Document 87JM3bdNX6ORw2o6b39RBXXK
3M Environmental Laboratory P0003268; Interim Report#2
Analytical Report
Analysis of PFBS, PFHS, and PFOS from 3M Decatur Offsite Sediment Samples
Interim Report #2 MPI GLP Protocol Number P0003268
Data Requirement
40 CFR Part 792
Author
Michelle D. M alinsky, Ph.D.
Phase Completion Date
Date of signing
Performing Laboratory
3M Environmental Health and Safety Operations Environmental Laboratory
3M Center, Bldg 260-05-N-17 Maplewood, MN 55144
Project Identification
GLP07-02-01
Total Number of Pages 209
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 1 of 209
3M Environmental Laboratory P0003268; Interim ReporW2
This page has been reserved for specific country requirements.
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 2 of 209
3M Environmental Laboratory P0003268; Interim Report#2
GLP Compliance Statement
Project Title: Analysis of PFBS, PFHS, and PFOS from 3M Decatur Offsite Sediment Samples Project Identification Number: GLP07-02-01 MPI Protocol Number P0003728, Interim Report #2 This analytical phase was conducted in compliance with Toxic Substances Control Act (TSCA) Good Laboratory Practice (GLP) Standards, 40 CFR 792, with the exceptions listed below:
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 3 of 209
3M Environmental Laboratory P0003268; Interim Report#2
Quality Assurance Statement
Study Title: Analysis of PFBS, PFHS, and PFOS from 3M Decatur Offsite Sediment Samples Study Identification Number: GLP07-02-01; 3M Protocol Number GLP07-02 (MPI Protocol Number P0003268 Interim Report #2) 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.
Inspection Dates
10/19/2007 12/19-12/22/2007; 12/27-12/29/2007;
1/2 -1/4/2008; 1/9-1/11/2008
Phase
In-Phase Data & Report Audit
Date Reported To
Principal Analytical Investigator
Study
Study
Director's
Director
Management__________
11/1/2007
1/23/2008
1/23/2008
1/1 1/2008
1/23/2008
1/23/2008
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 4 of 209
3M Environmental Laboratory P0003268; Interim Report#!
Table of Contents
GLP Compliance Statement.................................................................................................................. 3 Quality Assurance Statement................................................................................................................4 Table of Contents.................................................................................................................................. 5 List of Tables.......................................................................................................................................... 6 Study Information.................................................................................................................................. 7 Summary and Introduction.....................................................................................................................8 Test System/Samples..........................................................................................................................15 Reference Substances.........................................................................................................................16 Method Summaries..............................................................................................................................17
Preparatory and Analytical Methods.............................................................................................. 17 Analytical Results.................................................................................................................................18
Calibration...................................................................................................................................... 18 Limit of Quantitation (LOQ)............................................................................................................ 19 Blanks............................................................................................................................................19 Continuing Calibration....................................................................................................................21 Lab Control Spikes (LCSs)............................................................................................................ 22 Sample Duplicates........................................................................................................................ 25 Dry Weight Determination............................................................................................................. 25 Laboratory Matrix Spikes (LMSs)...................................................................................................25 Data Summary and Discussion........................................................................................................... 27 Statistical Methods and Calculations................................................................................................... 96 Accuracy and Precision Equations................................................................................................96 Determination of Analytical Method Uncertainty............................................................................ 96 Statement of Conclusion......................................................................................................................97
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 5 of 209
3M Environmental Laboratory P0003268; Interim Report#2
References.......................................................................................................................................... 97 List of Attachments.............................................................................................................................. 97 Signatures............................................................................................................................................ 98
List of Tables
Table 1. Sample Results Summary.......................................................................................................9 Table 2. Sample Description Key Code.............................................................................................. 16 Table 3. Study Reference Substances................................................................................................ 16 Table 4. Instrument Parameters.... ..................................................................................................... 17 Table 5. Liquid Chromatography Program.......................................................................................... 18 Table 6. Mass Transitions................................................................................................................... 18 Table 7. Method Blank Results for Extraction Day 9/25/2007........................................................19 Table 8. Method Blank Results for Extraction Day 10/11/2007......................................................20 Table 9. Method Blank Results for Extraction Day 10/19/2007..................................................... 20 Table 10. Method Blank Results for Extraction Day 10/22/2007........................................................ 21 Table 11. Non-compliant CCVs.......................................................................................................... 22 Table 12. Lab Control Spike Results...................................................................................................23 Table 13. Laboratory Matrix Spike Concentrations............................................................................. 26 Table 14. PFBS Sample Results with QC...........................................................................................28 Table 15. PFHS Sample Results with QC...........................................................................................51 Table 16. PFOS Sample Results and QC...........................................................................................74 Table 17. Analytical Method Uncertainties.......................................................................................... 96
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 6 of 209
Study Information
3M Environmental Laboratory P0003268; Interim Report#2
Sponsor
3M Company
Sponsor Representative
Michael Santoro Director Regulatory Affairs 3M Bldg. 236-01-B10 Maplewood, MN 55144 Telephone No. (651) 733-6374 FAX No. (651)733-1958
Study Director
Jaisimha Kesari, P.E., DEE Weston Solutions, Inc. 1400 Weston Way West Chester, PA 19380
Study Location
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., 3M Environmental Laboratory Manager, Technical Reviewer Michelle D. Malinsky, Ph.D., Principal Analytical Investigator Cliffton B. Jacoby, Ph.D., 3M Environmental Laboratory Management Zhuojing Liu, Analyst Vallabha Tantry, Analyst
Study Dates
Interim Experimental Initiation: September 11,2007
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. All samples (specimens) will be retained and stored according to current 3M Environmental Laboratory standard operating procedures.
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 7 of 209
3M Environmental Laboratory P0003268; Interim Report#2
Summary and Introduction
The 3M Environmental Laboratory extracted and analyzed sediment samples collected offsite from the 3M Decatur, AL facility by Weston Solutions personnel on August 28-29, 2007. Sample were submitted for analysis under 3M Environmental Laboratory Project Number GLP07-02-01. The GLP protocol number is P0003268: "Analysis of Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil, Sediment, Fish, and Clams Using LC/MS/MS for the 3M Decatur Monitoring Program". According to the General Project Outline written for this specific sampling event (located after Protocol Amendment #1 in Attachment C), both surface water and sediment samples were to be collected. However, the surface water samples were not collected as the designated sampling locations did not have any standing water to sample. A GPO deviation has been written and can be found in Attachment D. The water trip blank samples prepared for the sampling event were returned to the laboratory, but were not analyzed. (These samples were logged as GLP07-02-01-033 through GLP07-02-01-036.)
The sediment samples were analyzed for PFBS, PFHS, and PFOS using method 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". The experimental start date was September 11,2007 (the date samples were first extracted) and the experimental completion date was October 31, 2007. Initially, a single aliquot of each sample was extracted and analyzed to quickly approximate the levels of the target analytes. The purpose of the initial screening analysis was twofold: (1) to determine if a clean sediment sample (target analytes less than the lower limit of quantitation) could be used to construct extracted calibration curves and other quality control samples and (2) to estimate the appropriate laboratory matrix spike levels needed for each sample for accurate quantitation. Results of the screening analysis were not reported nor audited. During the screening phase, sample GLP07-02-01-048 was determined to be one of the sediment samples with the lowest levels of target analytes present. Therefore, this sample was used to prepare the extracted calibration curve and laboratory QC samples (method blanks and laboratory control samples) during the official quantitative analysis. Multiple method blanks of this sample were prepared and analyzed each day samples were extracted and confirmed that the concentration of the target analytes of this sediment was less than the approximate LOQ. All other samples were then re-extracted in duplicate with a low and high level laboratory matrix spike to determine sample accuracy. The dry weight (%solids) was determined in duplicate for each sediment sample. Sample results were corrected for the average dry weight determination. Samples producing lab matrix spike recoveries exceeding 10030% or bracketed by a non-compliant continuing calibration verification standard have been flagged with an expanded sample uncertainty.
Table 1 below summarizes the sample results.
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 8 of 209
Table 1. Sample Results Summary.
Sample Description GLP07-01-01-001 GLP07-01-01-001 Duplicate
GLP07-02-01-002 GLP07-02-01 -002 Duplicate
GLP07-02-01-003 GLP07-02-01 -003 Duplicate
GLP07-02-01-004 GLP07-02-01-004 Duplicate
GLP07-02-01-005 GLP07-02-01-005 Duplicate
GLP07-01-01-006 GLP07-01-01-006 Duplicate
GLP07-01-01-007 GLP07-01-01-007 Duplicate
Sample Comment DAL SD EP01 0 0010 DAL SD EP01 0 0010 Average %RPD Average %Solids DAL SDEP02 0 0010 DAL SD EP02 0 0010 Average %RPD Average %Solids DAL SD EP02 0 0030 DAL SD EP02 0 0030 Average %RPD Average %Sotids DAL SD EP02 0 0045 DAL SD EP02 0 0045 Average %RPD Average %Solids DAL SD EP03 0 0010 DAL SD EP03 0 0010 Average %RPD Average %Solids DAL SD EP03 0 0030 DAL SD EP03 0 0030 Average %RPD Average %Solids DAL SD EP03 0 0045 DAL SD EP03 0 0045 Average %RPD Average %Solids
3M Environmental Laboratory P0003268; Interim Report#2
Mass Extracted
(9) 0.9580 0.9951
84.0 1.0685 1.0194
86.9 1.0315 0.9915
85.4 0.9039 0.9822
84.3 1.0507 1.0281
90.0 0.9672 1.0847
84.0 1.0897 0.9493
86.2
,VPFBS
mPFHS
mPFOS
Cone, ng/g (dry weight)
0.964 0.270 0.617 m110
Cone, ng/g (dry weighty
0.428 0.278 0.353 42
Cone, ng/g (dry weighty
238 193 215 21
0.671 0.654 0.663
2.6
6.84 6.96 6.90 1.8
537 537 537 0.1
2.51 3.49 3.00 33
17.9 18.4 18.2 2.9
203 167 185 20
3.58 3.32 3.45 7.4
(3,2 1 .3 (3)22.6 22.0
5.9
125 195 f60 44
0.745 0.734 0.739
1.5
9.99 9.77 9.88 2.2
388 381 384 1.8
0.782 0.585 0.683
29
4.31 3.28 3.80 27
155 95.7 125 47
0.499 0.379 0.439
27
3.18 2.74 2.96
15
83.9 66.7 75.3 23
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 9 o f209
Sample Description GLP07-02-01-008 GLP07-02-01-008 Dup
GLP07-02-01-009 GLP07-02-01-009 Duplicate
GLP07-02-01-010 GLP07-02-01-010 Dup
GLP07-02-01-011 GLP07-02-01-011 Dup
GLP07-02-01-012 GLP07-02-01-012 Duplicate
GLP07-02-01-013 GLP07-02-01-013 Duplicate
GLP07-02-01-014 GLP07-02-01-014 Dup
Sample Comment DAL SDEP04 0 0010 DAL SD EP04 0 0010 Average %RPD Average %Solids DAL SD EP04 0 0030 DAL SD EP04 0 0030 Average %RPD Average %Solids DAL SD EP05 0 0010 DAL SD EP05 0 0010 Average %RPD Average %Solids DAL SD EP05 DB 0010 D ALSDEP05 DB 0010 Average %RPD Average %Solids DAL SD EP05 0 0030 DAL SD EP05 0 0030 Average %RPD Average %Solids DAL SDEP06 0 0010 DAL SDEP06 0 0010 Average %RPD Average %Soiids DAL SD EP07 0 0010 DAL SD EP07 0 0010 Average %RPD Average %Solids
3M Environmental Laboratory P0003268; Interim Report#2
Mass Extracted
(9) 1.0529 0.9872
84.9 0.9885 1.0153
85.1 0.9200 1.0568
82.0 1.0015 1.0151
82.0 0.9960 0.9317
83.6 0.9909 0.9638
90.5 1.0017 1.0017
82.0
(VP F B $
Cone, ng/g (dry weight)
3.03 2.94 2.99 3.1
2.25 2.04 2.14
10
1.61 1.65 1.63 2.5
1.33 1.63 1.48 20
1.43 1.43 1.43 0.27
1.14 1.29 1.22
12
3.12 3.17 3.14 1.6
(1>PFHS
Cone, ng/g (dry weight)
33.2 32.4 32.8 2.3
12.8 12.5 12.7 2.7
15.5 16.7 16.1 7.6
14.0 15.6 14.8 11
8.70 9.25 8.97 6.1
8.77 11.2 9.98 24
(3,26.0 <3)25.7 m25.9
1.1
<1>PFOS
Cone, ng/g (dry weight)
(3)1500 (3)1450 m1480
3.6
(3)477 m454
10
1120 1210 1170 7.3
1020 1150 1090
12
235 268 252 13
387 507 447 27
<3)1020 <3>1041 p>1030
1.9
CM CO
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 10 of 209
Sample Description GLP07-02-01-015 GLP07-02-01-015 Duplicate
GLP07-02-01-016 GLP07-02-01-016 Duplicate
GLP07-02-01-017 GLP07-02-01-017 Duplicate
GLP07-02-01-018 GLP07-02-01-018 Dup
GLP07-02-01-019 GLP07-02-01-019 Dup
GLP07-02-01-020 GLP07-02-01-020 Dup
GLP07-02-01-021 GLP07-02-01-021 Dup
Sample Comment DAL SD EP07 0 0030 DAL SD EP07 0 0030 Average %RPD Average %Solids DAL SD EP07 0 0045 DAL SD EP07 0 0045 Average %RPD Average %Solids DAL SD EP07 DB 0045 DAL SD EP07 DB 0045 Average %RPD Average %Solids DAL SD EP08 0 0010 DAL SD EP08 0 0010 Average %RPD Average %Solids DAL SDEP09 0 0010 DAL SD EP09 0 0010 Average %RPD YoSolids DAL SD EP09 0 0030 DAL SD EP09 0 0030 Average %RPD YoSolids DAL SD EP09 0 0045 DAL SD EP09 0 0045 Average YoRPD Average YoSolids
3M Environmental Laboratory P0003268; Interim Report#2
Mass Extracted
(9) 1.0663 1.0606
85.3 1.0546 1.0472
87.2 1.0298 0.9724
85.2 0.9513 0.9857
85.0 1.0559 1.0364
83.9 0.9214 1.0577
84.3 1.0314 0.9683
83.3
mPFBS
Cone, ng/g (dry weight)
1.35 1.32 1.34 2.8
0.887 1.05 0.969
17
1.04 0.995 1.02
4.4
1.08 1.15 1.11 6.1
1.51 1.73 1.62
14
0.889 1.14 1.01 25
0.892 0.947 0.920
6.0
(VPFHS
Cone, ng/g (dry weight)
10.9 9.55 10.2
13
7.92 9.28 8.60
16
7.49 7.40 7.45 1.2
7.57 7.49 7.53 1.1
17.2 14.6 15.9 16
7.77 9.15 8.46
16
<3>5.95 (3)7.67 6.81
25
,vPFOS
Cone, ng/g (dry weight)
(4)355 (` >273 <4>314
26
(3>259 (3)300 P'279
14
208 194 201 6.9
856 880 868 2.8
(3,681 <3)659 ^670
3.3
172 202 187 16
<3)65.7 (3)121 P'93.3 59
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 11 of 209
Sample Description GLP07-02-01-022 GLP07-02-01-022 Dup
GLP07-02-01-023 GLP07-02-01-023 Dup
GLP07-02-01 -024 GLP07-02-01-024 Dup
GLP07-02-01-025 GLP07-02-01-025 Dup
GLP07-02-01-026 GLP07-02-01-026 Dup
GLP07-02-01-027 GLP07-02-01-027 Dup
GLP07-02-01-028 GLP07-02-01-028 Dup
Sample Comment DAL SD EP10 0 0010 DAL SD EP10 0 0010 Average %RPD Average %Solids DAL SD EP10 0 0030 DAL SD EP10 0 0030 Average %RPD Average %Solids DAL SDEP10 0 0045 DAL SDEP10 0 0045 Average %RPD Average %Solids DALSDEP11 0 0010 DAL SD EP11 0 0010 Average %RPD Average %Solids DAL SD EP11 0 0030 DALSDEP11 0 0030 Average %RPD Average %Solids DAL SD EP11 DB 0030 DAL SD EP11 DB 0030 Average %RPD Average %Soiids DAL SD EP12 0 0010 DAL SD EP12 0 0010 Average %RPD Average %Solids
3M Environmental Laboratory P0003268; Interim Reportt2
Mass Extracted
(g) 0.9243 1.0539
84.7 0.9282 1.0811
82.8 1.0419 0.9957
85.1 0.9626 0.9955
92.0 1.0064 0.9796
85.9 0.9617 0.9785
85.2 1.0701 0.9479
88.1
mPFBS
mPFHS
lvPFOS
Cone, ng/g (dry weight)
1.29 1.28 1.28 0.47
Cone, ng/g (dry weight)
16.5 17.3 16.9 5.0
Cone, ng/g (dry weight)
<3)960 (3)977
968 1.8
1.12 1.11 1.12 1.4
7.00 7.18 7.09 2.5
171 154 162 10
1.30 1.19 1.24 8.8
8.08 7.63 7.86 5.8
172 106 139 48
5.41 5.37 5.39 0.72
25.9 26.5 26.2 2.06
744 729 736 2.0
1.18 1.24 1.21 5.0
7.80 12.9 10.4 49
150 252 201 m51
1.10 1.24 1.17 11
11.3 12.4 11.9
9
238 264 251 10
0.484 0.487 0.485 0.61
4.67 4.62 4.64 1.1
w347 (4)317 m332
9.0
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 12 of 209
Sample Description GLP07-02-01 -029 GLP07-02-01-029 Dup
GLP07-02-01-030 GLP07-02-01-030 Dup
GLP07-02-01-031 GLP07-02-01-031 Dup
GLP07-02-01-032 GLP07-02-01 -032 Dup
Sample Comment DAL SDEP13 0 0010 DAL SD EP13 0 0010 Average %RPD Average %Solids DAL SD EP13 0 0030 DAL SD EP13 0 0030 Average %RPD Average %Solids DAL SDEP14 0 0010 DAL SD EP14 0 0010 Average %RPD Average %Solids D ALSDEP14DB 0010 DALSDEP14DB 0010 Average %RPD Average %Solids
GLP07-02-01 -037
DAL SD DU01 RB 0010
GLP07-02-01-038 GLP07-02-01-038 Dup
GLP07-01-01-039 GLP07-01-01-039 Duplicate
GLP07-01-01-040 GLP07-01-01-040 Duplicate
DAL SD DU01 0 0010 DAL SD DU01 0 0010 Average %RPD Average %Solids DAL SD DU02 0 0010 DAL SDDU02 0 0010 Average %RPD Average %Solids DAL SD DU03 0 0010 DAL SD DU03 0 0010 Average %RPD Average %Solids
3M Environmental Laboratory P0003268; Interim Repor
Mass Extracted
(9) 1.0167 0.9516
92.0 1.0329 0.9524
85.2 0.9305 1.0403
91.6 0.9524 0.9351
91.0
WPFBS
<VPFHS
n PFOS
Cone, ng/g (dry weight)
2.90 2.92 2.91 0.72
Cone, ng/g (dry weight)
15.8 16.2
16.0 2.9
Cone, ng/g (dry weight)
744 737 741 1.0
1.35 1.29 1.32 4.8
13.0 12.6 12.8 3.0
351 340 345 3.1
2.51 2.76 2.64 9.7
32.9 34.1 33.5 3.7
<3)948 (3)966 p>957
1.8
2.49 2.33 2.41 6.7
31.6 30.6 31.1 3.3
913 886 900 3.0
1.0294
(s)<0.196
(5)<0.213
(5)<0.380
0.9486 1.0004
90.3 0.9853 0.9781
89.3 0.9563 1.0574
90.2
2.10 2.39 2.25
13
0.277 0.264 0.270
4.7
<0.234 <0.211 <0.223
NA
14.1 16.6 15.3 16
2.96 3.02 2.99 2.3
1.32 1.25 1.28 5.2
CO CO
S
713 824 769 14
<3)444 P)441
1.4
286 248 267 14
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 13 o f 209
Sample Description GLP07-02-01-041 GLP07-02-01-041 Dup
GLP07-02-01-042 GLP07-02-01-042 Dup
Sample Comment DAL SD DU04 0 0010 DAL SDDU04 0 0010 Average %RPD Average %Solids DAL SD DU05 0 0010 DAL SD DU05 0 0010 Average %RPD Average %Solids
GLP07-02-01-043
DAL SD DU05 RB 0010
GLP07-01 -01-044 GLP07-01-01-044 Duplicate
GLP07-01-01-045 GLP07-01 -01 -045 Duplicate
GLP07-01-01-046 GLP07-01-01-046 Duplicate
GLP07-02-01-047 GLP07-02-01-047 Dup
DAL SD DS01 0 0010 DAL SD DS01 0 0010 Average %RPD Average %Sollds DAL SD DS01 0 0010 DAL SD DS01 0 0010 Average %RPD Average %Solids DAL SD DS02 0 0010 DAL SDDS02 0 0010 Average %RPD Average %Solids DAL SD DS02 0 0030 DAL SD DS02 0 0030 Average %RPD Average %Solids
GLP07-02-01-048
DALSDWP01 0 0010
3M Environmental Laboratory P0003268; Interim Reportt2
Mass Extracted
(9) 0.9389 0.9654
90.5 0.9372 0.9475
85.6
WPFBS
(1>PFHS
mPFOS
Cone, ng/g (dry weight)
3.69 3.82
3.75 3.4
Cone, ng/g (dry weight)
16.0 16.5 16.2 2.9
Cone, ng/g (dry weight)
696 70S 702 1.7
1.09 1.01 1.05 7.7
(6,10.3 (6)9.78 m10.0
4.9
(6>770 (6)748 <*>759
2.9
1.0375
<5)<0.195
(5)<0.211
(5,<0.378
0.9684 0.9392
92.0 1.0345 1.0823
91.3 0.9512 0.9792
92.8 0.9725 0.9180
91.4
<0.227 <0.234 <0.230
NA
0.300 0.302 0.301 0.71
<0.228 <0.222 <0.225
NA
0.389 0.386 0.387 0.69
2.87 2.61 2.74 9.6
3.22 2.91 3.06
10
1.64 1.47 1.55 11
(6)4.77 (6)4.74 m4.75 0.66
639 615 627 3.8
304 242 273 23
616 616 616 0.0
<6)552 (6)558 m555
1.1
NA
(7,<l o q
(7)<l o q
(7)<l o q
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 14 o f 209
3M Environmental Laboratory P0003268; Interim Report#2
Sample Description GLP07-01-01-049 GLP07-01-01-049 Duplicate
Sample Comment DAL SD WP02 0 0010 DAL SD WP02 0 0010 Average %RPD Average %Solids
Mass Extracted
(9) 1.0349 0.9924
84.7
mPFBS
mPFHS
mPFOS
Cone, ng/g (dry weight)
<0.230 <0.240 <0.235
NA
Cone, ng/g (dry weight)
<0.254 <0.265 <0.259
NA
Cone, ng/g (dry weight)
<0.223 <0.233 <0.228
NA
(1) Unless otherwise specified, the recovery of associated laboratory matrix spikes was within 10030% indicating that method was appropriate for the given matrix. Sample results are considered accurate to within the overall analytical method uncertainty 10020% (PFBS), 10021% (PFHS), and 10030% (PFOS). See Determination o f Analytical Method Uncertainty section for more information. Sample results are reported to three significant figures and %RPD to two significant figures. Additional significant figures were used to calculate the average, %RPD, and %recovery. Values in the raw data may vary slightly due to rounding.
(2) %RPD of sample and sample duplicate exceeded 30%.
(3) One or more lab matrix spike recoveries exceeded 10030% but was within 10050%; therefore, sample uncertainty expanded to 100+50%. See Data and Results Discussion section for more information.
(4) One of the lab matrix spike recoveries exceeded 10050% but was within 10060%; therefore, sample uncertainty expanded to 10060%.
(5) Sample was an aqueous equipment rinseate blank. Results are reported in units of ng/g (based on native wet weight). Rinseate sample was not extracted in duplicate. The aqueous rinseate sample was treated the same as a "solid" sediment sample during the extraction and analysis. Results may be biased low by approximately 11 % as the sample contained no visible solids and was actually "diluted" during the extraction procedure.
(6) Sample uncertainty expanded to 100+40% due to a non-compliant CCV recovery. See Continuing Calibration section for more information.
(7) GLP07-02-01-048 was used as a matrix blank for the extracted calibration curve, method blanks, and lab control spike samples throughout the analyses and produced results less than the LOQ for the given extraction day for each target analyte. Each day samples were extracted, six separate method blank extractions of GLP07-02-01-048 were prepared. See Method Blanks section for more details.
Test System/Samples
Forty-nine samples (43 sediment samples, 2 aqueous "rinse blank" samples, and 4 aqueous trip blanks and trip blank spikes) were received at the 3M Environmental Laboratory at ambient conditions on August 31,2007 from Weston Solutions, Inc personnel. The samples were logged in by 3M Environmental Laboratory personnel and placed in refrigerated storage on August 31,2007 until they were removed for the screening extraction on September 11, 2007. The aqueous trip blanks and trip blank spikes were not analyzed as they were intended to be QC samples for surface water samples that were not collected. Samples were re-extracted on September 26, October 5, October 11, October 16, October 19, and October 22, 2007.
The test system for this study is sediment and aqueous rinseate samples collected off-site from the 3M Decatur facility. Samples for this study are "real world" samples, not dosed with a specific lot of test substance. The table below provides the key code for sample descriptions.
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 15 of 209
3M Environmental Laboratory P0003268; Interim Report#2
Table 2. Sample Description Key Code.
String Number
String Descriptor
Example
1 General Sampling Location
DAL= Decatur, Alabama
2 Sample Type
SD=Sediment;
RB= Equipment Rinseate Blank
3 Sampling Location, Sample Number
EP = East Pond WP = West Pond
DU = Drainageway Upgradient of the East Pond
DS = Swamp Area Drainageway Downgradlent of the East Pond
4 Sample Type
0=primary sample volume
DB=duplicate sample
5 Sampling Interval (Depth) 0010 = sample collected 0.5 to 1.0 feet below ground surface
0030 = sample collected 2.5 to 3.0 feet below ground surface
0045 = sample collected 4.5 to 5.0 feet below ground surface
Reference Substances
Table 3 lists the pertinent information regarding the reference substances used for this study.
Table 3. Study Reference Substances.
R eference Substance
PFBS
PFHS
(1>PFO S
Chemical Name
Perfluorobutanesulfonate Perfluorohexanesulfonate Perfluorooctanesulfonate
Chemical Formula
C4F9SO3K*
CeFnSOj'K*
CeF,7S 0 3K*
Identifier
CAS # 29420-49-3
CAS #3871-99-6
CAS # 2795-39-3
Source Expiration Date
3M 01/18/2017
3M 2/12/2017
3M 8/31/2016 (Lot 217) 12/14/2016 (Lot 171)
Storage Conditions
Frozen
Frozen
Frozen
Chemical Lot Number TCR Number
Lot 2 TCR-359
NB# 120067-69 TCR-83 (SE036)
217,171 TCR-1166 (Lot 217) TCR-696 (Lot 171)
Physical Description
White Crystals
White Powder
White powder
Purity
97.3%
98.6%
86.9% (Lot 217) 86.4% (Lot 171)
(1) TCR-1166 was used to prepare the Lab Matrix Spiking standards. TCR-696 was used to prepare the extracted calibration curves.
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 16 of 209
3M Environmental Laboratory P0003268; Interim ReporW2
Method Summaries
Preparatory and Analytical Methods
Extraction
All samples, calibration standards, and associated quality control samples were extracted using the procedure outlined in ETS-8-12.1. Briefly, 1 g of sediment was accurately weighed into a 15 mL centrifuge tube and 8 mL of 80:20 acetonitrile:water extraction solvent was added. After thoroughly mixing the sediment/solvent system, the samples were then sonicated for two hours at room temperature. After sonication, the sample aliquots were centrifuged at approximately 3000 rpm for 15 minutes to pellet the solids. An aliquot of clarified supernatant (extract) was then transferred to an autovial for analysis.
Samples were extracted for the screening analysis on September 11,2007 and were re extracted for the final analysis on selected days from September 25, 2007 through October 22, 2007.
For the final analysis, samples were extracted in duplicate using the same procedure described above. Additionally, a low level and a high level laboratory matrix spike were prepared for each sample. Laboratory matrix spikes were prepared by spiking a separate 1 g sediment aliquot with known amounts of the target analytes prior to adding the extraction solvent. The spike levels prepared were dependent on the approximate concentration level estimated during the initial screening analysis. Several of the high level PFOS laboratory matrix spikes required dilution to produce area counts within the established calibration range. A five-fold instrument dilution for these samples was accomplished by using a 2 nL injection volume against a curve established with a 10 aL injection volume. During this run, 2 nL injections of high level CCV standards were also injected to verify that accurate dilutions could be obtained via this approach.
Analysis
All sample and quality control extracts were analyzed for PFBS, PFHS, and PFOS using high performance liquid chromatography/ tandem mass spectrometry (HPLC/MS/MS). Pertinent instrument parameters, the liquid chromatography program, and the specific mass transitions analyzed are described in the tables below.
Table 4. Instrument Parameters.
Instrument Name
ETSOIlie or ETSStan
Liquid Chromatograph
Agilent 1100
Guard column
Betasil C8 (4.6 mm X 150 mm), 5 pm
Analytical column
Betasil C18 (4.6 mm X100 mm), 5 pm
Injection Volume
10 pL
Mass Spectrometer
Applied Biosystem API 4000
Ion Source
Turbo Spray
Polarity
Negative
S o ftw a re
Analyst 1.4.2
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 17 of 209
3M Environmental Laboratory P0003268; Interim Report#2
Table 5. Liquid Chromatography Program.
Step Number
Total Time (min)
Flow Rate (fiL/min)
Percent A
2 mM Ammonium Acetate (aq)
0 0.00 1 0.5 2 11.0
1000 1000 1000
97.0 97.0 5.0
3 13.5
1000
5.0
4 13.6
1000
97.0
5 17.0
1000
97.0
PercentB Methanol
3.0 3.0 95.0 95.0 3.0 3.0
Table 6. Mass Transitions.
Analyte
Mass Transition Q1/Q3
PFBS
299/99
299/80
PFHS
399/99
399/80
PFOS
499/99
499/80
499/130
Dwell Time (msec) ETSOIlie 125 125 125 125 125 125 125
Dwell Time (msec) ETSStan 100 100 100 100 100 100 100
Analytical Results
Calibration
Calibration standards were prepared by spiking known amounts of stock solutions containing the target analytes into 1g aliquots of GLP07-01-01-048. Each spiked sediment standard was then extracted in the same manner as the collected samples. A total of fifteen standards were prepared ranging in nominal concentrations of 0.2 ng/g (wet weight) to 8000 ng/g (wet weight) which corresponds to 0.025 ng/mL to 1000 ng/mL. Quadratic, 1/x weighted, calibration curves were used to fit the data. The correlation coefficients (r) were greater than 0.999. The data were not forced through zero during the fitting process. Calculating the standard concentration using the peak area counts and the resultant calibration curve confirmed the accuracy of each curve point. ETS 8-12.1 requires that each standard used to generate the final calibration should back calculate to within 10025% of the theoretical value (10030% for the LOQ standard) and that mid-level calibration points may not be deactivated. Curve points at the very low and high end may be deactivated as needed to produce an accurate curve over the desired calibration range.
On 9/27/2007, the 0.1 ng/mL (mid-level) PFBS calibration point was deactivated because it produced an accuracy of 135%. Eleven extracted calibration points ranging from 0.025 ng/mL to 100 ng/mL were used to establish the final curve. As all PFBS lab control spikes and lab matrix spikes produced recoveries within the given method criteria, the overall impact to the data quality objectives of this method non-compliance is considered minimal. A method deviation has been issued. See Attachment D for additional information.
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 18 of 209
3M Environmental Laboratory P0003268; Interim R eports
Limit of Quantitation (LOQ)
The LOQ for this analysis, as defined in 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(s) and meets the calibration accuracy requirement described above (10030%).
Blanks
Three types of blanks were prepared and analyzed with the samples: method blanks, solvent blanks, and equipment rinseate blanks. Each blank type is described below.
Solvent Blanks
Several extraction solvent blanks (80:20 acetonitrile:water) were analyzed to assess system contamination and/or instrument carryover. In general, analyte peak area counts in 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. A minimum of four blanks were analyzed after the 1000 ng/mL calibration standard to verify the instrument was clean prior to analyzing the first method blanks. A solvent blank was analyzed after all high level LMS samples. When carryover was observed (for the highest level PFOS LMSs), the amount was minimal (<1%) compared to the sample concentrations analyzed after the solvent blank. Therefore, the reported sample concentrations were impacted minimally.
Method Blanks
Six method blanks were prepared each day samples were extracted by extracting separate 1g aliquots of GLP07-01-01-048. The average area counts of the six method blanks was calculated and verified to be less than half the area counts of the resultant LOQ standard. The tables below provide the average LOQ each day samples were extracted and from which results were reported herein.
Table 7. Method Blank Results for Extraction Day 9/25/2007.
mLOQ Concentration (ng/g dry weight)
Sample Comment
Sample ID
Amount Extracted (g)
PFBS
PFHS
mPFOS
MB-070925-1
Method Blank-1
0.9816
MB-070925-2 Method Blank-2
1.0617
MB-070925-3 Method Blank-3
1.0086
MB-070925-4 Method Blank-4
1.0847
MB-070925-5 Method Blank-5
0.9732
MB-070925-6 Method Blank-6
1.0618
Average LOQ ng/g dry weight
<0.240 <0.222 <0.234 <0.217 <0.242 <0.222 <0.229
<0.265 <0.245 <0.258 <0.240 <0.267 <0.245 <0.253
<0.233 <0.215 <0.227 <0.211 <0.235 <0.215 <0.223
%RSD
NA NA NA
%Solids GLP07-02-01-048
85.6
(1) LOQs in ng/mL: PFBS LOQ =0.0252 ng/mL, PFHS LOQ = 0.0278 ng/mL, PFOS LOQ = 0.0245 ng/mL
(2) A separate "low level" curve was established to achieve a lowest possible PFOS LOQ for GLP07-02-048 (QC) and GLP07-02-049 (sample). All other sediment samples extracted on this and subsequent days were well above the LOQ.
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 19 of 209
3M Environmental Laboratory P0003268; Interim Reporm
Table 8. Method Blank Results for Extraction Day 10/11/2007.
(1)LOQ Concentration (ng/g) dry weight
Sample Comment
Sample ID
Amount Extracted (g)
PFBS
PFHS
PFOS
MB-071011-1 MB-071011-2 MB-071011-3 MB-071011-4 MB-071011-5 MB-071011-6
Method Blank-1 Method Blank-2 Method Blank-3 Method Blank-4 Method Blank-5 Method Blank-6
0.9523 1.0450 1.0595 1.0035 1.0883 1.0155
<0.248 <0.226 <0.223 <0.235 <0.217 <0.232
<0.273 <0.249 <0.245 <0.259 <0.239 <0.256
<0.300 <0.274 <0.270 <0.285 <0.263 <0.282
Average LOQ ng/g dry weight
<0.230
<0.253
<0.279
%RSD
NA NA
NA
%Solids GLP07-02-01-048
85.6
(1) LOQs in ng/mL: PFBS LOQ =0.0252 ng/mL, PFHS LOQ = 0.0278 ng/mL, PFOS LOQ = 0.0306 ng/mL
(2) The 0.0245 ng/mL calibration standard for PFOS was deactivated from the calibration curve as it did not meet method calibration accuracy requirements. It was not deactivated because the area counts of the method blanks were greater than half the area counts of the lowest level standard. Sample concentrations analyzed on this day well exceeded the 0.279 ng/g LOQ so no additional effort was made to obtain the lowest possible LOQ.
Table 9. Method Blank Results for Extraction Day 10/19/2007.
LOQ Concentration (ng/g) dry weight
Sample Comment
Sample ID
Amount Extracted (g)
PFBS
PFHS
00PFOS
(,)MB-071019-1 Method Blank-1
0.9825
<0.240
<0.265
<0.291
<1)MB-071019-2 Method Blank-2
0.9502
<0.248
<0.274
<0.301
(2)MB-071019-3 Method Blank-3
0.9437
<0.250
<0.275
<0.485
(2)MB-071019-4 Method Blank-4
0.9603
<0.246
<0.271
<0.477
(2)MB-071019-5 Method Blank-5
0.9776
<0.241
<0.266
<0.468
(2)MB-071019-6 Method Blank-6
0.9703
<0.243
<0.268
<0.472
Average LOQ ng/g dry weight
<0.245
<0.270
<0.416
%RSD
NA NA
NA
%SolidS GLP07-02-01-048
85.6
(1) Method Blank-1 and Method Blank-2 were reported from a run started on 10/22/2007. The run was terminated due to an instrument collection error. LOQs in ng/mL: PFBS 0.0252 ng/mL, PFHS LOQ=0.0278 ng/mL and PFOS LOQ = 0.0306 ng/mL.
(2) Method Blanks-3 through -6 were analyzed in a new instrument collection batch started on 10/23/2007. LOQs in ng/mL: PFBS 0.0252 ng/mL, PFHS LOQ=0.0278 ng/mL and PFOS LOQ = 0.0490 ng/mL.
(3) Low level calibration standards for PFOS were deactivated to meet method calibration accuracy criteria while expanding the upper calibration range needed for several of the samples. Low level calibration points were not deactivated because the area counts of the method blanks were greater than half the area counts of the low level standards. As samples extracts analyzed on these days produced concentrations >0.5 ng/mL no effort was made to obtain a lower LOQ.
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 20 of 209
3M Environmental Laboratory P0003268; Interim R eports
Table 10. Method Blank Results for Extraction Day 10/22/2007.
(vLOQ Cone, (ng/g) dry weight
Sample Comment
Sample ID
Amount Extracted (g)
PFBS
PFHS
121PFOS
MB-071022-1 MB-071022-2 MB-071022-3 MB-071022-4 MB-071022-5 MB-071022-6
Method Blank-1 Method Blank-2 Method Blank-3 Method Blank-4 Method Blank-5 Method Blank-6
1.046 0.9904 1.0688 1.0692 1.0735 1.0016
<0.225 <0.238 <0.221 <0.221 <0.220 <0.235
<0.248 <0.262 <0.243 <0.243 <0.242 <0.259
<0.437 <0.462 <0.428 <0.428 <0.426 <0.457
Average LOQ ng/g dry weight
<0.227
<0.250
<0.440
%RSD
NA NA
NA
%Solids GLP07-02-01-048
85.6
(1) LOQs in ng/mL: PFBS LOQ =0.0252 ng/mL, PFHS LOQ = 0.0278 ng/mL, PFOS LOQ = 0.0490 ng/mL
(2) Low level calibration standards for PFOS were deactivated to meet method calibration accuracy criteria while expanding the upper calibration range needed for several of the samples. The sediment extracts analyzed on this day were in the range of 50 to 1200 ng/mL so no additional effort was made to obtain the lowest possible LOQ.
Equipment Rinseate Blanks
Two aqueous equipment rinseate blanks were submitted as samples: GLP07-02-01-037 and GLP07-02-01-043. These two water samples were treated as sediment samples both during the extraction procedure and final analysis (1 g weighed and extracted in the same manner as sediment, the extract analyzed against a sediment extracted curve). When determining the final concentration, the sample was treated as if it were a "solid" sample: the calculated concentration in ng/mL was multiplied by 8, the volume of extraction solvent added. As the rinseate samples contained no visible solids, the sample was actually diluted by a factor of 9 (1 mL of aqueous sample + 8 mL of extraction solvent). Therefore, reported concentrations in ng/g may be biased low by approximately 11%.
Both rinseate blank samples produced target analyte concentrations less than the analytical LOQ for the given day indicating that equipment contamination was not present in the targeted calibration range. Equipment rinseate blanks were not extracted in duplicate.
Continuing Calibration
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. All CCVs met the ETS 8-12.1 method acceptance criteria for accuracy of 10025% recovery except for the instances listed below in Table 11. Samples bracketed by these non-compliant CCVs were not reanalyzed as the degree of non-compliance was minimal. A method deviation has been issued and can be found in Attachment D of this report. Samples bracketed by non-compliant CCVs have been footnoted when necessary.
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 21 of 209
3M Environmental Laboratory P0003268; Interim Report#2
Table 11. Non-compliant CCVs.
Injection Number
Analyte
%Recovery
Samples Bracketed by Non-Compliant
CCVs
Action Taken/Comment
o070927a078 PFBS o070927a078 PFHS
(,)Not Calculated
(,)Not Calculated
GLP07-02-01-045, 046,-049
GLP07-02-01 -045, 046, -049
Area counts of CCV injection was 109% of the area counts of the original curve point injection. Instrument response still stable. No action necessary.
Area counts of CCV injection was 101% of the area counts of the original curve point injection. Instrument response still stable. No action necessary.
o071023a051 PFOS
126%
GLP07-02-01-024, 026, -027, -028
CCV non-compliance was still within overall PFOS method uncertainty of 10030%. No action necessary.
o071023a063 PFOS
128%
GLP07-02-01-027, 028-030, -041
CCV non-compliance was still within overall PFOS method uncertainty of 10030%. No action necessary.
o071023a087 PFOS
131%
GLP07-02-01-042, 047
Uncertainty of affected samples expanded to 10040% to account for CCV non compliance.
o071023a087 PFHS
126%
GLP07-02-01-042, 047
Uncertainty of affected samples expanded to 10040% to account for CCV non compliance.
(1) Curve point selected as a CCV was not used in the final calibration curve. Consequently, the concentration of the CCV exceeded the upper calibration range and a concentration value was not calculated by the software.
Lab Control Spikes (LCSs)
Triplicate low (0.3 ng/mL nominal concentration) and high (10 ng/mL nominal concentration) lab control spikes (LCSs) were prepared each day samples were extracted. LCSs were prepared by spiking known amounts of the target analytes into separate 1 g aliquots of GLP07-02-01-048 sediment to produce the desired concentration. The spiked sediment 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 (from which sample results were reported) are presented in the data table below. Each day, the average recovery of the pooled LCSs met ETS 8-12.1 method criteria for accuracy (10020%) and precision (RSD<20%). The LCS recovery data indicate that the sample results for GLP0702-01-048 can be reported with the stated overall method uncertainty of each analyte.
The tables below provide spike concentrations in units of ng/mL. Values In ng/g dry weight depend on the amount of sample weighed for each lab control spike sample. As approximately 1 g of sediment was weighed for each control sample, nominal spike concentrations in units of ng/g (dry weight) are as follows: PFBS low: 2.94 ng/g, high: 94.4 ng/g; PFHS low: 3.25 ng/g, high: 104 ng/g; and PFOS low: 2.85 ng/g; and high: 91.5 ng/g.
Spike
Concentration
(--nq
)
dryweight
=
Spike Concentration-- * 8mL ____________________mL_______
9 Sample Weight (g) * Percent Solids
%Solids for GLP07-02-01-048 = 85.6%.
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 22 of 209
3M Environmental Laboratory P0003268; Interim Report#2
Table 12. Lab Control Spike Results.
Extraction Day: 9/25/2007
,VPFBS
Sample Comment
Sample ID
LCS-070925-1 LCS-070925-2 LCS-070925-3 LCS-070925-4 LCS-070925-5 LCS-070925-6 Average %RSD
LCS Low 1 LCS Low 2 LCS Low 3 LCS High 1 LCS High 2 LCS High 3
Extraction Day: 10/11/2007
Spiked Cone. (ng/mL)
0.315 0.315
0.315 10.1 10.1 10.1
Calc. Cone. (ng/mL)
0.327 0.356 0.350 11.0 11.0 10.8
mPFBS
Sample Comment
LCS-071011-1 LCS-071011-2 LCS-071011-3 LCS-071011-4 LCS-071011-5 LCS-071011-6 Average %RSD
Sample ID
LCS Low 1 LCS Low 2 LCS Low 3 LCS High 1 LCS High 2 LCS High 3
Spiked Cone. (ng/mL)
0.315 0.315 0.315 10.1 10.1 10.1
Calc. Cone. (ng/mL)
0.322 0.320 0.325 10.0 10.0 10.1
%Rec. 104 113 111 109 109 107 109 3.0
%Rec. 102 101 103 99.1 99.1 100 101 1.6
Spiked Cone. (ng/mL)
0.348
0.348 0.348 11.1 11.1 11.1
<1>PFHS
Calc. Cone. (ng/mL) 0.367 0.405 0.374 11.4 11.2 11.4
Spiked Cone. (ngAnL)
0.348 0.348 0.348 11.1 11.1 11.1
n PFHS
Cafe. Cone. (ng/mL) 0.337 0.341 0.353 11.0 11.1 10.5
%Rec. 105 116 107 103 101 103 106 5.3
%Rec. 97.0 98.1 102 98.9 100 94.4 98.3 2.5
Spiked Cone. (ng/mL)
0.306 0.306 0.306 9.79 9.79 9.79
mPFOS
Calc. Cone. (ngAnL) 0.304 0.312 0.300 11.0 10.7 10.7
Spiked Cone. (ng/mL)
0.306 0.306 0.306 9.79 9.79 9.79
OpFOS
Calc. Cone. (ngAnL) 0.301 0.304 0.309 9.70 9.96 9.72
%Rec. 99.3 102 98.0 112 109 109 105 5.7
%Rec. 98.4 99.3 101 99.1 102 99.3 100 1.3
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 23 of 209
3M Environmental Laboratory P0003268; Interim Report#2
Extraction Day: 10/13/2007
<1IPFBS
mPFHS
mPFOS
Sample Comment
Sample ID
LCS-071019-1
LCS Low 1
LCS-071019-2 LCS Low 2
LCS-071019-3 LCS Low 3
LCS-071019-4 LCS High 1
LCS-071019-5 LCS High 2
LCS-071019-6 LCS High 3
Average
%RSD
Extraction Day: 10/22/2007
Spiked Cone. (ng/mL)
0.315
0.315 0.315 10.1 10.1 10.1
Calc. Cone. (ng/mL)
0.276 0.259 0.273 8.47 8.81 9.85
mPFBS
%Rec.
87.5 82.1 86.6 83.9 87.3 97.6 87.5 6.1
Spiked Cone. (ng/mL)
0.348 0.348
0.348 11.1 11.1 11.1
Cate. Cone. (ng/mL)
0.302 0.327 0.335 9.84 10.5 10.6
(,,PFHS
%Rec.
86.9 94.1 96.4 88.5 94.4 95.3 926 4.2
Spiked Cone. (ng/mL)
0.306 0.306 0.306 9.79 9.79 9.79
Calc. Cone. (ng/mL)
0.287 0.252 0.281 9.08 9.46 10.1
mPFOS
%Rec.
93.8 82.4 91.8 92.7 96.6 103 93.4 7.3
Sample Comment
Sample ID
Spiked Cone. (ng/mL)
Calc. Cone. (ng/mL)
%Rec.
Spiked Cone. (ng/mL)
Calc. Cone. (ng/mL)
%Rec.
Spiked Cone. (ng/mL)
Calc. Cone. (ng/mL)
%Rec.
LCS-071022-1
LCS Low 1
0.315
0.299
94.8
0.348
0.345
99.3
0.306
0.291
95.1
LCS-071022-2 LCS Low 2
0.315
0.298
94.5
0.348
0.344
99.0
0.306
0.290
94.8
LCS-071022-3 LCS Low 3
0.315
0.286
90.7
0.348
0.345
99.3
0.306
0.281
91.8
LCS-071022-4 LCS High 1 10.1 9.72 96.3 11.1 11.5 103 9.79 10.2 104
LCS-071022-5 LCS High 2 10.1 9.43 93.5 11.1 11.2 101 9.79 10.1 103
LCS-071022-6 LCS High 3
10.1
9.49
94.1
11.1
10.9
98.0
9.79
9.84
100
Average
94.0 99.9 98.3
%RSD
2.0 1.9 5.1
(1) Table displays rounded values for all concentration and percent recovery values (3 significant figures) and %RSD (2 significant figures). Reported values may vary slightly from the raw data.
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 24 of 209
3M Environmental Laboratory P0003268; Interim Report#2
Sample Duplicates
All submitted sediment samples were extracted in duplicate (except GLP07-02-01-048 which was extracted numerous times as method blanks) to assess the sample homogeneity. The relative percent difference (%RPD) for each sample and extraction duplicate is provided in Table 1. Samples with a %RPD exceeding 30% have been footnoted in the results tables.
Dry Weight Determination
The dry weight (%solids) was determined for each sample. Briefly, a 1 g aliquot of the well mixed sediment sample was placed in a pre-weighed aluminum weighing pan (tare weight recorded) and the mass of the sediment plus the pan was accurately measured using an analytical balance. The pan containing the wet sediment sample was then placed in an oven at 1055C 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. The dry weight (percent solids) was determined in duplicate for each sample (two separate aliquots of sample measured independently on the same day) except for GLP0702-01-048. A single measurement for this sample was recorded as the duplicate pan was spilled during the weighing process.
Percent solids = KPan + Average Dry Weight)(g) - (Tared Pan Weight)(g)] , 1QQ%
[(Pan + Wet Weight)(g) - (Tared Pan Weight)(g)]
The average percent solids used to determine the concentration of the target analytes in the soil sample on a ng/g (dry weight) basis. It should be emphasized that this approach assumes all the reported fluorochemical (FC) concentration was adsorbed to the sediment surface. No attempt was made to differentiate or to determine the partitioning of the detected FCs between the sediment surface and the water fraction extracted.
sample extract concentration (-- ) * 8 mL extraction solvent -- (wet weight) = ---------------------------------------------- ------------------------------------g mass extracted native (wet) sediment(g)
sample extract concentration (-- ) * 8 mL extraction solvent -- (dry weight) = ___________________ ml________________ 9 mass extracted native (wet) sediment(g) * percent solids
Laboratory Matrix Spikes (LMSs)
Separate laboratory matrix spikes at two different levels were prepared for each submitted sediment sample. The low and high level spike concentrations varied depending on the native concentration estimated during the initial screening analysis. ETS-8-12.1 states that laboratory matrix spike levels should be between 0.5 and 10 times the endogenous level for the laboratory matrix spike recoveries to be used to determine the statement of accuracy for the sample results without further justification. Because the screening analyses indicated that the PFOS needed to be at a much higher level than PFBS and PFHS, a separate PFOS
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 25 of 209
3M Environmental Laboratory P0003268; Interim Report#2
spiking solution was prepared. The "A" solution contained PFBS, PFHS, and another analyte not analyzed as part of this study. The "B" solution contained PFOS only. A total of five different spike group classifications were used, with each group consisting of an "A" spike and a separate "B" spike. (Each group had a low and high level spike.) The table below lists the final concentrations of the low and high spikes for each of the five groups.
Table 13. Laboratory Matrix Spike Concentrations.
n Spike Concentration (ng)
Solution A PFBS
Solution A PFHS
Solution B PFOS
Spike Group 1 (A1, B1)
A1 low, B1 low A1 high, B1 high
1.01 1.04 1.00 10.1 10.4 10.0
Spike Group 2 (A1, B2)
A1 low, B2 low A1 high, B2 high
4.05 12.8 250 22.6 58.7 1030
Spike Group 3 (A2, B2)
A2 low, B2 low
4.05 21.6
250
A2 high, B2 high
22.6 147 1030
Spike Group 4 (A2, B3)
<2|A2 low, B3 low
13.6 58.6 1030
(2)A2 high, B3 high
133 574 10100
Spike Group 5 (A3, B3)
(2)A3 low, B3 low
13.6 58.6 1030
<2)A3 high, B3 high
133 574 10100
(1) Spike concentrations provided in units of ng for simplicity. (Values provided here are reported to three significant figures and may vary slightly with the values used in the raw data to calculate recovery.) Spike concentrations in units of ng/g (wet weight) depend on the amount of sample weighed for the given LMS sample. As approximately 1 g of sample was weighed, the ng values provided in the table are roughly equivalent to the ng/g (wet weight) value. However, the spike concentrations in units of ng/g (dry weight) depend on the percent solids for the given sample.
(2) Solutions A2 and A3 had equivalent concentrations of PFBS, PFHS, and PFOS, but varied in the amount of the other analyte which was not part of this study. Therefore, Spike Group 4 and Spike Group 5 were equivalent for this study.
(Cone. LMS sample(-- ) * 8 mL - (Average Wet Weight Cone.-- * LMS Amount Extracted (g)) LMS Spike Recovery = __________________ mL_________________________________ g_________________________ 100%
Spike Amount (ng)
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 26 of 209
3M Environmental Laboratory P0003268; Interim ReporW2
Data Summary and Discussion
The tables (Table 14, Table 15, and Table 16) below summarize the sample results and lab matrix spike (LMS) recoveries for each sample submitted (tables separate results by analyte). Each table provides the sample, sample duplicate and average concentration, the lab matrix spike concentrations 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 10030% 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. However, if the spike concentration was greater than 10 times the endogenous concentration, the spike recoveries were calculated and reported. The spike level range of 0.5 to 10 times the endogenous concentration listed in ETS 8-12.1 is intended to be a guideline with the lower range limit a more critical factor for accurate quantitation than the upper limit. A method deviation has been issued that addresses the acceptability of reporting recoveries from spikes that exceed the upper range and can be found in Attachment D.
In general, lab matrix spike recoveries of the submitted samples were within 10030% and the results were considered accurate to within the overall analytical method uncertainty of 10020% (PFBS), 10021% (PFHS), and 10030% (PFOS) (see Determination o f Analytical Method Uncertainty for more information). Exceptions have been assigned an expanded sample uncertainty of 10040%, 10050%, or 10060% and have been footnoted accordingly in Table 1 and in the full QC tables below.
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 27 of 209
3M Environmental Laboratory P0003268; Interim Reportt2
Table 14. PFBS Sample Results with QC.
A Spte: Level 1; B Spte: Level 2
Sample Description GLP07-01-01-001 GLP07-01-01-001 Duplicate GLP07-01-01-001 LMS Low GLP07-01-01-001 LMS High
A Spike: Leve* 1; B Spike: Level 2
Sample Comment
DALSDEP01 00010 DAL SDEP01 0 0010 DAL SDEP01 0 0010 DAL SD EP01 0 0010 Average %RPD Average %Solids
Sample Description
GLP07-02-01 -002 GLP07-02-01-002 Duplicate GLP07-02-01-002 LMS Low GLP07-02-01-002 LMS High
Sample Comment
DAL SDEP02 0 0010 DAL SDEP02 00010 DAL SDEP02 00010 DAL SDEP02 0 0010 Average %RPD Average %So!ids
<VPFBS
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9580 0.9951 0.9804 0.9933
Calculated Cone. (ng/mL)
0.0970 0.0282 0.609
3.14
84.0
Cone, ng/g (wet weight)
0.810 0.227
NA NA 0.518 m110
Cone, ng/g (dry weight)
0.964 0.270
NA NA 0.617 m110
(1 PFBS
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0685 1.0194 1.0139 1.0271
Calculated Cone. (ng/mL)
0.0779 0.0724 0.645 2.98
86.9
Cone, ng/g (wet weight)
0.583 0.568
NA NA 0.576 2.6
Cone, ng/g (dry weight)
0.671 0.654
NA NA 0.663 2.6
5{Recovery NA NA 108 109
%Recovery NA NA 113 103
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 28 of 209
3M Environmental Laboratory P0003268; Interim Repori#2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-003 GLP07-02-01 -003 Duplicate GLP07-02-01-003 LMS Low GLP07-02-01-003 LMS High
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-004 GLP07-02-01 -004 Duplicate GLP07-02-01-004 LMS Low GLP07-02-01-004 LMS High
Sample Comment DALSD EP02 0 0030 DAL SDEP02 0 0030 DAL SDEP02 0 0030 DALSD EP02 0 0030 Average %RPD Average %Solids
Sample Comment DAL SDEP02 0 0045 DALSD EP02 0 0045 DALSD EP02 0 0045 DAL SDEP02 0 0045 Average %RPD Average %Solkfs
<1>PFBS
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0315 0.9915 0.9969 0.9543
Calculated Cone. (ng/mL)
0.277 0.370 0.853 3.21
85.4
Cone, ng/g (wet weight)
2.15 2.99 NA NA 2.57 33
Cone, ng/g (dry weight)
2.51 3.49 NA NA 3.00 33
mPFBS
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9039 0.9822 0.9468 1.0287
Calculated Cone. (ng/mL)
0.341 0.344 0.743 2.60
84.3
Cone, ng/g (wet weight)
3.02 2.80 NA NA 2.91 7.4
Cone, ng/g (dry weight)
3.58 3.32 NA NA 3.45 7.4
%Recovery NA NA 105 103
%Recovery NA NA 78.8 78.8
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 29 of 209
3M Environmental Laboratory P0003268; Interim Report#2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-005 GLP07-02-01-005 Duplicate GLP07-02-01 -005 LMS Low GLP07-02-01-005 LMS High
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-01-01-006 GLP07-01 -01-006 Duplicate GLP07-01-01-006 LMS Low GLP07-01-01-006 LMS High
Sample Comment DAL SD EP03 00010 DAL SD EP03 0 0010 DAL SDEP03 0 0010 DAL SDEP03 0 0010 Average %RPD Average %Solids
Sample Comment DAL SDEP03 0 0030 DAL SD EP03 0 0030 DAL SDEP03 0 0030 DAL SD EP03 0 0030 Average %RPD Average %Solids
(1PFBS
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0507 1.0281 1.0365 1.0530
Calculated Cone. (ng/mL)
0.0880 0.0848 0.638
3.09
90.0
Cone, ng/g (wet weight)
0.670 0.660
NA NA 0.665 1.5
Cone, ng/g (dry weight)
0.745 0.734
NA NA 0.739 1.5
d PFBS
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9672 1.0847 0.9442 1.0643
Calculated Cone. (ng/mL)
0.0794 0.0666 0.599
3.08
84.0
Cone, ng/g (wet weight)
0.657 0.491
NA NA 0.574 29
Cone, ng/g (dry weight)
0.782 0.585
NA NA 0.683 29
%Recovery NA NA 109 106
"/Recovery NA NA 105 106
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 30 of 209
3M Environmental Laboratory P0003268; Interim Report#2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-01-01-007 GLP07-01-01-007 Duplicate GLP07-01 -01-007 LMS Low GLP07-01-01-007 LMS High
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01 -008 GLP07-Q2-01 -008 Dup GLP07-02-01 -008 LMS Low GLP07-02-01-008 LMS High GLP07-02-01-008 LMS High
Sample Comment DAL SDEP03 0 0045 DAL SDEP03 0 0045 DAL SDEP03 0 0045 DAL SDEP03 0 0045 Average %RPD Average %Solids
Sample Comment DALSD EP04 0 0010 DAL SDEP04 0 0010 DAL SD EP04 0 0010 DALSD EP04 0 0010 DAL SDEP04 0 0010 Average %RPD Average %Solids
,1,PFBS
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0897 0.9493 1.0507 1.0036
Calculated Cone. (ng/mL)
0.0586 0.0388 0.565
2.92
86.2
Cone, ng/g (wet weight)
0.430 0.327
NA NA 0.379 27
Cone, ng/g (dry weight)
0.499 0.379
NA NA 0.439 27
mPFBS
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
1.0529 0.9872 0.9229 0.9492 0.9492
Calculated Cone. (ng/mL)
0.339 0.308 2.17 18.8 19.0
84.9
Cone, ng/g (wet weight)
2.58 2.50 NA NA NA 2.54 3.1
Cone, ng/g (dry weight)
3.03 2.94 NA NA NA 2.99 3.1
%,Recovery NA NA 102 102
%Recovery NA NA 110 111 113
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 31 of 209
3M Environmental Laboratory P0003268; Interim Repori#2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-009 GLP07-02-01-009 Duplicate GLP07-02-01-009 LMS Low GLP07-02-01-009 LMS High
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01-010 GLP07-02-01-010 Dup GLP07-02-01-010 LMS Low GLP07-02-01-010 LMS High GLP07-02-01-010 LMS High
Sample Comment DALSD EP04 0 0030 DAL SDEP04 0 0030 DAL SDEP04 0 0030 DALSD EP04 0 0030 Average %RPD Average %Solids
Sample Comment DALSD EP05 0 0010 DALSD EP05 0 0010 DALSD EP05 0 0010 DAL SD EP05 0 0010 DAL SDEP05 0 0010 Average %RPD Average %Solids
(1,PFBS
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9885 1.0153 1.0266 1.0372
Calculated Cone. (ng/mL)
0.237 0220 0.725 3.19
85.1
Cone, ng/g (wet weight)
1.92 1.73 NA NA 1.83 10
Cone, ng/g (dry weight)
2.25 2.04 NA NA 2.14 10
`/Recovery
NA NA 97.0 105
mPFBS
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
0.9200 1.0568 0.9131 1.0361 1.0361
Calculated Cone. (ng/mL)
0.152 0.179 1.83 17.2 17.3
82.0
Cone, ng/g (wet weight)
1.32 1.36 NA NA NA 1.34 2.5
Cone, ng/g (dry weight)
1.61 1.65 NA NA NA 1.63 2.5
`/Recovery
NA NA 98.6 102 103
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 32 of 209
31VI Environmental Laboratory P0003268; Interim ReportR2
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01-011 GLP07-02-01-011 Dup GLP07-02-01 -011 LMS Low GLP07-02-01-011 LMS High GLP07-02-01-011 LMS High
4 Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-012 GLP07-02-01 -012 Duplicate GLP07-02-01-012 LMS Low GLP07-02-01-012 LMS High
Sample Comment DAL SD EP05 DB 0010 DAL SD EP05 DB 0010 DAL SD EP05 DB 0010 DAL SD EP05 DB 0010 DAL SD EP05 DB 0010 Average %RPD Average %So!ids
Sample Comment DAL SD EP05 0 0030 DAL SD EP05 0 0030 DAL SD EP05 0 0030 DAL SD EP05 0 0030 Average Y.RPD Average %Solids
mPFBS
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
1.0015 1.0151 0.9279 0.9456 0.9456
Calculated Cone. (ng/mL)
0.137 0.170 1.86 17.0 17.9
82.1
Cone, ng/g (w et weight)
1.09 1.34 NA NA NA 1.22 20
Cone, ng/g (dry weight)
1.33 1.63 NA NA NA 1.48 20
(1PFBS
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9960 0.9317 1.0002 1.0336
Calculated Cone. (ng/mL)
0.149 0.139 0.683 2.95
83.6
Cone, ng/g (w et weight)
1.20 1.19 NA NA 1.20 0.27
Cone, ng/g (thy weight)
1.43 1.43 NA NA 1.43 0.27
YoRecovery NA NA 101 101 107
YaRecovery NA NA 105 99.0
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 33 of 209
3M Environmental Laboratory P0003268; Interim Report#2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-013 GLP07-02-01 -013 Duplicate GLP07-02-01 -013 LMS Low GLP07-02-01-013 LMS High
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01-014 GLP07-02-01-014 Dup GLP07-02-01-014 LMS Low GLP07-02-01-014 LMS High GLP07-02-01-014 LMS High
Sample Comment DALSD EP06 0 0010 DALSD EP06 0 0010 DALSD EP06 0 0010 DALSD EP06 0 0010 Average %RPD Average "/Solids
Sample Comment DALSD EP07 0 0010 DAL SDEP07 0 0010 DALSD EP07 0 0010 DAL SDEP07 0 0010 DAL SDEP07 0 0010 Average %RPD Average %Solids
,1IPFBS
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9909 0.9638 1.0492 1.0153
Calculated Cone. (ngAnL)
0.128 0.141 0.707 3.15
90.5
Cone, ng/g (w et weight)
1.03 1.17 NA NA 1.10 12
Cone, ng/g (dry weight)
1.14 1.29 NA NA 1.22 12
<VPFBS
Dilution Factor
1 1 1 1 5
Mass Extracted(g)
1.0017 1.0017 0.9555 1.0250 1.0250
Calculated Cone. (ng/mL)
0.320 0.325 1.92 15.8 16.5
82.0
Cone, ng/g (w et weight)
2.56 2.60 NA NA NA 2.58 1.6
Cone, ng/g (dry weight)
3.12 3.17 NA NA NA 3.14 1.6
"/Recovery NA NA 111 107
"/Recovery NA NA 94.8 93.1 97.3
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 34 of 209
3M Environmental Laboratory P0003268; Interim Repor#2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01 -015 GLP07-02-01-015 Duplicate GLP07-02-01-015 LMS Low GLP07-02-01-015 LMS High
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-016 GLP07-02-01-016 Duplicate GLP07-02-01-016 LMS Low GLP07-02-01-016 LMS High
Sample Comment DAL SDEP07 0 0030 DAL SDEP07 0 0030 DAL SDEP07 0 0030 DALSD EP07 0 0030 Average %RPD Average %Solids
Sample Comment DAL SDEP07 0 0045 DALSD EP07 0 0045 DAL SDEP07 0 0045 DAL SD EP07 0 0045 Average %RPD Average %Solids
mPFBS
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0663 1.0606 1.0706 1.0711
Calculated Cone. (ng/lnL)
0.154 0.149 0.681 2.83
85.3
Cone, ng/g (w et weight)
1.16 1.12 IMA NA 1.14 2.8
Cone, ng/g (dry weight)
1.35 1.32 NA NA 1.34 2.8
n PFBS
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0546 1.0472 1.0852 0.9515
Calculated Cone. (ng/mL)
0.102 0.120 0.649 3.01
87.2
Cone, ng/g (w et weight)
0.774 0.917
NA NA 0.845 17
Cone, ng/g (dry weight)
0.887 1.05 NA NA 0.969 17
%Recovery NA NA 104 94.8
%Recovery NA NA 106 103
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 35 of 209
3M Environmental Laboratory P0003268; Interim Report#2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-017 GLP07-02-01-017 Duplicate GLP07-02-01-017 LMS Low GLP07-02-01-017 LMS High
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01-018 GLP07-02-01 -018 Dup GLP07-02-01-018 LMS Low GLP07-02-01-018 LMS High GLP07-02-01 -018 LMS High
Sample Comment DALSD EP07DB0045 DAL SDEP07DB 0045 DALSD EP07DB0045 DAL SD EP07 DB 0045 Average %RPD Average %Solids
Sample Comment DALSD EP08 0 0010 DALSD EP08 0 0010 DAL SD EP08 0 0010 DAL SDEP08 0 0010 DAL SDEP08 0 0010 Average %RPD Average %Solids
(1PFBS
Dilution Factor
1 1 1 1
Mass Extracted(g)
1.0298 0.9724 1.0019 0.9140
Calculated Cone. (ng/mL)
0.114 0.103 0.681 3.17
85.2
Cone, ng/g (w et weight)
0.886 0.847
NA NA 0.866 4.4
Cone, ng/g (dry weight)
1.04 0.995
NA NA 1.02 4.4
(1PFBS
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
0.9513 0.9857 1.0233 0.9459 0.9459
Calculated Cone. (ng/mL)
0.109 0.120 1.88 17.8 18.5
85.0
Cone, ng/g (w et weight)
0.917 0.974
NA NA NA 0.945 6.1
Cone, ng/g (dry weight)
1.08 1.15 NA NA NA 1.11 6.1
%Recovery NA NA 113 109
%Recovery NA NA 103 106 111
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 36 of 209
3M Environmental Laboratory P0003268; Interim Repordt2
Sample Description GLP07-02-01-019 GLP07-02-01-019 Dup GLP07-02-01-019 LMS Low GLP07-02-01-019 LMS High
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-020 GLP07-02-01-020 Dup GLP07-02-01 -020 LMS Low GLP07-02-01 -020 LMS High
Sample Comment DALSD EP09 0 0010 DALSD EP09 0 0010 DAL SD EP09 0 0010 DALSD EP09 0 0010 Average %RPD %Solids
Sample Comment DAL SD EP09 0 0030 DALSD EP090 0030 DAL SD EP09 0 0030 DAL SD EP09 0 0030 Average %RPD %So!ids
fl PFBS
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0559 1.0364 1.0085 1.0674
Calculated Cone. (ngAnL)
0.167 0.188 0.663 2.80
83.9
Cone, ng/g (w et weight)
1.27 1.45 NA NA 1.36 14
Cone, ng/g (dry weight)
1.51 1.73 NA NA 1.62 14
(1PFBS
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9214 1.0577 1.0120 1.0741
Calculated Cone. (ng/mL)
0.086 0.127 0.592 2.82
84.3
Cone, ng/g (w et weight)
0.749 0.961
NA NA 0.855 25
Cone, ng/g (dry weight)
0.889 1.14 NA NA 1.01 25
/Recovery NA NA 97.2 92.7
%Recovery NA NA 95.6 95.8
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 37 of 209
3M Environmental Laboratory P0003268; Interim Repor&2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-021 GLP07-02-01-021 Dup GLP07-02-01-021 LMS Low GLP07-02-01 -021 LMS High
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01-022 GLP07-02-01 -022 Dup GLP07-02-01-022 LMS Low GLP07-02-01 -022 LMS High GLP07-02-01-022 LMS High
Sample Comment DALSD EP09 0 0045 DAL SDEP09 0 0045 DAL SDEP09 0 0045 DALSD EP09 0 0045 Average %RPD Average %Solids
Sample Comment DALSD EP10 0 0010 DALSD EP10 0 0010 DAL SDEP10 0 0010 DALSD EP10 0 0010 DAL SD EP10 0 0010 Average %RPD Average %Solids
mPFBS
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0314 0.9683 0.9274 1.0552
Calculated Cone. (ngAnL)
0.0958 0.0955 0.520 2.48
83.3
Cone, ng/g (w et weight)
0.743 0.789
NA NA 0.766 6.0
Cone, ng/g (dry weight)
0.892 0.947
NA NA 0.920 6.0
<1PFBS
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
0.9243 1.0539 1.0876 1.0918 1.0918
Calculated Cone. (ngAnL)
0.126 0.143 1.98 17.9 18.9
84.7
Cone, ng/g (w et weight)
1.09 1.09 NA NA NA 1.09 0.47
Cone, ng/g (dry weight)
1.29 1.28 NA NA NA 1.28 0.47
%Recovery NA NA 85.2 84.2
%Recovery NA NA 108 107 113
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 38 of 209
3M Environmental Laboratory P0003268; Interim Repori#2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-023 GLP07-02-01-023 Dup GLP07-02-01-023 LMS Low GLP07-02-01-023 LMS High
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-024 GLP07-02-01-024 Dup GLP07-02-01 -024 LMS Low GLP07-02-01-024 LMS High
Sample Comment DAL SD EP10 0 0030 DALSD EP10 00030 DAL SDEP10 0 0030 DALSD EP100 0030 Average %RPD Average %Solids
Sample Comment DALSD EP10 0 0045 DALSD EP10 00045 DAL SDEP10 0 0045 DALSD EP10 0 0045 Average %RPD Average %Solids
,VPFBS
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9282 1.0811 1.0848 0.9999
Calculated Cone. (ng/mL)
0.108 0.124 0.594 2.71
82.8
Cone, ng/g (w et weight)
0.931 0.918
NA NA 0.924 1.4
Cone, ng/g (dry weight)
1.12 1.11 NA NA 1.12 1.4
(1PFBS
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0419 0.9957 1.0422 1.0300
Calculated Cone. (ng/mL)
0.144 0.126 0.642 2.95
85.1
Cone, ng/g (w et weight)
1.11 1.01 NA NA 1.06 8.8
Cone, ng/g (dry weight)
1.30 1.19 NA NA 1.24 8.8
%Recovery NA NA 92.6 91.8
%Recovery NA NA 100 100
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 39 of 209
3M Environmental Laboratory P0003268; Interim Report#2
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01-025 GLP07-02-01-025 Dup GLP07-02-01-025 LMS Low GLP07-02-01-025 LMS High GLP07-02-01-025 LMS High
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-026 GLP07-02-01-026 Dup GLP07-02-01-026 LMS Low GLP07-02-01 -026 LMS High
Sample Comment DALSD EP11 0 0010 DALSD EP11 0 0010 DALSDEP11 0 0010 DALSD EP11 0 0010 DALSD EP11 0 0010 Average %RPD Average %Solids
Sample Comment DALSD EP11 0 0030 DAL SDEP11 0 0030 DAL SDEP11 0 0030 DAL SDEP11 0 0030 Average %RPD Average %So!ids
(1IPFBS
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
0.9626 0.9955 1.0097 1.0241 1.0241
Calculated Cone. (ng/mL)
0.599 0.615 2.50 18.2 18.4
92.0
Cone, ng/g (w et weighty
4.98 4.94 NA NA NA 4.96 0.72
Cone, ng/g (dry weight)
5.41 5.37 NA NA NA 5.39 0.72
mPFBS
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0064 0.9796 1.0121 1.0583
Calculated Cone. (ng/mL)
0.127 0.130 0.720 3.28
85.9
Cone, ng/g (w et weighty
1.01 1.06 NA NA 1.04 5.0
Cone, ng/g (dry weight
1.18 1.24 NA NA 1.21 5.0
%Recovery NA NA 110 106 107
%Recovery NA NA 116 111
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 40 of 209
3M Environmental Laboratory P0003268; Interim ReporW2
A Spte: Level 1; B Spte: Level 2
Sample Description GLP07-02-01-027 GLP07-02-01-027 Dup GLP07-02-01-027 LMS Low GLP07-02-01-027 LMS High
A Spte: Level 1; B Spte: Level 2
Sample Description GLP07-02-01-028 GLP07-02-01-028 Dup GLP07-02-01 -028 LMS Low GLP07-02-01-028 LMS High
Sample Comment DALSDEP11 DB 0030 DAL SD EP11 DB 0030 DALSDEP11 DB 0030 DAL SD EP11 DB 0030 Average %RPD Average %Solids
Sample Comment DALSD EP12 0 0010 DAL SDEP12 0 0010 DAL SDEP12 0 0010 DAL SDEP12 0 0010 Average %RPD Average %So!ids
mPFBS
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9617 0.9785 0.9672 1.0278
Calculated Cone. (ng/mL)
0.113 0.129 0.729 3.47
85.2
Cone, ng/g (w et weight)
0.940 1.05 NA NA 0.997 11
Cone, ng/g (dry weight)
1.10 1.24 NA NA 1.17 11
mPFBS
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0701 0.9479 0.9288 0.9653
Calculated Cone. (ng/mL)
0.0570 0.0508 0.662
3.02
88.1
Cone, ng/g (w et weight)
0.426 0.429
NA NA 0.427 0.61
Cone, ng/g (dry weight)
0.484 0.487
NA NA 0.485 0.61
"/Recovery NA NA 120 118
%Recovery NA NA 121 105
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 41 of 209
3M Environmental Laboratory P0003268; Interim Report#2
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01-029 GLP07-02-01-029 Dup GLP07-02-01-029 LMS Low GLP07-02-01-029 LMS High GLP07-02-01-029 LMS High
A Spike: Level 1; B Spike: Level 2
Sample Desorption GLP07-02-01-030 GLP07-02-01-030 Dup GLP07-02-01-030 LMS Low GLP07-02-01-030 LMS High
Sample Comment DALSD EP13 0 0010 DAL SDEP13 0 0010 DAL SDEP13 0 0010 DAL SDEP13 0 0010 DALSD EP13 0 0010 Average %RPD Average %Solids
Sim ple Comment DALSD EP13 0 0030 DAL SDEP13 0 0030 DALSD EP13 0 0030 DAL SDEP13 0 0030 Average %RPD Average %Solids
mPFBS
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
1.0167 0.9516 0.9971 0.9561 0.9561
Calculated Cone. (ng/mL)
0.349 0.329 2.33 18.9 19.2
94.7
Cone, ng/g (w et weight)
2.75 2.77 NA NA NA 2.76 0.72
Cone, ng/g (dry weight)
2.90 2.92 NA NA NA 2.91 0.72
<1>PFBS
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0329 0.9524 1.0468 1.0301
Calculated Cone. (ng/mL)
0.149 0.131 0.696 3.22
85.2
Cone, ng/g (w et weight)
1.15 1.10 NA NA 1.13 4.8
Cone, ng/g (dry weight)
1.35 1.29 NA NA 1.32 4.8
%Recovery NA NA 117 112 114
%Recovery NA NA 108 109
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 42 of 209
3M Environmental Laboratory P0003268; Interim Repori#2
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01-031 GLP07-02-01-031 Dup GLP07-02-01-031 LMS Low GLP07-02-01 -031 LMS High GLP07-02-01-031 LMS High
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01 -032 GLP07-02-01-032 Dup GLP07-02-01-032 LMS Low GLP07-02-01-032 LMS High GLP07-02-01-032 LMS High
Sample Comment DAL SDEP14 0 0010 DAL SDEP14 0 0010 DAL SDEP14 0 0010 DAL SD EP14 0 0010 DAL SDEP14 0 0010 Average %RPD Average %Solids
Sample Comment DAL SD EP14DB0010 DAL SD EP14 DB 0010 DAL SD EP14 DB 0010 DALSDEP14DB 0010 DAL SDEP14DB 0010 Average %RPD Average %Soiids
<1PFBS
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
0.9305 1.0403 0.9865 0.9939 0.9939
Calculated Cone. (ng/mL)
0.267 0.329 2.15 18.5 19.0
91.6
Cone, ng/g (w et weight)
2.30 2.53 NA NA NA 2.41 9.7
Cone, ng/g (d iy weight)
2.51 2.76 NA NA NA 2.64 9.7
a PFBS
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
0.9524 0.9351 0.9486 0.9398 0.9398
Calculated Cone. (ng/mL)
0.270 0.248 2.07 18.1 19.2
91.0
Cone, ng/g (w et weight)
2.27 2.12 NA NA NA 2.19 6.7
Cone, ng/g (dry weight)
2.49 2.33 NA NA NA 2.41 6.7
%Recovery NA NA 109 110 113
%Recovery NA NA 106 107 114
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 43 of 209
3M Environmental Laboratory P0003268; Interim Reportit2
A Spike: Level 1; B Spike: Level 1
Sample Description |3|GLP07-02-01 -037 GLP07-02-01-037 LMS Low
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01-038 GLP07-02-01-038 Dup GLP07-02-01-038 LMS Low GLP07-02-01-038 LMS High GLP07-02-01-038 LMS High
Sample Comment DALSDDU01 RB0010 DALSD DU01 RB0010
Sample Comment DAL SD DU01 0 0010 DALSD DU01 0 0010 DALSD DU01 0 0010 DALSD DU01 0 0010 DALSD DU01 0 0010 Average %RPD Average %Solids
<VPFBS
Dilution Factor
1 1
Mass Extracted (g)
1.0294 1.0481
Calculated Cone. (ng/mL)
<0.0252 0.0939
Cone, ng/g (w et weight)
(3|<0.196 NA
Cone, ng/g (dry weight)
NA NA
%Recovery NA 74.3
mPFBS
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
0.9486 1.0004 0.9503 0.9572 0.9572
Calculated Cone. (ng/mL)
0.225 0.270 2.10 17.5 18.0
90.3
Cone, ng/g (w et weight)
1.90 2.16 NA NA NA 2.03 13
Cone, ng/g (dry weight)
2.10 2.39 NA NA NA 2.25 13
%Recovery
NA NA 109 104 107
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 44 of 209
3M Environmental Laboratory P0003268; Interim Reportit2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-01-01-039 GLP07-01 -01-039 Duplicate GLP07-01-01-039 LMS Low GLP07-01-01-039 LMS High
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-01-01-040 GLP07-01-01-040 Duplicate GLP07-01-01-040 LMS Low GLP07-01-01-040 LMS High
Sample Comment DALSD DU02 0 0010 DAL SD DU02 0 0010 DALSD DU02 0 0010 DALSD DU02 0 0010 Average %RPD Average %Solids
Sim ple Comment DALSD DU03 0 0010 DAL SDDU03 0 0010 DAL SDDU03 0 0010 DALSD DU03 0 0010 Average %RPD Average %Solids
,VPFBS
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9853 0.9781 0.9854 1.0066
Calculated Cone. (hg/mL)
0.0304 0.0288 0.561
3.15
89.3
Cone, ng/g (w et weight)
0.247 0.236
NA IMA 0.241 4.7
Cone, ng/g (dry weight)
0.277 0.264
NA NA 0.270 4.7
(1PFBS
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9563 1.0574 0.9385 0.9280
Calculated Cone. (ng/mL)
<0.0252 <0.0252
0.592 3.150
90.2
Cone, ng/g (w et weight)
<0.211 <0.191
NA NA <0.201 NA
Cone, ng/g (dry weight)
<0234 <0.211
NA NA <0.223 NA
%Recovery NA NA 105 110
%Recovery NA NA 117 112
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 45 of 209
3M Environmental Laboratory P0003268; Interim Report#2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-041 GLP07-02-01-041 Dup GLP07-02-01-041 LMS Low GLP07-02-01-041 LMS High
A Spike: Level 1; B Spire: Level 2
Sample Description GLP07-02-01-042 GLP07-02-01-042 Dup GLP07-02-01-042 LMS Low GLP07-02-01-042 LMS High
Sample Comment DALSD DU04 0 0010 DALSD DU04 0 0010 DAL SD DU04 0 0010 DALSD DU04 0 0010 Average %RPD Average %Solids
Sample Comment DALSD DU05 0 0010 DAL SD DU05 0 0010 DALSD DU05 0 0010 DALSD DU05 0 0010 Average %RPD Average %Solids
(1PFBS
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9389 0.9654 0.9899 0.9516
Calculated Cone. (ng/mL)
0.392 0.417 0.915 3.42
90.5
Cone, ng/g (w et weight)
3.34 3.46 NA NA 3.40 3.4
Cone, ng/g (dry weight)
3.69 3.82 NA NA 3.75 3.4
n PFBS
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9372 0.9475 1.0648 0.9434
Calculated Cone. (ng/mL)
0.109 0.102 0.742 3.27
85.6
Cone, ng/g (w et weight)
0.930 0.861
NA NA 0.896 7.7
Cone, ng/g (dry weight)
1.09 1.01 NA NA 1.05 7.7
%Recovery NA NA 97.7 107
%Recovery NA NA 123 112
3M Environmental Laboratory
GLP07-02-Q1, Decatur Sediments Sulfonates
Page 46 of 209
3M Environmental Laboratory P0003268; Interim Report#2
A Spike: Level 1; B Spike: Level 1
Sample Description (3|GLP07-02-01 -043 GLP07-02-01-043 LMS Low
A Spte: Level 1; B Spte: Level 2
Sample Description GLP07-01-01-044 GLP07-01 -01-044 Duplicate GLP07-01-01-044 LMS Low GLP07-01 -01-044 LMS High
Sample Comment DAL SD DU05 RB 0010 DALSD DU05 RB 0010
Sample Comment DAL SDDS01 0 0010 DAL SDDS01 0 0010 DALSDDS01 0 0010 DALSDDS01 0 0010 Average %RPD Average %Solids
(1PFBS
Dilution Factor
1 1
Mass Extracted (g)
1.0375 0.9990
Calculated Cone. (ng/mL)
<0.0252 0.0984
Cone, ng/g (w et weight)
,3,<0.195 NA
Cone, ng/g (dry weight)
NA NA
%Recovery NA 77.8
<1PFBS
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9684 0.9392 0.9528 1.0091
Calculated Cone. (ng/mL)
<0.0252 <0.0252
0.576 3.18
92.0
Cone, ng/g (w et weight)
<0.208 <0.215
NA NA <0.211 NA
Cone, ng/g (dry weight)
<0.227 <0.234
NA NA <0.230 NA
%Recovery
NA NA 114 113
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 47 of 209
3M Environmental Laboratory P0003268; Interim Reportlt2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-01-01-045 GLP07-01-01-045 Duplicate GLP07-01-01-045 LMS Low GLP07-01 -01-045 LMS High
A Spike: Level 1; B Spte: Level 2
Sample Description GLP07-01-01-046 GLP07-01-01-046 Duplicate GLP07-01-01-046 LMS Low GLP07-01-01-046 LMS High
Sample Comment DAL SDDS01 0 0010 DAL SD DS01 0 0010 DAL SDDS01 00010 DAL SD DS01 0 0010 Average %RPD Average %Solids
Sample Comment DAL SD DS02 0 0010 DALSD DS02 0 0010 DAL SD DS02 0 0010 DAL SDDS02 0 0010 Average %RPD Average %Solids
0 PFBS
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0345 1.0823 0.9614 0.9936
Calculated Cone. (ng/mL)
0.0354 0.0373 0.605
3.20
91.3
Cone, ng/g (w et weighty
0.274 0.276
NA NA 0.275 0.71
Cone, ng/g (dry weight)
0.300 0.302
NA NA 0.301 0.71
(1PFBS
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9512 0.9792 0.9756 0.9964
Calculated Cone. (ng/mL)
<0.0252 <0.0252
0.633 3.25
92.8
Cone, ng/g (wet weight)
<0.212 <0.206
NA NA <0.209 NA
Cone, ng/g (dry weight)
<0.228 <0.222
NA NA <0.225 NA
%Recovery NA NA 113 112
%Recovery NA NA 125 115
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 48 of 209
3M Environmental Laboratory P0003268; Interim Reportit2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01 -047 GLP07-02-01 -047 Dup GLP07-02-01-047 LMS Low GLP07-02-01-047 LMS High
(4|GLP07-02-01 -048
A Spike: Level 1; B Spike: Level 1
Sample Description GLP07-01-01-049 GLP07-O1-01-049 Duplicate GLP07-01 -01-049 LMS Low GLP07-01 -01-049 LMS High
Sample Comment DAL SDDS02 0 0030 DAL SD DS02 0 0030 DAL SD DS02 0 0030 DAL SD DS02 0 0030 Average %RPD Average %Solids
DAL SDWP01 0 0010
Sample Comment DAL SDWP02 0 0010 DAL SDWP02 0 0010 DALSD WP02 0 0010 DAL SDWP02 0 0010 Average %RPD Average %Solids
mPFBS
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9725 0.9180 0.9951 1.0723
Calculated Cone. (ng/mL)
0.0432 0.0405 0.607
3.23
91.4
Cone, ng/g (w et weight)
0.355 0.353
NA NA 0.354 0.69
Cone, ng/g (dry weight)
0.389 0.386
NA NA 0.387 0.69
% R ecovery
NA NA 111 113
1 NA
(4)n a
|4|n a
(4,NA
(1PFBS
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0349 0.9924 1.0687 1.0343
Calculated Cone. (ng/mL)
<0.0252 <0.0252
0.115 1.22
84.7
Cone, ng/g (w et weight)
<0.195 <0.203
NA NA <0.199 NA
Cone, ng/g (dry weight)
<0.230 <0.240
NA NA <0.235 NA
|4)n a
%Recovery NA NA 91.0 96.5
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 49 of 209
3M Environmental Laboratory P0003268; Interim Report#2
(1) Unless otherwise specified, the recovery of associated laboratory matrix spikes was within 10030% indicating that method was appropriate for the given matrix. Sample results are considered accurate to within the overall analytical method uncertainty 100+20%. See Determination of Analytical Method Uncertainty section for more information. Sample results are reported to three significant figures and %RPD to two significant figures. Additional significant figures were used to calculate the average, %RPD, and %recovery. Values in the raw data may vary slightly due to rounding.
(2) %RPD of sample and sample duplicate exceeded 30%. (3) Sample was an aqueous equipment rinseate blank. Results are reported in units of ng/g (based on native wet weight). Rinseate sample was not extracted in duplicate.
The aqueous rinseate sample was treated the same as a "solid" sediment sample during the extraction and analysis. Results may be biased low by approximately 11 % as the sample contained no visible solids and was actually "diluted" during the extraction procedure. Only one level of LMS was prepared for rinseate samples. (4) GLP07-02-01-048 was used as a matrix blank throughout the analyses and produced results less than the LOQ for the given extraction day for each target analyte. See Method Blanks section for more details. Each day samples were extracted, six individual method blanks, triplicate low level, and triplicate high level spikes were prepared using this matrix. LCS recoveries were reported in Table 12 and indicate that results for this sample are accurate to within the overall method uncertainty of 10020%.
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page SOof 209
3M Environmental Laboratory P0003268; Interim Report#2
Table 15. PFHS Sample Results with QC.
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-01-01-001 GLP07-01-01-001 Duplicate GLP07-01-01-001 LMS Low GLP07-01-01-001 LMS High
A Spike: Level 1; B Spike: Level 2
Sample Comment
DAL SD EP01 0 0010 DALSDEP01 00010 DAL SD EP01 00010 DAL SD EP01 0 0010 Average %RPD Average %Solids
Sample Description
GLP07-02-01-002 GLP07-02-01-002 Duplicate GLP07-02-01 -002 LMS Low GLP07-02-01 -002 LMS High
Sample Comment
DAL SDEP02 0 0010 DAL SDEP02 0 0010 DAL SDEP02 0 0010 DAL SD EP02 0 0010 Average %RPD Average %Solids
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9580 0.9951 0.9804 0.9933
Calculated Cone. (ng/mL)
0.0431 0.0291
1.34 6.01
84.0
<VPFHS
Cone, ng/g (wet weight)
0.360 0.234
NA NA 0.297 42
Cone, ng/g (dry weight)
0.428 0.278
NA NA 0.353 42
mPFHS
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0685 1.0194 1.0139 1.0271
Calculated Cone. (ng/mL)
0.794 0.771 2.91 16.1
86.9
Cone, ng/g (w et weight)
5.94 6.05 NA NA 6.00 1.8
Cone, ng/g (dry weight)
6.84 6.96 NA NA 6.90 1.8
%Recovery NA NA 81.5 81.4
"/Recovery NA NA 79.6 83.6
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 51 of 209
3M Environmental Laboratory P0003268; Interim Report2
A Spike: Level 1; 8 Spike; Level 2
Sample Description GLP07-02-01-003 GLP07-02-01 -003 Duplicate GLP07-02-01-003 LMS Low GLP07-02-01-003 LMS High
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-004 GLP07-02-01-004 Duplicate GLP07-02-01-004 LMS Low GLP07-02-01-004 LMS High
Sample Comment DALSD EP02 0 0030 DAL SDEP02 0 0030 DAL SDEP02 00030 DALSD EP02 0 0030 Average %RPD Average %Solids
Sample Comment DAL SDEP02 0 0045 DAL SDEP02 0 0045 DAL SDEP02 0 0045 DAL SD EP02 0 0045 Average %RPD Average %Solids
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0315 0.9915 0.9969 0.9543
Calculated Cone. (ng/mL)
1.97 1.95 3.93 17.0
85.4
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9039 0.9822 0.9468 1.0287
Calculated Cone. (ng/mL)
2.03 2.34 3.81 14.5
84.3
mPFHS
Cone, ng/g (w et weight)
15.3 15.7 NA NA 15.5 2.9
Cone, ng/g (dry weighty
17.9 18.4 NA NA 18.2 2.9
mPFHS
Cone, ng/g (w et weighty
,3,18.0 ,3|19.1
NA NA m18.5 5.9
Cone, ng/g (dry weighty
(3,21.3 (3,22.6
NA NA m22.0 5.9
"/Recovery NA NA 74.0 82.6
%Recovery NA NA
(3,60.0 (3)66.1
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 52 of 209
3M Environmental Laboratory P0003268; Interim Report#2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-005 GLP07-02-01 -005 Duplicate GLP07-02-01-005 LMS Low GLP07-02-01-005 LMS High
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-01-01-006 GLP07-01-01-006 Duplicate GLP07-01-01-006 LMS Low GLP07-01-01-006 LMS High
Sample Comment DALSD EP03 0 0010 DALSD EP03 0 0010 DALSD EP03 00010 DAL SDEP03 0 0010 Average %RPD Average %Soiids
Sample Comment DALSD EP03 0 0030 DAL SD EP03 00030 DAL SD EP03 0 0030 DALSDEP03 0 0030 Average %RPD Average %Solids
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0507 1.0281 1.0365 1.0530
Calculated Cone. (ng/mL)
1.18 1.13 3.64 17.1
90.0
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9672 1.0847 0.9442 1.0643
Calculated Cone. (ng/mL)
0.438 0.374 1.56 6.46
84.0
mPFHS
Cone, ng/g (wet weight)
8.98 8.79 NA NA 8.89 2.2
Cone, ng/g (dry weight)
9.99 9.77 NA NA 9.88 2.2
(VPFHS
Cone, ng/g (w et weight)
3.62 2.76 NA NA 3.19 27
Cene, ng/g (dry weight)
4.31 3.28 NA NA 3.80 27
%Recovery NA NA 92.2 86.8
%Recovery NA NA 74.0 82.2
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page S3 of 209
3M Environmental Laboratory P0003268; Interim Reportlt2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-01 -01-007 GLP07-01 -01-007 Duplicate GLP07-01-01-007 LMS Low GLP07-01-01-007 LMS High
A Spike: Level 3; B Spike: Level 3
Sample Descripton GLP07-02-01 -008 GLP07-02-01-008 Dup GLP07-02-01-008 LMS Low GLP07-02-01-008 LMS High GLP07-02-01-008 LMS High
Sample Comment DAL SD EP03 0 0045 DAL SDEP03 0 0045 DALSD EP03 0 0045 DAL SD EP03 0 0045 Average %RPD Average %Solids
Sample Comment DALSD EP04 0 0010 DALSD EP04 0 0010 DALSD EP04 0 0010 DALSD EP04 0 0010 DAL SDEP04 0 0010 Average %RPD Average %Solids
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0897 0.9493 1.0507 1.0036
Calculated Cone. (ng/mL)
0.373 0.280 1.49 5.93
86.2
mPFHS
Cone, ng/g (wet weight)
2.74 2.36 NA NA 2.55 15
Cone, ng/g (dry weight)
3.18 2.74 NA NA 296 15
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
1.0529 0.9872 0.9229 0.9492 0.9492
Calculated Cone. (ng/mL)
3.71 3.40 9.38 60.3 64.1
84.9
mPFHS
Cone, ng/g (wet weight)
28.2 27.6 NA NA NA 27.9 2.3
Cone, ng/g (dry weight)
33.2 32.4 NA NA NA 32.8 2.3
%Recovery NA NA 72.3 76.4
%Recovery NA NA 84.2 79.5 84.8
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 54 of 209
3M Environmental Laboratory P0003268; Interim Report#2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01 -009 GLP07-02-01-009 Duplicate GLP07-02-01 -009 LMS Low GLP07-02-01-009 LMS High
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01-010 GLP07-02-01 -010 Dup GLP07-02-01-010 LMS Low GLP07-02-01-010 LMS High GLP07-02-01-010 LMS High
Sample Comment DALSD EP04 0 0030 DALSD EP04 0 0030 DALSD EP04 0 0030 DALSD EP04 0 0030 Average %RPD Average %Solids
Sample Comment DALSD EP05 0 0010 DALSD EP05 0 0010 DALSD EP05 0 0010 DAL SDEP05 0 0010 DAL SDEP05 0 0010 Average %RPD Average %Solids
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9885 1.0153 1.0266 1.0372
Calculated Cone. (ng/mL)
1.35 1.35 3.42 17.5
85.1
mPFHS
Cone, ng/g (wet weight)
10.9 10.6 NA NA 10.8 2.7
Cone, ng/g (dry weight)
12.8 12.5 NA NA 12.7 2.7
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
0.9200 1.0568 0.9131 1.0361 1.0361
Calculated Cone. (ng/mL)
1.46 1.81 7.14 54.1 58.9
82.0
mPFHS
Cone, ng/g (w et weight)
12.7 13.7 NA NA NA 13.2 7.6
Cone, ng/g (dry weight)
15.5 16.7 NA NA NA 16.1 7.6
%Recovery NA NA 75.4 87.8
%Recovery NA NA 76.9 73.1 79.8
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 55 of 209
3M Environmental Laboratory P0003268; Interim Report#2
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01-011 GLP07-02-01-011 Dup GLP07-02-01-011 LMS Low GLP07-02-01-011 LMS High GLP07-02-01-011 LMS High
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-012 GLP07-02-01-012 Duplicate GLP07-02-01-012 LMS Low GLP07-02-01-012 LMS High
Sample Comment DALSDEP05 DB0010 DALSD EP05DB0010 DALSD EP05DB0010 DAL SD EP05 DB 0010 DALSD EP05DB0010 Average %RPD Average %Solids
Sample Comment DAL SDEP05 0 0030 DAL SDEP05 0 0030 DAL SDEP05 0 0030 DAL SDEP05 00030 Average %RPD Average %Solids
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
1.0015 1.0151 0.9279 0.9456 0.9456
Calculated Cone. (ng/mL)
1.44 1.63 7.11 54.8 61.2
82.1
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9960 0.9317 1.0002 1.0336
Calculated Cone. (ng/mL)
0.906 0.901 3.16 16.0
83.6
mPFHS
Cone, ng/g (w et weight)
11.5 12.8 NA NA NA 12.2 11
Cone, ng/g (dty weight)
14.0 15.6 NA NA NA 14.8 11
mPFHS
Cone, ng/g (w et weight)
7.28 7.74 NA NA 7.51 6.1
Cone, ng/g (dry weight)
8.70 9.25 NA NA 8.97 6.1
%Recovery NA NA 77.8 74.4 83.3
%Recovery NA NA 82.3 81.9
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 56 of 209
3M Environmental Laboratory P0003268; Interim Repori2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01 -013 GLP07-02-01-013 Duplicate GLP07-02-01-013 LMS Low GLP07-02-01-013 LMS High
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01-014 GLP07-02-01-014 Dup GLP07-02-01-014 LMS Low GLP07-02-01-014 LMS High GLP07-02-01-014 LMS High
Sample Comment DAL SDEP06 0 0010 DALSD EP06 0 0010 DAL SD EP06 0 0010 DALSD EP06 0 0010 Average %RPD Average %Solids
Sample Comment DAL SDEP07 0 0010 DAL SDEP07 0 0010 DAL SDEP07 0 0010 DALSD EP07 0 0010 DAL SDEP07 0 0010 Average %RPD Average %Solids
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9909 0.9638 1.0492 1.0153
Calculated Cone. (ng/mL)
0.983 1.22 3.60 17.4
90.5
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
1.0017 1.0017 0.9555 1.0250 1.0250
Calculated Cone. (ng/mL)
2.67 2.64 7.62 53.8 58.6
82.0
mPFHS
Cone, ng/g (wet weight)
7.94 10.1 NA NA 9.03 24
Cone, ng/g (dry weight)
8.77 11.2 NA NA 9.98 24
mPFHS
Cone, ng/g (wet weight)
(3)21.3 |3|21.1
NA NA NA m21.2 1.1
Cone, ng/g (dry weighty
(3|26.0 (3|25.7
NA NA NA m25.9 1.1
"/Recovery NA NA 89.5 88.6
%Recovery NA NA
<3)69.5 71.2 81.5
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 57 of 209
3M Environmental Laboratory P0003268; Interim Report#2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-015 GLP07-02-01-015 Duplicate GLP07-02-01-015 LMS Low GLP07-02-01 -015 LMS High
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-016 GLP07-02-01-016 Duplicate GLP07-02-01-016 LMS Low GLP07-02-01-016 LMS High
Sample Comment DALSD EP07 0 0030 DALSD EPQ7 0 0030 DALSD EP07 0 0030 DALSD EP07 0 0030 Average %RPD Average %Solids
Sample Comment DALSD EP07 0 0045 DAL SDEP07 0 0045 DALSD EP07 0 0045 DALSD EP07 00045 Average %RPD Average %Solids
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0663 1.0606 1.0706 1.0711
Calculated Cone. (ng/mL)
1.24 1.08 3.26 15.6
85.3
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0546 1.0472 1.0852 0.9515
Calculated Cone. (ng/mL)
0.911 1.06 3.11 16.5
87.2
mPFHS
Cone, ng/g (met weighty
9.30 8.15 NA NA 8.72
13
Cone, ng/g (dry weighty
10.9 9.55 NA NA 10.2 13
f'P F H S
Cone, ng/g (w et weighty
6.91 8.10 NA NA 7.50 16
Cone, ng/g (dry weighty
7.92 9.28 NA NA 8.60 16
%Recovery NA NA 77.5 78.7
%Recovery NA NA 77.5 85.1
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 58 of 209
3M Environmental Laboratory P0003268; Interim Report82
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01 -017 GLP07-02-01-017 Duplicate GLP07-02-01-017 LMS Low GLP07-02-01-017 LMS High
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01-018 GLP07-02-01 -018 Dup GLP07-02-01-018 LMS Low GLP07-02-01-018 LMS High GLP07-02-01-018 LMS High
Sample Comment DAL SD EP07DB0045 DALSD EP07DB0045 DALSD EP07DB 0045 DALSD EP07DB0045 Average %RPD Average %Solids
Sample Comment DALSD EP08 0 0010 DALSD EP08 0 0010 DAL SDEP08 00010 DAL SDEP08 0 0010 DAL SDEP08 0 0010 Average %RPD Average %Solids
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0298 0.9724 1.0019 0.9140
Calculated Cone. (ng/mL)
0.821 0.766 3.17 17.1
85.2
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
0.9513 0.9857 1.0233 0.9459 0.9459
Calculated Cone. (ng/mL)
0.765 0.784 6.84 57.5 59.7
85.0
mPFHS
Cone, ng/g (w et weight)
6.38 6.30 NA NA 6.34 1.2
Cone, ng/g (dry weight)
7.49 7.40 NA NA 7.45 1.2
mPFHS
Cone, ng/g (wet weight)
6.43 6.36 NA NA NA 6.40 1.1
Cone, ng/g (dry weight)
7.57 7.49 NA NA NA 7.53 1.1
%Recovery NA NA 88.0 89.2
"/,,Recovery NA NA 82.2 79.1 82.2
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 59 of 209
3M Environmental Laboratory P0003268; Interim Reportif2
Sample Description GLP07-02-01-019 GLP07-02-01-019 Dup GLP07-02-01-019 LMS Low GLP07-02-01-019 LMS High
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-C2-01 -020 GLP07-02-01-020 Dup GLP07-02-01-020 LMS Low GLP07-02-01-020 LMS High
Sample Comment DAL SD EP09 0 0010 DAL SD EP09 0 0010 DALSD EP09 0 0010 DAL SD EP09 0 0010 Average %RPD %Solids
Sample Comment DALSD EP09 0 0030 DALSD EP09 0 0030 DAL SD EP09 0 0030 DAL SDEP09 0 0030 Average %RPD %Solids
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0559 1.0364 1.0085 1.0674
Calculated Cone. (ng/mL)
1.90 1.59 3.72 14.8
83.9
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9214 1.0577 1.0120 1.0741
Calculated Cone. (ng/mL)
0.755 1.02 2.91 15.1
84.3
WPFHS
Cone, ng/g (w et weight)
14.4 12.3 NA NA 133 16
Cone, ng/g (dry weight)
17.2 14.6 NA NA 15.9 16
mPFHS
Cone, ng/g (w et weight)
6.56 7.71 NA NA 7.14 16
Cone, ng/g (dry weight)
7.77 9.15 NA NA 8.46 16
%Recovery NA NA 75.5 71.0
%Recovery NA NA 74.4 77.1
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 60 of 209
3M Environmental Laboratory P0003268; Interim Report#2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-021 GLP07-02-01-021 Dup GLP07-02-01-021 LMS Low GLP07-02-01 -021 LMS High
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01-022 GLP07-02-01-022 Dup GLP07-02-01-022 LMS Low GLP07-02-01-022 LMS High GLP07-02-01-022 LMS High
Sample Comment DAL SDEP09 0 0045 DAL SD EP09 0 0045 DAL SD EP09 0 0045 DAL SD EP09 0 0045 Average %RPD Average %Solids
Sample Comment DAL SD EP10 0 0010 DAL SD EP10 0 0010 DAL SD EP10 0 0010 DAL SDEP10 0 0010 DAL SDEP10 0 0010 Average %RPD Average %Solids
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0314 0.9683 0.9274 1.0552
Calculated Cone. (ngAnL)
0.639 0.773 2.21 14.2
83.3
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
0.9243 1.0539 1.0876 1.0918 1.0918
Calculated Cone. (ngAnL)
1.61 1.93 8.04 57.5 62.5
84.7
mPFHS
Cone, ng/g (w et weight)
,3)4.96 (3)6.39
IMA NA ra5.67 25
Cone, ng/g (dry weight)
|3)5.95 |3|7.67
NA NA Pl6.81 25
mPFHS
Cone, ng/g (wet weight)
13.9 14.7 IMA NA NA 14.3 5.0
Cone, ng/g (tby weight)
16.5 17.3 NA NA NA 16.9 5.0
%Recovey NA NA
(3|57.5 73.3
"/R e c o v e ry NA NA 83.3 77.5 84.4
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 61 of 209
3M Environmental Laboratory P0003268; Interim Reportt2
A Spte: Level 1; B Spte: Level 2
Sample Description GLP07-02-01-023 GLP07-02-01-023 Dup GLP07-02-01 -023 LMS Low GLP07-02-01-023 LMS High
A Spte: Level 1; B Spte: Level 2
Sample Description GLP07-02-01 -024 GLP07-02-01 -024 Dup GLP07-02-01 -024 LMS Low GLP07-02-01 -024 LMS High
Sample Comment DAL SDEP10 0 0030 DAL SDEP10 0 0030 DAL SD EP10 0 0030 DAL SD EP10 0 0030 Average %RPD Average %Solids
Sample Comment DAL SDEP10 0 0045 DAL SDEP10 0 0045 DAL SD EP10 0 0045 DAL SDEP10 0 0045 Average %RPD Average %Solids
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9282 1.0811 1.0848 0.9999
Calculated Cone. (ng/mL)
0.673 0.804 2.74 14.9
82.8
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0419 0.9957 1.0422 1.0300
Calculated Cone. (ng/mL)
0.896 0.808 3.07 17.3
85.1
mPFHS
Cone, ng/g (w et weight)
5.80 5.95 NA IMA 5.87 2.5
Cone, ng/g (dry weight)
7.00 7.18 NA NA 7.09 2.5
mPFHS
Cone, ng/g (w et weight)
6.88 6.49 IMA IMA 6.69 5.8
Cone, ng/g (dry weighty
8.08 7.63 NA NA 7.86 5.8
%Recovery NA NA 72.0 77.2
VoRecovery NA NA 81.5 89.6
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 62 of 209
3M Environmental Laboratory P0003268; Interim Report&2
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01-025 GLP07-02-01-025 Dup GLP07-02-01-025 LMS Low GLP07-02-01-025 LMS High GLP07-02-01-025 LMS High
A Spte: Level 1; B Spte: Level 2
Sample Description GLP07-02-01-026 GLP07-02-01-026 Dup GLP07-02-01-026 LMS Low GLP07-02-01 -026 LMS High
Sample Comment DALSDEP11 0 0010 DAL SD EP11 0 0010 DALSD EP11 0 0010 DALSDEP11 0 0010 DALSD EP11 0 0010 Average %RPD Average %Solids
Sample Comment DAL SDEP11 0 0030 DAL SDEP11 0 0030 DALSD EP11 0 0030 DAL SDEP11 0 0030 Average %RPD Average %Solkfs
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
0.9626 0.9955 1.0097 1.0241 1.0241
Calculated Cone. (ng/mL)
2.87 3.03 8.97 58.6 63.3
92.0
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0064 0.9796 1.0121 1.0583
Calculated Cone. (ng/mL)
0.843 1.36 3.67 18.1
85.9
mPFHS
Cone, ng/g (w et weight)
23.9 24.3 NA NA NA 24.1 2.1
Cone, ng/g (dry weight)
25.9 26.5 NA NA NA 26.2 2.06
(1IPFHS
Cone, ng/g (w et weight)
6.70 11.1 NA NA 8.90 49
Cone, ng/g (dry weight)
7.80 12.9 NA NA 10.4 49
%Recovery NA NA 81.0 77.4 84.0
%Recovery NA NA 94.2 92.2
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 63 of 209
3M Environmental Laboratory P0003268; Interim Report#2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-027 GLP07-02-01-027 Dup GLP07-02-01-027 LMS Low GLP07-02-01 -027 LMS High
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01 -028 GLP07-02-01 -028 Dup GLP07-02-01-028 LMS Low GLP07-02-01-028 LMS High
Sample Comment DALSDEP11 DB 0030 DALSDEP11 DB 0030 DAL SD EP11 DB 0030 DAL SD EP11 DB 0030 Average %RPD Average %Solids
Sample Comment DALSD EP12 0 0010 DALSD EP12 0 0010 DAL SDEP12 0 0010 DALSD EP12 0 0010 Average %RPD Average %Solids
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9617 0.9785 0.9672 1.0278
Calculated Cone. (ng/mL)
1.16 1.29 3.90 20.1
85.2
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0701 0.9479 0.9288 0.9653
Calculated Cone. (ng/mL)
0.550 0.482 3.22 17.9
88.1
n PFHS
Cone, ng/g (w et weight)
9.65 10.5 NA NA 10.1 8.9
Cone, ng/g (dry weight)
11.3 12.4 NA NA 11.9 8.9
mPFHS
Cone, ng/g (w et weight)
4.11 4.07 NA NA 4.09 1.1
Cone, ng/g (dry weight)
4.67 4.62 NA NA 4.64 1.1
"/(Recovery NA NA 99.2 102
%Recovery NA NA 102 94.9
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 64 of 209
3M Environmental Laboratory P0003268; Interim Reportit2
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01 -029 GLP07-02-01-029 Dup GLP07-02-01-029 LMS Low GLP07-02-01-029 LMS High GLP07-02-01 -029 LMS High
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01 -030 GLP07-02-01-030 Dup GLP07-02-01 -030 LMS Low GLP07-02-01-030 LMS High
Sample Comment DAL SD EP13 0 0010 DALSD EP13 0 0010 DAL SD EP13 0 0010 DALSD EP13 0 0010 DAL SD EP13 0 0010 Average %RPD Average %Solids
Sample Comment DALSD EP13 0 0030 DAL SD EP13 0 0030 DALSD EP13 0 0030 DAL SD EP13 0 0030 Average %RPD Average %Solids
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
1.0167 0.9516 0.9971 0.9561 0.9561
Calculated Cone. (ng/mL)
1.90 1.83 8.72 59.0 62.7
94.7
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0329 0.9524 1.0468 1.0301
Calculated Cone. (ng/mL)
1.43 1.28 3.84 18.3
85.2
mPFHS
Cone, ng/g (wet weight)
15.0 15.4 NA NA NA 15.2 2.9
Conc. ng/g (dry weight)
15.8 16.2 NA NA NA 16.0 2.9
mPFHS
Conc. ng/g (wet weight)
11.1 10.8 NA NA 10.9 3.0
Conc. ng/g (dry weight)
13.0 12.6 NA NA 12.8 3.0
%Recovery NA NA 93.3 79.8 84.9
%Recovery NA NA 89.3 92.1
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 65 of 209
3M Environmental Laboratory P0003268; Interim ReportM2
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01-031 GLP07-02-01-031 Dup GLP07-02-01-031 LMS Low GLP07-02-01 -031 LMS High GLP07-02-01 -031 LMS High
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01-032 GLP07-02-01-032 Dup GLP07-02-01 -032 LMS Low GLP07-02-01-032 LMS High GLP07-02-01 -032 LMS High
Sample Comment DALSD EP14 0 0010 DALSD EP14 0 0010 DAL SDEP14 0 0010 DALSD EP14 0 0010 DALSD EP14 0 0010 Average %RPD Average %Solids
Sample Comment DAL SDEP14DB 0010 DAL SDEP14DB 0010 DALSD EP14DB0010 DAL SDEP14DB 0010 DAL SDEP14DB 0010 Average %RPD Average %Solids
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
0.9305 1.0403 0.9865 0.9939 0.9939
Calculated Cone. (ng/mL)
3.50 4.06 9.50 59.6 66.3
91.6
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
0.9524 0.9351 0.9486 0.9398 0.9398
Calculated Cone. (ng/mL)
3.42 3.25 9.17 59.4 64.3
91.0
mPFHS
Cone, ng/g (w et weight)
30.1 31.2 NA NA NA 30.7 3.7
Cone, ng/g (dry weight)
32.9 34.1 NA NA NA 33.5 3.7
,VPFHS
Cone, ng/g (wet weight)
28.7 27.8 NA NA NA 28.3 3.3
Cone, ng/g (dry weight)
31.6 30.6 NA NA NA 31.1 3.3
%Recovery NA NA 78.1 77.8 87.1
`/Recovery NA NA 79.5 78.2 85.0
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 66 of 209
3M Environmental Laboratory P0003268; Interim Reportt2
A Spike: Level 1; B Spike: Level 1
Sample Description wGLP07-02-01-037 GLP07-02-01-037 LMS Low
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01 -038 GLP07-02-01 -038 Dup GLP07-02-01 -038 LMS Low GLP07-02-01 -038 LMS High GLP07-02-01-038 LMS High
Sample Comment DALSDDU01 RB 0010 DAL SD DU01 RB 0010
Sample Comment DALSD DU01 0 0010 DALSD DU01 0 0010 DAL SD DU01 0 0010 DAL SDDU01 0 0010 DALSD DU01 0 0010 Average %RPD Average %Solids
Dilution Factor
1 1
Mass Extracted (g)
1.0294
1.0481
Calculated Cone. (ng/mL)
<0.0278 0.0948
mPFHS
Cone, ng/g (wet weight)
w<0.213 NA
Cone, ng/g (dry weight)
NA NA
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
0.9486 1.0004 0.9503 0.9572 0.9572
Calculated Cone. (ngAnL)
1.51 1.87 7.42 54.7 59.0
90.3
mPFHS
Cone, ng/g (wet weight)
12.7 15.0 NA NA NA 13.8 16
Cone, ng/g (dry weight)
14.1 16.6 NA NA NA 15.3 16
%Recovery NA 72.8
"/Recovery NA NA 78.9 74.0 80.0
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 67 of 209
3M Environmental Laboratory P0003268; Interim Report#2
A Spike: Level 1; B Spike: Level 2
Sim ple Description GLP07-01-01-039 GLP07-01-01-039 Duplicate GLP07-01-01-039 LMS Low GLP07-01-01-039 LMS High
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-01-01-040 GLP07-01-01-040 Duplicate GLP07-01-01-040 LMS Low GLP07-01-01-040 LMS High
Sample Comment DALSD DU02 0 0010 DALSD DU02 0 0010 DALSD DU02 0 0010 DALSD DU02 0 0010 Average %RPD Average %Solids
Sample Comment DALSD DU03 0 0010 DALSD DU03 0 0010 DALSD DU03 00010 DAL SD DU03 0 0010 Average %RPD Average %Solids
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9853 0.9781 0.9854 1.0066
Calculated Cone. (ng/mL)
0.325 0.330 1.48 6.39
89.3
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9563 1.0574 0.9385 0.9280
Calculated Cone. (ng/mL)
0.142 0.149 1.39 5.96
90.2
mPFHS
Cone, ng/g (w et weight)
2.64 2.70 IMA NA 2.67 2.3
Cone, ng/g (dry weight)
2.96 3.02 NA NA 2.99 2.3
<VPFHS
Cone, ng/g (wet weight)
1.19 1.13 NA NA 1.16 5.2
Cone, ng/g (dry weight)
1.32 1.25 NA NA 1.28 5.2
%Recovery NA NA 72.0 82.5
VoRecovery NA NA 78.4 79.4
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 68 of 209
3M Environmental Laboratory P0003268; Interim Report#2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-041 GLP07-02-01 -041 Dup GLP07-02-01 -041 LMS Low GLP07-02-01 -041 LMS High
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-042 GLP07-02-01-042 Dup GLP07-02-01-042 LMS Low GLP07-02-01-042 LMS High
Sample Comment DAL SD DU04 0 0010 DAL SD DU04 0 0010 DALSD DU04 0 0010 DALSD DU04 0 0010 Average %RPD Average %Solids
Sample Comment DAL SD DU05 0 0010 DAL SD DU05 0 0010 DALSD DU05 0 0010 DAL SD DU05 0 0010 Average %RPD Average %Solids
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9389 0.9654 0.9899 0.9516
Calculated Cone. (ng/mL)
1.70 1.80 3.74 18.4
90.5
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9372 0.9475 1.0648 0.9434
Calculated Cone. (ng/mL)
1.03 0.992 3.67 19.2
85.6
mPFHS
Cone, ng/g (wet weighp
14.5 14.9 NA NA 14.7 2.9
Cone, ng/g (dry weighp
16.0 16.5 NA NA 16.2 2.9
mPFHS
Cone, ng/g (wet weighp
,5|8.79 (5>8.38
NA NA 8.58 4.9
Cone, ng/g (dry weighp
<5,10.3 (5)9.78
NA NA ^10.0 4.9
%Recovery NA NA 712 90.8
"/Recovery NA NA
(S)93.6 |5)99.1
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 69 of 209
3M Environmental Laboratory P0003268; Interim Report#2
A Spike: Level 1; B Spike: Level 1
Sample Description WGLP07-02-01-043 GLP07-02-01 -043 LMS Low
A Spte: Level 1; B Spte: Level 2
Sample Description GLP07-01-01-044 GLP07-01-01-044 Duplicate GLP07-01-01-044 LMS Low GLP07-01-01-044 LMS High
Sample Comment DALSD DU05 RB 0010 DALSD DU05 RB0010
Sample Comment DAL SD DS01 0 0010 DAL SDDS01 0 0010 DAL SDDS01 0 0010 DALSD DS01 00010 Average %RPD Average %Solids
Dilution Factor
1 1
Mass Extracted (g)
1.0375 0.9990
Calculated Cone. (ng/mL)
<0.0278 0.107
mPFHS
Cone, ng/g (w et weight,)
m <0.211 NA
Cone, ng/g (dry weight)
NA NA
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9684 0.9392 0.9528 1.0091
Calculated Cone. (ng/mL)
0.320 0.282 1.51 6.40
92.0
(i,PFHS
Cone, ng/g (w et weight)
2.64 2.40 NA NA 2.52 9.6
Cone, ng/g (dry weight)
2.87 2.61 NA NA 2.74 9.6
%Recovery NA 82.2
"/Recovery NA NA 75.7 82.8
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 70 of 209
3M Environmental Laboratory P0003268; Interim Reportt2
A Spte: Level 1; B Spte: Level 2
Sample Description GLP07-01-01-045 GLP07-01-01-045 Duplicate GLP07-01-01-045 LMS Low GLP07-01-01-045 LMS High
A Spte: Level 1; B Spte: Level 2
Sample Description GLP07-01-01-046 GLP07-01-01-046 Duplicate GLP07-01-01-046 LMS Low GLP07-01 -01-046 LMS High
Sample Comment DALSDDS01 00010 DAL SDDS01 0 0010 DAL SDDS01 0 0010 DALSD DS01 0 0010 Average %RPD Average %Solids
Sample Comment DAL SDDS02 0 0010 DAL SDDS02 0 0010 DAL SDDS02 0 0010 DAL SD DS02 0 0010 Average %RPD Average %Solids
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0345 1.0823 0.9614 0.9936
Calculated Cone. (ng/mL)
0.380 0.359 1.67 6.67
91.3
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9512 0.9792 0.9756 0.9964
Calculated Cone. (ng/mL)
0.181 0.167 1.53 6.48
92.8
mPFHS
Cone, ng/g (w et weight)
2.94 2.65 NA NA 2.80 10
Cone, ng/g (dry weight)
3.22 2.91 NA NA 3.06
10
mPFHS
Cone, ng/g (w et weight)
1.52 1.36 NA NA 1.44 11
Cone, ng/g (dry weight)
1.64 1.47 NA NA 1.55 11
%Recovery NA NA 83.4 86.1
%Recovery NA NA 84.7 85.8
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 71 of 209
3M Environmental Laboratory P0003268; Interim Repori#2
A Spike: Level 1; B Spte: Level 2
Sample Description GLP07-02-01-047 GLP07-02-01-047 Dup GLP07-02-01-047 LMS Low GLP07-02-01-047 LMS High
|6|GLP07-02-01-048
A Spte: Level 1; B Spike: Level 1
Sample Description GLP07-01 -01-049 GLP07-01 -01-049 Duplicate GLP07-01-01-049 LMS Low GLP07-01-01-049 LMS High
Sample Comment DAL SDDS02 0 0030 DALSD DS02 00030 DAL SDDS02 0 0030 DALSD DS02 00030 Average %RPD Average %Solids
DAL SDWP01 0 0010
Sample Comment DAL SDWP02 0 0010 DAL SDWP02 0 0010 DAL SDWP02 0 0010 DAL SDWP02 0 0010 Average %RPD Average %Sotids
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9725 0.9180 0.9951 1.0723
Calculated Cone. (ng/mL)
0.530 0.497 3.06 16.9
91.4
mPFHS
Cone, ng/g (w et weight)
|5)4.36 |S)4.33
NA NA 4.35 0.66
Cone, ng/g (dry weight)
|S)4.77 |S)4.74
NA NA " 4.75 0.66
NA NA
(6)n a
(6)NA
,6)n a
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0349 0.9924 1.0687 1.0343
Calculated Cone. (ng/mL)
<0.0278 <0.0278
0.122 1.18
84.7
mPFHS
Cone, ng/g (w et weight)
<0.215 <0.224
NA NA <0.220 NA
Cone, ng/g (dry weight)
<0.254 <0.265
NA NA <0.259
% R ecovery NA NA
(5)93.3 (5l88.9
(6|n a
%Recovery NA NA 93.7 90.7
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 72 of 209
3M Environmental Laboratory P0003268; Interim Repori#2
(1) Unless otherwise specified, the recovery of associated laboratory matrix spikes was within 10030% indicating that method was appropriate for the given matrix. Sample results are considered accurate to within the overall analytical method uncertainty: 10021% (PFHS). See Determination o f Analytical Method Uncertainty section for more information. Sample results are reported to three significant figures and %RPD to two significant figures. Additional significant figures were used to calculate the average, %RPD, and %recovery. Values in the raw data may vary slightly due to rounding.
(2) %RPD of sample and sample duplicate exceeded 30%. (3) One or more lab matrix spike recoveries exceeded 10030% but was within 100+50%; therefore, sample uncertainty expanded to 10050%. See Data and Results
Discussion section for more information. (4) Sample was an aqueous equipment rinseate blank. Results are reported in units of ng/g (based on native wet weight). Rinseate sample was not extracted in duplicate.
The aqueous rinseate sample was treated the same as a "solid" sediment sample during the extraction and analysis. Results may be biased low by approximately 11 % as the sample contained no visible solids and was actually "diluted" during the extraction procedure. Only one level of LMS was prepared for rinseate samples. (5) Sample uncertainty expanded to 10040% as the samples and spikes were not bracketed by a compliant CCV. See Continuing Calibration section for more information. (6) GLP07-02-01-048 was used as a matrix blank throughout the analyses and produced results less than the LOQ for the given extraction day for each target analyte. See Method Blanks Section for more details. Each day samples were extracted, six individual method blanks, triplicate low level, and triplicate high level lab control spikes were prepared using this matrix. LCS recoveries were reported in Table 12 and indicate that results are accurate to within the overall method uncertainty of 100+21%.
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 73 of 209
3M Environmental Laboratory P0003268; Interim Report2
Table 16. PFOS Sample Results and QC.
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-01-01-001 GLP07-01-01-001 Duplicate GLP07-01-01-001 LMS Low GLP07-01-01-001 LMS High
A Spte: Level 1; B Spike: Level 2
Sample Comment
DALSD EP01 0 0010 DAL SDEP01 0 0010 DALSD EP01 0 0010 DALSD EP01 0 0010 Average %RPD Average %Solids
Sample Description
GLP07-02-01-002 GLP07-02-01-002 Duplicate GLP07-02-01-002 LMS Low GLP07-02-01-002 LMS High
Sample Comment
DAL SDEP02 0 0010 DALSD EP02 0 0010 DAL SDEP02 0 0010 DAL SDEP02 0 0010 Average %RPD Average %Solids
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9580 0.9951 0.9804 0.9933
Calculated Cone. (ng/mL)
23.9 20.2
49.2
129
84.0
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0685 1.0194 1.0139 1.0271
Calculated Cone. (ng/mL)
62.3
59.5
83.8
159
86.9
01PFOS
Cone, ng/g (w et weight)
200 162 NA NA 181 21
Cone, ng/g (dry weight)
238 193 NA NA 215 21
mPFOS
Cone, ng/g (w et weight)
466 467 NA NA 467 0.11
Cone, ng/g (dry weight)
537 537 NA NA 537 0.11
%Recovery NA NA 86.5 82.5
%Recovery NA NA 78.9 76.7
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 74 of 209
3M Environmental Laboratory P0003268; Interim Reportit2
A Spte: Level 1; B Spte: Level 2
Sample Description GLP07-02-01-003 GLP07-02-01-003 Duplicate GLP07-02-01-003 LMS Low GLP07-02-01-003 LMS High
A Spte: Level 1; B Spte: Level 2
Sample Description GLP07-02-01 -004 GLP07-02-01 -004 Duplicate GLP07-02-01 -004 LMS Low GLP07-02-01 -004 LMS High
Sample Comment DALSD EP02 0 0030 DALSD EP02 0 0030 DALSD EP02 0 0030 DALSD EP02 0 0030 Average %RPD Average %Solids
Sample Comment DALSD EP02 0 0045 DAL SD EP02 0 0045 DAL SDEP02 0 0045 DAL SDEP02 0 0045 Average %RPD Average %Solids
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0315 0.9915 0.9969 0.9543
Calculated Cone. (ng/mL)
22.4
17.7
43.9
117
85.4
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9039 0.9822 0.9468 1.0287
Calculated Cone. (ng/mL)
11.9 20.2
42.8
107
84.3
mPFOS
Cone, ng/g (w et weight)
174 143 NA NA 158 20
Cone, ng/g (dry weight)
203 167 NA NA 185 20
mPFOS
Cone, ng/g (w et weight)
(3|105 (3|165
NA NA <*135 <*44
Cone, ng/g (dry weight)
(3|125 (3|195
NA NA <*160 <*44
"/Recovery NA NA 77.4 75.9
%Recovery NA NA 85.9
|3,69.4
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 75 of 209
3M Environmental Laboratory P0003268; Interim ReportH2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-005 GLP07-02-01-005 Duplicate GLP07-02-Q1-005 LMS Low GLP07-02-01-005 LMS High
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-01-01-006 GLP07-01-01-006 Duplicate GLP07-01-01-006 LMS Low GLP07-01 -01-006 LMS High
Sample Comment DALSD EP03 0 0010 DAL SDEP03 0 0010 DAL SDEP03 0 0010 DAL SDEP03 00010 Average %RPD Average %Solids
Sample Comment DALSD EP03 0 0030 DALSD EP03 0 0030 DALSD EP03 0 0030 DAL SD EP03 0 0030 Average %RPD Average %Sotids
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0507 1.0281 1.0365 1.0530
Calculated Cone. (ng/mL)
45.8
44.0
74.0
154
90.0
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9672 1.0847 0.9442 1.0643
Calculated Cone. ( ng/mL)
15.7 10.9
40.3
124
84.0
mPFOS
Cone, ng/g (w et weight)
349 342 NA NA 346 1.8
Cone, ng/g (dry weight)
388 381 NA NA 384 1.8
,1>PFOS
Cone, ng/g (w et weight)
130 80.4 NA NA 105 47
Conc.ng/g (dry weight)
155 95.7 NA NA 125 47
%Recovery NA NA 93.6 84.0
%Recovery NA NA 89.3 85.2
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 76 of 209
3M Environmental Laboratory P0003268; Interim Reportit2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-01-01-007 GLP07-01-01-007 Duplicate GLP07-01 -01-007 LMS Low GLP07-01-01-007 LMS High
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01-008 GLP07-02-01-008 Dup GLP07-02-01-008 LMS Low GLP07-02-01-008 LMS High GLP07-02-01-008 LMS High
Sample Comment DAL SD EP03 0 0045 DAL SDEP03 00045 DALSD EP03 0 0045 DAL SDEP03 0 0045 Average %RPD Average %Solids
Sample Comment DAL SDEP04 0 0010 DALSD EP04 0 0010 DAL SDEP04 0 0010 DAL SDEP04 0 0010 DAL SDEP04 0 0010 Average XoRPD Average %Solids
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0897 0.9493 1.0507 1.0036
Calculated Cone.
(ng/mL)
9.85
6.82
34.3
107
86.2
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
1.0529 0.9872 0.9229 0.9492 0.9492
Calculated Cone.
(ng/mL)
168 152
233 NC
1170
84.9
mPFOS
Cone, ng/g (w et weight)
72.3 57.5 NA NA 64.9 23
Cone, ng/g (dry weight)
83.9 66.7 NA NA 75.3 23
(ilPFOS
Cone, ng/g (w et weight)
P)1280 (3,1230
NA NA NA 1311250 3.6
Cone, ng/g (dry weight)
|3,1500 (3|1450
NA NA NA m14S0 3.6
%,Recovery NA NA 82.5 76.5
%Recovery NA NA
|3|68.4 NA 81.1
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 77 of 209
3M Environmental Laboratory P0003268; Interim Reportif2
A Spike: Level 1; B Spike: Level 2
Sample Desorption GLP07-02-01-009 GLP07-02-01-009 Duplicate GLP07-02-01-009 LMS Low GLP07-02-01-009 LMS High
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01 -010 GLP07-02-01-010 Dup GLP07-02-01 -010 LMS Low GLP07-02-01 -010 LMS High GLP07-02-01 -010 LMS High
Sample Comment DALSD EP04 0 0030 DALSD EP04 0 0030 DAL SDEP04 0 0030 DAL SDEP04 0 0030 Average %RPD Average %Solids
Sample Comment DALSD EP05 0 0010 DAL SDEP05 0 0010 DALSD EP05 0 0010 DAL SDEP05 0 0010 DAL SDEP05 0 0010 Average %RPD Average %Solids
Dilution Factor
1 1 1 1
Mass Extracted(g)
0.9885 1.0153 1.0266 1.0372
Calculated Cone. (ng/mL)
45.4
51.6 66.0
166
85.1
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
0.9200 1.0568 0.9131 1.0361 1.0361
Calculated Cone. (ng/mL)
106 131 200 NC 1090
82.0
mPFOS
Cone, ng/g (w et weight)
|3,367 (3,407
NA NA 131387 10
Cone, ng/g (dry w eight
t3,432 (3|477
NA NA m454 10
(vPFOS
Cone, ng/g (w et weight)
922 992 NA NA NA 957 7.3
Cone, ng/g (dry weight)
1120 1210 NA NA NA 1170 7.3
%Recovery NA NA
(3)52.3 89.6
%,Recovery NA NA 70.3 NA 76.7
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 78 of 209
3M Environmental Laboratory P0003268; Interim Reportlt2
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01-011 GLP07-02-01-011 Dup GLP07-02-01-011 LMS Low GLP07-02-01-011 LMS High GLP07-02-01-011 LMS High
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-012 GLP07-02-01 -012 Duplicate GLP07-02-01-012 LMS Low GLP07-02-01 -012 LMS High
Sample Comment DAL SD EP05 DB 0010 DAL SD EP05 DB 0010 DAL SD EP05 DB 0010 DAL SD EP05DB0010 DAL SD EP05DB0010 Average %RPD Average %Solids
Sample Comment DAL SDEP05 0 0030 DALSD EP05 0 0030 DAL SD EP05 0 0030 DALSD EP05 0 0030 Average %RPD Average %Solids
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
1.0015 1.0151 0.9279 0.9456 0.9456
Calculated Cone.
(ng/mL)
105 120 195
NC 1100
82.1
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9960 0.9317 1.0002 1.0336
Calculated Cone. (ng/mL)
24.5
26.1
55.8
123
83.6
mPFOS
Cone, ng/g (w et weight)
839 946 NA NA NA 892 12
Cone, ng/g (dry weight)
1020 1150 NA NA NA 1090
12
mPFOS
Cone, ng/g (w et weight)
197 224 NA NA 210 13
Cone, ng/g (dry weight)
235 268 NA NA 252 13
%Recovery NA NA 70.8 NA 79.0
%Recovery NA NA 94.4 74.2
3U Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 79 of 209
3M Environmental Laboratory P0003268; Interim Report#2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-013 GLP07-02-01-013 Duplicate GLP07-02-01-013 LMS Low GLP07-02-01-013 LMS High
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01-014 GLP07-02-01-014 Dup GLP07-02-01-014 LMS Low GLP07-02-01-014 LMS High GLP07-02-01-014 LMS High
Sample Comment DALSD EP06 0 0010 DALSD EP06 0 0010 DAL SDEP06 0 0010 DALSD EP06 0 0010 Average %RPD Average %Solids
Sample Comment DAL SDEP07 0 0010 DALSD EP07 0 0010 DALSD EP07 0 0010 DALSD EP07 0 0010 DALSD EP07 0 0010 Average %RPD Average %Solids
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9909 0.9638 1.0492 1.0153
Calculated Cone. (ng/mL)
43.4
55.3
91.9
175
90.5
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
1.0017 1.0017 0.9555 1.0250 1.0250
Calculated Cone. (ng/mL)
105 107
173
NC 1030
82.0
lvPFOS
Cone, ng/g (w et weight)
350 459 NA NA 405 27
Cone, ng/g (dry weight)
387 507 NA NA 447 27
,1lPFOS
Cone, ng/g (w et weight)
(3,839 (3|855
NA NA NA m847 1.9
O CM O
Cone, ng/g (dry weight)
|3)1040 NA NA NA
m1030 1.9
"/Recovery NA NA 124 95.7
%Recovery NA NA
w55.6 NA 73.2
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 80 of 209
3M Environmental Laboratory P0003268; Interim Report#2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-015 GLP07-02-01-015 Duplicate GLP07-02-01 -015 LMS Low GLP07-02-01-015 LMS High
A Spite: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-016 GLP07-02-01-016 Duplicate GLP07-02-01-016 LMS Low GLP07-02-01-016 LMS High
Sample Comment DAL SDEP07 0 0030 DAL SD EP07 0 0030 DAL SD EP07 0 0030 DAL SDEP07 0 0030 Average %RPD Average %Solids
Sample Comment DAL SD EP07 0 0045 DALSD EP07 0 0045 DALSD EP07 0 0045 DAL SD EP07 0 0045 Average %RPD Average %Solids
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0663 1.0606 1.0706 1.0711
Calculated Cone. (ng/mL)
40.4
30.9
50.8
123
85.3
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0546 1.0472 1.0852 0.9515
Calculated Cone. (ng/mL)
29.8
34.2
53.5
128
87.2
PFOS
Cone, ng/g {wet weight)
(4)303 t4233
NA NA (4I268 26
Cone, ng/g {dryweight)
|4)355 (4|273
NA NA m314 26
PFOS
Cone, ng/g (w et weight)
Cone, ng/g {dryweight)
o> to CM
(3|261 NA NA
m244 14
(3|300 NA NA
m279 14
%Recovery NA NA
(4|47.8 (4|67.4
%Recovery NA NA
(3|65.5 76.6
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 81 of 209
3M Environmental Laboratory P0003268; Interim Reportlt2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-017 GLP07-02-01-017 Duplicate GLP07-02-01-017 LMS Low GLP07-02-01-017 LMS High
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01-018 GLP07-02-01-018 Dup GLP07-02-01-018 LMS Low GLP07-02-01-018 LMS High GLP07-02-01-018 LMS High
Sample Comment DALSD EP07DB0045 DALSD EP07 DB0045 DALSD EP07DB0045 DAL SD EP07 DB 0045 Average %RPD Average %Solids
Sample Comment DAL SDEP08 0 0010 DAL SDEP08 0 0010 DAL SDEP08 0 0010 DAL SDEP08 0 0010 DAL SDEP08 0 0010 Average %RPD Average %Solids
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0298 0.9724 1.0019 0.9140
Calculated Cone. (ng/mL)
22.8
20.1
48.3
129
85.2
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
0.9513 0.9857 1.0233 0.9459 0.9459
Calculated Cone.
(ng/mL)
86.5 92.2
188 NC 1110
85.0
{)PFOS
Cone, ng/g {wet weight)
177 165 NA NA 171 6.9
Cone, ng/g (dry weight)
208 194 NA NA 201 6.9
mPFOS
Cone, ng/g (w et weight)
727 748 NA NA NA 738 2.8
Cone, ng/g (dry weight)
856 880 NA NA NA 868 2.8
%Recovery NA NA 86.0 84.7
%Recovery NA NA 72.5 NA 81.2
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 82 of 209
3M Environmental Laboratory P0003268; Interim Report#2
Sample Description GLP07-02-01-019 GLP07-02-01-019 Dup GLP07-02-01-019 LMS Low GLP07-02-01-019 LMS High
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-020 GLP07-02-01-020 Dup GLP07-02-01 -020 LMS Low GLP07-02-01-020 LMS High
Sample Comment DAL SD EP09 0 0010 DAL SDEP09 0 0010 DAL SDEP09 0 0010 DAL SDEP09 0 0010 Average %RPD "/Solids
Sample Comment DAL SDEP09 0 0030 DAL SDEP09 0 0030 DAL SDEP09 0 0030 DALSD EP09 0 0030 Average %RPD %Solids
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0559 1.0364 1.0085 1.0674
Calculated Cone. (ng/mL)
75.4
71.6
86.6
158
83.9
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9214 1.0577 1.0120 1.0741
Calculated Cone. (ng/mL)
16.7
22.5
46.9
125
84.3
mPFOS
Cone, ng/g (w et weight)
|3)571 ,3|553
NA NA p)562 3.3
Cone, ng/g (dry w eight
|3)681 p)659
NA NA m670 3.3
VpFOS
Cone, ng/g (w et weight)
145 170 NA NA 158 16
Cone, ng/g (dry weight)
172 202 NA NA 187 16
%Recovery NA NA
,3)50.4 (3)64.3
%Recovery NA NA 86.3 80.4
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 83 of 209
3M Environmental Laboratory P0003268; Interim Reportit2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-021 GLP07-02-01-021 Dup GLP07-02-01-021 LMS Low GLP07-02-01-021 LMS High
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01-022 GLP07-02-01-022 Dup GLP07-02-01-022 LMS Low GLP07-02-01-022 LMS High GLP07-02-01 -022 LMS High
Sample Comment DALSD EP09 0 0045 DALSD EP09 0 0045 DAL SD EP09 0 0045 DALSD EP09 0 0045 Average %RPD Average %Solids
Sample Comment DALSD EP100 0010 DALSD EP10 0 0010 DALSD EP10 0 0010 DALSD EP10 0 0010 DALSD EP10 0 0010 Average %RPD Average %Solicls
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0314 0.9683 0.9274 1.0552
Calculated Cone.
(ng/mL)
7.05 12.2
30.5
117
83.3
Dilution Factor
1 1 1 1 5
Mass Extracted(g)
0.9243 1.0539 1.0876 1.0918 1.0918
Calculated Cone.
(ng/mL)
93.9 109 199
NC 1120
84.7
mPFOS
Cone, ng/g (w et weight)
(3,54.7 (3|101
NA IMA 77.7 59
Cone, ng/g (dry weight)
(3)65.7 ,3>121
NA NA 93.3 59
PFOS
Cone, ng/g (w et weight)
(3)813 (3|827
NA NA NA 820 1.8
Cone, ng/g (dry weight)
(3|960 <3,977
NA NA NA 968 1.8
%Recovery NA NA
(3|68.8 82.6
%Recovery NA NA
|3|67.7 NA 80.0
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 84 o f 209
3M Environmental Laboratory P0003268; Interim Reportit2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-023 GLP07-02-01-023 Dup GLP07-02-01-023 LMS Low GLP07-02-01-023 LMS High
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-024 GLP07-02-01-024 Dup GLP07-02-01-024 LMS Low GLP07-02-01-024 LMS High
Sample Comment DAL SD EP10 0 0030 DAL SD EP10 0 0030 DAL SD EP10 0 0030 DAL SDEP10 0 0030 Average %RPD Average %Solids
Sample Comment DALSD EP10 0 0045 DALSD EP10 0 0045 DALSD EP10 0 0045 DALSD EP10 0 0045 Average %RPD Average %Solids
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9282 1.0811 1.0848 0.9999
Calculated Cone. (ng/mL)
16.4
17.2
41.0 122
82.8
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0419 0.9957 1.0422 1.0300
Calculated Cone. (ng/mL)
19.1 11.2
44.3
125
85.1
mPFOS
Cone, ng/g (w et weight)
141 127 NA NA 134 10
Cone, ng/g (dry weight)
171 154 NA NA 162 10
,1lPFOS
Cone, ng/g (w et weight)
147 90.0 NA NA 118 48
Cone, ng/g (dry weight)
172 106 NA NA 139 m48
%Recovery NA NA 72.9 81.4
%Recovery NA NA 92.5 85.0
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 85 of 209
3M Environmental Laboratory P0003268; Interim Reportif2
A Spre: Level 3; B Spike: Level 3
Sample Description GLP07-02-01-025 GLP07-02-01-025 Dup GLP07-02-01-025 LMS Low GLP07-02-01-025 LMS High GLP07-02-01-025 LMS High
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01 -026 GLP07-02-01-026 Dup GLP07-02-01-026 LMS Low GLP07-02-01 -026 LMS High
Sample Comment DALSD EP11 0 0010 DALSD EP11 0 0010 DALSD EP11 0 0010 DALSD EP11 00010 DALSD EP11 0 0010 Average %RPD Average %Solids
Sample Comment DALSD EP11 0 0030 DALSD EP11 0 0030 DALSD EP11 0 0030 DALSD EP11 0 0030 Average %RPD Average %Solids
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
0.9626 0.9955 1.0097 1.0241 1.0241
Calculated Cone.
(ng/mL)
82.3 83.4
181
NC 1080
92.0
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0064 0.9796 1.0121 1.0583
Calculated Cone. (ng/mL)
16.2
26.5
52.1
141
85.9
,1)PFOS
Cone, ng/g (w et weight)
684 670 NA NA NA 677 2.0
Cone, ng/g (dry weight)
744 729 NA NA NA 736 2.0
mPFOS
Cone, ng/g (w et weight)
129 216 NA NA 173 n 51
Cone, ng/g (dry weight)
150 252 NA NA 201 51
%Recovery NA NA 73.9 NA 78.9
% R ecovery NA NA 96.9 91.5
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 86 of 209
3M Environmental Laboratory P0003268; Interim Repori#2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-027 GLP07-02-01-027 Dup GLP07-02-01-027 LMS Low GLP07-02-01-027 LMS High
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-028 GLP07-02-01-028 Dup GLP07-02-01-028 LMS Low GLP07-02-01-028 LMS High
Sample Comment DALSD EP11 DB 0030 DAL SD EP11 DB 0030 DALSD EP11 DB0030 DALSD EP11 DB 0030 Average %RPD Average %Solids
Sample Comment DALSD EP120 0010 DALSD EP120 0010 DALSD EP12 0 0010 DALSD EP120 0010 Average %RPD Average %Solids
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9617 0.9785 0.9672 1.0278
Calculated Cone.
(ng/mL)
24.4
27.5
59.1
143
85.2
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0701 0.9479 0.9288 0.9653
Calculated Cone.
(ng/mL)
40.9
33.1
82.8
143
88.1
mPFOS
Cone, ng/g (w et weight)
203 225 NA NA 214 10
Cone, ng/g (dry weight)
238 264 NA NA 251 10
mPFOS
Cone, ng/g (w et weight)
(4|306 |4|279
NA NA m293 9.0
Cone, ng/g (dry weight)
(4|347 (4|317
NA NA m332 9.0
% R ecovery NA NA 106 89.4
%,Recovery NA NA
<4'156 83.4
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 87 of 209
3M Environmental Laboratory P0003268; Interim Repordt2
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01-029 GLP07-02-01-029 Dup GLP07-02-01-029 LMS Low GLP07-02-01-029 LMS High GLP07-02-01-029 LMS High
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-030 GLP07-02-01 -030 Dup GLP07-02-01-030 LMS Low GLP07-02-01-030 LMS High
Sample Comment DAL SDEP13 0 0010 DAL SDEP13 0 0010 DALSDEP13 0 0010 DAL SDEP13 0 0010 DALSD EP13 0 0010 Average %RPD Average %Solids
Sim ple Comment DALSD EP13 0 0030 DALSD EP13 0 0030 DALSD EP13 0 0030 DALSD EP13 0 0030 Average %RPD Average %Solids
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
1.0167 0.9516 0.9971 0.9561 0.9561
Calculated Cone.
(ng/mL)
89.6
83.0 199
NC 1120
94.7
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0329 0.9524 1.0468 1.0301
Calculated Cone.
(ng/mL)
38.6
34.5
62.5
148
85.2
mPFOS
Cone, ng/g (w et weight)
705 698 NA NA NA 701 1.0
Cone, ng/g (dry weight)
744 737 NA NA NA 741 1.0
VpFOS
Cone, ng/g (w et weight)
299 290 NA NA 294 3.1
Cone, ng/g (dry weighty
351 340 NA NA 345 3.1
%Recovery NA NA 86.4 NA 82.3
%Recovery NA NA 76.8 85.2
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 88 of 209
3M Environmental Laboratory P0003268; Interim ReportM2
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01-031 GLP07-02-01-031 Dup GLP07-02-01-031 LMS Low GLP07-02-01-031 LMS High GLP07-02-01 -031 LMS High
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01-032 GLP07-02-01-032 Dup GLP07-02-01-032 LMS Low GLP07-02-01-032 LMS High GLP07-02-01-032 LMS High
Sample Comment DALSD EP14 0 0010 DAL SD EP14 0 0010 DALSD EP14 0 0010 DALSD EP140 0010 DALSD EP14 0 0010 Average %RPD Average %Solids
Sample Comment DALSD EP14DB0010 DALSD EP14DB0010 DAL SDEP14DB 0010 DALSD EP14DB0010 DALSD EP14DB 0010 Average %RPD Average %Solids
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
0.9305 1.0403 0.9865 0.9939 0.9939
Calculated Cone. (ng/mL)
101
115 193
NC 1120
91.6
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
0.9524 0.9351 0.9486 0.9398 0.9398
Calculated Cone. (ng/mL)
98.9 94.2
195 NC 1110
91.0
mPFOS
Cone, ng/g (w et weight)
(3)868 |3,884
NA NA NA m876 1.8
00
Cone, ng/g (dry weight)
|3)966 NA NA NA
m9S7 1.8
,vPFOS
Cone, ng/g (w et weight)
831 806 NA NA NA 818 3.0
Cone, ng/g (dry weight)
913 886 NA NA NA 900 3.0
%Recovery NA NA
<3)65.7 NA 80.3
%Recovery NA NA 75.8 NA 80.5
3M Environmental Laboratory
GLPQ7-02-01, Decatur Sediments Sulfonates
Page 89 of 209
3M Environmental Laboratory P0003268; Interim Repori#2
A Spike: Level 1; B Spike: Level 1
Sample Description wGLP07-02-01 -037 GLP07-02-01-037 LMS Low
A Spike: Level 3; B Spike: Level 3
Sample Description GLP07-02-01-038 GLP07-02-01-038 Dup GLP07-02-01-038 LMS Low GLP07-02-01-038 LMS High GLP07-02-01-038 LMS High
Sample Comment DAL SD DU01 RB 0010 DAL SD DU01 RB 0010
Sample Comment DALSD DU01 0 0010 DAL SD DU01 0 0010 DALSDDU01 0 0010 DALSD DU01 0 0010 DALSDDU01 0 0010 Average %RPD Average %Solids
Dilution Factor
1 1
Mass Extracted (g)
1.0294 1.0481
Calculated Cone.
(ng/mL)
<0.0490
0.0963
(vPFOS
Cone, ng/g (w et weight)
0.380 NA
Cone, ng/g (dry weight)
NA NA
"/(Recovery NA 77.1
Dilution Factor
1 1 1 1 5
Mass Extracted (g)
0.9486 1.0004 0.9503 0.9572 0.9572
Calculated Cone.
(ng/mL)
76.4
93.1 173 NC 1050
90.3
mPFOS
Cone, ng/g (w et weight)
644 745 NA NA NA 694 14
Cone, ng/g (dry weight)
713 824 NA NA NA 769 14
"/R ecovery
NA NA 70.1 NA 76.8
3M Environmental Laboratory
GLP07-02-Q1, Decatur Sediments Sulfonates
Page 90 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ft Spike: Level 1; B Spike: Level 2
Sample Description GLP07-01-01-039 GLP07-01-01-039 Duplicate GLP07-01-01-039 LMS Low GLP07-01-01-039 LMS High
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-01-01-040 GLP07-01 -01-040 Duplicate GLP07-01 -01-040 LMS Low GLP07-01-01-040 LMS High
Sample Comment DALSD DU02 0 0010 DALSD DU02 0 0010 DALSD DU02 0 0010 DALSD DU02 0 0010 Average %RPD Average %Solids
Sample Comment DALSD DU03 0 0010 DALSD DU03 0 0010 DALSD DU030 0010 DALSD DU03 0 0010 Average %RPD Average %Solids
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9853 0.9781 0.9854 1.0066
Calculated Cone. (ng/mL)
48.2
48.5
66.9
161
89.3
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9563 1.0574 0.9385 0.9280
Calculated Cone.
(ng/mL)
30.8
29.5
55.1
139
90.2
(1,PFOS
Cone, ng/g (w et weight)
|3)391 |3)397
NA NA m394 1.4
Cone, ng/g (dry weight)
(3,438 (3)444
NA NA m441 1.4
mPFOS
Cone, ng/g (w et weight)
258 223 NA NA 240 14
Cone, ng/g (dry weight)
286 248 NA NA 267 14
%Recovery NA NA
ra58.8 86.2
%Recovery NA NA 86.1 86.0
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 91 of 209
3M Environmental Laboratory P0003268; Interim Report#2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-041 GLP07-Q2-01-041 Dup GLP07-02-01 -041 LMS Low GLP07-02-01 -041 LMS High
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-042 GLP07-02-01-042 Dup GLP07-02-01 -042 LMS Low GLP07-02-01-042 LMS High
Sample Comment DALSD DU04 0 0010 DAL SD DU040 0Q10 DALSD DU04 0 0010 DAL SDDU04 0 0010 Average %RPD Average %Soiids
Sample Comment DALSD DU05 0 0010 DALSD DU05 0 0010 DALSD DU05 0 0010 DAL SDDU05 0 0010 Average %RPD Average yoSolids
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9389 0.9654 0.9899 0.9516
Calculated Cone. (ng/mL)
74.0
77.4
88.9
180
90.5
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9372 0.9475 1.0648 0.9434
Calculated Cone. (ng/mL)
77.2
75.8
107
191
85.6
mPFOS
Cone, ng/g (w et weight)
631 641 NA NA 636 1.7
Cone, ng/g (dry w eight
696 708 NA NA 702 1.7
,vPFOS
Cone, ng/g (w et weight)
(6)659 |6,640
NA NA ,e>649 2.9
Cone, ng/g (dry weight)
|6)770 (S|748
NA NA m759 2.9
%Recovery NA NA NR 80.8
"/Recovery NA NA NR
|6|88.6
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 92 of 209
3M Environmental Laboratory P0003268; Interim ReportH2
A Spike: Level 1; B Spike: Level 1
Sample Description WGLP07-02-01-043 GLP07-02-01-043 LMS Low A Spte: Level 1; B Spike: Level 2
Sample Desorption GLP07-01-01-044 GLP07-01-01-044 Duplicate GLP07-01-01-044 LMS Low GLP07-01-01-044 LMS High
A Spike: Level 1; B Spike: Level 2
Sample Desorption GLP07-01-01-045 GLP07-01-01-045 Duplicate GLP07-01-01-045 LMS Low GLP07-01-01-045 LMS High
Sample Comment DAL SD DU05RB 0010 DAL SD DU05RB0010
Sample Comment DAL SDDS01 0 0010 DAL SDDS01 0 0010 DAL SDDS01 0 0010 DAL SDDS01 0 0010 Average %RPD Average "/Solids
Sample Comment DALSDDS01 00010 DAL SDDS01 0 0010 DALSDDS01 0 0010 DAL SDDS01 0 0010 Average %RPD Average %Solids
Dilution Factor
1 1
Mass Extracted (g)
1.0375 0.9990
Calculated Cone. (ng/mL)
<0.0490
0.110
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9684 0.9392 0.9528 1.0091
Calculated Cone. (ng/mL)
71.1
66.4
89.6 174
92.0
Dilution Factor
1 1 1 1
Mass Extracted (g)
1.0345 1.0823 0.9614 0.9936
Calculated Cone. (ng/mL)
35.9
29.9
55.5
140
913
mPFOS
Cone, ng/g (w et weight)
Cone, ng/g (dry weight)
w<0.378 NA mPFOS
NA NA
Cone, ng/g (w et weight)
587 566 NA NA 576 3.8
Cone, ng/g (dry weight)
639 615 NA NA 627 3.8
mPFOS
Cone, ng/g (w et weight)
278 221 NA NA 249 23
Cone, ng/g (dry weight)
304 242 NA NA 273 23
%Recovery NA 88.0
%Recovery NA NA NR 78.4
"/Recovery NA NA 81.7 84.4
3M Environmental Laboratory
GLP07-02-01, Dec tur Sediments Sulfonates
Page 93 of 209
3M Environmental Laboratory P0003268; Interim Report#2
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-01 -01-046 GLP07-01-01-046 Duplicate GLP07-01-01-046 LMS Low GLP07-01-01-046 LMS High
A Spike: Level 1; B Spike: Level 2
Sample Description GLP07-02-01-047 GLP07-02-01-047 Dup GLP07-02-01 -047 LMS Low GLP07-02-01-047 LMS High
(7|GLP07-02-01 -048
Sample Comment DAL SD DS02 0 0010 DAL SDDS02 0 0010 DAL SDDS02 0 0010 DAL SDDS02 0 0010 Average %RPD Average %Solids
Sample Comment DAL SDDS02 0 0030 DAL SDDS02 0 0030 DAL SDDS02 0 0030 DAL SDDS02 0 0030 Average %RPD Average %Solids
DAL SDWP01 0 0010
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9512 0.9792 0.9756 0.9964
Calculated Cone. (ng/mL)
68.0
70.0
98.6
184
92.8
Dilution Factor
1 1 1 1
Mass Extracted (g)
0.9725 0.9180 0.9951 1.0723
Calculated Cone.
(ng/mL)
61.3
58.5
94.9
171
91.4
n PFOS
Cone, ng/g (met weight)
572 572 NA NA 572 0.0
Cone, ng/g (dry weight)
616 616 NA NA 616 0.0
mPFOS
Cone, ng/g (w et weight)
|6)504 |6|510
NA NA <6I507 1.1
Cone, ng/g (dry weight)
,6|552 (s|558
NA NA m555 1.1
%Recovery NA NA NR 87.3
%Recovery NA NA
|s|102 (6|79.8
NA NA
(7|n a
,7|n a
|7)n a
|7)n a
3U Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 94 of 209
3M Environmental Laboratory P0003268; Interim Report#2
A Spike: Level 1; B Spike: Level 1
tvPFOS
Sample Description
Sample Comment
Dilution Factor
Mass Extracted (g)
Calculated Cone. (ng/mL)
Cone, ng/g (w et weight)
Cone, ng/g (dry weight)
%Recovery
GLP07-01 -01-049 GLP07-01 -01-049 Duplicate GLP07-01-01-049 LMS Low GLP07-01-01-049 LMS High
DAL SDWP02 0 0010 DAL SDWP02 0 0010 DAL SDWP02 00010 DAL SDWP02 0 0010
1
1.0349
<0.0245
<0.189
1
0.9924
<0.0245
<0.198
1
1.0687
0.102
NA
1 1.0343 1.21
NA
<0.223 <0.233
NA NA
NA NA 81.6 96.8
Average
<0.193
<0.228
%RPD
NA NA
Average %Solids
84.7
(1) Unless otherwise specified, the recovery of associated laboratory matrix spikes was within 10030% indicating that method was appropriate for the given matrix. Sample results are considered accurate to within the overall analytical method uncertainty of 10030% (PFOS). See Determination of Analytical Method Uncertainty section for more information. Sample results are reported to three significant figures and %RPD to two significant figures. Additional significant figures were used to calculate the average, %RPD, and %recovery. Values in the raw data may vary slightly due to rounding.
(2) %RPD of sample and sample duplicate exceeded 30%.
(3) One or more lab matrix spike recoveries exceeded 10030% but was within 10050%; therefore, sample accuracy expanded to 10050%. See Data and Results Discussion section for more information.
(4) One of the lab matrix spike recoveries exceeded 10050% but was within 10060%; therefore the sample uncertainty expanded to 10060%. See Data and Results Discussion section for more information.
(5) Sample was an aqueous equipment rinseate blank. Results are reported in units of ng/g (based on native wet weight). Rinseate sample was not extracted in duplicate. The aqueous rinseate sample was treated the same as a "solid" sediment sample during the extraction and analysis. Results may be biased low by approximately 11 % as the sample contained no visible solids and was actually "diluted" during the extraction procedure. Only one level of LMS was prepared for rinseate samples.
(6) Sample uncertainty expanded to 10040% as the samples and spikes were not bracketed by a compliant CCV. See Continuing Calibration section for more information.
(7) GLP07-02-01-048 was used as a matrix blank throughout the analyses and produced results less than the LOQ for the given extraction day for each target analyte. See Method Blanks Section for more details. Each day samples were extracted, six individual method blanks, triplicate low level, and triplicate high level spikes were prepared using this matrix. LCS recoveries were reported in Table 12 and indicate that results are accurate to within the overall method uncertainty of 10030%.
NC: Not calculated. Instrument could not calculate a concentration as the resultant area counts exceeded the upper limit of the calibration curve.
NR: Not reported. Spike level was less than half the endogenous concentration.
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 95 of 209
3M Environmental Laboratory P0003268; Interim Report#2
Statistical Methods and Calculations
Statistical methods used to interpret sample results include averages and standard deviations. The Analyst software programs calculated sample concentrations using resultant analyte peak areas and the established quadratic, 1/x weighted, calibration curve. Sample calculations and equations used to report method accuracy and precision are described below.
Accuracy and Precision Equations
Calculated Concentration LCS Percent Recovery =
100%
Spike Concentration
% RSD (Relative Standard Deviation) = standard deviation of replicates . 1Q0% replicate average
% RPD (Relative Percent Difference) = Absolute_difference between sample duplicates . 10Q% average sample concentration
Determination of Analytical Method Uncertainty
The analytical method uncertainty for the PFBS, PFHS, and PFOS results was determined using the procedures outlined in ETS 12-12.2 "Estimation of Uncertainty of Measurements" where the standard deviation of all the lab control spikes and reportable lab matrix spike recoveries was calculated (in %). The expanded uncertainty was determined by multiplying the standard deviation by a factor of 2, which corresponds to the 95% confidence level. All LCS recoveries were presented in Table 12 and all reportable LMS recoveries can be found in Table 14, Table 15, and Table 16. Table 17 below summarizes the average LCS and LMS recovery and the standard deviation. The expanded analytical method uncertainty (95% confidence level) was used to assign the overall analytical method uncertainty to the final results presented in Table 1 and the QC summary tables when the lab matrix spikes produced recoveries within 10030%. If the lab matrix spike recoveries exceeded 10030% or the samples were bracketed by a non-compliant CCV recovery, the overall sample uncertainty was extended accordingly.
Table 17. Analytical Method Uncertainties.
PFBS
Average LCS and LMS Recovery
Standard Deviation of LCS and LMS Recoveries
104 9.8
2* Standard Deviation of LCS and LMS Recoveries
19.7
Reported Analytical Method Uncertainty
10020%
PFHS 85.3 10.4
20.8
10021%
PFOS 85.1 15.1
30.3
10030%
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 96 of 209
3M Environmental Laboratory P0003268; Interim Report#2
Statement of Conclusion
Sample results were summarized in Table 1. Lab control spikes and lab matrix spike recoveries were used to determine the overall analytical method uncertainty: 10020% (PFBS), 10021% (PFHS), and 10030% (PFOS). Sample results with lab matrix spike recoveries within 10030% were considered to be accurate within the stated method uncertainty. Samples with lab matrix spike recovery exceeding 10030% or bracketed by a non-compliant CCV recovery were reported with an expanded sample uncertainty.
References
ETS 8-12.1 "Method of Analysis for the Determination of Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid (PFPeA), Perfluorohexanoic Acid (PFHA), Periluoroheptanoic Acid (PFHpA), Periluorooctanoic 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".
ETS 12-012.2 "Estimation of Uncertainty of Measurements".
List of Attachments
Attachment A: Selected Chromatograms and Calibration Curves Attachment B: Extraction and Analytical Methods Attachment C: Protocol and Protocol Amendments Attachment D: Protocol and/or Method Deviations
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 97 of 209
Signatures
3M Environmental Laboratory P0003268; Interim Report#2
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 98 of 209
3M Environmental Laboratory P0003268; Interim ReporW2
Attachment A: Sample Chromatograms and Calibration Curves
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 99 of 209
3M Environmental Laboratory P0003268; Interim Reporttt2
'Stan VI660305
Resulta Nans: s071 0 2 tra1.idb
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 100 of 209
Stan VI660305
3M Environmental Laboratory P0003268; Interim Report#2
Rasulta Nana: 80710234 final.rdb
8 ]"
Stan V166030S
'1*11'
,___
' "
'
" '
'rlntin 'rintin Data: Monday. January 21. 2006
'
Raaulta Nana: a071023a_fInal.rdb
8 iTM
Pag* 6 of 24
1 ... ' * ` ' ,__ M * " " "
'rintin 'rlntin Data; Monday. January 21. 2006
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 101 of 209
3M Environmental Laboratory P0003268; Interim Reporttt2
Ilk ,, f. =
ir # l
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 102 of 209
V166030S
3M Environmental Laboratory P0003268; Interim Report#2
Risulta Nan; a031023a_finai.fdb
V166030S
Risulta NAM; 031023a_finai.idb
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 103 of 209
3M Environmental Laboratory P0003268; Interim Report#2
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 104 o f 209
"Stan V166030S
3M Environmental Laboratory P0003268; Interim Report#2
Riults Man: sOH 023a_finai.rdb
Stan V166030S
Resulta Nam: 9011023a final.rdb
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 105 of 209
'1660305
3M Environmental Laboratory P0003268; Interim Report#2
' 1023#_ftnal.rdb
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 106 of 209
Stan vl660305
3M Environmental Laboratory P0003268; Interim Report#2
Raaults Ham: 011023a_flnal.rdb
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 107 of 209
'Stiri VI660305
3M Environmental Laboratory P0003268; Interim ReporW2
Rulta Nana: a0H023a_fInal.rdb
Stan V1660305
Rasulta Nan: a071023a_final.rdb
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 108 o f 209
"Stan V166030S
!r
Pg. 19 of 2^ "Scan VI660305
3M Environmental Laboratory P0003268; Interim Report#2
Rsaults Nans: a03102 3_finai.rdb
_ j j.....
Printing Tin: 2:16 Printing Oat; Honda January 21, 2006 Paaults Nam: s07102
-
Pag. 20 of 2*
_____________ ,_________________________________ _______ _______ .___.________ -v.__
L
Printing Tim: 2:16 .5 PM
.
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 109 of 209
Stan VIM03QS
I '**
1:::
Pg. 21 of 24 Still V16S030S
3M Environmental Laboratory P0003268; Interim Report#2
Rtault* SbF.i' 0
. ___________________________ Printing Tim: 2 Printing Dat: Honday, January 21, 2009 Raaulta Nam) 0 1023a_final,rdb
i:
Pig* 22 of 24
, ,______________________________
Printing Tin: 16:15 PM Printing Dat: Honday, January 21, 2006
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 110 of 209
'Stan VI660305
3M Environmental Laboratory P0003268; Interim Report#2
Rasulta Nana: aQ 1023a_(inal.rdb
t ...
Pa,. 23 of 24 Stan VI660305
, ,______________________________ Printing Tina: 2 Printing Data: H nday, January 21, 2006
Paaulta Nana: SO 1023a_flnal.rdb
I-
P.g. 24 of 24
, . ___________________________
Printing Tima: 2
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 111 of 209
**Stan V1660305
3M Environmental Laboratory P0003268; Interim Report#2
Results Name: s071023a_finai.rdb
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 112 of 209
**Stan V1660305
3M Environmental Laboratory P0003268; Interim Report#2
Results Name: s071023a final.rdb
Page 1 of 1
3M Environmental Laboratory
Printing Time: 2:21:16 PM Printing Date: Monday, January 21, 2008
GLP07-02-01, Decatur Sediments Sulfonates
Page 113 of 209
* * Stan V1660305
3M Environmental Laboratory P0003268; Interim Report#2
Results Name: sD71023a_final.rdb
3M Environmental Laboratory
QLP07-02-01, Decatur Sediments Sulfonates
Page 114 of 209
3M Environmental Laboratory P0003268; Interim Report#2
Attachment B: Extraction and A nalytical Methods
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 115 of 209
3M Environmental Laboratory P0003268; Interim Reporf#2
3M Environm ental Laboratory
Method
Method o f Analysis for the Determination o f Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid (PFPeA), Perfluorohexanoic A cid (PFHA), Perfluoroheptanoic Acid (PFHpA), Perfiuorooctanoic Acid (PFOA), Perfluorononanoic Acid (PFNA), Perfiuorodecanoic A cid (PFDA),
Perfluoroundecanoic Acid (PFUnA), Perfluorododecanoic Acid (PFDoA), Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soii and Sediment b y LC/MS/MS
Method Number: ETS-8-012.1
Adoption Date: Upon Signing
Effective Date:
Approved By:
William K. Reagen, Technical Manager
Date
ETS-8-012.1
Page 1 o f! 2
MethodofAnalysisfortheDeterminationofPerfluorobutanoicAdd (PFBA),PerfluoropentanoicAcid(PFPeA),Perfluorohexanoic
Acid(PFHA),PerfluoroheptanoicAcid(PFHpA),PerfiuorooctanoicAcid(PFOA),PerfluorononanoicAdd (PFNA),Perfiuorodecanoic Add(PFDA),PerfluoroundecanoicAdd(PFUnA),perfluorododecanoicAdd (PFDoA),Perfluorobutanesulfonate(PFBS). Perfluorohexanesulfonate(PFHS),andPerfluorooctanesulfonate(PFOS)inWater,SoilandSedimentbyLC/MS/MS
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 116 of 209
3M Environmental Laboratory P0003268; Interim Report#2
1 Scope and Application
This method is to be used to quantify Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid (PFPeA), Perfluorohexanoic Acid (PFHA), Perfluoroheptanoic Acid (PFHpA), Perfluorooctanoic Acid (PFOA), Perfiuorononanoic Acid (PFNA), Perfluorodecanoic Acid (PFDA), Perfluoroundecanoic Acid (PFUnA), Perfluorododecanoic Acid (PFDoA), Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfbnate (PFHS), and Perfluorooctanesulfonate (PFOS) by High Performance Liquid Chromatography coupled to a tandem Mass Spectromtrie Detector (LC/MS/MS) in water, soil and sediment. The method is designed to target a lower limit of quantitation (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 LC/MS/MS. Similarly, one-gram aliquots of soil and sediments are mixed with 80:20 acetonitrile:water mixture, thoroughly mixed, centrifuged, and aliquoted for analysis by LC/MS/MS.
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 matrix spikes (aqueous samples) or laboratory matrix spikes (soil and sediment) to verify that the method is applicable to each sample matrix. Sample results for spikes outside of 70% to 130%, will not be reported due to non-compliant 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 Defin document may be used, if current, for 14 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)/Trip 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
MethodofAnalysisfortheDeterminationofPerfluorobutanoicAdd (PFBA),PerfluoropentanoicAdd (PFPeA),Perfluorohexanoic Add (PFHA),PerfluoroheptanoicAcid(PFHpA),PerfluoroodanoicAdd (PFOA),PerfiuorononanoicAdd (PFNA),Perfluorodecanoic
Add (PFDA),PerfluoroundecanoicAdd (PFUnA),PerfluorododecanoicAdd (PFDoA),Perfluorobutanesulfonate(PFBS), Perfluorohexanesulfonate(PFHS),and Perfluorooctanesulfonate(PFOS) inWater, Soiland SedimentbyLC/MS/MS
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 117 of 209
icum;
3M Environmental Laboratory P0003268; Interim Report#2
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 quantitation (LLOQ) for a dataset is the lowest concentration that can be reliably quantitated within the specified limits of precision and accuracy during routine operating conditions. To simplify data reporting, the LLOQ is generally selected as the lowest non-zero standard in the calibration curve that meets method criteria. Sample LLOQs are matrix-dependent.
The upper limit of 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
MethodofAnalysisfortheDeterminationofPerfluorobutanoicAcid(PFBA),PerfluoropentanolcAdd (PFPeA),Perfluorohexanoic Acid(PFHA),PerfluoroheptanoicAcid(PFHpA),PerfluorooctanolcAdd (PFOA),PerfluorononanolcAdd (PFNA),Perfluorodecanolc
Add (PFDA),PerfluoroundecanolcAdd (PFUnA),PerfluorododecanolcAdd (PFDoA),Perfluorobutanesulfonate(PFBS), Perfluorohexanesulfonate(PFHS),andPerfluorooctanesulfonate(PFOS)InWater,SoilandSedimentbyLC/MS/MS
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 118 o f 209
This docum ent m ay be u s e d b c u irs n l, for 14 davs fro-:" 11 -;3
3M Environmental Laboratory P0003268; Interim Report#2
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 quantity 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 quality 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 Warnings and Cautions
4.1 Health and Safety
The acute and chronic toxicity of the standards for this method have not been precisely determined; however, each should be treated as a potential health hazard. 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
MethodofAnalysisfortheDeterminationofPerfluorobutanoicAcid(PFBA),PerfluoropentanoicAdd (PFPeA),Perfluorohexanoic
Add (PFHA),PerfluoroheptanoicAcid(PFHpA),PerfluorooctanoicAdd (PFOA),PerfluorononanoicAdd (PFNA),Perfluorodecanoic Add (PFDA),PerfluoroundecanoicAcid(PFUnA),PerfluorododecanoicAdd (PFDoA),Perfluorobutanesulfonate(PFBS), Perfluorohexanesulfonate(PFHS),andPerfluorooctanesulfonate(PFOS)inWater,SoilandSedimentbyLC/MS/MS
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 119 o f 209
3M Environmental Laboratory P0003268; Interim Report#2
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/MS/MS). Applied Biosystems Sciex API 5000 instrumentation is required to meet the LOQs of 0.025 ng/mL (water) and 0.20 ng/g (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 collect raw data for peak integration and quantitation.
15-mL 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 (P/N: 00M-4248-D0-CE)
Temperature: 35C
Mobile Phase (A): 2 mM Ammonium Acetate in Water
Mobile Phase (B): Methanol
Gradient Program:
Time (mini
%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 (mL/minl
0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75
Quantitation: Peak Area - external standard calibration curve, 1/x weighted. ETS-8-012.1
Page 5 o f 12
MethodofAnalysisfortheDeterminationofPerfluorobutanoicAcid(PFBA),PerfluoropentanoicAdd (PFPeA),Perfluorohexanoic Acid(PFHA),PerfluoroheptanoicAcid(PFHpA),PerfluorooctanoicAdd (PFOA),PerfluorononanoicAdd (PFNA),Perfluorodecanoic
Add (PFDA),PerfluoroundecanoicAdd (PFUnA),PerfluorododecanoicAdd (PFDoA),Perfluorobutanesulfonate(PFBS), Perfluorohexanesulfonate(PFHS),andPerfluorooctanesulfonate(PFOS)inWater,SoilandSedimentbyLC/MS/MS
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 120 of 209
w;;:? iiH v he used, h c u s s e s tor 14 have from t l a ! 3
3M Environmental Laboratory P0003268; Interim R e p o rts
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 MS/MS System
6.3.1
Mode: Electrospray Negative MRM mode, monitoring the following transitons:
Analyte
Transition Monitored
PFBA
213 -> 169
PFPeA
263 ->219
PFHA
3 1 3 -> 2 6 9 and 313 -> 1 1 9
PFHpA
363 -> 319, 363 -> 169 and 363 -> 1 1 9
PFOA
413 -> 369, 413 -> 219 and 413 -> 169
PFNA
463 -> 419, 463 -> 169 and 463 - > 2 1 9
PFDA
5 1 3 -> 4 6 9 , 5 1 3 -> 2 1 9 and 5 1 3 -> 2 6 9
PFUnA
563 -> 519, 563 -> 269 and 563 -> 219
PFDoA
613 -> 569, 613 -> 169 and 613 - > 3 1 9
PFBS
299 -> 80 and 299 -> 99
PFHS
399 -> 80 and 399 -> 99
PFOS
499 -> 80, 499 -> 99 and 499 -> 130
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.
7 Reagents and Standards
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 PerfluorohexanoicAcid (PFHA) - Oakwood Products, Inc Perfluoroheptanoic Acid (PFHpA) - Oakwood Products, Inc Perfluorooctanoic Acid (PFOA) - Oakwood Products, Inc Perfluorononanolc Acid (PFNA) - Oakwood Products, Inc PerfluorodecanoicAcid (PFDA) - Oakwood Products, Inc Perfluoroundecanoic Acid (PFUnA) - Oakwood Products, Inc Perfluorododecanoic Acid (PFDoA) - Oakwood Products, Inc
ETS-8-012.1
Page 6 o f 12
MethodofAnalysisfortheDeterminationofPerfluorobutanoicAcid(PFBA),PerfluoropentanoicAcid(PFPeA),Perfluorohexanoic Acid(PFHA),PerfluoroheptanoicAcid(PFHpA),PerfluorooctanoicAcid(PFOA),PerfluorononanoicAcid(PFNA),Perfluorodecanoic
Acid(PFDA),PerfluoroundecanoicAcid(PFUnA),PerfluorododecanoicAcid(PFDoA),Perfluorobutanesulfonate(PFBS),
Perfluorohexanesulfonate(PFHS),and Perfluorooctanesulfonate(PFOS) inWater,Soiland SedimentbyLC/MS/MS
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 121 of 209
3M Environmental Laboratory P0003268; Interim Report#2
Perfluorobutanesulfnate (PFBS) - 3M Perfluorohexanesulfonate (PFHS) - 3M Perfluorooctanesulfonate (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
8.1.1
Measure 10mL of sample into a 50-mL polypropylene centrifuge tube. Fortifications are to be done at this point, if necessary. Other volumes and containers may be used as appropriate.
8.1.2 Add 10 mL of acetonitrile to the sample in the centrifuge tube. Cap tightly and shake.
8.1.3 Sonicate sample for ~2 hours at room temperature. This step is optional, but is recommended if particulates appear to be present.
8.1.4 Centrifuge for ~10 minutes at -3000 rpm. This step is optional, but is recommended if samples are sonicated.
8.1.5 Transfer a portion of the supernatant to an autosampler vial for analysis.
8.1.6 Dilute sample, if necessary, with 50:50 acetonitrilewater.
8.2 Soil and Sediment Extraction
8.2.1 W eighl g of sample into a 15-mL polypropylene centrifuge tube. Fortifications are to be done at this point, if necessary.
8.2.2 Add 8 mL of 80:20 acetonitrilewater to the sample in the centrifuge tube. Cap tightly and shake.
8.2.3 Sonicate sample for ~2 hours at room temperature.
8.2.4 Centrifuge for ~10 minutes at ~3000 rpm.
8.2.5 Transfer a portion of the supernatant to an autosampler vial for analysis.
8.2.6 Dilute sample, if necessary, with 50:50 acetonitrilewater.
8.2.7
Analyze samples using electrospray LC/MS/MS
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.
9 Sample Analysis - LC/MS/MS
ETS-8-012.1
Page 7 o f 12
MethodofAnalysisfortheDeterminationofPerfluorobutanoicAdd (PFBA),PerfluoropentanoicAdd (PFPeA),Perfluorohexanoic Acid(PFHA),PerfluoroheptanoicAdd (PFHpA),PerfluorooctanoicAdd (PFOA),PerfluorononanoicAdd (PFNA),Perfluorodecanoic
Add (PFDA),PerfluoroundecanoicAdd (PFUnA),PerfluorododecanoicAdd (PFDoA),Perfluorobutanesulfonate(PFBS), Perfluorohexanesulfonate(PFHS), and Perfluorooctanesulfonate(PFOS) inWater, Soiland SedimentbyLC/MS/MS
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 122 of 209
3M Environmental Laboratory P0003268; Interim Reporttf2
9.1.1 A minimum of six calibration levels must be present in the final calibration curve.
9.1.2
An entire set of calibration standards is injected at the beginning of a sample set prior to sample analysis. 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 5-10 samples (to account for a second set of standards). 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 curve be analyzed prior to samples and that the continued accuracy of the initial calibration curve be confirmed by the analysis of continuing calibration verification standards. The same approach should be used throughout the entire study unless reasons are documented and technical justification to change is approved prior to sample analysis.
9.1.3
The standard curve is plotted by quadratic fit (y = ax2+ bx + c), weighted 1/x or unweighted, or using a linear fit, weighted 1/x, using suitable software. TTie calibration curves may include but should not be forced through zero. The mathematical method used to calculate the calibration curve should be applied consistentlythroughout a study. Any change should be documented in the raw data.
9.1.4 Samples containing analytes that are quantitated above the concentration of the highest standard in the curve should be further diluted and reanalyzed or re-injected 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 +1-30% 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 Blanks
10.2.1 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.
10.2.2 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.
10.3 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
MethodofAnalysisfortheDeterminationofPerfluorobutanoioAcid(PFBA),PerfluoropentanoicAcid(PFPeA),Perfluorohexanoic
Acid(PFHA),PerfluoroheptanoicAcid(PFHpA),PerfluorooctanoicAcid(PFOA),PerfluorononanoicAcid(PFNA),Perfluorodecanoic Add (PFDA),PerfluoroundecanoicAcid(PFUnA),PerfluorododecanoicAdd (PFDoA),Perfluorobutanesulfonate(PFBS), perfluorohexanesulfonate(PFHS), and Perfluorooctanesulfonate(PFOS)inWater,Soiland SedimentbyLC/MS/MS
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 123 of 209
3M Environmental Laboratory P0003268; Interim Report#2
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 / 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 necessary) 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.100 mg) and divide by the purity in decimal form (i.e. 99.6% = 0.996). The result is the weight that is needed to make the solution corrected for purity (i.e. weigh 100.4 mg). For salt correction, calculate the salt content by taking the molecular weight of the target compound (i.e. PFOS = 499) and dividing by the molecular weight of the entire compound (i.e. PFOS potassium salt (CeF17S03-K* = 538). The result is the salt content in decimal form (i.e. 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 (i.e. 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 alternative 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 1000 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
MethodofAnalysisfortheDeterminationofPerfluorobutanoicAdd (PFBA),PerfluoropentanoioAdd (PFPeA),Perfluorohexanoic Add (PFHA),PerfluoroheptanoicAdd (PFHpA),PerfluorooctanoicAdd (PFOA),PerfluorononanoicAdd (PFNA),Perfluorodecanoic
Add (PFDA),PerfluoroundecanoicAdd (PFUnA),PerfluorododecanoicAdd (PFDoA),Perfluorobutanesulfonate(PFBS), Perfluorohexanesulfonate(PFHS),and Perfluorooctanesulfonate(PFOS) inWater, Soiland SedimentbyLC/MS/MS
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 124 o f 209
Ih :;, dacui'neT :n4y
...:/'T 4 rup'enh T;/ 14 ;/h-y;:- from 11/13/
3M Environmental Laboratory P0003268; Interim Report#2
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 50:50 aceton'itrile:water 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
Initial Solution Aliquoted Volume Final Solution
Calibration Standard
(ng/mL)
(mL)
Volume (mL)
(ng/mL)
100 5
100
5.0
100 2.5
100
2.5
10 10
100
1.0
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 ng/mL, based on peak area) using the standard curve (linear regression parameters) generated by an appropriate soflware program:
Analyte found (ng/mL) = (Peak Area-Intercept) x QF 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.
Recove - Total analyte found (ng/mL) - Average analyte found in sample (ng/mL) ^ ^ Analyte added (ng/mL)
Use the following equation to convert the amount of analyte found in ng/mL to ng/g (ppb).
Analyte found(ng/mL) x Volume extracted (mL) Analyte found (ppb) = -
Sample weight (g)
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 [100% / total solids (%)]
12 Method Performance
ETS-8-012.1
Page 10 of 12
MethodofAnalysisfortheDeterminationofPerfluorobutanoicAcid(PFBA),PerfluoropentanoicAdd (PFPeA),Perfiuorohexanoic Acid(PFHA),PerfluoroheptanoicAdd (PFHpA),PerfluorooctanoicAdd (PFOA),PerfluorononanoicAdd (PFNA),Perfluorodecanoic
Add (PFDA),PerfluoroundecanoicAdd (PFUnA),PerfluorododecanoicAcid(PFDoA),Perfluorobutanesulfonate(PFBS), Perfluorohexanesulfonate(PFHS),and Perfluorooctanesulfonate(PFOS) inWater,Soiland SedimentbyLC/MS/MS
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 125 of 209
3M Environmental Laboratory P0003268; Interim Report#2
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 (nonGLP 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 5% and a retention time RSD of 2% to be compliant.
12.2 Quantitation
Calibration Curve: The coefficient of determination (r2) 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 25% 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 accuracy 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 foe 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: Specificity 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
ETS-8-012.1
Page 11 o f 12
MethodofAnalysisfortheDeterminationofPerfluorobutanoicAcid(PFBA),PerfluoropentanoicAdd (PFPeA),Perfluorohexanoic Add (PFHA),PerfluoroheptanoicAcid(PFHpA),PerfluoroodanoicAdd (PFOA),PerfluorononanoicAdd (PFNA),Perfluorodecanoic
Add (PFDA),PerfluoroundecanoicAcid(PFUnA),PerfluorododecanoicAdd (PFDoA),Perfluorobutanesulfonate(PFBS), Perfluorohexanesulfonate(PFHS),andPerfluorooctanesulfonate(PFOS)inWater,SoilandSedimentbyLC/MS/MS
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 126 of 209
Th; document may cs sscus T
3M Environmental Laboratory P0003268; Interim Report#2
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 sheets/records, instrument run log (instrument batch records, instrument acquisition method, summary pages), instalment results files, chromatograms, calibration curves, and data calculations.
15 References
Exygen Research Analytical Method V0003305-1 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
11/10/06
made optional. The accuracy requirements of the analytical balance were updated.
The method was updated to allow the use of a linear 1/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
MethodofAnalysisfortheDeterminationofPerfluorobutanoicAcid(PFBA),PerfluoropentanoicAcid(PFPeA),Perfluorohexanoic Acid(PFHA),PerfluoroheptanoicAcid(PFHpA),PerfluorooctanoicAdd (PFOA),PerfluorononanoicAdd (PFNA),Perfluorodecanoic
Add (PFDA),PerfluoroundecanoicAcid(PFUnA),PerfluorododecanoicAcid(PFDoA),Perfluorobutanesulfonate(PFBS), Perfluorohexanesulfonate(PFHS),andPerfluorooctanesulfonate(PFOS)inWater,SoilandSedimentbyLC/MS/MS
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 127 of 209
3M Environmental Laboratory P0003268; Interim Reporttf2
Attachment C: Protocol and Protocol A mendments
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 128 of 209
3M Environmental Laboratory P0003268; Interim ReportH2
ExyLIMS Protocol Number: P0003268
STUDY PROTOCOL
Study Title: Analysis of Perfluorobutanesulfonate (PFBS),
Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil, Sediment,
Fish, and Clams Using LC/MS/MS for the 3M Decatur Monitoring Program
MPI Research Study Number.: 0137.0219 ExyLIMS Protocol Number: P0003268
Performing Laboratory: MPI Research, Inc. State College 3058 Research Drive State College, PA 16801 Phone: (814)272-1039
Sponsor Representative: Michael A. Santoro Director o f Regulatory Affairs 3M Building 0236-01-B-10 St. Paul, MN 55144 Phone: (651)733-6374
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 1 o f 57 Page 129 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
DISTRIBUTION:
1) Jaisimha Kesari, Study Director, Weston Solutions, Inc. 2) Karen Risha, Principal Investigator, MPI Research, Inc. 3) Michael A. Santoro, Sponsor Representative, 3M Company 4) MPI Research Quality Assurance Unit
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 2 o f 57 Page 130 of 209
3M Environmental Laboratory P0003268; Interim Reportlt2
ExyLlMS Protocol Number: P0003268
PROTOCOL APPROVAL
S tudy T itle:
A nalysis o f Perfluorobutanesulfonate (PFB S), Perfluorohexanesulfonate
(P F H S ), and P e rflu o ro o c ta n e su lfo n a te (P F O S ) in W ater. Soil. S edim ent,
F ish, and Ctonn lin in g L L /M S /M S fo r th e 3*t D e o d a r M o n ito rin g
Program
;
M PI Research Study N um ber: 0137.0219 ExyLlM S Protocol N um ber: P0003268
APPROVALS
Jaisim ha Kesari, Study D irector W eston Solutions
D ate
M PI R esearch, Inc.
06flB[P7
D ate
/ 'M fiJ ' D ate
Page 3 o f 57
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 131 of 209
3M Environmental Laboratory P0003268; Interim ReportM
ExyLIMS Protocol Number: P0003268
TABLE OF CONTENTS
TITLE PAGE.......................................................................................................................................................1 DISTRIBUTION................................................................................................................................................. 2 PROTOCOL APPROVAL.................................................................................................................................. 3 TABLE OF CONTENTS.................................................................................................................................... 4 INTRODUCTION............................................................................................................................................... 5 TEST MATERIALS........................................................................................................................................... 5 OBJECTIVE....................................................................................................................................................... 6 TESTING FACILITY......................................................................................................................................... 7 STUDY DIRECTOR...........................................................................................................................................7 SPONSOR REPRESENTATIVE........................................................................................................................7 PRINCIPAL INVESTIGATOR..........................................................................................................................7 PROPOSED EXPERIMENTAL START AND TERMINATION DATES......................................................8 IDENTIFICATION AND JUSTIFICATION OF THE TEST SYSTEM.......................................................... 8 SAMPLE PROCUREMENT, RECEIPT AND RETENTION.......................................................................... 8 SAMPLE IDENTIFICATION............................................................................................................................9 ANALYTICAL PROCEDURE SUMMARY.................................................................................................... 9 VERIFICATION OF ANALYTICAL PROCEDURE........................................................................................10 METHOD FOR CONTROL OF BIAS...............................................................................................................11 STATISTICAL METHODS............................................................................................................................... 11 GLP STATEMENT.............................................................................................................................................11 R E PO RT .............................................................................................................................................................. 12 SAFETY AND HEALTH................................................................................................................................... 13 AMENDMENTS TO PROTOCOL.................................................................................................................... 13 DATA RECORD KEEPING.............................................................................................................................. 13 QUALITY ASSURANCE.................................................................................................................................. 14 RETENTION OF DATA AND ARCHIVING...................................................................................................14 APPENDIX I, ANALYTICAL METHODS....................................................................................................... 15
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 4 o f 57 Page 132 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
INTRODUCTION
The purpose of this study is to perform analysis for perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (PFHS) and perfluorooctanesulfonate (PFOS) in water, soil, sediment, fish, and clams using LC/MS/MS for the 3M Decatur Monitoring Program.
The study will be audited for compliance with EPA TSCA Good Laboratory Practice Standards 40 CFR 792 by the Quality Assurance Unit of MPI Research.
TEST MATERIALS
The test materials are perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (PFHS) and perfluorooctanesulfonate (PFOS).
PFBS Chemical Name: Perfluorobutanesulfonate Molecular Weight: 338 supplied as the potassium salt (CiFiSOaK.*) Transitions Monitored: 299 - 80, 99 Structure:
FF FF
FF FF
3
PFHS Chemical Name: Perfluorohexanesulfonate Molecular Weight: 438 supplied as the potassium salt (CeFnSOsX^ Transitions Monitored: 399 -> 80, 99 Structure:
FF
F
F
F
F
FF
FF
F
F
3
PFOS Chemical Name: Perfluorooctanesulfonate Molecular Weight: 538 supplied as the potassium salt (CgFivSC^TC)
Transitions Monitored: 499 -> 80,99
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 5 o f 57 Page 133 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLlMS Protocol Number: P0003268
Structure:
FPFF FFFF
FFFF FFFF
3
OBJECTIVE
The purpose of this study is to perform analysis for perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (PFHS) and perfluorooctanesulfonate (PFOS) in water, soil, sediment, fish, and clams for the 3M Decatur Monitoring Program using the current versions of the following 3M Company and MPI Research analytical methods:
ETS-8-012: "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"
V0001780: "Method of Analysis for the Determination of Perfluorooctanoic
Acid (PFOA) in Water by LC/MS/MS"
V0001781: "Method of Analysis for the Determination of Perfluorooctanoic
Acid (PFOA) in Soil by LC/MS/MS"
V0001782: "Method of Analysis for the Determination of Perfluorooctanoic
Acid (PFOA) in Sediment by LC/MS/MS"
V0001783: "Method of Analysis for the Determination of Perfluorooctanoic
Acid (PFOA) in Fish and Clams by LC/MS/MS"
The primary analytical method for the analysis of the water, soil, and sediment samples is the ETS-8-012 method. In instances where quantitative analytical results are not obtained by this method, the Study Director may direct the performing laboratory to analyze the samples by alternate methods (V0001780 for water samples, V0001781 for soil samples, and V0001782 for sediment samples).
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 6 o f 57 Page 134 of 209
TESTING FACILITY
MPI Research, Inc. (formerly Exygen Research, Inc.) State College 3058 Research Drive State College, PA 16801 Phone: (814) 272-1039 Fax: (814) 231-1580
STUDY DIRECTOR
Jaisimha Kesari P.E., DEE Weston Solutions, Inc. 1400 Weston Way West Chester, PA 19380 Phone: (610) 701-3761 Fax: (610) 701-7401 j .kesari@westonsolutions.com
SPONSOR REPRESENTATIVE
Michael A. Santoro 3M Company Director of Regulatory Affairs 3M Building 0236-01-B-10 St. Paul, MN 55144 Phone:(651)733-6374
PRINCIPAL INVESTIGATOR
Karen Risha MPI Research, Inc. State College 3058 Research Drive State College, PA 16801 Phone: (814) 272-1039 karen.risha@mpiresearch.com
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 7 o f 57 Page 135 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
PROPOSED EXPERIMENTAL START AND TERMINATION DATES
It is proposed that the analytical portion of this study be conducted from June 14, 2007 to December 31, 2007. The actual experimental start and termination dates will be included in the interim reports and the final report.
IDENTIFICATION AND JUSTIFICATION OF THE TEST SYSTEM
The following are the test systems for this study: Water (groundwater and surface water) Soil Sediment Fish Clams
The samples will be collected by Weston Solutions. The control samples will be purchased and prepared by the testing facility. Purchase and processing details for the control samples will be included in the appropriate interim report and/or final report associated with this study.
The analysis of PFBS, PFHS, and PFOS are included in a voluntary effort by 3M to gain additional characterization of samples collected to comply with the 3M Letter of Intent (LOI) with the U.S. EPA to collect PFOA data. Additional samples not part of the LOI may be analyzed at the discretion of the Study Director.
SAMPLE PROCUREMENT, RECEIPT AND RETENTION
Water, soil, sediment, fish, and clam samples are being received at MPI Research directly from Weston Solutions. The details of sample procurement procedures for this study are outlined in the 3M work plan entitled "Phase 2 Work Plan for Sampling Environmental Media for PFOA at the 3M Decatur, AL Plant." The number and types of samples received and analyzed will vary depending on data needs for additional characterization of PFBS, PFHS, and PFOS concentrations in various environmental media and availability in the field. The total number of samples received and analyzed for each matrix will be documented in the appropriate interim report associated with this study.
Water, soil, and sediment samples will be used as received at MPI Research. These samples will be homogenized before the extraction process by vigorously shaking the sample bottles. These samples will be stored refrigerated at 2C-8C. Fish and clam samples will be processed according
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 8 o f 57 Page 136 of 209
3M Environmental Laboratory P0003268; Interim Reportlf2
ExyLIMS Protocol Number: P0003268
to the appropriate analytical method (see Appendix I). These samples will be stored frozen at < -10C.
The receipt and processing of the samples will be documented in the appropriate interim report and raw data associated with the study.
SAMPLE IDENTIFICATION
Prior to analysis, each sample will be assigned a laboratory sample reference number. The reference number will be unique and will distinguish each laboratory sample that is processed throughout the analytical procedure. Chromatographic data will be identified by the laboratory sample reference number.
Sample storage conditions and locations will be documented throughout the study.
ANALYTICAL PROCEDURE SUMMARY
References:
ETS-8-012: "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"
V0001780: "Method of Analysis for the Determination of Perfluorooctanoic
Acid (PFOA) in Water by LC/MS/MS"
V0001781: "Method of Analysis for the Determination of Perfluorooctanoic
Acid (PFOA) in Soil by LC/MS/MS"
V0001782: "Method of Analysis for the Determination of Perfluorooctanoic
Acid (PFOA) in Sediment by LC/MS/MS"
V0001783: "Method of Analysis for the Determination of Perfluorooctanoic
Acid (PFOA) in Fish and Clams by LC/MS/MS"
The primary analytical method for the analysis of the water, soil, and sediment samples is the ETS-8-012 method. In instances where quantitative analytical results are not obtained by this method, the Study Director may direct the performing laboratory to analyze the samples by alternate methods (V0001780 for water samples, V0001781 for soil samples, and V0001782 for sediment samples).
Page 9 o f 57
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 137 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
The above referenced methods are to be followed for the analysis of the samples with the following exceptions:
If sludge samples are received by MPI Research to be included in the study, the sludge samples will be extracted and analyzed following the method for soil samples.
If necessary for the preparation of appropriate standards levels, alternate weights of test material and alternate volumes o f suitable solvent (acetonitrile, methanol, etc.) may be used.
If necessary, the duplicate bottle of a water sample may be used in an extraction if the primary bottle does not have enough volume available.
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, MPI Research 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 PFBS, PFHS and PFOS. Samples will be added to each container to a volumetric fill line at 200 mL. A field duplicate, a low field spike, a mid field spike (optional, at the discretion of the Study Director), and a high field spike of each sample will be collected. The low, mid (optional), and high field spike bottles will contain PFBS, PFHS and PFOS as well as perfluorooctanoic acid (PFOA) and 1,2-'3C perfluorooctanoic acid (13C PFOA, optional). PFOA and l3C PFOA (optional) are included in the solutions used to spike the samples. The results for PFOA and 13C PFOA (optional) will not be reported in this study. MPI Research will supply one field blank (control water) and two or three field blank spikes (control water fortified with PFBS, PFHS and PFOS at a low, mid (optional) and high level) for every twenty aqueous samples collected. At the testing facility, each water sample (excluding field duplicates and field spikes) may be extracted in duplicate and may also be fortified at a low, mid (optional), and high concentration and processed through the described procedure. The use of the in lab duplicate and the in lab fortified spikes is not a requirement but may be requested to determine method accuracy and to check for bias at the discretion of the Study Director.
For soil, sediment, fish, and clams, MPI Research will supply one 500 mL precleaned Sci/Spec Premier wide mouth HDPE bottle per sample collected or a zip-seal bag. All containers/bags used for sample collection will be shipped to the sample location. Samples will be added to each container or bag in the
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 10 o f 57 Page 138 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
field. At the testing facility, each sample will be extracted in duplicate and will also be fortified at a known concentration with PFBS, PFHS and PFOS at a low, mid (optional, at the discretion of the Study Director), and high level and processed through the described procedure to determine method accuracy and to check for bias.
Low, mid, and high spiking levels for each matrix are definec below:
Matrix
Low PFOA
Mid PFOA High PFOA
Spiking Levels Spiking Levels Spiking Level
Water
0.25 ng/mL
5.0 ng/mL
100 ng/mL
Soil
2 ng/g
40 ng/g
800 ng/g
Sediment
2 ng^g
40 ng/g
800 ng/g
Fish
2 ng/g
40 ng/g
-
Clams
2 ng/g
40 ng/g
-
Low, mid and high spiking levels of the analytes for each matrix may be altered depending on sample size, sample availability, and/or to cover analyte concentrations expected in the samples. In instances where the expected analyte concentrations exceed the relevant range of the lower level spikes, the lower level spikes may be deferred.
Recoveries are anticipated to be between 70% and 130% of the fortified levels; however, the exact precision and accuracy will be determined by the analysis of the quality control samples described above. A statement of accuracy will be included in the appropriate interim report.
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.
STATISTICAL METHODS
Statistics will be limited to those specified in the subject methods and to the calculation of average recoveries, as applicable.
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
Page I I o f 57
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 139 of 209
3M Environmental Laboratory P0003268; Interim Reportlf2
ExyLIMS Protocol Number: P0003268
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
Interim reports will be prepared by the principal investigator or their designee for specific sampling sites and sample matrices due to the size of the data sets and the phased nature of sample collection activities. A final report will be prepared by the principal investigator or their designee at the conclusion of the study. All reports 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 MPI 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.
Description of the instrumentation used and operating conditions.
All results from all sets analyzed. Control and fortified samples will be identified and the data table will include sample number and fortification level.
Representative chromatograms for each analyte in each matrix, including chromatograms of a standard and a control sample, and a chromatogram at a fortification level. The location of the analyte peaks will be clearly identified in all chromatograms.
All circumstances that may have affected the quality or integrity of the data will be documented in the report.
Locations where raw data, interim reports, and the final report are to be archived.
Page 12 o f57
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 140 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
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.
All applicable requirements for reporting of study results as per 40 CFR 792.185.
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 or from the analytical 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
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 13 o f 57 Page 141 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
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 chromatograms will additionally include the concentration (e.g., pg/mL).
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.
QUALITY ASSURANCE
The QA Unit of MPI 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, MPI Research Management, and the Sponsor Representative.
RETENTION OF DATA AND ARCHIVING
All hard copy raw data, including, but not limited to, the original chromatograms, worksheets, correspondence, and results shall be included with the data package submitted to the Study Director. These will be archived with the original study plan, amendments, final report, and all pertinent information from the Sponsor.
The testing facility shall keep all electronic raw data and any instrument, equipment, and storage logs for the period of time specified in 40 CFR 792.195. An exact copy of the materials submitted to the study director will also be kept at MPI Research, State College.
MPI Research will obtain permission from the study director before discarding or returning samples.
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 14 o f 57 Page 142 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
APPENDIX I
ANALYTICAL METHODS
ETS-8-012: "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"
V0001780: "Method of Analysis for the Determination of Perfluorooctanoic
Acid (PFOA) in Water by LC/MS/MS"
V0001781: "Method of Analysis for the Determination of Perfluorooctanoic
Acid (PFOA) in Soil by LC/MS/MS"
V0001782: "Method of Analysis for the Determination of Perfluorooctanoic
Acid (PFOA) in Sediment by LC/MS/MS"
V0001783: "Method of Analysis for the Determination of Perfluorooctanoic
Acid (PFOA) in Fish and Clams by LC/MS/MS"
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 15 o f 57 Page 143 of 209
3M Environmental Laboratory POOO3268; Interim Report#2
ExyLIMS Protocol Number: P0003268
3 M E n v iro n in e n ta l L a b o ra to ry
. Method
,
Method o f Analysis fo r the Determination o f Perftuorobutanoic A cid (PFBA), Perlluoropentanoic A d d (PFPeA), Perfluorohexanoic A cid (PFHA), Perfluoroheptanolc A cid (PFHpA), Perfluorooctanolc A cid (PFQ), Perftuorononanoic A cid (PFNA), Perfluomdecanolc A c id (PFOA),
Perfiuoroundecanoic A cid (PFUnA), Perfluorododecanoic A cid (PFDoA), Perfluorobutanesulfonate (PFBS), Peruorohexanesullonate (PFHS), and Perfluorooctanesulfonate (PFQS) in Water, Soil and Sediment b y LC/MS/MS
Method Number: ETS-8-012.1
Adoption Date: Upon Signing
Effective Date:
ApprovedBy:
WiliamK.Reagen,TechnicalManager
Date
ETS-8-012.1
PageIoM2
Method ot Analysis lo r IM Determination or P e rfo re bu tin ote Add {PFBA), P artitore pantinaie Add (PFPeA). Pirtuorebexanoic Add (PFHA). PertHwforttpUndc Add (PFHpA). Psfluoroodm oie Add (PFOA), P orfluorenoniiiolc Add (PFNA). Pertuoredeoano
Acid (PFOA), ParHuoioundacinoic Add (PFUnA). PcrduoradodecanoleAdd (PFOoA). P irtltrorebutanisulfonile (PFBS). PerflueroMxanesuKonate (PFHS). and Portltw oocianoiuifenate (F^OS) In Water. Soil and Sediment by IC/MS/MS
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 6 o f 57 Page 144 of 209
3M Environmental Laboratory P0003268; Interim Reporttt2
ExyLIMS Protocol Number: P0003268
1 Scope and Application
ThismethodistobeusedtoquantityPerfluorubutanoicAcid(PFBA),PerfluorapentanoicAdd (PFPeA), Perfluorohexanoie Add (PFHA), Peifluoroheptmoic Acid (PFHpA), Perfluorooetanoic Add (PFOA), Perfluorononanoic Add (PFNA), Pedluorodecanoic Acid (PFDA), Perfiuoroundecanoic Add (PFUnA), PerfluorododecanoicAdd(PFDoA),Pertluonobulanesulfbnate(PFBS),Perfluorohexanesulfonate(PFHS),and Pertluorooctanesulfonate(PFOS) byHighPerformanceLiquidChromatographycoupledtoa tandem Mass SpecirometricDetector(LC/MS/MS)inwater,soilandsediment.Themethodisdesignedtotargetalowerlimit of quantitation(LOQ)of0.025ng/mL(water)and0.20ng/g(solandsediment).
2 Method Summary
Aqueoussamplesaremixedwithequalvolumesofacetonitrile,thoroughlymixed,centrifugedifnecessary,and aDquotedforanalysisbyLC/MS/MS. Similarly,one-gramaliquotsofsoilandsedimentsaremixedwith90:20 acetonkrfleiwatermixture,thoroughlymixed,centrifuged,andaliquotedforanalysisbyLC/MS/MS. .
ThisIsaperformance-basedmethod. Methodaccuracyisdeterminedforeachsamplesetusingmufflple laboratorycontrolspikesatmultipleconcentrations.Thismethodalsorequiresthattheprecisionandaccuracy foreachsamplebedeterminedusingHeldmatrixspikes(aqueoussamples)orlaboratorymatrixspflees(soil andsediment)toverifythatthemethodisapplicabletoeachsamplematrix. Sampleresultsforspikesoutside of70% to130%,willnotbereportedduelonon-compfantqualitycontrolsamples.
Fortificationlevelsfor Held matrixspikesandforlaboratorymatrixspikesshouldbeatleast50% ofthe endogenousleveland lessthan10limestheendogenousleveltobe usedtodeterminethestatementof accuracyforanalyticalresults.
3 Definitions
3.1 Calibration Standard
.
AsolutionpreparedbyspikingaknownvolumeoftheWorkingStandard(WS)intoapredeterminedamountof ASTMtypeIorHPLCgradewater,dilutedwithacetonitrile,andanalyzedaccordinglothismethod. Calibration standardsareusedtocafbratetheinstrumentresponsewithrespecttoanalyteconcentration.
3.2 Laboratory Duplicate Sample (LDS, or Lab Dup)
A laboratoryduplicatesampleisa separatealiquotofasampletakenintheanalyticallaboratorythatis extractedandanalyzedseparatelywithidenticalprocedures. AnalysisofLDSscomparedtothatofthefirst. aliquotgiveameasureoftheprecisionassociatedwithlaboratoryprocedures,butnotwithsamplecollection, preservation,orstorageprocedures.
3.3 Field Blank (FB)/Trip Blank
ASTMTypeIorHPLCgradewaterplacedinasamplecontainerinthelaboratoryandtreatedasasampleInall
respects,Includingexposuretosamplingsiteconditions,storage,preservationandalanalyticalprocedures.
The purposeoftheFB istodetermineiftestsubstancesorotherinterferencesarepresentinthefield
environment ThissampleIsalsoreferredtoasaTripBlank. Tripblanksarenoterequirementforsoilor
sedimentsamples.
.
3.4 Field Duplicate Sample (FDS, Field Dup)
A samplecollectedIndupicateatthesametimefromthesamelocationasthesample. TheFDSisplaced underidenticalcircumstancesand treatedexactlythesame throughoutFeldand laboratoryprocedures.
ETS-5-012.1
Page2of12
Method of Analysis for (ho Oolcrmlnallon of Perituorobutanolc Add (PFBA), Perfluoropenlanoic Add (PFPoA), Perilucrohexanote A dd (PFHA). Perfluoroheplinric A dd (PFHpA), Peribrarooclinalc Add (PFOA). PorSuaranononole Add (PFNA), PerlluorodecinoJc
A dd (PFOA), PoriluoroundoconolcAdd (PFUnA). PerSooradodecsnolc Add (PFPoA), PsiSuorobutsnosulIbnolo (PFBS) Perfluaratiexanosulfonale (PFHS). and Psriluoroactanesijlfonats (PFOS) inW alsr, Soil and Sediment by LC/MSIMS
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 17 o f 57 Page 145 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
AnalysisoftheFDS comparedtothatofthefirstsamplegivesameasureoftheprecisionassociatedwith samplecollection,preservationandstorage,aswellaswithlaboratoryprocedures.
3.5 Field Matrix Spike (FMS)
A sampletowhichknownquantitiesofthetargetanalytesareaddedtothesamplebottleinthelaboratory beforethebottlesaresenttothefieldforcollectionofaqueoussamples. Aknown,specificvolumeofsample mustbeaddedtothesamplecontainerwithoutrinsing. Thismaybeaccomplishedbymakinga'filltothis level'lineontheoutsideofthesamplecontainer.TheFMSshouldbespitedbetweenapproximately50%and 10timestheexpectedanalyteconcentrationinthesample. IftheexpectedrangeofanalyteconcentrationsIs unknown, multiplespikesatvaryinglevelsmay be preparedtoincreasethelikelihoodthata spikeatan appropriate'levelIsmade. TheFMS isanalyzedtoascertainifanymatrixeffects,interferences,orstability issuesmaycomplicatetheinterpretationofthesampleanalysis.
3.6 Trip Blank Spike (Field Spike Control Sample, FSCS)
AnaliquotofASTMTypeIorHPLCgradewatertowhichknownquantitiesofthetargetanalytesareaddedin thelaboratorypriortotheshipmentofthecolectionbottles.TheFSCSisextractedendanalyzedexactlylikea sampletohelpdetermineifthemethodisincontrolandwhetheralossofanalytecouldbeattributedtoholding rime,samplestorageand/orshipmentissues. A lowandhighFSCSareappropriatewhenexpectedsample concentrationsarenotknownormayvary. Atleastoneseparate,umspikedsamplemustbetakenatthe sametimeandplaceaseachFMS. .
3.7 Laboratory Control Sample (LCS)
'
Analiquotofcontrolmatrixtowhichknownquantitiesofthetargetanalytesareaddedinthelaboratoryatthe
timeofsampleextraction.Atleasttwolevelsareincluded,onegenerallyatthelowendofthecalibrationcurve
andonenearthemidtoupperrangeofthecurve. TheLCSsareextractedandanalyzedexactlylikea
laboratorysampletodeterminewhetherthemethodisincontrolLCSsshouldbepreparedeachdaysamples
areextracted.
.
3.8 Laboratory Matrix Spike (LMS)
AlaboratorymatrixspikeIsanaliquotofasampletowhichknownquantitiesoftargetanalytesareaddedinthe
laboratory. TheLMS isextractedandanalyzedexactlylikealaboratorysampletodeterminewhetherthe
samplematrixcontributesbiastotheanalyticalresults.Theendogenousconcentrationsoftheanalytesinthe
samplemalrucmustbedeterminedinaseparatealiquotandthemeasuredvaluesintheLMS correctedfor
theseconcentrations. LMSsarerequiredforsoilsandsedimentsandareoptionalforanalysisofaqueous
samples.
.
3.9 Laboratory Sample
.
Aportionoraliquotofasamplereceivedfromthefieldfortesting.
3.10 Limit of Quantitation (LOQ)
ThekxirerIM ofquantitation(LLOQ)foradatasetisthelowestconcentrationthatcanbereliablyquantitated withinthespecifiedlimitsofprecisionandaccuracyduringroutineoperatingcondlions. Tosimplifydata reporting,theLLOQ isgenerallyselectedasthelowestnon-zerostandardinthecalibrationcurvethatmeets methodcriteria.SampleLLOQsarematrix-dependent
Theupperlimitofquantitation(ULOQ)foradatasetisthehighestconcentrationthatcanbereliablyquantitated withinthespecifiedlimitsofprecisionandaccuracyduringroutineoperatingconditions. Thehigheststandard InthecalibrationcurvethatmeetsmethodcriteriaisdefinedastheULOQ.
ETS-8-012.1
Page3of12
Method o fAnalysis fo r the Determ ination o f P eriloorobutmote A dd (PFBA), Perfluoropenianoic A dd (PFPeA). P eriluorohtxinofc
A dd (PFHA), Partuoroheptanote A dd (PFHpA). PerHuoroodanote A dd {PFOA). Periluorononanole A dd (PFNA). Periluprodecanole Add (PFOA). P arfluw cirdacahgiC Add (PFUnA), Parflvorododecandc A dd IPFDoA), Parituorobutanaautfonata (PFBS), Perituorohexaneaulfonste (PFHS), and Paifluoroodonetuironate (PFOS) In W dler, Soil and Sediment by LDMS/MS
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 18 o f 57 Page 146 of 209
3M Environmental Laboratory P0003268; Interim R eports
ExyLIMS Protocol Number: P0003268
3.11 Method Blank
..
AnaliquotofcontrolmatrixthatistreatedexactlyIkeelaboratorysampleincludingexposuretoallglassware, equipment,solvents,andreagentsthatareusedwithotherlaboratorysamples.Themethodblankisusedto determinetestsubstancesorotherInterferencesarepresentinthelaboratoryenvironment,thereagents,or theapparatus.
3.12 Sample
A sampleisanaliquotremovedfromalargerquantityofmaterialIntendedtorepresenttheoriginalsource material
3.13 Stock Standard Solution (SSS)
Aconcentratedsolutionofasingle-analytepreparedinthelaboratorywithanassayedreferencecompound.
3.14 Surrogate
Acompoundsimilartothetargetenalyte(s)inchemicalcompositionandbehaviorthatisnotnormallyfoundIn thesample(s). A surrogatecompoundjstypicallyatargetanalytewithatleastoneatomcontainingan isotopicallylabeledsubstitution. Ifused,'surrogate^)ereaddedtoallsamplesandqualitycontrolsamples (exceptsolventblanksandhalfofthepreparedmethodblanks). Surrogate^)areaddedtoquantitatively evaluatetheentireanalyticalprocedureincludingsamplecollection,aidraction,andanalysis. Inclusionofa surrogateanalyteisanoptionalqualitycontrolmeasureandisNOTrequired.
3.15 Working Standard (WS)
A solutionofseveralanalytespreparedinthelaboratoryfromSSSs and dilutedasneededtoprepare
calibrationstandardsandotherrequiredanalytesolutions.
.
4 Warnings and Cautions
______________
_________
4.1 Health and Safety
Theacuteandchronictoxicityofthestandardsforthismethodhavenotbeenpreciselydetermined;however, eachshouldbetreatedasapotentialhealthhazard. Theanalystshouldweargloves,alabcoat,andsafety glassestopreventexposuretochemicalsthatmightbepresent
The laboratoryisresponsibleformaintaininga saleworkenvironmentand a currentawareness oflocal regulationsregardingthehandlingofthechemicalsusedInthismethod.Areferencefileofmaterialsafetydata sheets(MSDS)shouldbeavailabletoallpersonnelinvolvedintheseanalyses.
4.2 Cautions
.
Theanalystmustbefamiliarwiththelaboratoryequipmentsndpotentialhazardsincluding,butnotfmitedto,
theuseBl solvents,pressurizedgasandsolventlines,highvoltage,andvacuumsystems. Refertothe appropriateequipmentprocedureoroperatormanualforadditionalinformationandcautions.
5 Interferences
Duringextractionandanalysis,majorpotentialcontaminantsourcesarereagentsandglassware.Allmaterials usedintheanalysesshallbedemonstratedtobetheefromInterferencesunderconditionsofanalysisby runningmethodblanks.
ETS-8-012.1
Page4Of12
Mothod of Analysts fo r tho Oolerm lnatlon o f Parduorobutanolc Add (PF8A), Pstfluoropontonoic A dd (PFPoA), Poriluorohoxw rolc A dd (PFHA). P erflgorofiepunoic A dd (PFHpA). PerSuoroodanole A dd (PFOA), Porfludranonsnolc A dd (PFNAJ Perfiuorodecanoie
Add (PFOA), PirSuorow docotiD ic Add (PFUnAI. Ptriluorododecandc Add (PFOoA). PerduoroOulanoaullonate (PFBS), Perfluorohoxanasuironsle (PFHS). and PotSuoroodonoaurtOnoto (PFOS) In W ater, Soil and S edim tnl by LC/MS/MS
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 19 o f 57 Page 147 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
PartsandsuppliesthatcontainTeflonshouldbeavoidedorminimizedduetothepossibilityofinterference
and/orcontamination. Thesemayinclude,butarenotlimitedto:washbattles,Teflon*linedceps,sutovisJ
caps,HPLCparts,etc.
'
The useofdisposablemicropipettesorpipettestoaliquotstandardsolutionsisrecommendedtomake calibrationstandardsandmatrixspikes.
6 Instrumentation, Supplies, and Equipment______________________ _________
6.1 Instrumentation and Equipment
A highperformance(quidchromatographcapableofpumpingupto2solventsandequippedwithavariable
volumeinjectorcapableofinjecting5-200pLconnectedtoatandemMassSpectrometer(LC/MS/MS). Applied BiosystemsSdexAPI5000instrumentationisrequiredtomeettheLOQsof0.025nglM.(water]and0.20ng/g
(solandsediment). Ifanalyteconcentrationsrequiredilutionsforoneormoreanalytesthatprecludethe targetedLOQsfrombeingreached,AppliedBiosystemsSdexAPI4000instrumentationmaybeutilizedsince
theLOQswillalreadyberaised.
Analyticalbalancecapableofreadingto0.0001gram.
Adevicetocoiledrawdataforpeakintegrationandquantitation.
15-mLand50-mLdisposablepolypropylenecenlrifugetubes.
Disposablemicropipettes(10-20pL,25-50pL.50-100pL.100-200pL).
125-mLLDPEnarrow-mouthbottles.
'
2-mLdearHPLCvialkit.
Disposablepipettes,polypropyleneorglassasappropriate.
Ultrasonicbath.
Centrifugecapableofspinning15-mt.and50-mLpolypropylenetubesat3000rpm.
6.2 Chromatographic System
'
AnalyticalColumn:Luna3pmC8(2)Mercury(Phenomenex),2mmx4mm,3pm (P/N:OOM-424SOOCE)
Temperature: 35*C
MobilePhase(A):2mM AmmoniumAcetateinWater
MobilePhase(B):Methanol
GradientProgram:
Tknefmin)
%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 80 10
10.0 90 10
InjectionVolume: 5pL(canbeincreasedtoasmuchas50pL).
Row Rate 'imL/min)
0.75 0.75
0.75
0.75 0.75
0.75 0.75 0.75
Quantitation: PeakArea-externalstandardcalibrationcurve,1htweighted. ETS-B-012.1
Page5of12
Method o fAnatyala tor the OetermlnaUon or P eilluerobulanolc Add (PFBAJ, Perftuoropentanolc Add (PFPeA). Pertucrohexanoic A dd (PFHA). Pertluorofieptanolc Add (PFHpA). P e rtuorofldanolc Add (PFOAI, Pertuoranonsnoie Add (PFNA), Pertuorodecanoie
A dd (PFOAJ, P ertuoraundecaiidcA dd (PFUnA), Periluoradedecanale A dd (PFOoA), PerituorobutaneeullanatB IPFBS), Perikiorohexanesulfonate tPFHS). and Peffluoraodaneaurfonala (PFOS) In W ater. Soil and Sedim ent by LC/MSIMS
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 20 o f 57 Page 148 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
RunTime:-10minutes.
ThepreviousinformationisIntendedasaguide:alternateconditionsandequipmentmaybeused
providedthatdataqualityobjectivesaremet.
.
6.3 MS/MS System
6.3.1 Mode BecbosprayNegativeMRMrrode,rrontoringthetblcwlngtransitions;
Analyte
TransitionMonitored
PFBA 213->169
PFPeA
263-t219
PFHA 313->269and313->119
PFHpA : 363-319.363-a169and363-119
PFOA
413->369.413->219and413->169
PFNA 463-f419.463-e169and463-219
PFDA
513- t 469.513-*219and513->269
PFUnA
563-*519.563->269and563->219
PFDoA
613->569.613-169and613->319'
PFBS 299-80and299->99
PFHS
399->60and399->99
PFOS
499-*80.499->99and499->130
Multipletransitionsformonitoringtheanalytesisanoptionbecausesummingmultipletransitions
mayprovidequantitationofisomersthatmorecloselymatchesNMRdataandmayhavethe
addedbenefitofincreasedanaiytesignal.Theuseofonedaughterionisacceptableifmethod
sensitivityisachieved,providedthatretentiontimecriteriaaremettoassureadequatespecificity.
Thepreviousinformationisintendedasaguide,alternateinstrumentsandequipmentmay be used.
7 Reagents and Standards
________
Water-HPLCgrade Methanol-HPLCgrade AmmoniumAcetate-A.C.S ReagentGrade Acetonitrile-HPLCgrads PerlluorobutanoicAcid(PFBAJ-OakwoodProducts,Inc PeriluoropentanoicAcid(PFPeA)-Sigma-Aldrich PetfluorohexandicAcid(PFHA)-OakwoodProducts.Inc PertluoroheptanoicAdd(PFHpA)-OakwoodProducts,Inc PerfluorooctanoicAcid(PFOA)-OakwoodProducts,Inc PerfluorunonanoicAcid(PFNA)-OakwoodProducts.Inc PertluorodeeanoicAcid(PFOA)-OakwoodProducts.Inc PerfluoroundecanoicAcid(PFUnA)-OakwoodProducts,Inc PedluorododecanoicAcid(PFDoA)-OakwoodProducts,Inc
ETS-8-012.1
Page6oft2
Method o f Analysis for the Oetermlnattan o f P erfluorobuinolc A dd (PFBAJ. PsrSuoropentanolc A dd (PFPeA). PerSuorohexanofc
A dd (PFHA), Perttuoroheptanek; A dd (PFHpA), PslSuoroodanolc A dd (PFOA), PerSuorononanolc A dd (PFNA), PetSuorodecanolc A dd (PFOA). Perfluoroundecanoic Add (PFUnA). PerSoorododecanoic A dd (PFDoA). Pehluorohgtanesulfonate (PFBS), Perdiiorahexanesdfonate (PFHSI, and Porfluoroodanesulfonale (PFOS) In W ater, Soil and Sedim ent by LCAUSIMS
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 21 o f 57 Page 149 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
Perfluorobutanesulfonete(PFBS)-3M
Perfluorohexanesulfonate(PFHS)-3M
Perfluoroactanesutfonate(PFOS)-Fluka
.
Thepreviousinformationisintendedasaguide. Reagentsandstandardsfromalternatesources maybeused.
8 Sample Handling
__________________________ ______________________
8.1 W ater Sample Extraction
8.1.1 Measure10mlofsampleintoa50-mLpolypropylenecentrifugatube.Fortificationsamtobedoneatthis point8 necessary.Othervolumesandcontainersmaybeusedasappropriate.
8.12 Add10mLofacetonitriletothesampleinthecentrifugetube.Captightlyandshake.
8.1.3 Sonicatesamplefor-2hoursatroomtemperature.Thisstepisoptional,butisrecommended9particulates
appeartobepresent
.
8.1.4 Centrifugefor-10minutesat-3000rpmThisstepisoptional,butisrecommendedifsamplesare sonicated. -
8.1.5 Transferaportionofthesupernatanttoanautosampiervialforanalysis.
8.1.6 Dilutesample,ifnecessary,wfth50:50acetanitrie:water.
8.2 Soil and Sediment Extraction
8.2.1 Weigh1gofsampleintoa15^nLpolypropylenecentrifugetube.Fortificationsaretobedoneatthispoint,if necessary.
62.2 Add8mlof80:20actionKrile.'watartothesampleinthecentrifugetube.Captightlyandshake.
82.3 -Sonicatesamplefor-2hoursatroomtemperature.
8.2.4 Centfugefor-10minutesat-3000rpm. 62.5 Transferaportionofthesupernatanttoanautosamplerviafforanalysis.
626 Dilutesample,ifnecessary,with50:50aceionitrtevvater.
827 AnalyzesamplesusingeleetrospreyLCTMS/MS OtherweightsandvolumescanbeusedaslongastheQC elementsspecifiedinthismethodare satisfiedamiettsamplepreparationproceduresmaybereconstructed.
9 Sample Analysis - LC/MS/MS
ETS-8-012.1
Page7of12
M e tta ti o f Anelyele fo r the Determ ination o f Perfluorobutenolc A dd (PFBA), Pertluowpentenole Add (PFPeA), PerfluorohcienQ ic A dd (PFHA), Perfluoroheptanoic Add (PFHpA), PerSuoroodenole A dd (PFA), PerduorononanolC A dd (PFNA). PerfluorodecanoJc
A dd (PFOA), PerfluorountiecanoieAcid (PFUnA), Periuorododeeanoic A dd (PFDoA), Perfiuorobutenesulfonale (PFBS), Perfluorohexaneedfonele (PFHS),and Perfluorooctanesutfenale (PFOS) In w ater. S oil end Sediment by LC/MS/MS
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 22 o f 57 Page 150 of 209
3M Environmental Laboratory P0003268; Interim Reporttf2
ExyLIMS Protocol Number: P0003268
9.1.1 AminimumoflxcalibrationlevelsmustbepresentintheinalcaSbraticncurve.
9.12 Anentiresetofcaibrationstandardsseededa!thebeginningofasamplesetpriortosampleanalysis.As analternative,anentiresetofcaibrationstandardsmaybeinjectedatthebeginningofasamplesetWowed 'bycalibrationstandardsInterspersedevery5-10samples(toaccountfora secondsetofstandanis).In eilhercase,caibrationstandardsoraoonfrusigcalibrationverificationstandardmustbracketthefts! sampleandthelastsample.AnalyticalstoriesmayonlyrequirethataninitialcaBxationcurvebesneezed priortosamplesandthat(hecontinuedaccuracyoftheinitialcaibrationcurvebeconfirmedbytheanalysisof contbuingcaibrationverifcaionstandards.Thesameapproachshouldbeusedthroughoutlheentirestudy unlessreasonsamdocumentedandtechnicaljustificationtochangeisapprovedpriortosampleanalysis.
9.1.3 ThestandardcuiveIsplaitedbyquadraticft(yax*+bx+c),weiredtoeorunweighted,orusingafnear -fit.weighted1/x,usingsuitablesoftware. Thecaibrationcurvesmayincludebutshouldnotbsfbrced throughzero.Themathematicalmethodusedtocalculatettwcalbrationcurveshouldbeapplied consistentlythroughoutastudy.AnychangeshouldbedocumentedIntherawdale.
9.1.4 Samplesconlainriganalytesthatarequantitatedabovetheconcentrationofthehigheststandardinthe curveshouldbefurtherdilutedandreanalyzedorre-injectedusingasmallervolume.
10 Quality Control___________
10.1 Data Quality Objectives.
'
Thismethodandrequiredqualitycontrolsamplesisdesignedtogeneratedataaccurateto+/-30%witha targetedLOQof0025ng/mL(water)or0.20ng/g.Wetweight(soilandsediment). Anydeviationsfromthe qualitycontrolmeasuresspeledoutbelowwibedocumentedIntherawdataandfootnotedinthefinalreport.
10.2 Blanks
102.1 MethodBlank
Methodblanksmustbepreparedwitheachextractionbatch.Arangeofthreetosevenmethodblanks mustbeprepared. Thesemethodblanksmustbeinterspersedthroughouttheextractionbelchand analyzedinterspersedthroughouttheanalyticalsequence.
. ThemeanareacountforeachanalyteInthemethodblanksmustbelessthan50%oftheareacount oftheLOQstandard. Thestandarddeviationoftheareacountsofthesemethodblanksshouldbe calculatedandreported. Ifthemeanareacountsofthemelhodblanksexceed50% oftheLOQ standard,thentheLOO mustberaisedtothe.firststandardlevelinthecurvethatmeetscriteria,or alternatively,themethodblanks mustbe evaluatedstatisticallytodetermineoutliersortechnical justificationtoeliminateoneormoreresultsshouldbemade.
1022 SolventBlank
Solventblanksmustbeanalyzedthroughouttheanalyticalsequence. Solventblanksthatshowarea countsgreaterthan50% oftheareacountsoftheLOO standardmustbeevaluatedtodetermineif analyticalresultsaresignificantlyimpactedbysamplecarry-overoranunacceptablebuildupofanalyte Intheinstrumentalbackground.
10.3 Sample Replicates
.
SamplesshouldbepreparedinduplicateInthelab(soilandsediment)orcollectedInduplicateInthefield (Water). Therelativepercentdifference,RPD,shouldbereported. RPDresultsgreaterthan20%(water)or
ETS-8-012.1
PageIof12
Method of Anatyol fo r the Determ ination o f P erfluorobutinolc Add (PFBAJ, Pedluoropentanolc A dd (PFPeA), Perfluorohexanolc A dd (PFHA), Perfluoroheplandc Ado (PFHpA), PerfluoroocUnoio A dd (PFOA}. Perfluorononartoie A dd (PFNA). Pertuorodecanoic
A dd (PFOA), Pertuoroundecanoie Add (PFUnA), Periluorododecanoic A dd (PFDeA). Periluon>butanesUfontta (PFBS),
Periluoroheieneeutfonete (PFHS). end P erfluoroocttnetulfonele (PFOS) in W ater. Sod and Sediment by LOMS/MS
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 23 o f 57 Page 151 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
30%(solandjtdimenl)willbeflaggedinthereport,butwinnotbeexcludedfromreporting. Therequirement
forreplicatesexcludesfieldblanksandrinseblanks.
.
10.4 Surrogate Spikes
Surrogatespikesarenotrequiredbutmaybeusedonprojectspecificrequirements.
10.5 Lab Control Sample
Triplicatelabcentralspikesata minimumoftwodifferentconcentrationsaretobe preparedwitheach extractionbatch. Lowlabcontrolspikesshouldbepreparedatconcentrationsintherangeoffivetotentimes higherthanthetargetedLOQandhighlabcontrolspikesshouldbepreparedatconcentrationsnearthemid pointofthecurve. Therelativestandarddeviationofthecontrolspitesforthesesixpooledcontrolsamples mustbelessthanorequalto20%andtheaveragerecoverymustbe80-120%. Iftheabovecriteriaarenot met,theentiresetofsamplesshouldbere-injectedorre-extractedasappropriate.
10.6 Field Matrix Spikes / Lab Matrix Spikes
Recoveriesoffieldmatrixspikes(aqueoussamples)andlaboratorymatrixspikes(soilsandsediments)are anticipatedtobebetween70%and130%ofthefortifiedlevels. Iftherecoveriesofthespikesfanoutsidethe acceptablerange,thesampleresultwlbereportedas`NR`(notreportedduetonon-compliantQCresults).
Thetargetedfbttificationlevelsshouldbqatleast80%oftheendogenouslevelandlessthan10timesthe endogenousleveltobeusedwithoutJustificationtodeterminethestatementofaccuracyforanalyticalresuts.
Theaverageofthesampleandthelabduplcate(solsandsediment)orfieldduplicate(water)shouldbeused
tocalculatetherecovery.
.
10.7 Standard Preparation
.
10.7.1 StandardStockSolutions
Prepareindividualstocksolutionsofeachanalyteat-1000pgfmLbyweighing100mgofanalyticalstandard
(correctedforpurityandsaltcontentifnecessary)anddiluteto100mL withmethanoloracetonitrisin
separata100-mLvolumetricflasks. Forpuritycorrection,taketheamountofanalytethatisneededfor
weighing(i.e.100mg)anddividebythepurityindecimalform(i.e.99.6%<0.996). Theresultistheweightthat
isneededtomakethesolutioncorrectedforpurity(i.e.weigh100.4mg). Forsaltcorrection,calculatethesalt
contentbytakingthemolecularweightofthetargetcompound(i.e.PFOS*499)anddividingbythemolecular
weightoftheentirecompound(re.PFOSpotassiumsalt(CsFiySOj-K**638). TheresultisthesaltcontentIn
decimalform(i.e.0.9275). Taketheamountofanalytethatisneededforweighing(le.100mg)anddivideby
thesaltcontentindecimalform. Theresultistheweightthatisneededtomakethesolutioncorrectedforsalt
content(ie.weigh107.6mg). Storealstocksolutionsinappropriatecontainersandatappropriatestorage
conditionsforupto6monthsfromthedaleofpreparation.
'
Alternatestocksolutionconcentrationscanbemade,Ifnecessary,usingalternativemassesandvolumes.
10.7.2 StandardFortificationSolutions
A 10pgfinLmixedfortificationsolutioncontainingalloftheanalytesispreparedbybringing1mL ofeachofthe 1000pgilnLstocksolutionstoafinalvolumeof100mLwUiacetonitrileina100-mLvolumetricflask. A 1.0 pg/mLmixedfortificationsolutioncontainingalloftheanalytesispreparedbybringing10mLofIhe10pgfmL mixedsolutiontoaAnalvolumeof100withacetonitrileina100mLvolumetricflask. A 0.1pglmLmixed fortificationsolutioncontainingalloftheanalytesispreparedbybringing10mLofthe1.0pgM.mixedsolution toafinalvolumeof100withacetonitrileina10(knLvolumetricflask.A 0.01pgfotLmixedfortificationsolution
containingalloftheanalytesIspreparedbybringing10mLofthe0.1pg/mLsolutionloafinalvolumeof100
withacetonitrileIna100-mLvolumetricflask. Storealfortkicab'onstandardsupto6monthsfromthedateof preparation .
ETS-8-012.1
Page9of12
Metnod o fAnalysis for the Determ ination o f PeriluorDbutanoie A dd (PFBA), Periluoropentanole A dd (PPPeA), Periluororiaxanolc
A dd fPFH A], Perlluoroheptandc Add (PFHpA), Peffluoreoctanolc A dd (PFQA). Perttuarononanotc A dd (PFNA). PerSuorodecandc A dd (PFOAJ. PerfluoroiardecanoleAdd (PPUnAJ, Perlluorododecandc Add (PFOoA), PerSuorodutaneauIbnala (PFBS). Peffluorahexanaadronste (PFHS). and Perduoroodanasdlonala (PFOS) In w ater, S ell and Sediment by LC/MSIMS
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 24 o f 57 Page 152 of 209
3M Environmental Laboratory P0003268; Interim Reports
ExyLIMS Protocol Number: P0003268
Alternatefortificationsolutionconcentrationscanbemade,Ifnecessary. Likewise,alternativevolumesmaybe used.
10.8 Instrument Calibration
108.1 LCAASMScaforsTjcnstandardsarepreparedoiemaityinXr.50acetonWierwaierandareusedtoconstruct thecalibrationcurvesforthewater,sol,andsedimentprocedures.
10.8.2 Thefotowingisatypicalexamplec#acaibration set Alternateoradditionalconcentrationsmaybeprepared
asneeded.
.
Concentration InitialSolution
ofInitialSolutionAliquotedVolume FinalSolution
(ng/ml)
(mL) Volume(ml)
10 5
100
too
2.5 .
100
10 10 100
5 10 100
2.5
10
100
1 10 100
0.5
10
100
1 2.5 100
FinalConcentrationof CalibrationStandard
(ng/mL) 5.0 2.S
1.0
0.5 0.25
0.1 0.05
0.025
bepreparedasneeded.
11 Data Analysis and Calculations
Usethefollowingequationtocalculatetheamountofanalytebund(inngAnL,basedonpeakarea)usingtire standardcurve(linearregressionparameters)generatedbyanappropriatesoftwareprogram:
Analytefound(ng/ml)=(nakArearlntercept)xpp Slops
OF =factorbywhichthefinalvolumewasdiluted,ifnecessary.
Forsamplesfortifiedwithknownamountsofanalytepriortoextraction,usethefollowingequationtocalculate thepercentrecovery.
P0ttr.Qr.,|Totalanalytefound(ng/mL)-AverageanalytefoundInsample(ng/mL)
AnaJyteadded(ngAnL)
*
Usethefollowingequationtoconverttheamountofanalytefoundinng/mLtong/g(ppb).
s-reMefound(ppb)-Analyte<ounii<n'mt->Volumeexlfac1edlmL> Sampleweight(g)
' *
Usethefollowingequationtocalculatetheamountofanalytefoundinppbbasedondryweight.
Analytefound(ppb)dryweightAnalytefound(ppb)x[100%/totalsolids(%)]
12 Method Performance
ETS-8-012.1
Page 10oft2
Method o fAnatyale fo r (he Determ ination o f PerfluorobuUnolc A dd (PFBA), Perfluorepentanolc A dd (PFPaA), P erftorahexsndc Add (PFHA). PertuorohepUnofc A dd (PFHpA). Peritoorocctanoie Add (PFOA), P eriluorononanoic A dd (PFNA), P eriluorodec*noie
A dd (PFOA). P vrftoroundecanoic Add (PFUnA), Periluorododecanoic A dd (PFDoA). P erttuorobuttneiulfonale (PFBS). P eritarohexaneeuifonate (PFHS), end P eriluoroodenesiifnate (PFOS) In W ater. Soil end Sedim ent by LC/MSMS
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 25 o f 57 Page 153 of 209
3M Environmental Laboratory P0003268; Interim ReporW2
ExyLIMS Protocol Number: P0003268
Anymethodperformanceparametersthatarenotachievedmustbeconsideredintheevaluationo(thedata. NonconformancetoanyspecifiedparametersmustbedescribedanddiscussediftheTechnicalManager(nonGLPstudy)orStudyDirector(GLPstudy)choosestoreportthedata.
IfcriteriaIstedInthismethodperformancesectionarenotmetmaintenancemaybeperformedonthesystem andsamplesreanalyzed,orotheractionstakenasappropriate.Documental!actionsIntherawdata. .
Ifdataaretobereportedwhenperformancecriteriahavenotbeenmet,thedatamustbefootnotedontables anddiscussedinthetextofthereport
12.1 System Suitability
-.
.SystemSuitabilitystandardsarenotarequiredcomponentofthismethod. Ifrequiredbyprotooolorbythe technicalmanager, a minimum ofthreesystemsuitabilitysamplesare Injectedatthebeginning ofeach analyticalranpriortothecalibrationcurve.Typicallythesesamplesareataconcentrationnearthemidlevelof
thecalibrationcurveandarerepealedinjectionsfromoneautosamplervial.Thesystemsuitabilityinjections musthaveareacountswithanRSDofS5%andaretentiontimeRSDofS2% tobecompliant
12.2 Quantitation
.
CalibrationCurve:Thecoefficientofdetermination(r3)valueforthecalibrationcurvemustbegreaterthanor equalto0.985. Theconcentrationofeachpointinthecurvemustbackcalculatetobewithin25%ofthe
theoreticalconcentrationwiththeexceptionoftheLLOQ,whichmaybewithin30%. Calbretioncurvepoints thatarenotatthehighorlowendofthecurvemaynotbedeactivated.
CCV Performance: Thecontinuedaccuracyofthecalibrationcurvemustbedemonstratedbyanalyzing continuing'calfeiationverification(CCV)standards. EachCCV may bea calibrationcurvepointthatis
reinjectedora separatelyprepared standard,and istypicallynearthemiddleofthecalibrationcurve. Alternativeconcentrationsormultipleconcentrationsmaybechosendependingonprojectrequirements. Not
morsthantensamplesorspitesmaybeanalyzedbetweentheinitialcalibrationandaCCVorbracketing CCVs. Theaccuracyofeachanalytemustbewithin25%ofthetheoreticalvalue.Samplesthatarebracketed byCCVsnotmeetingthesecriteriamustbereanalyzed.
DemonstrationofSpecificity:Specificityisdemonstratedbychromatographicretentiontime(within4% of standard)andthemassspectralresponseofuniqueions.
12.3 Sensitivity
Thetargetedlimitofquantitationforallanalytesis0.025ng/tnL(water)and0.20ngfg(soilsandsediments,wet weight).TheLOQforanyspecificanalytemayvarydependingontheevaluationofappropriateblanksandthe accuracyofthelow-levelcalibrationcurvepoints.RefertoSection10foradditionaldetails.
12.4 Accuracy
Thismethodandrequiredqualitycontrolsampleseredesignedtogeneratedatathatareaccurateto+/-30%. Section10containsadditionalinformationregardingtherequiredaccuracyoflaboratorycontrolspares,field matrixspikes(watersamples)andlaboratorymatrixspkes(soilsandsediments).
12.5 Precision
Samplesshouldbepreparedinduplicateinthelab(solandsediment)orcollectedinduplicateInthefield (aqueous). Therelativepercentdifference,RPD,shouldbereported.RPDresultsgreaterthan20%(water)or 30%(soilandsediment)willbeflaggedinthereport,butwillnotbeexcludedfromreporting.Therequirement forreplicatesexcludesfieldblanksorrinseblanks
Section10containsadditionalinformationregardingtherequiredprecisionoflaboratorycontrolspites.
13 Pollution Prevention and Waste Management
---------------------- ETS-MTI'l-----------PageItof12------
Method o fAnalyst lo r lire D eteim ination o f P tifluorobulanote A dd (PFBA), Porfluoroponlanofc A dd (PFPaA), ParfluorohM onoie Acid (PFHA). P ertuorohepianolc A dd (PFHpA), Pertuoroodanoic A dd (PFOA), Parfluorononanoie Add (PFNA). Pertuorodecanoic
A dd (PFOA), Rertuoroundecanoic Acid (PFUnA), Perltuorododscanoic Add (PFOaA), Perfluorobulaneauironatt (PFBS), Pertuorohexaneaulfonale (PFKS), and Pertuoroodanesujtonate'fPFO S) in W ater, Sell and Sediment by LC/MS/MS
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 26 o f 57 Page 154 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
Wastegeneratedwhenperformingthismethodwillbedisposedofappropriately.Theoriginalsampleswillbe archivedatthe3MEnvironmentalLaboratoryinaccordancewithinternalprocedures.
14 Records__________________________________________________ _________ _
Eachdatapackagegeneratedforastudymustincludeailsupportinginformationforreconstiuctionofthedata. Informationforthedatapackagemustinclude,butisnotmitedtothefollowingitems:studyorprojectnumber, sampteandstandardprepsheets/records,instrumentrunlog(instrumentbatchrecords,instrumentacquisition method,summarypages),instrumentresultsfiles,chromatograms,calbratiortcurves,anddatacalculations.
15 References_____________________________________ '______________________
ExygenResearchAnalyticalMethodV0Q03305-1detailsmethoddevelopmentandverificationofrecoveryfor multipleanalytesingroundwater,surfacewater,soil,andsediment.ThiswillbearchivedaspartofE06-0549.
16 Affected Documents_________________ __________________
None.
__________
17 Revisions
Revision Number
RevisionDescription
Revision Date
1 Thesonleationandcentrifugationstepsofthewatersamplepreparationwere
11/10/06
madeoptional.Theaccuracyrequirementsoftheanalyticalbalancewereupdated.
Themethodwasupdatedtoallowtheuseofalinear1/xweightedcaKbrationcurve.
Thetableofrequireddaughterionsfortheanalyteswasupdated.Themethod
wasupdatedtoflowdifferentsamplevolumestobeextractedandtoallow
cBfferentstandardbottlesendstorageconditionstobeused.Calibrationrequirements
wereupdatedtoshowthatanalyzingcontinuingcalibrationverificationstandardsatone '
concentrationwasanacceptablealternativetoreinjectingallcurvepointsusedtoconstruct
thecalibrationcurve. Minorwordingchangesweremadethroughout
ETS-8-Q1M
Page12oU2
Method o fAnalysis for the Determ ination of PerftuoroOuttnoic A dd (PFBA), Perfluoropentanolc Add (PFPeA), P e riuorohexanole A dd (PFHA). PerBuorohsptanolc A dd (PFHpA), PerfluoroocUnoic Add (PFOA), P arttorononanoic Acid (PFNA). Periluorodacanoie
A dd (PFOA). Perfluoraundectndc Add (PFUnA). Pariluorododacanoic A dd (PFDoA), P eriluorobutanesulionita (PFBS), . Perduorohexanesuironale (PFHS), and Perfluorooctanesulbnata (PFOS) In WStar, S oli and Satfm errt by LCTMS/MS
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 27 o f 57 Page 155 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 28 o f 57 Page 156 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
ANALYTICAL METHOD
Method Number: V0001780
Method of Analysts for the Determination of Ferfluorooctanoic Acid (PFOA) in Water by LC/MS/MS
Analytical Testing Facility.
Exygen Research 3058 Research Drive State College, PA 16801
Approved By:
'r ~ Y t \ C,-- _____________
Paul Connolly
'
Technical Leader, LC-MS, Exygen Research
_jo|za/W
Date
'John Flaherty Vice President, Operations, Exygen Research
Date
Total Pages: 7
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 29 o f 57 Page 157 of 209
3M Environmental Laboratory P0003268; Interim Repordf2
ExyLIMS Protocol Number: P0003268
Exygen Research
Method Number V0001780
_____________________________ A N A L Y T IC A L m e t h o d _____________________________
Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Water by LC/MS/MS
1.0 Scope
This method is to be employed for the isolation and quantitation of perfluorooctanoic acid by High Performance Liquid Chromatography coupled to a tandem Mass Spectromtrie Detector (LC/MS/MS) in water.
2.0 Safety
2.1 Always observe safe laboratory practices. 2.2 Consult the appropriate MSDS before handling any chemical for proper safety
precautions.
3.0 Sample Requirement
3.1 At least 40 mL o f test sample for extraction. 3.2 No sample processing is needed for water samples. 3.3 Samples stored refrigerated should be allowed to equilibrate to room
temperature. 3.4 All samples must be thoroughly mixed before being sampled for extraction. 3.3 Any samples containing particles should be centrifuged at -3000 rpm for -5
minutes and the supernatant used for the extraction. 3.6 Sample collection procedures will be specified in the sampling plan for this
project.
4.0 Reagents and Standards
4.1 W ater- HPLC grade 4.2 Methanol - HPLC grade 4.3 Ammonium Acetate - A.C.S. Reagent Grade 4.4 Perfluorooctanoic Acid - Sigma-Aldrich
S.0 Instrument and Equipment
5.1 A high performance liquid chromatograph capable o f pumping up to 2 solvents equipped with a variable volume injector capable o f injecting 3-200 pL connected to a tandem Mass Spectrometer (LC/MS/MS).
3.2 A device to collect raw data for peak integration and quantitation. 3.3 Analytical balance capable o f reading to 0.00001 g. 3.4 30 mL disposable polypropylene centrifuge tubes. 3.3 13 mL disposable polypropylene centrifuge tubes. 3.6 Disposable micropipets (50-100uL, 100-200uL). 5.7 125-mL LDPE narrow-mouth bottles. 5.8 2 mL clear HPLC vial kit. 5.9 Disposable pipettes. 5.10 Aulopipettes (100-1000 pL and 10-100 pL), with disposable tips. 5.11 Waters Sep Pak Vac 6 cc (lg) tC18 SPE cartridges.
Page 2 of 7
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 30 o f 57 Page 158 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
Exygen Research
MethodNumberV0001780
_________________________ AINa LVTICAL METHOD_________________________
Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Water by LC/MS/MS
5.12 SPE vacuum manifold. 5.13 Centrifuge capable of spinning SOmL polypropylene lubes at 3000 rpm.
6.0 Chromatographic System
6.1 Analytical Column: Fluophase RP (Keystone Scientific), 2.1 mm x SO mm, 5p (P/N: 82505-052130)
6.2 Temperature: 30'C 6.3 Mobile Phase (A) : 2 mM Ammonium Acetate in Water 6.4 Mobile Phase (B) : Methanol 6.5 Gradient Program:
Time iminl
0.0
l.O
8.0
20.0 22.5
%A 65 65 25 25 65
Flow Rate % B fmL/minl 35 0.3 35 0.3 75 0.3 75 0.3 35 0.3
6.6 Injection Volume: 15 pL (can be increased to as much as 50 pL). 6.7 Quantitation: Peak Area - external standard calibration curve. 6.8 Run T im e:- 2 3 minutes.
The above conditions are intended as a guide and may be changed in order to optimize the HPLC system.
7.0 MS/MS System 7.1 Mode: Electrospray Negative MRM mode, monitoring 413 - 369 m/z.
The above conditions are intended as a guide and may be changed in order to optimize the MSMS system.
8.0 Preparation o f Solutions 8.1 Mobile Phase
8.1.1 2 mM ammonium acetate in water is prepared by adding 0.154 g of ammonium acetate to 1000 mL of water.
Alternate volumes may be prepared.
Page 3 of^
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 31 o f 57 Page 159 o f 209
3M Environmental Laboratory P0003268; Interim ReporW2
ExyLIMS Protocol Number: P0003268
Exygen Research
Method Number V0001780
ANALYTICAL METHOD
Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Water by LC/MS/MS
9.0 Standard Preparation
9.1 Standard Stock/Fortification Solution 9.1.1 Prepare a stock solution o f -100 pg/mL of PFOA by weighing 10 mg of analytical standard (corrected for purity) and dilute to 100 mL with methanol in a 125-mL LDPE bottle. 9.1.2 A 10 pg/mL fortification solution o f PFOA is prepared by bringing 10 mL of the 100 pg/mL solution to a final volume o f 100 with methanol in a 125 mL LDPE bottle. 9.1.3 A 1.0 pg/mL fortification solution of PFOA is prepared by bringing 10 mL of the 10 pg/mL solution to a final volume o f 100 with methanol in a 125 mL LDPE bottle. 9.1.4 A 0.1 pg/mL fortification solution of PFOA is prepared by bringing 10 mL of the 1.0 pg/mL solution to a final volume o f 100 with methanol in a 125 mL LDPE bottle. 9.1.5 A 0.01 pg/mL fortification solution o f PFOA is prepared by bringing 10 mL of the 0.1 pg/mL solution to a final volume of 100 with methanol in a 125 mL LDPE bottle. 9.1.6 The stock and fortification solutions are to be stored in a refrigerator at approximately 4'C and are stable for a maximum period of 6 months from the date of preparation.
9.2 Standard Calibration Solutions
9.2.1 9.2.2
LC/MS/MS calibration standards are prepared in HPLC water. The calibration standards are processed through the extraction procedure, identical to samples. The following is a typical example: additional concentrations may be prepared as needed.
Final
Concentration Fortification Volumeof Concentrationof Calibration
ofFortification Volume FortifiedControl Calibration StandardID
Solution(ppb) (pL) Sample(mL) Standard(ppt)* (example)
0 0 40
0 XCmmddyy-0
to 100 40
23 XCmmddyy-1
IO 200 40
50 XCmmddyy-2
IO 400 40
100 XCmmddyy-3
100 100 40
250 XCmmddyy-J
100 200 40
500 XCmmddyy-5
100 400
40
1000 XCmmddw-6
* The extracted concentration of the calibration standard is equal to 8x its initial
concentration, due to the concentration of the standard during the extraction (SPE).
XC *=extracted calibration standard.
pge4or7
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 32 o f 57 Page 160 of 209
3M Environmental Laboratory P0003268; Interim Report62
ExyLIMS Protocol Number: P0003268
Exygen Research
Method Number V0001780
ANALYTICAL METHOD_________________________
Method o f Analysis for the Detetmination o f Perfluorooctanoic Acid (PFOA) in Water by LC/MS/MS
9.2.3 9.2.4 9.2.3
A zero standard solution (reagent blank) must be prepared with each set of standards extracted. Store all extracted calibration standards in 15-mL polypropylene tubes at 2C to 6C, up to two weeks. Alternate volumes and concentrations o f standards may be prepared as needed.
10.0 Batch Set Up
10.1 Each batch o f samples extracted (typically 20 or less) must Include at least one reagent control (method blank using HPLC water) and two reagent controls fortified at known concentrations (lab control spike) to verify procedural recovery for the batch.
10.2 Requirements for held and laboratory duplicates and spikes will be specified in the quality assurance plan for this project.
11.0 Sample Extraction
11.1 Measure 40 mL of sample or a portion o f sample diluted to 40 mL with water into SO mL polypropylene centrifuge tubes (fortify as needed, replace lid and mix well).
11.2 Condition the Cis SPE cartridges (I g, 6 mL) by passing 10 mL methanol followed by 5 mL of HPLC water (- 2 drop/sec). Do not let column run dry
11.3 Load sample on conditioned Cu SPE cartridge. Discard eluate. 11.4 Elute with ~5 mL 100% methanol. Collect 5 mL of eluate into graduated
15 mL polypropylene centrifuge tubes (final volume - 5 mL). 11.5 Analyze samples using electrospray LC/MS/MS.
12.0 Chromatography
12.1 Inject the same amount of each standard, sample and fortified sample into the LC/MS/MS system. A calibration standard must precede and follow ail analyzed samples.
12.2 Standards of PFOA corresponding to at least five or more concentration levels must be included in an analytical set.
12.3 An entire set of extracted calibration standards must be included at the beginning and at the end of a sample set. Extracted standards must be interspersed between every 5-10 samples. As an alternative, an entire set of extracted calibration standards may be injected at the beginning of a set followed by extracted calibration standards interspersed every 5-10 samples (to account for a second set of extracted standards). In either case, extracted calibration standards must be the first and last injection in a sample set.
12.4 Use linear standard curves for quantitation. Linear standard curves are generated for the analyte by linear regression using 1/x weighting of peak area
Page 5 o f 7
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 33 o f 57 Page 161 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
Exygen Research
Method Number VOOO1780
_________________________ ANALYTICAL m e t h o d
Method of Analysis for the Determination o f Perfluorooctanoic Acid (PFOA) in Water by LC/MS/MS
versus calibration standard concentration using MassLynx 3.3 (or equivalent) software system. 12.3 Sample response should not exceed standard responses. Any samples that exceed standard responses should be further diluted and reanalyzed.
13.0 Acceptance Criteria
13.1 Chromatogram must show a peak of a daughter ion at 369 amu from a parent of 413 amu. The 413 amu parent corresponds to the PFOA anion, while the daughter ion (369 amu) represents the loss o f carbon dioxide.
13.2 Method blanks must not contain PFOA at levels greater than the LOQ. If a blank contains PFOA at levels greater than SO ng/L, then a new blank sample must be obtained and the entire set must be re-extracted.
13.3 Recoveries o f control spikes and matrix spikes must be between 70-130% of their known values. If a control spike falls outside the acceptable limits, the entire set of samples should be re-extracted. Any matrix spike outside 70 130% should be evaluated by the analyst to determine if re-extraction is warranted.
13.4 Any calibration standard found to be a statistical outlier by using the Huge Error Test, may be excluded from the calculation o f the calibration curve. However, the total number of extracted calibration standards that could be excluded must not exceed 20% of the total number o f extracted standards injected.
13.5 The correlation coefficient (R) for calibration curves generated must be 20.992 (RJ 20.96$). If calibration results fall outside these limits, then appropriate steps must be taken to adjust instrument operation, and the standards or the relevant set of samples should be reanalyzed.
13.6 Retention times between standards and samples must not drift more than 4 % within an analytical run. If retention time drift exceeds this limit within an analytical run then the set must be reanalyzed.
14.0 Calculations
14.1 Use the following equation to calculate the amount of PFOA found (in ng/L, based on peak area) using the standard curve (linear regression parameters) generated by the Mass Lynx software program:
PFOA found (ng/L) = (Peak area - intercept) x DF slope
DF = factor by which the final volume was diluted, if necessary.
Page 6 of 7
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 34 o f 57 Page 162 of 209
3M Environmental Laboratory P0003268; Interim ReporW2
ExyLIMS Protocol Number: P0003268
Exygeo Research
MethodNumberV0001780
ANALYTICAL METHOD_________________________
Method of Analysis for the Determination of Perftuorooctanoic Acid (PFOA) in Water by LC/MS/MS
14.2 For samples fortified with known amounts o f PFOA prior to extraction, use the following equation to calculate the percent recovery.
Recovery (%) -
[ total analyte found (ng/L) analyte found in control (ng/L)] ^ analyte added (ng/L)
Page 7 o f 7
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 35 o f 57 Page 163 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
ANALYTICAL METHOD
Method Number: V0001781
Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Soil by LOMS/MS
Analytical Testing Facility:
Exygen Research 3058 Research Drive State College, PA 16801
Approved By:
" U A C -JL
Paul Connolly
'
Technical Leader, LC-MS, Exygen Research
lolaj(.M
Date
Date
Total Pages: 7
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 36 o f 57 Page 164 of 209
3M Environmental Laboratory P0003268; Interim Reports
ExyLIMS Protocol Number: P0003268
Exygen Research
Method Number V0001781
| ANALYTICAL METHOD
Method of Analysis for the Determination o f Perfluorooctanoic Acid (PFOA) in Soil by LC/MS/MS
1.0 Scope
This method is to be employed for the isolation and quantitation o f perfluorooctanoic acid by High Performance Liquid Chromatography coupled to a tandem Mass Spectrometric Detector (LC/MS/MS) in soil.
2.0 Safety
2.1 Always observe safe laboratory practices. 2.2 Consult the appropriate MSDS before handling any chemical for proper safely
precautions.
3.0 Sample Requirement
3.1 At least 13 g of test sample for extraction. 3.2 No sample processing is needed for soil samples. 3.3 Samples stored refrigerated should be allowed to equilibrate to room
temperature. 3.4 All samples must be thoroughly mixed before being sampled for extraction. 3.3 Sample collection procedures will be specified in the sampling plan for this
project.
4.0 Reagents and Standards
4.1 Water - HPLC grade 4.2 Methanol - HPLC grade 4.3 Ammonium Acetate - A.C.S. Reagent Grade 4.4 Perfluorooctanoic Acid - Sigma-Aldrich
3.0 Instrument and Equipment
3.1 A high performance liquid chromatograph capable of pumping up to 2 solvents equipped with a variable volume injector capable of injecting S-200 pL connected to a tandem Mass Spectrometer (LC/MS/MS).
3.2 A device to collect raw data for peak integration and quantitation. 3.3 Analytical balance capable of reading to 0.00001 g. 3.4 30 mL disposable polypropylene centrifuge tubes. 3.3 13 mL disposable polypropylene centrifuge tubes. 3.6 Disposable micropipets (30-lOOuL, 100-200uL). 5.7 125-mL LDPE narrow-mouth bottles. 5.8 2 mL clear HPLC vial kit. 5.9 Disposable pipettes. 5.10 Autopipettes (100-1000 pL and 10-100 pL), with disposable tips. 5.11 Waters Sep Pak Vac 6 cc (lg) tCIS SPE cartridges. 5.12 SPE vacuum manifold. 5.13 Ultrasonic bath.
Page 2 of 7
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 37 o f 57 Page 165 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
Exygen Research
Method Number V0001781
|
ANALYTICAL METHOD
~
Method of Analysis for the Determination o f Perfluorooctanoic Acid (PFOA) in Soil by LC/MS/MS
5.14 Wrist-action shaker. i .15 Centrifuge capable of spinning SOmL polypropylene tubes at 5000 rpm.
6.0 Chromatographic System
6.1 Analytical Column: Fluophase RP (Keystone Scientific), 2.1 mm x 50 mm, 5p (P/N: 82505-052130)
6.2 Temperature: 30C 6.3 Mobile Phase (A) : 2 mM Ammonium Acetate in Water
Mobile Phase (B) : Methanol Gradient Program:
Time fmin) 0.0 1.0 8.0 20.0 22.5
%A
65 65 25 25 65
Flow Rate
% B (mUminl 35 0.3 35 0.3 75 0.3 75 0.3 35 0.3
6.6 Injection Volume: 15 pL (can be increased to as much as 50 pL). 6.7 Quantitation: Peak Area - external standard calibration curve. 6.8 Run Time: - 23 minutes.
The above conditions are intended as a guide and may be changed in order to optimize the HPLC system.
7.0 MS/MS System
7.1 Mode: Electrospray Negative MRM mode, monitoring 413 -- 369 m/z for PFOA.
The above conditions are intended as a guide and may be changed in order to optimize the MSMS system.
8.0 Preparation of Solutions 8.1 Mobile Phase
8.1.1 2 mM ammonium acetate in water is prepared by adding 0.154 g of ammonium acetate to 1000 mL of water.
Alternate volumes may be prepared.
Page 3 o f 7
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 38 o f 57 Page 166 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
Exygen Research
Method Number V0001781
ANALYTICAL METHOD
Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Soil by LC/MS/MS
9.0 Standard Preparation
9.1 Standard Stock/Fortification Solution 9.1.1 Prepare a stock solution of ~100 pg/mL of PFOA by weighing 10 mg of analytical standard (corrected for purity) and dilute to 100 mL with methanol in a 125-mL LDPE bottle. 9.1.2 A 10 pg/mL fortification solution of PFOA is prepared by bringing 10 mL of the 100 pg/mL solution to a final volume of 100 with methanol in a 125 mL LDPE bottle. 9.1.3 A 1.0 pg/mL fortification solution of PFOA is prepared by bringing 10 mL of the 10 pg/mL solution to a final volume of 100 with methanol in a 125 mL LDPE bottle. 9.1.4 A 0.1 pg/mL fortification solution o f PFOA is prepared by bringing 10 mL of (he 1.0 pg/mL solution to a final volume of 100 with methanol in a 125 mL LDPE bottle. 9.1.5 A 0.01 pg/mL fortification solution o f PFOA is prepared by bringing 10 mL of the 0.1 pg/mL solution to a final volume of 100 with methanol in a 125 mL LDPE bottle. 9.1.6 The stock and fortification solutions are to be stored in a refrigerator at approximately 4C and are stable for a maximum period of 6 months from the date of preparation.
9.2 Standard Calibration Solutions
9.2.1 9.2.2
LC/MS/MS calibration standards are prepared in HPLC water. The calibration standards are processed through the extraction procedure, identical to samples. The following is a typical example: additional concentrations may be prepared as needed.
Final
Concentration Forti fcation Volume o f Concentration o f Calibration
o f Fortification Volume Fortified Control Calibration
Standard ID
Solution (nob) 0
<M 0
Sample fmL) 40
Standard (ppt)* 0
(example) XCmmddyy-0
IO 100 40
25 XCmmddyy-1
10 200 40
50 XCmmddyy-2
10 400 40
100 XCmmddyy-3
100 100 40
250 XCmmddyy-4
100 200
40
500 XCmmddyy-5
100 400
40
1000
XCnunddyy-6
* The extracted concentration of the calibration standard is equal to 8x its initial
concentration, due to the concentration of the standard during the extraction (SPE).
XC - extracted calibration standard.
Page 4 o f 7
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 39 o f 57 Page 167 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
ExygeD Research
Method Number V00017S1
________________________ ANALYTICAL METHOD
Method o f Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Soil by LC/MS/MS
9.2.3 9.2.4 9.2.5
A zero standard solution (reagent blank) must be prepared with each set of standards extracted. Store all extracted calibration standards in 15-mL polypropylene tubes at 2"C to 6C, up to two weeks. Alternate volumes and concentrations o f standards may be prepared as needed.
10.0 Batch Set Up
10.1 Each batch o f samples extracted (typically 20 or less) must include at least one reagent control (method blank using S mL of methanol) and two reagent controls fortified at known concentrations (lab control spike) to verify procedural recovery for the batch.
10.2 Requirements for held and laboratory duplicates and spikes will be specified in the quality assurance plan for this project.
11.0 Sample Extraction
11.1 Weigh 5 g of sample into 50 mL polypropylene centrifuge tubes (fortify as needed, replace lid and mix well).
11.2 Add 5 mL of methanol and shake on a wrist action shaker for ~15 minutes. 11.3 Transfer the tubes to an ultrasonic bath and sonicate for-15 minutes. 11.4 Bring the volume up to 40 mL with water in the 50 mL polypropylene
centrifuge tube. I t .5 Centrifuge for-10 minutes a t-3000 rpm. 11.6 Condition the Cis SPE cartridges (1 g, 6 mL) by passing 10 mL methanol
followed by 5 mL o f HPLC water (~ 2 drop/sec). Do not let column run dry 11.7 Load (decant) the sample on the conditioned C n SPE cartridge. Discard
eluate. 11.8 Elute with -5 mL 100% methanol. Collect 5 mL of eluate into graduated
15 mL polypropylene centrifuge tubes (final volume = 5 mL). 11.9 Analyze samples using electrospray LC/MS/MS.
12.0 Chromatography
12.1 Inject the same amount of each standard, sample and fortified sample into the LC/MS/MS system. A calibration standard must precede and follow all analyzed samples.
12.2 Standards of PFOA corresponding to at least five or more concentration levels must be included in an analytical set.
12.3 An entire set of extracted calibration standards must be included at the beginning and at the end of a sample set. Extracted standards must be interspersed between every 5-10 samples. As an alternative, an entire set of
Page 5 of 7
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 40 o f 57 Page 168 of 209
3M Environmental Laboratory P0003268; Interim Report#!
ExyLIMS Protocol Number: P0003268
Exygen Research
Method Number V0001781
| ANALYTICAL METHOD
Method o f Analysis for the Determination ofPerfluorooctanoic Acid (PFOA) in Soil by LC/MS/MS
extracted calibration standards may be injected at the beginning of a set followed by extracted calibration standards interspersed every 5-10 samples (to account for a second set of extracted standards). In either case, extracted calibration standards must be the first and last injection In a sample set. 12.4 Use linear standard curves for quantitation. Linear standard curves are generated for the analyte by linear regression using 1/x weighting o f peak area versus calibration standard concentration using MassLynx 3.3 (or equivalent) software system. 12.5 Sample response should not exceed standard responses. Any samples that exceed standard responses should be further diluted and reanalyzed.
13.0 Acceptance Criteria
13.1 Chromatogram must show a peak of a daughter ion at 369 amu from a parent of 413 amu. The 413 amu parent corresponds to the PFOA anion, while the daughter ion (369 amu) represents the loss o f carbon dioxide.
13.2 Method blanks must not contain PFOA at levels greater than the LOQ. If a blank contains PFOA at levels greater than 50 ng/L, then a new blank sample must be obtained and the entire set must be re-extracted.
13.3 Recoveries of control spikes and matrix spikes must be between 70-130% of their known values. If a control spike falls outside the acceptable limits, the entire set of samples should be re-extracted. Any matrix spike outside 70 130% should be evaluated by the analyst to determine if re-extraction is warranted.
13.4 Any calibration standard found to be a statistical outlier by using the Huge Hrror Test, may be excluded from the calculation o f the calibration curve. However, the total number of extracted calibration standards that could be excluded must not exceed 20% of the total number o f extracted standards injected.
13.5 The correlation coefficient (R) for calibration curves generated must be 0.992 (RJ 0.985). If calibration results fall outside these limits, then appropriate steps must be taken to adjust instrument operation, and the standards or the relevant set of samples should be reanalyzed.
13.6 Retention times between standards and samples must not drift more than
4 % within an analytical run. If retention time drift exceeds this limit within an analytical run then the set must be reanalyzed.
Page 6 of 7
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 41 o f 57 Page 169 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
Exygen Roearch
Method Number V0001761
________________________ ANALYTICAL METHOD
Method of Analysis for the Deteimination of Perfluorooctanoic Acid (PFOA) in Soil by LC/MS/MS
14.0 Calculations 14.1 Use the following equation to calculate the amount of PFOA found (in ng/L, based on peak area) using the standard curve (linear regression parameters) generated by the Mass Lynx software program:
PFOA found (ng/L) (Peak area - intercept! x DF slope
DF = factor by which the final volume was diluted, if necessary.
14.2 For samples fortified with known amounts of PFOA prior to extraction, use the following equation to calculate the percent recovery.
Recovery (%) =
[total analyte found (ng/L) - analyte found in control (ng/L)] analyte added (ng/L)
14.3 Use the following equation to convert the amount of PFOA found in ng/L to ng/g (ppb).
PFOA found (ppb) - fPFOA found fng/L) x volume extracted (0.04LV1 sample weight (3 g)
14.4 Use the following equation to calculate the amount of PFOA found in ppb based on dry weight.
PFOA found (ppb) dry weight = PFOA found (ppb) x [100% / total solids(%)]
Page 7 of 7
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 42 o f 57 Page 170 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
ANALYTICAL METHOD
Method Number: V0001782
Method of Analysis for the Determination of Perfluorooctanolc Acid (PFOA) in
Sediment by LC/MS/MS
Analytical Testing Facility:
Exygen Research 3058 Research Drive State College, PA 16801
Approved By:
"VlA Cj iL
Paul Connolly
!
Technical Leader LC-MS, Exygen Research
Date
/iohn Flaherty f Vice President, Operations, Exygen Research
'L Date
Total Pages: 7
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 43 o f 57 Page 171 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
Exygen Research
Method Number V00017*2
|__________________________ ANALYTICAL METHOD
|
Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Sediment by LC/MS/MS
1.0 Scope
This method is to be employed for the isolation and quantitation of perfluorooctanoic acid by High Perfotmance Liquid Chromatography coupled to a tandem Mass Spectrometric Detector (LC/MS/MS) in sediment.
2.0 Safety
2.1 Always observe safe laboratory practices. 2.2 Consult the appropriate MSDS before handling any chemical for proper safety
precautions.
3.0 Sample Requirement
3.1 At least 30 g of test sample for extraction. 3.2 No sample processing is needed for sediment samples. 3.3 Samples stored refrigerated should be allowed to equilibrate to room
temperature. 3.4 All samples must be thoroughly mixed before being sampled for extraction. 3.5 Sample collection procedures will be specified in the sampling plan for this
project.
4.0 Reagents and Standards
4.1 Water -H P L C grade 4.2 Methanol - HPLC grade 4.3 Acetic Acid - Reagent grade 4.4 Ammonium Acetate - A.C.S. Reagent Grade 4.5 Perfluorooctanoic Acid - Sigma-Aldrich
5.0 Instrument and Equipment
5.1 A high performance liquid chromatograph capable o f pumping up to 2
solvents equipped with a variable volume injector capable o f injecting 5-200
pL connected to a tandem Mass Spectrometer (LC/MS/MS).
5.2 A device to collect raw data for peak integration and quantitation.
5.3 Analytical balance capable of reading to 0.00001 g.
5.4 50 mL disposable polypropylene centrifuge lubes.
5.5 15 mL disposable polypropylene centrifuge tubes.
5.6 Disposable micropipets (50-100uL, 100-200uL).
5.7 125-mLLDPE narrow-mouth bottles.
5.8 2 mL clear HPLC vial kit.
.
5.9 Disposable pipettes.
5.10 Autopipettes (100-1000 pL and 10-100 pL), with disposable tips.
5.11 Waters Sep Pak Vac 6 cc (Ig) tC18 SPE cartridges.
5.12 SPE vacuum manifold.
Pige 2 of 7
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 44 o f 57 Page 172 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
Exygen Research
Method Number V000I7S2
______________________ ANALYTICAL METHOD
|
Method of Analysis for the Determination of Periluorooctanoic Acid(PFOA) in Sediment by LC/MS/MS
5.13 Vortexer. 5.14 Wrist-action shaker. 5.15 Centrifuge capable of spinning 50 mL polypropylene tubes at 3000 ipm.
6.0 Chromatographic System
6.1 Analytical Column: Fluophase RP (Keystone Scientific), 2.1 mm x 50 mm, 5p (P/N: 82505-052130)
6.2 Temperature: 30C 6.3 Mobile Phase (A) : 2 mM Ammonium Acetate in Water 6.4 Mobile Phase (B) : Methanol 6.5 Gradient Program:
Time fminl 0.0 1.0 8.0 20.0 22.5
%A 65 65 25 25 65
Flow Rate % B imL/min) 35 0.3 35 0.3 75 0.3 75 0.3 35 0.3
6.6 Injection Volume: 15 pL (can be increased to as much as 50 pL). 6.7 Quantitation: Peak Area - external standard calibration curve. 6.8 Run Time: - 23 minutes.
The above conditions are intended as a guide and may be changed in order to optimize the HPLC system.
7.0 MS/MS System
7.1 Mode: Electrospray Negative MRM mode, monitoring 413 -> 369 m/z for PFOA.
The above conditions are intended as a guide and may be changed in order to optimize the MSMS system.
8.0 Preparation o f Solutions 8.1 Mobile Phase
8.1.1 2 mM ammonium acetate in water is prepared by adding 0.154 g of ammonium acetate to 1000 mL of water.
Page 3 o f 7
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 45 o f 57 Page 173 of 209
3M Environmental Laboratory P0003268; Interim Reporttti
ExyLIMS Protocol Number: P0003268
Exygen Research
Method Number V0001782
|__________________________ ANALYTICAL METHOD
|
Method o f Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Sediment by LC/MS/MS
8.2 Extraction Solutions
8.2.1 1% acetic acid in water is prepared by adding 10 mL of acetic acid to 1000 mL of water.
Alternate volumes may be prepared.
9.0 Standard Preparation
9.1 Standard Stock/Fortification Solution 9.1.1 Prepare a stock solution of -100 pg/mL o f PFOA by weighing 10 mg o f analytical standard (corrected for purity) and dilute to 100 mL with methanol in a 125-mL LDPE bottle. 9.1.2 A 10 pg/mL fortification solution of PFOA is prepared by bringing 10 mL of the 100 pg/mL solution to a final volume o f 100 with methanol in a 125 mL LDPE bottle. 9.1.3 A 1.0 pg/mL fortification solution of PFOA is prepared by bringing 10 mL of the 10 pg/mL solution to a final volume of 100 with methanol in a 12S mL LDPE bottle. 9.1.4 A 0.1 pg/mL fortification solution o f PFOA is prepared by bringing 10 mL of the 1.0 pg/mL solution to a final volume o f 100 with methanol in a 123 mL LDPE bottle. 9.1.3 A 0.01 pg/mL fortification solution of PFOA is prepared by bringing 10 mL of the 0.1 pg/mL solution to a final volume of 100 with methanol in a 125 mL LDPE bottle. 9.1.6 The stock and fortification solutions are to be stored in a refrigerator at approximately 4C and are stable for a maximum period o f 6 months from the date of preparation.
9.2 Standard Calibration Solutions
9.2.1 LC/MS/MS calibration standards are prepared in methanol via dilution
of the 0.1 pg/mL fortification solution.
9.2.2 The following is a typical example: additional concentrations may be
_______ prepared as needed.______________________________
Concentration
Final
of Fortification Volume Solution (na/mL) (mL)
Diluted to (mL)
Concentration (ng/mL)
100 10 100 too 5 100
10.0 5.0
100 2 100
2.0
10 10 100 5 10 100 2 10 100
1.0 0.5 0.2
Page 4 o f 7
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 46 o f 57 Page 174 o f 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
Exygen Research
Method Number VOOOP82
ANALYTICAL METHOD
Method o f Analysis for the Determination o f Pcrfluorooctanoic Acid (PFOA) in Sediment by LC/MS/MS
9.2.3 9.2.4
Store all calibration standards in 125-mL LDPE narrow-mouth bottles at 2C to 6C, up to six months. Alternate volumes and concentrations o f standards may be prepared as needed.
10.0 Batch Set Up
10.1 Each batch of samples extracted (typically 20 or less) must include at least one untreated control and two untreated controls fortified at known concentrations (lab control spike) to verify procedural recovery for the batch.
10.2 Requirements for field and laboratory duplicates and spikes will be specified in the quality assurance plan for this project.
11.0 Sample Extraction
11.1 Weigh 5 g o f sample into SO mL polypropylene centrifuge tubes (fortify as needed, replace lid and mix well).
11.2 Add 35 mL o f 1% acetic acid, cap, vortex and shake on a wrist action shaker for-6 0 minutes.
11.3 Centrifuge the tubes at -3000 rpm for -20 minutes. 11.4 Condition the Cis SPE cartridges (1 g, 6 mL) by passing 10 mL methanol
followed by 20 mL of HPLC water (~ 2 drop/sec). Do not let column run dry 11.5 Load (decant) the sample on the conditioned C u SPE cartridge. Discard
eluate. 11.6 Add 20 mL of methanol to the sediment left in the bottom of the SO mL
centrifuge tube. Cap, vortex and shake on a wrist action shaker for -30 minutes. 11.7 Centrifuge the tubes at -3000 rpm for -20 minutes. 11.8 Decant the methanol onto the same SPE cartridge. Collect the eluate. 11.9 Wash the column with 4 mL of methanol. Collect the eluate and add it to the eluate collected in step 11.8. 11.10 Condition a second Cu SPE cartridge (1 g, 6 mL) by passing lOmL methanol followed by 20 mL o f HPLC water (~ 2 drop/sec). Do not let column run dry 11.11 Add the methanol to -200 mL of water and load on the second conditioned SPE cartridge. 11.12 Elute with -5 mL 100% methanol. Collect 5 mL o f eluate into graduated 15 mL polypropylene centrifuge tubes (final volume " 5 mL). 11.13 Analyze samples using electrospray LC/MS/MS.
Page 5 of 7
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 47 o f 57 Page 175 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
Exygcn R esearch
Method Number VOOO1782
I____________ ;_____________ ANALYTICAL METHOD______________________ |
Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Sediment by LC/MS/MS
12.0 Chromatography
12.1 Inject the same amount of each standard, sample and fortified sample into the
LC/MS/MS system. A calibration standard must precede and follow all
analyzed samples.
'
12.2 Standards of PFOA corresponding to at least five or more concentration levels
must be included in an analytical set.
12.3 An entire set o f extracted calibration standards must be included at the
beginning and at the end of a sample set. Standards must be interspersed
between every 5-10 samples. As an alternative, an entire set of calibration
standards may be injected at the beginning of a set followed by calibration
standards interspersed every 5-10 samples (to account for a second set of
standards). In either case, calibration standards must be the first and last
injection in a sample set.
12.4 Use linear standard curves for quantitation. Linear standard curves are
generated for the analyte by linear regression using 1/x weighting of peak area
versus calibration standard concentration using MassLynx 3.3 (or equivalent)
software system.
12.5 Sample response should not exceed standard responses. Any samples that
exceed standard responses should be further diluted and reanalyzed.
13.0 Acceptance Criteria
13.1 Chromatogram must show a peak of a daughter ion at 369 amu from a parent of 413 amu. The 413 amu parent corresponds to the PFOA anion, while the daughter ion (369 amu) represents the loss o f carbon dioxide.
13.2 Method blanks must not contain PFOA at levels greater than the LOQ. If a blank contains PFOA at levels greater than 0.2 ng/mL, then a new blank sample must be obtained and the entire set must be re-extracted.
13.3 Recoveries of control spikes and matrix spikes must be between 70-130% of their known values. If a control spike falls outside the acceptable limits, the entire set of samples should be re-extracted. Any matrix spike outside 70 130% should be evaluated by the analyst to determine if re-extraction is warranted.
13.4 Any calibration standard found to be a statistical outlier by using the Huge Error Test, may be excluded from the calculation of the calibration curve. However, the total number o f extracted calibration standards that could be excluded must not exceed 20% o f the total number o f extracted standards injected.
13.5 The correlation coefficient (R) for calibration curves generated must be 20.992 (R2 20.985). If calibration results fall outside these limits, then appropriate steps must be taken to adjust instrument operation, and the standards or the relevant set of samples should be reanalyzed.
Page 6 o f 7
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 48 o f 57 Page 176 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
Exygen Research
Method Number V0001782
ANALYTICAL METHOD
Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Sediment by LC/MS/MS
13.6 Retention times between standards and samples must not drift more than 4 % within an analytical run. If retention time drift exceeds this limit within an analytical run then the set must be reanalyzed.
14.0 Calculations 14.1 Use the following equation to calculate the amount o f PFOA found (in ng/mL, based on peak area) using the standard curve (linear regression parameters) generated by the Mass Lynx software program:
PFOA found (ng/mL) = (Peak area - intercept) x DF slope
DF = factor by which the final volume was diluted, if necessary.
14.2 For samples fortified with known amounts of PFOA prior to extraction, use the following equation to calculate the percent recovery.
Recovery (% )
[total analyte found (ng/mL) analyte found in control (ng/mL)] analyte added (ng/mL)
14.3 Use the following equation to convert the amount o f PFOA found in ng/mL to ng/g (ppb).
PFOA found (ppb) = (PFOA found (ng/mL) x final volume (S mLH sample weight (3 g)
14.4 Use the following equation (if necessary) to calculate the amount o f PFOA found in ppb based on dry weight.
PFOA found (ppb) dry weight = PFOA found (ppb) x [100% / total solids(%)]
Page 7 o f 7
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 49 o f 57 Page 177 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
ANALYTICAL METHOD
Method Number: V0001783
Method of Analysis for the Dtermination of Perfluorooctanoic Acid (PFOA) in Fish and Clams by LC/MS/MS
Analytical Testing Facility:
Exygen Research
3058 Research Drive State College, PA 16801
Approved By:
r tl
Paul Connolly
1
Technical Leader, LC-MS, Exygen Research
Ila-faM
Date
2a John Flaherty
''V ic e President, Operations, Exygen Research
Date
Total Pages: 8
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 50 o f 57 Page 178 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
Exygen Research
Method Number V0001783
| AftALTflCAL METHOD
Method of Analysis for the Determination o f Perfluorooctanoic Acid (PFOA) in Fish and Clams by LC/MS/MS
1.0 Scope
This method is to be employed for the isolation and quantitation o f perfluorooctanoic acid by High Performance Liquid Chromatography coupled to a tandem Mass Spectrometric Detector (LC/MS/MS) in fish and clams.
2.0 Safety
2.1 Always observe safe laboratory practices. 2.2 Consult the appropriate MSDS before handling any chemical for proper safety
precautions.
3.0 Sample Requirement
3.1 At least 20 g of test sample for extraction. 3.2 Samples should be processed before extraction. Place the frozen sample in a
food processor and homogenize with dry ice. Place the samples in containers and leave open in frozen storage overnight to allow for carbon dioxide sublimation. Seal and place the samples in frozen storage undl time of . analysis. 3.3 Sample collection procedures will be specified in the sampling plan for this project.
4.0 Reagents and Standards
4.1 Water - HPLC grade 4.2 Acetonitrile - HPLC grade 4.3 Carbon (120-400 mesh)-Reagent grade 4.4 Methanol - HPLC grade 4.3 Silica gel (60-200 mesh) - Reagent grade 4.6 Florisil (60-100 m esh)-Reagent grade 4.7 Superclean LC-NHj - Reagent grade 4.8 l-O ctanol- HPLC grade 4.9 L-Ascorbic acid - Reagent grade 4 .10 Dimethyldichlorosilane - Reagent grade 4.11 Toluene-Reagent grade 4.12 Ammonium Acetate - A.C.S. Reagent Grade 4.13 Perfluorooctanoic Acid - Sigma-Aldrich
5.0 Instrument and Equipment
5.1 A high performance liquid chromatograph capable of pumping up to 2 solvents equipped with a variable volume injector capable of injecting 3-200 pL connected to a tandem Mass Spectrometer (LC/MS/MS).
3.2 A device to collect raw data for peak integration and quantitation. 3.3 Analytical balance capable of reading to 0.00001 g.
Page 2 of 8
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 51 o f 57 Page 179 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
Exygco Research
Method Number V0001783
ANALYTICAL METHOD
Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Fish and Clams by LOMS/MS
5.4 Rotary evaporator. 5.5 Tissumizer. 5.6 125 mL pear-shaped flasks. 5.7 50 mL disposable polypropylene centrifuge tubes. 5.8 15 mL disposable polypropylene centrifuge tubes. 5.9 Disposable micropipets (S0-100uL, 100-200uL). 5.10 125-mLLDPE narrow-mouth bottles. 5.11 2 mL clear HPLC vial kit. 5.12 Disposable pipettes. 5.13 Autopipettes (100-1000 pL and 10-100 pL), with disposable tips. 5.14 SPE tubes (20mL) (Supelco cat. no. N057177). 5.15 Wrist action shaker. 5.16 Centrifuge capable of spinning 50 mL polypropylene tubes at 2000 rpm.
6.0 Chromatographic System
6.1 Analytical Column: Fluophase RP (Keystone Scientific), 2.1 mm x 50 mm, 5p ( P /N :82505-052130)
6.2 Temperature: 30"C 6.3 Mobile Phase (A) : 2 mM Ammonium Acetate in Water 6.4 Mobile Phase (B) : Methanol 6.5 Gradient Program:
Time (mini 0.0 1.0 8.0 20.0 22.5
%A 65 65 25 25 65
Flow Rate % . CmL/minl 35 0.3 35 0.3 75 0.3 75 0.3 35 0.3
6.6 Injection Volume: 15 pL (can be increased to as much as 50 pL). 6.7 Quantitation: Peak Area - external standard calibration curve. 6.8 Run Time: ~ 23 minutes.
The above conditions are intended as a guide and may be changed in order to optimize the HPLC system.
Page 3 o f 8
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 52 o f 57 Page 180 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
Exygen Research
Method Number V000I783
_________________________ANALYTICAL METHOD____________ .____________
Method o t Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Fish and Clams by LC/MS/MS
7.0 MS/MS System
7.1 Mode: Electrospray Negative MRM mode, monitoring 4 13 -> 369 m/z for PFOA.
The above conditions are intended as a guide and may be changed in order to optimize the MSMS system.
8.0 Preparation of Solutions 8.1 Mobile Phase
8.1.1 2 mM ammonium acetate in water is prepared by adding 0.1S4 g of ammonium acetate to 1000 mL of water.
8.2 Extraction Solutions
8.2.1 8.2.2
2% ascorbic acid in methanol is prepared by dissolving 2 g of ascorbic acid in 100 mL of methanol. 30% Dimethyldichlorosilane in toluene is prepared by bringing 3 mL o f dimethyldichlorosilane to a final volume o f 10 mL with toluene.
Alternate volumes may be prepared.
9.0 Standard Preparation 9.1 Standard Stock/Fortification Solution
9.1.1
9.1.2
9.1.3 . 9.1.4
9.1.5
Prepare a stock solution o f --100 pg/mL of PFOA by weighing 10 mg of analytical standard (corrected for purity) and dilute to 100 mL with methanol in a 125-raL LDFE bottle. A 1.0 pg/mL fortification solution of PFOA is prepared by bringing I mL of the 100 pg/mL solution to a final volume of 100 with methanol in a 12S mL LDPE bottle. A 0.1 pg/mL fortifreation solution of PFOA is prepared by bringing 10 mL of the 1.0 pg/mL solution to a final volume o f 100 with methanol in a I2S mL LDPE bottle. A 0.01 pg/mL fortification solution of PFOA is prepared by bringing 10 mL of the 0.1 pg/mL solution to a final volume of 100 with methanol in a 125 mL LDPE bottle. The stock and fortification solutions are to be stored in a refrigerator at approximately 4C and are stable for a maximum period of 6 months from the date of preparation.
Page 4 of 8
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 53 o f 57 Page 181 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
Exygcn Research
Method Number V0001783
r _________________________ANALYTICAL m e t h o d _________________________
Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Fish and Clams by LC/MS/MS
9.2 Standard Calibration Solutions
9.2.1 9.2.2
LC/MS/MS calibration standards are prepared in methanol via dilution of the 1.0 pg/mL fortification solution. The following is a typical example: additional concentrations may be prepared as needed.
Concentration
Final
o f Fortification Volume
Diluted to
Concentration
Solution (wt/mL) (mL)
(mL)
(m(t/mL)
l.O 3.0 100
0.05
l.O 2.5 100
0.025
1.0 1.0 100
0.01
0.03 10 100
0.005
0.025
10
100
0.0025
0.1 10 100
0.001
0.005
10
100
0.0005
9.2.3 Store all calibration standards in 125-mL LDPE narrow-mouth bottles
at 2C to 6C, up to six months.
9.2.4 Alternate volumes and concentrations of standards may be prepared as
needed.
10.0 Batch Set Up
10.1 Each batch o f samples extracted (typically 20 or less) must include at least one untreated control and two untreated controls fortified at known concentrations (lab control spike) to verify procedural recovery for the batch.
10.2 Requirements for field and laboratory duplicates and spikes will be specified in the quality assurance plan for this project.
11.0 Sample Extraction
11.1 Weigh 5 g of frozen sample into 30 mL polypropylene centrifuge tubes (fortify as needed, replace lid and mix well).
11.2 Add 30 mL of acetonitrile and shake on a wrist action shaker for-13 minutes. 11.3 Place the tubes in a freezer for -1 hour. 11.4 Pack and condition the SPE tubes and silanize the pear-shaped flasks. 11.3 Pack the 20 mL SPE tubes in sequence with 2 g florisil, 2 g silica gel, 2 g
carbon, and 1 g LC-NHj. Condition 1he columns with 20 mL of methanol, then 20 mL of acetonitrile. Discard all washes. Do not allow the column to dry. ll.fi Silanize the 123 mL pear-shaped flasks by rinsing with the 30% dimethyldichlorosilane in toluene solution. Rinse the flask with toluene once, followed by methanol (three times). Dry the flasks completely before use, either by air-drying or with a stream o f nitrogen.
Page 5 o f 8
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 54 o f 57 Page 182 of 209
3M Environmental Laboratory P0003268; Interim Report#2
ExyLIMS Protocol Number: P0003268
Exygen Research
Method Number VOOO1783
| ANALYTICAL METHOD
Method o f Analysis for the Determination ofPerfluorooctanoic Acid (PFOA) in Fish and Clams by LC/MS/MS
11.7 Centrifuge the SO mL polypropylene tubes containing sample at ~2000 rpm for -10 minutes.
11.8 Decant the extract on to a conditioned SPE column fitted inside the mouth of the pear-shaped flask. Collect the eluate in the 12S mL silanized pear-shape flask.
11.9 Add 10 mL o f acetonitrile to the sample in the SO mL centrifuge tube. Homogenize the frozen fat phase using a tissumizer for -3 0 seconds and rinse the tissumizer with -10 mL of acetonitrile into the tube.
11.10 Shake the sample again for~IO minutes on a wrist-action shaker. 11.11 Place the tubes in a freezer for - 1 hour more. 11.12 Centrifuge the SO mL polypropylene tubes containing sample at -2000 rpm
for-1 0 minutes. 11.13 Decant the extract onto the same SPE column. Collect the eluate into the
same pear-shaped flask and combine with the eluent from the initial extraction. 11.14 Pass 20 mL of acetonitrile through the SPE column and combine the eluate in the same pear-shaped flask. 11.15 Add 3-4 drops of 1-octanol to the extract in the pear-shaped flask and evaporate at reduced pressure using a rotary evaporator (at < 40C). 11.16 Make the final volume, by adding 2 mL of 2% ascorbic acid in methanol to the pear-shaped flask and swirl to mix/dissolve. 11.17 Transfer the extracts to HPLC vials using disposable pipets. 11.18 Analyze samples using electrospray LC/MS/MS.
12.0 Chromatography
12.1 Inject the same amount of each standard, sample and fortified sample into the LC/MS/MS system. A calibration standard must precede and follow all analyzed samples.
12.2 Standards o f PFOA corresponding to at least five or more concentration levels must be included in an analytical set.
12.3 An entire set of calibration standards must be included at the beginning and at the end of a sample set. Standards must be interspersed between every 5-10 samples. As an alternative, an entire set o f calibration standards may be injected at the beginning of a set followed by calibration standards interspersed every 5-10 samples (to account for a second set o f standards). In either case, calibration standards must be the first and last injection in a sample set.
12.4 Use linear standard curves for quantitation. Linear standard curves are generated for the analyte by linear regression using 1/x weighting o f peak area versus calibration standard concentration using MassLynx 3.3 (or equivalent) software system.
Page 6 of 8
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 55 o f57 Page 183 of 209
3M Environmental Laboratory P0003268; Interim ReporW2
ExyLIMS Protocol Number: P0003268
Exygen Research
Method Number VOOO1783
I a n a ly tica l m eth o d
Method of Analysts for the Determination of Perfluorooctanoic Acid (PFOA) in Fish and Clams by LC/MS/MS
12.5 Sample response should not exceed standard responses. Any samples that exceed standard responses should be further diluted and reanalyzed.
13.0 Acceptance Criteria
13.1 Chromatogram must show a peak o f a daughter ion at 369 amu from a parent
of 413 amu. The 413 amu parent corresponds to the PFOA anion, while the
daughter ion (369 amu) represents the loss of carbon dioxide.
13.2 Method blanks must not contain PFOA at levels greater than the LOQ. If a
blank contains PFOA at levels greater than 0.5 ppb, then a new blank sample
must be obtained and the entire set must be re-extracted.
13.3 Recoveries of control spikes and matrix spikes must be between 70-130% of
their known values. If a control spike falls outside the acceptable limits, the
entire set o f samples should be re-extracted.
.
13.4 Any calibration standard found to be a statistical outlier by using the Huge
Error Test, may be excluded from the calculation o f the calibration curve.
However, the total number of calibration standards that could be excluded
must not exceed 20% of the total number of standards injected.
13.5 The correlation coefficient (R) for calibration curves generated must be
20.992 (RJ 20.985). If calibration results fall outside these limits, then
appropriate steps must be taken to adjust instrument operation, and the
standards or the relevant set of samples should be reanalyzed.
13.6 Retention times between standards and samples must not drift more than
4 % within an analytical run. If retention time drift exceeds this limit within
an analytical run then the set must be reanalyzed.
14.0 Calculations
14.1 Use the following equation to calculate the amount o f PFOA found (in ng/mL, based on peak area) using the standard curve (linear regression parameters) generated by the Mass Lynx software program:
PFOA found (ng/mL) * (Peak area - intercept! slope
14.2 Use the following equation to convert the amount o f PFOA found in ng/mL to ng/g (ppb).
PFOA found (ppb) " (PFOA found (ng/mL) x final volume (m l) x DF1 sample weight (g)
DF = factor by which the final volume was diluted, if necessary.
Page 7 of 8
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 56 o f 57 Page 184 o f 209
3M Environmental Laboratory P0003268; Interim R eports
ExyLIMS Protocol Number: P0003268
Exygen Research
Method Number V0001783
I ANALYTICAL METHOD
Method o f Analysis for the Detemiination of Perfluorooctanoic Acid (PFOA) in Fish and Clams by LC/MS/MS
14.3 For samples fortified with known amounts of PFOA prior to extraction, use the following equation to calculate the percent recovery.
Recovery (%) =
[ total analyte found (ng/g) analyte found in control (ng/g)] analyte added (ng/g)
Page d o r s
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 57 o f 57 Page 185 of 209
3M Environmental Laboratory P0003268; Interim R eports
Exygen Protocol P0003268 Amendment 1
Study Title "Analysis of Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in W ater, Soil, Sediment, Fish, and Clams Using LC/MS/MS
for the 3M Decatur Monitoring Program"
PROTOCOL AMENDMENT NO. 1
Am endm ent Date: August 24, 2007
Perform ing Laboratory 3M Environmental, Health, and Safety Operations
3M Environmental Laboratory Building 260-5N-17
Maplewood, MN 55144-1000
Laboratory P roject Identification GLP07-0003
Page 1 of 4
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 186 of 209
3M Environmental Laboratory P0003268; Interim Reports
Exygen Protocol P0003268 Amendment 1
This amendment modifies the following portion of protocol: "Analysis o f Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil, Sediment, Fish, and Clams Using LC/MS/MS
for the 3M Decatur Monitoring Program"
Protocol reads:
Testing Facility
MPI Research, Inc. (formerly Exygen Research, Inc.) State College 3058 Research Drive State College, PA 16801 Phone: (814)272-1039 Fax: (814) 231-1580
A m end to read:
Testing Facility
MPI Research, Inc. (formerly Exygen Research, Inc.) State College 3058 Research Drive State College, PA 16801 Phone: (814) 272-1039 Fax: (814) 231-1580
3M Environmental, Health, and Safety Operations 3M Environmental Laboratory Building 260-5N-17 Maplewood, MN 55144-1000
Reason:
Additon of the 3M Environmental Laboratory as a testing facility allows samples to be sent to the 3M Environmental Laboratory for analysis. The initial sample analysis is outlined in the attached General Project Outline (GPO) authored by Michelle Mallnsky, 3M Principal Analytical Investigator.
Page 2 of 4
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 187 of 209
3M Environmental Laboratory P0003268; Interim Report#2
Exygen Protocol P0003268 Amendment 1
Protocol reads:
Analytical Procedure Sum m ary
References: ETS-8-12.0: Method of Analysis for the Determination of Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid (PFPeA), Perfluorohexanoic Acid (PFHA), Perfluoroheptanoic Acid (PFHpA), Perfiuorooctanoic Acid (PFOA), Perfluorononanoic Acid (PFNA), Perfluorodecanoic Acid (PFDA), Perfluoroundecanoic Acid (PFUnA), Perfluorododecanoic Acid (PFDoA), Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfiuorooctanesulfonate (PFOS) in Water, Soil and Sediment by LC/MS/MS
A m end to read:
Analytical Procedure Sum m ary
References: ETS-8-12: Method of Analysis for the Determination of Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid (PFPeA), Perfluorohexanoic Acid (PFHA), Perfluoroheptanoic Acid (PFHpA), Perfiuorooctanoic Acid (PFOA), Perfluorononanoic Acid (PFNA), Perfluorodecanoic Acid (PFDA), Perfluoroundecanoic Acid (PFUnA), Perfluorododecanoic Acid (PFDoA), Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfiuorooctanesulfonate (PFOS) in Water, Soil and Sediment by LC/MS/MS
ETS-8-154: Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates in W ater by Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry
ETS-8-044: Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection Analysis
Reason:
These additional 3M Environmental Laboratory methods allow samples to be analyzed by other methods if deemed appropriate by the 3M principal analytical investigator and 3M Environmental Laboratory management.
Page 3 of 4
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 188 of 209
3M Environmental Laboratory P0003268; Interim Report2
Amendment Approval
Exygen Protocol P 0003268 Amendment 2
Michael Aa, Sanjdb, oS--ponsorRepresentative '
....
t \. / .'
J.J'tCU ,H'/i: -J.- .. ] i i
.
Michelle D. Malinsfcy,Ph.D., Prin^pal Analytical investigaior
'.." Date
'itb at
EHS Opns Environmental Lab Management Jaisimha Kesari P.E., DEE, Study Director
Date * Date
Page 3 o f3
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 189 of 209
3M Environmental Laboratory P0003268; Interim Report#2
Amendment Approval
Exygsn Protocol PQQ3268 Amendment 2
Michael A. Santoro, Sponsor Representative
Date
Michelie D.
oal Analytical investigator
EHS Opns Environmental Lab Management Jaisimha Kesari P.E., D Eii Study Director
Bau
Date
Page 3 of 3
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 190 of 209
3M Environmental Laboratory P0003268; Interim Report#2
H w l Environmental Health & Safety Operations, Environmental Laboratory General Project Outline
To: Gary Hohenstein, 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 Dale Bacon, 3M EHS&Opns; Environmental Lab Casey Howell, QAI, 3M EHS&Opns; Environmental Lab Tim Frinak, Weston Solutions, Inc. Jai Kesari, Weston Solutions, Inc.
Date: Subject:
August 23,2007
Decatur Off-site Surface Water and Sediment Sampling week of August 27, 2007 under GLP Protocol P3268 (3M Environmental Laboratory Request GLP07-003)
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 191 of 209
3M Environmental Laboratory P0003268; Interim Report#2
1 General Project Information
ProjectCoordinators)
GLP StudyDirector GLP SponsorRepresentative AnalyticalFacilityManagement LabRequestNumber SixDigitDepartmentNumber ProjectSchedule/TestDates
3M OverallProjectCoordinator GaryHohenstein 3M EHS Operationo 42-2E-27 651-778-5150 gahohenstein@mmm.com
FieldSamplingCoordinator TimFrinak Weston Solutions,Inc.
3M AnalyticalProjectManagement KentLindstrom 3M EHS Opns,EnvironmentalLaboratory 260-5N-17 651-733-9882 krlindstromIBmmmcom
PrincipalAnalyticalInvestigator MichelleMalinsky 3M EHS Opns,EnvironmentalLaboratory 260-5N-17 651-733-9859 mmalinskv(mmm.com JafelmhaKesari
Weston Solutions,Inc. 1400WestonWay Westchester,PA 19380 MichaelA.Santoro
3M Company
WilliamK.Reagen
3M EnvironmentalLaboratoryManager
3M EHS Opns,EnvironmentalLaboratory 260-5N-17 651-733-9739 wkreagen@m mm.com
GLP07-0002
530711
SamplingtoCommence on August28,2007
A ll verbal and written correspondence will be directed to Gary Hohenstein.
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 192 of 209
3M Environmental Laboratory P0003268; Interim Report#2
2 Background Information and Project Objective(s)
On August 28,2007, personnel from Weston Solutions, Inc. will collect sediment and surface water samples from an off-site location near the 3M Decatur facility. The EHS Operations Environmental Laboratory will analyze the water samples for perfluorobutanesulfonate (PFBS), perfluorohexanesulfbnate (PFHS), and perfluorooctanesulfonate (PFOS) under GLP study GLP07-0003 (MPI Protocol #P3268). The final report will be submitted to Gary Hohenstein upon completion.
3 Project Schedule
Sample collection bottles will be prepared by 3M Environmental Laboratory professional services personnel for arrival in Decatur, AL no later than Monday August 27,2007. Collection bottles will be sent to the Weston Solutions, Inc. office located at the 3M Decatur facility.
4 Test Param eters
4.1 W ater Sam ples
Estimated reporting limits will be 0.025ng/mL (ppb) for the three target analytes.
A total of five sample sites have been specified. For each sampling location, a total of four or five sample bottles will be collected (sample, sample duplicate, low-level field matrix spike, mid-level matrix spike when appropriate, and high-level matrix spike). The `Till to here" line on each 500 mL Nalgene bottle will be 450 mL. The table below provides the spike levels associated with each location. Additionally, Weston has requested two bottles for equipment rinseate samples. Additionally, three trip blank sets consisting of reagent-grade water, a low-level trip blank spike, mid-level trip blank spike, and a high-level trip blank spike will be prepared at the 3M Env. Laboratory and sent to the sampling location with the other bottles. Three trip blank sets will allow for samples to be sent back to the laboratory in three separate shipments if necessary. A total of 37 sample bottles will be prepared. Additionally, the lab will send two one-liter bottles of reagent grade water to be used for equipment rinsing.
Table 1. Sample Locations and Spike Levels for Surface Water Samples.
Sample Location WestPond Location1
*Historical PFBS Cone. (ng/mL)
NA
historical PFHS Cone. (ng/mL)
NA
historical PFOS Cone. (ng/mL)
NA
Low Spike Cone. (ng/mL)
0.25
WestPond Location2
NA NA NA 0.25
EastPond Location1
7.63 61.8 437
10
EastPond Location2
7.63 61.8 437
10
Swamp Location1(EmergentMarsh)
7.63 61.8 437
10
EquipmentRinseate1
NA NA NA **NA
EquipmentRinseate2
NA NA NA **NA
TripBlankSet1
NA NA NA 0.25
TripBlankSet2
NA NA NA 0.25
TripBlankSet3
NA NA NA 0.25
Maximum surfacewaterconcentrationswithinthe"EastPond"samplingarea.
"EquipmentRinseatesdonotrequirefieldmatrixspikes.
Mid Spike Cone. (ng/mL)
NA NA 100 100 100 **NA **NA 10 10 10
High Spike Cone. (ng/mL)
5.0 5.0 500 500 500 **NA **NA 500 500 500
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 193 of 209
3M Environmental Laboratory P0003268; Interim Report#2
4.2 Sediment Samples
Estimated reporting limits will be 0.20 ng/g for sediment samples.
A total of 39 primary field sediment samples will be collected. Duplicate sediment samples will be collected for four selected locations. Weston has requested two extra sediment collection bottles. Matrix spikes for sediment will be prepared in the laboratory. Each location will have only one sample bottle. If a blank sediment matrix is available, two sediment trip blanks will be sent to the facility with the bottles.
5 Test Methods
5.1 Water Samples
Water samples will be extracted and analyzed by LC/MS/MS using procedures outlined in ETS 8-154 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In Water By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry". This method has been validated for PFOS; however, specific quality control samples analyzed with the samples will be used to determine overall method precision and accuracy for all analytes. The data quality objectives for these studies are quantitative results for the target analytes with an analytical accuracy of 10030%. Field matrix spikes not yielding recoveries within 10030% will be addressed in the report and the final accuracy statement may be adjusted accordingly. Additional water analysis methods that may be used if deemed appropriate by the PAI and 3M laboratory management include the following: ETS 8-44 "Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis" ETS 8-12 "Method of Analysis for the Determination of Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid (PFPeA), Perfluorohexanolc Acid (PFHA), Perfluoroheptanoic Acid (PFHpA), Perfluorooctanoic Acid (PFOA), PerfluorononanolcAcid (PFNA), Perfluorodecanoic Acid (PFDA), Perfluoroundecanoic Acid (PFUnA), PerfluorododecanoicAcid (PFDoA), Perfluorobutanesulfbnate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil, and Sediment by LC/MS/MS.
5.2 Sediment Samples
Sediment samples will be extracted and analyzed by LC/MS/MS using procedures outlined in ETS 8-12 "Method ofAnalysisforthe Determination of Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid (PFPeA), PerfluorohexanoicAcid (PFHA), Perfluoroheptanoic Acid (PFHpA), Perfluorooctanoic Acid (PFOA), PerfluorononanolcAcid (PFNA), Perfluorodecanoic Acid (PFDA), Perfluoroundecanoic Acid (PFUnA), PerfluorododecanoicAcid (PFDoA), Perfluorobutanesulfbnate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil, and Sediment by LC/MS/MS". If a blank sediment matrix Is available, an extracted calibration curve will be prepared to analyze the sample extracts. If not, sample extracts may be analyzed against a calibration curve prepared using the solvent mix used to extract the samples. If necessary, a curve may be prepared using a sample sediment that was screened and determined to have low levels of the target analyte. Lab matrix spikes will be prepared for each sample. Lab matrix spikes not yielding recoveries within 10030% will be addressed in the report and the final accuracy statement may be adjusted accordingly. Laboratory duplicates will be prepared for each sample. The four field duplicates collected will assess sample collection precision.
6 Reporting Requirements
6.1 Water Samples
For each sampling location, the report will contain the results for the sample, sample duplicate, and the two (or three) field matrix spikes. Trip blank(s) and associated trip blank spikes will also be reported. Laboratory control
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 194 of 209
3M Environmental Laboratory P0003268; Interim Report#2
spikes of reagent water prepared at the time of sample extraction will also be reported and used to evaluate the overall method accuracy and precision.
6.2 Sediment Samples
For each sample location, the report will contain the results for the sample, laboratory duplicate, field duplicate if appropriate, and the prepared laboratory matrix spike(s). If a blank sediment matrix is available, lab control spikes prepared at the time of sample extraction will also be reported and used to evaluate the overall method accuracy and precision.
7 Attachments
None. GLP protocol is available upon request. Not attached due to file size limitations.
8 E-mail Communications
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 195 of 209
3M Environmental Laboratory P0003268; Interim Report#2
"Young, Charles T." <Char1es.Young@WestonSol utions.com>
08/22/2007 03:32 PM
To ''Kent Lindstrom" <krlindstrom@mmm.com> 'Michelle Malinsky" <mmalinsky@mmm.com>
cc "Kesari, Jal" <J.Kesarl@WestonSolutlons.com> "Frinak, Timothy R." <T.Frinak@WestonSolutions.com>
bcc
Subject P3267 / P3268 Decatur off-site SW/SD sampling
[ History
jgi this message has been replied to.
Kent and Michelle:
The off-site sediment (SD) and surface water (SW) samples to be collected at Decatur starting on Tuesday 8/28 and analyzed under the GLP Protocols P3267 and P3268 include the following:
39 primary sediment samples 4 field duplicate sediment samples Please add two spare bottles for the sediments
5 surface water samples 2 Equipment rinseate samples
3 Trip blank samples
Of the S W samples, 2 are from a location upgradient of sources It is anticipated that only 0.25 and 5 ng/mL spikes would be required for these "West Pond" samples.
Based on earlier sampling, the maximum SW concentrations within the "East Pond" sampling area were 526 ppb PFOA, 7.63 ppb PFBS, 61.8 ppb PFHS and 437 ppb PFOS. Current concentrations may be lower than previous so low range coverage by field spikes will be necessary in the event that concentrations have dropped appreciably.
I will provide information that may be helpful in determining lab spiking levels for the sediments in a subsequent email.
Thanks, Charlie
Charles T. Young
Technical Director Weston Solutions, Inc. 1400 Weston Way (4-2) West Chester, PA 19380 (610) 701-3787 fax x7401
CONFIDENTIALITY : This e-mail and attachments may contain information which is confidential and proprietary. Disclosure or use o f any such information without the written permission o f W eston Solutions, Inc. is strictly prohibited. I f 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.
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 196 of 209
3M Environmental Laboratory P0003268; Interim Report#2
Exygen Protocol P0003268 Amendment 2
Study Title "Analysis o f Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil, Sediment, Fish, and Clams Using LC/MS/MS
for the 3M Decatur Monitoring Program"
PROTOCOL AMENDMENT NO. 2
Am endm ent Date: September 5, 2007
Perform ing Laboratory 3M Environmental, Health, and Safety Operations
3M Environmental Laboratory Building 260-5N-17
Maplewood, MN 55144-1000
Laboratory P roject Identification GLP07-02
Page 1 o f 3
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 197 of 209
3M Environmental Laboratory P0003268; Interim Reports
Exygen Protocol P0003268 Amendment 2
This amendment modifies the following portion of protocol: "Analysis o f Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil, Sediment, Fish, and Clams Using LC/MS/MS
for the 3M Decatur Monitoring Program"
P rotocol A m endm ent 1 reads: Laboratory Project Identification GLP07-0003
A m end to read: Laboratory Project Identification GLP07-02
Reason: When the original GLP project was created using the 3M Environmental Laboratory's Laboratory Information Management System (LIMS), the wrong project template was used. With the correct template, all samples collected under protocol P0003268 and analyzed at the 3M Environmental Lab will be logged in under GLP program number GLP07-02. Samples from individual sampling events or different subcategories of samples (i.e. water vs. sediment) will be logged under separate projects under the same GLP program number. For example, the sediment samples collected on August 28-29, 2007 will be logged under GLP project number G LP 07-02-01. Samples from the next event will be logged under project number GLP07-02-02. The new GLP program template allows for easier sample tracking and management when numerous samples will be collected over an extended period of time.
Page 2 of 3
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 198 o f 209
3M Environmental Laboratory P0003268; Interim Report#2
Am endm ent Approvai
Exygen Protocol P0003268 Amendment 2
Michael A. Santoro, Sponsor Representative
V1 - , . / \ A
i/it dJ IIIiy j.M /y ic y " Michelle D. Malinsky, |Ph.D., Principal Analytical Investigator
Date dat
EHS Opns Environmental Lab Management Jaisimha Kesari P.E., DEE, Study Director
Date Date
Page 3 o f 3
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 199 of 209
3M Environmental Laboratory P0003268; Interim Reportt2
Amendment Approval
Exygen Protocol P 00 03 26 8
Amendment 2
d
Michael A. Sanfriro, Sponsor Representative
Michelle D. Malinsky. Ph.D.. Priiysjjjal Analytical Investigator EHS Opns Environmental Lab Management Jaisimha Kesari P.E., DEE, Study Director
Date Date
Page 3 o f 3
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 200 of 209
3M Environmental Laboratory P0003268; Interim Report#2
Amendment Approvai
Exygen P rotocol POO3268 Amendment 2
Michael A. Samoro, Sponsor Representative
Date
Micheli.: ! '
' . < ' I al Analytical investigator
Baie
Page 3 o f 3
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 201 of 209
Attachment D: Method Deviations
3M Environmental Laboratory P0003268; Interim Report#2
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 202 of 209
3M Environmental Laboratory P0003268; Interim Reporttf2
3M Confidential
Record of Nonconformance / Deviation
___:......... _ ....... ................................................ I. Id e n tific atio n
Study / Project No.
Date(s) of Occurrence:
Q LF07-02-0 1 .. .................... ..........I 9/27/2007; 10/23/2007
Document Number: ETS-8-12.1
Delation type SOP
o Equipment Procedure 0 Method
(Check one) Protocol_______ GPQ_____________
O ther____________
________________________________________ II. D e s c rip tio n ______________________
Method Requirements:
Section 12.2 CCV Performance The accuracy of each analyte must be within 25% of the theoretical value.
Actual procedure/process:
The following injections did not meet method acceptance criteria.
Injection Num ber o070927a078
o071023a051 o071023a063 o071023a087 o071023a087
Analyte PFBS
PFHS
PFOS PFOS PFOS PFHS
%Recovery Not
Calculated, >ULOQ
Not Calculated,
>ULOQ
126% 128% 131% 126%
Comment
Curve point above upper calibration range (not in original curve) Area counts of CCV were 109% Of tire area counts of the original injection. Instrument still stable. Curve point above upper calibration range (not in original curve). Area counts of CCV injection were 101% of the area counts of the original injection. Instrument still stable. Within overall method uncertainty of 10030% Within overall method uncertainty of 100+30% Exceeds overall method uncertainty by 1% Exceeds overall method uncertainty by 5% and method accuracy requirement by 1%.
III. Actions Taken (such as amendment issued, SOP revision, etc.)
Corrective Action ( Yes 0 No) Reference:
Acceptability of the nonconforming work:
The degree of CCV non-compliance w as minimal. Deviation will be mentioned In the report. Affected samples will be footnoted accordingly with an expanded uncertainty if appropriate.
Actions: Halting of Work Client Notification Work Recall Withholding of Report 0 Other: See above.
Print Date: 1/15/2008 Print Time: 12:08:40 PM
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 1 of 2 Page 203 of 209
3M Environmental Laboratory P0003268; Interim Reportft2
3M Confidential
Record of Nonconformance / Deviation
R ecordedby: Michelle D. Malinsky
I
/ / !/ '
\ / * 'V . . -
'-y-; sui;
GLP Study BSrector A dtoorizatioi^
..... J&ZML .4 ........................................
GLP Sponsor Approval / G ^ Protocols):
..................;.... ...............................................................................
Technical Manager Approval (ifhalting ofwortcor work recall are Indicated)!
Date: 1/15/2008
IfiS X o g '
Date: / /
:
z/
Date:
'7$
/
: .........
I Date: `
IV. Authorization to Resum e W ork
_______ Wham halting o f work occurred, resumption of work must first be approved by Technical Management
Technical Manager Approval:
Date:
D eviation No.
(a ssig ne d b y S tu d y D ire c to r o r P ro je c t L e a d a t the a n d o f s tu d y o r protect)
Print Date: 1/15/2008 Print Time: 12:08:40 PM
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 2 of 2 Page 204 o f 209
3M Environmental Laboratory P0003268; Interim Report#2
3M Confidential
Record of Nonconformance / Deviation
Study / Project No.
G IPQ 7-02-01
Deviation type
(C h e c k one)
SOP Protocol
Method Requirements:
/. Identification
Date(s) of Occurrence: 9 /2 7 /2 0 0 7
Equipment Procedure GPO
//. D escription
! Document Number: ; ETS-8-12.1
0 Method Other:
Section 12.2 Calibration Curve
.......................... ........ .......................
The concentration o f each point in the curve must back calculate to be within 125%
theoretical....
concentration with the exception o f 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.
Actual procedure/process:
The 0.1 ng/mL calibration standard for PFBS w as deactivated because it produced an accuracy of
135%._______________________ ;____________________________________________
III, A ctio n s Taken
___________________________________ (such as amendment issued, SOP revismn, etc.) ____________________________
Corrective Action ( Yes 0 No) Reference:
Acceptability o f the nonconforming work:
The PFBS curve was used with the deactivated (or non-compliant) m id-level point. Aii PFBS LCSs and
LMSs m et method criteria for this batch. Three of the fifteen pants prepared w ere deactivated with two
of the points being at the uppermost calibration range where a non-linear response w as observed.
Consequently, one point out o f the twelve in the final overall calibration range w as deactivated which
corresponds to less than 25% of the standards in the overall final calibration range being excluded. This
falls under the acceptance criteria set forth in the FDA guidance to validation o f analytical methods when
using extracted calibration standards referenced in ETS 4-010.2. ...... ...........
...................
Actions: Halting of Work Client Notification W ork Recall Withholding of Report
.................. O th er:........................................................................
............ ....................... ............................
Recorded by: M ichelle D. M alinsky
.
Date: 12/17/2007
A u th o riza tio n :
Date:
Sponsor Approval (GLP Protocols):, , , /
7 / cx>,
......................................
.... i
Technical Manager Approval (ifhaltingofworkorworkricallareindicated):
Date: ' f / . Of<.m i n
' Date: // 7
IV, A uthorization to Resume Work
_______ Where halting o f work occurred, resumption of work must first be approved by Technical Management
Technical Manager Approval:
Date:
D eviation N o .______ 2________
Project(a s s ig n e d b y S tu d y D ir e c to r o r
L ea d a t the e n d o f s tu d y o r pre lect)
ETS -4-08.4
Page 1 of 1
Attachm ent A: Record of Nonconformance / Deviation form
Documentation of Deviations and Control of Nonconforming Testing
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 205 of 209
3M Environmental Laboratory P0003268; Interim Report#2
3M Confidential
Record of Nonconformance I Deviation
Study / Project No. G LP07-02-01
Deviation type
(C heck one)
SOP Protocol
Method Requirements:
I. Identification
Date(s) o f Occurrence: All dates samples analzyed
Document Number: E T S -8 -1 2 .1
Equipment Procedure 0 Method
GPO
Other.
//. Description
Section 10.6 Field Matrix Spikes/Lab Matrix Spikes
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 determ ine the statem ent of accuracy for analytical results.
Actual procedure/process:
All spike levels that w ere less than 0.5 times the endogenous level w ere listed as "NR" (not reportable);
however, spike levels greater than 10 times the endogenous level w ere not flagged in the data tables as
not reportable._________________________________________________________________________________
III. A ctions Taken ___________________________________ (such as amendment issued, SOP revision, etc.)_____________
_______
Corrective Action ( Yes 0 No) Reference:
Acceptability of the nonconforming work:
The spiking range provided In the method is intended to be a guideline. The lower limit Is considered
more critical for assigning the sample accuracy as it is more difficult to accurately quantitate a recovery
for a small change In overall concentration when the sample Is spiked. The upper limit is provided to
prevent samples being spiked with an "excessive* concentration w ere the amount attributed to the
sample is negligible. For this report (in general), if a spike level exceeded 10X the endogenous
concentration, the low level spike was within the target range and produced an acceptable recovery
unless otherwise noted. If the low level spike did not m eet criteria, the sam ple result was assigned an
expanded uncertainty.
...........
..................................................................
Actions: Halting of W ork Client Notification W ork Recall Withholding of Report
0 Other: Deviation addressed in report.
Recorded by: M ichelle D. Malinsky
Date: 12/20(2007
A u th o riz a tio n :
2
..........
J ... v / ,,
Sponsor Approval (G IP Protocols) : , , ' ,
vV i/ /y.'
T echnica! Manager Approval (ifhaltingofworkorworkraallareindicated):
Date:
Date: . / . . p iM M
Date:
IV. A uthorization to Resum e W ork Where halting of work occurred, resumption o f work must first be approved by Technical Management
Technical Manager Approval:
Date:
D e v ia tio n N o . ________ 3___________
(a ssig ne d b y S tu d y D ire c to r o r P ro ject L e a d a t the e n d o f s tu d y o r p ro ject)
ETS -4-08.4
PaQe 1 of 1
Attachment A: Record o f Nonconformance / Deviation form
Documentation of Deviations and Control of Nonconforming Testing
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 206 of 209
3M Environmental Laboratory P0003268; Interim Reporttt2
3M Confidential
Record of Nonconformance / Deviation
Study / Project No. G LP 07-02-01
Deviation type
(Check one)
GPO directive:
S O P ....... Protocol
i. identification
; Date(s) of Occurrence:
i August 31,2007
................................................
Equipment Procedure
0 6P0
it. Description
Document Number: GPO - no document number assigned ...................... ..... Method Other:
The GPO written for this sampling event indicated t a t both sediment and surface water samples were to be collected.
Actual procedure/process:
Only sediment samples were returned to the laboratory for analysis. The attached e-mail dated 9/5/2007 from Charles Young to Michelle Malinsky indicates that water samples were not collected as no standing water was available for sampling in any of the pre-designated areas. ...............................
HI. Actions Taken
{such as amendment Issued, SOP revision, etc.)
Corrective Action ( Yes 0 No) Reference:
Acceptability of the nonconforming work:
W ater samples not being collected was addressed in the final report.
Actions: Halting of W o k Client Notification Work Recall O Withholding of Report Other:
Recorded by: Michelle D. Malinsky
GLP Study Director orization:
GLP Sponsor Approval:
his
Technical Manager Approval (haltingofwoVorwofkrecallareindicated):
Date: 1/14/2008 Date:
IV. Authorization to Resume Work
_______ WhemJis!ting_of work occurred, resumption of work must first be approved by Technical Management
Technical Manager Approval:
Date:
PrintDate: 01/14/2005
Deviation No.
(assigned b y S tudy D irector o r P roject L ea d a t the e nd o f stud y o r project)
Page1of3
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 207 of 209
3M Environmental Laboratory P0003268; Interim R eports
"Young, Charles T * <Chartes.Young@WestonSolu Hons.com>
09/05/2007 02:10 PM
To <mm8linsky@mmm.com> cc bcc
S ub ject R E: D ecatu r S am ples
Wtetory:.................... f Th is m essage has beert rep lied to.
Michelle:
You have the full set samples from this collection effort. There was no standing water in any of the areas designated for sampling and consequently, no samples were collected. The SW bottles were sent back with the GDP sediment and non-GhP water samples shipment.
Sorry that we didn't advise you of the change in sample matrices / quantities earlier.
Regards,
Charlie
Charles T. Young
Technical Director Heston Solutions, Inc. 1400 Weston Way (4-2) West Chester, PA 19380 !610) 701-3787 fax x7401
-----Original Message----From: mmalinsky@mmnv.com mailto:mmalinsky@miraji.com} Sent: Wednesday, September 05, 2007 2:25 PM To: Young, Charles T. Subject: Decatur Samples
Charlie,
Hello. Hope you had a good long weekend. I just wanted to let you know that we received all the sediment samples and non-GI,P water samples from Decatur on Friday. We have not received the GLP water samples. Do you know when we should expect them??? I 'm just trying to do some strategic planning regarding lab personnel and equipment for the next week or so {the lab as a whole has a ton of stuff going on right now...) and a heads up would be appreciated.
Thanks, Michelle
Regards, Michelle D. Malinsky 3M EHS Operations Environmental Lab Bldg. 26Q-5N-17 St. Paul, m 55144-1000
Tel: 651-733-9859
PrintData: 01/14/2008
Page2of3
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 208 o f 209
3M Environmental Laboratory P0003268; Interim R eporm
FAX: 651-733-4687 wmalifts k y @ m m m .c o m CONFIDENTIAL This communication is intended only for the addresseets) 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.
printDate: 01/14/2008
Page3of3
3M Environmental Laboratory
GLP07-02-01, Decatur Sediments Sulfonates
Page 209 of 209
