# 3

GLP10-01-01 Interim Report 26: Analysis for PFOA in Sediments Collected

from the Jeffries Property in February 2012



## 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 GLP10-01-01-26

Total Number of Pages

19Study: GLP10-01-01, Interim Report 26 Analysis for PFOA in Sediments Collected from the J effries Property, Feb. 2012

Page 2 of 19 This page has been reserved for specific country re quirements.Study: GLP10-01-01, Interim Report 26 Analysis for PFOA in Sediments Collected from the J effries Property, Feb. 2012

Page 5 of 19 

## 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) ..................

................................................... .................. 14

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

................................................... .................. 15

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

................................................... .................. 16

7.8 Individual Sample Results .........................

................................................... ........................ 16Study: GLP10-01-01, Interim Report 26 Analysis for PFOA in Sediments Collected from the J effries Property, Feb. 2012

Page 6 of 19 8 Conclusion ........................................

................................................... .............................................. 17

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

................................................... ..................................... 17

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

................................................... .......................................... 17

11 Signatures ........................................

................................................... ............................................... 18


## L IST OF 

## T

ABLES

Table 1. PFOA Results for Sediments from Jeffries Property, February 2012 ........................... ........... 8
Table 2. LMS PFOA Recovery Results for Sediments fr om Jeffries Property, February 2012 ............. 8

Table 3. Reference Substances ....................

................................................... ........................................ 9

Table 4. Instrument Information ..................

................................................... ......................................... 12
Table 5. Gradient Liquid Chromatography Conditions (ETS-8-053)....................................... .............. 12

Table 6. Mass Transitions ........................

................................................... ............................................ 12
Table 7. PFOA Calibration Summary (Calibrated with linear PFOA) ..................................... .............. 13

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

................................................... .............................................. 15
Table 10. Percent Moistures for Jeffries Property Sediments, February 2012 .......................... .......... 16

Table 11. Individual PFOA Results for Jeffries Pro perty Sediments, February 2012 .................... ...... 16Study: GLP10-01-01, Interim Report 26 Analysis for PFOA in Sediments Collected from the J effries Property, Feb. 2012

Page 7 of 19 

### 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: March 02, 2012 Interim Analytical Completion: March 23, 2012 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 792.Study: GLP10-01-01, Interim Report 26 Analysis for PFOA in Sediments Collected from the J effries Property, Feb. 2012

Page 8 of 19 

### 2 Summary

This interim report provides the PFOA concentration results for five sediments collected from the Jeff ries property (Bert Jeffries Landfill) located in Northe rn Alabama. One travel blank (trip blank), contain ing approximately 10-25 grams of control soil in a samp le bottle, accompanied the sample bottles to and fr om the collection site and was also analyzed. Samples were received on March 02, 2012 and logged into th e 3M Environmental Laboratory electronic LIMS system under project GLP10-01-01-26. Prior to extraction, sediments were aliquoted from each sample bottle in triplicate into extraction vessels and accurately weighed. The first and second aliquot served as an alytical sample and duplicate sample. The third replicate of each was fortified with nominal 2.00 n g of PFOA as a laboratory matrix spike (LMS). A s ingle LMS for the trip blank was also prepared and fortif ied with nominal 1.00 ng of PFOA. Each aliquot was extracted and analyzed per method ETS-8-053 by liqu id chromatography with triple quadrapole mass spectrometric detection (LC/MS/MS). The PFOA recov ery results from LMSs provided a measure of sample-specific accuracy for the results. The rela tive percent difference (RPD) of the duplicate samp le results was used to assess the analytical precision of the sample results. The percent moisture of ea ch soil was also determined as part of the study and r esults reported on a dry sediment weight basis. Th e PFOA concentrations and RPDs are summarized in Table 1 . The LMS fortification concentrations and recoveries for PFOA are summarized in Table 2

.

Table 1. PFOA Results for Sediments from Jeffries Property, February 2012

**3M LIMS ID Sample ID Avg. PFOA**  **Concentration (ng/g; dry weight)**  **Relative Percent Difference** 

GLP10-01-01-26-001 JPAL SD TRIP1 0 0000 BLQ NA
GLP10-01-01-26-002 JPAL SD ET01 0 0000 0.629 14%
GLP10-01-01-26-003 JPAL SD ET02 0 0000 0.671 23%
GLP10-01-01-26-004 JPAL SD ET02 DB 0000 0.819 42%
GLP10-01-01-26-005 JPAL SD ET03 0 0000 1.06 1.4%
GLP10-01-01-26-006 JPAL SD ET04 0 0000 2.39 11%
BLQ; The integrated peak area response for PFOA in the sample was below the PFOA peak area response fo r the lowest standard that was used to construct the calibration curve (< nominal 0.200 ng/g). NA; not applicable

Table 2. LMS PFOA Recovery Results for Sediments fr om Jeffries Property, February 2012

**3M LIMS ID Sample ID PFOA Spike**  **Concentration (ng/g; dry weight)**  **PFOA Recovery**

**(Data Accuracy)**

GLP10-01-01-26-001 LMS JPAL SD TRIP1 0 0000, LMS 1. 00 ng 0.980 89.6% GLP10-01-01-26-002 LMS JPAL SD ET01 0 0000, LMS 2.0 0 ng 1.38 92.5% GLP10-01-01-26-003 LMS JPAL SD ET02 0 0000, LMS 2.0 0 ng 1.67 89.3% GLP10-01-01-26-004 LMS JPAL SD ET02 DB 0000, LMS 2. 00 ng 1.45 85.0% GLP10-01-01-26-005 LMS JPAL SD ET04 0 0000, LMS 2.0 0 ng 2.13 91.8% GLP10-01-01-26-006 LMS JPAL SD TRIP1 0 0000, LMS 2. 00 ng 3.34 101% [a] Samples with an endogenous PFOA level of BLQ we re treated as a concentration of zero to calculate recovery.Study: GLP10-01-01, Interim Report 26 Analysis for PFOA in Sediments Collected from the J effries Property, Feb. 2012

Page 9 of 19 

### 3 Introduction

The analyses reported herein were conducted as part of the Phase 3 Environmental Monitoring and Assessment Program for the 3M facility located in D ecatur, Alabama. The objective of the overall program is to gain information regarding concentrat ions 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 resu lts from analysis of sediments collected from the Jeffries property. The samples were collected by W eston Solutions, Inc. personnel in February 2012 and shipped to the 3M Environmental Laboratory for quantitative analysis of PFOA. One soil travel blank (trip blank) accompanied the sample bottles t o the site, during collection and during samples shipment and was analyzed to evaluate for any poten tial contamination of samples during the sample shipment and collection period. This report describes the sample shipment, receipt, extraction and quantitative LC/MS/MS analysis procedures conducted for determination of PFOA in t he soils for project GLP10-01-01-26. Additionally, included in this report are the asses sment of the analytical precision and accuracy for the reported PFOA concentration results, the recove ry results for a stable isotope labeled 13 C 4 -PFOA surrogate recovery standard (SRS) that was added to each soil aliquot prior to extraction, and the determined percent moisture content of each soil.



### 4 Test, Control and Reference Substances

This study does not have a test substance in the cl assic sense of a GLP study because this study was purely analytical in nature. The analytical re ference substances are listed in Table 3

.

Table 3. Reference Substances

Test Substance PFOA (linear isomer), free acid Technical PFOA (linear

+ branched isomers), ammonium salt 13 C 4 -PFOA 13 C 8 -PFOA

Use Calibration & LMSs LCSs Surrogate Internal Stan dard Source Oakwood 3M Wellington Labs Wellington Labs Expiration Date Jan.17, 2018 Feb. 27, 2017 Dec. 07, 2013 May 24, 2014 Storage Conditions Frozen Frozen Frozen Frozen
Chemical Lot 3440 332 MPFOA1210 052411

TCR Number TCR07-0041-1/1 TCR-123 TCR11-0001-11/14 TCR11-0016-13/17 & TC R11-0016-14/17 Physical Description Powder White Powder Methanol S olution [a] Methanol Solution [a ] Purity 99.6% 95% >98% >98% [a] Stable isotope labeled materials are typically provided as methanol solutions by the commercial ve ndor and are treated as 100% pure; the vendor’s reported methanol stock con centration is used for calculating concentrations o f diluted standards made from them.Study: GLP10-01-01, Interim Report 26 Analysis for PFOA in Sediments Collected from the J effries Property, Feb. 2012

Page 10 of 19 

### 5 Test System

There was not a test system for this study in the c lassic sense of a GLP study. This study was conducted for analysis of sediments collected from the Jeffries property that is located in Northern Alabama. Samples for this study are “real world” e nvironmental samples. 

### 6 Method Summary

6.1 Methods

The sample extractions and quantitative LC/MS/MS an alyses were performed following validated method ETS-8-053.0. Two analytical batches were prepared for this study as o120309c and o120316a. The resul t for the trip blank was reported from batch o120309c and results for field samples were reported from r un 120316a

.


### 6.2 Sample Receipt

On February 21, 2012 seven empty 250-mL HDPE Nalgen eTM sample bottles, and one travel blank (trip blank) containing approximately 10-25 grams o f a control soil TCR-455, were sent from the 3M Environmental Laboratory to Weston Solutions, Inc. field personnel for collection of sediments from the property known as the Bert Jeffries landfill. Following the sample collections by Weston Solutions, Inc. personnel, five sediment-filled sam ple bottles and the trip blank were returned in the bottles to the 3M Environmental Laboratory for quan titative analysis of PFOA. The samples were received with sample chains of custody numbers 1529 0 on March 02, 2012. Soil samples from Alabama are regulated and the sed iments for this study were shipped in accordance with USDA/APHIS soil permit number P330- 09-00125. Sample nomenclature follows the form JPAL-SD-ET-xxx x where the first string defines the Jeffries Property Alabama (JPAL), the second string defines the sample media (i.e., SD= sediment, SB –field sample duplicate), the third string defines the sit e location (ET = eastern tributary), the fourth str ing defines the field sample (1,2,3... or DB = duplicate field sa mple) . The fourth string defines the sediment samp ling depth (0000 = 0 ft to 0.5 ft interval).

6.3 Sample Preparation

Sample preparation was conducted as two analytical batches, o120309c and o120316a. The first batch was prepared with LMSs fortified at 20 and 200 ng o f PFOA, which was later determined to be too high f or a proper evaluation of PFOA recovery from the sedim ents which contained much lower PFOA levels. The trip blank was prepared with a 1 ng PFOA LMS and wa s reported from that batch. The samples were prepared a second time as o120316a with a 2 ng fort ified LMS for each sample, and the sample results reported from that batch.
Each soil or sediment extraction involved removal o f a 1 cubic centimeter (1 cc; 1 mL) aliquot of fiel d sample (typically ~ 1 gram) from each sample bottle using a fixed volume 1 cc spoon, transferring it t o a 15 mL conical centrifuge tube, followed by accurate we ight determination of the aliquot on a 5-place bala nce. Then, nominal 3.0 ng of internal standard (IS; nomi nal 3.0 ng) and 3.0ng of surrogate recovery standar d (SRS) was added to each soil aliquot and a known qu antity of PFOA was added to each LMS. Then each was extracted by addition of 8 mL of a 4:1 acetonit rile:water solution followed by sonication for 1 to 2 hours followed by centrifugation to remove solids. The s upernatant from each was then transferred to an aut ovialStudy: GLP10-01-01, Interim Report 26 Analysis for PFOA in Sediments Collected from the J effries Property, Feb. 2012

Page 11 of 19 for analysis. An accurately measured volume of eac h supernatant was analyzed by LC/MS/MS. During preparation, each sample additionally receiv ed nominal 3.0 ng of a stable isotope labeled surro gate recovery standard (SRS) as 13 C 4 -PFOA. Although not included as part of the data accuracy assessment for this study, SRS recovery determinations were in cluded as part of an ongoing method validation aspe ct for SRS behavior in environmental soil samples for potential future applications. The SRS was quantif ied from a SRS calibration curve constructed from analy sis of calibration standards prepared from the SRS in calibration standards. The SRS recovery was determ ined based on the calculated concentration of SRS from the analysis and recovery of SRS from each sam ple is included in Table 10 , but was not used for evaluation of data accuracy for this study and is o therwise excluded from the discussions in the repor t. Each analytical sample was prepared in duplicate fo r analysis of PFOA in the sample. Additionally, a third and/or fourth replicate was weighed out and used to prepare LMSs. The LMS results were used for determination of data accuracy. RPD of duplicate s amples results was used for determination of data precision. Appropriate LMS levels are considered t hose that are within 0.5-times to 10-times the meas ured endogenous PFOA level in the equivalent non-fortifi ed soil/sediment sample. 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 mas s of 1 cc of control soil TCR-455 is 1.0 gram (dry), therefore, the nominal calibration standard range prepared and analyzed was 0.200 ng/g to 500 ng/g. Laboratory control spike (LCS) samples were prepare d with each sample preparation batch; prepared at three levels (nominal 3.00 ng/g, 30.0 ng/g and 300 ng/g) and each level in triplicate. The LCSs were prepared using control soil TCR-455, same as calibr ation standards, and were fortified with technical PFOA (linear + branched isomer). The LCS results were used to estimate the analytical method uncertainty.

6.4 Percent Soil Moisture Determination

The percent moisture of sediments and soils were us ed to calculate the dry weight of the wet soil and sediment samples 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 determ ine the percent moisture, duplicate aliquots of eac h soil sample were removed and the accurate “wet” wei ght determined for each. All aliquots were dried a t > 100°C until no further mass loss occurred from wate r evaporation, at which time the accurate dried wei ghts were determined. The difference in mass, attribute d to water evaporation, was used to calculate the percent moisture of the original soil. The average d percent moisture result for each was then used to calculate the soil PFOA concentration on a dry weig ht basis, and is reported for each sample in Table 9

.

6.5 LC/MS/MS Analysis

The LC/MS/MS analysis was performed as described in method 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 f ortified PFOA from the LMS samples was used as a measure of sample-specific analytical accuracy. Recovery of the surrogate ( 13 C 4 -PFOA) is included within this report in Table 10 as an indirect measure of analytical data accuracy , and is not considered in the accuracy assessment for this stud y and is only included as part of an on-going method validation aspect in which surrogate recover y behavior is being evaluated in “real world” environmental samples for possible future applicati ons. Details of the specific instrument parameters, the liquid chromatography gradient program, and the spe cific mass transitions analyzed are detailed in the raw d ata, and are briefly described below in Table 4
, Table 5 and Table 6

.Study: GLP10-01-01, Interim Report 26 Analysis for PFOA in Sediments Collected from the J effries Property, Feb. 2012

Page 12 of 19 Table 4. Instrument Information

Instrument Name ETS-Ollie 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 Oasis HLB (3 x 20 mm, 25 μ ); 30°C Analytical column Betasil C18 (2.1 x 100 mm, 5 μ ) Injection Volume 25 μ L Mass Spectrometer API 4000 Ion Source TurboIon Spray Polarity Negative Software Analyst 1.4.2

Table 5. 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 6. Mass Transitions

Analyte Mass Transitions Monitored PFOA 413>169, 413>219, 413>369

13 C 4 -PFOA (Surrogate) 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 26 Analysis for PFOA in Sediments Collected from the J effries Property, Feb. 2012

Page 13 of 19 

### 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.

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) a liquots of 3M Environmental Laboratory matrix soil TCR-455 (nominal 1.0 gram per mL). A total of twelve (12) soil matrix calibration standards ranging from nominal P FOA concentration 0.200 ng/g to 500 ng/g were prepared and analyzed. Following the analysis of calibration standards, th e nominal concentration of each standard was plotted versus the measured analyte pe ak area/IS peak area response ratio. A quadratic equation with 1/x weighting was used to fit the cal ibration response data. Calibration curves were no t forced through zero. Calculating the determined st andard concentration using the resultant calibratio n curve and comparing to the known concentration conf irmed accuracy of each curve point within 100 ± 30% (+ 35% at the LLOQ). The correlation coefficient (r) was greater than 0.998, and coefficient of determination (r 2 ) was greater than 0.990. Calibration results for PFOA are summarized in Table 7

. Because soil weights vary significantly for a 1 cc (1 mL) soil sample, depending on soil type and mois ture 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 calibratio n standard prior to extraction ( e.g. calibrated in this study for a range of 0.200 ng/g to 200 ng/g PFOA). Because a 1cc aliquot of control soil TCR-455 weig hs approximately 1.0 gram (dry weight) and has less th an 5% moisture content, the nominal concentration range of the calibration was essentially 0.200 ng/g to 200 ng/g. However, because the sample soils an d sediments can vary in moisture content, composition and density, 1 cc aliquots of field soil and sedim ent samples typically weigh more or less than 1.0 gram. Therefore, the final measured results from the analysis were adjusted for the accurate determined dry weight of the 1 cc sample aliquot that was extracted.

Table 7. 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 Conc. 0.200 0.500 0.750 1.00 2.50 5.00 9.99 25.0 50.0 100 200 500 N/A

o120309c excluded 0.342 0.651 1.01 2.78 5.13 11.9 27.2 53.5 101 183 5 12 0.9984

o120316a 0.166 0.511 0.763 0.911 2.62 5.45 10.4 26. 3 51.7 96.8 198 502 0.9998
**Average (ng)** 0.166 0.427 0.707 0.961 2.70 5.29 11.2 26.8 52.6 98 .9 191 507 0.9991 **Avg. Recovery (%)**  83.0% 85.3% 94.3% 96.1 % 108% 106% 112% 107% 105% 98.9% 95.3% 101% NA
NA; not applicable [a] PFOA concentrations are nominal ng/g (dry soil wt) concentration based on a nominal mass of 1.0 gr am (dry wt.) for each 1 cubic centimeter of control soil used to prepare each calibration st andard.Study: GLP10-01-01, Interim Report 26 Analysis for PFOA in Sediments Collected from the J effries Property, Feb. 2012

Page 14 of 19 

### 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 blanks. The LLOQ for analytical run o120309c, from which the trip blank result was reported, was nomin al 0.500 ng/g calibration standard. The LLOQ for analytical batch o120316a, from which the study sam ple results were reported, was nominal 0.200 ng/g. All sample analyte responses less than the response of the 0.200 ng/g calibration standard were report ed as BLQ (below the limits of quantitation).

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 for PFOA from CCVs were used to confirm that the instrument response and the initial calibration curve were sti ll in control. All CCVs flanking reported PFOA dat a met the method criteria of 100% ± 30% accuracy, except for in o120309c where one of the CCVs for PFOA was at 131% and the PFOA result for the trip blank in that run reported with a method deviation.

7.4 Blanks

Three types of blanks were analyzed during this ana lysis: solvent blanks; and method blanks, which wer e prepared with blank matrix soil TCR-455 and were sp iked with IS and surrogate; and travel blanks (trip blanks) prepared from aliquots of soil TCR-455 cont ained in sealed sample bottles that accompanied the bottle order to Decatur, AL and the collection site , and returned with the sample shipment back to 3M Environmental Laboratory. The different blanks res ults were reviewed to evaluate potential contaminat ion during shipment and sampling, to evaluate method pe rformance parameters such as injector carry over and also to establish the LLOQ and the performance of the blanks were considered in the reporting of a ll results.

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 + bra nched isomer). The linear + branched isomer quantitation using a linear PFOA calibration curve provided a measure of accuracy in quantifying the sum of poten tial linear + branched PFOA isomers that are commonly associated with environmental samples. Ea ch LCS level was prepared in triplicate. The averaged results of the LCS analyses are shown in Table 8 and calculated analytical method uncertainty is shown in Table 9. The method acceptance criteria of 100 ± 30% was m et for all LCSs. The LCS recoveries were calculated using the following equa tion:



### 100% * ion Concentrat Spike LCS)

of ion Concentrat d (Determine Recovery LCS =Study: GLP10-01-01, Interim Report 26 Analysis for PFOA in Sediments Collected from the J effries Property, Feb. 2012

Page 15 of 19 Table 8. LCS Results

**Sample ID PFOA Recovery** 
**3.00 ng LCS 30.0 ng LCS**  **300 ng LCS**

LCSs (o120309c) 114% 114% 129% 97.0% 108% 104% 108% 110% 107%

LCSs (o120316a) 89.7% 93.7% 102% 97.0% 93.7% 95.0% 95.3% 88.3% 96.3% **Average Recovery** 100% 101% 106% **Std Dev.** 9.1% 10% 12% **RSD** 9.1% 10% 12% **Overall Average** 102%
**Overall Std. Dev.** 10%
**Overall RSD** 10% **Method Uncertainty (95% CI) = 2 x Std Dev. all levels**  **21%** LCS concentrations were 3.00 ng, 30.0 ng and 300 ng of PFOA (linear + branched isomers) added to each nominal 1 gram of control soil used to prepare the LCSs (1 cc of soil TCR-455 equal to nominal 1.0 gram; dry wei ght).

7.6 Laboratory Matrix Spikes (LMSs)

Laboratory matrix spikes (LMSs) were generated by s piking a known quantity of PFOA (linear) to an aliq uot of each soil/sediment sample and then preparing the sample the same as regular non-fortified samples. For this study, LMSs were prepared for each field s ample at 20 and 200 ng PFOA as a low LMS and high LMS, respectively, in run o120309c. However, those LMS levels were too high and samples re-prepared in o120316a with LMSs fortified with 2 ng PFOA. One LMS was prepared for the trip blank and fortifi ed with nominal 1.00 ng PFOA in run o120309c and was r eported from that run. The LMS recoveries for PFOA are shown in Table 2 . The method acceptance criteria of 100 ± 30% wa s met for all LMSs. 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 −

=Study: GLP10-01-01, Interim Report 26 Analysis for PFOA in Sediments Collected from the J effries Property, Feb. 2012

Page 16 of 19 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 10

. 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 10. Percent Moistures for Jeffries Property Sediments, February 2012

LIMS ID Sample ID Average Percent Moisture (w/w) [a] Relative Percent Difference [a]

GLP10-01-01-26-001 JPAL SD TRIP1 0 0000 2.72% 2.5%
GLP10-01-01-26-002 JPAL SD ET01 0 0000 28% 0.78%
GLP10-01-01-26-003 JPAL SD ET02 0 0000 30% 1.5%
GLP10-01-01-26-004 JPAL SD ET02 DB 0000 30% 0.78%
GLP10-01-01-26-005 JPAL SD ET03 0 0000 40% 3.6%
GLP10-01-01-26-006 JPAL SD ET04 0 0000 61% 0.096% [a] Percent moisture determined for duplicate samp les of soil/sediment taken from each sample bottle

7.8 Individual Sample Results

The individual sample concentration results are sho wn in Table 11.

Table 11. Individual PFOA Results for Jeffries Pro perty Sediments, February 2012

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) JPAL SD TRIP1 0 0000 101% NA BLQ NA BLQ JPAL SD TRIP1 0 0000 Duplicate 113% BLQ JPAL SD TRIP1 0 0000 LMS [c] 113% 0.980 0.878 89.6% NA JPAL SD ET01 0 0000 98.2% NA 0.671 NA 0.629 JPAL SD ET01 0 0000 Duplicate 103% 0.586 JPAL SD ET01 0 0000 LMS 94.5% 1.38 1.91 92.5% 14% JPAL SD ET02 0 0000 109% NA 0.592 NA 0.671 JPAL SD ET02 0 0000 Duplicate 106% 0.749 JPAL SD ET02 0 0000 LMS 97.2% 1.67 2.16 89.3% 23% JPAL SD ET02 DB 0000 96.2% NA 0.990 NA 0.819Study: GLP10-01-01, Interim Report 26 Analysis for PFOA in Sediments Collected from the J effries Property, Feb. 2012

Page 17 of 19 Table 11. Individual PFOA Results for Jeffries Pro perty Sediments, February 2012

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) JPAL SD ET02 DB 0000 Duplicate 94.5% 0.649 JPAL SD ET02 DB 0000 LMS 104% 1.45 2.05 85.0% 42% JPAL SD ET03 0 0000 109% NA 1.07 NA 1.06 JPAL SD ET03 0 0000 Duplicate 104% 1.05 JPAL SD ET03 0 0000 LMS 101% 2.13 3.02 91.8% 1.4% JPAL SD ET04 0 0000 100% NA 2.25 NA 2.39 JPAL SD ET04 0 0000 Duplicate 108% 2.53 JPAL SD ET04 0 0000 LMS 104% 3.34 5.76 101% 11% NA; Not applicable BLQ; Below the lower limit of quantitation [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, [b] LMSs prepared using PFOA (linear isomer). [c] Values below the LLOQ (BLQ) were treated as a c oncentration of zero for LMS recovery calculations



### 8 Conclusion

Analysis of the sediments collected from the Jeffri es property was successfully completed following 3M Environmental Laboratory method ETS-8-053.0 and conducted as 3M study GLP10-01-01-26. The average PFOA concentration results for the samp les and trip blank are summarized in Table 1 and associated LMS recoveries are summarized in Table 2 . The PFOA results for each individual analytical sample replicate used for reporting are provided in Table 10

. All sample results were reported with LMS recoverie s within 100 + 15%, and duplicate results gave RPDs of less than 50%. The travel blank that accom panied the sample bottles shipments was below the low limit of quantitation (BLQ, less than nomin al 0.500 ng/g), indicating there wasn’t any contamination of samples during sample shipment, st orage and preparation for analysis.

9 Data/Sample Retention

All soil samples and associated project data (hardc opy and electronic) will be archived as project GLP 10- 01-01-26 according to 3M Environmental Laboratory s tandard operating procedures.

10 List of Attachments

Attachment A: Preparation Forms, Raw Data and ChromatogramsStudy: GLP10-01-01, Interim Report 26 Analysis for PFOA in Sediments Collected from the J effries Property, Feb. 2012

Page 19 of 19 

## Attachment A
Preparation Forms, Raw Data and Chromatograms