Document o9r15jKYbJY4wzBDqb8mOpawo

.a A z24,-1933 \ Analytical Report 3M Company Analysis of PFOA and PFOS in Water Samples from Oakdale Municipality E04-0911 Exygen Report No. L0004145 Revised Testing Laboratory Exygen Research 3058 Research Drive State College, PA 16801 Requester Gary A. Rohenstein Manager, Environmental Operations EHS Oprations 3M Company Building 42-3E-27 St. Paul, MN 55106 `rii I 4 J & 3 0 5 8 ReseIanch Drive <#^^State College, PA 16801, USA PAGE 1 0 F S T; 800.2281.3219 F F:: 814.272.1019 4 exygen.com 1 Introduction In this revised report, results are reported tor the analysis of perfluorooctanoic acid (PFO A ) and perfluorooctanesulfonate (PFO S) in water samples received at Exygen as requested by Gary Hohenstein of 3M Company. The report was revised to update the requester information and to m ake minor changes to the text of the report Analytical results were not changed in this revision. T he Exygen project number assigned to the sam ples is L0004145. Table I lists the target analytes quantitated for the samples. Table I. Target Analytes for Quantitation Param eter Acronym Form ula Perfluorooctanoic Acid PFOA C7F15CO O H Perfluorooctanesulfonate PFOS C8F17S 0 3H 2 Sample Receipt Twenty-seven samples were received at Exygen in 500 mL white plastic narrow-mouth bottles. At the request of 3M , all samples were analyzed. A copy of all sam ple log-in information is presented in Attachment A. The samples were received on 12/28/04. The sam ples were shipped am bient via UPS. The samples were stored refrigerated from time of receipt until analysis. 3 Methods - Analytical and Preparatory 3.1 Water Sample Preparation Solid phase extraction (SPE) was used to prepare the w ater sam ples for LC/M S/M S analysis. Forty milliliters of the water sam ple was transferred to a C 18 S PE cartridge. The cartridge was washed with 5 mL of a 40% methanol: 60% water wash. The cartridge was eluted with 5 mL of 100% methanol. A portion of the extract was transferred to autosam pler vials and analyzed using electrospray LC/M S/M S. 3.2 Sample Analysis by LC/MS/MS In High Pressure Liquid Chromatography (HPLC), an aliquot of extract is injected and passed through a liquid-phase chromatographic column. Based on the affinity of the analyte for the stationary phase in the column relative to the liquid mobile phase, the analyte is retained for a PAGE2 OF5 characteristic amount of time. Following HPLC separation, mass spectrometry provides a rapid and accurate means for analyzing a wide range of organic compounds. Molecules are ionized, fragmented, and detected. The ions characteristic of the compounds are observed and quantitated against extracted standards. An H P1100 system interfaced to an Applied Biosystems API 4000 was used to analyze the sample extracts for quantitation. Isomer separation was obtained using a gradient elution through a Therm o Fluophase RP, 50 x 2.1 mm x 5pm column. The sum of the isomers is reported as a single value for each of the analytes. The following gradient was performed: Mobile Phase (A): Mobile Phase (B): 2m M Ammonium Acetate in W ater Methanol Tim e 0 .0 1.0 8 .0 10.0 11.0 18.0 %A 65 65 25 25 65 65 % 35 35 75 75 35 35 The following parameters were used for operation of the m ass spectrometer: Param eter Ionization Mode Polarity Transitions Monitored Gas Tem perature Drying Gas (N2) S etting Electrospray N eg ative 413->369 (PFO A), 499-> 80 (PFO S), 415->370 (13C -PFO A) 350C 7.0 L/min 4 Analysis 4.1 Calibration A 7-point calibration curve was analyzed initially and throughout the analytical sequence for PFOA, PFO S and 13C PFOA. The calibration points were prepared at 0 ,2 5 ,5 0 ,1 0 0 ,2 5 0 ,5 0 0 , and 1000 ng/L (ppt) for LC/M S/M S analysis. Calibration standards are prepared using the sam e SPE procedure used for samples. The instrument response versus the concentration was plotted for each point. Using linear regression with 1/x weighting, the slope, y-intercept and coefficient of determination ( r ) were determined. A calibration curve is acceptable if r* > 0 .9 8 5 . For the results reported here, calibration criteria were met. The calibration curves are included in the raw data in Attachment C . PAGE3 OF5 4.2 Surrogates ,3C PFO A is used as a surrogate tor the water samples. '3C PFO A was added to the empty sam ple containers before the bottles were sent to the field for sampling. In the field, the bottles were filled to a volumetric fill line with the sample. 13C PFO A recoveries can be found in Attachment B. 4.3 Laboratory Control Spikes Laboratory control spikes in the analytical set were prepared by adding a known concentration of PFO A, 13C -PFO A, and PFO S to laboratory reagents. Laboratory control spikes are used to assess method accuracy. The laboratory control spikes must show recoveries between 70130% or the data is rejected. For the results reported here, the laboratory control spikes were within the acceptable range. 4.4 Field Matrix Spikes A low and high matrix spike was prepared for every water sample in the field. Compounds were added to the empty sam ple containers before the bottles were sent to the field for sampling. Matrix spikes are used to assess method accuracy in the matrix. The matrix spikes should show recoveries between 70-130% . For the results reported here, the matrix spikes were within the acceptable range, except as noted in Section 6 of this report. 4.5 Sample Related Comments All w ater samples were collected in duplicate. Duplicate sample results are reported along with the sam ple results in Attachment B. 5 Data Summary Please see Attachment B for a detailed listing of the analytical results. The results are reported in parts per billion (ng/mL) for PFO A and PFOS. 6 Statement of Accuracy Based on results of laboratory control spikes, field matrix spikes, and surrogate spikes, the analytical accuracy for PFO S and PFOA results is 30% . Laboratory control spikes, surrogate spikes and field matrix spikes showed recoveries within these ranges, with the following exceptions: The PFOA and PFO S recovery in 0 -W 5 -1 27287 Low Spike and O -W 8-572608 Low Spike could not be calculated because the inherent sam ple concentration In this sample was over 3 times greater than the spiking concentration. The PFO S recovery for sample 0 -W 7 -4 6 3 53 4 Low Spike was 48% . The PFOA recovery for sam ple O -W 2-208463 Low Spike was 61 % . PACE4 OFS Specific sample recoveries are given in Attachment B. 7 Data/Sample Retention Samples will be returned to 3M 60 days after final reporting. All electronic data is archived on retrievable media and hard copy reports are stored in data folders maintained by Exygen. Hardcopy data is stored for a minimum of five years. The client will be notified 30 days prior to the disposal of hardcopy data. I 8 Attachments ill 7.1 Attachment A: Analytical Results 4 7.2 Attachment B: Spike Recovery Data 7.3 Attachment C: Chain of Custody Forms M 7.4 Attachment D: Raw Analytical Data Ii 9 Signatures li itf ^ -fo r l u A xU fZ-t/os Karen Risha, Principal Investigator D ate li Date li >4 4 Ml 4 ill PAGE5 OFS ill Section A Summary of PFOA and PFOS in Water Samples E04-0911 Exygen IP L 4 1 4 5 -3 L 4 1 4 5 -4 L 4145-7 L 4 1 4 5 -8 L 4 1 4 5 -1 1 L 4 1 4 5 -1 2 L 4 1 4 5 -1 5 L 4 1 4 5 -1 6 L 4 1 4 5 -1 7 L 4 1 4 5 -1 8 L4145-21 L 414 5 -2 2 L 414 5 -2 5 \ S a m p le ID Q -W 1-208462 O -V i/1-208462 Dup O -W 2-208463 O -W 2-208463 Dup O -W 5-127287 0 -W 5 -1 2^287 Dup 0-W 7-463534 0-W 7-463534 Dup O -W 8-572608 O -W 8-572608 Dyp O -W 3-208454 O -W 3-208454 Dup . E 0 4 -0 9 1 1 Trip Blank \ A n alyte Found (n g /m L ) C 8 A cid P FO A Perfluorooctanoic Acid C8 S u lfo n ate PFO S Perfluorooctanesulfonate 0.0891 0 .0 9 6 5 0 .0764 0 .0 5 6 1 0 .0 5 6 6 NQ 0 .0 9 9 9 NQ 0 .8 1 5 0 .8 6 1 0 .9 0 0 1 .0 7 0 .3 2 2 0 .250 0 .3 1 7 0 .262 0 .6 7 6 0 .895 0 .6 7 7 0 .869 ND ND ND ND ND ND ND = Not detected at or above 0.025 ng/mL. NQ = Not quantifiable = Measured concentration between 0.025 ng/mL and the Limit of Quantitation (LOQ) which is 0.050 ng/mL. ri m A xA 3 0 58 Research Drive ^ r m s tSatatte College, PA 16801, U SA T: 814.272.1039 VA F: 814.231.1580 exygen.com 30 Section B 3/ 4 Fidjd Matrix Spike Recovery Summary for PFOAand PFOS in Water E04-0911 i C8 Acid PFOA_______________ C8 Sulfonate PFOS S8SSSSSSSSS5SSSSSSSSSSBSXBS8SS=SSSSSSSSSSSS&=8sasSSasS0^ SSSSSSSS Amount Amt Found Amount Amt Found Amount li Sample''.. Description.. Spiked in Sample Recovered Recovery in Sample Recovered Recovery (ng/mL) (ng/mL) ("S/rnL)____ (%) (ng/mL) (ng/mL) (%) 0-W 1-208462 Low Spike (L4145-S, 0.1 ppb Spike) 0.1 0.0891 0.195 106 0.0561 0.182 126 i 0-W 1-208462 High Spike (L4145-S, 5 ppb Splka) 5 0.0891 6.42 127 0.0561 6.30 125 i O-W2-208463 Low Spike (L414S-9,0.1 ppb Splka) 0.1 0.0764 0.137 61 NQ 0.119 119 O-W2-208463 High Spike 4 (L4145-10, S ppb Splka) \5 0.0764 5.78 114 NQ 6.20 124 0-W5-127287 Low Spike (L414S43,0.1 ppb Splka) 0.1 0.815 0.976 0.861 1.23 * i 0-W5-127287 High Spike (L4145-14, S ppb Splka) 5 -, 0.815 6.37 111 0.861 7.35 130 4 0-W7-463534 Low Spike (L4145-1,0.1 ppb Splka) 0.1 0:322 0.402 80 0.250 0.298 48 0 -W 7 -4 6 3 5 3 4 High Spike 4 (L414S-2, 5 ppb Splka) 5 0.322 5.54 104 0.250 5.53 106 O-W8-572608 Low Spike (L4145-19,0.1 ppb Splka) 0.1 0.676 , 0.768 * 0.895 0.885 * m O-W8-572608 High Spike (L414S-20, 5 ppbS plk} 5 0.6 7 6 30 112 0 .8 9 5 5.7 9 98 4 O-W3-208454 Low Spike (L4145-23,0.1 ppb Splka) 0.1 ND 0.092 , 92 ND 0.126 126 O-W3-208454 H ig h Spike . (L4145-24, 5 ppb Splka) 5 ND 5.13 \ 103 ND 5.88 118 E04-0911 Trip Blank Low Spk (L4145-26,0.1 ppb Splka) 0.1 ND 0.088 88, ND 0.103 103 ml IE04-0911 Trip Blank High Spk (L4145-27, 5 ppb Splka) 5 ND 5.59 112 ND 5.61 112 4 'Sam ple residue exceeds the spiking level significantly; therefore, an accurate recovery value cannot be calcinated NO = Not detected at or above 0.025 ng/mL. NQ = Not quantifiable = Measured concentration between 0.025 ng/mL and the Limit of Quantitation (LOQ) which is 0.050 ng/mL. 4 nXr m 30 58 Research s tSatalte College, D rive PA 16801, USA 4 VJ; 800.281.3219 F; 814.272.1019 exygen.com 3X Exygen m# {^RESEARCH Precise Research. Proven Results. Surrogate Spike Recovery Summary for 13CPFOA in W ater E04-0911 13c -p f o a ill A m o u n t A m o u n t xygen S am p le S piked R ecovered R eco very JD D escrip tio n (n g /m L ) (n g /m L ) (% ) L 4145.-3 0 -W 1 -208462 0.5 0 .5 7 0 114 L 4 1 4 5 -4 0 -W 1 -208462 Dup 0.5 0 .557 111 L4145-5 L 4 1 4 5 -6 O -W 1-208462 Low Spk 0 -W 1 -2 0 8 4 6 2 High Spk 0 .5 0 .5 0 .579 0 .5 8 3 116 117 L 4 1 4 5 -7 O -W 2-208463 0.5 0 .5 4 8 L 4 1 4 5 -8 , O -W 2-208463 Dup 0 .5 0 .602 L 4 145-9 -W 2-208463 Low Spk 0 .5 0 .3 7 9 L 4 1 4 5 -1 0 O -VV2-208463 High Spk 0 .5 0 .573 110 120 76 115 L 4145-11 C M /V 5-12 7 2 8 7 0 .5 0.466 93 L 4 1 4 5 -1 2 0 -W 5 -1 27287 Dup 0.5 0 .5 6 9 114 L 4 1 4 5 -1 3 L 4 1 4 5 -1 4 0 -W 5 -1 27287 Low Spk 0 -W 5 -1 272 8 7 High Spk 0 .5 0 .5 0 .5 7 8 0 .5 2 8 116 106 L 4 1 4 5 -1 5 0 -W 7 -4 63534 0 .5 0.541 108 L 4 1 4 5 -1 6 0-W 7-463534 Dup 0 .5 0.551 110 L 4 1 4 5 -1 0-W 7 -4 6 3 53 4 Low Spk 0 .5 0 .558 112 L 4 1 4 5 -2 0 -W 7 -4 6 3 5 3 4 High Spk 0 .5 0.541 108 L 4 1 4 5 -1 7 O -W 8-572608 . 0.5 0 .5 1 6 103 L 4 1 4 5 -1 8 O -W 8-572608 Dup \ 0 .5 0 .5 3 6 107 L 4 1 4 5 -1 9 O -W 8-572608 Low Spk . 0 .5 0 .5 7 5 115 L 4 1 4 5 -2 0 O -W 8 -5 7 2 6 0 8 High Spk 0 .5 0 .5 3 4 107 L4145-21 L 4 1 4 5 -2 2 L 4145-23 L 4 1 4 5 -2 4 O -W 3-208454 O -W 3-208454 Dup O -W 3-208454 Low Spk O -W 3 -2 0 8 4 5 4 High Spk . 0.5 \ 0.5 0 .5 0 .5 0 .566 0.581 0 .608 0.541 113 116 122 108 L 4 1 4 5 -2 5 L 4145-26 L414 5 -2 7 E 0 4 -0 9 1 1 Trip Blank E 04-0911 Trip Blank Low Spk E 04-0911 Trip Blank High Spk 0 .5 \ 0 .5 0 .5 0 .5 1 3 0 .5 2 0 0 .5 1 4 103 104 103 I ^ ^ 3 0 5 8 Research Drive * State College, PA 16801, U SA ^ T : 800.281.3219 m F : 814.272.1019 exygen.com 33