Abstract

Benzotriazoles are a new class of organic emerging pollutants ubiquitously found in the environment. The increase of their concentration to detectable values is the consequence of the inability of the Conventional Waste Water Plants (CWWPs) to abate these products. We subjected 1H-benzotriazole (BTz), tolyltriazole (TTz), and Tinuvin P (TP, a common UV plastic stabilizer) to photocatalytic degradation under UV-irradiated TiO2 in different conditions. The principal photoformed intermediates, the relationship between the degradation rate and the pH, the degree of mineralization, and the fate of the organic nitrogen were investigated. Under the adopted experimental conditions, all the studied substrates were rapidly photocatalytically transformed (the maximum degradation rates for BTz and TTz were (3.88 ± 0.05) × 10−2 and (2.11 ± 0.09) × 10−2 mM min−1, respectively) and mineralized (the mineralization rate for BTz and TTz was 4.0 × 10−3 mM C min−1 for both substrates). Different from the 1,2,4-triazole rings that are not completely mineralized under photocatalytic conditions, 1H-benzotriazole and tolyltriazole were completely mineralized with a mechanism that involved a partial conversion of organic nitrogen to N2. The photocatalytic process activated by UV-irradiated TiO2 is an efficient tool to abate 1H-benzotriazole and its derivatives, avoiding their release in the environment.

Highlights

  • Human activities release in the environment xenobiotic compounds that are often not biodegradable and not removed by the Conventional Waste Water Plants (CWWPs)

  • The accurate molecular weight of the principal intermediates obtained during the photocatalytic degradation of BTz, TTz, and Tinuvin P was determined analyzing the irradiated solution by High performance liquid chromatography—Electrospray tandem mass spectrometry (HPLC-ESI-MS/MS) with a high-resolution MS detector (LTQ-Orbitrap, Thermo Scientific, Waltham, MA, USA)

  • Due tNoanthomeaitrereiaxlstr2e02m0,e10s,txaFbOilRitPyEuERnRdEeVrIUEWV irradiation, the effect of direct photolysis on the compo5uonf d15s is negligible in the conditions here explored

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Summary

Introduction

Human activities (e.g., industrial processes and agricultural productions) release in the environment xenobiotic compounds that are often not biodegradable and not removed by the Conventional Waste Water Plants (CWWPs). The most used compounds of this class are 1H-benzotriazole (BTz) and tolyltriazole (a mixture of 4-methyl- and 5-methyl-1H-benzotriazole, TTz). These chemicals show strong complexing properties and are used as anticorrosive agents in cooling, hydraulic, and antifreezing fluids; they are additives in washing powders containing detergents or bleaching agents. The photocatalytic processes over irradiated semiconductors have been proposed for the abatement of BTz. Chen et al compared the transformation rate of benzotriazole by UV/H2O2 and UV/TiO2, investigating the kinetics of transformation and the nature of the main by-products, and they observed the decrease of the toxicity with the progressive disappearance of BTz [22]. The photocatalytic degradation of 1-H-1,2,4-triazole and of its derivates p3h-aomtoicnaota-1ly-Htic-1,d2e,4g-rtardiaaztoiolen (oafm1it-rHol-e1),2,a4n-tdria3z,o5l-ediaamndinoo-f1-iHts-1d,2e,r4iv-tartiaeszo3le-am(reincoo-g1n-iHze-1d,2,a4s-trEiaDzAolse), (caommitprooluen) dasndsi3m,5il-adriatmo iBnToz-1-aHnd-1,T2T,4z-tr(inaoztoeleth(reedcoiffgenrieznedt paossEitDioAns)o,fcnomitrpooguenndastosimmsilianr ttoheBtTrziaaznodle TrTinzg()n, wotaestchaerrdiiefdfeoreunt tbpyoWsiatitoannaobfenaintrdogcoen-waotorkmerssin[3t0h].eTtrhieazpohloetroimngin),ewraaliszcaatirornieodfothuetsbeycWomaptaonuanbdes awnadscloo-ww,oarnkdertsh[e30re].teTnhteiopnhooftonmitriongereanliiznattihoen ionftetrhmeseedicaotmespwouansdrsepwoartsedlowas, aancdontsheequreetnecnetioonf tohfe nfiotrrmogaetnioninotfhceyainntuerrimc aecdiidataessawlaasstrbeyp-oprrtoedduacst, awchoinchseiqsuaewnceell-onfotthede fsotarbmleatmioonleocfucleyainnuprhioctaocciadtaalystaic lcaostndbiyti-opnrosd[3u1c,t3,2w]. hTihche pishoatowcaetlal-lnyotitceddesgtraabdleatimonoloecfuclyeaninurpichaoctoidcawtaalsytpichoctooncdatiatiloyntisca[l3ly1,3o2b]t.aiTnheed puhnodtoercastuarlfyatcice-dpelagtriandizaetidontitoafnciyuamnudriiocxaidcied, wasarsepphoortteodcabtyalMytiaccayllkyaonbdtacion-ewdournkderesr [s3u3r]f.ace-platinized t1itHan-biTuTehmnhezedoaaitiimromixaiozodfofetl,tehhai(issBsrwTwezopo)ro,rkrkttowewldyaalsbtsryttioaoMzssotatulucedyd(ykyTtaTthhnzeed, pipcnhhoot-ohwttoiosoccarwakttaoealrrlysyktti[tic3hc3ded]e.5egg-rmraadedtahattyiiooln-n1uHunn-dbdeeenrrzUUoVtVr-i-iairrzrraoadldeiiaaitsteoedmdTTeiriOO) 2a2noodff 1THin-buevninzoPtr(iTaPz,oaleco(BmTmz)o, ntoUlyVltrsitaazboillieze(Tr Tuzs,edininthpislawstoicrkmtahteer5ia-mlsebtehlyoln-1gHin-gbetonzthoteribaeznozloetirsioazmoeler)calansds) T(sineue vTianbPle(TS1P,oafctohme mSuopnpUleVmsetnatbairliyzeMr uatseerdiailnfpolradsteictamilsa)t.erTiahles bdeelgornagdiantgiotno trhaeteboenf zthoetrsieazmoloelecclauslse)s ((sceheeTmaibclael Sst1ruocftuthreesSruepppolretmedenintarFyigMuraete1r)iaalnfdorthdeetfaoilrsm).aTtihoendoefgtrhaedaptrioinncirpaatel ionftethrmeseedmiaotelsecwuleerse (iitncnhhvveeeemfssattiitigcegaaaolttfeesdtdthr..ueAAcnttttiuteterrnnoettsgiioeornnnepwawotaoarstmsedddseeivvinnoottthFeeedidgttutrooiraettzhho1eel)eaaabbrniiilndliitgtyyt.hoToefhfiferiorrarraaimdmdiaaiatotietfoedtndhTeoTiOfpiO2rteh2tseoteonmpmtriiwninnecoreiraprklaailziliseziaenBltTBseozTrmtzaoneagddniidvTaeTtTeziTsnazswniagdenhrdtetos tiontthoetfhaetemoefcthhaenniistmrogoefnpahtootmocsaitnatlyhteictrtiraaznosleforrimnga.tTiohne oaifmthoisf tchlaespsroesfecnotmwpooruknisdasl.sFootor tghiveefiirnsstigtihmtse, itnhteo ftahtee mofetchheaonrigsmaniocfnpithrootgoecnatianlythtiecsteraunnsufsourmalacthioenmoicfatlhsitsrucclatussreosfhcaosmbpeoenunindvse. sFtoigrattheed.first time, the fate of the organic nitrogen in these unusual chemical structures has been investigated

Materials and Methods
H-Benzotriazole Photodegradation
Conclusions
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