3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

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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

– April 2013

Laboratory Request Number: ISO13

- 07

- 04

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 accordance with the A2LA Testing Certificate # 2052.01.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

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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** 

**- 04** 

3M Decatur Groundwater Treatment Plant System; April 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 April 29 , 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

- 04

. 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 Calibration Laboratories”, in

accordance with the A2LA Test ing Certificate # 2052.01.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

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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

- 04

- 001 DAL

- GW

- ACI ; Sample 1450 1340 767 1620

ISO13

- 07

- 04

- 002 DAL

- GW

- ACI ; Sample Dup 1500 1380 786 1720

Average 148 0 (1) 1360 (1) 777 (1) 1670 (1)

%RPD Sample/Sample Dup 3.4 2.9 2.4 6.0

ISO13

- 07

- 04

- 004 DAL

- GW

- ACM2; Sample 298 1530 683 0.400

ISO13

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- 04

- 005 DAL

- GW

- ACM2 ; Sample Dup 293 1490 659 0.354

Average 296 (1,2 ) 1510 ( 1 ,2 ) 671 (1,2 ) 0.377 ( 2, 3 )

%RPD Sample /Sample Dup 1.7 2.6 3.6 12

ISO13

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- 04

- 007 DAL

- GW

- ACE; Sample 0.0420 0.393 0.0551 <0.0232

ISO13

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- 008 DAL

- GW

- ACE ; Sample Dup 0.0424 0.391 0.0588 <0.0232

Average 0.0422 (3 ) 0.392 ( 3 ) 0.0570 ( 3 ) <0.0232 ( 3 )

%RPD Sample/Sample Dup 0.95 0.51 6.5 N A

ISO13

- 07

- 04

- 010 DAL

- GW

- WW8R; Sample 3180 364 1600 4840

ISO13

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- 04

- 011 DAL

- GW

- WW8R ; Sample Dup 3200 364 1620 4820

Average 3190 (1) 364 (1) 1610 (1) 4830 (1)

%RPD Sample/Sample Dup 0.63 0.0 1.2 0.41

ISO13

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- 04

- 013 DAL

- GW

- WW9R; Sample 2600 240 1 180 4260

ISO13

- 07

- 04

- 014 DAL

- GW

- WW9R ; Sample Dup 2690 247 1210 4410

Average 2650 (1) 244 (1) 1200 (1) 4340 (1)

%RPD Sample/Sample Dup 3.4 2.9 2.5 3.5

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

- 8

- 044. 1 using external stan dard calibration . The analytical method uncertainties associated with the reported results are as follows: PFOA ±15 %, PFBS ± 14 %, PFHS ±14 %, and PFOS ± 1 4 %. (2) Sample did not have an appropriate FMS to access recovery. See section 4 for more details. (3) Report ed 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 ± 15 %, PFBS ± 15 %, PFHS ± 14 %, and PFOS ±
13 %.



# 2 Methods

- Analytical an d 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 Tar get Analytes.

Target Analytes Acronym Reference
Material Structure

Perfluorooctanoic Acid (C8 Acid) PFOA Linear + Branched

Perfluorobutanesulfonate (C4 Sulfonate ) PFBS Linear

Perfluorohexanesulfonate (C6 Sulfonate) PFHS Linear

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

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PAGE 4 OF 21 

## 2.2 Sample Collection
Samples were collected on April 29 , 201 3 in Nalgene TM 

### (high

- density polyethylene) bottles prepared at the 3M Environmental Laboratory. Prior to sample collection, bottles designated for field matr ix 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

conditions on May 3 , 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 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 analytes by transferr ing 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 sta ndard 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 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 the analytical peak, manual integration of the analytical peak is necessary. All manual integrations are performed following the procedures outlined in method ETS

- 12

- 010. The consistency of the laboratory’s integration is ensured through the training of laboratory personnel, the peer review process required for all manual integrations, the review of manual integrations by the QAU, and where necessary the review of manual integrations by laboratory management.3M ENVIRONMENTAL LAB ORATORY

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PAGE 5 OF 21 

### Table 3 . Instrument Parameters.

Instrument Name ETS Kirk ETS Bust er
Analysis Dates 5/7 /13

– ex ternal standard calibration 5/8 /13

– in ternal standard calibration

Analytical Method ETS

- 8

- 044.1 ETS

- 8

- 044.1

Liquid Chromatograph Agilent 1 260 Agilent 1 10 0

Guard column Betasil C18 (4.6 mm X 100 mm), 5 μ Betasil C18 (4.6 m m 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 2 5 μ L

Mass Spectrometer Applied Biosystems TripleQuad 55 00 Applied Biosystems API 40 00

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/ 99 399/80

PFOS 499/99

[ 13 C 8 ]PFOS 50 7/80 499/80

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 chromatogram” (TIC) , wh ich was u sed for quantitation.

(1) Internal standard s were used for the analysis on 5/ 8 /13.3M ENVIRONMENTAL LAB ORATORY

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PAGE 6 OF 21 

# 3 Data Analysis

3.1 Calibration

Internal Standard Calibration Analysis : Samples were analyzed against a matrix

- matched stable isotope internal standard calibration c urve. 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 quad ratic, 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 coefficient (r) was gre ater 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 containing the target anal ytes 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 the peak area coun ts 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% for the lowest cur ve point) were met for all analytes. The correlation coefficient (r) was greater than 0.995 for all analytes

.



## 3.2 System Suitability

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

demonstrate overall system suit ability. T he acceptance criteria for system suitability samples is less than or equal to 5% relative standard deviation (RSD) for peak area /ratio and retention time criteria of less than or equal to 2% RSD

. These cri teria were met for all analytes

.



## 3.3 Limi t 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

.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

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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 Internal 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 Bl anks

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 (LC Ss)
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 eith er 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 that the

average re covery of LCS s at each spiking level be within 80%

- 120% wi th a RSD ≤20%. All LCS sampl es met method accuracy criteria

.

All LCSs were used in the determination of the analytical method uncertainty in section 3.9.

T he following calculations were used t o generate data in Table 7

.

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

100% * recovery LCS average replicates LCS deviation standard RSD LCS%
=3M ENVIRONMENTAL LAB ORATORY

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PAGE 8 OF 21 

### Table 7 . Lab Control Spike Results.

ETS

- 8

- 044.1

Ex

ternal Standard

Calibration

Analyzed 5/7 / 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

- 130507

- 1 0.191 0.172 89.9 0.185 0.190 103

LCS

- 130507

- 2 0.191 0.183 95.6 0.185 0.192 104

LCS

- 1305 07

- 3 0.191 0.186 97.4 0.185 0.197 107

Average ± %RSD 94.3% ± 4.2 % 105 % ± 2.0 %

LCS

- 130507

- 4 1.91 1.96 103 1.85 2.09 113

LCS

- 130507

- 5 1.91 1.93 101 1.85 2.07 112

LCS

- 130507

- 6 1.91 1.96 102 1.85 2.05 111

Average ± %RSD 1 02 % ± 0.98 % 112 % ± 0.89 %

LCS

- 1305 07

- 7 19.1 18.7 97.8 18.5 20.1 109

LCS

- 130507

- 8 19.1 17.2 90.3 18.5 19.5 105

LCS

- 130507

- 9 19.1 18.4 96.2 18.5 20.2 109

Average ± %RSD 94.8 % ± 4.2 % 108 % ± 2.1 %

ETS

- 8

- 044.1

Ex

ternal Standard

Calibration

Analyzed 5/7 /13 PFBS PFHS

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

LCS

- 130507

- 1 0.199 0.207 104 0.199 0.198 99.7

LCS

- 130507

- 2 0.199 0.213 107 0.199 0.203 102

LCS

- 130507

- 3 0.199 0.21 7 109 0.199 0.214 107

Average ± %RSD 107 % ± 2.4 % 103 % ± 3.6 %

LCS

- 130507

- 4 1.99 2.36 119 1.99 2.20 111

LCS

- 130507

- 5 1.99 2.32 116 1.99 2.16 108

LCS

- 130507

- 6 1.99 2.31 116 1.99 2.19 110

Average ± %RSD 117 % ± 1.5 % 1 10 % ± 1.4 %

LCS

- 130507

- 7 20.0 20.9 105 20.0 19.6 98.2

LCS

- 130507

- 8 20 .0 19.9 99.4 20.0 18.9 94.6

LCS

- 130507

- 9 20.0 21.2 106 20.0 19.4 97.0

Average ± %RSD 103 % ± 3.4 % 96.6 % ± 1.9 %3M ENVIRONMENTAL LAB ORATORY

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PAGE 9 OF 21 

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

ETS

- 8

- 044.1

Ex

ternal Standard

Calibration

Analyzed 5/7 /13 PFOA surrogate PFOS surroga te

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

LCS

- 130507

- 1 0.199 0.186 93.2 0.190 0.207 109

LCS

- 130507

- 2 0.199 0.185 92.7 0.190 0.206 108

LCS

- 130507

- 3 0.199 0.191 95.9 0.190 0.209 110

Average ± %RSD 93.9 % ± 1.8 % 109 % ± 0.92 %

LCS

- 130507

- 4 1.99 1.90 95.4 1.90 2.05 108

LCS

- 130507

- 5 1.99 1.95 97.8 1.90 2.08 109

LCS

- 130507

- 6 1.99 1.98 99.6 1.90 2.10 110

Average ± %RSD 97.6 % ± 2.2 % 109 % ± 0.92 %

ETS

- 8

- 044.1

In ternal Standard

Calibration

Analyz ed 5/8 /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

- 130508

- 1 0.190 0.193 101 0.184 0.184 99.8

LCS

- 130508

- 2 0.190 0.180 94.6 0.184 0.178 96.9

LCS

- 130508

- 3 0.190 0.189 99.4 0.184 0.178 97.0

Average ± %RSD 98.3 % ± 3.4 % 97.9 % ± 1.7 %

LCS

- 130508

- 4 1.90 2.05 108 1.84 2.01 109

LCS

- 130508

- 5 1.90 2.02 106 1.84 1.92 104

LCS

- 130508

- 6 1.90 2.05 108 1.84 1.97 107

Average ± %RSD 107 % ± 1.1 % 1 07 % ± 2.4 %

LCS

- 130508

- 7 9.52 9.01 94.6 9.21 9.65 105

LCS

- 130508

- 8 9.52 8.80 92.4 9.21 9.15 99.4

LCS

- 130508

- 9 9.52 8.93 93.8 9.21 8.60 93.3

Average ± %RSD 93.6 % ± 1.2 % 99.2 % ± 5.9 %3M ENVIRONMENTAL LAB ORATORY

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PAGE 10 OF 21 

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

ETS

- 8

- 044.1

In ternal Standard

Calibration

Analyzed 5/8 /13 PFBS PFHS

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

LCS

- 130508

- 1 0.198 0.197 99.5 0.198 0.211 106

LCS

- 130508

- 2 0.198 0.197 99.7 0.198 0.195 98.4

LCS

- 130508

- 3 0.198 0.196 99.0 0.198 0.209 106

Average ± %RSD 99.4 % ± 0.36 % 103 % ± 4.2 %

LCS

- 130508

- 4 1.98 2.27 115 1.98 2.22 112

LCS

- 130508

- 5 1.98 2.19 111 1.98 2.16 109

LCS

- 130508

- 6 1.98 2.09 105 1.98 2.14 108

Average ± %RSD 1 10 % ± 4.6 % 1 10 % ± 1.9 %

LCS

- 130508

- 7 9.94 9.48 95.3 9.94 9.96 100

LCS

- 130508

- 8 9.94 9.37 94.2 9.94 9.48 95.4

LCS

- 130508

- 9 9.94 9.62 96.8 9.94 9.68 97.4

Average ± %RSD 95.4 % ± 1.4 % 97.6 % ± 2.4 %

ETS

- 8

- 044.1

In ternal Standard

Calibration

Analyzed 5/8 /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

- 130508

- 1 0.198 0.217 109 0.189 0.198 105

LCS

- 130508

- 2 0.198 0.217 110 0.189 0.207 109

LCS

- 130508

- 3 0.198 0.218 110 0.189 0.223 118

Averag e ± %RSD 110 % ± 0.53 % 111 % ± 6.0 %

LCS

- 130508

- 4 1.98 2.13 107 1.89 2.04 108

LCS

- 130508

- 5 1.98 2.13 108 1.89 2.06 109

LCS

- 130508

- 6 1.98 2.17 110 1.89 2.21 117

Average ± %RSD 10 8 % ± 1.4 % 111 % ± 4.4 %3M ENVIRONMENTAL LAB ORATORY

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PAGE 11 OF 21 

## 3.7 Analytical Method Uncertainty
Analytical unc ertainty 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 %) o btained 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 Calibrat ion Method Standard Deviation Method Uncertainty

PF OA External Standard 7.56 ± 15 %

PFBS External Standard 6.86 ± 14 %

PFHS External Standard 6.92 ± 14 %

PFOS External Standard 7.21 ± 1 4 %

PFOA Internal Standard 7.51 ± 15 %

PFBS Internal Standard 7.53 ± 15 %

PF HS Internal Standard 6.91 ± 14 %

PFOS Internal Standard 6.51 ± 13 %
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 mat rix 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 criteri a 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 referen ce 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 Concentrat ion (ng/mL)

Location Description PFOA PFBS PFHS PFOS

ACI Field Matrix Spike 2 000 201 0 200 0 1990

ACM2 Field Matrix Spike 10 0 100 99.8 99.4

ACE Field Matrix Spike 10.0 10.0 9.99 10.0

WW8R, WW9R Field Matrix Spike 4 000 4020 3990 3980

Trip Blank Low Fiel d Matrix Spike 10.0 10.0 9.99 10.0

High Field Matrix Spike 4000 4020 3990 39803M ENVIRONMENTAL LAB ORATORY

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# 4 Data Summary and Discussion

The tables below summarize the sample results and field m atrix spike recoveries for the five locations as well as the Trip Blank. Each table pro vides 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

f igures. 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 sample s 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

, PFHS , or PFOS; however, the surrogate recovery standards 13 

### C 4 

### - PFOA and 13 

### C 4 

### - PFOS

, met m ethod acceptance

criteria. No additional QC samples were prepared.3M ENVIRONMENTAL LAB ORATORY

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PAGE 13 OF 21 

### Table 10

. DAL GW ACI 130429 (1)

PFOA PFBS

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

ISO13

- 07

- 04

- 001 DAL

- GW

- A CI

- 0

- 130429 1450 NA 1340 NA

ISO13

- 07

- 04

- 002 DAL

- GW

- ACI

- DB

- 130429 1500 NA 1380 NA

ISO13

- 07

- 04

- 003 DAL

- GW

- ACI

- FMS

- 130429 3270 89.8 3430 103

Average Concentration (ng/mL) ± %RPD 1480 ng/mL ± 3.4 % 1360 ng/mL ± 2.9 %

PFHS PFOS

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

ISO13

- 07

- 04

- 001 DAL

- GW

- ACI

- 0

- 130429 767 NA 1620 NA

ISO13

- 07

- 04

- 002 DAL

- GW

- ACI

- DB

- 130429 786 NA 1720 NA

ISO13

- 07

- 04

- 003 DAL

- GW

- ACI

- FMS

- 130429 2650 93.7 3770 106

Average Concentration (ng/mL) ± %RPD 777 ng/mL ± 2.4 % 1670 ng/mL ± 6.0 %

13 C 4 - PFOA 13 C 4 - PFOS

3M LIMS ID Description %Recovery %Recovery

ISO13

- 07

- 04

- 001 DAL

- GW

- ACI

- 0

- 130429 89.7 105

ISO13

- 07

- 04

- 002 DAL

- GW

- ACI

- DB

- 130429 88.8 110

ISO13

- 07

- 04

- 003 DAL

- GW

- ACI

- FMS

- 130429 87.6 104

Ave rage Concentration (ng/mL) ± %RSD 88.7 % ± 1.2 % 106 % ± 3.1 %

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

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PAGE 14 OF 21 

### Table 11

. DAL GW ACM2 130429

PFOA ( 1 ) PFBS ( 1 )

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

ISO13

- 07

- 04

- 004 DAL

- GW

- ACM2

- 0

- 130429 298 NA 1530 NA

ISO13

- 07

- 04

- 005 DAL

- GW

- ACM2

- DB

- 1304 29 293 NA 1490 NA

ISO13

- 07

- 04

- 006 DAL

- GW

- ACM2

- FMS

- 130429 394 NC 1630 NC

Average Concentration (ng/mL) ± %RPD 296 ng/mL ± 1.7 % 1510 ng/mL ± 2.6 %

PFHS (1 ) PFOS ( 2 )

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

ISO13

- 07

- 04

- 004 DAL

- GW

- ACM2

- 0

- 130429 683 NA 0.400 NA

ISO13

- 07

- 04

- 005 DAL

- GW

- ACM2

- DB

- 130429 659 NA 0.354 NA

ISO13

- 07

- 04

- 006 DAL

- GW

- ACM2

- FMS

- 130429 792 NC NA (3) NA (3)

Average Concentration (ng/mL) ± %RPD 671 ng/mL ± 3.6 % 0.377 ng/mL ± 12 %

13 C 4 - PF OA (1) 13 C 4 - PFOS ( 2 )

3M LIMS ID Description %Recovery %Recovery

ISO13

- 07

- 04

- 004 DAL

- GW

- ACM2

- 0

- 130429 95.5 103

ISO13

- 07

- 04

- 005 DAL

- GW

- ACM2

- DB

- 130429 91.4 93.0

ISO13

- 07

- 04

- 006 DAL

- GW

- ACM2

- FMS

- 130429 93.9 NA (3)

Average Concentration (ng/mL) ± % RPD/ RSD 9 3.6 % ± 2.2 % 98.1 % ± 10 %

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 recovery standards 13 C 4 - PFOA and 13 C 4 - PFOS were

ad ded to the samples during sample preparation. (2) Samples were analyzed by i nternal standard calibration

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

REPORT NO. ISO13

- 07

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PAGE 15 OF 21 

### Table 12

. DAL GW ACE 1304 29 (1)

PFOA PFBS

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

ISO13

- 07

- 04

- 007 DAL

- GW

- ACE

- 0

- 130429 0.0420 NA 0.393 NA

ISO13

- 07

- 04

- 008 DAL

- GW

- ACE

- DB

- 130429 0.0424 NA 0.391 NA

ISO13

- 07

- 04

- 009 DAL

- GW

- ACE

- FMS

- 13 0429 7.94 79.0 9.61 92.2

Average Concentration (ng/mL) ± %RPD 0. 0422 ng/mL ± 0. 9 5 % 0. 392 ng/mL ± 0. 51%

PFHS PFOS

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

ISO13

- 07

- 04

- 007 DAL

- GW

- ACE

- 0

- 130429 0.0551 NA < 0.0232 NA

ISO13

- 07

- 04

- 008 DAL

- GW

- ACE

- DB

- 130429 0.0588 NA <0.0232 NA

ISO13

- 07

- 04

- 009 DAL

- GW

- ACE

- FMS

- 130429 8.26 82.1 9.63 96.3

Average Concentration (ng/mL) ± %RPD 0.0570 ng/mL ± 6.5 % <0.0232 ng/mL

13 C 4 - PFOA 13 C 4 - PFOS

3M LIMS ID Description %Recover y %Recovery

ISO13

- 07

- 04

- 007 DAL

- GW

- ACE

- 0

- 130429 92.1 105

ISO13

- 07

- 04

- 008 DAL

- GW

- ACE

- DB

- 130429 93.4 99.1

ISO13

- 07

- 04

- 009 DAL

- GW

- ACE

- FMS

- 130429 100 103

Average Concentration (ng/mL) ± %RSD 95.2 % ± 4.6 % 102 % ± 2.8 %

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

.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

- 07

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PAGE 16 OF 21 

### Table 13

. DAL GW WW8R 130429 (1)

PFOA PFBS

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

ISO13

- 07

- 04

- 010 DAL

- GW

- WW8R

- 0

- 130429 3180 NA 364 NA

ISO 13

- 07

- 04

- 011 DAL

- GW

- WW8R

- DB

- 130429 3200 NA 364 NA

ISO13

- 07

- 04

- 012 DAL

- GW

- WW8R

- FMS

- 130429 6960 94.3 4170 94.7

Average Concentration (ng/mL) ± %RPD 3 190 ng/mL ± 0.63 % 364 ng/mL ± 0.0 %

PFHS PFOS

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

ISO13

- 07

- 04

- 010 DAL

- GW

- WW8R

- 0

- 130429 1600 NA 4840 NA

ISO13

- 07

- 04

- 011 DAL

- GW

- WW8R

- DB

- 130429 1620 NA 4820 NA

ISO13

- 07

- 04

- 012 DAL

- GW

- WW8R

- FMS

- 130429 5390 94.7 8230 85.4

Average Concentration (ng/mL) ± %RPD 1610 ng/mL ± 1.2 % 483 0 ng/mL ± 0.41 %

13 C 4 - PFOA 13 C 4 - PFOS

3M LIMS ID Description %Recovery %Recovery

ISO13

- 07

- 04

- 010 DAL

- GW

- WW8R

- 0

- 130429 89.0 103

ISO13

- 07

- 04

- 011 DAL

- GW

- WW8R

- DB

- 130429 88.6 104

ISO13

- 07

- 04

- 012 DAL

- GW

- WW8R

- FMS

- 130429 84.3 94.9

Average Concentration (ng/mL) ± %RSD 87.3 % ± 3.0 % 100 % ± 4.8 %

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

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PAGE 17 OF 21 

### Table 14

. DAL GW WW9R 130429 (1)

PFOA PFBS

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

ISO13

- 07

- 04

- 013 DAL

- GW

- WW9R

- 0

- 130429 2600 NA 240 NA

ISO13

- 07

- 04

- 014 DAL

- GW

- WW9R

- DB

- 130429 2690 NA 247 NA

ISO13

- 07

- 04

- 015 DAL

- GW

- WW9R

- FMS

- 130429 5840 79.9 3530 81.8

Average Concentration (ng/mL) ± %RPD 2650 ng/mL ± 3.4 % 2 44 ng/mL ± 2.9 %

PFHS PFOS

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

ISO13

- 07

- 04

- 013 DAL

- GW

- WW 9R

- 0

- 130429 1180 NA 4260 NA

ISO13

- 07

- 04

- 014 DAL

- GW

- WW9R

- DB

- 130429 1210 NA 4410 NA

ISO13

- 07

- 04

- 015 DAL

- GW

- WW9R

- FMS

- 130429 4480 82.3 8870 114

Average Concentration (ng/mL) ± %RPD 1200 ng/mL ± 2.5 % 4 340 ng/mL ± 3.5 %

13 C 4 - PFOA 13 C 4 - PFOS

3M LIMS ID Desc ription %Recovery %Recovery

ISO13

- 07

- 04

- 013 DAL

- GW

- WW9R

- 0

- 130429 88.8 104

ISO13

- 07

- 04

- 014 DAL

- GW

- WW9R

- DB

- 130429 94.1 105

ISO13

- 07

- 04

- 015 DAL

- GW

- WW9R

- FMS

- 130429 86.7 93.7

Average Concentration (ng/mL) ± %RSD 89.8 % ± 4.3 % 1 01 % ± 6.0 %

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

.3M ENVIRONMENTAL LAB ORATORY

REPORT NO. ISO13

- 07

- 04

PAGE 18 OF 21 

### Table 15 . Trip Blank Res ults

PFOA PFBS

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

ISO13

- 07

- 04

- 016 DAL

- GW

- TRIP01

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

ISO13

- 07

- 04

- 017 DAL

- GW

- TRIP01

- LS 8.12 (1) 81.2 8.78 (1) 87.8

ISO13

- 07

- 04

- 018 DAL

- GW

- TRIP01

- HS 3570 (2) 89.3 3880 (2) 96.5

PFHS PFOS

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

ISO13

- 07

- 04

- 016 DAL

- GW

- TRIP01

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

ISO13

- 07

- 04

- 017 DAL

- GW

- TRIP01

- LS 9.32 (1) 93.3 8.8 8 (1) 88.8

ISO13

- 07

- 04

- 018 DAL

- GW

- TRIP01

- HS 3730 (2) 93.5 4 030 (2) 101

13 C 4 - PFOA 13 C 4 - PFOS

3M LIMS ID Description %Recovery %Recovery

ISO13

- 07

- 04

- 016 DAL

- GW

- TRIP01

- 0 97.1 (1) 90.6 (1)

ISO13

- 07

- 04

- 017 DAL

- GW

- TRIP01

- LS 99.9 (1) 88.8 (1)

ISO13

- 07

- 04

- 018 DAL

- GW

- TRIP01

- HS 89.6 (2) 102 (2)

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

.3M ENVIRONMENTAL LABORATORY

REPORT

NO. ISO13-07-04



# 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 Pr/ncma 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 Qualit y Assuranc e Uni t ha s audite d th e dat a an d repor t fo r thi s project

.

Quality Assuranc e V?epresenftativ e ' Dat e

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

- 04

PAGE 20 OF 21 

### Atta chment 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 4/29/2013

PFOA 1410 1180 1650 1410 2580 1910 2300 2220 1480

PFBS 1110 792 1410 1830 723 588 830 1060 1360

PFHS 983 1100 1460 1390 1380 895 1580 1090 777

PFOS 691 782 964 172 2810 1810 2940 2490 1670



### 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 4/29/2013

PFOA 2.57 1250 0.387 0.102 <0.0240 0.124 0.0380 0.0422

PFBS 11.9 818 0.256 <0.0250 <0.0250 0.0360 <0.0250 0.392

PFHS 2.50 1240 0.552 0.117 <0.0250 0.178 0.0477 0.0570

PFOS 2.07 741 0.103 0.0376 <0.0232 0.0329 <0.0232 <0.0232

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

REPORT NO. ISO13

- 07

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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

PFOA 3630 4350 3250 3640 3190

PFBS 441 410 354 385 364

PFHS 1740 1930 1900 1760 1610

PFOS 4920 5710 4850 5120 4830



### WW9R

- Sample Results in ng/mL

WW9R 12/13/201 2 1/17/2013 2/13/2013 3/27/2013 4/29/2013

PFOA 3360 2710 2850 3330 2650

PFBS 321 184 236 278 244

PFHS 1480 954 1400 1440 1200

PFOS 4080 3690 4100 4660 4340