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Lancaster Laboratories 2425 New Holland Pike Lancas'ter. PA^YBT Analysis #0615.01 Revision 01 Supersedes Date: None AR226-2725 Page f o n e " APR 9 9 2001 FC-143 in WaterA/Vastewater by SPME/GCMS Reference: 1. Low-Level Determination of FC-143 in Water, CH2M H'll Inc , October 1f 91 2. Method 8260B, Revision 2, SW-846, USEPA, Decempet 1936. (BFB Tuning) Sarrion, M.N.; Santos, F.J.; Galceran, M.T. A K L * '^sbwhB1' 3. In Situ Denvatization/Solid-Phase Microe nrac ion for thw Determination of Haloacetic Acids in Water. Analytical Cnern.str* 7ol, 72, No. 201, October 15, 2000, pp. 4865-4873. *nm- je-t _ . "- 4. SPME Applications Guide Bulletin 92CA -- Supelco. .- 5. Agilent Technolog es Opcnat.oi is M cnulll. - Cross Reference: The following procedu-s is uoss referenced in this document ` lifts,. MC-EX-001 ' GC/iy'S Prevcms-i/e and Corrective Maintenance." Scope: This method is app'.cab'e to the measurement of the ammonium perfluorooctanoate in w atepind water. The limit of quantitation is 1.0 pgT. 'COMPANY CONFIDENTIAL Lancaster Laboratories 2 4 2 5 N e w Holland Pike * Lancaster, PA 1 7 S 0 I Analysis #0615.01 Revision 01 Supersedes Date: None Effective Date: ApR g g 3 ,5, Paqe 2 of 16 Basic Principle: %I I # Ethyl esters of the target and surrogate are converted from their respective acidic'. compounds using techniques for esterification. The sample is a c id ifie d ^ ^ s in g jil HCL. Ion paring agent, diethyl sulfate, ethanol and sulfuric acid am us%4d Convert the acid into the ethyl esters. The sample is mixed on a stir plate at 'p|cif|etting for a specific time. The sample is then absorbed onto a 100 l m PDITS fiber foJ-10.0 minutes and injected into a GC/MS system equipped with a capiliap/-to umn. Th analysis is performed using internal standard calibration by GC/MS Apparatus: 1. Hewlett-Packard Model 5B90 ( S e ^ . ^ 'd j p r 6890 Gas Chromatograph or equivalent _'*%OESS*J8gF 2. Hewlett-Packard Model r ZOJXlm 5973 Mass Selective Detector or equivalent 3. Hewlett-Packard ChernstatWffoftware, Thru-Put Systems Target data system or equivalent 4. Solid Phase Microextraction (SPME) - Supelco - 100 pm Polyd'ncthylsi'pxane (PDMS) fiber, fiber pen for manual injection, and injector gutce, or equivalent 5 15 mL - Clear vial with Teflon/silicon septum or equivalent 3. Stir Plate - VWR - mini stirrer, Model 200 or equivalent ' Stir Bars - VWR Teflon stir bars Yz X 5/16" or equivalent 8. Disposable Glass pipettes 9, 10 mL Class A graduated cylinder COMPANY CONFIDENTIAL I ancaster Laboratories 2 4 2 5 N e w H o lland Piks Lancaster, PA 17601 Analysis #0615.01 Revision 01 Supersedes Date: None Effective Date: APR 0 9 2001 10. Syringes --1 mL, 10 mL, 10 pL, 25 pL, 50 pL 11. j i mers _ Capable of measuring time to 30 minutes. 12. Class A volumetric flasks, assorted sizes 13. Analytical balance - Capable of weighing tc 0 0001 g s t*, jm !SSS5Hnra;ssnn:?i:F::=;yr Reagents: ... 1. 1:1 HCL reagent grade or equivalent - 2. Ethanol - AAPEI t Cnem cal - ADSOlute 200 P x o f or equivalent 3. Chromatography c.o'umn --J&V7 DB-5MS, oOM x 0.25 mm ID, 1.0 pm df or equivalent 4. UPC helium for carr e; : 5. Pentadecafluoiooctauoic acid Ammonium salt -- Fluka, 98% pure or equivalent 6 4-B rcm ofIuorobcnzcne - 2000 ppm BFB Chem Service ampulated solution in methylene dhjpride or equivalent, for tuning agent and internal standard 3 . Hepla^scafluorononanoic acid - Fluka, 97 % pure or equivalent for surrogate staitfSrd .. . . S Tetrabutylammonium hydrogen sulfate (TBA-HS) - Fluka, 99% pure or equivalent. Ion pairing reagent 9. Diethyl Sulfate -Aldrich, 98% or equivalent Ethylation reagent 10. Sulfuric A c id -A C S grade or equivalent COMPANY CONFIDENTIAL 1anraster Laboratories 2 4 2 5 N e w Holland Pike Lancaster. PA 176 0 1 Analysis #0615.01 Revision 01 Supersedes Date: None Effective Date ri-- ~ a ^ -IC PR 0 S 2001 11. Deionized water .iS Standards: . Note: Working stocks are prepared by diluting stock solutior'S iO the appropriate concentration with a syringe and volumetric flask. 1. Stock Pentadecafluorooctanoic acid Ammoniui^i_a1||rC-143] - Weigh approximately 0.02 g pentadecafluorooctanoL$#cidi^gt0nium salt into a 10 mL volumetric flask and dilute to volume wiT ethanol. Record in database or Dept 26 spikes and special mixes nc'ebook 1 his is a stock solution. 2 . Working Stock FC-143 -pentadeopuaipocfaloic acid ammonium salt Dilute the stock p e n ta d e c a flu o fo i^ b io p id ammonium salt solution to 500 ppm using ethanol in 3. Internal standard/T^ing:^blutib0:BFB - 4-Bromofluorobenzene Dilute 2000 ppm ampul.afedv^ck'^pJfltion to 50 ppm in MeOH. This is the internal standard soike Spike o'i standards and samples with 20 pL per 1 mL of final , vo.ume "" 4. Stock H ejptstfecaffuorononanoic acid surrogate - Weigh approximately 0.02 g HeptadecaOorononanoic acid into a 10-mL volumetric flask and dilute to -_ynlwrre with ethanol Record in database or Dept 26 spikes and special - mues notfeoook. This is a stock solution. % ' Working Stock Heptadecafluorononanoic acid - Dilute the stock Jjfeptadecafluorononanoic acid solution to 500 ppm using ethanol. 6. Ion Paring Agent - Tetrabutylammonium hydrogen sulfate (TBA-HS) weigh approximately (0.016 g to 100 mL deionized water) 7. Diethyl Sulfate solution 0.15 Molar in ethanol --2mL of diethyl sulfate in 100 mL of ethanol. COMPANY CONFIDENTIAL 1anraster Laboratories 2425 New Holland Pike Lancaster, PA 17601 Analysis #0615.01 Revision 01 Supersedes Date: None Effective Date: Page 5 of 16 ^pp ' qg 2001 8. Calibration Levels Level 1: F1432.5: 25 pL of calibration and surrogate intermediate + 10 pL of internal standard Level 2: F1435.0 50 pL of calibration and surrogateintermediate + 10 pL of interna. Level 3: F14310.0: standard 100 pL of calibration and surrogate^ intermediate + 10 pL j , interna' / Level 4: F14315.00: standard . 150 pL of caiibrat on and sirrogate in te rm e d ia te 10. u L ^in te rna l standard Level 5: F14320.00: 200 ptrotjcafiarllon and surrogate in te irite Ife + 10 pL of internal slandard Leve' G F1^325.0 250 uL of calibration and surrogate J if f _ intlrfnediate + 10 pL of internal standard IvIDL/LOO standard' 10 pL of calibration and surrogate ,!H intermediate + 10 pL of internal standard M.. A to o.o.mLs--"; - uzBjj^water, 0,5 mL 1 1HCL, to 5 0 mLs dfeionized water, 0.5 mL 1:1 HCL, to 5.0 mLs deionized water, 0.5 mL 1:1 HCL, to 5.0 mLs deionized water, 0.5 mL 1:1 HCL, to 5.0 mLs deionized water, 0.5 mL 1:1 HCL, to 5.0 mLs deionized water, 0.5 mL 1:1 HCL, to 5.0 mLs deionized water 0.5 mL 1:1 HCL, fsB COMPANY CONFIDENTIAL Lancaster Laboratories 2 4 2 5 N e w Holland Pike * Lancaster, PA 17601 Analysis #0615.01 Revision 01 Supersedes Date: None Effective Date: Page 6 of 16 APR 0 S 200! Safety Precautions: ", FC-143 is extremely dangerous in the neat room form. The time weighted aveiuge exposure lim its is 0.1 mg/m3. Therefore, extreme care m ust be used when working with this compound. Also, heating of the neat standard or any concentrated solution m ust be avoided. Any handling o f the neat product m ust be done in a hood with a second analyst observing the process ancjJacting as a safety spotter. ' The compounds used as surrogate standards are alsc ocmgeroui: These compounds form hydrofluoric acid upon heating or breakcow - the exposure of the neat material to any concentrated solution must be ayoiaeSv.,""'-^' Sample Preservation and Holding Timi Samples must be prepared within cays of date collected. Extracts should be analyzed at time of ethylation. Extracts and standards must b -20 to -1QDC prior to analysis. Personnel Training and Qualifications: Each analyst . instrumental analysis will work with an experienced analyst for a period of t-mc, until they can independently calibrate the instrument, use the chromafpgraph=ic idata system to set up sequences, perform the calculations, interpret the jghrbhj^iogr'ams, and enter the data into the LIMS. They will also follow the depW tm ^ilraining manual for analysts. Proficiency is measured through c fiA ip e c ^ io n audits of the tasks listed and overchecking of data. Extraction/Ethylation Procedure: NOTE: Prepare Standards/ Samples only when ready for analysis as variations in ethylation time and absorption time will affect results. A timer is used which can measure two separate times, one for ethylation and one for absorption onto the fiber. COMPANY CONFIDENTIAL I anraster Laboratories 2 4 2 5 N e w Holland Pike * Uncaster, PA 17S01 Analysis #0615.01 Revision 01 Supersedes Date: None Effective Date: ^ 0 g 2001 Page 7 of 16 ' ' 1. Measure 5.0 mL of deionized water (standards) or sample into 15 mL clear ^ vial and add 0.5 mL of 1:1 HCL to pH the solution below 3. . - 2. Spike Standards with appropriate amount of target and s u rr^a fe ^o ^-irig stock solution and samples with 50 pL of 500 ppm Heptadecailuorononanoir acid surrogate solution. Add 10 pL of 50 ppm BFB internal standard to each vial prior to ethylation. -S? 3 Add a rinsed stir bar and 250 p L o f TBA-H3 ion pari, y -wa^e-.k. 4. Add 1.0 mL of 0.15 molar Diethyl Sulfa e and 1 0 mL 200 proof ethanol. 5. Cautiously add 10 drops, of concanPated Sulfuric Acid. 6. Recap vial tightly and place zn the VWR mini stirrer, Model 200, stir plate at speed 4 for 30.0 minutes isee N J PE below). 7. Following the 30 0 m rure ethylahon process, insert the 100 pm PDMS fiber in its withdrawn Vjsit'on at a setting of 1.0 on the fiber pen through the T e flon/silicon'^fum , lower the fiber into the headspace for 10.0 minutes to allow absorption. 8. After 10 C m notes, raise the fiber into the up position and remove it from the the pen height from 1.0 to 3.6 on the fiber pen. Insert the pen into the n jlc tio n port and lower the fiber into the port. Press the START button .to initiate the injection. NOTE: Consistent speed rate and timing for the ethylation, absorption and insertion steps greatly increases the reproducibility and precision ofthe ~ method. Conditions above may change to increase sensitivity, reproducibility and overall chromatography. COMPANY CONFIDENTIAL IHvr i anraster Laboratories2-125 New Holland Pike Lancaster. PA 17501 Analysis #0615.01 Revision 01 Supersedes Date; None Effective Date: pp ft q pnn-s Page 8 of 16 Ari .L ^0 U i GC/MS Analysis: Instrument Setup Detector - Mass selective detector (MSD Detector temperature Oven Temperature Program - 300C ' 45C for 3 minutes, 5GMnutCto 85C, then 70C/minute to finaj-femperatUref 300C, hold for 10 minutes lerap ' Carrier -- Injection - Helium, Const-, rf few ir"*5n35s?' Tib^r insertion A >nitpites 1.5 ml/minute Injector Temperature- 275X Injection Mode -- Spiitless7?-"? ' _ sPlit vent 40 at 2 minutes The conditions listed above.rnsyrbe. chfiriged to improve the linearity, sensitivity, or overall chromatography o'- e a g h ^ ^ ^ lS system. Calibration A. Calibration txn s'sls of analyzing standards at 6 concentration levels and producing responseJaS^mj-The relative standard deviation of the response factor d e tim T fe S h e ^tiita b ility of the average relative response factor for calculation of 4=15:31% oil? j , aliquot of 0.5 ng/pL BFB must analyzed and meet the criteria described in . Table I. If the criteria are not met, the mass spectrometer must be retuned and BFB reanalyzed until all criteria are met. For BFB fiber analysis, Spike 50 pL of 50 ppm BFB working standard into 5.0 mL deionized water with 0.5 mL 1:1 HCLand place on the stir plate, insert the fiber pen, set to 1.0 through the septum and lower the fiber for 10.0 minutes. Raise the fiber, remove the pen and insert into the injection port. Start the injection. COMPANY CONFIDENTIAL Lancaster Laboratories 2 4 2 5 N e w H olland Pike * Lancaster, PA 17601 Analysis #0615.01 Revision 01 Supersedes Date: None Effective Date: . Page 9 of 16 APR 0 9 2001 2. If the performance criteria are met for the BFB solution, perform anjnitial calibration by injecting the six calibration standard solutions referenced previously. '' ,,, --- --- " allSsi 3. At the end of the calibration standard injections, inject the MQL/LO)QU soelul tion. The system must be able to detect FC-143 in the MDL/LOQ so.ulon. If the system does not detect FC-143, then the tuning and" car,brazen procedure must be repeated under conditions that will yield a deectioiffor FC-143 in the MDL/LOQ solution. Instrument maintenance as outlined in MC-EX-001, may be required. , 4. Due to the nature of the technique, initiaj|_&^lbRaS#iis may require multiple days for analysis. In the event a ^libradoTtravnes into a second day, prior to resuming calibration standard injection, fust inject and pass BFB as stated previously, then inject a comparison standard from the already injected standards and confirm sy^fetesiaBjlity by response factor comparison. Response factors musf^Jslgthig^fi% drift in order to continue with calibration. If the % dr.it exceeus 20%, then corrective action and a new initial caIibratiorumay --tobe performed. B. Calculate the resMonseffactor for FC-143 and the PFNA surrogate for each ' s ~ - - .... ~ calibration solu i_- w Calculation of the response factor (RF): i: rf [a jx) X C (is)] \ a (is,) x C (x)] Where- '' A,(x) = Area of the quantitation ion for the compound being measured C(is) = Concentration of the specific internal standard A(is) = Area of the quantitation ion for the specific internal standard C(x) = Concentration of the compound being measured COMPANY CONFIDENTIAL I Lancaster Laboratories 2 4 2 5 N ew Holland Pike Lancaster. PA 17501 Analysis #0615.01 Revision 01 Supersedes Date: None Effective Date: p R Q g 2001 Page 10 of 16 - C. For FC-143 and the surrogate PFNA, calculate the mean RF from the Rgs of the six calibration standards. Calculate the relative standard deviation: %RSD = SD x 100 Avg RF Where: ^ R F -a v g RF SD = n-1 and M Avci FtF - - T R__F.' t) If the RSD of the response factors >s less than j i equal to 15%, then the average relative response factor is used ft* qua "i* lation. If the %RSD exceeds 15% then a linear curve rr ay be used fcr quantitation. D. Continuing calibrations Verify the MS tune and initial"cslibratidrt'at the beginning of every 12-hour work shift during which analyses are per*cim3d. 1. An aliquot of 0 5 ngV1- BFB roust be analyzed and meet the criteria described rn Table 1. If the criteria are not met, the mass spectrometer must be retujed^Stil aflfnteria are met. See A 1. above for injection procedure. 2. Pejforrfin'Ccpffinuing calibration check by injecting an aliquot of the mid-point calibration standard. Calculate the percent drift: > -jg-S%,,kk Drift* = C(/) x 100 . ' Where: ` C(i) = Calibration check compound standard concentration C(c)' = Measured concentration using selected quantitation method COMPANY CONFIDENTIAL I anraster Laboratories 2 4 2 5 N e w H o lla n d Pike Lancaster. PA 17601 Analysis #0615.01 Revision 01 Supersedes Date: None Effective Date: pp Q % 2001 Page 11 of 16 The percent drift for FC-143 should not be greater than 20%. _If the %drift exceeds 20%, then corrective action must be taken and a new in'ti 1 calibration may need to be performed. 3. The absolute areas of the quantitation ions of the internal stanjdsrd5fh_u_s.t'fall within -50% to +100% of the average area from th 'as* initial oa 'brat,on If the area for the internal standard is not within this window then cc jrective action must betaken and documented. 4. The MDL/LOQ standard must be injected after a corny:,,an* BFB and a compliant continuing calibration check standard You must be able to detect FC-143 in the MDL/LOQ solution. If th e ;fe jste ^d ie s not detect FC-143, then the tuning and calibration procedure must be reueabd under conditions that will yield a detection for FC-143 in the MDL/LOQ solution. Instrument maintenance as outlined in MC=EX-QGTmay.be required. Analysis of Samples: 1. Analyze a 5.0 mL aliquo* cf each samp e extract under the same conditions used for the initial and conrinilrig calibrgtjdhs. . 2. At the conclusionjqf.yhfqjacquisition, use the same software to tentatively identify peaks within tie retention t tie window of interest. Examine the ion abundances of component ? q*the chromatogram. If the ion abundance of the FC-143 ion used for quantitation (65a il]u j exceeds the calibration range, dilute the aliquot and reanalyze.bWhen-preparing dilutions, add sufficient internal standard to maintain the same cooncenr tration as that of the ICAL. COMPANY CONFIDENTIAL Lancaster Laboratories 2 4 2 5 N e w Holland Pike Lancaster, PA 17601 Analysis #0615.01 Revision 01 Supersedes Date: None Effective Date: Paqe 12 of 16 ? o a 2001 Qualitative Analysis: %. - fes SSuSisEffliS-ir A compound is identified by comparison of the sample mass spectrum (aftar_ 'Ss*!!"' "H i background subtraction) with the mass spectrum of a standard of the ia rg tCompound (standard reference spectra). In order to verify identification, the foJlowing-^crffei should be me.t: 4|gg? n-|pr. 1. The sample component retention time should be^Jthin^l 0 seconds of the time observed for the component when a ca1ibratiob^piutibp- was analyzed. 2. All ions in the reference spectra a > 10% of me most abundant ion should be present in the sample mass spectra and should agree within absolute 20%. An example spectrum for the ethylated fojrribfTC -143 is presented in Figure 1. Quantitative Analysis: ' 'llllls, TUP Once a compound has oeen identified quant tation will be based on the internal standard technique and the-|nieg?a|jf abundance from the extracted ion current profile (EICP) of the primary characteustic ion. . A(x) x l{is) Concentration [jig IL) = ~A(is) x RFV{o) Where: ' A(x)J~ Ai&u ' quantitation ion for the compound to be measured . l(is ||it Am |pnt of interna! standard added to the water sample (in micrograms) A(is) = Area of the quantitation ion for the appropriate internal standard RF = Average response factor from the current initial calibration V(o) = Original water sample volume (in liters) COMPANY CONFIDENTIAL 1ant-aster Laboratories 2 4 2 5 H e w H olland Pike * Lancaster, PA 1 7 601 Analysis #0615.01 Revision 01 Supersedes Date: None Effective Date: Page 13 of 16 * nn U* 2001 Quality Assurance: "-ifwSS|i? At least one deionized water blank, laboratory control spike, and spike dupycate-Is analyzed with every group. A matrix spike and matrix spike duplicate per analytical batch, unless insufficient client sample volume is supplied. in!\ie,"fc^ises, a LCSD must be substituted for the MS/MSD extraction. The spi kintfso Iuttejflonta ins all analytes of interest. A surrogate standard spiking solution c o n t t t b i r i f u ' 6rononanoic acid is also added. The advisory QC windows are 70 - 130 for the mean -=ry offlffe LCS/LCSD, MS/MSD, and surrogate. If the recovery falls outbid lows, corrective action may be taken based on the nature of the non-cg le corrective action must be documented and may include reinjection je fix tr a ^ in s tru m e n t maintenance, and preparation of new calibration standards. S*a:i3tico ip C windows will be generated and acted upon once sufficient data points have SlIftooHected. Revision Log: Initiated Date: 03/28/01 4* P-H5,i ? ili ''iBssP'' Ver. Effective Date Change 01 Ncw 0615_01 040901 COMPANY CONFIDENTIAL Lancaster Laboratories 2 4 2 5 N e w H olland Pike Lancaster, PA 1 7 601 Analysis #0615.01 Revision 01 Supersedes Date:* None Effective Date: ,, Page 14 of 16 APR 0 0 2O0f Prepared by: ^ S Hate o-j -L?y "=&/ Approved by: 'natp . y / w ^ y . Approved by: ~ 7 T 'V m '\l L ^ Y Y ~ \ c~~ioi<=--------- LC " Quality AssuraWse ' _ 4m m * rv> . 4 / 7/07 *^ COMPANY CONFIDENTIAL Lancaster Laboratories 2425 New Holland Pike Lancaster PA 17601 Analysis #0615.01 Revision 01 Supersedes Date: None Effective Date: Page 15 of 16 Q g 001 , Table l BFB Key Ion Abundance Criteria Mass 50 75 95 96 173 174 175 176 177 Ion Abundance Criteria 15% to 40% of mass 95 30% to 60% of mass 95 base peak, 100% relative abundances^-J_-=. -! 5% to 9% of mass 95 less than 2% of mass 174 1 rV ,. ",m 7"" =-ssr greater than 50% of mas^a5-,-^' ,==. 5% to 9% of massj1Z4-"r_ ''hF greater than ut f l i f l i a n 101% of mass 174 s'sliflW 5% to 9%"of mat V COMPANY CONFIDENTIAL Lancaster Laboratories 2 4 2 5 N e w H o llan d Pike * Lancaster, PA 17601 Analysis #0615.01 Revision 01 Supersedes Date: None Effective Date: Paqe 16 of 16 Figure 1 COMPANY CONFIDENTIAL