Document 2NazqBGNL7y5VRmgBMp0DoRNr

BACK TO MAIN CEntrE Analutical Laboratorks. Inc. =Phone: (814)231-8032 Fax:(814)231-1253or (814)231-1580 Analytical Report Fluorochemical Characterization of Sediment, POTW Sludge, and Landfill Leachate Samples Pensacola, FL (W2176) Centre Analytical Laboratory Report No. 023-014T (Revision 1) Revision Date 3/28/01 Testing Laboratory Centre Analytical Laboratoy, 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 Hansen Ph.D. 3M Environmental Technology & Safety Services Bldg. 2-3E-09 P.O. Box 33331 St. Paul, MN 55133-3331 PAGE 1 OF5 BACK TO MAIN 1 Introduction Results are reported for the analysis of a series of sedliment, leachate, and sludge samples received by Centre Analytical Laboratories, Inc. (Centre) flrom the 3M Environmental Laboratory. The samples were collected from Pensacola, Florida and are part of 3M Project W2176. The Centre study number assigned to the projectis 023-014. Specific fluorochemicalcharacterization by liquid chromatography / tandem mass spectrometry (LC/MS/MS) was requestedfor all samples. A total of 9 samples were receivedfor analysis. The samples were prepared and analyzed by LC/MS/MS for the following list of fluorochemicals: ComDound Name Perfluorooctane Sulfonate Perfluorooctane Sulfonvlamide . Perfluorooctanoate Acronvm PFOS PFOSA I'OAA The analytical methods used for originally developed for water samples and were validated by Centre. The water sample validation protocol and results iwe 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 A. 3 Holding Times The analytical method used was validated against a maxirnum 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. PAGE2W5 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 mgR sodium thiosulfate solution to remove residual chlorine. !3olid phase extraction (SPE) was used to prepare the samples for LC/MS/MS analysis. A forty-milliliter portion of sample was transferredto a CIS 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 resultedin an eight-foldconcentration 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, beginningwith 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-phasechromatographic 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 fluorochemicalsare observed and quantitated against standards. A Hewlett-PackardHP1100 HPLC system coupledto a Micromass Ultima MS/MS was usedto analyze the sample extracts. Analysis was performed using selected reaction monitoring (SRM). Samples were extracted between 8/22/00and 8/23/00and analyzed by M S / M S between 8/25/00 and 8/28/00. The HPLC and MSIMS 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 ngn (ppt) for LC/MS/MS analysis. The instrument response versus the concentration was plottedfor each point. Using linear regression with l / x weighting, the slope, y-intercept and correlationcoefficient (r) and coefficient of determination (?) were determined. A calibration curve is acceptable if r ~ 0 . 9 8 5(?2 0.970). Calibration standards are prepared using the same SPE procedure used for samples. PAGE 3OF5 BACK TO MAIN 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-levelcalibration standard. For these samples, the extractionblanks 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 anaiytes 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 spik.eswere collectedfrom 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 DatdSample 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 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 Kevin J Lloyd, Vice President Other Lab Members Contributing to Data Karen Smith BACK TO MAIN Date 28rnAecH 2 6 0 I Date PAGE5OF5 CEntrE Analytical Caboratorks, Inc. 3048 Research Drive, State College PA 16801 814-231-8032 FAX 814-231-1253 BACK TO MAIN Analytical Results W2176 Pensacola, Florida (GEN 017) 3M Sample Identification PFOS (ng/L) PFOSA (ng/L) POAA (ng/L) MC-313K Field Blank ND ND ND MC-314K Field Blank ND ND ND MC-335K Landfill Leachate ND ND ND MC-335K Landfill Leachate dup ND ND ND MC-336K Field Blank ND ND ND MC-345K 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 c LOD < NQ < LOQ 43 Please refer to the reverse side for our standard terms and conditions. (A\\ laboratorks. Inc. CEntre Analytical 5148 Research Drive, State College PA 16801 814-231-8032 FAX 814-231-1253 BACK TO MAIN Analytical Results W2176 Pensacola, Florida (GEN 017) 3M Sample Identification MC-31OK Sediment Site 1 MC-3lOK Sediment Site 1 dup MC-311K Sediment Site 2 MC-311K Sediment Site 2 dup MC-312K Sediment Site 3 MC-312K Sediment Site 3 dup MC-344K P O W Sludge MC-344K POTW Sludge dup PFOS (ug/Kg) (as received) ND ND 0.205 ND 0.329 NQ 27.8 28.2 PFOSA (uglKg) (as received) ND ND ND ND ND ND 0.285 0.289 POAA (ug/Kg) (as received) ND ND NQ ND ND ND 0.564 0.540 3M Sample Identification PFOS (ug/Kg) (dry weight) PFOSA (uglKg) (dry weight) POAA (ug/Kg) (dry weight) MC-31OK Sediment Site 1 ND ND ND MC-310K Sediment Site 1 dup ND ND ND MC-311K Sediment Site 2 0.242 ND NQ MC-311K Sediment Site 2 dup ND ND ND MC-312K Sediment Site 3 0.408 NO ND MC-312K Sediment Site 3 dup NQ ND ND MC-344K POTW Sludge 124 1.27 2.51 MC-344K POTW Sludge dup 125 1.29 2.40 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 c LOD < NQ < LOQ % Solids 78.87 78.87 84.78 84.78 80.66 80.66 22.48 22.48 - 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: I Spiked Amount (ng/L): L MC-31OK 1 ~ 250 PFOS PFOSA rPOAA Sample Concentration (ng/L) 0 0 0 Matrix Spike Result (ng/L) 198 186 196 Lower Recovery Limit: I Upper Recovery Limit: I 70 1 130 I Concentrations represent the amount present in the sample extract Matrix Spike Result (% Recovery) 79.2 74.4 78.4 Criteria (Pass / Fail) PASS PASS PASS BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: MC-311K I Spiked Amount (ng/L): 1 250 I PFOS PFOSA POAA Sample Concentration 25.6 0 10.6 Matrix Spike Result (ng/L) 205 191 21 0 Lower Recovery Limit: I 70 Upper Recovery Limit: I 130 I Matrix Spike Result (% Recovery) 71.8 76.4 79.8 Criteria (Pass / Fail) PASS PASS PASS 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 the amount present in the sample extract BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: I MC-312K I Spiked Amount (ng/L): I 250 PFOS PFOSA POAA Sample Concentration 0-w 41.1 0 0 Matrix Spike Result (ng/L) 624 149 263 Matrix Spike Result (% Recovery) 233.2 59.6 105.2 Criteria (Pass / Fail) FAIL FAIL PASS BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: MC-344K I Spiked Amount (ng/L): I 250 I PFOS PFOSA POAA Sample Concentration (ng/L) 3477 35.7 70.5 Matrix Spike Result (ng/L) 4062 54.2 249 Lower Recovery Limit: I 70 I Upper Recovery Limit: I 130 Concentrations represent the amount present in the sample extract Matrix Spike Result (% Recovery) 234.0 7.4 71.4 PFOSsarnple concentration is greater than 1OX the spiking level Criteria (Pass / Fail) FAIL FAIL PASS BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: I MC-335K I Spiked Amount (ng/L): I 100 1 PFOS PFOSA POAA Sample Concentration (ng/L) 0 0 0 Matrix Spike Result (ng/L) 84.8 69.2 92.7 Lower Recovery Limit: I Upper Recovery Limit: I 70 I 130 I Matrix Spike Result (% Recovery) 84.8 69.2 92.7 Criteria (Pass / Fail) PASS FAIL PASS 3M Environmental Laboratory F M 3~8778 - PWO Shinning Addrass. 3M Btdp 2-3E-09 935 Bush Avenue SL Pad. MN 55106 TdiphnCi: Sample Recelvlng:(651) 778-4948 Alternate: (651) 7784753 FAX: (651) 7786176 BACK TO MAIN 1 50 8 9 Chain of Custo& /Request for Laboratory Analytical -017 Project ID/Project Name Wa)es S c ~ i ) . M C k~ 4ddc Sdhpl... v,t, kig;&/.-, %,,kGci,, TemplatZi MA Final Report Due Date 3M Env. Lab Project # For Internal Use Only ;3nfi?Lci!c Project Lead E;suis J.I4&n5.Cn Dept. # (main) Y a 4 1 Internal Due Date Class/Job/Project # / ) D I 01-3.5 0 09 I Ill 1322x9 -emperatwe. 'C her AssocialedCoCr d e c e i v e d on Ice Copies lo Original ~ Accnmpanyng Sampler Mc Lasl Page -Originator See Reverse Side lor lnslrucliuns