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敌敌畏的大气归宿:光解和OH引发的氧化研究。

Atmospheric fate of dichlorvos: photolysis and OH-initiated oxidation studies.

作者信息

Feigenbrugel V, Le Person A, Le Calvé S, Mellouki A, Muñoz A, Wirtz K

机构信息

Centre de Geochimie de la Surface, CNRS and Université Louis Pasteur, 1 rue Blessig, F-67084 Strasbourg, France.

出版信息

Environ Sci Technol. 2006 Feb 1;40(3):850-7. doi: 10.1021/es051178u.

Abstract

The OH-initiated oxidation of dichlorvos (a widely used insecticide) has been investigated under atmospheric conditions at the large outdoor European photoreactor (EUPHORE) in Valencia, Spain. The rate constant of OH reaction with dichlorvos, k, was measured by using a conventional relative rate technique where 1,3,5-trimethylbenzene (TMB) and cyclohexane were taken as references. With the use of the rate constants of 5.67 x 10(-11) and of 6.97 x 10(-12) cm3 molecule(-1) s(-1) for the reactions OH + TMB and OH + cyclohexane, respectively, the resulting value of the OH reaction rate constant with dichlorvos was derived to be k = (2.6 +/- 0.3) x 10(-11) cm3 molecule(-1) s(-1). The tropospheric lifetime of dichlorvos with respect to reaction with OH radical has been estimated to be around 11 h. The major carbon-containing products observed for the OH reaction with dichlorvos in air under sunlight condition were phosgene and carbon monoxide. The formation of a very stable toxic primary product such as phosgene associated with the relatively short lifetime of dichlorvos may make the use of this pesticide even more toxic for humans when released into the atmosphere.

摘要

在西班牙巴伦西亚的大型户外欧洲光化学反应器(EUPHORE)中,研究了大气条件下OH引发的敌敌畏(一种广泛使用的杀虫剂)氧化反应。通过使用传统的相对速率技术,以1,3,5-三甲基苯(TMB)和环己烷为参比物,测定了OH与敌敌畏反应的速率常数k。分别使用OH + TMB和OH + 环己烷反应的速率常数5.67×10⁻¹¹和6.97×10⁻¹² cm³·分子⁻¹·s⁻¹,得出OH与敌敌畏反应速率常数的值为k = (2.6 ± 0.3)×10⁻¹¹ cm³·分子⁻¹·s⁻¹。据估计,敌敌畏与OH自由基反应的对流层寿命约为11小时。在阳光条件下,空气中OH与敌敌畏反应观察到的主要含碳产物是光气和一氧化碳。与敌敌畏相对较短的寿命相关联的一种非常稳定的有毒初级产物光气的形成,可能使得这种农药释放到大气中时对人类毒性更大。

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