Document KGarye2rR8v6Mn10rd7d1jZvQ

BACK TO MAIN CEntrE Analytical LaboratoriEs, Inc. 3048 Research Drive State College, PA 16801 www.centrelab.com (814)231-8032 Fax: (814)231-1253 or (814)231-1 580 Analytical Report Fluorochemical Characterization of Surface Water Samples Columbus, GA (W2336) Centre Analytical Laboratory Report No. 023-014E (Revision 1) Revision Date 3/22/01 Testing Laboratory Centre Analytical Laboratory, Inc. 3048 Research Drive State College, PA 1680'1 3M Environmental Laboratory Contact Kent R. Lindstrorri Bldg. 2-3E-09 P.O.Box 33331 St. Paul, MN 55133-3331 Phone: (651) 778-5352 Requester Kris J. Hansen, Ph.lD. 3M Environmental Technology & Safety Services Bldg. 2-3E-09 P.O. Box 33331 St. Paul, MN 55133-3331 PAGE 1 OF5 BACK TO MAIN 7 Introduction Results are reported for the analysis of a series of sutface water samples received by Centre Analytical Laboratories, Inc. (Centre) from the 3M EnvironmentalLaboratory. The samples were collectedfrom Columbus, GA. The Centre study number assignedto the project is 023-014. Specific fluorochemicalcharacterization by liquid chromatography/ 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/MS for the following list of fluorochemicals: Table 1: Target Analysis Compound Name Perfluorooctane Sulfonate Perfluorooctane Sulfonvlamide Perfluorooctanoate The analytical method used was validated by Centre. The validation protocol and results are on file with Centre. Data presentedhere is the highest quality data available at this time. 2 Sample Receipt The samples were submitted in individual plastic containers and were not preserved. Eight individualsample containers were received. Samples were received on 05/03/00. The sample collection dates were not supplied. Chain-of-custody inforniation is presented in Attachment C. 3 Holding Times The analytical method used was validated against a niaximum 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 acceptable recoveries at 100 and 1000 ng/L for periods longer than 14 days. PAGE2OF5 BACK TO MAIN 4 Methods -Analytical and Preparatory 4.1 LCIMSIMS 4.1.1 Sample Preparation for LC/Ms/MS Analysis Samples were initially treated with 200 ULof 250 m a 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 C18SPE cartridge. The cartridge was first eluted with 5 mL of 40% metlianlol in water solution. The eluate was discarded and the SPE column was then eluted with 100/o 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 thrlough 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 observedand quantitated against standards. A Hewlett-PackardHP1100HPLC system coupledto a Nlicromass Ultima MSNS was usedto analyze the sample extracts. Analysis was performed using selected reaction monitoring (SRM). Samples were extracted on 5/18/00 and analyzed by MS/MS between 5/20/00 and 5/21/00. 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 ngR (ppt) The response of the quantitation ion versus the concentration was plotted for each point. Using linear regression with `I/x weighting, the slope, y-intercept and correlation coefficient (r) and coefficient of determination (12) were determined. A calibration curve is acceptable if r 10.985(12 2 0.970). Calibration standards are prepared using the same SF'E 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. PAGE 3OF5 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-levelcalibration standard. For these samples, the extraction blanks were compliant. Instrument blanks in the form of clean methanol solvent were also analyzed after every high- level 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 cornpliant. 5.3 Surrogates Surrogate spikes are not a component of the LC/MS/hAS ;analytical method. 5.4 Matrix Spikes Matrix spikes were prepared for every field sample (excluding blanks) at a concentration of 100 ng/L using all compounds of interest. Matrix spike recoveries are given in Attachment B. All compounds showed matrix spike recoveries between `70-130% in all samples. Field spikes were prepared on sample MC-501H at a concentration of 100 n g R using all compounds of interest. The field spike is identilied as sample MC-504H. Field spike recoveries are also given in Attachment B. The field spike results showed low recovery for PFOSA. All other compounds showed matrix spike recovleries between 70-130%. 5.5 Duplicates All samples (excluding blanks) were analyzed in duplicale. 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 215 and 250 ngR. All recoveries for all compounds were between 70-130% in each LCS. Results are given along 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 emlpty container and analyzed in the same manner as the other samples. 6 Datasummary 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. PAGE4W5 BACK TO MAIN 8 Attachments 8.1 Attachment A: Resub 8.2 Attachment 6:Matrix Spike Recoveries(Fieldand Laboratory Spikes) 8.3 Attachment C: Chain of Custody 8.4 Attachment D: LC/MS/MS Raw Analytical Data 9 Signatures - Operations Manager - Kevin J Lloyd, Vice President Date j 3 MA&%U a I Date Other Lab Members Contributing to Data Enaksha Wickremesinhe Karen Smith David Bell PAGE 5OF5 BACK TO MAIN 3048 Research Drive, State College PA 16801 814-231-8032 FAX 814-231-1253 Analytical Results W2336 Columbus, GA :3MSample Identification Sample Description PFOS (iig/L.) PFOSA (ngL) IWC-501 H IUC-503H MC-506H NA MC-507H NA MC-508H MC-584H NA Site 1 P/N Surface Water 63.8 NQ Site 1 P/N Surface Water Duplicate 59.9 NQ Site 2 P/N Surface Water 76.6 NQ Site 2 PIN Surface Water Duplicate 83.3 NQ Site 3 P/N Surface Water 55.4 NQ Site 3 P/N Surface Water Duplicate 55.4 NQ Field Blank-P/N Empty ND ND Quiet Surface Water ND ND Quiet Surface Water Duplicate 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 ND - Compound not detected NQ - Compound detected at a level between the LOD and LOQ. Result is not quantifiable. ND < LOD c NQ c LOQ POAA (ng/L) 26.1 25.6 26.1 26.7 NQ NQ ND ND ND - - 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: I MC-505H 1 !Spiked Amount (ng/L): I ~~ 100 Lower Recovery Limit: IJpper Recovery Limit: k Sample Concentration (ng/L) 63.8 11.7 26.1 Matrix Spike Result (ng/L) 164 107 121 I 70 I [ 130 -Matrix Spike - Result (% Recovery) 100.2 - 95.3 94.9 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-505H is a laboratory spike of sample MC-501H BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery !Sample ID: I MC-506H I !SpikedAmount (ng/L): 1 100 I 1IPFOS IPFOSA IPOAA Sample Concentration (ng/L) 76.6 16.5 26.1 Matrix Spike Result (ng/L) 162 114 124 -Matrix Spike - Result (% Recovery) 85.4 - 97.5 97.9 Criteria (Pass / Fail) PASS PASS PASS IUpper Recovery Limit: 130 I IVote: Sample results less than 25 ng/L are reported as NQ in the resullts section as they are Ibelow 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: MC-507H 1 Sample Matrix Spike Concentration Result IIPFOS IPFOSA IPOAA (ng/L) 55.4 12.0 23.6 (ng/L) 159 117 125 Lower Recovery Limit: I 70 1 IJpper Recovery Limit: I 130 I -Matrix Spike - Result (% Recovery) 103.6 105.0 101.4 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 rectovery calculations only. BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: I MC-584H I Spiked Amount (ng/L): I 100 I POAA Lower Recovery Limit: Upper Recovery Limit: Sample Concentration (ng/L) 0 0 0 Matrix Spike Result (ng/L) 79.9 94.5 103 I 70 1 1 130 I -Matrix Spike Result (% Recovery) 9 79.9 94.5 103.0 9 Criteria (Pass / Fail) PASS PASS PASS BACK TO MAIN Attachment B: LC/MS/MS Field Spike Recovery !Sample ID: MC-504H I Sample Concentration Matrix Spike Result -Matrix Spike Result 69.0 26.1 124 97.9 Criteria (Pass / Fail) PASS FAIL PASS I-ower Recovery Limit: I 70 I IJpper Recovery Limit: I 130 1 IVote: Sample results less than 25 ng/L are reported as NQ in the results section as they are Ibelow the limit of quantitation. Results are given in this table for recovery calculations only. ,Also note that sample MC-504H is a field spike of sample MC-501I-i 3M Environmental Laboratory F M 3~8778 - PWO "c"LpIp-.-.I"-.-Y .AA """I.--. . _ _ I ._ L . . I .8.&#U",,.. 3MBldg 2-3E-09 Samplm Receiving: (651) 7784940 935 BushAvenue Alternate: (651) 7716753 SI Paul.MN 55106 FAX: (651) 7784170 BACK TO MAIN Chain of Custody /Request for Laboratory Analytical 1 42 69 Project IDlProJect N a m e ~ f / L l ~ ~ / / ~ ~ ~ ~ ~ ~ R 4 LIp , flldj ,-I )~- hdf-~,lAy 4l Template # Proiect Lead I1FinaI Report Due Date Internal Due Date 6 mB&eil 3M Env. Lab Project # For Internal Use Only wa= lethod, lmit of detedlMI.reporlng u n l s . etc ) Client Sample Identification I 3M LIMS# Sam led Time Sam led lh Matrix/ Media L4-J ti4 Analysis Requested: I I. I ICollector's signature: 0IA I I sample Condition Upon Receipt: dAcceptable 0 Other: remperature: 'C d e c e i v e d on Ice IWAssoualedCoCI 1 4 3 ~,3\ ~ a c o l p , \ ~ a ~ ~ , '-kab%\L, ta 70 Oriiinal -AccompanyingSamples I I I I Comments Last Paga - Originator See Reverse Side fw Inslructions I I