Document 85L0K7n5Bn4KdeEYVOMbmNZvZ
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-02
Final Report
Analysis of PFOA, PFBS, PFHS, and PFOS in Aqueous Samples from 3M Decatur, Alabama: Groundwater Treatment Plant GAC System February 2013
Laboratory Request Number: ISO13-07-02 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 that complies with this International Standard also meets principles of ISO 9001:2000.
Testing Cert #2052.01
PAGE 1 OF 20
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-02
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 ISO13-07-02
3M Decatur Groundwater T reatment Plant System; February 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 February 13, 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 ISO13-07-02. 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 that complies with this International Standard also meets principles of ISO 9001:2000.
Testing Cert #2052.01
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-02
Table 1. Sample Results Summary
3M LIMS ID
Sample Description
ISO13-07-02-001 ISO13-07-02-002
ISO13-07-02-004 ISO13-07-02-005
ISO13-07-02-007 ISO13-07-02-008
ISO13-07-02-010 ISO13-07-02-011
ISO13-07-02-013 ISO13-07-02-014
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)
2250
2350 2300 (1)
4.3 <0.0240 0.0320 0.0320 (2)
NA (4) 0.126 0.121 0.124 (2)
4.0 3240 3260 3250 (1) 0.62 2840 2860 2850 (1) 0.70
PFBS Concentration
(ng/mL)
826
833 830 (1) 0.84 1680 1660 1670 (13)
1.2 0.0372 0.0348 0.0360 (2)
6.7 357 350 354 (1) 2.0 232 239 236 (1) 3.0
PFHS Concentration
(ng/mL)
1550
1600 1580 (1)
3.2 0.0417 0.0802 0.0610 (2) 63 (5) 0.170 0.185 0.178 (2)
8.5 1920 1870 1900 (1) 2.6 1420 1370 1400 (1) 3.6
PFOS Concentration
(ng/mL)
2950
2930 2940 (1)
0.68 0.120 0.0726 0.0963 (2) 49 (5) 0.0381 0.0276 0.0329 (2) 32 (5) 4860 4830 4850 (1) 0.62 4130 4060 4100 (1)
1.7
NA = Not Applicable (1) Reported results were prepared and analyzed by ETS-8-044.1 using external calibration. The analytical method uncertainties
associated with the reported results are as follows: PFOA 16%, PFBS 12%, PFHS 11 %, and PFOS 16%. (2) Reported results were prepared and analyzed by ETS-8-044.1 using internal calibration. The analytical method uncertainties
associated with the reported results are as follows: PFOA 22%, PFBS 23%, PFHS 22%, and PFOS 19%. (3) Sample did not have an appropriate FMS to access recovery. See section 4 for more details. (4) Sample/sample duplicate RPD could not be determined since the initial sample concentration was BLOQ. (5) Sample/sample duplicate RPD did not meet acceptance criteria of <20%.
2 Methods - Analytical and Preparatory
2.1 Methods
Analysis was completed using 3M Environmental Laboratory Method ETS-8-044.1 "Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis".
Table 2 Target Analytes.
Target Analytes Perfluorooctanoic Acid (C8 Acid) Perfluorobutanesulfonate (C4 Sulfonate ) Perfluorohexanesulfonate (C6 Sulfonate) Perfluorooctanesulfonate (C8 Sulfonate)
Acronym PFOA PFBS PFHS PFOS
Reference Material Structure
Linear + Branched Linear Linear
Linear + Branched
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-02
2.2 Sample Collection
Samples were collected on February 13, 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 February 15, 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. Further dilution may have been applied by using a lower injection volume on the instrument.
The ACE sample set and the Trip Blank sample and low spike were prepared and analyzed for all analytes 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). The ACM2 sample set was re-analyzed using a 1:2 dilution. Prepared samples were analyzed by internal standard calibration.
During the preparation of the laboratory control samples for internal 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. ISO13-07-02
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 2/26/13 - external calibration
ETS-8-044.1 Agilent 1100 Betasil C18 (4.6 mm X 100 mm), 5 x Betasil C18 (4.6 mm X 100 mm), 5 x
5 or 20 xL Applied Biosystems API 4000
Turbo Spray Negative
Analyst 1.6.1
ETS Buster 2/28/13 - internal calibration
ETS-8-044.1 Agilent 1100 Betasil C18 (4.6 mm X 100 mm), 5 x Betasil C18 (4.6 mm X 100 mm), 5 x
25 xL 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 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 2/28/13.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-02
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 synthetic groundwater. 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. O f 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 twelve spiked standards ranging from 0.02 ng/mL to 100 ng/mL (nominal) were analyzed. Of these twelve calibration standards, ten 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 the table below.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-02
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 (2) 0.0200 (2) 0.0200 (2) 0.0185 (2)
(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.
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. ISO13-07-02
Table 7. Lab Control Spike Results.
ETS-8-044.1 External Standard Calibration Analyzed 2/26/13
Lab ID
PFOA (Linear + Branched)
Spiked
Calculated
Concentration Concentration
(ng/mL)
(ng/mL)
%Recovery
LCS-130226-1 LCS-130226-2 LCS-130226-3 Average %RSD
LCS-130226-4 LCS-130226-5 LCS-130226-6 Average %RSD
0.479 0.479 0.479
4.79 4.79 4.79
0.472 0.472 0.476 98.9% 0.53%
4.95 5.02 4.92 104% 1.1%
98.6 98.6 99.5
103 105 103
LCS-130226-7 LCS-130226-8 LCS-130226-9 Average %RSD
19.1 19.1 19.1
20.0 19.7 20.1 104% 1.1%
105 103 105
PFOS (Linear + Branched)
Spiked Concentration
(ng/mL)
Calculated Concentration
(ng/mL)
%Recovery
0.464 0.464 0.464
0.492 0.492 0.490 106% 0.0%
106 106 106
4.64 5.12 4.64 5.15 4.64 5.17
111% 0.52%
110 111 111
18.5 20.6 18.5 20.5 18.5 21.3
112% 2.1%
111 111 115
ETS-8-044.1 External Standard Calibration Analyzed 2/26/13
Lab ID
Spiked Concentration
(ng/mL)
PFBS
Calculated Concentration
(ng/mL)
LCS-130226-1 LCS-130226-2 LCS-130226-3 Average %RSD
LCS-130226-4 LCS-130226-5 LCS-130226-6 Average %RSD
LCS-130226-7 LCS-130226-8 LCS-130226-9 Average %RSD
0.500 0.500 0.500
5.00 5.00 5.00
20.0 20.0 20.0
0.498 0.494 0.487 98.6% 1.1%
5.16 5.16 5.12 103% 0.56%
20.4 20.3 21.2 103% 2.6%
%Recovery 99.6 98.7 97.4
103 103 102
102 101 106
Spiked Concentration
(ng/mL) 0.500 0.500 0.500
5.00 5.00 5.00
20.0 20.0 20.0
PFHS Calculated Concentration
(ng/mL)
0.496 0.500 0.492 99.2% 0.76%
5.17 5.15 5.19 103% 0.56%
19.9 19.7 20.1 99.7% 1.2%
%Recovery 99.1 100 98.5
103 103 104
99.3 98.7 101
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-02
Table 7 continued. Lab Control Spike Results.
ETS-8-044.1 External Standard Calibration Analyzed 2/26/13
Lab ID
Spiked Concentration
(ng/mL)
PFOA surrogate
Calculated Concentration
(ng/mL)
LCS-130226-1 LCS-130226-2 LCS-130226-3 Average %RSD
LCS-130226-4 LCS-130226-5 LCS-130226-6 Average %RSD
0.499 0.499 0.499
4.99 4.99 4.99
0.496 0.488 0.496 98.9% 0.96%
4.43 4.65 4.71 92.1% 3.2%
%Recovery 99.4 97.8 99.5
88.8 93.2 94.4
Spiked Concentration
(ng/mL)
PFOS surrogate
Calculated Concentration
(ng/mL)
0.478 0.478 0.478
0.470 0.502 0.490 102% 3.4%
4.78 4.71 4.78 4.74 4.78 4.76
99.1% 0.52%
%Recovery 98.3 105 103
98.5 99.2 99.5
ETS-8-044.1 Internal Standard Calibration Analyzed 2/28/13
Lab ID
PFOA (Linear + Branched)
Spiked
Calculated
Concentration Concentration
(ng/mL)
(ng/mL)
%Recovery
LCS-130227-1 LCS-130227-2 LCS-130227-3 Average %RSD
LCS-130227-4 LCS-130227-5 LCS-130227-6 Average %RSD LCS-130227-7 LCS-130227-8 LCS-130227-9 Average %RSD
0.190 0.190 0.190
1.90 1.90 1.90
9.52 9.52 9.52
0.189 0.191 0.186 99.6% 1.4%
1.91 1.95 1.92 102% 1.1%
9.66 9.40 8.91 97.8% 3.9%
99.6 101 98.2
101 103 101
101 98.7 93.6
PFOS (Linear + Branched)
Spiked Concentration
(ng/mL)
Calculated Concentration
(ng/mL)
%Recovery
0.184 0.184 0.184
0.192 0.189 0.215 108% 7.2%
104 103 117
1.84 1.84 1.84 1.85 1.84 1.84
100% 0.058%
99.9 100 100
9.21 9.76 106 9.21 8.90 96.6 9.21 9.51 103
102% 4.7%
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-02
Table 7 continued. Lab Control Spike Results.
ETS-8-044.1 Internal Standard Calibration Analyzed 2/28/13
Lab ID
Spiked Concentration
(ng/mL)
PFBS
Calculated Concentration
(ng/mL)
LCS-130227-1 LCS-130227-2 LCS-130227-3 Average %RSD
LCS-130227-4 LCS-130227-5 LCS-130227-6 Average %RSD
0.198 0.198 0.198
1.98 1.98 1.98
0.211 0.210 0.211 106% 0.54%
2.06 1.97 2.09 103% 2.7%
LCS-130227-7 LCS-130227-8 LCS-130227-9 Average %RSD
9.94 9.94 9.94
10.2 9.49 9.72 98.4% 3.3%
%Recovery 107 106 106
104 99.7 105
102 95.5 97.8
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)
0.206 0.215 0.218 108% 3.0%
1.90 2.00 2.06 100% 4.1%
10.2 9.29 9.54 97.5% 5.1%
%Recovery 104 109 110
95.8 101 104
103 93.5 96.0
ETS-8-044.1 Internal Standard Calibration Analyzed 2/28/13
Lab ID
Spiked Concentration
(ng/mL)
PFOA surrogate
Calculated Concentration
(ng/mL)
LCS-130227-1 LCS-130227-2 LCS-130227-3 Average %RSD
0.198 0.198 0.198
0.200 0.200 0.201 101% 0.57%
LCS-130227-4 LCS-130227-5 LCS-130227-6 Average %RSD
1.98 1.98 1.98
2.03 2.13 2.00 104% 3.7%
%Recovery 101 101 102
102 108 101
Spiked Concentration
(ng/mL)
PFOS surrogate
Calculated Concentration
(ng/mL)
0.189 0.189 0.189
0.201 0.210 0.225 112% 5.9%
1.89 2.04 1.89 2.03 1.89 2.06
108% 0.53%
%Recovery 106 111 119
108 108 109
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-02
3.7 Analytical Method Uncertainty
Analytical uncertainty is based on historical QC data that is control charted and used to evaluate method accuracy and precision. The method uncertainty is calculated following ETS-12-012.2. The standard deviation is calculated for the set of accuracy results (in %) obtained for the QC samples. The expanded uncertainty is calculated by multiplying the standard deviation by a factor of 2, which corresponds to a confidence level of 95%.
Table 8. Analytical Method Uncertainty.
Analyte PFOA PFBS PFHS PFOS PFOA PFBS PFHS PFOS
Calibration Method External Standard External Standard External Standard External Standard Internal Standard Internal Standard Internal Standard Internal Standard
Standard Deviation 8.05 6.21 5.46 7.88 11.1 11.7 10.8 9.62
Method Uncertainty 16% 12% 11% 16% 22% 23% 22% 19%
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.
,, (Sample Concentration of FMS - Average Concentration: Field Sample & Field Sample Dup.) FMS Recovery = ------- - -------------------------------------------- - -------------------------------------- - ------------------- - ------ -- * 100%
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. ISO13-07-02
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. DAL-GW-ACM2; the FMS sample (10 ng/mL) was not appropriate for PFBS; however, the FMS sample for PFOA, PFOS, and the surrogate recovery standards 13C4-PFOA and 13C4-PFOS, met method acceptance criteria. No additional QC samples were prepared. Sample/sample duplicate RPD did not meet acceptance criteria of <20% for PFHS and PFOS. DAL-GW-ACE; sample/sample duplicate RPD did not meet acceptance criteria of <20% for PFOS.
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3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-02
Table 10. DAL GW ACI 130213 (1)
3M LIMS ID
Description
ISO13-07-02-001
DAL-GW-ACI-0-130213
ISO13-07-02-002 DAL-GW-ACI-DB-130213
ISO13-07-02-003 DAL-GW-ACI-FMS-130213
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
2250
NA
2350
NA
4050
82.9
2300 ng/mL 4.3%
Concentration
(ng/mL)
%Recovery
826 NA
833 NA
2600
89.0
830 ng/mL 0.84%
3M LIMS ID
Description
ISO13-07-02-001
DAL-GW-ACI-0-130213
ISO13-07-02-002 DAL-GW-ACI-DB-130213
ISO13-07-02-003 DAL-GW-ACI-FMS-130213
Average Concentration (ng/mL) %RPD
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
1550
NA
1600
NA
3270
86.0
1580 ng/mL 3.2%
Concentration
(ng/mL)
%Recovery
2950
NA
2930
NA
4780
92.0
2940 ng/mL 0.68%
13C4-PFOA
13C4-PFOS
3M LIMS ID
Description
ISO13-07-02-001
DAL-GW-ACI-0-130213
ISO13-07-02-002
DAL-GW-ACI-DB-130213
ISO13-07-02-003
DAL-GW-ACI-FMS-130213
Average Concentration (ng/mL) %RSD
%Recovery
89.9 92.3 88.6 90.2% 2.1%
%Recovery
93.6 88.0 100 93.9% 6.4%
NA = Not Applicable (1) Samples were analyzed by external standard calibration. The surrogate recovery standards 13C4-PFOA and 13C4-PFOS were
added to the samples during sample preparation.
PAGE 13 OF 20
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-02
Table 11. DAL GW ACM2 130213
3M LIMS ID
Description
ISO13-07-02-004
DAL-GW-ACM2-0-130213
ISO13-07-02-005
DAL-GW-ACM2-DB-130213
ISO13-07-02-006
DAL-GW-ACM2-FMS-130213
Average Concentration (ng/mL) %RPD
3M LIMS ID
Description
ISO13-07-02-004
DAL-GW-ACM2-0-130213
ISO13-07-02-005
DAL-GW-ACM2-DB-130213
ISO13-07-02-006
DAL-GW-ACM2-FMS-130213
Average Concentration (ng/mL) %RPD
PFOA (1)
PFBS (2)
Concentration
(ng/mL)
%Recovery
<0.0240
NA
0.0320
NA
9.91 93.7
0.0320 ng/mL (3)
Concentration
(ng/mL)
%Recovery
1680
NA
1660
NA
1700
NC
1670 ng/mL 1.2%
PFHS (1)
PFOS (1)
Concentration
(ng/mL)
%Recovery
0.0417
NA
0.0802
NA
9.77 98.5
0.0610 ng/mL 63% (4)
Concentration
(ng/mL)
%Recovery
0.120
NA
0.0726
NA
11.5 114
0.0963 ng/mL 49% (4)
13C4-PFOA (1) 13C4-PFOS (1)
3M LIMS ID
Description
ISO13-07-02-004
DAL-GW-ACM2-0-130213
ISO13-07-02-005
DAL-GW-ACM2-DB-130213
ISO13-07-02-006
DAL-GW-ACM2-FMS-130213
Average Concentration (ng/mL) %RSD
%Recovery
94.3 97.1 95.9 95.8% 1.5%
%Recovery
100 92.9 104 99.0% 5.6%
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 standards 13C4-PFOA and 13C4-PFOS were
added to the samples during sample preparation. (3) Sample/sample duplicate RPD could not be determined since the initial sample concentration was BLOQ. (4) Sample/sample duplicate RPD did not meet acceptance criteria of <20%.
PAGE 14 OF 20
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-02
Table 12. DAL GW ACE 130213 (1)
3M LIMS ID
Description
ISO13-07-02-007
DAL-GW-ACE-0-130213
ISO13-07-02-008
DAL-GW-ACE-DB-130213
ISO13-07-02-009
DAL-GW-ACE-FMS-130213
Average Concentration (ng/mL) %RPD
3M LIMS ID
Description
ISO13-07-02-007
DAL-GW-ACE-0-130213
ISO13-07-02-008
DAL-GW-ACE-DB-130213
ISO13-07-02-009
DAL-GW-ACE-FMS-130213
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
0.126
NA
0.121
NA
10.1 94.7
0.124 ng/mL 4.0%
Concentration
(ng/mL)
%Recovery
0.0372
NA
0.0348
NA
10.1 101
0.0360 ng/mL 6.7%
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
0.170
NA
0.185
NA
10.4 104
0.178 ng/mL 8.5%
Concentration
(ng/mL)
%Recovery
0.0381
NA
0.0276
NA
11.3 113
0.0329 ng/mL 32% (2)
13C4-PFOA
13C4-PFOS
3M LIMS ID
Description
ISO13-07-02-007
DAL-GW-ACE-0-130213
ISO13-07-02-008
DAL-GW-ACE-DB-130213
ISO13-07-02-009
DAL-GW-ACE-FMS-130213
Average Concentration (ng/mL) %RSD
%Recovery
91.3 104 96.2 97.2% 6.7%
%Recovery
104 95.1 101 100% 4.5%
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 20
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-02
Table 13. DAL GW WW8R 130213 (1)
3M LIMS ID
Description
ISO13-07-02-010
DAL-GW-WW8R-0-130213
ISO13-07-02-011
DAL-GW-WW8R-DB-130213
ISO13-07-02-012
DAL-GW-WW8R-FMS-130213
Average Concentration (ng/mL) %RPD
3M LIMS ID
Description
ISO13-07-02-010
DAL-GW-WW8R-0-130213
ISO13-07-02-011
DAL-GW-WW8R-DB-130213
ISO13-07-02-012
DAL-GW-WW8R-FMS-130213
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
3240
NA
3260
NA
6650
80.6
3250 ng/mL 0.62%
Concentration
(ng/mL)
%Recovery
357 NA
350 NA
3880
88.6
354 ng/mL 2.0%
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
1920
NA
1870
NA
5370
88.2
1900 ng/mL 2.6%
Concentration
(ng/mL)
%Recovery
4860
NA
4830
NA
8930
102
4850 ng/mL 0.62%
13C4-PFOA
13C4-PFOS
3M LIMS ID
Description
ISO13-07-02-010
DAL-GW-WW8R-0-130213
ISO13-07-02-011
DAL-GW-WW8R-DB-130213
ISO13-07-02-012
DAL-GW-WW8R-FMS-130213
Average Concentration (ng/mL) %RSD
%Recovery
88.2 90.1 83.2 87.1% 4.1%
%Recovery
99.0 97.7 93.5 96.7% 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 20
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-02
Table 14. DAL GW WW9R 130213 (1)
3M LIMS ID
Description
ISO13-07-02-013
DAL-GW-WW9R-0-130213
ISO13-07-02-014
DAL-GW-WW9R-DB-130213
ISO13-07-02-015
DAL-GW-WW9R-FMS-130213
Average Concentration (ng/mL) %RPD
3M LIMS ID
Description
ISO13-07-02-013
DAL-GW-WW9R-0-130213
ISO13-07-02-014
DAL-GW-WW9R-DB-130213
ISO13-07-02-015
DAL-GW-WW9R-FMS-130213
Average Concentration (ng/mL) %RPD
PFOA
PFBS
Concentration
(ng/mL)
%Recovery
2840
NA
2860
NA
6100
77.0
2850 ng/mL 0.70%
Concentration
(ng/mL)
%Recovery
232 NA
239 NA
3610
84.8
236 ng/mL 3.0%
PFHS
PFOS
Concentration
(ng/mL)
%Recovery
1420
NA
1370
NA
4950
90.2
1400 ng/mL 3.6%
Concentration
(ng/mL)
%Recovery
4130
NA
4060
NA
8260
104
4100 ng/mL 1.7%
13C4-PFOA
13C4-PFOS
3M LIMS ID
Description
ISO13-07-02-013
DAL-GW-WW9R-0-130213
ISO13-07-02-014
DAL-GW-WW9R-DB-130213
ISO13-07-02-015
DAL-GW-WW9R-FMS-130213
Average Concentration (ng/mL) %RSD
%Recovery %Recovery
90.5 89.9 79.3 86.5% 7.3%
99.6 98.0 97.9 98.5% 0.95%
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 20
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-02
Table 15. Trip Blank Results
3M LIMS ID
ISO13-07-02-016 ISO13-07-02-017 ISO13-07-02-018
Description
DAL-GW-TRIP01 -0 DAL-GW-TRIP01 -LS DAL-GW-TRI P01-HS
3M LIMS ID
ISO13-07-02-016 ISO13-07-02-017 ISO13-07-02-018
Description
DAL-GW-TRI P01-0 DAL-GW-TRI P01-LS DAL-GW-TRI P01-HS
PFOA
PFBS
Concentration (ng/mL)
<0.0240 (1) 9.39 (1) 3560 (2)
%Recovery
NA 89.1 84.4
Concentration (ng/mL)
<0.0250 (1) 9.96 (1) 3680 (2)
%Recovery
NA 100 92.5
PFHS
PFOS
Concentration (ng/mL)
<0.0250 (1) 9.56 (1) 3760 (2)
%Recovery
NA 97.0 95.4
Concentration (ng/mL)
<0.0232 (1) 10.2 (1) 4190 (2)
%Recovery NA 102 105
13C4-PFOA
13C4-PFOS
3M LIMS ID
ISO13-07-02-016 ISO13-07-02-017 ISO13-07-02-018
Description
DAL-GW-TRI P01-0 DAL-GW-TRI P01-LS DAL-GW-TRI P01-HS
%Recovery
101 (1) 95.7 (1) 87.3 (2)
NA = Not Applicable (1) Samples were analyzed by internal standard calibration. (2) Samples were analyzed by external standard calibration.
%Recovery
104 (1) 104 (1) 96.1 (2)
PAGE 18 OF 20
3M ENVIRONMENTAL LABORATORY REPORT NO. IS013-07-02
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
Appendix A: Trend Data for Activated Carbon Influent (ACI) Appendix B: Trend Data for Activated Carbon Effluent (ACE)
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
This test report shall not be reproduced except in full, without written approval of the 3M Environmental Laboratory.
PAGE 19 OF 20
3M ENVIRONMENTAL LABORATORY REPORT NO. ISO13-07-02
Appendix A: Analyte T rend Data for select sampling points at the Decatur Ground Water T reatment Plant (GWTP) GAC System ACI (Activated Carbon Influent) - Sample Results in ng/mL
FC Charting for DAL_GWTP_ACI
PFOA------- -------PFOS------- --------
PFBS------- --------
PFHS ------
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
ACE (Activated Carbon Effluent) - Sample Results in ng/mL
FC Charting for DAL GWTP ACE
1/17/2013 1910 588 895 1810
2/13/2013 2300 830 1580 2940
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
PAGE 20 OF 20
