. The FMS should be spiked at approximately 50-150% of the expected analyte concentration in the sample. The FMS is analyzed to ascertain if any matrix effects, interferences, or stability issues may complicate the interpretation o f the sample analysis.
3.7 Field Spike Control Sample (FSCS)--An aliquot of type I water to which known quantities o f the target analytes are added in the field at file time o f sample collection (at an appropriate concentration to be determined by the project lead). The FSCS is extracted and analyzed exactly like a sample to determine whether a loss of analyte could be attributed to sample storage and/or shipment.
3.8 Laboratory Control Sample (LCS)--An aliquot of type I water to which known quantities of the target analytes are added in the laboratory. Two levels are included, one at the LOQ (approx. 25Pg/mL), the other at a concentration o f approx. 100-250Pg/mL or another concentration to be determined by the project lead. The LCS is extracted and analyzed exactly like a laboratory sample to determine whether 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 L aboratory Sample--A portion of a sample received from the field for testing.
3.10 L im it of Detection (LOD)--The lowest concentration of an analyte that can be measured and reported with 99% confidence that the analyte concentration is greater than zero. The LOD can be determined in several ways, including signal-to-noise ratio and statistical calculations.
3.11 L im it of Q uantitation (LOQ)--The lowest concentration (LLOQ) or highest concentration (ULOQ) that can be reliably achieved within the specified limits o f precision and accuracy during routine operating conditions.
Note: The LLOQ is generally 5-10 times the LOD. For many analytes, the LLOQ analyte concentration is selected as the lowest non-zero standard in file calibration curve. However, it may be nominally chosen within these stated guidelines to simplify data reporting. Sample LLOQs are matrix-dependent.
3.12 M atrix 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 determine whether the sample matrix contributes bias to the analytical results. The background concentrations of the analytes in the sample matrix must be determined in a separate aliquot and the measured vailues 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 substances or other interferences are present in the laboratory environment, the reagents, or the apparatus.
3.14 Method Detection Limit (MDL) Determination--One of several processes that may be used to establish a LOD value. The statistically calculated minimum amount o f 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 Sample--A sample is a small portion collected from a larger quantity o f material intended to represent the original source material.
3.16 Spiking Stock Standard (SSS)--A solution prepared from stock standards used to prepare the working standard.
3.17 Stock Standard (SS)--A concentrated solution of a single analyte prepared in the laboratory with an assayed reference compound.
3.18 Working Standard (WS)--A solution of several analytes prepared in the laboratory from SSs and diluted as needed to prepare calibration standards and other required analyte solutions.
4.0 W a r n in g s a n d C a u t io n s ______________________________________________________________
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 contain high concentrations o f volatile toxic compounds. Sample containers should be 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 o f the chemicals used in this method. A reference file of material safety data sheets (MSDS) should be available to all personnel involved in these analyses.
5.0 I n t e r f e r e n c e s ___________________________________________________________
5.1 During extraction and analysis, major potential contaminant sources are reagents and liquid-solid extraction devices.
5.2 All materials used in the analyses shall be demonstrated to be free from interferences under conditions o f analysis by running method blanks.
5.3 Teflon containing materials (e.g. caps, wash bottles) contain, fluorocompounds which may cause interferences and should not be used during collection, storage, extraction, or analysis o f the samples.
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6.0 E quipment, Supplies, and Materials
Note: Brand names, suppliers, and part numbers are for illustrative purposes only. Equivalent performance may be achieved using apparatus and materials other than those specified here, but demonstration of equivalent performance that meets the requirements o f this method is the responsibility of the laboratory.
6.1 Sampling Equipment 6.1.1 Sample collection bottles--LDPE (e.g., NalgeneTM) narrow-mouth bottles with screw cap.
Note: Do not use Teflon bottles or Teflon lined caps. 6.1.2 Coolers for sample shipment 6.1.3 Ice for sample shipment. 6.1.4 Bottles must be lot-certified to be free o f artifacts by running Method blanks
according to this method.
6.2 Laboratory Equipment (Extraction and Analytical) 6.2.1 Balance, analytical (display at least 0.000Ig), Mettler. 6.2.2 Vacuum pump, Buchi. 6.2.3 Visiprep vacuum manifold, Supelco. 6.2.4 Sep Pak Vac 6cc (lg) tC,t cartridges (part # WAT 036795),Waters. 6.2.5 50mL disposable polypropylene centrifuge tubes, VWR. 6.2.6 15mL disposable polypropylene centrifuge tubes, VWR. 6.2.7 Disposable micropipettes (50-1 OOpL, 100-200pL), Drummond. 6.2.8 Class A pipettes and volumetric flasks, various. 6.2.9 Hypercarb drop-in guard column (4mm) (part # 844017-400), Keystone. 6.2.10 Stand-alone drop-in guard cartridge holder, Keystone. 6.2.11 125mL LDPE narrow-mouth bottles, Nalgene. 6.2.12 HPLC pump (LC10AD), 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 described in 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 containers or 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 "filtered type I water", hereafter in this report. 6.3.4 It is necessary to check the solvents (methanol) for the presence o f 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 micropipettes or pipettes to aliquot standard solutions to make calibration standards and matrix spikes.
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7.0 R e a g e n t s a n d S t a n d a r d s _________________________________._______________
Note: Suppliers and catalog numbers are for illustrative purposes only. Equivalent performance may be achieved using chemicals obtained from other suppliers. Do not use a lesser grade of chemical than those listed.
7.1 Chemicals 7.1.1 Methanol (MeOH), HPLC grade, JT Baker, Catalog No. JT9093-2. 7.1.2 Ammonium Acetate, Reagent grade, Sigma-Aldrich, Catalog No. A-7330. 7.1.3 Water, type I, prepared in-house. 7.1.4 Sodium Thiosulfate, Reagent grade, JT Baker.
7.2 Standards 7.2.1 Potassium perfluorooctane sulfonate (see Attachment A, Figure 1). 7.2.2 Perfluorooctane sulfonylamide (see Attachment A, Figure 2). 7.2.3 Ammonium perfluorooctanoate (see Attachment A, Figure 3).
7.3 Reagent Preparation 7.3.1 250mg/mL sodium thiosulfate solution (Extraction)--Dissolve 25g o f sodium thiosulfate in lOOmL reagent water. 7.3.2 40% m ethanol (Extraction)--Measure 400mL methanol and adjust the volume to 1.0L with reagent water. 7.3.3 lOOmM ammonium acetate solution (Analysis)--Weigh 7.71g o f ammonium acetate and dissolve in 1.0L o f reagent water. Dilute the lOOmM solution by a factor o f 50 to make the 2mM ammonium acetate solution used for mobile phase A.
Note: Alternative volumes may be prepared as long as the ratios of the solvent to solute ratios are maintained.
7.4 Spiking Stock S tandard (SSS) Preparation 7.4.1 1OOpg/mL each PFOS, PFOSA, and POAA SSSs~W eigh out 1Qmg of analytical standard (corrected for percent salt and purity--i.e., 10 mg C,F17S03K purity 90% = 8.35mg C,F17S03-) and dilute to lOOmL with methanol in a lOOmL volumetric flask. Transfer to a 125mL LDPE bottle. Prepare a separate solution for each analyte. Store solutions in a refrigerator at 42C for a maximum period of 6 months from the date of preparation. 7.4.2 lpg/m L mixed SSS--Add l.OmL each of the 1OOpg/mL SSSs (from 7.4.1) to a lOOmL volumetric flask and bring up to volume with methanol. 7.4.3 0.1pg/mL mixed SSS--Add 10.OmL of the 1.0pg/mL-mixed solution (from 7.4.2) to a lOOmL volumetric flask and bring up to volume with methanol. 7.4.4 0.01pg/mL mixed SSS--Add 10.OmL of the 0.1 pg/mL-mixed solution (from 7.4.3) to a lOOmL volumetric flask and bring up to volume with methanol. 7.4.5 Storage Conditions--Store all SSSs in a refrigerator in 125mL LDPE bottles at 42C for a maximum period of 3 months from the date of preparation.
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7.5 C alibration Standards
'
7.5.1 lOOpg/mL each PFOS, PFOSA, and POAA stock standard solutions--Weigh
out lOmg of analytical standard (corrected for percent salt and purity) and dilute
to lOOmL with methanol in a lOOmL volumetric flask. Transfer to a 125mL
LDPE bottle. Prepare a separate solution for each analyte. Store solutions in a
refrigerator at 42C for a maximum period of 6 months from the date of
preparation.
7.5.2 1pg/mL W orking Standard--Add 1.OmL each of the lOOpg/mL SS solutions
(from 7.5.1) to a lOOmL volumetric flask and bring up to volume with methanol.
7.5.3 O.lpg/mL W orking Standard --Add lO.OmL of the 1.Opg/mL mixed solution
(from 7.5.2) to a lOOmL volumetric flask and bring up to volume with methanol.
7.5.4 O.Olpg/mL W orking Standard --Add lO.OmL o f the 0.1 pg/mL mixed solution
(from 7.5.3) to a lOOmL volumetric flask and bring up to volume with methanol.
7.5.5 Storage Conditions--Store all WSs in a refrigerator (in 125mL LDPE bottles)
at 42C for a maximum period of 3 months from the date o f preparation.
7.5.6 Calibration Standard--Prepare a minimum of five calibration solutions in
filtered type I water according to the following table:
Concentration Volume of final Calibration Standard
of WS, pg/mL WS, pL
Volume, mL
0.0 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 0.10 400
40 40
l M ay b e prepared to extend the range beyond 500Pg/m L.
2 May be prepared to extend the range beyond 750Pg/mL.
Final Concentration of Calibration Standard, Pg/mL
0 . 25
50 100 250 500 7501 10002
Note: The absolute volumes of the standards may be varied by the analyst as long as the correct proportions of solute to solvent are maintained. 7.5.7 The standards are processed through the extraction procedure (Section 9.0),
identical to the laboratory samples. The extracted concentration o f the calibration standard is equal to 8X the initial concentration, due to the concentration o f the standard during the extraction process. 7.5.8 Storage Conditions--Store all extracted calibration standards in 15mL polypropylene tubes at 42C, for a maximum period o f two weeks from the date ofpreparation.
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8.0 S a m p l e C o l l e c t i o n , P r e s e r v a t io n a n d S t o r a g e ________
.
Note: Sampling equipment, including automatic samplers, must be free of Teflon tubing, gaskets, and other parts that may leach interfering analytes into the water sample. Automatic samplers that composite samples over time should use refrigerated polypropylene sample containers if possible. Sample bottles should not be rinsed before sample collection.
8.1 Tap Water--Open the tap and allow the system to flush until the water temperature (1510C) has stabilized (usually about two minutes). Adjust the flow to about SOOmL/min and collect samples from the flowing stream.
8.2 G round W ater--Purge the well of standing water using a pump or a bailer. Collect the sample directly from the pump or from the bailer.
8.3 Surface W ater--When sampling from an open body o f water, fill the sample container with water from a representative area.
8.4 Sample Dechlorination--All samples should be iced or refrigerated at 42C and kept in the dark from the time of collection until extraction. Residual chlorine should be reduced by adding 200pL of a 250mg/mL sodium thiosulfate solution to each water sample, FB, and FSCS (which may be placed in each bottle before leaving for the sampling site.).
8.5 Holding Time (HT)-- Results of the time/storage study o f all target analytes showed that the three compounds are stable for 14 days in water samples when the samples are dechlorinated and stored as described in section 8.4 (see also reference 18.3). Therefore, laboratory samples must be extracted within 14 days and the extracts analyzed within 30 days of sample collection. If the HT exceeds 14 days, great care is used when evaluating field spikes to avoid misrepresentation of the sample concentration.
8.6 Field Blanks 8.6.1 Process a Field Blank Control Sample (FB) along with each sample set (samples collected from the same general sample site at approximately the same time). At the laboratory, prior to sample collection, fill a sample container with filtered type I water, seal, and ship the FB to the sampling site along with the empty sample containers. 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
th eF B .
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 Separate FDs 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 o f samples, each cooler must
contain a FSCS.
8.8.2 At the laboratory, fill a sample container with lOOmL of type I water. Seal and
ship to the sampling site along with the empty sample containers and FBs.
8.8.3 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 E x t r a c t io n P r o c e d u r e ___________________________________________ .___________________
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 40mL o f sample into 50mL polypropylene centrifuge tubes (Spike the QC and Matrix spikes as required*, replace lid and mix well).
Note: * Samples may need to be prescreened to determine an appropriate matrix spike level (typically 50-150% of sample concentration). 9.1.3 Condition the Clg 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 flow rate. Do not allow the column to run 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 5mL of eluate into graduated 15mL
polypropylene centrifuge tubes. This is the target elution fraction (final volume =
5mL). 9.1.7 Analyze a portion of the target elution fraction eluent using negative electrospray
HPLC/MS/MS (Section 10.2).
Note: Samples are concentrated by a factor of eight during the extraction; Initial Vol = 40mL
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 42C until analysis. 9.1.9 Standardization of Clt SPE columns--I f poor recoveries are observed, it may
be necessary to standardize the ClgSPE columns in the following manner before
analyzing samples. 9.1.9.1 Use a standard with an analyte concentration between 1000 and 4000
Pg/mL. Follow the extraction scheme as outlined from steps 9.1.1 to 9.1.6, except, collect the eluate fraction separately (approx..5mL), as well as the target elution fraction. 9.1.9.2 After step 9.1.6, collect a post-elution fraction by, eluting with an
9.1.9.3
9.1.9.4 9.1.9.5
additional 5mL o f 100% methanol. Analyze all three fractions by HPLC/MS/MS. If the target fraction contains a minimum of 85% o f the respective analytes, it may be
considered acceptable. If the wash contains significant standard (>15%), either the wash volume or percentage o f 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 Calibration and Standardization (Analytical Setup)
.
Note: Other instruments may be used and the equipment and conditions may be very different as long as the method criteria are m et The operator must optimize and document the equipment and settings used.
10.1 Establish the LC/MS/MS system and operating conditions equivalent to the following: Mass Spec: Micromass Quattro Ultima (Micromass) Interface: Electrospray (Micromass) Mode: Electrospray Negative, Multiple Response Monitoring (MRM) Harvard infusion pump (Harvard Instruments), for timing Computer COMPAQ Professional Workstation AP200 Software: Windows NT, MassLynx 3.3 HPLC: Hewlett Packard (HP) Series 1100 HP Quat Pump HP Vacuum Degasser HP Autosampler HP Column Oven
Note: A 4 x 10mm Hypercarb drop-in guard cartridge (Keystone, part # 844017-400) is attached on-line after the purge valve and before the sample injector port to trap any residue contaminants that may be in the mobile phase and/or HPLC system.
HPLC Column: Genesis C, (Jones Chromatography), 2.1mm x 50mm, 4jim Column Temperature: 35C Injection Volume: 15pL Mobile Phase (A): 2mM Ammonium Acetate in filtered type I water (See 7.3.1) Mobile Phase (B): Methanol
HPLC G radient Program :
Time, Percent Mobile Percent Mobile
min Phase A
Phase B
0.0 6 0
40
0.4 6 0
40
1.0 10
90
7.0 10
90
7.5 0
100
9.0 0
100
9.5 60
40
13.5 60
40
14.0 60
40
Flow 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 m et
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It may be necessary to adjust the HPLC gradient in order to optimize instrument performance. Columns with different dimensions (e.g. 2.1mm x 30mm) and columns from different manufacturers (Keystone Betasil C,, etc.) may be used.
Ions M onitored: Analyte Prim ary Ion Product Ion
POAA PFOS PFOSA
413.0 499.0 498.0
169.0 99.0 78.0
A pproxim ate Retention Time
5..0 5.2 5.8
Other product ions may be chosen at the discretion o f the analyst, although m/z 99 is suggested for PFOS. Use o f the suggested primary ion is recommended. Retention times may vary slightly, on a day-to-day basis, depending on the batch of mobile phase etc. Drift in retention times is acceptable within an analytical run, as long as the drift continues through the entire analysis and the standards are interspersed throughout the analytical run.
10.2 Tune File Param eters 10.2.1 The following values are provided as an example. Actual values may vary from instrument to instrument Also, these values may be changed from time to time in order to optimize for greatest sensitivity.
A nalyte POAA PFOS PFOSA
Dwell, sec 0.2-0.4 0.2-0.4 0.2-0.4
Collision Energy, eV
10-25 30-60 20-50
Cone, V 20-30 50-80 30-60
Source Capillary Hexapole 1 Aperture 1 Hexapole 2 Source Block Temp. Desolvation Temp.
Set 2.56-3.5kV
0.5V 0.2V 0.8V 100-150C 250-400C
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A nalyzer LM Resl H M Resl EEnergy 1 Entrance
Exit LM Res2 HMRes 2 EEnergy 2 M ultiplier
Set 12.O-15.0V 12.0-15.0V
0.7V -2V IV 11.OV 11.0V 1.0V 650V
Gas Flows Cone Gas Desolvation
Set 150L/hr 700L/hr
Pressures Gas Cell
Set 3.0e-3m bar
11.0 ANALYTICAL QUALITY CONTROL____________________________________________
11.1 Analytical results o f the FB, FMS, FD, and FSCS should be evaluated at the conclusion o f the study to help interpret the data quality o f samples data. Analytical results for these control/duplicate samples must be reported with the sample data.
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""LIM5Ei-
12.0 Analytical Procedure___________________________
12.1 Sam ple Analysis 12.1.1 Set up analysis sample queue. 12.1.2 Inject the same aliquot (between 5-25jiL) o f 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 o f the highest, active calibration curve level must be diluted and reanalyzed.
12.2 Calibration Carve 12.2.1 Starting with the standard o f lowest concentration, inject the same size aliquot (between 10-25p.L) o f each extracted calibration standard according to Section 12.1 and tabulate the response (peak height or area) versus the concentration in the standard. Use linear standard curves for quantitation generated for each analyte by linear regression with 1/x weighting o f peak area versus calibration standard concentration. The correlation coefficient (r) for the calibration curves must be >0.990 (PSO^SO). If calibration results fall outside these limits, then appropriate steps must be taken to adjust instrument operation and the standards reanalyzed. 12.2.2 Curve--The measured value for each curve point must be within 30% o f theoretical values when curve is evaluated over a range appropriate to the data. High or low points may be deactivated to achieve these criteria, but an acceptable curve must contain at least five active curve points. 12.2.3 Continuing Curve Verification (CCV)--Mid- and low-level calibration checks should be analyzed every 5-10 injections. The analyte level measured in the CCVs should be within 30% o f theoretical values. If CCVs fall outside o f this range, data collected subsequent to the last passing CCV should not be used. Only data collected between acceptable CCVs or the initial curve can be used.
13.0 Data Analysis and Calculations
13.1 Calculate the analytical sample (extract) concentration from the standard curve using the following equation: (Peak area, -intercept) Extract Concentration,pg/mL=(slope)
13.2 Calculate the percent recovery o f the FSCS using the following equation:
FSCS % rec. ,, (FSCS cone., P g M . ) x m (Cone, added, Pg/mL)
13.3 Calculate the percent recovery o f the MSs using the following equation:
MS%rec. = (MSco;o ..Pg/? L -S ampleC onc,P^m L) |<100 (Cone, added, Pg/mL)
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LIM5 E 0 1 -0 09 6
14.0 M ethod Performance Parameters _________
Note: Any method performance parameters that are not achieved must be considered in the evaluation of the data. Nonconformance to any specified parameters must be described and discussed in any reporting o f the data.
14.1 Linearity--Linear standard curves for quantitation generated for each analyte by linear regression with 1/x weighting o f peak area versus calibration standard concentration. The correlation coefficient (r) for the calibration curves must be 0.990 (^0.980).
14.2 Calibration Curve Standards--The measured value for each curve point must be within 30% o f theoretical values when curve is evaluated over a range appropriate to the data. High or low points may be deactivated to achieve these criteria, but an acceptable curve 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 30% o f theoretical values. If CCVs fall outside of this range, data collected subsequent to the last passing CCV should not be used. Only data collected between acceptable CCVs can be used.
14.4 Limit of Detection (LOD)--The lowest calibration standard with a peak area at least 2X the peak area of the extraction blank that can be measured at a concentration greater than zero.
14.5 Limits of Quantitation (LOQ)--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 o f the LLOQ must be within 30% o f the theoretical value.
14.6 M atrix Spikes--Matrix spike percent recoveries must be within 30% o f the spiked concentration.
14.7 Solvent Blanks, Method Blanks, and Matrix Blanks--Values must be below the lowest non-zero active standard in the calibration curve. Matrix blanks are considered compliant if no test substance is detected above the LOD for that analyte.
14.8 R eproducibility--Reproducibility o f the method is defined by the results o f the matrix spikes and matrix spike duplicates. The MS/MSD should be reproducible to within 20%.
14.9 Use of Confirmatory Methods--None
14.10 Demonstration of Specificity--Specificity is demonstrated by chromatographic retention time (within 3% o f standard) and the mass spectral response o f unique product ions generated from a characteristic primary 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 actions in the appropriate logbook. 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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ClMiS 01-0096'
15.0 P ollution Prevention and Waste Management
15.1 Sample extract waste and flammable solvent is 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 following information included, either in the header or hand-written on die 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 acquisition method from MassLynx to include in the appropriate study folder. Copy these pages and tape into the instrument run log.
16.3 Plot the calibration curves as described in this method, then print these graphs and store in the study folder.
16.4 Print data integration summary, integration method, and chromatograms, from MassLynx, and store in the study folder.
16.5 Summarize data using suitable software (MS Excel 97) and store in the study folder.
16.6 Back up electronic data to appropriate medium. Record in study notebook the file name and location o fbackup electronic data.
17.0 Attachments___________________________________________________________ 17.1 Attachment A: Figures--Fluorochemical Compounds
18.0 References
18.1 "Guidelines and Format for Methods to be Proposed at 40 CFR Part 136 or Part 141", U.S. Environmental Protection Agency, Office of Science and Technology Office of Water, Washington, D.C. Draft 1996.
18.2 "Method of Analysis for the Determination o f Perfluorooctane sulfonate (PFOS), Perfluorooctane sulfonylamide (PFOSA), and Perfiuorooctanoate (POAA) in Water", E. Wickremesinhe and J. Flaherty, Study Number 023-002, Centre Analytical Laboratories, Inc., State College, Pennsylvania, January 2000.
18.3 Validation report for the "Method of Analysis for the Determination o f Perfluorooctane sulfonate (PFOS), Perfluorooctane sulfonylamide (PFOSA), and Perfiuorooctanoate (POAA) in Water", E. Wickremesinhe and J. Flaherty, Study Number 023-002, Centre Analytical Laboratories, Inc., State College, Pennsylvania, (Approval pending)
19.0 Revisions______________________________________________________________
Revision Number.
Reason For Revision
Revision D ate
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Figure 1: PFOS
Chemical Name Molecular ion
Perfluorooctane sulfonate 499(C ,F17S03-)
C 8 F 17S -O -
O
PFOS
Note: Standards are made from the salt, potassium perfluorooctane sulfonate [C8F17SO3K], m/w 538.
Figure 2: PFOSA
Chemical Name Molecular ion
= =
Perfluorooctane sulfonylamide 498 (CjFi7S02NH2)
C8F17S------ NHo
I
O
PFOSA
Figure 3: POAA
Chemical Name =
Molecular ion
=
Perfluorooctanoate 413 (QFuCOCT)
.
C7F15CO
POAA
Note: Standards are made from die salt, ammonium perfluorooctanoate [C7F15COONH4], m/w 431
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__________________________________________________________________LIMS E01-0096
Appendix B: Data Summary Tables
Table 4. Port St. Lucie Resample January 24,2001 Sample Results for GEN-050
Sample Number and Description
Site 1
E00-0096-19527 E 0 0 - 0 0 9 6 - 19541 E00-0096-19545 E00-0096-19549 E00-0096-19553
East South West North Culvert Discharge
PFOS ng/m L
1.60 1.54 1.59 1.78 1.38
PFOA ng/m L <0.0250A 0.123 0.107 0.397 0.081
PFOSA ng/m L 0.0283 0.0238 0.0258 0.299* 0.0363
Average
1.58
0.180
0.029
Std. Dev.
0.15
0.15
0.005
RSD (% )
9.2
83.5
19.2
Site II
E00-0096-19555 E00-0096-19557
Sited Site II, Dupe
<0.0100A 0.0148
<0.0250A 0.0290
<0.0100A <0.0100A
A verag e
0.0099
0.0208
<0.0100A
Site III
E00-0096-19565
Site III
<0.0100A
0.0420
<0.0100A
It is not possible to verify true recovery of endogenous analyte from samples without radio-labeled reference material. The only measurement of accuracy available at this time, matrix spike studies, indicate that the data quantitative to 30%.
Averages are calculated with the value of Y* LOQ assigned to samples reported at <LOQ.
A = No Limit of Detection (LOD) determined for this analysis. LOQ/LOD is the same concentration and is equal to the following:
LOQ = 0.0100 ng/ml for PFOS & PFOSA LOQ = 0.0250 ng'mL for PFOA.
* Not included in calculation of site averaae.
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Appendix C: Data Spreadsheets
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PO R T ST. LUCIE RESAMPLEi JANUARY 24,2001
Fjrtfirtioi 028201 OK Analyaia 02*401 H O J, 020601 HOJ (Ruby)
S ta p le lum ber
pros
extract
PPOS
m apk
( r i / - L>
POS
Sam ple (o f/m L )
N otes
File nam e
B leak
enter, ext blank-1 water, ex t blank-2 w ater, ext blank-3 w a te r, e x t b lan k -4
E x tra ctio n Blank Ex& actioii Blank E xtraction Blank E xtraction Blank
aoo aoo < I O p g /m L
0.00 aoo < 1 0 p f / m L
OjOO
aoo < I O p f / m l
aoo aoo < lQ p g /m L
(010206019 (010206020 (010206021 (010206022
BOI 0090 19525
F ield Blank
0.00
01-0096-19524
Field Blank
0.00
*LOQ crilcm iU ud in the method were not met for PPOA fix repotted valuci <2.5 ng/raL
aoo aoo
< 10pg/m L
<IOpg/mI.
(010206025 (010206026
PPOA
0 182 47 0 0 157
SITE I
B 01-0096-19527 E 0 1 -0096-19541 EO I-0096-19545 EO I-0096-19549 EO I-0096-19553
S I T E 11
E O I-0096-19555 E O I-0096-19557
S ite I, c a rt
Su* I, south Site I, w est S ite 1, n o rth S ite 1, culvcct d tsch sig c
12797 12326 12746 14253 11010
S ite 11 S ite 11, d u p e
0 118
15994 1540.8 1593.3 17814 13765
ao
14.8
140 154 1.59 1.78 158 A venge Std. D ev. R SD fA )
< 10gg/m L 0.0148 Avenge
Std. D ev. R SD (% )
1.58 0.15 9.2
0 .0 0 9 9 NA NA
R 010206045 (010206056 (010206059 (010206060 (010206061
(010206029 (010206032
158 981 857 3173 645
28 232
PPOA aam plc
PPOA
( /m l)* N ew
ppo sa F ilen am e (m / L )
PPOSA
PPOSA
Sam ple (p c/a> L )
N ote F ile n a m e
aoo
2275 548 OjOO
0 194
<25p^m L <25pgm L <25pgm L < 2 S p g itil
< 2S pgjnl, <25 pgjnL
(010200019 (010200020 (010200021 (010200022
(010200025 (010200026
0 0 0 0
0 0
0 <10pg/m L 0 < 10 p k / hvL 0 < 10 g g /m L 0 < 10pg/m L
0 <10pg/m L 0 <10p/m L
(010206019 (010206020 (010206021 (010206022
(010206025 (010206026
194 123 107 397 81
3.5 29.0 Avenge Std. D ev. RSD (% )
<25pgm L
am ai07
0597 0061 Avenge Std. Dev. RSD (W )
<25 pg/m L 00290 0.0208 NA NA
R012804S (010206056 (010206059 (010206060 (010206061
an ais
833
(010206029 (010206032
226 190 206 2391 290
0 0
2R25 23.75 25.75 298.9 365
04 0.0 Avenge Std. Dev.
R SD (%)
0.0283 00238 00258 0299* 00363 A veng: Sed. Dev. R S D (*/)
< l0 p g /m L <10 pg/m L <10pg/m L
NA NA
O29 0005 19.2
R 010206045 (010206056 (010206059 (010206060 (010206061
(010206029 (010206032
A
Average* u * cak u alted w ith th e vahie o f 1 /2 L O Q u n e d to sample repotted
1 BO-0096-19569
Blind
11983
14M
1.498
(010206036
664
830
0083
(010206036
4 o u tlie r n o t in clu d ed in ca lc u la tio n o f site venge
166 2 0 4 ------- E E i------
010206036 1
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,
Analytical Report: FACT GEN-050 LIMS E01-0096
PO RT ST. LUCIE RESAMPLEi JANUARY 24,2001
Ekhmoob *20201 OK
Ajudyua
020*4! H O J , 20001 H O j (R uby)
B O 1-0096-19S2S B 0 1-0096-19526
R eid M a u n Spike*
B01-0096 19531
B 0 1 -0096-19532
E O I-0096-19535
B O I-0096-19536
B O I0 0 96-19559 BOI 0096-19560
L a b w a J w y Matrix S p ik e BO1-009619555 M S-100 ppt B 01O 09619555 M SD-lOOppt BOI009619565 MS-100ppt B O I0 0 9 6 1 9 5 6 5 M SD -100 p p t B01-009619541-M S-250 ppt B 0 1 0 0 9 6 19541-MSO-2SO p p t E 0 1 0 0 9 6 19541-M S-5 p p b 1:10 B O !0 0 9 6 1 9 5 4 l-M S O -5 p p b t 1:10
P n ew io Q
E O I-0096-19527 B 0 0 0 0 9 6 -19577-1 E O I-0096-19527-2 B O I-0096-19527-3 E O I-0096-19529
P SC S -200ppt PSC S-lppb
Site I, c u t P M S 1 p p b Sue 1, e u t F M S 25 p p b Site I . e u t P M S 1 p p b Sit 1, e u t F M S 25 p p b
Site H. PM S 200 p p t S*te II, P M S 1 p pb
Site 11, MS Site II, M SD Site IH . M S Site 11!. M S D Site 1, MS Site I. M SD Site I,M S Sit I.M S D
Site l . e u t Site 1 d u p e Site l d u p c Site I d u p e Site l . c u t P D
1287 5768
161 721
0.161 0.721
SREC 80.4 711
(010206027 (010206028
16542 1,760 19908
S6--
2068 22000 2489 19825
1260 5669
157.5 709
107 22 149 20
a s 0.709
48.9 (010206052 81.7 (010206053 9 1 0 (010206054 73.0 (010206055
7 3 3 (010206033 69.9 (010206034
810 822 1149 957 14359 14917 48180 52330
a to i ao ai4 4 ai3 o 1.795 1.865 6.023 6341
91.4 919
139 US 102 130 896
too
(010206039 (010206040 (010206041 (010206042 (010206062 (010206063 (010206066 (010206067
12797 12562 12647 12436 14699
15993 1570
130 137
1581 1555 1837
138 135 1.84
P rec ia o a, extrac tio c (ViRSD) Preciiioa, collection QQ
130 117
RO10206045 (010206046 (010206047 (010206048 (010206049
KftfiC
1107
138
Q.138
692 (010208027
6907
863
0363
863 (010208028
7274 1428 8320 1649
1504 7797
909 17850 1040 20613
188 975
0.91 18 1.04 21
a is e 0.975
733 (010208052 70.7 010208053 863 (010208054 81.7 (010206055
940 (010208033 973 (010208034
1353 985 1357 1339 2382 2943 37760 44670
0169 0123 0170 0167 0298 0368 4.720 5.584
141 108 121 12t 70.1
UM
91J 109
(010208039 (010208040 (010200041 (010208042 (010208062 (010208063 (010208066 (010208067
158 19.8 < 2 5 p g jn L
182 21 8 < 25 p g /m L
533 6 63 00666
34 435 <2$ pg/m L
648
81 JO
00810
Pcecion, extraction (H RSD) PracUkxL, coQectk>o 0 4 )
NA 122
(010208046 (010208047 (010208048 (010208049
HREC
1445
Ul
0.181
9 0 3 (010206027 I
5625
703
0.703
703 (010206028 1
7864 1857 8437 I960
1412 6796
983 23213 1055 24750
1763 850
0.983 23 1J5 23
0.177 0.850
95.5 (010206052 9 1 7 (010206053 103 (010206054 9 8 9 (010206055
883 8 5 jO
(010206033 (010206034
859 874 699 799 2290 2524 41890 44440
0.107 0.109 a087 0.100 0386 0316 5.236 5355
107.4 1093 87.4 99.9 105 117 104 111
(010206039 (010206040 (010206041 (010206042 [010206062 (010206063 010206066 (010206067
226 2 8 3 0 0 2 8 3 202 253 00253 235 29.4 0 0 2 9 4 207 25.9 O2S9 235 29.4 00294
Poe cision,cxtraction (% RSD) P w tiH on, collection M
7.17 108
RO10206045 (010206046 (010206047 (010206048 (010206049
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Analytical Report: FACT GEN-050 LIMS E01-0096
Appendix D: Example Calculations
Formula Used for W ater Analyses in Study FACT GEN-050
AR (pg/m L) X FV (mL) x 1.0 ng = R ep o rted C o n cen tratio n (ng/m L ) IV (mL) 1000 pg
Calculation Used fo r PFOS Concentration in EOO-0096-19527
12797 pg/m L x 5 mL x 1.0 ng = 1.60 ng/mL
40 mL lOOOpg
AR-- A nalytical result from M assLynx sum m ary IV-- Initial Volume o f H 2 0 Extracted FV-- Final Volume o f Extract
Formula Used for Spike Recovery Analyses in Study FACT GEN-050 ( RCsoiked (ng/m L) - RCunsniked (ng/m L)) x 100% = % R ecovery
SL (ng/mL)
Calculation Used fo r E 00-0096-19535a (Site i)
(2.49 ng/m L -1 .5 8 ng/mL) x 100% = 91% 1.0 ng/mL
"A verage concentration o f all Site I sam ples used for RCumpiked-
RC-- Reported Concentration SL-- Spike Level
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3M Environmental Laboratory Study
Appendix E: Interim Certificates of Analysis
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Analytical Report: FA C T G E N -050 LIM S E01-0096
Centre Analytical Laboratories, Inc.
3 0 4 8 R esearch Drive Phone: (814) 231-8032
State College, PA 16801 Fax: (814) 231-1253 or (814) 231-1580
INTERIM CERTIFICATE OF ANALYSIS
Revision 1(9/7/00) Centre A nalytical Laboratories COA Reference #: 023-021
3M Product: PFOS, Prim ary Standard T est Control Reference #: TCR00017-46
Purity: 97.9%
Purity*
Test Name
A ppearance Identification
NMR
M etals (ICP/MS) 1. Calcium 2. Magnesium 3. Sodium 4. Potassium* 5. Nickel 6. Iron 7. Manganese
Total % Impurity (NMR)
Total % Impurity (LC/MS)
Total % Im purity (GC/MS)
Related Compounds - POAA Residual Solvents (TGA)
Purity by DSC Inorganic Anions (IC) .
1. Chloride 2. Fluoride 3. Bromide 4. Nitrate 5. Nitrite 6. Phosphate 7. Sulfate3
Organic A cids4(IC) 1. TFA 2. PFPA 3. HFBA 4. NFPA
Elemental Analysis': 1. Carbon 2. Hydrogen 3. Nitrogen 4. Sulfur 5. Fluorine
. Yv
Specifications '' ''V;^
White Crystalline Powder
--T
: ._
,!. :
- *J
u ..
'
. ' *'*
_.
' ' - .
V ' '
'
V O ' V . '. ..
: ;
.
*
'
; :v!r*V -''/ r ' y ' '
.-
-'
.
; ` -
,;7 .
. . . .
'V - -- - -___--
': .
'. .
.
'
. .. v-
1. Theoretical Value = 17.8% 2. Theoretical Value = 0% 3. Theoretical Value = 0% 4. Theoretical Value = 5.95% 5. Theoretical Value = 60%
. Result 97.9%
Conforms
Positive
1. 0.006 w t/w t% 2. 0.002 wt/w t.% 3. 1.216 w t/w t% 4. 6.685 w t/w t% 5. <0.001 wt/w t.% 6. 0.002 w t/w t% 7. <0.001 w t/w t.%
0.13 w t/w t% 0.14w t/w t% None Detected <0.01 wt/w t.% None Detected 97.5 Mol. % .
1. <0.015 w t/w t.% 2. 0.60 wt/wt.% 3. <0.040 wt/wt.% 4. <0.009 wt/wt.% 5. <0.006 w t./w t% 6. <0.007 w t/w t% 7. 7.88 w t/w t%
1. <0.1 wt/w t.% 2. <0.1 wt/w t.% 3. <0.1 w t/w t% 4. <0.25 w t/w t%
1. 11.39 wt/wt.% 2. 0.456 w t/w t% 3. 1.51 w t/w t.% 4. 7.80 wt/wt.% 5. 58.0 wt/wt.%
COA023-021 3M Environmental Laboratory
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Centre Analytical Laboratories, Inc.
3 0 4 8 Research Drive Phone: (814) 231-8032
State College, PA 16801 Fax: (814) 231-1253 or (814) 231-1580
INTERIM CERTIFICATE OF ANALYSIS
Centre Analytical Laboratories COA Reference #: 023-021
Date of Last Analysis: 08/31/00
Expiration Date: 08/31/01
Storage Conditions: Frozen <-10C
Re-assessment Date: 08/31/01
'Purity = 100% - (sum o f metal impurities, 1.226% +LC/MS impurities, 0.14%+Inorganic Fluoride, 0.60%+NMR Impurity, 0.13%).
Total impurity from all tests = 2.09% Purity = 100% - 2.09% = 97.9%
.
2Potassium is expected in this, salt form and is therefore not considered an impurity.
3Sulfur in the sample appears to be converted to SO and hence detected using the inorganic anion method conditions. The anion result agrees well with the sulfur
determination in the elemental analysis, lending confidence to this interpretation. Based ' on the results, the SO4is not considered an impurity.
4TFA HFBA NFPA PFPA
Trifluoroacetic acid Heptafluorobutyric acid Nonofluoropentanoic acid Pentafluoropropanoic acid
sTheoretical value calculations based on the empirical formula, CjsFi7S03"K.+ (MW=538).
This work was conducted under EPA Good Laboratory Practice Standards (40 CFR 160).
i COA023-021
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Centre Analytical Laboratories, Inc.
3 0 4 8 Research Drive
PJ
State College, PA 16801 A V & U \Z 5 & o r (814) 231-1580
Centre Analytical Laboratories COA Reference #: 023-021
LC/MS Purity Profile:
Im purity C4 C5 C6 C7
Total
W t/w t. %
ND ND ND 0.14 0.14
Note: The C7 value was calculated using the average response factors from the C6 and C8 standard curves.
V
Prepared By:
S. Bell
?f o / r Date
lytical Laboratories
Reviewed By:
Date
Laboratory Manager, Centre Analytical Laboratories
n
COA023-021
3M Environmental Laboratory
.
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Analytical Report: FA C T G E N -050 LIM S E 0 1-0096
Centre Analytical Laboratories, Inc.
3 0 4 8 Research Drive Phone: (814) 231-8032
State College, PA 16801 Fax: (814) 231-1253 or (814) 231-1580
P u rity 1
INTERIM CERTIFICATE OF ANALYSIS
Revision 1 (11/6/00)
Centre A nalytical Laboratories COA Reference #: 023-034
3M Product: PFOA, Prim ary Standard
Test Control Reference #: TCR-99030-30
___________________ P arity: 95.0%______
Test Name
Specifications
Result 95.0%
Appearance
White, crystalline solid
Conforms
Identification
NMR
Positive
M etals (ICP/MS) 1. Calcium 2. Magnesium
v -jg: f - ig r
1. 0.001 w t/w t% 2. <0.001 w t/w t.%
3. Sodium
3. 0.001 wt/w t.%
4. Potassium
4. <0.001 wt/w t.%
5. Nickel
5. <0.001 w t/w t.%
6. Iron
6. <0.001 w t/w t.%
7. Manganese
7. <0.001 w t/w t.%
Total % Impurity (NMR)
0.36 w t/w t.%
Total % Impurity (LC/MS)
4.68w t/w t%
Total % Impurity (GC/MS)
y/m -.
O Residual Solvents (TGA)
None Quantified.% None Detected
Purity by DSC
99.8%
Inorganic Anions (IC)
. ..ii.v iiJ .:.
s*'
1. Chloride
1. <0.015 w t/w t.%
2. Fluoride
2. <0.005 w t/w t%
3. Bromide
3. <0.040 w t./w t%
4. Nitrate
4. <0.009 w t/w t%
5. Nitrite
6. Phosphate 7. Sulfate
- [$']if;
5. <0.006 w t/w t.%
6. <0.006 w t/w t% v 7. <0.040 w t/w t.%
Organic Acids2 (IQ 1. TFA 2. PFPA
p!; 7.'-;Ca: '.- f - : r ' i - f i ^ --
*' 1. <0.1 w t/w t.% 2. <0.1 w t/w t%
3. HFBA
3. <0.1 w t/w t%
4. NFPA
4. <0.25 w t/w t%
Elemental Analysis1:
1. Carbon
1. Theoretical Value = 22.3%
1. 18.9w t./w t%
2. Hydrogen .
2. Theoretical Value = 0.935%
2. 1.27 w t/w t.%
3. Nitrogen
3. Theoretical Value =*3.25%
3. 3.76 w t./w t%
4. Sulfur
4. Theoretical Value = 0%
4. 4.38 w t./w t%
5. Fluorine
5. Theoretical Value = 66.1%
5. 62.1 w t/w t%
Ammonium Analysis1
Ion Selective Electrode
Theoretical Value = 4.18%
2.94 w t/w t %
COA023034.doc 3M Environmental Laboratory
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Analytical Report: FACT G EN -050 LIMS E 01-0096
Centre Analytical Laboratories, Inc.
3048 Research Drive Phone: (814) 231-8032
State College, PA 16801 Fax: (814) 231-1253 or (814) 231-1580
INTERIM CERTIFICATE OF ANALYSIS
Centre Analytical Laboratories COA Reference #: 023-034
Date o f Last Analysis: 10/31/00
Expiration Date: 10/31/01
Storage Conditions: <-10C
Re-assessment Date: 10/31/01
lPurity = 100% - (total metal impurities, 0.002% + Total NMR impurities, 0.36 + Total LC/MS impurities, 4.68 %)
Total impurity from all tests = 5.042% Purity = 100% - 5.042% = 95.0%
2 TFA HFBA NFPA PFPA
Trifluoroacetic acid Heptafluorobutyric acid Nonafluoropentanoic acid Pentafluoropropanoic acid
3Theoretical value calculations based on the empirical formula, CgFisOi^NH/*'* (MW=431.1)
This work was conducted under EPA Good Laboratory Practice Standards (40 C FR 160).
LC/MS Purity Profile:
'
Peak# i 2 3
Total
Retention Time (min) 12.144 13.533 14.238 -
Mass(s) 29.0
331,319 369 *
Identity C6
Fis/C7 PFOA
-
Area 205859 903329 22630600 3739788
% Area 0.87
3.81 -
4.68
Prepared By:
Date
Reviewed By:
Laboratories
s/c/o *
John Flaherty y
Date
Laboratory Manager, Centre Analytical Laboratories
COA023034.doc 3M Environmental Laboratory
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3M Environmental Laboratory Study
Appendix F: Report Signature Page
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A nalytical R eport: F A C T G E N -0 5 0 L IM S E 0 1 -0 0 9 6
Kristen J. Hansen, Ph.D., Principal Analytical Investigator
Date
3M Environmental Laboratory
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