Document MJwY3NVxobEbZRyNXBmYVe5VM

i P h o n e : (814) 231-8032 BACK TO MAIN Fax: (814) 231-1253 or (814) 231-1580 Analytical Repart Fluorochemical Characterization of Surface Water Samples Cleveland, Tennessee (W'I 973) Centre Analytical Laboratory Report No!. 023-014A (Revision 1) Revision Date 3/:21/01 Testing Laboratory Centre Analytical Laboratory, Inc. 3048 Research Drive State College, PA 1613011 3M Environmental Laboratory Contact Kent R. Lindstrom Bldg. 2-3E-09 P.O. Box 33331 St. Paul, MN 55133-3:33'1 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 55133-3:331 PAGE 1 OF5 BACK TO MAIN 1 Introduction Results are reported for the analysis of a series of surface water samples received by Centre Analytical Laboratories, Inc. (Centre)from the 3M Environrnental Laboratory. The samples were collected from Cleveland, Tennessee. The Centre study number assigned to the project is 02301 4. Specific fluorochemical characterization by liquid chrornatography / tandem mass spectrometry (LC/MS/MS)was requestedfor all samples. A total of 8 samples were receivedfor analysis. The samples were prepared and analyzed by LC/MS/NIS fior the following list of fluorochemicals: Table 1:Target Analysis I ComDound Name Perfluorooctane Sulfonate Perfluorooctane Sulfonvlamide I Perfluorooctanoate E\cronvm 1 The analytical method used here was validated by Centre. The validation protocol and results are on file with Centre. Data presentedhere is the highest quality data availableat this time. 2 Sample Receipt The samples were submitted in individual plastic contairiers and were not preserved. Eight individual sample containers were received. Samples were received on 05/03/00. The sample collection dates were not supplied. Chain-of-custodyinformationis presentedin Attachment C. Sample MC-102H was not analyzed as per client request. (E-mail communication from Kris Hansenon 9 16/00). Please note that no "quiet water" sarniples were collectedfor this site. 3 Holding Times The analytical method used was validated against a rnax:imum 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 have shown acceptiable recoveries at 100 and 1000 ng/L for periods longer than 14 days. PAGE 2 OF5 BACK TO MAIN 4 Methods - Analytical and Preparatory 4.1 4.1.1 4.1.2 LC/MS/MS Sample Preparationfor 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-milliliterportion of sample was transferredto a Cla SPE cartridge. The cartridge was first eluted with 5 mL of 40% methariol 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 concentrationof the samples prior to analysis. Sample Analysis by LC/MS/MS In HPLC, an aliquot of extract is injectedand passed through a liquid-phasechromatographic 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-PackardHP1100 HPLC system coupled to a Micromass Ultima MS/MS was usedto analyze the sample extracts. Analysis was performecl using selected reaction monitoring (SRM).Samples were extractedon 5/16/00 and analyzed by MS/MS on 5118/00. Sample MC108H was extracted on 5/22/00 and analyzed on 5/23/00. 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 wlere 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 l/x weighting, the slope, y-intercept and correlation coefficient (r) and coefficient of determinatiori ( P ) were determined. A calibration curve is acceptable if r ~ 0 . 9 8 5(?2 0.970). Calibration standards are prepared using the same SPE procedure used for samples. Calibration check standards were analyzed periodically (:everythree to five sample injections) throughout the analysis sequence. Compliance is obtained if the standard analyte concentrations are within +/-20Yo0f the actual value. For the results reported here, calibration criteria were met. PAGE3OF5 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 prlesent at or above the concentration of the low-levelcalibrationstandard. For these samples, the extraction blanks were compliant. Instrument blanks in the form of clean methanol solveni 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 Matrix Spikes Matrix spikes were prepareg for every field sample (excluding blanks) at a concentration of 100 ng/L using all compounds of interest. Matrix spike lrecoveries are given in Attachment 8. All laboratory matrix spikes showed recoveries of all compounds between 70-130%. Field spikes were prepared on sample MC-1OlH at a. concentration of 100 ngL using all compounds of interest. The field spike sample is ildentified as MC-104H. Field spike recoveries are also given in Attachment B. PFOSA showed low recovery in the field spike. All other compounds showed recoveries between 70-130%. 5.5 Duplicates All field samples (excluding blanks) were analyzed in duplicate. Results are given along with the sample results in Attachment A. 5.6 Laboratory Control Samples Milliq water was spiked with all compound of interest at 25 and 250 ngR. All recoveries for all compounds were between 70-130% in each LCS. Recoveries are given with the raw data in Attachment D. 5.7 Sample Related Comments 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 DatdSample 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. PAGE4OF5 BACK TO MAIN 8 Attachments 8.1 Attachment A: Results 8.2 Attachment 6:Matrix Spike Recoveries(Fieldand LaboratorySpikes) 8.3 Attachment C: Chain of Custody 8.4 Attachment D: LC/MS/MS Raw Analytical Data 9 Signatures Kevin J Lloyd, Vice President Other Lab Members Contributing to Data Enaksha Wickremesinhe Karen Smith David Bell Date PAGE5OF5 r*\ Inc. CEntrE Analytical Laboratories,. -3048 Research Drive, State College PA 16801 814-231-8032 FAX 814-231-1253 BACK TO MAIN Analytical Results W1973 Cleveland, Tennesse :3MSample Identification IMC-lOIH IMC-103H MC-lO6H .NA MC-107H NA MC-IOBH Sample Description Site 1 P/N Surface Water Site 1 P/N Surface Water Duplicate Site 2 P/N Surface Water Site 2 PIN Surface Water Duplicate Site 3 P/N Surface Water Site 3 PIN Surface Water Duplicate Field Blank P/N Empty PFOS (ng/L) NQ ND ND ND ND ND ND PFOSA (ng/L) NQ ND ND ND ND ND 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 :VD - Compound not detected IVQ - Compound detected at a level between the LOD and LOQ. Result is not quantifiable. IVD c LOD < NQ < LOQ POAA (ng/L) NQ ND ND ND ND ND ND - Please refer to the reverse side for our standard terms and conditions. BACK TO MAIN Attachment 8: LC/MS/MS Laboratory Spike Ftecovery Sample ID: 1 Spiked Amount (ng/L): I MC-105H 1 100 1 PFOS PFOSA POAA Sample Concentration (ngU 14.7 5.6 16.7 Matrix Spike Result 93.3 102 113 Lower Recovery Limit: [ 70 1 Upper Recovery Limit: I 130 I Matrix Spike Result (% Recovery) 78.6 96.4 96.3 Criteria (Pass / Fail) PASS PASS PASS 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. Also note that sample MC-105H is a laboratory spike of sample MC-1131H BACK TO MAIN !Sample ID: MC-106H !Spiked Amount (ng/L): 1 100 I PFOS Sample Concentration (ng/L) 0 0 0 Matrix Spike Result (ng/L) 115 108 113 Lower Recovery Limit: I Upper Recovery Limit: I 70 130 1 Matrix Spike Result (% Recovery) 115.0 108.0 113.0 Criteria (Pass / Fail) PASS PASS PASS BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery !Sample ID: MC-107H I !Spiked Amount (ng/L): I 100 Sample Concentration (n!m 0 0 0 I-ower Recovery Limit: I 70 lllpper Recovery Limit: I 130 Matrix Spike Result (ng/L) 107 106 106 Matrix Spike Result ("A Recovery) 107.0 106.0 106.0 Criteria (Pass / Fail) PASS PASS PASS BACK TO MAIN Attachment B: LC/MS/MS Field Spike Recoveiry !Sample ID: I !Spiked Amount (ng/L): I MC-104H 100 Lower Recovery Limit: /Upper Recovery Limit: Sample Concentration (ng/L) 14.7 5.6 16.7 Matrix Spike Result 0-w) 101 34.5 95.4 [ 70 1 1 130 1 Matrix Spike Result (% Recovery) 86.3 28.9 78.7 Criteria (Pass / Fail) PASS FAIL PASS INote: Sample results less than 25 ng/L are reported as NQ in the resul,tssection as they are Ibelow the limit of quantitation. Results are given in this table for recovery calculations only. Also note that sample MCl04-H is a field spike of sample MC-101H a Environmental Laboratory F - M 38~778 PWO Shipping Address: JMBlda 2-JEW 935 Bush Avenue SL Paul. MN 55106 Telephone: Alternate: (651) 7716753 FAX:(651) n o 6 1 7 8 - 6f,a b m Contact Name - 3 Company 3y'n Special InstrucUons andlor Spaciflc Regulatory Requirements: [rnelhod.limit of deledion. reportingunils. elc.) BACK TO MAIN Chain of Custodv /Remest fnt I ahnmtnrv Analytical Project IDlProject Name GFN 1 4265 Am T- em. plate # lrroject Lead IDept. # (main) 4eaQ1 Final Report Due Date r m Internal Due Date ClasslJoblProject# 001 0 5 3 Dale Available II r3M Env. Lab Project # For Internal Use Only w1473 (bSI \77'tS-b17b Date Due - Contract Lab Analysis Requested: eceived on Ice Orgnal - Accompanyw Samples Last Page - Originator See Reverse Side for lnslrucl~ons