Nemanja D. Banić

Degradation of thiacloprid in aqueous solution by UV and UV/H2O2 treatments.

Although some studies concerning flash photolysis and photocatalytic ozonation of thiacloprid have already been published, no complete investigation and explanation of the effects of thiacloprid photodegradation under the conditions of UV and UV/H(2)O(2) (high-pressure mercury lamp and H(2)O(2)) have been reported yet. The photochemical degradation of thiacloprid (0.32 mM) was studied under a variety of solution conditions, by varying the initial concentrations of H(2)O(2) from 0 to 162 mM and the pH from 2.8 to 9. In the UV/H(2)O(2) system, thiacloprid reacted rapidly, the maximum first-order rate constant (2.7 x 10(-2)min(-1), r=0.9996) being observed at the H(2)O(2)/thiacloprid molar ratio of 220 and pH 2.8. Under these conditions, 97% of the thiacloprid was removed in about 120 min. The thiacloprid degradation is accompanied by the formation of a number of ionic byproducts (Cl(-), acetate, formate, SO(4)(2-), and NH(4)(+)) and organic intermediates, so that after 35 h of irradiation, 17% of organic carbon remained non-degraded. The application of UV radiation, or H(2)O(2) alone, yielded no significant thiacloprid degradation. The study of the rate of removal of thiacloprid from natural water showed that it is dominantly influenced by the presence of HCO(3)(-).

Efficient removal of sulcotrione and its formulated compound Tangenta® in aqueous TiO2 suspension: Stability, photoproducts assessment and toxicity.

The photocatalytic degradation of the herbicide sulcotrione (0.05 mM) and its formulated compound Tangenta® in aqueous suspensions of TiO2 Degussa P25 was examined as a function of the different operational parameters. The optimum of the catalyst loading was found to be 2.0 mg mL(-1) under UVA light. In the first stage of the reaction, the photocatalytic degradation of sulcotrione alone and in Tangenta® followed the pseudo-first order kinetics, in which the heterogeneous catalysis proceeds via OH and holes. Further, it can be concluded that degradation rate of sulcotrione alone is about two times higher compared to formulated compound. The results showed that the disappearance of sulcotrione led to the formation of three organic intermediates and ionic byproducts (Cl(-), SO4(2-), acetate and formate), whereas their mineralization was about 90% after 4 h. Tentative photodegradation pathways were proposed and discussed. Also, there was no significant toxicity observed after the irradiation of sulcotrione solution and Tangenta® formulation using TiO2 catalyst on three mammalian cell lines.

Advanced oxidation processes for the removal of [bmim][Sal] third generation ionic liquids: effect of water matrices and intermediates identification

Unique properties of ionic liquids make them green alternatives for conventional volatile organic compounds. Due to increased production and the high stability of these substances, they could be classified as persistent pollutants and could break through classical treatment systems into natural waters. A preliminary ionic liquid hydrolysis study demonstrated a pH dependent degradation profile with a significant decrease in hydrolysis efficiency as pH lowered from 10.0 to 2.8. In order to examine future prospects for ionic liquid removal, different advanced oxidation processes (TiO2 Degussa P25/H2O2, TiO2 Degussa P25, 7.2Fe/TiO2/H2O2, and H2O2) were studied for their applicability in the degradation of imidazolium-based ionic liquids in aqueous solution. These processes were conducted in the dark as well as in the presence of UVA and simulated sunlight (SS) radiation. Among the investigated dark processes, the 7.2Fe/TiO2/H2O2 system showed the highest efficiency, which can be attributed to a dark heterogeneous Fenton process. Otherwise, the most efficient among all the studied degradation processes was the UVA/TiO2 Degussa P25/H2O2 process. In order to make degradation processes more similar to that of the practical process SS radiation was used. Among studied processes, the 7.2Fe/TiO2/H2O2 system showed the greatest potential for the removal of ionic liquids. Also, it was observed that the impact of anions on the cation degradation efficiency was much more pronounced. Due to the possible fate of ionic liquids in the environment, for five different waters (pond, rain, tap, river, and condensate) degradations in the dark and under simulated sunlight were studied. For all processes, and all water types in the presence of SS radiation a remarkable positive effect of naturally dissolved organic matter on the degradation efficiency was observed. Also, in all experiments, the anion was less stable than the cation. The major photodegradation products identified using liquid chromatography-mass spectrometry (HPLC-MS/MS) techniques were hydroxylated compounds.

Photocatalytic decomposition of selected biologically active compounds in environmental waters using TiO2/polyaniline nanocomposites: Kinetics, toxicity and intermediates assessment

A comprehensive study of the removal of selected biologically active compounds (pharmaceuticals and pesticides) from different water types was conducted using bare TiO2 nanoparticles and TiO2/polyaniline (TP-50, TP-100, and TP-150) nanocomposite powders. In order to investigate how molecular structure of the substrate influences the rate of its removal, we compared degradation efficiency of the initial substrates and degree of mineralization for the active components of pharmaceuticals (propranolol, and amitriptyline) and pesticides (sulcotrione, and clomazone) in double distilled (DDW) and environmental waters. The results indicate that the efficiency of photocatalytic degradation of propranolol and amitriptyline was higher in environmental waters: rivers (Danube, Tisa, and Begej) and lakes (Moharač, and Sot) in comparison with DDW. On the contrary, degradation efficacy of sulcotrione and clomazone was lower in environmental waters. Further, of the all catalysts applied, bare TiO2 and TP-100 were found to be most effective in the mineralization of propranolol and amitriptyline, respectively, while TP-150 appeared to be the most efficient in terms of sulcotrione and clomazone mineralization. Also, there was no significant toxicity observed after the irradiation of pharmaceuticals or pesticides solutions using appropriate catalysts on rat hepatoma (H-4-II-E), mouse neuroblastoma (Neuro-2a), human colon adenocarcinoma (HT-29), and human fetal lung (MRC-5) cell lines. Subsequently, detection and identification of the formed intermediates in the case of sulcotrione photocatalytic degradation using bare TiO2 and TP-150 showed slightly different pathways of degradation. Furthermore, tentative pathways of sulcotrione photocatalytic degradation were proposed and discussed.