Document NGz11K95bjZbQ19LJvJRy4Zrw

3M Environmental Laboratory Final Project Report Amendment Project number: E12-0849 Project title: "Analysis of PFOS, PFHS, PFBS and PFOA in Soils from Decatur, AL in December 2012" Project Lead: Cleston Lange Amendment date: 2/13/2013 Am endm ent number: 01 This amendment modifies the following portion of the final report: 1) Correction to the title of Table 1 2) Update the title page to refer to the amended report as revision 1 3) Corrections to Table 11 and 12 based on Weston comments. Reason for the amendment: Based on comments from Weston after issue of the report: 1) The title of Table 1 was incorrect in original version and referred to the samples as Cordova soils. The new version correctly identifies them as Decatur Soils. 2) Added footnote [d] that indicates the NR value for PFHS was because it was not 2times trip blank result, and removed the NR footnote in the footer of table. 3) Table 11, last result before trip blank had RPD of 8.7%, not 87% in original report. This was corrected 4) Table 12 (NR) result was flagged with [c] footnote, which indicates why it was NR, was accidentally omitted in original report. 5) Update the title to accurately reflect the amended report as "revision 1" Approved by: Cieston Lange, Project Lead Date William Reagen, Laboratory Technical Director Date Page I of l 3M ENVIRONMENTAL LABORATORY STUDY NO. E12-0849, REVISED REPORT Final Report-Revision 1 Analysis of PFOS, PFHS, PFBS and PFOA in Soils from Decatur, AL in December 2012 Laboratory Request Number: E12-0849 Method Requirement: 3M Method ETS-8-053.0 Regulatory Requirement: Non-GLP Report Date - Date of Final Signature Testing Laboratory 3M EHS Operations 3M Environmental Laboratory Building 260-5N-17 Maplewood, MN 55144-1000 Requester Gary Hohenstein Manager, Environ/Regulatory Affairs 3M, Environmental Health and Safety Operations 3M Center, Bldg 224-5W-03 Saint Paul, MN 55144-1000 Phone: (651) 737-3395 gahohenstein@mmm.com PAGE 1 OF 16 3M ENVIRONMENTAL LABORATORY STUDY NO. E12-0849, REVISED REPORT 3M Environmental Laboratory, Analytical Study E12-0849 3M Environmental Laboratory Manager: William K. Reagen, Ph.D. 3M Principal Analytical Investigator: Cleston Lange, Ph.D. 1 Introduction / Summary_____________ The 3M Environmental Laboratory received six (6) Decatur, AL soil samples on December 20, 2012. The objective of this project was to analyze the collected soil samples for perfluorooctanoic acid (PFOA), perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHS) and perfluorooctane sulfonate (PFOS). Samples were analyzed following 3M Environmental Laboratory method ETS-8-053.0 "Solvent Extraction and LC/MS/MS Analysis of Soils for C6-C12 Perfluorinated Carboxylic Acids, and Perfluorobutane Sulfonate, Perfluorohexane Sulfonate, Perfluorooctane Sulfonate and Perfluorooctane Sulfonamide (FOSA): Quantification Using Stable Isotope Labeled Internal Standards". One soil trip blank, included with the shipments to the field and back to the laboratory, was also analyzed with the samples. Several samples required dilutions to attain PFOS and PFOA results within the range of the calibration curve. Results from the analysis of the soil samples and trip blank are summarized in Table 1. Concentrations of PFOS were the highest in the Decatur soil samples, followed generally by PFOA, PFHS and then PFBS. Laboratory matrix spike (LMS) recoveries were within 100 + 30% for all analytes in all samples, except for one PFOA result with LMS recovery of 59.1%, one PFBS result with a LMS recovery of 63.9% and PFBS in one sample for which a reliable LMS recovery could not be achieved and a PFBS result not reported (NR) for that sample. Results for laboratory control samples (LCSs) were used to determine the analytical method uncertainty (95%CI) for PFOS at + 12%, PFHS at + 30%, PFBS at + 7.9% and PFOA at + 25%. The relative standard deviation (RSD) for the added stable isotope labeled surrogate recovery standards (SRSs) was a measure of the analytical method precision and was determined at 11% for 13C4-PFOA and 9.9% for 13C4-PFOS (representing the three sulfonates). Table 1. Results for Decatur Soils Analysis LIMS ID Sample ID Average Concentration (ng/g; dry weight) PFOS PFHS PFBS PFOA E12-0849-001 DAL SB DF601 0 0000 121213 3890 33.3 NR 158 E12-0849-002 DAL SB DF601 0 0050 121213 229 5.04 1.67 [a'c] 38.0 E12-0849-003 DAL SB DF602 0 0000 121213 851 3.56 0.373 17.0 E12-0849-004 DAL SB DF602 0 0050 121213 1730 270 64.8 1410 [c] E12-0849-005 DAL SB DF603 0 0000 121213 112 NR [d] 0.423 23.5 E12-0849-006 DAL SB DF603 0 0050 121213 3.86 6.58 2.43 35.0 E12-0849-007 Trip Blank 1 BLOQ 0.910 [b] BLOQ BLOQ [a] RPD > 50% [b] Trip blank result indicated possible low level contamination of PFHS at ~ 1 ng/g (dry wt.) [c] LMS recovery result was outside of 100+ 30%, but within 100 + 50% [d] Value was not reported (NR) because it was not 2-times the measured trip blank concentration for that analyte PAGE 2 OF 16 3M ENVIRONMENTAL LABORATORY STUDY NO. E12-0849, REVISED REPORT 2 Methods- Analytical and Preparatory 1.1 Methods Analyses were performed following 3M Environmental Laboratory Method ETS-8-053.0. The analytical reference substances listed in Table 2 were used during this study. Table 2. Reference Substances R e fe r e n c e ID P F O S (linear) Chemical Name Chem ical Formula Use Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity R e fe re n c e ID Chemical Name Chem ical Formula Use Pefluoro-n-octane-1sulfonate potassium salt n-C8Fi7SO3 K+ Reference Standard for Calibration and LMSs Sigma-Aldrich February 4, 2014 Frozen 1424328V TCR11-0028-1/1 Powder 99.7% M 8-PFO S [13C8]-Perfl uorooctane-1 sulfonate sodium salt 13C8F17SO3 Na+ Internal standard for PFOS Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity R e fe re n c e ID Chemical Name Chem ical Formula Use Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Wellington October 3, 2015 Frozen 100212 TCR12-0038-1/16, -2/16, -3/16, -4/16 Liquid 98% M 4-PFO A [1,2,3,4-l3C4]-Perfluoro-noctanoic acid 13C412C3F15CO2H PFOA Surrogate Recovery Standard Wellington December 7, 2013 Frozen MPFOA1210 TCR11-0001-5/14 Physical Description Purity Liquid >98% T ech nical-P FO S (lin ear + b ranched) Perfluorooctane-1-sulfonate potassium sait C8F17SO3 K+ Reference standard for LCSs Wellington December 14, 2014 Frozen Br-PFOSK1111 TCR12-0026-1/20 Liquid >98% P F O A (linear) Perfluoro-n-octanoic acid M 4-PFO S [1 ,2 ,3 ,4 -13C4]-Perfluorooctane-1 sulfonate sodium salt 13C4I2C4F17SO3 Na+ PFOS Surrogate Recovery Standard Wellington December 21, 2014 Frozen MPFOS1211 TCR12-0003-4/14 Liquid >98% T ech nical P F O A (lin ear + b ranched) Ammonium perfluorooctanoate n-C7F15CO2H Reference Standard for Calibration and LMSs Sigma-Aldrich July 27, 2016 Frozen MKBD4574V TCR11-0029-1/1 Powder 96.8% M 8-PFO A 13C8-Perfluorooctanoic acid 13C8F15O2H Internal standard for PFOA Wellington October 3, 2015 Frozen 100212 TCR12-0038-1/16, -2/16, -3/16, -4/16 Liquid 98% C7F15CO2 H Reference standard for LCSs Wellington March 17, 2014 Frozen TPFOA0311 TCR11-0042-15/20 Liquid >97% PFBS Perfluorobutane sulfonate Potassium salt C4F9SO3 K+ Reference Standard for Calibration, LMSs and LCSs 3M January 10, 2017 Frozen 101 TCR-121 White Powder 96.7% PAGE 3 OF 16 3M ENVIRONMENTAL LABORATORY STUDY NO. E12-0849, REVISED REPORT I Table 2. Reference Substances Reference ID 18O 2-PFB S Chemical Name Chem ical Formula Use [ l8O]-Perfluorobutane sulfonate Ammonium salt C4F9S[1O2] o n h 4+ Internal standard for PFBS Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity Reference ID Chemical Name Chem ical Formula Use Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity 3M March 9, 2015 Frozen 11546-107-2 TCR-964 & TCR-965 Liquid N/A M 3-PFH S [1,2,3-13C4]-Perfluoro-1hexanesulfonate sodium salt 13C312C3F13S03Na Internal standard for PFHS Wellington October 3, 2015 Frozen 100212 TCR12-0038-1/16, -2/16, -3/16, -4/16 Liquid 98% P F H S (linear) Perfluoro-1-hexanesulfonate sodium salt n-C6F13SO3 Na+ Reference Standard for Calibration and LMSs Wellington March 25, 2015 Frozen LPFHxSAM08 TCR12-0021-1/1 Powder >98% EC F-PFH S (lin ear + b ranch ed) Perfluoro-1-hexanesulfonate Potassium salt C6F13SO3 K+ Reference standard for LCSs 3M February 12, 2017 Frozen NB 120067-69 TCR-083 White Powder 98.6% -- ' r= = --= = r -- - - "-- '-- ~ -- -- - - - - IZzr====-- = = m m -- - - " - 1.2 Sample Collection Ten empty 250-mL HDPE sample bottles and one soil trip blank were prepared and sent to Decatur, AL on December 10, 2012 to Weston Solutions, Inc. personnel. Six soil samples were collected from soil borings by Weston Solutions, Inc. personnel on December 13, 2012 near Field 6 and the railroad tracks located on the 3M Decatur Property. Samples were then shipped to 3M on December 19, 2012 and received at the 3M Environmental Laboratory on December 20, 2012 and logged into LIMS under project E12-0849. 1.3 Sample Preparation Samples were prepared by the extraction procedure defined in method ETS-8-053.0. In summary, preparation involves removal of a 1 cubic centimeter (1 cc) soil sample aliquot (typically ~ 1 gram) from each sample bottle using a fixed volume 1 cc spoon, followed by accurate weight determination of the aliquot on a 5-place balance. Stones and debris generally larger than 5 mm were typically removed during weighing to ensure better sample homogeneity. Prior to extraction, each weighed sample aliquot was fortified with a fixed quantity of stable isotope labeled internal standards (IS) and surrogate recovery standards (SRS) as defined in Table 2. Following the addition of IS and SRS compounds, each was extracted by adding 8 mL of a 4:1 acetonitrile:water solution followed by sonication for 1-2 hours, then centrifugation to separate out the solids. An aliquot of the clear supernatant was transferred to an autovial for LC/MS/MS analysis. PAGE 4 OF 16 3M ENVIRONMENTAL LABORATORY STUDY NO. E12-0849, REVISED REPORT Soil matrix blanks and calibration standards are prepared sim ilar to sam ples using a control soil TCR -455. A 1 cc aliquot o f soil TC R -455 weighed nom inal 1.0 gram (dry weight). Because environm ental soil and sedim ent sam ples can vary significantly by dry w eight for a 1 cc sam ple, the instrum ent response is calibrated for each analyte based on the m ass o f target analyte added to the standard calibration soil matrix prior to extraction. Calibration standards w ere fortified from the range of 0.200 ng to 500 ng fo r each analyte; nom inal calibrated range w a s 0.200 ng/g to 500 ng/g in control soil TCR -455. Percent m oistures used for calculating soil dry weights for the environm ental sam ples w ere determ ined from separate w eighings o f sam ple. 1.4 LC/MS/MS Analysis Each extract w a s analyzed fo r PFO S , P FH S , P FB S and P F O A by LC /M S /M S as de scrib e d in m ethod ETS-8-053.0. Sam ple analyte concentrations for LMS preparations w ere estim ated from a range finding (screening) analyses as analytical runs s130102b and s130103a. Results o f the screening analysis were not used for reporting. Data for definitive reporting o f results w ere obtained from analysis o f analytical batch s1 3 0 1 0 9 a and s 1 30111 a. S a m p le s w ith Q C failure in run s 1 3 0 1 09a or s130111a w e re reassayed in analytical batch s 1 3 0 1 1 7a (P FO S , P F O A and P FB S only). Details o f the specific instrum ent param eters, the liquid chrom atography gradient program , and the specific m ass transitions analyzed are described in th e ra w d ata w h ich are provided as hard copies in the final stu d y data packet, and are briefly described below in Tables 3, 4 and 5. All data used fo r reporting these results were from analytical runs Table 3. Instrument Information Instrument Name Analytical Method ID Liquid Chromatograph Guard Column Analytical column 1 Analytical column 2 Injection Volume Mass Spectrometer Ion Source Polarity Software Definitive Analysis (s) ETS-Stan ETS-8-053.0 A gilent/H P 1100 H PLC Prism RP O asis HLP C 18 Betasil 25 pL API 4000 T urbo Ion S pray N egative Ion A n a ly s t 1.6.1 PAGE 5 OF 16 3M ENVIRONMENTAL LABORATORY STUDY NO. E12-0849, REVISED REPORT Table 4. Isocratic Liquid Chromatography Conditions (ETS-8-053) Step Number 1 2 3 4 5 6 7 8 Total Time [min] 0.0 3.0 3.5 17.0 17.5 19.5 20.0 23.0 Flow Rate [m L /m in ] 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Percent A [2 mm Aqueous Ammonium Acetate] 97 97 70 40 10 10 97 97 Percent B [Acetonitrile] 3 3 30 60 90 90 3 3 Table 5. Mass Transitions Analyte Mass Transitions Monitored PFOA 413>169, 413>219, 413>369 13C 4-PFO A (S R S ) 417>372 13C s-P F O A (IS) PFOS 421>376 499>130, 499>99, 499>80 13C s-P F O S (IS) 507>80 PFHS 399>99, 399>80 13C3t P F H S (IS) 402>80 PFBS 299>99, 299>80 18O -P F B S (IS) 303>84 13C 4-P FO S (S R S ) 503>80 Note: Multiple mass transitions are summed to give the instrument response for that analyte. 3 Results 3.1 Calibration Internal Standard Calibration: All samples were analyzed against a matrix-matched stable isotope IS calibration curve. Calibration standards were prepared by spiking known amounts of target analytes into 1cc aliquots of control soil TCR-455. Linear isomers of target analytes were used for calibration. Each soil calibration standard received nominal 3 ng of each IS and 3 ng of each SRS. A total of twelve spiked standards ranging from nominal 0.200 ng to 500 ng of each target analyte were prepared and analyzed. To meet linearity and accuracy criteria, the high calibration standard (500 ng) was disabled for PFBA. The plot of the analyte/IS ratio for each standard versus known standard analyte fortification amount was fitted using a quadratic, 1/x weighted linear regression. The data were not forced through zero during the fitting process. Back-calculating the standard concentrations using the peak area ratios and the resultant calibration curve confirmed accuracy of each curve point at within 100 + 30% (+ 35% at LLOQ). The correlation coefficient (r) was greater than 0.995 for each analyte fitted calibration curve. PAGE 6 OF 16 3M ENVIRONMENTAL LABORATORY STUDY NO. E12-0849, REVISED REPORT 3.2 Limits of Quantitation The lower limit of quantitation (LLOQ) for each analyte was the lowest non-zero calibration standard in the curve that met linearity and accuracy requirements and for which the peak area ratio was at least two times the average peak area response of the method blanks. The LLOQs for this analysis were the nominal 0.200 ng calibration standard (nominal 0.2 00 ng/cc soil) for all analytes. The reportable LLOQ for PFHS was adjusted up to 1.8 ng/g based on the trip blank result. The ULOQ was the highest standard in the curve, and was the 500 ng calibration for all analyses. Values above the ULOQ were appropriately diluted to achieve results within the range of the curve. In some instances, samples were diluted 100-fold to achieve results within the range of the calibration. 3.3 Continuing Calibration Reinjection of calibration standards during analytical runs were conducted to verify the analytical run was maintained in control throughout the analysis. During the course of the analytical sequence, several mid-level 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 criterion of 100% 30% for CCVs was met for all analytes in the analytical runs used for reporting results. 3.4 Blanks Two types of blanks were prepared and analyzed with the samples: method blanks (procedural blanks) consisting of extracted control soil matrix and instrument blanks (zero volume injections). Method blank results were reviewed and used to evaluate method performance to determine the LLOQ for each analyte. Instrument blanks provided the ability to monitor for potential instrument carry over from injection to injection. Significant carry over was not observed. 3.5 Surrogate Recovery Standards (SRSs) Two stable isotope-labeled SRSs were added to each soil sample aliquot during preparation and extraction, one representing perfluorinated carboxylate (13C4-PFOA for PFOA) and the other representing the perfluorinated sulfonates (13C4-PFOS for PFOS, PFHS and PFBS). The SRS recovery results for the Decatur soils were used to evaluate the analytical method precision overall. The average SRS recoveries and standard deviations for the Decatur soil samples was determined at 97.7% + 10% for 13C4-PFOA (n = 58) and 97.7% + 9.6% for 13C4-PFOS (n = 58). The analytical method precision was indicated by the RSDs and was 11% 13C4-PFOA and 9.9 % for 13C4-PFOS. Overall, the SRSs results demonstrate excellent analytical method precision. 3.6 Lab Control Spikes (LCSs) Laboratory control samples were prepared with each analytical batch and were prepared by fortifying target analytes into 1 cc aliquots of control soil TCR-455 at three levels of nominal 3.00 ng, 30.0 ng and 300 ng, with each LCS level prepared in triplicate. In analytical runs containing diluted samples, 10-fold diluted (DF10) and 100-fold (DF100) LCSs were also included. The LCSs for PFOS, PFHS, PFBS and PFOA were all within acceptance criteria of 100 + 30% as shown in Table 6, Table 7, Table 8 and Table 9, respectively, except for one LCS for PFOA which was at 138%. The analytical method uncertainties (95%Cl) determined from LCS results were + 12% for PFOS, + 30% for PFHS, + 7.9% for PFBS and + 25% for PFOA. PAGE 7 OF 16 3M ENVIRONMENTAL LABORATORY STUDY NO. E12-0849, REVISED REPORT Table 6. LCS Results (PFOS) Sample ID LCSs (s130109a) LCSs (s130111a) LCSs (s130117a) Average Recovery Std. Dev. RSD Overall Average Overall Std. Dev. Overall RSD PFOS Method Uncertainty (2 x Std. Deviation, 95% CI) 3.0 ng LCS 110% 107% 108% 107% 106% 110% 117% 110% 102% 108% 4.1% 3.8% PFOS Recovery 30 ng LCS 300 ng LCS 115% 116% 123% 112% 111% 127% 105% 97.3% 103% 112% 9.5% 8.4% 110% 111% 110% 103% 101% 103% 108% 107% 101% 106% 4.0% 3.8% 108% 6.0% 5.6% + 12% 300 ng LCS (DF 10) NA NA NA 106% 104% 104% 105% 103% 107% 105% 1.4% 1.4% 300 ng LCS (DF 100) NA NA NA 104% 109% 105% 98.0% 109% 110% 106% 4.7% 4.4% Table 7. LCS Results (PFHS) Sample ID LCSs (s130109a) LCSs (s130111a) LCSs (s130117a) Average Recovery Std. Dev. RSD Overall Average Overall Std. Dev. Overall RSD PFHS Method Uncertainty (2 x Std. Deviation, 95% CI) 3.0 ng LCS 130% 125% 124% 124% 130% 121% NA NA NA 126% 3.7% 3.0% PFHS Recovery 30 ng LCS 300 ng LCS 97.3% 97.3% 111% 101% 93.3% 103% NA NA NA 100% 6.0% 6.0% 93.3% 96.0% 95.7% 91.3% 93.3% 87.0% NA NA NA 92.8% 3.3% 3.6% 107% 15% 14% + 30% 300 ng LCS (DF 10) NA NA NA 96.7% 92.7% 93.7% NA NA NA 94.3% 2.1% 2.2% 300 ng LCS (DF 100) NA NA NA 125% 121% 119% NA NA NA 122% 3.4% 2.8% PAGE 8 OF 16 3M ENVIRONMENTAL LABORATORY STUDY NO. E12-0849, REVISED REPORT Table 8. LCS Results (PFBS) Sample ID LCSs (s130109a) LCSs (s130111a) LCSs (s130117a) Average Recovery Std. Dev. RSD Overall Average Overall Std. Dev. Overall RSD PFBS Method Uncertainty (2 x Std. Deviation, 95% CI) 2.99 ng LCS 93.6% 97.3% 94.6% 97.7% 99.0% 99.7% 104% 95.3% 97.0% 97.6% 3.2% 3.3% PFBS Recovery 29.9 ng LCS 299 ng LCS 98.7% 95.0% 97.0% 98.3% 99.0% 107% 88.0 % 91.0 % 94.3% 96.4% 5.3% 5.5% 91.6% 92.3% 90.6% 100% 99.0% 95.7% 97.7% 98.7% 94.3% 95.6% 3.5% 3.7% 96.2% 3.9% 4.1% + 7.9% 299 ng LCS (DF 10) NA NA NA 102% 91.0% 97.7% 93.0% 96.7% 96.0% 96.0% 3.7% 3.9% 299 ng LCS (DF 100) NA NA NA 96.0% 95.0% 91.3% 89.0% 99.3% 97.3% 94.6% 3.9% 4.1% Table 9. LCS Results (PFOA) Sample ID 3.0 ng LCS LCSs (s130109a) LCSs (s130111a) LCSs (s130117a) 85.6% 102% 111% 89.6% 92.3% 85.6% 95.3% 89.6% 96.3% Average Recovery 94.1% Std. Dev. 8.2% RSD Overall Average Overall Std. Dev. Overall RSD PFOA Method Uncertainty (2 x Std. Deviation, 95% CI) 8.7% [a] Result was outside of 100 + 30% PFOA Recovery 30 ng LCS 300 ng LCS 108% 115% 121% 82.3% 93.3% 101% 104% 94.3% 83.3% 100% 13% 13% 107% 112% 101% 119% 138% [a] 102% 123% 96.0% 105% 111% 13% 12% 100% 13% 13% + 25% 300 ng LCS (DF 10) NA NA NA 100% 93.6% 87.0% 100% 96.0% 101% 96.3% 5.4% 5.6% 300 ng LCS (DF 100) NA NA NA 87.0% 75.3% 102% 95.3% 115% 101% 96.0% 14% 14% PAGE 9 OF 16 3M ENVIRONMENTAL LABORATORY STUDY NO. E12-0849, REVISED REPORT 3.7 Laboratory Matrix Spikes (LMS) Laboratory matrix spikes (LMSs) were prepared for each sample at a level that was appropriate relative to the endogenous target analyte level. All LMS recoveries were within method acceptance criteria of 100 30%, except for the PFBA result of the Trip Blank which was 143%. Overall, the LMS results confirmed that "unknown" components in the sample matrix did not significantly interfere with the extraction and analysis of the analytes of interest for most samples. The reference materials used for fortification of LMS was comprised of primarily linear isomers for PFOA and PFOS. The LMS recovery results are shown with sample results in Table 11, Table 12, Table 13 and Table 14 for PFOS, PFHS, PFBS and PFOA, respectively. TL,M,,S Recovery = -(-D--e-t-e-r--m--i-n-e--d--C--o--n-c-e--n-t-r-a--ti-o--n--o--f--L--M--S------D--e--t-e-r-m--i-n--e-d--C--o--n--c-e-n--t-r-a-t-i-o-n---o-f--F--i-e-l-d--S--a-m--p*l1e0)0% Spike Concentration 3.8 Percent Moisture Determination The percent moisture was determined in duplicate for each soil sample. For each replicate, a sample aliquot is accurately weighed to determine the "wet" weight. Then the aliquot is dried at > 105C unt il no further loss in mass occurs (due to water evaporation), and then the dry weight is accurately determined. The average percent moisture and RPD of the duplicate determinations for each is reported in Table 10. The percent moisture was calculated by the following equation: ,,Percent ,,M,oi.sture = -(--Orig-in--a-l--S--o-i-l-W---e--t-M---a-s--s-----D--r-i-e--d--S--o-i-l-M---a-s--s)- * 100% Original Soil Wet Mass Table 10. Percent Moistures for Decatur Soils (December 2012) LIMS ID Sample ID Average Percent Moisture (w/w) [a] Relative Percent Difference [a] E12-0849-001 DAL SB DF601 0 0000 121213 13.6% 3.8% E12-0849-002 DAL SB DF601 0 0050 121213 20.2% 11% E12-0849-003 DAL SB DF602 0 0000 121213 16.0% 0.92% E12-0849-004 DAL SB DF602 0 0050 121213 17.4% 6.8% E12-0849-005 DAL SB DF603 0 0000 121213 13.3% 0.86% E12-0849-006 DAL SB DF603 0 0050 121213 15.1% 1.1% E12-0849-007 Trip Blank 1 2.23% 8.9% [a] Percent moisture determined for duplicate samples of soil taken from each sample bottle, RPD is the relative percent difference of the duplicate determined values. PAGE 10 OF 16 3M ENVIRONMENTAL LABORATORY STUDY NO. E12-0849, REVISED REPORT 3.9 Sample Results Table 11. Individual PFOS Results for Decatur Soils (December 2012) Sample Description Surrogate (1 3 C4 -PFOS) Recovery [a] LMS Spike Concentration (ng/g; dry weight) Measured PFOS Concentration (ng/g; dry weight) LMS recovery (Data Accuracy) Average PFOS Concentration (ng/g; dry wt.) and RPD (Data Precision) DAL SB DF601 0 0000 121213 92.4% NA 3420 NA 3890 DAL SB DF601 0 0000 121213 Duplicate 90.7% 4350 DAL SB DF601 0 0000 121213 LMS 96.2% 9220 14800 118% 24% DAL SB DF601 0 0050 121213 94.1% NA 251 NA 229 DAL SB DF601 0 0050 121213 Duplicate 90.7% 207 DAL SB DF601 0 0050 121213 Low LMS DAL SB DF601 0 0050 121213 High LMS 87.9% NR 450 NR 665 1660 96.8% NR 19% DAL SB DF602 0 0000 121213 93.4% NA 846 NA 851 DAL SB DF602 0 0000 121213 Duplicate 92.7% 856 DAL SB DF602 0 0000 121213 Low LMS DAL SB DF602 0 0000 121213 High LMS 96.6% NR 432 NR 1280 1620 99.0% NR 1.2% DAL SB DF602 0 0050 121213 DAL SB DF602 0 0050 121213 Duplicate 98.0% 98.0% NA 1420 2040 NA 1730 DAL SB DF602 0 0050 121213 Low LMS DAL SB DF602 0 0050 121213 High LMS NR 94.8% NR 1360 3520 3000 NR 93.5% 36% DAL SB DF603 0 0000 121213 DAL SB DF603 0 0000 121213 Duplicate 95.5% 95.2% NA 115 109 NA 112 DAL SB DF603 0 0000 121213 Low LMS DAL SB DF603 0 0000 121213 High LMS 94.8% NR 428 NR 534 1980 98.5% NR 4.8% DAL SB DF603 0 0050 121213 85.4% 4.02 NA NA 3.86 DAL SB DF603 0 0050 121213 Duplicate 93.4% 3.69 DAL SB DF603 0 0050 121213 Low LMS DAL SB DF603 0 0050 121213 High LMS 91.4% NR 4.13 NR 7.74 37.3 94.2% NR 87% [c] Trip Blank 1 Trip Blank 1 Duplicate 92.7% NA BLOQ NA BLOQ 104% BLOQ Trip Blank 1 Lab Matrix Spike 87.5% 1.01 1.14 113% NA Concentration values are rounded to 3 significant figures, statistical results rounded to 2 significant figures, but non-rounded values used for data calculations. [a] SRS recovery only shown from the analytical run used to report the results for that analyte in that sample [b] Recovery was outside of 100 + 30% [c] RPD > 20% BLOQ; result was less than the analyte/IS response for the lowest (nominal 0.200 ng) calibration standard NA; Not applicable NR; Not Reported because LMS fortification level was not appropriate relative to the determined level of analyte in the sample PAGE 11 OF 16 3M ENVIRONMENTAL LABORATORY STUDY NO. E12-0849, REVISED REPORT Table 12. Individual PFHS Results for Decatur Soils (December 2012) Sample Description Surrogate (1 3 C4 -PFOS) Recovery [a] LMS Spike Concentration (ng/g; dry weight) Measured PFHS Concentration (ng/g; dry weight) LMS recovery (Data Accuracy) Average PFHS Concentration (ng/g; dry wt.) and RPD (Data Precision) DAL SB DF601 0 0000 121213 122% NA 27.5 NA 33.3 DAL SB DF601 0 0000 121213 Duplicate 132% [b] 39.0 DAL SB DF601 0 0000 121213 Low LMS DAL SB DF601 0 0000 121213 High LMS 125% 108% NR 120 NR 152 NR 98.8% 34% DAL SB DF601 0 0050 121213 94.1% NA 5.60 NA 5.04 DAL SB DF601 0 0050 121213 Duplicate 90.7% 4.49 DAL SB DF601 0 0050 121213 Low LMS DAL SB DF601 0 0050 121213 High LMS 103% 101% 4.50 NR 9.89 NR 108% NR 22% DAL SB DF602 0 0000 121213 94.8% 3.49 NA NA 3.56 DAL SB DF602 0 0000 121213 Duplicate 95.9% 3.64 DAL SB DF602 0 0000 121213 Low LMS DAL SB DF602 0 0000 121213 High LMS 97.3% 102% 4.32 NR 8.37 NR 111% NR 4.2% DAL SB DF602 0 0050 121213 95.5% 256 NA NA 270 DAL SB DF602 0 0050 121213 Duplicate 99.4% 283 DAL SB DF602 0 0050 121213 Low LMS DAL SB DF602 0 0050 121213 High LMS 95.2% 94.8% NR 340 NR 517 NR 72.8% 9.9% DAL SB DF603 0 0000 121213 DAL SB DF603 0 0000 121213 Duplicate 95.5% 95.2% NA 0.963 1.14 NA NR [c] DAL SB DF603 0 0000 121213 Low LMS DAL SB DF603 0 0000 121213 High LMS 97.6% 91.0% 4.28 NR 5.83 NR 112% NR 17% DAL SB DF603 0 0050 121213 85.4% NA 6.44 NA 6.58 DAL SB DF603 0 0050 121213 Duplicate 93.4% 6.72 DAL SB DF603 0 0050 121213 Low LMS DAL SB DF603 0 0050 121213 High LMS 91.4% 92.1% 4.13 NR 10.8 NR 103% NR 4.3% Trip Blank 1 Trip Blank 1 Duplicate 92.7% 0.868 NA NA 0.910 104% 0.952 Trip Blank 1 Lab Matrix Spike 87.5% 1.01 2.17 126% 9.2% Concentration values are rounded to 3 significant figures, statistical results rounded to 2 significant figures, but non-rounded values used for data calculations. [a] SRS recovery only shown from the analytical run used to report the results for that analyte in that sample [b] Recovery was outside of 100 + 30%, but within 100 + 50% [c] Result was not 2-times the trip blank response and was not reportable (NR) BLOQ; result was less than the analyte/IS response for the lowest (nominal 0.200 ng) calibration standard NA; Not applicable NR; Not Reported because LMS fortification level was not appropriate relative to the determined level of analyte in the sample PAGE 12 OF 16 3M ENVIRONMENTAL LABORATORY STUDY NO. E12-0849, REVISED REPORT Table 13. Individual PFBS Results for Decatur Soils (December 2012) Sample Description Surrogate (1 3 C8 -PFOS) Recovery [a] LMS Spike Concentration (ng/g; dry weight) Measured PFBS Concentration (ng/g; dry weight) LMS recovery (Data Accuracy) Average PFBS Concentration (ng/g; dry wt.) and RPD (Data Precision) DAL SB DF601 0 0000 121213 DAL SB DF601 0 0000 121213 Duplicate NR* NR* NR* NR* NR* NR* NR* DAL SB DF601 0 0000 121213 LMS NR* NR* NR* NR* NR* DAL SB DF601 0 0050 121213 DAL SB DF601 0 0050 121213 Duplicate 100% 103% NA 2.53 0.801 NA 1.67 DAL SB DF601 0 0050 121213 LMS DAL SB DF601 0 0050 121213 High LMS 136% [c] NA 1.80 NR 2.82 NR 63.9% [c] NR 104% [b] DAL SB DF602 0 0000 121213 94.1% NA 0.385 NA 0.373 DAL SB DF602 0 0000 121213 Duplicate 90.7% 0.361 DAL SB DF602 0 0000 121213 Low LMS DAL SB DF602 0 0000 121213 High LMS 87.9% 96.2% 1.73 NR 2.27 NR 110% NR 6.5% DAL SB DF602 0 0050 121213 94.8% 60.8 NA NA 64.8 DAL SB DF602 0 0050 121213 Duplicate 95.9% 68.9 DAL SB DF602 0 0050 121213 Low LMS DAL SB DF602 0 0050 121213 High LMS 97.3% 102% NR 34.0 NR 93.1 NR 83.1% 13% DAL SB DF603 0 0000 121213 95.5% NA 0.452 NA 0.423 DAL SB DF603 0 0000 121213 Duplicate 99.4% 0.393 DAL SB DF603 0 0000 121213 Low LMS DAL SB DF603 0 0000 121213 High LMS 95.2% 107% 1.71 NR 2.52 NR 122% NR 14% DAL SB DF603 0 0050 121213 95.5% NA 2.45 NA 2.43 DAL SB DF603 0 0050 121213 Duplicate 95.2% 2.40 DAL SB DF603 0 0050 121213 Low LMS DAL SB DF603 0 0050 121213 High LMS 97.6% 91.0% 1.65 NR 3.96 NR 93.1% NR 2.0% Trip Blank 1 Trip Blank 1 Duplicate 85.4% BLOQ NA NA BLOQ 93.4% BLOQ Trip Blank 1 Lab Matrix Spike 91.4% 1.01 1.19 118% NA Concentration values are rounded to 3 significant figures, statistical results rounded to 2 significant figures, but non-rounded values used for data calculations. [a] SRS recovery only shown from the analytical run used to report the results for that analyte in that sample [b] RPD > 50% [c] Recovery was outside of 100 + 30%, but within 100 + 50% BLOQ; result was less than the analyte/IS response for the lowest (nominal 0.200 ng) calibration standard NA; Not applicable NR; Not Reported because LMS fortification level was not appropriate relative to the determined level of analyte in the sample NR*; Not reported because of QC failure PAGE 13 OF 16 3M ENVIRONMENTAL LABORATORY STUDY NO. E12-0849, REVISED REPORT Table 14. Individual PFOA Results for Decatur Soils (December 2012) Sample Description Surrogate (1 3 C4 PFOA) Recovery [a] LMS Spike Concentration (ng/g; dry weight) Measured PFOA Concentration (ng/g; dry weight) LMS recovery (Data Accuracy) Average PFOA Concentration (ng/g; dry wt.) and RPD (Data Precision) DAL SB DF601 0 0000 121213 DAL SB DF601 0 0000 121213 Duplicate 92.5% 97.5% NA 145 171 NA 158 DAL SB DF601 0 0000 121213 LMS 95.5% 307 455 96.6% 16% DAL SB DF601 0 0050 121213 92.5% NA 39.6 NA 38.0 DAL SB DF601 0 0050 121213 Duplicate 121% 36.3 DAL SB DF601 0 0050 121213 Low LMS DAL SB DF601 0 0050 121213 High LMS 112% NR 45.0 NR 91.7 NR 120% NR 8.7% DAL SB DF602 0 0000 121213 DAL SB DF602 0 0000 121213 Duplicate 111% 93.9% NA 18.6 15.5 NA 17.0 DAL SB DF602 0 0000 121213 Low LMS DAL SB DF602 0 0000 121213 High LMS 98.5% NR 43.2 NR 65.4 NR 112% NR 18% DAL SB DF602 0 0050 121213 DAL SB DF602 0 0050 121213 Duplicate 97.9% 101% NA 1396 1426 NA 1410 DAL SB DF602 0 0050 121213 LMS 88.8% 1025 2017 59.1% [b] 2.2% DAL SB DF603 0 0000 121213 95.5% NA 22.9 NA 23.5 DAL SB DF603 0 0000 121213 Duplicate 106% 24.0 DAL SB DF603 0 0000 121213 Low LMS DAL SB DF603 0 0000 121213 High LMS 104% 83.5% 42.8 470 79.0 440 130% 88.6% 4.7% DAL SB DF603 0 0050 121213 DAL SB DF603 0 0050 121213 Duplicate 103% 124% NA 30.8 39.2 NA 35.0 DAL SB DF603 0 0050 121213 Low LMS DAL SB DF603 0 0050 121213 High LMS 113% 98.9% 41.3 362 85.9 ULOQ 123% ULOQ 24% Trip Blank 1 Trip Blank 1 Duplicate 102% BLOQ NA NA BLOQ 99.2% BLOQ Trip Blank 1 Lab Matrix Spike 103% 1.01 1.09 108% NA Concentration values are rounded to 3 significant figures, statistical results rounded to 2 significant figures, but non-rounded values used for data calculations. [a] SRS recovery only shown from the analytical run used to report the results for that analyte in that sample [b] LMS recover was outside of 100 + 30%, but within 100 + 50% BLOQ; result was less than the analyte/IS response for the lowest (nominal 0.200 ng) calibration standard NA; Not applicable NR; Not Reported because LMS fortification level was not appropriate relative to the determined level of analyte in the sample PAGE 14 OF 16 3M ENVIRONMENTAL LABORATORY STUDY NO. E12-0849, REVISED REPORT 4 Data/Sample Retention All remaining sample and associated project data (hardcopy and electronic) will be archived according to 3M Environmental Laboratory standard operating procedures. 5 Conclusion The quantitative analysis of the Decatur soils collected from near Field 6 and near the railroad tracks at the 3M Decatur facility was complete. The levels of PFOS were generally the highest concentrations, followed by PFOA, PFHS and then PFBS. PFOS concentrations ranged from 3.86 ng/g (dry wt) to 3890 ng/g (dry wt.) ;PFOA ranged from 23.5 ng/g (dry wt.) to 1410 ng/g (dry wt.); PFHS ranged from 3.56 ng/g (dry wt.) to 270 ng/g (dry wt.) and PFBS ranged from 0.373 ng/g to 64.8 ng/g (dry wt.). One result for PFBS could not be reported (NR) due quality control failure. Laboratory matrix spike recoveries were used to determine the sample specific accuracy and showed good recoveries within 100 + 30% for all analytes reported in samples, except one PFBS result which could not be reported because of poor LMS recovery. The relative percent difference (RPDs) between duplicate analytical sample results was typically less than 20%, and less than 50% for all samples except for one PFBS result with a RPD of 104% and one PFOS result with a RPD of 87%. The analytical data accuracy determined from SRS recoveries showed acceptable recovery at within 100 + 30% and the RSD (data precision) was less than 10%. The analytical method uncertainties (95%CI) determined from LCS results were + 12% for PFOS, + 30% for PFHS, + 7.9% for PFBS and + 25% for PFOA. 6 Attachments None PAGE 15 OF 16 7 Signatures 3M ENVIRONMENTAL LABORATORY STUDY NO. E12-0849, REVISED REPORT Cleston Lange, Ph.D., 3M Principal Analytical Investigator William K. Reagen, Ph.D., 3M Environmental Laboratory Manager T Date /3 /ZT& O /. ? Date The 3M Environmental Laboratory's Quality Assurance Unit has audited the data and report for this project. Ul Quality Assurance Representative a-a'/i Date PAGE 16 OF 16