Document 2q02zew7Ow1Oq9vRwZ3MkpYo5
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-01
Final Report
Analysis of PFOA, PFBS, PFHS, and PFOS in Ground Water Samples Collected from Decatur, AL 1st Quarter 2013
Laboratory Request Number: ISO13-05-01 Method Requirement: 3M Method ETS-8-044.1
Report Date - Date of Final Signature
Testing Laboratory 3M Environmental Health and Safety Operations
Environmental Laboratory 3M Center, Bldg 260-05-N-17
St. Paul, MN 55144
Requester Gary Hohenstein 3M Building 224-5W-03 Saint Paul, MN 55144-1000 Phone: (651) 737-3570
The testing reported herein meet the requirements o f ANSI/ISO/IEC 17025:2005 "General Requirements for the Competence of Testing and Calibration Laboratories", in accordance with the A2LA Testing Certificate # 2052.01.
PAGE 1 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-01
3M Environm ental Laboratory 3M Environmental Laboratory Technical Director: William K. Reagen, Ph.D. 3M Principal Analytical Investigator: Susan Wolf Report Author: Kevin Eich
Analytical Report ISO13-05-01
Analysis of PFOA, PFBS, PFHS, and PFOS in Ground Water Samples Collected from Decatur, AL 1st Quarter 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 on March 21, March 22, March 27, and March 28, 2013 and returned to the 3M Environmental Laboratory on March 29, 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 ISO13-05-01. 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 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 the A2LA Testing Certificate # 2052.01.
Testing Cert, ft 2052.01
PAGE 2 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-01
Table 1. Sample Results Summary (1)
3M LIMS ID ISO13-05-01-001 ISO13-05-01-002
ISO13-05-01-005 ISO13-05-01-006
ISO13-05-01-008 ISO13-05-01-009
ISO13-05-01-011 ISO13-05-01-012
ISO13-05-01-015 ISO13-05-01-016
ISO13-05-01-019 ISO13-05-01-020
ISO13-05-01-023 ISO13-05-01-024
ISO13-05-01-026 ISO13-05-01-027
ISO13-05-01-029 ISO13-05-01-030
Sample Description
DAL-GW-203L-0-130328 DAL-GW-203L-DB-130328
Average %RPD Sample/Sample Dup DAL-GW-220R-0-130327 DAL-GW-220R-DB-130327
Average %RPD Sample/Sample Dup DAL-GW-220L-0-130327 DAL-GW-220L-DB-130327
Average %RPD Sample/Sample Dup DAL-GW-222R-0-130328 DAL-GW-222R-DB-130328
Average %RPD Sample/Sample Dup DAL-GW-227R-0-130321 DAL-GW-227R-DB-130321
Average %RPD Sample/Sample Dup DAL-GW-227L-0-130321 DAL-GW-227L-DB-130321
Average %RPD Sample/Sample Dup DAL-GW-310R-0-130322 DAL-GW-310R-DB-130322
Average %RPD Sample/Sample Dup DAL-GW-312R-0-130328 DAL-GW-312R-DB-130328
Average %RPD Sample/Sample Dup DAL-GW-317L-0-130322 DAL-GW-317L-DB-130322
Average %RPD Sample/Sample Dup
PFOA Concentration
(ng/mL)
220 219 220 0.46 40.8 41.3 41.1 1.2 45.0 44.8 44.9 0.45 219 232 226 5.8 273 273 273 0.0 76.7 81.7 79.2 6.3 925 917 921 0.87 1160 1080 1120 7.1 0.244 0.240 0.242 1.7
PFBS Concentration
(ng/mL)
35.3 35.9 35.6 1.7 7.01 7.00 7.01 0.14 7.89 7.99 7.94 1.3 41.8 42.8 42.3 2.4 16.5 17.1 16.8 3.6 198 204 201 3.0 1190 1190 1190 0.0 1160 1070 1120 8.1 <0.0400 <0.0400 <0.0400 NA
PFHS Concentration
(ng/mL)
233 241 237 3.4 30.2 31.9 31.3 5.5 37.4 36.4 36.9 2.7 246 258 252 4.8 69.4 72.5 71.0 4.4 37.4 37.0 37.2 1.1 289 278 284 3.9 501 475 488 5.3 0.0809 0.0918 0.0864 13
PFOS Concentration
(ng/mL)
796 760 778 4.6 62.0 59.8 60.9 3.6 63.8 66.5 65.2 4.1 406 422 414 3.9 574 577 576 0.52 238 244 241 2.5 647 641 644 0.93 809 738 774 9.2 0.155 0.207 0.181 (2) 29 (3)
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 13%, PFBS 14%, PFHS 15%, and PFOS 22%. (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: PFOS 25%. (3) The RPD value did not meet method acceptance criteria of <20%. (4) The analytical method uncertainty has been expanded to 32% for PFOA. See section 4 for further discussion. (5) The analytical method uncertainty has been expanded to 31 % for PFOA. See section 4 for further discussion. (6) The analytical uncertainty has been expanded to 34% for PFOA. See section 4 for further discussion.
PAGE 3 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-01
Table 1 continued. Sample Results Summary (1)
3M LIMS ID ISO13-05-01-032 ISO13-05-01-033
ISO13-05-01-035 ISO13-05-01-036
ISO13-05-01-039 ISO13-05-01-040
ISO13-05-01-043 ISO13-05-01-044
ISO13-05-01-047 ISO13-05-01-048
ISO13-05-01-051 ISO13-05-01-052
ISO13-05-01-054 ISO13-05-01-055
ISO13-05-01-057 ISO13-05-01-058
ISO13-05-01-060 ISO13-05-01-061
Sample Description DAL-GW-324L-0-130321 DAL-GW-324L-DB-130321
Average %RPD Sample/Sample Dup DAL-GW-RW327R-0-130328 DAL-GW-RW327R-DB-130328
Average %RPD Sample/Sample Dup DAL-GW-328R-0-130321 DAL-GW-328R-DB-130321
Average %RPD Sample/Sample Dup DAL-GW-328L-0-130321 DAL-GW-328L-DB-130321
Average %RPD Sample/Sample Dup DAL-GW-330R-0-130322 DAL-GW-330R-DB-130322
Average %RPD Sample/Sample Dup DAL-GW-330L-0-130322 DAL-GW-330L-DB-130322
Average %RPD Sample/Sample Dup DAL-GW-RW331S-0-130328 DAL-GW-RW331S-DB-130328
Average %RPD Sample/Sample Dup DAL-GW-335R-0-130328 DAL-GW-335R-DB-130328
Average %RPD Sample/Sample Dup DAL-GW-GRS04-0-130328 DAL-GW-GRS04-DB-130328
Average %RPD Sample/Sample Dup
PFOA Concentration
(ng/mL) 254 260
257 (4) 2.3 711 715
713 (5) 0.56 321 323 322 (5) 0.62 91.4 91.0 91.2 0.44 265 284
275 6.9 167 164
166 1.8 765 750 758 (6) 2.0 3670 3860
3770 5.0 3190 3300
3250 3.4
PFBS Concentration
(ng/mL) 67.0 76.4 71.7 13 65.3 63.7
64.5 2.5 32.2 32.3 32.3 0.31 45.6 44.6 45.1 2.2 1560 1640
1600 5.0 549 545
547 0.73 843 841 842 0.24 1340 1410
1380 5.1 2080 2040
2060 1.9
PFHS Concentration
(ng/mL) 71.0 73.6 72.3 3.6 140 140
140 0.0 50.8 50.1 50.5 1.4 16.8 16.8 16.8 0.0 147 156
152 5.9 300 288
294 4.1 299 291 295 2.7 1540 1600
1570 3.8 6680 6950
6820 4.0
PFOS Concentration
(ng/mL) 203 212 208 4.3 344 348
346 1.2 185 174 180 6.1 0.905 0.855 0.880 5.7 498 547
523 9.4 176 187
182 6.1 653 630 642 3.6 4860 4920
4890 1.2 2800 3380
3090 19
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 13%, PFBS 14%, PFHS 15%, and PFOS 22%. (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: PFOS 25%. (3) The RPD value did not meet method acceptance criteria of <20%. (4) The analytical method uncertainty has been expanded to 32% for PFOA. See section 4 for further discussion. (5) The analytical method uncertainty has been expanded to 31 % for PFOA. See section 4 for further discussion. (6) The analytical uncertainty has been expanded to 34% for PFOA. See section 4 for further discussion.
PAGE 4 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-01
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 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 21, March 22, March 27, and March 28, 2013 and returned to the 3M Environmental Laboratory on March 29, 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.
Sample Description Key Code.
String Number Example 1 2 3 4
5 6
String Descriptor DAL-GW-317L-0-130322 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 130322 - March 22, 2013 0 =primary sample DB =duplicate sample FMS = Field Matrix Spike LS = Low field matrix spike HS = High field matrix spike
2.3 Sample Preparation
4/2/13: 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 diluting it with 9.0 mL of methanol. Samples requiring a 1:20 dilution were prepared by removing a 0.5 mL aliquot of the well mixed sample and diluting it with 9.5 mL of methanol. Samples requiring a 1:50 dilution were prepared by removing a 0.2 mL aliquot of the well mixed sample and diluting it with 9.8 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. Samples requiring a 1:200 dilution were prepared by removing a 0.05 mL aliquot of
PAGE 5 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-01
the well mixed sample and diluting it with 10 mL of methanol. Sample injection values were increased for some samples if a smaller dilution factor (i.e.2 or 5) was desired.
4/5/13: Solvent dilution / external standard analysis. Samples and laboratory control spikes were diluted with methanol prior to sample analysis and spiked with surrogate recovery standards (SRSs) 13C4-PFOA and 13C4-PFOS to be used in lieu of target analyte matrix spikes. Sample sets LCS130405a, 203L, and 220R required a 1:10 dilution and were prepared removing 1.0 mL of the well mixed sample and diluting it with 8.9 mL of methanol and 0.1 mL of a solution containing SRSs (spiked at a nominal concentration of 1 ng/mL). The 203L samples were spiked with SRSs in lieu of appropriate target analyte field matrix spike samples. The 220R samples were spiked with SRSs since it was noted on the chain of custody for the field matrix spike that the cap was loose upon arrival at the sampling site thus making the recovery of this sample questionable. Sample set GRS04 required a 1:1000 dilution and were prepared by removing a 0.01 mL aliquot of the well mixed sample and diluting it with 10 mL of methanol. Due to high recoveries for PFBS, PFHS, and PFOS determined during the initial analysis of the samples, a laboratory matrix spike (LMS) was prepared by spiking an aliquot of the primary sample at the same level as the target analyte field matrix spike (nominal concentration of 5000 ng/mL).
4/5/13: Direct injection/ internal standard analysis. Sample set 317L was 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. The following analytical runs were processed and reported herein:
4/2/13: Solvent dilution / external standard analysis for PFOA, PFBS, PFHS, PFOS; locations 220L, 222R, 227R, 227L, 310R, RW312R, 317L, 324L, RW327R, 328R, 328L, 330R, 330L RW331S, 335R, GRS04, Trip Blanks and Rinseate Blank sample.
4/5/13: Solvent dilution / external standard analysis for PFOA, PFBS, PFHS, PFOS, 13C4-PFOA and 13C4-PFOS; locations 203L, 220R, and GRS04.
4/6/13: Direct injection / internal standard analysis for PFOS; location 317L.
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.
PAGE 6 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-01
Table 3. Instrument Parameters
Instrument Name Analysis Dates Analytical Method Liquid Chromatograph Guard column Analytical column Injection Volume Mass Spectrometer Ion Source Polarity Software
ETS Buster 4/2/13, 4/5/13, 4/6/13
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, 50 gL Applied Biosystems API 4000 Turbo Spray
Negative Analyst 1.6.1
Table 4. Liquid Chrom atography 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 5. 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
Mass Transition Q1/Q3
Reference Material Structure
413/369
PFOA
413/219
NA
NA Linear and Branched
413/169
PFBS
299/80 NA NA Linear
299/99
PFHS
399/99 NA NA Linear
399/80
499/99
PFOS
499/80
[13Cs]-PFOS (1)
507/80
Linear and Branched
499/130
[13C4]-PFOA surrogate
417/372
NA
NA
Linear
[13C4]-PFOS surrogate
503/80
NA
NA
Linear
Dwell time was 50 msec for each transition. The individual transitions were summed to produce a "total ion chromatogram" (TIC), which was used for quantitation.
NA = Not Applicable
(1) Internal standard was used for the analysis of sampling location 317L for PFOS on 4/6/13.
PAGE 7 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-01
3 Data Analysis
3.1 Calibration
4/2/13: Solvent dilution / external standard calibration. Diluted samples were analyzed against an external standard calibration curve for PFOA, PFBS, PFHS, and PFOS. 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 thirteen calibration standards ranging from 0.02 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.
4/5/13: Solvent dilution / external standard calibration. Diluted samples were analyzed against an external standard calibration curve for, PFOA, PFBS, PFHS, PFOS, 13C4-PFOA and 13C4-PFOS. 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 thirteen calibration standards ranging from 0.02 ng/mL to 150 ng/mL (nominal) were analyzed (0.02 ng/mL to 25 ng/mL for the SRSs). 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.
4/6/13: 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 the stock solution into laboratoryprepared reagent water. The calibration standards contained an internal standard mix at a nominal concentration of 1 ng/mL. A total of ten curve points were analyzed with the samples ranging from 0.025 ng/mL to 5.0 ng/mL. 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.
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 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.
PAGE 8 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-01
Table 6. LOQ
Analysis Date
4/2/13
4/5/13 4/6/13
Calibration
External standard External standard Internal standard
Dilution Factor
2 5 10 20 50 100 200 10 1000 NA
PFBA LOQ, ng/mL
0.0384 0.0960 0.192 0.384 0.960
1.92 3.84 0.192 19.2 NA
PFOA LOQ, ng/mL
0.0400 0.100 0.200 0.400 1.00 2.00 4.00 0.200 20.0
NA
PFBS LOQ, ng/mL
0.0400 0.100 0.200 0.400 1.00 2.00 4.00 0.200 20.0
NA
PFOS LOQ, ng/mL
0.0370 0.0925 0.185 0.370 0.925
1.85 3.70 0.185 18.5 0.0232
NA=Not Applicable
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, while only low and high lab control spikes were prepared for the surrogates. 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 LCSs with the following exceptions:
4/5/13 analysis: The acceptance criteria for accuracy were met with the exception of the high set of LCS for PFOS (122%).
4/6/13 analysis: The acceptance criteria for accuracy were met with the exception of the low and mid set of LCS for PFOS (123% and 125% respectively).
A method deviation is filed in the raw data. 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 7.
Calculated Concentration * LCS Percent Recovery
Spike Concentration
LCS% RSD = standard deviation LCS replicates * 1QQ% average LCS recovery
PAGE 9 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-01
Table 7. Lab Control Spike Results
ETS-8-044.1 Analyzed 4/2/13 External Standard Calibration
Lab ID LCS-130402-1 LCS-130402-2 LCS-130402-3 Average %RSD LCS-130402-4 LCS-130402-5 LCS-130402-6 Average %RSD LCS-130402-7 LCS-130402-8 LCS-130402-9 Average %RSD
PFOA (Linear and Branched)
Spiked Concentration
(ng/mL)
Calculated Concentration
(ng/mL)
%Recovery
0.958 0.958 0.958
9.58 9.58 9.58
38.2 38.2 38.2
1.00 0.981 1.01 104% 1.5% 10.9 10.6 10.8 112% 1.5% 41.6 41.8 43.0 110% 2.1%
104 102 105
113 110 113
109 109 113
Spiked Concentration
(ng/mL) 1.00 1.00 1.00
10.0 10.0 10.0
39.8 39.8 39.8
PFBS Calculated Concentration
(ng/mL)
1.07 1.05 1.03 105% 1.9% 11.7 11.8 11.8 118% 0.49% 44.7 44.9 45.5 113% 0.88%
%Recovery 107 105 103
117 118 118
112 113 114
ETS-8-044.1 Analyzed 4/2/13 External Standard Calibration
Lab ID LCS-130402-1 LCS-130402-2 LCS-130402-3 Average %RSD LCS-130402-4 LCS-130402-5 LCS-130402-6 Average %RSD LCS-130402-7 LCS-130402-8 LCS-130402-9 Average %RSD
Spiked Concentration
(ng/mL)
PFHS
Calculated Concentration
(ng/mL)
1.00 1.05 1.00 1.03 1.00 1.02
103% 1.5% 10.0 11.3 10.0 11.2 10.0 11.3
39.8 39.8 39.8
113% 0.51% 43.1 43.3 44.3
109% 1.4%
%Recovery 105 103 102
113 112 113
108 109 111
PFOS (Linear and Branched)
Spiked Concentration
(ng/mL)
Calculated Concentration
(ng/mL)
%Recovery
0.927 0.927 0.927
9.27 9.27 9.27
0.967 0.948 0.950 103% 1.1% 10.4 10.7 10.6
104 102 102
112 115 115
36.9 36.9 36.9
114% 1.5% 42.1 42.3 43.0
115% 1.3%
114 115 117
PAGE 10 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-01
Table 7 continued. Lab Control Spike Results
ETS-8-044.1 Analyzed 4/5/13 External Standard Calibration
Lab ID LCS-130405a-1 LCS-130405a-2 LCS-130405a-3 Average %RSD LCS-130405a-4 LCS-130405a-5 LCS-130405a-6 Average %RSD LCS-130405a-7 LCS-130405a-8 LCS-130405a-9 Average %RSD
PFOA (Linear and Branched)
Spiked Concentration
(ng/mL)
Calculated Concentration
(ng/mL)
%Recovery
0.958 0.958 0.958
9.58 9.58 9.58
38.2 38.2 38.2
0.954 0.973 0.974 101% 1.4% 10.8 10.3 10.6 110% 2.8% 43.2 44.7 45.0 116% 2.3%
99.6 102 102
113 107 111
113 117 118
Spiked Concentration
(ng/mL) 1.00 1.00 1.00
10.0 10.0 10.0
39.8 39.8 39.8
PFBS Calculated Concentration
(ng/mL)
1.05 1.03 0.975 102% 3.8% 10.9 10.9 11.1 110% 1.1% 45.6 46.4 46.1 116% 1.3%
%Recovery 105 103 97.5
109 109 111
114 117 116
ETS-8-044.1 Analyzed 4/5/13 External Standard Calibration
Lab ID LCS-130405a-1 LCS-130405a-2 LCS-130405a-3 Average %RSD LCS-130405a-4 LCS-130405a-5 LCS-130405a-6 Average %RSD LCS-130405a-7 LCS-130405a-8 LCS-130405a-9 Average %RSD
Spiked Concentration
(ng/mL)
PFHS
Calculated Concentration
(ng/mL)
1.00 1.10 1.00 1.02 1.00 0.997
104% 5.2% 10.0 11.3 10.0 11.1 10.0 11.5
39.8 39.8 39.8
113% 1.8% 45.3 47.0 46.6
116% 1.8%
%Recovery 110 102 99.7
113 111 115
114 118 117
PFOS (Linear and Branched)
Spiked Concentration
(ng/mL)
Calculated Concentration
(ng/mL)
%Recovery
0.927 0.927 0.927
9.27 9.27 9.27
0.939 0.948 0.947 102% 0.57% 10.5 10.4 10.5
101 102 102
113 112 114
36.9 36.9 36.9
113% 0.88% 44.5 44.8 45.6
122% 1.4% (1)
121 121 124
(1) Average LCS recovery did not meet method acceptance criteria of 100 30%.
PAGE 11 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-01
Table 7 continued. Lab Control Spike Results
ETS-8-044.1 Analyzed 4/5/13 External Standard Calibration
Lab ID LCS-130405a-1 LCS-130405a-2 LCS-130405a-3 Average %RSD LCS-130405a-4 LCS-130405a-5 LCS-130405a-6 Average %RSD
Spiked Concentration
(ng/mL)
13C4 p f o a
Calculated Concentration
(ng/mL)
0.998 0.998 0.998
9.98 9.98 9.98
0.969 0.992 0.971 97.9% 1.3% 10.2 10.1 10.1 102% 1.1%
%Recovery 97.1 99.4 97.3
103 101 101
Spiked Concentration
(ng/mL) 0.956 0.956 0.956
9.56 9.56 9.56
13C4 p f o s Calculated Concentration
(ng/mL)
1.01 1.02 1.00 106% 0.94% 9.87 9.79 9.83 103% 0.56%
%Recovery 106 107 105
103 102 103
ETS-8-044.1 Analyzed 4/6/13 Internal Standard Calibration
Lab ID LCS-130405b-1 LCS-130405b-2 LCS-130405b-3 Average %RSD LCS-130405b-4 LCS-130405b-5 LCS-130405b-6 Average %RSD LCS-130405b-7 LCS-130405b-8 LCS-130405b-9 Average %RSD
PFOS (Linear and Branched)
Spiked Concentration
(ng/mL)
Calculated Concentration
(ng/mL)
%Recovery
0.0921 0.0921 0.0921
0.921 0.921 0.921
2.30 2.30 2.30
0.110 0.108 0.121 123% 6.1%(1) 1.15 1.11 1.18 125% 3.2%(1) 2.64 2.57 2.68 114% 1.8%
120 118 132
125 121 129
115 112 116
(1) Average LCS recovery did not meet method acceptance criteria of 100 30%.
PAGE 12 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-01
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%.
The analytical method uncertainty as calculated by ETS-12-012.2 for PFOS by external standard calibration was 14%. The recovery of the high set of LCS analyzed on 4/5/13 was 122% for PFOS by external standard calibration for the samples analyzed on this date. The analytical method uncertainty was expanded to 22%.
The analytical method uncertainty as calculated by ETS-12-012.2 for PFOS by internal standard calibration was 19%. The recovery of the mid set of LCS analyzed on 4/6/13 was 125% for PFOS by internal standard calibration for the samples analyzed on this date. The analytical method uncertainty was expanded to 25%.
Table 8. A nalytical Method Uncertainty
Analyte PFOA PFBS PFHS PFOS PFOS
Calibration External External External External Internal
Standard Deviation (%) 6.64 6.93 7.25 NA NA
Method Uncertainty 13% 14% 15% 22% 25%
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.
FMS ,,Recovery = 4(-S--a-m--p- -le---C--o--n--c-e--n-t-r-a--t-i-o-n---o--f-F--M---S------A--v-e--r-a-g2-e---C--o--n--c--e-n--t-r-a--t-i-o-n--:-F--i-e-l-d--S--a--m--pL-le---&---F--ie--ld---S--a--m- pL-le---D--u-p*.1)0 0 % Spike Concentraton
PAGE 13 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-01
Table 9. Field Matrix Spike Concentrations
Sampling location 203L 220R and 220L 22R
227R and 328R
227L and 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
1.05 10.5 52.7 105 527 52.7 527 527 1054 1054 1.05 211 105 1054 1.05 105 527 5270 1.05 105 1054
PFBS ng/mL 0.996
9.96 49.8 99.6 498 49.8 498 498 996 996 0.996 199 99.6 996 0.996 99.6 498 4980 0.996 99.6 996
PFHS ng/mL 0.986
9.86 49.3 98.6 493 49.3 493 493 986 986 0.986 197 98.6 986 0.986 98.6 493 4930 0.986 98.6 986
PFOS ng/mL
1.00 10.0 50.0 100 500 50.0 500 500 1000 1000 1.00 200 100 1000 1.00 100 500 5000 1.00 100 1000
4 Data Summary and Discussion
Tables 10-29 below summarize the sample results and target analyte field matrix spike recoveries for the sampling locations as well as the Trip Blank. Where applicable, the data tables also include the recovery results for lab matrix spike and surrogate recovery standards. 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, surrogate recovery standard laboratory matrix spikes, and laboratory matrix spikes met method acceptance criteria with the following exceptions:
Location 203L; The low and high field matrix spikes prepared for the sample set was not appropriate as compared to the sample concentrations detected. The sample and sample duplicate were re-analyzed and spiked with surrogate recovery standard at a nominal concentration of 1 ng/mL and acceptable recoveries were obtained.
Location 220R; It was noted on the chain of custody that the FMS sample container arrived with a loose cap prior to sampling. In lieu of a target analyte matrix spike, the sample and sample duplicate were spiked with surrogate recovery standard at a nominal concentration of 1 ng/mL and acceptable recoveries were obtained.
PAGE 14 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-01
Location 324L; The FMS recovery for PFOA was 68.8%. The analytical uncertainty for this location was expanded to 32%.
Location RW327R; The FMS recovery for PFOA was 69.0%. The analytical uncertainty for this location was expanded to 31%.
Location 328R; The FMS recovery for PFOA was 69.3%. The analytical uncertainty for this location was expanded to 31%.
Location RW331S; The FMS recovery for PFOA was 66.7%. The analytical uncertainty for this location was expanded to 34%.
Location GRS04; The FMS recovery was outside the method acceptance criteria for PFBS (238%), PFHS (407%), and PFOS (610%). A laboratory matrix spike (LMS) was prepared on the primary sample (ISO13-05-01 -60) at the same spike level as the FMS sample (nominal concentration 5000 ng/mL). The LMS sample met method acceptance criteria. The sample results for GRS04 for this sampling event are similar to results observed for this location during previous sampling events in 2010, 2011, and 2012. FMS recoveries for these previous sampling events met method acceptance criteria, demonstrating that the method is appropriate for the sample matrix. Therefore, the recovery of the LMS was used to assess method accuracy for GRS04.
PAGE 15 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-01
Table 10. DAL GW 203L
3M LIMS ID
Description
ISO13-05-01-001
DAL-GW-203L-0-130328
ISO13-05-01-002
DAL-GW-203L-DB-130328
ISO13-05-01-003
DAL-GW-203L-LS-130328
ISO13-05-01-004
DAL-GW-203L-HS-130328
Average Concentration (ng/mL) %RPD
3M LIMS ID
Description
ISO13-05-01-001
DAL-GW-203L-0-130328
ISO13-05-01-002
DAL-GW-203L-DB-130328
ISO13-05-01-003
DAL-GW-203L-LS-130328
ISO13-05-01-004
DAL-GW-203L-HS-130328
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
220 NA 219 NA NR NR NR NR
220 ng/mL 0.46%
PFBS
Concentration (ng/mL)
%Recovery
35.3
NA
35.9
NA
NR NR
NR NR
35.6 ng/mL 1.7%
PFHS
Concentration (ng/mL)
%Recovery
233 NA 241 NA NR NR NR NR
237 ng/mL 3.4%
PFOS
Concentration (ng/mL)
%Recovery
796 NA 760 NA NR NR NR NR
778 ng/mL 4.6%
13C4-PFOA (1)
13C4-PFOS (1)
3M LIMS ID
Description
ISO13-05-01-001
DAL-GW-203L-0-130328
ISO13-05-01-002
DAL-GW-203L-DB-130328
Average Concentration (ng/mL) %RPD
%Recovery
93.1 98.9 96.0% 6.1%
NA = Not Applicable NR= Not Reported; Spike levels were less than 0.5x the endogenous sample concentration. Samples were diluted 1:10 and analyzed by external standard quantitation. (1) Surrogate recovery standards were added to the samples during sample preparation.
%Recovery
102 97.0 99.5% 5.1%
PAGE 16 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-01
Table 11. DAL GW 220R
3M LIMS ID
Description
ISO13-05-01-005
DAL-GW-220R-0-130327
ISO13-05-01-006
DAL-GW-220R-DB-130327
ISO13-05-01-007
DAL-GW-220R-FMS-130327
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
40.8
NA
41.3
NA
NR NR
41.1 ng/mL 1.2%
PFBS
Concentration (ng/mL)
%Recovery
7.01 NA
7.00
NA
NR NR
7.01 ng/mL 0.14%
3M LIMS ID
Description
ISO13-05-01-005
DAL-GW-220R-0-130327
ISO13-05-01-006
DAL-GW-220R-DB-130327
ISO13-05-01-007
DAL-GW-220R-FMS-130327
Average Concentration (ng/mL) %RPD
PFHS
Concentration (ng/mL)
%Recovery
30.2
NA
31.9
NA
NR NR
31.1 ng/mL 5.5%
PFOS
Concentration (ng/mL)
%Recovery
62.0
NA
59.8
NA
NR NR
60.9 ng/mL 3.6%
13C4-PFOA (1)
13C4-PFOS (1)
3M LIMS ID
Description
ISO13-05-01-005
DAL-GW-220R-0-130327
ISO13-05-01-006
DAL-GW-220R-DB-130327
Average Concentration (ng/mL) %RPD
%Recovery
98.9 94.2 96.5% 4.9%
%Recovery
106 99.6 103% 5.9%
NA = Not Applicable NR= Not Reportable; Note on chain of custody form indicated that the sample cap was loose prior to sampling, thus making the FMS recovery questionable. Samples were diluted 1:10 and analyzed using external standard quantitation. The injection volume was increased to produce a dilution factor of 5. (1) Surrogate recovery standards were added to the samples during sample preparation.
PAGE 17 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-01
Table 12. DAL GW 220L
3M LIMS ID
Description
ISO13-05-01-008 ISO13-05-01-009 ISO13-05-01-010
DAL-GW-220L-0-130327 DAL-GW-220L-DB-130327 DAL-GW-220L-FMS-130327
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
45.0 NA 44.8 NA 85.7 77.4
44.9 ng/mL 0.45%
PFBS
Concentration (ng/mL)
%Recovery
7.89 NA 7.99 NA 51.0 86.5
7.94 ng/mL 1.3%
3M LIMS ID
Description
ISO13-05-01-008
DAL-GW-220L-0-130327
ISO13-05-01-009
DAL-GW-220L-DB-130327
ISO13-05-01-010
DAL-GW-220L-FMS-130327
Average Concentration (ng/mL) %RPD
PFHS
Concentration (ng/mL)
%Recovery
37.4 NA 36.4 NA 76.4 80.1
36.9 ng/mL 2.7%
PFOS
Concentration (ng/mL)
%Recovery
63.8 NA 66.5 NA 108 85.7
65.2 ng/mL 4.1%
NA = Not Applicable Samples were diluted 1:10 and analyzed using external standard quantitation. The injection volume was increased to produce a dilution factor of 5.
Table 13. DAL GW 222R
3M LIMS ID
Description
ISO13-05-01-011
DAL-GW-222R-0-130328
ISO13-05-01-012
DAL-GW-222R-DB-130328
ISO13-05-01-013
DAL-GW-222R-LS-130328
ISO13-05-01-014
DAL-GW-222R-HS-130328
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
219 NA 232 NA 313 NC 606 72.2
226 ng/mL 5.8%
PFBS
Concentration (ng/mL)
%Recovery
41.8 NA 42.8 NA 132 90.1 571 106
42.3 ng/mL 2.4%
PFHS
3M LIMS ID
Description
ISO13-05-01-011
DAL-GW-222R-0-130328
ISO13-05-01-012
DAL-GW-222R-DB-130328
ISO13-05-01-013
DAL-GW-222R-LS-130328
ISO13-05-01-014
DAL-GW-222R-HS-130328
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
246 NA 258 NA 345 NC 828 117
252 ng/mL 4.8%
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
406 NA 422 NA 513 NC 932 104
414 ng/mL 3.9%
PAGE 18 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-01
Table 14. DAL GW 227R
3M LIMS ID
Description
ISO13-05-01-015
DAL-GW-227R-0-130321
ISO13-05-01-016
DAL-GW-227R-DB-130321
ISO13-05-01-017
DAL-GW-227R-LS-130321
ISO13-05-01-018
DAL-GW-227R-HS-130321
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
273 NA 273 NA 320 NC 650 71.5
273 ng/mL 0.0%
PFBS
Concentration (ng/mL)
%Recovery
16.5 NA 17.1 NA 59.4 85.5 422 81.4
16.8 ng/mL 3.6%
PFHS
3M LIMS ID
Description
ISO13-05-01-015
DAL-GW-227R-0-130321
ISO13-05-01-016
DAL-GW-227R-DB-130321
ISO13-05-01-017
DAL-GW-227R-LS-130321
ISO13-05-01-018
DAL-GW-227R-HS-130321
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
69.4 NA 72.5 NA 113 85.3 488 84.6
71.0 ng/mL 4.4%
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
574 NA
577 NA
655 NC
1070
98.9
576 ng/mL 0.52%
Table 15. DAL GW 227L
3M LIMS ID
Description
ISO13-05-01-019
DAL-GW-227L-0-130321
ISO13-05-01-020
DAL-GW-227L-DB-130321
ISO13-05-01-021
DAL-GW-227L-LS-130321
ISO13-05-01-022
DAL-GW-227L-HS-130321
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
76.7 NA 81.7 NA 483 76.6 877 75.7
79.2 ng/mL 6.3%
PFBS
Concentration (ng/mL)
%Recovery
198 NA
204 NA
615 83.1
1020
82.2
201 ng/mL 3.0%
PFHS
3M LIMS ID
Description
ISO13-05-01-019 ISO13-05-01-020 ISO13-05-01-021 ISO13-05-01-022
DAL-GW-227L-0-130321 DAL-GW-227L-DB-130321 DAL-GW-227L-LS-130321 DAL-GW-227L-HS-130321
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
37.4 NA 37.0 NA 430 79.7 814 78.8
37.2 ng/mL 1.1%
NA = Not Applicable Samples were diluted 1:50 and analyzed using external standard quantitation.
PFOS
Concentration (ng/mL)
%Recovery
238 244 634 1050
NA NA 78.6 80.9
241 ng/mL 2.5%
PAGE 19 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-01
Table 16. DAL GW 310R
3M LIMS ID
Description
ISO13-05-01-023
DAL-GW-310R-0-130322
ISO13-05-01-024
DAL-GW-310R-DB-130322
ISO13-05-01-025
DAL-GW-310R-FMS-130322
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
925 NA
917 NA
1680
72.0
921 ng/mL 0.87%
PFBS
Concentration (ng/mL)
%Recovery
1190
NA
1190
NA
1990
80.3
1190 ng/mL 0.0%
PFHS
3M LIMS ID
Description
ISO13-05-01-023 ISO13-05-01-024 ISO13-05-01-025
DAL-GW-310R-0-130322 DAL-GW-310R-DB-130322 DAL-GW-310R-FMS-130322
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
289 278 1090
NA NA 81.8
284 ng/mL 3.9%
NA = Not Applicable Samples were diluted 1:50 and analyzed using external standard quantitation.
PFOS
Concentration (ng/mL)
%Recovery
647 641 1560
NA NA 91.6
644 ng/mL 0.93%
Table 17. DAL GW RW312R
PFOA
3M LIMS ID
Description
Concentration (ng/mL)
%Recovery
ISO13-05-01-026
DAL-GW-RW312R-0-130328
ISO13-05-01-027
DAL-GW-RW312R-DB-130328
ISO13-05-01-028
DAL-GW-RW312R-FMS-130328
Average Concentration (ng/mL) %RPD
1160
NA
1080
NA
1860
70.2
1120 ng/mL 7.1%
PFBS
Concentration (ng/mL)
%Recovery
1160
NA
1070
NA
1900
78.8
1120 ng/mL 8.1%
PFHS
3M LIMS ID
Description
Concentration (ng/mL)
%Recovery
ISO13-05-01-026
DAL-GW-RW312R-0-130328
ISO13-05-01-027
DAL-GW-RW312R-DB-130328
ISO13-05-01-028
DAL-GW-RW312R-FMS-130328
Average Concentration (ng/mL) %RPD
501 NA
475 NA
1300
82.4
488 ng/mL 5.3%
NA = Not Applicable Samples were diluted 1:50 and analyzed using external standard quantitation.
PFOS
Concentration (ng/mL)
%Recovery
809 NA
738 NA
1600
82.7
774 ng/mL 9.2%
PAGE 20 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-01
Table 18. DAL GW 317L
3M LIMS ID
Description
ISO13-05-01-029
DAL-GW-317L-0-130322
ISO13-05-01-030
DAL-GW-317L-DB-130322
ISO13-05-01-031
DAL-GW-317L-FMS-130322
Average Concentration (ng/mL) %RPD
PFOA (1)
Concentration (ng/mL)
%Recovery
0.244
NA
0.240
NA
1.06 77.6
0.242 ng/mL 1.7%
PFBS (1)
Concentration (ng/mL)
%Recovery
<0.0400
NA
<0.0400
NA
0.824
82.7
<0.0400 ng/mL
PFHS (1)
PFOS (2)
3M LIMS ID
Description
ISO13-05-01-029
DAL-GW-317L-0-130322
ISO13-05-01-030
DAL-GW-317L-DB-130322
ISO13-05-01-031
DAL-GW-317L-FMS-130322
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
0.0809
NA
0.0918
NA
0.859
78.4
0.0864 ng/mL 13%
Concentration (ng/mL)
%Recovery
0.155
NA
0.207
NA
0.931
75.0
0.181 ng/mL 29% (3)
NA = Not Applicable (1) Samples were diluted 1:10 and analyzed using external standard quantitation. The injection volume was increased to produce
a dilution factor of 2. (2) Samples were analyzed using internal standard quantitation. (3) The RPD value did not meet method acceptance criteria of <20%.
Table 19. DAL GW 324L
3M LIMS ID
Description
ISO13-05-01-032
DAL-GW-324L-0-130321
ISO13-05-01-033
DAL-GW-324L-DB-130321
ISO13-05-01-034
DAL-GW-324L-FMS-130321
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
254 NA 260 NA 402 68.8 (1) 257 ng/mL 2.3% (2)
PFBS
Concentration (ng/mL)
%Recovery
67.0 NA 76.4 NA 243 86.0
71.7 ng/mL 13%
PFHS
3M LIMS ID
Description
ISO13-05-01-032
DAL-GW-324L-0-130321
ISO13-05-01-033
DAL-GW-324L-DB-130321
ISO13-05-01-034
DAL-GW-324L-FMS-130321
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
71.0 NA 73.6 NA 234 82.0
72.3 ng/mL 3.6%
NA = Not Applicable Samples were diluted 1:10 and analyzed using external standard quantitation. (1) FMS did not meet acceptance criteria of 100 30%. (2) The analytical uncertainty for PFOA was expanded to 32%.
PFOS
Concentration (ng/mL)
%Recovery
203 NA 212 NA 394 93.3
208 ng/mL 4.3%
PAGE 21 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-01
Table 20. DAL GW RW327R
PFOA
3M LIMS ID
Description
ISO13-05-01-035
DAL-GW-RW327R-0-130328
ISO13-05-01-036
DAL-GW-RW327R-DB-130328
ISO13-05-01-037
DAL-GW-RW327R-LS-130328
ISO13-05-01-038
DAL-GW-RW327R-HS-130328
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
711 NA
715 NA
815 NC
1440
69.0 (1)
713 ng/mL 0.56% (2)
PFBS
Concentration (ng/mL)
%Recovery
65.3 NA 63.7 NA 156 91.9 871 81.0
64.5 ng/mL 2.5%
PFHS
3M LIMS ID
Description
ISO13-05-01-035
DAL-GW-RW327R-0-130328
ISO13-05-01-036
DAL-GW-RW327R-DB-130328
ISO13-05-01-037
DAL-GW-RW327R-LS-130328
ISO13-05-01-038
DAL-GW-RW327R-HS-130328
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
140 NA 140 NA 230 91.3 952 82.4
140 ng/mL 0.0%
NA = Not Applicable NC = Not Calculated; Spike level was less than 0.5x the endogenous sample concentration Samples were diluted 1:20 and analyzed using external standard quantitation. (1) FMS did not meet acceptance criteria of 100 30%. (2) The analytical uncertainty for PFOA was expanded to 31%.
PFOS
Concentration (ng/mL)
%Recovery
344 NA
348 NA
435 NC
1200
85.4
346 ng/mL 1.2%
PAGE 22 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-01
Table 21. DAL GW 328R
3M LIMS ID
Description
ISO13-05-01-039
DAL-GW-328R-0-130321
ISO13-05-01-040
DAL-GW-328R-DB-130321
ISO13-05-01-041
DAL-GW-328R-LS-130321
ISO13-05-01-042
DAL-GW-328R-HS-130321
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
321 NA 323 NA 364 NC 687 69.3 (1) 322 ng/mL 0.62% (2)
PFBS
Concentration (ng/mL)
%Recovery
32.2 NA 32.3 NA 76.4 88.7 449 83.7
32.3 ng/mL 0.31%
PFHS
3M LIMS ID
Description
ISO13-05-01-039
DAL-GW-328R-0-130321
ISO13-05-01-040
DAL-GW-328R-DB-130321
ISO13-05-01-041
DAL-GW-328R-LS-130321
ISO13-05-01-042
DAL-GW-328R-HS-130321
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
50.8 NA 50.1 NA 95.0 90.4 459 82.9
50.5 ng/mL 1.4%
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. (1) FMS did not meet acceptance criteria of 100 30%. (2) The analytical uncertainty for PFOA was expanded to 31%
PFOS
Concentration (ng/mL)
%Recovery
185 NA 174 NA 226 NC 626 89.3
180 ng/mL 6.1%
PAGE 23 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-01
Table 22. DAL GW 328L
3M LIMS ID
Description
ISO13-05-01-043
DAL-GW-328L-0-130321
ISO13-05-01-044
DAL-GW-328L-DB-130321
ISO13-05-01-045
DAL-GW-328L-LS-130321
ISO13-05-01-046
DAL-GW-328L-HS-130321
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
91.4 NA 91.0 NA 98.2 NC 170 74.8
91.2 ng/mL 0.44%
PFBS
Concentration (ng/mL)
%Recovery
45.6 NA 44.6 NA 46.0 NC 128 83.2
45.1 ng/mL 2.2%
PFHS
PFOS
3M LIMS ID
Description
ISO13-05-01-043
DAL-GW-328L-0-130321
ISO13-05-01-044
DAL-GW-328L-DB-130321
ISO13-05-01-045
DAL-GW-328L-LS-130321
ISO13-05-01-046
DAL-GW-328L-HS-130321
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
16.8 NA 16.8 NA 18.2 NC 96.0 80.3
16.8 ng/mL 0.0%
Concentration (ng/mL)
%Recovery
0.905
NA
0.855
NA
1.72 84.0
75.9 75.0
0.880 ng/mL 5.7%
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. The injection volume was increased to produce a dilution factor of 2 (0, DB, and LS) or 5 (HS).
Table 23. DAL GW 330R
3M LIMS ID
Description
ISO13-05-01-047
DAL-GW-330R-0-130322
ISO13-05-01-048
DAL-GW-330R-DB-130322
ISO13-05-01-049
DAL-GW-330R-LS-130322
ISO13-05-01-050
DAL-GW-330R-HS-130322
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
265 NA
284 NA
740 88.3
1140
82.1
275 ng/mL 6.9%
PFBS
Concentration (ng/mL)
%Recovery
1560
NA
1640
NA
2110
NC
2410
81.3
1600 ng/mL 5.0%
PFHS
3M LIMS ID
Description
Concentration (ng/mL)
%Recovery
ISO13-05-01-047
DAL-GW-330R-0-130322
147
NA
ISO13-05-01-048
DAL-GW-330R-DB-130322
156
NA
ISO13-05-01-049
DAL-GW-330R-LS-130322
586
88.1
ISO13-05-01-050
DAL-GW-330R-HS-130322
1010
87.1
Average Concentration (ng/mL) %RPD
152 ng/mL 5.9%
NA = Not Applicable
NC = Not Calculated; Spike level was less than 0.5x the endogenous sample concentration
Samples were diluted 1:50 and analyzed using external standard quantitation.
PFOS
Concentration (ng/mL)
%Recovery
498 NA
547 NA
1020
99.5
1350
82.8
523 ng/mL 9.4%
PAGE 24 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-01
Table 24. DAL GW 330L
3M LIMS ID
Description
ISO13-05-01-051
DAL-GW-330L-0-130322
ISO13-05-01-052
DAL-GW-330L-DB-130322
ISO13-05-01-053
DAL-GW-330L-FMS-130322
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
167 NA 164 NA 589 80.4
166 ng/mL 1.8%
PFBS
Concentration (ng/mL)
%Recovery
549 NA 545 NA 969 84.7
547 ng/mL 0.73%
PFHS
3M LIMS ID
Description
ISO13-05-01-051
DAL-GW-330L-0-130322
ISO13-05-01-052
DAL-GW-330L-DB-130322
ISO13-05-01-053
DAL-GW-330L-FMS-130322
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
300 NA 288 NA 726 87.6
294 ng/mL 4.1%
NA = Not Applicable Samples were diluted 1:20 and analyzed using external standard quantitation.
PFOS
Concentration (ng/mL)
%Recovery
176 NA 187 NA 622 88.1
182 ng/mL 6.1%
Table 25. DAL GW RW331S
PFOA
3M LIMS ID
Description
Concentration (ng/mL)
%Recovery
ISO13-05-01-054
DAL-GW-RW331S-0-130328
ISO13-05-01-055
DAL-GW-RW331S-DB-130328
ISO13-05-01-056
DAL-GW-RW331S-FMS-130328
Average Concentration (ng/mL) %RPD
765 NA
750 NA
1460
66.7 (1)
758 ng/mL 2.0% (2)
PFBS
Concentration (ng/mL)
%Recovery
843 NA
841 NA
1600
76.1
842 ng/mL 0.24%
PFHS
3M LIMS ID
Description
Concentration (ng/mL)
%Recovery
ISO13-05-01-054
DAL-GW-RW331S-0-130328
ISO13-05-01-055
DAL-GW-RW331S-DB-130328
ISO13-05-01-056
DAL-GW-RW331S-FMS-130328
Average Concentration (ng/mL) %RPD
299 NA
291 NA
1060
77.6
295 ng/mL 2.7%
NA = Not Applicable Samples were diluted 1:50 and analyzed using external standard quantitation. (1) FMS did not meet acceptance criteria of 100 30%. (2) The analytical uncertainty for PFOA was expanded to 34%
PFOS
Concentration (ng/mL)
%Recovery
653 NA
630 NA
1370
72.9
642 ng/mL 3.6%
PAGE 25 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-01
Table 26. DAL GW 335R
3M LIMS ID
Description
ISO13-05-01-057
DAL-GW-335R-0-130328
ISO13-05-01-058
DAL-GW-335R-DB-130328
ISO13-05-01-059
DAL-GW-335R-FMS-130328
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
3670
NA
3860
NA
7550
71.8
3770 ng/mL 5.0%
PFBS
Concentration (ng/mL)
%Recovery
1340
NA
1410
NA
5770
88.3
1380 ng/mL 5.1%
PFHS
3M LIMS ID
Description
ISO13-05-01-057
DAL-GW-335R-0-130328
ISO13-05-01-058
DAL-GW-335R-DB-130328
ISO13-05-01-059
DAL-GW-335R-FMS-130328
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
1540
NA
1600
NA
5980
89.5
1570 ng/mL 3.8%
NA = Not Applicable Samples were diluted 1:100 and analyzed using external standard quantitation.
PFOS
Concentration (ng/mL)
%Recovery
4860
NA
4920
NA
9890
100
4890 ng/mL 1.2%
Table 27. DAL GW GRS04
PFOA
3M LIMS ID
Description
ISO13-05-01-060 ISO13-05-01-061 ISO13-05-01-062
DAL-GW-GRS04-0-130328 DAL-GW-GRS04-DB-130328 DAL-GW-GRS04-FMS-130328
ISO13-05-01-060
DAL-GW-GRS04-0-130328 LMS
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
3190 3300 9010
NA NA 109
NA NA 3250 ng/mL 3.4%
PFBS
Concentration (ng/mL)
%Recovery
2080 2040 13900
NA NA 238 (1)
8040
121
2060 ng/mL 1.9%
PFHS
PFOS
3M LIMS ID
Description
ISO13-05-01-060
DAL-GW-GRS04-0-130328
ISO13-05-01-061
DAL-GW-GRS04-DB-130328
ISO13-05-01-062
DAL-GW-GRS04-FMS-130328
ISO13-05-01-060
DAL-GW-GRS04-0-130328 LMS
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
6680
NA
6950
NA
26900
407 (1)
13000
129
6820 ng/mL 4.0%
Concentration (ng/mL)
%Recovery
2800
NA
3380
NA
33600
610 (1)
9250
130
3090 ng/mL 19%
NA = Not Applicable Samples were diluted 1:1000 and analyzed using external standard quantitation. (1) FMS did not meet acceptance criteria of 100 30%. The LMS sample was used to demonstrate method accuracy for PFBS,
PFHS, and PFOS.
PAGE 26 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-01
Table 28. Trip Blank
3M LIMS ID
ISO13-05-01-063 ISO13-05-01-064 ISO13-05-01-065 ISO13-05-01-066
Description
DAL-GW-TRIP01 -0 (1) DAL-GW-TRIP01 -LS (1) DAL-GW-TRI P01-MS DAL-GW-TRI P01-HS
PFOA
Concentration (ng/mL)
<0.0384 0.808 87.6 750
%Recovery
NA 76.7 83.1 71.2
PFBS
Concentration (ng/mL)
<0.0400 0.814 89.2 828
%Recovery
NA 81.7 89.6 83.1
PFHS
PFOS
3M LIMS ID
ISO13-05-01-063 ISO13-05-01-064 ISO13-05-01-065 ISO13-05-01-066
Description
DAL-GW-TRI P01-0 (1) DAL-GW-TRI P01-LS (1) DAL-GW-TRI P01-MS DAL-GW-TRI P01-HS
Concentration (ng/mL)
<0.0400 0.761 83.3 925
%Recovery
NA 77.2 84.5 93.8
Concentration (ng/mL)
<0.0370 0.782 85.4 926
%Recovery
NA 78.2 85.4 92.6
NA = Not Applicable Samples were diluted 1:10 and analyzed using external standard quantitation. The injection volume was increased to produce a dilution factor of 2 for select samples. (1) Samples were analyzed using a dilution factor of 2.
Table 29. Rinseate Blank
PFOA
PFBS
PFHS
PFOS
3M LIMS ID ISO13-05-01-067
Description DAL-GW-RB-222R-0-130328
Concentration (ng/mL)
<0.0384
Concentration (ng/mL)
<0.0400
Concentration (ng/mL)
<0.0400
Concentration (ng/mL)
<0.0370
Samples were diluted 1:10 and analyzed using external standard quantitation. The injection volume was increased to produce a dilution factor of 2 for select samples.
PAGE 27 OF 28
3M ENVIRONMENTAL LABORATORY REPORT NO. IS013-05-01
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.
7 Signatures
.L .
Susan T. Wolf, 3M Principal Analytical Investigator
/
Date
William K. Reagen, Ph.D., 3M Environmental Technical Director
(o io /^
Date
The 3M Environmental Laboratory's Quality Assurance Unit has audited the data and report for this project.
Quality
Representative
r- -/ 3
Date
This test report shall not be reproduced except in full, without written approval of the 3M Environmental Laboratory.
PAGE 28 OF 28
