Document VVBNo820mMbXxXy4vL14rzGw

BACK TO MAIN Centre Analytical Laboratories, Inc. 3048 Research Drive State College, PA 16801 www.centrelab.com ^P hone: (814) 231-8032 Fax: (814) 231-1253 or (814) 231-1580 Analytical Report Fluorochemical Characterization of Drinking Water Samples Cleveland, Tennessee (W1973) Centre Analytical Laboratory Report No. 023-007A (Revision 1) Revision Date 3/19/01 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 1 0 F 5 BACK TO MAIN 1 Introduction Results are reported for the analysis of a series of drinking water samples received by Centre Analytical Laboratories, Inc. (Centre) from the 3M Environmental Laboratory. The samples were collected from Cleveland, Tennessee. The Centre study number assigned to the project is 023 007. Specific fluorochemical characterization by liquid chromatography / tandem mass spectrometry (LC/MS/MS) was requested for all samples. A total of 17 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. Seventeen individual sample containers were received. Samples were received on 02/15/00. The sample collection dates were not supplied. Chain-of-custody information is presented in Attachment C. Samples MC-127H and MC-134H were not analyzed as per client request. (Telephone call to Kris Hansen on 2/16/00). 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. PAGE2 OF5 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 C18SPE 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 2/17/00 and analyzed by MS/MS between 2/17/00 and 2/18/00. 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 determinaition (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. PAGE 3 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 sample at a concentration of 100 ng/L using all compounds of interest. Matrix spike recoveries are given in Attachment B. Field spikes were also prepared on several samples at a concentration of 100 ng/L using all compounds of interest. Field spike recoveries are also given in Attachment B. 5.5 Duplicates All samples 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. Initial analysis of the 25 ng/L LCS showed low recovery for PFOS. The standard was reinjected and was found to have acceptable recovery (70-130%). All other recoveries for all compounds were between 70 130% in each LCS. 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 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 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 PAGE 5 OF5 , BACK TO MAIN ANALYTICAL REPORT ( K8S8Sk C en tre A n alyticalI L a b o ra to rie s , Inc. 3048 Research Drive, State College PA 16801 814-231-8032 FAX 814-231-1253 Analytical Results W1973 Cleveland, Tennesse 3M Sample Identification MC-115H MC-117H MC-120H MC-121H MC-123H MC-126H MC-128H MC-131H NA MC-132H NA MC-133H Sample Description Intake-P/N Intake-P/N duplicate Intake-Field Blank Outflow-P/N Outflow-P/N duplicate Site 1 P/N Site 1 P/N duplicate Site 2 P/N Site 2 P/N duplicate Site 3 P/N Site 3 P/N duplicate Field Blank P/N Empty PFOS (ng/L) ND ND ND ND ND ND ND ND ND ND ND ND PF( (ng/L) ND ND ND ND ND ND ND ND ND ND ND ND POAA (ng/L) ND ND ND ND ND ND ND ND ND ND ND ND 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 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-115H 100 PFOS PFOSA POAA Lower Recovery Limit: Upper Recovery Limit: Sample Concentration (ng/L) 0 0 0 70 130 Matrix Spike Result (ng/L) 88.5 114 103 Matrix Spike Result (% Recovery) 88.5 114.0 103.0 Criteria (Pass / Fail) PASS PASS PASS BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: Spiked Amount (ng/L): MC-125H 100 PFOS PFOSA POAA Lower Recovery Limit: Upper Recovery Limit: Sample Concentration (ng/L) 0 0 0 70 130 Matrix Spike Result (ng/L) 81.8 106 91.7 Matrix Spike Result (% Recovery) 81.8 106.0 91.7 Criteria (Pass / Fail) PASS PASS PASS BACK TO MAIN-- Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: Spiked Amount (ng/L): MC-130H 100 PFOS PFOSA POAA Lower Recovery Limit: Upper Recovery Limit: Sample Concentration (ng/L) 0 0 0 70 130 Matrix Spike Result (ng/L) 88.4 106 105 Matrix Spike Result (% Recovery) 88.4 106.0 105.0 Criteria (Pass / Fail) PASS PASS PASS BACK TO MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: Spiked Amount (ng/L): MC-131H 100 PFOS PFOSA POAA Lower Recovery Limit: Upper Recovery Limit: Sample Concentration (ng/L) 0 0 0 70 130 Matrix Spike Result (ng/L) 80.9 107 102 Matrix Spike Result (% Recovery) 80.9 107.0 102.0 Criteria (Pass / Fail) PASS PASS PASS BACK 10 MAIN Attachment B: LC/MS/MS Laboratory Spike Recovery Sample ID: MC-132H Spiked Amount (ng/L): [_______ 100 PFOS PFOSA POAA Lower Recovery Limit: Upper Recovery Limit: Sample Concentration (ng/L) 0 0 0 70 130 Matrix Spike Result (ng/L) 97.5 106 103 Matrix Spike Result (% Recovery) 97.5 106.0 103.0 Criteria (Pass / Fail) PASS PASS PASS BACK T MAIN * Attachment B: LC/MS/MS Field Spike Recovery Sample ID: Spiked Amount (ng/L): MC-118H 100 PFOS PFOSA POAA Lower Recovery Limit: Upper Recovery Limit: Sample Concentration (ng/L) 0 0 0 70 130 Matrix Spike Result (ng/L) 96.9 64.7 113 Matrix Spike Result (% Recovery) 96.9 64.7 113.0 Criteria (Pass / Fail) PASS FAIL PASS BACK TO MAIN Attachment B: LC/MS/MS Field Spike Recovery Sample ID: Spiked Amount (ng/L): MC-124H 100 PFOS PFOSA POAA Lower Recovery Limit: Upper Recovery Limit: Sample Concentration (ng/L) 0 .0 0 70 130 Matrix Spike Result (ng/L) 110 134 123 Matrix Spike Result (% Recovery) 110.0 134.0 123.0 Criteria (Pass / Fail) PASS FAIL PASS BACK TO MAIN Attachment B: LC/MS/MS Field Spike Recovery Sample ID: Spiked Amount (ng/L): MC-129H 100 PFOS PFOSA POAA Lower Recovery Limit: Upper Recovery Limit: Sample Concentration (ng/L) 0 0 0 70 130 Matrix Spike Result (ng/L) 105 125 114 Matrix Spike Result (% Recovery) 105.0 125.0 114.0 Criteria (Pass / Fail) PASS PASS PASS Report Results to: Total Number of Containers 3M Envil .mental Laboratory Form 38778 - PWO Shipping Address: 3M Bldg 2-3E-9 935 Bush Avenue St. Paul, M N 55106 Telephone: Sam ple Receiving: (651) 778-4948 Alternate: (651)778-6753 FAX: (651)778-6176 BACK TO MAIN Chain of Custody /Reque. or Laboratory Analytical 1 7 1 2 0 ~C IkJiProject ID/Preject Name 0 S t ? ) - r f T 7 Y\i ) tV \ i k l . 1 4 -Y id f-u /V T Template # FinaVtRepoh Due Date ([ Project Lead L r f c > f c U / t S e f \ Dept. # (main) <-(^1 | Internal Due Date Class/Job/Project# O C i f l ^ f S O O ^ 3M Env. Project # For Intei.i Use Only Contact Name Company ~AY\ Mailing Address 1 'O ^ fO City, State, Zip <C1 C b & l . r t i n #Telephone ( k f j - Q l l f g - _________ Special Instructions and/or Specific Regulatory Requirements: (m ethod, limit of detection, reporting units, etc.) ifa?/, *>Y> PAX# to -n fc- b ilia Date Available Date Due Contract Lab ct T9 Analysis Requested: Q i/J -o (3 Preservatives: Com plete below. A ttach any associated inform ation. to W 3 / 1.. OUn / UU- 1tiAA i/au/^\ _ (*1"/\Jy) oz JowN. Oo>V) Co4) O<u #Item 1. 2. `M e - i n fl Client Sample Identification 3M LIMS# JiM ____ \ Date Time Matrix/ Sampled Sampled Media aJIA _aJIA_ i l k M \ Enter the number of containers of each y l 1 (Enter an 'X' in the box below to indicate request) 3. 4. 5. \6. 7. 8. 9. 10. vrtO lltf H -^ -W u _ ^ U 6 p i^ -P i/U rn c- iaoH rnc-iM 'Qj 1Y\L-iZZ>U -O t i ff M ^FiV Id 'f to h - fy j i* ov io u -P lA /a ?_______________ AckkjU b-fX p -P rd \ _________ me- m r - o A i W -Pj/O m e -PSr/4~ 0 iA [la v -U b ^ p iis -P)'/0 me- - 5 /t i m C -l3Tti-S?L -PIA) 1 ,-te fc l ~ g '_______ !______ L_ p o s ___________ _____ \ \ 1- V \l/ J 7 A / /rY*---- ZL L 1i 1 1 l 1 1 Collected by (print): j jCollector's signature: T>O3* ot3fl Ho-- Item # 1- ( o C Relinquished by/AfTiliation A A D 7 /X ^ < -^ c^ Q Time -- Date Shipped Via: ' Received by/Affiliation ------ Time l<3^c Date Z-IS-oo OJtZo Sample Condition Upon Receipt: Acceptable O Other: Temperature: # Received on Ice jictv n i .m a n ia s man]Other Associated CoCs: Copies to: n i^ .n ijA , n iM , n iv t r ^ r t . i . a -c . ' S p Comments: Priya _l_ 01 A . Original - Accompanying Sam ples Last Page - Originator See Reverse Side for Instructions Report Results to: VOCs None Other Total Number of Containers 3M Envil .mental Laboratory Form 38776 - PWO Shipping Address: 3W Bldg 2-3E-Q9 935 Bush Avenu St Paul, M N 55106 Telephone: S im p le Receiving: (651) 776-4948 Alternate: (651)778-6753 FAX: (651) 778-6176 Contact Name Company ^ y Y ] \ \ Ar>b>e^ Chain of Custody /Reque. j r Laboratory Analytical 17121 nProject ID/Project Name 0 j ^ - l H u l h - ( /-fu T 3 * U M i v Y -v ilu ^ Template # Project Lead ^ Dept, it (main) r (tS2*\ \a 11 n < - s n ( fin a l Report Due Datw M Internal Due Date Class/Job/Project # O O i 0 ^ 2 3 S f^ r ) l Date Available BACK TO MAIN 3M Env I Project # For Interi,al Use Only Mailing Address O M lm C i - O l V O fa tf. ?***>?& 1 Cty, State, Zip f , ) , f u ( ! ( > f l / ) ' ^ ^ . t L l U S i X m - t D L ^ _______________________FAX# Special Instructio ns and/or Specific Regulatory Requirem ents: (method limit of d e t e c t io n , repoiting units, etc.) Date Due O o H i p ___________________ Contract Lab cL VT a L Analysis Requested: (y u o -o \b Preservatives: Com plete below. A ttach any associated inform ation. lO lV 3 \1Xn i IJ \ i /k 'rtf / *T9 yy C ^ or> o z *T* Wrv -U itItem Client Sample Identification 3M Date Time LIMS# Sampled Sampled 1. m L - m \ \ - \be - I n o l ^ l b c b D t p - P ________ L V r t j f e a A A /V. . A____ 2. -t> /-k 1 L - P |/U 3. J ffl L : 0-1 ~ s ;b z l . r - P l / O ___________ 4. y v ^ H 3 i l-i 0 0 ______________ 5. m c - i 3 ^ M - S A o * > - Q \ 0 6. Y Y \ t - f - $ / \ . f t U / iK - I r n p M ________ 7. \ L - 134)1 ' f i r i A f r U n h - T p k i P f f c \y \ 8. i9. ---------------- ^------------------------- ............... ..................................... -oi i t v- LJtr L ------- - 3^ J * H10 Matrix/ Media uM r \/ Enter the number o f containers of each / r/ -- y r J V T/ - Collected by (print) # MA-TO>J* *- Item Relinquished by/Affiliation o o*- L i M W lo l S4j * jY l c (T3 O-C Time Date Collector's signature Shipped Via: \ \ 1 i, \ 1 'X'(Enter an in the box below to indicate request) Sample Condition Upon Receipt: Temperature: Other Associated CoCs. 'C p iita - s , n t ^ m i q m 3 i, Acceptable 0 Other: Received on Ice O U J , l~ ) 1 2 3 , 0 0 7 , Copies to: a iPage or J L 2 . O rij.nal - Accompanying Samples Comments: Last Page - Originator See Reverse Side for Instructions