Document J3L8xNep4Z6Yd35vxm2NokgKr

P roven Results. m Analytical Report l i 3M Company Analysis of PFA and PFOS In Water Samples from Hastings Municipality E04-0909 Exygen Report No. L0004146 Revised m gl Testing Laboratory Exygen Research 3Q58 Research Drive m State College, PA 16801 Sequester Gary A. Hohenstein Manager, Environmental Operations EHS Oprations 3M Company Building 42-3E-27 St. Paul, MN 55106 m M_ ^ ^ 3 0 5 8 Research D rive m . State College, PA 16801, USA PAGE 10 F 5 8 0 0 2 8 1 .3 2 1 9 m F: 814.272.1019 i exygen.com 1 Introduction In this revised report, results are reported for the analysis of perfluorooctanoic acid (PFOA) and perfluorooctanesulfonate (PFOS) in water samples received at Exygen as requested by Gary Hohenstein of 3M Company. The report was revised to update the requester inform ation and to m ake m inor changes to the text of the report. Analytical results were not changed in this revision. The Exygen project number assigned to the samples is L0004146. Table I lists the target analytes quantitated for the samples. Table I. Target Analytes for Quantitation P aram eter Acronym Form ula Perfluorooctanoic acid PFOA C rF,sCOOH Perfluorooctanesulfonate PFOS CSF17SO3H 2 Sample Receipt Twenty-three samples were received at Exygen in 500 m L white plastic narrow-m outh bottles. A t the request of 3M, all samples were analyzed. A copy of all sam ple iog-in Information is presented in Attachment A. The samples were received on 12/28/04. The samples were shipped am bient via UPS. The samples w ere stored refrigerated from tim e 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 fo r LC/MS/MS analysis. Forty m illiliters of the water sample was transferred to a C18 SPE cartridge. The cartridge was washed with 5 mL of a 40% methanol: 60% w ater wash. The cartridge was eluted with 5 m L of 100% methanol. A portion of the extract was transferred to autosam pler vials and analyzed using electrospray LC/MS/MS. 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 fo r the stationary phase in the column relative to the liquid mobile phase, the analyte is retained fo r a PAGE2 O F5 characteristic am ount of tim e. Following HPLC separation, mass spectrom etry provides a rapid and accurate means fo r analyzing a wide range of organic compounds. M olecules are ionized, fragm ented, and detected. The ions characteristic o f the Compounds are observed and quantitated against extracted standards. An HP1100 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 isom ers is reported as a single value fo r each of the analytes. The following gradient was perform ed: Mobile Phase (A): Mobile Phase (B): 2mM Ammonium Acetate in W ater M ethanol Tim e 0.0 1.0 8.0 10.0 11.0 18.0 %A 65 65 25 25 65 65 %B 35 35 75 75 35 35 The following parameters were used for operation of the m ass spectrom eter: Param eter Ionization Mode Polarity Transitions Monitored Gas Tem perature Drying Gas (N2) S ettin g Electrospray Negative 413->369 (PFOA), 499->80 (PFOS), 415->370 (13C-PFOA) 350C 7.0 L/min 4 Analysis 4.1 Calibration A 7-point calibration curve was analyzed initially and throughout the analytical sequence fo r PFOA, PFOS 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/MS/MS analysis. Calibration standards are prepared using the sam e SPE procedure used fo r samples. The instrum ent response versus the concentration was plotted fo r each point. Using linear regression with 1/x weighting, fie slope, y-intercept and coefficient of determ ination { r ) were determ ined. A calibration curve is acceptable if ? > 0.985. For fie results reported here, calibration criteria were m et. The calibration curves are included in the raw data in Attachm ent C. PAGE3 OFS 4.2 Surrogates iaC PFOA is used as a surrogate fo r the water samples. 13C PFOA was added to the em pty sample containers before the bottles were sent to the field fo r sampling. In the field, the bottles were filled to a volumetric fill line with the sample. 13C PFOA recoveries can be found in Attachm ent B. 4.3 Laboratory Control Spikes Laboratory control spikes in the analytical set were prepared by adding a known concentration of PFOA, 13C-PFOA, and PFOS to laboratory reagents. Laboratory control spikes are used to assess method accuracy. The laboratory control spikes m ust 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 m atrix spike was prepared for every water sam ple in the field. Compounds were added to the empty sample containers before the bottles were sent to the field fo r sampling. Matrix spikes are used to assess m ethod accuracy in the m atrix. The m atrix spikes should show recoveries between 70-130%. For the results reported here, the m atrix spikes were within the acceptable range, except as noted in Section 6 of this report. 4.5 Sample Related Comments All water samples were collected in duplicate. Duplicate sam ple results are reported along with the sam ple results in Attachment B. 5 Data Summary Please see Attachm ent B for a detailed listing o f the analytical results. The results are reported in parts per billion (ng/mL) for PFOA and P F O S . 6 Statement of Accuracy Based on results of laboratory control spikes, field m atrix spikes, and surrogate spikes, the analytical accuracy fo r PFOS and PFOA results is 30%. Laboratory control spikes, surrogate spikes, and field m atrix spikes showed recoveries within these ranges, with the following exception: The PFOS recovery for sample H-W 6-207643 High Spike was 132%. Specific sample recoveries are given in Attachm ent B. PAGE 4 OF5 ri 7 Data/Sampie Retention ia Samples w ill be returned to 3M 60 days after final reporting. All electronic data is archived on retrievable m edia and hard copy rports are stored in data folders m aintained by Exygen. Hardcopy data is stored for a minimum of five years. The client w ill be notified 30 days prior to the disposal o f hardcopy data. I 8 Attachments 7.1 Attachm ent A: Analytical Results m 7.2 Attachm ent B: Spike Recovery Data 7.3 Attachm ent C: Chain of Custody Forms 7.4 Attachm ent D: Raw Analytical Data i tf 9 Signatures r a j -fa r Karen Risha, Principal Investigator <4 Q .//r 7 / ^ C f ,/O o h n M. Flaherty, Vice-President ri ri J n f is D a te '/7 / s T Date ii ri <ltf m PAGE5 OF5 a S Section A i P roven Results. Summary of PFOA and PFOS in Water Samples E04-0909 Exygen ID L4146-1 L4146*2 L4146-5 L4146-6 L4146-9 L4146-10 L 4 146-13 L4146-14 L4146-17 L4146-18 L 4 146-21 \ Sample ID H-W 6-207643 H-W 6-207643 Dup H-W 4-207993 H-W 4-207993 Dup H-W 5-207639 H-W 5-207639 Dup H-W 3-206333 H -W 3-206333 Dup H-W 7-50903 H-W 7-509053 Dup E04-0909 T rip Blank Analyte Found (ng/mL) C8 Acid PFOA C8 Sulfonate PFOS Perfiuorooctanoic Acid Perfluorooctanesulfonate NQ ND NQ ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND A 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\ A i I A XM l3058 Research D rive m SStatatte College, PA 16801, USA J: 814.272.1039 Vm F: 814.231.1580 exygen.com Section B H Field M atrix Spike Recovery Summary for PFOA and PFOS in W ater E04-0909 Sample Description H-W6-207643 Low Spike (L4146-3,0.1 ppbSpike) C8 Acid PFOA______________ 8 Sulfonate PFOS Amount Amt Found Amount Amt Found Amount Spiked in Sample Recovered Recovery in Sample Recovered Recovery (ng/mL) (ng/mL) (ng/mL) (%) (ng/mL) (ng/mL) 0.1 NQ 0.115 115 ND 0.119 119 H-W6-207643 High Spike (L4146-4,5 ppbSpike) 5 NQ 4.95 99 ND 6.58 132 H-W4-207993 Low Spike (L4146-7,0.1 ppbSpike) \ 0.1 ND 0.0903 90 ND 0.126 126 H-W4-207993 High Spike (L4146-8, SppbSpike) \ 5 ND 4.97 99 ND 5.94 119 H-W5-207639 Low Spike (U146-11,0.1 ppbSpike) 0.1. ND 0.0978 98 ND 0.118 118 H-W5-207639 High Spike (14146-12, 5ppbSpike) 5 ND 4.38 88 ND 4.66 93 H-W3-206333 Low Spike (L4146-15, 0.1 ppbSpike) 0.1 'ND 0.0937 94 ND 0.119 119 H-W3-206333 High Spike (L4146-16,5 ppb Spike) 5 N D \ 5.96 119 ND 6.36 127 H-W7-509053 Low Spike (L4146-1&,0.1 ppbSpk*) 0.1 ND 0.0844 84 ND 0.0952 95 H-W7-509053 High Spike (L4146-20,5 ppbSpike) 5 ND 6,21 124 ND 6.47 129 E04-0909 Trip Blank Low Spk (L4146-22,0.1 ppbSpike) 0.1 ND 0.100 100 ND 0.110 110 E04-0909 Trip Blank High Spk (L4146-23,5ppbSpike) 5 ND 5.58 112 ND 4.61 92 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. J& 30305518 Research D rive ^ ^ L S' tSatalte College, PA 16801, USA VT: 800.281.3219 F: 814.272.1019 exygen.com Surrogate Spike Recovery Summary for 1JC-PFOA in Water E04-0909 Exygen ID Sample Description Amount Spiked (ng/mL) 13C-PFOA Amount Recovered (ng/mL) Recovery (% ) L4146-1 L4146-2 L4146-3 L4146-4 H-W 6-207643 H-W 6-207643 Dup H-W 6-207643 Low S pk H -W 6-207643 High Spk 0.5 0.5 0.5 0.5 0.494 0.594 0.557 0.582 99 119 111 116 L4146-5 H-W 4-207993 0.5 0.570 L4146-6 . H-W 4-207993 Dup 0.5 0.512 L 4 146-7 HrW 4-207993 Low S pk 0.5 0 .5 4 7 L4146-8 H-VV4-207993 High Spk 0.5 0.513 114 102 109 103 L4146-9 H-W 5-207639 0.5 0.547 L4146-10 H-W 5-207639 Dup 0.5 0.535 L4146-11 H-W 5-207639 Low Spk 0.5 0.551 L4146-12 H-W 5-207639 High Spk 0.5 0 .4 8 7 109 107 110 97 L4146-13 L4146-14 L4146-15 L4146-16 H-W 3-206333 H-W 3-206383 Dup H-W 3-206333 Lbw Spk H-W 3-206333 High Spk 0.5 0.5 0.5 0.5 0 .5 5 0 0.621 0.576 0.574 110 124 115 115 L4146-17 . L4146-18 L4146-19 L4146-20 H-W 7-509053 , H-W 7-509053 Dup . H-W 7-509053 Low Spk H -W 7-509053 High Spk \ 0.5 0.5 0.5 0.5 0.571 0.484 0.524 0 .5 7 5 114 97 105 115 L 4 146-21 E04-0909 T rip Blank L4146-22 E04-0909 Trip Blank Low Spk L4146-23 E04-0909 T rip Blank High Spk 0.5 0.5 0 .5 0 .5 5 6 0.526 0.482 111 105 96 J ^ 3 030558i Research D rive State College, PA 16801, USA wJ: 800.281.3219 F: 814.272.1019 exygen.com