Document 3NzkX6VvLR1rz4Xg7Gxe5GJyy

3 3M Environmental Laboratory E05-0210 Interim Report#13 Interim Report #13: Analysis of Tennessee River Water Samples 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 Performing Laboratory 3M Environmental Laboratory Building 2-3E-09 935 Bush Ave. St. Paul, MN 55106 Project Identification E05-0210 160 Total Number of Pages E05-0210 Interim Report#13 Tennessee River Page 1 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 This page has been reserved for specific country requirements. E05-0210 Interim Report#13 Tennessee River Page 2 of 160 3M Envlronmental Laboratory E010210 lnterlm Report#13 GLP COMPLIANCSETATEMENT Study Title: Analysis of Pertluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Pertluorooctanesulfonate (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 Tennessee River Water Samples Interim Study IdentificationNumber: E05210 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 cotppliance: Jaisimha Kesan'P. E., DEE, Study Director .3b1/!7b DQte I Michael A. Santoro, &/k Company, Sponsor Representahve ' Date E050210 Interim Report#l3 Tennessee Rlver Page 3 of 160 3M EnvlrpnmefrtalLaboratory EO50210 Interim Reportl13 QUALITYASSURANCSETATEMENT Study Title: Analysisof Pefluorobutanesulfonate(PFBS), Perfhorohexanesulfonate (PFHS), and Pertluorooctanesulfonate(PFOS) nWater, Soil, Sediment, Fish, Clams,Vegetation, Small Mammal Liver and Small Mammal Serum Using LCIMSIMS for the 3M Decatur Monitoring Program InterimStudy: Analysisof Tennessee River Water Samples InterimStudy IdentificationNumber: E05-0210, Interim Report #I3 This study was audited by the 3M Environmental Laboratory Quality Assurance Unit (QAU), as indicated in the followingtable. The findings were reportedto the study director and laboratory management. July 27,2005 October 5-7,12,13,2005 Inphase Data/Final Report 11-07-2005 11-17-2005 11-07-2005 11-17-2005 - Date EO50210 Intetfm R e p o m 3 Tennessee River P8ge 4 O f 160 3M Environmental Laboratory E05-0210 Interim Report#13 TABLE OF CONTENTS GLP Compliance Statement ......................................................................................................................3 Quality Assurance Statement ....................................................................................................................4 Table of Contents .......................................................................................................................................5 List of Tables...............................................................................................................................................6 Study Information .......................................................................................................................................8 Summary and Introduction.........................................................................................................................9 Test Samples............................................................................................................................................15 Reference Substances.............................................................................................................................15 Control Substance....................................................................................................................................15 Method Summaries ..................................................................................................................................16 Sample Collection ........................................................................................................................16 Preparatory and Analytical Methods ...........................................................................................17 Extraction ......................................................................................................................................17 Analysis.........................................................................................................................................17 Analytical Results .....................................................................................................................................18 Calibration.....................................................................................................................................18 Limit of Quantitation (LOQ)..........................................................................................................18 Blanks ...........................................................................................................................................19 Solvent Blank................................................................................................................................19 Method Blank................................................................................................................................19 Trip Blank......................................................................................................................................21 System Suitability .........................................................................................................................21 Continuing Calibration..................................................................................................................21 Lab Control Spikes (LCSs) ..........................................................................................................21 Sample Duplicates .......................................................................................................................26 Surrogates ....................................................................................................................................26 E05-0210 Interim Report#13 Tennessee River Page 5 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Field Matrix Spikes.......................................................................................................................26 Data Summary and Discussion ...............................................................................................................26 PFBS.............................................................................................................................................26 PFHS ............................................................................................................................................26 PFOS ............................................................................................................................................27 PFOA[1,2 13C] Surrogate .............................................................................................................27 Statistical Methods and Calculations.......................................................................................................51 Accuracy and Precision Equations..............................................................................................51 Determination of Analytical Uncertainty ......................................................................................52 Statement of Conclusion..........................................................................................................................52 List of Attachments...................................................................................................................................52 Signature Page.........................................................................................................................................53 LIST OF TABLES Table 1. Sample Results Summary .......................................................................................................... 10 Table 2. Study Reference Substance. ...................................................................................................... 15 Table 3. Study Control Substance (Surrogate). ....................................................................................... 16 Table 4. Sample Collection Information.................................................................................................... 16 Table 5. Instrument Parameters................................................................................................................ 17 Table 6. Liquid Chromatography Gradient Program................................................................................ 17 Table 7. Mass Transitions.......................................................................................................................... 18 Table 8. LOQs by Extraction Set and Analysis Day................................................................................. 18 Table 9. Method Blank Area Counts for Extractions Performed on 07/26/2005; Samples Analyzed on 07/26/2005.................................................................................................................................. 19 Table 10. Method Blank Area Counts for Extractions Performed on 07/27/2005; Samples Analyzed on 07/28/2005 and 07/30/2005. ..................................................................................................... 20 Table 11. Method Blank Area Counts for Extraction Performed on 07/28/2005 (Centrifuged Samples); Samples Analyzed on 08/01/2005. ........................................................................................... 20 E05-0210 Interim Report#13 Tennessee River Page 6 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 12. Surrogate Spiked Method Blank Recoveries........................................................................... 21 Table 13. Lab Control Spike Results: Extraction Day 07/26/2005; Analysis Day 07/26/2005. ............ 23 Table 14. Lab Control Spike Results: Extraction Day 07/27/2005; Analysis Days 07/28/2005 & 07/30/2005.................................................................................................................................. 24 Table 15. Lab Control Spike Results: Extraction Day 07/28/2005 (Centrifuged Samples); Analysis Day: 08/01/2005........................................................................................................................ 25 Table 16. PFBS Sample Results............................................................................................................... 28 Table 17. PFHS Sample Results. ............................................................................................................. 34 Table 18. PFOS Sample Results. ............................................................................................................. 40 Table 19. PFOA[1,2 13C] Surrogate Results............................................................................................. 46 E05-0210 Interim Report#13 Tennessee River Page 7 of 160 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#13 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: July 26, 2005 Interim Experimental Completion: August 1, 2005 Interim Study Completion: State of Study Director's Signature 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. E05-0210 Interim Report#13 Tennessee River Page 8 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 SUMMARY AND INTRODUCTION The 3M Environmental Laboratory extracted and analyzed water samples collected from the Tennessee River by Weston Solutions personnel on July 18-22, 2005. Samples were collected from Tennessee River Mile (TRM) 307, located six miles upstream from the 3M Decatur Alabama facility to TRM 254, located 47 miles downstream from the 3M facility. Samples were submitted for analysis as part of 3M Environmental Laboratory project number E05-0210 (3M Decatur Fluorochemical GLP Monitoring Program, Interim Study #13: Analysis of Tennessee River Water Samples). 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). The analytical start date for this interim report was July 26, 2005 and the analytical termination date was August 1, 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 (0.05 ng/mL) and high field spike (0.5 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) for all the analytes varied depending on the extraction and analysis dates. All results for quality control samples prepared and analyzed with the samples will be reported and discussed elsewhere in this report. E05-0210 Interim Report#13 Tennessee River Page 9 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 1. Sample Results Summary Sample Description DLS-SW-TRM307-0-050718 DLS-SW-TRM307-0-050718 Dup DLS-SW-TRM301-0-050718 DLS-SW-TRM301-0-050718 Dup DLS-SW-TRM301-F-050718 DLS-SW-TRM301-F-050718 Dup DLS-SW-TRM295-0-050719 DLS-SW-TRM295-0-050719 Dup DLS-SW-TRM289-0-050719 DLS-SW-TRM289-0-050719 Dup DLS-SW-TRM289-F-050719 DLS-SW-TRM289-F-050719 Dup DLS-SW-TRM283-0-050719 DLS-SW-TRM283-0-050719 Dup DLS-SW-TRM277-0-050719 DLS-SW-TRM277-0-050719 Dup DLS-SW-TRM277-F-050719 DLS-SW-TRM277-F-050719 Dup DLS-SW-TRM271-0-050719 DLS-SW-TRM271-0-050719 Dup 3M LIMS ID Number E05-0210-86358 E05-0210-86359 Average %RPD E05-0210-86362 E05-0210-86363 Average %RPD E05-0210-86366 E05-0210-86367 Average %RPD E05-0210-86372 E05-0210-86373 Average %RPD E05-0210-86374 E05-0210-86375 Average %RPD E05-0210-86378 E05-0210-86379 Average %RPD E05-0210-86382 E05-0210-86383 Average %RPD E05-0210-86386 E05-0210-86387 Average %RPD E05-0210-86390 E05-0210-86391 Average %RPD E05-0210-86394 E05-0210-86395 Average %RPD (1)PFBS (ng/mL) (1)PFHS (ng/mL) < 0.00221 < 0.00221 (2)< 0.00221 NA < 0.00104 < 0.00104 (2)< 0.00104 NA < 0.00221 < 0.00221 (2)< 0.00221 NA < 0.00104 0.00134 (3)0.00134 NA < 0.00221 < 0.00221 (2)< 0.00221 NA (3)0.0143 (3)0.0150 0.0146 4.79 < 0.00104 < 0.00104 (2)< 0.00104 NA 0.0115 0.0118 0.0116 2.59 0.0225 0.0213 0.0218 5.50 0.0133 0.0123 0.0127 7.87 0.0197 0.0201 0.0199 2.01 0.0129 0.0120 0.0124 7.26 0.0203 0.0181 0.0192 11.4 0.00888 0.00883 0.00886 0.564 0.0115 0.0123 0.0119 6.72 0.00579 0.00704 0.00642 19.5 0.0111 0.0125 0.0118 11.9 0.00609 0.00672 0.00640 9.84 0.0133 0.0142 0.0138 6.52 0.00512 0.00574 0.00543 11.4 (1)PFOS (ng/mL) 0.0067 < 0.00496 (2)< 0.00496 NA < 0.00496 < 0.00496 (2)< 0.00496 NA < 0.00496 < 0.00496 (2)< 0.00496 NA 0.0736 0.0747 0.0742 1.48 0.0763 0.0722 0.0742 5.52 0.0588 0.0462 0.0524 24.0 0.0528 0.0703 0.0616 28.4 0.0336 0.0530 0.0432 44.9 0.0304 0.0390 0.0347 24.8 0.0320 0.0332 0.0326 3.68 E05-0210 Interim Report#13 Tennessee River Page 10 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 1. Sample Results Summary Continued. Sample Description DLS-SW-TRM265-0-050719 DLS-SW-TRM265-0-050719 Dup DLS-SW-TRM261-2-050720 DLS-SW-TRM261-2-050720 Dup DLS-SW-TRM261-0-050720 DLS-SW-TRM261-0-050720 Dup DLS-SW-TRM261-F-050720 DLS-SW-TRM261-F-050720 Dup DLS-SW-TRM256-0-050720 DLS-SW-TRM256-0-050720 Dup DLS-SW-TRM254-0-050720 DLS-SW-TRM254-0-050720 Dup DLS-SW-TRM254-F-050720 DLS-SW-TRM254-F-050720 Dup DLS-SW-TRM254-2-050720 DLS-SW-TRM254-2-050720 Dup DXS-SW-T01001-0-050721 DXS-SW-T01001-0-050721 Dup DXS-SW-T01002-0-050721 DXS-SW-T01002-0-050721 Dup 3M LIMS ID Number E05-0210-86398 E05-0210-86399 Average %RPD E05-0210-86402 E05-0210-86403 Average %RPD E05-0210-86406 E05-0210-86407 Average %RPD E05-0210-86410 E05-0210-86411 Average %RPD E05-0210-86414 E05-0210-86415 Average %RPD E05-0210-86418 E05-0210-86419 Average %RPD E05-0210-86422 E05-0210-86423 Average %RPD E05-0210-86426 E05-0210-86427 Average %RPD E05-0210-86430 E05-0210-86431 Average %RPD E05-0210-86434 E05-0210-86435 Average %RPD (1)PFBS (ng/mL) (1)PFHS (ng/mL) 0.0103 0.0104 0.0104 0.962 0.00525 0.00542 0.00534 3.18 < 0.00221 < 0.00221 (2)< 0.00221 NA < 0.00104 < 0.00104 (2)< 0.00104 NA 0.0118 0.0110 0.0114 7.02 0.0052 0.00481 0.00500 7.80 0.0116 0.0107 0.0112 8.04 0.00542 0.00486 0.00514 10.9 0.0111 0.0125 0.0118 11.9 0.00485 0.0047 0.00478 3.14 0.0124 0.0120 0.0121 3.30 0.0055 0.00481 0.00516 13.4 0.0128 0.0121 0.0124 5.64 0.00533 0.00525 0.00528 1.52 < 0.00221 < 0.00221 (2)<0.00221 NA < 0.00104 < 0.00104 (2)<0.00104 NA 0.0215 0.0201 0.0208 6.73 0.0121 0.0116 0.0118 4.24 0.0161 0.0164 0.0162 1.85 0.0101 0.00959 0.00984 5.18 (1)PFOS (ng/mL) 0.0377 0.0375 0.0375 0.533 < 0.00496 < 0.00496 (2)< 0.00496 NA 0.0324 0.0330 0.0323 1.86 0.0333 0.0232 0.0282 35.8 0.0326 0.0342 0.0333 4.80 0.0352 0.0341 0.0346 3.18 0.0300 0.0342 0.0321 13.1 < 0.00992 < 0.00992 (2)<0.00992 NA 0.0739 0.0680 0.0710 8.31 0.0607 0.0594 0.0600 2.17 E05-0210 Interim Report#13 Tennessee River Page 11 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 1. Sample Results Summary Continued. Sample Description DXS-SW-T01003-0-050721 DXS-SW-T01003-0-050721 Dup DXS-SW-T01004-0-050721 DXS-SW-T01004-0-050721 Dup DXS-SW-T01005-0-050721 DXS-SW-T01005-0-050721 Dup DXS-SW-T01006-0-050721 DXS-SW-T01006-0-050721 Dup DXS-SW-T01007-0-050721 DXS-SW-T01007-0-050721 Dup DXS-SW-T01008-0-050721 DXS-SW-T01008-0-050721 Dup DXS-SW-T01009-0-050721 DXS-SW-T01009-0-050721 Dup DXS-SW-T01010-0-050721 DXS-SW-T01010-0-050721 Dup DXS-SW-T02001-0-050721 DXS-SW-T02001-0-050721 Dup DXS-SW-T02002-0-050721 DXS-SW-T02002-0-050721 Dup 3M LIMS ID Number E05-0210-86438 E05-0210-86439 Average %RPD E05-0210-86442 E05-0210-86443 Average %RPD E05-0210-86446 E05-0210-86447 Average %RPD E05-0210-86450 E05-0210-86451 Average %RPD E05-0210-86454 E05-0210-86455 Average %RPD E05-0210-86458 E05-0210-86459 Average %RPD E05-0210-86462 E05-0210-86463 Average %RPD E05-0210-86466 E05-0210-86467 Average %RPD E05-0210-86470 E05-0210-86471 Average %RPD E05-0210-86474 E05-0210-86475 Average %RPD (1)PFBS (ng/mL) (1)PFHS (ng/mL) 0.0165 0.0166 0.0166 0.602 0.00827 0.00941 0.00884 12.9 0.0158 0.0165 0.0162 4.32 0.00967 0.0101 0.00988 4.35 0.00957 0.00985 0.00971 2.88 0.00633 0.00667 0.00649 5.24 0.00432 0.00366 0.00399 16.5 0.00346 0.00333 0.00340 3.82 0.00566 0.00564 0.00565 0.354 0.00419 0.00429 0.00424 2.36 0.00369 0.00502 0.00436 30.5 0.00316 0.00328 0.00321 3.74 0.00491 0.00444 0.00468 10.0 0.00301 0.0033 0.00316 9.18 0.00395 0.00385 0.00390 2.56 0.00332 0.00277 0.00304 18.1 0.0414 0.0423 0.0418 2.15 0.0205 0.0187 0.0195 9.23 0.0306 0.0316 0.0311 3.22 0.0124 0.0126 0.0125 1.60 (1)PFOS (ng/mL) 0.0542 0.0555 0.0548 2.37 0.056 0.0636 0.0598 12.7 0.0383 0.039 0.0386 1.81 0.0209 0.0219 0.0213 4.69 0.0273 0.0268 0.0270 1.85 0.0219 0.0217 0.0218 0.917 0.0202 0.0203 0.0202 0.495 0.0216 0.0219 0.0218 1.38 0.129 0.117 0.123 9.76 0.0707 0.0762 0.0734 7.49 E05-0210 Interim Report#13 Tennessee River Page 12 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 1. Sample Results Summary Continued. Sample Description DXS-SW-T02003-0-050721 DXS-SW-T02003-0-050721 Dup DXS-SW-T02004-0-050721 DXS-SW-T02004-0-050721 Dup DXS-SW-T02005-0-050721 DXS-SW-T02005-0-050721 Dup DXS-SW-T02006-0-050721 DXS-SW-T02006-0-050721 Dup DXS-SW-T02007-0-050721 DXS-SW-T02007-0-050721 Dup DXS-SW-T02008-0-050721 DXS-SW-T02008-0-050721 Dup DXS-SW-T02009-0-050721 DXS-SW-T02009-0-050721 Dup DXS-SW-T02010-0-050721 DXS-SW-T02010-0-050721 Dup DXS-SW-T03001-0-050721 DXS-SW-T03001-0-050721 Dup DXS-SW-T03002-0-050721 DXS-SW-T03002-0-050721 Dup 3M LIMS ID Number E05-0210-86478 E05-0210-86479 Average %RPD E05-0210-86482 E05-0210-86483 Average %RPD E05-0210-86486 E05-0210-86487 Average %RPD E05-0210-86490 E05-0210-86491 Average %RPD E05-0210-86494 E05-0210-86495 Average %RPD E05-0210-86498 E05-0210-86499 Average %RPD E05-0210-86502 E05-0210-86503 Average %RPD E05-0210-86506 E05-0210-86507 Average %RPD E05-0210-86510 E05-0210-86511 Average %RPD E05-0210-86514 E05-0210-86515 Average %RPD (1)PFBS (ng/mL) (1)PFHS (ng/mL) < 0.00221 < 0.00221 (2)<0.00221 NA < 0.00104 < 0.00104 (2)<0.00104 NA < 0.00221 < 0.00221 (2)<0.00221 NA < 0.00104 < 0.00104 (2)<0.00104 NA < 0.000883 < 0.00221 (2)<0.00221 NA < 0.0026 < 0.0026 (2)<0.0026 NA < 0.000883 0.00101 (4)0.00101 NA < 0.0026 < 0.0026 (2)<0.0026 NA < 0.000883 < 0.000883 (2)< 0.000883 NA < 0.0026 < 0.0026 (2)< 0.0026 NA 0.00109 0.00115 0.00111 5.40 < 0.0026 < 0.0026 (2)< 0.0026 NA 0.00288 0.00244 0.00266 16.5 < 0.0026 < 0.0026 (2)< 0.0026 NA 0.00628 0.00553 0.00590 12.7 0.00363 0.00342 0.00352 5.96 0.818 0.854 0.836 4.31 0.176 0.185 0.180 5.00 0.00519 0.00424 0.00472 20.1 < 0.0026 < 0.0026 (2)< 0.0026 NA (1)PFOS (ng/mL) < 0.00992 < 0.00992 (2)<0.00992 NA < 0.00992 < 0.00992 (2)<0.00992 NA < 0.00744 < 0.0496 (2)<0.0496 NA < 0.00744 0.00799 (4)0.00799 NA < 0.00744 < 0.00744 (2)< 0.00744 NA < 0.00744 < 0.00744 (2)< 0.00744 NA 0.00872 0.00883 0.00878 1.25 0.0426 0.0285 0.0356 39.6 0.782 0.807 0.794 3.15 0.0235 0.0169 0.0201 32.8 E05-0210 Interim Report#13 Tennessee River Page 13 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 1. Sample Results Summary Continued. Sample Description 3M LIMS ID Number (1)PFBS (ng/mL) (1)PFHS (ng/mL) (1)PFOS (ng/mL) DXS-SW-T03003-0-050721 DXS-SW-T03003-0-050721 Dup E05-0210-86518 E05-0210-86519 Average %RPD < 0.000883 < 0.000883 (2)< 0.000883 NA < 0.0026 < 0.0026 (2)< 0.0026 NA 0.0111 0.0118 0.0114 6.14 DXS-SW-T03004-0-050722 DXS-SW-T03004-0-050722 Dup E05-0210-86522 E05-0210-86523 Average %RPD 0.0043 0.00106 0.00268 121 0.00756 < 0.0026 0.00756 NA 0.0226 0.0167 0.0196 30.1 DXS-SW-T03005-0-050722 DXS-SW-T03005-0-050722 Dup E05-0210-86526 E05-0210-86527 Average %RPD < 0.000883 0.00171 (3)0.00171 NA < 0.0026 0.00331 (4)0.00331 NA < 0.00744 0.0773 (4)0.0773 NA DXS-SW-T03006-0-050722 DXS-SW-T03006-0-050722 Dup E05-0210-86530 E05-0210-86531 Average %RPD < 0.000883 < 0.000883 (2)< 0.000883 NA < 0.0026 < 0.0026 (2)< 0.0026 NA 0.00763 < 0.00744 (4)0.00763 NA DXS-SW-T03007-0-050722 DXS-SW-T03007-0-050722 Dup E05-0210-86534 E05-0210-86535 Average %RPD < 0.000883 0.00107 (4)0.00107 NA < 0.0026 0.00366 (4)0.00366 NA < 0.00744 < 0.0496 (2)<0.0496 NA DXS-SW-T03008-0-050722 DXS-SW-T03008-0-050722 Dup E05-0210-86538 E05-0210-86539 Average %RPD < 0.000883 < 0.000883 (2)< 0.000883 NA < 0.0026 < 0.0026 (2)< 0.0026 NA < 0.00744 < 0.00744 (2)< 0.00744 NA DXS-SW-T03009-0-050722 DXS-SW-T03009-0-050722 Dup E05-0210-86542 E05-0210-86543 Average %RPD < 0.000883 < 0.000883 (2)< 0.000883 NA < 0.0026 < 0.0026 (2)< 0.0026 NA 0.00809 < 0.00744 (4)0.00809 NA DXS-SW-T03010-0-050722 E05-0210-86546 0.000908 < 0.0026 0.00749 DXS-SW-T03010-0-050722 Dup E05-0210-86547 Average < 0.000883 (4)0.000908 < 0.0026 (2)< 0.0026 < 0.00744 (4)0.00749 %RPD NA NA NA (1) All results and calculations are presented with three significant figures. Sample concentrations, averages, and %RPD values may vary slightly from the raw data. The analytical uncertainty for the PFBS, PFHS, and PFOS results is 10010.6%, 10015.2%, and 10013.8%, respectively. (2) NA: Not applicable. %RPD values not determined when concentrations for the sample and/or sample duplicate are below the stated LOQ. (3) Sample descriptions were misidentified when checked into LIMS. Samples with LIMS ID numbers 86370 and 86371 were in bottles labeled low and high spike, respectively. Bottles with LIMS ID numbers 86372 and 86373 were surrogate spiked only (sample and sample duplicate bottles). (4) 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. E05-0210 Interim Report#13 Tennessee River Page 14 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 TEST SAMPLES Water samples (3M LIMS ID #86358-86558) were received on July 23, 2005 from Charles Young of Weston Solutions, Inc. Two hundred one (201) containers representing 48 samples and an equipment rinse blank 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 July 26-28, 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 Identifier (1)Source Expiration Date Storage Conditions Chemical Lot Number TCR Number C4F9SO3-K+ CAS # 29420-49-3 3M 10/17/2006 Frozen 101 TCR-116 (99030-023) C6F13SO3-K+ CAS # 3871-99-6 3M 10/18/2006 Frozen NB# 120067-69 TCR-83 (SE036) C8F17SO3K+ CAS # 2795-39-3 3M 8/31/2006 Frozen 171 TCR-696 Physical Description White Powder White Powder White powder Purity (2)Solubility (1) (2) 96.7% 98.6% 86.4% 54,400 ppm No Information available Documentation regarding synthesis of the test substances is located at the source. 680 ppm All test substances are believed to be soluble in water at the levels to be investigated. No visual precipitates observed. 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. E05-0210 Interim Report#13 Tennessee River Page 15 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 3. Study Control Substance (Surrogate). Reference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity PFOA [1,2 13C] Perfluorooctanoic Acid C6F15[13C]F2[13C]OOH N/A Perkin Elmer 03/29/2009 Frozen 3507-195 TCR-744 White powder >97% METHOD SUMMARIES Sample Collection Samples were collected on July 18-23, 2005 in pre-rinsed NalgeneTM (low-density polyethylene) bottles prepared at the 3M Environmental Laboratory on July 14, 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 analyte of interest. 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, three "Trip Blank" sample sets were 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 below details the spike amounts for the four bottles comprising the sample location set. Table 4. Sample Collection Information (1)Bottle Description Nominal Final Volume Collected (mL) PFBS Final Spike Concentration (ng/mL) PFHS PFOS PFOA [1,2 13C] (Surrogate) Sample 450 NA NA NA Sample Dup 450 NA NA NA Low Field Matrix Spike (LS) 450 0.0441 0.0521 0.0496 High Field Matrix Spike (HS) 450 0.441 0.521 0.496 (1) The sample description was assigned in the field by Weston Solutions personnel. 0.274 0.274 0.254 0.254 E05-0210 Interim Report#13 Tennessee River Page 16 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Preparatory and Analytical Methods Extraction All samples, calibration standards, and associated quality control samples were extracted using a modified procedure of 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, approximately 100 mL of sample were 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 2 mL of methanol This extraction procedure concentrates the samples by a factor of fifty. (Initial volume = 100 mL, final volume = 2 mL). As written, ETS-8-154.1 calls for a 40 mL and 5 mL extraction and elution volume, respectively. Due to the large number of samples associated with this project, samples were extracted over the course of three days (July 26-July 28, 2005). The extracted calibration curve used to quantify the data was only prepared on the first extraction day; however, method blanks and lab control spikes were prepared each day samples were extracted. During the second day of extraction, six samples clogged the SPE cartridge preventing complete loading of the sample. On the third extraction day, these six samples were centrifuged at 6000 rcf (relative centrifugal force) for 20 minutes prior to loading the SPE cartridge. Method blanks and lab control spikes were also centrifuged and extracted in a similar manner. 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 ETStan Agilent 1100 Betasil C18 2X50, 5 m Betasil C18 (2.1 mm X 100 mm), 5 m 5 L Applied Biosystems API 4000 Z-spray Turbo Spray Negative Analyst 1.4.1 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 E05-0210 Interim Report#13 Tennessee River Page 17 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 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) 150 150 150 150 150 150 150 150 (1) The individual 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 100 mL of ASTM type I water. Each spiked water standard was then extracted in the same manner as the collected samples. A total of twelve spiked standards ranging from 0.001 ng/mL to 2.5 ng/mL (nominal) were prepared. A quadratic, 1/x weighted, calibration curve was used to fit the data for each analyte. The data was 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%. Coefficients of determination (r2) were greater than 0.995 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 at least twice those of the method blank(s). The LOQ varied from day to day depending on instrument sensitivity and method blank area counts for the extraction set. This will be presented and discussed in more detail in the section below regarding method blanks. Table 8 below provides the individual LOQs for the three analytes of interest. Table 8. LOQs by Extraction Set and Analysis Day Extraction Set 07/26/2005 07/27/2005 07/28/2005 (Centrifuged Samples) Analysis Day 07/26/2005 07/28/2005 07/30/2005 08/01/2005 PFBS (ng/mL) 0.00221 0.00221 0.000883 0.00221 LOQ PFHS (ng/mL) 0.00104 0.00104 0.00260 0.00260 PFOS (ng/mL) 0.00496 0.00992 0.00744 0.0496 E05-0210 Interim Report#13 Tennessee River Page 18 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 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 blank samples were less than half the area counts of the calibration standard used to establish the LOQ. Method Blank Over the three days in which samples, calibration standards, and quality control samples were extracted, several method blanks were prepared by loading 100 mL of ASTM Type I water onto a C18 SPE cartridge and eluting with 2 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.) Approximately half of the method blanks prepared each day were spiked with a known amount of PFOA [1,2 13C] surrogate prior to extraction. Table 9 and Table 10 list the analyte area counts for the method blanks and the corresponding LOQ standard for the given analysis day. Table 11 lists the analyte area counts of the method blanks associated with the centrifuged samples. The PFOS LOQ for these six samples was raised to 0.0496 ng/mL due to higher amounts of PFOS detected in the method blanks prepared on that day. Surrogate recoveries for the spiked method blanks are presented in Table 12. Method blanks spiked with surrogate solution produced an average recovery of 176% with a RSD of 8.45%. An older spiking solution that had been used extensively since preparation is hypothesized to be the underlying cause of the high recovery. Solvent evaporation due to opening the storage container several times is plausible. Table 9. Method Blank Area Counts for Extractions Performed on 07/26/2005; Samples Analyzed on 07/26/2005. Sample Name Sample Comment s050726a028 Method Blank-1 s050726a029 Method Blank-2 s050726a030 Method Blank-3 s050726a031 Method Blank-4 s050726a032 Method Blank-5 s050726a033 Method Blank-6 s050726a034 Method Blank-7 s050726a035 Method Blank-8 LOQ Standard Area Counts LOQ Standard Concentration Sample ID MB-050726-1 MB-050726-2 MB-050726-3 MB-050726-4 MB-050726-5 MB-050726-6 MB-050726-7 MB-050726-8 PFBS Area PFHS Area PFOS Area Counts Counts Counts 2250 2770 4317 2314 8191 3771 3668 2600 26255 0.00221 1301 1881 1793 1754 1642 1804 1546 949 8250 0.00104 3358 5306 5128 2802 4514 4259 4700 3662 12939 0.00496 E05-0210 Interim Report#13 Tennessee River Page 19 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 10. Method Blank Area Counts for Extractions Performed on 07/27/2005; Samples Analyzed on 07/28/2005 and 07/30/2005. Sample Name Sample Comment s050728a025 Method Blank-1 s050728a026 Method Blank-2 s050728a027 Method Blank-5 s050728a028 Method Blank-6 LOQ Standard Area Counts LOQ Standard Concentration s050730a025 Method Blank-3 s050730a026 Method Blank-4 s050730a027 Method Blank-7 s050730a028 Method Blank-8 LOQ Standard Area Counts LOQ Standard Concentration Sample ID MB-050727-1 MB-050727-2 MB-050727-5 MB-050727-6 MB-050727-3 MB-050727-4 MB-050727-7 MB-050727-8 PFBS Area PFHS Area PFOS Area Counts Counts Counts 3215 4573 3369 3316 27360 0.00221 3414 5089 3632 3941 14056 0.000880 1001 1930 39 0 6707 0.00104 28 213 48 1796 15862 0.00260 3488 9299 3045 4497 21214 0.00992 4043 9052 5865 9632 20564 0.00744 Table 11. Method Blank Area Counts for Extraction Performed on 07/28/2005 (Centrifuged Samples); Samples Analyzed on 08/01/2005. Sample Name Sample Comment Sample ID PFBS Area PFHS Area PFOS Area Counts Counts Counts Centrifuge s050801a025 Method Blank-1 MB-050728-1 7312 3369 27461 Yes s050801a026 Method Blank-2 MB-050728-2 3505 2182 24740 Yes s050801a027 Method Blank-3 MB-050728-3 7853 5636 42506 No s050801a028 Method Blank-4 MB-050728-4 4363 2456 28031 No s050801a029 Method Blank-5 MB-050728-5 2528 925 19878 Yes s050801a030 s050801a031 s050801a032 Method Blank-6 Method Blank-7 Method Blank-8 MB-050728-6 MB-050728-7 MB-050728-8 2673 (1)73234 (1)29997 1104 18783 Yes (1)105441 (1)1495463 No (1)38166 (1)237882 No LOQ Standard Area Counts 26908 15530 107559 LOQ Standard Concentration 0.00221 0.00260 0.0496 (1) The area counts for Method Blank-7 and Method Blank-8 were determined to be statistical outliers using Dixon's Q test. These data points were excluded when determining the LOQs for the centrifuged samples. E05-0210 Interim Report#13 Tennessee River Page 20 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 12. Surrogate Spiked Method Blank Recoveries. Sample Name Sample Comment Sample ID Analyte Concentration (ng/mL) Calculated Concentration PFOA [1,2 13C] ng/mL Percent Surrogate Recovery s050726a032 Method Blank-5 MB-050726-5 0.102 0.197 193 s050726a033 Method Blank-6 MB-050726-6 0.102 0.169 166 s050726a034 Method Blank-7 MB-050726-7 0.102 0.197 193 s050726a035 Method Blank-8 MB-050726-8 0.102 0.175 172 s050728a027 Method Blank-5 MB-050727-5 0.102 0.16 157 s050728a028 Method Blank-6 MB-050727-6 0.102 0.163 160 s050730a027 s050730a028 Method Blank-7 Method Blank-8 MB-050727-7 MB-050727-8 0.102 0.102 0.166 <0.00249 163 (1)NA s050801a029 Method Blank-5 MB-050728-5 0.102 0.184 180 s050801a030 Method Blank-6 MB-050728-6 0.102 0.178 174 s050801a031 Method Blank-7 MB-050728-7 0.102 0.206 202 s050801a032 Method Blank-8 MB-050728-8 0.102 0.182 178 (1) NA: Not applicable. Surrogate not measured in final extract suggesting that the solution was inadvertently not spiked prior to extraction. (2) The average surrogate recovery in spiked method blanks was 176% (RSD=8.45%). Trip Blank Prior to sample collection, three sample containers were 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. These samples were analyzed as field/trip blanks. Trip blanks serve as additional method blanks that account for any storage conditions and/or holding time issues that the samples may experience. The resultant field/trip blank concentrations for PFBS, PFHS, and PFOS were <0.000883 ng/mL, <0.00260 ng/mL, and <0.00744 ng/mL, respectively. System Suitability A 1.0 ng/mL (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 was 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 was still in control. All CCVs for all four analytes produced recoveries within 25%, which met method criteria. Lab Control Spikes (LCSs) Replicate low (0.025 ng/mL nominal concentration) and high (1.25 ng/mL nominal concentration) lab control spikes were prepared and extracted each day samples or calibration standards were extracted. LCSs were prepared by spiking known amounts of the analytes into 100 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 each extraction day are E05-0210 Interim Report#13 Tennessee River Page 21 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 presented in the data tables below. LCSs were used to evaluate method accuracy and precision which was then used to determine analytical uncertainty for each of the analytes reported with the results in Table 1. Information on how the analytical uncertainty was determined is provided at the end of this report in the "Statistical Methods and Calculations" section. For the third extraction day (07/28/2005 - centrifuged samples), a total of twelve LCSs were prepared. Six of the twelve replicates (three low, three high) were centrifuged before extraction in a manner similar to the samples. The remaining six replicates (three low, three high) were not centrifuged prior to extraction. These samples were prepared to verify that the added centrifugation step did not result in loss of target analytes. All LCS recoveries for the first two extraction days met method criteria for accuracy (percent recovery:10025%) and precision (%RSD 15%) for all analytes (Table 13 and Table 14). However, for the third extraction day, three LCS measurements exceeded method criteria for accuracy (two high level replicates of PFOA[1,2 13C] both with 131% recovery and one high level PFBS with 129% recovery). Despite these three exceedences, the LCS recoveries demonstrate excellent accuracy and precision, at both individual levels, and when considered collectively for this extraction day. Therefore, the samples extracted on that day are considered to be accurate within the stated method uncertainty. The overall project accuracy (percent recovery) and precision (percent RSD) was determined for each analyte using the LCS data from the three separate extraction days. The overall project accuracy and precision for PFBS, PFHS, and PFOS was 1073.49%, 1104.72%, and 1085.79%, respectively. These values were used to estimate the analytical uncertainty for each analyte which is described in detail in the Statistical Methods and Calculations section of this report. E05-0210 Interim Report#13 Tennessee River Page 22 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 13. Lab Control Spike Results: Extraction Day 07/26/2005; Analysis Day 07/26/2005. Sample Description Sample ID LCS Low-1 LCS-050726-1 LCS Low-2 LCS-050726-2 LCS Low-3 LCS-050726-3 Average Low Recovery %RSD (Extraction Day 7/26/2005) LCS High-1 LCS-050726-4 LCS High-2 LCS-050726-5 LCS High-3 LCS-050726-6 Average High Recovery %RSD (Extraction Day 7/26/2005) Average All LCSs%RSD (Extraction Day 7/26/2005) (1)PFBS (1)PFHS (1)PFOS (1)PFOA [1,2 13C] Analyte Conc. (ng/mL) Calc. Conc. (ng/mL) Percent Recovery Analyte Conc. (ng/mL) Calc. Conc. (ng/mL) Percent Recovery Analyte Conc. (ng/mL) Calc. Conc. (ng/mL) Percent Recovery Analyte Conc. (ng/mL) Calc. Conc. (ng/mL) Percent Recovery 0.0221 0.0243 110 0.0221 0.0233 105 0.0221 0.0246 111 0.026 0.0285 110 0.0248 0.0244 98.4 0.0249 0.0262 105 0.026 0.0298 115 0.0248 0.0279 112 0.0249 0.0283 114 0.026 0.0294 113 0.0248 0.03 121 0.0249 0.0275 110 109% 2.83% 112% 2.28% 111% 10.3% 110% 4.26% 1.10 1.15 104 1.30 1.4 108 1.24 1.35 109 1.25 1.25 100 1.10 1.18 107 1.30 1.41 108 1.24 1.35 109 1.25 1.18 94.4 1.10 1.19 108 1.30 1.44 111 1.24 1.42 114 1.25 1.23 98.4 107%1.77% 109%1.47% 111%2.94% 97.6% 2.96% 108%2.40% 111%2.43% 111%6.78% 104%7.15% (1). Table displays rounded values for all concentration and percent recovery values (3 significant figures). Recovery and RSD values may vary slightly from the values in the raw data. E05-0210 Interim Report#13 Tennessee River Page 23 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 14. Lab Control Spike Results: Extraction Day 07/27/2005; Analysis Days 07/28/2005 & 07/30/2005. (1)PFBS (1)PFHS (1)PFOS (1)PFOA [1,2 13C] Sample Description Sample ID Analyte Conc. (ng/mL) Calc. Conc. (ng/mL) Percent Recovery Analyte Conc. (ng/mL) Calc. Conc. (ng/mL) Percent Recovery Analyte Conc. (ng/mL) Calc. Conc. (ng/mL) Percent Recovery Analyte Conc. (ng/mL) Calc. Conc. (ng/mL) Percent Recovery LCS Low-1 LCS-050727-1 0.0221 0.0238 108 0.026 0.029 112 0.0248 0.0243 98.0 0.0249 0.0255 102 LCS Low-2 LCS-050727-2 0.0221 0.0238 108 0.026 0.0286 110 0.0248 0.0241 97.2 0.0249 0.0275 110 LCS Low-3 LCS-050727-3 0.0221 0.0233 105 0.026 0.0278 107 0.0248 0.0257 104 0.0249 0.0241 96.8 Average Low Recovery %RSD (Extraction Day 7/27/2005) 107% 1.22% 109% 2.15% 99.6%3.53% 103% 6.86% LCS High-1 LCS-050727-4 1.1 1.11 101 1.3 1.37 105 1.24 1.31 106 1.25 1.08 86.4 LCS High-2 LCS-050727-5 1.1 1.14 104 1.3 1.41 108 1.24 1.32 106 1.25 1.02 81.6 LCS High-3 LCS-050727-6 1.1 1.12 102 1.3 1.37 105 1.24 1.28 103 1.25 1.05 84.0 Average High Recovery %RSD (Extraction Day 7/27/2005) 102%1.36% 106%1.67% 105%1.60% 84.0%2.86% Average All LCSs%RSD (Extraction Day 7/27/2005) 104%2.78% 108%2.33% 102%3.81% 93.6%12.3% (1). Table displays rounded values for all concentration and percent recovery values (3 significant figures). Recovery and RSD values may vary slightly from the values in the raw data. E05-0210 Interim Report#13 Tennessee River Page 24 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 15. Lab Control Spike Results: Extraction Day 07/28/2005 (Centrifuged Samples); Analysis Day: 08/01/2005. (1)PFBS (1)PFHS (1)PFOS (1)PFOA [1,2 13C] Sample Description Sample ID LCS Low-1 Centrifuged LCS-050728-1 LCS Low-2 Centrifuged LCS-050728-2 LCS Low-3 Centrifuged LCS-050728-3 Average Low Centrifuged (Extraction Day 7/28/2005) LCS High-1 Centrifuged LCS-050728-4 LCS High-2 Centrifuged LCS-050728-5 LCS High-3 Centrifuged LCS-050728-6 Average High Centrifuged (Extraction Day 7/28/2005) Average All Centrifuged LCSs (Extraction Day 7/28/2005) LCS Low-7 LCS-050728-7 LCS Low-8 LCS-050728-8 LCS Low-9 LCS-050728-9 Average Low Non-Centrifugeed (Extraction Day 7/28/2005) LCS High-10 LCS-050728-10 LCS High-11 LCS-050728-11 LCS High-12 LCS-050728-12 Average High Non-Centrifuged (Extraction Day 7/28/2005) Average All Non-Centrifuged LCSs (Extraction Day 7/28/2005) Analyte Conc. (ng/mL) Calculated Conc. Percent (ng/mL) Recovery 0.0221 0.024 108 0.0221 0.0241 109 0.0221 0.0235 106 108%1.35% 1.1 1.2 109 1.1 1.2 109 1.1 1.16 105 108%1.95% 108%1.50% 0.0221 0.0236 107 0.0221 0.0263 119 0.0221 0.023 104 110%7.23 1.1 1.12 102 1.1 1.17 106 1.1 1.15 104 104%2.19% 107%5.69% Analyte Calculated Conc. Conc. Percent (ng/mL) (ng/mL) Recovery 0.026 0.029 112 0.026 0.0284 109 0.026 0.0288 111 110%1.06% 1.3 1.43 110 1.3 1.38 106 1.3 1.37 105 107%2.47% 109%2.31% 0.026 0.0294 113 0.026 0.0335 129 0.026 0.0304 117 120%6.87% 1.3 1.36 105 1.3 1.36 105 1.3 1.38 106 105%0.888% 112%8.46% Analyte Conc. (ng/mL) 0.0248 0.0248 0.0248 Calculated Conc. Percent (ng/mL) Recovery (2)<0.0496 NA (2)<0.0496 NA ((2)<0.0496 NA NA 1.24 1.42 114 1.24 1.36 110 1.24 1.35 109 111%2.75% (3)111%2.75% 0.0248 (2)<0.0496 NA 0.0248 (2)<0.0496 NA 0.0248 ((2)<0.0496 NA NA 1.24 1.29 104 1.24 1.36 110 1.24 1.37 110 108%3.25% (3)108%3.25% Analyte Calculated Conc. Conc. Percent (ng/mL) (ng/mL) Recovery 0.0249 0.028 112 0.0249 0.0307 123 0.0249 0.0297 119 118%5.48% 1.25 1.45 116 1.25 1.49 119 1.25 1.45 116 117%1.58% 118%3.16% 0.0249 0.0295 118 0.0249 0.0326 131 0.0249 0.0289 116 121%7.98% 1.25 1.43 114 1.25 1.45 116 1.25 1.64 131 120%7.69% 121%6.41% (1). Table displays rounded values for all concentration and percent recovery values (3 significant figures). Recovery and RSD values may vary slightly from the values in the raw data. (2) The PFOS LOQ for this analysis set was raised to 0.0496 due to method blank contamination. LCS results and recoveries were not reported. (3) The average value and %RSD were calculated using only the high level results. E05-0210 Interim Report#13 Tennessee River Page 25 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 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 surrogate spikes and 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[1,213C] concentration was 0.274 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 0.05 ng/mL) and high (nominal concentration 0.5 ng/mL) field matrix spikes were collected at each sampling point to verify that the analytical method is applicable to the collected matrix. The PFOA [1,2 13C] surrogate was added to each field matrix spike at a final concentration of 0.254 ng/mL. 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 The data tables below individually summarize the sample results and field matrix spike recoveries for each of the three analytes and the surrogate for all of the sampling locations plus the three trip blanks. PFBS PFBS matrix spike recoveries were within method acceptance criteria of 10030% for all sampling locations with the following exceptions: 3M LIMS sample numbers 86448 (low spike 174%), 86452 (low spike 137%), 86456 (low spike 223%), 86460 (low spike 134%), 86489 (high spike 136%), 86528 (low spike 133%), 86533 (high spike 134%) and 86558 (trip blank #3 high spike 18.0%). (See Table 16). For each of these instances, the corresponding high or low spike for the given location produced a spike recovery within method criteria of 10030%. Therefore, the sample results for these locations are reported within the stated method analytical uncertainty and are considered accurate to within 10030% for the given location. PFHS PFHS matrix spike recoveries were within method acceptance criteria of 10030% for all sampling locations with the following exceptions: 3M LIMS sample numbers 86448 (low spike 170%), 86452 (low spike 134%), 86509 (high spike 67.8%), 86512 (low spike 133%), and 86532 (low spike 54.7%). Refer to Table 17 for more information. For each of these instances, the corresponding high or low spike for the given sampling location produced a spike recovery within method criteria of 10030%. Therefore, the sample results for these locations are reported within the stated method analytical uncertainty and are considered accurate to within 10030% for the given location. E05-0210 Interim Report#13 Tennessee River Page 26 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 PFOS In general, PFOS matrix spike recoveries were within method acceptance criteria of 10030% with a few exceptions. Six locations produced recoveries that exceeded method critera for the low-level spike but were acceptable for the high-level spike. The 3M LIMS sample numbers for these instances were 86380 (low spike 136%), 86448 (low spike 191%), 86452 (low spike 139%), 86460 (low spike 136%), 86489 (low spike 138%), and 86536 (low spike 134%). With the exception of sample number 86448, the low-level spike recovery was high, but less than 150%. Because the high-level spike recoveries for these samples met method criteria, the sample results for these locations are reported within the stated method analytical accuracy and are considered accurate to within 10030%. Additionally, three sampling locations produced matrix spike recoveries outside the 10030% criteria for both spike levels: DXS-SW-T02006-0-050721 (low spike 131%, high spike 133%), DXS-SW-T02010-0-050721 (low spike 47.4%, high spike 51.9%), and DXSSW-T03006-0-050722 (low spike 2.91%, high spike 132%). For locations DXS-SW-T020060-050721 and DXS-SW-T02010-050721, the accuracy for the sample/sample duplicate results has been increased to 10050% to account for the slightly high recoveries for DXSSW-T02006-0-050721 (132% average) and the low recoveries for DXS-SW-T02010-050721 (approximately 50% average). Furthermore, the sample/sample duplicate %RPD for DXSSW-T02010-050721 was greater than 30%. The accuracy for location DXS-SW-T03006-0050722 has been increased to of 10050% based solely on the high spike recovery (132%). All sample locations with adjusted accuracy statements for PFOS have been duly footnoted in Table 18. PFOA[1,2 13C] Surrogate Recoveries of the PFOA[1,213C] surrogate in the sample, sample duplicate, and field matrix spikes for each sampling location is provided in Table 19. When the results in Table 19 are considered collectively, one of the most noticeable observations was that the surrogate recovery was consistently low for all samples, sample duplicates, low matrix spikes and high matrix spikes. The overall average surrogate recovery was 56.1% with a RSD of 11.6%. The spiking solutions used to prepare the collection bottle spikes were evaluated prior to bottle preparation under non-GLP provisions. Surrogate recoveries from this study do not suggest that a solution preparation/calculation error is responsible for the recoveries observed here. At this time, the 3M Environmental Laboratory cannot explain the precise, but low surrogate recoveries. A separate investigation will be conducted to explore possible loss mechanisms/holding time issues. The average surrogate recovery was used as a correction factor to normalize surrogate recoveries for a potential holding time effect. Both the corrected and uncorrected recoveries are listed in Table 19. It should be emphasized that sample results for PFBS, PFHS, and PFOS were NOT corrected for surrogate recoveries. Of the 201 bottles extracted, only three produced corrected surrogate less than 70% (sample numbers 86509, 86527, and 86532). Sample number 86509 was a high-level matrix spike and exhibited low recoveries for the three target analytes (PFBS 76.7%, PFHS 67.8%, and PFOS 51.9%). Thus, the low recovery may be attributable to an error during spiking of the collection bottle. E05-0210 Interim Report#13 Tennessee River Page 27 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 16. PFBS Sample Results. 3M Sample Number Sample Description E05-0210-86358 DLS-SW-TRM307-0-050718 E05-0210-86359 DLS-SW-TRM307-0-050718 Dup E05-0210-86360 DLS-SW-TRM307-0-050718 LS E05-0210-86361 DLS-SW-TRM307-0-050718 HS E05-0210-86362 DLS-SW-TRM301-0-050718 E05-0210-86363 DLS-SW-TRM301-0-050718 Dup E05-0210-86364 DLS-SW-TRM301-0-050718 LS E05-0210-86365 DLS-SW-TRM301-0-050718 HS E05-0210-86366 DLS-SW-TRM301-F-050718 E05-0210-86367 DLS-SW-TRM301-F-050718 Dup E05-0210-86368 DLS-SW-TRM301-F-050718 LS E05-0210-86369 DLS-SW-TRM301-F-050718 HS E05-0210-86370 DLS-SW-TRM295-0-050719(4) E05-0210-86371 DLS-SW-TRM295-0-050719 Dup(4) E05-0210-86372 DLS-SW-TRM295-0-050719 LS(4) E05-0210-86373 DLS-SW-TRM295-0-050719 HS(4) E05-0210-86374 DLS-SW-TRM289-0-050719 E05-0210-86375 DLS-SW-TRM289-0-050719 Dup E05-0210-86376 DLS-SW-TRM289-0-050719 LS E05-0210-86377 DLS-SW-TRM289-0-050719 HS E05-0210-86378 DLS-SW-TRM289-F-050719 E05-0210-86379 DLS-SW-TRM289-F-050719 Dup E05-0210-86380 DLS-SW-TRM289-F-050719 LS E05-0210-86381 DLS-SW-TRM289-F-050719 HS E05-0210-86382 DLS-SW-TRM283-0-050719 E05-0210-86383 DLS-SW-TRM283-0-050719 Dup E05-0210-86384 DLS-SW-TRM283-0-050719 LS E05-0210-86385 DLS-SW-TRM283-0-050719 HS E05-0210-86386 DLS-SW-TRM277-0-050719 E05-0210-86387 DLS-SW-TRM277-0-050719 Dup E05-0210-86388 DLS-SW-TRM277-0-050719 LS E05-0210-86389 DLS-SW-TRM277-0-050719 HS E05-0210-86390 DLS-SW-TRM277-F-050719 E05-0210-86391 DLS-SW-TRM277-F-050719 Dup E05-0210-86392 DLS-SW-TRM277-F-050719 LS E05-0210-86393 DLS-SW-TRM277-F-050719 HS (1)PFBS Conc. (ng/mL) < 0.00221 < 0.00221 0.0490 0.508 < 0.00221 < 0.00221 0.0465 0.533 < 0.00221 < 0.00221 0.0479 0.524 0.0679 0.493 0.0143 0.0150 0.0225 0.0213 0.0706 0.453 0.0197 0.0201 0.0693 0.522 0.0203 0.0181 0.0677 0.508 0.0115 0.0123 0.0607 0.515 0.0111 0.0125 0.0633 0.464 (2) Field Matrix Spike % Recovery Average Result Sample/Sample Duplicate (ng/mL) %RPD Extraction Date NA 07/26/2005 NA < 0.00221 (3)NA 07/26/2005 111 07/26/2005 115 07/26/2005 NA 07/26/2005 NA < 0.00221 (3)NA 07/26/2005 105 07/26/2005 121 07/26/2005 NA 07/26/2005 NA < 0.00221 (3)NA 07/26/2005 109 07/26/2005 119 07/26/2005 121 07/26/2005 108 0.0147 4.78 07/26/2005 NA 07/26/2005 NA 07/26/2005 NA 07/26/2005 NA 0.0219 5.48 07/26/2005 110 07/26/2005 97.8 07/26/2005 NA 07/26/2005 NA 0.0199 2.01 07/26/2005 112 07/26/2005 114 07/26/2005 NA 07/26/2005 NA 0.0192 11.4 07/26/2005 110 07/26/2005 111 07/26/2005 NA 07/26/2005 NA 0.0119 6.72 07/26/2005 111 07/26/2005 114 07/26/2005 NA 07/26/2005 NA 0.0118 11.9 07/26/2005 117 07/26/2005 102 07/26/2005 E05-0210 Interim Report#13 Tennessee River Page 28 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 16. PFBS Sample Results Continued. 3M Sample Number Sample Description E05-0210-86394 DLS-SW-TRM271-0-050719 E05-0210-86395 DLS-SW-TRM271-0-050719 Dup E05-0210-86396 DLS-SW-TRM271-0-050719 LS E05-0210-86397 DLS-SW-TRM271-0-050719 HS E05-0210-86398 DLS-SW-TRM265-0-050719 E05-0210-86399 DLS-SW-TRM265-0-050719 Dup E05-0210-86400 DLS-SW-TRM265-0-050719 LS E05-0210-86401 DLS-SW-TRM265-0-050719 HS E05-0210-86402 DLS-SW-TRM261-2-050720 E05-0210-86403 DLS-SW-TRM261-2-050720 Dup E05-0210-86404 DLS-SW-TRM261-2-050720 LS E05-0210-86405 DLS-SW-TRM261-2-050720 HS E05-0210-86406 DLS-SW-TRM261-0-050720 E05-0210-86407 DLS-SW-TRM261-0-050720 Dup E05-0210-86408 DLS-SW-TRM261-0-050720 LS E05-0210-86409 DLS-SW-TRM261-0-050720 HS E05-0210-86410 DLS-SW-TRM261-F-050720 E05-0210-86411 DLS-SW-TRM261-F-050720 Dup E05-0210-86412 DLS-SW-TRM261-F-050720 LS E05-0210-86413 DLS-SW-TRM261-F-050720 HS E05-0210-86414 DLS-SW-TRM256-0-050720 E05-0210-86415 DLS-SW-TRM256-0-050720 Dup E05-0210-86416 DLS-SW-TRM256-0-050720 LS E05-0210-86417 DLS-SW-TRM256-0-050720 HS E05-0210-86418 DLS-SW-TRM254-0-050720 E05-0210-86419 DLS-SW-TRM254-0-050720 Dup E05-0210-86420 DLS-SW-TRM254-0-050720 LS E05-0210-86421 DLS-SW-TRM254-0-050720 HS E05-0210-86422 DLS-SW-TRM254-F-050720 E05-0210-86423 DLS-SW-TRM254-F-050720 Dup E05-0210-86424 DLS-SW-TRM254-F-050720 LS E05-0210-86425 DLS-SW-TRM254-F-050720 HS E05-0210-86426 DLS-SW-TRM254-2-050720 E05-0210-86427 DLS-SW-TRM254-2-050720 Dup E05-0210-86428 DLS-SW-TRM254-2-050720 LS E05-0210-86429 DLS-SW-TRM254-2-050720 HS E05-0210-86430 DXS-SW-T01001-0-050721 E05-0210-86431 DXS-SW-T01001-0-050721 Dup E05-0210-86432 DXS-SW-T01001-0-050721 LS E05-0210-86433 DXS-SW-T01001-0-050721 HS (1)PFBS Conc. (ng/mL) 0.0133 0.0142 0.0586 0.483 0.0103 0.0104 0.0544 0.484 < 0.00221 < 0.00221 0.0497 0.485 0.0118 0.0110 0.0556 0.456 0.0116 0.0107 0.0621 0.460 0.0111 0.0125 0.0607 0.498 0.0124 0.0120 0.0648 0.493 0.0128 0.0121 0.0598 0.530 < 0.00221 < 0.00221 0.0502 0.485 0.0215 0.0201 0.0707 0.519 (2)Field Matrix Spike % Recovery Average Result Sample/Sample Duplicate (ng/mL) NA NA 0.0138 102 106 NA NA 0.0104 99.9 107 NA NA < 0.00221 113 110 NA NA 0.0114 100 101 NA NA 0.0112 130 103 NA NA 0.0118 111 110 NA NA 0.0122 119 109 NA NA 0.0125 107 112 NA NA < 0.00221 114 110 NA NA 0.0208 113 113 %RPD Extraction Date 07/26/2005 6.54 07/26/2005 07/26/2005 07/26/2005 0.966 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 NA 07/26/2005 07/26/2005 07/26/2005 07/26/2005 7.02 07/26/2005 07/26/2005 07/26/2005 07/26/2005 8.07 07/26/2005 07/26/2005 07/26/2005 07/26/2005 11.9 07/26/2005 07/26/2005 07/26/2005 07/26/2005 3.28 07/26/2005 07/27/2005 07/27/2005 07/27/2005 5.62 07/27/2005 07/27/2005 07/27/2005 (3)NA 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 6.73 07/27/2005 07/27/2005 07/27/2005 E05-0210 Interim Report#13 Tennessee River Page 29 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 16. PFBS Sample Results Continued. 3M Sample Number Sample Description E05-0210-86434 DXS-SW-T01002-0-050721 E05-0210-86435 DXS-SW-T01002-0-050721 Dup E05-0210-86436 DXS-SW-T01002-0-050721 LS E05-0210-86437 DXS-SW-T01002-0-050721 HS E05-0210-86438 DXS-SW-T01003-0-050721 E05-0210-86439 DXS-SW-T01003-0-050721 Dup E05-0210-86440 DXS-SW-T01003-0-050721 LS E05-0210-86441 DXS-SW-T01003-0-050721 HS E05-0210-86442 DXS-SW-T01004-0-050721 E05-0210-86443 DXS-SW-T01004-0-050721 Dup E05-0210-86444 DXS-SW-T01004-0-050721 LS E05-0210-86445 DXS-SW-T01004-0-050721 HS E05-0210-86446 DXS-SW-T01005-0-050721 E05-0210-86447 DXS-SW-T01005-0-050721 Dup E05-0210-86448 DXS-SW-T01005-0-050721 LS E05-0210-86449 DXS-SW-T01005-0-050721 HS E05-0210-86450 DXS-SW-T01006-0-050721 E05-0210-86451 DXS-SW-T01006-0-050721 Dup E05-0210-86452 DXS-SW-T01006-0-050721 LS E05-0210-86453 DXS-SW-T01006-0-050721 HS E05-0210-86454 DXS-SW-T01007-0-050721 E05-0210-86455 DXS-SW-T01007-0-050721 Dup E05-0210-86456 DXS-SW-T01007-0-050721 LS E05-0210-86457 DXS-SW-T01007-0-050721 HS E05-0210-86458 DXS-SW-T01008-0-050721 E05-0210-86459 DXS-SW-T01008-0-050721 Dup E05-0210-86460 DXS-SW-T01008-0-050721 LS E05-0210-86461 DXS-SW-T01008-0-050721 HS E05-0210-86462 DXS-SW-T01009-0-050721 E05-0210-86463 DXS-SW-T01009-0-050721 Dup E05-0210-86464 DXS-SW-T01009-0-050721 LS E05-0210-86465 DXS-SW-T01009-0-050721 HS E05-0210-86466 DXS-SW-T01010-0-050721 E05-0210-86467 DXS-SW-T01010-0-050721 Dup E05-0210-86468 DXS-SW-T01010-0-050721 LS E05-0210-86469 DXS-SW-T01010-0-050721 HS E05-0210-86470 DXS-SW-T02001-0-050721 E05-0210-86471 DXS-SW-T02001-0-050721 Dup E05-0210-86472 DXS-SW-T02001-0-050721 LS E05-0210-86473 DXS-SW-T02001-0-050721 HS (1)PFBS Conc. (ng/mL) 0.0161 0.0164 0.0663 0.521 0.0165 0.0166 0.0624 0.460 0.0158 0.0165 0.0678 0.470 0.00957 0.00985 0.0863 0.482 0.00432 0.00366 0.0646 0.546 0.00566 0.00564 0.1040 0.485 0.00369 0.00502 0.0635 0.452 0.00491 0.00444 0.0532 0.535 0.00395 0.00385 0.0543 0.501 0.0414 0.0423 0.0856 0.499 (2)Field Matrix Spike % Recovery Average Result Sample/Sample Duplicate (ng/mL) %RPD Extraction Date NA 07/27/2005 NA 0.0163 1.85 07/27/2005 113 07/27/2005 114 07/27/2005 NA 07/27/2005 NA 07/27/2005 104 0.0166 0.604 07/27/2005 104 07/28/2005 centrifuged NA 07/27/2005 NA 0.0162 4.33 07/27/2005 117 07/27/2005 103 07/27/2005 NA 07/27/2005 NA 0.00971 2.88 07/27/2005 174 07/27/2005 107 07/27/2005 NA 07/27/2005 NA 0.00399 16.5 07/27/2005 137 07/27/2005 123 07/27/2005 NA 07/27/2005 NA 0.00565 0.354 07/27/2005 223 07/27/2005 109 07/27/2005 NA 07/27/2005 NA 0.00436 30.5 07/27/2005 134 07/27/2005 102 07/27/2005 NA 07/27/2005 NA 0.00468 10.0 07/27/2005 110 07/27/2005 120 07/27/2005 NA 07/27/2005 NA 0.00390 2.56 07/27/2005 114 07/27/2005 113 07/27/2005 NA 07/27/2005 NA 0.0419 2.15 07/27/2005 99.2 07/27/2005 104 07/27/2005 E05-0210 Interim Report#13 Tennessee River Page 30 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 16. PFBS Sample Results Continued. 3M Sample Number Sample Description (1)PFBS Conc. (ng/mL) (2)Field Matrix Average Result Spike % Sample/Sample Recovery Duplicate %RPD Extraction Date E05-0210-86474 DXS-SW-T02002-0-050721 0.0306 NA 07/27/2005 E05-0210-86475 DXS-SW-T02002-0-050721 Dup 0.0316 NA E05-0210-86476 DXS-SW-T02002-0-050721 LS 0.0783 107 0.0311 3.22 07/27/2005 07/27/2005 E05-0210-86477 DXS-SW-T02002-0-050721 HS 0.508 108 07/27/2005 E05-0210-86478 DXS-SW-T02003-0-050721 < 0.00221 NA 07/27/2005 E05-0210-86479 DXS-SW-T02003-0-050721 Dup < 0.00221 NA E05-0210-86480 DXS-SW-T02003-0-050721 LS 0.0479 109 < 0.00221 (3)NA 07/27/2005 07/27/2005 E05-0210-86481 DXS-SW-T02003-0-050721 HS 0.476 108 07/27/2005 E05-0210-86482 DXS-SW-T02004-0-050721 < 0.00221 NA 07/27/2005 E05-0210-86483 DXS-SW-T02004-0-050721 Dup < 0.00221 NA E05-0210-86484 DXS-SW-T02004-0-050721 LS 0.0544 122 < 0.00221 (3)NA 07/27/2005 07/27/2005 E05-0210-86485 DXS-SW-T02004-0-050721 HS 0.476 108 07/27/2005 E05-0210-86486 DXS-SW-T02005-0-050721 < 0.000883 NA 07/27/2005 E05-0210-86487 DXS-SW-T02005-0-050721 Dup < 0.00221 NA E05-0210-86488 DXS-SW-T02005-0-050721 LS 0.0511 116 < 0.00221 (3)NA 07/28/2005 centrifuged 07/27/2005 E05-0210-86489 DXS-SW-T02005-0-050721 HS 0.600 136 07/28/2005 centrifuged E05-0210-86490 DXS-SW-T02006-0-050721 < 0.000883 NA 07/27/2005 E05-0210-86491 DXS-SW-T02006-0-050721 Dup 0.00101 NA E05-0210-86492 DXS-SW-T02006-0-050721 LS 0.0534 119 (5)0.00101 NA 07/27/2005 07/27/2005 E05-0210-86493 DXS-SW-T02006-0-050721 HS 0.545 123 07/27/2005 E05-0210-86494 DXS-SW-T02007-0-050721 < 0.000883 NA 07/27/2005 E05-0210-86495 DXS-SW-T02007-0-050721 Dup < 0.000883 NA E05-0210-86496 DXS-SW-T02007-0-050721 LS 0.0470 106 < 0.000883 (3)NA 07/27/2005 07/27/2005 E05-0210-86497 DXS-SW-T02007-0-050721 HS 0.450 102 07/27/2005 E05-0210-86498 DXS-SW-T02008-0-050721 0.00109 NA 07/27/2005 E05-0210-86499 DXS-SW-T02008-0-050721 Dup 0.00115 NA E05-0210-86500 DXS-SW-T02008-0-050721 LS 0.0508 112 0.00112 5.36 07/27/2005 07/27/2005 E05-0210-86501 DXS-SW-T02008-0-050721 HS 0.468 106 07/27/2005 E05-0210-86502 DXS-SW-T02009-0-050721 0.00288 NA 07/27/2005 E05-0210-86503 DXS-SW-T02009-0-050721 Dup 0.00244 NA E05-0210-86504 DXS-SW-T02009-0-050721 LS 0.0541 117 0.00266 16.5 07/27/2005 07/27/2005 E05-0210-86505 DXS-SW-T02009-0-050721 HS 0.498 112 07/27/2005 E05-0210-86506 DXS-SW-T02010-0-050721 0.00628 NA 07/27/2005 E05-0210-86507 DXS-SW-T02010-0-050721 Dup 0.00553 NA E05-0210-86508 DXS-SW-T02010-0-050721 LS 0.0533 107 0.00591 12.7 07/27/2005 07/27/2005 E05-0210-86509 DXS-SW-T02010-0-050721 HS 0.344 76.7 07/27/2005 E05-0210-86510 DXS-SW-T03001-0-050721 E05-0210-86511 DXS-SW-T03001-0-050721 Dup E05-0210-86512 DXS-SW-T03001-0-050721 LS 0.818 0.854 0.911 NA NA (6)NR 0.836 07/27/2005 4.31 07/27/2005 07/27/2005 E05-0210-86513 DXS-SW-T03001-0-050721 HS 1.33 112 07/27/2005 E05-0210 Interim Report#13 Tennessee River Page 31 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 16. PFBS Sample Results Continued. 3M Sample Number Sample Description (1)PFBS Conc. (ng/mL) (2)Field Matrix Average Result Spike % Sample/Sample Recovery Duplicate %RPD Extraction Date E05-0210-86514 DXS-SW-T03002-0-050721 0.00519 NA E05-0210-86515 DXS-SW-T03002-0-050721 Dup 0.00424 NA E05-0210-86516 DXS-SW-T03002-0-050721 LS 0.0521 107 E05-0210-86517 DXS-SW-T03002-0-050721 HS 0.480 108 0.00472 07/27/2005 20.1 07/27/2005 07/27/2005 07/27/2005 E05-0210-86518 DXS-SW-T03003-0-050721 < 0.000883 NA E05-0210-86519 DXS-SW-T03003-0-050721 Dup < 0.000883 NA E05-0210-86520 DXS-SW-T03003-0-050721 LS 0.0519 118 E05-0210-86521 DXS-SW-T03003-0-050721 HS 0.487 110 < 0.000883 (3)NA 07/27/2005 07/27/2005 07/27/2005 07/27/2005 E05-0210-86522 DXS-SW-T03004-0-050722 0.00430 NA E05-0210-86523 DXS-SW-T03004-0-050722 Dup 0.00106 NA E05-0210-86524 DXS-SW-T03004-0-050722 LS 0.0536 115 E05-0210-86525 DXS-SW-T03004-0-050722 HS 0.516 116 0.00268 07/27/2005 121 07/27/2005 07/27/2005 07/27/2005 E05-0210-86526 DXS-SW-T03005-0-050722 < 0.000883 NA E05-0210-86527 DXS-SW-T03005-0-050722 Dup 0.00171 NA E05-0210-86528 DXS-SW-T03005-0-050722 LS 0.0588 133 E05-0210-86529 DXS-SW-T03005-0-050722 HS 0.536 122 (5)0.00171 07/27/2005 07/28/2005 NA centrifuged 07/27/2005 07/27/2005 E05-0210-86530 DXS-SW-T03006-0-050722 < 0.000883 NA E05-0210-86531 DXS-SW-T03006-0-050722 Dup < 0.000883 NA E05-0210-86532 DXS-SW-T03006-0-050722 LS 0.0430 97.5 E05-0210-86533 DXS-SW-T03006-0-050722 HS 0.591 134 < 0.000883 (3)NA 07/27/2005 07/27/2005 07/28/2005 centrifuged 07/27/2005 E05-0210-86534 DXS-SW-T03007-0-050722 < 0.000883 NA E05-0210-86535 DXS-SW-T03007-0-050722 Dup 0.00107 NA E05-0210-86536 DXS-SW-T03007-0-050722 LS 0.0564 128 E05-0210-86537 DXS-SW-T03007-0-050722 HS 0.513 116 (5)0.00107 07/27/2005 07/28/2005 NA centrifuged 07/27/2005 07/27/2005 E05-0210-86538 DXS-SW-T03008-0-050722 < 0.000883 NA E05-0210-86539 DXS-SW-T03008-0-050722 Dup < 0.000883 NA E05-0210-86540 DXS-SW-T03008-0-050722 LS 0.0513 116 E05-0210-86541 DXS-SW-T03008-0-050722 HS 0.507 115 < 0.000883 (3)NA 07/27/2005 07/27/2005 07/27/2005 07/27/2005 E05-0210-86542 DXS-SW-T03009-0-050722 < 0.000883 NA E05-0210-86543 DXS-SW-T03009-0-050722 Dup < 0.000883 NA E05-0210-86544 DXS-SW-T03009-0-050722 LS 0.0505 114 E05-0210-86545 DXS-SW-T03009-0-050722 HS 0.460 104 < 0.000883 (3)NA 07/27/2005 07/27/2005 07/27/2005 07/27/2005 E05-0210-86546 DXS-SW-T03010-0-050722 0.000908 NA E05-0210-86547 DXS-SW-T03010-0-050722 Dup < 0.000883 NA E05-0210-86548 DXS-SW-T03010-0-050722 LS 0.0498 111 E05-0210-86549 DXS-SW-T03010-0-050722 HS 0.449 102 (5)0.000908 07/27/2005 NA 07/27/2005 07/27/2005 07/27/2005 E05-0210 Interim Report#13 Tennessee River Page 32 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 16. PFBS Sample Results Continued. 3M Sample Number Sample Description (1)PFBS Conc. (ng/mL) (2)Field Matrix Average Result Spike % Sample/Sample Recovery Duplicate %RPD Extraction Date E05-0210-86550 DLS-SW-TRIP01 E05-0210-86551 DLS-SW-TRIP01 LS < 0.000883 NA 0.04710 107 07/27/2005 < 0.000883 NA 07/27/2005 E05-0210-86552 DLS-SW-TRIP01 HS 0.444 101 07/27/2005 E05-0210-86553 DXS-SW-TRIP02 E05-0210-86554 DXS-SW-TRIP02 LS < 0.000883 NA 0.0478 108 07/27/2005 < 0.000883 NA 07/27/2005 E05-0210-86555 DXS-SW-TRIP02 HS 0.440 99.8 07/27/2005 E05-0210-86556 DXS-SW-TRIP03 E05-0210-86557 DXS-SW-TRIP03 LS < 0.000883 NA 0.0495 112 07/27/2005 < 0.000883 NA 07/27/2005 E05-0210-86558 DXS-SW-TRIP03 HS 0.080 18.0 07/27/2005 (1) The analytical uncertainty of the PFBS resuts is 10010.6% based on method accuracy and precision. All results and calculations in this table are presented with three significant figures. Sample concentrations, averages, and %RPD values may vary slightly from the raw data. (2) Low field matrix spike concentration = 0.0441 ng/mL. High field matrix spike concentration = 0.441 ng/mL. (3) NA: Not applicable. %RPD value was not determined when concentrations for both the sample and sample duplicate were below the stated LOQ. (4) Sample descriptions were misidentified when checked into LIMS. Samples with LIMS ID numbers 86370 and 86371 were in bottles labeled low spike and high spike, respectively. Bottles with LIMS ID numbers 86372 and 86372 were surrogate spiked only (sample and sample duplicate bottles). (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. (6) NR: Not reported. Spike recovery not calculated as the endogenous sample concentration was at least three times the spiked amount. E05-0210 Interim Report#13 Tennessee River Page 33 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 17. PFHS Sample Results. 3M Sample Number Sample Description E05-0210-86358 DLS-SW-TRM307-0-050718 E05-0210-86359 DLS-SW-TRM307-0-050718 Dup E05-0210-86360 DLS-SW-TRM307-0-050718 LS E05-0210-86361 DLS-SW-TRM307-0-050718 HS E05-0210-86362 DLS-SW-TRM301-0-050718 E05-0210-86363 DLS-SW-TRM301-0-050718 Dup E05-0210-86364 DLS-SW-TRM301-0-050718 LS E05-0210-86365 DLS-SW-TRM301-0-050718 HS E05-0210-86366 DLS-SW-TRM301-F-050718 E05-0210-86367 DLS-SW-TRM301-F-050718 Dup E05-0210-86368 DLS-SW-TRM301-F-050718 LS E05-0210-86369 DLS-SW-TRM301-F-050718 HS E05-0210-86370 DLS-SW-TRM295-0-050719(5) E05-0210-86371 DLS-SW-TRM295-0-050719 Dup(5) E05-0210-86372 DLS-SW-TRM295-0-050719 LS(5) E05-0210-86373 DLS-SW-TRM295-0-050719 HS(5) E05-0210-86374 DLS-SW-TRM289-0-050719 E05-0210-86375 DLS-SW-TRM289-0-050719 Dup E05-0210-86376 DLS-SW-TRM289-0-050719 LS E05-0210-86377 DLS-SW-TRM289-0-050719 HS E05-0210-86378 DLS-SW-TRM289-F-050719 E05-0210-86379 DLS-SW-TRM289-F-050719 Dup E05-0210-86380 DLS-SW-TRM289-F-050719 LS E05-0210-86381 DLS-SW-TRM289-F-050719 HS E05-0210-86382 DLS-SW-TRM283-0-050719 E05-0210-86383 DLS-SW-TRM283-0-050719 Dup E05-0210-86384 DLS-SW-TRM283-0-050719 LS E05-0210-86385 DLS-SW-TRM283-0-050719 HS E05-0210-86386 DLS-SW-TRM277-0-050719 E05-0210-86387 DLS-SW-TRM277-0-050719 Dup E05-0210-86388 DLS-SW-TRM277-0-050719 LS E05-0210-86389 DLS-SW-TRM277-0-050719 HS (1)PFHS Conc. (ng/mL) (2)Field Matrix Average Result Spike % Sample/Sample Recovery Duplicate %RPD Extraction Date < 0.00104 NA 07/26/2005 < 0.00104 NA 0.0581 112 < 0.00104 (3)NA 07/26/2005 07/26/2005 0.584 112 07/26/2005 < 0.00104 NA 07/26/2005 0.00134 NA 0.0542 101 0.00134 (4)NA 07/26/2005 07/26/2005 0.600 115 07/26/2005 < 0.00104 NA 07/26/2005 < 0.00104 NA 0.0577 111 < 0.00104 (3)NA 07/26/2005 07/26/2005 0.576 110 07/26/2005 0.0719 116 07/26/2005 0.5490 103 0.0115 NA 0.0117 07/26/2005 2.58 07/26/2005 0.0118 NA 07/26/2005 0.0133 NA 07/26/2005 0.0123 NA 0.0666 103 0.01280 07/26/2005 7.81 07/26/2005 0.493 92.2 07/26/2005 0.0129 NA 07/26/2005 0.0120 NA 0.0706 112 0.01245 07/26/2005 7.23 07/26/2005 0.582 109 07/26/2005 0.00888 NA 07/26/2005 0.00883 NA 0.0645 107 0.00886 0.565 07/26/2005 07/26/2005 0.572 108 07/26/2005 0.00579 NA 07/26/2005 0.00704 NA 0.0637 110 0.00642 07/26/2005 19.5 07/26/2005 0.574 109 07/26/2005 E05-0210 Interim Report#13 Tennessee River Page 34 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 17. PFHS Sample Results Continued. 3M Sample Number Sample Description E05-0210-86390 DLS-SW-TRM277-F-050719 E05-0210-86391 DLS-SW-TRM277-F-050719 Dup E05-0210-86392 DLS-SW-TRM277-F-050719 LS E05-0210-86393 DLS-SW-TRM277-F-050719 HS E05-0210-86394 DLS-SW-TRM271-0-050719 E05-0210-86395 DLS-SW-TRM271-0-050719 Dup E05-0210-86396 DLS-SW-TRM271-0-050719 LS E05-0210-86397 DLS-SW-TRM271-0-050719 HS E05-0210-86398 DLS-SW-TRM265-0-050719 E05-0210-86399 DLS-SW-TRM265-0-050719 Dup E05-0210-86400 DLS-SW-TRM265-0-050719 LS E05-0210-86401 DLS-SW-TRM265-0-050719 HS E05-0210-86402 DLS-SW-TRM261-2-050720 E05-0210-86403 DLS-SW-TRM261-2-050720 Dup E05-0210-86404 DLS-SW-TRM261-2-050720 LS E05-0210-86405 DLS-SW-TRM261-2-050720 HS E05-0210-86406 DLS-SW-TRM261-0-050720 E05-0210-86407 DLS-SW-TRM261-0-050720 Dup E05-0210-86408 DLS-SW-TRM261-0-050720 LS E05-0210-86409 DLS-SW-TRM261-0-050720 HS E05-0210-86410 DLS-SW-TRM261-F-050720 E05-0210-86411 DLS-SW-TRM261-F-050720 Dup E05-0210-86412 DLS-SW-TRM261-F-050720 LS E05-0210-86413 DLS-SW-TRM261-F-050720 HS E05-0210-86414 DLS-SW-TRM256-0-050720 E05-0210-86415 DLS-SW-TRM256-0-050720 Dup E05-0210-86416 DLS-SW-TRM256-0-050720 LS E05-0210-86417 DLS-SW-TRM256-0-050720 HS E05-0210-86418 DLS-SW-TRM254-0-050720 E05-0210-86419 DLS-SW-TRM254-0-050720 Dup E05-0210-86420 DLS-SW-TRM254-0-050720 LS E05-0210-86421 DLS-SW-TRM254-0-050720 HS E05-0210-86422 DLS-SW-TRM254-F-050720 E05-0210-86423 DLS-SW-TRM254-F-050720 Dup E05-0210-86424 DLS-SW-TRM254-F-050720 LS E05-0210-86425 DLS-SW-TRM254-F-050720 HS (1)PFHS Conc. (ng/mL) 0.00609 0.00672 0.0637 0.529 0.00512 0.00574 0.0573 0.558 0.00525 0.00542 0.0568 0.561 < 0.00104 < 0.00104 0.0604 0.576 0.00520 0.00481 0.0568 0.530 0.00542 0.00486 0.0586 0.512 0.00485 0.00470 0.0611 0.559 0.00550 0.00481 0.0623 0.555 0.00533 0.00525 0.0639 0.585 (2)Field Matrix Average Result Spike % Sample/Sample Recovery Duplicate NA NA 0.00641 110 100 NA NA 0.00543 99.6 106 NA NA 0.00534 98.8 107 NA NA < 0.00104 116 110 NA NA 0.00501 99.4 101 NA NA 0.00514 103 97.3 NA NA 0.00478 108 106 NA NA 0.00516 110 106 NA NA 0.00529 112 111 %RPD Extraction Date 07/26/2005 07/26/2005 9.84 07/26/2005 07/26/2005 07/26/2005 07/26/2005 11.4 07/26/2005 07/26/2005 07/26/2005 07/26/2005 3.19 07/26/2005 07/26/2005 07/26/2005 (3)NA 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 7.79 07/26/2005 07/26/2005 07/26/2005 07/26/2005 10.9 07/27/2005 07/27/2005 07/27/2005 07/27/2005 3.14 07/27/2005 07/27/2005 07/27/2005 07/27/2005 13.4 07/27/2005 07/27/2005 07/27/2005 07/27/2005 1.51 07/27/2005 07/27/2005 E05-0210 Interim Report#13 Tennessee River Page 35 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 17. PFHS Sample Results Continued 3M Sample Number Sample Description E05-0210-86426 DLS-SW-TRM254-2-050720 E05-0210-86427 DLS-SW-TRM254-2-050720 Dup E05-0210-86428 DLS-SW-TRM254-2-050720 LS E05-0210-86429 DLS-SW-TRM254-2-050720 HS E05-0210-86430 DXS-SW-T01001-0-050721 E05-0210-86431 DXS-SW-T01001-0-050721 Dup E05-0210-86432 DXS-SW-T01001-0-050721 LS E05-0210-86433 DXS-SW-T01001-0-050721 HS E05-0210-86434 DXS-SW-T01002-0-050721 E05-0210-86435 DXS-SW-T01002-0-050721 Dup E05-0210-86436 DXS-SW-T01002-0-050721 LS E05-0210-86437 DXS-SW-T01002-0-050721 HS E05-0210-86438 DXS-SW-T01003-0-050721 E05-0210-86439 DXS-SW-T01003-0-050721 Dup E05-0210-86440 DXS-SW-T01003-0-050721 LS (1)PFHS Conc. (ng/mL) < 0.00104 < 0.00104 0.0578 0.575 0.0121 0.0116 0.0691 0.570 0.0101 0.00959 0.0637 0.593 0.00827 0.00941 0.0625 E05-0210-86441 DXS-SW-T01003-0-050721 HS 0.517 E05-0210-86442 DXS-SW-T01004-0-050721 E05-0210-86443 DXS-SW-T01004-0-050721 Dup E05-0210-86444 DXS-SW-T01004-0-050721 LS E05-0210-86445 DXS-SW-T01004-0-050721 HS E05-0210-86446 DXS-SW-T01005-0-050721 E05-0210-86447 DXS-SW-T01005-0-050721 Dup E05-0210-86448 DXS-SW-T01005-0-050721 LS E05-0210-86449 DXS-SW-T01005-0-050721 HS E05-0210-86450 DXS-SW-T01006-0-050721 E05-0210-86451 DXS-SW-T01006-0-050721 Dup E05-0210-86452 DXS-SW-T01006-0-050721 LS E05-0210-86453 DXS-SW-T01006-0-050721 HS E05-0210-86454 DXS-SW-T01007-0-050721 E05-0210-86455 DXS-SW-T01007-0-050721 Dup E05-0210-86456 DXS-SW-T01007-0-050721 LS E05-0210-86457 DXS-SW-T01007-0-050721 HS E05-0210-86458 DXS-SW-T01008-0-050721 E05-0210-86459 DXS-SW-T01008-0-050721 Dup E05-0210-86460 DXS-SW-T01008-0-050721 LS E05-0210-86461 DXS-SW-T01008-0-050721 HS 0.0097 0.0101 0.0692 0.512 0.00633 0.00667 0.0951 0.541 0.00346 0.00333 0.0731 0.611 0.00419 0.00429 0.0628 0.559 0.00316 0.00328 0.0686 0.507 (2)Field Matrix Average Result Spike % Sample/Sample Recovery Duplicate NA NA < 0.00104 111 110 NA NA 0.0119 110 107 NA NA 0.00985 103 112 NA NA 103 0.00884 99.2 NA NA 0.00989 114 96.4 NA NA 0.00650 170 102 NA NA 0.00340 134 117 NA NA 0.00424 112 106 NA NA 0.00322 125 96.7 %RPD Extraction Date 07/27/2005 (3)NA 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 4.22 07/27/2005 07/27/2005 07/27/2005 07/27/2005 5.18 07/27/2005 07/27/2005 07/27/2005 07/27/2005 12.9 07/27/2005 07/28/2005 centrifuged 07/27/2005 07/27/2005 4.35 07/27/2005 07/27/2005 07/27/2005 07/27/2005 5.23 07/27/2005 07/27/2005 07/27/2005 07/27/2005 3.83 07/27/2005 07/27/2005 07/27/2005 07/27/2005 2.36 07/27/2005 07/27/2005 07/27/2005 07/27/2005 3.73 07/27/2005 07/27/2005 E05-0210 Interim Report#13 Tennessee River Page 36 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 17. PFHS Sample Results Continued. 3M Sample Number Sample Description E05-0210-86462 DXS-SW-T01009-0-050721 E05-0210-86463 DXS-SW-T01009-0-050721 Dup E05-0210-86464 DXS-SW-T01009-0-050721 LS E05-0210-86465 DXS-SW-T01009-0-050721 HS E05-0210-86466 DXS-SW-T01010-0-050721 E05-0210-86467 DXS-SW-T01010-0-050721 Dup E05-0210-86468 DXS-SW-T01010-0-050721 LS E05-0210-86469 DXS-SW-T01010-0-050721 HS E05-0210-86470 DXS-SW-T02001-0-050721 E05-0210-86471 DXS-SW-T02001-0-050721 Dup E05-0210-86472 DXS-SW-T02001-0-050721 LS E05-0210-86473 DXS-SW-T02001-0-050721 HS E05-0210-86474 DXS-SW-T02002-0-050721 E05-0210-86475 DXS-SW-T02002-0-050721 Dup E05-0210-86476 DXS-SW-T02002-0-050721 LS E05-0210-86477 DXS-SW-T02002-0-050721 HS E05-0210-86478 DXS-SW-T02003-0-050721 E05-0210-86479 DXS-SW-T02003-0-050721 Dup E05-0210-86480 DXS-SW-T02003-0-050721 LS E05-0210-86481 DXS-SW-T02003-0-050721 HS E05-0210-86482 DXS-SW-T02004-0-050721 E05-0210-86483 DXS-SW-T02004-0-050721 Dup E05-0210-86484 DXS-SW-T02004-0-050721 LS E05-0210-86485 DXS-SW-T02004-0-050721 HS E05-0210-86486 DXS-SW-T02005-0-050721 (1)PFHS Conc. (ng/mL) 0.00301 0.00330 0.0595 0.601 0.00332 0.00277 0.0607 0.561 0.0205 0.0187 0.0729 0.560 0.0124 0.0126 0.0661 0.552 < 0.00104 < 0.00104 0.0553 0.528 < 0.00104 < 0.00104 0.0619 0.534 < 0.0026 E05-0210-86487 DXS-SW-T02005-0-050721 Dup < 0.0026 E05-0210-86488 DXS-SW-T02005-0-050721 LS 0.0544 E05-0210-86489 DXS-SW-T02005-0-050721 HS 0.675 E05-0210-86490 DXS-SW-T02006-0-050721 E05-0210-86491 DXS-SW-T02006-0-050721 Dup E05-0210-86492 DXS-SW-T02006-0-050721 LS E05-0210-86493 DXS-SW-T02006-0-050721 HS E05-0210-86494 DXS-SW-T02007-0-050721 E05-0210-86495 DXS-SW-T02007-0-050721 Dup E05-0210-86496 DXS-SW-T02007-0-050721 LS E05-0210-86497 DXS-SW-T02007-0-050721 HS < 0.0026 < 0.0026 0.0595 0.617 < 0.0026 < 0.0026 0.0529 0.526 (2)Field Matrix Average Result Spike % Sample/Sample Recovery Duplicate NA NA 0.00316 108 115 NA NA 0.00305 111 107 NA NA 0.0196 102 104 NA NA 0.0125 103 104 NA NA < 0.00104 106 101 NA NA < 0.00104 117 102 NA NA < 0.0026 104 119 NA NA < 0.0026 114 118 NA NA < 0.0026 102 101 %RPD Extraction Date 07/27/2005 07/27/2005 9.19 07/27/2005 07/27/2005 07/27/2005 07/27/2005 18.1 07/27/2005 07/27/2005 07/27/2005 07/27/2005 9.18 07/27/2005 07/27/2005 07/27/2005 07/27/2005 1.60 07/27/2005 07/27/2005 07/27/2005 (3)NA 07/27/2005 07/27/2005 07/27/2005 07/27/2005 (3)NA 07/27/2005 07/27/2005 07/27/2005 (3)NA 07/27/2005 07/28/2005 centrifuged 07/27/2005 07/28/2005 centrifuged 07/27/2005 (3)NA 07/27/2005 07/27/2005 07/27/2005 (3)NA 07/27/2005 07/27/2005 07/27/2005 07/27/2005 E05-0210 Interim Report#13 Tennessee River Page 37 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 17. PFHS Sample Results Continued. 3M Sample Number Sample Description E05-0210-86498 DXS-SW-T02008-0-050721 E05-0210-86499 DXS-SW-T02008-0-050721 Dup E05-0210-86500 DXS-SW-T02008-0-050721 LS E05-0210-86501 DXS-SW-T02008-0-050721 HS E05-0210-86502 DXS-SW-T02009-0-050721 E05-0210-86503 DXS-SW-T02009-0-050721 Dup E05-0210-86504 DXS-SW-T02009-0-050721 LS E05-0210-86505 DXS-SW-T02009-0-050721 HS E05-0210-86506 DXS-SW-T02010-0-050721 E05-0210-86507 DXS-SW-T02010-0-050721 Dup E05-0210-86508 DXS-SW-T02010-0-050721 LS E05-0210-86509 DXS-SW-T02010-0-050721 HS E05-0210-86510 DXS-SW-T03001-0-050721 E05-0210-86511 DXS-SW-T03001-0-050721 Dup E05-0210-86512 DXS-SW-T03001-0-050721 LS E05-0210-86513 DXS-SW-T03001-0-050721 HS E05-0210-86514 DXS-SW-T03002-0-050721 E05-0210-86515 DXS-SW-T03002-0-050721 Dup E05-0210-86516 DXS-SW-T03002-0-050721 LS E05-0210-86517 DXS-SW-T03002-0-050721 HS E05-0210-86518 DXS-SW-T03003-0-050721 E05-0210-86519 DXS-SW-T03003-0-050721 Dup E05-0210-86520 DXS-SW-T03003-0-050721 LS E05-0210-86521 DXS-SW-T03003-0-050721 HS E05-0210-86522 DXS-SW-T03004-0-050722 E05-0210-86523 DXS-SW-T03004-0-050722 Dup E05-0210-86524 DXS-SW-T03004-0-050722 LS E05-0210-86525 DXS-SW-T03004-0-050722 HS E05-0210-86526 DXS-SW-T03005-0-050722 E05-0210-86527 DXS-SW-T03005-0-050722 Dup E05-0210-86528 DXS-SW-T03005-0-050722 LS E05-0210-86529 DXS-SW-T03005-0-050722 HS E05-0210-86530 DXS-SW-T03006-0-050722 E05-0210-86531 DXS-SW-T03006-0-050722 Dup E05-0210-86532 DXS-SW-T03006-0-050722 LS E05-0210-86533 DXS-SW-T03006-0-050722 HS (1)PFHS Conc. (ng/mL) < 0.0026 < 0.0026 0.0578 0.528 < 0.0026 < 0.0026 0.0608 0.570 0.00363 0.00342 0.0554 0.357 0.176 0.185 0.250 0.742 < 0.0026 < 0.0026 0.0568 0.549 < 0.0026 < 0.0026 0.0581 0.558 0.00756 < 0.0026 0.0597 0.570 < 0.0026 0.00331 0.0649 0.589 < 0.0026 < 0.0026 0.0285 0.643 (2)Field Matrix Average Result Spike % Sample/Sample Recovery Duplicate %RPD Extraction Date NA 07/27/2005 NA < 0.0026 (3)NA 07/27/2005 111 07/27/2005 101 07/27/2005 NA 07/27/2005 NA < 0.0026 (3)NA 07/27/2005 117 07/27/2005 109 07/27/2005 NA 07/27/2005 NA 07/27/2005 0.00353 5.96 99.6 07/27/2005 67.8 07/27/2005 NA 07/27/2005 NA 07/27/2005 0.181 4.99 133 07/27/2005 108 07/27/2005 NA 07/27/2005 NA < 0.0026 (3)NA 07/27/2005 109 07/27/2005 105 07/27/2005 NA 07/27/2005 NA < 0.0026 (3)NA 07/27/2005 112 07/27/2005 107 07/27/2005 NA 07/27/2005 NA (4)0.00756 NA 07/27/2005 100 07/27/2005 108 07/27/2005 NA 07/27/2005 NA (4)0.00331 NA 07ce/2nt8rif/u2g0e0d 5 118 07/27/2005 112 07/27/2005 NA 07/27/2005 NA 54.7 < 0.0026 (3)NA 07/27/2005 07/28/2005 centrifuged 123 07/27/2005 E05-0210 Interim Report#13 Tennessee River Page 38 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 17. PFHS Sample Results Continued. 3M Sample Number Sample Description (1)PFHS Conc. (ng/mL) (2)Field Matrix Average Result Spike % Sample/Sample Recovery Duplicate %RPD Extraction Date E05-0210-86534 DXS-SW-T03007-0-050722 < 0.0026 NA 07/27/2005 E05-0210-86535 DXS-SW-T03007-0-050722 Dup 0.00366 NA E05-0210-86536 DXS-SW-T03007-0-050722 LS 0.0640 123 (4)0.00366 07/28/2005 NA centrifuged 07/27/2005 E05-0210-86537 DXS-SW-T03007-0-050722 HS 0.579 111 07/27/2005 E05-0210-86538 DXS-SW-T03008-0-050722 < 0.0026 NA 07/27/2005 E05-0210-86539 DXS-SW-T03008-0-050722 Dup < 0.0026 NA E05-0210-86540 DXS-SW-T03008-0-050722 LS 0.0551 106 < 0.0026 (3)NA 07/27/2005 07/27/2005 E05-0210-86541 DXS-SW-T03008-0-050722 HS 0.567 109 07/27/2005 E05-0210-86542 DXS-SW-T03009-0-050722 < 0.0026 NA 07/27/2005 E05-0210-86543 DXS-SW-T03009-0-050722 Dup < 0.0026 NA E05-0210-86544 DXS-SW-T03009-0-050722 LS 0.0568 109 < 0.0026 (3)NA 07/27/2005 07/27/2005 E05-0210-86545 DXS-SW-T03009-0-050722 HS 0.530 102 07/27/2005 E05-0210-86546 DXS-SW-T03010-0-050722 < 0.0026 NA 07/27/2005 E05-0210-86547 DXS-SW-T03010-0-050722 Dup < 0.0026 NA E05-0210-86548 DXS-SW-T03010-0-050722 LS 0.0547 105 < 0.0026 (3)NA 07/27/2005 07/27/2005 E05-0210-86549 DXS-SW-T03010-0-050722 HS 0.533 102 07/27/2005 E05-0210-86550 DLS-SW-TRIP01 < 0.0026 NA 07/27/2005 E05-0210-86551 DLS-SW-TRIP01 LS 0.0534 102 < 0.0026 NA 07/27/2005 E05-0210-86552 DLS-SW-TRIP01 HS 0.508 97.5 07/27/2005 E05-0210-86553 DXS-SW-TRIP02 < 0.0026 NA 07/27/2005 E05-0210-86554 DXS-SW-TRIP02 LS 0.0530 102 < 0.0026 NA 07/27/2005 E05-0210-86555 DXS-SW-TRIP02 HS 0.506 97.1 07/27/2005 E05-0210-86556 DXS-SW-TRIP03 < 0.0026 NA 07/27/2005 E05-0210-86557 DXS-SW-TRIP03 LS 0.0528 101 < 0.0026 NA 07/27/2005 E05-0210-86558 DXS-SW-TRIP03 HS 0.531 102 07/27/2005 (1) The analytical uncertainty of the PFHS resuts is 10015.2% based on method accuracy and precision. All results and calculations in this table are presented with three significant figures. Sample concentrations, averages, and %RPD values may vary slightly from the raw data. (2) Low field matrix spike concentration = 0.0521 ng/mL. High field matrix spike concentration = 0.521 ng/mL. (3) NA: Not applicable. %RPD value was not determined when concentrations for the both the sample and sample duplicate were below the stated LOQ. (4) 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. (5) Sample descriptions were misidentified when checked into LIMS. Samples with LIMS ID numbers 86370 and 86371 were in bottles labeled low spike and high spike, respectively. Bottles with LIMS ID numbers 86372 and 86372 were surrogate spiked only (sample and sample duplicate bottles). E05-0210 Interim Report#13 Tennessee River Page 39 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 18. PFOS Sample Results. 3M Sample Number Sample Description E05-0210-86358 DLS-SW-TRM307-0-050718 E05-0210-86359 DLS-SW-TRM307-0-050718 Dup E05-0210-86360 DLS-SW-TRM307-0-050718 LS E05-0210-86361 DLS-SW-TRM307-0-050718 HS E05-0210-86362 DLS-SW-TRM301-0-050718 E05-0210-86363 DLS-SW-TRM301-0-050718 Dup E05-0210-86364 DLS-SW-TRM301-0-050718 LS E05-0210-86365 DLS-SW-TRM301-0-050718 HS E05-0210-86366 DLS-SW-TRM301-F-050718 E05-0210-86367 DLS-SW-TRM301-F-050718 Dup E05-0210-86368 DLS-SW-TRM301-F-050718 LS E05-0210-86369 DLS-SW-TRM301-F-050718 HS E05-0210-86370 DLS-SW-TRM295-0-050719(5) E05-0210-86371 DLS-SW-TRM295-0-050719 Dup(5) E05-0210-86372 DLS-SW-TRM295-0-050719 LS(5) E05-0210-86373 DLS-SW-TRM295-0-050719 HS(5) E05-0210-86374 DLS-SW-TRM289-0-050719 E05-0210-86375 DLS-SW-TRM289-0-050719 Dup E05-0210-86376 DLS-SW-TRM289-0-050719 LS E05-0210-86377 DLS-SW-TRM289-0-050719 HS E05-0210-86378 DLS-SW-TRM289-F-050719 E05-0210-86379 DLS-SW-TRM289-F-050719 Dup E05-0210-86380 DLS-SW-TRM289-F-050719 LS E05-0210-86381 DLS-SW-TRM289-F-050719 HS E05-0210-86382 DLS-SW-TRM283-0-050719 E05-0210-86383 DLS-SW-TRM283-0-050719 Dup E05-0210-86384 DLS-SW-TRM283-0-050719 LS E05-0210-86385 DLS-SW-TRM283-0-050719 HS E05-0210-86386 DLS-SW-TRM277-0-050719 E05-0210-86387 DLS-SW-TRM277-0-050719 Dup E05-0210-86388 DLS-SW-TRM277-0-050719 LS E05-0210-86389 DLS-SW-TRM277-0-050719 HS E05-0210-86390 DLS-SW-TRM277-F-050719 E05-0210-86391 DLS-SW-TRM277-F-050719 Dup E05-0210-86392 DLS-SW-TRM277-F-050719 LS E05-0210-86393 DLS-SW-TRM277-F-050719 HS (1)PFOS Conc. (ng/mL) (2)Field Matrix Average Spike % Result Recovery Sample/Sample Duplicate %RPD Extraction Date 0.00670 NA 07/26/2005 < 0.00496 NA 0.05960 107 (3)0.00670 07/26/2005 NA 07/26/2005 0.564 112 07/26/2005 < 0.00496 NA 07/26/2005 < 0.00496 NA 0.0574 116 < 0.00496 (4)NA 07/26/2005 07/26/2005 0.607 122 07/26/2005 < 0.00496 NA 07/26/2005 < 0.00496 NA 0.0604 122 < 0.00496 (4)NA 07/26/2005 07/26/2005 0.558 112 07/26/2005 0.12900 111 07/26/2005 0.59000 104 0.0736 NA 0.0742 07/26/2005 1.48 07/26/2005 0.0747 NA 07/26/2005 0.07630 NA 07/26/2005 0.07220 NA 0.1340 121 0.0743 07/26/2005 5.52 07/26/2005 0.544 94.7 07/26/2005 0.0588 NA 07/26/2005 0.0462 NA 0.120 136 0.0525 07/26/2005 24.0 07/26/2005 0.631 117 07/26/2005 0.0528 NA 07/26/2005 0.0703 NA 0.0973 72.2 0.0616 07/26/2005 28.4 07/26/2005 0.605 110 07/26/2005 0.0336 NA 07/26/2005 0.0530 NA 0.0881 90.5 0.0433 07/26/2005 44.8 07/26/2005 0.575 107 07/26/2005 0.0304 NA 0.0390 NA 0.0861 104 0.515 96.8 0.0347 07/26/2005 24.8 07/26/2005 07/26/2005 07/26/2005 E05-0210 Interim Report#13 Tennessee River Page 40 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 18. PFOS Sample Results Continued. 3M Sample Number Sample Description (1)PFOS Conc. (ng/mL) (2)Field Matrix Average Spike % Result Recovery Sample/Sample Duplicate %RPD Extraction Date E05-0210-86394 DLS-SW-TRM271-0-050719 0.0320 NA 07/26/2005 E05-0210-86395 DLS-SW-TRM271-0-050719 Dup 0.0332 NA E05-0210-86396 DLS-SW-TRM271-0-050719 LS 0.0837 103 0.0326 07/26/2005 3.68 07/26/2005 E05-0210-86397 DLS-SW-TRM271-0-050719 HS 0.563 107 07/26/2005 E05-0210-86398 DLS-SW-TRM265-0-050719 0.0377 NA 07/26/2005 E05-0210-86399 DLS-SW-TRM265-0-050719 Dup 0.0375 NA E05-0210-86400 DLS-SW-TRM265-0-050719 LS 0.0820 89.7 0.0376 0.532 07/26/2005 07/26/2005 E05-0210-86401 DLS-SW-TRM265-0-050719 HS 0.596 112 07/26/2005 E05-0210-86402 DLS-SW-TRM261-2-050720 < 0.00496 NA 07/26/2005 E05-0210-86403 DLS-SW-TRM261-2-050720 Dup < 0.00496 NA E05-0210-86404 DLS-SW-TRM261-2-050720 LS 0.0593 120 < 0.00496 (4)NA 07/26/2005 07/26/2005 E05-0210-86405 DLS-SW-TRM261-2-050720 HS 0.571 115 07/26/2005 E05-0210-86406 DLS-SW-TRM261-0-050720 0.0324 NA 07/26/2005 E05-0210-86407 DLS-SW-TRM261-0-050720 Dup 0.0330 NA E05-0210-86408 DLS-SW-TRM261-0-050720 LS 0.0839 103 0.0327 07/26/2005 1.83 07/26/2005 E05-0210-86409 DLS-SW-TRM261-0-050720 HS 0.562 107 07/26/2005 E05-0210-86410 DLS-SW-TRM261-F-050720 0.0333 NA 07/26/2005 E05-0210-86411 DLS-SW-TRM261-F-050720 Dup 0.0232 NA E05-0210-86412 DLS-SW-TRM261-F-050720 LS 0.0783 101 0.0283 07/26/2005 35.8 07/27/2005 E05-0210-86413 DLS-SW-TRM261-F-050720 HS 0.525 100 07/27/2005 E05-0210-86414 DLS-SW-TRM256-0-050720 0.0326 NA 07/27/2005 E05-0210-86415 DLS-SW-TRM256-0-050720 Dup 0.0342 NA E05-0210-86416 DLS-SW-TRM256-0-050720 LS 0.0856 105 0.0334 07/27/2005 4.79 07/27/2005 E05-0210-86417 DLS-SW-TRM256-0-050720 HS 0.558 106 07/27/2005 E05-0210-86418 DLS-SW-TRM254-0-050720 0.0352 NA 07/27/2005 E05-0210-86419 DLS-SW-TRM254-0-050720 Dup 0.0341 NA E05-0210-86420 DLS-SW-TRM254-0-050720 LS 0.0927 117 0.0347 07/27/2005 3.17 07/27/2005 E05-0210-86421 DLS-SW-TRM254-0-050720 HS 0.594 113 07/27/2005 E05-0210-86422 DLS-SW-TRM254-F-050720 0.0300 NA 07/27/2005 E05-0210-86423 DLS-SW-TRM254-F-050720 Dup 0.0342 NA E05-0210-86424 DLS-SW-TRM254-F-050720 LS 0.0903 118 0.0321 07/27/2005 13.1 07/27/2005 E05-0210-86425 DLS-SW-TRM254-F-050720 HS 0.626 120 07/27/2005 E05-0210-86426 DLS-SW-TRM254-2-050720 < 0.00992 NA 07/27/2005 E05-0210-86427 DLS-SW-TRM254-2-050720 Dup < 0.00992 NA E05-0210-86428 DLS-SW-TRM254-2-050720 LS 0.0577 116 < 0.00992 (4)NA 07/27/2005 07/27/2005 E05-0210-86429 DLS-SW-TRM254-2-050720 HS 0.525 106 07/27/2005 E05-0210 Interim Report#13 Tennessee River Page 41 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 18. PFOS Sample Results Continued. 3M Sample Number Sample Description E05-0210-86430 DXS-SW-T01001-0-050721 E05-0210-86431 DXS-SW-T01001-0-050721 Dup E05-0210-86432 DXS-SW-T01001-0-050721 LS E05-0210-86433 DXS-SW-T01001-0-050721 HS E05-0210-86434 DXS-SW-T01002-0-050721 E05-0210-86435 DXS-SW-T01002-0-050721 Dup E05-0210-86436 DXS-SW-T01002-0-050721 LS E05-0210-86437 DXS-SW-T01002-0-050721 HS E05-0210-86438 DXS-SW-T01003-0-050721 E05-0210-86439 DXS-SW-T01003-0-050721 Dup E05-0210-86440 DXS-SW-T01003-0-050721 LS E05-0210-86441 DXS-SW-T01003-0-050721 HS (1)PFOS Conc. (ng/mL) 0.0739 0.0680 0.1230 0.602 0.0607 0.0594 0.1050 0.635 0.0542 0.0555 0.107 0.580 E05-0210-86442 DXS-SW-T01004-0-050721 E05-0210-86443 DXS-SW-T01004-0-050721 Dup E05-0210-86444 DXS-SW-T01004-0-050721 LS E05-0210-86445 DXS-SW-T01004-0-050721 HS E05-0210-86446 DXS-SW-T01005-0-050721 E05-0210-86447 DXS-SW-T01005-0-050721 Dup E05-0210-86448 DXS-SW-T01005-0-050721 LS E05-0210-86449 DXS-SW-T01005-0-050721 HS E05-0210-86450 DXS-SW-T01006-0-050721 E05-0210-86451 DXS-SW-T01006-0-050721 Dup E05-0210-86452 DXS-SW-T01006-0-050721 LS E05-0210-86453 DXS-SW-T01006-0-050721 HS E05-0210-86454 DXS-SW-T01007-0-050721 E05-0210-86455 DXS-SW-T01007-0-050721 Dup E05-0210-86456 DXS-SW-T01007-0-050721 LS E05-0210-86457 DXS-SW-T01007-0-050721 HS E05-0210-86458 DXS-SW-T01008-0-050721 E05-0210-86459 DXS-SW-T01008-0-050721 Dup E05-0210-86460 DXS-SW-T01008-0-050721 LS E05-0210-86461 DXS-SW-T01008-0-050721 HS E05-0210-86462 DXS-SW-T01009-0-050721 E05-0210-86463 DXS-SW-T01009-0-050721 Dup E05-0210-86464 DXS-SW-T01009-0-050721 LS E05-0210-86465 DXS-SW-T01009-0-050721 HS 0.0560 0.0636 0.114 0.521 0.0383 0.0390 0.133 0.605 0.0209 0.0219 0.0903 0.650 0.0273 0.0268 0.0865 0.586 0.0219 0.0217 0.0892 0.523 0.0202 0.0203 0.0770 0.631 (2)Field Matrix Average Result Spike % Sample/Sample Recovery Duplicate %RPD Extraction Date NA 07/27/2005 NA 07/27/2005 0.0710 8.32 105 07/27/2005 107 07/27/2005 NA 07/27/2005 NA 07/27/2005 0.0601 2.16 90.8 07/27/2005 116 07/27/2005 NA 07/27/2005 NA 07/27/2005 105 0.0549 2.37 07/27/2005 117 07/28/2005 centrifuged NA 07/27/2005 NA 07/27/2005 0.0598 12.7 109 07/27/2005 93.0 07/27/2005 NA 07/27/2005 NA 07/27/2005 0.0387 1.81 191 07/27/2005 114 07/27/2005 NA 07/27/2005 NA 07/27/2005 0.0214 4.67 139 07/27/2005 127 07/27/2005 NA 07/27/2005 NA 07/27/2005 0.0271 1.85 120 07/27/2005 113 07/27/2005 NA 07/27/2005 NA 07/27/2005 0.0218 0.917 136 07/27/2005 101 07/27/2005 NA 07/27/2005 NA 07/27/2005 0.0203 0.494 115 07/27/2005 123 07/27/2005 E05-0210 Interim Report#13 Tennessee River Page 42 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 18. PFOS Sample Results Continued. 3M Sample Number Sample Description E05-0210-86466 DXS-SW-T01010-0-050721 E05-0210-86467 DXS-SW-T01010-0-050721 Dup E05-0210-86468 DXS-SW-T01010-0-050721 LS E05-0210-86469 DXS-SW-T01010-0-050721 HS E05-0210-86470 DXS-SW-T02001-0-050721 E05-0210-86471 DXS-SW-T02001-0-050721 Dup E05-0210-86472 DXS-SW-T02001-0-050721 LS E05-0210-86473 DXS-SW-T02001-0-050721 HS E05-0210-86474 DXS-SW-T02002-0-050721 E05-0210-86475 DXS-SW-T02002-0-050721 Dup E05-0210-86476 DXS-SW-T02002-0-050721 LS E05-0210-86477 DXS-SW-T02002-0-050721 HS E05-0210-86478 DXS-SW-T02003-0-050721 E05-0210-86479 DXS-SW-T02003-0-050721 Dup E05-0210-86480 DXS-SW-T02003-0-050721 LS E05-0210-86481 DXS-SW-T02003-0-050721 HS E05-0210-86482 DXS-SW-T02004-0-050721 E05-0210-86483 DXS-SW-T02004-0-050721 Dup E05-0210-86484 DXS-SW-T02004-0-050721 LS E05-0210-86485 DXS-SW-T02004-0-050721 HS E05-0210-86486 DXS-SW-T02005-0-050721 E05-0210-86487 DXS-SW-T02005-0-050721 Dup E05-0210-86488 DXS-SW-T02005-0-050721 LS E05-0210-86489 DXS-SW-T02005-0-050721 HS E05-0210-86490 DXS-SW-T02006-0-050721 E05-0210-86491 DXS-SW-T02006-0-050721 Dup E05-0210-86492 DXS-SW-T02006-0-050721 LS E05-0210-86493 DXS-SW-T02006-0-050721 HS E05-0210-86494 DXS-SW-T02007-0-050721 E05-0210-86495 DXS-SW-T02007-0-050721 Dup E05-0210-86496 DXS-SW-T02007-0-050721 LS E05-0210-86497 DXS-SW-T02007-0-050721 HS E05-0210-86498 DXS-SW-T02008-0-050721 E05-0210-86499 DXS-SW-T02008-0-050721 Dup E05-0210-86500 DXS-SW-T02008-0-050721 LS E05-0210-86501 DXS-SW-T02008-0-050721 HS (1)PFOS Conc. (ng/mL) 0.0216 0.0219 0.0772 0.553 0.129 0.117 0.170 0.640 0.0707 0.0762 0.1260 0.606 < 0.00992 < 0.00992 0.0548 0.511 < 0.00992 < 0.00992 0.0659 0.523 < 0.00744 < 0.0496 0.0560 0.684 < 0.00744 0.00799 0.0728 0.667 < 0.00744 < 0.00744 0.0513 0.479 < 0.00744 < 0.00744 0.0579 0.493 (2)Field Matrix Average Result Spike % Sample/Sample Recovery Duplicate NA NA 0.0218 112 107 NA NA 0.123 94.9 104 NA NA 0.0735 106 107 NA NA < 0.00992 111 103 NA NA < 0.00992 119 104 NA NA < 0.0496 113 138 NA NA 131 133 NA NA 104 96.6 NA NA 117 99.4 (3)(6)0.00799 < 0.00744 < 0.00744 %RPD Extraction Date 07/27/2005 07/27/2005 1.38 07/27/2005 07/27/2005 07/27/2005 07/27/2005 9.76 07/27/2005 07/27/2005 07/27/2005 07/27/2005 7.49 07/27/2005 07/27/2005 07/27/2005 (4)NA 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 NA 07/27/2005 07/27/2005 (4)NA 07/27/2005 07/28/2005 centrifuged 07/27/2005 07/28/2005 centrifuged 07/27/2005 07/27/2005 NA 07/27/2005 07/27/2005 07/27/2005 (4)NA 07/27/2005 07/27/2005 07/27/2005 07/27/2005 (4)NA 07/27/2005 07/27/2005 07/27/2005 E05-0210 Interim Report#13 Tennessee River Page 43 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 18. PFOS Sample Results Continued. 3M Sample Number Sample Description E05-0210-86502 DXS-SW-T02009-0-050721 E05-0210-86503 DXS-SW-T02009-0-050721 Dup E05-0210-86504 DXS-SW-T02009-0-050721 LS E05-0210-86505 DXS-SW-T02009-0-050721 HS E05-0210-86506 DXS-SW-T02010-0-050721 E05-0210-86507 DXS-SW-T02010-0-050721 Dup E05-0210-86508 DXS-SW-T02010-0-050721 LS E05-0210-86509 DXS-SW-T02010-0-050721 HS E05-0210-86510 DXS-SW-T03001-0-050721 E05-0210-86511 DXS-SW-T03001-0-050721 Dup E05-0210-86512 DXS-SW-T03001-0-050721 LS E05-0210-86513 DXS-SW-T03001-0-050721 HS E05-0210-86514 DXS-SW-T03002-0-050721 E05-0210-86515 DXS-SW-T03002-0-050721 Dup E05-0210-86516 DXS-SW-T03002-0-050721 LS E05-0210-86517 DXS-SW-T03002-0-050721 HS E05-0210-86518 DXS-SW-T03003-0-050721 E05-0210-86519 DXS-SW-T03003-0-050721 Dup E05-0210-86520 DXS-SW-T03003-0-050721 LS E05-0210-86521 DXS-SW-T03003-0-050721 HS E05-0210-86522 DXS-SW-T03004-0-050722 E05-0210-86523 DXS-SW-T03004-0-050722 Dup E05-0210-86524 DXS-SW-T03004-0-050722 LS E05-0210-86525 DXS-SW-T03004-0-050722 HS E05-0210-86526 DXS-SW-T03005-0-050722 E05-0210-86527 DXS-SW-T03005-0-050722 Dup E05-0210-86528 DXS-SW-T03005-0-050722 LS E05-0210-86529 DXS-SW-T03005-0-050722 HS E05-0210-86530 DXS-SW-T03006-0-050722 E05-0210-86531 DXS-SW-T03006-0-050722 Dup E05-0210-86532 DXS-SW-T03006-0-050722 LS E05-0210-86533 DXS-SW-T03006-0-050722 HS E05-0210-86534 DXS-SW-T03007-0-050722 E05-0210-86535 DXS-SW-T03007-0-050722 Dup E05-0210-86536 DXS-SW-T03007-0-050722 LS E05-0210-86537 DXS-SW-T03007-0-050722 HS (1)PFOS Conc. (ng/mL) 0.00872 0.00883 0.0725 0.524 0.0426 0.0285 0.0590 0.293 0.782 0.807 0.909 1.330 0.0235 0.0169 0.0711 0.543 0.0111 0.0118 0.0715 0.549 0.0226 0.0167 0.0696 0.561 < 0.00744 0.0773 0.0762 0.594 0.00763 < 0.00744 < 0.0496 0.665 < 0.00744 < 0.0496 0.0664 0.576 (2)Field Matrix Average Result Spike % Sample/Sample Recovery Duplicate NA NA 0.00878 129 104 NA NA 47.4 (6)0.0356 51.9 NA NA (7)NR 0.795 108 NA NA 0.0202 103 105 NA NA 0.0115 121 108 NA NA 0.0197 101 109 NA NA (8)NR 104 NA NA (9)NR (3)0.0773 (3)0.00763 132 NA NA < 0.0496 134 116 %RPD Extraction Date 07/27/2005 07/27/2005 1.25 07/27/2005 07/27/2005 07/27/2005 07/27/2005 39.7 07/27/2005 07/27/2005 07/27/2005 07/27/2005 3.15 07/27/2005 07/27/2005 07/27/2005 07/27/2005 32.7 07/27/2005 07/27/2005 07/27/2005 07/27/2005 6.11 07/27/2005 07/27/2005 07/27/2005 07/27/2005 30.0 07/27/2005 07/27/2005 07/27/2005 07/28/2005 NA centrifuged 07/27/2005 07/27/2005 07/27/2005 07/27/2005 NA 07/28/2005 centrifuged 07/27/2005 (4)NA 07/27/2005 07/28/2005 centrifuged 07/27/2005 07/27/2005 E05-0210 Interim Report#13 Tennessee River Page 44 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 18. PFOS Sample Results Continued. 3M Sample Number Sample Description (1)PFOS Conc. (ng/mL) (2)Field Matrix Average Result Spike % Sample/Sample Recovery Duplicate %RPD Extraction Date E05-0210-86538 DXS-SW-T03008-0-050722 < 0.00744 NA 07/27/2005 E05-0210-86539 DXS-SW-T03008-0-050722 Dup < 0.00744 NA E05-0210-86540 DXS-SW-T03008-0-050722 LS 0.0600 121 < 0.00744 07/27/2005 NA 07/27/2005 E05-0210-86541 DXS-SW-T03008-0-050722 HS 0.561 113 07/27/2005 E05-0210-86542 DXS-SW-T03009-0-050722 0.00809 NA 07/27/2005 E05-0210-86543 DXS-SW-T03009-0-050722 Dup < 0.00744 NA E05-0210-86544 DXS-SW-T03009-0-050722 LS 0.0608 106 (3)0.00809 07/27/2005 NA 07/27/2005 E05-0210-86545 DXS-SW-T03009-0-050722 HS 0.508 101 07/27/2005 E05-0210-86546 DXS-SW-T03010-0-050722 0.00749 NA 07/27/2005 E05-0210-86547 DXS-SW-T03010-0-050722 Dup < 0.00744 NA E05-0210-86548 DXS-SW-T03010-0-050722 LS 0.0556 97.2 (3)0.00749 07/27/2005 NA 07/27/2005 E05-0210-86549 DXS-SW-T03010-0-050722 HS 0.506 100 07/27/2005 E05-0210-86550 DLS-SW-TRIP01 < 0.00744 NA 07/27/2005 E05-0210-86551 DLS-SW-TRIP01 LS 0.0551 111 < 0.00744 NA 07/27/2005 E05-0210-86552 DLS-SW-TRIP01 HS 0.457 92.1 07/27/2005 E05-0210-86553 DXS-SW-TRIP02 < 0.00744 NA 07/27/2005 E05-0210-86554 DXS-SW-TRIP02 LS 0.0516 104 < 0.00744 NA 07/27/2005 E05-0210-86555 DXS-SW-TRIP02 HS 0.491 99.0 07/27/2005 E05-0210-86556 DXS-SW-TRIP03 < 0.00744 NA 07/27/2005 E05-0210-86557 DXS-SW-TRIP03 LS 0.0552 112 < 0.00744 NA 07/27/2005 E05-0210-86558 DXS-SW-TRIP03 HS 0.537 108 07/27/2005 (1) The analytical uncertainty of the PFOS results is 10013.8 % based on method accuracy and precision. All results and calculations in this table are presented with three significant figures. Sample concentrations, averages, and %RPD values may vary slightly from the raw data. (2) Low field matrix spike concentration = 0.0496 ng/mL. High field matrix spike concentration = 0.496 ng/mL. (3) 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. (4) NA: Not applicable. %RPD value was not determined when concentrations for the both the sample and sample duplicate were below the stated LOQ. (5) Sample descriptions were misidentified when checked into LIMS. Samples with LIMS ID numbers 86370 and 86371 were in bottles labeled low spike and high spike, respectively. Bottles with LIMS ID numbers 86372 and 86372 were surrogate spiked only (sample and sample duplicate bottles). (6) Both field matrix spikes associated with this sampling location exceeded method acceptance criteria of 10030%. Analytical accuracy for this location should be considered 10050% due matrix contributions. (7) NR: Not reported. Spike recovery not calculated as the endogenous sample concentration was at least three times the spiked amount. (8) NR: Not reported. Concentration of spiked sample roughly equivalent to sample replicate producing a concentration above the stated LOQ. Reported sample concentration should be considered accurate to within 10050% based on high field matrix spike recovery only (poor precision between sample/sample duplicate). (9) NR: Not reported. PFOS not quantitated above the stated LOQ for the low matrix spike. Reported sample concentration should be considered accurate to within 10050% based on high field matrix spike recovery only. E05-0210 Interim Report#13 Tennessee River Page 45 of 160 Table 19. PFOA[1,2 13C] Surrogate Results. 3M Environmental Laboratory E05-0210 Interim Report#13 3M Sample Number E05-0210-86358 E05-0210-86359 E05-0210-86360 E05-0210-86361 E05-0210-86362 E05-0210-86363 E05-0210-86364 E05-0210-86365 E05-0210-86366 E05-0210-86367 E05-0210-86368 E05-0210-86369 E05-0210-86370 E05-0210-86371 E05-0210-86372 E05-0210-86373 E05-0210-86374 E05-0210-86375 E05-0210-86376 E05-0210-86377 E05-0210-86378 E05-0210-86379 E05-0210-86380 E05-0210-86381 E05-0210-86382 E05-0210-86383 E05-0210-86384 E05-0210-86385 E05-0210-86386 E05-0210-86387 E05-0210-86388 E05-0210-86389 E05-0210-86390 E05-0210-86391 E05-0210-86392 E05-0210-86393 E05-0210-86394 E05-0210-86395 E05-0210-86396 E05-0210-86397 Sample Description DLS-SW-TRM307-0-050718 DLS-SW-TRM307-0-050718 Dup DLS-SW-TRM307-0-050718 LS DLS-SW-TRM307-0-050718 HS DLS-SW-TRM301-0-050718 DLS-SW-TRM301-0-050718 Dup DLS-SW-TRM301-0-050718 LS DLS-SW-TRM301-0-050718 HS DLS-SW-TRM301-F-050718 DLS-SW-TRM301-F-050718 Dup DLS-SW-TRM301-F-050718 LS DLS-SW-TRM301-F-050718 HS DLS-SW-TRM295-0-050719 DLS-SW-TRM295-0-050719 Dup DLS-SW-TRM295-0-050719 LS DLS-SW-TRM295-0-050719 HS DLS-SW-TRM289-0-050719 DLS-SW-TRM289-0-050719 Dup DLS-SW-TRM289-0-050719 LS DLS-SW-TRM289-0-050719 HS DLS-SW-TRM289-F-050719 DLS-SW-TRM289-F-050719 Dup DLS-SW-TRM289-F-050719 LS DLS-SW-TRM289-F-050719 HS DLS-SW-TRM283-0-050719 DLS-SW-TRM283-0-050719 Dup DLS-SW-TRM283-0-050719 LS DLS-SW-TRM283-0-050719 HS DLS-SW-TRM277-0-050719 DLS-SW-TRM277-0-050719 Dup DLS-SW-TRM277-0-050719 LS DLS-SW-TRM277-0-050719 HS DLS-SW-TRM277-F-050719 DLS-SW-TRM277-F-050719 Dup DLS-SW-TRM277-F-050719 LS DLS-SW-TRM277-F-050719 HS DLS-SW-TRM271-0-050719 DLS-SW-TRM271-0-050719 Dup DLS-SW-TRM271-0-050719 LS DLS-SW-TRM271-0-050719 HS (2)Non-Corrected (3)Corrected (1)PFOA [1,2 13C] Surrogate Surrogate Concentration Percent Percent (ng/mL) Recovery Recovery 0.177 0.162 0.160 0.154 64.6 115 59.1 105 63.0 112 60.6 108 0.155 0.155 0.146 0.148 56.6 101 56.6 101 57.5 102 58.3 104 0.160 0.172 0.153 0.146 58.4 104 62.8 112 60.2 107 57.5 102 0.158 0.137 0.152 0.158 62.2 111 53.9 96.1 55.5 98.9 57.7 103 0.156 0.154 0.142 0.131 56.9 101 56.2 100 55.9 99.6 51.6 91.9 0.150 0.165 0.154 0.145 54.7 97.6 60.2 107 60.6 108 57.1 102 0.164 0.154 0.149 0.146 59.8 107 56.2 100 58.7 104 57.5 102 0.160 0.153 0.159 0.133 58.4 104 55.8 99.5 62.6 112 52.4 93.3 0.161 0.169 0.157 0.122 58.8 105 61.7 110 61.8 110 48.0 85.6 0.153 0.158 0.135 0.136 55.8 99.5 57.7 103 53.1 94.7 53.5 95.4 Extraction Date 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 E05-0210 Interim Report#13 Tennessee River Page 46 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 19. PFOA[1,2 13C] Surrogate Results 3M Sample Number Sample Description Continued. (1)PFOA [1,2 13C] Concentration (ng/mL) (2)Non-Corrected Surrogate Percent Recovery (3)Corrected Surrogate Percent Recovery E05-0210-86398 E05-0210-86399 E05-0210-86400 E05-0210-86401 DLS-SW-TRM265-0-050719 DLS-SW-TRM265-0-050719 Dup DLS-SW-TRM265-0-050719 LS DLS-SW-TRM265-0-050719 HS 0.148 0.157 0.133 0.138 54.0 96.3 57.3 102 52.4 93.3 54.3 96.8 E05-0210-86402 E05-0210-86403 E05-0210-86404 E05-0210-86405 DLS-SW-TRM261-2-050720 DLS-SW-TRM261-2-050720 Dup DLS-SW-TRM261-2-050720 LS DLS-SW-TRM261-2-050720 HS 0.158 0.159 0.150 0.129 57.7 103 58.0 103 59.0 105 50.8 90.5 E05-0210-86406 E05-0210-86407 E05-0210-86408 E05-0210-86409 DLS-SW-TRM261-0-050720 DLS-SW-TRM261-0-050720 Dup DLS-SW-TRM261-0-050720 LS DLS-SW-TRM261-0-050720 HS 0.147 0.156 0.141 0.134 53.6 95.6 56.9 101 55.5 99.0 52.8 94.0 E05-0210-86410 E05-0210-86411 E05-0210-86412 E05-0210-86413 DLS-SW-TRM261-F-050720 DLS-SW-TRM261-F-050720 Dup DLS-SW-TRM261-F-050720 LS DLS-SW-TRM261-F-050720 HS 0.154 0.141 0.140 0.123 56.2 100 51.4 91.7 55.1 98.2 48.4 86.3 E05-0210-86414 E05-0210-86415 E05-0210-86416 E05-0210-86417 DLS-SW-TRM256-0-050720 DLS-SW-TRM256-0-050720 Dup DLS-SW-TRM256-0-050720 LS DLS-SW-TRM256-0-050720 HS 0.143 0.148 0.145 0.133 52.2 93.0 54.0 96.3 57.1 102 52.4 93.3 E05-0210-86418 E05-0210-86419 E05-0210-86420 E05-0210-86421 DLS-SW-TRM254-0-050720 DLS-SW-TRM254-0-050720 Dup DLS-SW-TRM254-0-050720 LS DLS-SW-TRM254-0-050720 HS 0.158 0.154 0.158 0.132 57.7 103 56.2 100 62.2 111 52.0 92.6 E05-0210-86422 E05-0210-86423 E05-0210-86424 E05-0210-86425 DLS-SW-TRM254-F-050720 DLS-SW-TRM254-F-050720 Dup DLS-SW-TRM254-F-050720 LS DLS-SW-TRM254-F-050720 HS 0.160 0.164 0.159 0.147 58.4 104 59.8 107 62.6 112 57.9 103 E05-0210-86426 E05-0210-86427 E05-0210-86428 E05-0210-86429 DLS-SW-TRM254-2-050720 DLS-SW-TRM254-2-050720 Dup DLS-SW-TRM254-2-050720 LS DLS-SW-TRM254-2-050720 HS 0.162 0.157 0.145 0.138 59.1 105 57.3 102 57.1 102 54.3 96.8 E05-0210-86430 E05-0210-86431 E05-0210-86432 E05-0210-86433 DXS-SW-T01001-0-050721 DXS-SW-T01001-0-050721 Dup DXS-SW-T01001-0-050721 LS DXS-SW-T01001-0-050721 HS 0.172 0.164 0.159 0.142 62.8 112 59.8 107 62.6 112 55.9 99.6 E05-0210-86434 E05-0210-86435 E05-0210-86436 E05-0210-86437 DXS-SW-T01002-0-050721 DXS-SW-T01002-0-050721 Dup DXS-SW-T01002-0-050721 LS DXS-SW-T01002-0-050721 HS 0.167 0.164 0.139 0.146 60.9 109 59.8 107 54.7 97.6 57.5 102 Extraction Date 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/26/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 E05-0210 Interim Report#13 Tennessee River Page 47 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 19. PFOA[1,2 13C] Surrogate Results 3M Sample Number Sample Description Continued. (1)PFOA [1,2 13C] Concentration (ng/mL) (2)Non-Corrected Surrogate Percent Recovery (3)Corrected Surrogate Percent Recovery E05-0210-86438 E05-0210-86439 E05-0210-86440 E05-0210-86441 DXS-SW-T01003-0-050721 DXS-SW-T01003-0-050721 Dup DXS-SW-T01003-0-050721 LS DXS-SW-T01003-0-050721 HS 0.158 0.161 0.142 0.135 57.7 103 58.8 105 55.9 99.6 53.1 94.7 E05-0210-86442 E05-0210-86443 E05-0210-86444 E05-0210-86445 E05-0210-86446 E05-0210-86447 E05-0210-86448 E05-0210-86449 E05-0210-86450 E05-0210-86451 E05-0210-86452 E05-0210-86453 E05-0210-86454 E05-0210-86455 E05-0210-86456 E05-0210-86457 E05-0210-86458 E05-0210-86459 E05-0210-86460 E05-0210-86461 E05-0210-86462 E05-0210-86463 E05-0210-86464 E05-0210-86465 E05-0210-86466 E05-0210-86467 E05-0210-86468 E05-0210-86469 E05-0210-86470 E05-0210-86471 E05-0210-86472 E05-0210-86473 E05-0210-86474 E05-0210-86475 E05-0210-86476 E05-0210-86477 DXS-SW-T01004-0-050721 DXS-SW-T01004-0-050721 Dup DXS-SW-T01004-0-050721 LS DXS-SW-T01004-0-050721 HS DXS-SW-T01005-0-050721 DXS-SW-T01005-0-050721 Dup DXS-SW-T01005-0-050721 LS DXS-SW-T01005-0-050721 HS DXS-SW-T01006-0-050721 DXS-SW-T01006-0-050721 Dup DXS-SW-T01006-0-050721 LS DXS-SW-T01006-0-050721 HS DXS-SW-T01007-0-050721 DXS-SW-T01007-0-050721 Dup DXS-SW-T01007-0-050721 LS DXS-SW-T01007-0-050721 HS DXS-SW-T01008-0-050721 DXS-SW-T01008-0-050721 Dup DXS-SW-T01008-0-050721 LS DXS-SW-T01008-0-050721 HS DXS-SW-T01009-0-050721 DXS-SW-T01009-0-050721 Dup DXS-SW-T01009-0-050721 LS DXS-SW-T01009-0-050721 HS DXS-SW-T01010-0-050721 DXS-SW-T01010-0-050721 Dup DXS-SW-T01010-0-050721 LS DXS-SW-T01010-0-050721 HS DXS-SW-T02001-0-050721 DXS-SW-T02001-0-050721 Dup DXS-SW-T02001-0-050721 LS DXS-SW-T02001-0-050721 HS DXS-SW-T02002-0-050721 DXS-SW-T02002-0-050721 Dup DXS-SW-T02002-0-050721 LS DXS-SW-T02002-0-050721 HS 0.175 0.160 0.162 0.126 0.167 0.171 0.151 0.137 0.157 0.162 0.178 0.151 0.148 0.159 0.152 0.144 0.149 0.149 0.180 0.123 0.163 0.163 0.144 0.141 0.168 0.170 0.145 0.134 0.152 0.165 0.141 0.131 0.148 0.145 0.138 0.137 63.9 114 58.4 104 63.8 114 49.6 88.4 60.9 109 62.4 111 59.4 106 53.9 96.1 57.3 102 59.1 105 70.1 125 59.4 106 54.0 96.3 58.0 103 59.8 107 56.7 101 54.4 96.9 54.4 96.9 70.9 126 48.4 86.3 59.5 106 59.5 106 56.7 101 55.5 99.0 61.3 109 62.0 110 57.1 102 52.8 94.0 55.5 98.9 60.2 107 55.5 99.0 51.6 91.9 54.0 96.3 52.9 94.3 54.3 96.8 53.9 96.1 Extraction Date 07/27/2005 07/27/2005 07/27/2005 07/28/2005 centrifuged 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 E05-0210 Interim Report#13 Tennessee River Page 48 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 19. PFOA[1,2 13C] Surrogate Results 3M Sample Number Sample Description Continued. (1)PFOA [1,2 13C] Concentration (ng/mL) (2)Non-Corrected Surrogate Percent Recovery (3)Corrected Surrogate Percent Recovery E05-0210-86478 E05-0210-86479 E05-0210-86480 E05-0210-86481 DXS-SW-T02003-0-050721 DXS-SW-T02003-0-050721 Dup DXS-SW-T02003-0-050721 LS DXS-SW-T02003-0-050721 HS 0.149 0.165 0.136 0.133 54.4 96.9 60.2 107 53.5 95.4 52.4 93.3 E05-0210-86482 E05-0210-86483 E05-0210-86484 E05-0210-86485 DXS-SW-T02004-0-050721 DXS-SW-T02004-0-050721 Dup DXS-SW-T02004-0-050721 LS DXS-SW-T02004-0-050721 HS 0.172 0.154 0.161 0.131 62.8 112 56.2 100 58.8 105 47.8 85.2 E05-0210-86486 DXS-SW-T02005-0-050721 0.178 70.1 125 E05-0210-86487 E05-0210-86488 E05-0210-86489 DXS-SW-T02005-0-050721 Dup DXS-SW-T02005-0-050721 LS DXS-SW-T02005-0-050721 HS 0.170 0.139 0.177 62.0 110 54.7 97.6 69.7 124 E05-0210-86490 E05-0210-86491 E05-0210-86492 E05-0210-86493 E05-0210-86494 E05-0210-86495 E05-0210-86496 E05-0210-86497 E05-0210-86498 E05-0210-86499 E05-0210-86500 E05-0210-86501 E05-0210-86502 E05-0210-86503 E05-0210-86504 E05-0210-86505 E05-0210-86506 E05-0210-86507 E05-0210-86508 E05-0210-86509 E05-0210-86510 E05-0210-86511 E05-0210-86512 E05-0210-86513 E05-0210-86514 E05-0210-86515 E05-0210-86516 E05-0210-86517 DXS-SW-T02006-0-050721 DXS-SW-T02006-0-050721 Dup DXS-SW-T02006-0-050721 LS DXS-SW-T02006-0-050721 HS DXS-SW-T02007-0-050721 DXS-SW-T02007-0-050721 Dup DXS-SW-T02007-0-050721 LS DXS-SW-T02007-0-050721 HS DXS-SW-T02008-0-050721 DXS-SW-T02008-0-050721 Dup DXS-SW-T02008-0-050721 LS DXS-SW-T02008-0-050721 HS DXS-SW-T02009-0-050721 DXS-SW-T02009-0-050721 Dup DXS-SW-T02009-0-050721 LS DXS-SW-T02009-0-050721 HS DXS-SW-T02010-0-050721 DXS-SW-T02010-0-050721 Dup DXS-SW-T02010-0-050721 LS DXS-SW-T02010-0-050721 HS DXS-SW-T03001-0-050721 DXS-SW-T03001-0-050721 Dup DXS-SW-T03001-0-050721 LS DXS-SW-T03001-0-050721 HS DXS-SW-T03002-0-050721 DXS-SW-T03002-0-050721 Dup DXS-SW-T03002-0-050721 LS DXS-SW-T03002-0-050721 HS 0.151 0.156 0.151 0.143 0.142 0.154 0.139 0.146 0.151 0.161 0.147 0.128 0.159 0.151 0.153 0.138 0.143 0.143 0.131 0.086 0.144 0.146 0.141 0.127 0.165 0.142 0.142 0.126 55.1 98.2 56.9 101 59.4 106 56.3 100 51.8 92.4 56.2 100 54.7 97.6 57.5 102 55.1 98.2 58.8 105 57.9 103 50.4 89.8 58.0 103 55.1 98.2 60.2 107 54.3 96.8 52.2 93.0 52.2 93.0 51.6 91.9 33.8 60.2 52.6 93.7 53.3 95.0 55.5 99.0 50.0 89.1 60.2 107 51.8 92.4 55.9 99.6 49.6 88.4 Extraction Date 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/28/2005 centrifuged 07/27/2005 07/28/2005 centrifuged 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 E05-0210 Interim Report#13 Tennessee River Page 49 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 19. PFOA[1,2 13C] Surrogate Results 3M Sample Number Sample Description Continued. (1)PFOA [1,2 13C] Concentration (ng/mL) (2)Non-Corrected Surrogate Percent Recovery (3)Corrected Surrogate Percent Recovery E05-0210-86518 E05-0210-86519 E05-0210-86520 E05-0210-86521 DXS-SW-T03003-0-050721 DXS-SW-T03003-0-050721 Dup DXS-SW-T03003-0-050721 LS DXS-SW-T03003-0-050721 HS 0.153 0.136 0.142 0.124 55.8 99.5 49.6 88.5 55.9 99.6 48.8 87.0 E05-0210-86522 E05-0210-86523 E05-0210-86524 E05-0210-86525 DXS-SW-T03004-0-050722 DXS-SW-T03004-0-050722 Dup DXS-SW-T03004-0-050722 LS DXS-SW-T03004-0-050722 HS 0.154 0.142 0.146 0.135 56.2 100 51.8 92.4 57.5 102 53.1 94.7 E05-0210-86526 DXS-SW-T03005-0-050722 0.139 50.7 90.4 E05-0210-86527 DXS-SW-T03005-0-050722 Dup 0.048 17.7 31.5 E05-0210-86528 E05-0210-86529 DXS-SW-T03005-0-050722 LS DXS-SW-T03005-0-050722 HS 0.165 0.138 65.0 116 54.3 96.8 E05-0210-86530 E05-0210-86531 DXS-SW-T03006-0-050722 DXS-SW-T03006-0-050722 Dup 0.151 0.138 55.1 98.2 50.4 89.8 E05-0210-86532 DXS-SW-T03006-0-050722 LS 0.012 4.61 8.21 E05-0210-86533 DXS-SW-T03006-0-050722 HS 0.155 61.0 109 E05-0210-86534 E05-0210-86535 DXS-SW-T03007-0-050722 DXS-SW-T03007-0-050722 Dup 0.164 0.179 59.8 107 65.3 116 E05-0210-86536 E05-0210-86537 DXS-SW-T03007-0-050722 LS DXS-SW-T03007-0-050722 HS 0.155 0.127 61.0 109 50.0 89.1 E05-0210-86538 E05-0210-86539 E05-0210-86540 E05-0210-86541 DXS-SW-T03008-0-050722 DXS-SW-T03008-0-050722 Dup DXS-SW-T03008-0-050722 LS DXS-SW-T03008-0-050722 HS 0.162 0.158 0.141 0.132 59.1 105 57.7 103 55.5 99.0 52.0 92.6 E05-0210-86542 E05-0210-86543 E05-0210-86544 E05-0210-86545 DXS-SW-T03009-0-050722 DXS-SW-T03009-0-050722 Dup DXS-SW-T03009-0-050722 LS DXS-SW-T03009-0-050722 HS 0.161 0.144 0.147 0.132 58.8 105 52.6 93.7 57.9 103 52.0 92.6 E05-0210-86546 E05-0210-86547 E05-0210-86548 E05-0210-86549 DXS-SW-T03010-0-050722 DXS-SW-T03010-0-050722 Dup DXS-SW-T03010-0-050722 LS DXS-SW-T03010-0-050722 HS 0.148 0.140 0.145 0.127 54.0 96.3 51.1 91.1 57.1 102 50.0 89.1 Extraction Date 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/28/2005 centrifuged 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/28/2005 centrifuged 07/27/2005 07/27/2005 07/28/2005 centrifuged 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 E05-0210 Interim Report#13 Tennessee River Page 50 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Table 19. PFOA[1,2 13C] Surrogate Results 3M Sample Number Sample Description Continued. (1)PFOA [1,2 13C] Concentration (ng/mL) (2)Non-Corrected Surrogate Percent Recovery (3)Corrected Surrogate Percent Recovery E05-0210-86550 E05-0210-86551 E05-0210-86552 DLS-SW-TRIP01 DLS-SW-TRIP01 LS DLS-SW-TRIP01 HS 0.139 0.138 0.117 50.7 90.4 50.4 89.8 46.1 82.1 E05-0210-86553 E05-0210-86554 E05-0210-86555 DXS-SW-TRIP02 DXS-SW-TRIP02 LS DXS-SW-TRIP02 HS 0.137 0.130 0.112 50.0 89.1 51.2 91.2 44.1 78.6 E05-0210-86556 E05-0210-86557 E05-0210-86558 DXS-SW-TRIP03 DXS-SW-TRIP03 LS DXS-SW-TRIP03 HS 0.144 0.128 0.129 52.6 93.7 50.4 89.8 50.8 90.5 Extraction Date 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 07/27/2005 (1) All results and calculations in this table are presented with three significant figures. Sample concentrations, values may vary slightly from the raw data. (2) Surrogate concentration in sample/sample duplicates = 0.274 ng/mL. Surrogate concentration in low and high field matrix spikes = 0.254 ng/mL. (3) A correction factor of 56.1% was applied to all surrogate recoveries. The overall average raw surrogate recovery was used to determine the correction factor. Corrected Surrogate Percent Recovery = Non - Corrected Surrogate Percent Recovery 56.1 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 E05-0210 Interim Report#13 Tennessee River Page 51 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 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. For example, the overall accuracy and precision for PFBS based on LCS results was 107%3.49% (three significant figures). The measured precision (%RSD) is then used to determine the range of the accuracy. Example: 106.8*(0.0349) = 3.73 106.8 + 3.73 = 110.6; 107 - 3.73 = 103 Thus, LCS accuracy results range from 103% to 110.6%. The absolute difference of the low and high ends of this range, when compared 100%, are then calculated. 110.6%-100%= 10.6% 103%-100 = 3%. The most conservative (largest) absolute difference is then used as the analytical uncertainty for the given analyte. Therefore, the analytical uncertainty for PFBS is given as 10010.6% for this set of data. For PFHS, the overall project accuracy and precision of the the LCS results was 110%4.72%. This produced an estimated analytical uncertainty of 10015.2%. For PFOS, the overall project accuracy and precision was 108%%5.79% resulting in an estimated analytical accuracy of 10013.8%. STATEMENT OF CONCLUSION Sample results for PFBS, PFHS, and PFOS were presented in Table 1. Laboratory control spikes were used to determine the method accuracy and precision for each analyte. The accuracy and precision were then used to estimate the analytical uncertainty. Recoveries of field matrix spiked samples within 10030% demonstrated that the overall analytical method was appropriate for the matrix collected. Analytical accuracy for select PFOS results was adjusted to 10050% for samples whose associated field matrix spikes produced recoveries exceeding 10030%. LIST OF ATTACHMENTS Attachment A: Sample Chromatograms and Calibration Curves Attachment B: Extraction and Analytical Methods Attachment C: Protocol and Protocol Amendments E05-0210 Interim Report#13 Tennessee River Page 52 of 160 3M EnvSrOnmental laboratory E050210 lnterlm R e p o d 1 3 SIGNATURPEAGE We certify that this report is a true and complete representation of the data for this study: Jaisimha Kesari, P.E., DEE, Study Director -Date Micheble D. Malinsky, Ph.D., enior Chemist Date Testing Facility Management Date Sponsor Representative ' / Date E050210 lnterlm R e p o d 1 3 Tennessee RIver Page 53 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 ATTACHMENT A: SAMPLE CHROMATOGRAMS AND CALIBRATION CURVES E05-0210 Interim Report#13 Tennessee River Page 54 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Sample Name: "s050726a020" Sample ID: "EC-050726-009 0.25 ppb extracted curve point" Peak Name: "13C pfoa" Mass(es): "414.9/369.8 amu" Comment: "" Annotation: "" Sample Index: 20 Sample Type: Standard Concentration: 0.2490 Calculated Conc: 0.253 ng/mL ng/mL 2.9e5 Acq. Date: Acq. Time: 07/26/2005 10:24:23 PM 2.9e5 2.8e5 Modified: No Proc. Algorithm: IntelliQuan - MQII 2.8e5 Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 2.7e5 2.7e5 Report Largest Peak: No Min. Peak Height: 0.00 cps 2.6e5 Min. Peak Width: 0.00 sec 2.6e5 Smoothing Width: RT Window: 3 30.0 points sec 2.5e5 Expected RT: Use Relative RT: 13.9 min No 2.5e5 2.4e5 Int. Type: Valley Retention Time: 13.869 min 2.4e5 Area: Height: Start Time: 1581772 counts 2.92e+005 cps 13.704 min 2.3e5 2.3e5 End Time: 14.241 min 2.2e5 File: "s050726a.wiff" 13.87 2.2e5 2.1e5 2.1e5 2.0e5 2.0e5 1.9e5 1.9e5 1.8e5 1.8e5 1.7e5 1.7e5 1.6e5 1.6e5 Intensity, cps 1.5e5 1.5e5 1.4e5 1.4e5 1.3e5 1.3e5 1.2e5 1.2e5 1.1e5 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 14.32 0.0 12.9 13.0 13.1 13.2 13.3 13.4 13.5 13.6 13.7 13.8 13.9 14.0 14.1 14.2 14.3 14.4 14.5 14.6 14.7 14.8 Time, min Sample Name: "s050726a020" Sample ID: "EC-050726-009 0.25 ppb extracted curve point" Peak Name: "pfbs (tic)" Mass(es): "298.9/79.8 amu,298.9/99.0 amu" Comment: "" Annotation: "" Sample Index: 20 Sample Type: Standard Concentration: 0.2210 ng/mL Calculated Conc: 0.227 ng/mL Acq. Date: 07/26/2005 3.4e5 Acq. Time: 10:24:23 PM Modified: No Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 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: 10.7 min Use Relative RT: No 3.3e5 3.2e5 3.1e5 3.0e5 2.9e5 File: "s050726a.wiff" Int. Type: Valley Retention Time: 10.645 min Area: 2136402 counts Height: 3.48e+005 cps Start Time: 10.417 min End Time: 10.996 min 2.8e5 2.7e5 2.6e5 10.64 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 5.0e4 4.0e4 3.0e4 2.0e4 1.0e4 0.0 9.7 9.8 9.9 10.0 10.1 10.2 10.3 10.4 10.5 10.6 10.7 10.8 10.9 11.0 11.1 11.2 11.3 11.4 11.5 11.6 Time, min E05-0210 Interim Report#13 Tennessee River Page 55 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Sample Name: "s050726a020" Sample ID: "EC-050726-009 0.25 ppb extracted curve point" Peak Name: "pfhs (tic)" Mass(es): "399.0/79.8 amu,399.0/99.0 amu" Comment: "" Annotation: "" Sample Index: 20 Sample Type: Standard Concentration: 0.2600 ng/mL Calculated Conc: 0.264 ng/mL Acq. Date: 07/26/2005 2.2e5 Acq. Time: 10:24:23 PM 2.1e5 Modified: Yes RT Window: 30.0 sec Expected RT: 13.1 min Use Relative RT: No 2.1e5 2.0e5 File: "s050726a.wiff" Int. Type: Manual Retention Time: 13.094 min Area: 1376832 counts Height: 2.25e+005 cps Start Time: 12.732 min End Time: 13.290 min 2.0e5 1.9e5 1.9e5 1.8e5 13.10 1.8e5 1.7e5 1.7e5 1.6e5 1.6e5 1.5e5 1.5e5 1.4e5 1.4e5 1.3e5 1.3e5 1.2e5 Intensity, cps 1.2e5 1.1e5 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 12.88 2.5e4 2.0e4 1.5e4 1.0e4 5000.0 0.0 12.2 12.3 12.4 12.5 12.6 12.7 12.8 12.9 13.0 13.1 13.2 13.3 13.4 13.5 13.6 13.7 13.8 13.9 14.0 14.1 Time, min Sample Name: "s050726a020" Sample ID: "EC-050726-009 0.25 ppb extracted curve point" Peak Name: "pfos (tic)" Mass(es): "498.9/99.2 amu,498.9/130.0 amu,498.9/80.0 amu" Comment: "" Annotation: "" Sample Index: 20 Sample Type: Standard Concentration: 0.2480 ng/mL Calculated Conc: 0.256 ng/mL Acq. Date: 07/26/2005 6.0e4 Acq. Time: 10:24:23 PM Modified: Yes RT Window: 30.0 sec Expected RT: 14.6 min Use Relative RT: No 5.8e4 5.6e4 File: "s050726a.wiff" Int. Type: Manual Retention Time: 14.534 min Area: 483642 counts Height: 6.12e+004 cps Start Time: 13.972 min End Time: 14.716 min 5.4e4 5.2e4 5.0e4 14.53 4.8e4 4.6e4 4.4e4 4.2e4 4.0e4 3.8e4 3.6e4 3.4e4 Intensity, cps 3.2e4 3.0e4 2.8e4 2.6e4 2.4e4 2.2e4 2.0e4 14.32 1.8e4 1.6e4 1.4e4 1.2e4 1.0e4 8000.0 6000.0 4000.0 2000.0 0.0 13.6 13.7 13.8 13.9 14.0 14.1 14.2 14.3 14.4 14.5 14.6 14.7 14.8 14.9 15.0 15.1 15.2 15.3 15.4 15.5 Time, min E05-0210 Interim Report#13 Tennessee River Page 56 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Sample Name: "s050726a030" Sample ID: "MB-050726-3 Method Blank-3" Peak Name: "13C pfoa" Mass(es): "414.9/369.8 amu" Comment: "" Annotation: "" Sample Index: 30 Sample Type: Unknown Concentration: N/A 370 Calculated Conc: < 0 Acq. Date: 07/27/2005 Acq. Time: 01:55:44 AM 360 File: "s050726a.wiff" Modified: No 350 Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min 340 Peak-Split. Factor: 2 Report Largest Peak: No Min. Peak Height: 0.00 cps 330 Min. Peak Width: 0.00 sec Smoothing Width: 3 points 320 RT Window: 30.0 sec Expected RT: 13.9 min Use Relative RT: No 310 Int. Type: Valley 300 Retention Time: 13.848 min Area: 1834 counts Height: 3.70e+002 cps 290 Start Time: 13.704 min End Time: 13.993 min 280 270 260 250 240 230 220 210 200 Intensity, cps 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 12.9 13.0 13.1 13.2 13.3 13.4 13.5 13.6 13.7 13.8 13.9 14.0 14.1 14.2 14.3 14.4 14.5 14.6 14.7 14.8 Time, min Sample Name: "s050726a030" Sample ID: "MB-050726-3 Method Blank-3" Peak Name: "pfbs (tic)" Mass(es): "298.9/79.8 amu,298.9/99.0 amu" Comment: "" Annotation: "" Sample Index: 30 Sample Type: Unknown Concentration: N/A 820 Calculated Conc: < 0 Acq. Date: 07/27/2005 800 Acq. Time: 01:55:44 AM Modified: No 780 Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 760 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 740 Report Largest Peak: No Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec 720 Smoothing Width: 3 points RT Window: 30.0 sec 700 Expected RT: 10.7 min Use Relative RT: No 680 Int. Type: Valley Retention Time: 10.645 min 660 Area: 4317 counts Height: 6.65e+002 cps 640 Start Time: 10.562 min End Time: 10.893 min 620 File: "s050726a.wiff" 10.64 11.18 600 580 560 540 520 500 480 460 440 Intensity, cps 420 400 380 360 340 320 300 280 260 240 220 200 180 10.50 160 140 120 100 80 60 40 9.76 9.98 10.05 10.13 10.27 20 0 9.7 9.8 9.9 10.0 10.1 10.2 10.3 10.4 10.5 10.6 10.7 10.8 10.9 11.0 11.1 11.2 11.3 11.4 11.5 11.6 Time, min E05-0210 Interim Report#13 Tennessee River Page 57 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Sample Name: "s050726a030" Sample ID: "MB-050726-3 Method Blank-3" Peak Name: "pfhs (tic)" Mass(es): "399.0/79.8 amu,399.0/99.0 amu" Comment: "" Annotation: "" Sample Index: 30 Sample Type: Unknown Concentration: N/A Calculated Conc: < 0 310 Acq. Date: 07/27/2005 Acq. Time: 01:55:44 AM Modified: Yes 300 RT Window: 30.0 sec Expected RT: 13.1 min 290 Use Relative RT: No File: "s050726a.wiff" Int. Type: Manual 280 Retention Time: 13.096 min Area: 1793 counts Height: 2.56e+002 cps 270 Start Time: 12.898 min End Time: 13.187 min 260 13.10 13.44 250 240 230 220 210 200 190 180 170 Intensity, cps 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 12.2 12.3 12.4 12.5 12.6 12.7 12.8 12.9 13.0 13.1 13.2 13.3 13.4 13.5 13.6 13.7 13.8 13.9 14.0 14.1 Time, min Sample Name: "s050726a030" Sample ID: "MB-050726-3 Method Blank-3" File: "s050726a.wiff" Peak Name: "pfos (tic)" Mass(es): "498.9/99.2 amu,498.9/130.0 amu,498.9/80.0 amu" Comment: "" Annotation: "" Sample Index: 30 Sample Type: Unknown Concentration: N/A Calculated Conc: 0.000243 ng/mL 570 Acq. Date: 07/27/2005 Acq. Time: 01:55:44 AM 560 14.53 Modified: Yes 550 RT Window: 30.0 sec 540 Expected RT: 14.6 min Use Relative RT: No 530 520 Int. Type: Manual Retention Time: 14.523 min 510 Area: 5128 counts Height: 5.60e+002 cps 500 Start Time: 14.035 min 490 End Time: 14.634 min 480 470 460 450 440 430 420 410 400 390 380 370 360 350 340 330 320 310 Intensity, cps 300 290 280 270 260 250 240 230 220 210 14.32 14.86 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 13.6 13.7 13.8 13.9 14.0 14.1 14.2 14.3 14.4 14.5 14.6 14.7 14.8 14.9 15.0 15.1 15.2 15.3 15.4 15.5 Time, min E05-0210 Interim Report#13 Tennessee River Page 58 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Sample Name: "s050726a041" Sample ID: "LCS-050726-3 25 ppt Lab Control Spike" Peak Name: "13C pfoa" Mass(es): "414.9/369.8 amu" Comment: "" Annotation: "" Sample Index: 41 Sample Type: Unknown Concentration: N/A 3.5e4 Calculated Conc: 0.0275 ng/mL Acq. Date: Acq. Time: 07/27/2005 05:48:45 AM 3.4e4 File: "s050726a.wiff" Modified: No Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 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: 13.9 min Use Relative RT: No Int. Type: Valley Retention Time: 13.849 min Area: 184532 counts Height: 3.51e+004 cps Start Time: 13.683 min End Time: 14.572 min 3.3e4 3.2e4 3.1e4 3.0e4 2.9e4 2.8e4 2.7e4 2.6e4 13.85 2.5e4 2.4e4 2.3e4 2.2e4 2.1e4 2.0e4 1.9e4 Intensity, cps 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 2000.0 1000.0 0.0 14.72 12.9 13.0 13.1 13.2 13.3 13.4 13.5 13.6 13.7 13.8 13.9 14.0 14.1 14.2 14.3 14.4 14.5 14.6 14.7 14.8 Time, min Sample Name: "s050726a041" Sample ID: "LCS-050726-3 25 ppt Lab Control Spike" Peak Name: "pfbs (tic)" Mass(es): "298.9/79.8 amu,298.9/99.0 amu" Comment: "" Annotation: "" Sample Index: 41 Sample Type: Unknown Concentration: N/A Calculated Conc: 0.0246 ng/mL 4.2e4 Acq. Date: Acq. Time: 07/27/2005 05:48:45 AM 4.1e4 File: "s050726a.wiff" 10.67 Modified: No Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 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: 10.7 min Use Relative RT: No Int. Type: Base To Base Retention Time: 10.665 min Area: 246081 counts Height: 4.23e+004 cps Start Time: 10.479 min End Time: 10.955 min 4.0e4 3.9e4 3.8e4 3.7e4 3.6e4 3.5e4 3.4e4 3.3e4 3.2e4 3.1e4 3.0e4 2.9e4 2.8e4 2.7e4 2.6e4 2.5e4 2.4e4 2.3e4 Intensity, cps 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 2000.0 1000.0 0.0 9.7 9.8 9.9 10.0 10.1 10.2 10.3 10.4 10.5 10.6 10.7 10.8 10.9 11.0 11.1 11.2 11.3 11.4 11.5 11.6 Time, min E05-0210 Interim Report#13 Tennessee River Page 59 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Sample Name: "s050726a041" Sample ID: "LCS-050726-3 25 ppt Lab Control Spike" Peak Name: "pfhs (tic)" Mass(es): "399.0/79.8 amu,399.0/99.0 amu" Comment: "" Annotation: "" Sample Index: 41 Sample Type: Unknown Concentration: N/A Calculated Conc: 0.0294 ng/mL Acq. Date: 07/27/2005 2.7e4 Acq. Time: 05:48:45 AM 2.6e4 File: "s050726a.wiff" 13.08 Modified: No Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 5 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: 13.1 min Use Relative RT: No Int. Type: Valley Retention Time: 13.084 min Area: 158887 counts Height: 2.68e+004 cps Start Time: 12.753 min End Time: 13.270 min 2.6e4 2.5e4 2.5e4 2.4e4 2.4e4 2.3e4 2.3e4 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 Intensity, cps 1.4e4 1.4e4 1.3e4 1.3e4 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 12.88 2500.0 2000.0 1500.0 1000.0 500.0 0.0 12.2 12.3 12.4 12.5 12.6 12.7 12.8 12.9 13.0 13.1 13.2 13.3 13.4 13.5 13.6 13.7 13.8 13.9 14.0 14.1 Time, min Sample Name: "s050726a041" Sample ID: "LCS-050726-3 25 ppt Lab Control Spike" Peak Name: "pfos (tic)" Mass(es): "498.9/99.2 amu,498.9/130.0 amu,498.9/80.0 amu" Comment: "" Annotation: "" Sample Index: 41 Sample Type: Unknown Concentration: N/A Calculated Conc: 0.0300 ng/mL Acq. Date: 07/27/2005 7400 Acq. Time: 05:48:45 AM 7200 Modified: Yes RT Window: 30.0 sec Expected RT: 14.6 min Use Relative RT: No 7000 6800 Int. Type: Retention Time: Area: Height: Start Time: End Time: Manual 14.526 min 60906 counts 7.54e+003 cps 13.952 min 14.675 min 6600 6400 6200 File: "s050726a.wiff" 14.53 6000 5800 5600 5400 5200 5000 4800 4600 4400 4200 4000 Intensity, cps 3800 3600 3400 3200 3000 2800 2600 2400 14.30 2200 2000 1800 1600 1400 1200 1000 800 600 400 200 0 13.6 13.7 13.8 13.9 14.0 14.1 14.2 14.3 14.4 14.5 14.6 14.7 14.8 14.9 15.0 15.1 15.2 15.3 15.4 15.5 Time, min E05-0210 Interim Report#13 Tennessee River Page 60 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Sample Name: "s050726a034" Sample ID: "MB-050726-7 Method Blank-7" Peak Name: "13C pfoa" Mass(es): "414.9/369.8 amu" Comment: "" Annotation: "" Sample Index: 34 Sample Type: Unknown Concentration: Calculated Conc: N/A 0.197 ng/mL 2.3e5 Acq. Date: Acq. Time: 07/27/2005 03:20:27 AM 2.3e5 Modified: Yes Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 0 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: 13.9 min Use Relative RT: No Int. Type: Valley Retention Time: 13.869 min Area: 1238274 counts Height: 2.32e+005 cps Start Time: 13.621 min End Time: 14.138 min 2.2e5 2.2e5 2.1e5 2.1e5 2.0e5 2.0e5 1.9e5 1.9e5 1.8e5 1.8e5 File: "s050726a.wiff" 13.87 1.7e5 1.7e5 1.6e5 1.6e5 1.5e5 1.5e5 1.4e5 1.4e5 1.3e5 1.3e5 Intensity, cps 1.2e5 1.2e5 1.1e5 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 12.9 13.0 13.1 13.2 13.3 13.4 13.5 13.6 13.7 13.8 13.9 14.0 14.1 14.2 14.3 14.4 14.5 14.6 14.7 14.8 Time, min Sample Name: "s050726a034" Sample ID: "MB-050726-7 Method Blank-7" Peak Name: "pfbs (tic)" Mass(es): "298.9/79.8 amu,298.9/99.0 amu" Comment: "" Annotation: "" Sample Index: 34 Sample Type: Unknown Concentration: N/A Calculated Conc: < 0 Acq. Date: 07/27/2005 660 Acq. Time: 03:20:27 AM Modified: Yes 640 Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 620 Base. Sub. Window: 1.00 min Peak-Split. Factor: 0 Report Largest Peak: No 600 Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec Smoothing Width: 3 points 580 RT Window: 30.0 sec Expected RT: 10.7 min Use Relative RT: No 560 File: "s050726a.wiff" Int. Type: Valley Retention Time: 10.686 min 540 Area: 3668 counts Height: 5.37e+002 cps 520 Start Time: 10.562 min End Time: 10.872 min 500 480 460 440 420 400 380 360 Intensity, cps 340 320 300 280 260 240 220 200 180 160 140 120 100 80 60 40 20 0 9.7 9.8 9.9 10.0 10.1 10.2 10.3 10.4 10.5 10.6 10.7 10.8 10.9 11.0 11.1 11.2 11.3 11.4 11.5 11.6 Time, min E05-0210 Interim Report#13 Tennessee River Page 61 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Sample Name: "s050726a034" Sample ID: "MB-050726-7 Method Blank-7" Peak Name: "pfhs (tic)" Mass(es): "399.0/79.8 amu,399.0/99.0 amu" Comment: "" Annotation: "" Sample Index: 34 Sample Type: Unknown Concentration: N/A Calculated Conc: < 0 275 Acq. Date: 07/27/2005 Acq. Time: 03:20:27 AM 270 Modified: Yes 265 RT Window: 30.0 sec 260 Expected RT: 13.1 min Use Relative RT: No 255 File: "s050726a.wiff" 13.10 13.48 Int. Type: Manual 250 Retention Time: 13.107 min 245 Area: 1546 counts Height: 2.22e+002 cps 240 Start Time: 12.897 min End Time: 13.208 min 235 230 225 220 215 210 205 200 195 190 14.10 185 180 175 170 165 160 155 150 Intensity, cps 145 140 135 130 125 120 115 110 105 100 95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0 12.2 12.3 12.4 12.5 12.6 12.7 12.8 12.9 13.0 13.1 13.2 13.3 13.4 13.5 13.6 13.7 13.8 13.9 14.0 14.1 Time, min Sample Name: "s050726a034" Sample ID: "MB-050726-7 Method Blank-7" File: "s050726a.wiff" Peak Name: "pfos (tic)" Mass(es): "498.9/99.2 amu,498.9/130.0 amu,498.9/80.0 amu" Comment: "" Annotation: "" Sample Index: 34 Sample Type: Unknown Concentration: N/A 580 Calculated Conc: 0.0000147 ng/mL Acq. Date: 07/27/2005 570 Acq. Time: 03:20:27 AM 560 14.53 Modified: Yes 550 RT Window: 30.0 sec 540 Expected RT: 14.6 min Use Relative RT: No 530 Int. Type: Manual 520 Retention Time: 14.535 min 510 Area: 4700 counts Height: 5.66e+002 cps 500 Start Time: 14.055 min End Time: 14.634 min 490 480 470 460 450 440 430 420 410 400 390 380 370 360 350 340 330 320 310 Intensity, cps 300 290 280 270 260 250 240 230 220 14.34 14.82 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 13.6 13.7 13.8 13.9 14.0 14.1 14.2 14.3 14.4 14.5 14.6 14.7 14.8 14.9 15.0 15.1 15.2 15.3 15.4 15.5 Time, min E05-0210 Interim Report#13 Tennessee River Page 62 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Sample Name: "s050726a042" Sample ID: "LCS-050726-4 1250 ppt Lab Control Spike" Peak Name: "13C pfoa" Mass(es): "414.9/369.8 amu" Comment: "" Annotation: "" Sample Index: 42 Sample Type: Unknown Concentration: Calculated Conc: N/A 1.25 ng/mL 1.18e6 Acq. Date: Acq. Time: 07/27/2005 06:09:59 AM 1.16e6 1.14e6 Modified: Yes Proc. Algorithm: IntelliQuan - MQII 1.12e6 Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 0 1.10e6 1.08e6 Report Largest Peak: No Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec 1.06e6 1.04e6 Smoothing Width: RT Window: 3 30.0 points sec 1.02e6 Expected RT: 13.9 min 1.00e6 Use Relative RT: No 9.80e5 File: "s050726a.wiff" 13.87 Int. Type: Valley Retention Time: 13.869 min Area: 6801439 counts Height: 1.19e+006 cps Start Time: 13.724 min End Time: 14.365 min 9.60e5 9.40e5 9.20e5 9.00e5 8.80e5 8.60e5 8.40e5 8.20e5 8.00e5 7.80e5 7.60e5 7.40e5 7.20e5 7.00e5 6.80e5 6.60e5 6.40e5 Intensity, cps 6.20e5 6.00e5 5.80e5 5.60e5 5.40e5 5.20e5 5.00e5 4.80e5 4.60e5 4.40e5 4.20e5 4.00e5 3.80e5 3.60e5 3.40e5 3.20e5 3.00e5 2.80e5 2.60e5 2.40e5 2.20e5 2.00e5 1.80e5 1.60e5 1.40e5 1.20e5 1.00e5 8.00e4 6.00e4 4.00e4 2.00e4 0.00 13.66 14.72 14.82 12.9 13.0 13.1 13.2 13.3 13.4 13.5 13.6 13.7 13.8 13.9 14.0 14.1 14.2 14.3 14.4 14.5 14.6 14.7 14.8 Time, min Sample Name: "s050726a042" Sample ID: "LCS-050726-4 1250 ppt Lab Control Spike" Peak Name: "pfbs (tic)" Mass(es): "298.9/79.8 amu,298.9/99.0 amu" Comment: "" Annotation: "" Sample Index: 42 Sample Type: Unknown Concentration: Calculated Conc: N/A 1.15 ng/mL 1.6e6 Acq. Date: 07/27/2005 Acq. Time: 06:09:59 AM 1.5e6 Modified: No Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 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: 10.7 min Use Relative RT: No 1.5e6 1.4e6 1.4e6 1.3e6 File: "s050726a.wiff" Int. Type: Valley Retention Time: 10.686 min Area: 9587562 counts Height: 1.56e+006 cps Start Time: 10.479 min End Time: 11.058 min 1.3e6 1.2e6 1.2e6 10.69 1.1e6 1.1e6 1.0e6 9.5e5 9.0e5 8.5e5 Intensity, cps 8.0e5 7.5e5 7.0e5 6.5e5 6.0e5 5.5e5 5.0e5 4.5e5 4.0e5 3.5e5 3.0e5 2.5e5 2.0e5 1.5e5 1.0e5 5.0e4 0.0 9.7 9.8 9.9 10.0 10.1 10.2 10.3 10.4 10.5 10.6 10.7 10.8 10.9 11.0 11.1 11.2 11.3 11.4 11.5 11.6 Time, min E05-0210 Interim Report#13 Tennessee River Page 63 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Sample Name: "s050726a042" Sample ID: "LCS-050726-4 1250 ppt Lab Control Spike" Peak Name: "pfhs (tic)" Mass(es): "399.0/79.8 amu,399.0/99.0 amu" Comment: "" Annotation: "" Sample Index: 42 Sample Type: Unknown Concentration: Calculated Conc: N/A 1.40 ng/mL 1.02e6 Acq. Date: Acq. Time: 07/27/2005 06:09:59 AM 1.00e6 Modified: No Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 5 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: 13.1 min Use Relative RT: No 9.80e5 9.60e5 9.40e5 9.20e5 9.00e5 8.80e5 8.60e5 Int. Type: Base To Base Retention Time: 13.104 min Area: 6769060 counts Height: 1.03e+006 cps Start Time: 12.649 min End Time: 13.724 min 8.40e5 8.20e5 8.00e5 7.80e5 File: "s050726a.wiff" 13.10 7.60e5 7.40e5 7.20e5 7.00e5 6.80e5 6.60e5 6.40e5 6.20e5 6.00e5 5.80e5 5.60e5 Intensity, cps 5.40e5 5.20e5 5.00e5 4.80e5 4.60e5 4.40e5 4.20e5 4.00e5 3.80e5 3.60e5 3.40e5 3.20e5 3.00e5 2.80e5 2.60e5 2.40e5 2.20e5 2.00e5 1.80e5 1.60e5 12.90 1.40e5 1.20e5 1.00e5 8.00e4 6.00e4 4.00e4 2.00e4 0.00 12.2 12.3 12.4 12.5 12.6 12.7 12.8 12.9 13.0 13.1 13.2 13.3 13.4 13.5 13.6 13.7 13.8 13.9 14.0 14.1 Time, min Sample Name: "s050726a042" Sample ID: "LCS-050726-4 1250 ppt Lab Control Spike" Peak Name: "pfos (tic)" Mass(es): "498.9/99.2 amu,498.9/130.0 amu,498.9/80.0 amu" Comment: "" Annotation: "" Sample Index: 42 Sample Type: Concentration: Calculated Conc: Acq. Date: Acq. Time: Unknown N/A 1.35 ng/mL 07/27/2005 06:09:59 AM 2.9e5 2.8e5 Modified: No Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 5 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: 14.6 min Use Relative RT: No 2.8e5 2.7e5 2.7e5 2.6e5 2.6e5 2.5e5 2.5e5 2.4e5 File: "s050726a.wiff" 14.55 Int. Type: Base To Base Retention Time: 14.551 min Area: 2472736 counts Height: 2.88e+005 cps Start Time: 13.972 min End Time: 15.026 min 2.4e5 2.3e5 2.3e5 2.2e5 2.2e5 2.1e5 2.1e5 2.0e5 2.0e5 1.9e5 1.9e5 1.8e5 1.8e5 1.7e5 1.7e5 1.6e5 1.6e5 Intensity, cps 1.5e5 1.5e5 1.4e5 1.4e5 1.3e5 1.3e5 1.2e5 1.2e5 1.1e5 14.32 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 13.6 13.7 13.8 13.9 14.0 14.1 14.2 14.3 14.4 14.5 14.6 14.7 14.8 14.9 15.0 15.1 15.2 15.3 15.4 15.5 Time, min E05-0210 Interim Report#13 Tennessee River Page 64 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Sample Name: "s050726a060" Sample ID: "E05-0210-86370 DLS-SW-TRM295-0-050719" Peak Name: "13C pfoa" Mass(es): "414.9/369.8 amu" Comment: "" Annotation: "" Sample Index: 60 Sample Type: Unknown Concentration: N/A Calculated Conc: 0.158 ng/mL Acq. Date: 07/27/2005 1.9e5 Acq. Time: 12:30:53 PM 1.9e5 Modified: Yes Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 1.8e5 Base. Sub. Window: 1.00 min Peak-Split. Factor: 0 1.8e5 Report Largest Peak: No Min. Peak Height: Min. Peak Width: 0.00 cps 0.00 sec 1.7e5 Smoothing Width: RT Window: 3 30.0 points sec 1.7e5 Expected RT: 13.9 min Use Relative RT: No 1.6e5 File: "s050726a.wiff" Int. Type: Valley Retention Time: 13.848 min Area: 1000036 counts Height: 1.93e+005 cps Start Time: 13.704 min End Time: 14.117 min 1.6e5 1.5e5 1.5e5 13.85 1.4e5 1.4e5 1.3e5 1.3e5 1.2e5 1.2e5 1.1e5 1.1e5 Intensity, cps 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 12.9 13.0 13.1 13.2 13.3 13.4 13.5 13.6 13.7 13.8 13.9 14.0 14.1 14.2 14.3 14.4 14.5 14.6 14.7 14.8 Time, min Sample Name: "s050726a060" Sample ID: "E05-0210-86370 DLS-SW-TRM295-0-050719" Peak Name: "pfbs (tic)" Mass(es): "298.9/79.8 amu,298.9/99.0 amu" Comment: "" Annotation: "" Sample Index: 60 Sample Type: Unknown Concentration: N/A Calculated Conc: 0.0679 ng/mL 1.10e5 Acq. Date: Acq. Time: 07/27/2005 12:30:53 PM 1.08e5 Modified: No Proc. Algorithm: IntelliQuan - MQII 1.06e5 1.04e5 Noise Percentage: Base. Sub. Window: 50 1.00 min 1.02e5 Peak-Split. Factor: 2 Report Largest Peak: No 1.00e5 Min. Peak Height: 0.00 cps 9.80e4 Min. Peak Width: Smoothing Width: 0.00 3 sec points 9.60e4 RT Window: Expected RT: 30.0 sec 10.7 min 9.40e4 Use Relative RT: No 9.20e4 File: "s050726a.wiff" 10.62 Int. Type: Valley Retention Time: 10.624 min Area: 657459 counts Height: 1.11e+005 cps Start Time: 10.417 min End Time: 10.955 min 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 9.7 9.8 9.9 10.0 10.1 10.2 10.3 10.4 10.5 10.6 10.7 10.8 10.9 11.0 11.1 11.2 11.3 11.4 11.5 11.6 Time, min E05-0210 Interim Report#13 Tennessee River Page 65 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Sample Name: "s050726a060" Sample ID: "E05-0210-86370 DLS-SW-TRM295-0-050719" Peak Name: "pfhs (tic)" Mass(es): "399.0/79.8 amu,399.0/99.0 amu" Comment: "" Annotation: "" Sample Index: 60 Sample Type: Unknown Concentration: N/A Calculated Conc: 0.0719 ng/mL Acq. Date: Acq. Time: 07/27/2005 12:30:53 PM 6.0e4 File: "s050726a.wiff" Modified: Yes RT Window: 30.0 sec Expected RT: 13.1 min Use Relative RT: No Int. Type: Manual Retention Time: 13.075 min Area: 382281 counts Height: 6.32e+004 cps Start Time: 12.732 min End Time: 13.270 min 5.8e4 5.6e4 5.4e4 5.2e4 13.08 5.0e4 4.8e4 4.6e4 4.4e4 4.2e4 4.0e4 3.8e4 3.6e4 3.4e4 Intensity, cps 3.2e4 3.0e4 2.8e4 2.6e4 2.4e4 2.2e4 2.0e4 1.8e4 1.6e4 1.4e4 1.2e4 1.0e4 8000.0 12.88 6000.0 4000.0 2000.0 0.0 12.2 12.3 12.4 12.5 12.6 12.7 12.8 12.9 13.0 13.1 13.2 13.3 13.4 13.5 13.6 13.7 13.8 13.9 14.0 14.1 Time, min Sample Name: "s050726a060" Sample ID: "E05-0210-86370 DLS-SW-TRM295-0-050719" Peak Name: "pfos (tic)" Mass(es): "498.9/99.2 amu,498.9/130.0 amu,498.9/80.0 amu" Comment: "" Annotation: "" Sample Index: 60 Sample Type: Unknown Concentration: Calculated Conc: N/A 0.129 ng/mL 2.8e4 Acq. Date: Acq. Time: 07/27/2005 12:30:53 PM 2.7e4 2.7e4 Modified: RT Window: Yes 30.0 sec 2.6e4 Expected RT: Use Relative RT: 14.6 min No 2.6e4 2.5e4 Int. Type: Manual Retention Time: 14.511 min 2.5e4 Area: Height: 246900 counts 2.76e+004 cps 2.4e4 Start Time: End Time: 13.952 min 14.675 min 2.4e4 2.3e4 File: "s050726a.wiff" 14.51 2.3e4 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 Intensity, cps 1.5e4 1.4e4 1.4e4 1.3e4 1.3e4 14.28 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 13.6 13.7 13.8 13.9 14.0 14.1 14.2 14.3 14.4 14.5 14.6 14.7 14.8 14.9 15.0 15.1 15.2 15.3 15.4 15.5 Time, min E05-0210 Interim Report#13 Tennessee River Page 66 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Sample Name: "s050726a061" Sample ID: "E05-0210-86371 DLS-SW-TRM295-0-050719 Dup" Peak Name: "13C pfoa" Mass(es): "414.9/369.8 amu" Comment: "" Annotation: "" Sample Index: 61 Sample Type: Unknown Concentration: N/A Calculated Conc: 0.137 ng/mL Acq. Date: Acq. Time: 07/27/2005 12:51:56 PM 1.6e5 File: "s050726a.wiff" Modified: Yes Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 0 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: 13.9 min Use Relative RT: No Int. Type: Valley Retention Time: 13.828 min Area: 875346 counts Height: 1.64e+005 cps Start Time: 13.683 min End Time: 14.117 min 1.6e5 1.5e5 1.5e5 1.4e5 1.4e5 1.3e5 1.3e5 1.2e5 13.83 1.2e5 1.1e5 1.1e5 1.0e5 9.5e4 9.0e4 Intensity, cps 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 12.9 13.0 13.1 13.2 13.3 13.4 13.5 13.6 13.7 13.8 13.9 14.0 14.1 14.2 14.3 14.4 14.5 14.6 14.7 14.8 Time, min Sample Name: "s050726a061" Sample ID: "E05-0210-86371 DLS-SW-TRM295-0-050719 Dup" Peak Name: "pfbs (tic)" Mass(es): "298.9/79.8 amu,298.9/99.0 amu" Comment: "" Annotation: "" Sample Index: 61 Sample Type: Unknown Concentration: Calculated Conc: N/A 0.493 ng/mL 7.4e5 Acq. Date: 07/27/2005 Acq. Time: 12:51:56 PM 7.2e5 File: "s050726a.wiff" Modified: No Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 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: 10.7 min Use Relative RT: No 7.0e5 6.8e5 6.6e5 6.4e5 6.2e5 Int. Type: Valley Retention Time: 10.603 min Area: 4473167 counts Height: 7.46e+005 cps Start Time: 10.397 min End Time: 10.955 min 6.0e5 5.8e5 5.6e5 10.60 5.4e5 5.2e5 5.0e5 4.8e5 4.6e5 4.4e5 4.2e5 4.0e5 Intensity, cps 3.8e5 3.6e5 3.4e5 3.2e5 3.0e5 2.8e5 2.6e5 2.4e5 2.2e5 2.0e5 1.8e5 1.6e5 1.4e5 1.2e5 1.0e5 8.0e4 6.0e4 4.0e4 2.0e4 0.0 9.7 9.8 9.9 10.0 10.1 10.2 10.3 10.4 10.5 10.6 10.7 10.8 10.9 11.0 11.1 11.2 11.3 11.4 11.5 11.6 Time, min E05-0210 Interim Report#13 Tennessee River Page 67 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Sample Name: "s050726a061" Sample ID: "E05-0210-86371 DLS-SW-TRM295-0-050719 Dup" Peak Name: "pfhs (tic)" Mass(es): "399.0/79.8 amu,399.0/99.0 amu" Comment: "" Annotation: "" Sample Index: 61 Sample Type: Unknown Concentration: Calculated Conc: N/A 0.549 ng/mL 4.5e5 Acq. Date: Acq. Time: 07/27/2005 12:51:56 PM 4.4e5 Modified: No Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 5 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: 13.1 min Use Relative RT: No Int. Type: Base To Base Retention Time: 13.063 min Area: 2807276 counts Height: 4.52e+005 cps Start Time: 12.608 min End Time: 13.642 min 4.3e5 4.2e5 4.1e5 4.0e5 3.9e5 3.8e5 3.7e5 3.6e5 3.5e5 3.4e5 File: "s050726a.wiff" 13.06 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 12.86 5.0e4 4.0e4 3.0e4 2.0e4 1.0e4 0.0 12.2 12.3 12.4 12.5 12.6 12.7 12.8 12.9 13.0 13.1 13.2 13.3 13.4 13.5 13.6 13.7 13.8 13.9 14.0 14.1 Time, min Sample Name: "s050726a061" Sample ID: "E05-0210-86371 DLS-SW-TRM295-0-050719 Dup" Peak Name: "pfos (tic)" Mass(es): "498.9/99.2 amu,498.9/130.0 amu,498.9/80.0 amu" Comment: "" Annotation: "" Sample Index: 61 Sample Type: Unknown Concentration: N/A 1.3e5 Calculated Conc: 0.590 ng/mL Acq. Date: 07/27/2005 Acq. Time: 12:51:56 PM 1.3e5 Modified: No Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 5 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: 14.6 min Use Relative RT: No 1.2e5 1.2e5 1.1e5 File: "s050726a.wiff" Int. Type: Base To Base Retention Time: 14.510 min Area: 1097936 counts Height: 1.30e+005 cps Start Time: 13.931 min End Time: 14.944 min 1.1e5 1.0e5 9.5e4 14.51 9.0e4 8.5e4 8.0e4 7.5e4 7.0e4 Intensity, cps 6.5e4 6.0e4 5.5e4 5.0e4 14.28 4.5e4 4.0e4 3.5e4 3.0e4 2.5e4 2.0e4 1.5e4 1.0e4 5000.0 0.0 13.6 13.7 13.8 13.9 14.0 14.1 14.2 14.3 14.4 14.5 14.6 14.7 14.8 14.9 15.0 15.1 15.2 15.3 15.4 15.5 Time, min E05-0210 Interim Report#13 Tennessee River Page 68 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Sample Name: "s050726a062" Sample ID: "E05-0210-86372 DLS-SW-TRM295-0-050719 LS" Peak Name: "13C pfoa" Mass(es): "414.9/369.8 amu" Comment: "" Annotation: "" Sample Index: 62 Sample Type: Unknown Concentration: N/A Calculated Conc: 0.152 ng/mL Acq. Date: 07/27/2005 1.8e5 Acq. Time: 01:13:06 PM 1.8e5 Modified: Yes Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 1.7e5 Base. Sub. Window: 1.00 min Peak-Split. Factor: 0 Report Largest Peak: No 1.7e5 Min. Peak Height: Min. Peak Width: 0.00 cps 0.00 sec 1.6e5 Smoothing Width: 3 points RT Window: Expected RT: 30.0 sec 13.9 min 1.6e5 Use Relative RT: No 1.5e5 Int. Type: Valley Retention Time: 13.828 min Area: 965249 counts 1.5e5 Height: 1.83e+005 cps Start Time: End Time: 13.662 min 14.076 min 1.4e5 File: "s050726a.wiff" 1.4e5 13.83 1.3e5 1.3e5 1.2e5 1.2e5 1.1e5 1.1e5 1.0e5 Intensity, cps 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 12.9 13.0 13.1 13.2 13.3 13.4 13.5 13.6 13.7 13.8 13.9 14.0 14.1 14.2 14.3 14.4 14.5 14.6 14.7 14.8 Time, min Sample Name: "s050726a062" Sample ID: "E05-0210-86372 DLS-SW-TRM295-0-050719 LS" Peak Name: "pfbs (tic)" Mass(es): "298.9/79.8 amu,298.9/99.0 amu" Comment: "" Annotation: "" Sample Index: 62 Sample Type: Concentration: Unknown N/A 2.6e4 Calculated Conc: 0.0143 ng/mL Acq. Date: 07/27/2005 2.5e4 Acq. Time: 01:13:06 PM 2.5e4 Modified: No Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 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: 10.7 min Use Relative RT: No 2.4e4 2.4e4 2.3e4 2.3e4 2.2e4 2.2e4 2.1e4 Int. Type: Valley Retention Time: 10.624 min Area: 148036 counts Height: 2.54e+004 cps Start Time: 10.397 min End Time: 10.893 min 2.1e4 2.0e4 2.0e4 1.9e4 File: "s050726a.wiff" 10.62 1.9e4 1.8e4 1.8e4 1.7e4 1.7e4 1.6e4 1.6e4 1.5e4 1.5e4 1.4e4 1.4e4 Intensity, cps 1.3e4 1.3e4 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 9.7 9.8 9.9 10.0 10.1 10.2 10.3 10.4 10.5 10.6 10.7 10.8 10.9 11.0 11.1 11.2 11.3 11.4 11.5 11.6 Time, min E05-0210 Interim Report#13 Tennessee River Page 69 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Sample Name: "s050726a062" Sample ID: "E05-0210-86372 DLS-SW-TRM295-0-050719 LS" Peak Name: "pfhs (tic)" Mass(es): "399.0/79.8 amu,399.0/99.0 amu" Comment: "" Annotation: "" Sample Index: 62 Sample Type: Unknown Concentration: N/A Calculated Conc: 0.0115 ng/mL Acq. Date: 07/27/2005 1.08e4 1.06e4 Acq. Time: 01:13:06 PM 1.04e4 Modified: No Proc. Algorithm: IntelliQuan - MQII Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 5 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: 13.1 min Use Relative RT: No 1.02e4 1.00e4 9800.00 9600.00 9400.00 9200.00 9000.00 File: "s050726a.wiff" 13.06 Int. Type: Retention Time: Area: Height: Start Time: End Time: Valley 13.063 min 64360 counts 1.07e+004 cps 12.608 min 13.270 min 8800.00 8600.00 8400.00 8200.00 8000.00 7800.00 7600.00 7400.00 7200.00 7000.00 6800.00 6600.00 6400.00 6200.00 6000.00 5800.00 Intensity, cps 5600.00 5400.00 5200.00 5000.00 4800.00 4600.00 4400.00 4200.00 4000.00 3800.00 3600.00 3400.00 3200.00 3000.00 2800.00 2600.00 2400.00 2200.00 2000.00 1800.00 1600.00 1400.00 1200.00 1000.00 800.00 600.00 400.00 200.00 0.00 12.2 12.3 12.4 12.5 12.6 12.7 12.8 12.9 13.0 13.1 13.2 13.3 13.4 13.5 13.6 13.7 13.8 13.9 14.0 14.1 Time, min Sample Name: "s050726a062" Sample ID: "E05-0210-86372 DLS-SW-TRM295-0-050719 LS" Peak Name: "pfos (tic)" Mass(es): "498.9/99.2 amu,498.9/130.0 amu,498.9/80.0 amu" Comment: "" Annotation: "" Sample Index: 62 Sample Type: Unknown Concentration: N/A Calculated Conc: 0.0736 ng/mL 1.4e4 Acq. Date: 07/27/2005 Acq. Time: 01:13:06 PM 1.4e4 Modified: Yes RT Window: 30.0 sec Expected RT: Use Relative RT: 14.6 min No 1.3e4 File: "s050726a.wiff" Int. Type: Manual Retention Time: 14.502 min Area: 142631 counts Height: 1.43e+004 cps Start Time: 13.931 min End Time: 14.675 min 1.3e4 1.2e4 1.2e4 14.51 1.1e4 1.1e4 1.0e4 9500.0 9000.0 8500.0 8000.0 14.28 7500.0 Intensity, cps 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 14.10 500.0 0.0 13.6 13.7 13.8 13.9 14.0 14.1 14.2 14.3 14.4 14.5 14.6 14.7 14.8 14.9 15.0 15.1 15.2 15.3 15.4 15.5 Time, min E05-0210 Interim Report#13 Tennessee River Page 70 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 s050726a.rdb (pfbs (tic)): "Quadratic" Regression ("1 / x" weighting): y = -1.12e+006 x^2 + 9.6e+006 x + 1.09e+004 (r = 0.9996) 1.6e7 1.5e7 1.4e7 1.3e7 1.2e7 1.1e7 1.0e7 9.0e6 8.0e6 7.0e6 6.0e6 5.0e6 4.0e6 3.0e6 2.0e6 1.0e6 0.0 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 Concentration, ng/mL Area, counts Area, counts s050726a.rdb (pfhs (tic)): "Quadratic" Regression ("1 / x" weighting): y = -3.43e+005 x^2 + 5.3e+006 x + 3.26e+003 (r = 0.9999) 1.15e7 1.10e7 1.05e7 1.00e7 9.50e6 9.00e6 8.50e6 8.00e6 7.50e6 7.00e6 6.50e6 6.00e6 5.50e6 5.00e6 4.50e6 4.00e6 3.50e6 3.00e6 2.50e6 2.00e6 1.50e6 1.00e6 5.00e5 0.00 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 Concentration, ng/mL E05-0210 Interim Report#13 Tennessee River Page 71 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 s050726a.rdb (pfos (tic)): "Quadratic" Regression ("1 / x" weighting): y = -4.11e+004 x^2 + 1.88e+006 x + 4.67e+003 (r = 0.9999) 4.4e6 4.2e6 4.0e6 3.8e6 3.6e6 3.4e6 3.2e6 3.0e6 2.8e6 2.6e6 2.4e6 2.2e6 2.0e6 1.8e6 1.6e6 1.4e6 1.2e6 1.0e6 8.0e5 6.0e5 4.0e5 2.0e5 0.0 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2.0 2.1 2.2 2.3 2.4 Concentration, ng/mL Area, counts Area, counts s050726a.rdb (13C pfoa): "Quadratic" Regression ("1 / x" weighting): y = -7.78e+005 x^2 + 6.41e+006 x + 9.03e+003 (r = 0.9995) 1.13e7 1.10e7 1.05e7 1.00e7 9.50e6 9.00e6 8.50e6 8.00e6 7.50e6 7.00e6 6.50e6 6.00e6 5.50e6 5.00e6 4.50e6 4.00e6 3.50e6 3.00e6 2.50e6 2.00e6 1.50e6 1.00e6 5.00e5 0.00 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2.0 2.1 2.2 2.3 2.4 2.5 Concentration, ng/mL E05-0210 Interim Report#13 Tennessee River Page 72 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 ATTACHMENT B: EXTRACTION AND ANALYTICAL METHODS E05-0210 Interim Report#13 Tennessee River Page 73 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 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 Page 1 of 17 Determination of Perfluorinated Compounds in Water Using SPE and LCIMS. E05-0210 Interim Report#13 Tennessee River Page 74 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 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 Page 2 of 17 Determination of Perfluorinated Compounds in Water Using SPE and LC/MS. E05-0210 Interim Report#13 Tennessee River Page 75 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 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 Page 3 of 17 Determination of Perfluorinated Compounds in Water Using SPE and LC/MS. E05-0210 Interim Report#13 Tennessee River Page 76 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 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 Page 4 of 17 Determination of Perfluorinated Compounds in Water Using SPE and LC/MS. E05-0210 Interim Report#13 Tennessee River Page 77 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 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 Page 5 of 17 Determination of Perfluorinated Compounds in Water Using SPE and LC/MS. E05-0210 Interim Report#13 Tennessee River Page 78 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 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. ETS-8-154.1 Page 6 of 17 Determination of Perfluorinated Compounds in Water Using SPE and LC/MS. E05-0210 Interim Report#13 Tennessee River Page 79 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 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 Page 7 of 17 Determination of Perfluorinated Compounds in Water Using SPE and LC/MS. E05-0210 Interim Report#13 Tennessee River Page 80 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 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. ETS-8-154.1 Page 8 of 17 Determination of Perfluorinated Compounds in Water Using SPE and LC/MS. E05-0210 Interim Report#13 Tennessee River Page 81 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 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. ETS-8-154.1 Page 9 of 17 Determination of Perfluorinated Compounds in Water Using SPE and LC/MS. E05-0210 Interim Report#13 Tennessee River Page 82 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 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 ETS-8-154.1 Page 10 of 17 Determination of Perfluorinated Compounds in Water Using SPE and LC/MS. E05-0210 Interim Report#13 Tennessee River Page 83 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 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 ETS-8-154.1 Page 11 of 17 Determination of Perfluorinated Compounds in Water Using SPE and LC/MS. E05-0210 Interim Report#13 Tennessee River Page 84 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 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 ETS-8-154.1 Page 12 of 17 Determination of Perfluorinated Compounds in Water Using SPE and LC/MS. E05-0210 Interim Report#13 Tennessee River Page 85 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 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. ETS-8-154.1 Page 13 of 17 Determination of Perfluorinated Compounds in Water Using SPE and LC/MS. E05-0210 Interim Report#13 Tennessee River Page 86 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 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: ETS-8-154.1 Page 14 of 17 Determination of Perfluorinated Compounds in Water Using SPE and LC/MS. E05-0210 Interim Report#13 Tennessee River Page 87 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 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. ETS-8-154.1 Page 15 of 17 Determination of Perfluorinated Compounds in Water Using SPE and LC/MS. E05-0210 Interim Report#13 Tennessee River Page 88 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 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. ETS-8-154.1 Page 16 of 17 Determination of Perfluorinated Compounds in Water Using SPE and LC/MS. E05-0210 Interim Report#13 Tennessee River Page 89 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 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 ETS-8-154.1 Page 17 of 17 Determination of Perfluorinated Compounds in Water Using SPE and LC/MS. E05-0210 Interim Report#13 Tennessee River Page 90 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 ATTACHMENT C: PROTOCOL AND PROTOCOL AMENDMENTS E05-0210 Interim Report#13 Tennessee River Page 91 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 E05-0210 Interim Report#13 Tennessee River Page 92 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 E05-0210 Interim Report#13 Tennessee River Page 93 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 E05-0210 Interim Report#13 Tennessee River Page 94 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 E05-0210 Interim Report#13 Tennessee River Page 95 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 E05-0210 Interim Report#13 Tennessee River Page 96 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 E05-0210 Interim Report#13 Tennessee River Page 97 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 E05-0210 Interim Report#13 Tennessee 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of 160 3M Environmental Laboratory E05-0210 Interim Report#13 E05-0210 Interim Report#13 Tennessee River Page 151 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 E05-0210 Interim Report#13 Tennessee River Page 152 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 E05-0210 Interim Report#13 Tennessee River Page 153 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 E05-0210 Interim Report#13 Tennessee River Page 154 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 E05-0210 Interim Report#13 Tennessee River Page 155 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 E05-0210 Interim Report#13 Tennessee River Page 156 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 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 E05-0210 E05-0210 Interim Report#13 GLP Protocol Amendment #3 Tennessee River Page 1 of 4 Page 157 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 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 E05-0210 GLP Protocol Amendment #3 Page 2 of 4 E05-0210 Interim Report#13 Tennessee River Page 158 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 Protocol Exygen P0001131; 3M Study Number E05-0210 Amendment 3 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. E05-0210 E05-0210 Interim Report#13 GLP Protocol Amendment #3 Tennessee River Page 3 of 4 Page 159 of 160 3M Environmental Laboratory E05-0210 Interim Report#13 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 GLP Protocol Amendment #3 E05-0210 Interim Report#13 Tennessee River Page 4 of 4 Page 160 of 160