Modeling of Reductive Biodegradation of TCE to ETH. Adam Worsztynowicz, Dorota Rzychon, Sebastian Iwaszenko, Tomasz Siobowicz

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1 Modlig of Rduciv Biodgradaio of o ETH Adam Worszyowicz, Doroa Rzycho, Sbasia Iwaszo, Tomasz Siobowicz Isiu for Ecology of Idusrial Aras Kossuha S., Kaowic, Polad l. (+-) 5, fax: (+-) mail: iu@iu.aowic.pl Absrac A rduciv biormdiaio procss of chloriad solv () was modld usig iic approach. Dgradaio of o ETH was cosidrd as a coscuiv s of biochmical rasformaios. Exprimal daa wr usd for procss aalysis ad assssig ordr of ach procss sp. I was assumd, ha biochmical racios corol ovrall quicss of h procss. Accordig o rsuls of xprims modl was dividd io wo pars ad VC ETH covrsio. Small bioracor gas laag, cd durig xprim, was icorporad i modl quaios. Aalyical soluios wr rmid ad calculaios wr compard o xprimal daa. Modl was hacd o iclud biological aur of aalyzd procsss: a logisic quaio was usd o dscrib iic paramr dpdcy o microorgaisms populaio. Calculaios prformd wih hacd modl quaios wr compard o xprimal daa wih saisfacory rsuls. Iroducio Usig ad disposal of volail orgaic compouds (VOC) of rsul i soil ad groud war viromal problms. Chloriad solvs, such as rachloroh (PCE), richloroh (), richloroha (TCA) ad carbo rachlorid (CT) ar cosidrd o b o of h mos viromally dagrous VOCs. Amog fw chologis which ar capabl of rmovig hos compouds from soil ad groudwar, biormdiaio sm o b rlaivly chap ad viromally fridly. Trasformaio of chloriad solv durig biodgradaio procss ca follow ihr rduciv dhalogaio (halorspiraio) or oxidaio racios (arobic ad aarobic oxidaio). A ypical rduciv dchloriaio procss of ca b rad as a s of hr sps, cosqu racios. Th is firs covrd o cis ad ras dichloroh (). is h covrd o viyl chlorid (VC) ad VC is chagd io hyl (ETH) which ds h dgradaio pah. Modlig biodgradaio of o ETH ivolvs aalysis of possibl biochmical racios i a paricular biormdiaio sysm, xprimal daa aalysis, maig rasoabl simplifyig assumpio ad formulaig s of quaios dscribig cosidrd sysm. Oc h quaios ar formulad ad paramrs ar assssd, calculaios ar mad ad modl is vrifid wih xprimal daa. Exprimal Bacgroud A small, pocd bad, coiuous gas rcirculaio bioracor was dvlopd i Isiu for Ecology of Idusrial Aras (Polad) wih coopraio wih Wsighous Savaah Rivr Compay (USA) o cla up a limid (up o cubic mrs) ams of coamiad soil. Th sysm was dsigd o a advaag of aarobic biodgradaio of ad is quippd wih procss moiorig ad corollig sysm. Priodically, sampls of soil gass wr a for laboraory aalysis. As h procss was carrid i aarobic codiios, aig soil sampls was impossibl. Figur prss masurd avrag,, VC ad ETH cocraio chags i soil gass. Th rsuls obaid durig biodgradaio xprim wr uss as a basis for formulaio of mahmaical procss dscripio. I was assumd ha quilibrium i,, VC ad ETH cocraios amog gas, liquid ad solid-adsorbd phass ar maiaid hrough procss duraio. O ha basis, calculaig of oal am of ach compoud ca b do by usig appropria Hry s law ad adsorpio cosas, providig ha volum of ach phas is ow.

2 cocraios [mmol/m ] Figur.,, VC ad ETH ma cocraio i soil gas. VC ETH im, days Modl formulaio Rsuls of xprim prov h coscuiv characr of assumd racios s. Thr diffr priods ca b iifid i h bioracor opraio: Sharp dcras of cocraio (afr shor priod of sabl cocraio) accompaid wih disic icras i DEC cocraio, cocraios of VC ad ETH wr gligibl; Ngligibl cocraios of, clos o zro cocraios of VC ad ETH bu slow icras may b obsrvd a h d of h priod, cocraio d o dcli wh VC d ETH bgu o ris; cocraio gligibl, dcras of cocraio o zro, VC cocraio gaid a maximum ad h droppd o vry small valus. Th cocraio chags of ETH wr similar bu h maximum was highr ad shifd i im. Bcaus o rasformaio was sparad from furhr rasformaio of o ETH hrough VC, h modl was dividd io wo pars: (i) dscripio of o racio ad (ii) dscripio of cosqu o VC ad h o ETH racios. As ETH was a fial produc of h rduciv biodgradaio of ad o sigs of ETH dgradaio producs wr foud, i was assumd ha obsrvd dcras i ETH cocraio was causd by gas laag from h bioracor vssl. Gass (mosly CO ad O) producio durig rduciv dgradaio of sludg was cosidrd as a drivig forc for prssur icras isid h vssl, ad, i cosquc, gas laag. I was assumd ha gas scap oo plac durig whol biormdiaio procss. Chags i gas phas cocraio of chloriad aliphaic compouds ar schmaically illusrad i h figur : Figur. Chags i gas phas cocraio of chloriad aliphaic compouds schma mi = vici m = G c m = v c whr: m i, c i mass ad cocraio of chloriad aliphaic compouds flowig io h racor ovr im v i flow ra of gass io h racor (i his cas h ra of gass graio i sludg dgradaio) m, c mass ad cocraio of chloriad aliphaic compouds flowig of h racor ovr im v flow ra of gass laig from h racor m, c icras i chloriad aliphaic compouds mass co ad cocraio i h racor gas phas ovr im G gas phas volum i h racor.

3 Mass balac quaio for gas volum i h bioracor may b wri i h form: m G c i ci c As h flowig gass dos o coai ay chloriad compouds, c i =. Rarragig abov quaio ad subsiuig ci = : c G c dc c G which shows, ha loos of chloriad aliphaic compouds causd by gas laag ca b dscribd by firs ordr iic quaio. Th formula is also ru i cas of ETH. Th procss of o rduciv biodgradaio, icludig looss(firs par of whol procss), ca b dpicd as follows: c c Assumig ha o dgradaio procss ca b dscribd by zro ordr iics, h followig s of ordiary diffrial quaios ca b formulad: Th iiial valus for is qual is bgiig co i h vssl ad for ad is zro. d ( Aalyical soluios of prsd abov quaio ca b wri as follows: ; ; d d d Compariso bw calculad ad masurd ad cos ovr im ar prsd i h figur Th scod par of h rduciv biodgradaio (dchloriaio of followd by dchloriaio of VC) is prsd o schmaic diagram blow: ) l ; ; VC ETH

4 Figur. Chags i ad cos i h bioracor ovr im. xp cis- xp mod mod co, mol 5 im, days Assumig firs ordr racio modl for as wll as VC dgradaio, h followig quaios ca b obaid: d d ETH VC ETH VC ETH VC VC Thir aalyical soluios ca b wri as follows: ETH ( ) d d ( VC ETH ) VC Compariso bw calculad ad masurd valus is prsd i h figur blow.

5 Figur. Chags i, VC ad ETH cos i h bioracor ovr im. co, mol xp VC VC xp ETH ETH xp xp im, days Modl hacm Assumig ha h ra cosas ar proporioal o umbr of microorgaisms aciv i a giv racio a biological aur of procsss may b icorporad. I was addiioally assumd ha chags i populaio of microorgaisms ovr h im follows h logisic quaio. Applyig appropria modificaios o modl quaios rsuld i br modl fi o xprimal daa (fig 5) Figur 5. Chags i, VC ad ETH cos ovr im logisic apporoach xp VC VC xp ETH ETH xp xp Coclusios Rduciv biormdiaio of ca b modld as a s of coscuiv racios. Though firs ordr iics dos o fi wll o xprimal daa, modl ca b furhr hacd. Maig iic cosa proporioal o logisic quaio rsuls i sigifica improvm of modl fi o xprimal daa. Acowldgms This projc was dsigd, maagd ad implmd udr h dircio of h Isiu for Ecology of Idusrial Aras (IETU) ad h Wsighous Savaah Rivr Compay (WSRC) for h Uid Sas Dparm of Ergy (DOE). WSRC providd chical suppor ad srvd as h IETU's cusomr whil Florida Sa Uivrsiy providd projc maagm suppor o h IETU. All paris coopra udr DOE EM-5 Joi Coordiaig Commi for Eviromal Sysms (JCCES) agrm.

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