Ozonation of diclofenac in aqueous solution in the presence and absence of an *OH scavenger, tertiary butanol (t-BuOH), was studied, and the most important reaction intermediates and products were identified. The second-order O3 rate constantwas determined by competition with buten-3-ol and was found to be 6.8 x 10(5) M(-1) s(-1) at 20 degrees C. From this high rate constant, it has been concluded that O3 must initially add on the amino nitrogen. Decomposition of the adduct results in the formation of O3*- (--> *OH) and aminyl radical precursors. A free *OH yield of 30% was estimated based on the HCHO yields generated upon reaction of *OH with 0.01 M t-BuOH. Almost all diclofenac reacted when the molar ratio of O3/diclofenac was approximately 5:1 in the presence of t-BuOH and approximately 8:1 in its absence. As primary reaction products (maximum yield), diclofenac-2,5-iminoquinone (32%), 5-hydroxydiclofenac (7%), and 2,6-dichloroaniline (19%) were detected with respect to reacted diclofenac in the presence of t-BuOH. These primary products degraded into secondary ones when the O3 dose was increased. In the *OH-mediated reaction (absence of t-BuOH) small yields of 5-hydroxydiclofenac (4.5%), diclofenac-2,5-iminoquinone (2.7%), and 2,6-dichloroaniline (6%) resulted. Practically all Cl- (95%) was released in the absence of t-BuOH but only about 45% in the presence of t-BuOH at an O3/diclofenac molar ratio of 10: 1. Based on the reaction products, mechanisms that may account for the high O3 consumption during ozonation of diclofenac are suggested. For technical applications, adequate supply of O3 is needed not only to eliminate diclofenac, but also for the degradation of its potentially toxic products like diclofenac-2,5-iminoquinone and 5-hydroxydiclofenac.

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In this work, a single sector lean burn model combustor operating in pilot only mode has been investigated using both experiments and computations with the main objective of analyzing the flame structure and soot formation at conditions relevant to aero-engine applications. Numerical simulations were performed using the large eddy simulation (LES) approach and the conditional moment closure (CMC) combustion model with detailed chemistry and a two-equation model for soot. The CMC model is based on the time-resolved solution of the local flame structure and allows to directly take into account the phenomena associated to molecular mixing and turbulent transport, which are of great importance for the prediction of emissions. The rig investigated in this work, called big optical single sector rig, allows to test real scale lean burn injectors. Experiments, performed at elevated pressure and temperature, corresponding to engine conditions at part load, include planar laser-induced fluorescence of OH (OH-PLIF) and phase Doppler anemometry (PDA) and have been complemented with new laser-induced incandescence (LII) measurements for soot location. The wide range of measurements available allows a comprehensive analysis of the primary combustion region and can be exploited to further assess and validate the LES/CMC approach to capture the flame behavior at engine conditions. It is shown that the LES/CMC approach is able to predict the main characteristics of the flame with a good agreement with the experiment in terms of flame shape, spray characteristics and soot location. Finite-rate chemistry effects appear to be very important in the region close to the injection location leading to the lift-off of the flame. Low levels of soot are observed immediately downstream of the injector exit, where a high amount of vaporized fuel is still present. Further downstream, the fuel vapor disappears quite quickly and an extended region characterized by the presence of pyrolysis products and soot precursors is observed. The strong production of soot precursors together with high soot surface growth rates lead to high values of soot volume fraction in locations consistent with the experiment. Soot oxidation is also very important in the downstream region resulting in a decrease of the soot level at the combustor exit. The results show a very promising capability of the LES/CMC approach to capture the main characteristics of the flame, soot formation, and location at engine relevant conditions. More advanced soot models will be considered in future work in order to improve the quantitative prediction of the soot level.