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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-06
Final Report
Analysis of PFOA, PFBS, PFHS, and PFOS in Aqueous Samples from 3M Decatur, Alabama: Groundwater Treatment Plant GAC System June 2013
Laboratory Request Number: ISO13-07-06 Method Requirement: 3M Method ETS-8-044.1
Report Date - Date of Last Signature
Testing Laboratory 3M EHS&S Operations 3M Environmental Laboratory
Building 260-5N-17 Maplewood, MN 55144-1000
Requester Gary Hohenstein 3M Building 224-5W-03 Saint Paul, MN 55144-1000 Phone: (651) 737-3570
The testing reported herein meet the requirements of ANSI/ISO/IEC 17025:2005 "General Requirements for the Competence of Testing and Calibration Laboratories", in accordance with the A2LA Testing Certificate # 2052.01. Additionally, the laboratory's quality system has been audited and was determined to be in conformance with the EPA GLPs (40 CFR 792) by an independent A2LA assessment.
PAGE 1 OF 21
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-06
3M Environmental Laboratory
3M Environmental Laboratory Technical Director: William K. Reagen, Ph.D. 3M Principal Analytical Investigator: Susan Wolf Report Author: Chelsie Grochow
Analytical Report ISO13-07-06
3M Decatur Groundwater Treatment Plant System; June 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 June 27, 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 ISO13-07-06. 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.
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. ISO13-07-06
Table 1. Sample Results Summary
3M LIMS ID
Sample Description
ISO13-07-06-001 DAL-GW-ACI; Sample
ISO13-07-06-002
ISO13-07-06-004 ISO13-07-06-005
ISO13-07-06-007 ISO13-07-06-008
ISO13-07-06-010 ISO13-07-06-011
ISO13-07-06-013 ISO13-07-06-014
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)
1460 1500 1480 (1) 2.7 1220 1200 1210 (1) 1.7 0.0568 0.0866 0.0717 (3) 42 (4) 2710 2800 2760 (1) 3.3 2590 2660 2630 (1) 2.7
PFBS Concentration
(ng/mL)
706 710 708 (1) 0.56 1030 1020 1030 (12) 0.98 108 113 111 (1) 4.5 274 289 282 (1) 5.3 224 225 225 (1) 0.45
PFHS Concentration
(ng/mL)
935 948 942 (1) 1.4 2040 2000 2020 (1) 2.0 0.0850 0.150 0.118 (3) 55 (4) 1300 1380 1340 (1) 6.0 1140 1130 1140 (1) 0.88
PFOS Concentration
(ng/mL)
1580 1600 1590 (1) 1.3 0.806 0.738 0.772 (3) 8.8 <0.0232 <0.0232 <0.0232 (3) NA 4010 4210 4110 (1) 4.9 4170 4130 4150 (1) 0.96
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 14%, PFBS 13%, PFHS 13%, and PFOS 16%. (2) Method uncertainty has been expanded to 35% for PFBS based on the FMS recovery. See section 4 for more information. (3) 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 19%, PFHS 19%, and PFOS 21 %. (4) Sample/sample duplicate RPD did not meet acceptance criteria of <20%.
2 Methods - Analytical and Preparatory
2.1 Methods
Analysis was completed using 3M Environmental Laboratory Method ETS-8-044.1 "Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis".
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. ISO13-07-06
2.2 Sample Collection
Samples were collected on June 27, 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 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 28, 2013.
2.3 Sample Preparation
All sample sets 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 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. ISO13-07-06
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 7/1/13 & 7/5/13 - external standard calibration
7/2/13 - internal calibration ETS-8-044.1 Agilent 1260
Betasil C18 (4.6 mm X 100 mm), 5 x Betasil C18 (4.6 mm X 100 mm), 5 x
2, 5, or 20 xL Applied Biosystems TripleQuad 5500
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 (pL/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
413/219 413/169
[13Cs]PFOA
421/376
PFBS PFHS
299/80 299/99 399/99 399/80
[18O2]PFBS [13Cs]PFHS
303/84 402/99
499/99
PFOS
499/80 499/130
[13Cs]PFOS
507/80
[13C4]PFOA surrogate [13C4]PFOS surrogate
417/372 503/80
[13Cs]PFOA [13Cs]PFOS
421/376 507/80
Dwell time was 20 msec for each transition. The individual transitions were summed to produce a "total ion chromatogram" (TIC), which was used for quantitation.
(1) Internal standards were used for the analysis on 7/2/13.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-06
3 Data Analysis
3.1 Calibration
Internal Standard Calibration Analysis on 7/2/13: Samples were analyzed against a matrix-matched stable isotope internal standard calibration curve. Calibration standards were prepared by spiking known amounts of stock solutions into laboratory prepared reagent water. The calibration standards contained an internal standard mix at a nominal concentration of 1 ng/mL. A total of 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 on 7/1/13 and 7/5/13: 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. The reference standards of PFOA and PFOS used to prepare the calibration standards consisted of both linear and branched isomers. Each curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method calibration accuracy requirements of 10025% (10030% for the lowest curve point) were met for all analytes. The correlation coefficient (r) was greater than 0.995 for all analytes.
3.2 System Suitability
A calibration standard was analyzed four times at the beginning of the analytical sequence to demonstrate overall system suitability. The acceptance criteria for system suitability samples is less than or equal to 5% relative standard deviation (RSD) for peak area/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. ISO13-07-06
Table 6. LOQ
Analyte PFOA PFBS PFHS PFOS PFOA PFBS PFHS PFOS
Analysis Date 7/2/13 7/2/13 7/2/13 7/2/13 7/1/13
7/1/13, 7/5/13 7/1/13 7/1/13
Calibration Internal standard Internal standard Internal standard Internal standard External standard External standard External standard External standard
LOQ, ng/mL 0.0240 0.0250 0.0250 0.0232
0.0192 (1) 0.0200 (1) 0.0200 (1) 0.0185 (1)
(1) The dilution factor was not applied to the LOQ.
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.
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. ISO13-07-06
Table 7. Lab Control Spike Results.
ETS-8-044.1 External Standard Calibration Analyzed 7/1/13
Lab ID
PFOA (Linear + Branched)
Spiked
Calculated
Concentration Concentration
(ng/mL)
(ng/mL)
%Recovery
LCS-130701-1 LCS-130701-2 LCS-130701-3
Average %RSD
0.191 0.191 0.191
0.180 0.176 0.180 93.7% 1.4%
94.4 92.1 94.5
LCS-130701-4 LCS-130701-5 LCS-130701-6
Average %RSD
1.91 1.91 1.91
1.95 1.93 1.93 101% 0.57%
102 101 101
LCS-130701-7 LCS-130701-8 LCS-130701-9
Average %RSD
19.1 19.1 19.1
20.4 19.3 19.0 103% 3.8%
107 101 99.6
Spiked Concentration
(ng/mL)
PFOA surrogate
Calculated Concentration
(ng/mL)
0.199 0.199 0.199
0.218 0.203 0.209 106% 3.8%
1.99
2.11
1.99
2.12
1.99
2.18
107% 1.4%
%Recovery 110 102 105
106 107 109
ETS-8-044.1 External Standard Calibration Analyzed 7/1/13
Lab ID
Spiked Concentration
(ng/mL)
PFBS
Calculated Concentration
(ng/mL)
LCS-130701-1 LCS-130701-2 LCS-130701-3
Average %RSD
0.199 0.199 0.199
0.190 0.188 0.196 96.0% 2.3%
LCS-130701-4 LCS-130701-5 LCS-130701-6
Average %RSD
LCS-130701-7 LCS-130701-8 LCS-130701-9
Average %RSD
1.99 1.99 1.99
20.0 20.0 20.0
2.10 2.08 2.08 105% 0.0%
20.1 19.1 19.4 97.5% 2.4%
%Recovery 95.3 94.3 98.5
105 105 105
100 95.4 97.1
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)
0.197 0.190 0.196 97.6% 2.1%
2.09 2.10 2.12 106% 1.1%
20.7 19.7 19.4 99.8% 3.8%
%Recovery 99.1 95.3 98.4
105 105 107
104 98.4 96.9
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-06
Table 7 continued. Lab Control Spike Results.
ETS-8-044.1 External Standard Calibration Analyzed 7/1/13
Lab ID
PFOS (Linear + Branched)
Spiked
Calculated
Concentration Concentration
(ng/mL)
(ng/mL)
%Recovery
LCS-130701-1 LCS-130701-2 LCS-130701-3
Average %RSD
0.185 0.185 0.185
0.192 0.184 0.183 101% 2.7%
104 99.5 99.1
LCS-130701-4 LCS-130701-5 LCS-130701-6
Average %RSD
LCS-130701-7 LCS-130701-8 LCS-130701-9
Average %RSD
1.85 1.85 1.85
18.5 18.5 18.5
1.95 1.96 1.97 106% 0.0%
20.3 20.0 19.6 108% 1.9%
106 106 106
110 108 106
Spiked Concentration
(ng/mL)
PFOS surrogate
Calculated Concentration
(ng/mL)
0.190 0.190 0.190
0.187 0.183 0.183 97.1% 1.3%
1.90
1.91
1.90
1.95
1.90
1.95
102% 1.5%
%Recovery 98.6 96.3 96.5
100 103 102
ETS-8-044.1 Internal Standard Calibration Analyzed 7/2/13
Lab ID
PFOA (Linear + Branched)
Spiked
Calculated
Concentration Concentration
(ng/mL)
(ng/mL)
%Recovery
LCS-130702-1 LCS-130702-2 LCS-130702-3
Average %RSD LCS-130702-4 LCS-130702-5 LCS-130702-6
Average %RSD LCS-130702-7 LCS-130702-8 LCS-130702-9
Average %RSD
0.190 0.190 0.190
1.90 1.90 1.90
9.52 9.52 9.52
0.176 0.177 0.188 95.1% 3.8%
1.92 1.97 1.89 101% 2.3%
10.0 9.13 9.75 101% 4.6%
92.6 93.4 99.2
101 104 99.3
105 95.9 102
Spiked Concentration
(ng/mL)
PFOA surrogate
Calculated Concentration
(ng/mL)
0.198 0.198 0.198
0.218 0.232 0.225 114% 3.1%
1.98
2.12
1.98
2.15
1.98
2.11
107% 0.54%
%Recovery 110 117 114
107 108 107
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-06
Table 7 continued. Lab Control Spike Results.
ETS-8-044.1 Internal Standard Calibration Analyzed 7/2/13
Lab ID
Spiked Concentration
(ng/mL)
PFBS
Calculated Concentration
(ng/mL)
LCS-130702-1 LCS-130702-2 LCS-130702-3
Average %RSD
0.198 0.198 0.198
0.210 0.209 0.222 108% 3.5%
LCS-130702-4 LCS-130702-5 LCS-130702-6
Average %RSD
LCS-130702-7 LCS-130702-8 LCS-130702-9
Average %RSD
1.98 1.98 1.98
9.94 9.94 9.94
2.21 2.17 2.22 111% 0.90%
11.4 10.2 11.5 111% 6.5%
%Recovery 106 105 112
111 110 112
115 103 116
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)
0.192 0.197 0.197 98.6% 1.3%
2.07 1.99 2.01 103% 2.0%
10.3 9.25 10.5 101% 6.6%
%Recovery 97.1 99.4 99.4
105 101 102
104 93.1 105
ETS-8-044.1 Internal Standard Calibration Analyzed 7/2/13
Lab ID
PFOS (Linear + Branched)
Spiked
Calculated
Concentration Concentration
(ng/mL)
(ng/mL)
%Recovery
LCS-130702-1 LCS-130702-2 LCS-130702-3
Average %RSD
0.184 0.184 0.184
0.186 0.173 0.185 98.7% 4.0%
101 94.1 101
LCS-130702-4 LCS-130702-5 LCS-130702-6
Average %RSD
1.84 1.84 1.84
1.84 1.86 1.97 103% 3.7%
100 101 107
LCS-130702-7 LCS-130702-8 LCS-130702-9
Average %RSD
9.21 9.21 9.21
9.63 8.84 9.59 102% 4.9%
105 96.0 104
Spiked Concentration
(ng/mL)
PFOS surrogate
Calculated Concentration
(ng/mL)
0.189 0.189 0.189
0.192 0.185 0.200 102% 4.0%
1.89
1.90
1.89
1.99
1.89
1.97
103% 2.6%
%Recovery 102 97.9 106
100 105 104
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-06
Table 7 continued. Lab Control Spike Results.
ETS-8-044.1 External Standard Calibration Analyzed 7/5/13
Lab ID
Spiked Concentration
(ng/mL)
PFBS
Calculated Concentration
(ng/mL)
LCS-130705-1 LCS-130705-2 LCS-130705-3
Average %RSD
0.199 0.199 0.199
0.201 0.200 0.205 102% 1.1%
LCS-130705-4 LCS-130705-5 LCS-130705-6
Average %RSD
LCS-130705-7 LCS-130705-8 LCS-130705-9
Average %RSD
1.99 1.99 1.99
20.0 20.0 20.0
2.15 2.27 2.17 110% 2.9%
19.1 19.9 19.5 97.5% 2.3%
%Recovery 101 101 103
108 114 109
95.3 99.7 97.5
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%.
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 6.94 6.50 6.68 8.07 9.56 9.13 9.41 10.7
Method Uncertainty 14% 13% 13% 16% 19% 18% 19% 21%
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-06
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.
FMS Recovery - (Sample Concentration of FMS - Average Concentration:Field Sample & Field Sample Dup.) * 1 0 0 % Spike Concentraton
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 or PFHS; however, the surrogate recovery standard 13C4-PFOS, met method acceptance criteria. No additional QC samples were prepared. The FMS sample recovery was 65.5% for PFBS. The method uncertainty has been expanded for PFBS to 35% based on the FMS recovery %bias.
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. ISO13-07-06
Table 10. DAL GW ACI 130627 (1)
3M LIMS ID
Description
ISO13-07-06-001
DAL-GW-ACI-0-130627
ISO13-07-06-002
DAL-GW-ACI-DB-130627
ISO13-07-06-003
DAL-GW-ACI-FMS-130627
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
1460
NA
1500
NA
3070
79.5
1480 ng/mL 2.7%
Concentration
(ng/mL)
%Recovery
706 NA
710 NA
2280
78.2
708 ng/mL 0.56%
3M LIMS ID
Description
ISO13-07-06-001
DAL-GW-ACI-0-130627
ISO13-07-06-002
DAL-GW-ACI-DB-130627
ISO13-07-06-003
DAL-GW-ACI-FMS-130627
Average Concentration (ng/mL) %RPD
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
935 NA
948 NA
2520
78.9
942 ng/mL 1.4%
Concentration
(ng/mL)
%Recovery
1580
NA
1600
NA
3380
89.9
1590 ng/mL 1.3%
13C4-PFOA
13C4-PFOS
3M LIMS ID
Description
ISO13-07-06-001
DAL-GW-ACI-0-130627
ISO13-07-06-002
DAL-GW-ACI-DB-130627
ISO13-07-06-003
DAL-GW-ACI-FMS-130627
Average Concentration (ng/mL) %RSD
%Recovery
99.1 101 96.7 99.0% 2.3%
%Recovery
95.9 95.5 99.3 96.9% 2.1%
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. ISO13-07-06
Table 11. DAL GW ACM2 130627
3M LIMS ID
Description
ISO13-07-06-004
DAL-GW-ACM2-0-130627
ISO13-07-06-005
DAL-GW-ACM2-DB-130627
ISO13-07-06-006
DAL-GW-ACM2-FMS-130627
Average Concentration (ng/mL) %RPD
3M LIMS ID
Description
ISO13-07-06-004
DAL-GW-ACM2-0-130627
ISO13-07-06-005
DAL-GW-ACM2-DB-130627
ISO13-07-06-006
DAL-GW-ACM2-FMS-130627
Average Concentration (ng/mL) %RPD
PFOA (1)
PFBS (1)
Concentration
(ng/mL)
%Recovery
1220
NA
1200
NA
1970
76.0
1210 ng/mL 1.7%
Concentration
(ng/mL)
%Recovery
1030
NA
1020
NA
1680
65.5 (2)
1030 ng/mL 0.98% (3)
PFHS (1)
PFOS (5)
Concentration
(ng/mL)
%Recovery
2040
NA
2000
NA
NA (4)
NA (4)
2020 ng/mL 2.0%
Concentration
(ng/mL)
%Recovery
0.806
NA
0.738
NA
NA (6)
NA (6)
0.772 ng/mL 8.8%
13c 4-p f o a (1) 13C4-PFOS (5)
3M LIMS ID
Description
ISO13-07-06-004
DAL-GW-ACM2-0-130627
ISO13-07-06-005
DAL-GW-ACM2-DB-130627
ISO13-07-06-006
DAL-GW-ACM2-FMS-130627
Average Concentration (ng/mL) %RPD/RSD
%Recovery
99.3 96.8 96.1 97.4% 1.7%
%Recovery
81.3 75.8 NA (6) 78.6% 6.9%
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. (2) FMS recovery did not meet acceptance criteria of 100 30%. (3) Method uncertainty has been expanded to 35% based on the FMS recovery %bias. (4) Analyte concentration exceeded calibration range. (5) Samples were analyzed by internal standard calibration. (6) Sample was not analyzed using internal calibration due to the high FMS concentration.
PAGE 14 OF 21
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-06
Table 12. DAL GW ACE 130627
3M LIMS ID
Description
ISO13-07-06-007
DAL-GW-ACE-0-130627
ISO13-07-06-008
DAL-GW-ACE-DB-130627
ISO13-07-06-009
DAL-GW-ACE-FMS-130627
Average Concentration (ng/mL) %RPD
3M LIMS ID
Description
ISO13-07-06-007
DAL-GW-ACE-0-130627
ISO13-07-06-008
DAL-GW-ACE-DB-130627
ISO13-07-06-009
DAL-GW-ACE-FMS-130627
Average Concentration (ng/mL) %RPD
PFOA (1)
PFBS (3)
Concentration
(ng/mL)
%Recovery
0.0568
NA
0.0866
NA
8.52
84.5
0.0717 ng/mL 42% (2)
Concentration
(ng/mL)
%Recovery
108 NA
113 NA
NA (4)
NA (4)
111 ng/mL 4.5%
PFHS (1)
PFOS (1)
Concentration
(ng/mL)
%Recovery
0.0850
NA
0.150
NA
8.52
84.1
0.118 ng/mL 55% (2)
Concentration
(ng/mL)
%Recovery
<0.0232
NA
<0.0232
NA
8.72
87.2
<0.0232 ng/mL
13C4-PFOA (1) 13C4-PFOS (1)
3M LIMS ID
Description
ISO13-07-06-007
DAL-GW-ACE-0-130627
ISO13-07-06-008
DAL-GW-ACE-DB-130627
ISO13-07-06-009
DAL-GW-ACE-FMS-130627
Average Concentration (ng/mL) %RSD
%Recovery
90.1 82.4 84.6 85.7% 4.6%
%Recovery
78.0 81.4 79.2 79.5% 2.1%
NA = Not Applicable (1) Samples were analyzed by internal standard calibration. (2) Sample/sample duplicate RPD did not meet acceptance criteria of <20%. (3) Samples were analyzed by external standard calibration. (4) Sample was not analyzed by external standard calibration due to the inappropriate FMS spike level.
PAGE 15 OF 21
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-06
Table 13. DAL GW WW8R 130627 (1)
3M LIMS ID
Description
ISO13-07-06-010
DAL-GW-WW8R-0-130627
ISO13-07-06-011
DAL-GW-WW8R-DB-130627
ISO13-07-06-012
DAL-GW-WW8R-FMS-130627
Average Concentration (ng/mL) %RPD
3M LIMS ID
Description
ISO13-07-06-010
DAL-GW-WW8R-0-130627
ISO13-07-06-011
DAL-GW-WW8R-DB-130627
ISO13-07-06-012
DAL-GW-WW8R-FMS-130627
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
2710
NA
2800
NA
6900
103
2760 ng/mL 3.3%
Concentration
(ng/mL)
%Recovery
274 NA
289 NA
4070
94.2
282 ng/mL 5.3%
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
1300
NA
1380
NA
5380
101
1340 ng/mL 6.0%
Concentration
(ng/mL)
%Recovery
4010
NA
4210
NA
8370
107
4110 ng/mL 4.9%
13C4-PFOA
13C4-PFOS
3M LIMS ID
Description
ISO13-07-06-010
DAL-GW-WW8R-0-130627
ISO13-07-06-011
DAL-GW-WW8R-DB-130627
ISO13-07-06-012
DAL-GW-WW8R-FMS-130627
Average Concentration (ng/mL) %RSD
%Recovery
95.0 99.0 94.7 96.2% 2.5%
%Recovery
95.6 98.6 99.5 97.9% 2.1%
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. ISO13-07-06
Table 14. DAL GW WW9R 130627 (1)
3M LIMS ID
Description
ISO13-07-06-013
DAL-GW-WW9R-0-130627
ISO13-07-06-014
DAL-GW-WW9R-DB-130627
ISO13-07-06-015
DAL-GW-WW9R-FMS-130627
Average Concentration (ng/mL) %RPD
3M LIMS ID
Description
ISO13-07-06-013
DAL-GW-WW9R-0-130627
ISO13-07-06-014
DAL-GW-WW9R-DB-130627
ISO13-07-06-015
DAL-GW-WW9R-FMS-130627
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
2590
NA
2660
NA
6330
92.4
2630 ng/mL 2.7%
Concentration
(ng/mL)
%Recovery
224 NA
225 NA
3970
93.2
225 ng/mL 0.45%
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
1140
NA
1130
NA
5000
96.9
1140 ng/mL 0.88%
Concentration
(ng/mL)
%Recovery
4170
NA
4130
NA
7240
77.6
4150 ng/mL 0.96%
13C4-PFOA
13C4-PFOS
3M LIMS ID
Description
ISO13-07-06-013
DAL-GW-WW9R-0-130627
ISO13-07-06-014
DAL-GW-WW9R-DB-130627
ISO13-07-06-015
DAL-GW-WW9R-FMS-130627
Average Concentration (ng/mL) %RSD
%Recovery
99.6 98.5 88.1 95.4% 6.7%
%Recovery
95.4 98.2 99.0 97.5% 1.9%
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. ISO13-07-06
Table 15. Trip Blank Results
3M LIMS ID ISO13-07-06-016 ISO13-07-06-017 ISO13-07-06-018
Description DAL-GW-TRIP01 -0 DAL-GW-TRIP01 -LS DAL-GW-TRI P01 -HS
3M LIMS ID ISO13-07-06-016 ISO13-07-06-017 ISO13-07-06-018
Description DAL-GW-TRI P01 -0 DAL-GW-TRI P01 -LS DAL-GW-TRI P01 -HS
PFOA
PFBS
Concentration (ng/mL)
<0.0240 (1) 8.07 (1) 3850 (2)
%Recovery NA 80.7 96.0
Concentration (ng/mL)
<0.0250 (1) 9.75 (1) 3730 (2)
%Recovery NA 97.5 92.8
PFHS
PFOS
Concentration (ng/mL)
<0.0250 (1) 8.47 (1) 3750 (2)
%Recovery NA 84.8 94.0
Concentration (ng/mL)
<0.0232 (1) 8.44 (1) 4050 (2)
%Recovery NA 84.4 102
13C4-PFOA
13C4-PFOS
3M LIMS ID ISO13-07-06-016 ISO13-07-06-017 ISO13-07-06-018
Description DAL-GW-TRI P01 -0 DAL-GW-TRI P01 -LS DAL-GW-TRI P01 -HS
%Recovery 80.1 (1) 76.8 (1) 96.7 (2)
%Recovery 81.9 (1) 78.5 (1) 92.8 (2)
NA = Not Applicable (1) Samples were analyzed by internal standard calibration. (2) 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 18 OF 21
3M ENVIRONMENTAL LABORATORY REPORT NO. IS013-07-06
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
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.
-e /C ? _______________________7 - / ? - Q
Quality Assu&nce 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. ISO13-07-06
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
FC Charting for DAL_GWTP_ACI
ACI PFOA PFBS PFHS PFOS
2 /8 /1 2 1180 792 1100 782
6/29/12 1650 1410 1460 964
8 /2 8 /1 2 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
ACE (Activated Carbon Effluent) - Sample Results in ng/mL
FC Charting for DAL_GWTP_ACE
3 /2 7 /1 3 2220 1060 1090 2490
4/29/13 1480 1360 777 1670
5 /3 1 /1 3 1860 1040 940 2150
6/27/13 1480 708 942 1590
ACE PFOA PFBS PFHS PFOS
2 /8 /1 2 1250 818 1240 741
8/28/12 0 .3 8 7 0 .2 5 6 0 .5 5 2 0 .1 0 3
1 2 /1 4 /1 2 0.102
< 0 .0 2 5 0 0 .1 1 7
0 .0 3 7 6
1 /1 7 /1 3 < 0 .0 2 4 0 < 0 .0 2 5 0 < 0 .0 2 5 0 < 0 .0 2 3 2
The ACE location was not sampled on 6/29/12.
2 /1 3 /1 3 0 .1 2 4
0 .0 3 6 0 0.178
0.0329
3/27/13 0 .0 3 8 0
< 0 .0 2 5 0 0 .0 4 7 7
< 0 .0 2 3 2
4 /2 9 /1 3 0.0422 0.392 0 .0 5 7
< 0 .0 2 3 2
5/31/13 0.0725 24.8 0 .1 0 5
< 0 .0 2 3 2
6 /2 7 /1 3 0 .0 7 1 7 111 0.118
< 0 .0 2 3 2
PAGE 20 OF 21
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-06
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
W W 8R PFOA PFBS PFHS PFOS
1 2 /1 3 /2 0 1 2 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
6/27/2013 2760 282 1340 4110
W W 9R PFOA PFBS PFHS PFOS
1 2 /1 3 /2 0 1 2 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
6/27/2013 2630 225 1140 4150
PAGE 21 OF 21
