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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 -1253or (814) 231 -1580 Analytical Report Fluorochemicai Characterization of Sediment, POTW Sludge, and Landfill Leachate Samples Decatur, AL (W1979) Centre Analytical Laboratory Report No. 023-014R (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 10 F 5 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 -1253o r (814) 231 -1580 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 Decatur, Alabama and are part of 3M Project W1979. 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 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 OF5 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 C18 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 8/21/00 and 8/29/00 and analyzed by MS/MS between 8/24/00 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. PAGE 3 OF 5 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 made on these samples 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 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. 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 RftfiK Tfl MAIN Analytical Results W1974 Decatur, Alabama (GEN 014] 3M Sample Identification PFOS (ng/L) PFOSA (ng/L) POAA (ng/L) MC-213K Field Blank MC-214K Field Blank MC-235K Landfill Leachate MC-235K Landfill Leachate dup MC-236K Field Blank MC-245K Field Blank ND ND 53100 52300 ND ND ND ND 258 249 ND ND ND ND 48100 46800 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 0 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 W1974 Decatur, Alabama (GEN 014) 3M Sample Identification MC-21 OK Sediment Site 1 MC-210K Sediment Site 1 dup MC-211K Sediment Site 2 MC-211K Sediment Site 2 dup MC-212K Sediment Site 3 MC-212K Sediment Site 3 dup MC-244K POTW Sludge MC-244K POTW Sludge dup PFOS (ug/Kg) (as received) NQ NQ 0.253 0.673 0.292 0.299 99.8 110 PFOSA (ug/Kg) (as received) ND NQ NQ NQ NQ NQ 3.76 3.44 POAA (ug/Kg) (as received) ND NQ NQ NQ NQ NQ 3.55 8.57 3M Sample Identification MC-21 OK Sediment Site 1 MC-21 OK Sediment Site 1 dup MC-211K Sediment Site 2 MC-211K Sediment Site 2 dup MC-212K Sediment Site 3 MC-212K Sediment Site 3 dup MC-244K POTW Sludge MC-244K POTW Sludge dup PFOS (ug/Kg) (dry weight) NQ NQ 0.295 0.785 0.36 0.368 2840 3120 PFOSA (ug/Kg) (dry weight) ND NQ NQ NQ NQ NQ 107 97.8 POAA (ug/Kg) (dry weight) ND NQ NQ NQ NQ NQ 101 244 Limit of Detection (LOD) for the procedure is appoximately 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 76.06 76.06 85.79 85.79 81.23 81.23 3.52 3.52 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-210K 250 PFOS PFOSA POAA Sample Concentration (ng/L) 18.2 0 0 Matrix Spike Result (ng/L) 221 213 218 Matrix Spike Result (% Recovery) 81.1 85.2 87.2 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 Recovery Sample ID: Spiked Amount (ng/L): MC-211K 250 PFOS PFOSA POAA Sample Concentration (ng/L) 31.6 4.5 9.0 Matrix Spike Result (ng/L) 242 214 230 Matrix Spike Result (% Recovery) 84.2 83.8 88.4 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 present in the sample extract BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Ftecovery Sample ID: Spiked Amount (ng/L): MC-212K 250 PFOS PFOSA POAA Sample Concentration (ng/L) 36.5 4.0 16.1 Matrix Spike Result (ng/L) 216 203 218 Matrix Spike Result (% Recovery) 71.8 79.6 80.8 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 present in the sample extract BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: Spiked Amount (ng/L): MC-244K 250 PFOS PFOSA POAA Sample Concentration (ng/L) 12500 470 444 Matrix Spike Result (ng/L) 7920 362 446 Matrix Spike Result (% Recovery) -1832.0 -43.2 0.8 Lower Recovery Limit: 70 Upper Recovery Limit: 130 PFOS sample concentration exceeds the spiking amount by greater than 10X Concentrations represent amounts present in the sample extract Criteria (Pass / Fail) FAIL FAIL FAIL BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: Spiked Amount (ng/L): MC-235K 100 PFOS PFOSA POAA Sample Concentration (ng/L) 53100 258 48100 Matrix Spike Result (ng/L) 47000 307 47300 Matrix Spike Result (% Recovery) -6100.0 49.0 -800.0 Criteria (Pass / Fail) FAIL FAIL FAIL Lower Recovery Limit: 70 Upper Recovery Limit: 130 PFOS and POAA sample concentration exceeds the spiking amount by greater than 10X BACK TO MAIN 3M Environmental Laboratory Chain of Custody /Request for Laboratory Analytical 1 5 0 9 3 Form 38770 - PWO snipping A ddress: 3M Bldg 2-3E-09 935 Bush Avenue St. Paul. MN 55106 Telephone: Sample Receiving: (651)778-4940 Alternate: (651)778*6753 FAX: (651) 778-6176 Project ID/Projec! Name Tem plate # / \ J /A i 4 D p.p o L r A i Final R eport Due Date Project Lead K r t } J 7 h i z/'i'StS'T'- ' D ept. # (m ain) - IQ / Internal Due Date C la s s /J o b /P ro je c t # r > b l 3 ' ? S f ) f t <t Contact Name U t> C L , :3..' Company 2> f Y } OaC> Mailing Address . c\ ' aS ' \ % A ^ I V c . Date Available Date Due D7 City, State, Zip p b ill Telephone # ' * 3 5 L ) 3M Env. Lab Project # For Internal Use Only u>m 9 aa Sample Condition Upon Receipt: O^cceptable O Other: ` Temperature: Other Associated CoCs: 'C t D e c e iv e d on Ice Copies to: m t ________________________ k jr t- , tA c iPage _ L Original - Accompanying Samples Last Page - Originator Comments: See Reverse Side for Instructions