Photochemical reaction kinetics and mechanisms of diethyl phthalate with N (III) in the atmospheric aqueous environment | Health & Environmental Research Online (HERO)

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Citation
Tags

HERO ID

5933505

Reference Type

Journal Article

Title

Photochemical reaction kinetics and mechanisms of diethyl phthalate with N (III) in the atmospheric aqueous environment

Author(s)

Lei, Yu; Zhu, C; Lu, Jun; Zhu, Y; Zhu, M; Chen, T; Peng, S

Year

2018

Is Peer Reviewed?

Yes

Journal

Journal of Photochemistry and Photobiology A: Chemistry
ISSN: 1010-6030
EISSN: 1873-2666

Publisher

Elsevier B.V.

Location

LAUSANNE

Volume

362

Page Numbers

21-30

Language

English

DOI

10.1016/j.jphotochem.2018.05.006

Web of Science Id

WOS:000437368300003

Abstract

Diethyl phthalate (DEP) and N (III) are both ubiquitous pollutants in atmospheric hydrometeors. The cross-reaction pathways and kinetic parameters between DEP and N (III) in the atmospheric aqueous environment are explored by using 355 nm laser flash photolysis techniques combined with 365 nm UV light steady-state irradiation. Quantum yields of H2ONO+, HONO and NO2- under 355 nm illuminations are measured as 0.116, 0.231 and 0.036, respectively. Species-specific reaction rate constants of DEP with H2ONO+, HONO and NO2 are determined to be 0.039, 0.07 and 0.008 L mol(-1) s(-1), respectively. Laser flash photolysis studies indicated HO. radicals originating from N (III) photolysis mainly attack aromatic ring of DEP to produce center dot DEP-OH adducts with a second-order rate constant of (4.2 +/- 0.1) x 10(9) L mol(-1) s(-1). The major transformation products, ethyl salicylate and diethyl 4-hydroxyphthalate (m-OH-DEP) are produced from the attacking of HO center dot on the aromatic ring of DEP, while a small amount of dimethyl phthalate is generated by the hydrogen abstraction on the side chain. center dot DEP-OH is identified as a dominated intermediate which undergoes several decay pathways containing monomolecular decay, interaction with N (III), NO2 and oxygen, the nitration processes of center dot DEP-OH by N (III) and NO2 are crucial to the formation of nitro-compounds. The atmospheric implication of reactions between DEP and HO center dot in bulk water and surface water are also discussed.

Keywords

Diethyl phthalate; N (III); Hydroxyl radical; Photo-induced transformation; The atmospheric aqueous phase