Document YDqj56xx6gvxdVY9beMrdzMr0

BACK TO MAIN JttStSSbk. Centre Analytical Laboratories. Inc. 3048 Research Drive State College, PA 16801 www.centrelab.com (814) 231-8032 Fax: (814) 231-1253 or (814) 231-1580 Analytical Report Fluorochemical Characterization of Surface Water Samples Port St. Lucie, FI (W2363) Centre Analytical Laboratory Report No. 023-014F (Revision 1) Revision Date 3/22/01 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. Box 33331 St. Paul, MN 55133-3331 Phone: (651)778-5352 Requester Kris J. 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 surface water samples received by Centre Analytical Laboratories, Inc. (Centre) from the 3M Environmental Laboratory. The samples were collected from Port St. Lucie, FI. 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 8 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 Comoound Name Perfluorooctane Sulfonate Perfluorooctane Sulfonvlamide Perfluorooctanoate Acronvm PFOS PFOSA POAA The analytical method used was validated by Centre. The validation protocol and results are on file with Centre. 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. Eight individual sample containers were received. Samples were received on 05/03/00. The 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. The stability of the analytes of interest for longer periods has not been determined. However, it should be noted that field fortifications prepared 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 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-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. 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 5/19/00 and analyzed by MS/MS between 5/22/00 and 5/23/00. An initial analysis was performed on 5/21/00, however, the data was rejected because of unacceptable standard curves. The data is included in Attachment D for informational purposes only. The HPLC and MS/MS methods used for analysis and instrument parameters can be found in attachment 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) The response of the quantitation ion 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. For the results reported here, calibration criteria were met. PAGE3 OF5 BACK TO MAIN 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 method. 5.4 Matrix Spikes Matrix spikes were prepared for every field sample (excluding blanks) at a concentration of 100 ng/L using all compounds of interest. Matrix spike recoveries are given in Attachment B. Sample MC-684H had PFOS at levels significantly greater than 10 times the spiking level; therefore accurate matrix spike recoveries could not be determined. All other compounds in all samples showed matrix spike recoveries between 70-130%. Field spikes were also prepared on sample MC-601H for all compounds at a concentration of 100 ng/L using all compounds of interest. The field spike is identified as sample MC604H. Field spike recoveries are also given in Attachment B. All compounds showed recoveries between 70-130% in the field spikes. 5.5 Duplicates . All field samples (excluding blanks) were analyzed in duplicate. Results are given along with the sample results in Attachment A. 5.6 Laboratory Control Samples Milliq water was spiked with all compound of interest at 25 and 250 ng/L. PFOS showed a recovery of 133% in the 25 ng/L spike. All recoveries for all other compounds were between 70-130% in each LCS. Results are given along with the raw data in Attachment D. 5.7 Sam ple Related Com m ents Field blank samples consisted of empty containers. Forty milliliters of type I water filtered through a hypercarb cartridge was added to the empty container and analyzed in the same manner as the other samples. The field blank for this sample did show PFOS above the reporting limit. 6 Data Summary Please see Attachment A for a detailed listing of the analytical results. 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 BACK TO MAIN 8 Attachments 8.1 Attachment A: Results 8.2 Attachment B: Matrix Spike Recoveries (Field and Laboratory Spikes) 8.3 Attachment C: Chain of Custody 8.4 Attachment D: LC/MS/MS Raw Analytical Data 9 Signatures Other Lab Members Contributing to Data Enaksha Wickremesinhe Karen Smith David Bell Tiffany Proctor PAGE5 OF5 Analytical Results W2363 Port St. Lucie, FI 3M Sample Identification Sample Description PFOS (ng/L) PFOSA (ng/L) MC-601H MC-603H MC-606H NA MC-607H NA MC-608H MC-684H NA Site 1 Surface Water Site 1 Surface Water Duplicate Site 2 Surface Water Site 2 Surface Water Duplicate Site 3 Surface Water Site 3 Surface Water Duplicate Field Blank-P/N Empty Quiet Surface Water Quiet Surface Water Duplicate ND ND 138 137 NQ NQ 43.1 45300 51100 ND ND ND ND ND ND ND 83.6 95.2 Limit of Detection (LOD) for the procedure is appoximately 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 POAA ( ND ND NQ NQ ND ND ND 737 760 Please refer to the reverse side for our standard terms and conditions. 0 BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: Spiked Amount (ng/L): MC-605H 100 PFOS PFOSA POAA Sample Concentration (ng/L) 0 0 0 Matrix Spike Result (ng/L) 93.3 84.4 94.9 Matrix Spike Result (% Recovery) 93.3 84.4 94.9 Lower Recovery Limit: 70 Upper Recovery Limit: 130 Note that sample MC-605H is a laboratory spike of sample MC-601H Criteria (Pass / Fail) PASS PASS PASS BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: Spiked Amount (ng/L): MC-606H 100 PFOS PFOSA POAA Sample Concentration (ng/L) Matrix Spike Result (ng/L) 138 0 ' 18.4 222 92.7 118 Matrix Spike Result (% Recovery) 84.0 92.7 99.6 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. BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: Spiked Amount (ng/L): 1 MC-607H 1 PFOS PFOSA POAA Sample Concentration (ng/L) 18.8 0 0 Matrix Spike Result (ng/L) 97.6 102 95.6 Matrix Spike Result (% Recovery) 78.8 102.0 95.6 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. BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: Spiked Amount (ng/L): MC-684H 100 PFOS PFOSA POAA Sample Concentration (ng/L) 45300 83.6 737 Matrix Spike Result (ng/L) 39000 174 820 Matrix Spike Result (% Recovery) -6300.0 90.4 83.0 Lower Recovery Limit: 70 Upper Recovery Limit: 130 The PFOS sample concentration is greater than 10X the spiking level. Matrix spike recoveries are not applicable for the interpretation of the PFOS result. Criteria (Pass / Fail) FAIL PASS PASS BACK TO MAIN Attachment B: LC/MS/MS Field Spike Recovery Sample ID: Spiked Amount (ng/L): MC-604H 100 PFOS PFOSA POAA Sample Concentration (ng/L) 0 0 0 Matrix Spike Result (ng/L) 99.4 74.4 103 Lower Recovery Limit: 70 Upper Recovery Limit: 130 Note that sample MC-604H is a field spike of sample MC-601H Matrix Spike Result (% Recovery) 99.4 74.4 103.0 Criteria (Pass / Fail) PASS PASS PASS 3M Environmental Laboratory Form 38778 - PWO Shipping Address: 3M Bldg, 2-3E-09 935 Bush Avenue St. Paul, MN 55106 Telephone: Sample Receiving: (651) 778-494 Alternate: (651)778-8753 BACK TO MAIN Chain of Custody /Request for Laboratory Analytical 1 4 2 7 0 Project ID/Project Name/ Template # Project Lead t^*X\A~ SfAJm uti Vbrltt.Lpue tP L Final Report Due Date farm *NHelU Internal Due Date 3M Env. Lab Project # For Internal Use Only [Jj'H'ifo' a 3. tti8S .0. t: oa0) 0 : : Contact Name Company g )YY*\ Mailing Address City, State, Z.p t l k 0 0 ^ 3 , Telephone# ( ( 0 ^ n /V I H 2 Special InstAiCtions and/or Specific Regulatory Requirements: (method, limit of detection, reporting units, etc ) S I? s :S to t S tt FAX# ( / n ^ l M l k - l o H i n Date Available Date Due Contract Lab Preservatives: o o 5o O c AJ T R 1 . Analysis Requested: Complete below. Attach any associated inform ation . Other .i Total Number of Containers M o z X * o CNO x VOCs None .#A V \ Item # Client Sample Identification 1. iT\C - (oOV Vt - >.**, l PI A/ T o r> Wsoi H PLC - i S r r i a - ffe rV aV .Lo N i-f , T L XUC-2. iTr>j_-UDaiA-&.<= l - j-tevU ul>0 O ^ p - P l p n PaJjC P o r f "t-cv. 1 n t i C . 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Received by/Affiliation Time Date /J <-S'Cd Chain of Custody Sample Condition Upon Receipt: ^Acceptable 0 Other: Temperature: Other Associated CoCs: `C j deceived on Ice Copies to: __________________ Page JiL or l o Original - Accompanying Samples Comments: Last Page - Originator See Reverse Side for Instructions