Document 447wo8zQvOaM39Q1BZXGpO05G

BACK TO MAIN Centre Analytical Laboratories, Inc. 3048 Research Drive State College, PA 16801 www.centrelab.com ^P hone: (814)231-8032 Fax: (814) 231-1253or (814) 231-1580 Analytical Report Fluorochem ical Characterization of Drinking W ater Sam ples Colum bus, GA (W 2336) Centre Analytical Laboratory Report No. 023-007F (Revision 2) (Revision Date 3/21/01) Testing Laboratory Centre Analytical Laboratory, Inc. 3048 Research Drive State College, PA 16801 3M Environmental Laboratory Contact Kent R. Lindstrom Bldg. 2-3E-09 P.O. Box 33331 St. Paul, MN 55133-3331 Phone: (651)778-5352 Requester Kris J. Hansen, Ph.D. 3M Environmental Technology & Safety Services Bldg. 2-3E-09 P.O. Box 33331 St. Paul, MN 55133-3331 PAGE 1 0 F 5 BACK TO MAIN 1 Introduction Results are reported for the analysis of a series of drinking water samples received by Centre Analytical Laboratories, Inc. (Centre) from the 3M Environmental Laboratory. The samples were collected from Columbus, GA. The Centre study number assigned to the project is 023-007. Specific fluorochemical characterization by liquid chromatography / tandem mass spectrometry (LC/MS/MS) was requested for all samples. A total of 16 samples were received for analysis. The samples were prepared and analyzed by LC/MS/MS for the following list of fluorochemicals: Table 1: Target Analysis Compound Name Perfluorooctane Sulfonate Perfluorooctane Sulfonvlamide Perfluorooctanoate Acronvm PFOS F'FOSA F'OAA The analytical method used was validated by Centre. The validation protocol and results are on file with Centre. Data presented here is the highest quality data available at this time. 2 Sample Receipt The samples were submitted in individual plastic containers and were not preserved. Sixteen individual sample containers were received. Samples were received on 02/15/00. The sample collection dates were not supplied. Chain-of-custody information is presented in Attachment C. 3 Holding Times The analytical method used was validated against a maximum holding time of 14 days. The stability of the analytes of interest for longer periods has not been determined. However, it should be noted that field fortifications in water and other matrices have shown acceptable recoveries at 100 and 1000 ng/L for periods longer than 14 days. PAGE2 OF5 BACK TO MAIN 4 Methods - Analytical and Preparatory 4.1 LC /M S/M S 4.1.1 Sample Preparation for LC/MS/MS Analysis Samples were initially treated with 200 uL of 250 mg/L sodium thiosulfate solution to remove residual chlorine. Solid phase extraction (SPE) was used to prepare the samples for LC/MS/MS analysis. A forty-milliliter portion of sample was transferred to a C18SPE cartridge. The cartridge was first eluted with 5 mL of 40% methanol in water solution. The eluate was discarded and the SPE column was then eluted with 100% methanol. A 5 ml portion of methanol was collected for analysis by LC/MS/MS. This treatment resulted in an eight-fold concentration of the samples prior to analysis. 4.1.2 Sample Analysis by LC/MS/MS In 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 characteristic amount of time. Following HPLC separation, ES/MS provides a rapid and accurate means for analyzing a wide range of organic compounds, including fluorochemicals. Electrospray Is generally operated at relatively mild temperatures; molecules are Ionized, fragmented, and detected. Ions characteristic of known fluorochemicals are observed and quantitated against standards. A Hewlett-Packard HP1100 HPLC system coupled to a Micromass Ultima MS/MS was used to analyze the sample extracts. Analysis was performed using selected reaction monitoring (SRM). Samples were extracted on 2/24/00 and analyzed by MS/MS between 2/26/00 and 2/27/00. The HPLC and MS/MS methods used for analysis and instrument parameters can be found in attachment D. 5 Analysis 5.1 Calibration A 7-point calibration curve was analyzed at the beginning and end of the analytical sequence for the compounds of interest. The calibration points were prepared at 0, 25, 50, 100, 250, 500, and 1000 ng/L (ppt) The response of the quantitation ion versus the concentration was plotted for each point. Using linear regression with 1/x weighting, the slope, y-lntercept and correlation coefficient (r) and coefficient of determination (r2) were determined. A calibration curve is acceptable if r >.0.985 (r2 > 0.970). Calibration standards are prepared using the same SPE procedure used for samples. Calibration check standards were analyzed periodically (every three to five sample injections) throughout the analysis sequence. Compliance is obtained if the standard analyte concentrations are within +/-20% of the actual value. For the results reported here, calibration criteria were met. PAGE3 OF5 BACK TO MAIN 5.2 Blanks Extraction blanks were prepared and analyzed with every extraction batch of samples. The extraction blanks should not have any target analytes present at or above the concentration of the low-level calibration standard. For these samples, the extraction blanks were compliant. Instrument blanks in the form of clean methanol solvent were also analyzed after every highlevel calibration standard, and after known high-level samples. Again, the blanks should not have any target analytes present at or above the low-level calibration standard. For the samples presented here the instrument blanks are compliant. 5.3 Surrogates Surrogate spikes are not a component of the LC/MS/MS analytical method. 5.4 M atrix Spikes Matrix spikes were prepared for every sample at a concentration of 100 ng/L using all compounds of interest. Matrix spike recoveries are given in Attachment B. Field spikes were also prepared on several samples at a concentration of 100 ng/L using all compounds of interest. Field spike recoveries are also given in Attachment B. The field spike results for sample MC-529H gave recoveries for all compounds of approximately 1000 %, indicating that this sample was possibly spiked at 1000 ppt instead of 100 ppt. 5.5 Duplicates All samples were analyzed in duplicate. Results are given along with the sample results in Attachment A. 5.6 Laboratory Control Sam ples Milliq water was spiked with all compound of interest at 25 and 250 ng/L. All recoveries for all compounds were between 70-130% in each LCS. 5.7 Sam ple Related Com m ents Field blank samples consisted of empty containers. Forty milliliters of type I water filtered through a hypercarb cartridge was added to the empty container and analyzed in the same manner as the other samples. 6 Data Summary Please see Attachment A for a detailed listing of the analytical results. 7 Data/Sample Retention Samples are disposed of one month after the report is issued unless otherwise specified. All electronic data is archived on retrievable media and hard copy reports are stored in data folders maintained by Centre. PAGE 4 O F5 8 Attachments 8.1 Attachment A: Results 8.2 Attachment B: Matrix Spike Recoveries (Field and Laboratory Spikes) 8.3 Attachment C: Chain of Custody 8.4 Attachment D: LC/MS/MS Raw Analytical Data 9 Signatures BACK TO MAIN Other Lab Members Contributing to Data Enaksha Wickremesinhe Karen Smith PAGE 5 OF5 ___R A C K T O M A I M ___ ______ :__ i ANALY If iS S IS t f H Centre Analytical Laboratories, Inc. 3048 Research Drive, State College PA 16801 814-231-8032 FAX 814-231-1253 Analytical Results W2336 Columbus, GA 3M Sample Identification MC-515H MC-517H MC-520H MC-521H MC-523H MC-526H MC-528H MC-531H NA MC-532H NA MC-533H Sample Description Intake-P/N Intake-P/N duplicate Intake-Field Blank Empty Outflow-P/N Outflow-P/N duplicate Site 1 P/N Site 1 P/N duplicate Site 2 P/N Site 2 P/N duplicate Site 3 P/N Site 3 P/N duplicate Field Blank-P/N Empty PFOS (ng/L) 61.2 53.3 ND 61.5 62.5 57.5 55.7 57.4 55.4 61.7 57.8 ND PFOSA (ng/L) NQ NQ ND NQ NQ NQ NQ NQ NQ NQ NQ ND POAA (ng/c) 25.5 NQ ND 28.8 25.3 26.0 NQ 26.3 NQ 25.4 NQ ND Limit of Detection (LOD) for the procedure is appoximately 2.5 ng/L for PFOS and PFOSA and 7.5 ng/L for POAA Limit of Quantitation (LOQ) for the procedure is 25 ng/L for all compounds IMD - Compound not detected NQ - Compound detected at a level between the LOD and LOQ. Result is not quantifiable. IMD < LOD < NQ < LOQ Please refer to the reverse side for our standard terms and conditions. BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: Spiked Amount (ng/L): MC-519H 100 PFOS PFOSA POAA Sample Concentration (ng/L) 61.2 11.7 25.5 Matrix Spike Result (ng/L) 166 125 129 Matrix Spike Result (% Recovery) 104.8 113.3 103.5 Criteria (Pass / Fail) PASS PASS PASS Lower Recovery Limit: 70 Upper Recovery Limit: 130 Note: Sample results less than 25 ng/L are reported as NQ in the results section as they are below the limit of quantitation. Results are given in this table for recovery calculations only. BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: Spiked Amount (ng/L): MC-525H 100 PFOS PFOSA POAA Sample Concentration (ng/L) 61.5 14.9 28.8 Matrix Spike Result (ng/L) 172 125 139 Matrix Spike Result (% Recovery) 110.5 110.1 110.2 Criteria (Pass / Fail) PASS PASS PASS Lower Recovery Limit: 70 Upper Recovery Limit: 130 Note: Sample results less than 25 ng/L are reported as NQ in the results section as they are below the limit of quantitation. Results are given in this table for recovery calculations only. BAk T MAIM Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: Spiked Amount (ng/L): MC-530H 100 PFOS PFOSA POAA Sample Concentration (ng/L) 57.5 14.9 26.0 Matrix Spike Result (ng/L) 185 130 148 Matrix Spike Result (% Recovery) 127.5 115.1 122.0 Criteria (Pass / Fail) PASS PASS PASS Lower Recovery Limit: 70 Upper Recovery Limit: 130 Note: Sample results less than 25 ng/L are reported as NQ in the results section as they are below the limit of quantitation. Results are given in this table for recovery calculations only. BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: Spiked Amount (ng/L): MC-531H 100 PFOS PFOSA POAA Sample Concentration (ng/L) 57.4 12.6 26.3 Matrix Spike Result (ng/L) 176 132 132 Matrix Spike Result (% Recovery) 118.6 119.4 105.7 Criteria (Pass / Fail) PASS PASS PASS Lower Recovery Limit: 70 Upper Recovery Limit: 130 Note: Sample results less than 25 ng/L are reported as NQ in the results section as they are below the limit of quantitation. Results are given in this table for recovery calculations only. BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: Spiked Amount (ng/L): MC-532H 100 PFOS PFOSA POAA Sample Concentration (ng/L) 61.7 14.8 25.4 Matrix Spike Result (ng/L) 168 121 128 Matrix Spike Result (% Recovery) 106.3 106.2 102.6 Criteria (Pass / Fail) PASS PASS PASS Lower Recovery Limit: 70 Upper Recovery Limit: 130 Note: Sample results less than 25 ng/L are reported as NQ in the results section as they are below the limit of quantitation. Results are given in this table for recovery calculations only. BACK TO MAIN Attachment B: LC/MS/MS Field Spike Recovery Sample ID: Spiked Amount (ng/L): MC-518H 100 PFOS PFOSA POAA Sample Concentration (ng/L) 61.2 11.7 25.5 Matrix Spike Result (ng/L) 185 137 144 Matrix Spike Result (% Recovery) 123.8 125.3 118.5 Criteria (Pass / Fail) PASS PASS PASS Lower Recovery Limit: 70 Upper Recovery Limit: 130 Note: Sample results less than 25 ng/L are reported as NQ in the results section as they are below the limit of quantitation. Results are given in this table for recovery calculations only. BACK TO MAIN Attachment B: LC/MS/MS Field Spike Recovery Sample ID: Spiked Amount (ng/L): MC-524H 100 PFOS PFOSA POAA Sample Concentration (ng/L) 61.5 14.9 28.8 Matrix Spike Result (ng/L) 167 128 138 Matrix Spike Result (% Recovery) 105.5 113.1 109.2 Criteria (Pass / Fail) PASS PASS PASS Lower Recovery Limit: 70 Upper Recovery Limit: 130 Note: Sample results less than 25 ng/L are reported as NQ in the results section as they are below the limit of quantitation. Results are given in this table for recovery calculations only. BACK TO MAIN Attachment B: LC/MS/MS Field Spike Recovery Sample ID: Spiked Amount (ng/L): MC-529H 100 PFOS PFOSA POAA Sample Concentration (ng/L) 57.5 14.9 26.0 Matrix Spike Result (ng/L) 1410 1551 1293 Matrix Spike Result (% Recovery) 1352.5 1536.1 1267.0 Criteria (Pass / Fail) FAIL FAIL FAIL Lower Recovery Limit: 70 Upper Recovery Limit: 130 Note: Sample results less than 25 ng/L are reported as NQ in the results section as they are below the limit of quantitation. Results are given in this table for recovery calculations only. Matrix spike recoveries indicate that this sample was spiked at 1000 ng/L instead of the 100 ng/L level indicated by the samplers BACK TO MAIN 3M Envil .mental Laboratory Form 3877B - PWO Shipping Address: 3M Bldg 2-3E-09 Telephone: Sample Receiving: (651) 778*4948 Chain of Custody /Reque. Project ID/Project Mama O X ^ - O O l Template U Jr Laboratory Analytical 1 7 1 3 0 ^ Tk n L f ) r i / 1IJ .1 3 it p fflnal Report Due Date 0 ^ . /u ^ fs 0. 3M Env. Project # For I n t e l . U s e Only 935 Bush Avenue St Paui, MN 55106 Alternate: (651)778-6763 FAX: (651)778-8178 Contact Name fk n S W . Project Lead Dept. # (main) * fU ^ s r/V ' U iS 'i | _.. Internal Due Date Class/Job/Project # 0 0 | Date Available Company Mailing Address t u t f A ^ n a Z - Q ! ..P_ 0 K W .J 3 =5 3 ^ j _______________________ Date Due City, State, Z.p #JTelephone y y ) ? ) *5 ^ T lV 5 ... ......................... TTft- ' 1* O t fc______________FAX* ( f a 'Z i 'S T P * - b P l a ________ _ Contract Lab c 1 AJ T Z i Special Instructions and/or SpacificR egulatory Requirem ents: (m eth od , lim it of detection, reporting units, etc ) " Analysis Requested: Preservatives: Complete below. A ttach any associated Inform ation. Report Results to: Total Number of Containers C v I l m ib^3 / & A #Item Client Sample Identification 1. -O^vVaVa - P i / O 3M L IM S # W 'X d k 2. m l - s n W - 3 ^ ' V ^ S p L ' - P i c A i L . / L * J n - P -3. * A / \ < i S p i \ J L - P ) b 4. 65.. mr n m C - ,5'liiM i -S iO 5 im -l - -1^ n^V 4^U tr U>iSpiiUL - J A t \< L 'H a u)-P//^ -P rJk /a -P J A J . 7. y y u -OtHltouO-^FidA/l^Jo-Ou^-P 8. A > )a J - a9. j+ ^ lt u ) A j J S p i . J > i/ 10. S H U - !f f \ L - S * b A ' Q/a 2__ ____________ SJ Collecled by (print). coV3i *ob- Item # J r l . O : Relinquished by/Affiliatlon ozzM 0* 1tNfl OO>M z0co> o0) Date Sampled yUA- T im e Sampled a j \A Matrix/ Media L( h t v i Enter the number of containers of each /\r \ r--- S<tk /4/ j ...\ V Collector's signature: Time,;;: : Date ijj p 1 1 1 1 1 11 l \l Sam ple Condition Upon Receipt: e Acceptable 0 Other: Tem peratu re: `C e Received on Ice OUw Associated CoCs: j- j l i f t , f p T - t , | - j t l _ , 1 1 1 1 .3 , 0124 Copies to: 3 .n 1r ? , n t u r , m Paga Of x % n /a i *n > 3 3 , n i 3 -r & \L L M Original - Accompanying Samples Comments J E ___________ Last Paga - Originator Saa R e ve rse Side for Instrtidio m `X'(E nter an in the b o * below to in dicale request) C>O o 7--;i o