Document pBXx3vZgb3qgpdmJrbwdmrkjB

BACK TO MAIN Centre Analytical Laboratories. Inc. 3048 Research Drive State College, PA 16801 www.centrelab.com ^P hone: (814) 231-8032 Fax: (814) 231-1253 or (814) 231-1580 Analytical Report Fluorochemical Characterization of POTW Effluent Pensacola, Florida Centre Analytical Laboratory Report No. 023-014L (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 Pensacola, Florida. 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 fluorochemlcals: Table 1: Target Analysis Compound Name Perfluorooctane Sulfonate Perfluorooctane Sulfonvlamide Perfluorooctanoate Acronym 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 discarded and the SPE column was then eluted with 100% methanol. A 5 ml portion of PAGE2 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 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 initially extracted on 6/12/00 and analyzed by MS/MS on 6/14/00. The data from samples MC-339H and MC-342H were considered unusable due to inconsistent results between the sample and sample duplicate. These samples were re-extracted on 6/29/00 and re-analyzed by MS/MS between 6/29/00 and 6/30/00. 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 +/-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 1000 ng/L using all compounds of interest. Matrix spike recoveries are given in Attachment B. All matrix spikes showed recoveries between 70 -130% . Field spikes were also prepared at a concentration of 1000 ng/L. Field spike recoveries are also given in Attachment B. Based upon the spike recoveries, it appears that the field spikes were prepared at 100 ng/L rather than the 1000 ng/L listed on the field data sheets. Recovery results are calculated based on a 100 ng/L spiking level. 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 PAGE40F5 9 Signatures Other Lab Members Contributing to Data Enaksha Wickremesinhe Karen Smith BACK TO MAIN PAGE 5 OF5 ANALY 3048 Research Drive, State College PA 16801 814-231-8032 FAX 814-231-1253 Analytical Results W2176 Pensacola, Florida 3M Sample Identification MC-339H POTW Effluent NA Duplicate POTW Effluent MC-343H Sample Description P/N Ion Pair P/N Ion Pair Duplicate Field Blank P/N Empty PFOS (ng/L) 833 959 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) 84.3 89.9 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: Spiked Amount (ng/L): MC-342H 1000 PFOS PFOSA POAA Sample Concentration (ng/L) 833 8.8 84.3 Matrix Spike Result (ng/L) 1752 1011 1050 Matrix Spike Result (% Recovery) 91.9 100.2 96.6 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. BACK TO MAIN Attachment B: LC/MS/MS Field Spike Recovery Sample ID: Spiked Amount (ng/L): | MC-341H 1(50 PFOS PFOSA POAA Sample Concentration (ng/L) 833 8.8 84.3 Matrix Spike Result (ng/L) 724 112 159 Matrix Spike Result (% Recovery) -109.0 103.2 74.7 Criteria (Pass / Fail) FAIL 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. Environmental Laboratory Form 38778 - PWO Shipping Address: 3M Bldg 2-3E-09 93b Uukh Avenue St. Paul, MN 55106 Telephone: Sample Receiving: (651) 776-4946 Alternate: (651) 776 6753 FAX: (651) 778-6176 Contact Name Company STY^ S z ,n BACK TO MAIN Chain of Custody /Request for Laboratory Analytical 14673 Project ID/Project Nam e C & A J O f f U J c A C v i Template # Project Lead Dept. # (main) p l b -k U n 'W v | Linai Report Due Date Internal Due Date Class/Job/Project # C>o i c S S S T O O ^ 3M Env. 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