Document vVNKGzGQx4QDK0d9ZvaNw7Q7Y

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 -1253 or (814) 231 -1580 Analytical Report Fluorochemical Characterization of Sediment, POTW Sludge, and Landfill Leachate Samples Port St. Lucie, Florida (W2363) Centre Analytical Laboratory Report No. 023-014V (Revision 1) Revision Date 3/28/01 Testing Laboratory Centre Analytical Laboratory, Inc. 3048 Research Drive State College, PA 16801 3 M E nvironm ental Laboratory C ontact Kent R. Lindstrom Bldg. 2-3E-09 P.O. Box 33331 St. Paul, MN 55133-3331 Phone: (651)778-5352 Requester Kris 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 sediment, leachate, and sludge 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 W2363. 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 9 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 methods used for originally developed for water samples and were validated by Centre. The water sample validation protocol and results are on file with Centre. The methods were modified for the sediment and sludge samples. The procedures have not been fully validated for these matrices. 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. Seven individual sample containers were received. Samples were received on 7/28/00. 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 in water samples. Stability after this time period has not been validated. 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. PAGE 2 OF 5 BACK TO MAIN 4 Methods - Analytical and Preparatory 4.1 LC/MS/MS 4.1.1 Sample Preparation for LC/MS/MS Analysis Water samples (leachate and field blanks) 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 Ci8 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 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 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 8/28/00 and analyzed by MS/MS between 8/29/00 and 8/30/00. The HPLC and MS/MS methods used for analysis and instrument parameters can be found in Attachments 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) for LC/MS/MS 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. 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. PAGE3 OF5 BACK 10 MAIN 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 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 B. No field spikes were collected from this site. 5.5 Duplicates All field samples were analyzed in duplicate. Results are given along with the sample results in Attachment A. 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. 5.7 Sample Related Comments Empty containers were submitted as filed blanks. The containers were treated with 40 mL of Milliq water and analyzed as per the method. There are no other sample related comments for this data set. 6 Data Summary Please see Attachment A for a detailed listing of the analytical results. Field blank water and leachate results are reported in parts per trillion (ppt) (ng/L). Sediment and sludge sample results are reported in parts per billion (ppb) (ug/Kg) on both an as-received and dry-weight basis. 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. PAGE 4 OF 5 8 Attachments 8.1 Attachment A: Results 8.2 Attachment B: Matrix Spike Recoveries 8.3 Attachment C: Chain of Custody 8.4 Attachment D: LC/MS/MS Raw Analytical Data 9 Signatures BACK TO MAIN Other Lab Members Contributing to Data Karen Smith PAGE5 OF5 ANALY Centre Analytical Laboratories, Inc. 3048 Research Drive, State College PA 16801 814-231-8032 FAX 814-231-1253 -K T O M A IM Analytical Results W2363 Port St. Lucie, Florida (GEN 019) 3M Sample Identification PFOS (ng/L) PFOSA (ng/L) POAA MC-613K Field Blank ND ND ND MC-614K Field Blank NQ NQ ND MC-635K Landfill Leachate 344 NQ 953 MC-635K Landfill Leachate dup 329 NQ 939 MC-636K Field Blank ND ND ND MC-645K Field Blank ND ND NQ Limit of Detection (LOD) for the procedure is approximately 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 Please refer to the reverse side for our standard terms and conditions. 3048 Research Drive, State College PA 16801 814-231-8032 FAX 814-231-1253 Analytical Results W2363 Port St. Lucie, Florida (GEN 019) 3M Sample Identification MC-610K Sediment Site 1 MC-610K Sediment Site 1 dup MC-611K Sediment Site 2 MC-611K Sediment Site 2 dup MC-612K Sediment Site 3 MC-612K Sediment Site 3 dup MC-644K POTW Sludge MC-644K POTW Sludge dup PFOS (ug/Kg) (as received) NQ NQ 0.934 0.906 0.594 0.626 NQ NQ PFOSA (ug/Kg) (as received) NQ NQ NQ NQ NQ NQ NQ NQ POAA (ug/Kg) (as received) 0.291 0.257 0.262 0.244 1.31 1.36 NQ NQ 3M Sample identification PFOS (ug/Kg) (dry weight) PFOSA (ug/Kg) (dry weight) POAA (ug/Kg) (dry weight) MC-610K Sediment Site 1 MC-61 OK Sediment Site 1 dup MC-611K Sediment Site 2 MC-611K Sediment Site 2 dup MC-612K Sediment Site 3 MC-612K Sediment Site 3 dup MC-644K POTW Sludge MC-644K POTW Sludge dup NQ NQ 1.13 1.09 0.763 0.804 NQ NQ NQ NQ NQ NQ NQ NQ NQ NQ 0.37 0.326 0.316 0.294 1.68 1.75 NQ NQ Limit of Detection (LOD) for the procedure is approximately 0.08 ug/Kg for all compounds (as received) Limit of Quantitation (LOQ) for the procedure is 0.20 ug/Kg for all compounds (as received) ND - Compound not detected N Q - C om pound detected at a level betw een the L O D and LO Q . Result Is not quantifiable. ND < LOD < NQ < LOQ % Solids 78.66 78.66 83.01 83.01 77.91 77.91 0.24 0.24 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-610K 250 PFOS PFOSA POAA Sample Concentration (ng/L) 13.9 6.8 36.4 Matrix Spike Result (ng/L) 275 208 270 Matrix Spike Result (% Recovery) 104.4 80.5 93.4 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. Concentrations represent amounts found in the sample extracts BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: Spiked Amount (ng/L): MC-611K 250 PFOS PFOSA POAA Sample Concentration (ng/L) 117 . 6.6 32.8 Matrix Spike Result (ng/L) 316 206 263 Matrix Spike Result (% Recovery) 79.6 79.8 92.1 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. Concentrations represent amounts found in the sample extracts BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: Spiked Amount (ng/L): MC-612K 250 PFOS PFOSA POAA Sample Concentration (ng/L) 74.3 3.7 164 Matrix Spike Result (ng/L) 284 200 392 Matrix Spike Result (% Recovery) 83.9 78.5 91.2 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. Concentrations represent amounts found in the sample extracts BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: Spiked Amount (ng/L): MC-644K 250 PFOS PFOSA POAA Sample Concentration (ng/L) 21.8 4.3 16.5 Matrix Spike Result (ng/L) 204 185 251 Matrix Spike Result (% Recovery) 72.9 72.3 93.8 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. Concentrations represent amounts found in the sample extracts BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Ftecovery Sample ID: Spiked Amount (ng/L): MC-635K 100 PFOS PFOSA POAA Sample Concentration (ng/L) 344 7.2 953 Matrix Spike Result (ng/L) 422 88.8 1049 Matrix Spike Result (% Recovery) 78.0 81.6 96.0 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 3 M Environmental Laboratory Form 38778 - PWO Shipping A d dratt: 3M Btdg~2-3E-Q9 935 Bush Avenue St Paul, MN 55106 T jljn h n n j; Sample Receiving: (51) 778-4948 Alternate: (651)776*6753 FAX: (651) 778-6176 Chain of Custody /Request for Laboratory Analytical 15 0S4 Project ID/Project Name --D t Q Template # Project Lead |<iA1 <> T . 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