Document b5GxrBjJ35BZXZ29EGzwxwG46
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-05
Final Report
Analysis of PFOA, PFBS, PFHS, and PFOS in Aqueous Samples from 3M Decatur, Alabama: Groundwater Treatment Plant GAC System May 2013
Laboratory Request Number: ISO13-07-05 Method Requirement: 3M Method ETS-8-044.1
Report Date - Date of Last Signature
Testing Laboratory 3M EHS 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. ISO13-07-05
3M Environmental Laboratory
3M Environmental Laboratory Technical Director: William K. Reagen, Ph.D. 3M Principal Analytical Investigator: Susan Wolf Report Author: Kevin Eich
Analytical Report ISO13-07-05
3M Decatur Groundwater Treatment Plant System; May 2013 Sampling
Report Date: Date of Last Signature
1 Introduction/Summary
The 3M Environmental Laboratory analyzed water samples from the groundwater treatment plant GAC system at the 3M Decatur, AL facility. Water samples were collected by Weston Solutions personnel on May 31, 2013. Samples were returned to the 3M Environmental Laboratory for analysis of Perfluorooctanoate (PFOA), Perfluorobutane sulfonate (PFBS), Perfluorohexane sulfonate (PFHS), Perfluorooctane sulfonate (PFOS), and the surrogate recovery standards 13C4-PFOA and 13C4-PFOS under laboratory project number ISO13-07-05. Analysis of the samples was completed as specified under 3M Environmental Laboratory General Project Outline (GPO) number GPO11-1006.
The 3M Environmental Laboratory provided sample containers for five sampling locations; ACI, ACM2, ACE, WW8R, and WW9R. The sample set consisted of a field sample, field sample duplicate and a field matrix spike. Each empty container was marked with a "fill to here" line that corresponded to a final volume of 200 mL. Containers reserved for field matrix spikes were fortified with an appropriate matrix spike solution containing all analytes prior to being sent to the field for sample collection. Sample bottles for sampling locations ACM2 and ACE, along with the Trip Blank sample and low spike, were fortified with internal standards and surrogates 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.
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 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. ISO13-07-05
Table 1. Sample Results Summary
3M LIMS ID
Sample Description
ISO13-07-05-001 ISO13-07-05-002
ISO13-07-05-004 ISO13-07-05-005
ISO13-07-05-007 ISO13-07-05-008
ISO13-07-05-010 ISO13-07-05-011
ISO13-07-05-013 ISO13-07-05-014
DAL-GW-ACI; Sample DAL-GW-ACI; Sample Dup
Average %RPD Sample/Sample Dup DAL-GW-ACM2; Sample DAL-GW-ACM2; Sample Dup
Average %RPD Sample/Sample Dup DAL-GW-ACE; Sample DAL-GW-ACE; Sample Dup
Average %RPD Sample/Sample Dup DAL-GW-WW8R; Sample DAL-GW-WW8R; Sample Dup
Average %RPD Sample/Sample Dup DAL-GW-WW9R; Sample DAL-GW-WW9R; Sample Dup
Average %RPD Sample/Sample Dup
PFOA Concentration
(ng/mL)
1840 1880 1860 (1) 2.2 868 885 877 (1) 1.9 0.0706 0.0744 0.0725 (2) 5.2 2750 2770 2760 (1) 0.72 2680 2640 2660 (1) 1.5
PFBS Concentration
(ng/mL)
1010 1070 1040 (1) 5.8 1240 1230 1240 (1) 0.81 24.9 24.7 24.8 (2) 0.81 287 291 289 (1) 1.4 231 221 226 (1) 4.4
PFHS Concentration
(ng/mL)
924 956 940 (1) 3.4 1660 1630 1650 (1) 1.8 0.108 0.102 0.105 (2) 5.7 1320 1340 1330 (1) 1.5 1130 1110 1120 (1) 1.8
PFOS Concentration
(ng/mL)
2090 2200 2150 (1) 5.1 0.571 0.598 0.585 (2) 4.6 <0.0232 <0.0232 <0.0232 (2) NA 4130 4220 4180 (1) 2.2 4210 4200 4210 (1) 0.24
NA = Not Applicable (1) Reported results were prepared and analyzed by ETS-8-044.1 using external standard calibration. The analytical method
uncertainties associated with the reported results are as follows: PFOA 16%, PFBS 17%, PFHS 15%, and PFOS 27%. (2) Reported results were prepared and analyzed by ETS-8-044.1 using internal standard calibration. The analytical method
uncertainties associated with the reported results are as follows: PFOA 13%, PFBS 16%, PFHS 19%, and PFOS 10%.
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 Perfluorooctanoic Acid (C8 Acid) Perfluorobutanesulfonate (C4 Sulfonate ) Perfluorohexanesulfonate (C6 Sulfonate) Perfluorooctanesulfonate (C8 Sulfonate)
Acronym PFOA PFBS PFHS PFOS
Reference Material Structure
Linear + Branched Linear Linear
Linear + Branched
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-05
2.2 Sample Collection
Samples were collected on May 31,2013 in NalgeneTM (high-density polyethylene) bottles prepared at the 3M Environmental Laboratory. 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 bottles for sampling locations ACM2 and ACE, along with the Trip Blank sample and Trip Blank low spike, were fortified with a mixture of mass-labeled internal standards at a nominal concentration of 1 ng/mL and a mixture of surrogate recovery standards at a nominal concentration of 0.1 ng/mL. Collected sample bottles were received by the laboratory at ambient conditions on June 6, 2013.
2.3 Sample Preparation
Sample sets ACI, ACM2, WW8R, WW9R, and the Trip Blank high spike were diluted 1:100 and analyzed for all analytes. The 1:100 dilutions were prepared by removing a 0.1 mL aliquot of the well mixed sample and adding 9.8 mL of methanol and 0.1 mL of a surrogate spiking solution. Prepared samples were analyzed by external standard calibration.
The ACE and ACM2 sample sets and the Trip Blank sample and Trip Blank low spike were prepared and analyzed for all analytes by transferring an aliquot of the well mixed sample into an autovial. Prepared samples were analyzed by internal standard calibration.
During the preparation of the laboratory control samples for internal standard calibration, 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 for ACE, ACM2, and Trip Blank were spiked with an internal standard mix at a nominal concentration of 1 ng/mL prior to being sent to the field for sample collection. The laboratory control samples were analyzed in the same manner as the samples.
2.4 Analysis
All samples and quality control samples were analyzed for 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. ISO13-07-05
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 Kirk
6/17/13 - external standard calibration
ETS-8-044.1 Agilent 1260 Betasil C18 (4.6 mm X 100 mm), 5 p Betasil C18 (4.6 mm X 100 mm), 5 p 2, 5, or 20 pL Applied Biosystems TripleQuad 5500 Turbo Spray
Negative Analyst 1.6.1
ETS Buster 6/19/13 - external standard calibration 6/21/13 - internal standard calibration
ETS-8-044.1 Agilent 1100 Betasil C18 (4.6 mm X 100 mm), 5 p Betasil C18 (4.6 mm X 100 mm), 5 p 2, 5, 20, or 25 pL Applied Biosystems API 4000 Turbo Spray
Negative Analyst 1.6.1
Table 4. Liquid Chromatography Gradient Program.
Step Number
0 1 2 3 4 5 6 7 8 9
Total Time (min)
0.00 0.50 4.00 6.00 11.0 13.0 13.5 16.0 16.5 19.0
Flow Rate (p L/min)
750 750 750 750 750 750 750 750 750 750
Percent A (2 mM ammonium acetate)
90.0 90.0 70.0 70.0 20.0 20.0 10.0 10.0 90.0 90.0
Percent B (Methanol)
10.0 10.0 30.0 30.0 80.0 80.0 90.0 90.0 10.0 10.0
Table 5. Mass Transitions
Analyte
Mass Transition Q1/Q3
Internal Standard (1)
Mass Transition Q1/Q3
413/369
PFOA
413/219
[13Cs]PFOA
421/376
413/169
PFBS PFHS
299/80 299/99 399/99 399/80
[18O2]PFBS [13Cs]PFHS
303/84 402/99
499/99
PFOS
499/80
[13Cs]PFOS
507/80
499/130
[13C4]PFOA surrogate
417/372
[13Cs]PFOA
421/376
[13C4]PFOS surrogate
503/80
[13Cs]PFOS
507/80
Dwell time was 20 (ETS Kirk) or 50 (ETS Buster) msec for each transition. The individual transitions were summed to produce a "total ion chromatogram" (TlC), which was used for quantitation.
(1) Internal standards were used for the analysis on 6/21/13.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-05
3 Data Analysis
3.1 Calibration
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 100 mL of laboratory prepared reagent water. The calibration standards contained an internal standard mix at a nominal concentration of 1 ng/mL. A total of thirteen calibration standards ranging from 0.025 ng/mL to 25 ng/mL (nominal) were analyzed with the prepared samples. Of these thirteen calibration standards, eleven contained the surrogates at concentrations ranging from 0.025 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. Calculating the standard concentrations using the peak area ratios 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. 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.
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: Milli-Q laboratory water. A total of ten spiked standards ranging from 0.02 ng/mL to 25 ng/mL (nominal) were analyzed. The ten standards also contained the surrogates at concentrations ranging from 0.02 ng/mL to 25 ng/mL nominal. 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. 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/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 area counts are at least twice those of the appropriate blanks. The LOQs associated with the sample analysis are listed in Table 6.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-05
Table 6. LOQ
Analyte PFOA PFBS PFHS PFOS PFOA PFBS PFHS PFOS
Analysis Date 6/21/13 6/21/13 6/21/13 6/21/13 6/17/13 6/17/13 6/17/13 6/19/13
Calibration Internal standard Internal standard Internal standard Internal standard External standard External standard External standard External standard
(1) The dilution factor was not applied to the LOQ.
LOQ, ng/mL 0.0240 0.0250 0.0250 0.0232
0.0192 (1) 0.0200 (1) 0.0200 (1) 0.0185 (1)
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.
3.5 Blanks
Two types of blanks were prepared and analyzed with the samples: method blanks/solvent blanks and field/trip blanks. Each blank result was 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 spikes were prepared for the surrogates. LCSs were prepared by spiking known amounts of the analytes into either 10 mL of laboratory-prepared matrix matched water or 1 mL of Milli-Q water to produce the desired concentration. When applicable, the LCSs were then diluted with methanol in the same manner as the samples. Method ETS-8-044.1 states that the average recovery of LCSs at each spiking level be within 80%-120% with a RSD <20%. All LCS samples met method accuracy criteria with the following exceptions:
6/19/13 analysis: The acceptance criteria for accuracy were met with the exception of the high set of LCS for PFOS (127%).
6/21/13 analysis: The acceptance criteria for precision were met with the exception of the low set of LCS for PFHS (27%).
A method deviation for LCS not meeting method acceptance criteria is filed with the raw data.
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 7.
Calculated Concentration * ____ _ LCS Percent Recovery -------------------------------------* 100%
Spike Concentration
LCS% RSD = standard deviation LCS replicates * 1QQ% average LCS recovery
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-05
Table 7. Lab Control Spike Results.
ETS-8-044.1 External Standard Calibration Analyzed 6/17/13
Lab ID
PFOA (Linear + Branched)
Spiked
Calculated
Concentration Concentration
(ng/mL)
(ng/mL)
%Recovery
LCS-130617-1 LCS-130617-2 LCS-130617-3
Average %RSD
LCS-130617-4 LCS-130617-5 LCS-130617-6
Average %RSD
0.191 0.191 0.191
1.91 1.91 1.91
0.179 0.189 0.192 97.8% 3.9%
2.01 1.98 2.02 105% 0.95%
93.5 98.8 101
105 104 106
LCS-130617-7 LCS-130617-8 LCS-130617-9
Average %RSD
19.1 19.1 19.1
21.8 20.8 22.0 113% 2.9%
114 109 115
Spiked Concentration
(ng/mL)
PFOA surrogate
Calculated Concentration
(ng/mL)
0.199 0.199 0.199
0.220 0.221 0.218 110% 0.52%
1.99 2.21 1.99 2.21 1.99 2.25
112% 1.0%
%Recovery 110 111 110
111 111 113
ETS-8-044.1 External Standard Calibration Analyzed 6/17/13
Lab ID
Spiked Concentration
(ng/mL)
PFBS
Calculated Concentration
(ng/mL)
LCS-130617-1 LCS-130617-2 LCS-130617-3
Average %RSD
LCS-130617-4 LCS-130617-5 LCS-130617-6
Average %RSD
LCS-130617-7 LCS-130617-8 LCS-130617-9
Average %RSD
0.199 0.199 0.199
1.99 1.99 1.99
20.0 20.0 20.0
0.202 0.201 0.207 102% 1.7%
2.11 2.10 2.18 107% 2.0%
23.1 21.8 23.8 114% 4.4%
%Recovery 101 101 104
106 105 109
115 109 119
Spiked Concentration
(ng/mL) 0.199 0.199 0.199
1.99 1.99 1.99
20.0 20.0 20.0
PFHS Calculated Concentration
(ng/mL)
0.187 0.197 0.197 97.4% 2.9%
2.06 2.06 2.16 106% 2.0%
23.2 21.5 24.2 115% 6.2%
%Recovery 94.2 98.8 99.2
105 104 108
116 107 121
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-05
Table 7 continued. Lab Control Spike Results.
ETS-8-044.1 External Standard Calibration Analyzed 6/19/13
Lab ID
PFOS (Linear + Branched)
Spiked
Calculated
Concentration Concentration
(ng/mL)
(ng/mL)
%Recovery
LCS-130617-1 LCS-130617-2 LCS-130617-3
Average %RSD
LCS-130617-4 LCS-130617-5 LCS-130617-6
Average %RSD
0.185 0.185 0.185
1.85 1.85 1.85
0.180 0.186 0.183 99.0% 1.9%
1.94 1.92 1.99 106% 2.0%
97.3 101 98.7
105 104 108
LCS-130617-7 18.5 24.0
130
LCS-130617-8 18.5 22.6
122
LCS-130617-9 18.5 23.9
129
Average %RSD
127% 3.4% (1)
Spiked Concentration
(ng/mL)
PFOS surrogate
Calculated Concentration
(ng/mL)
0.190 0.190 0.190
0.190 0.184 0.196 99.9% 3.2%
1.90 1.93 1.90 1.90 1.90 1.97
102% 2.0%
%Recovery 99.9 96.7 103
102 99.9 104
ETS-8-044.1 Internal Standard Calibration Analyzed 6/21/13
Lab ID
PFOA (Linear + Branched)
Spiked
Calculated
Concentration Concentration
(ng/mL)
(ng/mL)
%Recovery
LCS-130621-1 LCS-130621-2 LCS-130621-3
Average %RSD
0.190 0.190 0.190
0.163 0.158 0.171 86.2% 4.0%
85.8 83.0 89.9
LCS-130621-4 LCS-130621-5 LCS-130621-6
Average %RSD
LCS-130621-7 LCS-130621-8 LCS-130621-9
Average %RSD
1.90 1.90 1.90
9.52 9.52 9.52
2.00 1.76 1.80 97.5% 6.8%
8.23 9.28 9.13 93.3% 6.4%
105 92.5 94.9
86.4 97.5 95.9
PFOS (Linear + Branched)
Spiked Concentration
(ng/mL)
Calculated Concentration
(ng/mL)
%Recovery
0.184 0.184 0.184
0.169 0.161 0.166 89.7% 2.4%
91.6 87.4 90.0
1.84 1.84 1.84 1.73 1.84 1.79
97.1% 3.1%
100 94.0 97.2
9.21 8.25 89.6 9.21 8.65 93.9 9.21 8.84 96.0
93.2% 3.5%
(1) LCS average or RSD did not meet method acceptance criteria.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-05
Table 7 continued. Lab Control Spike Results.
ETS-8-044.1 Internal Standard Calibration Analyzed 6/21/13
Lab ID
Spiked Concentration
(ng/mL)
PFBS
Calculated Concentration
(ng/mL)
LCS-130621-1 LCS-130621-2 LCS-130621-3
Average %RSD
LCS-130621-4 LCS-130621-5 LCS-130621-6
Average %RSD
0.198 0.198 0.198
1.98 1.98 1.98
0.187 0.185 0.186 93.9% 0.69%
1.96 1.98 1.91 98.5% 1.7%
LCS-130621-7 LCS-130621-8 LCS-130621-9
Average %RSD
9.94 9.94 9.94
8.87 9.67 9.48 94.0% 4.4%
%Recovery 94.5 93.2 93.9
99.0 99.8 96.6
89.3 97.3 95.4
Spiked Concentration
(ng/mL) 0.198 0.198 0.198
1.98 1.98 1.98
9.94 9.94 9.94
PFHS Calculated Concentration
(ng/mL)
0.177 0.276 0.176 106% 27% (1)
1.96 1.78 1.88 94.6% 4.8%
8.13 9.48 9.30 90.2% 8.2%
%Recovery 89.5 139 88.6
98.9 89.8 95.0
81.7 95.3 93.6
ETS-8-044.1 Internal Standard Calibration Analyzed 6/21/13
Lab ID
Spiked Concentration
(ng/mL)
PFOA surrogate
Calculated Concentration
(ng/mL)
LCS-130621-1 LCS-130621-2 LCS-130621-3
Average %RSD
0.198 0.198 0.198
0.197 0.188 0.202 98.8% 3.7%
LCS-130621-4 LCS-130621-5 LCS-130621-6
Average %RSD
1.98 1.98 1.98
2.18 2.01 2.03 104% 4.7%
%Recovery 99.6 94.9 102
110 101 102
Spiked Concentration
(ng/mL)
PFOS surrogate
Calculated Concentration
(ng/mL)
0.189 0.189 0.189
0.180 0.186 0.186 97.5% 2.0%
1.89 1.96 1.89 1.87 1.89 1.89
101% 2.2%
%Recovery 95.2 98.6 98.7
103 98.8 100
(1) LCS average or RSD did not meet method acceptance criteria.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-05
3.7 Analytical Method Uncertainty
Analytical 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-12-012.2. 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 19%. The recovery of the high set of LCS analyzed on 6/19/13 was 127% for PFOS by external standard calibration for the samples analyzed on this date. The analytical uncertainty was expanded to 27% for all samples quantitated using external standard for PFOS.
Table 8. Analytical Method Uncertainty.
Analyte PFOA PFBS PFHS PFOS PFOA PFBS PFHS PFOS
Calibration Method External Standard External Standard External Standard External Standard Internal Standard Internal Standard Internal Standard Internal Standard
Standard Deviation (%) 8.18 8.60 7.33 NA 6.58 7.76 9.55 5.19
Method Uncertainty 16% 17% 15% 27% 13% 16% 19% 10%
NA= Not Applicable
3.8 Field Matrix Spikes (FMS)
A field matrix spike was collected at each sampling point 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 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 standards used for the preparation of the field matrix spiking solutions contained reference materials comprised of both linear and branched isomers for PFOA and PFOS. Field matrix spikes are presented in section 4 of this report.
In addition, field matrix spikes for this project consisted of stable isotope surrogate recovery standard spikes of [13C4]-PFOA and [13C4]-PFOS, which were added at a nominal concentration of 0.1 ng/mL to sample bottles associated with sampling locations ACM2 and ACE, and the Trip Blank sample and Trip Blank low spike, prior to sample collection. The [13C4]-labeled PFOA was selected to represent PFOA. The [13C4]-labeled PFOS was selected to represent PFBS, PFHS, and PFOS. Surrogate spike recoveries within method acceptance criteria of 10030% confirm that "unknown" components in the sample matrix do not significantly interfere with the preparation and analysis of the analytes of interest.
FMS Recovery - (Sample Concentration of FMS - Average Concentration: Field Sample & Field Sample Dup.) *100% Spike Concentraton
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-05
Table 9. Field Matrix Spike Concentrations
Location ACI ACM2 ACE WW8R, WW9R
Trip Blank
Description Field Matrix Spike Field Matrix Spike Field Matrix Spike Field Matrix Spike Low Field Matrix Spike High Field Matrix Spike
Final Concentration (ng/mL
PFOA
PFBS
PFHS
PFOS
2000
2010
2000
1990
1000 1000 998 994
10.0
10.0 9.99 10.0
4010
4020
3990
3980
10.0
10.0 9.99 10.0
4010
4020
3990
3980
4 Data Summary and Discussion
The tables below summarize the sample results and field matrix spike recoveries for the five locations as well as the Trip Blank. Each table provides the average concentration and the relative percent difference (%RPD) of the sample and sample duplicate. Results and average values are rounded to three significant figures. Percent relative difference (%RPD) values are rounded to two significant figures. Because of rounding, values may vary slightly from those listed in the raw data. Field matrix spikes meeting the method acceptance criteria of 30%, demonstrate that the method is appropriate for the given matrix.
All field matrix spike samples and surrogate recovery standards met method acceptance criteria except where noted below.
DAL-GW-ACM2; the FMS sample (1000 ng/mL) was not appropriate for PFOS; however, the surrogate recovery standard 13C4-PFOS, met method acceptance criteria. No additional QC samples were prepared.
DAL GW ACE; the FMS sample (10 ng/mL) was not appropriate for PFBS; however, the surrogate recovery standard 13C4-PFOS, met method acceptance criteria. No additional QC samples were prepared.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-05
Table 10. DAL GW ACI 130531 (1)
3M LIMS ID
Description
ISO13-07-05-001
DAL-GW-ACI-0-130531
ISO13-07-05-002 DAL-GW-ACI-DB-130531
ISO13-07-05-003 DAL-GW-ACI-FMS-130531
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
1840
NA
1880
NA
3820
98.0
1860 ng/mL 2.2%
Concentration
(ng/mL)
%Recovery
1010
NA
1070
NA
2950
95.0
1040 ng/mL 5.8%
3M LIMS ID
Description
ISO13-07-05-001
DAL-GW-ACI-0-130531
ISO13-07-05-002 DAL-GW-ACI-DB-130531
ISO13-07-05-003 DAL-GW-ACI-FMS-130531
Average Concentration (ng/mL) %RPD
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
924 NA
956 NA
2910
98.5
940 ng/mL 3.4%
Concentration
(ng/mL)
%Recovery
2090
NA
2200
NA
4350
111
2150 ng/mL 5.1%
13C4-PFOA
13C4-PFOS
3M LIMS ID
Description
ISO13-07-05-001
DAL-GW-ACI-0-130531
ISO13-07-05-002
DAL-GW-ACI-DB-130531
ISO13-07-05-003
DAL-GW-ACI-FMS-130531
Average Concentration (ng/mL) %RSD
%Recovery
100 100 96.6 98.9% 2.0%
%Recovery
94.4 96.1 91.9 94.1% 2.2%
NA = Not Applicable (1) Samples were analyzed by external standard calibration. The surrogate recovery standards 13C4-PFOA and 13C4-PFOS were
added to the samples during sample preparation.
PAGE 13 OF 21
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-05
Table 11. DAL GW ACM2 130531
3M LIMS ID
Description
ISO13-07-05-004
DAL-GW-ACM2-0-130531
ISO13-07-05-005
DAL-GW-ACM2-DB-130531
ISO13-07-05-006
DAL-GW-ACM2-FMS-130531
Average Concentration (ng/mL) %RPD
3M LIMS ID
Description
ISO13-07-05-004
DAL-GW-ACM2-0-130531
ISO13-07-05-005
DAL-GW-ACM2-DB-130531
ISO13-07-05-006
DAL-GW-ACM2-FMS-130531
Average Concentration (ng/mL) %RPD
PFOA (1)
PFBS (1)
Concentration
(ng/mL)
%Recovery
868 NA
885 NA
1800
92.4
877 ng/mL 1.9%
Concentration
(ng/mL)
%Recovery
1240
NA
1230
NA
2130
89.5
1240 ng/mL 0.81%
PFHS (1)
PFOS (2)
Concentration
(ng/mL)
%Recovery
1660
NA
1630
NA
2440
79.7
1650 ng/mL 1.8%
Concentration
(ng/mL)
%Recovery
0.571
NA
0.598
NA
NA (3)
NA (3)
0.585 ng/mL 4.6%
13C4-PFOA (1) 13C4-PFOS (2)
3M LIMS ID
Description
ISO13-07-05-004
DAL-GW-ACM2-0-130531
ISO13-07-05-005
DAL-GW-ACM2-DB-130531
ISO13-07-05-006
DAL-GW-ACM2-FMS-130531
Average Concentration (ng/mL) %RPD/RSD
%Recovery
101 103 94.9 99.7% 4.3%
%Recovery
117 118 NA (3) 98.1% 10%
NA = Not Applicable The surrogate recovery standards 13C4-PFOA and 13C4-PFOS were added to the samples during sample preparation. (1) Samples were analyzed by external standard calibration. (2) Samples were analyzed by internal standard calibration. (3) Sample was not analyzed using internal calibration due to the high FMS concentration.
PAGE 14 OF 21
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-05
Table 12. DAL GW ACE 130531 (1)
3M LIMS ID
Description
ISO13-07-05-007
DAL-GW-ACE-0-130531
ISO13-07-05-008
DAL-GW-ACE-DB-130531
ISO13-07-05-009
DAL-GW-ACE-FMS-130531
Average Concentration (ng/mL) %RPD
3M LIMS ID
Description
ISO13-07-05-007
DAL-GW-ACE-0-130531
ISO13-07-05-008
DAL-GW-ACE-DB-130531
ISO13-07-05-009
DAL-GW-ACE-FMS-130531
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
0.0706
NA
0.0744
NA
8.13 80.6
0.0725 ng/mL 5.2%
Concentration
(ng/mL)
%Recovery
24.9 NA
24.7 NA
NA (2)
NC
24.8 ng/mL 0.81%
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
0.108
NA
0.102
NA
8.81 87.1
0.105 ng/mL 5.7%
Concentration
(ng/mL)
%Recovery
<0.0232
NA
<0.0232
NA
9.76 97.6
<0.0232 ng/mL
13C4-PFOA
13C4-PFOS
3M LIMS ID
Description
ISO13-07-05-007
DAL-GW-ACE-0-130531
ISO13-07-05-008
DAL-GW-ACE-DB-130531
ISO13-07-05-009
DAL-GW-ACE-FMS-130531
Average Concentration (ng/mL) %RSD
%Recovery
105 111 112 110% 3.5%
%Recovery
123 110 115 116% 5.9%
NA = Not Applicable NC = Not Calculated; Spike level was less than 0.5x the endogenous sample concentration. (1) Samples were analyzed by internal standard calibration. (2) The sample concentration exceeded to the calibration range of 25 ng/mL.
PAGE 15 OF 21
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-05
Table 13. DAL GW WW8R 130531 (1)
3M LIMS ID
Description
ISO13-07-05-010
DAL-GW-WW8R-0-130531
ISO13-07-05-011
DAL-GW-WW8R-DB-130531
ISO13-07-05-012
DAL-GW-WW8R-FMS-130531
Average Concentration (ng/mL) %RPD
3M LIMS ID
Description
ISO13-07-05-010
DAL-GW-WW8R-0-130531
ISO13-07-05-011
DAL-GW-WW8R-DB-130531
ISO13-07-05-012
DAL-GW-WW8R-FMS-130531
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
2750
NA
2770
NA
6320
88.8
2760 ng/mL 0.72%
Concentration
(ng/mL)
%Recovery
287 NA
291 NA
3910
90.1
289 ng/mL 1.4%
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
1320
NA
1340
NA
5110
94.7
1330 ng/mL 1.5%
Concentration
(ng/mL)
%Recovery
4130
NA
4220
NA
7550
84.8
4180 ng/mL 2.2%
13C4-PFOA
13C4-PFOS
3M LIMS ID
Description
ISO13-07-05-010
DAL-GW-WW8R-0-130531
ISO13-07-05-011
DAL-GW-WW8R-DB-130531
ISO13-07-05-012
DAL-GW-WW8R-FMS-130531
Average Concentration (ng/mL) %RSD
%Recovery
96.0 94.5 99.1 96.5% 2.4%
%Recovery
95.2 96.0 93.5 94.9% 1.3%
NA = Not Applicable (1) Samples were analyzed by external standard calibration. The surrogate recovery standards 13C4-PFOA and 13C4-PFOS were
added to the samples during sample preparation.
PAGE 16 OF 21
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-05
Table 14. DAL GW WW9R 130531 (1)
3M LIMS ID
Description
ISO13-07-05-013
DAL-GW-WW9R-0-130531
ISO13-07-05-014
DAL-GW-WW9R-DB-130531
ISO13-07-05-015
DAL-GW-WW9R-FMS-130531
Average Concentration (ng/mL) %RPD
3M LIMS ID
Description
ISO13-07-05-013
DAL-GW-WW9R-0-130531
ISO13-07-05-014
DAL-GW-WW9R-DB-130531
ISO13-07-05-015
DAL-GW-WW9R-FMS-130531
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
2680
NA
2640
NA
6620
98.8
2660 ng/mL 1.5%
Concentration
(ng/mL)
%Recovery
231 NA
221 NA
4030
94.6
226 ng/mL 4.4%
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
1130
NA
1110
NA
4910
95.0
1120 ng/mL 1.8%
Concentration
(ng/mL)
%Recovery
4210
NA
4200
NA
8530
109
4210 ng/mL 0.24%
13C4-PFOA
13C4-PFOS
3M LIMS ID
Description
ISO13-07-05-013
DAL-GW-WW9R-0-130531
ISO13-07-05-014
DAL-GW-WW9R-DB-130531
ISO13-07-05-015
DAL-GW-WW9R-FMS-130531
Average Concentration (ng/mL) %RSD
%Recovery
100 95.4 92.5 96.0% 4.0%
%Recovery
93.8 92.6 99.3 95.2% 3.7%
NA = Not Applicable (1) Samples were analyzed by external standard calibration. The surrogate recovery standards 13C4-PFOA and 13C4-PFOS were
added to the samples during sample preparation.
PAGE 17 OF 21
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-05
Table 15. Trip Blank Results
3M LIMS ID
ISO13-07-05-016 ISO13-07-05-017 ISO13-07-05-018
Description
DAL-GW-TRIP01 -0 DAL-GW-TRIP01 -LS DAL-GW-TRI P01-HS
3M LIMS ID
ISO13-07-05-016 ISO13-07-05-017 ISO13-07-05-018
Description
DAL-GW-TRI P01-0 DAL-GW-TRI P01-LS DAL-GW-TRI P01-HS
PFOA
PFBS
Concentration (ng/mL)
<0.0240 (1) 7.99 (1) 4250 (2)
%Recovery
NA 79.9 106
Concentration (ng/mL)
<0.0250 (1) 9.88 (1) 3870 (2)
%Recovery
NA 98.8 96.3
PFHS
PFOS
Concentration (ng/mL)
<0.0250 (1) 8.89 (1) 4080 (2)
%Recovery
NA 89.0 102
Concentration (ng/mL)
<0.0232 (1) 9.11 (1) 4190 (2)
%Recovery NA 91.1 105
C13 4 -PFOA
C13 4 -PFOS
3M LIMS ID
ISO13-07-05-016 ISO13-07-05-017 ISO13-07-05-018
Description
DAL-GW-TRI P01-0 DAL-GW-TRI P01-LS DAL-GW-TRI P01-HS
00 CM
%Recovery
111 (1) 105 (2)
NA = Not Applicable (1) Samples were analyzed by internal standard calibration. (2) Samples were analyzed by external standard calibration.
%Recovery
111 (1) 112 (1) 92.5 (2)
PAGE 18 OF 21
3M ENVIRONMENTAL LABORATORY REPORT NO. IS013-07-05
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 matrix spike recoveries demonstrated that the analytical method was appropriate for the given sample matrix. Analysis was completed using 3M Environmental Laboratory Method ETS-8044.1 "Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis". Analytical results are reported in Table 1 and 10-15 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 Attachments
Attachment A: Analyte Trend Data for select sampling points at the Decatur Ground Water Treatment Plant (GWTP) GAC System.
8 Signatures
Susan T. Wolf, 3M Prjfidipal Analytical Investigator
William K. Reagen, Ph.D., 3M Environmental Laboratory Technical Director
Date
The 3M Environmental Laboratory's Quality Assurance Unit has audited the data and report for this project.
Quality Assurance Representative
Date
This test report shall not be reproduced except in full, without written approval of the 3M Environmental Laboratory.
PAGE 19 OF 21
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-05
Attachment A: Analyte Trend Data for select sampling points at the Decatur Ground Water Treatment Plant (GWTP) GAC System ACI (Activated Carbon Influent) - Sample Results in ng/mL
ACI PFOA PFBS PFHS PFOS
6/17/11 1410 1110 983 691
2/8/12 1180 792 1100 782
6/29/12 1650 1410 1460 964
8/28/12 1410 1830 1390 172
12/14/12 2580 723 1380 2810
1/17/13 1910 588 895 1810
2/13/13 2300 830 1580 2940
3/27/13 2220 1060 1090 2490
4/29/13 1480 1360 777 1670
5/31/13 1860 1040 940 2150
ACE (Activated Carbon Effluent) - Sample Results in ng/mL
ACE PFOA PFBS PFHS PFOS
6/17/11 2.57 11.9 2.50 2.07
2/8/12 1250 818 1240 741
8/28/12 0.387 0.256 0.552 0.103
12/14/12 0.102
<0.0250 0.117
0.0376
1/17/13 <0.0240 <0.0250 <0.0250 <0.0232
2/13/13 0.124
0.0360 0.178
0.0329
3/27/13 0.0380 <0.0250 0.0477 <0.0232
4/29/13 0.0422 0.392 0.0570
<0.0232
5/31/13 0.0725 24.8 0.105 <0.0232
The ACE location was not sampled on 6/29/12.
PAGE 20 OF 21
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-05
Attachment A: Analyte Trend Data for select sampling points at the Decatur Ground Water Treatment Plant (GWTP) GAC System WW8R - Sample Results in ng/mL
WW8R PFOA PFBS PFHS PFOS
12/13/2012 3630 441 1740 4920
1/17/2013 4350 410 1930 5710
2/13/2013 3250 354 1900 4850
WW9R - Sample Results in ng/mL
3/27/2013 3640 385 1760 5120
4/29/2013 3190 364 1610 4830
5/31/2013 2760 289 1330 4180
WW9R PFOA PFBS PFHS PFOS
12/13/2012 3360 321 1480 4080
1/17/2013 2710 184 954 3690
2/13/2013 2850 236 1400 4100
3/27/2013 3330 278 1440 4660
4/29/2013 2650 244 1200 4340
5/31/2013 2660 226 1120 4210
PAGE 21 OF 21
