3M ENVIRONMENTAL LAB ORATORY REPORT NO. ISO13 - 05 - 03

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# Final Report Analysis of PFOA, PFBS, PFHS, and PFOS in Surface and Ground Water Samples Collected at the Browns Ferry Road Site Located in Decatur, AL 3 rd 

## Quarter 201 3 Laboratory Request Number: ISO13 - 05 - 03 Method Re quirement: 3M Method ETS - 8 - 044.1 Report Date

– Date of Final Signature 

## Testing Laboratory 3M Environmental Health and Safety Operations Environmental Laboratory 3M Center, Bldg 260 - 05 - N - 17 St. Paul, MN 55144 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 A2LA Certificate # 2052.01. Additionally, the laboratory’s quality system h as been audited and was determined to be in conformance with the EPA GLPs (40 CFR 792) by an independent assessment.3M ENVIRONMENTAL LAB ORATORY REPORT NO. ISO13 - 05 - 03

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### 3M Environmental Laboratory 3M Environmental Laboratory T echnical Director : William K. Reagen, Ph.D. 3M Principal Analytical Investigator : Susan Wolf Report Author: Kevin Eich 

## Analytical Report **ISO13 -**  **05 -**  **03** Analysis of PFOA, PFBS, PFHS, and PFOS in Surface and Ground Water Samples Collected at the Browns Ferry Road Site Located in Decatur, AL 3 rd 

### Quarter 2013 Report Date: Date of Final Signature 

## 1 Introduction/Summary The 3M Environmental Laboratory prepared and analyzed water samples collected by Weston Solutions personnel from Decatur, AL

. S ample s were collected on August 27 and 28, 2013 and returned to the 3M Environment al Laboratory on September 4 , 201 3 at ambient conditions

. All samples were analyzed for perfluorooctanoic acid (PFOA), per fluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHS) and perfluorooctane sulfonate (PFOS) under laboratory project number ISO13 - 05 - 03

. The 3M Environmental Laboratory prepared sample containers for fourteen groundwater well and three surface water locations

. Also included was a sample container for the collection of a soil/sediment rinseate blank. The results for the rinseate blank are included herein. The results for the soil/sediment samples are reported under project E13 - 0618. Each empty container was marked with a “fill to here” line that corresponded to a final volume of 200 mL. Sample bottl e sets for each sampling location included a field sample and field sample duplicate

. Select locations also included a target analyte field matrix spike. Containers designated for field matrix spikes were fortified with an appropriate matrix spike solution containing PFOA, PFBS, PFHS, and PFOS prior to being sent to the field for sample collection. All sample containers were fortified with internal standards and surrogate recovery standards prior to being sent to the field for sample collect ion. Samples were analyzed for PFOA, PF B S, PF H S, and PFOS by ETS - 8 - 044.1 “ Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis”. 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 A2LA 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 assessment.3M ENVIRONMENTAL LAB ORATORY REPORT NO. ISO13 - 05 - 03

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### Table 1 . Sample Results Summary (1)

3M LIMS ID Sample Description PFOA Concentration (ng/mL) PFBS Concentration (ng/mL) PF HS Concentration (ng/mL) PFOS Concentration (ng/mL) ISO13 - 05 - 03 - 001 BFRS - GW - MW1R - 0 - 130827 1.79 0.108 0.874 1.69 ISO13 - 05 - 03 - 002 BFRS - GW - MW1R - DB - 130827 1.70 0.110 0.869 1.69 Average 1.75 0.109 0.872 1.69 %RPD Sample/Sample Dup 5.2 1.8 0.57 0.0 ISO13 - 05 - 03 - 004 BFRS - GW - MW3R - 0 - 130827 22.0 4.34 21.8 26.0 ISO13 - 05 - 03 - 005 BFRS - GW - MW3R - DB - 130827 16.8 3.47 17.4 20.4 Average 19.4 3.91 19.6 23.2 %RPD Sample/Sample Dup 27 (2) 22 (2) 22 (2) 24 (2) ISO13 - 05 - 03 - 006 BFRS - GW - MW4R - 0 - 130827 9.87 0.728 18.5 25.8 ISO13 - 05 - 03 - 007 BFRS - GW - MW4R - DB - 130827 7.59 0.567 14.5 20.9 Average 8.73 0.648 16.5 23.4 %RPD Sample/Sample Dup 26 (2) 25 (2) 24 (2) 21 (2) ISO13 - 05 - 03 - 008 BFRS - GW - MW4L - 0 - 130827 0.269 0.0964 0.263 0.524 ISO13 - 05 - 03 - 009 BFRS - GW - MW4L - DB - 130827 0.264 0.0906 0.245 0.556 Average 0.267 0.0935 0.254 0.540 %RPD Sample/Sample Dup 1.9 6.2 7.1 5.9 ISO13 - 05 - 03 - 011 BFRS - GW - MW5R - 0 - 130828 0.212 0.0535 0.131 0.0874 ISO13 - 05 - 03 - 012 BFRS - GW - MW5R - DB - 130828 0.206 0.0675 0.144 0.0905 Average 0.209 0.0605 0.138 0.0890 %RPD Sample/Sample Dup 2.9 23 (2) 9.5 3.5 ISO13 - 05 - 03 - 013 BFRS - GW - MW5L - 0 - 130828 0.635 0.165 0.262 1.24 ISO13 - 05 - 03 - 014 BFRS - GW - MW5L - DB - 130828 0.591 0.170 0.284 1.29 Average 0.613 0.168 0.273 1.27 %RPD Sample/Sample Dup 7.2 3.0 8.1 4.0 ISO13 - 05 - 03 - 016 BFRS - GW - MW6R - 0 - 130828 2.57 0.249 0.665 7.64 ISO13 - 05 - 03 - 017 BFRS - GW - MW6R - DB - 130828 2.65 0.250 0.688 7.71 Average 2.61 0.250 0.677 7.68 %RPD Sample/Sample Dup 3.1 0.40 3.4 0.91 ISO13 - 05 - 03 - 018 BFRS - GW - MW6L - 0 - 130828 0.195 0.0536 0.0853 0.324 ISO13 - 05 - 03 - 019 BFRS - GW - MW6L - DB - 130828 0.238 0.0565 0.0857 0.360 Average 0.217 0.0551 0.0855 0.342 %RPD Sample/Sample Dup 20 5.3 0.47 11 ISO13 - 05 - 03 - 020 BFRS - GW - MW7R - 0 - 130827 8.79 0.533 1.80 24.4 ISO13 - 05 - 03 - 021 BFRS - GW - MW7R - DB - 130827 8.24 0.497 1.74 25.7 Average 8.52 0.515 1.77 25.1 %RPD Sample/Sample Dup 6.5 7.0 3.4 5.2 NA = Not Applicable (1) All samples associated with the reported sampling location were analyzed by internal standard calibration

. The analytical method uncertainties for the reported results using method ETS - 8 - 044.1 by direct injection are as follows: PFOA ± 1 3 %, PFBS ± 1 3 %, PF HS ± 12%, and PFOS ± 1 6 %. (2) The RPD value did not meet method acceptance criteria of ≤ 20%.3M ENVIRONMENTAL LAB ORATORY REPORT NO. ISO13 - 05 - 03

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### Table 1 continued . Sample Results Summary (1)

3M LIMS ID Sample Description PFOA Concentration (ng/mL) PFBS Concentration (ng/mL) PF HS Concentration (ng/mL) PFOS Concentration (ng/mL) ISO13 - 05 - 03 - 022 BFRS - GW - MW8R - 0 - 130828 0.220 0.0590 0.121 0.268 ISO13 - 05 - 03 - 023 BFRS - GW - MW8R - DB - 130828 0.216 0.0575 0.117 0.250 Average 0.218 0.0583 0.119 0.259 %RPD Sample/Sample Dup 1.8 2.6 3.4 6.9 ISO13 - 05 - 03 - 025 BFRS - GW - MW9R - 0 - 130827 0.112 <0.0250 0.0579 <0.0232 ISO13 - 05 - 03 - 026 BFRS - GW - MW9R - DB - 130827 0.109 <0.0250 0.0510 <0.0232 Average 0.111 <0.0250 0.0545 <0.0232 %RPD Sample/Sample Dup 2.7 NA 13 NA ISO13 - 05 - 03 - 027 BFRS - GW - MW9L - 0 - 130827 0.0301 <0.0250 <0.0250 0.0446 ISO13 - 05 - 03 - 028 BFRS - GW - MW9L - DB - 130827 0.0344 <0.0250 <0.0250 0.0443 Average 0.0323 <0.0250 <0.0250 0.0445 %RPD Sample/Sample Dup 13 NA NA 0.67 ISO13 - 05 - 03 - 029 BFRS - GW - MW10R - 0 - 130827 0.644 0.0692 0.293 0.536 ISO13 - 05 - 03 - 030 BFRS - GW - MW10R - DB - 130827 0.669 0.0658 0.306 0.594 Average 0.657 0.0675 0.300 0.565 %RPD Sample/Sample Dup 3.8 5.0 4.3 10 ISO13 - 05 - 03 - 032 BFRS - GW - MW11L - 0 - 130828 0.286 <0.0250 0.0823 0.387 ISO13 - 05 - 03 - 033 BFRS - GW - MW11L - DB - 130828 0.275 <0.0250 0.0730 0.378 Average 0.281 <0.0250 0.0777 0.383 %RPD Sample/Sample Dup 3.9 NA 12 2.4 ISO13 - 05 - 03 - 034 BFRS - SW - ET02 - 0 - 130828 0.0314 0.0350 <0.0250 0.0547 ISO13 - 05 - 03 - 035 BFRS - SW - ET02 - DB - 130828 0.0313 0.0350 <0.0250 0.0544 Average 0.0314 0.0350 <0.0250 0.0546 %RPD Sample/Sample Dup 0.32 0.0 NA 0.55 ISO13 - 05 - 03 - 036 BFRS - SW - ET03 - 0 - 130828 0.147 0.0565 0.0820 0.295 ISO13 - 05 - 03 - 037 BFRS - SW - ET03 - DB - 130828 0.178 0.0560 0.0792 0.260 Average 0.163 0.0563 0.0806 0.278 %RPD Sample/Sample Dup 19 0.89 3.5 13 ISO13 - 05 - 03 - 039 BFRS - SW - ET04 - 0 - 130828 0.0507 0.0371 <0.0250 0.113 ISO13 - 05 - 03 - 040 BFRS - SW - ET04 - DB - 130828 0.0465 0.0352 <0.0250 0.105 Average 0.0486 0.0362 <0.0250 0.109 %RPD Sample/Sample Dup 8.6 5.3 NA 7.3 ISO13 - 05 - 03 - 041 BFRS - SS08 - RB - 0 - 130828 <0.0240 <0.0250 <0.0250 <0.0232 ISO13 - 05 - 03 - 042 BFRS - GW - TRIP01 - 0 <0.0240 <0.0250 <0.0250 <0.0232 NA = Not Applicable (1) All samples associated with the reported sampling location were analyzed by internal standard calibration

. The analytical method uncertainties for the reported results using method ETS - 8 - 044.1 by direct injection are as follows: PFOA ± 1 3 %, PFBS ± 1 3 %, PFHS ± 12%, and PFOS ± 1 6 %

. (2) The RPD value did not meet method acceptance criteria of ≤ 20%.3M ENVIRONMENTAL LAB ORATORY REPORT NO. ISO13 - 05 - 03

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## 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 Acronym Reference Material Structure Perfluorobutanoic Acid (C4 Acid) PF O A Linear and Branched Perfluorooctanoic Acid (C8 Acid) PF BS Linear Perfluorobutanesulfonate (C4 Sulfonate ) PF H S Linear Perfluorooctanesulfonate (C8 Sulfonate) PFOS Linear and Branched 

## 2.2 Sample Collection All samples were collected in 250 mL Nalgene TM 

### (high - density polyethylene) bottles prepared at the 3M Environmental Laboratory. S amples were collected on August 27 and 28, 2013 and returned to the 3M Environmental Laboratory on September 4, 2013 at ambient conditions

. 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 PF OA , PF BS , PF H S , and PFOS

. Table 3 . Sample Description Key Code.

String Number String Descriptor Example : BFRS - GW - MW4L - 0 - 130827 1 Sample Location BFRS = Browns Ferry Road Site 2 Sample Type GW= Ground Water SW=Surface Water 3 Well Identifier Example: MW4 4 Well Level R = Residuum shallow water - bearing zone L = Bedrock water - bearing zone 5 Sample Type 0 =primary sample DB =duplicate sample FMS = Field Matrix Spike 6 Sampling Date 130827 – August 27 , 2013 

## 2.3 Sample Preparation 9/10/13: Samples were pre pared by removing an aliquot of the well mixed sample and placing it in an autovial for analysis. 9/13/13: Samples requiring dilution prior to analysis were pre pared 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). All samples were analyzed by internal standard calibration . D uring the prepar ation 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.3M ENVIRONMENTAL LAB ORATORY REPORT NO. ISO13 - 05 - 03

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## 2.4 Analysis All samples and quality control samples were analyzed for the four target analytes using high per formance 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. The following analytical runs were processed and reported herein:

• 9/10 /13 : Direct Injection/internal standard analysis PFOA, PFBS, PFHS, PFOS , 13 

### C 4 

### - PFOA, and 13 

### C 4 

### - PFOS; all locations

.

• 9/13/13 : Solvent dilution / in ternal standard analysis PFOS and 13 

### C 4 

### - PFOS ; location s BFRS GW - MW3R, BFRS - GW - MW4R, and BFRS - GW - MW7R

. Due to the nature of the sample s , the wide range of concentrations found in the sample s , 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 integrat e 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 o f 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 4 . Instrumen t Parameters

Instrument Name ETS Buster Analysis Dates 9/10/13 and 9/13/13 Analytical Method ETS - 8 - 044.1 Liquid Chromatograph Agilent 1 100 Guard column Betasil C18 (4.6 mm X 100 mm), 5 μ Analytical column Betasil C18 (4.6 mm X 100 mm), 5 μ Injection Volume 20 μL Mass Spectrometer Applied Biosystems API 4000 Ion Source Turbo Spray Polarity Negative Software Analyst 1.6.1 

### Table 5 . Liquid Chromatography Gradient Program Step Total Time (min) Flow Rate ( μ L/min) 2 mM Ammonium Acetate Methanol 0 0 750 90.0 10.0 1 0.5 750 90.0 10.0 2 4.0 750 70.0 30.0 3 6.0 750 70.0 30.0 4 11.0 750 20.0 80.0 5 13.0 750 20.0 80.0 6 13.5 750 10.0 90.0 7 16.0 750 10.0 90.0 8 16.5 750 90.0 10.0 9 19.0 750 90.0 10.03M ENVIRONMENTAL LAB ORATORY REPORT NO. ISO13 - 05 - 03

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### T able 6 . Mass Transitions Analyte Mass Transition Q1/Q3 Internal Standard Mass Transition Q1/Q3 PFOA 413/369 [ 13 C 8 ]PFOA 421/376 413/219 413/169 PFBS 299/80 [ 18 O 2 ]PFBS 303/84 299/99 PFHS 399/99 [ 13 C 3 ]PFHS 402/99 399/80 PFOS 499/99 [ 13 C 8 ] - PFOS 507/80 499/80 499/130 [ 13 C 4 ] - PFOA surrogate 417/372 [ 13 C 8 ] - PFOA 421/376 [ 13 C 4 ] - PFOS surrogate 503/80 [ 13 C 8 ] - PFOS 507/80 Dwell time was 50 msec for each transition. The individual transitions were summed to produce a “total ion chromatogram” (TIC) , which was u sed for quantitation. 

## 3 Data Analysis 3.1 Calibration 9/10/13: Direct Injection / in ternal standard calibration. Samples were analyzed against a matrix - matched stable isotope internal standard calibration curve. Calibration standards were prepared by spiking known amounts of the stock solution into laboratory prepared reagent water . The calibration standards contai ned an internal standard mix at a nominal concentration of 1.0 ng/mL. T en curve points ranging from 0.025 ng/mL to 25 ng/mL (nominal) were analyzed with the samples

. Of these ten calibration standards, nine contained the surrogates at concentrations rang ing from 0.0250 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 throu gh zero during the fitting process. 9/13/13: Solvent Dilution / in ternal standard calibration. Samples were analyzed against an internal standard matrix - matched calibration curve. Calibration standards were prepared by spiking known amounts of the stock solution into a 50:50 Methanol: Laboratory Reagent Water. The calibration standards contained an internal standard mix at a nominal concentration of 0.5 ng/mL. Twelve standards ranging from 0.0125 ng/mL to 25 ng/mL (nominal) were analyzed with the sampl es . Of 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 standa rd peak area counts was used to fit the data for each analyte. The data were not forced through zero during the fitting process

. For both analyses, e ach curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method calibration accuracy requirements of 100±25% (100±30% 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. T he acceptance criteria for system suitability samples is less3M ENVIRONMENTAL LAB ORATORY REPORT NO. ISO13 - 05 - 03

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### than or equal to 5% relative standard deviation (RSD) for peak area or peak area ratio and retention time crite ria of less than or equal to 2% RSD

. These cri teria 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 an d for which the peak area ratio (or peak area) is at least two times the average peak area ratio (or peak area) of the method blanks. The LOQs associated with the sample analysis are listed in the table below. T able 7 . LOQ Analysis

Date Calibration Dilution Factor PF O A LOQ, ng/mL PF BS LOQ, ng/mL PF H S LOQ, ng/mL PFOS LOQ, ng/mL 9/10/13 Internal standard NA <0.0240 <0.0250 <0.0250 <0.0232 9/13/13 Internal standard 2 NA NA NA <0.0232 NA=Not Applicable 

## 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 acce ptance criteria of 100% ± 25% was met for all analytes for all analyses

. 

## 3.5 Blanks Three types of blanks were prepared and analyzed w ith the samples: method/procedural blanks , a field/trip blank, and a single equipment rinseate blank

. Method blank result s were 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 samples were prepared for the surrogates. LCSs were prepared by spiking known amounts of the analytes into laborato ry reagent water to produce the desired concentration. The LCS samples were then diluted in a similar manner as the samples (if diluted) prior to sample analysis . The method acceptance criteria, average of each level of LCS should be with in 100% ± 20 % wi th an RSD ≤20% , was met for all LCSs

. All batch LCS recovery results were used in the evaluat ion of the analytical method uncertainty in section 3.7 of the report. T he following calculations were used to generate data in Table 8

. 100% * ion Concentrat Spike ion Concentrat Calculated Recovery Percent LCS =

100% * recovery LCS average replicates LCS deviation standard RSD LCS% =3M ENVIRONMENTAL LAB ORATORY REPORT NO. ISO13 - 05 - 03

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### T able 8 . Lab Control Spike Results ETS - 8 - 044.1 Analyzed 9/10/13 In ternal Standard Calibration PFOA (Linear and Branched) PFBS Lab ID Spiked Concentration (ng/mL) Calculated Concentration (ng/mL) %Recovery Spiked Concentration (ng/mL) Calculated Concentration (ng/mL) %Recovery LCS - 130910 - 1 0.190 0.179 94.2 0.198 0.192 97.1 LCS - 130910 - 2 0.190 0.187 98.6 0.198 0.200 101 LCS - 130910 - 3 0.190 0.177 93.3 0.198 0.195 98.3 Average ± %RSD 95.4 % ± 3.0 % 98.8 % ± 2.0 % LCS - 130910 - 4 1.90 1.97 103 1.98 2.19 110 LCS - 130910 - 5 1.90 1.98 104 1.98 2.05 103 LCS - 130910 - 6 1.90 1.99 105 1.98 2.07 104 Average ± %RSD 104 % ± 0.96 % 106 % ± 3.6 % LCS - 130910 - 7 16.2 14.4 89.0 16.9 15.7 92.9 LCS - 130910 - 8 16.2 14.5 89.7 16.9 15.6 92.3 LCS - 130910 - 9 16.2 14.4 89.0 16.9 15.5 91.8 Average ± %RSD 89.2 % ± 0.45 % 92.3 % ± 0.60 % ETS - 8 - 044.1 Analyzed 9/10/13 Internal Standard Calibration PFHS PFOS (Linear and Branched) Lab ID Spiked Concentration (ng/mL) Calculated Concentration (ng/mL) %Recovery Spiked Concentration (ng/mL) Calculated Concentration (ng/mL) %Recovery LCS - 130910 - 1 0.198 0.197 99.7 0.184 0.180 97.7 LCS - 130910 - 2 0.198 0.211 107 0.184 0.180 97.9 LCS - 130910 - 3 0.198 0.193 97.3 0.184 0.202 110 Average ± %RSD 101 % ± 5.0 % 102 % ± 6.9 % LCS - 130910 - 4 1.98 2.21 112 1.84 1.98 107 LCS - 130910 - 5 1.98 2.42 122 1.84 1.89 103 LCS - 130910 - 6 1.98 2.21 112 1.84 1.81 98.6 Average ± %RSD 115 % ± 5.0 % 103 % ± 4.1 % LCS - 130910 - 7 16.9 16.8 99.6 15.7 13.7 87.0 LCS - 130910 - 8 16.9 16.1 95.1 15.7 13.6 86.6 LCS - 130910 - 9 16.9 16.2 95.6 15.7 13.6 86.9 Average ± %RSD 96.8 % ± 2.5 % 86.8 % ± 0.24 %3M ENVIRONMENTAL LAB ORATORY REPORT NO. ISO13 - 05 - 03

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### Table 8 continued. Lab Control Spike Results ETS - 8 - 044.1 Analyzed 9/10/13 Internal Standard Calibration 13 C 4 - PFOA 13 C 4 - PFOS Lab ID Spiked Concentration (ng/mL) Calculated Concentration (ng/mL) %Recovery Spiked Concentration (ng/mL) Calculated Concentration (ng/mL) %Recovery LCS - 130910 - 1 0.198 0.203 103 0.189 0.208 110 LCS - 130910 - 2 0.198 0.209 106 0.189 0.195 103 LCS - 130910 - 3 0.198 0.209 106 0.189 0.219 116 Average ± %RSD 105 % ± 1.6 % 110 % ± 5.9 % LCS - 130910 - 4 1.98 2.15 109 1.89 2.11 112 LCS - 130910 - 5 1.98 2.01 102 1.89 1.93 102 LCS - 130910 - 6 1.98 2.08 105 1.89 1.88 99.4 Average ± %RSD 105 % ± 3.3 % 104 % ± 6.4 % ETS - 8 - 044.1 Analyzed 9/13 /13 Internal Standard C alibration PFOS (Linear and Branched) 13 C 4 - PFOS Lab ID Spiked Concentration (ng/mL) Calculated Concentration (ng/mL) %Recovery Spiked Concentration (ng/mL) Calculated Concentration (ng/mL) %Recovery LCS - 130913 - 1 0.184 0.166 90.2 0.189 0.181 95.5 LCS - 130913 - 2 0.184 0.158 86.1 0.189 0.184 97.2 LCS - 130913 - 3 0.184 0.170 92.5 0.189 0.181 95.6 Average ± %RSD 89.6 % ± 3.6 % 96.1 % ± 0.99 % LCS - 130913 - 4 1.84 1.80 98.0 1.89 1.76 93.1 LCS - 130913 - 5 1.84 1.70 92.6 1.89 1.85 98.0 LCS - 130913 - 6 1.84 1.77 96.2 1.89 1.88 99.4 Average ± %RSD 95.6 % ± 2.9 % 96.8 % ± 3.4 % LCS - 130913 - 7 32.2 31.1 96.6 LCS - 130913 - 8 32.2 31.7 98.4 LCS - 130913 - 9 32.2 31.4 97.6 Average ± %RSD 97.5 % ± 0.92 %3M ENVIRONMENTAL LAB ORATORY REPORT NO. ISO13 - 05 - 03

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## 3.7 Analytical Method Uncertainty Analytical method 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 9 . Analytical Method Uncertainty Analyte Calibration Standard Deviation (%) Method Uncertainty PFOA Internal 6.42 ±1 3 % PFBS Internal 6.72 ±13 % PFHS Internal 6.12 ±12% PFOS Internal 8.22 ±16 % 

## 3.8 Field Matrix Spikes (FMS) Field matrix spike sample containers were prepared for select sampling locations 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 to the field for sample collection. Field matrix spikes must be at least 0.5 times the analyte concentration to be considered an appropriate spike level. Field matrix spike recoveries within method acceptance criteria of 100±30% confirm that “unknown” components in the sample matrix do not significantly interfere with the extraction and analysis of the analytes of interest. The reference standards for PFOA and PFOS in the field matrix spiking solution consisted of linear and branched isomers. The locations for which FMS sample containers were prepared are listed in Table 10

. Field matrix spikes are presented in section 4 of this report. 100% * on Concentrat Spike Dup.) Sample Field & Sample Field : ion Concentrat Average FMS of ion Concentrat (Sample Recovery FMS − = 

### Table 10 . Field Matrix Spike (FMS) Concentrations

Samp ling location PFO A ng/mL PFBS ng/mL PF HS ng/mL PF OS ng/mL GW - MW1R, GW - MW4L, GW - MW5L, GW MW8R, GW - MW10R, SW - ET03, and Trip Blank 0.958 1.00 1.00 0.927 

## 4 Data Summary and Discussion Tables 11 - 18 below summarize the sample results and target analyte field matrix spike recoveries for the sampling locations as well as the T rip Blank

. The surrogate recovery standard recoveries are presented in Table 1 9 . 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 sig nificant figures. Field matrix spikes meeting the method acceptance criteria of ± 30%, demonstrate that the method is appropriate for the given matrix.3M ENVIRONMENTAL LAB ORATORY REPORT NO. ISO13 - 05 - 03

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### All target analyte field matrix spike s met method acceptance criteria with the following exception :

• BFRS - SW - ET03 ; The 13 

### C 4 

### - PFOS results for this location are not reportable due to the analyte area counts were below the LLOQ area counts and less than t wo times the average area counts for the method blanks. This location had acceptable FMS recoveries for each analyte. Table 11 . BFRS - GW - MW1R PFO A PF BS 3M LIMS ID Description Concentration (ng/mL) %Recovery Concentration (ng/mL) %Recovery ISO13 - 05 - 03 - 001 BFRS - GW - MW1R - 0 - 130827 1.79 NA 0.108 NA ISO13 - 05 - 03 - 002 BFRS - GW - MW1R - DB - 130827 1.70 NA 0.110 NA ISO13 - 05 - 03 - 003 BFRS - GW - MW1R - FMS - 130827 2.55 84.0 1.02 91.1 Average Concentration (ng/mL) ± %RPD 1.75 ng/mL ± 5.2 % 0.109 ng/mL ± 1.8 % PFH S PFOS 3M LIMS ID Description Concentration (ng/mL) %Recovery Concentration (ng/mL) %Recovery ISO13 - 05 - 03 - 001 BFRS - GW - MW1R - 0 - 130827 0.874 NA 1.69 NA ISO13 - 05 - 03 - 002 BFRS - GW - MW1R - DB - 130827 0.869 NA 1.69 NA ISO13 - 05 - 03 - 003 BFRS - GW - MW1R - FMS - 130827 1.92 105 2.62 100 Average Concentration (ng/mL) ± %RPD 0.872 ng/mL ± 0.57 % 1.69 ng/mL ± 0.0 % NA = Not Applicable 

### Table 12 . BFRS - GW - MW4L PFO A PF BS 3M LIMS ID Description Concentration (ng/mL) %Recovery Concentration (ng/mL) %Recovery ISO13 - 05 - 03 - 008 BFRS - GW - MW4L - 0 - 130827 0.269 NA 0.0964 NA ISO13 - 05 - 03 - 009 BFRS - GW - MW4L - DB - 130827 0.264 NA 0.0906 NA ISO13 - 05 - 03 - 010 BFRS - GW - MW4L - FMS - 130827 1.22 99.5 1.10 101 Average Concentration (ng/mL) ± %RPD 0.267 ng/mL ± 1.9 % 0.0935 ng/mL ± 6.2 % PFH S PFOS 3M LIMS ID Description Concentration (ng/mL) %Recovery Concentration (ng/mL) %Recovery ISO13 - 05 - 03 - 008 BFRS - GW - MW4L - 0 - 130827 0.263 NA 0.524 NA ISO13 - 05 - 03 - 009 BFRS - GW - MW4L - DB - 130827 0.245 NA 0.556 NA ISO13 - 05 - 03 - 010 BFRS - GW - MW4L - FMS - 130827 1.32 107 1.55 109 Average Concentration (ng/mL) ± %RPD 0.254 ng/mL ± 7.1 % 0.540 ng/mL ± 5.9 % NA = Not Applicable3M ENVIRONMENTAL LAB ORATORY REPORT NO. ISO13 - 05 - 03

PAGE 13 OF 17 

### Table 13 . BFRS - GW - MW5L PFO A PF BS 3M LIMS ID Description Concentration (ng/mL) %Recovery Concentration (ng/mL) %Recovery ISO13 - 05 - 03 - 013 BFRS - GW - MW5L - 0 - 130828 0.635 NA 0.165 NA ISO13 - 05 - 03 - 014 BFRS - GW - MW5L - DB - 130828 0.591 NA 0.170 NA ISO13 - 05 - 03 - 015 BFRS - GW - MW5L - FMS - 130828 1.59 102 1.11 94.3 Average Concentration (ng/mL) ± %RPD 0.613 ng/mL ± 7.2 % 0.168 ng/mL ± 3.0 % PFH S PFOS 3M LIMS ID Description Concentration (ng/mL) %Recovery Concentration (ng/mL) %Recovery ISO13 - 05 - 03 - 013 BFRS - GW - MW5L - 0 - 130828 0.262 NA 1.24 NA ISO13 - 05 - 03 - 014 BFRS - GW - MW5L - DB - 130828 0.284 NA 1.29 NA ISO13 - 05 - 03 - 015 BFRS - GW - MW5L - FMS - 130828 1.35 108 2.26 107 Average Concentration (ng/mL) ± %RPD 0.273 ng/mL ± 8.1 % 1.27 ng/mL ± 4.0 % NA = Not Applicable 

### Table 14

. BFRS - GW - MW8R PFO A PF BS 3M LIMS ID Description Concentration (ng/mL) %Recovery Concentration (ng/mL) %Recovery ISO13 - 05 - 03 - 022 BFRS - GW - MW8R - 0 - 130828 0.220 NA 0.0590 NA ISO13 - 05 - 03 - 023 BFRS - GW - MW8R - DB - 130828 0.216 NA 0.0575 NA ISO13 - 05 - 03 - 024 BFRS - GW - MW8R - FMS - 130828 1.23 106 1.01 95.2 Average Concentration (ng/mL) ± %RPD 0.218 ng/mL ± 1.8 % 0.0583 ng/mL ± 2.6 % PFH S PFOS 3M LIMS ID Description Concentration (ng/mL) %Recovery Concentration (ng/mL) %Recovery ISO13 - 05 - 03 - 022 BFRS - GW - MW8R - 0 - 130828 0.121 NA 0.268 NA ISO13 - 05 - 03 - 023 BFRS - GW - MW8R - DB - 130828 0.117 NA 0.250 NA ISO13 - 05 - 03 - 024 BFRS - GW - MW8R - FMS - 130828 1.15 103 1.17 98.3 Average Concentration (ng/mL) ± %RPD 0.119 ng/mL ± 3.4 % 0.259 ng/mL ± 6.9 % NA = Not Applicable3M ENVIRONMENTAL LAB ORATORY REPORT NO. ISO13 - 05 - 03

PAGE 14 OF 17 

### Table 15 . BFRS - GW - MW10R PFO A PF BS 3M LIMS ID Description Concentration (ng/mL) %Recovery Concentration (ng/mL) %Recovery ISO13 - 05 - 03 - 029 BFRS - GW - MW10R - 0 - 130827 0.644 NA 0.0692 NA ISO13 - 05 - 03 - 030 BFRS - GW - MW10R - DB - 130827 0.669 NA 0.0658 NA ISO13 - 05 - 03 - 031 BFRS - GW - MW10R - FMS - 130827 1.50 88.0 1.15 108 Average Concentration (ng/mL) ± %RPD 0.657 ng/mL ± 3.8 % 0.0675 ng/mL ± 5.0 % PFH S PFOS 3M LIMS ID Description Concentration (ng/mL) %Recovery Concentration (ng/mL) %Recovery ISO13 - 05 - 03 - 029 BFRS - GW - MW10R - 0 - 130827 0.293 NA 0.536 NA ISO13 - 05 - 03 - 030 BFRS - GW - MW10R - DB - 130827 0.306 NA 0.594 NA ISO13 - 05 - 03 - 031 BFRS - GW - MW10R - FMS - 130827 1.26 96.1 1.42 92.2 Average Concentration (ng/mL) ± %RPD 0.300 ng/mL ± 4.3 % 0.565 ng/mL ± 1 0 % NA = Not Applicable 

### Table 16 . BFRS - SW - ET03 PFO A PF BS 3M LIMS ID Description Concentration (ng/mL) %Recovery Concentration (ng/mL) %Recovery ISO13 - 05 - 03 - 036 BFRS - SW - ET03 - 0 - 130828 0.147 NA 0.0565 NA ISO13 - 05 - 03 - 037 BFRS - SW - ET03 - DB - 130828 0.178 NA 0.0560 NA ISO13 - 05 - 03 - 038 BFRS - SW - ET03 - FMS - 130828 1.16 104 1.04 98.4 Average Concentration (ng/mL) ± %RPD 0.163 ng/mL ± 19 % 0.0563 ng/mL ± 0.89 % PFH S PFOS 3M LIMS ID Description Concentration (ng/mL) %Recovery Concentration (ng/mL) %Recovery ISO13 - 05 - 03 - 036 BFRS - SW - ET03 - 0 - 130828 0.0820 NA 0.295 NA ISO13 - 05 - 03 - 037 BFRS - SW - ET03 - DB - 130828 0.0792 NA 0.260 NA ISO13 - 05 - 03 - 038 BFRS - SW - ET03 - FMS - 130828 1.06 97.9 1.36 117 Average Concentration (ng/mL) ± %RPD 0.0806 ng/mL ± 3.5% 0.278 ng/mL ± 13 % NA = Not Applicable3M ENVIRONMENTAL LAB ORATORY REPORT NO. ISO13 - 05 - 03

PAGE 15 OF 17 

### Table 17 . Trip Blank PFO A PF BS 3M LIMS ID Description Concentration (ng/mL) %Recovery Concentration (ng/mL) %Recovery ISO13 - 05 - 03 - 042 BFRS - GW - TRIP01 - 0 < 0.0240 NA <0.0250 NA ISO13 - 05 - 03 - 043 BFRS - GW - TRIP01 - FMS 0.874 91.2 0.974 97.4 PFH S PFOS 3M LIMS ID Description Concentration (ng/mL) %Recovery Concentration (ng/mL) %Recovery ISO13 - 05 - 03 - 042 BFRS - GW - TRIP01 - 0 <0.0250 NA <0.0232 NA ISO13 - 05 - 03 - 043 BFRS - GW - TRIP01 - FMS 1.03 103 0.856 92.3 NA = Not Applicable 

### Table 18 . Soil/Sediment Rinseate Blank PFO A PF BS PF HS PFOS 3M LIMS ID Description Concentration (ng/mL) Concentration (ng/mL) Concentration (ng/mL) Concentration (ng/mL) ISO13 - 05 - 03 - 041 BFRS - SS08 - RB - 0 - 130828 <0.0240 <0.0250 <0.0250 <0.0232

. 

### Table 19 . Surrogate Recovery

3M LIMS ID Description 13 C 4 - PFOA 13 C 4 - PFOS %Recovery %Recovery ISO13 - 05 - 03 - 001 BFRS - GW - MW1R - 0 - 130827 100 91.9 ISO13 - 05 - 03 - 002 BFRS - GW - MW1R - DB - 130827 89.9 95.8 ISO13 - 05 - 03 - 003 BFRS - GW - MW1R - FMS - 130827 84.7 106 ISO13 - 05 - 03 - 004 BFRS - GW - MW3R - 0 - 130827 91.2 97.8 , 94.7 (2) ISO13 - 05 - 03 - 005 BFRS - GW - MW3R - DB - 130827 90.6 100 , 85.7 (2) ISO13 - 05 - 03 - 006 BFRS - GW - MW4R - 0 - 130827 97.6 99.7 , 93.3 (2) ISO13 - 05 - 03 - 007 BFRS - GW - MW4R - DB - 130827 90.8 101 , 90.3 (2) ISO13 - 05 - 03 - 008 BFRS - GW - MW4L - 0 - 130827 84.3 99.5 ISO13 - 05 - 03 - 009 BFRS - GW - MW4L - DB - 130827 90.1 99.1 ISO13 - 05 - 03 - 010 BFRS - GW - MW4L - FMS - 130827 89.9 94.5 ISO13 - 05 - 03 - 011 BFRS - GW - MW5R - 0 - 130828 95.4 88.7 ISO13 - 05 - 03 - 012 BFRS - GW - MW5R - DB - 130828 91.3 91.9 ISO13 - 05 - 03 - 013 BFRS - GW - MW5L - 0 - 130828 96.6 98.6 ISO13 - 05 - 03 - 014 BFRS - GW - MW5L - DB - 130828 92.0 95.0 ISO13 - 05 - 03 - 015 BFRS - GW - MW5L - FMS - 130828 94.9 106 (1) NR=Not Reportable; Area counts were below the LLOQ and were not two times the method blank area counts. (2) R esult from analysis on 9/13/13 for PFOS and 13 C 4 - PFOS surrogate

.3M ENVIRONMENTAL LAB ORATORY REPORT NO. ISO13 - 05 - 03

PAGE 16 OF 17 

### Table 19 continued. Surrogate Recovery

3M LIMS ID Description 13 C 4 - PFOA 13 C 4 - PFOS %Recovery %Recovery ISO13 - 05 - 03 - 016 BFRS - GW - MW6R - 0 - 130828 103 102 ISO13 - 05 - 03 - 017 BFRS - GW - MW6R - DB - 130828 98.4 95.8 ISO13 - 05 - 03 - 018 BFRS - GW - MW6L - 0 - 130828 94.5 94.7 ISO13 - 05 - 03 - 019 BFRS - GW - MW6L - DB - 130828 109 91.8 ISO13 - 05 - 03 - 020 BFRS - GW - MW7R - 0 - 130827 101 98.8 , 95.4 (2) ISO13 - 05 - 03 - 021 BFRS - GW - MW7R - DB - 130827 94.2 90.1 , 92.2 (2) ISO13 - 05 - 03 - 022 BFRS - GW - MW8R - 0 - 130828 96.0 105 ISO13 - 05 - 03 - 023 BFRS - GW - MW8R - DB - 130828 94.3 90.3 ISO13 - 05 - 03 - 024 BFRS - GW - MW8R - FMS - 130828 94.1 97.4 ISO13 - 05 - 03 - 025 BFRS - GW - MW9R - 0 - 130827 91.5 99.2 ISO13 - 05 - 03 - 026 BFRS - GW - MW9R - DB - 130827 86.5 85.3 ISO13 - 05 - 03 - 027 BFRS - GW - MW9L - 0 - 130827 91.9 92.9 ISO13 - 05 - 03 - 028 BFRS - GW - MW9L - DB - 130827 101 93.0 ISO13 - 05 - 03 - 029 BFRS - GW - MW10R - 0 - 130827 88.4 90.4 ISO13 - 05 - 03 - 030 BFRS - GW - MW10R - DB - 130827 92.6 105 ISO13 - 05 - 03 - 031 BFRS - GW - MW10R - FMS - 130827 91.3 103 ISO13 - 05 - 03 - 032 BFRS - GW - MW11L - 0 - 130828 89.7 104 ISO13 - 05 - 03 - 033 BFRS - GW - MW11L - DB - 130828 76.0 107 ISO13 - 05 - 03 - 034 BFRS - SW - ET02 - 0 - 130828 85.1 97.0 ISO13 - 05 - 03 - 035 BFRS - SW - ET02 - DB - 130828 93.7 110 ISO13 - 05 - 03 - 036 BFRS - SW - ET03 - 0 - 130828 91.3 NR (1) ISO13 - 05 - 03 - 037 BFRS - SW - ET03 - DB - 130828 87.2 NR (1) ISO13 - 05 - 03 - 038 BFRS - SW - ET03 - FMS - 130828 94.5 NR (1) ISO13 - 05 - 03 - 039 BFRS - SW - ET04 - 0 - 130828 98.2 99.8 ISO13 - 05 - 03 - 040 BFRS - SW - ET04 - DB - 130828 92.4 94.6 ISO13 - 05 - 03 - 041 BFRS - SS08 - RB - 0 - 130828 90.8 95.7 ISO13 - 05 - 03 - 042 BFRS - GW - TRIP01 - 0 98.9 109 ISO13 - 05 - 03 - 043 BFRS - GW - TRIP01 - FMS 93.6 93.3 (1) NR=Not Reportable; Area counts were below the LLOQ and were not two times the method blank area counts. (2) Result from analysis on 9/13/13 for PFOS and 13 C 4 - PFOS surrogate.3M ENVIRONMENTAL LABORATORY REPORT

NO. IS013-05-03



### 5 Conclusio n Laborator y contro l spike s wer e use d t o determin e th e analytica l metho d accurac y an d precisio n fo r al l analytes

. Th e accurac

y an d precisio n wer e the n use d t o estimat e th e metho d uncertaint y fo r th e results

. Fiel d an d laborator y matri x spik e recoverie s demonstrate d tha t th e analytica l metho d wa s appropriat e fo r th e give n sampl e matrix

. Metho d ETS-8-044. 1 "Metho d o f Analysi s fo r th e Determinatio n o f Perfluorinate d Compound s i n Wate r b y LC/MS/MS ; Direc

t Injectio n Analysis " wa s use d fo r analysis

. Analytica l result s ar e reporte d i n Tabl e 1 an d 1 1 -1 9 o f thi s report . 

## 6 Dat a /

Sampl e Retentio n Al l remainin g sampl e an d associate d projec t dat a (hardcop y an d electronic ) wil l b e archive d accordin g t o 3 M Environmenta l Laborator y standar d operatin g procedures

. 

## 7 Signature s

Susa n T

. Wolf , 3 M Pmnjcipa l Analytica l Investigato r Dat e

Willia m K

. Reagen , Ph.D. , 3 M Envirorimenta l Technica l Directo r Dat e

Th e 3 M Environmenta l Laboratory' s Quality Assuranc e Uni t ha s audite d th e dat a an d repor t fo r thi s project

.

Quality Assuranc e Redresentativ e / Dat e

This test report shall not be reproduced

except in full, without

written approval

of the 3NI Environmental

Laboratory.

PAG E 1 7 O F 1 7