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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 Columbus, GA (W2336) Centre Analytical Laboratory Report No. 023-014U (Revision 1) Revision Date 3/28/01 Testing Laboratory Centre Analytical Laboratory, Inc. 3048 Research Drive State College, PA 16801 3M Environm ental Laboratory Contact 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 10F5 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 Columbus, Georgia and are part of 3M Project W2336. 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 Acronym 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 d a te s w e re not supplied. C h a in -o f-cu sto d y info rm a tio n is p re se n te d in A tta ch m e n t 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. PAGE2 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 C i8 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 between 8/25/00 and 8/28/00 and analyzed by MS/MS between 8/28/00 and 8/29/00. The HPLC and MS/MS methods used for analysis and in stru m e n t p a ra m e te rs can be fo u n d in A tta ch m e n ts 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 TO 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 RelatedComments 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 Sum m ary 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. PAGE4 OF5 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 Centre Analytical Laboratories, Inc. 3048 Research Drive, State College PA 16801 814-231-8032 FAX 814-231-1253 Analytical Results W2336 Columbus, Georgia (GEN 018) 3M Sample Identification PFOS (ng/L) PFOSA (ng/L) POAA (ng/L) MC-513K Field Blank NQ ND ND MC-514K Field Blank ND ND ND MC-535K Landfill Leachate ND ND NQ MC-535K Landfill Leachate dup ND ND 27.9 MC-536K Field Blank ND ND ND MC-545K Field Blank ND ND ND 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. BACK TO MAIN | ANALY 3048 Research Drive, State College PA 16801 814-231-8032 FAX 814-231-1253 Analytical Results W2336 Columbus, Georgia (GEN 018) 3M Sample Identification MC-510K Sediment Site 1 MC-510K Sediment Site 1 dup MC-511K Sediment Site 2 MC-511K Sediment Site 2 dup MC-512K Sediment Site 3 MC-512K Sediment Site 3 dup MC-544K POTW Sludge MC-544K POTW Sludge dup PFOS (ug/Kg) (as received) 0.342 0.304 NQ NQ 0.318 0.264 5.12 5.19 PFOSA (ug/Kg) (as received) NQ NQ NQ NQ NQ NQ 1.35 1.42 POAA (ug/Kg) (as received) ND ND ND ND ND ND 0.537 0.532^ 3M Sample Identification PFOS (ug/Kg) (dry weight) PFOSA (ug/Kg) (dry weight) POAA (ug/Kg) (dry weight) MC-51 OK Sediment Site 1 MC-51OK Sediment Site 1 dup MC-511K Sediment Site 2 MC-511K Sediment Site 2 dup MC-512K Sediment Site 3 MC-512K Sediment Site 3 dup MC-544K POTW Sludge MC-544K POTW Sludge dup 0.472 0.419 NQ NQ 0.467 0.388 157 159 NQ NQ NQ NQ NQ NQ 41.3 43.4 ND ND ND ND ND ND 16.5 16.3 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 NQ - Compound detected at a level between the LOD and LOQ. Result Is not quantifiable. ND < LOD < NQ < LOQ % Solids 72.50 72.50 71.20 71.20 68.00 68.00 3.26 3.26 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-510K 250 PFOS PFOSA POAA Sample Concentration (ng/L) 42.8 6.3 0 Matrix Spike Result (ng/L) 285 231 244 Matrix Spike Result (% Recovery) 96.9 89.9 97.6 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. Concentrations represent amounts present in the sample extract BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: Spiked Amount (ng/L): MC-511K 250 PFOS PFOSA POAA Sample Concentration (ng/L) 21.8 8.4 0 Matrix Spike Result (ng/L) 235 206 248 Matrix Spike Result (% Recovery) 85.3 79.0 99.2 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 present in the sample extract BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Ftecovery Sample ID: Spiked Amount (ng/L): MC-512K 250 PFOS PFOSA POAA Sample Concentration (ng/L) 39.7 4.0 0 Matrix Spike Result (ng/L) 250 215 254 Matrix Spike Result (% Recovery) 84.1 84.4 101.6 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. Concentrations represent amounts present in the sample extract BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: Spiked Amount (ng/L): MC-544K 250 PFOS PFOSA POAA Sample Concentration (ng/L) 640 168 67.1 Matrix Spike Result (ng/L) 1093 239 313 Lower Recovery Limit: 70 Upper Recovery Limit: 130 Concentrations represent amounts present in the sample extract Matrix Spike Result (% Recovery) 181.2 28.4 98.4 Criteria (Pass / Fail) FAIL FAIL PASS BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: Spiked Amount (ng/L): MC-535K 100 PFOS PFOSA POAA Sample Concentration (ng/L) 0 0 19.9 Matrix Spike Result (ng/L) 97.7 94.8 141 Matrix Spike Result (% Recovery) 97.7 94.8 121.1 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. Environmental Laboratory Form 38778 - PWO Shipping Address: 3M Bldg 2-3E-09 935 Bush Avenue St. Paul, MN 55106 Telephon: Sample Receiving: (651) 778-4946 Alternate: (651) 778-6753 FAX: (651) 778-6176 BACK TO MAIN 15 0S2Chain of Custody /Request for Laboratory Analytical Project ID/Project Name Template # A L A Project Lead )C n S 3 . Dept. # (main) S l | 0 1% H anS aJO P .h Ga Final Report Due Date Internal Due Date Class/Job/Project# D S S h ^ 3M Envf Lab Project # For Internal Use Only 10233k Sample Condition Upon Receipt: Temperature: mOther Associated CoCs 'C Page !_ 0(_ L Acceptable 0 Other: Comments: sm lem. u\c-Tfeceived on Ice Copies to- W oTja7k- ... _____________________________ Original - Accompanying Samples Last Page - Originator See Reverse Side for Instructions