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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-01 Final Report Analysis of PFOA, PFBS, PFHS, and PFOS in Aqueous Samples from 3M Decatur, Alabama: Groundwater Treatment Plant GAC System January 2013 Laboratory Request Number: ISO13-07-01 Method Requirement: 3M Method ETS-8-044.1 Report Date - Date of Last Signature Testing Laboratory 3M EHS&S Operations 3M Environmental Laboratory Building 260-5N-17 Maplewood, MN 55144-1000 Requester Gary Hohenstein 3M Building 224-5W-03 Saint Paul, MN 55144-1000 Phone: (651) 737-3570 The testing reported herein meet the requirements of ANSI/ISO/IEC 17025:2005 "General Requirements for the Competence of Testing and Calibration Laboratories", in accordance with the A2LA Testing Certificate # 2052.01. Testing that complies with this International Standard also meets principles of ISO 9001:2000. Testing Cert #2052.01 PAGE 1 OF 20 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-01 3M Environmental Laboratory 3M Environmental Laboratory Technical Director: William K. Reagen, Ph.D. 3M Principal Analytical Investigator: Susan Wolf Report Author: Chelsie Grochow Analytical Report ISO13-07-01 3M Decatur Groundwater Treatment Plant System; January 2013 Sampling Report Date: Date of Last Signature 1 Introduction/Summary The 3M Environmental Laboratory analyzed water samples from the groundwater treatment plant GAC system at the 3M Decatur, AL facility. Water samples were collected by Weston Solutions personnel on January 17, 2013. Samples were returned to the 3M Environmental Laboratory for analysis of Perfluorooctanoate (PFOA), Perfluorobutane sulfonate (PFBS), Perfluorohexane sulfonate (PFHS), Perfluorooctane sulfonate (PFOS), and the surrogate recovery standards 13C4-PFOA and 13C4-PFOS under laboratory project number ISO13-07-01. The 3M Environmental Laboratory provided sample containers for five sampling locations; ACI, ACM2, ACE, WW8R, and WW9R. The sample set consisted of a field sample, field sample duplicate and a field matrix spike. Each empty container was marked with a "fill to here" line that corresponded to a final volume of 200 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. Sample bottles for sampling locations ACM2 and ACE, along with the Trip Blank sample and low spike, were fortified with internal standards and surrogates prior to being sent to the field for sample collection. Samples were prepared and analyzed by method ETS-8-044.1 "Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis". Select internal standards were used to aid in the data quality objectives. 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. The testing reported herein meet the requirements of ANSI/ISO/IEC 17025:2005 "General Requirements for the Competence of Testing and Calibration Laboratories", in accordance with the A2LA Testing Certificate # 2052.01. Testing that complies with this International Standard also meets principles of ISO 9001:2000. Testing Cert #2052.01 PAGE 2 OF 20 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-01 Table 1. Sample Results Summary 3M LIMS ID Sample Description PFOA Concentration (ng/mL) ISO13-07-01-001 ISO13-07-01-002 ISO13-07-01-004 ISO13-07-01-005 ISO13-07-01-007 ISO13-07-01-008 ISO13-07-01-010 ISO13-07-01-011 ISO13-07-01-013 ISO13-07-01-014 DAL-GW-ACI; Sample DAL-GW-ACI; Sample Dup Average %RPD Sample/Sample Dup DAL-GW-ACM2; Sample DAL-GW-ACM2; Sample Dup Average %RPD Sample/Sample Dup DAL-GW-ACE; Sample DAL-GW-ACE; Sample Dup Average %RPD Sample/Sample Dup DAL-GW-WW8R; Sample DAL-GW-WW8R; Sample Dup Average %RPD Sample/Sample Dup DAL-GW-WW9R; Sample DAL-GW-WW9R; Sample Dup Average %RPD Sample/Sample Dup 1920 1890 1910 (1) 1.6 <0.0240 <0.0240 <0.0240 (2) NA <0.0240 <0.0240 <0.0240 (2) NA 4410 4290 4350 (1) 2.8 2670 2740 2710 (1) 2.6 PFBS Concentration (ng/mL) 600 575 588 (1) 4.3 1290 1250 1270 (1) 3.1 <0.0250 <0.0250 <0.0250 (2) NA 414 405 410 (1) 2.2 182 186 184 (1) 2.2 PFHS Concentration (ng/mL) 901 888 895 (1) 1.5 <0.0250 <0.0250 <0.0250 (23) NA <0.0250 <0.0250 <0.0250 (2) 3.4 1950 1900 1930 (1) 2.6 936 972 954 (1) 3.8 PFOS Concentration (ng/mL) 1830 1780 1810 (1) 2.8 <0.0232 <0.0232 <0.0232 (2) NA <0.0232 <0.0232 <0.0232 (2) NA 5840 5580 5710 (1) 4.6 3620 3760 3690 (1) 3.8 NA = Not Applicable (1) Reported results were prepared and analyzed by ETS-8-044.1 using external calibration. The analytical method uncertainties associated with the reported results are as follows: PFOA 19%, PFBS 16%, PFHS 17%, and PFOS 17%. (2) Reported results were prepared and analyzed by ETS-8-044.1 using internal calibration. The analytical method uncertainties associated with the reported results are as follows: PFOA 21 %, PFBS 23%, PFHS 21 %, and PFOS 19%. (3) The method uncertainty has been expanded for PFHS to 31%. See section 4 of the report for additional information. 2 Methods - Analytical and Preparatory 2.1 Methods Analysis was completed using 3M Environmental Laboratory Method ETS-8-044.1 "Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis". Table 2 Target Analytes. T arg et A nalytes Perfluorooctanoic Acid (C8 Acid) Perfluorobutanesulfonate (C4 Sulfonate ) Perfluorohexanesulfonate (C6 Sulfonate) Perfluorooctanesulfonate (C8 Sulfonate) A cronym PFOA PFBS PFHS PFOS R eference M aterial S tructure Linear + Branched Linear Linear Linear + Branched PAGE 3 OF 20 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-01 2.2 Sample Collection Samples were collected on January 17, 2013 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 PFOA, PFBS, PFHS, and PFOS. Sample bottles for sampling locations ACM2 and ACE, along with the Trip Blank sample and low spike, were fortified with a mixture of mass-labeled internal standards at a nominal concentration of 1 ng/mL and a mixture of surrogate recovery standards at a nominal concentration of 0.1 ng/mL. Collected sample bottles were received by the laboratory at ambient conditions on January 22, 2013. 2.3 Sample Preparation Sample sets ACI, ACM2, WW8R, WW9R, and the Trip Blank field matrix spikes were diluted 1:100 and analyzed for all analytes. The 1:100 dilutions were prepared by removing a 0.1 mL aliquot of the well mixed sample and adding 9.8 mL of methanol and 0.1 mL of a surrogate spiking solution. Prepared samples were analyzed by external standard calibration. The ACE sample set and the Trip Blank sample were prepared and analyzed for all analytes by removing a 0.4 mL aliquot of the well mixed sample and diluting it with 0.4 mL of methanol (dilution factor of 2). The ACM2 sample set and the Trip Blank low spike sample were re-analyzed using a 1:2 dilution. Prepared samples were analyzed by internal standard calibration. During the preparation of the laboratory control samples, an aliquot of a separate internal standard spiking solution was added to the laboratory control samples (nominal concentration of 1 ng/mL). The sample bottles were spiked with an internal standard mix at a nominal concentration of 1 ng/mL prior to being sent to the field for sample collection. The laboratory control samples were then diluted with methanol in the same manner as the ACE and Trip Blank samples. 2.4 Analysis All samples and quality control samples were analyzed for four 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. Due to the nature of the sample, the wide range of concentrations found in the sample, and the environmental occurrence of multiple isomers of the laboratory's analytes of interest, the software used for processing the analytical results is not able to consistently integrate the analytical peak, manual integration of the analytical peak is necessary. All manual integrations are performed following the procedures outlined in method ETS-12-010. The consistency of the laboratory's integration is ensured through the training of laboratory personnel, the peer review process required for all manual integrations, the review of manual integrations by the QAU, and where necessary the review of manual integrations by laboratory management. PAGE 4 OF 20 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-01 Table 3. Instrument Parameters. Instrument Name Analysis Dates Analytical Method Liquid Chromatograph Guard column Analytical column Injection Volume Mass Spectrometer Ion Source Polarity Software ETS Kirk 1/24/13 - external calibration ETS-8-044.1 Agilent 1260 Betasil C18 (4.6 mm X 100 mm), 5 x Betasil C18 (4.6 mm X 100 mm), 5 x 20 xL Applied Biosystems API 5500 Turbo Spray Negative Analyst 1.6.1 ETS Kirk 1/30/13 - internal calibration ETS-8-044.1 Agilent 1260 Betasil C18 (4.6 mm X 100 mm), 5 x Betasil C18 (4.6 mm X 100 mm), 5 x 40 xL Applied Biosystems API 5500 Turbo Spray Negative Analyst 1.6.1 Table 4. Liquid Chromatography Gradient Program. Step Number 0 1 2 3 4 5 6 7 8 9 Total Time (min) 0.00 0.50 4.00 6.00 11.0 13.0 13.5 16.0 16.5 19.0 Flow Rate (pL/min) 750 750 750 750 750 750 750 750 750 750 Percent A (2 m M ammonium acetate) 90.0 90.0 70.0 70.0 20.0 20.0 10.0 10.0 90.0 90.0 Percent B (Methanol) 10.0 10.0 30.0 30.0 80.0 80.0 90.0 90.0 10.0 10.0 Table 5. Mass Transitions Analyte Mass Transition Q1/Q3 Internal Standard(1> Mass Transition Q1/Q3 413/369 PFOA 413/219 [13Cs]PFOA 421/376 413/169 PFBS 299/80 299/99 [18O2]PFBS 303/84 PFHS 399/99 399/80 [13Cs]PFHS 402/80 499/99 PFOS 499/80 [13Cs]PFOS 507/80 499/130 [13C4]PFOA surrogate 417/372 [13Cs]PFOA 421/376 [13C4]PFOS surrogate 503/80 [13Cs]PFOS 507/80 Dwell time was 20 msec for each transition. The individual transitions were summed to produce a "total ion chromatogram" (TIC), which was used for quantitation. (1) Internal standards were used for the analysis on 1/30/13. PAGE 5 OF 20 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-01 3 Data Analysis 3.1 Calibration Internal Standard Calibration Analysis: Samples were analyzed against a matrix-matched stable isotope internal standard calibration curve. Calibration standards were prepared by spiking known amounts of stock solutions into 50 mL of 50:50 methanol:laboratory reagent water. The calibration standards contained an internal standard mix at a nominal concentration of 0.5 ng/mL. A total of twelve calibration standards ranging from 0.0125 ng/mL to 25 ng/mL (nominal) were analyzed with the prepared samples. O f these twelve calibration standards, ten contained the surrogates at concentrations ranging from 0.0125 ng/mL to 10 ng/mL nominal. A quadratic, 1/x weighted, calibration curve of the ratio of the standard peak area counts over the internal standard peak area counts was used to fit the data for each analyte. The data were not forced through zero during the fitting process. Calculating the standard concentrations using the peak area ratios and the resultant calibration curve confirmed accuracy of each curve point. The reference standards of PFOA and PFOS used to prepare the calibration standards consisted of both linear and branched isomers. Each curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method calibration accuracy requirements of 10025% (10030% for the lowest curve point) were met for all analytes. The correlation coefficient (r) was greater than 0.995 for all analytes. External Standard Calibration Analysis: Samples were analyzed against an external standard calibration curve. Calibration standards were prepared by spiking known amounts of the stock solution containing the target analytes into 90:10 Methanol:Milli-Q laboratory water. A total of twelve spiked standards ranging from 0.02 ng/mL to 100 ng/mL (nominal) were analyzed. Of these twelve calibration standards, ten contained the surrogates at concentrations ranging from 0.02 ng/mL to 25 ng/mL nominal. A quadratic, 1/x weighted, calibration curve of the standard peak area counts was used to fit the data for each analyte. The data were not forced through zero during the fitting process. Calculating the standard concentrations using the peak area counts and the resultant calibration curve confirmed accuracy of each curve point. Each curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method calibration accuracy requirements of 10025% (10030% for the lowest curve point) were met for all analytes. The correlation coefficient (r) was greater than 0.995 for all analytes. 3.2 System Suitability A calibration standard was analyzed four times at the beginning of the analytical sequence to demonstrate overall system suitability. The acceptance criteria for system suitability samples is less than or equal to 5% relative standard deviation (RSD) for peak area/ratio and retention time criteria of less than or equal to 2% RSD. These criteria were met for all analytes except for PFOA and PFOA surrogate analyzed using external calibration which had area counts RSDs of 6.3% and 6.2%, respectively. A method deviation is included with the raw data. 3.3 Limit of Quantitation (LOQ) The LOQ as defined in method ETS-8-044.1 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 LOQs associated with the sample analysis are listed in the table below. PAGE 6 OF 20 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-01 Table 6. LOQ Analyte PFOA PFBS PFHS PFOS PFOA PFBS PFHS PFOS Calibration Internal standard Internal standard Internal standard Internal standard External standard External standard External standard External standard LOQ, ng/mL 0.0240 (1) 0.0250 (1) 0.0250 (1) 0.0232 (1) 24.0 (2) 2.00 (2) 2.00 (2) 23.2 (2) (1) The dilution factor of 2 was applied to the LOQ. (2) The dilution factor of 100 was applied to the LOQ. 3.4 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. The method acceptance criteria of 100% 25% was met for all analytes. 3.5 Blanks Two types of blanks were prepared and analyzed with the samples: method blanks/solvent blanks and field/trip blanks. Each blank result was reviewed and used to evaluate method performance to determine the LOQ for each analyte. 3.6 Lab Control Spikes (LCSs) Low, mid, and high lab control spikes were prepared for the target analytes and analyzed in triplicate, while only low and high lab control spikes were prepared for the surrogates. LCSs were prepared by spiking known amounts of the analytes into either 10 mL of laboratory-prepared matrix matched water or 1 mL of Milli-Q water to produce the desired concentration. The LCSs were then diluted with methanol in the same manner as the samples. Method ETS-8-044.1 states that the average recovery of LCSs at each spiking level be within 80%-120% with a RSD <20%. All LCS samples met method accuracy criteria with the following exception: 1/30/13 Analysis (internal standard calibration): The high set of LCS samples for PFOA had an average recovery of 78.9% and PFHS had an average recovery of 79.2%. A method deviation is included with the raw data. All LCSs were used in the determination of the analytical method uncertainty in section 3.9. The following calculations were used to generate data in Table 7. Calculated Concentration * ____ _ LCS Percent Recovery -------------------------------------* 100% Spike Concentration standard deviation LCS replicates LCS% RSD = 100% average LCS recovery PAGE 7 OF 20 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-01 Table 7. Lab Control Spike Results. ETS-8-044.1 External Standard Calibration Analyzed 1/24/13 Lab ID LCS-130124-1 LCS-130124-2 LCS-130124-3 Average %RSD LCS-130124-4 LCS-130124-5 LCS-130124-6 Average %RSD LCS-130124-7 LCS-130124-8 LCS-130124-9 Average %RSD PFOA (Linear + Branched) Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) % R ecoveiy 0.479 0.479 0.479 0.46 0.46 0.46 96.1% 0.12% 96.0 96.0 96.2 4.79 5.67 118 4.79 5.60 117 4.79 5.62 117 117% 0.49% 19.1 20.5 107 19.1 19.9 104 19.1 19.5 102 104% 2.4% PFOS (Linear + Branched) Spiked Concentration (ng/mL) Calculated Concentration (ng/mL) %Recovery 0.464 0.464 0.464 0.45 0.44 0.443 95.8% 0.67% 96.5 95.3 95.5 4.64 5.32 4.64 5.29 4.64 5.37 115% 0.87% 115 114 116 18.5 20.4 18.5 19.7 18.5 19.3 107% 2.9% 110 106 104 ETS-8-044.1 External Standard Calibration Analyzed 1/24/13 Lab ID LCS-130124-1 LCS-130124-2 LCS-130124-3 Average %RSD LCS-130124-4 LCS-130124-5 LCS-130124-6 Average %RSD LCS-130124-7 LCS-130124-8 LCS-130124-9 Average %RSD Spiked Concentration (ng/mL) PFBS Calculated Concentration (ng/mL) 0.500 0.500 0.500 0.531 0.544 0.531 107% 1.6% 5.00 5.50 5.00 5.44 5.00 5.66 111% 1.9% 20.0 21.4 20.0 20.2 20.0 19.7 102% 4.2% %Recovery 106 109 106 110 109 113 107 101 98.6 Spiked Concentration (ng/mL) 0.500 0.500 0.500 5.00 5.00 5.00 20.0 20.0 20.0 PFHS Calculated Concentration (ng/mL) 0.545 0.524 0.528 107% 2.0% 5.30 5.25 5.38 106% 1.4% 19.6 18.6 18.2 94.1% 3.7% (1) LCSs did not meet acceptance criteria of 100 20%. %Recovery 109 105 106 106 105 108 97.9 93.2 91.2 PAGE 8 OF 20 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-01 Table 7 continued. Lab Control Spike Results. ETS-8-044.1 External Standard Calibration Analyzed 1/24/13 Lab ID LCS-130124-1 LCS-130124-2 LCS-130124-3 Average %RSD LCS-130124-4 LCS-130124-5 LCS-130124-6 Average %RSD Spiked Concentration (ng/mL) PFOA surrogate Calculated Concentration (ng/mL) 0.499 0.499 0.499 0.502 0.498 0.500 100% 0.64% 4.99 4.83 4.99 4.80 4.99 4.91 97.1% 1.1% %Recovery 101 99.8 100 96.8 96.2 98.3 Spiked Concentration (ng/mL) PFOS surrogate Calculated Concentration (ng/mL) 0.478 0.478 0.478 0.468 0.468 0.455 97.0% 1.6% 4.78 4.62 4.78 4.61 4.78 4.68 97.0% 0.76% %Recovery 97.8 97.9 95.2 96.7 96.4 97.8 ETS-8-044.1 Internal Standard Calibration Analyzed 1/30/13 Lab ID LCS-130130-1 LCS-130130-2 LCS-130130-3 Average %RSD LCS-130130-4 LCS-130130-5 LCS-130130-6 Average %RSD LCS-130130-7 LCS-130130-8 LCS-130130-9 Average %RSD PFOA (Linear + Branched) Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) %Recovery 0.190 0.190 0.190 0.162 0.161 0.167 85.8% 1.9% 85.1 84.6 87.7 1.90 1.57 82.8 1.90 1.60 84.5 1.90 1.54 81.1 82.8% 2.1% 19.0 15.7 82.6 19.0 13.9 73.1 19.0 15.4 81.1 78.9% 6.5% (1) PFOS (Linear + Branched) Spiked Concentration (ng/mL) Calculated Concentration (ng/mL) %Recovery 0.184 0.184 0.184 0.157 0.156 0.157 85.3% 0.38% 85.5 84.9 85.4 1.84 1.52 1.84 1.55 1.84 1.55 83.6% 0.83% 82.8 84.0 84.0 18.4 15.5 18.4 13.6 18.4 15.4 80.6% 7.0% 84.1 74.1 83.6 (1) LCSs did not meet acceptance criteria of 100 20%. PAGE 9 OF 20 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-01 Table 7 continued. Lab Control Spike Results. ETS-8-044.1 Internal Standard Calibration Analyzed 1/30/13 Lab ID LCS-130130-1 LCS-130130-2 LCS-130130-3 Average %RSD LCS-130130-4 LCS-130130-5 LCS-130130-6 Average %RSD LCS-130130-7 LCS-130130-8 LCS-130130-9 Average %RSD Spiked Concentration (ng/mL) PFBS Calculated Concentration (ng/mL) 0.198 0.198 0.198 0.173 0.165 0.170 85.6% 2.3% 1.98 1.62 1.98 1.67 1.98 1.65 83.2% 1.6% 19.9 16.8 19.9 14.8 19.9 16.3 80.2% 6.5% %Recovery 87.3 83.4 86.0 81.9 84.5 83.3 84.4 74.4 81.7 Spiked Concentration (ng/mL) PFHS Calculated Concentration (ng/mL) 0.198 0.198 0.198 0.170 0.164 0.172 85.2% 2.5% 1.98 1.64 1.98 1.61 1.98 1.64 82.3% 1.1% 19.9 16.6 19.9 14.5 19.9 16.1 79.2% 7.0% (1) %Recovery 86.1 82.7 86.7 82.7 81.2 82.9 83.5 72.9 81.1 ETS-8-044.1 Internal Standard Calibration Analyzed 1/30/13 Lab ID LCS-130130-7 LCS-130130-8 LCS-130130-9 Average %RSD LCS-130130-4 LCS-130130-5 LCS-130130-6 Average %RSD Spiked Concentration (ng/mL) PFOA surrogate Calculated Concentration (ng/mL) 0.198 0.198 0.198 0.186 0.187 0.185 93.8% 0.54% 1.98 1.78 1.98 1.82 1.98 1.75 90.0% 1.9% %Recovery 93.9 94.3 93.3 90.0 91.7 88.2 Spiked Concentration (ng/mL) PFOS surrogate Calculated Concentration (ng/mL) 0.189 0.189 0.189 0.173 0.173 0.168 90.7% 1.6% 1.89 1.69 1.89 1.71 1.89 1.72 90.3% 0.89% %Recovery 91.7 91.3 89.0 89.6 90.2 91.2 (1) LCSs did not meet acceptance criteria of 100 20%. PAGE 10 OF 20 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-01 3.7 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 a factor of 2, which corresponds to a confidence level of 95%. The method uncertainty was determined to be 19% for PFOA and 20% for PFHS using internal standard calibration, but based on the percent bias of the high level LCSs, the method uncertainty has been expanded for PFOA and PFHS. Table 8. Analytical Method Uncertainty. Analyte Calibration Method PFOA External Standard PFBS External Standard PFHS External Standard PFOS External Standard PFOA Internal Standard PFBS Internal Standard PFHS Internal Standard PFOS Internal Standard NA = Not Applicable Standard Deviation 9.36 7.88 8.28 8.60 NA 11.4 NA 9.66 Method Uncertainty 19% 16% 17% 17% 21% 23% 21% 19% 3.8 Field Matrix Spikes (FMS) A field matrix spike was 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. The standards used for the preparation of the field matrix spiking solutions contained reference materials comprised of both linear and branched isomers for PFOA and PFOS. Field matrix spikes are presented in section 4 of this report. FMS Recovery - (Sample Concentration of FMS - Average Concentration: Field Sample & Field Sample Dup.) * 1 0 0 % Spike Concentraton Table 9. Field Matrix Spike Concentrations Location ACI ACM2, ACE WW8R, WW9R Trip Blank Description Field Matrix Spike Field Matrix Spike Field Matrix Spike Low Field Matrix Spike High Field Matrix Spike Final Concentration (ng/mL PFOA PFBS PFHS PFOS 2020 1990 1970 2000 10.1 9.96 9.86 10.0 4040 3980 3940 4000 10.1 9.96 9.86 10.0 4040 3980 3940 4000 PAGE 11 OF 20 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-01 4 Data Summary and Discussion The tables below summarize the sample results and field matrix spike recoveries for the three locations as well as the Trip Blank. Each table provides the average concentration and the relative percent difference (%RPD) of the sample and sample duplicate. Results and average values are rounded to three significant figures. 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. DAL-GW-ACM2; the FMS sample (10 ng/mL) was not appropriate for PFBS; however, the FMS sample for PFOA, PFOS, and the surrogate recovery standards 13C4-PFOA and 13C4-PFOS, met method acceptance criteria. No additional QC samples were prepared. The FMS did not meet acceptance criteria for PFHS with a recovery of 69.1%. Since this is the only appropriate spike level, the sample method uncertainty will be expanded to 31% for PFHS. PAGE 12 OF 20 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-01 Table 10. DAL GW ACI 130117 (1) 3M LIMS ID Description ISO13-07-01-001 DAL-GW-ACI-0-130117 ISO13-07-01-002 DAL-GW-ACI-DB-130117 ISO13-07-01-003 DAL-GW-ACI-FMS-130117 Average Concentration (ng/mL) %RPD PFOA PFBS Concentration (ng/mL) %Recovery 1920 NA 1890 NA 4060 107 1910 ng/mL 1.6% Concentration (ng/mL) %Recovery 600 NA 575 NA 2660 104 588 ng/mL 4.3% 3M LIMS ID Description ISO13-07-01-001 DAL-GW-ACI-0-130117 ISO13-07-01-002 DAL-GW-ACI-DB-130117 ISO13-07-01-003 DAL-GW-ACI-FMS-130117 Average Concentration (ng/mL) %RPD PFHS PFOS Concentration (ng/mL) %Recovery 901 NA 888 NA 3020 108 895 ng/mL 1.5% Concentration (ng/mL) %Recovery 1830 NA 1780 NA 4140 117 1810 ng/mL 2.8% 13C4-PFOA 13C4-PFOS 3M LIMS ID Description ISO13-07-01-001 DAL-GW-ACI-0-130117 ISO13-07-01-002 DAL-GW-ACI-DB-130117 ISO13-07-01-003 DAL-GW-ACI-FMS-130117 Average Concentration (ng/mL) %RSD %Recovery 88.6 88.1 84.4 87.0% 2.6% %Recovery 95.9 93.8 87.9 92.5% 4.5% NA = Not Applicable (1) Samples were diluted 1:100 with methanol and analyzed by external standard calibration on 1/24/13. The surrogate recovery standards 13C4-PFOA and 13C4-PFOS were added to the samples during sample preparation. PAGE 13 OF 20 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-01 Table 11. DAL GW ACM2 130117 3M LIMS ID Description ISO13-07-01-004 DAL-GW-ACM2-0-130117 ISO13-07-01-005 DAL-GW-ACM2-DB-130117 ISO13-07-01-006 DAL-GW-ACM2-FMS-130117 Average Concentration (ng/mL) %RPD 3M LIMS ID Description ISO13-07-01-004 DAL-GW-ACM2-0-130117 ISO13-07-01-005 DAL-GW-ACM2-DB-130117 ISO13-07-01-006 DAL-GW-ACM2-FMS-130117 Average Concentration (ng/mL) %RPD P F O A (1) P F B S (2) Concentration (ng/mL) %Recovery <0.0240 NA <0.0240 NA 7.66 75.8 <0.0240 ng/mL Concentration (ng/mL) %Recovery 1290 NA 1250 NA 1250 NC 1270 ng/mL 3.1% P F H S (1) P F O S (1) Concentration (ng/mL) %Recovery <0.0250 NA <0.0250 NA 6.81 69.1 (3) <0.0250 ng/m L(4) Concentration (ng/mL) %Recovery <0.0232 NA <0.0232 NA 7.06 70.6 <0.0232 ng/mL 13C4-PFOA(1) 13C,tPFOS (1) 3M LIMS ID Description ISO13-07-01-004 DAL-GW-ACM2-0-130117 ISO13-07-01-005 DAL-GW-ACM2-DB-130117 ISO13-07-01-006 DAL-GW-ACM2-FMS-130117 Average Concentration (ng/mL) %RSD %Recovery 93.0 87.8 86.2 89.0% 4.0% %Recovery 91.1 86.7 86.6 88.1% 2.9% NA = Not Applicable NC = Not Calculated; Spike level was less than 0.5x the endogenous sample concentration. (1) Samples were diluted 1:2 with methanol and analyzed by internal standard calibration on 1/30/13. (2) Samples were diluted 1:100 with methanol and analyzed by external standard calibration on 1/24/13. (3) FMS did not meet acceptance criteria of 100 30%. (4) Method uncertainty has been expanded to 31 % for PFHS. PAGE 14 OF 20 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-01 Table 12. DAL GW ACE 130117 (1) 3M LIMS ID Description ISO13-07-01-007 DAL-GW-ACE-0-130117 ISO13-07-01-008 DAL-GW-ACE-DB-130117 ISO13-07-01-009 DAL-GW-ACE-FMS-130117 Average Concentration (ng/mL) %RPD 3M LIMS ID Description ISO13-07-01-007 ISO13-07-01-008 ISO13-07-01-009 DAL-GW-ACE-0-130117 DAL-GW-ACE-DB-130117 DAL-GW-ACE-FMS-130117 Average Concentration (ng/mL) %RPD PFOA PFBS Concentration (ng/mL) %Recovery <0.0240 NA <0.0240 NA 7.60 75.2 <0.0240 ng/mL Concentration (ng/mL) %Recovery <0.0250 NA <0.0250 NA 7.33 73.6 <0.0250 ng/mL PFHS PFOS Concentration (ng/mL) %Recovery <0.0250 <0.0250 7.15 NA NA 72.5 <0.0250 ng/mL Concentration (ng/mL) %Recovery <0.0232 <0.0232 7.38 NA NA 73.8 <0.0232 ng/mL 13C4-PFOA 13C4tPFOS 3M LIMS ID Description ISO13-07-01-007 DAL-GW-ACE-0-130117 ISO13-07-01-008 DAL-GW-ACE-DB-130117 ISO13-07-01-009 DAL-GW-ACE-FMS-130117 Average Concentration (ng/mL) %RSD %Recovery 82.9 84.4 87.2 84.8% 2.6% %Recovery 78.1 85.7 87.3 83.7% 5.9% NA = Not Applicable (1) Samples were diluted 1:2 with methanol and analyzed by internal standard calibration on 1/30/13. PAGE 15 OF 20 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-01 Table 13. DAL GW WW8R 130117 (1) 3M LIMS ID Description ISO13-07-01-010 DAL-GW-WW8R-0-130117 ISO13-07-01-011 DAL-GW-WW8R-DB-130117 ISO13-07-01-012 DAL-GW-WW8R-FMS-130117 Average Concentration (ng/mL) %RPD 3M LIMS ID Description ISO13-07-01-010 DAL-GW-WW8R-0-130117 ISO13-07-01-011 DAL-GW-WW8R-DB-130117 ISO13-07-01-012 DAL-GW-WW8R-FMS-130117 Average Concentration (ng/mL) %RPD PFOA PFBS Concentration (ng/mL) %Recovery 4410 NA 4290 NA 9070 117 4350 ng/mL 2.8% Concentration (ng/mL) %Recovery 414 NA 405 NA 4460 102 410 ng/mL 2.2% PFHS PFOS Concentration (ng/mL) %Recovery 1950 NA 1900 NA 5620 (2) 93.8 1930 ng/mL 2.6% Concentration (ng/mL) %Recovery 5840 NA 5580 NA 9390 (2) 92.0 5710 ng/mL 4.6% 13C4-PFOA 13C-PFO S 3M LIMS ID Description ISO13-07-01-010 DAL-GW-WW8R-0-130117 ISO13-07-01-011 DAL-GW-WW8R-DB-130117 ISO13-07-01-012 DAL-GW-WW8R-FMS-130117 Average Concentration (ng/mL) %RSD %Recovery 81.5 81.2 72.2 78.3% 6.7% %Recovery 86.3 83.8 86.9 (2) 85.7% 1.9% NA = Not Applicable (1) Samples were diluted 1:100 with methanol and analyzed by external standard calibration on 1/24/13. The surrogate recovery standards 13C4-PFOA and 13C4-PFOS were added to the samples during sample preparation. (2) Samples re-analyzed using a 1:400 dilution. PAGE 16 OF 20 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-01 Table 14. DAL GW WW9R 130117 (1) 3M LIMS ID Description ISO13-07-01-013 DAL-GW-WW9R-0-130117 ISO13-07-01-014 DAL-GW-WW9R-DB-130117 ISO13-07-01-015 DAL-GW-WW9R-FMS-130117 Average Concentration (ng/mL) %RPD 3M LIMS ID Description ISO13-07-01-013 ISO13-07-01-014 ISO13-07-01-015 DAL-GW-WW9R-0-130117 DAL-GW-WW9R-DB-130117 DAL-GW-WW9R-FMS-130117 Average Concentration (ng/mL) %RPD PFOA PFBS Concentration (ng/mL) %Recovery 2670 NA 2740 NA 6720 99.4 2710 ng/mL 2.6% Concentration (ng/mL) %Recovery 182 NA 186 NA 3980 95.4 184 ng/mL 2.2% PFHS PFOS Concentration (ng/mL) %Recovery 936 972 4520 (2) NA NA 90.5 954 ng/mL 3.8% Concentration (ng/mL) %Recovery 3620 3760 7310 (2) NA NA 90.5 3690 ng/mL 3.8% 13C4-PFOA 13C4-PFOS 3M LIMS ID Description ISO13-07-01-013 DAL-GW-WW9R-0-130117 ISO13-07-01-014 DAL-GW-WW9R-DB-130117 ISO13-07-01-015 DAL-GW-WW9R-FMS-130117 Average Concentration (ng/mL) %RSD %Recovery 85.2 89.4 75.7 834% 8.4% %Recovery 89.7 92.8 86.6 (2) 89.7% 34% NA = Not Applicable (1) Samples were diluted 1:100 with methanol and analyzed by external standard calibration on 1/24/13. The surrogate recovery standards 13C4-PFOA and 13C4-PFOS were added to the samples during sample preparation. (2) Samples re-analyzed using a 1:400 dilution. PAGE 17 OF 20 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-01 Table 15. Trip Blank Results 3M LIMS ID ISO13-07-01-016 ISO13-07-01-017 ISO13-07-01-018 Description DAL-GW-TRI P-0DAL-GW-TRIP-LS DAL-GW-TRIP-HS 3M LIMS ID ISO13-07-01-016 ISO13-07-01-017 ISO13-07-01-018 Description DAL-GW-TRIP-0DAL-GW-TRIP-LS DAL-GW-TRIP-HS PFOA PFBS Concentration (ng/mL) <0.0240 (1) 7.60 (1) 4300 (2) % R ecoveiy NA 75.2 106 Concentration (ng/mL) <0.0250 (1) 7.36 (1) 4020 (2) %Recovery NA 73.9 101 PFHS PFOS Concentration (ng/mL) <0.0250 (1) 7.44 (1) 3830 (23) %Recovery NA 75.5 97.2 Concentration (ng/mL) <0.0232 (1) 7.37 (1) 4430 (2) %Recovery NA 73.7 111 13C4-PFOA 13C4-PFOS 3M LIMS ID ISO13-07-01-016 ISO13-07-01-017 ISO13-07-01-018 Description DAL-GW-TRIP-0DAL-GW-TRIP-LS DAL-GW-TRIP-HS %Recovery 85.6 (1) 88.4 (1) 84.7 (2) %Recovery 82.9 (1) 85.0 (1) 85.8 (2) NA = Not Applicable (1) Samples were diluted 1:2 with methanol and analyzed by internal standard calibration on 1/30/13. (2) Sample was diluted 1:100 with methanol and analyzed by external standard calibration on 1/24/13. (3) Sample re-analyzed using a 1:400 dilution. PAGE 18 OF 20 3M ENVIRONMENTAL LABORATORY REPORT NO. IS013-07-01 5 Conclusion Laboratory control spikes were used to determine the analytical method accuracy and precision for all analytes. 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 using 3M Environmental Laboratory Method ETS-8044.1 "Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis". Analytical results are reported in Table 1 and 10-15 of this report. 6 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 Attachments Appendix A: Trend Data for Activated Carbon Influent (ACI) Appendix B: Trend Data for Activated Carbon Effluent (ACE) 8 Signatures William K. Reagen, Ph.D., 3M Environmental Laboratory Technical Director Date The 3M Environmental Laboratory's Quality Assurance Unit has audited the data and report for this This test report shall not be reproduced except in full, without written approval of the 3M Environmental Laboratory. PAGE 19 OF 20 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-01 Appendix A: Analyte T rend Data for select sampling points at the Decatur Ground Water T reatment Plant (GWTP) GAC System ACI (Activated Carbon Influent) - Sample Results in ng/mL ACI PFOA PFBS PFHS PFOS 6/17/2011 1410 1110 983 691 2/8/2012 1180 792 1100 782 6/29/2012 1650 1410 1460 964 8/28/2012 1410 1830 1390 172 12/14/2012 2580 723 1380 2810 ACE (Activated Carbon Effluent) - Sample Results in ng/mL 1/17/2013 1910 588 895 1810 ACE PFOA PFBS PFHS PFOS 6/17/2011 2.57 11.9 2.50 2.07 2/8/2012 1250 818 1240 741 8/28/2012 0.387 0.256 0.552 0.103 The ACE location was not sampled on 6/29/12. 12/14/2012 0.102 <0.0250 0.117 0.0376 1/17/2013 <0.0240 <0.0250 <0.0250 <0.0232 PAGE 20 OF 20