Document Rgp13nr2kQa6d0Z047RkEROX

3M Environmental Laboratory Report No. ISO12-01-01-02 Final Report Analysis of Water Samples from the Tennessee River - April 2012 Laboratory Request Number: ISO12-01 -01 -02 Method Requirement: 3M Method ETS-8-044.1 Report Date - April 26, 2012 Testing Laboratory 3M Environmental Health and Safety Operations Environmental Laboratory 3M Center, Bldg 260-05-N-17 St. Paul, MN 55144 Requester Gary Hohenstein 3M EHS Operations 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 11 3M Environmental Laboratory Report No. ISO12-01-01-02 3M Environmental Laboratory 3M Environmental Laboratory Manager: William K. Reagen, Ph.D. 3M Principal Analytical Investigator and Report Author: Susan Wolf Analytical Report ISO12-01-01-02 Analysis of Water Samples from the Tennessee River April 2012 Report Date: April 26, 2012 1 Summary/Introduction The 3M Environmental Laboratory prepared and analyzed samples collected by Weston personnel from the Tennessee River, conducted per the study work plan titled "Work Plan for Fish Sampling and Analysis for PFOS in Largemouth Bass from the Tennessee River in the Vicinity of the 3M Decatur Facility". Samples were collected April 5 and 6, 2012. Samples were returned to the 3M Environmental Laboratory on April 13, 2012 at ambient conditions and analyzed for perfluorooctane sulfonate (PFOS) under 3M Environmental Laboratory project number ISO12-01-01-02. The 3M Environmental Laboratory prepared sample containers for nine sampling locations, however only three sampling locations were collected. Each empty container was marked with a "fill to here" line that corresponded to a final volume of 200 mL. Each sample set consisted of a field sample, field sample duplicate, and a field matrix spike. All samples bottles included the addition of internal standard [13C8]-PFOS and surrogate recovery standard [13C4]-PFOS, which were added to the sample containers prior to being sent to the field for sample collection. Sample bottles reserved for field matrix spikes were fortified with appropriate matrix spike solutions containing PFOS, internal standard [13C8]-PFOS and surrogate recovery standard [13C4]-PFOS prior to being sent to the field for sample collection. Samples were prepared and analyzed using either direct injection or solvent dilution according to 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". The internal standard [13C8]-PFOS was used to aid in the quantitation of the samples. 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. PAGE 2 OF 11 3M Environmental Laboratory Report No. ISO12-01-01-02 Table 1. Sample Results Summary. 3M LIMS ID ISO12-01 -01 -02-001 ISO12-01 -01 -02-002 ISO12-01 -01 -02-004 ISO12-01 -01 -02-005 ISO12-01 -01 -02-007 ISO12-01 -01 -02-008 ISO12-01 -01 -02-010 ISO12-01 -01 -02-011 ISO12-01 -01 -02-012 ISO12-01 -01 -02-013 Sample Description PFOS Concentration (ng/mL) -ocation 1 - Sample -ocation 1 - Sample Duplicate Average %RPD Sample/Sample Dup Location 2 - Sample Location 2 - Sample Duplicate Average %RPD Sample/Sample Dup Location 3 - Sample Location 3 - Sample Duplicate Average %RPD Sample/Sample Dup Equipment Blank 1 Equipment Blank 2 Equipment Blank 3 Trip Blank 0.516 0.450 0.483 14 0.720 0.661 0.691 8.5 0.0210 0.0263 0.0237 22 (2) <0.00928 <0.00928 <0.00928 <0.00928 NA = Not Applicable (1) The analytical method uncertainty for the reported results using method ETS-8-044.1 by direct inject for PFOS is 18%. (2) The sample / sample duplicate RPD value did not meet method acceptance criteria of <20%. 2 Method Summary 2.1 Methods Analysis for PFOS was completed following 3M Environmental Laboratory method ETS-8-044.1 "Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS". Table 2. Target Analytes. Target Analytes Perfluorooctanesulfonate (C8 Sulfonate) A c ro n y m PFOS R e fere n ce M aterial Structure Linear + Branched 2.2 Sample Collection Water samples were collected in 250 mL NalgeneTM (high-density polyethylene) bottles prepared at the 3M Environmental Laboratory. A laboratory prepared Trip Blank and Trip Blank field matrix spike were sent with the set of collection bottles. Sample bottles were received by the laboratory at ambient conditions on April 13, 2012. Samples were stored refrigerated at the laboratory after receipt. 2.3 Sample Preparation An aliquot of sample was removed for analysis and placed in an autovial. During the preparation of the laboratory control samples, an aliquot of a separate internal standard spiking solution and surrogate recovery standard solution was added to the laboratory control samples (nominal concentration of 0.1 ng/mL). The sample bottles were spiked with an internal standard at a PAGE 3 OF 11 3M Environmental Laboratory Report No. ISO12-01-01-02 nominal concentration of 0.1 ng/mL and a surrogate recovery standard at a nominal concentration of 0.025 ng/ml prior to being sent to the field for sample collection. 2.4 Analysis All samples and quality control samples were analyzed for PFOS and the surrogate recovery standard [13C4]-PFOS using high performance liquid chromatography/ tandem mass spectrometry (HPLC/MS/MS). Detailed instrument parameters, the liquid chromatography gradient program, and the specific mass transitions analyzed are described in the raw data hard copies placed in the final data packet, and are briefly described below. Table 3. Instrument Parameters. Instrum ent Nam e Analysis Dates A nalytical Method Liquid Chrom atograph G uard colum n Analytical colum n Injection V olum e Mass Spectrom eter Ion S ource E le c tro d e P o la rity S o ftw a re ETS Kirk 4/24/12 ETS-8-044.1 Agilent 1290 Betasil C18 (4.6 mm X 100 mm), 5 g Betasil C18 (4.6 mm X 100 mm), 5g 50 gL Applied Biosystems API 5500 Turbo Spray Turbo ion electrode Negative Analyst 1.5.2 Table 4. Liquid Chromatography Conditions. S te p Num ber 0 1 2 3 4 5 6 7 8 9 Total Tim e (m in) 0.00 0.50 4.00 6.00 11.0 13.0 13.5 16.0 16.5 19.0 F lo w Rate (pL/m in) 750 750 750 750 750 750 750 750 750 750 Percent A (5m M am m onium acetate:0.1% acetic acid) 90.0 90.0 70.0 70.0 20.0 20.0 10.0 10.0 90.0 90.0 Percent B (M ethanol) 10.0 10.0 30.0 30.0 80.0 80.0 90.0 90.0 10.0 10.0 PAGE 4 OF 11 3M Environmental Laboratory Report No. ISO12-01-01-02 Table 5. Mass Transitions. A n a ly te M ass Transition Q 1/Q 3 Internal Standard M ass Transition Q 1 /Q 3 499/99 PFOS 499/80 [ 13Cs]-P F O S 507/80 499/130 [ 13C 4]-P FO S 503/80 [ 13Cs]-P F O S 507/80 Dwell time was 30 msec for each transition. The individual transitions were summed to produce a "total ion chrom atogram " (TIC), which was used for quantitation. 3 Analytical Results 3.1 Calibration Samples were analyzed for PFOS and [13C4]-PFOS against a stable isotope internal standard calibration curve. Calibration standards were prepared by spiking known amounts of the stock solution containing the target analyte and surrogate recovery standard into a laboratory-prepared synthetic groundwater containing calcium and magnesium. A separate internal standard spiking solution was prepared and an aliquot was added at the same level to all calibration standards and laboratory control samples at a nominal concentration of 1 ng/mL. A calibration curve ranging from approximately 0.005 ng/mL to 15 ng/mL was analyzed (0.005 ng/mL to 5 ng/mL for [13C4]-PFOS). The low and high curve points were disabled for PFOS to meet accuracy or method blank criteria. A quadratic, 1/x weighted, calibration curve of the standard peak area ratios 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. 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 PFOS and [13C4]-PFOS. It should be noted that the calibration curve that was used to analyze the samples on 4/24/12, expired on 4/17/12. The expiration date assigned to the curve was based on the expiration date of the solutions containing the surrogate recovery standard [13C4]-PFOS, which were used to prepared the calibration standards. The solutions containing PFOS that were used to prepare the calibation curve were not expired. The solutions containing [13C4]-PFOS that were used to prepared the high set of LCS samples and the sample collection bottles, were not expired. The high set of LCSs for [13C4]-PFOS surrogate met method acceptance criteria, as did the [13C4]-PFOS surrogate in the Tennessee River samples. A method deviation is included in the raw data. 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 of 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 were met for PFOS and [13C4]-PFOS. 3.3 Limit of Quantitation (LOQ) The LOQ for this analysis 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 Lo Q for PFOS was 0.00928 ng/mL. PAGE 5 OF 11 3M Environmental Laboratory Report No. ISO12-01-01-02 3.4 Continuing Calibration During the course of each analytical sequence, continuing calibration verification samples (CCVs) were analyzed to confirm that the instrument response and the initial calibration curve were still in control. All reported sample results were bracketed by CCVs that met method criteria of 100% 25%. 3.5 Blanks Three types of blanks were prepared and analyzed with the samples: solvent blanks (procedural blanks), field/trip blanks, and equipment rinseate blanks for the groundwater samples. Each blank result was reviewed and used to evaluate method performance. Procedural blank results were reviewed according to the method 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 and analyzed in triplicate for PFOS, while only low and high lab control spikes were prepared for the [13C4]-PFOS surrogate. The LCS samples were prepared by spiking known amounts of the analyte into 10 mL of synthetic groundwater to produce the desired concentration. The spiked water samples (LCSs) were then analyzed in the same manner as the samples. The method acceptance criteria states that the average recovery of LCSs be 100% 20% with a RSD <20%, when evaluated independently at each concentration level. All LCSs met these criteria. The LCS results were used to determine overall method uncertainty in Section 3.7. The following calculations were used to generate data in Table 6 for laboratory control spikes. Calculated Concentration LCS Percent Recovery Spike Concentration % LCS% RSD = standard deviation LCS replicates * 10Q% average LCS recovery PAGE 6 OF 11 Table 6. Laboratory Control Spike Recovery. ETS-8-044.1 Analyzed 4/24/12 Lab ID LCS-120424-1 LCS-120424-2 LCS-120424-3 Average %RSD LCS-120424-4 LCS-120424-5 LCS-120424-6 Average %RSD LCS-120424-7 LCS-120424-8 LCS-120424-9 Average %RSD PFOS (Linear + Branched) Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) %Recovery 0.0231 0.0231 0.0231 0.185 0.185 0.185 4.64 4.64 4.64 0.0273 0.0257 0.0253 113% 3.9% 0.174 0.186 0.175 96.1% 3.6% 3.75 4.01 4.19 85.8% 5.7% 118 111 110 93.8 100 94.4 80.7 86.4 90.4 ETS-8-044.1 Analyzed 4/24/12 Lab ID LCS-120424-1 (1) LCS-120424-2 (1) LCS-120424-3 (1) Average %RSD LCS-120424-4 LCS-120424-5 LCS-120424-6 Average %RSD [13C4]-PFOS Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) 0.0238 0.0238 0.0238 0.190 0.190 0.190 0.0246 0.0249 0.0240 103% 1.9% 0.204 0.200 0.202 106% 0.94% %Recovery 103 105 101 107 105 106 (1) The solution used to prepare this set of LCS samples expired 4/17/12. 3M Environmental Laboratory Report No. ISO12-01-01-02 PAGE 7 OF 11 3M Environmental Laboratory Report No. ISO12-01-01-02 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. For method ETS-8-044.1, the most recent fifty QC samples were used. The analytical method uncertainty is calculated by multiplying the standard deviation by a factor of 2, which corresponds to a confidence level of 95%. Table 7. Analytical Method Uncertainty Analyte PFOS [13C4]-PFOS Standard Deviation 8.75 6.74 Method Uncertainty (%) 18 13 3.8 Field Matrix Spikes (FMS) A field matrix spike was collected at each sampling location 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 reference standards for PFOS in the field matrix spiking solution consisted of linear and branched isomers. In addition, field matrix spikes for this project also included the use of stable isotope surrogate spikes of [13C4]-PFOS, which was added at a nominal concentration of 0.025 ng/mL to all sample bottles prior to sample collection. Surrogate matrix spike recoveries within method acceptance criteria of 10030% confirm that "unknown" components in the sample matrix do not significantly interfere with the preparation and analysis of the analytes of interest. Table 8. Field Matrix Spike Level. Sampling location All locations and Trip Blank PFOS ng/mL 0.0232 FMS Recovery = (-S-a--m- ple Concentration ofsFMS - Average Spike CCoonncceennttrraattiioonn :Field Sample & Field Samp-l-e-D--u--p.)*100% 4 Data Summary and Discussion The tables below summarize the sample results and field matrix spike and surrogate recoveries for the sampling locations as well as the Trip Blanks. Results and average values are rounded to three significant figures according to EPA rounding rules. Because of rounding, values may vary slightly from those listed in the raw data. Field matrix spike and surrogate recoveries meeting the method acceptance criteria of 30%, demonstrate that the method(s) were appropriate for the given matrix and their respective quantitative ranges. PAGE 8 OF 11 3M Environmental Laboratory Report No. ISO12-01-01-02 Table 9. Tennessee River; Location 1 3 M LIM S ID D e s c rip tio n ISO12-01 -01 -02-001 ISO12-01 -01 -02-002 ISO12-01 -01 -02-003 Location 1 Location 1 Sample Duplicate Location 1 FMS A verag e Concentration (ng/m L) % R P D / % R SD PFOS C o n c e n tra tio n (ng/m L) % Recovery 0.516 0.450 0.537 NA NA NC 0.483 ng/m L 14% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration is greater than 2x spiking level. [ 13C 4 -P F O S % Recovery 108 105 106 106% 0.99% Table 10. Tennessee River; Location 2 3 M LIM S ID D e s c rip tio n ISO12-01 -01 -02-004 ISO12-01 -01 -02-005 ISO12-01 -01 -02-006 Location 2 Location 2 Sample Duplicate Location 2 FMS A verag e Concentration (ng/m L) % R P D / % R SD PFOS C o n c e n tra tio n (ng/m L) % Recovery 0.720 0.661 0.654 NA NA NC 0.691 ng/m L 8.5% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration is greater than 2x spiking level. [ 13C 4 -P F O S % Recovery 108 106 109 108% 1.5% Table 11. Tennessee River; Location 3 3 M LIM S ID D e s c rip tio n ISO12-01 -01 -02-007 ISO12-01 -01 -02-008 ISO12-01 -01 -02-009 Location 3 Location 3 Sample Duplicate Location 3 FMS A verag e Concentration (ng/m L) % R P D / % R SD PFOS C o n c e n tra tio n (ng/m L) % Recovery 0.0210 0.0263 0.0430 NA NA 83.4 0.0237 ng/m L 2 2 % 1 NA = Not Applicable (1) The sample / sample duplicate RPD did not meet method acceptance criteria of <20%. [ 13C 4 -P F O S % Recovery 105 108 106 106% 1.6% PAGE 9 OF 11 Table 12. Rinseate Blanks 3 M LIM S ID ISO12-01 -01 -02-010 ISO12-01 -01 -02-011 ISO12-01 -01 -02-012 D e s c rip tio n Equipment Blank 1 Equipment Blank 2 Equipment Blank 3 Table 13. Trip Blanks 3 M LIM S ID ISO12-01 -01 -02-013 ISO12-01 -01 -02-014 D e s c rip tio n Trip Blank Trip Blank FMS 3M Environmental Laboratory Report No. ISO12-01-01-02 PFOS C o n c e n tra tio n (ng/m L) <0.00928 <0.00928 <0.00928 [ 13C 4]-P FO S % Recovery 108 105 108 PFOS C o n c e n tra tio n (ng/m L) <0.00928 0.0209 % Recovery NA 90.1 [ 13C 4]-P FO S % Recovery 105 103 PAGE 10 OF 11 3M Environmental Laboratory Report No. IS012-01-01-02 5 Conclusion Laboratory control spikes were used to determine the analytical method accuracy and precision for PFOS. 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-8-044.1 "Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection Analysis". Analytical results are reported in Tables 1 and 9-13 of this report. 6 Data/Sample Retention All remaining samples and associated project data (hardcopy and electronic) will be archived according to 3M Environmental Laboratory standard operating procedures. William K. Reagen, Ph.D., 3M Environmental Laboratory Manager Date The 3M Environmental Laboratory's Quality Assurance Unit has audited the data and report for this project. A /1 . ~ < Quality Assurance Representative Date PAGE 11 OF 11