Environmental context Aromatic amines are widely used chemicals, which show enhanced toxicity and longer environmental persistence when halogenated. We investigated the chlorination of aniline in seawater and in natural aqueous solutions containing Fe3+ and Cl–, under simulated sunlight irradiation. The results increase our understanding of the transformation pathway of typical nitrogen-containing aromatic contaminants in the environment. Photochlorination of aniline was observed in aqueous solutions containing dissolved FeIII and chloride ions under simulated solar light irradiation. Effects of O2, Cl–, Fe3+ and pH on the formation of chloroanilines (CAs) were investigated. para-chloroaniline (4CA) was identified as the main chlorinated product. The formation of 4CA is enhanced with increased concentrations of Cl– or Fe3+, and decreased pH, whereas oxygen plays a negligible role in the process. The results indicate that, Cl• is formed mainly by the photodissociation of FeCl2+–FeCl2+ complexes, and reacts with Cl– to produce Cl2•–. Aniline is then oxidised by Cl2•– into an anilino radical cation, which further reacts with Cl2•– to generate CAs. The photochlorination of aniline in natural seawater was also observed. Other phototransformation products of aniline were detected and a transformation pathway was proposed. This work provides evidence for the photochemical chlorination path of aniline-based aromatic amines in aqueous solutions.
The individual IC 50 (the concentrations causing a 50% inhibition of bioluminescence after 15 min exposure) of cadmium ion (Cd) and nine chlorinated anilines to Photobacterium phosphoreum ( P. phosphoreum ) were determined. In order to evaluate the combined effects of the nine chlorinated anilines and Cd, the toxicities of chlorinated anilines combined with different concentrations of Cd were determined, respectively. The results showed that the number of chlorinated anilines manifesting synergy with Cd decreased with the increasing Cd concentration, and the number manifesting antagonism decreased firstly and then increased. The joint toxicity of mixtures at low Cd concentration was weaker than that of most binary mixtures when combined with Cd at medium and high concentrations as indicated by TU Total . QSAR analysis showed that the single toxicity of chlorinated anilines was related to the energy of the lowest unoccupied molecular orbital ( E LUMO ). When combined with different concentrations of Cd, the toxicity was related to the energy difference ( E HOMO − E LUMO ) with different coefficients. Van der Waals’ force or the complexation between chlorinated anilines and Cd had an impact on the toxicity of combined systems, which could account for QSAR models with different physico-chemical descriptors.
Deyang Kong,Qing Xia,Guoqiang Liu,Qingguo Huang,Junhe Lu
Covalent coupling to natural humic constituents comprises an important transformation pathway for anilinic pollutants in the environment. We systematically investigated the reactions of chlorine substituted anilines with catechol and syringic acid in horseradish peroxidase (HRP) catalyzed systems. It was demonstrated that although nucleophilic addition was the mechanism of covalent bonding to both catechol and syringic acid, chloroanilines coupled to the 2 humic constituents via slightly different pathways. 1,4-addition and 1,2-addition are involved to catechol and syringic acid, respectively. 1,4-addition showed empirical 2nd order kinetics and this pathway seemed to be more permanent than 1,2-addition. Stability experiments demonstrated that cross-coupling products with syringic acid could be easily released in acidic conditions. However, cross-coupling with catechol was relatively stable at similar conditions. Thus, the environmental behavior and bioavailability of the coupling products should be carefully assessed.
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