Document j4G8Y0djMXgeo36BOoyBnOR2

3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-02 Final Report Analysis of PFOA, PFBS, PFHS, and PFOS in Aqueous Samples from 3M Decatur, Alabama: Groundwater Treatment Plant GAC System February 2014 Laboratory Request Number: ISO14-07-02 Method Requirement: 3M Method ETS-8-044.1 Report Date - Date of Last Signature Testing Laboratory 3M EHS 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 24 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-02 3M Environmental Laboratory 3M Environmental Laboratory Technical Director: William K. Reagen, Ph.D. 3M Principal Analytical Investigator: Susan Wolf Report Author: Susanna Emond Analytical Report ISO14-07-02 3M Decatur Groundwater Treatment Plant System; February 2014 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 February 27, 2014. 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 ISO14-07-02. Analysis of the samples was completed as specified under 3M Environmental Laboratory General Project Outline (GPO) number GPO13-1289. 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 surrogate recovery standard 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". Internal standards were used for select samples 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 24 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-02 Table 1. Sample Results Summary (1) 3M LIMS ID Sample Description PFOA Concentration (ng/mL) ISO14-07-02-001 DAL-GW-ACI-0 - 140227 ISO14-07-02-002 DAL-GW-ACI-DB - 140227 Average %RPD Sample/Sample Dup ISO14-07-02-004 DAL-GW-ACM2-0 - 140227 ISO14-07-02-005 DAL-GW-ACM2-DB - 140227 Average %RPD Sample/Sample Dup ISO14-07-02-007 DAL-GW-ACE-0- (100x) ISO14-07-02-008 DAL-GW-ACE-DB- (100x) Average %RPD Sample/Sample Dup ISO14-07-02-010 DAL-GW-WW8R-0 - 140227 ISO14-07-02-011 DAL-GW-WW8R-DB - 140227 Average %RPD Sample/Sample Dup ISO14-07-02-013 DAL-GW-WW9R-0 - 140227 ISO14-07-02-014 DAL-GW-WW9R-DB - 140227 Average %RPD Sample/Sample Dup ISO14-07-02-016 DAL-GW-WW10R-0 - 140227 ISO14-07-02-017 DAL-GW-WW10R - 140227 Average %RPD Sample/Sample Dup ISO14-07-02-019 DAL-GW-WW11R-0 - 140227 ISO14-07-02-020 DAL-GW-WW11R-DB - 140227 Average %RPD Sample/Sample Dup 1860 1880 1870 1.1 0.182 0.173 0.178 (2) 5.1 0.129 0.147 0.138 (2) 13 2540 2580 2560 1.6 2640 2620 2630 0.76 1820 1740 1780 4.5 1220 1370 1300 12 PFBS Concentration (ng/mL) 1470 1470 1470 0.0 1250 1150 1200 8.3 0.0342 0.0377 0.0360 (2) 10 326 336 331 3.0 265 274 270 3.3 264 256 260 3.1 251 272 262 8.0 PFHS Concentration (ng/mL) 722 751 737 3.9 0.0835 0.0821 0.0828 (2) 1.7 0.0637 0.0774 0.0706 (2) 19 1350 1380 1370 2.2 1390 1340 1370 3.7 919 950 935 3.3 683 709 696 3.7 PFOS Concentration (ng/mL) 1830 1760 1800 3.9 0.676 0.709 0.693 (2) 4.8 0.0970 0.0962 0.0966 (2) 0.83 4130 4210 4170 1.9 4580 4730 4660 3.2 2840 2880 2860 1.4 1850 2340 2100 23 (3) NA = Not Applicable (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 15%, PFBS 10%, PFHS 14%, and PFOS 14%. (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 15%, PFBS 9.5%, PFHS 9.9%, and PFOS 12%. (3) Sample set did not meet sample / sample duplicate RPD acceptance criteria of <20%. PAGE 3 OF 24 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-02 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 February 27, 2014 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 prior to being sent to the field for sample collection. Collected sample bottles were received by the laboratory at ambient conditions on March 5, 2014. 2.3 Sample Preparation All samples were initially prepared by diluting with methanol (dilution factor of 100) and analyzing for all target 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 (nominal concentration of 1 ng/mL). Prepared samples were analyzed by external standard calibration. The ACE and ACM2 sample sets and the Trip Blank sample and low spike were subsequently prepared 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). 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 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. 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 PAGE 4 OF 24 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-02 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 Buster 3/06/14 - external standard calibration ETS-8-044.1 Agilent 1100 Betasil C18 (4.6 mm X 100 mm), 5 g Betasil C18 (4.6 mm X 100 mm), 5 g 10 gL Applied Biosystems API 4000 Turbo Spray Negative Analyst 1.6.1 ETS Kirk 3/13/14- internal standard calibration ETS-8-044.1 Agilent 1260 Betasil C18 (4.6 mm X 100 mm), 5 g Betasil C18 (4.6 mm X 100 mm), 5 g 10 gL 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 (gL/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 24 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-02 Table 5. Mass Transitions. Analyte Mass Transition Q1/Q3 Internal Standard (1) Mass Transition Q1/Q3 PFOA PFBS PFHS 413/369 413/219 413/169 299/80 299/99 399/99 399/80 [13C8]PFOA [18O2]PFBS [13Cs]PFHS 421/376 303/84 402/99 PFOS 499/99 499/80 [13C8]PFOS 507/80 [13C4]PFOA surrogate [13C4]PFOS surrogate 499/130 417/372 503/80 [13C8]PFOA [13C8]PFOS 421/376 507/80 Dwell time was between 20 and 50 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 3/13/14. 3 Data Analysis 3.1 Calibration External Standard Calibration Analysis on 3/06/14: 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 0.1 ng/mL to 150 ng/mL (nominal) were analyzed. The standards also contained the surrogates at concentrations ranging from 0.1 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 3/13/14: Samples were analyzed for all analytes 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 thirteen calibration standards ranging from 0.0125 ng/mL to 50 ng/mL (nominal) were analyzed (0.0125 ng/mL to 10 ng/mL (nominal) for the SRSs). Low or high points may have been disabled to meet method criteria. 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 24 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-02 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 with the exception of the peak area count RSD for PFHS analyzed on 3/06/14 (10%). 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 Table 6. Table 6. LOQ Analyte LOQ, ng/mL 3/06/14 Analysis (1) LOQ, ng/mL 3/13/14 Analysis (2) PFOA 9.58 0.0240 PFBS 10.0 0.0250 PFHS 10.0 0.0250 PFOS 9.27 0.0232 (1) The dilution factor of 100 was applied to the LOQ. (2) The dilution factor of 2 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. 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 with the following exception: 3/06/14 Analysis: The high level LCSs for PFOS-Surrogate had an average recovery of 125%. A method deviation is included with the raw data. 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 LCS% RSD = standard deviation LCS replicates * 100% average LCS recovery PAGE 7 OF 24 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-02 Table 7. Lab Control Spike Results. ETS-8-044.1 External Standard Calibration Analyzed 3/06/14 Lab ID PFOA (Linear + Branched) Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) %Recovery 13C4-PFOA surrogate Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) %Recovery LCS-140306-1 LCS-140306-2 LCS-140306-3 Average %RSD 0.958 0.958 0.958 0.926 0.844 0.880 92.2% 4.6% 96.6 88.1 91.8 0.998 0.998 0.998 1.06 1.08 1.08 107% 1.1% 106 108 108 LCS-140306-4 LCS-140306-5 LCS-140306-6 Average %RSD 9.58 10.10 9.58 9.61 9.58 10.20 104% 3.3% 106 100 106 9.98 11.3 9.98 11.8 9.98 11.2 114% 2.8% 113 118 112 LCS-140306-7 LCS-140306-8 LCS-140306-9 Average %RSD 38.2 38.6 38.2 38.5 38.2 37.6 100% 1.4% 101 101 98.5 ETS-8-044.1 External Standard Calibration Analyzed3/06/14 Lab ID Spiked Concentration (ng/mL) PFBS Calculated Concentration (ng/mL) LCS-140306-1 LCS-140306-2 LCS-140306-3 Average %RSD LCS-140306-4 LCS-140306-5 LCS-140306-6 Average %RSD 1.00 1.05 1.00 0.95 1.00 1.06 102% 6.0% 10.0 10.8 10.0 11.2 10.0 10.9 110% 1.9% LCS-140306-7 LCS-140306-8 LCS-140306-9 Average %RSD 39.8 41.8 39.8 42.3 39.8 40.9 105% 1.5% %Recovery Spiked Concentration (ng/mL) PFHS Calculated Concentration (ng/mL) 105 1.00 1.06 95.0 1.00 1.05 106 1.00 1.09 107% 2.0% 108 10.0 11.4 112 10.0 11.2 109 10.0 11.3 113% 0.88% 105 39.8 43.6 106 39.8 42.5 103 39.8 42.5 108% 1.6% %Recovery 106 105 109 114 112 113 110 107 107 (1) LCS recovery did not meet acceptance criteria of 100 20%. PAGE 8 OF 24 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-02 Table 7 continued. Lab Control Spike Results. ETS-8-044.1 External Standard Calibration Analyzed 3/06/14 Lab ID PFOS (Linear + Branched) Spiked Concentration (ng/mL) Calculated Concentration (ng/mL) %Recovery 13C4-PFOS surrogate Spiked Concentration (ng/mL) Calculated Concentration (ng/mL) %Recovery LCS-140306-1 LCS-140306-2 LCS-140306-3 Average %RSD 0.927 0.927 0.927 0.928 0.942 0.911 100% 1.9% 100 102 98.2 0.956 0.956 0.956 1.07 1.07 1.08 112% 0.51% 112 112 113 LCS-140306-4 LCS-140306-5 LCS-140306-6 Average %RSD 9.27 9.97 9.27 9.71 9.27 10.1 107% 1.9% 108 105 109 9.56 11.9 9.56 12.0 9.56 11.7 125% 1.2% (1) 125 126 123 LCS-140306-7 LCS-140306-8 LCS-140306-9 Average %RSD 36.9 38.2 36.9 39.4 36.9 38.1 104% 2.2% 103 107 103 ETS-8-044.1 Internal Standard Calibration Analyzed 3/13/14 Lab ID LCS-140313-1 LCS-140313-2 LCS-140313-3 Average %RSD LCS-140313-4 LCS-140313-5 LCS-140313-6 Average %RSD LCS-140313-7 LCS-140313-8 LCS-140313-9 Average %RSD PFOA (Linear + Branched) Spiked Concentration (ng/mL) Calculated Concentration (ng/mL) %Recovery 13C4-PFOA surrogate Spiked Concentration (ng/mL) Calculated Concentration (ng/mL) %Recovery 0.190 0.190 0.190 0.202 0.208 0.208 108% 1.9% 106 110 109 0.198 0.198 0.198 0.204 0.211 0.230 108% 6.3% 103 106 116 9.50 10.5 9.50 10.2 9.50 10.8 110% 2.3% 110 108 113 1.98 2.21 1.98 2.33 1.98 2.50 118% 6.3% 111 118 126 38.0 45.0 38.0 42.8 38.0 44.8 116% 2.5% 118 113 118 (1) LCS recovery did not meet acceptance criteria of 100 20%. PAGE 9 OF 24 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-02 Table 7 continued. Lab Control Spike Results. ETS-8-044.1 Internal Standard Calibration Analyzed 3/13/14 Lab ID LCS-140313-1 LCS-140313-2 LCS-140313-3 Average %RSD LCS-140313-4 LCS-140313-5 LCS-140313-6 Average %RSD LCS-140313-7 LCS-140313-8 LCS-140313-9 Average %RSD Spiked Concentration (ng/mL) PFBS Calculated Concentration (ng/mL) 0.198 0.198 0.198 0.190 0.199 0.202 99.6% 3.3% 9.92 10.0 9.92 10.3 9.92 10.4 103% 2.0% 39.6 44.1 39.6 41.4 39.6 42.2 108% 2.8% %Recovery Spiked Concentration (ng/mL) PFHS Calculated Concentration (ng/mL) 95.9 0.198 0.226 101 0.198 0.220 102 0.198 0.223 113% 1.4% 101 9.92 11.1 104 9.92 10.9 105 9.92 11.0 111% 0.90% 111 39.6 45.9 105 39.6 43.1 107 39.6 45.8 114% 3.6% %Recovery 114 111 113 112 110 111 116 109 116 ETS-8-044.1 Internal Standard Calibration Analyzed 3/13/14 Lab ID LCS-140313-1 LCS-140313-2 LCS-140313-3 Average %RSD LCS-140313-4 LCS-140313-5 LCS-140313-6 Average %RSD LCS-140313-7 LCS-140313-8 LCS-140313-9 Average %RSD PFOS (Linear + Branched) Spiked Concentration (ng/mL) Calculated Concentration (ng/mL) %Recovery 13C4-PFOS surrogate Spiked Concentration (ng/mL) Calculated Concentration (ng/mL) %Recovery 0.184 0.184 0.184 0.197 0.222 0.221 116% 6.7% 107 121 120 0.189 0.189 0.189 0.184 0.196 0.206 104% 5.6% 97.5 104 109 9.20 9.87 9.20 10.1 9.20 10.1 109% 1.4% 107 109 110 1.90 2.10 1.90 2.34 1.90 2.32 118% 6.1% 110 123 122 36.7 43.2 36.7 40.2 36.7 41.6 114% 3.6% 118 110 113 (1) LCS recovery did not meet acceptance criteria of 100 20%. PAGE 10 OF 24 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-02 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 PFBS PFHS PFOS Calibration Method External Standard External Standard External Standard External Standard Internal Standard Internal Standard Internal Standard Internal Standard Standard Deviation (%) 7.73 5.07 7.04 6.88 7.42 4.73 4.95 5.81 Method Uncertainty 15% 10% 14% 14% 15% 9.5% 9.9% 12% 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.) *100% Spike Concentraton Table 9. Field Matrix Spike Concentrations. Location ACI ACM2, ACE WW8R, WW9R WW10R, WW11R Trip Blank Description Field Matrix Spike Field Matrix Spike Field Matrix Spike Field Matrix Spike Low Field Matrix Spike High Field Matrix Spike Firial Concentr.tion (ng/mL PFOA PFBS PFHS PFOS 1980 4.96 2480 1980 4.96 2480 2000 5.00 2500 2000 5.00 2500 2000 5.00 2510 2000 5.00 2510 2000 4.99 2500 2000 4.99 2500 PAGE 11 OF 24 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-02 4 Data Summary and Discussion The tables below summarize the sample results and field matrix spike recoveries for the seven 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. Relative percent 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 samples met method acceptance criteria except where noted below. DAL-GW-ACM2: the FMS spike level at 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. DAL-GW-WW11R: sample / sample duplicate %RPD was 23% for PFOS. PAGE 12 OF 24 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-02 Table 10. DAL GW ACI 140227 (1) 3M LIMS ID Sample Description ISO14-07-02-001 DAL-GW-ACI-0 - 140227 ISO14-07-02-002 DAL-GW-ACI-DB - 140227 ISO14-07-02-003 DAL-GW-ACI-FMS - 140227 Average Concentration (ng/mL) %RPD PFOA PFBS Concentration (ng/mL) %Recovery 1860 NA 1880 NA 3610 87.7 1870 ng/mL 1.1% Concentration (ng/mL) %Recovery 1470 NA 1470 NA 3340 93.5 1470 ng/mL 0.0% 3M LIMS ID Sample Description ISO14-07-02-001 DAL-GW-ACI-0 - 140227 ISO14-07-02-002 DAL-GW-ACI-DB - 140227 ISO14-07-02-003 DAL-GW-ACI-FMS - 140227 Average Concentration (ng/mL) %RPD PFHS PFOS Concentration (ng/mL) %Recovery 722 NA 751 NA 2890 107 737 ng/mL 3.9% Concentration (ng/mL) %Recovery 1830 NA 1760 NA 3780 99.4 1800 ng/mL 3.9% 13C4-PFOA 13C4-PFOS 3M LIMS ID Sample Description ISO14-07-02-001 DAL-GW-ACI-0 - 140227 ISO14-07-02-002 DAL-GW-ACI-DB - 140227 ISO14-07-02-003 DAL-GW-ACI-FMS - 140227 Average Concentration (ng/mL) %RSD %Recovery 110 97.6 102 103% 6.2% %Recovery 110 112 105 109% 3.5% 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 24 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-02 Table 11. DAL GW ACM2 140227 3M LIMS ID Sample Description ISO14-07-02-004 DAL-GW-ACM2-0 - 140227 ISO14-07-02-005 DAL-GW-ACM2-DB - 140227 ISO14-07-02-006 DAL-GW-ACM2-FMS - 140227 Average Concentration (ng/mL) %RPD PFOA (1) PFBS (2) Concentration (ng/mL) %Recovery 0.182 NA 0.173 NA 5.84 114 0.178 ng/mL 5.1% Concentration (ng/mL) %Recovery 1250 NA 1150 NA 1240 NC 1200 ng/mL 8.3% 3M LIMS ID Sample Description ISO14-07-02-004 DAL-GW-ACM2-0 - 140227 ISO14-07-02-005 DAL-GW-ACM2-DB - 140227 ISO14-07-02-006 DAL-GW-ACM2-FMS - 140227 Average Concentration (ng/mL) %RPD PFHS (1) PFOS (1) Concentration (ng/mL) %Recovery 0.0835 NA 0.0821 NA 5.77 114 0.0828 ng/mL 1.7% Concentration (ng/mL) %Recovery 0.676 NA 0.709 NA 6.28 112 0.693 ng/mL 4.8% 13C4-PFOA (1) 13C4-PFOS (1) 13C4-PFOS (2) 3M LIMS ID Sample Description ISO14-07-02-004 DAL-GW-ACM2-0 - 140227 ISO14-07-02-005 DAL-GW-ACM2-DB - 140227 ISO14-07-02-006 DAL-GW-ACM2-FMS - 140227 Average Concentration (ng/mL) %RSD %Recovery 98.5 93.3 92.3 94.7% 3.5% %Recovery 100 98.5 95.3 98.0% 2.5% %Recovery 115 113 109 112% 2.8% 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 standard 13C4-PFOS was added to the samples during sample preparation. PAGE 14 OF 24 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-02 Table 12. DAL GW ACE 140227 (1) 3M LIMS ID Sample Description ISO14-07-02-007 DAL-GW-ACE-0 - 140227 ISO14-07-02-008 DAL-GW-ACE-DB - 140227 ISO14-07-02-009 DAL-GW-ACE-FMS - 140227 Average Concentration (ng/mL) %RPD PFOA PFBS Concentration (ng/mL) %Recovery 0.129 NA 0.147 NA 5.76 113 0.138 ng/mL 13% Concentration (ng/mL) %Recovery 0.0342 NA 0.0377 NA 5.17 103 0.0360 ng/mL 9.7% 3M LIMS ID Sample Description ISO14-07-02-007 DAL-GW-ACE-0 - 140227 ISO14-07-02-008 DAL-GW-ACE-DB - 140227 ISO14-07-02-009 DAL-GW-ACE-FMS - 140227 Average Concentration (ng/mL) %RPD PFHS PFOS Concentration (ng/mL) %Recovery 0.0637 NA 0.0774 NA 5.54 109 0.0706 ng/mL 19% Concentration (ng/mL) %Recovery 0.0970 NA 0.0962 NA 5.76 113 0.0966 ng/mL 0.83% 13C4-PFOA 13C4-PFOS 3M LIMS ID Sample Description ISO14-07-02-007 DAL-GW-ACE-0 - 140227 ISO14-07-02-008 DAL-GW-ACE-DB - 140227 ISO14-07-02-009 DAL-GW-ACE-FMS - 140227 Average Concentration (ng/mL) %RSD %Recovery 95.1 91.6 91.4 92.7% 2.2% %Recovery 96.2 89.3 94.7 93.4% 3.9% NA = Not Applicable (1) Samples were analyzed by internal standard calibration. PAGE 15 OF 24 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-02 Table 13. DAL GW WW8R 140227 (1) 3M LIMS ID Sample Description ISO14-07-02-010 DAL-GW-WW8R-0 - 140227 ISO14-07-02-011 DAL-GW-WW8R-DB - 140227 ISO14-07-02-012 DAL-GW-WW8R-FMS - 140227 Average Concentration (ng/mL) %RPD PFOA PFBS Concentration (ng/mL) %Recovery 2540 NA 2580 NA 5000 98.4 2560 ng/mL 1.6% Concentration (ng/mL) %Recovery 326 NA 336 NA 2890 102 331 ng/mL 3.0% 3M LIMS ID Sample Description ISO14-07-02-010 DAL-GW-WW8R-0 - 140227 ISO14-07-02-011 DAL-GW-WW8R-DB - 140227 ISO14-07-02-012 DAL-GW-WW8R-FMS - 140227 Average Concentration (ng/mL) %RPD PFHS PFOS Concentration (ng/mL) %Recovery 1350 NA 1380 NA 4060 108 1370 ng/mL 2.2% Concentration (ng/mL) %Recovery 4130 NA 4210 NA 6790 105 4170 ng/mL 1.9% 13C4-PFOA 13C4-PFOS 3M LIMS ID Sample Description ISO14-07-02-010 DAL-GW-WW8R-0 - 140227 ISO14-07-02-011 DAL-GW-WW8R-DB - 140227 ISO14-07-02-012 DAL-GW-WW8R-FMS - 140227 Average Concentration (ng/mL) %RSD %Recovery 95.6 101 94.7 97.2% 3.6% %Recovery 99.0 119 108 109% 9.4% 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 24 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-02 Table 14. DAL GW WW9R 140227 (1) 3M LIMS ID Sample Description ISO14-07-02-013 DAL-GW-WW9R-0 - 140227 ISO14-07-02-014 DAL-GW-WW9R-DB - 140227 ISO14-07-02-015 DAL-GW-WW9R-FMS - 140227 Average Concentration (ng/mL) %RPD PFOA PFBS Concentration (ng/mL) %Recovery 2640 NA 2620 NA 4830 88.7 2630 ng/mL 0.76% Concentration (ng/mL) %Recovery 265 NA 274 NA 2740 98.8 270 ng/mL 3.3% 3M LIMS ID Sample Description ISO14-07-02-013 DAL-GW-WW9R-0 - 140227 ISO14-07-02-014 DAL-GW-WW9R-DB - 140227 ISO14-07-02-015 DAL-GW-WW9R-FMS - 140227 Average Concentration (ng/mL) %RPD PFHS PFOS Concentration (ng/mL) %Recovery 1390 NA 1340 NA 3840 98.8 1370 ng/mL 3.7% Concentration (ng/mL) %Recovery 4580 NA 4730 NA 6920 90.8 4660 ng/mL 3.2% 13C4-PFOA 13C4-PFOS 3M LIMS ID Sample Description ISO14-07-02-013 DAL-GW-WW9R-0 - 140227 ISO14-07-02-014 DAL-GW-WW9R-DB - 140227 ISO14-07-02-015 DAL-GW-WW9R-FMS - 140227 Average Concentration (ng/mL) %RSD %Recovery 101 98.3 97.6 99.0% 1.9% %Recovery 109 109 107 108% 1.1% 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 17 OF 24 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-02 Table 15. DAL GW WW10R 140227 (1) 3M LIMS ID Sample Description ISO14-07-02-016 DAL-GW-WW10R-0 - 140227 ISO14-07-02-017 DAL-GW-WW10R-DB - 140227 ISO14-07-02-018 DAL-GW-WW10R-FMS - 140227 Average Concentration (ng/mL) %RPD PFOA PFBS Concentration (ng/mL) %Recovery 1820 NA 1740 NA 3710 97.3 1780 ng/mL 4.5% Concentration (ng/mL) %Recovery 264 NA 256 NA 2130 93.5 260 ng/mL 3.1% 3M LIMS ID Sample Description ISO14-07-02-016 DAL-GW-WW10R-0 - 140227 ISO14-07-02-017 DAL-GW-WW10R-DB - 140227 ISO14-07-02-018 DAL-GW-WW10R-FMS - 140227 Average Concentration (ng/mL) %RPD PFHS PFOS Concentration (ng/mL) %Recovery 919 NA 950 NA 3220 114 935 ng/mL 3.3% Concentration (ng/mL) %Recovery 2840 NA 2880 NA 4770 95.7 2860 ng/mL 1.4% 13C4-PFOA 13C4-PFOS 3M LIMS ID Sample Description ISO14-07-02-016 DAL-GW-WW10R-0 - 140227 ISO14-07-02-017 DAL-GW-WW10R-DB - 140227 ISO14-07-02-018 DAL-GW-WW10R-FMS - 140227 Average Concentration (ng/mL) %RSD %Recovery 103 103 96.8 101% 3.7% %Recovery 106 114 106 108% 4.5% 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 24 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-02 Table 16. DAL GW WW11R 140227 (1) 3M LIMS ID Sample Description ISO14-07-02-019 DAL-GW-WW11R-0 - 140227 ISO14-07-02-020 DAL-GW-WW11R-DB - 140227 ISO14-07-02-021 DAL-GW-WW11R-FMS - 140227 Average Concentration (ng/mL) %RPD PFOA PFBS Concentration (ng/mL) %Recovery 1220 NA 1370 NA 3090 90.5 1300 ng/mL 12% Concentration (ng/mL) %Recovery 251 NA 272 NA 2430 108 262 ng/mL 8.0% 3M LIMS ID Sample Description ISO14-07-02-019 DAL-GW-WW11 R-0 - 140227 ISO14-07-02-020 DAL-GW-WW11 R-DB - 140227 ISO14-07-02-021 DAL-GW-WW11 R-FMS - 140227 Average Concentration (ng/mL) %RPD PFHS PFOS Concentration (ng/mL) %Recovery 683 NA 709 NA 2910 110 696 ng/mL 3.7% Concentration (ng/mL) %Recovery 1850 NA 2340 NA 3790 84.9 2100 ng/mL 23% (2) 13C4-PFOA 13C4-PFOS 3M LIMS ID Sample Description ISO14-07-02-019 DAL-GW-WW11 R-0 - 140227 ISO14-07-02-020 DAL-GW-WW11 R-DB - 140227 ISO14-07-02-021 DAL-GW-WW11 R-FMS - 140227 Average Concentration (ng/mL) %RSD %Recovery 102 111 95.4 103% 7.7% %Recovery 113 111 109 111% 1.9% 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 (2) Sample RPD set did not meet acceptance criteria of 20%. PAGE 19 OF 24 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-02 Table 17. Trip Blank Results 3M LIMS ID ISO14-07-02-022 ISO14-07-02-023 ISO14-07-02-024 Sample Description DAL-GW-TRIP-0 - 140227 DAL-GW-TRIP-LS - 140227 DAL-GW-TRIP-HS - 140227 3M LIMS ID ISO14-07-02-022 ISO14-07-02-023 ISO14-07-02-024 Sample Description DAL-GW-TRIP-0 - 140227 DAL-GW-TRIP-LS - 140227 DAL-GW-TRIP-HS - 140227 PFOA PFBS Concentration (ng/mL) <0.0240 (1) 5.46 (1) 2390 (2) %Recovery NA 110 96.4 Concentration (ng/mL) <0.0250 (1) 5.15 (1) 2450 (2) %Recovery NA 103 98.0 PFHS PFOS Concentration (ng/mL) <0.0250 (1) 5.47 (1) 2630 (2) %Recovery NA 109 105 Concentration (ng/mL) <0.0232 (1) 5.35 (1) 2660 (2) %Recovery NA 107 107 13C4-PFOA (1) 13C4-PFOS (1) 13C4-PFOA (2) 13C4-PFOS (2) 3M LIMS ID ISO14-07-02-022 ISO14-07-02-023 ISO14-07-02-024 Sample Description DAL-GW-TRIP-0 - 140227 DAL-GW-TRIP-LS - 140227 DAL-GW-TRIP-HS - 140227 %Recovery 86.9 93.5 NA %Recovery 95.8 93.7 NA %Recovery 108 103 92.7 %Recovery 99.2 103 102 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 24 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-02 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 10-17 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 the Decatur Ground Water Treatment Plant (GWTP) GAC System. 8 Signatures Digitally signed by Susan T. Wolf DN: c=US, st=MN, l=St. Paul, ou=3M Environmental Laboratory - authenticated by LRA, email=stwolf@mmm.com, o=3M, cn=Susan T. Wolf Reason: I have reviewed this document Date: 2014.04.09 08:26:38 ~05'00' Susan T. Wolf, 3M Principal Analytical Investigator Digitally signed by William K. Reagen DN: c=US, st=MN, l=St. Paul, ou=Laboratory Director, ou=3M Environmental Laboratoryauthenticated by LRA, email=wkreagen@mmm.com, o=3M, cn=William K. Reagen Reason: I am approving this document Date: 2014.04.09 12:45:57 -05*00* William K. Reagen, Ph.D., 3M Environmental Laboratory Technical Director The 3M Environmental Laboratory's Quality Assurance Unit has audited the data and report for this project. Digitally signed by Tanya K. Rude DN: c=US, st=MN, l=St. Paul, ou=3M Environmental Laboratory - authenticated by LRA, emaiNrude@mmm.com, o=3M, placement of my signature on this document Date: 2014.04.09 13:40:48 -05'00* Quality Assurance Representative This test report shall not be reproduced except in full, without written approval of the 3M Environmental Laboratory. PAGE 21 OF 24 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-02 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 03/27/13 2220 1060 1090 2490 04/29/13 1480 1360 777 1670 05/31/13 1860 1040 940 2150 06/27/13 1480 708 942 1590 07/23/13 1630 1230 749 1680 09/30/13 2320 356 1400 3240 10/28/13 1880 1590 866 2100 11/18/13 2190 1100 1330 2240 12/13/13 1830 1350 695 1970 01/30/14 1580 202 845 2700 02/27/14 1870 1470 737 1800 ACE (Activated Carbon Effluent) - Sample Results in ng/mL ACE PFOA PFBS PFHS PFOS 03/27/13 0.0380 <0.0250 0.0477 <0.0232 04/29/13 0.0422 0.392 0.057 <0.0232 05/31/13 0.0725 24.8 0.105 <0.0232 06/27/13 0.0717 111 0.118 <0.0232 07/23/13 0.0641 1960 0.0778 0.0277 09/30/13 0.115 1950 0.156 0.0452 10/28/13 0.231 0.379 0.180 0.0785 11/18/13 0.478 0.592 0.366 0.0726 12/13/13 0.0798 0.0766 0.0648 0.0303 01/30/14 0.490 0.257 0.219 0.209 02/27/14 0.138 0.0360 0.0706 0.0966 PAGE 22 OF 24 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-02 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 W W 8R PFOA PFBS PFHS PFOS 03/27/13 3640 385 1760 5120 04/29/13 3190 364 1610 4830 05/31/13 2760 289 1330 4180 06/27/13 2760 282 1340 4110 07/23/13 2640 263 1260 3910 09/30/13 2890 303 1370 4100 10/28/13 2830 312 1300 4410 11/18/13 3040 362 1440 4750 12/13/13 2720 316 1270 4060 01/30/14 2660 326 1460 3990 02/27/14 2560 331 1370 4170 WW9R - Sample Results in ng/mL W W 9R PFOA PFBS PFHS PFOS 03/27/13 3330 278 1440 4660 04/29/13 2650 244 1200 4340 05/31/13 2660 226 1120 4210 06/27/13 2630 225 1140 4150 07/23/13 2410 212 1030 3670 09/30/13 2730 249 1220 4200 10/28/13 2820 286 1280 4380 11/18/13 2950 305 1340 4540 12/13/13 2690 259 1170 4190 01/30/14 2900 317 1460 4800 02/27/14 2630 270 1370 4660 PAGE 23 OF 24 3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-02 Attachment A: Analyte Trend Data for select sampling points at the Decatur Ground Water Treatment Plant (GWTP) GAC System WW10R - Sample Results in ng/mL FC Charting tar DAL WW10R PFOA------- -------PFOS------- -------- PFBS------- -------- PFHS------- W W 10R PFOA PFBS PFHS PFOS 9/30/2013 2070 247 1030 2770 10/28/2013 2150 264 1030 3160 11/18/2013 2400 303 1120 3890 12/13/2013 1890 239 885 2920 1/30/2014 1330 250 757 1570 2/27/2014 1780 260 935 2860 WW11R - Sample Results in ng/mL W W 11R PFOA PFBS PFHS PFOS 9/30/2014 1720 299 1000 2200 10/28/2014 1100 240 511 1670 11/18/2014 1320 287 680 1850 12/13/2013 1060 198 512 1570 1/30/2014 814 168 362 1540 2/27/2014 1300 262 696 2100 PAGE 24 OF 24