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Removal of carbamazepine from urban wastewater by sulfate radical oxidation

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Abstract

The occurrence of bioactive trace pollutants such as pharmaceuticals in natural waters is an emerging issue. Numerous pharmaceuticals are not completely removed in conventional wastewater treatment plants. Advanced oxidation processes may represent an interesting alternative to completely mineralize organic trace pollutants. In this article, we show that sulfate radicals generated from peroxymonosulfate/CoII are more efficient than hydroxyl radicals generated from the Fenton’s reagent (H2O2/FeII) for the degradation of the pharmaceutical compound, carbamazepine. The second-order rate constant for the reaction of SO4 ·− with carbamazepine is 1.92·109 M−1 s−1. In laboratory grade water and in real urban wastewater, SO4 ·− yielded a faster degradation of carbamazepine compared to HO· . Under strongly oxidizing conditions, a nearly complete mineralization of carbamazepine was achieved, while under mildly oxidizing conditions, several intermediates were identified by LC–MS. These results show for the first time in real urban wastewater that sulfate radicals are more selective than hydroxyl radicals for the oxidation of an organic pollutant and may represent an interesting alternative in advanced oxidation processes.

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References

  • Anipsitakis GP, Dionysiou DD (2004) Radical generation by the interaction of transition metals with common oxidants. Environ Sci Technol 38:3705–3712

    Article  CAS  Google Scholar 

  • Anipsitakis GP, Dionysiou DD, Gonzallez MA (2006) Cobalt-mediated activation of peroxymonosulfate and sulfate radical attack on phenolic compounds. Implications of chloride ions. Environ Sci Technol 40:1000–1007

    Article  CAS  Google Scholar 

  • Buxton GV, Greenstock CL, Helman WP, Ross AB (1988) Critical review of rate constant for reaction of hydrated electrons, hydrogen atoms and hydroxyl radicals (HO·/O·−) in aqueous solution. J Phys Chem Ref Data 17:513–886

    CAS  Google Scholar 

  • Caregnato P, David Gara PM, Bosio GN, Gonzalez MC, Russo N, del Carmen Michelini M, Mártire DO (2008) Theoretical and experimental investigation on the oxidation of gallic acid by sulfate radical anions. J Phys Chem A 112:1188–1194

    Article  CAS  Google Scholar 

  • Chiron S, Minero C, Vione D (2006) Photodegradation processes of the antiepileptic drug carbamazepine, relevant to estuarine waters. Environ Sci Technol 40:5977–5983

    Article  CAS  Google Scholar 

  • Clifton CL, Huie RE (1989) Rate constants for hydrogen abstraction reactions of the sulfate radical, SO4 ·−alcohols. Int J Chem Kinet 21:677–687

    Article  CAS  Google Scholar 

  • Directive 2000/60/EC of the European Parliament and of the Council of 23 October 2000

  • Drewes JE, Heberer T, Reddersen K (2002) Fate of pharmaceuticals during indirect potable reuse. Water Sci Technol 46:73–80

    CAS  Google Scholar 

  • Grigor’ev AE, Makarov IE, Pikaev AK (1987) Formation of Cl2 in the bulk solution during the radiolysis of concentrated aqueous-solutions of chlorides. High Energy Chem 21:99–102

    Google Scholar 

  • House DA (1962) Kinetics and mechanism of oxidations by peroxydisulfate. Chem Rev 62:185–203

    Article  CAS  Google Scholar 

  • Huie RE, Clifton CL (1990) Temperature-dependence of the rate constants for reactions of the sulfate radical, SO4 , with anions. J Phys Chem 94:8561–8567

    Article  CAS  Google Scholar 

  • Huber MM, Canonica S, Park GY, von Gunten U (2003) Oxidation of pharmaceuticals during ozonation and advanced oxidation processes. Environ Sci Technol 37:1016–1024

    Article  CAS  Google Scholar 

  • Khursan SL, Semes’ko DG, Teregulova AN, Safiullin RL (2008) Analysis of the reactivities of organic compounds in hydrogen atom abstraction from their C-H bonds by the sulfate radical anion SO4 ·−. Kinet Catal 49:202–211

    Article  CAS  Google Scholar 

  • Kim J, Edwards JO (1995) A study of cobalt catalysis and copper modification in the coupled decompositions of hydrogen-peroxide and peroxomonosulfate ion. Inorg Chim Acta 235:9–13

    Article  CAS  Google Scholar 

  • Logager T, Sehested K, Holcman J (1993) Rate constants of the equilibrium reactions SO4 ·− + HNO3 ⇆ HSO4  + NO3 · and SO4 ·− + NO3  ⇆ SO4 2− + NO3 ·. J Radiat Phys Chem 41:539–543

    Article  Google Scholar 

  • Miao XS, Metcalfe CD (2003) Determination of carbamazepine and its metabolites in aqueous samples using liquid chromatography-electrospray tandem mass spectrometry. Anal Chem 75:3731–3788

    Article  CAS  Google Scholar 

  • Munter R (2001) Advanced oxidation processes–current status and prospects. Proc Estonien Acad Sci Chem 50:59–80

    CAS  Google Scholar 

  • Neta P, Madhavan V, Zemel H, Fessenden RW (1977) Rate constants and mechanism of reaction of SO4 ·− with aromatic-compounds. J Am Chem Soc 99:163–164

    Article  CAS  Google Scholar 

  • Padmaja S, Neta P, Huie RE (1993) Rate constants for some reactions of inorganic radicals with inorganic-ions—temperature and solvent dependence. Int J Chem Kinet 25:447–455

    Google Scholar 

  • Stan HJ, Heberer T, Linkerhaegner M (1994) Occurrence of clofibric acid in the aquatic system—is the use in human medical care the source of the contamination of surface, ground and drinking water? Vom Wasser 83:57–68

    CAS  Google Scholar 

  • Ternes TA (1998) Occurrence of drugs in German sewage treatment plants and rivers. Water Res 32:3245–3260

    Article  CAS  Google Scholar 

  • Tsao MS, Wilmarth WK (1959) The aqueous chemistry of inorganic free radicals 1. The mechanism of the photolytic decomposition of aqueous persulfate ion and evidence regarding the sulfatehydroxyl radical interconversion equilibrium. J Phys Chem 63:346–353

    Article  CAS  Google Scholar 

  • Warneck P, Ziajka J (1995) Reaction-mechanism of the iron(III)-catalyzed autoxidation of bisulfite in aqueous-solution—steady-state description for benzene as radical scavenger. Ber Bunsenges Phys Chem 99:59–65

    CAS  Google Scholar 

  • Warneck P, Ziajka J, Pasiuk-Bronikowska W (1994) Scavengers of SO4 ·− in S(IV) autoxidation catalyzed by Fe. In: G. Angeletti, G. Restelli (eds) Proceedings of the Sixth European Symposium Physico-Chemical Behaviour of Atmospheric Pollutants. Varese 18–22 October 1993, vol 2. Report EUR 15609/2 EN, Office of Official Publications of the European Communities, Luxemburg 1994, pp 901–906

  • Warnken KW, Davison W, Zhang H, Galceran J, Puy J (2008) Interpretation of in situ speciation measurements of inorganic and organically complexed trace metals in freshwater by DGT. Environ Sci Technol 41:3179–3185

    Article  Google Scholar 

  • Yang Q, Choi H, Chen Y, Dionysiou D (2008) Heterogeneous activation of peroxymonosulfate by supported cobalt catalysts for the degradation of 2, 4-dichlorophenol in water: The effect of support, cobalt precursor, and UV radiation. Appl Cat B 77:300–307

    Article  CAS  Google Scholar 

  • Zemel H, Fessenden W (1978) Mechanism of reaction of so4 − with some derivatives of benzoic-acid. J Phys Chem 82:2670–2676

    Article  CAS  Google Scholar 

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Correspondence to Stéphane Barbati.

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Matta, R., Tlili, S., Chiron, S. et al. Removal of carbamazepine from urban wastewater by sulfate radical oxidation. Environ Chem Lett 9, 347–353 (2011). https://doi.org/10.1007/s10311-010-0285-z

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