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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-04
Final Report
Analysis of PFOA, PFBS, PFHS, and PFOS in Groundwater Samples Collected from Decatur, Alabama 3rd Quarter 2013
Laboratory Request Number: ISO13-05-04 Method Requirement: 3M Method ETS-8-044.1
Report Date - Date of Final Signature
Testing Laboratory 3M EHS&S Operations 3M Environmental Laboratory
Building 260-5N-17 Maplewood, MN 55144-1000
Requester Gary Hohenstein 3M Building 224-5W-03 Saint Paul, MN 55144-1000 Phone: (651) 737-3570
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 the A2LA Testing 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 A2LA assessment.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-04
3M Environmental Laboratory
3M Environmental Laboratory Technical Director: William K. Reagen, Ph.D. 3M Principal Analytical Investigator: Susan Wolf Report Author: Chelsie Grochow
Analytical Report ISO13-05-04
Analysis of PFOA, PFBS, PFHS, and PFOS in Groundwater Samples Collected from Decatur, AL 3rdQuarter 2013
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 from September 27 - October 11, 2013 and returned to the 3M Environmental Laboratory on October 16, 2013 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 ISO13-05-04.
The 3M Environmental Laboratory prepared sample containers for eighteen 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, field sample duplicate, and at least one field 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.
Samples were prepared and analyzed by method ETS-8-044.1 "Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis". Select internal standards were used to aid in the data quality objectives.
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 the A2LA Testing 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 A2LA assessment.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-04
Table 1. Sample Results Summary (1)
3M LIMS ID ISO13-05-04-001 ISO13-05-04-002
ISO13-05-04-005 ISO13-05-04-006
ISO13-05-04-008 ISO13-05-04-009
ISO13-05-04-011 ISO13-05-04-012
ISO13-05-04-015 ISO13-05-04-016
ISO13-05-04-019 ISO13-05-04-020
ISO13-05-04-023 ISO13-05-04-024
ISO13-05-04-026 ISO13-05-04-027
ISO13-05-04-029 ISO13-05-04-030
Sample Description
DAL-GW-203L-0-131001 DAL-GW-203L-DB-131001
Average %RPD Sample/Sample Dup DAL-GW-220R-0-131003 DAL-GW-220R-DB-131003
Average %RPD Sample/Sample Dup DAL-GW-220L-0-131003 DAL-GW-220L-DB-131003
Average %RPD Sample/Sample Dup DAL-GW-222R-0-131001 DAL-GW-222R-DB-131001
Average %RPD Sample/Sample Dup DAL-GW-227R-0-131001 DAL-GW-227R-DB-131001
Average %RPD Sample/Sample Dup DAL-GW-227L-0-131001 DAL-GW-227L-DB-131001
Average %RPD Sample/Sample Dup DAL-GW-310R-0-131002 DAL-GW-310R-DB-131002
Average %RPD Sample/Sample Dup DAL-GW-312R-0-131011 DAL-GW-312R-DB-131011
Average %RPD Sample/Sample Dup DAL-GW-317L-0-131002 DAL-GW-317L-DB-131002
Average %RPD Sample/Sample Dup
PFOA Concentration
(ng/mL)
153 152 153 0.65 51.5 47.0 49.3 9.1 26.3 26.4 26.4 0.38 317 323 320 (23) 1.9 241 235 238 (2) 2.5 178 172 175 3.4 953 928 941 2.7 6740 6860 6800 1.8 0.290 0.308 0.299 (2) 6.0
PFBS Concentration
(ng/mL)
23.3 24.0 23.7 3.0 8.38 7.85 8.12 6.5 4.88 5.04 4.96 3.2 44.3 46.6 45.5 5.1 15.3 14.9 15.1 2.6 264 254 259 3.9 1310 1300 1310 0.76 7220 7300 7260 1.1 <0.0250 <0.0250 <0.0250 (2) NA
PFHS Concentration
(ng/mL)
147 147 147 0.0 41.6 39.0 40.3 6.5 17.0 17.5 17.3 2.9 298 317 308 6.2 58.3 55.8 57.1 4.4 83.0 81.9 82.5 1.3 310 304 307 2.0 1320 1280 1300 3.1 0.0932 0.104 0.0986 (2) 11
PFOS Concentration
(ng/mL)
787 794 791 0.88 80.9 76.8 78.9 5.2 49.5 49.5 49.5 0.0 444 474 459 6.5 660 653 657 1.1 826 838 832 1.4 778 755 767 3.0 2850 2860 2860 0.35 0.241 0.245 0.243 (2) 1.6
NA = Not Applicable (1) All samples associated with the reported sampling location were 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 using solvent dilution are as follows: PFOA 14%, PFBS 14%, PFHS 12%, and PFOS 15%. (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 17%, PFBS 17%, PFHS 16%, and PFOS 18%. (3) The analytical method uncertainty has been expanded to 34% for PFOA. See section 4 for further discussion.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-04
Table 1 continued. Sample Results Summary (1)
3M LIMS ID ISO13-05-04-032 ISO13-05-04-033
ISO13-05-04-035 ISO13-05-04-036
ISO13-05-04-039 ISO13-05-04-040
ISO13-05-04-043 ISO13-05-04-044
ISO13-05-04-047 ISO13-05-04-048
ISO13-05-04-051 ISO13-05-04-052
ISO13-05-04-054 ISO13-05-04-055
ISO13-05-04-057 ISO13-05-04-058
ISO13-05-04-060 ISO13-05-04-061
Sample Description DAL-GW-324L-0-130927 DAL-GW-324L-DB-130927
Average %RPD Sample/Sample Dup DAL-GW-RW327R-0-131011 DAL-GW-RW327R-DB-131011
Average %RPD Sample/Sample Dup DAL-GW-328R-0-130927 DAL-GW-328R-DB-130927
Average %RPD Sample/Sample Dup DAL-GW-328L-0-130927 DAL-GW-328L-DB-130927
Average %RPD Sample/Sample Dup DAL-GW-330R-0-130927 DAL-GW-330R-DB-130927
Average %RPD Sample/Sample Dup DAL-GW-330L-0-130927 DAL-GW-330L-DB-130927
Average %RPD Sample/Sample Dup DAL-GW-RW331S-0-131011 DAL-GW-RW331S-DB-131011
Average %RPD Sample/Sample Dup DAL-GW-335R-0-131002 DAL-GW-335R-DB-131002
Average %RPD Sample/Sample Dup DAL-GW-GRS04-0-131011 DAL-GW-GRS04-DB-131011
Average %RPD Sample/Sample Dup
PFOA Concentration
(ng/mL) 219 203 211 7.6 1180 1190
1190 (2) 0.84 409 397 403 (2) 3.0 108 109 109 (2) 0.92 278 281 280 1.1 83.9 82.5 83.2 1.7 422 428 425 1.4 4680 4650 4670 0.64 5530 5410 5470 2.2
PFBS Concentration
(ng/mL) 74.6 69.7 72.2 6.8 59.9 63.8 61.9 6.3 33.8 32.5 33.2 3.9 45.7 44.9
45.3 (2) 1.8 1430 1440 1440 0.69 1360 1310 1340 3.7 432 427 430 1.2 1230 1250 1240 1.6 2830 2730 2780 3.6
PFHS Concentration
(ng/mL) 55.3 53.3 54.3 3.7 159 169 164 6.1 52.4 51.0 51.7 2.7 17.6 16.1 16.9 8.9 163 163 163 0.0 462 455 459 1.5 160 161 161 0.62 1650 1660 1660 0.60 9540 9140 9340 4.3
PFOS Concentration
(ng/mL) 78.0 77.7 77.9 0.39 617 708 663 14 274 265 270 3.3 1.29 1.18 1.24 8.9 676 688 682 1.8 181 177 179 2.2 465 457 461 1.7 6440 6510 6480 1.1 2690 2940 2820 8.9
NA = Not Applicable (1) All samples associated with the reported sampling location were 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 using solvent dilution are as follows: PFOA 14%, PFBS 14%, PFHS 12%, and PFOS 15%. (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 17%, PFBS 17%, PFHS 16%, and PFOS 18%. (3) The analytical method uncertainty has been expanded to 34% for PFOA. See section 4 for further discussion.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-04
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".
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 + Branched Linear Linear
Linear + 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 from September 27 - October 11,2013 and returned to the 3M Environmental Laboratory on October 16, 2013 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 Example 1 2 3 4
5 6
String Descriptor DAL-GW-317L-0-131002 Sample Location Sample Type Well Identifier Well Level
Sampling Date Sample Type
Example
DAL= Decatur, Alabama GW= Ground Water Example: 317 R = Residuum shallow water-bearing zone L = Bedrock water-bearing zone S = Epikarst middle water-bearing zone 131002 - October 2, 2013 0 =primary sample DB =duplicate sample FMS = Field Matrix Spike LS = Low field matrix spike HS = High field matrix spike
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-04
2.3 Sample Preparation
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 diluting it with 9.0 mL of methanol. Samples requiring a 1:100 dilution were prepared by removing a 0.1 mL aliquot of the well mixed sample and diluting it with 9.9 mL of methanol. Sample injection values were decreased for some samples if a larger dilution factor was desired. Samples that did not have appropriate field matrix spike (FMS) levels based on the initial analysis, a laboratory matrix spike (LMS) sample was prepared by spiking the target analytes in a diluted aliquot of the primary sample (nominal concentration of 1000 ng/mL or 5000 ng/mL). Samples with low FMS recoveries based on the initial analysis, were analyzed with internal standard. Samples requiring dilution were diluted with synthetic groundwater and fortified with internal standard (nominal concentration of 1 ng/mL). Sample set 317L, trip blank sample, and rinseate blank were also analyzed using internal standard and prepared by removing an aliquot of well mixed sample and fortifying with internal standard prior to sample analysis. During the preparation of the laboratory control samples, an aliquot of an internal standard spiking solution was added to the laboratory control samples (nominal concentration of 1 ng/mL).
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. 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.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-04
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 Kirk 10/18/13, 10/21/13, 10/22/13
ETS-8-044.1 Agilent 1260 Betasil C18 (4.6 mm X 100 mm), 5 g Betasil C18 (4.6 mm X 100 mm), 5 g
5 or 20 |jL Applied Biosystems TripleQuad 5500
Turbo Spray Negative
Analyst 1.6.1
Table 5. Liquid Chromatography Gradient Program
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
Flow Rate (pL/min)
750 750 750 750 750 750 750 750 750 750
Table 6. Mass Transitions
2 mM Ammonium Acetate 90.0 90.0 70.0 70.0 20.0 20.0 10.0 10.0 90.0 90.0
Methanol 10.0 10.0 30.0 30.0 80.0 80.0 90.0 90.0 10.0 10.0
Analyte
Mass Transition Q1/Q3
Internal Standard (1)
Mass Transition Q1/Q3
Reference Material Structure
413/369
PFOA
413/219
[13Cs]PFOA
421/376
Linear + Branched
413/169
PFBS PFHS
299/80 299/99 399/99 399/80
[18O2]PFBS [13Cs]PFHS
303/84 402/80
Linear Linear
499/99
PFOS
499/80
[13Cs]-PFOS
507/80
Linear + Branched
499/130
Dwell time was 20 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 10/22/13.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-04
3 Data Analysis
3.1 Calibration
External Standard Calibration Analysis: Samples were analyzed against an external standard calibration curve. Calibration standards were prepared by spiking known amounts of the stock solution containing the target analytes into 90:10 methanol:laboratory Milli-QTM water. A total of eleven spiked standards ranging from 0.02 ng/mL to 50 ng/mL (nominal) were analyzed. A quadratic, 1/x weighted, calibration curve of the standard peak area counts was used to fit the data for each analyte. The data were not forced through zero during the fitting process. Calculating the standard concentrations using the peak area counts and the resultant calibration curve confirmed accuracy of each curve point.
Internal Standard Calibration Analysis: 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 laboratory prepared reagent water. The calibration standards contained an internal standard mix at a nominal concentration of 1 ng/mL. A total of fourteen calibration standards ranging from 0.025 ng/mL to 50 ng/mL (nominal) were analyzed with the prepared samples. 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. The data were not forced through zero during the fitting process. Calculating the standard concentrations using the peak area ratios and the resultant calibration curve confirmed accuracy of each curve point.
For each calibration curve, the reference standards of PFOA and PFOS used to prepare the calibration standards consisted of both linear and branched isomers. 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 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
10/18/13
Calibration External Standard
10/21/13
External standard
10/22/13
Internal standard
Dilution Factor
10 100 400 100 400
1 10 100
PFBA LOQ, ng/mL
0.192 1.92 7.68 1.92 7.68 0.0240 0.240 2.40
PFOA LOQ, ng/mL
0.200 2.00 8.00 2.00 8.00 0.0250 0.250 2.50
PFBS LOQ, ng/mL
0.200 2.00 8.00 2.00 8.00 0.0400 0.400 4.00
PFOS LOQ, ng/mL
0.185 1.85 7.40 1.85 7.40 0.0232 0.232 2.32
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-04
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%, was met for all LCS samples.
Note: Lab matrix spike samples (LMS) for locations RW312R and 333L were prepared on 10/21/13 without additional LCSs. This is a deviation from the method that states that LCSs should be prepared each day that samples are aliquoted. While this is a deviation from the method, the LMS samples were analyzed in an analytical batch with samples for which LCS samples were prepared. Both the LMS and LCS samples analyzed on 10/21/13 met method acceptance criteria.
All LCSs were used in the determination of the analytical method uncertainty in section 3.7.
The following calculations were used to generate data in Table 8.
LCS Percent Recovery Calculated Concentration * 10 0 % Spike Concentration
standard deviation LCS replicates
LCS% RSD =
100%
average LCS recovery
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-04
Table 8. Lab Control Spike Results
ETS-8-044.1 Analyzed 10/18/13 External Standard Calibration
Lab ID LCS-131018-1 LCS-131018-2 LCS-131018-3 Average %RSD LCS-131018-4 LCS-131018-5 LCS-131018-6 Average %RSD LCS-131018-7 LCS-131018-8 LCS-131018-9 Average %RSD
PFOA (Linear and Branched)
Spiked
Calculated
Concentration Concentration
(ng/mL)
(ng/mL)
%Recovery
0.191 0.191 0.191
4.77 4.77 4.77
38.2 38.2 38.2
0.193 0.206 0.193 103% 3.9% 5.15 5.14 5.22 108% 0.53% 37.8 35.9 36.6 96.3% 2.6%
101 108 101
108 108 109
98.9 94.0 95.9
Spiked Concentration
(ng/mL) 0.200 0.200 0.200
4.98 4.98 4.98
39.8 39.8 39.8
PFBS Calculated Concentration
(ng/mL)
0.212 0.221 0.210 107% 3.0% 5.20 5.38 5.33 106% 2.0% 40.0 37.8 38.5 97.5% 3.2%
%Recovery 106 111 105
104 108 107
101 94.9 96.7
ETS-8-044.1 Analyzed 10/18/13 External Standard Calibration
Lab ID LCS-131018-1 LCS-131018-2 LCS-131018-3 Average %RSD LCS-131018-4 LCS-131018-5 LCS-131018-6 Average %RSD LCS-131018-7 LCS-131018-8 LCS-131018-9 Average %RSD
Spiked Concentration
(ng/mL)
PFHS
Calculated Concentration
(ng/mL)
0.200 0.200 0.200
4.98 4.98 4.98
39.8 39.8 39.8
0.202 0.209 0.207 103% 1.5% 5.29 5.34 5.40 107% 1.4% 40.2 36.6 38.0 96.1% 4.8%
%Recovery 101 104 103
106 107 109
101 91.9 95.4
PFOS (Linear and Branched)
Spiked Concentration
(ng/mL)
Calculated Concentration
(ng/mL)
%Recovery
0.185 0.185 0.185
4.61 4.61 4.61
36.9 36.9 36.9
0.201 0.211 0.202 111% 2.6% 5.21 5.34 5.30 115% 1.3% 38.3 35.7 36.8 100% 3.6%
109 114 109
113 116 115
104 96.8 99.9
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-04
Table 8 continued. Lab Control Spike Results
ETS-8-044.1 Analyzed 10/21/13 External Standard Calibration
Lab ID LCS-131018-1 LCS-131018-2 LCS-131018-3 Average %RSD LCS-131018-4 LCS-131018-5 LCS-131018-6 Average %RSD LCS-131018-7 LCS-131018-8 LCS-131018-9 Average %RSD
PFOA (Linear and Branched)
Spiked
Calculated
Concentration Concentration
(ng/mL)
(ng/mL)
%Recovery
0.191 0.191 0.191
4.77 4.77 4.77
38.2 38.2 38.2
0.202 0.207 0.212 108% 2.3% 5.31 5.35 5.35 112% 0.52% 41.5 38.6 40.5 105% 3.8%
106 108 111
111 112 112
109 101 106
Spiked Concentration
(ng/mL) 0.200 0.200 0.200
4.98 4.98 4.98
39.8 39.8 39.8
PFBS Calculated Concentration
(ng/mL)
0.220 0.221 0.221 111% 0.52% 5.35 5.62 5.61 111% 3.1% 43.1 39.6 42.1 105% 4.2%
%Recovery 110 111 111
107 113 113
108 99.6 106
ETS-8-044.1 Analyzed 10/21/13 External Standard Calibration
Lab ID LCS-131018-1 LCS-131018-2 LCS-131018-3 Average %RSD LCS-131018-4 LCS-131018-5 LCS-131018-6 Average %RSD LCS-131018-7 LCS-131018-8 LCS-131018-9 Average %RSD
Spiked Concentration
(ng/mL)
PFHS
Calculated Concentration
(ng/mL)
0.200 0.200 0.200
4.98 4.98 4.98
39.8 39.8 39.8
0.215 0.219 0.210 107% 1.9% 5.32 5.53 5.42 109% 1.8% 41.7 38.2 41.3 102% 4.8%
%Recovery 108 109 105
107 111 109
105 96.0 104
PFOS (Linear and Branched)
Spiked Concentration
(ng/mL)
Calculated Concentration
(ng/mL)
%Recovery
0.185 0.185 0.185
4.61 4.61 4.61
36.9 36.9 36.9
0.212 0.215 0.215 116% 0.50% 5.45 5.58 5.59 120% 1.4% 40.9 37.4 40.3 107% 4.9%
115 116 116
118 121 121
111 101 109
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-04
Table 8 continued. Lab Control Spike Results
ETS-8-044.1 Analyzed 10/22/13 Internal Standard Calibration
Lab ID LCS-131022-1 LCS-131022-2 LCS-131022-3 Average %RSD LCS-131022-4 LCS-131022-5 LCS-131022-6 Average %RSD LCS-131022-7 LCS-131022-8 LCS-131022-9 Average %RSD
PFOA (Linear and Branched)
Spiked
Calculated
Concentration Concentration
(ng/mL)
(ng/mL)
%Recovery
0.190 0.190 0.190
4.74 4.74 4.74
38.0 38.0 38.0
0.178 0.195 0.197 100% 5.6% 5.04 4.82 5.00 105% 2.2% 37.5 36.7 36.0 96.7% 2.1%
93.9 103 104
106 102 106
98.8 96.5 94.7
Spiked Concentration
(ng/mL) 0.199 0.199 0.199
4.95 4.95 4.95
39.6 39.6 39.6
PFBS Calculated Concentration
(ng/mL)
0.196 0.203 0.196 99.6% 2.1% 5.20 5.13 5.29 105% 1.5% 42.2 39.3 39.2 102% 4.5%
%Recovery 98.4 102 98.4
105 104 107
107 99.3 98.9
ETS-8-044.1 Analyzed 10/22/13 Internal Standard Calibration
Lab ID LCS-131022-1 LCS-131022-2 LCS-131022-3 Average %RSD LCS-131022-4 LCS-131022-5 LCS-131022-6 Average %RSD LCS-131022-7 LCS-131022-8 LCS-131022-9 Average %RSD
Spiked Concentration
(ng/mL)
PFHS
Calculated Concentration
(ng/mL)
0.199 0.199 0.199
4.95 4.95 4.95
39.6 39.6 39.6
0.199 0.204 0.208 103% 2.5% 5.22 5.29 5.21 106% 1.1% 39.9 38.3 37.9 97.8% 2.9%
%Recovery 99.8 103 105
105 107 105
101 96.7 95.6
PFOS (Linear and Branched)
Spiked Concentration
(ng/mL)
Calculated Concentration
(ng/mL)
%Recovery
0.184 0.184 0.184
4.59 4.59 4.59
36.7 36.7 36.7
0.194 0.203 0.191 106% 3.0% 4.89 4.93 4.93 107% 0.0% 38.9 37.2 36.7 102% 3.2%
105 110 104
107 107 107
106 101 99.9
PAGE 12 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-04
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 (%) 6.91 6.88 6.04 7.65 8.54 8.32 7.79 8.80
Method Uncertainty 14% 14% 12% 15% 17% 17% 16% 18%
3.8 Field Matrix Spikes (FMS)
Field matrix spike sample containers were prepared for all 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 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 9. Field matrix spikes are presented in section 4 of this report.
TMFMS Recovery =(-S--a-m--p-l-e--C--o-n--c-e--n-t-r-a-t-i-o-n---o-f--F--M--S------A--v-e--r-a-g2e---C--o-n--c-e-n--t-r-a-t-i-o-n---:-F-i-e-l-d--S--a-m--p-l-e--&---F-i-e--ld---S-a--m--p-l-e--D--u-p--.) *100% Spike Concentration
PAGE 13 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-04
Table 10. Field Matrix Spike Concentrations
Sampling location 203L 220R and 220L 222R and 227L
227R and 328R
330R 310R, RW312R, and RW331S 317L 324L RW327R
328L 330L 335R and GRS04
Trip Blank
Spike Level Low High FMS Low High Low High Low High FMS FMS FMS Low High Low High FMS FMS Low
Mid High
PFOA ng/mL
100 501 50.0 100 501 50.0 501 501 1000 1000 1.00 200 100 1000 1.00 100 501 5010 1.00 100 1000
PFBS ng/mL
100 502 50.0 100 502 50.0 502 502 1000 1000 1.00 200 100 1000 1.00 100 502 5020 1.00 100 1000
PFHS ng/mL
99.8 499 49.9 99.8 499 49.9 499 499 998 998 0.999 200 99.8 998 0.999 99.8 499 4990 0.999 99.8 998
PFOS ng/mL
99.4 497 49.7 99.4 497 49.7 497 497 994 994 1.00 199 99.4 994 1.00 99.4 497 4970 1.00 99.4 994
3.9 Lab Matrix Spikes (LMS)
Due to inappropriate field matrix spike levels, lab matrix spike samples were prepared for locations RW312R and 330L to verify that the analytical method is applicable to the collected matrix. Lab matrix spikes are generated by adding a measured volume of spiking solution to an aliquot of the primary sample post-dilution from each sample set. The LMS sample was spiked at a nominal concentration of 5000 ng/mL for sampling location RW312R and 1000 ng/mL for sampling location 330L.
Lab 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. Lab matrix spikes are presented in section 4 of this report.
LM S Recovery - (Sample Concentration of LM S - Concentration:Field Sample ) * 100% Spike Concentration
PAGE 14 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-04
4 Data Summary and Discussion
The tables below summarize the sample results and target analyte field matrix spike recoveries for the sampling locations as well as the T rip Blank. Where applicable, the data tables also include the recovery results for a lab matrix spike. 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 and laboratory matrix spikes met method acceptance criteria with the following exceptions: Location 222R; The FMS recovery for PFOA was 66.1%. The analytical uncertainty for this location was expanded to 34%.
PAGE 15 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-04
Table 11. DAL GW 203L 131001
3M LIMS ID
Description
ISO13-05-04-001
DAL-GW-203L-0-131001
ISO13-05-04-002
DAL-GW-203L-DB-131001
ISO13-05-04-003
DAL-GW-203L-LS-131001
ISO13-05-04-004
DAL-GW-203L-HS-131001
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
153 NA 152 NA 236 83.0 517 72.7
153 ng/mL 0.65%
PFBS
Concentration (ng/mL)
%Recovery
23.3 NA 24.0 NA 113 89.3 459 86.7
23.7 ng/mL 3.0%
PFHS
3M LIMS ID
Description
ISO13-05-04-001
DAL-GW-203L-0-131001
ISO13-05-04-002
DAL-GW-203L-DB-131001
ISO13-05-04-003
DAL-GW-203L-LS-131001
ISO13-05-04-004
DAL-GW-203L-HS-131001
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
147 NA 147 NA 234 87.2 596 90.0
147 ng/mL 0.0%
NA = Not Applicable NC= Not Calculated; Spike levels were less than 0.5x the endogenous sample concentration. Samples were diluted 1:100 and analyzed by external standard quantitation.
PFOS
Concentration (ng/mL)
%Recovery
787 NA
794 NA
858 NC
1410
125
791 ng/mL 0.88%
Table 12. DAL GW 220R 131003
3M LIMS ID
Description
ISO13-05-04-005
DAL-GW-220R-0-131003
ISO13-05-04-006
DAL-GW-220R-DB-131003
ISO13-05-04-007
DAL-GW-220R-FMS-131003
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
51.5 NA 47.0 NA 88.8 79.0
49.3 ng/mL 9.1%
PFBS
Concentration (ng/mL)
%Recovery
8.38 NA 7.85 NA 51.2 86.2
8.12 ng/mL 6.5%
PFHS
3M LIMS ID
Description
ISO13-05-04-005
DAL-GW-220R-0-131003
ISO13-05-04-006
DAL-GW-220R-DB-131003
ISO13-05-04-007
DAL-GW-220R-FMS-131003
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
41.6 NA 39.0 NA 85.0 89.6
40.3 ng/mL 6.5%
NA = Not Applicable Samples were diluted 1:10 and analyzed using external standard quantitation.
PFOS
Concentration (ng/mL)
%Recovery
80.9 NA 76.8 NA 128 98.8
78.9 ng/mL 5.2%
PAGE 16 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-04
Table 13. DAL GW 220L 131003
3M LIMS ID
Description
ISO13-05-04-008
DAL-GW-220L-0-131003
ISO13-05-04-009
DAL-GW-220L-DB-131003
ISO13-05-04-010
DAL-GW-220L-FMS-131003
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
26.3 NA 26.4 NA 68.2 83.6
26.4 ng/mL 0.38%
PFBS
Concentration (ng/mL)
%Recovery
4.88 NA 5.04 NA 49.5 89.1
4.96 ng/mL 3.2%
3M LIMS ID
Description
ISO13-05-04-008
DAL-GW-220L-0-131003
ISO13-05-04-009
DAL-GW-220L-DB-131003
ISO13-05-04-010
DAL-GW-220L-FMS-131003
Average Concentration (ng/mL) %RPD
PFHS
Concentration (ng/mL)
%Recovery
17.0 NA 17.5 NA 63.2 92.0
17.3 ng/mL 2.9%
PFOS
Concentration (ng/mL)
%Recovery
49.5 NA 49.5 NA 98.5 98.6
49.5 ng/mL 0.0%
NA = Not Applicable Samples were diluted 1:10 and analyzed using external standard quantitation.
Table 14. DAL GW 222R 131001
3M LIMS ID
Description
ISO13-05-04-011
DAL-GW-222R-0-131001
ISO13-05-04-012
DAL-GW-222R-DB-131001
ISO13-05-04-013
DAL-GW-222R-LS-131001
ISO13-05-04-014
DAL-GW-222R-HS-131001
Average Concentration (ng/mL) %RPD
PFOA (1)
Concentration (ng/mL)
%Recovery
317 NA
323 NA
NR (3)
NR (3)
651 66.1 (4)
320 ng/mL 1.9% (5)
PFBS (2)
Concentration (ng/mL)
%Recovery
44.3 NA 46.6 NA 135 89.5 420 74.6
45.5 ng/mL 5.1%
PFHS (2)
PFOS (2)
3M LIMS ID
Description
Concentration (ng/mL)
%Recovery
Concentration (ng/mL)
%Recovery
ISO13-05-04-011
DAL-GW-222R-0-131001
298 NA 444
NA
ISO13-05-04-012
DAL-GW-222R-DB-131001
317
NA
474
NA
ISO13-05-04-013
DAL-GW-222R-LS-131001
401
NC 548
NC
ISO13-05-04-014
DAL-GW-222R-HS-131001
707
80.0
861
80.9
Average Concentration (ng/mL) %RPD
308 ng/mL 6.2%
459 ng/mL 6.5%
NA = Not Applicable
NC = Not Calculated; Spike level was less than 0.5x the endogenous sample concentration.
(1) Samples were diluted 1:100 and analyzed using internal standard quantitation. Internal standard was added to the samples
during sample preparation.
(2) Samples were diluted 1:100 and analyzed using external standard quantitation.
(3) NR = Not reportable; sample was not repeated since the spike level was less than 0.5x the sample concentration.
(4) FMS did not meet acceptance criteria of 100 30%.
(5) The analytical uncertainty was expanded to 34% for PFOA.
PAGE 17 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-04
Table 15. DAL GW 227R 131001
3M LIMS ID
Description
ISO13-05-04-015
DAL-GW-227R-0-131001
ISO13-05-04-016
DAL-GW-227R-DB-131001
ISO13-05-04-017
DAL-GW-227R-LS-131001
ISO13-05-04-018
DAL-GW-227R-HS-131001
Average Concentration (ng/mL) %RPD
PFOA (1)
Concentration (ng/mL)
%Recovery
241 NA
235 NA
NR (3)
NR (3)
609 74.1
238 ng/mL 2.5%
PFBS (2)
Concentration (ng/mL)
%Recovery
15.3 NA 14.9 NA 59.7 89.2 443 85.2
15.1 ng/mL 2.6%
PFHS (2)
PFOS (2)
3M LIMS ID
Description
ISO13-05-04-015
DAL-GW-227R-0-131001
ISO13-05-04-016
DAL-GW-227R-DB-131001
ISO13-05-04-017
DAL-GW-227R-LS-131001
ISO13-05-04-018
DAL-GW-227R-HS-131001
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
58.3 NA 55.8 NA 102 90.0 505 89.8
57.1 ng/mL 4.4%
Concentration (ng/mL)
%Recovery
660 NA
653 NA
811 NC
1140
97.2
657 ng/mL 1.1%
NA = Not Applicable NC = Not Calculated; Spike level was less than 0.5x the endogenous sample concentration. (1) Samples were diluted 1:100 and analyzed using internal standard quantitation. Internal standard was added to the samples
during sample preparation. (2) Samples were diluted 1:100 and analyzed using external standard quantitation. (3) NR = Not reportable; sample was not repeated since the spike level was less than 0.5x the sample concentration.
PAGE 18 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-04
Table 16. DAL GW 227L 131001
3M LIMS ID
Description
ISO13-05-04-019
DAL-GW-227L-0-131001
ISO13-05-04-020
DAL-GW-227L-DB-131001
ISO13-05-04-021
DAL-GW-227L-LS-131001
ISO13-05-04-022
DAL-GW-227L-HS-131001
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
178 NA 172 NA 254 79.0 540 72.9
175 ng/mL 3.4%
PFBS
Concentration (ng/mL)
%Recovery
264 NA 254 NA 338 NC 706 89.0
259 ng/mL 3.9%
PFHS
3M LIMS ID
Description
ISO13-05-04-019
DAL-GW-227L-0-131001
ISO13-05-04-020
DAL-GW-227L-DB-131001
ISO13-05-04-021
DAL-GW-227L-LS-131001
ISO13-05-04-022
DAL-GW-227L-HS-131001
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
83.0 NA 81.9 NA 167 84.7 538 91.3
82.5 ng/mL 1.3%
NA = Not Applicable NC = Not Calculated; Spike level was less than 0.5x the endogenous sample concentration. Samples were diluted 1:100 and analyzed using external standard quantitation.
PFOS
Concentration (ng/mL)
%Recovery
826 NA
838 NA
905 NC
1310
96.2
832 ng/mL 1.4%
Table 17. DAL GW 310R 131002
3M LIMS ID
Description
ISO13-05-04-023
DAL-GW-310R-0-131002
ISO13-05-04-024
DAL-GW-310R-DB-131002
ISO13-05-04-025
DAL-GW-310R-FMS-131002
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
953 NA
928 NA
1750
80.9
941 ng/mL 2.7%
PFBS
Concentration (ng/mL)
%Recovery
1310
NA
1300
NA
2200
89.0
1310 ng/mL 0.76%
PFHS
3M LIMS ID
Description
ISO13-05-04-023
DAL-GW-310R-0-131002
ISO13-05-04-024
DAL-GW-310R-DB-131002
ISO13-05-04-025
DAL-GW-310R-FMS-131002
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
310 NA
304 NA
1230
92.5
307 ng/mL 2.0%
NA = Not Applicable Samples were diluted 1:100 and analyzed using external standard quantitation.
PFOS
Concentration (ng/mL)
%Recovery
778 NA
755 NA
1720
95.9
767 ng/mL 3.0%
PAGE 19 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-04
Table 18. DAL GW RW312R 131011
PFOA
3M LIMS ID
Description
Concentration (ng/mL)
%Recovery
ISO13-05-04-026
DAL-GW-RW312R-0-131011
ISO13-05-04-027
DAL-GW-RW312R-DB-131011
ISO13-05-04-028
DAL-GW-RW312R-FMS-131011
ISO13-05-04-026; LMS
DAL-GW-RW312R-0-LMS
Average Concentration (ng/mL) %RPD
6740
NA
6860
NA
NR (1)
NR (1)
12400
119
6800 ng/mL 1.8%
PFBS
Concentration (ng/mL)
%Recovery
7220
NA
7300
NA
NR (1)
NR (1)
12600
108
7260 ng/mL 1.1%
PFHS
PFOS
3M LIMS ID
Description
Concentration (ng/mL)
%Recovery
ISO13-05-04-026
DAL-GW-RW312R-0-131011
ISO13-05-04-027
DAL-GW-RW312R-DB-131011
ISO13-05-04-028
DAL-GW-RW312R-FMS-131011
ISO13-05-04-026; LMS
DAL-GW-RW312R-0-LMS
Average Concentration (ng/mL) %RPD
1320
NA
1280
NA
2260
96.2
NA NA
1300 ng/mL 3.1%
Concentration (ng/mL)
%Recovery
2850
NA
2860
NA
NR (1)
NR (1)
8550
124
2860 ng/mL 0.35%
NA = Not Applicable Samples were diluted 1:100 and analyzed using external standard quantitation. The injection volume was decreased to produce a dilution factor of 400. (1) NR = Not reportable; sample was not repeated since the spike level was less than 0.5x the sample concentration.
Table 19. DAL GW 317L 131002
3M LIMS ID
Description
ISO13-05-04-029
DAL-GW-317L-0-131002
ISO13-05-04-030
DAL-GW-317L-DB-131002
ISO13-05-04-031
DAL-GW-317L-FMS-131002
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
0.290
NA
0.308
NA
1.18 88.1
0.299 ng/mL 6.0%
PFBS
Concentration (ng/mL)
%Recovery
<0.0250
NA
<0.0250
NA
0.989
98.9
<0.0250 ng/mL
3M LIMS ID
Description
ISO13-05-04-029
DAL-GW-317L-0-131002
ISO13-05-04-030
DAL-GW-317L-DB-131002
ISO13-05-04-031
DAL-GW-317L-FMS-131002
Average Concentration (ng/mL) %RPD
PFHS
Concentration (ng/mL)
%Recovery
0.0932
NA
0.104
NA
1.10 100
0.0986 ng/mL 11%
PFOS
Concentration (ng/mL)
%Recovery
0.241
NA
0.245
NA
1.23 98.7
0.243 ng/mL 1.6%
NA = Not Applicable Samples were analyzed using internal standard quantitation. Internal standard was added to the samples during sample preparation.
PAGE 20 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-04
Table 20. DAL GW 324L 130927
3M LIMS ID
Description
ISO13-05-04-032
DAL-GW-324L-0-130927
ISO13-05-04-033
DAL-GW-324L-DB-130927
ISO13-05-04-034
DAL-GW-324L-FMS-130927
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
219 NA 203 NA 363 76.0
211 ng/mL 7.6%
PFBS
Concentration (ng/mL)
%Recovery
74.6 NA 69.7 NA 236 81.9
72.2 ng/mL 6.8%
PFHS
PFOS
3M LIMS ID
Description
ISO13-05-04-032
DAL-GW-324L-0-130927
ISO13-05-04-033
DAL-GW-324L-DB-130927
ISO13-05-04-034
DAL-GW-324L-FMS-130927
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
55.3 NA 53.3 NA 228 86.9
54.3 ng/mL 3.7%
Concentration (ng/mL)
%Recovery
78.0 NA 77.7 NA 264 93.5
77.9 ng/mL 0.39%
NA = Not Applicable Samples were diluted 1:10 and analyzed using external standard quantitation.
Table 21. DAL GW RW327R 131011
3M LIMS ID
Description
ISO13-05-04-035
DAL-GW-RW327R-0-131011
ISO13-05-04-036
DAL-GW-RW327R-DB-131011
ISO13-05-04-037
DAL-GW-RW327R-LS-131011
ISO13-05-04-038
DAL-GW-RW327R-HS-131011
Average Concentration (ng/mL) %RPD
PFOA (1)
Concentration (ng/mL)
%Recovery
1180
NA
1190
NA
NR (3)
NR (3)
1910
72.0
1190 ng/mL 0.84%
PFBS (2)
Concentration (ng/mL)
%Recovery
59.9 NA 63.8 NA 150 88.1 943 88.1
61.9 ng/mL 6.3%
PFHS (2)
PFOS (2)
3M LIMS ID
Description
ISO13-05-04-035
DAL-GW-RW327R-0-131011
ISO13-05-04-036
DAL-GW-RW327R-DB-131011
ISO13-05-04-037
DAL-GW-RW327R-LS-131011
ISO13-05-04-038
DAL-GW-RW327R-HS-131011
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
159 NA
169 NA
257 93.2
1050
88.8
164 ng/mL 6.1%
Concentration (ng/mL)
%Recovery
617 NA
708 NA
747 NC
1530
87.2
663 ng/mL 14%
NA = Not Applicable NC = Not Calculated; Spike level was less than 0.5x the endogenous sample concentration (1) Samples were diluted 1:100 and analyzed using internal standard quantitation. Internal standard was added to the samples
during sample preparation. (2) Samples were diluted 1:100 and analyzed using external standard quantitation. (3) NR = Not reportable; sample was not repeated since the spike level was less than 0.5x the sample concentration.
PAGE 21 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-04
Table 22. DAL GW 328R 130927
3M LIMS ID
Description
ISO13-05-04-039
DAL-GW-328R-0-130927
ISO13-05-04-040
DAL-GW-328R-DB-130927
ISO13-05-04-041
DAL-GW-328R-LS-130927
ISO13-05-04-042
DAL-GW-328R-HS-130927
Average Concentration (ng/mL) %RPD
PFOA (1)
Concentration (ng/mL)
%Recovery
409 NA
397 NA
NR (3)
NR (3)
787 76.6
403 ng/mL 3.0%
PFBS (2)
Concentration (ng/mL)
%Recovery
33.8 NA 32.5 NA 74.1 81.8 428 78.6
33.2 ng/mL 3.9%
PFHS (2)
PFOS (2)
3M LIMS ID
Description
ISO13-05-04-039
DAL-GW-328R-0-130927
ISO13-05-04-040
DAL-GW-328R-DB-130927
ISO13-05-04-041
DAL-GW-328R-LS-130927
ISO13-05-04-042
DAL-GW-328R-HS-130927
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
52.4 NA 51.0 NA 94.8 86.4 461 82.0
51.7 ng/mL 2.7%
Concentration (ng/mL)
%Recovery
274 NA 265 NA 311 NC 693 85.1
270 ng/mL 3.3%
NA = Not Applicable NC = Not Calculated; Spike level was less than 0.5x the endogenous sample concentration (1) Samples were diluted 1:10 (0, DB, LS) or 1:100 (HS) and analyzed using internal standard quantitation. Internal standard
was added to the samples during sample preparation. (2) Samples were diluted 1:10 (0, DB, LS) or 1:100 (HS) and analyzed using external standard quantitation. (3) NR = Not reportable; sample was not repeated since the spike level was less than 0.5x the sample concentration.
PAGE 22 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-04
Table 23. DAL GW 328L 130927
3M LIMS ID
Description
ISO13-05-04-043
DAL-GW-328L-0-130927
ISO13-05-04-044
DAL-GW-328L-DB-130927
ISO13-05-04-045
DAL-GW-328L-LS-130927
ISO13-05-04-046
DAL-GW-328L-HS-130927
Average Concentration (ng/mL) %RPD
PFOA (1)
Concentration (ng/mL)
%Recovery
108 NA
109 NA
NR (3)
NR (3)
207 98.0
109 ng/mL 0.92%
PFBS (1)
Concentration (ng/mL)
%Recovery
45.7 NA
44.9 NA
NR (3)
NR (3)
143 97.7
45.3 ng/mL 1.8%
PFHS (2)
PFOS (2)
3M LIMS ID
Description
ISO13-05-04-043
DAL-GW-328L-0-130927
ISO13-05-04-044
DAL-GW-328L-DB-130927
ISO13-05-04-045
DAL-GW-328L-LS-130927
ISO13-05-04-046
DAL-GW-328L-HS-130927
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
17.6 NA 16.1 NA 17.0 NC 92.6 75.9
16.9 ng/mL 8.9%
Concentration (ng/mL)
%Recovery
1.29 NA 1.18 NA 1.97 73.0 87.0 86.3
1.24 ng/mL 8.9%
NA = Not Applicable NC = Not Calculated; Spike level was less than 0.5x the endogenous sample concentration (1) Samples were diluted 1:10 and analyzed using internal standard quantitation. Internal standard was added to the samples
during sample preparation. (2) Samples were diluted 1:10 and analyzed using external standard quantitation. (3) NR = Not reportable; sample was not repeated since the spike level was less than 0.5x the sample concentration.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-04
Table 24. DAL GW 330R 130927
3M LIMS ID
Description
ISO13-05-04-047
DAL-GW-330R-0-130927
ISO13-05-04-048
DAL-GW-330R-DB-130927
ISO13-05-04-049
DAL-GW-330R-LS-130927
ISO13-05-04-050
DAL-GW-330R-HS-130927
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
278 NA
281 NA
669 77.6
1130
85.0
280 ng/mL 1.1%
PFBS
Concentration (ng/mL)
%Recovery
1430
NA
1440
NA
1860
NC
2320
88.0
1440 ng/mL 0.69%
3M LIMS ID
Description
ISO13-05-04-047
DAL-GW-330R-0-130927
ISO13-05-04-048
DAL-GW-330R-DB-130927
ISO13-05-04-049
DAL-GW-330R-LS-130927
ISO13-05-04-050
DAL-GW-330R-HS-130927
Average Concentration (ng/mL) %RPD
PFHS
Concentration (ng/mL)
%Recovery
163 NA
163 NA
613 90.2
1080
91.9
163 ng/mL 0.0%
PFOS
Concentration (ng/mL)
%Recovery
676 NA
688 NA
1160
96.2
1730
105
682 ng/mL 1.8%
NA = Not Applicable NC = Not Calculated; Spike level was less than 0.5x the endogenous sample concentration Samples were diluted 1:100 and analyzed using external standard quantitation.
Table 25. DAL GW 330L 130927
3M LIMS ID
Description
ISO13-05-04-051
DAL-GW-330L-0-130927
ISO13-05-04-052
DAL-GW-330L-DB-130927
ISO13-05-04-053
DAL-GW-330L-FMS-130927
ISO13-05-04-051; LMS
DAL-GW-330L-0-LMS
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
83.9 NA 82.5 NA 481 79.4 NA NA
83.2 ng/mL 1.7%
PFBS
Concentration (ng/mL)
%Recovery
1360
NA
1310
NA
NR (1)
NR (1)
2350
99.1
1340 ng/mL 3.7%
PFHS
PFOS
3M LIMS ID
Description
ISO13-05-04-051
DAL-GW-330L-0-130927
ISO13-05-04-052
DAL-GW-330L-DB-130927
ISO13-05-04-053
DAL-GW-330L-FMS-130927
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
462 NA 455 NA 925 93.4
459 ng/mL 1.5%
Concentration (ng/mL)
%Recovery
181 NA 177 NA 681 101
179 ng/mL 2.2%
NA = Not Applicable Samples were diluted 1:00 and analyzed using external standard quantitation. (1) NR = Not reportable; sample was not repeated since the spike level was less than 0.5x the sample concentration.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-04
Table 26. DAL GW RW331S 131011
PFOA
3M LIMS ID
Description
Concentration (ng/mL)
%Recovery
ISO13-05-04-054
DAL-GW-RW331S-0-131011
ISO13-05-04-055
DAL-GW-RW331S-DB-131011
ISO13-05-04-056
DAL-GW-RW331S-FMS-131011
Average Concentration (ng/mL) %RPD
422 NA
428 NA
1200
77.5
425 ng/mL 1.4%
PFBS
Concentration (ng/mL)
%Recovery
432 NA
427 NA
1270
84.0
430 ng/mL 1.2%
PFHS
3M LIMS ID
Description
Concentration (ng/mL)
%Recovery
ISO13-05-04-054
DAL-GW-RW331S-0-131011
ISO13-05-04-055
DAL-GW-RW331S-DB-131011
ISO13-05-04-056
DAL-GW-RW331S-FMS-131011
Average Concentration (ng/mL) %RPD
160 NA
161 NA
1040
88.1
161 ng/mL 0.62%
NA = Not Applicable Samples were diluted 1:00 and analyzed using external standard quantitation.
PFOS
Concentration (ng/mL)
%Recovery
465 NA
457 NA
1410
95.5
461 ng/mL 1.7%
Table 27. DAL GW 335R 131002
3M LIMS ID
Description
ISO13-05-04-057
DAL-GW-335R-0-131002
ISO13-05-04-058
DAL-GW-335R-DB-131002
ISO13-05-04-059
DAL-GW-335R-FMS-131002
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
4680
NA
4650
NA
9820
103
4670 ng/mL 0.64%
PFBS
Concentration (ng/mL)
%Recovery
1230
NA
1250
NA
6110
97.0
1240 ng/mL 1.6%
PFHS
3M LIMS ID
Description
ISO13-05-04-057
DAL-GW-335R-0-131002
ISO13-05-04-058
DAL-GW-335R-DB-131002
ISO13-05-04-059
DAL-GW-335R-FMS-131002
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
1650
NA
1660
NA
6540
97.8
1660 ng/mL 0.60%
NA = Not Applicable Samples were diluted 1:100 and analyzed using external standard quantitation.
PFOS
Concentration (ng/mL)
%Recovery
6440
NA
6510
NA
11900
109
6480 ng/mL 1.1%
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-04
Table 28. DAL GW GRS04 131011
PFOA
3M LIMS ID
Description
ISO13-05-04-060
DAL-GW-GRS04-0-131011
ISO13-05-04-061
DAL-GW-GRS04-DB-131011
ISO13-05-04-062
DAL-GW-GRS04-FMS-131011
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
5530
NA
5410
NA
10800
106
5470 ng/mL 2.2%
PFBS
Concentration (ng/mL)
%Recovery
2830
NA
2730
NA
7940
103
2780 ng/mL 3.6%
PFHS
3M LIMS ID
Description
ISO13-05-04-060
DAL-GW-GRS04-0-131011
ISO13-05-04-061
DAL-GW-GRS04-DB-131011
ISO13-05-04-062
DAL-GW-GRS04-FMS-131011
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
9540
NA
9140
NA
15400
121
9340 ng/mL 4.3%
NA = Not Applicable Samples were diluted 1:100 and analyzed using external standard quantitation.
PFOS
Concentration (ng/mL)
%Recovery
2690
NA
2940
NA
7720
98.6
2820 ng/mL 8.9%
Table 29. Trip Blank
3M LIMS ID
ISO13-05-04-063 ISO13-05-04-064 ISO13-05-04-065 ISO13-05-04-066
Description
DAL-GW-TRIP01 -0 (1) DAL-GW-TRIP01 -LS (2) DAL-GW-TRI P01-MS (2) DAL-GW-TRI P01-HS (2)
PFOA
Concentration (ng/mL)
<0.0240 0.856 98.2 964
%Recovery
NA 85.6 98.2 96.4
PFBS
Concentration (ng/mL)
<0.0250 0.974 95.3 932
%Recovery
NA 97.4 95.3 93.2
PFHS
PFOS
3M LIMS ID
ISO13-05-04-063 ISO13-05-04-064 ISO13-05-04-065 ISO13-05-04-066
Description
DAL-GW-TRI P01-0 (1) DAL-GW-TRI P01-LS (2) DAL-GW-TRI P01-MS (2) DAL-GW-TRI P01-HS (2)
Concentration (ng/mL)
<0.0400 0.915 98.2 968
%Recovery
NA 91.6 98.4 97.0
Concentration (ng/mL)
<0.0232 0.894 106 1130
%Recovery
NA 89.4 107 114
NA = Not Applicable (1) Samples were analyzed using internal standard quantitation. Internal standard was added to the sample during sample
preparation. (2) Samples were diluted 1:10 (LS, MS) or 1:100 (HS) and analyzed using external standard quantitation.
PAGE 26 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-04
Table 30. Rinseate Blank
PFOA
PFBS
PFHS
PFOS
3M LIMS ID ISO13-05-04-067
Description DAL-GW-324L-RB-130927
Concentration (ng/mL)
<0.0240
Concentration (ng/mL)
<0.0250
Concentration (ng/mL)
<0.0400
Concentration (ng/mL)
<0.0232
Samples were analyzed using internal standard quantitation. Internal standard was added to the sample during sample preparation.
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 Table 1 and 10-29 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.
PAGE 27 OF 28
7 Signatures
3M ENVIRONMENTAL LABORATORY REPORT NO. IS013-05-04
William K. Reagen, Ph D., 3M Environmental Technical Director
Date
The 3M Environmental Laboratory's Quality Assurance Unit has audited the data and report for this project.
!/ Quality Assurance Representative
U N 3
Date
This test report shall not be reproduced except in full, without written approval of the 3M Environmental Laboratory. _
