Document LJ9BQzJ55XadYNXV8Jbnjy0yb

3M Manufacturing Facilities Analysis of Alfalfa Harvested from 3M Cordova, Illinois Plant Facility BACK TO MAIN Executive Summary 3M Environmental Laboratory June 21, 2001 In the fall of 2000, samples of alfalfa being grown on the 3M Cordova Plant (Cordova, Illinois) property were collected by plant personnel. There was no sampling plan in place prior to harvest. No documentation was made of sampling procedures, locations, or handling. The alfalfa was submitted for analysis of methyl FOSE alcohol, ethyl FOSE alcohol, PFOS, PFOA, and PFOSA. The method developed for the extraction and analysis of green beans was adapted to use on the alfalfa. The QC samples included with the sample analyses indicated that a true blank matrix was not used for spiking, and that recoveries were occasionally unacceptably low. For all of the reasons listed above, interpretation of analytical results from these alfalfa samples is not recommended. All of the alfalfa grown at the 3M Cordova Plant property was landfilled after harvest. BACK TO MAIN Centre Study No. 023-046 ALFALFA SUMMARY SPONSOR 3M Environmental Technology and Safety Services Building 2-3E-09 PO Box 33331 St. Paul, MN 55133-3331 DATA REQUIREMENTS Non-GLP TESTING LABORATORY Centre Analytical Laboratories, Inc. (Centre) 3048 Research Drive State College, PA 16801 Phone 814-231-8032 CENTRE IDENTIFICATION NUMBER 023-046 Centre Analytical Laboratories, Inc. Page 1 of 5 BACK TO MAIN Centre Study No. 023-046 1. PURPOSE The purpose of this study was to find the amount of MeFOSE-OH, EtFOSE-OH, PFOS, PFOSA and PFOA in alfalfa samples using the method titled "M ethod of Analysis for the Determination of Fluorochemicals in green beans, apples, pork muscle, cow milk, chicken muscle, chicken eggs, bread, hotdogs, and catfish by L C /M S/M S." 2. TEST MATERIALS The following analytical standards were used: Test Material Lot or TCR Number Purity (%) Expiration Date MeFOSE-OH EtFOSE-OH NA Purified from Lot 30107 NA TBD 01/01/10 04/07/01 PFOS TCR00017-46 97.9 08/31/01 PFOA 332 TBD 07/06/01 PFOSA L -15709 TBD= To be determined 95.1 02/15/01 Note: GLP characterization data for MeFOSE-OH, EtFOSE-OH, PFOA and PFOSA was unavailable at the time of standard preparation. Therefore, PFOS was the only analyte corrected for percent purity when preparing standard solutions. 3. SAMPLE PROCESSING AND IDENTIFICATION All samples were processed with dry ice in a Hobart food processor. The samples were labeled as follows: Client Sample ID 14978 14979 14980 14981 Centre ID 0009591 0009592 0009593 0009594 Description Control Alfalfa Alfalfa Sample Alfalfa Sample Alfalfa Sample Centre Analytical Laboratories, Inc. Page 2 of 5 BACK TO MAIN Centre Study No. 023-046 4. ANALYTICAL M ETHOD The samples will be analyzed according to the analytical method titled "Method of Analysis for the Determination of Fluorochemicals In Green Beans, Apples, Pork Muscle, Cow Milk, Chicken Muscle, Chicken Eggs, Bread, Hotdogs, and Catfish by LC/MS/MS" following the green bean extraction steps, (see Appendix for a copy of the method). 5. E X PE R IM E N T A L D ESIG N 1. A reagent blank, a control and two spikes of control alfalfa were extracted following the green bean extraction steps of the method entitled "Method of Analysis for the Determination of Fluorochemicals In Green Beans, Apples, Pork Muscle, Cow Milk, Chicken Muscle, Chicken Eggs, Bread, Hotdogs, and Catfish by LC/MS/MS" in order to verify that the green bean extraction would sufficiently work on alfalfa. See A ttachm ent 1: D ata set 100600. 2. A reagent blank, a control, 2 recovery spikes (control alfalfa spiked at 0.5 ng/g and atlO.O ng/g) and duplicate portions of the 3 remaining alfalfa samples were extracted and analyzed according to the method listed in experiment 1. See A ttachm ent 2: D ata set 100900 Alfalfa. 3. Experiment 2 was repeated but spiking was done at 5.0 ng/g and 20 ng/g for EtFOSE-OH, MeFOSE-OH, PFOSA and PFOA. Since the amount of PFOS found in the control samples in experiment 2 was ~30 ng/g the spiking for PFOS was done at 50 ng/g and 200 ng/g in order to ensure that recoveries could be calculated. See A ttachm ent 3: D ata set 101100 Alfalfa and Dilution D ata set 101100R Alfalfa. 4. A reagent blank, 2 reagent spikes (one at 1.25 ng/mL and the other at 50 ng/mL), an alfalfa sample and an alfalfa sample spiked at 10 ng/g) was extracted according to the method listed in experiment 1 with the following changes to the column cleanup: a. Section 4.3.4 of the method: a pre-packed carbon column from supelco was used instead of the florisil/silica gel/carbon/LC-NH2 column. b. Section 4.3.4 of the method: The column was conditioned with 10 mL of saturated ascorbic acid, followed by 10 mL of ACN. c. Section 4.3.1 step c of the method: After all fractions had been placed through the carbon column, the column was washed with 10 mL of ACN followed by 20 mL of 90:10 ACN:2% ascorbic acid in methanol. The wash was also collected into the same flask as the original extract and the method continued with step e. See A ttachm ent 4: D ata set 101300 Test. Centre Analytical Laboratories, Inc. Page 3 of 5 6. RESULTS BACK TO MAIN Centre Study No. 023-046 1. Experiment 1 results: Sample ID 0009591 Spk A 0009591 Spk B Fort Level 5.0 ng/g 20ng/g EtFOSE-OH 85 96 % Recovery MeFOSE-OH PFOS 95 38 98 63 PFOSA 68 63 PFOA 52 65 Even though recoveries for PFOS, PFOSA and PFOA seemed low it was thought that the method as written for green beans would sufficiently work on alfalfa. 2. Experiment 2 results: Sample ID 0009591 Spk A 0009591 Spk B Fort Level 0.5 ng/g 10 ng/g EtFOSE-OH 85 73 % Recovery MeFOSE-OH PFOS 103 41 78 -53 PFOSA 71 62 PFOA 94 53 The recoveries for PFOSA and PFOA were still a little low. Being that there was more PFOS in the blank than the level that was spiked, recovery numbers for PFOS were inaccurate. It was decided to repeat the experiment using a higher spiking level for PFOS. 3. Experiment 3. results: Sample ID Fort Level EtFOSE-OH 0009591 Spk A 5.0 ng/g 92 0009591 SpkB 20 ng/g 98 * PFOS was spiked at 50 and 200 ng/g. % Recovery MeFOSE-OH PFOS 97 85* 96 102* PFOSA 78 65 PFOA 127 54 Sample results: Centre Sample ID 0009591 Blank A 0009592 0009592 Dup 0009593 0009593 Dup 0009594 0009594 Dup Client ID 14978 14979 14979 14980 14980 14981 14981 EtFOSE-OH 0.153 0.201 0.582 0.235 0.293 0.144 0.135 Analyte Found (ng/g) MeFOSE-OH PFOS PFOSA 0.135 54.9 0.439 0.0818 53.8 0.124 0.0852 54.9 0.322 0.182 245 0.164 0.186 275 0.205 0.137 41.1 0.0590 0.128 42.8 0.0575 PFOA 2.54 1.08 1.09 1.94 5.25 3.67 1.78 Centre Analytical Laboratories, Inc. Page 4 of 5 BACK TO MAIN Centre Study No. 023-046 Even though the high spike for PFOA was low, the PFOA results were still accepted based on the fact that the low spike was acceptable and all PFOA residues found were at the same level or lower than the low spike level. 4. Experiment 4 results: Sample ID Reagent Spk A Reagent Spk B 0009594 SpkC Fort Level 1.25 ng/mL 50 ng/mL 50 ng/mL EtFOSE-OH 107 87 20 % Recovery MeFOSE-OH PFOS 85 0 88 55 18 65 PFOSA 82 83 45 PFOA 51 76 33 It appears that the alternative clean up did not improve the recoveries for the samples containing matrix. Centre Analytical Laboratories, Inc. Page 5 of 5