3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

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PAGE 1 OF 25 

# Final Report

Analysis of PFOA, PFBS, PFHS, and PFOS in Aqueous Samples from

3M Decatur, Alabama : Groundwater Treatment Plant GAC System

– December 2013

Laboratory Request Number: ISO13

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Method Re quirement: 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

a ccordance 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.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

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PAGE 2 OF 25 

### 3M Enviro nmental Laboratory

3M Environmental Laboratory Technical Director: William K. Reagen, Ph.D

. 3M Principal Analytical Investigator: Susan Wolf Report Author: Chelsie Grochow



## Analytical Report ISO13

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3M Decatur Groundwater Treatment Plant System; Dece mber 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 S olutions personnel

on December 1 3 , 2013

. Samples were returned to the 3M Environmental Laboratory for analysis of

P erfluorooctanoate (PFOA) , Perfluorobutane sulfonate (PFBS), Perf luorohexane sulfonate (PFHS), Perfluorooctane sulfonate (PFOS) under la borat ory project number ISO13

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. Analysis of the samples was completed as specified under 3M Environmental Laboratory General Project Outline (GPO) number GPO11

- 1006.

T he 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

sa mple 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. Contain ers 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. S ample bottles for sampling locations ACM2 and ACE

, along with the Trip Blank

sam ple and low spike

, were fortified with internal standards and surrogates prior to being sent to the field for sample collection. Due to an error during the bottle prep, internal standard was not added to

the AC E FMS sample prior to analysis.

Samples we re prepared and analyzed by method ETS

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- 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 su mmarizes 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 requiremen ts 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 t o be in conformance with the EPA GLPs (40 CFR 792) by an independent A2LA assessment.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

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PAGE 3 OF 25 

### Table 1 . Sa mple Results Summary

3M LIMS ID Sample Description PFOA

Concentration (ng/mL) PFBS

Concentration (ng/mL) PFHS

Concentration (ng/mL) PFOS

Concentration (ng/mL)

ISO13

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- 001 DAL

- GW

- ACI ; Sample 1840 1330 687 1960

ISO13

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- 002 DAL

- GW

- ACI ; Sample Dup 1820 1360 703 1980

Average 1830 (1) 1350 (1) 695 (1) 1970 (1)

%RPD Sample/Sample Dup 1.1 2.2 2.3 1 .0

ISO13

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- 004 DAL

- GW

- ACM2; Sample 0.0729 1430 0.0587 0.531

ISO13

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- 005 DAL

- GW

- ACM2 ; Sample Dup 0.0775 1440 0.0829 0.606

Average 0.0752 (2 ) 1440 (1) 0.0708 (2 ) 0.569 (2 )

%RPD Sample/Sample Dup 6.1 0.69 34 (3 ) 13

ISO13

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- 007 DAL

- GW

- ACE; Sample 0.0728 0.0725 <0.0500 0.0276

ISO13

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- 008 DAL

- GW

- ACE ; Sample Dup 0.0868 0.0806 0.0648 0.0330

Average 0.0798 (2 ) 0.0766 (2 ) 0.0648 (2 ) 0.0 3 03 (2 )

%RPD Sample/Sample Dup 1 8 11 NA 18

ISO13

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- 010 DAL

- GW

- WW8R; Sample 2700 316 1260 4070

ISO13

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- 011 DAL

- GW

- WW8R ; Sample Dup 2730 316 1270 4050

Average 2720 (1) 316 (1) 1270 (1) 4060 (1)

%RPD Sample/Sample Dup 1. 1 0. 0 0. 79 0.49

ISO13

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- 013 DAL

- GW

- WW9R; Sample 2670 264 1170 4160

ISO13

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- 014 DAL

- GW

- WW9R ; Sample Dup 2700 253 1160 4210

Average 2690 (1) 259 (1) 1170 (1) 4190 (1)

%RPD Sample/Sample Dup 1.1 4.2 0.85 1.2

ISO13

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- 019 DAL

- GW

- WW10R; Sample 1910 239 889 2950

ISO13

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- 020 DAL

- GW

- WW10R ; Sample Dup 1870 238 880 2890

Average 1890 (1) 239 (1) 885 (1) 2920 (1)

%RPD Sample/Sample Dup 2.1 0. 42 1.0 2. 1

ISO13

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- 022 DAL

- GW

- WW11R; Sample 1050 200 515 1570

ISO13

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- 023 DAL

- GW

- WW11R ; Sample Dup 1060 195 508 1560

Average 1 060 (1) 198 (1) 512 (1) 1570 (1)

%RPD Sample/Sample Dup 0.94 2.5 1.4 0.64

NA = Not Applicable (1) Reported results were prepared and analyzed by ETS

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- 044. 1 using external standard calibration . The analytical method

uncertainties assoc iated with the reported results are as follows: PFOA ±17 %, PFBS ± 1 7 %, PFHS ±16 %, and PFOS ± 21 %. (2) Reported results were prepared and analyzed by ETS

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- 044.1 using internal standard calibration. The analytical method
uncertainties associated with the reporte d results are as follows: PFOA ± 1 7 %, PFBS ±1 4 %, PFHS ± 23 %, and PFOS ± 21 %. (3) Sample/sample duplicate RPD did not meet acceptance criteria of ≤ 20%.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

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PAGE 4 OF 25 

# 2 Methods

- Analytical and Preparatory

2.1 Methods
Analysis was completed using 3M Environmental Laboratory Method ETS

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- 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

Perfluorooctanoic Acid (C8 Acid) PFOA Linear + Branched

Perfluorobutanesulfonate (C4 Sulfonate ) PFBS Linear

Perfluorohexanesulfonate (C6 Sulfonate) P FHS Linear

Perfluorooctanesulfonate (C8 Sulfonate) PFOS Linear + Branched



## 2.2 Sample Collection
Samples were collected on December 1 3 , 201 3 in Nalgene TM 

### (high

- density polyethylene) bottles prepared at the 3M Environmental Laboratory. Prior to sample collec tion, 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 Tr ip Bla nk sample and low spike, were fortified with a mixture of mass

- labeled

internal standards at a nom inal 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 b y the laboratory at

ambient conditions on December 18 , 201 3

.



## 2.3 Sample Preparation

All s ample s 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 m L 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 b y external standard calibration. Further dilution may have been applied by using a lower injection volume on the instrument.

The ACE and ACM2 sample set s and the Trip Blank sample were prepared and analyzed for all analytes by transferring a n aliquot o f the well mixed sample into an autovial. Prepared samples were analyzed by internal standard calibration. Following sample analysis, it was discovered that the AC E FMS sample was not fortified with internal standard. Therefore, internal standard was ad ded to an aliquot of the AC E FMS sample, and the AC E sample set was re

- analyzed by internal standard

calibration.

During the preparation of the laboratory control samples for internal standard calibration , an aliquot of a separate internal standard spik ing 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 f our target analytes using high per formance liquid chromatography/ tandem mass spec trometry (HPLC/MS/MS). Pertinent instrument parameters, the liquid chromatography gradient program, and the specific mass transitions analyzed are described

in the tables below.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

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PAGE 5 OF 25 

### Due to the nature of the sample, the wide range of concentrations found in th e 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

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- 010. The consistency of the laboratory’s integration is ensured through the training of laboratory personnel, the peer review process required fo r 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 ETS Buster

Analysis Dates 1/ 8/14

– external standard calibration

1/9/14 and 1/10/14

– internal standard calibration

Analytical Method ETS

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- 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 5 or 20 μ L

Mass Spectrometer Applied Biosystems API 4000

Ion Source Turbo Spray

Polarity Negative

Software Analyst 1.6.1



### Table 4 . Liquid Chromatography Gradient Program.

Step

Number Total Time (min) Flow Rate ( μ L/min) Percent A

(2 mM ammonium acetate) Percent B

(Methanol)

0 0.00 750 90.0 10.0

1 0.50 750 90.0 10.0

2 4.00 750 70.0 30.0

3 6.00 750 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

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PAGE 6 OF 25 

### Table 5 . Mass Transitions

.

Analyte Mass Transition

Q1/Q3 Internal Standard (1) Mass Transition
Q1/Q3

PFOA 413/369

[ 13 C 8 ] PFOA 421/ 376 413/219

413/169

PFBS 299/80 [ 1 8 O 2 ]PFB S 303/84 299/99

PFHS 399/99 [ 13 C 3 ]PFHS 402/ 80 399/80

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 5 07/80

Dwell time was 20 msec for each transition. The individual transitions were summed to produce a “total ion chromatogram” (TIC) , which was u sed for quantitation.

(1) Internal standard s were used for the analysis on 1/9/14 and 1/10/14.



# 3 Data Analy sis

3.1 Calibration
External Standard Calibration Analysis on 1/8/14 : 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 0.02 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 quadr atic, 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 1/9/14 and 1/10/14 : 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

calibra tion standards ranging from 0 .0 25 ng/mL to 25 ng/mL (nominal) were analyzed with the prepared samples. Of these t hirteen calibration standards, eleven contained the surrogates at concentrations ranging from 0.0 25 ng/mL to 10 ng/mL nominal. A quadratic, 1/x weighted, calibration cur ve 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 pe ak area ratios and the resultant calibration curve confirmed accuracy of each curve point.

For each calibration curve, t he 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 100±25% (100±30% for the lowest curve point) were met for all analyte s. The correlation coefficient r was greater than 0.995 for all analytes

.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

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PAGE 7 OF 25 

## 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 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 cri teria were met for all analytes

.



## 3.3 Limit of Quantitation (LOQ)

The LOQ as defined in method ETS

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- 044. 1 is the lowest non

- zer o 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

.

T able 6 . LOQ

Analyte LOQ, ng/mL

1/8/14 Analysis LOQ, ng/mL

1/9/14 Analysis LOQ, ng/mL

1/10/14 Analysis

PFOA 0.0192 (1) 0.0240 0.0287

PFBS 0.0200 (1) 0.0250 0.0250

PFHS 0.0200 (1) 0.0500 0.0500

PFOS 0.0185 (1) 0.0232 0.0232
(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 w ith the samples: method blanks/solvent blanks and field/trip blanks . Each blank result wa s reviewed and used to ev aluate 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 fo r 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, t he LCSs were then

diluted with me thanol in the same manner as the samples

. Method ETS

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- 044.1 states that the average recovery of LCS s at each spiking level be within 80%

- 120% wi th a RSD ≤20%. All LCS sampl es met method accuracy criteri a except for the mid level LCSs for PFHS (123%) on 1/9/14 and

PFOS (121%) on 1/10/14. A method deviation is included with the raw data.

All LCSs were used in the determination of the analytical m ethod uncertainty in section 3.7

.

T he following calculations were used to generate data in Table 7

.

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

=

100% * recovery LCS average replicates LCS deviation standard RSD LCS%

=3M ENVIRONMENTAL LAB ORATORY

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PAGE 8 OF 25 

### Table 7 . Lab Control Spike Results.

ETS

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- 044.1

Ex

ternal Standard

Calibration

Analyzed 1/8/14 PFOA (Linear + Branched ) PFOA surrogate

Lab ID Spiked

Concentration (ng/mL) Calculated

Concentration (ng/mL) %Recovery Spiked

Concentration (ng/mL) Calculated

Concentration (ng/mL) %Recovery

LCS

- 140108

- 1 0.191 0.180 94.2 0.199 0.222 112

LCS

- 140108

- 2 0.191 0.174 91.1 0.199 0.219 110

LCS

- 140108

- 3 0.191 0.176 92.1 0.199 0.217 109

Avera ge ± %RSD 92.5 % ± 1.7 % 1 10 % ± 1

. 4 %

LCS

- 140108

- 4 4.74 4.86 102 4.94 5.16 105

LCS

- 140108

- 5 4.74 4.82 102 4.94 5.07 103

LCS

- 140108

- 6 4.74 4.79 101 4.94 5.07 103

Average ± %RSD 102 % ± 0.57 % 104 % ± 1.1 %

LCS

- 140108

- 7 38.2 38.0 99.6

LCS

- 140108

- 8 38.2 36.3 9 5.1

LCS

- 140108

- 9 38.2 35.9 94.0

Average ± %RSD 96.2 % ± 3.1 %

ETS

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- 044.1

External Standard

Calibration

Analyzed 1/8/14 PFBS PFHS

Lab ID Spiked

Concentration (ng/mL) Calculated

Concentration (ng/mL) %Recovery Spiked

Concentration (ng/mL) Calculated

Concentration (ng/mL) %Recovery

LCS

- 140108

- 1 0.199 0.204 102 0.199 0.194 97.7

LCS

- 140108

- 2 0.199 0.201 101 0.199 0.211 106

LCS

- 140108

- 3 0.199 0.195 97.9 0.199 0.198 99.4

Average ± %RSD 100 % ± 2 .1 % 1 01 % ± 4.3 %

LCS

- 140108

- 4 4.95 5.04 102 4 .95 4.89 98.7

LCS

- 140108

- 5 4.95 5.03 102 4.95 4.83 97.6

LCS

- 140108

- 6 4.95 4.94 99.9 4.95 4.82 97.4

Average ± %RSD 1 01 % ± 1.2 % 97.9 % ± 0.72 %

LCS

- 140108

- 7 39.8 41.9 105 39.8 >ULOQ NA

LCS

- 140108

- 8 39.8 41.3 104 39.8 >ULOQ NA

LCS

- 140108

- 9 39.8 40.1 101 3 9.8 >ULOQ NA

Average ± %RSD 10 3 % ± 2.0 % NA

>ULOQ = analyte concentration exceeded upper limit of quantitation
NA = Not Applicable (1) LCS recovery did not meet acceptance criteria of 100 ± 20%.3M ENVIRONMENTAL LAB ORATORY

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PAGE 9 OF 25 

### Table 7 continued. Lab Control Spike Results.

ETS

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External Standard

Calibration

Analyzed 1/8/14 PFOS (Linear + Branched) PFOS surrogate

Lab ID Spiked

Concentration (ng/mL) Calculated

Concentration (ng/mL) %Recovery Spiked

Concentration (ng/mL) Calculated

Concentration (ng/mL) %Recovery

L CS

- 140108

- 1 0.185 0.178 96.2 0.190 0.226 119

LCS

- 140108

- 2 0.185 0.185 99.8 0.190 0.220 116

LCS

- 140108

- 3 0.185 0.179 96.7 0.190 0.236 124

Average ± %RSD 97.6 % ± 2.0 % 120 % ± 3.4 %

LCS

- 140108

- 4 4.59 4.79 104 4.73 5.38 114

LCS

- 140108

- 5 4.59 4.71 103 4.73 5.40 114

LCS

- 140108

- 6 4.59 4.76 104 4.73 5.35 113

Average ± %RSD 1 04 % ± 0.56 % 114 % ± 0.51 %

LCS

- 140108

- 7 36.9 37.4 101

LCS

- 140108

- 8 36.9 36.0 97.6

LCS

- 140108

- 9 36.9 35.9 97.2

Average ± %RSD 98.6 % ± 2.1 %

ETS

- 8

- 044.1

In ternal Standard

Calibration

Analyzed 1/9/14 PFOA (Linear + Branched) PFOA surrogate

Lab ID Spiked

Concentration (ng/mL) Calculated

Concentration (ng/mL) %Recovery Spiked

Concentration (ng/mL) Calculated

Concentration (ng/mL) %Recovery

LCS

- 140109

- 1 0.190 0.201 106 0.198 0.230 116

LCS

- 140109

- 2 0.190 0.202 106 0.198 0.244 123

LCS

- 140109

- 3 0.190 0.208 110 0.198 0.235 119

Average ± %RSD 107 % ± 2.2 % 119 % ± 3.0 %

L CS

- 140109

- 4 1.90 2.20 116 1.98 2.40 121

LCS

- 140109

- 5 1.90 2.12 112 1.98 2.31 117

LCS

- 140109

- 6 1.90 2.20 116 1.98 2.35 119

Average ± %RSD 115 % ± 2.0 % 119 % ± 1.7 %

LCS

- 140109

- 7 19.0 20.7 109

LCS

- 140109

- 8 19.0 21.6 114

LCS

- 140109

- 9 19.0 22.1 116

Average ± %RSD 113 % ± 3.2 %

>ULOQ = analyte concentration exceeded upper limit of quantitation
NA = Not Applicable (1) LCS recovery did not meet acceptance criteria of 100 ± 20%.3M ENVIRONMENTAL LAB ORATORY

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PAGE 10 OF 25 

### Table 7 continued. Lab Control Spike Results.

ETS

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- 044.1

Internal S tandard

Calibration

Analyzed 1/9/14 PFBS PFHS

Lab ID Spiked

Concentration (ng/mL) Calculated

Concentration (ng/mL) %Recovery Spiked

Concentration (ng/mL) Calculated

Concentration (ng/mL) %Recovery

LCS

- 140109

- 1 0.198 0.210 106 0.198 0.179 90.4

LCS

- 140109

- 2 0.198 0.212 107 0.198 0.235 119

LCS

- 140109

- 3 0.198 0.229 116 0.198 0.211 106

Average ± %RSD 1 10 % ± 5.0 % 105 % ± 1 4 %

LCS

- 140109

- 4 1.98 2.15 109 1.98 2.47 125

LCS

- 140109

- 5 1.98 2.08 105 1.98 2.40 121

LCS

- 140109

- 6 1.98 2.08 105 1.98 2.41 122

Average ± %RSD 106 % ± 2.2 % 123 % ± 1 .7 % (1)

LCS

- 140109

- 7 19.9 20.3 102 19.9 21.5 108

LCS

- 140109

- 8 19.9 21.1 106 19.9 21.9 110

LCS

- 140109

- 9 19.9 22.0 111 19.9 22.6 114

Average ± %RSD 106 % ± 4.3 % 111 % ± 2.8 %

ETS

- 8

- 044.1

Internal Standard

Calibration

Analyzed 1/9/14 PFOS (Linear + Branched) PFOS surrogate

Lab ID Spiked

Concentration (ng/mL) Calcu lated

Concentration (ng/mL) %Recovery Spiked

Concentration (ng/mL) Calculated

Concentration (ng/mL) %Recovery

LCS

- 140109

- 1 0.184 0.224 122 0.189 0.199 105

LCS

- 140109

- 2 0.184 0.216 117 0.189 0.207 109

LCS

- 140109

- 3 0.184 0.219 119 0.189 0.257 136

A

verage ± %RSD 119 % ± 2.1 % 117 % ± 14 %

LCS

- 140109

- 4 1.84 2.11 115 1.89 2.01 106

LCS

- 140109

- 5 1.84 2.09 113 1.89 1.95 103

LCS

- 140109

- 6 1.84 2.18 119 1.89 2.05 108

Average ± %RSD 116 % ± 2.6 % 1 06 % ± 2.4 %

LCS

- 140109

- 7 18.4 20.6 112

LCS

- 140109

- 8 18.4 20.5 112

LCS

- 140109

- 9 18.4 21.1 115

Average ± %RSD 113 % ± 1.5 %

>ULOQ = analyte concentration exceeded upper limit of quantitation
NA = Not Applicable (1) LCS recovery did not meet acceptance criteria of 100 ± 20%.3M ENVIRONMENTAL LAB ORATORY

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PAGE 11 OF 25 

### Table 7 continued. Lab Control Sp ike Results.

ETS

- 8

- 044.1

Internal Standard

Calibration

Analyzed 1/10/14 PFOA (Linear + Branched) PFOA surrogate

Lab ID Spiked

Concentration (ng/mL) Calculated

Concentration (ng/mL) %Recovery Spiked

Concentration (ng/mL) Calculated

Concentration (ng/mL) %Recovery

LCS

- 140110

- 1 0.190 0.196 103 0.198 0.237 120

LCS

- 140110

- 2 0.190 0.194 102 0.198 0.217 109

LCS

- 140110

- 3 0.190 0.202 106 0.198 0.249 126

Average ± %RSD 104 % ± 2.0 % 118 % ± 7 .3 %

LCS

- 140110

- 4 1.90 2.18 115 1.98 2.35 119

LCS

- 140110

- 5 1.90 2.08 110 1.98 2.23 112

LCS

- 140110

- 6 1.90 2.26 119 1.98 2.27 115

Average ± %RSD 115 % ± 3.9 % 115 % ± 3.1 %

LCS

- 140110

- 7 19.0 21.3 112

LCS

- 140110

- 8 19.0 21.2 112

LCS

- 140110

- 9 19.0 20.7 109

Average ± %RSD 111 % ± 1.6 %

ETS

- 8

- 044.1

Internal Standard

Calibration

Analyzed 1/10/14 PFBS PFHS

Lab ID Spiked

Concentration (ng/mL) Calculated

Concentration (ng/mL) %Recovery Spiked

Concentration (ng/mL) Calc ulated

Concentration (ng/mL) %Recovery

LCS

- 140110

- 1 0.198 0.201 101 0.198 0.208 105

LCS

- 140110

- 2 0.198 0.212 107 0.198 0.213 107

LCS

- 140110

- 3 0.198 0.204 103 0.198 0.245 124

Average ± %RSD 104 % ± 2.9 % 112 % ± 9.3 %

LCS

- 140110

- 4 1.98 2.12 107 1.98 2.21 112

LCS

- 140110

- 5 1.98 2.20 111 1.98 2.28 115

LCS

- 140110

- 6 1.98 2.25 114 1.98 2.18 110

Average ± %RSD 111 % ± 3.2 % 112 % ± 2.2 %

LCS

- 140110

- 7 19.9 20.8 104 19.9 22.9 115

LCS

- 140110

- 8 19.9 20.6 103 19.9 22.1 111

LCS

- 140110

- 9 19.9 20.1 101 19.9 21.2 107

Average ± %RSD 103 % ± 1.5 % 111 % ± 3.6 %

>ULOQ = analyte concentration exceeded upper limit of quantitation
NA = Not Applicable (1) LCS recovery did not meet acceptance criteria of 100 ± 20%.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

- 07

- 11

PAGE 12 OF 25 

### Table 7 continued. Lab Control Spike Results.

ETS

- 8

- 044. 1

Internal Standard

Calibration

Analyzed 1/10/14 PFOS (Linear + Branched) PFOS surrogate

Lab ID Spiked

Concentration (ng/mL) Calculated

Concentration (ng/mL) %Recovery Spiked

Concentration (ng/mL) Calculated

Concentration (ng/mL) %Recovery

LCS

- 140110

- 1 0.184 0.208 113 0.189 0.204 108

LCS

- 140110

- 2 0.184 0.222 121 0.189 0.218 115

LCS

- 140110

- 3 0.184 0.198 107 0.189 0.197 104

Average ± %RSD 114 % ± 6.2 % 109 % ± 5.1 %

LCS

- 140110

- 4 1.84 2.26 123 1.89 2.35 125

LCS

- 140110

- 5 1.84 2.12 115 1.89 2.18 115

LCS

- 140110

- 6 1.84 2.28 124 1.89 2.26 120

Average ± %RSD 121 % ± 4.1 % (1) 120 % ± 4.2 %

LCS

- 140110

- 7 18.4 21.1 114

LCS

- 140110

- 8 18.4 20.8 113

LCS

- 140110

- 9 18.4 19.1 104

Average ± %RSD 110 % ± 5.0 %

>ULOQ = analyte concentration exceeded upper limit of quantitation
NA = Not Applicable (1) LCS recovery did not meet acceptance criteria of 100 ± 20%.



## 3.7 Analytical Method Uncertainty

An alytical 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 resu lts (in %) obtained for the QC samples. The expanded uncertainty is calculated by multiplying the standard deviation by a factor of 2, which corresponds to a confidence level of 95%. The method uncertainty determined by ETS

- 12

- 012.2 was

± 21% for PFHS and ± 18% for PFOS, but the method uncertainty has been expanded based on the

%bias of the non

- compliant mid

- level LCSs.

Table 8 . Analytical Method Uncertainty.

Analyte Calibration Method Standard Deviation (%) Method Uncertainty

PF O A External Standard 8.56 ± 17 %

PFBS External Standard 8.70 ± 17 %

PFHS External Standard 7.92 ± 16 %

PFOS External Standard 10.7 ± 21 %

PFOA Internal Standard 8.50 ±1 7 %

PFBS Internal Standard 6.80 ± 1 4 %

PFHS Internal Standard 10.7 ± 2 3 %

PFOS Internal Standar d 9.12 ± 21 %3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

- 07

- 11

PAGE 13 OF 25 

## 3.8 Field Matrix Spikes (FMS)

A field matrix spike w as 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 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 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.

100% *

on Concentrat Spike Dup.) Sample Field & Sample Field : ion Concentrat Average FMS of ion Concentrat (Sample Recovery FMS −

=



### Table 9 . Field Matrix Spike Concentrations

.

Final Concentration (ng/mL)

Location Description PFOA PFBS PFHS PFOS

ACI Field Matri x Spike 2480 2500 2510 2500

ACM2 Field Matrix Spike 4.9 6 5.00 5.00 4.99

ACE Field Matrix Spike 4.9 6 5.00 5.00 4.99

WW8R, WW9R, WW10R, WW11R Field Matrix Spike 2480 2500 2510 2500

Trip Blank Low Field Matrix Spike 4.9 6 5.00 5.00 4.99

High Field Matrix Spike 2480 2500 2510 2500



# 4 Data Summary and Discussion

The tables below summarize the sample results and field m atrix spike recoveries for the seven locations as well as the Trip Blank. Each table provides the average concentration and the relative

perc ent 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 slightl y 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 accepta nce criteria except

where noted below.

DAL

- GW

- ACM2 ; the FMS sample ( 5 ng/mL) was not appropriate for PFBS ; however, t he surrogate recovery standard 13 

### C 4 

### - PFOS met method acceptance criteria. No additional QC samples were prepared.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

- 07

- 11

PAGE 14 OF 25 

### Table 10

. DAL GW ACI 131213 (1)

PFOA PFBS

3M LIMS ID Description Concentration (ng/mL) %Recovery Concentration (ng/mL) %Recovery

ISO13

- 07

- 11

- 001 DAL

- GW

- ACI

- 0

- 131213 1840 NA 1330 NA

ISO13

- 07

- 11

- 002 DAL

- GW

- ACI

- DB

- 131213 1820 NA 1360 NA

ISO13

- 0 7

- 11

- 003 DAL

- GW

- ACI

- FMS

- 131213 4200 95.6 3690 93.6

Average Concentration (ng/mL) ± %RPD 1830 ng/mL ± 1.1 % 1350 ng/mL ± 2.2 %

PFHS PFOS

3M LIMS ID Description Concentration (ng/mL) %Recovery Concentration (ng/mL) %Recovery

ISO13

- 07

- 11

- 001 DAL

- GW

- ACI

- 0

- 131213 687 NA 1960 NA

ISO13

- 07

- 11

- 002 DAL

- GW

- ACI

- DB

- 131213 703 NA 1980 NA

ISO13

- 07

- 11

- 003 DAL

- GW

- ACI

- FMS

- 131213 3210 100 4780 112

Average Concentration (ng/mL) ± %RPD 695 ng/mL ± 2.3 % 1970 ng/mL ± 1.0 %

13 C 4 - PFOA 13 C 4 - PFOS

3M LIMS ID Description %Recovery %Recovery

ISO13

- 07

- 11

- 001 DAL

- GW

- ACI

- 0

- 131213 94.2 110

ISO13

- 07

- 11

- 002 DAL

- GW

- ACI

- DB

- 131213 93.1 115

ISO13

- 07

- 11

- 003 DAL

- GW

- ACI

- FMS

- 131213 89.7 110

Average Concentration (ng/mL) ± %RSD 92.3 % ± 2.5 % 112 % ± 2.6 %

NA = Not Applicable (1) S amples w ere analyzed by external standard calibration

. The surrogate recovery standards 13 C 4 - PFOA and 13 C 4 - PFOS were
added to the samples during sample preparation.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

- 07

- 11

PAGE 15 OF 25 

### Table 11

. DAL GW ACM2 131213

PFOA ( 1 ) PFBS ( 2 )

3M LIMS ID D escription Concentration (ng/mL) %Recovery Concentration (ng/mL) %Recovery

ISO13

- 07

- 11

- 004 DAL

- GW

- ACM2

- 0

- 131213 0.0729 NA 1430 NA

ISO13

- 07

- 11

- 005 DAL

- GW

- ACM2

- DB

- 131213 0.0775 NA 1440 NA

ISO13

- 07

- 11

- 006 DAL

- GW

- ACM2

- FMS

- 131213 5.51 110 1460 NC

Average Concentration (ng/mL) ± %RPD 0.0752 ng/mL ± 6.1 % 1440 ng/mL ± 0.69 %

PFHS (1 ) PFOS ( 1 )

3M LIMS ID Description Concentration (ng/mL) %Recovery Concentration (ng/mL) %Recovery

ISO13

- 07

- 11

- 004 DAL

- GW

- ACM2

- 0

- 131213 0.0587 NA 0.531 NA

ISO13

- 07

- 11

- 005 DA L

- GW

- ACM2

- DB

- 131213 0.0829 NA 0.606 NA

ISO13

- 07

- 11

- 006 DAL

- GW

- ACM2

- FMS

- 131213 5.47 108 6.00 109

Average Concentration (ng/mL) ± %RPD 0.0708 ng/mL ± 34 % (3) 0.569 ng/mL ± 13 %

13 C 4 - PFOA (1) 13 C 4 - PFOS (1 )

3M LIMS ID Description %Recovery %Recovery

ISO 13

- 07

- 11

- 004 DAL

- GW

- ACM2

- 0

- 131213 110 102

ISO13

- 07

- 11

- 005 DAL

- GW

- ACM2

- DB

- 131213 105 93.6

ISO13

- 07

- 11

- 006 DAL

- GW

- ACM2

- FMS

- 131213 108 88.3

Average Concentration (ng/mL) ± % RSD 108 % ± 2 .3 % 94.6 % ± 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. (3) Sample/sample duplicate RPD did not meet acceptance criteria of ≤ 20%.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

- 07

- 11

PAGE 16 OF 25 

### Table 12

. DAL GW ACE 131213 (1)

PFOA PFBS

3M LIMS ID Description Concentration (ng/mL) %Recovery Concentration (ng/mL) %Recovery

ISO13

- 07

- 11

- 007 DAL

- GW

- ACE

- 0

- 131213 0.0728 NA 0.0725 NA

ISO13

- 07

- 11

- 008 DAL

- GW

- ACE

- DB

- 131213 0.0868 NA 0.0806 NA

ISO13

- 07

- 11

- 009 DAL

- GW

- ACE

- FMS

- 131213 5.22 104 4.65 91.5

Average Concentration (ng/mL) ± %RPD 0. 0798 ng/mL ± 1 8 % 0. 0766 ng/mL ± 11 %

PFHS PFOS

3M LIMS ID Description Concentration (ng/mL) %Recovery Concentration (ng/mL) %Recove ry

ISO13

- 07

- 11

- 007 DAL

- GW

- ACE

- 0

- 131213 <0.0500 NA 0.0276 NA

ISO13

- 07

- 11

- 008 DAL

- GW

- ACE

- DB

- 131213 0.0648 NA 0.0330 NA

ISO13

- 07

- 11

- 009 DAL

- GW

- ACE

- FMS

- 131213 4.72 93.1 4.75 94.6

Average Concentration (ng/mL) ± %RPD 0.0648 ng/mL 0.0303 ng/mL ± 18 %

13 C 4 - PFOA 13 C 4 - PFOS

3M LIMS ID Description %Recovery %Recovery

ISO13

- 07

- 11

- 007 DAL

- GW

- ACE

- 0

- 131213 98.5 112

ISO13

- 07

- 11

- 008 DAL

- GW

- ACE

- DB

- 131213 102 91.7

ISO13

- 07

- 11

- 009 DAL

- GW

- ACE

- FMS

- 131213 104 94.1

Average Concentration (ng/mL) ± %RSD 100 % ± 2.8 % 102 % ± 11 %

NA = Not Applicable (1) Samples were analyzed by internal standard calibration

.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

- 07

- 11

PAGE 17 OF 25 

### Table 13

. DAL GW WW8R 131213 (1)

PFOA PFBS

3M LIMS ID Description Concentration (ng/mL) %Recovery Concentration (ng/mL) %Recovery

ISO13

- 07

- 1 1

- 010 DAL

- GW

- WW8R

- 0

- 131213 2700 NA 316 NA

ISO13

- 07

- 11

- 011 DAL

- GW

- WW8R

- DB

- 131213 2730 NA 316 NA

ISO13

- 07

- 11

- 012 DAL

- GW

- WW8R

- FMS

- 131213 4930 89.1 2640 93.0

Average Concentration (ng/mL) ± %RPD 2720 ng/mL ± 1.1 % 316 ng/mL ± 0.0 %

PFHS PFOS

3M LIMS ID D escription Concentration (ng/mL) %Recovery Concentration (ng/mL) %Recovery

ISO13

- 07

- 11

- 010 DAL

- GW

- WW8R

- 0

- 131213 1260 NA 4070 NA

ISO13

- 07

- 11

- 011 DAL

- GW

- WW8R

- DB

- 131213 1270 NA 4050 NA

ISO13

- 07

- 11

- 012 DAL

- GW

- WW8R

- FMS

- 131213 3610 93.2 6490 97.2

Average C oncentration (ng/mL) ± %RPD 1270 ng/mL ± 0.79 % 4060 ng/mL ± 0.49 %

13 C 4 - PFOA 13 C 4 - PFOS

3M LIMS ID Description %Recovery %Recovery

ISO13

- 07

- 11

- 010 DAL

- GW

- WW8R

- 0

- 131213 90.6 108

ISO13

- 07

- 11

- 011 DAL

- GW

- WW8R

- DB

- 131213 86.5 107

ISO13

- 07

- 11

- 012 DAL

- GW

- WW8 R

- FMS

- 131213 82.7 101

Average Concentration (ng/mL) ± %RSD 86.6 % ± 4.6 % 105 % ± 3.6 %

NA = Not Applicable (1) Samples were analyzed by external standard calibration. The surrogate recovery standards 13 C 4 - PFOA and 13 C 4 - PFOS were
added to the samples during sa mple preparation

.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

- 07

- 11

PAGE 18 OF 25 

### Table 14

. DAL GW WW9R 131213 (1)

PFOA PFBS

3M LIMS ID Description Concentration (ng/mL) %Recovery Concentration (ng/mL) %Recovery

ISO13

- 07

- 11

- 013 DAL

- GW

- WW9R

- 0

- 131213 2670 NA 264 NA

ISO13

- 07

- 11

- 014 DAL

- GW

- WW9R

- DB

- 131213 2700 NA 253 NA

ISO13

- 07

- 11

- 015 DAL

- GW

- WW9R

- FMS

- 131213 4820 85.9 2590 93.2

Average Concentration (ng/mL) ± %RPD 2690 ng/mL ± 1.1 % 259 ng/mL ± 4.2 %

PFHS PFOS

3M LIMS ID Description Concentration (ng/mL) %Recovery Concentration (ng/mL) %Recovery

ISO13

- 07

- 11

- 013 DAL

- GW

- WW9R

- 0

- 131213 1170 NA 4160 NA

ISO13

- 07

- 11

- 014 DAL

- GW

- WW9R

- DB

- 131213 1160 NA 4210 NA

ISO13

- 07

- 11

- 015 DAL

- GW

- WW9R

- FMS

- 131213 3460 91.2 6640 98.0

Average Concentration (ng/mL) ± %RPD 1170 ng/mL ± 0.85 % 4190 ng/mL ± 1.2 %

13 C 4 - PFOA 13 C 4 - PFOS

3M LIMS ID Description %Recovery %Recovery

ISO13

- 07

- 11

- 013 DAL

- GW

- WW9R

- 0

- 131213 88.3 111

ISO13

- 07

- 11

- 014 DAL

- GW

- WW9R

- DB

- 131213 89.6 105

ISO13

- 07

- 11

- 015 DAL

- GW

- WW9R

- FMS

- 131213 85.5 106

Average Concentration (ng/mL) ± %RSD 87.8 % ± 2 .4 % 107 % ± 3.0 %

NA = Not Applicable (1) Samples were analyzed by external standard calibration. The surrogate recovery standards 13 C 4 - PFOA and 13 C 4 - PFOS were
added to the samples during sample preparation

.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

- 07

- 11

PAGE 19 OF 25 

### Table 15

. DAL GW WW1 0R 131213 (1)

PFOA PFBS

3M LIMS ID Description Concentration (ng/mL) %Recovery Concentration (ng/mL) %Recovery

ISO13

- 07

- 11

- 016 DAL

- GW

- WW10R

- 0

- 131213 1910 NA 239 NA

ISO13

- 07

- 11

- 017 DAL

- GW

- WW10R

- DB

- 131213 1870 NA 238 NA

ISO13

- 07

- 11

- 018 DAL

- GW

- WW10R

- F MS

- 131213 3940 82.7 2460 88.8

Average Concentration (ng/mL) ± %RPD 1890 ng/mL ± 2.1 % 239 ng/mL ± 0. 42 %

PFHS PFOS

3M LIMS ID Description Concentration (ng/mL) %Recovery Concentration (ng/mL) %Recovery

ISO13

- 07

- 11

- 016 DAL

- GW

- WW10R

- 0

- 131213 889 NA 2950 NA

ISO13

- 07

- 11

- 017 DAL

- GW

- WW10R

- DB

- 131213 880 NA 2890 NA

ISO13

- 07

- 11

- 018 DAL

- GW

- WW10R

- FMS

- 131213 3110 88.6 5110 87.6

Average Concentration (ng/mL) ± %RPD 885 ng/mL ± 1 .0 % 2920 ng/mL ± 2. 1 %

13 C 4 - PFOA 13 C 4 - PFOS

3M LIMS ID Description %Recovery % Recovery

ISO13

- 07

- 11

- 016 DAL

- GW

- WW10R

- 0

- 131213 90.3 109

ISO13

- 07

- 11

- 017 DAL

- GW

- WW10R

- DB

- 131213 86.8 102

ISO13

- 07

- 11

- 018 DAL

- GW

- WW10R

- FMS

- 131213 84.2 111

Average Concentration (ng/mL) ± %RSD 87.1 % ± 3. 5 % 107 % ± 4 .4 %

NA = Not Applicable (1) Samples were an alyzed by external standard calibration. The surrogate recovery standards 13 C 4 - PFOA and 13 C 4 - PFOS were
added to the samples during sample preparation.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

- 07

- 11

PAGE 20 OF 25 

### Table 16

. DAL GW WW11R 131213 (1)

PFOA PFBS

3M LIMS ID Description Concentration (ng/mL) % Recovery Concentration (ng/mL) %Recovery

ISO13

- 07

- 11

- 019 DAL

- GW

- WW11R

- 0

- 131213 1050 NA 200 NA

ISO13

- 07

- 11

- 020 DAL

- GW

- WW11R

- DB

- 131213 1060 NA 195 NA

ISO13

- 07

- 11

- 021 DAL

- GW

- WW11R

- FMS

- 131213 3260 88.7 2420 88.9

Average Concentration (ng/mL) ± %RPD 1 060 n g/mL ± 0.94 % 198 ng/mL ± 2.5 %

PFHS PFOS

3M LIMS ID Description Concentration (ng/mL) %Recovery Concentration (ng/mL) %Recovery

ISO13

- 07

- 11

- 019 DAL

- GW

- WW11R

- 0

- 131213 515 NA 1570 NA

ISO13

- 07

- 11

- 020 DAL

- GW

- WW11R

- DB

- 131213 508 NA 1560 NA

ISO13

- 07

- 11

- 021 DAL

- GW

- WW11R

- FMS

- 131213 2730 88.4 3940 94.8

Average Concentration (ng/mL) ± %RPD 512 ng/mL ± 1.4 % 1570 ng/mL ± 0.64 %

13 C 4 - PFOA 13 C 4 - PFOS

3M LIMS ID Description %Recovery %Recovery

ISO13

- 07

- 11

- 019 DAL

- GW

- WW11R

- 0

- 131213 91.7 108

ISO13

- 07

- 11

- 020 D AL

- GW

- WW11R

- DB

- 131213 90.0 110

ISO13

- 07

- 11

- 021 DAL

- GW

- WW11R

- FMS

- 131213 84.7 104

Average Concentration (ng/mL) ± %RSD 88.8 % ± 4.1 % 107 % ± 2 .9 %

NA = Not Applicable (1) Samples were analyzed by external standard calibration. The surrogate recovery standards 13 C 4 - PFOA and 13 C 4 - PFOS were
added to the samples during sample preparation.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

- 07

- 11

PAGE 21 OF 25 

### Table 17 . Trip Blank Results

PFOA PFBS

3M LIMS ID Description Concentration (ng/mL) %Recovery Concentration (ng/mL) %Recovery

ISO13

- 07

- 11

- 022 DAL

- GW

- TRIP

- 0

- 131213 <0.0240 (1) NA <0. 0 25 0 (1 ) NA

ISO13

- 07

- 11

- 023 DAL

- GW

- TRIP

- LS

- 131213 4.37 (2 ) 88.1 4.74 (2 ) 94.8

ISO13

- 07

- 11

- 024 DAL

- GW

- TRIP

- HS

- 131213 220 0 (2) 88.7 2110 (2) 84.4

PFHS PFOS

3M LIMS ID Description Concentration (ng/mL) %Recovery Concentration (ng/mL ) %Recovery

ISO13

- 07

- 11

- 022 DAL

- GW

- TRIP

- 0

- 131213 <0.05 00 (1) NA <0.0232 (1) NA

ISO13

- 07

- 11

- 023 DAL

- GW

- TRIP

- LS

- 131213 4.45 (2 ) 89.0 4.54 (2 ) 91.0

ISO13

- 07

- 11

- 024 DAL

- GW

- TRIP

- HS

- 131213 2160 (2) 86.1 2420 (2) 96.8

13 C 4 - PFOA 13 C 4 - PFOS

3M LIMS ID Descri ption %Recovery %Recovery

ISO13

- 07

- 11

- 022 DAL

- GW

- TRIP

- 0

- 131213 115 (1) 92.0 (1)

ISO13

- 07

- 11

- 023 DAL

- GW

- TRIP

- LS

- 131213 100 (2 ) 114 (2 )

ISO13

- 07

- 11

- 024 DAL

- GW

- TRIP

- HS

- 131213 94.0 (2) 115 (2 )

NA = Not Applicable (1) Samples were analyzed by internal standard calibration. (2) Sample s w ere analyzed by exte rnal standard calibration

. The surrogate recovery standards 13 C 4 - PFOA and 13 C 4 - PFOS were
added to the samples during sample preparation.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

- 07

- 11

PAGE 22 OF 25 

# 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 matr ix

. 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 ”

. Analytical results are reported in Table 1 and 10

- 1 7 o f 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 s elect sampling points at the Decatur Ground Water Treatment Plant (GWTP) GAC System

.



# 8 Signatures

Susan T. Wolf, 3M Principal Analytical Investigator Date

William K. Reagen, Ph.D., 3M Environmental Laboratory Technical Director Date

The 3M Envir onmental Laboratory’s Quality Assurance Unit has audited the data and report for this project.

Quality Assurance Representative Date

**This test report shall not be reproduced except in full, without written approval of the 3M**  **Environmental Laboratory**

**.**3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

- 07

- 11

PAGE 23 OF 25 

### 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 1/17/13 2/13/13 3/27/13 4/29/13 5/31/13 6/27/13 7/23/13 9/30/ 13 10/28/13 11/18/13 12/13/13

PFOA 1910 2300 2220 1480 1860 1480 1630 2320 1880 2190 1830

PFBS 588 830 1060 1360 1040 708 1230 356 1590 1100 1350

PFHS 895 1580 1090 777 940 942 749 1400 866 1330 695

PFOS 1810 2940 2490 1670 2150 1590 1680 3240 2100 224 0 1970



### AC E (Activated Carbon Ef fluent)

- Sample Results in ng/mL

ACE 1/17/13 2/13/13 3/27/13 4/29/13 5/31/13 6/27/13 7/23/13 9/30/13 10/28/13 11/18/13 12/13/13

PFOA <0.0240 0.124 0.0380 0.0422 0.0725 0.0717 0.0641 0.115 0.231 0.478 0.0798

PFBS <0. 0250 0.0360 <0.0250 0.392 24.8 111 1960 1950 0.379 0.592 0.0766

PFHS <0.0250 0.178 0.0477 0.057 0 0.105 0.118 0.0778 0.156 0.180 0.366 0.0648

PFOS <0.0232 0.0329 <0.0232 <0.0232 <0.0232 <0.0232 0.0277 0.0452 0.0785 0.0726 0.03033M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

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PAGE 24 OF 25 

### 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

WW8R 1/17/13 2/13/13 3/27/13 4/29/13 5/31/13 6/27/13 7/23/13 9/30/13 10/28/13 11/18/13 12/13/13

PFOA 4350 3250 3640 31 90 2760 2760 2640 2890 2830 3040 2720

PFBS 410 354 385 364 289 282 263 303 312 362 316

PFHS 1930 1900 1760 1610 1330 1340 1260 1370 1300 1440 1270

PFOS 5710 4850 5120 4830 4180 4110 3910 4100 4410 4750 4060



### WW9R

- Sample Results in ng/mL

WW9R 1/17 /13 2/13/13 3/27/13 4/29/13 5/31/13 6/27/13 7/23/13 9/30/13 10/28/13 11/18/13 12/13/13

PFOA 2710 2850 3330 2650 2660 2630 2410 2730 2820 2950 2690

PFBS 184 236 278 244 226 225 212 249 286 305 259

PFHS 954 1400 1440 1200 1120 1140 1030 1220 1280 1340 117 0

PFOS 3690 4100 4660 4340 4210 4150 3670 4200 4380 4540 41903M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

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PAGE 25 OF 25 

### 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

WW10R 9/30/2013 10/28/2013 1 1/18/2013 12/13/2013

PFOA 2070 2150 2400 1890

PFBS 247 264 303 239

PFHS 1030 1030 1120 885

PFOS 2770 3160 3890 2920



### WW11R

- Sample Results in ng/mL

WW11R 9/30/2013 10/28/2013 11/18/2013 12/13/2013

PFOA 1720 1100 1320 1060

PFBS 299 240 287 198

PFHS 1000 511 680 512

PFOS 2200 1670 1850 1570