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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-10
Final Report
Analysis of PFOA, PFBS, PFHS, and PFOS in Aqueous Samples from 3M Decatur, Alabama: Groundwater Treatment Plant GAC System November 2013
Laboratory Request Number: ISO13-07-10 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.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-10
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 ISO13-07-10
3M Decatur Groundwater Treatment Plant System; November 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 November 18, 2013. Samples were returned to the 3M Environmental Laboratory for analysis of Perfluorooctanoate (PFOA), Perfluorobutane sulfonate (PFBS), Perfluorohexane sulfonate (PFHS), Perfluorooctane sulfonate (PFOS) under laboratory project number ISO13-07-10. 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 seven sampling locations; ACI, ACM2, ACE, WW8R, WW9R, WW10R, and WW11R. 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.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-10
Table 1. Sample Results Summary
3M LIMS ID
Sample Description
ISO13-07-10-001 ISO13-07-10-002
ISO13-07-10-004 ISO13-07-10-005
ISO13-07-10-007 ISO13-07-10-008
ISO13-07-10-010 ISO13-07-10-011
ISO13-07-10-013 ISO13-07-10-014
ISO13-07-10-019 ISO13-07-10-020
ISO13-07-10-022 ISO13-07-10-023
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 DAL-GW-WW10R; Sample DAL-GW-WW10R; Sample Dup
Average %RPD Sample/Sample Dup DAL-GW-WW11R; Sample DAL-GW-WW11R; Sample Dup
Average %RPD Sample/Sample Dup
PFOA Concentration
(ng/mL)
2190 2190 2190 (1) 0.0 0.0539 0.0527 0.0533 (2) 2.3 0.511 0.445 0.478 (2)
14 3060 3010 3040 (1) 1.6 2910 2980 2950 (1) 2.4 2410 2380 2400 (1) 1.3 1300 1330 1320 (1) 2.3
PFBS Concentration
(ng/mL)
1100 1090 1100 (1) 0.91 1130 1110 1120 (1) 1.8 0.620 0.563 0.592 (2) 9.6 363 360 362 (1) 0.83 301 309 305 (1) 2.6 301 304 303 (1) 0.99 286 288 287 (1) 0.70
PFHS Concentration
(ng/mL)
1320 1340 1330 (1) 1.5 0.0728 0.0670 0.0699 (2) 8.3 0.401 0.331 0.366 (2)
19 1440 1440 1440 (1) 0.0 1300 1370 1340 (1) 5.2 1120 1120 1120 (1) 0.0 673 687 680 (1) 2.1
PFOS Concentration
(ng/mL)
2260 2220 2240 (1) 1.8 0.206 0.198 0.202 (2) 4.0 0.0979 0.0472 0.0726 (2) 70 (3) 4790 4710 4750 (1) 1.7 4430 4640 4540 (1) 4.6 3940 3840 3890 (1) 2.6 1790 1900 1850 (1) 5.9
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 17%, PFBS 18%, PFHS 15%, and PFOS 21 %. (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 15%, PFBS 16%, PFHS 20%, and PFOS 17%. (3) Sample/sample duplicate RPD did not meet acceptance criteria of <20%.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-10
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
2.2 Sample Collection
Samples were collected on November 18, 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 November 25, 2013.
2.3 Sample Preparation
All samples were diluted with methanol and analyzed for all analytes. Samples diluted 1:10 were prepared by removing a 1 mL aliquot of the well mixed sample and adding 8.9 mL of methanol and 0.1 mL of a surrogate spiking solution. 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. Further dilution may have been applied by using a lower injection volume on the instrument.
The ACE and ACM2 sample sets and the Trip Blank sample 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.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-10
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.
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 12/12/13 - external standard calibration 12/13/13 - internal standard calibration
ETS-8-044.1 Agilent 1260 Betasil C18 (4.6 mm X 100 mm), 5 g Betasil C18 (4.6 mm X 100 mm), 5 g 2, 5, or 20 gL 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 (gL/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
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-10
Table 5. Mass Transitions.
Analyte
Mass Transition Q1/Q3
Internal Standard (1)
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
402/80
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 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 12/13/13.
3 Data Analysis
3.1 Calibration
External Standard Calibration Analysis on 12/12/13: 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 eleven spiked standards ranging from 0.02 ng/mL to 50 ng/mL (nominal) were analyzed. The 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.
Internal Standard Calibration Analysis on 12/13/13: 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.
For each calibration curve, the reference standards of PFOA and PFOS used to prepare the calibration standards consisted of both linear and branched isomers. Each curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method calibration accuracy requirements of 10025% (10030% for the lowest curve point) were met for all analytes. The correlation coefficient r was greater than 0.995 for all analytes.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-10
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.
Table 6. LOQ
Analyte
Calibration
LOQ, ng/mL
PFOA
Internal standard
0.0240
PFBS
Internal standard
0.0250
PFHS
Internal standard
0.0400
PFOS
Internal standard
0.0232
PFOA
External standard
0.0958 (1)
PFBS
External standard
0.0200 (1)
PFHS
External standard
0.0200 (1)
PFOS
External standard
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
______ ,, ,, ,, standard deviation LCS replicates LCS% RSD = ------------------------------------- - --------- * 100%
average LCS recovery
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-10
Table 7. Lab Control Spike Results.
ETS-8-044.1 External Standard Calibration Analyzed 12/12/13
Lab ID
PFOA (Linear + Branched)
Spiked
Calculated
Concentration Concentration
(ng/mL)
(ng/mL)
%Recovery
LCS-131212-1 LCS-131212-2 LCS-131212-3 Average %RSD
LCS-131212-4 LCS-131212-5 LCS-131212-6 Average %RSD
0.191 0.191 0.191
4.74 4.74 4.74
0.194 0.188 0.184 98.9% 2.9%
5.37 5.32 5.48 114% 1.8%
102 98.4 96.3
113 112 116
LCS-131212-7 LCS-131212-8 LCS-131212-9 Average %RSD
38.2 38.2 38.2
41.5 38.1 38.1 103% 5.2%
109 99.6 99.7
Spiked Concentration
(ng/mL)
PFOA surrogate
Calculated Concentration
(ng/mL)
0.199 0.199 0.199
0.223 0.214 0.214 109% 2.4%
4.94 5.22 4.94 5.23 4.94 5.11
105% 1.1%
%Recovery 112 108 107
106 106 104
ETS-8-044.1 External Standard Calibration Analyzed 12/12/13
Lab ID
Spiked Concentration
(ng/mL)
PFBS
Calculated Concentration
(ng/mL)
LCS-131212-1 LCS-131212-2 LCS-131212-3 Average %RSD LCS-131212-4 LCS-131212-5 LCS-131212-6 Average %RSD LCS-131212-7 LCS-131212-8 LCS-131212-9 Average %RSD
0.199 0.199 0.199
4.95 4.95 4.95
39.8 39.8 39.8
0.219 0.220 0.214 109% 1.1%
5.70 5.76 5.78 116% 0.86%
41.5 40.6 40.0 102% 2.0%
%Recovery 110 110 108
115 116 117
104 102 100
Spiked Concentration
(ng/mL) 0.199 0.199 0.199
4.95 4.95 4.95
39.8 39.8 39.8
PFHS Calculated Concentration
(ng/mL)
0.207 0.202 0.204 103% 1.1%
5.46 5.41 5.56 110% 1.4%
>ULOQ >ULOQ >ULOQ
NA
%Recovery 104 102 102
110 109 112
NA NA NA
>ULOQ = analyte concentration exceeded upper limit of quantitation NA = Not Applicable
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-10
Table 7 continued. Lab Control Spike Results.
ETS-8-044.1 External Standard Calibration Analyzed 12/12/13
Lab ID
PFOS (Linear + Branched)
Spiked
Calculated
Concentration Concentration
(ng/mL)
(ng/mL)
%Recovery
LCS-131212-1 LCS-131212-2 LCS-131212-3 Average %RSD
LCS-131212-4 LCS-131212-5 LCS-131212-6 Average %RSD
LCS-131212-7 LCS-131212-8 LCS-131212-9 Average %RSD
0.185 0.185 0.185
4.59 4.59 4.59
36.9 36.9 36.9
0.204 0.197 0.197 108% 1.6%
5.37 5.34 5.38 117% 0.49%
39.3 36.1 36.5 101% 4.4%
110 107 107
117 116 117
106 97.9 98.8
Spiked Concentration
(ng/mL)
PFOS surrogate
Calculated Concentration
(ng/mL)
0.190 0.190 0.190
0.215 0.208 0.207 110% 2.1%
4.73 5.11 4.73 5.19 4.73 5.01
108% 1.9%
%Recovery 113 109 109
108 110 106
ETS-8-044.1 Internal Standard Calibration Analyzed 12/13/13
Lab ID
PFOA (Linear + Branched)
Spiked
Calculated
Concentration Concentration
(ng/mL)
(ng/mL)
%Recovery
LCS-131213-1 LCS-131213-2 LCS-131213-3 Average %RSD
LCS-131213-4 LCS-131213-5 LCS-131213-6 Average %RSD
LCS-131213-7 LCS-131213-8 LCS-131213-9 Average %RSD
0.190 0.190 0.190
1.90 1.90 1.90
19.0 19.0 19.0
0.199 0.190 0.200 103% 2.8%
2.15 2.06 2.04 110% 2.8%
20.7 20.2 19.4 106% 3.3%
105 100 105
113 109 107
109 106 102
Spiked Concentration
(ng/mL)
PFOA surrogate
Calculated Concentration
(ng/mL)
0.198 0.198 0.198
0.232 0.225 0.229 116% 1.3%
1.98 2.32 1.98 2.18 1.98 2.28
114% 3.2%
%Recovery 117 114 116
117 110 115
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-10
Table 7 continued. Lab Control Spike Results.
ETS-8-044.1 Internal Standard Calibration Analyzed 12/13/13
Lab ID
Spiked Concentration
(ng/mL)
PFBS
Calculated Concentration
(ng/mL)
LCS-131213-1 LCS-131213-2 LCS-131213-3 Average %RSD
LCS-131213-4 LCS-131213-5 LCS-131213-6 Average %RSD
0.198 0.198 0.198
1.98 1.98 1.98
0.213 0.206 0.218 107% 2.9%
2.25 2.24 2.25 114% 0.51%
LCS-131213-7 LCS-131213-8 LCS-131213-9 Average %RSD
19.9 19.9 19.9
21.6 21.0 20.7 106% 1.9%
%Recovery 108 104 110
114 113 114
108 106 104
Spiked Concentration
(ng/mL) 0.198 0.198 0.198
1.98 1.98 1.98
19.9 19.9 19.9
PFHS Calculated Concentration
(ng/mL)
0.205 0.198 0.208 103% 2.4%
2.34 2.29 2.35 118% 1.3%
21.7 21.6 20.8 107% 1.9%
%Recovery 103 100 105
118 116 119
109 108 105
ETS-8-044.1 Internal Standard Calibration Analyzed 12/13/13
Lab ID
PFOS (Linear + Branched)
Spiked
Calculated
Concentration Concentration
(ng/mL)
(ng/mL)
%Recovery
LCS-131213-1 LCS-131213-2 LCS-131213-3 Average %RSD
LCS-131213-4 LCS-131213-5 LCS-131213-6 Average %RSD
0.184 0.184 0.184
1.84 1.84 1.84
0.203 0.195 0.206 110% 2.9%
2.15 2.11 2.11 115% 1.3%
111 106 112
117 114 115
LCS-131213-7 LCS-131213-8 LCS-131213-9 Average %RSD
18.4 18.4 18.4
21.7 21.1 20.4 115% 3.1%
118 115 111
Spiked Concentration
(ng/mL)
PFOS surrogate
Calculated Concentration
(ng/mL)
0.189 0.189 0.189
0.216 0.209 0.219 113% 2.7%
1.89 2.15 1.89 2.08 1.89 2.16
113% 2.0%
%Recovery 114 110 116
114 110 114
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-10
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 (%) 8.37 8.78 7.69 10.4 7.68 7.99 9.94 8.42
Method Uncertainty 17% 18% 15% 21% 15% 16% 20% 17%
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, WW10R, WW11R
Trip Blank
Description Field Matrix Spike Field Matrix Spike Field Matrix Spike Field Matrix Spike Low Field Matrix Spike High Field Matrix Spike
Firial Concentr.tion (ng/mL
PFOA
PFBS
PFHS
PFOS
2480 4.96 4.96
2500 5.00 5.00
2510 5.00 5.00
2500 4.99 4.99
2480
2500
2510
2500
4.96 2480
5.00 2500
5.00 2510
4.99 2500
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-10
4 Data Summary and Discussion
The tables below summarize the sample results and field matrix spike recoveries for the seven 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. Relative percent 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 (5 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. ISO13-07-10
Table 10. DAL GW ACI 131118 (1)
3M LIMS ID
Description
ISO13-07-10-001
DAL-GW-ACI-0-131118
ISO13-07-10-002
DAL-GW-ACI-DB-131118
ISO13-07-10-003
DAL-GW-ACI-FMS-131118
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
2190
NA
2190
NA
4670
100
2190 ng/mL 0.0%
Concentration
(ng/mL)
%Recovery
1100
NA
1090
NA
3440
93.6
1100 ng/mL 0.91%
3M LIMS ID
Description
ISO13-07-10-001
DAL-GW-ACI-0-131118
ISO13-07-10-002
DAL-GW-ACI-DB-131118
ISO13-07-10-003
DAL-GW-ACI-FMS-131118
Average Concentration (ng/mL) %RPD
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
1320
NA
1340
NA
3840
100
1330 ng/mL 1.5%
Concentration
(ng/mL)
%Recovery
2260
NA
2220
NA
4700
98.4
2240 ng/mL 1.8%
13C4-PFOA
13C4-PFOS
3M LIMS ID
Description
ISO13-07-10-001
DAL-GW-ACI-0-131118
ISO13-07-10-002
DAL-GW-ACI-DB-131118
ISO13-07-10-003
DAL-GW-ACI-FMS-131118
Average Concentration (ng/mL) %RSD
%Recovery
107 107 111 108% 2.1%
%Recovery
108 109 112 110% 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 13 OF 24
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-10
Table 11. DAL GW ACM2 131118
3M LIMS ID
Description
ISO13-07-10-004
DAL-GW-ACM2-0-131118
ISO13-07-10-005
DAL-GW-ACM2-DB-131118
ISO13-07-10-006
DAL-GW-ACM2-FMS-131118
Average Concentration (ng/mL) %RPD
3M LIMS ID
Description
ISO13-07-10-004
DAL-GW-ACM2-0-131118
ISO13-07-10-005
DAL-GW-ACM2-DB-131118
ISO13-07-10-006
DAL-GW-ACM2-FMS-131118
Average Concentration (ng/mL) %RPD
PFOA (1)
PFBS (2)
Concentration
(ng/mL)
%Recovery
0.0539
NA
0.0527
NA
4.88 97.3
0.0533 ng/mL 2.3%
Concentration
(ng/mL)
%Recovery
1130
NA
1110
NA
1120
NC
1120 ng/mL 1.8%
PFHS (1)
PFOS (1)
Concentration
(ng/mL)
%Recovery
0.0728
NA
0.0670
NA
5.30 105
0.0699 ng/mL 8.3%
Concentration
(ng/mL)
%Recovery
0.206
NA
0.198
NA
5.41 104
0.202 ng/mL 4.0%
13C4-PFOA (1) 13C4-PFOS (1)
3M LIMS ID
Description
ISO13-07-10-004
DAL-GW-ACM2-0-131118
ISO13-07-10-005
DAL-GW-ACM2-DB-131118
ISO13-07-10-006
DAL-GW-ACM2-FMS-131118
Average Concentration (ng/mL) %RSD
%Recovery
105 110 105 107% 2.7%
%Recovery
106 108 106 107% 1.1%
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) Samples were analyzed by external standard calibration.
PAGE 14 OF 24
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-10
Table 12. DAL GW ACE 131118 (1)
3M LIMS ID
Description
ISO13-07-10-007
DAL-GW-ACE-0-131118
ISO13-07-10-008
DAL-GW-ACE-DB-131118
ISO13-07-10-009
DAL-GW-ACE-FMS-131118
Average Concentration (ng/mL) %RPD
3M LIMS ID
Description
ISO13-07-10-007
DAL-GW-ACE-0-131118
ISO13-07-10-008
DAL-GW-ACE-DB-131118
ISO13-07-10-009
DAL-GW-ACE-FMS-131118
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
0.511
NA
0.445
NA
5.37 98.6
0.478 ng/mL 14%
Concentration
(ng/mL)
%Recovery
0.620
NA
0.563
NA
5.56 99.4
0.592 ng/mL 9.6%
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
0.401
NA
0.331
NA
5.58 104
0.366 ng/mL 19%
Concentration
(ng/mL)
%Recovery
0.0979
NA
0.0472
NA
5.13 101
0.0726 ng/mL 70% (2)
13C4-PFOA
13C4-PFOS
3M LIMS ID
Description
ISO13-07-10-007
DAL-GW-ACE-0-131118
ISO13-07-10-008
DAL-GW-ACE-DB-131118
ISO13-07-10-009
DAL-GW-ACE-FMS-131118
Average Concentration (ng/mL) %RSD
%Recovery
106 105 109 107% 1.9%
%Recovery
104 105 106 105% 0.95%
NA = Not Applicable (1) Samples were analyzed by internal standard calibration. (2) Sample/sample duplicate RPD did not meet acceptance criteria of <20%.
PAGE 15 OF 24
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-10
Table 13. DAL GW WW8R 131118 (1)
3M LIMS ID
Description
ISO13-07-10-010
DAL-GW-WW8R-0-131118
ISO13-07-10-011
DAL-GW-WW8R-DB-131118
ISO13-07-10-012
DAL-GW-WW8R-FMS-131118
Average Concentration (ng/mL) %RPD
3M LIMS ID
Description
ISO13-07-10-010
DAL-GW-WW8R-0-131118
ISO13-07-10-011
DAL-GW-WW8R-DB-131118
ISO13-07-10-012
DAL-GW-WW8R-FMS-131118
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
3060
NA
3010
NA
5130
84.3
3040 ng/mL 1.6%
Concentration
(ng/mL)
%Recovery
363 NA
360 NA
2790
97.1
362 ng/mL 0.83%
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
1440
NA
1440
NA
3960
100
1440 ng/mL 0.0%
Concentration
(ng/mL)
%Recovery
4790
NA
4710
NA
7360
104
4750 ng/mL 1.7%
13C4-PFOA
13C4-PFOS
3M LIMS ID
Description
ISO13-07-10-010
DAL-GW-WW8R-0-131118
ISO13-07-10-011
DAL-GW-WW8R-DB-131118
ISO13-07-10-012
DAL-GW-WW8R-FMS-131118
Average Concentration (ng/mL) %RSD
%Recovery
101 96.6 97.3 98.3% 2.4%
%Recovery
111 109 109 110% 1.0%
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 24
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-10
Table 14. DAL GW WW9R 131118 (1)
3M LIMS ID
Description
ISO13-07-10-013
DAL-GW-WW9R-0-131118
ISO13-07-10-014
DAL-GW-WW9R-DB-131118
ISO13-07-10-015
DAL-GW-WW9R-FMS-131118
Average Concentration (ng/mL) %RPD
3M LIMS ID
Description
ISO13-07-10-013
DAL-GW-WW9R-0-131118
ISO13-07-10-014
DAL-GW-WW9R-DB-131118
ISO13-07-10-015
DAL-GW-WW9R-FMS-131118
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
2910
NA
2980
NA
5050
84.7
2950 ng/mL 2.4%
Concentration
(ng/mL)
%Recovery
301 NA
309 NA
2750
97.8
305 ng/mL 2.6%
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
1300
NA
1370
NA
3940
104
1340 ng/mL 5.2%
Concentration
(ng/mL)
%Recovery
4430
NA
4640
NA
7240
108
4540 ng/mL 4.6%
13C4-PFOA
13C4-PFOS
3M LIMS ID
Description
ISO13-07-10-013
DAL-GW-WW9R-0-131118
ISO13-07-10-014
DAL-GW-WW9R-DB-131118
ISO13-07-10-015
DAL-GW-WW9R-FMS-131118
Average Concentration (ng/mL) %RSD
%Recovery
98.4 98.7 93.8 97.0% 2.8%
%Recovery
110 112 107 110% 2.3%
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 17 OF 24
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-10
Table 15. DAL GW WW10R 131118 (1)
3M LIMS ID
Description
ISO13-07-10-016
DAL-GW-WW10R-0-131118
ISO13-07-10-017
DAL-GW-WW10R-DB-131118
ISO13-07-10-018
DAL-GW-WW10R-FMS-131118
Average Concentration (ng/mL) %RPD
3M LIMS ID
Description
ISO13-07-10-016
DAL-GW-WW10R-0-131118
ISO13-07-10-017
DAL-GW-WW10R-DB-131118
ISO13-07-10-018
DAL-GW-WW10R-FMS-131118
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
2410
NA
2380
NA
4530
85.9
2400 ng/mL 1.3%
Concentration
(ng/mL)
%Recovery
301 NA
304 NA
2790
99.5
303 ng/mL 0.99%
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
1120
NA
1120
NA
3690
102
1120 ng/mL 0.0%
Concentration
(ng/mL)
%Recovery
3940
NA
3840
NA
6390
100
3890 ng/mL 2.6%
13C4-PFOA
13C4-PFOS
3M LIMS ID
Description
ISO13-07-10-016
DAL-GW-WW10R-0-131118
ISO13-07-10-017
DAL-GW-WW10R-DB-131118
ISO13-07-10-018
DAL-GW-WW10R-FMS-131118
Average Concentration (ng/mL) %RSD
%Recovery
100 97.0 93.5 96.8% 3.4%
%Recovery
111 110 108 110% 1.4%
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 18 OF 24
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-10
Table 16. DAL GW WW11R 131118 (1)
3M LIMS ID
Description
ISO13-07-10-019
DAL-GW-WW11R-0-131118
ISO13-07-10-020
DAL-GW-WW11R-DB-131118
ISO13-07-10-021
DAL-GW-WW11R-FMS-131118
Average Concentration (ng/mL) %RPD
3M LIMS ID
Description
ISO13-07-10-019
DAL-GW-WW11 R-0-131118
ISO13-07-10-020
DAL-GW-WW11 R-DB-131118
ISO13-07-10-021
DAL-GW-WW11 R-FMS-131118
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
1300
NA
1330
NA
3620
92.7
1320 ng/mL 2.3%
Concentration
(ng/mL)
%Recovery
286 NA
288 NA
2810
101
287 ng/mL 0.70%
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
673 NA
687 NA
3220
101
680 ng/mL 2.1%
Concentration
(ng/mL)
%Recovery
1790
NA
1900
NA
4480
105
1850 ng/mL 5.9%
13c 4-p f o a
13c 4-p f o s
3M LIMS ID
Description
ISO13-07-10-019
DAL-GW-WW11 R-0-131118
ISO13-07-10-020
DAL-GW-WW11 R-DB-131118
ISO13-07-10-021
DAL-GW-WW11 R-FMS-131118
Average Concentration (ng/mL) %RSD
%Recovery
100 101 98.1 99.7% 1.5%
%Recovery
110 113 109 111% 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 19 OF 24
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-10
Table 17. Trip Blank Results
3M LIMS ID
ISO13-07-10-022 ISO13-07-10-023 ISO13-07-10-024
Description
DAL-GW-TRI P-0-131118 DAL-GW-TRIP-LS-131118 DAL-GW-TRIP-HS-131118
3M LIMS ID
ISO13-07-10-022 ISO13-07-10-023 ISO13-07-10-024
Description
DAL-GW-TRI P-0-131118 DAL-GW-TRI P-LS-131118 DAL-GW-TRIP-HS-131118
PFOA
PFBS
Concentration (ng/mL)
<0.0240 (1) 5.17 (2) 2710 (2)
%Recovery
NA 104 109
Concentration (ng/mL)
<0.0250 (1) 5.13 (2) 2490 (2)
%Recovery
NA 103 99.6
PFHS
PFOS
Concentration (ng/mL)
<0.0400 (1) 4.84 (2) 2530 (2)
%Recovery
NA 96.8 101
Concentration (ng/mL)
<0.0232 (1) 4.98 (2) 2650 (2)
%Recovery
NA 99.8 106
13C4-PFOA
13C4-PFOS
3M LIMS ID
ISO13-07-10-022 ISO13-07-10-023 ISO13-07-10-024
Description
DAL-GW-TRI P-0-131118 DAL-GW-TRI P-LS-131118 DAL-GW-TRIP-HS-131118
%Recovery
107 (1) 116 (2) 114 (2)
%Recovery
106 (1) 115 (2) 113 (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 20 OF 24
3M ENVIRONMENTAL LABORATORY REPORT NO. IS013-07-10
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 10-17 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(Ppincipal Analytical Investigator
Date
6>
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 A s s ig n e e Representative
Ihl M
Date
This test report shall not be reproduced except in full, without written approval of the 3M Environmental Laboratory.
PAGE 21 OF 24
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-10
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 1/17/2013 2/13/2013 3/27/2013 4/29/2013 5/31/2013 6/27/2013 7/23/2013 9/30/2013 10/28/2013 11/18/2013 PFOA 1910 2300 2220 1480 1860 1480 1630 2320 1880 2190 PFBS 588 830 1060 1360 1040 708 1230 356 1590 1100 PFHS 895 1580 1090 777 940 942 749 1400 866 1330 PFOS 1810 2940 2490 1670 2150 1590 1680 3240 2100 2240
ACE (Activated Carbon Effluent) - Sample Results in ng/mL
ACE 1/17/2013 2/13/2013 3/27/2013 4/29/2013 5/31/2013 6/27/2013 7/23/2013 9/30/2013 10/28/2013 11/18/2013
PFOA <0.0240
0.124 0.0380 0.0422 0.0725 0.0717 0.0643
0.115
0.231
0.478
PFBS <0.0250 0.0360 <0.0250 0.392
24.8
111 1960 1950 0.379 0.592
PFHS <0.0250 0.178 0.0477 0.057 0.105 0.118 0.0778 0.156 0.180 0.366
PFOS <0.0232 0.0329 <0.0232 <0.0232 <0.0232 <0.0232 0.0277 0.0452 0.0785 0.0726
PAGE 22 OF 24
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-10
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
1/17/2013 4350 410 1930 5710
2/13/2013 3250 354 1900 4850
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
7/23/2013 2640 263 1260 3910
9/30/2013 2890 303 1370 4100
10/28/2013 2830 312 1300 4410
110/18/2013 3040 362 1440 4750
WW9R - Sample Results in ng/mL
5000-
FC C harting fo r DAL_W W 9R
P F O A -------- --------PFOS------- --------
P F B S -------- ---------
P FH S --------
WW9R PFOA PFBS PFHS PFOS
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
7/23/2013 2410 212 1030 3670
9/30/2013 2730 249 1220 4200
10/28/2013 2820 286 1280 4380
11/18/2013 2950 305 1340 4540
PAGE 23 OF 24
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-10
Attachment A: Analyte Trend Data for select sampling points at the Decatur Ground Water Treatment Plant (GWTP) GAC System WW10R - Sample Results in ng/mL
WW10R PFOA PFBS PFHS PFOS
9/30/2013 2070 247 1030 2770
10/28/2013 2150 264 1030 3160
11/18/2013 2400 303 1120 3890
WW11R - Sample Results in ng/mL
WW11R PFOA PFBS PFHS PFOS
9/30/2013 1720 299 1000 2200
10/28/2013 1100 240 511 1670
11/18/2013 1320 287 680 1850
PAGE 24 OF 24
