3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

- 07

- 03

PAGE 1 OF 21 

# Final Report

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

3M Decatur, Alabama : Groundwater Treatment Plant GAC System

– March 2013

Laboratory Request Number: ISO13

- 07

- 03

Method Re quirement: 3M Method ETS

- 8

- 044.1

Report Date

– Dat e 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

Testing Cert #2052. 01 The testing reported herein meet the requirements of ANSI/ISO/IEC 17025:2005 “General Requirements for the Competence of Testing and Calibration Laboratories”, in acco rdance with the A2LA Testing Certificate # 2052.01.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

- 07

- 03

PAGE 2 OF 21 

### 3M Environmental 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** 

**- 03** 

3M Decatur Groundwater Treatment Plant System; March 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 colle cted by Weston Solutions personnel

on March 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 recovery standards 13 

### C 4 

### - PFOA and 13 

### C 4 

### - PFOS

under la boratory project number ISO13

- 07

- 03

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

- 1006.

T he 3M Enviro nmental Laboratory provided 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 sa mpling 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 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 summarizes the sample results using the analytical metho d identified above. All results for quality control samples prepared and analyzed with the samples will be reported and discussed elsewhere in this report.

Testing Cert #2052.01 The testing reported herein meet the requirements of ANSI/ISO/IEC 17025:2005 “General Requirements for the Competence of Testing and Calib ration Laboratories”, in accordance with the A2LA Testing Certificate # 2052.01.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

- 07

- 03

PAGE 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

- 07

- 03

- 001 DAL

- GW

- ACI ; Sample 2190 1060 1080 2450

ISO13

- 07

- 03

- 002 DAL

- GW

- ACI ; Sample Dup 2250 1060 1090 2520

Average 2 220 (1) 1060 (1) 1090 (1) 2490 (1)

%RPD Sample/Sample Dup 2.7 0. 0 0.92 2.8

ISO13

- 07

- 03

- 004 DAL

- GW

- ACM2; Sample 52.9 2300 170 0.0509

ISO13

- 07

- 03

- 005 DAL

- GW

- ACM2 ; Sample Dup 50.9 2330 171 0.0526

Average 51.9 (1,2 ) 2320 ( 1 ,2 ) 171 (1,2 ) 0.0518 (3 )

%RP D Sample/Sample Dup 3.9 1 .3 0.59 3.3

ISO13

- 07

- 03

- 007 DAL

- GW

- ACE; Sample 0.0362 <0.0250 0.0433 <0.0232

ISO13

- 07

- 03

- 008 DAL

- GW

- ACE ; Sample Dup 0.0398 <0.0250 0.0521 <0.0232

Average 0.0380 (3 ) <0.0250 ( 3 ) 0.0477 ( 3 ) <0.0232 ( 3 )

%RPD Sample/Sample Dup 9.5 NA 18 NA

ISO13

- 07

- 03

- 010 DAL

- GW

- WW8R; Sample 3660 380 1760 5170

ISO13

- 07

- 03

- 011 DAL

- GW

- WW8R ; Sample Dup 3620 389 1760 5070

Average 3640 (1) 385 (1) 1760 (1) 5120 (1)

%RPD Sample/Sample Dup 1.1 2. 3 0.0 2.0

ISO13

- 07

- 03

- 013 DAL

- GW

- WW9R; Sample 3260 273 1410 4530

ISO13

- 07

- 03

- 014 DAL

- GW

- WW9R ; Sample Dup 3400 283 1470 4780

Average 3330 (1) 278 (1) 1440 (1) 4660 (1)

%RPD Sample/Sample Dup 4.2 3. 6 4.2 5.4

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

- 8

- 044. 1 using ext ernal standard calibration . The analytical method uncertainties associated with the reported results are as follows: PFOA ±18 %, PFBS ± 21 %, PFHS ±15 %, and PFOS ± 24 %. (2) Sample did not have an appropriate FMS to access recovery. See section 4 for more detai ls. (3) Reported results were prepared and analyzed by ETS

- 8

- 044. 1 using internal standard calibration . The analytical method uncertainties associated with the reported results are as follows: PFOA ± 16 %, PFBS ± 2 2 %, PFHS ± 14 %, and PFOS ±
24 %.



# 2 Methods

- Ana lytical and Preparatory

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

- 8

- 044. 1 “ Method of Analysis

for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis ”

.

Table 2 Target Analytes.

Target Analytes Acronym Reference
Material Structure

Perfluorooctanoic Acid (C8 Acid) PFOA Linear + Branched

Perfluorobutanesulfonate (C4 Sulfonate ) PFBS Linear

Perfluorohexanesulfonate (C6 Sulfonate) PFHS Linear

Perfluorooctan esulfonate (C8 Sulfonate) PFOS Linear + Branched3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

- 07

- 03

PAGE 4 OF 21 

## 2.2 Sample Collection
Samples were collected on March 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 Trip 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

. Collected sample bottles were received by the laboratory at

ambient c onditions on April 1 , 201 3

.



## 2.3 Sample Preparation
Sample sets ACI, ACM2, WW8R, WW9R, 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 sample an d 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 analytes 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 separate 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 be ing 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 chromatog raphy/ 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 con centrations 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 integr ation of the analytical peak is necessary. All manual integrations are performed following the procedures outlined in method ETS

- 12

- 010. The consistency of the laboratory’s integration is ensured through the training of laboratory personnel, the peer rev iew 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

REPORT NO. ISO13

- 07

- 03

PAGE 5 OF 21 

### Table 3 . Instrument Parameters.

Instrument Name ETS K irk ETS Kirk

Analysis Dates 4/3 /13

– ex ternal standard calibration 4/4 /13

– in ternal standard calibration

Analytical Method ETS

- 8

- 044.1 ETS

- 8

- 044.1

Liquid Chromatograph Agilent 1 260 Agilent 1 260

Guard column Betasil C18 (4.6 mm X 100 mm), 5 μ Betasil C18 (4.6 mm X 100 mm), 5 μ
Analytical column Betasil C18 (4.6 mm X 100 mm), 5 μ Betasil C18 (4.6 mm X 100 mm), 5 μ
Injection Volume 2, 5

, or 2 0 μ L 20 μ L

Mass Spectrometer Applied Biosystems TripleQuad 55 00 Applied Biosystems TripleQuad 5500

Ion Source Turbo Spray Turbo Spray

Polarity Negative Negative

Software Analyst 1.6.1 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 10.0



### Table 5 . Mass Transitions

Analyte Mass Transition

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

PFOA 413/369

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

413/169

PFBS 299/80 [ 18 O 2 ]PFBS 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 507/80

Dwell time was 5 0 msec for each transition. The individual transitions were summed to produce a “total ion chroma togram” (TIC) , which was u sed for quantitation.

(1) Internal standard s were used for the analysis on 4/4 /13.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

- 07

- 03

PAGE 6 OF 21 

# 3 Data Analysis

3.1 Calibration

Internal Standard Calibration Analysis : Samples were analyzed against a matrix

- matched stable isotope internal stand ard calibration curve. Calibration standards were prepared by spiking known

amounts of stock solutions into 50 mL of 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 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. The reference standards of PFOA and PFOS used to prepare the

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

correlation coeffi cient (r) was greater than 0.995 for all analytes.

External Standard Calibration Analysis: Samples were analyzed against an external standard calibration curve. Calibration standards were prepared by spiking known amounts of the stock solution

containin g the target analytes into 90:10 m ethanol: Mil li

- Q laboratory water. A total of t en spiked standards ranging from 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 fit the data for each analyte. The data were not forced through zero during the fitting process. Calculating the standard concentrations using t he peak area counts and the resultant calibration curve confirmed accuracy of each curve point. Each curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method calibration accuracy requirements of 100±25% (100±30% f or the lowest curve point) were met for all analytes. The correlation coefficient (r) was greater than 0.995 for all analytes

.



## 3.2 System Suitability

A calibration standard was analyzed four times at the beginning of the analytical sequence to

demonstrate ov erall 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 al l analytes

.



## 3.3 Limit of Quantitation (LOQ)

The LOQ as defined in method ETS

- 8

- 044. 1 is the lowest non

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

.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

- 07

- 03

PAGE 7 OF 21 

### T able 6 . LOQ

Analyte Calibration LOQ, ng/mL

PFOA Internal standard 0.0240

PFBS Internal standard 0.0250

PFHS Internal standard 0.0250

PFOS Int ernal standard 0.0232

PFOA External standard 0.0192 ( 1 )

PFBS External standard 0.0200 (1 )

PFHS External standard 0.0200 (1 )

PFOS 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 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 evaluate method performance to determine the LOQ for each analyte.



## 3.6 Lab C ontrol 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 a nalytes 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

- 8

- 044.1 states th at 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 criteria except where noted below.

External standard analysis: Mid level LCSs did not meet average recovery criteria for PFBS ( 121%)
and PFOS (122%) . High level LCSs did not meet average recovery criteria PFOS (124%)

.

Internal standard analysis: Mid level LCSs did not meet average recovery criteria for PFOS (124%)

. High level LCSs did not meet average recovery criteria for PFBS (122%) and PFOS (122%)

.

A method deviation is included with the raw data. All LCSs were used in the determination of the analytical method uncertainty in section 3.9.

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

REPORT NO. ISO13

- 07

- 03

PAGE 8 OF 21 

### Table 7 . Lab Control Spike Results.

ETS

- 8

- 044.1

Ex

ternal Standard

Calibration

Analyzed 4/3 / 13 PFOA (Linear + Branched ) PFOS (Linear + Branched)

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

LCS

- 130403

- 1 0.191 0.212 111 0.185 0.198 107

LCS

- 130403

- 2 0.191 0.201 105 0.185 0.199 108

LCS

- 130403

- 3 0.191 0.211 110 0.185 0.200 108

Average ± %RSD 109 % ± 3.0 % 108 % ± 0.54 %

LCS

- 130403

- 4 1.91 2.29 120 1.85 2.24 121

LCS

- 130403

- 5 1.91 2.26 118 1.85 2.24 121

LCS

- 130403

- 6 1.91 2.33 122 1.85 2.28 123

Average ± %RSD 1 20 % ± 1.7 % 122 % ± 0.95 % (1)

LCS

- 130403

- 7 19.1 22.1 116 18.5 23.0 124

LCS

- 130403

- 8 19.1 21.0 110 18.5 22.3 121

LCS

- 130403

- 9 19.1 22.1 116 18.5 23.5 127

Average ± %RSD 114 % ± 3.0 % 124 % ± 2.4 % (1)

ETS

- 8

- 044.1

Ex

ternal Standard

Calibration

Analyzed 4/3/13 PFBS PFHS

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

LCS

- 130403

- 1 0.199 0.221 111 0.199 0.216 108

LCS

- 130403

- 2 0.199 0.219 110 0.199 0.214 108

LCS

- 130403

- 3 0.199 0.223 112 0.199 0.223 112

Average ± %RSD 111 % ± 0.90 % 109 % ± 2.1 %

LCS

- 130403

- 4 1.99 2.39 120 1.99 2.32 117

LCS

- 130403

- 5 1.99 2.41 121 1.99 2.36 119

LCS

- 130403

- 6 1.99 2.45 123 1.99 2.37 119

Average ± %RSD 121 % ± 1.3 % (1) 1 18 % ± 0.98 %

LCS

- 130403

- 7 20.0 22.9 114 20.0 22.1 110

LCS

- 130403

- 8 20.0 22.1 1 10 20.0 21.1 105

LCS

- 130403

- 9 20.0 23.8 119 20.0 21.9 109

Average ± %RSD 114 % ± 3.9 % 108 % ± 2.4 %

(1) LCSs did not meet acceptance criteria of 100 ± 20%.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

- 07

- 03

PAGE 9 OF 21 

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

ETS

- 8

- 044.1

Ex

ternal Standard

Calibration

Analy zed 4/3/13 PFOA surrogate PFOS surrogate

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

LCS

- 130403

- 1 0.199 0.202 101 0.190 0.196 103

LCS

- 1304 03

- 2 0.199 0.206 104 0.190 0.197 103

LCS

- 130403

- 3 0.199 0.208 104 0.190 0.195 103

Average ± %RSD 103 % ± 1.7 % 103 % ± 0.0 %

LCS

- 130403

- 4 1.99 2.09 105 1.90 2.06 109

LCS

- 130403

- 5 1.99 2.13 107 1.90 2.05 108

LCS

- 130403

- 6 1.99 2.12 106 1.90 2.05 108

Average ± %RSD 106 % ± 0.94 % 108 % ± 0.53 %

ETS

- 8

- 044.1

In ternal Standard

Calibration

Analyzed 4/ 4 /13 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

- 130404

- 1 0.190 0.205 108 0.184 0.217 118

LCS

- 130404

- 2 0.190 0.202 106 0.184 0.215 117

LCS

- 130404

- 3 0.190 0.197 104 0.184 0.218 119

Average ± %RSD 106 % ± 1. 9 % 1 18 % ± 0.85 %

LCS

- 130404

- 4 1.90 2.25 118 1.84 2.35 128

LCS

- 130404

- 5 1.90 2.21 116 1.84 2.17 118

LCS

- 130404

- 6 1.90 2.23 117 1.84 2.32 126

Average ± %RSD 117 % ± 0.85 % 1 24 % ± 4.3 % (1)

LCS

- 130404

- 7 9.52 10.5 111 9.21 10.4 113

LCS

- 130404

- 8 9.52 11.8 124 9.21 11.4 124

LCS

- 130404

- 9 9.52 12.0 126 9.21 11.9 129

Average ± %RSD 120 % ± 6.8 % 1 22 % ± 6 .7 % (1)

(1) LCSs did not meet acceptance criteria of 100 ± 20%.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

- 07

- 03

PAGE 10 OF 21 

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

ETS

- 8

- 044.1

In ternal Standard

Cali bration

Analyzed 4/ 4 /13 PFBS PFHS

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

LCS

- 130404

- 1 0.198 0.215 108 0.198 0.219 111

LCS

- 130404

- 2 0. 198 0.221 112 0.198 0.216 109

LCS

- 130404

- 3 0.198 0.217 110 0.198 0.213 108

Average ± %RSD 1 10 % ± 1.8 % 109 % ± 1.4 %

LCS

- 130404

- 4 1.98 2.34 118 1.98 2.32 117

LCS

- 130404

- 5 1.98 2.34 118 1.98 2.29 116

LCS

- 130404

- 6 1.98 2.44 123 1.98 2.38 120

Average ± %RSD 1 20 % ± 2. 4 % 1 18 % ± 1.8 %

LCS

- 130404

- 7 9.94 11.3 114 9.94 11.0 111

LCS

- 130404

- 8 9.9 4 12.5 126 9.94 11.8 119

LCS

- 130404

- 9 9.94 12.6 127 9.94 12.2 123

Average ± %RSD 122 % ± 5.9 % (1) 118 % ± 5.2 %

ETS

- 8

- 044.1

In ternal Standard

Calibration

Analyzed 4/ 4 /13 PFOA surrogate PFOS surrogate

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

LCS

- 130404

- 1 0.198 0.191 96.4 0.189 0.186 98.4

LCS

- 130404

- 2 0.198 0.189 95.5 0.189 0.186 98.4

LCS

- 130404

- 3 0.198 0.186 93.9 0.189 0.190 101

Averag e ± %RSD 95.3 % ± 1.3 % 99.3 % ± 1.5 %

LCS

- 130404

- 4 1.98 1.95 98.5 1.89 1.95 103

LCS

- 130404

- 5 1.98 2.01 102 1.89 1.87 98.8

LCS

- 130404

- 6 1.98 2.00 101 1.89 1.92 102

Average ± %RSD 10 1 % ± 1.8 % 101 % ± 2.2 %

(1) LCSs did not meet acceptance criteria of 100 ± 20%.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

- 07

- 03

PAGE 11 OF 21 

## 3.7 Analytical Method Uncertainty
Analytical uncertainty is based on historical QC data that is control charted and used to evaluate method accuracy and precision. The method uncertainty is calculated following ETS

- 12

- 012.2. The

standard deviation is calculated for the set of accuracy results (in %) obtained for the QC samples. The expanded uncertainty is calculated by multiplying the standard deviation by a factor of 2, which corresponds to a confidence level of 95%. The method uncertainty was d etermined to be ± 17% for
PFBS and ± 16% for PFOS using internal calibration and ±15% for PFBS and ±20% for PFOS using external calibration, but based on the percent bias of the LCSs, the method uncertainty has been expanded for PFBS and PFOS.

Table 8 . Analytical Method Uncertainty.

Analyte Calibration Method Standard Deviation Method Uncertainty

PF OA External Standard 8.86 ± 18 %

PFBS External Standard NA ± 21 %

PFHS External Standard 7.71 ± 15 %

PFOS External Standard NA ± 24 %

PFOA Internal Standard 8.02 ± 16 %

PFBS Internal Standard NA ± 2 2 %

PFHS Internal Standard 7.02 ± 14 %

PFOS Internal Standard NA ± 24 %
NA= Not Applicable



## 3.8 Field Matrix Spikes (FMS)
A field matrix spike w as collected at each sampling point to verify that the analy tical 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 prepa ration 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 2 110 1990 1970 2000

ACM2, ACE Field Matrix Spike 10. 5 9.96 9.86 10.0

WW8R, WW9R Field Matrix Spike 4 220 3980 3940 4000

Trip Blank Low Field Matrix Spike 10. 5 9.96 9.86 10.0

High Field Matrix Spike 4220 3980 3940 40003M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

- 07

- 03

PAGE 12 OF 21 

# 4 Data Summary and Discussion

The tables below summarize the sample results and field matrix spike recoveries for the t hree locations

as well as the T rip 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 ro unded 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 (1 0 ng/mL) was not appropriate for PFOA, PFBS , or PFHS ; however, the FMS sample for PFOS and the surrogate r ecovery standards 13 

### C 4 

### - PFOA and 13 

### C 4 

### - PFOS

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

REPORT NO. ISO13

- 07

- 03

PAGE 13 OF 21 

### Table 10

. DAL GW ACI 130327 (1)

PFOA PFBS

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

ISO13

- 07

- 03

- 001 DAL

- GW

- ACI

- 0

- 130327 2190 NA 1060 NA

ISO13

- 07

- 03

- 002 DAL

- GW

- ACI

- DB

- 130327 2250 NA 1060 NA

ISO13

- 07

- 03

- 003 DAL

- GW

- ACI

- FMS

- 130327 4210 94.3 2930 94.0

Average Concentration (ng/mL) ± %RPD 2220 ng/mL ± 2.7 % 1060 ng/mL ± 0. 0 %

PFHS PFOS

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

ISO13

- 07

- 03

- 001 DAL

- GW

- ACI

- 0

- 130327 1080 NA 2450 NA

ISO13

- 07

- 03

- 002 DAL

- GW

- ACI

- DB

- 130327 1090 NA 2520 NA

ISO13

- 07

- 03

- 003 DAL

- GW

- ACI

- FMS

- 130327 2950 94.7 4590 105

Average Concentration (ng/mL) ± %RPD 1090 ng/mL ± 0.92 % 2490 ng/mL ± 2.8 %

13 C 4 - PFOA 13 C 4 - PFOS

3M LIMS ID Description %Recovery %Recovery

ISO13

- 07

- 03

- 001 DAL

- GW

- ACI

- 0

- 130327 100 101

ISO13

- 07

- 03

- 002 DAL

- GW

- ACI

- DB

- 130327 104 102

ISO13

- 07

- 03

- 003 DAL

- GW

- ACI

- FMS

- 130327 96.8 103

Average Concentration (ng/mL) ± %RSD 100 % ± 3.7 % 102 % ± 0.91 %

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

- 03

PAGE 14 OF 21 

### Table 11

. DAL GW ACM2 130327

PFOA ( 1 ) PFBS ( 1 )

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

ISO13

- 07

- 03

- 004 DAL

- GW

- ACM2

- 0

- 130327 52.9 NA 2300 NA

ISO13

- 07

- 03

- 005 DAL

- GW

- ACM2

- DB

- 130327 50.9 NA 2330 NA

ISO13

- 07

- 03

- 006 DAL

- GW

- ACM2

- FMS

- 130327 61.9 NC 2320 NC

Average Concentration (ng/mL) ± %RPD 51.9 ng/mL ± 3.9 % 2320 ng/mL ± 1. 3 %

PFHS (1 ) PFOS ( 2 )

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

ISO13

- 07

- 03

- 004 DAL

- GW

- ACM2

- 0

- 130327 170 NA 0.0509 NA

ISO13

- 07

- 03

- 005 DAL

- GW

- ACM2

- DB

- 130327 171 NA 0.0526 NA

ISO13

- 07

- 03

- 006 DAL

- GW

- ACM2

- FMS

- 130327 176 NC 10.1 100

Average Concentration (ng/mL) ± %RPD 171 ng/mL ± 0.59 % 0.0518 ng/mL ± 3.3 %

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

3M LIMS ID Description %Recovery %Recovery

ISO13

- 07

- 03

- 004 DAL

- GW

- ACM2

- 0

- 130327 103 94.1

ISO13

- 07

- 03

- 005 DAL

- GW

- ACM2

- DB

- 130327 103 98.5

ISO13

- 07

- 03

- 006 DAL

- GW

- ACM2

- FMS

- 130327 1 03 94.7

Average Concentration (ng/mL) ± %RSD 103 % ± 0.0 % 95.8 % ± 2.5 %

NA = Not Applicable NC = Not Calculated; Spike level was less than 0.5x the endogenous sample concentration. (1) Samples were analyzed by external standard calibration. The surrogate rec overy standards 13 C 4 - PFOA and 13 C 4 - PFOS were added to the samples during sample preparation. (2) Samples were analyzed by i nternal standard calibration

.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

- 07

- 03

PAGE 15 OF 21 

### Table 12

. DAL GW ACE 130327 (1)

PFOA PFBS

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

ISO13

- 07

- 03

- 007 DAL

- GW

- ACE

- 0

- 130327 0.0362 NA <0.0250 NA

ISO13

- 07

- 03

- 008 DAL

- GW

- ACE

- DB

- 130327 0.0398 NA <0.0250 NA

ISO13

- 07

- 03

- 009 DAL

- GW

- ACE

- FMS

- 130327 10.2 96.4 9.85 98.9

Average C oncentration (ng/mL) ± %RPD 0. 0380 ng/mL ± 9.5 % <0.0250 ng/mL

PFHS PFOS

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

ISO13

- 07

- 03

- 007 DAL

- GW

- ACE

- 0

- 130327 0.0433 NA <0.0232 NA

ISO13

- 07

- 03

- 008 DAL

- GW

- ACE

- DB

- 1 30327 0.0521 NA <0.0232 NA

ISO13

- 07

- 03

- 009 DAL

- GW

- ACE

- FMS

- 130327 9.31 93.9 10.4 104

Average Concentration (ng/mL) ± %RPD 0.0477 ng/mL ± 18 % <0.0232 ng/mL

13 C 4 - PFOA 13 C 4 - PFOS

3M LIMS ID Description %Recovery %Recovery

ISO13

- 07

- 03

- 007 DAL

- GW

- ACE

- 0

- 13 0327 102 112

ISO13

- 07

- 03

- 008 DAL

- GW

- ACE

- DB

- 130327 105 110

ISO13

- 07

- 03

- 009 DAL

- GW

- ACE

- FMS

- 130327 104 107

Average Concentration (ng/mL) ± %RSD 104 % ± 1.5 % 109 % ± 2.4 %

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

.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

- 07

- 03

PAGE 16 OF 21 

### Table 13

. DAL GW WW8R 130327 (1)

PFOA PFBS

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

ISO13

- 07

- 03

- 010 DAL

- GW

- WW8R

- 0

- 130327 3660 NA 380 NA

ISO13

- 07

- 03

- 011 DAL

- GW

- WW8R

- DB

- 130327 3620 NA 389 N A

ISO13

- 07

- 03

- 012 DAL

- GW

- WW8R

- FMS

- 130327 7620 94.3 4100 93.4

Average Concentration (ng/mL) ± %RPD 3 640 ng/mL ± 1.1 % 385 ng/mL ± 2.3 %

PFHS PFOS

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

ISO13

- 07

- 03

- 010 DAL

- GW

- WW8R

- 0

- 130327 1760 NA 5170 NA

ISO13

- 07

- 03

- 011 DAL

- GW

- WW8R

- DB

- 130327 1760 NA 5070 NA

ISO13

- 07

- 03

- 012 DAL

- GW

- WW8R

- FMS

- 130327 5520 95.4 9670 114

Average Concentration (ng/mL) ± %RPD 1760 ng/mL ± 0.0 % 5120 ng/mL ± 2.0 %

13 C 4 - PFOA 13 C 4 - PFOS

3M LIM S ID Description %Recovery %Recovery

ISO13

- 07

- 03

- 010 DAL

- GW

- WW8R

- 0

- 130327 96.0 101

ISO13

- 07

- 03

- 011 DAL

- GW

- WW8R

- DB

- 130327 94.6 101

ISO13

- 07

- 03

- 012 DAL

- GW

- WW8R

- FMS

- 130327 93.4 96.0

Average Concentration (ng/mL) ± %RSD 94.7 % ± 1.4 % 99.3 % ± 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

- 03

PAGE 17 OF 21 

### Table 14

. DAL GW WW9R 130327 (1)

PFOA PFB S

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

ISO13

- 07

- 03

- 013 DAL

- GW

- WW9R

- 0

- 130327 3260 NA 273 NA

ISO13

- 07

- 03

- 014 DAL

- GW

- WW9R

- DB

- 130327 3400 NA 283 NA

ISO13

- 07

- 03

- 015 DAL

- GW

- WW9R

- FMS

- 130327 7570 100 4260 100

Average Concentration (ng/mL) ± %RPD 3330 ng/mL ± 4.2 % 278 ng/mL ± 3.6 %

PFHS PFOS

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

ISO13

- 07

- 03

- 013 DAL

- GW

- WW9R

- 0

- 130327 1410 NA 4530 NA

ISO13

- 07

- 03

- 014 DAL

- GW

- WW9R

- DB

- 130327 1470 NA 4780 NA

ISO13

- 07

- 03

- 015 DAL

- GW

- WW9R

- FMS

- 130327 5470 102 9070 110

Average Concentration (ng/mL) ± %RPD 1440 ng/mL ± 4.2 % 4 660 ng/mL ± 5.4 %

13 C 4 - PFOA 13 C 4 - PFOS

3M LIMS ID Description %Recovery %Recovery

ISO13

- 07

- 03

- 013 DAL

- GW

- W W9R

- 0

- 130327 102 103

ISO13

- 07

- 03

- 014 DAL

- GW

- WW9R

- DB

- 130327 105 106

ISO13

- 07

- 03

- 015 DAL

- GW

- WW9R

- FMS

- 130327 96.3 101

Average Concentration (ng/mL) ± %RSD 101 % ± 4.5 % 103 % ± 2.2 %

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

- 03

PAGE 18 OF 21 

### Table 15 . Trip Blank Results

PFOA PFBS

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

ISO13

- 07

- 03

- 016 DAL

- GW

- TRIP01

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

ISO13

- 07

- 03

- 017 DAL

- GW

- TRIP01

- LS 10.2 (1) 96.4 9.60 (1) 96.4

ISO13

- 07

- 03

- 018 DAL

- GW

- TRIP01

- HS 4360 (2) 103 4070 (2) 102

PFHS PFOS

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

ISO13

- 07

- 03

- 016 DAL

- GW

- TRIP01

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

ISO13

- 07

- 03

- 017 DAL

- GW

- TRIP01

- LS 9.10 (1) 92.3 9.44 (1) 94.4

ISO13

- 07

- 03

- 018 DAL

- GW

- TRIP01

- HS 4020 (2) 102 4 650 (2) 116

1 3 C 4 - PFOA 13 C 4 - PFOS

3M LIMS ID Description %Recovery %Recovery

ISO13

- 07

- 03

- 016 DAL

- GW

- TRIP01

- 0 94.9 (1) 98.5 (1)

ISO13

- 07

- 03

- 017 DAL

- GW

- TRIP01

- LS 91.0 (1) 94.0 (1)

ISO13

- 07

- 03

- 018 DAL

- GW

- TRIP01

- HS 102 (2) 105 (2)

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

.3M ENVIRONMENTAL LABORATORY

REPORT

NO. IS013-07-03



# 5 Conclusio n

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

. Th e accurac

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

. Fiel d 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 gpncipa ! 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

.



# / H^I^^~/iJ\

Quality Assuranc

^ Representativ e Dat e

This test report sfiall not be reproduced

except in full, wittiout

written approval

of ttie 3M

Environmental

Laboratory.

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

REPORT NO. ISO13

- 07

- 03

PAGE 20 OF 21 

### 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 6/17/2011 2/8/2012 6/29/2012 8/28/2012 12/14/2012 1/17/2013 2/13/2013 3/27/2013

PFOA 1410 1180 1650 1410 2580 1910 2300 2220

PFBS 1110 792 1410 1 830 723 588 830 1060

PFHS 983 1100 1460 1390 1380 895 1580 1090

PFOS 691 782 964 172 2810 1810 2940 2490



### AC E (Activated Carbon Ef fluent)

- Sample Results in ng/mL

ACE 6/17/2011 2/8/2012 8/28/2012 12/14/2012 1/17/2013 2/13/2013 3/27/2013

PFOA 2.57 1250 0.387 0.102 <0.0240 0.0124 0.0380

PFBS 11.9 818 0.256 <0.0250 <0.0250 0.0360 <0.0250

PFHS 2.50 1240 0.552 0.117 <0.0250 0.178 0.0477

PFOS 2.07 741 0.103 0.0376 <0.0232 0.0329 <0.0232

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

REPORT NO. ISO13

- 07

- 03

PAGE 21 OF 21 

### Attachment A : Ana lyte 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

PFOA 3630 4350 3250 3640

PFBS 441 410 354 385

PFHS 1740 1930 1900 1760

PFOS 4920 5710 4850 5120



### WW9R

- Sample Results in ng/mL

WW9R 12/13/2012 1/17/2013 2/13/2013 3/27/2013

PFOA 3360 2710 2850 3330

PFBS 321 184 236 278

PFHS 1480 954 1400 1440

PFOS 4080 3690 4100 4660