Document MJRwXr6B2ya6JVkV5YvQNdR0z

3M ENVIRONMENTAL LABORATORY REPORT NO. 07-0650 Final Report Analysis of PFBA, PFOA, PFBS, PFOS, FBSA, and FOSA in Aqueous Samples from 3M Decatur, Alabama 3M Decatur NPDES Permit Number AL0000205: Quarterly FC Monitoring of Outfall DSN001; 4th Quarter 2007 Sampling Laboratory Request Number: E07-0650 Method Requirement: 3M Method ETS-8-154.1 Report Date -December 10, 2007 Testing Laboratory 3M EHS Operations 3M Environmental Laboratory Building 260-5N-17 Maplewood, MN 55144-1000 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 1ir accredited] Certificate #2052-01 The testing reported herein meet the requirements of ISO/IEC17025-2005 "General Requirements for the Competence of Testing and Calibration Laboratories", in accordance with the A2LA Certificate #2052-01. Testing that complies with this International Standard also operate in accordance with ISO 9001/ISO 9002 (2000). PAGE 1 OF 11 3M ENVIRONMENTAL LABORATORY REPORT NO. E07-0650 3M Environmental Laboratory 3M Environmental Laboratory Technical Manager: William K. Reagen, Ph.D. 3M Principal Analytical Investigator and Report Author: Susan Wolf Analytical Report E07-0650 3M Decatur NPDES Permit Number AL0000205: Quarterly FC Monitoring of Outfall DSN001 ; 4thQuarter 2007 Sampling Report Date: December 10,2007 1 Introduction/Summary The 3M Environmental Laboratory prepared and analyzed outfall samples collected by Enersolv Corporation personnel on October 9, 2007, from 3M Decatur location DSN001. Samples were returned to the 3M Environmental Laboratory for analysis of Perfluorobutanoic acid (PFBA), Perfluorooctanoic acid (PFOA), Perfluorobutane sulfonate (PFBS), Perfluorooctane sulfonate (PFOS), Perfluorobutanesulfonylamide (FBSA) and Perfluorooctanesulfonylamide (FOSA) under laboratory project number E07-0650. The 3M Environmental Laboratory prepared sample containers for one sampling location. The sample set consisted of a field sample, field sample duplicate, low field spike, mid field spike, and high field spike. Each empty container was marked with a "fill 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. Samples were prepared and analyzed using ETS-8-154.3 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates in Water by Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry". Samples were initially extracted on October 29, 2007. Only the FBSA results from that run are reported, as the field matrix spikes did not meet acceptance criteria for the other analytes of interest. Samples were re-extracted on November 14, 2007 for PFBA, PFOA, PFBS, PFOS, and FOSA. Table 1 summarizes the sample results using the analytical method identified above. All results for quality control samples prepared and analyzed with the samples will be reported and discussed elsewhere in this report. I (CREDITED The testing reported herein meet the requirements of ISO/IEC17025-2005 "General Requirements for the Competence of Testing and Calibration Laboratories", in accordance with the A2LA Certificate #2052-01. Testing that complies with this International Standard also operate in accordance with ISO 9001/ISO 9002 (2000). Certificate #2052-01 PAGE 2 OF 11 3M ENVIRONMENTAL LABORATORY REPORT NO. E07-0650 Table 1. Sample Results Summary(1,2) 3M LIMS ID E07-0650-001 E07-0650-002 Sample Description PFBA PFOA PFBS Concentration Concentration Concentration (ng/mL) (ng/mL) (ng/mL) DSN001, Sample DSN001 Sample Duplicate Average %RPD Sample/Sample Dup 1.26 1.49 1.38 17 5.52 5.16 5.34 6.7 9.71 9.18 9.45 5.6 3M LIMS ID E07-0650-001 E07-0650-002 Sample Description PFOS FBSA FOSA Concentration Concentration Concentration (ng/mL) (ng/mL) (ng/mL) DSN001, Sample DSN001 Sample Duplicate Average %RPD Sample/Sample Dup 11.0 11.5 11.3 4.4 21.0 19.6 20.3 6.9 0.636 0.562 0.599 12 NA = Not Applicable (1) The analytical method uncertainties associated with the reported results are as follows: PFBA100% + 35%, PFOA100% 20%, PFBS 100% 21%, PFOS 100% 14%, FBSA 100% 30%, and FOSA 100% 19%. (2) Sample results for FBSA were reported from analysis performed on October 31,2007. Sample results for PFBA, PFOA, PFBS, PFOS, and FOSA were reported from analysis performed on November 14, 2007. 2 Methods - Analytical and Preparatory 2.1 Methods Analysis was completed following 3M Environmental Laboratory method ETS-8-154.3 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates in Water by Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry". 2.2 Sample Collection Samples were collected in NalgeneTM (high-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 laboratory at ambient conditions on October 10, 2007. 2.3 Sample Preparation All samples, calibration standards, and associated quality control samples were extracted using ETS-8154.3. 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). PAGE 3 OF 11 3M ENVIRONMENTAL LABORATORY REPORT NO. E07-0650 2.4 Analysis All samples and quality control samples were analyzed for seven target analytes using high performance liquid chromatography/ tandem mass spectrometry (HPLC/MS/MS). Pertinent instrument parameters, the liquid chromatography gradient program, and the specific mass transitions analyzed are described in the tables below. Table 2. Instrument Parameters. Instrument Name Analytical Method followed Liquid Chromatograph Guard column Analytical column Injection Volume Mass Spectrometer Ion Source Electrode Polarity Software ETS Stan ETS-8-154.3 Agilent 1100 Betasil C18 (2.1 m m X 50 mm), 5p Betasil C 18 (2.1 m m X 100 mm), 5p 5 nL Applied Biosystems API 4000 Turbo Spray Turbo ion electrode Negative Analyst 1.4.2 Table 3. Liquid Chromatography Gradient Program. Step Number 0 1 2 3 4 5 Total Time (m in ) 0 2.0 14.5 15.5 16.5 20.0 Flow Rate (fjL/min) 300 300 300 300 300 300 Percent A (2 m M am m onium acetate) 90.0 90.0 10.0 10.0 90.0 90.0 Percent B (M e th a n o l) 10.0 10.0 90.0 90.0 10.0 10.0 Table 4. Mass Transitions A n a ly te PFBA PFOA PFBS PFOS FBSA FOSA M ass Transition Q 1/Q 3 213/169 413/369 413/219 413/169 299/80 299/99 499/99 499/80 499/130 298/78 498/78 PAGE 4 OF 11 3M ENVIRONMENTAL LABORATORY REPORT NO. E07-0650 3 Data Analysis 3.1 Calibration Calibration standards were prepared by spiking known amounts of stock solutions containing the analytes of interest into 40 ml_ of laboratory reagent water. Each spiked water standard was then extracted in the same manner as the collected samples. A total of twelve spiked standards ranging from 0.025 ng/ml_ to 25 ng/mL (nominal) were prepared. A quadratic, 1/x weighted, calibration curve was used to fit the data for each analyte. The data were not forced through zero during the fitting process. Calculating the standard concentration using the peak area counts and the resultant calibration curve confirmed accuracy of each curve point. Each curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method calibration accuracy requirements of 100+25% (10030% for the lowest curve point) were met. The correlation coefficient (r) was greater than 0.995 for all anlaytes. 3.2 Limit of Quantitation (LOQ) The LOQ as defined in method ETS-8-154.3 is the lowest non-zero calibration standard in the curve that meets linearity and accuracy requirements and for which the area counts are at least twice those of the appropriate blanks. The nominal LOQ for PFOA, PFOS, FBSA and FOSA was 0.025 ng/mL, 0.030 ng/mL for PFBS, and 0.050 ng/mL for PFBA. 3.3 Continuing Calibration During the course of the analytical sequence, several continuing calibration verification samples (CCVs) were analyzed to confirm that the instrument response and the initial calibration curve were still in control. Method acceptance criteria is 100% 25%. All CCVs met method criteria. 3.4 Blanks Three types of blanks were prepared and analyzed with the samples: method blanks, solvent blanks, and field/trip blanks. Each blank result is reviewed and used to evaluate method performance to determine the LOQ for each analyte. 3.5 Lab Control Spikes (LCSs) 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 laboratory reagent water to produce the desired concentration. The spiked water samples were then extracted and analyzed in the same manner as the samples. The method acceptance criteria states that the average recovery be between 80% 120% with a RSD <20%. All LCS samples met method acceptance criteria with the exception of one high LCS for FBSA which had a recovery of 46.6%. This was determined to be a sample preparation error and therefore, was not used in the determination of average and RSD. LCS were used in the determination of analytical uncertainty. The following calculations were used to generate data in Table 5. LCS Percent Recovery Calculated Concentration --------------------------------------- 100% Spike Concentration LCS% RSD = i ^ d a r d deviation LCS replicates . 10Q% average LCS recovery PAGE 5 OF 11 3M ENVIRONMENTAL LABORATORY REPORT NO. E07-0650 Table 5. Lab Control Spike Results. PFBA Lab ID S p ik e d Calculated Concentration Concentration (n g /m L ) (n g /m L ) LCS-071114-1 LCS-071114-2 LCS-071114-3 LCS-071114-4 LCS-071114-5 LCS-071114-6 Average %RSD 0.201 0.201 0.201 5.02 5.02 5.02 0.200 0.196 0.210 5.49 5.21 5.28 103% 4.4 % R eco very 99.5 97.6 105 109 104 105 PFOA Spiked Calculated Concentration Concentration (n g /m L ) (ng /m L ) 0.199 0.199 0.199 4.98 4.98 4.98 0.227 0.219 0.222 5.03 5.09 5.27 108% 15.5% PFBS VoRecovery Spiked Calculated Concentration Concentration (ng /m L ) (ng /m L ) 114 0.199 0.230 110 0.199 0.219 112 0.199 0.211 101 4.99 4.75 102 4.99 4.72 106 4.99 5.09 104% 8.7% VoRecovery 115 110 106 95.2 94.5 102 PFOS FOSA FBSA Lab ID S p ik e d Calculated Concentration Concentration (ng /m L ) (ng /m L ) VoRecovery S p ik e d Calculated Concentration Concentration (ng /m L ) (n g /m L ) VoRecovery Lab ID S p ik e d Calculated Concentration Concentration (n g /m L ) (ng /m L ) VoRecovery LCS-071114-1 0.200 0.210 105 0.199 0.217 109 LCS-071029-1 0.201 0.211 105 LCS-071114-2 LCS-071114-3 0.200 0.200 0.208 0.207 104 104 0.199 0.199 0.216 0.208 109 LCS-071029-2 105 LCS-071029-3 0.201 0.201 0.200 0.208 99.5 104 LCS-071114-4 LCS-071114-5 LCS-071114-6 5.00 5.00 5.00 4.77 4.85 4.99 95.5 97.0 99.8 4.97 4.97 4.97 4.26 4.20 4.87 85.6 84.4 98.0 LCS-071029-4 LCS-071029-5 LCS-071029-6 5.02 5.02 5.02 4.50 4.62 2.34 89.6 92.0 46.6(1) Average %RSD 101% 4.4% 98.6% 13% 98.0% 7.1% (1) Results of other analytes analyzed from this sample that were not reported, indicate that this control sample was prepared in error and therefore, not used on the determination of average and RSD. It also was not used in the determination of method uncertainty. PAGE 6 OF 11 3M ENVIRONMENTAL LABORATORY REPORT NO. 07-0650 3.6 Analytical Method Uncertainty Analytical uncertainty Is based on historical QC data that is control charted and used to evaluate method accuracy and precision. The method uncertainty is calculated following ETS-12-012.2. The standard deviation is calculated for the set of accuracy results (in %) obtained for the QC samples. The expanded uncertainty is calculated by multiplying the standard deviation by factor of 2, which correspond with a confidence level of 95%. A minimum of twenty data points is needed to determine method uncertainty by this method. In the case of FBSA, where there was an insufficient number of laboratory control samples available, field matrix spike recoveries were used to determine analytical uncertainty. As the field matrix spikes meet the acceptance criteria of 100% 30% in this project, the FBSA results herein were assigned an analytical uncertainty of 30%. Analyte Number of data points used for determining uncertainty PFBA 50 PFOA 50 PFBS 50 PFOS 50 FBSA NA FOSA 24 NA = Not Applicable (1) Field matrix spikes were used to assign uncertainty. Standard Deviation 17.5 10.1 10.6 6.81 NA 9.68 Method Uncertainty 100%+35% 100%20% 100%21 % 100%14% 100%30%(1) 100%19% 3.7 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 sample 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 the section 4 of this report. FMS Recovery = (Sample Concentration of FMS - Average Concentration: Field Sample & Field Sample Dup.) 100% Spike Concentraton PAGE 7 OF 11 3M ENVIRONMENTAL LABORATORY REPORT NO. E07-0650 Table 6. Field Matrix Spike Concentrations Location Description Low Field Matrix Spike DSN001 Mid Field Matrix Spike High Field Matrix Spike Low Field Matrix Spike Trip Blank Mid Field Matrix Spike High Field Matrix Spike Final Concentration (ng/mL) PFBA PFOA PFBS PFOS FBSA FOSA 0.251 0.249 0.249 0.252 0.251 0.249 5.02 4.98 4.99 5.04 5.02 4.97 100 99.5 99.7 100 100 99.4 0.251 0.249 0.249 0.252 0.251 0.249 5.02 4.98 4.99 5.04 5.02 4.97 100 99.5 99.7 100 100 99.4 4 Data Summary and Discussion The tables below summarize the sample results and field matrix spike recoveries for sample location DSN001 as well as the Trip Blank. An equipment blank sample was also collected in the field. The table provides the average concentration and the relative percent difference (RPD) of the sample and sample duplicate. Results and average values are rounded to three significant 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 listed in the raw data. Field matrix spikes meeting the method acceptance criteria of 30%, demonstrate that the method is appropriate for the given matrix. Trip Blank - The low and high FMS recoveries for FOSA did not meet method acceptance criteria, with recoveries of 60.4% and 54.4%, respectively. However, the sample FMS recoveries did meet method acceptance criteria for FOSA, therefore, no further action was taken. PAGE 8 OF 11 3M ENVIRONMENTAL LABORATORY REPORT NO. E07-0650 Table 7. DSN001 Results 3M LIM S ID Description E07-0650-001 E07-0650-002 E07-0650-003 E07-0650-004 E07-0650-005 DSN001, Sample DSN001, Sample Duplicate DSN001, Field Matrix Spike Low DSN001, Field Matrix Spike Mid DSN001, Field Matrix Spike High Average Concentration (ng/mL) % RPD PFBA PFOA PFBS C o n c e n tra tio n (ng /m L ) % R ecovery 1.26 NA 1.49 1.34 4.95 87.7 NA NC 71.1 85.9 1.38 ng/m L 1 7 % Concentration (ng /m L ) % R ecovery 5.52 NA 5.16 5.27 9.59 114 NA NC 85.4 109 5.34 ng/m L 6 .7% C o n c e n tra tio n (ng /m L ) 9.71 % R eco verv NA 9.18 NA 9.46 NC 14.5 101 112 103 9.45 ng/m L 5 .6% PFOS FBSA FOSA 3 M LIM S ID D e s c rip tio n E07-0650-001 E07-0650-002 E07-0650-003 E07-0650-004 E07-0650-005 DSN001, Sample DSN001, Sample Duplicate DSN001, Field Matrix Spike Low DSN001, Field Matrix Spike Mid DSN001, Field Matrix Spike High Average Concentration (ng/mL) %RPD C o n c e n tra tio n (ng /m L ) % R eco very 11.0 NA 11.5 NA 10.9 NC 15.9 92.4 111 99.7 11.3 ng/m L 4 .4 % C o n c e n tra tio n (ng /m L ) 21.0 % R eco very NA 19.6 18.7 27.2 123 NA NC NC 102 20.3ng/m L 6.9% C o n c e n tra tio n (ng /m L ) % R eco very 0.636 NA 0.562 NA 0.870 6.38 108 NC 116 108 0.599 ng/m L 1 2 % NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. PAGE 9 OF 11 3M ENVIRONMENTAL LABORATORY REPORT NO. E07-0650 Table 8. Trip Blank Results 3M LIM S ID E07-0650-009 E07-0650-006 E07-0650-007 E07-0650-008 E07-0650-010 Description Trip Blank Sample Trip Blank FMS Low Trip Blank FMS Mid Trip Blank FMS High Equipment Blank PFBA PFOA PFBS C o n c e n tra tio n (ng /m L ) <0.0502 0.271 5.44 114 <0.0502 % R ecovery NA NA 108 113 NA C o n c e n tra tio n (ng /m L ) <0.0249 0.277 5.43 104 <0.0249 % R ecovery NA 111 109 105 NA C o n c e n tra tio n (ng /m L ) <0.0299 0.285 5.33 93.4 <0.0299 % R eco very NA 114 107 93.7 NA 3M L IM S ID D e s c rip tio n E07-0650-009 Trip Blank Sample E07-0650-006 Trip Blank FMS Low E07-0650-007 Trip Blank FMS Mid E07-0650-008 Trip Blank FMS High E07-0650-010 Equipment Blank PROS FBSA FOSA C o n c e n tra tio n (ng /m L ) <0.0250 0.254 5.51 104 <0.0250 C o n c e n tra tio n VoRecoverv (n g /m L ) NA <0.0251 101 0.232 109 4.42 104 108 NA <0.0251 % R eco verv NA 92.5 88.1 108 NA Concentration (ng /m L ) <0.0249 0.150 3.57 54.1 <0.0249 VoRecovery NA 60.4(,) 71.8 54.4(1) NA N/A = Not Applicable (1) Field matrix spike did not meet method acceptance criteria of 100% + 30%. PAGE 10 OF 11 3M ENVIRONMENTAL LABORATORY REPORT NO. E07-0650 5 Conclusion Laboratory control spikes were used to determine the analytical method accuracy and precision for all analytes, except for FBSA for which field matrix spikes were used. 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 completed following 3M Environmental Laboratory method ETS-8-154.3 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates in Water by Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry". Analytical results are reported in Table 1 of this report. g Data / Sample Retention All remaining sample and associated project data (hardcopy and electronic) will be archived according to 3M Environmental Laboratory standard operating procedures. 7 Signatures The 3M Environmental Laboratory's Quality Assurance Unit has audited the data and report for this project. Quality Assurance Representative / A . / i - o -) Date PAGE 11 OF 11