Document YrmojGNwXq5B786qKJq6eqjwK

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) 231-1580 Analytical Report Fluorochemical Characterization of POTW Effluent Port St. Lucie, FL Centre Analytical Laboratory Report No. 023-014N (Revision 1) Revision Date 3/27/01 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 OF 5 BACK TO MAIN 1 Introduction Results are reported for the analysis of a series of P O W effluent samples received by Centre Analytical Laboratories,Inc. (Centre) from the 3M EnvironmentalLaboratory. The samples were collectedfrom Port St. Lucie, FL. 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 4 samples were receivedfor analysis. The samples were prepared and analyzed by LC/MS/MS for the following list of fluorochemicals: Table 1:Target Analysis I ComDound Name Perfluorooctane Sulfonate Perfluorooctane Sulfonvlamide I Perfluorooctanoate I Acronvm 1 I PFOS I PFOSA I 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. Four individual sample containers were received. Samples were received on 6/6/00. 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. 4 Methods - Analytical and Preparatory 4.1 LC/MS/MS 4.1.1 Sample Preparationfor LC/Ms/MSAnalysis Samples were initially treated with 200 ULof 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 Cle 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 PAGE 2 OF5 BACK TO MAIN 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 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 quantitatedagainst standards. A Hewlett-PackardHP1100 HPLC system coupledto a Micromass UltimaMS/MS was usedto analyze the sample extracts. Analysis was performed using selected reaction monitoring (SRM). Samples were initially extracted on 6/12/00 and analyzed by MS/MS on 6/15/00. The initial run was rejected because of control sample recoveries outside of acceptable ranges. The samples were re-extractedon 6/28/00 and re-analyzed by MS/MS between 6/28/00 and 6/29/00. Both sets of raw data are included for informational purposes. The HPLC and MS/MS methods usedfor analysis and instrument parameterscan 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 ( e ) plotted for each point. Using linear regression with l/x weighting, the slope, y-intercept and correlation coefficient (r) and coefficient of determination curve is acceptable if r 20.985 (?2 0.970). were determined. A calibration Calibration standards are preparedusingthe same SPE procedureusedfor 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 reportedhere, calibration criteria were met. 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 calibrationstandard. For these samples, the extractionblankswere 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. PAGE3OF5 BACK TO MAIN 5.4 Matrix Spikes Matrix spikes were prepared for every sample at a concentration of 1000 ng/L using all compounds of interest. Matrix spike recoveries are given in Attachment B. All recoveries were between 70-130%. Field spikes were also prepared at a concentration of 1000 ng/L. All field spike recoveries were between 70 -130%. Field spike recoveries are also given in Attachment B. 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 ngR. All recoveries for all compounds were between 70-130% 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. 8 Attachments 8.1 Attachment A: Results 8.2 Attachment 6:Matrix Spike Recoveries(Field and Laboratory Spikes) 8.3 Attachment C: Chain of Custody 8.4 Attachment D: LC/MS/MS Raw Analytical Data PAGE 4 OF5 9 Signatures Kevin J Lloyd, Vice President Other Lab Members Contributingto Data Enaksha Wickremesinhe Karen Smith BACK TO MAIN Date PAGE 5OF 5 a\Laboratories. Inc. Centre Analytical 3048 Research Drive, State College PA 16801 814-231-8032 FAX 8 - 14-231 1253 BACK TO MAIN Analytical Results W2363 Port St. Lucie, FL 3M Sample Identification MC-639HP O W Effluent NA Duplicate P O W Effluent MC-643H Sample Description PIN ion Pair P/N Ion Pair Duplicate Field Blank P/N Empty PFOS (ng/L) 47.7 62.6 ND PFOSA (ng/L) NQ NQ ND Limit of Detection (LOD)for the procedureis appoximately2.5 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 - Compoundnot detected NQ - Compounddetected at a level betweenthe LOD and LOQ. Result is not quantifiable. ND c LOD c NQ < LOQ POAA (ng/L) 41.2 43.6 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-642H I Spiked Amount (ng/L): I 1000 PFOS PFOSA POAA Sample Concentration 47.7 3.7 41.2 Matrix Spike Result 1017 970 907 Matrix Spike Result (% Recovery) 96.9 96.6 86.6 Criteria (Pass / Fail) PASS PASS PASS Lower Recovery Limit: I Upper Recovery Limit: I 70 1 130 1 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: MC-641H PFOS PFOSA POAA Lower Recovery Limit: Upper Recovery Limit: Sample Concentration (ng/L) 47.7 3.7 41.2 Matrix Spike Result (ng/L) 1110 1206 1176 1 70 I 130 I Matrix Spike Result (% Recovery) 106.2 120.2 113.5 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. a Environmental Laboratory F m 30776 - PWO Shipp4ng Address: 3M Bldg 2-3E09 935 Bush Avenue SI Paul, MN 55106 Tmlephonm: Sample Recmivlng: (651) 7 7 1 4 9 U Altcrnatm: (651) 7716753 BACK TO MAIN Chain of Custody /Request for Laboratory Analytical 'Project IDlProject Name GFuo1q wd Template Y Project Lead wH %-brnw Final Report Due Date [Internal Due Date 146 7 5 3M Env. Lab Project # For Internal Use Only 5\,l,,&f , F W bhBe+-k/(f- w 2 3 3 e2 Company 0) ' e Mailing Address . Bu'aiflk7 -32-07 L >+, city, State, zip 5- I e ]Telephone # ( b ) n k -boIsr ipecld Instructions and/or Specific Rmgulotory Requirmunls: melhod. lunlt of delednn. report- units. elc ) ?n -31 FAX# (IPS11T )&-lP 17 b Date Available Date Due Contract Lab Preservatives: Analysis Requested: Item # Client Sample Identification I $ > Z0 O 3M LIMS# Date Time Sampled Sampled Matrix/ Media nter the number ol contaners of eacl 6. ~ 7. 8. 9. 10. fl Collected by (print): Item # \-4 Relinquished by/Affiliation I L3W c Time AJIA Coltectots signature: /2,IA Date Shipped Via: 1pl4m~ d w RecelredpylAffiliation 3-46&,4 L, A 4 A/d/@] I I Sample Condition Upon Receipt: dAcceptable 0 Other: I I I Temperature: 'C 0 Received on Ice )LhW & 5 5 W l e d COCS i4bP7O1rqlP7W4 b31:lL.lb37, w b74 I L&!omA Copas I page 0f-k Ongtnal- Acccinpanyw Smplos Last Page - Originalor I Comments: See Reverse Side for lnslructlons Time Date //20 6/3/00 ~ I I