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The study is an extension of our previous work on sonolytic and sonocatalytic decomposition of Diclofenac-Na (DCF) to depict and highlight further operation parameters of significance, and to assess the effect of a novel home-made catalyst made of magnetic nanoparticles of zero-valent iron (ZVI). It was found that high-frequency was more effective than power ultrasound (20 kHz), and the efficiency was a maximum at 861 kHz, acetate-buffered pH 3.0 and air bubbling provided that samples were prepared from a pre-heated stock solution to enhance solubility of the compound. As such, 40-min sonication rendered nearly complete transformation of DCF to intermediate products that were more biodegradable than itself, but with little mineralization of organic carbon. Catalytic sono-treatment showed that the effect of the catalyst was largest in a non-buffered acidic solution and the rate of DCF elimination increased with increasing concentrations of solids up to a "critical" mass, above which it declined via the coalescence of particles and bubbles. Sonocatalysis using the "effective" solid mass also enhanced the overall degradation or mineralization of the compound as portrayed by the accumulation of chloride and nitrate ions in solution after prolonged contact. The production of excess H(2)O(2) during catalysis with ZVI was attributed to the presence of additional and major routes of (·)OH and/or H(2)O(2) formation (other than water pyrolysis). The initial rate of DCF degradation in the presence of nanoparticles was found highly sensitive to the mass of solids in solution, declining sharply as the mass exceeded a "critical" effective level. A catalyst efficacy factor was defined as a function of the initial mass ratio of Fe(0) to DCF and found to be one order of magnitude larger than that obtained by using commercial microparticles with a threefold larger Fe content. The result signifies that the role of aqueous Advanced Fenton reactions (Fe(0)/H(2)O(2)) was less significant in the presence of nanoparticles relative to that of heterogeneous reactions with reactive Fe and oxygen species on the massive surface areas with enriched reaction/adsorption and nucleation sites.

The study covers a thorough assessment of the overall degradation of diclofenac-Na (DCF) by high-frequency ultrasound, focusing particularly on identification, interpretation, and characterization of the oxidation byproducts and their reaction mechanisms. It was found that sonication of 5 mg L(-1) DCF at near neutral pH rendered complete conversion of the compound, 45 % carbon, 30 % chlorine, and 25 % nitrogen mineralization. Density functional theory (DFT) calculations confirmed the experimentally detected major byproduct 2,6-dichloroaniline, the formation of which was explained by OH• addition to the ipso-position of the amino group. The stability of UV absorption at around 276-280 nm throughout reaction was in agreement with the detected byproduct structures, i.e., the presence of amino/amine groups and phenolic, aniline, benzene, and quinine-type derivatives, which all absorbed at around the same band. Microtox toxicity of the reactor aliquots at early reaction showed that initially the reaction products, specifically 1-(2,6-dichlorophenyl)-2-indoline-one, were very toxic; subsequently toxicity exhibited a fluctuating pattern, and a steady declination towards the "non-toxic" level was observed only after 90 min. Oxygen uptake analysis also revealed the formation of harmful products at early reaction, but the reactor was totally biodegradable upon 1-h sonication.