Document g2aRvknkvVgQkoOQB1gngKDna

BACK TO MAIN Centre Analytical Laboratories, Inc. 3048 Research Drive State College, PA 16801 www.centrelab.com ^P h on e : (814)231 -8032 Fax: (814) 231 -1253or (814) 231 -1580 Analytical Report Fluorochemical Characterization of POTW Effluent Cleveland, Tennessee (W1973) Centre Analytical Laboratory Report No. 023-0141 (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 Environmental Technology & Safety Services Bldg. 2-3E-09 P.O. Box 33331 St. Paul, MN 55133-3331 PAGE 10 F 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 Environmental Laboratory. The samples were collected from Cleveland, Tennessee. The Centre study number assigned to the project is 023 014. Specific fluorochemical characterization by liquid chromatography / tandem mass spectrometry (LC/MS/MS) was requested for all samples. A total of 4 samples were received for 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 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 information is presented in 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 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 C18SPE cartridge. The cartridge was first eluted with 5 mL of 40% methanol in water solution. The eluate was PAGE2 OF5 BACK TO MAIN 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-Packard HP1100 HPLC system coupled to a Micromass 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 1/x weighting, the slope, y-intercept and correlation coefficient (r) and coefficient of determination (r2) were determined. A calibration curve is acceptable if r >.0.985 (r2 > 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 +1-20% 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-level calibration standard. 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 LC/MS/MS analytical method. PAGE 3 OF5 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 given in Attachment B. High matrix spike recoveries were observed for PFOS and P O M ; however, the indigenous amount of material in these samples was greater than four times the spiking amount. Field spikes were also prepared at concentrations of 1000 ng/L. 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 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 Data/Sample 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 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 Other Lab Members Contributing to Data Enaksha Wickremesinhe Karen Smith BACK TO MAIN PAGE 5 OF5 Centre Analytical Laboratories, Inc. 3048 Research Drive, State College PA 16801 814-231-8032 FAX 814-231-1253 R A r * i n MAIM Analytical Results W1973 Cleveland, Tennesse 3M Sample Identification MC-139H POTW Effluent NA Duplicate POTW Effluent MC-143H Sample Description P/N Ion Pair P/N Ion Pair Duplicate Field Blank P/N Empty PFOS (ng/L) 417 454 ND PFOSA (ng/L) NQ NQ 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 < LOQ POAA (ng/L) 655 674 ND Please refer to the reverse side for our standard terms and conditions. 0 BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: Spiked Amount (ng/L): MC-142H 100 PFOS PFOSA POAA Sample Concentration (ng/L) 417 3.8 655 Matrix Spike Result (ng/L) 562 116 829 Matrix Spike Result (% Recovery) 145.0 112.2 174.0 Criteria (Pass / Fail) FAIL PASS FAIL Lower Recovery Limit: 70 Upper Recovery Limit: 130 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 PFOS and POAA sample concentrations are greater than 4X the spiking level BACK TO MAIN Attachment B: LC/MS/MS Field Spike Recovery Sample ID: Spiked Amount (ng/L): MC-141H 1000 PFOS PFOSA POAA Sample Concentration (ng/L) 417 3.8 655 Matrix Spike Result (ng/L) 1424 814 1670 Matrix Spike Result (% Recovery) 100.7 81.0 101.5 Criteria (Pass / Fail) PASS PASS PASS Lower Recovery Limit: 70 Upper Recovery Limit: 130 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. 3M Environmental Laboratory Form 38778 - PWO Shipping Address: 3M Bktg 2-3E-09 935 Bush Avenue S t Paul. MN 55106 Telephone: Sample Receiving: (651) 778-4948 Alternate: (651)778-6753 FAX: (651) 778-6176 Chain of Custody /Request for Laboratory Analytical 1 4 6 7 0 Projec tip /P f o je c t N a m e ^ D l3 T em plate# Project Lead Vin a k C U x k n k . T A J ^ 4 W , fFininaall DRenpnonrr*t rD\.u.ne nDate Internal Due Date 3MFoEr nInvt.erLnaalbUPsreoOjenclyt # (a j A h a i2 3 W .. ^o *oa & Contact Name A ________________________________ Company "p^C C \ Mailing Address City, State, Zip S v V . Q u J T v Y l A TelePh ( t f l S l 3 - n . f c - L . O I X ___________________ FAX* special in siru cu o n and/or ftpacinc Regulatory Requirem ents: (method, limit of detection, reporting units, etc.) (b S -m ^ - t e n l n ________________ Date Available Date Due Contract Lab Preservatives: b0 L? 0 0 o a AJ T n L pm alyrsis R eqirested: Com p lets be low . / attach any as sociated info rm atior . VOCs None Other Total Number of Containers Item # Client Sample Identification 3M LIMS# 1. rn C -ty tH -1 > l> L > l o r x ( W _______________________________ U f O 2. W S C r^W t XJL-PIA/ T d a P W ` 3. m C H a y t - L A b S p . U - P I O & /-. ____________________ 4. P i W ^ R io .v \K -P tA /-im p h j Po,-, ffcd v XI/" 5. 6. 7. --------------------------------------------------------1 8. 9. _________ 10. .................. - -- Collected by (print): a J \ A f Item # o3 *o*C ffl O-C Relinquished by/Afflliatlon IS M Date Sampled M A >< Time Sampled > t ____ on * O z X (N/) X 8 rt 2 3 Matrix/ Media Enter the number of containers of each \ 1 1 ^ \A 1 iM Xt X 1 MA*X r t A c. % -------- ^ ----- V pi Time ASIA Date M oo / aj\A.Collector's signature: Shipped Via: \ r NJ ~ Y Received by/Affiliation 9 p___ \ $\ V- SpA C.___ ~C.--y-- -- Time ji l Date BACK TO MAIN Sample Condition Upon Receipt: Temperature: Other Associated CoCs: c As.Page Of ^ A c c e p ta b le O Other: O Received on Ice Copies to: LA C-.K M A Original - Accompanying Samples Last Page - O riginator C o m m e n ts : See Reverse Side for Instructions