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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-01
Final Report
Analysis of PFOA, PFBS, PFHS, and PFOS in Aqueous Samples from 3M Decatur, Alabama: Groundwater Treatment Plant GAC System January 2014
Laboratory Request Number: ISO14-07-01 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. ISO14-07-01
3M Environmental Laboratory 3M Environmental Laboratory Technical Director: William K. Reagen, Ph.D. 3M Principal Analytical Investigator: Susan Wolf Report Author: Kevin Eich
Analytical Report ISO14-07-01
3M Decatur Groundwater T reatment Plant System; January 2014 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 January 30, 2014. 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 ISO14-07-01. Analysis of the samples was completed as specified under 3M Environmental Laboratory General Project Outline (GPO) number GPO13-1289. 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. ISO14-07-01
Table 1. Sample Results Summary (1)
3M LIMS ID
Sample Description
ISO14-07-01-001 ISO14-07-01-002
ISO14-07-01-004 ISO14-07-01-005
ISO14-07-01-007 ISO14-07-01-008
ISO14-07-01-010 ISO14-07-01-011
ISO14-07-01-013 ISO14-07-01-014
ISO14-07-01-016 ISO14-07-01-017
ISO14-07-01-019 ISO14-07-01-020
DAL-GW-ACI-0-140130 DAL-GW-ACI-DB-140130
Average %RPD Sample/Sample Dup DAL-GW-ACM2-0-140130 DAL-GW-ACM2-DB-140130
Average %RPD Sample/Sample Dup DAL-GW-ACE-0-140130 DAL-GW-ACE-DB-140130
Average %RPD Sample/Sample Dup DAL-GW-WW8R-0-140130 DAL-GW-WW8R-DB-140130
Average %RPD Sample/Sample Dup DAL-GW-WW9R-0-140130 DAL-GW-WW9R-DB-140130
Average %RPD Sample/Sample Dup DAL-GW-WW10R-0-140130 DAL-GW-WW10R-DB-140130
Average %RPD Sample/Sample Dup DAL-GW-WW11R-0-140130 DAL-GW-WW11R-DB-140130
Average %RPD Sample/Sample Dup
PFOA Concentration
(ng/mL)
1550 1610 1580 3.8 0.336 0.320 0.328 (2) 4.9 0.495 0.485 0.490 (2) 2.0 2770 2550 2660 8.3 3090 2710 2900 13 1310 1340 1330 2.3 827 801 814 3.2
PFBS Concentration
(ng/mL)
192 211 202 9.4 2710 2620 2670 3.4 0.238 0.276 0.257 (2) 15 348 303 326 14 338 295 317 14 226 274 250 19 170 165 168 3.0
PFHS Concentration
(ng/mL)
861 829 845 3.8 0.253 0.212 0.233 (2) 18 0.230 0.207 0.219 (2) 11 1510 1400 1460 7.6 1500 1410 1460 6.2 752 762 757 1.3 362 361 362 0.28
PFOS Concentration
(ng/mL)
2670 2720 2700 1.9 1.99 1.84 1.92 (2) 7.8 0.210 0.208 0.209 (2) 0.96 4180 3790 3990 9.8 5050 4540 4800
11 1530 1600 1570 4.5 1570 1500 1540 4.6
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 11 %, PFBS 10%, PFHS 14%, and PFOS 9.0%. (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 16%, PFHS 17%, and PFOS 11 %.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-01
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 January 30, 2014 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 February 11,2014.
2.3 Sample Preparation
All samples were diluted with methanol 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 by removing a 0.4 mL aliquot of the well mixed sample and diluting it with 0.4 mL of methanol (dilution factor of 2). 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, Trip Blank sample and low spike 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
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-01
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 Buster
2/14/14 and 2/19/14
ETS-8-044.1 Agilent 1100 Betasil C18 (4.6 mm X 100 mm), 5 u Betasil C18 (4.6 mm X 100 mm), 5 u
10, 50 uL Applied Biosystems API 4000
Turbo Spray Negative
Analyst 1.6.1
Table 4. Liquid Chromatography Gradient Program.
Step Number
0 1 2 3 4 5 6 7 8 9
Total Time (min)
0.00 0.50 4.00 6.00 11.0 13.0 13.5 16.0 16.5 19.0
Flow Rate (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
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-01
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
402/99
499/99
PFOS
499/80
[13C8]PFOS
507/80
499/130
[13C4]PFOA surrogate
417/372
[13C8]PFOA
421/376
[13C4]PFOS surrogate
503/80
[13C8]PFOS
507/80
Dwell time was 50 msec for each transition. The individual transitions were summed to produce a "total ion chromatogram" (TIC), which was used for quantitation.
(1) Internal standards were used for the analysis on 2/19/14
3 Data Analysis
3.1 Calibration
External Standard Calibration Analysis on 2/14/14: 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 0.1 ng/mL to 150 ng/mL (nominal) were analyzed. The standards also contained the surrogates at concentrations ranging from 0.1 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 2/19/14: Samples were analyzed for all analytes against a matrix-matched stable isotope internal standard calibration curve. Calibration standards were prepared by spiking known amounts of stock solutions into 50 mL of 50:50 methanol:laboratory reagent water. The calibration standards contained an internal standard mix at a nominal concentration of 0.5 ng/mL. Calibration standards ranging from 0.0125 ng/mL to 100 ng/mL (nominal) were analyzed (0.0125 ng/mL to 10 ng/mL (nominal) for the SRSs). Low or high points may have been disabled to meet method criteria. 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. ISO14-07-01
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 with the following exceptions:
2/19/14 Analysis: The system suitability area count ratio exceeded 5% for PFBS (8.1%). A method deviation is included with the raw data.
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
LOQ, ng/mL 2/14/14 Analysis (1)
LOQ, ng/mL 1/9/14 Analysis (2)
PFOA
9.58
0.0240
PFBS
10.0
0.0250
PFHS
10.0
0.0250
PFOS
9.27
0.0232
(1) The dilution factor of 100 was applied to the LOQ.
(2) The dilution factor of 2 was 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
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LCS% RSD standard deviation LCS replicates 100% average LCS recovery
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-01
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-01
Table 7. Lab Control Spike Results.
ETS-8-044.1 External Standard Calibration Analyzed 2/14/14
Lab ID
PFOA (Linear + Branched)
Spiked
Calculated
Concentration Concentration
(ng/mL)
(ng/mL)
%Recovery
LCS-140214-1 LCS-140214-2 LCS-140214-3 Average %RSD
LCS-140214-4 LCS-140214-5 LCS-140214-6 Average %RSD
0.958 0.958 0.958
9.58 9.58 9.58
1.01 0.943 0.938 101% 4.5%
9.38 9.60 9.32 98.4% 1.4%
106 98.4 97.9
97.9 100 97.3
LCS-140214-7 LCS-140214-8 LCS-140214-9 Average %RSD
38.2 38.2 38.2
37.8 35.9 36.0 95.7% 3.0%
99.0 93.9 94.3
13C4-PFOA surrogate
Spiked Concentration
(ng/mL)
Calculated Concentration
(ng/mL)
%Recovery
0.998 0.998 0.998
1.11 1.01 1.16 110% 6.5%
111 102 116
9.98 10.8 9.98 10.5 9.98 10.6
106% 1.4%
108 105 106
ETS-8-044.1 External Standard Calibration Analyzed 2/14/14
Lab ID
Spiked Concentration
(ng/mL)
PFBS
Calculated Concentration
(ng/mL)
LCS-140214-1 LCS-140214-2 LCS-140214-3 Average %RSD LCS-140214-4 LCS-140214-5 LCS-140214-6 Average %RSD LCS-140214-7 LCS-140214-8 LCS-140214-9 Average %RSD
1.00 1.00 1.00
10.0 10.0 10.0
39.8 39.8 39.8
1.05 1.06 1.06 106% 0.55%
10.6 10.4 10.8 106% 1.9%
40.1 39.3 39.8 99.9% 1.2%
%Recovery 105 106 106
106 104 108
101 98.7 100
Spiked Concentration
(ng/mL) 1.00 1.00 1.00
10.0 10.0 10.0
39.8 39.8 39.8
PFHS Calculated Concentration
(ng/mL)
1.08 1.15 1.19 114% 4.9%
10.7 11.4 11.2 111% 3.2%
41.7 39.6 39.6 101% 3.2%
%Recovery 108 115 119
107 114 112
105 99.5 99.4
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-01
Table 7 continued. Lab Control Spike Results.
ETS-8-044.1 External Standard Calibration Analyzed 2/14/14
Lab ID
PFOS (Linear + Branched)
Spiked Concentration
(ng/mL)
Calculated Concentration
(ng/mL)
%Recovery
LCS-140214-1 LCS-140214-2 LCS-140214-3 Average %RSD
LCS-140214-4 LCS-140214-5 LCS-140214-6 Average %RSD
0.927 0.927 0.927
9.27 9.27 9.27
0.973 0.935 0.983 104% 2.5%
9.12 9.68 9.58 102% 2.9%
105 101 106
98.4 104 103
LCS-140214-7 LCS-140214-8 LCS-140214-9 Average %RSD
36.9 36.9 36.9
37.8 36.3 38.9 102% 3.2%
102 98.4 105
13C4-PFOS surrogate
Spiked Concentration
(ng/mL)
Calculated Concentration
(ng/mL)
%Recovery
0.956 0.956 0.956
1.13 1.19 1.11 120% 3.8%
119 125 116
9.56 10.8 9.56 11.5 9.56 11.2
117% 3.0%
113 120 117
ETS-8-044.1 Internal Standard Calibration Analyzed 2/19/14
Lab ID
PFOA (Linear + Branched)
Spiked Concentration
(ng/mL)
Calculated Concentration
(ng/mL)
%Recovery
LCS-140219-1 LCS-140219-2 LCS-140219-3 Average %RSD
LCS-140219-4 LCS-140219-5 LCS-140219-6 Average %RSD
0.190 0.190 0.190
9.50 9.50 9.50
0.186 0.190 0.205 102% 5.1%
11.1 10.2 11.4 115% 5.9%
98.1 100 108
117 107 120
LCS-140219-7 LCS-140219-8 LCS-140219-9 Average %RSD
38.0 38.0 38.0
41.9 38.9 39.4 105% 4.0%
110 102 104
13C4-PFOA surrogate
Spiked Concentration
(ng/mL)
Calculated Concentration
(ng/mL)
%Recovery
0.198 0.198 0.198
0.196 0.205 0.221 105% 5.8%
98.9 104 111
1.98 2.35 1.98 2.30 1.98 2.23
116% 2.6%
119 116 113
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-01
Table 7 continued. Lab Control Spike Results.
ETS-8-044.1 Internal Standard Calibration Analyzed 2/19/14
Lab ID
Spiked Concentration
(ng/mL)
PFBS
Calculated Concentration
(ng/mL)
LCS-140219-1 LCS-140219-2 LCS-140219-3 Average %RSD
LCS-140219-4 LCS-140219-5 LCS-140219-6 Average %RSD
0.198 0.198 0.198
9.92 9.92 9.92
0.212 0.211 0.209 106% 0.54%
10.9 9.60 10.7 105% 6.6%
LCS-140219-7 LCS-140219-8 LCS-140219-9 Average %RSD
39.6 39.6 39.6
38.9 41.0 39.5 100% 2.4%
%Recovery
107 106 106
Spiked Concentration
(ng/mL)
0.198 0.198 0.198
110 9.92 96.8 9.92 107 9.92
98.3 39.6 103 39.6 99.7 39.6
PFHS Calculated Concentration
(ng/mL)
0.235 0.193 0.214 108% 9.8%
11.2 10.9 11.3 112% 2.4%
38.8 48.5 46.5 112% 11%
%Recovery 119 97.7 108
113 109 114
98.0 122 117
ETS-8-044.1 Internal Standard Calibration Analyzed 2/19/14
Lab ID
PFOS (Linear + Branched)
Spiked Concentration
(ng/mL)
Calculated Concentration
(ng/mL)
%Recovery
LCS-140219-1 LCS-140219-2 LCS-140219-3 Average %RSD
LCS-140219-4 LCS-140219-5 LCS-140219-6 Average %RSD
0.184 0.184 0.184
9.20 9.20 9.20
0.214 0.202 0.213 114% 3.0%
11.0 9.84 9.64 110% 6.9%
116 110 116
119 107 105
LCS-140219-7 LCS-140219-8 LCS-140219-9 Average %RSD
36.7 36.7 36.7
39.3 41.4 41.8 111% 3.4%
107 113 114
13C4-PFOS surrogate
Spiked Concentration
(ng/mL)
Calculated Concentration
(ng/mL)
%Recovery
0.189 0.189 0.189
0.205 0.187 0.220 108% 8.0%
109 98.8 116
1.90 2.17 1.90 222 1.90 2.11
114% 2.6%
114 117 111
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-01
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 (%) 5.59 5.06 6.78 4.51 8.19 8.07 8.59 5.53
Method Uncertainty 11% 10% 14% 9.0% 16% 16% 17% 11%
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
1984 4.96 4.96
2000 5.00 5.00
2004 5.00 5.00
1996 4.99 4.99
2480 4.96 2480
2500 5.00 2500
2505 5.00 2505
2495 4.99 2495
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-01
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. ISO14-07-01
Table 10. DAL GW ACI 140130 (1)
3M LIMS ID
Sample Description
ISO14-07-01-001
DAL-GW-ACI-0-140130
ISO14-07-01-002 DAL-GW-ACI-DB-140130
ISO14-07-01-003 DAL-GW-ACI-FMS-140130
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
1550
NA
1610
NA
3000
71.6
1580 ng/mL 3.8%
Concentration
(ng/mL)
%Recovery
192 NA
211 NA
2310
105
202 ng/mL 9.4%
3M LIMS ID
Sample Description
ISO14-07-01-001
DAL-GW-ACI-0-140130
ISO14-07-01-002 DAL-GW-ACI-DB-140130
ISO14-07-01-003 DAL-GW-ACI-FMS-140130
Average Concentration (ng/mL) %RPD
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
861 NA
829 NA
2910
103
845 ng/mL 3.8%
Concentration
(ng/mL)
%Recovery
2670
NA
2720
NA
4890
110
2700 ng/mL 1.9%
13C4-PFOA
13C4-PFOS
3M LIMS ID
Sample Description
ISO14-07-01-001
DAL-GW-ACI-0-140130
ISO14-07-01-002 DAL-GW-ACI-DB-140130
ISO14-07-01-003 DAL-GW-ACI-FMS-140130
Average Concentration (ng/mL) %RSD
%Recovery
98.5 98.4 90.6 95.8% 4.7%
%Recovery
110 110 101 107% 4.6%
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.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-01
Table 11. DAL GW ACM2 140130
3M LIMS ID
Sample Description
ISO14-07-01-004 DAL-GW-ACM2-0-140130 ISO14-07-01-005 DAL-GW-ACM2-DB-140130 ISO14-07-01-006 DAL-GW-ACM2-FMS-140130
Average Concentration (ng/mL) %RPD
3M LIMS ID
Sample Description
ISO14-07-01-004 DAL-GW-ACM2-0-140130 ISO14-07-01-005 DAL-GW-ACM2-DB-140130 ISO14-07-01-006 DAL-GW-ACM2-FMS-140130
Average Concentration (ng/mL) %RPD
PFOA (1)
PFBS (2)
Concentration
(ng/mL)
%Recovery
0.336
NA
0.320
NA
5.17 97.6
0.328 ng/mL 4.9%
Concentration
(ng/mL)
%Recovery
2710
NA
2620
NA
2750
NC
2670 ng/mL 3.4%
PFHS (1)
PFOS (1)
Concentration
(ng/mL)
%Recovery
0.253
NA
0.212
NA
4.92 93.8
0.233 ng/mL 18%
Concentration
(ng/mL)
%Recovery
1.99 NA 1.84 NA 6.73 96.5 1.92 ng/mL 7.8%
13C4-PFOA (1) 13C4-PFOS (1) 13C4-PFOS (2)
3M LIMS ID
Sample Description
ISO14-07-01-004 DAL-GW-ACM2-0-140130 ISO14-07-01-005 DAL-GW-ACM2-DB-140130 ISO14-07-01-006 DAL-GW-ACM2-FMS-140130
Average Concentration (ng/mL) %RSD
%Recovery
79.2 84.1 100 87.8% 12%
%Recovery
97.3 97.4 99.1 97.9% 1.0%
%Recovery
112 108 116 112% 3.7%
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. The surrogate recovery standard 13C4-PFOS was added to the
samples during sample preparation.
PAGE 15 OF 25
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-01
Table 12. DAL GW ACE 140130 (1)
3M LIMS ID
Sample Description
ISO14-07-01-007 DAL-GW-ACE-0-140130 ISO14-07-01-008 DAL-GW-ACE-DB-140130 ISO14-07-01-009 DAL-GW-ACE-FMS-140130
Average Concentration (ng/mL) %RPD
3M LIMS ID
Sample Description
ISO14-07-01-007 DAL-GW-ACE-0-140130 ISO14-07-01-008 DAL-GW-ACE-DB-140130 ISO14-07-01-009 DAL-GW-ACE-FMS-140130
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
0.495
NA
0.485
NA
5.22 95.4
0.490 ng/mL 2.0%
Concentration
(ng/mL)
%Recovery
0.238
NA
0.276
NA
5.05 95.9
0.257 ng/mL 15%
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
0.230
NA
0.207
NA
5.32 102
0.219 ng/mL 11%
Concentration
(ng/mL)
%Recovery
0.210
NA
0.208
NA
5.36 103
0.209 ng/mL 0.96%
13C4-PFOA
13C4-PFOS
3M LIMS ID
Sample Description
ISO14-07-01-007 DAL-GW-ACE-0-140130 ISO14-07-01-008 DAL-GW-ACE-DB-140130 ISO14-07-01-009 DAL-GW-ACE-FMS-140130
Average Concentration (ng/mL) %RSD
%Recovery
94.5 80.9 86.3 87.2% 7.9%
%Recovery
79.8 80.6 99.8 86.7% 13%
NA = Not Applicable (1) Samples were analyzed by internal standard calibration.
PAGE 16 OF 25
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-01
Table 13. DAL GW WW8R 140130 (1)
3M LIMS ID
Sample Description
ISO14-07-01-010 DAL-GW-WW8R-0-140130
ISO14-07-01-011
DAL-GW-WW8R-DB-140130
ISO14-07-01-012 DAL-GW-WW8R-FMS-140130
Average Concentration (ng/mL) %RPD
3M LIMS ID
Sample Description
ISO14-07-01-010 DAL-GW-WW8R-0-140130
ISO14-07-01-011
DAL-GW-WW8R-DB-140130
ISO14-07-01-012 DAL-GW-WW8R-FMS-140130
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
2770
NA
2550
NA
5270
105
2660 ng/mL 8.3%
Concentration
(ng/mL)
%Recovery
348 NA
303 NA
3040
109
326 ng/mL 14%
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
1510
NA
1400
NA
4350
116
1460 ng/mL 7.6%
Concentration
(ng/mL)
%Recovery
4180
NA
3790
NA
7000
121
3990 ng/mL 9.8%
13C4-PFOA
13C4-PFOS
3M LIMS ID
Sample Description
ISO14-07-01-010 DAL-GW-WW8R-0-140130
ISO14-07-01-011
DAL-GW-WW8R-DB-140130
ISO14-07-01-012 DAL-GW-WW8R-FMS-140130
Average Concentration (ng/mL) %RSD
%Recovery
95.3 80.8 84.6 86.9% 8.7%
%Recovery
112 102 104 106% 4.8%
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 25
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-01
Table 14. DAL GW WW9R 140130 (1)
3M LIMS ID
Sample Description
ISO14-07-01-013 DAL-GW-WW9R-0-140130 ISO14-07-01-014 DAL-GW-WW9R-DB-140130 ISO14-07-01-015 DAL-GW-WW9R-FMS-140130
Average Concentration (ng/mL) %RPD
3M LIMS ID
Sample Description
ISO14-07-01-013 DAL-GW-WW9R-0-140130 ISO14-07-01-014 DAL-GW-WW9R-DB-140130 ISO14-07-01-015 DAL-GW-WW9R-FMS-140130
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
3090
NA
2710
NA
5450
103
2900 ng/mL 13%
Concentration
(ng/mL)
%Recovery
338 NA
295 NA
3000
107
317 ng/mL 14%
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
1500
NA
1410
NA
4210
110
1460 ng/mL 6.2%
Concentration
(ng/mL)
%Recovery
5050
NA
4540
NA
7580
112
4800 ng/mL 11%
13C4-PFOA
13C4-PFOS
3M LIMS ID
Sample Description
ISO14-07-01-013 DAL-GW-WW9R-0-140130 ISO14-07-01-014 DAL-GW-WW9R-DB-140130 ISO14-07-01-015 DAL-GW-WW9R-FMS-140130
Average Concentration (ng/mL) %RSD
%Recovery
86.6 83.6 86.6 85.6% 2.0%
%Recovery
107 102 96.9 102% 4.8%
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 25
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-01
Table 15. DAL GW WW10R 140130 (1)
3M LIMS ID
Sample Description
ISO14-07-01-016 DAL-GW-WW10R-0-140130 ISO14-07-01-017 DAL-GW-WW10R-DB140130 ISO14-07-01-018 DAL-GW-WW10R-FMS-140130
Average Concentration (ng/mL) %RPD
3M LIMS ID
Sample Description
ISO14-07-01-016 DAL-GW-WW10R-0-140130 ISO14-07-01-017 DAL-GW-WW10R-DB140130 ISO14-07-01-018 DAL-GW-WW10R-FMS-140130
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
1310
NA
1340
NA
3940
105
1330 ng/mL 2.3%
Concentration
(ng/mL)
%Recovery
226 NA
274 NA
3030
111
250 ng/mL 19%
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
752 NA
762 NA
3610
114
757 ng/mL 1.3%
Concentration
(ng/mL)
%Recovery
1530
NA
1600
NA
4160
104
1570 ng/mL 4.5%
13C4-PFOA
13C4-PFOS
3M LIMS ID
Sample Description
ISO14-07-01-016 DAL-GW-WW10R-0-140130 ISO14-07-01-017 DAL-GW-WW10R-DB140130 ISO14-07-01-018 DAL-GW-WW10R-FMS-140130
Average Concentration (ng/mL) %RSD
%Recovery
94.1 99.0 88.3 93.8% 5.7%
%Recovery
108 107 107 107% 0.56%
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 25
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-01
Table 16. DAL GW WW11R 140130 (1)
3M LIMS ID
Sample Description
ISO14-07-01-019 DAL-GW-WW11R-0-140130
ISO14-07-01-020 DAL-GW-WW11R-DB-140130
ISO14-07-01-021
DAL-GW-WW11R-FMS-140130
Average Concentration (ng/mL) %RPD
3M LIMS ID
Sample Description
ISO14-07-01-019 DAL-GW-WW11 R-0-140130
ISO14-07-01-020 DAL-GW-WW11R-DB-140130
ISO14-07-01-021
DAL-GW-WW11R-FMS-140130
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
827 NA
801 NA
3240
97.8
814 ng/mL 3.2%
Concentration
(ng/mL)
%Recovery
170 NA
165 NA
2850
107
168 ng/mL 3.0%
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
362 NA
361 NA
3020
106
362 ng/mL 0.28%
Concentration
(ng/mL)
%Recovery
1570
NA
1500
NA
4120
104
1540 ng/mL 4.6%
13C4-PFOA
13C4-PFOS
3M LIMS ID
Sample Description
ISO14-07-01-019 DAL-GW-WW11 R-0-140130
ISO14-07-01-020 DAL-GW-WW11R-DB-140130
ISO14-07-01-021
DAL-GW-WW11R-FMS-140130
Average Concentration (ng/mL) %RSD
%Recovery
94.4 88.9 80.4 87.9% 8.0%
%Recovery
116 103 92.6 104% 11%
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 20 OF 25
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-01
Table 17. Trip Blank Results
3M LIMS ID
ISO14-07-01-022 ISO14-07-01-023 ISO14-07-01-024
Sample Description
DAL-GW-TRI P-0-140130 DAL-GW-TRIP-LS-140130 DAL-GW-TRI P-HS-140130
3M LIMS ID
ISO14-07-01-022 ISO14-07-01-023 ISO14-07-01-024
Sample Description
DAL-GW-TRI P-0-140130 DAL-GW-TRI P-LS-140130 DAL-GW-TRI P-HS-140130
PFOA
PFBS
Concentration (ng/mL)
<0.0240 (1) 4.50 (1) 2310 (2)
%Recovery
NA 90.7 93.1
Concentration (ng/mL)
<0.0250 (1) 5.83 (1) 2470 (2)
%Recovery
NA 117 98.8
PFHS
PFOS
Concentration (ng/mL)
<0.0250 (1) 4.61 (1) 2550 (2)
%Recovery
NA 92.2 102
Concentration (ng/mL)
<0.0232 (1) 4.73 (1) 2550 (2)
%Recovery
NA 94.8 102
13C4-PFOA
13C4-PFOS
3M LIMS ID
ISO14-07-01-022 ISO14-07-01-023 ISO14-07-01-024
Sample Description
DAL-GW-TRI P-0-140130 DAL-GW-TRI P-LS-140130 DAL-GW-TRI P-HS-140130
%Recovery
84.6 (1) 91.7 (1) 84.8 (2)
%Recovery
108 (1) 91.2 (1) 97.8 (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 21 OF 25
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-01
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 the Decatur Ground Water Treatment Plant (GWTP) GAC System.
8 Signatures
Digitally signed by Susan T. Wolf DN: c=US, st=MN, l=St. Paul, ou=3M Environmental Laboratory - authenticated by LRA, email=stwolf@mmm.com, o=3M, cn=Susan T. Wolf Reason: I have reviewed this document Date: 2014.02.28 10:58:06 ~06'00'
Susan T. Wolf, 3M Principal Analytical Investigator
Digitally signed by William K. Reagen DN: c=US, st=MN, l=St. Paul, ou=Laboratory Director, ou=3M Environmental Laboratoryauthenticated by LRA, email=wkreagen@mmm.com, o=3M, cn=William K. Reagen Reason: I am approving this document Date: 2014.02.28 15:33:28 -06*00*
William K. Reagen, Ph.D., 3M Environmental Laboratory Technical Director
The 3M Environmental Laboratory's Quality Assurance Unit has audited the data and report for this project.
Digitally signed by Daryl K. Peterson DN: c=US, st=MN, l=St. Paul, ou=3M Environmental Laboratory - authenticated by LRA, email=dpeterson2@mmm.com, o=3M, cn=Daryl K. Peterson Reason: I am approving this document Date: 2014.03.03 07:52:31 ~06'00'
Quality Assurance Representative
This test report shall not be reproduced except in full, without written approval o f the 3M Environmental Laboratory.
PAGE 22 OF 25
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-01
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
2/13/13 2300 830 1580 2940
3/27/13 2220 1060 1090 2490
4/29/13 1480 1360 777 1670
5/31/13 1860 1040 940 2150
6/27/13 1480 708 942 1590
7/23/13 1630 1230 749 1680
9/30/13 2320 356 1400 3240
10/28/13 1880 1590 866 2100
11/18/13 2190 1100 1330 2240
12/13/13 1830 1350 695 1970
1/30/14 1580 202 845 2700
ACE (Activated Carbon Effluent) - Sample Results in ng/mL
ACE PFOA PFBS PFHS PFOS
2/13/13 0.124
0.0360 0.178
0.0329
3/27/13 0.0380
<0.0250 0.0477
<0.0232
4/29/13 0.0422 0.392 0.0570
<0.0232
5/31/13 0.0725 24.8 0.105
<0.0232
6/27/13 0.0717 111 0.118
<0.0232
7/23/13 0.0641 1960 0.0778 0.0277
9/30/13 0.115 1950 0.156
0.0452
10/28/13 0.231 0.379 0.180
0.0785
11/18/13 0.478 0.592 0.366
0.0726
12/13/13 0.0798 0.0766 0.0648 0.0303
1/30/14 0.490 0.257 0.219 0.209
PAGE 23 OF 25
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-01
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
2/13/13 3250 354 1900 4850
3/27/13 3640 385 1760 5120
4/29/13 3190 364 1610 4830
5/31/13 2760 289 1330 4180
WW9R - Sample Results in ng/mL
6/27/13 2760 282 1340 4110
7/23/13 2640 263 1260 3910
9/30/13 2890 303 1370 4100
10/28/13 2830 312 1300 4410
11/18/13 3040 362 1440 4750
12/13/13 2720 316 1270 4060
1/30/14 2660 326 1460 3990
W W 9R PFOA PFBS PFHS PFOS
2/13/13 2850 236 1400 4100
3/27/13 3330 278 1440 4660
4/29/13 2650 244 1200 4340
5/31/13 2660 226 1120 4210
6/27/13 2630 225 1140 4150
7/23/13 2410 212 1030 3670
9/30/13 2730 249 1220 4200
10/28/13 2820 286 1280 4380
11/18/13 2950 305 1340 4540
12/13/13 2690 259 1170 4190
1/30/14 2900 317 1460 4800
PAGE 24 OF 25
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO14-07-01
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
11/18/2013 2400 303 1120 3890
12/13/2013 1890 239 885 2920
1/30/2014 1330 250 757 1570
WW11R - Sample Results in ng/mL
W W 11R PFOA PFBS PFHS PFOS
9/30/2014 1720 299 1000 2200
10/28/2014 1100 240 511 1670
11/18/2014 1320 287 680 1850
12/13/2013 1060 198 512 1570
1/30/2014 814 168 362
1540
PAGE 25 OF 25
