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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-03
Final Report
Analysis of PFOA, PFBS, PFHS, and PFOS in Aqueous Samples from 3M Decatur, Alabama: Groundwater Treatment Plant GAC System March 2013
Laboratory Request Number: ISO13-07-03 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.
Testing Cert #2052.01
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-03
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 IS13-07-03
3M Decatur Groundwater Treatment Plant System; March 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 March 27, 2013. Samples were returned to the 3M Environmental Laboratory for analysis of Perfluorooctanoate (PFOA), Perfluorobutane sulfonate (PFBS), Perfluorohexane sulfonate (PFHS), Perfluorooctane sulfonate (PFOS), and the surrogate recovery standards 13C4-PFOA and 13C4-PFOS under laboratory project number ISO13-07-03. Analysis of the samples was completed as specified under 3M Environmental Laboratory General Project Outline (GPO) number GPO11-1006. The 3M Environmental Laboratory provided sample containers for five sampling locations; ACI, ACM2, ACE, WW8R, and WW9R. The sample set consisted of a field sample, field sample duplicate and a field matrix spike. Each empty container was marked with a "fill to here" line that corresponded to a final volume of 200 mL. Containers reserved for field matrix spikes were fortified with an appropriate matrix spike solution containing all analytes prior to being sent to the field for sample collection. Sample bottles for sampling locations ACM2 and ACE, along with the Trip Blank sample and low spike, were fortified with internal standards and surrogates prior to being sent to the field for sample collection. Samples were prepared and analyzed by method ETS-8-044.1 "Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis". Select internal standards were used to aid in the data quality objectives. Table 1 summarizes the sample results using the analytical method identified above. All results for quality control samples prepared and analyzed with the samples will be reported and discussed elsewhere in this report.
The testing reported herein meet the requirements of ANSI/ISO/IEC 17025:2005 "General Requirements for the Competence of Testing and Calibration Laboratories", in accordance with the A2LA Testing Certificate # 2052.01.
Testing Cert #2052.01
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-03
Table 1. Sample Results Summary
3M LIMS ID
Sample Description
ISO13-07-03-001 ISO13-07-03-002
ISO13-07-03-004 ISO13-07-03-005
ISO13-07-03-007 ISO13-07-03-008
ISO13-07-03-010 ISO13-07-03-011
ISO13-07-03-013 ISO13-07-03-014
DAL-GW-ACI; Sample DAL-GW-ACI; Sample Dup
Average %RPD Sample/Sample Dup DAL-GW-ACM2; Sample DAL-GW-ACM2; Sample Dup
Average %RPD Sample/Sample Dup DAL-GW-ACE; Sample DAL-GW-ACE; Sample Dup
Average %RPD Sample/Sample Dup DAL-GW-WW8R; Sample DAL-GW-WW8R; Sample Dup
Average %RPD Sample/Sample Dup DAL-GW-WW9R; Sample DAL-GW-WW9R; Sample Dup
Average %RPD Sample/Sample Dup
PFOA Concentration
(ng/mL)
2190
2250 2220 (1)
2.7 52.9 50.9 51.9 (12) 3.9 0.0362 0.0398 0.0380 (3) 9.5 3660 3620 3640 (1) 1.1 3260 3400 3330 (1) 4.2
PFBS Concentration
(ng/mL)
1060
1060 1060 (1)
0.0 2300 2330 2320 (1,2) 1.3 <0.0250 <0.0250 <0.0250 (3) NA 380 389 385 (1) 2.3 273 283 278 (1) 3.6
PFHS Concentration
(ng/mL)
1080
1090 1090 (1)
0.92 170 171 171 (1,2)
0.59 0.0433 0.0521 0.0477 (3)
18 1760 1760 1760 (1) 0.0 1410 1470 1440 (1) 4.2
PFOS Concentration
(ng/mL)
2450
2520 2490 (1)
2.8 0.0509 0.0526 0.0518 (3)
3.3 <0.0232 <0.0232 <0.0232 (3)
NA 5170 5070 5120 (1) 2.0 4530 4780 4660 (1) 5.4
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 18%, PFBS 21 %, PFHS 15%, and PFOS 24%. (2) Sample did not have an appropriate FMS to access recovery. See section 4 for more details. (3) Reported results were prepared and analyzed by ETS-8-044.1 using internal standard calibration. The analytical method
uncertainties associated with the reported results are as follows: PFOA 16%, PFBS 22%, PFHS 14%, and PFOS 24%.
2 Methods - Analytical and Preparatory
2.1 Methods
Analysis was completed using 3M Environmental Laboratory Method ETS-8-044.1 "Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis".
Table 2 Target Analytes.
Target Analytes Perfluorooctanoic Acid (C8 Acid) Perfluorobutanesulfonate (C4 Sulfonate ) Perfluorohexanesulfonate (C6 Sulfonate) Perfluorooctanesulfonate (C8 Sulfonate)
Acronym PFOA PFBS PFHS PFOS
Reference Material Structure
Linear + Branched Linear Linear
Linear + Branched
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-03
2.2 Sample Collection
Samples were collected on March 27, 2013 in NalgeneTM (high-density polyethylene) bottles prepared at the 3M Environmental Laboratory. Prior to sample collection, bottles designated for field matrix spikes were spiked in the laboratory with a known volume of an appropriate matrix spiking solution containing PFOA, PFBS, PFHS, and PFOS. Sample bottles for sampling locations ACM2 and ACE, along with the Trip Blank sample and low spike, were fortified with a mixture of mass-labeled internal standards at a nominal concentration of 1 ng/mL and a mixture of surrogate recovery standards at a nominal concentration of 0.1 ng/mL. Collected sample bottles were received by the laboratory at ambient conditions on April 1,2013.
2.3 Sample Preparation
Sample sets ACI, ACM2, WW8R, WW9R, and the Trip Blank high spike were diluted 1:100 and analyzed for all analytes. The 1:100 dilutions were prepared by removing a 0.1 mL aliquot of the well mixed sample and adding 9.8 mL of methanol and 0.1 mL of a surrogate spiking solution. Prepared samples were analyzed by external standard calibration.
The ACE and ACM2 sample sets and the Trip Blank sample and low spike were prepared and analyzed for all analytes by transferring an aliquot of the well mixed sample into an autovial. Prepared samples were analyzed by internal standard calibration.
During the preparation of the laboratory control samples for internal standard calibration, an aliquot of a separate internal standard spiking solution was added to the laboratory control samples (nominal concentration of 1 ng/mL). The sample bottles for ACE, ACM2, and Trip Blank were spiked with an internal standard mix at a nominal concentration of 1 ng/mL prior to being sent to the field for sample collection. The laboratory control samples were analyzed in the same manner as the samples.
2.4 Analysis
All samples and quality control samples were analyzed for four target analytes using high performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS). Pertinent instrument parameters, the liquid chromatography gradient program, and the specific mass transitions analyzed are described in the tables below.
Due to the nature of the sample, the wide range of concentrations found in the sample, and the environmental occurrence of multiple isomers of the laboratory's analytes of interest, the software used for processing the analytical results is not able to consistently integrate the analytical peak, manual integration of the analytical peak is necessary. All manual integrations are performed following the procedures outlined in method ETS-12-010. The consistency of the laboratory's integration is ensured through the training of laboratory personnel, the peer review process required for all manual integrations, the review of manual integrations by the QAU, and where necessary the review of manual integrations by laboratory management.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-03
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 4/3/13 - external standard calibration
ETS-8-044.1 Agilent 1260 Betasil C18 (4.6 mm X 100 mm), 5 x Betasil C18 (4.6 mm X 100 mm), 5 x 2, 5, or 20 xL Applied Biosystems TripleQuad 5500 Turbo Spray
Negative Analyst 1.6.1
ETS Kirk 4/4/13 - internal standard calibration
ETS-8-044.1 Agilent 1260 Betasil C18 (4.6 mm X 100 mm), 5 x Betasil C18 (4.6 mm X 100 mm), 5 x
20 xL Applied Biosystems TripleQuad 5500
Turbo Spray Negative
Analyst 1.6.1
Table 4. Liquid Chromatography Gradient Program.
Step Number
0 1 2 3 4 5 6 7 8 9
Total Time (min)
0.00 0.50 4.00 6.00 11.0 13.0 13.5 16.0 16.5 19.0
Flow Rate (pL/min)
750 750 750 750 750 750 750 750 750 750
Percent A (2 m M ammonium acetate)
90.0 90.0 70.0 70.0 20.0 20.0 10.0 10.0 90.0 90.0
Percent B (Methanol)
10.0 10.0 30.0 30.0 80.0 80.0 90.0 90.0 10.0 10.0
Table 5. Mass Transitions
Analyte
Mass Transition Q1/Q3
Internal Standard (1)
Mass Transition Q1/Q3
413/369
PFOA
413/219
[13Cs]PFOA
421/376
413/169
PFBS
299/80 299/99
[1 8 O2 ]PFBS
303/84
PFHS
399/99 399/80
[13Cs]PFHS
402/80
499/99
PFOS
499/80
[13Cs]PFOS
507/80
499/130
[13C4]PFOA surrogate
417/372
[13Cs]PFOA
421/376
[13C4]PFOS surrogate
503/80
[13Cs]PFOS
507/80
Dwell time was 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 4/4/13.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-03
3 Data Analysis
3.1 Calibration
Internal Standard Calibration Analysis: Samples were analyzed against a matrix-matched stable isotope internal standard calibration curve. Calibration standards were prepared by spiking known amounts of stock solutions into 50 mL of laboratory prepared reagent water. The calibration standards contained an internal standard mix at a nominal concentration of 1 ng/mL. A total of thirteen calibration standards ranging from 0.025 ng/mL to 25 ng/mL (nominal) were analyzed with the prepared samples. Of these thirteen calibration standards, eleven contained the surrogates at concentrations ranging from 0.025 ng/mL to 10 ng/mL nominal. A quadratic, 1/x weighted, calibration curve of the ratio of the standard peak area counts over the internal standard peak area counts was used to fit the data for each analyte. The data were not forced through zero during the fitting process. Calculating the standard concentrations using the peak area ratios and the resultant calibration curve confirmed accuracy of each curve point. The reference standards of PFOA and PFOS used to prepare the calibration standards consisted of both linear and branched isomers. Each curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method calibration accuracy requirements of 10025% (10030% for the lowest curve point) were met for all analytes. The correlation coefficient (r) was greater than 0.995 for all analytes.
External Standard Calibration Analysis: Samples were analyzed against an external standard calibration curve. Calibration standards were prepared by spiking known amounts of the stock solution containing the target analytes into 90:10 methanol: Milli-Q laboratory water. A total of ten spiked standards ranging from 0.02 ng/mL to 25 ng/mL (nominal) were analyzed. The ten standards also contained the surrogates at concentrations ranging from 0.02 ng/mL to 25 ng/mL nominal. A quadratic, 1/x weighted, calibration curve of the standard peak area counts was used to fit the data for each analyte. The data were not forced through zero during the fitting process. Calculating the standard concentrations using the peak area counts and the resultant calibration curve confirmed accuracy of each curve point. Each curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method calibration accuracy requirements of 10025% (10030% for the lowest curve point) were met for all analytes. The correlation coefficient (r) was greater than 0.995 for all analytes.
3.2 System Suitability
A calibration standard was analyzed four times at the beginning of the analytical sequence to demonstrate overall system suitability. The acceptance criteria for system suitability samples is less than or equal to 5% relative standard deviation (RSD) for peak area/ratio and retention time criteria of less than or equal to 2% RSD. These criteria were met for all analytes.
3.3 Limit of Quantitation (LOQ)
The LOQ as defined in method ETS-8-044.1 is the lowest non-zero calibration standard in the curve that meets linearity and accuracy requirements and for which the area counts are at least twice those of the appropriate blanks. The LOQs associated with the sample analysis are listed in Table 6.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-03
Table 6. LOQ
Analyte PFOA PFBS PFHS PFOS PFOA PFBS PFHS PFOS
Calibration Internal standard Internal standard Internal standard Internal standard External standard External standard External standard External standard
LOQ, ng/mL 0.0240 0.0250 0.0250 0.0232
0.0192 (1) 0.0200 (1) 0.0200 (1) 0.0185 (1)
(1) The dilution factor was not applied to the LOQ.
3.4 Continuing Calibration
During the course of the analytical sequence, several continuing calibration verification samples (CCVs) were analyzed to confirm that the instrument response and the initial calibration curve were still in control. The method acceptance criteria of 100% 25% was met for all analytes.
3.5 Blanks
Two types of blanks were prepared and analyzed with the samples: method blanks/solvent blanks and field/trip blanks. Each blank result was reviewed and used to evaluate method performance to determine the LOQ for each analyte.
3.6 Lab Control Spikes (LCSs)
Low, mid, and high lab control spikes were prepared for the target analytes and analyzed in triplicate, while only low and high lab control spikes were prepared for the surrogates. LCSs were prepared by spiking known amounts of the analytes into either 10 mL of laboratory-prepared matrix matched water or 1 mL of Milli-Q water to produce the desired concentration. When applicable, the LCSs were then diluted with methanol in the same manner as the samples. Method ETS-8-044.1 states that the average recovery of LCSs at each spiking level be within 80%-120% with a RSD <20%. All LCS samples met method accuracy criteria except where noted below.
External standard analysis: Mid level LCSs did not meet average recovery criteria for PFBS (121%) and PFOS (122%). High level LCSs did not meet average recovery criteria PFOS (124%).
Internal standard analysis: Mid level LCSs did not meet average recovery criteria for PFOS (124%). High level LCSs did not meet average recovery criteria for PFBS (122%) and PFOS (122%).
A method deviation is included with the raw data. All LCSs were used in the determination of the analytical method uncertainty in section 3.9.
The following calculations were used to generate data in Table 7.
Calculated Concentration * ____ _ LCS Percent Recovery -------------------------------------* 100%
Spike Concentration
LCS% RSD = standard deviation LCS replicates * 1QQ% average LCS recovery
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-03
Table 7. Lab Control Spike Results.
ETS-8-044.1 External Standard Calibration Analyzed 4/3/13
Lab ID
PFOA (Linear + Branched)
Spiked
Calculated
Concentration Concentration
(ng/mL)
(ng/mL)
%Recovery
LCS-130403-1 LCS-130403-2 LCS-130403-3
Average %RSD
LCS-130403-4 LCS-130403-5 LCS-130403-6
Average %RSD
0.191 0.191 0.191
1.91 1.91 1.91
0.212 0.201 0.211 109% 3.0%
2.29 2.26 2.33 120% 1.7%
111 105 110
120 118 122
LCS-130403-7 LCS-130403-8 LCS-130403-9
Average %RSD
19.1 19.1 19.1
22.1 21.0 22.1 114% 3.0%
116 110 116
PFOS (Linear + Branched)
Spiked Concentration
(ng/mL)
Calculated Concentration
(ng/mL)
%Recovery
0.185 0.185 0.185
0.198 0.199 0.200 108% 0.54%
107 108 108
1.85 2.24 1.85 2.24 1.85 2.28
122% 0.95% (1)
121 121 123
18.5 23.0 18.5 22.3 18.5 23.5
124% 2.4% (1)
124 121 127
ETS-8-044.1 External Standard Calibration Analyzed 4/3/13
Lab ID
Spiked Concentration
(ng/mL)
PFBS
Calculated Concentration
(ng/mL)
LCS-130403-1 LCS-130403-2 LCS-130403-3
Average %RSD
LCS-130403-4 LCS-130403-5 LCS-130403-6
Average %RSD
LCS-130403-7 LCS-130403-8 LCS-130403-9
Average %RSD
0.199 0.199 0.199
1.99 1.99 1.99
20.0 20.0 20.0
0.221 0.219 0.223 111% 0.90%
2.39 2.41 2.45 121% 1.3% (1)
22.9 22.1 23.8 114% 3.9%
%Recovery 111 110 112
120 121 123
114 110 119
Spiked Concentration
(ng/mL) 0.199 0.199 0.199
1.99 1.99 1.99
20.0 20.0 20.0
PFHS Calculated Concentration
(ng/mL)
0.216 0.214 0.223 109% 2.1%
2.32 2.36 2.37 118% 0.98%
22.1 21.1 21.9 108% 2.4%
(1) LCSs did not meet acceptance criteria of 100 20%.
%Recovery 108 108 112
117 119 119
110 105 109
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-03
Table 7 continued. Lab Control Spike Results.
ETS-8-044.1 External Standard Calibration Analyzed 4/3/13
Lab ID
Spiked Concentration
(ng/mL)
PFOA surrogate
Calculated Concentration
(ng/mL)
LCS-130403-1 LCS-130403-2 LCS-130403-3
Average %RSD
LCS-130403-4 LCS-130403-5 LCS-130403-6
Average %RSD
0.199 0.199 0.199
1.99 1.99 1.99
0.202 0.206 0.208 103% 1.7%
2.09 2.13 2.12 106% 0.94%
%Recovery 101 104 104
105 107 106
Spiked Concentration
(ng/mL)
PFOS surrogate
Calculated Concentration
(ng/mL)
0.190 0.190 0.190
0.196 0.197 0.195 103% 0.0%
1.90 2.06 1.90 2.05 1.90 2.05
108% 0.53%
%Recovery 103 103 103
109 108 108
ETS-8-044.1 Internal Standard Calibration Analyzed 4/4/13
Lab ID
PFOA (Linear + Branched)
Spiked
Calculated
Concentration Concentration
(ng/mL)
(ng/mL)
%Recovery
LCS-130404-1 LCS-130404-2 LCS-130404-3
Average %RSD
LCS-130404-4 LCS-130404-5 LCS-130404-6
Average %RSD
0.190 0.190 0.190
1.90 1.90 1.90
0.205 0.202 0.197 106% 1.9%
2.25 2.21 2.23 117% 0.85%
108 106 104
118 116 117
LCS-130404-7 LCS-130404-8 LCS-130404-9
Average %RSD
9.52 9.52 9.52
10.5 11.8 12.0 120% 6.8%
111 124 126
PFOS (Linear + Branched)
Spiked Concentration
(ng/mL)
Calculated Concentration
(ng/mL)
%Recovery
0.184 0.184 0.184
0.217 0.215 0.218 118% 0.85%
118 117 119
1.84 2.35 1.84 2.17 1.84 2.32
124% 4.3% (1)
128 118 126
9.21 10.4 9.21 11.4 9.21 11.9
122% 6.7% (1)
113 124 129
(1) LCSs did not meet acceptance criteria of 100 20%.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-03
Table 7 continued. Lab Control Spike Results.
ETS-8-044.1 Internal Standard Calibration Analyzed 4/4/13
Lab ID
Spiked Concentration
(ng/mL)
PFBS
Calculated Concentration
(ng/mL)
LCS-130404-1 LCS-130404-2 LCS-130404-3
Average %RSD
LCS-130404-4 LCS-130404-5 LCS-130404-6
Average %RSD
0.198 0.198 0.198
1.98 1.98 1.98
0.215 0.221 0.217 110% 1.8%
2.34 2.34 2.44 120% 2.4%
LCS-130404-7 LCS-130404-8 LCS-130404-9
Average %RSD
9.94 9.94 9.94
11.3 12.5 12.6 122% 5.9% (1)
%Recovery 108 112 110
118 118 123
114 126 127
Spiked Concentration
(ng/mL) 0.198 0.198 0.198
1.98 1.98 1.98
9.94 9.94 9.94
PFHS Calculated Concentration
(ng/mL)
0.219 0.216 0.213 109% 1.4%
2.32 2.29 2.38 118% 1.8%
11.0 11.8 12.2 118% 5.2%
%Recovery 111 109 108
117 116 120
111 119 123
ETS-8-044.1 Internal Standard Calibration Analyzed 4/4/13
Lab ID
Spiked Concentration
(ng/mL)
PFOA surrogate
Calculated Concentration
(ng/mL)
LCS-130404-1 LCS-130404-2 LCS-130404-3
Average %RSD
0.198 0.198 0.198
0.191 0.189 0.186 95.3% 1.3%
LCS-130404-4 LCS-130404-5 LCS-130404-6
Average %RSD
1.98 1.98 1.98
1.95 2.01 2.00 101% 1.8%
%Recovery 96.4 95.5 93.9
98.5 102 101
Spiked Concentration
(ng/mL)
PFOS surrogate
Calculated Concentration
(ng/mL)
0.189 0.189 0.189
0.186 0.186 0.190 99.3% 1.5%
1.89 1.95 1.89 1.87 1.89 1.92
101% 2.2%
%Recovery 98.4 98.4 101
103 98.8 102
(1) LCSs did not meet acceptance criteria of 100 20%.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-03
3.7 Analytical Method Uncertainty
Analytical uncertainty is based on historical QC data that is control charted and used to evaluate method accuracy and precision. The method uncertainty is calculated following ETS-12-012.2. The standard deviation is calculated for the set of accuracy results (in %) obtained for the QC samples. The expanded uncertainty is calculated by multiplying the standard deviation by a factor of 2, which corresponds to a confidence level of 95%. The method uncertainty was determined to be 17% for PFBS and 16% for PFOS using internal calibration and 15% for PFBS and 20% for PFOS using external calibration, but based on the percent bias of the LCSs, the method uncertainty has been expanded for PFBS and PFOS.
Table 8. Analytical Method Uncertainty.
Analyte
Calibration Method
PFOA
External Standard
PFBS
External Standard
PFHS
External Standard
PFOS
External Standard
PFOA
Internal Standard
PFBS
Internal Standard
PFHS
Internal Standard
PFOS NA= Not Applicable
Internal Standard
Standard Deviation 8.86 NA 7.71 NA 8.02 NA 7.02 NA
Method Uncertainty 18% 21% 15% 24% 16% 22% 14% 24%
3.8 Field Matrix Spikes (FMS)
A field matrix spike was collected at each sampling point to verify that the analytical method is applicable to the collected matrix. Field matrix spikes are generated by adding a measured volume of field sample to a container spiked by the laboratory with the target analytes prior to shipping sample containers for sample collection. Field matrix spike recoveries within method acceptance criteria of 10030% confirm that "unknown" components in the sample matrix do not significantly interfere with the extraction and analysis of the analytes of interest. The standards used for the preparation of the field matrix spiking solutions contained reference materials comprised of both linear and branched isomers for PFOA and PFOS. Field matrix spikes are presented in section 4 of this report.
FMS Recovery - (Sample Concentration of FMS - Average Concentration: Field Sample & Field Sample Dup.) * 1 0 0 % Spike Concentraton
Table 9. Field Matrix Spike Concentrations
Location ACI ACM2, ACE WW8R, WW9R
Trip Blank
Description Field Matrix Spike Field Matrix Spike Field Matrix Spike Low Field Matrix Spike High Field Matrix Spike
Final Concentration (ng/mL
PFOA
PFBS
PFHS
PFOS
2110
1990
1970
2000
10.5
9.96
9.86
10.0
4220
3980
3940
4000
10.5
9.96
9.86
10.0
4220
3980
3940
4000
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-03
4 Data Summary and Discussion
The tables below summarize the sample results and field matrix spike recoveries for the three 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 (10 ng/mL) was not appropriate for PFOA, PFBS, or PFHS; however, the FMS sample for PFOS and the surrogate recovery standards 13C4-PFOA and 13C4-PFOS, met method acceptance criteria. No additional QC samples were prepared.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-03
Table 10. DAL GW ACI 130327 (1)
3M LIMS ID
Description
ISO13-07-03-001
DAL-GW-ACI-0-130327
ISO13-07-03-002 DAL-GW-ACI-DB-130327
ISO13-07-03-003 DAL-GW-ACI-FMS-130327
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
2190
NA
2250
NA
4210
94.3
2220 ng/mL 2.7%
Concentration
(ng/mL)
%Recovery
1060
NA
1060
NA
2930
94.0
1060 ng/mL 0.0%
3M LIMS ID
Description
ISO13-07-03-001
DAL-GW-ACI-0-130327
ISO13-07-03-002 DAL-GW-ACI-DB-130327
ISO13-07-03-003 DAL-GW-ACI-FMS-130327
Average Concentration (ng/mL) %RPD
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
1080
NA
1090
NA
2950
94.7
1090 ng/mL 0.92%
Concentration
(ng/mL)
%Recovery
2450
NA
2520
NA
4590
105
2490 ng/mL 2.8%
13C4-PFOA
13C4-PFOS
3M LIMS ID
Description
ISO13-07-03-001
DAL-GW-ACI-0-130327
ISO13-07-03-002
DAL-GW-ACI-DB-130327
ISO13-07-03-003
DAL-GW-ACI-FMS-130327
Average Concentration (ng/mL) %RSD
%Recovery
100 104 96.8 100% 3.7%
%Recovery
101 102 103 102% 0.91%
NA = Not Applicable (1) Samples were analyzed by external standard calibration. The surrogate recovery standards 13C4-PFOA and 13C4-PFOS were
added to the samples during sample preparation.
PAGE 13 OF 21
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-03
Table 11. DAL GW ACM2 130327
3M LIMS ID
Description
ISO13-07-03-004
DAL-GW-ACM2-0-130327
ISO13-07-03-005
DAL-GW-ACM2-DB-130327
ISO13-07-03-006
DAL-GW-ACM2-FMS-130327
Average Concentration (ng/mL) %RPD
3M LIMS ID
Description
ISO13-07-03-004
DAL-GW-ACM2-0-130327
ISO13-07-03-005
DAL-GW-ACM2-DB-130327
ISO13-07-03-006
DAL-GW-ACM2-FMS-130327
Average Concentration (ng/mL) %RPD
PFOA (1)
PFBS (1)
Concentration
(ng/mL)
%Recovery
52.9 NA 50.9 NA 61.9 NC 51.9 ng/mL 3.9%
Concentration
(ng/mL)
%Recovery
2300
NA
2330
NA
2320
NC
2320 ng/mL 1.3%
PFHS (1)
PFOS (2)
Concentration
(ng/mL)
%Recovery
170 NA 171 NA 176 NC 171 ng/mL 0.59%
Concentration
(ng/mL)
%Recovery
0.0509
NA
0.0526
NA
10.1 100
0.0518 ng/mL 3.3%
13c 4-p f o a (1) 13c 4-p f o s (2)
3M LIMS ID
Description
ISO13-07-03-004
DAL-GW-ACM2-0-130327
ISO13-07-03-005
DAL-GW-ACM2-DB-130327
ISO13-07-03-006
DAL-GW-ACM2-FMS-130327
Average Concentration (ng/mL) %RSD
%Recovery
103 103 103 103% 0.0%
%Recovery
94.1 98.5 94.7 95.8% 2.5%
NA = Not Applicable NC = Not Calculated; Spike level was less than 0.5x the endogenous sample concentration. (1) Samples were analyzed by external standard calibration. The surrogate recovery standards 13C4-PFOA and 13C4-PFOS were
added to the samples during sample preparation. (2) Samples were analyzed by internal standard calibration.
PAGE 14 OF 21
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-03
Table 12. DAL GW ACE 130327 (1)
3M LIMS ID
Description
ISO13-07-03-007
DAL-GW-ACE-0-130327
ISO13-07-03-008
DAL-GW-ACE-DB-130327
ISO13-07-03-009
DAL-GW-ACE-FMS-130327
Average Concentration (ng/mL) %RPD
3M LIMS ID
Description
ISO13-07-03-007
DAL-GW-ACE-0-130327
ISO13-07-03-008
DAL-GW-ACE-DB-130327
ISO13-07-03-009
DAL-GW-ACE-FMS-130327
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
0.0362
NA
0.0398
NA
10.2 96.4
0.0380 ng/mL 9.5%
Concentration
(ng/mL)
%Recovery
<0.0250
NA
<0.0250
NA
9.85 98.9
<0.0250 ng/mL
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
0.0433
NA
0.0521
NA
9.31 93.9
0.0477 ng/mL 18%
Concentration
(ng/mL)
%Recovery
<0.0232
NA
<0.0232
NA
10.4 104
<0.0232 ng/mL
13C4-PFOA
13C4-PFOS
3M LIMS ID
Description
ISO13-07-03-007
DAL-GW-ACE-0-130327
ISO13-07-03-008
DAL-GW-ACE-DB-130327
ISO13-07-03-009
DAL-GW-ACE-FMS-130327
Average Concentration (ng/mL) %RSD
%Recovery
102 105 104 104% 1.5%
%Recovery
112 110 107 109% 2.4%
NA = Not Applicable (1) Samples were analyzed by internal standard calibration.
PAGE 15 OF 21
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-03
Table 13. DAL GW WW8R 130327 (1)
3M LIMS ID
Description
ISO13-07-03-010
DAL-GW-WW8R-0-130327
ISO13-07-03-011
DAL-GW-WW8R-DB-130327
ISO13-07-03-012
DAL-GW-WW8R-FMS-130327
Average Concentration (ng/mL) %RPD
3M LIMS ID
Description
ISO13-07-03-010
DAL-GW-WW8R-0-130327
ISO13-07-03-011
DAL-GW-WW8R-DB-130327
ISO13-07-03-012
DAL-GW-WW8R-FMS-130327
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
3660
NA
3620
NA
7620
94.3
3640 ng/mL 1.1%
Concentration
(ng/mL)
%Recovery
380 NA
389 NA
4100
93.4
385 ng/mL 2.3%
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
1760
NA
1760
NA
5520
95.4
1760 ng/mL 0.0%
Concentration
(ng/mL)
%Recovery
5170
NA
5070
NA
9670
114
5120 ng/mL 2.0%
13C4-PFOA
13C4-PFOS
3M LIMS ID
Description
ISO13-07-03-010
DAL-GW-WW8R-0-130327
ISO13-07-03-011
DAL-GW-WW8R-DB-130327
ISO13-07-03-012
DAL-GW-WW8R-FMS-130327
Average Concentration (ng/mL) %RSD
%Recovery
96.0 94.6 93.4 94.7% 1.4%
%Recovery
101 101 96.0 99.3% 2.9%
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 16 OF 21
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-03
Table 14. DAL GW WW9R 130327 (1)
3M LIMS ID
Description
ISO13-07-03-013
DAL-GW-WW9R-0-130327
ISO13-07-03-014
DAL-GW-WW9R-DB-130327
ISO13-07-03-015
DAL-GW-WW9R-FMS-130327
Average Concentration (ng/mL) %RPD
3M LIMS ID
Description
ISO13-07-03-013
DAL-GW-WW9R-0-130327
ISO13-07-03-014
DAL-GW-WW9R-DB-130327
ISO13-07-03-015
DAL-GW-WW9R-FMS-130327
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
3260
NA
3400
NA
7570
100
3330 ng/mL 4.2%
Concentration
(ng/mL)
%Recovery
273 NA
283 NA
4260
100
278 ng/mL 3.6%
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
1410
NA
1470
NA
5470
102
1440 ng/mL 4.2%
Concentration
(ng/mL)
%Recovery
4530
NA
4780
NA
9070
110
4660 ng/mL 5.4%
13C4 -PFOA
13C4 -PFOS
3M LIMS ID
Description
ISO13-07-03-013
DAL-GW-WW9R-0-130327
ISO13-07-03-014
DAL-GW-WW9R-DB-130327
ISO13-07-03-015
DAL-GW-WW9R-FMS-130327
Average Concentration (ng/mL) %RSD
%Recovery
102 105 96.3 101% 4.5%
%Recovery
103 106 101 103% 2.2%
NA = Not Applicable (1) Samples were analyzed by external standard calibration. The surrogate recovery standards 13C4-PFOA and 13C4-PFOS were
added to the samples during sample preparation.
PAGE 17 OF 21
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-03
Table 15. Trip Blank Results
3M LIMS ID
ISO13-07-03-016 ISO13-07-03-017 ISO13-07-03-018
Description
DAL-GW-TRIP01 -0 DAL-GW-TRIP01 -LS DAL-GW-TRI P01-HS
3M LIMS ID
ISO13-07-03-016 ISO13-07-03-017 ISO13-07-03-018
Description
DAL-GW-TRI P01-0 DAL-GW-TRI P01-LS DAL-GW-TRI P01-HS
PFOA
PFBS
Concentration (ng/mL)
<0.0240 (1) 10.2 (1) 4360 (2)
%Recovery
NA 96.4 103
Concentration (ng/mL)
<0.0250 (1) 9.60 (1) 4070 (2)
%Recovery
NA 96.4 102
PFHS
PFOS
Concentration (ng/mL)
<0.0250 (1) 9.10 (1) 4020 (2)
%Recovery
NA 92.3 102
Concentration (ng/mL)
<0.0232 (1) 9.44 (1) 4650 (2)
%Recovery NA 94.4 116
13C4 -PFOA
13C4 -PFOS
3M LIMS ID
ISO13-07-03-016 ISO13-07-03-017 ISO13-07-03-018
Description
DAL-GW-TRI P01-0 DAL-GW-TRI P01-LS DAL-GW-TRI P01-HS
%Recovery
94.9 (1) 91.0 (1) 102 (2)
NA = Not Applicable (1) Samples were analyzed by internal standard calibration. (2) Samples were analyzed by external standard calibration.
%Recovery
98.5 (1) 94.0 (1) 105 (2)
PAGE 18 OF 21
3M ENVIRONMENTAL LABORATORY REPORT NO. IS013-07-03
5 Conclusion
Laboratory control spikes were used to determine the analytical method accuracy and precision for all analytes. The accuracy and precision were then used to estimate the method uncertainty for the results. Field matrix spike recoveries demonstrated that the analytical method was appropriate for the given sample matrix. Analysis was completed using 3M Environmental Laboratory Method ETS-8044.1 "Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis". Analytical results are reported in Table 1 and 10-15 of this report.
6 Data / Sample Retention
All remaining sample and associated project data (hardcopy and electronic) will be archived according to 3M Environmental Laboratory standard operating procedures.
7 Attachments
Attachment A: Analyte Trend Data for select sampling points at the Decatur Ground W ater Treatment Plant (GWTP) GAC System.
8 Signatures
Susan T. Wolf, 3M Qjncipal Analytical Investigator
Date
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.
Ol^ J Quality Assurance Represent!ative
/
Date
This test report shall not be reproduced except in full, without written approval of the 3M Environmental Laboratory.
PAGE 19 OF 21
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-03
Attachment A: Analyte Trend Data for select sampling points at the Decatur Ground Water Treatment Plant (GWTP) GAC System ACI (Activated Carbon Influent) - Sample Results in ng/mL
ACI PFOA PFBS PFHS PFOS
6/17/2011 1410 1110 983 691
2/8/2012 1180 792 1100 782
6/29/2012 1650 1410 1460 964
8/28/2012 1410 1830 1390 172
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
ACE (Activated Carbon Effluent) - Sample Results in ng/mL
ACE PFOA PFBS PFHS PFOS
6/17/2011 2.57 11.9 2.50 2.07
2/8/2012 1250 818 1240 741
8/28/2012 0.387 0.256 0.552 0.103
The ACE location was not sampled on 6/29/12.
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 0.0124 0.0360 0.178 0.0329
3/27/2013 0.0380
<0.0250 0.0477
<0.0232
PAGE 20 OF 21
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-03
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
WW9R - Sample Results in ng/mL
3/27/2013 3640 385 1760 5120
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
PAGE 21 OF 21
