Document KGdBnM3MJROpGaYRyX4arQjyN

p. 1 -kR oU 6 36W 3M ENVIRONMENTAL LABORATORY REPORT NO. E0"199 Subreport Analysis of PFOA, PFOS, PFHS, and PFBS in Aqueous Samples : 3M Decatur Offsite Sampling Event (BPP Sample Sites ) Laborato ry Request Number: E06-0199 Method Requirement: 3M Method ETS-8-154 .1 (modified) Testing Laboratory 3M EHS Operations 3M Environmental Laboratory Building 2-3E-09 935 Bush Avenue St. Paul, MN 55106 Requeste r Gary Hohenstein 3M Building 42-02-c-27 PO Box 333 1 Saint Paul, MN 55133-3331 Phone : (651) 778-5150 Fax : (651) 778-7203 ~ccweo~Teo The testing reported herein meet the requUernents of 180AEC 17025-1999 "General Requitunwnts for the Compqsnce of Testing and Calibration Laboratories", In accordance with the A21-A Cerifficaft $2062-01 . Testing that compiles with this International standard also operate In accordance wkh ISO 9001A80 8002 ( 1994). Certificate #2052 -01 PAGE 1 OF 21 p. 2 3M ENVIRONMENTAL LABORATOR Y REPORT NO. E06-0199 3FJ Enaironrnental Laboratory 3M Environmental Laboratory Manager: 'd.iliiam K . Reagen, Ph .D . 3M Technical Lead: Michelle Malinsky, Ph .D. Report Author: Michelle Malinsky, Ph .D. Analytical Subreport E06-019 9 Surface Water Samples BPPO9, BPPO2, and BPPO3; Ground Water Sample BPWeII Decatur Offsite Sampling Event Report Date : May 1, 2006 1 IntroductloNSumnrary The 3M Environmental Laboratory extracted and analyzed ground water and surface water samples collected by Weston Solutions personnel on April 12 and 13, 2006 near the 3M Decatur facility. Samples were returned to the 3M Envir,)nmenUl Laboratory fo, analysis of perfluorooctanoate (PFOA), perfluorooctane sutfonate (PFOS), perfluorohexane sulfonate (PFFi") and perfluorobutane sulfonate (PFBS) under laboratory project number E06-0199 using modified 3M Environmental Laboratory Method ETS 8-154 .1 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates in Water by Solid Phase Extraction and High Performance Liquid C.-irornatography/Mass Spectrometry" . Per the client's request, an initial subreport is being issued for the io ;iowng four sample locations only: DAL SWS BPPO 1 DAL SWS BPPO2 DAL S'dVS BPPO3 DAL. GWS BPINEL L This report will contain information relevant to these four sample collection points only . These results will be reissued in a comprehensive final project report that inci ; .;oes results for all samples collected under E06-0199 . The 3M Environmental Laboratory prepared sets of sample contaires for thirty-trve separate sampling locations . At a minimum, each sample set consisted of a field sample, fieid sample duplicate, low field spike and high field spike . For some locations, a third m ;d-leval field sp,kz was prepared . Each empty container was marked with a"fill to here" line which corresponded io a final volume of 450 mL . Containers reserved for field matrix spikes were fortified with an appropriate matrix spike solution containing the four target analytes prior to being sent .a the field for sample collection- The spike amounts prepared for each of the four locations presented here will be provided later in this report . AOGpECITED Certificate #2052-01 The testing reported herein meet the requirements of ISO/IEC 17025-1999 "General Requirements for the Competence of Testing and Calibration Laboratories", in accordance with the P21-0, Certificate #2052-01 . Testing that complies with this Iniemational Standard aiso operate in accordance with ISO PAGE 2 OF 21 p. 3 3M ENVIRONMENTAL LABORATOR Y REPORT NO . E06-0199 Samples were initially extracted and analyzed on April 19, 2006 . Samples were diluted,, reextracted, and analyzed on April 21, 2006 . Laboratory matrix spikes were prepared, diluted, extracted, and analyzed on April 25, 2006 in the analytical batch initiated on April 24, 2006 : Table 1 below summarizes the sample results . All results for quality control samples prepared and analyzed with the samples will be reported and discussed elsewhere in this report . All samples were diluted 1 :50 in ASTM Type I water prior to extraction . Table 1 . Sample Results Summary . - , 3M LM ID tion roPFOA '4PFOS ^PFHS ^DPFBS t:oncanbaborl Concen6sHon concentration conesnbation MAYMO mL --L-Z'-LL- E06-0199-055 DAL SWS BPPO1 0 060413 293 M>423 53 .3 . E06 -0 199-056 DAL SN5 BPPO 1 DB 060413 307 (4>380 54.3 Av9rage 300 ra>402 53,8 6 .98 7 .17 7,08 YfLPD Sam e 4 .7 ' NA 1.8 27 E06-0199-060 DAL SWS BPP02 0 0604f 3 . 206 ~>295 38.2 E06-0199-061 DAL SWS BPP02 DB 0604 13' 219 '4>314 39.8 4 .30 4 .72 Avel -6 e 212 M>304 Y.RPD Sam alSam 6.1 NA 39.0 4.1 4.66 26 E06-0199-065 DAL SWS BPPO3 0 060413 219 '4>272 39 .1 E06-0 199-066 DAL SINS BPP03 D8060413 214 1A>256 40.1 4 .69 5 .05 Average %RPD Sam 216 23 fa>264 NA 39.6 : 4.87 25 7.4 E06-0199-070 DAL GWS BPWELL 0 060413 1=1>774 14>1460 "''a146 17 .2 E06-0199-071 DAL GWS BPINELL DB 060413 "'>778 r">1170 '2'>145 17 .6 Average m>776 f-0>1320 'a>145 17.4 YsRPD' NA ` NA NA 2.3 (1) The analytical method uncertainty for PFOA, PFHS, and PFBS was 100t11%, 100t5 .8%, and 100t8 .8"/0 , respectively based on method aoaraq and precision . 'Seb'Section 3.7 for additional explanation . The limit of quantitation (LOO) for thes9 samples only was Z50 ng/mL (PFOA) and 1 .25 nghnL (PFHS and PFBS) . Results and average values are rounded to twee signi ficant figures accOrding to EPA rounding rules . Percent relative difference (%RPD) values are rounded to two significant figures . Because of rounding, .values may vary slightly from those liste d in the raw d9ta : - (2) All PFOS sample results present ad here should be conside red estimated minimum values as quality control samples (field matrix spikes and lab matrix spikes) associated with th ese four samples did not demonstrate adequate method performance. The accuracy of the PFOS results could be within an order of magnitude. 9'.RPD values not calculated. BPWeN results for PFOA and PFHS should also be considered estimated minimums as field matrix spike rocoveries did not meet method acceptance criteria of 100t305: . The analytical accuracy of the PFOA and PFHS estimated values for this sample only could be within an order of magni. tud,e ,Y.RPD values not calculated. 2 Methods - Analytlcararid P~parafory ` ~ : , :. . : .ti ir : ,_ ., .. 2.1 Sample Collectio n Samples were collected in Nalgene'"' (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 th e PAGE 3 OF 21 p. 4 3M ENVIRONMENTAL LABORATOR Y REPORT NO. E06-0199 fo,1; analytes of interest (PFOA, PFOS, PFHS and PF3S) . CtAec".ed sample bottles were received at the i.3bo.-atory at ambient conditions cw^ Apol 19, 2006 . Table 2 belrrw details the sampies collected and spikes added to each bottle Table 2. Samp le Collection and Spike information . 311t UMS /DM Weston Sample 3M Bo1Ue 9ou 1e ' tion Number Nominal Spike GPO Location Level (nqMLL CommerK E06-0199-055 DAL S'JYS BP? 01 0 060413 109 Sample NA FSIA Drainage E06-0199-056 DAL SWS BPPOt C430600 3 110 Sample Dup NA FSIA Drainaga EVE-01 W057 DAL SINS BPP^ i LS :0"C414 FMS Low 1 .0 FSIA Drainage E06-0198-058 :;AL SWS BPP0t MS %,00, 13 1 ;2 FMS Mid 10 FSut Drainage E06-0199-059 DAL S1NS BPP01 HS 060413 113 FMS High 100 FSIA Drainage E06-0199-060 DAL SWS BPPO2 0 060413 119 Sample NA FSIA Drainage E06-0199-061 DAL SWS BPPO2 DB 060413 120 Sample Dup NA FSIA Drainage E06-0199-062 DAL SWS BPPO2 LS 060413 f 2i FMS Low 1 .0 FSIA Drainage E06-0199-063 DAL SWS BPPO2 MS 060413 122 FMS Mid 10 FSIA Drainage E06-0199-064 DAL SWS BPP02 HS 060413 123 FMS High 100 FSW Drainaqe E06-0199-065 DAL S1hS BPPO3 0 060413 114 Sample NA FSIA Drainage E06-0199-066 DAL SWS BPPO3 DB 060413 115 Sample Gup NA FSIA Drainage E06-0199-067 DAL SWS BPPO3 LS 060413 116 FMS LaN 1 .0 FSIA Drainage E06-0199-068 DAL SWS BPPO3 MS 060413 11? FMS Mid 10 FSI .4 Drainage E06-0199-069 DAL SWS BPPO3 HS 060413 '13 FMS High 100 FSIA Drainage E06-0199-070 DAL GW5 BPVUEL'- 0 060413 72 Sample NA BP Property E06-0199-071 DAL GWS BPVVELL D8 063413 73 Sample Dup NA BP Property E06-0199-072 DAL GWS BPWELL LS 060413 74 FMS Low 10 BP Property E06-019"73 DAL GWS 2PWELL MS 060413 75 FMS %Atii 100 BP Prcmerty E06-0199-074 DAL GWS Br'WELL F.S 060413 - FMS High DAL = Decatur, AL SWS = Surface Water Sample GWS = Ground Water Sample 0 = Sample DB = Duplicate LS = Low Spike MS = kiid Spike HS = High Spike 1000 BP Fruperty 2.2 Extractio n All samples, calibration standards, and associated quality control samples were extracted using a modified procedure of ETS-8-1 54 .1 "Determination-of PerAuorinated Acids, Aicohols, Amides, and Sutfonates in Water by Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry". 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 manifold . 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 . PAGE 4 OF21 p. 5 3M ENVIRONMENTAL LABORATORY REPORT NO . E060199 The samples and sample duplicates for BPPO1, BPPO2, and BPPO3 were initially extracted undiluted on April 19, 2006 . Initial analysis of the undiluted samoles exceeded the upper limit -of quantiation (25 ng/mL nominal) for PFOA and PFOS. Likewise, the sample and sample duplicate for BPV1fELL were initially extracted on April 19, 2006 . The final extracts were diluted 1 :10 prior to analysis . Analysis of these diluted extracts also exceeded the upper limitofqtrantitation . All the samples, sample duplicates, and field matrix spikes were reextracted on April 21, 2006 . For BPPO1, BPPO2, and BPPO3, the samples and associated QC were diluted 1 :50 using ASTM Type I water prior to extraction . For BPWELL, the sample, sample duplicate., low spike and mid spike were diluted 1 :50, while the hig h spike was diluted 1 :500 . 2 .3 Analysis Al sample and quality control extracts were analyzed for PFOA, PFOS, PFHS, and PFBS using high performance liquid chromatography/ tandem mass spectrometry (HPLClMSlMS) . Pertinent instrument parameters, the liquid chromatography gradient program, and the specific mass transitions analyzed are described in the tables below . Table 3. Instrument Parameters . Instrument Name ETSStan uid Ch ra h ilent 1100 Guard column Betastl C18 (2.1 m m .X100 mm), 5 m Ma cat column Betasi C18 (2 .1 mm X 100 mm , 5 m M n Volume 5pL Mass specounveter Applied ems API 4000 Ion source Turbo Spray Electrode Z-Spray Pola Hoe Software Analyst 1 .4. 1 Table 4. Liquid Chromatography Gradient Program . Step Number ToW Trne now Rate Percent A (min) (frLhnin) m1M ammonium acetm*) Percent B Meow" 0 0 300 80.0 1 1 .0 300 80.0 2 14 .5 300 10.0 3 15 .5 300 10.0 4 16 .5 300 80.0 5 20 .0 300 80.0 20.0 20 .0 90.0 90.0 20 .0 20.0 PAGE 5 OF 21 p. 6 3M ENVIRONMENTAL LABORATOR Y REPORT NO. E06-0199 Table S . Mass Transitions . Analyte "IPFBS "'PFHS "'PFOS 1"i'FOA OSS M Q~%03 ~n DwoU Time (msec) 299/80 125 299/99 12 5 399/80 125 399/39 125 4S9/13 0 12 5 499/99 125 499.'EO 125 49 5 +365 12 5 413P119 125 I 413/1(i9 1 25 ~ ( 1) The individ u al b ,aa.,i;ions were sun imed to produoe a"totai ia- i dttomalogram" (TIC) . The TICs were usea for quantitati on . 3 Data Analysis 3.1 Calibration Calibration standards were prepared by spiking known amounts of stock solutions containing the target analytes intc 40 rnL of ASTM type I water, Each spiked wate r standard was then extracted in the same manner as the, .oCec:ted samples . A!otal of twelve spiked sta ndards ranging from 0.025 ng/mL to 25 ng/mL. .(r+.ominal`, were prepared . A quadrati c, IN weighted, c2 librati on curve was used to fit the data for each analyts . The data were not hr. cEd trough zero duri ng the fitting process . Calculati ng the standard concsntration using the peak area owrrts and the resultant calibrati on cu rve confirmed accuracy of each curve point. Each extracted calibration standard used to generate the fina l calibrati on curve met the method calibration accuracy requirement of 10025% . The correlation coefficients (r) were greater than 0 .999 for all analytes . 3.2 Limit of Quantitation . (LOQ) The LOQ for this analysis, as defin ed ;n ETS-8-154 .1, is the lowest non-zero calibrati on standard in the curve in which the area counts are at least Wee those of the method and solvent blar.k(s) . The LOQs for PFOA, PFOS, PFHS, and PF BS were 0 .050C ng/mL ., 0 .0999 ng/mL, 0 .0250 ng/mL, and 0 .0250 ng/mL, respectively . Note: these LOQ values have not been corrected for sample specific dilution factors. Area count compari son for the method blanks and the lowest calibration standard will be provided in Section 3 .5 .1 . 3.3 System Suitability . Replicate injections of the 1 ng/mL extracted-calibraton standard were analyzed at the beginning and end of the analytical sequence to demonstrate overall system suitability . All analytes met method acceptance criteri a of less than 5% relstiv~ standard deviation (RSD) for peak area and less than 2% RSD for retention time for both opening and cbsinc, system suitabili ty injecti ons . 3.4 Continuing Calibratio n Duri ng the course of the ana:ytical sequence, sevena l continuing calibration verificati on samples (CCVs) were analyzed to confirm that the instrument response and the initia : calibration curve were s ti ll in control . One PFOS :,CV (139%) and one PFHS CCV (153%) exceeded method acceptance cri teria of 10025% for accuracy. Both of these non-compliant CCVs followed a contaminated solvent blank and the high recovery is most likely carryover from the previous injection . A method deviation has been PAGE 6 OF 21 p. 7 3M ENVIRONMENTAL LABORATOR Y REPORT NO. E06-0199 issued . The overall impact to the data quality objectives for the sample results is considered minima l as all sample injections and sample related QC injections were bracketed by compliant CCVs . 3 .5 Blanks Three types of blanks were prepared and analyzed with the samples : method blanks, solvent blanks, and fieki/trip blanks . Each blank type is described below . 35.1 Method Blanks Several method blanks were prepared by loading 40 mL of ASTM Type f water onto a C18 SPE cartridge and eluting with 5 mL of methanol using the same extraction procedure as the samples . Method blanks were prepared to evaluate the levels of background xntamination in the overall extraction process (reagent water, glassware, SPE cartridges, etc .) The calibration curve was prepared on a separate day as the samples. (Calibration standards : April 10, 2006 ; diluted samples : April 21, 2006). The method blanks prepared with the calibration standards as well as with the samples were both analyzed during the April 21, 2006 analysis. Additional lab matrix spikes were prepared and analyzed in a separate analytical run initiated on April 24, 2006 . Again, the method blanks prepared with the calibration curve and the method blanks prepared with the spikes were analyzed . Method blank area count comparisons to the LOQ standard are provided in the Attachments section at the end of this report. 3.5.2 Solvent Blanks Several methanol solvent blanks were analyzed to assess system contamination and/or instrument carryover. For the April 21, 2006 ana.ysis, three separate vials of methanol solvent blanks were contaminated and produced area counts of the target anaiytes greatei- thanone-half those of the LOQ standard . A method deviation has been issued . The solvent blank area count compadson for the April 21, 2006 is provided in the Attachments section at tha end of this report. For the lab matrix spike m sanlyzedoApri24,06nlytheiasovbnkjectdforhpnigsyte suitabilities ano the solvent blanks analyzed after the righest calibration standard exhibited area counts greater than one-half the LOQ standard . 3.5 .3 Fled/Trip Blanks Prior to sample collection, seven sets of trip/field blanks were prepared . A trip blank consists of a sample container filled with 450 mL of ASTM Type I water, sealed, and shipped to the sample collection site along with the empty containers . The trip blank serves as an additional method blank tRheastualctscoouf nthtse ftorirpabnlaynsktoarnaagleysceosndwitililonbse apnrodv/oidrehdolidnintige tfiimnael icsosmuepsrethhaetntshiveesraemppolret .s may experience . 3 .6 Lab Control Spikes (LCSs ) Lab control spikes at nominal concentrations of 0 .050 ng/mL, 5 .0 ng/mL, 100 nymL, and 1000 ng/mL sapndic5es.0wnegrJernpLreLpCarSesdwaenrdeapnraeipyazreeddebaycshpdikafyigsa:cmrxp)vlems ::wmeoreunetxstroafcttheedaannadlyatensaliynztoed40. TmhLeo0f .A0S5T0Mng/mL Type I water to produce the desired concentration . The spiked water samples were then extracted and analyzed in the same manner as the samp!es . . For the 100 ng/mL and 1000 ng/mL LCSs, target aalniqaulyotteosfwtheereLaCdSdewdastoth4e5n0dmiluLteodf A1S:5T0MoTr y1p:e50I0wwatitehr AtoSpTrModTuycpeethI ewfaintearl pdreiosirretodecxotnraccetniotrna,tiionnth.eAn same manner as the diluted samples . This technique was done to demonstrate that the dilution procedure used for the samples was able to produce accurate results . Analysis of replicate LCSs a t tfrhoemvEarTioSu8sle15ve4l.s1 .crAodsdsi-tvioanliadlalyte, sLCthSe raensaullytsticwailllmbeethuosde,datso udseetedrhmeinree, ofovrearanlyl mmeotdhiofidcautinocnesr/tdaeinvtiyatiinons ; Section 3 .7 . Table 6 summarizes the LCS recovery results . PAGE 7 OF 21 p. 8 3M ENVIRONMENTAL LABORATOR Y REPORT NO . E06-0199 LCS Percent R CaelcuclaotedvCeornycen=trati1on0,0% Spike Conce ntrati o n LCS% RSD = standard deviation LCS replicates 100% average LCS recovery PAGE 8 OF 21 p. 9 ? rn a: C o r r * -: m n awo u a~ ~w coo f~MN m ui crnc r ~ o r mrn Oo `=o y , go ~~~g~~$a<~~o ~ 2 V c o O O o 0 '- o o f? M r r ui m tG rn O ~ W V O gsa~~~ga~~~~ m --R ~ C O o O o o O O OD f0 .~`. Q f0 o ~p ~p Q~ f0 O~ odci S ~ t0 aD n ui O pp ad p Y oi O W N ai c0oa_O (o O N c0 oO m ~p W ~p t~~ O) Oi O7 O1 ~ r Q1 W W O~ Ol p T Gf ~ T Ol O) ~ ~L 4 LO y~ cp p p p co to E o gM ~ W O~ N 3 v a o~~ r ap~u 0 O v v o~$ ~, rn R OPN~ T V c o c o 0 0 0 0 0 O m Yi ei ~~ ~~~sgg~~~sssssg~~~gggosg~~ C 0 0 [7 ~n tL') C 0 C Y'i ui ~ - - - C~~ ~ qQr 'o Q n q Orn o c? {o ta o o Orn q tv, al m o -co ano a'o m (-M rnm rn 9 m eno ~ U~ W ~ CI ~ M 1ry ~jj M Of C~ ~ Q1 ess< sss<~~ G O O 1n Y 10 LO Gn O m 0 ) 0m-M N K] rj Q~ P1 T u7 Cj Y m ap co p) ^ g$s~~~sss m 0 m wi ui ui 0 VJ V C G O G C O N ~ C G~ ~ O i Q O~O ^ O Q~ O p N O O r cy M M<O N h 6Z ~i =Z rn~' C") a rnn rn rn rn o~~ ~ es~ 9 9 ~~ .~ co g~ssssgg~~~~ ggss~~ C3, CD 0 o 'a 'o 7 aaga~ q 7 ~ M Y] ~- N N~1 q 1n f h aP W N M N n N N N N N N N N N N N N N N N N N N N N ,a ~ J J J J J J J J J J J J J J J J J J J J JJ J J J to co w U) CO w co J J J U U U J J J U V U,~ ~ J -~ J J U U J J J a n .a ~ 1 n01 ~ n n ~ ~ ~ ~ n n n R ~ o 0 0 0 0 CL0 0 0' o 0 0$ g g$$$ o Q~~ g S$$~ 1- o 0 o vS vi ~ci o 0 0 ui in LO P . 10 ro cc cn e W g- ~ O O cm CD 0 L L LU0 $ o ~c i c F w Ec $ a ro- N N Lu ~ om n Q a n$ 8 Ei. N E P . 11 3M ENVIRONMENTAL LABORATOR Y REPORT NO E06-0199 3.7 Analytical Method Uncertaint y 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, the overall a(%ccRuSraDc)y iasntdhepnreucsiesdiotnofdoertPerFmOiAnebtahseerdanogneLoCfSthreeascucltusrwacays .1010/6+9 .7% . The measured precision Example: 101'(0 .097) = 9 .84 101+9.84=111 .1 ; 101 -9.84=91 .4 5 Thus, LCS accuracy results range from 91 .45% to 111 .1 %. The absolute difference of the low and high ends of this range, when compared to 100%, are then calculated . 111 .1/r100=11 .1% 100%-91 .45 = 8 .54% . Th e most conservative (largest) absolute difference is then used as the analytical uncertainty for the given analyte . Therefore, the analytical uncertainty fix PFOA is given as 100t11 % (two significant figures) for these results . For PFOS, PFHS, and PFBS, the analytical method uncertainty is 10016%, 1005 .8%, and 1008.8%, respectively. It should be emphasized that the analytical method uncertainty desc ribed above only applies to the method and the procedures performed within . Additi onal quality cont rol samples specific to the sample mat rix, in the form of field mat ri x spikes and lab matrix spikes, demons trate that the individual sample results are accurate to within 10030%, the targeted data quality objectives . 3.8 Field Matrix Spikes (FMS ) At a minimum, low and high field mat ri x spikes were collected at each sampling point to verify that the analytical method is applicable to the collected mat rix . For some locations, a mid-level spike was also collected . Field matrix spike recove ries within method acceptance crite ri a of 100f30% 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 field mat rix spike should be at least 50% with the sample data. Th e appropriate spike level for the given of the endogenous sample matr ix . sample con ce ntration to be considered an FMS Recove ry =( Sample Con centration of FMS-Average Con ce ntration Field Sample & Field Sample Dup .) , Spike Concentraton 100% 3 .9 Lab Matrix Spikes (LMS ) If the sample and sample spikes were at least 50% duplicate produ ced of the endogenous concentrations where none of the associated field matri x prepared concentration, then laboratory matrix spikes ( LMS) were . LMSs were prepared by spiking a known amount of target analytes into a measured aliquot of the sample matrix . The spiked matri x was then diluted, if necessary, and extracted in the same manner as the samples . LMS recoveries within 10030% demonstrated that the analytical method was appropriate for the given sample matrix only in the absen ce of an appropriate field matrix spike. 4 Data Summayr The data tables below summarize the matrix spike recoveries for the four sample results, field mat rix spike recoveries, and laboratory pro vides the average locations ( BPPO concentration and the relative 1, BPPO2, BPPO3, percent difference and BPWeII) ( RPD) of the . Each table sample and sample duplicate . PAGE 11 OF 21 p . 12 3M ENVIRONMENTAL LABORATOR Y REPORT NO . E06-0199 BPPO 1 The endogenous concentration for BPPO1 was at least twice the spike concentration for the low spike (1 ng/mL), mid spike (10 ng/mL) and high spike (100 ng/mL) for both PFOA and PFOS . A laboratory matrix spike at 500 ng/mL was prepared and analyzed. The LMS recovery met method acceptance criteria of 10030h for PFOA (79.6%), but not for PFOS (606%) . Therefore, the sample results for PFOS should be considered estimated minimums with a sample analytical accuracy within an order of magnitude as the analytical method has not been demonstrated to be suitable for the given sample matrix . FMS and/or LMS recoveries within 10030% for PFOA, PFHS, and PFBS demonstrate that the analytical method is appropriate for the given sample matrix for these analytes . BPPO 2 The endogenous concentration for BPPO2 was at least twice the spike concentration for the low spike (1 ng/mL) and mid spike (10 ng/mL) for both PFOA and PFOS as well as the high spike (100 ng/mL) for PFOS only . A laboratory matrix spike at 250 VmL was prepared and analyzed . The LMS recovery met method acceptance criteria of 10030% for PFOA (75 .0%), but not PFOS (59.8%) . Therefore, the sample results for PFOS should be considered estimated minimums with a sample analytical accuracy within an order of magnitude as the analytical method has not been demonstrated to be suitable for the given sample mat ri x . FMS ar,d/or LMS recoveries within 10030% for PFOA, PFHS, and PFBS demonstrate that the analytical method is appropriate for the given sample matrix for these analytes . BPPO 3 The endogenous concentration for BPPO3 was at !east twice me spike concentration for the !ow spike (1 rig/mL) and mid spike (10 ng/mL) for both PFOA and PFOS as well as the high spike (100 ng/mL) for PFOS only . A laboratory matrix spike at 250 ng/mL was prepared and analyzed. The LMS srTeahcmeorvpeelferoyraemn,eatthlymetiesctaahmloadpclacecucrreeaspcutyaltnscefocrriPteFriOa Sofs1h0o0ul3d0b%e fcoornPsFidOeAre(d73e.s8t%im),abteudt nmotinPiFmOuSm(s60w.i8t%h )a. within an order of magnitude as the analytical method has not been demonstrated to be suitable for the given sample matrix. The high level PFBS FMS exceeded method acceptance criteria of 10030% (134%). However, the PFBS results for this sample are still considered accurate within 10030% because the criteria exceedence was minimal (within 4%) and mid level FMS and LMS recoveries were excellent . 101 % and 90 .2%, respectively . High level FMS and LMS recoveries within 10030% for PFOA and PFHS also demonstrate that the analytical method is appropriate for the given sample matrix for these two analytes as well . BPWeII The endogenous concentration for BPWell was at least twice the spike concentration for the low spike (10 ng/mL) for PFOA, PFOS, PHFS, and PFBS as well as the mid spike for PFOA, PFOS, and PFHS . Although the high level spike (1000 nglmL'j was an appropriate level for all four analytes, the recoveries were consistently less than 30% for all analytas, with PFOS showing no measuring recovery . The high FMS was reextracted to rule out a potential preparatory error during the extraction process . The second extraction produced similar recoveries as the tirst . A laboratory matrix spike at 1000 ng/mL was aPlFsHo Sp(r9e3pa.5re%d)., Tanhde PLMFBSSr(e9c7o.v2e%ry) mbuettnmoet tfhoor dPFaOccSep(1ta3n.5ce%)c.riTtehrieareoffo1r0e0,t3h0e%safomrpPlFeOreAs(u8l5ts.f4o%r), PFOS should be considered estimated mi n imums with a sample analytical accuracy within an ogrivdeenr osfammapglenimtuadterixa.sAthltehoaungalhyttihcealLmMeSthpordodhuacsensoatcbceeepntadbelme orencsotrvaetreidestofobrePFsOuAitaabnled fPoFrHthSe, the sample results should be considered estimated minimums as no app ro priate supplementa ry FMS recovery was available . Low and mid level FMS and LMS recoveries within 10030% for PFBS demonstrate that the analytical method is appropriate for the given sample matrix for this analyte only. Further method development for the BP Well sample matrix will be performed to see if improved PFOA, PFOS, and PFHS recoveries can be achieved . PAGE 12 OF 21 p . 13 q %o6 LU Z mColl cc WW W 0 > Cl) tocp N CN ?? aD r . ~ Hg~ ~ ~p$ ~ E a Zj tnh c~ Y tD ~ M aCl. aV C ~A u~i o~ c~f COf W g ~,~ . b q Q to $ Z 2~ 2 2 $ o #11 . N LL 0 w a ~ P N g v " z rgE o. C f7 1p~ N GD ~p aD C . ~ 2O~ ~ ~ 12 ~ 3 If ~Sr~S m~Smmmm HilJ1 ~ l E ~ .~ 3 It i t to 1 -9 .~ 1"' W W W W W J Q p . 14 oW z ~ ~~ b mo gZ Q~ W W a y qs J Q0 N rn~ N M v C a~~ O N ~o p Of 2 W a E~ ~ N ~p ~ C C'f 0.0i C Cri Y N (TiT 4 \' O Z ? ? z J N ~p c~n`~ n E z W a v9 .\ 2 2 c = 0,i~ . ~ m g E a pS ~p Q N L ~C c~n+ ~G N N 4 10 zfN g CG.~_ ~<<Q ~.F p a, N 'P Pf M_ p p7 g~ C g E a Q a m qJ cO l, ~~~~ ~J o (L g ~ a. I m co in m i n E Ja cn U) lp Ja J J ~ .~ u O 0~~ aZ,~tnOa ~ a 04 y Of _~ ~ ~~ N V Z W W W W W~~ C4 w m2 iLl OR a, Q~ Z a ~ Y J ~l) 1G O p~ p' h Y'7 ~ N W az co ~ ~ J7 c Va C ~ g g~i N a V 95! 4 E~ ~ .rc N N N Nu, M Q Q cn ~ ~~ a O w r~ rn v " N N N e~ N p `+J gE 0 ~ N a t~ ~ M M N '~ g D~ C ~~U. C~ . ~ ~~ ~ m Mm m if CL w ~ W W w J~ Z p . 15 w p . 16 An W P c w o2 W N z ~ " ` ! , 4Z 'D o gk CW) co _-~ . .I en W) N~ L. ,V F a s F y W N~~, ~ o v .s Z Z 72 a I~' wZ St W g r A E e 4 nvj a ~U) N 2-2 M a - Jz V z L ? GI Z, -- .A ? . 'R em~ ~ts = ~Fi a c .a $ IE LL 0 co aw a ~ I r J J J J _.1 JJ J 1~1 E _J sEa d ~ J J J J J J J4 L~~ ~ Z Q, Z a r~ N O ~ TI z~~z Jo- A O to WWw'~w~Q$ p . 17 3M ENVIRONMENTAL LABORATOR Y REPORT NO . E06-0199 5 Conclusion Sample mat rix QC samples for the four samples repo rted herein did not meet method acceptance crite ria of 100t30k for PFOS . Therefore, the values-listed in Table land Tables 7-10 for PFOS should be considered estimated minimums. The sample analytical accuracy is arbitrarily estimated to be within an order of magnitude. Further method development is needed for this matrix as the QC results demonstrated that unknowP mat rix components preclude ac cu rate analysis with the method as performed here. Field matri x spikes yielding recoveries within 10030% demonstrated that the analytical method was suitable for the given sample mat ri ces for PFOA, PFHS, and PFBS for BPPO 1, BPPO2, and BPPO3 . The analytical method uncertainty for these analytes was presented in Tablel . PFOA and PFHS results for BPWeN should also be considered estimated minimums with a sample analytical accuracy within an order of magnitude as no acceptable field matrix spikes recoveries were produced = . g Data / Sample Retention Atoll3rMemEaninviinrognsmaemnptalel aLnadboarsastoocryiastetadnpdraorjdecotpdeartaati n(ghaprrdoccoepdyuraensd. electronic) will be archived according PAGE 17 OF 21 p . 18 3M ENVIRONMENTAL LABORA TOR Y REPORT NO. E06 -0 1 99 7 Signatures .~< , '%' r '% ^ ! ~~ Mich tle D. Malinsky, Ph-.D ., M Technicat e ad ~ ~ i'! . Date I ,~- ~ ~- ~ _ P, Kertt R . Lindstrom ,'3M Technical Reviewer Date =- :~~ _ ~~~ ~ __ C C Ci ~, William K. Reagen, Ph .D ., Environmental Labor ;-to-v Management Dat e The 3M Envi ro nmental Laboratory's Quality Assurance Unit has aud ited the data and repo rt for this proj ect . Quality As d nce Representative Dat e 3M CONFIDENTIAL PAGE 18 OF 21 P . 19 3M ENVIRONMENTAL LABORA TOR Y REPORT NO . E06-0199 8 Attachments 8.1 Method Blank/LOQ Area Count Comparison . Table 11 . Method Blank/LOQ Area Count Compa ri son : April 21, 2006 . Armikitmil Run: D*&Wft 21,21W Name Aisa Counts PFOA PFOS PFHS PFBS Meg" Blanks wlfh On Extraeled Curve 5060421&025 Method Blank-1 MB-050410-1 s060421a026 Method Blank-2 MB-0604102 s060421 a027 Method Blank-3 MB-060410-3 s060421a028 Method Blank -4 MB-060410 -4 55982 3413 1591 2760 18376 1082 668 2001 16127 1718 1970 2336 22714 1116 639 1305 s060421a029 Method Blank-5 MB -0G04105 s060421 a030 Method Blank-6 MB-0G0410-6 s060421a031 Method Blank-7 MB -060410-7 s060421a032 Method Blank-8 MB -0G0410-8 Method Blanks wid 0e Exbacted 21587 792 25928 4338 21060 2143 16383 1776 1686 2109 2077 5711 2436 3561 1660 4235 s060421a045 Method Blank-1 MB-0G0421-1 12933 1437 ")121128 277 s060421a046 Method Blank-2 MB-060421-2 12809 1446 n'129379 715 s060421a047 Method Blank-3 MB-06( 421-3 13875 2228 o66834 595 s060421a048 Method Blank -4 MB-060421-4 22242 2053 n)42902 1052 s060421a049 Method Blank-5 MB-060421-5 19675 1762 (1)33923 826 s060421a050 Method Blank -6 MB-060421-6 17774 1568 ") 13105 2071 s060421a051 Method Blank-7 MB-060421-7 1384 ; 1084 6059 9'19419 s060421a052 Method Blank-8 M&060421-8 14073 1492 5570 450 Area Counts of the LOQ standard 163373 14600 13176 25766 A rea Counts of the LOQ standard'0 .5 81686.5 7300 6588 12883 Concentration of LOQ standard fnaftiL) 0.0500 0 .0999 0 .025 0 .025 (1) Method blanks injected krxnediatey af. ter a hm ighly contamp inated r solve ent blas nk . Ce a oven r t. Values excluded when establishing the LOQ for PFHS (2) Method blank determined to be a statis tical outlier at the 99% confidence level using Dbron 's Q-test . Value exduded when establishing the LOQ for PFBS . PAGE 19 OF 21 p . 20 3M ENVIRONMENTAL LABORATORY REPORT NO E06-0199 Table 12 . Method Blank/1-00 Area Count Comparison : ! . April 24, 2006. DetaAle Run : 24, 200s SwIpie, Area Court s Name PFOA PFOS PFNS PFBS Method Blanks Ph P&'Wd wltl the Exbacted Curve s060424a025 Method Blank-1 MB-0604141 "36625 3514 2029 3078 s060424a026 Method Blank-2 MB-060410-2 "~42239 2274 2890 3938 s060424427 Method Blank-3 MB-060410-3 25302 2950 1147 2248 s060424a028 Method Blank-4 MB-060410-4 22151 804 1197 1638 s060424a029 Method Blank-5 MB-060410-5 30401 2565 1955 2593 s060424a030 Method B&ank-6 MB-060410-6 i 17458 827 1275 5242 s060424a031 Methoa dianlc-7 MB-060410-7 26074 1195 1974 3516 s060424a032 Method Blanc-8 M3-060410-8 22049 1192 1512 4294 Metlod BNnks with the Extracted Labonitoty Matrix Sp#m s060424a090 AAelhod Eiank-1 M13-06L'425-1 30448 2301 1778 1906 5060424a091 Method Blank-2 MB-060425-2 15006 1266 1311 2990 s060424a092 Method Blank-3 MB-060425-3 11262 991 1039 1703 s060424a093 Method Blank-4 MB-060425-4 11867 836 707 6142 s060424a094 Method BIar1R-5 MB-060425-5 ; 16236 1024 717 2723 s060424a095 Method Blank-6 MB-0f'6042" 15924 1107 589 5446 s060424a026 Method Bla :k-7 MB-030425-7 22750 1530 1038 4355 s060424a097 Method 84ank -8 MB-0B:N.25-8 Area Counts of the LOQ sfandard Are a Counts of the LOQ atandard'0.6 Concentration of L04 standard jngIrnL) 19234 1071 1135 1677 36(i6U 6724 12166 27032 18030 3362 6083 1351E 0.0-'5 0 .04 0.025 0 .025 (1) Value excluded for the LOO determination for the given set. Area counts are very close to one-half the LOQ value. Pnor anatysis of this extract demonstrated area counts below one-had the 25 ppt standard . LMSs analyzed on this day are well above the LOO. PAGE 20 OF 21 p . 21 3M ENVIRONMENTAL LABORATOR Y REPORT NO . E06-0199 8.2 Solvent Blank/1-00 Comparison . Table 13. Area Counts of Solven*. Blank. Area Counts Fde Yul Posit/on PFOA PFOS PFMS PFBS 060421401 91 70233 3067 1853 192 s060421a002 91 16249 2196 1851 563 s060421a003 91 18222 16A2 567 471 s060421a009 91 48287 4524 1505 447 s060421a010 92 "184762 5006 2424 889 s060421a023 92 48308_, 4192 , 4524 6609 s060421a024 92 "'84666 .5317 . 4738 7007 s060421a035 93 ")162166 0)283547 " )52950 ( ' )41582 s060421a037 93 23806, N904 2706 2357 s060421a042 93 15939 2135 1693 1823 s060421a044 94 49169, . M8, "'274j54 1118, . s060421a055 94 126815 1141 ")328841 547 s060421a057 94 47071 . 338~ "1257946 946 s060421a068 95 53696 2525 5237 1137 s060421a070 95 74125 5907 6588 975 s060421a081 95 62139 24.24 3945 1225 s060421a083 95 68329 3139 3951 1149 5060421094 96 76799 4192 3512 1054' s060421a096 96 77269, 3358 3905 1173 s060421a107 97 14824 1166 852 335 - s060421a109 97 19120 1763 1499 1289 s060421a120 97 9916 1028 .1024 698 s060421a122 98 24599 1589 2321 3275 s060421a127 98 " 37573 t305 6127 2190 s060421a129 99 18673 1100 1909 937 s060421a135 99 31743 1944 1472 632 LOQ Standard 163373 14600 13176 25766 %i LOQ Standard 81687 7300 6588 12883 (1) Area oounts of the solvent blank were greater than %,'the LOQ standard area counts . PAGE 21 0F 21