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P. 1 3M ENVlRONMEN TAL LABORATOR Y REPORT NO. E48-0294 `7 Final Report Analysis of PFBA, NFPA, PFHA, PFOA, PFBS, PFHS, and PFOS in Aqueous Samples From Oakdale, Minnesota Municipal Wells Laboratory Request Number E06-029 4 Method Requirement: 3M Methods ETS-8-11 .0 and ETS,8-154 .1 (modified) Report- Revision 1, 07/18/06 (supersedes report 06109/06) Testing Laboratory 3M EHS Operation s 3M Environmental Laboratory Building 2-3E-09 935 Bush Avenue St. Paul, MN 55106 Requeste r Gary Hohenstein 3M Building 42-02-E-27 PO Box 333 1 Saint Paul, MN 55133-3331 Phone: (651) 778-5150 Fax: (651) 778-7203 The testing reported herein meet the requi rements of ISO/tEC 17025-1999 "General Requirements for the Competence of Testktg and Ca libration laboratories'". in accordance with AGCliEO TE the A2LA Certificate #2052-0 1 . Testing that comp6es with this international Standard also operate in accordance with ISO 900111SO 9002 ( 1994). Ce rtificate #2052-01 PAGE 10F21 p. 2 3M ENVIRONMENTAL LABORATOR Y REPORT NO. F06-0294 Reason for Report Revision This report was revised in order to achieve analytical data of the highest quality for all target compounds . The PFBA data reported here were generated using method ETS-8-11 .0 and was not changed from the original report . All other target analytes were requantitated using method ETS-8-154 .1 . PFOS and PFOA data generated by ETS-8-1 1 .0 did not consistently meet method acceptance crite ria requirements . Improved t'FOS .and PFOA data accuracy was obtained using ETS-8-154 .1, a method validated For PFOS and PFOA . Data for the remaining target compounds were consistent between the methods . Only data from ETS-8-154 .1 was reported for those anaiytes . PAGE 2OF21 p. 3 'IM ENVIRONMENTAL LABORATOR Y REPORT NO. E06-0294 3M Environmental Laborato ry 3M Environmental Laboratory Technical Manager : William K . Reagen, Ph .D . 3M Technical Le:^ads: Mark E . Ellefson, Kent R. Lindstrom Report Author : Susan Wolf Analytical Report E06-0294, Revision ? Oakdale Municipal Well Samples : Minnesota Department of Health Co-SamplinglliFay 11, 2006 Report Date : July 18, 2006 Supersedes report dated June 9, 2006 :. ... . . , ~ - - 14 ~^~;t~if~. {;~ i .~ ; f: ~ ?k: : .~s-' - y1~, ~. . : Al . . - r :: .R-,...: .... .. . :: . - +:?n~{!r .' :[.': : : . .~ ;:".~. 4`1;E~4:~~ : . ~ .:;,,!,i ~ S . ,, ...-. :: . : : . ;~ Zi: The 3M Environmental Laboratory prepared and analyzed municipal water samples collected by Pace Analytical Field Services personnel on May 11, 2006, from Oakdale municipal wells 1, 2, 3, 5, 7, 8, and 9 in conjunction with the monthly Minnesota Department of Health sampling . Samples were returned to the 3M Environmental Laboratory for analysis of perfluorvbutanoic acid (PFBA), nonafluoropentanoic acid (NFPA), perfluorohexanoic acid (PFHA), perfluorooctanoic acid (PFOA), perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHS) and perFluorooctane sulfonate (PFOS) under laboratory project number E06-0294 . Analysis was completed following 3M Environmental Laboratory method ETS 8-11 .0 "Determination of C,, -- CH Highly Fluorinated Acids, Alcohols, Amides, and Sulfonates in Water by High Performance Liquid Chromatography/Mass Spectrometry" and ETS-8-154 .1 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates in Water by Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectnometr}I" . The 3M Environmental Laboratory prepared sets of sample containers for seven sampling locations . Each sample set consisted of a field sample, field sample duplicate, low field spike, and high field spike . Each empty container was marked with a"fil to here" line that corresponded to a final volume of 450 mL . Containers reserved for field matrix spikes were fortified with an appropriate matrix spike solution containing all analytes prior to being sent to the field for sample collection. Table I summarizes the sample results using both analytical methods identified above . All results for quality control samples prepared and analyzed with the samples will be reported and discussed elsewhere in this report . ACCREDiTE Certificate #2052-01 The testing reported herein meet the requirements of ISO/IEC 170251999 "General Requirements for the Conpethnce of Testing and Caibration Laboratories", in accordance wi th the A21A Certificate #2052-01 . Testing that axnjlies with this Intemational Standard also operate in accordance with ISO 9001JISO 9002 ( 1994). 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M d N nl N N 0) AS `$~ ~~ ~~ A w ~ w ui, ~~ : ww w9d9 dw ~ ~ ~ w ~ ' p. 5 3M ENVIRONMENTAL LABORATOR Y REPORT NO. E06-0294 N/A = Not App6cabl e (1) The analytlcal method uncertainties are as follows: PFBA is 100% t 8.0%, NFPA is 1000k 8.4%. PFHA jr, 100% 1200/6, PFOA is 100"/0 3 8.9`.'a, PFBS is 1pp9f, # 4.6%, PFHS fs 1WAt 3.310, PFOS is 10Q'Yo t 5 .5.6 . Refer to Sections 3 and 4 for data acceptance criteria and discussion . (2) Sanlple results tot' PFBA were de6emiined fopOwing method ETS-8-1 1 .0. (3) Semple results for NFPA, PFHA, PFOA, PFBS, PFHS, and PFOS were determined idlawing meUxad ETS-8-154 .1 (4) The Relative Peroent (xfference between the Samplel5arnple Duplmte exceeds 15% . (5) Average and %RPD were not calculated due to one sarnple bein8 <LOQ. Reported the higher of the two values . S, ,"; ;i' :~~-1 : ,.. : ;. .r'lTIMU: ., , : . . , . : .., . ,!:it . . !. ,r.:.. - y4~ 1 :~ y.: . .n . . y "' _ ,nr : . r: . :: : ..... .!.. s . ~ .!~ .,.. :~. '~':': .~ ':?e ;.r., .., . .. .' : ::~'i,! ....,..a. ~. t :. : : :. . ._ .': :n, ;, , ..: ...!.t. .._. , . , ,.,.. ~h~l .. ..#. .fw. . ::.e, .~s ;r . .'arilY!.~It.P 2.1 Method s Analysis was completed following 3M Environmental Laboratory method ETS 8-11 .0"Determ!nation of C4 - C8 Highly Fluorinated Adds, Alcohols, Amides, and Sutonates in Water by High Performance Liquid Chromatography/Mass Spectrometry' and ETS-8-154 .1 Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In Water by Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry" . ETS-8-154 .1 is currently on the laboratory's scope of accreditation to ISO/IEC 17025:1999 . ET"-1 1,0 is not currently on the laboratory's scope of accreditation . 2 .2 Sample Collectio n Samples were collected in Nalgene7'"' (low-density polyethylene) bottles prepared at the 3M Environmental Laboratory. Prior to sample collection, bottles designated for field matrix spikes were spiked in the laboratory with a known volume of an appropriate matrix spiking solution containing the analytes of interest . Collected sample bottles were returned to the iaboratory at ambient conditions on May 12, 2006. 2 .3 Sample Preparation PFBA Analysis : All samples, calibration standards, and associated quality control samples were prepared using method ETS 8-11 .0 "Determination of C4 - Co Highly Fluorinated Acids, Alcohols, Amides, and Sulfonates in Water by High Performance Liquid Chromatography/Mass Spectrometry". Briefly, aqueous samples and calibrations standards were prepared for analysis by diluting the samples 1 :1 using a 10-mM ammoniurn hydroxide in methanol solution . This method is currently not on the laboratory's scope of accreditation to ISOfIEC 17025:1999 . NFPA, PFHA, PFOA, PFBS, PFHS, and PFOS Analysis : An samples, calibration standards, and associated quality control samples were extracted using a modified procedure of ETS-8-154 .1 . Briefly, 40 mL of sample were loaded onto a pre-conditioned Waters C18 solid phase extraction (SPE) cartridge (Sep-Pak, 1 .0 g, 6 cc) using a vacuum marufold . The loaded SPE cartridges were then eluted with 5 mL of methanol . This extraction procedure concentrates the samples by a factor of eight. (Initial volume = 40 mL, final volume = 5 mL) . Lab control spikes extracted in the same manner cross-validate all the method modifications/deviations from ETS-8-154 .1 . See Section 3 .6 for additional information . Modifications from ETS-8-1 54 .1 that were used for this analysis : Samples were not extracted in duplicate as samples were collected in duplicate in the field_ Extraction columns were not rinsed with 40% methanol after sample loading . After loading the sample onto the column, and just prior to eluting the column with methanol, vacuum was applied for approximateiy 5 minutes to remove as much sample as possible . PAGE 54F 21 p. 6 3M ENVIRONMENTAL LA130RATOR Y REPORT NO. E06-0294 2.4 Analysi s Ail samples and quality control samples were analyzed for seven target analytes using high perPormance liquid chromatography/ tandem mass spectrometry (HPLt,IMSIMS) . Pertinent instrument parameters, the liquid chromatography gradient program, and the specific mass transitions analyzed are described in the tables below. Table 2 . Instrument Parameters . InstnmrentName Analytical Method followed Liquid Chromat h Guard column cal column ETSGin er ETS01lie ETS-8-11.0 _ ETS-8-154 .1 AQIient 1100 Prism RP (2 nxri .X 50 mm). 5 prn Betasil C18 2 .1 mm X.100 mm), 5 m Agile nt 1100 Betasil C18 t2,1 mm .X100 mm , 5 rn Betaa C18 2.1 mm X 100 mm) , 5 Lm Injection Volume Mass Spectrometer Ion Sour ce Electrode 10 & Applied B' tems API 5000 Turbo Spray Z-40M ApoiedgiosysterrisAP14DO00trep Turbo Spray Z-s pra Polarity Negadve Negative Software Ana t 1 .4.1 Analyst 1 .4 .1 Table 3 . Liquid Chromatography Gradient Program . ETS step Total Time Number (mfn) Ginger Flow Rate PercentA (9ji" in) 2mM ammonium Acetate --, Percen t B MeLhano 0 1 2 .0 2 10.0 300 g0.0 300 90.0 300 10.0 10.0 10.0 90 .0 3 5 12.0 300 12.5 300 16 .0 300 10 .0 90 .0 90.0 90 . 0 10.0 10.0 ETS o1lle Step Number Total rime Flow Rat~e (mie} (RdJmin} Percent A x mMammonieim acetate) Percent B Methano 0 0 300 80_0 20 .0 1 1 .0 300 80. 0 20 .0 2 14 .5 300 10.0 90 .0 3 15 .5 300 10.0 90 .0 4 16 .5 300 80.0 20 .0 5 20-0 300 80 .0 24.0 i PAGE 6 OF 21 p. 7 3M ENVIRONMENTAL LABORATOR Y REPORT NO . E06-0294 Table 4 . Mass Transitions Analyfe PFBA PFOA PFOS PFHS p~ PI HA NFPA Mass Transition Dwi eN T/mQ pnsoc) DwoA Tum (msac) U1/Q3 ETSG E7SOJlie 213/169 80 - 413/369 80 100 413/219 80 100 413/169 8o 100 49 *W 8o 100 499W 80 100 4991130 80 100 392W .80 100 39 M 8o 100 29S/8b 80 100 299/99 80 10 0 313/119 80 100 26309 8 0 100 .tit !v'~ ~ . ' N! r 4 i `?19iAT.~,-3i,r ~ ...yi?,?cil ~~~* :!i!Ii f11'RIR r ~I ~~YRI r ,~'~F"r :'r"l:u,>: ;~t~ri~t: ,r. . a. ,?dtu, :s , :r s: :.. . . ._ . . . ,, . _ . .,, .~ . . . . . . . W. 'IN : . ..: .t'.ak: :xi' a. .'ixrCa :e -i,fiir.oi':r,N...lic.;: t:t"::;.'a;IF:~,i+i :ii+i :i I'. :. : : i~}~: .. 3 . 1 Calibration PFBA Analysis : Calibration standards were prepared by spiking known amounts of stock solutions containing the target analytes into 2 mL of ASTM type I water . A T5OuL aliquot of each water standard was then transferred to an autosampier vial . Subsequently, a 750u.L aliquot of a 10mM ammonium hydroxide in methanol solution was added to the vial . Ten spiked standards ranging from 0 .025 ng/mL to 10 nglmL (nominal) were prepared . After dilution, the nominal concentration of each analyte in the vial was 0 .0125 nglmL to 5.0 nglmL, Quadratic, IN weighted, calibration curves were used to fit the data for each analyte_ NFPA, PFHA PFOA, PFBS, PFHS, and PFOS Analysis : Calibration standards were prepared by spiking known amounts of stock solutions containing the analyles of interest into 40 mL of ASTM type I water. Each spiked water standard was then extracted in the same manner as the collected samples . A total of eleven spiked standards ranging from 0 .025 ng/mL to 10 ng/mL (nominal) were prepared . A quadratic, 1/x weighted, calibration curve was used to fit the data for each analyte . The data were not forced through zero during the fitting process . Calculating the standard concentration using the peak area counts and the resultant calibration curve confirmed accuracy of each curve point. Each curve point was quantitated using the overall calibration curve and reviewed for accuracy . Method calibration accuracy requirements of 10025% (10030% for the lowest curve point) were met . The correlation coefficients (r) were greater than 0 .999 for each analyte . The analytes PFBA, NFPA, and PFFIA were initially dissolved in acetonitrie before being further diluted into an intermediate standard solution . This is a deviation for ETS-8-154 .1 which specifies that analytes should be dissolved In Methanol . This deviation has no adverse affect on the sample results . 3 .2 Limit of Quantitation (LOQ ) The LOQ for this analysis, as defined in methods ETS-8-11 .0 and ETS-8-154 .1, is the lowest non-zero calibration standard in the curve that meets linearity and accuracy requirements and which the area counts are at least twice those of the appropriate blanks . The nominal LOQ for PFBA was 0.050ng/mL . The nominal LOQ for NFPA, PFHA, PFOA, PFBS, PFHS, and PFOS was 0-025ng/mL. . PAGE 7 OF 21 p. 8 .3M ENVIRONMENTAL LABORATOR Y REPORTNO. E06-0294 3.3 System Suitability PFBA Analysis : The 5ng/mL calibration standard was analyzed in triplicate at the beginning and end of the analytical sequence to demonstrate overall system suitability . Method acceptance criteria of less than 5% relative standard deviation (RSD) for peak area and less than 2% RSD for retention time for both opening and closing system suitability injections were met. NFPA, PFHA, PFOA, PFBS, PFHS, and PFOS Analysis : The 1 .0 ng1mL extracted-calibration standard was analyzed five times at the beginning and end of the analytical sequence to demonstrate overall system suitability . All compounds met the acceptance criteria of less than 5% relative standard deviation (RSD) for peak area and less than 2% RSD for retention time for the opening and closing system suitability injections with exception of NFPA and PFOA. The RSD for the area counts for the closing system suitability for NFPA was 6 .2% and 6 .9% for PFOA. As laboratory control samples and field matrix spikes are used to qualify the samples results, any instrument variability that may have occurred would be accounted for with these samples . 3 .4 Continuing Calibration PFBA Analysis : During the course of the analytical sequence, several continuing calibration verification samples (CCVs) were analyzed to confirm that the instrument response and the initial curve were still in control . These CCVs were re-injections of two different concentrations of calibration standards from the first calibration curve (curve not used for quantitation) that were quantitated against the second curve (used for quantitation). All CCVs for PFBA met method criteria . NFPA, PFHA, PFOA, PFBS, PFHS, and PFOS Analysis : During the course of the analytical sequence, several continuing calibration verification samples (CCVs) were analyzed to confirm that the instrument response and the initial calibration curve were still in control . One CCV level for PFHA analyzed twice during the course of the run had recoveries of 129% and 131 %, which did not meet method criteria of 10025% . All other CCVs met method criteria. 3 .5 Blank s Three types of blanks were prepared and analyzed with the samples : method blanks, solvent blanks, and field/trip blanks . Each blank result was reviewed and used to evaluate method performance to determine the LOQ for each analyte _ 3 .6 Lab Control Spikes (LCSs) PFBA Analysis : Low and high lab control spikes were prepared and analyzed in triplicate . LCSs were prepared by spiking known amounts of the analytes into 2 mL of ASTM Type I water and prepared exactly like the samples and standards . LCS results were be used to determine overall method uncertainty in Section 3 .7 . NFPA, PFHA, PFOA, PFBS, PFHS, and PFOS Analysis : Low and high lab control spikes were prepared and analyzed in triplicate . LCSs were prepared by spiking known amounts of the analytes into 40 ml- of ASTM Type I water to produce the desired concentration . The spiked water samples were then extracted and analyzed in the same manner as the samples . Analysis of triplicate LCSs at the two specified levels cross-validates the analytical method as used here for any modifications/deviations from ETS 8-1541 . Additionally, LCS results were used to determine overall method uncertainty in Section 3 .7 . The RSD for the six LCS prepared for PFHA was 19%, which did not meet method acceptance criteria of <15% . The following calculations were used to generate data in Table 5. PAGE 8 OF 21 LCS Percent Recovery - Calculated Concentration . 1 00 1/0 Spike Concentration = standard deviation LCS reo cates LCS% RSD 1 00% average LCS recove ry p. 9 3M ENVIRONMENTAL LABORATOR Y REPORT NO. E06-0294 :,, PAGE 9 OF 21 P . 10 ~ z zz C a A, 4 O ` ~ rA Q5r ~o ' c7 O O V ~i tl y fi p r 1~ r C e~ " F' ~+ . .5 41 O U (~O O]i c~6 ~CQ1 ix- E X O C O 1 O -O 3 ~ lLl w m r r r~ O ~ ct J1 J a w - -- --- o o -4. oo Q~ o M No n o c r c a A~ O Pgz N 0 r O- 6Q1 O a r p M ~ctt U ~ fh a0 t1 C 0 r r ai Qi ~ ~ Z fi o r C 00, 32 Q N y~ o 0 0 0 0 o N r~ C o 0 o O O 4 Ic ~..~ ~ M> CQ1 QI ~. QJ ? ~O y p M Q ro n i a , O~ rn U 3 z 4m ~ C1 V III -0 ar ~ pppp 6~ y L~ ~~~ 01 01 07OQ i /I '6* V c1C` r Qr4 - y V~ O O O 6i Oi O O O O e+ r . ~ ~~ ~ f2 N O D 7 y oc n ~ e 1A O O I - dp~; ON] W p Q . }p 67 co (4 m OnI ~ o~~' N i G(p 4) toY ~ I p U "Y F d . e\q4 . C~ 44 ro ~ I C y Z q~ 4 C. m Y r ai z9F nil C aiO+ V a' Z a X C~ ~ c~i ~i a;l C) ~ ~, ~ o 0 0 a a ;3,1CL C mo c o co 0i f6 (1 i 67 g G y da) .0 O c_ "D 08 V 'e r r us u~~ir 1> li y ~ ~ V7 a~ 3~ Cn ~ Q~ Qt a' i N M tn Co . 0 A .t J~ Qt u~r ~ : ~e~ ; r r~ r fiI Z~' mP 0 +J J J _t J J . Q . J J J J J J ~, P . 11 3M ENVIRONMENTAL LABORATOR Y REPORT NO. E06-0294 3.7 Analytical Method Uncertainty Both the accuracy (percent recovery) and precision (%RSD) of the lab control spikes were used to estimate the overall method's analytical uncertainty for a given analyte. For example, if the overatl accuracy and precision for PFOS based on LCS results was 99 .9~05.4% . The measured precision (%RSD) is then used to determine the range of the accuracy . Example: 99 .9*(0 .054) = 5.4 99 .9+5.4=105.3 ;99 .9--5.4=94 . 5 Thus, LCS accuracy results range from 94 .5% to 105.3% . The absolute differelice of the low and high ends of this range, when compared to 100%, are then calculated . 100%-105.3= 5.3% 1001/6-94-5 = 5 .5% . The most conservative (largest) absolute difference is then used as the analytical uncertainty for the given analyte . Table 6 . Analytical Method Uncertainty Analyte Method Uncertainty PF BA 100% +/- 8.0% NFPA 100%+/-8.4% PFHA 100%+1-20% PFt7A 1 00% +!- 8.9% PFBS 100"/n +/- 4 .6% PFHS 100% +/-3.3% PFOS 10Q96 +/- 5.5 % 3.8 Field Matrix Spikes (FMS) Low and high field matrix spikes were collected at each sampling point to verify that the analytical method is applicable to the collected matrix. Field matrix spikes are generated by adding a measured volume of field sample to a container spiked by the laboratory with the target analytes prior to shipping sarnpte containers for sample collection . Field matrix spike recoveries within method acceptance criteria of 10030% confirm that "unknown" components in the sample matrix do not significantly interfere with the extraction and analysis of the analytes of interest . Field matrix spikes are presented in section 4 of this report. FMS Recovery = (Sample Concentration of FMS - Average Concentration : Field Sample & Field Sample Dup .) ,1 DO% Spike Concentraton PAGE 11 OF 21 p . 12 3M ENVlH ONMENTAL L48URATOFt Y REPORT NO. E06-0294 Table 7 . Field Matrix Spike Concentrations Final Con centration (ng1mL) Location Description PFBA NFPA PFHA PFaA PFBS PFWS PFOS Well 5 Well 7 Low Field Matrix Spike 0 .0987 0.0990 0 .101 0.508 0.0999 0.101 0 .503 High Field Matrix Sp&e 0 .987 0.990 1 .01 1 .02 0.999 1-01 1 .01 Low Field Matrix Spike 0 .0987 .00990 0 .101 0.102 0.0999 0.101 0 .101 High Field Matrix Spike 0.987 0 .990 1 .01 1 :02 0.999 1 .01 1 .01 ! WeR8 Low Field Matrix Spike 0.0987 0.0990 0.101 0 .805 0 .0999 0.101 0 .302 High Field Matrix Spike 0.987 0-990 1 .01 1 :D2 0.999 1 .01 1 .01 Well 9 Trip Blank Low Field Matrix Spike 0 .0987 0.0990 0.101 0. :105 0.0999 0.101 0 .302 High Field Matrix Spike 0.987 0.990 1 .01 1 .02 0 .999 1 .01 1 .01 Low Field Matrix Spike 0.0987 0.0990 0.101 0_0508 0.0999 0.101 0.503 High Field Mat rix Spice 0.987 0 .990 1 .01 1 .02 0.999 1 .01 1 .01 well 1 Low Field Matrix Spike 0 .0987 0.0990 0.101 0 .1 02 0.0999 0.101 0.101 iHigh Field Matrix Spike 0.987 0 .990 1 .01 1 .02 ~ 0 .999 -, .01 1 .01 Well 2 - Low Field Matrix Spike High Field MatTixSpike 0 .0987 0.0990 0 .101 0 . 02 0-0999 0.101 0 .101 0.987 i 0 .990 1 .01 1 .02 0.999 1 .01 1,01 IWei 3 11:Low Field Matrix Sp_ ike1 0 .0987 0.0990 0 .101 0. :02 0.0999 0.101 0 .101 ;High Field Ma tr ix Spike 0.987 0.9g0 ! 1 .01 1 .02 0.999 1 .01 1 .0 1 . . :.. ~ .: ;. : . :~~~. :,: :.v. "r:' .% .t . . .~,,,,}j , . . ~T ir ''S' i~tat71FUt4.'r=,J.t~.Y;: .,. iJ swL.::'3sseih:;.5r .. . : .. . ;. h. . . : ;y. .i.' . :l . - -'. ._ . . . . :. i .t .' :w'~':_I. 1..~ .`~. ..~~-.`X ...t. (S '. .1_.:.:. . ..}_ . ~ . _,...t.`:.: :~ ' .L .u 3'' .'. ~ . . . . ...::....... ... :: '1."I- atf.t" .:~. :,. ....~;::}7 ' .. .~'TA:;.ta.t. .a.4' ' < . .i ::.. . ... .:. :,. ..:: . . .. " .. ..... . .i:L'(R,'1:. ". :,'}::i . . ..: . . . . . .. . :' . .-~:. 1 S!c~ Z.-{ ,y The tables below summarize the sample results and field matrix spike recoveries for the seven locations as well as the Trip Blank . Each table provides the average concentration and the relative percent difference (RPD) of the sample and sample duplicate . PAGE 12 OF 21 p . 13 0 o E C, ~a4 * gz N~~ a a a ! a z a ! $ co c o 0 0`~ iv 19 V' a . . ._ .. .. . . ___.-_ +i +1 c~ ,4S E s ai aa O O Q a O O d a p, 7. .p SK~c ~ f+j Z z z -H Y a lIP C p y~ G fV O O r Q IQ E~ N LL yN a n~ w 0 a A 22 u'~ [n ui ui ,ri 3 3 3 3 b, N <7 V I[j 1! s IL7 n NM R 12 N c~ C .-- N ~'i LD U- ~ Z .~ Lu V ~ co Q ~.'. ~ W ~ Q Q O O t0 QQ t0 0 , LO z v .N+ w p . 14 a 8zzz ~ p S z ~ c~n cav I- a Nnm r i~ u r a o 0 o c Z4 w~ U z ; w IR d 44 * 16 nN c o 0 0~ f o 0 20~ " o `-~ r c~ a s y ~~ N 4 E O g a * r~ st *i fi C Q tr ^. C cJ o U` n r sN 8 c 42 $ E- -, ~ Q -0 ~f z o00 0! g gp~ I C~ OD OD rn 00 eNO I C o o r N'c t~ w C6 5 S\ + 1 c a H ~ ~ ~ ~ ~ y ~ ~ ~ b 4) 1 U.) fn lL IL ~.' 0 VJ N l!. LL -0 LL C' P 1~ ~: M C EL N ~ ~ 3 co U $ 1~ m S LL LL ~' i } z h aD . u7 tL~~ii ~ `S }S 7 }~ c7 i-= ~D C d Qf 3 $ . pl r A $ l wi COO 2 m .2 coo C2 ~ a to co on ao' ry ~ ~vi ~m O O O co ~ w w w <TDDD ~ LL O O O (~ ~ Z ~^ > o\ cr rn z z oOa +i w E 52 z w g Q $ z C (~V ~ W cr~ b z ~ N o a C C 4 0 O O r CS ~ . Vmm~J ,~ V U +i 41 A o 0 0 0 o t~ o o a c V C9 i 4,~ ~ 'a222~~~ * 4z 332 ; N CO ~ rE M N ~ C - w~ E ~~ ol cr) ab N~~~ 61 I IIS G i G ~ IO I C Cp o y ~ n ~~ W Q t 0. x co ID C `~ + ~x a m ~': x o Ya ~ d G v1 L iL a E aE4 ~ u3 ' LL 4 9 T ~ w 4* od 06 .0 - Cd m m' OD 3: C6 c r N OD CL Z _ Q O r _N r ~", 4 HH ZE ~Z .. N-- tv ~ i Z(n (n O/9 ~ P- p . 15 W CL p . 16 4q N z z co co ti re C? E V, to W oi cli E Nel 8 .,~ q C o 0 0'' o 0 Z W q w (~`w U a \z zz z ~~~ e +1 SzC^~9+~iS3 -4 fi 4 m O 4 4 ~j O O o b r td J p 2 E a < C M aE o a z z~' z 44 o~~ .4 C~c iY A a iiflE :1c ( , rfa iC y ~ C C+ rl 4 ~8 WF a ~ zz~ ;~ k ~~z~~~ ~ ~ ~ a .tn b c ;W 4) -H x ~~` O O N N~ 8 fi (V N cM N~ ~ C O o~ ~ Qi D w a $ [V 0 L9 a 'm CIO: ~~i ~~ ~a ~ ~ ~ ;a QY a ' 10: cr * cQ n ~ E n 7t ~ m ~ o ~ a~m E Ty ~~ vI ~ ~ U~ +n ii l~ p I m N LL N ~ d o r,+ oi (3i 065 Q; a~ a d cz C" CD ~ O T 3 AAG : ri -q~ Le {i e ri 4 "i tO I afii0aAz- ~ d 9 Bu ~ : a~ m d ! . d 11 JD .!~ m V' I m ~~ ~ V m m on crr v In ~O ~ O p~, ~ I . O M d_ ! c n c ~. . ~ a) O O ~N j C~ Q~g, : .I ~ N f V N ~ (D E . Z Z!n fA to 11 =~ !IJ W I LL1 LL l!J W ~ Z 1.C"1000. p . 17 a a0 Z H b q F cc uj ~Q N --t o wb o N a w Q_ Z Z Z~ $ Q d y fl 5 ~ M 4 ~o N ~s g ' N m x N z R (D _j z ~ ~,~~t w Q ~ ~ `r dr 'Z5 a Z ~+1 00 W a J N N ~y O 4 O G V O O . {~ O C O r O O O'~ ~~~ +I Lr) (D 0 0 $ II' o N LN U ~N 9 ~= LLa LL 41 +1 y 2~~3~ liul ; ~~~3 A N N N N N N N N LL (y H `o q q w w 4a~ w w ~Z_. . . .. .. p . 18 w co z LU a < Z N ti P~ 44 Zcd~ +1 J 8 ~.0 A ~~ `~ J `~ ~ r `$i o ~ a d o o C Q C ro 4 d Q c a q n z ~ z z rk ,~ - co C y ~ N ,a co CD ~Eoor~ e W L. O p O ', v O ti O . ~~' 4$7 .. . . -4_... `.'_. .. .._ ' zIl :P z z m .4 E oe J C YL a~ c M vi ~ I y~ o~' o O T CS U o o ci ", '~ F' O ~ ... v v p 0o LU -j N gS M LL _ d o m ~. LL I a e. aa3 EF NvX_ 3~ ~a cn rn ~ 4 N ( V (V A N (V N N~ Q g~ a ~ N N N N W N 0 _47 . . N W NN N : N 97i ~ r2 m t~ I 4 N0 '.0V a ~ x vl o~ t- ~l ! TO ~ y d u. Z f] U m x Q 4) R `y o ~ N , ~1 072` C~ C`JJ~ ~ tt~Q VV Z C!) ~ fA o a o w .u1 cu M ut ~ u! w ~ ur'T ~ z P . 19 }~r O~ A zz A ~ gz a o C o o J c;~ z o Q o> $; _ C y Ir ee esb C~ U N y 6 $ !~ ~~zz -, n ~ -~ c~ o 0 0 0~i c~ . N ro tj 9 w a Q Q N a ^ Z r b z z r n r ~~ J ~ tn N N ~ Q O 4 o r ~pj 9 aa r_ p g 8 r O L is It ~ L a y 9 T ~ a VO 9 1 1 o L x c m x x a a a ~ +' ~vJ g E V) Vj ~LL mlL ~ 4 (n 1 ~. vi Ni vi 43 2 3333 3333 ~~ m mm ~ m al m z ln p n p~ _ U N ~ p . 20 O o Q~ a mo 0 $ - Q~ z~ o 0 za u w 0 0 a O LZU d a j `9L! . a . N ti .. p . , cz ~o~ . . N s pp L (D Cb , Q'~~ ^ - O y ,~ N a~^j p~ r W o .~ as col N T r 'Ct~+ C .J pp ~~ 4v C p . o tt OV O r ~ f~} 0 5 0 Q o a _ xx H i CD a ~ Q to Cn ~ m LL m coa LN E c `a C .C 2 2 c O 3 I Z m pp 'c .CU,'. m m c Z m pa ~~~3 P,: C _ ~ g4)z : $ z a~ ; Q Q~~a C a~ oi m oi i a Z~x Y m r t~ ~ 40 f' Q n' cp T", 4 4 4 ti q r y ~ ~ an rn r r ~ N ~ w w W 1! ! 21 3M ENVIRONMENTAL LABORATOR Y REPORT NO- E06-0294 -. .. . : . . ... : . .:... ... _ . .. ..: .. . .-> y:~- . . .j,:- : -L- '--. - - - - - - : - - _ ~.- -.,_ ~..... ,; _ . .. : . :. :,~ :. . ..,;.z:.r..'..~_ ... . :'' . -.-. .,.._ _ -::_ Is. ..:= -.~ .' -c ~, -_. .-_- : . .___ _. :. . ._ . --~ . . . . .. - .:...:._:.. .,.~'. . .- , -- - . - . .. . _- .. - . .~ -. Laboratory control spikes were used to determine the analytical method accuracy and precision for all anatytes . The accuracy and precision were then used to estimate the method uncertainty for the results . Field matrix spike recoveries demonstrated that the analytical method was appropriate for the given sample matrix . Analysis was successfully completed folbwing 3M Environmental Laboratory method ETS 8-11 .0 "Determination of C4 - Ca Highly Fluorinated Acids, Alcohols . Amides, and Sulfonates in Water by High Performance Liquid Chromatography/Mass Spectnometry .~qnd ETS-8154 .1 'Determination of Perfluorinated Acids, Alcohols, Amides, and Salfonates in Water by Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry" . Analytical results are reported in Table 1 of this report look .. . +:,: .. . A :i . ......,,.-....... , .. : ; . . _ _ ~. - .. .~_Y'.n . . . ., . . _. .._ .. .. .,., ~ .._ . . ..- . .. - . ;.^at=z;-,_ y,~~ -_ -:#:`~= .:: ~ .~~'~ s All remaining sample and associated p roject data (hardcopy and electronic) will be archived accordin g to 3M Environmental Laboratory standard operating procedu res . .i.. _: , . ~ . . ; _ .: :: .. ,.,:,~,.._ .. . _. .,~-.a.: .. . ~' . . .. . .. . ... -~,.. . .._..-,-:~x,_~P-.-.~->.~.~.. ~.*..:~..~-.F .__` __~: . - -- Susan T. Wolf, 3 llynior Chemist Date Mar E . Ellefson, 3M Senior Ch-6-mist D te Kent R . Lindstrom, 3M Senior Chemist Date William K . Reagen, Ph .D., Environmental Laboratory Technical Manager /Dat e The 3M Environmental Laborator}~s Quality Assurance Unit has audited the data and report for this project. ~ ~711 s oG Quality Assurance R sentative Date ..~ PAGE 21OF 21