Document e9rDXbJB4jB164MBYVoyVLrM
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-03
Final Report
A n a ly s is o f P F O A , P F B S , P F H S , a n d P F O S in S u rfa c e a n d G ro u n d W a te r S a m p le s C o lle c te d a t th e B ro w n s F e rry R o a d S ite L o c a te d in D e c a tu r, A L 3 rd Q u a r t e r 2 0 1 3
L a b o ra to ry R e q u e s t N u m b e r: IS O 1 3 -0 5 -0 3 M e th o d R e q u ire m e n t: 3 M M e th o d E T S -8 -0 4 4 .1
Report Date - Date of Final Signature
T e s tin g L a b o ra to ry 3 M E n v iro n m e n ta l H e a lth a n d S a fe ty O p e ra tio n s
E n v iro n m e n ta l L a b o ra to ry 3 M C e n te r, B ld g 2 6 0 -0 5 -N -1 7
S t. P a u l, M N 5 5 1 4 4
Requester
G a ry H o h e n s te in 3 M B u ild in g 2 2 4 -5 W -0 3 S a in t P a u l, M N 5 5 1 4 4 -1 0 0 0 P ho ne : (6 5 1 ) 7 3 7 -3 5 7 0
The testing reported herein meet the requirements of ANSI/ISO/IEC 17025:2005 "General Requirements for the Competence of Testing and Calibration Laboratories", in accordance with A2LA Certificate # 2052.01. Additionally, the laboratory's quality system has been audited and was determined to be in conformance with the EPA GLPs (40 CFR 792) by an independent assessment.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-03
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 ISO13-05-03
Analysis of PFOA, PFBS, PFHS, and PFOS in Surface and Ground W ater Samples Collected at the Browns Ferry Road Site Located in 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 on August 27 and 28, 2013 and returned to the 3M Environmental Laboratory on September 4, 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 ISO13-05-03.
The 3M Environmental Laboratory prepared sample containers for fourteen groundwater well and three surface water locations. Also included was a sample container for the collection of a soil/sediment rinseate blank. The results for the rinseate blank are included herein. The results for the soil/sediment samples are reported under project E13-0618. 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 sampling location included a field sample and field sample duplicate. Select locations also included a target analyte field matrix spike. Containers designated for field matrix spikes were fortified with an appropriate matrix spike solution containing PFOA, PFBS, PFHS, and PFOS prior to being sent to the field for sample collection. All sample containers were fortified with internal standards and surrogate recovery standards 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.
........
Testing Cert. # 2052.01
The testing reported herein meet the requirements of ANSI/ISO/IEC 17025:2005 "General Requirements for the Competence of Testing and Calibration Laboratories", in accordance with A2LA Certificate # 2052.01. Additionally, the laboratory's quality system has been audited and was determined to be in conformance with the EPA GLPs (40 CFR 792) by an independent assessment.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-03
Table 1. S am ple R e su lts S um m ary (1)
3M LIMS ID ISO13-05-03-001 ISO13-05-03-002
ISO13-05-03-004 ISO13-05-03-005
ISO13-05-03-006 ISO13-05-03-007
ISO13-05-03-008 ISO13-05-03-009
ISO13-05-03-011 ISO13-05-03-012
ISO13-05-03-013 ISO13-05-03-014
ISO13-05-03-016 ISO13-05-03-017
ISO13-05-03-018 ISO13-05-03-019
ISO13-05-03-020 ISO13-05-03-021
Sample Description
BFRS-GW-MW1R-0-130827 BFRS-GW-MW1R-DB-130827
Average %RPD Sample/Sample Dup BFRS-GW-MW3R-0-130827 BFRS-GW-MW3R-DB-130827
Average %RPD Sample/Sample Dup BFRS-GW-MW4R-0-130827 BFRS-GW-MW4R-DB-130827
Average %RPD Sample/Sample Dup BFRS-GW-MW4L-0-130827 BFRS-GW-MW4L-DB-130827
Average %RPD Sample/Sample Dup BFRS-GW-MW5R-0-130828 BFRS-GW-MW5R-DB-130828
Average %RPD Sample/Sample Dup BFRS-GW-MW5L-0-130828 BFRS-GW-MW5L-DB-130828
Average %RPD Sample/Sample Dup BFRS-GW-MW6R-0-130828 BFRS-GW-MW6R-DB-130828
Average %RPD Sample/Sample Dup BFRS-GW-MW6L-0-130828 BFRS-GW-MW6L-DB-130828
Average %RPD Sample/Sample Dup BFRS-GW-MW7R-0-130827 BFRS-GW-MW7R-DB-130827
Average %RPD Sample/Sample Dup
PFOA Concentration
(ng/mL)
1.79 1.70 1.75 5.2 22.0 16.8 19.4 27 (2) 9.87 7.59 8.73 26 (2) 0.269 0.264 0.267 1.9 0.212 0.206 0.209 2.9 0.635 0.591 0.613 7.2 2.57 2.65 2.61 3.1 0.195 0.238 0.217 20 8.79 8.24 8.52 6.5
PFBS
PFHS
PFOS
Concentration Concentration Concentration
(ng/mL)
(ng/mL)
(ng/mL)
0.108 0.110 0.109
1.8 4.34 3.47 3.91 22 (2)
0.874 0.869 0.872 0.57 21.8 17.4 19.6 22 (2)
1.69 1.69 1.69 0.0 26.0 20.4 23.2 24 (2)
0.728 0.567 0.648 25 (2)
18.5 14.5 16.5 24 (2)
25.8 20.9 23.4 21 (2)
0.0964 0.0906 0.0935
6.2
0.263 0.245 0.254
7.1
0.524 0.556 0.540
5.9
0.0535 0.0675 0.0605
23(2)
0.131 0.144 0.138
9.5
0.0874 0.0905 0.0890
3.5
0.165 0.170 0.168
3.0 0.249 0.250
0.262 0.284 0.273
8.1 0.665 0.688
1.24 1.29 1.27 4.0 7.64 7.71
0.250 0.40
0.677 3.4
7.68 0.91
0.0536 0.0565 0.0551
5.3
0.0853 0.0857 0.0855
0.47
0.324 0.360 0.342
11
0.533 1.80 24.4 0.497 1.74 25.7 0.515 1.77 25.1
7.0 3.4 5.2
NA = Not Applicable (1) 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 13%, PFBS 13%, PFHS 12%, and PFOS 16%. (2) The RPD value did not meet method acceptance criteria of <20%.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-03
Table 1 c o n tin u e d . S am ple R esu lts S um m ary (1)
3M LIMS ID ISO13-05-03-022 ISO13-05-03-023
ISO13-05-03-025 ISO13-05-03-026
ISO13-05-03-027 ISO13-05-03-028
ISO13-05-03-029 ISO13-05-03-030
ISO13-05-03-032 ISO13-05-03-033
ISO13-05-03-034 ISO13-05-03-035
ISO13-05-03-036 ISO13-05-03-037
ISO13-05-03-039 ISO13-05-03-040
ISO13-05-03-041 ISO13-05-03-042
Sample Description
BFRS-GW-MW8R-0-130828 BFRS-GW-MW8R-DB-130828
Average %RPD Sample/Sample Dup BFRS-GW-MW9R-0-130827 BFRS-GW-MW9R-DB-130827
Average %RPD Sample/Sample Dup BFRS-GW-MW9L-0-130827 BFRS-GW-MW9L-DB-130827
Average %RPD Sample/Sample Dup BFRS-GW-MW10R-0-130827 BFRS-GW-MW10R-DB-130827
Average %RPD Sample/Sample Dup BFRS-GW-MW11L-0-130828 BFRS-GW-MW11L-DB-130828
Average %RPD Sample/Sample Dup BFRS-SW-ET02-0-130828 BFRS-SW-ET02-DB-130828
Average %RPD Sample/Sample Dup BFRS-SW-ET03-0-130828 BFRS-SW-ET03-DB-130828
Average %RPD Sample/Sample Dup BFRS-SW-ET04-0-130828 BFRS-SW-ET04-DB-130828
Average %RPD Sample/Sample Dup BFRS-SS08-RB-0-130828 BFRS-GW-TRIP01 -0
PFOA Concentration
(ng/mL)
0.220 0.216 0.218
1.8 0.112 0.109 0.111
2.7 0.0301 0.0344 0.0323
13 0.644 0.669 0.657
3.8 0.286 0.275 0.281
3.9 0.0314 0.0313 0.0314
0.32 0.147 0.178 0.163
19 0.0507 0.0465 0.0486
8.6 <0.0240 <0.0240
PFBS Concentration
(ng/mL)
0.0590 0.0575 0.0583
2.6 <0.0250 <0.0250 <0.0250
NA <0.0250 <0.0250 <0.0250
NA 0.0692 0.0658 0.0675
5.0 <0.0250 <0.0250 <0.0250
NA 0.0350 0.0350 0.0350
0.0 0.0565 0.0560 0.0563
0.89 0.0371 0.0352 0.0362
5.3 <0.0250 <0.0250
PFHS Concentration
(ng/mL)
0.121 0.117 0.119
3.4 0.0579 0.0510 0.0545
13 <0.0250 <0.0250 <0.0250
NA 0.293 0.306 0.300
4.3 0.0823 0.0730 0.0777
12 <0.0250 <0.0250 <0.0250
NA 0.0820 0.0792 0.0806
3.5 <0.0250 <0.0250 <0.0250
NA <0.0250 <0.0250
PFOS Concentration
(ng/mL)
0.268 0.250 0.259
6.9 <0.0232 <0.0232 <0.0232
NA 0.0446 0.0443 0.0445
0.67 0.536 0.594 0.565
10 0.387 0.378 0.383
2.4 0.0547 0.0544 0.0546
0.55 0.295 0.260 0.278
13 0.113 0.105 0.109
7.3 <0.0232 <0.0232
NA = Not Applicable (1) 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 13%, PFBS 13%, PFHS 12%, and PFOS 16%. (2) The RPD value did not meet method acceptance criteria of <20%.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-03
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. T arget A n a lyte s
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 August 27 and 28, 2013 and returned to the 3M Environmental Laboratory on September 4, 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. S am ple D e s c rip tio n Key Code.
String Number 1 2
String Descriptor Sample Location Sample Type
3 Well Identifier 4 Well Level
5 Sample Type
6 Sampling Date
Example: BFRS-GW-MW4L-0-130827
BFRS= Browns Ferry Road Site GW= Ground Water SW=Surface Water Example: MW4 R = Residuum shallow water-bearing zone L = Bedrock water-bearing zone 0 =primary sample DB =duplicate sample FMS = Field Matrix Spike 130827 - August 27, 2013
2.3 Sample Preparation
9/10/13: Samples were prepared by removing an aliquot of the well mixed sample and placing it in an autovial for analysis.
9/13/13: Samples requiring dilution prior to analysis were prepared by removing a 0.4 mL aliquot of the well mixed sample and diluting it with 0.4 mL of methanol (dilution factor of 2).
All samples were analyzed by internal standard calibration. During the preparation of the laboratory control samples, an aliquot of a separate internal standard spiking solution was added to the laboratory control samples (nominal concentration of 1 ng/mL). The sample bottles were spiked with an internal standard mix at a nominal concentration of 1 ng/mL prior to being sent to the field for sample collection.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-03
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:
9/10/13: Direct Injection/internal standard analysis PFOA, PFBS, PFHS, PFOS, 13C4-PFOA, and 13C4-PFOS; all locations.
9/13/13: Solvent dilution / internal standard analysis PFOS and 13C4-PFOS; locations BFRSGW-MW3R, BFRS-GW-MW4R, and BFRS-GW-MW7R.
Due to the nature of the samples, the wide range of concentrations found in the samples, and the environmental occurrence of multiple isomers of the laboratory's analytes of interest, the software used for processing the analytical results is not able to consistently integrate the analytical peak, manual integration of the analytical peak is necessary. All manual integrations are performed following the procedures outlined in method ETS-12-010. The consistency of the laboratory's integration is ensured through the training of laboratory personnel, the peer review process required for all manual integrations, the review of manual integrations by the QAU, and where necessary the review of manual integrations by laboratory management.
Table 4. In s tru m e n t P aram eters
Instrument Name Analysis Dates Analytical Method Liquid Chromatograph Guard column Analytical column Injection Volume Mass Spectrometer Ion Source Polarity Software
ETS Buster 9/10/13 and 9/13/13
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
20 ijL Applied Biosystems API 4000
Turbo Spray Negative
Analyst 1.6.1
Table 5. L iq u id C h ro m a to g ra p h y G radient P rogram
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
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
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-03
Table 6. M ass T ra n s itio n s
Analyte
Mass Transition Q1/Q3
Internal Standard
Mass Transition Q1/Q3
413/369
PFOA
413/219
[13C8]PFOA
421/376
413/169
PFBS
299/80 299/99
[18O2]PFBS
303/84
PFHS
399/99 399/80
[13Cs]PFHS
402/99
499/99
PFOS
499/80
[13C8]-PFOS
507/80
499/130
[13C4]-PFOA surrogate
417/372
[13C8]-PFOA
421/376
[13C4]-PFOS surrogate
503/80
[13C8]-PFOS
507/80
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.
3 Data Analysis
3.1 Calibration
9/10/13: 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 1.0 ng/mL. Ten curve points ranging from 0.025 ng/mL to 25 ng/mL (nominal) were analyzed with the samples. Of these ten calibration standards, nine contained the surrogates at concentrations ranging from 0.0250 ng/mL to 10 ng/mL (nominal). A quadratic, 1/x weighted, calibration curve of the ratio of the standard peak area counts over the internal standard peak area counts was used to fit the data for each analyte. The data were not forced through zero during the fitting process.
9/13/13: Solvent Dilution / internal standard calibration. Samples were analyzed against an internal standard matrix-matched calibration curve. Calibration standards were prepared by spiking known amounts of the stock solution into a 50:50 Methanol: Laboratory Reagent Water. The calibration standards contained an internal standard mix at a nominal concentration of 0.5 ng/mL. Twelve standards ranging from 0.0125 ng/mL to 25 ng/mL (nominal) were analyzed with the samples. Of these twelve calibration standards, ten contained the surrogates at concentrations ranging from 0.0125 ng/mL to 10 ng/mL (nominal). A quadratic, 1/x weighted, calibration curve of the ratio of the standard peak area counts over the internal standard peak area counts was used to fit the data for each analyte. The data were not forced through zero during the fitting process.
For both 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
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-03
than or equal to 5% relative standard deviation (RSD) for peak area or peak area ratio and retention time criteria of less than or equal to 2% RSD. These criteria were met for all analytes.
3.3 Limit of Quantitation (LOQ)
The LOQ as defined in method ETS-8-044.1 is the lowest non-zero calibration standard in the curve that meets linearity and accuracy requirements and for which the peak area ratio (or peak area) is at least two times the average peak area ratio (or peak area) of the method blanks. The LOQs associated with the sample analysis are listed in the table below.
Table 7. LOQ
Analysis Date
Calibration
9/10/13
9/13/13 NA=Not Applicable
Internal standard Internal standard
Dilution Factor
NA 2
PFOA LOQ, ng/mL
<0.0240 NA
PFBS LOQ, ng/mL
<0.0250 NA
PFHS LOQ, ng/mL
<0.0250 NA
PFOS LOQ, ng/mL
<0.0232 <0.0232
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 for the target analytes and analyzed in triplicate, while only low and high lab control samples were prepared for the surrogates. LCSs were prepared by spiking known amounts of the analytes into laboratory reagent 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.
All batch LCS recovery results were used in the evaluation of the analytical method uncertainty in section 3.7 of the report.
The following calculations were used to generate data in Table 8.
Calculated Concentration LCS Percent Recovery
Spike Concentration
%
LCS% RSD = standard deviation LCS replicates * 10Q% average LCS recovery
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-03
Table 8. Lab C o n tro l S pike R esults
ETS-8-044.1 Analyzed 9/10/13 Internal Standard Calibration
Lab ID LCS-130910-1 LCS-130910-2 LCS-130910-3 Average %RSD LCS-130910-4 LCS-130910-5 LCS-130910-6 Average %RSD LCS-130910-7 LCS-130910-8 LCS-130910-9 Average %RSD
PFOA (Linear and Branched)
Spiked Concentration
(ng/mL)
Calculated Concentration
(ng/mL)
%Recovery
0.190 0.190 0.190
1.90 1.90 1.90
16.2 16.2 16.2
0.179 0.187 0.177 95.4% 3.0% 1.97 1.98 1.99 104% 0.96% 14.4 14.5 14.4 89.2% 0.45%
94.2 98.6 93.3
103 104 105
89.0 89.7 89.0
Spiked Concentration
(ng/mL)
PFBS
Calculated Concentration
(ng/mL)
0.198 0.198 0.198
1.98 1.98 1.98
16.9 16.9 16.9
0.192 0.200 0.195 98.8% 2.0% 2.19 2.05 2.07 106% 3.6% 15.7 15.6 15.5 92.3% 0.60%
%Recovery 97.1 101 98.3
110 103 104
92.9 92.3 91.8
ETS-8-044.1 Analyzed 9/10/13 Internal Standard Calibration
Lab ID LCS-130910-1 LCS-130910-2 LCS-130910-3 Average %RSD LCS-130910-4 LCS-130910-5 LCS-130910-6 Average %RSD LCS-130910-7 LCS-130910-8 LCS-130910-9 Average %RSD
Spiked Concentration
(ng/mL) 0.198 0.198 0.198
1.98 1.98 1.98
16.9 16.9 16.9
PFHS Calculated Concentration
(ng/mL)
0.197 0.211 0.193 101% 5.0% 2.21 2.42 2.21 115% 5.0% 16.8 16.1 16.2 96.8% 2.5%
%Recovery 99.7 107 97.3
112 122 112
99.6 95.1 95.6
PFOS (Linear and Branched)
Spiked Concentration
(ng/mL)
Calculated Concentration
(ng/mL)
%Recovery
0.184 0.184 0.184
1.84 1.84 1.84
15.7 15.7 15.7
0.180 0.180 0.202 102% 6.9% 1.98 1.89 1.81 103% 4.1% 13.7 13.6 13.6 86.8% 0.24%
97.7 97.9 110
107 103 98.6
87.0 86.6 86.9
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-03
Table 8 continued. Lab C ontrol Spike Results
ETS-8-044.1 Analyzed 9/10/13 Internal Standard Calibration
Lab ID LCS-130910-1 LCS-130910-2 LCS-130910-3 Average %RSD LCS-130910-4 LCS-130910-5 LCS-130910-6 Average %RSD
Spiked Concentration
(ng/mL) 0.198 0.198 0.198
1.98 1.98 1.98
13C4-PFOA Calculated Concentration
(ng/mL)
0.203 0.209 0.209 105% 1.6% 2.15 2.01 2.08 105% 3.3%
%Recovery 103 106 106
109 102 105
Spiked Concentration
(ng/mL) 0.189 0.189 0.189
1.89 1.89 1.89
13C4-PFOS Calculated Concentration
(ng/mL)
0.208 0.195 0.219 110% 5.9% 2.11 1.93 1.88 104% 6.4%
%Recovery 110 103 116
112 102 99.4
ETS-8-044.1 Analyzed 9/13/13 Internal Standard Calibration
Lab ID
LCS-130913-1 LCS-130913-2 LCS-130913-3 Average %RSD LCS-130913-4 LCS-130913-5 LCS-130913-6 Average %RSD LCS-130913-7 LCS-130913-8 LCS-130913-9 Average %RSD
PFOS (Linear and Branched)
Spiked Concentration
(ng/mL)
Calculated Concentration
(ng/mL)
%Recovery
0.184 0.184 0.184
1.84 1.84 1.84
32.2 32.2 32.2
0.166 0.158 0.170 89.6% 3.6% 1.80 1.70 1.77 95.6% 2.9% 31.1 31.7 31.4 97.5% 0.92%
90.2 86.1 92.5
98.0 92.6 96.2
96.6 98.4 97.6
Spiked Concentration
(ng/mL)
13C4-PFOS
Calculated Concentration
(ng/mL)
0.189 0.189 0.189
1.89 1.89 1.89
0.181 0.184 0.181 96.1% 0.99% 1.76 1.85 1.88 96.8% 3.4%
%Recovery 95.5 97.2 95.6
93.1 98.0 99.4
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-03
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. A n a ly tic a l M ethod U n ce rta in ty
Analyte PFOA PFBS PFHS PFOS
Calibration Internal Internal Internal Internal
Standard Deviation (%) 6.42 6.72 6.12 8.22
Method Uncertainty 13% 13% 12% 16%
3.8 Field Matrix Spikes (FMS)
Field matrix spike sample containers were prepared for select sampling locations to verify that the analytical method is applicable to the collected matrix. Field matrix spikes are generated by adding a measured volume of field sample to a container spiked by the laboratory with the target analytes prior to shipping sample containers to the field for sample collection. Field matrix spikes must be at least 0.5 times the analyte concentration to be considered an appropriate spike level. Field matrix spike recoveries within method acceptance criteria of 10030% confirm that "unknown" components in the sample matrix do not significantly interfere with the extraction and analysis of the analytes of interest. The reference standards for PFOA and PFOS in the field matrix spiking solution consisted of linear and branched isomers. The locations for which FMS sample containers were prepared are listed in Table 10. Field matrix spikes are presented in section 4 of this report.
FMS ,,Recovery = 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
Table 10. Field M a trix S pike (FMS) C o n ce n tra tio n s
Sampling location
GW-MW1R, GW-MW4L, GW-MW5L, GWMW8R, GW-MW10R, SW-ET03, and Trip Blank
PFOA ng/mL
0.958
PFBS ng/mL
1.00
PFHS ng/mL
1.00
PFOS ng/mL
0.927
4 Data Summary and Discussion
Tables 11-18 below summarize the sample results and target analyte field matrix spike recoveries for the sampling locations as well as the Trip Blank. The surrogate recovery standard recoveries are presented in Table 19. 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. Field matrix spikes meeting the method acceptance criteria of 30%, demonstrate that the method is appropriate for the given matrix.
PAGE 11 OF 17
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-03
All target analyte field matrix spikes met method acceptance criteria with the following exception:
BFRS-SW-ET03; The 13C4-PFOS results for this location are not reportable due to the analyte area counts were below the LLOQ area counts and less than two times the average area counts for the method blanks. This location had acceptable FMS recoveries for each analyte.
Table 11. BFRS-GW -MW 1R
3M LIMS ID
Description
ISO13-05-03-001
BFRS-GW-MW1R-0-130827
ISO13-05-03-002
BFRS-GW-MW1R-DB-130827
ISO13-05-03-003
BFRS-GW-MW1R-FMS-130827
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
1.79 NA 1.70 NA 2.55 84.0
1.75 ng/mL 5.2%
PFBS
Concentration (ng/mL)
%Recovery
0.108
NA
0.110
NA
1.02 91.1
0.109 ng/mL 1.8%
3M LIMS ID
Description
ISO13-05-03-001
BFRS-GW-MW1 R-0-130827
ISO13-05-03-002
BFRS-GW-MW1 R-DB-130827
ISO13-05-03-003
BFRS-GW-MW1 R-FMS-130827
Average Concentration (ng/mL) %RPD
NA = Not Applicable
PFHS
Concentration (ng/mL)
%Recovery
0.874
NA
0.869
NA
1.92 105
0.872 ng/mL 0.57%
PFOS
Concentration (ng/mL)
%Recovery
1.69 NA 1.69 NA 2.62 100
1.69 ng/mL 0.0%
Table 12. BFRS-GW -MW 4L
3M LIMS ID
Description
ISO13-05-03-008
BFRS-GW-MW4L-0-130827
ISO13-05-03-009
BFRS-GW-MW4L-DB-130827
ISO13-05-03-010
BFRS-GW-MW4L-FMS-130827
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
0.269
NA
0.264
NA
1.22 99.5
0.267 ng/mL 1.9%
PFBS
Concentration (ng/mL)
%Recovery
0.0964
NA
0.0906
NA
1.10 101
0.0935 ng/mL 6.2%
3M LIMS ID
Description
ISO13-05-03-008
BFRS-GW-MW4L-0-130827
ISO13-05-03-009
BFRS-GW-MW4L-DB-130827
ISO13-05-03-010
BFRS-GW-MW4L-FMS-130827
Average Concentration (ng/mL) %RPD
NA = Not Applicable
PFHS
Concentration (ng/mL)
%Recovery
0.263
NA
0.245
NA
1.32 107
0.254 ng/mL 7.1%
PFOS
Concentration (ng/mL)
%Recovery
0.524
NA
0.556
NA
1.55 109
0.540 ng/mL 5.9%
PAGE 12 OF 17
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-03
Table 13. BFRS-GW-MW5L
3M LIMS ID
Description
ISO13-05-03-013
BFRS-GW-MW5L-0-130828
ISO13-05-03-014
BFRS-GW-MW5L-DB-130828
ISO13-05-03-015
BFRS-GW-MW5L-FMS-130828
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
0.635
NA
0.591
NA
1.59 102
0.613 ng/mL 7.2%
PFBS
Concentration (ng/mL)
%Recovery
0.165
NA
0.170
NA
1.11 94.3
0.168 ng/mL 3.0%
3M LIMS ID
Description
ISO13-05-03-013
BFRS-GW-MW5L-0-130828
ISO13-05-03-014
BFRS-GW-MW5L-DB-130828
ISO13-05-03-015
BFRS-GW-MW5L-FMS-130828
Average Concentration (ng/mL) %RPD
NA = Not Applicable
PFHS
Concentration (ng/mL)
%Recovery
0.262
NA
0.284
NA
1.35 108
0.273 ng/mL 8.1%
PFOS
Concentration (ng/mL)
%Recovery
1.24 NA 1.29 NA 2.26 107
1.27 ng/mL 4.0%
Table 14. BFRS-GW -MW 8R
3M LIMS ID
Description
ISO13-05-03-022
BFRS-GW-MW8R-0-130828
ISO13-05-03-023
BFRS-GW-MW8R-DB-130828
ISO13-05-03-024
BFRS-GW-MW8R-FMS-130828
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
0.220
NA
0.216
NA
1.23 106
0.218 ng/mL 1.8%
PFBS
Concentration (ng/mL)
%Recovery
0.0590
NA
0.0575
NA
1.01 95.2
0.0583 ng/mL 2.6%
3M LIMS ID
Description
ISO13-05-03-022
BFRS-GW-MW8R-0-130828
ISO13-05-03-023
BFRS-GW-MW8R-DB-130828
ISO13-05-03-024
BFRS-GW-MW8R-FMS-130828
Average Concentration (ng/mL) %RPD
NA = Not Applicable
PFHS
Concentration (ng/mL)
%Recovery
0.121
NA
0.117
NA
1.15 103
0.119 ng/mL 3.4%
PFOS
Concentration (ng/mL)
%Recovery
0.268
NA
0.250
NA
1.17 98.3
0.259 ng/mL 6.9%
PAGE 13 OF 17
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-03
Table 15. BFRS-GW-MW10R
3M LIMS ID
Description
ISO13-05-03-029
BFRS-GW-MW10R-0-130827
ISO13-05-03-030
BFRS-GW-MW10R-DB-130827
ISO13-05-03-031
BFRS-GW-MW10R-FMS-130827
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
0.644
NA
0.669
NA
1.50 88.0
0.657 ng/mL 3.8%
PFBS
Concentration (ng/mL)
%Recovery
0.0692
NA
0.0658
NA
1.15 108
0.0675 ng/mL 5.0%
PFHS
3M LIMS ID
Description
ISO13-05-03-029
BFRS-GW-MW10R-0-130827
ISO13-05-03-030
BFRS-GW-MW10R-DB-130827
ISO13-05-03-031
BFRS-GW-MW10R-FMS-130827
Average Concentration (ng/mL) %RPD
Concentration (ng/mL)
%Recovery
0.293
NA
0.306
NA
1.26 96.1
0.300 ng/mL 4.3%
NA = Not Applicable
PFOS
Concentration (ng/mL)
%Recovery
0.536
NA
0.594
NA
1.42 92.2
0.565 ng/mL 10%
Table 16. BFRS-SW-ET03
3M LIMS ID
Description
ISO13-05-03-036
BFRS-SW-ET03-0-130828
ISO13-05-03-037
BFRS-SW-ET03-DB-130828
ISO13-05-03-038
BFRS-SW-ET03-FMS-130828
Average Concentration (ng/mL) %RPD
PFOA
Concentration (ng/mL)
%Recovery
0.147
NA
0.178
NA
1.16 104
0.163 ng/mL 19%
PFBS
Concentration (ng/mL)
%Recovery
0.0565
NA
0.0560
NA
1.04 98.4
0.0563 ng/mL 0.89%
3M LIMS ID
Description
ISO13-05-03-036
BFRS-SW-ET03-0-130828
ISO13-05-03-037
BFRS-SW-ET03-DB-130828
ISO13-05-03-038
BFRS-SW-ET03-FMS-130828
Average Concentration (ng/mL) %RPD
NA = Not Applicable
PFHS
Concentration (ng/mL)
%Recovery
0.0820
NA
0.0792
NA
1.06 97.9
0.0806 ng/mL 3.5%
PFOS
Concentration (ng/mL)
%Recovery
0.295
NA
0.260
NA
1.36 117
0.278 ng/mL 13%
PAGE 14 OF 17
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-03
Table 17. Trip Blank
3M LIMS ID ISO13-05-03-042 ISO13-05-03-043
Description BFRS-GW-TRIP01 -0 BFRS-GW-TRIP01-FMS
PFOA
Concentration (ng/mL)
<0.0240 0.874
%Recovery NA 91.2
PFBS
Concentration (ng/mL)
<0.0250 0.974
%Recovery NA 97.4
3M LIMS ID ISO13-05-03-042 ISO13-05-03-043
NA = Not Applicable
Description BFRS-GW-TRI P01-0 BFRS-GW-TRIP01-FMS
PFHS
Concentration (ng/mL)
<0.0250 1.03
%Recovery NA 103
PFOS
Concentration (ng/mL)
<0.0232 0.856
%Recovery NA 92.3
Table 18. S o il/S e d im e n t Rinseate B lank
3M LIMS ID ISO13-05-03-041
Description BFRS-SS08-RB-0-130828
PFOA
PFBS
PFHS
PFOS
Concentration (ng/mL)
<0.0240
Concentration (ng/mL)
<0.0250
Concentration (ng/mL)
<0.0250
Concentration (ng/mL)
<0.0232
Table 19. S u rro g a te R ecovery
3M LIMS ID ISO13-05-03-001 ISO13-05-03-002 ISO13-05-03-003 ISO13-05-03-004 ISO13-05-03-005 ISO13-05-03-006 ISO13-05-03-007 ISO13-05-03-008 ISO13-05-03-009 ISO13-05-03-010 ISO13-05-03-011 ISO13-05-03-012 ISO13-05-03-013 ISO13-05-03-014 ISO13-05-03-015
Description BFRS-GW-MW1R-0-130827 BFRS-GW-MW1R-DB-130827 BFRS-GW-MW1R-FMS-130827 BFRS-GW-MW3R-0-130827 BFRS-GW-MW3R-DB-130827 BFRS-GW-MW4R-0-130827 BFRS-GW-MW4R-DB-130827 BFRS-GW-MW4L-0-130827 BFRS-GW-MW4L-DB-130827 BFRS-GW-MW4L-FMS-130827 BFRS-GW-MW5R-0-130828 BFRS-GW-MW5R-DB-130828 BFRS-GW-MW5L-0-130828 BFRS-GW-MW5L-DB-130828 BFRS-GW-MW5L-FMS-130828
13C4-PFOA %Recovery
100 89.9 84.7 91.2 90.6 97.6 90.8 84.3 90.1 89.9 95.4 91.3 96.6 92.0 94.9
13C4-PFOS %Recovery
91.9 95.8 106 97.8, 94.7 (12) 100, 85.7 (2) 99.7, 93.3 (2) 101, 90.3 (2) 99.5 99.1 94.5 88.7 91.9 98.6 95.0 106
(1) NR=Not Reportable; Area counts were below the LLOQ and were not two times the method blank area counts. (2) Result from analysis on 9/13/13 for PFOS and 13C4-PFOS surrogate.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-05-03
Table 19 co n tin u e d . S u rro g a te R ecovery
3M LIMS ID ISO13-05-03-016 ISO13-05-03-017 ISO13-05-03-018 ISO13-05-03-019 ISO13-05-03-020 ISO13-05-03-021 ISO13-05-03-022 ISO13-05-03-023 ISO13-05-03-024 ISO13-05-03-025 ISO13-05-03-026 ISO13-05-03-027 ISO13-05-03-028 ISO13-05-03-029 ISO13-05-03-030 ISO13-05-03-031 ISO13-05-03-032 ISO13-05-03-033 ISO13-05-03-034 ISO13-05-03-035 ISO13-05-03-036 ISO13-05-03-037 ISO13-05-03-038 ISO13-05-03-039 ISO13-05-03-040 ISO13-05-03-041 ISO13-05-03-042 ISO13-05-03-043
Description BFRS-GW-MW6R-0-130828 BFRS-GW-MW6R-DB-130828 BFRS-GW-MW6L-0-130828 BFRS-GW-MW6L-DB-130828 BFRS-GW-MW7R-0-130827 BFRS-GW-MW7R-DB-130827 BFRS-GW-MW8R-0-130828 BFRS-GW-MW8R-DB-130828 BFRS-GW-MW8R-FMS-130828 BFRS-GW-MW9R-0-130827 BFRS-GW-MW9R-DB-130827 BFRS-GW-MW9L-0-130827 BFRS-GW-MW9L-DB-130827 BFRS-GW-MW10R-0-130827 BFRS-GW-MW10R-DB-130827 BFRS-GW-MW10R-FMS-130827 BFRS-GW-MW11L-0-130828 BFRS-GW-MW11L-DB-130828 BFRS-SW-ET02-0-130828 BFRS-SW-ET02-DB-130828 BFRS-SW-ET03-0-130828 BFRS-SW-ET03-DB-130828 BFRS-SW-ET03-FMS-130828 BFRS-SW-ET04-0-130828 BFRS-SW-ET04-DB-130828 BFRS-SS06-RB-0-130628 BFRS-GW-TRIP01 -0 BFRS-GW-TRIP01-FMS
13C4-PFOA %Recovery
103 98.4 94.5 109 101 94.2 96.0 94.3 94.1 91.5 86.5 91.9 101 88.4 92.6 91.3 89.7 76.0 85.1 93.7 91.3 87.2 94.5 98.2 92.4 90.8 98.9 93.6
13C4-PFOS %Recovery
102 95.8 94.7 91.8 98.8, 95.4 (2) 90.1,92.2 (2) 105 90.3 97.4 99.2 85.3 92.9 93.0 90.4 105 103 104 107 97.0 110 NR (1) NR (1) NR (1) 99.8 94.6 95.7 109 93.3
(1) NR=Not Reportable; Area counts were below the LLOQ and were not two times the method blank area counts. (2) Result from analysis on 9/13/13 for PFOS and 13C4-PFOS surrogate.
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3M ENVIRONMENTAL LABORATORY REPORT NO. IS013-05-03
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 11-19 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
Susan T. Wolf, 3M Pmnjcipal Analytical Investigator
&
Date
William K. Reagen, Ph.D., 3M Environmental Technical Director
33
Date
The 3M Environmental Laboratory's Quality Assurance Unit has audited the data and report for this
This test report shall not be reproduced except in full, without written approval of the 3M Environmental Laboratory.
PAGE 17 OF 17
