Analytical Interim ReporW15: Phase I Phase II · 2012. 10. 4. · Interim Experimental Initiation (Phase I): October 15, 2007 Interim Experimental Completion (Phase 11): November

3M Environmental Laboratory €06-0549 Interim Report #15

Analytical Interim ReporW15: Phase I & Phase II Analysis of PFBA, PFOA, PFBS, PFHS, and PFOS in Soil Samples from the Woodbury Waste Disposal Site; October 2007: Analytical

Phase I & Phase II

Data Requirement 40 CFR Part 792

Author Michelle D. Malinsky, Ph.D.

Phase Completion Date Date of signing

Performing Laboratory 3M Environmental Health and Safety Operations

Environmental Laboratory 3M Center, Bldg 26O5-N-I 7

Maplewood, MN 55144

Project Identification E06-0549

Total Number of Pages 156

€06-0549 Interim Report #15 Woodbury Soils: October 2007 Page I of 156

3M Environmental Laboratory EO6-0549 Interim Report #15

This page has been reserved for specific country requirements.

€06-0549 Interim Report #15 Woodbury Soils: October 2007 Page 2 of 156

3M Envimnmental Laboratory E064549 lnterim Report #15

Inspection Dates

1011 812007

11112/2007-11114/2007~ 11/19/2007~ 1 1 I2612007

11/29/2007-11/30/2007

Quality Assurance Statement

Date Reported to Phase Laboratory Study Director

Management

In-Phase 11/2/2007 12/6/2007

12/4/2007 12/6/2007

Data & Report Audit 12/4/2007 12/6/2007

Data & ReportAudit

Study Title: Analysis of PFBA, PFOA, PFBS, PFHS and PFOS in Soil Samples from the Woodbury Waste Disposal Site October, 2007: Phase I. Study Identification Number: E06-0549; Exygen Protocol PO002561

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 study director and laboratory management.

~~

/ zb6 /o 7 QAU Representative Date

€06-0549 lnterim Report # I5 Woodbury Soils: October 2007 Page 4 of 156

3M Environmental Laboratory E064549 Interim Report # f5

Table ofcontents

GLP Compliance Statement ...................................................................................................................... 3

Quality Assurance Statement .................................................................................................................... 4

Table of Contents ....................................................................................................................................... 5

List of Tables ............................................................................................................................................... 6

Study Information ....................................................................................................................................... 7

Summary and Introduction ......................................................................................................................... 8

Test Samples ............................................................................................................................................ 19

Reference Substances ............................................................................................................................. 19

Control Substance .................................................................................................................................... 20

Method Summaries .................................................................................................................................. 20

Preparatory and Analytical Methods ......................................................... 20

Analytical Results ..................................................................................................................................... 24

Cali bration ................................................................................................... 24

Limit of Quantitation (LOQ) ........................................................................ 24

Blanks ......................................................................................................... 24

Continuing Calibration ................................................................................ 25

Lab Control Spikes (LCSs) ........................................................................ 25

Sample Duplicates ..................................................................................... 29

Dry Weight Determination ......................................................................... 29

Laboratory Matrix Spikes (LMSs) .............................................................. 30

Data Summary and Discussion ............................................................................................................... 30

Phase I ........................................................................................................ 30

Phase I I ....................................................................................................... 31

Statistical Methods and Calculations ....................................................................................................... 41

Accuracy and Precision Equations ........................................................... 41

Determination of Analytical Method Uncertainty ...................................... 41


3M Environmental Laboratory EO6-0549 Interim Report #I5

Statement of Conclusion .......................................................................................................................... 44

Phase I ........................................................................................................ 44

Phase II ....................................................................................................... 44

References ............................................................................................................................................... 44

List of Attachments ................................................................................................................................... 44

Signatures ................................................................................................................................................. 45

List of Tables

Table 1 . Sample Results Summary: Phase I .......................................................................................... 9

Table 2 . Sample Results Summary: Phase II (PFBA only) .................................................................. 13

Table 3 . Sample Description Key Code ................................................................................................. 19

Table 4 . Study Reference Substances ................................................................................................... 19

Table 5 . Study Control Substance (Surrogate) ...................................................................................... 20

Table 6 . Instrument Parameters: Phase I ............................................................................................. 21

Table 7 . Liquid Chromatography Program (Phase I: Isocratic) ............................................................ 21

Table 8 . Mass Transitions ....................................................................................................................... 22

Table 9 . Instrument Parameters: Phase II (PFBA and PFOA) ............................................................. 22

Table 10 . Liquid Chromatography Program: Phase II PFBA (Gradient) ............................................. 23

Table 11 . Liquid Chromatography Program: Phase II PFOA (Gradient) ............................................. 23

Table 12 . Mass Transitions: Phase I1 PFBA ......................................................................................... 23

Table 13 . Mass Transitions: Phase II PFOA ......................................................................................... 23

Table 14 . Lab Control Spike Results: Phase I Extraction Day 10/15/2007(1. 2) .................................. 26

Table 15 . Lab Control Spike Results: Phase I Extraction Day 10/18/2007(1. 2) .................................. 27

Table 16 . Lab Control Spike Results: Phase II ..................................................................................... 28

Table 17 . Phase II PFBA Sample and QC Results ............................................................................... 32

Table 18 . PFOA Results Sample E06.0549.1572 ................................................................................. 40

Table 19 . Phase I Analytical Method Uncertainty Determination .......................................................... 42


3M Envitvnmental Laboratory E064549 Interim Report #15

Study Information

Sponsor

3M Company

Sponsor Representative

Robert A. Paschke 3M Corporate Occupational Medicine 3M Center, Bldg. 220-06-W-08 Maplewood, MN 55144 Telephone No. (651) 737-8569

Study Director

Jaisimha Kesari, P.E., DEE Weston Solutions, Inc. 1400 Weston Way West Chester, PA 19380

Study Location

FAX NO. (651) 733-9066

Testing Facility

3M Environmental Health and Safety Operations 3M Center, Bldg. 260-05-N-17 Maplewood, MN 55144

Study Personnel

William K. Reagen, Ph.D., Testing Facility Management Michelle D. Malinsky, Ph.D., Principal Analytical Investigator Cliffton Jacoby, Ph.D., Technical Reviewer Cleston Lange, Ph.D. Zhuojing Liu Vallabha Tantry

Study Dates

Interim Experimental Initiation (Phase I): October 15, 2007

Interim Experimental Completion (Phase 11): November 29, 2007

Interim Completion: Date of interim report signing

Location of Archives

All original raw data, protocol, and 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.

E064549 Interim Report #15 Woodbury Soils: October 2007 Page 7 of f56

3M Environmental laboratory €06-0549 Interim Report #15

Summary and Introduction

The 3M Environmental Laboratory extracted and analyzed soil samples collected from the Woodbury, MN waste disposal site by Weston Solutions personnel on October 2-4, 2007. Sample were submitted for analysis as part of 3M Environmental Laboratory project number E06-0549 Interim Report # I 5(Analysis of Fluorochemicals in Water, Soil, and Sediment Using LC/MS/MS for the 3M Cottage Grove Monitoring Program Phase 2). The GLP protocol number for this project is P0002561. As delineated in the general project outline for this sampling event (see Protocol Amendment #I 3), samples were to be analyzed in two phases for an abbreviated target analyte list. Phase I was a rapid part-per-million (pg/g) screening analysis intended to differentiate soil samples with endogenous "high-level" (ppm) fluorochemical levels in the approximate range of 0.25 pg/g to 250 pg/g. All samples were then reanalyzed in Phase II for a targeted LOQ of 1 nglg for PFBA only. The target analyte list for this sampling event included perfluorobutanoate (PFBA), perfluorooctanoate (PFOA), perfluorobutane sulfonate (PFBS), perfluorohexanesulfonate (PFHS), and perfluorooctanesulfonate (PFOS).

For the Phase I analytical portion of this investigation, soil samples were analyzed for the target analytes using 3M Environmental Laboratory Method ETS 8-42.0 "Solvent Extraction and lsocratic LCIMSIMS Analysis of Soils for C4-CI2 Perfluorinated Carboxylic Acids and Perfluorobutane Sulfonate, Perfluorohexane sulfonate, and Perfluorooctane sulfonate". The analytical start date for Phase I was October 15,2007 and the analytical termination date was October 19, 2007. For this initial screening phase, every fifth sample was analyzed in duplicate to assess extraction reproducibility. Each sample was spiked with a known amount of isotopically labeled perfluorooctanoic acid, PFOA[I ,2 13C], as a surrogate. Laboratory matrix spikes were not prepared. All samples produced results either below or near the approximate LOQ of 0.1 pg/g for PFBA. Because it was determined that a lower LOQ was required for PFBA, all samples were reextracted and analyzed in the Phase I1 analytical portion of this study for PFBA only using 3M Environmental Laboratory Method ETS 8-12.1 "Method of Analysis for the Determination of Perfluorinated Compounds in Water, Soil, and Sediment by LC/MS/MS". (The extraction procedure for ETS 8-42.0 is equivalent to the extraction procedure in ETS 8-12.1 .) For Phase II, each soil sample was extracted in duplicate and two different levels of lab matrix spikes were prepared. Both the Phase I and Phase II analytical results have been corrected for the dry soil weight. (The percent moisture content was determined for each sample after completion of the Phase I analysis.)

At the request of the study director, Phase II extracts for E06-0549-1572 were diluted and analyzed for PFOA only.

Table 1 below summarizes the sample results for the Phase I analytical for PFOA, PFBS, PFHS, and PFOS. Table 2 summarizes the sample results for the Phase II analytical for PFBA.



Table 1. Sample Results Summary: Phase 1.

PFOA bg/sl dry

weight

PFHS

weight Pg/sl dry

('"Mass extracted Average

Sample Description fg) %Solids

PFBS

weight cg/sl dry Analytical

Comment Sample ID

E06-0549-1556

E06-0549-1557

E06-0549-1558

E06-0549-1559

E06-0549-1560

E06-0549-1560 dup

weight Recovery

0.201

c0.121

c0.130

~0.106 133

co.144 122

WBMN SB GP103 0 0145 0,9812 84.9

WBMN SB GP103 0 0200 0.9926 93.7

WBMN SB GP102 0 0240 0.9285 88.9

WBMN SB GP102 0 0195 0.9635 79.9

WBMN SB GPlOl 0 0080 1.163 81.3

WBMN SB GPlOl 0 0080 1.084 81.3

0.182

0.334

0.154

0.135

~0.105

c0.113

c0.120

C0.107

c0.121

C0.130

c0.105

c0.113

<0.122

co.109

c0.123

c0.132

c0.107

c0.115

<LOQ

NA

CLOQ

NA

<LOQ

NA NA I : average €06-0549-7 560

%RPD €06-0549-7560

E06-0549-1561 WBMN SB GPlOl 0 0120 1.041 95.5

E06-0549-1562 WBMN SB GPFOl 0 01 10 0.9531 86.0

E06-0549-1563 WBMN SB GPFOl 0 0230 0.9677 73.0

E06-0549-1564 WBMN SB GPFOl 0 0270 0.9164 85.6

E06-0549-1565 WBMN SB GPFOl RB 0000 1.1669 NA

E06-0549-1566 WBMN SB GPAOl 0 0080 I .055 87.6

E06-0549-1566 dup WBMN SB GPAOl 0 0080 1.017 87.6

average €06-0549-7 566

% RPD €0069549-1 566

<0.100

0.545

~0.141

c0.127

(31c0.0853

0.547

0.61 1

~0.100

1.24

c0.141

c0.127

'3'<0.0833

0.820

1.08

c0.102

'"8.85

c0.144

0.190

'3'<0.0871

'2'7.09

'"7.13

0.101

"'16.6

0.256

0.477

(3)c0.0858

6.45

6.53

143

104

131

134

106

88.4

95.8

0.579

l i

0.950

27

7.11

0.56 6-49 1.1 I :: E06-0549-1567 WBMN SB GPAO2 0 0200 0.9588 86.7

E06-0549-1568 WBMN SB GPA02 0 0240 1.015 93.1

E06-0549-1569 WBMN SB GPA03 0 0200 1.071 90.0

E06-0549-1570 WBMN SB GPA03 0 0200 1.096 90.3

E06-0549-1570 dup WBMN SB GPA03 0 0200 0.9987 90.3

1.16

0.305

0.106

0.113

0.115

1.79

0.915

C0.104

0.204

0.216

c0.122

'"7.75

1.08

1 A8

1.61

'"16.6

0.960

0.305

0.294

0.299 133

3.8 3.2

average €06-0549-1570

%RPD €06-0549-1570

0.114

1.9

0.210

5.8

1.54

8.1

€06-0549 Interim Report #15 Woodbwy Soils: October 2007 Page 9 of 156


<LOO

NA

5.39

cO.117

c0.105

<0.110

<0.100

CLOQ

NA

“Mass extracted Average

Sample ID Sample Description (91 %Solids

0.585 137

0.57 1.9

4.93 87.1 b

<0.116 107 b

c0.103 118 b

0.129 119 b

0.141 121 b

0.135 120

8.6 0.98

E06-0549-1571 WBMN SB GPAO3 0 0080 0.9617 82.2

E06-0549-1572 WBMN SB GPA 04 0 0165 1.0520 89.0

E06-0549-1573 WBMN SB GPA 04 0 0200 0.9630 94.0

E06-0549-1574 WBMN SB GPA 05 0 0080 0.9182 84.3

E06-0549-1575 WBMN SB GPA 05 0 0195 1.0042 91.2

E06-0549-1575 dup WBMN SB GPA 05 0 01 95 0.9723 91.2

average €00605494575

%RPD €06-0549-1575

CLOQ

NA

~~

E06-0549-1576 WBMN SB GPBOl 0 0120 1.0660 89.2

E06-0549-1577 WBMN SB GPBOl 0 0170 1.0040 86.3

E06-0549-1578 WBMN SB GPCOl 0 0160 1.0301 94.0

E06-0549-1579 WBMN SB GPCOl 0 0210 0.9654 96.1

E06-0549-1579 dup WBMN SB GPCOl 0 021 0 1.0557 96.1

0.349 121

17 7.6

average €06-0549-1579

%RPD €06-0549-1579

E06-0549-1580 WBMN SB GPC02 0 0160 1.0007 79.5

E06-0549-1581 WBMN SB GPC02 0 021 0 1.0919 87.4

E06-0549-1582 WBMN SB GPBO2 0 0160 1.0287 94.2

E06-0549-1583 WBMN SB GPBOP 0 01 10 0.9614 85.6

E06-0549-1584 WBMN SB GPDOl 0 0120 1.0906 93.1

E06-0549-1584 dup WBMN SB GPDOl 0 0120 1.0750 93.1

average €06-0549-1584

%RPD €06-0549-1584

PF OA

weight

0.643

‘241>250

‘*’17.0

‘“0.497

‘“0.183

‘‘0.114

6 d g ) dry

“)O. 149

47

1.34

c0.115

<0.103

C0.107

c0.0981

CLOQ

NA

0.145

<0.104

c0.103

1.79

e0.0980

c0.0994

CLOQ

NA

PFBS

weight

1.37

1.49

0.168

<0.129

co.109

c0.112

f w g ) dry

CLOQ

NA

1.54

c0.0968

co.0944

co.101

c0.0921

CLOQ

NA

0.130

<0.0890

C0.0945

0.248

<0.0891

C0.0904

CLOQ

NA

0.702 0.694

c0.131

<0.111 0.583

c0.115 0.586

Surrogate % 1 Analytical

Recovery Comment

136

138 a

0.365

<0.107

c0.105

1.79

<0.100

<0.102

2.76

0.197

0.367

<0.122

0.379

0.320

105

117

116

53.3

125

116



PFOS

weight CS/s)dry

(’’Mass extracted Average

SamDle ID SamDle DeSCnDtiOn (9) %Solids

Surrogate %

Recovery

E06-0549-1585 WBMN SB GPDOl 0 0080 0.9687 83.0

E06-0549-1586 WBMN SB GPEOl 0 0120 1.0276 81.8

E06-0549-1587 WBMN SB GPEOl 0 0160 1.0196 95.2

E06-0549-1588 WBMN SB GPJOl 0 0085 1.0899 86.7

E06-0549-1589 WBMN SB GPJOl 0 0135 0.9625 97.1

E06-0549-1589 dUp WBMN SB GPJOl 0 0135 1.0417 97.1

~ ~

c0.102

<0.0900

%0.0996

0.197

<0.0971

~0.104

average €06-0549-1 589

%RPD €06-0549-1589

E06-0549-1590 WBMN SB GPGOl 0 0058 0.9564 88.6

E06-0549-1591 WBMN SB GPGOl 0 0108 1.0797 96.7

E06-0549-1592 WBMN SB GPJOl RB 0000 0.9758 NA

E06-0549-1593 WBMN SB GPHOl 0 0155 0.921 1 86.3

E06-0549-1594 WBMN SB GPHOl 0 0205 1.001 3 91.8

E06-0549-1594 duo WBMN SB GPHOl 0 0205 0.9346 91.8

0.1 58

c0.0973

(3k0.104

1.30

0.185

0.125

average €06-0549-1 594

%RPD EO6-0549-1594

E06-0549-1595 Soil Trip Blank 1 1.062 95.8

E06-0549-1596 Soil Trip Blank 2 0.941 1 95.7

E06-0549-1597 Soil Trip Blank 3 1.0555 95.8

~ ~

C0.0984

co.111

co.0990

PFOA

weight h / 9 ) dry

137

114

112

~ ~~

c0.124

0.610

c0.103

C0.105

c0.106

c0.0984

CLOQ

NA

c0.117

c0.0953

(3)~0.102

0.333

c0.108

c0.116

CLOQ

NA

‘5’0.118

co.110

c0.0984

~0.100

0.327

c0.0953

~0.0892

co.101

~0.0933

PFHS

weight hg/sl dry

c0.126

3.16

c0.105

c0.108

co.109

<0.100

NA I e:

0.155

0.271

c0.103

c0.106

c0.107

c0.0989

eLOQ

8.9 I

1.84

c0.0959

‘3)~0.1 03

5.49

1.20

0.986

1.09

19

111

118

110

99.3

113

113

113

0.17

Analytical Comment


3M Environmental Laboratory €06-0549 Interim Report #f 5

(1) Mass of soil extracted is the native wet weight. Reported concentrations have been corrected for the average dry weight (percent solids).

(2) Sample result reported from a high level calibration curve.

(3) Concentration of aqueous rinse blank samples reported in pg/g (wet weight).

(4) Area counts of the sample extract greatly exceeded the area counts of a 250 pg standard. Per request of the study director, dilutions of the Phase II sample extracts were prepared to determine an accurate PFOA concentration (Average = 3020 pg/g, XRPD = 5.2%). See Data Summary and Discussion for more information.

(5) Sample extracts produced concentrations within the established calibration range; however, instrument carryover from E06-0549-1572 (PFOA >250 pg/g) is suspected.

Analytical Comments

(a) Sample results are estimated to be accurate to within 100&60% based on sample surrogate recovery and limited laboratory QC samples (lab control spike recoveries).

(b) Sample results are estimated to be accurate to within 100t42% based on sample surrogate recovery and limited laboratory QC samples (lab control spike recoveries) See Determination of Analytical Method Uncertainty for more information.

(c) Surrogate recovery exceeded 100+60%. Excessive PFOA concentration (>250 pg/g) in native soil likely suppressing surrogate signal that elutes from the LC column at the same time. Sample results for other analytes reported despite the low surrogate recovery.

€06-0549 Interim Repoft #f 5 Woodbury Soils: October 2007 Page f 2 of f 56


3M LlMS ID

€06-0549-1 556

E06-0549-1556 DUP

Table 2. Sample Results Summary: Phase II (PFBA only).

extracted amount Conc. Conc. (ngidg)

Sample Description (91 dry weight

WBMN SB GP103 0 0145 0.9446 7.50 9.35

WBMN SB GP103 0 0145 0.9970 7.53 8.90

Average Concentration (nglg)

%RPD

Average %Solids

E06-0549-1557 WBMN SB GP103 0 0200 0.9500 6.50

E06-0549-1557 DuP WBMN SB GP103 0 0200 1.0371 6.50


% RPD

Average %Solids

"9.12

5.0

84.9

7.30

6.69

7.00

8.8

93.7

E06-0549-1558

E06-0549-1558 DuP

62.4 I lo

WBMN SB GP102 0 0240 1.0297 60.0 65.5

WBMN SB GP102 0 0240 0.9905 52.1 59.2

Average %Solids I 88.9

E06-0549-1559 WBMN SB GP102 0 0195 1.0981 128

E06-0549-1559 DuP WBMN SB GP102 0 01 95 1.0235 126

146

154


% RPD

Average %Solids

150

5.5

79.9

1.091 0 4.00 4.13

4.20 I 1.0220 I 4.00 I E06-0549-1560

E06-0549-1560 DUP

WBMN SB GPlOl 0 0080


E06-0549-1562 1 WBMN SB GPFOl 0 0110


% RPD

Average %Solids

E06-0549-1561 WBMN SB GPlOl 0 0120 0.9207 4.00

E06-0549-1561 DUP WBMN SB GPlOl 0 0120 0.9624 <1.00


Average %Solids

%RPD

e1.17

NA

81.3

4.14

4.09

e1.11

NA

95.5

36.7 I 6.8

E06-0549-1562 DUP

Average %Solids 1 86.0

WBMN SB GPFOl 0 0110 1.0760 32.8 35.4

€06-0549 Interim Report #I5 Woodbury Soils: October 2007 Page 13 of 156

3M Environmental Laboratory E060549 Interim Report #15

extracted amount

3M LJMS ID Sample Description (SI

E06-0549-1563 WBMN SB GPFOl 0 0230 1.0612

E06-0549-1563 Dup WBMN SB GPFOl 0 0230 1.0463

'"PFBA

Conc. Conc. (nglg) @a) dry weight

1.04 1.34

1.33 1.74


%RPD

Average %Solids

E06-0549-1564

E06-0549-1564 Dup

1.54

26

73.0

WBMN SB GPFO1 0 0270

WBMN SB GPFOl 0 0270


%RPD

Average %Solids

E06-0549-1565 1 WBMN SB GPFOl RB 0000 I 0.9600 I <1.00

1.0099 2.46 2.85

2.25 1 1.0693 I 2.06 1 2.55

23

85.6

'3k1.04

E06-0549-1566

E06-0549-1566 Dup

I WBMN SB GPAOl 0 0080

WBMN SB GPAOl 0 0080


% RPD

Average %Solids

E06-0549-1567 WBMN SB GPA02 0 0200 0.9796 50.8

E06-0549-1567 dup WBMN SB GPAO2 0 0200 1.0265 43.7

0.9140 72.0 89.9

118 I 1.0156 I 105 I 104

27

87.6

59.8

49.1

Average Concentration (ngla)

%RPD

Average %Solids

E06-0549-1568 WBMN SB GPAO2 0 0240 0.9351 28.4

E06-0549-1568 dup WBMN SB GPAO2 0 0240 0.9224 27.0


54.4

20

86.7

32.6

31.5

32.0

% RPD I 3.7

~

E06-0549-1569

E06-0549-1569 dup

Average %Solids I 93.1 ~~ ~~

WBMN SB GPA03 0 0130 1.0899 2.81

WBMN SB GPA03 0 0130 0.9750 3.33

~

2.86

3.79

3.33

28

90.0

E06-0549 Interim Report #I5 Woodbuty Soils: October 2007 Page 14 of 156


3M LlMS ID

E06-0549-1570

E06-0549-1570 dup

extracted amount Conc. Conc. (nglg)

Sample Description (g) (ng) dry weight

WBMN SB GPAO3 0 0200 0.9508 7.30 8.50

WBMN SB GPA03 0 0200 0.9089 7.57 9.22

%RPD

Average %Solids

E06-0549-1571 WBMN SB GPAOB 0 0080 0.9061 23.6

E06-0549-1571 dup WBMN SB GPA03 0 0080 0.9263 33.2

Average Concentration (ng/g)

%RPD

Average %Solids

8.86

8.1

90.3

I

31.7

43.6

E06-0549-1572

E06-0549-1572 dup

37.6

“32

82.2

WBMN SB GPAW 0 0165 0.9491 21 8

WBMN SB GPA04 0 0165 0.9971 170

E06-0549-1573

E06-0549-1573 dup

258

192

m225

30

89.0

WBMN SB GPA04 0 0200


E06-0549-1574

E06-0549-1574 dup

0.9773 4.26 I 1.0112 I 4.37

WBMN SB GPAO5 0 0080


4.64

4.60

E06-0549-1575

E06-0549-1575 dup


%RPD

Average %Solids



4.62

0.86

94.0

E06-0549-1576

E06-0549-1576 dup

WBMN SB GPBOl 0 0120


1.0604 2.02 I 1.0776 I 1.48

Average %Solids

2.26

1.63

89.2


%RPD

Average %Solids

1.94

“32

84.3

0.9549 -4 .oo I 0.9673 1 -4.00

4.15

-4.13


%RPD

Average %Solids

d.14

NA

91.2

0.9338 99.7 1 1.0344 1 106

120

115


%RPD

m117

4.1


3M Environmental Laboratory EOf3-0549 Interim Report #I5

3M LlMS ID

E06-0549-1577

E06-0549-1577 duD

I I PFBA

extracted amount Conc. Conc. (nglg)

Sample Description (9) (ng) dry weight

WBMN SB GPBOl 0 0170 0.9135 1.70 2.16

WBMN SB GPBOl 0 0170 0.9206 1.74 2.19

Average %Solids

E06-0549-1578 WBMN SB GPCOl 0 0160 1.031 7 2.19

E06-0549-1578 dup WBMN SB GPCOl 0 0160 1.0102 5.14


%RPD

86.3

2.26

5.41

2.17 1 1.6

E06-0549-1579 WBMN SB GPCOl 0 0210 0.9145 1.48

E06-0549-1579 dup WBMN SB GPCOl 0 0210 1.0450 1.25

1.68

1.24


% RPD


%RPD

Average %Solids

E06-0549-1580 WBMN SB GPC02 0 0160 1.0759 19.1

E06-0549-1580 dup WBMN SB GPC02 0 0160 1.0921 23.2

‘*‘a2 I 3.84

1.46

30

96.1

22.3

26.7

I Average %Solids I 94.0


%RPD

Average %Solids

24.5

18

79.5

E06-0549-1581

E06-0549-1581 dup

WBMN SB GPCO2 0 0210 1.0862 21.1 22.2

WBMN SB GPCO2 0 0210 1.0029 19.2 21.9


%RPD

Average %Solids

E06-0549-1582 WBMN SB GPBO2 0 0160 1.0726 2.30

E06-0549-1582 dUp WBMN SB GPB02 0 0160 0.9521 1.66


%RPD

Average %Solids

E06-0549-1583 WBMN SB GPB02 0 01 10 0.9360 29.7

E06-0549-1583 dUp WBMN SB GPB02 0 0110 0.9345 23.0


%RPD

Average %Solids

€06-0549 Interim Report #I5

22.1

1.5

87.4

2.28

1.85

2.06

21

94.2

37.1

28.7

32.9

25

85.6

Woodbury Soils: October 2007 Page 16 of 156


3M LlMS ID

E06-0549-1584

E06-0549-1584 dup

extracted amount Conc. Conc. (ng/g)

Sample Description (a) (na) dry weight

WBMN SB GPDOl 0 0120 0.9438 1.49 1.70

WBMN SB GPDOl 0 01 20 1.0567 1.59 1.62


%RPD

Average %Solids

E06-0549-1585 WBMN SB GPDOl 0 0080 1.0218 3.81

E06-0549-1585 dUp WBMN SB GPDOl 0 0080 0.9556 3.50


%RfD

Average %Solids

E06-0549-1586 WBMN SB GPEOl 0 0120 1.0103 37.5

E06-0549-1586 dUp WBMN SB GPEOl 0 0120 0.9906 44.6


%RPD

Average %Solids

1.66

4.8

93.1

4.49

4.41

4.45

1-8

83.0

45.4

55.0

50.2

19

81.8

E06-0549-1587 WBMN SB GPEOl 0 0160 0.9424 17.2

E06-0549-1587 dup WBMN SB GPEOl 0 0160 1.0383 18.3

19.2

18.5

1.0781 < l .oo 4.07

4.07 I 1.0768 I 4.00 1


%RfD

Average %Solids

18.9

3.5

95.2

E06-0549-1588

E06-0549-1588dup

0.9901 <1 .oo -4.04

4.07 I 0.9654 1 4.00 I

WBMN SB GPJOl 0 0085



%RPD

Average %Solids

€06-0549 Interim Report #15

c1.07

NA

86.7

Woodbuty Soils: October 2007

E06-0549-1589

E06-0549-1589d~p

Page 17 of 156




%RPD

Average %Solids

E06-0549-1590 WBMN SB GPGOl 0 0058 1.0327 8.49

E06-0549-1590dup WBMN SB GPGOl 0 0058 1.0718 5.84


%RfD

Average %Solids

a . 0 5

NA

97.1

9.28

6.15

@7.71

(q41

88.6

3M Environmental Laboratory E064549 Interim Report # I5

extracted amount

3M LlMS ID Sample Description (a)

E06-0549-1591 WBMN SB GPGOl 0 0108 0.9505

E06-0549-1591d~p WBMN SB GPGOl 0 0108 1.0726

(‘’PFBA

Conc. Conc. (nglg) (ng) dry weight

4 . 0 0 4.09

<1 .oo co.964


%RPD

Average %Solids

E06-0549-1593

E06-0549-1593dup

~~ ~~

d.03

NA

96.7

WBMN SB GPHOl 0 0155 0.9782 45.6 54.0

WBMN SB GPHOl 0 0155 0.9698 43.9 52.5

E06-05481592 I WBMN SB GPJOl RB 0000 1 1.0751 I 4.00 1 ‘3’<0.930


%RPD

Average %Solids

E06-0549-1594 WBMN SB GPHOl 0 0205 0.9499 5.39

E06-0549-1594d~p WBMN SB GPHOl 0 0205 0.971 3 6.50


%RPD

Average %Solids

N53.3

2.9

86.3

6.18

7.29

6.74

16

91.8

E06-0549-1595 1 Soil Trip Blank Set 1

%Solids

E06-0549-1596 I Soil Trip Blank 2 I 1.0571 1 c1.00

95.8

c0.988

%Solids

E06-0549-1597

I ~ 95.7

Soil Trip Blank 3 0.9622 I @’IE NA

%Solids

(1) Except where noted, Phase I I PFBA sample results are considered accurate to within 100*30% based on lab matrix spike recoveries and other laboratory QC samples. The overall analytical method uncertainty for this project was determined to be 100*29%. See the Data Summary and Discussion and the Statistical Methods and Calculations sections or more information.

(2) PFBA results are considered accurate to within 100*50% based on lab matrix spike recoveries and other laboratory QC samples. See the Data Summary and Discussion Section for more information.

(3) Concentration of aqueous rinse blank samples reported in ng/g (wet weight).

(4) %RPD of sample and sample duplicate exceeded 30%.

(5) Lab matrix spike recovery exceeded 100*50%; however, spiking error suspected. Phase I I results agree well with Phase I results (average 117 ng/g). Results estimated to be accurate within 100i42% based on Phase I analytical method uncertainty.

(6) IE = Instrument Error. Instrument sohare error occurred during the injection of this sample and no data was recorded. Sample concentration is not reported.

95.8

€06-0549 Interim Report # I5 Woodbury Soils: October 2007 Page 18 of 156


Chemical Name

Chemical Formula

Identifier

Test Samples

Perfluorobutanoate Perfluorooctanoate

GFSOO-H' C~F&OO-NH;

CAS # 37522-4 CAS # 335-67-1

Forty-two samples (40 soil samples and 2 aqueous "rinse blank" sample) were received at the 3M Environmental Laboratory on October 5, 2007 from Weston Solutions, Inc personnel. The samples were logged in by 3M Environmental Laboratory personnel and placed in refrigerated storage on October 5, 2007 until they were removed for extraction on October 15 and October 18, 2007. Samples were re-extracted on November 15, 16, 19, and 20, 2007 for the Phase II analysis. Samples for this study are "real world" samples, not dosed with a sDecific lot of test substance. The table below provides the key code for sample

source

Expiration Date

descript'ions.

Table 3. Sample Descri

Aldrich 3M

2/16QOI 7 2/27/2017

String Number

1

Chemical Lot Number

TCR Number

Physical Description

tion Key Code.

0971 3EC 332

TCR-757 TCR-123

Colorless Liquid White Powder

String Descriptor

General Sampling Location

Sample Type

Sampling Method (GP=Geoprobe), Boring Location (A through J), Boring

Number

Sample Type

Sampling Interval (Depth)

Example

WBMN= Woodbury, MN

SB=Soil Boring

GPCO2 is the second geoprobe sampling location within the "C"

area

O=primary sample volume

RB=equipment rinseate blank

0145= grab sample colleceted 14.5 feet below ground surface

Reference Substances

Table 4 lists the pertinent information regarding the reference substance used for this study.

1 Storage Conditions I Frozen I Frozen I

I Purity I 98.7% I 95.0% I

€064549 Interim Report #75 Woodbury Soils: October 2007 Page f 9 of 756

3M Environment81 Laboratory €06-0549 Interim Report #I5

Chemical Formula

Identifier

source

Chemical Name ~~~~~

C~FSSOCK' CsF&OCK' C~F~TSO~.K*

CAS # 29420-49-3 CAS # 3871-99-6 CAS # 2795-39-3

3M 3M 3M

Storage Conditions

Chemical Lot Number

I Expiration Date I 01i18l2017 I 211 21201 7 I 6/31 I201 6 I Frozen Frozen Frozen

Lot 2 NB# 12006789 217

Purity

I TCR Number I TCR-359 I TCR-83(SE036) I TCR-1166 I

97.3% 98.6% 86.9%

I Physical Description I WhitePowder I White Powder [ White powder 1

Control Substance

Chemical Name

Chemical Formula

Identifier

~

PFOA[1,2 I3C]

Pemuorooctanoate[l ,~''CI

GF15[13C]F,[13C]OOH+

NA

Control Substance

Table 5 provides the pertinent information regarding the control (surrogate) substance used in this study.

Table 5. Study Control Substance (Surrogate).

711 5l2010

I ChemicalLotNumber 1 3507-277 I

Purity 97.6%

Method Summaries

Preparatory and Analytical Methods

Extraction All samples, calibration standards, and associated quality control samples were extracted using the procedure outlined in ETS-8-042.0 for the Phase I analysis. (Extraction by ETS-8-

E064549 Interim Report # I5 Woodbwy Soils: October 2007 Page 20 of 156


Software

042.0 is equivalent to the extraction procedure outlined in ETS-8-12.1.) Briefly, 1 g of soil was accurately weighed into a 15 mL centrifuge tube. The soil aliquot was spiked with a known amount of surrogate and 8 mL of 80:20 acetonitri1e:water extraction solvent was added. After thoroughly mixing the soiVsolvent system, the samples were then sonicated for two hours at room temperature. After sonication, the sample aliquots were centrifuged at 3000 rpm for 15 minutes to pellet the solids. An aliquot of clarified supernatant (extract) was then removed to an autovial for analysis.

Samples were extracted for Phase I analysis on October 15 and October 18,2007 and analyzed on October 16 and October 19,2007.

For Phase II analysis, samples were extracted in duplicate using the same procedure described above (ETS-8-12.1); however, the surrogate spike was omitted. Additionally, two laboratory matrix spikes (LMSs) were prepared for each sample. A low level spike was prepared at approximately 5 ng and a higher level spike was prepared at approximately 75 ng. Sample extracts of E06-0549-1572 prepared in Phase II were diluted (1:5000) with extraction solvent and analyzed separately for PFOA in a subsequent analytical run. An additional on-column dilution factor of 5 was achieved by only injecting 1 pL of the diluted sample extract versus a calibration curve prepared using 5 pL injection volumes. Lab matrix spikes of the sample extract were also prepared and diluted. See the Laboratory Matrix Spike section for more information.

Mass Lynx Version

Analysis Phase I

All sample and quality control extracts were analyzed for PFBA, PFOA, PFBS, PFHS, PFOS, and PFOA[I ,2 13C] using high performance liquid chromatography/ tandem mass spectrometry (HPLC/MS/MS). The isocratic LC method described in ETS-8-042.0 was used. Pertinent instrument parameters, the liquid chromatography program, and the specific mass transitions analyzed are described in the tables below.

Table 6. Instrument Parameters: Phase I I Instrument Name I ETSAmelia I

Guard column

I Z-spray I Ion Source I I Polarity I Negative I

E064549 Interim Report #15 Woodbury Soils: October 2007 Page 21 of 156


(I'PFHS

Table 8. Mass Transitions

399199 80

399180 80

Mass Transition Dwell Time (msec)

Instrument Name ETSOllie

49911 30

499199

499180

"'PFOS

Ion Source

Polarity

Software

Z-spray

Negative

Analyst 1.4.2

~ ~

I Liquid Chromatograph 1 Agilent 1100 ~~ I I Guard column I Betasil C8 (4.6 mm X 150 mm), 5 pm I I Analytical column I Betasil C18 (4.6 mm XI00 mm), 5 pm I I Injection Volume I 5 PL I 1 Mass Spectrometer I Applied Biosystem API 4000 Q trap 1



Step Number

0

1

Table I O . Liquid Chromatography Program: Phase II PFBA (Gradient) - - - ~~

Total Time Flow Rate Percent A Percent B

2 mM Ammonium Methanol (min) (pUmin)

Acetate (as)

0.00 1000 97.0 3.0

0.5 1000 97.0 3.0

2

3

6.0 1000 3.0 97.0

9.0 1000 3.0 97.0

I 4 I 9.01 I 1000 I 97.0 I 3.0 I 5 12.0 1000 97.0 3.0

Table 11. Liquid Chromatography Program: Phase II PFOA (Gradient)

1

2

3

Step Total Time Flow Rate Percent A Percent B

Methanol Acetate (as)

0.5 1000 97 .O 3.0

11.0 1000 5.0 95.0

13.5 1000 5.0 95.0

4

5

13.6 1000 97.0 3.0

17.0 1000 97 .o 3.0 ~

Table 12. Mass Transitions: Phase II PFBA Mass Transition

Analyte I QVQ3 Dwell Time (msec)

PFBA

Table 13. Mass Transitions: Phase II PFOA

2131169 200

Mass Transition Analyte 1 QVQ3

Dwell Time (msec)

€06-0549 Interim Report #I5

PFOA

Woodbury Soils: October 2007

41 31369 150

4131219 150

41 311 69 150

Page 23 of 156

3M Envimnmental Laboratory E064549 Interim Report # I5

Analytical Results

Calibration Calibration standards were prepared by spiking known amounts of stock solutions containing the target analytes into I g aliquots of 3M Environmental Laboratory soil matrix TCR-842. Each spiked soil standard was then extracted in the same manner as the collected samples. For Phase I, a total of eleven standards were prepared ranging from 0.1 pg to 250 pg per standard. For Phase I I , a total of ten standards were prepared ranging from 1 ng (0.001 pg to 250 ng (0.250 pg). A quadratic, l /x weighted or 1/x2 weighted, calibration curve was used to fit the data. The data was 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 extracted calibration standard used to generate the final calibration curve met the method calibration accuracy requirement (Phase I: ETS 8-42.0 100&30%; 100&35% for the LOQ standard and Phase II: ETS 8-12.1 100&25%; 100*30% for the LOQ standard.) Calibration standards on the high (or low) end were disabled as necessary to generate a curve that met the accuracy requirements over the desired calibration range. The coefficient of determination (R2) was greater than 0.999 for all analytes.

Limit of Quanfifafion (LOQ) The LOQ for this analysis, as defined in ETS-8-42.0 and ETS-8-12.1, is the lowest non-zero calibration standard in the curve in which the area counts are at least twice those of the method blank(@ and meets the calibration accuracy requirement described above (Phase I ETS-8-42.0: 1 OOi35%; Phase II ETS-8-12.1: 100*30%).

Blanks Four types of blanks were prepared and analyzed with the samples: method blanks, solvent blanks, equipment rinseate blanks, and field/trip blanks. Each blank type is described below.

Solvent Blank Several extraction solvent blanks (80:20 acetonitri1e:water) were analyzed to assess system contamination and/or instrument carryover. Analyte peak area counts in all solvent blank samples were less than half the area counts of the calibration standard used to establish the LOQ except when following a high level standard or sample extract.

Six method blanks were prepared with each day samples were extracted by extracting separate 1 g aliquots of soil matrix TCR-842.

For Phase I, three blanks were spiked with surrogate and three were not. Method blanks were prepared to evaluate the levels of background contamination in the overall extraction process (vials, etc). All area counts for the method blanks were less than half the area counts of the calibration standard used to establish the LOQ. For the first extraction set, the three method blanks spiked with surrogate produced recoveries of 119%, 115%, and 119%. For the second extraction set, the spiked blanks gave surrogate recoveries of 113%, 119%, and 11 9%.

For Phase II, six unspiked method blanks were prepared and analyzed each day samples were extracted. Area counts for all method blanks were less than half the area counts of the LOQ standard on the given day.

Method Blank

Equipment Rinseate Blanks



Two aqueous equipment rinseate blanks were submitted as samples: E06-0549-1565 and E06-0549-1592. These two water samples were treated as soil samples (1 g weighed and extracted in the same manner). Both rinseate blank samples produced concentrations of the target analytes less than the analytical LOQ indicating that equipment contamination was not present in the targeted calibration range.

Prior to sample collection, three sample containers were filled with soil matrix TCR-842, sealed, and shipped to the sample collection site along with the empty containers. These samples were analyzed as the trip blanks. The trip blanks serve as additional method blanks that account for any storage conditions andlor holding time issues that the samples may experience. For Phase I , the resultant field blank concentrations for all analytes was less than the LOQ of approximately 0.1 pglg with the following exception. E06-0549-1595 (Soil Trip Blank 1) produced a PFOA concentration slightly above the LOQ at 0.1 13 pglg. It is believed that this measurable amount of PFOA was caused by instrument carryover from E06-0549-1572 (PFOA>250 pg/g) and is not actually present in the soil extract. For Phase II, all three trip blanks produced PFBA concentrations less than the approximate LOQ of 1

Trip Blank

nglg.

Continuing Calibration

Phase I During the course of the analytical sequence, several continuing calibration verification samples (CCVs) were analyzed to confirm that the instrument response and the initial calibration curve were still in control. ETS-8-42.0 states that all CCV recoveries must be within 100*30% for the data to be acceptable. For the initial analysis on October 16,2007, several of the standards selected for CCV analysis were above the final established calibration range. Consequently, the instrument was not able to produce a concentration to establish accuracy. However, when the raw area counts of the CCV injections are compared to the raw area counts of the same standards injected during the initial calibration sequence, the CCV area counts are all within 30% of the initial values. This indicates that the instrument response did not drift significantly during the course of the analytical run. Since the approximate instrument response was established during the run on October 16, 2007, CCV standards for the October 19, 2007 were selected in the lower end of the calibration range. For this run, all CCV injections met method acceptance criteria of 100*30% except one PFBA injection that consequently was the highest calibration standard in the curve. The area counts of the CCV injection were slightly higher than the uppermost calibration range and the software was unable to calculate a concentration. However, the area counts of the non-compliant injection were within 3% of those from the injection used to establish the curve. Since all PFBA sample extracts were below or near the LOQ and were reanalyzed in Phase I I , sample results were preliminarily reported to the study director without reanalysis. A method deviation has been issued to address all non-compliant CCVs and the acceptability of the data. The method deviation can be found in the raw data.

All CCV samples analyzed during the course of Phase II met method acceptance criteria of 1OOe5% recovery as required by ETS-8-12.1.

Phase II

Lab Control Spikes (LCSs)

Phase I Triplicate low (1.5 pg nominal concentration) and high (30 pg nominal concentration) lab control spikes (LCSs) were prepared each day samples were extracted. LCSs were

E06-0549 Interim Report #15 Woodbury Soils: October 2007 Page 25 of I56


Sample Description

LCS-071015-1

LCS-071015-2

LCS-071015-3

LCS-0710154

LCS-071015-5

LCS-0710154

prepared by spiking known amounts of the target analytes into separate 1 g aliquots of the laboratory control soil matrix TCR-842 to produce the desired concentration. The spiked soil samples were then extracted and analyzed in the same manner as the samples. Individual LCS results, along with the average and percent RSD, for each extraction set are presented in the data table below. All LCSs within the established calibration range produced recoveries that met ETS-8-42.0 method criteria of 100*30%.

Spiked Sample Conc. Conc. (ug) (ug) %Rec.

1.50 1.52 101

1.50 1.53 102

1.50 1.59 106

29.9 >ULOQ NA

29.9 >ULOQ NA

29.9 >ULOQ NA

Table 14. Lab Control Spike Results: Phase I Extraction Day 10/15/2007'1'2'. PFBA

Sample Description

LCS-071015-1

LCS-071015-2

LCS-071015-3

LCS-071015-4

LCS-071015-5

LCS-071015-6

Spiked Sample Conc. Conc. (usl (ug) %Rec.

1.51 1.705 113

1.51 1.653 109

1.51 1.565 104

30.2 WLOQ NA

30.2 NLOQ NA

30.2 WLOQ NA

Average %Recovery f %RSD 109%#.3%

I PFBS

Average %Recovery f %RSD 103%f2.3%

PFOA

Spiked Sample Conc. Conc. (ug) (ug) %Rec.

1.49 1.739 117

1.49 1.722 116

1.49 1.751 118

29.9 '"27.8 93.1

29.9 '"27.5 92.1

29.9 '"26.1 87.3

11 7%f0.84%

PFHS

Spiked Sample Conc. Conc. (ugl (ug) %Rec.

1.52 1.57 103

1.52 1.51 99.2

1.52 1.54 102

30.5 WLOQ NA

30.5 NLOQ NA

30.5 WLOQ NA

l O l % f Z . l %

(1) Table displays rounded values for all concentration and percent recovery values (3 (2 significant figures). Reported values may vary slightly from the raw data.

Surrogate


1.49 1.78 119

1.49 1.72 115

1.49 1.78 119

29.9 NLOQ NA

29.9 WLOQ NA

29.9 WLOQ NA

11 8%fZ.O%

PFOS


1.50 1.61 107

1.50 1.53 102

1.50 1.56 104

30.0 NLOQ NA

30.0 WLOQ NA

30.0 WLOQ NA

104%f2.5% lnificant figures) and %RSD

(2) High level LCSs were above the upper calibration range for all analytes (ULOQ ranged from 2.5 pg to 10 pg depending on the analyte.) A higher level calibration curve was established in a separate analysis on 10/19/2007; however, high level LCSs were still above the upper calibration range for all analytes except for PFOA. The high level PFOA LCS recoveries are reported from the higher level calibration curve.



Table 15. Lab Control Spike Results: Phase I Extraction Day 10118/2007('~2'.

Sample Description

LCS-071018-1

LCS-071018-2

LCS-071018-3

LCS-071018-4

LCS-071018-5

LCS-071018-6

Sample Description

Spiked Sample Spiked Sample Spiked Sample Cone. Cone. Cone. Cone. Cone. Cone. (pg) %ReC* (A (,N) %me. (A (pg) %Rec.

1.50 1.47 98.1 1.52 1.53 100 1.50 1.45 96.6

1.50 1.51 101 1.52 1.57 103 1.50 1.47 98.1

1.50 1.50 100 1.52 1.59 104 1.50 1.52 101

29.9 >ULOQ NA 30.5 WLOQ NA 30.0 NLOQ NA

29.9 >ULOQ NA 30.5 WLOQ NA 30.0 NLOQ NA

29.9 NLOQ NA 30.5 >ULOQ NA 30.0 >ULOQ NA

LCS-071018-1

LCS-071018-2

LCS-071018-3

LCS-071018-4

LCS-071018-5

LCS-071018-6

Average %Recovery f %RSD 100%f1.4%

PFBA

Spiked Sample Cone. Cone. (M) (pg) %Rec.

102%f1.8% 98.5%f2.2%

1.51 1.55 102

1.51 1.50 99.2

1.51 1.54 102

30.2 NLOQ NA

30.2 NLOQ NA

30.2 >ULOQ NA

PFOA

Spiked Sample Cone. Cone.

(pg) %Ree.

1.49 1.67 112

1.49 1.62 108

1.49 1.69 113

29.9 '"27.1 90.9

29.9 '"26.8 89.9

29.9 '"27.1 90.7

Surroaate

Spiked Sample Cone. Conc.

(pg) %Rec.

1.49 1.47 98.6

1.49 1.47 98.3

1.49 1.54 103

NA 29.9 NLOQ

NA 29.9 NLOQ

NA 29.9 NLOQ

Average %Recovery f %RSD lOl%fl.8% I 11 1 %f2.2% I lOO%f2.7%

(1)

(2)

Table displays rounded values for all concentration and percent recovety values (3 significant figures) and %RSD (2 significant figures). Reported values may vary slightly from the raw data.

High level LCSs were above the upper calibration range (5 or 10 pg depending on the analyte). A higher level calibration curve was established in a separate analysis on 10/19/2007; however, high level LCSs were still above the upper calibration range for all analytes except for PFOA. High level PFOA LCS recoveries are reported from the higher calibration curve.

Phase I1 Triplicate low (3 ng nominal concentration) and high (30 ng nominal concentration) lab control spikes (LCSs) were prepared each day samples were extracted. LCSs were prepared by spiking known amounts of the target analyte into separate 1 g aliquots of the laboratory control soil matrix TCR-842 to produce the desired concentration. The spiked soil samples were then extracted and analyzed in the same manner as the samples. Individual LCS results, along with the average and percent RSD, for each extraction set are presented in the data table below. All LCSs met ETS8- 12.1 method accuracy criteria of pooled average recovery of 1 O O e O % and precision criteria of pooled %RSD 520%. Phase II LCS results are presented below.


3M Envimnmenfal Laboratory €06-0549 lnferim Report #i5

Ocbaction Day: 11/1W2007

Table 16. Lab Control Spike Results: Phase II.

PFBA

Extmcthn Day: lI/lZ2007 I PFBA

Sample Comment Sample ID

LCS-071119-1 LCS Low 1 3 ng

LCS-071119-2 LCSLow2 3ng


LCS-071119-5 LCS High 2-30 ng


LCS-0711ls4 LCS High 1-30 ng


Spiked Conc. Cak. Conc. (nd (nd % R e

3.02 2.79 92.3

3.02 2.98 98.6

3.02 3.09 102

30.1 31.7 105

30.1 30.8 1 02

30.1 32.7 1 09

LCS-071115.1 LCSLow1 3ng

LCS-0711152 LCSLow2 3ng

LCS-0711153 LCSLow3 3ng

LCS-0711154 LCS High 1-30 ng


LGS-0711156 LCS High 3-30 ng

Spiked Conc. Calc. Conc. (nd (nd %RK.

3.02 3.07 1 02

3.02 2.94 97.4

3.02 2.94 97.4

30.1 30.9 103

30.1 30.2 100

30.1 31.6 105

Average %Recovery

%RSD

101

3. I

Extraction Dav: 11/1&2007








PFBA

Spiked Conc. Calc, Conc. (nd (nd %ReC.

3.02 3.49 115

3.02 3.58 119

3.02 3.51 116

30.1 30.9 103

30.1 31 .O 103

30.1 30.4 101

Average %Recovery

%RSD

110

7.3

~~

Average %Recovery

%RSD

101

5.6

E060549 Interim Report # I 5 Woodbury Soils: October 2007 Page 28 of 156









~~~~~~ ~

Spiked Conc. Calc. Conc. (nd %ReC.

3.02 2.19 72.8

3.02 2.54 84.3

3.02 2.54 84.2

30.1 26.1 86.6

30.1 26.7 88.6

30.1 27.9 92.7

Sample Duplicates

Phase I For Phase I, every fifth soil sample was extracted in duplicate to demonstrate reproducibility. The relative percent difference (%RPD) for the sample and extraction duplicate is provided in Table 1.

Phase II For Phase II, all submitted soil samples (excluding the trip blanks) were extracted in duplicate to assess the sample homogeneity. The relative percent difference (%RPD) for each sample and extraction duplicate is provided in Table 2. Samples with a %RPD exceeding 30% have been footnoted in the table.

Dry Weight Determination After completion of Phase I, the dry weight (%solids) was determined for each sample in duplicate. Briefly, a 10 g aliquot of the well mixed soil sample was placed in a pre-weighed aluminum weighing pan (tare weight recorded) and the mass of the soil plus the pan was accurately measured using an analytical balance. The pan containing the wet soil sample was then placed in an oven at 105k5"C overnight. The next day the pan was transferred to a desiccator to cool to room temperature for 15 minutes before the dry weight was recorded. After recording the new weight, the pan was returned back to the desiccator for at least another hour before weighing the dried sample a second time to verify that the mass did not change significantly. The average of the first and second dry measurement was used to determine the percent solids.

[(Pan + Average Dry Weight)(g) - (Tared Pan Weight)(g)] , [(Pan +Wet Weight)(g)- (Tared Pan Weight)(g)]

Percent solids =

The average percent solids for a given sample was used to determine the concentration of the target analytes in the soil sample on a ng/g (dry weight) basis.

sample extract concentration (ng) mass extracted native soil(g) percent solids

x ( d r y weight) = g

EO6-0549 Interim Report #I5 Woodbury Soils: October 2007 Page 29 of 156

3M Environmental Laboratory €06-0549 lntedm Report #15

Laboratory Matrix Spikes (LMSs)

Phase I For Phase I analysis, each sample was spiked with approximately 1 pg of PFOA[I ,2 13C] surrogate. Separate laboratory matrix spikes with the target analytes were not prescribed for Phase I analysis as detailed in the general project outline. Surrogate recoveries exceeding 100*30%, but still within 1 OOH30% were considered reportable with an expanded method uncertainty. Surrogate recoveries outside of 1 O O % i 6 0 % were flagged separately in the data table.

Phase II For Phase II analysis, separate laboratory matrix spikes at two different levels were prepared for each submitted soil sample (excluding the trip blanks). The low and high level PFBA spike concentrations were 5.03 ng and 75.4 ng respectively. ETS-8-12.1 states that laboratory matrix spike levels should be between 0.5 and 10 times the endogenous level for the lab matrix spike recoveries to be used to determine the statement of accuracy for the sample results without further justification. Phase II laboratory matrix spike recoveries are presented in the Data Summary and Discussion section below. The following equation was used to calculate the LMS recovery.

(Conc. spiked sample(ng) -(Average Conc. dry weight(ng/g) * Amount extracted (9) % solids ,oo% LMS Spike Recovery = Spike Amount (ng)

For the sample extracts of E06-0549-1572, separate laboratory matrix spikes of the final extracts were prepared for the PFOA analysis (high levels present in the soil precluded direct spiking of the soil prior to extraction). Briefly, a 1 mL aliquot of the sample extract was removed and spiked with a 1 mL aliquot of a 500 pg/mL standard solution. (Initial sample dilution factor =2). The spiked aliquot was then diluted 15000 with extraction solvent for a final extract dilution factor of 10,000. An additional dilution factor of 5 was achieved by injecting 1 pL of the diluted LMSs versus a calibration curve established using a 5 pL injection volume. PFOA LMS spike recoveries are presented in the next section. LMS recoveries of the spiked extracts were determined using the equation below.

(Conc. spiked extract(B) - (Extract Conc. (s) Spike Concentration (x) PFOA LMS Spike Recovery = mL mL "100%

mL

Data Summary and Discussion

Phase I Table 1 summarizes the Phase I sample results and surrogate recoveries for all of the sampling locations plus the trip blanks and rinseate blanks. In general, surrogate recoveries produced recoveries within the acceptance criteria of 100%k30%. Samples with surrogate recoveries exceeding 100*30% but within 1 OOMO% were assigned an expanded method uncertainty. The Phase I overall analytical method uncertainty was determined to be 100&42% based on the pooled surrogate recovery for all samples. See Determination of Analytical Method Method Uncertainty section for more information.

Sample E06-0549-1572 produced a PFOA concentration that greatly exceeded 250 pg/g. Consequently, samples analyzed immediately following this sample (E06-0549-1573 through E06-0549-1575 duplicate, plus E06-0549-1595 (Soil Trip Blank 1) may have experienced instrument carryover from the high level sample extract. The effected sample results have been flagged accordingly in Table 1.


3M Environmental Laboratory €06-0549 interim Report #15

All sample locations produced PFBA concentrations below or near the estimated LOQ of 0.1 Iglg (100 ppb). All samples were reanalyzed for a lower PFBA LOQ in Phase 11.

Phase II

PFBA Table 17 summarizes the Phase II PFBA sample results and lab matrix spike (LMS) recoveries for each sample submitted. Lab matrix spikes were not prepared for the three trip blanks and the two rinseate blanks. The table provides the average concentration and the relative percent difference (%RPD) of the sample and sample duplicate. Results and average values are rounded to three significant figures. Percent relative difference (%RPD) values are rounded to two significant figures. Because of rounding, values may vary slightly from those listed in the raw data. Lab matrix spikes meeting the method acceptance criteria of 100*30% demonstrate that the analytical method is appropriate for the given matrix. If the low level spike amount was less than half the resultant endogenous concentration, the LMS recovery was not reported as the spike level was not appropriate for the given sample concentration.

LMS recoveries were within 100*30% except for the following samples: E06-0549-1556 (Low Spike 141 %), E06-0549-1572 (High Spike 62.3%), E06-0549-1576 (High Spike 222%), E06-549-1590 (Low Spike 131%), and E06-0549-1593 (High Spike 64.9%). For E06-0549- 1576, a sample spike preparation error is suspected (sample was inadvertently spiked twice as the recovery is approximately 200%). The average concentration agreed well with the PFBA results observed during Phase I. The surrogate recovery for the Phase I analysis of this sample was 87.1%. Therefore, the results for this sample location are reported with an analytical accuracy of 1 OOH2%, the Phase I analytical method uncertainty. All of the remaining non-compliant sample results have been flagged in Table 2 and Table 17 with an expanded sample uncertainty of 100&50% to reflect the LMS recovery. For samples E06- 0549-1572 and E06-0549-1590, the sample and sample duplicate produced a high %RPD which may contribute to the LMS recovery exceeding method acceptance criteria.

PFOA Phase I1 extracts for E07-0549-1572 were diluted and analyzed separately for PFOA at the request of the study director. (The PFOA Phase I result for this location was >250 pg/g.) The Phase I1 results are presented in Table 18. Lab matrix spikes of the final extracts produced recoveries within 100*30%. Although the extraction replicates produced similar results (%RPD = 5.2%) and the LMS recoveries of the spiked extracts was excellent (96.9% and 102%), it should be noted that the extraction method has not been evaluated for soil concentrations at this level (Le. 8 mL of solvent and 2 hours of sonication may not be sufficient to completely extract all of the fluorochemicals adsorbed to the surface of the soil). Therefore, the concentrations should be considered minimum estimates.

€06-0549 Interim Report #15 Woodbuty Soils: October 2007 Page 31 of 156


extracted amount wet

3M LlMS ID Sample Description w g h t (a ~~~~

E06-0549-1556 WBMN SB GP103 0 0145 0.9446

E06-0549-1556 Dup WBMN SB GP103 0 0145 0.9970

E06-0549-1556 LMS LOW WBMN SB GP103 0 0145 1.0026

E06-0549-1556 LMS High WBMN SB GP103 0 0145 0.9688

Table 17. Phase II PFBA Sample and QC Results. @PFBA

Conc. (nsJgj Conc. (ngl dry weight %Recovery

7.50 9.35 NA 7.53 8.90 NA

15.0 NA "1 44

89.8 NA 109

E06-0549-1557

E06-0549-1557 DUP

E06-0549-1557 LMS Low

WBMN SB GP103 0 0200 0.9500 6.50 7.30 NA WBMN SB GP103 0 0200 1.0371 6.50 6.69 NA WBMN SB GP103 0 0200 0.9386 11.5 NA 106

Average %Solids 93.7

E06-0549-1557 LMS High WBMN SB GP103 0 0200 1.0772 93.7 NA 115

E06-0549-1558

E06-0549-1558 Dup

E06-0549-1558 LMS Low

E06-0549-1558 LMS High

WBMN SB GP102 0 0240 1.0297 60.0 65.5 NA WBMN SB GP102 0 0240 0.9905 52.1 59.2 NA WBMN SB GP102 0 0240 1.0239 63.5 NA NR

WBMN SB GP102 0 0240 0.9896 134 NA 105

Average Concentration ( n & )

%RPD

Average %Solids

E06-0549-1559

€0645481559 Dup

€06-05441559 LMS Low

E06-0549-1559 LMS High

4.17

NA

81.3

WBMN SB GP102 0 0195 1.0981 128 146 NA WBMN SB GP102 0 0195 1.0235 126 154 NA

WBMN SB GP102 0 0195 1.0102 95.2 NA NR

WBMN SB GP102 0 0195 1.0438 183 NA 76.8


E06-0549-1560

E06-0549-1560 Dup

E0645441 560 LMS Low

E06-0549-1560 LMS High


WBMN SB GPlOl 0 0080 1.091 0 c1 .oo C1.13 NA WBMN SB GPlOl 0 0080 1.0220 c1 .oo c1.20 NA WBMN SB GPlOl 0 0080 0.9716 4.35 NA 86.6

WBMN SB GPlOl 0 0080 0.9918 70.0 NA 92.9

Page 32 of 156

3M Envimnmental Laboratory €06-0549 Interim Report #15

extracted amount wef

3M LlMS ID Sample Description weight (g)

E06-0549-1561 WBMN SB GPlOl 0 0120 0.9207

E06-0549-1561 DUP WBMN SB GPlOl 0 0120 0.9624

E0645491561 LMS High WBMN SB GPlOl 0 0120 0.9818

E06-0549-1561 LMS Low WBMN SB GPlOl 0 0120 1.0385

"PFBA

Conc. (ndg) Conc. (ng) dry weight %Recovery

<1 .oo 4.14 NA 4 .oo 4.09 NA 5.39 NA 107

83.8 NA 111

Average Concentration (ndgj

%RPD

Average %Solids

E06-0549-1562

E06-0549-1 562 Dup

E06-0549-1562 LMS High

E06-0549-1562 LMS Low

36.7

6.8

86.0

WBMN SB GPFOl 0 01 10 1.0360 33.8 37.9 NA WBMN SB GPFOl 0 01 10 1.0760 32.8 35.4 NA WBMN SB GPFOl 0 01 10 0.9582 38.8 NA NR

WBMN SB GPFOl 0 01 10 0.9875 111 NA 106

E06-0549-1563

E06-0549-1563 Dup

E06-0549-1563 LMS Low

E06-0549-1563 LMS High

Average Concenttation (np'g)

%RPD

Average %Solids

E06-0549-1564 Dup

E06-0549-1564 LMS Low



Average Concentration (np'gj

%RPD

Average %Solids

WBMN SB GPFOl 0 0230 1.0612 1.04 1.34 NA WBMN SB GPFOl 0 0230 1 .M63 1.33 1.74 NA WBMN SB GPFOl 0 0230 0.9130 5.36 NA 86.2

WBMN SB GPFOl 0 0230 1.071 1 63.4 NA 82.5

1.54

26

1.0099

1.0693

0.9698 6.47 86.7

0.9683

2.55

23

85.6

E06-0549-1566

E06-0549-1566 Dup

E06-0549-1 566 LMS Low

E06-0549-1566 LMS High

E06-0549-1 565 1 WBMNSBGPFOl RBOOOO I 0.9600 I 4.00 (3)~1 .04 NFl

WBMN SB GPAOl 0 0080 0.9140 72.0 89.9 NA WBMN SB GPAOl 0 0080 1.01 56 105 118 NA WBMN SB GPAOl 0 0080 1.0887 126 NA NR

WBMN SB GPAOl 0 0080 0.9301 166 NA 108



extracied amountwet

3M LIMS ID Sample Description weight (g)

"PFBA

Conc. (ng/g) Conc. (ng) dry weight %Recovery

Average Conceniation (ng/g)

%RPD

Average %Solids

E06-0549-1567

E06-0549-1567 dup

E06-0549-1567 LMS High

E06-0549-1567 LMS Low

32.0

3.7

93.1

WBMN SB GPA02 0 0200 0.9796 50.8 59.8 NA WBMN SB GPAO2 0 0200 1.0265 43.7 49.1 NA WBMN SB GPA02 0 0200 1.0046 50.6 NA NR

WBMN SB GPA02 0 0200 0.9819 121 NA 99.0

EM-0549-1568

E0645491 568 dup

E06-0549-1568 LMS Low

E06-0549-1568 LMS High

Average Concenttation (nglg)

%RPO

Average %Solids

E06-0549-1570 dup

E06-0549-1570 LMS Low




%RPD

Average %Solids

WBMN SB GPAO2 0 0240 0.9351 28.4 32.6 NA WBMN SB GPA02 0 0240 0.9224 27.0 31.5 NA WBMN SB GPA02 0 0240 1.01 62 32.8 NA NR

WBMN SB GPAO2 0 0240 0.9143 120 NA 123

E06-0549-1569

E06-0549-1569 dup

E06-0549-1569 LMS Low

E06-0549-1569 LMS High

3.33

28

0.9508 1 0.9089 0.9830

1.0047 87.9

8.86

8.1

90.3





1.0899

0.9750

0.9606

0.9983

Average Concentation (nglg)

%RPD

Average %Solids

2.81 2.86 NA 3.33 3.79 NA 8.56 NA 113

83.2 NA 106

EO6-0549-1571

E06-0549-1571 dup

E06-0549-1571 LMS Low

E06-0549-1571 LMS High

37.6

@32

82.2



WBMN SB GPAOB 0 0080



0.9061

0.9263

1.0504

0.9123


23.6 31.7 N4

33.2 43.6 NA 57.8 NA NR

102 N4 97.9

Page 34 of 756

3M LlMS ID

E06-0549-1572

E0645491572 dup 1 WBMN SB GPA04 0 0165 1 0.9971 1 170 192 NA

extracted amount wet Conc. (ngg)

Sample Descripiion weight (gJ Conc. (ngJ dry weight %Recovery

WBMN SB GPA04 0 0165 0.9491 218 258 NA

E06-0549-1572LMSLow I WBMNSBGPAOQO0165 I 1.0117 I 152 NA NR

E06-0549-1572 LMS High WBMN SB GPA04 0 0165 1.0697 261 NA "62.3

%RPD

Average %Solids

E06-0549-1573

E06-0549-1573 dup

E06-0549-1573 LMS High

€06-0549-1 573 LMS Low

30

89.0

WBMN SB GPAM 0 0200 0.9773 4.26 4.64 NA WBMN SB GPA04 0 0200 1.0112 4.37 4.60 NA WBMN SB GPA04 0 0200 1.0071 10.2 NA 116

WBMN SB GPAW 0 0200 1.0508 81.6 NA 102

3M Environmental Laboratory 1506-0549 Interim Report #15

I

~

E06-0549-1574

E06-0549-1574 dup

E06-0549-1574 LMS Low

E06-0549-1574 LMS High

WBMN SB GPAO5 0 0080 1.0604 2.02 2.26 NA WBMN SB GPAO5 0 0080 1.0776 1.48 1.63 NA WBMN SB GPAO5 0 0080 0.9585 6.84 NA 105

WBMN SB GPAO5 0 0080 0.9251 73.7 NA 95.8

Average Concentration (nglg) 4.62

0.9549

0.9673

1.0216

0.9968

%RPD 0.86

<1 .oo <1.15 NA <1.00 4.13 NA 5.53 NA 110

75.7 NA 100

€06-05491576

E06-0549-1576 dup

E06-0549-1576 LMS Low

E06-0549-1576 LMS High

Average Concentmtbn (nglg)

%RPD

Average %Solids

E06-0549-1575 dup

E06-0549-1575 LMS LOW



Average Concentration (ngg)

%RPD

Average %Solids





84.3

0.9338

1 .ow 0.91 51

1.0016

99.7 120 NA 106 115 NA 86.2 NA NR

272 NA "'222

d.14

NA

91.2

Average Concentration (nglg) 117

%RPD 4.1


€064549 Interim Report #f 5 Woodbury Soils: October 2007 Page 35 of 156


3M LIMS ID

E06-0549-1577

E06-0549-1577 dup

E06-0549-1577LMS low

E06-0549-1577LMS high

~

exfiacfed amount wet

Sample Description wisht (s, WBMN SB GPBOl 0 0170 0.9135

WBMN SB GPBO10 0170 0.9206

WBMN SB GPBOl 0 0170 1.0923

WBMN SB GPBOl 0 0170 1.0768

Conc. (ng/sl) Conc. (na) dry weight %Recovery

€06-0549-1578

E06-0549-1578 dup

E0645491 578LMS high

E06-0549-1578LMS low

1.70 2.16 NA 1.74 2.19 NA 7 .84 NA 115

84.3 NA 109

WBMN SB GPCOl 0 0160 1.0317 2.19 2.26 NA WBMN SB GPCOl 0 0160 1.01 02 5.14 5.41 NA

WBMN SB GPCOl 0 0160 1.0072 8.30 NA 92.9

WBMN SB GPCOl 0 0160 1.0660 88.4 NA 112

2.17

1.6

86.3

WBMN SB GPC02 0 0210


WBMN SB GPCO2 0 0210


1.0862

1.0029

0.9892

0.9644

E06-0549-1579

E06-0549-1579 dup

E06-0549-1579LMS low

€06-0549-1 579LMS high

Average Concenfmtion (ng@

%RPD

Average %Solids

WBMN SB GPCOl 0 0210



Average Concentration (ngg)

%RPD

Average %Solids

1.0450

0.9630

1.0345

3.84

@82

94.0

1.48 1.68 NA 1.25 1.24 NA 7.18 NA 116

86.2 NA 112

1.46

30

96.1

E06-0549-1580

E06-0549-1 580 dup

E06-0549-1580LMS low

E06-0549-1580LMS high



WBMN SB GPCOP 0 0160


Average Concenfmtbn ( n & j

%RPD

Average %Solids

~ ~~ ~

19.1 22.3 NA

23.2 26.7 NA 28.0 NA NR

93.1 NA 96.5

24.5

18

79.5

E06-0549-1581

E06-0549-1581 dup

E06-0549-1581 LMS IOW

E06-0549-1581 LMS high

21.1 22.2 NA

19.2 21.9 NA

22.1 NA NR

92.1 NA 97.5

Average Concentration (ng/g) 22.1

%RPD 1.5



3M Environmental Laboratory EO64549 Interim Report #15

3M LlMS ID

Eo6-0549-1582

E06-0549-1582 dup

E06-0549-1582LMS low

E06-0549-1582LMS high

I "PFBA

exfncted amount wet Conc. (nglgj

Sample Description weight (gj Conc. (ngj dry weight %Recovery

WBMN SB GPB02 0 0160 1.0726 2.30 2.28 NA WBMN SB GPB02 0 0160 0.9521 1.66 1.85 NA

WBMN SB GPBOZ 0 0160 0.9553 7.90 NA 120

WBMN SB GPBO2 0 0160 1.0186 85.0 NA 110

E06-0549-1583

E06-0549-1583 dup

E06-0549-1583LMS low

E06-0549-1583LMS high


%RPD

Average %Soli&

WBMN S B GPBOZ 0 01 10

WBMN SB GPBOZ 0 01 10

WBMN SB GPBO2 0 01 10

WBMN SB GPBOZ 0 01 10

2*06

21

94.2

0.9360

0.9345

0.9681

0.9516

29.7 37.1 NA 23.0 28.7 NA

32.5 NA NR

108 NA 108

Avemge Concentration (nglgj

%RPD

Average %Soli&

E06-0549-1584 dup

Eo6-0549-1584LMS low WBMN SB GPWl 0 0120

WBMN SB GPWl 0 0120

WBMN SB GPWl 0 0120

Average ConcenMion (nglg)

%RPD

Avemge %Solids

0.9438

1.0567

1.0076

1 .@I99

1.49 1.70 NA 1.59 1.62 NA 6.99 NA 108

78.9 NA 103

Eo6-0549-1585

E06-0549-1585 dup E06-0549-1585LMS IOW

E0645491 585LMS high

32.9

25

85.6

WBMN SB GPWl 0 0080

WBMN S B GPWl 0 0080

WBMN SB GPWl 0 0080

WBMN SB GPWl 0 0080

1.0218

0.9556

I .0274

1.0474

1.66

4.8

93.7

3.81 4 A9 NA

3.50 4.41 NA 9.07 NA 105

74.5 NA 98.8

E06-0549-1586

E06-0549-1586 dup E06-0549-1586LMS low

E06-0549-1586LMS high

Average Concentation (nglg)

%RPD

Average %Solids

WBMN SB GPEO1 0 0120

WBMN SB GPEOl 0 0120



4.4s

1.8

83.0

1.01 03

0.9906

1.0542

1.0456

37.5 45.4 NA 44.6 55.0 NA 53.1 NA NR

118 NA 100

Average Concentation (np" 50.2

%RPD 19

Average %Soli& 81.8

€064549 Interim Report #15 Woodbury Soils: October 2007 Page 37 of 156


Sample Description

WBMN GPE 01 SB 0160

WBMN GPE 01 SB 0160

WBMN GPE 01 SB 0160

WBMN GPE 01 SB 0160

E06-0549-1587 dup

E06-0549-1587 LMS low

E06-0549-1587 LMS high

axtracted

we~ghi (s) Conc. (ns) dry weight %Recovery amount wet Conc. (n&!)

0.9424 17.2 19.2 NA 1.0383 18.3 18.5 NA 1.01 72 22.5 NA NR

0.9771 99.0 NA 108

E06-0549-1588

E06-0549-1588dup

€0645441 588 LMS low

E06-0549-1588 LMS high

Average Concentration (ns/s)

%RPD

Average %Solids

WBMN GPJ 01 SB 0085 1.0781 <1 .00 <I .07 NA WBMN GPJ 01 SB 0085 1.0768 <I .oo 4.07 NA WBMN GPJ 01 SB 0085 0.9585 4.83 NA 96.1

WBMN GPJ 01 SB 0085 1.0568 75.6 NA 100

18.9

3.5

95.2

E06-0549-1589

E06-05441589dup

E06-0549-1589 LMS low

E06-05441589 LMS high

WBMN GPJ 01 SB 0135 0.9901 <1 .oo d.04 NA WBMN GPJ 01 SB 0135 0.9654 4 .oo 4.07 NA WBMN GPJ 01 SB 0135 1.0079 5.06 NA 101

WBMN GPJ 01 SB 0135 0.9973 80.6 NA 107

E06-0549-1590

E06-0549-1590dup

E0645441 590 LMS low

E06-0549-1590 LMS high

WBMN GPG 01 SB 0058

WBMN GPG 01 SB 0058

WBMN GPG 01 SB 0058

WBMN GPG 01 SB 0058

1.0327 8.49 9.28 NA 1.071 8 5.84 6.15 NA 1.0097 13.5 NA "'131

0.9478 78.1 NA 95.0

E06-0549-1591

E06-0549-1591dup

E06-0549-1591 LMS low

E06-0549-1591 LMS high

I E0645491592 I WBMNGPJ01 RB0000 I 1.0751 I 4.00 <0.930 NA

WBMN GPG 01 SB 0108 0.9505 4 .oo 4.09 NA WBMN GPG 01 SB 0108 1.0726 4 .oo <0.964 NA WBMN GPG 01 SB 0108 0.9853 5.98 NA 119

WBMN GPG 01 SB 0108 1.0812 78.0 NA 103

€06-0549 Interim Report #15 Woodbury Soils: October 2007 Page 38 of 1 56


3M LlMS ID

E06-0549-1593

Em-0549-1 593dup

EO645441 593 LMS low

Em-0549-1593 LMS high

I "PFBA

Sample Description

WBMN GPH 01 SB 0155

WBMN GPH 01 SB 01 55

WBMN GPH 01 SB 0155

WBMN GPH 01 SB 0155

axbzrcted amount wet weight (a)

0.9782

0.9698

1.0124

0.9554

Conc. (nSJg) Conc. (na) dry weight %Recovery

45.6 54.0 NA 43.9 52.5 NA 35.5 NA NR

92.8 NA %4.9

m53.3

2.9

86.3

E06-0549-1594

EW5491594dup

Em-0549-1594 LMS IOw

E06-0549-1594 LMS hiah

WBMN GPH 01 SB 0205

WBMN GPH 01 SB 0205

WBMN GPH 01 SB 0205

WBMN GPH 01 SB 0205

0.9499

0.9713

0.9682

0.9795

5.39 6.18 NA 6.50 7.29 NA 12.3 NA 126

82.1 NA 101

E06-0549-1 595

%Solids

Soil Trip Blank Set 1 [ 0.9860 I <1 .oo 4.06 NA

~

95.7

€06-05441 596

E0645491597 I Soil Trip Blank 3 I 0.9622 I IE NA NA

Soil Trip Blank 2 1 1.0571 I e1 .oo co.988 NA

%Solids 95.8

(1) Except where noted, Phase II PFBA results are considered accurate to within 100f30% based on lab matrix spike recoveries and other laboratory QC samples. The overall analytical method uncertainty for this project was determined to be 100*29%. See the Statistical Methods and Calculations sections or more information.

(2) PFBA results are considered accurate to within 100*50% based on lab matrix spike recoveries and other laboratory QC samples.

(3) Concentration of aqueous rinse blank samples reported in nglg (wet weight).

(4) %RPD of sample and sample duplicate exceeded 30%.

(5) Lab matrix spike recovery exceeded 100f50%; however, spiking error suspected. Phase II results agree well with Phase I results (average 117 ng/g). Results reported with an uncertainty of 100&42% based on Phase I analytical method uncertainty.

NR= Not Reportable. Spike amount not appropriate for the endogenous sample concentration.

IE = Instrument Error. Instrument software error occurred during the injection of this sample and no data was recorded. Sample concentration is not reported.



I PFOA

3M LlMS ID

E0645441572(1:5000)

E0645441572 LMS(1:lOOOO)

LMS % Extract lnsbument Final Dilution Dilution Dilution exftaeted Cone. Conc.@d Cone.&&)

Sample Description Factor Factor factor amount(gl (ng/inL) wetweight dryweight Recovery

WBMN SB GPAW 0 0165 5,000 5 25,000 0.9491 311,000 2488 2945 NA WBMN SB GPAW 0 0165 10,000 5 50,000 0.9491 793,000 NA NA 96.9

~~ ~

EM5491572 dup(l:5000)

E0605491572 dup LMS(1:lOOOO)


WBMN SB GPAW 0 0165 5,000 5 25,000 0.9971 344,000 2752 3101 NA WBMN SB GPAW 0 0165 10,000 5 1 50,000 I 0.9971 I 849,000 NA NA 102


~~ ~~ ~ ~

flJAverage Coneentiation (j&J

%RPD

Average %Soli&

Spike Concentration (ClghLj

Page 40 of 156

3020

5.2

89.0

49%


Statistical Methods and Calculations

Statistical methods used to interpret sample results include averages and standard deviations. The Mass Lynx (Phase I) and Analyst (Phase II) software programs calculated sample concentrations using resultant analyte peak areas and the established quadratic, l /x or 11x2 weighted, calibration curve. Equations used to report method accuracy and precision are described below.

Accuracy and Precision Equations Calculated Concentration ,oo% LCSlSurrogate Percent Recovery =

Spike Concentration

'100% standard deviation of replicates

replicate average % RSD (Relative Standard Deviation) =

Absolute difference between sample duplicates , oo% % RPD (Relative Percent Difference) =

average sample concentration

Determination of Analytical Method Uncertainty

Phase I Analytical uncertainty for the Phase I results was determined by using statistical evaluation of the surrogate recoveries. The standard deviation was calculated for the surrogate recoveries (in %). The expanded uncertainty was calculated by multiplying the standard deviation by a factor of 2, which corresponds with a confidence level of 95%. All surrogate recoveries were taken from the low level calibration curve analysis. If the surrogate recovery of EN-0549-1 572 (sample with ~ 2 5 0 pg/g of PFOA) is excluded, the analytical uncertainty for the Phase I analysis is 42%. Table 19 displays the surrogate recoveries used to determine the analytical method uncertainty.

The analytical method uncertainty for the Phase II results was determined by calculating the standard deviation of all the reportable lab matrix spike recoveries (in %). The expanded uncertainty was calculated by multiplying the standard deviation by a factor of 2, which corresponds with a confidence level of 95%. All LMS recoveries can be found in Table 17. When all recoveries were included in the calculations, the average LMS recovery was 107% with a standard deviation of 21 % (analytical uncertainty of 42%). If the LMS recovery of E06-0549-1576 is excluded (222% - double spike error suspected), the average LMS recovery is 105% with a standard deviation of 14.3%. This produces an analytical method uncertainty of 29% (two significant figures).

Phase II


3M Environmental Laboratory E064549 Interim Reporf #15

Table 19. Phase I Analytical Method Uncertainty Determination.

extracted Surrogate Mass

Sample ID Sample Description (9) Conc. pg %Recovery

E06-0549-1556

E06-0549-1557

E06-0549-1558

E06-0549-1559

E06-0549-1560

E06-0549-1560 dup

E06-0549-1561

E06-0549-1562

E06-0549-1563

E06-0549-1564

E06-0549-1566

E06-0549-1566dup

E06-0549-1567

E06-0549-1568

E06-0549-1569

E06-0549-1570

E06-0549-1570 dUp

E06-0549-1571

E06-0549-1572

E06-0549-1573

E06-0549-1574

E06-0549-1575

E06-0549-1575 dUp

E06-0549-1595

E06-0549-1565

E06-0549-1576

E06-0549-1577

E06-0549-1578

E06-0549-1579

E06-0549-1579 dUp

E06-0549-1580

E06-0549-1581

E06-0549-1582

E06-0549-1583

E06-0549-1584

E06-0549-1584 dUp

E06-0549-1585

E06-0549-1586

E06-0549-1587

WBMN SB GP103 0 0145







WBMN SB GPFOl 0 01 10



WBMN SB GPAOl 0 0080

W M N SB GPAOl 0 0080




W M N SB GPA03 0 0200








Soil Trip Blank 1

WBMN SB GPFOl RB 0000





WBMN SB GPCOl 0 021 0



WBMN SB GPB02 0 0160

WBMN SB GPBO2 0 01 10

WBMN SB GPDOl 0 0120





0.9812

0.9926

0.9285

0.9635

1.163

1.084

1.041

0.9531

0.9677

0.9164

1.055

1.01 7

0.9588

1.015

1.071

1.096

0.9987

0.9617

1.052

0.9630

0.91 a2

1.0042

0.9723

1.062

1.1669

1.0660

1.0040

1.0301

0.9654

1.0557

1.0007

1.091 9

1.0287

0.9614

1.0906

1.0750

0.9687

1.0276

1.01 96

1.37

1.42

1.40

1.39

1.36

1.25

1.45

1.06

1.33

1.36

0.900

0.976

0.669

0.925

1.36

1.38

1.34

0.587

0.205

0.809

1.32

1.38

1.41

1.40

1.08

0.887

1.09

1.20

1.22

1.23

1.07

1.19

1.18

0.543

1.28

1.18

1.09

0.990

1.18

135

139

138

136

133

122

143

104

131

134

88.4

95.8

65.7

90.8

133

136

131

57.6

20.1

79.4

130

136

138

137

106

87.1

107

118

119

121

105

117

116

53.3

125

116

107

97.2

116



Mass extracted Surrogate

Sample ID Sample Description (s) Conc. jig %Recovery

E06-0549-1588 WBMN SB GPJOI 0 0085 1.0899 1.16 114

€06-0549-1 589 WBMN SB GPJOl 0 0135 0.9625 1.26 124

E06-0549-1589 dup WBMN SB GPJOl 0 0135 1.041 7 1.15 113

E06-0549-1590 WBMN SB GPGOI 0 0058 0.9564 1.13 111

E06-0549-1591 WBMN SB GPGOI 0 0108 1.0797 1.20 118

€06-0549-1 592 WBMN SB GPJOl RB 0000 0.9758 1.12 110

E06-0549-1593 WBMN SB GPHOI 0 0155 0.921 1 1.01 99.3

E06-0549-1594 WBMN SB GPHOl 0 0205 1.001 3 1.15 113

E06-0549-1594 dup WBMN SB GPHOI 0 0205 0.9346 1.15 113

E06-0549-1596 Soil Trip Blank 2 0.941 1 1.17 114

€06-0549-1 597 Soil Trip Blank 3 1.0555 1.15 112

Spiked Surrogate Concentration (pg) 1.02

All Data Points

Average 112

Analytical Uncertainty (Std. Deviation*2) 49%

Std. Deviation 24.6

~~ ~ ~

Excluding €06-05494572

Average 114

Std. Deviation 20.9

Analytical Uncertainty (Std. Deviation.2) 42%

E064549 Interim Report #15 Woodbury Soils: October 2007 Page 43 of 156


Statement of Conclusion

Phase I Sample results for the Phase I analytical portion of this project (PFOA, PFBS, PFHS, and PFOS) were presented in Table 1. Surrogate recoveries were used to determine the overall analytical method uncertainty (1 00&42%). Sample results with surrogate recoveries that exceeded 100*30%, but were within 1 O O g O % were flagged with an expanded sample uncertainty in Table 1.

Phase II Sample results for the Phase II analytical portion of this project (PFBA) were presented in Table 2. Lab matrix spike recoveries were used to determine the overall analytical method uncertainty (1 00&29%). Samples with lab matrix spike recoveries exceeding 100k30% were flagged with an expanded sample uncertainty of 100*50%.

The average PFOA concentration of sample E06-0549-1572 from the Phase I I extracts was 3020 pglg (%RPD=5.2). Lab matrix spikes of the final extract produced recoveries with 100*30%.

References

ETS 8-042.0 "Solvent Extraction and lsocratic LC/MS/MS Analysis of Soils for C4-Cl2 Perfluorinated Carboxylic Acids and Perfluorobutane Sulfonate, Perfluorohexane Sulfonate, and Perfluorooctane Sulfonate".

ETS 8-12.1 "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".

List of Attachments

Attachment A: Selected Chromatograms and Calibration Curves Attachment 6: Extraction and Analytical Methods Attachment C: Protocol and Protocol Amendments Attachment D: Protocol andlor Method Deviations


J


ATTACHMENT A: SAMPLE CHROMATOGRAMS AND CALIBRATION CURVES

EO 64549 Interim Repom1 5 Woodbury Soils: October 2007 Page 46 of 156


U-: a071016a-007 T a t : Sol-t B l a n k 07 004-184 0 0 : 2 0 A C U : W i k

1: PerfluorobutanaoaCe [PFBA; C41

Solvent Blank 07 004184 80:20 ACN:Water a071016a-007 MRM of 12 Channels ES-

213 > 16: 27:

% 5

Time 0.50 1.00 1.50 2.00 2.50 3.00 3.50

: perfluorobutane sulfonate iPFB

iolvent Blank 07 004-184 80:20 ACN:Water i071016a-007 MRM of 12 Channels ES-

1.71 299 > 80+299 > 9E 39 A 48E

PerflU0*00etanOatelPmA: CBI

iolvent Blank 07 004184 80:20 ACN:Water 1071 01 6a-007 MRM of 12 Channels ES-

2.07

2gi Sun 56;

Arez

0 0.50 1.00 1.50 2.00 2.50 3.00 3.50

perfluorohexam Sulfonate ic6

iolvent Blank 07 004-184 80:20 ACN:Water 1071 016a-007 MRM of 12 Channels ES-

399 > 80+399 > 91 86:

Arez

1.92 79 A

Analyst - mi&lh w i n s k y

€06-0549 Interim Report#lB Woodbury Soils: October 2007 Page 47 of 156

3M Environmental Laboratory €064549 intwim Report #15

5 pertluorooctane sulfonate ipm

Solvent Blank 07 004-184 80:20 ACN:Water a071 016a-007 MRM of 12 Channels ES-

1.52e3 Sum

Area

2.22 164 100-

%-

Time 0 7 h a 8 I I I I I I I I I I I I I I 1 I . I I I I I , I 1 1 1 , I I I I 8 , I I I , I I 1 1 1 1 1 , , , , , I , , , , , , I , , , ,- 0.50 1.00 1.50 2.00 2.50 3.00 3.50

6 13C-l.Z-Pcrfluorooctanoate (PF

Solvent Blank 07 004-184 80:20 ACN:Water a071016a-007 MRM of 12 Channels ES.

2.07 415 > 371

Are, 36 44

100-

%-

0 I I I I I I I I I I I I I I I I I I I I I I I I ,, I I I I I I I I I I I I I

0.50 1.00 1.50 2.00 2.50 3.00 3.50 I I I ,, I , , , , I , I I I I Time

Analyst - Yish.lh w r r u g

€06-0549 Interim Repott#lS Woodbury Soils: October 2007 Page 48 of 156

3M Environmental Laboratory €06-0549 Interim Repori # I 5

3 : perfluarobutane iulfonate (PFB

EC-071015-5 (2.5 Ug) 16-0~t-200711:30:56 a071 016a-012 MRM of 12 Channels ES-

1.71 299>80+299>99 206507 1.79e5

Area

100-

%-

O ~ J 1 1 I I I I I I I I I I I I - 1 I I I I I I a I I 1 I I I , p-n I I I I I I I I , I C Time 0.50 1.00 1.50 2.00 2.50 3.00 3.50

Prinbd: 2U. DK 04 O9:20:51 2001

4: perfluorohexane sulfonate I C 6

EC-071015-5 (2.5 Ug) 16-0~t-200711:30:5€ a071016a-012 MRM of 12 Channels ES- 100- 1.92 399 > 80+399 > 95

237577 2.04e5 Area

%-

0- I , I I I I I I I I I I I I a a I I I I I I I .TI’. I rliq. I I I I I I ,. I I I I I I a I I I I I I I I I I I I I I I I. Time 0.50 1.00 1.50 2.00 2.50 3.00 3.50

Y-: ~011016~-012 T u t : Lc-0’11015-5 (2.5 ug)

: Perfluarobutanaoate IPFBA; c41

IC-071015-5 (2.5 Ug) 16-0~t-200711:30:5€ 3071 016a-012 MRM of 12 Channels ES-

213 > 16s 5.08e4

Arei

3071 016a-012 MRM of 12 Channels ES- 213 > 16s

5.08e4 Arei

I I

0 Time 0.50 1.00 1.50 2.00 2.50 3.00 3.50

: Pe~fluo~oost.noate(PFDAi CBI

IC-071015-5 (2.5 Ug) 16-0~t-200711:30:5€

SUN 3071 016a-012 MRM of 12 Channels ES-

10743 8.68e4 Are:

2.09 n

€06-0549 Interim RepottUl5 Woodbuty Soils: October 2007 Page 49 of 156


u-: 107101S~-012 k t : EC-071015-5 12.5 ugl

: perfiuorooctane sulfonate ipm

X-071015-5 (2.5 Ug) 16-0~t-200711:30:5~

SUN 3071 016a-012 MRM of 12 Channels ES-

1.17et Are:

0 Time 0.50 1.00 1.50 2.00 2.50 3.00 3.50

: 13C-l.Z-PeTflUOIOOCt~"~~t= (PF

X-071015-5 (2.5 ug) 16-0~t-200711:30:5~ 3071 016a-012 MRM of 12 Channels ES- 100

%.

0.

10203

2.11 n I \

415 > 37t 8.59eL

Are2

Time 0.50 1.00 1.50 2.00 2.50 3.00 3.50

Analyst - miuetrll. ullilury

€06-0549 Interim Repod15 Woodbury Soils: October 2007 Page 50 of 156


Printrd: hu DIc 04 09:20:51 2007

I r a : a011016a-023 h.t: m-071015-1

1071016a-023

Perfluorobutanaoate I P m : c4I

AB-071015-1 16-0~t-200712:25:3€ MRM of 12 Channels ES-

213 > 16s 46E

I 1.60

a4 %

: Perfluorooctanoate(P~A: E81

AB-071015-1 16-0~t-200712:25:3€ a071 016a-023 MRM of 12 Channels ES-

S u r 984

Area

a071016a-023 MRM of 12 Channels ES- a071016a-023 MRM of 12 Channels ES- 299>80+299>99 1.92 399 > 80+399 > 9!

672 144 1.17e: I O 7 Area "7 Are;

" / I Time

0.50 1.00 1.50 2.00 2.50 3.00 3.50

Analyst - U&lh Uzlilug

€06-0549 Interim Report#l5 Woodbury Soils: October 2007 Page 51 of 156


*.thod: D:L.u.lyru\-11.062491.PRO~tbDB\.071Dl6. W ~ o Q n u y soi ls

Job cod.:

Prinrrd: Tu. D.s 04 09:20:51 2 0 0 1

l u t roditid: on no- 05 1 4 : ~ ~ : ~ s 2 0 0 1

n-: ~071016.-02~ l’ut: WB-071015-1

5 : perfiuorooctane sulfonate 6: 1 3 C - l . Z - P C l f l l l O = D o c t a n D a t e 1PF

/MB-071015-1 16-0Ct-200712:25:36I IMB-071015-1 16-O~t-200712:25:3( a071 016a-023 MRM of 12 Channels ES-

2.22 Sum 1.54e3

Area

I - -

a071016a-023 100-

MRM of 12 Channels ES- 2.1 1 415 > 37( 90 76; 7

Are:

%-

uuly.t - Ki&ll. minsky

€06-0549 Interim Repott#15 Woodbury Soils: October 2007 Page 52 of 156


%-

P.9. 59

u-: .011016.-030 T a t : US-071015-2

Perfluorobutanaoate IPE'BA: C41

.CS-071015-2 16-0~t-200713:00:1! MRM of 12 Channels ES-

1.68 213 > 16! 42191 3.77er

Are:

1071016a-030

perfluombutane sulfonate IPW

.CS-071015-2 1071016a-030

lo? 1.72

133831

16-0~t-200713:00:1! MRM of 12 Channels ES-

299 > 80+299 > 9! 1.19e!

Pe=flU~~00ctsnO=telPmA: C 8 l

.CS-071015-2 16-0~t-200713:00:1!

'"7 1071016a-030 MRM of 12 Channels ES-

Sun 6.39e~ "n Are:

..~n&

1

Time 0.50 1.00 1.50 2.00 2.50 3.00 3.50

perfluorohexane sulfonate I C 6

.CS-071015-2 16-0~t-200713:00:1! 1071016a-030 MRM of 12 Channels ES-

1.92 399 > 80+399 > 9! 145681 1.28e!

Area

Time 0.50 1.00 1.50 2.00 2.50 3.00 3.50

m y s t - nifbrll. Yllln'ky

€06-0549 Interim Repom15 Woodbury Soils: October 2007 Page 53 of 756


n-: .oiioi6.-030 hrt: XI-011015-2

: perflvoraoctanc sulfonate I P R )

XS-071015-2 16-O~t-200713:OO :I C 3071016a-030 MRM of 12 Channels ES-

2.24 Sum I O 0 7 95587\ 7.08e4

1 3 C - 1 . 2 - P e T f l " O = O O c t a n o a r e IPF

.CS-071015-2 16-0~t-200713:00:1I 3071 016a-030 MRM of 12 Channels ES-

2.09 415 =. 37C 77231 6.58e4


3M Environmental Laboratory E064549 Interim Report #I5

U u : a0110161-05e hrt: L06-0549-1510

1: Perfluarobutanaoate (PFBA: c41

E06-0549-1570 16-0~t-200715:19:5~ a071016a-058 MRM of 12 Channels ES- 1 oa

%

0

213 > 16s 50i

Are:

perfluorobutane sulfonate ( P F B

E06-0549-1570 16-0~t-200715:19 5 4 1071 01 6a-058 MRM of 12 Channels ES- 100

%

299 > 80+299 =. 9: 1.86e4

Ares

0 1 - Time 0.50 1.00 1.50 2.00 2.50 3.00 3.50

An8ly.t - uichll. Whky

€06-0549 Interim Report#fS

P.lfluorooctanoate(PDA: C81

iO6-0549-1570 1071 016a-058

% I1 2.( 4:

16-0~t-200715:19:5~ MRM of 12 Channels ES-

Sun 3.70e:

Are:

0 Time 0.50 1.00 1.50 2.00 2.50 3.00 3.50

: Derfluorohenane sulfonate (C6

IO6-0549-1570 r071016a-058 100

%

0

1.93 130221

16-0~t-200715:19~5~ MRM of 12 Channels ES-

399 > 80+399 > 95 1.15eE

Ares

I\ 0.50 1.00 1.50 2.00 2.50 3.00 3.50 Time



5: perfluoroactane SUlfOnatC [Pro

16-0~t-200715:19:54 MRM of 12 Channels ES-

Sum 1.53e4

Area

E06-0549-1570 a071 016a-058

Time 0.50 1.00 1.50 2.00 2.50 3.00 3.50

6 : 13C-l.Z-Pelflu0~00stdnoate I P F

E06-0549-1570 16-0~t-200715:19:5~ a071016a-058 MRM of 12 Channels ES-

2.09 415 > 37( 5.46ef

Are:

100-

%-

0 , , , I ( I I I I I I I I I ( I I I I ~ , I I . I , , , , I , , , , , I I I I , I I I I 1 a I I I I I I I I I I I I I I I I I I I Time 0.50 1.00 1.50 2.00 2.50 3.00 3.50

Aaaly.t - N i & l b m l h s k y

€06-0549 Interim Repotf#I5 Woodbury Soils: October 2007 Page 56 of 156


EC-071015-4 (1.0 Ug) 16-0~t-200716:29:58 a071016a-072 MRM of 12 Channels ES-

P a p 143

EC-071015-4 (1.0 ug) 16-O~t-200716:29:5t a071016a-072 MRM of 12 Channels ES-

perfluarobutane sulfonate IPFB

IC-071015-4 (1.0 Ug) 16-0~t-200716:29:51 1071 016a-072 MRM of 12 Channels ES- l1 %

299 > 80+299 > 9! 7.92el

Arei

Time 0.50 1.00 1.50 2.00 2.50 3.00 3.50

qerfluorohcxane sulfonate I C 6

IC-071015-4 (1.0 Ug) 16-0~t-200716:29:5€ 1071 016a-072 MRM of 12 Channels ES-

1.92 399 > 80+399 > 9E 90281 7.99e4

Ares

€06-0549 Interim Repom15 Woodbury Soils: October 2007 Page 57 of i56

3M Environmental Laboratory €06-0549 lnterim Repoti #15

5: perfiuorooctane sulfonate ipm

EC-071015-4 (1.0 Ug) 16-0Ct-200716:29:58 a071 01 6a-072 MRM of 12 Channels ES-

Sum 4.51e4

Area

Ii Time

0.50 1.00 1.50 2.00 2.50 3.00 3.50

: 1 3 c - l . Z - P e ~ f l ~ ~ 1 0 0 ~ t ~ ~ ~ ~ t ~ (Pf

X-071015-4 (1.0 Ug) 16-0~t-200716:29:51 a071 016a-072

7 MRM of 12 Channels ES- 415 > 37(

4.98er Are:

m y s t - yich.lh U l i M k y

€06-0549 Interim Repori#l5 Woodbury Soils: October 2007 Page 58 of 156


7.02e4-

Response

C.IIb..U"I D;\u.ly..\.-ll.e"." ..,,.O,,.,k b.* -I** - - 0, I l . l . i l . 1.0, .,I.Wi m. h. 04 I. I.:.. 20-7

:ompound 1 name: Pelfluotobulanaoate (PFBA: C4) :oefflcient of Determination: 0,999333 :alibration cutve: -324.755 * XY + 3163.37 ' x + -122.317 !esponse type: External Std. Area :uwe type: 2nd Order, Origin: Exdude. Weighting: IW?. Axis trans: None

m

.

'-

.

0.0- ,! 20.0 ' ' ' ' ' 40.0 ' ' ' ' ' 4.0: ug

.

IC 2

ompound 2 name: Perhoroxlanoate(PF0A C8) oefficlent of Determination: 0.999636 alibration wwe: -382.600 ' xA2 + 5381.97 * x + -162.911 esponse type: External Std. Area UNe type: 2nd Order, Origin: Exclude. Weighting: l /x . Axis trans: None

1.47e

-1fi 1

€06-0549 Interim Repoti#l5 Woodbury Soils: October 2007 Page 59 of 156

3M Environmental Laboratory €064549 Interim Report #15

:ompound 3 name: peffluombutane sulfonate (PFB :~effiuent of Determination: 0.999797 :alibratiin WNe: -561.137 * x Y + 9529.31 * X + 124.243 Zesponse type: External Std. Area :urn type: 2nd Order. Origin: Exclude, Weighting: l l x . Axis trans: Ncme

2.10ee

Response

.

.

ornpound 4 name: peffluorohexane sulfonate (C6 Deficient of Determination: 0.999471 allbration curve: 492.322 * xA2 + 10335.9 * x + 103.443 esponoe type: External Std. Area UNB type: 2nd Order, Origin: Exclude, Weighting: I/& Axis trans: None .

.

0 0.0 20.0 40.0 60.0 80.0 100.0 120.0 140.0 160.0 180.0 2W.O 220.0 240.0



:ompound 5 name: perfluoroodane sulfonate (PFO hffldent of Determination: 0.999571 :alibrationcurve:-15.105'x*2+6345.94'x+ 229.152 iesponse type: External Std. Area :urve type: 2nd Order, Origin: Exclude. Weighting: 1/xA2, Axis trans: None

2.13e!

Responsf

.

rn

20.0 40.0 60.0 80.0 1M1.0 120.0 140.0 160.0 180.0 200.0 220.0 240.0 ug

ompound 6 name: 13C-1.2-Perfluorooclanoate (PF oeffldent of Determination: 0.099128 alibratiwn curve: -373.486 * xA2 + 5244.39 * x i -1 78.934 esponse type: External Std. Area urve type: 2nd Order, Origin: Exclude, Weighting: l/x. Axis trans: None

.



E064549 Interim Repom15 Woodbury Soils: October 2007 Page 62 of 156


€06-0549 Interim Reporn15 Woodbury Soils: October 2007 Page 63 of 156

3M Envimnmental Laboratory €06-0549 Interim Report #15

..



.- I- .- .-I

€06-0549 Interim Report#15 Woodbury Soils: October 2007 Page 65 of 156


E064549 Interim RepoMl5 Woodbury Soils: October 2007 Page 66 of 156

3M Environmental Laboratory €06-0549 Interim Repori #15

'Ollie: U00110402 Resul ts Name: o011115a.rdb

0071 115a.rdb (pfba): "Quadratic" Regression ("1 I x" weighting): y = -8.01 xV! + 1.56e+004 x + 8.4e+003 (r = 0.9997)

3.4e6

3.2eE

3.0e6

2.8e6

2.6e6

2.4e6

2.2e6

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*Ollie: U00110402


Results Name: o071129a.rdb

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3M Environmental Laboratory E064549 Interim Report #lS

ATTACHMENT B: EXTRACTION AND ANALYTICAL METHODS

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w-- Method

Solvent Extraction and isocratic LC/MWMS Anatysis of Soils for C4ClZ Perfluorinated Carboxylic Acids and Perfhorobutane Sulfonate, Perfluomhewane

Sulfonate and Perf-uorooctane Sulfonate

Method Number: EfS-8-042.0

Adoption Dafe: Upon Signing

Revision Rate: NA

Effective Date: Y/)%/Oq

William K. Reagen Date Laboratory Manager

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1 Scope and Application

This is a performance-based LC/MS/MS method that describes the extraction of targeted fluorochemical analytes from soil or water matrices. The method was developed for extraction of 1 mL of soil (typically 1 to 2 grams of soil depending on soil densityhype). Target analytes in extracted samples are quantified against extracted matrix-matched calibration standards prepared with standardized soils. This method may be extended to other matrices and test systems (e.g. sludge and sediments) if the data quality objectives defined herein are met. This analytical method applies to perfluorinated carboxylic acids (C4 to C12) and perfluorinated alkyl sulfonates (C4, C6 and CS), or mixtures thereof.

2 Method Summary

Soil samples are measured to 1 mL and accurately weighed and then are extracted. Extraction consists of adding 8 mL of an 80:20 (acetonitri1e:water) extraction solvent, sonication for 1 hour and then centrifugation to pellet solids. An aliquot of the clarified supernatant (extract) is transferred to an autosampler vial for analysis. Analysis is conducted using liquid chromatography with triple-quadrupole mass spectrometric detection (LC/MS/MS). The extraction and general LC/MS/MS instrument and conditions are as specified in this procedure.

3 Definitions

3.1 Reagent grade water Reagent grade water is defined as water with no detectable target analyte or other impurities present at or above a level that affects data quality objectives. A Millipore Milli-QTM water purification system, or equivalent water purification system, is used to provide ASTM Type I reagent water for the 3M Environmental Laboratory.

3.2 Method Blank An aliquot of control matrix that is treated exactly like a laboratory sample including exposure to all glassware, equipment, solvents, and reagents used with other laboratory samples. The method blank is used to determine if test substances or other interferences are present in the laboratory environment, the reagents, or the testing apparatus.

3.3 Sample A sample is an aliquot removed from a larger quantity of material intended to represent the original source material.

3.4 Surrogate A compound similar to the target analyte(s) in chemical composition and behavior and not normally found in the sample(s), but is added to the samples. A surrogate compound is typically a target analyte with at least one atom containing an isotopic isotopic-labeled substitution (e.g. I3C-labeled). If used, surrogate is added to all samples and quality control samples (except solvent blanks and half of the prepared method blanks). Inclusion of a surrogate analyte is an optional quality control measure and is not required.

3.5 Calibration Standards Solutions prepared by spiking known quantities of target analytes at varying levels into a predetermined amounts of matrix and that are extracted and analyzed according to the method. Calibration standards are used to calibrate the instrument response with respect to analyte concentration

3.6 Field BlanWTrip Blank A representative clean matrix 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.

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The purpose of F ie la r ip Blanks is to determine if test substance or other interferences are present in the field environment.

3.7 Laboratory Matrix Spike A laboratory matrix spike (LMS) is an aliquot of a sample to which low quantities of target analytes are added in the laboratory. The LMS is extracted and analyzed exactly like a laboratory sample to determine whether the sample matrix contributes bias to the analytical results. The endogenous concentration of analytes in the sample matrix must be determined in a separate aliquot, and measured values in the LMS corrected for the endogenous concentrations. LMSs are required for soils and sediments.

3.8 Laboratory Sample

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

The lower limit of quantitation (LLOQ) for a dataset is the lowest concentration that can be reliably quantified within the specified limits of precision and accuracy. To simplify data reporting, the LLOQ is generally selected as the lowest non-zero standard in the calibration curve that meets method specified criteria. The upper limit of quantitation (ULOQ) is the highest concentration that can be reliably quantified within the specified limits of precision and accuracy. The highest standard in the calibration curve that meets method criteria is defined as the ULOQ.

4 Warnings and Cautions

4.1 Health and Safety Warnings Always wear appropriate protective equipment (e.g. gloves, safety glasses, and lab coat) when performing this procedure. Some soils are regulated for importing to the 3M Environmental Laboratory. Consult the 3M Environmental Laboratory sample receiving custodian for soils permit requirements when working with soil samples.

5 Interferences

Contaminants in solvents, reagents, glassware, hardware or standardized matrices may cause interference. The routine analysis of laboratory method blanks must be used to demonstrate that there is no interference under the conditions of the analysis.

6 Instrumentation, Supplies, and Materials

6.1 Instrumentation Jouan C412 Centrifuge with swinging bucket rotor able to hold 50 mL conical centrifuge vials, or equivalent.

Agilent 1100 HPLC system with autosampler, thermostat-controlled column compartment and binary pump system, or equivalent.

Triple-quadrupole mass spectrometer with electrospray ionization source with sufficient sensitivity for the intended analytical range.

6.2 Supplies and Materials 10 mL disposable graduated pipettes, glass Pasteur pipets (glass) and rubber bulbs. Volumetric flasks, glass, type A (variable sizes) 50 mL Falcon Blue MaxTM polystyrene conical centrifuge tubes (part no. 352074), or equivalent

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Labels Hamilton syringes, graduated, various sizes for delivering solvent solution Crimp-top glass autovials and caps Crimpers and Decappers, as needed Betasil C8 column (4.6 x 150 mm; 5 um particle). Thermo Electron Cop., Part No. 70205-154630 1 mL Bel-Art Mini-Sampler Spoons, disposable polystyrene. VWR Part No. 74950-178 250 mL graduated cylinder (glass or plastic)

7 Reagents and Standards

Reagent grade water Methanol, HPLC grade or equivalent. Acetonitrile, HPLC grade or equivalent Ammonium Acetate (99%), ACS grade Acetic Acid C4 to C12 perfluorinated carboxylic acids, or equivalent salts C4, C6 and C8 perfluorinated alkyl sulfonic acids, or equivalent salts

8 Sample Handling

Samples should be stored refrigerated, unless the protocol or GPO specifies different storage conditions. Storage conditions and locations will be documented for samples on the chain of custody received with the samples. Allow samples to equilibrate to room temperature prior to extraction. At least one set of extracted matrix standards and appropriate blanks are prepared with each batch. Extracted standards, blanks and samples can be stored at room temperature. Calibration standards and QCs will be matrix-matched with the samples (e.g. soil-matrix standards for analysis of soil matrix samples).

9 Method Performance Data Quality Objectives

The following performance criteria will be met in the application of this method:

9.1 Extracted Matrix Calibration A calibration curve will be prepared from the analysis of extracted soil-matrix standards that are prepared at the desired concentrations by spiking in known quantities of target analytes. Calibration standards will be analyzed at the beginning of each LCMSMS analytical set (batch or run). Typically, eight or more calibration standards are prepared and analyzed, and the final regression will consist of a minimum of six (6) levels. Values obtained from blanks (e.g. for use as a zero value curve points) will not be included in regressions unless specified differently in the protocol or GPO. The curve range should encompass the expected concentrations in samples. The equation of the calibration curve will be determined by regression analysis using the integrated analyte peak area, or using the analyteLS peak area ratio if internal standard method is employed. The curves will typically be the best fit obtainable with the data during interpretation of R-values, calibration standard accuracies and QC accuracies. Curves should be quadratic or linear fit. Weighting of the curves to facilitate low end quantitation is acceptable as l/x or 1/x2 weighting. R-values (correlation coefficients) for acceptable curves should be 2 0.99 (R2 2 0.98). Curve parameters chosen for each analyte should be consistent throughout a study, or otherwise documented. The accuracy of each calibration level will be verified against their theoretical values. Any calibration level outside 100% k 30% (100 5 35% for LLOQ) of theoretical must be deactivated and the regression recalculated, except if used as an anchor point outside of the range of quantitation. The LLOQ must have an accuracy of within 100 k 35% of theoretical and an analyte response of at least 2 times a method blank response.

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9.2 Quality Control (QC) Samples Quality control (QC) samples such as Laboratory Control spikes or Field Matrix Spikes are often used to verify sample preparation and analyte extractability. If included in the study design, QCs should be treated identical to samples once spiked. At a minimum, determined spike concentrations in QCs should be within 100 rt 30% deviation from theoretical, unless specified differently in the study protocol or general project outline (GPO).

9.3 Limits of Quantitation (LOQ) The lower limit of quantitation (LLOQ) for each analyte is defined as the lowest calibration level that shows a determined recovery of 100 rt 35% for the target analyte and demonstrates a response greater than or equal to twice that of the method blank. If the lowest level non-zero calibration point has to be deactivated in a particular data set, the LLOQ for that set will be revised to the acceptable next highest concentration in the calibration curve range. An out of spec calibration standard may remain active in the calibration curve if it is outside of the acceptable LOQ range, but only to serve as an anchor point if needed to improve quantitation accuracy. Only one anchor point may be used in a curve. The upper limit of quantitation (ULOQ) is defined as the highest calibration level that remains active in the curve and that meets acceptance criteria of 100 f. 30%. Calibration standards at the low and/or high end of the curve may be deactivated to meet accuracy and detection limit requirements of the method for a particular analytical sample batch, but minimally six calibration points must be included to construct a curve,

9.4 Continuing Calibration Verification (CCV) The use of CCVs will be applied in all analytical runs to verify control of the instrumental analysis. The continued accuracy of the calibration for a run will be verified by the repeated injection of a mid-level standard throughout the analytical run. Typically, CCVs are also flanked by blanks as appropriate to evaluate or minimize carryover. The CCV and appropriate blanks should be injected every 15 samples in a run to continuously verify quantitative accuracy. An analytical run should always end with injection of a CCV and blanks. A run will be considered acceptable if all CCVs meet the acceptance as defined herein or otherwise specified in the study protocol or GPO. The CCVs must show a recovery within 100 f 30% to be considered acceptable. CCVs at the LLOQ level must show a recovery within 100 f 35% of theoretical to be considered acceptable.

9.5 Blanks

9.5.1 Solvent Blank An aliquot of extraction solvent is typically injected as a solvent blank. Solvent blanks may contain internal standard to evaluate potential contaminants in the IS or the extraction solution.

9.5.2 Method Blank Analytical runs must include method blanks that are prepared using the same or similar matrix used to prepare the calibration standards. The matrix blank analyte response is used to define the acceptable LLOQ for the run. The frequency and exact makeup of the matrix blanks will depend on the scope of the study. Specific requirements, if any, will be addressed in the study protocol and/or the raw data.

9.6 Sample Replicate When required, sample replicates are prepared according to each study protocol and will be documented in the raw data. Samples prepared and analyzed in duplicate will have their average value and relative percent difference (RPD) of the two values reported. Samples prepared in triplicate, or greater, will have their mean values with the relative standard deviations (RSD) reported.

9.7 Surrogate Standard If a surrogate standard is a component of the study, all samples will be spiked at a pre-defined concentration of surrogate analyte prior to extraction in the laboratory. Solvent blanks are not spiked with surrogate. Acceptance criteria for the surrogate standard recovery during analysis will be defined by the GPO or study protocol. If not defined, acceptable recovery will be 100 2 30% of theoretical recovery based on the response from analysis of calibration standards.

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9.8 Internal Standard An internal standard (IS) is an analyte added to samples during sample preparation that is expected to behave similar to targeted endogenous analytes in the sample, but is not expected to be present in samples. The IS is typically added at a fixed concentration to laboratory samples and is used to evaluate instrument performance during the run. The IS may be used quantitatively to account for instrument response drift during a run. When used quantitatively, the calibration curve is constructed by plotting the known concentration versus the analyte/IS response ratio. Analyte concentrations in samples are then determined by correlating their respective analyte/IS ratios back to the fit of the calibration curve.

9.9 Matrix Spike Matrix spikes are samples fortified with a known amount of the target analyte(s) in the laboratory during preparation and are extracted in identical manner as the samples. If matrix spikes are a required component of the study, the recoveries of target analytes, determined after subtracting values for non-spiked samples, should typically be within 100 f 30% of the theoretical spiked concentration. Matrix spike results are used to determine the statement of accuracy included in the analytical report. The requirement of, and frequency of, matrix spikes will be based on the data quality objectives of the study and will be defined by the study protocol or GPO.

9.10 Sample Dilution Any sample extract with an analyte response greater than that of the highest acceptable calibration standard will need to be diluted into the range of the calibration curve and re-analyzed, unless otherwise specified in the GPO or study protocol. If sample extracts are diluted, they should be diluted with the extracts from an equivalent clean extracted method blank (matrix blanks) as the diluent. Alternatively, instrumental-applied dilutions may be performed by partial volume injection of samples compared to calibration standards, but should be assessed with appropriate partial-volume injected CCVs for evaluating the accuracy of the partial- volumes. For example, injecting 10 UL of each calibration standard to construct a curve, but injecting 1 uL of sample (effectively a 10-fold dilution). All dilutions should be documented in the raw data and final values reported will be corrected for the dilution factors applied,

10 Procedures

10.1 Sample Preparation and Extraction Prepare one liter of an 80% acetonitrile in water extraction solution. Using a 250 mL graduated cylinder, add 200 mL of reagent grade water to a clean one-liter volumetric flask and then bring to the mark with acetonitrile. If required, add internal standard (IS) at a concentration that is appropriate to the analytical quantitative range prior to finalizing the volume to the mark with acetonitrile. Volumes may be scale up or down to accommodate the number of samples to be extracted.

Prepare laboratory samples. For each sample, tare a clean and appropriately labeled 50 mL centrifuge tube using a balance capable of measuring minimally to 0.01 grams. Using a 1 mL disposable sampling spoon, dispense 1 mL of soil sample into the 50 mL centrifuge tube and accurately determine the weight of the soil. Record the sample weight on an appropriate sample preparation form (Attachment A), or other appropriate data entry location (e.g. technical notebook). Repeat for each sample.

Extract laboratory samples. For each weighed sample contained in a 50 mL centrifuge tube, use a graduated glass pipette to add 8.0 mL of extraction solution to the 1 mL soil or water sample. Record the volume of solution added to the sample on an appropriate sample preparation form (Attachment A), or other appropriate data entry location (e.g. technical notebook). Cap and then briefly mix the contents of the vessel by briefly vortexing or shaking by hand. Then place in a water bath sonicator at ambient temperature and sonicate for one hour. Record the ID of the sonicator and the length of time sonicated on the preparation form. Centrifuge the sonicated sample for approximately five minutes and at approximately 2000 RPM to sufficiently pellet the soil and to create a clarified supernatant. If debris is still observed after centrifugation, centrifuge up to 3000 RPM or for an additional length of times as necessary to pellet the soil debris. Record the centrifugation time and RPM on the sample preparation form (Attachment A), or other appropriate data entry location (e.g. technical notebook).

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Prepare the extract for analysis. Using a disposable glass Pasteur pipette, transfer an aliquot of each clarified supernatant to appropriately labeled autosampler vials and cap.

Analyze the aliquoted samples. 10.2 LClMSlMS Analysis

Analyte optimization may be required prior to analysis. Optimization should be performed for best sensitivity using an infusion pump directly coupled to the mass spectrometer and injecting a single or mixed analyte standard solution at a very slow rate. During infusion, the MS/MS parameters should be adjusted to the desired optimal settings and those settings used with the chromatographic conditions defined below. The following settings have been found to be adequate for many, but not all, fluorochemical analytes.

10.2.1 Liquid Chromatography (LC) Conditions Prepare one liter of 1% acetic acid in water as mobile phase A. using a 10 mL glass volumetric pipette, dispense 10 mL of glacial acetic acid into a one liter volumetric flask and bringing to the mark with reagent grade water.

Prepare one liter of I O mM ammonium acetate in methanol: acetonitrile (4: 1) as mobile phase B. Weigh 0.77 grams of ammonium acetate into a one-liter volumetric flask and add 200 mL of acetonitrile using a 250 mL graduated cylinder. Then bring to the mark with methanol.

The HPLC method uses a Betasil C8 (4.6 x 150 mm; 5 um particle) column maintained at 50°C in a thermostat-controlled column compartment. The method utilizes isocratic mobile phase conditions (15% mobile phase A and 85% mobile phase B) at 1 mL/min flow rate.

Extracts are typically injected as 1 to 10 pL. Instrumental applied dilutions may be performed by partial- volume injection of samples compared to full volume injection of calibration standards, but should be assessed with appropriately partial volume injected CCVs for evaluating the accuracy of the partial volumes injections. For example, injecting 10 pL of standard and 1 pL of samples (effectively a 10-fold dilution) can be performed, but appropriate CCVs injected at 1 pL should also be assessed. Instrument blanks may be used to evaluate injector and other instrument contamination by injection of zero pL from an uncapped and empty autovial.

The method cycle time is 4 minutes and all mass spectrometer data collection should be set to a maximum collection time of 4 minutes.

Typical backpressures on the system should range from -50 to -150 mbar.

For Micromass Z-spray sources, the LC flow from the column outlet to the mass spectrometer inlet may need to be partially split to waste in order to accommodate a lower flow rate to the source. The amount of split is typically determined visually by inspecting the spray source in the mass spectrometer while adjusting the splitter. A barely visible spray should be observed through one entire gradient cycle using a flashlight and minimal condensation should be observed in the spray chamber after multiple injections. Some mass spectrometer sources (e.g. Applied Biosystems TurboIonTM Spray) may accommodate 21 mL/minute flow rates and may not require a split.

HPLC effluents should be captured to the appropriate high-BTU waste receptacles and disposed of according to standard 3M waste disposal practices.

The HPLC conditions used per analytical run will be recorded with the raw data and should be recorded for replication of the analysis. Typical HPLC settings from a Quattro-I1 are shown below to facilitate rapid instrument set up if using a Micromass Quattro I1 or Quattro Ultima.


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10.2.2 Mass Spectrometer (MSIMS) Typical Conditions The triple quadrupole mass spectrometer (MSMS) conditions will vary depending on instrument manufacturer, source design, and analytes being detected. The provided examples are for a Micromass Quattro I1 or Quattro Ultima triple quadrupole mass spectrometer fitted with a 2-spray electrospray source and Mass Lynx operating software. The examples provided should be generally transferable between equivalent or better instruments with some minor adjustments for terminology, special system requirements, software differences, and electrospray source designs. All instruments should be operated according to the manufacturer’s recommended operating conditions and specifications for that instrument.

The Quattro I1 2-spray electrospray source requires a drying gas (typically Nitrogen) flow at - 450 Lihr and a nebulizer gas (typically Nitrogen) flow at - 18 L h . These gases can be optimized to improve the spray shape and increase droplet evaporation rate, which should be optimized to reduce condensation and to improve ionization of the analytes. The collision cell requires a collision gas (typically Nitrogen or Argon) and must be turned on for MSMS analysis.

The triple quadrupole mass spectrometer requires specific voltages applied to certain components of the mass spectrometer such as electrospray source, ion beam focusing components, collision cell, quadrupoles and the electron multiplier(s) for detection of ions. Additionally, MSMS dwell times may be optimized to adjust signal intensity and number of scans across a peak, as needed. Other instrument designs may control these settings differently and the operator should be qualified with operation of those instruments, their software, and the instrument parameters before attempting to transfer methods to those instrument types. A typical tune page setting and mass spectrometer method file for a Quattro I1 and for analyzing the fluorochemical acids of this method, is shown below, and may serve as a starting place to begin analyte specific optimization procedures.

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Each analytical run requires that a mass spectrometer method include the unique mass transitions to be monitored, ion detector dwell times, and other analyte-specific voltages that require operator specification. Perfluorinated carboxylates and sulfonates are monitored using negative-ion mode detection (e.g. detection of anions). Unique analyte mass transitions should be determined based on parent and daughter ions that are distinguishable from matrix ions and other interferences, and that also provide ample signal to noise response in the quantitative range being measured. Examples of some fluorochemical acid mass transitions, dwell times, and source voltages are shown below, but are not meant to be all inclusive of all analytes that can be quantified by this method. See Table 1 for additional mass transitions that may be used for the analytes listed in this method.

ETS-8-042.0 Solvent Extraction and LC/MS/MS Analysis of Soils for Perfluorinated Carboxylates and Sulfonates


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L

Perfluorododecanoate (C12; PFDoA) 613 > 569 613 > 169 X

Perfluorobutane sulfonate (PFBS) 299 > 80 299>99 X

Perfluorohexanes sulfonate (PFHS) 399 > 80 399 > 99 X

'3~-1,2-pe~uorooctanoate (I3c-1,2- 415 >370 X X

Trimethylsilylpropane sulfonate (TMS- 195 > 80 X x PSI

Perfluorooctane sulfonate (PFOS) 499 > 80 499 > 99 499 > 130

PFOA)

11 Data Analysis and Calculations

11 .I Calculations The following calculations should be used, when applicable to the study. If calculations other than those listed are used, they will be documented in the raw data

Calculate Matrix Spike recovery as percent recoveries using the following equation:

Measured Conc. - Matrix Blank Conc. Theoretical Conc.

Spike Recover (%) = x 100%

Calculate the Mean (Average) of n_ values by the following equation:

C (values)

n Mean =

Calculate Standard Deviation (SD) by the following equation:


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Calculate relative standard deviation (RSD), also know as coefficient of variance (C.V.%) as a measure of precision, using the following: equation:

Standard Deviation RSD = x 100% M a

Calculate percent deviation, also referred to as relative error (RE%),fiom theoretical values using the following equation:

Theoretical Conc. - Measured Conc. Theoretical Conc.

RE% =

Calculate relative percent difference (RPD) of two values using the following equation:

Value 1 - Value 2 RPD = x 200% Value 1 + Value 2

12 Pollution Prevention and Waste Management

Non-flammable waste is disposed of in low BTU, or other appropriate, waste stream.

Soil waste is disposed of in special soil waste containers, or other waste stream destined for incineration.

Flammable solvent wastes, including HPLC effluents, are disposed of in high BTU containers.

Glass pipette waste is disposed of in broken glass containers located in the laboratory.

Biohazardous waste should be disposed of in biohazardous waste receptacles

Needles and razor blades discarded to an appropriate sharps container.

13 Records

Complete the extraction worksheet (Attachment A) for all samples extracted and store with the study raw data. Summarize data using suitable software and store hard copies in the study folder

14 Attachments

Attachment A: Sample Extraction Worksheet (Example only)

15 References

None

16 Affected Documents

None

17 Revisions

Revision Number Revision Descriution

0 New method procedure written by Cleston Lange

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Attachment A: Sample Extraction Worksheet (example)

t 1 I f



4

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Method

Method of Analysis for the Determination of Perfluorobufanoic Acid (PFBA), Petfluoropentanoic Acid (PFPeA), Perfluorohexanoic Acid (PFHA), Perfluoroheptanoic Acid (PFHpA), Perfluoroocfanoic Acid (PFOA), Petfluorononanoic Acid (PFNA), Perfluorodecanoic Acid (PFDA),

Perfluoroundecanoic Acid (PFUnA), Perfluorododecanoic Acid (PFOoA), Perfluorobufanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and

Perfluorooctanesulfonate (PFOS) in Water, Soil and Sediment by LC/MS/MS

Method Number: ETS-8-012.1

Adoption Date: Upon Signing

Effective Date:

Approved By:

ETS-8-012.1 Page 1 of 12

Method of Analysis for the OetenlnaUon of Perlluwobutanoic Aad (PFBA), Perllumopentanoic Acid (PFPeA). Periluorohexanoic 466 (PFHA). Pemuorohaplanoic Acid (PFHpA). Perfluorooctanoic Acid (PFOA). Perfluorononanoic Acid (PFNA). PerRuwodecanoic

Add (PFDA). Perlluomundecanoic Acid (PFUnA). Perlluorodcdecanoic Acid (PFOoA), Perlluorobutanesulfonate (PFBS). Parllua-ohexanesuifonate (PFHS), and Periluoroodanesulfonate (PFOS) in Water, Soil and Sediment by LC/MS/MS

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* - < *


1 Scope and Application

This method is to be used to quant i Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid (PFPeA), Perfluorohexanoic Acid (PFHA), Perfluoroheptanoic Acid (PFHpA), Peffluorooctanoic Acid (PFOA), Perfluorononanoic Acid (PFNA), Perfluorodecanoic Acid (PFDA), Perfluoroundecanoic Acid (PFUnA), Perfluorododecanoic Acid (PFDoA), Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) by High Performance Liquid Chromatography coupled to a tandem Mass Spectrometric Detector (LCMSMS) in water, soil and sediment. The method is designed to target a lower limit of quantiation (LOQ) of 0.025 ng/mL (water) and 0.20 ng/g (soil and sediment).

2 Method Summary

Aqueous samples are mixed with equal volumes of acetonitrile, thoroughly mixed, centrifuged if necessary, and aliquoted for analysis by LCMSMS. Similarly, onegram aliquots of soil and sediments are mixed with 80:20 acetonitri1e:water mixture, thoroughly mixed, centrifuged, and aliquoted for analysis by LCMSMS.

This is a performance-based method. Method accuracy is determined for each sample set using multiple laboratory control spikes at multiple concentrations. This method also requires that the precision and accuracy for each sample be determined using field matrii spikes (aqueous samples) or laboratory matrix spikes (soil and sediment) to verify that the method is applicable to each sample math. Sample results for spikes outside of 70% to 130%, will not be reported due to noncompliant quality control samples.

Fortification levels for field matrix spikes and for laboratory matrix spikes should be at least 50% of the endogenous level and less than 10 times the endogenous level to be used to determine the statement of accuracy for analytical results.

3 Defini$b&dOCUme!?f /?My be used, if Curref?f, for I # days from

3.1 Calibration Standard A solution prepared by spiking a known volume of the Working Standard (WS) into a predetermined amount of ASTM type I or HPLC grade water, diluted with acetonitrile, and analyzed according to this method. Calibration standards are used to calibrate the instrument response with respect to analyte concentration.

3.2 Laboratory Duplicate Sample (LDS, or Lab Dup) 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.

3.3 Field Blank (FB)ITrip Blank 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 conditions, storage, preservation and all analytical procedures. The purpose of the FB is to determine if test substances or other interferences are present in the field environment. This sample is also referred to as a Trip Blank. Trip blanks are not a requirement for soil or sediment samples.

3.4 Field Duplicate Sample (FDS, Field Dup) 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.

ETS-8-012.1 Page 2 of 12

Method of Analysis for the Determination of Pemuorobutanoic Acid (PFBA), Perfluoropentanoic Add (PFPeA). Pertluorohexanoic Acid (PFHA). Perfluoroheptanoic Acid (PFHpA), Peffluorooctanoic Acid (PFOA), Peffluorononanoic Acid (PFNA), Pemuorodecanoic

noic Acid (PFDoA), Perfluorobutanesulfonate (PFBS), (PFOS) in Water, Soil and Sediment by LCiMS/MS

€06-0549 Interim Report#lS Woodbury Soils: October 2007 Page 91 of 156

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3M Environmental Laboratory €06-0549 Interim Report #I 5

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.

3.5 Field Matrix Spike (FMS) A sample to which known quantities of the target analytes are added to the sample bottle in the laboratory before the bottles are sent to the field for collection of aqueous samples. 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 between approximately 50% and 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. The FMS is analyzed to ascertain if any matrix effects, interferences, or stability issues may complicate the interpretation of the sample analysis.

3.6 Trip Blank Spike (Field Spike Control Sample, FSCS) An aliquot of ASTM Type I or HPLC grade water to which known quantities of the target analytes are added in the laboratory prior to the shipment of the collection bottles. The FSCS is extracted and analyzed exactly like a sample to help determine if the method is in control and whether a loss of analyte could be attributed to holding time, sample storage and/or shipment issues. A low and high FSCS are appropriate when expected sample concentrations are not known or may vary. At least one separate, un-spiked sample must be taken at the same time and place as each FMS.

3.7 Laboratory Control Sample (LCS) An aliquot of control matrix 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 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.

3.8 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 determine whether the sample matrix contributes bias to the analytical results. The endogenous concentrations of the analytes in the sample matrix must be determined in a separate aliquot and the measured values in the LMS corrected for these concentrations. LMSs are required for soils and sediments and are optional for analysis of aqueous samples.

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

3.10 Limit of Quantitation (LOQ) The lower limit of quantiation (LLOQ) for a dataset is the lowest concentration that can be reliably quantitated within the speafied 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 matrixdependent.

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

ETS-8-012.1 Page 3 of 12

Method of Analysis for the Determination of Perfluorobulanoic Add (PFBA). Pemuoropenlanoic Aad (PFPeA), PeAuomhexanoic Acid (PFHA). Peffluoroheptanoic Acid (PFHpA), Pemuoroodanoic Acid (PFOA), Pemuorononanoic Add (PFNA), Pefluomdecanoic

Add (PFDA). Pemuoroundecanoic Acid (PFUnA), Pemuorododecanoic Acid (PFDoA), Pemuombutanesulfonate (PFES), Pernuorohexanesulfonale (PFHS). and Pertluomoclanesulfonale (PFOS) in Water, Soil and Sediment by LClMSlMS

EO6-0549 Interim ReporMI 5 Woodbury Soils: October 2007 Page 92 of 156

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3M Environmental Laboratory E06-0549 Interim Report #15

3.11 Method Blank An aliquot of control matrix 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 determine if test substances or other interferences are present in the laboratory environment, the reagents, or the apparatus.

3.12 Sample A sample is an aliquot removed from a larger quant i of material intended to represent the original source material.

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

3.14 Surrogate A compound similar to the target analyte(s) in chemical composition and behavior that is not normally found in the sample(s). A surrogate compound is typically a target analyte with at least one atom containing an isotopically labeled substitution. If used, surrogate(s) are added to all samples and qualii control samples (except solvent blanks and half of the prepared method blanks). Surrogate(s) are added to quantitatively evaluate the entire analytical procedure including sample collection, extraction, and analysis. Inclusion of a surrogate analyte is an optional quality control measure and is NOT required.

3.15 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.


4.1 Health and Safety The acute and chronic toxiuty of the standards for this method have not been preasely determined; however, each should be treated as a potential health hazard. The analyst should wear gloves, a lab coat, and safety glasses to prevent exposure to chemicals that might be present.

The laboratory is responsible for maintaining a safe work environment and a current 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 Cautions The analyst must be familiar with the laboratory equipment and potential hazards including, but not limited to, 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 information and cautions.

5 Interferences

During extraction and analysis, major potential contaminant sources are reagents and glassware. All materials used in the analyses shall be demonstrated to be free from interferences under conditions of analysis by running method blanks.

ETS-8-012.1 Page 4 of 12

Method Of Analysis for the Determination of Peffluorobutanoic Add (PFBA). Peffluoropsntanoic Add (PFPeA), Peffluorohexanoic Add (PFHA). Perfluoroheptanoic Acid (PFHpA). Perfluorooctanoic Add (PFOA), Peffluorononanoic Add (PFNA). Peffluorodecanoic

Acid (PFDA). Peffluoroundecanoic Acid (PFUnA), Peffluorododecanoic Add (PFDoA), Peffluorobutanesulfonate (PFBS). Pemuorohexanesulfonate (PFHS), and Peffluorooctanesulfonate (PFOS) in Water, Soil and Sediment by LCIMSiMS


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E064549 Interim Report #15

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 Equipment

6.1 Instrumentation and Equipment A high performance liquid chromatograph capable of pumping up to 2 solvents and equipped with a variable volume injector capable of injecting 5-200 pL connected to a tandem Mass Spectrometer (LC/?vlS/?vlS). Applied Biosystems Suex API 5000 instrumentation is required to meet the LOQs of 0.025 ng/mL (water) and 0.20 nglg (soil and sediment). If analyte concentrations require dilutions for one or more analytes that preclude the targeted LOQs from being reached, Applied Biosystems Sciex API 4000 instrumentation may be utilized since the LOQs will already be raised.

Analytical balance capable of reading to 0.0001 gram.

A device to colled raw data for peak integration and quantitation.

15mL and 50-mL disposable polypropylene centrifuge tubes.

Disposable micropipettes (10-20 pL, 25-50 pL, 50-100 pL, 100-200 pL).

125-mL LDPE narrow-mouth bottles.

2-mL clear HPLC vial kit.

Disposable pipettes, polypropylene or glass as appropriate.

Ultrasonic bath.

Centrifuge capable of spinning 15-mL and 50-mL polypropylene tubes at 3000 rpm.

6.2 Chromatographic System Analytical Column: Luna 3 pm C8 (2) Mercury (Phenomenex), 2 mm x 4 mm, 3 pm (PM: 00M4248-DO-CE)

Temperature: 35°C

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

Mobile Phase (6): Methanol

Gradient Program:

Time Imin) - % A - % B 0.0 90 10 0.5 90 10 2.0 10 90 5.0 10 90 5.1 0 100 6.0 0 100 6.1 90 10 10.0 90 10

Injection Volume: 5 pL (can be increased to as much as 50 pL).

Flow Rate (mumin) 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75

Quantiation: Peak Area -external standard calibration curve, l /x weighted. ETS-8-012.1 Page 5 of 12

Method of Analysis for the Determination of Pemuorobutanoic Acid (PFBA), Pemuoropentanoic Acid (PFPeA). Periluorohexanoic Acid (PFHA), Perfluomheptanoic Acid (PFHpA). Pemuorooctanoic Acid (PFOA), Perfluorononanoic Acid (PFNA). Petluorodecanoic

Acid (PFDA). Peffluoroundecanoic Acid (PFUnA). Pertluorododecanoic Acid (PFDoA), Pemuombutanesulfonate (PFBS). Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil and Sediment by LCIMSIMS


9h 14 &hi


Run Time: - 10 minutes.

The previous information is intended as a guide; alternate conditions and equipment may be used provided that data quality objectives are met.

6.3 MSlMS System

6.3.1 Mode: Eledrospray Negat've MRM mode, monitoring the following transitions:

Multiple transitions for monitoring the analytes is an option because 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 method sensitivity is achieved, provided that retention time criteria are met to assure adequate specificity.

The previous information is intended as a guide, alternate instruments and equipment may be used.


Water - HPLC grade

Methanol - HPLC grade

Ammonium Acetate - A.C.S. Reagent Grade

Acetonitrile - HPLC grade

Perfluorobutanoic Acid (PFBA) - Oakwood Products, Inc

Perfluoropentanoic Acid (PFPeA) - Sigma-Aldrich

Perfluorohexanoic Acid (PFHA) - Oakwood Products, Inc

Perfluoroheptanoic Acid (PFHpA) - Oakwood Products, Inc

Perfluorooctanoic Acid (PFOA) - Oakwood Products, Inc

Perfluorononanoic Acid (PFNA) - Oakwood Products, Inc

PerRuorodecanoic Acid (PFDA) - Oakwood Products, Inc

Perfluoroundecanoic Acid (PFUnA) - Oakwood Products, Inc

Perfluorododecanoic Acid (PFDoA) - Oakwood Products, Inc

ETS-8-012.1 Page 6 of 12

Method Of Analysis for the Determination of Pertluorobutanoic Add (PFBA), Pertluoropentanoic Add (PFPeA), Pertluorohexanoic Add (PFHA). Pemuoroheptanoic Acid (PFHpA). Pemuoroodanoic Add (PFOA), Perfluorononanoic Add (PFNA), Pertluomdecanoic

Add (PFDA). Perfluoroundecanoic Acid (PFUnA), Pertluorododecanoic Acid (PFDoA). Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil and Sediment by LC/MS/MS


TI f L 1 i 3 *


Perfluorobutanesulfonate (PFBS) - 3M

Perfluorohexanesulfonate (PFHS) - 3M

Perfluoroodanesulfonate (PFOS) - Fluka

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

8 Sample Handling

8.1 Water Sample Extraction

8.1 .I Measure 10 mL of sample into a 5o-mL polypropylene centrifuge tube. Fortifications are to be done at this point, ifnecessary. Other volumes and containers may be used as approptiate.

Add 10 mL of acetonitrile to the sample in the centrifuge tube. Cap tghtly and shake.

Sonicate sample for -2 hours at mom temperature. This step is optional, but is recommended if particulates appear to be present.

8.1.2

8.1.3

8.1.4 Centrifuge for -10 minutes at -3000 rpm. This step is optional, but is recommended if samples are sonicated.

8.1.5

8.1.6

Transfer a poltion of the supematant to an autosampler vial for analysis.

Dilute sample, if necessary, wivl50:50 acetonitrkwater.

8.2 Soil and Sediment Extraction

8.2.1 Wegh 1 g of sample into a 15mL polypropylene centrifuge tube. Fortifications are to be done at this point, if necessary.

Add 8 mL of 80:20 acetonitrilewater to the sample in the centrifuge tube. Cap tghtly and shake.

Sonicate sample for -2 hours at mom temperature.

Centrifuge for -1 0 minutes at -3OOO rpm.

Transfer a portion of the supematant to an autosampler vial for analysis.

Dilute sample, if necessary, with 5050 acetonitrilewater.

Analyze samples using eledrospray LCIMSIMS

Other weights and volumes can be used as long as the QC elements specified in this method are satisfied and all sample preparation procedures may be reconstructed.

8.2.2

8.2.3

8.2.4

8.2.5

8.2.6

8.2.7

9 Samde Analvsis - LClMSlMS

ETS-8-012.1 Page 7 of 12

Method of Analysis for the Determination of Pemuorobutanoic Acid (PFBA), Pemuoropentanoic Acid (PFPeA), Perfluorohexanoic Acid (PFHA). Pemuoroheptanoic Acid (PFHpA), Pemuorooctanoic Acid (PFOA), Pemuomnonanoic Acid (PFNA), Pemuorodecanoic

Acid (PFDA), Peffluoroundecanoic Acid (PFUnA). Pemuorododecanoic Acid (PFDoA), Pemuorobutanesulfonate (PFBS). Pemuorohexanesulfonate (PFHS). and Perfluoroodanesulfonate (PFOS) in Water, Soil and Sediment by LCIMSIMS

€06-0549 Interim Repoti#l5 Woodbury Soils: October 2007 Page 96 of 156

i


9.1.1

9.1.2

9.1.3

9.1.4

A minimum of six calibration levels must be present in the final calibration curve.

An entire set of calibration standards is injected at the beginning of a sample set prior to sample a n a m . As an alternative, an entire set of calibration standards may be injected at the beginning of a sample set followed by calibration standards interspersed every 510 samples (to account for a second set ofstandards). In either case, calibration standards or a continuing calibration verification standard must bracket the first sample and the last sample. Analytical studies may only require that an initial calibration cutve be analyzed prior to samples and that the continued accuracy of the initial calibration curve be confirmed by the analysls of continuing calibration verification standards. The same approach should be used throughout the entire study unless reasons are documented and technical justifcation to change is approved prior to sample analysls.

The standard curve is plotted by quadratic iit (y = d + bx + c), weighted l /x or unweghted, or using a linear fit, weighted lk, using suitable &are. The calibration cum 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 documented in the raw data.

Samples containing analytes that are quantitated above the concentration of the hghest standard in the curve should be further diluted and reanalyzed or reinjected using a smaller volume.

10 Quality Control

10.1 Data Quality Objectives. This method and required quality control samples is designed to generate data accurate to +/-30% with a targeted LOQ of 0.025 ng/mL (water) or 0.20 ng/g, wet weight (soil and sediment). Any deviations from the quality control measures spelled out below will be documented in the raw data and footnoted in the final report.

10.2

10.2.1

10.2.2

10.3

Blanks

Method Blank

Method blanks must be prepared with each extraction batch. A range of three to seven method blanks must be prepared. These method blanks must be interspersed throughout the extraction batch and analyzed interspersed 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. 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, or alternatively, the method blanks must be evaluated statistically to determine outliers or technical justification to eliminate one or more results should be made.

Solvent Blank

Solvent blanks must be analyzed throughout the analytical sequence. Solvent blanks that show area counts greater than 50% of the area counts of the LOQ standard must be evaluated to determine if analytical results are significantly impacted by sample carry-over or an unacceptable buildup of analyte in the instrumental background.

Sample Replicates Samples should be prepared in duplicate in the lab (soil and sediment) or collected in duplicate in the field (water). The relative percent difference, RPD, should be reported. RPD results greater than 20% (water) or

ETS-8-012.1 Page 8 of 12

Method of Analysis for the Determination of Perfworobutanoic Acid (PFBA), Petfluoropentanoic Acid (PFPeA), Pemuorohexanoic Acid (PFHA), PerRuomheptanoic Acid (PFHpA), Pemuorooctanoic Acid (PFOA), Pemuorononanoic Add (PFNA), Pemuorodecanoic

Acid (PFDA), Pemuoroundecanoic Acid (PFUnA), Pemuomdodecanoic Acid (PFDoA), Peffluorobutanesulfonate (PFBS), Perfhomhexanesulfonate (PFHS). and Pemuorooctanesulfonate (PFOS) in Water, Soil and Sediment by LC/MS/MS

€06-0549 Interim Reporl#l5 Woodbury Soils: October 2007 Page 97 of 156

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3M Environmental Laboratory €06-0549 Interim Repoti # I5

30% (soil and sediment) will be flagged in the report, but will not be excluded from reporting. The requirement for replicates excludes field blanks and rinse blanks.

10.4 Surrogate Spikes Surrogate spikes are not required but may be used on project specific requirements.

10.5 Lab Control Sample Triplicate lab control spikes at a minimum of two different concentrations are to be prepared with each extraction batch. Low lab control spikes should be prepared at concentrations in the range of 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. The relative standard deviation of the control spikes for these six pooled control samples must be less than or equal to 20% and the average recovery must be 80-120%. If the above criteria are not met, the entire set of samples should be re-injected or re-extracted as appropriate.

10.6 Field Matrix Spikes I Lab Matrix Spikes Recoveries of field matrix spikes (aqueous samples) and laboratory matrix spikes (soils and sediments) are anticipated to be between 70% and 130% of the fortified levels. If the recoveries of the spikes fall outside the acceptable range, the sample result will be reported as “NR” (not reported due to non-compliant QC results).

The targeted fortification levels should be at least 50% of the endogenous level and less than 10 times the endogenous level to be used without justification to determine the statement of accuracy for analytical results.

The average of the sample and the lab duplicate (soils and sediment) or field duplicate (water) should be used to calculate the recovery.

10.7 Standard Preparation

10.7.1 Standard Stock Solutions

Prepare individual stock solutions of each analyte at -1000 pg/mL by weighing 100 mg of analytical standard (corrected for purity and salt content, if necessaty) and dilute to 100 mL with methanol or acetonitrile in separate 100-mL volumetric flasks. For purity correction, take the amount of analyte that is needed for weighing (i.e.lOO mg) and divide by the punty in decimal form (i.e. 99.6% = 0.996). The result is the weight that is needed to make the solution corrected for purity (Le. weigh 100.4 mg). For salt correction, calculate the salt content by taking the molecular weight of the target compound (Le. PFOS = 499) and dividing by the molecular weight of the entire compound (Le. PFOS potassium salt (CaF1,SO3-K‘ = 538). The result is the salt content in decimal form (Le. 0.9275). Take the amount of analyte that is needed for weighing (i.e. 100 mg) and divide by the salt content in decimal form. The result is the weight that is needed to make the solution corrected for salt content (Le. weigh 107.8 mg). Store all stock solutions in appropriate containers and at appropriate storage conditions for up to 6 months from the date of preparation.

Alternate stock solution concentrations can be made, if necessary, using alternatie masses and volumes.

10.7.2 Standard Fortification Solutions

A 10 pg/mL mixed fortification solution containing all of the analytes is prepared by bringing 1 mL of each of the lo00 pg/mL stock solutions to a final volume of 100 mL with acetonitrile in a 100-mL volumetric flask. A 1.0 pg/mL mixed fortification solution containing all of the analytes is prepared by bringing 10 mL of the 10 pg/mL mixed solution to a final volume of 100 with acetonitrile in a 100-mL volumetric flask. A 0.1 pg/mL mixed fortification solution containing all of the analytes is prepared by bringing 10 mL of the 1.0 pg/mL mixed solution to a final volume of 100 with acetonitrile in a 100-mL volumetric flask. A 0.01 pg/mL mixed fortification solution containing all of the analytes is prepared by bringing 10 mL of the 0.1 pg/mL solution to a final volume of 100 with acetonitrile in a 100-mL volumetric flask. Store all fortification standards up to 6 months from the date of preparation

ETS-8-012.1 Page 9 of 12

Method of Analysis for the Determination of Pemuorobutanoic Acid (PFBA), Pemuoropenlanoic Acid (PFPeA), Perfluorohexanoic Acid (PFHA), Pemuoroheptanoic Acid (PFHpA), Perfluorooctanoic Acid (PFOA), Perfluorononanoic Add (PFNA). Pemuorodecanoic

Acid (PFDA), Pemuoroundecanoic Acid (PFUnA), Pemuorododecanoic Acid (PFDoA), Pemuorobutanesulfonate (PFBS), Pemuorohexanesulfonate (PFHS), and Pemuorooctanesulfonale (PFOS) in Water, Soil and Sediment by LCIMSIMS

€06-0549 Interim Report#l5 Woodbury Soils: October 2007 Page98of156

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Alternate fortification solution concentrations can be made, if necessary. Likewise, alternative volumes may be used.

10.8 Instrument Calibration

10.8.1 Lc/Ms/MS calibration standards are prepared externally in 50:s acetonitrikwater and are used to construct the calibration curves for the water, soil, and sediment procedures.

10.8.2 The following is a typical example of a calibration set Alternate or additional concentrations may be prepared as needed.

Concentration Initial Solution Final Concentration of of Initial Solution Aliquoted Volume Final Solution Calibration Standard

(nglmL) ( m u Volume (mL) (ng/mL) 100 5 100 5.0 100 2.5 100 2.5 10 10 100 1 .o 5 10 100 0.5

2.5 10 100 0.25 1 10 100 0.1

0.5 10 100 0.05 1 2.5 100 0.025

Store all calibration standards for up to three months. Alternate volumes and concentrations of standards may be prepared as needed.

11 Data Analysis and Calculations

Use the following equation to calculate the amount of analyte found (in nglmL, based on peak area) using the standard curve (linear regression parameters) generated by an appropriate soflware program:

(Peak Area -Intercept) DF Analyte found (nglmL) = Slope

DF = factor by which the final volume was diluted, if necessary.

For samples fortified with known amounts of analyte prior to extraction, use the following equation to calculate the percent recovery.

Total analyte found (nglmL) -Average analyte found in sample (nglmL) Analyte added (nglmL)

oo Recovery =

Use the following equation to convert the amount of analyte found in ng/mL to nglg (ppb).

Analyte found(nglmL) x Volume extracted (mL) Sample weight (9)

Analyte found (ppb) =

Use the following equation to calculate the amount of analyte found in ppb based on dry weight.

Analyte found (ppb) dry weight = Analyte found (ppb) x [I 00% I total solids (%)I

12 Method Performance

ETS-8-012.1 Page 10 of 12

Method of Analysis for the Determination of Pemuorobutanoic Acid (PFBA), Pemuoropentanoic Acid (PFPeA), Perfluorohexanoic Acid (PFHA), Perfluoroheptanoic Acid (PFHpA), Perfluorwctanoic Acid (PFOA), Perfluomnonanoic Acid (PFNA), Perfluorodecanoic

Add (PFDA), Pemuoroundecanoic Acid (PFUnA). Pemuomdodecanoic Acid (PFDoA). Pemuombutanesulfonate (PFES), Pemuorohexanesulfonate (PFHS), and Pemuorooctanesulfonate (PFOS) in Water, Soil and Sediment by LC/MS/MS

€06-0549 Interim Report#lS Woodbury Soils: October 2007 Page 99 of 156

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Any method performance parameters that are not achieved must be considered in the evaluation of the data. Nonconformance to any specified parameters must be described and discussed if the Technical Manager (non- GLP study) or Study Director (GLP study) chooses to report the data.

If criteria listed in this method performance section are not met, maintenance may be performed on the system and samples reanalyzed, or other actions taken as appropriate. 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.

12.1 System Suitability System Suitability standards are not a required component of this method. If required by protocol or by the technical manager, a minimum of three system suitability samples are injected at the beginning of each analytical run prior to the calibration curve. Typically these samples are at a concentration near the mid level of the calibration curve and are repeated injections from one autosampler vial. The system suitability injections must have area counts with an RSD of 55% and a retention time RSD of 52% to be compliant.

12.2 Quantitation Calibration Curve: The coefficient of determination (?) value for the calibration curve must be greater than or equal to 0.985. The concentration of each point in the curve must back calculate to be within Q5% of the theoretical concentration with the exception of the LLOQ, which may be within ?30%. Calibration curve points that are not at the high or low end of the curve may not be deactivated.

CCV Performance: The continued amracy of the calibration curve must be demonstrated by analyzing continuing calibration verification (CCV) standards. Each CCV may be a calibration curve point that is reinjected or a separately prepared standard, and is typically near the middle of the calibration curve. Alternative concentrations or multiple concentrations may be chosen depending on project requirements. Not more than ten samples or spikes may be analyzed between the initial calibration and a CCV or bracketing CCVs. The accuracy of each analyte must be within 25% of the theoretical value. Samples that are bracketed by CCVs not meeting these criteria must be reanalyzed.

Demonstration of Specificity: Specifiuty is demonstrated by chromatographic retention time (within 4% of standard) and the mass spectral response of unique ions.

12.3 Sensitivity The targeted limit of quantitation for all analytes is 0.025 ng/mL (water) and 0.20 ng/g (soils and sediments, wet weight). The LOQ for any specific analyte may vary depending on the evaluation of appropriate blanks and the accuracy of the low-level calibration curve points. Refer to Section 10 for additional details.

12.4 Accuracy This method and required quality control samples are designed to generate data that are accurate to +/-30%. Section 10 contains additional information regarding the required accuracy of laboratory control spikes, field matrix spikes (water samples) and laboratory matrix spikes (soils and sediments).

12.5 Precision Samples should be prepared in duplicate in the lab (soil and sediment) or collected in duplicate in the field (aqueous). The relative percent difference, RPD, should be reported. RPD results greater than 20% (water) or 30% (soil and sediment) will be flagged in the report, but will not be excluded from reporting. The requirement for replicates excludes field blanks or rinse blanks.

Section 10 contains additional information regarding the required precision of laboratory control spikes.

13 Pollution Prevention and Waste Management Page 11 of 12 ETS-8-012.1

Method of Analysis for the Determination of Pemuorobutanoic Acid (PFBA). Pertluoropentanoic Acid (PFPeA), PeAuorohexanoic Acid (PFHA). Peffluoroheptanoic Acid (PFHpA). Pemuomoctanoic Acid (PFOA), Pemuorononanoic Acid (PFNA), Penluorodecanoic

Acid (PFDA), Pemuoroundecanoic Acid (PFUnA), Pertluorododecanoic Acid (PFDoA), Pemuombutanesulfonate (PFBS), Peffluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil and Sediment by LCIMSIMS


vs f r i s *,


Waste generated when performing this method will be disposed of appropriately. The original samples will be archived at the 3M Environmental Laboratory in accordance with internal procedures.

14 Records

Each data package generated for a study must include all supporting information for reconstruction 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 sheetstrecords, instrument run log (instrument batch records, instrument acquisition method, summary pages), instrument results files, chromatograms, calibration curves, and data calculations.

15 References

Exygen Research Analytical Method VOOO3305-1 details method development and verification of recovery for multiple analytes in groundwater, surface water, soil, and sediment. This will be archived as part of E06-0549.

16 Affected Documents

None.

17 Revisions

Revision

Number Revision Description

Revision

- Date

1 The sonication and centrifugation steps of the water sample preparation were 11110106

made optional. The accuracy requirements of the analytical balance were updated.

The method was updated to allow the use of a linear l /x weighted calibration curve.

The table of required daughter ions for the analytes was updated. The method

was updated to allow different sample volumes to be extracted and to allow

different standard bottles and storage conditions to be used. Calibration requirements

were updated to show that analyzing continuing calibration verification standards at one

concentration was an acceptable alternative to reinjecting all curve points used to construct

the calibration curve. Minor wording changes were made throughout.

ETS-8-012.1 Page 12 of 12

Method of Analysis for the Determination of Pertluorobulanoic Add (PFBA), Pemuoropentanoic Add (PFPeA), Pertluorohexanoic Add (PFHA), Perfluoroheptanoic Acid (PFHpA). Pemuoroodanoic Add (PFOA), Pemuorononanoic Add (PFNA), Pertluorodecanoic

Add (PFDA), Pemuomundecanoic Add (PFUnA). Pertluomdodecanoic Acid (PFDoA). Pertluombutanesulfonate (PFBS). Pemuorohexanesulfonate (PFHS), and Pertluorooctanesulfonate (PFOS) in Water, Soil and Sediment by L C N S N S



ATTACHMENT c: PROTOCOL AND PROTOCOL AMENDMENTS



Exygen Study Number: PO002561

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 Perfluorooctanesulfonate (PFOS) in Water, Soil,

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


Performing Laboratow: Exygen Research 3058 Research Drive State College, PA 1680 1 Phone: (814) 272-1039

SDonsor Representative: Robert A. Paschke Manager, 3M Corporate Environmental Programs

St. Paul, MN 55144 Phone: (65 1) 778-5200

Bldg 42-02-E-27

Page I of 37


3M Environmental Laboratory EO6-0549 Interim Report #15


' DISTRIBUTION:

1) Jaisimha Kesari, Study Director, Weston Solutions

2) John M. Flaherty, Principal Investigator, Ex ygen Research

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

4) Exygen Research Quality Assurance Unit

Page 2 of3 7

EO6-0549 Interim Report#l5 Woodbury Soils: October 2007 Page 104 of 156

3M Environmental Laboratory E064549 Interim Report #IS

Exygen Study Number: PO00256 I

,PROTQCOL APPROVAL

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


APPROVA$f3

Weston Solutions

Robert A. Paschke, Sponsor Representative 3M Company

Date

J6hn M. Flaherty,.Principal Investigator Date / Exygen Research

z3-0Qy- mob Date

Page 3 o j 3 7

E06-0549 Interim Repori#75 Woodbury Soils: October 2007 Page 705 of 156

3M Environmental Laboratory €06-0549 Interim Repod #15


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

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 Perfluorooctanesulfonate (PFOS) in Water, Soil, and Sediment Using LCIMSMS for the 3M Cottage Grove Monitoring Program Phase 2


APPROVALS

Jaisimha Kesari, Study Director Weston Solutions

r

Robert A. Paschke, Sponsor Representative 3M Company

John M. Flaherty, Principal Investigator Exygen Research

Richard A. Grazzini, Management Exygen Research

Lydia Shaffer, Technical Lead, Quality Assurance Unit Exygen Research

Date

Date

Date

Date

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3M Environmental Laboratory €06-0549 Interim Reporl#l5

Exygen Study Number: PO00256 I

TABLE OF CONTENTS

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

DISTRIBUTION ............................................................................................................................................... 2 PROTOCOL APPROVAL ................................................................................................................................ 3

TABLE OF CONTENTS .................................................................................................................................. 4

INTRODUCTION ............................................. ......................................................... TEST MATERIAL ............................................................................................................................................ 5

OBJECTIVE ..................................................................................................................................................... IO TESTING FACILITY ....................................................................................................................................... 10

STUDY DIRECTOR ......................................................................................................................................... 10

SPONSOR REPRESENTATIVE ...................................................................................................................... 11

PRINClPAL 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 ......................................... METHOD FOR CONTROL OF BIAS ................................................................ STATISTICAL METHODS ............................................................................................................................. 15

GLP STATEMENT ........................................................ ............................................. 15

REPORT ........................................................................................................................................................... 15

SAFETY AND HEALTH ................................................................................................................................. 16

AMENDMENTS TO PROTOCOL .................................................................................................................. 16

DATA RECORD KEEPING ........ ......................................................................... QUALITY ASSURANCE ............ .................................................................................... 17

RETENTION OF DATA AND ARCHIVING .................................. ............................................ 18

APPENDIX I, ANALYTICAL METHODS ..................................................................................................... 19

APPENDIX 11 . MINNESOTA POLLUTION CONTROL GUIDANCE DOCUMENTS ................................ 32

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3M Environmental Laboratory €064549 Interim Report # I5

Exygen Study Number: PO00256 1

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), pertluorododecanoic acid' (PFDoA), perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (PFHS), and perfluorooctanesulfonate (PFOS) in water, soil, and sediment using LCIMSIMS 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), perfluorohexanesul fonate (PFHS), and perfluorooctanesulfonate (PFOS).

PFBA Chemical Name: Perfluorobutanoic acid Molecular Weight: 214 Lot Number: U02C

Supplier: Oakwood Products, Inc. Transitions Monitored: 213 + 169 Structure:

Purity: 99%

Page 5 of3 7




PFPeA Chemical Name: Perfluoropentanoic acid Molecular Weight: 264 Lot Number: 20524JB

Supplier: Sigma-Aldrich Chemical Co. Transitions Monitored: 263 + 219 Structure:

Purity: 99.1%

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

F F O F F F

F OH

F F F

PFHpA Chemical Name: Perfluoroheptanoic acid Molecular Weight: 364 Lot Number: H3002

Supplier: Oakwood Products, Inc. Transitions Monitored: 363 + 319,363 + 169 and 363 -+ 119 Structure:

Purity: 99%

F F F O

F OH

F F F

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3M Environmental Laboratory €06-0549 Interim Report #I 5


PFOA Chemical Name: Perfluorooctanoic acid Molecular Weight: 414 Lot Number: Y16G Punty: 98% Supplier: Oakwood Products, Inc. Transitions Monitored: 413 4 369,413 + 219 and 413 + 169 Structure:

F OH

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 4 219 Structure:

F OH F F F F

PFDA Chemical Name: Perfluorodecanoic acid Molecular Weight: 514 Lot Number: Y31J Purity: 98% Supplier: Oakwood Products, Inc. Transitions Monitored: 513 + 469,513 + 219 and 513 4 2 6 9 Structure:

F F F F O F

OH F F F F F

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3M Environmental Laboratory E060549 Interim Report #f5


PFUnA Chemical Name: Perfluoroundecanoic acid Molecular Weight: 564 Lot Number: U11N

Supplier: Oakwood Products, Inc. Transitions Monitored: 563 + 519,563 + 269 and 563 + 219 Structure:

Purity: 99%

F F F F 0

OH F F F F F

PFDoA Chemical Name: Perfluorododecanoic acid Molecular Weight: 614 Lot Number: YOlJ

Supplier: Oakwood Products, Inc. Transitions Monitored: 613 + 569,613 + 169 and 613 + 319 Structure:

Purity: 98%

F F F F F O F

OH F F F F F F

PFBS Chemical Name: Perfluorobutanesulfonate Molecular Weight: 338 supplied as the potassium salt (C4F9SO3-K') Lot Number: 2

Supplier: 3M Transitions Monitored: 299 + 80 and 299 + 99 Structure:

Purity: 97.3%

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3M Environmental Laboratory €06-0549 Interim Report # I5


PFHS Chemical Name: Perfluorohexanesulfonate Molecular Weight: 438 supplied as the potassium salt (C~FI~SO~K') Lot Number: NB 120067-69 Purity: 98.6% Supplier: 3M Transitions Monitored: 399 + 80 and 399 + 99 Structure:

PFOS Chemical Name: Perfluorooctanesulfonate Molecular Weight: 538 supplied as the potassium salt (CsF,7S03Xt) Lot Number: 430180/1

Supplier: Fluka Corporation Transitions Monitored: 499 + 80,499 -+ 99 and 499 -+ 130 Structure:

Purity: 101.2%

Page9of37




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 (PFLJnA), 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), Perfluoroundecanoic 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

Jaisirnha Kesari P.E., DEE Weston Solutions, Inc. 1400 Weston Way West Chester, PA 19380 Phone: (610) 701-3761 Fax: (610) 701-7401 j .kesari@westonsolut ions.com

Page 10 of 37


3M Environmental Laboratory €06-0549 Interim Report ##15


SPONSOR REPRESENTATIVE

Robert A. Paschke Manager, 3M Corporate Environmental Programs

St. Paul, MN 55144 Phone: (651) 778-5200

Bldg 42-02-E-27

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 environmental impact of the test substances in the Cottage Grove, Minnesota area.

€06-0549 Interim ReporHl5 Woodbury Soils: October 2007 Page 114 of 156



SAMPLE PROCUREMENT, RECEIPT AND RETENTION

Water, soil, and sediment samples will be received at Exygen from 3M after 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 refrigerated at 2OC-8"C.

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

SAMPLE IDENTIFICATION 0

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 LCMSIMS”

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 free 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 duplicates 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 containershags used for sample collection will be shipped to the sample

Page 13 of 37




e

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 enhance 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. Alternatively, the method blanks could be evaluated statistically to determine outliers 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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3M Environmental Laboratory €06-0549 Interim Report #I5


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 compliance 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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3M Environmental Laboratory €06-0549 Interim Repod #15


Description of the instrumentation used and operating conditions.

All results fiom 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 fmal report are to be archived.

Additions or corrections to the final report shall be in the form of an amendment signed by the Study 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.

0 SAFETY AND HEALTH

Laboratory personnel will practice good sanitation and health habits.

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

AMENDMENTS TO PROTOCOL

All significant changes to the analytical protocol outlined 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 Director 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 OT fi-om the analytical

Page 16 of 37

€06-0549 Interim RepoMlS Woodbury Soils: October 2007 Page 119 of 156



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 instrumental conditions Sample extraction and analysis dates A complete listing of study personnel, 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 chromatogra& will additionally include the concentration (e.g., pg/mL).

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

8 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.

Page 17 of37




RETENTION OF DATA AND ARCHIVING e

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 ~ c r M s / m * *

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3MEm'v#menQ1 - Method

Method of Analysis for the DetumInaUon of Perfluombvlanoic Acid (PFBA), Pertluoropentanoic Acid (PfPeA), Penluomhwenoic Acid (PFHA), Pefluorohepfanoic Acid (WrrpA), PemUOrooclanoic Acid(PFOAj, Porlluomnonmoic Add (PFNA), PotflUO~dCCMOk Acid (PFDA),

Perfluomundecanoic Acld (PFUnA), Pd?uomdodecanoic Add (PFDoA), Pemuombutanarulfonate (PFBS), Pefluorohaxanerulfonate (PFHS), and

Pedluorooctanesuifonrte (PFOS) in Water, Soil and Sediment by LUMS/MS

Method Number: ITS-8-012.0

Adoption Dste: Upon Signlng

Page 20 of 37




1 Scow and ADdication

This muhod is b be used b quitnW Pedluombup!c Acid (PW). Perlluompentandc Acid (PFPeA). PenluorchennoiC Acd (PFM). P u l l t t d q m ~ ~ Add (PFHM)). P e r R w m Add (PFOA). PeAoDmnsnoic Add (PFN4). Psrfiuorodeanok Acid (PFDA), perlluomund~snok Acid (PFURA), P a m u w o d o d d Acd (PFDOA), PwthcbmnesuW (PFBS). PemuwDhsxanasunDaote (PFHS). md M n n a I e (WOS) by H i Padommm Liquid ChwnfoORphy 9 o d lo a tandm MUS S p a h n e t k 0.hdCr (LCMWS) in watu, aoil and redvMnt The mmod is desgned lo oblain a bww Imk d Quanlitslion ( L O O ) ol0.025 ~QM (waler) and 0.20 n& (sol and d i n t ) .

2 Method Summary

Page 2 I of3 7




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€06.0549 Interim Repott#l5 Woodbury Soils: October 2007 Page 125 of 156



...

3.13 Method Blank An aliquot olmmol mawl tul u b s a e d m Ike a Wuatory rmph Wuding ebqosum lo a I glarrursR w.War4, nnhmb. and ~~gamkthatam wed with other laboratwycamplsr. fhs memod blark is usad to debnniu Yted wbdnur u dharinkiermcu enpreent in UH latuatov mnimnmr* tlarswpnlr. or tho sppalatur.

3.12 Sample A -le 6 an aliquot nnrowd f m a b 9 r quanti of nmtefid intended to m p r s n t Ihr origin& wtw maleeria.

3.13 Stock Standard Solution (SSS) A mrrcnlrszsd roldin of a s i n g b ~ piupand in the lsbonlw M h an rrrr/sd refemme compand

3.14 Surrogate A compound rinilar to ha kugat mame) in chemii wrnpanum ud behaviu that io M Mmylhl found in the ssmpk(s). A sumgae mnpound a typicdly a tam m e MI at least w alun mntahing an iwbpkdy labeled s V b s t i M i I used, sunogale(s) am added lo aY rsmples and quaky amtrol ssmples

scbwl blar*r and hH d tho pmpared method blanks). Sunogi4e(S) us added to quanWhiy mmMe the W I ~ an~ElficpI pmcedure hcrudlrg sample collndbn, eatndm. and analysk InduJOn d a sumgate maw 6 n optimal qudw wnlrd massum and 6 NOT mqu'ked

3.15 Working Standard (WS) A rdllion of sews! ar&ies prepared in the labraby b m SSSs and diluted PS needed lo prepare cabdon W a r d s and DYW mind WE sohfUme.


4.1 Health and Safety

me acuie and chmnic tadci)y OC he standards for vli method have not been determined; houvever. eam s h n be veaw as a potonhl heah haurd. me -st should W B ~ I pioves. a w w i and safety g b s c to pRvenl iq~~vl to chem'kala !ha m'@t be present

me bbakxy ir Rsponsibh IW msWning a safe work envimman and a currpnl mmiu of lagl regtdakns repa* the h a d q dtha cherncdf used.m lhs mamod. A reference lib dmteria l saffty dab sheets (MSOS) shouY be m b b l e to aP personnel hutd In Ihu analyses.

4.2 Cautions Ths Matys! mI Ln tmibr wth tha laboratory equrpmenl and paehntial l u w d r in61ing, M nQ Emit& too. the UK of aobntr, pressubed gar Md sooCMI lines, high vonp9e. d vacuum sy%tems. Refer lo the appc0PdOtS SrlUpmOni praedure of opentor manual for add- intomuliDn and caWonr.

5 Interferances

D U M c r ( m d i a d analysis. M w pelsnlial mlarninant scums am reagents and glassware. AI mrPcrialr used in he ana* shall be demonshated lo k free from if!hxfmncer under wnditnnr d ana* by r~MLng M o d blanks.

Page 23 of37




6 Indrumenbtlon, Supplies, and Equipment

0.5 90 10 0.75 2.0 10 90 0.75 5.0 10 90 0.75

€06-0549 Interim RepoM15 Woodbury Soils: October 2007

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Page 127 of 156



Runrvnr - 1 o m i n w The p v b u ~ Infomation is inlended as a guida; mlt~mpte wndi t i and equipment mry h used prarided that data qua4 cb]savcr are met.

6.3 MSlMS System

tranrlbnr 1 of

insreard’anws rigna~.

The prevbur infonnatbn n inlended aa a guide, akernala iwlments and wuipment may be used.


Page 25 of3 7


3M Environmental Laboratory €06-0549 Interim Report # I5


P M U ~ ~ ~ ~ X U - (PW) - 3M PerlluorPodansa*wub (PFOS) - FLkl

The previous infonnaion is intended as a guide. Reagenlr and sttydards fmm ammate f w l o c ~ may be used.

8 Sample Handling

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9.1.3

9.1.4


10 Quality Control

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Exygen Study Number PO002561

Page 28 of 3 7




10.8.1

10.82

Concenhti i Initial Solution Final Concentration of of Initial Wi AliapUQtod Vdums nnsl Solution Calibration Stmdwd (y;L) (W Vdum (mL) (nW-)

5 100 5.0 loo 2.5 100 2.5 10 10 100 1 .o 5 10 100 0.5

2.5 10 100 0.25 1 10 loo 0.1

0.5 10 100 0.05 1 2.5 100 0.025

Store aH sEbrauon standards m 125inL pdVpoWlenn b0ttl.r d 2% lo 8% up to thna ronth. Mamale M l m and canantnlionr d rtndlrds may ba prepinad m W e d .

11 Data Analvsb and Calculations

Total anaiyle found (ng/mL) - Average anawe found In sanpla (ng/mL) Analytsadded (nghL1

oo ROCOWI~ =

V u t h W n g aqualm lo cdal;rle the a w l d analyie found in ppb basnd m dr/ wQhL Ana)ylefound(ppb)dy welpht-Analytelound(ppb)x[lOO%/lolal~ids(%)~

12 Method Perfarmance

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Woodbury Soils: October 2007 €06-0549 Interim ReportMS Page 733 of 756



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€06-0549 Interim Report#75 Woodbuty Soils: October 2007 Page 734 of 756



APPENDIX I1

MNNESOTA POLLUTION CONTROL GUIDANCE DOCUMENTS

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EO6-0549 Interim RepoM15 Woodbury Soils: October 2007 Page 735 of 156



AugwI18.2006

h. William Reagan, Labomlory Manager 3M Envimnmatai Labontory Environmenul. Hcdtb, and Safety Operations

Maplewood. Mh' 55144 3M Cmter. MS 260-SN-17

Re: Cuidmcc fov Pcrflwrocbcmical Analysis in Watn

Dcsr Dr. Reagan:

I have brm asked to provide method pidance (along with QC ncccptrnce criteria) for thc perfluomchemical nnalyris in water. 'llusc criteria should k consided as minimum rtandprdc (the labontoy may use Str ick criteria) and should be met when ULalyLing and repom pamplc results b the Minnesota Pollution Conhal Agency. 'Ibe criteria appcar below. Please review lhoccricai..nd, ifyou have say questionrJcoMnmts/wmti~plcace contact me at (651) 296844445 or via unail at b i l l s m c f o n ~ a r r m n u s .

lnltiil Calibndoq

The Initial Calibrslion Cwcs should contain at lwl six calibration points. Tbc must k @er than or qd to 0.990. Ihe recovey (accuracy) for each point in thc eurvc must bc 75% 10 125% excepl for ths lowcsl point in the e w e which musI be 70% to 130%. me lows1 ulibration point in chc c w c s rMl bc at the d y t ~ report level. If a vmpk wncenhntion c x d h e highest calibration ~ndard 6um rhc Initial Calibration, thc s ~ p l c mwl be diluted into the falibration m g e and reanalyzed. If Ihc instrument salibntion nnrlU arc outside the acceptance critcrin, a number of actions CYI be taken:

for each curve

1) Checkthe kitnunat operating conditions. IrMnmcnt maiatcnana may k q u i d

2) Review the rerpansc at each calibration level to insm chat the pmblan is not associated with one sbndard. If the problem appean to bL issmiatcd with one of the standardr. that standard can be re-injected. If the problem pmuu, re-make the standard and re-mdyz it.

Page 33 of 37

E069549 Interim Repo#75 Woodbury Soils: October 2007 Page 736 of d56



Dr. William R e m August 18,2006 Page 2

3) Tbc last altanativc is to m w the calibdon curve by removing the top or bottom point. If the ulibracion criteria ue now met, the aralydc can p m d . However. thcre we Mlificntionr in nmoving calibration points. If thc top pint is moved, tho need for diluting samples aad rc-anaiyLino will occur at a l o w concentration Icvcl. lfthe low point in the curve is mnmcd. the sensitivity of the &sir ha changed and thus the report level will need focbm~. This may impact sctioa I&.

Continmior CaUbntion

The Initial Cllibrsdon Cwu M verified ever), 12 bun by walyzing a mid-led strradard. The dtift must be within 70% to 130%. If rhc in?&ument calibration rcsdts are outside the acceptance dkrh chock the insoumwf opcdng condidma and/or pcrform instnVncnt mpintCnaoce. Re-arulyzc the calibrdon standud. If the calibdoo critcria am still not met, a new Initial Calibration must bc performed. All samples that were analyzed since the lart passing ulibrMion atandad m w be re-analyzed.

Mahod detection levels (MLKs) and repon levels (RLs) are determined annually or after P mjor ehpngcto the illpcrumeDtconditioni. The MD~~andetennincdpathc p d w definuj in 40 CFR 136. Appendix B. The nprt levels (IUS) should k three thes the MDLS. The I U S NC

also thc lowest Sandard in the alihtion curves. If the lccurscy of thc RL standard doa not mect the 70% to 130% aitcria. new RL gtandards an chosen and rnalyd until the acmJraCy aiteriaam met

Batch OC;

A batcb ig d c h d as up to 20 CnvimnmCntal samples. At a d h u m . each batch mwt conlain 0

method blank, a duplicated d p i s (either a sample duplicate M a duplicated spike), and a Laboratory Conml Sample (US). Every envimxuncdrl umplc must bc spiked.

1) The c~ncentraticn of each target d y i c in the melhod bl8nk mu1 be less than the wocinted port level. Ifthe method blank is conlaminatsd, measures must be taken to eliminate the problem. Affected sunplu must Uun bc regra*sEcd. If chc CcnWaiMtiOo CBII not be Climbted, the r+sults must be qualified to indicate the problcm. All concentration levels fm thc Itfcctcd target analylc wbich uc less thsn (en times thc eoncentration in t h ~ blank should k qualified with a “6” to indiucs l b ~ t tho mpk rrsultr may conUin a bias relaled to the b h k contamination. ConcennatiOnr ofthe .ffedcd analytc which an above an times the blank contamination will not nccd to bc qualified.

Page 34 of 3 7




Dr. William Reagm August IS. 2506 Page 3

2) The Relative Pcrceni D~mnoe (IU’D) bdwoca sample duplicates. mabix spike duplicate firs (MSMSD pairs)$ or LCSlLcSD pain mlut be less than or equal to 20%. Howeva. if the concumation of the q n anal% in the o~lpldsample duplicatc is less chan five tima the repd lcvcl, the differmce ktwcen duplicates is used to mcmure precision n e diffennce musi than k Im rhrn or equal to the report lveel. If the RPD between duplicates is outside the aceepwce c r i t h , comcive action8 must be taka and all assoeined ampler re-enrlyzcb If the criteria are still not mct &r corrective actions, contact the MPCA QA Coordinator for advice.

3) All target andm are to k spiked into th Ma~rix Spike (MS) or LCS. The spiking le-vels should k five to ten times the as. The LCS is made &om KWgCnt-gradC water. The % recoveria of Ihe target dylu h the MS mwt be between 70% and 130% while the %recoveries of I& target wlrtcp in the LCS must k benuca 80% and 120%. If the W ncoverier arc outside the a w p m c e criteria, comt ive ~ctions must be taka and dl associated samples r e - d p d . Ulhc aitcria arc still not met after consCtive actions, contact the MPCA QA Coordinator for advice.

Thanks for your anention on this mslta.

SiDcCrely,

William Scruton, QA Coordiior Performance Management and Quality Section Eovinmmental Analyris and Ourconw Division

E: G a r y ~ ( M P C A ) DCuW Wetznein W C A ) Fred Campbcll (MPCA)

Page 35 of 37




September 1 I , 2006

Dr. William Reagan. Lsboratory Manager 3M Environmental laboratory Environmdal. Health, and Safety Operations 3M Center, MS 260-5N-I 7 Maplcwwd,MN S5l44

Re: Guidancc for Perfluorochemical Analysis in Water

Dear Dr. Reagan:

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

1. Whal report Ievcls to w. 2. How to handle analyses that do not met acceptance criteria, 3. Matrix spikes, and 4. lnitial calibration rqu~ments.

At the meeting. you presented the m e for using 25-nglL (25 ppt) 89 the reporling lwel for each target adyte . The Minnesota Pollulion Control Agcncy(MPCA) will accept this level for the Cottage Gmve Phase 2 FC Assessment. However, we reserve k right to change the reponing level for any future work u FC analytical method development improves.

The MPCA only.wpatr tlac mou ~ c c u n l c data thrt un bo produced for the Phase 2 hrrurment Therefore, we will qu i re Uut only ?crulU that meet 111 QNQC acccpunos lhib will bo rspwtd tD the MPCA. However, we ask lhrt p u submit in mitmg what d o n s Will bc wnduclcd LO p resulIs that mctt the criteria (re-analysis, wextraction and re.anal)air, dilution of the matrix, insrmmenl maintenance, CV.). We will also require that you maintain L e mulU and raw data of all analyses that do not meet QNQC critaia Tor our review if requested at a future dale.

Matrix spiking of cvcry water sample is q u i d for the pmjat. You rup@cd tha all samples be spiked in the field and that p u will be doing this procedure Tor Ihe upcoming sampling round. We will acccpl the data that you genuatc in this fashion. However, the MPCA may plit smplcr at some locations for QMQC purposes and we will M( require that the matrix spikes lor those wnples be held spiked. The MPCA will monitor chc agreement between the splits and, if the rcsultr don’t seem to agee. will rc-cvrluate the mwix spiking procedure.

Page 36 of 37




Dr. William Reagan September I I , 2006 Page 2

The 1rrt issue concerns the ability to delete calibration points h m the middle of h e curve. Before an ~ d f i deletes a data point horn the c w e , hdshc mu1 review the response at each calibration level lo insure that thcprobltm is not associp(ed with one standard. If the probkm appears la be associated with one of the slandardr, that standard should be re-injected. If the problem persists, re-make the standard and r~rnrlfie it. AAcr these effom, a point may be eligible for m o v d fmm the curve. The Agacy will allow the removal of a calibration point from the curve under the following provisions. If a non-lhcar cdibntion model is used in the initial calibration curve. a quadratic (second order) curve will q u i n at last six non-zera standud levels while I polynomial (third order) CUNC will require at leut seven nan-zm standard levels. Care must be taken to insure thrt thm M enough remaining calibration points for the initial calibration curve.

Plcpsc rcviw these criteria and, ifyou have any questionr/comcn~cor~ions, p l u x wnwt me at (6Sl) 296-8445 or via emdl at bi l l . rcnr ron~ .sro fe .~n .w.

Thanks for your attention on these maners.

Sincerely.

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

cc: Gary KNega (WCA) Douglas Weustein (MPCA) F d Campbell (MPC.4)

Page 37 of 37

€06-0549 Interim Repom1 5 Woodbuty Soils: October 2007 Page 140 of 156

3M Environmental Laboratory E064549 Interim Report # l S

Exygen Protocol PO002561 Amendment 13

Study Title

“Analysis of Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid (PFPeA), Perfluorohexanoic Acid (PFHxA), 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 LCMSMS for the 3M Cottage Grove Monitoring Program Phase 2”.

PROTOCOL AMENDMENT NO. 13

Amendment Date: September 26, 2007

Performing Laboratory 3M Environmental, Health, and Safety Operations

3M Environmental Laboratory Building 260-51\1-17

Maplewood, MN 55144-1000

Laboratory Project Identification E06-0549

E064549 Interim Repom15 Woodbury Soils: October 2007

Page 1 of 3

Page 141 of 156


Exygen Protocol PO002561 Amendment 13

This amendment modifies the following portion of protocol:

“Analysis of Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid (PFPeA), Perfluorohexanoic Acid (PFHxA), Perfluoroheptanoic Acid (PFHpA), Perfluorooctanoic Acid

(PFOA), Perfluorononanoic Acid (PFNA), Perfluorodecanoic Acid (PFDA), Perfluoroundecanoic Acid (PFUnA), Perfluorododecanoic Acid (PFDo A), Perfluorobutanesulfonate (PFBS),

Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil, and Sediment Using LCIMSNS for the 3M Cottage Grove Monitoring Program Phase 2”.

PROTOCOL READS: /NTRODUCTlON 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), peffluorodecanoic 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.

AMEND TO READ:

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 target analyte list may be truncated for certain sampling events at the directive of the Study Director.

Reason:

Per request of the study director, this protocol amendment calls for an abbreviated target analyte list for the Woodbury soils collected the week of October 1,2007. See attached GPO for more information.

Page 2 of 3


3M Environmental Laboratory €06-0549 lnterim Report #15

€06-0549 Interim Repo-15 Woodbury Soils: October 2007 Page 143 of 156


a Environmental Health & Safety Operations, Environmental Laboratory

General Project Outline ~

To: Robert Paschke, 3M EHS&Opns;

From:

CC:

Michelle Malinsky, 3M EHS&Opns; Environmental Lab

Kent Lindstrom, 3M EHS&Opns; Environmental Lab

William Reagen, 3M EHS&Opns; Environmental Lab

Casey Howell, QAI, 3M EHS&Opns; Environmental Lab

Jai Kesari, Weston Solutions, Inc.

Date: September 25,2007

Subject: Woodbury Soil Sampling Event: Week of October 1,2007 (GLP MPI Protocol P0002561)

1 General Project Information

GLP Study Director

GLP Sponsor Representative

Contacts

Lab Request Number

I Six Digit Department Number

I Project Schedulemest Dates

Jaisimha Kesari

Weston Solutions. Inc. 1400 Weston Way Westchester, PA 19360

3M Sponsor Representative Robert A. Paschke Manager, 3M Corporate 3M EHS Operations 42-2E-27

[email protected] 651 -778-5200

William K. Reagen 3M EHS Opns, Environmental Laboratory 260-5N-17 651 -733-9739 [email protected]

Principal Analytical Investigator Michelle Malinsky 3M EHS Opns, Environmental Laboratory 260-5N-17 651 -733-9859

[email protected] I I E06-0549

53071 1 I I Sampling to commence the week of October 1,2007



2 Background Information and Project Objective(s)

Beginning the week of October 1,2007, Weston Solutions is planning to collect soil samples from Woodbury, MN. The 3M EHS Operations Laboratory (3M Environmental Lab) will receive and analyze the soil and any accompanying control samples. Analyses will be conducted under the GLP requirements of EPA TSCA Good Laboratory Practice Standards 40 CFR 792. The analytes measured will be perfluorobutanoate (PFBA), petfluorooctanoate (PFOA), perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (PFHS) and petfluorooctanesulfonate (PFOS).

There will be eighteen geoprobe soil borings performed at the main and municipal disposal areas at the Woodbury site. Two soil samples will be collected from each boring for a total of 36 samples. Forty soil sample bottles have been requested. Additionally, three rinseate blanks will be collected from any non- disposable sampling equipment. Once received, all samples will be stored refrigerated until sample preparation for analysis by 3M Environmental Laboratory Methods as defined below. Preparation and analysis of the received soil samples and control samples will be performed in two phases. Sample preparation for both phases will be performed by extraction of sub-samples from each with acetonitri1e:water (80:20) followed with 1 hour of sonication and then centrifugation to clarify extracts. The initial phase (Phase-I) analysis will be performed by isocratic LCIMSIMS method ETS-8-42.0 to assess those soil samples with "high-level" of perfluorocarbon analyte(s) concentration ( 20.250 pglg). Recovery of a surrogate (13C-1 ,2-PFOA) will be used to assess analyte recoveries for Phase-I. The second phase (Phase-2) will be conducted to confirm soil samples with "low-level" perfluorocarbon analyte concentrations (e.g. those with all perfluorocarbon analytes at below 0.25 pg/g level). Phase-2 will be conducted by re-extraction of the low-level samples with inclusion of a duplicate preparation and a separate matrix spike. Matrix spike recovery values will be used to assess the accuracy of phase-2 results.

Phase 1 results that will be reported are those that range from greater than or equal to 0.25 pg/g and Phase 2 results will be reported for those samples with concentrations less than 0.25 pg/g.



PerRuorooctanoic Acid

Perfluorobutanesulfonate

Penluorohexanesulfonate

3 Project Schedule

Sample collection bottles will be prepared by 3M Environmental Laboratory professional services personnel. Weston Solutions personnel will pick the bottles up on Monday October 1,2007 with the first sample collection anticipated for October 2, 2007.

PFOA

PFBS

PFHS

4 Test Parameters

The lowest targeted limit of quantitation (LLOQ), for phase9 as described below, will be nominally 1 .O ng/g (ppb) for all compounds of interest. Table-I lists the target analytes for this sampling event:

Table 1. Target Analytes Target Analyte I Acronym PerRuorobutanoic Acid PFBA

1 Pemuorooctanesulfonate I PFOS I

Per Weston communications, a total of thirty-six (36) primary samples are expected. For each sample, a total of one 250 mL Nalgene @ sample bottle will be provided for primary sample collections. Additionally, four (4) extra bottles will be provided for soil. Three (3) bottles will be provided for instrument rinses “Rinse Blanks” and two (2) more bottles provided as ‘Trip Blanks”. Each Trip blank will contain approximately 25 grams of a soil that is predetermined to be devoid of target analytes (below the reportable LLOQ). The “Rinse Blanks’’ will be expected to be water rinses and will be prepared as similar to soil samples and analyzed against soil matrix calibration curves and repotted as such. A total of 46 sample bottles will be provided. For the collected primary field samples, each sample bottle will receive enough soil to be half-full with soil during collection at the site and lefl with half the bottle volume as headspace. This will allow each to be homogenized briefly by vigorous shaking in the laboratory prior to removal of sub-samples by laboratory personnel during processing for analysis.

As the sampling location descriptions are not available at this time, sample bottles will be identified as assigned by Weston personnel at the site and at the time of sampling and indicated on the sample chain of custody form. 3M will use the sample descriptions provided by Weston Solutions once the samples are received at the 3M Environmental Laboratory.

5 Test Methods

The soils sample analysis will be performed in two phases. The initial phase of analysis (Phase-1) will be performed to differentiate soil samples with endogenous “high-level” fluorocarbon analyte levels. The second phase (Phase-2) will be performed to quantitatively verify soil samples with “low-level’’ perfluorocarbon analyte levels. The 3M Environmental Laboratory Methods ETS-8-42.0 will be followed for Phase-I. The Phase-2 will be conducted by combined Methods ETS-8-12.1 for sample extract preparation and ETS-8-1 .O for analysis of those prepared extracts.

The initial phase of analysis (Phase-1) will be performed to differentiate soil samples with endogenous levels of targeted FC analyte(s) in a range of approximately 0.25 pg/g (250 ppb) to 250 pg/g (250 ppm)

E069549 Interim RepoN15 Woodbury Soils: October 2007 Page 146 of 156


level using 3M Environmental Laboratory Method 8-42.0. All concentrations reported will be based on native soil weight, not dried weight (i.e. will not account for percent moisture in soils). Phase-I analysis will be performed on extracted samples via a rapid screen LClMSlMS analysis. Samples with 250 pglg or greater will be reported as 1250 pglg.

The second phase (Phase-2) will be performed to q u a n t i soil samples with all analytes at, or less than, the range 0.0010 pglg (1 ppb) to 0.25 pglg (250 ppb) and using 3M Environmental Laboratory Method ETS-8-12.1 for sample extraction and LClMSIMS analysis by ETS-8-1 .O. Phase-2 analysis will include a duplicate re-preparation of those samples determined at below 0.25 pglg in phase-I analysis. Additionally a laboratory matrix spike (LMS) of each sample will be prepared by spiking a separate sub-sample with target FC analytes at a nominal concentration to be determined. Results of matrix spikes will be used to evaluate analyte(s) recovery for each sample. Detailed method information will be provided with the final data. All soil weights and sample preparation information will be recorded on appropriate sample preparation forms. All analytical results, including detailed method parameters, chromatograms, and data spreadsheets will be printed and retained with the final archived study file with the final report.

In addition to the sample preparation requirements defined below in phase-1 and phase-2 below, additional matrix spikes and duplicate samples may be prepared as needed to evaluate data accuracy.

Phase 1 Analysis: The 3M method ETS-8-12.1 will be followed for sample preparation. Each sample will be measured to 1 mL volume (approximately 1 to 1.5 gram of soil, depending on soil type) and placed in a 50 mL conical polypropylene centrifuge tube on a balance capable of measuring minimally to 0.01 g. Additionally, every fifth (5") soil sample will be measured out in similar fashion to 1 mL, weighed, and extracted in duplicate and results from the duplicate samples analysis results used to evaluate sample preparation variability (measured as RPD of the duplicative analytical results). Each soil sample will receive 1 .O pg of isotopic bi-labeled 13C2-l ,2-PFOA (C6F1~3CF~3C02-), delivered as 100 UL of a 10 pglmL stock solution prepared in an organic solvent. After surrogate analyte addition, samples will be extracted by addition of 8 mL of an 80:20 acetonitri1e:water solution, thoroughly mixed and sonicated for two hours at room temperature, centrifuged and then aliquoted for LCIMSIMS analysis (per method ETS- 8-12.1). The extraction solution may optionally contain an additional non-fluorinated internal standard (trimethylsilylpropane sulfonate; TMS-PS) at 1 pg/mL in the extraction solvent for additional evaluation of extraction and analysis procedures. In order to facilitate analysis of anticipated high-concentration samples, phase-I analysis will be performed by a rapid and accurate isocratic LClMSlMS analysis with a nominal quantitative range of 0.25 to 250 pglg. Appropriate solvent blank(s) may be injected between each sample to ensure removal of residual instrument contamination (carry over), as needed.

Phase 2 Analysis: Samples measured with all analytes at less than 0.25 pglg in Phase-I will be re- prepared in duplicate for phase-2, same as in phase-1 except that a laboratory matrix spike will additionally be prepared for each sample. The LMS will be prepared by fortifying a separate sub-sample with the targeted FCs at a level to be determined. Surrogate will not be added to the Phase II preparations. Each sample will be extracted with 8 mL of an 80:20 acetonitri1e:water solution, thoroughly mixed, sonicated at room temperature for two hours, centrifuged and then aliquoted for LC/MS/MS analysis (per preparation method described in ETS-8-12.1). The phase-2 LCIMSIMS analysis will be performed according to the LClMSlMS conditions described in method ETS-8-1 .O. Soil matrix calibration standards and blanks will not contain surrogate addition in phase-2 preparations. Detailed method information will be provided with the final data. Samples re-prepared and analyzed in phase-2 will be reported and the original phase 1 results for those samples will not be reported.

Calibration and Calibration Verification. Soil matrix calibration standards will be prepared utilizing approximately 1 mL of a pre-evaluated soil (verified sufficiently clean of target analytes). Soils will be measured consistently for each standard using a disposable 1 mL sampling spoon (resulting in approximately 1 .O to 1.5 g of soil per standard depending on soil density). Hence, each standard will contain a consistent quantity of soil (1 mL), weights will be recorded for each, and then each will be spiked with known quantities of target analytes and surrogate analyte and then solvent extracted per method ETS-8-12.1. Calibration standard sets with a quantitative range of 0.010 to 250 pg per standard



(nominally 0.0010 to 250 pg/g for a 1 .O gram standard soil) will be prepared. A set of calibration standards will include 12-1 5 prepared soil matrix calibration standards (nominal soil concentration range 0.001 0 to 250 ng/g), triplicate prepared soil blanks (soil plus surrogate, no target analytes) and minimally a triplicate preparation of soil double blanks (no surrogate and no target analytes). The standards that range from 0.25 to 250 pg (0.25, 0.50, 1.0,2.5,5.0, 10,25, 100 and 250) will be used for phase-I analysis. The 0.0010 to 0.25 pg standards (0.0010, 0.0025, 0.0050, 0.010, 0.025,0.10, and 0.25) will be used for phase-2 analysis. A mid-level calibration standard will be re-injected every 15 unknown samples in a run and used as continuing calibration verification (CCV).

Quality ControllAcceptance Criteria: The surrogate ('3C-1 ,2-PFOA) analyte recovery (fortified at 1 .O pgkample) will be used to evaluate recovery of perfluorinated target anaiytes in Phase-I . Samples with surrogate recoveries outside of 100% +/- 30% but within 100% +/- 60% are reportable. Matrix spike recoveries for the added known quantities of target analytes will be used to evaluate recovery of native analyte from soil samples in phase-2. Samples with matrix spike recoveries outside of 100% +/- 30% but within 100% +/- 60% are reportable. Results are flagged if outside of 100% +/- 30% as having an expanded uncertainty of 100% +I- 60%. Samples with spike recoveries outside of 100% +/- 60% will be reported as "NR (not reported due to QC failure).

Percent recovery of back-calculated standards should be 100 5 30 % (2 35% at LLOQ) of theoretical and any standards included in constructed calibration curves that are outside of those criteria will be noted in the final report. The lowest calibration standard may be dropped from curves in the event that the analyte response is not twice the analyte response in appropriate blanks. In that event, LLOQs will be revised to the next highest standard that meets that criterion of being twice the response of the blank. Calibration standards within a range should not be excluded without proper documentation of a valid reason for doing so (e.g. known preparation errors or consistent failing of a standard that is suggestive of an isolated problem). All calibration curves should contain at least six calibration points. Regression may be linear or quadratic, non-zero origin, and may be either non-weighted or weighted l / x or 1/xA2, as needed.

CCV results should be within 100 2 30% of theoretical for acceptance of the results. Partial acceptance of runs is allowed if data sets are flanked by passing CCVs.

All data that are reported and that give spike recovery or surrogate recovery data that show accuracy outside of 100 +30%, or flanked by CCV with results outside of 100 5 30%, will be flagged andlor footnoted in the final report data tables

6 Reporting Requirements

The report will contain the results for each sample and any corresponding QC samples. Phase 1 results that will be reported are those that range from greater than or equal to 0.25 pg/g and Phase 2 results will be reported for those samples with concentrations less than 0.25 pg/g.

7 Attachments ~~~

None. GLP protocol is available upon request. Not attached due to file size limitations.

8 E-mail Communications


3M Environmental Laboratory €06-0549 Interim Report # I 5

Kent R. To LindstromlUS-Cotporate/3M/U cc S

bcc 09/20/2007 02:43 PM Subject

.Michelle Malinsky/US-Corporate/3M/US@3M-C01porate

William K. Reagen/US-Corporate/3M/US@3M-Corporate

Fw: Woodbury Main / Municipal Disposal Area Sampling - Bottle Request

Michelle,

Weston has provided an exact sample bottle count request for the Woodbury soil samples that are to be collected in the first week of October. They are requesting that the bottle order be ready for pick-up on Monday, Oct 1, 2007. FYI, I separately responded to Charlie indicating that this would not be a problem.

Kent R. Lindstrom Senior Research Chemist 3M Environmental, Health, and Safety Operations Building 260-5N-17 Maplewood, MN 55144-1000

Tel: 651- 733-9882

[email protected]

CONFIDENTIAL

FAX: 651-733-4687

This communication is intended only for the addressee(s) named above. It contains confidential information. Unauthorized use, disclosure, dissemination or copying of this communication, or any part thereof, is strictly prohibited. If the reader of this message is not the intended recipient please notify us immediately by telephone or electronic mail and delete or destroy this message and all copies thereof, including attachments.

----- Forwarded by Kent R. LindstromlUS-Corporatel3MIUS on 09/20/2007 02:40 PM ----- "Young, Charles T." <Charles.Young@WestonSol To utions.com 09/20/2007 02:25 PM

cc

Subject

"Kent Lindstrom" <[email protected]> "Witmer, Gary" <[email protected]> "Kesari, Jai" <[email protected]> Woodbury Main / Municipal Disposal Area Sampling - Bottle Request

Kent:

The Woodbury main disposal area and municipal waste disposal area sampling will be performed on the week of October 1, 2007 with the first of the samples to be collected on Tuesday Oct 2. Please add a few bottles of milliQ water for use in equipment rinseate sampling. The sample count is described below in Gary Witmer's request.

Can this bottle order be prepared for pickup on Monday Oct I?

Thanks, Charlie

E060549 Interim RepoM15 Woodbury Soils: October 2007 Page 149 of 156


From: Witmer, Gary

Sent: Thursday, Septembw 20,2007 3 :08 PM

To: Young, Charles T.

Cc: Kesari, Jai

Subjed: Woodbury Sample Bottle Request

Charlie, please forward to Kent.

There will be 18 Geoprobe soil borings performed at the main and municipal disposal areas at the Woodbury site. Two soil samples will be collected from each boring for a total of 36 samples. Additionally 3 rinseate blanks will be collected from any non-disposable sampling equipment.

Analyses for both soil and water samples will be for 5 FC parameters: PFOS, PFOA, PFBA, PFHS and PFBS.

The bottle order should consist of 40 soil sample bottles and 3 rinseate sample bottles.

Gary Witmer Project Manager Weston Solutions, Inc. 1400 Weston Way West Chester, PA 19380 610-701-3141

CONFIDENTIALITY: This e-mail and attachments may contain information which is confidential and proprietary. Disclosure or use of any such information without the written permission of Weston Solutions, Inc. is strictly prohibited. If you received this e-mail in error, please notify the sender by return e-mail and delete this e-mail from your system. Thank You.

E064549 Interim Repom15 Woodbury Soils: October 2007 Page 150 of 156

3M Environmental Laboratory E06-0549 Interim Report #15

William K. TO .Michelle Malinsky/US-Corporate/3M/US@3M-Corporate ReagenNSCorporate/3M/US 09/20/2007 10:26 AM

cc

bcc Subject Fw: Woodbury soil sampling - Week of Oct 1,2007

History: This message has been replied lo and forwarded. I

William Reagen Laboratory Manager 3M Environmental Laboratory Environmental, Health, and Safety Operations 3M Center, MS 260-51\1-17, Maplewood MN, 55144

[email protected] 651 -733-9739

CONFIDENTIAL This communication is intended only for the addressee@) named above. It contains confidential information. Unauthorized use, disclosure, dissemination or copying of this communication, or any part thereof, is strictly prohibited. If the reader of this message is not the intended recipient please notify us immediately by telephone or electronic mail and delete or destroy this message and all copies thereof, including attachments. ----- Fotwarded by William K. ReagenlUS-Corporatel3MIUS on 09/20/2007 10:26 AM -----

Kent R. LindstromlUSCorporatel3M/U To William K. Reagen/US-Corporate/3M/US@3M-Corporate S 09/20/2007 0954 AM

cc

Subject Woodbury soil sampling -Week of Oct 1,2007

Bill,

Jai Kesari called with a "heads up" that there will be a Woodbury soil sampling event during the week of Oct 1, 2007. He indicated that this was mentioned several weeks ago in a conference call, but due to the call cancellation today, he wanted to confirm that this was to take place. This will be in the vicinity of the sample site where the 1994 work was done.

This will be GLP. The target list is PFBS, PFHS, PFOS, PFBA, and PFOA. (If this list is different than previous lists, we will need to review previous amendments to determine if the target analyte list change needs to be incorporated into the protocol or is allowed based on previous wording in another amendment.) Bob Paschke is the Sponsor, Jai Kesari is the Study Director. There will be approx 40 to 45 samples. Weston will notify us of the exact number when the sampling date gets a bit closer. FYI.

Kent R. Lindstrom Senior Research Chemist 3M Environmental, Health, and Safety Operations Building 260-5N-17 Maplewood, MN 55144-1000

Tel: 651- 733-9882



FAX: 651-733-4687 [email protected]

CONFIDENTIAL

This communication is intended only for the addressee@) named above. It contains confidential information. Unauthorized use, disclosure, dissemination or copying of this communication, or any part thereof, is strictly prohibited. If the reader of this message is not the intended recipient please notify us immediately by telephone or electronic mail and delete or destroy this message and all copies thereof, including attachments.



~~~ ~ ~

ATTACHMENT D: METHOD DEVIATIGS



E064549 Interim Report #15 Woodbury Soils: October 2007 Page 154 of I56


EO64549 Interim Report #15 Woodbury Soils: October 2007 Page 155 of 756

3M Confidential

e * 52 g s q o

RECORD OF NONCONFORMANCE / DEVIATION

4p:

n ~ 0 0 1 1 o t s - 4 ~ t o ~ 2112~ sw 116 ~ M B 8016 m mi e780 100 a m ma tm go+z 80e iwz 48fr1 5175 $22

7e manmsa(Y)uDi m m sir139 r~zs 6sfs.1 mi7 ss.5 IWZ w o w 859 to8427 ism ix tiw? t o m s 01.2 6 2 ~ ~ 972

Several of the CCV injectiorw for aO71016a ended up being above the tfppef liml ofqUantitati6n (>ULOQ). Raw area counts of the CCV inj&bn wefe compared to the raw area counts of the same standard when inwed during the initial calibration wwe. CCV area counts, when compared to the initial calibration cum, werewdhin 25% IndiCatSng that instrument response was not drifting signirjcantiy during the analybcal run. Therefore, atl data. will be reported even if not bracketed by method compliant CCVs.

At1 CCVs in analytical bat& S071019a (low level cuwes) met method acceptanca &Ma except injedion #34 for PFBA. All samples will be reanatyzed for PFBA in Phase I1 for a lower FDO. Additmnally, raw area count comparison for PFBA in@ction#34 was within 3 1 of the initial curve’s area counts.

For a n a l y t i i batch a071019b (high level curves). eli WOA sample results reported from this bakh met method accaptsnw criteria The first CNO bracketing CCVs for PFHS, WOS and the surrogate (lnjedion numbers 97,111) were above the initial caiibrafion range. However, area counts were within *5% when compared to the initial curve injections. Additionally. the final bracketing CCV met method acceptance meria.

h 0 R

.E

1 h

EfS-4-08.4 Print Date: 1112MOO7; Print Tim 11:12:23 AM

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