Document GK4pqy9o0aXrrKN1oQ5zr5Z9x

3M ENVIRONMENTAL LABORATORY REPORT NO. E08-0185 Final Report Analysis of PFBA, PFOA, PFBS, PFOS, FBSA, and FOSA in Aqueous Samples from 3M Decatur, Alabama 3M Decatur NPDES Permit Number AL0000205: Quarterly FC Monitoring of Outfall DSN001; 2nd Quarter 2008 Sampling Laboratory Request Number: E08-0185 Method Requirement: 3M Method ETS-8-154.3 Report Date - May 5, 2008 Testing Laboratory 3M EHS Operations 3M Environmental Laboratory Building 260-5N-17 Maplewood, MN 55144-1000 Requester Gary Hohenstein 3M Building 42-02-E-27 PO Box 3331 Saint Paul, MN 55133-3331 Phone: (651)778-5150 Fax: (651)778-7203 1 ^CREDITED Certificate #2052-01 The testing reported herein meet the requirements of ISO/IEC 17025-2005 "General Requirements for the Competence of Testing and Calibration Laboratories", in accordance with the A2LA Certificate #2052-01. Testing that complies with this International Standard also operate In accordance with ISO 9001/ISO 9002 (2000). PAGE 1 OF 12 3M ENVIRONMENTAL LABORATORY REPORT NO. E08-0185 3M Environmental Laboratory 3M Environmental Laboratory Technical Manager: William K. Reagen, Ph.D. 3M Principal Analytical Investigator and Report Author: Susan Wolf Analytical Report E08-0185 3M Decatur NPDES Permit Number AL0000205: Quarterly FC Monitoring of Outfall DSN001 ; 2ndQuarter 2008 Sampling Report Date: May 5, 2008 11 Introduction/Summary The 3M Environmental Laboratory prepared and analyzed outfall samples collected by Enersolv Corporation personnel on April 8, 2008, from 3M Decatur location DSN001. Samples were returned to the 3M Environmental Laboratory for analysis of Perfluorobutanoic acid (PFBA), Perfluorooctanoic acid (PFOA), Perfluorobutane sulfonate (PFBS), Perfluorooctane sulfonate (PFOS), Perfluorobutanesulfonylamide (FBSA) and Perfluorooctanesulfonylamide (FOSA) under laboratory project number E08-0185. The 3M Environmental Laboratory prepared sample containers for one sampling location. The sample set consisted of a field sample, field sample duplicate, low field spike, mid field spike, and high field 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. Samples were prepared using ETS-8-154.3 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates in Water by Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry" on April 14, 008 and analyzed on April 15 and 18, 2008. Due to field matrix spikes not meeting method acceptance criteria for FOSA, samples were re-extracted along with a laboratory matrix spike on April 22, 2008 and analyzed on April 23,2008. 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. mm a c c r e d it e d ) The testing reported herein meet the requirements of ISO/IEC 17025-2005 "General Requirements for the Competence of Testing and Calibration Laboratories", in accordance with the A2LA Certificate #2052-01. Testing that complies with this International Standard also operate in accordance with ISO 9001/ISO 9002(2000). Certificate #2052-01 PAGE 2 OF 12 3M ENVIRONMENTAL LABORATORY REPORT NO. E08-0185 Table 1. Sample Results Summary. 3M LIMS ID E08-0185-001 E08-0185-002 Sample Description P F B A (1) Concentration (n g /m L ) DSN001, Sample DSN001 Sample Duplicate 3.38 3.50 Average %RPD Sample/Sample Dup 3.44 3.5 PFO A <2> Concentration (n g /m L ) 6.58 6.76 6.67 2.7 PFB S(1) Concentration (n g /m L ) 13.9 15.8 14.8 13 3M LIMS ID Sample Description PFO S(1) Concentration (n g /m L ) F B S A (1) Concentration (n g /m L ) f o s a (3) Concentration (n g /m L ) E08-0185-001 DSN001, Sample 13.5 43.6 1.47 E08-0185-002 DSN001 Sample Duplicate 14.2 45.8 1.61 Average 13.8 44.7 1 .5 4 (3) %RPD Sample/Sample Dup 5.1 4.9 9.1 (1) Samples were extracted by solid-phase extraction using method ETS-8-154.3 on April 14, 2008 and analyzed on April 15, 2008. The analytical method uncertainties associated with the reported results are as follows: PFBA 100% 16%, PFBS 100% 13%, PFOS 100% 7.7%, and FBSA100% 12%. (2) Samples were extracted by solid-phase extraction using method ETS-8-154.3 on April 14, 2008 and analyzed on April 18, 2008. The analytical method uncertainty associated with the reported results for PFOA is 100% 13%. (3) Samples were re-extracted by solid-phase extraction for FOSA using method ETS-8-154.3 on April 22, 2008. The analytical uncertainty for FOSA has been adjusted for matrix spike recoveries to 100% 45%. See section 4 of the report for additional information. 2 Methods - Analytical and Preparatory 2.1 Methods Analysis was completed following 3M Environmental Laboratory method ETS-8-154.3 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates in Water by Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry". 2.2 Sample Collection Samples were collected 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 the analytes of interest. Collected sample bottles were returned to the laboratory at ambient conditions on April 10, 2008. 2.3 Sample Preparation All samples, calibration standards, and associated quality control samples were extracted using ETS-8154.3. Briefly, 40 mL of sample were loaded onto a pre-conditioned solid-phase extraction (SPE) cartridge (Sep-Pak, 1.0 g, 6 cc or Oasis HLB, 0.2 g, 6 cc) using a vacuum manifold. The loaded SPE cartridges were then eluted with 5 mL of methanol. This extraction procedure concentrates the samples by a factor of eight. (Initial volume = 40 mL, final volume = 5 mL). 2.4 Analysis All samples and quality control samples were analyzed for six target analytes using high performance liquid chromatography/ tandem mass spectrometry (HPLC/MS/MS). Pertinent instrument parameters, PAGE 3 OF 12 3M ENVIRONMENTAL LABORATORY REPORT NO. E08-0185 the liquid chromatography gradient program, and the specific mass transitions analyzed are described in the tables below. Table 2. Instrument Parameters. Instrument Name Analytical Method followed Liquid Chrom atograph Guard column Analytical column Injection Volume Mass Spectrometer Ion Source Electrode Polarity Software ETS Stan ETS-8-154.3 Agilent 1100 Betasil C18 (2.1 mm X 100 mm), 5p Betasil C18 (2.1 mm X 100 mm), 5g 5pL Applied Biosystems API 4000 Turbo Spray Turbo ion electrode Negative Analyst 1.4.2 Table 3. Liquid Chromatography Gradient Program. Step Number 0 1 2 3 4 5 Total Time (min) 0 2.0 14.5 15.5 16.5 20.0 Table 4. Mass Transitions Flow Rate (pL/min) 300 300 300 300 300 300 Percent A (2 m M am m onium acetate) 90.0 90.0 10.0 10.0 90.0 90.0 Percent B (Methanol) 10.0 10.0 90.0 90.0 10.0 10.0 A n a ly te Mass Transition Q 1/Q 3 PFBA 213/169 413/369 PFOA 413/219 413/169 PFBS 299/80 299/99 499/99 PFOS 499/80 499/130 FBSA 298/78 FOSA 498/78 The individual transitions were summed to produce a "total ion chromatogram" (TIC), which was used for quantitation. PAGE 4 OF 12 3M ENVIRONMENTAL LABORATORY REPORT NO. E08-0185 |3 Data Analysis i___________ _____________________________________________________________________ _ .... 3.1 Calibration Calibration standards were prepared by spiking known amounts of stock solutions containing the analytes of interest into 40 mL of laboratory reagent water. Each spiked water standard was then extracted in the same manner as the collected samples. A total of twelve spiked standards ranging from 0.025 ng/mL to 25 ng/mL (nominal) were prepared. A quadratic, 1/x weighted, calibration curve was used to fit the data for each analyte. The data were 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 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. The correlation coefficient (r) was greater than 0.995 for all analytes. The stock standard used to prepare the calibration standards contained neat materials that have expired. The expired neat materials were not the analytes of interest in this report. The expired neat materials have been sent out for recertification and are not expected to have any impact on the results contained in this report. 3.2 Limit of Quantitation (LOQ) The LOQ as defined in method ETS-8-154.3 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 analytical LOQs are listed below. Table 5. Limit of Quantitation (LOQ). Analyte PFBA PFOA PFBS PFOS FBSA FOSA LOQ, ng/mL 0.0262 0.0245 0.0252 0.0251 0.0252 0.0250 3.3 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. Method acceptance criteria are 100% 25%. All CCVs met method criteria. 3.4 Blanks Four types of blanks were prepared and analyzed with the samples: method blanks, solvent blanks, field/trip blanks, and equipment blanks. Each blank result is reviewed and used to evaluate method performance to determine the LOQ for each analyte. 3.5 Lab Control Spikes (LCSs) Low and high lab control spikes were prepared and analyzed in triplicate for all analytes, except for the FOSA LCSs extracted on 4/23/08, for which there were three concentration levels of control spikes. LCSs were prepared by spiking known amounts of the analytes into 40 mL of laboratory reagent water to produce the desired concentration. The spiked water samples were then extracted and analyzed in the same manner as the samples. Analysis of triplicate LCSs at the two specified levels cross-validates PAGE 5 OF 12 3M ENVIRONMENTAL LABORATORY REPORT NO. E08-0185 the analytical method as used here for any modificatlons/deviations from ETS 8-154.3. The method acceptance criteria states that the average recovery of all LCS be between 80%-120% with a RSD <20%. All LCS samples met method acceptance criteria and were used in the determination of analytical uncertainty where applicable. The following calculations were used to generate data in Table 6. LCS Percent Recovery Calculated Concentration 100---------------- -- --------- -- --------------- ------------ % Spike Concentration LCS% RSD = standard deviation LCS replicates ,, 10Q% average LCS recovery PAGE 6 OF 12 3M ENVIRONMENTAL LABORATORY REPORT NO. E08-0185 Table 6. Lab Control Spike Results. Extracted 4/14/08 Lab ID LCS-080414-1 LCS-080414-2 LCS-080414-3 LCS-080414-4 LCS-080414-5 LCS-080414-6 Average %RSD P F B A <1> Spiked Calculated Concentration Concentration (ng /m L ) (n g /m L ) 0.209 0.179 0.209 0.209 5.24 0.192 0.196 5.03 5.24 5.24 5.32 5.23 94.8% 6.2% VoRecovery 85.6 91.9 93.7 96.0 102 99.8 p f o a (2> PFB S<1> Spiked Calculated Concentration Concentration (ng /m L ) (ng /m L ) % R eco very Spiked Calculated Concentration Concentration (n g /m L ) (n g /m L ) 0.196 0.195 99.7 0.202 0.203 0.196 0.196 4.90 4.90 4.90 0.183 0.188 4.86 4.88 4.95 93.2 95.7 99.1 99.6 101 0.202 0.202 5.04 5.04 5.04 0.200 0.194 5.00 4.93 5.09 98.1% 3.0% 98.9% 1.8% VoRecovery 100 99.2 96.0 99.3 97.8 101 Extracted 4/14/08 PFOSm Lab ID Spiked Calculated Concentration Concentration (ng /m L ) (n g /m L ) LCS-080414-1 0.201 0.191 LCS-080414-2 LCS-080414-3 LCS-080414-4 LCS-080414-5 LCS-080414-6 0.201 0.201 5.02 5.02 5.02 0.180 0.188 4.66 4.83 4.69 Average %RSD 93.4% 2.3% (1) Samples analyzed April 15,2008. (2) Samples analyzed April 18,2008. VoRecovery 94.8 89.8 93.7 92.8 96.2 93.3 FBSAm Spiked Calculated Concentration Concentration (ng /m L ) (ng /m L ) VoRecovery FOSAm S p ik e d Calculated Concentration Concentration (n g /m L ) (n g /m L ) 0.202 0.207 103 0.200 0.253 0.202 0.202 5.04 5.04 5.04 0.206 0.199 5.12 4.87 5.10 102 98.7 102 96.7 101 0.200 0.200 5.01 5.01 5.01 0.227 0.235 5.69 4.93 4.95 101% 2.4% 111% 9.7% VoRecovery 126 113 117 114 98.4 98.8 PAGE 7 OF 12 3M ENVIRONMENTAL LABORATORY REPORT NO. E08-0185 Table 6 continued. Lab Control Spike Results. Analyzed 4/23/08 FOSA Lab ID Spiked Calculated Concentration Concentration (ng /m L ) (ng /m L ) % R eco very LCS-080422-1 0.200 0.232 116 LCS-080422-2 LCS-080422-3 LCS-080422-4 LCS-080422-5 LCS-080422-6 LCS-080422-7 LCS-080422-8 0.200 0.200 5.01 5.01 5.01 10.0 10.0 0.227 0.233 5.07 5.16 4.94 12.2 12.5 114 116 101 103 98.6 122 125 Average %RSD 112% 8.8% 3.6 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 factor of 2, which correspond with a confidence level of 95%. A minimum of twenty data points is needed to determine method uncertainty by this method. Table 7. Analytical Uncertainty. Analyte PFBA PFOA PFBS PFOS FBSA FOSA Number of data points used for determining uncertainty 50 50 50 50 41 50 Standard Deviation 8.18 6.63 6.55 3.86 6.12 11.3 Method Uncertainty 100%16% 100%13% 100%13% 100%7.7% 100%12% 100%23% 3.7 Laboratory Matrix Spike (LMS) Due to the field matrix spike recoveries not meeting method acceptance criteria for FOSA on the initial sample extraction and analysis (data not reported for sample set DSN001, but reported for the trip blanks and equipment blank samples), a laboratory matrix spike was prepared on an aliquot of sample DSN001 Sample (E08-0185-001) prior to re-extraction of the samples on April 22, 2008. LMS recovery for FOSA on this sample is presented in Table 10. Table 8. Lab Matrix Spike Concentration. D e s c rip tio n DSN001 Sample; 2.5 ppb Lab Matrix Spike Concentration (ng/mL) FOSA 2.50 LMS Recovery = (LMS Sample Concentration - Average Concentration : Sample & Sample D up.). ^ LMS Spike Concentraton PAGE 8 OF 12 3M ENVIRONMENTAL LABORATORY REPORT NO. E08-0185 3.8 Field Matrix Spikes (FMS) Low, mid, and high field matrix spikes were 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. Field matrix spikes are presented in the section 4 of this report. FMS Recovery - (Sample Concentration of FMS - Average Concentration: Field Sample & Field Sample Pup.) ,, 1 Spike Concentrator! Table 9. Field Matrix Spike Concentrations Location Description Low Field Matrix Spike DSN001 Mid Field Matrix Spike High Field Matrix Spike Low Field Matrix Spike Trip Blank Mid Field Matrix Spike High Field Matrix Spike Final Concentration (ng/mL) PFBA PFOA PFBS PFOS FBSA FOSA 0.251 0.262 0.252 0.261 0.252 0.250 5.02 5.25 5.04 5.22 5.04 5.01 100 105 101 104 101 100 0.251 0.262 0.252 0.261 0.252 0.250 5.02 5.25 5.04 5.22 5.04 5.01 100 105 101 104 101 100 !4 Data Summary and Discussion \ The tables below summarize the sample results and field matrix spike recoveries for sample location DSN001 as well as the Trip Blank. An equipment blank sample was also collected in the field. The 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 according to EPA rounding rules. Relative percent difference 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. DNS001 - The recovery of the mid and high FMS for FOSA was 131 %. A laboratory matrix spike (LMS) prepared at 2.5 ppb had a recovery of 145%. Since neither the FMS or LMS recoveries met method acceptance criteria of 100% 30%, the analytical uncertainty for FOSA has been adjusted to 100% 45%. PAGE 9 OF 12 3M ENVIRONMENTAL LABORATORY REPORT NO. E08-0185 Table 10. DSN001 Results 3M LIM S ID Description E08-0185-001 E08-0185-002 E08-0185-003 E08-0185-004 E08-0185-005 DSN001, Sample DSN001, Sample Duplicate DSN001, Field Matrix Spike Low DSN001, Field Matrix Spike Mid DSN001, Field Matrix Spike High Average Concentration (ng/mL) %RPD PFBAm PFOAm P F B S f 1> C o n c e n tra tio n (n g /m L ) % R eco very 3.38 NA 3.50 3.83 8.18 90.4 NA NC 94.4 86.6 3.44 ng/mL 3.5% C o n c e n tra tio n (ng /m L ) % R eco very 6.58 NA 6.76 NA 7.40 NC 11.4 90.1 100 88.9 6.67 ng/m L 2.7% Concentration (n g /m L ) % R eco very 13.9 NA 15.8 NA 15.7 NC 19.0 NC 104 88.4 14.8 ng/m L 13% 3M LIM S ID Description E08-0185-001 DSN001, Sample E08-0185-002 DSN001, Sample Duplicate E08-0185-003 DSN001, Field Matrix Spike Low E08-0185-004 DSN001, Field Matrix Spike Mid E08-0185-005 DSN001, Field Matrix Spike High E08-0185-001 LMS DSN001, Sample; 2.5ppb LMS A v erag e C oncentration (ng/m L) %>RPD PFO Sf1> FBSAm f o s a (3> C o n c e n tra tio n (ng /m L ) % R eco very 13.5 NA 14.2 NA 14.1 NC 18.9 96.7 95.7 78.3 NA NA 13.8 ng/m L 5.1% C o n c e n tra tio n (ng /m L ) % R eco very 43.6 NA ?" < z 45.8 n a (4) 158 NA NA NC NC 112 NA 44.7 ng/mL 4.9% Concentration (n g /m L ) % R eco very 1.47 NA 1.61 1.93 8.08 133 NA NC 131(5) 131(5) 5.17 145(5) 1.54 ng/m L 9.1 % m NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. (1) Samples extracted April 14,2008 and analyzed April 15, 2008. (2) Samples extracted April 14,2008 and analyzed April 18, 2008. (3) Samples extracted April 22, 2008 and analyzed April 23, 2008. (4) Value exceeded calibration range. Dilution of FMS sample was not prepared since the FMS concentration was not appropriate as compared to the sample concentration. (5) Matrix spikes did not meet method acceptance criteria of 100% 30%. The analytical uncertainty for FOS has been adjusted for matrix spike recoveries to 100% 45%. PAGE 10 OF 12 3M ENVIRONMENTAL LABORATORY REPORT NO. E08-0185 Table 11. Trip Blank Results 3 M U M S ID E08-0185-006 E08-0185-007 E08-0185-008 E08-0185-009 E08-0185-010 Description Trip Blank Sample Trip Blank FMS Low Trip Blank FMS Mid Trip Blank FMS High Equipment Blank PFBAm PFOAm P FB S f1> Concentration (n g /m L ) <0.0262 0.248 4.73 94.1 <0.0262 C o n c e n tra tio n % R eco very (n g /m L ) NA <0.0245 98.8 0.254 94.2 4.77 93.7 99.6 NA <0.0245 % R eco very NA 96.8 90.9 94.9 NA Concentration (n g /m L ) <0.0252 0.241 4.44 90.2 <0.0252 % R eco very NA 95.6 88.1 89.5 NA 3M U M S ID E08-0185-006 E08-0185-007 E08-0185-008 E08-0185-009 E08-0185-010 E08-0185-006 E08-0185-007 E08-0185-008 E08-0185-009 Description Trip Blank Sample Trip Blank FMS Low Trip Blank FMS Mid Trip Blank FMS High Equipment Blank Trip Blank Sample Trip Blank FMS Low Trip Blank FMS Mid Trip Blank FMS High PFO Sf1> FBSAn FOSA Concentration (n g /m L ) <0.0251 0.201 4.18 87.3 0.0450 NA NA NA NA C o n c e n tra tio n % R eco very (ng /m L ) NA <0.0252 76.9 0.307 80.0 83.5 6.09 122 NA <0.0252 NA NA NA NA NA NA NA NA VoRecovery NA 122 121 121 NA NA NA NA NA Concentration (n g /m L ) <0.0250(1) 0.253(1) 5.70(1) 103<1) <0.0250(1) <0.0250(3) 0.221(3) 4.19(3) 79.0<3) VoRecovery NA 101 114 103 NA NA 88.2 83.6 78.8 N/A = Not Applicable (1) Samples extracted April 14,2008 and analyzed April 15,2008. (2) Samples extracted April 14,2008 and analyzed April 18,2008. (3) Samples extracted April 22,2008 and analyzed April 23, 2008. PAGE 11 OF 12 3M ENVIRONMENTAL LABORATORY REPORT NO. E08-0185 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 with the exception of FOSA, for which results have been footnoted with an expanded uncertainty. Analysis was completed following 3M Environmental Laboratory method ETS8-154.3 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates in Water by Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry". Analytical results are reported in Table 1 of this report. ig D ata/ Sample Retention All remaining sample and associated project data (hardcopy and electronic) will be archived according to 3M Environmental Laboratory standard operating procedures. \7 Signatures Susan T. Wolf, 3M Principal Analytical Investigator r /Af Date Cliffton B\/oby, Ph.D., 3^f Technical Reviewer Date . ______________________ /vry a h 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. Quality Assurance Representative G oo^ 7 Date PAGE 12 OF 12