Comparative Study on the Removal Efficiency of Clomazone and Amitriptyline via Adsorption and Photocatalysis in Aqueous Media: Kinetic Models and Toxicity Assessment.

This study aimed to compare the effectiveness of adsorption and photocatalysis techniques at removing the herbicide clomazone (CLO) and the antidepressant known as amitriptyline (AMI) from water. This study employed kinetic models to analyze the removal processes and assess the potential toxicity of the treated water. The structure and morphology of the prepared multi-walled carbon nanotubes were characterized as adsorbents by transmission electron microscopy, X-ray diffraction, Fourier transform infrared techniques, and Raman spectroscopy. The adsorption kinetics of CLO and AMI were studied on the pristine and functionalized multi-walled carbon nanotubes. Kinetic studies were performed by modeling the obtained experimental data using three kinetic models: pseudo-first-order, pseudo-second-order, and Elovich kinetic models. On the other hand, the efficiency of CLO and AMI photodegradation was examined as a function of the type of irradiation (UV and simulated solar irradiation) and type of TiO2 photocatalyst (Aeroxide and Kronos). Under the experimental conditions employed, the reaction followed pseudo-first-order kinetics. Additionally, in order to assess the toxicity of water containing CLO, AMI, and their intermediates, toxicity assessments were conducted using human fetal lung fibroblast cells. The results obtained indicate the effectiveness of both methods and provide valuable insights into their removal mechanisms, contributing to the advancement of sustainable water treatment strategies.

Reusable Fe2O3/TiO2/PVC Photocatalysts for the Removal of Methylene Blue in the Presence of Simulated Solar Radiation.

Currently, environmental pollution by various organic pollutants (e.g., organic dyes) is a serious, emerging global issue. The aqueous environment is highly exposed to the harmful effects of these organic compounds. Furthermore, the commonly applied conventional purification techniques are not sufficient enough. Heterogeneous photocatalysis and the photo-Fenton process are effective, low-cost and green alternatives for the removal of organic pollutants. In this study, different iron(III) oxide/titanium(IV) oxide/polyvinyl chloride (Fe2O3/TiO2/PVC) nanocomposites in tablet form were investigated in the photodegradation of methylene blue (MB) under simulated sunlight, and their possible antibacterial effects were examined. The newly synthesized nanocomposites were characterized by scanning electron microscope, X-ray diffraction, UV-Vis diffuse reflectance spectroscopy, and Raman spectroscopy. The results showed a hematite crystal form in the case of Fe2O3(2) and Fe2O3 samples, while the Fe2O3(1) sample showed a combination of hematite and synthetic mineral akaganeite. The highest photocatalytic efficiency was achieved in the presence of Fe2O3/TiO2/PVC, when 70.6% of MB was removed. In addition, the possible photo-cleaning and reuse of the mentioned photocatalyst was also examined. Based on the results, it can be seen that the activity did not decrease after five successive runs. Nanocomposites also exhibited mild antibacterial effects against the two tested Gram-positive bacteria (S. aureus and B. cereus).

Sustainable Removal of Tolperisone from Waters by Application of Photocatalysis, Nanotechnology, and Chemometrics: Quantification, Environmental Toxicity, and Degradation Optimization.

Environmental pollution is an emerging global issue. Heterogenous photocatalytic degradation, which belongs to the advanced oxidation processes, is a promising sustainable technique for the removal of harmful pollutants (e.g., pharmaceuticals) from natural resources (surface and underground waters), as well as wastewaters. In our study, we examined the efficiency of photocatalytic degradation (with TiO2 and ZnO as photocatalysts) of tolperisone hydrochloride (TLP) and the effect of TLP and its degradation intermediates on germination, photosynthetic capacity, and biomass production of wheat. According to the UFLC-DAD and LC-ESI-MS results, we found that the complete degradation of TLP can be reached after 60.83 min of UV irradiation using TiO2 as a photocatalyst. Furthermore, we determined that germination, biomass production, and chlorophyll b (Chl b) were not related to the percentage of TLP after irradiation. Chlorophyll a (Chl a) (r = -0.61, p ≤ 0.05), Chl a+b (r = -0.56, p ≤ 0.05), and carotenoid (car) (r = -0.57, p ≤ 0.05) were strongly inversely (negatively) correlated with TLP, while Chl a+b/car (r = 0.36, p ≤ 0.05) was moderately (positively) related.

Rapid Removal of Organic Pollutants from Aqueous Systems under Solar Irradiation Using ZrO2/Fe3O4 Nanoparticles.

Pure water scarcity is an emerging, all-around problem that globally affects both the life quality and the world's economy. Heterogeneous photocatalysis under solar irradiation is a promising technique for the organic pollutants (e.g., pesticides, drugs) removal from an aqueous environment. Furthermore, the drawbacks of commercially available photocatalysts can be successfully overcome by using innovative nanoparticles, such as ZrO2/Fe3O4. Four ZrO2/Fe3O4 nanopowders with a different mass ratio of ZrO2 and Fe3O4 were synthesized using the chemical co-precipitation method. XRD analysis showed the presence of magnetite and hematite Fe-oxide phases in all samples. The content of the magnetite phase increased with the addition of 19% ZrO2. The efficiency of the newly synthesized ZrO2/Fe3O4 nanoparticles was investigated in the rapid removal of selected pollutants under various experimental conditions. Nevertheless, the influence of the water matrix on photocatalytic degradation was also examined. The obtained data showed that using ZrO2/Fe3O4 nanosystems, an appropriate removal rate of the selected pesticides and pharmaceuticals can be reached after 120 min of solar irradiation. Further, the total organic carbon measurements proved the mineralization of the target emerging pollutants. ZrO2/Fe3O4 nanoparticles are economically feasible, as their removal from the suspension can be easily achieved using affordable, environmentally-friendly magnetic separation.

Sustainable Green Nanotechnologies for Innovative Purifications of Water: Synthesis of the Nanoparticles from Renewable Sources.

Polluting the natural water resources is a serious global issue, which is confirmed by the fact that today at least 2 billion people consume water from contaminated sources. The conventional wastewater treatment methods cannot effectively remove the persistent pollutants (e.g., drugs, organic dyes, pesticides) from the aqueous environment. Heterogeneous photocatalysis is a promising and sustainable alternative for water remediation. It is based on the interaction between light irradiation and the semiconductors (e.g., TiO2, ZnO) as photocatalysts, but these compounds, unfortunately, have some disadvantages. Hence, great attention has been paid to the nanotechnology as a possible way of improvement. Nanomaterials have extraordinary properties; however, their conventional synthesis is often difficult and requires a significant amount of dangerous chemicals. This concise topical review gives recent updates and trends in development of sustainable and green pathways in the synthesis of nanomaterials, as well as in their application for water remediation. In our review we put emphasis on the eco-friendly, mostly plant extract-based materials. The importance of this topic, including this study as well, is proved by the growing number of publications since 2018. Due to the current serious environmental issues (e.g., global warming, shortage of pure and quality water), it is necessary for the traditional TiO2 and ZnO semiconductors to be replaced with the harmless, non-toxic, and more powerful nanocomposites as photocatalysts. Not only because of their higher efficiency as compared to the bulk semiconductors, but also because of the presence of biomolecules that can add up to the pollutant removal efficiency, which has been already confirmed in many researches. However, despite the fact that the application of heterogeneous photocatalysis together with green nanotechnology is absolutely the future in water purification, there are some challenges which have to be overcome. The exact effects of the biomolecules obtained from plants in the synthesis of nanoparticles, as well as in the photocatalytic processes, are not exactly known and require further investigation. Furthermore, heterogeneous photocatalysis is a well-known and commonly examined process; however, its practical use outside the laboratory is expensive and difficult. Thus, it has to be simplified and improved in order to be available for everyone. The aim of our review is to suggest and prove that using these bio-inspired compounds it is possible to reduce human footprint in the nature.

Environmental Photocatalytic Degradation of Antidepressants with Solar Radiation: Kinetics, Mineralization, and Toxicity.

This work is focused on the kinetics, mineralization, and toxicological assessments of the antidepressant drug amitriptyline hydrochloride (AMI) in UV or solar illuminated aqueous suspensions of ZnO, TiO2 Degussa P25, and TiO2 Hombikat. ZnO was proven to be the most effective photocatalyst, and it was used for all further experiments under solar irradiation. The highest reaction rate was observed at 1.0 mg/mL of catalyst loading. In the investigated initial concentration range (0.0075-0.3000 mmol/L), the degradation rate of AMI increased with the increase of initial concentration in the investigated range. The effects of H2O2, (NH4)2S2O8, and KBrO3, acting as electron acceptors, along with molecular oxygen were also studied. By studying the effects of ethanol and NaI as a hydroxyl radical and hole scavenger, respectively, it was shown that the heterogeneous catalysis takes place mainly via free hydroxyl radicals. In the mineralization study, AMI photocatalytic degradation resulted in ~30% of total organic carbon (TOC) decrease after 240 min of irradiation; acetate and formate were produced as the organic intermediates; NH4+, NO3-, NO2- ions were detected as nitrogen byproducts. Toxicity assessment using different mammalian cell lines, showed that H-4-II-E was the most sensitive one.

Removal of Emerging Pollutants from Water Using Environmentally Friendly Processes: Photocatalysts Preparation, Characterization, Intermediates Identification and Toxicity Assessment.

Pharmaceuticals and pesticides are emerging contaminants problematic in the aquatic environment because of their adverse effects on aquatic life and humans. In order to remove them from water, photocatalysis is one of the most modern technologies to be used. First, newly synthesized photocatalysts were successfully prepared using a sol-gel method and characterized by different techniques (XRD, FTIR, UV/Vis, BET and SEM/EDX). The photocatalytic properties of TiO2, ZnO and MgO nanoparticles were examined according to their removal from water for two antibiotics (ciprofloxacin and ceftriaxone) and two herbicides (tembotrione and fluroxypyr) exposed to UV/simulated sunlight (SS). TiO2 proved to be the most efficient nanopowder under UV and SS. Addition of (NH4)2S2O8 led to the faster removal of both antibiotics and herbicide fluroxypyr. The main intermediates were separated and identified for the herbicides and antibiotic ciprofloxacin. Finally, the toxicity of each emerging pollutant mixture and formed intermediates was assessed on wheat germination and biomass production.

Potential of TiO2 with Various Au Nanoparticles for Catalyzing Mesotrione Removal from Wastewaters under Sunlight.

Nowadays, great focus is given to the contamination of surface and groundwater because of the extensive usage of pesticides in agriculture. The improvements of commercial catalyst TiO2 activity using different Au nanoparticles were investigated for mesotrione photocatalytic degradation under simulated sunlight. The selected system was 2.43 × 10-3% Au-S-CH2-CH2-OH/TiO2 (0.5 g/L) that was studied by transmission electron microscopy and ultraviolet-visible (UV-Vis) spectroscopy. It was found that TiO2 particles size was ~20 nm and ~50 nm, respectively. The Au nanoparticles were below 10 nm and were well distributed within the framework of TiO2. For 2.43 × 10-3% Au-S-CH2-CH2-OH/TiO2 (0.5 g/L), band gap energy was 2.45 eV. In comparison to the pure TiO2, addition of Au nanoparticles generally enhanced photocatalytic removal of mesotrione. By examining the degree of mineralization, it was found that 2.43 × 10-3% Au-S-CH2-CH2-OH/TiO2 (0.5 g/L) system was the most efficient for the removal of the mesotrione and intermediates. The effect of tert-butanol, NaF and ethylenediaminetetraacetic acid disodium salt on the transformation rate suggested that the relative contribution of various reactive species changed in following order: h+ > ●OHads > ●OHbulk. Finally, several intermediates that were formed during the photocatalytic treatment of mesotrione were identified.

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 (Moharac, 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.

Enhancement of nano titanium dioxide coatings by fullerene and polyhydroxy fullerene in the photocatalytic degradation of the herbicide mesotrione.

The surface modification of commercial TiO2 Hombikat (TiO2) using nanoparticles of fullerene C60 with tetrahydrofuran (THF-nC60), as well as fullerenol C60(OH)24 nanoparticles (FNP) was investigated in this study. Characterization of THF-nC60, FNP, TiO2, TiO2/THF-nC60, and TiO2/FNP was studied by using DES, ELS, TEM, SEM, DRS and BET measurements and their photoactivity has been examined on the mesotrione degradation under simulated sunlight. It was found that FNP in self-assembled nanocomposite TiO2/FNP increased negatively charge, as well as catalytic surface of TiO2. In addition, TiO2/FNP exhibits a shift of band gap energy to lower values compared to TiO2 and TiO2/THF-nC60. BET surface area has not showed significant differences among catalysts. Furthermore, it was found that the highest photoactivity was obtained for TiO2/FNP system. Besides, influence of different concentrations of electron acceptors (H2O2 and KBrO3), as well as scavengers on the kinetics of mesotrione removal in aqueous solution with/without TiO2 and FNP under simulated sunlight was investigated. Namely, addition of mentioned electron acceptors has resulted in higher mesotrione degradation efficiency compared to O2 alone. Besides, in the first period substrate degradation probably takes place via hydroxyl radicals and after 60 min of irradiation the reaction mechanism proceeds mainly via holes. The most efficient system for mesotrione degradation and mineralization were TiO2/7 mM KBrO3 and TiO2/7 mM KBrO3/40 µl FNP, respectively.