Document 911VeZOrr9rGdLnXyj8VGBdn5
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-09
Final Report
Analysis of PFOA, PFBS, PFHS, and PFOS in Aqueous Samples from 3M Decatur, Alabama: Groundwater Treatment Plant GAC System October 2013
Laboratory Request Number: ISO13-07-09 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. ISO13-07-09
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 ISO13-07-09
3M Decatur Groundwater T reatment Plant System; October 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 October 28, 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 ISO13-07-09. 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. ISO13-07-09
Table 1. Sample Results Summary
3M LIMS ID
Sample Description
ISO13-07-09-001 ISO13-07-09-002
ISO13-07-09-004 ISO13-07-09-005
ISO13-07-09-007 ISO13-07-09-008
ISO13-07-09-010 ISO13-07-09-011
ISO13-07-09-013 ISO13-07-09-014
ISO13-07-09-019 ISO13-07-09-020
ISO13-07-09-022 ISO13-07-09-023
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)
1880 1870 1880 (1) 0.53 0.164 0.152 0.158 (2) 7.6 0.261 0.200 0.231 (2) 26 (3) 2970 2680 2830 (1) 10 2890 2740 2820 (1) 5.3 2110 2190 2150 (1) 3.7 1100 1090 1100 (1) 0.91
PFBS Concentration
(ng/mL)
1620 1560 1590 (1) 3.8 803 825 814 (1) 2.7 0.460 0.297 0.379 (2) 43 (3) 327 296 312 (1) 9.9 287 285 286 (1) 0.70 255 272 264 (1) 6.4 241 239 240 (1) 0.83
PFHS Concentration
(ng/mL)
873 858 866 (1) 1.7 0.289 0.273 0.281 (2) 5.7 0.198 0.161 0.180 (2) 21 (3) 1350 1250 1300 (1) 7.7 1290 1260 1280 (1) 2.3 1010 1040 1030 (1) 2.9 511 510 511 (1) 0.20
PFOS Concentration
(ng/mL)
2080 2120 2100 (1) 1.9 0.407 0.973 0.690 (2) 82 (3) 0.0785 <0.0232 0.0785 (2) NA 4580 4230 4410 (1) 7.9 4490 4260 4380 (1) 5.3 3080 3230 3160 (1) 4.7 1690 1650 1670 (1) 2.4
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 15%, PFBS 16%, PFHS 13%, and PFOS 15%. (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 16%, PFBS 14%, PFHS 19%, and PFOS 14%. (3) Sample/sample duplicate RPD did not meet acceptance criteria of <20%.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-09
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 October 28, 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 October 31,2013.
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.
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. ISO13-07-09
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 11/19/13 - external standard calibration 11/20/13 - 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 5, 20, or 40 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. ISO13-07-09
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 11/20/13.
3 Data Analysis
3.1 Calibration
External Standard Calibration Analysis on 11/19/13: 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 11/20/13: 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. ISO13-07-09
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
0.0192 (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. ISO13-07-09
Table 7. Lab Control Spike Results.
ETS-8-044.1 External Standard Calibration Analyzed 11/19/13
Lab ID
PFOA (Linear + Branched)
Spiked
Calculated
Concentration Concentration
(ng/mL)
(ng/mL)
%Recovery
LCS-131118-1 LCS-131118-2 LCS-131118-3 Average %RSD
LCS-131118-4 LCS-131118-5 LCS-131118-6 Average %RSD
0.191 0.191 0.191
4.74 4.74 4.74
0.210 0.209 0.220 111% 2.9%
5.49 5.41 5.37 114% 1.3%
110 109 115
116 114 113
LCS-131118-7 LCS-131118-8 LCS-131118-9 Average %RSD
38.2 38.2 38.2
38.7 39.8 39.3 103% 1.5%
101 104 103
Spiked Concentration
(ng/mL)
PFOA surrogate
Calculated Concentration
(ng/mL)
0.199 0.199 0.199
0.228 0.223 0.220 112% 2.2%
4.94 5.45 4.94 5.21 4.94 5.28
107% 2.4%
%Recovery 115 112 110
110 105 107
ETS-8-044.1 External Standard Calibration Analyzed 11/19/13
Lab ID
Spiked Concentration
(ng/mL)
PFBS
Calculated Concentration
(ng/mL)
LCS-131118-1 LCS-131118-2 LCS-131118-3 Average %RSD
LCS-131118-4 LCS-131118-5 LCS-131118-6 Average %RSD
LCS-131118-7 LCS-131118-8 LCS-131118-9 Average %RSD
0.199 0.199 0.199
4.95 4.95 4.95
39.8 39.8 39.8
0.226 0.223 0.223 113% 1.0%
5.70 5.54 5.51 113% 1.8%
40.8 41.8 41.0 103% 1.5%
%Recovery 114 112 112
115 112 111
102 105 103
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)
0.220 0.217 0.226 111% 2.4%
5.68 5.64 5.54 114% 1.3%
40.2 41.3 40.6 102% 1.5%
%Recovery 110 109 114
115 114 112
101 104 102
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-09
Table 7 continued. Lab Control Spike Results.
ETS-8-044.1 External Standard Calibration Analyzed 11/19/13
Lab ID
PFOS (Linear + Branched)
Spiked
Calculated
Concentration Concentration
(ng/mL)
(ng/mL)
%Recovery
LCS-131118-1 LCS-131118-2 LCS-131118-3 Average %RSD
LCS-131118-4 LCS-131118-5 LCS-131118-6 Average %RSD
0.185 0.185 0.185
4.59 4.59 4.59
0.221 0.209 0.220 117% 3.2%
5.53 5.41 5.43 119% 1.5%
120 113 119
121 118 118
LCS-131118-7 LCS-131118-8 LCS-131118-9 Average %RSD
36.9 36.9 36.9
39.0 40.0 39.1 107% 1.1%
106 108 106
Spiked Concentration
(ng/mL)
PFOS surrogate
Calculated Concentration
(ng/mL)
0.190 0.190 0.190
0.215 0.206 0.207 110% 2.4%
4.73 5.14 4.73 5.02 4.73 5.09
108% 1.4%
%Recovery 113 108 109
109 106 108
ETS-8-044.1 Internal Standard Calibration Analyzed 11/20/13
Lab ID
PFOA (Linear + Branched)
Spiked
Calculated
Concentration Concentration
(ng/mL)
(ng/mL)
%Recovery
LCS-131120-1 LCS-131120-2 LCS-131120-3 Average %RSD
LCS-131120-4 LCS-131120-5 LCS-131120-6 Average %RSD
0.190 0.190 0.190
1.90 1.90 1.90
0.179 0.167 0.190 94.0% 6.5%
1.91 1.95 1.93 102% 1.5%
94.3 87.7 99.9
100 103 102
LCS-131120-7 LCS-131120-8 LCS-131120-9 Average %RSD
19.0 19.0 19.0
18.6 18.6 17.7 96.4% 2.8%
97.8 98.1 93.2
Spiked Concentration
(ng/mL)
PFOA surrogate
Calculated Concentration
(ng/mL)
0.198 0.198 0.198
0.195 0.200 0.199 99.8% 1.4%
1.98 1.91 1.98 1.95 1.98 1.91
97.0% 1.3%
%Recovery 98.3 101 100
96.3 98.4 96.2
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-09
Table 7 continued. Lab Control Spike Results.
ETS-8-044.1 Internal Standard Calibration Analyzed 11/20/13
Lab ID
Spiked Concentration
(ng/mL)
PFBS
Calculated Concentration
(ng/mL)
LCS-131120-1 LCS-131120-2 LCS-131120-3 Average %RSD
LCS-131120-4 LCS-131120-5 LCS-131120-6 Average %RSD
0.198 0.198 0.198
1.98 1.98 1.98
0.185 0.182 0.204 96.0% 6.3%
2.14 2.14 2.10 107% 1.1%
LCS-131120-7 LCS-131120-8 LCS-131120-9 Average %RSD
19.9 19.9 19.9
19.5 19.2 18.4 95.7% 3.0%
%Recovery 93.3 91.8 103
108 108 106
98.2 96.3 92.5
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)
0.198 0.190 0.204 99.6% 3.5%
2.19 2.16 2.15 110% 1.0%
19.1 19.5 19.4 97.1% 0.99%
%Recovery 99.9 96.0 103
111 109 109
96.1 98.0 97.3
ETS-8-044.1 Internal Standard Calibration Analyzed 11/20/13
Lab ID
PFOS (Linear + Branched)
Spiked
Calculated
Concentration Concentration
(ng/mL)
(ng/mL)
%Recovery
LCS-131120-1 LCS-131120-2 LCS-131120-3 Average %RSD
0.184 0.184 0.184
0.181 0.175 0.188 98.4% 3.6%
98.2 95.0 102
LCS-131120-4 LCS-131120-5 LCS-131120-6 Average %RSD
LCS-131120-7 LCS-131120-8 LCS-131120-9 Average %RSD
1.84 1.84 1.84
18.4 18.4 18.4
1.95 1.97 1.92 106% 0.94%
18.6 18.0 17.8 98.5% 2.2%
106 107 105
101 97.7 96.9
Spiked Concentration
(ng/mL)
PFOS surrogate
Calculated Concentration
(ng/mL)
0.189 0.189 0.189
0.196 0.189 0.194 102% 2.0%
1.89 1.92 1.89 1.94 1.89 1.89
102% 1.5%
%Recovery 104 100 103
102 103 100
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-09
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 (%) 7.44 7.96 6.60 7.66 7.76 6.98 9.46 7.07
Method Uncertainty 15% 16% 13% 15% 16% 14% 19% 14%
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 4.95 4.95
2500 5.00 5.00
2510 5.00 5.00
2500 5.00 5.00
2480
2500
2510
2500
4.95 2480
5.00 2500
5.00 2510
5.00 2500
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-09
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. 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 (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. ISO13-07-09
Table 10. DAL GW ACI 131028 (1)
3M LIMS ID
Description
ISO13-07-09-001
DAL-GW-ACI-0-131028
ISO13-07-09-002
DAL-GW-ACI-DB-131028
ISO13-07-09-003
DAL-GW-ACI-FMS-131028
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
1880
NA
1870
NA
4090
89.1
1880 ng/mL 0.53%
Concentration
(ng/mL)
%Recovery
1620
NA
1560
NA
3740
86.0
1590 ng/mL 3.8%
3M LIMS ID
Description
ISO13-07-09-001
DAL-GW-ACI-0-131028
ISO13-07-09-002
DAL-GW-ACI-DB-131028
ISO13-07-09-003
DAL-GW-ACI-FMS-131028
Average Concentration (ng/mL) %RPD
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
873 NA
858 NA
3270
95.8
866 ng/mL 1.7%
Concentration
(ng/mL)
%Recovery
2080
NA
2120
NA
4500
96.0
2100 ng/mL 1.9%
13c 4-p f o a
13C4-PFOS
3M LIMS ID
Description
ISO13-07-09-001
DAL-GW-ACI-0-131028
ISO13-07-09-002
DAL-GW-ACI-DB-131028
ISO13-07-09-003
DAL-GW-ACI-FMS-131028
Average Concentration (ng/mL) %RSD
%Recovery
99.8 99.3 96.1 98.4% 2.0%
%Recovery
102 99.6 103 102% 1.7%
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 13 OF 24
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-09
Table 11. DAL GW ACM2 131028
3M LIMS ID
Description
ISO13-07-09-004
DAL-GW-ACM2-0-131028
ISO13-07-09-005
DAL-GW-ACM2-DB-131028
ISO13-07-09-006
DAL-GW-ACM2-FMS-131028
Average Concentration (ng/mL) %RPD
3M LIMS ID
Description
ISO13-07-09-004
DAL-GW-ACM2-0-131028
ISO13-07-09-005
DAL-GW-ACM2-DB-131028
ISO13-07-09-006
DAL-GW-ACM2-FMS-131028
Average Concentration (ng/mL) %RPD
PFOA (1)
PFBS (2)
Concentration
(ng/mL)
%Recovery
0.164
NA
0.152
NA
5.07 99.2
0.158 ng/mL 7.6%
Concentration
(ng/mL)
%Recovery
803 NA 825 NA 860 NC 814 ng/mL 2.7%
PFHS (1)
PFOS (1)
Concentration
(ng/mL)
%Recovery
0.289
NA
0.273
NA
5.34 101
0.281 ng/mL 5.7%
Concentration
(ng/mL)
%Recovery
0.407
NA
0.973
NA
5.89 104
0.690 ng/mL 82% (3)
13C4-PFOA (1) 13C4-PFOS (1)
3M LIMS ID
Description
ISO13-07-09-004
DAL-GW-ACM2-0-131028
ISO13-07-09-005
DAL-GW-ACM2-DB-131028
ISO13-07-09-006
DAL-GW-ACM2-FMS-131028
Average Concentration (ng/mL) %RSD
%Recovery
101 101 104 102% 1.7%
%Recovery
110 107 103 107% 3.3%
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. (3) Sample/sample duplicate RPD did not meet acceptance criteria of <20%.
PAGE 14 OF 24
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-09
Table 12. DAL GW ACE 131028 (1)
3M LIMS ID
Description
ISO13-07-09-007
DAL-GW-ACE-0-131028
ISO13-07-09-008
DAL-GW-ACE-DB-131028
ISO13-07-09-009
DAL-GW-ACE-FMS-131028
Average Concentration (ng/mL) %RPD
3M LIMS ID
Description
ISO13-07-09-007
DAL-GW-ACE-0-131028
ISO13-07-09-008
DAL-GW-ACE-DB-131028
ISO13-07-09-009
DAL-GW-ACE-FMS-131028
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
0.261
NA
0.200
NA
4.80 92.3
0.231 ng/mL 26% (2)
Concentration
(ng/mL)
%Recovery
0.460
NA
0.297
NA
5.38 100
0.379 ng/mL 43% (2)
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
0.198
NA
0.161
NA
5.37 104
0.180 ng/mL 21% (2)
Concentration
(ng/mL)
%Recovery
0.0785
NA
<0.0232
NA
5.35 105
0.0785 ng/mL
13C4-PFOA
13C4-PFOS
3M LIMS ID
Description
ISO13-07-09-007
DAL-GW-ACE-0-131028
ISO13-07-09-008
DAL-GW-ACE-DB-131028
ISO13-07-09-009
DAL-GW-ACE-FMS-131028
Average Concentration (ng/mL) %RSD
%Recovery
99.7 94.4 101 98.4% 3.6%
%Recovery
93.9 101 107 101% 6.5%
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. ISO13-07-09
Table 13. DAL GW WW8R 131028 (1)
3M LIMS ID
Description
ISO13-07-09-010
DAL-GW-WW8R-0-131028
ISO13-07-09-011
DAL-GW-WW8R-DB-131028
ISO13-07-09-012
DAL-GW-WW8R-FMS-131028
Average Concentration (ng/mL) %RPD
3M LIMS ID
Description
ISO13-07-09-010
DAL-GW-WW8R-0-131028
ISO13-07-09-011
DAL-GW-WW8R-DB-131028
ISO13-07-09-012
DAL-GW-WW8R-FMS-131028
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
2970
NA
2680
NA
5450
106
2830 ng/mL 10%
Concentration
(ng/mL)
%Recovery
327 NA
296 NA
2830
101
312 ng/mL 9.9%
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
1350
NA
1250
NA
3930
105
1300 ng/mL 7.7%
Concentration
(ng/mL)
%Recovery
4580
NA
4230
NA
7340
117
4410 ng/mL 7.9%
13C4-PFOA
13C4-PFOS
3M LIMS ID
Description
ISO13-07-09-010
DAL-GW-WW8R-0-131028
ISO13-07-09-011
DAL-GW-WW8R-DB-131028
ISO13-07-09-012
DAL-GW-WW8R-FMS-131028
Average Concentration (ng/mL) %RSD
%Recovery
101 99.8 100 100% 0.64%
%Recovery
108 108 102 106% 3.3%
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 24
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-09
Table 14. DAL GW WW9R 131028 (1)
3M LIMS ID
Description
ISO13-07-09-013
DAL-GW-WW9R-0-131028
ISO13-07-09-014
DAL-GW-WW9R-DB-131028
ISO13-07-09-015
DAL-GW-WW9R-FMS-131028
Average Concentration (ng/mL) %RPD
3M LIMS ID
Description
ISO13-07-09-013
DAL-GW-WW9R-0-131028
ISO13-07-09-014
DAL-GW-WW9R-DB-131028
ISO13-07-09-015
DAL-GW-WW9R-FMS-131028
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
2890
NA
2740
NA
5420
105
2820 ng/mL 5.3%
Concentration
(ng/mL)
%Recovery
287 NA
285 NA
2780
99.8
286 ng/mL 0.70%
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
1290
NA
1260
NA
3800
100
1280 ng/mL 2.3%
Concentration
(ng/mL)
%Recovery
4490
NA
4260
NA
7090
108
4380 ng/mL 5.3%
13C4-PFOA
13C4-PFOS
3M LIMS ID
Description
ISO13-07-09-013
DAL-GW-WW9R-0-131028
ISO13-07-09-014
DAL-GW-WW9R-DB-131028
ISO13-07-09-015
DAL-GW-WW9R-FMS-131028
Average Concentration (ng/mL) %RSD
%Recovery
103 99.4 103 102% 2.0%
%Recovery
104 106 97.6 103% 4.3%
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. ISO13-07-09
Table 15. DAL GW WW10R 131028 (1)
3M LIMS ID
Description
ISO13-07-09-019
DAL-GW-WW10R-0-131028
ISO13-07-09-020
DAL-GW-WW10R-DB-131028
ISO13-07-09-021
DAL-GW-WW10R-FMS-131028
Average Concentration (ng/mL) %RPD
3M LIMS ID
Description
ISO13-07-09-019
DAL-GW-WW10R-0-131028
ISO13-07-09-020
DAL-GW-WW10R-DB-131028
ISO13-07-09-021
DAL-GW-WW10R-FMS-131028
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
2110
NA
2190
NA
4520
95.6
2150 ng/mL 3.7%
Concentration
(ng/mL)
%Recovery
255 NA
272 NA
2670
96.2
264 ng/mL 6.4%
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
1010
NA
1040
NA
3490
98.0
1030 ng/mL 2.9%
Concentration
(ng/mL)
%Recovery
3080
NA
3230
NA
5710
102
3160 ng/mL 4.7%
13C4-PFOA
13C4-PFOS
3M LIMS ID
Description
ISO13-07-09-019
DAL-GW-WW10R-0-131028
ISO13-07-09-020
DAL-GW-WW10R-DB-131028
ISO13-07-09-021
DAL-GW-WW10R-FMS-131028
Average Concentration (ng/mL) %RSD
%Recovery
102 102 97.6 101% 2.5%
%Recovery
105 104 102 104% 1.5%
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. ISO13-07-09
Table 16. DAL GW WW11R 131028 (1)
3M LIMS ID
Description
ISO13-07-09-022
DAL-GW-WW11R-0-131028
ISO13-07-09-023
DAL-GW-WW11R-DB-131028
ISO13-07-09-024
DAL-GW-WW11R-FMS-131028
Average Concentration (ng/mL) %RPD
3M LIMS ID
Description
ISO13-07-09-022
DAL-GW-WW11 R-0-131028
ISO13-07-09-023
DAL-GW-WW11 R-DB-131028
ISO13-07-09-024
DAL-GW-WW11 R-FMS-131028
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
1100
NA
1090
NA
3380
91.9
1100 ng/mL 0.91%
Concentration
(ng/mL)
%Recovery
241 NA
239 NA
2560
92.8
240 ng/mL 0.83%
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
511 NA
510 NA
2860
93.6
511 ng/mL 0.20%
Concentration
(ng/mL)
%Recovery
1690
NA
1650
NA
4160
99.6
1670 ng/mL 2.4%
13C4-PFOA
13C4-PFOS
3M LIMS ID
Description
ISO13-07-09-022
DAL-GW-WW11 R-0-131028
ISO13-07-09-023
DAL-GW-WW11 R-DB-131028
ISO13-07-09-024
DAL-GW-WW11 R-FMS-131028
Average Concentration (ng/mL) %RSD
%Recovery
95.6 97.6 101 98.1% 2.8%
%Recovery
103 102 104 103% 0.97%
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. ISO13-07-09
Table 17. Trip Blank Results
3M LIMS ID
ISO13-07-09-016 ISO13-07-09-017 ISO13-07-09-018
Description
DAL-GW-TRIP01 -0-131028 DAL-GW-TRIP01 -LS-131028 DAL-GW-TRI P01-HS-131028
3M LIMS ID
ISO13-07-09-016 ISO13-07-09-017 ISO13-07-09-018
Description
DAL-GW-TRI P01-0-131028 DAL-GW-TRI P01-LS-131028 DAL-GW-TRI P01-HS-131028
PFOA
PFBS
Concentration (ng/mL)
<0.0240 (1) 5.23 (2) 2430 (2)
%Recovery
NA 106 98.0
Concentration (ng/mL)
<0.250 (1) 5.18 (2) 2390 (2)
%Recovery
NA 104 95.6
PFHS
PFOS
Concentration (ng/mL)
<0.400 (1) 5.05 (2) 2450 (2)
%Recovery
NA 101 97.6
Concentration (ng/mL)
<0.0232 (1) 5.27 (2) 2620 (2)
%Recovery NA 105 105
13C4-PFOA
13C4-PFOS
3M LIMS ID
ISO13-07-09-016 ISO13-07-09-017 ISO13-07-09-018
Description
DAL-GW-TRI P01-0-131028 DAL-GW-TRI P01-LS-131028 DAL-GW-TRI P01-HS-131028
%Recovery
111 (1) 107 (2) 107 (2)
%Recovery
111 (1) 110 (2) 106 (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. IS013-07-09
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 Principal Analytical Investigator
Date
William K. Reagen, Ph.D., 3M Environmental Laboratory Technical Director
M ct)/3
Date
The 3M Environmental Laboratory's Quality Assurance Unit has audited the data and report for this project.
This test report shall not be reproduced except In full, without written approval o f the 3M Environmental Laboratory.
PAGE 21 OF 24
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-09
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
12/14/2012 2580 723 1380 2810
1/17/2013 1910 588 895 1810
2/13/2013 2300 830 1580 2940
3/27/2013 2220 1060 1090 2490
4/29/2013 1480 1360 777 1670
5/31/2013 1860 1040 940 2150
6/27/2013 1480 708 942 1590
7/23/2013 1630 1230 749 1680
9/30/2013 2320 356 1400 3240
10/28/2013 1880 1590 866 2100
ACE (Activated Carbon Effluent) - Sample Results in ng/mL
ACE PFOA PFBS PFHS PFOS
12/14/2012 0.102
<0.0250 0.117
0.0376
1/17/2013 <0.0240 <0.0250 <0.0250 <0.0232
2/13/2013 0.124
0.0360 0.178
0.0329
3/27/2013 0.0380
<0.0250 0.0477
<0.0232
4/29/2013 0.0422 0.392 0.057
<0.0232
5/31/2013 0.0725 24.8 0.105
<0.0232
6/27/2013 0.0717 111 0.118
<0.0232
7/23/2013 0.0643 1960 0.0778 0.0277
9/30/2013 0.115 1950 0.156
0.0452
10/28/2013 0.231 0.379 0.180
0.0785
PAGE 22 OF 24
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-09
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
12/13/2012 3630 441 1740 4920
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
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 --------
W W 9R 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
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
PAGE 23 OF 24
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-09
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
W W 10R PFOA PFBS PFHS PFOS
9/30/2013 2070 247 1030 2770
10/28/2013 2150 264 1030 3160
WW11R - Sample Results in ng/mL
W W 11R PFOA PFBS PFHS PFOS
9/30/2013 1720 299 1000 2200
10/28/2013 1100 240 511 1670
PAGE 24 OF 24
