Document N2qzDo9LoQrKdkqQZRxw9gByV

p. 1 M A U ^ 3 7 -2 6 3MENVIRONMENTAL LABORATORY REPORT NO. E06-0199 V Subreport Analysis of PFOA, PFOS, PFH, and PFBS in Aqueous Samples: 3M Decatur Offerte Sampling Event (BPP Sample Sites) ! Laboratory Request Number: 06-0199 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 Requester Gary Hohenstein 3M Building 42-02-E-27 PO Box 3331 Saint Paul, MN 55133-3331 Phone: (651)778-5150 Fax: (651) 778-7203 TrtCX> 9? Ca> ro The testing reported herein meet the requirements of ISO /IEC17025-1999 "General Requirements for the Competence o f Testing and Calibration. Laboratories", in accordance with the A2LA Certificate #2052-01. Testing that complies with this International Standard also operate in accordance with ISO 9001/ISO 9002 (1994). . Certificate #2052-01 PAGE 1 OF 21 000003 P-2 3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0199 3M Environm ental Laboratory 3M Environmental Laboratory Manager: William K. Reagen, Ph.D. 3M Technical Lead: Michelle Malinsky, Ph.D. Report Author: Michelle Malinsky, Ph.D. Analytical Subreport E06-0199 Surface Water Samples BPP01, BPP02, and BPP03; Ground Water Sample BPWell Decatur Offsite Sampling Event Report Date: May 1 ,2 0 0 6 1 Introduction/Sum m ary The 3M Environmental Laboratory extracted and analyzed ground water and surface water samples collected by Weston Solutions personnel on April 12 and 1 3 ,2 0 0 6 near the 3M Decatur facility. Samples were returned to the 3M Environmental Laboratory for analysis of perfiuorooctanoate (PFOA), perfluorooctane sulfonate (PFO S), perfluorohexane sulfonate (PFHS) and perfluorobutane sulfonate (PFBS) under laboratory project number E 06-0199 using modified 3M Environmental Laboratory Method ETS 8-154.1 "Determination of Perfluorinated Adds, Alcohols, Amides, and Sulfonates in W ater by Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry". Per the dient's request, an initial subreport is being issued for the following four sample locations only: DAL SW S BPP01 DAL SW S BPP02 . DAL S'W S BPP03 DAL GW S BPWELL This report will contain information relevant to ihese four sample collection points only. These results will be reissued in a comprehensive final projed report that indudes results for all samples collected under E06-0199. The 3M, Environmental Laboratory prepared sets of sample containers for thirty-two separate sampling locations. At a minimum, each sample set consisted of a field sample, field sample duplicate, low field spike and high field spike. For some locations, a third mid-levei field spike was prepared. Each empty container was marked with a "fill to here" line which corresponded to 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 fo the field for sample collection. The spike amounts prepared for each of the four locations presented here will be provided later in this report. Certificate #2052-01 The testing reported herein m eet the requirements of ISO /IEC 17025-1999 "General Requirements for the Competence of Testing and Calibration Laboratories", in accordance with the A2LA Certificate #2052-01. Testing that complies with this International Standard also operate in accordance with ISO PAGE 2 OF 21 OOCHM4. 3M ENVIRONMENTAL LABORATORY 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 2 5 ,2 0 0 6 in the analytical batch initiated on April 2 4,2006.., - . ,; 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 w ater prior to extraction. Table 1. Sample Results Summary. - , ., 3M UNIS ID E06-0199-055 E06-0199-056 E06-0199-060 E06-0199-061 E06-0199-065 E06-0199-066 E06-0199-070 E06-0199-071 Sample Descnption '1 ' .' 'i : mPFOA Concentration (ng/mL) PFOS Concentration (ng/mL) n PFHS Concentration (ng/mL) DAL SWS BPP01 0 060413 DAL SWS BPP01 DB 060413 Average 293 307 300 ^> 4 2 3 ,, w>380 m>402 ,, 5 3 .3 . 54.3 53,8 %RPD Sample/Sample Dqp 4.7 AM . DAL SWS BPP02 0 060413 . : </ DAL SWS BPP02 DB 0 6 0 41 3 '- ! ' 06 . j m>295 . 219 7 . ^>314 ' "" Average 212 ' m>304 %RPD Sample/Sample Duo j 6.1 , AM ' DAL SWS BPP03 0 060413 DAL SWS BPP03 DB 060413 : , Average 219 214 216 ^>272 ; , w>256 ^ . m>264 %RPD Sample/Sample Dup 2.3 NA - DAL GWS BPWELL 0 060413 DAL GWS BPWELL DB 060413 (2|>774 *> 7 7 9 w>1460 ' *>1170 ' Average %RPD Sample/Sample Dup m>776 NA ' *>1320 AM 1.8 38.2 39.8 39.0 ' 4.1 39.1 40.1 39.6 2.5 '/ (2|>145 ' ,2)>145 m>145 NA mPFBS Concentration (ng/mL) 6.98 7.17 7.08 2.7 4.50 4.72 4.66 2.6 4.69 5.05 . 4.87 7.4 17.2 17.6 17.4 2.3 (1) The analytical methpd uncertainty, for PFOA, PFHS, and PFBS was 10Q11%, 10O5.8%, and 1008.8%, respectively based on method accuracy &rid precision. Se^'Sectlon 3.7 for additional explanation. The lim it of 'quantitation (LOQ) for these samples only was 2.50 ng/mL (PFOA) and 1.25 ng/mL (PFHS and PFBS). Results and average values arprounded to three significant figures according to EPA rounding rules. Percent relative difference (%RPD) values are rounded to two significant, figures. Because o f rounding,.values may vary slightly from those listed In the raw data. ,; ; (2) A ll PFOS sample results presented here should be considered estimated minimum values as quality control samples (field matrix spikes and lab matrix spikfs) associated with these four samples did not demonstrate adequate method performance. The accuracy o f the PFOS results could be within an order o f magnitude. %RPD values not calculated. BPWell results for PFOA and PFHS should also be considered estimated minimurns as field matrix spike recovenes did not m eet method acceptance critena o f 100130%. The analytical accuracy o f the PFOA and PFHS estimated values fo r mis sample only could be within an order o f magnitude. %RPD values not calculated. . 2 Methods - ' 1 . > ' - 'r \.. T .7 .. ' . 2.1 Sample Collection Samples were collected in NalgeneTM (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 PAGE 3 OF 21 000005 P- 4 3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0199 four analytes of interest (PFOAj PFOS, PFHS and PFBS). Collected sample bottles were received at the laboratory at ambient conditions on April 1 9 ,2 0 0 6 . Table 2 below details the samples collected and spikes added to each bottle. ' Table 2. Sample Collection and Spike Information. 3M UM SIDH Weston Sample Description E06-0199-055 E06-0199-056 E06-0199-057 E06-0199-058 E06-0199-059 DAL S'WS BPP01 0 060413 DAL SWS BPP01 DB 060413 DAL SWS BPPC1 LS 06C413 DAL SWS BPP01 MS 060413 DAL SWS BPP01 HS 060413 E06-0199-060 E06-0199-061 E06-0199-062 E06-0199-063 E06-0199-064 DAL SWS BPP02 0 060413 DAL SWS BPP02 DB 060413 DAL SWS BPP02 LS 060413 DAL SWS BPP02 MS 060413 DAL SWS BPP02 HS 060413 E06-0199-065 DAL SWS BPP03 0 060413 E06-0199-066 DAL SWS BPP03 DB 060413 E06-0199-067 DAL SWS BPP03 LS 060413 E06-0199-068 DAL SWS BPP03 MS 060413 E06-0199-069 DAL SWS BPP03 HS 060413 E06-0199-070 DAL GWS BPWELL 0 060413 E06-0199-071 DAL GWS BPWELL DB 060413 E06-0199-072 DAL GWS BPWELL LS 060413 E06-0199-073 DAL GWS BPWELL MS 060413 E06-0199-074 DAL GWS BPWELL HS 060413 DAL = Decatur, AL SWS = Surface Water Sample GWS = Ground W ater Sample 0 = Sample DB = Duplicate LS = Low Spike MS = Mid Spike HS = High Spike , 3M Bottle Number 109 110 111 '112 113 119 120 121, 122 123 114 115 116 117 113 72 73 74 75 ___ Z l _ : Bottle Designation Sample Sample Dup FMS Lov/ FMS Mid FMS High Sample Sample Dup FMS Low FMS Mid FMS High Sample Sample Dup FMS Low FMS Mid FMS High Sample Sample Dup FMS Low FMS Mid FMS High Nominal Spike Level (ng/mL) NA NA 1.0 10 100 NA NA 1.0 10 100 NA NA 1.0 10 100 NA NA 10 100 1000 GPO Location Com m ent, FSIA Drainage FSIA Drainage FSIA Drainage FSIA Drainage FSIA Drainage FSIA Drainage FSIA Drainage FSIA Drainage FSIA Drainage FSIA Drainage FSIA Drainage FSIA Drainage FSIA Drainage FSIA Drainage FSIA Drainage BP Property BP Property BP Property BP Property BP Property 2.2 Extraction All samples, calibration standards, and associated quality control samples were extracted using a modified procedure of E TS -8-154.1 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates in W ater by Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry". Briefly, 40 mL of sample were loaded onto a pre-conditioned W aters C 18 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 E TS -8-154.1. See Section 3.6 for additional information. PAGE 4 OF 21 000006 P-5 3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0199 The samples and sample duplicates for BPP01, BPP02, and BPP03 were Initially extracted undiluted on April 1 9 ,2006. Initial analysis of the undiluted samples exceeded the upper limit o f quantiation (25 ng/mL nominal) for PFOA and PFO S. Likewise, the sample and sample duplicate for BPW ELL were initially extracted on April 1 9 ,2 0 0 6 . The final extracts were diluted 1:10 prior to analysis. Analysis of these diluted extracts also exceeded the upper lim it of-quantitation. ,A|I the samples, sample duplicates, and field matrix spikes were reextracted on April 2 1 ,2 0 0 6 . For B PP01, BPP02, and BPP03, the samples and associated QC were diluted 1:50 using ASTM Type I w ater prior to extraction. For BPW ELL, the sample, sample duplicate Jow spike arid mid spike were diluted 1:50, while the high spike was diluted 1:500. . . . - u, 2.3 Analysis i All sample and quality control extracts were analyzed for PFOA, P F 6 s , PFHS, arid FTBS using high performance liquid chromatography/tandem mass Spectrometry (H PLC /M S/M S). 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 Liquid Chromatograph Guard column Analytical column Injection Volume Mass Spectrometer Ion Source Electrode Polarity Software ' ETSStan ' ; : Agilent 1100 , Betasil C18 (2.1 mmXlOO mm), 5 urn Betasil C18 (2.1 mm X 100 mm), 5 urn 5 iiL ' Applied Biosystems API 4000 ' Turbo Spray ' '1 Z-spray Negative ,, . Analyst 1.4.1 Table 4. 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 (fiUm in) 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 t *< f' PAGE 5 OF 21 00000*7 P-6 3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0199 Table 5. Mass Transitions. . Analyte <1)PFBS (,)PFHS (,|PFOS n)P rO A Mass Transition Q1/Q3 Dwell Time (msec) 299/80 125 299/99 125 399/80 125 , 399/99 : ' 125 .. 499/130 125 499/99 ' 125 . 499/80 - 125 413/369 125 413/219 125 413/169 125 (1) The individual transitions were summed to produce a "total ion chromatogram" (TIC). The TICs were used for quantitation. 3.1 Calibration Calibration standards were prepared by spiking known amounts of stock solutions containing the target analytes 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 twelve spiked standards ranging from 0.02,5 ng/mL to 25 ng/mL (nominal) were prepared. A quadratic, 1/x weighted, calibration curve was used to fit the data for each analyte. The data were not forced rough 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% . The correlation coefficients (r) were greater than 0.999 for all analytes. 3.2 Limit of Quantitation. (LOQ) . The LOQ for this analysis, as defined in E TS -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 and solvent blank(s). The LOQs for PFOA, PFOS, PFHS, and PFBS 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 comparison 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-calibration standard were analyzed at the beginning and end of the analytical sequence to demonstrate overall system suitability. All analytes met method acceptance criteria of less than 5% relative standard deviation (R SD) for peak area and less than 2% RSD for retention time for both opening and closing system suitability .injections. 3.4 Continuing Calibration > During the course of the analytical sequence, several continuing calibration verification samples (CCVs) were analyzed to confirm that th e instrument response and the initial calibration curve were still in control. O ne PFO S C C V (139% ) and one PFH S C C V (153% ) exceeded method acceptance criteria of 100+25% for accuracy. Both of thesenon-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 OOOQO P-7 3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0199 issued. The overall impact to the data quality objectives for the sample results is considered minimal 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 field/trip blanks. Each blank type is described below. 3.5.1 Method Blanks Several method blanks were prepared by loading 40 mL of ASTM Type I water onto a C18 SPE cartridge and eluting with 5 mL of methanol using the same extraction procedure as the samples. Method blanks were prepared to evaluate the levels of background contamination in the overall extraction process (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 2 1 ,2 0 0 6 ). 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 2 4 ,2 0 0 6 . 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 2 1 ,2 0 0 6 analysis,three separate vials of methanol solvent blanks were < contaminated and produced area counts of the target analytes greater than one-half those of the LOQ standard. A method deviation has b een 'issued. The solvent blank area'count comparison for the April 2 1 ,2 0 0 6 is provided in the Attachments section at the end of this report. For the lab matrix-Spikes'' analyzed on April 2 4 ,2 0 0 6 , only the initial solvent blanks injected before the opening system ' . suitabilities ana the solvent blanks analyzed after the highest calibration standard exhibited area counts greater than one-half the LOQ standard. - r -. 3.5.3 Field/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 A STM Type I water, seafed, and shipped to the sample collection site along with the empty containers. The trip blank serves as an additional method blank that accounts for any storage conditions and/or holding time issues that the samples may experience. Results of the trip blank analyses will be provided in the final comprehensive report. > 3.6 Lab Control Spikes (LCSs) Lab control spikes at nominal concentrations of 0.050 ng/mL, 5.0 ng/mL, 100 ng/mL, and 1000 ng/mL spikes were prepared and analyzed each day samples were extracted and analyzed. The 0.050 ng/mL and 5.0 ng/mL LCSs were prepared by spiking knov/n amounts of the analytes into 40 mL of ASTM Type I w ater to produce the desired concentration. Tine spiked w ater samples w ere then extracted and analyzed in the sam e manner as the samples. For the 100 ng/mL and 1000 ng/mL LCSs, target analytes were added to 450 mL of A STM Type I water to produce the final desired concentration. An aliquot of the LCS was then diluted 1:50 or 1:500 with ASTM Type I water prior to extraction, in the 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 at the various levels cross-validates the analytical method, as used here, for any modifications/deviations from ETS 8-154.1. Additionally, LCS results will be used to determine overall method uncertainty in Section 3.7. Table 6 summarizes the LCS recover/ results. PAGE 7 OF 21 000009 p .8 3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0199 Calculated Concentration 1 LCS Percent Recovery Spike Concentration LCS% r s d = standard deviation LCS replicates , 1m % average LCS recovery PAGE 8 OF 21 OOOOiO 3 M ENVIRONMENTAL LABORATORY REPORT NO. E06-0199 Table 6. (1>Lab Control Spike Results. PFOA Sample Description Lab ID Spiked Cone. (ng/mL) Cale. Cone. (ng/mL) % Recovery 0.05 ppb LCS LCS-060410-1 0.05 ppb LCS LCS-060410-2 0.05 ppb LCS LCS-060410-3 5.0 ppb LCS LCS-060410-4 5.0 ppb LCS LCS-060410-5 5.0 ppb LCS LCS-060410-6 0.05 ppb LCS LCS-060421-1 0.05 ppb LCS LCS-060421-2 0.05 ppb LCS LCS-060421-3 5.0 ppb LCS LCS-060421-4 5.0 ppb LCS LCS-060421-5 5.0 ppb LCS LCS-060421-6 100 ppb LCS LCS-060421-7 100 ppb LCS LCS-060421-8 100 ppb LCS LCS-060421-9 1000 ppb LCS LCS-060421-10 1000 ppb LCS LCS-060421-11 1000 ppb LCS LCS-060421-12 0.05 ppb LCS LCS-060425-1 0.05 ppb LCS LCS-060425-2 5.0 ppb LCS LCS-060425-3 5.0 ppb LCS LCS-060425-4 100 ppb LCS LCS-060425-5 100 ppb LCS LCS-060425-6 1000 ppb LCS LCS-060425-7 1000 ppb LCS LCS-060425-8 Average %Recovery J%RSD | 0.0500 0.0500 0.0500 5.00 5.00 5.00 0.0500 0.0500 0.0500 5.00 5.00 5.00 100.0 100.0 100.0 1000 1000 1000 0.0500 0.0500 5.00 5.00 100.0 100.0 1000 1000 <0.0500 <0.0500 0.0517 4.93 4.86 5.30 <0.05 <0.05 0.0514 5.02 4.81 4.82 95.0 99.7 96.9 928 977 1030 0.0689 0.0600 4.91 4.87 95.3 98.6 977 972 101%9.7% ,2'n a ,2)n a 104 98.6 97.2 106 ,2|n a (2|n a 103 100 96.2 96.4 95.0 99.7 96.9 92.8 97.7 103 ,4)138 120 98.2 97.3 95.3 98.6 97.7 97.2 PFOS Spiked Cone. (ng/mL) Cale. Cone. (ng/mL) % Recovery 0.0500 <0.0999 0.0500 <0.0999 0.0500 <0.0999 5.00 4.93 5.00 5.01 5.00 5.05 0.0500 <0.0999 0.0500 <0.0999 0.0500 <0.0999 5.00 4.53 5.00 4.34 5.00 4.49 99.9 87.3 99.9 89.2 99.9 88.5 999 855 999 899 999 929 0.0500 0.0631 0.0500 0.152 5.00 4.79 5.00 4.94 99.9 84.5 99.9 89.8 999 878 999 849 93.1%10% (2)n a PINA (2,n a 98.7 100 101 ,2)n a '"NA ,2,n a 90.7 86.9 89.9 87.4 89.3 88.6 85.6 90.0 93.0 |4)126 |5)304 95.9 98.9 84.6 89.9 87.9 85.0 PFHS Spiked Cone. (ng/mL) Ca/c. Conc. (ng/mL) % Recovery 0.0500 0.0504 0.0500 0.0480 0.0500 5.00 0.0483 4.98 5.00 4.94 5.00 4.98 0.0500 0.0501 0.0500 0.0485 0.0500 5.00 0.145 4.88 5.00 4.79 5.00 4.90 100 98.1 100 100.0 100 99.4 1000 940 1000 988 1000 1020 0.0500 0.0578 0.0500 0.0592 5.00 4.98 5.00 5.08 100 95.9 100 96.8 1000 978 1000 966 99.8%5.6% 101 96.0 96.6 99.6 98.8 99.6 100 97.0 (3|289 97.6 95.8 98.0 98.1 100.0 99.4 94.0 98.8 102 116 118 99.6 102 95.9 96.8 97.8 96.6 PFBS Spiked Conc. (ng/mL) Cale. Conc. (ng/mL) % Recovery 0.0499 0.0505 0.0499 0.0456 0.0499 0.0480 4.99 4.94 4.99 4.88 4.99 4.94 0.0499 0.0426 0.0499 0.0427. - 0.0499 0.0441: -. 4.99 4.80 4.99 ` 4.71 4.99 4.76 .. 99.9 98.5- 99.9 100.0 99.9 : 98.0 999 909 999 973 999 1040 0.0499 0.0563 0.0499 0.0507 4.99 4.89 4.99 4.86 99.9 95.2 99.9 96.6 999 988 999 975 96.8%5.8/ 101 91.3 96.1 98.9 97.7 98.9 85.3 85.5 88.3 96.1 94.3 95.3 98.6 100 98.1 91.0 97.4 104 113 102 97.9 97.3 95.3 96.7 98.9 97.6 000011 PAGE 9 OF 21 3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0199 (1) All results and average values listed to three significant figures according to EPA rounding rules. %RSD values given to bvo significant figures. Due to rounding, values may vary slightly from those in the raw data. (2) Low end of the calibration curve disabled for PFOS and PFOA due to solvent blank contamination. Recovered LCS concentrations were below the established LOQ and are not reported. (3) High recovery due to instrument carryover from the previous injection of a contaminated methanol blank. Recovery excluded from average and %RSD calculations. (4) Recovery was outside the method acceptance criteria of 100+25%; however, the recovery was included in the calculation of the overall average and %RSD. (5) Recovery was outside the method acceptance criteria of 10025%; the recovery value was not included in the calculation of the overall average and %RSD as it was dearly a statistical outlier. The 5 ppb, 100 ppb, and 1000 ppb LCSs are more representative of the sample concentrations for the results reported in this subreport. Impact to data quality objectives is minimal. I PAGE 10 OF 21 p. 10 000012 3M ENVIRONMENTAL LABORA TORY REPORT NO. E06-0199 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, the overall accuracy and precision for PFO A based on LCS results was 101% 9.7% . The measured precision (% RSD) is then used to determ ine the range of the accuracy. Example: 101*(0.097) = 9.84 1 0 1 + 9 .8 4 = 1 1 1 .1 ; 1 0 1 -9 .8 4 = 91.45 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% -100= 11.1% 100% -91.45 = 8.54% . : The most conservative (largest) absolute difference is then used as the analytical uncertainty for the given analyte. Therefore, the analytical uncertainty for PFOA is given as 10011% (two significant figures) for these results. For PFO S, PFHS, and PFBS, the analytical method uncertainty is 100+16% , 100+5.8% , and 100+8.8% , respectively. It should be emphasized that the analytical method uncertainty described above only applies to the method and the procedures performed within. Additional quality control samples specific to the sample matrix, in the form of field matrix spikes and lab matrix spikes, demonstrate that the individual sam ple results are accurate to within 100+30% , the targeted data quality objectives. 3.8 Field Matrix Spikes (FMS) At a minimum, low and high field matrix spikes were collected at each sampling point to verify that the analytical method is applicable to the collected matrix. For some locations, a mid-level spike was also collected. Field matrix spike recoveries within method acceptance criteria of 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. The field matrix spike should be at least 50% of the endogenous sample concentration to be considered an appropriate spike level for the given sample matrix. FMS Recovery = (SamP|e Concentration of FMS - Average Concentration : Field Sample & Field Sample P u p .), 10QO/ Spike Concentratori 3.9 Lab Matrix Spikes (LMS) If the sample and sample duplicate produced concentrations where none of the associated field matrix spikes were at least 50% of the endogenous concentration, then laboratory matrix spikes (LMS) were prepared. LMSs were prepared by spiking a known amount of target analytes into a measured aliquot of the sample matrix. The spiked matrix was then diluted, if necessary, and extracted in the same m anner as the samples. LMS recoveries within 10030% demonstrated that the analytical method was appropriate for the given sample matrix only in the absence of an appropriate field matrix spike. 4 Data Sum m ary The data tables below summarize the sample results, field matrix spike recoveries, and laboratory matrix spike recoveries for the four locations (B PP01, BPP02, BPP03, and BPW ell). Each table provides the average concentration and the relative percent difference (RPD) of the sample and sample duplicate. PAGE 11 OF 21 000013 p. 12 3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0199 BPP01 . The endogenous concentration for BPP01 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 PFO S. A laboratory matrix spike at 500 ng/mL was prepared and analyzed. The LMS recovery met method acceptance criteria of 100+30% for PFOA (79.6% ), but not for PFOS (60.6% ). 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. FM S and/or LMS recoveries within 100+30% for PFOA, PFHS, and PFBS demonstrate that the analytical method is appropriate for the given sample matrix for these analytes. BPP02 The endogenous concentration for BPP02 was at least twice the spike concentration for the low spike (1 ng/mL) and mid spike (10 ng/mL) for both PFOA and PFO S as well as the high spike (100 ng/mL) for PFO S only. A laboratory matrix spike at 250 ng/mL was prepared and analyzed. The LMS recovery met method acceptance criteria of 100+30% for PFOA (75.0% ), but not PFO S (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 matrix. FM S 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. BPP03 The endogenous concentration for BPP03 was at least twice the spike concentration for the low spike (1 ng/mL) and mid spike (10 ng/mL) for both PFO A and PFO S as well as the high spike (100 ng/mL) for PFO S only. A laboratory matrix spike at 250 ng/mL was prepared and analyzed. The LMS recovery met method acceptance criteria of 10030% for PFOA (73.8% ), but not PFO S (60.8% ). 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 matrix. The high level PFBS FMS exceeded method acceptance criteria of 100+30% (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 FM S and LMS recoveries were excellent, 101% and 90.2% , respectively. High level FMS and LMS recoveries within 100+30% for PFOA and PFHS also demonstrate that the analytical method is appropriate for the given sample matrix for these two analytes as well. BPWell 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 ng/mL) was an appropriate level for all four analytes, the recoveries were consistently less than 30% for all analytes, with PFO S 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 first. A laboratory matrix spike at 1000 ng/mL was also prepared. The LMS recovery met method acceptance criteria of 10030% for PFOA (85.4% ), PFHS(93.5% ), and PFBS(97.2% ) but not for PFO S (13.5% ). 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. Although the LMS produces acceptable recoveries for PFOA and PFHS, the sample results should be considered estimated minimums as no appropriate supplementary 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 W ell sample matrix will be performed to see if improved PFOA, PFO S, and PFHS recoveries can be achieved. PAGE 12 OF 21 (00014 3MENVIRONMENTAL LABORATORY REPORT NO. E06-0199 ..hr r* Table 7. ,1,BPP01 Results. PFOA PFOS PFHS PFBS 3M U M S ID Description E06-0199-055 DAL SWS BPP01 0 060413 E06-0199-056 DAL SWS BPP01DB 060413 E06-0199-057 DAL SWS BPP01 LS 060413 E06-0199-058 DAL SWS BPP01 MS 060413 E06-0199-059 DAL SWS BPP01 HS 060413 ' ., LMS-060425-1 DAL SWS BPP01 0 060413 500ppb LMS Average Concentration (ng/mL) %RPD Cone. (ng/mL) % Recovery 293 NA 307 NA 292 |2!n r 328 |2)n r . 361 ,2!m r. 698 79.6 30014.7% Cone. (ng/mL) % Recovery 423 NA 380 NA 338 (2|n r 484 - P,NR 365 <2)n r 704 ,3)6 0 .e ' '*>402 Cone, (ng/mL) % Recovery 53.3 NA 54.3 NA 53.4 (2|n r 66.6 |2,n r . 136 82.2 485 . 86.2 53.811.9% Cone. (ng/mL) % Recovery 6.98 NA 7.17 NA 7.44 (2|n r 18.8 117 93.8 86.8 444 87.5 7.0812.7% NA= Not Applicable. - - i - (1) Table displays rounded values for a ll concentrations and percent recovery values (3 significant figures), %RPD values (2 significant figures). Recovery and RPD values may vary slightly from the values in foe raw data. All samples and associated FMSs were diluted 1:50 in ASTM Type I water prior to extraction: LJVISwas diluted 1:100 prior to extraction. (2) NR=Not reportable. FMS level not appropriate for the given mafrix. The endogenous sample concentration was at least twice spike level. .? (3) LMS recovery outside of riiethod acceptance criteria of 10030%. - (4) PFOS sample results should be considered estimated minimums .only. Sample matrix specific QG did not meet method criteria. The analytical sample accuracy is arbitrarily estimated to within an order of magnitude. %RPD values not reported. ^ p. 13 000015 PAGE 13 OF 21 3M ENVIRONMENTAL LABORATORY REPORT NO. 06-0199 Table 8. (1)BPP02 Results. 3M IM IS ID Description E06-0199-060 DAL SWS BPP02 0 060413 E06-0199-061 DAL SWS BPP02 DB 060413 E06-0199-062 DAL SWS BPP02 LS 060413 E06-0199-063 DAL SWS BPP02 MS 060413 E06-0199-064 DAL SWS BPP02 HS 060413 LMS-060425-2 DAL SWS BPP02 0 060413 250ppb Average Concerilration (nq/mL) % RPD PFOA Cone. (nq/mL) % Recovery 206 NA 219 NA 234 (2)n r 220 |2|n r 314 102 400 75.0 2126.f% PFOS Cone. (ng/mL) % Recovery 295 NA 314 NA 388 |2|n r 346 P,NR 437 PINR 454 |3)59.8 w>304 P F HS Cone. (ng/mL) % Recovery 38.2 NA 39.8 NA 42.3 (2|n r 48.0 (2)n r 134 95.0 256 86.8 39.04.1% PF BS Cone. (ng/mL) % Recovery 4.6 NA 4.72 NA 5.9 (2)n r 14.4 97.5 102 97.5 223 87.4 4.66t2.6% NA=Not Applicable *' (1) Table displays rounded values for all concentrations and percent recovery values (3 significant figures), %RPD values (2 significant figures). Recovery and RPD values may vary slightly from the values in the raw data. All camples and associated QC were diluted 1:50 in ASTM Type I water prior to extraction. (2) NR=Not reportable. FMS level not appropriate for the given matrix. Endogenous concentration was at least twice spike level. (3) LMS recovery outside of method acceptance criteria of 10030% - ... ... (4) PFOS sample results should be considered estimated minimums onty. Sample matrix specific QC did not meet mettiod criteria. The analytical sample accuracy ts arbitranly estimated to within an order of magnitude. %RPD values not reported. p. 14 O O O O iG PAGE 14 OF 21 3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0199 Table 9. BPP03 Results. PFOA PFOS PFHS PFBS M U M S ID Description Cone. (ng/mL) % Recovery Cone. (ng/mL) % Recovery Cone. (ng/mL) % Recovery Cone. (ng/mL) % Recovery E06-0199-065 DAL SWS BPP03 0 060413 E06-0199-066 DAL SWS BPP03 DB 060413 E06-0199-067 DAL SWS BPP03 LS 060413 E06-0199-068 DAL SWS BPP03 MS 060413 E06-0199-069 DAL SWS BPP03 HS 060413 LMS-060425-3 DAL SWS BPP03 0 060413 250ppb LMS Average Concentration (ng/mU %RPD NA=Not Applicable. 219 NA 214 NA 211 ,2)n r 228 (2)n r 324 108 401 73.8 2 1 6 tZ 3 % 272 NA 256 NA 258 |2)n r 255 raNR 315 |2|n r 416 |4)60.8 p>>264 39.1 NA 40.1 NA 40.2 (2)n r 50.0 (2,n r 143 103 262 89.0 39.62.5% 4.69 NA 5.05 NA 5.76 (2)n r 15.0 101 139 |3,134 230 90.2 4.87 7.4% (1) Table displays rounded values for all concentrations and percent recovery values (3 significant figures), %RPD values (2 significant figures). Recovery and RPD values may vary slightly from the values in the raw data. A ll samples and associated QC were diluted 1:50 in ASTM Type I water prior to extraction. (2) NR-Not reportable. FMS level not appropriate for the given matrix. Endogenous concentration was at least twice spike level. (3) FMS recoveries outside method acceptance criteria of 10030%. (4) LMS recovery outside of method acceptance criteria of 100+30% - (5) PFOS sample results should be considered estimated minimums only. Sample matrix specific QC did not meet method criteria.' The analytical sample accuracy is arbitrarily estimated to within an order o f magnitude. %RPD values not reported. p. 15 000017 PAGE 15 OF 21 3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0199 Table 10. (1)BPWell results. PFOA PFOS PFHS PF BS 3M U M S ID Description E06-0199-070 DAL GWS BPWELL 0 060413 E06-0199-071 DAL GWS BPWELL DB 060413 E06-0199-072 DAL GWS BPWELL LS 060413 E06-0199-073 DAL GWS BPWELL MS 060413 t3,E06-0199-074 DAL GWS BPWELL HS 060413 ,4|E06-0199-074 DAL GWS BPWELL HS 060413 LMS-060425-4 DAL GWS BPWELL 0 060413 1000ppb LMS Average Concentration (ng/mL) % RPD Cone. (ng/mL) % Recovery 774 NA 779 NA 723 plNR 821 ,2|n r 1020 (S)24.4 987 <5)21.0 1630 85.4 **>776 Cone. (ng/mL) % Recovery 1460 NA 1170 NA 960 (2|n r 1020 |2)n r 1200 (6)n m r 1320 |f)NMR 1450 (7)13.5 m>1.T20 Cone. (ng/mL) % Recovery 145 NA 145 NA 152 |2,n r 244 raNR 375 (S|23.0 348 (S)20.3 1080 63.5 **>145 Cone. (ng/inL) % Recovery 17.2 NA 7.6 NA 26.9 95.1 122 105 286 |5)26.9 254 (5)23.7 988 97.2 17.4i2.TA (1) Table displays rounded values for all concentrations and percent recovery values (3 significant figures), %RPD values (2 significant figures). Recovery and RPD values may vary slightly from the values in the raw data. The sample, sample duplicate, low FMS, and mid FMS were diluted 1:50 in ASTM Type I water prior to extraction. The high FMS and 1000 ppb LMS were diluted 1:500 prior to extraction. (2) NR=Not reportable. FMS level not appropriate for the given matrix. Endogenous concentration was at least twice spike level. (3) FMS extracted on 4-21-2006 with the samples. (4) FMS re-extracted on 4-25-0006. (5) FMS recovery outside of method acceptance criteria of 10030%. -, (6) NMR = No measurable recovery. (7) LMS recovery outside method acceptance criteria of 10030%. (8) PFOA, PFOS, and PFHS sample results should be considered estimated minimums only. Field matrix spikes did not meet method criteria. The analytical sample accuracy is arbitrarily estimated to within an order of magnitude. %RPD values not reported. p. 16 000018 PAGE 16 OF 21 3MENVIRONMENTAL LABORATORY REPORT NO. E06-0199 ic lu s io n 'Pi#!ty. 'mi Sam ple matrix QC samples for the four samples reported herein did not m eet method acceptance criteria of 10030% for PFOS. Therefore, the values listed in Table l and Tables 7-10 for PFOS should be considered estimated minimums. The siample analytical accuracy is arbitrarily estimated to be within an order o f magnitude. Further;method development is needed for this matrix as the QC results demonstrated that unknown matrix components preclude accurate analysis with the method as performed here. Field matrix spikes yielding recoveries within 1Q030% demonstrated that the analytical method was suitable for the yen sample matrices for PFOA, PFHS, and PFBS for B PP01, BPP02, and BPP03. The analytical method uncertainty for these analytes was presented in T a b le l. PFOA and PFHS results for BPWeH should also be considered estimated minimums with a sample analytical accuracy within an Order o f magnitude as no acceptable field matrix spikes recoveries were produced. / 6 Data / Sam ple Retention . All remaining sample and associated project data (hardcopy and electronic) will be archived according to 3M Environmental Laboratory standard operating procedures. PAGE 17 OF 21 000019 3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0199 7 "' Signatures \ <:- } / / M sm j - Michtte D, Malinsky, PK D ., M Technic^r ilead ^r Kerft R. Lindstrom, 3M Technical Reviewer ^ /t/O L Date / PZ> / 0 J / C Date William K. Reagen, Ph.D., Environmental Laboratory Management Date The 3M Environmental Laboratory's Quality Assurance Unit has audited the data and report for this project. Quality A s k a n c e Representative Date ' 3M CONFIDENTIAL PAGE 18 OF 21 000020 p . 19 3M ENVIRONMENTAL LABORA TORY REPORT NO. E06-0199 8 Attachm ents 8.1 Method Blank/LOQ Area Count Comparison. Table 11. Method Blank/LOQ Area Count Comparison: April 21, 2006. Analytical Run: A Olii 21,2006 Datafile Sample Description Sample Name Method Blanks Pnspared with the Extracted Curve PFOA Area Counts PFOS PFHS PFBS s060421a025 Method Blank-1 MB-060410-1 s060421a026 Method Blank-2 MB-060410-2 S060421a027 Method Blank-3 MB-060410-3 s060421a028 Method Blank-4 MB-060410-4 S060421a029 Method Blank-5 MB-060410-5 s060421a030 Method Blank-6 MB-060410-6 s060421a031 Method Blank-7 MB-060410-7 s060421a032 Method Blank-8 MB-060410-8 Method Blanks P n pared with the Extracted Samples 55982 18376 16127 22714 21587 25928 21060 16383 3413 1082 1718 1116 792 4338 2143 1776 1591 668 1970 639 1686 2077 2436 1660 2760 2001 2336 1305 2109 5711 3561 42M s060421a045 Method Blank-1 MB-060421-1 12933 1437 (1,121128 277 s060421a046 Method Blank-2 MB-060421-2 12809 1446 (1)129379 715 s060421a047 S060421a048 Method Blank-3 Method Blank-4 MB-060421-3 MB-060421-4 13875 22242 2228 2053 (1)66834 ,1)42902 595 1052 S060421a049 Method Blank-5 MB-060421-5 19675 1762 (1,33923 826 s060421a050 Method Blank-6 MB-060421-6 17774 1568 (1)13105 2071 s060421a051 Method Blank-7 MB-060421 -7 13843 1084 6059 19419 s060421a052 Method Blank-8 MB-060421-8 14073 1492 5570 450 Area Counts of the LOQ standard 63373 14600 13176 25766 Area Counts of the LOQ standard*0.5 81686.5 7300 6588 12883 Concentration of LOQ standard (no/mL) 0.0500 0.0999 0.025 0.025 ' ' --------------------- 1--...............ira a iMMinjr uuiiiaiiraieueu suiveniDianK. oanyoverDresent Vauesexcfoded when establishing the LOQ for PFHS. (2) Method blank determined to be a statistical outlier at the 99% confidence level using Dixon's Q-test Value excluded when establishing the LOQ for PFBS. MMH t PAGE 19 OF 21 000021 3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0199 Table 12. Method Blank/LOQ Area Count Comparison:. April 24,2006. b tao 1 p 5 0 1 Area C Datafile Sample Description Sample ame PF PFOS MothnH Blanks Pneoared with the Extracted Curve s060424a025 s060424a026 s060424a027 s060424a028 s060424a029 s060424a030 s060424a031 s060424a032 Method Blank-1 Method Blank-2 Method Blank-3 Method Blank-4 Method Blank-5 Method Blank-6 Method Blank-7 Method Blank-8 MB-060410-1 MB-060410-2 MB-060410-3 MB-060410-4 MB-060410-5 MB-06041-6 MB-060410-7 MB-060410-8 ">36625 "'42239 25302 22151 30401 , 17458 ' 23074 22049 3514 2274 2950 804 2565 827 1195 1192 MothnH Blanks P ntoared with the Extracted Laboratory Matrix Spikes______ .___________ s060424a090 Method Biank-1 MB-060425-1 | 30448 ' 2301 s060424a091 Method Blank-2 MB-060425-2 15006 1266 s060424a092 Method Blank-3 MB-060425-3 11262 991 s060424a093 Method Blank-4 MB-060425-4 : 11867 836 s060424a094 Method Blank-5 MB-060425-5 ; 16236 1024 s060424a095 Method Blank-6 MB-060425-6 15924 1107 s060424a096 Method Blank-7 Method Blank-8 MB-0S0425-7 MB-060425-8 22758 I j 19234 1530 1071 Area Counts o f the LOQ standard Area Counts o f th e LOQ standard*0.5 ! 36060 I 18030 6724 3362 C oncentration o f IOQ standard (ng/m L) ! 0.025 I 0.04 PFHS I 2029 2890 1147 1197 1955 1275 1974 1512 1778 1311 1039 707 717 589 1038 1135 12166 6083 0.025 PFBS 3078 3938 2248 1638 2593 5242 3516 4294 1906 2990 1703 6142 2723 5446 4359 1677 27032 13516 0.025 (1) Value excluded for the LOQ determination for the given set. Area counts are very dose to one-half ^ L9 ? wr analysis of this extract demonstrated area counts below one-half the 25 ppt standard. LMSs analyzed on this day are well above the LOQ. PAGE 20 OF 21 000022 3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0199 8.2 Solvent Blank/LOQ Comparison. Table 13. Area Counts of Solvent Blank. ____________________ i Area Counts File Vial Position PFOA PFOS PFHS PFBS s060421a001 91 70233 3067 - 1853 . 192 s060421a002 91 16249 .2196 1851 ` 563 s060421a003 91 18222 ,1642 - ,567 . 471 . . s060421a009 91 48287 4524 . 1505 447 s060421a010 92 , (1)84762 , 5006 2424 889 , s060421a023 92 , 48308 . ,4192 . 4524 , 66Q9 s060421a024 92 |1'84666 -5317, ; 4738 . . , 7007 s060421a035 93 ; (1|162166, m283547 , (1|52950 mf1 5 82 s060421a037 93 , 23806, . ,<1)8904 2706 2357 , , s060421a042 93 15939 , v , 2135 1693 1823 S060421a044 s060421a055 94 49169 , , m . i. ,1,27454 i 1118, 94 1266^ .1141 , (1)328841 547 s060421a057 94 47071 338? ` (1)257946 946 s060421a068 95 53698' 2525 . 5237 1137 s060421a070 95 74125 . . 5907 6588 975 s060421a081 95 62139 2124 3945 1225 s060421a083 95 68329 3139 3951 1149 s060421a094 96 76799 4192 3512 10 5 4'. s060421a096 96 -, 77269, . 3358 3905 1173 s060421a107 97 14824 1166 852 335 - , s060421a109 97 19120 , 1763 1499 1289 s060421a120 97 , 9918 1028 . .1024 698 s060421a122 98 24599 1589 2321 3275 s060421a127 s060421a129 98 ' 99 37573' 18673 1305 f i . i , , ;, 1106 ' 6127 1909 2190 937 s060421a135 I 99 31743 1944 1472 632 LOQ Standard 163373 14600 13176 25766 Vi' LOQ Standard I 81687 7300 6588 12883 C ) Area counts of the solvent blank were greater than '/*the LOQ standard area counts. PAGE 21 OF 21 000023