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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-05-02
Final Report
A n a ly s is o f P F O A , P F B S , P F H S a n d P F O S in G ro u n d W a te r S a m p le s C o lle c te d a t th e F o rm e r S lu d g e In c o rp o ra tio n A re a (F S IA ) fro m D e c a tu r, A L 1 st Q u a r t e r 2 0 1 4
L a b o ra to ry R e q u e s t N u m b e r: IS O 1 4 -0 5 -0 2 M e th o d R e q u ire m e n t: 3 M M e th o d E T S -8 -0 4 4 .1
Report Date - Date of Final Signature
T e s tin g L a b o ra to ry 3 M E n v iro n m e n ta l H e a lth a n d S a fe ty O p e ra tio n s
E n v iro n m e n ta l L a b o ra to ry 3 M C e n te r, B ld g 2 6 0 -0 5 -N -1 7
S t. P a u l, M N 5 5 1 4 4
Requester
G a ry H o h e n s te in 3 M B u ild in g 2 2 4 -5 W -0 3 S a in t P a u l, M N 5 5 1 4 4 -1 0 0 0 P ho ne : (6 5 1 ) 7 3 7 -3 5 7 0
The testing reported herein meet the requirements of ANSI/ISO/IEC 17025:2005 "General Requirements for the Competence of Testing and Calibration Laboratories", in accordance with A2LA Certificate # 2052.01. Additionally, the laboratory's quality system has been audited and was determined to be in conformance with the EPA GLPs (40 CFR 792) by an independent assessment.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-05-02
3M Environmental Laboratory
3M Environmental Laboratory Technical Director: William K. Reagen, Ph.D. 3M Principal Analytical Investigator: Susan Wolf Report Author: Kevin Eich
Analytical Report ISO14-05-02
Analysis of PFOA, PFBS, PFHS, and PFOS in Ground Water Samples Collected at the Former Sludge Incorporation Area (FSIA) from Decatur, AL 1st Quarter 2014
Report Date: Date of Final Signature
1 Introduction/Summary
The 3M Environmental Laboratory prepared and analyzed water samples collected by Weston Solutions personnel from Decatur, AL. Samples were collected on March 11, March 12 and March 13, 2014 and returned to the 3M Environmental Laboratory on March 14, 2014 at ambient conditions. All samples were analyzed for perfluorooctanoic acid (PFOA), perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHS) and perfluorooctane sulfonate (PFOS) under laboratory project number ISO14-05-02.
The 3M Environmental Laboratory prepared sample containers for thirty-one groundwater well locations. Each empty container was marked with a "fill to here" line that corresponded to a final volume of 200 mL. Sample bottle sets for each groundwater sampling location included a field sample and field sample duplicate. Select locations also included a target analyte field matrix spike sample. Containers designated for field matrix samples were fortified with an appropriate matrix spike solution containing PFOA, PFBS, PFHS, and PFOS prior to being sent to the field for sample collection. Sampling locations DAL-GW-136R and DAL-GW-137R were not collected due to the wells being dry.
Samples were analyzed for PFOA, PFBS, PFHS and PFOS by ETS-8-044.1 "Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis".
Table 1 summarizes the sample results using the analytical method identified above. All results for quality control samples prepared and analyzed with the samples will be reported and discussed elsewhere in this report.
The testing reported herein meet the requirements of ANSI/ISO/IEC 17025:2005 "General Requirements for the Competence of Testing and Calibration Laboratories", in accordance with A2LA Certificate # 2052.01. Additionally, the laboratory's quality system has been audited and was determined to be in conformance with the EPA GLPs (40 CFR 792) by an independent assessment.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-05-02
Table 1. Sample Results Summary (1)
3M LIMS ID ISO14-05-02-001 ISO14-05-02-002
ISO14-05-02-003 ISO14-05-02-004
ISO14-05-02-005 ISO14-05-02-006
ISO14-05-02-008 ISO14-05-02-009
ISO14-05-02-010 ISO14-05-02-011
ISO14-05-02-013 ISO14-05-02-014
ISO14-05-02-016 ISO14-05-02-017
ISO14-05-02-018 ISO14-05-02-019
Sample Description
DAL-GW-130R-0-140312 DAL-GW-130R-DB-140312
Average %RPD Sample/Sample Dup DAL-GW-130S-0-140313 DAL-GW-130S-DB-140313
Average %RPD Sample/Sample Dup DAL-GW-130L-0-140312 DAL-GW-130L-DB-140312
Average %RPD Sample/Sample Dup DAL-GW-131R-0-140311 DAL-GW-131R-DB-140311
Average %RPD Sample/Sample Dup DAL-GW-131S-0-140312 DAL-GW-131S-DB-140312
Average %RPD Sample/Sample Dup DAL-GW-131L-0-140312 DAL-GW-131L-DB-140312
Average %RPD Sample/Sample Dup DAL-GW-133R-0-140311 DAL-GW-133R-DB-140311
Average %RPD Sample/Sample Dup DAL-GW-133S-0-140311 DAL-GW-133S-DB-140311
Average %RPD Sample/Sample Dup
PFOA Concentration
(ng/mL)
875 851 863 2.8 186 197 192 5.7 57.5 58.6 58.1 1.9 2510 2490 2500 0.80 38.7 35.6 37.2 2) 8.3 119 110 115 (2) 7.9 60.6 58.9 59.8 (2) 2.8 439 378 409 15
PFBS Concentration
(ng/mL)
17.0 16.5 16.8 3.0 4.58 4.06 4.32 12 1.59 1.56 1.58 1.9 64.7 71.7 68.2 10 1.03 0.962 0.996 (2) 6.8 2.94 3.02 2.98 (2) 2.7 2.37 2.19 2.28 (2) 7.9 10.8 9.82 10.3 9.5
PFHS Concentration
(ng/mL)
115 124 120 7.5 33.6 36.2 34.9 7.4 10.7 10.6 10.7 0.94 384 355 370 7.8 6.28 5.88 6.08 (2) 6.6 22.2 20.9 21.6 (2) 6.0 15.4 15.5 15.5 (2) 0.65 76.2 70.5 73.4 7.8
PFOS Concentration
(ng/mL)
522 506 514 3.1 148 148 148 0.0 66.8 68.9 67.9 3.1 1120 1170 1150 4.4 7.03 6.62 6.83 (2) 6.0 45.3 46.1 45.7 (2) 1.8 25.3 25.5 25.4 (2) 0.79 336 301 319 11
NA = Not Applicable (1) All samples associated with the reported sampling location were diluted and analyzed by external standard calibration unless
noted otherwise. The analytical method uncertainties for the reported results using method ETS-8-044.1 by direct injection are as follows: PFOA 17%, PFBS 12%, PFHS 14%, and PFOS 14%. (2) All samples associated with the reported sampling location were analyzed by internal standard calibration. The analytical method uncertainties for the reported results using method ETS-8-044.1 by direct injection are as follows: PFOA 18%, PFBS 22%, PFHS 24%, and PFOS 20%. (3) The analytical uncertainty for location 140R was expanded to 37% for PFOA. See section 4 of the report for additional information. (4) The analytical uncertainty for location 142R was expanded to 48% for PFOA. See section 4 of the report for additional information. (5) The RPD value did not meet method acceptance criteria of <20%.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-05-02
Table 1 continued. Sample Results Summary (1)
3M LIMS ID ISO14-05-02-020 ISO14-05-02-021
ISO14-05-02-023 ISO14-05-02-024
ISO14-05-02-025 ISO14-05-02-026
ISO14-05-02-027 ISO14-05-02-028
ISO14-05-02-029 ISO14-05-02-030
ISO14-05-02-031 ISO14-05-02-032
ISO14-05-02-033 ISO14-05-02-034
ISO14-05-02-037 ISO14-05-02-038
Sample Description
DAL-GW-133L-0-140311 DAL-GW-133L-DB-140311
Average %RPD Sample/Sample Dup DAL-GW-134R-0-140313 DAL-GW-134R-DB-140313
Average %RPD Sample/Sample Dup DAL-GW-134S-0-140313 DAL-GW-134S-DB-140313
Average %RPD Sample/Sample Dup DAL-GW-134L-0-140313 DAL-GW-134L-DB-140313
Average %RPD Sample/Sample Dup DAL-GW-135R-0-140313 DAL-GW-135R-DB-140313
Average %RPD Sample/Sample Dup DAL-GW-135S-0-140313 DAL-GW-135S-DB-140313
Average %RPD Sample/Sample Dup DAL-GW-135L-0-140313 DAL-GW-135L-DB-140313
Average %RPD Sample/Sample Dup DAL-GW-136S-0-140311 DAL-GW-136S-DB-140311
Average %RPD Sample/Sample Dup
PFOA Concentration
(ng/mL)
457 420 439 8.4 2130 2210 2170 3.7 23.8 23.4 23.6 (2) 1.7 521 518 520 0.58 4000 4240 4120 5.8 94.4 89.2 91.8 (2) 5.7 371 381 376 2.7 114 117 116 2.6
PFBS Concentration
(ng/mL)
9.43 9.62 9.53 2.0 53.2 50.9 52.1 4.4 0.502 0.490 0.496 (2) 2.4 10.3 9.48 9.89 8.3 65.2 65.0 65.1 0.31 2.26 2.25 2.26 (2) 0.44 11.6 12.1 11.9 4.2 3.19 3.43 3.31 7.3
PFHS Concentration
(ng/mL)
74.0 71.3 72.7 3.7 512 527 520 2.9 6.04 6.15 6.10 (2) 1.8 92.7 92.7 92.7 0.0 721 746 734 3.4 25.9 26.3 26.1 (2) 1.5 81.1 75.8 78.5 6.8 20.2 20.1 20.2 0.50
PFOS Concentration
(ng/mL)
525 503 514 4.3 1420 1470 1450 3.5 23.9 23.9 23.9 (2) 0.0 494 508 501 2.8 1450 1490 1470 2.7 23.8 24.3 24.1 (2) 2.1 91.4 93.7 92.6 2.5 130 124 127 4.7
NA = Not Applicable (1) All samples associated with the reported sampling location were diluted and analyzed by external standard calibration unless
noted otherwise. The analytical method uncertainties for the reported results using method ETS-8-044.1 by direct injection are as follows: PFOA 17%, PFBS 12%, PFHS 14%, and PFOS 14%. (2) All samples associated with the reported sampling location were analyzed by internal standard calibration. The analytical method uncertainties for the reported results using method ETS-8-044.1 by direct injection are as follows: PFOA 18%, PFBS 22%, PFHS 24%, and PFOS 20%. (3) The analytical uncertainty for location 140R was expanded to 37% for PFOA. See section 4 of the report for additional information. (4) The analytical uncertainty for location 142R was expanded to 48% for PFOA. See section 4 of the report for additional information. (5) The RPD value did not meet method acceptance criteria of <20%.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-05-02
Table 1 continued. Sample Results Summary (1)
3M LIMS ID ISO14-05-02-039 ISO14-05-02-040
ISO14-05-02-043 ISO14-05-02-044
ISO14-05-02-045 ISO14-05-02-046
ISO14-05-02-047 ISO14-05-02-048
ISO14-05-02-049 ISO14-05-02-050
ISO14-05-02-052 ISO14-05-02-053
ISO14-05-02-054 ISO14-05-02-055
ISO14-05-02-056 ISO14-05-02-057
Sample Description
DAL-GW-136L-0-140311 DAL-GW-136L-DB-140311
Average %RPD Sample/Sample Dup DAL-GW-137S-0-140312 DAL-GW-137S-DB-140312
Average %RPD Sample/Sample Dup DAL-GW-137L-0-140312 DAL-GW-137L-DB-140312
Average %RPD Sample/Sample Dup DAL-GW-138R-0-140313 DAL-GW-138R-DB-140313
Average %RPD Sample/Sample Dup DAL-GW-138S-0-140313 DAL-GW-138S-DB-140313
Average %RPD Sample/Sample Dup DAL-GW-138L-0-140313 DAL-GW-138L-DB-140313
Average %RPD Sample/Sample Dup DAL-GW-CW26C-0-140311 DAL-GW-CW26C-DB-140311
Average %RPD Sample/Sample Dup DAL-GW-CW26L-0-140311 DAL-GW-CW26L-DB-140311
Average %RPD Sample/Sample Dup
PFOA Concentration
(ng/mL)
92.9 93.5 93.2 0.64 1.38 1.38 1.38 (2) 0.0 0.460 0.474 0.467 (2) 3.0 306 307 307 0.33 208 203 206 2.4 0.523 0.552 0.538 (2) 5.4 417 420 419 0.72 973 948 961 2.6
PFBS Concentration
(ng/mL)
2.48 2.40 2.44 3.3 0.201 0.175 0.188 (2) 14 0.101 0.108 0.105 2) 6.7 9.67 7.68 8.68 23(3) 6.02 5.63 5.83 6.7 <0.0250 0.0324 0.0324 (2) NA 7.76 7.51 7.64 3.3 15.9 15.6 15.8 1.9
PFHS Concentration
(ng/mL)
15.7 17.2 16.5 9.1 0.255 0.275 0.265 (2) 7.5 0.109 0.119 0.114 (2) 8.8 37.4 37.9 37.7 1.3 26.2 26.4 26.3 0.76 0.0691 0.0688 0.0690 (2) 0.44 57.6 58.1 57.9 0.86 122 122 122 0.0
PFOS Concentration
(ng/mL)
93.8 95.5 94.7 1.8 0.697 0.708 0.703 (2) 1.6 1.68 1.70 1.69 (2) 1.2 368 370 369 0.54 316 294 305 7.2 0.362 0.362 0.362 (2) 0.0 430 442 436 2.8 1570 1530 1550 2.6
NA = Not Applicable (1) All samples associated with the reported sampling location were diluted and analyzed by external standard calibration unless
noted otherwise. The analytical method uncertainties for the reported results using method ETS-8-044.1 by direct injection are as follows: PFOA 17%, PFBS 12%, PFHS 14%, and PFOS 14%. (2) All samples associated with the reported sampling location were analyzed by internal standard calibration. The analytical method uncertainties for the reported results using method ETS-8-044.1 by direct injection are as follows: PFOA 18%, PFBS 22%, PFHS 24%, and PFOS 20%. (3) The analytical uncertainty for location 140R was expanded to 37% for PFOA. See section 4 of the report for additional information. (4) The analytical uncertainty for location 142R was expanded to 48% for PFOA. See section 4 of the report for additional information. (5) The RPD value did not meet method acceptance criteria of <20%.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-05-02
Table 1 continued. Sample Results Summary (1)
3M LIMS ID ISO14-05-02-058 ISO14-05-02-059
ISO14-05-02-061 ISO14-05-02-062
ISO14-05-02-064 ISO14-05-02-065
ISO14-05-02-067 ISO14-05-02-068
ISO14-05-02-069 ISO14-05-02-070
ISO14-05-02-072 ISO14-05-02-071
Sample Description
DAL-GW-140R-0-140312 DAL-GW-140R-DB-140312
Average %RPD Sample/Sample Dup DAL-GW-141R-0-140313 DAL-GW-141R-DB-140313
Average %RPD Sample/Sample Dup DAL-GW-142R-0-140312 DAL-GW-142R-DB-140312
Average %RPD Sample/Sample Dup DAL-GW-143R-0-140313 DAL-GW-143R-DB-140313
Average %RPD Sample/Sample Dup DAL-GW-145R-0-140311 DAL-GW-145R-DB-140311
Average %RPD Sample/Sample Dup DAL-GW-TRI P-0-140313 DAL-GW-141R-RB-140313
PFOA Concentration
(ng/mL)
113 116 115 (3) 2.6 2.45 2.60 2.53 (2) 5.9 76.8 75.1 76.0 (4) 2.2 27.0 25.3 26.2 (2) 6.5 33.1 32.2 32.7 2.8 <0.0240 <0.0240
PFBS Concentration
(ng/mL)
1.45 1.49 1.47 2.7 0.0769 0.0670 0.0720 (2) 14 2.59 2.67 2.63 3.0 1.33 1.45 1.39 (2) 8.6 0.723 0.899 0.811 22 (5)
<0.0250 <0.0250
PFHS Concentration
(ng/mL)
14.4 15.5 15.0 7.4 0.383 0.404 0.394 (2) 5.3 13.7 15.0 14.4 9.1 5.22 4.80 5.01 (2) 8.4 4.07 3.90 3.99 4.3 <0.0250 <0.0250
PFOS Concentration
(ng/mL)
127 131 129 3.1 6.74 6.83 6.79 (2) 1.3 204 208 206 1.9 24.5 25.0 24.8 (2) 2.0 92.1 89.9 91.0 2.4 <0.0232 <0.0232
NA = Not Applicable (1) All samples associated with the reported sampling location were diluted and analyzed by external standard calibration unless
noted otherwise. The analytical method uncertainties for the reported results using method ETS-8-044.1 by direct injection are as follows: PFOA 17%, PFBS 12%, PFHS 14%, and PFOS 14%. (2) All samples associated with the reported sampling location were analyzed by internal standard calibration. The analytical method uncertainties for the reported results using method ETS-8-044.1 by direct injection are as follows: PFOA 18%, PFBS 22%, PFHS 24%, and PFOS 20%. (3) The analytical uncertainty for location 140R was expanded to 37% for PFOA. See section 4 of the report for additional information. (4) The analytical uncertainty for location 142R was expanded to 48% for PFOA. See section 4 of the report for additional information. (5) The RPD value did not meet method acceptance criteria of <20%.
2 Methods - Analytical and Preparatory
2.1 Methods
Analysis was completed using 3M Environmental Laboratory Method ETS-8-044.1 "Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis".
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-05-02
Table 2. Target Analytes
Target Analytes Perfluorobutanoic Acid (C4 Acid) Perfluorooctanoic Acid (C8 Acid) Perfluorobutanesulfonate (C4 Sulfonate ) Perfluorooctanesulfonate (C8 Sulfonate)
Acronym PFOA PFBS PFHS PFOS
Reference Material Structure
Linear and Branched Linear Linear
Linear and Branched
2.2 Sample Collection
All samples were collected in 250 mL NalgeneTM (high-density polyethylene) bottles prepared at the 3M Environmental Laboratory. Samples were collected on March 11, March 12 and March 13, 2014 and returned to the 3M Environmental Laboratory on March 14, 2014 at ambient conditions. Prior to sample collection, bottles designated for field matrix spikes were spiked in the laboratory with a known volume of an appropriate matrix spiking solution containing PFOA, PFBS, PFHS, and PFOS.
Table 3. Sample Description Key Code.
String Number 1 2 3 4
String Descriptor Sample Location Sample Type Well Identifier Well Level
5 Sample Type
6 Sampling Date
Example: DAL-GW-130R-DB-140312
DAL= Decatur, Alabama GW= Ground Water Example: 130 R = Residuum shallow water-bearing zone L = Bedrock water-bearing zone S = Epikarst middle water-bearing zone 0 =primary sample DB =duplicate sample FMS = Field Matrix Spike LS = Low field matrix spike HS = High field matrix spike 140312 - March 12, 2014
2.3 Sample Preparation
3/26/14, 4/14/14: Solvent dilution / external standard analysis. All samples and laboratory control spikes were diluted with methanol prior to sample analysis. Samples requiring a 1:10 dilution were prepared by removing a 1.0 mL aliquot of the well mixed sample and spiking it with 0.1 mL of surrogate solution and diluting it with 8.9 mL of methanol. Samples requiring a 1:20 dilution were prepared by removing a 0.5 mL aliquot of the well mixed sample and spiking it with 0.1 mL of surrogate solution and diluting it with 9.4 mL of methanol. Samples requiring a 1:50 dilution were prepared by removing a 0.2 mL aliquot of the well mixed sample and spiking it with 0.1 mL of surrogate solution and diluting it with 9.7 mL of methanol. Samples requiring a 1:100 dilution were prepared by removing a 0.1 mL aliquot of the well mixed sample and spiking it with 0.1 mL of surrogate solution and diluting it with 9.8 mL of methanol.
4/10/14: All samples were prepared by adding 0.01 mL of a surrogate solution to 10.0 mL of sample and then removing a 0.4 mL aliquot of the well mixed sample and diluting it with 0.4 mL of methanol (dilution factor of 2). During the preparation of the laboratory control samples, an aliquot of a separate internal standard spiking solution was added to the laboratory control samples (nominal concentration of 1 ng/mL). The sample bottles were spiked with an internal standard mix at a nominal concentration of 1 ng/mL prior to being sent to the field for sample collection. The laboratory control samples were then diluted with methanol in the same manner as the samples.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-05-02
2.4 Analysis
All samples and quality control samples were analyzed for the four target analytes using high performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS). Pertinent instrument parameters, the liquid chromatography gradient program, and the specific mass transitions analyzed are described in the tables below. The following analytical runs were processed and reported herein:
3/26/14: Solvent dilution / external standard analysis for PFOA, PFBS, PFHS, PFOS, and surrogates (samples extracted 3/26/14); locations 130R, 130S, 130L, 131R, 133S, 133L, 134R, 134L, 135R, 135L, 136S, 136L, 138R, CW26C, CW26L, 145R, Trip Blank high FMS. PFOA, PFBS, PFHS, and 13C4-PFOA; location 138S. PFBS, PFHS, PFOS, and 13C4-PFOS; locations 140R and 142R.
4/10/14: Solvent dilution / internal standard analysis for PFOA, PFBS, PFHS, PFOS and surrogates (samples extracted 4/10/13); locations 131S, 131L, 133R, 134S, 135S, 137S, 137L, 138L, 141R, 143R, rinseate blanks, trip blank and trip blank low FMS.
4/17/14: Solvent dilution / external standard analysis for PFOA and C4-PFOA (samples prepared 4/14/14); locations 140R and 142R. PFOS and 13C4-PFOS; location 138S.
Due to the nature of the sample, the wide range of concentrations found in the sample, and the environmental occurrence of multiple isomers of the laboratory's analytes of interest, the software used for processing the analytical results is not able to consistently integrate the analytical peak, manual integration of the analytical peak is necessary. All manual integrations are performed following the procedures outlined in method ETS-12-010. The consistency of the laboratory's integration is ensured through the training of laboratory personnel, the peer review process required for all manual integrations, the review of manual integrations by the QAU, and where necessary the review of manual integrations by laboratory management.
Table 4. Instrument Parameters
Instrument Name Analysis Dates Analytical Method Liquid Chromatograph Guard column Analytical column Injection Volume Mass Spectrometer Ion Source Polarity Software
ETS Buster 3/26/14
ETS-8-044.1 Agilent 1100 Betasil C18 (4.6 mm X 100 mm), 5 g Betasil C18 (4.6 mm X 100 mm), 5 g 5, 10, 25, gL(1) Applied Biosystems API 4000 Turbo Spray
Negative Analyst 1.6.1
ETS McCoy 4/10/14
ETS-8-044.1 Agilent 1290 Betasil C18 (4.6 mm X 100 mm), 5 g Betasil C18 (4.6 mm X 100 mm), 5 g
10 pL Applied Biosystems API 5500
Turbo Spray Negative
Analyst 1.6.1
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-05-02
Table 4 continued. Instrument Parameters
Instrument Name Analysis Dates Analytical Method Liquid Chromatograph Guard column Analytical column Injection Volume Mass Spectrometer Ion Source Polarity Software
ETS DaVinci 4/17/14
ETS-8-044.1 Agilent 1290 Prism RP (2.1 mm X 50 mm), 5 u Betasil C18 (2.1 mm X 100 mm), 5 u
5 pL Applied Biosystems API 6500
Turbo Spray Negative
Analyst 1.6.1
(1) Larger injection volumes were used for select samples to achieve a lower dilution factor.
Table 5. Liquid Chromatography Gradient Program
Step
0 1 2 3 4 5 6 7 8 9
Step
0 1 2 3 4 5 6 7 8 9
Total Time (min)
0 0.5 4.0 6.0 11.0 13.0 13.5 16.0 16.5 19.0
Total Time (min)
0 0.5 4.0 6.0 11.0 13.0 13.5 16.0 16.5 19.0
Flow Rate (uL/min)
2 mM Ammonium Acetate
3/26/14, 4/10/14
750 90.0
750 90.0 750 70.0
750 70.0
750 20.0
750 20.0
750 10.0
750 10.0
750 90.0
750 90.0
Flow Rate (uL/min)
2 mM Ammonium Acetate
4/17/14
300 90.0
300 90.0
300 70.0
300 70.0
300 20.0
300 20.0
300 10.0
300 10.0
300 90.0
300 90.0
Methanol
10.0 10.0 30.0 30.0 80.0 80.0 90.0 90.0 10.0 10.0
Methanol
10.0 10.0 30.0 30.0 80.0 80.0 90.0 90.0 10.0 10.0
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-05-02
Table 6. Mass Transitions
Analyte
Mass Transition Q1/Q3
Internal Standard
Mass Transition Q1/Q3
Reference Material Structure
413/369
PFOA
413/219
[13C8]PFOA (1)
421/376
Linear and Branched
413/169
PFBS
299/80 299/99
[18O2]PFBS (1)
303/84
Linear
PFHS
399/99 399/80
[13Qb]PFHS (1)
402/80
Linear
499/99
PFOS
499/80
[13C8]-PFOS (1)
507/80
Linear and Branched
499/130
[13C4]PFOA surrogate
417/372
[13C8]PFOA (1)
421/376
Linear
[13C4]PFOS surrogate
503/80
[13C8]PFOS (1)
507/80
Linear
Dwell time was 20 or 50 msec for each transition. The individual transitions were summed to produce a "total ion chromatogram" (TIC), which was used for quantitation.
(1) Internal standard was used for the analysis on 4/10/14.
3 Data Analysis
3.1 Calibration
3/26/14, 4/17/14: Solvent dilution / external standard calibration. Diluted samples were analyzed against an external standard calibration curve. Calibration standards were prepared by spiking known amounts of stock solutions containing the analytes of interest into 50 mL of 90:10 methanol: laboratory Milli-QTM water. A total of eleven calibration standards ranging from 0.1 ng/mL to 150 ng/mL (nominal) were analyzed. A quadratic, 1/x weighted, calibration curve was used to fit the data for each analyte. The data were not forced through zero during the fitting process. Calculating the standard concentration using the peak area counts and the resultant calibration curve confirmed accuracy of each curve point. The reference standards of PFOA and PFOS used to prepare the calibration standards consisted of both linear and branched isomers.
4/10/14: Direct Injection / internal standard calibration. Samples were analyzed against a matrix-matched stable isotope internal standard calibration curve. Calibration standards were prepared by spiking known amounts of stock solutions into 50 mL of 50:50 methanol: laboratory reagent water. The calibration standards contained an internal standard mix at a nominal concentration of 0.5 ng/mL. A total of fourteen spiked standards ranging from 0.0125 ng/mL to 100 ng/mL (nominal) were analyzed with the prepared samples. Of these fourteen calibration standards, ten contained the surrogates at concentrations ranging from 0.0125 ng/mL to 10 ng/mL (nominal). A quadratic, 1/x weighted, calibration curve of the ratio of the standard peak area counts over the internal standard peak area counts was used to fit the data for each analyte.
For all analyses, each curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method calibration accuracy requirements of 10025% (10030% for the lowest curve point) were met for all analytes. The correlation coefficient (r) was greater than 0.995 for all analytes.
3.2 System Suitability
A calibration standard was analyzed four times at the beginning of the analytical sequence to demonstrate overall system suitability. The acceptance criteria for system suitability samples is less
PAGE 10 OF 24
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-05-02
than or equal to 5% relative standard deviation (RSD) for peak area or peak area ratio and retention time criteria of less than or equal to 2% RSD. These criteria were met for all analytes,
3.3 Limit of Quantitation (LOQ)
The LOQ as defined in method ETS-8-044.1 is the lowest non-zero calibration standard in the curve that meets linearity and accuracy requirements and for which the peak area ratio (or peak area) is at least two times the average peak area ratio (or peak area) of the method blanks. The LOQs associated with the sample analysis are listed in the table below.
Table 7. LOQ
Analysis Date
Calibration
3/26/14
External standard
4/10/14
Internal standard
4/17/14
External standard
NA= Not Applicable
Dilution Factor
2 5 10 20 50 100 2 10
PFOA LOQ, ng/mL
0.192 0.479 0.958 1.92 4.79 9.58 0.0240 0.958
PFBS LOQ, ng/mL
0.200 0.500 1.00 2.00 5.00 10.0 0.0250
NA
PFHS LOQ, ng/mL
0.200 0.500 1.00 2.00 5.00 10.0 0.0250
NA
PFOS LOQ, ng/mL
0.185 0.464 0.927 1.85 4.64 9.27 0.0232 0.927
3.4 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. The method acceptance criteria of 100% 25% was met for all analytes for all analyses.
3.5 Blanks
Three types of blanks were prepared and analyzed with the samples: method/procedural blanks, a field/trip blank, and a single equipment rinseate blank. Method blank results were reviewed and used to evaluate method performance to determine the LOQ for each analyte.
3.6 Lab Control Spikes (LCSs)
Low, mid, and high lab control spikes were prepared with each sample preparation batch for the target analytes and analyzed in triplicate. LCSs were prepared by spiking known amounts of the analytes into synthetic groundwater or laboratory Milli Q water to produce the desired concentration. The LCS samples were then diluted in a similar manner as the samples (if diluted) prior to sample analysis. The method acceptance criteria, average of each level of LCS should be within 100% 20% with an RSD <20%, were met for all LCSs.
All batch LCS recovery results were used in the evaluation of the analytical method uncertainty in section 3.7 of the report.
The following calculations were used to generate data in Table 8.
Calculated Concentration LCS Percent Recovery
Spike Concentration
%
standard deviation LCS replicates
LCS% RSD =
100%
average LCS recovery
PAGE 11 OF 24
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-05-02
Table 8. Lab Control Spike Results
ETS-8-044.1 Analyzed 3/26/14 External Standard Calibration
Lab ID LCS-140326-1 LCS-140326-2 LCS-140326-3 Average %RSD LCS-140326-4 LCS-140326-5 LCS-140326-6 Average %RSD LCS-140326-7 LCS-140326-8 LCS-140326-9 Average %RSD
PFOA (Linear and Branched)
Spiked Concentration
(ng/mL)
Calculated Concentration
(ng/mL)
%Recovery
0.479 0.479 0.479
4.79 4.79 4.79
38.2 38.2 38.2
0.430 0.494 0.427 93.9% 8.4% 4.66 4.53 4.59 95.9% 1.4% 35.9 37.9 36.8 96.5% 2.7%
89.7 103 89.1
97.3 94.6 95.9
94.0 99.2 96.4
Spiked Concentration
(ng/mL) 0.499 0.499 0.499
4.99 4.99 4.99
13C4-PFOA Calculated Concentration
(ng/mL)
0.473 0.472 0.553 100% 9.5% 5.39 5.71 5.34 110% 3.5%
%Recovery 94.7 94.5 111
108 114 107
ETS-8-044.1 Analyzed 3/26/14 External Standard Calibration
Lab ID LCS-140326-1 LCS-140326-2 LCS-140326-3 Average %RSD LCS-140326-4 LCS-140326-5 LCS-140326-6 Average %RSD LCS-140326-7 LCS-140326-8 LCS-140326-9 Average %RSD
Spiked Concentration
(ng/mL) 0.500 0.500 0.500
5.00 5.00 5.00
39.8 39.8 39.8
PFBS Calculated Concentration
(ng/mL)
0.531 0.543 0.443 101% 11% 6.01 5.44 4.60 107% 13% 39.9 41.0 39.5 101% 2.0%
%Recovery 106 109 88.7
120 109 91.9
100 103 99.1
Spiked Concentration
(ng/mL) 0.500 0.500 0.500
5.00 5.00 5.00
39.8 39.8 39.8
PFHS Calculated Concentration
(ng/mL)
0.476 0.506 0.482 97.5% 3.1% 5.02 5.19 4.54 98.3% 6.8% 38.6 38.3 39.6 97.4% 1.8%
%Recovery 95.2 101 96.4
100 104 90.9
96.9 96.0 99.4
PAGE 12 OF 24
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-05-02
Table 8 continued. Lab Control Spike Results
ETS-8-044.1 Analyzed 3/26/14 External Standard Calibration
Lab ID
LCS-140326-1 LCS-140326-2 LCS-140326-3 Average %RSD LCS-140326-4 LCS-140326-5 LCS-140326-6 Average %RSD LCS-140326-7 LCS-140326-8 LCS-140326-9 Average %RSD
PFOS (Linear and Branched)
Spiked Concentration
(ng/mL)
Calculated Concentration
(ng/mL)
%Recovery
0.464 0.464 0.464
4.63 4.63 4.63
36.9 36.9 36.9
0.416 0.404 0.402 87.9% 1.9% 4.77 4.49 4.32 97.7% 5.0% 35.7 35.5 36.3 97.0% 1.1%
89.8 87.2 86.8
103 96.8 93.3
96.6 96.1 98.2
Spiked Concentration
(ng/mL) 0.478 0.478 0.478
4.78 4.78 4.78
13C4-PFOS Calculated Concentration
(ng/mL)
0.413 0.498 0.514 99.4% 12% 5.11 4.86 4.61 102% 5.2%
%Recovery 86.3 104 108
107 102 96.4
ETS-8-044.1 Analyzed 4/10/14 Internal Standard Calibration
Lab ID
LCS-140410-1 LCS-140410-2 LCS-140410-3 Average %RSD LCS-140410-4 LCS-140410-5 LCS-140410-6 Average %RSD LCS-140410-7 LCS-140410-8 LCS-140410-9 Average %RSD
PFOA (Linear and Branched)
Spiked Concentration
(ng/mL)
Calculated Concentration
(ng/mL)
%Recovery
0.190 0.190 0.190
9.50 9.50 9.50
38.0 38.0 38.0
0.181 0.173 0.182 94.0% 2.7% 8.68 9.35 9.38 96.2% 4.3% 36.0 36.8 38.7 97.9% 3.8%
95.1 91.1 95.8
91.4 98.4 98.7
94.7 96.9 102
Spiked Concentration
(ng/mL)
0.198 0.198 0.198
1.98 1.98 1.98
13C4-PFOA Calculated Concentration
(ng/mL)
0.194 0.196 0.200 99.2% 1.6% 1.91 1.86 1.89 95.3% 1.3%
%Recovery 97.9 98.8 101
96.5 94.1 95.4
PAGE 13 OF 24
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-05-02
Table 8 continued. Lab Control Spike Results
ETS-8-044.1 Analyzed 4/10/14 Internal Standard Calibration
Lab ID LCS-140410-1 LCS-140410-2 LCS-140410-3 Average %RSD LCS-140410-4 LCS-140410-5 LCS-140410-6 Average %RSD LCS-140410-7 LCS-140410-8 LCS-140410-9 Average %RSD
ETS-8-044.1 Analyzed 4/10/14 Internal Standard Calibration
Lab ID LCS-140410-1 LCS-140410-2 LCS-140410-3 Average %RSD LCS-140410-4 LCS-140410-5 LCS-140410-6 Average %RSD LCS-140410-7 LCS-140410-8 LCS-140410-9 Average %RSD
Spiked Concentration
(ng/mL) 0.198 0.198 0.198
9.92 9.92 9.92
39.6 39.6 39.6
PFBS Calculated Concentration
(ng/mL)
0.170 0.173 0.170 86.4% 1.1% 7.69 7.78 8.32 80.0% 4.3% 30.6 32.0 32.3 79.9% 2.9%
%Recovery 86.0 87.4 85.7
77.6 78.4 83.9
77.3 80.9 81.6
Spiked Concentration
(ng/mL) 0.198 0.198 0.198
9.92 9.92 9.92
39.6 39.6 39.6
PFHS Calculated Concentration
(ng/mL)
0.184 0.180 0.183 92.1% 1.3% 8.75 9.16 9.56 92.3% 4.4% 37.4 37.8 40.8 97.6% 4.9%
%Recovery 93.1 90.8 92.3
88.2 92.3 96.4
94.3 95.4 103
PFOS (Linear and Branched)
Spiked Concentration
(ng/mL)
Calculated Concentration
(ng/mL)
%Recovery
0.184 0.184 0.184
9.20 9.20 9.20
36.7 36.7 36.7
0.173 0.174 0.171 93.8% 0.91% 8.66 8.86 8.80 95.4% 1.1% 33.4 34.3 36.7 94.8% 4.8%
93.8 94.7 93.0
94.2 96.3 95.7
91.0 93.6 99.9
Spiked Concentration
(ng/mL) 0.189 0.189 0.189
1.90 1.90 1.90
13C4-PFOS Calculated Concentration
(ng/mL)
0.178 0.184 0.178 95.1% 2.1% 1.93 1.84 1.88 99.1% 2.0%
%Recovery 94.0 97.4 94.0
101 97.1 99.2
PAGE 14 OF 24
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-05-02
Table 8 continued. Lab Control Spike Results
ETS-8-044.1 Analyzed 4/17/14 External Standard Calibration
Lab ID
LCS-140414-1 LCS-140414-2 LCS-140414-3 Average %RSD LCS-140414-4 LCS-140414-5 LCS-140414-6 Average %RSD LCS-140414-7 LCS-140414-8 LCS-140414-9 Average %RSD
PFOA (Linear and Branched)
Spiked Concentration
(ng/mL)
Calculated Concentration
(ng/mL)
%Recovery
0.479 0.479 0.479
4.79 4.79 4.79
38.2 38.2 38.2
0.570 0.568 0.499 114% 7.6% 4.78 4.91 4.62 99.4% 2.8% 37.3 37.1 38.1 98.2% 1.4%
119 119 104
99.7 102 96.4
97.5 97.2 99.8
Spiked Concentration
(ng/mL) 0.499 0.499 0.499
4.99 4.99 4.99
13C4-PFOA Calculated Concentration
(ng/mL)
0.492 0.509 0.498 100% 1.7% 4.76 4.95 4.82 97.1% 1.9%
%Recovery 98.6 102 99.7
95.5 99.1 96.6
ETS-8-044.1 Analyzed 4/17/14 External Standard Calibration
Lab ID
LCS-140414-1 LCS-140414-2 LCS-140414-3 Average %RSD LCS-140414-4 LCS-140414-5 LCS-140414-6 Average %RSD LCS-140414-7 LCS-140414-8 LCS-140414-9 Average %RSD
PFOS (Linear and Branched)
Spiked Concentration
(ng/mL)
Calculated Concentration
(ng/mL)
%Recovery
0.464 0.464 0.464
4.64 4.64 4.64
36.9 36.9 36.9
0.509 0.508 0.489 108% 2.7% 4.77 4.92 4.78 104% 1.7% 38.3 36.6 38.7 103% 3.0%
110 110 105
103 106 103
104 99.2 105
Spiked Concentration
(ng/mL)
0.478 0.478 0.478
4.78 4.78 4.78
13C4-PFOS Calculated Concentration
(ng/mL)
0.509 0.517 0.497 106% 1.9% 4.79 4.91 4.82 101% 1.5%
%Recovery 106 108 104
100 103 101
PAGE 15 OF 24
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-05-02
3.7 Analytical Method Uncertainty
Analytical method uncertainty is based on historical QC data that is control charted and used to evaluate method accuracy and precision. The method uncertainty is calculated following ETS-12012.2. The standard deviation is calculated for the set of accuracy results (in %) obtained for the QC samples. The expanded uncertainty is calculated by multiplying the standard deviation by a factor of 2, which corresponds to a confidence level of 95%.
Table 9. Analytical Method Uncertainty
Analyte PFOA PFBS PFHS PFOS PFOA PFBS PFHS PFOS
Calibration External External External External Internal Internal Internal Internal
Standard Deviation (%) 8.29 5.88 7.14 7.16 9.07 11.2 11.8 10.0
Method Uncertainty 17% 12% 14% 14% 18% 22% 24% 20%
3.8 Field Matrix Spikes (FMS) and Laboratory Matrix Spikes (LMS)
Field matrix spike sample containers were prepared for select locations to verify that the analytical method is applicable to the collected matrix. Field matrix spikes are generated by adding a measured volume of field sample to a container spiked by the laboratory with the target analytes prior to shipping sample containers to the field for sample collection. Field matrix spikes must be at least 0.5 times the analyte concentration to be considered an appropriate spike level. Field matrix spike recoveries within method acceptance criteria of 10030% confirm that "unknown" components in the sample matrix do not significantly interfere with the extraction and analysis of the analytes of interest. The reference standards for PFOA and PFOS in the field matrix spiking solution consisted of linear and branched isomers. The locations for which FMS sample containers were prepared are listed in Table 10.
Field matrix spikes are presented in section 4 of this report.
FMS Recovery - (Sample Concentration of FMS - Average Concentration: Field Sample & Field Sample Dup.) * 1 0 0 % Spike Concentraton
Table 10. Field Matrix Spike (FMS) Concentrations
Sampling location 141R 131S 130L and 131L 140R and 142R 133L and 138S
Trip Blank
Spike Level FMS FMS FMS FMS FMS FMS Low FMS High
PFOA ng/mL
4.96 24.8 49.6 99.2 198 4.96 198
PFBS ng/mL
5.00 25.0 50.0 100 200 5.00 200
PFHS ng/mL
5.00 25.0 50.0 100 200 5.00 200
PFOS ng/mL
4.99 25.0 49.9 99.8 200 4.99 200
PAGE 16 OF 24
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-05-02
4 Data Summary and Discussion
Tables 11-20 below summarize the sample results and target analyte field matrix spike recoveries for the sampling locations as well as the Trip Blank. Each table provides the average concentration and the relative percent difference (%RPD) of the sample and sample duplicate. Results and average values are rounded to three significant figures. Percent relative difference (%RPD) values are rounded to two significant figures. Because of rounding, values may vary slightly from those listed in the raw data. Field matrix spikes meeting the method acceptance criteria of 30%, demonstrate that the method is appropriate for the given matrix. All target analyte field matrix spikes met method acceptance criteria with the following exceptions:
An appropriate field matrix spike was not available for PFOA for sampling locations DAL GW 131L and DAL GW 133L and for PFOS for sampling location DAL-GW-133L; all samples were spiked with surrogate recovery standards prior to extraction. The surrogate recovery standard recoveries met method acceptance criteria.
DAL-GW-140R; The FMS recovery for PFOA was 63.0%. The analytical uncertainty for this location was expanded to 37%.
DAL-GW-142R; The FMS recovery for PFOA was 52.5%. The analytical uncertainty for this location was expanded to 48%.
Table 11. DAL-GW-130L
3M LIMS ID
Description
ISO14-05-02-005
DAL-GW-130L-0-140312
ISO14-05-02-006 ISO14-05-02-007
DAL-GW-130L-DB-140312 DAL-GW-130L-FMS-140312
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
57.5 NA 58.6 NA 109 103
58.1 ng/mL 1.9%
PFBS
Concentration (ng/mL)
%Recovery
1.59 NA 1.56 NA 56.7 110
1.58 ng/mL 1.9%
PFHS
3M LIMS ID
Description
ISO14-05-02-005
DAL-GW-130L-0-140312
ISO14-05-02-006 ISO14-05-02-007
DAL-GW-130L-DB-140312 DAL-GW-130L-FMS-140312
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
10.7 NA 10.6 NA 63.8 106
10.7 ng/mL 0.94%
NA = Not Applicable Samples were diluted 1:10 and analyzed using external standard quantitation.
PFOS
Concentration (ng/mL)
%Recovery
66.8 NA 68.9 NA 124 113
67.9 ng/mL 3.1%
PAGE 17 OF 24
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-05-02
Table 12. DAL-GW-131S
3M LIMS ID
Description
ISO14-05-02-010
DAL-GW-131S-0-140312
ISO14-05-02-011 ISO14-05-02-012
DAL-GW-131S-DB-140312 DAL-GW-131S-FMS-140312
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
38.7 NA 35.6 NA 62.6 103
37.2 ng/mL 8.3%
PFBS
Concentration (ng/mL)
%Recovery
1.03 NA
0.962
NA
21.9 83.6
0.996 ng/mL 6.8%
PFHS
3M LIMS ID
Description
ISO14-05-02-010 ISO14-05-02-011 ISO14-05-02-012
DAL-GW-131S-0-140312 DAL-GW-131S-DB-140312 DAL-GW-131S-FMS-140312
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
6.28 NA 5.88 NA 30.6 98.1
6.08 ng/mL 6.6%
NA = Not Applicable Samples were diluted 1:2 and analyzed using internal standard quantitation.
PFOS
Concentration (ng/mL)
%Recovery
7.03 NA 6.62 NA 32.8 104
6.83 ng/mL 6.0%
Table 13. DAL-GW-131L
3M LIMS ID
Description
ISO14-05-02-013
DAL-GW-131L-0-140312
ISO14-05-02-014 ISO14-05-02-015
DAL-GW-131L-DB-140312 DAL-GW-131L-FMS-140312
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
119 NA 110 NA 160 NC
115 ng/mL 7.9%
PFBS
Concentration (ng/mL)
%Recovery
2.94 NA 3.02 NA 49.6 93.2
2.98 ng/mL 2.7%
PFHS
3M LIMS ID
Description
ISO14-05-02-013
DAL-GW-131L-0-140312
ISO14-05-02-014
DAL-GW-131L-DB-140312
ISO14-05-02-015
DAL-GW-131L-FMS-140312
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
22.2 NA 20.9 NA 74.9 107
21.6 ng/mL 6.0%
NA = Not Applicable NC = Not Calculated; Spike level was less than 0.5x the endogenous sample concentration. Samples were diluted 1:2 and analyzed using internal standard quantitation.
PFOS
Concentration (ng/mL)
%Recovery
45.3 NA 46.1 NA 97.7 104
45.7 ng/mL 1.8%
PAGE 18 OF 24
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-05-02
Table 14. DAL-GW-133L
3M LIMS ID
Description
ISO14-05-02-020
DAL-GW-133L-0-140311
ISO14-05-02-021
DAL-GW-133L-DB-140311
ISO14-05-02-022
DAL-GW-133L-FMS-140311
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
457 NA 420 NA 639 NC
439 ng/mL 8.4%
PFBS
Concentration (ng/mL)
%Recovery
9.43 NA 9.62 NA 193 91.7
9.53 ng/mL 2.0%
PFHS
3M LIMS ID
Description
ISO14-05-02-020
DAL-GW-133L-0-140311
ISO14-05-02-021 ISO14-05-02-022
DAL-GW-133L-DB-140311 DAL-GW-133L-FMS-140311
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
74.0 NA 71.3 NA 263 95.0
72.7 ng/mL 3.7%
NA = Not Applicable NC = Not Calculated; Spike level was less than 0.5x the endogenous sample concentration. Samples were diluted 1:10 and analyzed using external standard quantitation.
PFOS
Concentration (ng/mL)
%Recovery
525 NA 503 NA 776 NC
514 ng/mL 4.3%
Table 15. DAL-GW-138S
3M LIMS ID
Description
ISO14-05-02-049
DAL-GW-138S-0-140313
ISO14-05-02-050
DAL-GW-138S-DB-140313
ISO14-05-02-051
DAL-GW-138S-FMS-140313
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
208 NA 203 NA 366 80.9
206 ng/mL 2.4%
PFBS
Concentration (ng/mL)
%Recovery
6.02 NA 5.63 NA 224 109
5.83 ng/mL 6.7%
PFHS
3M LIMS ID
Description
ISO14-05-02-049
DAL-GW-138S-0-140313
ISO14-05-02-050
DAL-GW-138S-DB-140313
ISO14-05-02-051
DAL-GW-138S-FMS-140313
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
26.2 NA 26.4 NA 240 107
26.3 ng/mL 0.76%
NA = Not Applicable Samples were diluted 1:10 and analyzed using external standard quantitation.
PFOS
Concentration (ng/mL)
%Recovery
316 NA 294 NA 534 115
305 ng/mL 7.2%
PAGE 19 OF 24
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-05-02
Table 16. DAL-GW-140R
3M LIMS ID
Description
ISO14-05-02-058
DAL-GW-140R-0-140312
ISO14-05-02-059
DAL-GW-140R-DB-140312
ISO14-05-02-060
DAL-GW-140R-FMS-140312
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
113 NA 116 NA 177 63.0 (1) 115 ng/mL 2.6% (2)
PFBS
Concentration (ng/mL)
%Recovery
1.45 NA 1.49 NA 110 109
1.47 ng/mL 2.7%
PFHS
3M LIMS ID
Description
ISO14-05-02-058
DAL-GW-140R-0-140312
ISO14-05-02-059 ISO14-05-02-060
DAL-GW-140R-DB-140312 DAL-GW-140R-FMS-140312
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
14.4 NA 15.5 NA 121 106
15.0 ng/mL 7.4%
NA = Not Applicable Samples were diluted 1:10 and analyzed using external standard quantitation. (1) FMS did not meet method acceptance criteria of 30. (2) The analytical uncertainty was expanded to 37%.
PFOS
Concentration (ng/mL)
%Recovery
127 NA 131 NA 212 83.2
129 ng/mL 3.1%
Table 17. DAL-GW-141R
3M LIMS ID
Description
ISO14-05-02-061
DAL-GW-141R-0-140313
ISO14-05-02-062 ISO14-05-02-063
DAL-GW-141R-DB-140313 DAL-GW-141R-FMS-140313
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
2.45 NA 2.60 NA 7.43 98.9
2.53 ng/mL 5.9%
PFBS
Concentration (ng/mL)
%Recovery
0.0769
NA
0.0670
NA
4.47 88.0
0.0720 ng/mL 14%
PFHS
3M LIMS ID
Description
ISO14-05-02-061 ISO14-05-02-062 ISO14-05-02-063
DAL-GW-141R-0-140313 DAL-GW-141R-DB-140313 DAL-GW-141R-FMS-140313
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
0.383
NA
0.404
NA
4.98 91.7
0.394 ng/mL 5.3%
NA = Not Applicable Samples were diluted 1:2 and analyzed using internal standard quantitation.
PFOS
Concentration (ng/mL)
%Recovery
6.74 NA 6.83 NA 11.5 94.5
6.79 ng/mL 1.3%
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-05-02
Table 18. DAL-GW-142R
3M LIMS ID
Description
ISO14-05-02-064
DAL-GW-142R-0-140312
ISO14-05-02-065
DAL-GW-142R-DB-140312
ISO14-05-02-066
DAL-GW-142R-FMS-140312
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
76.8 NA 75.1 NA 128 52.5 (1) 76.0 ng/mL 2.2% (2)
PFBS
Concentration (ng/mL)
%Recovery
2.59 NA 2.67 NA 99.2 96.6
2.63 ng/mL 3.0%
3M LIMS ID
Description
ISO14-05-02-064 ISO14-05-02-065 ISO14-05-02-066
DAL-GW-142R-0-140312 DAL-GW-142R-DB-140312 DAL-GW-142R-FMS-140312
Average Concentration (ng/mL) %RPD
PFHS
Concentration (ng/mL)
%Recovery
13.7 NA 15.0 NA 112 97.5
14.4 ng/mL 9.1%
PFOS
Concentration (ng/mL)
%Recovery
204 NA 208 NA 277 71.1
206 ng/mL 1.9%
NA = Not Applicable Samples were diluted 1:10 and analyzed using external standard quantitation. (1) FMS did not meet method acceptance criteria of 30. (2) The analytical uncertainty was expanded to 48%.
Table 19. Trip Blank
3M LIMS ID ISO14-05-02-072 ISO14-05-02-073 ISO14-05-02-074
Description
DAL-GW-TRI P-0-140313 DAL-GW-TRIP-LS-140313 DAL-GW-TRI P-HS-140313
PFOA
Concentration (ng/mL)
<0.0240 (1) 5.14 (1) 195 (2)
%Recovery
NA 104 98.3
PFBS
Concentration (ng/mL)
<0.0250 (1) 4.49 (1) 200 (2)
%Recovery
NA 89.8 100
PFHS
3M LIMS ID ISO14-05-02-072 ISO14-05-02-073 ISO14-05-02-074
Description
DAL-GW-TRI P-0-140313 DAL-GW-TRI P-LS-140313 DAL-GW-TRI P-HS-140313
Concentration (ng/mL)
<0.0250 (1) 4.76 (1) 199 (2)
%Recovery
NA 95.2 99.3
NA = Not Applicable (1) Samples were diluted 1:2 and analyzed using internal standard quantitation. (2) Samples were diluted 1:10 and analyzed using external standard quantitation.
PFOS
Concentration (ng/mL)
<0.0232 (1) 4.70 (1) 201 (2)
%Recovery
NA 94.2 101
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-05-02
Table 20. Surrogate Recovery Standards (1)
3M LIMS ID ISO14-05-02-001 ISO14-05-02-002 ISO14-05-02-003 ISO14-05-02-004 ISO14-05-02-005 ISO14-05-02-006 ISO14-05-02-007 ISO14-05-02-008 ISO14-05-02-009 ISO14-05-02-010 ISO14-05-02-011 ISO14-05-02-012 ISO14-05-02-013 ISO14-05-02-014 ISO14-05-02-015 ISO14-05-02-016 ISO14-05-02-017 ISO14-05-02-018 ISO14-05-02-019 ISO14-05-02-020 ISO14-05-02-021 ISO14-05-02-022 ISO14-05-02-023 ISO14-05-02-024 ISO14-05-02-025 ISO14-05-02-026 ISO14-05-02-027 ISO14-05-02-028 ISO14-05-02-029 ISO14-05-02-030 ISO14-05-02-031 ISO14-05-02-032 ISO14-05-02-033 ISO14-05-02-034
Description DAL-GW-130R-0-140312 DAL-GW-130R-DB-140312 DAL-GW-130S-0-140313 DAL-GW-130S-DB-140313 DAL-GW-130L-0-140312 DAL-GW-130L-DB-140312 DAL-GW-130L-FMS-140312 DAL-GW-131R-0-140311 DAL-GW-131R-DB-140311 DAL-GW-131S-0-140312 DAL-GW-131S-DB-140312 DAL-GW-131S-FMS-140312 DAL-GW-131L-0-140312 DAL-GW-131L-DB-140312 DAL-GW-131L-FMS-140312 DAL-GW-133R-0-140311 DAL-GW-133R-DB-140311 DAL-GW-133S-0-140311 DAL-GW-133S-DB-140311 DAL-GW-133L-0-140311 DAL-GW-133L-DB-140311 DAL-GW-133L-FMS-140311 DAL-GW-134R-0-140313 DAL-GW-134R-DB-140313 DAL-GW-134S-0-140313 DAL-GW-134S-DB-140313 DAL-GW-134L-0-140313 DAL-GW-134L-DB-140313 DAL-GW-135R-0-140313 DAL-GW-135R-DB-140313 DAL-GW-135S-0-140313 DAL-GW-135S-DB-140313 DAL-GW-135L-0-140313 DAL-GW-135L-DB-140313
13C4-PFOA %Recovery
83.4 79.3 91.2 90.7 90.2 95.6 95.0 96.2 104 104 84.0 89.5 95.9 81.3 87.7 95.6 101 91.3 79.5 80.1 74.2 87.9 90.0 91.4 94.3 95.2 98.1 87.9 99.2 92.1 100 86.7 88.1 96.9
(1) All surrogate recovery standards were added during sample preparation.
13C4-PFOS %Recovery
83.1 85.3 82.6 86.3 83.7 90.6 99.8 106 92.3 99.1 95.4 102 94.6 88.6 87.4 92.6 100 97.1 73.5 77.0 77.0 87.3 93.1 101 109 95.7 87.1 91.3 85.7 90.2 96.2 98.2 94.4 82.3
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-05-02
Table 20 continued. Surrogate Recovery Standards (1)
3M LIMS ID ISO14-05-02-037 ISO14-05-02-038 ISO14-05-02-039 ISO14-05-02-040 ISO14-05-02-043 ISO14-05-02-044 ISO14-05-02-045 ISO14-05-02-046 ISO14-05-02-047 ISO14-05-02-048 ISO14-05-02-049 ISO14-05-02-050 ISO14-05-02-051 ISO14-05-02-052 ISO14-05-02-053 ISO14-05-02-054 ISO14-05-02-055 ISO14-05-02-056 ISO14-05-02-057 ISO14-05-02-058 ISO14-05-02-059 ISO14-05-02-060 ISO14-05-02-061 ISO14-05-02-062 ISO14-05-02-063 ISO14-05-02-064 ISO14-05-02-065 ISO14-05-02-066 ISO14-05-02-067 ISO14-05-02-068 ISO14-05-02-069 ISO14-05-02-070 ISO14-05-02-071 ISO14-05-02-072 ISO14-05-02-073 ISO14-05-02-074
Description DAL-GW-136S-0-140311 DAL-GW-136S-DB-140311 DAL-GW-136L-0-140311 DAL-GW-136L-DB-140311 DAL-GW-137S-0-140312 DAL-GW-137S-DB-140312 DAL-GW-137L-0-140312 DAL-GW-137L-DB-140312 DAL-GW-138R-0-140313 DAL-GW-138R-DB-140313 DAL-GW-138S-0-140313 DAL-GW-138S-DB-140313 DAL-GW-138S-FMS-140313 DAL-GW-138L-0-140313 DAL-GW-138L-DB-140313 DAL-GW-CW26C-0-140311 DAL-GW-CW26C-DB-140311 DAL-GW-CW26L-0-140311 DAL-GW-CW26L-DB-140311 DAL-GW-140R-0-140312 DAL-GW-140R-DB-140312 DAL-GW-140R-FMS-140312 DAL-GW-141R-0-140313 DAL-GW-141R-DB-140313 DAL-GW-141R-FMS-140313 DAL-GW-142R-0-140312 DAL-GW-142R-DB-140312 DAL-GW-142R-FMS-140312 DAL-GW-143R-0-140313 DAL-GW-143R-DB-140313 DAL-GW-145R-0-140311 DAL-GW-145R-DB-140311 DAL-GW-141R-RB-140313 DAL-GW-TRI P-0-140313 DAL-GW-TRIP-LS-140313 DAL-GW-TRI P-HS-140313
13C4-PFOA %Recovery
95.2 94.2 96.0 94.8 94.3 93.0 82.1 87.6 90.3 99.0 92.2 95.7 94.7 89.9 96.0 90.8 95.9 94.7 97.3 79.9 80.5 78.9 93.9 89.2 91.0 85.7 83.1 81.3 95.2 88.9 98.7 98.2 102 94.8 93.8 94.0
(1) All surrogate recovery standards were added during sample preparation.
13C4-PFOS %Recovery
92.9 92.9 87.7 88.5 98.1 98.0 99.6 101 91.2 91.9 92.1,84.0 93.6, 81.1 86.3, 77.8 118 118 92.8 86.5 85.9 94.5 86.3 92.1 86.8 104 104 99.7 95.7 94.7 84.7 106 104 86.3 85.3 106 94.1 93.0 85.5
PAGE 23 OF 24
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-05-02
5 Conclusion
Laboratory control spikes were used to determine the analytical method accuracy and precision for all analytes. The accuracy and precision were then used to estimate the method uncertainty for the results. Field and laboratory matrix spike recoveries demonstrated that the analytical method was appropriate for the given sample matrix. Method ETS-8-044.1 "Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis" was used for analysis. Analytical results are reported in Tables 1 and 11-20 of this report.
6 Data / Sample Retention
All remaining sample and associated project data (hardcopy and electronic) will be archived according to 3M Environmental Laboratory standard operating procedures.
7 Signatures
D igitally s ign ed b y S usan T . W o lf DN: c=US, st=MN, l=S t. Paul, ou=3M Environmental Laboratory - authenticated by LRA, em all=stw olf@ m m m .com , o=3M, cn=Susan T. W olf Reason: i have reviewed th is document Date: 2014.05.05 13:43:21 -05 '00 '
Susan T. Wolf, 3M Principal Analytical Investigator
Digitally signed by William K. Reagen DN: c=US, st=MN, l=St. Paul, ou=Laboratory Director, ou=3M Environmental Laboratory - authenticated by LRA, emall=wkreagen@ mmm.com, o=3M, cn=Wi!!iam K. Reagen Reason: i am approving this document Date: 2014.05.05 14:56:28-05*00'
William K. Reagen, Ph.D., 3M Environmental Technical Director
The 3M Environmental Laboratory's Quality Assurance Unit has audited the data and report for this
project.
Digitally signed by Casey Howell DN: c=US, st=MN, l=St. Paul, ou=Quality Assurance Unit. ou=3lvl Environmental Laboratory - authenticated by LRA. email=chowell@mmm.com. o=3M, cn=Casey
Howell Reason: I agree to the terms defined by the placement of my signature on this document
Date: 2014.05.06 09:27:13 -05'00'
Quality Assurance Representative
This test report shall not be reproduced except in full, without written approval o f the 3M Environmental Laboratory.
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