summary of analytical results: multi-city food study · analytical report completion date june...

SUMMARY OF ANALYTICAL RESULTS: MULTI-CITY FOOD STUDY

The Multi-City Study was originally designed by Battelle Memorial Institute (Columbus,OH), to obtain preliminary data about the presence of fluorochemicals in foods and indrinking water to understand the potential sources of human exposure. The Multi-CityStudy paired each of three cities having manufacturing or commercial use offluorochemical products (test cities) with three cities that do not (control cities).

Information on residues in selected foods was obtained from analyses of food samplescollected in a market basket study. The market basket sampling of the original Multi-City Study design was implemented by Pace Analytical Services, Inc., Minneapolis, MN.The samples were analyzed for PFOS, PFOA, and FOSA by Centre AnalyticalLaboratories, Inc., State College, PA.

The distributions of the PFOS, PFOA, and FOSA residue data by food and city categoryreveal similar patterns of residue concentrations in the control and test cities for each typeof food. A total of 12 samples were found to contain levels of fluorochemical residuesabove the limit of quantification. Of the 12 samples with measurable fluorochemicalresidue levels, eight were samples collected in test cities.

Measurable quantities of PFOS were found in five samples: four whole milk samples(three from test cities) and a ground beef sample (test city). PFOS residues found in thefoods ranged from non-quantifiable levels to 0.852 ng/g.

Measurable quantities of PFOA were found in seven samples: two ground beef samples(neither from test cities); two bread samples (one from a test city); two apple samples(both from test cities); and one green bean sample (from a test city). PFOA residue levelsranged from non-quantifiable levels to 2.35 ng/g. A value of 14.7 ng/g was found forPFOA in a bread sample from a control city, but was considered “suspect” by CentreAnalytical.

Unknown

ANALYTICAL REPORT

STUDY TITLE

Analysis of PFOS, FOSA and PFOA From Various Food Matrices Using HPLC ElectrosprayMass Spectrometry

DATA REOUrREMENTS

EPA TSCA Good Laboratory Practice Standards 40 CFR 792

STUDY DIKECTOR

Karen Smith, Centre

SPONSOR REPRESENTATIVE

Susan A. Beach, 3M

ANALYTICAL REPORT COMPLETION DATE

June 21,2001

PERFORMING LABORATORY / TESTING FACILITY

Centre Analytical Laboratories, Inc. (Centre) 3048 Research Drive

State College, PA 16801 Phone: 8 14-23 1-8032

STUDY SPONSOR

31 Environmental Technology and S a d y Services Building 2-3E-09

PO Box 33331 St. Paul, MN 55133-3331

PROJECT IDENTIFICATION

Centre Protocol Number: OOP-023-057 Centre Study Number: 023-057

Total Pages: 151

Centre Study No.: 023-057 Centre Protocol No: OOP-023-057

GOOD LABORATORY PRACTICE COMPLIANCE STATEMENT

Centre Study Number 023-057, entitled “Analysis of PFOS, FOSA and PFOA From Various Food Matrices Using HPLC ElectrosprayNass Spectrometry,’’ conducted for 3M Environmental Technology and Safety Services, was performed in compliance with EPA TSCA Good Laboratory Practice Standards (40 CFR, Part 792) by Centre Analytical Laboratories, Inc. with the following exceptions:

1. The FOSA reference substance (analytical standard) used in this study has not been characterized under GLP’s. §792.105(a).

2. Specimen (egg sample) identification for three samples was not according to 792.130(c) because the labels became removed from the containers.

I

KarenSmith ” Study Director Centre Analytical Laboratories, Inc.

Susan A. Beach Sponsor Representative 3M Environmental Technology and Safety Serv:ices

CblZllO I Date

Centre Analytical Laboratories, Inc. Page 2 of 15 1


QUALITY ASSURANCE STATEMENT

Centre Analytical Laboratories’ Quality Assurance Unit reviewed Centre Study Number 023-057, entitled, “Analysis of PFOS, FOSA and PFOA From Various Food Matrices Using HPLC Electrosprayhlass Spectrometry”. All phases were reviewed for conduct according to Centre Analytical Laboratories’ Standard Operating Procedures, the Study Protocol, and all applicable Good Laboratoiy Practice Standards. All findings were reported to the Study Director and to management.

Date Phase Inspected

1. Protocol Review 02/14/01

2. Extraction and 02/14/01 Fortification

3. Raw Data and Draft Report Review

041 10- 1310 1

4. Raw Data and Draft Report 05/30/01 Review

5 . Final Report 06/19/01 Review

Date Reported Date Reported to to Centre

Studv Director* Management 03/23/01 02/26/0 1

02/26/0 1 03/23/01

0512 1/01 06/04/0 1

0610 1 /O 1 06/04/0 1

06/20/0 1 06/21/01

Date Reported to Sponsor

Management 03/23/0 1

03/23/01

06/15/01

0611 510 1

0612 1 /O 1

*The Study Director resided at the sponsor until 05/01/01 at which time a protocol amendment transferred Study Director duties to Centre Analytical Laboratories.

- u - 1 , * p e---

Naomi Lovallo Senior Quality Assurance Auditor

6 / a - i h Date

Centre Analytical Laboratories, Inc. Page 3 of 151


CERTIFICATION OF AUTHENTICITY

This report, for Centre Study Number 023-05’7, is a true and complete representation of the raw data for the study.

Submitted by: Centre Analytical Laboratories, Inc. 3048 Research Drive State College, PA 16801 (814) 231-8032

Study Director, Centre: I A ’

Study Director Centre Analytical Laboratories, Inc.

Centre Analytical Laboratories, Inc. Facility Management:

/ -

$hn Flaherty Laboratory Manager Centre Analytical Laboratories, Inc.

Spoyor Representative, 3M

I -

Suss: A. Beach 3M Environmental Technology and Safety Services

Centre Analytical Laboratories, Inc.

J&I21Jo I Date

Date

Date

Page 4 of 151


STUDY IDENTIFICATION

Analysis of PFOS, FOSA and PFOA From Various Food Matrices Using HPLC ElectrosprayMass Spectrometry

CENTRE PROTOCOL NUMBER: OOP-023-057

TYPE OF STUDY:

TEST SYSTEM:

Residue

Green beans, apples, pork muscle, cow milk, chicken muscle, chicken eggs, bread, hot dogs, catfish and ground beef

TEST MATERIAL: PFOS, FCSA and PFOA

SPONSOR:

STUDY DIRECTOR:

TESTING FACILITY:

ANALYTICAL PHASE TIMETABLE:


3M Environmental Technology and Safety Services Building 2-3E-09 PO Box 33331 St. Paul, MN 55133-3331

Karen Smith Centre Analytical Laboratories, Inc. Phone: (814) 231-8032

Centre Analytical Laboratories, Inc. 3048 Research Drive State College, PA 16801

Study Initiation Date: 0 1/09/0 1 Analytical Start Date: 01/11/01 Analytical Termination Date: 05/22/01

Page 5 of 151

Centre Study No.: 023-057 Centre Protocol No: 0013-023-057

PROJECT PERSONNEL

The Study Director for this project at Centre Analytical Laboratories, Inc. was Karen Smith. The following personnel from Centre Analytical Laboratories, Inc., were associated with various phases of the study:

Name

Karen Smith

Title

Scientist

Emily Stauffer Scientist

Angela Morgan Technician

Tiffany Proctor Technician

Rickey Keller Sample Custodian

Lawrence Ord Sample Custodian

Dave Bell Scientist

Sharareh Zolghadr Technician

Jason Farabaugh Scientist

Mi tra Arjmand

Yu Qiong Tan

Technician

Technician

Ling Ling Liu Technician

Xlaoming Zhu Technician


.

Centre Study No . . 023-057 Centre Protocol No: OOP-023-057

TABLE OF CONTENTS

TITLE PAGE ...................................................................................................................... 1

GOOD LABORATORY PRACTICE COMPLIANCE STATEMENT ............................. 2 QUALITY ASSURANCE STATEMENT .......................................................................... 3 CERTIFICATION OF AUTHENTIClTY ........................................................................... 4 STUDY IDENTIFICATION ............................................................................................... 5 PROJECT PERSONNEL .................................................................................................... 6

TABLE OF CONTENTS .................................................................................................... 7 LIST OF TABLES .............................................................................................................. 8

LIST OF FIGURES ............................................................................................................. 9 LIST OF APPENDICES ................................................................................................... 11

1.0 SUMMARY ............................................................................................................... 12 2.0 OBJECTIVE ................................................................................................................ 12 3.0 INTRODUCTION ....................................................................................................... 12 4.0 TEST SYSTEM ......................................................................................................... 13 5.0 REFERENCE MATERIAL ....................................................................................... 14

6.0 EXPERIMENTAL DESIGN ...................................................................................... 15

7.0 DESCRIPTION OF ANALYTICAL, METHOD ....................................................... 15 7.1 Extraction Procedure ........................................................................................... 15

7.2 Preparation of Standards and Fortification Solutions .......................................... 15 7.3 Chromatography .................................................................................................. 16 7.4 Instrument Sensitivity .......................................................................................... 17

7.5 Description of Instrument and Operathg Conditions .......................................... 17 7.6 Quantitation and Example Calculation ................................................................ 18

8.0 RESULTS AND DISCUSSION ............................................................................... 20

9.0 CIRCUMSTANCES THAT MAY H A W . AFFECTED THE DATA .................... 21 10.0 RETENTION OF DATA AND SAMPLES ............................................................. 21 11.0 TABLES ................................................................................................................... 22 12.0 FIGURES ................................................................................................................. 41 13.0 APPENDICES .......................................................................................................... 65

Centre Analytical Laboratories. Inc . Page 7 of 15 1


LIST OF TABLES

Table I. Summary of PFOS, FOSA and PFOA Fortification Recoveries ........................ 23

Table II. Summary of PFOS, FOSA and PFOA Residues Found in Samples ................. 26


Figure 1.

Figure 2.

Figure 3.

Figure 4.

Figure 5.

Figure 6.

Figure 7.

Figure 8.

Figure 9.

Figure 10.

Figure 11.

Figure 12.

Figure 13.

Figure 14.

Figure 15.

Figure 16.

Centre Study No.: 023-057 Centre Protocol No: 00P-023-057

LIST OF FIGURES

Typical Calibration Curve for PFOS .............................................................. 42

Typical Calibration Curve for FOSA ............................................................. 43

Typical Calibration Curve for PFOA ............................................................. 44

Chromatogram Representing a 0.5 ng/mL mixed calibration standard of PFOS, FOSA and PFOA ................................................................................ 45

Chromatogram Representing a 2.5 ng/mL mixed calibration standard of PFOS, FOSA and PFOA ................................................................................ 46

Chromatogram Representing a Control Apple Sample (Centre ID: 0009347 Blank Al, Data Set: 020901C Apple) ............................................................ 47

Chromatogram Representing a Control Apple Sample Fortified with 2.5 ng/g of PFOS, FOSA and PFOA (Centre ID: 0009347 Spk Al, Data Set: 020901C Apple) ............................................................................. 48

Chromatogram Representing an Apple Sample (Centre ID: 0012927, Sponsor ID: Publix, 18257, Data Set: 020901C Apple) ................................ 49

Chromatogram Representing a Control Green Bean Sample (Centre ID: 0009346 Blank A2, Data Set: 020601C Bean) .............................................. 50

Chromatogram Representing a Control Green Bean Sample Fortified with 2.5 ng/g of PFOS, FOSA and PFOA (Centre ID: 0009346 Spk A2, Data Set: 020601C Bean) ............................................................................... 51

Chromatogram Representing a Green Bean Sample (Centre ID: 0012910, Sponsor ID: Bruno’s, 18341, Data Set: 020601C Bean) ................................ 52

Chromatogram Representing a Control Pork Muscle Sample (Centre ID: 0009348 Blank Al, Data Set: 011501A Pork) ............................................... 53

Chromatogram Representing a Control Pork Muscle Sample Fortified with 2.5 ng/g of PFOS, FOSA and PFOA (Centre ID: 0009348 Spk Al, Data Set: 011501A Pork) ............................................................................... 54

Chromatogram Representing a Pork Muscle Sample (Centre ID: 0012795, Sponsor ID: Winn-Dixie, 18227, Data Set: 011501A Pork) .......................... 55

Chromatogram Representing a Control Milk Sample (Centre ID: 0009349 Blank Al, Data Set: 020701A Milk) ............................................................. 56

Chromatogram Representing a Control Milk Sample Fortified with 2.5 ng/g of PFOS, FOSA and PFOA (Centre ID: 0009349 Spk Al, Data Set: 020701A ~ l k ) ............................................................................... 57



Figure 17.

Figure 18.

Figure 19.

Figure 20.

Figure 21.

Figure 22.

Figure 23.

LIST OF FIGURES (CONTINUED)

Chromatogram Representing a Milk Sample (Centre ID: 0012871, Sponsor ID: Winn-Dixie, 18202, Data Set: 020701A Milk) ......................... 58

Chromatogram Representing a Control Chicken Egg Sample (Centre ID: 0009342 Blank A3, Data Sets: 050901A Egg for PFOS, 012401A Egg for FOSA, and 052101A Egg for PFOA) ....................................................... 59

Chromatogram Representing a Control Chicken Egg Sample Fortified with 2.5 ng/g of PFOS, FOSA and PF0,4 (Centre ID: 0009342 Spk A3, Data Sets: 050901A Egg for PFOS, 012401A Egg for FOSA, and 052101A Egg for PFOA) ............................................................................... 60

Chromatogram Representing a Chicken Egg Sample (Centre ID: 0012861, Sponsor ID: Save, 18167 and 21224, Data Sets: 050901A Egg for PFOS,

Chromatogram Representing a Control Bread Sample (Centre ID: 0009343 Blank Al, Data Set: 020901A Bread) ............................................................ 62

Chromatogram Representing a Control Bread Sample Fortified with 2.5 ng/g of PFOS, FOSA and PFOA (Centre ID: 0009343 Spk Al, Data Set: 020901A Bread) ............................................................................. 63

012401A Egg for FOSA, and 052101A Egg for PFOA) ............................... 61

Chromatogram Representing a Bread Sample (Centre ID: 0012887, SDonsor ID: Albertson’s. 18244. Data Set: 020901A Bread) ........................ 64



LIST OF APPENDICES &

Appendix A Study Protocol OOP-023-057 (Centre Study No. 023-057), Amendments and Deviation ...................................................................... 65



1.0 SUMMARY

The purpose of this study was to analyze residues of PFOS, FOSA and PFOA in various food matrices as specified in Centre Protocol OOP-023-057. The analytical method used for this study was entitled, “Method of Analysis for the Determination of Fluorochemicals in Green Beans, Apples, Pork Muscle, Cow Milk, Chicken Muscle, Chicken Eggs, Bread, Hot Dogs, and Catfish by LCMSMS.”

The limit of quantification for PFOS, FOSA and PFOA in food was 0.5 ppb (ng/g).

Average fortification recoveries and relative standard deviations were 101% f 9.0% for PFOS, 96% k 13% for FOSA and 104% f 14% for PFOA.

Residues ranging from non-quantifiable levels to 0.852 ppb (ng/g) for PFOS, non- quantifiable levels for FOSA, and non-quantifiable to 2.35 ng/g for PFOA (one value of 14.7 ppb (ng/g) was found for PFOA but was Considered suspect) were found in the food samples.

2.0 OBJECTIVE

The objective of this study was to determine levels of PFOS, FOSA and PFOA in food samples collected from local grocery stores from six test cities outlined in 3M Quality Assurance Project Plan for Empirical Human Exposure Assessment Multi-City Study Sampling Task using the analytical method entitled “Method of Analysis for the Determination of Fluorochemicals in Green Beans, Apples, Pork Muscle, Cow Milk, Chicken Muscle, Chicken Eggs, Bread, Hot Dogs, and Catfish by LCMSMS.”

3.0 INTRODUCTION

This report details the results of the residues of PFOS, FOSA and PFOA detected in green beans, apples, pork muscle, cow milk, chicken muscle, chicken eggs, bread, hot dogs, catfish and ground beef, using the analytical method entitled, “Method of Analysis for the Determination of Fluorochemicals in Green Beans, Apples, Pork Muscle, Cow Milk, Chicken Muscle, Chicken Eggs, Bread, Hot Dogs, and Catfish by LCMSMS.” Complete details of the analytical methodology can be found in Appendix A.

The study was initiated on January 09, 2001, when the study director signed the protocol OOP-023-057. The complete protocol and amendments can be found in Appendix A. The analytical start date was January 11 , 2001, and the analytical termination date was May 22,2001.



0009341

4.0 TEST SYSTEM

Chicken Muscle

The food samples analyzed in this study were received frozen from Pace Analytical on December 09, 2000 and stored frozen (c-10°C) upon receipt. Pace Analytical collected the samples for 3M Environmental Laboratory. The samples were then logged in on December 18, 2000 by Centre personnel and transferred to different frozen storage locale. All of the samples were processed according to the method, “Method of Analysis for the Determination of Fluorochemicals in Green Beans, Apples, Pork Muscle, Cow Milk, Chicken Muscle, Chicken Eggs, Bread, Hot Dogs, and Catfish by LCMSRMS.” Exact details of processing can be found on page 91 of this report. After processing, the samples were stored in a freezer at a temperature of -10°C or below until used and placed back into a freezer immediately after use.

Chicken Eggs ~

At the request of the sponsor, the egg samples were returned frozen to 3M Environmental Laboratory on February 26, 2001 for possible reanalysis. The egg samples were returned unanalyzed from 3M Environmental Laboratory to Centre Analytical Laboratories, Inc. These samples were received frozen from 3M Environmental Laboratory on May 03, 2001 for PFOS and PFOA re-extraction and analysis. They were assigned different 3M and Centre ID’S.

0009344 0009345

The food samples used for the controls and matrix spikes were the same samples used in the method validation study (Centre Study No. 023-043). They were purchased from Giant, Store #111 in State College, PA and assigned the following sample IDS upon log in at Centre:

Hot Dogs Catfish

I CentreSarnDle~~ I Samde DescriDtion I

Green Beans

Pork Muscle Whole Milk Ground Beef

All of the control samples were purchased on September 27, 2000 except for the ground beef, which was purchased on January 03, 2001. The samples were stored in a refrigerator (4” k 2OC) until processed. All of tlhese control samples were processed with dry ice in a Hobart food chopper on October OZ!, 2000 except for the ground beef, which was processed on January 03, 2001. After processing, the samples were stored in a freezer at a temperature of -10°C or below until used and placed back into a freezer immediately after use.



Sample login and chain of custody information can be found in the raw data package associated with this study. Storage records will be kept at Centre Analytical Laboratories, Inc. and a true copy of the storage records can be found in the raw data package associated with this study.

5.0 REFERENCE MATERIAL

PFOS was received at Centre on June 05, 2000, FOSA was received on February 15, 2000 and PFOA was received on July 06, 2000 from 3M Environmental Technology and Services. Characterization of the reference materials PFOS and PFOA was performed at Centre on August 3 1,2000 and November 06,2000, respectively, and documentation can be found in raw data package associated with this report. The characterization of FOSA is in progress and the necessary information will be added upon complete characterization of the reference materials. All analyses were completed prior to standard expiration dates.

The available information for the reference material is listed below. FOSA was stored at room temperature and PFOS and PFOA were stored frozen at I -1OOC.

Compound TCR Substance No. Batch No. Purity (%) Expiration Date PFOS TCROOO 17-46 NA 97.9 FOSA SD-029 L- 15709 95.1 PFOA TCR99030-30 332 95.0

0813 1/01 02/15/01 10/31/01

Molecular structures of PFOS, FOSA and PFOA are given below.

PFOS Chemical Name -

Molecular weight = 499 (CsF17S03-) Perfluorooctane sulfonate -

0

Note: The neutral molecule and standard form which PFOS (anion) is derived from is potassium perfluorooctane sulfoinate [CSF~~SO~K], molecular weight 538.

FOSA Chemical Name - Perfluorooctane sulfonylamide -

Molecular weight = 499 0



PFOA Chemical Name -

Molecular weight = 413 Perfluorooctanoate -

Note: The neutral molecule and standard form which PFOA (anion) is derived from is ammonium perfluoroctanoate [C7F&OONH4], molecular weight 43 1.

6.0 EXPERIMENTAL DESIGN

Each sample was extracted in duplicate. A set contained one matrix blank and two matrix blanks spiked with known amounts of PFOS, FOSA and PFOA and 6 - 10 samples. The re-extracted egg sets also included one reagent blank.

The extracts were analyzed by LCMSMS. Samples with residues below the linear range of the calibration curve were not quantified; however, residues in the control samples were calculated up to 20% of the LOQ by extrapolation of the calibration curve, in order to correct fortification recoveries.

7.0 DESCRIPTION OF ANALYTICAL METHOD

Analytical method entitled “Method of Analysis for the Determination of Fluorochemicals in Green Beans, Apples, Pork Muscle, Cow Milk, Chicken Muscle, Chicken Eggs, Bread, Hot Dogs, and Catfish by LCMS/MS” was used for this study.

7.1 Extraction Procedure

Five grams of processed sample were weighed into 50 mL polypropylene centrifuge tubes and fortified (if necessary). The samples were extracted with ACN followed by a SPE column (florisil, silica gel, carbon and LC-NH2) clean up. The column eluate was collected and concentrated to near dryness. Final volume was adjusted to 2 mL with 2% ascorbic acid in methanol. The samples were analyzed using electrospray LCMSMS.

7.2 Preparation of Standards and Fortification Solutions

Standard stock solutions of PFOS, PFOA and FOSA were prepared on September 18, 2000, September 26, 2000 and October 03, 2000, respectively. Fortification and calibration standard solutions were prepared on October 17, 2000 as specified in Centre Analytical Laboratories’ analytical method entitled, “Method of Analysis for the Determination of Fluorochemicals in Green FJeans, Apples, Pork Muscle, Cow Milk,



Initial Concentration

Chicken Muscle, Chicken Eggs, Bread, Hotdogs, and Catfish by LC/MS/MS.” Individual stock standard solutions of PFOS, FOSA and PFOA were prepared at concentrations of 100 pg/mL by taking 10 mg of the standard (corrected for purity and salt content where applicable) and bringing it up to 100 mL with methanol. From these solutions, a 1 pg/mL mixed fortification standard solution was prepared by taking 1 mL of each stock and bringing the volume up to 100 mL with methanol.

Volume Diluted to Final concentration

The 1 pg/mL mixed fortification standard was diluted ten-fold with methanol to make the 0.1 p g / d mixed fortification standard. Then, the 0.1 pg/mL mixed standard was diluted ten-fold with methanol to make the 0.01 pg/mL fortification standard.

1000 1000

LC/MS/MS calibration standards were prepared in methanol at the following concentrations 50,25, 10,5.0,2.5, 1.0, and 0.5 ng/mL according to the following table:

5.0 1010 50 2.5 100 25

5 .O 10.0 100 0.5 1 10.0 10.0 100 1 .o

New standard stock, fortification and calibration solutions were made for PFOS and PFOA in order to perform the egg re-extraction and analysis. The PFOS standard stock solution was prepared on March 14, 2001 and the PFOA standard stock solution was prepared on April 11, 2001. Mixed fortification and calibration solutions of PFOS and PFOA were prepared from the stock solutions ‘on May 03,2001 as described above. The only modification from the above procedure is that FOSA was omitted from the mix since the re-extraction and analysis was for PFOS and PFOA only.

The stock standard solution and all fortificaticln and calibration standard solutions were stored in a refrigerator (4” k 2°C) when not in use. Documentation of standard preparation can be found in the raw data associated with this report.

7.3 Chromatography

Quantification of PFOS, FOSA and PFOA was accomplished by LC/MS/MS analysis using electrospray LC/MS/MS.

The retention times of PFOS, FOSA and PFOA were - 5.4 min, - 6.0 min and - 5.3 min., respectively. The matrices Qd not contribute any interfering peaks corresponding to the



analyte retention times; however, there were some occasions where the control matrices appeared to contain analyte.

7.4 Instrument Sensitivity

The smallest standard amount injected during the chromatographic run was 0.5 ng/mL which is equivalent to 0.2 ng/g of PFOS, FOSA and PFOA in matrix.

7.5 Description of Instrument and Operating Conditions

A Micromass Quattro Ultima LC/MS/MS coupled to a Hewlet Packard HPLC system was used. Data acquisition and processing were performed using Masslynx 3.4 software. Detailed operating conditions are listed below:

Instrument : Micromass Quattro Ultima

ELECTROSPRAY ION SOURCE: Capillary: 2.0 kV Hexapole 1: 0 V Aperture 1: 0 V

Hexapole 2: 0 V Source Block Temp.: 100°C Desolvation Temp.: 400°C

ANALYmR: LM Res 1: 10.5 V HMRes 1: 10.5 V IEnergy 1: 1.0 V Entrance: -2 V Exit: 2 V

LM Res 2: 12.0 V HM Res 2: 12.0 V IEnergy 2: 2.0 V Multiplier: 650 V

GAS FLOWS AND PRESSURE: Desolvation N2 Flow Rate:: -700 L/hr Nebuliser Nz Flow Rate: -150 L/hr Gas Cell Pressure: -0.003 1 mbar

Computer: COMPAQ Professional Workstation AP200

Software: Microsoft Windows NT: Version 4 Build 1381: Service Pack 5 Micromass Limited: Masslynx 3.4 Build 004

HPLC Equipment: Hewlett Packard (HP) Series 1100 HP Binary Pump HP Autosampler HP Column Oven

HP Vacuum Degasser

HPLC Column: Genesis C-8, 5 cm x 2.1 mni i.d. x 4 p

Column Temperature: 35°C

Mobile Phase (A) : 2 mM Ammonium Acetate iin Type I Water



Mobile Phase (B) : Methanol

Time (min) % A 0.0 60.0 0.4 60.0 1 .o 10.0 7.0 10.0 7.5 0.0 9.0 0.0 9.5 60.0 13.5 60.0 14.0 60.0

Total run time = 14 min

Injected Volume: 15 pL

% B 40.0 40.0 90.0 90.0 100.0 100.0 40.0 40.0 40.0

Flow Rate (mWmin) 0.3 0.3 0.3 0.3 0.3 0.4 0.4 0.4 0.3

Ions monitored : Anal yte Parent ion Daughter ion Dwell Csecs) Coll Energy CeV) Cone CV) PFOA 413 369 0.2 10 30 FOSA 498 78 0.2 40 30 PFOS 499 99 0.2 50 30

7.6 Quantitation and Example Calculation

Fifteen microliters of sample or calibration standard was injected into the LC/MS/MS. The peak area was measured and the standard curve was generated (using l/x weighted linear regression) by Masslynx software using seven concentrations of standards. The residue concentration in food samples was determined using the following equations:

Equation 1 was used to calculate the amount of analyte found (in ng/mL, based on peak area) using the standard curve (linear regression parameters) generated by the Masslynx software program.

Equation 1:

Analyte found (ng/mL) = &ak area - intercept) slope

The component residue concentration (in ng/g) in matrix was determined by using Equation 2.



Equation 2:

Analyte found (ng/g) =

[analyte found (ng/mL) - average analyte found in blanks (ng/mT.J] x DF x FV (mL) sample weight (g)

where DF = dilution factor and FV = final volume Note: the process of subtracting the average analyte found in the blanks was done

only for control matrix spikes or if a reagent blank contained residue.

For samples fortified with known amounts of analytes prior to extraction, Equation 3 was used to calculate the percent recovery.

Equation 3:

x 100 analyte: found (ng/g) analyte added (ng/g)

Recovery (%) = -

An example of a calculation using an actual sample follows:

Pork sample Centre ID 0009348 Spk A1 (Set No.: 01 1501A Pork), fortified at 2.5 ng/g of PFOS, FOSA and PFOA: (Calculation is using values from FOSA)

Where: peak area intercept slope final volume dilution factor sample weight ng/g added (fort level) amt found in control

149454 2524.48 25194.9 2 I d .

1

2.5 nglg 0 (NQ = Not quantifiable; assumed to be 0)

5 €;

From equation 1:

Analyte found (ng/mL) = 1149484 - 2524.481 25 194.9

= 5.83 nghd.



From equation 2:

Analyte found (ng/g) = (5.832 - 0) x 1 x 2 5.0

= 2.33 mg/g

From equation 3:

% Recovery = 2.33 :< 100 2.5

= 93%

Note: This example calculation was done using rounded numbers, and therefore may be slightly different from the values shown in the RAW DATA.

Any residues found for PFOA were adjusted for PFOA purity (95%). This was done by taking the residue found (ng/g) for PFOA and multiplying by the purity (0.95).

Other statistical methods used in analyzing this data were:

Standard Deviation = i=l 1 n-1

Relative Standard Deviation (RSD or Coeflcient of Variation (CV)) =

Standard Deviatic3 x 100% Mean

8.0 RESULTS AND DISCUSSION

Average fortification recoveries and relative standard deviations were 101% f 9.0% for PFOS, 96% f 13% for FOSA and 104% f 14% for PFOA. A summary of all of the fortification recoveries can be found in Table I.

Residues ranging from non-quantifiable levells to 0.852 ppb (ng/g) for PFOS, non- quantifiable levels for FOSA, and non-quantifiable to 2.35 ng/g for PFOA (one value of 14.7 ppb (ng/g) was found for PFOA but was considered suspect) were found in the food samples. The residues found in all of the samples are detailed in Table 11.



Typical calibration curves and chromatograms representing standards, controls, fortifications, and samples are depicted in Figures 1-23.

In this study, analytes were not quantified below 0.5 ng/g. If lower detection levels are required, a more definitive study, including extraction blanks in addition to matrix blanks, could be done.

Initially the PFOA standard and fortification solutions were not corrected for purity, as purity information had not been received at the time. Purity data was received after residue analyses were completed and the residues found were then corrected for PFOA purity. All ng/g residues of PFOA in this report have been adjusted to reflect the purity of the PFOA used in this study.

There was some PFOA contamination from the lab while performing the extraction for eggs. It was believed to be coming from the (extraction solvent itself. Using a different brand and lot number of ACN alleviated the problem because upon reanalysis, there were no quantifiable residues of PFOA in the egg samples.

9.0 CIRCUMSTANCES THAT MAY HAVE AFFECTED THE DATA

There were no circumstances that may have afkcted the quality or integrity of the data.

10.0 RETENTION OF DATA AND SAMPLES

When the final report is complete, all original paper data generated by Centre Analytical Laboratories, Inc. will be shipped to the sponsor. This does not include facility-specific raw data such as instrument logs, however exact copies of temperature logs will be submitted. Exact copies of all raw data, as well as a signed copy of the final analytical report and all original facility-specific raw data, will be retained in the Centre Analytical Laboratories, Inc. archives for the period of time specified in 40 CFR 792.195 (b). Retained samples of reference substances are arlchived by the sponsor.



11.0 TABLES



Table I. Summary of PFOS, FOSA and PFOA Fortification Recoveries

Extraction Analysis Fort Level Recovery (%)

Centre ID Sample Description Date Date (ng/g) PFOS FOSA PFOA

0009341 Spk A1 0009341 Spk B1 0009341 Spk A2 0009341 Spk B2 0009341 Spk A3 0009341 Spk B3 0009341 Spk A4 0009341 Spk B4 0009348 Spk AI 0009348 Spk B 1 0009348 Spk A2 0009348 Spk B2 0009348 Spk A3 0009348 Spk B3 0009348 Spk A4 0009348 Spk B4 0009344 Spk A1 0009344 Spk B 1 0009344 Spk A1 0009344 Spk B 1 0009344 Spk A2 0009344 Spk B2 0009344 Spk A3 0009344 Spk B3 0009344 Spk A4 0009344 Spk B4 0009345 Spk A1 0009345 Spk B 1 0009345 Spk A2 0009345 Spk B2 0009345 Spk A2 0009345 Spk B2 0009345 Spk A3 0009345 Spk B3 0009345 Spk A4 0009345 Spk B4

Chicken Chicken Chicken Chicken Chicken Chicken Chicken Chicken

Pork Pork Pork Pork Pork Pork Pork Pork

Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog

Fish Fish Fish Fish Fish Fish Fish Fish Fish Fish

01/11/01 01/11/01 01/11/01 01/11/01 0 1/12/0 1 0 1/ 1 210 1 0 I/ 12/0 1 0 1/12/0 1 01/15/0 1 0 1/ 15/0 1 0 1/15/0 1 0 1/1 5/0 1 0 1/16/0 1 0 1/16/0 1 0 1/ 1610 1 0 I/ 1610 1 0 1/17/0 1 01/17/0 1 0 1/ 1710 1 0 1/17/0 1 0 I/ 1710 1 0 1/17/0 1 01/18/01 0 1/18/0 1 011 1810 1 0 1/18/0 1 0 1 I1 910 1 0 1/19/0 1 01/19/01 0 1/19/0 1 0 1/30/0 1 0 1 /30/0 1 0 1 /22/0 1 01/22/01 0 1/22/01 0 1 /22/0 1

0 1/11-12/01 0 MI-12/01

0 1/12/0 1 10 1/12/0 1 10 1/15/0 1 (3 1/1 5/0 1 01/15/01 O1/15/0 1

0 I / 15- 16/0 1 0 I /15- 1 6/0 1

0 1/16/0 1 0 1/16/0 1 0 1/ 16/0 1 0 1/16/0 1

01/16-17/01 01/16- 17/01 0 1/ 17- 1 8/0 1 0 1/17- 18/0 1

0 1/ 18/0 1 01/18/01 01/18/01 0 1/18/0 1

01.118-19/01 0 1.1 1 8- 1910 1

01 1/ 1 9/0 1 011/19/01

01/19-20/01 0 lJ19-20/01

0 1/20/0 1 0 1 /20/0 1 01/3 1/01 0 1/3 1 /O 1

0 1~’22-23/01 0 1122-23/0 1

01/23/01 01/23/01

2.5 10 2.5 10 2.5 10 2.5 10 2.5 10 2.5 10 2.5 10 2.5 10 2.5 10

2.5 10 2.5 10 2.5 10 2.5 10 2.5 10 2.5 10 2.5 10 2.5 10 2.5 10

* = Rejected due to an unacceptable recovery. Replaced .with re-extracted data. - = Not Analyzed For

104 89 110 91 108 106 106 97 105 99 98 84 98 81 90 82 102 95

113 95 99 89 104

91 100 87 86 86

111 95 106 89

93 84 94 89 107 105 105 90 93 86 87 76 93 78 86 79 100 92

106 91 94 77 95 84 68 56 * *

126 110 76 65 73 62

94 87 98 91 106 111 107 98 116 110 105 95 106 91 93 92 * *

97 95 114 87 1 02 89 96 84 105 87 85 86

111 101 103 89



Table I continued: Summary of PFOS, FOSA and PFOA Fortification Recoveries

Extraction Analysis Fort Level Recovery (%)

Centre ID Sample Description Date Date (nglg) PFOS FOSA PFOA 0009342 Spk A1 0009342 Spk B 1 0009342 Spk A2 0009342 Spk B2 0009342 Spk A3 0009342 Spk B3 0009342 Spk A4 0009342 Spk B4 0009346 Spk A1 0009346 Spk B 1 0009346 Spk A2 0009346 Spk B2 0009346 Spk A3 0009346 Spk B3 0009346 Spk A4 0009346 Spk B4 0009349 Spk A1 0009349 Spk B 1 0009349 Spk A2 0009349 Spk B2 0009349 Spk A3 0009349 Spk B3 0009349 Spk A4 0009349 Spk B4 0009347 Spk A1 0009347 Spk B 1 0009347 Spk A2 0009347 Spk B2 0009347 Spk A3 0009347 Spk B3 0009347 Spk A4 0009347 Spk B4

Egg Egg Egg Egg Egg Egg Egg Egg

Green Bean Green Bean Green Bean Green Bean Green Bean Green Bean Green Bean Green Bean

Milk Milk Milk Milk Milk Milk Milk Milk Apple Apple Apple Apple Apple Apple Apple Apple

01/23/01 0 112310 1 0 1/23/01 0 112310 1 0 112410 1 01/24/01 0 112410 1 0 112410 1 02/05/0 1 02/05/0 1 02/06/01 02/06/0 1 02/08/01 02/08/0 1 02/08/0 1 02/08/0 1 02/07/0 1 02/07/0 1 02/07/0 1 02/07/0 1 02108/0 1 02/08/0 1 02/08/0 1 0210810 1 02/0910 1 02/09/0 1 02/12/01 021 1 210 1 021 1 210 1 021 1 210 1 021 1 210 1 0211 210 1

0 Y./23-24/0 1 01.123-2410 1

O1/24/0 1 01/24/01

01124-25/01 0 1/24-2510 1

01/25/01 01/25/01 02/05/01 0210510 1 02/07/0 1 02/07/0 1 02/09/0 1 O2l09lO 1 021 1 210 1 02/12/0 1

02/09- 1010 1 02109- 1010 1

0121 1 010 1 0'21 1010 1 021 1 010 1 021 1 010 1

02,'lO-11/01 02,'lO-11/01

02/12/0 1 021 1 210 1 0211 310 1 021 1 310 1

021 13- 1410 1 021 1 3- 1410 1

0:2/14/01 021 1410 1

2.5 10 2.5 10 2.5 10

2.5 10 2.5 10 2.5 10 2.5 10 2.5 10 2.5 10 2.5 10 2.5 10 2.5 10 2.5 10 2.5 10

2.5 10 2.5 10

104 98 117 101 115 92 117 102 98 106 92 111 99 94 83 96 99 91 114 90 101 89 113 93 113 105 111 100 109 98 108 99

96 80 106 98 109 90 111 97 114 106 99 103 100 97 85 95 103 90 101 91 103 91 103 94 110 104 107 102 105 96 101 96

84 67 78 77 105 85 90 82 129 128 124 130 125 125 103 112 129 128 123 123 126 129 124 123 122 119 108 101 110 100 102 99



Table I continued: Summary of PFOS, FOSA and PFOA Fortification Recoveries

Extraction Analysis Fort Level Recovery (%) Date (ng/g) PFOS FOSA PFOA

0009343 Spk A1 0009343 Spk B1 0009343 Spk A2 0009343 Spk B2 0009343 Spk A3 0009343 Spk B3 0009343 Spk A4 0009343 Spk B4 0100006 Spk A1 0100006 Spk B1 01oooO6 Spk A2 01oooO6 Spk B2 0100006 Spk A3 0100006 Spk B3 0100006 Spk A4 0100006 Spk B4 0009342 Spk A1 0009342 Spk B 1 0009342 Spk A2 0009342 Spk B2 0009342 Spk A3 0009342 Spk B3 0009342 Spk A4 0009342 Spk B4 0009342 Spk A1

0009342 Spk B 1 0009342 Spk A2 0009342 Spk B2 0009342 Spk A3 0009342 Spk B3 0009342 Spk A4 0009342 Spk B4

Bread Bread Bread Bread Bread Bread Bread Bread

Ground Beef Ground Beef Ground Beef Ground Beef Ground Beef Ground Beef Ground Beef Ground Beef

Egg Egg Egg Egg Egg Egg Egg Egg Egg Egg Egg Egg Egg Egg Egg Egg

02/08-09/01 02/08-09/01 02/08-09/0 1 02/08-09/0 1 02/12- 1310 1 02/ 12- 13/0 1 02/12-13/01 02/12- 13/0 1

02/13/0 1 02/13/01 02/ 1310 1 02/ 1 310 1 02/ 1410 1 02/ 14/0 1 02/ 1 4/0 1 02/ 1410 1

05/07-08/0 1 05/07-08/01 05/07-08/01 0907-08/01 05/08-09/01 0908-09/0 1 05/08-09/0 1 05/08-09/01

OW1 810 1

05/ 1 810 1 091 8/0 1 05/18/01

05/20-2 1/01 0920-21/01 05/20-2 1/01 05/20-2 110 1

Q2/11/01 02/11/01 02/11/01 02/11/01 02/14/0 1 02/ 14/0 1 02/ 14/0 1 02/ 14/0 1

02./14- 15/0 1

02/15/01 02/15/01 02/15/0 1 02/15/01

02/ 14- 190 1

02/15 16/01 02/15- 16/0 1

05/08/01 05/08/01

05108-0910 1 05/08-09/0 1

O5/09/0 1 05/09/0 1

05,109- 10/0 1 05,109-10/01

0’51 1 8/0 1

05/18/01 05r’l 8- 19/01 0511 8- 19/0 1

092 1/01 05/21/01

0512 1 -22/0 1 0512 1 -22/0 1

2.5 10 2.5 10 2.5 10 2.5 10 2.5 10 2.5 10 2.5 10 2.5 10 2.5 10 2.5 10 2.5 10 2.5 10 2.5 10 2.5 10 2.5 10 2.5 10

AVERAGE: STD DEV:

RELATIVE STD DEV: n:

87 96 106 94 106 99 111 102 104 103 111 103 121 106 112 102 111 99 111 102 106 94 109 102

101 9.0 9.0 88

106 96 101 93 103 92 109 100 104 99 102 98 123 116 108 101

96 13 13 80

118 109 119 106 103 97 106 100 100 95 103 98 120 114 105 102

110 99 102 108 96 96 95 96 104 14 14 88

- = Not Analyzed For



Table 11. Summary of PFOS, FOSA arid PFOA Residues Found in Samples

Residue Found (ng/g)* Centre ID Data Set No. Sponsor ID Store Name Location Matrix PFOS FOSA PFOA 0012776 01 1 lOlA Chicken

0012776 Dup 01 1 lOlA Chicken 0012777 01 1 lOlA Chicken




0012780 Dup 01 1 lOlA Chicken 0012781 01 1 lOlB Chicken

0012781 Dup 01 1 lOlB Chicken 0012782 01 1 lOlB Chicken

0012782 Dup 01 1 lOlB Chicken 0012783 011 lOlB Chicken



0012785 Dup 011 lOlB Chicken 0012786 011201A Chicken

0012786 Dup 01 1201A Chicken 0012787 01 1201A Chicken



0012789 Dup 011201A Chicken 0012790 01 1201A Chicken

0012790 Dup 01 1201A Chicken 0012791 011201B Chicken

0012791 Dup 011201B Chicken

18249 18249 18226 18226 18239 18239 18356 18356 18197 18197 18345 18345 18209 18209 18335 18335 18323 18323 18312 18312 18301 18301 18187 18187 18174 18174 18163 18163 18283 18283 18260 18260

Publix Port St. Lucie, FL Publix Port S t . Lucie, FL

Winn-Dixie Port St. Lucie, FL Winn-Dixie Port St. Lucie, FL Albertson’s Port St. Lucie, FL Albertson’s Port St. Lucie, FL

Delchamps I1 Mobile, AL Delchamps I1 Mobile, AL Winn-Dixie Columbus, GA Winn-Dixie Columbus, GA Delchamps I Mobile, AL Delchamps I Mobile, AL

Piggly Wiggly Columbus, GA Piggly Wiggly Columbus, GA

Bruno’s Mobile, AL Bruno’s Mobile, AL Kroger’s Decatur, AL Kroger’s Decatur, AL

Winn-Dixie Decatur, AL Winn-Dixie Decatur, AL

Haloway Decatur, AL Haloway Decatur, AL

Cub Columbus, GA Cub Columbus, GA

B i-Lo Cleveland, TN Bi-Lo Cleveland, TN

Save-a-Lot Cleveland, TN Save-a-Lot Cleveland, TN Albertson’s Pensacola, FL Albertson’s Pensacola, FL Food World Pensacola, FL Food World Pensacola, FL

Chicken Chicken Chicken Chicken Chicken Chicken Chicken Chicken Chicken Chicken Chicken Chicken Chicken Chicken Chicken Chicken Chicken Chicken Chicken Chicken Chicken Chicken Chicken Chicken Chicken Chicken Chicken Chicken Chicken Chicken Chicken Chicken

NQ = Not Quantifiable. The residue detected, if any, was below the limit of the study which is 0.5 ng/g. *Value is based on wet weight (5.0 g sample processed as received) ** Values rejected based on unacceptable recoveries. Data has been replaced with either reanalysis or re-extraction values.

- = Not analyzed for = Results rejected based on apparent contamination. Data has been replaced with re-extracted values.



Table I1 continued: Summary of PFOS,, FOSA and PFOA Residues Found in Samples

Residue Found (ng/g)* Centre ID Data Set No. Sponsor ID Store Name Location Matrix PFOS FOSA PFOA 0012792 01 1201B Chicken

0012792 Dup 01 1201B Chicken 0012793 01 1201B Chicken

0012793 Dup 01 1201B Chicken 0012794 01 1501A Pork

0012794 Dup 01 1501A Pork 0012795 01 1501A Pork

0012795 Dup 01 1501A Pork 0012796 01 1501A Pork

0012796 Dup 01 1501A Pork 0012797 01 1501A Pork

0012797 Dup 01 1501A Pork 0012798 01 1501A Pork

0012798 Dup 01 1501A Pork 0012799 01 1501B Pork

0012799 Dup 01 1501B Pork 0012800 01 1501B Pork

0012800 Dup 01 1501B Pork 0012801 01 1501B Pork

0012801 Dup 01 1501B Pork 0012802 01 1501B Pork

0012802 Dup 011501B Pork 0012803 01 1501B Pork

0012803 Dup 011501B Pork 0012804 01 1601A Pork

0012804 Dup 01 1601A Pork 0012805 01 1601A Pork

0012805 Dup 01 1601A Pork 0012806 011601A Pork

0012806 Dup 01 1601A Pork 0012807 011601A Pork

0012807 Dup 011601APork

18151 Watson’s Cleveland, TN Chicken 18151 Watson’s Cleveland, TN Chicken 18272 18272 18250 18250 18227 18227 18238 18238 18357 18357 18198 18198 18346 18346 18210 18210 18334 18334 18322 18322 18311 18311 18299 18299 18186 18186 18175 18175 18164 18164

Food World I1 Pensacola, FL Food World I1 Pensacola, FL

Publix Port St. Lucie, FL Publix Port St. Lucie, FL


Delchamps 11 Mobile, AL Delchamps I1 Mobile, AL Winn-Dixie Columbus, GA Winn-Dixie Columbus, GA Delchamps I Mobile, AL Delchamps I Mobile, AL

Piggly Wiggly Columbus, GA Piggly Wiggly Clolumbus, GA



Haloway .Decatur, AL Haloway Decatur, AL



Save-a-Lot Cleveland, TN Save-a-Lot Cleveland, TN

Chicken Chicken

Pork Pork Pork Pork Pork Pork Pork Pork Pork Pork Pork Pork Pork Pork Pork Pork Pork Pork Pork Pork Pork Pork Pork Pork Pork Pork Pork Pork

NQ = Not Quantifiable. The residue detected, if any, was below the limit of the study which is 0.5 ng/g. *Value is based on wet weight (5.0 g sample processed as received) ** Values rejected based on unacceptable recoveries. Data has been replaced with either reanalysis or re-extraction values. AA = Results rejected based on apparent contamination. Data has been replaced with re-extracted values. - = Not analyzed for


0012808 01 1601A Pork 0012808 Dup 01 1601A Pork

0012809 01 1601B Pork 0012809 Dup 01 1601B Pork

0012810 01 1601B Pork 0012810 Dup 01 1601B Pork

001281 1 01 1601B Pork 001281 1 Dup 01 1601B Pork

0012812 01 1701A Hot Dog 0012812 Dup 01 1701A Hot Dog

0012813 011701A Hot Dog 0012813 Dup 01 1701A Hot Dog

0012814 01 1701A Hot Dog 0012814 Dup 011701A Hot Dog



0012812 01 1701AR Hot Dog 0012812 Dup 011701AR Hot Dog

0012813 011701AR Hot Dog 0012813 Dup 011701AR Hot Dog

0012814 011701AR Hot Dog 0012814 Dup 01 1701AR Hot Dog

0012815 01 1701AR Hot Dog 0012815 Dup 011701AR Hot Dog

0012816 011701AR Hot Dog 0012816 Dup 011701AR Hot Dog

0012817 011701B Hot Dog 0012817 Dup 011701B Hot Dog

0012818 011701B Hot Dog 0012818 Dup 01 1701B Hot Dog

18282 18282 1826 1 18261 18152 18152 18271 1827 1 1825 1 18251 18228 18228 18240 18240 18358 18358 18199 18199 1825 1 1825 1 18228 18228 18240 18240 18358 18358 18199 18199 18347 18347 18211 18211

Albertson’s Pensacola, FL Albertson’s Pensacola, FL Food World Pensacola, FL Food World Pensacola, FL

Watson’s Cleveland, TN Watson’s Cleveland, TN




Delchamps I1 Mobile, AL Delchamps I1 Mobile, AL Winn-Dixie Columbus, GA Winn-Dixie Columbus, GA





Pork Pork Pork Pork Pork Pork Pork Pork

Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog

NQ NQ NQ NQ NQ NQ NQ NQ ** ** ** ** ** ** ** ** ** **

NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ

NQ = Not Quantifiable. The residue detected, if any, was below the limit of the study which is 0.5 ng/g. *Value is based on wet weight (5.0 g sample processed as received)


Table I1 continued: Summary of PFOS, FOSA and PFOA Residues Found in Samples

Residue Found (ng/g)* Centre ID Data Set No. Sponsor ID Store Name Location Matrix PFOS FOSA PFOA

** Values rejected based on unacceptable-recoveries. Data has been replaced with either reanalysis or re-extraction values.





Residue Found (ng/g)* Centre ID Data Set No. Sponsor ID Store Name Location Matrix PFOS FOSA PFOA 0012819 011701B Hot Dog

0012819 Dup 011701B Hot Dog 0012820 01 1701B Hot Dog

0012820 Dup 011701B Hot Dog 0012821 01 1701B Hot Dog

0012821 Dup 01 1701B Hot Dog 0012822 01 1801A Hot Dog

0012822 Dup 01 1801A Hot Dog 0012823 01 1801A Hot Dog

0012823 Dup 011801AHotDog 0012824 01 1801A Hot Dog



0012826 Dup 01 1801A Hot Dog 0012827 01 1801B Hot Dog

0012827 Dup 01 1801B Hot Dog 0012828 01 1801B Hot Dog

0012828 Dup 01 1801B Hot Dog 0012829 011801B Hot Dog

0012829 Dup 01 1801B Hot Dog 0012830 01 1901A Fish

0012830 Dup 011901A Fish 0012831 01 1901A Fish

0012831 Dup 011901AFish 0012832 01 1901A Fish

0012832 Dup 01 1901A Fish 0012833 01 1901A Fish

0012833 Dup 01 1901A Fish 0012834 01 1901A Fish

0012834 Dup 011901AFish

18336 18336 18324 18324 18313 18313 18302 18302 18188 18188 18176 18176 18165 18165 18285 18285 18263 18263 18153 18153 18273 18273 18252 18252 18229 18229 1824 1 1824 1 18359 18359 18200 18200






Save-a-Lot Cleveland, TN Save-a-Lot Cleveland, TN Albertson’s I’ensacola, FL Albertson’s I’ensacola, FL Food World Pensacola, FL Food World Pensacola, FL


Food World I1 F’ensacola, FL Food World I1 F’ensacola, FL

Publix Poirt St. Lucie, FL Publix Port St. Lucie, FL

Winn-Dixie Port St. Lucie, FL

Albertson’s Port St. Lucie, FL Albertson’s Port St. Lucie, FL

Winn-Dixie Port St. Lucie, FL

Delchamps I1 Mobile, AL Delchamps I1 Mobile, AL Winn-Dixie Columbus, GA Winn-Dixie Columbus, GA

Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog Hot Dog

Fish Fish Fish Fish

Fish Fish Fish Fish Fish Fish






Residue Found (ng/g)* Centre ID Data Set No. Sponsor ID Store Name Location Matrix PFOS FOSA PFOA 0012835

0012835 Dup 0012836

0012836 Dup 0012837

0012837 Dup 0012838

0012838 Dup 0012839

0012839 Dup 0012835

0012835 Dup 0012836

0012836 Dup 0012837

0012837 Dup 0012838

0012838 Dup 0012839

0012839 Dup 0012840

0012840 Dup 0012841

0012841 Dup 00 12842

0012842 Dup 0012843

0012843 Dup 0012844

0012844 Dup 0012845

0012845 Dup

01 1901B Fish 01 1901B Fish 01 1901B Fish 01 1901B Fish 01 1901B Fish 01 1901B Fish 01 1901B Fish 01 1901B Fish 01 1901B Fish 01 1901B Fish 013001A Fish 013001A Fish 013001A Fish 013001A Fish 013001AFish 013001A Fish 013001A Fish 013001A Fish 013001A Fish 013001A Fish 012201A Fish 012201A Fish 012201A Fish 012201A Fish 012201A Fish 012201A Fish 012201A Fish 012201A Fish 012201A Fish 012201A Fish 012201B Fish 012201B Fish

18348 18348 18212 18212 18337 18337 18325 18325 183 14 18314 18348 18348 18212 18212 18337 18337 18325 18325 18314 18314 18303 18303 18177 18177 18166 18166 18284 18284 18262 18262 18154 18154

Delchamps Delchamps

Piggly Wiggly Piggly Wiggly

Bruno’s Bruno’s Kroger’s Kroger ’s

Winn-Dixie Winn-Dixie Delchamps Delchamps


Bruno’s Bruno’s Kroger’s Kroger’s

Winn-Dixie Winn-Dixie

Halo way Haloway

Bi-Lo Bi-Lo

Save-a-Lot Save-a-Lot Albertson’s Albertson’s Food World Food World

Watson’s Watson’s

Mobile, AL Mobile, AL

Columbus, GA Columbus, GA

Mobile, AL Mobile, AL Decatur, AL Decatur, AL Decatur, AL Decatur, AL Mobile, AL Mobile, AL

Columbus, GA Clolumbus, GA

Mobile, AL Mobile, AL Decatur, AL Decatur, AL Decatur, AL Decatur, AL :Decatur, AL IDecatur, AL

Cleveland, TN Cleveland, TN Cleveland, TN Cleveland, TN Pensacola, FL Pensacola, FL Pensacola, FL Plensacola, FL Cleveland, TN Clleveland, TN

Fish Fish Fish Fish Fish Fish Fish Fish Fish Fish Fish Fish Fish Fish Fish Fish Fish Fish Fish Fish Fish Fish Fish Fish Fish Fish Fish Fish Fish Fish Fish Fish

** ** ** ** ** ** ** ** ** **

NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ

NQ = Not Quantifiable. The residue detected, if any, was below the limit of the study which is 0.5 ng/g. *Value is based on wet weight (5.0 g sample processed as received) ** Values rejected based on unacceptable recoveries. Data has been replaced with either reanalysis or re-extraction values. Ah = Results rejected based on apparent contamination. Data has been replaced with re-extracted values. - = Not analyzed for





0012846 Dup 0012903

0012903 Dup 0012904

0012904 Dup 00 12905

0012905 Dup 00 12906

00 12906 Dup 00 12907

0012907 Dup 0012908

0012908 Dup 00 12909

0012909 Dup 0012910

0012910 Dup 0012911

001291 1 Dup 0012912

0012912 Dup 0012913

0012913 Dup 0012914

0012914 Dup 0012915

0012915 Dup 00129 16

0012916 Dup 0012917

0012917 Dup

012201B Fish 012201B Fish 020501A Bean 020501A Bean 020501A Bean 020501A Bean 020501A Bean 020501A Bean 020501A Bean 020501A Bean 020501A Bean 020501A Bean 020601C Bean 020601C Bean 020601C Bean 020601C Bean 020601C Bean 020601C Bean 02060 1 C Bean 020601C Bean 020601C Bean 020601C Bean 020801C Bean 020801C Bean 020801C Bean 020801C Bean 020801C Bean 020801C Bean 020801C Bean 020801C Bean 020801C Bean 020801C Bean

18274 18274 18256 18256 18234 18234 18245 18245 18363 18363 18204 18204 18352 18352 18216 18216 1834 1 18341 18329 18329 18318 18318 18307 18307 18193 18193 18182 18182 18289 18289 18267 18267

Food World I1 Pensacola, FL Fish Food World I1 Pensacola, FL Fish

Publix Port St. Lucie, FL Green Bean Publix Port St. Lucie, FL Green Bean

Winn-Dixie Port St. Lucie, FL Green Bean Winn-Dixie Port St. Lucie, FL Green Bean Albertson’s Port St. Lucie, FL Green Bean Albertson’s Port St. Lucie, FL Green Bean

Delchamps I1 Mobile, AL Green Bean Delchamps I1 Mobile, AL Green Bean Winn-Dixie Columbus, GA Green Bean Winn-Dixie Columbus, GA Green Bean Delchamps I Mobile, AL Green Bean Delchamps I Mobile, AL Green Bean

Piggly Wiggly Columbus, GA Green Bean Piggly Wiggly Columbus, GA Green Bean

Bruno’s Mobile, AL Green Bean Bruno’s Mobile, AL Green Bean Kroger’s Decatur, AL Green Bean Kroger’s Decatur, AL Green Bean

Winn-Dixie Decatur, AL Green Bean Winn-Dixie Decatur, AL Green Bean

Haloway Decatur, AL Green Bean Haloway Decatur, AL Green Bean

Cub Columbus, GA Green Bean Cub Columbus, GA Green Bean

Bi-Lo Cleveland, TN Green Bean Bi-Lo Cleveland, TN Green Bean

Albertson’s Pensacola, FL Green Bean Albertson’s Pensacola, FL Green Bean Food World Pensacola, FL Green Bean Food World Pensacola, FL Green Bean






0012918 Dup 0012919

0012919 Dup 0012867

0012867 Dup 0012868

0012868 Dup 0012869

0012869 Dup 0012870

0012870 Dup 0012871

0012871 Dup 0012872

0012872 Dup 0012873

0012873 Dup 0012874

0012874 Dup 0012875

0012875 Dup 0012876

0012876 Dup 0012877

0012877 Dup 0012878

0012878 Dup 0012879

0012879 Dup 0012880

0012880 Dup

020801D Bean 020801D Bean 020801D Bean 020801D Bean 020701A Milk 020701A Milk 020701A Milk 020701A Milk 020701A Milk 020701A Milk 020701A Milk 020701A Milk 020701A Milk 020701A Milk 020701B Milk 020701B Milk 020701B Milk 020701B Milk 020701B Milk 020701B Milk 020701B Milk 020701B Milk 020701B Milk 020701B Milk 020801A Milk 020801A Milk 020801A Milk 020801A Milk 020801A Milk 020801A Milk 020801A Milk 020801A Milk

36868 36868 18278 18278 18254 18254 1823 1 18231 18243 18243 1836 1 18361 18202 18202 18350 18350 18214 18214 18339 18339 18327 18327 18316 18316 18305 18305 18190 18190 18179 18179 18168 18168

Watson’s Cleveland, TN Green Bean Watson’s Cleveland, TN Green Bean

Food World I1 :Pensacola, FL Green Bean Food World I1 Pensacola, FL Green Bean




Piggly Wiggly Columbus, GA Piggly Wiggly Clolumbus, GA





Bi-Lo Cleveland, TN Bi-Lo Cleveland, TN

Save-a-Lot Cleveland, TN Save-a-Lot Cleveland, TN

Milk Milk Milk Milk Milk Milk Milk Milk Milk Milk Milk Milk Milk Milk Milk Milk Milk Milk Milk Milk Milk Milk Milk Milk Milk Milk Milk Milk

NQ = Not Quantifiable. The residue detected, if any, was below the limit of the study which is 0.5 ng/g. *Value is based on wet weight (5.0 g sample processed as received) ** Values rejected based on unacceptable recoveries. Data has beten replaced with either reanalysis or re-extraction values. AA = Results rejected based on apparent contamination. Data has been replaced with re-extracted values. - = Not analyzed for





0012881 Dup 0012882

0012882 Dup 0012883

0012883 Dup 0012884

0012884 Dup 0012926

0012926 Dup 0012927

0012927 Dup 0012928

0012928 Dup 0012929

0012929 Dup 0012930

0012930 Dup 0012931

0012931 Dup 0012932

0012932 Dup 0012933

0012933 Dup 0012934

0012934 Dup 0012935

0012935 Dup 0012936

0012936 Dup 0012937

0012937 Dup

020801A Milk 020801A Milk 020801B Milk 020801B Milk 020801B Milk 020801B Milk 020801B Milk 020801B Milk 020901C Apple 020901C Apple 020901C Apple 020901C Apple 020901C Apple 020901C Apple 020901C Apple 02090 1C Apple 020901C Apple 020901C Apple 02 120 1 A Apple 02 120 1 A Apple 02 120 1 A Apple 021201A Apple 02 120 1 A Apple 021201A Apple 021201A Apple 021201A Apple 021201A Apple 021201A Apple 021201B Apple 021201B Apple 021201B Apple 021201B Apple

18287 18287 18265 18265 18156 18156 18276 18276 18205 18205 18257 18257 18235 18235 18246 18246 18364 18364 18353 18353 18217 18217 18342 18342 18330 18330 18319 18319 18308 18308 18194 18194

Albertson’s Pensacola, FL Albertson’s Pensacola, FL Food World Pensacola, FL Food World Pensacola, FL



Winn-Dixie Columbus, GA Winn-Dixie Columbus, GA


Winn-Dixie Port St. Lucie, FL Winn-Dixie Polrt St. Lucie, FL Albertson’s Port St. Lucie, FL Albertson’s Port St. Lucie, FL

Delchamps I1 Mobile, AL Delchamps I1 Mobile, AL Delchamps I Mobile, AL Delchamps I Mobile, AL



Winn-Dixie Decatur, AL Winn-Dixie IDecatur, AL

Haloway IDecatur, AL Haloway IDecatur, AL

Cub Columbus, GA Cub Clolumbus, GA






Centre ID 0012938

0012938 Dup 0012939

0012939 Dup 0012940

00 12940 Dup 00 1294 1

0012941 Dup 0012942

0012942 Dup 0012943

0012943 Dup 0012885

0012885 Dup 0012886

0012886 Dup 0012887

0012887 Dup 0012888

0012888 Dup 0012889

0012889 Dup 0012890

0012890 Dup 0012891

0012891 Dup 0012892

0012892 Dup 0012893

0012893 Dup 0012894

0012894 Dup

Data Set No. 021201B Apple 02 120 1 B Apple 021201B Apple 02 120 1 B Apple 021201B Apple 02 120 1 B Apple 02 120 1 C Apple 021201C Apple 021201C Apple 021201C Apple 021201C Apple 021201C Apple 02090 1 A Bread 02090 1 A Bread 020901A Bread 020901A Bread 020901A Bread 020901A Bread 020901A Bread 020901A Bread 020901A Bread 020901A Bread 020901B Bread 020901B Bread 020901B Bread 020901B Bread 020901B Bread 020901B Bread 020901B Bread 02090 1 B Bread 020901B Bread 020901B Bread

Sponsor ID Store Name Location 18183 Bi-Lo Cleveland, TN 18183 Bi-Lo Cleveland, TN 18170 Save-a-Lot Cleveland, TN 18170 Save-a-Lot Cleveland, TN 18290 Albertson’s Pensacola, FL 18290 Albertson’s I’ensacola, FL 18268 Food World Pensacola, FL 18268 Food World I’ensacola, FL 18159 Watson’s Cleveland, TN 18159 Watson’s Cleveland, TN 18279 Food World I1 Pensacola, FL 18279 Food World I1 Pensacola, FL 18255 Publix Port St. Lucie, FL 18255 Publix Port St. Lucie, FL 18233 Winn-Dixie Port St. Lucie, FL 18233 Winn-Dixie Port St. Lucie, FL 18244 Albertson’s Port St. Lucie, FL 18244 Albertson’s Port St. Lucie, FL 18362 Delchamps I1 Mobile, AL 18362 Delchamps I1 Mobile, AL 18203 Winn-Dixie Columbus, GA 18203 Winn-Dixie Columbus, GA 18351 Delchamps I Mobile, AL 1835 1 Delchamps I Mobile, AL 18215 Piggly Wiggly Columbus, GA 18215 Piggly Wiggly Columbus, GA

18340 Bruno’s Mobile, AL 18340 Bruno’s Mobile, AL 18328 Kroger’s Ilecatur, AL 18328 Kroger’s IJecatur, AL 183 17 Winn-Dixie Decatur, AL 183 17 Winn-Dixie Decatur, AL

Matrix

Apple Apple Apple Apple Apple Apple Apple Apple Apple Apple Apple Apple Bread Bread Bread Bread Bread Bread Bread Bread Bread Bread Bread Bread Bread Bread

Bread Bread Bread Bread Bread Bread


- = Not analyzed for A = Sample result fell below 0.5 ng/g when adjusting for purity of I’FOA.

= Results rejected based on apparent contamination. Data has been replaced with re-extracted values.



le I1 continuec Summary of PFOS, FOSA and PFOA Residues Found in Samples


0012895 Dup 0012896

0012896 Dup 0012897

0012897 Dup 0012898

0012898 Dup 0012899

0012899 Dup 00 12900

0012900 Dup 0012901

0012901 Dup 00 1 2902

0012902 Dup 0012758

0012758 Dup 0012759

0012759 Dup 0012760

0012760 Dup 0012761

0012761 Dup 0012762

0012762 Dup 0012763

0012763 Dup 0012764

0012764 Dup 0012765

00 12765 Dup

021301A Bread 021301A Bread 021301A Bread 02 130 1 A Bread 021301A Bread 021301A Bread 021301A Bread 021301A Bread 021301A Bread 021301A Bread 021301B Bread 021301B Bread 021301B Bread 021301B Bread 021301B Bread 021301B Bread 021301C Beef 021301C Beef 021301C Beef 021301C Beef 021301C Beef 021301C Beef 021301C Beef 021301C Beef 021301C Beef 021301C Beef 021301D Beef 021301D Beef 021301D Beef 021301D Beef 021301D Beef 021301D Beef

18306 18306 18192 18192 18181 18181 18172 18172 18288 18288 18266 18266 18158 18158 18277 18277 18248 18248 18225 18225 18237 18237 18355 18355 18196 18196 18344 18344 18208 18208 18333 18333

Haloway Haloway

Cub Cub

Bi-Lo Bi-Lo

Save-a-Lot Save-a-Lot Albertson’s Albertson’s

Food World Food World


Food World I1 Food World I1

Decatur, AL Decatur, AL

Columbus, GA Columbus, GA Cleveland, TN Cleveland, TN Cleveland, TN Cleveland, TN l’ensacola, FL I’ensacola, FL l’ensacola, FL I’ensacola, FL Cleveland, TN Cleveland, TN I’ensacola, FL Pensacola, FL

Bread NQ Bread NQ Bread NQ Bread NQ Bread NQ Bread NQ Bread NQ Bread NQ Bread NQ Bread NQ Bread NQ Bread NQ Bread NQ Bread NQ Bread NQ Bread NQ

Publix Port St. Lucie, FL Ground Beef NQ Publix Port St. Lucie, FL Ground Beef NQ

Winn-Dixie Port St. Lucie, FL Ground Beef NQ Winn-Dixie Port St. Lucie, FL Ground Beef NQ Albertson’s Port St. Lucie, FL Ground Beef NQ Albertson’s Port St. Lucie, FL Ground Beef NQ

Delcharnps I1 Mobile, AL Ground Beef NQ Delchamps I1 Mobile, AL Ground Beef NQ Winn-Dixie Columbus, GA Ground Beef NQ Winn-Dixie Columbus, GA Ground Beef NQ Delchamps I Mobile, AL Ground Beef 0.570 Delchamps I Mobile, AL Ground Beef 0.587

Piggly Wiggly Columbus, GA Ground Beef NQ Piggly Wiggly Columbus, GA Ground Beef NQ

Bruno’s Mobile, AL Ground Beef NQ Bruno’s Mobile, AL Ground Beef NQ

NQ = Not Quantifiable. The residue detected, if any, was below the limit of the study which is 0.5 ng/g. *Value is based on wet weight (5.0 g sample processed as received) ** Values rejected based on unacceptable recoveries. Data has been replaced with either reanalysis or re-extraction values. A = Result is suspect. Apparent contamination.






0012766 Dup 0012767

0012767 Dup 0012768

0012768 Dup 0012769

0012769 Dup 0012770

0012770 Dup 0012771

0012771 Dup 0012772

0012772 Dup 0012773

0012773 Dup 00 12774

0012774 Dup 0012775

0012775 Dup 0012847

0012847 Dup 0012848

0012848 Dup 00 12849

0012849 Dup 0012850

0012850 Dup 0012851

0012851 Dup 0012852

0012852 Dup

021301D Beef 021301D Beef 021301D Beef 021301D Beef 021401A Beef 021401ABeef 021401A Beef 021401A Beef 021401A Beef 021401A Beef 021401A Beef 021401A Beef 021401A Beef 021401A Beef 021401B Beef 021401B Beef 021401B Beef 021401B Beef 021401B Beef 021401B Beef 012301A Egg 012301A Egg 012301A Egg 012301A Egg 012301A Egg 012301A Egg 012301A Egg 012301A Egg 012301A Egg 012301A Egg 012301B Egg 012301B Egg

18321 18321 18310 18310 18300 18300 18185 18185 18173 18173 18162 18162 18281 1828 1 18259 18259 18161 18161 18270 18270 18253 18253 18230 18230 18242 18242 18360 18360 18201 18201 18349 18349

Kroger’s Decatur, AL Ground Beef Kroger’s Decatur, AL Ground Beef

Winn-Dixie Decatur, AL Ground Beef Winn-Dixie Decatur, AL Ground Beef

Haloway Decatur, AL Ground Beef Haloway Decatur, AL Ground Beef

Cub Columbus, GA Ground Beef Cub Columbus, GA Ground Beef

Bi-Lo Cleveland, TN Ground Beef Bi-Lo Cleveland, TN Ground Beef

Save-a-Lot Cleveland, TN Ground Beef Save-a-Lot Cleveland, TN Ground Beef Albertson’s l’ensacola, FL Ground Beef Albertson’s l’ensacola, FL Ground Beef Food World I’ensacola, FL Ground Beef Food World I’ensacola, FL Ground Beef

Watson’s Cleveland, TN Ground Beef Watson’s Cleveland, TN Ground Beef

Food World I1 Pensacola, FL Ground Beef Food World I1 Pensacola, FL Ground Beef

Publix Port St. Lucie, FL Egg Publix Port St. Lucie, FL Egg

Winn-Dixie Port St. Lucie, FL Egg Winn-Dixie Port St. Lucie, FL Egg Albertson’s Po.rt St. Lucie, FL Egg Albertson’s Port St. Lucie, FL Egg

Delchamps I1 Mobile, AL Egg Delchamps I1 Mobile, AL Egg Winn-Dixie Columbus, GA Egg Winn-Dixie Columbus, GA Egg Delchamps I Mobile, AL Egg Delchamps I Mobile, AL Egg




Table I1 continued: Summary of PFOS., FOSA and PFOA Residues Found in Samples


0012853 Dup 0012854

0012854 Dup 0012855

0012855 Dup 0012856

0012856 Dup 0012857

0012857 Dup 0012858

0012858 Dup 0012859

0012859 Dup 0012860

0012860 Dup 0012861

0012861 Dup 0012862

0012862 Dup 0012863

0012863 Dup 00 12864

0012864 Dup 0012865

0012865 Dup 0012866

0012866 Dup 0 106429

0106429 Dup 0106430

0106430 Dup

012301B Egg 012301B Egg 012301B Egg 012301B Egg 012301B Egg 012301B Egg 012301B Egg 012301B Egg 012401A Egg 012401A Egg 012401A Egg 012401A Egg 012401A Egg 012401A Egg 012401A Egg 012401A Egg 012401A Egg 012401A Egg 012401B Egg 012401B Egg 012401B Egg 012401B Egg 012401B Egg 012401B Egg 012401B Egg 012401B Egg 012401B Egg 012401B Egg 050801A Egg 050801A Egg 050801A Egg 050801A Egg

18219 18219 18213 18213 18338 18338 18326 18326 18315 18315 18304 18304 18189 18189 18178 18178 18167 18167 18286 18286 18264 18264 18296 18296 18155 18155 1827 5 18275 21213 21213 21214 21214

Peggy’s Port St. Lucie, FL Peggy’s Port St. Lucie, FL


Bruno’s Bruno’s Kroger’s Kroger’s

W inn-Dixie Winn-Dixie

Haloway Haloway

Cub Cub

Bi-Lo Bi-Lo

Save-a-Lot Save-a-Lot Albertson’s Albertson’s Food World Food World

Farmer’s Market Farmer’s Market


Food World I1 Food World I1

Columbus, GA Columbus, GA

Mobile, AL Mobile, AL Decatur, AL Decatur, AL Decatur, AL Decatur, AL Decatur, AL Decatur, AL

Columbus, GA Columbus, GA Cleveland, TN Cleveland, TN Cleveland, TN Cleveland, TN Pensacola, FL Pensacola, FL Pensacola, FL Pensacola, FL Mobile, AL Mobile, AL

Cleveland, TN Cleveland, TN Pensacola, FL Pensacola, FL

Winn-Dixie Port St. Lucie, FL Winn-Dixie Port St. Lucie, FL Albertson’s Port St. Lucie, FL Albertson’s Port St. Lucie. FL

A h

A h

Ah

A h

A h

A h

AA

AA

AA

AA

AA

A h

A h

AA

A h

Ah

A h

A h

A h

AA

Ah

AA

AA

AA

Ah

AA

AA

AA

NQ NQ NQ NQ

A l l

A h

A h

A h

AA

AA

AA

A h

A h

A h

AA

A h

A h

AA

A h

A h

A h

AA

AA

AA

A h

AA

AA

A h

A h

AA

A h

AA

Ah

A h

AA

A h

NQ = Not Quantifiable. The residue detected, if any, was below the limit of the study which is 0.5 nglg. *Value is based on wet weight (5.0 g sample processed as received) ** Values rejected based on unacceptable recoveries. Data has been replaced with either reanalysis or re-extraction values. AA = Results rejected based on apparent contamination. Data has been replaced with re-extracted values. - = Not analyzed for




Centre ID 0106431

0106431 Dup 0106432

0106432 Dup 0 106433

0106433 Dup 0 106434

0106434 Dup 0106435

0106435 Dup 0106436

0106436 Dup 0106437

0106437 Dup 0106438

0106438 Dup 0106439

0106439 Dup 0106440

0106440 Dup 0106441

0106441 Dup 0106442

0106442 Dup 0 106443

0106443 Dup 0106444

0106444 Dup 0 106445

0106445 Dup 0106446

0106446 Dup

Data Set No. 050801A Egg 050801A Egg 050801A Egg 050801A Egg 050801A Egg 050801A Egg 050801B Egg 050801B Egg 050801B Egg 050801B Egg 050801B Egg 050801B Egg 050801B Egg 050801B Egg 050801B Egg 050801B Egg 050901A Egg 05090 1 A Egg 050901A Egg 050901A Egg 050901A Egg 050901A Egg 050901A Egg 050901A Egg 05090 1 A Egg 050901A Egg 050901B Egg 050901B Egg 050901B Egg 050901B Egg 050901B Egg 050901B Egg

Sponsor ID Store Name Location 21216 Winn-Dixie Columbus, GA 21216 Winn-Dixie Columbus, GA 21217 Delchamps I Mobile, AL 21217 Delchamps I Mobile, AL 21218 Peggy’s Port St. Lucie, FL 21218 Peggy’s F’ort St. Lucie, FL 21219 Piggly Wiggly Columbus, GA 21219 Piggly Wiggly Columbus, GA 21221 Kroger’s Decatur, AL 21221 Kroger’s Decatur, AL 21222 Winn-Dixie Decatur, AL 21222 Winn-Dixie Decatur, AL 21223 Haloway Decatur, AL 21223 Haloway Decatur, AL 21224 Cub Columbus, GA 21224 Cub Columbus, GA 21225 Bi-Lo Cleveland, TN 21225 Bi-Lo Cleveland, TN 21226 Save-a-Lot Cleveland, TN 21226 Save-a-Lot Cleveland, TN 21227 Albertson’s Pensacola, FL 21227 Albertson’s Pensacola, FL 21228 Food World Pensacola, FL 21228 Food World Pensacola, FL 21229 Fanner’s Market Mobile, AL 21229 Farmer’s Market Mobile, AL 21230 Watson’s Cleveland, TN 21230 Watson’s Cleveland, TN 21231 Food World I1 Pensacola, FL 2123 1 Food World I1 Pensacola, FL

na $ .$ na $ $

Residue Found (ng/g)* PFOS FOSA PFOA

A h

A h

AA

A h

A h

A h

A h

A h

A h

AA

A h

A h

A h

A h

AA

A h

AA

A h

AA

A h

A h

AA

A h

A h

AA

A h

A h

AA

A h

A h

A h

A h

NQ - NQ - NQ - NQ NQ - NQ - NQ - NQ - NQ - NQ - NQ - NQ - NQ - NQ - NQ - NQ - NQ - NQ - NQ - NQ - NQ - NQ - NQ - NQ - NQ - NQ NQ -

NQ - NQ - NQ - NQ - NQ -


- = Not analyzed for $ = Sample labels fell off during second shipping and there was ncl way of telling samples apart.

= Results rejected based on apparent contamination. Data has been replaced with re-extracted values.




Centre ID 0 106447

0106447 Dup 0106448

0106448 Dup 0 106429

0106429 Dup 0106430

0106430 Dup 0106431

0106431 Dup 0 106432

0106432 Dup 0106433

0106433 Dup 0106434

0106434 Dup 0106435

0106435 Dup 0106436

0106436 Dup 0106437

0106437 Dup 0 10643 8

0106438 Dup 0106439

0106439 Dup 0 106440

0106440 Dup 0 10644 1

0106441 Dup 0 106442

0106442 Dup

Data Set No. 050901B Egg 050901B Egg 050901B Egg 050901B Egg 051801AEgg 051801A Egg 051801A Egg 051801A Egg 051801A Egg 051801AEgg 051801A Egg 05 180 1A Egg 051801A Egg 051801A Egg 051801B Egg 051801B Egg 051801B Egg 051801B Egg 051801B Egg 051801B Egg 051801B Egg 05 180 1B Egg 051801B Egg 051801B Egg 052101A Egg 052101A Egg 052101A Egg 052101A Egg 052101A Egg 052101AEgg 052101A Egg 052101A Egg

na $ $ na $ $ na $ $ na $ $

21213 Winn-Dixie Port St. Lucie, FL 21213 Winn-Dixie Port St. Lucie, FL 21214 Albertson’s Port St. Lucie, FL 21214 Albertson’s Port St. Lucie, FL 2 12 16 Winn-Dixie Columbus, GA 21216 Winn-Dixie Columbus, GA 21217 Delchamps I Mobile, AL 21217 Delchamps I Mobile, AL 21218 Peggy’s Port St. Lucie, FL 21218 Peggy’s Port St. Lucie, FL 21219 Piggly Wiggly Columbus, GA 21219 Piggly Wiggly Columbus, GA 21221 Kroger’s :Decatur, AL 21221 Kroger’s Decatur, AL 21222 Winn-Dixie Decatur, AL 21222 Winn-Dixie Decatur, AL 21223 Haloway Decatur, AL 21223 Haloway Decatur, AL 21224 Cub Columbus, GA 21224 Cub Columbus, GA 21225 B i-Lo Cleveland, TN 21225 Bi-Lo Cleveland, TN 21226 Save-a-Lot Cleveland, TN 21226 Save-a-Lot Cleveland, TN 2 1227 Albertson’s Pensacola, FL 21227 Albertson’s Pensacola, FL 21228 Food World Pensacola, FL 21228 Food World Pensacola, FL

Residue Found (ng/g)* PFOS FOSA PFOA

AA

/\A

AA

AA

NQ - NQ - NQ - NQ -

NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ

NQ = Not Quantifiable. The residue detected, if any, was below the limit of the study which is 0.5 ng/g. *Value is based on wet weight (5.0 g sample processed as received) ** Values rejected based on unacceptable recoveries. Data has been replaced with either reanalysis or re-extraction values. Ah = Results rejected based on apparent contamination. Data has been replaced with re-extracted values. - = Not analyzed for $ = Sample labels fell off during second shipping and there was no way of telling samples apart.




Residue Found (ng/g)* Centre ID Data Set No. Sponsor ID Store Name Location Matrix PFOS FOSA PFOA 0106443 052101A Egg 21229 Farmer’s Market Mobile, AL Egg NQ

0106443 Dup 052101A Egg 21229 Farmer’s Market Mobile, AL Egg NQ 0106444 052101B Egg 21230 Watson’s Cleveland, TN Egg NQ

0106444 Dup 052101B Egg 21230 Watson’s Cleveland, TN Egg NQ 0106445 052101B Egg 21231 Food World I1 Pensacola, FL Egg NQ

0106445 Dup 052101B Egg 21231 Food World I1 Pensacola, FL Egg NQ 0106446 052101B Egg na $ $ Egg NQ

0106446 Dup 052101B Egg na $ $ Egg NQ 0106447 052101B Egg na $ $ Egg NQ

0106447 Dup 052101B Egg na $ $ Egg NQ 0106448 052101B Egg na $ $ Egg NQ

0106448 Dup 052101B Egg na $ $ Egg NQ

NQ = Not Quantifiable. The residue detected, if any, was below the limit of the study which is 0.5 ng/g. *Value is based on wet weight (5.0 g sample processed as received) ** Values rejected based on unacceptable recoveries. Data has been replaced with either reanalysis or re-extraction values. AA = Results rejected based on apparent contamination, Data has been replaced with re-extracted values. - = Not analyzed for $ = Sample labels fell off during second shipping and there was no way of telling samples apart.



12.0 FIGURES



Figure 1. Typical Calibration Curve for PFOS

:ompound 1 name: PFOS hefficient of Determination: 0.993160 ’ Xibration awe: 7518.25 x + 2045.22 3esponse type: External Std, Area hrve type: Linear, Origin: Exclude, Weighting: l/x, Axis trans: None

Contro &8lytieal L.boratorios, Ina.



Figure 2. Typical Calibration Curve for FOSA

-

ompound 2 name: FOSA oefficient of Determination: 0.997449 ahbration cuwe: 29189.8 x + 4791.49 esponse type: Extemai Std, Area uwe type: Linear, Origin: Exclude, Weighting: lh, Axis trans: None

>.. . .. .... ... ... . . . i ng/mL 010 I ' S!O I ' 16.0 26.0 I 2i.O ' 36.0 Ti.0 I 4 0 7 d.0 ' 50.0



Figure 3. Typical Calibration Curve for PFOA

bmpound 3 name: PFOA Mficiint of Detenination: 0.997082 Ubration CUM: 104281 x + 20236.1 lesponse type: External Std, Area :unm type: Unear, Origin: Exdude, Weighting: lh, Axis trans: None

523&

Response



C101700-7,0.5 ng/mL Standard 13-Feb-2001 14:11:38 LC/MS/MS it6

021201A-1001 Sm (Mn, 2x3) MRM of 3 Channels ES- ’ 4 l l - ” 499 > 99

Time 1 .00 2.00 3.00 4.00 5.00 6.00 7.00

Figure 4. Chromatogram Representing a 0.5 n g / d mixed calibration standard of PFOS, FOSA and PFOA

C101700-7,0.5 ng/mL Standard 13-Feb-2001 14:11:38 LC/MS/MS #6

021201A-1001 Sm (Mn, 2x3) MRM of 3 Channels ES- 498 > 78

’3 . , , ‘ , ; , , * , , , , , I . , . , I , , , , I , , , . , , , , , , , , , , , , , , * , , , , , , , , , , 7.z: Time 1 .00 2.00 3.00 4.00 5.00 6.00 7.00

C101700-7,0.5 n@mL Standard 13-Feb-2001 14:11:3d LC/MS/MS Y6

021201A-1001 Sm (Mn, 2x3) MRM Of 3 Channels ES- 413 > 369

4.44e5 Area

Time 1 .00 2.00 3.00 4.00 5.00 6.00 7.00



C101700-5,25 ng/mL Standard 13-Feb-200114:42:56 L C I I V I ~ S #6

021MlA-1003 Sm (Mn, 2x3) MRM of 3 Channels ES-

23032 12605 1 3 , * , , 1 . , . , I , , , , I ..,, ) . , , I , . , - i : , , , I , , , , I , , , , I , 'I,, , ' I " ' , , ' , , , I , , . ,

Time 1 .00 2.00 3.00 4.00 5.00 6.00 7.00

Figure 5. Chromatogram Representing a 2.5 n g / d mixed calibration standard of PFOS, FOSA and PFOA

C10170M, 2.5 ng/mL Standard 13-Feb-2001 14:42:56 LC/Ms/MS #e

375397 1.7w

021201A-1003 Sm (Mn, 2x3) MRM of 3 Channels ES- , " ' , ' " ' I , , , , I , , , , , , I , . I , , , , I . * , , I , , . , , , , ) i , , , ~ , * l , , , , l,;3>z

Tim 1 .00 2.00 3.00 4.00 5.00 6.00 7.00

1021201A-1003 Sm (Mn, 2x3) MRM Of 3 Channels ES- 5.85 498 > 78

81 7351 4.0705

3.00 4.00 5.00 6.00

Area

Time 7.00



0009347 Blank A1 12-Feb-2001 18:28:02 LC/MS/MS #6

020901c3009 Sm (Mn, 2x3) MRM of 3 Channels ES- 499>99

1.4884 Area lrnJ--- 1 .oo 2.00 3.00 4.00 5.00 6.00 7.00 8.00 Time

Figure 6. Chromatogram Representing a Control Apple Sample (Centre ID: 0009347 Blank Al, Data Set: 020901C Apple)

12-Feb-2001 182802 LC/MWMS X6

MRM of 3 Channels ES-

0009347 Blank A1

020901 C-3009 Sm (Mn, 2x3)

2: FOSA 0009347 Blank A1 12-Feb-2001 18:28:0

I LC/MS/MS # 020901 C-3009 Sm (Mn, 2x3) * MRM Of 3 Chan~ls ES-

7-27 7.51 7.80 3.26 3.633eg6 4*39 4.61 5.2 5.44

~ . ~ . . . . ~ . . . . ~ . . . . ~ . , . , ~ , , . , ~ , , . , ~ . . . . ~ T j m ~ 1 .00 2.00 3.00 4.00 5.00 6.00 7.00 8.00

Contra a l ~ i c . 1 ~aboratorias, Ina.

Centre Analytical Laboratories, Inc. Page 47 of 15 I


0009347 Spk Al, 2.5 ppb

020901C-3010 Sm (Mn, 2x3)

12-Feb-2001 18:43:4C LCNSIMS it6

MRM of 3 Channels ES- 498 w 78

'3 , , , . I , , , , I , , , , I , . , , I , , , , I , , , , I , , , , I , , ) , 1 , , ~ , , , , , , , , " " I , , , , Time 1 .oo 2.00 3.00 4.00 5.00 6.00 7.00 8.00

Figure 7. Chromatogram Representing a Control Apple Sample Fortified with 2.5 ng/g of PFOS, FOSA and PFOA (Centre ID: 0009347 Spk Al, Data Set: 020901C Apple)

0009347 Spk Al, 2.5 ppb 12-Feb-2001 18:43:40 LC/MS/MS #6

020901 C-3010 Sm (Mn, 2x3) MRM of 3 Channels E S 413 w 369 '3,. , , I . , , . I , . , * , , , , , I , , I , I , , , I . , , , I , , , , I , , ,Ill,, , , I , , , , I , , , , I , , ,-4.4-7-7

Time 1 .00 2.00 3.00 4.00 5.00 6.00 7.00 8.00

-: 020901C-3010 Tuttr 0009347 splc ALr 2.5 pob

1: PFOS 0009347 Spk Al , 2 5 ppb 12-Feb-2001 18:43:

IO;;lG3010 Srn (Mn, 2x3) MRM of 3 Channels ES- 5.21 499 > 99

549311 2.9085

Contra U l y f i a a Z Laboratorian. ~nc.



001 2927 12-Feb-2001 20:1258 Lc/MSAmS#6

020901C-3016 Sm (Mn, 2x3) MRM of 3 Channels ES-

1.6284 Area

I ~ . . . I . . . . I . . . . , . . . . I . . , , I . . , . I . . . . r T i ~ 1 .oo 2.00 3.00 4.00 5.00 6.00 7.00 8.00

Figure 8. Chromatogram Representing an Apple Sample (Centre ID: 0012927, Sponsor ID: Publix, 18257, Data Set: 020901C Apple)

MRM of 3 Channels ES- 020901C-3016 Sm (Mn, 2x3) V

I " " I ' " ' " ' I " " I " ~ ~ I ~ ' ~ ' I ~ ' ~ ' 1

1 .00 2.00 3.00 4.00 5.00 6.00 7.00 8.00

3 : PFOA 001 2927 12-Feb-2001 201758

020901C-3016 Sm (Mn, 2x3) MRM of 3 Channels ES- . LC/MS/MS #f

1

3.04 I . . ..I....I....,....I.,..I...,I....~~m~

1 .oo 2.00 3.00 4.00 5.00 6.00 7.00 8.00



LC/MS/MS 16 MRM of 3 Channels ES- 020601C-5009 Sm (Mn, 2x3)

Figure 9. Chromatogram Representing a Control Green Bean Sample (Centre ID: 0009346 Blank A2, Data Set: 020601C Bean)

OOO9346 Blank A2 07-Feb-2001 08:59:49

020601 C-5009 Sm (Mn, 2x3) 1 MRM of 3 Channels ES6 5.94 498 > 78

1 . a 3

LC/MS/MS #

6.18 6*75 7.27 7 . q q e 2

3.233.56

l . . . . I . ~ . . I . . . . I . . . . I , . . , I . . . . I . . . . - ~ m e 1 .OO 2.00 3.00 4.00 5.00 6.00 7.00

1S.w: 020601C-5000 ‘putt: 0009346 D I M f i

0009346 Blank A2 07-Feb-2001 08:59:4 LC/MS/MS f

020601C-5009 Sm (Mn, 2x3) MRM Of 3 Chan~le ES-

2971 7 1.-

~ ~ . ~ ~ l . ~ ~ ~ l . . ~ . l ~ . . ~ l , . . . l . . . , , , , , , Time 1 .OO 2.00 3.00 4.00 5.00 6.00 7.00



OOO9346 Spk A2,2.5 ppb 07-Feb-2001 09:15: LC/Ms/MS

Figure 10. Chromatogram Representing a Control Green Bean Sample Fortified with 2.5 ng/g of PFOS, FOSA and PFOA (Centre ID: 0009346 Spk A2, Data Set: 020601C Bean)

020601G5010 Sm (Mn, 2x3) MRM of 3 Channels ES-

l&j , , , , I , , , . ) , , , , I , , , , , , , , , ) , , , , ) , , , , I ) , , , I , , , , , , , , ) , , , , I , , , I I , , , ,

606443 3.3986 Area

1 .00 2.00 3.00 4.00 5.00 6.00 7.00 8.00

U r n : 020601C-1010 0009346 eplr A 2 8 2.1 oob

1: PFOS OOO9346 Spk A2,2.5 ppb 07-Feb-2001 09:15:

LC/MS/MS 020601C-5010 Sm (Mn, 2x3) MRM of 3 Channels ES- '4, , " I . , , , , , . , ) , , . , . , , , , , , , I , , , , I , . , , ) , ,,,l,;l,l, , " I , , , , I , , , , 1.

1 .oo 2.00 3.00 4.00 5.00 6.00 7.00 8.00

2: FOSA OOO9346 Spk A2,2.5 ppb 07-Feb-2001 09:15:3

LC/MS/MS # 020601C-5010 Sm (Mn, 2x3) MRM of 3 Channels ES-

498 > 78 lj ..,, I , , , * I , , , * I , , * , I , , , , ) . , , , , " ' , , ' ~ , 1 , * , , I , , , , l,,"i,l , , , , I ,"',',":"~

Time 1 .00 2.00 3.00 4.00 5.00 6.00 7.00 8.00



0010010 07-Feb-2001 11 :53:24 LC/Ms/MS#6

MRM of 3 Channels ES- 020601C-5020 Sm (Mn, 2x3) 499 > 99

6.5864 Area

l l z 1 .00 2.00 3.00 4.00 5.00 6.00 7.00 Time

Figure 11. Chromatogram Representing a Green Bean Sample (Centre ID: 0012910, Sponsor ID: Bruno’s, 18341, Data Set: 020601C Bean)

001 291 0 07-Feb-2001 11 :53:24 LCIMSNS #6

020601 C-5020 Sm (Mn, 2x3) MRM of 3 Channels ES- 100- 5.97 498 > 78

b %-

0.64 2 - n 0 I I I #*.. ,?. r . , 1 1 I ,T. , . , I I I I

1 .00 2.00 3.00 4.00 5.00 6.00 7.00

- 8 020601C-5020 T a x t r 0012910



0009348 Blank A1

01 1501A-1009 Sm (Mn, 2x3)

163an-2001 01 :48:47 LC/MS/MS #6


. , . , I , . , , ~ ~ , 1 , , , , ,i\dn- ii! 1209

Time 1 .oo 2.00 3.00 4.00 5.00 6.00 7.00

Figure 12. Chromatogram Representing a Control Pork Muscle Sample (Centre ID: 0009348 Blank A l , Data Set: 011501A Pork)

0oO9348 Blank A1 1 Wan-2001 01 :48:47 LC/MS/MS #6

01 1501A-1009 Sm (Mn, 2x3) MRM of 3 Channels ES- 498 > 78 '3,. , , , , , . 1 , .00 , , , , , I , , , 2.00 , , , I , , , 3.00 , lee 4.00 5.00 6.00 7.00 .82e3

Area

~ ~ . ~ ~ ~ . . ~ . l . . ~ . l ~ . ~ . I , . , , I . , , , Time

- 8 0115OlA-1009 Text: 0009348 BluJL Al

0009348 Blank A1

011501A-1009 Sm (Mn, 2x3)

16Jan-2001 01 :48:47 LC/MS/MS #6

MRM of 3 Channels ES- 413 > 369

1.3385 Area

Time 1 .oo 2.00 3.00 4.00 5.00 6.00 7.00



0009348 Spk Al, 2.5 ppb 16Jan-2001 02:04:26 LC/MS/MS #6

Figure 13. Chromatogram Representing a Control Pork Muscle Sample Fortified with 2.5 ng/g of PFOS, FOSA and PFOA (Centre ID: 0009348 Spk. Al, Data Set: 011501A Pork)

3 : PFOA 0009348 Spk A l , 2 5 ppb

011501A-1010 Sm (Mn, 2x3)

16Jan-2001 02:04:26 LC/MS/MS #6


777851 5.2586 Area

1 9 , . . , , , , I , , . . I . , , , , , , , I , , , , I , , , ,:a:,*, , I , , , . I , , , , I , , . , I , , , . 413>369

Time 1 .oo 2.00 3.00 4.00 5.00 6.00 7.00 8.00

m: 01150l&-1010 Tut: 0009348 splr A l n 2.5 opb

011501A-1010 Sm (Mn, 2x3) MRM of 3 Channels ES- 499 > 99 !j,, , . I , , , , I . , , , I " , , , , , . , * , , , , , I , , , , I Il,. , , I , ~ , , I , , , , I , T , , I , , , , 'r

Time 1 .OO 2.00 3.00 4.00 5.00 6.00 7.00 8.00

2: FOSA

0009348 Spk Al, 2.5 ppb 16Jan-2001 02:04:2 LC/MS/MS #

MRM of 3 Channels ES- 5.81 498 > 78 I '"1 1494541 8.1585

Area

, . , . . I I . . I - . 1 Time ' 1 . b ' 2.b ' 3.00 ' 4.00 5.00 6.00 7.00 8.00

"



L

Figure 14. Chromatogram Represei~ting a Pork Muscle Sample (Centre ID: 0012795, Sponsor ID: Winn-Dixie, 18227, Data Set: 011501A Pork)

001 2795 1 Wan-2001 03:39:09 LC/AIISfMS #6


1 9 , . , , 1 ~ , , 1 , , , , I , . . , I , , , , I . , , .

l5e;

Time I 1 .00 2.00 3.00 4.00 5.00 6.00 7.00

Bl-: 01150lA-1016 T o x t r 0011795

001 2795

01 1501A-1016 Sm (Mn, 2x3)

1'7 16Jan-2001 03:39:0

LCNSIMS #

3 : PFOA 001 2795 16Jan-2001 03:39:0!

LC/MS/IIIIS It( 01 1 3 , 1501A-1016 , , . I , , , Sm , (Mn, * , I . , 2x3) . , I , , , , I , , , , I ~, , , I , , , , I , , , 5*OmL MRM of 3 Channels 413>:: ES.

15654 1 Joe!

1 .oo 2.00 3.00 4.00 5.00 6.00 7.00 , - . . . I . I I r l I . . . . I . . . . I . . . . Time



OOO9349 Blank A1 09-Feb-2001 23:46:11 LCIMSNS #6

020701A-3009 Sin (Mn, 2x3) MRM of 3 Channels ES- 413 > 369

1.41 e5 Area 'rnn 1 .oo 2.00 3.00 4.00 5.00 6.00 7.00 Time

Figure 15. Chromatogram Representing a Control Milk Sample (Centre ID: 0009349 Blank A l , Data Set: 020701A Milk)

1: PFOS OOO9349 Blank A1 09-Feb-20012346:1

LC/MS/MS # I y i l A - 3 0 0 9 Sin (Mn, 2x3) MRM of 3 Channels ES-

5.04 499 > 99 99741 4.6384

Area

2: FOSA OSFeb-2001 23:46:1

LC/MS/MS #I 020701A-3009 Srn (Mn, 2x3) i MRM of 3 Channels ES.

5.89 498 > 71 A 1 sa: 6.59 7.15

Time 1 .00 2.00 3.00 4.00 5.00 6.00 7.00



0009349 Spk Al , 2.5 ppb

020701A-3010 Sm (Mn, 2x3)

10-Feb-2001 00:01:51 LC/Ms/MSM

MRM of 3 Channels ES- '4 , . , . I , , , , ) , ' , , , ' ~ ' , I , , , , l~172.E: 499 > 99

Time 1 .00 2.00 3.00 4.00 5.00 6.00 7.00 8.00

Figure 16. Chromatogram Representing a Control Milk Sample Fortified with 2.5 ng/g of PFOS, FOSA and PFOA (Centre ID: 0009349 Spk Al, Data Set: 020701A Milk)

0009349 Spk Al , 2.5 ppb

020701A-3010 Sm (Mn, 2x3)

1 0-Feb-2001 00:01:51 LC/MWS #6


'Cj , , , , I , , , . ) , , . , I , * , , I , . , , ) , , , , ) , , , , I , , , 7;;L,,,l.'" Time

1 .OO 2.00 3.00 4.00 5.00 6.00 7.00 8.00

020701A-3010 Sm (Mn, 2x3) MRM of 3 Channels ES- 498 78

'3 ,. , , I * , . , I , , , ' ) , , , . ) , ~ * , ) . , , , ) , , . , I , , , , I , , , , ) , , , , ) , , , , ) , , , , ;:. 1 .00 2.00 3.00 4.00 5.00 6.00 7.00 8.00



Figure 17. Chromatogram Representing a Milk Sample (Centre ID: 0012871, Sponsor ID: Winn-Dixie, 18202, Data Set: 020701A Milk)

- 8 02Q70l.A-3014 T u t r 0012871

1: PFOS 001 2871 10-Feb-2001 03:42:

10;;1A-3024 Sm (Mn, 2x3) MRM of 3 Channels ES- 5.05 499 > 99

I 7 2 : FOSA 001 2871 10-Feb-2001 03:42:3

I LC/MS/MS It IO;!lA-3024 Sm (Mn. 2x3) Y MRM of 3 Channels ES-

5.84 498 > 78 A 988

3 : PFOA 001 2871 10-Feb-2001 03:42:38

020701A-3024 Srn (Mn, 2x3)

1.1885 Area

1

I ~ ~ . . l . ~ ~ ~ l ~ . . ~ I . . . . I . . . , I . . . . Time 1 .00 2.00 3.00 4.00 5.00 6.00 7.00

Cuitro Analytical trboratorioa, m.



Figure 18. Chromatogram Representing a Control Chicken Egg Sample (Centre ID: 0009342 Blank A3, Data Sets: 050901A Egg for PFOS, 012401A Egg for FOSA, and 052101A Egg for PFOA)

N m : 0509OLA-3010 T e x t : 0009342 Blank A3

1: PFOS

0009342 Blank A3 09-May-2001 19:16:31 LC/MS/MS #6

MRM of 3 Channels ES- 050901A-3010 Sm (Mn, 2x3)

1 3 , , ( , , ( , , , ( . , , , 1 1 , , , , , ~, , _I,(, , ( , , ;$r::

Time 1 .oo 2.00 3.00 4.00 5.00 6.00 7.00 8.00

2: FOSA 0009342 Blank A3 244an-2001 19:27:4


1: PFOA 0009342 Blank A3 21-May-2001 17:37:0

LC/MS/MS # 052101A-3010 Sm (Mn, 2x3) MRM of 3 Channels ES-

Area %

r l I I j , , I l l l ~ l l l , I I l , . , , , , , , , , , Time 2.00 3.00 4.00 5.00 6.00 7.00



0009342 Spk A3,2.5 ppb 244an-2001 19:43:27 LCIMSIMS #6


1 .ow Area

~ ~ 1 ~ ~ 1 0 ~ ~ ~ ~ , . . . , I , . , , , , , . , I , , , . I , , , , I . . , . I , :I, , I . . . , I . . . , , . ,

> 78

Time 1 .oo 2.00 3.00 4.00 5.00 6.00 7.00 I

Figure 19. Chromatogram Representing a Control Chicken Egg Sample Fortified with 2.5 ng/g of PFOS, FOSA and PFOA (Centre ID: 0009342 Spk; A3, Data Sets: 050901A Egg for PFOS, 012401A Egg for FOSA, and 052101A Egg for PFOA)



21 -May-2001 19:26:45 7

LC/MS/MS #7 MRM of 3 Channels ES-

413 > 369 3.14e4

Area

Figure 20. Chromatogram Representing a Chicken Egg Sample (Centre ID: 0012861, Sponsor ID: Save, 18167 and 21226, Data Sets: 050901A Egg for PFOS, 012401A Egg for FOSA, and 052101A Egg for PFOA)

N m : 0509OlA-3017 Text : 0106440

1: PFOS

01 06440 09-May-2001 21 :06:31 LC/MS/MS #E

MRM of 3 Channels ES- 050901A-3017 Srn (Mn, 2x3)

1 3 , I , , , , / ~ , , , , , I , ~ , , 1 , , ,,_--;-.l-...-I.(z;

I ' * " ' ' ( ' ' ~ ~ ' l ' ~ ' ' l ~ ~ ~ ~ l ~ , / , , I ~ I I ,

1 .oo 2.00 3.00 4.00 5.00 6.00 7.00 8.00

2: FOSA 0012861 243an-2001 23:24:1 - - . - - -. .I

V MRM of 3 Channels ES- )012401A-5024 Sm (Mn, 2x3) 1OqI

1: PFOA 101 06440

052101A-3017 Srn (Mn, 2x3)

lo?

I - I ' ' ' ~ I " ' ' " ' ' l ~ ' ~ Time

I 1.00' " 2.00 ' 3.00' ' I 4.00 5.00 6.00 I " 7.00 ' ' ' ' I " '

" '



0009343 Blank A1 11-Feb-2001 03:36:14 LC/MS/MS #6


Time 1 .00 2.00 3.00 4.00 5.00 6.00 7.00

Figure 21. Chromatogram Representing a Control Bread Sample (Centre ID: 0009343 Blank Al, Data Set: 020901A Bread)

0009343 Blank A1 11-Feb-2001 03:36:14 LC/MrnS it6

020901A-1009 Sm (Mn, 2x3) MRM of 3 Channels ES-

5.28

, . . . . I . . s . I q . q ~ I . . . . I ~ . . . I . , . . I , . . . Time 1 .00 2.00 3.00 4.00 5.00 6.00 7.00

-1 0209OlA-1009 Toxtr 0009343 Blank Al

Contro Analytical Laboratories, Tpo.



0009343 Spk Al, 2 5 ppb

020901A-1010 Sm (Mn, 2x3)

11-Feb-2001 03:52:01 LC/MS/MS #6

MRM of 3 Channels ES- 499 > 99 '3 , , , . I , , , , I , , , , I , , , , I , . , , I , , , . I , , , , I , , , , I , , , ,

1 .oo 2.00 3.00 4.00 5.00 6.00 7.00

Figure 22. Chromatogram Representing a Control Bread Sample Fortified with 2.5 nglg of PFOS, FOSA and PFOA (Centre ID: 0009343 Spk A l , Data Set: 020901A Bread)

IO09343 Spk Al, 2.5 ppb

D20901A-1010 Sm (Mn, 2x3)

11-Feb-2001 03:52:01 LC/MS/MS 16

MRM of 3 Channels ES- 490 > 70

Area '9, , , , , , , , , I , , , , I , , , , I , , , , I , , , , I , , , , , . , , , , I , , , , l , ~ ~ , l a , , , I , , , , I , , , . 1.2386

Time 1 .oo 2.00 3.00 4.00 5.00 6.00 7.00

'


0009343 Spk Al, 2.5 ppb

020901A-1010 Sm (Mn, 2x3)

11-Feb-2001 03:52:01 LC/MS/MS #6


, , , , I , , , , 1 , , ~ ~ 1 , , , ) , , , , I , , , , I , , , , I , , , , , , , , , ~ -,,, l,,,:g Time 1 .OO 2.00 3.00 4.00 5.00 6.00 7.00

Page 63 of 15 1


Figure 23. Chromatogram Representing a Bread Sample (Centre ID: 0012887, Sponsor ID: Albertson's, 18244, Data Set: 020901A Bread)

-8 0209OlA-1020 T u t r 0012887

: PFOS lo12887 11 -~~tb-200106:29:4

LC/MS/MS #C MRM of 3 Channels ES-

499 > 9s 320901A-1020 Sm (Mn, 2x3) ll , , , , I , . . , ) , ' , ' I . , , , I , , , , I , , , , ~ ~ , , ) , " ' , ' , j ;=

Time 1 .OO 2.00 3.00 4.00 5.00 6.00 7.00

: FDSA -

11-Feb-2001 06:29:43 01 2887

120901A-1020 Sm (Mn, 2x3) 498 > 78

1.1883

I . . . . I . . . ~ I . . . . I . ~ . . l . , , . I . , . . , . . . . Time 1 .oo 2.00 3.00 4.00 5.00 6.00 7.00

3 : PFOA 0012887 ii-~~tb-200106:29:4:

LC/Ms/MS #t MRM of 3 Channels ES-

Area

020901A-1020 Sm (Mn, 2x3) 1

I ~ ~ . . I . ~ ~ ~ I . ~ . . I ~ . . . I . , . , I . . , , I . . . . Time 1.00 2.00 3.00 4.00 5.00 6.00 7.00



13.0 APPENDICES



APPENDIX A Study Protocol OOP-023-057

(Centre Study No. 023-057), Amendments

and


Deviation

Page 66 of 15 1


. .- -. ... . . - . . - . . . . . . - . . .. . -. . . . . . - . ._.. .. . -.-

Centre Protocol No. OOP-023-057

STUDY PROTOCOL

STUDY TITLE

. . SPONSOR

3M Environmentd Technology and Safety Services . Building 2-3E-09

St. Paul, MN 55133-3331 . PO BOX 33331

DATA REQUIREMENTS

EPA TSCA Good Laboratory Practice Standards 40 CFR 792

TESTING LABORATORY

Centre Analytical Laboratories, Inc. (Centre) 3048 Research Drive

State College, FA 16801 Phone 814-231-8032

PROTOCOL IDENTIFI(:ATION NUMBER

.--


Centre Analytical Laboratories, Inc. _ _ -. - _ _ _ ._ -

OOP-023-057

Page 1 of 81

Page 67 of 15 1



Title: E m k c T I O N OF PFOS, FOSA A N D PFOA FROM VARIOUS FOOD MATRICES FOR ANALYSIS USING HPLC ELECTROSPRAYM4SS

SPECTROMETRY TABLE OF CONTENTS Page.

1 STUDY TrrLE ...................................................................................................................

3

3

5 3. SPONSOR ............................................. .. .................................................................

1. PURPOSE ............................................. . .................................................................

2. . TESTMATERM3 ................................................................................................

4. TESTING F A C I L ~ Y AND PERFORMBGG LABORATORY ............................. 5

5. PROPOSED EXPERIMENTAL T . I h 4 E - m ..... . ............................................. 5

5

JUSTIFICATION FOR THE SELECT'I(XI OF THE TESTSYSTEM ................. 6

6. . TEST SYSTEM .......................................................................................................

7.

8. SAMPLE PROCESSING, STORAGE AND EX3'4TIFICATION ........................ 6

9. ANALYTICAL METHOD ................................................... 1 ................................ 6

10. - EXPERIMENTAL DESIGN ................................................................................... 7

11. - STATISTICAL METHODS TO BE USED ............. 1 ............................................. 7

12. PROTOCOL AMENDMENTS AND DEV~ATIONS ....._... :: ................................. 7

13. RECORDS AND DATA REPORTING . ................................................................ 8

8 14. QUALITY ASSURANCE ......................................................................................

8 15. DATA AND REPORT .......... ....... . ......... ............. .. . .. ........ . ... .............. ............ ........ 10 16. ARCHIVE STATEMENT ..................... . ............................... : ..............................

17. REFERENCES .................................. .................................... 1 ..................: ............ 10

18. PROTOCOL APPROVAL .................................................................................... 1 1

APPENDIX: ANALYTICAL METHOD ...................................... : ................................... 12

. .


Centre Analytical Laboratories, Inc. - . - ~ -

Page 2 of 81

Page 68 of 151

Centre Study No.: 023-057 Centre Protocol No: OOP-O23:057

Purity (%)

97.9

TBD

95.1

. .. .

Expiration Date

08/31/01

07/06/01

0211 5/01

Centre Protocol No. OOP423-057

Test Materiai

PFOS

PFOA

FOSA

1. PURPOSE The purpose of this study is to analyze PFOS, FOSA and PFOA in various food matrices using the analytical method entitled “Method of Analysis for the Determination of Fluorochemicals in Green- Beans, Apples, Pork Muscle, Cow Milk, Chicken Muscle, Chicken Eggs, Bread, Hotdogs, and Catfish by LC/MS/MS”. A copy of the method is ,appended to this protocol (Appendix).

The Quality Assurance Unit of Centre 14ndytkal Laboratories, Inc. will audit the study for compliance with EPA TSCA Good Labontory Practice standards 40 CFR 792 (1).

- Lot or TCR Number

TCR00017-46

332.

L-15709

- -

-

-

-

2. TEST MATERIALS The following analytical standards will be used:

-Note: G.& characterization, solubility and stability data for PFOA and FOSA are unavailable at this time. However, available characterization data for the test materials will be supplied t6 the testing facility (Centre) by the sponsor (3M). Therefore, do not correct for percent purity when preparing standard solutions for these two fluorochemicals.

1

Centre Analytical Laboritones. Inc.

Centre Analytical Laboratories, Inc. __.._ -

Page 3 of 81

Page 69 of 15 1

Centre Study No.: 023-057 Centre Protocol NO: OOP-023-057

~ .__.. -.-- . -...- ....

Centre Protocol No. oOP-023-057

I Chemical names and structures of the compounds are presented below.

PFOS Chemical Name: I-Octanesulfonic acid, 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-

heptadecafluoro-, potassium salt. Molecular Weight: 499 (CgFd03') CAS Number: 2795-39-3

0

- Note: The neutral molecule and standard form which PFOS (anion) is derived from is perfluorooctanesulfonate potassium salt [CsFi7SO&], molecular weight 538.

PFOA Chemical Name: Molecular Weight: 413

Octanoic acid, penkdecafluoro-, ammonium salt

- CAS Number: 3825-26-1 (FC-143)

- Note: The neutral molecule and standard.form which PFOA (anion) is derived from is perfluoroctanoate ammonium salt [C7FisCOONHi], molecular weight 431.

FOSA Chemical Name: I-Octanesulfonamide, 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-

heptadecafluoro- - Molecular Weight: 499 - CAS Number: 754-9 1-6

A record of test and reference substance receipt, storage conditions, and a record of use will be maintained at Centre Analytical Laboratories, Inc. Chain-of- custody forms and shipping documents for tracking of the test substances will be included as part of the raw data packag.



Page 4 of 81

Page 70 of 151 .


. .. . - . . . . . _. . -. - - . . . . . . . . .


I

All standardshest substances and any prepared solutions must be identified with a unique label or number on the container or cross-referenced to the'container.

HAZARD INFORMATION

A current MSDS for the chemical(s) used in this study will be maintained ai the testing facility.

I -

3. SPONSOR 3M EnGronmental Technology and Safety Services Building 2-3E-09 PO Box 33331 St. Paul, MN 55133-3331

STUDY DIRECTOR: Susan A. Beach, 3M TELEPHONE: 651-778-7452 .

FAX NUMBER: 651-778-6176

4. TESTING FACILITY AND PERFORPdING LABORATORY

Centre Analytical Laboratories, Inc. (Centre) 3048 Research Drive State College, PA 16801

PRINCIPAL INVESTIGATOR: Karen Smith, Centre-

FAX NUMBER 814-231-1580 TELEPHONE: 814-231-5032

5. PROPOSED EXPERIMENTAL TIME-FRAME

Experimental Start Date January 8,2001 Experimental Termination Date February 8,2001 Report Issued March 8,2001

6. TEST SYSTEM Food samples obtained by Centre Analytical Laboratories, Inc. and used in the validation study (Centre Study NO. 023-043) will be used the control samples. Samples will be collected from local grocery StOreS from six test cities outlined in


Centre Analytical Laboratories, Inc. . .. . - . . -. . ._ . . . . . . . . .. . . _.__ ~

~. .. .. . --. . . . . - - . . .

Page 71 of 151 - - -



7.

3M Quality Assurance Project Plan for Empirical ,Human Exposure Assessment Multi-City Study Sampling Task. All food samples obtained from grocery stores in the six- test cities by the sponsor will be shipped to Centre Analytical Laboratories, Inc. for analysis.

JUSTIFICATION FOR THE SELECTION OF-THE TEST SYSTEM Representative samples such as, honey, vegetable (green beans, carrot, radish, lettuce, potato), fruit (Apple), livestock (pork muscle, cow milk), poultry (chicken muscle, egg), fish and processed foods (bread, hot dogs), will be collected by the sponsor and shipped to Cmtre for traCe-k!Vel analysis Of fluorochemical residues. The cities chosen as the collection sites either have major fluorochemicd production facilities, major fluoroche+cal users, or no major fluorochemical production or usage facilities. The matrices were chosen to determine if fluorochemicals are being transferred froni the environment to food sources.

8. SAMPLE PROCESSING, STORAGE AND 1.DENTIFICATION All food samples will be processed accorlding to the method entitled, "Method of Analysis for the Determination of Fluorochemicals In Green Beans, Apples, Pork Muscle, COW Milk, Chicken Muscle, Chicken Eggs, Bread, Hotdogs, and Catfish by LC/MS/MS."

Upon receipt at Centre, the fwd samples will -be assigned unique sample identification numbers, which will be used for tracking and identification of the samples. The samples will be stored in a temperature monitored freezer, maintained at < -10" C, except when removed for amlysis as described in the method. The samples will be kept isolated from the test substance during storage.

Sample receipt and storage location and conditions -during the study must be documented. All samples and any resu1::ing sample extracts must be identified with a unique label or sample number. Such identification will be either. on the container or cross-referenced to the contai ner. . .

9. ANALYTICAL METHOD The samples will be analyzed according to the analytical method entitled "Method of Analysis for the Determination of Fluorochemicals in Green Beans, Apples, Pork Muscle, Cow Milk, Chicken Muscle, Chicken Eggs, Bread, Hotdogs, and Catfish by LC/MS/MS" (see Appendix).

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10. EXPERIMENTAL DESIGN I

For each matrix, a set of samples will be extracted in duplicate and analyzed. Each set of samples analyzed will Contain at least one matrix control and two matrix control samples fortified at known Concentrations and camed through the extraction procedure to verify recovery.

Metho& to control bias will includl: assay of untreated control samples, fortification of untreated control smples to obtain recovery data, and replicate analysis of fortified samples to provide an indication of reproducibility.

11. STATISTICAL METHODS TO BE USED Standard (hear, l/x weighted) curves used to determine the concentration of the compound being analyzed will be constructed from a minimum of six concentrations. Quantification of residues will only occur within the range of the standard curve (residues in control samples may be calculated up to 20% of. the LOQ [2O% of LOQ = 0.1 ppbl by extrapolation of the calibration curve, in order to correct fortification recoveries). The correlation coefficient (r) for calibration curves generated must be greater than or equal to 0.9925 (32 0.985).

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Overall averages, standard deviations and relative standard deviations of fortification recoveries will be calculatedr -

Other than these descriptive statistics, no other statistical methods will be used during the course of this study. -

12. PROTOCOL AMENDMENTS AND I~EVIATIONS . Any deviations from the protocol or from the analytical method as provided will be documented and reported promptly to the Study Director. Planned changes to this protocol or to the analytical method *Nil1 be made in writing as an amendment or modification and approved by the Principal Investigator and the Study Director. Any amendments will be appended to this protocol and included in the final report.

1. Protocol amendments: Planned changes to the approved protocol shall be documented by amendments that c1e:uly describe the change, justification for the change, and impact on the study. Amendments will be signed and dated by the Principal Investigator and Study Director. Copies of amendments will be sent to the quality assurance Unit.

2. Protocol deviations: Protocol deviations, which are one time and unplanned deviations from the protocol shall be documented in the study'records, noting the nature of the deviation, potentid effect or impact on the study, and corrective action if required. Protocol deviations are signed by the Principal Investigator and Study Director and reviewed by QAU.

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15.

RECORDS AND DATA REPORTING Records to be maintained include, but appropriate): 1. Sample tracking sheet($


are not limited to the following (as

- 2. Sample receipt records, storage history, and chains of custody 3. History and preparation of standards (stock, fortification, calibration) 4. Description of any modifications to h e method 5 . Instrument run sheets, bench-sheets or logs 6 . Analytical data tables 7. All chromatographic and instrumental conditions 8. Sample extraction and analysis dates 9. A complete listing of study personnel, sisatures and initials

10. Chronological presentation of all study correspondence 11. Any other data necessary for the reconstruction of the study

All chromatopms will contain the following:

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a. Sample identification, date, arrow or other indication of the area of interest, and injection number corresponding to the run.

b. Additionally, fortifications will include the fortification level of each analyte.

c. Analytical standard chromatograms will additionally include the concentration (e.g., pg/ml, ng/d- , ppb, ppt. etc.).

Each data set will contain information on temperatures, flow rates, column parameters, gases, instrument parametea;, and instrument type, etc. if any of these differ from the method. The Centre study number will also be recorded on the first chromatogram of each daily ana1yiic:al run.

QUALITY ASSURANCE Centre QA Unit will review the protocol and audit the study conduct and the study documentation (including raw data and final report) to ascertain that all QNGLP procedures are adhered to. Ckntre QA Unit will inspect the study at intervals adequate to assure compliance to GI-F”S, and will report the findings of the audits to the Principal Investigator, Centre Management, and the Study Director.

DATA AND REPORT 1. All raw data and the original signed protocol will be maintained i; the study

file. This data includes the protocol amendments, protocol deviations, laboratory notebooks, analytical sthdard solution preparation, sample chain of custody sheets, sample work sheets, chromatograms, calibration curves, and any other appropriate data generated. Raw data not used will be stored in the study file. The reason for exclusion will be documented.


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2. A final report will be issued by Clintre, approved and signed by the Study Director and sufficient for submission to EPA. The report contents should include, but are not limited to:

1. Objectives and procedures stated. in the protocol 2. Analytical and statistical methods used 3. Test materials identified by name, lot, purity and other characteristics 4. Name of testing facility and study initiation and completion dates 5. Statement prepared andsigned by the quality assurance unit 6. Tables containing all applicable data 7. All chromatographic and instrumental conditions 8. A complete listing of Centre study personnel .

Centre will send a copy of the draft report to the Study Director, who will return the report with comments. Centre Analytical Will make revisions and finalize the

- report with the approval of the Study D:irector. The Centre QA unit will conduct an audit of the final draft report and data files to assure accuracy and GLP compliance. The final report and copies of the raw data must be approved by the

- Study Director prior to signature. A statement of inspections and a statement of compliance will be included in the final :report.

Any corrections or additions to the final report shall be in the form of dn ame&nent by the Principal Investigator. The amendment shall clearly identify the part of the final report that.is -being corrected and the justification for correction. The amendment shall tle signed -and dated by the Principal Investigator and the Study Director.

REPORT DISTRIBUTION: Original: Study Director Copy: Centre Archives

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Centre Protocol No. 0013-023-057

I 16. ARCHIVE STATEMENT Study records to be maintained: Records to be maintained for the study include all raw data, observations recorded during the conduct of the study, documentation, chromatograms, specimens, and study related correspondence. This includes a

'- description of equipment used during the conduct of the study. All characterization data and any shipping records shall be retained.

Document archives: Upon completion of the study, the study records, protocol and amendments, and the final report and amendments shall be retained in the 3M document archives. If it is necessary to substitute a copy for an original record, it will be certified as an exact copy. Centre -will retain facility-related originals and a copy of the final report and raw data package.

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17. REFERENCES 1. U.S. Environmental Protection Agency, Toxic Substances Control Act (TSCA).

Good Laboratory Practice Standards. Final Rule, 40 CFR Part 792.


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18. PROTOCOL APPROVAL

This protocol was audited by the Quality Assurance Unit of Centre Analytical Laboratories; Inc.

Quality Assurance Reviewer, Centre

b! /03/0 1 %baa B. Kinne 1 Date Qudity Assurance Auditor

Principai Investigator, Centre

Facility Management, Centre

Laboratory Manager

0 3 - @ - 6 I Date

President

Study,Director, 3M

V L - . 6 /e&+ Susan A. Beach

S p o n i s o T23M -

Dale acon ’ Date Technical Director

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APPENDIX: ANALYTICAL METHOD

METHOD OF ANALYSIS FOR ‘rm DETERMINATION OF FLUOROCHEMICALS IN GREEN BEANS, APPLES, PORK MUSCLE,

COW MILK; CHICKEN MUSCLE, CHICKEN EGGS, BREAD, HOTDOGS, AND CATFISH BY LC/MS/MS.


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TITLE

Method of Analysis for the Dertmination of Fluorochemicals in Green Beans, A ~ ~ ] ~ ~ , Pork Muscle, COW Milk, Chicken Muscle, Chickm Eggs, Bread, Hotdoss, and Catfish by

LCIMSIMS I

AUTHORS . . . --

Enaksha Wickremesinhe, Shaozhi Zheng and John H & e q

DATE ISSU@

September 13,2000

. . -- SPONSOR .

jhl Environmend Technology and Safety Services Building 2-3E-09 -PO BOX 33331 . '

St. Pad, MN 5512'3-3331

PERFORMING LABORATORY

Centre Analytical Laboratories, Inc. (Centre) 3048 Research 1)rive

State College. PA 16801

C E m STUDY NUMBER

023401 . .

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9-13-00 Shaozhi Zheng Date Author, Principal Investigator Centre Analytical Laboratories, Inc. , .

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' hboratory Manager Centre Analyticai Laboratories, Inc..

R i c h s d k Grauini, PhD. Date President' . Centre Analytical Laboratories, Inc. . -

Hans.cn, PhD. . Date Sponsor Representative '. 3M Environmental Labontory

. . Cenrre Amlyrical kbontorics. Inc. Study C 023601

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TABLE OF C 0 ” T S ?rrr;E PAGE .................................................. ................ 1 .............................. W A G - AppROVAL ............................... 2 TABLE OF c o r n s ...._.... : ~ ~ ............................ 3 LIST OF TABLES ...................... : .............................................................. : LIST O F R G W ............._.... i ................................................ ................_. 1. SUMMARY ...................._.... : :...i ...................................... 7 2. COMPOUNDS : ................................. 8 3. .bJvD S ~ P W .................................................................

3 . 1 ; . m w ..........__............... ” ............................... g 3.2. STANDARDS .................................?....e. ................................... .......................... g . 3.3. E ~ J ~ , W A M ) ~ ................................... 10. 3.4. S O L ~ O ~ ~ . . . . . . 11

. 3.5. PREPARA~ON OF mcx FOR~XATIOX C-U~ON S O L ~ O N ~ ....... 1 1 .

3.5.2. Fortifidon SOlUuOnS ......................... 11 3.5.3. Cdbntim St anndards .............................................................................. 12

1 ..................... ............................................................ ..................... ...................... ................ . .

. ....................... 4 ...................... 5 . .

.................................. ......... ... .... ..................................

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

. ..........................................

. ..............................................

. ........ ; ................................................................ ........................

.......... ...................... 11 3.j.1. Stock Soludons ...................................... ............ . ..............................................

. ........................... .................................................... .... 4. METHOD 1 .............................. 12 . :

. ......... .......................................................... .............................. I2 4.2. S&p~pRo(zssING...; ................................ 13

. 4.3. O ON...... .-... ......................................................... ................... : .......... 13

4.3.2. Chicken md Milk ....................... 14 . 1 j 4.3;3. E% and atfish ........................................ :

4.3.4. SpE Column PrcpantiOn ................................................................... 16 . 43,5. Sil&adon of Pear-Shaped FMcs ................ : ................... ................. 16

16 43.6. Sm&-&arion of SPE column^ ...................................................... 16

4.4.1. h C i / M S System and openti% (hdit ions filectrospmy) ......... 16 ........................... 18

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

20

4.1; OWD DUG^ . ......................................................

.. 4.3.1. Apple, Green Beans, Bmd, Ho~!DoiL and Pork ........ I...................... 13. ............................ . . ...........................

............................. ...........

................................... 4.4. & ~ ~ ~ ~ B Y L C / M S / M S ....: ....._............. ..................... . . .

. ............................... 4.4.2. h m p l e Tunc File Pmmten

4.4.4. sample hdysis .- ........................................................ ...................... 19

4.6. &QVIR~, A)S ANI\LyS Is ............................ 21 .

5. C A L W n O N S ................................. 1 .. .. ....... ................ 21 5.1. C 0 m m - r m b i CokcEEinunON 2 .... I ..................... 21

6. s m ........................ 22

.............................. ........................ 4.4.3. Cdibntion h c t d u m :-

. . . . . . ................................................................. ...... 4. j. pERFO&\WE .......... .............................................

....................... ................ . . ............... ............

5.7.. F O R ~ ~ ~ O N RECOVERY ...................................................... ....................... 22. ............................................................................................

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LISTOFTAI3LES . . .

Table 1: Su-~y of Recoveries for Et-FOSE-OH, Me-FOSE-OHjFOS,

Tiible 2 Summary of Kecoveries for Et-FOSE-OH, Me-FOSE-OH, PFQS,

-Table 3: Summary of Recoveries for Et-FOSE-OH, Me-FOSE-OH, PFOS,

Table 4: Summary of Recoveries for Et-FOSE-01% Me-FOSE-OH. PFOS,

Table 5: Summary of.Recoveries for Et-FOSE-011, Me-FOSE-OH, PFOS, '

p o u and pK)SA in Whole Apple ............................................................... - p0,A.A a d PFOSA in Ge:n Beans' ........................................................ .......... 25

POAA and PFOSA in Chicken E,,

p0,A.A a d PFOSA in Chicken Muscle ............................................................ 27

74

26 QUS ......................................... :. ....................

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.............................................................. pOAA and PFOSA in cow Milk ....... 28

. . . Table 6: Summary of Recoveries for Et-FOSE-011, Me-FOSE-OYPFOS, .

. Table 7: Summary of Recoveries for Et-FOSE-OH, hfe-FOSE-OH, PFOS, ....... ................................................... p o u and pFOSA in Breid : ................. 29

POAA and pF0S.A in Hot DO g.'........................ ........................... ..................... 30 Table 8: Summary of Recoveries for PFOS, and F'FOU in Cmish ................. 31 Table 9: Summary of Recoveries for Et-FOSE-011, Me-FOSE-OHJFOS,

pOAA and PFOSA in Pofi'Muscle 32.

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LIST OF FIGURES (:CONTIiNTJED)

F = p e 17: Repnsentative Chromatogmm from the Injection of Control Catfish

........... ..................... 65 Figure 18: Representative Chromato-guns of a Control Pork Muscle Sample

(Set 172199 Pork, Centre'D 9911783 Pork Blank B) .......... 66 Figure 19: Repmentauve Chromatogruns from the hjxtion Of Control Pork hiuscle

Fonified at 500 ppt each of Et-FOSE-OH. M:-FOSE-OH, PFOS, POAA, and PFOSA (Set 122199 Pork, Ccnm ID 9911783 Spk B)

Fodfied at j00 ppt each of PFOS, PC)hl, and PFOSA (Set 012$00 ...... ....................... Catfish, C e n k ID 99120.52 Spk A)

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2. EXPERTILIENTAL COMPOUNIIS

Molecular structures of Et-FOSE-OH. Me-FOSIXW PFOS, POA.4, and PFOSA are given below. . .

. . PFOS molecular weight: 499 (CgF17S037 '

- - Chauical Nanc = P c d u o m n r ~ c sulfonate

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PFOSA molecular weight: 499

0

3. cHEMIc.QLs SUPPLES

3.i. CIEMICALS . '

Source Chemicti G n d e Acetonide (ACN) . HPLC m) J.T. Baker J T ~ O I ~ : ~

57210-U Carbon .. 120/400 . Supelco . . Methmol~eOH) HPLC 0 J. T. Baker n9093-2. .

. Silica gel (60-200 mesh) Reagent J. T. Baker 340 5-0 j FIon'siI (60-100 mesh) Reagent m) J. T. Baker 3372-08 S uperclem'LC-N& Reagent Supelco .5-7205 I-Octanol Reagent Aldnch Chemical 1 11-57-5 Ammonium Acetate Reagent . Si,gna-Aldn'ch - . ~ - 7 3 3 0

Toluene ... Reagent m) J. T. Baker J'l-946013 Type1 - inhouse Water

nype I water = e!ectricd resistivity, minie:um of 16.67 W c m at 25°C. from a Lbconco waterpro workst3tion)

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Catalog Nr

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L-Ascorbic acid . Reagent Si-m-AIdn'ch L-5960 . Dimetyldichlorosilane Reagent SuPelco 3-3009

3.2. STANDARDS

Standad Gnde Source Et-FOSE-OH - Andytid 3M Me-FOSE-OH Analytical . 3 M PFOS AildytiCal 3M ~

POAA Analytical 3M . PFOSX . AndvdCal 3M

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3.3. EQUIPMDT AND SUPPLES

EQUIPMENT SOURCE Balance, analvrical ' Mettler- Balance. top-loading '

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Mettler . Buck Rotary ev$orator

Rotary evaporator trap : Buchi Tissumizei . . Tekmar Sorvall RC 5C plus Centrifuge Dupont

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IEC HN SII centrifuge IEC Pm-shaFd flasks . P P X SPE tubes (20 ILL) cat no. NO57177 Supelco

Visiprep vacuiim manifold Supelco Wrisi-action s@cr. . Burrell Bench-top centrifuge IEC 50 mL disposable polypropylene.centlifuge tubes . . VWR Disposable pipei, tes! tubes etc. . . V W R - 125-mL LDPE narrow-mouth bottles Nalgene 2-mZ.~levHPLCvialkit(catn'5181-3400) - . - . H P Standard lab equipment (clgs A pipets and volumetric flasks, graduated cylinders, etc.) LUMS~S- and HPLC systems are . . As described in

Vacuum pump . Buchi

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1 .o 2.5 100 * 0.025 0.01

0.005 0.0025 0.00 1

100 0.0005

1.0 1.0 100 . 0.05 10.0 100 0.025 10.0 ' 100 0.01 10.0 - 100 0.005 10.0-

each of Et-FOSE-OH, h.lc-FOSE-OH. PFOS, POAA, and-PFOSA

4. METHOD

4.1. FLOW DUGRAM The flow &;gam of the method is g h I k l O W , followed by a 'detailed description of a c h step. - . . . .

. 5 g of matrix. Fortify if needed

E.xtnct with ACX 1

3. . . . SPE column clean up

: 1 . Concenmte to dmost dryness

1 ' Adjust final volume

5 LCRrlSh4.S analysis

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HPLC: Hewlett Packard (HP) Series 1100 HP Quat Pump Hp Vacuum De= w s e r HP Autosampier

. Hp Column Oven

, - Note: A 4 x 10 mm hypermi dropin guard canridge (Keystone, parr :: 841017400) is aaachecl on-line after the purge valve and before the sample injector pOn 10 m p my residue contaminants [hat may be in the mobile phase and/or HPLC system.

HPLC Cslury: Genesis CS (Jones iChromatopphy), 2.1 rnm 50 rnm, 4p ColumnTemp.: 35" C . Injection V O ~ : . IO PL . Mobile Phase (A):? mM Ammonium Acetat in Type I water Mobile Phase (B): Methanol

% A ' . - Time - 0.4 . 60'

7.0 1 0 ' . '

75 0 - . .

. o 60

1.0 - 10

- : 9.0 - 0 . 95 60 135 60 . 14.0 60

- % B 40 40 90 90 100 100 40 40 . 40

0.i00 0300 0300 0.500 0.400 0.400 0.400 . 0.300

Ions monitored: Approximate - - Mode Tnnsition Monitored Retention.Time Analvte -

6 7 Et-FOSE-OH negative 6ZlO,+J 59' .a. I

6.7 5.3 . . 5.1

. 6.0

Me-FOSE-OH negative 616 9 59

POM . negative 413 369 PFOSA negative - 498 9 78

PFOS negative 499 3 99

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Dwell (sl . - Collision Enerp (em Cone 30

Arialvte Et-FOSE-OH . 0.2 31 Me-FOSE-OH - 0.2

PFOS . 0.2 - POAA . . 0.2. PFOSA 0.1

' -Source 7 . Capiilary

Hexipole 1 -

Hexawle 2 Sourcc Block Temp. Desolvation Temp.

. A w l

G s Flows 'ConeG~ . Desolvation . I

Pressures GY Cell

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31 30 43 76 11' 25 2s 34

- Set. 2.56 kV -

. O S V - .- 0.1 v 0.8 V . lo0T

. 400T

. Set 13.0 V 13.0 V

. 0.7 V . - 2 v

IV 11.ov

. l l . 0 V 1.0 v

. 650V ,

- .

Set - 1 5 F ! - 700 I/hr

Read back - 3.Oe-3 mbar

. I

Page 30 of 81

. .

Page 96 of 15 1


. :

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~ .. ... . ...

Centre Analytical Laboratories, Inc. . . . . _ - . _ .

Page 97 of 15 1


. . - - .. -- . . ~ - . ..

.. . .. . , I _ . . ' .

. . , Centre Protocol No. COP-023-057 .. ._ .

- .

I '

Centre'Analytical 'Laboatories, Inc.

, :

Page 32 of 81


Centre Study NO.: 023-057 Centre Protocol No: OOP-023-057

. ..... .- .

.. . . -- - . . .- . ..

Centre Protocol No. OOP-023-057 . -- -.

5. CALCULATIONS

Equationk .

Determine the component residue concentntion using Equation 2.

Equation ?:

c=-!~t Analytical Laboratories. h c . . 'Page33of81 ' '

- . .. . . ._ . . . . . . - - .. -. .- . . . . . . . . . . .



. . . . . ._

Centre Protocol No. 0013-023-057

5.2. FORTIFICATION R E C O ~ Y Y

- Equation 3:

. . Recovery (%) =

(ndg found - (avengen&/:ifound in control)) XI00

' ndgadded

or

6, SAFETY

. ._

Centre Analytical Laboratories; Inc. .' Page 34 of 81 - .

' - .- --__ _. ... . - . -- . . .



.................... . . . . . - - - - - .---- -


. . .

. .

. . .

:TABLES .

Centre Anal)tical Laboratories. he. ....

..... - . - . ........

Centre Analytical Laboratories, Inc. . ... . . . . . . . . . . . . . . . . .

Page 13 of 69

Page 35 of 81

......

Page 101 of 151

, . . .

'I'nhlc 1: S I I I I I I I I ~ ~ Y of Itccovcrics for IZITOSE-011, ILlc-FOSII-011, I'FOS, POAA ntd I'FOSA in \Vl~olc Applc 6 E-OH

Trlal 2

a2 '6

Me-FOSE-OH ' PFOS . Trial 1 Trlal2

PI

1 1 1 1 1 K

TrlJl 1

9.024 I 09

91 ' 5

W o\ z . ' % ' Celilre Amlytical I.aliornlorics. Iiic. Sliitly N 023-001 00 c %

I

c 0 N . . . - % c

c VI

PF Trld 2 Trlnl 1

111 - i r k ND

NQ ND ND

0.432 0.411 0.892 0.840 1.787

1.781 4.514 4.787 9.100

0.134 -

Trlrl 2 . 89 I SA

-

41

I

1':igc 24 of 63

I

. . .

1

I

!

i

f

I I

I I

Trlal 2

: hde-F( Trlal E

1W20180

El-FOSE-OH Trlal 1 Trlal 2

114100

NO *

NO NQ - NO NO *

10.030

10' 16 15

F.' Y , . A'

PI A Trlal 2

PI Trlal 1 Trlrl 1

NQ

11c 9

I- &

03

08. 111

115

103

90 W 98 01

101

100 8

I

-

I

83 08

81.

03

69

60

71

88

se 87 7 G 15

- -

Reegenl Blenk B Malrlx Blank A Malrlx Blank'B

1.0 ppb Spk D

2.0 ppb'Spk F

i 10.0 ppb Spk I

AVERAQE

! . . . . . . . . ' .

NO NQ

NO 0.465

0.488

1.1 11

1.163

2.060

1.081

4.623

4.807

0.120

to.lra

Nil NQ EIQ

0.436

0.466

1 . 0 ~ 2 ,

1.120

2.138

2.145

5.203 6.410

10.400

NO

NU

0.311

0.492

0.615

0.831

1.po 1.206

3.642 4.4OQ

&OS0

8.708 - L

NO

k.rb 0.302 0.380

0.898

0.042

1.683

1.726

4.004

P.038 8107

0.220 - -

78

00

60 04

79

86 07

101

08

02

OB 0

- -

I / . , , . : .. - !

01

107

107

! '

. ~ * .

I

, . I . . ! I 8

. : w a . a . c1 m rD W 00 . . % m

Ccnlrc Arinlylical ~.~bnralor ics. Inc. Sliidy It 023-001 c-.

h g c 26 01-69

. ' I . -

. .

~

PFOS P . Et-F( Trlal 1

11f20/99

ND

10.058

95 7

5-01-1 Trlil2

11/22199

101 40

Trlal,e-FjSE-OH Trlal2

\ A ' I

Trlol 2

94 6

PF Trlal 1

1 1120/88

I 06 10

Trld 1 Trlal 2 I . 9- nai -

84

84

88 07 98 82 as 81 101

88 95 -

p9

42 53 60

'66

60

62

85 -- ,, 80 1 O(

66 -

11/21

WtL

-

ND

ND NO

NQ

D.488

0.470

0.881

0.669 1.921 1.848

4.761

4.628 10.166

9.920 -

.. . Roagonl'Blank B

Malrlx Blank A ' Malrlx Blank B

, Aeagenl BlankA G

, 2 0 3. p

I

Ei 0

. . .

. .. ,

0.5 ppb Spk A 0.5 ppb Spk B 1 .O ppb Spk C 1.0 ppb Spk D 2.0 ppb Spk E 2.0 ppb Spk F 6.0 ppb Spk G

AVERAOE

. - . .

10 !

5

,

s Ccnlrc Aiialylicnl 1-nbornlorics. Inc. Sliidy N 023-001 00 - I'ngc 27 of G9

! I !

. . ' 2 1 ;5

'I'JIIIIC 5: S u i i l i i i n r y of Rccoverics for El-~os~-oII, hfc-IPOSE-OIi, I'FOS, POAA rind I'FOSA i t I C e ~ v Millc

Mc-F Trl.1 1

llI9B9

4.417 7.832

F Trl.1 1

11mm9 j &L

D.604 101 0.632 105

0.951 05

0.007 87 1.578 79

1.787 88

,4.02e 99 , I e?? 93

5.782 88

8262 53

1 . 93 8

PI Trlil 1

llmloo

8.200 8.152

00 7

;A - .

.. - Trial 2

l l t l 8B9

. _ . .- 1.423

. . . .

I. Trlil2 '

llIlU&S

10.880 1 O i

8

- i l t l

!!!YL NO NO NQ

ND 3.449

D.480

1.030

0.908

1.785

1.971

5.380

6.314 0.168

44. 39 88

68

68

80

89

Ro

01

01

75 I

.453

,335 8.332 1.552 1.570

2 1 7

1.018

1.844

1.038

4.800 4.810 0.388

o . a e -

: ' ' F 9

. . , .

1 . . .7 g ' 10 20

- . . - -. . - . -. . - . . .- .. . .

2 0 , .

0 0 - . o

. . . . z 0

Cciilrc Aiialylicnl Lnlmratorics, Iiic. Stiidy N 023-001 . I

. . I I .

. .

I

El-F . Trlsl 1

iE-OH Trial 2

11118/99

ig;:4:'/ 973

103 9

Me-F Trlal 1

11/16/90

. 07 a10

IS II P Trlal2 Trlal 1

;€-OH P . Trlall

AA Trlal 2

PFOSA Trlal2

9I) (R.l

71

77

88

05

88

85

103

88

110

87 91 -

)o L net -

84

85

04

107

101

105

08

88

100

111 00 -

rn

. _

07

72

100

101

00

85

02

02

08

08 -

1 I/ - 32IL , ND

ND

ND'

NO 0.356

0.305

0.058

0.047

1.728

1.700

5.188

.4.8n8

i i.0ii

0.708 -

BB *

84

78

88

111

07

107

82 an

100

105 - 96

111 - 3t!L 0.248

0.523

0.363 0.040

0.693

0.168

1.204

1.218

2.178

2.087

4.684

4.700 @.e20

8.700 -

19

73

78

88

84

72. 73.

85

88

100

00

03 9

- -

111 - 22% NO'

NO

NO

NO 0.4 18

0.423

0.038

1.071

2.010

2.001

4.707

4.814 10.031

1111 - NO

ND

NO

NO

0.421

0.388

0.884

1.116

1.041

2.141

4.801

4.394

i 0.001

10.402 -

Malrlx Blank B 0.5 ppb Spk A 0.5 ppb Spk B

'

' ' RosgenlBlankE I C

! . 2 .

I F

; 5. . -

0 1 .O ppb Spk C ,

1 .O ppb Spk D 2.0 ppb Spk E 2.0 ppb Spk F 5.0 ppb Spk 6 5.0 ppb Spk H .n n _ _ L _ _ I _ . I"." I.#'" q , m I

' ! . ..

I

. .

i ' !

I

- . . : . . 12 9 10

T:ilile 7: Suiitrilnry of Recoveries for Bl-FOS&-OII, Me-ITOSE-011, I'ITOS, I'OAA nr~t l YFOSA ill IIot Dog

Et-FI Trlal 1

95 12

Mo-F -- Trial 1 '

-,P Trlnl 1

P Trlsl 1

11/8/00

11.830

' 106 6

AA Trlal2

f l l l l lD0

10.428

97 B

PI Trl.1 1

0.380

88

7

Trlal 2

0.441 , 88

0.353 71

0.879 88

0.088. 07

2.001 100 1.820 , 08.

10.120

06

10

Trlsl 2 . 1111 1/00

103 0

89 *

I 07

73

Io0 103'

00

00

09

107

108

112 - rpo

'9- %

77

78

04

02

67

so 11;

107 114

108 90 -

Trlal2 3 2w4

NO

NO NO

NO 0.488

0.385

1,004

1.027

1.000

1.080

4.950

6.340

io.6oa

11.240 -

'e (R.c

87

84

92

1 or 03

00

103

100 too 87 90 -

111 - 34L

m NO

0.307

NO 0.448

0.453

1.Do1

0.083

i.ie5

1.253

6.805

1.380 11.462

Io.BBB

111 - 2 L L 0.178

NO 0.070

0.173

0.857

0.640

1.041

1.137,

1.087

2.008

6.248

6.1 17 10.080

0.812 -

RoaQenl Blank B

EAalflw Blenk B 0.5 ppb Spk A 0.6 ppb Spk 0 , 1 .O ppb Spk C

2.0 ppb Spk E

6.0 ppb Spk Q 6.0 ppb Spk H 10.0 ppb Spk I 10.0 b S k J

Malf lX Blank A

AVEnAOe

10 21 6 .. -. - . .

.

I'npc 30 of 63

I

I

I’P0S.- in ‘ h l h 8: Suttiitinry of Itccovcric for I’liOS, I’OAA :ti11 IliSll

sn] ’ ~

PI Trlal 1

llZl/OO

11.140

117 9 I

P! Trhl 1

112 1/00

115 26

PI Trial 1 ,

- .

., 108 6

1A Trlal 2 Trlrl2

. .

0 - * 4 ’

120

120

132.

140

143 I.:&

113 .^^ I 4 0

121

120 -

1 li

2dlL -

0.710

Oi737

1.320

1.166

1.650

1.044

2.200

2.224

3.608

3.710 e.210

0.800

12.07~

12.08:

0 - if&

61

120

102

00

113

123

00

315

108

108 -

112 - S!L ND ND

NQ NQ

0.506

0.642

1.310

1.300

2.884

2.031 6.074

3.363

12.101

1 1; - 2dlL ND ND

NQ NQ

0.401

0.500

1.003

1.116

2.141

1.892

4.942

5.701

11.43:

3

E .

- .

. . 06

101

1 00

112

107

9s

9 0 114

. . . .

I

Raogonl Blank P

Malrix Blank A Malilx Olank B 0.5 ppb. Spk A

0.5 ppb Spk B 1.0 ppb Spk C 1.0 ppb Spk D 2.0 ppb Spk E 2.0 P P ~ Spk F 5.0 ppb Spk G 5.0.ppb Spk,H 10.0 ppb Splc I

AVERAGE: . I

, ’

107 12

,130 11

P

I

F : ?

+ CI 0

. 'E: c-i VI Y

0 1 c

8

x I

I

. .

I

:, .

....... - . ._


. . . . . . . . . . . . . .... ....... . -. .... - ---- - ._. - . _ _

. .


'FIGURES

Ccnuc An;llytid LbOnto r i~ . In:. Study # 023-W

I


...... .. ...........

Centre Analytical Laboratories, Inc. . - - .

!

I I .

.Page33 of 69

I . Page45 of 81 !. .

. _-__ ! ....... . . . .

Page 111 of 151


................. . - . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... . :: '. .

. . . . . ._ ::.

. _ :.. -. -.. . . : - .

Centre Protocol No. oOP-023-057 , .... ;. . . . . . . . . 1:: ,. ....... -

I . . . . , . - . 1 . .

Centre Analytical Laboratories, Inc. .

Centre Analytical Laboratories, Inc.. .. __ - __ - - - - - - - _ _ _ _____ _ _ . _.

!

!

. !

i

. . . . . . . . . . . .

page 34 Of 69

Page 46 of 81

Page 112 of 15 1

Centre Study No.: 023-057 Centre Protocol No: OOP-023-.057

_ . - - . . . . . . . . . . . . . . . . . .

. . . . . . . . ..... ... .- ... . . .... Centre ... Protocol No. OOP-023-057 -------____

I . .

!

Centre Analytical Laboratories, Inc. - ._ ._ - - - - - - - __ - -

Page 47 of 81

Page 113 of 15 1

!


.. .. - . . . -. . - . . F -- ----- -- . . . . . -. - --_ -. . . - - . . - . .

. . . .

'lentre Protocol No. OOP-023-057 ------..- --__ --.__ - . -. - - . .-. -- .- . -- __ . . .

I . .

Figure 2: Representative Chromato,-; ofa Control Whole Apple sample (set ,111799 Apple, Centre ID 983732 tipple Blank A)

I cmrc h l y f i a l ' L b o n t o n ~ . Inc. Study':: 02391 . I

. Centre Analytical Laboratories, Inc. ' '

- . . . . .. ~ . . . .... -- .- __. I

Centre Analytical Laboratories, Inc. - - __-

. .. _ .

Page 114 of 151

i

Centre Study No.: 023-057 Centre Protocol No: OOP-023-057 . .

......... . . . . . . . . . . . ...... .. -- . . . . . . . . . . .

Centre Protocol No. COP-023-057

Figure 2 (continued): Representative Chromatograms of a Control )nole ~ & l ~ Sample (Set 111799 Apple, Centre ID 9 S X ? Apple Blank A)

.

. .

4 : POXX 1983732 Apple Blank A

. . ..

. _ . .

I


. . - . . . . .- .......... -.- -.___ _ _ .

Centre Analytical Laboratories, Inc. .. ... ............... . . - . . . .

Page 49 of j8 1 . .

Page 115 of 15 1


-- . ... . . -. . . .

Centre Protocol No. OOP-023-057 - - .

i . . .. . .

! -

I 1 0

. ' l.bO ' 2.bo 3.00 4.b0 ' 5 . b 6.00 7

I

!

! Page 38 of 69 !

I i . Centre Analytical Labol,+ories, Inc. I Page 50 of 8 I

,. ____. . .. . ._ . . . . . - . . Centre Analytical Laboratories, Inc.

. .

Page 116 of 151 - .

Centre Study No.: 023-057 . Centre Protocol No: OOP-023-057

. . . . . . . . . . . . . . . . . . . . . .. ..... . . . . . - - -. -. ..... _ _ - . . . . .

. . - - . . . . . .

. Centre Protbcol NO. OOP-023-057 . . . . . . . . . . . . . . . . . ----- -2--- . . . I

!

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Centre Analytical Liboratones, Inc.

- - - - . -

Centre Analytic a1 Labor at ories , Inc . _ . .

pig: 39 of 69

Page.51 of 81

Page 117 of 151


. . ................. ........... . .-.-_.- __-. . .

...... ... ...... .- - ... Centre P r o t ~ o 1 . ~ . . ~ ~ ~ ~ 2 3 - 0 5 . 7 . .

i

LCIMSNS unit 6' MfiM of5 Channels ES-

630 > 59 1.30e3

-2,

2137

3: P?OS bS08032 Green Eeans Blank A . . .

i . . ! Centre Analytical Laboratories', IW..

. . . . ...... . ~ __.._-.-. . -.---I .-_._ ___._ ...... - ......

Page 40 of 69

Page 52 of 5 1 . . ..


Centi-e Study No.: 023-057 Centre Protocol No: OOP-023-057

Centre Protocol No. 00P-023-057 - . .. . .- ..

I . .

I .?! l.bO " 2.b0 ' 3.b0 '

Area/ . .

. . . . -. . . ...- ------___- - .

h$41 of 69

. . I . Page 53 of 81'



................... . -. -. - -. - - - - . , ..

- . . .

............ . . . . . . . .... Centre Protocol No. COP-023-057 . . .- -- _ _ . . . . . . . . . . . . . . . - - - --- -. ..

1: E t - F O s i a - 9908032 Spk B, Green Beans 500 ppt . . . .

I 1

I . . Centre Analytical Laboratories; hc. Page 54 of 8 1 . .

. ._ . _ _ .. , . , , .

Centre Analytical Laboratories, Inc. Page 120 of 151 ............. ... ..... . . . . . . . . . . . . . . . . . . . . . ...............


. ... .

' I , . . Centre Analytical Laboratories, Inc..

. ._. . .. . - . - - . . . . . ... -..- -- ..-_ . ~ a g e 5 i O f ~ 1 .

-

Centre Analytical Laboratories, Inc. . _. . .

Page 121 of 151


. . . . . . . . . . -- . . . . .

. . . . . . . . . -------_- - -_ . . - . .

i ' . ........... Centre Protocol No. OOP-623-057 ' . . . . . . ...- ....

!

4 . 20. - 2 : ne-?os-oE 912031 Egg BIankA . -

'i22CCS-1011 Srn (SG, 2x2) - . 620 - -

. - .nn

I . - 1.30e31

I . . ._ 3.09e4

Area

!

Centre Analytical Labora'tories. bc., Page 56 of 81; ' .. ..-__ . -. -. . -. .____ -. . -. _ _

Centre Analytical Laboratories, Inc. Page 122 of 151 . . . . . . . . . . . . . . . . .- . _ _ -


...... . ........ . . .

. . . . . . . . . . . Centre Protocol No. OOP-023-057

. . - . -

. . i : I . .

m990-1011 9912031 Lpg Bl& X

1: . 29-Dec-1999 of 5 Channels ES- .. . 5.87 .

122?991011 Srn (SG, 2x2)

. 4sa 78

. . . . . .

! ! ! . 45 of69 I

C:me myrid ~.,bo~toria ~nc s~udy a c r h o i . .

I Page 57 of 81 . I

Centre Analytical Laboratories, Inc. i

....... . . . ........... .---- .... - - . I ----. ___

Centre Analytical Laboratories, Inc. Page 123 of 151 ........ - - .... .. . . ...... ~ . . _ ~ ...... ..

Centre Study No.: 023-057 Centre Protocol No: OOP-023.057

. . r

._

I

1.f 1 : 7.18e31 Area

I

1"

6.58e4 . . ' . I .

I Page 58 of 81 , Centre Analytical Laboratories. Inc. ' !

. ... . . . .. ... . . . . . .. . . I

.......... -.

Centre Analytical Laboratories, Inc. . - - _ - _ . - --- - - .

Page 124 of 151


- . . . . . -. . . . -. . . -. .

. .

.. . ----- . _.._ __. . . ... . - - .- _ _ .. . .

-. . . . . . . .... . . . . .

. . . . . . .. 'Centre . . . . Protocol . ~ No. COP-023-057

I

. ..

. .

"entre Analytical Labojtories, Inc.

. - .-_. . . . . _. . . I . .. . . - . .


page 47 of 69

Page 59 of 8 I

.

Page 125 of 15 1


. ...... .. .. - - - . . . . . . . . .

Centre Protocol No. .@P:023r057--. l-..

I

6 . E 10

. -

I

~

I: PCOS

310292 Chicken Ejlank B 20-Nov-10(1903:41:4a . LCIMS/MS unit d .

M%V af 5 Channeh ES- 49s > cc

420e3

4.75 11 l,OSP612 Sm (SG, 2x2) '

. . . pentre Analytical Laboratories, Inc.' . .

- . - - -. -. - . . . - .. . _. .____.___C_...---- -. . . .. .

Centre Analytical Laboratories, Inc. . .--.- .--I .-- .- - - . _. ... . ~ - -- -

P& 48 af 69

I

Page 60 of 8 1

Page 126 of 151 ._ -


. .. . . . - . - - . - - -..- - . . ..

. ' .. Centre P r o t o c o f ~ . . ~ P - 0 2 ~ ~ 7 - - - - 1 .

1 - 4.16e4 ATOa[

. .

. .

Page 49 of 69

. I

Page61of81 . . .

Centre Analytical Laboratories, In'c. . .

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Centre Analytical Laboratories, Inc. .------I - - _ _ _ _

Page 127 of 15 1


. . . , ... , .

. . . !

1: Et-FOSz-oE

.. - . . . . 9910292 Spk A, Chicken 500 ppt

I . . Areal I

. .

50 of 69 , GWC A n d y t i d hhntorio. Inc. Snrdy t 0 3 3 - ~ 1 . . .

. .

Centre Anhytical Laboratories. Inc. Page 62 of 8 1 . . - -..--. . . .- ~ . .. -

Centre Analytical Laboratories, Inc. -.._ -_ _ _ _ _ _ _ .

Page 128 of 151


MRM of5 Channels ES-

9.Ei.4

. 559 1003 49a 78

Centre Analytical. Labontorie;. Inc: . Page63.of81 ,

- . . . . . . - .. . . . . - -. ---- _ _



. . . . Centre Protocol No.lX)P~023=05.7'-.

I .

I

09-Nov-1s,o9 20:43:5$

MRM Of 5 Channels ES- 1 6.60 630 > 591

u a I I

Centre Analyticai Laoorat, L, !x. . . .

. . - ._ . . . . . . . ..... . . ----

Centre Analytical Laboratories, Inc. -- . . ........... . _ _ ~ __ .....

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Page 130 of 15 1 ... .... . . .- _I ... .........


. .

. . . . . . . _. . . . . . . .

........ . . . . . . . . . . -- . .- .

. . . _. Centre pro t&o&-IMEa't -0 57

110999-2012 Sm (SG, 2x2) 1 , - . . 4.07 . . 9024 1 * -

413 > 369 3.99e4

. Area

!

Centre myrid ~b~uorio, Inc. Study 03CO1 . j of 69 1 :

. I Page 65 of 8 1 ! Centre Analytical Laboratories, Inc.

. , . . . . . . .... . - -__.. . - , - - . .

Centre Analytical Laboratories, Inc. Page 131 of 151 .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . - . ---


I

1: Et-XJOS2-m ' . - 572627 Spike A, Milk 500 ppt

CenUc hdyrid I;lbonmrics, he. SNdy n' 023-Wl

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Centre Study No.: 023-057 Centre Protocol NO: OOP-023-057

Centre A n d y t h Laboratories, h c . . i . Page65of51 . . ' !

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E,We 12 (continued): ‘Representative bomato,$pms Of a Control Brmd sample .(Set 111999 Bread, Centre ID 9905031 Bread Blank A) .

11 1929-51 1 Sm (SG, 2Y2)

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Figure 14 (continued): Representative C ~ ~ ~ ~ ~ O W I L S of a Control Hot Dog Sample (Set 110899 Hot Dog, Centre ID 9903035 Hot Dog Blank B)

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Figure 15 (continued): Representative C h r o m a t o m from the Injection of Control Hot Dog Fortified at 500 ppt each of Et-FOSE-OH, Me-FOSE-OH, PFOS, POA.4, and PFOSA (Set 110899 Hot Dog, Centre ID 9908035 Spk B)

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N-: Ol2400-101( . . 9912032 S;k A, mtfish 500

1: PFOS . 9912032 Spk A, Catfish 500 ppt . 24-Jan-2000 20:;3:11

LC/MShlS unit 6 MRM of 5 Channels ES-

012-1014 Sm (SG. 2Q)

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Figure 18 (continued): Representative Chromatograms of a Control Pork &rucle Sample (Set 122199 Pork, Centre ID 9911753 Pork Blank B) '

4: PFOOSX -9911783 Pork Blank B

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N-: 122139-2s . . . Tax:: 9911783 spk 9, Pork 530 P P C

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Centre Study No.: 023-05L1.- Centre Protocol No: 00P-023-057

CEntrE Analytical Laboratorks, Inc. 3048 Research Drive State College, PA 16801 phone: (814) 231-8032 Fax: (814) 231-1253 or (814) 231-1580 - _ - . .

Page 1 of

PROTOCOL A . ? V l E ~ M E ~

Amendment Number: 1 Effective Date: March 26,2001

Centre Study Number: 023-057 Centre Protocol Number: OOP-023-057

DESCRTPTION OF AMENDED SECTION

1. Page 5 of Protocol: Assips Susan Beach as the Study Director at 3M.

1. Change the study director to Karen Smith at Centre Anidyt.iCd Laboratories and make Susan Beach the Sponsor Representative at 3M.

RATIONALE

. . Reassignment of responsibi1ities for study at the request of Sponsor.

IMPACT ON THE STUDY

. There is no negative impact on the study.

- presentative Signature Date


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Cmtrr Analytical Laboratorks, Inc. a\ 3048 Research Drive State College, PA I 6801 Fax: (814) 231-1253 or (814) 231-1580 Phone: (814) 231-8032 -

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PROTOCOL AMENDMENT Amendment Number: 2

Effective Date: April 30.2001 Centre Study Number: 023-057 Centre Protocol Number: OOP-023-057

DESCRIPTION OF AMENDED SECTION

1. Page 7 of Protocol-Experimental Design: States that each set Of samples analyzed will contain at least one matrix coilti01 and two fcrtificaticns.

AMENDEQ! .

1. Add that each set of samples analyzed will also contain a reagent blank.

RATIONALE

1. Added at request of the sponsor.

W A C T ON THE STUDY

1. There is no negative impact on the study.

- b Date

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Date &

Sponsor Representative Signature

CAL QAU Review

.Centre Analytical Laboratories, Inc. Page 149 of 15 1

3048 Research Drive State College, PA 16801 W&w.centrelab.com Phone: (814) 231-8032 (814) 231-1253 or (814) 231-1580

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Page 1 of 1

PROTOCOL A M E " E N T

Amendment Number: 3 Effective Date: June 15,200 1

Centre Study Number: 023-057 Centre Protocol Number: OOP-023-057

DESCRIPTION OF AMENDED SECTION

1. Study Title

AMENDEDB

1. Analysis of PFOS, FOSA and PFOA From Various Food Matrices Using HPLC Electrospray/Mass Spectrometry.

RATIONALE

1. Changed for clarity at the request of the sponsor.

IMPACT ON THE STUDY

1. There is no negative impact on the study.

Centre Analytical Laboratories, Inc. Page 150 of 151 .__


CEntre Analytical Laboratories, Inc. 3048 Research Drive phone: (814) 231-8032

State College, PA I 6801 Fax: (814) 231-1253 or (814) 231-1580

Page'l of PROTOCOL DEVIATION

Deviation Number: 1 Date of Occurrence: 1) January 19,2001; 2) February 15,2001

Centre Study Number: 023-057 Sponsor Study Number: NA

DESCRIPTION OF DEVIATION

1) A recovery of 56% for FOSA is being accepted for the 10.0 n d g Spk B in data set 011901A Fish.

2) A CCV recovery oi 143% is being accepted for the 2.5 nd/mL standard for FOSA in data set 021401A Beef.

ACTIONS TAKEN i.e.. amendment issued, SOP revision. etc ...

1) Deviation issued. 2) Deviation issued.

tecorded ByiDate:

U IMPACT ON THE STUDY

1) There was no negative impact on the study since the 2.5 n g h d Spk A for FOSA in lata set 01 1901A Fish was within the 60-130% acceptable range and the levels of residue

found in the fish samples were: all below 2.5 ng/pd?@ 2) There was no negative impact on the study since the CCV'S before and the C C v run

after the standard in question were acceptable.

30

@@ ky - Date

/ *lizh gncipal u t i g a t o r Signature

FJk c

3-?,//-- s- WA,A kudy Director Signature Date

ponsor Manazement Signature Date

Centre QAU Review 6 hh,


summary of analytical results: multi-city food study · analytical report completion date june...

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