Document KJnM5OzBR9BME8BGj4m6G25RX

Centre Analytical Laboratories, Inc. 3048 Research Drive Phone: (814) 231-8032 State College, PA 16801 www.centrelab.com Fax: (814) 231-1253 or (814) 231-1580 Analytical Report Fluorochemical Characterization of Water and Sediment Samples Port St. Lucie Resampling (E00-2003) Centre Analytical Laboratory Report No. 023-014P 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 .B ox 33331 St. Paul, MN 55133-3331 Phone: (651)778-5352 Requester Dale Bacon Ph.D. 3M Environmental Technology & Safety Services Bldg. 2-3E-09 P.O. Box 33331 St. Paul, MN 55133-3331 1 Introduction Results are reported for the analysis of a series of water and sediment samples received by Centre Analytical Laboratories, Inc. (Centre) from the 3M Environmental Laboratory. The samples were collected from Port St. Lucie, Florida and are part of 3M Project E00-2003. The Centre study number assigned to the project is 023-014. Specific fluorochemical characterization by liquid chromatography / tandem mass spectrometry (LC/MS/MS) and ion chromatography was requested for all samples. A total of 45 samples' were received for analysis. The samples were prepared and analyzed by LC/MS/MS for the following list of fiuorochemicals: Table 1: Target Analysis Compound Name Perfluorooctane Sulfonate Perfluorooctane Sulfonvlamide Perfluorooctanoate Acronym PFOS PFOSA POAA The analytical methods used for water samples were validated by Centre. The validation protocol and results are on file with Centre. The methods were modified for the sediment samples, however the procedures have not been fully validated for this matrix. 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. Forty-five individual sample containers were received. Samples were received on 7/25/00. The samples were collected between 7/18/00 and 7/19/00. Chain-of-custody information is presented in Attachment A. 3 Holding Times - The analytical method used was validated against a maximum holding time of 14 days. Stability after this time period has not been validated, however it should be noted that field fortifications have shown acceptable recoveries at the 100 ng/L for periods longer than 14 days. PAGE 2 OF5 4 Methods - Analytical and Preparatory 4.1 LC/MS/MS 4.1.1 Sample Preparation for LC/M S/M S Analysis Water 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 C ,8 SPE cartridge. The cartridge was firsTeluted 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. For the sediment and sludge samples, a representative portion of sample (5 grams) was first extracted into 5 ml of methanol. The extracts were filtered and diluted to a final volume of 40 mL with Type I water. The diluted extracts were then treated in the same manner as the water samples, beginning with the solid phase extraction. 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 HP1.100 HPLC system coupled to a Micromass Ultima MS/M S was used to analyze the sample extracts. Analysis was performed using selected reaction monitoring (SRM). W ater samples were extracted between 8/15/00 and 8/17/00 and analyzed by MS/MS between 8/18/00 and 8/23/00. Sediment and sludge samples were extracted on 8/18/00 and were analyzed by MS/M S on 8/21/00. The HPLC and MS/M S methods used for analysis and instrument parameters can be found in Attachments D and E. , 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) for LC/MS/M S analysis. The instrument response 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. PAGE 3 OF 5 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 blanksjn. 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 methods. 5.4 Matrix Spikes Matrix spikes were prepared for every field sample using all compounds of interest Matrix spike recoveries are given in Attachment C. Field spikes were submitted with the water samples. Field spike recoveries are also included in Attachment C. The results from the 200 ppt field spike for sample Q SW Palm City-C-FMS200ppt A indicate that this sample was spiked at 1000 ppt rather than 200 ppt. The results for QSW Paim City-C-FMS-200ppt B indicate a 200 ppt spiking concentration. 5.5 Duplicates All field samples were analyzed in duplicate. Results are given along with the sample results in Attachment B. 5.6 Laboratory Control Samples For LC/MS/MS analyses, Milliq water was spiked with all compounds of interest at 25 and 250 ng/L during each extraction set. All recoveries for all compounds were between 70-130% in each LCS. Results are given along with the raw data in Attachments D and E. 5.7 Sample Related Comments There are no other sample related comments for this data set 6 Data Summary Please see Attachment B for a detailed listing of the analytical results. Surface water results are reported in parts per trillion (ppt) (ng/L). Sediment and sludge sample results are reported in parts per billion (ppb) (ng/g) on both an as-received and dry-weight basis. PAGE 4 OF 5 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: Chain-of-Custody 8.2 Attachment B: Results. 8.3 Attachment C: Matrix Spike Recoveries ' 8.4 Attachment D: LC/MS/MS Raw Analytical Data (Surface W ater Samples) 8.5 Attachment E: LC/MS/MS Raw Analytical Data (Sediment and Sludge Samples) 9 Signatures ^ /O o h n M. Flaherty,IWsinadfo- Operations Manager Kevin J Uoyd, Vice President Date Other Lab Members Contributing to Data Karen Smith PAGE 5 OF5 ANALYTICAL REPORT M & Centre Analytical Laboratories. Inc. 3048 R esearch Drive, State C ollege PA 16801 814-231-8032 FAX 814-231-1253 Analytical Results E00-2003 Port St. Lucie, FL Resampling (water sam ples) 3M Sample Identification MDW PIN-R-O-C M D W PIN -R -O -C dup M D W P IN -Lim e-C M DW PIN-Lim e-C dup MDW POut -C M DW POut-C dup NPW W TPEff -C NPW W TPEff-C dup NPW W TPCC-C N PW W TPC C -C dup PSLF Leach-C PSLF Leach-C dup T W #2 Fire Dept-C T W #2 Fire Dept-C dup SW #3 SH-C S W #3 SH -C dup TW #3 Penpark-C T W #3 Penpark-C dup SW#1 Penpark-C SW#1 Penpark-C dup TW#1 Holiday Inn-C TW #1 Holiday Inn-C dup SW #2 MCM-C SW #2 M CM -C dup Q SW Palm City-C Q S W Palm City-C dup Blind Dup C1 Blind Dup C1 dup Blind Dup C2 Blind Dup C2 dup f PFOS (ng/L) <25 <25 <25 <25 <25 <25 14.7 J 16.6 J 85.5 78.8 429 425 <25 <25 7.8 J 5.4 J <25 <25 5.2 J 4.1 J <25 <25 7.7 J 9.3 J 2930 2850 <25 <25 8.0 J 9.8 J . PFOSA (ng/L) <25 <25 . <25 <25 <25 <25 <25 <25 4.4 J 3.5 J 7.0 J 8.0 J <25 <25 <25 <25 <25 <25 <25 <25 <25 <25 <25 <25 30.0 27.5 <25 - <25 <25 <25 POAA (ng/L) <25 <25 <25 <25 <25 <25 15.1 J 14.1 J 42.9 40.2 1030 1020 <25 . <25 <25 <25 <25 <25 <25 <25 <25 <25 <25 <25 96.9 97.1 <25 <25 <25 <25 I J - Compound is present, but below the reporting limit of 25 ng/L. The result is an estimated value. Method Detection Limits are approximately 2.5 ng/L for PFO S and P FO S A and 7.5 ng/L for POAA. I Please refer to the reverse side for our standard terms and conditions. ' ANALYTICAL REPORT f iggSSS^ Centre Analytical ygWSSft, Laboratories. Inc. 3048 R esearch D rive, S tate C olleg e PA 16801 8 1 4 -231-8032 FAX 814-231-1253 Analytical Results E00-2003 Port St. Lucie, FL Resam pling (solids) 3M Sam ple Identification N PW W TP Sludge-C N PW W TP Sludge-C dup SED #3 SH-C SED #3 SH-C dup SED#1 Penpark-C SED#1 Penpark-C dup SED#2 MCM-C SED#2 M CM -C dup PFOS (ug/Kg) * T (as received) PFOSA (ug/Kg) (as received) POAA (ug/Kg) (as received) 1.36 1.30 < 0.200 < 0.200 < 0.200 < 0.200 < 0.200 < 0.200 ' < 0.200 <0.200 <0.200 < 0.200 < 0.200 < 0.200 < 0.200 < 0.200 - < 0.200 < 0.200 < 0.200 < 0.200 < 0.200 < 0.200 < 0.200 < 0.200 3M Sam ple Identification N PW W TP Sludge-C N P W W T P Sludge-C dup SED #3 SH-C SED #3 SH -C dup SED#1 Penpark-C SED#1 Penpark-C dup SED#2 MCM-C SED#2 M CM -C dup PFOS (ug/Kg) (dry weight) 62.9 60.2 < 0.261 < 0.261 < 0.263 < 0.263 < 0.304 < 0.304 PFOSA (ug/Kg) (dry weight) <9.3 <9.3 < 0.261 < 0.261 < 0.263 < 0.263 < 0.304 < 0.304 POAA (ug/Kg) (dry weight) <9.3 <9.3 < 0.261 < 0.261 < 0.263 < 0.263 < 0.304 < 0.304 J - Compound is present, but below the reporting limit. The result is an estimated value. Please refer to the reverse side for our standard terms and conditions. i V Adsdhiotiwonnaolnsasomupthlinmgaspites Environmental Sampling Sites North of Port St. Lucie, FL ; 01008 GDT, Ino. Environmental Sampling Sites South of Port St. Lucie, FL