Photodegradation of the antibiotics nitroimidazoles in aqueous solution by ultraviolet radiation.

The objective of this study was to analyze the efficacy of ultraviolet (UV) radiation in the direct photodegradation of nitroimidazoles. For this purpose, i) a kinetic study was performed, determining the quantum yield of the process; and ii) the influence of the different operational variables was analyzed (initial concentration of antibiotic, pH, presence of natural organic matter compounds, and chemical composition of water), and the time course of total organic carbon (TOC) concentration and toxicity during nitroimidazole photodegradation was studied. The very low quantum yields obtained for the four nitroimidazoles are responsible for the low efficacy of the quantum process during direct photon absorption in nitroimidazole phototransformation. The R(254) values obtained show that the dose habitually used for water disinfection is not sufficient to remove this type of pharmaceutical; therefore, higher doses of UV irradiation or longer exposure times are required for their removal. The time course of TOC and toxicity during direct photodegradation (in both ultrapure and real water) shows that oxidation by-products are not oxidized to CO(2) to the desired extent, generating oxidation by-products that are more toxic than the initial product. The concentration of nitroimidazoles has a major effect on their photodegradation rate. The study of the influence of pH on the values of parameters ɛ (molar absorption coefficient) and k'(E) (photodegradation rate constant) showed no general trend in the behavior of nitroimidazoles as a function of the solution pH. The components of natural organic matter, gallic acid (GAL), tannic acid (TAN) and humic acid (HUM), may act as promoters and/or inhibitors of OH· radicals via photoproduction of H(2)O(2). The effect of GAL on the metronidazole (MNZ) degradation rate markedly differed from that of TAN or HUM, with a higher rate at low GAL concentrations. Differences in MNZ degradation rate among waters with different chemical composition are not very marked, although the rate is slightly lower in wastewaters, mainly due to the UV radiation filter effect of this type of water.

Kinetic study of the adsorption of nitroimidazole antibiotics on activated carbons in aqueous phase.

The adsorption kinetics of four nitroimidazoles, Dimetridazole (DMZ), Metronidazole (MNZ), Ronidazole (RNZ) and Tinidazole (TNZ), were studied on three activated carbons: two commercial carbons from Sorbo-Norit (S) and Merck (M) and a third prepared by chemical activation of petroleum coke (C). Experimental data of the corresponding adsorption kinetics were analyzed by applying pseudo-first and pseudo-second-order models and a general diffusion model. Application of pseudo-first and pseudo-second-order kinetic models verified the following: (i) The kinetic model used that better predicts the adsorption rates depends of both the adsorbent and adsorbate studied. (ii) Nitroimidazole adsorption rate decreases in the order MNZ>DMZ>RNZ>TNZ; therefore, in the case of MNZ, molecular size does not appear to be a determining factor in the process. (iii) Nitroimidazole adsorption rate on carbons increases in the order C

Removal of tinidazole from waters by using ozone and activated carbon in dynamic regime.

The main objective of the present study was to analyze the efficacy of technologies based on ozone and activated carbon in dynamic regime to remove organic micropollutants from waters, using the antibiotic tinidazole (TNZ) as a model compound. Results obtained in static regime show that the presence of activated carbon (GAC) during tinidazole ozonation: (i) increases its removal rate, (ii) reduces oxidation by-product toxicity, and (iii) reduces the concentration of dissolved organic matter. Study of the ozone/activated carbon system in dynamic regime showed that ozonation of tinidazole before the adsorption process considerably improves column performance, increasing the volume of water treated. It was observed that the efficacy of the treatment considerably increased with a shorter contact time between TNZ and O(3) streams before entering the column allowing a much higher volume of TNZ solution to be treated compared with the use of activated carbon alone, and reducing by 75% the amount of activated carbon required per unit of treated water volume. TNZ removal by the O(3)/GAC system is lower in natural waters and especially in wastewaters, than in ultrapure water. The toxicity results obtained during TNZ treatment with O(3)/GAC system showed that toxicity was directly proportional to the concentration of TNZ in the effluent, verifying that oxidation of the organic matter in the natural waters did not increase the toxicity of the system.

Gamma irradiation of pharmaceutical compounds, nitroimidazoles, as a new alternative for water treatment.

The main objectives of this study were: (1) to investigate the decomposition and mineralization of nitroimidazoles (Metronidazole [MNZ], Dimetridazole [DMZ], and Tinidazole [TNZ]) in waste and drinking water using gamma irradiation; (2) to study the decomposition kinetics of these nitroimidazoles; and (3) to evaluate the efficacy of nitroimidazole removal using radical promoters and scavengers. The results obtained showed that nitroimidazole concentrations decreased with increasing absorbed dose. No differences in irradiation kinetic constant were detected for any nitroimidazole studied (0.0014-0.0017 Gy(-1)). The decomposition yield was higher under acidic conditions than in neutral and alkaline media. Results obtained showed that, at appropriate concentrations, H(2)O(2) accelerates MNZ degradation by generating additional HO(); however, when the dosage of H(2)O(2) exceeds the optimal concentration, the efficacy of MNZ degradation is reduced. The presence of t-BuOH (HO() radical scavenger) and thiourea (HO(), H() and e(aq)(-) scavenger) reduced the MNZ irradiation rate, indicating that degradation of this pollutant can take place via two pathways: oxidation by HO() radicals and reduction by e(aq)(-) and H(). MNZ removal rate was slightly lower in subterranean and surface waters than in ultrapure water and was markedly lower in wastewater. Regardless of the water chemical composition, MNZ gamma irradiation can achieve i) a decrease in the concentration of dissolved organic carbon, and ii) a reduction in the toxicity of the system with higher gamma absorbed dose.

Removal of nitroimidazole antibiotics from aqueous solution by adsorption/bioadsorption on activated carbon.

The objective of the present study was to analyse the behaviour of activated carbon with different chemical and textural properties in nitroimidazole adsorption, also assessing the combined use of microorganisms and activated carbon in the removal of these compounds from waters and the influence of the chemical nature of the solution (pH and ionic strength) on the adsorption process. Results indicate that the adsorption of nitroimidazoles is largely determined by activated carbon chemical properties. Application of the Langmuir equation to the adsorption isotherms showed an elevated adsorption capacity (X(m)=1.04-2.04 mmol/g) for all contaminants studied. Solution pH and electrolyte concentration did not have a major effect on the adsorption of these compounds on activated carbon, confirming that the principal interactions involved in the adsorption of these compounds are non-electrostatic. Nitroimidazoles are not degraded by microorganisms used in the biological stage of a wastewater treatment plant. However, the presence of microorganisms during nitroimidazole adsorption increased their adsorption on the activated carbon, although it weakened interactions between the adsorbate and carbon surface. In dynamic regime, the adsorptive capacity of activated carbon was markedly higher in surface water and groundwater than in urban wastewaters.

Removal of pharmaceutical compounds, nitroimidazoles, from waters by using the ozone/carbon system.

The main objective of this study was to analyze the effectiveness of technologies based on the use of ozone and activated carbon for the removal of nitroimidazoles from water, considering them as model of pharmaceutical compounds. A study was undertaken of the influence of the different operational variables on the effectiveness of each system studied (O(3), O(3)/activated carbon), and on the kinetics involved in each process. Ozone reaction kinetics showed that nitroimidazoles have a low reactivity, with K(O)(3) values <350 M(-1)s(-1) regardless of the nitroimidazole and solution pH considered. However, nitroimidazoles have a high affinity for HO radicals, with radical rate constant (k(HO)) values of around 10(10)M(-1)s(-1). Among the nitroimidazole ozonation by-products, nitrate ions and 3-acetyl-2-oxazolidinone were detected. The presence of activated carbon during nitroimidazole ozonation produces (i) an increase in the removal rate, (ii) a reduction in the toxicity of oxidation by-products, and (iii) a reduction in the concentration of dissolved organic matter. These results are explained by the generation of HO radicals at the O(3)-activated carbon interface.