clay and nitrobenzene

A new photoreduction pathway for nitro-aromatic compounds (NACs) and the underlying degradation mechanism are described. 1,3-Dinitrobenzene was reduced to 3-nitroaniline by the widely distributed aromatic molecule indole; the reaction is facilitated by montmorillonite clay mineral under both simulated and natural sunlight irradiation. The novel chemical reaction is strongly affected by the type of exchangeable cation present on montmorillonite. The photoreduction reaction is initiated by the adsorption of 1,3-dinitrobenzene and indole in clay interlayers. Under light irradiation, the excited indole molecule generates a hydrated electron and the indole radical cation. The structural negative charge of montmorillonite plausibly stabilizes the radical cation hence preventing charge recombination. This promotes the release of reactive hydrated electrons for further reductive reactions. Similar results were observed for the photoreduction of nitrobenzene. In situ irradiation time-resolved electron paramagnetic resonance and Fourier transform infrared spectroscopies provided direct evidence for the generation of hydrated electrons and the indole radical cations, which supported the proposed degradation mechanism. In the photoreduction process, the role of clay mineral is to both enhance the generation of hydrated electrons and to provide a constrained reaction environment in the galley regions, which increases the probability of contact between NACs and hydrated electrons.

Topics: Adsorption; Aluminum Silicates; Aniline Compounds; Bentonite; Cations; Clay; Dinitrobenzenes; Electron Spin Resonance Spectroscopy; Electrons; Indoles; Light; Nitro Compounds; Nitrobenzenes; Photochemical Processes; Spectroscopy, Fourier Transform Infrared

In 2005 a pollution accident occurred in the Songhua River, which is geographically located next to groundwater supply plants. This caused public concern about the transport and fate of nitrobenzene (NB) in the groundwater. This paper discusses the mechanisms and effects of the transport and fate of NB in groundwater based on pilot scale experiments conducted in the laboratory, including a simulation experiment, bench-scale batch tests and a one-dimensional numerical model. Parallel batch tests showed that the adsorption of NB to the clay and sand followed the Langmuir-type isotherm, and clay had a greater NB adsorption capacity than sand. NB biodegradation in different conditions was well fitted by the Monod equation and the q(max) values varied from 0.018 to 0.046 h(-1). Results indicated that NB's biodegradation was not affected by the initial NB concentration. Numerical modeling results indicated a good match between computed and observed data, and in the prediction model NB entered the groundwater after the pollution accident. However, the highest concentration of NB was much lower than the allowable limit set by the national standard (0.017 mg/L).

Topics: Adsorption; Aluminum Silicates; Biodegradation, Environmental; Chemical Hazard Release; Clay; Environmental Exposure; Environmental Monitoring; Models, Statistical; Nitrobenzenes; Reference Standards; Rivers; Silicon Dioxide; Water Movements; Water Pollutants, Chemical; Water Pollution; Water Supply