Application of new nanostructured photocatalysts in the decomposition of active substances of selected pharmaceuticals in the aquatic matrix

U okviru doktorske disertacije je ispitivana mogućnost implementacije novosintetisanih nanomaterijala (ZnO/SnO2, ZnO/In2O3, ZnO/TiO2) za fotokatalitičku dekompoziciju selektovanih nestereoidnih antiinflamatornih lekova. Sinteza novih nanomaterijala je sprovedena mehanohemijskom solid-state metodom. Niz laboratorijskih postupaka je sprovedeno sa ciljem utvrđivanja najoptimalnijih uslova fotokatalitičkog procesa pri kojim se postiže zadovoljavajuću procenat eliminacije ketoprofena, naproksena, diklofenaka i ibuprofena. Najintezivniji proces razgradnje je postignut u slučaju ketoprofena, dok je ibuprofen predstavljao najrezistentniji farmaceutik čija kompletna degradacija nije postignuta nakon jednočasovnog fotokatalitičkog tretmana. Dodatkom neorganskih konstituenata u akvatični rastvor farmaceutskih jedinjenja, promena degradacione konstante varira od porasta do pada u vrednosti. Inhibitorski uticaj na fotokatalitičku dekompoziciju farmaceutika su pokazali nitratni joni, dok poboljšanje procesa je postignuto dodatkom hloridnih jona. Kompetitivnim fotokatalitičkim reakcijama nesteroidnih antiinflamatornih lekova je pokazana zadovoljavajuća stabilnost i efikasnost nanostrukturnih materijala. Citotoksični testovi su sprovedeni sa ciljem utvrđivanja biokompatibilnost analiziranog naprednog oksidacionog procesa. Ekonomska analiza ukazuje da je primena novih nanomaterijala u fotokatalitičkom procesu isplatljiv proces sa mogućnošću primene u realnim industrijskim postrojenjima.The possibility of implementation of newly synthesized nanomaterials (ZnO/SnO2, ZnO/In2O3, ZnO/TiO2) for photocatalytic decomposition of selected non - steroidal anti - inflammatory drugs was investigated within the doctoral dissertation. The synthesis of new nanomaterials was carried out by the mechanochemical solid-state method. A number of laboratory procedures were performed with the aim of determining the most optimal conditions of the photocatalytic process in which a satisfactory percentage of elimination of ketoprofen, naproxen, diclofenac and ibuprofen is achieved. The most intensive degradation process was achieved in the case of ketoprofen, while ibuprofen was the most resistant pharmaceutical whose complete degradation was not achieved after a one-hour photocatalytic treatment. By adding inorganic constituents to an aquatic solution of pharmaceutical compounds, the change in degradation constant varies from increase to decrease in value. Nitrate ions showed an inhibitory effect on the photocatalytic decomposition of pharmaceuticals, while the improvement of the process was achieved by the addition of chloride ions. Competitive photocatalytic reactions of nonsteroidal anti-inflammatory drugs have shown satisfactory stability and efficiency of nanostructured materials. Cytotoxicity tests were performed to determine the biocompatibility of the analyzed advanced oxidation process. Economic analysis indicates that the application of new nanomaterials in the photocatalytic process is a cost-effective process with the possibility of application in real industrial plants

Application of new nanostructured photocatalysts in the decomposition of active substances of selected pharmaceuticals in the aquatic matrix

U okviru doktorske disertacije je ispitivana mogućnost implementacije novosintetisanih nanomaterijala (ZnO/SnO2, ZnO/In2O3, ZnO/TiO2) za fotokatalitičku dekompoziciju selektovanih nestereoidnih antiinflamatornih lekova. Sinteza novih nanomaterijala je sprovedena mehanohemijskom solid-state metodom. Niz laboratorijskih postupaka je sprovedeno sa ciljem utvrđivanja najoptimalnijih uslova fotokatalitičkog procesa pri kojim se postiže zadovoljavajuću procenat eliminacije ketoprofena, naproksena, diklofenaka i ibuprofena. Najintezivniji proces razgradnje je postignut u slučaju ketoprofena, dok je ibuprofen predstavljao najrezistentniji farmaceutik čija kompletna degradacija nije postignuta nakon jednočasovnog fotokatalitičkog tretmana. Dodatkom neorganskih konstituenata u akvatični rastvor farmaceutskih jedinjenja, promena degradacione konstante varira od porasta do pada u vrednosti. Inhibitorski uticaj na fotokatalitičku dekompoziciju farmaceutika su pokazali nitratni joni, dok poboljšanje procesa je postignuto dodatkom hloridnih jona. Kompetitivnim fotokatalitičkim reakcijama nesteroidnih antiinflamatornih lekova je pokazana zadovoljavajuća stabilnost i efikasnost nanostrukturnih materijala. Citotoksični testovi su sprovedeni sa ciljem utvrđivanja biokompatibilnost analiziranog naprednog oksidacionog procesa. Ekonomska analiza ukazuje da je primena novih nanomaterijala u fotokatalitičkom procesu isplatljiv proces sa mogućnošću primene u realnim industrijskim postrojenjima.The possibility of implementation of newly synthesized nanomaterials (ZnO/SnO2, ZnO/In2O3, ZnO/TiO2) for photocatalytic decomposition of selected non - steroidal anti - inflammatory drugs was investigated within the doctoral dissertation. The synthesis of new nanomaterials was carried out by the mechanochemical solid-state method. A number of laboratory procedures were performed with the aim of determining the most optimal conditions of the photocatalytic process in which a satisfactory percentage of elimination of ketoprofen, naproxen, diclofenac and ibuprofen is achieved. The most intensive degradation process was achieved in the case of ketoprofen, while ibuprofen was the most resistant pharmaceutical whose complete degradation was not achieved after a one-hour photocatalytic treatment. By adding inorganic constituents to an aquatic solution of pharmaceutical compounds, the change in degradation constant varies from increase to decrease in value. Nitrate ions showed an inhibitory effect on the photocatalytic decomposition of pharmaceuticals, while the improvement of the process was achieved by the addition of chloride ions. Competitive photocatalytic reactions of nonsteroidal anti-inflammatory drugs have shown satisfactory stability and efficiency of nanostructured materials. Cytotoxicity tests were performed to determine the biocompatibility of the analyzed advanced oxidation process. Economic analysis indicates that the application of new nanomaterials in the photocatalytic process is a cost-effective process with the possibility of application in real industrial plants

Removal of carbendazim from aqueous solutions by adsorption on different types of zeolite

Objective: Due to the avid interest in devising economically and environmentally viable and readily available materials for pesticide-contaminated water treatment, the effectiveness of clinoptilolite, a natural zeolite, its modified Na-form, as well as ZSM-5, a synthetic zeolite, was investigated for the removal of the fungicide carbendazim from aqueous solutions. Methods: The removal was investigated using batch adsorption by mixing zeolite and the carbendazim solution at different contact times. At the end of each experiment, the suspensions were filtered, and the residual concentration of carbendazim in the filtrates was measured using high-performance liquid chromatography (HPLC). The experimental results were used to calculate the efficiency of tested zeolite types for the removal of carbendazim from aqueous solutions. Results: Synthetic zeolite was highly effective (94.5%) in removal of carbendazim from aqueous solutions when compared to natural zeolite (19.5–23.3%) and its Na-form (22.5–29.0%). However, the residual carbendazim concentration for all three zeolites tested was above the maximum allowable concentration (MAC). Conclusion: Zeolite ZSM-5 exhibited outstanding properties for the removal of the carbendazim fungicide from aqueous solutions; however, high production costs could be a limiting factor for a wider application in water treatment. For practical applications, natural zeolite may be a more economically viable choice, regardless of its significantly lower removal efficiency. Its surface properties would need to be modified and improved by organic surfactants, which would require additional experiments. Finally, the cost-effectiveness of modified natural zeolite should be compared to the production cost of synthetic zeolite to determine the most effective, economically advantageous, and environmentally friendly solution for the treatment of pesticide-contaminated water

Influence of inorganic consistuents on photocatalytic degradation of ibuprofen

Non-steroidal anti-inflammatory pollutants such as ibuprofen are continuously introduced in water media through various environmental routes. Due to their variability in physico-chemical properties, characteristics of sludge used in secondary treatment and other features, pharmaceutical residues are partially removed in conventional wastewater treatment plants. The effect of inorganic constituent (nitrates) present in real aquatic matrices was examined to assess the overall efficacy of the photocatalytic removal of ibuprofen by nanostructured mixture ZnO/SnO2

Leachate quality assessment of protected water bodies in Serbia and Croatia

Modern agricultural production can not be imagined without the use of pesticides and, if their use is improper, it could lead to continuous introduction of pesticide residues to different environmental media. Water pollution which originates from agricultural activities is a common problem in both observed countries, Serbia and Croatia. The paper provides evaluation of leachate water quality of protected water bodies, Tompojevački ritovi, Croatia, and Lake Zobnatica, Serbia, with the results of detected pesticide residues and other relevant organic micropollutants

Removal of isoproturon from aqueous solution by ZSM-5 zeolite

ZSM-5 zeolite was used to remove isoproturon pesticide from aqueous solutions. The main parameters of adsorption process such as dosages of adsorbent, contact time and initial concentration of isoproturon were investigated. Adsorption equilibrium studies were carried out in batch systems. Results were modeled by adsorption isotherms: Langmuir, Freundlich and Temkin isotherms. The best correlation was achieved with Temkin adsorption isotherm. The maximum adsorption capacity of isoproturon calculated from the Langmuir isotherm was 4,12 mg g-1 at room temperature. Adsorption kinetics of isoproturon has been studied by commonly used kinetic models, i.e., the pseudo-first-order model, the pseudo-second-order model and the intraparticle diffusion model. The kinetic modeling studies showed that kinetics of isoproturon on Zeolite ZSM-5 followed the model of pseudo - second order. This study proved that ZSM-5 zeolite could be used for the removal of isoproturon from aqueous media

Adsorption study of carbendazim pesticide by bentonite clay

Bentonite clay (BC) was used for the adsorption of carbendazim pesticide from aqueous solution. Adsorption with BC was investigated because of its large surface area and high cation exchange capacity. Influence of pH, dose of adsorbent, contact time and initial concentration of carbendazim were studied in adsorption processes by BC. Adsorption experiments were conducted in a batch system and found to be with maximum effectiveness at pH 3. The maximum recoveries of adsorption processes were 0.44mg/g and 0.25mg/g with 0.5 g and 1.0 g of BC, respectively. Contact time was 10 min and initial concentration of carbendazim was 5 mg/L for both experiments

Influence of photocatalysts mass on photocatalytic degradation of mixture of pharmaceuticals by oxide ZnO/TiO2 nanopowder

In this paper, the efficiency of photocatalytic degradation of mixture of pharmaceuticals (naproxen, diclofenac, ketoprofen and ibuprofen) in the aqueous medium using nanoparticle photocatalysts powder ZnO/TiO2, activated by UV radiation, has been examined. It has been shown that the degradation of diclofenac, ketoprofen and ibuprofen takes place efficiently regardless of the mass of the catalyst. Naproxen has proven to be the most resistant pharmaceutical and degradation constants are calculated for naproxen only, which may be used as guidelines in further research. Keywords: photocatalysis, pharmaceuticals, naproxen, diclofenac, ketoprofe, ibuprofen, ZnO/TiO2

Photodegradation of diclofenac sodium in aqueous solution by ZnO/SnO2 powder mixture catalyst

The occurrence of xenobiotics such as drugs, pesticides, personal care products has been widely reported in the last decade. Pharmaceuticals represent emerging micropollutants which are extensively used in medical and veterinary propose. Although pharmaceutical residues are measured in low concentrations, ngL-1 in water, they may have negative impacts on ecosystems. The dominant route of pharmaceuticals into environment is by wastewater effluents discharged from treatment plants mainly based on application of biological treatment such as active sludge. The photodegradation of diclofenac sodium under UV irradiation was investigated using ZnO/SnO2 mixture.After 60 minute of UV exposure, diclofenac was completely degraded

Adsorptive removal of anti-epileptic drug - carbamazepine by activated carbon

This work describes the adsorption process of one of the most dominant pharmaceuticals detected in water sources, carbamazepine (CBZ), from aqueous solutions with commercially available activated carbon (AC). Adsorption studies were performed on powdered activated carbon Norit SA2, in ambient temperature, on pH value between 2 – 10, with different masses of adsorbent (6 – 20 mg), time intervals (5 – 60 min). The CBZ adsorption is explained by chemisorption which involves chemical reaction between surface and adsorbate. The results show that commercial activated carbon Norit SA2 can be applied in the process of adsorption for the purpose of removing carbamazepine from aqueous solution