3M ENVIRONMENTAL LAB ORATORY
REPORT NO. ISO13

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PAGE 1 OF 20 

# Final Report

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

3M Decatur, Alabama : Groundwater Treatment Plant GAC System

– February 2013

Laboratory Request Number: ISO13

- 07

- 0 2

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

Testing Ce rt #2052. 01 The testing reported herein meet the requirements of ANSI/ISO/IEC 17025:2005 “General Requi rements for the Competence of Testing and Calibration Laboratories”, in accordance with the A2LA Testing Certificate # 2052.01. Testing that complies with this International Standard also meets principles of ISO 9001:2000.3M ENVIRONMENTAL LAB ORATORY
REPORT NO. ISO13

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PAGE 2 OF 20 

### 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** 

**- 0** 

**2**

3M Decatur Groundwater Treatm ent Plant System; February 2013 Sampling

Report Date: Date of Last Signature



# 1 Introduction/Summary

The 3M Environmental Laboratory analyzed water samples from the groundwater treatment plant GAC system at the 3M Decatur, AL facility. Water samples were collected by Weston Solutions personnel

on February 13 , 2013

. Samples were returned to the 3M Environmental Laboratory for analysis of
P erfluorooctanoate (PFOA) , Perfluorobutane sulfonate (PFBS), Perf luorohexane sulfonate (PFHS),
Perfluorooctane sulfonat e (PFOS)

, and the surrogate recovery standards 13 

### C 4 

### - PFOA and 13 

### C 4 

### - PFOS
under la boratory project number ISO13

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

- 1006.

T he 3M Environmental Laboratory provided sample containers for 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 bottl es 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 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 analyti cal method 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 Testing Certificate # 2052.01. Testing that complies with this International Standard also meets principles of ISO 9001:2000.3M ENVIRONMENTAL LAB ORATORY
REPORT NO. ISO13

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PAGE 3 OF 20 

### 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 2250 826 1550 2950

ISO13

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- 002 DAL

- GW

- ACI ; Sample Dup 2350 833 1600 2930

Ave rage 2300 (1) 830 (1) 1580 (1) 2940 (1)

%RPD Sample/Sample Dup 4.3 0.84 3.2 0.68

ISO13

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- 004 DAL

- GW

- ACM2; Sample <0.0240 1680 0.0417 0.120

ISO13

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- 005 DAL

- GW

- ACM2 ; Sample Dup 0.0320 1660 0.0802 0.0726

Average 0.0320 (2 ) 1670 ( 1 ,3 ) 0.0610 ( 2 ) 0.0963 (2 )

%RPD Sample/Sample Dup NA (4 ) 1.2 63 (5 ) 49 (5 )

ISO13

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- 007 DAL

- GW

- ACE; Sample 0.126 0.0372 0.170 0.0381

ISO13

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- 008 DAL

- GW

- ACE ; Sample Dup 0.121 0.0348 0.185 0.0276

Average 0.124 (2 ) 0.0360 (2 ) 0.178 (2 ) 0.0329 (2 )

%RPD Samp le/Sample Dup 4.0 6.7 8.5 32 (5 )

ISO13

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- 010 DAL

- GW

- WW8R; Sample 3240 357 1920 4860

ISO13

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- 011 DAL

- GW

- WW8R ; Sample Dup 3260 350 1870 4830

Average 3250 (1) 354 (1) 1900 (1) 4850 (1)

%RPD Sample/Sample Dup 0.62 2. 0 2. 6 0.62

ISO13

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- 013 DAL

- GW

- WW9R; Sample 2840 232 1420 4130

ISO13

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- 014 DAL

- GW

- WW9R ; Sample Dup 2860 239 1370 4060

Average 2850 (1) 236 (1) 1400 (1) 4100 (1)

%RPD Sample/Sample Dup 0.70 3.0 3. 6 1.7

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

- 8

- 044. 1 using external calibration . The analytical method uncertainties associated with the reported results are as follows: PFOA ±16 %, PFBS ± 12 %, PFHS ±1 1 %, and PFOS ±16 %. (2) Reported results were prepared and analyzed by ETS

- 8

- 044. 1 using internal ca libration . The analytical method uncertainties associated with the reported results are as follows: PFOA ±22 %, PFBS ±23 %, PFHS ±22 %, and PFOS ± 19 %. (3) Sample did not have an appropriate FMS to access recovery. See section 4 for more details. (4) Sample/sample d uplicate RPD could not be determined since the initial sample concentration was BLOQ. (5) Sample/sample duplicate RPD did not meet acceptance criteria of ≤ 20%.



# 2 Methods

- Analytical and Preparatory

2.1 Methods Analysis was completed using 3M Environmental Laborato ry 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

Perfluor ooctanoic 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
REPORT NO. ISO13

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PAGE 4 OF 20 

## 2.2 Sample Collection Samples were coll ected on February 13 , 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 appropr iate 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 concentra tion 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 February 15 , 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. Prep ared samples were analyzed by external standard calibration. Further dilution may have been applied by using a lower injection volume on the instrument.

The ACE sample set and the Trip Blank sample and low spike were prepared and analyzed for all analyte s by removing a 0.4 mL aliquot of the well mixed sample and diluting it with 0.4 mL of methanol ( dilution factor of 2). The ACM2 sample set w as re

- analyzed using a 1: 2 dilution. Prepared samples were analyzed by internal standard calibration.

During th e preparation of the laboratory control samples for internal 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 Tri p 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 qua lity 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 process ing 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 labo ratory management.3M ENVIRONMENTAL LAB ORATORY
REPORT NO. ISO13

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PAGE 5 OF 20 

### Table 3 . Instrument Parameters.

Instrument Name ETS Buster ETS Buster

Analysis Dates 2/26 /13

– ex ternal calibration 2/28 /13

– in ternal calibration
Analytical Method ETS

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- 044.1 ETS

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- 044.1
Liquid Chromatogr aph Agilent 1 10 0 Agilent 1 10 0

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 5 or 2 0 μ L 25 μ L
Mass Spectrometer Applied Biosystems API 4 0 00 Applied Biosystems API 4 0 00

Ion Source Turbo Sp ray 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** 
**(Metha nol)** 

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 chromatogram” (TIC) , which was u sed for quantitation.
(1) Internal standard s were used for the analysis on 2/28 /13.3M ENVIRONMENTAL LAB ORATORY
REPORT NO. ISO13

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PAGE 6 OF 20 

# 3 Data Analysis

3.1 Calibration

Internal Standard Calibration Analysis : Samples were analyzed against a matrix

- matched stable isotope internal standard cal ibration curve. Calibration standards were prepared by spiking known
amounts of stock solutions into 50 mL of laboratory prepared synthetic groundwater . 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/m L 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 an d 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 coeff icient (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
containi ng the target analytes into 90:10 Methanol:Mil li

- Q laboratory water. A total of twelve spiked standards ranging from 0. 0 2 ng/mL to 10 0 ng/mL (nominal) were analyzed. Of these twelve calibration standards, ten contained the surrogates at concentrations ra nging 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 standar d concentrations using the 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 requiremen ts 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 se quence to demonstrate overall system suitability. T he acceptance criteria for system suitability samples is less than or equal to 5% relative standard deviation (RSD) for peak area /ratio and retention time criteria of less than or equal to 2% RSD

. These cri teria were met for all analytes

.



## 3.3 Limit of Quantitation (LOQ)

The LOQ as defined in method ETS

- 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 twi ce those of the appropriate blanks. The LOQs associated with the sample analysis are listed in the table below.3M ENVIRONMENTAL LAB ORATORY
REPORT NO. ISO13

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PAGE 7 OF 20 

### T able 6 . LOQ

Analyte Calibration LOQ, ng/mL

PFOA Internal standard 0.0240

PFBS Internal standard 0.0250

PFHS In ternal standard 0.0250

PFOS Internal standard 0.0232

PFOA External standard 0.0192 (2 )

PFBS External standard 0.0200 (2 )

PFHS External standard 0.0200 (2 )

PFOS External standard 0.0185 (2 )

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



## 3.4 Continuin g 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 cr iteria 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 control spikes were prepared for the surrogates . LCSs were prepared by spiking known amounts of the analytes into either 10 mL of laboratory

- prepared matrix matched water
or 1 mL of Milli

- Q water to produce the desired concentration. When applicable, t he LCSs were then diluted with methanol in the same manner as the sampl es

. Method ETS

- 8

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

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

.

A method deviation is included with the raw data. All LCSs were used in the determi nation 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

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PAGE 8 OF 20 

### Table 7 . Lab Control Spike Results.

ETS

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- 044.1

Ex

te rnal Standard

Calibration
Analyzed 2/26 / 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

- 130226

- 1 0.479 0.47 2 98.6 0.464 0.492 106

LCS

- 130226

- 2 0.479 0.47 2 98.6 0.464 0.492 106

LCS

- 130226

- 3 0.479 0.476 99.5 0.464 0.490 106

Average ± %RSD 98.9 % ± 0.53 % 106 % ± 0.0 %

LCS

- 130226

- 4 4.79 4.95 103 4.64 5.12 110

LCS

- 130226

- 5 4.79 5.02 105 4.64 5.15 111

LCS

- 130226

- 6 4.79 4.92 103 4.64 5.17 111

Average ± %RSD 104 % ± 1.1 % 111 % ± 0.52 %

LCS

- 130226

- 7 19.1 20.0 105 18.5 20.6 111

LCS

- 130226

- 8 19.1 19.7 103 18.5 20.5 111

LCS

- 130226

- 9 19.1 20.1 105 18.5 21.3 115

Average ± %RSD 104 % ± 1.1 % 112 % ± 2 .1 %

ETS

- 8

- 044.1

Ex

ternal Standard

Calibration
Analyzed 2 / 2 6

/13 PFBS PFHS

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

LCS

- 130226

- 1 0.5 00 0.498 99.6 0.500 0.496 99.1

LCS

- 130226

- 2 0.500 0.494 98.7 0.500 0.500 100

LCS

- 130226

- 3 0.500 0.487 97.4 0.500 0.492 98.5

Average ± %RSD 98.6 % ± 1.1 % 99.2 % ± 0.76 %

LCS

- 130226

- 4 5.00 5.16 103 5.00 5.17 103

LCS

- 130226

- 5 5.00 5.16 103 5.00 5.15 103

LCS

- 130226

- 6 5.00 5.12 102 5.00 5.19 104

Average ± %RSD 103 % ± 0.56 % 1 03 % ± 0.56 %

LCS

- 130226

- 7 20.0 20.4 102 20.0 19.9 99.3

LCS

- 130226

- 8 20.0 20.3 101 20.0 19.7 98.7

LCS

- 130226

- 9 20.0 21.2 106 20.0 20.1 101

Average ± %RSD 103 % ± 2 .6 % 99.7 % ± 1.2 %3M ENVIRONMENTAL LAB ORATORY
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PAGE 9 OF 20 

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

ETS

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Ex

ternal Standard

Calibration
Analyzed 2/26 /13 PFOA surrogate PFOS su rrogate

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

LCS

- 130226

- 1 0.499 0.496 99.4 0.478 0.470 98.3

LCS

- 130226

- 2 0.499 0.488 97.8 0.478 0.5 02 105

LCS

- 130226

- 3 0.499 0.496 99.5 0.478 0.490 103

Average ± %RSD 98.9 % ± 0.96 % 102 % ± 3.4 %

LCS

- 130226

- 4 4.99 4.43 88.8 4.78 4.71 98.5

LCS

- 130226

- 5 4.99 4.65 93.2 4.78 4.74 99.2

LCS

- 130226

- 6 4.99 4.71 94.4 4.78 4.76 99.5

Average ± %RSD 92.1 % ± 3.2% 99.1 % ± 0.52 %

ETS

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- 044.1

In ternal Standard

Calibration

An alyzed 2/28 /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

- 130227

- 1 0.190 0.189 99.6 0.184 0.192 104

LCS

- 130227

- 2 0.190 0.191 101 0.184 0.189 103

LCS

- 130227

- 3 0.190 0.186 98.2 0.184 0.215 117

Average ± %RSD 99.6 % ± 1.4 % 108 % ± 7.2 %

LCS

- 130227

- 4 1.90 1.91 101 1.84 1.84 99.9

LCS

- 130227

- 5 1.90 1.95 103 1.84 1.85 100

LCS

- 130227

- 6 1.90 1.92 101 1.84 1.84 100

Average ± %RSD 102 % ± 1 .1 % 100 % ± 0.058 %

LCS

- 130227

- 7 9.52 9.66 101 9.21 9.76 106

LCS

- 130227

- 8 9.52 9.40 98.7 9.21 8.90 96.6

LCS

- 130227

- 9 9.52 8.91 93.6 9.21 9.51 103

Average ± %RSD 97.8 % ± 3.9 % 102 % ± 4.7 %3M ENVIRONMENTAL LAB ORATORY
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PAGE 10 OF 20 

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

ETS

- 8

- 044.1

In ternal Standard

Calibration
Analyzed 2/28 /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

- 130227

- 1 0.198 0.211 107 0.198 0.206 104

LCS

- 130227

- 2 0.198 0.210 106 0.198 0.215 109

LCS

- 130227

- 3 0.198 0.2 11 106 0.198 0.218 110

Average ± %RSD 106 % ± 0.54 % 108 % ± 3.0 %

LCS

- 130227

- 4 1.98 2.06 104 1.98 1.90 95.8

LCS

- 130227

- 5 1.98 1.97 99.7 1.98 2.00 101

LCS

- 130227

- 6 1.98 2.09 105 1.98 2.06 104

Average ± %RSD 103 % ± 2.7 % 100 % ± 4 .1 %

LCS

- 130227

- 7 9.94 10.2 102 9.94 10.2 103

LCS

- 130227

- 8 9.94 9.49 95.5 9.94 9.29 93.5

LCS

- 130227

- 9 9.94 9.72 97.8 9.94 9.54 96.0

Average ± %RSD 98.4 % ± 3.3 % 97.5 % ± 5.1 %

ETS

- 8

- 044.1

In ternal Standard

Calibration
Analyzed 2/28 /13 PFOA surrogate PFOS surrogate

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

LCS

- 130227

- 1 0.198 0.200 101 0.189 0.201 106

LCS

- 130227

- 2 0.198 0.200 101 0.189 0.210 111

LCS

- 130227

- 3 0.198 0.201 102 0.189 0.225 119

Avera ge ± %RSD 101 % ± 0.57 % 112 % ± 5.9 %

LCS

- 130227

- 4 1.98 2.03 102 1.89 2.04 108

LCS

- 130227

- 5 1.98 2.13 108 1.89 2.03 108

LCS

- 130227

- 6 1.98 2.00 101 1.89 2.06 109

Average ± %RSD 104 % ± 3.7 % 108 % ± 0.53 %3M ENVIRONMENTAL LAB ORATORY
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PAGE 11 OF 20 

## 3.7 Analytical Method Uncertainty Analytical u ncertainty 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%.

Table 8 . Analytical Method Uncertainty.

Analyte Calib ration Method Standard Deviation Method Uncertainty

PF OA External Standard 8.05 ± 16 %

PFBS External Standard 6.21 ± 1 2 %

PFHS External Standard 5.46 ± 11 %

PFOS External Standard 7.88 ± 16 %

PFOA Internal Standard 11.1 ± 22 %

PFBS Internal Standard 11.7 ± 23 %

PFHS Internal Standard 10.8 ± 22 %

PFOS Internal Standard 9.62 ± 19 %



## 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 g enerated 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% con firm that “unknown” components in the sample matrix do not significantly interfere with the extraction and analysis of the analytes of interest. The standards used for the preparation of the field matrix spiking solutions contained reference materials com prised 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)

Loc ation 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 Matri x Spike 4220 3980 3940 40003M ENVIRONMENTAL LAB ORATORY
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PAGE 12 OF 20 

# 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 Trip Blank. Each table provides the average concentration and the relative per cent 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 slight ly 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.

DAL

- GW

- ACM2 ; the FMS sample (1 0 ng/mL) was not appropriate for PFBS; however, the FMS sample for PFOA, PFOS, and the surrogate recovery standards 13 

### C 4 

### - PFOA and 13 

### C 4 

### - PFOS

, met method acceptance criteria. No additional QC samples were prepared. Sample/sample duplicate RPD did not meet acceptance criteria of ≤ 20% for PFHS and PFOS.

DAL

- GW

- ACE ; sample/sample duplicate RPD did not meet acceptance criteria of ≤20% for PFOS.3M ENVIRONMENTAL LAB ORATORY
REPORT NO. ISO13

- 07

- 02

PAGE 13 OF 20 

### Table 10

. DAL GW ACI 1 30 213 (1)

PFOA PFBS

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

ISO13

- 07

- 02

- 001 DAL

- GW

- ACI

- 0

- 130213 2250 NA 826 NA

ISO13

- 07

- 02

- 002 DAL

- GW

- ACI

- DB

- 130213 2350 NA 833 NA

ISO13

- 07

- 02

- 003 DAL

- GW

- ACI

- FMS

- 130213 4050 82.9 2600 89.0

Average Concentration (ng/mL) ± %RPD 2300 ng/mL ± 4.3 % 830 ng/mL ± 0. 84 %

PFHS PFOS

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

ISO13

- 07

- 02

- 001 DAL

- GW

- ACI

- 0

- 130213 1550 NA 2950 NA

ISO13

- 07

- 02

- 002 DAL

- GW

- ACI

- DB

- 130213 1600 NA 2930 NA

ISO13

- 07

- 02

- 003 DAL

- GW

- ACI

- FMS

- 130213 32 70 86.0 4780 92.0

Average Concentration (ng/mL) ± %RPD 1580 ng/mL ± 3.2 % 2940 ng/mL ± 0.68 %

13 C 4 - PFOA 13 C 4 - PFOS

3M LIMS ID Description %Recovery %Recovery

ISO13

- 07

- 02

- 001 DAL

- GW

- ACI

- 0

- 130213 89.9 93.6

ISO13

- 07

- 02

- 002 DAL

- GW

- ACI

- DB

- 130213 92.3 88.0

ISO13

- 07

- 02

- 003 DAL

- GW

- ACI

- FMS

- 130213 88.6 100

Average Concentration (ng/mL) ± %RSD 90.2 % ± 2.1 % 93.9 % ± 6.4 %

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

ad ded to the samples during sample preparation.3M ENVIRONMENTAL LAB ORATORY
REPORT NO. ISO13

- 07

- 02

PAGE 14 OF 20 

### Table 11

. DAL GW ACM2 1 30 213

PFOA ( 1 ) PFBS (2 )

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

ISO13

- 07

- 02

- 004 DAL

- GW

- ACM2

- 0

- 1302 13 <0.0240 NA 1680 NA

ISO13

- 07

- 02

- 005 DAL

- GW

- ACM2

- DB

- 130213 0.0320 NA 1660 NA

ISO13

- 07

- 02

- 006 DAL

- GW

- ACM2

- FMS

- 130213 9.91 93.7 1700 NC

Average Concentration (ng/mL) ± %RPD 0.0320 ng/mL (3) 1 670 ng/mL ± 1.2 %

PFHS (1 ) PFOS ( 1 )

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

ISO13

- 07

- 02

- 004 DAL

- GW

- ACM2

- 0

- 130213 0.0417 NA 0.120 NA

ISO13

- 07

- 02

- 005 DAL

- GW

- ACM2

- DB

- 130213 0.0802 NA 0.0726 NA

ISO13

- 07

- 02

- 006 DAL

- GW

- ACM2

- FMS

- 130213 9.77 98.5 11.5 114

Average Concen tration (ng/mL) ± %RPD 0.0610 ng/mL ± 63% (4) 0.0963 ng/mL ± 49% (4)

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

3M LIMS ID Description %Recovery %Recovery

ISO13

- 07

- 02

- 004 DAL

- GW

- ACM2

- 0

- 130213 94.3 100

ISO13

- 07

- 02

- 005 DAL

- GW

- ACM2

- DB

- 130213 97.1 92.9

ISO13

- 07

- 02

- 00 6 DAL

- GW

- ACM2

- FMS

- 130213 95.9 104

Average Concentration (ng/mL) ± %RSD 95.8 % ± 1.5 % 99.0 % ± 5.6 %

NA = Not Applicable NC = Not Calculated; Spike level was less than 0.5x the endogenous sample concentration. (1) Samples were analyzed by i nternal standard cali bration

. (2) Sample s 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. (3) Sample/sample duplicate RPD could not be determined since the initial sample con centration was BLOQ. (4) Sample/sample duplicate RPD did not meet acceptance criteria of ≤ 20%.3M ENVIRONMENTAL LAB ORATORY
REPORT NO. ISO13

- 07

- 02

PAGE 15 OF 20 

### Table 12

. DAL GW ACE 1 30 213 (1)

PFOA PFBS

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

ISO13

- 07

- 02

- 007 DAL

- GW

- ACE

- 0

- 130213 0.126 NA 0.0372 NA

ISO13

- 07

- 02

- 008 DAL

- GW

- ACE

- DB

- 130213 0.121 NA 0.0348 NA

ISO13

- 07

- 02

- 009 DAL

- GW

- ACE

- FMS

- 130213 10.1 94.7 10.1 101

Average Concentration (ng/mL) ± %RPD 0.124 ng/mL ± 4.0% 0.0360 ng/mL ± 6. 7%

PFHS PFOS

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

ISO13

- 07

- 02

- 007 DAL

- GW

- ACE

- 0

- 130213 0.170 NA 0.0381 NA

ISO13

- 07

- 02

- 008 DAL

- GW

- ACE

- DB

- 130213 0.185 NA 0.0276 NA

ISO13

- 07

- 02

- 009 DAL

- GW

- ACE

- FMS

- 1302 13 10.4 104 11.3 113

Average Concentration (ng/mL) ± %RPD 0.178 ng/mL ± 8.5% 0.0329 ng/mL ± 32% (2)

13 C 4 - PFOA 13 C 4 - PFOS

3M LIMS ID Description %Recovery %Recovery

ISO13

- 07

- 02

- 007 DAL

- GW

- ACE

- 0

- 130213 91.3 104

ISO13

- 07

- 02

- 008 DAL

- GW

- ACE

- DB

- 130213 104 95.1

ISO13

- 07

- 02

- 009 DAL

- GW

- ACE

- FMS

- 130213 96.2 101

Average Concentration (ng/mL) ± %RSD 97.2 % ± 6.7 % 100 % ± 4.5 %

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

. (2) Sample/sample duplicate RPD did not meet acceptance criteria of ≤ 20%.3M ENVIRONMENTAL LAB ORATORY
REPORT NO. ISO13

- 07

- 02

PAGE 16 OF 20 

### Table 13

. DAL GW WW8R 130 213 (1)

PFOA PFBS

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

ISO13

- 07

- 02

- 010 DAL

- GW

- WW8R

- 0

- 130213 3240 NA 357 NA

ISO13

- 07

- 02

- 011 DAL

- GW

- WW8R

- DB

- 1 30213 3260 NA 350 NA

ISO13

- 07

- 02

- 012 DAL

- GW

- WW8R

- FMS

- 130213 6650 80.6 3880 88.6

Average Concentration (ng/mL) ± %RPD 3250 ng/mL ± 0.62 % 354 ng/mL ± 2.0 %

PFHS PFOS

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

ISO13

- 07

- 02

- 010 DAL

- GW

- WW8R

- 0

- 130213 1920 NA 4860 NA

ISO13

- 07

- 02

- 011 DAL

- GW

- WW8R

- DB

- 130213 1870 NA 4830 NA

ISO13

- 07

- 02

- 012 DAL

- GW

- WW8R

- FMS

- 130213 5370 88.2 8930 102

Average Concentration (ng/mL) ± %RPD 1900 ng/mL ± 2.6 % 4850 ng/mL ± 0. 6 2 %

13 C 4 - P FOA 13 C 4 - PFOS

3M LIMS ID Description %Recovery %Recovery

ISO13

- 07

- 02

- 010 DAL

- GW

- WW8R

- 0

- 130213 88.2 99.0

ISO13

- 07

- 02

- 011 DAL

- GW

- WW8R

- DB

- 130213 90.1 97.7

ISO13

- 07

- 02

- 012 DAL

- GW

- WW8R

- FMS

- 130213 83.2 93.5

Average Concentration (ng/mL) ± %RSD 87.1 % ± 4.1 % 96.7 % ± 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

- 02

PAGE 17 OF 20 

### Table 14

. DAL GW W W9R 130 213 (1)

PFOA PFBS

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

ISO13

- 07

- 02

- 013 DAL

- GW

- WW9R

- 0

- 130213 2840 NA 232 NA

ISO13

- 07

- 02

- 014 DAL

- GW

- WW9R

- DB

- 130213 2860 NA 239 NA

ISO13

- 07

- 02

- 015 DAL

- GW

- WW9R

- FMS

- 130213 6100 77.0 3610 84.8

Average Concentration (ng/mL) ± %RPD 2850 ng/mL ± 0.70 % 236 ng/mL ± 3.0 %

PFHS PFOS

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

ISO13

- 07

- 02

- 013 DAL

- GW

- WW9R

- 0

- 130213 1420 NA 4130 NA

ISO13

- 07

- 02

- 014 DAL

- GW

- WW9R

- DB

- 130213 1370 NA 4060 NA

ISO13

- 07

- 02

- 015 DAL

- GW

- WW9R

- FMS

- 130213 4950 90.2 8260 104

Average Concentration (ng/mL) ± %RPD 1400 ng/mL ± 3.6 % 4100 ng/mL ± 1.7 %

13 C 4 - PFOA 13 C 4 - PFOS

3M LIMS ID Description %Recovery %Recov ery

ISO13

- 07

- 02

- 013 DAL

- GW

- WW9R

- 0

- 130213 90.5 99.6

ISO13

- 07

- 02

- 014 DAL

- GW

- WW9R

- DB

- 130213 89.9 98.0

ISO13

- 07

- 02

- 015 DAL

- GW

- WW9R

- FMS

- 130213 79.3 97.9

Average Concentration (ng/mL) ± %RSD 86.5 % ± 7.3 % 98.5 % ± 0.95 %

NA = Not Applicable (1) Samples were analy zed 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

- 02

PAGE 18 OF 20 

### Table 15 . Trip Blank Results

PFOA PFBS

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

ISO13

- 07

- 02

- 016 DAL

- GW

- TRIP01

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

ISO13

- 07

- 02

- 017 DAL

- GW

- TRIP01

- LS 9.39 (1) 89.1 9.96 (1) 100

ISO13

- 07

- 02

- 018 DAL

- GW

- TRIP01

- HS 3560 (2) 84.4 3680 (2) 92.5

PFHS PFOS

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

ISO13

- 07

- 02

- 016 DAL

- GW

- TRIP01

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

ISO13

- 07

- 02

- 017 DAL

- GW

- TRIP01

- LS 9.56 (1) 97.0 10.2 (1) 102

ISO13

- 07

- 02

- 018 DAL

- GW

- TRIP0 1

- HS 3760 (2) 95.4 4190 (2) 105

13 C 4 - PFOA 13 C 4 - PFOS

3M LIMS ID Description %Recovery %Recovery

ISO13

- 07

- 02

- 016 DAL

- GW

- TRIP01

- 0 101 (1) 104 (1)

ISO13

- 07

- 02

- 017 DAL

- GW

- TRIP01

- LS 95.7 (1) 104 (1)

ISO13

- 07

- 02

- 018 DAL

- GW

- TRIP01

- HS 87.3 (2) 96.1 (2)

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

.3 M ENVIRONMENTA L LABORATOR Y
REPOR T NO

. /S O 73-07-0 2



# 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

Appendi x A : Tren d Dat a fo r Activate d Carbo n Influen t (ACI ) Appendi x B : Tren d Dat a fo r Activate d Carbo n Effluen t (ACE )



# 8 Signature s



# i

. Susa n T

. Wolf

, 3 M Pricfcioja 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

,

Quality Assuranc e Representativ 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 03M ENVIRONMENTAL LAB ORATORY
REPORT NO. ISO13

- 07

- 02

PAGE 20 OF 20 

### Appendix 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

PFOA 1410 1180 1650 1410 2580 1910 2300

PFBS 11 10 792 1410 1830 723 588 830

PFHS 983 1100 1460 1390 1380 895 1580

PFOS 691 782 964 172 2810 1810 2940



### 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

PFOA 2.57 1250 0.387 0 .102 <0.0240 0.0124

PFBS 11.9 818 0.256 <0.0250 <0.0250 0.0360

PFHS 2.50 1240 0.552 0.117 <0.0250 0.178

PFOS 2.07 741 0.103 0.0376 <0.0232 0.0329

The ACE location was not sampled on 6/29/12.