3M ENVIRONMENTAL LABORATORY

REPORT NO. ISO14-07-02

PAGE 1 OF 24

Final Report

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

3M Decatur, Alabama: Groundwater Treatment Plant GAC System –

February 2014

Laboratory Request Number: ISO14-07-02

Method Requirement: 3M Method ETS-8-044.1

Report Date – Date of Last Signature

Testing Laboratory

3M EHS Operations

3M Environmental Laboratory

Building 260-5N-17

Maplewood, MN 55144-1000

Requester 

Gary Hohenstein

3M Building 224-5W-03

Saint Paul, MN 55144-1000

Phone: (651) 737-3570

The testing reported herein meet the requirements of ANSI/ISO/IEC 17025:2005 

“General Requirements for the Competence of Testing and Calibration Laboratories”, in 

accordance with the A2LA Testing Certificate # 2052.01. Additionally, the laboratory’s 

quality system has been audited and was determined to be in conformance with the 

EPA GLPs (40 CFR 792) by an independent A2LA assessment.
3M ENVIRONMENTAL LABORATORY

REPORT NO. ISO14-07-02

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3M Environmental Laboratory

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

3M Principal Analytical Investigator: Susan Wolf

Report Author: Susanna Emond

Analytical Report ISO14-07-02

3M Decatur Groundwater Treatment Plant System; February 2014 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 27, 2014. Samples were returned to the 3M Environmental Laboratory for analysis of 

Perfluorooctanoate (PFOA), Perfluorobutane sulfonate (PFBS), Perfluorohexane sulfonate (PFHS),

Perfluorooctane sulfonate (PFOS) under laboratory project number ISO14-07-02. Analysis of the 

samples was completed as specified under 3M Environmental Laboratory General Project Outline 

(GPO) number GPO13-1289.

The 3M Environmental Laboratory provided sample containers for seven sampling locations; ACI, 

ACM2, ACE, WW8R, WW9R, WW10R, and WW11R. The sample set consisted of a field sample, field 

sample 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. Sample bottles for sampling locations ACM2 and ACE, along with the Trip Blank 

sample and low spike, were fortified with internal standards and surrogate recovery standard 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”. Internal 

standards were used for select samples to aid in the data quality objectives. 

Table 1 summarizes the sample results using the analytical method identified above. All results for 

quality control samples prepared and analyzed with the samples will be reported and discussed 

elsewhere in this report.

The testing reported herein meet the requirements of ANSI/ISO/IEC 17025:2005 “General 

Requirements for the Competence of Testing and Calibration Laboratories”, in 

accordance with the A2LA Testing Certificate # 2052.01. Additionally, the laboratory’s 

quality system has been audited and was determined to be in conformance with the EPA 

GLPs (40 CFR 792) by an independent A2LA assessment.
3M ENVIRONMENTAL LABORATORY

REPORT NO. ISO14-07-02

PAGE 3 OF 24

Table 1. Sample Results Summary (1)

3M LIMS ID Sample Description

PFOA 

Concentration 

(ng/mL)

PFBS 

Concentration 

(ng/mL)

PFHS 

Concentration 

(ng/mL)

PFOS 

Concentration 

(ng/mL)

ISO14-07-02-001 DAL-GW-ACI-0 - 140227 1860 1470 722 1830

ISO14-07-02-002 DAL-GW-ACI-DB - 140227 1880 1470 751 1760

Average 1870 1470 737 1800

%RPD Sample/Sample Dup 1.1 0.0 3.9 3.9

ISO14-07-02-004 DAL-GW-ACM2-0 - 140227 0.182 1250 0.0835 0.676

ISO14-07-02-005 DAL-GW-ACM2-DB - 140227 0.173 1150 0.0821 0.709

Average 0.178 (2) 1200 0.0828 (2) 0.693 (2)

%RPD Sample/Sample Dup 5.1 8.3 1.7 4.8

ISO14-07-02-007 DAL-GW-ACE-0- (100x) 0.129 0.0342 0.0637 0.0970

ISO14-07-02-008 DAL-GW-ACE-DB- (100x) 0.147 0.0377 0.0774 0.0962

Average 0.138 (2) 0.0360 (2) 0.0706 (2) 0.0966 (2)

%RPD Sample/Sample Dup 13 10 19 0.83

ISO14-07-02-010 DAL-GW-WW8R-0 - 140227 2540 326 1350 4130

ISO14-07-02-011 DAL-GW-WW8R-DB - 140227 2580 336 1380 4210

Average 2560 331 1370 4170

%RPD Sample/Sample Dup 1.6 3.0 2.2 1.9

ISO14-07-02-013 DAL-GW-WW9R-0 - 140227 2640 265 1390 4580

ISO14-07-02-014 DAL-GW-WW9R-DB - 140227 2620 274 1340 4730

Average 2630 270 1370 4660

%RPD Sample/Sample Dup 0.76 3.3 3.7 3.2

ISO14-07-02-016 DAL-GW-WW10R-0 - 140227 1820 264 919 2840

ISO14-07-02-017 DAL-GW-WW10R - 140227 1740 256 950 2880

Average 1780 260 935 2860

%RPD Sample/Sample Dup 4.5 3.1 3.3 1.4

ISO14-07-02-019 DAL-GW-WW11R-0 - 140227 1220 251 683 1850

ISO14-07-02-020 DAL-GW-WW11R-DB - 140227 1370 272 709 2340

Average 1300 262 696 2100

%RPD Sample/Sample Dup 12 8.0 3.7 23 (3)

NA = Not Applicable

(1) Reported results were prepared and analyzed by ETS-8-044.1 using external standard calibration. The analytical method 

uncertainties associated with the reported results are as follows: PFOA ±15%, PFBS ±10%, PFHS ±14%, and PFOS ±14%.

(2) Reported results were prepared and analyzed by ETS-8-044.1 using internal standard calibration. The analytical method 

uncertainties associated with the reported results are as follows: PFOA ±15%, PFBS ±9.5%, PFHS ±9.9%, and PFOS ±12%.

(3) Sample set did not meet sample / sample duplicate RPD acceptance criteria of ≤20%. 
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REPORT NO. ISO14-07-02

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2 Methods - Analytical and Preparatory

2.1 Methods

Analysis was completed using 3M Environmental Laboratory Method ETS-8-044.1 “Method of Analysis 

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

Table 2. Target Analytes

Target Analytes Acronym

Reference 

Material Structure

Perfluorooctanoic Acid (C8 Acid) PFOA Linear + Branched

Perfluorobutanesulfonate (C4 Sulfonate ) PFBS Linear

Perfluorohexanesulfonate (C6 Sulfonate) PFHS Linear

Perfluorooctanesulfonate (C8 Sulfonate) PFOS Linear + Branched

2.2 Sample Collection

Samples were collected on February 27, 2014 in NalgeneTM (high-density polyethylene) bottles 

prepared at the 3M Environmental Laboratory. Prior to sample collection, bottles designated for field 

matrix spikes were spiked in the laboratory with a known volume of an appropriate matrix spiking 

solution containing PFOA, PFBS, PFHS, and PFOS. Sample bottles for sampling locations ACM2 and 

ACE, along with the Trip Blank sample and low spike, were fortified with a mixture of mass-labeled 

internal standards at a nominal concentration of 1 ng/mL and a mixture of surrogate recovery standards 

at a nominal concentration of 0.1 ng/mL prior to being sent to the field for sample collection. Collected 

sample bottles were received by the laboratory at ambient conditions on March 5, 2014.

2.3 Sample Preparation

All samples were initially prepared by diluting with methanol (dilution factor of 100) and analyzing for all 

target 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 (nominal 

concentration of 1 ng/mL). Prepared samples were analyzed by external standard calibration. 

The ACE and ACM2 sample sets and the Trip Blank sample and low spike were subsequently 

prepared 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). Prepared samples were analyzed by internal standard calibration. 

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

separate internal standard spiking solution was added to the laboratory control samples (nominal 

concentration of 1 ng/mL). The laboratory control samples were analyzed in the same manner as the 

samples. 

2.4 Analysis

All samples and quality control samples were analyzed for four target analytes using high performance 

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 
3M ENVIRONMENTAL LABORATORY

REPORT NO. ISO14-07-02

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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.

Table 3. Instrument Parameters.

Instrument Name ETS Buster ETS Kirk

Analysis Dates 3/06/14 – external standard calibration 3/13/14– internal standard calibration

Analytical Method ETS-8-044.1 ETS-8-044.1

Liquid Chromatograph Agilent 1100 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 10 μL 10 μL

Mass Spectrometer Applied Biosystems API 4000 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 

(μL/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
3M ENVIRONMENTAL LABORATORY

REPORT NO. ISO14-07-02

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Table 5. Mass Transitions.

Analyte

Mass Transition

Q1/Q3

Internal Standard (1) Mass Transition

Q1/Q3

PFOA

413/369

[

13 413/219 C8]PFOA 421/376

413/169

PFBS

299/80

[

18

O2]PFBS 303/84

299/99

PFHS

399/99

[

13C3]PFHS 402/99

399/80

PFOS

499/99

[

13 499/80 C8]PFOS 507/80

499/130

[

13C4]PFOA surrogate 417/372 [13C8]PFOA 421/376

[

13C4]PFOS surrogate 503/80 [13C8]PFOS 507/80

Dwell time was between 20 and 50 msec for each transition. The individual transitions were summed to produce a “total ion 

chromatogram” (TIC), which was used for quantitation. 

(1) Internal standards were used for the analysis on 3/13/14.

3 Data Analysis

3.1 Calibration

External Standard Calibration Analysis on 3/06/14: 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: Milli-Q laboratory water. A total of 

eleven spiked standards ranging from 0.1 ng/mL to 150 ng/mL (nominal) were analyzed. The 

standards also contained the surrogates at concentrations ranging from 0.1 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 counts and the resultant calibration curve confirmed 

accuracy of each curve point. 

Internal Standard Calibration Analysis on 3/13/14: Samples were analyzed for all analytes 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 thirteen calibration standards ranging from 0.0125 ng/mL to 50 ng/mL (nominal) were 

analyzed (0.0125 ng/mL to 10 ng/mL (nominal) for the SRSs). Low or high points may have been 

disabled to meet method criteria. 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.

For each calibration curve, 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 greater than 0.995 for all analytes.
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3.2 System Suitability

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

demonstrate overall system suitability. The 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 criteria were met for all analytes with the exception of the peak 

area count RSD for PFHS analyzed on 3/06/14 (10%). A method deviation is included with the raw 

data.

3.3 Limit of Quantitation (LOQ)

The LOQ as defined in method ETS-8-044.1 is the lowest non-zero calibration standard in the curve 

that meets linearity and accuracy requirements and for which the area counts are at least twice those of 

the appropriate blanks. The LOQs associated with the sample analysis are listed in Table 6.

Table 6. LOQ

Analyte LOQ, ng/mL

3/06/14 Analysis (1)

LOQ, ng/mL

3/13/14 Analysis(2)

PFOA 9.58 0.0240

PFBS 10.0 0.0250

PFHS 10.0 0.0250

PFOS 9.27 0.0232

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

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

3.4 Continuing Calibration 

During the course of the analytical sequence, several continuing calibration verification samples 

(CCVs) were analyzed to confirm that the instrument response and the initial calibration curve were still

in control. The method acceptance criteria of 100% ± 25% was met for all analytes.

3.5 Blanks

Two types of blanks were prepared and analyzed with the samples: method blanks/solvent blanks and 

field/trip blanks. Each blank result was 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, the LCSs were then 

diluted with methanol in the same manner as the samples. Method ETS-8-044.1 states that the 

average recovery of LCSs at each spiking level be within 80%-120% with a RSD ≤20%. All LCS 

samples met method accuracy criteria with the following exception:

3/06/14 Analysis: The high level LCSs for PFOS-Surrogate had an average recovery of 125%. A 

method deviation is included with the raw data.

All LCSs were used in the determination of the analytical method uncertainty in section 3.7. 

The following calculations were used to generate data in Table 7.

* 100%

Spike Concentration

Calculated Concentration LCSPercent Recovery =

* 100%

average LCS recovery

standard deviation LCS replicates LCS% RSD =
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REPORT NO. ISO14-07-02

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Table 7. Lab Control Spike Results.

ETS-8-044.1

External Standard Calibration

Analyzed 3/06/14 PFOA (Linear + Branched) 13C4-PFOA surrogate

Lab ID

Spiked 

Concentration 

(ng/mL)

Calculated 

Concentration 

(ng/mL) %Recovery

Spiked 

Concentration 

(ng/mL)

Calculated 

Concentration 

(ng/mL) %Recovery

LCS-140306-1 0.958 0.926 96.6 0.998 1.06 106

LCS-140306-2 0.958 0.844 88.1 0.998 1.08 108

LCS-140306-3 0.958 0.880 91.8 0.998 1.08 108

Average ± %RSD 92.2% ± 4.6% 107% ± 1.1%

LCS-140306-4 9.58 10.10 106 9.98 11.3 113

LCS-140306-5 9.58 9.61 100 9.98 11.8 118

LCS-140306-6 9.58 10.20 106 9.98 11.2 112

Average ± %RSD 104% ± 3.3% 114% ± 2.8%

LCS-140306-7 38.2 38.6 101

LCS-140306-8 38.2 38.5 101

LCS-140306-9 38.2 37.6 98.5

Average ± %RSD 100% ± 1.4%

ETS-8-044.1

External Standard Calibration

Analyzed3/06/14 PFBS PFHS

Lab ID

Spiked 

Concentration 

(ng/mL)

Calculated 

Concentration 

(ng/mL) %Recovery

Spiked 

Concentration 

(ng/mL)

Calculated 

Concentration 

(ng/mL) %Recovery

LCS-140306-1 1.00 1.05 105 1.00 1.06 106

LCS-140306-2 1.00 0.95 95.0 1.00 1.05 105

LCS-140306-3 1.00 1.06 106 1.00 1.09 109

Average ± %RSD 102% ± 6.0% 107% ± 2.0%

LCS-140306-4 10.0 10.8 108 10.0 11.4 114

LCS-140306-5 10.0 11.2 112 10.0 11.2 112

LCS-140306-6 10.0 10.9 109 10.0 11.3 113

Average ± %RSD 110% ± 1.9% 113% ± 0.88%

LCS-140306-7 39.8 41.8 105 39.8 43.6 110

LCS-140306-8 39.8 42.3 106 39.8 42.5 107

LCS-140306-9 39.8 40.9 103 39.8 42.5 107

Average ± %RSD 105% ± 1.5% 108% ± 1.6%

(1) LCS recovery did not meet acceptance criteria of 100 ± 20%.
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Table 7 continued. Lab Control Spike Results.

ETS-8-044.1

External Standard Calibration

Analyzed 3/06/14 PFOS (Linear + Branched) 13C4-PFOS surrogate

Lab ID

Spiked 

Concentration 

(ng/mL)

Calculated 

Concentration 

(ng/mL) %Recovery

Spiked 

Concentration 

(ng/mL)

Calculated 

Concentration 

(ng/mL) %Recovery

LCS-140306-1 0.927 0.928 100 0.956 1.07 112

LCS-140306-2 0.927 0.942 102 0.956 1.07 112

LCS-140306-3 0.927 0.911 98.2 0.956 1.08 113

Average ± %RSD 100% ± 1.9% 112% ± 0.51%

LCS-140306-4 9.27 9.97 108 9.56 11.9 125

LCS-140306-5 9.27 9.71 105 9.56 12.0 126

LCS-140306-6 9.27 10.1 109 9.56 11.7 123

Average ± %RSD 107% ± 1.9% 125% ± 1.2% (1)

LCS-140306-7 36.9 38.2 103

LCS-140306-8 36.9 39.4 107

LCS-140306-9 36.9 38.1 103

Average ± %RSD 104% ± 2.2%

ETS-8-044.1

Internal Standard Calibration

Analyzed 3/13/14 PFOA (Linear + Branched) 13C4-PFOA surrogate

Lab ID

Spiked 

Concentration 

(ng/mL)

Calculated 

Concentration 

(ng/mL) %Recovery

Spiked 

Concentration 

(ng/mL)

Calculated 

Concentration 

(ng/mL) %Recovery

LCS-140313-1 0.190 0.202 106 0.198 0.204 103

LCS-140313-2 0.190 0.208 110 0.198 0.211 106

LCS-140313-3 0.190 0.208 109 0.198 0.230 116

Average ± %RSD 108% ± 1.9% 108% ± 6.3%

LCS-140313-4 9.50 10.5 110 1.98 2.21 111

LCS-140313-5 9.50 10.2 108 1.98 2.33 118

LCS-140313-6 9.50 10.8 113 1.98 2.50 126

Average ± %RSD 110% ± 2.3% 118% ± 6.3%

LCS-140313-7 38.0 45.0 118

LCS-140313-8 38.0 42.8 113

LCS-140313-9 38.0 44.8 118

Average ± %RSD 116% ± 2.5%

(1) LCS recovery did not meet acceptance criteria of 100 ± 20%.
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Table 7 continued. Lab Control Spike Results.

ETS-8-044.1

Internal Standard Calibration

Analyzed 3/13/14 PFBS PFHS

Lab ID

Spiked 

Concentration 

(ng/mL)

Calculated 

Concentration 

(ng/mL) %Recovery

Spiked 

Concentration 

(ng/mL)

Calculated 

Concentration 

(ng/mL) %Recovery

LCS-140313-1 0.198 0.190 95.9 0.198 0.226 114

LCS-140313-2 0.198 0.199 101 0.198 0.220 111

LCS-140313-3 0.198 0.202 102 0.198 0.223 113

Average ± %RSD 99.6% ± 3.3% 113% ± 1.4%

LCS-140313-4 9.92 10.0 101 9.92 11.1 112

LCS-140313-5 9.92 10.3 104 9.92 10.9 110

LCS-140313-6 9.92 10.4 105 9.92 11.0 111

Average ± %RSD 103% ± 2.0% 111% ± 0.90%

LCS-140313-7 39.6 44.1 111 39.6 45.9 116

LCS-140313-8 39.6 41.4 105 39.6 43.1 109

LCS-140313-9 39.6 42.2 107 39.6 45.8 116

Average ± %RSD 108% ± 2.8% 114% ± 3.6%

ETS-8-044.1

Internal Standard Calibration

Analyzed 3/13/14 PFOS (Linear + Branched) 13C4-PFOS surrogate

Lab ID

Spiked 

Concentration 

(ng/mL)

Calculated 

Concentration 

(ng/mL) %Recovery

Spiked 

Concentration 

(ng/mL)

Calculated 

Concentration 

(ng/mL) %Recovery

LCS-140313-1 0.184 0.197 107 0.189 0.184 97.5

LCS-140313-2 0.184 0.222 121 0.189 0.196 104

LCS-140313-3 0.184 0.221 120 0.189 0.206 109

Average ± %RSD 116% ± 6.7% 104% ± 5.6%

LCS-140313-4 9.20 9.87 107 1.90 2.10 110

LCS-140313-5 9.20 10.1 109 1.90 2.34 123

LCS-140313-6 9.20 10.1 110 1.90 2.32 122

Average ± %RSD 109% ± 1.4% 118% ± 6.1% 

LCS-140313-7 36.7 43.2 118

LCS-140313-8 36.7 40.2 110

LCS-140313-9 36.7 41.6 113

Average ± %RSD 114% ± 3.6%

(1) LCS recovery did not meet acceptance criteria of 100 ± 20%.
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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 

standard deviation is calculated for the set of accuracy results (in %) obtained for the QC samples. The 

expanded uncertainty is calculated by multiplying the standard deviation by a factor of 2, which 

corresponds to a confidence level of 95%. 

Table 8. Analytical Method Uncertainty.

Analyte Calibration Method Standard Deviation (%) Method Uncertainty

PFOA External Standard 7.73 ±15%

PFBS External Standard 5.07 ±10%

PFHS External Standard 7.04 ±14%

PFOS External Standard 6.88 ±14%

PFOA Internal Standard 7.42 ±15%

PFBS Internal Standard 4.73 ±9.5%

PFHS Internal Standard 4.95 ±9.9%

PFOS Internal Standard 5.81 ±12%

3.8 Field Matrix Spikes (FMS)

A field matrix spike was collected at each sampling point to verify that the analytical method is 

applicable to the collected matrix. Field matrix spikes are generated by adding a measured volume of 

field sample to a container spiked by the laboratory with the target analytes prior to shipping sample 

containers for sample collection. Field matrix spike recoveries within method acceptance criteria of 

100±30% confirm that “unknown” components in the sample matrix do not significantly interfere with 

the extraction and analysis of the analytes of interest. The standards used for the preparation of the 

field matrix spiking solutions contained reference materials comprised of both linear and branched 

isomers for PFOA and PFOS. Field matrix spikes are presented in section 4 of this report. 

*100%

Spike Concentraton

(Sample Concentration of FMS Average Concentration:FieldSample & FieldSample Dup.) FMS Recovery − =

Table 9. Field Matrix Spike Concentrations.

Final Concentration (ng/mL)

Location Description PFOA PFBS PFHS PFOS

ACI Field Matrix Spike 1980 2000 2000 2000

ACM2, ACE Field Matrix Spike 4.96 5.00 5.00 4.99

WW8R, WW9R Field Matrix Spike 2480 2500 2510 2500

WW10R, WW11R Field Matrix Spike 1980 2000 2000 2000

Trip Blank

Low Field Matrix Spike 4.96 5.00 5.00 4.99

High Field Matrix Spike 2480 2500 2510 2500
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4 Data Summary and Discussion

The tables below summarize the sample results and field matrix spike recoveries for the seven

locations as well as the Trip Blank. Each table provides the average concentration and the relative 

percent difference (%RPD) of the sample and sample duplicate. Results and average values are 

rounded to three significant figures. Relative percent difference (%RPD) values are rounded to two 

significant figures. Because of rounding, values may vary slightly from those listed in the raw data. 

Field matrix spikes meeting the method acceptance criteria of ±30%, demonstrate that the method is 

appropriate for the given matrix. 

All field samples met method acceptance criteria except where noted below.

DAL-GW-ACM2: the FMS spike level at 5 ng/mL was not appropriate for PFBS; however, the 

surrogate recovery standard 13C4-PFOS met method acceptance criteria. No additional QC samples 

were prepared. 

DAL-GW-WW11R: sample / sample duplicate %RPD was 23% for PFOS. 
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Table 10. DAL GW ACI 140227 (1)

PFOA PFBS

3M LIMS ID Sample Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO14-07-02-001 DAL-GW-ACI-0 - 140227 1860 NA 1470 NA

ISO14-07-02-002 DAL-GW-ACI-DB - 140227 1880 NA 1470 NA

ISO14-07-02-003 DAL-GW-ACI-FMS - 140227 3610 87.7 3340 93.5

Average Concentration (ng/mL) ± %RPD 1870 ng/mL ± 1.1% 1470 ng/mL ± 0.0%

PFHS PFOS

3M LIMS ID Sample Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO14-07-02-001 DAL-GW-ACI-0 - 140227 722 NA 1830 NA

ISO14-07-02-002 DAL-GW-ACI-DB - 140227 751 NA 1760 NA

ISO14-07-02-003 DAL-GW-ACI-FMS - 140227 2890 107 3780 99.4

Average Concentration (ng/mL) ± %RPD 737 ng/mL ± 3.9% 1800 ng/mL ± 3.9% 

13C4-PFOA 13C4-PFOS

3M LIMS ID Sample Description %Recovery %Recovery

ISO14-07-02-001 DAL-GW-ACI-0 - 140227 110 110

ISO14-07-02-002 DAL-GW-ACI-DB - 140227 97.6 112

ISO14-07-02-003 DAL-GW-ACI-FMS - 140227 102 105

Average Concentration (ng/mL) ± %RSD 103% ± 6.2% 109% ± 3.5%

NA = Not Applicable

(1) Samples were analyzed by external standard calibration. The surrogate recovery standards 13C4-PFOA and 13C4-PFOS were 

added to the samples during sample preparation.
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Table 11. DAL GW ACM2 140227

PFOA (1) PFBS (2)

3M LIMS ID Sample Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO14-07-02-004 DAL-GW-ACM2-0 - 140227 0.182 NA 1250 NA

ISO14-07-02-005 DAL-GW-ACM2-DB - 140227 0.173 NA 1150 NA

ISO14-07-02-006 DAL-GW-ACM2-FMS - 140227 5.84 114 1240 NC

Average Concentration (ng/mL) ± %RPD 0.178 ng/mL ± 5.1% 1200 ng/mL ± 8.3%

PFHS (1) PFOS (1)

3M LIMS ID Sample Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO14-07-02-004 DAL-GW-ACM2-0 - 140227 0.0835 NA 0.676 NA

ISO14-07-02-005 DAL-GW-ACM2-DB - 140227 0.0821 NA 0.709 NA

ISO14-07-02-006 DAL-GW-ACM2-FMS - 140227 5.77 114 6.28 112

Average Concentration (ng/mL) ± %RPD 0.0828 ng/mL ± 1.7% 0.693 ng/mL ± 4.8%

13C4-PFOA (1) 13C4-PFOS (1) 13C4-PFOS (2)

3M LIMS ID Sample Description %Recovery %Recovery %Recovery

ISO14-07-02-004 DAL-GW-ACM2-0 - 140227 98.5 100 115

ISO14-07-02-005 DAL-GW-ACM2-DB - 140227 93.3 98.5 113

ISO14-07-02-006 DAL-GW-ACM2-FMS - 140227 92.3 95.3 109

Average Concentration (ng/mL) ± %RSD 94.7% ± 3.5% 98.0% ± 2.5% 112% ± 2.8%

NA = Not Applicable

NC = Not Calculated; Spike level was less than 0.5x the endogenous sample concentration.

(1) Samples were analyzed by internal standard calibration.

(2) Samples were analyzed by external standard calibration. The surrogate recovery standard 13C4-PFOS was added to the 

samples during sample preparation.
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Table 12. DAL GW ACE 140227 (1)

PFOA PFBS

3M LIMS ID Sample Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO14-07-02-007 DAL-GW-ACE-0 - 140227 0.129 NA 0.0342 NA

ISO14-07-02-008 DAL-GW-ACE-DB - 140227 0.147 NA 0.0377 NA

ISO14-07-02-009 DAL-GW-ACE-FMS - 140227 5.76 113 5.17 103

Average Concentration (ng/mL) ± %RPD 0.138 ng/mL ± 13% 0.0360 ng/mL ± 9.7%

PFHS PFOS

3M LIMS ID Sample Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO14-07-02-007 DAL-GW-ACE-0 - 140227 0.0637 NA 0.0970 NA

ISO14-07-02-008 DAL-GW-ACE-DB - 140227 0.0774 NA 0.0962 NA

ISO14-07-02-009 DAL-GW-ACE-FMS - 140227 5.54 109 5.76 113

Average Concentration (ng/mL) ± %RPD 0.0706 ng/mL ± 19% 0.0966 ng/mL ± 0.83%

13C4-PFOA 13C4-PFOS

3M LIMS ID Sample Description %Recovery %Recovery

ISO14-07-02-007 DAL-GW-ACE-0 - 140227 95.1 96.2

ISO14-07-02-008 DAL-GW-ACE-DB - 140227 91.6 89.3

ISO14-07-02-009 DAL-GW-ACE-FMS - 140227 91.4 94.7

Average Concentration (ng/mL) ± %RSD 92.7% ± 2.2% 93.4% ± 3.9%

NA = Not Applicable

(1) Samples were analyzed by internal standard calibration.
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Table 13. DAL GW WW8R 140227 (1)

PFOA PFBS

3M LIMS ID Sample Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO14-07-02-010 DAL-GW-WW8R-0 - 140227 2540 NA 326 NA

ISO14-07-02-011 DAL-GW-WW8R-DB - 140227 2580 NA 336 NA

ISO14-07-02-012 DAL-GW-WW8R-FMS - 140227 5000 98.4 2890 102

Average Concentration (ng/mL) ± %RPD 2560 ng/mL ± 1.6% 331 ng/mL ± 3.0%

PFHS PFOS

3M LIMS ID Sample Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO14-07-02-010 DAL-GW-WW8R-0 - 140227 1350 NA 4130 NA

ISO14-07-02-011 DAL-GW-WW8R-DB - 140227 1380 NA 4210 NA

ISO14-07-02-012 DAL-GW-WW8R-FMS - 140227 4060 108 6790 105

Average Concentration (ng/mL) ± %RPD 1370 ng/mL ± 2.2% 4170 ng/mL ± 1.9%

13C4-PFOA 13C4-PFOS

3M LIMS ID Sample Description %Recovery %Recovery

ISO14-07-02-010 DAL-GW-WW8R-0 - 140227 95.6 99.0

ISO14-07-02-011 DAL-GW-WW8R-DB - 140227 101 119

ISO14-07-02-012 DAL-GW-WW8R-FMS - 140227 94.7 108

Average Concentration (ng/mL) ± %RSD 97.2% ± 3.6% 109% ± 9.4%

NA = Not Applicable

(1) Samples were analyzed by external standard calibration. The surrogate recovery standards 13C4-PFOA and 13C4-PFOS were 

added to the samples during sample preparation.
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Table 14. DAL GW WW9R 140227 (1)

PFOA PFBS

3M LIMS ID Sample Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO14-07-02-013 DAL-GW-WW9R-0 - 140227 2640 NA 265 NA

ISO14-07-02-014 DAL-GW-WW9R-DB - 140227 2620 NA 274 NA

ISO14-07-02-015 DAL-GW-WW9R-FMS - 140227 4830 88.7 2740 98.8

Average Concentration (ng/mL) ± %RPD 2630 ng/mL ± 0.76% 270 ng/mL ± 3.3%

PFHS PFOS

3M LIMS ID Sample Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO14-07-02-013 DAL-GW-WW9R-0 - 140227 1390 NA 4580 NA

ISO14-07-02-014 DAL-GW-WW9R-DB - 140227 1340 NA 4730 NA

ISO14-07-02-015 DAL-GW-WW9R-FMS - 140227 3840 98.8 6920 90.8

Average Concentration (ng/mL) ± %RPD 1370 ng/mL ± 3.7% 4660 ng/mL ± 3.2%

13C4-PFOA 13C4-PFOS

3M LIMS ID Sample Description %Recovery %Recovery

ISO14-07-02-013 DAL-GW-WW9R-0 - 140227 101 109

ISO14-07-02-014 DAL-GW-WW9R-DB - 140227 98.3 109

ISO14-07-02-015 DAL-GW-WW9R-FMS - 140227 97.6 107

Average Concentration (ng/mL) ± %RSD 99.0% ± 1.9% 108% ± 1.1%

NA = Not Applicable

(1) Samples were analyzed by external standard calibration. The surrogate recovery standards 13C4-PFOA and 13C4-PFOS were 

added to the samples during sample preparation.
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Table 15. DAL GW WW10R 140227 (1)

PFOA PFBS

3M LIMS ID Sample Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO14-07-02-016 DAL-GW-WW10R-0 - 140227 1820 NA 264 NA

ISO14-07-02-017 DAL-GW-WW10R-DB - 140227 1740 NA 256 NA

ISO14-07-02-018 DAL-GW-WW10R-FMS - 140227 3710 97.3 2130 93.5

Average Concentration (ng/mL) ± %RPD 1780 ng/mL ± 4.5% 260 ng/mL ± 3.1%

PFHS PFOS

3M LIMS ID Sample Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO14-07-02-016 DAL-GW-WW10R-0 - 140227 919 NA 2840 NA

ISO14-07-02-017 DAL-GW-WW10R-DB - 140227 950 NA 2880 NA

ISO14-07-02-018 DAL-GW-WW10R-FMS - 140227 3220 114 4770 95.7

Average Concentration (ng/mL) ± %RPD 935 ng/mL ± 3.3% 2860 ng/mL ± 1.4%

13C4-PFOA 13C4-PFOS

3M LIMS ID Sample Description %Recovery %Recovery

ISO14-07-02-016 DAL-GW-WW10R-0 - 140227 103 106

ISO14-07-02-017 DAL-GW-WW10R-DB - 140227 103 114

ISO14-07-02-018 DAL-GW-WW10R-FMS - 140227 96.8 106

Average Concentration (ng/mL) ± %RSD 101% ± 3.7% 108% ± 4.5%

NA = Not Applicable

(1) Samples were analyzed by external standard calibration. The surrogate recovery standards 13C4-PFOA and 13C4-PFOS were 

added to the samples during sample preparation.
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Table 16. DAL GW WW11R 140227 (1)

PFOA PFBS

3M LIMS ID Sample Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO14-07-02-019 DAL-GW-WW11R-0 - 140227 1220 NA 251 NA

ISO14-07-02-020 DAL-GW-WW11R-DB - 140227 1370 NA 272 NA

ISO14-07-02-021 DAL-GW-WW11R-FMS - 140227 3090 90.5 2430 108

Average Concentration (ng/mL) ± %RPD 1300 ng/mL ± 12% 262 ng/mL ± 8.0%

PFHS PFOS

3M LIMS ID Sample Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO14-07-02-019 DAL-GW-WW11R-0 - 140227 683 NA 1850 NA

ISO14-07-02-020 DAL-GW-WW11R-DB - 140227 709 NA 2340 NA

ISO14-07-02-021 DAL-GW-WW11R-FMS - 140227 2910 110 3790 84.9

Average Concentration (ng/mL) ± %RPD 696 ng/mL ± 3.7% 2100 ng/mL ± 23% (2)

13C4-PFOA 13C4-PFOS

3M LIMS ID Sample Description %Recovery %Recovery

ISO14-07-02-019 DAL-GW-WW11R-0 - 140227 102 113

ISO14-07-02-020 DAL-GW-WW11R-DB - 140227 111 111

ISO14-07-02-021 DAL-GW-WW11R-FMS - 140227 95.4 109

Average Concentration (ng/mL) ± %RSD 103% ± 7.7% 111% ± 1.9%

NA = Not Applicable

(1) Samples were analyzed by external standard calibration. The surrogate recovery standards 13C4-PFOA and 13C4-PFOS were 

added to the samples during sample preparation

(2) Sample RPD set did not meet acceptance criteria of ± 20%.
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REPORT NO. ISO14-07-02

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Table 17. Trip Blank Results

PFOA PFBS

3M LIMS ID Sample Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO14-07-02-022 DAL-GW-TRIP-0 - 140227 <0.0240 (1) NA <0.0250 (1) NA

ISO14-07-02-023 DAL-GW-TRIP-LS - 140227 5.46 (1) 110 5.15 (1) 103

ISO14-07-02-024 DAL-GW-TRIP-HS - 140227 2390 (2) 96.4 2450 (2) 98.0

PFHS PFOS

3M LIMS ID Sample Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO14-07-02-022 DAL-GW-TRIP-0 - 140227 <0.0250 (1) NA <0.0232 (1) NA

ISO14-07-02-023 DAL-GW-TRIP-LS - 140227 5.47 (1) 109 5.35 (1) 107

ISO14-07-02-024 DAL-GW-TRIP-HS - 140227 2630 (2) 105 2660 (2) 107

13C4-PFOA (1) 13C4-PFOS (1) 13C4-PFOA (2) 13C4-PFOS (2)

3M LIMS ID Sample Description %Recovery %Recovery %Recovery %Recovery

ISO14-07-02-022 DAL-GW-TRIP-0 - 140227 86.9 95.8 108 99.2

ISO14-07-02-023 DAL-GW-TRIP-LS - 140227 93.5 93.7 103 103

ISO14-07-02-024 DAL-GW-TRIP-HS - 140227 NA NA 92.7 102

NA = Not Applicable

(1) Samples were analyzed by internal standard calibration.

(2) Samples were analyzed by external standard calibration. The surrogate recovery standards 13C4-PFOA and 13C4-PFOS were 

added to the samples during sample preparation

.
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5 Conclusion

Laboratory control spikes were used to determine the analytical method accuracy and precision for all 

analytes. The accuracy and precision were then used to estimate the method uncertainty for the 

results. Field matrix spike recoveries demonstrated that the analytical method was appropriate for the 

given sample matrix. 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”. Analytical results are reported in Table 1 and 10-17 of this report.

6 Data / Sample Retention

All remaining sample and associated project data (hardcopy and electronic) will be archived according 

to 3M Environmental Laboratory standard operating procedures.

7 Attachments

Attachment A: Analyte Trend Data for the Decatur Ground Water Treatment Plant (GWTP) GAC 

System.

8 Signatures

Susan T. Wolf, 3M Principal Analytical Investigator

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

The 3M Environmental Laboratory’s Quality Assurance Unit has audited the data and report for this 

project.

Quality Assurance Representative 

This test report shall not be reproduced except in full, without written approval of the 3M Environmental 

Laboratory.
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REPORT NO. ISO14-07-02

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Attachment A: Analyte Trend Data for select sampling points at the Decatur Ground Water Treatment 

Plant (GWTP) GAC System 

ACI (Activated Carbon Influent) - Sample Results in ng/mL

ACI 03/27/13 04/29/13 05/31/13 06/27/13 07/23/13 09/30/13 10/28/13 11/18/13 12/13/13 01/30/14 02/27/14

PFOA 2220 1480 1860 1480 1630 2320 1880 2190 1830 1580 1870

PFBS 1060 1360 1040 708 1230 356 1590 1100 1350 202 1470

PFHS 1090 777 940 942 749 1400 866 1330 695 845 737

PFOS 2490 1670 2150 1590 1680 3240 2100 2240 1970 2700 1800

ACE (Activated Carbon Effluent) - Sample Results in ng/mL

ACE 03/27/13 04/29/13 05/31/13 06/27/13 07/23/13 09/30/13 10/28/13 11/18/13 12/13/13 01/30/14 02/27/14

PFOA 0.0380 0.0422 0.0725 0.0717 0.0641 0.115 0.231 0.478 0.0798 0.490 0.138

PFBS <0.0250 0.392 24.8 111 1960 1950 0.379 0.592 0.0766 0.257 0.0360

PFHS 0.0477 0.057 0.105 0.118 0.0778 0.156 0.180 0.366 0.0648 0.219 0.0706

PFOS <0.0232 <0.0232 <0.0232 <0.0232 0.0277 0.0452 0.0785 0.0726 0.0303 0.209 0.0966
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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 03/27/13 04/29/13 05/31/13 06/27/13 07/23/13 09/30/13 10/28/13 11/18/13 12/13/13 01/30/14 02/27/14

PFOA 3640 3190 2760 2760 2640 2890 2830 3040 2720 2660 2560

PFBS 385 364 289 282 263 303 312 362 316 326 331

PFHS 1760 1610 1330 1340 1260 1370 1300 1440 1270 1460 1370

PFOS 5120 4830 4180 4110 3910 4100 4410 4750 4060 3990 4170

WW9R - Sample Results in ng/mL

WW9R 03/27/13 04/29/13 05/31/13 06/27/13 07/23/13 09/30/13 10/28/13 11/18/13 12/13/13 01/30/14 02/27/14

PFOA 3330 2650 2660 2630 2410 2730 2820 2950 2690 2900 2630

PFBS 278 244 226 225 212 249 286 305 259 317 270

PFHS 1440 1200 1120 1140 1030 1220 1280 1340 1170 1460 1370

PFOS 4660 4340 4210 4150 3670 4200 4380 4540 4190 4800 4660
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Attachment A: Analyte Trend Data for select sampling points at the Decatur Ground Water Treatment 

Plant (GWTP) GAC System 

WW10R - Sample Results in ng/mL

WW10R 9/30/2013 10/28/2013 11/18/2013 12/13/2013 1/30/2014 2/27/2014

PFOA 2070 2150 2400 1890 1330 1780

PFBS 247 264 303 239 250 260

PFHS 1030 1030 1120 885 757 935

PFOS 2770 3160 3890 2920 1570 2860

WW11R - Sample Results in ng/mL

WW11R 9/30/2014 10/28/2014 11/18/2014 12/13/2013 1/30/2014 2/27/2014

PFOA 1720 1100 1320 1060 814 1300

PFBS 299 240 287 198 168 262

PFHS 1000 511 680 512 362 696

PFOS 2200 1670 1850 1570 1540 2100