3 

GLP10-01-01 Interim Report 25: Analysis for PFOA in Potting Soils Used for

a PFOA Vegetative Uptake Study with Turnip Greens

Study Title

3M Environmental Laboratory Analytical Protocol GLP10-01-01: Analysis of Perfluorooctanoic 

Acid (PFOA) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related 

Monitoring Program 

Data Requirement

EPA TSCA Good Laboratory Practice Standards 40 CFR Part 792 

Study Director

Jaisimha Kesari P.E., DEE 

Weston Solutions, Inc. 

1400 Weston Way 

West Chester, PA 19380 

Phone: 610-701-3761 

Principal Analytical Investigator

Cleston C. Lange, Ph.D. 

3M Environmental Laboratory 

Interim Report Completion Date 

Upon Signing 

Performing Laboratory 

3M Environmental Health and Safety Operations 

Environmental Laboratory 

3M Center, Bldg 260-05-N-17 

St. Paul, MN 55144 

Project Identification

GLP10-01-01-25 

Total Number of Pages 

20
Study: GLP10-01-01, Interim Report 25 

Analysis for PFOA in Potting Soils Used for a Vegetative Uptake Study with Turnip Greens

Page 2 of 20

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Study: GLP10-01-01, Interim Report 25 

Analysis for PFOA in Potting Soils Used for a Vegetative Uptake Study with Turnip Greens 

GLP COMPLIANCE STATEMENT 

Report Title: GLP10-01-01 Interim Report 25: Analysis for PFOA in Potting Soils Used for a 

PFOA Vegetative Uptake Study with Turnip Greens. 3M Environmental Laboratory Analytical 

Protocol GLP10-01-01: Analysis of Perfluorooctanoic Acid (PFOA) in Groundwater, Soil and 

Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program. 

This analytical phase was conducted in compliance with Toxic Substances Control Act 

(TSCA) Good Laboratory Practice (GLP) Standards, 40 CFR 792, with the exceptions listed 

below: 

Exceptions to GLP compliance: 

The analytical reference substances were not all characterized under GLPs. 

Samples are environmental samples; there was no dosing and no specific test substance or 

control substance for this study and only analytical reference substances. 

Gary Hobjfenstein, Sponsor Representative 

Date 

Jaisimha Kesari, P.E., DEE, Study Director 

Date 

Page 3 of 20 
study GLP10-01-01, Interim Report 25 

Analysis for PFOA in Potting Soils Used for a Vegetative Uptake Study with Turnip Greens 

QUALITY ASSURANCE STATEMENT 

Report Title: GLP10-01-01 Interim Report 25: Analysis for PFOA in Potting Soils Used for a 

PFOA Vegetative Uptake Study with Turnip Greens. 3M Environmental Laboratory Analytical 

Protocol GLP10-01-01: Analysis of Perfluorooctanoic Acid (PFOA) in Groundwater, Soil and 

Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program. 

This interim study report and the accompanying data were audited by the 3M Environmental 

Laboratory Quality Assurance Unit (QAU), as indicated below. The findings were reported to the 

principal investigator (P.I.), laboratory management and study director. 

study Inspection 

Dates 

Date Reported to 

study Inspection 

Dates 

Phase P.I. Study Director 

iVIanagement 

study Director 

Jan 12,13&16,2012 Interim Report 

and Data 

Jan. 19,2012 Jan 26,2012 Jan 26, 2012 

/•-lt>^ €^ a-iQAU Representative Date 

Page 4 of 20 
Study: GLP10-01-01, Interim Report 25 

Analysis for PFOA in Potting Soils Used for a Vegetative Uptake Study with Turnip Greens

Page 5 of 20

TABLE OF CONTENTS

GLP Compliance Statement ...................................................................................................................... 3

Quality Assurance Statement .................................................................................................................... 4

Table of Contents ....................................................................................................................................... 5

List of Tables ............................................................................................................................................... 6

1 Study Information ................................................................................................................................ 7

2 Summary ............................................................................................................................................. 8

3 Introduction .......................................................................................................................................... 9

4 Test, Control and Reference Substances .......................................................................................... 9

5 Test System ....................................................................................................................................... 10

6 Method Summary .............................................................................................................................. 10

6.1 Methods ................................................................................................................................ 10

6.2 Sample Receipt .................................................................................................................... 10

6.3 Sample Preparation .............................................................................................................. 10

6.4 Percent Soil Moisture Determination ................................................................................... 11

6.5 LC/MS/MS Analysis .............................................................................................................. 11

7 Analytical Results .............................................................................................................................. 13

7.1 Calibration ............................................................................................................................. 13

7.2 Limits of Quantitation (LOQs) .............................................................................................. 14

7.3 Continuing Calibration .......................................................................................................... 14

7.4 Blanks .................................................................................................................................... 14

7.5 Laboratory Control Spikes (LCSs) ....................................................................................... 15

7.6 Laboratory Matrix Spikes (LMSs) ........................................................................................ 15

7.7 Percent Moisture Determinations ........................................................................................ 16

7.8 Individual Sample Results .................................................................................................... 17
Study: GLP10-01-01, Interim Report 25 

Analysis for PFOA in Potting Soils Used for a Vegetative Uptake Study with Turnip Greens

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8 Conclusion ......................................................................................................................................... 18

9 Data/Sample Retention ..................................................................................................................... 19

10 List of Attachments ............................................................................................................................ 19

11 Signatures .......................................................................................................................................... 19

LIST OF TABLES

Table 1. PFOA Results: Potting Soils for Vegetative Uptake in Turnip Greens (December 2011) ..... 8

Table 2. Reference Substances ............................................................................................................... 9

Table 3. Instrument Information .............................................................................................................. 12

Table 4. Gradient Liquid Chromatography Conditions (ETS-8-053)..................................................... 12

Table 5. Mass Transitions ....................................................................................................................... 12

Table 6. PFOA Calibration Summary (Calibrated with linear PFOA) ................................................... 13

Table 7. 13C4-PFOA (SRS) Calibration Summary .................................................................................. 14

Table 8. LCS Results ............................................................................................................................... 15

Table 9. Percent Moisture Results for Soils from PFOA Vegetative Uptake Study with Turnip 

Greens (December 2011) ................................................................................................................. 16

Table 10. Individual PFOA Results for Potting Soils for Turnip Greens (December 2011) ................. 17
Study: GLP10-01-01, Interim Report 25 

Analysis for PFOA in Potting Soils Used for a Vegetative Uptake Study with Turnip Greens

Page 7 of 20

1 Study Information 

Sponsor 

3M Company 

Sponsor Representative 

Gary A. Hohenstein 

Environmental Manager 

Special Projects, EHS Operations 

Bldg 224-5W-03 

St. Paul, MN 55144 

Phone: (651) 737-3570 

gahohenstein@mmm.com

Study Director

Jaisimha Kesari, P.E., DEE 

Weston Solutions, Inc. 

1400 Weston Way 

West Chester, PA 19380 

Study Analytical Testing Facility 

3M EHS Operations 

Environmental Laboratory 

Building 260-5N-17 

St. Paul, MN 55144 

Study Personnel (3M Environmental Laboratory) 

Cleston C. Lange, Ph.D., Principal Analytical Investigator 

William K. Reagen, Ph.D., Laboratory Manager 

Patrick Kenney, Laboratory Technician (Pace Analytical, Professional Services) 

Marlene Heying, Laboratory Technician (Pace Analytical, Professional Services) 

Study Dates 

Study Initiation: March 08, 2010 

Interim Analytical Initiation: December 08, 2011 

Interim Analytical Completion: December 28, 2011 

Interim Report Completion: Upon final Signatures 

Location of Archives 

All original raw data and analytical reports have been archived at the 3M Environmental 

Laboratory according to 40 CFR Part 792. The test substance and analytical reference 

standard reserve samples are archived at the 3M Environmental Laboratory according to 40 

CFR Part 79
Study: GLP10-01-01, Interim Report 25 

Analysis for PFOA in Soils Used for a Vegetative Uptake Study with Turnip Greens

Page 8 of 20

2 Summary 

Reported herein are the PFOA concentrations determined for fourteen potting soils used for a PFOA 

vegetative uptake study with turnip greens. Results for a travel blank (trip blank) containing a control soil 

TCR-455 in a sealed sample bottle that traveled with the sample bottles to and from the site and an 

equipment rinseate sample are also reported. Samples were received in December 2011 and logged into 

the 3M Environmental Laboratory LIMS system under project GLP10-01-01-25. The samples were 

extracted and analyzed as a single analytical batch with matrix matched soil calibration standards, blanks 

and laboratory control samples (LCSs). For preparation of each sample, four aliquots of soil were 

removed from each sample bottle, transferred to a centrifuge tube and accurately weighed and fortified

with a fixed amount of internal standard (IS). The first and second aliquot served as analytical sample and 

sample duplicate for determining PFOA in the sample. The third and fourth replicates were fortified with 

nominal 1.00 and 10.0 ng of PFOA as a low laboratory matrix spike (LMS) and high LMS respectively, to 

evaluate PFOA recovery. A single LMS was prepared for the trip blank and was fortified with nominal 1.00 

ng of PFOA. Sample aliquots were extracted and then analyzed by liquid chromatography with triple 

quadrapole mass spectrometric detection (LC/MS/MS). Quantitation of PFOA was performed by internal 

standard method. The recovery of fortified PFOA from LMSs was used as a measure of sample data 

accuracy. The %RPD of the duplicate analytical sample results was used to assess the precision of the

sample results. The percent moisture of each soil was determined for reporting PFOA concentrations on

a dry weight basis. The PFOA concentrations, %RPDs and LMS recoveries are summarized in Table 1. 

Based on LMS results, the data accuracy was within 100 + 26%, except for one sample which had a data 

accuracy of158%. Excellent precision was demonstrated with RPDs <10% for each duplicate set of 

results. The method uncertainty (95% CI) was determined at + 9.0% based on LCS results. 

Table 1. PFOA Results: Potting Soils for Vegetative Uptake in Turnip Greens (December 2011) 

3M LIMS ID Sample ID 

Average Soil PFOA 

Concentration 

 (ng/g; dry wt.) 

%RPD LMS PFOA Fortified 

Amount [a] LMS Recovery [a]

GLP10-01-01-25-001 DAL SS CONT POT 0 0 111214 BLQ N/A 0.933 112% [c]

GLP10-01-01-25-002 DAL SS 025 POT 0 0 111214 0.409 9.1% 0.860 101% [c]

GLP10-01-01-25-003 DAL SS 050 POT 0 0 111214 0.887 5.7% 0.880 97.3% [c]

GLP10-01-01-25-004 DAL SS 100 POT 0 0 111214 1.66 3.7% 0.889 , 8.55 112% [c], 112% [d]

GLP10-01-01-25-005 DAL SS 200 POT 0 0 111214 3.77 4.0% 8.49 102% [d]

GLP10-01-01-25-006 DAL SS 400 POT 0 0 111214 6.69 2.3% 9.21 101% [d]

GLP10-01-01-25-007 DAL SS 800 POT 0 0 111214 14.9 4.4% 7.38 88.6% [d]

GLP10-01-01-25-008 DAL SS CONT TG1 0 111214 BLQ N/A 0.923 107% [c]

GLP10-01-01-25-009 DAL SS 025 TG1 0 111214 0.639 2.8% 0.980 102% [c]

GLP10-01-01-25-010 DAL SS 050 TG1 0 111214 0.999 6.9% 0.868 , 9.99 103% [c], 104% [d]

GLP10-01-01-25-011 DAL SS 100 TG1 0 111214 2.02 3.4% 0.973 107% [d]

GLP10-01-01-25-012 DAL SS 200 TG1 0 111214 3.46 4.1% 9.98 103% [d]

GLP10-01-01-25-013 DAL SS 400 TG1 0 111214 9.40 5.1% 8.30 74.8% [d]

GLP10-01-01-25-014 DAL SS 800 TG1 0 111214 13.5 [b] 3.3% 10.6 158% [d]

GLP10-01-01-25-016 TRIP BLANK-1 BLQ N/A 1.02 106% [c]

GLP10-01-01-25-015 DAL SS 800TG1 RB 111214 <0.287 ng/mL [e] N/A N/A N/A 

[a] Two LMSs were prepared at different levels, but recovery is shown for the one LMS fortified with PFOA at a level most similar to the 

endogenous level. 

[b] LMS recovery (data accuracy) for the sample was 158%, and outside of 100 + 30%. 

BLQ; The integrated peak area response for PFOA in the sample was below the response of the nominal 0.200 ng/g calibration standard 

N/A; not applicable since result was BLQ. 

[c] LMS recovery value shown is for the nominal 1.00 ng fortified LMS 

[d] LMS recovery value shown is for the nominal 10.0 ng fortified LMS 

[e] The aqueous equipment rinseate blank was analyzed by method ETS-8-044.1 with an LLOQ of 0.0287 ng/mL 
Study: GLP10-01-01, Interim Report 25 

Analysis for PFOA in Soils Used for a Vegetative Uptake Study with Turnip Greens

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3 Introduction 

The soil analysis results reported herein were conducted as part of the Phase 3 Environmental 

Monitoring and Assessment Program for the 3M facility located in Decatur, Alabama. The objective 

of the overall program is to gain information regarding concentrations of perfluorooctanoate (PFOA) 

in various environmental media such as groundwater, soils and sediments that are associated with 

and near the Decatur facility. Reported herein are the results from analysis of potting soils used for 

planting of turnip/turnip greens as part of a PFOA vegetative uptake study GLP10-01-03. The 

samples were prepared and collected by Weston Solutions, Inc. personnel and shipped to the 3M 

Environmental Laboratory for quantitative analysis of PFOA in December 2011. One soil travel 

blank (trip blank) which accompanied the sample bottle shipment was also analyzed and the PFOA 

results reported herein. 

This report describes the sample shipment, receipt, extraction and quantitative LC/MS/MS analysis 

procedures conducted for determination of PFOA in the potting soils as project GLP10-01-01-25. 

Additionally, included in this report are the assessment of the sample-specific analytical precision and 

accuracy for the reported PFOA concentration results and the determined percent moisture content 

of each soil was determined and is reported. Additionally included are the recovery results for 13C4-

PFOA as a surrogate recovery standard (SRS) that was added to each soil aliquot prior to extraction 

and was included as part of a method validation study for method ETS-8-053 to evaluate SRS 

recovery in environmental samples, and was not used for assessment of the data for this study. 

4 Reference Substances 

This study does not have a test substance or control substance in the classic sense of a GLP study 

as it would be used in an eco-toxicological study. This evaluation was purely analytical in nature and 

was not the dosing study. The reference and control substances are listed in Table 2. 

Table 2. Reference Substances 

Test 

Substance 

PFOA (linear 

isomer), free acid 

PFOA (linear + 

branched 

isomers), 

ammonium salt 

13C4-PFOA 13C8-PFOA 

Use Calibration & LMSs LCSs SRS IS 

Source Oakwood 3M Wellington Labs Wellington Labs 

Expiration Date 9/29/2012 2/27/2017 10/22/2012 10/22/2012 

Storage 

Conditions Frozen Frozen Frozen Frozen 

Chemical Lot 3440 332 MPFOA1009 M8PFOA0408 

TCR Number TCR07-0041 1/1 TCR-123 TCR09-0075 2/9 TCR09-0067 5/9 

Physical 

Description Powder White Powder Methanol Solution [a]

Methanol Solution 

[a]

Purity 99.5% 95% >98% 97.9% 

[a] Stable isotope labeled materials are typically provided as methanol solutions by the vendor (source) and are 

treated as 100% pure; the vendor’s reported methanol stock concentration is used for calculating concentrations of 

diluted standards made from them 
Study: GLP10-01-01, Interim Report 25 

Analysis for PFOA in Soils Used for a Vegetative Uptake Study with Turnip Greens

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5 Test System 

There was not a test system for this study in the classic sense of a GLP study since this aspect 

reported here was purely analytical. 

6 Method Summary 

6.1 Methods 

Soil extractions and quantitative LC/MS/MS analysis were performed following validated method 

ETS-8-053.0. The analysis of soils for reporting these results was performed on December 23, 2011 as 

analytical run s111223a. The analysis of the aqueous equipment rinseate was by following method ETS8-044.1 and was performed on December 28 as analytical run mc111228a. The analysis parameters 

and QC results for the water analysis are omitted from this report but are contained in a condensed 

summary report and will be maintained within the data package for this soil analysis project. Only the 

PFOA concentration result for the equipment rinseate was reported herein, in Table 1. 

6.2 Sample Receipt 

On December 8, 2011 fifteen (15) empty 250-mL HDPE NalgeneTM sample bottles, two 500-mL 

bottles of Milli-QTM water for use in equipment rinsing, and one travel blank (trip blank) containing 

approximately 25 grams of a control soil TCR-455, were sent from the 3M Environmental 

Laboratory to Weston Solutions, Inc. field personnel for collection of potting soils. Following the

soil sample collections by Weston Solutions, Inc. personnel, fourteen (14) soil-filled sample 

bottles, one equipment rinse blank (aqueous) and the one soil trip blank were returned back to the 

laboratory for analysis. The samples were received with sample chains of custody numbers 16915 

and 16916 on December 20, 2011. The samples were logged into the 3M LIMS under project 

GLP10-01-01-25. Samples were stored refrigerated until they could be extracted and analyzed. 

Soil samples from Decatur, AL are regulated and were appropriately shipped in accordance with 

USDA/APHIS soil permit number P330-09-00125. 

Sample nomenclature follows the form DAL-SS-xxxxxxx-xx-xxxx where the first string defines the 

Decatur Alabama (DAL) project area, the second string defines the sample media (i.e., SS = soil 

sample), the third string defines the targeted level of PFOA for the potting soil (i.e., CONT = control, 025 

= 0.25 ng/g target concentration, etc.), the vegetation type planted (POT = potato, TG = turnip green and 

TOM = tomato) and whether an initial (0) or final (1) sample, the fourth string defines the sample type (0 

= primary sample, DB = field duplicate, RB = equipment rinseate blank). The fifth string indicates the

sampling date in YYMMDD format (i.e., 111214 = December 14, 2011). 

6.3 Sample Preparation 

Sample preparation (extraction) for soils was conducted as a single analytical batch from December 21-

22, 2011. The analytical batch was analyzed as analytical run s111223a. 

Each soil extraction involved removal of a 1 cubic centimeter (1 cc; 1 mL) soil aliquot (typically ~ 1 gram) 

from each sample bottle using a fixed volume 1 cc spoon, transferring it to a 15 mL conical centrifuge

tube, followed by accurate weight determination of the aliquot on a 5-place balance. Then, nominal 3.0 

ng of internal standard (IS; nominal 3.0 ng) was added to each soil aliquot. Then the soil aliquot was 

extracted by addition of 8 mL of a 4:1 acetonitrile:water solution followed by brief mixing and sonication 

for 1 hour, then centrifugation to remove solids. The supernatant from each was then transferred to an 
Study: GLP10-01-01, Interim Report 25 

Analysis for PFOA in Soils Used for a Vegetative Uptake Study with Turnip Greens

Page 11 of 20

autovial for analysis. An accurately measured volume of each supernatant was analyzed by LC/MS/MS. 

Each analytical sample was prepared in quadruplicate, with the first and second samples being the 

sample and duplicate sample, and the third and fourth replicates fortified with 1.00 ng and 10.0 ng of

PFOA as a low-LMS and high LMS, respectively. For each LMS preparation, the PFOA fortified was the 

predominantly linear isomer. The trip blank was prepared in triplicate, with sample, sample duplicate and 

one LMS fortified with 1.00 ng PFOA (linear isomer)

Calibration standards were prepared by spiking known quantities of PFOA (linear isomer) into 1-cubic 

centimeter (1 cc, 1 mL) aliquots of 3M Environmental Laboratory control soil TCR-455. The nominal 

mass of 1 cc of control soil TCR-455 is 1.0-1.1 gram (dry). The nominal calibration standard soil 

concentration range was 0.200 ng/g to 200 ng/g based on a nominal dry weight of 1.0 gram for TCR455. 

During preparation, each soil aliquot received nominal 3.0 ng of 13C4-PFOA as a stable isotope labeled 

surrogate recovery standard (SRS). Although not included as part of the data accuracy assessment for

this study, SRS recovery determinations were included as part of an ongoing method validation aspect 

for SRS behavior in environmental soil samples for potential future applications. The SRS was 

quantified from a SRS calibration curve constructed from analysis of calibration standards prepared from 

the SRS in calibration standards. The SRS recovery was determined based on the calculated 

concentration of SRS from the analysis and recovery of SRS from each sample is included in Table 9, 

but was not used for evaluation of data accuracy for this study and is otherwise excluded from the 

discussions in the report. 

Laboratory control spike (LCS) samples were prepared with each sample preparation batch; prepared at 

two levels (nominal 3.0 ng/g and 30 ng/g) and each level in triplicate. Each LCS received 3.00 ng of 

13C4-PFOA (SRS). The LCSs were prepared using control soil TCR-455, same as calibration standards, 

and were fortified with PFOA (linear isomer). 

6.4 Percent Soil Moisture Determination 

The percent moisture of soils was used to calculate the dry weight of the wet soils weighed during 

sample preparations for PFOA analysis, and was determined by gravimetric analysis. Dry weights were 

determined for separate weighings than the weighings used for PFOA extraction and analysis 

procedures. To determine the percent moisture, duplicate aliquots of each soil sample were removed 

and the accurate “wet” weight determined for each. All aliquots were dried at > 100°C until no further 

mass loss occurred from water evaporation, at which time the accurate dried weights were determined. 

The difference in mass, attributed to water evaporation, was used to calculate the percent moisture of

the original soil. The averaged percent moisture result for each was then used to calculate the soil 

PFOA concentration on a dry weight basis, and is reported for each soil in Table 9. 

6.5 LC/MS/MS Analysis 

The LC/MS/MS analysis of the analytical batch was conducted on December 23, 2011 as analytical 

run s111223a and was performed by as described in method ETS-8-053.0 

The relative percent difference (RPD) of the duplicate sample results was used as a measure of 

the analytical precision. The determined recovery of fortified PFOA from the LMS samples was 

used as a measure of sample-specific analytical accuracy. Recovery of the surrogate (13C4-PFOA) 

in samples is included within this report in Table 10 as an indirect measure of analytical data 

accuracy, and was not considered in the accuracy assessment for this study and is only included 

as part of an on-going method validation aspect in which surrogate recovery behavior is being 

evaluated in “real world” environmental samples for possible future applications. 

Details of the specific instrument parameters, the liquid chromatography gradient program, and the 

specific mass transitions analyzed are detailed in the raw data, and are briefly described below in 

Table 3, Table 4 and Table 5. 
Study: GLP10-01-01, Interim Report 25 

Analysis for PFOA in Soils Used for a Vegetative Uptake Study with Turnip Greens

Page 12 of 20

Table 3. Instrument Information 

Instrument Name ETS-Stan 

Analytical Method ID ETS-8-053.0 

Liquid Chromatograph Agilent 1100 with Binary Pump 

Guard column Pre-Autosampler; Prism RP (2.1 x 50 mm, 5 μ) 

Extraction column Betasil C18 (2.1 x 100 mm, 5μ) 

Analytical column Oasis HLB (3 x 20 mm, 25 μ); 30°C 

Injection Volume 25 μL 

Mass Spectrometer API 4000 

Ion Source TurboIon Spray 

Polarity Negative 

Software Analyst 1.4.2 

Table 4. Gradient Liquid Chromatography Conditions (ETS-8-053) 

Step 

Number 

Total Time 

[min] 

Flow Rate 

[mL/min] 

Percent A 

[2 mm Aqueous 

Ammonium Acetate] 

Percent B 

[ Acetonitrile] 

1 0.0 0.400 97.0 3.0 

2 3.0 0.400 97.0 3.0 

3 3.5 0.400 70.0 30.0 

4 17.0 0.400 40.0 60.0 

5 17.5 0.400 10.0 90.0 

6 19.5 0.400 10.0 90.0 

7 20.0 0.400 97.0 3.0 

8 23.0 0.400 97.0 3.0 

Table 5. Mass Transitions 

Analyte Mass Transitions Monitored 

PFOA 413>169, 413>219, 413>369 

13C4-PFOA (SRS) 417>169, 417>219, 417>372 

13C8-PFOA (IS) 421>172, 421>223, 421>376 

Note: Multiple mass transitions are summed to give the instrument response for that 

analyte. 
Study: GLP10-01-01, Interim Report 25 

Analysis for PFOA in Soils Used for a Vegetative Uptake Study with Turnip Greens

Page 13 of 20

7 Analytical Results 

All results are rounded to three significant figures according to EPA rounding rules. Because of 

rounding, values may vary slightly from those found in the raw data. All results were calculated from

accurate values in the raw data. Laboratory matrix spikes (LMS) meeting the method acceptance 

criteria of 100 ± 30%, demonstrate that the method was appropriate. The LMS most adequate with 

respect to the endogenous PFOA measured in the samples was the LMS used for data accuracy 

evaluations, as noted in Table 1 and Table 10. In some instances both LMSs were appropriate, and 

in those cases the result for both LMSs was used in accuracy statistical calculations.

7.1 Calibration 

Calibration standards were prepared by spiking varying known quantities of PFOA (linear isomer) and 

surrogate, and a fixed quantity of internal standard, into separate 1-cubic centimeter (1 cc, 1 mL) 

aliquots of 3M Environmental Laboratory control soil matrix TCR-455 (nominal 1.0 gram per mL). A total 

of eleven (11) soil matrix calibration standards ranging from nominal PFOA concentration 0.200 ng/g to

200 ng/g were prepared for the definitive analysis. Following the analysis of calibration standards, the 

nominal concentration of each standard was plotted versus the measured analyte peak area/IS peak 

area response ratio. A quadratic equation with 1/x weighting was used to fit the calibration response

data. Calibration curves were not forced through zero. Calculating the determined standard 

concentration using the resultant calibration curve and comparing to the known concentration confirmed

accuracy of each curve point within 100 ± 30% (+ 35% at the LLOQ). The correlation coefficient (r) was 

greater than 0.999, and coefficient of determination (r2) was greater than 0.990. Calibration results for 

PFOA are summarized in Table 6 and for the 13C4-PFOA SRS in Table 7. 

Because soil weights can vary significantly for a 1 cc (1 mL) soil sample, depending on soil type and 

moisture content, the instrument response was calibrated for the known concentrations of PFOA based 

on the mass quantity of PFOA added to each 1 cc soil calibration standard prior to extraction (e.g.

calibrated in this study for a range of 0.200 ng to 500 ng PFOA). Because a 1cc aliquot of control soil 

TCR-455 weighs approximately 1.0-1.1 gram (dry weight) and has less than 5% moisture content, the 

nominal concentration range of the calibration was nominal 0.200 ng/g to 200 ng/g. However, 

environmental soils vary in moisture content and soil composition and 1 cc aliquots of those soil samples 

typically weighed more than 1.0 gram. Therefore, the final measured results from the analysis (ng 

PFOA) were adjusted for the accurate weight of the 1 cc sample aliquot that was extracted, and then 

adjusted for percent moisture of the sample for the final result. 

Table 6. PFOA Calibration Summary (Calibrated with linear PFOA)

Analytical 

Run 

PFOA (ng) [a]

r STD 

1 

STD 

2 

STD 

3 

STD 

4 

STD 

5 

STD 

6 

STD 

7 

STD 

8 

STD 

9 

STD 

10 

STD 

11 

STD 

12 

Actual (ng) 0.200 0.500 0.750 1.00 2.50 5.00 10.0 25.0 50.0 100 200 500 N/A 

s111223a 0.190 0.521 0.764 0.997 2.41 5.01 10.4 23.7 51.5 103 195 501 0.9997 

Recovery (%) 95.0% 104% 102% 99.7% 96.4% 100% 104% 94.8% 103% 103% 97.5% 100% N/A 

N/A; not applicable 

[a] PFOA concentrations are nominal 0.200 to 500 ng/g based on nominal 1.0 gram of TCR-455 soil (dry weight) 
Study: GLP10-01-01, Interim Report 25 

Analysis for PFOA in Soils Used for a Vegetative Uptake Study with Turnip Greens

Page 14 of 20

Table 7. 13C4-PFOA (SRS) Calibration Summary

Analytical 

Run 

13C4-PFOA (ng) [a]

r STD 

1 

STD 

2 

STD 

3 

STD 

4 

STD 

5 

STD 

6 

STD 

7 

STD 

8 

STD 

9 

STD 

10 

STD 

11 

STD 

12 

Actual (ng) 0.200 0.499 0.749 0.998 2.50 4.99 9.98 25.0 49.9 99.8 200 499 N/A 

s111223a 0.247 0.518 0.726 0.982 2.30 4.59 9.74 22.7 51.5 100 202 497 0.9998 

Recovery (%) 124% 104% 97.0% 98.4% 92.2% 92.0% 97.6% 91.0% 103% 100% 101% 99.6% N/A 

N/A; not applicable 

[a] 13C4-PFOA concentrations are nominal 0.200 to 500 ng/g soil based on nominal 1.0 gram of TCR-455 soil (dry weight) 

7.2 Limits of Quantitation (LOQs) 

The lower limit of quantitation (LLOQ) was the lowest non-zero calibration standard in the curve that met 

linearity and accuracy requirements (100 + 35%) and for which the area counts were at least 2X that of 

the average response determined from the method blanks. The LLOQ for this study was nominal 

concentration 0.200 ng/g, and was the lowest prepared calibration standard. All sample analyte 

responses less than the response of the nominal 0.200 ng/g calibration standard were reported as BLQ 

(below the limits of quantitation). The upper limit of quantitation (ULOQ) was nominal concentration 500 

ng/g. 

7.3 Continuing Calibration 

During the course of each analysis, continuing calibration verifications (CCVs) was performed by regular 

injection of a mid-level calibration standard after approximately every 15 samples in the analytical run. 

The back calculated concentration results were used to confirm that the instrument response and the 

initial calibration curve were still in control. All CCVs flanking reported data met the method criteria of 

100% ± 30% accuracy. 

7.4 Blanks 

Three types of blanks were analyzed during this analysis: method blanks were prepared with blank 

matrix soil TCR-455 and were spiked with IS and surrogate; travel blanks (trip blanks) prepared from 

aliquots of soil TCR-455 contained in sealed bottles that accompanied the bottle order to Decatur, and

sample shipment back to 3M Environmental Laboratory; and solvent blanks containing extraction 

solvent. The different blanks results were reviewed to evaluate potential contamination during shipment 

and sampling, to evaluate method performance parameters such as injector carry over and also to 

establish the LLOQ and the performance of the blanks were considered in the reporting of all results. 
Study: GLP10-01-01, Interim Report 25 

Analysis for PFOA in Soils Used for a Vegetative Uptake Study with Turnip Greens

Page 15 of 20

7.5 Laboratory Control Spikes (LCSs) 

Laboratory control spikes were prepared by spiking known quantities of PFOA (linear + branched 

isomers) into 1 cc aliquots of soil TCR-455, fortified with nominal 3.0 ng, 30 ng and 300 ng PFOA (linear 

+ branched isomer). The 13C4-PFOA (SRS) was fortified at 3.00 ng. The linear + branched isomer 

quantitation using a linear PFOA calibration curve provided a measure of accuracy in quantifying the 

sum of potential linear + branched PFOA isomers that are commonly associated with environmental 

samples. Each LCS level was prepared in triplicate. The averaged results of the LCS analyses and 

calculated analytical method uncertainty are shown in Table 8. The method acceptance criteria of 100 ± 

30% was met for all LCS results. The LCS recoveries were calculated using the following equation: 

*100%

Spike Concentration

(Determine d Concentration of LCS) LCS Recovery =

Table 8. LCS Results

LCS ID PFOA Recovery 

13C4-PFOA (SRS) 

Recovery 

LCS-111221-01 (3.00 ng LCS) 96.3% 96.7% 

LCS-111221-02 (3.00 ng LCS) 101% 105% 

LCS-111221-03 (3.00 ng LCS) 99.0% 96.3% 

LCS-111221-04 (30.0 ng LCS) 101% 104% 

LCS-111221-05 (30.0 ng LCS) 100% 96.3% 

LCS-111221-06 (30.0 ng LCS) 110% 107% 

LCS-111221-07 (300 ng LCS) 106% 104% 

LCS-111221-08 (300 ng LCS) 98.7% 98.0% 

LCS-111221-09 (300 ng LCS) 108% 103% 

Average 102% 101% 

Standard Deviation 4.5% 4.3% 

%RSD 4.4% 4.3% 

Method Uncertainty (95% CI) 9.0% 8.7% 

Each LCS was prepared by fortifying 1cc of soil (nominal 1.0 g/cc) with 3.00 ng (Low LCS), 30.0 ng (Mid 

LCS) or 300 ng (High LCS) of PFOA. 

7.6 Laboratory Matrix Spikes (LMSs) 

Laboratory matrix spikes (LMSs) were generated by spiking a known quantity of PFOA (linear) to an 

aliquot of each soil sample and then preparing the sample the same as regular non-spiked samples. 

For this study, two LMSs were prepared for each field sample, with fortification of 1.00 ng PFOA and 

10.0 ng PFOA into 1 cc aliquots of sample; as a low LMS and high LMS, respectively. One LMS was 

prepared for the trip blank and was fortified with nominal 1.00 ng PFOA. Typically, LMS fortifications are 

at a level that is between 0.5-times and 10-times the endogenous level. Two levels were prepared for 

each sample in this study because endogenous PFOA levels in the soil samples was not known at the 

time of preparation. The recovery of PFOA from the LMS fortified with PFOA at a level most similar to

the endogenous PFOA level in the corresponding soil sample was used for determination of the sample 

data accuracy, and those LMS recoveries are shown in Table 1 and Table 10. 
Study: GLP10-01-01, Interim Report 25 

Analysis for PFOA in Soils Used for a Vegetative Uptake Study with Turnip Greens

Page 16 of 20

The method acceptance criteria of 100 ± 30% was met for all LMSs, except one which had a recovery 

of158% for sample GLP10-01-01-25-016 (DAL SS 800 TG1 0 111214). 

The PFOA recovery calculations for LMS samples used the following equation: 

*100%

Spike Concentration

(Determine d Concentration of LMS Determined Concentration of Field Sample) LMS Recovery −

=

7.7 Percent Moisture Determinations 

The percent moisture was determined in duplicate for each soil sample. For each replicate, a sample 

aliquot is accurately weighed to determine the “wet” weight. Then the aliquot is dried at > 100°C unt il no 

further loss in mass occurs (due to water evaporation), and then the dry weight is accurately determined. 

The average percent moisture and RPD of the duplicate determinations for each is reported in Table 9. 

The percent moisture was calculated by the following equation: 

*100%

Original Soil Wet Mass

(Original Soil Wet Mass Dried Soil Mass) Percent Moisture −

= 

Table 9. Percent Moisture Results for Soils from PFOA Vegetative Uptake Study with Turnip 

Greens (December 2011) 

LIMS ID Sample ID Average Percent 

Moisture (w/w) [a] %RPD 

GLP10-01-01-25-001 DAL SS CONT POT 0 0 111214 6.50% 4.5% 

GLP10-01-01-25-002 DAL SS 025 POT 0 0 111214 6.55% 0.41% 

GLP10-01-01-25-003 DAL SS 050 POT 0 0 111214 4.33% 3.0% 

GLP10-01-01-25-004 DAL SS 100 POT 0 0 111214 4.74% 0.35% 

GLP10-01-01-25-005 DAL SS 200 POT 0 0 111214 3.41% 0.77% 

GLP10-01-01-25-006 DAL SS 400 POT 0 0 111214 5.81% 4.9% 

GLP10-01-01-25-007 DAL SS 800 POT 0 0 111214 3.33% 5.7% 

GLP10-01-01-25-008 DAL SS CONT TG1 0 111214 9.22% 4.9% 

GLP10-01-01-25-009 DAL SS 025 TG1 0 111214 5.46% 0.50% 

GLP10-01-01-25-010 DAL SS 050 TG1 0 111214 9.82% 1.5% 

GLP10-01-01-25-011 DAL SS 100 TG1 0 111214 6.69% 4.6% 

GLP10-01-01-25-012 DAL SS 200 TG1 0 111214 10.7% 13% 

GLP10-01-01-25-013 DAL SS 400 TG1 0 111214 9.18% 0.18% 

GLP10-01-01-25-014 DAL SS 800 TG1 0 111214 7.39% 1.4% 

GLP10-01-01-25-016 TRIP BLANK-1 2.38% 1.7% 

 [a] Percent moisture determined for duplicate samples of soil taken from each sample bottle 
Study: GLP10-01-01, Interim Report 25 

Analysis for PFOA in Soils Used for a Vegetative Uptake Study with Turnip Greens

Page 17 of 20

7.8 Individual Sample Results 

The individual sample concentration results are shown in Table 10. 

Table 10. Individual PFOA Results for Potting Soils for Turnip Greens (December 2011) 

Sample Description 

Surrogate 

(

13C4-PFOA) 

Recovery [a]

LMS Spike 

Concentration 

(ng/g; dry 

weight) 

Measured 

PFOA 

Concentration 

(ng/g; dry 

weight) 

LMS Recovery 

(Data 

Accuracy) [b]

Average PFOA 

Concentration 

(ng/g; dry wt.) and 

%RPD (Data 

Precision) 

DAL SS CONT POT 0 0 111214 101% N/A BLQ N/A BLQ 

DAL SS CONT POT 0 0 111214 Duplicate 99.2% BLQ 

DAL SS CONT POT 0 0 111214 LMS Low 93.9% 0.933 1.04 112% 

N/A 

DAL SS CONT POT 0 0 111214 LMS High 99.2% 8.86 8.78 N/A [b]

DAL SS 025 POT 0 0 111214 99.5% N/A 0.428 N/A 0.409 

DAL SS 025 POT 0 0 111214 Duplicate 97.9% 0.391 

DAL SS 025 POT 0 0 111214 LMS Low 102% 0.860 1.28 101% 

9.1% 

DAL SS 025 POT 0 0 111214 LMS High 98.2% 9.51 10.6 N/A [b]

DAL SS 050 POT 0 0 111214 102% N/A 0.861 N/A 0.887 

DAL SS 050 POT 0 0 111214 Duplicate 105% 0.912 

DAL SS 050 POT 0 0 111214 LMS Low 101% 0.880 1.7 97.3% 

5.7% 

DAL SS 050 POT 0 0 111214 LMS High 96.5% 9.27 9.9 N/A [b]

DAL SS 100 POT 0 0 111214 101% N/A 1.63 N/A 1.66 

DAL SS 100 POT 0 0 111214 Duplicate 99.5% 1.69 

DAL SS 100 POT 0 0 111214 LMS Low 104% 0.889 2.66 112% 

3.7% 

DAL SS 100 POT 0 0 111214 LMS High 103% 8.55 11.2 112% 

DAL SS 200 POT 0 0 111214 98.5% N/A 3.70 N/A 3.77 

DAL SS 200 POT 0 0 111214 Duplicate 95.9% 3.85 

DAL SS 200 POT 0 0 111214 LMS Low 95.2% 0.843 4.66 N/A [b]

4.0% 

DAL SS 200 POT 0 0 111214 LMS High 87.8% 8.49 12.4 102% 

DAL SS 400 POT 0 0 111214 98.2% N/A 6.76 N/A 6.69 

DAL SS 400 POT 0 0 111214 Duplicate 93.5% 6.61 

DAL SS 400 POT 0 0 111214 LMS Low 97.9% 0.983 7.94 N/A [b]

2.3% 

DAL SS 400 POT 0 0 111214 LMS High 96.2% 9.21 16.0 101% 

DAL SS 800 POT 0 0 111214 92.2% N/A 14.6 N/A 14.9 

DAL SS 800 POT 0 0 111214 Duplicate 94.5% 15.3 

DAL SS 800 POT 0 0 111214 LMS Low 97.9% 0.753 14.4 N/A [b]

4.4% 

DAL SS 800 POT 0 0 111214 LMS High 90.5% 7.38 21.5 88.6% 

DAL SS CONT TG1 0 111214 99.9% N/A BLQ N/A BLQ 

DAL SS CONT TG1 0 111214 Duplicate 94.5% BLQ 

DAL SS CONT TG1 0 111214 LMS Low 97.2% 0.923 0.987 107% 

N/A 

DAL SS CONT TG1 0 111214 LMS High 91.2% 8.81 8.99 N/A [b]

DAL SS 025 TG1 0 111214 87.8% N/A 0.648 N/A 0.639 

DAL SS 025 TG1 0 111214 Duplicate 93.9% 0.630 

DAL SS 025 TG1 0 111214 LMS Low 89.8% 0.980 1.64 102% 

2.8% 

DAL SS 025 TG1 0 111214 LMS High 97.5% 9.72 10.3 N/A [b]
Study: GLP10-01-01, Interim Report 25 

Analysis for PFOA in Soils Used for a Vegetative Uptake Study with Turnip Greens

Page 18 of 20

Table 10. Individual PFOA Results for Potting Soils for Turnip Greens (December 2011) 

Sample Description 

Surrogate 

(

13C4-PFOA) 

Recovery [a]

LMS Spike 

Concentration 

(ng/g; dry 

weight) 

Measured 

PFOA 

Concentration 

(ng/g; dry 

weight) 

LMS Recovery 

(Data 

Accuracy) [b]

Average PFOA 

Concentration 

(ng/g; dry wt.) and 

%RPD (Data 

Precision) 

DAL SS 050 TG1 0 111214 99.9% N/A 1.03 N/A 0.999 

DAL SS 050 TG1 0 111214 Duplicate 93.5% 0.964 

DAL SS 050 TG1 0 111214 LMS Low 98.2% 0.868 1.89 103% 

6.9% 

DAL SS 050 TG1 0 111214 LMS High 97.2% 9.99 11.4 104% 

DAL SS 100 TG1 0 111214 101% N/A 2.06 N/A 2.02 

DAL SS 100 TG1 0 111214 Duplicate 97.2% 1.99 

DAL SS 100 TG1 0 111214 LMS Low 91.2% 0.973 3.03 N/A [b]

3.4% 

DAL SS 100 TG1 0 111214 LMS High 99.5% 10.4 13.1 107% 

DAL SS 200 TG1 0 111214 86.5% N/A 3.53 N/A 3.46 

DAL SS 200 TG1 0 111214 Duplicate 89.8% 3.39 

DAL SS 200 TG1 0 111214 LMS Low 99.2% 0.934 4.43 N/A [b]

4.1% 

DAL SS 200 TG1 0 111214 LMS High 93.9% 9.98 13.8 103% 

DAL SS 400 TG1 0 111214 98.9% N/A 9.64 N/A 9.40 

DAL SS 400 TG1 0 111214 Duplicate 96.9% 9.16 

DAL SS 400 TG1 0 111214 LMS Low 89.8% 0.926 9.81 N/A [b]

5.1% 

DAL SS 400 TG1 0 111214 LMS High 96.5% 8.30 15.6 74.8% 

DAL SS 800 TG1 0 111214 94.9% N/A 13.3 N/A 13.5 [d]

DAL SS 800 TG1 0 111214 Duplicate 92.2% 13.7 

DAL SS 800 TG1 0 111214 LMS Low 97.9% 0.943 18.2 N/A [b]

3.3% 

DAL SS 800 TG1 0 111214 LMS High 99.5% 10.6 30.2 158% 

TRIP BLANK-1 95.5% N/A BLQ N/A BLQ 

TRIP BLANK-1 Duplicate 96.5% BLQ 

TRIP BLANK-1 LMS 92.5% 1.02 1.08 106% N/A 

DAL SS 800 TGI RB 111214 101% N/A <0.0287 [e] N/A <0.0287 [e]

N/A; not applicable 

[a] Surrogate recovery determined for samples fortified with 3.0 ng of 13C4-PFOA and quantified from a 13C4-PFOA calibration curve, but 

otherwise not used for data accuracy assessments for the study. 

[b] LMS Recovery was not appropriate relative to the endogenous PFOA concentration and not used for LMS recovery determinations 

for the study data accuracy evaluation. 

[c] Endogenous sample PFOA concentrations less than LLOQ (BLQ) were treated as zero for LMS recovery calculations 

[d] LMS recovery for the result was outside of 100 + 30% at 158%. 

[e] Results was determined from an water analysis method and the result was below the LLOQ of 0.0287 ng/mL (BLQ), the SRS was 

fortified at nominal concentration 0.100 ng/mL. 

8 Conclusion 

Analysis of potting soils used for the growth of turnip greens in the PFOA vegetative uptake study 

GLP10-01-03 was successfully completed following 3M Environmental Laboratory method ETS-8-

053.0 and was conducted as 3M study GLP10-01-01-25. The average PFOA concentration results 

and LMS recoveries for the soil samples are summarized in Table 1. The PFOA results for each 

individual sample replicate are provided in Table 10. Concentrations of PFOA in the soils were 

almost 2-times higher than anticipated based on the desired blended concentrations. 
study: GLP10-01-01, Interim Report 25 

Analysis for PFOA in Soils Used for a Vegetative Uptake Study with Turnip Greens 

All sample results were reported with good data accuracy of within 100 + 26%, except sample 

GLP10-01-01-25-016 (DAL SS 800 TG1 0 111214) with a LMS recovery (data accuracy) of 158%. 

All analytical duplicate sample results demonstrated excellent precision with RPDs of less than 

10%. The travel blank that accompanied the sample bottles shipments was below the lower limit 

of quantitation (BLQ, less than nominal 0.200 ng/g), indicating proper handling of samples during 

sample shipment, storage and preparation for analysis. Similarly, the PFOA in the aqueous 

equipment rinseate was < 0.0287 ng/mL for that sample, and demonstrated that cross 

contamination during soil sampling did not occur. 

9 Data/Sample Retention 

All soil samples and associated project data (hardcopy and electronic) will be archived as project GLP10-

01-01-25 according to 3M Environmental Laboratory standard operating procedures. 

10 Listtof Attachments 

Attachment A: Preparation Forms, Raw Data, Chromatograms and Analytical Summary for Equipment 

Rinseate 

11 Signatures 

Report Approval: 

Cleston C. Lange, Ph.D., Principal Analytical Investigator i Date 

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

Gary A. Hohenstein, Sponsor Representative Date 

Jaisimha Kesari, Study Director Date 

Page 19 of 20 
Study: GLP10-01-01, Interim Report 25 

Analysis for PFOA in Soils Used for a Vegetative Uptake Study with Turnip Greens

Page 20 of 20

Attachment A 

Preparation Forms, Raw Data, Chromatograms and Analytical 

Summary for Equipment Rinseate