Study Title Data Requirement Study Director Author · 8.5 Lab Control Spikes (LCSs) 16 8.6 Analytical Method Uncertainty 22 9 Data Summary and Discussion 22 10 Conclusion 103 Page

Interim Report #16-Analvsis of Woodbury Waste Site Water Samples

Study Title Exygen Protocol P0002561: Analysis of Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid

(PFPeA), Perfluorohexanoic Acid (PFHxA), Perfluoroheptanoic Acid (PFHpA), Perfluorooctanoic Acid (PFOA), Perfiuorononanoic Acid (PFNA), Perfluorodecanoic Acid (PFDA), Perfluoroundecanoic Acid

(PFUnA), Perfluorododecanoic Acid (PFDoA), Perfluorobutanesulfonate (PFBS), Perfluoroiiexanesulfonate (PFHS), and Perfiuorooctanesulfonate (PFOS) in Water, Soil, and

Sediment Using LC/MS/MS for the 3M Cottage Grove Monitoring Program Phase 2

Data Requirement EPA TSCA Good Laboratory Practice Standards 40 CFR Part 792

Study Director Jaisimha Kesari P.E., DEE

Weston Solutions, Inc. 1400 Weston Way

Westchester, PA 19380 Phone: 610-701-3761

Author Susan Wolf.

3M Environmental Laboratory

Interim Report Completion Date Date of signing

Performing Laboratory 3M Environmental Health and Safety Operations

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

Maplewood, MN 55144

Project Identification E06-0549

Total Number of Pages 207

Exygen Protocol P0002561; Interim Report #16 3M Project E06-0549

Analysis of Woodbury Waste Site Groundwater Samples; 3rd Quarter 2007

This page has been reserved for specific country requirements.

Page 2 of 207

Exygen Protocol P0002561; Interim Report #16 3IV1 Project E06-0549


GLP COMPLIANCE STATEMENT

Report Title: Interim Report #16 Analysis of Woodbury Waste Site Water Samples: Study Title: Analysis of Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid (PFPeA), Perfluorohexanoic Acid (PFHxA), Perfluoroheptanoic Acid (PFHpA), Perfluorooctanoic Acid (PFOA), Perfiuorononanoic Acid (PFNA), Perfluorodecanoic Acid (PFDA), Perfluoroundecanoic Acid (PFUnA), Perfluorododecanoic Acid (PFDoA), Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfiuorooctanesulfonate (PFOS) in Water, Soil, and Sediment Using LC/MS/MS for the 3M Cottage Grove Monitoring Program Phase 2. Exygen Protocol P0002561.

This analytical phase was conducted in compliance with Toxic Substances Control Act (TSCA) Good Laboratory Practice (GLP) Standards, 40 CFR 792, with the exceptions listed below:

Exceptions to GLP compliance:

• The documentation of all extractions was performed using Excel and then printed out. For all extractions, the extraction prep sheet was printed out later than the extraction date.

^^S-O-. \^C^<JoJ^ i:2^-2.ilo'j Robert A. P^schke, Sponsor Representative Date

'0 A ^ i . JaisimhaKesari, P.E., DEE, Study Director ' ' Date

Page 3 of 207



QUALITY ASSURANCE STATEMENT

Report Title: Interim Report #16 Analysis of Woodbury Waste Site Soil Samples: Study Title: Analysis of Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid (PFPeA), Perfluorohexanoic Acid (PFHxA), Perfluoroheptanoic Acid (PFHpA), Perfluorooctanoic Acid (PFOA), Perfiuorononanoic Acid (PFNA), Perfluorodecanoic Acid (PFDA), Perfluoroundecanoic Acid (PFUnA), Perfluorododecanoic Acid (PFDoA), Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfiuorooctanesulfonate (PFOS) in Water, Soil, and Sediment Using LC/MS/MS for the 3M Cottage Grove Monitoring Program Phase 2. Exygen Protocol P0002561.

This analytical phase was audited by the 3M Environmental Laboratory Quality Assurance Unit (QAU), as indicated in the following table. The findings were reported to the principal investigator (P.I.), laboratory management and study director.

Inspection Dates

August 22, 2007

November 13-15, 2007

November 26-29, 2007

Phase

In-Phase

Data Audit

Date Reported to

P.I.

August 24, 2007

December 3, 2007

Testing Facility

Management

January 14, 2008

January 14,2008

Study Director

January 14,2008

January 14, 2008

u>4^^^ H/^-^^j<jy QAU Representative

f-JlJi-oY Date

Page 4 of 207



TABLE OF CONTENTS

GLP Compliance statement 3

Quality Assurance Statement 4

Table of Contents 5

List of Tables 6

1 Study Information 8

2 Summary 9

3 Introduction 9

4 Test & Control Substances 10

5 Reference Substances 10

6 Test System 12

7 Method Summary 12

7.1 Methods 12

7.2 Sample Collection 12

7.3 Sample Preparation 12

7.4 Analysis 12

8 Analytical Results 14

8.1 Calibration 14

8.2 Limit of Quantitation (LOQ) 15

8.3 Continuing Calibration 15

8.4 Blanks 15

8.5 Lab Control Spikes (LCSs) 16

8.6 Analytical Method Uncertainty 22

9 Data Summary and Discussion 22

10 Conclusion 103

Page 5 of 207



11 Data/Sample Retention 103

12 Attachments 103

13 Signatures 104

LIST OF TABLES

Table 1. Instrument Parameters 13

Table 2. Liquid Chromatography Conditions f 13

Table 3. Mass Transitions 14

Table 4. Limit of Quantitation (LOQ) 15

Tables. Laboratory Matrix Spike Recovery 17

Table 6. Analytical Method Uncertainty 22

Table 7. Sample Concentrations 23

Table 8. Field Matrix Spike Concentrations 32

Table 9. WBMN GWTripl 070808 38

Table 10. WBMNGWS01PC 39

Table 11. WBMN GW SOUS 41

Table 12. WBMNGWWR3 43

Table 13. WBMNGWS08JS 45


Table 15. WBMN GWTRIP2 070809 49


Table 17. WBMNGWS04SP 52



Table20. WBMNGWS07PC 58

Table21. WBMNGWS07JS 60

Table22. WBMNGWS07SP 62

Page 6 of 207






Table 26. WBMN GW TRIPS 070809 70

Table 27. WBMN GWMWH 71

Table28. WBMNGWS05SP 73


Table30. WBMNGWMWG 77



Table 33. WBMN GWS02PC 82

Table 34. WBMN GWS02DR 84

Table 35. WBMN GWS09JS 86

Table 36. WBMN GWMW4L 88


Table 38. WBMNGWB1 91

Table39. WBMNGWB2 93



Table 42. OKMNGWW203 99

Table43. WBMNGWMW2 101

Page 7 of 207



1 Study Information

Sponsor

3M Company

Sponsor Representative

Robert A. Paschke Manager, 3M Corporate Environmental Programs Bldg 42-02-E-27 St. Paul, MN 55144 Phone: (651) 778-5200

Study Director

Jaisimha Kesari, P.E., DEE Weston Solutions, Inc. Westchester, PA 19380 Phone:(610)701-3761 Fax:(610)701-7401 [email protected]

Study Location

Testing Facility

3M EHS Operations 3M Environmental Laboratory Building 260-5N-17 Maplewood, MN 55106

Study Personnel

William K. Reagen, Ph.D., Laboratory Manager Susan Wolf, Principal Investigator, ([email protected]): phone (651)-733-9851 Cliff Jacoby, Technical Review Vallabha Tantry; professional services support staff personnel Zhuojing Liu; professional services support staff personnel

Study Dates

Study Initiation: 20-October-2006 Interim Analytical Initiation: 10-August-2007 Interim Analytical Completion: 8-October 2007 Interim Report Completion: Date of Interim Report Signing

Location of Archives

All original raw data and the analytical report have been archived at the 3M Environmental Laboratory according to 40 CFR Part 792. The test substance and analytical reference standard reserve samples are archived at the 3M Environmental Laboratory according to 40 CFR Part 792

Page 8 of 207

mailto:[email protected]




2 Summary

The 3M Environmental Laboratory received one hundred forty-four samples including five sets of trip blanks fi'om the Woodbury, MN waste disposal site. One hundred twenty-two battles were received fi-om Weston personnel on August 10,2007 along with chain of custody (3M C.O.C. # 13570,13571, 13572,13573,13574,13575,13576,13577.13592,13594,13600, 13595,13596, and 13597), twenty-two bottles were received fl"om Weston personnel on August 15, 2007 along with chain of custody (3M C.O.C. #13593,13599, and 09687). Samples were prepared and analyzed for Perfluorobutanoate (PFBA), Perfluoropentanoate (PFPeA), Perfluorohexanoate (PFHA), Perfluoroheptanoate (PFHpA) Perfluorooctanoate (PFOA), Perfiuorononanoate (PFNA), Perfluorodecanoate (PFDA), Perfluoroundecanoate (PFUnA), Perfluorododecanoate (PFDoA), Perfluorobutane sulfonate (PFBS), Perfluorohexane sulfonate (PFHS) and Perfluorooctane sulfonate (PFOS) under 3M Environmental Laboratory project number E06-0549.

3 In t roduct ion

The objective of this study was to analyze collected water samples from the Woodbury waste site for the selected perfluorocarbon acid analytes in effort to aid identification of historical FC waste disposal locations at the site. This report also contains one sampling location fi-om Oakdale, MN.

The 3M Environmental Laboratory prepared sample containers (500 mL polyethylene bottles) which were picked up by Weston Solutions personnel prior to field sampling. Sample containers for each sampling location included a field sample, field sample duplicate, and a minimum of two field spike samples. Each empty container was marked with a "fill to here" line to produce a final sample volume of 450 mL. Containers designated for field matrix samples were fortified with an appropriate matrix spike solution containing the analytes of interest, prior to being sent to the field for sample collection. See section 8.7 of the report for field matrix spike levels.

Samples were prepared and analyzed according to that defined in 3M Environmental Laboratory method ETS-8-154.3, "Detemiination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates in Water by Solid Phase Extraction and High Perfbnnance Liquid Chromatography/Mass Spectrometry".

Section 9 summarizes the sample results using the analytical method identified above. All results for quality control samples prepared and analyzed with the samples will be reported and discussed elsewhere in this report.

Page 9 of 207

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Reference Substance

Chemical Name

Chemical Formula

Identifier

Source

Expiration Date

Storage Conditions

Chemical Lot Number

TOR Number

Physical Description

Purity

PFOA

Perfluorooctanoate

CyFisCOQ-

/^monium Salt, CAS # 335-67-1

3M

02/27/2017

Frozen

332

TCR-123

White powder

95%

PFNA

Perfiuorononanoate

CsFirCOQ-

Add, CAS #375-95-1

Oakwood Products

10/28C007

Frozen

H7568

TCR-618

White crystals

98.02%

PFDA

Pertluorodecanoate

CgFigCOO'

Add, CAS #335-76-2

Oakwood Products, Inc.

10/28/2007

Frozen

R11K

TCR-036, SD036

White solid

98.01%

PFUnA

Perfluoroundecanoate

C10F21COO"

Add, CAS #4234-23-5

Oakwood Products, Inc.

10/29/2007

Frozen

U11N

TCR-619

Solid

96.4%

Reference Substance

Chemical Name

Chemical Formula

Identifier

Source

Expiration Date

Storage Conditions

Chemical Lot Number

TCR Number

Physical Description

Purity

PFDoA

Perfluorododecanoate

C11F23COO"

Add, CAS #307-55-1

OakwDod Products, Inc.

10/28/2007

Frozen

R24K

TCR-037

White solid

99.65%

PFBS

Perfluorobutanesulfonate

C4F9SO3"

Potassium Salt,

CAS #2942049-3

3M

01/18/2017

Frozen

Lot 2

TCR-359

White powder

97.3%

PFHS

Perfluorohexanesulfonate

C6F13SO3'

Potassium Salt,

CAS #3871-99^

3M

02/12/2017

Frozen

NB 120067-69

TCR-083

White powder

98.6%

PFOS

Perfluorooctane sulfonate

C8F17SO3'

Potassium Salt, CAS #2795-39-3

3M

08/31/2016

Frozen

217

TCR-696

White powder

86.4%

Page 11 of 207



6 Test System

The test system for this study is water samples fi-om Woodbury, MN waste site collected in August 2007 by Weston Solutions, Inc. personnel. The test system for one sample in this study is a water sample fi-om Oakdale, MN waste site collected in August 2007 by Weston Solutions, Inc. personnel. Samples for this study are "real worid" samples, not dosed with a specific lot of test substance.

7 Method Summary

7.1 Methods

All samples were prepared and analyzed by the procedure defined In method ETS-8-154.3 "Detemiination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates in Water by Solid Phase Extractions and High Performance Liquid Chromatography/Mass Spectrometry".

7.2 Sample Col lect ion

Samples were collected in 500 mL Nalgene™ (high-density polyethylene) bottles prepared at the 3M Environmental Laboratory. Sample bottles were returned to the laboratory at ambient conditions on August 10 and August 15,2007. Samples were stored refiigerated at the laboratory after receipt. A set of laboratory prepared Trip Blank and Trip Blank field matrix spikes were sent with each set of collection bottles

7.3 Sample Preparat ion

All samples, calibration standards, and associated quality control samples were extracted using a modified procedure of ETS-8-154.2. Briefly, 40 mL of sample were loaded onto a pre-conditioned Waters CI 8 solid-phase extraction (SPE) cartridge (Sep-Pak, 1.0 g, 6 cc) using a vacuum manifold. The loaded SPE cartridges were then eluted with 5 mL of methanol. This extraction procedure concentrates the samples by a factor of eight. (Initial volume = 40 mL, final volume = 5 mL).

7.4 Analys is

All samples and quality control samples were analyzed for the target analytes listed previously using high performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS). Detailed instalment parameters, the liquid chromatography gradient program, and the specific mass transitions analyzed are described in the raw data hard copies placed in the final data packet, and are briefly described below.

Page 12 of 207



Table 1. Instrument Parameters.

Instrument Name

Analysis Date(s)

Liquid Chromatograpli

Guard column

Analytical column

Injection Volume

Mass Spectrometer

Ion Source Electrode

Polarity Software

ETSStan

September 2-3,2007 September 8-9,2007

Agilent 1100

Betasil C18 (100 mm X 2.1 mm), 5 n

Betas!) CI 8 (100 mm X 2.1 mm), 5 n

100 uL

Applied Biosystems API 4000

Turbo Spray

Z-spray

Negative

Analyst 1.4.2

ETS OIlie

October 5-6,2007 October 8,2007

Agilent 1100

Betasil CI 8 (100 mm X 2.1 mm), 5 n

Betasil C18 (100 mm X 2.1 mm), 5 n

5nL

Applied Biosystems API 4000

Turtw Spray

Z-spray

Negative

Analyst 1.4.2

Table 2. Liquid Chromatography Conditions

step Number

0 1

2

3 4

5

Total Time (min)

0

2.0

14.5

15.5 16.5

20,0

Flow Rate (fJJmIn)

300

300

300

300

300

300

Percent A

(2 mM ammonium acetate)

90

90

10

10

90

90

PercentB

(MethanoO

10

10

90

90

10

10

Page 13 of 207



Table 3. Mass Transitions.

Analyte

PFBA

PFPeA

PFHxA

PFHpA

PFOA

PFNA

PFDA

PFUnA

PFDoA

PFBS

PFHS

PFOS

Mass Transition

Q1/Q3

213/169

263/219

313/169

313/269

363/319

413/369

413/219

413/169

463/419

513/469

563/519

613/569

299/80

299/99

399/99

399/80

499/99

499/80

499/130

Note: Dwell times vary wittt mettiod and instniment and are recorded with tfie raw data for each run

8 Analytical Results

8.1 Calibration Calibration standards were prepared by spiking known amounts of stock solutions containing the analytes of interest into 40 mL of laboratory water. Each spiked water standard was then extracted in the same manner as the collected samples. A total of twelve spiked standards ranging fi-om 0.025 ng/mL to 25 ng/mL (nominal) were prepared. A quadratic, 1/x weighted, calibration curve was used to fit the data for each analyte. The data were not forced through zero during the fitting process. Calculating the standard concentration using the peak area counts and the resultant calibration curve confirmed accuracy of each curve point.

Each curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method calibration accuracy requirements of 100±25% (100±30% for the lowest curve point) were met with the following exceptions:

• 9/2/07 analysis - The 0.1 ng/mL curve point for PFUnA had a recoveriy of 73.7% and was retained in the curve.

• 9/8/07 analysis - The 0.1 ng/mL curve point for PFNA had a recovery of 72.1 % and was retained in the curve.

• 10/08/07 analysis - The 0.5 ng/mL cun/e point for PFNA had a recovery of 128% and was reatined in the curve.

A minimum of nine curve points were used to establish the curve. Retaining points just outside of the acceptance criteria has a neglible effect on the sample results.

The con-elation coefficients (r) were greater than 0.995 for all analytes in each analysis.

Page 14 of 207



8.2 Limi t of Quant i tat ion (LOQ)

The LOQ for this analysis is the lowest non-zero calibration standard in the curve that meets linearity and accuracy requirements and for which the area counts are at least twice those of the appropriate blanks. The nominal LOQ for analytes by analysis date can be found in Table 4.

Table 4. Limit of Quantitation (LOQ)

Analyte

PFBA

PFPeA

PFHxA

PFHpA

PFOA

PFNA

PFDA

PFUnA

PFDoA

PFBS

PFHS

PFOS

Analysis Date 9/02/07

LOQ, ng/mL 0.0946

0.0356

0.0371

0.0300

0.0963

0.0397

0.0492

0.0493

0.101

0.0795

0.0413

0.0245


LOQ, ng/mL 0.0946

0.0356

0.0232

0.0250

0.0241

0.0298

0.0246

0.0986

0.101

0.0795

0.0413

0.0245


LOQ, ng/mL ------

0.0492

0.0986

0.101

---


LOQ, ng/mL 0.0946

0.0356

0.0232

0.0250

0.0481

0.0298

0.0492

0.0986

0.101

0.0795

0.0413

0.0245

8.3 Cont inu ing Cal ibrat ion

During the course of each analytical sequence, continuing calibration verification samples (CCVs) were analyzed to confimri that the instrument response and the initial calibration curve were still in control. All CCVs met method criteria of 100% ± 25% with the following exceptions:

• 9/02/07 analysis - Several samples were re-analyzed on 10/05/07 due to CCVs not meeting method acceptance criteria for PFDA, PFUnA and PFDoA. In addition to these CCVs, one CCV for PFUnA, which bracketed reported sample results LCS-070821 and Trip Blank-1, had a recovery of 74.5%.

• 9/08/07 analysis - Twelve CCV were analyzed during the course of the mn. One CCV for PFHxA, which bracketed reported sample results WBMN GWB-4 MS and HS, LCS-070827 and diluted Trip Blank -1 and -2 HS samples, had a recovery of 70.8%. One CCV for PFHpA, which bracketed reported sample results LCS-070822, method blanks prepared on 08/22/07 and WBMN GW S06PC HS, and sample set WBMN GW S06JS, had a recvoery of 126%. One CCV for PFDoA which bracketed reported sample results LCS-070822, method blanks prepared on 08/22/07 and WBMN GWS06PC HS, and sample set WBMN GWS06JS had a recovery of 130%.

• 10/08/07 analysis - Two CCV were analyzed during the course of the mn. One CCV for PFHpA, which bracketed reported sample set WBMN GW MW2, had a recovery of 65.5%.

Samples bracketed by CCVs not meeting method acceptance criteria have been flagged.

8.4 Blanks

Two types of blanks were prepared and analyzed with the samples: method blanks and field/trip blanks. Each blank result is reviewed and used to evaluate method perfonnance to detemiine the LOQ for each analyte

Page 15 of 207



8.5 Lab Contro l Spikes (LCSs)

Low and mid-level lab control spikes were prepared and analyzed in triplicate with each preparation set. LCSs were prepared by spiking known amounts of the analytes into laboratory water to produce the desired concentration. The spiked water samples were then prepared and analyzed in the same manner as the samples. Analysis of triplicate LCSs at the two specified levels aoss-validates the analytical method as used here for any modifications/deviations fi-om method and ETS-8-154.3. In those instances where LOS did not meet method acceptance criteria, data have been flagged as such. All LCS were used in the detemiination of analytical uncertainty.

The following calculations were used to generate data in Table 5 for laboratory control spikes.

, .-, Calculated Concentration . , „ - . , LCS Percent Recovery = * 100%

Spike Concentration

LCS%RSD = standard deviation LCS replicates ,^^^,^^ average LCS recovery

Page 16 of 207



Table 5. Laboratory Control Spike Recovery

Analyzed 9/2A)7

Lab ID

LCS-070821-1

LCS-070821-2

LCS-070821-3

LCS-070821-4

LCS-070821-5

LCS-070821-6

Average ±%RSD

PFBA

Spiked Concentration

(ngAnL)

0.189

0.189

0.189

4.73

4.73

4.73

Calculated Concentration

(ngAnQ

0.280

0.275

0.278

4.61

4.71

4.88 ,

VoRecovery

148

145

147

97.5

99.7

103

123% ± 21%<>

PFPeA


(ng/inL)

0.285

0.285

0.285

7.13

7.13

7.13


(ng/mQ

0.287

0.280

0.302

7.23

6.91

7.51

VoRecovery

101

98.3

106

101

97.0

105

101% ± 3.5%

PFHxA


(ng/inL)

0.185

0.185

0.185

4.63

4.63

4.63


0.172

0.165

0.188

4.71

4.78

4.81

%Recovery

92.9

89.1

101

102

103

104

98.7% ± 6.2%

PFHpA

Spiked ConcentraOon

(ngAnL)

0.200

0.200

0.200

5.00

5.00

5.00


(ngAnL)

0.196

0.191

0.207

4.75

4.59

5.05

%Recovefy

97.9

95.6

104

94.9

91.7

101

97.5% ± 4.6%

Analyzed 912107

Lab ID

LCS-070821-1

LCS-070821-2

LCS-070821-3

LCS-070821-4

LCS-070821-5

LCS-070821-6

Average ±%RSD

PFOA

Spa(ed Concentration

(ngAnL)

0.193

0.193

0.193

4.81

4.81

4.81


(ngAnL)

0.212

0.181

0.187

4.66

4.72

4.89

%Recovety

110

93.7

96.9

96.9

98.2

102

99.6% ± 5.8 %

PFNA

Spiked Concentratnn

(ngAnL)

0.199

0.199

0.199

4.97

4.97

4.97


(ngAnL)

0.184

0.178

0.175

4.69

4.39

4.90

%Recoi'ery

92.5

89.5

88.1

94.3

88.4

98.6

91.9% ± 4.4%

PFDA

Spaced Concentration

0.197

0.197

0.197

4.92

4.92

4.92


(ngAnL)

0.222

0.182

0.196

4.53

5.29

5.02

%Recovery

113

92.5

99.7

92.1

108

102

101% ± a.r/o

PFUhA®


0.197

0.197

0.197

4.93

4.93

4.93


(ngAnL)

0.228

0.246

0.246

4.88

5.59

4.76

%Recoi'ery

116

125

125

99.0

113

96.5

112% ±11%

(1) Average recovery did not meet mettiod acceptance criteria of 100% ± 20% and RSD s 20%. (2) Samples were bracketed by a CCV that did not meet mettiod acceptance criteria of 100% ± 25%. Recovery was 74.5%.

Page 17 of 207



Table 5 continued. Laboratory Control Spike Recovery

Analyzed 9/2/07

Lab ID

LCS-070821-1

LCS-070821-2

LCS-070821-3

LCS-070821-4

LCS-070821-5

LCS-070821-6

Average ±%RSD

PFDoA

Spiked Concentratfon

(ngAnL)

0.202

0.202

0.202

5.06

5.06

5.06

C^culated Concentration

(ng/hnL)

0.284

0.291

0.281

4.44

4.98

4.53

%Recovery

141

144

139

87.7

98.5

89.5

117%±24%">

PFBS


(ngAnL) j

0.636

0.636

0.636

15.9

15.9

15.9

C^cuiated Concentration

(ngAnL)

0.645

0.675

0.681

14.6

14.5

14.8

%Recovefy

101

106

107

91.8

91.4

93.4

98.4% ± 7.3%

PFHS


(ngAnL)

0.331

0.331

0.331

8.26

8.26

8.26


(ngAnL)

0.336

0.348

0.344

8.33

8.30

8.53

VoRecovery

101

105

104

101

101

103

102% ± f .7%

PFOS

Spiked Cortcentration

(ngAnL)

0.196

0.196

0.196

4.90

4.90

4.90

Osculated Concentration

(ngAnL)

0.189

0.211

0.201

5.02

5.01

5.13

VoRecovery

96.5

108

102

102

102

105

103% ± 3.7%

Analyzed 9/8/07

Lab ID

LCS-070822-1

LCS-070822-2

LCS-070822-3

LCS-070822-4

LCS-070822-5

LCS-070822-6

Average ±%RSD

PFBA


(ngAnL)

0.189

0.189

0.189

4.73

4.73

4.73


(ngAnL)

0.203

0.208

0.191

4.32

4.56

4.56

VoRecovery

108

110

101

91.3

96.4

96.3

101% ± 7.3%

PFPeA


0.285

0.285

0.285

7.13

7.13

7.13

Calculated Cortcentration

(ngAnL)

0.292

0.292

0.282

7.06

7.43

7.23

VoRecovery

102

102

98.8

99.1

104

101

101% ± 1.9%

PFHxA


(ngAnL)

0.185

0.185

0.185

4.63

4.63

4.63


(ngAnL)

0.211

0.169

0.183

4.32

4.31

4.78

VoRecovery

114

91.4

99.2

93.2

93.0

103

99.0% ± 8.7%

PFHpAf


(ngAnL)

0.200

0.200

0.200

5.00

5.00

5.00


(ngAnL)

0.225

0.224

0.194

4.72

5.33

5.01

%Recovefy

112

112

96.8

94.4

107

100

104% ± 7.4% (1) RSD did not meet mettiod acceptance criteria of ^ 0 % . (2) Samples were bracketed by a CCV ttiat did not meet mettKKl acceptance criteria of 100% ± 25%. Recovery was 126%.

Page 18 of 207




Analyzed 9/8/07

LabfD

LCS-070822-1

LCS-070822-2

LCS-070822-3

LCS-070822-4

LCS-070822-5

LCS-070822-6

Average ±%RSD

PFOA


(ngAnL)

0.193

0.193

0.193

4.81

4.81

4.81

emu la ted Concentration

fngAnU

0.218

0.189

0.179

4.79

5.28

5.53

%Recoveiy

113

97.8

92.6

99.7

110

115

105% ± 8.8 %

PFAM

Sp«<ed Concentration

0.199

0.199

0.199

4.97

4.97

4.97


(ngAnL)

0.239

0.226

0.226

5.19

5.35

5.52

%Recovefy

120

113

114

104

108

111

* f 2 % ± 4 . 9 %

PFDA


0.197

0.197

0.197

4.92

4.92

4.92


0.243

0.221

0.215

5.68

5.90

6.08

%Recoveiy

124

112

109

115

120

124

f f 7% ± 5.4%

PFUnA

SpH<ed Concentration

fngtoL)

0.197

0.197

0.197

4.93

4.93

4.93


(ngAnL)

0.312

0.299

0.288

4.89

5.51

5.62

%Recovery

158

152

146

99.2

112

114

130% ± 19%">

Analyzed 9/8/07

Lab ID

LCS-070822-1

LCS-070822-2

LCS-070822-3

LCS-070822-4

LCS-070822-5

LCS-070822-6

Average ±%RSD

PFDoA»


(ngAnL)

0.202

0.202

0.202

5.06

5.06

5.06


(ngAnL)

0.399

0.401

0.322

5.86

6.21

6.10

%Recoveiy

198

198

159

116

123

121

f 52% ± 25 Vof

PFBS


(ngAnL)

0.636

0.636

0.636

15.9

15.9

15.9


(ngAnL)

0.633

0.639

0.609

14.6

15.2

15.6

VoRecovery

99.5

100

95.8

91.9

95.3

97.9

96.7% ± 3 . * %

PFHS


(ngAnL)

0.331

0.331

0.331

8.26

8.26

8.26


(ngAnL)

0.330

0.317

0.313

8.22

8.75

8.62

%Recovefy

100

95.7

94.5

100

106

104

99.9% ±4.5%

PFOS

Sp9<ed CotKentration

(ngAnL)

0.196

0.196

0.196

4.90

4.90

4.90


(ngAnL)

0.200

0.193

0.183

4.86

5.12

5.06

%Recovery

102

98.5

93.3

99.3

104

103

100% ± 3.9%

(1) Average recovery did not meet method acceptance criteria of 100% + 20%. (2) Samples were bracketed by a CCV that did not meet method acceptance criteria of 100% ± 25%. Recovery was 130%. (3) Average recovery did not meet method acceptance criteria of 100% ± 20% and RSD 2 20%.

Page 19 of 207




Analyzed 9/8/07

L ^ I D

LCS-070827-1

LCS-070827-2

LCS-070827-3

LCS-070827-4

LCS-070827-5

LCS-070827-6

Averaqe±%RSD

PFBA


(ngAnL)

0.189

0.189

0.189

4.73

4.73

4.73


(ngAnL)

0.172

0.171

0.121

4.09

4.56

4.30

VoRecovery

90.9

90.4

64.0

86.6

96.4

90.8

86.5% ± 13%

PFPeA


(ngAnL)

0.285

0.285

0.285

7.13

7.13

7.13


(ngAnL)

0.253

0.265

0.251

6.65

6.42

6.37

VoRecovery

88.8

93.0

88.2

93.3

90.1

89.3

90.5% ± 2.4%

P F H X A " '

Spaced Concentration

(ngAnL)

0.185

0.185

0.185

4.63

4.63

4.63


(ngAnL)

0.139

0.164

0.136

3.73

3.81

3.57

% R e c o m y

74.9

88.9

73.3

80.6

82.2

77.0

79.5% ± 7.2%'"

PFHpA

SpfteoT Concentration

(ngAnL)

0.200

0.200

0.200

5.00

5.00

5.00


(ngAnL)

0.161

0.177

0.165

4.63

4.53

4.24

%Recovefy

80.6

88.4

82.6

92.5

90.5

84.9

86.6% ± 5.4%

Analyzed 9/8«)7

Lab/D

LCS-070827-1

LCS-070827-2

LCS-070827-3

LCS-070827-4

LCS-070827-5

LCS-070827-6

Averaqe±%RSD

PFOA

SpOfed Concentration

(ngAnL)

0.193

0.193

0.193

4.81

4.81

4.81


(ngAnL)

0.135

0.148

0.14

4.15

4.14

4.09

%Recovei^

69.9

76.6

72.5

86.3

86.2

85.1

79.4% ± 9 . 3 % " - ^

PFAM


(ngAnL)

0.199

0.199

0.199

4.97

4.97

4.97


(ngAnL)

0.141

0.150

0.142

4.43

4.74

4.15

%Recoveiy

70.6

75.4

71.4

89.2

95.3

83.4

80.9% ± 12%

PFDA


(ngAnL)

0.197

0.197

0.197

4.92

4.92

4.92


(ngAnL)

0.132

0.115

0.132

4.61

4.57

4.23

VoRecovery

66.9

58.1

67.0

93.7

92.9

86.0

77 .4%±20%" ' ' '

PFtftiA


(ngAnL)

0.197

0.197

0.197

4.93

4.93

4.93


(ngAnL)

0.165

0.167

0.194

4.66

4.78

4.33

%Recoveiy

83.8

84.8

98.4

94.5

96.9

87.8

91.0% ± 7.0%

(1) Samples were bracketed by a CCV that did not meet method acceptance criteria of 100% ± 25%. Recovery was 70.8%. (2) Average recovery did not meet method acceptance criteria of 100% ± 20%

Page 20 of 207




Analyzed 9/8/07

Lab/0

LCS-070827-1

LCS-070827-2

LCS-070827-3

LCS-070827-4

LCS-070827-5

LCS-070827-6

Average ±%RSD

PFDoA


(ngAnL)

0.202

0.202

0.202

5.06

5.06

5.06


(ngAnL)

0.158

0.166

0.167

4.47

5.30

4.63

VoRecovery

78.2

82.3

82.5

88.3

105

91.5

88.0% ± 1 1 %

PFBS


(ngAnL)

0.636

0.636

0.636

15.9

15.9

15.9


(ngAnL)

0.594

0.588

0.574

13.2

13.6

12.7

VoRecovery

93.4

92.5

90.3

83.2

85.6

80.1

87.5% ± 6.1%

PFHS


(ngAnL)

0.331

0.331

0.331

8.26

8.26

8.26


(ngAnL)

0.310

0.319

0.306

7,45

7.84

7.39

VoRecovery

93.6

96.5

92.4

90.3

94.9

89.4

92.9% ± 2.9%

PFOS


(ngAnL)

0.196

0.196

0.196

4.90

4.90

4.90


(ngAnL)

0.160

0.171

0.158

4.40

4.54

4.26

VoRecovery

81.4

87.5

80.5

89.9

92.7

87.0

86.5% ±5.5%

Page 21 of 207



8.6 Analyt ica l Method Uncertainty The analytical uncertainty was determined based on historical QC data that is used to evaluate method accuracy and precision. The method uncertainty is calculated following ETS-12-012.2. The analytical uncertainty was detennined by the statistical evaluation of the recoveries for the individual analyte recovery as determined for laboratory matrix spiked samples. The standard deviation was calculated for the set of recovery results (in %). The expanded uncertainty is calculated by multiplying the standard deviation by a factor of 2, which correspond with a confidence level of 95%. A minimum of twenty data points is needed to determine method uncertainty by this method.

Table 6. Analytical Method Uncertainty

Analyte

PFBA

PFPeA

PFHxA

PFHpA

PFOA

PFNA

PFDA

PFUnA

PFDoA

PFBS

PFHS

PFOS

Number of data points (n) used for determining uncertainty values

50

50

50

36

50

48

48

48

48

50

50

50

Mean Recovery (%)

98.5

97.2

96.6

96.1

97.1

97.2

99.0

104

103

96.7

98.5

100

Standard Deviation (%)

+ 18.9

+ 10.3

+ 11.1

+ 9.70

+ 11.3

+ 12.5

+ 15.0

+ 18.4

+ 28.6

+ 10.6

+ 6.64

+ 7.39

•Method Uncertainty (%)

+ 38

+ 21

+ 22

+ 19

+ 23

+ 25

+ 30

+ 37

+ 57

+ 21

+ 13

+ 15

8.7 Sample Results Table 7 summarizes the sample results using the analytical method identified above. All results for quality control samples prepared and analyzed with the samples are reported in section 9 of the report.

Page 22 of 207



Table 7. Sample Concentrations' (1)

3MUIMSID

E06O549-1406

E06-0549-1407

Sample Description

WBMN GW S01PC 0 070808

WBMN GWS01PC DB 070808

Average

VoRSD Sample/Sample DuplKate

E06-0549-1411

E064)549-1412

WBMN GW SOUS 0 070808

WBMN GW SOUS DB 070808

Average

VoRSD Sample/Sample DuplKate

E06-0549-1415

E06-0549-1416

WBMN GW WR3 0 070808

WBMN GW WR3 DB 070808

Average

VoRSD Simple/Sample DuplKate

E06-0549-1419

E06-0549-1420

WBMN GWS08JS 0 070808

WBMN GW S08JS DB 070808

Average

VoRSD Sample/Sample Duplkate

Sample Concentration (ng/mL)

PFBA

0.635

0.617

0.626

2.9

<0.0946

<0.0946

<0.0946

NA

<0.0946

<0.0946

<0.0946

NA

0.209

0.234

0.222

11

PFPeA

<0.0356

<0.0356

<0.0356

NA

<0.0356

<0.0356

<0.03S6

NA

<0.0356

<0.0356

<0.03S6

NA

<0.0356

<0.0356

<0.0356

NA

PFHxA

0.233

0.252

0.242

7.8

0.106

0.100

0.103

5.8

<0.0371

<0.0371

<0.0371

NA

0.0966

0.0453

0.0710

72'"

PFHpA

<0.0300

<0.0300

<O.D300

NA

<0.0300

<0.0300

<0.0300

NA

<0.0300

<0.0300

<0.0300

NA

<0.0300

<0.0300

<0.0300

NA

PFOA

<0.0963

<0.0963

<0.0963

NA

<0.0963

<0.0963

<0.0963

NA

<0.0963

<:0.0963

<0.0963

NA

<0.0963

<0.0963

<0.0963

NA

PFNA

<0.0397

<0.0397

<0.0397

NA

<0.0397

<0.0397

<0.0397

NA

<0.0397

<0.0397

<0.0397

NA

<0.0397

<0.0397

<0.0397

NA

PFDA

<0.0492

<0.0492

<0.0492

NA

<0.0492

<0.0492

<0.0492

NA

<0.0492

<0.0492

<0.0492

NA

<0.0492

<0.0492

<0.0492

NA

PFUnA

<0.0493

<0.0493

<0.0493

NA

<0.0493

<0.0493

<0.0493

NA

<0.0986

<0.0986

<0.0986

NA

<0.0986

<0.0986

<0.0986

NA

PFDoA

<0.101

<0.101

<0.101

NA

<0.101

<0.101

<0.101

NA

NR

NR

NR'"'

NA

<0.101

<0.101

<0.101

NA

PFBS

<0.0795

<0.0795

<0.0795

NA

<0.0795

<0.0795

<0.0795

NA

<0.G795

<0.0795

<0.079S

NA

<0.0795

<0.0795

<0.0795

NA

PFHS

<0.0413

<0.0413

<0.0413

NA

<0.0413

<0.0413

<0.0413

NA

<0.0413

<0.0413

<0.0413

NA

<0.0413

<0.0413

<0.0413

NA

PFOS

<0.0245

<0.0245

<0.024S

NA

<0.0245

<0.0245

<0.0245

NA

<0.0245

<0.0245

<0.024S

NA

<0.0245

<0.0245

<0.0245

NA

(1) Some sample results may have adjusted analytKal uncertainties due to field matrix spike recoveries. See tables in secSon 9 of the report for additkinal sample comments. (2) Sample results are not reportable since the recovery of most appropriate field matrix spike was <50%. (3) Tiie relative percent difference (RPD) dkl not meet method acceptance criteria of S20%.

Page 23 of 207



Table 7 continued. Sample Results' (1)

3MLIIMSI0

E06-0549-1423

E06-0549-1424

Sample Description

WBMN GWS08PC 0 070808

WBMN GW S08PC DB 070808

Average

%RSD Sample/Sample Duplicate

E06-0549-1431

E06-0549-1432



Average

VoRSD Sample/Sample Duplicate

E06 )549-1435

E06-0549-1436

WBMN GW S04SP 0 070809

WBMN GW S04SP DB 070809

Average

VoRSD Smnple/Sample Dup/icafe

E06-0549-1439

E06-0549-1440

WBMN GW S03JS 0 070809


Average

VoRSD Smiph/Sample Duplicate


PFBA

<0.0946

<0.0946

<0.0946

NA

0.529

0.507

0.518

4.2

0.669

0.693

0.681

3.5

0.181

0.194

0.188

6.9

PFPeA

<0.0356

<0.0356

<0.0356

NA

<0.0356

<0.0356

<0.03S6

NA

<0.0356

<0.0356

<0.0356

NA

<0.0356

<0.0356

<0.03S6

NA

PFHxA

<0.0371

<0.0371

<0.0371

NA

<0.0371

0.0397

0.0397

NC' '

0.135

0.201

0.168

39'*'

<0.0371

<0.0371

<0.0371

NA

PFHpA

<0.0300

<0.0300

<0.0300

NA

<0.0300

<0.0300

<0.0300

NA

<0.0300

<0.0300

<0.0300

NA

<0.0300

<0.0300

<0.0300

NA

PFOA

<0.0963

<0.0963

<0.0963

NA

<0.0963

<0.0963

<0.0963

NA

<0.0963

<0.0963

<0.0963

NA

<0.0963

<0.0963

<0.0963

NA

PFNA

<0.0397

<0.0397

<0.0397

NA

<0.0397

<0.0397

<0.0397

NA

<0.0397

<0.0397

<0.0397

NA

<0.0397

<0.0397

<0.0397

NA

PFDA

<0.0492

<0.0492

<0.0492

NA

<0.0492

<0.0492

<0.0492

NA

<0.0492

<0.0492

<0.0492

NA

<0.0492

<0.0492

<0.0492

NA

PFUnA

<0.0986

<0.0986

<0.0986

NA

<0.0986

<0.0986

<0.0986

NA

<0.0986

<0.0986

<0.0986

NA

<0.0986

<0.0986

<0.0986

NA

PFDoA

<0.101

<0.101

<0.101

NA

NR

NR

NR'"

NA

NR

NR

NR'"

NA

<0.101

<0.101

<0.101

NA

PFBS

<0.0795

<0.0795

<0.0795

NA

<0.0795

<0.0795

<0.0795

NA

<0.0795

<0.0795

<0.0795

NA

<0.0795

<0.0795

<0.0795

NA

PFHS

<0.0413

<0.0413

<0.0413

NA

<0.0413

<0.0413

<0.0413

NA

<0.0413

<0.0413

<0.0413

NA

<0.0413

<0.0413

<0.0413

NA

PFOS

<0.0245

<0.0245

<0.024S

NA

<0.0245

<0.0245

<0.0245

NA

<0.0245

<0.0245

<0.0245

NA

<0.0245

<0.0245

<0.0245

NA

(1) Some sample resuRs may have adjusted analytKal uncertainties due to fieM matrix spike recoveries. See tables in section 9 of ttie report for additnnal sample comments. (2) The sample and sample duplicate produced one result above the LOQ and one result bekiw ttie LOQ. The reported average concentratnn represents only the result above the

LOQ. A taie average was not cakulated (NC). (3) Sample results are not reportable since the recovery of most appropriate fieW matrix spike was <50%. (4) The relative percent difference (RPD) dW not meet mettiod acceptance criteria of S20%.

Page 24 of 207




3MUIMSI0

E06-054&-1443

E06 )549-1444

Sample Description



Average

VoRSD Sample/Sample Duplhate

E06-0549-1448

E06-0549-1449



Average


E06^549-1453

E06-0549-1454



Average

%fiSD Sample/Sample Duplhate

E06 )549-1458

E06-0549-1459



Average



PFBA

0.539

0.511

0.525

S.3

0.742

0.711

0.727

4.3

<0.0946

<0.0946

<0.0946

NA

0.837

0.852

0.845

1.8

PFPeA

<0.0356

<0.0356

<0.03S6

NA

<0.0356

<0.0356

<0.0356

NA

<0.0356

<0.0356

<0.03S6

NA

<0.0356

<0.0356

<0.0356

NA

PFHxA

0.0568

0.158

0.107

94'"

<0.0371

<0.0371

<0.0371

NA

<0.0371

<0.0371

<0.0371

NA

<0.0371

<0.0371

<0.0371

NA

PFHpA

<0.0300

<0.0300

<0.0300

NA

<0.0300

<0.0300

<0.0300

NA

<0.0300

<0.0300

<0.0300

NA

<0.0300

<0.0300

<0.0300

NA

PFOA

<0.0963

<0.0963

<0.0963

NA

<0.0963

<0.0963

<0.0963

NA

<0.0963

<0.0963

<0.0963

NA

<0.0963

<0.0963

<0.0963

NA

PFNA

<0.0397

<0.0397

<0.0397

NA

<0.0397

<0.0397

<0.0397

NA

<0.0397

<0.0397

<0.0397

NA

<0.0397

<0.0397

<0.0397

NA

PFDA

<0.0492

<0.0492

<0.0492

NA

<0.0492

<0.0492

<0.0492

NA

<0.0492

<0.0492

<0.0492

NA

<0.0492

<0.0492

<0.0492

NA

PFUnA

<0.0986

<0.0986

<0.0986

NA

<0.0986

<0.0986

<0.0493

NA

<0.0986

<0.0986

<0.0986

NA

<0.0986

<0.0986

<0.0986

NA

PFDoA

<0.101

<0.101

•SO.IOI

NA

NR

NR

NR'"

NA

NR

NR

NR<"

NA

<0.101

<0.101

<0.101

NA

PFBS

<0.0795

<0.0795

<0.0795

NA

<0.0795

<0.0795

<0.079S

NA

<0.0795

<0.0795

<0.0795

NA

<0.0795

<0.0795

<0.0795

NA

PFHS

<0.0413

<0.0413

<0.0413

NA

<0.0413

<0.0413

<0.0413

NA

<0.0413

<0.0413

<0.0413

NA

<0.0413

<0.0413

<0.0413

NA

PFOS

<0.0245

<0.0245

<0.0245

NA

<0.0245

<0.0245

<0.0245

NA

<0.0245

<0.0245

<0.0245

NA

<0.0245

<0.0245

<0.0245

NA

(1) Some sample results may have adjusted analytical uncertainties due to fieki matrix spike recoveries. See tables in sectran 9 of the report for additfonal sample comments. (2) The relative percent difference (RPD) dW not meet method acceptance criteria of S20%. (3) Sample results are not reportatile since the recovery of most appropriate fiekl matrix spike was <50%

Page 25 of 207




3IM UMS ID

E06-0549-1468

E06-0549-1469

Sample Description



Average

%RSD Sampie/Simph Duplhate

E06-0549-1473

£06^)549-1474



Average


E06-0549-1477

E06-0549-1478



Average

%RS0 Stunple/Sample Di^hate

E06-0549-1488

E06-0549-1489

WBMN GW MWH 0 070810

WBMN GW MWH DB 070810

Average

VoRSD Sample/Smiple Duplhate


PFBA

0.819

0.815

0.817

0.49

<0.0946

<0.0946

<0.0946

NA

<0.0946

<0.0946

<0.946

NA

<0.0946

<0.0946

<0.0946

NA

PFPeA

<0.0356

<0.0356

<0.0356

NA

<0.0356

<0.0356

<0.03S6

NA

<0.0356

<0.0356

<0.03S6

NA

<0.0356

<0.0356

<0.03S6

NA

PFHxA

<0.0371

<0.0371

<0.0371

NA

<0.0232

<0.0232

<0.0232

NA

<0.0232

<0.0232

<0.0232

L NA

<0.0232

<0.0232

<0.0232

NA

PFHpA

<0.0300

<0.0300

<0.0300

NA

<0.0250

<0.0250

<0.0250

NA

<0.0250

<0.0250

<0.02S0

NA

<0.0250

<0.0250

<0.0250

NA

PFOA

<0.0963

<0.0963

<0.0963

NA

<0.0241

<0.0241

<0.0241

NA

<0.0241

<0.0241

<0.0241

NA

<0.0241

<0.0241

<0.0241

NA

PFNA

<0.0397

<0.0397

<0.0397

NA

<0.0298

<0.0298

<0.0298

NA

<0.0298

<0.0298

<0.0298

NA

<0.0298

<0.0298

<0.0298

NA

PFDA

<0.0492

<0.0492

<0.0492

NA

NR

NR

NR'"

NA

NR

NR

NR'"

NA

NR

NR

NR'"

NA

PFUnA

<0.0986

<0.0986

<0.0986

NA

<0.0986

<0.0986

<0.0986

NA

<0.0986

<0.0986

<0.0986

NA

<0.0986

<0.0986

<0.0986

NA

PFDoA

NR

NR

NR'"

NA

NR

NR

NR'"

NA

<0.101

<0.101

<0.101

NA

NR

NR

NR'"

NA

PFBS

<0.0795

<0.0795

<0.0795

NA

<0.0795

<0.0795

<0.0795

NA

<0.0795

<0.0795

<0.0795

NA

<0.0795

<0.0795

<0.0795

NA

PFHS

<0.0413

<0.0413

<0.0413

NA

<0.0413

<0.0413

<0.0413

NA

<0.0413

<0.0413

<0.0413

NA

<0.0413

<0.0413

<0.0413

NA

PFOS

<0.0245

<0.0245

<0.024S

NA

<0.0245

<0.0245

<0.0245

NA

<0.0245

<0.0245

<0.0245

NA

<0.0245

<0.0245

<0.024S

NA

(1) Some sample results may have adjusted analytical uncertainties due to field matrix spike recoveries. See tables in sectkin 9 of ttie report for additional sample comments. (2) Sample results are not reportable since the recovery of most appropriate fieM mataix spike was <50%

Page 26 of 207



Table 7 continued. Sample Results (1)

3IMUIMSID

E06-0549-1490

E06-0549-1491

Sample Description

WBMN GWS05SP 070810


Average

%RSD Sample/Sample Duplicate

E06-0549-1494

E06-0549-1495



Average

%RSD Sampfe/Sampfe Dupfrcatc

E06-O549-1498

E06^549-1499

WBMN GW MWG 0 070810

WBMN GWMWG DB 070810

Averagt

VoRSD Sample/Smnple Duplhate

E06-0549-1506

E06^549-1507


WBMN GWS02JS DB 070810

Average

VoRSD Sample/Sample D^ylhate


PFBA

0.857

0.828

0.843

3.4

0.442

0.423

0.433

4.4

0.150

0.126

0.138

17

<0.0946

<0.0946

<0.0946

NA

PFPeA

<0.0356

<0.0356

<0.0356

NA

<0.0356

<0.0356

<0.0356

NA

<0.0356

<0.0356

<0.0356

NA

<0.0356

<0.0356

<0.0356

NA

PFHxA

<0.0232

<0.0232

<0.0232

NA

<0.0232

<0.0232

<0.0232

NA

<0.0232

<0.0232

<0.0232

NA

0.0295

<0.0232

0.0295

NC'"

PFHpA

<0.0250

<0.0250

<0.0250

NA

<0.0250

<0.0250

<0.0250

NA

<0.0250

<0.0250

<0.0250

NA

<0.0250

<0.0250

<0.0250

NA

PFOA

<0.0241

<0.0241

<0.0241

NA

<0.0241

<0.0241

<0.0241

NA

<0.0241

<0.0241

<0.0241

NA

<0.0241

<0.0241

<0.0241

NA

PFNA

<0.0298

<0.0298

<0.0298

NA

<0.0298

<0.0298

<0.0298

NA

<0.0298

<0.0298

<0.0298

NA

<0.0298

<0.0298

<0.0298

NA

PFDA

NR

NR

NR'"

NA

NR

NR

NR'"

NA

NR

NR

NR'"

NA

<0.0246

<0.0246

<0.0246

NA

PFUnA

<0.0986

<0.0986

<0.0986

NA

<0.0986

<0.0986

<0.0986

NA

<0.0986

<0.0986

<0.0986

NA

<0.0986

<0.0986

<0.0986

NA

PFDoA

<0.101

<0.101

<0.101

NA

<0.101

<0.101

<0.101

NA

NR

NR

NR'"

NA

<0.101

<0.101

<0.101

NA

PFBS

<0.0795

<0.0795

<0.0795

NA

<0.0795

<0.0795

<0.079S

NA

<0.0795

<0.0795

<0.0795

NA

<0.0795

<0.0795

<0.0795

NA

PFHS

<0.0413

<0.0413

<0.0413

NA

<0.0413

<0.0413

<0.0413

NA

<0.0413

<0.0413

<0.0413

NA

<0.0413

<0.0413

<0.0413

NA

PFOS

<0.0245

<0.0245

<0.0245

NA

<0.0245

<0.0245

<0.0245

NA

0.0657

0.0604

0.0631

8.4

<0.0245

<0.Q245

<0.024S

NA

(1) Some sample results may have adjusted analytnal uncertainties due to fieki matrix spike recoveries. See tables in section 9 of ttie report for addittonal sample comments. (2) Sample results are not reportable since the recovery of most appropriate fieM matrix spike was <50% (3) TTie sample and sample duplicate produced one result above the LOQ and one result bekiw the LOQ. Tfie reported average concentration represents only the result above the

LOQ. A tme average was not calculated.

Page 27 of 207



Table 7 continued. Sample Results' .(1)

SIM UMS ID

E06-0549-1510

E06-0549-1511

Sample Descriptton



Average


E06-0549-1515

E06.0549-1516

WBMN GW S02DR 0 070810

WBMN GWS02DR DB 070810

Average


E06-0549-1523

E06-0549-1524



Average

%RSD Sample/Sample Duplhate

E06-0549-1525

E06-0549-1526

WBMN GW MW4L 0 070810

WBMN GW MW4L DB 070810

Avaage

VoRSD Sample/Smnple Duplhate


PFBA

1.21

1.30

1.26

7,2

0.542

0.553

0.548

2.0

<0.0946

<0.0946

<0.0946

NA

0.673

0.613

0.643

9.3

PFPeA

<0.0356

<0.0356

<0.0356

NA

<0.0356

<0.0356

<0.0356

NA

<0.0356

<0.0356

<0.03S6

NA

<0.0356

<0.0356

<0.0356

NA

PFHxA

<0.0232

<0.0232

<0.0232

NA

<0.0232

<0.0232

<0.0232

NA

<0.0232

<0.0232

<0.0232

NA

<0.0232

0.0251

0.0251

NC'"

PFHpA

<0.0250

<0.0250

<0.0250

NA

<0.0250

<0.0250

<0.0250

NA

<0.0250

<0.0250

<:0.0250

NA

<0.0250

<0.0250

<0.0250

NA

PFOA

<0.0241

<0.0241

<0.0241

NA

<0.0241

<0.0241

<0.0241

NA

<0.0241

<0.0241

<0.0241

NA

<0.0241

<0.0241

<0.0241

NA

PFNA

<0.0298

<0.0298

<0.0298

NA

<0.0298

<0.0298

<0.0298

NA

<0.0298

<0.0298

<0.0298

NA

<0.0298

<0.0298

<0.0298

NA

PFDA

NR

NR

NR'"

NA

NR

NR

NR'"

NA

NR

NR

NR'"

NA

NR

NR

NR'"

NA

PFUnA

<0.0986

<0.0986

<0.0986

NA

<0.0986

<0.0986

<0.0986

NA

<0.0986

<0.0986

<0.0986

NA

<0.0986

<0.0986

<0.0986

NA

PFDoA

<0.101

<0.101

<0.101

NA

NR

NR

NR'"

NA

<0.101

<0.101

<0.101

NA

NR

NR

NR'"

NA

PFBS

<0.0795

<0.0795

<0.0795

NA

<0.0795

<0.0795

<0.0795

NA

<0.0795

<0.0795

<0.0795

NA

0.192

0.173

0.183

10

PFHS

0.0458

<0.0413

0.0458

NC'"

0.0479

0.0477

0.0478

0.42

<0.0413

<0.0413

<0.0413

NA

0.368

0.367

0.368

0.27

PFOS

<0.0245

<0.0245

<0.0245

NA

<0.0245

<0.0245

<0.0245

NA

<0.0245

<0.0245

<0.0245

NA

0.119

0.107

0.113

11

(1) Some sample results may have adjusted analytKal uncertainties due to fieki matrix spike recoveries. See tattles in section 9 of ttie report for additional sample comments. (2) Sample resuMs are not reportable since the recovery of most appropriate fieM matiix spike was <50% (3) The sample and sample duplicate produced one result above ttie LOQ and one result bekiw ttie LOQ. The reported average concenb tion represents only ttie result above the

LOQ. A tiue average was not cakxilated.

Page 28 of 207




3M UMIS ID

E06^54&-1534

£06^549-1535

Sample Description

WBMN GW 81 0070813

WBMN GWB1DB 070813

Average


E06-0549-1538

£06-0549-1539

WBMN GWB2 0 070813

WBMN GWB2IDB 070813

Average

VoRSD Swnple/Sample Duplicate

E06-0549-1542

E06-0549-1543

WBMN GWB3 0 070813

WBMN GWB3DB 070813

Average


E06-0549-1547

£06^549-1548

WBMN GWB4 0070813

WBMN GWB4DB 070813

Average

VoRSD Sample/Sample Diîicate


PFBA

1.67

1.65

1.66

1.2

0.412

0.455

0.434

9.9

0.676

0.687

0.682

1.6

1.38

1.39

1.38

0.72

PFPeA

0.494

0.477

0.486

3.5

<0.0356

<0.0356

<0.0356

NA

0.0406

0.0377

0.0392

7.4

0.320

0.345

0.332

7.5

PFHxA

0.824

0.832

0.828

1.0

<0.0232

<0.0232

<0.0232

NA

0.0445

0.0669

0.0557

40'"

0.545

0.547

0.546

0.37

PFHpA

0.106

0.109

0.108

2.8

<0.0250

<0.0250

<0.0250

NA

<0.0250

<0.0250

<0.0250

NA

0.254

0.232

0.243

9.1

PFOA

1.41

1.33

1.37

5.8

<0.0241

<0.0241

<0.0241

NA

0.150

0.149

0.150

0.67

2.07

1.90

1.98

8.6

PFNA

<0.0298

<0.0298

<0.0298

NA

<0.0298

<0.0298

<0.0298

NA

<0.0298

<0.0298

<0.0298

NA

<0.0298

<0.0298

<0.0298

NA

PFDA

NR

NR

NR'"

NA

NR

NR

NR'"

NA

NR

NR

NR'"

NA

NR

NR

NR'"

NA

PFUnA

NR

NR

NR'"

NA

NR

NR

NR'"

NA

<0.0986

<0.0986

<0.0986

NA

NR

NR

NR'"

NA

PFDoA

NR

NR

NR'"

NA

NR

NR

NR'"

NA

NR

NR

NR'"

NA

NR

NR

NR'"

NA

PFBS

1.93

1.94

1.94

0.52

<0.0795

<0.0795

<0.0795

NA

0.407

0.406

0.407

0.25

3.75

3.80

3.78

1.3

PFHS

1.53

1.55

1.54

1.3

<0.0413

<0.0413

<0.0413

NA

1.35

1.37

1.36

1.5

11.7

11.5

11.6

1.7

PFOS

0.0412

0.0362

0.0387

13

<0.0245

<0.0245

<0.0245

NA

0.139

0.136

0.138

2.2

1.73

1.63

1.68

6.0

(1) Some sample results may have adjusted analytical uncertainties due to fieki matrix spike recoveries. See tables in section 9 of ttie report for additi'onal sample comments. (2) Sample results are not reportable shoe the recovery of most appropriate fiekl matrix spike was <50%. (3) The relative percent difierence (RPD) did not meet method acceptance criteria of S20%.

Page 29 of 207




3MUIUiSID

£06-0549-1552

E06-0549-1553

Sample Description

OKMN GWW203 0 070809

OKMN GWW203 DB 070809

Average


£06-0549-1463

£06-0549-1464

WBMN GW MW2 0 070809

WBMN GW MW2 DB 070809

Average



PFBA

0.294

0.326

0.310

10

81.2

75.6

78.4

7.1

PFPeA

<0.0356

<0.0356

<0.03S6

NA

9.82

9.33

9.58

5.1

PFHxA

<0.0232

<0.0232

<0.0232

NA

8.31

8.04

8.18

3.3

PFHpA

<0.0250

<0.0250

<0.0250

NA

3.17

2.62

2.90

19

PFOA

0.186

0.210

0.198

12

4.61

4.50

4.56

2.4

PFNA

<0.0298

<0.0298

<0.0298

NA

<0.0298

<0.0298

<0.0298

NA

PFDA

NR

NR

NR'"

NA

NR

NR

NR'"

NA

PFUnA

NR

NR

NR'"

NA

<0.0986

<0.0986

<0.0986

NA

PFDoA

NR

NR

NR'"

NA

NR

NR

NR'"

NA

PFBS

<0.0795

<0.0795

<0.0795

NA

13.6

12.9

13.3

5.3

PFHS

<0.0413

<0.0413

<0.0413

NA

3.43

3.34

3.39

Z7

PFOS

0.614

0.614

0.614

0.0

0.0371

0.0362

0.0367

2.5

(1) Some sample results may have adjusted analytical uncertainties due to fiekl matrix spike recoveries. See tables in section 9 of the report for additkinal sample comments. (2) Sample resets are not reportable since ttie recovery of most appropriate fieH mablx spike was <50%

Page 30 of 207



8.8 Field Matrix Spikes (FMS) Low and high field matrix spikes were collected at each sampling point to verify that the analytical method is applicable to the collected matrix. Field matrix spikes are generated by adding a measured volume of field sample to a container spiked by the laboratory with the target analytes prior to shipping sample containers for sample collection. Field matrix spike recoveries within method acceptance criteria of 100±30% confimn that "unknown" components in the sample matrix do not significantly interiere with the extraction and analysis of the analytes of interest. Field matrix spikes are presented in the section 4 of this report.

R - (Sample Concentration of FMS - Average Concentration : Field Sample & Field Sample Pup.) ^

Spike Concentraton

Page 31 of 207

Exygen Protocol P0002561; Interim Report #16 3M Project E06-Q549


Table 8. Field Matrix Spike Concentrations

Location

B-1

B-2

B-3

&4

MW-2

MW-4L

Description

Low FieM Mablx Spike

Mkl Field Matiix Spike

High FieW Matiix Spike

Low FieM Matrix Spike

High FieW Matrix Spike


Mki FieM Matiix Spike

High FieW Matiix Spike


MM FieM Matiix Spike

High FieM Matrix Spike



High FieM Matiix Spike




Final Concentration (ng/mL)

PFBA

0.237

0.946

4.73

0.237

4.73

0.237

0.946

4.73

0.237

2.37

9.46

0.237

9.46

94.6

0.237

0.946

4.73

PFPeA

0.242

0.970

4.85

0.242

4.85

0.242

0.970

4.85

0.242

2.42

9.70

0.242

9.70

97.0

0.242

0.970

4.85

PFHxA

0.232

0.927

4.63

0.232

4.63

0.232

0.927

4.63

0.232

2.32

9.27

0.232

9.27

92.7

0.232

0.927

4.63

PFHpA

0.250

1.00

5.00

0.250

5.00

0.250

1.00

5.00

0.250

2.50

10.0

0.250

10.0

100

0.250

1.00

5.00

PFOA

0.241

0.963

4.81

0.241

4.81

0.241

0.963

4.81

0.241

2.41

9.63

0.241

9.63

96.3

0.241

0.963

4.81

PFNA PFDA PFUnA PFDoA PFBS

0.248

0.994

4.97

0.248

4.97

0.248

0.994

4.97

0.248

2.48

9.94

0.248

9.94

99.4

0.248

0.994

4.97

0.246

0.984

4.92

0.246

4.92

0.246

0.984

4.92

0.246

2.46

9.84

0.246

9.84

98.4

0.246

0.984

4.92

0.247

0.986

4.93

0.247

4.93

0.247

0.986

4.93

0.247

2.47

9.86

0.247

9.86

98.6

0.247

0.986

4.93

0.253

1.01

5.06

0.253

5.06

0.253

1.01

5.06

0.253

2.53

10.1

0.253

10.1

101

0.253

1.01

5.06

0.254

1.02

5.08

0.254

5.08

0.254

1.02

5.08

0.254

2.54

10.2

0.254

10.2

102

0.254

1.02

5.08

PFHS

0.244

0.978

4.89

0.244

4.89

0.244

0.978

4.89

0.244

2.44

9.78

0.244

9.78

97.8

0.244

0.978

4.89

PFOS

0.256

1.02

5.12

0.256

5.12

0.256

1.02

5.12

0.256

2.56

10.2

0.256

10.2

102

0.256

1.02

5.12

Page 32 of 207

Exygen Protocol P0002561; Interim Report #16 3M Project EQ6-0549


Table 8 continued. Field Matrix Spike Concentrations

Location

MW-B

WR3

MWG

MW-H

SOI PC

SOUS

S02DR

Description






Low FieM Matiix Spike













PFBA

0.237

4.73

94.6

0.237

4.73

0.237

4.73

0.237

4.73

0.237

0.946

4.73

0.237

4.73

0.237

0.946

4.73

PFPeA

0.242

4.85

97.0

0.242

4.85

0.242

4.85

0.242

4.85

0.242

0.970

4.85

0.242

4.85

0.242

0.970

4.85

PFHxA

0.232

4.63

92.7

0.232

4.63

0.232

4.63

0.232

4.63

0.232

0.927

4.63

0.232

4.63

0.232

0.927

4.63

PFHpA

0.250

5.00

100

0.250

5.00

0.250

5.00

0.250

5.00

0.250

1.00

5.00

0.250

5.00

0.250

1.00

5.00

PFOA

0.241

4.81

96.3

0.241

4.81

0.241

4.81

0.241

4.81

0.241

0.963

4.81

0.241

4,81

0.241

0.963

4.81

PFNA

0.248

4.97

99.4

0.248

4.97

0.248

4.97

0.248

4.97

0.248

0.994

4.97

0.248

4.97

0.248

0.994

4.97

PFDA

0.246

4.92

98.4

0.246

4.92

0.246

4.92

0.246

4.92

0.246

0.984

4.92

0.246

4.92

0.246

0.984

4.92

PFUnA

0.247

4.93

98.6

0.247

4.93

0.247

4.93

0.247

4.93

0.247

0.986

4.93

0.247

4.93

0.247

0.986

4.93

PFDoA

0.253

5.06

101

0.253

5.06

0.253

5.06

0.253

5.06

0.253

1.01

5.06

0.253

5.06

0.253

1.01

5.06

PFBS

0.254

5.08

102

0.254

5.08

0.254

5.08

0.254

5.08

0.254

1.02

5.08

0.254

5.08

0.254

1.02

5.08

PFHS

0.244

4.89

97.8

0.244

4.89

0.244

4.89

0.244

4.89

0.244

0.978

4.89

0.244

4.89

0.244

0.978

4.89

PFOS

0.256

5.12

102

0.256

5.12

0.256

5.12

0.256

5.12

0.256

1.02

5.12

0.256

5.12

0.256

1.02

5.12

Page 33 of 207

Exygen Protocol P0002561; Interim Report #16 3M Project £06-0549


Table 8 continued. Field Matrix Spii<e Concentrations

Location

S02PC

S02JS

S03PC

S03JS

S04SP

S04PC

S05SP

S05PC

Description





















PFBA

0.237

0.946

4.73

0.237

4.73

0.237

0.946

4.73

0.237

4.73

0.237

0.946

4.73

0.237

4.73

0.237

4.73

0.237

4.73

PFPeA

0.242

0.970

4.85

0.242

4.85

0.242

0.970

4.85

0.242

4.85

0.242

0.970

4.85

0.242

4.85

0.242

4.85

0.242

4.85

PFHxA

0.232

0.927

4.63

0.232

4.63

0.232

0.927

4.63

0.232

4.63

0.232

0.927

4.63

0.232

4.63

0.232

4.63

0.232

4.63

PFHpA

0.250

1.00

5.00

0.250

5.00

0.250

1.00

5.00

0.250

5.00

0.250

1.00

5.00

0.250

5.00

0.250

5.00

0.250

5.00

PFOA

0.241

0.963

4.81

0.241

4.81

0.241

0.963

4.81

0.241

4.81

0.241

0.963

4.81

0.241

4.81

0.241

4.81

0.241

4.81

PFNA

0.248

0.994

4.97

0.248

4.97

0.248

0.994

4.97

0.248

4.97

0.248

0.994

4.97

0.248

4.97

0.248

4.97

0.248

4.97

PFDA

0.246

0.984

4.92

0.246

4.92

0.246

0.984

4.92

0.246

4.92

0.246

0.984

4.92

0.246

4.92

0.246

4.92

0.246

4.92

PFUnA

0.247

0.986

4.93

0.247

4.93

0.247

0.986

4.93

0.247

4.93

0.247

0.986

4.93

0.247

4.93

0.247

4.93

0.247

4.93

PFDoA

0.253

1.01

5.06

0.253

5.06

0.253

1.01

5.06

0.253

5.06

0.253

1.01

5.06

0.253

5.06

0.253

5.06

0.253

5.06

PFBS

0.254

1.02

5.08

0.254

5.08

0.254

1.02

5.08

0.254

5.08

0.254

1.02

5.08

0.254

5.08

0.254

5.08

0.254

5.08

PFHS

0.244

0.978

4.89

0.244

4.89

0.244

0.978

4.89

0.244

4.89

0.244

0.978

4.89

0.244

4.89

0.244

4.89

0.244

4.89

PFOS

0.256

1.02

5.12

0.256

5.12

0.256

1.02

5.12

0.256

5.12

0.256

1.02

5.12

0.256

5.12

0.256

5.12

0.256

5.12

Page 34 of 207




Location

S05JS

S06PC

S06JS

S07SP

S07PC

S07JS

S08PC

S08JS

Description















High FieM Mablx Spike






PFBA

0.237

4.73

0.237

0.946

4.73

0.237

4.73

0.237

0.946

4.73

0.237

0.946

4.73

0.237

4.73

0.237

4.73

0.237

4.73

PFPeA

0.242

4.85

0.242

0.970

4.85

0.242

4.85

0.242

0.970

4.85

0.242

0.970

4.85

0.242

4.85

0.242

4.85

0.242

4.85

PFHxA

0.232

4.63

0.232

0.927

4.63

0.232

4.63

0.232

0.927

4.63

0.232

0.927

4.63

0.232

4.63

0.232

4.63

0.232

4.63

PFHpA

0.250

5.00

0.250

1.00

5.00

0.250

5.00

0.250

1.00

5.00

0.250

1.00

5.00

0.250

5.00

0.250

5.00

0.250

5.00

PFOA

0.241

4.81

0.241

0.963

4.81

0.241

4.81

0.241

0.963

4.81

0.241

0.963

4.81

0.241

4.81

0.241

4.81

0.241

4.81

PFNA

0.248

4.97

0.248

0.994

4.97

0.248

4.97

0.248

0.994

4.97

0.248

0.994

4.97

0.248

4.97

0.248

4.97

0.248

4.97

PFDA

0.246

4.92

0.246

0.984

4.92

0.246

4.92

0.246

0.984

4.92

0.246

0.984

4.92

0.246

4.92

0.246

4.92

0.246

4.92

PFUnA

0.247

4.93

0.247

0.986

4.93

0.247

4.93

0.247

0.986

4.93

0.247

0.986

4.93

0.247

4.93

0.247

4.93

0.247

4.93

PFDoA

0.253

5.06

0.253

1.01

5.06

0.253

5.06

0.253

1.01

5.06

0.253

1.01

5.06

0.253

5.06

0.253

5.06

0.253

5.06

PFBS

0.254

5.08

0.254

1.02

5.08

0.254

5.08

0.254

1.02

5.08

0.254

1.02

5.08

0.254

5.08

0.254

5.08

0.254

5.08

PFHS

0.244

4.89

0.244

0.978

4.89

0.244

4.89

0.244

0.978

4.89

0.244

0.978

4.89

0.244

4.89

0.244

4.89

0.244

4.89

PFOS

0.256

5.12

0.256

1.02

5.12

0.256

5.12

0.256

1.02

5.12

0.256

1.02

5.12

0.256

5.12

0.256

5.12

0.256

5.12

Page 35 of 207




Location

S09JS

IW203

Frip Blank

Description









PFBA

0.237

4.73

0.237

4.73

0.237

4.73

94.6

PFPeA

0.242

4.85

0.242

4.85

0.242

4.85

97.0

PFHxA

0.232

4.63

0.232

4.63

0.232

4.63

92.7

PFHpA

0.250

5.00

0.250

5.00

0.250

5.00

100

PFOA

0.241

4.81

0.241

4.81

0.241

4.81

96.3

PFNA

0.248

4.97

0.248

4.97

0.248

4.97

99.4

PFDA

0.246

4.92

0.246

4.92

0.246

4.92

98.4

PFUnA

0.247

4.93

0.247

4.93

0.247

4.93

98.6

PFDoA

0.253

5.06

0.253

5.06

0.253

5.06

101

PFBS

0.254

5.08

0.254

5.08

0.254

5.08

102

PFHS

0.244

4.89

0.244

4.89

0.244

4.89

97.8

PFOS

0.256

5.12

0.256

5.12

0.256

5.12

102

Page 36 of 207



9 Data Summary a n d D iscuss ion

The tables below summarize the sample results and field matrix spike recoveries for the sampling locations as well as the Trip Blanks. Results and average values are rounded to three significant figures according to EPA rounding rules. Because of rounding, values may vary slightly from those listed in the raw data. Field matrix spikes recoveries meeting the method acceptance criteria of ± 30%, demonstrate that the method(s) were appropriate for the given matrix and their respective quantitative ranges. In those instances where the most appropriate field matrix spike recoveries did not meet method acceptance aiteria, and where recoveries are outside of the analytical method uncertainty listed in Table 6, analytical uncertainty has been adjusted accordingly and the data footnoted.

Trip Blanks- In general, the Trip Blank FIVIS low samples were recovering at <70% for PFBA, PFOA, PFDA, and PFDoA, while PFBS was recovering close to 130%. This was also observed for many of the low FMS samples for the well locations.

Page 37 of 207



Table 9. WBMN GW Tripl 070808' (1)

3MUMSID

E06-0549-1402

£06-0549-1403

£06-0549-1404

£06-0549-1405

Desavition

WBMN GWTRIP1 0 070808

WBMN GWTRIP1 LS 070808

WBMNGWTRIP1 MS 070808

WBMNGWTR1P1 HS 070808 dill :20

PFBA

Concentration (ngAnL)

<0.0946

0.161

4.66

78.0

VoRecovery

NA

68.0'^'

98.5

82.4

PFPeA


<0.0356

0.237

5.02

91.7

VoRecovery

NA

97.8

104

94.5

PFHxA

Concentrafian (ngAnL)

<0.0371

0.169

4.60

71.1'"

VoRecovery

NA

72.9

99.3

76.7

PFHpA


<0.0300

0.261

4.84

96.5

VoRecovery

NA

104

96.8

96.5

3MUMSID

£06-0549-1402

E06-0549-1403

E06-0549-1404

£06-0549-1405

Descrqotibn


WBMN GWTR1P1 LS 070808

WBMNGWTRIP1 MS 070808

WBMN GWTRIP1 HS 070808 dil1:20

PFOA


<0.0963

0.164

4.09

72.5

VoRecovery

NA

68.1'^'

85.0

75.3

PFNA


<0.0397

0.187

3.98

71.9

VoRecovery

NA

75.3

80.1

72.4

PFDA


<0.0492

0.172

3.52

60.3

^Recovery

NA

69.9

71.5

61.2'^'

PFUnA


<0.0493''"

0.223'"'

5.87'"'

87.1

VoRecovery

NA

90.4

119

88.3

3IMLJMS/D

£06-0549-1402

£06-0549-1403

£06-0549-1404

£06-0549-1405

Descrpthn



WBMN GWTRIP1 MS 070808


PFDoA


<0.101

0.151

5.38

84.2

^Recovery

NA

59.7"'

106

85.4

PFBS


<0.0795

0.356

6.87

119

VoRecovery

NA

140'"

135'»

117

PFHS

Concentiration (ngAnL)

<0.0413

0.303

5.67

101

%Recovefy

NA

124

116

103

PFOS


<0.0245

0.296

5.99

104

VoRecovery

NA

116

117

101 NA = Not Applicable (1) Samples were prepared August 21,2007 and analyzed September 2,2007. (2) FieM matiix spike recovery dM not meet metiiod acceptance criteria of 100% ± 30%. (3) Samples were bracketed by a GOV for PFHxA ttiat dM not meet method acceptance criteria of 100% + 25%. Recovery was 70.8%. (4) Samples were bracketed by a CCV for PFUnA ttiat dM not meet method acceptance criteria of 100% ± 25%. Recovery was 74.5%.

Page 38 of 207



Table 10. WBMN GW S01PC (1)

3iyiUMSID

£06-0549-1406

£06-0549-1407

£06-0549-1408

£06-0549-1409

£06-0549-1410

Desavtion

WBMN GW SOI PC 0 070808

WBMN GW SOI PC DB 070808

WBMN GW SOI PC LS 070808

WBMN GW SOI PC MS 070808

WBMN GW S01 PC HS 070808

Average Concentration (ngAnL) ± %RPD

PFBA


0.635

0.617

0.861

1.46

5.01

VoRecovery

NA

NA

99.3

88.1

92.6

0.626 ng/mL± 2.9%

PFPeA


<0.0356

<0.0356

0.272

1.12

5.50

VoRecovery

NA

NA

112

115

113

<0.0356 ngAnL

PFHxA


0.233

0.252

0.421

1.15

4.23

NA

NA

77.0

97.9

86.0

0.242 n g ^ L t 7.8^

PFHpA


<0.0300

<0.0300

0.247

1.09

4.79

VoRecovery

NA

NA

98.8

109

95.8

<0.0300 ngAnL

3MLIMSID

£06-0549-1406

£06-0549-1407

£06-0549-1408

£06-0549-1409

£06-0549-1410

Descrvtion

WBMN GW SOI PC 0 070808

WBMN GW SOI PC DB 070808


WBMN GW SOI PC MS 070808

WBMN GW SOI PC HS 070808


PFOA


<0.0963

<0.0963

0.154

0.850

4.12

VoRecovery^

NA

NA

64.0'^'

88.3

85.6

<0.0963 ngAnL'

PFNA


<0.0397

<0.0397

0.171

0.856

4.54

VoRecovery

NA

NA

68.8'^'

86.2

91.4

<0.0397ngAnL<^

PFDA


<0.0492

<0.0492

0.153

0.786

3.53

^Recovery

NA

NA

62.2'^'

79.9

71.7

<0.0492ng^L''

PFIMA

Concentration

<0.0493

<0.0493

0.255

1.31

6.03

VoRecovery

NA

NA

103

133' '

122

<0.0493 ngAnL

Page 39 of 207



Table 10 continued. WBMN GW SOIPC' (1)

3MLmiSID

£06-0549-1406

£06-0549-1407

£06-0549-1408

E06-0549-1409

E06-0549-1410

Desa^tion




WBMN GW SOIPC MS 070808

WBMN GW SOI PC HS 070808

Average Concentrathn (ng/mL) ± %RPD

PFDoA


<0.101

<0.101

0.194

1.02

5.44

VoRecovery

NA

NA

76.7

101

108

<0.101 ng/mL

PFBS


<0.0795

<0.0795

0.363

1.43

6.56

VoRecovery

NA

NA

143"'

141'^'

129

<0.079SngAnL'

PFHS


<0.0413

<0.0413

0.292

1.13

5.39

VoRecovery

NA

NA

119

116

110

<0.0413 ngAnL

PFOS


<0.0245

<0.0245

0.311

1.25

5.84

VoRecovery

NA

NA

121

122

114

<0.0245 ngAnL

NA = Not Applicable (1) Samples were prepared August 21,2007 and analyzed September 2,2007. (2) FieM matiix spike recovery dM not meet method acceptance criteria of 100% + 30%. (3) The analytical uncertainty has been adjusted for PFOA to 100% ± 36%, PFNA 100% ±31%, PFDA 100% ± 38%, and PFBS 100% + 43%.

Page 40 of 207



Table 11. WBMN GW SOUS ;(1)

3UUMSID

£06-0549-1411

£06-0549-1412

£06-0549-1413

£06-0549-1414

Description


WBMN GW SOI JS DB 070808

WBMN GWS01JS LS 070808

WBMN GW SOUS HS 070808

Average Concentration (ngAnL) ± VoRPD

PFSA


<0.0946

<0.0946

0.190

4.21

<0.0946

VoRecovery

NA

NA

80.3

89.0

ngAnL

PFPeA

Concentrati'on (ngAnL)

<0.0356

<0.0356

0.243

4.74

<0.0356

VoRecovery

NA

NA

100

97.8

ng/inL

PFHxA


0.106

0.100

0.296

4.15

VoRecovery

NA

NA

83.3

87.3

0.103 ngAnLt 5.8%

PFHpA


<0.0300

<0.0300

0.235

4.86

NA

NA

94.0

97.2

<0.0300 ngAnL

3MUMSID

£06-0549-1411

£06-0549-1412

£06-0549-1413

£06-0549-1414

Descrption


WBMN GW SOUS DB 070808

WBMN GW SOUS LS 070808



PFOA


<0.0963

<0.0963

0.164

4.18

VoRecovery

NA

NA

68.1'''

86.8

<0.0963ngAnL<^

PFAM


<0.0397

<0.0397

0.197

3.91

VoRecovety

NA

NA

79.3

78.7

<0.0397 ngAnL

PFDA


<0.0492

<0.0492

0.191

3.73

VoRecovery

NA

NA

77.6

75.8

<0.0492 ngAnL

PFUnA


<0.0493

<0.0493

0.300

7.22

VoRecovery

NA

NA

122

146' '

<0.0493 ngAnL

Page 41 of 207



Table 11 continued. WBMN GW SOUS' (1)

3MLIM$ID

£06-0549-1411

£06-0549-1412

£06-0549-1413

£06-0549-1414

Description

WBMN GWSOUS 0 070808

WBMN GWSOUS DB 070808

WBMN GW SOUS LS 070808



PFDoA


<0.101

<0.101

0.218

6.27

VoRecovery

NA

NA

86.2

124

<0.101 ngAnL

PFBS


<0.0795

<0.0795

0.342

6.49

VoRecovery

NA

NA

135'='

128

<0.0795ngAnL<^

PFHS


<0.0413

<0.0413

0.274

5.32

VoRecovery

NA

NA

112

109

<0.0413 ngAnL

PFOS


<0.0245

<0.0245

0.312

5.69

VoRecovery

NA

NA

122

111

<0.0245 ngAnL

NA = Not Applicable (1) Samples were prepared August 21,2007 and analyzed September 2,2007. (2) FieM matiix spike recovery dM not meet mettiod acceptance criteria of 100% ± 30%. (3) Ttie analytical uncertainty has been adjusted for PFOA to 100% ± 32% and PFBS 100% ± 35%.

Page 42 of 207



Table 12. WBMNGWWR3 (1)

SMLIMSID

£06-0549-1415

£06-0549-1416

£06-0549-1417

£06-0549-1418

Desaption


WBMN GWWR3 DB 070808

WBMN GWWR3 LS 070808

WBMN GWWR3 HS 070808

Average Concenfration (ngAnL) ± VoRPD

PFBA

Concentration

<0.0946

<0.0946

0.171

4.36

VoRecovery

NA

NA

72.3

92.1

<0.0946ng*ni.

PFPeA

CorKentration (ngAnL)

<0.0356

<0.0356

0.235

4.87

VoRecovery

NA

NA

96.9

100

<0J)356 ngAnL

PFHxA


<0.0371

<0.0371

0.182

3.85

VoRecovery

NA

NA

78.5

83.1

<0.0371 ngAnL

PFHpA


<0.0300

<0.0300

0.229

4.78

VoRecovery

NA

NA

91.6

95.6

<a.0300 ng/mL

3NIUMSID

£06-0549-1415

£06-0549-1416

£06-0549-1417

£06-0549-1418

Description



WBMN GW WR3 LS 070808

WBMN GWWR3 HS 070808


PFOA

(ngAnL)

<0.0963

<0.0963

0.126

3.91

VoRecovery

NA

NA

52.3'='

81.2

<0.0963ngAnL^

PFNA


<0.0397

<0.0397

0.157

3.73

VoRecovery

NA

NA

63.2'='

75.1

<0.0397ngAnL'

PFDA

Concentrathn (ngAnL)

<0.0492

<0.0492

0.116

2.98

VoRecovery

NA

NA

47.2'='

60.6

<0.0492ngAnL<^

PFUnA


<0.0986

<0.0986

0.165

3.81

VoRecovery

NA

NA

66.9'='

77.3

<0.0986 ngAnL

Page 43 of 207



Table 12 continued. WBMNGWWR3' (1)

3MLmiSID

£06-0549-1415

£06-0549-1416

£06-0549-1417

E06-0549-1418

Description



WBMN GW WR3 LS 070808

WBMN GW WR3 HS 070808


PFDoA


<0.101

<0.101

<0.101

3.50

VoRecovery

NA

NA

* 69.2'='

Not Reported <

PFBS


<0.0795

<0.0795

0.329

6.43

VoRecovery

NA

NA

130

127

<0.0795 ngAnL

PFHS


<0.0413

<0.0413

0.261

5.21

VoRecovery

NA

NA

107

107

<0.0413 ngAnL

PFOS


<0.0245

<0.0245

0.264

5.12

^Recovery

NA

NA

103

99.9

<0.0245ng^L

NA = Not Applicable * = FieM matrix spike recovery couM not be calculated as ttie sample result was not detected above tiie analytical LOQ. (1) Samples were prepared August 21,2007 and analyzed September 2,2007. PFUnA was re-analyzed on October 5,2007. (2) FieM matiix spike recovery did not meet mettiod acceptance criteria of 100% ± 30%. (3) TTie analytical uncertainty has been adjusted for PFOA to 100% ± 48%, PFNA 100% + 37%, and PFDA 100% ± 53%. (4) Sample results are not reportable since ttie recovery of most appropriate fieM mataix spike was <50%.

Page 44 of 207



Table 13. WBMN GW S08JS (1)

PFBA PFPeA PFHxA PFHpA

3MLIMSID Desciption Concentration

("9AnL) VoRecovery Concentration

("9AnL) VoRecovery Concentration

("SAnL) VoRecovery Concentrathn

(ngAnL) VoRecovery

£06-0549-1419

£06-0549-1420

E06-0549-1421

£06-0549-1422



WBMN GW S08JS LS 070808

WBMN GW S08JS HS 070808

0.209

0.234

0.455

4.59

NA

NA

98.7

92.3

<0.0356

<0.0356

0.230

5.33

NA

NA

94.9

110

0.0966

0.0453

0.285

4.19

NA

NA

92.4

88.9

<0.0300

<0.0300

0.229

4.88

NA

NA

91.6

97.6

Average Concentrathn (ngAnL) ± VoRPD 0.222 ngAnLtHVo <0.0356 ngAnL 0.0710 ngAnL±72%'^ <0.0300 ngAnL

3MUMSID

£06-0549-1419

£06-0549-1420

£06-0549-1421

£06-0549-1422

Description






PFOA


<0.0963

<0.0963

0.129

4.18

VoRecovery

NA

NA

53.6'^'

86.8

<0.0963 ngAnU^

PFNA

CorKentration

<0.0397

<0.0397

0.169

4.10

%Recovery

NA

NA

68.0'^'

82.5

<0.0397n9*nL''*'

PhDA


<0.0492

<0.0492

0.155

3.71

VoRecovery

NA

NA

63.0'^'

75.4

<0.0492ngAnL'^

PFUnA


<0.0986

<0.0986

0.233

4.99

VoRecovery

NA

NA

94.5

101

<0.0986ngAnL

Page 45 of 207



Table 13 continued. WBMNGWS08JS' (1)

3MLIMSID

£06-0549-1419

£06-0549-1420

£06-0549-1421

£06-0549-1422

Description




WBMN GWS08JS HS 070808

Average Concentration (ng/mL) ± VoRPD

PFDoA

Concenfration (ngAnL)

<0.101

<0.101

0.190

4.29

VoRecovery

NA

NA

75.1

84.8

<0.101 ngAnL

PFBS


<0.0795

<0.0795

0.320

6.55

VoRecovery

NA

NA

126

129

<0.0795ng4nL

PFHS

Concentrîon (ngAnL)

<0.0413

<0.0413

0.262

5.54

VoRecovery

NA

NA

107

113

<0.0413 ngAnL

PFOS


<0.0245

<0.0245

0.285

5.81

VoRecovery

NA

NA

111

113

<0.024S ngAnL

NA = Not Applicable (1) Samples were prepared August 21,2007 and analyzed September 2,2007. PFUnA was-re-analyzed on October 5,2007. (2) The relative percent diflierence (RPD) dM not meet method acceptance criteria of S20%. (3) FieM matiix spike recovery dM not meet method acceptance criteria of 100% ± 30%. (4) The analytical uncertainty has been adjusted for PFOA to 100% ± 46%, PFNA 100% + 32%, and PFDA 100% + 37%.

Page 46 of 207




3MUMSID

£06-0549-1423

£06-0549-1424

£06-0549-1425

£06-0549-1426

Descrption



WBMN GW S08PC LS 070808

WBMN GW S08PC HS 070808


PFBA


<0.0946

<0.0946

0.257

4.35

NA

NA

109

91.9

<0.0946 ngAnL

PFPeA


<0.0356

<0.0356

0.249

5.07

VoRecovery

NA

hIA

103

105

<0.0356 ngAnL

PFHxA


<0.0371

<0.0371

0.239

4.21

VoRecovery

NA

NA

103

90.9

<0.0371 ngAnL

PFHpA


<0.0300

<0.0300

0.246

4.58

VoRecovery

NA

NA

98.4

91.6

<0.0300 ngAnL

3MUMSID

£06-0549-1423

£06-0549-1424

E06-0549-1425

£06-0549-1426

Descrption






PFOA


<0.0963

<0.0963

0.178

4.04

VoRecovery

NA

NA

74.0

83.9

<0.0963 ngAnL

PFNA


<0.0397

<0.0397

0.177

4.21

VoRecovery

NA

NA

71.3

84.7

<0.0397 ngAnL

PFDA


<0.0492

<0.0492

0.179

3.96

%Recovefy

NA

NA

72.8

80.5

<0.0492 ngAnL

PFlMiA


<0.0986

<0.0986

0.270

6.37

VoRecov&y

NA

NA

110

129

<0.0986 ngAnL

Page 47 of 207



Table 14 continued. WBMN GW S08PC (1)

3MLIMSID

£06-0549-1423

£06-0549-1424

£06-0549-1425

E06-0549-1426

Descrption






PFDoA


<0.101

<0.101

0.237

6.85

VoRecovery

NA

NA

93.7

135'='

<0.101 ngAnL

PFBS


<0.0795

<0.0795

0.323

6.71

VoRecovery

NA

NA

127

132'='

<0.0795 ngAnL

PFHS


<0.0413

<0.0413

0.275

5.55

VoRecovery

NA

NA

112

113

<0.0413 ngAnL

PFOS


<0.0245

<0.0245

0.314

6.37

VoRecovery

NA

NA

123

124

<0.0245 ngAnL

NA= Not Applicable (1) Samples were prepared August 21,2007 and analyzed September 2,2007. PFUnA was re-analyzed on October 5,2007. (2) Field matiix spike recovery dM not meet mettiod acceptance criteria of 100% ± 30%.

Page 48 of 207



Table 15. WBMN GW TRIP2 070809 (1)

3MUMSID

£06-0549-1427

E06-0549-1428

£06-0549-1429

£06-0549-1430

Desayytion

WBMN GWTR1P2 0 070809

WBMN GW TRIP2 LS 070809

WBMN GW TRIP2 MS 070809

WBMN GW TRIP2 HS 070809 dil 1:20

PFBA


<0.0946

0.140

4.58

82.3

VoRecovery

NA

59.2'='

96.8

87.0

PFPeA

Concentrathn

<0.0356

0.247

4.96

87.4

%Recovery

NA

102

102

90.1

PFHxA


<0.0371

0.175

3.96

76.3'^'

^Recovery

NA

75.5

85.5

82.3

PFHpA


<0.0300

0.233

4.82

93.6

%Recovery

NA

93.2

96.4

93.6

3liSUMSID

£06-0549-1427

E06-0549-1428

£06-0549-1429

£06-0549-1430

Descrption



WBMN GWTR1P2 MS 070809

WBMN GWTR1P2 HS 070809 dil 1:20

PFOA


<0.0963

0.135

4.12

79.0

^Recovery

NA

56.1'='

85.6

82.0

PFNA


<0.0397

0.170

3.57

77.3

%Recoveiy

NA

68.4'='

71.9

77.8

PFDA

Conc&itration (ngAnL)

<0.0492

0.160

3.56

64.0

%Recoveiy

NA

65.0'='

72.4

65.0'='

PFUnA


<0.0986

0.249

5.69

93.7

^Recovery

NA

101

115

95.0

3MUMSID

£06-0549-1427

£06-0549-1428

£06-0549-1429

£06-0549-1430

Descrption





PFDoA


<0.101

0.187

5.28

79.9

VoRecovery

NA

73.9

104

81.0

PFBS


<0.0795

0.333

6.71

123

%Recovery

NA

131'='

132'='

121

PFHS


<0.0413

0.273

5.65

96.1

^Recovery

NA

112

116

98.3

PFOS


<0.0245

0.290

5.98

102

VoRecovery

NA

113

117

99.5

NA = Not Applk:able (1) Samples were prepared August 21,2007 and analyzed September 2,2007. PFDA and PFUnA were re-analyzed on October 5,2007. (2) Field matiix spike recovery did not meet method acceptance criteria of 100% ±30%. (3) Samples were bracketed by a CCV for PFHxA ttiat dM not meet method acceptance criteria of 100% + 25%. Recovery was 70.8%.

Page 49 of 207



Table 16. WBMN GW S04PC' (1)

3IVILIMSID

£06-0549-1431

£06-0549-1432

E06-0549-1433

£06-0549-1434

Description






PFBA


0.529

0.507

0.693

4.98

VoRecovery

NA

NA

74.0

94.3

0.518 ngAnL± 4.2%

PFPeA


<0.0356

<0.0356

0.246

5.43

<0.0356

VoRecovery

NA

NA

101

112

ngAnL

PFHxA


<0.0371

0.0397

0.372

4.41

VoRecovery

NA

NA

143'='

94.3

0.0397 ngAnL'^^

PFHpA


<0.0300

<0.0300

0.270

4.98

VoRecovery

NA

NA

108

100

<0.0300 ngAnL

3MUMSID

£06-0549-1431

E06-0549-1432

£06-0549-1433

£06-0549-1434

Description






PFOA

ConccnOmOon

<0.0963

<0.0963

0.154

4.36

VoRecovery

NA

NA

64.0'='

90.6

<0.0963 ngAnW^

PFWA


<0.0397

<0.0397

0.178

4.64

NA

NA

71.7

93.4

<0.0397 ngAnL

PFDA


<0.0492

<0.0492

0.159

3.42

VoRecovery

NA

NA

64.6'='

69.5'='

<0.0492ngAnL<^

PFUnA

Concentration (ngAnU

<0.0986

<0.0986

0.222

4.89

VoRecovery

NA

NA

90.0

99.2

<0.0986 ngAnL

Page 50 of 207



Table 16 continued. WBMN GW S04PC (1)

3MLIMSID

£06-0549-1431

£06-0549-1432

£06-0549-1433

E06-0549-1434

Descrpthn






PFDoA


<0.101

<0.101

0.109

4.46

VoRecovery

NA

NA

43.1'='

88.1

Not Reported'^

PFBS


<0.0795

<0.0795

0.339

6.77

VoRecovery

NA

NA

133'='

133'='

<0.0795ngAnL''

PFHS


<0.0413

<0.0413

0.280

5.56

VoRecovery

NA

NA

115

114

<0.0413 ngAnL

PFOS


<0.0245

<0.0245

0.299

5.80

VoRecovery

NA

NA

117

113

<0.0245ng*iiL

NA = Not Applicable (1) Samples were prepared August 21,2007 and analyzed September 2,2007. PFDA and PFUnA were re-analyzed on October 5,2007. (2) Field matiix spike recovery dM not meet mettiod acceptance criteria of 100% ± 30%. (3) Ttie sample and sample duplicate produced one result above the LOQ and one result beMw the LOQ. Tiie reported average concentrati'on represents only the result above the LOQ. A

tme average was not calculated. (4) The analytical uncertainty has been adjusted for PFHxA to 100% ± 43%, PFOA 100% ± 36%, PFDA 100% ± 35%, and PFBS 100% ± 33%. (5) Sample results are not reportable since ttie recovery of most appropriate field matiix spike was <50%.

Page 51 of 207



Table 17. WBMN GW S04SP' d)

3MUMSID

£06-0549-1435

£06-0549-1436

£06-0549-1437

£06-0549-1456

£06-0549-1438

Desayithn

WBMN GWS04SP 0 070809


WBMN GW S04SP LS 070809

WBMNGWS04SP MS 070809

WBMN GW S04SP HS 070809

Average Concentrathn (ngAnL) ± VoRPD

PFBA


0.669

0.693

0.888

1.57

5.43

VoRecovery

NA

NA

87.5

93.9

100

0.681 ngAnL± 3.5%

PFPeA


<0.0356

<0.0356

0.264

1.12

5.51

<0.0356

VoRecovery

NA

NA

109

115

114

ng/mL

PFHxA


0.135

0.201

0.306

1.09

4.77

VoRecovery

NA

NA

59.6'='

92.6

99.3

0.168 ngAnLt 39%^ "

PFHpA


<0.0300

<0.0300

0.275

1.19

5.88

VoRecovery

NA

NA

110

119

118

<0.0300 ngAnL

3MUMSID

£06-0549-1435

£06-0549-1436

£06-0549-1437

£06-0549-1456

£06-0549-1438

Description







PFOA


<0.0963

<0.0963

0.184

0.911

4.74

VoRecovery

NA

NA

76.4

94.6

98.5

<0.0963 ngAnL

PFNA

Concentration

<0.0397

<0.0397

0.237

0.975

4.20

VoRecovery

NA

NA

95.4

98.1

84.5

<0.0397 ngAnL

PFDA


<0.0492

<0.0492

0.137

0.658

3.36

VoRecovery

NA

NA

55.7'='

66.9'='

68.3'='

<0.0492ngAnL '

PFUnA


<0.0986

<0.0986

0.173

0.812

4.12

VoRecovery

NA

NA

70.2

82.3

85.4

<0.0986ngAnL

Page 52 of 207


Analysis of Woodbury Waste Site Groundwater Samples; 3fd Quarter 2007

Table 17 continued. WBMN GW S04SP< id)

3MLMSID

£06-0549-1435

£06-0549-1436

£06-0549-1437

£06-0549-1456

£06-0549-1438

Description






Average Concenti-ation (ngAnL) ± VoRPD

PFDoA


<0.101

<0.101

0.116

0.792

4.21

VoRecovery

NA

NA

45.8'='

78.3'='

83.2'='

Not Reported <

PFBS


<0.0795

<0.0795

0.352

1.42

6.91

VoRecovery

NA

NA

139'='

140'='

136'='

<0.O795ngAnL '"

PFHS


<0.0413

<0.0413

0.284

1.16

5.73

VoRecovery

NA

NA

116

119

117

<0.0413 ngAnL

PFOS


<0.0245

<0.0245

0.282

1.11

5.60

VoRecovery

NA

NA

110

108

109

<0.0245 ngAnL

NA = Not Applicable (1) Samples were prepared August 21,2007 and analyzed September 2,2007. PFDA and PFUnA were re-analyzed on October 5,2007. (2) FieM matiix spike recovery dM not meet method acceptance criteria of 100% ± 30%. (3) The relative percent difference (RPD) dM not meet mettiod acceptance criteria of S20%. (4) The analytical uncertainty has been adjusted for PFHxA to 100% ± 40%, PFDA 100% + 44% and PFBS 100% ± 39%. (5) Sample results are not reportable since the recovery of most appropriate fieM matiix spike was <50%.

Page 53 of 207



Table 18. WBMN GW SOS JS' (1)

3MLIMSID

£06-0549-1439

£06-0549-1440

£06-0549-1441

E06-0549-1442

Descrmtion






PFBA

CorKentrathn (ngAnL)

0.181

0.194

0.436

5.05

VoRecovery

NA

NA

105

103

0.188 ngAnL± 6.9%

PFPeA


<0.0356

<0.0356

0.283

5.60

VoRecovery

NA

NA

117

115

<0.0356 ngAnL

PFHxA


<0.0371

<0.0371

0.239

5.28

VoRecovery

NA

NA

103

114

<0.0371 ngAnL

PFHpA


<0.0300

<0.0300

0.276

5.98

VoRecovery

NA

NA

110

120

<0.0300 ngAnL

3MLIMSID

£06-0549-1439

£06-0549-1440

£06-0549-1441

£06-0549-1442

Description






PFOA


<0.0963

<0.0963

0.196

4.81

VoRecovery

NA

NA

81.4

100

<0.0963 ngAnL

PFNA

Concentiation (ngAnL)

<0.0397

<0.0397

0.206

4.86

VoRecovery

NA

NA

82.9

97.8

<0.0397 ngAnL

PFDA


<0.0492

<0.0492

0.166

3.88

VoRecovery

NA

NA

67.5'='

78.9

<0.0492ngAnL'

PFUnA


<0.0986

<0.0986

0.233

5.25

VoRecovery

NA

NA

94.5

106

<0.0986 ngAnL

Page 54 of 207



Table 18 continued. WBMN GW S03JS* ;(1)

3MLIUSID

£06-0549-1439

£06-0549-1440

£06-0549-1441

E06-0549-1442

Descrption






PFDoA


<0.101

<0.101

0.178

5.48

VoRecovery

NA

NA

70.4

108

<0.101 ngAnL

PFBS


<0.0795

<0.0795

0.348

7.07

VoRecovery

NA

NA

137'='

139'='

<0.0795ngAnL'^

PFHS


<0.0413

<0.0413

0.295

5.91

NA

NA

121

121

<0.0413 ngAnL

PFOS


<0.0245

<0.0245

0.300

6.04

VoRecMvery

NA

NA

117

118

<0.0245 ngAnL

NA = Not Applicable (1) Samples were prepared August 21,2007 and analyzed September 2,2007. PFDA and PFUnA were re-analyzed on October 5,2007. (2) Field matiix spike recovery did not meet method acceptance criteria of 100% ± 30%. (3) The analytical uncertainty has tieen adjusted for PFDA to 100% + 32% and PFBS 100% ± 37%.

Page 55 of 207

Exygen Protocol P0002561; Interim Report #16 3IM Pralect E06-0549


Table 19. WBMNGWS03PC (1)

3MLmiSID

£06-0549-1443

£06-0549-1444

£06-0549-1445

£06-0549-1446

£06-0549-1447

Description




WBMN GW S03PC MS 070809

WBMN GWS03PC HS 070809


PFBA


0.539

0.511

0.752

1.48

5.03

VoRecovery

NA

NA

95.9

101

95.2

0.525 ng*nL± 5.3%

PFPeA


<0.0356

<0.0356

0.296

1.11

5.26

VoRecovery

NA

NA

122

114

108

<0.0356 ngAnL

PFHxA


0.0568

0.158

0.256

1.06

4.64

VoRecovery

NA

NA

64.1'='

103

97.8

0.107 ngAnLt 94%^'^

PFHpA


<0.0300

<0.0300

0.284

1.24

5.60

VoRecovery

NA

NA

114

124

112

<0.0300 ngAnL

3MLmiSID

£06-0549-1443

£06-0549-1444

£06-0549-1445

£06-0549-1446

£06-0549-1447

Descrption







PFOA

Concmtrathn (ngAnL)

<0.0963

<0.0963

0.190

0.942

4.84

VoRecovery

NA

NA

78.9

97.8

101

<0.0963 ngAnL

PFNA


<0.0397

<0.0397

0.242

0.855

4.66

VoRecovery

NA

NA

97.4

86.1

93.8

<0.0397 ngAnL

PFDA


<0.0492

<0.0492

0.156

0.625

3.53

VoRecovery

NA

NA

63.4'='

63.5'='

71.7

<0.0492ngAnL ''

PFUnA


<0.0986

<0.0986

0.235

0.878

5.12

VoRecovery

NA

NA

95.3

89.0

104

<0.0986ngAnL

Page 56 of 207


Analysis of IMjodbury Waste Site Groundwater Samples; 3fd Quarter 2007

Table 19 continued. WBMN GW S03PC' (1)

3MLMSID

£06-0549-1443

£06-0549-1444

E06-0549-1445

£06-0549-1446

£06-0549-1447

Desctption



WBMN GWS03PC LS 070809




PFDoA


<0.101

<0.101

0.141

0.754

4.65

VoRecovery

NA

NA

55.7'='

74.5

91.9

<0.101 ng/mL

PFBS


<0.0795

<0.0795

0.362

1.45

6.72

VoRecovery

NA

NA

143'='

143'='

132'='

<0.0795ng^l.

PFHS


<0.0413

<0.0413

0.303

1.15

5.58

VoRecovery

NA

NA

124

118

114

<0.0413 ngAnL

PFOS


<0.0245

<0.0245

0.304

1.06

5.84

VoRecovery

NA

NA

119

103

114

<0.0245 ngAnL

NA = Not Applicable (1) Samples were prepared August 21,2007 and analyzed September 2,2007. PFDA, PFUnA and PFDoA were re-analyzed on October 5,2007. (2) FieM matiix spike recovery did not meet mettiod acceptance criteria of 100% ± 30%. (3) The relative percent difierence (RPD) dM not meet mettiod acceptance criteria of S20%. (4) The analytical uncertainty has been adjusted for PFHxA to 100% ± 36%, PFDA 100% ± 37% and PFBS 100% + 43%.

Page 57 of 207




3MUMSID

£06-0549-1448

E06-0549-1449

£06-0549-1450

£06-0549-1451

£06-0549-1452

Description







PFSA

Concenti-ation (ngAnL)

0.742

0.711

0.991

1.60

5.68

VoRecovery

NA

NA

112

92.3

105

0.727 ngAnLt 4.3%

PFPeA


<0.0356

<0.0356

0.282

1.17

5.42

VoRecovery

NA

NA

116

121

112

<0.0356 ngAnL

PFHxA


<0.0371

<0.0371

0.191

1.02

5.06

VoRecovery

NA

NA

82.4

110

109

<0.0371 ngAnL

fVHpA


<0.0300

<0.0300

0.257

1.32

5.65

VoRecov&y

NA

NA

103

132'='

113

<0.0300 ngAnL

3MLIMSID

E06-0549-1448

£06-0549-1449

£06-0549-1450

£06-0549-1451

E06-0549-1452

Description







PFOA


<0.0963

<0.0963

0.183

1.02

4.91

VoRecovery

NA

NA

76.0

106

102

<0.0963 ngAnL

PFAM


<0.0397

<0.0397

0.208

0.946

4.83

VoRecovery

NA

NA

83.7

95.2

97.2

<0.0397 ngAnL

PFDA

Ccmcentration (ngAnL)

<0.0492

<0.0492

0.127

0.650

2.98

VoRecovery

NA

NA

51.6'='

66.1'='

60.6'='

<0.0492ngAnL'

PFUnA


<0.0986

<0.0986

0.154

0.723

3.81

VoRecovery

NA

NA

62.5'='

73.3

77.3

<0.0986ngAnL'

Page 58 of 207



Table 20 continued. WBMNGWS07PC' (1)

3MUMSID

£06-0549-1448

£06-0549-1449

£06-0549-1450

£06-0549-1451

£06-0549-1452

Description






Average Concentration (ng/rnL) ± VoRPD

PFDoA


<0.101

<0.101

<0.101

0.410

2.55

VoRecovery

NA

NA

* 40.5'='

50.4'='

Not Reported''^

PFBS

Concentrathn rn^hiy

<0.0795

<0.0795

0.331

1.45

7.04

%Recoveo'

NA

NA

130

143'='

139'='

<0.0795ng^L

PFHS


<0.0413

<0.0413

0.278

1.21

5.91

VoRecovery

NA

NA

114

124

121

<0.0413 ngAnL

PFOS


<0.0245

<0.0245

0.269

1.07

5.59

VoRecovery

NA

NA

105

104

109

<0.0245 ngAnL

NA = Not Applicable * = FieM matiix spike recovery could not be calculated as ttie sample result was not detected above the analytical LOQ. (1) Samples were prepared August 21,2007 and analyzed September 2,2007. PFDA, PFUnA and PFDoA were re-analyzed on October 5,2007 (2) FieM matiix spike recovery did not meet method acceptance criteria of 100% ± 30%. (3) The analytical uncertainty has been adjusted for PFDA to 100% + 48% and PFUnA 100% + 38%. (4) Sample results are not reportable since the recovery of most appropriate fieM matiix spike was <50%.

Page 59 of 207



Table 21. WBMN GW S07JS (i»

3Af L/MS/D

£06-0549-1453

£06-0549-1454

£06-0549-1455

£06-0549-1457

Description






PFBA

Concenti-ation (ngAnL)

<0.0946

<0.0946

0.186

4.64

VoRecovery

NA

NA

78.6

98.1

<0.0946 ngAnL

PFPeA


<0.0356

<0.0356

0.250

5.33

VoRecovery

NA

NA

103

110

<0.0356n9*nL

PFHxA


<0.0371

<0.0371

0.247

4.77

VoRecovery

NA

NA

107

103

<0.0371 ngAnL

PFHpA


<0.0300

<0.0300

0.292

5.57

VoRecovery

NA

NA

117

111

<0.0300 ngAnL

m Lots ID

£06-0549-1453

£06-0549-1454

£06-0549-1455

£06-0549-1457

Descrvftion






fVOA


<0.0963

<0.0963

0.174

4.78

VoRecovery

NA

NA

72.3

99.3

<0.0963 ngAnL

PFNA


<0.0397

<0.0397

0 7??

3.93

VoRecovery

NA

NA

89.4

79.1

<0.0397 ngAnL

PFDA


<0.0492

<0.0492

0.145

3.06

VoRecovery

NA

NA

58.9'='

62.2'='

<0.0492ngAnL'^

PFUnA


<0.0986

<0.0986

0.206

4.05

VoRecovery

NA

NA

83.6

82.1

<0.0986 ngAnL

Page 60 of 207



Table 21 continued. WBMN GW S07JS' (1)

3MUMSID

£06-0549-1453

£06-0549-1454

£06-0549-1455

£06-0549-1457

Descrption





Average CorKentration (ngAnL) ± VoRPD

PFDoA


<0.101

<0.101

0.116

3.04

%Recovefy

NA

NA

45.8'='

60.1'='

iVot Reported"'

PFBS


<0.0795

<0.0795

0.331

6.84

VoRecovery

NA

NA

130

135'='

<0.0795 ngAnL

PFHS


<0.0413

<0.0413

0.283

5.66

Vol^covery

NA

NA

116

116

<O.0413 ngAnL

PFOS


<0.0245

<0.0245

0.289

5.49

VoRecovery

NA

NA

113

107

<0.0245 ngAnL

NA = Not Applicable (1) Samples were prepared August 21,2007 and analyzed September 2,2007. PFDA, PFUnA and PFDoA were re-analyzed on October 5,2007 (2) Field matiix spike recovery dM not meet method acceptance criteria of 100% ± 30%. (3) The analytical uncertainty has been adjusted for PFDA is 100% ± 41 %. (4) Sample results are not reportable since the recovery of most appropriate fieM matiix spike was <50%.

Page 61 of 207



Table 22. WBMN GW S07SP' (1)

3MUMSID

E06-0549-1458

£06-0549-1459

£06-0549-1460

£06-0549-1461

£06-0549-1462

Descripti'on




WBMN GW S07SP MS 070809


Average Concentrathn (ng/rnL) ± %RPD

PFBA


0.837

0.852

1.04

1.68

5.48

VoRecovery

NA

NA

82.6

88.3

98.0

0.845 ngAnL± 1.8%

PFPeA


<0.0356

<0.0356

0.286

1.07

5.24

VoRecovery

NA

NA

118

110

108

<0.0356 ngAnL

PFHxA


<0.0371

<0.0371

0.236

0.959

4.78

VoRecovery

NA

NA

102

103

103

<0.0371 ngAnL

PFHpA


<0.0300

<0.0300

0.279

1.18

5.50

VoRecovery

NA

NA

112

118

110

<0.0300 ngAnL

3MLMSiD

£06-0549-1458

£06-0549-1459

£06-0549-1460

£06-0549-1461

£06-0549-1462

Descrption






Average Concentration (ng/mL) ± %RPD

PFOA


<0.0963

<0.0963

0.192

0.893

4.83

VoRecovery

NA

NA

79.8

92.8

100

<0.O963 ngAnL

PFNA


<0.0397

<0.0397

0.194

0.907

4.92

VoRecovery

NA

78.1

91.3

99.0

<0.0397 ngAnL

PFDA


<0.0492

<0.0492

0.153

0.628

3.30

VoRecovery

NA

NA

62.2'='

63.8'='

67.1'='

<0.0492ngAnL'

PFUnA


<0.0986

<0.0986

0.220

0.759

4.70

VoRecovery

NA

NA

89.2

77.0

95.3

<0.0986 ngAnL

Page 62 of 207



Table 22 continued. WBMNGWS07SP' ,(1)

3MLMSID

£06-0549-1458

£06-0549-1459

£06-0549-1460

£06-0549-1461

£06-0549-1462

Descrption






Average Concentrathn (ng/rnL) ± VoRPD

PFDoA


<0.101

<0.101

0.143

0.510

4.11

VoRecovery

NA

NA

56.5'='

50.4'='

81.2

<0.101 ngAnL

PFBS

ConcentiTithn (ngAnL)

<0.0795

<0.0795

0.342

1.41

6.70

VoRecovery

NA

NA

135'='

139'='

132'='

<0.0795ngAnL'

PFHS


<0.0413

<0.0413

0.296

1.16

5.83

VoRecovery

NA

NA

121

119

119

<0.0413 ngAnL

PFOS


<0.0245

<0.0245

0.291

1.12

5.92

VoRecovery

NA

NA

114

109

116

<0.0245 ngAnL

NA = Not Applicable (1) Samples were prepared August 21,2007 and analyzed September 2,2007. PFDA, PFUnA and PFDoA were re-analyzed on October 5,2007 (2) FieM matiix spike recovery dM not meet mettiod acceptance criteria of 100% ± 30%. (3) Ttie analytical uncertainty has been adjusted for PFDA is 100% ± 38% and PFBS ± 35%.

Page 63 of 207




3MUMSID

£06-0549-1468

£06-0549-1469

£06-0549-1470

£06-0549-1471

£06-0549-1472

Descnption






Average Concentrathn (ng/mL) ± %RRD

PFBA


0.819

0.815

1.02

1.76

5.99

VoRecovery

NA

NA

85.8

99.6

109

0.817 ngAnLt 0.49%

PFPeA


<0.0356

<0.0356

0.278

1.18

5.67

<0.0356

VoRecovery

NA

NA

115

122

117

ng/rnL

PFHxA


<0.0371

<0.0371

0.210

1.01

4.86

VoRecovery

NA

NA

90.6

109

105

<0.0371 ngAnL

PFHpA


<0.0300

<0.0300

0.302

1.17

5.58'='

VoRecovery

NA

NA

121

117

112

<0.0300 ngAnL

3MUIIASID

£06-0549-1468

£06-0549-1469

£06-0549-1470

£06-0549-1471

£06-0549-1472

Descrption




WBMN GWS06PC MS 070809



PFOA


<0.0963

<0.0963

0.187

0.965

4.95

VoRecovery

NA

NA

77.7

100

103

<0.0963 ngAnL

PFNA


<0.0397

<0.0397

0.246

0.958

4.14

VoRecovery

NA

NA

99.0

96.4

83.3

<0.0397 ngAnL

PFDA


<0.0492

<0.0492

0.145

0.633

4.07

VoRecovery

NA

NA

58.9'"

64.3'"

82.7

<0.0492ngAnL'

PFUnA


<0.0986

<0.0986

0.195

0.839

4.40

VoRecovery

NA

NA

79.1

85.1

89.2

<0.0986 ngAnL

Page 64 of 207



Table 23 continued. WBMN GW S06PC* >

3MUMSID

£06-0549-1468

£06-0549-1469

£06-0549-1470

£06-0549-1471

£06-0549-1472

Des i^ thn







PFDoA


<0.101

<0.101

<0.101

0.632

3.14

%Recovefy

NA

NA

62.5'"

62.1'"

MotReportec/^

PFBS


<0.0795

<0.0795

0.356

1.41

7.22

VoRecovery

NA

NA

140'"

139'"

142'"

<0.0795ngAnL'

PFHS


<0.0413

<0.0413

0.289

1.15

5.99

VoRecovery

NA

NA

118

118

122

<0.0413 ngAnL

PFOS


<0.0245

<0.0245

0.296

1.12

6.52

VoRecovery

NA

NA

116

109

127

<0.0245ng^L

NA = Not Applicable * - FieM matiix spike recovery could not be calculated as ttie sample result was not detected above the analytical LOQ. (1) Samples were prepared August 21,2007 and analyzed September 2,2007. PFDA, PFUnA and PFDoA were re-analyzed on October 5,2007. (2) Samples were bracketed by a CCV for PFHpA tiiat did not meet method acceptance criteria of 100% + 25%. Recovery was 126%. (3) FieM matiix spike recovery dM not meet mettiod acceptance criteria of 100% ± 30%. (4) The analytical uncertainty has been adjusted for PFDA to 100% ± 41 % and PFBS 100% + 42%. (5) Sample results are not reportable since the recxivery of most appropriate fieM mataix spike was <50%.

Page 65 of 207



Table 24. WBMN GW S06JS (1)

3MUMSID

£06-0549-1473

£06-0549-1474

£06-0549-1475

E06-0549-1476

Descrption






PFBA


<0.0946

<0.0946

0.224

5.15

%Recovefy

NA

NA

94.7

109

<0.0946ng*iL

PFPeA


<0.0356

<0.0356

0.268

5.66

VoRecovery

NA

NA

111

117

<0.0356 ng/mL

PFHxA


<0.0232

<0.0232

0.197

4.58

VoRecovery

NA

NA

85.0

98.8

<0.0232 ngAnL

PFHpA


<0.0250'='

<0.0250'='

0.286'='

5.51'='

VoRecovery

NA

NA

114

110

<0.0250 ngAnL

3MLMSID

£06-0549-1473

£06-0549-1474

£06-0549-1475

£06-0549-1476

Description





Average Concentrathn (ngAnL) ± %RPD

PFOA


<0.0241

<0.0241

0.203

4.76

VoRecovery

NA

NA

84.3

98.9

<0.0241 ngAnL

PFNA


<0.0298

<0.0298

0.224

4.50

VoRecovery

NA

NA

90.2

90.6

<0.0298 ngAnL

PFDA


<0.0246

<0.0246

0.101

3.19

VoRecovery

NA

NA

41.1'"

64.8'"

NotReportecf"

PFUnA


<0.0986

<0.0986

0.171

4.08

VoRecovery

NA

NA

69.4'"

82.7

<0.0986 ngAnL

Page 66 of 207



Table 24 continued. WBMNGWS06JS ;(1)

3MLIMSID

£06-0549-1473

£06-0549-1474

E06-0549-1475

£06-0549-1476

Descrption






PFDoA

Concenlration (ngAnL)

<0.101

<0.101

<0.101

3.13

VoRecovery

NA

NA

* 61.9'"

NofReportec/"

PFBS


<0.0795

<0.0795

0.367

7.29

%Recovery

NA

NA

144'"

144'"

<0.0795ng^L'^'

PFHS

Conceirtration (ngAnL)

<0.0413

<0.0413

0.312

6.25

VoRecovery

NA

NA

128

128

<O.0413 ngAnL

PFOS


<0.0245

<0.0245

0.309

6.00

VoRecovery

NA

NA

121

117

<0.0245 ngAnL

NA = Not Applicable * - FieM matrix spike recovery could not be calculated as tiie sample result was not detected above the analytical LOQ. (1) Samples were prepared August 22,2007 and analyzed September 8,2007. (2) Samples were bracketed by a CCV for PFHpA that dM not meet method acceptance criteria of 100% ± 25%. Recovery was 126%. (3) FieM matrix spike recovery dM not meet method acceptance criteria of 100% ± 30%. (4) Sample resiAs are not reportable since the recovery of most appropriate fieM matiix spike was <50%. (5) Tiie analytical uncertainty has been adjusted forPFBS100%± 44%.

Page 67 of 207



Table 25. WBMN GW S05JS' (1)

3MUMSID

E06-0549-1477

£06-0549-1478

£06-0549-1479

£06-0549-1480

Descrption






PhBA


<0.0946

<0.0946

0.156

4.72

VoRecovery

NA

NA

65.9'='

99.7

<0.0946 ngAnL

PFPeA


<0.0356

<0.0356

0.221

5.26

VoRecovery

NA

NA

91.2

108

<0.0356 ngAnL

PFHxA

Concentrathn (ng/rnL)

<0.0232

<0.0232

0.204

4.18

VoRecovery

HA

NA

88.0

90.2

<0.0232 ngAnL

PFHpA


<0.0250

<0.0250

0.247

4.78

VoRecovery

NA

NA

98.8

95.6

<0.0250 ngAnL

3MUMSID

£06-0549-1477

£06-0549-1478

£06-0549-1479

£06-0549-1480

Description






PFOA

Conixntrathn (ngAnL)

<0.0241

<0.0241

0.158

4.36

VoRecovery

NA

NA

65.6'='

90.6

<0.0241 ngAnL^

PFNA

Concentration

<0.0298

<0.0298

0.197

4.29

VoRecovery

NA

NA

79.3

86.4

<0.0298 ngAnL

PFDA


<0.0246

<0.0246

0.117

3.54

%Recovefy

NA

NA

47.6'='

72.0

Wot Reported'*

PFUnA


<0.0986

<0.0986

0.226

4.79

VoRecovery

NA

NA

91.7

97.1

<0.0986 ngAnL

Page 68 of 207



Table 25 continued. WBMN GW SOSJS' '

3MLmiSID

E06-0549-1477

E06-0549-1478

E06-0549-1479

E06-0549-1480

Description






PFDoA


<0.101

<0.101

0.174

4.21

VoRecovery

NA

NA

68.8'='

83.2

<0.101 ngAnL

PFBS


<0.0795

<0.0795

0.309

6.44

VoRecovery

NA

NA

122

127

<0.079S ngAnL

PFHS


<0.0413

<0.0413

0.254

5.41

VoRecovery

NA

NA

104

111

<0.0413 ngAnL

PFOS


<0.0245

<0.0245

0.275

5.62

VoRecovery

NA

NA

107

110

<0.0245 ngAnL

NA = Not Applicable (1) Samples were prepared August 22,2007 and analyzed Septemtier 8,2007. (2) Field matrix spike recovery dM not meet mettiod acceptance criteria of 100% ± 30%. (3) The analytical uncertainty has been adjusted for PFOA to 100% ± 34%. (4) Sample results are not reportable since the recovery of most appropriate fieM matrix spike was <50%.

Page 69 of 207



Table 26. WBMN GW TRIPS 070809 (1)

3MLIMSID

£06-0549-1481

£06-0549-1482

£06-0549-1483

£06-0549-1484

Descrption



WBMN GW TRIP3 MS 070809

WBMN GWTRIP3 HS 070809 dil 1:20

PFBA


<0.0946

0.153

4.55

80.1

VoRecovery

NA

64.7'='

96.2

84.6

PFPeA


<0.0356

0.220

4.88

93.5

%Recovefy

NA

90.7

101

96.4

PFHxA


<0.0232

0.157

4.07

71.9

VoRecovery

NA

67.8'='

87.8

77.6

PFHpA


<0.0250

0.245

5.51

93.5

%Recovefy

NA

98.0

110

93.5

3IVILIMSID

£06-0549-1481

£06-0549-1482

£06-0549-1483

£06-0549-1484

Descrption

WBMN GW TR1P3 0 070809




PFOA


<0.0241

0.172

4.40

82.4

%Recoveiy

NA

71.5

91.4

85.6

PFNA


<0.0298

0.203

4.59

78.4

%Recoveiy

NA

81.7

92.4

78.9

PhDA


<0.0246

0.109

3.41

65.5

%Recovery

NA

44.3'='

69.3'='

66.5'='

PFUnA


<0.0986

0.215

5.36

108

%Recovefy

NA

87.2

109

110

- - • •

3MLIMSID

£06-0549-1481

£06-0549-1482

£06-0549-1483

E06-0549-1484

Descrption





PFDoA


<0.101

0.158

6.20

97.1

%Recovefy

NA

62.5'='

123

95.9

PFBS


<0.0795

0.325

6.57

114

%Recoveiy

NA

128

129

112

PFHS


<0.0413

0.285

5.68

100

VoRecovery

NA

117

116

102

PFOS


<0.0245

0.277

6.09

104

VoRecovery

NA

108

119

101

NA = Not Applicable (1) Samples were prepared August 22,2007 and analyzed September 8,2007. (2) FieM matiix spike recovery did not meet mettiod acceptance criteria of 100% ± 30%.

Page 70 of 207



Table 27. WBMN GW MWH (1)

3MLIMSID

£06-0549-1488

£06-0549-1485

£06-0549-1486

£06-0549-1487

£06-0549-1489

Desi:rption

WBMN GW MWH RB 070810



WBMN GW MWH LS 070810

WBMN GW MWH HS 070810


PFSA


<0.0946

<0.0946

<0.0946

0.176

4.54

<0.0946

VoRecovery

NA

NA

NA

74.4

95.9

ngAnL

PFPeA


<0.0356

<0.0356

<0.0356

0.225

5.11

<0.0356

VoRecovery

NA

NA

NA

92.8

105

ng^L

PFHxA


<0.0232

<0.0232

<0.0232

0.185

4.13

VoRecovery

NA

NA

NA

79.8

89.1

<0.0232 ngAnL

PFHpA


<0.0250

<0.0250

<0.0250

0.245

4.86

VoRecovery

NA

NA

NA

98.0

97.2

<0.0250 ngAnL

3iyiUMSID

E06-0549-1488

£06-0549-1485

£06-0549-1486

£06-0549-1487

£06-0549-1489

Description






Average Concenti-ation (ngAnL) ± %RPD

PFOA


<0.0241

<0.0241

<0.0241

0.152

4.72

VoRecovery

NA

NA

NA

63.1'='

98.0

<0.0241 ngAnL^

PFNA


<0.0298

<0.0298

<0.0298

0.208

4.03

VoRecovery

NA

NA

NA

83.7

81.1

<0.0298 ngAnL

PFDA


<0.0246

<0.0246

<0.0246

0.0906

3.17

^Recovefy

NA

NA

NA

36.8'='

64.4'='

NofReportec/*

PFUnA


<0.0986

<0.0986

<0.0986

0.154

3.74

VoRecovery

NA

NA

NA

62.5'='

75.8

<a0986 ngAnL"

Page 71 of 207



Table 27continued. WBMN GWMWH' (1)

3MLmSID

E06-0549-1488

£06-0549-1485

£06-0549-1486

£06-0549-1487

£06-0549-1489

Description







PFDoA


<0.101

<0.101

<0.101

<0.101

2.81

VoRecovery

NA

NA

NA

* 55.5'='

Not Reportec/*'

PFBS


<0.0795

<0.0795

<0.0795

0.337

6.34

VoRecovery

NA

NA

NA

133'='

125

<0.0795 ngAnL'

PFHS


<0.0413

<0.0413

<0.0413

0.266

5.38

VoRecovery

NA

NA

NA

109

110

<0.0413 ngAnL

PFOS


<0.0245

<0.0245

<0.0245

0.273

5.54

NA

NA

NA

107

108

<0.0245 ngAnL

NA = Not Applicable RB= Rinse Blank * - FieM matrix spike recovery could not be calculated as ttie sample result was not detected above ttie analytical LOQ. (1) Samples vrere prepared August 22,2007 and analyzed September 8,2007. (2) Field matiix spike recovery did not meet method acceptance criteria of 100% ± 30%. (3) The analytical uncertainty has been adjusted for PFOA to 100% + 37%, PFUnA 00% ± 38%, and PFBS 100% ± 33%. (4) Sample results are not reportable since the recovery of most appropriate fieM matiix spike was <50%.

Page 72 of 207



Table 28. WBMNGWS05SP' (1)

3MUMSiD

£06-0549-1490

£06-0549-1491

£06-0549-1492

£06-0549-1493

Descrption




WBMN GWS05SP HS 070810

Average Concentiation (ngAnL) ± VoRPD

PFBA


0.857

0.828

1.03

5.50

VoRecovery

NA

NA

79.2

98.4

0.843 ngAnL± 3.4%

PFPeA


<0.0356

<0.0356

0.289

5.22

%Recovery

NA

NA

119

108

<0.0356ng^L

PFHxA


<0.0232

<0.0232

0.211

4.22

VoRecovery

NA

NA

91.1

91.1

<0.0232 ngAnL

PFHpA


<0.0250

<0.0250

0.246

5.00

VoRecovery^

NA

NA

98.4

100

<O.02S0 ngAnL

3MUMSID

£06-0549-1490

£06-0549-1491

£06-0549-1492

£06-0549-1493

Descripti'on


WBMN GWS05SP DB 070810




PFOA


<0.0241

<0.0241

0.180

4.43

VoRecovery

NA

NA

74.8

92.0

<0.0241 ngAnL

PFNA


<0.0298

<0.0298

0.191

4.12

VoRecovery

NA

NA

76.9

82.9

<0.0298 ngAnL

PFDA

ConcentratKin (ngAnL)

<:0.0246

<0.0246

0.111

3.36

VoRecovery

NA

NA

45.1'='

68.3'='

NotReportetP

PFUnA


<0.0986

<0.0986

0.224

4.22

VoRecovery

NA

NA

90.9

85.6

<0.0986 ngAnL

Page 73 of 207



Table 28 continued. WBMNGWS05SP' ,(1)

3MUMSID

E06-0549-1490

£06-0549-1491

£06-0549-1492

£06-0549-1493

Desi:rptmn






PFDoA


<0.101

<0.101

0.165

3.33

VoRecovery

NA

NA

65.2'='

65.8'='

<0.101 ngAnL

PFBS


<0.0795

<0.0795

0.335

6.62

VoRecovery

NA

NA

132'='

130

<0.0795ngAnL"'

PFHS


<0.0413

<0.0413

0.267

5.55

VoRecovery

NA

NA

109

113

<0.0413 ngAnL

PFOS


<0.0245

<0.0245

0.314

5.71

VoRecovery

NA

NA

123

111

<0.0245 ngAnL

NA = Not Applicable (1) Samples were prepared August 22,2007 and analyzed September 8,2007. (2) Field matiix spike recovery dM not meet mettiod acceptance criteria of 100% ± 30%. (3) Sample results are not reportable since the recovery of most appropriate fieM matiix spike was <50% (4) Ttie analytical uncertainty has been adjusted for PFBS to 100% + 32%.

Page 74 of 207



Table 29. WBMNGWS05PC (1)

3MLIMSID

£06-0549-1494

E06-0549-1495

£06-0549-1496

£06-0549-1497

Description





Average Concentrathn (ng/mL) ± VoRPD

PFBA


0.442

0.423

0.722

5.32

VoRecovery

NA

NA

122

103

0.433 ngAnLt 4.4%

fV=PeA


<0.0356

<0.0356

0.264

5.67

VoRecovery

NA

NA

109

117

<0.0356 ngAnL

PFHxA


<0.0232

<0.0232

0.237

4.68

%Recoveiy

NA

NA

102

101

<0.0232n9tnL

PFHpA


<0.0250

<0.0250

0.272

5.48

%Recovefy

NA

NA

109

110

<0.0250ng/hiL

3MUI\fSID

£06-0549-1494

£06-0549-1495

£06-0549-1496

£06-0549-1497

Descrption





Aveiage Concentrathn (ngAnL) ± VoRPD

PFOA


<0.0241

<0.0241

0.201

4.98

VoRecovery

NA

NA

83.5

103

<0.0241 ngAnL

PFNA


<0.0298

<0.0298

0.221

4.55

VoRecovery

NA

NA

89.0

91.6

<0.0298 ngAnL

PFDA


<0.0246

<0.0246

0.108

4.33

VoRecovery

NA

NA

43.9'='

88.0

NotReportecP

PFUnA


<0.0986

<0.0986

0.272

6.09

VoRecovery

NA

NA

110

124

<0.0986 ngAnL

Page 75 of 207



Table 29 continued. WBMN GW S05SPC (1)

3MLBitSID

£06-0549-1494

£06-0549-1495

£06-0549-1496

£06-0549-1497

Descrption






PFDoA


<0.101

<0.101

0.200

6.60

VoRecovery

NA

NA

79.1

130

<0.101 ngAnL

PFBS


<0.0795

<0.0795

0.360

7.15

VoRecovery

NA

NA

142'='

141'='

<0.0795ngAnL<^

PFHS


<0.0413

<0.0413

0.305

5.95

VoRecovery

NA

NA

125

122

<0.0413 ngAnL

PFOS


<0.0245

<0.0245

0.310

6.26

VoRecovery

NA

NA

121

122

<0.0245 ngAnL

NA = Not Applicable (1) Samples were prepared August 22,2 07 and analyzed September 8,2007. (2) FieM matiix spike recovery did not meet method acceptance criteria of 100% ± 30%. (3) Sample results are not reportable since the recovery of most appropriate fieM matiix spike was <50% (4) Ttie analytical uncertainty has been adjusted for PFBS to 100% ± 42%.

Page 76 of 207



Table 30. WBMN GW MWG (1)

3MUMSID

E06-0549-1498

£06-0549-1499

£06-0549-1500

£06-0549-1501

Descqption


WBMN GW MWG DB 070810

WBMN GW MWG LS 070810

WBMN GW MWG HS 070810

Average Concentratran (ngAnL) ± %RPD

PFBA


0.150

0.126

0.336

4.47

%Recovefy

NA

NA

83.7

91.5

0.138 ngAnLt 17%

PFPeA


<0.0356

<0.0356

0.259

5.21

VoRecovery

NA

NA

107

107

<0.0356ng*iL

PFHxA


<0.0232

<0.0232

0.198

3.82

VoRecovery

NA

NA

85.5

82.4

<0.0232 ngAnL

PFHpA


<0.0250

<0.0250

0.264

4.83

VoRecovery

NA

NA

106

96.6

<0.0250 ngAnL

3MLIMSID

£06-0549-1498

£06-0549-1499

£06-0549-1500

£06-0549-1501

Description






PFOA

Concentrathn fng/htLj

<0.0241

<0.0241

0.213

3.94

VoRecovery

NA

NA

88.5

81.8

<0.0241 ngAnL

PFNA


<0.0298

<0.0298

0.192

3.70

VoRecovery

NA

NA

77.3

74.5

<0.0298 ngAnL

PFDA


<0.0246

<0.0246

0.115

2.95

%Recovery

NA

NA

46.7'='

60.0'='

Not Reported'^

PFUnA


<0.0986

<0.0986

0.191

3.66

VoRecovery

NA

NA

77.5

74.2

<0.0986 ngAnL

Page 77 of 207



Table 30 continued. WBMN GW MWG 1)

3MLmiSID

£06-0549-1498

£06-0549-1499

£06-0549-1500

£06-0549-1501

Description





Av&age Concentration (ngAnL) ± VoRPD

PFDoA


<0.101

<0.101

<0.101

2.84

VoRecovery

NA

NA

* 56.1

Not Reported' '

PFBS


<0.0795

<0.0795

0.326

6.17

%Recove#y

NA

NA

128

121

<0.0795ng*nl.

PFHS

Concentratran (ngAnL)

<0.0413

<0.0413

0.309

5.16

VoRecovery

NA

NA

126

106

<0.0413 ngAnL

PFOS

Concerttifation (ngAnL)

0.0657

0.0604

0.309

5.25

VoRecovery

NA

NA

96.0

101

0.0631 ngAnL± 8.4%

NA = Not Applicable * - FieM matrix spike recovery could not be calculated as the sample result was not detected above the analytical LOQ. (1) Samples were prepared August 22,2007 and analyzed September 8,2007. (2) FieM matiix spike recovery dM not meet method acceptance criteria of 100% ±30%. (3) Sample results are not reportable since ttie recovery of most appropriate fieM matrix spike was <50%.

Page 78 of 207



Table 31. WBMN GW TRIP4 070810' i(i)

3IVIUMSID

£06-0549-1502

£06-0549-1503

£06-0549-1504

£06-0549-1505

Descrption





PFBA


<0.0946

0.153

4.70

76.8

VoRecovery

NA

64.7'='

99.3

81.1

PFPeA


<0.0356

0.217

5.09

91.6

VoRecovery

NA

89.5

105

94.4

PFHxA


<0.0232

0.158

4.15

64.8

%Recove»y

NA

68.2'='

89.6

69.9

PFHpA


<0.0250

0.210

5.16

90.5

VoRecovery

NA

84.0

103

90.5

3MUMSID

£06-0549-1502

£06-0549-1503

£06-0549-1504

£06-0549-1505

Descrption

WBMN GW TRIP4 0 070810




PFOA


<0.0241

0.144

4.62

86.2

%Recovefy

NA

59.8'='

96.0

89.5

PFNA


<0.0298

0.191

4.49

71.7

VoRecovery

NA

76.9

90.4

72.2

PFDA


<0.0246

0.0840

3.70

59.6

VoRecovery

NA

34.1'='

75.2

60.5'='

PFUnA


<0.0986

0.197

5.10

86.9

%Recovefy

NA

79.9

103

88.1

3MUMSID

£06-0549-1502

£06-0549-1503

£06-0549-1504

£06-0549-1505

Description




WBMN GWTRIP4 HS 070810 dil 1:20

PFDoA


<0.101

0.113

5.45

91.0

VoRecovery

NA

44.7'='

107

89.3

PFBS


<0.0795

0.296

6.72

116

%Recovery

NA

117

132'='

114

PFHS


<0.0413

0.257

5.63

98.9

VoRecovery

NA

105

115

101

PFOS


<0.0245

0.262

5.92

105

VoRecovery

NA

102

116

102

NA = Not Applicable (1) Samples were prepared August 22,2007 and analyzed September 8,2007. (2) FieM matiix spike recovery dM not meet method acceptance criteria of 100% ± 30%.

Page 79 of 207



Table 32. WBMNGWS02JS' (1)

3MUMSID

£06-0549-1506

£06-0549-1507

£06-0549-1508

£06-0549-1509

Descrijptidn






PFBA


<0.0946

<0.0946

0.192

3.79

VoRecovery

NA

NA

81.1

80.1

0.0946 ngAnL

PFPeA


<0.0356

<0.0356

0.220

4.25

%Recoveiy

NA

NA

90.7

87.6

<0.0356ng*nL

PFHxA


0.0295

<0.0232

0.305

3.70

VoRecovery

NA

NA

119

79.2

0.0295 ngAnL*

PFHpA


<0.0250

<0.0250

0.267

4.17

VoRecovery

NA

NA

107

83.4

<0.0250 ngAnL

3MLmiSID

£06-0549-1506

E06-0549-1507

£06-0549-1508

£06-0549-1509

Descrption






PFOA


<0.0241

<0.0241

0.182

3.79

VoRecovery

NA

NA

75.6

78.7

<0.0241 ngAnL

PFNA


<0.0298

<0.0298

0.181

3.81

VoRecovery

NA

NA

72.9

76.7

<0.0298ng4nL

PFDA


<0.0246

<0.0246

0.132

2.73

VoRecovery

NA

NA

53.7'^'

55.5' '

<0.0246ng^L'*

PFUnA


<0.0986

<0.0986

0.271

4.34

VoRecovery

NA

NA

110

88.0

<0.0986 ngAnL

Page 80 of 207



Table 32 continued. WBMNGWS02JS 1)

3MLIMSID

£06-0549-1506

£06-0549-1507

£06-0549-1508

£06-0549-1509

Descrption





Averse Concentration (ngAnL) ± VoRPD

PFDoA


<0.101

<0.101

0.216

4.74

VoRecovery

NA

NA

85.4

93.7

<0.101 ngAnL

PFBS


<0.0795

<0.0795

0.320

5.43

VoRecovery

NA

NA

126

107

<0.0795 ngAnL

PFHS


<0.0413

<0.0413

0.254

4.64

VoRecovery

NA

NA

104

94.9

<0.0413 ngAnL

PFOS


<0.0245

<0.0245

0.288

4.76

%Recovefy

NA

NA

112

92.9

<0.0245ng^L

NA = Not Applicable (1) Samples were prepared August 22,2007 and analyzed September 8,2007. (2) Tiie sample and sample duplicate produced one result above tiie LOQ and one result below ttie LOQ. The reported average concenti:ation represents only ttie result above ttie LOQ. A

true average was not calculated. (3) FieM matrix spike recovery dM not meet mettiod acceptance criteria of 100% ± 30%. (4) Ttie analytical uncertainty has been adjusted for PFDA to 100% ± 46% and PFBS 100% ± 32%.

Page 81 of 207




3MLIMSID

£06-0549-1510

£06-0549-1511

£06-0549-1512

£06-0549-1513

£06-0549-1514

Description







PFBA


1.21

1.30

1.47

2.13

5.46

VoRecovery

NA

NA

90.9

92.5

88.9

1.26 ngAnLt 7.2%

PFPeA


<0.0356

<0.0356

0.269

1.10

4.84

VoRecovery

NA

NA

111

113

100

<0.0356 ngAnL

PFHxA


<0.0232

<0.0232

0.225

0.911

3.96

<0.0232

VoRecovery

NA

NA

97.1

98.3

85.5

ngAnL

PFHpA


<0.0250

<0.0250

0.243

1.15

4.98

VoRecovery^

NA

NA

97.2

115

100

<0.0250 ngAnL

3MLUSID

£06-0549-1510

£06-0549-1511

E06-0549-1512

£06-0549-1513

£06-0549-1514

Descrption






Average Concenfration (ngAnL) ± VoRPD

PFOA


<0.0241

<0.0241

0.175

0.901

4.39

%Recovefy

NA

NA

72.7

93.6

91.2

<0.0241 ngAnL

PFNA


<0.0298

<0.0298

0.192

0.882

4.19

%Recovefy

NA

NA

77.3

88.8

84.3

<0.0298ngtoL

PFDA


<0.0246

<0.0246

0.0866

0.740

3.56

VoRecovery

NA

NA

35.2'='

75.2

72.4

NofReportedf*

PFUnA


<0.0986

<0.0986

0.227

1.09

4.92

VoRecovery

NA

NA

92.1

111

100

<0.0986 ngAnL

Page 82 of 207


Analysis of Woodbury Waste Site Groundwater Samples; 3nj Quarter 2007

Table 33 continued. WBMN GW S02PC< >

3MLIMSID

£06-0549-1510

E06-0549-1511

£06-0549-1512

£06-0549-1513

£06-0549-1514

Description






Average Concentrathn (ng/mL) ± VoRPU

PFDoA

Ccjncentrathn (ngAnL)

<0.101

<0.101

0.168

1.16

4.67

VoRecovery

NA

NA

66.4'='

115

92.3

<0.101 ngAnL

PFBS


<0.0795

<0.0795

0.302

1.35

6.20

VoRecovery

NA

NA

119

133'='

122

<0.0795n9*nL

PFHS


0.0458

<0.0413

0.302

1.14

5.26

VoRecovery

NA

NA

105

112

107

0.0458 ngAnU"

PFOS

Ccutcentrati'on (ngAnL)

<0.0245

<0.0245

0.266

1.14

5.25

VoRecovery

NA

NA

104

111

102

<0.024 ngAnL

NA = Not Applicable (1) Samples were prepared August 22,2007 and analyzed September 8,2007. (2) FieM matrix spike recovery dM not meet metticM acceptance criteria of 100% ± 30%. (3) Sample results are not reportable since ttie recovery of most appropriate fieM matiix spike was <50%. (4) The sample and sample duplicate produced one result above ttie LOQ and one result below the LOQ. The reported average concentiation represents only the result above the LOQ. A

tnje average was not calculated.

Page 83 of 207



Table 34. WBMN GW S02DR< (1)

3MUMSID

£06-0549-1515

£06-0549-1516

£06-0549-1517

E06-0549-1518

£06-0549-1519

Descrption

WBMN GW S02DR 0 070810

WBMN GW S02DR DB 070810

WBMN GW S02DR LS 070810

WBMN GW S02DR MS 070810

WBMN GW S02DR HS 070810

Average Concentiation (ngAnL) ± %RPD

PFBA


0.542

0.553

0.783

1.44

5.00

VoRecovery

NA

NA

99.5

94.3

94.1

0.548 ngAnL ±2.0%

PhPeA


<0.0356

<0.0356

0.274

1.14

5.28

VoRecovery

NA

NA

113

118

109

<0.0356 ngAnL

PFHxA


<0.0232

<0.0232

0.228

0.907

4.20

VoRecovery

NA

NA

98.4

97.9

90.6

<0.0232 ngAnL

PFHpA


<0.0250

<0.0250

0.281

1.12

5.27

VoRecovery

NA

NA

112

112

105

<0.02S0 ngAnL

3MUMSID

E06-0549-1515

£06-0549-1516

£06-0549-1517

£06-0549-1518

E06-0549-1519

Description

WBMN GWS02DR 0 070810

WBMN GW S02DR DB 070810

WBMN GWS02DR LS 070810

WBMN GWS02DR MS 070810

WBMN GW S02DR HS 070810


PFOA


<0.0241

<0.0241

0.240

0.959

4.60

VoRecovery

NA

NA

99.7

99.6

95.6

<0.0241 ngAnL

PFNA


<0.0298

<0.0298

0.214

0.941

4.67

VoRecovery

NA

NA

86.2

94.7

94.0

<0.0298 ngAnL

PFDA


<0.0246

<0.0246

0.112

0.643

3.69

VoRecovery

NA

NA

45.5'='

65.3

75.0

NotReportecP

PFUnA


<0.0986

<0.0986

0.214

0.994

4.94

VoRecovery

NA

NA

86.8

101

100

<0.0986 ngAnL

Page 84 of 207



Table 34 continued. WBMN GW S02DR' id)

3MLKI/ISID

£06-0549-1515

£06-0549-1516

£06-0549-1517

£06-0549-1518

£06-0549-1519

Descrption

WBMN GWS02DR 0 070810

WBMN GWS02DR DB 070810

WBMN GW S02DR LS 070810

WBMN GW S02DR MS 070810

WBMN GWS02DR HS 070810


PFDoA


<0.101

<0.101

<0.101

0.740

3.77

VoRecovery

NA

NA

73.1

74.5

NotReportecP

PFBS


<0.0795

<0.0795

0.350

1.39

6.46

VoRecovery

NA

NA

138'='

137'='

127

<0.0795ngAnL'''

PFHS


0.0479

0.0477

0.351

1.19

5.55

VoRecovery

NA

NA

124

117

113

0.0478 ngAnLt 0.42%

PFOS


<0.0245

<0.0245

0.287

1.11

5.57

VoRecovery

NA

NA

112

108

109

<0.024S ngAnL

NA = Not Applicable * - FieM matrix spike recovery could not be calculated as the sample resutt was not detected above the analytical LOQ. (1) Samples were prepared August 22,2007 and analyzed September 8,2007. (2) FieM matiix spike recovery dM not meet method acceptance criteria of 100% + 30%. (3) Sample results are not reportable since the recovery of most appropriate fieM matrix spike was <50%. (4) The analytical uncertainty has been adjusted for PFBS to 100% ± 38%.

Page 85 of 207



Table 35. WBMN GW S09JS' (1)

3MUMSID

£06-0549-1523

£06-0549-1520

£06-0549-1521

£06-0549-1522

£06-0549-1524

Descrption

WBMN GW S09JS RB 070810






PFBA


<0.0946

<0.0946

<0.0946

0.174

3.76

VoRecovery

NA

NA

NA

73.5

79.5

<0.0946 ngAnL

PFPeA


<0.0356

<0.0356

<0.0356

0.250

4.46

VoRecovery

NA

NA

NA

103

92.0

<0.0356 ngAnL

PFHxA


<0.0232

<0.0232

0.0971

0.271

3.58

VoRecovery

NA

NA

NA

75.1

75.2

<0.0232 ngAnL

PFHpA


<0.0250

<0.0250

<0.0250

0.287

4.88

<0.0250

VoRecovery^

NA

NA

NA

115

97.6

ngAnL

3MLIMSID

£06-0549-1523

£06-0549-1520

£06-0549-1521

£06-0549-1522

£06-0549-1524

Descrption

WBMN GWS09JS RB 070810






PFOA


<0.0241

<0.0241

<0.0241

0.191

4.13

VoRecovery

NA

NA

NA

79.4

85.8

<0.0241 ngAnL

PFNA


<0.0298

<0.0298

<0.0298

0.215

4.13

VoRecovery

NA

NA

NA

86.6

83.1

<0.0298 ngAnL

PFDA


<0.0246

<0.0246

<0.0246

0.121

3.48

VoRecovery

NA

NA

NA

49.2'='

70.7

Not Reported''

PFUnA


<0.0986

<0.0986

<0.0986

0.283

4.47

VoRecovery

NA

NA

NA

115

90.7

<0.0986 ngAnL

Page 86 of 207



Table 35 continued. WBMN GW S09JS' :m

3MLIMSID

£06-0549-1523

£06-0549-1520

£06-0549-1521

£06-0549-1522

£06-0549-1524

Descrption

WBMN GWS09JS RB 070810






PFDoA


<0.101

<0.101

<0.101

0.229

5.17

VoRecovery

NA

NA

NA

90.5

102

<0.101 ngAnL

PFBS


<0.0795

<0.0795

<0.0795

0.338

5.83

%Recove#y

NA

NA

NA

133'='

115

<O.O795nfi0nL'*

PFHS


<0.0413

<0.0413

<0.0413

0.272

4.76

VoRecovery

NA

NA

NA

111

97.3

<0.0413 ngAnL

PFOS


<0.0245

<0.0245

<0.0245

0.305

5.03

VoRecovery

NA

NA

NA

119

98.1

<0.0245 ngAnL

NA = Not Applicable RB = Rinse Blank (1) Samples were prepared August 22,2007 and analyzed September 8,2007. (2) FieM matiix spike recovery dM not meet method acceptance criteria of 100% ± 30%. (3) Sample results are not reportable since tiie recovery of most appropriate fieM matiix spike was <50%. (4) The analytical uncertainty has been adjusted for PFBS to 100% ± 33%.

Page 87 of 207



Table 36. WBMN GW MW4U (1)

3MLIMSID

E06-0549-1525

£06-0549-1526

£06-0549-1527

£06-0549-1528

£06-0549-1529

Description



WBMN GW MW4L LS 070810

WBMN GW MW4L MS 070810

WBMN GW MW4L HS 070810

Average Concentrathn (ng/rnL) ± %RPD

PFSA


0.673

0.613

0.798

1.39

4.51

VoRecovery

NA

NA

NC

78.9

81.7

0.643 ngAnL± 9.3%

PFPeA


<0.0356

<0.0356

0.288

1.10

5.33

<0.0356

VoRecovery

NA

NA

119

113

110

ng/mL

PFHxA


<0.0232

0.0251

0.185

0.785

4.35

VoRecovery

NA

NA

69.0'='

82.0

93.3

0.025* ngAnL'^'^

PFHpA


<0.0250

<0.0250

0.257

1.07

5.36

VoRecovery

NA

NA

103

107

107

<0.0250 ngAnL

3MLUi»SID

£06-0549-1525

£06-0549-1526

£06-0549-1527

£06-0549-1528

£06-0549-1529

Description






Aveiage Conc&itration (ngAnL) ± VoRPD

PFOA

Concenfratfon (ngAnL)

<0.0241

<0.0241

0.212

0.980

4.69

VoRecovery

NA

NA

88.1

102

97.4

<0.0241 ngAnL

PFNA


<0.0298

<0.0298

0.209

1.06

4.72

VoRecovery

NA

NA

84.1

107

95.0

<0.0298 ngAnL

PFDA


<0.0246

<0.0246

0.0930

0.682

3.52

VoRecovery

NA

NA

37.8'='

69.3'='

71.5

NotReporte</^

PFUnA


<0.0986

<0.0986

0.190

0.85

4.49

VoRecovery

NA

NA

77.1

86.4

91.1

<0.0986 ngAnL

Page 88 of 207



Table 36 continued. WBMN GW MW4L' (1)

3MLMSID

E06-0549-1525

£06-0549-1526

£06-0549-1527

£06-0549-1528

£06-0549-1529

Description






Average CorKentration (ng/rnL) ± VoRPD

PFDoA


<0.101

<0.101

<0.101

0.534

3.33

VoRecovery

NA

NA

* 52.8'='

65.8'='

NotReporte<P

PFBS

ConcentratKin (ngAnL)

0.192

0.173

0.507

1.51

6.50

VoRecovery

NA

NA

128

131'='

124

0.183 ngAnLt 10%

PFHS


0.368

0.367

0.618

1.47

5.76

VoRecovery

NA

NA

102

113

110

0.368 ngAnL± 0.27%

PFOS


0.119

0.107

0.353

1.20

5.40

VoRecovery

NA

NA

93.7

106

103

0.113 ngAnL± 11%

NA = Not Applicable NO = Not Calculated - Endogenous sample concenti'ation is greater tiian 2x spike level. * - FieM matrix spike recoveiy couM not be calculated as tiie sample result was not detected above the analytical LOQ. (1) Samples were prepared August 22,2007 and analyzed September 8,2007. (2) FieM matiix spike recovery dM not meet method acceptance criteria of 100% ± 30%. (3) The sample and sample duplk:ate produced one result above the LOQ and one result below the LOQ. The reported average concentiation represents only ttie result above the LOQ. A

true average was not calculated. (4) The analytical uncertainty has been adjusted for PFHxA to 100% ± 31 %. (5) Sample results are not reportable since ttie recovery of most appropriate fieM matiix spike was <50%.

Page 89 of 207



Table 37. WBMN GW TRIPS 070813' (1)

3MUMSID

£06-0549-1530

£06-0549-1531

£06-0549-1532

E06-0549-1533

Description




WBMN GWTR1P5 HS 070813 dill -.20

PFSA


<0.0946

0.141

4.59

76.1

VoRecovery

NA

59.6'='

97.0

60.4

PFPeA


<0.0356

0.244

5.04

84.0

%Recovefy

NA

101

104

66.6

PFHxA


<0.0232

0.166

4.21

65.2

%Recovefy

NA

71.6

90.9

70.3

PFHpA


<0.0250

0.224

5.46

89.7

VoRecovery

NA

89.6

109

89.7

3MLfMS/D

£06-0549-1530

£06-0549-1531

£06-0549-1532

E06-0549-1533

Descrption


WBMN GW TR1P5 LS 070813


WBMN GW TRIPS HS 070813 dil V.20

PFOA


<0.0241

0.163

4.73

76.6

%Recovefy

NA

67.7'='

98.3

79.5

PFWA


<0.0298

0.185

5.05

75.4

%Recovefy

NA

74.5

102

75.9

PFDA


<0.0246

0.120

3.80

65.5

VoRecovery

NA

48.8'='

77.2

66.5'='

PFUnA


<0.0986

0.264

5.26

91.1

VoRecovery

NA

107

107

92.4

3MLIMSID

£06-0549-1530

£06-0549-1531

£06-0549-1532

£06-0549-1533

Descnptfon





PFDoA


<0.101

0.117

6.31

82.8

%Recovefy

NA

46.2'='

125

81.8

PFBS


<0.0795

0.311

6.42

107

%Recovefy

NA

122

126

105

PFHS


<0.0413

0.262

5.49

93.8

VoRecovery

NA

107

112

95.9

PFOS

CorKentiTition (ngAnL)

<0.0245

0.255

5.54

97.6

VoRecovery

NA

100

108

95.2

NA = Not Applicable (1) Samples were prepared August 22,2007 and analyzed September 8,2007. (2) FieM matiix spike recovery dM not meet method acceptance criteria of 100% + 30%.

Page 90 of 207



Table 38. WBMN GW B1 (1)

3MLIMSID

£06-0549-1534

E06-0549-1535

£06-0549-1536

£06-0549-1537

Descrption

WBMN GWB1 0 070813

WBMN GWB1DB 070813

WBMN GWB1LS 070813

WBMN GWB1HS 070813


PFSA


1.67

1.65

1.82

5.34

VoRecovery

NA

NA

NC

77.8

1.66 ngAnLt 1.2%

PFPeA


0.494

0.477

0.729

5.25

VoRecovery

NA

NA

100

98.3

0.486 ngAnL± 3.5%

PFHxA


0.824

0.832

0.927

4.74

VoRecovery

NA

UA

NC

84.4

0.828 ng^L± 1.0%

PFHpA


0.106

0.109

0.399

5.04

VoRecovery

NA

NA

117

98.7

0.108 ngAnLt 2.8%

3MLmSID

£06-0549-1534

£06-0549-1535

£06-0549-1536

£06-0549-1537

Description

WBMN GWB1 0 070813

WBMN GWB1DB 070813

WBMN GWB1LS 070813

WBMN GWB1HS 070813

Average Concentration (ngAnL) i VoRPD

PFOA


1.41

1.33

1.59

5.95

VoRecovery

NA

NA

NC

95.1

1.37 ngAnLt 5.8%

PFNA


<0.0298

<0.0298

0.172

4.15

VoRecovery

NA

NA

69.2'='

83.5

<0.0298 ngAnL'

PFDA


<0.0246

<0.0246

0.0624

3.11

VoRecovery

NA

NA

25.4'='

63.2'='

NotR^Mrter/^

PFUnA


<0.0986

<0.0986

0.115

3.78

VoRecovery

NA

NA

46.6'='

76.7

NotReportedP

Page 91 of 207



Table 38 continued. WBMN GW B1 (1)

3MLIMSID

£06-0549-1534

£06-0549-1535

£06-0549-1536

£06-0549-1537

Descrption

WBMN GWB1 0 070813

WBMN GWB1DB 070813

WBMN GWB1LS 070813

WBMN GWB1HS 070813

Average CorKentration (ngAnL) i VoRPD

PFDoA


<0.101

<0.101

<0.101

1.66

VoRecovery

NA

NA

* 32.8'='

NotReporte(P

PFBS


1.93

1.94

2.16

7.60

VoRecovery

NA

NA

NC

112

1.94 ngAnLt 0.52%

PFHS


1.53

1.55

1.75

6.51

VoRecovery

NA

NA

NC

102

1.54 ngAnLt 1.3%

PFOS


0.0412

0.0362

0.259

4.88

VoRecovery

NA

NA

86.0

94.5

0.0387 ngAnLt 13%

NA = Not Applicable NC = Not Calculated - Endogenous sample concentiation is greater ttian 2x spike level. * - FieM matrix spike recovery could not be calculated as ttie sample result was not detected above the analytical LOQ. (1) Samples were prepared August 22,2007 and analyzed September 8,2007. (2) FieM matiix spike recovery dM not meet mettiod acceptance criteria of 100% ± 30%. (3) The analytical uncertainty has been adjusted for PFNA to 100% ± 31 %. (4) Sample results are not reportable since the recovery of most appropriate fieM matiix spike was <50%.

Page 92 of 207



Table 39. WBMN GW B2' (1)

3MUMSID

£06-0549-1538

£06-0549-1539

£06-0549-1540

£06-0549-1541

Description

WBMN GWB2 0 070813

WBMN GWB2DB 070813

WBMN GWB2LS 070813

WBMN GWB2HS 070813

Average Concentration (ng/mL) t VoRPD

PFSA


0.412

0.455

0.634

4.40

VoRecovery

NA

NA

84.7

83.8

0.434 ngAnLt 9.9%

PFPeA


<0.0356

<0.0356

0.256

4.70

%Recovefy

NA

NA

106

96.9

<0.0356ng^L

PFHxA


<0.0232

<0.0232

0.175

3.97

VoRecovery

NA

NA

75.5

85.7

<0.0232 ngAnL

PFHpA


<0.0250

<0.0250

0.248

5.05

VoRecovery

NA

NA

99.2

101

<0.0250 ngAnL

3MUMSID

£06-0549-1538

£06-0549-1539

£06-0549-1540

£06-0549-1541

Description

WBMN GWB2 0070813

WBMN GWB2DB 070813

WBMN GWB2LS 070813

WBMN GWB2HS 070813

Average ConcentiTition (ngAnL) t VoRPD

PFOA


<0.0241

<0.0241

0.169

4.15

VoRecovery

NA

NA

70.2

86.2

<0.0241 ngAnL

PFNA


<0.0298

<0.0298

0.182

4.02

VoRecovery

NA

NA

73.3

80.9

<0.0298 ngAnL

PFDA


<0.0246

<0.0246

0.0836

2.86

VoRecovery

NA

NA

34.0'='

58.1'='

NotReportecP

PFUnA


<0.0986

<0.0986

0.107

3.00

VoRecovery

NA

NA

43.4'='

60.8'='

NotReportetP

Page 93 of 207



Table 39 continued. WBMNGWB2' ,(1)

3MUMSID

£06-0549-1538

£06-0549-1539

£06-0549-1540

£06-0549-1541

Description

WBMN GWB2 0 070813

WBMN GWB2DB 070813

WBMN GWB2LS 070813

WBMNGWB2HS 070813

Average Concentration (ngAnL) t VoRPD

PFDoA


<0.101

<0.101

<0.101

1.44

VoRecovery

NA

NA

* 28.5'='

NotReportetP

PFBS


<0.0795

<0.0795

0.305

5.99

VoRecovery

NA

NA

120

118

<0.O795 ngAnL

PFHS


<0.0413

<0.0413

0.259

4.97

VoRecovery

NA

NA

106

102

<0.0413 ngAnL

PFOS


<0.0245

<0.0245

0.222

4.53

VoRecovery

NA

NA

86.6

88.4

<0.0245ng^L

NA = Not Applicable * - FieM matrix spike recovery couM not be calculated as ttie sample result was not detected above ttie analytical LOQ. (1) Samples were prepared August 22,2007 and analyzed September 8,2007. (2) FieM matiix spike recovery dM not meet mettiod acceptance criteria of 100% ± 30%. (3) Sample results are not reportable since the recovery of most appropriate fieM matiix spike was <50%.

Page 94 of 207



Table 40. WBMN GW B3' (1)

3MUMSID

£06-0549-1542

£06-0549-1543

£06-0549-1544

£06-0549-1545

£06-0549-1546

Descrption

WBMN GWB3 0 070813

WBMN GWB3DB 070813

WBMN GWB3LS 070813

WBMN GWB3 MS 070813

WBMN GWB3HS 070813


PFBA


0.676

0.687

0.887

1.46

4.53

VoRecovery

NA

NA

NC

82.3

81.3

0.682 ngAnLt 1.6%

PFPeA


0.0406

0.0377

0.312

0.977

4.47

%Recovery

NA

NA

113

96.7

91.4

0.0392 ns^L± 7.4%

PFHxA


0.0445

0.0669

0.253

0.851

3.97

VoRecovery

NA

NA

85.2

85.8

84.5

0.0557 ngAnLt 40%*

PFHpA


<0.0250

<0.0250

0.271

1.05

4.70

%Recov&y

NA

NA

108

105

94.0

<0.0250 ngAnL

3MUMSID

£06-0549-1542

£06-0549-1543

E06-0549-1544

£06-0549-1545

£06-0549-1546

Description

WBMN GWB3 0 070813

WBMN GWB3DB 070813

WBMN GWB3LS 070813

WBMN GWB3 MS 070813

WBMN GWB3HS 070813


PFOA


0.150

0.149

0.392

1.00

4.36

VoRecovery

NA

NA

101

88.3

87.5

0.*50nffhii±0.67%

PFNA

Concentration JngAnL)

<0.0298

<0.0298

0.197

0.788

3.93

VoRecovery

NA

NA

79.3

79.3

79.1

<0.0298 ngAnL

PFDA


<0.0246

<0.0246

0.0810

0.499

3.16

VoRecovery

NA

NA

32.9' '

50.7"'

64.2'"

NotReportecP

PFtAiA


<0.0986

<0.0986

0.132

0.636

2.95

%Recovefy

NA

NA

53.5'"

64.5'"

59.8'"

<0.0986ng>4n/.''

Page 95 of 207



Table 40 continued. WBMN GW B3' (1)

3MUMSID

£06-0549-1542

£06-0549-1543

£06-0549-1544

£06-0549-1545

£06-0549-1546

Description

WBMN GWB3 0 070813

WBMN GWB3DB 070813

WBMN GWB3LS 070813

WBMN GWB3 MS 070813

WBMN GWB3HS 070813

Average Concentration (ngAnL) t VoRPD

PFDoA


<0.101

<0.101

<0.101

0.217

1.54

VoRecovery

NA

NA

* 21.4'"

30.4'"

NotReportecP

PFBS


0.407

0.406

0.721

1.69

7.31

VoRecovery

NA

NA

124

126

136'='

0.407 ngAnLt 0.25%

PFHS


1.35

1.37

1.67

2.42

6.63

VoRecovery

NA

NA

NC

108

108

1.36 ngAnLt 1.5%

PFOS


0.139

0.136

0.374

1.08

4.98

VoRecovery^

NA

NA

92.3

92.0

94.5

0.138 ngAnLt 2.2%

NA = Not Applicable NC = Not Cak:ulated - Endogenous sample concentiation is greater than 2x spike level. * - FieM matrix spike recovery couM not be calculated as ttie sample result was not detected above ttie analytical LOQ. (1) Samples were prepared August 22,2007 and analyzed September 8,2007. (2) The relative percent difference (RPD) did not meet mettiod acceptance criteria of £20%. (3) FieM matiix spike recovery dM not meet mettiod acceptance criteria of 100% ± 30%. (4) Sample results are not reportable since the recovery of most appropriate fieM matiix spike was <50%. (5) The analytical uncertainty has been adjusted for PFUnA to 100% + 46%.

Page 96 of 207



Table 41. WBMNGWB4' (1)

3MUMSID

£06-0549-1547

£06-0549-1548

£06-0549-1549

£06-0549-1550

£06-0549-1551

Descrption

WBMN GWB4 0 070813

WBMN GWB4DB 070813

WBMN GWB4LS 070813

WBMN GWB4 MS 070813

WBMN GWB4HS 070813


PFBA


1.38

1.39

1.54

3.42

9.28

VoRecovery

NA

NA

NC

86.0

83.4

1.38 ngAnLt 0.72%

PFPeA


0.320

0.345

0.588

2.84

9.29

VoRecovery

NA

NA

105

103

92.4

0.332 ngAnLt 7.5%

PFHxA


0.545

0.547

0.719

2.35

8.04

VoRecovery

NA

NA

74.7

77.9

80.9

0.546 ngAnLt 0.3r/o

PFHpA

Concentration (ngAnLJ^

0.254

0.232

0.454

2.20

7.89

VoRecovery

NA

NA

84.4

78.3

76.5

0.243 ngAnL± 9.1%

3MUMSID

£06-0549-1547

E06-0549-1548

£06-0549-1549

£06-0549-1550

E06-0549-1551

Descrption

WBMN GWB4 0 070813

WBMN GWB4DB 070813

WBMN GWB4LS 070813

WBMN GWB4 MS 070813

WBMN GWB4HS 070813


PFOA


2.07

1.90

2.14

3.82

8.67

VoRecovery

NA

NA

NC

76.2

69.4

1.98ngAnLt 8.6%

PFNA


<0.0298

<0.0298

0.140

1.81

5.81

%Recoveiy

NA

NA

56.4'^'

72.9

58.5'^'

<0.0298ngî.''

PFDA


<0.0246

<0.0246

0.0382

1.19

4.74

VoRecovery

NA

NA

15.5' '

48.4'"

48.2'"

Not Reported*'

PFUnA


<0.0986

<0.0986

<0.0986

1.25

4.94

VoRecovery

NA

NA

50.7'"

50.1'"

NotReporfe</^

Page 97 of 207



Table 41 continued. WBMN GW B4' i ( i |

3MUMSID

£06-0549-1547

£06-0549-1548

£06-0549-1549

£06-0549-1550

E06-0549-1551

Descrption

WBMN GWB4 0 070813

WBMN GWB4DB 070813

WBMN GWB4LS 070813

WBMN GWB4 MS 070813

WBMN GWB4HS 070813

Average Concenti-ation (ngAnL) ± VoRPD

PFDoA


<0.101

<0.101

<0.101

0.463

2.39

VoRecovery

NA

NA

* 18.3'"

23.6'"

Not Reported'*

PFBS


3.75

3.80

4.15

6.68

15.1

VoRecovery

NA

NA

NC

114

111

3.78 ngAnL± 1.3%

PFHS


11.7

11.5

12.1

13.7

20.7

VoRecovery

NA

NA

NC

NC

93.0

11.6ngAnLt1.7Vo

PFOS


1.73

1.63

1.95

4.11

11.8

VoRecovery

NA

NA

NC

94.8

98.7

1.68 ngAnLt 6.0%

NA = Not Applicable Not Calculated - Endogenous sample concentration is greater than 2x spike level. * - FieM matiix spike recovery couM not be calculated as the sample result was not detected above the analytical LOQ. (1) Samples were prepared August 22,2007 and analyzed September 8,2007. (2) Field matiix spike recovery dM not meet mettiod acceptance criteria of 100% ± 30%. (3) Tiie analytical uncertainty has been adjusted for PFNA to 100% ± 44%. (5) Sample results are not reportable since the recovery of most appropriate fieM matiix spike M/as <50%.

Page 98 of 207



Table 42. OKMNGWW203 (1)

3MUMSID

£06-0549-1552

£06-0549-1553

£06-0549-1554

E06-0549-1555

Descrption

OKMN GW W203 0 070809


OKMN GWW203 LS 070809

OKMN GWW203 HS 070809


PFBA


0.294

0.326

0.546

15.2

%Recoveiy

NA

NA

99.7

314'"

0.310 ngAnLt 10%

PFPeA


<0.0356

<0.0356

0.240

19.0

VoRecovery

NA

NA

99.0

392'"

<0.0356 ngAnL

PFHxA


<0.0232

<0.0232

0.182

14.1

VoRecovery

NA

NA

78.5

304'"

<0.0232 ngAnL

PFHpA


<0.0250

<0.0250

0.225

19.2

VoRecovery

NA

NA

90.0

384'"

<0.0250 ngAnL

3MLMSID

£06-0549-1552

£06-0549-1553

£06-0549-1554

£06-0549-1555

Descrption

OKMN GWW203 0 070809




Average Concentrathn (ngAnL) ± ^RPO

PFOA


0.186

0.210

0.399

16.6

VoRecovery

NA

NA

83.5

341'"

0.198 ngAnLt 12%

PFNA


<0.0298

<0.0298

0.139

17.0

%Recovefy

NA

NA

56.0'"

342'"

•<:0.0298ng^L''

PFDA


<0.0246

<0.0246

0.0545

10.0

VoRecovery

NA

NA

22.2'"

203'"

NotReportecf^

PFUnA


<0.0986

<0.0986

<0.0986

11.5

VoRecovery

NA

NA

• 233'"

NotReportecP

Page 99 of 207



Table 42 continued. OKMN GW W203' (1)

3MLfflfS/0

£06-0549-1552

£06-0549-1553

£06-0549-1554

£06-0549-1555

Description

OKMN GW W203 0 070809





PFDoA


<0.101

<0.101

<0.101

4.45

VoRecovery

NA

NA

* 87.9

Not Retorted*'

PFBS


<0.0795

<0.0795

0.300

23.8

VoRecovery

NA

NA

118

469'"

0.0795 ngAnL

PFHS


<0.0413

<0.0413

0.268

21.0

VoRecovery

NA

NA

110

429'"

O.0413 ngAnL

PFOS


0.614

0.614

0.804

20.7

VoRecovery

NA

NA

NC

392'"

0.614 ngAnLt 0%'

NA = Not Applicable Not Calculated - Endogenous sample concentiation is greater tiian 2x spike level. * - FieM matrix spike recovery couM not be calculated as ttie sample result was not detected above the analytical LOQ. (1) Samples were prepared August 27,2007 and analyzed September 8,2007. (2) Field matiix spike recovery did not meet mettiod acceptance criteria of 100% + 30%. (3) Tiie analytical uncertainty has been adjusted for PFNA to 100% ± 44%. (4) Sample resutts are not reportable since the recovery of most appropriate fieM matiix spike was <50%. (5) It appears ttiat ttie high FMS may have been spiked in enor. Since ttie tow FMS for PFOS was prepared at a level ttiat was not appropriate as compared to the sample concentration, the

analytical uncertainty has been adjusted for PFOS to 100% ± 392%.

Page 100 of 207



Table 43. WBMN GW MW2' (1)

3UUMSID

£06-0549-1463

£06-0549-1464

£06-0549-1465

£06-0549-1466

£06-0549-1467

Descrption



WBMN GW MW2 LS 070809

WBMN GW MW2 MS 070809

WBMN GW MW2 HS 070809 dil 1:20

Average Concentratran (ng/rnL) t %RPD

PFBA


81.2

75.6

-89.3

143

VoRecovery

NA

NA

-NC

68.3'"

78.4 ngAnLt 7.1%

PFPeA


9.82

9.33

-19.6

100

VoRecovery

NA

NA

-103

93.2

9.58 ngAnLt 5.1%

PFHxA


8.31'"

8.04'"

-15.9

84.9

VoRecovery

NA

NA

-83.4

82.8

8.18 ngAnLt 3.3%

PFHpA


3.17<"

2.62'"

2.96'"

11.8'"

96.1

VoRecovery

NA

NA

NR

89.1

93.2

2.90 ngAnLt 19%

3MUMSID

£06-0549-1463

£06-0549-1464

£06-0549-1465

£06-0549-1466

E06-0549-1467

Descrption





WBMN GW MW2 HS 070809 dil 1:20

Average CorKentration (ng/rnL) i VoRPD

PFOA


4.61

4.50

4.75

10.7

88.5

VoRecovery

NA

NA

NC

63.8'"

87.2

4.56 ngAnLt Z4%'^

PFNA


<0.0298

<0.0298

0.197

7.25

74.7

VoRecovery

NA

NA

79.3

73.0

75.2

O.0298 ngAnL

PFDA


<0.0492

<0.0492

0.119

5.13

63.8

VoRecovery

NA

NA

48.4'"

52.1'"

64.8'"

NotR^Jorted^

PFUnA


<0.0986

<0.0986

0.136

5.55

62.7

%Recovefy

NA

NA

55.2'"

52.9'"

63.6'"

<0.0986ng*nL''

Page 101 of 207



Table 43 continued. WBMN GW MW2 (1)

3MUMSID

£06-0549-1463

£06-0549-1464

£06-0549-1465

£06-0549-1466

£06-0549-1467

Descrption





WBMN GW MW2 HS 070809 dil1:20

Average Concentration (ng/mL) t VofiPD

PFDoA


<0.101

<0.101

<0.101

2.57

50.4

VoRecovery

NA

NA

NA

25.4'"

49.8'"

Not Reported^

PFBS


13.6

12.9

25.6

129

VoRecovery

NA

NA

122

114

13.3 ngAnLt 5.3%

PFHS


3.43

3.34

3.60

13.3

104

VoRecovery

NA

NA

NC

101

103

3.39 ngAnL ±2.7%

PFOS


0.0371

0.0362

0.321

8.94

102

VoRecovery

NA

NA

111

86.9

99.5

0.0367 ngAnL± 2.5%

NA = Not Applicable Not Calculated - Endogenous sample concentiation is greater than 2x spike level. - = Sample not analyzed for tliis analyte. * - FieM matiix spike recovery could not be calculated as ttie sample result was not detected above the analytical LOQ. (1) Samples were prepared on August 21 and dilutions were prepared on August 27,2007. Sample dilutions were analyzed on September 8,2007 and reported for PFBA, PFPeA and

PFHxA, Undiluted samples were analyzed on October 8,2007and reported for PFHpA, PFOA, PFNA, PFDA, PFUnA, PFDoA, PFBS, PFHS, and PFOS.. (2) FieM matiix spike recovery dM not meet metiiod acceptance criteria of 100% ±30%. (3) Samples were bracketed by a CCV for PFHxA and PFHpA ttiat dM not meet mettiod acceptance criteria of 100% ± 25%. Recovery for PFHxA was 70.8% and 65.5% for PFHpA. (4) The analytical uncertainty has been adjusted for PFOA to 100% ± 36% and PFUnA 100% ± 45%. (5) Sample results are not roportable since no recovery of most appropriate fieM matrix spike was <50%.

(

Page 102 of 207



10 Conc lus ion

Laboratory control spikes and field matrix spikes were used to determine the analytical method accuracy and precision for all analytes. Analysis was successfully completed following 3M Environmental Laboratory methods described herein.

11 Data/Sample Retent ion

All remaining samples and associated project data (hardcopy and electronic) will be archived according to 3M Environmental Laboratory standard operating procedures.

12 Attachments

Attachment A: Analytical Method Attachment B: Representative Chromatograms and Calibration Curves Attachment C: Protocol P0002561 Attachment D: Method Deviations

Page 103 of 207



13 Signatures

Report Approval:

' ^ ^ / t n Susan Wolf, 3M Principal Ar alytical Investigator Date

/^/c? ^y . William K. Reagen, Ph.D., 3M Environmental Laboratory Technical Manager Date

ClifftopflB^J^by, Ph.D., technical Review

^ - V'SCi^<>v^W Robert A^Paschke, Sponsor Representative

)Q}^hL Jaisimha Kesari, Study Director

/ o A ^ T ^ l Date

ia-fz(|07 Date

I / Date

Page 104 of 207



ATTACHMENT A: SAMPLE CHROMATOGRAMS AND CALIBRATION CURVES

Page 105 of 207

Printing Time: 15:34:00 Printing Date: Thursday, November 08, 2007



Collected by: N/A Electronic Signature: no Operator: Wolf,Susan T

Page 106 of 207




s070908a.rdb (NFPA): "Quadratic" Regression ("1 / x" weighting): y = -5.51e+003 x*2 + 5.66e+005 x + 2.21e+004 (r = 0.9993)

10 12 14 16 18 20 Concentration, ng/mL

22 24 26 28 30 32 34


Page 107 Of 207


Analysis of Woodbury Waste Site Groundwater Samples; 3rd Quarter 2007 Printing Time: 15:35:32 Printing Date: Thursday, November 08, 2007

• s070908a.rdb (PFHxA): "Quadratic" Regression ("1 / x" weighting): y =

2.2e6 ,

2.1e6-

2.0e6

1.9e6

1.8e6

1.7e6-

1.6e6'

1.5e6

1.4e6

1.3e6-

coun

ts

S I.OeS

< 9.0e5 -

a.oes -

7.0e5-

a.oes-

S.OeS-

4.0e5-

3.0e5 -

2.0e5 -

I.Oea-

0.0-

0 1 2 3 4 5 6 7

-3.47e+003 x*2 + 1.38e+005 X + 5.64e+003 (r = 0.9992)

^ ^ ^ ^ ^ ^ ^ ^

^^.^ '^^ ^^ ' '^

^//^'^

8 9 10 11 12 13 14 Concentration, ng/mL

_ ^

15

- —

16

—

17 18 19 20 21

—

22

O

- — -

23


Page 108 of 207


Analysis of Woodbury Waste Site Groundwater Samples; 3rd Quarter 2007 Printing Time; 15:36:31 Printing Date: Thursday, November 08, 2007

• s070908a.rdb (PFHpA): "Quadratic" Regression C'1 / x" weighting): y =

2.1e7-

2.0e7-

1.9e7-

1.8e7

1.7e7-

1.6e7

1.5e7

1.4e7-

1.3e7-

1.2e7-i2 i 1.1e7-g s • ' • ° ^ ^ "

"^ 9.0e6-

8.0e6 -

7.0e6

e.oea

5.0e6

4.0e6

3.0e6-

2.0e6-

I.Oee-

0.0-

y y ^

y ^

y^ y ^

X y

• /

y ^

0 1 2 3 4 5 6 7 8

-1.89e+004 x«2 + 1.28e+006 X + 6e+004 (r = 0.9978)

^ ^

^

y ^ / ^

/ ^ y ^

y ^ •

9 10 11 12 13 14 15 Concentration, ng/mL

^

16

- ^ ^

17

^ ^

18

^

19 20

^ ^

21

- - ^

22

^ ^

23

- - - - ^

24

• " " ^

25


Page 109 of 207





Page 110 of 207





Page 111 of 207


Analysis of Woodbury Waste Site Groundwater Samples; 3rd Quarter 2007 printing Time: 15:37:49 Printing Date: Thursday, November 08, 2007

s070908a.rdb (PFDA): "Quadratic" Regression ("1 / x" weighting): y = -6.54e+003 x*2 + 6.2e+005 x + 5.09e+004 (r = 0.9994)

10 11 12 13 14 Concentration, ng/mL

15 16 17 18 19 20 21 22 23 24


Page 112 Of 207

Printing Time: 15:38:11 Printing Date; Thursday, November 08, 2007



11 12 13 14 Concentration, ng/mL


Page 113 Of 207




Collected by; S/A Electronic Signature: no Operator: Wolf,Susan T

Page 114 of 207




s070908a.rdb (PFBS): "Quadratic" Regression ("1 / x" weighting): y = -2.06e+004 x»2 + 1.61e+006 x + 3.15e+004 (r = 0.9991)

5.4e7-

5.2e7-

5.0e7

4.8e7-

4.6e7-

4.4e7-

4.2e7-

4.0e7-

3.8e7

3.6e7

3.4e7

3.2e7-

3.0e7-

2.8e7-

2.6e7

2.4e7

2.2e7

2.0e7

1.8e7

1.6e7

1.4e7

1.2e7-

1.0e7-

8.0e6

6.0e6

4.0e6

2.0e6

0.0-

^ ^ ^ ^ ^ - " ^ ^ ' ^ ^ ^ ^ ^

y^ y ^

y ^

y i X /

/ /

/ /

y 7 ^

f

o

~~~~~~~~-^-.,^^^ ^~~^^-..,^

^ " ^ \ \ v

\ ^ \ ,

^ \ \ ^

\ ^ \

\ \

\ \

\

\ 10 15 20 25 30 35 40 45

Concentration, ng/mL 50 55 60 65 70 75 80

Collected by; S/A Electronic signature: n Operator: Wolf, Susan T

Page 115 Of 207

Printing Time; 15:39:23 Printing Date: Thursday, November 08, 2007



• s070908a.rdb (PFHS): "Quadratic" Regression ("1 / x" weighting): y = -1.17e+004 x*2 + 1.23e+006 x + 1.62e+004 (r = 0.9996)

3.2e7

3.0e7-

10 12 14 16 18 20 22 24 Concentration, ng/mL

26 28 30 32 34 36 38 40

Collected by: H/A Electronic Signature: no Operator: Wolf,Susan T

Page 116 Of 207




• s070908a.rdb (PFOA): "Quadratic" Regression ("1 / x" weighting): y =

2.9e7

2.8e7

2.6e7

2.4e7

2.2e7

2.0e7

1.8e7

« 1.6e7 C

! 1-4e7

1 1.2e7

1.0e7

8.0e6

6.0e6

4.0e6

2.0e6

0.0

y^ • / ^

y ^

r ^

• /

^

0 1 2 3 4 5 6 7

-1.77e+004 x*2 + 1.586+006 X + 1.08e+005 (r = 0.9979)

/ -

^ ^

^ ^

y ^

y ^ •

8 9 10 11 12 13 14 15 Concentration, ng/mL

^

16

^

17

^

18 19 20 21

^ ^

22 23

•

24


Page 117 of 207




IS M n p b N a n P a r t N w n a : C o i n T w n > : l

I S a f n p t * N M l w : ' s 0 n ) 9 0 e a 0 i r Sa inp ls lO: 'EC-a70B27-a ' F I B : - ( 0 7 l ) 9 0 S B . * j r Peak M a i m : - N F P A ' MMs(a4 : -263 .0 /21911 wnu-

ppti avtiacted curva pont* A i m o M b n : —

C a l ;

Mud i

Expa

D a t a : T i m e :

f i a d : i n d o w :

i n t . T y p e : ! ( e t e n t L o n T i n e :

H s i g h t : S t i r t T i m e : End T i m B i

1 J « 5

1 J « 5

1.2aS

12sS

1 . 1 ^

l . i a S

1J3BS

S5a4

9 i M

S504

i J M

7 J » t

7 i M

6 5 . 4

S i M

S.5e4

S i M

4 . 5 M

4 i M

3 5 M

3 0 o 4

2S»4

2Jto4

I5>4

I H M

soaojo

11 75

K » J i ! i E J ^ : ^ 5 ^ ^ 1 7 ^ ia.2B

12 13 14 15 IS IT 18 19

•ampU Type: •.jncenti-ati.jn: alculated C'lns

.elUQujn - I.3A


Page 118 of 207




I Sampl>NwnB:-s070906aO«- Sampto ID: 1.08470822-4-PMk Nvna:-NFPA- Mass(a):-363,0/21911 •rnu'

I Commanl: ^ J) ppb ntracM LCS'

:hin.j Width:

: ted RT:

Height:

End Time:

San^Nan*:-a07D9OSa10e- Sanvto ID:-E0»«54B-1Szr Fl«:-sOTOMBa.' Paak Nana:-NFPA' Ma»(*4: "263 ^219,0 amu-Con«nmt:'MBMNOWMIML0070S10- Annolalion:

?jmpl8 Inilax: ios Sample Type;

N M a q ,

Collected by: N/A Electronic Signature: n Operator: Wolf,Susan T

Page 119 of 207





Page 120 of 207




H S a n p l . N a n i a : - a O T 0 9 0 « a 0 4 5 - S»npte P : - L C S - 0 7 0 B 2 2 - r F f c : - r t 7 0 9 0 « a . > * r 1 P««1 :N»™: -PFBA- M B M ( « s ) : - 3 1 3 i K i e 9 f l a ™ -

Saraple T ^ f e : QC C o n c e n t i a t i o n : 4 . 7 3 n.,/ inL C a l c u l a t e d Cone : * . i Z n-j/mL 7-4*4

A c q . T i m e : l ^ : i l : 1 f > j ^ ^

H u d i f i a d : Mu P r i - ' j , . • . I q o r i t l m i : I n t e l l i Q u j n - l ^ A 7 I I B 4

J i ^ o t h i n J v J d t K ; 3 ^ ' " ] " p o i j t , « * -

E>:pectef l RT: 7 . 2 2 m i n B * K 4

K : t ; J l u r T i m e - " 1 ' - . i n ^ ' ^ A i -e . . : I . " 0 « 1 2 j ' " c o u n t 3 s j t o 4 H e i g h t : H 1 0 0 . cps

i ^ i ^ ' ;:ii :;: 5,ae4

S J M

S A a 4

S J « 4

SOeA

4 i « 4

4JSe4

4.4a4

* J i a 4

4.0a4

1 ,« 3 . 4 B 4

3 J a 4

3 i M

2 3 » 4

2.«e4

2 A M

2 ^ 1 4

2 I M

1JB»*

l * a 4

1.4e4

1 2 * 4

l i W

BOOOA

eoooi)

4000,0

2000,0

' "

6

•

1 2 3 4 5 1

»

15,85.15.96 19.34

Fl

^•*-*- * : * S M M ^ ' « • « l\

• 9 10 11 12 13 14 IS 16 17 -xJV

18 19

I S>mpbNB[<w: 'dTD908a109- Sampte I D : - E O & O S ^ - I S I T Fh:-«0T09OBB.v»ir I PMkNanMi : -PFBA- MaM(B*) : -213JV1S9.Damu-• C o n w n a n t : - V W M N G W M W 4 t . 0 0 7 0 8 i a ' A n n o l a t o n : -

C a l c u i a t e d C o n e : O . E l . l ng / i=L 1 . 4 ^ A c q . D j t e : " / " / i O O T

H . d i n e d : ^ ^ Y e , ^ ^ ^ ' - ^ ^

E x p e c t e d KT : 7 . 2 2 m i n U3B R e l a t i v e RT: No I J i M

I n t . T y p e : M<,nuai R e t e n t i o n T i ^ e : e . ^ ^ » i n A r e a : 2 2 1 9 3 0 c o u n t s ' " " " H e i g h t : l i € 0 0 . c p » S t j r t T i m a : € . 6 0 i-în End T i m s : 7 . < 1 i n i n ^ 2 • *

1.1a4

1.104

1 J M

9500 J>

9000,0

asoo.0

0000,0

75O0J>

* TOOOi)

S esooii

60D0J>

55OO.0

SOOOJJ

4500JI

4 0 0 0 i l

3500.0

3000 J)

2S0OJ3

2 0 o a j i

1500,0

1000J)

500J)

,w\MAvvV^4a*A* .-w jJ " • " 1 2 3 4 5 6

M * ..Ji /w ff r i f A ^

lk llltVIMm

/\iA r W ^ 1

\ / T

>, vv \ r B 9 10 11 12 13 14 IS 16 i V I B 19 j

' Collected by: N/A Electronic Signature: no Operator: Wolf,Susan T

Page 121 of 207




Collected by: N/A Electronic Signature: no Operator: Wolf, Susan T

Page 122 of 207

Printing Time; 15:48:07 Printing Date; Thursday, November 08, 2007



I P a a k N H n a : - P F B 5 - M B W ( « ) : - 2 9 6 . 9 / 7 9 . 9 a inu ,29SA99.0 amu-• C i ) i nmanb -SJ )ppbv [ t i a c lM l t J :S - A n n o t o l i o n : -Samp le I n d e x : 4 ^ Samp le T^-pe- CC C o n . ^ e n t n t i o n : 1 5 . ? n., /mL C a l ; u l a t e d Cone : U . = n., /mL ^ * ^ A c q . D a t e : " / i / i a a i ^ j ^ A c q . T i m e : 16 :2 . :C l fe

2 . 7 r t M u d l f l e d : Y B i KT Wind . , ^ . : JO.O s e c 2 * a 6 E x p e c t e d KT: 1 2 . J m i n Use R e l a t i v e RT: Ho ' • ' * * '

2 5 « « I n t . T y p e : > U n i i s l R e t e n t i o n Tir.Le: 1 2 . 2 m i n 2 5 a 6 A i 6 d : 1 9 1 7 0 6 ^ 1 C J U n t s H e i g h t : 2 8 0 0 0 0 0 . c p s ' • * "

End'TimiT" ! - : o : ! : ; ^ ^ 2 J a 6

Z J a 6

2 , 2 B 6

2 2 « 6

2.1a<

2.1a6

2 f l « e

Z i M

1Sa6

I B a e

I jSoe

1.7a6

1.7*6

1 £ a 6

1 J B « 8

1 £ « 6

% ' ^ j 1,4*6

1 1.4a« " 1 J « 6

1 3 * 6

\ 2 t B

U r t

l . l a G

1.1a6

1j0a6

9 £ « S

gDaS

a £ a S

S i laS

7 J a S

TJtoS

6 £ a S

ej>a6

5,5aS

SJtaS

4 5 a S

4 j ) a 5

3 3 * 5

3 A «

2 J 5 B 5

2Da5

1 5 a 5

IJ IaS

SJto4

1 2 3 4 5 6 7

13,21

B 9 10 11 12 13 14 15 16 17 16 I B

• S>ff l |>l*NB(lw:-sOT090eal09- Sample I D : - E 0 M 5 4 9 - 1 5 2 5 - Ffc:-»0709O6a.v»»r 1 Peak Name: T F B S ' M a a a f M ) : ' 2 9 6 « 7 9 . B aR»,2S8»BSJ] amu-

Samp le T / p e : 'Jnl:n.j-,jn O n c e n t r a t i o n : N/ . ' , g j ^ C a l c u l a t e d C o n e : • ) , 152 n g / n L h c i . D a t e : t / f l / i O O T 5.1»4 A c , . T i m e : H : M : i 1

S J M

RT HincJi,w: JO.O s e e * * ^ E x p e c t e d KT: 1 2 . 3 ™in . ^ Use R e l a t i v e RT: No ' " " ^

4.7a4 I n t . T y p e : H a n u s l R e t e n t i o n T i m e : 1 2 . 2 m i n 4 i « 4 M e a : 313547 c o u n t s H e i g h t : SJJOO. c p s 4 5 * 4

E n ^ T i m e r ' 1 2 : s ^ i n 4 A > 4

4 J « 4

4 ,2*4

4 .1*4

4 .0*4

3.9«4

3.e»4

3.7*4

3,6*4

3 5 * 4

3.4*4

3 J * 4

3.2*4

3.1*4

S J M

2.9*4

2 J * 4

1 2.7-4

f 2J^ i S 2 5 . 4

2.4*4

2 J * 4

2.2*4

2 .1*4

2 J ) B 4

1,0*4

1 J * 4

1.7*4

1.6*4

1.5*4

1.4*4

1 J * 4

1.2*4

1.1*4

1 i>*4

900011

Booajo

7000J)

GODOXI

SOOOJD

4000J)

3000.0

2000J)

1000.0 ft " i i i i i

1 A J A. . . /V ^ . . . . P ^ J V.„ ,^,>„, . -,~.«»-,^..^

6 T B 9 10 11 12 13 14 IS W 17 18 19

^ ^ ' ^ • i - * - u Collected by: N/A Electronic Signature; n Operator: Wolf,Susan T

Page 123 Of 207




I SanvlaMBnn:'s0ro90aa0ir Sanipta U:-EC-070627-S- Fla: PaaltNanw:TFDA* MaM(a*):-512.9f46e.6 amu-Conanant:'1 J) ppb Bxtractad curva poT

Sample Type

Cal;Li lated (

Expettsd RT:

Retention Time

Height; Stirt T End Tim

1J.S

IJaS

12aS

UaS

l.laS

l.leS

IJteS

95*4

8.0*4

B£*4

aj)*4

75*4

1 T*4

| . ^ 6JM

55*4

S.OM

4J*4

4J>M

35*4

3J(*4

25*4

2J)*4

15a4

1i(-4

5000JI

16 04

„ 5 6 7 1 9 11 12 13 14 15 16 17 16 19


Page 124 of 207




I Samiri I PaakI

Cal :u l a t Acq- Dat Acq. Tin

Hudified

-Ba7D90Ba045- SMnpto 10:-LCS-07D622-4- Fk:-a0709OSa.wi Mama:-PFDA- MasB(es):-S12J/466.B amu-

-5J1 ppb BXtrartaif Lf "

S.6aS

5.5aS

5.4*5

53a5

5.2*5

5.1*5

5As5

4Sa5

4.Sa5

4.7*5

4A>5

45.5

4.4*5

4J85

4.2*5

4.1*6

4J>*S

3A*5

iicS 3.7*5

3.6*5

35*5

3.4*5

3JaS

3.2*5

3.1*5

3XMS

2S*5

2.8*5

2.7*5

2.6a5

25*5

2.4*5

23*5

2J*5

2.1*5

2ila5

lJa5

15*6

1.7«5

15a5

15a5

1.4*5

1J*S

1J*5

1.1*5

1.0*5

9J>*4

SAA

75a4

GJ>a4

5 , 0 B 4

4 A i 4

3,0*4

2JM

I IM OJO

16 03

1 , , 15 IB 17 18

ISainf i laN«ni* : *s07090«a109- S a m p h D : - E 0 6 - 0 5 4 9 - 1 5 Z 5 - F la : - s070908a .w i r P*Bk Nam* : -PFDA- Mas»(*a) : -S12.9/4B85 a m u -C a n i n i * n t : - \ M M N O W I M H L 0 0 7 0 e i O ^ Annotat ion:

?j9iple Index; 109 Sample Type; Concent ra t ion: Calcula ted O n e :

. T ime 1 4 :

Modified: Pruc. Alqucithra: Int

Min. Peat Width: SuMthing Width: 3

Expected RT:

iQuan - IQA


Page 125 Of 207





Page 126 of 207




I Sam P..I Com

Sampta Nam*:-•07D908a04r SamplB ID: 1.CS-OT0622-4- Fla:-iO709O8a.Mir Paak Name:-PFDoA- Maaa(e4:-G13JV5Ea.7amu-Conini*nl: "SJ) ppb ailiactad LCS' Annotation: -

2i>aS

2J0SS

IJoS

15*5

15*5

15*5

1.7a5

A c q ,

Hurt i KT W

T i m e :

l e d : nduw:

•Js l R e l a t i v

I n t . T y p e :

^;r.,•,r End

T i m e : i m e ;

1.3*5

12*5

1.2*5

l.laS

S- t.laS

95a4

95*4

85*4

85M

75e4

75*4

65*4

65*4

55*4

55*4

45*4

45*4

35*4

35*4

25*4

Z5M

IS IS 17 18

I SanvtaNama:-iO709O8al09- Sanrls ID:-E06O549-152S' Fh:-tOTDBOSajufT Paak Mam*:-PFDoA- MBM<*C):'6135f56B.T amu' Comntant: -VUBMN QWMWMt 0 070810-


Page 127 of 207




[ SaR^Mana:-ta70906B0ir Samp4a D:-£04)70827-8- Fla:'sOTOOOSa.w^ •allNama:-PFHpA- Maaa<a4: "3635^195 amu,3635/16S5amu,H35/1l95

I Comnianl:'15ppba>tracladcU'vapainr Ann<âft>n:~ "ndeK: n

Collected by: S/A Electronic Signature: no Operator: Wolf,Susan T

Page 128 of 207





Page 129 of 207




I SBmplaHMn*:-a070906aOir Sample ID:-EC-070827-8- Fla:-BOTOSOea.wiir P«ai[ Nama:-PFHS- MaBa<*4:-399.0^5 amu,399.0»S5amu-Commant:-15ppbailladadcurvspaiM- Annc4atian:~

Collected by: N/A

Electronic Signature: n Operator: Wolf,Susan T

Page 130 of 207




ISampIg Nama;-«070a08a04S- Sampb ID: TCS-OT0622-4' FlB:'sa709O8a.«wr PaaliNama:-PFKS- Maaa<a*): "3995/795 amu,399JVBS.O amiT CamnwM:-55 ppb sltmclKJ LCS' Annolalion: "

Sample Index: 45 Sample Typ*: CC Concent ia t ion: 9.26 ng/mL Ca l ;u la ted cono; 9.22 n.j/mL

ftetenCit.n Ti Manual

.e: i l . j

SamplaNama:-rt70g08a10r SanTtalD:-E06-0549-152S- Fla:'aOTOgOBa.wir Psali Nam*:-PFHS- Ma«a(**): -3995/795 mnt3m.W99S) Commenl:-WBMN6WIAAMt.0070810- Annotalion:~

Hlfl>.rittim: Percentage:

Eealc-Split. Facte Report Latoej t ts Min- Feal: Heiqtit: Kin- Peat Width: îH'Ji'thing Width:

5 6 7 8 9 10 11 12 13 14 15 16 17 IB 19


Page 131 of 207




ISampI* Nam*: ->07D! Paak Nama: -PFHxA-Commant -15 ppb *<

->07D90BaOir Sampi*IO:-EC4}70827.«- fl*:-aOTOOOSa-t -PFHKA- Iriaaa(*a):-3135/1195anw.313a2e95amu-

BitiwlMt cun* pomr *nnota(ian:~

Sample TVTB: Standaid Con=ent ia t ion: 0.=27 nj/nL

Acq. Date: Acq. Time:

Modified: KT Window:

EKpetted KT: Use Relative RT

Int. Type: Retention Time:

Height:

B/a/;oo 00:31:2

Vei

Mo

13.> 3&fi53 23300.

n.,/mL

nin

cps

2.4*4

2-3*4

35*4

2.2*4

2.2*4

2.1*4

1.1*4

5 S 7 a 9 10 11 12 13 14 15 16 17 18 19

Expected RT:

1 2 3 4 5 6 7 8


Page 132 Of 207




I San«rf*NMn*:'s07090ea045- Sampb 10:1.05-070622-4- Fla:-•070908a.wir Paak Name:-PFftiA- Mas8(aB):-3135ni95amu,3135/2695amu-CommaM: ^ 5 p ^ oxliaclad LCS' AnnoWion: "

SanvlaNan«:-s070908al09- Sampla »:-E06-OS«-152r FIs:'•070908a.wir Paak Nam*:-PFHtA* IAK*(*4:-313.(V11S5amu,3135n695amu-

~ lifti OW liMML 0 DTOaiO-

t t a t i . i n ;

e d : Alqorit l iB:

e a t Width: inq Width:

ed RT:

yps :

Time-

l{%l°Ti

In te l l lQuan -

0.00 3e ; i point

l i . i min No

VQllay

iV.O min 13.6 min

mL

I 2 A

2950

2900

2850

2B00

2700

2650

2550

2450

2400

2350

2300

2250

22W

2150

2100

Collected by: N/A Electronic Signature; no Operator: Wolf,Susan T

Page 133 of 207




Page 134 of 207



I Sanîl* Mama:-ia7D90Ba045' Sampk ID:-LCS •070822-4- Flo:-M)709O8a.wir Pa*k Nama:-n'NA- Man(*4:-463.0/4185 amu-

it:"55ppb*WnK«*<tLr- "

: a l - ;ma t

\cq. Tin

1 ^

55aS

55*5

5.7*5

55*5

55*5

5.4*5

55*5

5.2aS

5.1*5

55*5

45*5

45*5

4.7*5

45a5

45*5

4,4a5

45*5

4i«5

4.1*5

45*5

35*5

35a5

3.7.5

35*5

35*5

3.4*5

35*5

3J2*5

3.1.5

35*5

25*5

25*5

2.7*5

25a6

25a5

2.4*6

2.3*5

22*5

2.1*5

25*5

15*5

15*5

1.7*5

15*5

15*5

1.4*5

15*5

1.2*5

1.1*5

15*5

95*4

85*4

7-0*4

65*4

55*4

45*4

35*4

25*4

15*4

15

14,26

54

10 11 13 13

I SanvbNanw:-t07O9O6a1O9- Sample ID:-EO641540-1525- FIs:-t070SaeB.w«r Paak Nam*:-PFNA' hta*s<as):'4635/4185 amu' CommBntlAGMNOWMMMLOOTDelO' Annotattan:

'ample Index: 10!<

Calculated C

Type: iun Tims

Height: Stait Time: End Time:


Page 135 of 207




Page 136 of 207




I Sample Nama:->070908a04S- Sample C: -LCS-070622-4- F la : - lOTOgoea .w i r • Paak N w n a : - P F O A - I M a H ( * c ) : ' 4 1 3 5 ) 3 6 8 5 amu , 4 1 3 . m 1 9 5 amu.413 A 1 6 9 5 amu-• C i ) m m B n l : - 5 5 p p b B M n e i a d L C S - A n n a t a l i o n : -San,pl8 i n d e x : * 5 Sa»,ple T y p e : CC C o n c e n t i a t i o n : t . ' - i n . j /m l . C a l : : u l a t e d C o n ^ t 4 . 7 9 n - j / n L 1 1 0 * 6 A c q . D a t e : o / * / : o o T A- ;q- T i m e : 1 6 : 2 7 06 1 5 6 * 6

M o d i f i e d : Nu 1 ^ » * P r u i . . " . I g u r i t h m : I n t a l l i O u a n - M C H 1f l4a« ( J u U a P e r c e n t j u e : 50

P e a l : - S p U t . F a c t o i : 5 R e p o r t L a i j e s t ?ealc: No 1 5 0 * 6

iil: I'.'.i S " ' °'°m I'.l " °^ K r i S H d " : " " " " 10.o' . . „ " ' ' ° " ' * " E x p e u t a d KT : 1 5 . 0 n l n 9 , 4 0 B 5

'Jse R e l a t i v e R T : No ^ ^ ^ ^ ^

I n t . T y p e : V a l l e y g j o ^

A c e i : 72e654S ' c o u n t s 8 5 0 ^ H e i g h t : 1 1 2 0 0 0 0 . c p s S t a r t T i m e : 14 .S m i n • 5 0 B t i

End T i m e : 1 5 . J m i n 8.40*5

B.20a5

8 5 0 a 5

7 5 0 * 5

7 5 0 * 5

7.40*5

7.20*5

7 5 0 * 5

S50*S

6 5 0 * 5

Sj40a5

6 2 0 i S

« 5 0 a 5

Ss«« f 550*5

1 5.4085

5.20*5

5 5 0 * 5

4 5 0 * 5

4 5 0 * 5

4.40a5

4 2 0 * 5

4 5 0 * 5

3 5 0 * 5

3 5 0 a 5

3.4a*5

3 2 0 * 5

3 5 0 * 5

2 5 0 * 5

2 5 0 * 5

2.40>5

2 2 0 * 5

2 5 0 * 5

1 5 0 * 5

150e5

1^40*5

1 2 0 t 5

1 5 0 * 5

8 5 0 * 4

850>4

4 5 0 * 4

2 5 0 * 4 0 5 5

" • " 1 2 3 4 5 6 7 8

145<k

^ 9 10 11 12 13 14 15 16 17 18 19

I Peak Mama: T F O A - M a a i < * a ) : ' 4 1 3 5 0 6 8 5 a m u , 4 1 3 5 a i 9 5 amu,4l35/16S.O amu* • C o m m e n t : - V W M N G W M W 4 L 0 0 7 0 e i O - A n n o t a t i o n : -S i m p l B I n d e K : lOS S a m p l e T y p e : UnLnown C o n s e n t i i t i . j n : N/A C a l c u l a t e d O n e : < 0 , ^ , 5 ^ A c q . D a t e : < i / « / ;OOT A c . , . T I M : H : 5 1 : i T l I M a 4

M > , d i r i a d : Nu 1 5 2 * 4 P r u = . A l g o r i t h m : I n t e l l i Q u a n - 1*311 M u i s e P e r c e n t a g e : 50 • . u u w E a s e . S u b . H i n d < . v : 1 .00 m i n 9800.00 P e a k - s p i l t . F a c t d i : 5 K e p o i t Larc fe .o t P e a l : : No 9 6 0 0 5 0 M i n . Pea l ; H e i g h t : O.OO c p a K i n . Pea l : H l d t h : 0 . 0 0 s e c 9 4 0 0 5 0

K r w l n d o ^ : " ' ' * ' " i O . o ' . e c " ' ' ' " " « " • "

U s e ' R e l a t i v e RT- l l \ ' ° " ' " ' ™ ' - "

R e t e n t i o n T i m e : 1 5 . 0 m i n 8800.00

H e i g f i t : W i B . c p s > * " • « ^ ^ f i / i ^ e : U y m i n , j oo_oo End T i m a : I S . Z m i n

8 0 0 0 5 0

780050

7 6 0 0 5 0

7 4 0 0 5 0

7 2 0 0 5 0

7 0 0 0 5 0

6 8 0 0 5 0

6 6 0 0 5 0

B4O05O

6 2 0 0 5 0

6 0 0 0 5 0

5 8 0 0 5 0

1 5 6 0 0 5 0

j ^ 5 4 0 0 5 0

1 520050

~ 5 0 0 0 5 0

4 8 0 0 5 0

4 6 0 0 5 0

4 4 0 0 5 0

4 2 0 0 5 0

4 0 0 0 5 0

3 8 0 0 5 0

3 0 0 0 5 0

3 4 0 0 5 0

3 2 0 0 5 0

2 8 0 0 5 0

2 5 0 0 5 0

2 4 0 0 5 0

2 2 0 0 5 0

2 0 0 0 5 0

180050

160050

140050

120050

100050

8 0 0 5 0

8 0 0 5 0

4 0 0 5 0

2 0 0 5 0

^ . WA>A..jhinMM,-A*-vA^^ " ' " 1 2 3 4 5 6

\

J[ ^lKM/f\f\/

1

1 J

i, W

. 1 LHi ^

t n \ fW

w , 1 } 1 1 v k r ' 1

, Y , , , jJfUV AyiUl/*^ \ tiWWWir I

^ Y T V ^ l ^ 7 8 9 10 11 12 13 14 15 16 17 18 19

Collected by; N/A Electronic Signature: no Operator: Wolf,Susan T

Page 137 Of 207




I SanvliNwna:-a070908aOir Sampb IO:'EC-070e27-8- Ffe:-•a70908a.wir Paak Nama:-PFOS- MMa(*a):-4985/805 afflu.49a 5^92 amu.49B5/1305 amu" CcHnmant:-15ppbi ~

ample Index:

i t io i n.j/ml Ca l ;u l a t ed Cone: 1. Acq. Date: 1 /4 / : Acq. Time: Oa-.i"

Ho.llfled: Ye

Use Rela t ive RT: No

I n t . Type: Hanu

He"ht: ''^lllL

End Time: 15

n.j/

1

cp..

Hi.

5 j j

1

65*4

65*4

6.4*4

62a4

65a4

S5«4

S5a4

S.4*4

52*4

55*4

45*4

45a4

4.4«4

4.2a4

45*4

35M

35*4

3,4*4

32*4

35a4

25»l

25*4

2/*a4

22a4

25a4

15«4

Collected by: K/A Electronic Signature: no Operator: Wolf,Susan T

Page 138 of 207




I I I Samp*. Nam*:-rt)7090aa045- Sampte P:-LCS-070a22-C I P*al[Nan»:-PFOS- Ma«a(,.):-498*805 • m u . 4 9 8 5 « 2 • CcHnmanl:-S5ppfaaxlracladLCS- AnmlatiaFi:-Sait^plB IndeK: i b Sample Type: CC Concent ra t ion : 4. »0 n.j/mL Calcu la ted Cone: l . s ? n. j /n i _ . . Acq. Date: 1/a/ :007 -^•*=* Acq. Time: 16:27:06

H u d i f i e d : NO 2 * 5 Pruc. A l go r i t hm : I n t e l l l Q u a n - HQII

Base' lub^Wlndow; l ! o 0 min 25*5 Pea! : -Sp l i t . Fac to r : i Report Largest teak : No Min. te i ) t Heiq l i t ; 0.00 cps 2.7*5

Sm.juthlnj Width: i pu in t? RT Window: JO.O sec 25*5 Expected RT: 15.5 min Use Re la t i ve RT: No

25*5 I n t . Type: Va l l ey Retent ion Time: 15.5 min Area: ^64^606 counts 2JteS Height ; 30=000. cps

End'^Timer' I f i l o min j j ^

22a5

2.1*5

25aS

15*5

15*5

1.7a5

1 ' ^ f l5aS

1.4*5

15 .5

12*5

1.1*5

15*5

95*4

S5e4

75*4

65*4

55*4

45*4

35*4

25*4

15*4

F l , : - r t 7 0 9 0 6 a . ^ amu,4985f1305amu-

1 2 3 4 5 6 7 8 9 10 11 12 = _ . Tima.mh

15

1555^

5 2

1

15.19v. l

13 14 i s 16 17 18 19

|S»,^Nam.:- ;07090ta109-^SSS|a.1b:-E«M)54»-1525- Fi»:-.OTTOOS-.-r • P*akNaffl*:TFOS- MaM(*4: '4985005 aln<.4085S92 Bmu,4985/1305 amu* • CommBnt:-WBMNCWMAMLQ07DalO^ AimotaHon:-Fample Index: lOS Sample Type: Unknown

Acq? Data: ' " " ' 1 /« / i007 " ' " 7000 .Acq. t i m e : 14:51:^1

M o d i f i e d : Ye» » " RT Window: JO.O sec EJipaEted KT: 15.5 a in 6600 Uje R e l a t i v e RT: No

I n t . Type: Kaniial M M ke tan t l on Time: 15.5 min

S t j r t Time: 15.1 min

End Time: IS.B min fiOOO

5800

5600

5400 5200

5000

4800

4600

4400

4200

4000

f "" 1 3400

3200

3000

2800

2600

2400

2200

2000

1B00

1600

1400

1200

1000

800

600

400

200

• A . . . i ' 2 3 4 'S* i 7 8 9 10 11

Tkni.(nin

...,..,.»-rtJ^Wl.,^. 12 13 14 15 16 17 18 19


Page 139 of 207

Printing Time: 15:4B:11 Printing Date: Thursday, November 08, 2007



I Sanvti Nairn:-aOTOOOeaOir SampI* ID:-£0-070627-6- Fh:-a070g08a.Mr I Paak Nam*:-PFUnA- Man(M}:-S63.WS18.7amu-

:'15 ppb extractad curva po'

O.SSf n.j/mL

Proc. Aiguri

. Peak Hidth;

Rela t ive RT:

Type:

4.4*4

45*4

42*4

4.1e4

45a4

35*4

35*4

3.7a4

35»<

35a4

3.4*4

35a4

32*4

3.1*4

J5a4

25*4

25*4

2.7*4

35*4

25*4

2,4a4

25*4

22e4

2.1*4

25*4

15*4

15a4

1.7*4

15*4

15*4

1.4*4

15*4

12*4

1.1*4

15*4

90005

80005

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Page 140 of 207




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Page 141 of 207



ATTACHMENT B: EXTRACTION AND ANALYTICAL METHODS

Page 142 of 207

current 1 ^



3IVI Environmental LaboratDiy

Method

Determination of Perfluorinated Adds, Alcohols, Amides, and Sulfonates In Water By Solid Phase Extraction and High Performance Liquid

Chromatography/Mass Spectrometry

Method Number: ETS'8-1S4.3

Adoption Date: 28 Apr 2000

Revision Date: Upon Signing

Effective Date: O t f z H l o i

Approved By:

O f i i J J ^ : ^ j ^ . — . ~ ^ . . . William K. Reagen Date Manager

ETS-8-154.3 Page 1 of 20 Determination of Perfluorinated Adds, Alcohds, Amides, and Sulfonates In Water By Solid

Phase Detraction and High Performance Liquid Chromatography/Mass Spectrometry

Page 143 of 207

rom



1 Scope and Application

This method describes the extraction of target analytes from water matrices using solid phase extraction (SPE) followed by separation, identification, and quantitation using high-performance liquid chromatography mass spectrometry (HPLC/MS) or tandem mass spectrometry (HPLC/MS/MS). This method has been validated for perfluorooctane sulfonate (PFOS), perfluorooctane sulfonylamide (FOSA), and perfluorooctanoate (PFOA) in groundwater, surface water, and drinking water samples. This method is considered a peifonnance-basec/method and may be applied to the determination of other perfluorinated acids, alcohols, amides, and sulfonates in similar matrices, as long as the defined QC elements are satisfied and with the understanding that the method is not validated for compounds outside the scope of the original protocol.

This method is based in part on the 3M Environmental Laboratory report E01-0454, "Method of Analysis for the Determination of Perfluorooctane sulfonate (PFOS), Perfluorooctane sulfonylamide (PFOSA), and Perfluorooctanoate (POAA) in Water", as developed and validated by Exygen Research (formeriy Centre Analytical Laboratories, Inc.). This method was originally validated using a 40 mL sample aliquot for extraction and a final elution volume of 5 mL. These volumes may be changed on a per project basis to meet the data quality objectives set forth by the project lead. Acceptable recoveries of laboratory quality control samples will demonstrate that the extraction and elution volumes do not impact the validity of the method.

Sample collection is not covered under this analytical procedure.

2 Method Summary

Water samples are collected from a site of interest and shipped to the analytical facility. Perfluorinated acids, alcohols, amides, and sulfonates are extracted from aliquots of the water samples using solid phase extraction (SPE) cartridges. The compounds are eluted from the SPE cartridge, using methanol. Separation, identification, and measurement are accomplished by high-performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS) analysis. High-performance liquid chromatography/mass spectrometry (HPLC/MS) may be used if the defined QC elements are satisfied and meets the data quality objectives outlined in the general project outline for the given project.

The concentration of each identified component is measured by comparing the MS response of the quantitation ion (or summed total of multiple ions) produced by that compound to the MS response of the quantitation ion (or summed total of multiple ions) produced by the same compound in an extracted calibration standard (external standard).

3 Definitions

3.1 SPE cartridge A column containing an open solvent reservoir, retaining frit, soriaent b)ed, retaining frit, and luer tip. The soriDent bed is bonded silica which is designed to selectively retain or elute the compounds of interest depending on the solvent conditions. The compounds of interest can be separated fi"om the water matrices and introduced into an appropriate solvent for analysis.

3.2 Analytical Sample A portion of an extracted laboratory sample prepared for analysis.

ETS-8-154.3 Page 2 of 20 Detemiination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In Water By Solid

Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry

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«d, If current, for 1



3.3 Calibration Standard An aqueous solution prepared by spiking a known volume of the Wori<ing Standard (WS) into a predetermined amount of ASTM type I water, HPLC grade reagent water, or other suitable water (i.e. matrix water), and extracting the solution according to this method. The calibration standard solutions are used to calibrate the instmment response with respect to analyte concentration.

3.4 Laboratory Dupl icate Sample (LDS)

A laboratory duplicate sample is a separate aliquot of a sample, taken in the analytical laboratory that is extracted and analyzed separately with identical procedures. Analysis of LDSs compared to that of the first aliquot give a measure of the precision associated with laboratory procedures, but not with sample collection, preservation, or storage procedures.

3.5 Field Blank (FB)/Trip Blank

ASTM Type I water, HPLC grade reagent water, or other suitable water, is placed in a sample container in the laboratory and treated as a sample in all respects, including exposure to sampling site conditions, storage, preservation and all analytical procedures. The purpose of the FB is to detemiine if test substances or other interferences are present in the field environment. This sample is also refen'ed to as a Trip Blank.

3.6 Field Dupl icate Sample (FDS)

A sample collected in duplicate at the same time from the same location as the sample. The FDS is placed under identical circumstances and treated exactly the same throughout field and laboratory procedures. Analysis of the FDS compared to that of the first sample gives a measure of the precision associated with sample collection, preservation and storage, as well as with laboratory procedures.

3.7 Field Matrix Spike (FMS) A sample to which known quantities of the target analytes are added to the sample bottle in the field or in the laboratory before the bottles are sent to the field. A known, specific volume of sample must be added to the sample container without rinsing. This may be accomplished by making a "fill to this level" line on the outside of the sample container. The FMS should be spiked at approximately 0.5-10 times the expected analyte concentration in the sample. If the expected range of analyte concentrations is unknown, multiple spikes at varying levels may be prepared to increase the likelihood that a spike at an appropriate level is made. Typically a low and a high spike are prepared for each sampling location. The FMS is analyzed to ascertain if matrix effects or sample holding time contributes bias to the analytical results.

3.8 Field Spike Contro l Sample (FSCS)/Trip Blank Matrix Spike

An aliquot of ASTM Type I water (HPLC grade reagent water or other suitable water may used) to which known quantities of the target analytes are added in the field at the time of sample collection (at an appropriate concentration to be determined by the project lead) or in the laboratory prior to the shipment of the collection bottles. The FSCS is extracted and analyzed exactly like a sample to detemiine whether a loss of analyte could be attributed to holding time, sample storage and/or shipment issues. A low and high FSCS may be appropriate when expected sample concentrations are not known. This sample may also be refen'ed to as Trip Blank Matrix Spike.

3.9 Laboratory Contro l Sample (LCS)

An aliquot of ASTM Type I water (HPLC grade reagent water or other suitable water may used) to which known quantities of the target analytes are added in the laboratory at the time of sample extraction. At least two levels are included, one generally at the low end of the calibration curve


Phase Extraction and High Perfonnance Liquid Chromatography/Mass Spectrometry

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^t c u • • ' . ' • •



and one near the mid to upper range of the curve. The LCSs are extracted and analyzed exactly like a laboratory sample to determine whether the method is in control. LCSs should be prepared each day samples are extracted.

3.10 Laboratory Matrix Spike (LMS)

A laboratory matrix spike is an aliquot of a sample to which known quantities of target analytes are added in the laboratory. The LMS is extracted and analyzed exactly like a laboratory sample to detemiine whether the sample matrix contributes bias to the analytical results. The endogenous concentrations of the analytes in the sample matrix must be detennined in a separate aliquot and the measured values in the LMS con-ected for these concentrations.

3.11 Laboratory Sample

A portion or aliquot of a sample received from the field for testing.

3.12 L imi t of Quant i tat ion (LOQ)

The lower limit of quantitation (LLOQ) for a dataset is the lowest concentration that can be reliably quantitated within the specified limits of precision and accuracy during routine operating conditions. To simplify data reporting, the LLOQ is generally selected as the lowest non-zero standard in the calibration curve that meets method criteria. Sample LLOQs are matrix-dependent.

The upper limit of quatitation (ULOQ) for a dataset is the highest concentration that can be reliably quantitatied within the specified limits of precision and accuracy during routine operating conditions. The highest standard in the calibration curve that meets method aiteria is defined as the ULOQ.

3.13 Method Blank

An aliquot of ASTM Type I water (HPLC grade reagent water or other suitable water may used) that is treated exactly like a laboratory sample including exposure to all glassware, equipment, solvents, and reagents that are used with other laboratory samples. The method blank is used to detemiine if test substances or other interferences are present in the laboratory environment, the reagents, or the apparatus.

3.14 Sample

A sample is a small portion collected from a larger quantity of material intended to represent the original source material.

3.15 Stock Standard Solution (SSS) A concentrated solution of a single analyte prepared in the laboratory with an assayed reference compound.

3.16 Surrogate

A compound similar to the target analyte(s) in chemical composition and behavior that is not normally found in the sample(s). A sun-ogate compound is typically a target analyte with at least one atom containing an isotopically labeled substitution. If used, sun'ogate(s) are added to all samples and quality control samples (except solvent blanks and half of the prepared method blanks). Sun-ogate(s) are added to quantitatively evaluate the entire analytical procedure including sample collection, extraction, and analysis. Inclusion of a sun'ogate analyte is an optional quality control measure and is NOT required. The project lead should indicate in the general project outline/protocol whether or not a sun-ogate compound will be part of the analysis.



Page 146 of 207



3.17 Working Standard (WS) A solution of several analytes prepared in the laboratory from SSSs and diluted as needed to prepare calibration standards and other required analyte solutions.

4 Warnings and Cautions

4.1 Health and Safety The acute and chronic toxicity of the standards for this method have not been precisely determined; however, each should be treated as a potential health hazard.

Unknown samples may contain high concentrations of volatile toxic compounds. Sample containers should be opened in a hood and handled with gloves to prevent exposure.

The laboratory is responsible for maintaining a safe wori< environment and a cun-ent awareness of local regulations regarding the handling of the chemicals used in this method. A reference file of material safety data sheets (MSDS) should be available to all personnel involved in these analyses.

4.2 Caut ions

The analyst must be familiar with the laboratory equipment and potential hazards including, but not limited too, the use of solvents, pressurized gas and solvent lines, high voltage, and vacuum systems. Refer to the appropriate equipment procedure or operator manual for additional infomiation and cautions.

5 Interferences

During extraction and analysis, be aware of potential contaminant sources from reagents and solid phase extraction devices.

All materials used in the analyses shall be demonstrated to be free from interferences under conditions of analysis by running method blanks.

Parts and supplies that contain Teflon® should be avoided or minimized due to the possibility of interference and/or contamination. These may include, but are not limited to: wash bottles. Teflon® lined caps, autovial caps, HPLC parts, etc.

The use of disposable micropipettes or pipettes to aliquot standard solutions is recommended to make calibration standards and matrix spikes.

6 Instrumentation, Supplies, and Materials

Note: Brand names, suppliers, and part numbers are for illustrative purposes only. Equivalent perfonnance may be achieved using apparatus and materials other than those specified here. Demonstration of equivalent perfonnance (quality control samples meeting method acceptance criteria) is the responsibility of the laboratory performing the analysis.

6.1 Instrumentat ion

Balance, analytical (display at least 0.0001 g), Mettler

HPLC/MS/MS or HPLC/MS system, as described in Section 10.

6.2 Suppl ies and Materials.



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for 14 davs froni 12/07/200;



Sample collection bottles—LDPE (e.g., Nalgene™) nan'ow-mouth bottles with screw cap. Note: Do not use Teflon bottles or Teflon lined caps.

Coolers or boxes for sample shipment.

AutoTrace automated SPE workstation. Caliper Life Sciences. A manual SPE manifold with vacuum pump may be used if desired. Supplies for the manual SPE manifold are included below.)

Vacuum pump, BQchi.

Visiprep vacuum manifold, Supelco.

15mL disposable polypropylene centrifuge tubes, VWR.

50mL disposable polypropylene centrifuge tubes, VWR

Sep Pak Vac 6cc (1 g) tC18 cartridges (part # WAT 036795), Waters. (Cartridges with other amount or types of sorbent material may be used depending on the data quality objectives of the project.)

15 mL disposable culture tubes (17 x 100 mm), VWR (Cat. No. 60818-626).

Disposable micropipettes (50-1 OOjjL, 100-200|JL) , Daimmond.

Class A pipettes and volumetric flasks, various.

LDPE nan"ow-mouth bottles, Nalgene (volumes may vary depending on analytical needs).

2 mL clear HPLC vial kit (cat # 5181-3400), Agilent/Hewlett Packard.

Standard lab equipment (graduated cylinders, disposable tubes, etc.), various.

7 Reagents and Standards

Note: Suppliers and catalog numbers are for illustrative purposes only. Equivalent perfonnance may be achieved using chemicals obtained fl'om other suppliers. Do not use a lesser grade of chemical than those listed.

7.1 Chemicals

Methanol (MeOH), HPLC grade, JT Baker, Catalog No. JT9093-2.

Ammonium Acetate, Reagent grade, Sigma-Aldrich, Catalog No. A-7330.

ASTM Type I Water, prepared in-house (HPLC grade reagent water or other suitable water may also be used)

Sodium Thiosulfate, Reagent grade, JT Baker.

7.2 Standards

PFBA, Heptafluorobutyric Acid, (C4 Perfluorinated Acid)

NFPA, NonafluoropentanoicAcid (C5 Perfluorinated Acid)

PFHA, Perfluorohexanoic Acid (Ce Perfluorinated Acid)

TDHA, Tridecafluoroheptanoic Acid, (C7 Perfluorinated Acid)

PFOA, Ammonium perfluorooctanoate, (Cs Perfluorinated Acid)

C9 Acid, Heptadecafluorononanoic Acid

PFDA, NonadecafluorodecanoicAcid (C10 Perfluorinated Acid)



Page 148 of 207



Cii Acid, Perfluoroundecanoic Acid

Ci2 Acid, Perfluorododecanoic Acid

FBSA, Perfluorobutanesulfonamide

FOSA, Perfluorooctanesulfonylamide

PFBS, Potassium Perfluorobutanesulfonate

PFHS, Perfluorohexanesulfonate

PFOS, Potassium perfiuorooctanesulfonate

THPFOS, 1H, 1H, 2H, 2H-perfiuorooctanesulfonic Acid

THPFDS, IH, IH, 2H, 2H-perfiuorodecanesulfonic Acid

PFOA [1,2-^^C], ^ C isotopically labeled perfluorooctanoic acid. Pertain Elmer

PFOS [ ^02], ^^02 isotopically labeled Ammonium Perfluoroocatanesulfonate

Others as required.

7.3 Reagent Preparat ion

250 mg/mL sodium thiosulfate solution — Dissolve 25g of sodium thiosulfate in 100 mL reagent water.

2 mM ammonium acetate solution (Analysis)—^Weigh 0.3 g of ammonium acetate and dissolve in 2.0 L of reagent water.

Note: Altemative volumes may be prepared as long as the ratios of the solvent to solute ratios are maintained.

7.4 Stock Standard Solution (SSS) and Working Standard Solution Preparation The following standard preparation procedure serves as an example. Weighed amounts and final volumes may be changed to suit the needs of a particular study. For example, JJL volumes may be spiked into volumetric flasks when diluting stock solutions to appropriate levels.

100 pg/mL target analyte SSSs—Weigh out 10 mg of analytical standard (corrected for percent salt and purity) and dilute to 10OmL with methanol or other suitable solvent, in a 10OmL volumetric fiask. Transfer to a 125mL LDPE bottle or other suitable container. Prepare a separate solution for each analyte. Expiration dates and storage conditions of stock solutions should be assigned in accordance with laboratory standard operating procedure. An example of purity and salt con-ection is given below for PFOS.

. , ^ molecular weight of anion salt correction factor =

moclecular weight of salt 499

PFOS (K^)salt correction factor = - ^ ^ = 0.9275 538

10 mg C8F17SO3K* with purity 90% = 8.35mg CSFITSOS"(10 mg*0.90*0.9275=8.35 mg)

1 pg/mL (1000 ng/mL) mixed working standard—Add I.OmL each of the lOOpg/mL SSSs to a lOOmL volumetric flask and bring up to volume with solvent.

0.1 \iglmL (100 ng/mL) mixed worlcing standard—Add lO.OmL of the 1.0|jg/mL-mixed wori<ing standard solution to a lOOmL volumetric fiask and bring up to volume with solvent.

ETS-8-154.3 Page 7 of 20 Detemiination of Perfiuorinated Acids, Alcohols, Amides, and Sulfonates In Water By Solid


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0.01 MQ/mL (10 ng/mL) mixed standard—Add lO.OmL of the 0.1|jg/mL-mixed wori<ing standard solution to a lOOmL volumetric fiask and bring up to volume with solvent.

Storage Conditions—Store all SSSs and wori<ing standards in accordance with laboratory standard operating procedure or in a refrigerator at 4°±2°C for a maximum period of 6 months fi-om the date of preparation.

7.5 Calibration Standards Using the worthing standards described above, prepare calibration solutions in ASTM Type I water, or other suitable water, using the following table as a guideline. Note: Volumes of water and wori<ing standards may be adjusted to meet the data quality objectives addressed in the general project outline. Calibration levels other than those listed below can be prepared as needed.

Concentration of WS, ng/mL

100

100

100

100

1000

1000

1000

10000

10000

10000

Volume of WS,

10

20

40

100

20

40

100

20

40

100

Final Volume of Calibration Standard (mL of ASTM Type 1 Water, or

other suitable water)

40

40

40

40

40

40

40

40

40

40

Final Concentration of Calibration Standard, ng/mL (ppb) in ASTM Type 1 Water,

or other suitable water

0.025

0.050

0.100

0.250

0.500

1.00

2.50

5.00

10.0

25.0

The calibration standards are processed through the entire extraction procedure (Section 11), identical to the laboratory samples. The concentration of the calibration standard in the final extract depends on the volume extracted and the final elufion volume.

Final sample concentration factor = Volume extracted (mL)/Elution Volume (mL)

Storage Conditions— Store all extracted calibrafion standards in 15mL polypropylene tubes or in labeled autovials at 4°±2°C. After analysis, archive all extracted standards with the sample extracts in accordance with laboratory standard operating procedures.

8 Sample Col lect ion Bott le Preparation

For most projects, sample collection bottles are prepared by 3M Environmental Laboratory personnel before they are shipped to the collection site. Typically, four separate collection bottles are associated with a single collection site: sample, field duplicate sample, low field matrix spike, and high field matrix spike. Depending on the scope of the project, additional replicates of the field sample and field matrix spikes may be added. Also, it is not uncommon for additional mid-level field matrix spikes to be collected if the expected sample concentrations are tmly unknown or could span a large concentration range.

Low-density polyethylene (LDPE) wide-mouth Nalgene bottles are used for the sample collection containers. (Volumes of the bottles may vary depending on how much sample is required to meet



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if current, TI

Exygen Protocol P0002561; Interim Report #16 3IVI Project E06-0549


data quality objectives.) The interiors of the Nalgene bottles may be rinsed multiple times with acetone and methanol and allowed to dry before adding the appropriate spikes. Note: rinsing of the bottles is opfional and is not required. The project lead will communicate what the final collection volume will be and a con-esponding "fill to here" line is drawn on the exterior of the bottle using a pemianent mariner. Typically, placement of the "fill to here" line is done by using a mariner template. Altematively, bottles with pre-mari<ed volume indicators may be purchased.

For the sample bottles designated for matrix spikes, an appropriate volume of matrix spiking solution is added to the empty bottle. The volume of spike solution added should produce the desired final concentration of target analytes once the bottle is filled with sample to the "fill to here line". (If a sunrogate is included for the project, the sun'ogate compound should also be added to the matrix spikes). The matrix spiking solution should be prepared in a suitable solvent and contains all of the target (and sun-ogate if applicable) analytes; however, multiple spike solutions may be used if an appropriate mixed component standard is not available. The matrix spiking solution is often the same as the wori<ing standards used to create the calibration standards. An example of a bottle spike is given below.

"Fill to here" volume = 450 mL (A 500 mL Nalgene bottle is used)

Desired Field Spike Concentration = 0.1 ng/mL

45|iL of a 1 ng/mL spiking solution (containing the target analytes) is added to the bottle and the bottle cap promptly sealed

If analysis of a sunrogate analyte is included in the project objectives, the preparatory analyst should also add an appropriate volume of sun-ogate standard solution to all the tsottles designated as samples or field duplicate samples.

All bottles should be cleariy labeled to indicate its intended use as a sample/field sample duplicate, low spike, or high spike. If each location has different designated spike levels, the label should also cleariy indicate the sample location designation. Generally, a set of bottles for a given collection site are then grouped together in plastic bags for organizational purposes.

For each collection event, at least one set of trip blank and trip blank matrix spikes are prepared. The number of trip blank sets required for a given project will be communicated by the project lead. For the trip blank, the sun'ogate spike is added to the bottle (if included) and then ASTM Type I water (HPLC grade reagent water or other suitable water may used) is added to the "fill to here" line. The bottle cap is replaced and tape may be placed around the outer edge of the cap. Trip blank matrix spikes are prepared by adding the appropriate volume of matrix spiking solution, filling the bottle to the desired volume with the appropriate water and replacing and sealing the cap.

The preparatory analyst should document bottle preparation in a Note to File or on a sample preparation wori<sheet. The Note to File should include the following infomiation: date prepared, total number of bottles prepared, number of sample sites, the standard identification numbers and spike volumes used to prepare spiked bottles, the "fill to here" volume, and any other pertinent information needed for reconstaictibility of the data. The Note to File will be included in the final data package for the project.



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1 9 / 0 T / 9 0 0 ? '



9 Quality Control and Data Quality Objectives

Analytical results of the FB, FMS, LMS, FD, and FSCS should be evaluated at the conclusion of the study to help interpret the quality of sample data. Analytical results for these control/duplicate samples must be reported with the sample data.

9.1 Solvent Blanks

Solvent blanks are analyzed with each sample set to detemiine contamination or canyover. In general, solvent blanks should have area counts that are less than 50% of the area count of the lowest calibration standard.

Solvent blanks should be analyzed prior to and following each calibration curve, each set of system suitability samples, and after no more than 10 unknown sample extracts. If instrument canyover is a problem, consecutive solvent blanks may be necessary. In this case, the area counts of the solvent blanks should return to <50% of the lowest calibration standard prior to the injection of further standards or samples.

9.2 Method Blanks

A method blank consists of an aliquot of ASTM Type I water (HPLC grade reagent water, or other suitable water may be used) equal in volume to the samples, and extracted in the same manner as the samples. At least five method blanks should be prepared and analyzed each day that extractions are peri'ormed for a particular study or project. Method blanks must be interspersed throughout the extraction batch and analyzed interspersed throughout the analytical sequence.

The average area counts for each analyte must be less than 50% of the area count of the LOQ standard. The standard deviation of the area counts should be calculated. A specific %RSD acceptance criteria is not specified but is assessed on a batch basis. If the mean area counts of the method blank exceed 50% of the LOQ standard, then the LOQ must be raised to the first standard level in the curve tiiat meets criteria. Method blanks may be eliminated if technical justification can be provided (e.g. the method blank was analyzed after an unexpectedly high level sample). If any method blanks are removed fi-om the LOQ detemiination, document in the raw data and report as appropriate.

9.3 Laboratory Sample Replicates / Field Duplicate Sample

Depending on the scope of the project, all or selected samples may be extracted at least in duplicate, and in triplicate if difficulties were encountered in the sampling and/or holding conditions of the samples. If field sample replicates are collected, duplicate and triplicate extractions of an individual sample may not be required. The relative percent difference (RPD) of duplicate samples or relative standard deviation (RSD) should be less than 20% for the precision of sample preparation and analysis to be considered in control. Replicate samples not meeting tiie 20% method criteria will be reviewed and evaluated on a case by case basis.

9.4 Laboratory Matrix Spikes (LMSs)

LMSs are peri'onned if FMSs have previously been perfonned for the sample matiix. Altematively, LMSs are perfonned for a sample matiix if the FMS levels were not appropriate for detemiining spike recoveries relative to endogenous levels. Generally, each sample location represents a different sample and sample matrix. LMSs are prepared for each sample and analyzed to detemiine the matrix eff'ect on spike recovery efficiency of each target analyte. Lab matrix spike recoveries should fall within ± 30% of expected values.

LMS concentrations should be prepared at approximately 0.5-10 times the endogenous concentration or approximately 4-10 times the LOQ concentration of each analyte.

ETS-8-154.3 Page 10 of 20 Determination of Perfiuorinated Acids, Alcohols, Amides, and Sulfonates In Water By Solid

Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometiy

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9.5 Laboratory Contro l Spike (LCS)

Lab control spikes are prepared for each extraction tjatch to detemnine method accuracy and precision. LCSs should be prepared at a minimum of two levels and in ta-iplicate. Low lab conb-ol spikes should be prepared at a concentration in the range of approximately four to ten times higher than the targeted LOQ and the high lab control spikes should be prepared at a concentration near the mid-point of the calibration curve. For each target analyte, the percent relative standard deviation (method precision) of the pooled control spikes must be less than or equal to 20% and tiie average recovery (method accuracy) must be 80-120%. Sample data for target analytes outside of the laboratory control spike acceptance criteria are not reportable.

9.6 Field Matr ix Spikes (FMSs)

FMSs are prepared for each sample and analyzed to detemiine the matrix effect and sample holding time on spike recovery efficiency of each target analyte. Generally, each sample location represents a different sample and sample matrix.

FMS samples are a sample to which known quantities of the target analytes are added to Uie sample bottle in the field or in the laboratory before the bottles are sent to the field. Typically a low and a high FMS are prepared for each sampling location. The ratio of endogenous analyte to field spike concenti-ation tiiat is appropriate to assess accuracy is defined as approximately 0.5 to 10 times the expected sample concentration. For example, if the endogenous level of analyte in the sample is expected to be 1.0 ng/mL, the appropriate range for FMS used to assess accuracy of results would be approximately 0.5 ng/mL to 10 ng/mL. For samples that are expected to have endogenous analytes present at or below the targeted LOQ, the appropriate range for FMS would be approximately 4 to 10 times ttie LOQ concentration. For example, if the analyte LOQ is 0.025 ng/mL, the appropriate range for low level FMS would be 0.1 ng/mL to 0.25 ng/mL. If the expected range of analyte concenti-ations is unknown, multiple spikes at varying levels may be prepared to increase the likelihood that a spike at an appropriate level is made.

Field matrix spike method acceptance criteria are recoveries within ±30% of the expected value. If FMS recovery is outside of ±30% of the expected value or could not be assessed because the FMS was spiked at an inappropriate level, tiie sample result is reported as NR, where NR is defined as "Not Reportable". For data reportability, a sample may be re-extracted and reanalyzed or an alternate analytical method may be applied to the sample. Altematively, resampling and reanalysis of a new sample may be completed. If re-extraction, resampling, and re-analysis fail to meet the FMS acceptance criteria, the sample result will be reported as "NR" (not reported due to noncompliant QC results).

Exceptions to the ±30% FMS acceptance aiteria for data reportability are as follows:

1.) If FMS recovery could not be assessed because FMS's were at an inappropriate level, then Laboratory Matrix Spikes (LMS) may be substituted. If LMS recoveries are within ±30% the data are reportable but flagged as not meeting the FMS method acceptance criteria.

2.) If multiple FMS's were prepared on a sample and the closest FMS level to the reported sample meets the ±30% acceptance criteria but additional FMS's are outside the ±30% acceptance range, tiie data are reportable but flagged witti an expanded uncertainty and as not meeting FMS method acceptance criteria.

3.) If the FMS recoveries are outside of the ±30% acceptance range but at least 20 acceptable historical reportable FMS sample results are available, the data may be reported but flagged with an expanded uncertainty and as not meeting FMS criteria.

10 Calibration and Standardization

ETS-8-154.3 Page 11 of 20 Detemnination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In Water By Solid

Phase Extraction and High Perfonnance Liquid Chromatography/Mass Spectrometiy

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Exygen Protocol P0002561; Interim Report #16 3IVI Project E06-0549


10.1 Inst rument Setup

Note: In this example, an Applied Biosystems Sciex API 4000 Tandem Mass Spedrometer (LC/MS/MS) is used. Ottier brands of LC/MS/MSs as well as single quadrupole mass spectrometers (LC/MS) may be used as long as the method criteria are met. Brand names, suppliers, part numbers, and models are for illusfa-ative purposes only. Equivalent performance may be achieved using apparatus and materials other tiian those specified here, but demonsti-ation of equivalent performance ttiat meets the requirements of ttiis method is the responsibility of the laboratory. The operator must optimize and document the equipment and settings used.

Establish the LC/MS/MS system and operating conditions equivalent to the following:

Mass Spec: Applied Biosystems API 4000

Ion Source: Turtx) Ion Spray (ABS)

Mode: Electrospray Negative

Scan Type: MRM (Multiple Reaction Monitoring)

Harvard infijsion pump (Harvard Instruments), for tuning

Computer: Dell DHM

Software: Windows 2000 or Windows XP, Analyst 1.4.1

HPLC: Agilent Series 1100

Agilent Quatemary Pump

Agilent Vacuum Degasser

Agilent Autosampler

Agilent Column Oven

Note: One or more C18 HPLC analytical columns (2.1 mm x 100 mm, 5nm or 2.1 mm x 50 mm, 5nm) may be attached on-line after the purge valve and before the sample injection port to retard and separate any residue contaminants ttiat may be in the mobile phase and/or HPLC system.

HPLC Column: Betasil C18,2.1mm x 100mm, 5nm (ThemioElecti-on Corporation)

Column Temperature: 35°C

Injection Volume: 5|JL

Mobile Phase (A): 2mM Ammonium Acetate in ASTM Type I water (See 7.3)

Mobile Phase (B): Methanol

ETS-8-154.3 Page 12 of 20 Detemnination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In Water By Solid


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jsed, If (current,



Liquid Chromatography Gradient Program.

step Number

0

1

2

3

4

5

Total Time (min)

0

1.0

14.5

15.5

16.5

20.0

Flow Rate (/dJmin)

300

300

300

300

300

300

Percent A (2 mM ammonium acetate)

80.0

80.0

10,0

10.0

80.0

80.0

Percent 8

(MethanoO

20.0

20.0

90.0

90.0

20.0

20.0

Note: Other HPLC gradients may be used as long as the method aiteria and project data quality objectives are met.

It may be necessary to adjust the HPLC gradient in order to optimize instmment performance. Columns with different dimensions (e.g. 2.1 mm x 30mm) and columns from different manufacturers (Keystone Betasil C18 etc.) may be used.

iVIass Transitions {Monitored.

Analyte

PFBA (C4 Add)

NFPA (Cs Acid)

PFHA (Ce Acid) TDHA (C7 Acid)

PFOA (Cs Add)

CgAdd

C10 Add

C„ Add

C12 Add

FBSA

FOSA

PFBS

PFHS

PFOS

THPFOS

THPFDS

PFOA[1,2"C]

PF0S[''02]

Mass Transition Q1 (amu)

213.0

262.9

313.0 362.9

413.0

463.0

512.9

563.0

613.0

297.7

497.9

298.9

398.9 498.9

426.9

526.9

414.9

503.0

Mass Trartsition 03 (amu)

169.0

219.0

268.7,118.9

318.7,168.8,118.9

368.9,219.0.169.0

418.7,168.9,218.9

468.8,218.9,269.1

518.7,268.9,218.8

568.7,168.9,318.7

78.0

77.9

98.9, 79.9

98.9, 80.0

80.0,98.8,130.0

406.8,80.9

506.7,81.0 369.8

103.0,84.0

Declustering Potential

-30

-30

-45

-35

-45

-45

-35

-45

-50

-55

-90

-65

-95 -120

-70

-70

-40

-100

ETS-8-154.3 Page 13 of 20 Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In Water By Solid


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Multiple transitions for monitoring the analytes is an option as summing multiple transitions may provide quantitation of isomers that more closely matches NMR data and may have the added benefit of increased analyte signal. The use of one daughter ion is acceptable if mettiod sensitivity is achieved, provided that retention time criteria are met to assure adequate specificity. While the daughter ions may be chosen at the discretion of the analyst, mass to-ansition 99 is suggested for PFOS. Quantitation may be performed using ttie total ion chromatogram (TIC) for a given analyte. For example, the PFOA TIC would sum all three of ttie monitored ti-ansitions. Use of tiie suggested primary ion is recommended. Retention times may vary slightly, on a day-to-day basis, depending on the batch of mobile phase and the gradient, column, guard column(s) used etc. Drift in retention times is acceptable within an analytical njn, as long as tiie drift continues through the entire analysis and the standards are interspersed throughout the analytical mn.

10.2 Method Acquisition Parameters The following values are provided as an example of method acquisition parameters for a single period, single experiment method using the Sciex insti-umentation. Actual values may vary from instnjment to Instixjment. Also, these values may be changed from time to time in order to optimize for greatest sensitivity. If a multiple period is used, each period may have different gas, temperature, and ion spray voltages.

Curtain Gas (CUR)

Collision Gas (CAD)

lonSpray Voltage (IS)

Temperature (TEM)

Gas 1 (Nebulizer) GS1

Gas 2 (Turbo Gas) GS2

Interface Heater (Ihe)

Entrance Potential (EP)

15.0

High

-4500

450.0

35.0

45.0

ON

-10

10.3 Cal ibrat ion Curve

Analyze the standard curve prior to each set of samples. The validated method specifies that the standard curve should be plotted using a linear fit, weighted 1/x or unweighted. However, the standard curve may also tie plotted by quadratic fit (y = ax + bx + c), weighted 1/x or unweighted, using suitable software. The calibration curves may include but should not be forced through zero. The mathematical method used to calculate the calibration curve should be applied consistently throughout a study. Any change should be thoroughly documented in the raw data.

If the calibration curve does not meet acceptance aiteria, perfomi routine maintenance or prepare a new standard curve (if necessary) and reanalyze.

For purposes of accuracy when quantitating low levels of analyte, it may be necessary to use the low end of the calibration curve rather than the fijil range. For example, when attempting to quantitate approximately 0.05 ng/mL of analyte, generate a calibration curve consisting of the standards fi-om 0.025 ng/mL to 10.0 ng/mL rather than the fijil range of the curve (0.025 ng/mL to 25.00 ng/mL). This will reduce inaccuracy attributed to linear regression weighting of high concentration standards.

High and/or low points may be excluded from the calibration curves to provide a better fit over the range appropriate to the data or because ttiey did not meet ttie pre-detennined acceptance criteria. Low-level curve points should also be excluded if their area counts are not at least twice that of the method and/or solvent blanks. Any curve point may be rejected due to a bad injection



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, I t •• • . ' t ro r t i



or failing to meet accuracy requirements of ± 25% (and ± 30% for the LLOQ). Justification for exclusion of calibration curve points will be noted in the raw data. A minimum of 6 points will be used to constmct the calibration curve. No more than 25% of the total extracted calibration standards should be excluded. This does not pertain to low and high levels that may need to be disabled to achieve an accurate curve in ttie concentration range of the samples, rather, this is intended to apply to mid curve points only.

10.4 Continuing Calibration Verification (CCV) Continuing calibration verifications (CCV) are analyzed to verify the accuracy of tiie calibration cun/e. Analyze a mid-range calibration standard, one of ttie same standards used to constmct the calibration curve, at a minimum after every tenth sample, not including solvent blanks, witii a minimum of one per sample set. Calibration verification injections must be wittiin ±25% to be considered acceptable. The calibration curve and the last passing CCV will then bracket acceptable samples. Multiple CCV levels may be used.

10.5 System Suitability A minimum of three system suitability samples will be injected at the beginning of each analytical njn, prior to the analysis of the calibration curve. Typically these samples are at a concentration near the mid-level of the calibration curve are repeated injections fi-om one autosampler vial. The system suitability injections must have area counts with an RSD of S5% and a retention time RSD of S2% to be compliant.

11 Procedures

11.1 Extraction Scheme The following steps represent a typical extraction scheme. Sample extraction volumes and final elution volumes may be adjusted to meet data quality objectives.

Allow samples to equilibrate to room temperature. Thoroughly mix samples by gently inverting the sample bottle.

Measure a 40mL representative aliquot of the well-mixed sample into a 50mL polypropylene centrifijge tubes (Spike the lab matrix spikes as required*, replace lid and mix well). Altemate volumes may be used depending on the scope of the project. Use a consistent sample volume for all extractions and document on the sample prep sheet.

Add 40|JL of 250 mg/mL sodium thiosulfeite solution to 40mL of sample. Adjust the amount of sodium thiosulfate solution added if altemate sample volumes are used. Thoroughly mix sample.

Note: * Samples may need to be presaeened to determine an appropriate matrix spike level (typically approximately 0.5 to 10 times the sample concenti-ation). Altematively the samples could be spiked at more tiian one level, allowing for the inappropriate spike level to be eliminated.

Condition the C18 SPE cartridges (1g, 6mL) by passing approximately lOmL methanol (at a minimum) followed by approximately 50mL (at a minimum) ASTM Type I water. Do not let column run dry. If column does run dry, recondition. SPE cartridges cannot be over conditioned.

Load the analytical sample onto ttie Cl 8 SPE cartridge. Once the entire sample has loaded onto the cartridge, isolate the cartridge fi-om the vacuum and wait until all samples on the vacuum manifold have been loaded. Discard eluate. Open manifold valves and pull a vacuum on the SPE cartridges for approximately 3 minutes to remove residual water fi-om the SPE cartridge.

Elute with exactly 5 mL of 100% methanol. Collect eluate into graduated 15mL polypropylene centrifuge tubes. This is the target elution fi-action (final volume approximately 4.5 mL as not all of the solvent will leave the SPE column. This will not affect ttie calculations in any way since the


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D • •:, : - i ( i , \ f a x \ : • • • : . ' ' ' 12 /0 / /2007



curve is also extracted). Note: the elution volume may be altered to meet project needs. The same elution volume needs to be used for all samples, calibration standards, and QC samples.

Intersperse the method blanks throughout the extraction batch.

Transfer well-mixed aliquots of the final extract to labeled autovials.

Analyze a portion of the target elution fraction eluent using negative electrospray HPLC/MS/MS or HPLC/MS.

Note: Samples are concentrated by a factor of eight during the extraction; Initial Vol = 40mL -> Final Vol. = 5mL.

11.2 Sample Analys is

Set up analysis sample queue. Mettiod blanks must be interspersed throughout the analytical sequence.

Inject the same volume (between 5-25^JL) of each standard, analytical sample and blank into the instalment (unless an on-insti-ument sample dilution is desired).

All sample extracts with a concentration > ULOQ must be diluted and reanalyzed. If dilution of the final extract î ls to produce acceptable results (e.g. poor MS recoveries) dilute ttie original sample and re-extract.

12 Data Analysis and Calculations

The chromatography analysis software will typically calculate the amount of target analyte in the sample extracts using the established calibration curve.

Calculate the percent recovery of the LCS using the following equation:

LCS Concentration {^-) LCS% recovery = Si i^* 100%

ng Spike Concentration (—^)

mL

Calculate the percent recovery of the FSCS using the following equation:

FSCS Concentration (^^) FSCS% recovery = SlI^* ioo%

ng Spike Concentration (•— )

mL

Calculate the percent recovery of the FMS using the following equation:

ng ng FMS Concentration ( ) - Average Concentration of Sample/Sample Duplicate (—^)

FMS % recovery = " ^ SlL- • i OQo/o ng

Spike Concentration (—^) mL


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tcsr



13 Method Performance

Any method perfonnance parameters that are not achieved must be considered in Uie evaluation of the data. Nonconfomiance to any specified parameters must be described and discussed if the project lead chooses to report the data.

If criteria listed in this mettiod perfonnance section are not met, maintenance may be performed on the system and samples reanalyzed, or other actions taken as determined by the analyst/project lead. Document all actions in the raw data.

If data are to be reported when performance criteria have not been met, the data must be footnoted on tables and discussed in the text of the report.

13.1 System Suitabi l i ty

A minimum of three system suitability samples will be injected at the beginning of each analytical run. These samples are mn prior to the calibration curve. The system suitability injections must have area counts with an RSD of s5% and a retention time RSD of ^2% to be compliant.

13.2 Quantitation Calibration Curve: The coefficient of determination (r ) value for the calibration curve must be greater than or equal to 0.990. Each point in the curve must be within ±25% of the theoretical concentration with the exception of the LLOQ, which may be within ±30%.

Demonstration of Specificity: Specificity is demonstrated by chromatographic retention time (wittiin 3% of standard) and the mass spectral response of unique ions.

13.3 Sensi t iv i ty

Solvent Bianl<s and iVietliod Bianl<s: Solvent and method blank area counts must be < 50% that of the lowest standard used in the calibration curve. Solvent blanks analyzed after high level samples or calibration standards may have area counts greater than 50% of the lowest standard fi-om instnjment canyover as long as subsequent solvent blanks analyzed before the next sample/QC sample demonsti-ate that the instalment canyover is decreasing back to expected levels.

Limits of Quantitation (LOQ): The lower LOQ (LLOQ) is the lowest non-zero active standard in the calibration curve; the peak area of the LLOQ must be at least 2X that of the method blank(s). By definition, the measured value of the LLOQ must be within 30% of tiie theoretical value.

13.4 Accuracy

CCV Performance: Calibration verification injections must be within ±25% to be considered acceptable. The calibration curve and the last passing CCV will then bracket acceptable samples. Multiple CCV levels may be used. LCS recoveries should be witiiin ±25% to be considered acceptable and to verify that the method is in control on a given day.

Lab Control Spil<es: The average recovery of the pooled LCSs for each target analyte should be within 80-120% and the percent relative standard deviation of the recoveries must be less than or equal to 20%.

13.5 Precis ion

Reproducibility: Reproducibility of the method is defined by the results of duplicate or triplicate analysis of samples. A RPD or RSD of s 20% will be considered acceptable for replicate lab control spikes. Because field sample duplicates account for variability in sample location (as well as variability in the extraction procedure), RPD or RSD values may be higher. Report the RPD or


Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometiy

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RSD of sample/field duplicates and discuss in ttie report if greater than 20% and the impact on field matrix spike recoveries, if any.

13.6 Analytical Method Uncertainty / Data Acceptability Analytical method uncertainty may be defined and reported in one of two ways. The first approach uses historical LCS data that is control charted and is used to evaluate method accuracy and precision, based on procedures defined in ETS-12-012. In ETS-12-012, a detailed estimation of uncertainty measurements was performed on ETS-8-231.2, "Solid Phase Extraction and Analysis of Perfiuorinated Acids, Alcohol, Amides, Sulfonates and other Fluorinated Compounds by High Perfonnance Liquid Chromatography/Mass Spectrometry". The procedure outlined in this method utilizes the same preparation and analysis steps as tiiose identified in ETS-8-231.2. In that evaluation it was detennined that the use of conti-ol charts was an acceptable approach to detemiining analytical method uncertainty. At least twenty data points are required when using this method for detemnining analytical uncertainty. The method uncertainty is defined as 2xthe standard deviation of the percent recoveries of the pooled lab control spikes. While all LCS data points are control charted, only the most recent fifty data points are used for detemiining the method uncertainty.

When less than twenty LCS data points have been generated for a given analyte, the batch LCS and FMS QC determine the data acceptability. If FMSs meet the ±30% recovery criteria at a level appropriate to the endogenous level, and the LCS meet the ±20% recovery criteria, then the uncertainty of the data is deemed accurate to within 100±20%. If FMS do not meet the ±30% recovery criteria, and historical FMS data does not exist, the analytical uncertainty is evaluated on a case-by-case basis and a discussion included in the final analytical report.

14 Pol lut ion Prevent ion and Waste Management

Sample extract waste and flammable solvent is discarded in high BTU containers, and glass pipette waste is discarded in broken glass containers located in the laboratory.

15 Records

Each data package generated for a study must include all supporting infomiation for reconstnjctibility of the data. Information for the data package must include, but is not limited to the following items: study or project number, sample and standard prep sheets/records, instiximent mn log (instmment batch records, instiximent acquisition method, summary pages), instmment results liles, chromatograms, calibration curves, and data calculations.

16 Attachments

None.

17 References

"Method of Analysis for the Detemiination of Perfluorooctane sulfonate (PFOS), Perfluorooctane sulfonylamide (PFOSA), and Perfluorooctanoate (POAA) in Water", E. Wickremesinhe and J. Flaherty, Study Number 023-002, Centi'e Analytical Labraratories, Inc., State College, Pennsylvania, January 2000.

E01 -0454: Validation report for the "Method of Analysis for the Detemnination of Perfluorooctane sulfonate (PFOS), Perfluorooctane sulfonylamide (PFOSA), and Perfluorooctanoate (POAA) in



Page 160 of 207

D . used, if current for 1 : ••. 12/07/200]



Water", E. Wickremesinhe and J. Flaherty, Study Number 023-002, Centre Analytical Laboratories, Inc., State College, Pennsylvania.

18 Affected Documents

None.

19 Revis ions

Revision Number Summary of Changes

1 Updated to the new format. Changed Title. Section 1: States the validation of 3 anaiytes, removes reference to EPA document that's no ionger applicabie. Section 2: Provided for the extraction of more than the 3 validated analytes, allows the use of a LC/MS system, not only the LSMS/MS previously mentioned. Section 3: Revised definitions for field matrix spike, field control spike, LLOQ, method blank, and MDL Section 5: Reworded the interferences, added recommendation to use disposable pipettes. Section 6: Re-categorized and pared down. Section 7: Changed storage time to 6 months. Added more calibration points to the table. Section 8:Added statement addressing labeling requirements and spiking procedures. Expanded section 8.8. Section 9: New Section Section 10: Changed some of the parameters in the tables. Allowed for use of different instrumentation. Added information from section 12 of previous version, extensively revised. Section 11 (section 9 in previous version): Clarification of wash step, stated exact volume of eluate is 5 mL, revised standardization process, removed requirement to use LC/MS/MS. Section 12 (section 13 in previous version: no changes Section 13 (section 14 in previous version): Extensively rewritten. Section 14 (section 15 in previous version): no changes Section 15 (section 16 in previous version): Minor changes to recording requirements. Section 16 (section 17 in previous version): Removed attachment. Section 17 (section 18 in previous version): Removed reference to EPA document that no longer applied to this SOP. Section 18: New section.

2 Section 1: Added emphasis that the method is a performance-based method. Added statement that this method does not cover sample collection. Section 2: Removed statement that samples are shipped cold as this is no longer the practice. Removed reference to specific C18 SPE cartridge. Added statement that other extraction and elution volumes may be used. Section 3. Minor edits/clarifications to several definitions. Added surrogate and SPE cartridge as a definition. Removed references to LOD and MDL as this


Phase Extraction and High Perfonnance Liquid Chromatography/Mass Spectrometiy

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laboratory does not report LCD and/or MDL values. Section 6. Added reference to automated SPE workstation. OSection 7. Added additional analytes and updated standard preparation examples. Section 8. Removed verbiage that pertained to sample collection as the 3M Environmental Lab personnel typically do not collect samples. Addressed sample bottle preparation. Section 9. Changed method blank criteria, LMS and FMS acceptance criteria from 100+25% to 100+30%, and LCS criteria where pooled recoveries are used to detemiine acceptance. Section 10. Updated all example instrument conditions for Sciex instrumentation -removed Micromass references Section 11. Clarified extraction procedure - removed inclusion of a 40% methanol wash step. Section 12. Minor edits. Section 13. Added section on determination of analytical uncertainty and changed performance criteria as appropriate.

Section 11.1. Added use of sodium thiosulfate


Phase Exti-action and High Perfonnance Liquid Chromatography/Mass Spectrometiy

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ATTACHMENT C: PROTOCOL

Page 163 of 207



Exygen Study Number: P0002561

STUDY PROTOCOL

Study Title:

Analysis of Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid (PFPeA), Perfluorohexanoic Acid

(PFHA), Perfluoroheptanoic Acid (PFHpA), Perfluorooctanoic Acid (PFOA), Perfluorononanoic Acid (PFNA),

Perfluorodecanoic Acid (PFDA), Perfluoroundecanoic Acid (PFUnA), Perfluorododecanoic Acid (PFDoA),

Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfiuorooctanesulfonate (PFOS) in Water, Soil,

and Sediment Using LC/MS/MS for the 3M Cottage Grove Monitoring Program Phase 2


Performing Laboratory: Exygen Research 3058 Research Drive State College, PA 16801 Phone:(814)272-1039

Sponsor Representative: Robert A. Paschke Manager, 3M Corporate Environmental Programs Bldg 42-02-E-27 St. Paul, MN 55144 Phone:(651)778-5200

Page I of 37

Page 164 of 207




DISTRIBUTION:

1) Jaisimha Kesari, Study Director, Weston Solutions

2) John M. Flaherty, Principal Investigator, Exygen Research

3) Robert A. Paschke, Sponsor Representative, 3M Company

4) Exygen Research Quality .Assurance Unit

Page 2 ofi?

Page 165 of 207



Exygen Study Number: P000256I

PROTOCOL APPROVAL

Study Title: Analysis of Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid (PFPeA), Perfluorohexanoic Acid (PFHA), Perfluoroheptanoic Acid (PFHpA), Perfluorooctanoic Acid (PFOA), Perfiuorononanoic Acid (PFNA), Perfluorodecanoic Acid (PFDA), Perfluoroundecanoic Acid (PFUnA), Perfluorododecanoic Acid (PFDoA), Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfiuorooctanesulfonate (PFOS) in Water, Soil, and Sediment Using LC/MS/MS for the 3M Cottage Grove Monitoring Program Phase 2

Exygen Study Number: P000256I

APPROVAI

')JJiLUy Jaisimha Kesari, Study Director Weston Solutions

Robert A. Paschice, Sponsor Representative 3M Company

Date

//^/^/i hn M. Flaherty, Principal Investigator

Exygen Research Date

Lydja'Shaffer, Technical I/ead, Quality Assurance Unit Exygen Research

Date

imm " Dat'«

^

Page 3 of 37

Page 166 of 207

JPROTOGOL! i&PPROVAL




.,;'-I-W'

Study Title: Analysis of Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid (PFPeA), Perfluorohexanoic Acid (PFHA), Perfluoroheptanoic Acid (PFHpA), Perfluorooctanoic Acid (PFOA), Perfluorononanoic Acid (PFNA), Perfluorodecanoic Acid (PFDA), Perfluoroundecanoic Acid (PFUnA), Perfluorododecanoic Acid (PFDoA), Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfiuorooctanesulfonate (PFOS) in Water, Soil, and Sediment Using LC/MS/MS for the 3M Cottage Grove Monitoring Program Phase 2


APPROVALS

Jaisimha Kesari, Study Director Date Weston Solutions

Robert A. Paschke, Sponsor Representative Date 3M Company

John M. Flaherty, Principal Investigator Date Exygen Research

Richard A. Grazzini, Management Date Exygen Research

Lydia Shaffer, Technical Lead, Quality Assurance Unit Date Exygen Research

Page 3 of 37

Page 167 of 207




TABLE OF CONTENTS

TITLE PAGE 1

DISTRIBUTION 2

PROTOCOL APPROVAL 3

TABLE OF CONTENTS 4

INTRODUCTION 5

TEST MATERIAL 5

OBJECnVE 10

TESTING FACILITY 10

STUDY DIRECTOR 10

SPONSOR REPRESENTATIVE 11

PRINCIPAL INVESTIGATOR 11

PROPOSED EXPERIMENTAL START AND TERMINATION DATES 11

IDENTIFICATION AND JUSTIFICATION OF THE TEST SYSTEM 11

SAMPLE PROCUREMENT, RECEIPT AND RETENTION 12

SAMPLE IDENTIFICATION 12

ANALYTICAL PROCEDURE SUMMARY 13

VERIFICATION OF ANALYTICAL PROCEDURE 13

METHOD FOR CONTROL OF BIAS 14

STATISTICAL METHODS 15

GLP STATEMENT 15

REPORT 15

SAFETY AND HEALTH 16

AMENDMENTS TO PROTOCOL 16

DATA RECORD KEEPING 17

QUALITY ASSURANCE 17

RETENTION OF DATA AND ARCHIVING 18

APPENDIX I, ANALYTICAL METHODS 19

APPENDIX U, MINNESOTA POLLUTION CONTROL GUIDANCE DOCUMENTS 32

Page 4 of 37

Page 168 of 207




INTRODUCTION

The purpose of this study is to perform analysis for perfluorobutanoic acid (PFBA), perfluoropentanoic acid (PFPeA), perfluorohexanoic acid (PFHA), perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnA), perfluorododecanoic acid (PFDoA), perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (PFHS), and perfluorooctanesulfonate (PFOS) in water, soil, and sediment using LC/MS/MS for the 3M Cottage Grove Monitoring Program Phase 2.

The study will be audited for compliance with EPA TSCA Good Laboratory Practice Standards 40 CFR 792 by the Quality Assurance Unit of Exygen Research.

TEST MATERIAL

The test materials are perfluorobutanoic acid (PFBA), perfluoropentanoic acid (PFPeA), perfluorohexanoic acid (PFHA), perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnA), perfluorododecanoic acid (PFDoA), perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (PFHS), and perfiuorooctanesulfonate (PFOS).

PFBA Chemical Name: Perfluorobutanoic acid Molecular Weight: 214 Lot Number: U02C Purity: 99% Supplier: Oakwood Products, Inc. Transitions Monitored: 213-^169 Structure:

F O F

F - .

i

/ I F II

F I

- ^ O H 7

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PFPeA Chemical Name: Perfluoropentanoic acid Molecular Weight: 264 Lot Number: 20524JB Purity: 99.1% Supplier: Sigma-Aldrich Chemical Co. Transitions Monitored: 263 -> 219 Structure:

PFHA Chemical Name: Perfluorohexanoic acid Molecular Weight: 314 Lot Number: 3131 Purity: 98% Supplier: Oakwood Products, Inc. Transitions Monitored: 313 -> 269 and 313 -> 119 Structure:

PFHpA Chemical Name: Perfluoroheptanoic acid Molecular Weight: 364 Lot Number: H3002 Purity: 99% Supplier: Oakwood Products, Inc. Transitions Monitored: 363 -> 319,363 -> 169 and 363 -> 119 Structure:

0 1

/ 1

I

H

1 4

^ I

I \

]

/ I

F

?

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PFOA Chemical Name: Perfluorooctanoic acid Molecular Weight: 414 Lot Number: Y16G Purity: 98% Supplier: Oakwood Products, Inc. Transitions Monitored: 413 -> 369,413 -)• 219 and 413 -^ 169 Structure:

F • F F 0

F F F F

PFNA Chemical Name: Perfluorononanoic acid Molecular Weight: 464 Lot Number: h7568 Purity: 99% Supplier: Oakwood Products, Inc. Transitions Monitored: 463 -* 419,463 -> 169 and 463 -» 219 Structure:

F F F F O

F F F F

PFDA Chemical Name: Perfluorodecanoic acid Molecular Weight: 514 Lot Number: Y31J Purity: 98% Suppher: Oakwood Products, Inc. Transitions Monitored: 513 ^ 469, 513 ^ 219 and 513 -> 269 Structure:

F F F F

F F F F F

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PFUnA Chemical Name: Perfluoroundecanoic acid Molecular Weight: 564 Lot Number: UllN Purity: 99% Supplier: Oakwood Products, Inc. Transitions Monitored: 563 ->• 519, 563 -> 269 and 563 -» 219 Structure:

F" F F F F F

F T F T F T F T F

PFDoA Chemical Name: Perfluorododecanoic acid Molecular Weight: 614 Lot Number: YOU Purity: 98% Supplier: Oakwood Products, Inc. Transitions Monitored: 613 -> 569, 613 -> 169 and 613 -> 319 Structure:

F | F | F I F I F I F

F I F I F I F I F

PFBS Chemical Name: Perfluorobutanesulfonate Molecular Weight: 338 supplied as the potassium salt (CApgSOs'K*) Lot Number: 2 Purity: 97.3% Supplier: 3M Transitions Monitored: 299 -» 80 and 299 -> 99 Structure:

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PFHS Chemical Name: Perfluorohexanesulfonate Molecular Weight: 438 supphed as the potassium salt (CeFnSOs'K^) Lot Number: NB 120067-69 Purity: 98.6% Suppher: 3M Transitions Monitored: 399 -> 80 and 399 -» 99 Structure:

PFOS Chemical Name: Perfluorooctanesulfonate Molecular Weight: 538 supplied as the potassium salt (CsFpSOj'K'^) Lot Number: 430180/1 Purity: 101.2% Suppher: Fluka Corporation Transitions Monitored: 499 -* 80, 499 -^ 99 and 499 -^ 130 Structure:

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Exygen Protocol P0002561; Interim Report #16 3I\/I Project E06-0549



OBJECTIVE

The purpose of this study is to perform analysis for perfluorobutanoic acid (PFBA), perfluoropentanoic acid (PFPeA), perfluorohexanoic acid (PFHA), perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnA), perfluorododecanoic acid (PFDoA), perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (PFHS), and perfluorooctanesulfonate (PFOS) in water, soil, and sediment for the 3M Decatur Monitoring Program Phase 2 using the current version 3M Environmental Laboratory analytical method ETS-8-012.0: Method of Analysis for the Determination of Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid (PFPeA), Perfluorohexanoic Acid (PFHA), Perfluoroheptanoic Acid (PFHpA), Perfluorooctanoic Acid (PFOA), Perfluorononanoic Acid (PFNA), Perfluorodecanoic Acid (PFDA), Perfluoroimdecanoic Acid (PFUnA), Perfluorododecanoic Acid (PFDoA), Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil and Sediment by LC/MS/MS

TESTING FACILITY

Exygen Research 3058 Research Drive State College, PA 16801 Phone:(814)272-1039

STUDY DIRECTOR

Jaisimha Kesari P.E., DEE Weston Solutions, Inc. 1400 Weston Way West Chester, PA 19380 Phone:(610)701-3761 Fax:(610)701-7401 [email protected]

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SPONSOR REPRESENTATIVE

Robert A. Paschke Manager, 3M Corporate Envirormiental Programs Bldg 42-02-E-27 SL Paul, MN 55144 Phone:(651)778-5200

PRINCIPAL INVESTIGATOR

John M. Flaherty Exygen Research 3058 Research Drive State College, PA 16801 Phone:(814)272-1039 [email protected]

PROPOSED EXPERIMENTAL START AND TERMINATION DATES

It is proposed that the analytical portion of this study be conducted from October 20, 2006 to December 31, 2007. The actual experimental start and termination dates will be included in the final report.

IDENTIFICATION AND JUSTIFICATION OF THE TEST SYSTEM

The following are the test systems for this study: • Water (groundwater, surface water and interstitial (pore) water) • Soil • Sediment

The samples will be collected by Weston Solutions. The control samples will be purchased or acquired and/or prepared by the testing facility Acquisition details for the control samples will be included in the final report associated with this study.

The test systems were chosen to assess the envirorunental impact of the test substances in the Cottage Grove, Miimesota area.

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SAMPLE PROCUREMENT, RECEIPT AND RETENTION

Water, soil, and sediment samples will be received at Exygen from 3M afler being collected by Weston Solutions. The details of sample procurement for this study are outlined in the 3M work plan entitled "Phase 2 FC Assessment Work Plan" dated July 2006, revised August 7, 2006. The number and types of samples collected will vary depending availability in the field. Additional samples may also be collected in the field at the discretion of the study director. The total number of samples received and analyzed for each matrix will be documented in the final report associated with this study.

Water, soil, and sediment samples will be used as received without further mechanical processing at Exygen. The samples will be mixed thoroughly by shaking by hand prior to taking an aliquot for the extraction. These samples will be stored refiigerated at 2°C-8°C.

The receipt of the samples will be documented in the final report and raw data associated with the study.

SAMPLE IDENTIFICATION

Prior to analysis, each sample will be assigned a laboratory sample reference number. The reference number will be unique and will distinguish each laboratory sample that is processed throughout the analytical procedure. Chromatographic data will be identified by the laboratory sample reference number.

Sample storage conditions and locations will be documented throughout the study.

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ANALYTICAL PROCEDURE SUMMARY

References: ETS-8-012.0: "Method of Analysis for the Determination of

Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid (PFPeA), Perfluorohexanoic Acid (PFHA), Perfluoroheptanoic Acid (PFHpA), Perfluorooctanoic Acid (PFOA), Perfluorononanoic Acid (PFNA), Perfluorodecanoic Acid (PFDA), Perfluoroundecanoic Acid (PFUnA), Perfluorododecanoic Acid (PFDoA), Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil and Sediment by LC/MS/MS"

VERIFICATION OF ANALYTICAL PROCEDURE

A laboratory control sample will be used for the preparation of fortified control samples. The test substance will be made into solutions as per the method, and added to the matrices via a micropipette.

For water sampling, Exygen will supply one bottle per sample collected. The bottles will be 500 mL precleaned Sci/Spec Premier wide mouth HDPE bottles. These bottles have been routinely used for fluorochemical sample collection at the testing facility and have been shown to be firee of fluorochemicals. All containers used for water sample collection will be shipped to the sample location. For water samples designated as field spikes, the water sample will be added to each container to a volumetric fill line. A field duplicate and at least two levels of field spikes of each sample will be collected. Some sites may have additional field spikes to bracket the possible concentration ranges of analytes in a location. The field spikes will contain PFBA, PFPeA, PFHA, PFHpA, PFOA, PFNA, PFDA, PFUnA, PFDoA, PFBS, PFHS and PFOS. The field spikes will be used to determine the precision and accuracy of the method for each site sampled. Laboratory spikes and laboratory duphcates for water will not be a component of this study but, if necessary, can be done with approval or by request of the study director.

For soil and sediment, Exygen will supply one 500 mL precleaned Sci/Spec Premier wide mouth HDPE bottle per sample collected or a zip-seal bag. All containers/bags used for sample collection will be shipped to the sample

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location. Samples will be added to each container or bag in the field. Laboratory duplicates and two laboratory matrix spikes will be performed for each soil/sediment sample received at Exygen Research.

Recoveries of field matrix spikes (FMS) are anticipated to be between 70% and 130% of the fortified levels. If the recoveries of the field spikes fall outside the acceptable range, the sample result will be reported as "NR" (not reported due to QC failures).

METHOD FOR CONTROL OF BIAS

Control of bias will be addressed by taking representative sub-samples from a homogeneous mixture of each matrix from untreated control samples, and by analyzing at least two levels of fortifications. Lab control spikes are used to determine the overall data uncertainty for each batch. HPLC grade water will be used to prepare the lab control spikes for aqueous samples and control soil or sediment will be used to prepare the lab control spikes for non-aqueous matrices. Triplicate lab control spikes at a minimum of two different concentrations are to be performed with each extraction batch. The relative standard deviation of the pooled recoveries must be less than or equal to 20.0% and the average recovery must be 80-120%. Low lab control spikes should be prepared at concentrations approximately five to ten times higher than the targeted LOQ and high lab control spikes should be prepared at concentrations near the mid-point of the curve.

Method blanks must be done with each extraction batch. A range of three to seven method blanks must be prepared interspersed throughout the extraction batch and analyzed throughout the analytical sequence. The mean area count for each analyte in the method blanks must be less than 50% of the area count of the LOQ standard. The standard deviation of the area counts of these method blanks should be calculated and reported. A large relative standard deviation (RSD) is expected if area counts are near the instrument noise levels due to the possibility that area counts might vary throughout a run depending on the minor target analyte background variability, minor instrument response variability, or other interference concentration present that may eiJiance or suppress the response. If the mean area counts of the method blanks exceed 50% of the LOQ standard, then the LOQ must be raised to the first standard level in the curve that meets criteria. Altematively, the method blanks could be evaluated statistically to determine outhers or technical justification to eliminate a blank may be made when determining the LOQ. The criteria are then applied again to evaluate method blank compliance. If any method blanks are removed from the LOQ determination, document in the report or the raw data as appropriate.

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STATISTICAL METHODS

Statistics will be limited to those specified in the subject method and to the calculation of average recoveries and relative standard deviations, as applicable. Each individual result for samples and lab or field duplicates will be reported; however, an average and a relative percent difference (RPD) calculation will also be done.

GLP STATEMENT

All aspects of this study shall be performed and reported in compliance with EPA TSCA Good Laboratory Practice Standards 40 CFR 792. The final report or data package (supplied to the Sponsor) shall contain a statement that the study was conducted in compUance with current and applicable GLP standards and will outline any deviations in the study from those standards. This statement will be signed by the Study Director and Sponsor Representative.

REPORT

A final report will be prepared by the principal investigator or their designee at the conclusion of the study. The report will include, but will not be limited to, the following:

• The name and address of the Study Director, Sponsor Representative, and of the testing facility.

• A statement of GLP compliance (any related documentation, such as chain-of-custody records, must be in the study records).

• The signed and dated statement by the Exygen Research Quality Assurance Unit regarding dates of study inspections and dates findings were reported to the Study Director and Management.

• A description of the exact analytical conditions employed in the study. If the subject method was followed exactly, it is necessary to include only a copy of the analytical method. Any modifications to this method will be incorporated into the report. If the method is photo-reduced, the project number and page number must be Included on each page.

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Description of the instmmentation used and operating conditions.

All results from all sets analyzed. Control and fortified samples will be identified and the data table will include sample number and fortification level.

Representative chromatograms for each analyte in each matrix, including chromatograms of a standard and a control sample, and a chromatogram at a fortification level. The location of the analyte peaks will be clearly identified in all chromatograms.

All circumstances that may have affected the quality or integrity of the data will be documented in the report.

Locations where raw data and the final report are to be archived.

Additions or corrections to the final report shall be in the form of an amendment signed by the Shidy Director. The amendment shall clearly identify that part of the report that is being altered and the reasons for the alterations. The amendment will be signed and dated by the Study Director and the Sponsor Representative.

SAFETY AND HEALTH

Laboratory personnel will practice good sanitation and health habits.

Every reasonable precaution shall be taken to prevent inadvertent exposure of persormel and the environment to the test or reference substance(s).

AMENDMENTS TO PROTOCOL

All significant changes to the analytical protocol outiined here will be expressed in writing, signed and dated by the Study Director and Sponsor Representative. Amendments usually will be issued prior to initiation of study plan change. However, when a change is required without sufficient time for the issue of a written amendment, that change may be effected verbally with supporting documentation signed and dated by the Study Durector and followed with a written amendment as soon as possible. In this case, the effective date of the written amendment will be the date of the documented change. Copies of the signed amendments will be appended to all distributed study plan copies. The original amendment will be maintained with the original study plan. Any deviations from the study plan or from the analytical

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Exygen Study Number; P0002561

method as provided will be documented and reported promptly to the Sponsor Representative.

DATA RECORD KEEPING

Records to be maintained include the following (as appropriate):

Sample tracking sheet(s) Sample receipt records, storage history, and chains of custody History and preparation of standards (stock, fortification, calibration) Description of any modifications to the method Instrument run sheets, bench-sheets or logs Analytical data tables All chromatographic and instiumental conditions Sample extraction and analysis dates A complete listing of study persormel, signatures and initials Chronological presentation of all study correspondence Any other documentation necessary for the reconstruction of the study

Chromatograms- All chromatograms will contain the following:

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

• Additionally, fortifications will include the amount of analyte added and the sample number of the sample that was fortified.

• Analytical standard chromatograms will additionally include the concentration (e.g., ng/mL).

• As part of the documentation the following sheets will be included in each analytical set: a run sheet listing the samples to be nm in the set, and an instrument conditions sheet describing the instrument type and operating conditions.

• All applicable requirements for reporting of study results as per 40 CFR 792.185.

QUALITY ASSURANCE

The QA Unit of Exygen Research will inspect the study at intervals adequate to assure compliance with GLP's, and will report the findings of audits to the Study Director, Exygen Management, and the Sponsor Representative.

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Exygen Protocol P0002561; Interim Report #16 ZM Project E06-0549



RETENTION OF DATA AND ARCHIVING

All hard copy raw data, including, but not limited to, the original chromatograms, worksheets, correspondence, and results shall be included with the data package submitted to the Study Director. These will be archived with the original study plan, amendments, final report, and all pertinent information from the Sponsor.

The testing facility shall keep all electronic raw data and any instrument, equipment, and storage logs for the period of time specified in 40 CFR 792.195. An exact copy of the materials submitted to the study director will also be kept at Exygen Research.

Exygen will obtain permission from the study director before discarding or returning samples.

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APPENDIX I

ANALYTICAL METHOD

ETS-8-012.0 "Method of Analysis for the Determination of Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid (PFPeA), Perfluorohexanoic Acid (PFHA), Perfluoroheptanoic Acid (PFHpA), Perfluorooctanoic Acid (PFOA), Perfluorononanoic Acid (PFNA), Perfluorodecanoic Acid (PFDA), Perfluoroundecanoic Acid (PFUnA), Perfluorododecanoic Acid (PFDoA), Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil and Sediment by LC/MS/MS"

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Exygen Protocol P0002561; Interim Report #16

3M Project E06-0549 Analysis of Woodbury Waste Site Groundwater Samples; 3rd Quarter 2007


^ Enviranmental Laboratory

Method

Method af Analysis for the DBtermlnaUon of PerfluorobutanDic Acid (PFBA), Perfluoropentanoic Acid (PFPeA), Pertluorohtxtnoie Ac id (PFHA), Perfluoro/iepttno/c Acid {PFHpA), Peifluoroadanolc Ac id (PFOA), Pareuarononanoic Acid (PFNA), Ptr f luorodtcmolc Acid (PFDA),

Periluoroundecanoic Acid (PFUnA), Perfluorododecmolc Ac id (PFDoA), PtrfluorobutBnesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and

Pertluorooctanesalfonate (PFOS) In Water, Soil and Sediment by LC/MS/MS

Method Number eTS-8-012.0

Adoption Date: Upon Signing

BffectiveOate: l O f h / o C

Approved By:

VUfliam K. Reagen, Technical Manager Dale

ET5-S-0I2.0 Past 1a f12 Mtttiod at Anatyi i i for Dw IM«rminiiJeA of Pcfltuerobutmeic Add (PFBA). Perlbjarapenlwialc Acid (PFPeA). Peif uercfieiEinoic

Add IPFHA). Pcrflueroheptande Add (PFHpA). PirftuorooctinDieAcid (PfOA). ParfluorenoranncAdd (PFNA). PerfluoradacanM Add (PFDA). PartuofoundwwMic Add (PFUnA). PtrfluorododecaMic Add (PPOoA). Pir i lwiabulanaBii irsnM (PFB$|.

Pei f lmrohaunuufcnal t [PFHS). and Par fuenodwmi i l on i l t (PFOS) in W « w . Sgl and SedimaM tnr LCMSMS

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1 Scope and Application

Thi» method I j to be used to quanlify Pertluofobutanoic Add (PFBA), Perfluofopentaroic Add (PFPeA), Perfhioiohexanok: Add (PFHA), Petfluoniheplanaic Add (PFHpA), Perfluorooctanoic Add (PFOA), PerfkwroronanoJc Add (PFNA). Perfluondecanoic Add (PFDA), Perfluoroundecanoic Add (PFUnA), Perfluorododecanoic Add (PFDoA), Perfluofobutanesulfenate (PFBS), PerfluorohexanasuKonale (PFHS), and PerfluoroodanasuHonate (PFOS) by High Performance Liquid Chronatognph)' coupled Io a tandem M a u Spectionetric Detecl« (LCMB/MS) in water, tol l and wdlment. The method is designed to obtain a kwer I'mt or quantitation (LOQ) of 0.02S ng/mL (water) and 0.20 ng/g (soU and sediment).

2 Msthod Summary

Aqueous sanvles are mixed with equal volumes of acetonMe, thoroughly mined, centrifuged and atquotsd f a analysis by LOMSMS. Similarly, o n » 9 n m atquols of soil and sediments are mixed with S020 ace(onil>ile.waler mixture, thoroughly mixed, cantiifuged, and aOquofad for analysis by LC/MSMS.

This is a peiiomunc».ba$ed method. Method accuracy is delemi'nad for each sample set using multiple lab«ato7 control spikes at multiple concenlralJonE. Ih is method also requires that the pradsion and accuracy Ibr each sample be detennined using feld matrix spkes (aqueous samples) or laboratory matrix spikes (soil and sediment) to verify Ihat the method Is appllcabia to each sample matrix. Sample resuNi for spkes outside of 70% to 13(ni, win not be reported due to quaUiy control sample failures.

Fortificalion levels for field matrix spikes and for labocalory matrix spikes shouki be at least 50% of the endogenous level and less than 10 times the endogenous level to be used to determine the statement of accuncy for analytkal results.

3 D e t i n i t i o n s _ ^

3.1 C a l i b r a t i o n S t a n d a r d

A sdutjon prepared by sfriking a known volume ol the Working Standanl (WS) into a predetermined amount of ASTM type I or HPLC grade water, diluted with acatonitrile, and analyzed according to INs method. Calibralkxi standards are used to calibiate the instrument response with resped to analyte concentration.

3 .2 L a b o r a t o r y D u p l i c a t e S a m p l e ( L D S , o r L a b D u p )

A laboratory dupficate sample is a separate alkguot of a sample taken In the analytkal laboratory that is extracted and analyzed separately with Identical pmeedures. Analysis of LOSS compared to Ihat of the f i r^ aliquot gfve a measure of Ihe precision associated with laboratory procedures, but not with sample collection, preservation, or storage piooedures.

3.3 F i e l d B l a n k ( F B ) / T r i p B l a n k

ASTM Type I or HPLC grade water placed in a sample container in the laboratory and treated as a sample in all respects, including exposure to sampling site condKions, storage, presenratnn and aH anaVtical procedures. The purpose of the FB is to detemiine if test substances or other interferences are present in the fleht environmenL This sample is also referred to as a Trip Blank. Trip blanks are not a requirement for soi or sedrmenl sampM.

3.4 F i e l d D u p l i c a t e S a m p l e ( F O S , F i e l d OupJ

A sample collected in duplicate at the same time from the same location as Ihe sample. The FDS is placed under klenlical drcumstances and treated exactly the same throughout field and laboratory procedures.

ETS-8-012.0 P a g e 2 o n 2

IMUiod or An»rysii Iw iTii o<ltnii)r<«non or Perfuorobulatwc Add ( fVM) . Pt{ tuonpenunM Add (PFPeA), ParfluDrohaxfriDie Add IPFHA), l^rfluorolwpunoic Add (r>FHpA>. Pvfluoroodandc Acid (PFOA), Poffluwononuiolc Add (PFNA), Perflunodduftoic

Add (PFOA). Pefljuorounddanolc Add (PFUnA). Pirfluorodadecanok Add (PFOoA^. PeriuorotlutanouiifortMt (PFaS). Piiikioronenneiil ldnau IPFKSI. u d PnSuotnidjiwuironsIa (PF(}S) In Wklw. Sol and Svilnicnl by LC/MSNS

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Analysis of the FDS compaied to Ihat of the first sample gives a measure of the predsion assodatad wth sample cdleclion, preservation end storage, as wel as with lat)oratory procedures.

3 .5 F i e l d M a t r i x S p i k e ( F M S )

A sample to whteh kno«n quantities of the target analytes are added to the sample boUe In the laboratory before the bodies are sent to the fleld for cofiedkin of aqueous samples. A known, specific volume of sample must be added to Ihe sample contakiar without rinsing. This may be accomplished by making a t i l to this lever line on Ihe oulsde of the sample container. The FIUIS should be spiked between eppnsidmataly S0% and 10 timet the expected aralyte concentiation in the sample. If llie expected range of analyte concentrat'xxis is unknown, muKpla spka* at varying levels may be prepared to increase the Italihood that a s p i n at an appiopitale level Is made The FMS is analyzed to ascertain if any matric etfeda, interferenoes, or stabiiily issues may compteale Vie interpretation of the sample analysis.

3 .6 T r i p B l a n k S p i k e ( F i e l d S p i k e C o n t r o l S a m p l e , F S C S )

An alkguol of ASTM Type I or HPLC grade water to whk:h known quanliUes of the target analytes are added in the tatxxatory prior to the shipment of Ihe collection battles. The FSCS is sxtieded and ana lêd exactly like a sample to help detemiine lithe method is in control and whethera lost oFanalyte couki be attributed to hoUing lime, sample storage and/or shipment istuas. A kiw and high FSCS are appropriate whan expected sample cancentFBIions are not known or may vary. At least one separate, un-splced sample must be taken at the same time and place as eadi FMS.

3 .7 L a b o r a t o r y C o n t r o l S a m p l e ( L C S )

An aliqual of control matrix to which known quantities of the target analytes are added in the laboratory at Ihe time of sample exbaction. At least two levels are inckidad. one generally at the k w end of the calbretbn cunre and one near ttw m'd to upper range of the cunre. The LCSs are e t radad and analyzed exactly like a laboratory sample to determine whether the method is in control. LCSs shouki be prepared each day samples are extracted.

3 .8 L a b o r a t o r y IMatr lx S p i k e ( L M S )

A laboratory mabir spike is an alX)iiot of a sample to whEh knoiui quantities of target analytes are added In the laboratory. The LMS is exbaded and analyzed exactly like a laboratory sample to deletmine whether Ihe sample matrix contributes bias to the anayical results. The endogenous concenlrstlons of the analytes in the sample matrix must be determined In a separate aliquot and the measured vakres in the LMS corrected for these conoentralkins. LtASs are required tor sdls and sediments and are optkxial for analysis of aqueous samples.

3 .9 L x i b o r a t o r y S a m p l e

A ponkm or aliquot of a samplB received liom the fiekl for testing.

3 .10 L i m i t o f Q u a n t i t a t i o n (LOG))

The bwer limit of quantitation (LLOQ) for a dataset b the kxvest concentratkn that can be reliably quantitated within the specified limits of precsnn and accuracy cfuring routine operating conditions. To siniplify data reporiing. Ihe LLOQ is generally selected as the k»est noozero standard in the calibration curve that meets method criteria. Sample LLOI3s are matrix-dependenL

The upper limit of quantitation (ULOQ) for a dataset is the highest concantrainn that can be reliably quantitated wUhrn the specified limits of precision and accuracy during routine operating condrtnns. The higtiest standard in the caibhslion cunre thai meets method criteria is defined as Ihe ULOQ.

ETS-8-012.0 Page 3 nf 12

Mdlhod or A n i l y i l i (dr lh« Oilenninatlon or PorlXiorgbulanolc Add (PF8A), PirSUDfopontanoie Add (PFPeA). PorfluorohaxanoJc A d d (PFHA), Ptrl luorohepunolc Add (PFHpA). Perfluoroodanolc A d d (PFOA), Perftjarano/unoic Add (PFMA). Perfluorodeconoic

A d d IPFOAi. perihjorounddcande Add (PFUnA). Perfk i rxododeunolcAdd (PFOoA). PdmuorobulanesuHonalQ (PFBS). PMuorot l t t ianoiu l ldnaK (PFHS), and PonhiorooclaMWildnala (PFOS) In Walar. SoU and Sodimant try l O M S I M S

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Exygen Study Number: P0002S61

3.11 M e t h o d B l a n k

An aliquot of control matrix thai is beated exactly Ike e laboratory sample induding exposure to a l giasswaie, equipinent. solvBnIs. and reagents that are used with other laboratory samples. The method blanic is used to detemiine K test substances or other interferences are present in the laboratory environment, the reagents, or

3.12 Sample A sample is an aliquot removed from a larger quantity of nialeriai intended to represent the original souree material.

3.13 S t o c k S t a n d a r d S o l u t i o n (SSS)

A ooncenlraled toiullon of a singleenaVIe prepared in the laboratory with an assayed reference compound.

3.14 Su r roga te

A compound similar to Ihe target analyte(s) In chemcal composition and behavior that it not nomnally found in the sarnple(s). A sunogate compound is typically a target analyle with at least one atom containing an isotopcaHy labeled aubsthution. If used, sunogalE^s) are added to all samples and qualHy control samples (except sdvem blanks and hall of Ihe prepared method blanks). Surrogale(s) are added to quantiiaiNeiy evakala the entire analytical pnicedure including sample collection, extradion, and analysis, Induskin c( a sunogate analyte is an optional quality contnil measure and is NOT required.

3.15 W o r k i n g S ta i ^da id (V\IS)

A sdulion of several anaVles prepared in the laboratoiy from SSSs and diluted as needed to prepare caSbrabon standanls and other required anatyte solutions.

4 Warnings and Cautions

4.1 Haa l th a n d Sa fe ty

The acute and dvortc loxidly of Ihe standanls for this method have not been precisely determined; however, each shouki be treated as a potential health hazard. The analyst shouU wear gtoves, a lab coal, and safety glasses to prevent eqMsure to chemrcats that might be present.

The bboiatoiy is responsible for maintaining a safe wort< environment and a cunent eviarenest of bcal regulations regarding Ihe handling of the chemicals used'n this method. A reference file of material saiely data sheets (MSDS) should be avaiabis to all peceonnd involved in these analytes.

4 .2 Cau t i ons

The analyst must be familiar with the laboratory equipment and potential hazards including, but not limited too, the use of solvents, pressurized gas end sohrent lines, high voltage, and vacuum systems. Refer to the appropriate equipment procedure or opemtor manual for additkxial infomiation and cautions.

5 In te r fe rences

During extiaiaion and analysis, major potential contaminant sources are reagents and glassware. A l materials used In the analyses shall be demonstrated to be free fmm interferences under condrlions of analysis by mnning method blanks.

ETS-8-012.0 Page 4 of 12

Method of Ajialyiia fo* Ihe Delenrlnallon o i PerSuorobulinoJc Add (PFBA). Perfuorapemanoic Add (PFPeAJ. PartuoralieKanoic A d d IPFHA). Poiluonihaplsnoic A d d (PFHpA), Pariluorooclanolo A d d (PFOA). Partkiorononanole Add (PFNAI. Partuoradecanolc

Add ( P f ^ A ) . ParthionMjndacanoie Add ( i ÛnA) , Periluorododecanofc A d d (PFOoA), PeftuorotMianesutonate (PFBS). PwfluGfohaxanaaullonale (PFHS), and PntuoraouanaMifonala (PFOS) In Waier. S o l and Sedhrwnlby LCIMSTMS

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Partt and tuppliet that contain TeflonV should be avoided or minimized due to the possibility of Interference endnor contamination. These may Include, but are not UmilBd to: wash boWes, TafVin* Ined caps, autovial caps, HPLC partt, etc.

The use of disposabla micnjpipettes or pipettes to allquct standard solutkxis Is lecommanded to make calibration standards and matrix spikes.

6 Instrumentation, Suppllas. and EquipBiant

6.1 Instrumentation and Equipment A high performance i f M rômatogtaph capable of pumping up to 2 sclents and equipped with a variable volume injector capable of injeding 5-200 \ i . connected to a tandem Mats Spectnmeler (LC/MSMS). Appied B'rosystems Sdex API WOO intbumenlatlon Is lequied to meet the LOQt of 0.025 ngiVnL (water) and 0.20 ng/g (soli and sediment). V analyte oonoentrations require diUions tor one or more analytes Ihat preckide the targeted LOQs from being reached. Applied Biotystems Sdex API 4000 inslmmentatton may be utilized since the LOQt wlll already be raised.

Analytical balance capable of reading to 0.00001 g.

A device to ooHed raw data for paak 'ntegtatkin and quant'itatton

15-mL and SCknL disposable polypropylene centrifuge tubes.

Disposable mterapipeltes (tO-20 pL, 25-50 p L 50-100 p L 100^001^.).

125-mL LOPE nanowHnoulh bottles.

2-mL clear HPLC vial kit.

Disposable pipettes.

Ubasonicbalh.

Centriiuge capable of spinning 15-mL and 50-mL pdypropylene tubes at 3000 rpm.

5.2 Chromatographic System Analytical Column: Luna 3 pm C8 (2) Mercury (Phenomanex), 2 mm x 4 mm, 3 (jrn (P/N; 0OM-424a-DOCE)

Temperature: 35*C

Mobile Phase (A): 2 mM Ammonium Acetate in Water

Mnhih Phase (B):Methand

Gradient Program:

Time Iminl 0.0 0.5 2.0 5.0 5.1 6.0 B.I 10.0

54A 90 90 10 10 0 0 90 90

Jt l 10 10 90 90 100 100 10 to

InjedkxiVohjme: 5 ^L (can be increased to as much as SO iJL).

Quant'itatioa' Peak Area - extemal standard caltxation curve, Mx weighted.

ETS-8-012.0

Flow Rate

lml/n»Bl 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75

Pages of 12

HoSiod o l AnaVila tor Ihe DeteminMion of Padhiorobiunol i : Add (PFBA), Parfkionfientandc A d d (PFPeA). PelSuoraneXHidc A d d (PFHA). Pefft ioiol iei i l tnelc A d ( (PFHpA). PertuonoCMnolc Add (PFOA). Pemuoionoivnolc A d d (PFNA), Pertkionideeanoic

Add (PFOA), ParfluoroundecandcAcM (PFUnA), Paifluorododecanolc Add (PFDoA). PoftuorofeulaneauVonate (PFBS), parfluararicxanesuironate (r>FHS). M d Pemuvoodenei i i ronale (PFOS) in VlWer. So l and SedimenI by LCMSIU&

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RunTime: '10minutes .

The preveut infonnation is intended as a guide; allemate eonditk)ns end equipment may be used provklBd that data qualty ofcjecdves are met.

6.3 MS/MS System

6J.1 Mode' Bedrosp i ^ Negative MRM mode, monloring the tilowinglranslions:

AnaMe PFBA

PFPeA PFHA

PFHpA PFOA PFNA PFDA

PFUnA

PFDoA

PFBS PFHS

PFOS

Transition Monitored

213-> 169

263 -» 219 313-> 269 and 3 1 3 - t 119

363 -» 319. 363 -»169 end 363 - » 1 1 9 413 -» 3 6 9 . 4 1 3 - • 219 and 4 1 3 - v 169

463 -> 419.463 -> 169 and 463 - » 2 1 9 5 1 3 - * 4 6 9 , 5 1 3 - « 2 1 9 a n d 5 1 3 - » 2 6 9 563-« 519,563-> 269 and 563-> 219

6 1 3 - * 569,613-> 169 and 613 -« 319 299 •« 80 and 2 9 9 - * 99 399-» 60 and 399-> 99

499 -> 80.499 -> 99 and 499 -> 130 Multiple transitions tot monitoring the analytes are required because summing multiple transitbns provides quantitation of isomers.that matches NMR data and has Ihe likely added beneTrl o l increased analyte signal.

The prevbus informatnn is intended as a guide, alternate instniments and equipment may be used.

7 Reagents and Standards

Walar -HPLC grade

Methand-HPLC grade

Ammonium Ace la le -AC.S. Reagent Grade

AcetonHriie-HPLC grade

Perfluorobutanoic Add (PFBA) - Oakvraod Produds. Inc

PerfkloicpeiiAanoic Ackl (PFPe^ - SigmsAlikrich

Perftuorahexanoic Add (PFHA) - Oakwood Produds, Inc

Perfluoroheptanoic Add (PFHpA) - Oakwood Products, Inc

Perfluorooaanote Add (PFOA) - Oakwood Produds, Inc

Perftuorononenoc Add (PFNA) - Oakwood Products. Inc

Perfluorodecanoic Ackf (PFDA) - Oakwood Products, Inc

Perfluoroundecandc Add (PFUnA) - Oakwood Products, Inc

Perfluorododecanoic Acid (PFOoA) - Oakwood Products, Inc

Periluorobutanesulfonate (PFBS) - 3M

ETS-8.012.0 Page 5 of 12

Method of Ana ly i i i for t i e Delenninaljon of Pedtuoroliutanoic Add (PFSA), Perfuoropenlanolc Add (PFPeA), Perfluorohexanoic Add (PFHA). Poilluoroheotinolc A d d (PFHpA), Perihiorooctanolc Add (PFOA), Pertuorononanolc A d d (PFNA). Perfluorodecanoic

A d d (PFOA), PertuoToundecanoic A d d (PFUnA), Peifluorododacandc Add (PFOoA), Perfluorobutanssuironale (PFBS). PtrfluoronaKanasulfonale (PFHS), and PaiDuoroodanetuirMiale (PFOS) In Water, SOU and SedlmerK by LCMSrMS

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Perfluonihexanasulbnals (PFhIS) - 3M

Perfluorooctanesulbnate (PF(}S) - Fkjke

The previous infomiation is intended as a guide. Reagentt and standards from alternate sources may be used.

8 Sannpla Handling

8.1 W a t e r S a m p i s E x t r a c t i o n

8.1.1 MeasuelOmLcfsamplelntoeSOmLpolypropylenecenliiugetubei FortKcetkxisaretobedaneatlhis

point, Uneoetsaty.

6.12 . Add 10 mL of acelonrHe to the sanvie in t i e centrifuge lube Cap dgHy a i d shake.

8.1J Sonicate sample for-2 hours St room tempeialuie.

8.1.4 Cenli i lugelbi-10miiutesat-3000rpm

8.1.5 Transferapcrtionofthesupemelanltoanautosaqplervlallaranalyss.

6.1;6 Dilute sample, ifnecassary, with 5(^50 BCetonilrile.'watBr.

8 .2 S o i l a n d S e d i m e n t E x t i n c t i o n

B2.1 Wsigh1g'cfsanipleMoa154nLpol)propyleneosnlrilugatube Fbrtrfcalicnsaietobedoneatlhispoint.1 necessary.

a Z 2 Add 8 mL of 8O20acelonilrilawaler to the sample in the cenlriliige tube. Cap tightly and shaka

82.3 Sonicate sample tor-2 hours St room temperature.

82.4 Centrifuge tor-10 ninules at-3000 ipm.

82.5 Tiansferaportionofthesupemalanltoaneutosanvlervialioranalvsis.

62.6 DilijtBsample. ?neces8ary,wth50:50ac8tonilr3e.'water.

B2.7 Aneiyze samples using dediosprayLC/MSJMS

Other weights and volumes can be used as king as the QC elements specified in this method are satisfied and all sample preparalk>n procedures may be leconslnided.

9 Sample Analysis - LC/MS/MS

9.1.1 Aminimunofsticalibrtitloilevelsmustbepresentintheflnalcalibralioncuve.

9.1.2 AnemrresetofcaOntlonstandaidsmustbefidudedatlhebeginnlngsidatlheendofasanipleset. As an atematlve, an entie set of caEbiabon slandanls may be irijacted at the begiining of a set followed by caS>rationstandanls'iitet8perBedeve(y5'10samplet(toaccountlbrasecondtetofstandardt). Ineither

ETS-8-012.0 P a g e 7 o n 2

Irfeiriod of Analysis for Ihe Dclenllination or PamuorDlMtanole Add (PF8A), Perfluoropenlano'c A d d (PFPeA). r*eifluorohezanolc Acid (PFHA). Pertuoroheprandc Add (PFHpA), Pemuoroodanelc Add (PFOA). Pailluorononanolc Aidd (PFNA). Perfluorodecanoic

Add (PFOA). Pariluoioundecandc Add (PFUnA). Petfluorododacenolc Aidd (f>FDoA), r*eifluDrobutanesullonate (PFeS). PenluorahexanesulfDnale (PFHS). and Perf t iMoodanMii lonale (PFOS) in Walar. Sou and SedimenI By LCMS/MS

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case, calbiatiinstandanis must be be i rn Ihe frst sample and iAer Ihe last sample The approach lypicaly depends on the length allhBaiidyecsltaquence,«herestx)nar sequences typically are bracketed by ccmplele ca ib ia ln i cunes.

9.1.3 The standanl cuve Is platted by quadratic fit ( ys ax'-^bx + c), weighted 1A< or unweighted, using siilsbls sdtwaie. The calbalkincunies may Include but shouU not be forced through zero. Themalhsmaical method used to c a k s j l ^ the calbraGan cunre should be appied consistanlly throughout a study. Any change shouki be thoroughly documvMd in t i e raw data.

9.1.4 Sample response should n d exceed standard responses. Any samples that exceed standard responses win

be further diluted and reanalyzed.

10 Quality Control

10.1 DaU Quality Objectlvas. This method and required quality contml samples is designed to generate data accurate to -i^-30K with a l imi of quantitation o l 0.025 ngfmL (water) or 0.20 ng/g, wet weight (sol end sedtnent). Any devlalions from the quality control measures spelled out below win be documented In the raw data and footnoted in the final report

10.2 Blanks

102.1 Method Blar*

Mettiod blanks must be prepared with each exbaction batch. A range of three to seven method blanks musi be prepared. These method blanks must be intersperaed throughout Ihe ext iadnn batch and analyzed InieispersBd throughout the analytical sequence.

The mean area count far each analyte in Ihe method blanks must be less than 50% of Ihe area count of the LOO standanl. The tlandanl deviatton of Ihe area counts of these method blanks should be eakulaled and reported. If the mean area counts of the method blanks exceed 50% of the LOQ standanl, then Ihe LOQ must be raited to the Tirst standard level in the cunre that meets Cfileria, or alternatively, the method blanks must be evak;a1ed statistically to detemiine outliers or technical justification to eliminate one or more results shouU be made.

1022 Solvent Blank

SofvenI blanks must be analyzed thmughout the enalytical sequence. Solvent blanks that show area counts greater than SOK of Ihe area counts of the LOQ standard mutt be evaluated to detemiine If analyticel results are significantly inpacted by semple carryover or an unacceptable buUup of analyte in the instrumental backgraund.

10 .3 S a m p l e R e p l i c a t e s

Samples should be pnepated in duplicate in the lab (sol and sediment) or collected in duplkate In the field (water). The relative penent iSflerence, RPD, should be reported. RPD results greater than 20% (vvater) or 30% (soil and sediment) will be flagged in (he report, but wi t not be eiduded f n m reporting. The requirement for repfcates exdudes field blanks and rinse blanks.

10 .4 S u r r o g a t e S p l i c e s

Surrogate spikes are not required but may be used on praied specific requirements.

ET5-8-012.0 P a g e S o r n

Method of Andysls for rhe OeleflnJnaUon ol PeifluoroCulandc Add (PFBA). Penluoropentenoic Add (PFI*eA). PBrtJorohaxanolc Add (PFHA). Pexfluoroneplanolc Add ( P F H ^ . Pwflueroodanoic Add (PFOA). Pwfluoiononandc A d d (PFMA). Paffluorodecanolc

Add (PFOA). Perihjoroundecanolc Add (PFUnA). Perfluorododecanoic Add (PFOoA), Perfluoiotwlaneaullsnale (PFBS). PetfluoronexencauNOAaw (PFHS), and PeifluoroodanesiJironale (PFOS] in WMef, Sd l and SedimenI by LCIMS/MS

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Exygen Study Number P0002561

i a , S L a b C o n t r o l S a m p l e

Tripicale lab conbol spikes al a mWmum of two different concentral'icns are to be peitoimed with each extractnn batch. Low lab oontrol spikes shoukf be prepared at oonoentrations in the range of five to ten timet higher than the taigsteij l O Q and high lab conbd splkei t ho iM be prepared al concenralioht naai the midpoint of Ihe cunre. The relative standard iaJsAsn of the pooled recoveries of Ihe contnal spkesmustbe iess than or equal to 20% end the average recovery must be 80-120%. If Ihe above criteria are not meL the entire set at saniples shouU be re-exlraded.

1 0 . 6 F i e l d M a t r i x S p i k e s / L a b M a M x S p i k e s

Recoveries of field mabix sptes (aqueous tamplet) and laboietoiy matrix spikes (soils and sediments) ere anlidpatad to be between 70% and 130% of Ihe foitifled levels. If the recoveries of the spikes (al outside the acceptable range, the semple result win be repotted a t 'NR' (not reported due to QC faiures).

The targeted (oriificalicn levels' should be al least 50% of the endogenous level and test than 10 times Ihe endogenous level to be used without justificalxxi to deteim'ne the statement of accuracy lor analytial results.

The aveiage of the semple and Ihe lab duprxale (soils and sediment) or field duplicate (water) shoukf be used to cakxilalB the recovery.

10.7 Standard Praparation

10.7.1 Standard StodcSdutiors

Prepare indlvklual stock toluliont of each analyto at -1000 \>slni. by weighing 100 mg of analytkial standard (corrected for purity and sat content, V necessary) and iflute to 100 mL with methanol or acelonilrila in separate lOOmL volumebii: flasks, f o r purity coned'on, take the amount of analyte that a needed for weighing (i.e.100 mg) and divide by the purity h dedmal tomi (i.e. 99.6% ' 0.996). The result is the weight that is needed to make the sobton conected tor puriy Ci.e. wegh 100.4 mg). For salt correction, catoulate Ihe salt content by taking the molecular weight of Ihe target compound ( i e PFOS ^ 499) end dividing by the molecular weight ol the enliie compound (i.e. PFOS potatskim sat (C8F17S03-K4' > 538). The resul is the s a l conlant In dedmal ioim Ci.e, 0.9275). Take the amount of analyte that is needed for weighing (Le. 100 mg) end dMde by the salt content In decimal loim. The resull is the weight that Is needed to make Ihe solutbn corrected tor sag content (i,e, weigh 107.8 mg). Store an slock solutions in 125 mL LOPE bottles, at-ZO'C 1 5 * 0 fiv up to 6 montiis fiom the date of preparatkin.

Altemate stock solution concentrations can be made, if necessary,

10.7.2 Standard Fortification Sdulxins

A 1 0 pg/mLmbcedfortifica5onsolutk)n containing all oftha analytes is prepared by bringing 1 mL of each of the 1000 pg/tnL slock solulkins to a final volume of 100 mL with acetonitrile in a 100-mL volumetric flask. A 1.0 ugfmL m'ned fortiflcatkin solutkin containing a l of Ihe ana^tes Is prepared by bringing 10 mL of the 10 pg/mL mbied sdutkin to a final volume of 100 with acetonHrik! in a 10(knL volumetric flask. A 0.1 pg/mL mixed fbitilicalior) solution containing aD of Ihe analytes is prepared I v l>ringing 10 mL of Ihe 1.0 o g M . mixed solulan to a Dnal volume of 100 with acetonMe n a lOOfliL volumetric flask. A 0.01 iig'mL mbiadfortiflcatton solution containing afl of the analytet Is prepared by bringing 10 mL o( the 0,1 pg/mL sohJlkn to a final volume of 100 with acetonibile in a 1C0mL volumcbic flask. Store all brtification standanls in 12S-mL LOPE bottles 2-B'C, up to 6 months fnxn Ihe date of preparatnn.

Alternate tortificalion solution concenlrations can be made, if necestaor.

10.8 Instrument Calibration

ETS-M12.0 Page; of 12

lAclhod o l Analyiia for the Detcnninelion or Periluorobulanolc Add (PFBA). Perfluotopentanoc Add (PFPeA). Perfluorohennolc A d d (PFHA), Pertluonhaplanoic Add (PFHpA), Peifluoroedandc Add (PF(M), Peifluon)nonandc A d d (Pt^r4AJ. Perfluorodecanoic

A d d (PFDA). Perfluoroundecanoic A d d (PFUnA). Perfluorododecanoic Add (PFOoA), Perfluoioliuteneiurronale (PFSa). Perfluofohexanelulfonete (PFHS). and Perrkioreoctanesutonate rPFOS) h vuater. Soil end Sedlmenr by I C M S r u S

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10.S.1 LCIMS/MScalbiaEcn standards ate prepared eidimaly in 50:50 acetomkiiewaler and are used to conslrud

t i e caRxelion curws for the weter, soil, end sediment procedures.

10.82 ThetbOowingisatypicaleienvlacifacalbta&insel AHemaboraddiionaloancenDalionsmaybeprepaied

a t needed.

Concentratxx) Initial Solution of Initial Solutkin ABquoted Volume

(ng/mL) (mL) 100 5 100 2.5 10 10 5 10

2.5 10 1 10

0.5 10

1 2.5

Rnal Solution Volume (mL)

100 10O 100 100 10O 100 100 100

Final Concantralton of Calibratton Standard

(ngWL) 5.0 2.5 1.0 0.5

0.25

0.1 0.05

0.025

Store an calibration standards in 1 2 5 ^ L polypropylene bottles at 2 'C to B'C, up to three months, AJIemale volumes and concentratnnt cf standanls may be prepared as needed.

11 Data Analysis and Calculations

Use Ihe fdkMing equalfan to eabulale the amount of analyta found (in ngfmU based on peak area) using the standanl cunre (linear regrestkin parameters) generated by an appropriate sollwaie program:

Analytefound(ng/mL). " ' " ' ' ^ ^ " - ' " " ' ^ ° " " ' . D F Stope

OF - fador by which the final volume was dikited, if necessa7.

For samples fortiried with known amounts of analyte prior to extradkm, use the following equation to calculate the penwnl recovery.

P Total analyte found (ng/mL) - Average analyle found in sample (ng/mL)

Analyte added (ngfmL)

Use Die Idlowing equation to convert the amount o l analyte bund in ng/mL to ng/g (ppb).

. ,.1 < , . ,., Analyte fbund(ng/mL)xVohjmeaxtrBcted(mL) Analyta found (ppb ~ — p — r - r r r r ' — -

Sample weight (g)

Use the following equation Io calaiate theamounlctfanalytefoundin ppb basatt on dry weight

Analyte found (ppb) dry weight - Analyte found (ppb) x [100% /total solids (%)|

1 2 M e t l t o d P e r f o r m a n c e

This is a performance-based method. Method aocutacy is detennined for each sample set using multiple laboratory control spkes at multiple concentrations. This method also requires that the predsion and accuracy for each sample be determined using field mabsr spikes (aqueous samples) or laboratory mabix sp9«s (soil and tedinent) to verify that the method is applcable to each sample matrix. Sample resutt for spikes outskia ol 70% to 13C^, will ncA t)e reported due to quaQty conbol sample faitures.

eTS-8-012.0 P a g e l » o f l 2

Utthoa of Analysfi lor ihe DatanhlnaUon of Perfluorobulandc Add (PFBA), Ptifluoropentanoic Add (PFPeA). Peifluorohexanofc Add (PFHA), Pcrfluoioheplanoic Acid IPFHpA). Peif luoroocunok Add ( fTOA) . Peffkjoninonanoic A d d (PFNA), Pcffluofodecanoic

A c d (PFOA), Perfluorouidecanoic Add (PFUnA). Perfluorododecanoic Acid (PFDo^ . PerfluorosuttneujHwiate (PFBS). PariluorDhexanasullanale (PFHS). and PerfluoroodanesuKonate (PFOS) In V^Tiler. Sofl and Sediment by LC/MSrMS

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Recoveries of fleld mabix spikes (aqueous samples) and laboratory mttoix spkes (sdb and sediments) are anfldpated to be betvireen 70% and 130% of the loriified levels. If the recoveries of the spikes fall outside the acceptable range, the sample result will be reported as t i t C (not reported due to QC laiures).

Any method peifoimsnce parameten Ihat are not achieved must be consUerBd in the evaiuatfori of the data Nonconformance to any tpedlied parameteit must be described and discusud if the Tecliiîcal Manager (nsn-GLP study) or Study DUectar (GLP study) chooses to repori the data.

K crileiia listed In this method perfonnance section are n d met, maintenance may be perfonned on the system and samples reanalyzed, or ottier actions taken as appropriate. Dccumemallactnnsinlherswdata.

If dale are to be reported when periinmance criteria have not been met, the data must be fbolnoled on tables and discussed in the text of Ihe report.

12 .1 S y s t a m S u i t a b i l i t y

System SuHabHiy standaidt are not a lequiiad component of this method. If required by pmtocol or by Ihe technicel manager, a iT&iimum of three system tultabillty samples are iniecled at the t i e g M n g of each analytkal mn prior to the calibratkxi cunre. Typicafly these samples are at a concenbation near the nsd level of the caibratiDn curve and are repealed injections Irijm one autosampler vial. The system tuAabUty Injedkma must have area counit vdth an RSD of £5% and a reteninn time RSD of $2% to be ccmpliant

12 .2 Q u a n t i t a t i o n

Calibration Curve: The coefficient of deleiminafion {/') vahie for the cefbraton curve must be greater than or equal to 0.985. Each point in the cunre must be within 125% of the Iheorelical concenbation wHh the exceptkxi of the U O Q , which may be within ±30%. Calbration curve points thet are not al the high or k m end of the cunre may not be deactivated. Other cunre pdnis may only be dropped if extracted standanls are used to buiki the cunre.

C O I Perfonnance: The caKirebon standards that are Interspersed throughout the analytical sequence to account for a second set of standards are evaluated as continuing caibralian verifications in addilion to being part of the caSbratnn cunre. The eocuracy ol each cunre point must be within 25% of the theoretical value (30% for towest cunre p o h l Samples that are bracketed by CCVt not meeting these criteria must be reanalyzed.

Damonatration of Specificity: Specificity is demonstrated by chmmalognaphic retention lime (within 4% of standard) end the mast spedrel response of unique nns,

12 .3 S e n s i t i v i t y

The targeted limit of quanllalnn for a l analytes is 0.025 ng/mL (water) and 0.20 ng/g (tolls and sediments, wet we'ighl). The LOQ for any specific analyte may vary depending on Ihe evabiatlon of appropriate blanks end Ihe accuracy of the low-level calibration cun/e points. Refer to Sednn 10 for additional details.

1 2 . 4 A c c u r a c y

This method and required quality control tanv>les are designed to generate date Ihat are accurate to * I - 3 M . Sednn 10 contains addNlanal infomialion regaming the required accuracy of laboratory oonlml spikes, fiekl matrix spikes (water samples) and laboratory matrix spkes (soils and sediments).

12 .5 P r e c i s i o n

Samples shoukf be prepared in duplicate In the lab (toll and sedimenI) or collected h duplicete in the fiefcl (aqueous). The relative percent dUierence, fW>, should be reported. RPO results greater than 20% (water) or 30% (soil and sedimenO wiH be flagged in the report but will not be exduded from reporting. The requirement for replcates exdudes fiekl blanks or rinse blanks.

Stcl icn 10 contains addSonal informalion regarding the required p iedsnn of laboratory ccnlrol t pke t .

Mciliod or Anat^ is (or the Oelcrminalion o l Perfluonibulanoie Add (PFBA). PerfluorDpenlanoic A d d (PFPeA), PerfluOTOhexanoic A d d (PFHA). ParflMicneptflnde A d d (PFHpA). Perfluorooctanoic M a (PFOA). Poffluorononanoic Add (PFNA), Paifluorodecsnoie

A d d (PFOA). Peflluereundecanoic Add (PFUnA). Perfluorododecanoic Add (PFDoA), PenkMrabutenesulfonBte (PF8S], Perfluorahaianasulfonale (PFHS), and PerfluoroodanesuHonata (PFOS) hi Walei , Sd l w a Sodimant by LjCJMSrUS

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1 3 P o l l u t i o n P r e v e n t i o n a n d W a s t a M a n a g e m e n t

Waste generated when pertomilrig this method will be disposed of appropriately. The original samples will be archived el Ihe 3M EnwraTnentarLaboraloty in accordance with Internal procedures.

1 4 R e c o r d s

Each data package generated tor a study must indude all supporting infonnation lor leconsbuctkin of the data. Information for the data package must indude, but is not limited to the following iems: study or project number, sample and standanl prep sheets/records, (istrument mn tog (instrument batch reconls, insbuiient acqulsitton meniod. summary pages), insbument results files, chromatograms, calibrîon cuves, and date calculaflcns.

1 5 R e f e r e n c e s

Exygen Research Analytical Method V00033OS-1 details method devekipment and verification of recoveiy for multiple analytes in gmundwater, suitice water, soil, and sediment This will be arehived as part of E0S4S49.

16 A f f e c t e d D o c u m e n t s

None.

1 7 R e v i s i o n s

Intone.

ETS-8-012.0 Page 12 of 12

Method o l Anaiysia for t lw DelanninalioA o l Peifluorobulanoic Add (PFBA), Peifluoropantanole Add (PFPeA), Peifluonriexenoic A d d (PFliA), PerfluoroneptanoicAeld (PFHpA). Perikjonwdsnoie Add (PFOA), Peifluo/ononanote A d d (PFNA). Perfluondecanolc

Add (PFDA), PerexHoundacanot: Add (PFUnA), Perfluorododecanoic Add (PFDoA), PcrfluorobUenesidlonale (PFBS). Paifluoroliejianeaullbnate (PFHS). and Perfluoroodaneautronate (PFOS) in Water, S d l end Sediment by LOMS/MS

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Exygen Protocol P0002561; Interim Report #16 ZM Project E06-0549



APPENDIX II

MINNESOTA POLLUTION CONTROL GUIDANCE DOCUMENTS

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E x y g e n S t u d y N u m b e r : P 0 0 0 2 5 6 1

August 18,2006

|}t. William Reagan, Labontoty Manager 3M Environmeotal Laboratoiy Envitonmenial, Health, and Safety Operatians 3M Center. MS 260-SN-I7 Maplewood, MN 55144

Re: Guidance for Peifluorochcmical Analysis in Water

Deer Dr. Reagan:

I have been asked to piovide melhod guidance (along wilb QC acceptance criteria) for the pcrSuotochemical aiuilysis in water. These criteria should be considered as minimum standards (the lahoiatoty may use stricter criteria) and shotJd be met when analyzing and itpoiting sample results to Oie Minnesota Pollution Control Agency. The criteria appear below. Please leview these criteria and, if you have a i^ questionsfcomments/conections, please conuci me at (£S I) 296-S44S or via emadl at [email protected].

Initial Calibratien

The Initial Calibration Curves should contain al least six calibration points. The r for each curve must be giealcr than or equal to 0.990. The recoveiy (accuracy) for each point in the curve must be 75% to 125% except for Ihe lowest point in the curve which must be 70»4 u> 130%, The lowest calibniion point in the ciuvcs shall be al the analyte report level. If a sample concentiation exceeds Ihe highest calibration sUuidard from the Initial Calibration, the sample must be diluted into the calibration range and reanalyzed. If the instrument calibration resulti are outside die acceptance criteria, a number of actions can be lakcn:

1) Check the instiument operating conditions, Irstiument maintenance may be required,

2} Review the response at each calibration level to insure that the problem is not associated with one standard. If the problem appeals to be associated with one of the standards, that standard can be re-injected. If Ihe problem persists, re-make the standard and re-analyze it.

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E x y g e n S t u d y N u m b e r : P 0 0 0 2 5 6 1

Dr. William Reagan August II, 20O( Page 2

3) The last alternative is to narrow the calibiation curve by removing the top or bottom point. Ifthe calibration criteria are now met, the analysis can proceed. However, theie are noiifications in removing calibration points. If the top point is removed, die need for diluting samples and le-analyzing will occur at a lower concentration level. Ifthe low point in the curve is removed, the sensitivity of die analysis has changed and thus the report level will need to change. This may impact action levels.

Centinelne Calibration

The Initial Calibration Curves aie verified every 12 hours by analyzing a mid-level suuidard. The drift must be within 70% to 13D%, Ifthe instnunent calibiation results aie outside the acceptance criteria, check die instnunent operating conditions and/or peifoim instrument maintenance. Re-analyze the calibration standard. Ifthc calibration criteria are still not met, a new Inidal Calibniion must be perfonned. All samples that were analyzed since the lost passing calibration standard must be le-enalyzed.

Method Detection Limits/Reeort Limits

Method detection levels (MDU) and report levels (RLs) are detennined annually or after a major change to Ihe insoument conditions. The MOLs are determined per die procedure defined in 40 CFR 136, Appendix B, The report levels (RLs) should be three times die MDLs, The RLs are also the lowest standard in the calibration curves. Ifthe accuracy of the RL standaid does not meet the 70% to 130% criteria, new RL standards are chosen and analyzed until the accuracy criteria are met

Batch PC

A batch is defined as op to 20 environmental samples. At a minimum, each batch must contain a mediod blank, a duplicated analysis (either a sample duplicate or a duplicated spike), and a Laboratory Control Sample (LCS). Every environmental sample must be spiked.

1) The concentration of each target analyte in Ihe method blank must be less than the associated repon level, Ifthe method blank is contaminated, measures must be taken to eliminate the problem. Affected samples must then be n-processed. If the contamination can not be eliminated, the results must he qualified to indicate the problem. All concentration levels for the affected taiget analyte which are less than ten times the concentration in Ihe blank should be qualified with a "B" to indicate that the sample results may contain a bias related to the bhuik contamination. Concentrations of the affected analyte which are above ten times the blank contamination will not need to be qualified.

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E x y g e n S tudy N u m b e r : P 0 0 0 2 5 6 1

Dr. William Reagan August It, 2006 Page 3

2) The Relative Percent Difference (RPD) between sample duplicates, matrix spike duplicate pain (MS/MSD pairs), or LCS/LCSO pairs must be less than or equal to 20Ve, However, if die concentration of the target analyte in die sample/sample duplicate is less than five times the report level, the diffeicnce between duplicates is used to measure precision. The difiisrence must than be less than or equal to the report level. Ifthc RPD between duplicates is outside the acceptance criteria, corrective actions must be taken and all associated samples re-aiulyzed. Ifthe criteria are still not met afler collective actions, contact (he MPCA QA Coordinator for advice,

3) All target analytes ate to be spiked into the Matrix Spike (MS) or LCS, The spiking levels should be five to ten times die RLs, The LCS is made fiom reagent-grade water. The % recoveries of the target analytes m the MS must be between 70% and 130% while the % recoveries of the taigcl analytes in the LCS must be between 80% and 120%. If die % recoveries are outside the accepunce criteria, coirective actions must be udcen and all associated samples re-analyzcd. If the criteria are still not met after corrective actions, contact die MPCA QA Cooidinator for advice.

Thanks for your attention on diis matter.

Sincerely,

William Sciuton, QA Coordinator Performance Management and Quality Section Environmental Analysis and Outcomes Division

cc: Gaiy Knieget (MPCA) Douglas Wetzstein (tvipCA) Fred Campbell (MPCA)

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Minnesota Pollution Control Agency SJOLaraireRefloadNorth | Sl.P«jl,MNSSIS5-41B4 | flS1.3ll6,flUO j BOMSr- lSM | flS 1-382-5333 TTT | 1Maw.pca.Mate4nn.ul

September 11,2006

Dr, William Reagan, Laboratory Manager 3M EnvironmcnuJ Laboratoiy Environmental, Health, and Safety Operations 3MCenter,MS260-5N-l7 Maplewood, MN 55144

Re: Guidance for Perfluorochemical Analysis in Water

Dear Dr. Reagan:

During our meeting of August 28,2006, the following four main issues were discussed:

1, What report levels to use,

2. How to handle analyses that do not meet acceptance criteria, 3. Matrix spikes, and 4, Initial calibration requirements.

At the meeting, you presented the case for using 25-ng/L (25 ppt) as the reporting level for each target analyte. The Minnesota Pollution Control Agency (MPCA) will accept this level for Uie Cottage Grove Phase 2 FC Assessment. However, we reserve the right to change the reporting level for any future work as FC analytical melhod development improves.

The MPCA only wants Ih» most accurate data that can be produced for the Phase 2 Assessment. Therefore, we will require that only results that meet all QA/QC accepunce limits will be reported to die MPCA. However, we ask ttiat you submit in writing what actions will be conducted to get results tiiat meet the criteria (re-analysis, re-extraction and rc-analysis, dilution of the matrix, inst]tumcnl maintenance, etc.). We will also require that you maintain the results and raw data of all analyses that do not meet QA/QC criteria for our review if requested at a fiituredate.

Matrix spiking of eveiy water sample is required for the project. You suggested that all samples be spiked in the field and that you will be doing this procedure for Ihe upcoming sampling round. We will accept the data Ihat you generate in this fashion. However, the MPCA may split samples at some locations for QA/QC purposes and we will not require that Ihe matrix spikes for those samples be field spiked. The MPCA will monitor Uie agreement between the splits and, if Uic results don't seem to agree, will re-evaluate Ihe matrix spiking procedure.

SlAaul I Inrocrd | DclroTlUIwi j Oulalh | Minkato | Manriali | Haehmttt ( MMmar | l^rntadon iaa«po(hcon>unwMCydMjp«fMf

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http://1Maw.pca.Mate4nn.ul




I>. Willjanl Reagan September 11,2006 Page 2

The last issue concents Uie ability to delete calibration points fiom the middle of die curve. Before an analyst deletes a data point from die curve, he/she must review the response at each calibration level to insure that the problem is not associated wiUi one standard, Ifthe problem appean to be associated with one of the standanls, Uiat standard should be re-injected. If Uie problem persists, re-make the standard and ic-anaiyze it. After these efforts, a point may be eligible for removal fiom the curve. The Agency will allow Ihe removal of a calibration point from the curve under Uie following provisions. If a non-linear calibration model is used in Oie initial calibration curve, a quadratic (second order) curve will require at least six non-zero standanl levels while a polyiuimiat (diird order) curve will require at least seven non-zero standard levels. Care must be taken to insure dial Uiere are enough remaining calibration points for the initial calibration curve.

Please review these criteria and, if you have any questions/commenls/coiicctions, please contact me at (651) 296-8445 or via email at [email protected].

Thanks for your attention on these matters.

Sincerely,

William Scruton, QA Cooidinator Perroimance Management and Quality Section Environmental Analysis and Outcomes Division

cc: Gaiy Knieger (MPCA) Douglas Wetzstein (MPCA) Fred Campbell (MPCA)

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ATTACHMENT D: METHOD DEVIATIONS

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3M Confidential Analysis of Woodbury Waste Site Groundwater Samples; 3rd Quarter 2007

RECORD OF NONCONFORMANCE / DEVIATION

/. Ident i f icat ion Study / Project No. Dat8(s) of Occurrence: Document Number: E06-0549 Sequence s0r0902a, ETS 8-154.3 Deviation type D SOP D Equipment Procedure 0 Method (Check one) D Protocol • GPO D Other:

//. Descr ip t ion Method Requirements:

1. System Suitability (section 10.5) area count RSD s 5% and retention time RSD s 2%. 2. Calibration curve points < ± 25% residuals, except LOQ of ±30% (section 12.2), 3. CCV recoveries (section 10.4). Recoveryof CCVwill be 100% i 2 5 % . 4. Laboratory Control Samples (section 9.5). Average r e c o v ^ ± 20%, RSD S20%. 5. Sample/Sample Dtiplicale RPO s 20% (section 9.3). 6. FMS recoveries within ± 30% (section 9.6).

Actual procedure/process:

(1) The opening system suitability samples did not inject properly for reasons unknown. Closingsystem suitability samples were analyzed, though not required, with all analytes meeting acceptance criteria. Other QC samples will be used to evaluate data.

(2) The 0.1 ng/mL curve point for PFUnA had an accuracy of 73,7% - point was retained. (3) Several later CCVs for PFDA, PFUnA and PFDoA exceeded acceptance criteria. Samples bracketed by

failing CCVs will be re-analyzed. (4) The average recovery for PFBA was 123% with a RSD of 21 %. The RSD for PFDoA was 24%. (5) A couple locations had PFHxA RPD values greater than 20% (6) Several locations had FMS recoveries that did not meet method acceptance criteria. Data will be footnoted

appropriately • •' ••• ;

///. Actions Taiien (such as amendment issued, SOP revision, <etc.)

Corrective Action (n Yes 0 No) Reference:

Acceptability of the nonconforming wori<:

1) System suitability - other QC items were used to assess data accuracy - calibration curve points and curve fit criteria were met (with the exception of PFUnA - see #2). All reported sample results were bracketed by passing CCVS, indicating that the instrument was operating properly. 2) Nine curve points were used to establish the curve for PFUnA. Retaining the 0.1 ng/mL curve point with an accuracy of 73,7% has a negligible affect on the sample results. 3) Sample braclceted by failing CCVs for PFUnA and PFDoA were re-analyzed. 4) This set of low level LCS for both PFBA and PFDoA had recoveries around 140%, which contributed to the average recovery and RSD not meeting method acceptance criteria. All LCS were control charted and used in the deteiminat ion of analytical uncertainty. 5) Samples with RPD values > 2 0 % will be footnoted in the results table of the report. 6) Where FMS exceeded method acceptance criteria, analytical uncertainties will be expanded when appropriate.

Actions; D Hatting of Work D Client Notification D Work Recall D Withholding of Report

B Other: Deviations will be noted in final report. Analyt lcai uncertainties will be adjusted as needed.

Recorded by: Susan Wolf f' -x Date: 12/03/2007 'x uaie: i//u,3/-

>S7\M /â/r/ Authoria^tion (Study Director): " Date:

Sponsor ADProva! (GLP Protocols): Date:

Technical Manager Approval {if hawng of work or vTO*recaii are indicated): NA Date: NA

ETS-4-06.4 Page 1 of 2 Attachment A: Record of Nonconformance / Deviation form

Documentation of Deviations and Control of Nonconforming Testing

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IV. Authorization to Resume Worii Where halting of work occurred, resumption of wori( must first be approved by Technical Management

Technical Manager Approval: NA Date: NA

Deviation No. (assigned by Study Director or Project Lmd at the end of study or project)

ETS-4-08.4 Page 2 ol 2 Attachment A: Record of Nonconformance / Deviation form


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/. Identification Study / Project No. Date(s) of Occunnence: Document Number: E06-0549 Sequence s070908a, ETS 8-154.3 Deviation type D SOP D Equipment Procedure 13 fêthod : (Check one) D Protocol D GPO D Other:

I I . D e s c r i p t i o n Method Requirennents;

1. System Suitability (sectlor> 10.5) area count RSD s 5% arid retention time RSD s 2%. 2. Calibration curve points <± 25% residuals.except LOQ of ±30% (section 2.2) 3. CCV recoveries (section 10.4). Recovery of CCV will be 100% ±25% 4. laboratory Control Samples (section 9.5). Average recovery i 20%, RSD S20%. 5. FMS recoveries within ± 30% (section 9.6).


(1) System Suitability - PFNA and PFDoA had an area count RSD values greater than 5% (6.5% and 7,2% respectively.

(2) The 0.1 ng/mL curve point for PFNA had an accuracy of 72.1% - point was retained, (3) PFHxA, PFHpA and PFDoA each had one of twelve CCVs that did not nheet method acceptance criteria

with recoveries of 70.8%, 126% and 130%, (4) 8/22/07 extracted LCS; tiie low set of LCS for PFUnA and PFDoA had recoveries in excess of 150%. As a

result, the average recovery and RSD for these two analytes did not meet method acceptance criteria. PFUnA average recovery was 130% was an RSD of 19%. PFDoA average recovery was 152% with an RSD of 25%. 8/27/07 extracted LCS; the average recovery for PFOA and PFDA were just under the acceptance criteria wth recoveries of 79.4% for PFOA and 77.4% for PFDA.

(5) Several locations had FMS recoveries that did not meet method acceptance criteria. Data will be footnoted appropriately. ^ ^ _ _ _ _ ^ ^ _

///. Actions Taken (such as amendment issued, SOP revision, etc.)

Corrective Action ( • Yes 0 No) Reference:

Acceptability of the nonconforming work:

1) System suitability criteria for PFNA and PFDoA were just outside method acceptance criteria. Calibration curve points and curve fit criteria were met. CCV recoveries indicate that the instrument was operating property. 2) Ten curve points were used to establish the curve for PFNA. Retaining the 0.1 ng/mL curve point with an accuracy of 73.7% has a negligible affect on the sample results. 3) Of the twelve CCVs analyzed during the course of the run. only one CCV for PFHxA, PFHpA and PFDoA fell Just outside method acceptance criteria. Noncompliant CCVs will be addressed (n the final report. 4) All LCS will be control charted and used in the determination of analytical uncertainty. 5) Where FMS exceeded method acceptance criteria, analytical uncertainties will be expanded when appropriate.

Actions: D Halting of Wori< O Client Notification D Work Recall D Witiholding of Report

S Other: Deviations will be noted in final report. Analytical uncertainties will be adjusted as needed. r

Reco rded by: S u s a n Wo l f I % D a t e : 12 /03 /2007

^ ? ^ 1 . tsiiM b-Authorizatiootetudy Director): u ~ ~ " Date: D a t e : •

Sponsor AppcovaKGlP PralDcete); , ^ ^ Date:

Technical Manager Approval (if haiung of work or work recaii are indicated): N A Date: N A

ETS-4-08.4 Page 1 of 2 Attachment A: Record of Nonconfomiance / Deviation form


Page 205 of 207




IV. Authorization to Resume Work Wfiere hatting of worK occurred, resumption of work must first be approved by Technical Manamment

Technical Manager /s jproval: NA Date: NA

Deviation No. (assigned by Study Director or Project Lead at tho end of study or prefect)

ETS-4-08.4 Page 2 of 2 Attachment A: Record of Nonconfonmance / Deviation form


Page 206 of 207




/. Identification Study / Project No. Date(s) of Occun-ence: Document Number: E06-0549 Sequence 0071008b, ETS 8-154^ Deviation type D SOP D Equipment Procedure El tvlethod (Check one) O Protocol D GPO D Other:

//. Description Method Requirements:

1. System Suitability (section 10.5) area count RSD s 5% and retention time RSD s 2%. 2. Calibraton cun/e points <± 25% residuals, except LOQ Of ±30% (section 12.2) 3. CCV recoveries (section 10.4). Recoveryof CCV will be 100% ±25% 4. FMS recoveries within ± 30% (section 9,6).


(1) System Suitability - PFHxA, PFHpA. PFDA, PFBS, and PFHS had an area count RSD >5% (2) The 0.5 ng/mL curve point for PFNA had an accuracy of 128% - point was retained. (3) PFHpA; one CCV that did not meet method acceptance aiteria witfi a recovery of 65.5%. (4) Several locations had FMS recoveries that did not meet method acceptance criteria. Data will be footnoted

appropriately

I I I . A c t i o n s T a k e n (such as amendment issued, SOP revision, etc.)

Corrective Action (D Yes 0 No) Reference:

Acceptability of the nonconforming work:

1) Calibration curve points and curve fit aiteria were met. CCV recoveries indicate that the instrument was operating properly and FMS recoveries will be used to assign analytical method uncertainty. 2) Ten curve points were used to establish the curve for PFNA. Retaining the 0.5 ng/mL curve point with an accuracy of 128% has a negligible affect on the sample results. 3) CCVs not meeting method criteria will be noted in the final report. 4) Where FMS exceeded method acceptance criteria, analytical uncertainties will be expanded when appropriate.

Actions: O Halting of Work D Client Notification P Worit Recall D Withholding of Report

0 Other: Deviations will be noted in final report. Analytical uncertainties will be adjusted as needed.

Recorded by: Susan Wolf ^K -x Date:, 12/03/2007

, r .:.. J l c -H /;^3/g7 Authorizatifll|> (Study Director): D Date: .

Sponsor ApprovaUiSLEJErot^cote^f -^ . Date:

Technical Manager Approval (if halting of vwrk or work recaii are indicated): NA Date: NA

N. Authorization to Resume Work Where halting of work occurred, resumption of work must first be approved by Technical Manamment

Technical Manager Approval: NA Date: NA

Deviation No. (assigned 6y Study Di'recfor or Pnêct Lead at the end of study or project)

ETS-4-08.4 Page 1 of 1 Attachment A: Record of Nonconformance / Deviation form


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