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Environmental Laboratory E05-0210 Interim Report#15
Interim Report #15: Analysis of Water Samples from Northern Alabama Potable Water Systems
Study Title
ANALYSIS OF PERFLUOROBUTANESULFONATE (PFBS), PERFLUOROHEXANESULFONATE (PFHS), AND PERFLUOROOCTANESULFONATE (PFOS) IN WATER, SOIL, SEDIMENT, FISH, CLAMS, VEGETATION, SMALL MAMMAL LIVER AND SMALL MAMMAL SERUM USING LC/MS/MS
FOR THE 3M DECATUR MONITORING PROGRAM
Data Requirement
EPA TSCA Good Laboratory Practice Standards 40 CFR 792
Author
Michelle D. Malinsky, Ph.D
3M Environmental Laboratory
Interim Report Completion Date
Date of signing
Certificate #2052-01
Performing Laboratory
3M Environmental Laboratory Building 2-3E-09 935 Bush Ave.
St. Paul, MN 55106
Project Identification
E05-0210
Total Number of Pages 123
The testing reported herein meet the requirements of ISO/IED 17025-1999 "General Requirements for the Competence of Testing and Calibration Laboratories", in accordance with the A2LA Certificate #2052-01. Testing that complies with this International Standard also operate in accordance with ISO 9001/ISO 9002 (1994).
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Environmental Laboratory 05-0210 Interim Report#15
GLP COMPLIANCSETATEMENT
Study Title: Analysis of Pertluorobutanesulfonate (PFBS), Pertluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate(PFOS) in Water, Soil, Sediment, Fish, Clams, Vegetation, Small Mammal Liver and Small Mammal Serum Using LClMSlMS for the 3M Decatur Monitoring Program
Interim Study: Analysis of Water Samples from NorthernAlabama Potable Water Systems
Interim Study IdentificationNumber:
E05-0210 Interim RepoMl5
This study was conducted in compliancewith Toxic Substances Control Act (TSCA) Good Laboratory Practice (GLP) Standards, 40 CFR 792, with the exceptions listed below:
Exceptions to GLP compliance:
None
Sponsor Representative
3I /z3/ud
date
Jaisimha Kesari P. E., DEE, Weston Solutions, Inc.
study Director
Date
Certiffcata #205241
The testingrepoltedhereinmeetthe requirementsof ISOAED 170251999"General
Requirementsforthe Competenceof Testingand Calibration Laboratories",in
accordance with the MIACertificateR052-01. Testingthat complieswith this InternationalStandard also operate in accordance with IS0 9001ASO 9002 (1994).
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3M EnvironmentalLaboratory EO5-0210 interim Report#15
QUALITY ASSURANCESTATEMENT
Study Title: Analysis of Perfluorobutanesulfonate(PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate(PFOS) in Water, Soil, Sediment, Fish, Clams,
Vegetation, Small Mammal Liver and Small Mammal Serum Using LC/MS/MS for the 3M Decatur Monitoring Program Interim Study: Analysis of Water Samples from Northern Alabama PotableWater Systems Interim Study Identification Number: E05-0210 Interim Repom15
This study was audited by the 3M EnvironmentalLaboratory Quality Assurance Unit (QAU), as indicated in the following table. The findings were reported to the study director and laboratory management.
1-2, 2005
I DaWReport I Dec. 12,2005 I Dec. 12,2005 I
/d-al- O S
Date
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TABLE OF CONTENTS
GLP Compliance Statement ......................................................................................................................3 Quality Assurance Statement ....................................................................................................................4 Table of Contents .......................................................................................................................................5 List of Tables...............................................................................................................................................6 Study Information .......................................................................................................................................7 Summary and Introduction.........................................................................................................................8 Test Samples............................................................................................................................................10 Reference Substances.............................................................................................................................10 Control Substance....................................................................................................................................11 Method Summaries ..................................................................................................................................11
Sample Collection ........................................................................................................................11 Preparatory and Analytical Methods ...........................................................................................12 Extraction ......................................................................................................................................12 Analysis.........................................................................................................................................12 Analytical Results .....................................................................................................................................13 Calibration.....................................................................................................................................13 Limit of Quantitation (LOQ)..........................................................................................................13 Blanks ...........................................................................................................................................14 Solvent Blank................................................................................................................................14 Method Blank................................................................................................................................14 Trip Blank......................................................................................................................................15 System Suitability .........................................................................................................................15 Continuing Calibration..................................................................................................................15 Lab Control Spikes (LCSs) ..........................................................................................................15 Sample Duplicates .......................................................................................................................17 Surrogates ....................................................................................................................................17
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Field Matrix Spikes.......................................................................................................................17 Data Summary and Discussion ...............................................................................................................17 Statistical Methods and Calculations.......................................................................................................20
Accuracy and Precision Equations..............................................................................................20 Determination of Analytical Uncertainty ......................................................................................20 Statement of Conclusion..........................................................................................................................21 List of Attachments...................................................................................................................................21 Signature Page.........................................................................................................................................22
LIST OF TABLES
Table 1. Sample Results Summary. ............................................................................................................9 Table 2. Study Reference Substance. ...................................................................................................... 10 Table 3. Study Control Substance (Surrogate). ....................................................................................... 11 Table 4. Sample Collection Information.................................................................................................... 12 Table 5. Instrument Parameters................................................................................................................ 12 Table 6. Liquid Chromatography Gradient Program................................................................................ 13 Table 7. Mass Transitions.......................................................................................................................... 13 Table 8. Method Blank Area Counts......................................................................................................... 14 Table 9. Surrogate Spiked Method Blank Recoveries............................................................................. 14 Table 10. Lab Control Spike (LCS) Results.............................................................................................. 16 Table 11. Detailed Sample and QC Results............................................................................................. 18
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STUDY INFORMATION
Sponsor 3M Company
Sponsor Representative Michael A. Santoro 3M Company 3M Building 0236-01-B-10 St. Paul, MN 55144 Study Director Jaisimha Kesari, P.E., DEE Weston Solutions, Inc. 1400 Weston Way West Chester, PA 19380
3M Environmental Laboratory E05-0210 Interim Report#15
Study Location
Testing Facilities
Exygen Research 3058 Research Drive State College, PA 16801
3M Environmental Laboratory 3M Building 2-3E-09 935 Bush Avenue St. Paul, MN 55144
Study Dates Study Initiation: 11/5/2004 Interim Experimental Initiation: October 11, 2005 Interim Experimental Completion: October 28, 2005 Interim Study Completion: Date of interim report signing
Location of Archives All original raw data, protocol, and analytical report have been archived at the 3M Environmental Laboratory according to 40 CFR Part 792. The test substance and analytical reference standard reserve samples are archived at the 3M Environmental Laboratory according to 40 CFR Part 792.
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SUMMARY AND INTRODUCTION
The 3M Environmental Laboratory extracted and analyzed water samples collected from six Northern Alabama potable water systems by Weston Solutions personnel on October 4 and 5, 2005. Samples were submitted for analysis as part of 3M Environmental Laboratory project number E05-0210 (3M Decatur Fluorochemical GLP Monitoring Program, Interim Report #15: Analysis of Water Samples from Northern Alabama Potable Water Systems).
Water samples were analyzed for perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHS), and perfluorobutane sulfonate (PFBS) using 3M Environmental Laboratory Method ETS 8-154.1 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates in Water by Solid Phase Extractions and High Performance Liquid Chromatography/Mass Spectrometry" in accordance with Exygen Research Protocol P0001131 (Attachment C). ETS 8-154.1 falls under the 3M Environmental Laboratory's current ISO/IED 17025-1999 scope of accreditation and the results reported herein were complient with this accreditation. The analytical start date for this interim report was October 11, 2005 and the analytical termination date was October 28, 2005.
Sample containers were prepared at the 3M Environmental Laboratory. Sample containers for each sampling location included a field sample, field sample duplicate, low field spike (0.1 ng/mL) and high field spike (1.0 ng/mL). Each empty container was marked with a "fill to here" line and was fortified with a surrogate spike or an appropriate matrix spike solution containing the surrogate and the three target analytes prior to being sent to the field for sample collection. Table 1 below summarizes the sample results. The average between the sample and the sample duplicate is provided along with the relative percent difference (%RPD) if applicable. The limit of quantitation (LOQ) of PFBS, PFHS, and PFOS for the sample set was 0.0249 ng/mL, 0.0247 ng/mL, and 0.0247 ng/mL, respectively. All results for quality control samples prepared and analyzed with the samples will be reported and discussed elsewhere in this report.
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Table 1. Sample Results Summary.
3M LIMS ID E05-0210-89707 E05-0210-89708
E05-0210-89714 E05-0210-89715
E05-0210-89718 E05-0210-89719
E05-0210-89722 E05-0210-89723
E05-0210-89726 E05-0210-89727
E05-0210-89730 E05-0210-89731
Sample Description
DPWS PW FW01 0 051004 DPWS PW FW01 DB 051004
Average Sample/Sample Duplicate %RPD
WMEL PW FW01 0 051004 WMEL PW FW01 DB 051004
Average Sample/Sample Duplicate %RPD
MSTP PW FW01 0 051004 MSTP PW FW01 DB 051004
Average Sample/Sample Duplicate %RPD
FWTP PW FW01 0 051004 FWTP PW FW01 DB 051004
Average Sample/Sample Duplicate %RPD
TVATP PW FW01 0 051004 TVATP PW FW01 DB 051004
Average Sample/Sample Duplicate %RPD
SWTP PW FW01 0 051005 SWTP PW FW01 DB 051005
Average Sample/Sample Duplicate %RPD
(1)PFBS Concentration
(ng/mL)
<0.0249 <0.0249 <0.0249
(4)NA
0.0374 0.0383 (5)0.0378
2.4 <0.0249 <0.0249 <0.0249
(4)NA
<0.0249 <0.0249 <0.0249
(4)NA
<0.0249 <0.0249 <0.0249
(4)NA
<0.0249 <0.0249
<0.0249 (4)NA
(2)PFHS Concentration
(ng/mL)
<0.0247 <0.0247 <0.0247
(4)NA
<0.0247 <0.0247 <0.0247
(4)NA <0.0247 <0.0247 <0.0247
(4)NA
<0.0247 <0.0247 <0.0247
(4)NA
<0.0247 <0.0247 <0.0247
(4)NA
<0.0247 <0.0247
<0.0247 (4)NA
(3)PFOS Concentration
(ng/mL)
<0.0247 <0.0247 <0.0247
(4)NA
0.0616 0.0819 0.0718
28 0.0258 <0.0247 (5)0.0258
NA
<0.0247 <0.0247 <0.0247
(4)NA
<0.0247 <0.0247 <0.0247
(4)NA
0.0398 <0.0247 (5)0.0398
NA
(1) The analytical uncertainty of the PFBS resuts is 1006.2% based on method accuracy and precision. All results and averages are presented with three significant figures, %RPD to two significant figures. Sample concentrations, averages, and %RPD values may vary slightly from the raw data. Samples with concentrations less than the LOQ of 0.0249 ng/mL may have detectable amounts of PFBS present; however, quantified concentrations less than the established LOQ are not assigned.
(2) The analytical uncertainty of the PFHS resuts is 1004.5% based on method accuracy and precision. All results and averages are presented with three significant figures, %RPD to two significant figures. Sample concentrations, averages, and %RPD values may vary slightly from the raw data. Samples with concentrations less than the LOQ of 0.0247 ng/mL may have detectable amounts of PFHS present; however, quantified concentrations less than the established LOQ are not assigned.
(3) The analytical uncertainty of the PFOS resuts is 1009.7% based on method accuracy and precision. All results and averages are presented with three significant figures, %RPD to two significant figures. Sample concentrations, averages, and %RPD values may vary slightly from the raw data. Samples with concentrations less than the LOQ of 0.0247 ng/mL may have detectable amounts of PFOS present; however, quantified concentrations less than the established LOQ are not assigned.
(4) NA: Not applicable. %RPD values not determined when concentrations for the sample and/or sample duplicate are below the stated LOQ.
(5) The average value listed is the concentration for the sample or sample duplicate that produced a value above the LOQ. A true average and %RPD between the sample and sample duplicate was not determined.
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TEST SAMPLES
Water samples from six locations were received on October 6, 2005 from Tim Frinak of Weston Solutions, Inc. Twenty-seven containers were submitted for analysis. The samples were logged in by 3M Environmental Laboratory professional services personnel and placed in refrigerated storage prior to extraction on October 6, 2005.
REFERENCE SUBSTANCES
Table 2 lists the pertinent information regarding the reference substance used for this study. Table 2. Study Reference Substance.
Reference Substance
PFBS
PFHS
PFOS
Chemical Name
Perfluorobutanesulfonate
Perfluorohexanesulfonate
Perfluorooctanesulfonate
Chemical Formula
C4F9SO3-K+
C6F13SO3-K+
C8F17SO3K+
Identifier (1)Source Expiration Date Storage Conditions Chemical Lot Number TCR Number
CAS # 29420-49-3 3M
1/17/2007 Frozen
2 TCR-282 (99131-040)
CAS # 3871-99-6 3M
10/18/2006 Frozen
NB# 120067-69 TCR-83 (SE036)
CAS # 2795-39-3 3M
8/31/2006 Frozen 171 TCR-696
Physical Description
White Powder
White Powder
White powder
Purity (2)Solubility
(1)
97.3%
98.6%
54,400 ppm
No Information available
Documentation regarding synthesis of the test substances is located at the source.
86.4% 680 ppm
(2)
All test substances are believed to be soluble in water at the levels to be investigated. No visual
precipitates observed.
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CONTROL SUBSTANCE
PFOA [1,2 13C] was analyzed as a surrogate against a multi-level extracted calibration curve. A known amount of PFOA [1,2 13C] was spiked into each sample container in the laboratory prior to sample collection. Table 3 lists the pertinent information regarding the study control substance.
Table 3. Study Control Substance (Surrogate).
Control Substance
PFOA [1,2 13C]
Chemical Name Chemical Formula Identifier Source Expiration Date
Perfluorooctanoic Acid C6F15[13C]F2[13C]OOH
N/A Perkin Elmer 03/29/2009
Storage Conditions
Frozen
Chemical Lot Number TCR Number Physical Description Purity
3507-195 TCR-744 White powder
>97%
METHOD SUMMARIES
Sample Collection
Samples were collected on October 4-5, 2005 in non-rinsed NalgeneTM (low-density polyethylene) bottles prepared at the 3M Environmental Laboratory on October 3, 2005. Prior to sample collection, all bottles were spiked in the laboratory with a known volume of a surrogate solution or appropriate matrix spiking solution containing the surrogate and the three target analytes. Four collection bottles were associated with each individual sampling location: sample, sample duplicate, low level field matrix spike (LS), and high level field matrix spike (HS). Additionally, one "Trip Blank" sample set was prepared. A Trip Blank set consisted of three individual bottles: trip blank sample, trip blank low spike, and trip blank high spike. The surrogate and matrix spike levels for the trip blanks were the same as the samples. Table 4 details the spike amounts for the four bottles comprising the sample location set.
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Table 4. Sample Collection Information.
(1)Bottle Description
Nominal Final Volume Collected (mL)
Final Spike Concentration (ng/mL)
PFBS
PFHS
PFOS
PFOA [1,2 13C] (Surrogate)
Sample
450
NA
NA
NA
Sample Dup
450
NA
NA
NA
Low Field Matrix Spike (LS)
450
0.0998
0.0987
0.0992
High Field Matrix Spike (HS)
450
0.998
0.987
0.992
(1) The sample description was assigned in the field by Weston Solutions personnel.
0.500 0.500 0.0998 0.998
Preparatory and Analytical Methods
Extraction
All samples, calibration standards, and associated quality control samples were extracted using the procedure outlined in ETS-8-154.1 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates in Water by Solid Phase Extractions and High Performance Liquid Chromatography/Mass Spectrometry". Briefly, 40 mL of sample was loaded onto a pre-conditioned Waters C18 solid phase extraction (SPE) cartridge (Sep-Pak, 6 cc) using a vacuum manifold. The loaded cartridges were then eluted with 5 mL of methanol. This extraction procedure concentrates the samples by a factor of eight. (Initial volume = 40 mL, final volume = 5 mL).
Analysis
All sample and quality control extracts were analyzed for PFBS, PFHS, PFOS, and PFOA [1,2 13C] using high performance liquid chromatography/ tandem mass spectrometry (HPLC/MS/MS). Pertinent instrument parameters, the liquid chromatography gradient program, and the specific mass transitions analyzed are described in the tables below.
Table 5. Instrument Parameters
Instrument Name Liquid Chromatograph Guard column Analytical column Injection Volume Mass Spectrometer Electrode Ion Source Polarity Software
ETSOllie Agilent 1100 Betasil C18 (2.1 mm X 100 mm),, 5 m Betasil C18 (2.1 mm X 100 mm), 5 m
5 L Applied Biosystems API 4000 Q Trap
Z-spray Turbo Spray
Negative Analyst 1.4.1
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Table 6. Liquid Chromatography Gradient Program
Step Number
0 1 2 3 4 5
Total Time (min)
0 1.0 14.5 15.5 16.5 20.0
Flow Rate (L/min)
300 300 300 300 300 300
Percent A (2 mM ammonium
acetate)
80.0 80.0 10.0 10.0 80.0 80.0
Percent B (Methanol)
20.0 20.0 90.0 90.0 20.0 20.0
Table 7. Mass Transitions
Analyte (1)PFBS (1)PFHS (1)PFOS
PFOA [1,2 13C]
Mass Transition Q1/Q3 299/80 299/99 399/80 399/99 499/130 499/99 499/80 415/370
Dwell Time (msec)
100 100 100 100 100 100 100 100
(1) All three transitions were summed to produce a "total ion chromatogram" (TIC). The TIC was used for quantitation.
ANALYTICAL RESULTS
Calibration
Calibration standards were prepared by spiking known amounts of stock solutions containing PFBS, PFHS, PFOS, and PFOA [1,2 13C] into 40 mL of ASTM type I water. Each spiked water standard was then extracted in the same manner as the collected samples. A total of ten spiked standards ranging from 0.025 ng/mL to 25 ng/mL (nominal) were prepared. A quadratic, 1/x weighted, calibration curve was used to fit the data for each analyte. The data were not forced through zero during the fitting process. Calculating the standard concentration using the peak area counts and the resultant calibration curve confirmed accuracy of each curve point. Each extracted calibration standard used to generate the final calibration curve met the method calibration accuracy requirement of 10025% (10030% for the LOQ standard). Coefficients of determination (r2) were greater than 0.996 for all analytes.
Limit of Quantitation (LOQ)
The LOQ for this analysis, as defined in ETS-8-154.1, is the lowest non-zero calibration standard in the curve in which the area counts are twice those of the method blank(s). This will be presented and discussed in more detail in the section below regarding method blanks.
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Blanks
Three types of blanks were prepared and analyzed with the samples: method blanks, solvent blanks, and field/trip blanks. Each blank type is described below.
Solvent Blank Several methanol solvent blanks were analyzed to assess system contamination and/or instrument carryover. Analyte peak area counts in all solvent blank samples were less than half the area counts of the calibration standard used to establish the LOQ.
Method Blank Eight method blanks were prepared by loading 40 mL of ASTM Type I water onto a C18 SPE cartridge and eluting with 5 mL of methanol using the same extraction procedure as the samples. Method blanks were prepared to evaluate the levels of background contamination in the overall extraction process (glassware, SPE cartridges, etc.). Four of the method blanks prepared were spiked with a known amount of PFOA [1,2 13C] surrogate prior to extraction. Table 8 lists the analyte area counts for the method blanks and the corresponding LOQ standard. Surrogate recoveries for the spiked method blanks are presented in Table 9.
Table 8. Method Blank Area Counts.
PFBS
PFHS
PFOS
PFOA [1,2 13C] Surrogate
Sample ID
Sample Comment
Area Counts
MB-051011-1 Method Blank-1
8487
MB-051011-2 Method Blank-2
5792
MB-051011-3 Method Blank-3
6269
MB-051011-4 Method Blank-4
6884
MB-051011-5 Method Blank-5
7210
MB-051011-6 Method Blank-6
6501
MB-051011-7 Method Blank-7
7573
MB-051011-8 Method Blank-8
6964
2*Area Counts of Highest Method Blank
16974
Area Counts of the LOQ Standard
90226
LOQ Concentration
(0.0249 ng/mL)
(1) Method Blanks spiked with 1 ng/mL surrogate.
8788 8039 6871 9454 10691 7848 6191 6207 21382 82409 (0.0247 ng/mL)
40536
2255
41506
1284
37883
1377
33212 36261 42680 37869 31373 85360
985 (1)703106 (1)741777 (1)715325 (1)737959
(2)4510
123012
81116
(0.0247 ng/mL) (0.0998 ng/mL)
(2) Method Blanks spiked with surrogate were excluded from LOQ verification.
Table 9. Surrogate Spiked Method Blank Recoveries.
Sample Name
O051020a031 O051020a032 O051020a033 O051020a034
Sample ID
MB-051011-5 MB-051011-6 MB-051011-7 MB-051011-8
Spiked Concentration
(ng/mL)
1.015 1.015 1.015 1.015
Calculated Conc. (ng/mL)
0.919 0.972 0.935 0.966
%Recovery
90.5 95.8 92.1 95.2
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Trip Blank Prior to sample collection, one sample container was filled with 450 mL of ASTM Type I water, spiked with surrogate, sealed, and shipped to the sample collection site along with the empty containers. This sample was analyzed as the field/trip blank. The trip blank serves as an additional method blank that accounts for any storage conditions and/or holding time issues that the samples may experience. The resultant field blank concentrations for PFBS, PFHS, and PFOS for the field/trip blank were <0.0249 ng/mL, <0.0247 ng/mL, and <0.0247 ng/mL, respectively.
System Suitability
A 5.0 ppb (nominal concentration) extracted calibration standard was analyzed in triplicate at the beginning and end of the analytical sequence to demonstrate overall system suitability. For all analytes, the relative standard deviation (RSD) of the analyte peak area counts and the RSD of the peak retention times were less than 5% and 2%, respectively, which met method criteria.
Continuing Calibration
During the course of the analytical sequence, several continuing calibration verification samples (CCVs) were analyzed to confirm that the instrument response and the initial calibration curve were still in control. ETS-8-154.1 states that all CCV recoveries must be within 25% for the data to be acceptable. All CCV recoveries met method criteria of 25% for all analytes.
Lab Control Spikes (LCSs)
Replicate low (0.25 ng/mL nominal concentration) and high (7.5 ng/mL nominal concentration) lab control spikes were prepared and extracted on the same day as the samples. LCSs were prepared by spiking known amounts of the analytes into 40 mL of ASTM Type I water to produce the desired concentration. The spiked water samples were extracted and analyzed in the same manner as the samples. Individual LCS results, along with the average and percent RSD, for the extraction set are presented in the data table below. LCS recoveries for all analytes met method criteria for both accuracy and precision.
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Table 10. Lab Control Spike (LCS) Results.
(1)PFBS
(1)PFHS
(1)PFOS
(1)PFOA [1,2 13C]
Sample Description
Lab ID
Spiked Conc. (ng/mL)
Calc. Conc. (ng/mL)
% Recovery
Spiked Conc. (ng/mL)
Calc. Conc. (ng/mL)
% Recovery
Spiked Conc. (ng/mL)
Calc. Conc. (ng/mL)
% Recovery
Spiked Conc. (ng/mL)
Calc. Conc. (ng/mL)
% Recovery
0.25 ppb LCS LCS-051011-1
0.249
0.254
102
0.247
0.241
97.6
0.248
0.221
89.1
0.249
0.239
96.0
0.25 ppb LCS LCS-051011-2
0.249
0.249
100.0
0.247
0.244
98.8
0.248
0.227
91.5
0.249
0.238
95.6
0.25 ppb LCS LCS-051011-3
0.249
0.259
104
0.247
0.242
98.0
0.248
0.233
94.0
0.249
0.274
110
7.5 ppb LCS LCS-051011-4
7.48
6.97
93.2
7.40
6.97
94.2
7.44
6.92
93.0
7.48
6.75
90.2
7.5 ppb LCS LCS-051011-5
7.48
7.18
96.0
7.40
7.32
98.9
7.44
7.32
98.4
7.48
6.36
85.0
7.5 ppb LCS LCS-051011-6
7.48
7.04
94.1
7.40
7.14
96.5
7.44
7.07
95.0
7.48
7.10
94.9
Average %Recovery %RSD
98.2%4.5%
97.2%1.8%
93.5%3.4%
95.2%8.8%
(1) Table displays rounded values for all concentration and percent recovery values (3 significant figures). %RSD values reported to two significant figures. Recovery and %RSD values
may vary slightly from the values in the raw data.
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Sample Duplicates
Because a field sample duplicate (separate container) was collected at each sampling location, duplicate/replicate extractions of a given sample were not performed. Overall method precision was determined using LCSs.
Surrogates
Although not specified in the ETS 8-154.1, PFOA [1,2 13C] was added to all samples and sample spikes as a surrogate to evaluate overall method performance. The final PFOA [1,2 13C] concentration for samples and sample duplicates was 0.500 ng/mL. Surrogate recoveries are reported in the next section with sample data and will be discussed in further detail in the Data Summary and Discussion section below.
Field Matrix Spikes
Low (nominal concentration of 0.1 ng/mL) and high (nominal concentration 1.0 ng/mL) field matrix spikes were collected at each sampling point to verify that the analytical method is applicable to the collected matrix. Field matrix spike recoveries within 10030% confirm that "unknown" components in the sample matrix do not interfere with the extraction and analysis of the analytes of interest. Field matrix spikes will be presented in the next section with the sample data.
DATA SUMMARY AND DISCUSSION
Table 11 below summarizes the sample results, field matrix spike recoveries, and surrogate spike recoveries for all of the sampling locations plus the trip blank.
Matrix spike recoveries for PFBS, PFHS, and PFOS were within method acceptance criteria of 10030% for all sampling locations with one exception. E05-0210-89716 (low level PFOS matrix spike associated with WMEL PW FW01) produced a recovery of 54.7%. However, the recovery of the high level matrix spike associated with location was 90.1%. Because the high level spike met method criteria, the sample results have been reported and are considered accurate within the stated method accuracy of 10030%. PFOA[1,2 13C] surrogate recoveries for sample/sample duplicate measurements ranged from 32.6% to 40.4%. The low and high field matrix spike surrogate recovery ranged from 18.2% to 35.2%. At this time, there is no explanation for the low surrogate recoveries. The 3M Environmental Laboratory will be investigating this in detail in a future study. Reported PFBS, PFHS,and PFOS sample concentrations have NOT been corrected for surrogate recovery as the field matrix spikes of the target analyte were within 10030%.
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3M Environmental Laboratory E05-0210 Interim Report#15
Table 11. Detailed Sample and QC Results.
3M LIMS ID E05-0210-89707 E05-0210-89708 E05-0210-89709 E05-0210-89710
E05-0210-89714 E05-0210-89715 E05-0210-89716 E05-0210-89717
E05-0210-89718 E05-0210-89719 E05-0210-89720 E05-0210-89721
E05-0210-89722 E05-0210-89723 E05-0210-89724 E05-0210-89725
Description
DPWS PW FW01 0 051004 DPWS PW FW01 DB 051004 DPWS PW FW01 LS 051004 DPWS PW FW01 HS 051004
Average %RPD
WMEL PW FW01 0 051004 WMEL PW FW01 DB 051004 WMEL PW FW01 LS 051004 WMEL PW FW01 HS 051004
Average %RPD
MSTP PW FW01 0 051004 MSTP PW FW01 DB 051004 MSTP PW FW01 LS 051004 MSTP PW FW01 HS 051004
Average %RPD
FWTP PW FW01 0 051004 FWTP PW FW01 DB 051004 FWTP PW FW01 LS 051004 FWTP PW FW01 HS 051004
Average %RPD
(1)PFBS Conc. (ng/mL)
<0.0249 <0.0249 0.0991
1.02 (4)<0.0249
NA
0.0374 0.0383 0.137
1.06 0.0378
2.4
<0.0249 <0.0249
0.115 1.05 <0.0249 (4)NA
<0.0249 <0.0249
0.121 1.05 <0.0249 (4)<NA
PFBS %Recovery
NA NA 99.3 102
NA NA 99.3 102
NA NA 115 105
NA NA 121 105
(2)PFHS Conc. (ng/mL)
<0.0247 <0.0247 0.0963
0.975 (4)<0.0247
NA
<0.0247 <0.0247
0.100 0.942 <0.0247 (4)NA
<0.0247 <0.0247 0.0985
0.936 <0.0247
(4)NA
<0.0247 <0.0247 0.0955
0.959 <0.0247 (4)<NA
PFHS %Recovery
NA NA 97.6 98.8
NA NA 101 95.4
NA NA 99.8 94.8
NA NA 96.8 97.2
(3)PFOS Conc. (ng/mL)
<0.0247 <0.0247 0.0933
0.908 (4)<0.0247
NA
0.0616 0.0819 0.126 0.966 0.0718
28
0.0258 <0.0247
0.131 0.892 0.0258 (5)NA
<0.0247 <0.0247
0.109 0.942 <0.0247 (4)<NA
PFOS %Recovery
NA NA 94.1 91.5
NA NA 54.7 90.1
NA NA 106 87.3
NA NA 110 95.0
Surrogate Conc. (ng/mL) 0.182 0.186 0.0351 0.202
0.181 0.169 0.0239 0.199
0.174 0.196 0.0288 0.223
0.202 0.184 0.0326 0.196
PFOA [1,2 13C] %Recovery 36.4 37.2 35.2 20.2
36.1 33.8 23.9 19.9
34.8 39.2 28.8 22.3
40.4 36.8 32.7 19.6
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3M Environmental Laboratory E05-0210 Interim Report#15
Table 11. Continued.
3M LIMS ID E05-0210-89726 E05-0210-89727 E05-0210-89728 E05-0210-89729
E05-0210-89730 E05-0210-89731 E05-0210-89732 E05-0210-89733
E05-0210-89711 E05-0210-89712 E05-0210-89713
Description TVATP PW FW01 0 051004 TVATP PW FW01 DB 051004 TVATP PW FW01 LS 051004 TVATP PW FW01 HS 051004
Average %RPD
SWTP PW FW01 0 051005 SWTP PW FW01 DB 051005 SWTP PW FW01 LS 051005 SWTP PW FW01 HS 051005
Average %RPD
DPWS PW Trip 0 051004 DPWS PW Trip LS 051004 DPWS PW Trip HS 051004
(1)PFBS Conc. (ng/mL)
<0.0249 <0.0249
0.121 1.00 <0.0249 (4)NA
<0.0249 <0.0249
0.112 0.985 <0.0249 (4)NA
< 0.0249 0.0929
1.02
PFBS %Recovery
NA NA 121 100
NA NA 112 98.7
NA 93.1 102
(2PFHS Conc. (ng/mL)
<0.0247 <0.0247 0.0908
0.912 <0.0247
(4)NA
<0.0247 <0.0247 0.0902
0.916 <0.0247
(4)NA
< 0.0247 0.0900 0.964
PFHS %Recovery
NA NA 92.0 92.4
NA NA 91.4 92.8
NA 91.2 97.7
(3)PFOS Conc. (ng/mL)
<0.0247 <0.0247
0.110 0.882 <0.0247 (4)NA
0.0398 <0.0247 0.0967
0.892 0.0398 (5)NA
< 0.0247 0.0743 0.904
PFOS %Recovery
NA NA 111 88.9
Surrogate Conc. (ng/mL)
0.175 0.186 0.0301 0.220
PFOA [1,2 13C] %Recovery
35.0 37.2 30.2 22.0
NA
0.194
38.8
NA
0.172
34.4
97.6
0.0296
29.6
89.9
0.182
18.2
NA
0.163
32.6
75.0
0.0247
24.7
91.1
0.192
19.2
(1) The analytical uncertainty of the PFBS resuts is 1006.2% based on method accuracy and precision. All results and averages are presented with three significant figures, %RPD to two significant figures. Sample concentrations, averages, and %RPD values may vary slightly from the raw data.
(2) The analytical uncertainty of the PFHS resuts is 1004.5% based on method accuracy and precision. All results and averages are presented with three significant figures, %RPD to two significant figures. Sample concentrations, averages, and %RPD values may vary slightly from the raw data.
(3) The analytical uncertainty of the PFOS resuts is 1009.7% based on method accuracy and precision. All results and averages are presented with three significant figures, %RPD to two significant figures. Sample concentrations, averages, and %RPD values may vary slightly from the raw data.
(4) NA: Not applicable. %RPD values not determined when concentrations for the sample and sample duplicate are below the stated LOQ.
(5) The average value listed is the concentration for the sample or sample duplicate that produced a value above the LOQ. A true average and %RPD between the sample and sample duplicate was not determined.
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3M Environmental Laboratory E05-0210 Interim Report#15
STATISTICAL METHODS AND CALCULATIONS
Statistical methods used to interpret sample results include averages and standard deviations. The Analyst software program calculated sample concentrations using resultant analyte peak areas and the established quadratic, 1/x weighted, calibration curve. None of the samples analyzed for this interim report required dilution. Sample calculations and equations used to report method accuracy and precision are described below.
Accuracy and Precision Equations
LCS/Surrogate Percent Recovery = Calculated Concentration * 100% Spike Concentration
Sample Spike Recovery = (Spiked Sample Concentration - Average Concentration : Field Sample & Field Sample Dup.) * 100% Spike Concentraton
% RSD (Relative Standard Deviation) = standard deviation of replicates * 100% replicate average
% RPD (Relative Percent Difference) = Absolute difference between sample duplicates * 100% average sample concentration
Determination of Analytical Uncertainty
Both the accuracy (percent recovery) and precision (%RSD) of the lab control spikes are used to estimate the analytical uncertainty for a given analyte. The measured precision (%RSD) is then used to determine the range of the accuracy. The example below shows how the analytical uncertainty for PFOS was determined for this sample set.
Example: 93.50 (accuracy)*0.03374 (precision)=3.155 (accuracy range) 93.50+ 3.155=96.66; 93.50- 3.155 = 90.35
Thus, LCS accuracy results range from 90.35% to 96.66%. The absolute difference of the low and high ends of this range, when compared to 100%, are then calculated.
100%-96.66% = 3.34% 100%-90.35%= 9.65%. The most conservative (largest) absolute difference is then used as the analytical uncertainty for the given analyte. Therefore, the analytical uncertainty for PFOS as defined here, is given as 1009.7% for the data associated with this project. Using this same approach, the analytical uncertainties for PFBS and PFHS were determined to be 1006.2% and 1004.5%, respectively.
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3M Environmental Laboratory E05-0210 Interim Report#15
STATEMENT OF CONCLUSION
PFBS, PFHS, and PFOS results for this project were presented in Table 1. Laboratory control spikes were used to determine the method accuracy and precision for the three target analytes for this data set. The accuracy and precision were then used to estimate the analytical uncertainty for the results (PFBS 1006.2%, PFHS 1004.5%, and PFOS 1009.7%). Recoveries of field matrix spiked samples demonstrated that the overall analytical method was appropriate for the matrix collected. Consequently, sample results are considered accurate to within 10030%.
LIST OF ATTACHMENTS
Attachment A: Sample Chromatograms and Calibration Curves Attachment B: Extraction and Analytical Methods Attachment C: Protocol and Protocol Amendments
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3M Environmental Laboratory 05-0210 Interim Reporn15
SIGNATURPEAGE
We certify that this report is a true and complete representationof the data for this study:
Jaisimha Kesari, P.E., DEE,
Study Director
Date
'William K. Reagen, Ph.D., Michael A. Santoro
3M Environmental Laboratory Manager Date
Sponsor Representative
' ' Date
05-0210 Interim Repom15
Northern Alabama Potable Water Systems
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3M Environmental Laboratory E05-0210 Interim Report#15
ATTACHMENT A: SAMPLE CHROMATOGRAMS AND CALIBRATION CURVES
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*Ollie U00110402
Results Name: o051020a.rdb
Sample Name: "O051020a020" Sample ID: "EC-051011-006" File: "o051020a.wiff"
Peak Name: "pfbs (tic)" Mass(es): "298.9/98.9 amu,298.9/79.9 amu"
Comment: "1.0 ppb extracted curve point" Annotation: ""
Sample Index:
20
Sample Type:
Standard
Concentration:
0.998
ng/mL
4.4e5
Calculated Conc:
1.06
ng/mL
Acq. Date: Acq. Time:
10/20/2005 08:25:21 AM
4.3e5
Modified:
No
Proc. Algorithm: IntelliQuan - IQA
Min. Peak Height: 0.00 cps
Min. Peak Width:
0.00 sec
Smoothing Width: 3
points
RT Window:
30.0
sec
Expected RT:
10.8 min
Use Relative RT:
No
Int. Type:
Valley
Retention Time:
10.8 min
Area:
3384359 counts
Height:
441048 cps
Start Time:
10.6 min
End Time:
11.2 min
4.2e5 4.1e5 4.0e5 3.9e5 3.8e5 3.7e5 3.6e5 3.5e5
10.79
3.4e5
3.3e5
3.2e5
3.1e5
3.0e5
2.9e5
2.8e5
2.7e5
2.6e5
2.5e5
2.4e5
Intensity, cps
2.3e5
2.2e5
2.1e5
2.0e5
1.9e5
1.8e5
1.7e5
1.6e5
1.5e5
1.4e5
1.3e5
1.2e5
1.1e5
1.0e5
9.0e4
8.0e4
7.0e4
6.0e4
5.0e4
4.0e4
3.0e4
2.0e4
1.0e4
0.0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Time, min
Printing Date: Tuesday, November 29, 2005
Page 20 of 88
Printing Time: 09:40:15 AM
*Ollie U00110402
Results Name: o051020a.rdb
Sample Name: "O051020a028" Sample ID: "MB-051011-2" File: "o051020a.wiff"
Peak Name: "pfbs (tic)" Mass(es): "298.9/98.9 amu,298.9/79.9 amu"
Comment: "Method Blank-2" Annotation: ""
Sample Index:
28
Sample Type:
Unknown
Concentration:
N/A
Calculated Conc:
< 0
Acq. Date:
10/20/2005
5500 5400
Acq. Time:
11:13:04 AM
5300
11.93
Modified:
No
Proc. Algorithm: IntelliQuan - IQA
Min. Peak Height: 0.00 cps
Min. Peak Width:
0.00 sec
Smoothing Width: 3
points
RT Window:
30.0
sec
Expected RT:
10.8 min
Use Relative RT:
No
5200 5100 5000 4900 4800
Int. Type: Retention Time: Area: Height: Start Time: End Time:
Valley 10.8 min
5792 counts 695 cps 10.7 min 11.0 min
4700 4600 4500 4400
4300
4200
4100
4000
3900
3800
3700
3600
3500
3400
3300
3200
3100
3000
Intensity, cps
2900
2800
2700
2600
2500
2400
2300
2200
2100
2000
0.88
1900 1800
17.13
1700
1600
1500
1400
1300
1200
1100
1000
900
10.79
800
18.94
700 16.44 18.64
600
15.70 16.25
18.44
500
12.73 13.68 13.96
18.03
19.16
400
12.94
14.95 15.22
300
200
100
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Time, min
Printing Date: Tuesday, November 29, 2005 Printing Time: 09:40:15 AM
Page 28 of 88
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*Ollie U00110402
Results Name: o051020a.rdb
Sample Name: "O051020a040" Sample ID: "LCS-051011-3" File: "o051020a.wiff"
Peak Name: "pfbs (tic)" Mass(es): "298.9/98.9 amu,298.9/79.9 amu"
Comment: "0.25 ppb Lab Control Spike" Annotation: ""
Sample Index:
40
Sample Type:
QC
Concentration: Calculated Conc:
0.249 0.259
ng/mL ng/mL
1.14e5
Acq. Date:
10/20/2005
1.12e5
Acq. Time:
03:41:17 PM
1.10e5
10.83
Modified:
No
Proc. Algorithm: IntelliQuan - IQA
Min. Peak Height: 0.00 cps
Min. Peak Width:
0.00 sec
Smoothing Width: 3
points
RT Window:
30.0
sec
Expected RT:
10.8 min
Use Relative RT:
No
1.08e5 1.06e5 1.04e5 1.02e5 1.00e5
Int. Type:
Valley
Retention Time:
10.8 min
Area:
861582 counts
Height:
114548 cps
Start Time:
10.6 min
End Time:
11.2 min
9.80e4 9.60e4 9.40e4 9.20e4 9.00e4
8.80e4
8.60e4
8.40e4
8.20e4
8.00e4
7.80e4
7.60e4
7.40e4
7.20e4
7.00e4
6.80e4
6.60e4
6.40e4
6.20e4
Intensity, cps
6.00e4
5.80e4
5.60e4
5.40e4
5.20e4
5.00e4
4.80e4
4.60e4
4.40e4
4.20e4
4.00e4
3.80e4
3.60e4
3.40e4
3.20e4
3.00e4
2.80e4
2.60e4
2.40e4
2.20e4
2.00e4
1.80e4
1.60e4
1.40e4
1.20e4
1.00e4
8000.00
6000.00
4000.00
2000.00
0.00
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Time, min
Printing Date: Tuesday, November 29, 2005 Printing Time: 09:40:15 AM
Page 40 of 88
*Ollie U00110402
Results Name: o051020a.rdb
Sample Name: "O051020a044" Sample ID: "E05-0210-89707" File: "o051020a.wiff"
Peak Name: "pfbs (tic)" Mass(es): "298.9/98.9 amu,298.9/79.9 amu"
Comment: "DPWS PW FW01 0 051004" Annotation: ""
Sample Index:
44
Sample Type:
Unknown
Concentration: Calculated Conc:
N/A < 0
3500
Acq. Date: Acq. Time:
10/20/2005 05:05:11 PM
3400
Modified:
No
Proc. Algorithm: IntelliQuan - IQA
Min. Peak Height: 0.00 cps
Min. Peak Width:
0.00 sec
Smoothing Width: 3
points
RT Window:
30.0
sec
Expected RT:
10.8 min
Use Relative RT:
No
Int. Type: Retention Time: Area: Height: Start Time: End Time:
Valley 10.8 min
27251 counts 3450 cps 10.6 min 11.1 min
3300 3200 3100 3000 2900 2800
2700
2600
2500
2400
2300
2200
2100
2000
1900
Intensity, cps
1800
1700
1600
1500
1400
1300
1200
1100
1000
900
800
700
600
500
400
300
200
100
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Time, min
Printing Date: Tuesday, November 29, 2005
Page 44 of 88
Printing Time: 09:40:15 AM
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*Ollie U00110402
Results Name: o051020a.rdb
Sample Name: "O051020a046" Sample ID: "E05-0210-89709" File: "o051020a.wiff" Peak Name: "pfbs (tic)" Mass(es): "298.9/98.9 amu,298.9/79.9 amu"
Comment: "DPWS PW FW01 LS 051004" Annotation: ""
Sample Index:
46
Sample Type:
Unknown
Concentration:
N/A
Calculated Conc: 0.0991
ng/mL
4.6e4
Acq. Date: Acq. Time:
10/20/2005 05:47:07 PM
4.5e4
Modified:
No
4.4e4
Proc. Algorithm: IntelliQuan - IQA Min. Peak Height: 0.00 cps
4.3e4
Min. Peak Width:
0.00 sec
Smoothing Width: 3
points
4.2e4
RT Window: Expected RT:
30.0
sec
10.8 min
4.1e4
Use Relative RT:
No
4.0e4
Int. Type:
Valley
Retention Time:
10.8 min
Area:
350907 counts
Height:
46057 cps
Start Time:
10.7 min
End Time:
11.1 min
3.9e4 3.8e4 3.7e4 3.6e4
10.83
3.5e4
3.4e4
3.3e4
3.2e4
3.1e4
3.0e4
2.9e4
2.8e4
2.7e4
2.6e4
2.5e4
Intensity, cps
2.4e4
2.3e4
2.2e4
2.1e4
2.0e4
1.9e4
1.8e4
1.7e4
1.6e4
1.5e4
1.4e4
1.3e4
1.2e4
1.1e4
1.0e4
9000.0
8000.0
7000.0
6000.0
5000.0
4000.0
3000.0 0.87
17.08
2000.0
11.99
16.45
1000.0 0.0
2.40 2.85
8.32
8.95
12.62 13.27 13.98 14.39 14.95 15.08 15.47 15.88
18.04 18.22
19.08 19.37
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Time, min
Printing Date: Tuesday, November 29, 2005
Page 46 of 88
Printing Time: 09:40:15 AM
*Ollie U00110402
Results Name: o051020a.rdb
o051020a.rdb (pfbs (tic)): "Quadratic" Regression ("1 / x" weighting): y = -4.83e+004 x^2 + 3.22e+006 x + 3.24e+004 (r = 0.9996)
5.0e7
4.8e7
4.6e7
4.4e7
4.2e7
4.0e7
3.8e7
3.6e7
3.4e7
3.2e7
3.0e7
Area, counts
2.8e7
2.6e7
2.4e7
2.2e7
2.0e7
1.8e7
1.6e7
1.4e7
1.2e7
1.0e7
8.0e6
6.0e6
4.0e6
2.0e6
0.0
0
1
2
3
4
5
6
7
8
9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25
Concentration, ng/mL
Printing Date: Tuesday, November 29, 2005 Printing Time: 09:43:07 AM
Page 1 of 1
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*Ollie U00110402
Results Name: o051020a.rdb
Sample Name: "O051020a020" Sample ID: "EC-051011-006" File: "o051020a.wiff"
Peak Name: "pfhs (tic)" Mass(es): "398.9/98.9 amu,398.9/80.0 amu,398.9/129.9 amu"
Comment: "1.0 ppb extracted curve point" Annotation: ""
Sample Index:
20
Sample Type:
Standard
Concentration:
0.987
ng/mL
Calculated Conc:
1.00
ng/mL
Acq. Date: Acq. Time:
10/20/2005 08:25:21 AM
3.5e5
Modified:
No
Proc. Algorithm: IntelliQuan - MQII
Noise Percentage:
50
Base. Sub. Window:
1.00 min
Peak-Split. Factor: 7
Report Largest Peak: No
Min. Peak Height:
0.00 cps
Min. Peak Width:
0.00 sec
Smoothing Width:
3
points
RT Window:
30.0
sec
Expected RT:
13.2 min
Use Relative RT:
No
3.4e5 3.3e5 3.2e5 3.1e5 3.0e5
Int. Type:
Base To Base
Retention Time:
13.2 min
Area:
3017176 counts
Height:
359590 cps
Start Time:
12.8 min
End Time:
13.6 min
2.9e5 2.8e5 2.7e5
13.24
2.6e5
2.5e5
2.4e5
2.3e5
2.2e5
2.1e5
2.0e5
1.9e5
Intensity, cps
1.8e5
1.7e5
1.6e5
1.5e5
1.4e5
1.3e5
1.2e5
1.1e5
1.0e5
9.0e4
8.0e4
7.0e4
6.0e4
13.03
5.0e4
4.0e4
3.0e4
2.0e4
1.0e4
0.0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Time, min
Printing Date: Tuesday, November 29, 2005
Page 20 of 88
Printing Time: 09:35:05 AM
*Ollie U00110402
Results Name: o051020a.rdb
Sample Name: "O051020a028" Sample ID: "MB-051011-2" File: "o051020a.wiff"
Peak Name: "pfhs (tic)" Mass(es): "398.9/98.9 amu,398.9/80.0 amu,398.9/129.9 amu"
Comment: "Method Blank-2" Annotation: ""
Sample Index:
28
Sample Type:
Unknown
Concentration:
N/A
Calculated Conc:
< 0
Acq. Date:
10/20/2005
2600
Acq. Time:
11:13:04 AM
2550
13.98
Modified:
No
Proc. Algorithm: IntelliQuan - MQII
Noise Percentage:
50
Base. Sub. Window:
1.00 min
Peak-Split. Factor: 7
Report Largest Peak: No
Min. Peak Height:
0.00 cps
Min. Peak Width:
0.00 sec
Smoothing Width:
3
points
RT Window:
30.0
sec
Expected RT:
13.2 min
Use Relative RT:
No
2500 2450 2400 2350 2300 2250 2200
Int. Type: Retention Time: Area: Height: Start Time: End Time:
Base To Base 13.3 min
8039 counts 990 cps 13.0 min 13.4 min
2150 2100 2050 2000
1950
1900
1850
1800
1750
1700
1650
1600
1550
1500
1450
1400
Intensity, cps
1350
1300
1250
1200
1150
1100
1050 1000
13.25
950
900
850
18.74
800 18.85
750
700
650
600
0.90
550
500
450
18.56
400
350
300
14.78
16.33
250
200
15.40 15.77
17.03 17.68 18.14
150
13.10
100
50
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Time, min
Printing Date: Tuesday, November 29, 2005
Page 28 of 88
Printing Time: 09:38:26 AM
E05-0210 Interim Report#15
Northern Alabama Potable Water Systems
Page 27 of 123
3M Environmental Laboratory E05-0210 Interim Report#15
*Ollie U00110402
Results Name: o051020a.rdb
Sample Name: "O051020a040" Sample ID: "LCS-051011-3" File: "o051020a.wiff"
Peak Name: "pfhs (tic)" Mass(es): "398.9/98.9 amu,398.9/80.0 amu,398.9/129.9 amu"
Comment: "0.25 ppb Lab Control Spike" Annotation: ""
Sample Index:
40
Sample Type:
QC
Concentration:
0.247
ng/mL
Calculated Conc: 0.242
ng/mL
8.8e4
Acq. Date:
10/20/2005
Acq. Time:
03:41:17 PM
8.6e4
13.30
Modified:
No
Proc. Algorithm: IntelliQuan - MQII
Noise Percentage:
50
Base. Sub. Window:
1.00 min
Peak-Split. Factor: 7
Report Largest Peak: No
Min. Peak Height:
0.00 cps
Min. Peak Width:
0.00 sec
Smoothing Width:
3
points
RT Window:
30.0
sec
Expected RT:
13.2 min
Use Relative RT:
No
8.4e4 8.2e4 8.0e4 7.8e4 7.6e4 7.4e4
Int. Type:
Base To Base
Retention Time:
13.3 min
Area:
750145 counts
Height:
89074 cps
Start Time:
12.9 min
End Time:
13.6 min
7.2e4 7.0e4 6.8e4 6.6e4
6.4e4
6.2e4
6.0e4
5.8e4
5.6e4
5.4e4
5.2e4
5.0e4
4.8e4
Intensity, cps
4.6e4
4.4e4
4.2e4
4.0e4
3.8e4
3.6e4
3.4e4
3.2e4
3.0e4
2.8e4
2.6e4
2.4e4
2.2e4
2.0e4
1.8e4
1.6e4 1.4e4
13.08
1.2e4
1.0e4
8000.0
6000.0
4000.0
2000.0
0.0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Time, min
Printing Date: Tuesday, November 29, 2005
Page 40 of 88
Printing Time: 09:38:27 AM
*Ollie U00110402
Results Name: o051020a.rdb
Sample Name: "O051020a044" Sample ID: "E05-0210-89707" File: "o051020a.wiff" Peak Name: "pfhs (tic)" Mass(es): "398.9/98.9 amu,398.9/80.0 amu,398.9/129.9 amu" Comment: "DPWS PW FW01 0 051004" Annotation: ""
Sample Index:
44
Sample Type:
Unknown
Concentration:
N/A
Calculated Conc: 0.00310
ng/mL
Acq. Date:
10/20/2005
3500
Acq. Time:
05:05:11 PM
3400
Modified:
No
Proc. Algorithm: IntelliQuan - MQII
Noise Percentage:
50
3300
Base. Sub. Window:
1.00 min
Peak-Split. Factor: 7 Report Largest Peak: No
3200
Min. Peak Height: Min. Peak Width:
0.00 cps 0.00 sec
3100
Smoothing Width:
3
points
RT Window: Expected RT:
30.0
sec
13.2 min
3000
Use Relative RT:
No
Int. Type:
Base To Base
2900
Retention Time:
13.3 min
Area:
29054 counts
2800
Height:
3510 cps
Start Time: End Time:
12.9 min 13.5 min
2700
2600
2500
2400
2300
2200
2100
2000
1900
Intensity, cps
1800
1700
1600
1500
1400
1300
1200
1100
1000
900
800
700
600
500
400
300
200
100
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Time, min
Printing Date: Tuesday, November 29, 2005
Page 44 of 88
Printing Time: 09:38:27 AM
E05-0210 Interim Report#15
Northern Alabama Potable Water Systems
Page 28 of 123
3M Environmental Laboratory E05-0210 Interim Report#15
*Ollie U00110402
Results Name: o051020a.rdb
Sample Name: "O051020a046" Sample ID: "E05-0210-89709" File: "o051020a.wiff"
Peak Name: "pfhs (tic)" Mass(es): "398.9/98.9 amu,398.9/80.0 amu,398.9/129.9 amu"
Comment: "DPWS PW FW01 LS 051004" Annotation: ""
Sample Index:
46
Sample Type:
Unknown
Concentration:
N/A
Calculated Conc: 0.0963
ng/mL
3.8e4
Acq. Date: Acq. Time:
10/20/2005 05:47:07 PM
3.7e4
Modified:
No
Proc. Algorithm: IntelliQuan - MQII
Noise Percentage:
50
Base. Sub. Window:
1.00 min
Peak-Split. Factor: 7
Report Largest Peak: No
Min. Peak Height:
0.00 cps
Min. Peak Width:
0.00 sec
Smoothing Width:
3
points
RT Window:
30.0
sec
Expected RT:
13.2 min
Use Relative RT:
No
Int. Type:
Base To Base
Retention Time:
13.3 min
Area:
311275 counts
Height:
38160 cps
Start Time:
12.8 min
End Time:
13.5 min
3.6e4 3.5e4 3.4e4 3.3e4 3.2e4 3.1e4 3.0e4 2.9e4
2.8e4
13.28
2.7e4
2.6e4
2.5e4
2.4e4
2.3e4
2.2e4
2.1e4
Intensity, cps
2.0e4
1.9e4
1.8e4
1.7e4
1.6e4
1.5e4
1.4e4
1.3e4
1.2e4
1.1e4
1.0e4
9000.0
8000.0
7000.0 6000.0
13.08
5000.0
4000.0
3000.0
2000.0
18.85
1000.0
0.88
14.01
17.08
14.43
15.40 16.11 16.36
17.46 17.63
19.23
0.0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Time, min
Printing Date: Tuesday, November 29, 2005
Page 46 of 88
Printing Time: 09:38:27 AM
*Ollie U00110402
Results Name: o051020a.rdb
o051020a.rdb (pfhs (tic)): "Quadratic" Regression ("1 / x" weighting): y = -3.67e+004 x^2 + 3.03e+006 x + 1.97e+004 (r = 0.9998)
5.3e7 5.2e7
5.0e7
4.8e7
4.6e7
4.4e7
4.2e7
4.0e7
3.8e7
3.6e7
3.4e7
3.2e7
3.0e7
Area, counts
2.8e7
2.6e7
2.4e7
2.2e7
2.0e7
1.8e7
1.6e7
1.4e7
1.2e7
1.0e7
8.0e6
6.0e6
4.0e6
2.0e6
0.0
0
1
2
3
4
5
6
7
8
9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24
Concentration, ng/mL
Printing Date: Tuesday, November 29, 2005 Printing Time: 09:43:43 AM
Page 1 of 1
E05-0210 Interim Report#15
Northern Alabama Potable Water Systems
Page 29 of 123
3M Environmental Laboratory E05-0210 Interim Report#15
*Ollie U00110402
Results Name: o051020a.rdb
Sample Name: "O051020a020" Sample ID: "EC-051011-006" File: "o051020a.wiff" Peak Name: "pfos (tic)" Mass(es): "498.8/98.9 amu,498.8/80.0 amu,498.8/129.9 amu" Comment: "1.0 ppb extracted curve point" Annotation: ""
Sample Index:
20
Sample Type:
Standard
Concentration: Calculated Conc:
0.992 0.960
ng/mL ng/mL
2.8e5
Acq. Date: Acq. Time:
10/20/2005 08:25:21 AM
2.8e5 2.7e5
Modified:
No
Proc. Algorithm: IntelliQuan - MQII
2.7e5
Noise Percentage:
50
Base. Sub. Window:
1.00 min
Peak-Split. Factor: 8
2.6e5 2.6e5
Report Largest Peak: No
Min. Peak Height:
0.00 cps
2.5e5
Min. Peak Width: Smoothing Width: RT Window:
0.00 sec
3
points
30.0
sec
2.5e5 2.4e5
Expected RT: Use Relative RT:
14.7 min No
2.4e5
Int. Type:
Base To Base
Retention Time:
14.7 min
2.3e5 2.3e5
Area: Height:
2852295 counts 281198 cps
2.2e5
Start Time: End Time:
14.1 min 14.9 min
2.2e5 2.1e5
14.67
2.1e5
2.0e5
2.0e5
1.9e5
1.9e5
1.8e5
1.8e5
1.7e5
1.7e5
1.6e5
1.6e5
1.5e5
Intensity, cps
1.5e5
1.4e5
1.4e5 1.3e5
15.38
1.3e5
1.2e5
1.2e5
1.1e5
14.45
1.1e5
1.0e5
9.5e4
9.0e4
8.5e4
8.0e4
7.5e4
7.0e4
6.5e4
6.0e4
5.5e4
5.0e4
4.5e4
4.0e4
3.5e4
3.0e4
2.5e4
2.0e4
1.5e4
1.0e4
5000.0
0.0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Time, min
Printing Date: Tuesday, November 29, 2005 Printing Time: 09:41:30 AM
Page 20 of 88
*Ollie U00110402
Results Name: o051020a.rdb
Sample Name: "O051020a028" Sample ID: "MB-051011-2" File: "o051020a.wiff"
Peak Name: "pfos (tic)" Mass(es): "498.8/98.9 amu,498.8/80.0 amu,498.8/129.9 amu"
Comment: "Method Blank-2" Annotation: ""
Sample Index:
28
Sample Type:
Unknown
Concentration:
N/A
Calculated Conc:
< 0
Acq. Date:
10/20/2005
1.3e5
Acq. Time:
11:13:04 AM
Modified:
No
Proc. Algorithm: IntelliQuan - MQII
Noise Percentage:
50
Base. Sub. Window:
1.00 min
Peak-Split. Factor: 8
Report Largest Peak: No
Min. Peak Height:
0.00 cps
Min. Peak Width:
0.00 sec
Smoothing Width:
3
points
RT Window:
30.0
sec
Expected RT:
14.7 min
Use Relative RT:
No
Int. Type: Retention Time: Area: Height: Start Time: End Time:
Base To Base 14.7 min
41506 counts 4144 cps 14.3 min 14.8 min
1.3e5 1.2e5 1.2e5 1.1e5 1.1e5 1.0e5
15.38
9.5e4
9.0e4
8.5e4
8.0e4
7.5e4
Intensity, cps
7.0e4
6.5e4
6.0e4
5.5e4
5.0e4
4.5e4
4.0e4
3.5e4
3.0e4
2.5e4
2.0e4
1.5e4
1.0e4
5000.0
0.0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Time, min
Printing Date: Tuesday, November 29, 2005
Page 28 of 88
Printing Time: 09:41:30 AM
E05-0210 Interim Report#15
Northern Alabama Potable Water Systems
Page 30 of 123
3M Environmental Laboratory E05-0210 Interim Report#15
*Ollie U00110402
Results Name: o051020a.rdb
Sample Name: "O051020a040" Sample ID: "LCS-051011-3" File: "o051020a.wiff"
Peak Name: "pfos (tic)" Mass(es): "498.8/98.9 amu,498.8/80.0 amu,498.8/129.9 amu"
Comment: "0.25 ppb Lab Control Spike" Annotation: ""
Sample Index:
40
Sample Type:
QC
Concentration:
0.248
ng/mL
Calculated Conc: 0.233
ng/mL
Acq. Date:
10/20/2005
1.20e5 1.18e5
Acq. Time:
03:41:17 PM
1.16e5
15.40
Modified:
No
Proc. Algorithm: IntelliQuan - MQII
Noise Percentage:
50
Base. Sub. Window:
1.00 min
Peak-Split. Factor: 8
Report Largest Peak: No
Min. Peak Height:
0.00 cps
Min. Peak Width:
0.00 sec
Smoothing Width:
3
points
RT Window:
30.0
sec
Expected RT:
14.7 min
Use Relative RT:
No
1.14e5 1.12e5 1.10e5 1.08e5 1.06e5 1.04e5 1.02e5 1.00e5
Int. Type:
Base To Base
Retention Time:
14.7 min
Area:
742478 counts
Height:
72701 cps
Start Time:
14.2 min
End Time:
14.9 min
9.80e4 9.60e4 9.40e4 9.20e4 9.00e4
8.80e4
8.60e4
8.40e4
8.20e4
8.00e4
7.80e4
7.60e4
7.40e4
14.70
7.20e4
7.00e4
6.80e4
6.60e4
6.40e4
Intensity, cps
6.20e4
6.00e4
5.80e4
5.60e4
5.40e4
5.20e4
5.00e4
4.80e4
4.60e4
4.40e4
4.20e4
4.00e4
3.80e4
3.60e4
3.40e4
3.20e4
3.00e4 2.80e4
14.50
2.60e4
2.40e4
2.20e4
2.00e4
1.80e4
1.60e4
1.40e4
1.20e4
1.00e4
8000.00
6000.00
4000.00
2000.00
0.00
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Time, min
Printing Date: Tuesday, November 29, 2005 Printing Time: 09:41:30 AM
Page 40 of 88
*Ollie U00110402
Results Name: o051020a.rdb
Sample Name: "O051020a044" Sample ID: "E05-0210-89707" File: "o051020a.wiff"
Peak Name: "pfos (tic)" Mass(es): "498.8/98.9 amu,498.8/80.0 amu,498.8/129.9 amu"
Comment: "DPWS PW FW01 0 051004" Annotation: ""
Sample Index:
44
Sample Type:
Unknown
Concentration:
N/A
Calculated Conc: 0.00204
ng/mL
1.18e5
Acq. Date: Acq. Time:
10/20/2005 05:05:11 PM
1.16e5 1.14e5
Modified:
No
Proc. Algorithm: IntelliQuan - MQII
1.12e5
Noise Percentage:
50
1.10e5
Base. Sub. Window:
1.00 min
Peak-Split. Factor: 8
1.08e5
Report Largest Peak: No
Min. Peak Height:
0.00 cps
Min. Peak Width:
0.00 sec
1.06e5 1.04e5
Smoothing Width: RT Window:
3 30.0
points sec
1.02e5
Expected RT:
14.7 min
1.00e5
Use Relative RT:
No
9.80e4
15.36
Int. Type: Retention Time: Area: Height: Start Time: End Time:
Base To Base 14.7 min
66575 counts 6679 cps 14.3 min 14.8 min
9.60e4 9.40e4 9.20e4 9.00e4
8.80e4
8.60e4
8.40e4
8.20e4
8.00e4
7.80e4
7.60e4
7.40e4
7.20e4
7.00e4
6.80e4
6.60e4
6.40e4
Intensity, cps
6.20e4
6.00e4
5.80e4
5.60e4
5.40e4
5.20e4
5.00e4
4.80e4
4.60e4
4.40e4
4.20e4
4.00e4
3.80e4
3.60e4
3.40e4
3.20e4
3.00e4
2.80e4
2.60e4
2.40e4
2.20e4
2.00e4
1.80e4
1.60e4
1.40e4
1.20e4
1.00e4
8000.00
6000.00
4000.00
2000.00
0.00
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Time, min
Printing Date: Tuesday, November 29, 2005 Printing Time: 09:41:30 AM
Page 44 of 88
E05-0210 Interim Report#15
Northern Alabama Potable Water Systems
Page 31 of 123
3M Environmental Laboratory E05-0210 Interim Report#15
*Ollie U00110402
Results Name: o051020a.rdb
Sample Name: "O051020a046" Sample ID: "E05-0210-89709" File: "o051020a.wiff"
Peak Name: "pfos (tic)" Mass(es): "498.8/98.9 amu,498.8/80.0 amu,498.8/129.9 amu"
Comment: "DPWS PW FW01 LS 051004" Annotation: ""
Sample Index:
46
Sample Type:
Unknown
Concentration:
N/A
1.16e5
Calculated Conc: 0.0933
ng/mL
Acq. Date:
10/20/2005
1.14e5
Acq. Time:
05:47:07 PM
1.12e5
15.38
Modified:
No
Proc. Algorithm: IntelliQuan - MQII
Noise Percentage:
50
Base. Sub. Window:
1.00 min
Peak-Split. Factor: 8
Report Largest Peak: No
Min. Peak Height:
0.00 cps
Min. Peak Width:
0.00 sec
Smoothing Width:
3
points
RT Window:
30.0
sec
Expected RT:
14.7 min
Use Relative RT:
No
1.10e5 1.08e5 1.06e5 1.04e5 1.02e5 1.00e5 9.80e4 9.60e4
Int. Type:
Base To Base
Retention Time:
14.7 min
Area:
333740 counts
Height:
31673 cps
Start Time:
14.1 min
End Time:
14.9 min
9.40e4 9.20e4 9.00e4 8.80e4 8.60e4
8.40e4
8.20e4
8.00e4
7.80e4
7.60e4
7.40e4
7.20e4
7.00e4
6.80e4
6.60e4
6.40e4
6.20e4
Intensity, cps
6.00e4
5.80e4
5.60e4
5.40e4
5.20e4
5.00e4
4.80e4
4.60e4
4.40e4
4.20e4
4.00e4
3.80e4
3.60e4
3.40e4 3.20e4
14.69
3.00e4
2.80e4
2.60e4
2.40e4
2.20e4
2.00e4
1.80e4
1.60e4
1.40e4 1.20e4
14.48
1.00e4
8000.00
6000.00
4000.00
2000.00
0.00
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Time, min
Printing Date: Tuesday, November 29, 2005 Printing Time: 09:41:31 AM
Page 46 of 88
*Ollie U00110402
Results Name: o051020a.rdb
o051020a.rdb (pfos (tic)): "Quadratic" Regression ("1 / x" weighting): y = -2.38e+004 x^2 + 2.93e+006 x + 6.06e+004 (r = 0.9998) 5.9e7 5.5e7
5.0e7
4.5e7
4.0e7
3.5e7
Area, counts
3.0e7
2.5e7
2.0e7
1.5e7
1.0e7
5.0e6
0.0
0
1
2
3
4
5
6
7
8
9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25
Concentration, ng/mL
Printing Date: Tuesday, November 29, 2005
Page 1 of 1
Printing Time: 09:44:09 AM
E05-0210 Interim Report#15
Northern Alabama Potable Water Systems
Page 32 of 123
3M Environmental Laboratory E05-0210 Interim Report#15
*Ollie U00110402
Results Name: o051020a.rdb
Sample Name: "O051020a020" Sample ID: "EC-051011-006"
Peak Name: "13C pfoa" Mass(es): "414.9/369.8 amu"
Comment: "1.0 ppb extracted curve point" Annotation: ""
Sample Index:
20
Sample Type:
Standard
Concentration:
0.998
ng/mL
1.12e5
Calculated Conc: 0.965
ng/mL
Acq. Date:
10/20/2005
1.10e5
Acq. Time:
08:25:21 AM
1.08e5
File: "o051020a.wiff"
13.98
Modified:
No
Proc. Algorithm: IntelliQuan - IQA
Min. Peak Height: 0.00 cps
Min. Peak Width:
0.00 sec
Smoothing Width: 3
points
RT Window:
30.0
sec
Expected RT:
14.0 min
Use Relative RT:
No
1.06e5 1.04e5 1.02e5 1.00e5 9.80e4
Int. Type:
Valley
Retention Time:
14.0 min
Area:
737174 counts
Height:
112287 cps
Start Time:
13.7 min
End Time:
14.2 min
9.60e4 9.40e4 9.20e4 9.00e4 8.80e4
8.60e4
8.40e4
8.20e4
8.00e4
7.80e4
7.60e4
7.40e4
7.20e4
7.00e4
6.80e4
6.60e4
6.40e4
6.20e4
6.00e4
Intensity, cps
5.80e4
5.60e4
5.40e4
5.20e4
5.00e4
4.80e4
4.60e4
4.40e4
4.20e4
4.00e4
3.80e4
3.60e4
3.40e4
3.20e4
3.00e4
2.80e4
2.60e4
2.40e4
2.20e4
2.00e4
1.80e4
1.60e4
1.40e4
1.20e4
1.00e4
8000.00
6000.00
4000.00
2000.00
0.00
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Time, min
Printing Date: Tuesday, November 29, 2005 Printing Time: 09:42:32 AM
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Results Name: o051020a.rdb
Sample Name: "O051020a028" Sample ID: "MB-051011-2" File: "o051020a.wiff"
Peak Name: "pfbs (tic)" Mass(es): "298.9/98.9 amu,298.9/79.9 amu"
Comment: "Method Blank-2" Annotation: ""
Sample Index:
28
Sample Type:
Unknown
Concentration:
N/A
Calculated Conc:
< 0
Acq. Date:
10/20/2005
5500 5400
Acq. Time:
11:13:04 AM
5300
11.93
Modified:
No
Proc. Algorithm: IntelliQuan - IQA
Min. Peak Height: 0.00 cps
Min. Peak Width:
0.00 sec
Smoothing Width: 3
points
RT Window:
30.0
sec
Expected RT:
10.8 min
Use Relative RT:
No
5200 5100 5000 4900 4800
Int. Type: Retention Time: Area: Height: Start Time: End Time:
Valley 10.8 min
5792 counts 695 cps 10.7 min 11.0 min
4700 4600 4500 4400
4300
4200
4100
4000
3900
3800
3700
3600
3500
3400
3300
3200
3100
3000
Intensity, cps
2900
2800
2700
2600
2500
2400
2300
2200
2100
2000
0.88
1900 1800
17.13
1700
1600
1500
1400
1300
1200
1100
1000
900
10.79
800
18.94
700 16.44 18.64
600
15.70 16.25
18.44
500
12.73 13.68 13.96
18.03
19.16
400
12.94
14.95 15.22
300
200
100
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Time, min
Printing Date: Tuesday, November 29, 2005 Printing Time: 09:40:15 AM
Page 28 of 88
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Results Name: o051020a.rdb
Sample Name: "O051020a040" Sample ID: "LCS-051011-3"
Peak Name: "13C pfoa" Mass(es): "414.9/369.8 amu"
Comment: "0.25 ppb Lab Control Spike" Annotation: ""
Sample Index:
40
Sample Type:
QC
Concentration:
0.249
ng/mL
Calculated Conc: 0.274
ng/mL
Acq. Date: Acq. Time:
10/20/2005 03:41:17 PM
3.0e4
File: "o051020a.wiff"
Modified:
No
Proc. Algorithm: IntelliQuan - IQA
Min. Peak Height: 0.00 cps
Min. Peak Width:
0.00 sec
Smoothing Width: 3
points
RT Window:
30.0
sec
Expected RT:
14.0 min
Use Relative RT:
No
2.9e4 2.8e4 2.7e4
Int. Type:
Valley
Retention Time:
14.0 min
Area:
226013 counts
Height:
30751 cps
Start Time:
13.9 min
End Time:
14.4 min
2.6e4 2.5e4 2.4e4
14.04
2.3e4
2.2e4
2.1e4
2.0e4
1.9e4
1.8e4
1.7e4
Intensity, cps
1.6e4
1.5e4
1.4e4
1.3e4
1.2e4
1.1e4
1.0e4
9000.0
8000.0
7000.0
6000.0
5000.0
4000.0
3000.0
2000.0
1000.0
0.0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Time, min
Printing Date: Tuesday, November 29, 2005
Page 40 of 88
Printing Time: 09:42:32 AM
*Ollie U00110402
Results Name: o051020a.rdb
Sample Name: "O051020a044" Sample ID: "E05-0210-89707"
Peak Name: "13C pfoa" Mass(es): "414.9/369.8 amu"
Comment: "DPWS PW FW01 0 051004" Annotation: ""
Sample Index:
44
Sample Type:
Unknown
Concentration:
N/A
Calculated Conc: 0.182
ng/mL
Acq. Date:
10/20/2005
2.3e4
Acq. Time:
05:05:11 PM
2.3e4
File: "o051020a.wiff"
Modified:
No
Proc. Algorithm: IntelliQuan - IQA
Min. Peak Height: 0.00 cps
Min. Peak Width:
0.00 sec
Smoothing Width: 3
points
RT Window:
30.0
sec
Expected RT:
14.0 min
Use Relative RT:
No
Int. Type:
Valley
Retention Time:
14.0 min
Area:
156428 counts
Height:
23339 cps
Start Time:
13.8 min
End Time:
14.3 min
2.2e4 2.2e4 2.1e4 2.1e4 2.0e4 2.0e4 1.9e4 1.9e4
1.8e4
1.8e4
1.7e4
1.7e4
1.6e4
1.6e4
1.5e4
1.5e4
1.4e4
1.4e4
1.3e4
1.3e4
Intensity, cps
1.2e4
1.2e4
1.1e4
1.1e4
1.0e4
9500.0
9000.0
8500.0
8000.0
7500.0
7000.0
6500.0
6000.0
5500.0
5000.0
4500.0
4000.0
3500.0
3000.0
2500.0
2000.0
1500.0
1000.0
500.0
0.0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Time, min
Printing Date: Tuesday, November 29, 2005
Page 44 of 88
Printing Time: 09:42:32 AM
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*Ollie U00110402
Results Name: o051020a.rdb
Sample Name: "O051020a046" Sample ID: "E05-0210-89709"
Peak Name: "13C pfoa" Mass(es): "414.9/369.8 amu"
Comment: "DPWS PW FW01 LS 051004" Annotation: ""
Sample Index:
46
Sample Type:
Unknown
Concentration:
N/A
Calculated Conc: 0.0351
ng/mL
7000
Acq. Date:
10/20/2005
Acq. Time:
05:47:07 PM
6800
Modified:
No
Proc. Algorithm: IntelliQuan - IQA
Min. Peak Height: 0.00 cps
Min. Peak Width:
0.00 sec
Smoothing Width: 3
points
RT Window:
30.0
sec
Expected RT:
14.0 min
Use Relative RT:
No
6600 6400 6200
File: "o051020a.wiff"
Int. Type: Retention Time: Area: Height: Start Time: End Time:
Valley 14.0 min
45506 counts 7091 cps 13.9 min 14.3 min
6000 5800 5600
14.03
5400
5200
5000
4800
4600
4400
4200
4000
3800
Intensity, cps
3600
3400
3200
3000
2800
2600
2400
2200
2000
1800
1600
1400
1200
1000
800
600
400
200
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Time, min
Printing Date: Tuesday, November 29, 2005
Page 46 of 88
Printing Time: 09:42:32 AM
*Ollie U00110402
Results Name: o051020a.rdb
o051020a.rdb (13C pfoa): "Quadratic" Regression ("1 / x" weighting): y = -1.68e+004 x^2 + 7.6e+005 x + 1.88e+004 (r = 0.9960)
1.3e7
1.3e7
1.2e7
1.2e7
1.1e7
1.1e7
1.0e7
9.5e6
9.0e6
8.5e6
8.0e6
7.5e6
Area, counts
7.0e6
6.5e6
6.0e6
5.5e6
5.0e6
4.5e6
4.0e6
3.5e6
3.0e6
2.5e6
2.0e6
1.5e6
1.0e6
5.0e5
0.0
0
1
2
3
4
5
6
7
8
9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25
Concentration, ng/mL
Printing Date: Tuesday, November 29, 2005 Printing Time: 09:44:41 AM
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3M Environmental Laboratory E05-0210 Interim Report#15
ATTACHMENT B: EXTRACTION AND ANALYTICAL METHODS
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3M EnvironmentalLabomlbory
Method Determination of Perfluorinaited Acids, Alcohols, Amides, and Sulfonates In
Water By Solid Phase Extraction and High Performance Liquid Chromatcigraphy/Mass Spectrorncstry Method Number: ETS-8-154.1 Adoption Date: 28 Apr 2000 Revision Date: 5 May, 2003 Effective Date: 5 May, 2003
Approved By:
William K. Reagen Manager
Date
ETS-8-154.1
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1 Scope and Application
This method was validated for the collection, extraction, and analytical procedure for the determination of Perfluorooctane sulfonate (PFOS), Perfluorooctane sulfonylamide (FOSA), and Perfluorooctanoate (PFOA) in groundwater, surface water, and drinking water samples. This method may also be applied to the determination of other perfluorinated acids, alcohols, amides, and sulfonates in similar matrices, as long as the defined QC elements are satisfied and with the understanding that the method is not validated for compounds outside the scope of the original protocol
This method is based in part on the report "Method of Analysis for the Determination of Perfluorooctane sulfonate (PFOS), Perfluorooctane sulfonylamide (PFOSA), and Perfluorooctanoate (POAA) in Water" (see Section 17), as developed and validated by Exygen Research (formerly Centre Analytical Laboratories, Inc.).
2 Method Summary
Water samples are collected from a site of interest and shipped cold to an analytical facility. Perfluorinated acids, alcohols, amides, and sulfonates are extracted from 40mL water samples using C18 solid phase extraction (SPE) cartridges. The compounds are eluted from the C18 cartridge, using methanol. Separation, identification, and measurement are accomplished by highperformance liquid chromatography/ tandem mass spectrometry (HPLC/MS/MS) analysis. Highperformance liquid chromatography/mass spectrometry (HPLC/MS) may be used if the defined QC elements are satisfied.
The concentration of each identified component is measured by comparing the MS response of the quantitation ion produced by that compound to the MS response of the quantitation ion produced by the same compound in an extracted calibration standard (external standard).
3 Definitions
3.1 Analytical Sample
A portion of an extracted Laboratory Sample prepared for analysis.
3.2 Calibration 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 Duplicate Sample (DS)
A DS is a separate aliquot of a sample, taken in the analytical laboratory that is extracted 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)
ASTM 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.
ETS-8-154.1
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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 of 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 Matrix 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. Alternatively, the known quantity of target analytes may be added to the sample bottle in the laboratory before the bottles are sent to the field. A known, specific volume of sample must be added to sample container without rinsing. This may be accomplished by making a "fill to this level" line on the outside of the sample container. The FMS should be spiked at approximately 50-150% of the expected analyte concentration in the sample. If the expected range of analyte concentrations is unknown, a low and a high spike may be prepared to increase the likelihood that a spike at an appropriate range is made. The FMS is analyzed to ascertain if any matrix effects, interferences, or stability issues may complicate the interpretation of the sample analysis.
3.7 Field Spike Control Sample (FSCS)
An aliquot of ASTM Type I water to which known quantities of the target analytes are added in the field at the time of sample collection (at an appropriate concentration to be determined by the project lead) or in the laboratory prior to the shipment of the collection bottles. 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. A low and high FSCS may be appropriate when expected sample concentrations are not known.
3.8 Laboratory Control Sample (LCS)
An aliquot of ASTM Type I water to which known quantities of the target analytes are added in the laboratory. Two levels are included, one at the LLOQ (approx. 25 pg/mL), the other at a concentration of approx. 100-250 pg/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 Laboratory Sample
A portion of a sample received from the field for testing.
3.10 Limit of Detection (LOD)
The LOD is the lowest concentration of an analyte that can be measured and reported with 99% confidence that the analyte concentration is greater than zero. If required, the LOD may be determined in several ways, including signal-to-noise ratio and statistical calculations.
3.11 Limit of Quantitation (LOQ)
The LOQ for a dataset is the lowest concentration (LLOQ) or highest concentration (ULOQ) that can be reliably achieved within the specified limits of precision and accuracy during routine operating conditions.
Note: For many analytes, the LLOQ analyte concentration is selected as the lowest non-zero standard in the calibration curve to simplify data reporting. Sample LLOQs are matrix-dependent.
3.12 Matrix Spike (MS)
ETS-8-154.1
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A matrix spike is 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 values in the MS corrected for background concentrations.
3.13 Method Blank
An aliquot of ASTM Type I water that is treated exactly like a laboratory sample including exposure to all glassware, equipment, solvents, and reagents that are used with other laboratory samples. The method blank is used to determine if test substances or other interferences are present in the laboratory environment, the reagents, or the apparatus.
3.14 Method Detection Limit (MDL) Determination
A MDL is the statistically calculated minimum amount of an analyte that can be measured with 99% confidence that the reported value is greater than zero. One of several processes that may be used to establish a LOD value is found in 40 CFR Part 136 Appendix B.
3.15 Sample
A sample is a small portion collected from a larger quantity of 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 Warnings and Cautions
4.1 Health and Safety
The acute and chronic toxicity of the standards for this method have not been precisely determined; however, each should be treated as a potential health hazard. Unknown samples may contain high concentrations of volatile toxic compounds. Sample containers should be opened in a hood and handled with gloves to prevent exposure. The laboratory is responsible for maintaining a safe work environment and a current awareness of local regulations regarding the handling of the chemicals used in this method. A reference file of material safety data sheets (MSDS) should be available to all personnel involved in these analyses.
4.2 Cautions
None
5 Interferences
ETS-8-154.1
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During extraction and analysis, major potential contaminant sources are reagents and solid phase extraction devices.
All materials used in the analyses shall be demonstrated to be free from interferences under conditions of analysis by running method blanks.
Parts and supplies that contain Teflon should be avoided due to the possibility of interference and/or contamination. These may include, but are not limited to: wash bottles, Teflon lined caps, autovial caps, HPLC parts, etc.
The use of disposable micropipettes or pipettes to aliquot standard solutions is recommended to make calibration standards and matrix spikes.
6 Instrumentation, 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 of this method is the responsibility of the laboratory performing the analysis.
6.1 Instrumentation
Balance, analytical (display at least 0.0001g), Mettler HPLC/MS/MS or HPLC/MS system, as described in Section 10.
6.2 Supplies and Materials.
Sample collection bottles--LDPE (e.g., NalgeneTM) narrow-mouth bottles with screw cap. Note: Do not use Teflon bottles or Teflon lined caps. Coolers for sample shipment. Ice for sample shipment. Vacuum pump, Bchi. Visiprep vacuum manifold, Supelco. Sep Pak Vac 6cc (1g) tC18 cartridges (part # WAT 036795),Waters. 50mL disposable polypropylene centrifuge tubes, VWR. 15mL disposable polypropylene centrifuge tubes, VWR. Disposable micropipettes (50-100L, 100-200L), Drummond. Class A pipettes and volumetric flasks, various. Hypercarb drop-in guard column (4mm) (part # 844017-400), Keystone. Stand-alone drop-in guard cartridge holder, Keystone. 125mL LDPE narrow-mouth bottles, Nalgene. 2mL clear HPLC vial kit (cat # 5181-3400), Agilent/Hewlett Packard. Standard lab equipment (graduated cylinders, disposable tubes, etc.), various.
7 Reagents and Standards
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.
ETS-8-154.1
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7.1 Chemicals
Methanol (MeOH), HPLC grade, JT Baker, Catalog No. JT9093-2.
Ammonium Acetate, Reagent grade, Sigma-Aldrich, Catalog No. A-7330.
ASTM Type I Water, prepared in-house.
Sodium Thiosulfate, Reagent grade, JT Baker.
7.2 Standards
Potassium perfluorooctane sulfonate
Perfluorooctane sulfonylamide
Ammonium perfluorooctanoate
Others as required.
7.3 Reagent Preparation
250mg/mL sodium thiosulfate solution -- Dissolve 25g of sodium thiosulfate in 100mL reagent water.
40% methanol wash solution - Measure 400mL methanol and adjust volume to 1.0L with reagent water.
100mM ammonium acetate solution (Analysis)--Weigh 7.71g of ammonium acetate and dissolve in 1.0L of reagent water. Dilute the 100mM solution by a factor of 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 Standard (SSS) Preparation
The following standard preparation procedure serves as an example and may be changed to suit the needs of a particular study. For example, L volumes may be spiked into volumetric flasks when diluting stock solutions to appropriate levels.
100g/mL each PFOS, PFOSA, and POAA SSSs--Weigh out 10mg of analytical standard (corrected for percent salt and purity--i.e., 10 mg C8F17S03K purity 90% = 8.35mg C8F17S03-) and dilute to 100mL with methanol in a 100mL volumetric flask. Transfer to a 125mL LDPE bottle or other suitable container. Prepare a separate solution for each analyte. Solutions may be stored in a refrigerator at 42C for a maximum period of 6 months from the date of preparation.
1g/mL mixed SSS--Add 1.0mL each of the 100g/mL SSSs (from 7.4.1) to a 100mL volumetric flask and bring up to volume with methanol.
0.1g/mL mixed SSS--Add 10.0mL of the 1.0g/mL-mixed solution (from 7.4.2) to a 100mL volumetric flask and bring up to volume with methanol.
0.01g/mL mixed SSS--Add 10.0mL of the 0.1g/mL-mixed solution (from 7.4.3) to a 100mL volumetric flask and bring up to volume with methanol.
Storage Conditions--Store all SSSs in a refrigerator at 42C for a maximum period of 6 months from the date of preparation.
7.5 Calibration Standards
The following standard preparation procedure serves as an example and may be changed to suit the needs of a particular study, provided the concentrations are calculated correctly.
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100g/mL each PFOS, PFOSA, and POAA stock standard solutions--Weigh out 10mg of analytical standard (corrected for percent salt and purity) and dilute to 100mL with methanol in a 100mL volumetric flask. Transfer to a 125mL LDPE bottle or other suitable container. 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.
1g/mL Working Standard--Add 1.0mL each of the 100g/mL SS solutions (from 7.5.1) to a 100mL volumetric flask and bring up to volume with methanol.
0.1g/mL Working Standard --Add 10.0mL of the 1.0g/mL mixed solution (from 7.5.2) to a 100mL volumetric flask and bring up to volume with methanol.
0.01g/mL Working Standard --Add 10.0mL of the 0.1g/mL mixed solution (from 7.5.3) to a 100mL volumetric flask and bring up to volume with methanol.
Storage Conditions--Store all WSs in a refrigerator at 42C for a maximum period of 6 months from the date of preparation.
Calibration Standard--Prepare calibration solutions in ASTM Type I using the following table as a guideline:
Concentration of WS, g/mL
0.0 0.010 0.010 0.010 0.10 0.10 0.10 0.10
1.0 1.0 1.0
Final Calibration Volume of Standard Volume, mL ,
WS, L of ASTM Type I Water
0
40
100
40
200
40
400
40
100
40
200
40
300
40
400
40
100
40
400
40
1000
40
Final Concentration of Calibration Standard, pg/mL, in ASTM Type I
Water
0 25 50 100 250 500 750 1000 2500 10000 25000
The standards are processed through the extraction procedure (Section 11), identical to the laboratory samples. The concentration of the calibration standard in the final extract is equal to 8X the initial concentration, due to the concentration of the standard during the extraction process.
Storage Conditions--Store all extracted calibration standards in 15mL polypropylene tubes at 42C, for a maximum period of two weeks from the date of preparation
8 Sample Collection and Handling
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.
Labeling: Each sample bottle must display information regarding the collection of that sample, the individual collecting the sample, and any matrix spike that has been added to the sample.
ETS-8-154.1
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This includes the volume and concentration of any spiking solution added and the volume and identification of any preservatives added in the field.
Spiking: The spiking scheme will be clearly outlined in the sampling plan, including whether the samples will be spiked in the field or in the laboratory prior to the shipment of the bottles to the site. If spiking is to be performed in the field, materials and specific instructions will be included in the sampling kit. Be sure to clearly label each bottle with spiking information if applicable.
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 500mL/min and collect samples from the flowing stream.
Ground Water: Purge the well of standing water using a pump or a bailer. Collect the sample directly from the pump or from the bailer.
Surface Water: When sampling from an open body of water, fill the sample container with water from a representative area.
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 eliminated by adding 200L of a 250mg/mL sodium thiosulfate solution to each tap-water sample and associated FB and FSCS (which may be placed in each bottle before leaving for the sampling site or done in the field.).
Holding Time (HT): Results of the time/storage study of 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 the previous section (see also references in section 17). 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.
8.1 Field Blanks
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 ASTM 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.
When sodium thiosulfate is added to samples, use the same procedure to preserve the FB.
8.2 Field Duplicates
Collect a Field Duplicate (FD) for every ten (10) samples collected or per each sampling set, if less than 10 samples are collected.
Separate FDs must be collected for each type of water sample (ground, tap, etc.) collected.
Collect the FD immediately after the sample.
Preserve, store and ship FD using the same procedures as used for the samples.
8.3 Field Spike Control Sample (FSCS)
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.
At the laboratory, fill a sample container with 100mL of ASTM Type I water. Seal and ship to the sampling site along with the empty sample containers and FBs. Samples may either be spiked in the field or in the laboratory prior to shipment. The method employed should be consistent throughout the study. If the samples are to be spiked in the field, be sure to send appropriate supplies and instructions for the field personnel to follow.
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Seal and gently invert the FSCS to mix. Store and ship the FSCS using the same procedures as used for the samples
Provide information on sample collection, preservation, shipment and storage. List applicable holding times. Include sample stability and extract storage requirements. Reference the method used for sample preparation, if applicable.
8.4 Field Matrix Spike (FMS)
A Field Matrix Spike (FMS) must be prepared for each sampling location. One unspiked sample from the same location must accompany the FMS to determine endogenous levels in the sample. The samples should be clearly identifiable as being from the same location.
Samples may either be spiked in the field or in the laboratory prior to shipment. The method employed should be consistent throughout the study. If the samples are to be spiked in the field, be sure to send appropriate supplies and instructions for the field personnel to follow.
9 Quality Control and Data Quality Objectives
Analytical results of the FB, FMS, FD, and FSCS should be evaluated at the conclusion of the study to help interpret the quality of sample data. Analytical results for these control/duplicate samples must be reported with the sample data.
9.1 Solvent Blanks
Solvent blanks are analyzed with each sample set to determine contamination or carryover. Aliquots of methanol represent the solvent used for the standard curve and the sample extraction. Solvent blanks should have area counts that are less than 50% of the area count of the lowest calibration standard.
Solvent blanks should be analyzed prior to and following each calibration curve, each set of system suitability samples, and after no more than 10 unknown sample extracts. If instrument carryover is a problem consecutive solvent blanks may be necessary. In this case the area counts of the solvent blanks should return to <50% of the lowest calibration standard prior to the injection of further standards or samples.
9.2 Method Blanks
A method blank consists of an aliquot of ASTM Type I water, equal in volume to the samples, and extracted in the same manner as the samples. At least two method blanks should be prepared and analyzed each day that extractions are performed for a particular study or project. When analyzed the area counts of these samples must be less than 50% of the area count of the lowest calibration standard.
9.3 Sample Replicates
All samples, including field spikes, trip blanks, etc., should be extracted at least in duplicate, and in triplicate if difficulties were encountered in the sampling and/or holding conditions of the samples. The relative percent difference (RPD) of duplicate samples or relative standard deviation (RSD) should be less than 15% for the precision of sample preparation and analysis to be considered in control.
9.4 Matrix Spike
Matrix spikes are prepared for each sample type and analyzed to determine the matrix effect on the recovery efficiency. Matrix spike recoveries should fall within 25% of expected values. If the matrix spikes fail, evaluate the lab control spikes. If the LCS are within acceptance criteria there may be matrix issues in the samples. Discuss these in the final report.
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Matrix spike duplicates are prepared periodically to measure the precision associated with the analysis.
Analyze a matrix spike and matrix spike duplicate (if prepared) in the same run as the original sample.
Matrix spike and matrix spike duplicate concentrations should fall in the mid-range of the initial calibration curve or should be prepared at 1.5-5 times the endogenous concentration of the analyte. Spike concentrations should fall in the low-range of the initial calibration curve if extremely low-levels are expected. Generally two or more levels are prepared, one in the low range of the curve and one in the mid-range. This avoids the need to pre-screen unknown samples prior to preparation.
9.5 Laboratory Control Spike
Lab control spikes are prepared for each study to ensure recovery of the target analytes. These should be prepared at a minimum of 2 levels and in duplicate or triplicate. Recovery of these samples should be within 25% of expected values, and the RPD (or RSD) be 15%. If recoveries fall outside these limits the samples should be addressed in the final report.
10 Calibration and Standardization
10.1 Instrument Setup
Note: In this example, a MicroMass UltimaTM Liquid Chromatography Tandem Mass Spectrometer (LC/MS/MS) is used. Other brands of LC/MS/MSs as well as single quadrupole mass spectrometers (LC/MS) may be used as long as the method criteria are met. Brand names, suppliers, part numbers, and models 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 of this method is the responsibility of the laboratory. The operator must optimize and document the equipment and settings used.
Establish the LC/MS/MS system and operating conditions equivalent to the following:
Mass Spec: Micromass Ultima (Micromass)
Interface: Electrospray (Micromass)
Mode: Electrospray Negative, Multiple Response Monitoring (MRM)
Harvard infusion pump (Harvard Instruments), for tuning
Computer: COMPAQ Professional Workstation AP200
Software: Windows NT, MassLynx 3.3
HPLC: Hewlett Packard (HP) Series 1100
HP Quaternary Pump
HP Vacuum Degasser
HP Autosampler
HP Column Oven
Note: A 4 10mm Hypercarb drop-in guard cartridge (Keystone, part # 844017-400) may be 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 C8 (Jones Chromatography), 2.1mm x 50mm, 4m
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Column Temperature: 35C Injection Volume: 15L Mobile Phase (A): 2mM Ammonium Acetate in ASTM Type I water (See 7.3.1) Mobile Phase (B): Methanol
Time, min
Percent Mobile Percent Mobile
Phase A
Phase B
Flow Rate, mL/min
0.0
60
40
0.3
0.4
60
40
0.3
1.0
10
90
0.3
7.0
10
90
0.3
7.5
0
100
0.3
9.0
0
100
0.4
9.5
60
40
0.4
13.5
60
40
0.4
14.0
60
40
0.3
Note: Other HPLC gradients may be used as long as the method criteria are met.
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 C18 etc.) may be used.
Ions Monitored:
Analyte
Primary Ion Product Ion
Approximate Retention Time
(minutes)
PFOA
413
169
5.0
PFOS
499
99
5.2
FOSA
498
78
5.8
Other product ions may be chosen at the discretion of the analyst, although m/z 99 is suggested for PFOS. Use of the suggested primary ion is recommended. Retention times may vary slightly, on a day-to-day basis, depending on the batch of mobile phase 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 Parameters
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.
Analyte
PFOA PFOS FOSA
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
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Source Capillary Hexapole 1 Aperture 1 Hexapole 2 Source Block Temp. Desolvation Temp.
Analyzer LM Res 1 HM Res 1 IEnergy 1 Entrance
Exit LM Res 2 HM Res 2 IEnergy 2 Multiplier
Gas Flows Cone Gas Desolvation
Pressures Gas Cell
Set 2.6-3.5kV
0.5V 0.2V 0.8V 100-150C 250-400C
Set 12.5-15.0V 12.5-15.0V
0.7V -2V 1V 11.0V 11.0V 1.0V 650V
Set 150L/hr 700L/hr
Set 3.0e-3mbar
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10.3 Calibration Curve
Analyze the standard curves prior to each set of samples. The validated method specifies that the standard curve should be plotted using a linear fit, weighted 1/x or unweighted. However, the standard curve may also be plotted by quadratic fit (y = ax2 + bx + c), weighted 1/x or unweighted, using suitable software. The calibration curves may include but should not be forced through zero. The mathematical method used to calculate the calibration curve should be applied consistently throughout a study. Any change should be thoroughly documented in the raw data.
If the calibration curve does not meet acceptance criteria perform routine maintenance or prepare a new standard curve (if necessary) and reanalyze.
For purposes of accuracy when quantitating low levels of analyte, it may be necessary to use the low end of the calibration curve rather than the full range. For example, when attempting to quantitate approximately 50 pg/mL of analyte, generate a calibration curve consisting of the standards from 25 pg/mL to 1000 pg/mL rather than the full range of the curve (25 pg/mL to 25000 pg/mL). This will reduce inaccuracy attributed to linear regression weighting of high concentration standards.
High and/or low points may be excluded from the calibration curves to provide a better fit over the linear range appropriate to the data or because they did not meet the pre-determined acceptance criteria. Low-level curve points should also be excluded if their area counts are not at least twice that of the method and/or solvent blanks. Any curve point may be rejected due to a bad injection or failing to meet accuracy requirements of 25% (and 30% for the LLOQ). Justification for exclusion of calibration curve points will be noted in the raw data. A minimum of 6 points will be used to construct the calibration curve.
10.4 Continuing Calibration Verification (CCV)
Continuing calibration verifications (CCV) are analyzed to verify the accuracy of the calibration curve. Analyze a mid-range calibration standard, one of the same standards used to construct the calibration curve, at a minimum after every tenth sample, not including solvent blanks, with a minimum of one per sample set. Calibration verification injections must be within 25% to be considered acceptable. The calibration curve and the last passing CCV will then bracket acceptable samples. Multiple CCV levels may be used.
10.5 System Suitability
A minimum of three system suitability samples will be injected at the beginning and end of each analytical run. Typically these samples are run prior to the calibration curve. The system suitability injections must have area counts with an RSD of 5% and a retention time RSD of 2% when evaluated independently.
11 Procedures
11.1 Extraction Scheme
Allow samples to equilibrate to room temperature. Thoroughly mix samples by gently inverting the sample bottle.
Measure 40mL of sample into 50mL polypropylene centrifuge tubes (Spike the 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). Alternatively the samples could be spiked at more than one level, allowing for the inappropriate spike level to be eliminated.
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Condition the C18 SPE cartridges (1g, 6mL) by passing approximately 10mL methanol followed by approximately 50mL ASTM Type I water (flow rate approximately 2 drop/sec). Do not let column run dry.
Note: For the following steps, maintain a ~1drop/sec flow rate. Do not allow the column to run dry at any time.
Load the analytical sample onto the C18 SPE cartridge. Discard eluate.
Ten mL of the 40% methanol in water wash mixture is passed through the C18 SPE cartridge to rinse away potential interferences and then discarded. This step must be omitted if perfluorinated compounds with chain lengths less than C8 are targeted since these will be lost during this wash step.
Elute with exactly 5mL of 100% methanol. Collect eluate into graduated 15mL polypropylene centrifuge tubes. This is the target elution fraction (final volume approximately 4.5 mL as not all of the solvent will leave the SPE column. This will not affect the calculations in any way since the curve is also extracted).
Analyze a portion of the target elution fraction eluent using negative electrospray HPLC/MS/MS or HPLC/MS.
Note: Samples are concentrated by a factor of eight during the extraction; Initial Vol = 40mL Final Vol. = 5mL.
Samples are stable at room temperature for at least 24 hours. Analytical samples may be stored in a refrigerator at 42C until analysis.
Standardization of C18 SPE columns--If poor recoveries are observed, it may be necessary to standardize the C18 SPE columns in the following manner before analyzing samples.
Use a standard with an analyte concentration between 1000 and 4000 pg/mL. Repeat the extraction scheme from the beginning up through the eluting with ~5mL 100% methanol.
After the eluting with ~5mL 100% methanol step, collect an additional post-elution fraction by eluting with an additional 5mL of 100% methanol.
Analyze both fractions by HPLC/MS/MS or HPLC/MS. If the target fraction contains a minimum of 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.
11.2 Sample Analysis
Set up analysis sample queue.
Inject the same volume (between 5-25L) of each standard, analytical sample and blank into the instrument.
All samples with a concentration > ULOQ must be diluted and reanalyzed. If dilution of the final extract fails to produce acceptable results (e.g. poor MS recoveries) dilute the original sample and re-extract.
12 Data Analysis and Calculations
Calculate the analytical sample (extract) concentration from the standard curve using the following equation:
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Extract Concentration, pg/mL = (Peak area - intercept) (slope)
Calculate the percent recovery of the FSCS using the following equation:
FSCS % rec. = (FSCS conc., pg/mL) x 100 (Conc. added, pg/mL)
Calculate the percent recovery of the MSs using the following equation:
MS % rec. = (MS conc., pg/mL - Sample conc., pg/mL) x 100 (Conc. added, pg/mL)
13 Method Performance
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 of the data. 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 raw data. 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.
13.1 System Suitability
A minimum of three system suitability samples will be injected at the beginning and end of each analytical run. Typically these samples are run prior to the calibration curve. The system suitability injections must have area counts with an RSD of 5% and a retention time RSD of 2% when evaluated independently.
13.2 Quantitation
Calibration Curve: The coefficient of determination (r2) value for the calibration curve must be greater than or equal to 0.990. Each point in the curve must be within 25% of the theoretical concentration with the exception of the LLOQ, which may be within 30%. Demonstration of Specificity: Specificity is demonstrated by chromatographic retention time (within 3% of standard) and the mass spectral response of unique ions.
13.3 Sensitivity
Solvent Blanks and Method Blanks: Solvent and method blank area counts must be < 50% that of the lowest standard used in the calibration curve. 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 of the LLOQ must be within 30% of the theoretical value.
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13.4 Accuracy
CCV Performance: Calibration verification injections must be within 25% to be considered acceptable. The calibration curve and the last passing CCV will then bracket acceptable samples. Multiple CCV levels may be used.
Matrix Spikes: Matrix spike percent recoveries must be within 25% of the spiked concentration. If matrix effects are suspected, evaluate the LCS results to determine if a matrix effects are present and if the method is in control based on compliant LCS results. Discuss all results in the analytical report.
13.5 Precision
Reproducibility: Reproducibility of the method is defined by the results of duplicate or triplicate analysis of samples. A RPD or RSD of 15% will be considered acceptable.
System Suitability: The system suitability injections must have area counts with an RSD of 5% and a retention time RSD of 2% when evaluated independently.
14 Pollution Prevention and Waste Management
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.
15 Records
Each data package generated for a study must have the following information included: study or project number, acquisition method, integration method, sample name, extraction date, dilution factor (if applicable), and analyst.
Print the tune page, sample list, and acquisition method to include in the appropriate study folder. Copy these pages and tape into the instrument run log.
Plot the calibration curves as described in this method, then print these graphs and store in the study folder.
Print data integration summary, integration method, and chromatograms and store in the study folder.
Summarize data using suitable software and store in the study folder.
16 Attachments
None.
17 References
"Method of Analysis for the Determination of Perfluorooctane sulfonate (PFOS), Perfluorooctane sulfonylamide (PFOSA), and Perfluorooctanoate (POAA) in Water", E. Wickremesinhe and J. Flaherty, Study Number 023-002, Centre Analytical Laboratories, Inc., State College, Pennsylvania, January 2000.
Validation report for the "Method of Analysis for the Determination of Perfluorooctane sulfonate (PFOS), Perfluorooctane sulfonylamide (PFOSA), and Perfluorooctanoate (POAA) in Water", E. Wickremesinhe and J. Flaherty, Study Number 023-002, Centre Analytical Laboratories, Inc., State College, Pennsylvania.
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18 Affected Documents
None.
19 Revisions
Revision Number
1
Revision Number Updated to the new format. Changed Title. Section 1: States the validation of 3 analytes, removes reference to EPA document that's no longer applicable. Section 2: Provided for the extraction of more than the 3 validated analytes, allows the use of a LC/MS system, not only the LS/MS/MS previously mentioned. Section 3: Revised definitions for field matrix spike, field control spike, LLOQ, method blank, and MDL. Section 5: Reworded the interferences, added recommendation to use disposable pipettes. Section 6: Recategorized and pared down. Section 7: Changed storage time to 6 months. Added more calibration points to the table. Section 8:Added statement addressing labeling requirements and spiking procedures. Expanded section 8.8. Section 9: New Section Section 10: Changed some of the parameters in the tables. Allowed for use of different instrumentation. Added information from section 12 of previous version, extensively revised. Section 11 (section 9 in previous version): Clarification of wash step, stated exact volume of eluate is 5 mL, revised standardization process, removed requirement to use LC/MS/MS. Section 12 (section 13 in previous version: no changes Section 13 (section 14 in previous version): Extensively rewritten. Section 14 (section 15 in previous version): no changes Section 15 (section 16 in previous version): Minor changes to recording requirements. Section 16 (section 17 in previous version): Removed attachment. Section 17 (section 18 in previous version): Removed reference to EPA document that no longer applied to this SOP. Section 18: New section.
Revision Date 7
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Protocol Exygen P0001131; 3M Study Number E05-0210 Amendment 3
Study Title ANALYSIS OF PERFLUOROBUTANESULFONATE (PFBS), PERFLUOROHEXANESULFONATE (PFHS),
AND PERFLUOROOCTANESULFONATE (PFOS) IN WATER, SOIL, SEDIMENT, FISH, CLAMS, VEGETATION, SMALL MAMMAL LIVER AND SMALL MAMMAL SERUM USING LC/MS/MS FOR THE 3M
DECATUR MONITORING PROGRAM
PROTOCOL AMENDMENT NO. 3
Amendment Date: May 16, 2005
Performing Laboratory 3M Environmental, Health, and Safety Operations
3M Environmental Laboratory 935 Bush Avenue
St. Paul, MN 55106
Laboratory Project Identification E05-0210
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Protocol Exygen P0001131; 3M Study Number E05-0210 Amendment 3
This amendment modifies the following portion(s) of the protocol:
PROTOCOL READS: TESTING FACILITY
Exygen Research 3058 Research Drive State College, PA 15801 Phone: (814) 272-1039
AMEND TO READ:
TESTING FACILITIES Exygen Research 3058 Research Drive State College, PA 15801 Phone: (814) 272-1039
3M Environmental Laboratory Building 2-3E-09 935 Bush Avenue St. Paul, MN 55106
REASON:
Addition of 3M Environmental Laboratory as a testing facility allows selected water samples to be sent to the 3M facility for analysis of PFBS, PFHS, and PFOS using the most current version of ETS 8-154 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates in Water by Solid Phase Extractions and High Performance Liquid Chromatography/Mass Spectrometry".
The following modifications to ETS 8-154.1 will be incorporated into the study:
(1) The sample volume extracted and the final SPE elution volume may be adjusted, at the analyst's discretion, to better achieve the detection limits specified in study objectives. As written, ETS 8154.1 calls for a 40 mL extraction volume with a 5 mL elution volume which results in an eightfold sample concentration. The actual volumes used and the resulting overall concentration factor will be given in the final report. Associated method quality control samples will demonstrate that the volume modifications do not impact method accuracy and precision.
(2) A solvent (unextracted) calibration curve may be analyzed with the extracted calibration curve to ascertain extraction efficiency. Samples will be analyzed using the extracted curve unless otherwise stated in the final report. Data from the solvent calibration curve will not be included or discussed in the final report unless it is used to strengthen experimental observations/explanations.
(3) ETS 8-154.1 makes no mention of sample surrogate spikes; however, all samples will be spiked with at least one of the following radiolabeled surrogates, PFOA [1,2 13C] (perfluorooctanoic acid), PFOS [18O2] and/or PFNA [1,2 13C] (perfluorononanoic acid - C9).The concentration of the surrogate spike may vary depending on the collection event, but typical samples are spiked with a nominal concentration of 0.05 ng/mL. Surrogate spike recoveries will be documented and discussed in the final report. Surrogate recoveries between 10025% will be deemed as meeting method criteria for accuracy.
(4) Several method blanks may be prepared and analyzed to better determine a "representative" area count value for the method blank. The method blank area count is instrumental in determining the method limit of quantitation and understanding the average and range of area counts possible is critical. If a method blank value is used as a "zero point" in the final calibration curve, then a brief explanation in the final report or in the raw data as a Note to File must be
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included to describe why that specific method blank was selected as the zero point (closest to the average value, most conservative (largest) value, etc.) (5) The overall analytical uncertainty for each target (non-surrogate) analyte will be estimated using both the method accuracy and precision. The method accuracy and precision will be calculated using data from laboratory contorl spike (LCS) samples prepared and analyzed with the sample set(s). Replicate LCSs must be prepared each day samples and/or other quality control samples are prepared. A sample calculation of how the analytical uncertainty was determined will be provided in the final report and/or raw data.
A new revision of ETS 8-154 may incorporate all or several of the modifications listed above. If a new version of ETS 8-154 is issued during the course of this study, sample results must meet the new method requirements regardless if they are listed above.
3M Environmental Laboratory management will approve all documented deviations to the 3M Environmental Laboratory quality system (SOPs, methods, etc.) that occur during the course of this investigation.
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Protocol Exygen PO001131; 3M Study Number E050270 Amendment 3
Amendment Approval
Michael A. Santd/ro,3M,
Sponsor Representative
Date
William K. Reapn, Ph.D.
3M Environmental Laboratory Manager
Date
W
Jaisimha Kesari, Weston Solutions,
Study Director
Date
E05-02 10
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