# 3

GLP10-01-02 Interim Report 25: Analysis of PFOS, PF HS and PFBS in

Sediments Collected from the Jeffries Property



## Study Title 3M Environmental Laboratory Analytical Protocol GLP 10-01-02: Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane Sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur P hase 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 GLP10-01-02-25

Total Number of Pages

24Study: GLP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collect ed from the Jeffries Property

Page 2 of 24 This page has been reserved for specific country re quirements.Study: GLP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collect ed from the Jeffries Property

Page 5 of 24 

## 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 ............

................................................... ......................... 10

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

................................................... ............................................. 11

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

................................................... ....................................... 11

6.1 Methods ...........................................

................................................... .................................. 11

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

................................................... ............................. 11

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

................................................... ........................... 12

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

................................................... ................. 13

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

................................................... .......................... 13

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

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

7.1 Calibration .......................................

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

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

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

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

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

7.4 Blanks ............................................

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

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

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

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

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

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

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

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

................................................... .................. 19Study: GLP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collect ed from the Jeffries Property

Page 6 of 24 8 Conclusion ........................................

................................................... .............................................. 22

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

................................................... ..................................... 23

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

................................................... .......................................... 23

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

................................................... ............................................... 23



## L IST OF 

## T

ABLES

Table 1. Results for Jeffries Property Sediments .

................................................... .................................. 8
Table 2. LMS Recovery for Jeffries Property Sedime nts ............................................... ........................... 9

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

................................................... ........................................... 13
Table 5. Gradient Liquid Chromatography Conditions (ETS-8-053)....................................... ................ 14

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

................................................... .............................................. 14
Table 7. PFOS Calibration Summary ................

................................................... .................................... 15
Table 8. PFHS Calibration Summary ................

................................................... .................................... 15
Table 9. PFBS Calibration Summary ................

................................................... .................................... 15
Table 10. LCS Results (PFOS, linear + branched iso mer) .............................................. ....................... 17
Table 11. LCS Results (PFHS, linear + branched iso mer) .............................................. ....................... 17
Table 12. LCS Results (PFBS) .....................

................................................... ......................................... 17
Table 13. Analytical Method Uncertainties ........

................................................... .................................... 18
Table 14. Percent Moistures for Jeffries Property Sediments ......................................... ........................ 19

Table 15. Individual PFOS Results for Jeffries Pro perty Sediments ................................... ................... 19

Table 16. Individual PFHS Results for Jeffries Pro perty Sediments.................................... ................... 20

Table 17. Individual PFBS Results for Jeffries Pro perty Sediments ................................... .................... 21Study: GLP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collect ed from the Jeffries Property

Page 7 of 24 

### 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 12, 2012 Interim Analytical Completion: May 29, 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: GLP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collect ed from the Jeffries Property

Page 8 of 24 

### 2 Summary

This interim report provides the PFOS, PFHS and PFB S concentration results for five sediment samples collected in March 2012 at the Jeffries property in northern Alabama. In addition, one travel blank ( trip blank), containing between10-25 grams of control so il in a sample bottle, accompanied the sample bottl es to and from the site and was also analyzed for qual ity control purposes. Samples were logged into the 3M Environmental Laboratory information management sys tem (LIMS) under project GLP10-01-01-26 and cross referenced to this project GLP10-01-02-25 for additional fluorochemical sulfonates analysis. Fo ur aliquots of sample were removed from each sample bo ttle and accurately weighed for extraction. The fi rst and second aliquot served as analytical sample and duplicate analytical sample. The third and fourth aliquots were fortified with nominal 20.0 and 200 n g each of PFOS (linear isomer), PFHS (linear isomer ) and PFBS as a low and high laboratory matrix spike (LMS), respectively. Three aliquots of the trip bl ank were taken, with the third prepared as a single LMS that was fortified with nominal 1.00 ng each of PF OS (linear isomer), PFHS (linear isomer) and PFBS. Sa mples were extracted and analyzed per method ETS8-053 by liquid chromatography with triple quadrapo le mass spectrometric detection (LC/MS/MS). The LMS recovery results provided a measure of the data accuracy. The relative percent difference (RPD) o f the duplicate analytical sample results was used to assess the data precision. The percent moisture o f each soil was also determined as part of the study. The PFOS, PFHS and PFBS concentrations are summarized in Table 1 . The PFOS, PFHS and PFBS recoveries from the LMS samples are summarized in Table 2 . The average data accuracy and standard deviation determined from LMS results was 107% + 7.9% for PFOS, 105% + 7.2% for PFHS and 106% + 5.2% for PFBS. The analytical method uncertainty (95% CI) was determined at + 7.3% for PFOS, + 10% for PFHS and + 12% for PFBS.

Table 1. Results for Jeffries Property Sediments



### 3M LIMS ID [d] 

### Sample ID Average Concentration (ng/g; dry) PFOS PFHS PFBS GLP10-01-01-26-001 JPAL SD TRIP1 0 0000 BLQ BLQ BLQ GLP10-01-01-26-002 JPAL SD ET01 0 0000 3.95 BLQ BLQ GLP10-01-01-26-003 JPAL SD ET02 0 0000 8.59 BLQ BLQ GLP10-01-01-26-004 JPAL SD ET02 DB 0000 10.0 BLQ BLQ GLP10-01-01-26-005 JPAL SD ET03 0 0000 12.1 BLQ BLQ GLP10-01-01-26-006 JPAL SD ET04 0 0000 23.8 BLQ BLQ All LMS recovery results were within acceptance cr iteria of 100 + 30% Average concentration of duplicate analytical resul t reported; RPDs of duplicates were less than 10% The analytical method uncertainty was determined fr om LCS results at + 12% for PFBS, + 10% for PFHS and + 7.2% for PFOS Concentration values are shown at 3 significant fig ures, but more precise data was used for data calcu lations. BLQ; analyte response was lower than the analyte re sponse of the lowest standard (LLOQ) which was the nominal 0.500 ng calibration standard (i.e. less than nominal 0.50 n g/g)Study: GLP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collect ed from the Jeffries Property

Page 9 of 24 Table 2. LMS Recovery for Jeffries Property Sedime nts



### 3M LIMS ID [b] 

### Sample ID LMS Recovery (%) PFOS PFHS PFBS GLP10-01-01-26-001 Low JPAL SD TRIP1 0 0000 LMS 130% 125% 105% GLP10-01-01-26-002 Low JPAL SD ET01 0 0000 LMS Low 102% 105% 114% GLP10-01-01-26-002 High JPAL SD ET01 0 0000 LMS High 103% 103% 103% GLP10-01-01-26-003 Low JPAL SD ET02 0 0000 LMS Low 104% 102% 110% GLP10-01-01-26-003 High JPAL SD ET02 0 0000 LMS High 104% 105% 103% GLP10-01-01-26-004 Low JPAL SD ET02 DB 0000 LMS Low 105% 100% 105% GLP10-01-01-26-004 High JPAL SD ET02 DB 0000 LMS High 104% 103% 98.5% GLP10-01-01-26-005 Low JPAL SD ET03 0 0000 LMS Low 111% 105% 108% GLP10-01-01-26-005 High JPAL SD ET03 0 0000 LMS High 108% 107% 104% GLP10-01-01-26-006 Low JPAL SD ET04 0 0000 LMS Low 105% 108% 115% GLP10-01-01-26-006 High JPAL SD ET04 0 0000 LMS High 104% 97.0% 101% Average Recovery 

### 107% 105% 106% Standard Deviation 

### 7.9% 7.2% 5.2% RSD 

### 7.4% 6.8% 4.9% LMSs were fortified with PFOS, PFHS and PFBS (linea r isomers only) at nominal 20.0 ng (low) and 200 ng (high). The LMS for the trip blank was fortified at nominal 1.0 ng each of PFOS, PFHS and PFBS Recovery values are shown at 3 significant figures, but more precise data was used for data calculatio ns.



### 3 Introduction

The soil analyses 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 perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHS) and perflu orobutane sulfonate (PFBS) 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 PFOS, PFHS and PFBS. One soil travel blank (trip blank) accompanied the sample bottles to the site, during collection and during samples shipment and was analyzed to evaluat e for any potential 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 PFOS, PFH S and PFBS in the sediment samples that were received. Additionally, included in this rep ort are the assessment of the analytical precision and accuracy for the reported PFOS, PFHS and PFBS c oncentration results based on duplicate analytical sample results and laboratory matrix spi ke (LMS) recovery results, respectively. The recovery results for a stable isotope labeled 13 C 4 -PFOS surrogate recovery standard (SRS) that was added to each soil aliquot prior to extraction, and the determined percent moisture content of each soil, are also included herein.Study: GLP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collect ed from the Jeffries Property

Page 10 of 24 

### 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 reference and control substances are listed in Table 3

. Table 3. Reference Substances

Reference ID PFOS (linear) PFOS (linear + branched) PFHS (linear)

Chemical Name n-Perfluorooctane-1- Sulfonate Potassium Salt Perfluorooctane Sulfonate Potassium Salt n-Perfluorohexane-1-sulfonate Sodium Salt

Chemical Formula n-C 8 F 17 SO 3 K C 8 F 17 SO 3 K n-C 6 F 13 SO 3 Na

Use Reference Standard for Calibration and LMSs Reference Standard for LCSs Reference Standard for Calibration and LMSs

Source Wellington Laboratories 3M Wellington Laboratories

Expiration Date 10/18/18 12/14/16 3/25/18

Storage Conditions Frozen Frozen Frozen

Chemical Lot Number LPFOSKBM06 171 LPFHxSAM08

TCR Number TCR08-0001-1/1 TCR-696 TCR08-0018-1/1

Physical Description Crystalline White Powder Crystalline

Purity 98% 86.4% >98%

Reference ID PFHS (linear + branched) PFBS (predominantly linear) 13 C 4 -PFOS

Chemical Name n-Perfluorohexane-1- sulfonate Potassium Salt Perfluorobutane-1-sulfonate Potassium Salt [1,2,3,4- 13 C 4 ]-Perfluorooctane1-Sulfonate Sodium Salt

Chemical Formula n-C 6 F 13 SO 3 K n-C 4 F 9 SO 3 K 13 C 4 12 C 4 F 17 SO 3 Na

Use Reference Standard for LCSs Reference Standard for All PFBS Surrogate

Source 3M 3M Wellington Laboratories

Expiration Date 2/12/17 1/10/17 9/8/2013 Storage Conditions Frozen Frozen Frozen Chemical Lot Number NB 120067-69 101 MPFOS0910 TCR Number TCR-083 TCR-121 TCR10-0044-2/9 Physical Description White Powder White Powder Liquid; Methanol solution Purity 98.6% 96.7% >98% [a]Study: GLP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collect ed from the Jeffries Property

Page 11 of 24 Reference ID 13 C 8 -PFOS 13 C 3 -PFHS 18 O 2 -PFBS

Chemical Name [ 13 C 8 ]-Perfluorooctane-1- Sulfonate Sodium Salt [ 13 C 3 ]-Perfluorohexane-1- Sulfonate Sodium Salt [ 18 O 2 ]-Perfluorobutane-1- Sulfonate Ammonium Salt

Chemical Formula 13 C 8 F 17 SO 3 Na 13 C 3 12 C 3 F 13 SO 3 Na C 4 F 9 S 18 O 2 16 O NH 4

Use Internal Standard for PFOS Internal Standard for PFHS Internal Standard for PFBS

Source Wellington Laboratories Wellington Laboratories RTI International

Expiration Date 9/28/2013 9/28/2013 3/9/15

Storage Conditions -20 ̊C -20 ̊C -20 ̊C

Chemical Lot Number 092310 092310 11546-107-2

TCR Number TCR10-0048-3/16, 4/16 TCR10-0048-3/16, 4/16 TCR-1042

Physical Description Liquid; Methanol solution Liquid; Methanol solution Liquid; Methanol solution

Purity >98% [a] >98% [a] >99% [a]
[a] The commercially provided material was a methan ol solutions and labeled with a weight/volume conce ntration purity value. However, the concentration of furthe r dilutions was based on the certified concentratio n of the stock material.



### 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 method ETS-8-053.0. The results reported herein were obta ined from analytical run j120507b. Two analytical runs were conducted as o120312a and o120313a, but result not used due to QC results that did not meet method acceptance criteria.



### 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 Jeffries Property, former ly the Bert Jeffries landfill. Following the sam pleStudy: GLP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collect ed from the Jeffries Property

Page 12 of 24 collections by Weston Solutions, Inc. personnel, fi ve sediment-filled sample bottles and the trip blan k were returned in the bottles to the 3M Environmenta l Laboratory for quantitative analysis of PFOS, PFHS and PFBS. The samples were received with samp le chains of custody numbers 15290 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

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 PFOS (linear isomer), PFHS (linear isomer ) and PFBS was added to each LMS. Then each was ext racted by addition of 8 mL of a 4:1 acetonitrile:water solution followed by sonication for 1 to 2 hours followed by centrifugation to remo ve solids. The supernatant from each was then transfe rred to an autovial for analysis. An accurately measured volume of each supernatant was analyzed by LC/MS/MS. During preparation, each sample and quality control sample received nominal 3.0 ng of a stable isotope labeled 13 C 4 -PFOS surrogate recovery standard (SRS). Although not included as part of the data accuracy assessment for this study, SRS recovery determinati ons were included as part of an ongoing method validation aspect for SRS behavior in environmental soil and sediment samples for potential future applications. The SRS was quantified from a SRS ca libration curve constructed from analysis of calibration standards prepared from the SRS in cali bration standards. The SRS recovery was determined based on the calculated concentration of SRS from t he analysis and recovery of SRS from each sample is included in Tables 15, 16 and 17 but was not used for evaluation of data accuracy fo r this study and is otherwise excluded from the discussions in the repo rt. Each analytical sample was prepared in duplicate fo r analysis of PFOS, PFHS and PFBS in the sample. Additionally, a third and/or fourth replicate was w eighed out and used to prepare LMSs. The LMS resul ts were used for determination of data accuracy. RPD of duplicate samples results was used for determination of data precision. Appropriate LMS l evels are considered those that are within 0.5-time s to 10-times the measured endogenous analyte level in t he equivalent non-fortified soil/sediment sample, a nd the fortification of 20 ng and 200 ng was sufficien t in at least one of the LMSs to be considered appr opriate for determination of the data accuracy for PFOS, bu t was greater than 10-times the PFBS and PFHS endogenous levels which were less than the LLOQ (BL Q) in all samples. Calibration standards were prepared by spiking know n quantities of PFOS (linear isomer), PFHS (linear isomer), PFBS and 13 C 4 -PFOS 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 gram (dry), therefore, the nominal calibration standard range p repared 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 PFOS (mixe d linear + branched isomers), PFHS (mixed linear + br anched isomers) and PFBS. The LCS results were used to estimate the analytical method uncertainty.Study: GLP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collect ed from the Jeffries Property

Page 13 of 24 

### 6.4 Percent Soil Moisture Determination

The percent moisture of sediment samples was determ ined by gravimetric analysis. Dry weights were determined from separate weighings than the sample aliquot weighings used for extractions. To determine the percent moisture, duplicate aliquots of each soil sample were removed and the accurate “wet” weight determined for each. Each aliquot was then dried at > 100°C until no further mass loss occurred from water evaporation, at which time the accurate dry sample weights were determined. The difference in mass, attributed to water evaporation , was used to calculate the percent moisture of the original sample. The averaged percent moisture res ult for each was then used to report the PFOS, PFHS and PFBS concentration on a dry weight basis.



### 6.5 LC/MS/MS Analysis

The analysis of sample extracts for PFOS, PFHS and PFBS was performed by LC/MS/MS as described in method ETS-8-053.0. The relative perc ent difference (RPD) of duplicate prepared sample results was used as a measure of the analyti cal precision. The determined recovery of fortified PFOS, PFHS and PFBS from LMS samples was used as a measure of analytical accuracy. Surrogate recoveries are reported in Tables 15, 16 and 17 , but were not used for evaluating analyte recovery for this study. The su rrogate data was collected as part of an on-going evaluation of surrogate recovery from environmental field samples for supporting a method validation of ETS-8-053. 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 4
, Table 5 and Table 6

.

Table 4. Instrument Information

Instrument Name ETS-Jonas (j) 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 m) 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 5000 Ion Source TurboIon Spray Polarity Negative Software Analyst 1.4.2Study: GLP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collect ed from the Jeffries Property

Page 14 of 24 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 PFBS 299>99, 299>80
18 O 2 -PFBS (IS) 303>84 PFHS 399>99, 399>80
13 C 3 -PFHS (IS) 402>80 PFOS 499>130, 499>99, 499>80
13 C 8 -PFOS (IS) 507>80
13 C 4 -PFOS (Surrogate) 503>80 Note: Multiple mass transitions are summed to give the instrument response for that analyte.



### 7 Analytical Results

Concentration values are rounded to three significa nt figures according to EPA rounding rules. Because of rounding some calculated values may vary slightly from those found in the raw data. Samples with RPDs for duplicate results of less tha n 50% and LMS results meeting the method criterion of within 100 ± 30% demonstrated that the method was appropriate for those samples and were reported without footnotes in results tables. The nominal 20.0 ng and 200 ng fortified quantitie s of PFOS, PFHS and PFBS into LMSs for field samples were at an appropriate level for evaluating sample-specific analyte recoveries for PFOS. Resul ts for PFHS and PFBS were all less than the LLOQ (BLQ) and therefore LMS fortifications were gr eater than 10-times the endogenous level measured in the samples.



### 7.1 Calibration

A set of calibration standards were prepared by spi king varying known quantities of PFOS (linear), PFH S (linear), PFBS and surrogate ( 13 C 4 -PFOS), and a fixed quantity of stable isotope labe led internal standards, into one cubic centimeter (1 cc, 1 mL) a liquots of 3M Environmental Laboratory control soil TCR-455 (nominal soil mass of 1.0 g/mL). A total o f twelve (12) calibration standards were prepared a s a set. The prepared standards were fortified from nominal 0.200 ng to 500 ng in 1 cubic centimeter ofStudy: GLP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collect ed from the Jeffries Property

Page 15 of 24 control soil TCR-455; equivalent to nominal 0.200 n g/g to 500 ng/g in soil TCR-455. Following analysi s of the calibration standards, the concentration of each standard was plotted against the measured analyte /IS peak area ratio. A quadratic equation with 1/x weighting was used to fit the data for eac h analyte. Calibration curves were not forced throug h zero. Determining the standard concentration usi ng the resultant calibration curve and comparing to th e known concentration confirmed accuracy of each curve point at within 100 ± 30% (+ 35% at the LLOQ). The correlation coefficient (r) was greater than 0.999 for all calibration curves, and the coefficie nt of determination (r 2 ) was greater than 0.990. Calibration results for PFOS, PFHS and PFBS are sum marized in Table 7
, Table 8 and Table 9
, respectively. Because soil and sediment weights can vary signific antly for a 1 cc (1 mL) field sample, depending on composition and moisture content, the instrument re sponse was calibrated for the known concentrations of target analytes based on the mass quantity of re ference substance added to a 1 cc soil (1 mL) calibration standard prior to extraction ( e.g. calibrated in this study for a range of 0.500 ng t o 500 ng PFOS, PFHS and PFBS; the 0.200 ng standard was excl uded). Because a 1cc aliquot of control soil TCR-455 weighs nominally 1.0 gram (dry weight) and has less than 5% moisture content, the nominal concentration range of the calibration was essentia lly 0.200 ng/g to 500 ng/g. However, because sampl e soil aliquots may weigh more than 1.0 gram and cont ain significant moisture, the determined concentrations during the analysis on an ng per sam ple aliquot basis from the calibration curve and th en adjusted for the accurate determined weight and per cent moisture so they could be reported on a ng/g (dry weight) basis.

Table 7. PFOS Calibration Summary

Analytical Run PFOS (ng) 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 0.199 0.499 0.748 0.997 2.49 4.99 9.97 24.9 49.9 99 .7 199 499 N/A

s111007a excluded 0.478 0.791 0.888 2.51 5.42 10.1 24.5 50.6 98.9 199 499 0.9999

Recovery N/A 95.8% 106% 89.1% 101% 109% 101% 98.4% 101% 99.2 % 100% 100% N/A

Table 8. PFHS Calibration Summary

Analytical Run PFHS (ng) r

STD 1 STD 2 STD 3 STD 4 STD 5 STD 6 STD 7 STD 8 ST D 9 STD 10 STD 11 STD 12

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

s111007a excluded 0.473 0.801 0.908 2.41 5.57 9.95 26.2 47.5 99.9 201 500 0.9998

Recovery N/A 94.6% 107% 90.8% 96.4% 111% 99.5% 105% 95.0% 99 .9% 101% 100% N/A

Table 9. PFBS Calibration Summary

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

s111007a excluded 0.415 0.773 0.944 2.54 5.90 9.76 25.5 51.5 97.7 199 501 0.9998

Recovery N/A 83.0% 103% 94.4% 102% 118% 97.6% 102% 103% 97.7 % 99.5% 100% N/AStudy: GLP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collect ed from the Jeffries Property

Page 16 of 24 

### 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 the linearity and accuracy requirement for a low st andard (100 + 35%) and for which the area counts were at least twice that of the average response de termined for the method blank injected just prior t o the calibration standards . The LLOQ for this stud y was the nominal 0.500 ng calibration standard (nominal 0.500 ng/g in soil TCR-455) for PFOS, PFHS and PFBS. All sample analyte responses less than the response of the 0.500 ng calibration stand ard were reported as BLQ (below the limits of quantitation). The upper limit of quantitation (UL OQ) was the nominal 500 ng calibration standard.



### 7.3 Continuing Calibration

During the course of each analysis, continuing cali bration verifications (CCVs) were performed by regu lar injection of a mid-level calibration standard after approximately every 15th sample injected in the analytical run. The back calculated concentration results were used to confirm that the instrument response and the initial calibration curve were sti ll 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 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 sealed in s ample bottle t hat accompanied the bottle order to and from the sampling site; and solvent blanks containing extrac tion solvent. The different blank results were reviewed to evaluate potential contamination during shipment, and to evaluate method performance parameters such as injector carry over and to estab lish the LLOQ. All blanks were below the LLOQ (BLQ)



### 7.5 Laboratory Control Spikes (LCSs)

Laboratory control spikes were prepared by spiking know quantities of PFOS (linear + branched), PFHS (linear + branched) and PFBS into 1 cc aliquots of soil TCR-455, fortified at nominal 3.0 ng and 30 ng and 300 ng levels, with each level prepared in trip licate. The results of the LCS analyses and calcul ation of analyte measurement accuracies (percent recovery ) for PFOS, PFHS and PFBS are shown in Table 10, Table 11 and Table 12 respectively. The analytical method uncertainty calculated from LCS results is shown in Table 13

.



### 100% * ion Concentrat Spike LCS)

of ion Concentrat d (Determine Recovery LCS =Study: GLP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collect ed from the Jeffries Property

Page 17 of 24 Table 10. LCS Results (PFOS, linear + branched iso mer)

Sample ID PFOS Recovery
3.00 LCS 30.0 LCS 300 LCS

LCSs (j120507b) 

### 114% 109% 118% 112% 109% 117% 108% 114% 113% Average Recovery 

### 111% 111% 116% Std Dev. 

### 2.9% 3.1% 2.8% RSD 

### 2.6% 2.8% 2.4% Nominal LCS concentrations were 3.00 ng/g. 30.0 ng/ g and 300 ng/g of PFOS (linear + branched isomers), each prepared and analyzed in triplicate.

Table 11. LCS Results (PFHS, linear + branched iso mer)

Sample ID PFHS Recovery
3.00 LCS 30.0 LCS 300 LCS

LCSs (j120507b) 

### 118% 109% 108% 116% 107% 113% 103% 107% 105% Average Recovery 

### 113% 108% 109% Std Dev. 

### 8.3% 1.1% 3.9% RSD 

### 7.4% 0.99% 3.5% Nominal LCS concentrations were 3.00 ng/g. 30.0 ng/ g and 300 ng/g of PFHS (linear + branched isomers), each prepared and analyzed in triplicate.

Table 12. LCS Results (PFBS)

Sample ID PFBS Recovery
3.00 LCS 30.0 LCS 300 LCS

LCSs (j120507b) 

### 116% 106% 98.3% 117% 114% 112% 113% 109% 106% Average Recovery 

### 116% 110% 106% Std Dev. 

### 2.1% 4.2% 7.0% RSD 

### 1.8% 3.8% 6.6% Nominal LCS concentrations were 3.00 ng/g. 30.0 ng/ g and 300 ng/g of PFBS, each prepared and analyzed in triplicate.Study: GLP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collect ed from the Jeffries Property

Page 18 of 24 Table 13. Analytical Method Uncertainties

Sample ID LCS Results
PFOS PFHS PFBS

3.00 LCSs 

### 114% 118% 116% 112% 116% 117% 109% 103% 113%

30.0 LCSs 

### 109% 109% 106% 109% 107% 114% 115% 107% 109%

300 LCSs 

### 119% 108% 98.3% 118% 113% 112% 113% 105% 106% Average Recovery 

### 113% 110% 110% Std Dev. 

### 3.7% 5.1% 6.1% RSD 

### 3.3% 4.7% 5.5% Method Uncertainty (2 x Std. Dev.); 95% CI 

### 7.3% 10% 12%


### 7.6 Laboratory Matrix Spikes (LMSs)

Laboratory matrix spikes (LMSs) were generated by a dding a known quantity of PFOS (linear), PFHS (linear) and PFBS to an aliquot of sediment sample, and then preparing the sample the same as nonspiked samples. Spikes for this study, LMSs were s piked at levels that were appropriate for the endogenous analyte levels in the soils, determined from screening analysis and fortified with the targ et analytes from 0.5-times to 10-times the endogenous analyte levels determined in the soil/sediment samples during the range finding analysis. The LMS method acceptance criterion of within 100 ± 30% were met for all LMS recoveries. The LMS recovery results are summarized in Table 2 . The nominal 20.0 ng and 200 ng fortified quantities of PFOS, PF HS and PFBS into LMSs for field samples were at an appropriate level for evaluating sample-specific an alyte recoveries for PFOS. Results for PFHS and PFBS were all less than the LLOQ (BLQ) and therefor e LMS fortifications were greater than 10-times the endogenous level measured in the samples. The PFOS, PFHS and PFBS recovery calculations for LMSs 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 for each soil s ample. Duplicate aliquots of each were taken and accurately weighed to determine the “wet” weight. Then each aliquot was dried at > 100°C until no further loss in mass occurred due to water evaporat ion, after which the dry weight was accurately determined. The average percent moisture and RPD o f the duplicate determinations for each soil are reported in Table 14 . The percent moisture was calculated by the follo wing equation:

100% * Mass Wet Soil Original Mass)

Soil Dried Mass Wet Soil (Original Moisture Percent −

=Study: GLP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collect ed from the Jeffries Property

Page 19 of 24 Table 14. Percent Moistures for Jeffries Property Sediments

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

GLP10-01-01-26-001 JPAL SD TRIP1 0 0000 2.7% 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 sampl e aliquots taken from each sample bottle



### 7.8 Individual Analytical Sample Results

The individual analytical sample results for PFOS, PFHS and PFBS concentrations are shown in Table 15
, Table 16 and Table 17, respectively

.

Table 15. Individual PFOS Results for Jeffries Pro perty Sediments

Sample Description Surrogate ( 13 C 4 -PFOS) Recovery LMS Spike

Concentration (ng/g; dry weight) Measured PFOS

Concentration (ng/g; dry weight) LMS

Recovery Average PFOS

Concentration (ng/g; dry wt.) and RPD (%)
GLP10-01-01-21-001 109% N/A BLQ N/A BLQ GLP10-01-01-21-001 Dup 110% BLQ GLP10-01-01-21-001 LMS 105% 1.04 1.35 130% N/A

GLP10-01-01-21-002 101% N/A 3.81 N/A 3.95 GLP10-01-01-21-002 Dup 103% 4.09

GLP10-01-01-21-002 Low LMS 102% 14.6 18.8 102% 7.0% GLP10-01-01-21-002 High LMS 104% 143 152 103% [a]

GLP10-01-01-21-003 106% N/A 8.99 N/A 8.59 GLP10-01-01-21-003 Dup 110% 8.20

GLP10-01-01-21-003 Low LMS 107% 15.0 24.1 104% 9.1% GLP10-01-01-21-003 High LMS 103% 151 166 104% [a]

GLP10-01-01-26-004 106% N/A 9.8 N/A 10.0 GLP10-01-01-26-004 Dup 104% 10.2Study: GLP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collect ed from the Jeffries Property

Page 20 of 24 Table 15. Individual PFOS Results for Jeffries Pro perty Sediments

Sample Description Surrogate ( 13 C 4 -PFOS) Recovery LMS Spike

Concentration (ng/g; dry weight) Measured PFOS

Concentration (ng/g; dry weight) LMS

Recovery Average PFOS

Concentration (ng/g; dry wt.) and RPD (%) GLP10-01-01-26-004 Low LMS 105% 16.6 27.5 105% 3.6% GLP10-01-01-26-004 High LMS 105% 152 168 104% [a]

GLP10-01-01-21-005 104% N/A 11.9 N/A 12.1 GLP10-01-01-21-005 Dup 106% 12.2

GLP10-01-01-21-005 Low LMS 104% 19.6 33.8 111% 2.9% GLP10-01-01-21-005 High LMS 104% 198 227 108% [a]

GLP10-01-01-21-006 104% N/A 23.5 N/A 23.8 GLP10-01-01-21-006 Dup 102% 24.1

GLP10-01-01-21-006 Low LMS 106% 35.8 61.4 105% 2.5% GLP10-01-01-21-006 High LMS 104% 380 418 104%

N/A; not applicable BLQ; analyte response was lower than the analyte re sponse of the LLOQ which was nominal 0.500 ng/g low standard. [a] LMS fortification level was greater than 10-tim es the endogenous analyte level.

Table 16. Individual PFHS Results for Jeffries Pro perty Sediments

Sample Description Surrogate ( 13 C 4 -PFOS) Recovery LMS Spike

Concentration (ng/g; dry weight) Measured PFHS

Concentration (ng/g; dry weight) LMS

Recovery Average PFHS

Concentration (ng/g; dry wt.) and RPD (%)
GLP10-01-01-21-001 109% N/A BLQ N/A BLQ GLP10-01-01-21-001 Dup 110% BLQ GLP10-01-01-21-001 LMS 105% 1.04 1.30 125% N/A

GLP10-01-01-21-002 101% N/A BLQ N/A BLQ GLP10-01-01-21-002 Dup 103% BLQ

GLP10-01-01-21-002 Low LMS 102% 14.6 15.3 105% [a] N/A GLP10-01-01-21-002 High LMS 104% 144 148 103% [a]

GLP10-01-01-21-003 106% N/A BLQ N/A BLQ GLP10-01-01-21-003 Dup 110% BLQ

GLP10-01-01-21-003 Low LMS 107% 15.1 15.4 102% [a] N/A GLP10-01-01-21-003 High LMS 103% 151 158 105% [a]Study: GLP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collect ed from the Jeffries Property

Page 21 of 24 Table 16. Individual PFHS Results for Jeffries Pro perty Sediments

Sample Description Surrogate ( 13 C 4 -PFOS) Recovery LMS Spike

Concentration (ng/g; dry weight) Measured PFHS

Concentration (ng/g; dry weight) LMS

Recovery Average PFHS

Concentration (ng/g; dry wt.) and RPD (%)
GLP10-01-01-26-004 106% N/A BLQ N/A BLQ GLP10-01-01-26-004 Dup 104% BLQ

GLP10-01-01-26-004 Low LMS 105% 16.7 16.7 100% [a] N/A GLP10-01-01-26-004 High LMS 105% 153 157 103% [a]

GLP10-01-01-21-005 104% N/A BLQ N/A BLQ GLP10-01-01-21-005 Dup 106% BLQ

GLP10-01-01-21-005 Low LMS 104% 19.7 20.7 105% [a] N/A GLP10-01-01-21-005 High LMS 104% 199 212 107% [a]

GLP10-01-01-21-006 104% N/A BLQ N/A BLQ GLP10-01-01-21-006 Dup 102% BLQ

GLP10-01-01-21-006 Low LMS 106% 36.0 38.7 108% [a] N/A GLP10-01-01-21-006 High LMS 104% 382 371 97.0% [a]
N/A; not applicable BLQ; analyte response was lower than the analyte re sponse of the LLOQ which was nominal 0.500 ng/g low standard. [a] LMS fortification level was too low relative to the endogenous analyte level to make an accurate d etermination of recovery.

Table 17. Individual PFBS Results for Jeffries Pro perty Sediments

Sample Description Surrogate ( 13 C 4 -PFOS) Recovery LMS Spike

Concentration (ng/g; dry weight) Measured PFBS

Concentration (ng/g; dry weight) LMS

Recovery Average PFBS

Concentration (ng/g; dry wt.) and RPD (%)
GLP10-01-01-21-001 109% N/A BLQ N/A BLQ GLP10-01-01-21-001 Dup 110% BLQ GLP10-01-01-21-001 LMS 105% 1.04 1.09 105% N/A

GLP10-01-01-21-002 101% N/A BLQ N/A BLQ GLP10-01-01-21-002 Dup 103% BLQ

GLP10-01-01-21-002 Low LMS 102% 14.6 16.6 114% [a] N/A GLP10-01-01-21-002 High LMS 104% 144 148 103% [a]

GLP10-01-01-21-003 106% N/A BLQ N/A BLQ GLP10-01-01-21-003 Dup 110% BLQ

GLP10-01-01-21-003 Low LMS 107% 15.1 16.6 110% [a] N/AStudy: GLP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collect ed from the Jeffries Property

Page 22 of 24 Table 17. Individual PFBS Results for Jeffries Pro perty Sediments

Sample Description Surrogate ( 13 C 4 -PFOS) Recovery LMS Spike

Concentration (ng/g; dry weight) Measured PFBS

Concentration (ng/g; dry weight) LMS

Recovery Average PFBS

Concentration (ng/g; dry wt.) and RPD (%) GLP10-01-01-21-003 High LMS 103% 151 148 103% [a]

GLP10-01-01-26-004 106% N/A BLQ N/A BLQ GLP10-01-01-26-004 Dup 104% BLQ

GLP10-01-01-26-004 Low LMS 105% 16.7 17.4 105% [a] N/A GLP10-01-01-26-004 High LMS 105% 153 150 98.5% [a]

GLP10-01-01-21-005 104% N/A BLQ N/A BLQ GLP10-01-01-21-005 Dup 106% BLQ

GLP10-01-01-21-005 Low LMS 104% 19.7 21.2 108% [a] N/A GLP10-01-01-21-005 High LMS 104% 199 206 104% [a]

GLP10-01-01-21-006 104% N/A BLQ N/A BLQ GLP10-01-01-21-006 Dup 102% BLQ

GLP10-01-01-21-006 Low LMS 106% 36.0 41.4 115% [a] N/A GLP10-01-01-21-006 High LMS 104% 382 384 101% [a]

N/A; not applicable BLQ; analyte response was lower than the analyte re sponse of the LLOQ which was nominal 0.500 ng/g low standard.



### 8 Conclusion

Sediments collected from the Jeffries Property in M arch 2012 were successfully analyzed for PFOS, PFHS and PFBS following 3M Environmental Laboratory method ETS-8-053.0 and conducted as 3M study GLP10-01-02-25. The average PFOS, PFHS and P FBS concentration results for the soil samples are summarized in Table 1 and the LMS recoveries are summarized in Table 2 . The individual analytical sample results are shown in Table 15
, Table 16 , and Table 17 for PFOS, PFHS and PFBS, respectively. The soil trip blank that ac companied the sample bottles to the site and then accompanied samples back to the laboratory was suff iciently devoid of PFOS, PFHS and PFBS, indicating that no contamination of the samples occ urred during sample shipment or sample to the laboratory. The PFHS and PFBS levels in the sample s were all less than the 0.5 ng/g calibration standard that defined the lower limit of quantitati on. The PFOS concentrations in the sediment samples ranged from 3.95 ng/g to 23.8 ng/g.
The data accuracy was within 100 + 30% and the data precision was excellent with RPDs less than 10%.
The analytical method uncertainties (95% CI) were d etermined by statistical examination of the LCS results for PFOS, PFHS and PFBS and were + 7.3% for PFOS, + 10% for PFHS and + 12% for PFBS, respectively, at the 95% confidence interval (95% CI).Study: GLP10-01-02, Interim Report 25 Analysis for PFOS, PFHS & PFBS in Sediments Collect ed from the Jeffries Property

Page 24 of 24 

## Attachment A
Preparation Forms, Raw Data and Chromatograms