Document dnw2LKkyO9vZE5Mg1wkEYGbj6

BACK TO MAIN CEntre Analytical Laboratories, Inc. 3048 Research Drive State C a ? g e ,PA 16801 www.centrelab.com (814) 231-8032 Fax: (814) 231-1253 or (814) 231-1580 Analytical Report Fluorochemical Characterizationof Surface Water Samples Mobile, Alabama (W2lfil) Centre Analytical Laboratory Report No. 023-014D (Revision 1) Revision Date 3/22/01 Testing Laboratory Centre Analytical Laboratory, lnc. 3048 Research Drive State College, PA 16801 3M Environmental LaboratloryContact Kent R. Lindstrorri Bldg. 2-3E-09 P.O. Box 33331 St. Paul, MN 55133-3331 Phone: (651) 778-5:352 Requester Kris J. Hansen, Ph.D. 3M EnvironmentalTechnology & Safety Services Bldg. 2-3E-09 P.O. Box 33331 St. Paul, MN 55133-333'1 PAGE 7 OF 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 Environniental Laboratory. The samples were collected from Mobile, Alabama. 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 I Comoound Name Perfluorooctane Sulfonate 1Perfluorooctane Sulfonvlamide Perfluorooctanoate &\cronvm p0AA 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 d& 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 in water and other matrices have shown acceptable recoveries at 100 and 1000 ng/L for periods longer than 14 days. PAGE2OF5 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 CIS SPE cartridge. The cartridge was first eluted with 5 mL of 40% mel.hanol 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 passecl 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. Electrosipray is generally operated at relatively mild temperatures; molecules are ionized, fragmentled, and detected. tons characteristic of known fluorochemicals are obsewed and quantitated against standards. A Hewlett-PackardHP1100 HPLC system coupledto a Micromass Ultima MS/MS was used to analyze the sample extracts. Analysis was performed using selected reaction monitoring (SRM). Samples were extracted on 5/17/00 and analyzed by MS/MS on 5/20/00. The HPLC and MS/MS methods used for analysis and instrumerit 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 point:; were prepared at 0, 25, 50, 100, 250, 500, and 1000 ng/L (ppt) The response of the quantitation ion versus the concentration was ( e plotted for each point. Using linear regression with l/x weighting, the slope, y-intercept and correlation coefficient (r) and coefficient of determination (?) were determined. A calibration curve is acceptable if r 20.985 2 0.970). Calibration standards are prepared using the same SPE procedure used for samples. Calibration check standards were analyzed periodically ((everythree 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. PAGE3OF5 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 LCIMSIAIIS analytical method. 5.4 Matrix Spikes Matrix spikes were prepared for every field sample (excluding blanks) at a concentration of 100 n g L using all compounds of interest. Matrix spike recoveries are given in Attachment C. POAA showed low matrix spike recoveries in samples MC-407H and MC-484H. All other compounds showed matrix spikes recoveries between 70-130% in all samples. Field spikes were prepared on sample MC-401H at a concentration of 100 ngL using all compounds of interest. The field spike is identified as sample MC-404H. Field spike recoveries are also given in Attachment B. All compounds showed recoveries between 701 30%. 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 2!5 and 250 ngL. All recoveries for all compounds were between 70-130% in each LCS. Recoveries are given with the raw data in Attachment D. 5.7 Sample Related Comments 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. 6 Data Summary Please see Attachment A for a detailed listing of the analytical results. 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 OF 5 BACK TO MAIN 8 Attachments 8.1 AttachmentA: Results 8.2 Attachment8:MatrixSpike Recoveries (Field and LaboriatorySpikes) 8.3 Attachment C: Chain of Custody 8.4 Attachment D: LC/MS/MS Raw Analytical Data 9 Signatures Kevin J Lloyh, Vicehesident Other Lab Members Contributingto Data Enaksha Wickremesinhe Karen Smith David Bell Date PAGE 5 OF5 \ 4 CLEabntorrEatAonriaelsy.tiIcnacl. 3048 Research Drive, State College PA 16801 814-231-8032 FAX 814-231-1253 BACK TO MAIN Analytical Results W2151 Mobile, Alabama 3M Sample Identification Sample Description PFOS (ng/l.) PFOSA (ng/L) MC-401H MC-403H MC-406H NA MC-407H NA MC-408H MC-484H NA Site I-P/N Surface Water NQ NQ Site I-P/N Surface Water Duplicate NQ NQ Site 2-PIN Surface Water 39.6 NQ Site 2-P/N Surface Water Duplicate 42.8 NQ Site 3-P/N Surface Water 34.7 NQ Site 3-P/N Surface Water Duplicate 36.3 NQ Field Blank-PIN Empty ND ND Quiet Surface Water 33.3 NQ Quiet Surface Water Duplicate 31.5 NQ 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 c LOD c NQ c LOQ POAA (nglL) 25.5 27.0 53.9 59.8 82.6 82.8 ND 27.0 NQ - - 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: MC-405H 1 Spiked Amount (ng/L): I 100 1 Sample Concentration (ng/L) 23.9 6.6 25.5 Matrix Spike Result (WL) 110 97.0 104.0 Lower Recovery Limit: 1 70 1 Upper Recovery Limit: I 130 -Matrix Spike - Result (% Recovery) 86.1 - 90.4 78.5 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. Also note that sample MC-405H is a laboratory spike of sample MC-401H BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery !Sample ID: MC-406H I !Spiked Amount (ng/L): I 100 I I-ower Recovery Limit: 'Upper Recovery Limit: Sample Concentration (ng/L) 39.6 12.9 53.9 L 70 I 130 Matrix Spike Result (ng/L) 118 103 130 -Matrix Spike - Result (% Recovery) 78.4 - 90.1 76.1 Criteria (Pass / Fail) PASS PASS PASS INote: Sample results less than 25 ng/L are reported as NQ in the resu:Itssection as they are lhelow 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 !SamDle ID: I MC-407H I !Spiked Amount (ng/L): I 100 I-ower Recovery Limit: IJpper Recovery Limit: Sample Concentration (ng/L) 34.7 8.6 82.6 Matrix Spike Result (ng/L) 110 96.5 134 I 70 I 130 I -Matrix Spike - Result (% Recovery) 75.3 - 87.9 51.4 Criteria (Pass / Fail) PASS PASS FAIL IVote: Sample results less than 25 ng/L are reported as NQ in the results section as they are lselow 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: !SpikedAmount (ng/L): I MC-484H ~~ 100 Sample Concentration (ng/L) 33.3 7.9 27.0 Matrix Spike Result (ng/L) 103 89.0 93.6 I-ower Recovery Limit: I 70 IJpper Recovery Limit: I 130 I -Matrix Spike - Result ("/. Recovery) 69.7 - 81.1 66.6 Criteria (Pass / Fail) FAIL PASS FAIL IVote: Sample results less than 25 ng/L are reported as NQ in the results section as they are Ibelow the limit of quantitation. Results are given in this table for recovery calculations only. BACK TO MAIN Attachment B: LC/MS/MS Field Spike Recovery PFOS PFOSA Sample Concentration (ng/L) 23.9 6.6 25.5 Matrix Spike Result (ng/L) 123 84.3 105 -Matrix Spike - Result (% Recovery) 99.1 - 77.7 79.5 Criteria (Pass / Fail) PASS PASS PASS Upper Recovery Limit: I 130 I 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. Also note that sample MC-404H is a field spike of sample MC-401ti 3NI Environmental Laboratory Form 38778 - pwo - - . (mehod. limit of deledion. repodng mils,elc.) BACK TO MAIN Date Available Preservatives: Time I Matrix/ Sampled Media 1 1 1 1 nler the number of conlainersof ea& Analysis Requested: Y. 10. saa - I--% 0 u0 e: -cm O Item # Relinquished by/Affiliation I ____I Time N!OO Date ShippedVia: s y m #-ci)c 6 Received by/Affiliation 7&4??L I I __-_ ~ m p p ~~ Time / d ) a.36 Date 5/3-cw! Orignal -Accompanying Samples Lesl Page - Originatw See Reverse Slde for Instructions