3M ENVIRONMENTAL LAB ORATORY

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# Final Report

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

3M Decatur, Alabama : Groundwater Treatment Plant GAC System

– June 2013

Laboratory Request Number: ISO13

- 07

- 06

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 re quirements 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 dete rmined 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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### 3M Environmen tal Laboratory

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

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



## Analytical Report ISO13

- 07

- 06

3M Decatur Groundwater Treatment Plant System; June 201 3 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 June 27 , 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)

, and the surrogate recove ry standards 13 

### C 4 

### - PFOA and 13 

### C 4 

### - PFOS

under la boratory project number ISO13

- 07

- 06

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

- 1006.

T he 3M Environmental Laboratory provid ed sample containers for five sampling locations; ACI, ACM2,

ACE , WW8R, and WW9R . 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 internal standards and surrogates prior to being sent to the field for sample collection.

Samples were prepared and analyzed by method ETS

- 8

- 044. 1 “ Method of Analysis for the

Dete rmination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis ”. Select internal standards were used to aid in the data quality objectives.

Table 1 summarizes the sample results using the analytical method identified above. All results for quality control samples prepared and analyzed with the samples will be reported and discussed elsewhere in this report.

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

REPORT NO. ISO13

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PA GE 3 OF 21 

### Table 1 . Sample 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 1460 706 935 1580

ISO13

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- 002 DAL

- GW

- ACI ; Sample Dup 1500 710 948 1600

Average 1 480 (1) 708 (1) 94 2 (1) 1590 (1)

%RPD Sample/Samp le Dup 2.7 0.56 1.4 1.3

ISO13

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- 004 DAL

- GW

- ACM2; Sample 1220 1030 2040 0.806

ISO13

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- 005 DAL

- GW

- ACM2 ; Sample Dup 1200 1020 2000 0.738

Average 1210 (1) 1 030 (1 ,2 ) 2020 (1) 0. 772 (3 )

%RPD Sample/Sample Dup 1.7 0.98 2.0 8.8

ISO13

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- 007 D AL

- GW

- ACE; Sample 0.0568 108 0.0850 <0.0232

ISO13

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- 008 DAL

- GW

- ACE ; Sample Dup 0.0866 113 0.150 <0.0232

Average 0.07 17 (3 ) 111 (1 ) 0.1 18 (3 ) <0.0232 (3 )

%RPD Sample/Sample Dup 42 (4 ) 4.5 55 (4) NA

ISO13

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- 010 DAL

- GW

- WW8R; Sample 2710 274 1 300 4010

ISO13

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- 06

- 011 DAL

- GW

- WW8R ; Sample Dup 2800 289 1380 4210

Average 2 760 (1) 28 2 (1) 13 40 (1) 41 10 (1)

%RPD Sample/Sample Dup 3.3 5.3 6.0 4.9

ISO13

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- 013 DAL

- GW

- WW9R; Sample 2590 224 1140 4170

ISO13

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- 014 DAL

- GW

- WW9R ; Sample Dup 2 660 225 1130 4130

Average 26 30 (1) 22 5 (1) 11 40 (1) 4 150 (1)

%RPD Sample/Sample Dup 2.7 0.45 0.88 0.96

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

- 8

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

uncertai nties associated with the reported results are as follows: PFOA ±14 %, PFBS ± 1 3 %, PFHS ±1 3 %, and PFOS ± 16 %. (2) Method uncertainty has been expanded to ± 35% for PFBS based on the FMS recovery. See section 4 for more information. (3) Reported results were prepare d and analyzed by ETS

- 8

- 044.1 using internal standard calibration. The analytical method uncertainties associated with the reported results are as follows: PFOA ± 1 9 %, PFHS ± 1 9 %, and PFOS ± 21 %. (4) Sample/sample duplicate RPD did not meet acceptance criteri a of ≤ 20%.



# 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) PF HS Linear

Perfluorooctanesulfonate (C8 Sulfonate) PFOS Linear + Branched3M ENVIRONMENTAL LAB ORATORY

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## 2.2 Sample Collection
Samples were collected on June 27 , 201 3 in Nalgene TM 

### (high

- density polyethylene) bottles prepared at the 3M Environmental Laboratory. Prior to sample collection, bottles designated for field matrix spikes were spiked in the laboratory with a known volume of an appropriate matrix spiking solution containing PFOA, PFBS, PFHS, and PFOS

. Sample bottles for sampling locations ACM2 and ACE, along with

the Tr ip Blank sa mple 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 by the laboratory at ambient

conditions on June 28 , 201 3

.



## 2.3 Sample Preparation

All s ample sets and the Trip Blank high spike were diluted 1:100 and analyzed for all analytes. The 1:100 dilutions were prepared by removing a 0.1 mL aliquot of the well mixed samp le and adding 9.8

mL of methanol and 0.1 mL of a surrogate spiking solution. Prepared samples were analyzed by

external standard calibration.

The ACE and ACM2 sample set s and the Trip Blank sample and low spike were prepared and analyzed for all anal ytes by transferring a n aliquot of the well mixed sample into an autovial. Prepared samples were analyzed by internal standard calibration.

During the preparation of the laboratory control samples for internal standard calibration , an aliquot of a

sepa rate internal standard spiking solution was added to the laboratory control samples (nominal concentration of 1 ng/mL). The sample bottles for ACE, ACM2, and Trip Blank were spiked with an internal standard mix at a nominal concentration of 1 ng/mL prior to being sent to the field for sample collection. The laboratory control samples were analyzed in the same manner as the samples.



## 2.4 Analysis
All samples and quality control samples were analyzed for f our target analytes using high per formance liquid chro matography/ 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 o f concentrations found in the sample, and the environmental occurrence of multiple isomers of the laboratory’s analytes of interest, the software used for processing the analytical results is not able to consistently integrate the analytical peak, manual

i ntegration 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 pee r 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.3M ENVIRONMENTAL LAB ORATORY

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### Table 3 . Instrument Parameters.

Instrument Name ETS Kirk

Analysis Dates 7/1/13 & 7/5/13

– external standard calibration

7/2/13

– internal calibration

Analytical Method ETS

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- 044.1

Liquid Chromatograph Agilent 1260

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 2, 5, or 20 μ L

Mass Spectrometer Applied Biosystems TripleQuad 5500

Ion Source Turbo Spray

Polarity Negative

Software Analyst 1.6.1



### Table 4 . Liquid Chr omatography 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 2 0.0 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 10.0



### Table 5 . Mass Transitions

.

Analyte Mass Transition

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

PFOA 413/369

[ 13 C 8 ] PFOA 421/3 76 413/219

413/169

PFBS 299/80 [ 18 O 2 ]PFBS 303/84 299/99

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

PFOS 499/99

[ 13 C 8 ]PFOS 507/80 499/80

499/130

[ 13 C 4 ]PFOA surrogate 417/372 [ 13 C 8 ]PFOA 421/376

[ 13 C 4 ]PFOS surrogate 503/80 [ 13 C 8 ]PFOS 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 7/2 /13

.3M ENVIRONMENTAL LAB ORATORY

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# 3 Data Analysis

3.1 Calibrat ion

Internal Standard Calibration Analysis on 7/2/13 : Samples were analyzed against a matrix

- matched stable isotope internal standard calibration curve. Calibration standards were prepared by spiking

known amounts of stock solutions into laboratory prepa red 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 th ese 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 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 cu rve point. The reference standards of PFOA and PFOS used to prepare the

calibration standards consisted of both linear and branched isomers. Each curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method calibrati on accuracy requirements of 100±25% (100±30% for the lowest curve point) were met for all analytes. The correlation coefficient (r) was greater than 0.995 for all analytes.

External Standard Calibration Analysis on 7/1/13 and 7/5/13 : Samples were analyz ed 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 m ethanol: Mil li

- Q laboratory water. A total of

t en spiked standards ranging fr om 0. 0 2 ng/mL to 25 ng/mL (nominal) were analyzed . The ten

standards also contained the surrogates at concentrations ranging from 0.02 ng/mL to 25 ng/mL

nominal. A quadratic, 1/x weighted, calibration curve of the standard peak area counts was used to fi t 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. The reference s tandards 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 analytes. The correlation coefficient (r) was greater than 0.995 for all analytes

.



## 3.2 System Suitability

A calibration standard was analyzed four times at the beginning of the analytical sequenc e 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 te ria 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

- zero calibration standard in the curve that meets linearity and accuracy requirements and for which the area counts are at least twice th ose of the appropriate blanks. The LOQs associated with the sample analysis are listed in Table 6

.3M ENVIRONMENTAL LAB ORATORY

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### T able 6 . LOQ

Analyte Analysis Date Calibration LOQ, ng/mL

PFOA 7/2/13 Internal standard 0.0240

PFBS 7/2/13 Internal standard 0. 0250

PFHS 7/2/13 Internal standard 0.0250

PFOS 7/2/13 Internal standard 0.0232

PFOA 7/1/13 External standard 0.0192 (1)

PFBS 7/1/13 , 7/5/13 External standard 0.0200 (1)

PFHS 7/1/13 External standard 0.0200 (1)

PFOS 7/1/13 External standard 0.0185 ( 1)

(1) The dilution factor was not applied to the LOQ.



## 3.4 Continuing Calibration
During the course of the analytical sequence, several continuing calibration verification samples (CCVs) were analyzed to confirm that the instrument response and the initial cal ibration 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 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 contro l spikes were prepared for the surrogates . LCSs were prepared by spiking known amounts of the analytes into either 10 mL of laboratory

- prepared matrix matched water

or 1 mL of Milli

- Q water to produce the desired concentration. When applicable, t he LCSs were then diluted with methanol 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

.

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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### Table 7 . Lab Control Spike Results.

ETS

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- 044.1

Ex

ternal Standard

Calibration

Analyzed 7/1 / 13 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

- 130701

- 1 0.191 0.180 94.4 0.199 0.218 110

LCS

- 130701

- 2 0.191 0.176 92.1 0.199 0.203 102

LCS

- 130701

- 3 0.191 0.180 94.5 0.199 0.209 105

Average ± %RSD 93.7 % ± 1.4 % 1 06 % ± 3.8 %

LCS

- 130701

- 4 1.91 1.95 102 1.99 2.11 106

LCS

- 130701

- 5 1.91 1.93 101 1.99 2.12 107

LCS

- 130701

- 6 1.91 1.93 101 1.99 2.18 109

Average ± %RSD 1 0 1 % ± 0. 57 % 107 % ± 1.4 %

LCS

- 130701

- 7 19.1 20.4 107

LCS

- 130701

- 8 19.1 19.3 101

LCS

- 130701

- 9 19.1 19.0 99.6

Average ± %RSD 1 03 % ± 3.8 %

ETS

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- 044.1

External Standard

Calib ration

Analyzed 7/1 /13 PFBS PFHS

Lab ID Spiked

Concentration (ng/mL) Calculated

Concentration (ng/mL) %Recovery Spiked

Concentration (ng/mL) Calculated

Concentration (ng/mL) %Recovery

LCS

- 130701

- 1 0.199 0.190 95.3 0.199 0.197 99.1

LCS

- 130701

- 2 0 .199 0.188 94.3 0.199 0.190 95.3

LCS

- 130701

- 3 0.199 0.196 98.5 0.199 0.196 98.4

Average ± %RSD 96.0 % ± 2.3 % 97.6 % ± 2.1 %

LCS

- 130701

- 4 1.99 2.10 105 1.99 2.09 105

LCS

- 130701

- 5 1.99 2.08 105 1.99 2.10 105

LCS

- 130701

- 6 1.99 2.08 105 1.99 2.12 107

Average ± %RSD 1 0 5 % ± 0 .0 % 106 % ± 1.1 %

LCS

- 130701

- 7 20.0 20.1 100 20.0 20.7 104

LCS

- 130701

- 8 2 0.0 19.1 95.4 20.0 19.7 98.4

LCS

- 130701

- 9 20.0 19.4 97.1 20.0 19.4 96.9

Average ± %RSD 97.5 % ± 2

. 4 % 99.8 % ± 3.8 %3M ENVIRONMENTAL LAB ORATORY

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

ETS

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External Standard

Calibration

Analyzed 7/1 /13 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

- 130701

- 1 0.185 0.192 104 0.190 0.187 98.6

LCS

- 130701

- 2 0.185 0.184 99.5 0 .190 0.183 96.3

LCS

- 130701

- 3 0.185 0.183 99.1 0.190 0.183 96.5

Average ± %RSD 101 % ± 2.7 % 97.1 % ± 1.3 %

LCS

- 130701

- 4 1.85 1.95 106 1.90 1.91 100

LCS

- 130701

- 5 1.85 1.96 106 1.90 1.95 103

LCS

- 130701

- 6 1.85 1.97 106 1.90 1.95 102

Average ± %RSD 10 6 % ± 0

. 0 % 10 2 % ± 1.5 %

LCS

- 130701

- 7 18.5 20.3 110

LCS

- 130701

- 8 18.5 20.0 10 8

LCS

- 130701

- 9 18.5 19.6 106

Average ± %RSD 108 % ± 1.9 %

ETS

- 8

- 044.1

In ternal Standard

Calibration

Analyzed 7/ 2 /13 PFOA (Linear + Branched) PFOA surrogate

Lab ID Spiked

Concentration (ng/mL) Calculated

Concentration (ng/mL) %Recovery Spike d
Concentration (ng/mL) Calculated

Concentration (ng/mL) %Recovery

LCS

- 130702

- 1 0.190 0.176 92.6 0.198 0.218 110

LCS

- 130702

- 2 0.190 0.177 93.4 0.198 0.232 117

LCS

- 130702

- 3 0.190 0.188 99.2 0.198 0.225 114

Average ± %RSD 95.1 % ± 3.8 % 1 14 % ± 3.1 %

LC S

- 130702

- 4 1.90 1.92 101 1.98 2.12 107

LCS

- 130702

- 5 1.90 1.97 104 1.98 2.15 108

LCS

- 130702

- 6 1.90 1.89 99.3 1.98 2.11 107

Average ± %RSD 101 % ± 2.3 % 107 % ± 0.5 4 %

LCS

- 130702

- 7 9.52 10.0 105

LCS

- 130702

- 8 9.52 9.13 95.9

LCS

- 130702

- 9 9.52 9.75 102

Average ± %RSD 101 % ± 4.6 %3M ENVIRONMENTAL LAB ORATORY

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

ETS

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In ternal Standard

Calibration

Analyzed 7/ 2 /13 PFBS PFHS

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

LCS

- 130702

- 1 0.198 0.210 106 0.198 0.192 97.1

LCS

- 130702

- 2 0.198 0.209 105 0.198 0.197 99.4

LCS

- 130702

- 3 0.198 0.222 112 0.198 0.197 99.4

Average ± %RSD 108 % ± 3.5 % 98.6 % ± 1.3 %

LCS

- 130702

- 4 1. 98 2.21 111 1.98 2.07 105

LCS

- 130702

- 5 1.98 2.17 110 1.98 1.99 101

LCS

- 130702

- 6 1.98 2.22 112 1.98 2.01 102

Average ± %RSD 1 11 % ± 0.90 % 1 03 % ± 2.0 %

LCS

- 130702

- 7 9.94 11.4 115 9.94 10.3 104

LCS

- 130702

- 8 9.94 10.2 103 9.94 9.25 93.1

LCS

- 130702

- 9 9.94 1 1.5 116 9.94 10.5 105

Average ± %RSD 111 % ± 6.5 % 101 % ± 6.6 %

ETS

- 8

- 044.1

In ternal Standard

Calibration

Analyzed 7/ 2 /13 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

- 130702

- 1 0.184 0.186 101 0.189 0.192 102

LCS

- 130702

- 2 0.184 0.173 94.1 0.189 0.185 97.9

LCS

- 130702

- 3 0.184 0.185 101 0.189 0.200 106

Average ± %RSD 98.7 % ± 4.0 % 102 % ± 4.0 %

LCS

- 13 0702

- 4 1.84 1.84 100 1.89 1.90 100

LCS

- 130702

- 5 1.84 1.86 101 1.89 1.99 105

LCS

- 130702

- 6 1.84 1.97 107 1.89 1.97 104

Average ± %RSD 103 % ± 3.7 % 10 3 % ± 2.6 %

LCS

- 130702

- 7 9.21 9.63 105

LCS

- 130702

- 8 9.21 8.84 96.0

LCS

- 130702

- 9 9.21 9.59 104

A

verage ± %RSD 102 % ± 4 .9%3M ENVIRONMENTAL LAB ORATORY

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

ETS

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External Standard

Calibration

Analyzed 7/5/13 PFBS

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

LCS

- 130705

- 1 0.199 0. 201 101

LCS

- 130705

- 2 0.199 0.200 101

LCS

- 130705

- 3 0.199 0.205 103

Average ± %RSD 102 % ± 1.1 %

LCS

- 130705

- 4 1.99 2.15 108

LCS

- 130705

- 5 1.99 2.27 114

LCS

- 130705

- 6 1.99 2.17 109

Average ± %RSD 110 % ± 2.9 %

LCS

- 130705

- 7 20.0 19.1 95.3

LCS

- 130705

- 8 20.0 19.9 99.7

LCS

- 130705

- 9 20.0 19.5 97.5

Average ± %RSD 97.5 % ± 2.3 %



## 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 i s calculated following ETS

- 12

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

Table 8 . Analytical Method Uncertainty.

Analyte Calibration Method Standard Deviation Method Uncertainty

PF OA External Standard 6.94 ± 14 %

PFBS External Standard 6.50 ± 13 %

PFHS External Standard 6. 68 ± 13 %

PFOS External Standard 8.07 ± 16 %

PFOA Internal Standard 9.56 ±19 %

PFBS Internal Standard 9.13 ± 18 %

PFHS Internal Standard 9.41 ± 19 %

PFOS Internal Standard 10.7 ± 21 %3M ENVIRONMENTAL LAB ORATORY

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## 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 sam ple 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 inte rest. 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 Matrix Spike 2 000 201 0 200 0 1990

ACM2 Field Matrix Spike 10 0 0 1000 998 994

ACE Field Ma trix Spike 10.0 10.0 9.99 10.0

WW8R, WW9R Field Matrix Spike 4 01 0 4020 3990 3980

Trip Blank Low Field Matrix Spike 10.0 10.0 9.99 10.0

High Field Matrix Spike 401 0 4020 3990 3980



# 4 Data Summary and Discussion

The tables below summarize the sample resul ts and field m atrix spike recoveries for the five locations as well as the Trip Blank. Each table provides the average concentration and the relative percent difference ( % RPD) of the sample and sample duplicate. Results and average values are rounded to three significant figures. Percent relative difference (%RPD) values are rounded to two significant figures. Because of rounding, values may vary slightly from those listed in the raw data. Field matrix spikes meeting the method acceptance criteria of ± 30%, demonstrate that the method is appropriate for the given matrix.

All field matrix spike samples and surrogate recovery standards met method acceptance criteria except

where noted below.

DAL

- GW

- ACM2 ; the FMS sample (10 00 ng/mL) was not appropriate for PFOS or PFHS ; however, t he surrogate recovery standard 13 

### C 4 

### - PFOS, met method acceptance criteria. No additional QC samples were prepared. The FMS sample recovery was 65.5% for PFBS. The method uncertainty has been expanded for PFBS to ± 35% based on the FMS recovery %bias.

DAL GW ACE ; the FMS sample (10 ng/mL) was not appropriate for PFBS; however, the 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

- 06

PA GE 13 OF 21 

### Table 10

. DAL GW ACI 130 627 (1)

PFOA PFBS

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

ISO13

- 07

- 06

- 001 DAL

- GW

- ACI

- 0

- 130627 1460 NA 706 NA

ISO13

- 07

- 06

- 002 DAL

- GW

- ACI

- DB

- 130627 1500 NA 710 NA

ISO13

- 07

- 06

- 003 DAL

- GW

- AC I

- FMS

- 130627 3070 79.5 2280 78.2

Average Concentration (ng/mL) ± %RPD 148 0 ng/mL ± 2.7 % 708 ng/mL ± 0.56 %

PFHS PFOS

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

ISO13

- 07

- 06

- 001 DAL

- GW

- ACI

- 0

- 130627 935 NA 1 580 NA

ISO13

- 07

- 06

- 002 DAL

- GW

- ACI

- DB

- 130627 948 NA 1600 NA

ISO13

- 07

- 06

- 003 DAL

- GW

- ACI

- FMS

- 130627 2520 78.9 3380 89.9

Average Concentration (ng/mL) ± %RPD 942 ng/mL ± 1 .4 % 1590 ng/mL ± 1.3 %

13 C 4 - PFOA 13 C 4 - PFOS

3M LIMS ID Description %Recovery %Reco very

ISO13

- 07

- 06

- 001 DAL

- GW

- ACI

- 0

- 130627 99.1 95.9

ISO13

- 07

- 06

- 002 DAL

- GW

- ACI

- DB

- 130627 101 95.5

ISO13

- 07

- 06

- 003 DAL

- GW

- ACI

- FMS

- 130627 96.7 99.3

Average Concentration (ng/mL) ± %RSD 99.0 % ± 2.3 % 96.9 % ± 2.1 %

NA = Not Applicable (1) S amples 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

- 06

PA GE 14 OF 21 

### Table 11

. DAL GW ACM2 130 627

PFOA ( 1 ) PFBS ( 1 )

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

ISO13

- 07

- 06

- 004 DAL

- GW

- ACM2

- 0

- 130627 1220 NA 1030 NA

ISO13

- 07

- 06

- 005 DAL

- GW

- ACM2

- DB

- 130627 1200 NA 1020 NA

ISO13

- 07

- 06

- 006 DAL

- GW

- ACM2

- FMS

- 130627 1970 76.0 1680 65.5 (2)

Average Concentrat ion (ng/mL) ± %RPD 1210 ng/mL ± 1.7 % 103 0 ng/mL ± 0.98 % (3)

PFHS (1 ) PFOS ( 5 )

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

ISO13

- 07

- 06

- 004 DAL

- GW

- ACM2

- 0

- 130627 2040 NA 0.806 NA

ISO13

- 07

- 06

- 005 DAL

- GW

- ACM2

- DB

- 130627 2000 NA 0.738 NA

ISO13

- 07

- 06

- 006 DAL

- GW

- ACM2

- FMS

- 130627 NA (4) NA (4) NA (6 ) NA (6 )

Average Concentration (ng/mL) ± %RPD 2020 ng/mL ± 2.0 % 0.772 ng/mL ± 8.8 %

13 C 4 - PFOA (1) 13 C 4 - PFOS ( 5 )

3M LIMS ID Description %Recovery %Recovery

ISO13

- 07

- 06

- 004 DAL

- GW

- ACM2

- 0

- 130627 99.3 81.3

ISO13

- 07

- 06

- 005 DAL

- GW

- ACM2

- DB

- 130627 96.8 75.8

ISO13

- 07

- 06

- 006 DAL

- GW

- ACM2

- FMS

- 130627 96.1 NA (6 )

Average Concentration (ng/mL) ± % RPD/ RSD 97.4 % ± 1.7 % 78.6 % ± 6.9 %

NA = Not Applicable (1) Samples were analyzed by ex ternal standard calibration. The surrogate recovery standards 13 C 4 - PFOA and 13 C 4 - PFOS were added to the samples during sample preparation. (2) FMS recovery did not meet acceptance criteria of 100 ± 30%. (3) Method uncertainty has been expanded to ± 35% based on th e FMS recovery %bias. (4) Analyte concentration exceeded calibration range. (5) Samples were analyzed by i nternal standard calibration

. (6) Sample was not analyzed using internal calibration due to the high FMS concentration.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

- 07

- 06

PA GE 15 OF 21 

### Table 12

. DAL GW ACE 130 627

PFOA (1) PFBS (3)

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

ISO13

- 07

- 06

- 007 DAL

- GW

- ACE

- 0

- 130627 0.0568 NA 108 NA

ISO13

- 07

- 06

- 008 DAL

- GW

- ACE

- DB

- 130627 0.0866 NA 113 NA

ISO13

- 0 7

- 06

- 009 DAL

- GW

- ACE

- FMS

- 130627 8.52 84.5 NA (4) NA (4)

Average Concentration (ng/mL) ± %RPD 0.0717 ng/mL ± 42 % (2) 111 ng/mL ± 4.5 %

PFHS (1) PFOS (1)

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

ISO13

- 07

- 0 6

- 007 DAL

- GW

- ACE

- 0

- 130627 0.0850 NA <0.0232 NA

ISO13

- 07

- 06

- 008 DAL

- GW

- ACE

- DB

- 130627 0.150 NA <0.0232 NA

ISO13

- 07

- 06

- 009 DAL

- GW

- ACE

- FMS

- 130627 8.52 84.1 8.72 87.2

Average Concentration (ng/mL) ± %RPD 0.118 ng/mL ± 55 % (2) <0.0232 ng/mL

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

3M LIMS ID Description %Recovery %Recovery

ISO13

- 07

- 06

- 007 DAL

- GW

- ACE

- 0

- 130627 90.1 78.0

ISO13

- 07

- 06

- 008 DAL

- GW

- ACE

- DB

- 130627 82.4 81.4

ISO13

- 07

- 06

- 009 DAL

- GW

- ACE

- FMS

- 130627 84.6 79.2

Average Concentration (ng/mL) ± %RSD 85.7 % ± 4.6 % 79.5 % ± 2.1 %

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

. (2) Sample/sample duplicate RPD did not meet acceptance criteria of ≤ 20%. (3) Samples were analyzed by external standard calibration. (4) Sample was not analyzed by external sta ndard calibration due to the inappropriate FMS spike level.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

- 07

- 06

PA GE 16 OF 21 

### Table 13

. DAL GW WW8R 130627 (1)

PFOA PFBS

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

ISO13

- 07

- 06

- 010 DAL

- GW

- WW8R

- 0

- 1306 27 2710 NA 274 NA

ISO13

- 07

- 06

- 011 DAL

- GW

- WW8R

- DB

- 130627 2800 NA 289 NA

ISO13

- 07

- 06

- 012 DAL

- GW

- WW8R

- FMS

- 130627 6900 103 4070 94.2

Average Concentration (ng/mL) ± %RPD 2760 ng/mL ± 3.3 % 282 ng/mL ± 5.3 %

PFHS PFOS

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

ISO13

- 07

- 06

- 010 DAL

- GW

- WW8R

- 0

- 130627 1300 NA 4010 NA

ISO13

- 07

- 06

- 011 DAL

- GW

- WW8R

- DB

- 130627 1380 NA 4210 NA

ISO13

- 07

- 06

- 012 DAL

- GW

- WW8R

- FMS

- 130627 5380 101 8370 107

Average Concentration (ng/mL) ± %RPD 134 0 ng/mL ± 6.0 % 4110 ng/mL ± 4.9 %

13 C 4 - PFOA 13 C 4 - PFOS

3M LIMS ID Description %Recovery %Recovery

ISO13

- 07

- 06

- 010 DAL

- GW

- WW8R

- 0

- 130627 95.0 95.6

ISO13

- 07

- 06

- 011 DAL

- GW

- WW8R

- DB

- 130627 99.0 98.6

ISO13

- 07

- 06

- 012 DAL

- GW

- WW8R

- FMS

- 130627 94.7 99.5

Ave rage Concentration (ng/mL) ± %RSD 96.2 % ± 2.5 % 97.9 % ± 2.1 %

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

- 06

PA GE 17 OF 21 

### Table 14

. DAL GW WW9R 130627 (1)

PFOA PFBS

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

ISO13

- 07

- 06

- 013 DAL

- GW

- WW9R

- 0

- 130627 2590 NA 224 NA

ISO13

- 07

- 06

- 014 DAL

- GW

- WW9R

- DB

- 130627 2660 NA 225 NA

ISO13

- 07

- 06

- 015 DAL

- GW

- WW9R

- FMS

- 130627 6330 92.4 3970 93.2

Average Concentration (ng/mL) ± %RPD 26 30 ng/mL ± 2.7 % 2 25 ng/mL ± 0 .4 5 %

PFHS PFOS

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

IS O13

- 07

- 06

- 013 DAL

- GW

- WW9R

- 0

- 130627 1140 NA 4170 NA

ISO13

- 07

- 06

- 014 DAL

- GW

- WW9R

- DB

- 130627 1130 NA 4130 NA

ISO13

- 07

- 06

- 015 DAL

- GW

- WW9R

- FMS

- 130627 5000 96.9 7240 77.6

Average Concentration (ng/mL) ± %RPD 114 0 ng/mL ± 0

. 8 8 % 415 0 ng/mL ± 0.96 %

13 C 4 - PFOA 13 C 4 - PFOS

3M LIMS ID Description %Recovery %Recovery

ISO13

- 07

- 06

- 013 DAL

- GW

- WW9R

- 0

- 130627 99.6 95.4

ISO13

- 07

- 06

- 014 DAL

- GW

- WW9R

- DB

- 130627 98.5 98.2

ISO13

- 07

- 06

- 015 DAL

- GW

- WW9R

- FMS

- 130627 88.1 99.0

Average Concentration (ng/mL) ± %RSD 95.4 % ± 6.7 % 97.5 % ± 1.9 %

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

- 06

PA GE 18 OF 21 

### Table 15 . Tri p Blank Results

PFOA PFBS

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

ISO13

- 07

- 06

- 016 DAL

- GW

- TRIP01

- 0 <0.0240 (1) NA <0.0250 (1) NA

ISO13

- 07

- 06

- 017 DAL

- GW

- TRIP01

- LS 8.07 (1) 80.7 9.75 (1) 97.5

ISO13

- 07

- 06

- 018 DAL

- GW

- TRIP01

- HS 3850 (2) 96.0 373 0 (2) 92.8

PFHS PFOS

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

ISO13

- 07

- 06

- 016 DAL

- GW

- TRIP01

- 0 <0.0250 (1) NA <0.0232 (1) NA

ISO13

- 07

- 06

- 017 DAL

- GW

- TRIP01

- LS 8.47 ( 1) 84.8 8.44 (1) 84.4

ISO13

- 07

- 06

- 018 DAL

- GW

- TRIP01

- HS 3750 (2) 94.0 405 0 (2) 102

13 C 4 - PFOA 13 C 4 - PFOS

3M LIMS ID Description %Recovery %Recovery

ISO13

- 07

- 06

- 016 DAL

- GW

- TRIP01

- 0 8 0.1 (1) 81.9 (1)

ISO13

- 07

- 06

- 017 DAL

- GW

- TRIP01

- LS 76.8 (1) 78.5 (1)

I SO13

- 07

- 06

- 018 DAL

- GW

- TRIP01

- HS 96.7 (2) 92.8 ( 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 LABORATORY

REPORT

NO. ISO13-07-06



# 5 Conclusio n

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

. Th e accurac

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

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

. Analysi s wa s complete d usin g 3 M Environmenta l Laborator y Metho d ETS-8

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

. Analytica l result s ar e reporte d i n Tabl e 1 an d 10-1 5 o f thi s report

.



# 6 Dat a /

Sampl e Retentio n

Al l remainin g sampl e an d associate d projec t dat a (hardcop y an d electronic ) wil l b e archive d accordin g

t o 3 M Environmenta l Laborator y standar d operatin g procedures

.



# 7 Attachment s

Attachmen t A : Analyt e Tren d Dat a fo r selec t samplin g point s a t th e Decatu r Groun d Wate r Treatmen t

Plan t (GWTP ) GA C System

.



# 8 Signature s

Susa n T

. Wolf

, 3 M Pranbipa l Analytica l Investigato r Dat e

Willia m K

. Reagen

, Ph.D.

, 3 M Environmenta l Laborator y Technica l Directo r Dat e

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

.



# Cd~&^ ^ HyQ-^—e^^ ^

7-/ 7 - Q

Quality Assu^nc e Representativ e ^ Date ^

This test report shall not be reproduced

except in full, without

written approval

of the 3M

Environmental

Laboratory.

PAG E 1 9 O F 2 13M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

- 07

- 06

PAGE 20 OF 21 

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

ACI (Activat ed Carbon Influent)

- Sample Results in ng/mL

ACI 2/8/ 12 6/29/ 12 8/28/ 12 12/14/ 12 1/17/ 13 2/13/ 13 3/27/ 13 4/29/ 13 5/31/ 13 6/27/ 13

PFOA 1180 1650 1410 2580 1910 2300 2220 1480 1860 1480

PFBS 792 1410 1830 723 588 830 1060 1360 1040 708

PFHS 1100 1460 1390 1380 895 1580 1090 777 940 942

PFOS 782 964 172 2810 1810 2940 2490 1670 2150 1590



### AC E (Activated Carbon Ef fluent)

- Sample Results in ng/mL

ACE 2/8/ 12 8/28/ 12 12/14/ 12 1/17/ 13 2/13/ 13 3/27/ 13 4/29/ 13 5/31/ 13 6/27/ 13

PFOA 1250 0.387 0.102 <0. 0240 0.124 0.0380 0.0422 0.0725 0.0717

PFBS 818 0.256 <0.0250 <0.0250 0.0360 <0.0250 0.392 24.8 111

PFHS 1240 0.552 0.117 <0.0250 0.178 0.0477 0.057 0.105 0.118

PFOS 741 0.103 0.0376 <0.0232 0.0329 <0.0232 <0.0232 <0.0232 <0.0232

The ACE location was not sampled on 6/29/12.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

- 07

- 06

PAGE 21 OF 21 

### 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 12/13/2012 1/17/2013 2/13/2013 3/27/2013 4/29/2013 5/31/2013 6/27/2 013

PFOA 3630 4350 3250 3640 3190 2760 2760

PFBS 441 410 354 385 364 289 282

PFHS 1740 1930 1900 1760 1610 1330 1340

PFOS 4920 5710 4850 5120 4830 4180 4110



### WW9R

- Sample Results in ng/mL

WW9R 12/13/2012 1/17/2013 2/13/2013 3/27/2013 4/29/2013 5/ 31/2013 6/27/2013

PFOA 3360 2710 2850 3330 2650 2660 2630

PFBS 321 184 236 278 244 226 225

PFHS 1480 954 1400 1440 1200 1120 1140

PFOS 4080 3690 4100 4660 4340 4210 4150