Photocatalytic, photolytic and radiolytic elimination of imidacloprid from aqueous solution: Reaction mechanism, efficiency and economic considerations

Georgina Rózsa, Máté Náfrádi, Tünde Alapi, Krisztina Schrantz, László Szabó, L. Wojnárovits, E. Takács, A. Tungler

Research output: Article

3 Citations (Scopus)

Abstract

The purpose of this work was the comparison of imidacloprid transformation in heterogeneous photocatalysis (TiO 2 ), UV 254 nm photolysis, UV 254 nm /VUV 185 nm photolysis and γ-radiolysis (also pulse radiolysis) in the presence and absence of dissolved oxygen, and the identification of intermediates formed during the applied treatments. All the methods tested were effective in the degradation of imidacloprid in 10 −4 mol dm −3 aqueous solution. In most cases the mineralization (TOC) and the disappearance of the starting molecules (detected by HPLC/DAD) occurs parallel. However, when the starting molecules were eliminated in oxygenated solutions the highest decrease in TOC values were only 30–40% in UV/VUV and TiO 2 /O 2 systems. In radiolysis and UV photolytic systems these values were 10–15%. In the absence of oxygen the mineralization was usually slower than in its presence. Beside the dominant photocatalytic process, a small-scale contribution of direct photolysis was observed in TiO 2 containing suspensions, irradiated with 300–400 nm light. Hydroxyl radicals show low reactivity with the N-containing aromatic ring, they attack the heterocyclic 5-member ring and the CH 2 bridge between the two rings in direct oxidation or in H-abstraction. In these reactions carbon centred α-aminoalkyl radicals form. In the presence of dissolved oxygen these radicals transform to hydroxylated or carbonylated stable products. Scavenging experiments suggest that in TiO 2 photocatalytic degradation beside hydroxyl radical based transformation, direct charge transfer has also important role in the degradation. Based on the degradation and mineralization results with imidaloprid, photocatalysis, UV/VUV photolysis and radiolysis are recommended for practical application, economic considerations (E EO ) suggest radiolysis as the method requiring lowest electric energy consumption.

Original languageEnglish
Pages (from-to)429-439
Number of pages11
JournalApplied Catalysis B: Environmental
Volume250
DOIs
Publication statusPublished - aug. 5 2019

Fingerprint

imidacloprid
Radiolysis
Photolysis
photolysis
aqueous solution
Degradation
degradation
Economics
Photocatalysis
Dissolved oxygen
mineralization
hydroxyl radical
economics
Hydroxyl Radical
dissolved oxygen
Molecules
Scavenging
Charge transfer
Reactive Oxygen Species
Suspensions

ASJC Scopus subject areas

  • Catalysis
  • Environmental Science(all)
  • Process Chemistry and Technology

Cite this

Photocatalytic, photolytic and radiolytic elimination of imidacloprid from aqueous solution : Reaction mechanism, efficiency and economic considerations. / Rózsa, Georgina; Náfrádi, Máté; Alapi, Tünde; Schrantz, Krisztina; Szabó, László; Wojnárovits, L.; Takács, E.; Tungler, A.

In: Applied Catalysis B: Environmental, Vol. 250, 05.08.2019, p. 429-439.

Research output: Article

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abstract = "The purpose of this work was the comparison of imidacloprid transformation in heterogeneous photocatalysis (TiO 2 ), UV 254 nm photolysis, UV 254 nm /VUV 185 nm photolysis and γ-radiolysis (also pulse radiolysis) in the presence and absence of dissolved oxygen, and the identification of intermediates formed during the applied treatments. All the methods tested were effective in the degradation of imidacloprid in 10 −4 mol dm −3 aqueous solution. In most cases the mineralization (TOC) and the disappearance of the starting molecules (detected by HPLC/DAD) occurs parallel. However, when the starting molecules were eliminated in oxygenated solutions the highest decrease in TOC values were only 30–40{\%} in UV/VUV and TiO 2 /O 2 systems. In radiolysis and UV photolytic systems these values were 10–15{\%}. In the absence of oxygen the mineralization was usually slower than in its presence. Beside the dominant photocatalytic process, a small-scale contribution of direct photolysis was observed in TiO 2 containing suspensions, irradiated with 300–400 nm light. Hydroxyl radicals show low reactivity with the N-containing aromatic ring, they attack the heterocyclic 5-member ring and the CH 2 bridge between the two rings in direct oxidation or in H-abstraction. In these reactions carbon centred α-aminoalkyl radicals form. In the presence of dissolved oxygen these radicals transform to hydroxylated or carbonylated stable products. Scavenging experiments suggest that in TiO 2 photocatalytic degradation beside hydroxyl radical based transformation, direct charge transfer has also important role in the degradation. Based on the degradation and mineralization results with imidaloprid, photocatalysis, UV/VUV photolysis and radiolysis are recommended for practical application, economic considerations (E EO ) suggest radiolysis as the method requiring lowest electric energy consumption.",
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AU - Rózsa, Georgina

AU - Náfrádi, Máté

AU - Alapi, Tünde

AU - Schrantz, Krisztina

AU - Szabó, László

AU - Wojnárovits, L.

AU - Takács, E.

AU - Tungler, A.

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