3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO14

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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

– April 2014

Laboratory Request Number: ISO14

- 07

- 04

Method Re quirement: 3M Method ETS

- 8

- 044.1

Report Date

– Da te 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 ANS I/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 c onformance with the EPA GLPs (40 CFR 792) by an independent A2LA assessment.3M ENVIRONMENTAL LAB ORATORY

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PAGE 2 OF 25 

### 3M Environmen tal 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

- 04

3M Decatur Groundwater Treatment Plant System; April 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 April 23

, 2014 . 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 laboratory project number ISO14

- 07

- 04

. Analysis of the samples was completed as specified under 3M Environmental Laboratory General Project Outline (GPO) number GPO1 3

- 1 289

.

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. 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. S ample bottles for sampling locations ACM2 and ACE

, along with the Trip Blank sample and low spike

, were fortified with i nternal standards and surrogate recovery standard s 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 ”. I nternal

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 qual ity control samples prepared and analyzed with the samples will be reported and discussed elsewhere in this report.

The testing reported herein meet the requirements of ANSI/ISO/IEC 17025:2005 “General Requirements for the Competence of Testing and Calibration Laboratories”, in accordance with the A2LA Testing Certificate # 2052.01. 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

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PAGE 3 OF 25 

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

3M LIMS ID Sample Description PFOA
Concentration (ng/mL) PFBS
Concentr ation (ng/mL) PFHS
Concentration (ng/mL) PFOS
Concentration (ng/mL)

ISO14

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- 001 DAL

- GW

- ACI

- 0

- 1 40 423 2080 1230 785 1440

ISO14

- 07

- 04

- 002 DAL

- GW

- ACI

- DB

- 140 423 2070 1260 794 1520

Average 20 80 12 50 7 90 1480

%RPD Sample/Sample Dup 0.48 2.4 1.1 5.4

ISO 14

- 07

- 04

- 004 DAL

- GW

- ACM2

- 0

- 140 423 0.128 2610 0.154 0.310

ISO14

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- 04

- 005 DAL

- GW

- ACM2

- DB

- 140 423 0.108 2590 0.153 0.309

Average 0.118 (2) 2600 0. 154 (2) 0.310 (2)

%RPD Sample/Sample Dup 1 7 0. 77 0.65 0.32

ISO14

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- 007 DAL

- GW

- ACE

- 0

- 140 423 0.175 67.4 0 .0742 0.0566

ISO14

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- 04

- 008 DAL

- GW

- ACE

- DB

- 140 423 0.168 71.9 0.0881 0.0567

Average 0. 172 (2) 69.7 0. 0812 (2) 0. 0567 (2)

%RPD Sample/Sample Dup 4.1 4.3 17 0.18

ISO14

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- 04

- 010 DAL

- GW

- WW8R

- 0

- 140 423 2690 280 1180 3770

ISO14

- 07

- 04

- 011 DAL

- GW

- WW8R

- DB

- 140 423 2760 285 1170 3910

Average 27 30 28 3 11 80 3840

%RPD Sample/Sample Dup 2.6 1.8 0.85 3.6

ISO14

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- 04

- 013 DAL

- GW

- WW9R

- 0

- 140 423 2770 256 1090 3580

ISO14

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- 014 DAL

- GW

- WW9R

- DB

- 140 423 2860 257 1140 4060

Average 28 20 257 11 20 3820 (3)

%RPD Sample/S ample Dup 3.2 0.39 4.5 13

ISO14

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- 016 DAL

- GW

- WW10R

- 0

- 140 423 1850 240 888 2190

ISO14

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- 017 DAL

- GW

- WW10R

- 140 423 1850 246 882 2060

Average 1850 243 885 2130 (3 )

%RPD Sample/Sample Dup 0.00 2.5 0.68 6.1

ISO14

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- 019 DAL

- GW

- WW11R

- 0

- 140 423 111 0 207 526 1480

ISO14

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- 04

- 020 DAL

- GW

- WW11R

- DB

- 140 423 1130 216 527 1770

Average 1120 212 527 16 30

%RPD Sample/Sample Dup 1.8 4.3 0.19 18

(1) Reported results from samples prepared and analyzed by ETS

- 8

- 044. 1 using external standard calibration except wh ere
otherwise noted . The analytical method uncertainties associated with the reported results are as follows: PFOA ±1 1 %, PFBS

± 1 1 %, PFHS ±1 1 %, and PFOS ± 10 %. (2) Sample set prepared and analyzed by ETS

- 8

- 044.1 using internal standard calibration. The analyti cal method uncertainties associated with the reported results are as follows: PFOA ± 1 4 %, PFBS ± 22 %, PFHS ± 11 %, and PFOS ± 1 6 %. (3) Results obtained without concurrent preparation and analysis of LCSs as a quality control measure. See section 3.6 and 4 for

de tai ls.3M ENVIRONMENTAL LAB ORATORY

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PAGE 4 OF 25 

# 2 Methods

- Analytical and Preparatory

2.1 Methods
Analysis was comple ted 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

Perfluorooctanoic Acid (C8 Acid) PFOA Linear + Branched

Perfluorobutanesulfonate (C4 Sulfonate ) PFBS Linear

Perfluorohexanesulfonate (C6 Sulfonate) PFHS Li near
Perfluorooctanesulfonate (C8 Sulfonate) PFOS Linear + Branched



## 2.2 Sample Collection
Samples were collected on April 23

, 2014 in Nalgene TM 

### (high

- density polyethylene) bottles prepared at the 3M Environmental Laboratory. Prior to sample collection, bot tles 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 Blank 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 prior to being sent to the field for sample collect ion

. Collected sample

bottles were received by the laboratory at ambient conditions on May 1

, 2014

.



## 2.3 Sample Preparation

All s ample s were initially prepared by diluting with methanol (dilution factor of 100) and analyzing for all target analytes

. The 1:10 0 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)

. On

- column sample dilution was utilized for dilution levels of 200

- fold

. Prepared samples were analyzed by external standard calibration.

The ACE and ACM2 sample set s 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 m ethanol ( 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 w as added to the laboratory control samples (nomi nal 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 f our 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.

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 t he analytical peak, manual integration of the analytical peak is necessary. All manual integrations are performed following the3M ENVIRONMENTAL LAB ORATORY

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PAGE 5 OF 25 

### procedures outlined in SOP ETS

- 12

- 010. 1 The consistency of the laboratory’s integration is ensured through the training of lab oratory 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 Par ameters.

Instrument Name ETS McCoy

Analysis Dates 5/06 /14

– external standard calibration
5/12/14

– internal standard calibration
5/29/14

– external standard calibration

Analytical Method ETS

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- 044.1

Liquid Chromatograph Agilent 1290

Guard column Betasi l C18 (4.6 mm X 100 mm), 5 μ Analytical column Betasil C18 (4.6 mm X 100 mm), 5 μ Injection Volume 10 or 5 μ L

Mass Spectrometer Applied Biosystems API 5500

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 )

ETS

- 8

- 044.1 Analysis

0 0.0 750 90 10

1 0.50 750 90 10

2 4.00 750 70 30

3 6.00 750 70 30

4 11.00 750 20 80

5 13.00 750 20 80

6 13.50 750 10 90

7 16.00 750 10 90

8 16.50 750 90 10

9 19.00 750 90 103M 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 4 21/376 413/219

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 ]PFO S 507/80

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 5/1 2 /14

.



# 3 Data Analysis

3.1 Calibrat ion
External Standard Calibration Analysis on 5/6/14 and 5/29/14 : 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

twelve spiked standards ranging from 0. 02 ng/mL to 1 00 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 5/12 /14 : Samples were analyzed for all analytes against a

matrix

- matched stable isotope internal standard calibration curve. Calibration sta ndards 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 c alibration standards ranging from 0.0125 ng/mL to 5 0 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 the analysis on 5/12/14 , there was a period near the middle of the internal standard calibration curve where the instrument failed to provide reliable chromatography

. This resulted in an either a highly inaccurate calibration standard concentration or decreased confidence in the ability of the chromatogram to represent the analyte of intere st. A single mid

- level standard for PFOA, PFBS, and

PFHS was disabled to give the best and mos t reliable curve . This is a deviation from the method , but was required for proper quantitation

.3M ENVIRONMENTAL LAB ORATORY

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PAGE 7 OF 25 

### 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 greate r 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 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 with the exception of the peak

area count RSD for PFBS analyzed on 5/6/ 14 ( 7.7 %)

. A m ethod deviation is filed 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

.

T able 6 . LOQ

Analyte LOQ, ng/mL

5/6/14 Analysis (1) LOQ, ng/mL

5/6/14 Analysis (2 ) LOQ, ng/mL

5/1 2 /14 Analysis (3 ) L OQ, ng/mL

5/

29

/14 Analysis (4 )

PFOA 1.92 3.84 0.0480 NA

PFBS 5.00 10.0 0.0500 NA

PFHS 2.00 4.00 0.0250 NA

PFOS 1.85 3.70 0.0232 18.5

NA = Not Applicable (1) The dilution factor of 100 was applied to the LOQ. Analysis for the Trip Blank HS and locations ACM2 and ACE for PFBS

. (2) The dilution factor of 200 was applied to the LOQ. Analysis for locations ACI, WW8R, WW9R, WW10R, and WW11R. (3) The dilution factor of 2 was applied to the LOQ. Analysis for the Trip Blank sample and low spike, and locations ACM2 and

AC E for PFOA, PFHS, and PFOS

. (4) The dilution factor of 200 was applied to the LOQ. Analysis for location WW11R for PFOS.



## 3.4 Continuing Calibration
During the course of the analytical sequence, several continuing calibration verification samples (CCVs) were anal yzed 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 bla nks/solvent blanks and field/trip blanks . Each blank result wa s 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. T he LCSs were then diluted with methanol in the same manner as the samples

. Method ETS

- 8

- 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 met hod accuracy criteria with the following exception:3M ENVIRONMENTAL LAB ORATORY

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PAGE 8 OF 25 

### 5/12 /14 Analysis: Th e mid level LCSs for PFBS had an average recovery of 7 7.8 %. A method

deviatio n is included with the raw data and the analytical method uncertainty has been expanded for sample result s for PFBS obtained via internal standard calibration.

According to ETS

- 8

- 044.1, low lab control spikes should be prepared at a concentration in the range of approximately four to ten times higher than the targeted lower LOQ , the mid LCS should be prepa red near the midpoint of the calibration curve and the high lab control spikes at approximately 80% of the upper LOQ (ULOQ). For the analysis on 5/6/14 , the low LCS concentrations (nominal 1 ng/mL ) were greater than ten times the L LOQ and the high LCS co ncentrations ( nominal 40 ng/mL) were less than
80% of the ULOQ. The high level LCSs were spiked at a lower concentration to represent the majority of the analytes based on the expected sample concentrations. While the high LCS concentrations

were not wit hin 80% of the ULOQ, all sample concentrations were within the concentration range of the three spiked LCS levels . I n the future, LCSs will be prepared that cover a wider range of the calibration curve and the expected values. A method deviation has been included with the raw data.

5/29/14 analysis: Samples associated with locations WW9R and WW10R were re

- prepared and analyzed for PFOS to confirm the FMS recoveries from initial sample analysis on 5/6/14. No LCSs

were included in the anal ytical batch. A method deviation is filed with the raw data. See section 4 for

discussion

.

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 9 OF 25 

### Table 7 . Lab Control Spike Results.

ETS

- 8

- 044.1

External Standard Calibration

Analyzed 5/6/14 PFBS PFHS

Lab ID Spiked
Concentration (ng/mL) Calculated
Concentration (ng/mL) %Recovery Spiked
Concentration (ng/mL) Calculated
Concentration (ng/mL) %Recovery

LCS

- 140506

- 1 1.00 0.972 97.2 1.00 1.01 101

LCS

- 140506

- 2 1.00 1.01 101 1.00 1.02 102

LCS

- 140506

- 3 1.00 0.9 86 98.6 1.00 1.00 99.7

Average ± %RSD 98.9 % ± 1.9 % 101 % ± 1.1%

LCS

- 140506

- 4 1 0.0 10.4 104 10.0 10.7 107

LCS

- 140506

- 5 10.0 10.4 104 10.0 10.9 109

LCS

- 140506

- 6 10.0 10.9 109 10.0 11.1 111

Average ± %RSD 106 % ± 2.7 % 109 % ± 1.8 %

LCS

- 140506

- 7 39.8 46.3 116 39.8 45.5 114

LCS

- 140506

- 8 39.8 45.4 114 39.8 43.5 109

LCS

- 140506

- 9 39.8 47 .3 119 39.8 44.7 112

Average ± %RSD 116 % ± 2.2 % 112 % ± 2.3 %

ETS

- 8

- 044.1

External Standard Calibration

Analyzed 5/6/14 PFOA (Linear + Branched) PFOS (Linear + Branched)

Lab ID Spiked
Concentration (ng/mL) Calculated
Concentration (ng/mL) %Recovery S piked
Concentration (ng/mL) Calculated
Concentration (ng/mL) %Recovery

LCS

- 140506

- 1 0.958 0.952 99.4 0.927 0.966 104

LCS

- 140506

- 2 0.958 0.987 103 0.927 1.00 108

LCS

- 140506

- 3 0.958 0.966 101 0.927 0.990 107

Average ± %RSD 101 % ± 1.8 % 106 % ± 2.0%

LC S

- 140506

- 4 9.58 10.4 109 9.27 10.4 112

LCS

- 140506

- 5 9.58 10.3 107 9.27 10.3 111

LCS

- 140506

- 6 9.58 10.6 111 9.27 10.5 113

Average ± %RSD 109 % ± 1.8 % 112 % ± 0.89 %

LCS

- 140506

- 7 38.2 44.0 115 36.9 42.3 115

LCS

- 140506

- 8 38.2 41.9 110 36.9 40.4 109

LCS

- 140 506

- 9 38.2 42.5 111 36.9 41.3 112

Average ± %RSD 112 % ± 2.4 % 112 % ± 2.7 %

(1) LCS average recovery did not meet method 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

- 8

- 044.1

External Standard Calibration

Analyzed 5/6/ 14 13 C 4 - PFO A surrogate 13 C 4 - PFO S surrogate

Lab ID Spiked
Concentration (ng/mL) Calculated
Concentration (ng/mL) %Recovery Spiked
Concentration (ng/mL) Calculated
Concentration (ng/mL) %Recovery

LCS

- 140506

- 1 0.998 1.07 108 0.956 1.02 106

LCS

- 1405 06

- 2 0.998 1.08 108 0.956 1.04 109

LCS

- 140506

- 3 0.998 1.13 113 0.956 1.05 109

Average ± %RSD 110 % ± 2.6 % 108 % ± 1.6 %

LCS

- 140506

- 4 9.98 11.7 117 9.56 11.2 118

LCS

- 140506

- 5 9.98 11.9 119 9.56 11.4 119

LCS

- 140506

- 6 9.98 12.0 120 9.56 11.4 119

Average ± %RSD 119 % ± 1.3 % 119 % ± 0.49 %

ETS

- 8

- 044.1

Internal Standard Calibration

Analyzed 5/12/ 14 PFBS PFHS

Lab ID Spiked
Concentration (ng/mL) Calculated
Concentration (ng/mL) %Recovery Spiked
Concentration (ng/mL) Calculated
Concentration (ng/mL) %Recovery

LCS

- 140512

- 1 0.198 0.200 101 0.198 0.216 109

LCS

- 140512

- 2 0.198 0.201 102 0.198 0 .203 102

LCS

- 140512

- 3 0.198 0.193 97.7 0.198 0.199 101

Average ± %RSD 100 % ± 2.2 % 104 % ± 4.2 %

LCS

- 140512

- 4 9.92 7.42 74.8 9.92 9.74 98.2

LCS

- 140512

- 5 9.92 7.71 77.7 9.92 9.56 96.4

LCS

- 140512

- 6 9.92 8.04 81.0 9.92 8.59 86.6

Average ± %RSD 77.8 % ± 4 .0 % (1) 93.7 % ± 6.7 %

LCS

- 140512

- 7 39.6 35.2 89.0 39.6 42.3 107

LCS

- 140512

- 8 39.6 34.1 86.2 39.6 38.5 97.3

LCS

- 140512

- 9 39.6 35.3 89.2 39.6 40.4 102

Average ± %RSD 88.1 % ± 1.9 % 102 % ± 4.8 %

(1) LCS average recovery did not meet method acceptance criteria of 100 ± 20%.3M ENVIRONMENTAL LAB ORATORY

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PAGE 11 OF 25 

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

ETS

- 8

- 044.1

Internal Standard Calibration

Analyzed 5/12/14 PFOA (Linear + Branched) PFOS (Linear + Branched)

Lab ID Spiked
Concentration (ng/mL) Calculated
Concentration (ng/mL) %Recovery Spiked
Concentration (ng/mL) Calculated
Concentration (ng/mL) %Recovery

LCS

- 140512

- 1 0.190 0.205 108 0.184 0.196 106

LCS

- 140512

- 2 0.190 0.201 106 0.184 0.208 113

LCS

- 140512

- 3 0.190 0.225 119 0.184 0.204 111

Average ± %RSD 111 % ± 6.3 % 110 % ± 3.3 %

LCS

- 140512

- 4 9.50 8.64 90.9 9.20 8.14 88.5

LCS

- 140512

- 5 9.50 8.65 91.0 9.20 8.22 89.4

LCS

- 140512

- 6 9.50 8.92 93.9 9.20 8.52 92.6

Average ± %RSD 91.9 % ± 1.9 % 90.2 % ± 2.4 %

LCS

- 140512

- 7 38.0 36.2 95.2 36.7 38.1 104

LCS

- 140 512

- 8 38.0 35.1 92.4 36.7 37.8 103

LCS

- 140512

- 9 38.0 38.6 102 36.7 37.1 101

Average ± %RSD 96.5 % ± 5 .1 % 103 % ± 1.5 %

ETS

- 8

- 044.1

Internal Standard Calibration

Analyzed 5/12/14 13 C 4 - PFO A surrogate 13 C 4 - PFO S surrogate

Lab ID Spiked
Concentration (ng/mL ) Calculated
Concentration (ng/mL) %Recovery Spiked
Concentration (ng/mL) Calculated
Concentration (ng/mL) %Recovery

LCS

- 140512

- 1 0.198 0.186 93.9 0.189 0.177 93.4

LCS

- 140512

- 2 0.198 0.188 95.0 0.189 0.209 111

LCS

- 140512

- 3 0.198 0.212 107 0.189 0. 200 106

Average ± %RSD 98.6 % ± 7.4 % 103 % ± 8.8 %

LCS

- 140512

- 4 1.98 1.92 96.9 1.90 1.85 97.4

LCS

- 140512

- 5 1.98 2.12 107 1.90 2.00 105

LCS

- 140512

- 6 1.98 2.00 101 1.90 1.89 99.7

Average ± %RSD 1 02 % ± 5.0 % 101 % ± 3.9 %

(1) LCS average recovery did not meet method acceptance c riteria of 100 ± 20%.3M ENVIRONMENTAL LAB ORATORY

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PAGE 12 OF 25 

## 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

sta ndard deviation is calculated for the set of accuracy results (in %) obtained for the QC samples. The expanded uncertainty is calculated by multiplying the standard deviation by a factor of 2, which corresponds to a confidence level of 95%.

• The analytic al method uncertainty as cal culated by ETS

- 12

- 012.2 for PFBS by internal standard

calibration was ± 1 3 %. The recovery of the mid set of LCSs for PFBS analyzed on 5/12 /14 was 77.8%; therefore, t he analytical method uncertainty was expanded to ± 2 2 % based on the LCS recovery %bias.

Table 8 . Analytical Method Uncertainty.

Analyte Calibration Method Standard Deviation (%) Method Uncertainty

PFOA External Standard 5.56 ± 11 %

PFBS External Standard 5.74 ± 11 %

PFHS External Standard 5.34 ± 11 %

PFOS External Standard 5.12 ± 10 %

PFOA Internal Standard 7.01 ±1 4 %

PFBS Internal Standard NA ± 22 %

PFHS Internal Standard 5.60 ± 11 %

PFOS Internal Standard 8.2 4 ± 16 %

NA = Not Applicable



## 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 shi pping sample containers for sample collection. Table 9 lists the concentrations of the spikes used for this sampling

round. 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 an d
PFOS. Field matrix spike recoveries and associated results for each sample set are presented in section 4 of this report.

The following calculation was used to generate data in section 4.

100% *

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

=3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO14

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PAGE 13 OF 25 

### Table 9 . Fi eld Matrix Spike Concentrations

.

Final Concentration (ng/mL)

Location Description PFOA PFBS PFHS PFOS



### ACI Field Matrix Spike 1980 1980 1980 1980



### ACM2 Field Matrix Spike 4.94 4.9 5 4.9 5 4.9 5



### ACE (1) Field Matrix Spike 4.47 4.48 4.48 4.48



### WW8R, WW9R F ield Matrix Spike 2470 2480 2480 2480



### WW10R, WW11R Field Matrix Spike 1980 1980 1980 1980

Trip Blank Low Field Matrix Spike 4.94 4.9 5 4.9 5 4.9 5

High Field Matrix Spike 2470 2480 2480 2480

(1) Sample b ottle was overfilled by more than 10%. The FMS spike levels were adjusted accordingly.



### In addition to target analyte field matrix spikes, sample bottles for locations ACM2 and ACE, along with the Trip Blank sample and low spike, contained stable isotope surrogate recovery standards 13 

### C 4 

### - PFOA and 13 

### C 4 

### - PFOS, which were added at a nominal concentration of 0.1 ng/mL prior to sample

collection. The 13 

### C 4 

### - labeled PFOA was selected to represent PFOA . The 13 

### C 4 

### - labeled PFOS was selected to represent the C4, C6, and C8 perfluorosul fonic acids. Surrogate recoveries within method acceptance criteria of 100±30% confirm that “unknown” components in the sample matrix do not significantly interfere with the preparation and analysis of the analytes of interest. S urrogate spike recoveries are presented in section 4 of this report

.

The following calculation was used to generate data in section 4.

100% * ion Concentrat Spike ion Concentrat Calculated Recovery SRS
=



# 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 B lank. 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 fiel d samples met method acceptance criter ia with the following exception :

T he FMS spike level at 5 ng/mL was not appropriate for PFBS for sampling location s ACM2 and ACE.

H owever, the surrogate recovery standard 13 

### C 4 

### - PFOS m et method acceptance criteria and t herefore;

no additional QC samples were prepared.

During the initial sample analysis on 5/6/14, t he FMS recoveries for PFOS for sampling locations

WW9R and WW10R did not meet acceptance criteria of ± 30%

. The samples were re

- prepared and analyzed again st an external standard calibration curve to verify the FMS results on 5/29/14

. Re

analysis of these samples produced FMS recoveries that met method acceptance criteria; however,
LCSs were not prepared and included with the re

- analysis. This is a devia tion from the method. T he3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO14

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PAGE 14 OF 25 

### presence of other compliant QC measures; system suitability, curve accuracy and fit, surrogate recoveries, CCVs , and FMS recovery, support the reporting of this data. Data is reported and flagged in Tables 1, 14, and 15.

Table 10

. DAL GW ACI 140423 (1)

PFOA PFBS

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

ISO14

- 07

- 04

- 001 DAL

- GW

- ACI

- 0

- 140 423 2080 NA 1230 NA

ISO14

- 07

- 04

- 002 DAL

- GW

- ACI

- DB

- 140 423 2070 N A 1260 NA

ISO14

- 07

- 04

- 003 DAL

- GW

- ACI

- FMS

- 140 423 3840 89.3 3180 97.7

Average Concentration (ng/mL) ± %RPD 2 080 ng/mL ± 0.48 % 1250 ng/mL ± 2.4 %

PFHS PFOS

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

ISO14

- 07

- 04

- 001 DAL

- GW

- ACI

- 0

- 140 423 785 NA 1440 NA

ISO14

- 07

- 04

- 002 DAL

- GW

- ACI

- DB

- 140 423 794 NA 1520 NA

ISO14

- 07

- 04

- 003 DAL

- GW

- ACI

- FMS

- 140 423 2730 98.0 3010 77.3

Average Concentration (ng/mL) ± %RPD 790 ng/mL ± 1.1 % 1480 ng/mL ± 5.4 %

13 C 4 - PFOA 13 C 4 - PFOS

3M LIMS ID Sample Description %Recovery %Recovery

ISO14

- 07

- 04

- 001 DAL

- GW

- ACI

- 0

- 140 423 112 105

ISO14

- 07

- 04

- 002 DAL

- GW

- ACI

- DB

- 140 423 111 106

ISO14

- 07

- 04

- 003 DAL

- GW

- ACI

- FMS

- 140 423 107 103

Average Concentration (ng/mL) ± %RSD 110 % ± 2.7 % 105 % ± 1.3 %

NA = Not Applicable (1) S amples were analyzed by external standard calibration on 5/6 /14

. 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. ISO14

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PAGE 15 OF 25 

### Table 11

. DAL GW ACM2 140 423 (1)

PFOA PFBS ( 2 )

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

ISO14

- 07

- 04

- 004 DAL

- GW

- ACM2

- 0

- 140 423 0.128 NA 2610 NA

ISO14

- 07

- 04

- 005 DAL

- GW

- ACM2

- DB

- 140 423 0.108 NA 2590 NA

ISO14

- 07

- 04

- 006 DAL

- GW

- ACM2

- FMS

- 140 423 4.31 84.9 2720 NC

Average Concentration (ng/mL) ± %RPD 0.118 ng/mL ± 17 % 2600 ng/mL ± 0.77 %

PFHS PFOS

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

ISO14

- 07

- 04

- 004 DAL

- GW

- ACM2

- 0

- 140 423 0. 154 NA 0.310 NA

ISO14

- 07

- 04

- 005 DAL

- GW

- ACM2

- DB

- 140 423 0.153 NA 0.309 NA

ISO14

- 07

- 04

- 006 DAL

- GW

- ACM2

- FMS

- 140 423 4.68 91.4 4.83 91.3

Average Concentration (ng/mL) ± %RPD 0. 154 ng/mL ± 0.65 % 0.310 ng/mL ± 0.32 %

13 C 4 - PFOA 13 C 4 - PFOS 13 C 4 - PFOS (2 )

3M LIM S ID Sample Description %Recovery %Recovery %Recovery

ISO14

- 07

- 04

- 004 DAL

- GW

- ACM2

- 0

- 140 423 108 95.7 107

ISO14

- 07

- 04

- 005 DAL

- GW

- ACM2

- DB

- 140 423 106 102 111

ISO14

- 07

- 04

- 006 DAL

- GW

- ACM2

- FMS

- 140 423 104 93.0 110

Average Concentration (ng/mL) ± % RSD 106 % ± 1. 9 % 96.9 % ± 4.7 % 109 % ± 2.0 %

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 on 5/12/14 except where otherwise noted

. (2) Samples were analyzed by external standard calibration on 5/6 /14. The surrogate recovery standard 13 C 4 - PFOS was added to the samples during sample preparation.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO14

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PAGE 16 OF 25 

### Table 12 . DAL GW ACE 140 423 (1)

PFOA PFBS (2)

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

ISO14

- 07

- 04

- 007 DAL

- GW

- ACE

- 0

- 1 40 423 0.175 NA 67.4 NA

ISO14

- 07

- 04

- 008 DAL

- GW

- ACE

- DB

- 140 423 0.168 NA 71.9 NA

ISO14

- 07

- 04

- 009 DAL

- GW

- ACE

- FMS

- 140 423 3.76 80.3 74.9 NC

Average Concentration (ng/mL) ± % RPD 0. 172 ng/mL ± 4.1 % 69.7 ng/mL ± 4.3 %

PFHS PFOS

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

ISO14

- 07

- 04

- 007 DAL

- GW

- ACE

- 0

- 1 40 423 0.0742 NA 0.0566 NA

ISO14

- 07

- 04

- 008 DAL

- GW

- ACE

- DB

- 140 423 0.0881 NA 0.0567 NA

ISO14

- 07

- 04

- 009 DAL

- GW

- ACE

- FMS

- 140 423 4.25 93.1 3.86 84.9

Average Concentration (ng/mL) ± %RPD 0. 0812 ng/mL ± 17 % 0. 0567 ng/mL ± 0.18 %

13 C 4 - PFOA 13 C 4 - PFO S 13 C 4 - PFOS (2 )

3M LIMS ID Sample Description %Recovery %Recovery %Recovery

ISO1 4

- 07

- 04

- 007 DAL

- GW

- ACE

- 0

- 1 40 423 107 108 109

ISO14

- 07

- 04

- 008 DAL

- GW

- ACE

- DB

- 140 423 96.3 103 110

ISO14

- 07

- 04

- 009 DAL

- GW

- ACE

- FMS

- 140 423 89.4 102 111

Average Concentration (ng/mL) ± %RSD 97.6 % ± 9.1 % 104 % ± 3.2 % 110 % ± 0.95 %

NA = Not Applicable

NC = Not Ca lculated; Spike level was less than 0.5x the endogenous sample concentration. (1) Samples were analyzed by internal standard calibration on 5/12 /14 except where otherwise noted. (2) Samples were analyzed by external standard calibration on 5/6/14. The surrogate re covery standard 13 C 4 - PFOS was added to the samples during sample preparation.3M ENVIRONMENTAL LAB ORATORY

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PAGE 17 OF 25 

### Table 13

. DAL GW WW8R 140 423 (1)

PFOA PFBS

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

ISO14

- 07

- 04

- 010 DAL

- GW

- WW8R

- 0

- 140 423 2690 NA 280 NA

ISO14

- 07

- 04

- 011 DAL

- GW

- WW8R

- DB

- 140 423 2760 NA 285 NA

ISO14

- 07

- 04

- 012 DAL

- GW

- WW8R

- FMS

- 140 423 5120 97.0 2560 92.0

Average Concentration (ng/mL) ± %RPD 2 730 ng/mL ± 2.6 % 283 ng/mL ± 1.8 %

PFHS PFOS

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

ISO14

- 07

- 04

- 010 DAL

- GW

- WW8R

- 0

- 140 423 1180 NA 3770 NA

ISO14

- 07

- 04

- 011 DAL

- GW

- WW8R

- DB

- 140 423 1170 NA 3910 NA

ISO14

- 07

- 04

- 012 DAL

- GW

- WW8R

- FMS

- 140 423 3490 93.5 6600 112

Av erage Concentration (ng/mL) ± %RPD 1180 ng/mL ± 0.85 % 3840 ng/mL ± 3 .6 %

13 C 4 - PFOA 13 C 4 - PFOS

3M LIMS ID Sample Description %Recovery %Recovery

ISO14

- 07

- 04

- 010 DAL

- GW

- WW8R

- 0

- 140 423 101 98.1

ISO14

- 07

- 04

- 011 DAL

- GW

- WW8R

- DB

- 140 423 110 110

ISO14

- 07

- 04

- 01 2 DAL

- GW

- WW8R

- FMS

- 140 423 108 102

Average Concentration (ng/mL) ± %RSD 107 % ± 4.3 % 104 % ± 6.1 %

NA = Not Applicable (1) Samples were analyzed by external standard calibration on 5/6 /14 . The surrogate recovery standards 13 C 4 - PFOA and 13 C 4 - PFOS were added to t he samples during sample preparation

.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO14

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PAGE 18 OF 25 

### Table 14

. DAL GW WW9R 140 423 (1)

PFOA PFBS

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

ISO14

- 07

- 04

- 013 DAL

- GW

- WW9R

- 0

- 140 423 2770 NA 256 NA

ISO14

- 07

- 04

- 014 DAL

- GW

- WW9R

- DB

- 140 423 2860 NA 257 NA

ISO14

- 07

- 04

- 015 DAL

- GW

- WW9R

- FMS

- 140 423 5370 103 2760 101

Average Concentration (ng/mL) ± %RPD 2820 ng/mL ± 3.2 % 257 ng/mL ± 0.39 %

PFHS PFOS (2)

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

ISO14

- 07

- 04

- 013 DAL

- GW

- WW9R

- 0

- 140 423 1090 NA 3580 NA

ISO14

- 07

- 04

- 014 DAL

- GW

- WW9R

- DB

- 140 423 1140 NA 4060 NA

ISO14

- 07

- 04

- 015 DAL

- GW

- WW9R

- FMS

- 140 423 3790 108 6860 123

Average Concentration (ng/mL) ± %RPD 11 20 ng/mL ± 4.5 % 3820 ng/mL ± 13 %

13 C 4 - PFOA 13 C 4 - PFOS 13 C 4 - PFOS (2)

3M LIMS ID Sample Description %Recovery %Recovery %Recovery

ISO14

- 07

- 04

- 013 DAL

- GW

- WW9R

- 0

- 140 423 106 104 88.9

ISO14

- 07

- 04

- 014 DAL

- GW

- WW9R

- DB

- 140 423 112 106 97.5

ISO14

- 07

- 04

- 015 DAL

- GW

- WW9R

- FMS

- 140 423 107 103 97.1

Average Concentration (ng/mL) ± %RSD 109 % ± 2.8% 104 % ± 1.5 % 94 .5 % ± 5.1%

NA = Not Applicable (1) Samples were analyzed by external standard calibration on 5/6/14 except where noted . The surrogate recovery standards

13 C 4 - PFO A and 13 C 4 - PFOS were added to the samples during sample preparation

. (2) Results obtained on 5/29/14 without concurrent preparation and analysis of LCSs as a quality control measure

.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO14

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PAGE 19 OF 25 

### Table 15 . DAL GW WW10R 140 423 (1)

PFOA PFBS

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

ISO14

- 07

- 04

- 016 DAL

- GW

- WW10R

- 0

- 140 423 1850 NA 240 NA

ISO14

- 07

- 04

- 017 DAL

- GW

- WW10R

- DB

- 140 423 1850 NA 246 NA

ISO14

- 07

- 04

- 018 DAL

- GW

- WW10R

- FMS

- 140 423 4060 112 2140 95.8

Average Concentration (ng/mL) ± %RPD 1850 ng/mL ± 0.00 % 243 ng/mL ± 2.5 %

PFHS PFOS (2)

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

ISO14

- 07

- 04

- 016 DAL

- GW

- WW10R

- 0

- 140 423 888 NA 2190 NA

ISO14

- 07

- 04

- 017 DAL

- GW

- WW10R

- DB

- 140 423 882 NA 2060 NA

ISO14

- 07

- 04

- 018 DAL

- GW

- WW10R

- FMS

- 140 423 2820 97.7 4410 115

Average Concentration (ng/mL) ± %RPD 885 ng/mL ± 0.68 % 2130 ng/mL ± 6.1 %

13 C 4 - PFOA 13 C 4 - PFOS 13 C 4 - PFOS (2)

3M LIMS ID Sample Description %Reco very %Recovery %Recovery

ISO14

- 07

- 04

- 016 DAL

- GW

- WW10R

- 0

- 140 423 109 104 99.2

ISO14

- 07

- 04

- 017 DAL

- GW

- WW10R

- DB

- 140 423 108 103 94.6

ISO14

- 07

- 04

- 018 DAL

- GW

- WW10R

- FMS

- 140 423 106 100 101

Average Concentration (ng/mL) ± %RSD 108 % ± 1.2% 103 % ± 2.0 % 98.1 % ± 3.2 %

NA = Not Applicable (1) Samples were analyzed by external standard calibration on 5/6 /14 except where noted . The surrogate recovery standards

13 C 4 - PFOA and 13 C 4 - PFOS were added to the samples during sample preparation. (2) Results obtained on 5/29/14 without concurrent preparation and analysis of LCSs as a quality control measure

.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO14

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PAGE 20 OF 25 

### Table 16 . DAL GW WW11R 140 423 (1)

PFOA PFBS

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

ISO14

- 07

- 04

- 019 DAL

- GW

- WW11R

- 0

- 140 423 1110 NA 207 NA

ISO14

- 07

- 04

- 020 DAL

- GW

- WW11R

- DB

- 140 423 1130 NA 216 NA

ISO14

- 07

- 04

- 021 DAL

- GW

- WW11R

- FMS

- 140 423 3110 101 2350 108

Average Concentration (ng/mL) ± %RPD 1120 ng/mL 1.8 % 212 ng/mL ± 4.3 %

PFHS PFOS

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

ISO14

- 07

- 04

- 019 DAL

- GW

- WW11R

- 0

- 140 423 526 NA 1480 NA

ISO14

- 07

- 04

- 020 DAL

- GW

- WW11R

- DB

- 140 423 527 NA 1770 NA

ISO14

- 07

- 04

- 021 DAL

- GW

- WW11R

- FMS

- 140 423 2480 98.7 3990 119

Aver age Concentration (ng/mL) ± %RPD 527 ng/mL ± 0.19 % 1630 ng/mL ± 18 %

13 C 4 - PFOA 13 C 4 - PFOS

3M LIMS ID Sample Description %Recovery %Recovery

ISO14

- 07

- 04

- 019 DAL

- GW

- WW11R

- 0

- 140 423 103 97.5

ISO14

- 07

- 04

- 020 DAL

- GW

- WW11R

- DB

- 140 423 101 99.0

ISO14

- 07

- 04

- 021 DAL

- GW

- WW11R

- FMS

- 140 423 104 98.7

Average Concentration (ng/mL) ± %RSD 10 3 % ± 1.7 % 98.4 % ± 0.80 %

NA = Not Applicable (1) Samples were analyzed by external standard calibration 5/6 /14 . The surrogate recovery standards 13 C 4 - PFOA and 13 C 4 - PFOS were added to t he samples during sample preparation3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO14

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PAGE 21 OF 25 

### Table 17 . Trip Blank Results

PFOA PFBS

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

ISO14

- 07

- 04

- 022 DAL

- GW

- TRIP

- 0

- 140 423 <0.0 480 (1) NA < 0.05 0 0 (1) NA

ISO14

- 07

- 04

- 023 DAL

- GW

- TRIP

- LS

- 140 423 4. 41 (1) 89.3 4. 19 (1) 84.6

ISO14

- 07

- 04

- 024 DAL

- GW

- TRIP

- HS

- 140 423 2510 (2) 102 2480 (2) 100

PFHS PFOS

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

ISO14

- 07

- 04

- 022 DAL

- GW

- TRIP

- 0

- 140 423 <0.0250 (1) NA <0.0232 (1) NA

ISO14

- 07

- 04

- 023 DAL

- GW

- TRIP

- LS

- 140 423 5.12 (1) 103 4. 73 (1) 95.6

ISO14

- 07

- 04

- 024 DAL

- GW

- TRIP

- HS

- 140 423 2510 (2) 101 2620 (2) 106

13 C 4 - PFOA (1) 13 C 4 - PFOS (1) 13 C 4 - PFOA (2) 13 C 4 - PFOS (2)

3M LIMS ID Sample Description %Recovery %Recovery %Recovery %Recovery

ISO14

- 07

- 04

- 022 DAL

- GW

- TRIP

- 0

- 140 423 104 104 112 111

ISO14

- 07

- 04

- 023 DAL

- GW

- TRIP

- LS

- 140 423 103 88.3 109 110

ISO14

- 07

- 04

- 024 DAL

- GW

- TRIP

- HS

- 140 423 NA NA 113 105

NA = Not Applica ble (1) Samples were analyzed by internal standard calibration on 5/1 2 /14

. (2) Sample s w ere analyzed by exte rnal standard calibration on 5/6/14

. The surrogate recovery standards 13 C 4 - PFOA and 13 C 4 - PFOS were added to the samples during sample preparation3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO14

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PAGE 22 OF 25 

# 5 Conclusi on

Laboratory control spikes were used to determine the analytical method accuracy and precisio n 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 u sing 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 of this report.



# 6 Data / Sampl e 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 Treat ment Plant (GWTP) GAC System

.



# 8 Signatures

Susan T. Wolf, 3M Principal Analytical Investigator

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

The 3M Environmental Laboratory’s Quality Assurance Unit has audited the d ata and report for this project.

Quality Assurance Representative

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

REPORT NO. ISO14

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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 5/31/13 6/27/13 7/23/13 9/30/13 10/28/13 11/18/13 12/13/13 1/30/14 2/27/14 3/31/14 4/23/14

PFOA 1860 1480 1630 2320 1880 2190 1 830 1580 1870 2410 2080

PFBS 1040 708 1230 356 1590 1100 1350 202 1470 541 1250

PFHS 940 942 749 1400 866 1330 695 845 737 1110 790

PFOS 2150 1590 1680 3240 2100 2240 1970 2700 1800 3600 1480



### ACE (Activated Carbon Effluent)

- Sample Results in ng/mL

ACE 5/31/13 6/27/13 7/23/13 9/30/13 10/28/13 11/18/13 12/13/13 1/30/14 2/27/14 3/31/14 4/23/14

PFOA 0.0725 0.0717 0.0641 0.115 0.231 0.478 0.0798 0.490 0.138 0.262 0.172

PFBS 24.8 111 1960 1950 0.379 0.592 0.0766 0.257 0.0360 0.224 69.7

PFHS 0.105 0 .118 0.0778 0.156 0.180 0.366 0.0648 0.219 0.0706 0.108 0.0812

PFOS <0.0232 <0.0232 0.0277 0.0452 0.0785 0.0726 0.0303 0.209 0.0966 0.139 0.05673M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO14

- 07

- 04

PAGE 24 OF 25 

### Attachment A : Analyte Trend Data for select sampling points at the Decatur Ground Water Treatment Plant (GW TP) GAC System

WW8R

- Sample Results in ng/mL

WW8R 5/31/13 6/27/13 7/23/13 9/30/13 10/28/13 11/18/13 12/13/13 1/30/14 2/27/14 3/31/14 4/23/14

PFOA 2760 2760 2640 2890 2830 3040 2720 2660 2560 3290 2730

PFBS 289 282 263 303 312 362 316 326 331 357 2 83

PFHS 1330 1340 1260 1370 1300 1440 1270 1460 1370 1470 1180

PFOS 4180 4110 3910 4100 4410 4750 4060 3990 4170 5790 3840



### WW9R

- Sample Results in ng/mL

WW9R 5/31/13 6/27/13 7/23/13 9/30/13 10/28/13 11/18/13 12/13/13 1/30/14 2/27/14 3/31/14 4/23/1 4

PFOA 2660 2630 2410 2730 2820 2950 2690 2900 2630 3380 2820

PFBS 226 225 212 249 286 305 259 317 270 341 257

PFHS 1120 1140 1030 1220 1280 1340 1170 1460 1370 1550 1120

PFOS 4210 4150 3670 4200 4380 4540 4190 4800 4660 5420 38203M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO14

- 07

- 04

PAGE 25 OF 25 

### Attachment A: Ana lyte Trend Data for select sampling points at the Decatur Ground Water Treatment Plant (GWTP) GAC System

WW10R

- Sample Results in ng/mL

WW10R 9/30/13 10/28/13 11/18/13 12/13/13 1/30/14 2/27/14 3/31/14 4/23/14

PFOA 2070 2150 2400 1890 1330 1780 2140 1850

PFBS 247 264 303 239 250 260 278 243

PFHS 1030 1030 1120 885 757 935 1030 885

PFOS 2770 3160 3890 2920 1570 2860 3490 2130



### WW11R

- Sample Results in ng/mL

WW11R 9/30/13 10/28/13 11/18/13 12/13/13 1/30/14 2/27/14 3/31/14 4/23/14

PFOA 1720 1 100 1320 1060 814 1300 1190 1120

PFBS 299 240 287 198 168 262 254 212

PFHS 1000 511 680 512 362 696 549 527

PFOS 2200 1670 1850 1570 1540 2100 1890 1630