Document ypEeDvedLkazKQ73ma3EV25BD

BACK TO MAIN Cmtre 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 Drinking Water Samples Pensacola, FI (W2176) Centre Analytical Laboratory Report No. 023-007D (Revision 1) Revision Date 3/20/01 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 OF5 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 Pensacola, FI. 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 receivedfor analysis. The samples were prepared and analyzed by LC/MS/MS for the following list of fluorochemicals: ComDound Name Perfluorooctane Sulfonate Perfluorooctane Sulfonvlamide Perfluorooctanoate Acronvm PFOS PFOSA POAA 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-custodyinformationis presentedin 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. PAGE2OF5 BACK TO MAIN 4 Methods - Analytical and Preparatory 4.1 LC/MS/MS 4.1.1 Sample Preparation for LC/MS/MS Analysis Samples were initially treated with 200 ULof 250 mgR 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 CIS SPE 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-PackardHPl100 HPLC system coupledto a Micromass Ultima MS/MS was used to analyze the sample extracts. Analysis was performed using selected reaction monitoring (SRM). Samples were extracted on 2/22/00 and analyzed by MS/MS on 2/23/00. 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 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 l/x weighting, the slope, y-intercept and correlation coefficient (r) and coefficient of determination (?) were determined. A calibration curve is acceptable if r 20.985 (?2 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. 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 present 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 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 LCNSIMS analytical method. 5.4 Matrix Spikes Matrix spikes were prepared for every sample at a concentration of 100 ngR 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 ngL using all compounds of interest. Field spike recoveries are also given in Attachment B.The field spike results for sample MC-329H gave recoveries for all compounds of approximately 1000 Yo, 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 Samples Milliq water was spiked with all compound of interest at 25 and 250 ng/L. Initial analysis of the 25 ng/L LCS showed low recovery for PFOS. The standard was reinjected and was found to have acceptable recovery (70-130%). All other recoveries for all compounds were between 70130% in each LCS. 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. PAGE 4 OF5 BACK TO MAIN 8 Attachments 8.1 Attachment A: Results 8.2 Attachment 6:MatrixSpike Recoveries (Fieldand Laboratory Spikes) 8.3 Attachment C: Chain of Custody 8.4 Attachment D: LC/MS/MS Raw Analytical Data 9 Signatures ions Manager Kevin J Lloyd, Vice President Date $3 n4vldRru 9 - 1 Date Other Lab Members Contributing to Data Enaksha Wickremesinhe Karen Smith PAGE 5 OF5 a\Laboratories. Inc. Centre Analytical 3048 Research Drive, State College PA 16801 814-231-8032 FAX 814-231-1253 BACK TO MAIN Analytical Results W2171 Pensacola, FI 3M Sample Identification MC-315H MC-317H MC-320H MC-321H MC-323H MC-326H MC-328H MC-331H NA MC-332H NA MC-333H Sample Description Intake-PIN Intake-P/N duplicate Intake-Field Blank Empty Outflow-P/N Outflow-P/N duplicate Site 1 P/N Site 1 PIN 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) ND ND ND ND ND ND ND ND ND 46.6 42.3 ND PFOSA (ng/L) ND ND ND ND ND ND ND ND ND ND ND ND POAA (ns/L) ND ND ND ND ND ND 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 ND - Compound not detected NQ - Compound detected at a level between the LOD and LOQ. Result is not quantifiable. ND c LOD < NQ c 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: I MC-319H Spiked Amount (ng/L): 100 I PFOS PFOSA POAA Sample Concentration (ng/L) 0 0 0 Matrix Spike Result (ng/L) 101 112 95.6 Lower Recovery Limit: I Upper Recovery Limit: 70 1 130 I Matrix Spike Result (% Recovery) 101 .o 1 12.0 95.6 Criteria (Pass / Fail) PASS PASS PASS BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: MC-325H 1 PFOS PFOSA Sample Concentration (ng/L) 0 0 Matrix Spike Result (ng/L) 103 124 Lower Recovery Limit: [ Upper Recovery Limit: I 70 130 1 Matrix Spike Result (% Recovery) 103.0 124.0 Criteria (Pass / Fail) PASS PASS BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: I MC-330H I Spiked Amount (ng/L): I 100 PFOS PFOSA POAA Sample Concentration (ngU 0 0 0 Matrix Spike Result (ng/L) 115 136 109 Lower Recovery Limit: I Upper Recovery Limit: [ 70 1 130 1 Matrix Spike Result (% Recovery) 115.0 136.0 109.0 Criteria (Pass / Fail) PASS FAIL PASS BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: MC-331H I Spiked Amount (ng/L): 1 100 PFOS PFOSA POAA Lower Recovery Limit: Upper Recovery Limit: Sample Concentration (ng/L) 0 0 0 Matrix Spike Result (ng/L) 104 135 105 1 70 1 L 130 1 Matrix Spike Result (% Recovery) 104.0 135.0 105.0 Criteria (Pass / Fail) PASS FAIL PASS BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: r MC-332H 1 Spiked Amount (ng/L): I 100 1 PFOS PFOSA POAA Sample Concentration (ng/L) 46.6 0 0 Lower Recovery Limit: I 70 Upper Recovery Limit: I 130 Matrix Spike Result (ng/L) 172 122 112 Matrix Spike Result (% Recovery) 125.4 122.0 112.0 Criteria (Pass / Fail) PASS PASS PASS BACK TO MAIN Attachment B: LC/MS/MS Field Spike Recovery Sample ID: Spiked Amount (ng/L): I MC-318H 1 100 I PFOS PFOSA POAA Sample Concentration (ng/L) 0 0 0 Lower Recovery Limit: I 70 Upper Recovery Limit: I 130 Matrix Spike Result (ng/L) 101 102 108 Matrix Spike Result (% Recovery) 101.o 102.0 108.0 Criteria (Pass / Fail) PASS PASS PASS BACK TO MAIN Attachment B: LC/MS/MS Field Spike Recovery Sample ID: MC-324H I Spiked Amount (ng/L): I 100 Sample Concentration PFOS PFOSA POAA Lower Recovery Limit: I Upper Recovery Limit: I 0 0 0 ~~~ 70 130 Matrix Spike Result (ng/L) 104 103 107 Matrix Spike Result (% Recovery) 104.0 103.0 107.0 Criteria (Pass / Fail) PASS PASS PASS BACK TO MAIN Attachment B: LC/MS/MS Field Spike Recovery Sample ID: MC-329H Spiked Amount (ng/L): [ 100 1 PFOS PFOSA POAA Sample Concentration (ngU 0 0 0 Matrix Spike Result (ngU 1124 1269 1046 Lower Recovery Limit: I 70 I Upper Recovery Limit: [ 130 Matrix Spike Result (% Recovery) 1124.0 1269.0 1046.0 Note: Results indicate that this sample was spiked at 1000 ng/L instead of 100 ng/L Criteria (Pass 1 Fail) FAIL FAIL FAIL 3cH Envii .mental Laboratory Form 30770 - PWO Shipping Address: 3M Bldg 2-3E-09 935 Bush Avenue SI Paul.MN 55106 - 3~ 3 Company 0) 5 h,,*bAd- 35 4 4 MailingAddress 5 3 p d f l m n n City, State. zip ' -Telephone# . \ 2 ,foxj{>&-jbo~h Special lnstruclions andlor'Spaclfic Regulatory Requirements: & P 5_sJ33 method. limit of diledion. repoilng unds. etc ) orn FAX# .;;t*;sCsl~* (&I 1-&-(&lp Ittetm I Client Sample Identification BACK TO MAIN Date Available - Date Due Contract Lab I I I I Analysis Requested: Complete below. Attach any associated infomution. A/ Collected by (print). 21 U .0L Item # "Y) 2 1-10 c 0 .C- m c 0 Samole Condition Uoon ReceiD!: Relinquished by/Affiliation 0 AcceDtable 0 Olher: Original -AccompanyingSamples Time .- Date Collector's signature: Shlpped Vla: 2% I Comments Lasl Page - Originator See Revarse Side for lnstrudlonr Time 1630 Dale 2-1 s - a I I 3M Envit .mental Laboratory Form 38778 - PWO Shippino Address: 3M Bldg 2-3E-09 935 Bush Avbnue SI Paul,MN 55iC6 Telephone: Sample Receiving:(651) 778-4948 Allemale: (651) 778-6753 FAX: (651) 778-6176 BACK TO MAIN Chain of Custody IReque. Jr Laboratory Analytical 17127 3M Env. 1 Project # For lnterital Use Only I&M Template C . . -3--- ---- Dept.# (main) Y mim w I , , , , IInternalDue Date I Class/JoblProject # I 3 Ill i I Y Special Instructions andlor Specific Reaulalow Requirements: (inelhod l m l of drledion. repoilmg unils. SIC ) Date Due Analysis Requested: Page le Origlnal- b r n p a n y n g Sampler Lasl Page - Originator See Reverse Sids IM Inrlnrlw.