3M ENVIRONMENTAL LABORATORY

REPORT NO. ISO13-07-08

PAGE 1 OF 23

Final Report

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

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

September 2013

Laboratory Request Number: ISO13-07-08

Method Requirement: 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

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. ISO13-07-08

PAGE 2 OF 23

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 ISO13-07-08

3M Decatur Groundwater Treatment Plant System; September 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 September 30, 2013. 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 ISO13-07-08. Analysis of the 

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

(GPO) number GPO11-1006.

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 surrogates prior to being sent to the 

field for sample collection. 

Samples were prepared and analyzed by method ETS-8-044.1 “Method of Analysis for the 

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

internal standards were used to aid in the data quality objectives. 

Table 1 summarizes the sample results using the analytical 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. ISO13-07-08

PAGE 3 OF 23

Table 1. Sample Results Summary

3M LIMS ID Sample Description

PFOA 

Concentration 

(ng/mL)

PFBS 

Concentration 

(ng/mL)

PFHS 

Concentration 

(ng/mL)

PFOS 

Concentration 

(ng/mL)

ISO13-07-08-001 DAL-GW-ACI; Sample 2280 349 1370 3170

ISO13-07-08-002 DAL-GW-ACI; Sample Dup 2350 363 1420 3310

Average 2320 (1) 356 (1) 1400 (1) 3240 (1)

%RPD Sample/Sample Dup 3.0 3.9 3.6 4.3

ISO13-07-08-004 DAL-GW-ACM2; Sample 1210 468 1550 1.31

ISO13-07-08-005 DAL-GW-ACM2; Sample Dup 1220 471 1570 1.29

Average 1220 (1) 470 (1) 1560 (1) 1.30 (2)

%RPD Sample/Sample Dup 0.82 0.64 1.3 1.5

ISO13-07-08-007 DAL-GW-ACE; Sample 0.109 1920 0.157 0.0419

ISO13-07-08-008 DAL-GW-ACE; Sample Dup 0.121 1980 0.154 0.0485

Average 0.115 (2) 1950 (1) 0.156 (2) 0.0452 (2)

%RPD Sample/Sample Dup 10 3.1 1.9 15

ISO13-07-08-010 DAL-GW-WW8R; Sample 2890 309 1360 4110

ISO13-07-08-011 DAL-GW-WW8R; Sample Dup 2890 296 1370 4090

Average 2890 (1) 303 (1) 1370 (1) 4100 (1)

%RPD Sample/Sample Dup 0.0 4.3 0.73 0.49

ISO13-07-08-013 DAL-GW-WW9R; Sample 2740 252 1230 4130

ISO13-07-08-014 DAL-GW-WW9R; Sample Dup 2720 245 1210 4270

Average 2730 (1) 249 (1) 1220 (1) 4200 (1)

%RPD Sample/Sample Dup 0.73 2.8 1.6 3.3

ISO13-07-08-019 DAL-GW-WW10R; Sample 2040 244 1020 2760

ISO13-07-08-020 DAL-GW-WW10R; Sample Dup 2090 250 1040 2780

Average 2070 (1) 247 (1) 1030 (1) 2770 (1)

%RPD Sample/Sample Dup 2.4 2.4 1.9 0.72

ISO13-07-08-022 DAL-GW-WW11R; Sample 1700 297 1010 2190

ISO13-07-08-023 DAL-GW-WW11R; Sample Dup 1730 301 993 2210

Average 1720 (1) 299 (1) 1000 (1) 2200 (1)

%RPD Sample/Sample Dup 1.7 1.3 1.7 0.91

(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 ±14%, PFBS ±13%, PFHS ±12%, and PFOS ±16%.

(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 ±13%, PFHS ±14%, and PFOS ±15%.
3M ENVIRONMENTAL LABORATORY

REPORT NO. ISO13-07-08

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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 September 30, 2013 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. Collected sample bottles were received by the laboratory at 

ambient conditions on October 9, 2013. The sample bottles for locations ACI, ACM2, ACE, WW8R, 

WW9R and the Trip Blank samples were prepared on August 20, 2013. Sample bottles for locations 

WW10R and WW11R were prepared on September 24, 2013. All sample bottles were prepared with 

spiking solutions that expired on September 29, 2013, just prior to sample collection on September 30, 

2013. A deviation is included with the raw data. 

2.3 Sample Preparation

All samples were diluted with methanol and analyzed for all analytes. Samples diluted 1:10 were 

prepared by removing a 1 mL aliquot of the well mixed sample and adding 8.9 mL of methanol and 0.1 

mL of a surrogate spiking solution. The 1:100 dilutions were prepared by removing a 0.1 mL aliquot of 

the well mixed sample and adding 9.8 mL of methanol and 0.1 mL of a surrogate spiking solution. 

Prepared samples were analyzed by external standard calibration. 

The ACE and ACM2 sample sets and the Trip Blank sample were prepared and analyzed for all 

analytes by transferring an aliquot of the well mixed sample into an autovial. Prepared samples were 

analyzed by internal standard calibration. 

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

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

concentration of 1 ng/mL). The sample bottles for ACE, ACM2, and Trip Blank were spiked with an 

internal standard mix at a nominal concentration of 1 ng/mL prior to being sent to the field for sample 

collection. The laboratory control samples were analyzed in the same manner as the samples. 

2.4 Analysis

All samples and quality control samples were analyzed for 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.
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REPORT NO. ISO13-07-08

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Due to the nature of the sample, the wide range of concentrations found in the sample, and the 

environmental occurrence of multiple isomers of the laboratory’s analytes of interest, the software used 

for processing the analytical results is not able to consistently integrate the analytical peak, manual 

integration of the analytical peak is necessary. All manual integrations are performed following the 

procedures outlined in method ETS-12-010. The consistency of the laboratory’s integration is ensured 

through the training of laboratory personnel, the peer review process required for all manual 

integrations, the review of manual integrations by the QAU, and where necessary the review of manual 

integrations by laboratory management.

Table 3. Instrument Parameters.

Instrument Name ETS Kirk

Analysis Dates

10/15/13 – external standard calibration

10/16/13 – internal standard calibration 

Analytical Method ETS-8-044.1

Liquid Chromatograph Agilent 1260

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

Analytical column Betasil C18 (4.6 mm X 100 mm), 5 μ

Injection Volume 5 or 20 μL

Mass Spectrometer Applied Biosystems TripleQuad 5500

Ion Source Turbo Spray

Polarity Negative

Software 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
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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

NA NA

299/99

PFHS

399/99

[

13C3]PFHS 402/80

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

NA=Not applicable

Dwell time was 20 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 of sampling locations ACM2, ACE, and the Trip Blank sample on 10/16/13.

3 Data Analysis

3.1 Calibration

External Standard Calibration Analysis on 10/15/13: 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 0.02 ng/mL to 50 ng/mL (nominal) were analyzed. The 

standards also contained the surrogates at concentrations ranging from 0.02 ng/mL to 25 ng/mL 

nominal. A quadratic, 1/x weighted, calibration curve of the standard peak area counts was used to fit 

the data for each analyte. The data were not forced through zero during the fitting process. Calculating 

the standard concentrations using the peak area counts and the resultant calibration curve confirmed 

accuracy of each curve point. 

Internal Standard Calibration Analysis on 10/16/13: 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 laboratory prepared reagent water. The calibration standards 

contained an internal standard mix at a nominal concentration of 1 ng/mL. A total of thirteen calibration 

standards ranging from 0.025 ng/mL to 25 ng/mL (nominal) were analyzed with the prepared samples. 

Of these thirteen calibration standards, eleven contained the surrogates at concentrations ranging from 

0.025 ng/mL to 10 ng/mL nominal. A quadratic, 1/x weighted, calibration curve of the ratio of the 

standard peak area counts over the internal standard peak area counts was used to fit the data for 

each analyte. The data were not forced through zero during the fitting process. Calculating the 

standard concentrations using the peak area ratios and the resultant calibration curve confirmed

accuracy of each curve point. 

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.

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 Calibration LOQ, ng/mL 

PFOA Internal standard 0.0240

PFHS Internal standard 0.0400

PFOS Internal standard 0.0232

PFOA External standard 0.0192 (1)

PFBS External standard 0.0200 (1)

PFHS External standard 0.0200 (1)

PFOS External standard 0.0185 (1)

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

3.4 Continuing Calibration 

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

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

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

3.5 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.

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. ISO13-07-08

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Table 7. Lab Control Spike Results.

ETS-8-044.1

External Standard 

Calibration

Analyzed 10/15/13 PFOA (Linear + Branched) PFOA surrogate

Lab ID

Spiked 

Concentration 

(ng/mL)

Calculated 

Concentration 

(ng/mL) %Recovery

Spiked 

Concentration 

(ng/mL)

Calculated 

Concentration 

(ng/mL) %Recovery

LCS-131015-1 0.191 0.200 105 0.199 0.216 109

LCS-131015-2 0.191 0.207 109 0.199 0.219 110

LCS-131015-3 0.191 0.224 117 0.199 0.193 97.2

Average ± %RSD 110% ± 5.6% 105% ± 6.8%

LCS-131015-4 4.74 5.39 114 4.94 5.35 108

LCS-131015-5 4.74 5.36 113 4.94 5.37 109

LCS-131015-6 4.74 5.32 112 4.94 5.43 110

Average ± %RSD 113% ± 0.88% 109% ± 0.92%

LCS-131015-7 38.2 40.8 107

LCS-131015-8 38.2 37.5 98.2

LCS-131015-9 38.2 37.5 98.3

Average ± %RSD 101% ± 5.0%

ETS-8-044.1

External Standard 

Calibration

Analyzed 10/15/13 PFBS PFHS

Lab ID

Spiked 

Concentration 

(ng/mL)

Calculated 

Concentration 

(ng/mL) %Recovery

Spiked 

Concentration 

(ng/mL)

Calculated 

Concentration 

(ng/mL) %Recovery

LCS-131015-1 0.199 0.226 113 0.199 0.220 110

LCS-131015-2 0.199 0.223 112 0.199 0.218 109

LCS-131015-3 0.199 0.235 118 0.199 0.228 115

Average ± %RSD 114% ± 2.8% 111% ± 2.9%

LCS-131015-4 4.95 5.55 112 4.95 5.61 113

LCS-131015-5 4.95 5.61 113 4.95 5.56 112

LCS-131015-6 4.95 5.47 110 4.95 5.50 111

Average ± %RSD 112% ± 1.4% 112% ± 0.89%

LCS-131015-7 39.8 42.6 107 39.8 42.5 107

LCS-131015-8 39.8 38.7 97.2 39.8 39.4 99.1

LCS-131015-9 39.8 38.4 96.4 39.8 38.6 97.0

Average ± %RSD 100% ± 5.9% 101% ± 5.2%
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Table 7 continued. Lab Control Spike Results.

ETS-8-044.1

External Standard 

Calibration

Analyzed 10/15/13 PFOS (Linear + Branched) PFOS surrogate

Lab ID

Spiked 

Concentration 

(ng/mL)

Calculated 

Concentration 

(ng/mL) %Recovery

Spiked 

Concentration 

(ng/mL)

Calculated 

Concentration 

(ng/mL) %Recovery

LCS-131015-1 0.185 0.210 114 0.190 0.206 108

LCS-131015-2 0.185 0.213 115 0.190 0.213 112

LCS-131015-3 0.185 0.217 117 0.190 0.193 101

Average ± %RSD 115% ± 1.3% 107% ± 5.2%

LCS-131015-4 4.59 5.34 116 4.73 5.26 111

LCS-131015-5 4.59 5.28 115 4.73 5.23 111

LCS-131015-6 4.59 5.24 114 4.73 5.30 112

Average ± %RSD 115% ± 0.87% 111% ± 0.52% 

LCS-131015-7 36.9 40.3 109

LCS-131015-8 36.9 37.1 101

LCS-131015-9 36.9 36.4 98.6

Average ± %RSD 103% ± 5.3%

ETS-8-044.1

Internal Standard 

Calibration

Analyzed 10/16/13 PFOA (Linear + Branched) PFOA surrogate

Lab ID

Spiked 

Concentration 

(ng/mL)

Calculated 

Concentration 

(ng/mL) %Recovery

Spiked 

Concentration 

(ng/mL)

Calculated 

Concentration 

(ng/mL) %Recovery

LCS-131016-1 0.190 0.187 98.5 0.198 0.185 93.6

LCS-131016-2 0.190 0.204 107 0.198 0.193 97.5

LCS-131016-3 0.190 0.194 102 0.198 0.195 98.5

Average ± %RSD 103% ± 4.1% 96.5% ± 2.7%

LCS-131016-4 1.90 2.07 109 1.98 2.11 106

LCS-131016-5 1.90 2.01 106 1.98 1.97 99.6

LCS-131016-6 1.90 1.98 104 1.98 1.97 99.6

Average ± %RSD 106% ± 2.4% 102% ± 3.6%

LCS-131016-7 19.0 19.7 104

LCS-131016-8 19.0 18.5 97.6

LCS-131016-9 19.0 19.1 100

Average ± %RSD 101% ± 3.2%
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Table 7 continued. Lab Control Spike Results.

ETS-8-044.1

Internal Standard 

Calibration

Analyzed 10/16/13 PFHS PFOS (Linear + Branched)

Lab ID

Spiked 

Concentration 

(ng/mL)

Calculated 

Concentration 

(ng/mL) %Recovery

Spiked 

Concentration 

(ng/mL)

Calculated 

Concentration 

(ng/mL) %Recovery

LCS-131016-1 0.198 0.200 101 0.184 0.195 106

LCS-131016-2 0.198 0.212 107 0.184 0.202 110

LCS-131016-3 0.198 0.193 97.6 0.184 0.185 100

Average ± %RSD 102% ± 4.7% 105% ± 4.8%

LCS-131016-4 1.98 2.13 108 1.84 1.97 107

LCS-131016-5 1.98 2.09 106 1.84 1.93 105

LCS-131016-6 1.98 1.99 100 1.84 1.92 105

Average ± %RSD 105% ± 4.0% 106% ± 1.1%

LCS-131016-7 19.9 20.9 105 18.4 18.5 100

LCS-131016-8 19.9 19.2 96.6 18.4 17.8 96.7

LCS-131016-9 19.9 19.7 99.0 18.4 17.7 96.0

Average ± %RSD 100% ± 4.3% 97.6% ± 2.2%

ETS-8-044.1

Internal Standard 

Calibration

Analyzed 10/16/13 PFOS surrogate

Lab ID

Spiked 

Concentration 

(ng/mL)

Calculated 

Concentration 

(ng/mL) %Recovery

LCS-131016-1 0.189 0.185 98.0

LCS-131016-2 0.189 0.194 103

LCS-131016-3 0.189 0.200 106

Average ± %RSD 102% ± 4.0%

LCS-131016-4 1.89 1.99 105

LCS-131016-5 1.89 1.83 96.9

LCS-131016-6 1.89 1.93 102

Average ± %RSD 101% ± 4.1%
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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 6.87 ±14%

PFBS External Standard 6.72 ±13%

PFHS External Standard 5.90 ±12%

PFOS External Standard 8.04 ±16%

PFOA Internal Standard 6.43 ±13%

PFHS Internal Standard 7.09 ±14%

PFOS Internal Standard 7.37 ±15%

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 2000 2010 2000 1990

ACM2 Field Matrix Spike 5.00 5.00 5.00 5.00

ACE Field Matrix Spike 5.00 5.00 5.00 5.00

WW8R, WW9R Field Matrix Spike 2510 2510 2500 2490

Trip Blank

Low Field Matrix Spike 5.00 5.00 5.00 5.00

High Field Matrix Spike 2510 2510 2500 2490
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4 Data Summary and Discussion

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

All field matrix spike samples and surrogate recovery standards met method acceptance criteria except 

where noted below.

DAL-GW-ACM2; the FMS sample (5 ng/mL) was not appropriate for PFOA, PFBS, or PFHS; however, 

the surrogate recovery standards 13C4-PFOA and 13C4-PFOS met method acceptance criteria. No 

additional QC samples were prepared. 

DAL-GW-ACE; the FMS sample (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.
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Table 10. DAL GW ACI 130930 (1)

PFOA PFBS

3M LIMS ID Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO13-07-08-001 DAL-GW-ACI-0-130930 2280 NA 349 NA

ISO13-07-08-002 DAL-GW-ACI-DB-130930 2350 NA 363 NA

ISO13-07-08-003 DAL-GW-ACI-FMS-130930 4230 95.5 2310 97.2

Average Concentration (ng/mL) ± %RPD 2320 ng/mL ± 3.0% 356 ng/mL ± 3.9%

PFHS PFOS

3M LIMS ID Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO13-07-08-001 DAL-GW-ACI-0-130930 1370 NA 3170 NA

ISO13-07-08-002 DAL-GW-ACI-DB-130930 1420 NA 3310 NA

ISO13-07-08-003 DAL-GW-ACI-FMS-130930 3700 115 4850 80.9

Average Concentration (ng/mL) ± %RPD 1400 ng/mL ± 3.6% 3240 ng/mL ± 4.3% 

13C4-PFOA 13C4-PFOS

3M LIMS ID Description %Recovery %Recovery

ISO13-07-08-001 DAL-GW-ACI-0-130930 94.9 94.5

ISO13-07-08-002 DAL-GW-ACI-DB-130930 99.5 97.9

ISO13-07-08-003 DAL-GW-ACI-FMS-130930 92.2 95.7

Average Concentration (ng/mL) ± %RSD 95.5% ± 3.9% 96.0% ± 1.8%

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.
3M ENVIRONMENTAL LABORATORY

REPORT NO. ISO13-07-08

PAGE 14 OF 23

Table 11. DAL GW ACM2 130930

PFOA (1) PFBS (1)

3M LIMS ID Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO13-07-08-004 DAL-GW-ACM2-0-130930 1210 NA 468 NA

ISO13-07-08-005 DAL-GW-ACM2-DB-130930 1220 NA 471 NA

ISO13-07-08-006 DAL-GW-ACM2-FMS-130930 1160 NC 442 NC

Average Concentration (ng/mL) ± %RPD 1220 ng/mL ± 0.82% 470 ng/mL ± 0.64%

PFHS (1) PFOS (2)

3M LIMS ID Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO13-07-08-004 DAL-GW-ACM2-0-130930 1550 NA 1.31 NA

ISO13-07-08-005 DAL-GW-ACM2-DB-130930 1570 NA 1.29 NA

ISO13-07-08-006 DAL-GW-ACM2-FMS-130930 1500 NC 6.39 102

Average Concentration (ng/mL) ± %RPD 1560 ng/mL ± 1.3% 1.30 ng/mL ± 1.5%

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

3M LIMS ID Description %Recovery %Recovery

ISO13-07-08-004 DAL-GW-ACM2-0-130930 104 114

ISO13-07-08-005 DAL-GW-ACM2-DB-130930 100 106

ISO13-07-08-006 DAL-GW-ACM2-FMS-130930 96.9 103

Average Concentration (ng/mL) ± %RSD 100% ± 3.6% 108% ± 5.3%

NA = Not Applicable

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

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

added to the samples during sample preparation.

(2) Samples were analyzed by internal standard calibration.
3M ENVIRONMENTAL LABORATORY

REPORT NO. ISO13-07-08

PAGE 15 OF 23

Table 12. DAL GW ACE 130930

PFOA (1) PFBS (2)

3M LIMS ID Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO13-07-08-007 DAL-GW-ACE-0-130930 0.109 NA 1920 NA

ISO13-07-08-008 DAL-GW-ACE-DB-130930 0.121 NA 1980 NA

ISO13-07-08-009 DAL-GW-ACE-FMS-130930 4.95 96.7 1970 NC

Average Concentration (ng/mL) ± %RPD 0.115 ng/mL ± 10% 1950 ng/mL ± 3.1%

PFHS (1) PFOS (1)

3M LIMS ID Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO13-07-08-007 DAL-GW-ACE-0-130930 0.157 NA 0.0419 NA

ISO13-07-08-008 DAL-GW-ACE-DB-130930 0.154 NA 0.0485 NA

ISO13-07-08-009 DAL-GW-ACE-FMS-130930 5.05 97.9 5.12 101

Average Concentration (ng/mL) ± %RPD 0.156 ng/mL ± 1.9% 0.0452 ng/mL ± 15%

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

3M LIMS ID Description %Recovery %Recovery

ISO13-07-08-007 DAL-GW-ACE-0-130930 84.3 90.7

ISO13-07-08-008 DAL-GW-ACE-DB-130930 94.4 99.5

ISO13-07-08-009 DAL-GW-ACE-FMS-130930 95.9 105

Average Concentration (ng/mL) ± %RSD 91.5% ± 6.9% 98.4% ± 7.3%

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 standards 13C4-PFOA and 13C4-PFOS were 

added to the samples during sample preparation.
3M ENVIRONMENTAL LABORATORY

REPORT NO. ISO13-07-08

PAGE 16 OF 23

Table 13. DAL GW WW8R 130930 (1)

PFOA PFBS

3M LIMS ID Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO13-07-08-010 DAL-GW-WW8R-0-130930 2890 NA 309 NA

ISO13-07-08-011 DAL-GW-WW8R-DB-130930 2890 NA 296 NA

ISO13-07-08-012 DAL-GW-WW8R-FMS-130930 5380 99.2 2740 97.1

Average Concentration (ng/mL) ± %RPD 2890 ng/mL ± 0.0% 303 ng/mL ± 4.3%

PFHS PFOS

3M LIMS ID Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO13-07-08-010 DAL-GW-WW8R-0-130930 1360 NA 4110 NA

ISO13-07-08-011 DAL-GW-WW8R-DB-130930 1370 NA 4090 NA

ISO13-07-08-012 DAL-GW-WW8R-FMS-130930 3920 102 6830 110

Average Concentration (ng/mL) ± %RPD 1370 ng/mL ± 0.73% 4100 ng/mL ± 0.49%

13C4-PFOA 13C4-PFOS

3M LIMS ID Description %Recovery %Recovery

ISO13-07-08-010 DAL-GW-WW8R-0-130930 94.2 96.3

ISO13-07-08-011 DAL-GW-WW8R-DB-130930 94.5 96.1

ISO13-07-08-012 DAL-GW-WW8R-FMS-130930 94.9 91.7

Average Concentration (ng/mL) ± %RSD 94.5% ± 0.37% 94.7% ± 2.7%

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.
3M ENVIRONMENTAL LABORATORY

REPORT NO. ISO13-07-08

PAGE 17 OF 23

Table 14. DAL GW WW9R 130930 (1)

PFOA PFBS

3M LIMS ID Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO13-07-08-013 DAL-GW-WW9R-0-130930 2740 NA 252 NA

ISO13-07-08-014 DAL-GW-WW9R-DB-130930 2720 NA 245 NA

ISO13-07-08-015 DAL-GW-WW9R-FMS-130930 5410 107 2810 102

Average Concentration (ng/mL) ± %RPD 2730 ng/mL ± 0.73% 249 ng/mL ± 2.8%

PFHS PFOS

3M LIMS ID Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO13-07-08-013 DAL-GW-WW9R-0-130930 1230 NA 4130 NA

ISO13-07-08-014 DAL-GW-WW9R-DB-130930 1210 NA 4270 NA

ISO13-07-08-015 DAL-GW-WW9R-FMS-130930 3930 108 7200 120

Average Concentration (ng/mL) ± %RPD 1220 ng/mL ± 1.6% 4200 ng/mL ± 3.3%

13C4-PFOA 13C4-PFOS

3M LIMS ID Description %Recovery %Recovery

ISO13-07-08-013 DAL-GW-WW9R-0-130930 94.7 94.6

ISO13-07-08-014 DAL-GW-WW9R-DB-130930 94.9 98.2

ISO13-07-08-015 DAL-GW-WW9R-FMS-130930 99.1 95.3

Average Concentration (ng/mL) ± %RSD 96.2% ± 2.6% 96.0% ± 2.0%

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.
3M ENVIRONMENTAL LABORATORY

REPORT NO. ISO13-07-08

PAGE 18 OF 23

Table 15. DAL GW WW10R 130930 (1)

PFOA PFBS

3M LIMS ID Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO13-07-08-019 DAL-GW-WW10R-0-130930 2040 NA 244 NA

ISO13-07-08-020 DAL-GW-WW10R-DB-130930 2090 NA 250 NA

ISO13-07-08-021 DAL-GW-WW10R-FMS-130930 4570 99.6 2670 96.5

Average Concentration (ng/mL) ± %RPD 2070 ng/mL ± 2.4% 247 ng/mL ± 2.4%

PFHS PFOS

3M LIMS ID Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO13-07-08-019 DAL-GW-WW10R-0-130930 1020 NA 2760 NA

ISO13-07-08-020 DAL-GW-WW10R-DB-130930 1040 NA 2780 NA

ISO13-07-08-021 DAL-GW-WW10R-FMS-130930 3550 101 5350 104

Average Concentration (ng/mL) ± %RPD 1030 ng/mL ± 1.9% 2770 ng/mL ± 0.72%

13C4-PFOA 13C4-PFOS

3M LIMS ID Description %Recovery %Recovery

ISO13-07-08-019 DAL-GW-WW10R-0-130930 96.5 99.8

ISO13-07-08-020 DAL-GW-WW10R-DB-130930 101 107

ISO13-07-08-021 DAL-GW-WW10R-FMS-130930 96.1 99.9

Average Concentration (ng/mL) ± %RSD 97.9% ± 2.8% 102% ± 4.0%

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.
3M ENVIRONMENTAL LABORATORY

REPORT NO. ISO13-07-08

PAGE 19 OF 23

Table 16. DAL GW WW11R 130930 (1)

PFOA PFBS

3M LIMS ID Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO13-07-08-022 DAL-GW-WW11R-0-130930 1700 NA 297 NA

ISO13-07-08-023 DAL-GW-WW11R-DB-130930 1730 NA 301 NA

ISO13-07-08-024 DAL-GW-WW11R-FMS-130930 4160 97.2 2660 94.1

Average Concentration (ng/mL) ± %RPD 1720 ng/mL ± 1.7% 299 ng/mL ± 1.3%

PFHS PFOS

3M LIMS ID Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO13-07-08-022 DAL-GW-WW11R-0-130930 1010 NA 2190 NA

ISO13-07-08-023 DAL-GW-WW11R-DB-130930 993 NA 2210 NA

ISO13-07-08-024 DAL-GW-WW11R-FMS-130930 3490 99.6 4610 96.8

Average Concentration (ng/mL) ± %RPD 1000 ng/mL ± 1.7% 2200 ng/mL ± 0.91%

13C4-PFOA 13C4-PFOS

3M LIMS ID Description %Recovery %Recovery

ISO13-07-08-022 DAL-GW-WW11R-0-130930 100 104

ISO13-07-08-023 DAL-GW-WW11R-DB-130930 101 104

ISO13-07-08-024 DAL-GW-WW11R-FMS-130930 96.3 96.8

Average Concentration (ng/mL) ± %RSD 99.1% ± 2.5% 102% ± 4.1%

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.
3M ENVIRONMENTAL LABORATORY

REPORT NO. ISO13-07-08

PAGE 20 OF 23

Table 17. Trip Blank Results

PFOA PFBS

3M LIMS ID Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO13-07-08-016 DAL-GW-TRIP01-0-130930 <0.0240 (1) NA <0.200 (2) NA

ISO13-07-08-017 DAL-GW-TRIP01-LS-130930 5.04 (2) 101 5.06 (2) 101

ISO13-07-08-018 DAL-GW-TRIP01-HS-130930 2870 (2) 114 2690 (2) 107

PFHS PFOS

3M LIMS ID Description

Concentration 

(ng/mL) %Recovery

Concentration 

(ng/mL) %Recovery

ISO13-07-08-016 DAL-GW-TRIP01-0-130930 <0.400 (1) NA <0.0232 (1) NA

ISO13-07-08-017 DAL-GW-TRIP01-LS-130930 5.17 (2) 103 5.40 (2) 108

ISO13-07-08-018 DAL-GW-TRIP01-HS-130930 2740 (2) 110 2900 (2) 116

13C4-PFOA 13C4-PFOS

3M LIMS ID Description %Recovery %Recovery

ISO13-07-08-016 DAL-GW-TRIP01-0-130930 94.2 (1) 105 (1)

ISO13-07-08-017 DAL-GW-TRIP01-LS-130930 102 (2) 108 (2)

ISO13-07-08-018 DAL-GW-TRIP01-HS-130930 101 (2) 105 (2)

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.
3M ENVIRONMENTAL LABORATORY 

REPORT NO. /SO ^ 3-07-08 

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 Periluorinated 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 select sampling points at the Decatur Ground Water Treatment 

Plant (GWTP) GAC System. 

8 Signatures 

llh/lS 

Susan T. Wolf, 3IV(P,cincipal Analytical Investigator Date 

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

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

project. 

Quality Assurance R^r^entative Date 

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

Environmental Laboratory. 

PAGE 21 OF 23 
3M ENVIRONMENTAL LABORATORY

REPORT NO. ISO13-07-08

PAGE 22 OF 23

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

Plant (GWTP) GAC System 

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

ACI 6/29/12 8/28/12 12/14/12 1/17/13 2/13/13 3/27/13 4/29/13 5/31/13 6/27/13 7/23/13 9/30/13

PFOA 1650 1410 2580 1910 2300 2220 1480 1860 1480 1630 2320

PFBS 1410 1830 723 588 830 1060 1360 1040 708 1230 356

PFHS 1460 1390 1380 895 1580 1090 777 940 942 749 1400

PFOS 964 172 2810 1810 2940 2490 1670 2150 1590 1680 3240

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

ACE 8/28/12 12/14/12 1/17/13 2/13/13 3/27/13 4/29/13 5/31/13 6/27/13 7/23/13 9/30/13

PFOA 0.387 0.102 <0.0240 0.124 0.0380 0.0422 0.0725 0.0717 0.0643 0.115

PFBS 0.256 <0.0250 <0.0250 0.0360 <0.0250 0.392 24.8 111 1960 1950

PFHS 0.552 0.117 <0.0250 0.178 0.0477 0.057 0.105 0.118 0.0778 0.156

PFOS 0.103 0.0376 <0.0232 0.0329 <0.0232 <0.0232 <0.0232 <0.0232 0.0277 0.0452

The ACE location was not sampled on 6/29/12.
3M ENVIRONMENTAL LABORATORY

REPORT NO. ISO13-07-08

PAGE 23 OF 23

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

Plant (GWTP) GAC System 

WW8R - Sample Results in ng/mL

WW8R 12/13/12 1/17/13 2/13/13 3/27/13 4/29/13 5/31/13 6/27/13 7/23/13 9/30/13

PFOA 3630 4350 3250 3640 3190 2760 2760 2640 2890

PFBS 441 410 354 385 364 289 282 263 303

PFHS 1740 1930 1900 1760 1610 1330 1340 1260 1370

PFOS 4920 5710 4850 5120 4830 4180 4110 3910 4100

WW9R - Sample Results in ng/mL

WW9R 12/13/12 1/17/13 2/13/13 3/27/13 4/29/13 5/31/13 6/27/13 7/23/13 9/30/13

PFOA 3360 2710 2850 3330 2650 2660 2630 2410 2730

PFBS 321 184 236 278 244 226 225 212 249

PFHS 1480 954 1400 1440 1200 1120 1140 1030 1220

PFOS 4080 3690 4100 4660 4340 4210 4150 3670 4200