Document 8VZYkzXeKeV0gE6758nqYVR7k

3M ENVIRONMENTAL LABORATORY REPORT NO. E05-0007 Final Report Analysis of PFOS and PFOA in Aqueous Samples 3M Dyneon, Oakdale Minnesota Laboratory Request Number: E05-0007 Method Requirement: 3M Method ETS-8-154.1 (modified) Testing Laboratory 3M EHS Operations 3M Environmental Laboratory Building 2-3E-09 935 Bush Avenue St. Paul, MN 55106 Requester Gary A. Hohenstein 3M Corporation Building 42-2E-27 Environmental Manager, Special Projects, EHS Opns Phone: (651)778-5150 PAGE 1 OF 8 3M ENVIRONMENTAL LABORATORY REPORT NO. E05-0007 3M Environmental Laboratory 3M Environmental Laboratory Manager: William K. Reagen 3M Technical Lead: Kent Lindstrom 3M Analytical Team: Mark Ellefson Michelle Malinsky 3M Environmental Laboratory Professional Service Personnel Mark Anderson, Braun Intertec Cindy Carlson, Pace Analytical, Lab Ops Kevin Eich, Quality Associates Marlene Heying, Pace Analytical, Lab Ops Analytical Report E05-0007 Oakdale Dyneon FC Grab Samples January 20, 2005 1 Introduction/Summary Water samples were collected on January 4, 2005, from various locations at the Dyneon Oakdale facility and analyzed for perfluorooctanoate (PFOA, C7F15COO') and perfluorooctane sulfonate (PFOS, C8F17S 0 3'). George Millet at Dyneon escorted the Pace Analytical Services field analyst at the site. Millet provided a map of the facility and determined that four locations should be sampled that are representative of the drinking water sites at the facility. Professional services personnel at the 3M Environmental laboratory prepared sample containers under the direction of Kent Lindstrom. Sample containers for each sampling location included a field sample, field sample duplicate, low field spike (0.05 ng/mL, ppb) and high field spike (1.0 ng/mL). Each empty container was marked with a "fill to here" line at 200 mL and was fortified with a surrogate spike or an appropriate matrix spike solution containing the surrogate, PFOA, and PFOS prior to being sent to the field for sample collection. Table 1. Sample Results Summary. Sample Identification E05-0007-77781 Reception area rest room E05-0007-77782 Reception area rest room Dup E05-0007-77785 Ctr office rest rm ftn E05-0007-77786 Ctr office rest rm fin Dup E05-0007-77789 Break room sink E05-0007-77790 Break room sink Dup E05-0007-77793 Utility room janitor sink E05-0007-77794 Utility room ianitor sink Dup *PFOA *PFOS Concentration PPB Concentration PPB (ng/mL) (ng/mL) 0.75 0.66 0.18 0.19 0.14 0.14 0.67 0.71 0.86 0.86 0.14 0.16 0.18 0.15 0.84 0.88 * Based on the analytical results of the surrogate, field matrix spikes, field duplicates, trip blank spikes, and laboratory control spikes, the analytical accuracy of the reported results is 30%. The lower limit of quantitation (LOQ) for the samples is 0.025 ng/mL. 35 PAGE 2 OF 8 3M ENVIRONMENTAL LABORATORY REPORT NO. E05-0007 2 Methods - Analytical and Preparatory 2.1 Sample Collection Samples were collected In pre-rinsed NalgeneTM (low-density polyethylene) bottles prepared at the 3M Environmental Laboratory. Prior to sample collection, all bottles were spiked in the laboratory with a known volume of either a surrogate solution or an appropriate matrix spiking solution containing the analytes of interest (PFOA and PFOS) and the surrogate. Table 2 below details the samples collected and spikes added to each bottle. Table 2. Sample Collection and Spike Information. Sample ID Sample Description Nominal Final Volume Collected (mL) Volume of Spike Splke Final Nominal Spike Concentration (ng/mL) Solution Solution (mL) Description PFOA [1 ,2 13Cl PFOA PFOS E05-0007-77781 Reception area rest room 200 1 Solution A E05-0007-77782 Reception area rest room Dup 200 1 Solution A E05-0007-77783 Reception area rest room Low Spike 200 1 Solution B E05-0007-77784 Reception area rest room High Spike 200 1 Solution C E05-0007-77785 Ctr office rest rm ftn 200 1 Solution A E05-0007-77786 Ctr office rest rm ftn Dup 200 1 Solution A E05-0007-77787 Ctr office rest rm ftn Low Spike 200 1 Solution B E05-0007-77788 Ctr office rest rm ftn High Spike 200 1 Solution C E05-0007-77789 Break room sink 200 1 Solution A E05-0007-77790 Break room sink Dup 200 1 Solution A E05-0007-77791 Break room sink Low Spike 200 1 Solution B E05-0007-77792 Break room sink High Spike 200 1 Solution C E05-0007-77793 Utility room janitor sink 200 1 Solution A E05-0007-77794 Utility room janitor sink Dup 200 1 Solution A E05-0007-77795 Utility room janitor sink Low spike 200 ' 1 Solution B E05-0007-77796 Utility room janitor sink High Spike 200 1 Solution C E05-0007-77797 Field blank 200 1 Solution A E05-0007-77798 Field blank Low Spike 200 1 Solution B E05-0007-77799 Field blank High Spike 200 1 Solution C Solution A = 20 ng/mL (nominal) PFOA [1,2 13cj Surrogate Solution B = 10 ng/mL (nominal) PFOS, PFOA, and ) PFOA [1,213C] Surrogate Solution C = 200 ng/mL (nominal) PFOS, PFOA, and ) PFOA [1,213C] Surrogate 0.1 0.1 0.05 1.0 0.1 0.1 0.05 1.0 0.1 0.1 0.05' 1.0 0.1 0.1 0.05 1.0 0.1 0.05 1.0 NA NA 0.05 1.0 NA NA 0.05 1.0 NA NA 0.05 1.0 NA NA 0.05 1.0 NA 0.05 1.0 NA NA 0.05 1.0 NA NA 0.05 1.0 NA NA 0.05 1.0 NA NA 0.05 1.0 NA 0.05 1.0 2.2 Extraction All samples, calibration standards, and associated quality control samples were extracted using a modified procedure of ETS-8-154.1 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates in Water by Solid Phase Extractions and High Performance Liquid Chromatography/Mass Spectrometry". Briefly, approximately eighty mL of sample were loaded onto a pre-conditioned Waters C18 solid phase extraction (SPE) cartridge (Sep-Pak, 0.5g, 3cc) using a vacuum manifold. The loaded SPE cartridges were then transferred to a Zymark Rapid Trace Automated SPE System where they were then eluted with 2 mL of methanol using positive pressure. This extraction procedure concentrates the samples by a factor of forty. (Initial volume = 80 mL, final volume = 2 mL). PAGE 3 OF 8 3M ENVIRONMENTAL LABORATORY REPORT NO. E05-0007 2.3 Analysis All extracts were analyzed for PFOA, PFOS, and PFOA [1,2 13C] 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. The analytical guard column is utilized to chromatographically separate instrument-associated background from the analytes of interest present in the injected sample. The combined use of the guard column, analytical column and liquid chromatography gradient program elute background analytes as one peak approximately 0.4 minutes after the analyte present in the injected sample. Isomers of compounds in samples elute in two or more peaks for which areas are summed for quantification. Table 3. Instrument Parameters Liquid Chromatograph Guard column Analytical column Injection Volume Mass Spectrometer Electrode Ion Source Polarity Agilent 1100 Betasil C18 2X50, 5 pm Betasil C18 (2.1 mm X 100 mm), 5 urn 10 pL Applied Biosystems API 4000 2-spray Turbo Spray Negative Table 4. Liquid Chromatography Gradient Program Step Number 0 1 2 3 4 5 Total Time (min) 0 1.0 14.5 15.5 16.5 20.0 Flow Rate (pL/min) 300 300 300 300 300 300 Table 5. Mass Transitions Percent A (2 mM ammonium acetate) 80.0 80.0 10.0 10.0 80.0 80.0 PercentB (Methanol) 20.0 20.0 90.0 90.0 20.0 20.0 Analyte Mass Transition Q1/Q3 Dwell Time (msec) *PFOA 413/369 413/219 150 150 413/169 150 *PFOS 499/99 150 499/130 150 499/80 150 PFOA [1,213C] 415/370 150 *Only the 413/369 and 499/99 transitions were used to quantify PFOA and PFOS, respectively. Other transitions were collected for confirmatory purposes only. 37 PAGE 4 OF 8 3M ENVIRONMENTAL LABORATORY REPORT NO. E05-0007 3 Data Analysis 3.1 Calibration Calibration standards were prepared by spiking known amounts of stock solutions containing PFOA, PFOS, and PFOA [1,2 13C] Into 80 mL of ASTM type I water. Each spiked water standard was then extracted in the same manner as the collected samples. A total of eight spiked standards ranging from 0.025 ng/mL to 5 ng/mL (nominal) were prepared. The 5 ng/mL curve point was deactivated for PFOA and the PFOA [1, 2 X ] surrogate in order to meet accuracy criteria. The calibrated range bracketing all sample results was 0.025 ng/mL to 2.5 ng/L for PFOA and the PFOA [1,2 13C] surrogate and 0.025 to 5 ng/L for PFOS. A quadratic, 1/x weighted, calibration curve was used to fit the data for each analyte. The data was not forced through zero during the fitting process. Calculating the standard concentration using the peak area counts and the resultant calibration curve confirmed accuracy of each curve point. Each extracted calibration standard used to generate the final calibration curve met the method calibration accuracy requirement of 25%. Coefficients of determination (r2) were greater than 0.997 for all analytes. 3.2 Limit of Quantitation (LOQ) The LOQ for this analysis, as defined in ETS-8-154.1, is the lowest non-zero active calibration standard in the curve. Here, the LOQ is 0.025 ng/mL for all analytes. 3.3 System Suitability The 1 ng/mL extracted-calibration standard was analyzed in triplicate at the beginning and end of the analytical sequence to demonstrate overall system suitability. For all analytes, the relative standard deviation (RSD) of the analyte peak area counts and the RSD of the peak retention times was less than 5% and 2%, respectively, which met method criteria. 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 was still in control. All CCVs, for all three analytes, produced recoveries within 25%, which met method criteria. 3.5 Blanks Three types of blanks were prepared and analyzed with the samples: method blanks, solvent blanks, and field/trip blanks. Each blank type is described below. Analyte peak area counts in all blank samples were less than half the area counts of the lowest calibration standard, which met method criteria for establishing the LOQ of 0.025 ng/mL. 3.5.1 Method Blanks Several method blanks were prepared by loading 80 mL of ASTM Type I water onto a C18 SPE cartridge and eluting with 2 mL of methanol using the same extraction procedure as the samples. Method blanks were prepared to evaluate the levels of background contamination in the overall extraction process (glassware, SPE cartridges, etc.) 3.5.2 Solvent Blanks Several methanol solvent blanks were analyzed to assess system contamination and/or instrument carryover. PAGE 5 OF 8 3M ENVIRONMENTAL LABORATORY REPORT NO. E05-0007 3.5.3 Field/Trip Blanks Prior to sample collection, one sample container was filled with 200 mL of ASTM Type I water, sealed, and shipped to the sample collection site along with the empty containers. This sample was analyzed as field/trip blank. 3.6 Lab Control Spikes (LCSs) Low (0.1 ng/mL nominal concentration) and high (1.0 ng/mL nominal concentration) lab control spikes were prepared and analyzed in triplicate. LCSs were prepared by spiking known amounts of the analytes into 80 mL of ASTM Type I water to produce the desired concentration. The spiked water samples were extracted and analyzed in the same manner as the samples. All LCSs produced recoveries within the method acceptance criteria of 25% for accuracy and 15% RSD for precision. Table 6 summarizes the LCS recovery results. Table 6. Lab Control Spike Results. Description Spike Level LCS 1 LCS 2 LCS 3 LCS 4 LCS 5 LCS 6 low (0.1 ng/mL) low (0.1 ng/mL) low (0.1 ng/mL) Average %RSD high (1.0 ng/mL) high (1.0 ng/mL) high (1.0 ng/mL) Average %RSD PFOA 103 97.3 99.0 99.8 + 2.9% 94.0 77.2 91.8 87.7 + 10% Percent Recovery PFOS 106 99.2 99.3 102 + 4.1% 101 90.6 100 97.5 6.1 % LCS Percent Recovery Calculated Concentration * 10QO/ Spike Concentration LCS%RSD = standard deviation LCS replicates 100% average LCS recovery PFOA [1 ,2 11C] 103 97.6 98.8 99.9 3.0% 90.7 80.9 94.6 88.8 + 8.0% 3.7 Surrogates PFOA [1,2 13C] was added to all samples and sample spikes to evaluate overall method performance. PFOA [1,2 13C] recoveries in collected samples and sample spikes ranged from 69.0% to 95.6% with an average recovery of 79.0%. Analytical results are not corrected for these recoveries. Table 7 lists the surrogate recoveries. 3.8 Sample Spikes A low (nominal concentration of 0.05 ng/mL) and a high (nominal concentration 1.0 ng/mL) field spike were collected at each sampling point. Endogenous levels of PFOA and PFOS were in some cases much higher than the low spike amount of 0.05 ng/mL and therefore not all low spike recoveries were reported. The PFOA [1,2 13C] surrogate meets criteria and therefore data quality is not impacted. Reported spike recoveries ranged from 73.8 to 116%. Actual spike concentrations may vary slightly depending of the accuracy of marking and adhering to the "fill to here" line on the bottle. It is estimated that this variability is less than 5% and therefore data are not corrected for actual collection volumes. Table 7 below lists the sample spike data and recoveries. PAGE 6 OF 8 3M ENVIRONMENTAL LABORATORY REPORT NO. E05-0Q07 Table 7. Summary of Sample Spike Recoveries PFOA PFOS PFOA r1,213C] Sample ID E05-0007-77781 Reception area rest room E05-00Q7-77782 Reception area rest room Dup E05-0007-77783 Reception area rest room Low Spike E05-0007-77784 Reception area rest room High Spike EQ5-0007-77785 Ctr office rest rm ftn E05-0007-77786 Ctr office rest rm ftn Dup E05-0007-77787 Ctr office rest rm ftn Low Spike E05-0007-77788 Ctr office rest rm fin High Spike E05-0007-77789 Break room sink E05-0007-77790 Break room sink Dup E05-0007-77791 Break room sink Low Spike E05-0007-77792 Break room sink High Spike EQ5-0007-77793 Utility room janitor sink E05-0007-77794 Utility room janitor sink Dup E05-0007-77795 Utility room janitor sink Low spike E05-0007-77796 Utility room anitorsink High Spike E05-0007-77797 Field blank E05-0007-77798 Field blank Low Spike E05-0007-77799 Field blank High Spike Concentration PPB (nq/mL) 0.75 0.66 0.72 1.6 0.18 0.19 0.22 ** 0.14 0.14 0.16 0.86 0.67 0.71 0.74 1.6 <0.025 0.042 0.77 %Spike Recovery NA NA * 93.5 NA NA 81.0 ** NA NA * 73.8 NA NA * 93.7 NA 85.4 79.0 Concentration PPB (ng/mL) 0.86 0.86 0.83 1.7 0.14 0.16 0.21 irk 0.18 0.15 0.18 1.1 0.84 0.88 0.85 . 1.9 <0.025 0.042 0.83 %Spike Recovery NA NA * 86.0 NA NA 116 ** NA NA * 94.3 NA NA * 106 NA 83.8 83.5 %Surrogate Recovery 77.4 78.0 . 76.7 81.4 69.0*** 79.4 82.0 ** 81.0 86.2 81.1 77.6 81.6 72.7 72.6 80.0 95.6 79.0 71.4 *Spike recoveries not calculated. The spiked amounts relative to the sample levels were too low to consistently evaluate the spike recoveries. The surrogate recoveries and the High Spike recoveries document analytical accuracy. "Sample spilled during extraction. No results available. " T h is field sample container was inadvertently filled past the 200 mL "fill to here" line by approximately 10-15%, resulting in a more dilute surrogate concentration. Results for PFOA and PFOS are not impacted since a known volume is removed for analysis. Sample Spike Recovery = i P ik-g-d S- i mP-le Con<?n]Lation ._Ave iageE nd_o9enous Concentration) . 1QQ% Spike Concentraton 4 Conclusion The analytical results reported here for the aqueous samples collected on January 4, 2005, at the Dyneon Oakdale facility meet the analytical precision and accuracy requirements of EHS Opns Laboratory method ETS-8-154.1. Results are deemed to be accurate to 30%. 5 Data / Sample Retention All hardcopy and electronic data will be archived according to 3M Environmental Laboratory standard operating procedures. In most cases, the entire volume of each sample was consumed during the course of sample preparation procedures. Where residual amounts remain, an Insufficient volume exists for further sample preparation. The sample bottles will not retained. iO PAGE 7 OF 8 3M ENVIRONMENTAL LABORATORY REPORT NO. E05-0007 6 Signatures Kent Lindstrom, Technical Lead Casey A. Howell, QAU Supervisor o 1/ z j j o s ^ Date Date William \C Reagen Ph.D., Environmental Laboratory Management Date PAGE 8 OF 8