Document ZzaELMvZJBvV3DQrggN5zVe8

3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-08 Final Report Analysis of PFOA, PFBS, PFHS, and PFOS in Aqueous Samples from 3M Decatur, Alabama: Groundwater Treatment Plant GAC System September 2013 Laboratory Request Number: ISO13-07-08 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. Additionally, the laboratory's quality system has been audited and was determined to be in conformance with the EPA GLPs (40 CFR 792) by an independent A2LA assessment. PAGE 1 OF 23 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-08 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 ISO13-07-08 3M Decatur Groundwater T reatment Plant System; September 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 September 30, 2013. Samples were returned to the 3M Environmental Laboratory for analysis of Perfluorooctanoate (PFOA), Perfluorobutane sulfonate (PFBS), Perfluorohexane sulfonate (PFHS), Perfluorooctane sulfonate (PFOS) under laboratory project number ISO13-07-08. Analysis of the samples was completed as specified under 3M Environmental Laboratory General Project Outline (GPO) number GPO11-1006. The 3M Environmental Laboratory provided sample containers for seven sampling locations; ACI, ACM2, ACE, WW8R, WW9R, WW10R, and WW11R. 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. PAGE 2 OF 23 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-08 Table 1. Sample Results Summary 3M LIMS ID Sample Description ISO13-07-08-001 ISO13-07-08-002 ISO13-07-08-004 ISO13-07-08-005 ISO13-07-08-007 ISO13-07-08-008 ISO13-07-08-010 ISO13-07-08-011 ISO13-07-08-013 ISO13-07-08-014 ISO13-07-08-019 ISO13-07-08-020 ISO13-07-08-022 ISO13-07-08-023 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 DAL-GW-WW10R; Sample DAL-GW-WW10R; Sample Dup Average %RPD Sample/Sample Dup DAL-GW-WW11R; Sample DAL-GW-WW11R; Sample Dup Average %RPD Sample/Sample Dup PFOA Concentration (ng/mL) 2280 2350 2320 (1) 3.0 1210 1220 1220 (1) 0.82 0.109 0.121 0.115 (2) 10 2890 2890 2890 (1) 0.0 2740 2720 2730 (1) 0.73 2040 2090 2070 (1) 2.4 1700 1730 1720 (1) 1.7 PFBS Concentration (ng/mL) 349 363 356 (1) 3.9 468 471 470 (1) 0.64 1920 1980 1950 (1) 3.1 309 296 303 (1) 4.3 252 245 249 (1) 2.8 244 250 247 (1) 2.4 297 301 299 (1) 1.3 PFHS Concentration (ng/mL) 1370 1420 1400 (1) 3.6 1550 1570 1560 (1) 1.3 0.157 0.154 0.156 (2) 1.9 1360 1370 1370 (1) 0.73 1230 1210 1220 (1) 1.6 1020 1040 1030 (1) 1.9 1010 993 1000 (1) 1.7 PFOS Concentration (ng/mL) 3170 3310 3240 (1) 4.3 1.31 1.29 1.30 (2) 1.5 0.0419 0.0485 0.0452 (2) 15 4110 4090 4100 (1) 0.49 4130 4270 4200 (1) 3.3 2760 2780 2770 (1) 0.72 2190 2210 2200 (1) 0.91 (1) Reported results were prepared and analyzed by ETS-8-044.1 using external standard calibration. The analytical method uncertainties associated with the reported results are as follows: PFOA 14%, PFBS 13%, PFHS 12%, and PFOS 16%. (2) Reported results were prepared and analyzed by ETS-8-044.1 using internal standard calibration. The analytical method uncertainties associated with the reported results are as follows: PFOA 13%, PFHS 14%, and PFOS 15%. PAGE 3 OF 23 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-08 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 Target Analytes Perfluorooctanoic Acid (C8 Acid) Perfluorobutanesulfonate (C4 Sulfonate ) Perfluorohexanesulfonate (C6 Sulfonate) Perfluorooctanesulfonate (C8 Sulfonate) Acronym PFOA PFBS PFHS PFOS Reference Material Structure Linear + Branched Linear Linear Linear + Branched 2.2 Sample Collection Samples were collected on September 30, 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 October 9, 2013. The sample bottles for locations ACI, ACM2, ACE, WW8R, WW9R and the Trip Blank samples were prepared on August 20, 2013. Sample bottles for locations WW10R and WW11R were prepared on September 24, 2013. All sample bottles were prepared with spiking solutions that expired on September 29, 2013, just prior to sample collection on September 30, 2013. A deviation is included with the raw data. 2.3 Sample Preparation All samples were diluted with methanol and analyzed for all analytes. Samples diluted 1:10 were prepared by removing a 1 mL aliquot of the well mixed sample and adding 8.9 mL of methanol and 0.1 mL of a surrogate spiking solution. 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 and ACM2 sample sets and the Trip Blank sample were prepared and analyzed for all analytes by transferring an aliquot of the well mixed sample into an autovial. Prepared samples were analyzed by internal standard calibration. During the preparation of the laboratory control samples for internal standard calibration, 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 for ACE, ACM2, and Trip Blank 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 analyzed in the same manner as the 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. PAGE 4 OF 23 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-08 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. 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 10/15/13 - external standard calibration 10/16/13 - internal standard 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 5 or 20 xL Applied Biosystems TripleQuad 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 (uL/min) 750 750 750 750 750 750 750 750 750 750 Percent A (2 mM 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 PAGE 5 OF 23 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-08 Table 5. Mass Transitions. Analyte Mass Transition Q1/Q3 Internal Standard (1) Mass Transition Q1/Q3 413/369 PFOA 413/219 413/169 [1 3 C8 ]PFOA 421/376 PFBS 299/80 299/99 NA NA PFHS 399/99 399/80 [13Cs]PFHS 402/80 499/99 PFOS 499/80 [1 3 C8 ]PFOS 507/80 499/130 [13C4]PFOA surrogate [13C4]PFOS surrogate 417/372 503/80 [1 3 C8 ]PFOA [1 3 C8 ]PFOS 421/376 507/80 NA=Not applicable 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 of sampling locations ACM2, ACE, and the Trip Blank sample on 10/16/13. 3 Data Analysis 3.1 Calibration External Standard Calibration Analysis on 10/15/13: 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 eleven spiked standards ranging from 0.02 ng/mL to 50 ng/mL (nominal) were analyzed. The standards also 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. Internal Standard Calibration Analysis on 10/16/13: 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 laboratory prepared reagent water. The calibration standards contained an internal standard mix at a nominal concentration of 1 ng/mL. A total of thirteen calibration standards ranging from 0.025 ng/mL to 25 ng/mL (nominal) were analyzed with the prepared samples. Of these thirteen calibration standards, eleven contained the surrogates at concentrations ranging from 0.025 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. For each calibration curve, 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. PAGE 6 OF 23 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-08 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. 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 Table 6. Table 6. LOQ Analyte Calibration LOQ, ng/mL PFOA Internal standard 0.0240 PFHS Internal standard 0.0400 PFOS Internal standard 0.0232 PFOA External standard 0.0192 (1) PFBS External standard 0.0200 (1) PFHS External standard 0.0200 (1) PFOS External standard 0.0185 (1) (1) The dilution factor was not 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. When applicable, 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. All LCSs were used in the determination of the analytical method uncertainty in section 3.7. The following calculations were used to generate data in Table 7. LCS Percent Recovery -C--a--l-c-u--l-a--t-e-d---C--o--n--c--e-n--t-r-a--t-i-o-n--**1. 00% Spike Concentration LC S% RSD = standard deviation LC S replicates *ioo% average LC S recovery PAGE 7 OF 23 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-08 Table 7. Lab Control Spike Results. ETS-8-044.1 External Standard Calibration Analyzed 10/15/13 Lab ID PFOA (Linear + Branched) Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) %Recovery LCS-131015-1 LCS-131015-2 LCS-131015-3 Average %RSD LCS-131015-4 LCS-131015-5 LCS-131015-6 Average %RSD 0.191 0.191 0.191 4.74 4.74 4.74 0.200 0.207 0.224 110% 5.6% 5.39 5.36 5.32 113% 0.88% 105 109 117 114 113 112 LCS-131015-7 LCS-131015-8 LCS-131015-9 Average %RSD 38.2 38.2 38.2 40.8 37.5 37.5 101% 5.0% 107 98.2 98.3 Spiked Concentration (ng/mL) PFOA surrogate Calculated Concentration (ng/mL) 0.199 0.199 0.199 0.216 0.219 0.193 105% 6.8% 4.94 5.35 4.94 5.37 4.94 5.43 109% 0.92% %Recovery 109 110 97.2 108 109 110 ETS-8-044.1 External Standard Calibration Analyzed 10/15/13 Lab ID Spiked Concentration (ng/mL) PFBS Calculated Concentration (ng/mL) LCS-131015-1 LCS-131015-2 LCS-131015-3 Average %RSD LCS-131015-4 LCS-131015-5 LCS-131015-6 Average %RSD LCS-131015-7 LCS-131015-8 LCS-131015-9 Average %RSD 0.199 0.199 0.199 4.95 4.95 4.95 39.8 39.8 39.8 0.226 0.223 0.235 114% 2.8% 5.55 5.61 5.47 112% 1.4% 42.6 38.7 38.4 100% 5.9% %Recovery 113 112 118 112 113 110 107 97.2 96.4 Spiked Concentration (ng/mL) 0.199 0.199 0.199 4.95 4.95 4.95 39.8 39.8 39.8 PFHS Calculated Concentration (ng/mL) 0.220 0.218 0.228 111% 2.9% 5.61 5.56 5.50 112% 0.89% 42.5 39.4 38.6 101% 5.2% %Recovery 110 109 115 113 112 111 107 99.1 97.0 PAGE 8 OF 23 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-08 Table 7 continued. Lab Control Spike Results. ETS-8-044.1 External Standard Calibration Analyzed 10/15/13 Lab ID PFOS (Linear + Branched) Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) %Recovery LCS-131015-1 LCS-131015-2 LCS-131015-3 Average %RSD LCS-131015-4 LCS-131015-5 LCS-131015-6 Average %RSD 0.185 0.185 0.185 4.59 4.59 4.59 0.210 0.213 0.217 115% 1.3% 5.34 5.28 5.24 115% 0.87% 114 115 117 116 115 114 LCS-131015-7 LCS-131015-8 LCS-131015-9 Average %RSD 36.9 36.9 36.9 40.3 37.1 36.4 103% 5.3% 109 101 98.6 Spiked Concentration (ng/mL) PFOS surrogate Calculated Concentration (ng/mL) 0.190 0.190 0.190 0.206 0.213 0.193 107% 5.2% 4.73 5.26 4.73 5.23 4.73 5.30 111% 0.52% %Recovery 108 112 101 111 111 112 ETS-8-044.1 Internal Standard Calibration Analyzed 10/16/13 Lab ID PFOA (Linear + Branched) Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) %Recovery LCS-131016-1 LCS-131016-2 LCS-131016-3 Average %RSD LCS-131016-4 LCS-131016-5 LCS-131016-6 Average %RSD 0.190 0.190 0.190 1.90 1.90 1.90 0.187 0.204 0.194 103% 4.1% 2.07 2.01 1.98 106% 2.4% 98.5 107 102 109 106 104 LCS-131016-7 LCS-131016-8 LCS-131016-9 Average %RSD 19.0 19.0 19.0 19.7 18.5 19.1 101% 3.2% 104 97.6 100 Spiked Concentration (ng/mL) PFOA surrogate Calculated Concentration (ng/mL) 0.198 0.198 0.198 0.185 0.193 0.195 96.5% 2.7% 1.98 2.11 1.98 1.97 1.98 1.97 102% 3.6% %Recovery 93.6 97.5 98.5 106 99.6 99.6 PAGE 9 OF 23 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-08 Table 7 continued. Lab Control Spike Results. ETS-8-044.1 Internal Standard Calibration Analyzed 10/16/13 Lab ID Spiked Concentration (ng/mL) PFHS Calculated Concentration (ng/mL) LCS-131016-1 LCS-131016-2 LCS-131016-3 Average %RSD LCS-131016-4 LCS-131016-5 LCS-131016-6 Average %RSD 0.198 0.198 0.198 1.98 1.98 1.98 0.200 0.212 0.193 102% 4.7% 2.13 2.09 1.99 105% 4.0% LCS-131016-7 LCS-131016-8 LCS-131016-9 Average %RSD 19.9 19.9 19.9 20.9 19.2 19.7 100% 4.3% %Recovery 101 107 97.6 108 106 100 105 96.6 99.0 PFOS (Linear + Branched) Spiked Concentration (ng/mL) Calculated Concentration (ng/mL) %Recovery 0.184 0.184 0.184 0.195 0.202 0.185 105% 4.8% 106 110 100 1.84 1.97 1.84 1.93 1.84 1.92 106% 1.1% 107 105 105 18.4 18.5 18.4 17.8 18.4 17.7 97.6% 2.2% 100 96.7 96.0 ETS-8-044.1 Internal Standard Calibration Analyzed 10/16/13 Lab ID Spiked Concentration (ng/mL) PFOS surrogate Calculated Concentration (ng/mL) LCS-131016-1 LCS-131016-2 LCS-131016-3 Average %RSD 0.189 0.189 0.189 0.185 0.194 0.200 102% 4.0% LCS-131016-4 LCS-131016-5 LCS-131016-6 Average %RSD 1.89 1.89 1.89 1.99 1.83 1.93 101% 4.1% %Recovery 98.0 103 106 105 96.9 102 PAGE 10 OF 23 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-08 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%. Table 8. Analytical Method Uncertainty. Analyte PFOA PFBS PFHS PFOS PFOA PFHS PFOS Calibration Method External Standard External Standard External Standard External Standard Internal Standard Internal Standard Internal Standard Standard Deviation (%) 6.87 6.72 5.90 8.04 6.43 7.09 7.37 Method Uncertainty 14% 13% 12% 16% 13% 14% 15% 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 =(-S--a--m--p"le---C--o--n--c-e--n--tr--a-t-i-o-n---o--f-F--M---S------A--v-e--r-a--g-e---C---o-n--c--e--n-t-r-a--t-i-o-n--:-F--i-e--ld---S--a-m---p"le---&---F--ie--l-d--S--a--m--p"le---D--u-p--.) * 100% 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 Field Matrix Spike Low Field Matrix Spike High Field Matrix Spike Final Concentration (ng/mL) PFOA PFBS PFHS PFOS 2000 2010 2000 1990 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 2510 2510 2500 2490 5.00 5.00 5.00 5.00 2510 2510 2500 2490 PAGE 11 OF 23 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-08 4 Data Summary and Discussion The tables below summarize the sample results and field matrix spike recoveries for the five 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. All field matrix spike samples and surrogate recovery standards met method acceptance criteria except where noted below. DAL-GW-ACM2; the FMS sample (5 ng/mL) was not appropriate for PFOA, PFBS, or PFHS; however, the surrogate recovery standards 13C4-PFOA and 13C4-PFOS met method acceptance criteria. No additional QC samples were prepared. DAL-GW-ACE; the FMS sample (5 ng/mL) was not appropriate for PFBS; however, the surrogate recovery standard 13C4-PFOS, met method acceptance criteria. No additional QC samples were prepared. PAGE 12 OF 23 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-08 Table 10. DAL GW ACI 130930 (1) 3M LIMS ID Description ISO13-07-08-001 DAL-GW-ACI-0-130930 ISO13-07-08-002 DAL-GW-ACI-DB-130930 ISO13-07-08-003 DAL-GW-ACI-FMS-130930 Average Concentration (ng/mL) %RPD PFOA PFBS Concentration (ng/mL) %Recovery 2280 NA 2350 NA 4230 95.5 2320 ng/mL 3.0% Concentration (ng/mL) %Recovery 349 NA 363 NA 2310 97.2 356 ng/mL 3.9% 3M LIMS ID Description ISO13-07-08-001 DAL-GW-ACI-0-130930 ISO13-07-08-002 DAL-GW-ACI-DB-130930 ISO13-07-08-003 DAL-GW-ACI-FMS-130930 Average Concentration (ng/mL) %RPD PFHS PFOS Concentration (ng/mL) %Recovery 1370 NA 1420 NA 3700 115 1400 ng/mL 3.6% Concentration (ng/mL) %Recovery 3170 NA 3310 NA 4850 80.9 3240 ng/mL 4.3% 13C4-PFOA 13C4-PFOS 3M LIMS ID Description ISO13-07-08-001 DAL-GW-ACI-0-130930 ISO13-07-08-002 DAL-GW-ACI-DB-130930 ISO13-07-08-003 DAL-GW-ACI-FMS-130930 Average Concentration (ng/mL) %RSD %Recovery 94.9 99.5 92.2 95.5% 3.9% %Recovery 94.5 97.9 95.7 96.0% 1.8% NA = Not Applicable (1) Samples were analyzed by external standard calibration. The surrogate recovery standards 13C4-PFOA and 13C4-PFOS were added to the samples during sample preparation. PAGE 13 OF 23 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-08 Table 11. DAL GW ACM2 130930 3M LIMS ID Description ISO13-07-08-004 DAL-GW-ACM2-0-130930 ISO13-07-08-005 DAL-GW-ACM2-DB-130930 ISO13-07-08-006 DAL-GW-ACM2-FMS-130930 Average Concentration (ng/mL) %RPD 3M LIMS ID Description ISO13-07-08-004 DAL-GW-ACM2-0-130930 ISO13-07-08-005 DAL-GW-ACM2-DB-130930 ISO13-07-08-006 DAL-GW-ACM2-FMS-130930 Average Concentration (ng/mL) %RPD PFOA (1) PFBS (1) Concentration (ng/mL) %Recovery 1210 NA 1220 NA 1160 NC 1220 ng/mL 0.82% Concentration (ng/mL) %Recovery 468 NA 471 NA 442 NC 470 ng/mL 0.64% PFHS (1) PFOS (2) Concentration (ng/mL) %Recovery 1550 NA 1570 NA 1500 NC 1560 ng/mL 1.3% Concentration (ng/mL) %Recovery 1.31 NA 1.29 NA 6.39 102 1.30 ng/mL 1.5% 13C4-PFOA (1) 13C4-PFOS (2) 3M LIMS ID Description ISO13-07-08-004 DAL-GW-ACM2-0-130930 ISO13-07-08-005 DAL-GW-ACM2-DB-130930 ISO13-07-08-006 DAL-GW-ACM2-FMS-130930 Average Concentration (ng/mL) %RSD %Recovery 104 100 96.9 100% 3.6% %Recovery 114 106 103 108% 5.3% NA = Not Applicable NC = Not Calculated; Spike level was less than 0.5x the endogenous sample concentration. (1) Samples were analyzed by external standard calibration. The surrogate recovery standards 13C4-PFOA and 13C4-PFOS were added to the samples during sample preparation. (2) Samples were analyzed by internal standard calibration. PAGE 14 OF 23 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-08 Table 12. DAL GW ACE 130930 3M LIMS ID Description ISO13-07-08-007 DAL-GW-ACE-0-130930 ISO13-07-08-008 DAL-GW-ACE-DB-130930 ISO13-07-08-009 DAL-GW-ACE-FMS-130930 Average Concentration (ng/mL) %RPD 3M LIMS ID Description ISO13-07-08-007 DAL-GW-ACE-0-130930 ISO13-07-08-008 DAL-GW-ACE-DB-130930 ISO13-07-08-009 DAL-GW-ACE-FMS-130930 Average Concentration (ng/mL) %RPD PFOA (1) PFBS (2) Concentration (ng/mL) %Recovery 0.109 NA 0.121 NA 4.95 96.7 0.115 ng/mL 10% Concentration (ng/mL) %Recovery 1920 NA 1980 NA 1970 NC 1950 ng/mL 3.1% PFHS (1) PFOS (1) Concentration (ng/mL) %Recovery 0.157 NA 0.154 NA 5.05 97.9 0.156 ng/mL 1.9% Concentration (ng/mL) %Recovery 0.0419 NA 0.0485 NA 5.12 101 0.0452 ng/mL 15% 13C4-PFOA (1) 13C4-PFOS (1) 3M LIMS ID Description ISO13-07-08-007 DAL-GW-ACE-0-130930 ISO13-07-08-008 DAL-GW-ACE-DB-130930 ISO13-07-08-009 DAL-GW-ACE-FMS-130930 Average Concentration (ng/mL) %RSD %Recovery 84.3 94.4 95.9 91.5% 6.9% %Recovery 90.7 99.5 105 98.4% 7.3% NA = Not Applicable NC = Not Calculated; Spike level was less than 0.5x the endogenous sample concentration. (1) Samples were analyzed by internal standard calibration. (2) Samples were analyzed by external standard calibration. The surrogate recovery standards 13C4-PFOA and 13C4-PFOS were added to the samples during sample preparation. PAGE 15 OF 23 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-08 Table 13. DAL GW WW8R 130930 (1) 3M LIMS ID Description ISO13-07-08-010 DAL-GW-WW8R-0-130930 ISO13-07-08-011 DAL-GW-WW8R-DB-130930 ISO13-07-08-012 DAL-GW-WW8R-FMS-130930 Average Concentration (ng/mL) %RPD 3M LIMS ID Description ISO13-07-08-010 DAL-GW-WW8R-0-130930 ISO13-07-08-011 DAL-GW-WW8R-DB-130930 ISO13-07-08-012 DAL-GW-WW8R-FMS-130930 Average Concentration (ng/mL) %RPD PFOA PFBS Concentration (ng/mL) %Recovery 2890 NA 2890 NA 5380 99.2 2890 ng/mL 0.0% Concentration (ng/mL) %Recovery 309 NA 296 NA 2740 97.1 303 ng/mL 4.3% PFHS PFOS Concentration (ng/mL) %Recovery 1360 NA 1370 NA 3920 102 1370 ng/mL 0.73% Concentration (ng/mL) %Recovery 4110 NA 4090 NA 6830 110 4100 ng/mL 0.49% 13C4-PFOA 13C4-PFOS 3M LIMS ID Description ISO13-07-08-010 DAL-GW-WW8R-0-130930 ISO13-07-08-011 DAL-GW-WW8R-DB-130930 ISO13-07-08-012 DAL-GW-WW8R-FMS-130930 Average Concentration (ng/mL) %RSD %Recovery %Recovery 94.2 94.5 94.9 94.5% 0.37% 96.3 96.1 91.7 94.7% 2.7% NA = Not Applicable (1) Samples were analyzed by external standard calibration. The surrogate recovery standards 13C4-PFOA and 13C4-PFOS were added to the samples during sample preparation. PAGE 16 OF 23 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-08 Table 14. DAL GW WW9R 130930 (1) 3M LIMS ID Description ISO13-07-08-013 DAL-GW-WW9R-0-130930 ISO13-07-08-014 DAL-GW-WW9R-DB-130930 ISO13-07-08-015 DAL-GW-WW9R-FMS-130930 Average Concentration (ng/mL) %RPD 3M LIMS ID Description ISO13-07-08-013 DAL-GW-WW9R-0-130930 ISO13-07-08-014 DAL-GW-WW9R-DB-130930 ISO13-07-08-015 DAL-GW-WW9R-FMS-130930 Average Concentration (ng/mL) %RPD PFOA PFBS Concentration (ng/mL) %Recovery 2740 NA 2720 NA 5410 107 2730 ng/mL 0.73% Concentration (ng/mL) %Recovery 252 NA 245 NA 2810 102 249 ng/mL 2.8% PFHS PFOS Concentration (ng/mL) %Recovery 1230 NA 1210 NA 3930 108 1220 ng/mL 1.6% Concentration (ng/mL) %Recovery 4130 NA 4270 NA 7200 120 4200 ng/mL 3.3% 13C4-PFOA 13C4-PFOS 3M LIMS ID Description ISO13-07-08-013 DAL-GW-WW9R-0-130930 ISO13-07-08-014 DAL-GW-WW9R-DB-130930 ISO13-07-08-015 DAL-GW-WW9R-FMS-130930 Average Concentration (ng/mL) %RSD %Recovery 94.7 94.9 99.1 96.2% 2.6% %Recovery 94.6 98.2 95.3 96.0% 2.0% NA = Not Applicable (1) Samples were analyzed by external standard calibration. The surrogate recovery standards 13C4-PFOA and 13C4-PFOS were added to the samples during sample preparation. PAGE 17 OF 23 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-08 Table 15. DAL GW WW10R 130930 (1) 3M LIMS ID Description ISO13-07-08-019 DAL-GW-WW10R-0-130930 ISO13-07-08-020 DAL-GW-WW10R-DB-130930 ISO13-07-08-021 DAL-GW-WW10R-FMS-130930 Average Concentration (ng/mL) %RPD 3M LIMS ID Description ISO13-07-08-019 DAL-GW-WW10R-0-130930 ISO13-07-08-020 DAL-GW-WW10R-DB-130930 ISO13-07-08-021 DAL-GW-WW10R-FMS-130930 Average Concentration (ng/mL) %RPD PFOA PFBS Concentration (ng/mL) %Recovery 2040 NA 2090 NA 4570 99.6 2070 ng/mL 2.4% Concentration (ng/mL) %Recovery 244 NA 250 NA 2670 96.5 247 ng/mL 2.4% PFHS PFOS Concentration (ng/mL) %Recovery 1020 NA 1040 NA 3550 101 1030 ng/mL 1.9% Concentration (ng/mL) %Recovery 2760 NA 2780 NA 5350 104 2770 ng/mL 0.72% 13C4-PFOA 13C4-PFOS 3M LIMS ID Description ISO13-07-08-019 DAL-GW-WW10R-0-130930 ISO13-07-08-020 DAL-GW-WW10R-DB-130930 ISO13-07-08-021 DAL-GW-WW10R-FMS-130930 Average Concentration (ng/mL) %RSD %Recovery 96.5 101 96.1 97.9% 2.8% %Recovery 99.8 107 99.9 102% 4.0% NA = Not Applicable (1) Samples were analyzed by external standard calibration. The surrogate recovery standards 13C4-PFOA and 13C4-PFOS were added to the samples during sample preparation. PAGE 18 OF 23 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-08 Table 16. DAL GW WW11R 130930 (1) 3M LIMS ID Description ISO13-07-08-022 DAL-GW-WW11R-0-130930 ISO13-07-08-023 DAL-GW-WW11R-DB-130930 ISO13-07-08-024 DAL-GW-WW11R-FMS-130930 Average Concentration (ng/mL) %RPD 3M LIMS ID Description ISO13-07-08-022 DAL-GW-WW11 R-0-130930 ISO13-07-08-023 DAL-GW-WW11 R-DB-130930 ISO13-07-08-024 DAL-GW-WW11 R-FMS-130930 Average Concentration (ng/mL) %RPD PFOA PFBS Concentration (ng/mL) %Recovery 1700 NA 1730 NA 4160 97.2 1720 ng/mL 1.7% Concentration (ng/mL) %Recovery 297 NA 301 NA 2660 94.1 299 ng/mL 1.3% PFHS PFOS Concentration (ng/mL) %Recovery 1010 NA 993 NA 3490 99.6 1000 ng/mL 1.7% Concentration (ng/mL) %Recovery 2190 NA 2210 NA 4610 96.8 2200 ng/mL 0.91% 13C4-PFOA 13C4-PFOS 3M LIMS ID Description ISO13-07-08-022 DAL-GW-WW11 R-0-130930 ISO13-07-08-023 DAL-GW-WW11 R-DB-130930 ISO13-07-08-024 DAL-GW-WW11 R-FMS-130930 Average Concentration (ng/mL) %RSD %Recovery 100 101 96.3 99.1% 2.5% %Recovery 104 104 96.8 102% 4.1% NA = Not Applicable (1) Samples were analyzed by external standard calibration. The surrogate recovery standards 13C4-PFOA and 13C4-PFOS were added to the samples during sample preparation. PAGE 19 OF 23 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-08 Table 17. Trip Blank Results 3M LIMS ID ISO13-07-08-016 ISO13-07-08-017 ISO13-07-08-018 Description DAL-GW-TRIP01 -0-130930 DAL-GW-TRIP01 -LS-130930 DAL-GW-TRI P01-HS-130930 3M LIMS ID ISO13-07-08-016 ISO13-07-08-017 ISO13-07-08-018 Description DAL-GW-TRI P01-0-130930 DAL-GW-TRI P01-LS-130930 DAL-GW-TRI P01-HS-130930 PFOA PFBS Concentration (ng/mL) <0.0240 (1) 5.04 (2) 2870 (2) %Recovery NA 101 114 Concentration (ng/mL) <0.200 (2) 5.06 (2) 2690 (2) %Recovery NA 101 107 PFHS PFOS Concentration (ng/mL) <0.400 (1) 5.17 (2) 2740 (2) %Recovery NA 103 110 Concentration (ng/mL) <0.0232 (1) 5.40 (2) 2900 (2) %Recovery NA 108 116 13C4-PFOA 13C4-PFOS 3M LIMS ID ISO13-07-08-016 ISO13-07-08-017 ISO13-07-08-018 Description DAL-GW-TRI P01-0-130930 DAL-GW-TRI P01-LS-130930 DAL-GW-TRI P01-HS-130930 %Recovery 94.2 (1) 102 (2) 101 (2) %Recovery 105 (1) 108 (2) 105 (2) NA = Not Applicable (1) Samples were analyzed by internal standard calibration. (2) Samples were analyzed by external standard calibration. The surrogate recovery standards 13C4-PFOA and 13C4-PFOS were added to the samples during sample preparation. PAGE 20 OF 23 3M ENVIRONMENTAL LABORATORY REPORT NO. IS013-07-08 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 Perfluorlnated Compounds in Water by LC/MS/MS; Direct Injection Analysis". Analytical results are reported in Table 1 and 10-17 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 Attachment A: Analyte Trend Data for select sampling points at the Decatur Ground Water Treatment Plant (GWTP) GAC System. 8 Signatures Susan T. Wolf, 3IV(Pcihdpal Analytical Investigator Il I i / l 3 Date 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 21 OF 23 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-08 Attachment A: Analyte Trend Data for select sampling points at the Decatur Ground Water Treatment Plant (GWTP) GAC System ACI (Activated Carbon Influent) - Sample Results in ng/mL ACI PFOA PFBS PFHS PFOS 6/29/12 1650 1410 1460 964 8/28/12 1410 1830 1390 172 12/14/12 2580 723 1380 2810 1/17/13 1910 588 895 1810 2/13/13 2300 830 1580 2940 3/27/13 2220 1060 1090 2490 4/29/13 1480 1360 777 1670 ACE (Activated Carbon Effluent) - Sample Results in ng/mL FC C harting fo r DAL_GW TP_ACE 5/31/13 1860 1040 940 2150 6/27/13 1480 708 942 1590 7/23/13 1630 1230 749 1680 9/30/13 2320 356 1400 3240 PFOA------- -------PFOS------- -------- PFBS------- -------- PFHS------- ACE PFOA PFBS PFHS PFOS 8/28/12 0.387 0.256 0.552 0.103 12/14/12 0.102 <0.0250 0.117 0.0376 1/17/13 <0.0240 <0.0250 <0.0250 <0.0232 2/13/13 0.124 0.0360 0.178 0.0329 The ACE location was not sampled on 6/29/12. 3/27/13 0.0380 <0.0250 0.0477 <0.0232 4/29/13 0.0422 0.392 0.057 <0.0232 5/31/13 0.0725 24.8 0.105 <0.0232 6/27/13 0.0717 111 0.118 <0.0232 7/23/13 0.0643 1960 0.0778 0.0277 9/30/13 0.115 1950 0.156 0.0452 PAGE 22 OF 23 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-08 Attachment A: Analyte Trend Data for select sampling points at the Decatur Ground Water Treatment Plant (GWTP) GAC System WW8R - Sample Results in ng/mL 5000- FC C harting fo r DAL W W 8R PFOA------- -------PFOS------- -------- PFBS------- -------- PFHS------- W W 8R PFOA PFBS PFHS PFOS 12/13/12 3630 441 1740 4920 1/17/13 4350 410 1930 5710 2/13/13 3250 354 1900 4850 WW9R - Sample Results in ng/mL 3/27/13 3640 385 1760 5120 4/29/13 3190 364 1610 4830 5/31/13 2760 289 1330 4180 6/27/13 2760 282 1340 4110 7/23/13 2640 263 1260 3910 9/30/13 2890 303 1370 4100 W W 9R PFOA PFBS PFHS PFOS 12/13/12 3360 321 1480 4080 1/17/13 2710 184 954 3690 2/13/13 2850 236 1400 4100 3/27/13 3330 278 1440 4660 4/29/13 2650 244 1200 4340 5/31/13 2660 226 1120 4210 6/27/13 2630 225 1140 4150 7/23/13 2410 212 1030 3670 9/30/13 2730 249 1220 4200 PAGE 23 OF 23