# 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 GLP 10-01-01: Analysis of Perfluorooctanoic Acid (PFOA) in Groundwater, Soil and Sediment for t he 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

20Study: GLP10-01-01, Interim Report 25 Analysis for PFOA in Potting Soils Used for a Veget ative Uptake Study with Turnip Greens

Page 2 of 20 This page has been reserved for specific country re quirements.Study : GLP10-01-01 , Interi m Repor t 2 5 Analysi s fo r PFO A i n Pottin g Soil s Use d fo r a Vegetativ e Uptak e Stud y wit h Turni p Greens



### GL P COMPLIANC E STATEMEN T

Repor t Title : GLP10-01-0 1 Interi m Repor t 25 : Analysi s fo r PFO A i n Pottin g Soil s Use d fo r a PFO A Vegetativ e Uptak e Stud y wit h Turni p Greens

. 3 M Environmenta l Laborator y Analytica l Protoco l GLP10-01-01 : Analysi s o f Perfluorooctanoi c Aci d (PFOA ) i n Groundwater , Soi l an d Sedimen t fo r th e 3 M Decatu r Phas e 3 Site-Relate d Monitorin g Program

.

Thi s analytica l phas e wa s conducte d i n complianc e wit h Toxi c Substance s Contro l Ac t (TSCA ) Goo d Laborator y Practic e (GLP ) Standards , 4 0 CF R 792 , wit h th e exception s liste d below :

Exception s t o GL P compliance : Th e analytica l referenc e substance s wer e no t al l characterize d unde r GLPs

. Sample s ar e environmenta l samples ; ther e wa s n o dosin g an d n o specifi c tes t substanc e o r contro l substanc e fo r thi s stud y an d onl y analytica l referenc e substances

.

Gar y Hobjfenstein , Sponso r Representativ e Dat e

Jaisimh a Kesari , P.E. , DEE , Stud y Directo r Dat e

Pag e 3 o f 2 0stud y GLP10-01-01 , Interi m Repor t 2 5 Analysi s fo r PFO A i n Pottin g Soil s Use d fo r a Vegetativ e Uptak e Stud y wit h Turni p Greens



### QUALIT Y ASSURANC E STATEMEN T

Repor t Title : GLP10-01-0 1 Interi m Repor t 25 : Analysi s fo r PFO A i n Pottin g Soil s Use d fo r a PFO A Vegetativ e Uptak e Stud y wit h Turni p Greens

. 3 M Environmenta l Laborator y Analytica l Protoco l GLP10-01-01 : Analysi s o f Perfluorooctanoi c Aci d (PFOA ) i n Groundwater , Soi l an d Sedimen t fo r th e 3 M Decatu r Phas e 3 Site-Relate d Monitorin g Program

.
Thi s interi m stud y repor t an d th e accompanyin g dat a wer e audite d b y th e 3 M Environmenta l Laborator y Qualit y Assuranc e Uni t (QAU) , a s indicate d below

. Th e finding s wer e reporte d t o th e principa l investigato r (P.I.) , laborator y managemen t an d stud y director

.

stud y Inspectio n Date s Dat e Reporte d t o stud y Inspectio n Date s Phas e P.I

. Stud y Directo r iVIanagemen t stud y Directo r

Ja n 12,13&16,201 2 Interi m Repor t an d Dat a Jan

. 19,201 2 Ja n 26,201 2 Ja n 26 , 201 2



# /•-lt>^ €^ a-iQA U Representativ e 

### Dat e

Pag e 4 o f 2 0Study: GLP10-01-01, Interim Report 25 Analysis for PFOA in Potting Soils Used for a Veget ative Uptake Study with Turnip Greens

Page 5 of 20 

## T ABLE OF 

## C ONTENTS
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 .........................

................................................... ........................ 17Study: GLP10-01-01, Interim Report 25 Analysis for PFOA in Potting Soils Used for a Veget ative Uptake Study with Turnip Greens

Page 6 of 20 8 Conclusion ........................................

................................................... .............................................. 18
9 Data/Sample Retention .............................

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

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

................................................... ............................................... 19



## L IST OF 

## T

ABLES Table 1. PFOA Results: Potting Soils for Vegetati ve 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. 13 C 4 -PFOA (SRS) Calibration Summary ...................

................................................... ............ 14
Table 8. LCS Results ..............................

................................................... .............................................. 15
Table 9. Percent Moisture Results for Soils from P FOA Vegetative Uptake Study with Turnip Greens (December 2011) ............................

................................................... .................................. 16 Table 10. Individual PFOA Results for Potting Soil s for Turnip Greens (December 2011) ............... .. 17Study: GLP10-01-01, Interim Report 25 Analysis for PFOA in Potting Soils Used for a Veget ative 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 Inves tigator William K. Reagen, Ph.D., Laboratory Manager Patrick Kenney, Laboratory Technician (Pace Analyti cal, Professional Services) Marlene Heying, Laboratory Technician (Pace Analyti cal, 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 b een 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 Env ironmental Laboratory according to 40 CFR Part 79Study: GLP10-01-01, Interim Report 25 Analysis for PFOA in Soils Used for a Vegetative Up take Study with Turnip Greens

Page 8 of 20 

### 2 Summary
Reported herein are the PFOA concentrations determi ned for fourteen potting soils used for a PFOA vegetative uptake study with turnip greens. Result s for a travel blank (trip blank) containing a cont rol soil TCR-455 in a sealed sample bottle that traveled wit h the sample bottles to and from the site and an equipment rinseate sample are also reported. Samp les were received in December 2011 and logged into the 3M Environmental Laboratory LIMS system under p roject GLP10-01-01-25. The samples were extracted and analyzed as a single analytical batch with matrix matched soil calibration standards, bl anks and laboratory control samples (LCSs). For prepara tion of each sample, four aliquots of soil were removed from each sample bottle, transferred to a c entrifuge tube and accurately weighed and fortified with a fixed amount of internal standard (IS). The first and second aliquot served as analytical samp le and sample duplicate for determining PFOA in the sample . The third and fourth replicates were fortified w ith nominal 1.00 and 10.0 ng of PFOA as a low laborator y 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 the n 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 f rom LMSs was used as a measure of sample data accuracy. The %RPD of the duplicate analytical sam ple 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 demonstr ated with RPDs <10% for each duplicate set of results. The method uncertainty (95% CI) was deter mined at + 9.0% based on LCS results. Table 1. PFOA Results: Potting Soils for Vegetati ve 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 n g/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 P FOA 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 1.0 0 ng fortified LMS [d] LMS recovery value shown is for the nominal 10. 0 ng fortified LMS [e] The aqueous equipment rinseate blank was analyz ed by method ETS-8-044.1 with an LLOQ of 0.0287 ng/ mLStudy: GLP10-01-01, Interim Report 25 Analysis for PFOA in Soils Used for a Vegetative Up take Study with Turnip Greens

Page 9 of 20 

### 3 Introduction
The soil analysis results reported herein were cond ucted as part of the Phase 3 Environmental Monitoring and Assessment Program for the 3M facili ty located in Decatur, Alabama. The objective of the overall program is to gain information regar ding 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 fo r planting of turnip/turnip greens as part of a PFOA vegetative uptake study GLP10-01-03. The samples were prepared and collected by Weston Solut ions, 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 bot tle 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 t he potting soils as project GLP10-01-01-25. Additionally, included in this report are the asses sment of the sample-specific analytical precision a nd accuracy for the reported PFOA concentration result s and the determined percent moisture content of each soil was determined and is reported. Addit ionally included are the recovery results for 13 C 4 - PFOA as a surrogate recovery standard (SRS) that was ad ded to each soil aliquot prior to extraction and was included as part of a method validation stu dy 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 contro l 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 an d was not the dosing study. The reference and contro l substances are listed in Table 2

. Table 2. Reference Substances

Test Substance PFOA (linear

isomer), free acid PFOA (linear + branched isomers), ammonium salt 13 C 4 -PFOA 13 C 8 -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 10/2 2/2012 Storage Conditions Frozen Frozen Frozen Frozen
Chemical Lot 3440 332 MPFOA1009 M8PFOA0408 TCR Number TCR07-0041 1/1 TCR-123 TCR09-0075 2/9 TC R09-0067 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 (sourc e) and are treated as 100% pure; the vendor’s reported methano l stock concentration is used for calculating conce ntrations of diluted standards made from themStudy: GLP10-01-01, Interim Report 25 Analysis for PFOA in Soils Used for a Vegetative Up take Study with Turnip Greens

Page 10 of 20 

### 5 Test System
There was not a test system for this study in the c lassic 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 t hese results was performed on December 23, 2011 as analytical run s111223a. The analysis of the aqueou s equipment rinseate was by following method ETS8-044.1 and was performed on December 28 as analyti cal run mc111228a. The analysis parameters and QC results for the water analysis are omitted f rom this report but are contained in a condensed summary report and will be maintained within the da ta package for this soil analysis project. Only th e PFOA concentration result for the equipment rinseat e 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 rins ing, and one travel blank (trip blank) containing approximately 25 grams of a control soil TCR-455, w ere sent from the 3M Environmental Laboratory to Weston Solutions, Inc. field personne l for collection of potting soils. Following the soil sample collections by Weston Solutions, Inc. p ersonnel, fourteen (14) soil-filled sample bottles, one equipment rinse blank (aqueous) and th e 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 l ogged 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 wer e 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 stri ng defines the sample media (i.e., SS = soil sample), the third string defines the targeted leve l of PFOA for the potting soil (i.e., CONT = contro l, 025 = 0.25 ng/g target concentration, etc.), the vegeta tion 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 typ e (0 = primary sample, DB = field duplicate, RB = equipm ent rinseate blank). The fifth string indicates the sampling date in YYMMDD format (i.e., 111214 = Dece mber 14, 2011). 

### 6.3 Sample Preparation
Sample preparation (extraction) for soils was condu cted as a single analytical batch from December 21- 22, 2011. The analytical batch was analyzed as ana lytical 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 s poon, 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 ad ded to each soil aliquot. Then the soil aliquot wa s extracted by addition of 8 mL of a 4:1 acetonitrile :water solution followed by brief mixing and sonica tion for 1 hour, then centrifugation to remove solids. The supernatant from each was then transferred to a nStudy: GLP10-01-01, Interim Report 25 Analysis for PFOA in Soils Used for a Vegetative Up take Study with Turnip Greens

Page 11 of 20 autovial for analysis. An accurately measured volu me of each supernatant was analyzed by LC/MS/MS. Each analytical sample was prepared in quadruplicat e, with the first and second samples being the sample and duplicate sample, and the third and four th 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 pr epared in triplicate, with sample, sample duplicate and one LMS fortified with 1.00 ng PFOA (linear isomer) Calibration standards were prepared by spiking know n quantities of PFOA (linear isomer) into 1-cubic centimeter (1 cc, 1 mL) aliquots of 3M Environmenta l Laboratory control soil TCR-455. The nominal mass of 1 cc of control soil TCR-455 is 1.0-1.1 gra m (dry). The nominal calibration standard soil concentration range was 0.200 ng/g to 200 ng/g base d on a nominal dry weight of 1.0 gram for TCR455. During preparation, each soil aliquot received nomi nal 3.0 ng of 13 C 4 -PFOA as a stable isotope labeled surrogate recovery standard (SRS). Although not i ncluded as part of the data accuracy assessment for this study, SRS recovery determinations were includ ed 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 fr om 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 fo r this study and is otherwise excluded from the discussions in the report. Laboratory control spike (LCS) samples were prepare d 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 13 C 4 -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 dete rmined by gravimetric analysis. Dry weights were determined for separate weighings than the weighing s used for PFOA extraction and analysis procedures. To determine the percent moisture, dup licate 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 evapora tion, was used to calculate the percent moisture of the original soil. The averaged percent moisture r esult for each was then used to calculate the soil PFOA concentration on a dry weight basis, and is re ported for each soil in Table 9

. 

### 6.5 LC/MS/MS Analysis
The LC/MS/MS analysis of the analytical batch was c onducted on December 23, 2011 as analytical run s111223a and was performed by as described in m ethod ETS-8-053.0 The relative percent difference (RPD) of the duplic ate 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 acc uracy. Recovery of the surrogate ( 13 C 4 -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 as sessment 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 Up take 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, 5 μ ) Analytical column Oasis HLB (3 x 20 mm, 25 μ ); 30°C Injection Volume 25 μ L 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
13 C 4 -PFOA (SRS) 417>169, 417>219, 417>372

13 C 8 -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 Up take Study with Turnip Greens

Page 13 of 20 

### 7 Analytical Results
All results are rounded to three significant figure s 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 matri x 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 samp les was the LMS used for data accuracy evaluations, as noted in Table 1 and Table 10 . In some instances both LMSs were appropriate, an d in those cases the result for both LMSs was used in accuracy statistical calculations.



### 7.1 Calibration
Calibration standards were prepared by spiking vary ing known quantities of PFOA (linear isomer) and surrogate, and a fixed quantity of internal standar d, into separate 1-cubic centimeter (1 cc, 1 mL) aliquots of 3M Environmental Laboratory control soi l matrix TCR-455 (nominal 1.0 gram per mL). A tota l of eleven (11) soil matrix calibration standards ra nging from nominal PFOA concentration 0.200 ng/g to 200 ng/g were prepared for the definitive analysis. Following the analysis of calibration standards, th e 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 z ero. 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 determinatio n (r 2 ) was greater than 0.990. Calibration results for PFOA are summarized in Table 6 and for the 13 C 4 -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 calib rated for the known concentrations of PFOA based on the mass quantity of PFOA added to each 1 cc soi l 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 so il TCR-455 weighs approximately 1.0-1.1 gram (dry weig ht) 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 so il composition and 1 cc aliquots of those soil samp les typically weighed more than 1.0 gram. Therefore, t he 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 10 3 195 501 0.9997
**Recovery (%)** 95.0% 104% 102% 99.7% 96.4% 100% 104% 94.8% 103% 10 3% 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 w eight)Study: GLP10-01-01, Interim Report 25 Analysis for PFOA in Soils Used for a Vegetative Up take Study with Turnip Greens

Page 14 of 20 Table 7. 13 C 4 -PFOA (SRS) Calibration Summary

Analytical Run 13 C 4 -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] 13 C 4 -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 low est non-zero calibration standard in the curve that met linearity and accuracy requirements (100 + 35%) and for which the area counts were at least 2 X that of the average response determined from the method bla nks. The LLOQ for this study was nominal concentration 0.200 ng/g, and was the lowest prepar ed calibration standard. All sample analyte responses less than the response of the nominal 0.2 00 ng/g calibration standard were reported as BLQ (below the limits of quantitation). The upper limi t of quantitation (ULOQ) was nominal concentration 500 ng/g.


### 7.3 Continuing Calibration
During the course of each analysis, continuing cali bration verifications (CCVs) was performed by regul ar injection of a mid-level calibration standard after approximately every 15 samples in the analytical r un. The back calculated concentration results were used to confirm that the instrument response and the initial calibration curve were still in control. A ll CCVs flanking reported data met the method crite ria of 100% ± 30% accuracy.



### 7.4 Blanks
Three types of blanks were analyzed during this ana lysis: method blanks were prepared with blank matrix soil TCR-455 and were spiked with IS and sur rogate; travel blanks (trip blanks) prepared from aliquots of soil TCR-455 contained in sealed bottle s 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 reviewe d to evaluate potential contamination during shipme nt and sampling, to evaluate method performance parame ters such as injector carry over and also to establish the LLOQ and the performance of the blank s were considered in the reporting of all results.Study: GLP10-01-01, Interim Report 25 Analysis for PFOA in Soils Used for a Vegetative Up take 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, fortif ied with nominal 3.0 ng, 30 ng and 300 ng PFOA (lin ear + branched isomer). The 13 C 4 -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 tha t 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 recoverie s were calculated using the following equation:



### 100% * ion Concentrat Spike LCS)

of ion Concentrat d (Determine Recovery LCS =

Table 8. LCS Results

**LCS ID PFOA Recovery**  **13 C**  **4 -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 (no minal 1.0 g/cc) with 3.00 ng (Low LCS), 30.0 ng (Mi d LCS) or 300 ng (High LCS) of PFOA. 

### 7.6 Laboratory Matrix Spikes (LMSs)
Laboratory matrix spikes (LMSs) were generated by s piking 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 fie ld 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 fortification s are at a level that is between 0.5-times and 10-times t he endogenous level. Two levels were prepared for each sample in this study because endogenous PFOA l evels 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 i n Table 1 and Table 10

.Study: GLP10-01-01, Interim Report 25 Analysis for PFOA in Soils Used for a Vegetative Up take 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 TG 1 0 111214). The PFOA recovery calculations for LMS samples used the following equation:



### 100% * ion Concentrat Spike Sample) Field of ion Concentrat Determined LMS of ion Concentrat d (Determine Recovery LMS −

=



### 7.7 Percent Moisture Determinations
The percent moisture was determined in duplicate fo r 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 evaporati on), and then the dry weight is accurately determin ed. The average percent moisture and RPD of the duplica te determinations for each is reported in Table 9

. The percent moisture was calculated by the followin g equation:



### 100% * Mass Wet Soil Original Mass)

Soil Dried Mass Wet Soil (Original Moisture Percent −

=

Table 9. Percent Moisture Results for Soils from P FOA 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 samp les of soil taken from each sample bottleStudy: GLP10-01-01, Interim Report 25 Analysis for PFOA in Soils Used for a Vegetative Up take Study with Turnip Greens

Page 17 of 20 

### 7.8 Individual Sample Results
The individual sample concentration results are sho wn in Table 10. Table 10. Individual PFOA Results for Potting Soil s for Turnip Greens (December 2011)

Sample Description Surrogate ( 13 C 4 -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 Up take Study with Turnip Greens

Page 18 of 20 Table 10. Individual PFOA Results for Potting Soil s for Turnip Greens (December 2011)

Sample Description Surrogate ( 13 C 4 -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 forti fied with 3.0 ng of 13 C 4 -PFOA and quantified from a 13 C 4 -PFOA calibration curve, but otherwise not used for data accuracy assessments fo r the study. [b] LMS Recovery was not appropriate relative to th e endogenous PFOA concentration and not used for LM S recovery determinations for the study data accuracy evaluation. [c] Endogenous sample PFOA concentrations less than LLOQ (BLQ) were treated as zero for LMS recovery c alculations [d] LMS recovery for the result was outside of 100 + 30% at 158%. [e] Results was determined from an water analysis m ethod and the result was below the LLOQ of 0.0287 n g/mL (BLQ), the SRS was fortified at nominal concentration 0.100 ng/mL.



### 8 Conclusion
Analysis of potting soils used for the growth of tu rnip 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 summari zed 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 , Interi m Repor t 2 5 Analysi s fo r PFO A i n Soil s Use d fo r a Vegetativ e Uptak e Stud y wit h Turni p Green s Al l sampl e result s wer e reporte d wit h goo d dat a accurac y o f withi n 10 0 + 26% , excep t sampl e GLP10-01-01-25-01 6 (DA L S S 80 0 TG 1 0 111214 ) wit h a LM S recover y (dat a accuracy ) o f 158%

. Al l analytica l duplicat e sampl e result s demonstrate d excellen t precisio n wit h RPD s o f les s tha n 10%

. Th e trave l blan k

tha t accompanie d th e sampl e bottle s shipment s wa s belo w th e lowe r limi t o f quantitatio n (BLQ , les s tha n nomina l 0.20 0 ng/g) , indicatin g prope r handlin g o f sample s durin g sampl e shipment , storag e an d preparatio n fo r analysis

. Similarly , th e PFO A i n th e aqueou s equipmen t rinseat e wa s < 0.028 7 ng/m L fo r tha t sample , an d demonstrate d tha t cros s contaminatio n durin g soi l samplin g di d no t occur

.

9 Data/Sampl e Retentio n

Al l soi l sample s an d associate d projec t dat a (hardcop y an d electronic ) wil l b e archive d a s projec t GLP10

- 01-01-2 5 accordin g t o 3 M Environmenta l Laborator y standar d operatin g procedures

.

1 0 Listto f Attachment s

Attachmen t A : Preparatio n Forms , Ra w Data , Chromatogram s an d Analytica l Summar y fo r Equipmen t Rinseat e

1 1 Signature s
Repor t Approval :

Clesto n C

. Lange , Ph.D. , Principa l Analytica l Investigato r i Dat e

Willia m K

. Reagen , Ph.D. , 3 M Environmenta l Laborator y Managemen t Dat e

Gar y A

. Hohenstein , Sponso r Representativ e Dat e

Jaisimh a Kesari , Stud y Directo r Dat e

Pag e 1 9 o f 2 0Study: GLP10-01-01, Interim Report 25 Analysis for PFOA in Soils Used for a Vegetative Up take Study with Turnip Greens

Page 20 of 20 

## Attachment A Preparation Forms, Raw Data, Chromatograms and Anal ytical

Summary for Equipment Rinseate