Document QX352EkxnmzXNXEMNX2yRb38v

Quantitative PCB Standards for Electron Capture Gas Chromatography bv RimM l Mb and Am C. MaCa* Southern* EnvirenmewW ftaaaarcfc laboratory, Hattonat Enrironmantal tiaaorrh Cartaf-ConaWa environmental Protection Aancy, Athene Qaortft MU nnetAHtWepiNM aaaa Haim aa*m pm aammatapaptfa (MM? earn la sahdlma at Oniw ittMMhmtaaaf * " ` ^ ------- t#M . at POM. A troll ta #na <ar aa* pamaat ataa* 1AM peal la fee Ini fteelm IMA MM and MM la , Mead aalaMaaa * to Maalan la at Me Malar aetiataea am atbiaeL QuMWtartnoMrf^olpMmtodad IM layh (POW Sadbmemm toECItaelae r--aadi dtaaHy to aa* PCS Immar (W). Iiaaftat1na bp *eat me pmta at adaiai 80 ahmlaraai Mil Seat at Arealtr almdm* la dtfaril baaaaaa briMMa) panda M iaaiiati1 aamplm aee aaeMSme abawmad by Tbaiull dual nWwddiAaaf aadee-mthma (9) ham pmoeaMtSMl tba PCVb M a ami* ba MavavM Is daaaMM^Mrol md dm 1C afcmd hem tUa - - ' * amaeei wbb ttwt bn aamarrim at latdimdm U04*a inn ibli iitblnaji atebeldaeBy mdtad taamiiaHir AredorlSM C. T144; H, 4.0; CA MLT4 1909 (X M.44; H, AM; CA OLIO 1949 C, 6404; H. 170; Cl, MM 1941 C. 4090; H, 1IT; 0, 4904 1254 C, 44.10; H, 1.01; CA 94X9 iaeo c,*i*KQi04;aoar Tim peed and Dm AMMvHae paeridad So primary riaadmd pjMJDB, U* mo need a* a r*> A MM 0 paa rimamtapapb vie apdppd waittfhtiaVCimlnd,aaaoAm,AmtMaaiHVri4ty idpatraiabtakr.aIabMa mMlmamlilmAe OS m 00/100 Oaa (Sam Q. Urn tmrim pa mm hMaHataraiaelpaeflaMmMtalaOamt 00MmOl/mthAeiAadl AMmalltatasaiaUaial at m%C; 10*9,1M0 md 1904 at WC; aad IMO * tOIPC. Tha chrometppima erne tmSM bp ..h...a..N..b..a..t...a...i......Mvdab. A > -J pa rbwrnampafb riO WOO 10 Urn--_rP ww apaiatad at 1040 V (DO) aad tVTCl TV eahpm me a 0 ft s ft M, e4, |bma IMapad Me peaM with 0% MJO m 00/100 ma* On Chtem Q. TW carrim pa aaa aibapB al 00 mi/aM. Arectaaa 1901 ftm 1904 a-- tmalhr at 000*C md Aaata 1900 al lire Aa MM 100 m liiaeiBlapai* rii tdha SO balm at 900*0 ma giritit al a yO toinri d bu oA, paM n 0% AMO aa n/100 ta i Q. 1b emriar pa ma 00% mpa ad in _____ m at mm ari/mda Al maplm am m mateevaphad laotonmdlr ri !9S*G Maaapaatoe OOaV) mm abttat aa a Ptapa UHOC pdnph mam paebamalm hMhai aOS a Oabto npaiatar ta a madta Vaba Mil OC. GC caadMam mte ari la paedeaa ------1--------aplvalmt ta thaw bam BO-QG. Ibai mahdhd by a DIG PDP4 <--------- rtaTbimm > A.mdtol Has (eamap d bOHli i *f film w Mwaaaltt tm aa# aapp mdMea at Ip It* larirwwmatal Pralirilm Afmaf. I. Ovromy, N. L. d. Oma Om (I). SOA M <UOS. 9. Stsa, V, Hahlapr> O, aad OMa i. M. Siba Cim TVakai A IP (WTl). 0. it. a Dfcaafe. P. U. md ftmaO iV.OA MONS 087309 1W #I t raa m> b M* oc pn* <i ' i Mil to alniky ha Ih Hn> ( (MM OC/MP MimM Hn M, ali OO MwMM>mMMiIH)i < inll'Moi <Mprti -- MMhml OC/M WtabiHi i tl AMm *M M an -' MiiiiiI >cr wtk 1MI11M mm- LnMMimMMWldC ran at* tifi m <4 ttowtef oktante m arfi mhI MpMi tl tan ran Itoi 4KM top to aw M> 0n * MM MM, VMM M%. ntoi to I ridtoiMkMikii ~ ' ___rdaMhTCBtnMM. nkl* mm MM M MMM (Mbr t pnimpah aw mM (n ntto tl MM> fCVi (l> aadntoMMdtoototlraniti Plpml btoanai 00 paak that h a nhtoi at ata <a i Wpltatob tod aa an tatatothnUptoairh. Tto nilinto toi patow at m/t SMI b trabal et toai rlitol M) m a/a m, an, w, wi a toaa tffaa* Man b aba a atnag PanPitoto paPm al m/a PM. Mb Mb aid Mb Ml b tto paial Ida daato at to lri.Mn.oMptoapKa). Ito Manta V mlt OMM M* aa alto baa at tot tonkin ! Pa tatattobnHptotal (Pa !(>< far tan W an italnto), rad Pa Paata at ml* 1M mat 1M an aa alto Mi tl tan Plato ton tai- (pate StMUlMHidte irSnte L fton l On tawntofnm at Ametar IMI an Itta an an itactnAAta aHidWIi aada. to paak tonMPnltaA nunpara oampana to aa ntottan ton alalia a pjr. OOCalOP Pam Inbcttan, a tta anan, la pnh Ml an tbml b min. UPiPp at tla nlitun. Han date am aaad te nl abb tta avanpa aababrtnWM at Pa antoW I UadCpaab 1>a Osteon ootedMtyteaalarrwpaMfcl^rt teortna. Unaar im--i to PCTa mm tear* tel ladhrUntl PCB lacaaavo (4) nwlihlM Hd I lb driMr mum mi li laprqdttcteMjr nmiI Nona te day tek pc*-! A typical Ooulaan 4ir--i--- lev IMS la tei Flgura 1 Paak iwoliitiwa uaa art caapteafr a Imi* c to the OC-M8 Marti ao tfMtth . would bo typical of thaoa te tta partfcMa i (5-10). Otfcar flute <4, It. It) tew l' but <Wa fwohrttan la adaqaata te route analyte. Ite araa of udi Avodor pate woa datentead a tha uoiflMa (nonopiM) of teteteo and PCS vara calculated uataf tha roapono of p^DDB Mlow: 9 DDE lnjeetad 4iatiCI ag Cl DDk paalt araa (cur*> K mol. vt bbk = cart --r x PCB paak ana (cart) dag Cl n,CI * Ho ot cUotten tenobtoniil.M'i* m pcb Tabtea I-VI j il l I pMtan l to i MT pate 91 ol tecte IN tea teoftn* atetea la ~ ^I te ateada aaaa aalte te/ok 4. Wcte, R. 0,, cad McCall, Aa C, I. Aw*. Offe AMi CWtete 44, 744 OPTS). 5. fita. V., BoD. tern. Oute IWItai I, CM IIPTt). 9. Mima P. i, Wcteac, A C . aad Mcdterp. An BA tern. Caate Taakai t. >17 (1VT0). T. Ovate D. U PUIte W. B. C. m4 VUteaauva, A. 9te latea. Onate TWcoiMlT (IMP). A Hte D. C. tewa A H, aad TaMaa. i OXJ. NaftuaBM. T (1007), *. Baftept (L R* MM, W. Ip, aad Cteartla. Bn l tea. OBte. AaaL flMdBi M, tel Utte). 14. tea, ^ Wn Mavote. P. On BrtL Bateau, teteaa TMteLAvrr narri). II. loflte BL.nl Hatete * N, J. Anaa QBte Ate fkiterti 44.441 (MTl). IB Bteaa IK aad WM. IX, 1. fttei|. 44. U (1PT1). jukv an MONS 087310 T*fel. CompotMon of Arcelor U21 MT* II 14 10 10 >1 U W^fkl fmtmt 114 104 III S4 104 M 1.4 i.r SUU.UDIwn.> 114 0.1 0.T 04 104 004 404 ChNfae.rolifw 1 t1 0f *r-Jioo%* iJ"% ***--*-- ! "Not Omtopptef Pib*>H--tin Mm rOiMti o |^pplwioo. fifMiriO IhurtM* lartaUai UlMlItlMIltltiMlM rmW0dCl/fMft1rafeiltiat,krHwnki alxttrt. of i Wadtotof. 5f" "f*** npnmM Ip Mfc 00 pA tf** to wr-wm Wi iMgBot on oo u WotmWIoliMiUNIrilS OC --W ^-------------- I----------J- O n L _ *Vt*m9mkaww+y,ih. *>***+- ! m ` oi--liOTillinlMftMOw^OwOmQ^m J ft tv* paaka -----_ t J j_ qJZ -- um. won. 4 Modern (11) km 1WmMhM*|_________ ^ (y TVr to-< U.7% bM--fl pmm atf mliBMmHmh^flivaiiMkkMklU^ I. Wmb ! iMa aamaM hr KM M M "W * mtahh la UM. K kak IXT% klk^i TibklN. Companion of Aioelor UQ TiMtH. CompooltlenofArocJarIZB OIT* FWMmMmifrlitt MMOo. Dttoot.* flkNirol.ao--f II 104 14 rL10 1TT04.4t 00 04 ITt 04 . 04 40 4.4 ?4 44 M94 TO0 04 '44 TO1*M l.T 044 0.4 1 04 1 U04 0 0 0 0.4 *HJw"%* 4.7 04 0 0.7 44 4 04 0.7 `JX 04 T4 Jw* 4 '*** tNf-DDBalM. Mmmni ItM <4*. ROT- Moaa Wolffct Ptrent Ilofetlvo M4.0n> Nan Cklwtaor n 1.1 10 0.0 01 11J 00 11.0 so 0.1 97 11.0 40 U.l 47 14 04 04 00.7 1 U0 >4 0 04 n* *_!* 4.7 0.7 04 0 44 4 04 n% M 04 70 104 04 04 n** J 70 0.0 44 04 0.7 00 14 0.7 0 0.4 104 109 04 1.0 10.4 0 00.4 n* 144 J* 1.0 104 n* Total 004 Rrtaatfca tin. ntoUm I* ar-001-lM a._____a fro* flrotWwnMfahal of iktama rf ttONMpB. rna OC/in 4m. rah Mah*. aMwoorf hoaan f kfhnat 4Ma MMtrMMumtMMBMmet . WD'I HONS 08 73U TiWVI. Companion of AnclorUM i--i s i M* n u 11? 1M 141 m t?4 an Mitt PormM 1.7 4.T II 14 UJ 14.1 44 U4 14 BoteUrt M. Dor.* 14 14 14 4.7 14 14 U If 44 No. of CMorlam* | i* J44% 1 nw* nto* JlO n cs am an a?t m Toy 14 114 44 44 4 14 au 14 ~lu% Tjn* !4 14 14 M4 1 114 t^naun tow-DDl-ioo. --i,,i OmAatat Moko * Hg5** 9k. OMMO * EC II liapiii at - l>n tmimSrmZZ. "* wmMcmm m> a f,n**9 lo WMW MONS 087313 iT mt Flfura I*. DC mod* EC chromatogram of (at tmnpl* a turfcay that had baan tad ftahmaal taalomlaafad odlfi cter 12*L Th* pttk tdantlflcatlen manbara eanrnpaad h ratanMan ttm* ratatha to p4T-OOtMI ftgum lb Standard praetor IMS ran and* th* arana dHtonaatflBirala. niMl BCOmUwi 9* $*wlw im thwl^inliiil * M4I v* W4S daMtiaiipiiMf m ft* OCmmi Tha l aaiwpaRd lo ttis ntMlon Kmc rvMhvto^-OOCBMa Tibia m, thoir MM<W valuaa cm to ralimlaM to rifora A panto 37 aaf 40 afota a* a atagla pato (or both tha aaiapfa and th* ifandaid. Ttoy aid qaa* Htatad by cMabfahyjha vakim hi ThM UL Ito ao accural* ooa^mriaon from tha ataaM ww avtel abla. Hara, fortunately, tha paak la aaly a Hi a Mai of Iha Mai and cm b* Jnorad wtthaat amteaaty WB't; DOS iad DDT v_______________ Tte PCB pMka <Mta( la dan nrr mlna ab bMIaf Arafat IMS uric ' ~ IbM Ma total PCB mfdaaaaaaaoM hr Me rafaari <aa ha iaillia.il hgr tta Mwttn lilhtlril (4 M>. l4athctoaraaha*aflablatpaapa*tteDPTlrpa pMl cfdaa ftreaa PGT* tf thaaa mIIb avo aiiira*| (1 10-17). of Mb mter. imrfiMa of aavanl AiNtam vMad tola tkraa aaparata mm ami patoa te an* mm by oatac tha appro*Ma AimM. Mb 11 HuM ipw. O.. M*. A, *ad Btot, V. iW AaaL Cham 100(1071). 11 Anaaar, fadUb, aad lab /, J. Aa CMUlHS (1070). om>.11 Mi 0. A* i. Am OMa. Aaai C IT. Lm(.Va J.Cte--lug. m (im>. J. * lAaaL Ml M AAV MM SI MOWS 087314 IMto In Aradot 1243, prtlu 84-174 with TM nd p~k* *l"> >wr RRT ltt< Aroclor 1280. Thra. thrra Aroclon havo bran chum for tou- UM lira 00 olandordo boaura they ora thr PCB'i mod found in environment*) samples, they were told in largest quantities (particularly 1242 end 1254). and ttttir chromatograms include ell the EC peaksnotmally found in other Aroclor mixture*. In rddilion. thia aye- tem of dividing the chromatforam* ten*rally matcher the chancre In chlorine numbers; i.e., the peaka used from the 1242 standard are the monn-threugh-tetre chiorobiphenyle, the peaka calculated with 1254 are pmta> and heiaehloroblphenyte, and the peaka fmm the 1260 atandard are.umd to measure the hepta- and octachlorobiphenyla. Figure 10 ia the chromatogram of a composite liver ntraet of threo bluefilla from a PCB-conteminated river. Thia aample obviously oontaino reaiduea of wv- eral Arociora and waa quantitated as daacribed above. However, tome aample chromatograme require a more rlioroue diviaioo. A schematic of thia division pro* cedurt Is ahown In Fleurs 11. Iha logic of thia division is based on several key (seta. Since Aroclor 1254 shows no appreciable peaka (tee Figure 7) before RRT 47, any peaks with a lower RRT indicate the preernce of some Aroclor <4 toae chlorine content. The most likely compound, from x(vrirncc nnd commercial usage, to 1242. Ideally, all lienlts through RRT 75 would be calculated agaimt 1242 (though many of them are praeent In 1254 ae well), beenufle |ieak 78 fa uniqu* to 1242 and not ordinarily diacrrmble in 1254 (compava Figures 5 and 6). However, when chromatographic reeohrttan 1a net optimum, mixtures of the two Arodore may show peak 78 as only a shoulder on peak 84. Experiaanta with known mixtures, described below, show that in thia cnee better results are obtained by making the division t RRT 70 end treating peak 78 + 84 m though it were nil penk 84 from 1254. A peak with RRT 117 ia praeent in Aroclor 1280, hut absent from 1254. The preernce or ahaence of this peak In the sample chromatogram determinas the Stan* dard used to quantitate the remaining peaks. Bines some columns do not reeolve peak 117, the inveetlga* tor will not elwaye know that 1260 it present. Expert* ments with mixtures show that calculations baaed on 1254 ere adequate In thia case. AH peaka of RRT larger than 174 ere calculated with Aroclor 1260 because the relative standard devta* (tons for these peaks are much lower in 1280 (Table VI) than in 1264 (Table V). These rules wave tasted with known-weighl-retio AToctar mixtures that were chromatographed through a low resolution ootumn with the CC detector operated in the pulsed mode. Table VII gives the amount of PCB measured as a percentage Figure 10. Division for quantitelion of a DC mode EC chro matogram of PCa's from btusgill liver extract. The column substrate wa SE-JO. The large peek at RUT SC Is an artifact. Figure IL Chromatogrem Olvitlon Flowchart. Table VII. Percent Recoveries of Aroclor Mixtures Using Chromatogram Division Rules Mixture < 1242 | 1254 1242 1 1264 ' 1242 . 1254 | 1242 | 1264 | 1242 1 1260 i 1261 > 1260 ' 1264 1260 1264 1 1260 r 1242 I 1254 1 1260 Weight Ratio 1 1 3 1 4 ! 6 1 2 1 15 1 1 15 1 4 4 l 2 'a Re covery 1242* 9fl 96 96 99 ion* 102* % Re covery 1242* 103 100 100 102 m* 104'* % Re covery 1264* 109 103 105 99* 105' % Re covery 1264' 101 94 96 99* 109` Peaks through RRT 70 calculated as 1142 (Table III). `Peaks through RRT 64 calculated as 1246 (Table III). 'Peaks through RRT 104 calculated as 1254 (Table V). Peaks through RRT 174 calculated as 1254 (Table V). All other peaks calculated as 1250 (Table VI). m * JULY 19/) XMJRNAl OF CHROMATOGRAPHIC SCIENCE VOL 11 MGNS 087315 vfW 00 i a- Mam dam a. iinaiiim......Mb m, v. Tim. aiMa * md Mia I-Vl *nU aba mrb t fcmupw naa m DOM OV-tt aad OVun |m Ihi. <J-I mi OV* ahda rcr b a M md* mrt tka Wba da Ml Mfe fa UM peek 110 fawe-< MT 9mk ItM fae 10HW to UV Ifafafl Aiocfar fafa. tfaer fa imiwtiiHf tj|l0y --0 fa PC --fa-- (10), amrel mM fcM mpmIh fa Amtae IMS Ml um (10 mfM Mm) mm pwjwl tat fllfai fill faewattre char phi mi ww M fa a wMof MmM wnwl to *Mk mHm me eMm* far BO-OO hi fee Mm- torn la a #adal mmL Tfe mm af Dm turiMjr farted* few ManwurtH rawKM Otttei |> 1W Mi> &, m4 Hirtilif, 0, NN i mi ovni. TtCHMQAL non Response of the Flame Ionization Detector to Nitrogen and Oxygen by IA 6. pM M- Mk>, A CBM**, and A N. M--aalrtiyA Inafflub o* Pabobum EaploraMon, O-HjO. Commtaalon, Dataadun, tntfh 1h ItD m nl b W hnM partly -- mimn (14). dt Hm, m mMk balbd m*nh to Dm FED art mM tab ab (4), ! w bapab tmmmmh tt adpk m mi Maffi, >Im tajja aad wi a* hImIh nil aki Mk Bar Va> MlniikttMblafendikMi . A wkbrt Aa* mm i 94 al * al Wo* tM M b 0m MhhllDkkM*wial<wiril ml |Mk 0mm alai aMkabi maki Ma dart aid d>k| ka. A Maad md dli 1T"A m adaamd a add da aaaaaaadrt ala dll ld-A. a*t bald wirtiid md ndMat Ai b aabm mdkb dm rt 0.0B al midil rnmndi *at amllb l. Mm A H, ' MkOar nmkiaad <u a nmmA.*timHmciiiimirtnFd-n.' Hmd llaW>A A bm A. *' b ............ a add. Trt tt- . a auamt art tar a ab. ntA a M A OMA A A. Drtb, T. A md Uk H IE. I. elm. mm AA ba<**|. A Idrtdrt A A. Aart Cbm 4A aa) (Mb. A ddaai. A A mdfWm D. M^l.tl.m--add. AdllMD. % bkarta. A A < Cl.iailna hi A1M (HTB. ir ONS 0873l6