Document yQO0DgB6YqjJno789bvoDw63

' E ,gen Exygen I1 4RESEARCH RESEARCH rove Ress Precise Research. Proven Results. 1 antsy rafftlu3ednt for Joey I I 1 AAnnaallyyttiiccaall RReeppoorrtt I Woodbury Combined Main FC Monitoring (E04-0241) 1 FFlluuoorroocchheemmiiccaall CChhaarraacctteerriizzaatiioonn ooff AAqueous Sammpplles Woodbury Combined Main FC Monitoring (E04-0241) I 1 EExxyyggeenn RReesseeaarrcchh LLaabboorraattoorryy RReeppoorrtt NNoo.. L0002234 RReevviisiioonn 1 I 1 TTeessttiinngg LLaabboorraattoorryy EExxyyggeenn RReesseeaarrcchh 1 33005588 RReesseeaarrcchh DDrriivvee I - SSttaattee CCoolllleeggee,, PPAA 1166880011 I 1 PPrroojjeecctt LLeeaadd I Todd Fasking Todd Fasking 33MM CCoorrppoorraattiioonn 1 Building 42-26-27 Building 42-2E-27 I PO Box 33331 PO Box 33331 !1 St.Paul, MN 55133-3331 St. Paul, MN 55.133-3331 II1 J~E,Stama, ExEhxihbibiitt 058 Research Drive te College, PA 16801. USA PAGE I~ : ~00.281.3219 ~F: 814.272.1019 eg xygena .com rime, 11994422 State of Minnesota v. 3M Co., Court File No. 27-CV-10-28862 aN_MNoO7 19267 3M_MN00719367 11994422..00000011 I 1I iocectan 1 ~oduc~on I Fs 9.9 A Sp Sn et PE Results are reported for the analysis of aqueous samples received by Exygen Research 1 eT20 sn wie in 1 So (Exygen) from 3M Corporation. The Exygen study number assigned to the project is L0002234. I I 1 (LCMSMS) was requested for al samples. A Specific fluorochemical characterization by liquid (LC/MS/MS) was requested for all samples. A cttoohttraaollmooaff t7o7gssraaapmmhppyilee/ssta((ninndccelkumudiinmnggasffiseieldsdpddeuuctpprloiicmcaateestsr,y, I Eerie blanks, arid spikes) were received for analysis. 1 T`Thheessaammpplleesswweerree pprreeppaarreeddaannddaannaallyyzzeeddbbyy LLCC//MMSSI/MMSSffoorrtthheeffoollloowwiinngglliissttoofffflluuoorroocchheemmicicalasls:: 1I remeron Table 1: Target Analysis I Compound Name Acronym I i Perfluorobutanesulfonate Perfluorohexanesulfonate C4 Sulfonate (PFBS) C6 Sulfonate (PFHS~ Perfluorooctanesulfonate C8 Sulfonate {PFOS) I Perfluorooctanesulfonamide C8 Primary Amide {FOSAI 1 Perfluorooctanoic Acid C8 Acid ('PFOA) TThheeanaanlayltyiticcaall mmeetthhooddss uusseeddwweerreeoroirgigininaallllyyddeevveellooppeeddfoforr ggrroouunnddwwaatteerrssaammplpelessaannddwweerree 1 riboyBedn. Tho sidanpoor and acts #0 0 flo inErgo Ory hn C8 validated by Exygen. The validation protocol and results are on file with Exygen. Only the C8 I rt rh Lh op, Sr) Sulfonate, C8 Primary Amide, and C8 Acid were included in the original method validation. It Sor 85m eg 8Aves ds rr eb wen 1 asaphppoipculiacldbaiblbitleiytyonofoftttehhdeemmteheattthhoothddettootqthuhaeelaitadyddidctiotiinoontnraaolllaanenalleaymlyteteesns.t.s included in this analysis demonstrate the 1I 2 Semple rcet Sample Receipt I EO ------ The water samples were submitted in plastic containers. Samples were received at ambient 1 tteemmpperearatuturere.. SSaammpplleess wweerree ssttoorreedd aatt 44CC ffrroomm rreecceeiipptt uunntitill aannaallyyssiiss.. SSeevveenn iinnddiivviidduuaall A rie containers were received. Field samples were collected on 4/1/04. Samples were received on I RT rt 4/3/04. Chain-of-custody information is presented in Attachment C. I 1 33 HHoollddiinnggTTiimmeess 1 i rt n aosay Field and laboratory spikes of these fluorochemicals have shown stability for periods greater I Bi than 90 days. Samples were analyzed within 30 days of collection. I I 1I cess PAGE2OF5 I 3M MN00719368 11994422..00000022 I 1! 4 Methods - Analytical and Preparatory 4 Methods - Analytical and Preparatory I 41 Lomsms LC/MS/MS 1 411 Sample reparation for LCMSIMS Analysis 4,1.1 Sample Preparation for LC/MS/MS Analysis I Wator samplos wero naltoate wih 20 uf 250 mL. som Foss son (0 Water samples were initially treated.with 200 uL of 250 mg/L sodium thiosulfate solution to remove escial chor,So phase exact (SPE)was158 0prep thesale or remove residual chlorine. Solid phase extraction (SPE) was used to prepare the samples for 1 CCRSHS rams: A 40m. Sam vane: ioof sas se 4 pcvy LCiMS/MS analysis. A 40 mL sample volume, or a portion of sample diluted to 40 mL was I usoraenalydsis. Thosanpioswere arsared 1 a CySPEcaridge.Thocariewes used for analysis. The samples were transferred to a C1~ SPE cartridge. The cartridge was auwiho51mdLof 100%metalThis Toament resuhed naneign concentaton of eluted with 5 mL of 100% methanol. This treatm ent resulted in an eight-fold concentration of 1 ne odsanpiprtlo aonahsse. the diluted samples pdor to analysis. I 412 Sample Analysis by LOMSMS. 4.1.2 Sample Analysis by LC/MS/MS 1 FT ---- In HPLC, an aliquot of extract is injected and passed through a liquid-phase chromatographic ! Gohan. Basedon theafin of he anayefor he siaonarypass in 6coun(oat 0 column. Based on the affinity of the analyte for the stationary phase in the column relative to ho quidmodephase, hs anaesreaned for a charactortcamountofima. Folowng the liquid mobile phase, the analyte is retained for a characteristic amount of time. Following 1 soy HPLC separation, ES/MS provides a rapid and accurate means for analyzing a wide range of i organiccompounc,ncnfuorochamical. Ecrospray s general opreldairely organic compounds, including fluorochemicals. Electrospray is generally operated at relatively mid tomparatrs: molctis aro ized, fragmento and Galo. ors characorsic of 1 Known fiorochomials aeobserved and quanilatedagainststandards. mild temperatures; molecules are ionized, fragmented, and detected. known fluorochemicals are observed and quantitated against standards. Ions characteristic of I AHoviotPatiard P1100 HPLCsystom coped10aMicromass Utima MSSwas sedto A Hewlett-Pa~kard HP1100 HPLC system coupled to a Micromass Ultima MS/MS was used to ansyzo to sample exacs. Analysis was porarnod using selected reaction manor analyze the sample extracts. Analys=s was performed using selected reaction monitoring (SR. Samples wero oxvaced on 47/04an anlyzod botweon 417/04 and 421154. Fa (SRM). Samples were extracted on 4,,7/04 and analyzed between 4/17/04 and 4/21/04. Raw I anayicldaa provid Araanmon:. analytical data is provided in Attachment D. I 1 55 AAnnaallyyssiiss 1 51 Calibration 5.1 Calibration I AT-pontcalbraion curvewascnalyzed a he begining and on of he naesequence A 7-point calibration curve was analyzed at the oeginning and end of the analytical sequence for ta compounds of eres. The Cabraion pois wero propard af 0. 25 8, 100, 2%, 1 500, and 1000 nL for the compounds of 500, and 1000 ng/l_ ((inppptpett)r)esffoto.rr LGMSMS analysis. The calibration points LC/MS/MS analysis. The were The iipnnrssettrpruaumrmeeednnttatrre0es,spp2oo5nn,sse5e0,vvee1rr0ss0uu,ss25tthh0ee, I concewans tlordafortcaichpoonn. Usingincrrogwirn eweisghinsg. oSpne, concentration was plotted for each point. Using linear regression with 1/x weighting, the slope, yinaropt an ortlaon cosfcan () and Goalie of Germination (5) wi Geomines. y-intercept and correlation coefficient (r) and coefficient of determination (r2) were determined. 1 cal ation cues accopate 30963 (= 2 0970) A calibration curve is acceptable if r >__0.985 (r2 > 0.970). I Caltrainstandards reproparo sing ho sameSPEproceduresedforsamples. Calibration standards are prepared using the same SPE procedure used for samples. 1 Caaliibratbioncrchheeccakksstttaannddiaarrddosswwenerreeanaanlaylyzzeeddpepreiroioddiiccaallly ((eevveerryytthhrreeoe oto ffiivveessaammppllee iinnjjeeccttiioonnss)) I troughaut ho anasis sequence. Compan. aiianed # To. sancard. ansys throughout the analysis sequence. Compliance is obtained if the standard analyte Concesawnhn4i420a4ofioacunase. concentrations are within +/-20% of the actual value. 1 Alcairaion crea were met fori anys. All calibration criteria were met for this analysis. I 52 Blanks 5.2 Blanks 1 EE ris we cos ss sn vy ton srs. Th Extraction blanks were prepared and analyzed with every extraction batct- of samples. The I xvacionbanks shou nonaveany age!anal present or abovetoconcatatonof extraction blanks should not have any target analytes present at or above the concentration of he lonevl cabrio SanGar.For osoamps, i exacion inks vers compian. the low-level calibration standard. For these samples, t~e extraction blanks were compliant. I 1 paceaces ! PAGE 3 OF 5 M_UNOOT10369 3M MN00719369 11994422..00000033 ! I Insiument barks i th fom of clean mathanl sortwo lo arahzedafer very Hg Instrument blanks in the form of clean methanol solvent were also analyzed after every high- ovo cabralon tana. and ae Known hes Sams AQar. Fe. Barts ast sot level calibration standard, and after known high-level samples. Again, the blanks should not Taio any age ana poser a abo nd owioe Cuzion Sana For have any target analytes present at or above the low-level calibration standard. For the I Canispsi har ms pane banks at mp samples presented here the instrument blanks are compliant. I 1 55.33 SSSuuurrrorrgooaggtaoatstepekssosronotacomponentof ioLMA anayical mths Surrogate spikes are not a componem of the LC/MS/IVl$ analytical methods. I 55..44 MMaattrriixx SSppiikkeess I Fitand abspaieswnero raped usingall compound of aos. Fld spies wero Field and laboratory spikes were prepared using all compounds of interest, Field spikes were reperby ding a measured vom o eksamp 10 container spiked wih he ret prepared by adding a measured volume of field sample to a container spiked with the target anosby no abort paoshipongcoornsatmaincleorns:Labor ses analytes by the laboratory prior to shipping containers for sample collection. Laboratory spikes covslied of hats of usp od amps hlworeforo thaay ne consisted of aliquots of un-spiked field samples that were fortified at the laboratory at the time I ofocracion. Fi bank sakescansred a oor var re a retry and of extraction. Field blank spikes consisted of laboratory water fortified at the laboratory and Shiop00 wihhasamicrntoh 64andback10. Hoey or Snes. 1 LasLchaoibproparetadotroyrwycitcohonnttrhtroeollssspapimikkeepssle((ssceeoeenstseaecitnciteioornsn 5t5o..66))taharereesfiseaaldmmpaplnieedsoobffa`claakbbootroraaottorhyreywwalatabetoerrrastiopkrikyeedfoaratt he me. analysis. the time I of curacion. Each pe of 5k pros omatan neecad ty assess anys suit, of extraction. Eact~ type of spike provides information needed to assess analyte stability, aracion acon, ond mar ofecs hal may pa andicl roe. Ma sie extraction efficiency, and matrix effects that may ~m~act analytical results. Matrix spike {aca1 Goonvin Artacormasn5 Passe sosSein 57 1 scone]deossion &f recovenes are given in Attachment B. Please see Section 5.7 for additional discussion of mas sp recovers. matrix spike recoveries. I 55 Duplicates 5,5 Duplicates 1 Fiod ard abratory ipictas wero roar for each fd sample. Dupicats resus ro Field and laboratory duplicates were prepared for each field sample. Duplicate resuits are I Gnalong win a apo route Ansnment A given along with the sar~ pie results in Attachment A. 1 55..66 LLaabboorraattoorryy CCoonnttrrooll SSaammpplleess I For LOMSMSanayse, ilvite vasspa winallcompoundsoffre at 100and For LC/MS/MS analyses, Milliq water was spiked with all compounds of interest at 100 and 500 ng uring each axtacisoatn. Al jacovre foraf campounds warsbeeen 7. 500 ng/mL during each extraction set. All recoveries for all compounds were between 70- 1 150% ae LCS. Rakutsao gn ong wi 1 raw a 1 Atachmant. 130% in each LCS. Results are given along with the raw data in Attachment D. I 57 Statement of Accuracy 5.7 Statement of Accuracy Based on resus of id spe, abort fre 0 samp, kd lark spas, and Based on results of field spikes, laboratory fortified field samples, field blank spikes, and 1 aboraor conv spikes,th araytial accuracy of al compounds Gxt PRO+ 90A%. laboratory control spikes, the analytical accuracy of all compounds except PFOA is __ 30%. I Thoacceacy for PFOR i SO. Ai os lark sphcs, oars oonkal spasand The accuracy for PFOA is 50%. All field blank spikes, laboratory control spikes and oratory mati spiesfor af compounds shows 1ecoreies wine hs ranges. Al sie 1 ddlaaatbtaoaaraarrteoerrryeemppooarrtttdeexdd siinnpittkhheeesddfaaottraaattlaal bbclleeossm.. pounds showed recoveries within these ranges. All spike 1I Data Summary 6 Data Summary I Plas seoAtachmentA for dtad sing of th analrss. Ress aro reporedin Please see Attachment A for a detailed listing of the analytical results. Results are reported in 1 paraper bon (oo) (00m) parts per billion (ppb) (ng/mL). I1 7 Data/Sample Retention : 7 Data/Sample Retention ! Samplo aro spose of onomont ser he reports sd ies hari spciod. Al Samples are disposed of one month after the "eport is issued unless othenNise specified. All 1 con Gta& Acheson evra Macsad has co eporssr sed 0 electronic data is archived on retrievable media and hard copy reports are stored in data I en en folders maintained by Exygen. II1 pacesors PAGE4OF5 SN_MNoOT19370 3M MN00719370 11994422..00000044 ! 1 1I Lo 8 TS I1 828A i ! 8.2 I 8.3 8.4 A ttachments ---- Attachment A: Results Ata5cMosht Smiaocnortes Attachment B: Matdx Spike Recoveries men Attachment C: Chain of Custody Attachment D: Raw Analytical Data I : 9 SSiiggnnaattuurreess I 2Lc th 1 FaiConTneaom Lloayder JLCHS I Paul ConnolI~LCMS I /,i"~ohn M. Flaher[y, Vice rP~esident 1 [E------ Other Lab Members Contributing to Data .II me Karen Smith 1I 1I 1I 1I I 1 I 1 I 1 1I 11994422..00000055 po Bote Date SZ Date PAGE 5 OF 5 3M MN00719371