Phototransformation of ibuprofen and ketoprofen in aqueous solutions.

The UV (254 nm) and UV/VUV (254/185 nm) photolysis of two anti-inflammatory drugs, ibuprofen and ketoprofen, have been studied in aqueous solutions as a possible process for the removal of non-biodegradable compounds. We have examined the effects of dissolved oxygen and initial target concentration. Upon irradiation at 254 nm, the decomposition rate of ketoprofen is almost forty times higher as it of ibuprofen whilst VUV irradiation only increased the ibuprofen decomposition rate. The presence of dissolved oxygen accelerated the photodegradation of ibuprofen, whereas no effect was observed on the degradation of ketoprofen. The maximum quantum yield for the phototransformation was 0.2. The rate of mineralization in both cases was ∼60%, even after 1h of treatment and this suggests the formation of stable by-products which were identified using GC-MS and HPLC-MS, respectively.

Direct VUV photolysis of chlorinated methanes and their mixtures in a nitrogen stream.

The gas-phase decomposition of CCl(4), CHCl(3) and CH(2)Cl(2) and their binary mixtures was studied in a flow-type reactor in a nitrogen gas stream, using a low-pressure mercury vapour lamp covered with a high-purity silica quartz sleeve. The 184.9 nm vacuum-ultraviolet (VUV) light emitted is able to rupture the C-Cl bond in these target substances. For H-containing compounds, the decomposition takes place not only by direct photolysis, but also by H abstraction by .Cl formed during the direct photolysis of the target substances. The relative contributions of direct photolysis and .Cl-sensitized reactions to the decomposition were estimated at different initial concentrations. The addition of CCl(4) to CHCl(3) or CH(2)Cl(2) increased their decomposition rates via increase of the .Cl concentration, whereas the addition of CH(2)Cl(2) to CHCl(3) decreased its degradation rate, suggesting that CH(2)Cl(2) acts as a .Cl radical scavenger. The variation of the product distribution confirms the effect of the composition of the irradiated gas mixtures on the relative contributions of .Cl-sensitized reactions and direct photolysis.

Direct VUV photolysis of chlorinated methanes and their mixtures in an oxygen stream using an ozone producing low-pressure mercury vapour lamp.

The gas-phase photooxidations of CCl(4), CHCl(3), CH(2)Cl(2) and their binary mixtures in an O(2) stream were studied in a flow reactor under various experimental conditions using a low-pressure mercury lamp as light source covered with a high-purity silica sleeve being used. The 184.9 nm VUV irradiation emitted is responsible for the Cl-C bond rupture in the chlorinated methanes and for the formation of O(3) from O(2). The rate of degradation of H-containing chlorinated methanes increased sharply on increase of their initial concentrations, most probably of a (*)Cl chain reaction, as indicated by the increase in the molar ratio of the amount of HCl formed to the amount of H-containing target substance decomposed. The experimental results suggested that the further transformations of the radicals and products formed play an important role as (*)Cl sources, causing a considerably higher rate of decomposition of the H-containing target substances. In a humidified O(2) stream, the (*)OH formed opens up another route for oxidation of the target substances. Thus, the rates of degradation of CH(2)Cl(2) and CHCl(3) increased on increase of the relative humidity, whereas the water vapour had no effect at all on the decomposition of CCl(4). At the same time, competition occurs between (*)Cl or (*)OH for reactions with the target substance. The photooxidation of binary mixtures was investigated too. The addition of CCl(4) or CHCl(3) to CH(2)Cl(2) strongly increased its degradation rate. The addition of CH(2)Cl(2) did not have a considerable effect on the rate of degradation of CHCl(3).

Decomposition of halogenated methanes in oxygen-free gas mixtures by the use of a silent electric discharge.

A silent electric discharge was applied to decompose halogenated methanes including CCl4, CHCl3, CFCl3, CF2Cl2 and CF3Cl, in argon-containing gas mixtures. The decompositions of the target compounds were studied in static reactors at a fixed electric field and room temperature. The reaction products were analyzed by FT-IR spectroscopy, gas chromatography and UV spectrophotometry. The results demonstrated, that the radical-type decomposition of chlorofluoromethanes led to products formed by realignment of the halogen atoms. The decomposition of CCl4 was faster than that of the cholorofluoromethanes, and produced perchloroethane and chlorine. CHCl3 exhibited the highest decomposition rate and produced a large variety of products.

Oxidation of [Fe(CN)6]4- and reduction of [Fe(CN)6]3- in VUV-irradiated aqueous solutions.

Vacuum ultraviolet (VUV) photolysis is one of the straightforward alternatives method among the advanced oxidation processes (AOPs) for the elimination of pollutants from water and air. The VUV photolysis of water produces hydroxyl radicals and hydrogen atoms, which have widely different oxidation and reduction abilities. In this work the oxidation and reduction properties of VUV-irradiated solutions were compared by investigating the reduction of [Fe(CN)6]3- and the oxidation of [Fe(CN)6]4-. The rate of oxidation of [Fe(CN)6]3- was found to be practically the same as the reduction rate of [Fe(CN)6]4- in the irradiated oxygen-free solutions under identical conditions. Dissolved oxygen strongly influences the redox properties of this system.

Disinfection of regenerated dialyzers with ozone.

Regenerated, ozone-disinfected dialyzers were use for a total of 190 hemodialyses in 35 patients without the occurrence of any complication or pyrogen reactions; the efficiency of hemodialysis was identical with that of new or formalin-disinfected dialyzers. The priming fluid contained in both compartments of ozone-disinfected dialyzers proved to be sterile. The ozone did not damage the dialyzer membrane or the supporting structure of dialyzer. Ozone can effectively substitute formalin and other chemical sterilants as a disinfectant of regenerated capillary dialyzers. The process can also be automated.