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

– January 2013

Laboratory Request Number: ISO13

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Method Re quirement: 3M Method ETS

- 8

- 044.1

Report Date

– D ate 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 Cer t #2052. 01 The testing reported herein meet the requirements of ANSI/ISO/IEC 17025:2005 “General Requirements for the Competence of Testing and Calibration Laborator ies”, 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** 

**- 01** 

3M Decatur Groundwater Treatme nt Plant System; January 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 c ollected by Weston Solutions personnel

on January 17 , 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

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.

T he 3M Environmental Laboratory provided sample containers for five sampling locations; ACI, ACM2, ACE , WW8R, and WW9R . The sample set consis ted 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 appropria te matrix spike solution containing all analytes prior to being sent to the field for sample collection. S ample bottles for sampling locations ACM2 and ACE

, along with the Trip Blank sample and low spike

, were fortified with internal standards and surroga tes prior to being sent to the field for sample collection.

Samples were prepared and analyzed by method ETS

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- 044. 1 “ Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis ”. Select internal standards were used to aid in the data quality objectives.

Table 1 summarizes the sample results using the analytical method identified above. All results for quality control samples prepared and analyzed with the samples will be reported and discusse d 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. T esting 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 1920 600 901 1830

ISO13

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- 002 DAL

- GW

- ACI ; Sample Dup 1890 575 888 1780
Average 1910 (1) 588 (1) 895 (1) 1810 (1)
%RPD Sample/Sample Dup 1.6 4 .3 1.5 2.8

ISO13

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- 004 DAL

- GW

- ACM2; Sample <0.0240 1290 <0.0250 <0.0232

ISO13

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- 005 DAL

- GW

- ACM2 ; Sample Dup <0.0240 1250 <0.0250 <0.0232 Average <0.0240 (2 ) 1270 ( 1 ) <0.0250 (2 ,3 ) <0.0232 (2 )
%RPD Sample/Sample Dup NA 3.1 NA NA

ISO13

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- 007 DAL

- GW

- ACE; Sample <0.0240 <0.0250 <0.0250 <0.0232

ISO13

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- 008 DAL

- GW

- ACE ; Sample Dup <0.0240 <0.0250 <0.0250 <0.0232 Average <0.0240 (2 ) <0.0250 (2 ) <0.0250 (2 ) <0.0232 (2 )
%RPD Sample/Sample Dup NA NA 3.4 NA

ISO13

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- 010 DAL

- GW

- WW8R; Sample 4410 414 1950 5840

ISO13

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- 011 DAL

- GW

- WW8R ; Sample Dup 4290 405 1900 5580 Average 4350 (1) 410 (1) 1930 (1) 5710 (1)
%RPD Sample/Sample Dup 2.8 2.2 2.6 4.6

ISO13

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- 013 DAL

- GW

- WW9R; Sample 2670 182 936 3620

ISO13

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- 014 DAL

- GW

- WW9R ; Sample Dup 2740 186 972 3760 Average 2710 (1) 184 (1) 954 (1) 3690 (1)
%RPD Sample/Sample Dup 2. 6 2.2 3. 8 3.8

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

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- 044. 1 using external calibration . The analytical method uncertainties associated with the reported results are as follows: PFOA ±1 9 %, PFBS ± 16 %, PFHS ±1 7 %, and PFOS ±17 %. (2) Reported results were prepared and analyzed by ETS

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- 044. 1 using internal calibration . The analytical method uncertainties associated with the reported results are as follows: PFOA ±21 %, PFBS ±23 %, PFHS ±21 %, and P FOS ± 19 %. (3) The method uncertainty has been expanded for PFHS to ± 31%. See section 4 of the report for additional information.



# 2 Methods

- Analytical and Preparatory

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

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- 044. 1 “ Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis ”

.

Table 2 Target Analytes.

**Target Analytes Acronym**  **Reference Material Structure** 
Perfluorooctanoic Acid (C8 Acid) PFOA Linear + Branched Perfluorobutanesulfonate (C4 Sulfonate ) PFBS Linear Perfluorohexanesulfonate (C6 Sulfonate) 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 collected on January 17 , 201 3 in N algene 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

co ntaining 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 o f surrogate recovery standards at a nominal concentration of 0.1 ng/mL

. Collected sample bottles were received by the laboratory at ambient conditions on January 22 , 201 3

.


## 2.3 Sample Preparation Sample sets ACI, ACM2, WW8R, WW9R, and the Trip Blank field m atrix spikes 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 analy zed by external standard calibration.

The ACE sample set and the Trip Blank sample were prepared and analyzed for all analytes 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 and the Trip Blank low spike sample were re

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

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

s piking solution was added to the laboratory control samples (nominal concentration of 1 ng/mL). The sample bottles 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 then diluted with methanol in the same manner as the ACE and Trip Blank 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

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- 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 REPORT NO. ISO13

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PAGE 5 OF 20 

### Table 3 . Instrument Parameters.

Instrument Name ETS Kirk ETS Kirk Analysis Dates 1/24/13

– ex ternal calibration 1/30/13

– in ternal calibration Analytical Method ETS

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- 044.1 ETS

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- 044.1 Liquid Chromatograph Agilent 1260 Agilent 1260

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 0 μ L 4 0 μ L Mass Spectrometer Applied Biosystems API 5500 Applied Biosystems API 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 Transit**  **ion**
**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 20 msec for each transition. The individual transitions were summed to produce a “total ion chromatogram” (TIC) , which was u sed for quantitation. (1) Internal standard s were used for the analysis on 1/30 /13.3M ENVIRONMENTAL LAB ORATORY REPORT NO. ISO13

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# 3 Data Analysis

3.1 Calibration
Internal Standard Calibration Analysis : Samples were analyzed against a matrix

- matched stable isotope internal standard calibration curve. Calibration standards were prepared by spiking known amounts of stock solutions into 50 mL of 50:50 methanol: laboratory reagent water . The calibration standards contained an internal standard mix at a nominal concentration of 0.5 ng/mL. A total of twelve calibration standards rang ing from 0.0125 ng/mL to 25 ng/mL (nominal) were analyzed with the prepared samples. Of these twelve calibration standards, ten contained the surrogates at concentrations ranging from 0.0125 ng/mL to 10 ng/mL nominal. A quadratic, 1/x weighted, calibrati on 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 quanti tated using the overall calibration curve and reviewed for accuracy. Method calibration accuracy requirements of 100±25% (100±30% for the lowest curve point) were met for all analytes. The correlation coefficient (r) was greater than 0.995 for all analyt es.

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 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 ranging from 0.02 ng/mL to 25 ng/mL nominal. A qu adratic, 1/x weighted, calibration curve of the standard peak area counts was used to fit the data for each analyte. The data were not forced through zero during the fitting process. Calculating the standard concentrations using the peak area counts and the resultant calibration curve confirmed accuracy of each curve point. 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 poin t) 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 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 except for PF OA and PFOA surrogate analyzed using external calibration which had area counts RSDs of 6.3% and 6.2%, respectively

. A method deviation is included with the raw data.



## 3.3 Limit of Quantitation (LOQ) The LOQ as defined in method ETS

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- 044. 1 is the lowest non

- zero calibration standard in the curve that meets linearity and accuracy requirements and for which the area counts are at least twice 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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### T able 6 . LOQ

**Analyte Calibration**  **LOQ, ng/mL**

PFOA Internal standard 0.0240 (1)

PFBS Internal standard 0.0250 (1)

PFHS Internal standard 0.0250 (1)

PFOS Internal standard 0.0232 (1)

PFOA External standard 24.0 (2 )

PFBS External standa rd 2.00 (2 )

PFHS External standard 2.00 (2 )

PFOS External standard 23.2 (2 )

(1) The dilution factor of 2 was applied to the LOQ. (2) The dilution factor of 100 was applied to the LOQ.



## 3.4 Continuing Calibration During the course of the analytical sequence, seve ral 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 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 lab oratory

- prepared matrix matched water or 1 mL of Milli

- Q water to produce the desired concentration. The LCSs were then diluted with methanol in the same manner as the samples

. Method ETS

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

- 120% wi th a RSD ≤20%. All LCS sampl es met method accuracy criteria with the following exception:

1/30/13 Analysis (internal standard calibration): The high set of LCS samples for PFOA had an average recovery of 78.9% and P FHS had an average recovery of 79.2%

.

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

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PAGE 8 OF 20 

### Table 7 . Lab Control Spike Results.

ETS

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- 044.1

Ex

ternal Standard Calibration Analyzed 1/ 24/ 13 **PF OA (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

- 130124

- 1 0.479 0.46 96.0 0.464 0.45 96.5
LCS

- 130124

- 2 0.479 0.46 96.0 0.464 0.44 95.3

LCS

- 130124

- 3 0.479 0.46 96.2 0.464 0.443 95.5 Average ± %RSD 96.1 % ± 0.12 % 95.8 % ± 0.67 %

LCS

- 130124

- 4 4.79 5.67 118 4.64 5.32 115

LCS

- 130124

- 5 4.79 5.60 117 4.64 5.29 114

LCS

- 130124

- 6 4.79 5.62 117 4.64 5.37 116
Average ± %RSD 117 % ± 0.49 % 115 % ± 0.87 %

LCS

- 130124

- 7 19.1 20.5 107 18.5 20.4 110

LCS

- 130124

- 8 19.1 19.9 104 18.5 19.7 106

LCS

- 130124

- 9 19.1 19.5 102 18.5 19.3 104
Average ± %RSD 104 % ± 2.4 % 107 % ± 2.9 %

ETS

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- 044.1

Ex

ternal Standard Calibration Analyzed 1/ 24

/13 **PFBS PFHS** 

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

LCS

- 130124

- 1 0.500 0.531 106 0.500 0.545 109
LCS

- 130124

- 2 0.500 0.544 109 0.500 0.524 105

LCS

- 130124

- 3 0.500 0.531 106 0.500 0.528 106 Average ± %RSD 107 % ± 1.6 % 107 % ± 2.0 %

LCS

- 1301 24

- 4 5.00 5.50 110 5.00 5.30 106

LCS

- 130124

- 5 5.00 5.44 109 5.00 5.25 105

LCS

- 130124

- 6 5.00 5.66 113 5.00 5.38 108 Average ± %RSD 111 % ± 1.9 % 1 06 % ± 1.4 %

LCS

- 130124

- 7 20.0 21.4 107 20.0 19.6 97.9

LCS

- 130124

- 8 20.0 20.2 101 20.0 18.6 93.2

LCS

- 130124

- 9 20.0 19.7 98.6 20.0 18.2 91.2 Average ± %RSD 102 % ± 4 .2 % 94.1 % ± 3.7 %

(1) LCSs did not meet acceptance criteria of 100 ± 20%.3M ENVIRONMENTAL LAB ORATORY REPORT NO. ISO13

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

ETS

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- 044.1

Ex

ternal Standard Calibration Analyzed 1/ 24

/13 **PFOA surro gate**  **PFOS surrogate**

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

LCS

- 130124

- 1 0.499 0.502 101 0.478 0.468 97.8
LCS

- 130124

- 2 0.499 0.498 99. 8 0.478 0.468 97.9

LCS

- 130124

- 3 0.499 0.500 100 0.478 0.455 95.2 Average ± %RSD 100 % ± 0.64 % 97.0 % ± 1.6 %

LCS

- 130124

- 4 4.99 4.83 96.8 4.78 4.62 96.7

LCS

- 130124

- 5 4.99 4.80 96.2 4.78 4.61 96.4

LCS

- 130124

- 6 4.99 4.91 98.3 4.78 4.68 97.8 Average ± %RSD 97.1 % ± 1. 1 % 97.0 % ± 0.76 %

ETS

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- 044.1

In ternal Standard Calibration

Ana lyzed 1/ 30

/13 **PF OA (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

- 130130

- 1 0.190 0.162 85.1 0 .184 0.157 85.5
LCS

- 130130

- 2 0.190 0.161 84.6 0.184 0.156 84.9

LCS

- 130130

- 3 0.190 0.167 87.7 0.184 0.157 85.4 Average ± %RSD 85.8 % ± 1.9 % 85.3 % ± 0.38 %

LCS

- 130130

- 4 1.90 1.57 82.8 1.84 1.52 82.8

LCS

- 130130

- 5 1.90 1.60 84.5 1.84 1.55 84.0

LCS

- 130130

- 6 1.90 1.54 81.1 1.84 1.55 84.0 Average ± %RSD 82.8 % ± 2.1 % 83.6 % ± 0.83 %

LCS

- 130130

- 7 19.0 15.7 82.6 18.4 15.5 84.1

LC S

- 130130

- 8 19.0 13.9 73.1 18.4 13.6 74.1

LCS

- 130130

- 9 19.0 15.4 81.1 18.4 15.4 83.6 Average ± %RSD 78.9 % ± 6. 5 % (1) 80.6 % ± 7.0 %

(1) LCSs did not meet acceptance criteria of 100 ± 20%.3M ENVIRONMENTAL LAB ORATORY REPORT NO. ISO13

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

ETS

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- 044.1

In te rnal Standard Calibration Analyzed 1/3 0/13 **PFBS PFHS** 

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

LCS

- 130130

- 1 0.198 0.173 87.3 0.198 0.170 86.1
LCS

- 130130

- 2 0.198 0.165 83.4 0.198 0.164 82.7

LCS

- 130130

- 3 0.198 0.170 86.0 0.198 0.172 86.7 Average ± %RSD 85.6 % ± 2.3 % 85.2 % ± 2.5 %

LCS

- 130130

- 4 1.98 1.62 81.9 1.98 1.64 82.7

LCS

- 130130

- 5 1.98 1.67 84.5 1.98 1.61 81.2

LCS

- 130130

- 6 1.98 1.65 83.3 1.98 1.64 82.9 Average ± %RSD 83.2 % ± 1. 6 % 82.3 % ± 1.1 %

LCS

- 130130

- 7 19.9 16.8 84.4 19.9 16.6 83.5

LCS

- 130130

- 8 19.9 14.8 74.4 19.9 14.5 72.9

LCS

- 130130

- 9 19.9 16.3 81.7 19.9 16.1 81.1 Average ± %RSD 80.2 % ± 6.5 % 79.2 % ± 7.0 % (1)

ETS

- 8

- 044.1

In ternal Standard Calibration Analyzed 1/3 0/13 **PFOA surrogate**  **PFOS surrogate** 

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

LCS

- 130130

- 7 0.198 0.186 93.9 0.189 0.173 91.7
LCS

- 130130

- 8 0.198 0.187 94.3 0.189 0.173 91.3

LCS

- 130130

- 9 0.198 0.185 93.3 0.189 0.168 89.0 Average ± %RSD 93.8 % ± 0.54 % 90.7 % ± 1.6 %

LCS

- 130130

- 4 1.98 1.78 90.0 1.89 1.69 89.6

LCS

- 130130

- 5 1.98 1.82 91.7 1.89 1.71 90.2

LCS

- 130130

- 6 1.98 1.75 88.2 1.89 1.72 91.2 Average ± %RSD 90.0 % ± 1.9 % 90.3 % ± 0.89 %

(1) LCSs did not meet acceptance criteria of 100 ± 20%.3M ENVIRONMENTAL LAB ORATORY REPORT NO. ISO13

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## 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
stan dard 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 unc ertainty was determined to be ± 19% for PFOA and ± 20% for PFHS using internal standard calibration, but based on the percent bias of the high level LCSs, the method uncertainty has been expanded for PFOA and PFHS.

Table 8 . Analyt ical Method Uncertainty.

Analyte Calibration Method Standard Deviation Method Uncertainty

PF OA External Standard 9.36 ± 19 %

PFBS External Standard 7.88 ± 1 6 %

PFHS External Standard 8.28 ± 17 %

PFOS External Standard 8.60 ± 17 %

PFOA Internal Standard NA ± 21 %

PFBS Internal Standard 11.4 ± 23 %

PFHS Internal Standard NA ± 21 %

PFOS Internal Standard 9.66 ± 19 % 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 applicab le 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 recov eries within method acceptance criteria of 100±30% confirm that “unknown” components in the sample matrix do not significantly interfere with the extraction and analysis of the analytes of interest. The standards used for the preparation of the field matr ix 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 Sp ike Concentrations

Final Concentration (ng/mL)

Location Description PFOA PFBS PFHS PFOS

ACI Field Matrix Spike 2020 1990 1970 2000

ACM2, ACE Field Matrix Spike 10.1 9.96 9.86 10.0

WW8R, WW9R Field Matrix Spike 4040 3980 3940 4000

Trip Blank Low Fie ld Matrix Spike 10.1 9.96 9.86 10.0

High Field Matrix Spike 4040 3980 3940 40003M ENVIRONMENTAL LAB ORATORY REPORT NO. ISO13

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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 p rovides the average concentration and the relative percent difference ( % RPD) of the sample and sample duplicate. Results and average values are rounded to three significant figures. Percent relative difference (%RPD) values are rounded to two significant figures. Because of rounding, values may vary slightly from those listed in the raw data. Field matrix spikes meeting the method acceptance criteria of ± 30%, demonstrate that the method is appropriate for the given matrix.

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. The FMS did not meet acceptance criter ia for PFHS with a recovery of 69.1%. Since this is the only appropriate spike level, the sample method uncertainty will be expanded to ± 31% for PFHS.3M ENVIRONMENTAL LAB ORATORY REPORT NO. ISO13

- 07

- 01

PAGE 13 OF 20 

### Table 10

. DAL GW ACI 1 30117 (1)

**PFOA PFBS** 

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

ISO13

- 07

- 01

- 001 DAL

- GW

- ACI

- 0

- 130117 1920 NA 600 NA

ISO13

- 07

- 01

- 002 DAL

- GW

- ACI

- DB

- 130117 1890 NA 575 NA

ISO13

- 07

- 01

- 003 DAL

- GW

- ACI

- FMS

- 130117 4060 107 2660 104 **Average Concentration (ng/mL) ±**  **% RPD**  **1910 ng/mL**  **± 1.6**  **% 588**  **ng/mL ±**  **4 .3**  **%**

**PFHS PFOS** 

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

ISO13

- 07

- 01

- 001 DAL

- GW

- ACI

- 0

- 130117 901 NA 1830 NA

ISO13

- 07

- 01

- 002 DAL

- GW

- ACI

- DB

- 130117 888 NA 1780 NA

ISO13

- 0 7

- 01

- 003 DAL

- GW

- ACI

- FMS

- 130117 3020 108 4140 117
**Average Concentration (ng/mL) ±**  **%RPD 895**  **ng/mL ±**  **1.5 %**  **1810 ng/mL**  **± 2.8**  **%**

**13 C** 

**4 -** 

**PFOA 13**  **C 4**  **-**

**PFOS**

**3M LIMS ID Description**  **%Recovery %Recovery** 

ISO13

- 07

- 01

- 001 DAL

- GW

- ACI

- 0

- 130117 88.6 95.9

ISO13

- 07

- 01

- 002 D AL

- GW

- ACI

- DB

- 130117 88.1 93.8

ISO13

- 07

- 01

- 003 DAL

- GW

- ACI

- FMS

- 130117 84.4 87.9 **Average Concentration (ng/mL) ±**  **%RSD 87.0**  **% ±**  **2.6 %**  **92.5 %**  **± 4.5**  **%**

NA = Not Applicable (1) S amples were diluted 1:100 with methanol and analyzed by external standard calibration on 1 /24 /13

. 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

- 01

PAGE 14 OF 20 

### Table 11

. DAL GW ACM2 1 30117

**PFOA (**  **1 )**  **PFBS (2**  **)**

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

ISO13

- 07

- 01

- 004 DAL

- GW

- ACM2

- 0

- 130117 <0.0240 NA 1290 NA

ISO13

- 07

- 01

- 005 DAL

- GW

- ACM2

- DB

- 130117 <0.0240 NA 1250 NA

ISO13

- 07

- 01

- 006 DAL

- GW

- ACM2

- FMS

- 130117 7.66 75.8 1250 NC
**Average Concentration (ng/mL) ±**  **%RPD <**  **0.0240 ng/mL**  **1 270**  **ng/mL ±**  **3.1 %** 

**PFHS (1**  **) PFOS**  **( 1**  **)**

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

ISO13

- 07

- 01

- 004 DAL

- GW

- ACM2

- 0

- 130117 <0.0250 NA <0.0232 NA

ISO13

- 07

- 01

- 005 DAL

- GW

- ACM2

- DB

- 130117 <0.0250 NA <0.0232 N A

ISO13

- 07

- 01

- 006 DAL

- GW

- ACM2

- FMS

- 130117 6.81 69.1 (3) 7.06 70.6
**Average Concentration (ng/mL) ±**  **%RPD <0.0250 ng/mL**  **(4) <0.0232 ng/mL** 

**13 C** 

**4 -** 

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

**PFOS (1)** 

**3M LIMS ID Description**  **%Recovery %Recovery** 

ISO13

- 07

- 01

- 004 DAL

- GW

- ACM2

- 0

- 130117 93.0 9 1.1

ISO13

- 07

- 01

- 005 DAL

- GW

- ACM2

- DB

- 130117 87.8 86.7

ISO13

- 07

- 01

- 006 DAL

- GW

- ACM2

- FMS

- 130117 86.2 86.6 **Average Concentration (ng/mL) ±**  **%RSD 89.0**  **% ±**  **4.0 %**  **88.1 %**  **± 2.9**  **%**

NA = Not Applicable NC = Not Calculated; Spike level was less than 0.5x the endogenous sample concentration. (1) Samples were diluted 1:2 with methanol and analyzed by internal standard calibration on 1/30 /13

. (2) Sample s were diluted 1:100 with methanol and analyzed by external standard calibration on 1/24 /13

. (3) FMS did not meet acceptance criteria o f 100 ± 30%. (4) Method uncertainty has been expanded to ± 31% for PFHS

.3M ENVIRONMENTAL LAB ORATORY REPORT NO. ISO13

- 07

- 01

PAGE 15 OF 20 

### Table 12

. DAL GW ACE 1 30117 (1)

**PFOA PFBS** 

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

ISO13

- 07

- 01

- 007 DAL

- GW

- ACE

- 0

- 130117 <0.0240 NA <0.0250 NA

ISO13

- 07

- 01

- 008 DAL

- GW

- ACE

- DB

- 130117 <0.0240 NA <0.0250 NA

ISO13

- 07

- 01

- 009 DAL

- GW

- ACE

- FMS

- 130117 7.60 75.2 7.33 73.6 **Average Concentration (ng/mL) ±**  **%RPD <0.0240 ng/mL**  **<0.0250 ng/mL**

**PFHS PFOS** 

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

ISO13

- 07

- 01

- 007 DAL

- GW

- ACE

- 0

- 130117 <0.0250 NA <0.0232 NA

ISO13

- 07

- 01

- 008 DAL

- GW

- ACE

- DB

- 130117 <0.0250 NA <0.0232 NA

ISO13

- 07

- 01

- 009 DAL

- GW

- ACE

- FMS

- 130117 7.15 72.5 7.38 7 3.8
**Average Concentration (ng/mL) ±**  **%RPD <0.0250 ng/mL**  **<0.0232 ng/mL**

**13 C** 

**4 -** 

**PFOA 13**  **C 4**  **-**

**PFOS**

**3M LIMS ID Description**  **%Recovery %Recovery** 

ISO13

- 07

- 01

- 007 DAL

- GW

- ACE

- 0

- 130117 82.9 78.1

ISO13

- 07

- 01

- 008 DAL

- GW

- ACE

- DB

- 130117 84.4 85.7

ISO13

- 07

- 01

- 009 DAL

- GW

- ACE

- FMS

- 130117 87.2 87.3 **Average Concentration (ng/mL) ±**  **%RSD 84.8**  **% ±**  **2.6 %**  **83.7 %**  **± 5.9**  **%**

NA = Not Applicable (1) Samples were diluted 1:2 with methanol and analyzed by internal standard calibration on 1/30 /13

.3M ENVIRONMENTAL LAB ORATORY REPORT NO. ISO13

- 07

- 01

PAGE 16 OF 20 

### Table 13

. DAL GW WW8R 130117 (1)

**PFOA PFBS** 

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

ISO13

- 07

- 01

- 010 DAL

- GW

- WW8R

- 0

- 130117 4410 NA 414 NA

ISO13

- 07

- 01

- 011 DAL

- GW

- WW8R

- DB

- 130117 4290 NA 405 NA

ISO13

- 07

- 01

- 012 DAL

- GW

- WW8R

- FMS

- 13 0117 9070 117 4460 102 **Average Concentration (ng/mL) ±**  **%RPD 4350**  **ng/mL ±**  **2.8 %**  **410 ng/mL**  **± 2.2**  **%**

**PFHS PFOS** 

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

ISO13

- 07

- 01

- 010 DAL

- GW

- WW8R

- 0

- 130117 1950 NA 5840 NA

I SO13

- 07

- 01

- 011 DAL

- GW

- WW8R

- DB

- 130117 1900 NA 5580 NA

ISO13

- 07

- 01

- 012 DAL

- GW

- WW8R

- FMS

- 130117 5620 (2) 93.8 9390 (2) 92.0
**Average Concentration (ng/mL) ±**  **%RPD 1930**  **ng/mL ±**  **2.6 %**  **5710 ng/mL**  **± 4.6**  **%**

**13 C** 

**4 -** 

**PFOA 13**  **C 4**  **-**

**PFOS**

**3M LIMS ID Description**  **%Recovery %Re**  **covery**

ISO13

- 07

- 01

- 010 DAL

- GW

- WW8R

- 0

- 130117 81.5 86.3

ISO13

- 07

- 01

- 011 DAL

- GW

- WW8R

- DB

- 130117 81.2 83.8

ISO13

- 07

- 01

- 012 DAL

- GW

- WW8R

- FMS

- 130117 72.2 86.9 (2)
**Average Concentration (ng/mL) ±**  **%RSD 78.3**  **% ±**  **6 .7** 

**% 85.7**  **% ±**  **1.9 %** 

NA = Not Applicable (1) Samples were diluted 1:100 with methanol and analyzed by external standard cal ibration on 1/24 /13. The surrogate recovery standards 13 C 4 - PFOA and 13 C 4 - PFOS were added to the samples during sample preparation. (2) Samples re

- analyzed using a 1:400 dilution.3M ENVIRONMENTAL LAB ORATORY REPORT NO. ISO13

- 07

- 01

PAGE 17 OF 20 

### Table 14

. DAL GW WW9R 130117 (1)

**PFOA PFBS** 

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

ISO13

- 07

- 01

- 013 DAL

- GW

- WW9R

- 0

- 130117 2670 NA 182 NA

ISO13

- 07

- 01

- 014 DAL

- GW

- WW9R

- DB

- 130117 2740 NA 1 86 NA

ISO13

- 07

- 01

- 015 DAL

- GW

- WW9R

- FMS

- 130117 6720 99.4 3980 95.4 **Average Concentration (ng/mL) ±**  **%RPD 2710**  **ng/mL ±**  **2.6 %**  **184 ng/mL**  **± 2.2**  **%**

**PFHS PFOS** 

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

ISO13

- 07

- 01

- 013 DAL

- GW

- WW9R

- 0

- 130117 936 NA 3620 NA

ISO13

- 07

- 01

- 014 DAL

- GW

- WW9R

- DB

- 130117 972 NA 3760 NA

ISO13

- 07

- 01

- 015 DAL

- GW

- WW9R

- FMS

- 130117 4520 (2) 90.5 7310 (2) 90.5
**Average Concentration (ng/mL) ±**  **%RPD 954**  **ng/mL ±**  **3.8 %**  **3690 ng/mL**  **± 3.8**  **%**

**13 C** 

**4 -** 

**PFOA 13**  **C 4**  **-**

**PFOS**

**3M LIMS ID Description**  **%Recovery %Recovery** 

ISO13

- 07

- 01

- 013 DAL

- GW

- WW9R

- 0

- 130117 85.2 89.7

ISO13

- 07

- 01

- 014 DAL

- GW

- WW9R

- DB

- 130117 89.4 92.8

ISO13

- 07

- 01

- 015 DAL

- GW

- WW9R

- FMS

- 130117 75.7 86.6 (2)
**Average Concentration (ng/mL) ±**  **%RSD 83.4**  **% ±**  **8.4 %**  **89.7 %**  **± 3.4**  **%**

NA = Not Applicable (1) Samples were diluted 1:100 with methanol and analyzed by exte rnal standard calibration on 1/24 /13. The surrogate recovery standards 13 C 4 - PFOA and 13 C 4 - PFOS were added to the samples during sample preparation. (2) Sample s re

- analyzed using a 1:400 dilution.3M ENVIRONMENTAL LAB ORATORY REPORT NO. ISO13

- 07

- 01

PAGE 18 OF 20 

### Table 15 . Trip Blank Results

**PFOA PFBS** 

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

ISO13

- 07

- 01

- 016 DAL

- GW

- TRIP

- 0

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

ISO13

- 07

- 01

- 017 DAL

- GW

- TRIP

- LS 7.60 (1) 75.2 7.36 (1) 73.9

ISO13

- 07

- 01

- 018 DAL

- GW

- TRIP

- HS 4300 (2) 106 4020 (2) 101

**PFHS PFOS** 

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

ISO13

- 07

- 01

- 0 16 DAL

- GW

- TRIP

- 0

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

ISO13

- 07

- 01

- 017 DAL

- GW

- TRIP

- LS 7.44 (1) 75.5 7.37 (1) 73.7

ISO13

- 07

- 01

- 018 DAL

- GW

- TRIP

- HS 3830 ( 2, 3) 97.2 4430 (2) 1 11

**13 C** 

**4 -** 

**PFOA 13**  **C 4**  **-**

**PFOS**

**3M LIMS ID Description**  **%Recovery %Recovery** 

ISO13

- 07

- 01

- 016 DA L

- GW

- TRIP

- 0

- 85.6 (1) 82.9 (1)

ISO13

- 07

- 01

- 017 DAL

- GW

- TRIP

- LS 88.4 (1) 85.0 (1)

ISO13

- 07

- 01

- 018 DAL

- GW

- TRIP

- HS 84.7 (2) 85.8 (2)

NA = Not Applicable (1) Samples were diluted 1:2 with methanol and analyzed by internal standard calibration on 1/30 /13

. (2) Sample was diluted 1:100 with methanol and analyzed by exte rnal standard calibration on 1/24 /13

. (3) Sample re

- analyzed using a 1:400 dilution.3M ENVIRONMENTAL LABORATORY REPORT

NO. ISO13-07-01



# 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



# Mil A 3
Susa n T

. Wolf

, 3 M Principa 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 Representative / /

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

- 01

PAG E 20 OF 20 

### Appendix A: Analyte Trend Data for select sampl ing 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

PFOA 1410 1180 1650 1410 2580 1910

PFBS 1110 792 1410 1830 723 588

PFHS 983 1100 1460 1390 1380 895

PFOS 691 782 964 172 2810 1810



### 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

PFOA 2.57 1250 0.387 0.102 <0.0240

PFBS 11.9 818 0.256 < 0.0250 <0.0250

PFHS 2.50 1240 0.552 0.117 <0.0250

PFOS 2.07 741 0.103 0.0376 <0.0232

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