Document 5k0brNZ87BLoRBwbvZVOXK8e

BACK TO MAIN 3048 Research Drive LPhone: (814) 231-8032 State College, PA 16801 . Inc. AI.-3, www.centrelab.com Fax: (814) 231-1253 or (814) 231-1580 Analytical Report Fluorochemical Characterization of POTW Effluent Decatur, Alabama (W1979) Centre Analytical Laboratory Report No. 023-014J (Revision 1) Revision Date 3/26/01 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 EnvironmentalTechnology & 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 POTW effluent samples received by Centre Analytical Laboratories, Inc. (Centre) from the 3M EnvironmentalLaboratory. The samples were collectedfrom Decatur, Alabama. The Centre study number assignedto the project is 023-014. Specific fluorochemical characterization 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/A/IS/MS for the following list of fluorochemicals: 0 Table 1: Target Analysis 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. Four individual sample containers were received. Samples were received on 6/6/00. The sample collection dates were not supplied. Chain-of-custody inforrriationis 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 ngR for periods longer than 14 days. 4 Methods - Analytical and Preparatory 4.1 4.1.1 LC/MS/MS 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 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 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 injected and passed thrlough 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 accumte means for analyzing a wide range of organic compounds, includingfluorochemicals. Electrosprayis generally operated at relatively mild temperatures; molecules are ionized, fragmented, and detected. Ions characteristic of known fluorochemicalsare observed and quantitated against standards. A Hewlett-PackardHPl100 HPLC system coupledto a Nlicromass Ultima MS/MS was used to analyze the sample extracts. Analysis was performed using selected reaction monitoring (SRM). Samples were extracted on 6/9/00 and analyzed by MS/MS on 6/13/00. Additional dilutions were performed and analyzed on 6/29/00. 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 `I/xweighting, the slope, y-intercept and correlation coefficient (r) and coefficient of determination (P) 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 concentrationsare within +/-20%of the actual value. For the results reported here, 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-levelcalibrationstandard. For these samples, the extractionblanks 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 presentedhere the instrument blanks are compliant. 5.3 Surrogates Surrogate spikes are not a component of the LC/MS/MS analytical method. PAGE 3OF5 BACK TO MAIN 5.4 Matrix Spikes Matrix spikes were prepared for every sample at a concentration of 100 ng/L using all compounds of interest. Matrix spike recoveries are givlen in Attachment B. Poor recoveries were observed for PFOS and POAA. However, the indigenous amount of material present in these samples was greater than four times the spiking amount. The sample was diluted 1/100 and spiked with each compound of interest at 100 nyL. Spike recoveries were within 70130% Field spikes were also prepared at a concentration of 1000 ng/L. Low field spike recoveries were observed for PFOS and PFOSA, and high recoveries were noted for POAA. 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 ng/L. All recoveries for all compounds were between70-130% 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 i:;sued 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 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 PAGE 4 OF5 9 Signatures Kevin J Lloyd, Vic'e President Other Lab Members Contributingto Data Enaksha Wickremesinhe Karen Smith BACK TO MAIN Date PAGE 5 OF 5 cw\ Laboratoriek,,Inc. CEntrE Analytical 30418 Research Drive, State College PA 16801 814-231-8032 EE814-231-1253 BACK TO MAIN Analytical Results W1979 Decatur, Alabama 3M Sample Identification MC-239H P O W Effluent NA Duplicate P O W Effluent MC-243H Sample Description P/N Ion Pair PIN Ion Pair Duplicate Field Blank P/N Empty PFOS (ng/l.) 5290 4670 ND PFOSA (ng/L) 55.7 56.1 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 < NQ c LOQ POAA (nglL) 2420 2140 ND Please refer to the reverse side for our standard t e r m and conditions. BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery !Sample ID: I MC-242H (1/100) ] !Spiked Amount (ng/L): I 125 I I-ower Recovery Limit: Upper Recovery Limit: Sample Concentration (ng/L) 46.7 56.5 21.4 Matrix Spike Result (ng/L) 185 146 160 I 70 1 I 130 1 -Matrix Spike - Result (% Recovery) 1 10.6 - 71.6 110.9 Note: A 1/100 dilution was performed for PFOS and POAA. PFOSA results are from the undiluted sample Criteria (Pass / Fail) PASS PASS PASS BACK TO MAIN Attachment B: LC/MS/MS Field Spike Recovery Sample ID: I MC-241H 1 Spiked Amount (ng/L): [ 1000 loA Sample Concentration (ng/L) 5290 55.7 2420 Matrix Spike Result 5755 726 3869 -Matrix Spike - Result (% Recovery) 46.5 - 67.0 144.9 Criteria (Pass / Fail) FAIL FAIL FAIL Rill Environmental Laboratory Form 30770 - PWO S3MhlpBpldlngg2A-d3dEr0e9ss: 335 Bush Avenue St Paul, MN 55106 TSealmepphleonRee:ceiving: (651)7784948 Alternate: (661)778.6753 FAX: (651)778-6176 -3 Contact Name 5 Company a! t: Mailing Address ,uh'Q a -3 2-0 9 Spacial Instructions andlor Specific Regulatory Requirements: [method.limit of detection. reporting units. SIC) BACK TO MAIN 1 46 71 Chain of Custody /Request for Laboratory Analytical .-.,. (. .-*-.- (Project IDIProject at-. &I-.-.. I~~~~~IV ,.-~ ,nY'". I 'I r m. % - o i a r e uu cc/ vm ~~~ ~~~ I Project Lead L'J-c\ Internal Due Date &++uLl ' 3M Env. Lab Project # I For Internal Use Only I Deot. # (main) 4=lQ\ IClasslJoblProject # ( 3 0 ) ~ ~ s ~ I Date Available . PD'S-3 1 Date Due t 0 - Contract Lab Analysis Requested: Complele below. Attach any associated Informetlon. Item Client Sample Identification # os r >zo 3M LIMS# Date Time Sampled Sampled Matrixl Media inter the number of conlainerr of ead 5. I - G! 7. 8. 9. 10. Y I I l---r- I <1 - I I I I I I I .C- . m 5 Xher Associated CoCs Copies to