Search results for: organic pollutant degradation

Authors: A. T. Toci, M. V. B. Zanoni

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The advanced oxidation processes have been defined as destructive technologies treatment of wastewater. These involve the formation of powerful oxidizing agents (usually hydroxyl radical .OH) capable of reacting with organic compounds present in wastewater, transforming damaging substances in CO2 and H2O (mineralization) or other innocuous products. However, the photochemical degradation with singlet oxygen has been little explored as oxidative pathway for the treatment of effluents containing food colorants. The molecular oxygen is an effective suppressor of organic molecules in the triplet excited state. One of the possible results of the physical withdrawal is the formation of singlet oxygen. Studies with singlet oxygen (1O2) show an high reactivity of the excited state of the molecule with olefins, aromatic hydrocarbons and a number of other organic and inorganic compounds. Its reactivity is about 2500 times larger than the oxygen in the ground state. Thus, in this work, it was studied the degradation of some dyes used in food industry (tartrazine, sunset yellow, erythrosine and carmoisine) by singlet oxygen. The sensitizer used for generating the 1O2 was methylene blue, which has a quantum yield generation of 0.50. Samples were prepared in water at a concentration of 5 ppm and irradiated with a sunlight simulator (Newport brand, model no. 67005) by consecutive 8h. The absorption spectra of UV-Vis molecules were made each hour irradiation. The degradation kinetics for each dye was determined using the maximum length of each dye absorption. The analysis by UV-Vis revealed that the processes were very efficient for the colorants sunset yellow and carmoisine. Both presented degradation kinetics of order zero with degradation constants 0.416 and 0.104, respectively. In the case of sunset yellow degradation reached 53% after 7h irradiation, Demonstrating the process efficiency. The erithrosine presented during the period irradiated a oscillating degradation kinetics, which requires further study. In the other hand, tartrazine was stable in the presence of 1O2. The investigation of the dyes degradation products owned degradation by 1O2 are underway, the techniques used for this are MS and NMR. The results of this study will enable the application of the cleanest methods for the treatment of industrial effluents, as there are other non-toxic and polluting molecules to generate 1O2.

Keywords: food colourants, singlet oxygen, degradation, wastewater, oxidative

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Authors: Anasheh Maridiroosi, Ali Reza Mahjoub, Hanieh Fakhri

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Heteropoly acid nanoparticles anchored on graphene oxide based on UiO-66 were synthesized via in-situ growth hydrothermal method and tested for photodegradation of a tetracycline as critical pollutant. Results showed that presence of graphene oxide and UiO-66 with high specific surface area, great electron mobility and various functional groups make an excellent support for heteropoly acid and improve photocatalytic efficiency up to 95% for tetracycline. Furthermore, total organic carbon (TOC) analysis verified 79% mineralization of this pollutant under optimum condition.

Keywords: heteropoly acid, graphene oxide, MOF, tetracycline

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Authors: Sudarat Issarapanacheewin, Katcharin Wetchakun, Sukon Phanichphant, Wiyong Kangwansupamonkon, Natda Wetchakun

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The photocatalytic degradation of Methylene blue (MB) and Rhodamine B (RhB) in the presence of ZnWO4-Bi2WO6 composite under visible light irradiation (λ ≥ 400 nm) were studied in this research. The structural and photophysical properties of ZnWO4-Bi2WO6 composite on the photocatalytic degradation process were investigated. The as-prepared ZnWO4-Bi2WO6 composite photocatalyst exhibits wide absorption in the visible-light region and display superior visible-light-driven photocatalytic activities in degradation of MB and RhB. The enhanced photocatalytic activity was attributed to electron-hole separation with the appropriate band potential and the physicochemical properties of ZnWO4 and Bi2WO6. The main active species for the degradation of organic dyes were investigated to explain the enhancement of photocatalytic performance of ZnWO4-Bi2WO6 composite. The possible photocatalytic degradation pathway of aqueous MB and RhB dyes and charge transfer of ZnWO4-Bi2WO6 composite was proposed.

Keywords: composite, dyes, photocatalytic activity, ZnWO4-Bi2WO6

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Authors: Miao Yang

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PPCPs (pharmaceutical and personal care products) in water, as an environmental pollutant, becomes an issue of increasing concern. Therefore, the techniques for degradation of PPCPs has been a hotspot in water pollution control field. Since there are several disadvantages for common degradation techniques of PPCPs, such as low degradation efficiency for certain PPCPs (ibuprofen and Carbamazepine) this proposal will adopt a combined technique by using CDs (carbon nanodots)/C₃N₄ composite and ultrasonic irradiation to mitigate or overcome these shortages. There is a significant scientific problem that the mechanism including PPCPs, major reactants, and interfacial active sites is not clear yet in the study of PPCPs degradation. This work aims to solve this problem by using both theoretical and experimental methodologies. Firstly, optimized parameters will be obtained by evaluating the kinetics and oxidation efficiency under different conditions. The competition between H₂O₂ and PPCPs with HO• will be elucidated, after which the degradation mechanism of PPCPs by the synergy of CDs/C₃N₄ composite and ultrasonic irradiation will be proposed. Finally, a sonolysis-adsorption-catalysis coupling mechanism will be established which is the theoretical basis and technical support for developing new efficient degradation techniques for PPCPs in the future.

Keywords: carbon nanodots/C₃N₄, pharmaceutical and personal care products, ultrasonic irradiation, hydroxyl radical, heterogeneous catalysis

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Authors: L. Obeid, A. Bee, D. Talbot, S. Abramson, M. Welschbillig

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The adsorption process is one of the most efficient methods to remove pollutants from wastewater provided that suitable adsorbents are used. In order to produce environmentally safe adsorbents, natural polymers have received increasing attention in recent years. Thus, alginate and chitosane are extensively used as inexpensive, non-toxic and efficient biosorbents. Alginate is an anionic polysaccharide extracted from brown seaweeds. Chitosan is an amino-polysaccharide; this cationic polymer is obtained by deacetylation of chitin the major constituent of crustaceans. Furthermore, it has been shown that the encapsulation of magnetic materials in alginate and chitosan beads facilitates their recovery from wastewater after the adsorption step, by the use of an external magnetic field gradient, obtained with a magnet or an electromagnet. In the present work, we have studied the adsorption affinity of magnetic alginate beads and magnetic chitosan beads (called magsorbents) for methyl orange (MO) (an anionic dye), methylene blue (MB) (a cationic dye) and p-nitrophenol (PNP) (a hydrophobic pollutant). The effect of different parameters (pH solution, contact time, pollutant initial concentration…) on the adsorption of pollutant on the magnetic beads was investigated. The adsorption of anionic and cationic pollutants is mainly due to electrostatic interactions. Consequently methyl orange is highly adsorbed by chitosan beads in acidic medium and methylene blue by alginate beads in basic medium. In the case of a hydrophobic pollutant, which is weakly adsorbed, we have shown that the adsorption is enhanced by adding a surfactant. Cetylpyridinium chloride (CPC), a cationic surfactant, was used to increase the adsorption of PNP by magnetic alginate beads. Adsorption of CPC by alginate beads occurs through two mechanisms: (i) electrostatic attractions between cationic head groups of CPC and negative carboxylate functions of alginate; (ii) interaction between the hydrocarbon chains of CPC. The hydrophobic pollutant is adsolubilized within the surface aggregated structures of surfactant. Figure c shows that PNP can reach up to 95% of adsorption in presence of CPC. At highest CPC concentrations, desorption occurs due to the formation of micelles in the solution. Our magsorbents appear to efficiently remove ionic and hydrophobic pollutants and we hope that this fundamental research will be helpful for the future development of magnetically assisted processes in water treatment plants.

Keywords: adsorption, alginate, chitosan, magsorbent, magnetic, organic pollutant

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Authors: Eder Amayuelas, Begoña Bazán, M. Karmele Urtiaga, Gotzone Barandika, María I. Arriortua

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Metal Organic Frameworks (MOFs) have attracted great interest in recent years, taking a lead role in the field of catalysis, drug delivery, sensors and absorption. In the past decade, promising results have been reported specifically in the field of adsorption, based on the topology and chemical features of this type of porous material. Thus, its application in industry and environment for the adsorption of pollutants is presented as a response to an increasingly important need. In this area, organic dyes are nowadays widely used in many industries including medicine, textile, leather, printing and plastics. The consequence of this fact is that dyes are present as emerging pollutants in soils and water where they remain for long periods of time due to their high stability, with a potential risk of toxicity in wildlife and in humans. On the other hand, the presence of iodine in soils, water and gas as a nuclear activity pollutant product or its extended use as a germicide is still a problem in many countries, which indicates the imperative need for its removal. In this context, this work presents the characterization as an adsorbent of the activated compound αMOP@Ei2-1 obtained from the already reported [Cu₂₄(m-BDC)₂₄(DMF)₂₀(H₂O)₄]•24DMF•40H₂O (MOP@Ei2-1), where m-BDC is the 1,3-benzenedicarboxylic ligand and DMF is N,N′-dimethylformamide. The structure of MOP@Ei2-1 consists of Cu24 clusters arranged in such a way that 12 paddle-wheels are connected through m-BDC ligands. The clusters exhibit an internal cavity where crystallization molecules of DMF and water are located. Adsorption of dyes and iodine as pollutant examples has been carried out, focusing attention on the kinetics of the rapid process.

Keywords: adsorption, organic dyes, iodine, metal organic frameworks

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Authors: Allah Bakhsh Javid, Ali Mashayekh-Salehi, Fatemeh Davardoost

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This study presents the preparation, characterization and catalytic activity of a novel natural mineral-based catalyst for destructive adsorption of tetracycline (TTC) as water emerging compounds. Degradation potential of raw and calcined magnetite catalyst was evaluated at different experiments situations such as pH, catalyst dose, reaction time and pollutant concentration. Calcined magnetite attained greater catalytic potential than the raw ore in the degradation of tetracycline, around 69% versus 3% at reaction time of 30 min and TTC aqueous solution of 50 mg/L, respectively. Complete removal of TTC could be obtained using 2 g/L calcined nanoparticles at reaction time of 60 min. The removal of TTC increased with the increase in solution temperature. Accordingly, considering its abundance in nature together with its very high catalytic potential, calcined pyrite is a promising and reliable catalytic material for destructive decomposition for catalytic decomposition and mineralization of such pharmaceutical compounds as TTC in water and wastewater.

Keywords: catalytic degradation, tetracycline, pyrite, emerging pollutants

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Authors: Sonia Ben Hamza, Sabra Habli, Nejla Mahjoub Said, Hervé Bournot, Georges Le Palec

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The distribution characteristics of pollutants released at different vertical inlet positions of an open channel are investigated with a three-dimensional numerical model. Pollutants are injected from time-dependent sources in a turbulent free surface flow. Numerical computations were carried out using ANSYS Fluent which is based on the finite volume approach. The air/water interface was modeled with the volume of the fluid method (VOF). By focusing on investigating the influences of flow on pollutants, it is found that pollutant released from the bottom position of the channel takes more time to disperse in the longitudinal direction of the flow in comparison with the case of pollutant released near the free surface. On the other hand, the pollutant released from the bottom position generates a vertical dispersion with decreased amplitude. These findings may assist in cost-effective scientific countermeasures to be taken for accident or planned pollutant discharged into a river.

Keywords: numerical simulation, pollutant release, turbulent free surface flow, VOF model

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Authors: Amina Adala, Nadra Debbache, Tahar Sehili

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Coordination polymers and uniformly {[Zn(II)(BIPY)(Pht)]n} (1), {[Zn (HYD)(Pht)]n} (2) (BIPY = 4,4’ bipyridine, Pht = terephtalic acid, HYD = 8-hydroxyquinoline) have been successfully synthesized by a hydrothermal process using aqueous zinc solution. The as-prepared compounds phases were characterized by X-ray diffraction (XRD), Fourier Transform Infrared spectroscopy, UV-visible spectroscopy, thermogravimetric analysis (TGA), and the electrochemistry study by the voltammetry cyclic. The results showed a crystalline phase for CP1 however, CP2 requires recrystallization; the FTIR showed the presence of characteristic bands of all ligands; besides that, TGA shows thermal stability up to 300°C. The electrochemistry study showed a good charge transfer between the ligands and Zn metal for the two components. UV-Vis measurement showed strong absorption in a wide range from UV to visible light with a band gap of 2.69 eV for CP1 and 2.56 eV for CP2, smaller than that of ZnO. This represents an alternative to using ZnO. The Ibuprofen IBP decomposition kinetics of 5.10⁻⁵ mol.L⁻¹ under solar and artificial light were studied for different irradiation conditions. Good photocatalytic properties were observed due to their high surface area.

Keywords: metal-organic frameworks, photocatalysis, photodegradation, organic pollutant, ibuprofen

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Authors: Mulugeta Gurum Gerechal

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Nowadays, the photocatalytic mechanism of water purification using nanoparticles has gained wider acceptance. For this purpose, the crystal form of N- TiO₂ and Ag-TiO₂ was prepared from TiCl₄, urea, NH₄OH, and AgNO₃ by sol-gel method and simple solid phase reaction followed by calcination at a temperature of 400°C for 4h at each. The synthesized photocatalysts were characterized using XRD, SEM, and UV-visible diffuse reflectance spectra. In the experiment, it was found that the absorption edge of N-TiO₂ was an efficient shift to visible light as compared to Ag-TiO₂. The XRD diffraction makes the particle size of N-TiO₂ smaller than Ag-TiO₂. The effect of catalyst loading and the effect of temperature on the photocatalytic efficiency of the prepared samples was tested using methylene blue as a target pollutant. The photocatalytic degradation efficiency of the catalysts for methylene blue was increased from 57.05 to 96.02% under solar radiation as the amount of the catalyst increased from 0.15 to 0.45 gram for N-TiO₂. Similarly, photocatalytic degradation of methylene blue was increased from 40.32 to 81.21% as the amount of Ag-TiO₂ increased from 0.05g to 0.1g. In addition, the photocatalytic degradation efficiency of the catalysts for the removal of methylene blue was increased from 58.00 to 98.00 and 47.00 to 81.21% under solar radiation as the calcination temperature of the catalyst increased from 300 to 500 for N-TiO₂ for Ag-TiO₂ 300 to 400⁰C. However, a further increase in catalyst loading and calcination temperature was found to decrease the degradation efficiency.

Keywords: photocatalysis, degradation, nanoparticles, catalyst loading, calcination, methylene blue

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Authors: S. V. Prabhakar Vattikuti, Chan Byon

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In this paper, we report a facile synthetic strategy of randomly disturbed Bi₂S₃ nanorods on WS₂ nanosheets, which are synthesized via a controlled hydrothermal method without surfactant under an inert atmosphere. We developed a simple hydrothermal method for the formation of heterostructured of Bi₂S₃/WS₂ with a large scale (>95%). The structural features, composition, and morphology were characterized by XRD, SEM-EDX, TEM, HRTEM, XPS, UV-vis spectroscopy, N₂ adsorption-desorption, and TG-DTA measurements. The heterostructured Bi₂S₃/WS₂ composite has significant photocatalytic efficiency toward the photodegradation of organic dye. The time-dependent UV-vis absorbance spectroscopy measurement was consistent with the enhanced photocatalytic degradation of rhodamine B (RhB) under visible light irradiation with the diminishing carrier recombination for the Bi₂S₃/WS₂ photocatalyst. Due to their marked synergistic effects, the supported Bi₂S₃ nanorods on WS₂ nanosheet heterostructures exhibit significant visible-light photocatalytic activity and stability for the degradation of RhB. A possible reaction mechanism is proposed for the Bi₂S₃/WS₂ composite.

Keywords: photocatalyst, heterostructures, transition metal disulfides, organic dye, nanorods

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Authors: Mulugeta Gurum Gerechal

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Nowadays, the photocatalytic mechanism of water purification using nanoparticles has gained wider acceptance. For this purpose, the Crystal form of N- TiO₂ and Ag-TiO₂ was prepared from TiCl₄, Urea, NH₄OH and AgNO₃ by sol-gel method and simple solid phase reaction followed by calcination at a temperature of 400 °C for 4h at each. The synthesized photocatalysts were characterized using XRD, SEM and UV-visible diffuse reflectance spectra. In the experiment, it was found that the absorption edge of N-TiO₂ was a well efficient shift to visible light as compared to Ag-TiO₂. The XRD diffraction makes the particle size of N-TiO₂ smaller than Ag-TiO₂. The effect of catalyst loading and the effect of temperature on the photocatalytic efficiency of the prepared samples was tested using methylene blue as a target pollutant. The photocatalytic degradation efficiency of the catalysts for methylene blue was increased from 57.05 to 96.02% under solar radiation as the amount of the catalyst increased from 0.15 to 0.45 gram for N-TiO₂. Similarly, photocatalytic degradation of methylene blue was increased from 40.32 to 81.21% as the amount of Ag-TiO₂ increased from 0.05g to 0.1g. In addition, the photocatalytic degradation efficiency of the catalysts for the removal of methylene blue was increased from 58.00 to 98.00 and 47.00 to 81.21 % under solar radiation as the calcination temperature of the catalyst increased from 300 to 500 for N-TiO₂ for Ag-TiO₂ 300 to 4000C. However, a further increase in catalyst loading and calcination temperature was found to decrease the degradation efficiency.

Keywords: photocatalysis, degradation, nanoparticles, catalyst loading, calcination and methylene blue

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Authors: Boonsiri Dandumrongsin, Halis Simsek, Chaiwat Rongsayamanont

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Dissolved organic nitrogen (DON) is known as one of the persistence nitrogenous pollutant being originated from secondary treated effluent of municipal sewage treatment plant. However, effect of key system operating condition on the fate and behavior of residual DON in the treated effluent is still not known. This study aims to investigate effect of organic loading rate (OLR) on the residual level of DON in the biofilm reactor effluent. Synthetic municipal wastewater was fed into moving bed biofilm reactors at OLR of 1.6x10-3 and 3.2x10-3 kg SCOD/m3-d. The results showed higher organic removal efficiency was found in the reactor operating at higher OLR. However, DON was observed at higher value in the effluent of the higher OLR reactor than that of the lower OLR reactor evidencing a clear influence of OLR on the residual DON level in the treated effluent of the biofilm reactors. It is possible that the lower DON being observed in the reactor at lower OLR is likely to be a result of providing the microbe with the additional period for utilizing the refractory DON molecules during operation at lower organic loading. All the experiments were repeated using raw wastewaters and similar trend was obtained.

Keywords: dissolved organic nitrogen, hydraulic retention time, moving bed biofilm reactor, soluble microbial products

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Authors: S. Shanthi

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Catalyzed oxidation processes show extraordinary guarantee for application in numerous wastewater treatment ranges. Advanced oxidation processes are emerging innovation that might be utilized for particular objectives in wastewater treatment. This research work provides a solution for removal a refractory organic compound 2,4-dichlorophenoxyaceticacid a common water pollutant. All studies were done in batch mode in a constantly stirred reactor. Alternative ozonation processes catalysed by transition metals or granular activated carbon have been investigated for degradation of organics. Catalytic ozonation under study are homogeneous catalytic ozonation, which is based on ozone activation by transition metal ions present in aqueous solution, and secondly as heterogeneous catalytic ozonation in the presence of Granular Activated Carbon (GAC). The present studies reveal that heterogeneous catalytic ozonation using GAC favour the ozonation of 2,4-dichlorophenoxyaceticacid by increasing the rate of ozonation and a much higher degradation of substrates were obtained in a given time. Be that it may, Fe2+and Fe3+ ions decreased the rate of degradation of 2,4-dichlorophenoxyaceticacid indicating that it acts as a negative catalyst. In case of heterogeneous catalytic ozonation using GAC catalyst it was found that during the initial 5 minutes of contact solution concentration decreased significantly as the pollutants were adsorbed initially. Thereafter the substrate started getting oxidized and ozonation became a dominates the treatment process. The exhausted GAC was found to be regenerated in situ. The percentage reduction of the substrate was maximum achieved in minimum possible time when GAC catalyst is employed.

Keywords: ozonation, homogeneous catalysis, heterogeneous catalysis, granular activated carbon

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Authors: Gabriela Rivadeneyra-Romero, Claudia del C. Gutierrez Torres, Sergio A. Martinez-Delgadillo, Victor X. Mendoza-Escamilla, Alejandro Alonzo-Garcia

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Ultrasonic degradation is currently being used in sonochemical reactors to degrade pollutant compounds from aqueous media, as emerging contaminants (e.g. pharmaceuticals, drugs and personal care products.) because they can produce possible ecological impacts on the environment. For this reason, it is important to develop appropriate water and wastewater treatments able to reduce pollution and increase reuse. Pollutants such as textile dyes, aromatic and phenolic compounds, cholorobenzene, bisphenol-A and carboxylic acid and other organic pollutants, can be removed from wastewaters by sonochemical oxidation. The effect on the removal of pollutants depends on the type of the ultrasonic frequency used; however, not much studies have been done related to the behavior of the fluid into the sonoreactors operated at different ultrasonic frequencies. Based on the above, it is necessary to study the hydrodynamic behavior of the liquid generated by the ultrasonic irradiation to design efficient sonoreactors to reduce treatment times and costs. In this work, it was studied the hydrodynamic behavior of the fluid in sonochemical reactors at different frequencies (250 kHz, 500 kHz and 1000 kHz). The performances of the sonoreactors at those frequencies were simulated using computational fluid dynamics (CFD). Due to there is great sound speed gradient between piezoelectric and fluid, k-e models were used. Piezoelectric was defined as a vibration surface, to evaluate the different frequencies effect on the fluid into sonochemical reactor. Structured hexahedral cells were used to mesh the computational liquid domain, and fine triangular cells were used to mesh the piezoelectric transducers. Unsteady state conditions were used in the solver. Estimation of the dissipation rate, flow field velocities, Reynolds stress and turbulent quantities were evaluated by CFD and 2D-PIV measurements. Test results show that there is no necessary correlation between an increase of the ultrasonic frequency and the pollutant degradation, moreover, the reactor geometry and power density are important factors that should be considered in the sonochemical reactor design.

Keywords: CFD, reactor, ultrasound, wastewater

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Authors: Marius Sebastian Secula, Andreea Vajda, Benoit Cagnon, Ioan Mamaliga

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One of the most important classes of pollutants is represented by dyes. The synthetic character and complex molecular structure make them more stable and difficult to be biodegraded in water. The treatment of wastewaters containing dyes in order to separate/degrade dyes is of major importance. Various techniques have been employed to remove and/or degrade dyes in water. Advanced oxidation processes (AOPs) are known as among the most efficient ones towards dye degradation. The aim of this work is to investigate the efficiency of a cheap Iron-impregnated activated carbon Fenton-like catalyst in order to degrade organic compounds in aqueous solutions. In the presented study an anionic dye, Indigo Carmine, is considered as a model pollutant. Various AOPs are evaluated for the degradation of Indigo Carmine to establish the effect of the prepared catalyst. It was found that the Iron(II)-embedded activated carbon composite enhances significantly the degradation process of Indigo Carmine. Using the wet impregnation procedure, 5 g of L27 AC material were contacted with Fe(II) solutions of FeSO4 precursor at a theoretical iron content in the resulted composite of 1 %. The L27 AC was impregnated for 3h at 45°C, then filtered, washed several times with water and ethanol and dried at 55 °C for 24 h. Thermogravimetric analysis, Fourier transform infrared, X-ray diffraction, and transmission electron microscopy were employed to investigate the structural, textural, and micromorphology of the catalyst. Total iron content in the obtained composites and iron leakage were determined by spectrophotometric method using phenantroline. Photo-catalytic tests were performed using an UV - Consulting Peschl Laboratory Reactor System. UV light irradiation tests were carried out to determine the performance of the prepared Iron-impregnated composite towards the degradation of Indigo Carmine in aqueous solution using different conditions (17 W UV lamps, with and without in-situ generation of O3; different concentrations of H2O2, different initial concentrations of Indigo Carmine, different values of pH, different doses of NH4-OH enhancer). The photocatalytic tests were performed after the adsorption equilibrium has been established. The obtained results emphasize an enhancement of Indigo Carmine degradation in case of the heterogeneous photo-Fenton process conducted with an O3 generating UV lamp in the presence of hydrogen peroxide. The investigated process obeys the pseudo-first order kinetics. The photo-Fenton degradation of IC was tested at different values of initial concentration. The obtained results emphasize an enhancement of Indigo Carmine degradation in case of the heterogeneous photo-Fenton process conducted with an O3 generating UV lamp in the presence of hydrogen peroxide. Acknowledgments: This work was supported by a grant of the Romanian National Authority for Scientific Research and Innovation, CNCS - UEFISCDI, project number PN-II-RU-TE-2014-4-0405.

Keywords: photodegradation, heterogeneous Fenton, anionic dye, carbonaceous composite, screening factorial design

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Authors: Yousef M. Al-Roomi, Kaneez Fatema Hussain

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This work evaluates the thermal degradation kinetic parameters of CaSO₄-complex isolated after the inhibition effect of maleic-anhydride based polymer (YMR-polymers). Pyrolysis experiments were carried out at four heating rates (5, 10, 15 and 20°C/min). Several analytical model-free methods were used to determine the kinetic parameters, including Friedman, Coats and Redfern, Kissinger, Flynn-Wall-Ozawa and Kissinger-Akahira–Sunose methods. The Criado model fitting method based on real mechanism followed in thermal degradation of the complex has been applied to explain the degradation mechanism of CaSO₄-complex. In addition, a simple dynamic model was proposed over two temperature ranges for successive decomposition of CaSO₄-complex which has a combination of organic and inorganic part (adsorbed polymer + CaSO₄.2H₂O scale). The model developed enabled the assessment of pre-exponential factor (A) and apparent activation-energy (Eₐ) for both stages independently using a mathematical developed expression based on an integral solution. The unique reaction mechanism approach applied in this study showed that (Eₐ₁-160.5 kJ/mole) for organic decomposition (adsorbed polymer stage-I) has been lower than Eₐ₂-388 kJ/mole for the CaSO₄ decomposition (inorganic stage-II). Further adsorbed YMR-antiscalant not only reduced the decomposition temperature of CaSO₄-complex compared to CaSO₄-blank (CaSO₄.2H₂O scales in the absence of YMR-polymer) but also distorted the crystal lattice of the organic complex of CaSO₄ precipitates, destroying their compact and regular crystal structures observed from XRD and SEM studies.

Keywords: CaSO₄-complex, maleic-anhydride polymers, thermal degradation kinetics and mechanism, XRD and SEM studies

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Authors: Akanimo Emene, Mark D. Ogden, Robert Edyvean

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Adsorption is a low cost, efficient and economically viable wastewater treatment process. Utilization of this treatment process has not been fully applied due to the complex and not fully understood nature of the adsorption system. To optimize its process is to choose a sufficient adsorbent and to study further the experimental parameters that influence the adsorption design system. Chemically modified adsorbent, Luffa cylindrica, was used to adsorb heavy metal ions and an organic pollutant, methylene blue, from aqueous environmental solution at varying experimental conditions. Experimental factors, adsorption time, initial metal ion or organic pollutant concentration, ionic strength, and pH of solution were studied. The experimental data were analyzed with kinetic and isotherm models. The antagonistic effect of the methylene and some heavy metal ions were recorded. An understanding of the use of this treated Luffa cylindrica for the removal of these toxic substances will establish and improve the commercial application of the adsorption process in treatment of contaminated waters.

Keywords: adsorption, heavy metal ions, Luffa cylindrica, wastewater treatment

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Authors: M. Tabatabaee, R. Mohebat, M. Baranian

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Textile industries produce large volumes of colored dye effluents which are toxic and non-biodegradable. Earlier studies have shown that a wide range of organic substrates can be completely photo mineralized in the presence of photocatalysts and oxidant agents. ZnO and TiO2 are important photocatalysts with high catalytic activity that have attracted much research attention. Zinc sulfide is one of the semiconductor nanomaterials that can be used for the production of optical sensitizers, photocatalysts, electroluminescent materials, optical sensors and for solar energy conversion. The synthesis of ZnS nanoparticles has been tried by various methods and sulfide sources. Elementary sulfur powder, H2S or Na2S are used as sulfide sources for synthesis of ZnS nano particles. Recently, solar energy is has been successfully used for photocatalytic degradation of dye pollutant. Studies have shown that the use of metal oxides or sulfides with ZnO or TiO2 can significantly enhance the photocatalytic activity of them. In this research, Nano-sized zinc sulfide was synthesized successfully by a simple method using thioasetamide as sulfide source in the presence of polyethylene glycol (PEG 2000). X-ray diffraction (XRD) spectroscopy scanning electron microscope (SEM) was used to characterize the structure and morphology synthesized powder. The effect of photocatalytic activity of prepared ZnS and ZnS/ZnO, on degradation of direct Black19 under UV and sunlight irradiation was investigated. The effects of various parameters such as amount of photocatalyst, pH, initial dye concentration and irradiation time on decolorization rate were systematically investigated. Results show that more than 80% of 500 mgL-1 of dye decolorized in 60-min reaction time under UV and solar irradiation in the presence of ZnS nanoparticles. Whereas, mixed ZnS/ZnO (50%) can decolorize more than 80% of dye in the same conditions.

Keywords: zinc sulfide, nano articles, photodegradation, solar light

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Authors: Hong Zhang

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Photocatalytic degradation is an appealing process to remove organic contaminants from industrial wastewater, but usually impeded by less effective photocatalysts. Here, we successfully synthesized Ag doped La₂Ti₂O₇ via a simple sol-gel route for photocatalytic methyl orange (MO) degradation. Their crystal structures, morphology, surface area and optical absorption activity were systematically characterized by X-ray diffraction, scanning electron microscope, BET N₂ adsorption-desorption study, and UV-vis diffuse reflectance spectra. The photocatalytic activity was evaluated by MO photodegradation under a 300 W xenon lamp. The results indicate that the doping of Ag has effectively narrowed the band gap, increased the specific area of La2Ti2O7, and supressed the recombination of photogenerated carriers. Compared with the pristine La₂Ti₂O₇, La₁.₉Ag₀.₁Ti₂O₇-δ revealed a superior performance for MO degradation with a degradation rate of 97% in only 60 min. Also, the pseudo-first order kinetic constant for La₁.₉Ag₀.₁Ti₂O₇-δ is ~ 11 times higher than that of undoped sample. The outstanding performance of Ag modified La₂Ti₂O₇ is probably attributed to the integrated factors. Active species trapping experiments indicated that h+ plays a critical role in MO degradation, while •O₂− has slight effect on the photocatalytic activity and the function of •OH can almost be neglected.

Keywords: Ag doped La₂Ti₂O₇, methyl orange, photodegradation, surface plasmon resonance

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Authors: Vrinda P. S. Borker

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Major water pollutants are dyes from effluents of industries. Different methods have been tried to degrade or treat the effluent before it is left to the environment. In order to understand the degradation process and later apply it to effluents, solar degradation study of methylene blue (MB) and methyl red (MR), the model dyes was carried out in the presence of photo-catalysts, the oxides of cobalt oxide Co₃O₄, and copper doped cobalt oxides (Co₀.₉Cu₀.₁)₃O₄ and (Co₀.₉₅Cu₀.₀₅)₃O₄. They were prepared from oxalate complex and hydrazinated oxalate complex of cobalt as well as mix metals, copper, and cobalt. The complexes were synthesized and characterized by FTIR. Complexes were decomposed to form oxides and were characterized by XRD. They were found to be monophasic. Solar degradation of MR and MB was carried out in presence of these oxides in acidic and basic medium. Degradation was faster in alkaline medium in the presence of Co₃O₄ obtained from hydrazinated oxalate. Doping of nanomaterial oxides modifies their characteristics. Doped cobalt oxides are found to photo-decolourise MR in alkaline media efficiently. In the absence of photocatalyst, solar degradation of alkaline MR does not occur. In acidic medium, MR is minimally decolorized even in the presence of photocatalysts. The industrial textile effluent contains chemicals like NaCl and Na₂CO₃ along with the unabsorbed dye. It is reported that these two chemicals hamper the degradation of dye. The chemicals like K₂S₂O₈ and H₂O₂ are reported to enhance degradation. The solar degradation study of MB in presence of photocatalyst (Co₀.₉Cu₀.₁)₃O₄ and these four chemicals reveals that presence of K₂S₂O₈ and H₂O₂ enhances degradation. It proves that H₂O₂ generates hydroxyl ions required for degradation of dye and the sulphate anion radical being strong oxidant attacks dye molecules leading to its fragmentation rapidly. Thus addition of K₂S₂O₈ and H₂O₂ during solar degradation in presence of (Co₀.₉Cu₀.₁)₃O₄ helps to break the organic moiety efficiently.

Keywords: cobalt oxides, Cu-doped cobalt oxides, H₂O₂ in dye degradation, photo-catalyst, solar dye degradation

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Authors: Ljerka Kratofil Krehula, Martina Perlog, Jasmina Stjepanović, Vanja Gilja, Marijana Kraljić Roković, Zlata Hrnjak-Murgić

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The composite preparation of titanium dioxide and zinc oxide photocatalysts with the conductive polymers gives the opportunity to carry out the catalysis reactions not only under UV light but also under visible light. Such processes may efficiently use sunlight in degradation of different organic pollutants and present new design for wastewater treatment. The paper presents the preparation procedure, material characteristics and photocatalytic efficiency of polypyrrole/titanium dioxide and polypyrrole/zinc oxide composites (PPy/TiO2 and PPy/ZnO). The obtained composite samples were characterized by Fourier transform infrared spectroscopy (FTIR), UV-Vis spectroscopy and thermogravimetric analysis (TGA). The photocatalytic efficiency of the samples was determined following the decomposition of Acid Blue 25 dye (AB 25) under UV and visible light by UV/Vis spectroscopy. The efficiency of degradation is determined by total organic carbon content (TOC) after photocatalysis processes. The results show enhanced photocatalytic efficiency of the samples under visible light, so the prepared composite samples are recognized as efficient catalysts in degradation process of AB 25 dye. It can be concluded that the preparation of TiO2 or ZnO composites with PPy can serve as a very efficient method for the improvement of TiO2 and ZnO photocatalytic performance under visible light.

Keywords: composite, photocatalysis, polypyrrole, titanium dioxide, zinc oxide

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Authors: M. S. Abd El-Sadek, M. A. Omar, Gharib M. Taha

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In recent years, photocatalytic degradation of various kinds of organic and inorganic pollutants using semiconductor powders as photocatalysts has been extensively studied. Owing to its relatively high photocatalytic activity, biological and chemical stability, low cost, nonpoisonous and long stable life, Tin oxide materials have been widely used as catalysts in chemical reactions, including synthesis of vinyl ketone, oxidation of methanol and so on. Tin oxide (SnO₂), with a rutile-type crystalline structure, is an n-type wide band gap (3.6 eV) semiconductor that presents a proper combination of chemical, electronic and optical properties that make it advantageous in several applications. In the present work, SnO₂ nanoparticles were synthesized at room temperature by the sol-gel process and thermohydrolysis of SnCl₂ in isopropanol by controlling the crystallite size through calculations. The synthesized nanoparticles were identified by using XRD analysis, TEM, FT-IR, and Uv-Visible spectroscopic techniques. The crystalline structure and grain size of the synthesized samples were analyzed by X-Ray diffraction analysis (XRD) and the XRD patterns confirmed the presence of tetragonal phase SnO₂. In this study, Methylene blue degradation was tested by using SnO₂ nanoparticles (at different calculations temperatures) as a photocatalyst under sunlight as a source of irradiation. The results showed that the highest percentage of degradation of Methylene blue dye was obtained by using SnO₂ photocatalyst at calculations temperature 800 ᵒC. The operational parameters were investigated to be optimized to the best conditions which result in complete removal of organic pollutants from aqueous solution. It was found that the degradation of dyes depends on several parameters such as irradiation time, initial dye concentration, the dose of the catalyst and the presence of metals such as silver as a dopant and its concentration. Percent degradation was increased with irradiation time. The degradation efficiency decreased as the initial concentration of the dye increased. The degradation efficiency increased as the dose of the catalyst increased to a certain level and by further increasing the SnO₂ photocatalyst dose, the degradation efficiency is decreased. The best degradation efficiency on which obtained from pure SnO₂ compared with SnO₂ which doped by different percentage of Ag.

Keywords: SnO₂ nanoparticles, a sol-gel method, photocatalytic applications, methylene blue, degradation efficiency

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Authors: Sangram Shamrao Patil, Hara Mohan Jena

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Phthalates are among the most common organic pollutant since they have become widespread in the environment and found in sediments, natural waters, soils, plants, landfill leachates, biota including human tissue and aquatic organisms. Diethyl phthalate (DEP) is a low molecular weight phthalate which has wide applications as plasticizer and become a major cause of environmental pollution. Environmental protection agency (EPA) listed DEP as priority pollutant because of its toxicity and they recommended human health ambient water quality criterion for diethyl phthalate (DEP) as 4 mg/l. Therefore, wastes containing phthalates require proper treatment before being discharged into the environment. Biodegradation is attractive and efficient treatment method as it is cost effective and produces non-toxic end products. In the present study, a DEP degrading aerobic bacterium was isolated from soil contaminated with plastic industry wastewater. Morphological and biochemical characteristics of isolate were performed. 16S rRNA sequencing and phylogenetic analysis of isolate was carried out and it was identified as Empedobacter brevis. Isolate has been found to tolerate up to 1650 mg/l of DEP. This study will be significant for exploring an application of microbes for remediation of phthalates and development of a suitable bioreactor.

Keywords: diethyl phthalate, plasticizer, pollutant, biodegradation

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Authors: H. Boucheloukh, N. Aoun, S. Rouissa, T. Sehili, F. Parrino, V. Loddo

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Photocatalysis has made a revolution in wastewater treatment and the elimination of persistent organic pollutants. This process is based on the use of semiconductors as photocatalysts. In this study, nickel ferrite spinel (NiFe2O4) nanoparticles were successfully synthesized by the sol-gel route. The structural, morphological, elemental composition, chemical state, particle size, optical and electrochemical characterizations using powder X-ray diffraction (P-XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy(SEM), energy-dispersive X-ray spectroscopy (EDAX ). We tested the prepared NiFe2O4(NPS)by monitoring the degradation of Rose Bengal (RB) dye in an aqueous solution under direct sunlight irradiation. The effects of catalyst dosage and dye concentration were also considered for the effective degradation of RB dye. The optimum catalyst dosage and concentration of dye were found to be 1 g/L and 10 μM, respectively. A maximum of 80% photocatalytic degradation efficiency (DE%) was achieved at 120 min of direct sunlight irradiation.

Keywords: Rose Bengal, Nickelate, photocatalysis, irradiation

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Authors: S. K. Gali

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Spentwash, An effluent of distillery is an environmental pollutant because of its high load of pollutants (pH: 2-4; BOD>40,000 mg/l, COD>100,000mg/l and TDS >70,000mg/l). But However, after subjecting it to primary treatment (bio-methanation), Its pollutant load gets drastically reduced (pH: 7.5-8.5, BOD<10,000 mg/l) and could be disposed off safely as a source of organic matter and plant nutrients for crop production. With the consent of State Pollution Control Board, the distilleries in Karnataka are taking up ‘one time controlled land application’ of bio-methanated spentwash in farmers’ fields. A monitoring study was undertaken in Belgaum district of Karnataka State with an objective of studying the effect of land application of bio-methanated spent wash of a distillery on soil properties and crop growth. The treated spentwash was applied uniformly to the fallow dry lands in different farmers’ fields during summer, 2012 at recommended rate (based on nitrogen requirement of crops). The application was made at least a fortnight before sowing/planting operations. The analysis of soils collected before land application of spentwash and after harvest of crops revealed that there was no adverse effect of applied spentwash on soil characteristics. A slight build up in soluble salts was observed but, however all the soils recorded EC of less than 2.0 dSm-1. An increase in soil organic carbon (SOC) and available nitrogen (N) by about 10 to 30 % was observed in the spentwash applied soils. The presence of good amount of biodegradable organics in the treated spentwash (BOD of 6550 mg/l) contributed for increase in SOC and N. A substantial build up in available potassium (K) status (50 to 200%) was observed due to spentwash application. This was attributed to the high K content in spentwash (6950 mg/l). The growth of crops in the spentwash applied fields was higher and farmers could get nearly 10 to 20 per cent higher yields, especially in sugarcane and corn. The analysis of ground water samples showed that the quality of water was not affected due to land application of treated spentwash. Apart from realizing higher crop yields, the farmers were able to save money on N and K fertilisers as the applied spentwash met the crop requirement. Hence, it could be concluded that the bio-methanated distillery spentwash can be gainfully utilized in crop production without polluting the environment.

Keywords: bio-methanation, pollutant, potassium status, soil organic carbon

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Authors: Bekan Bogale, Tsegaye Girma Asere, Tilahun Yai, Fekadu Melak

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Aims: To study photocatalytic degradation of methylene blue dye on cuprous oxide/graphene nanocomposite. Background: Cuprous oxide (Cu2O) nanoparticles are among the metal oxides that demonstrated photocatalytic activity. However, the stability of Cu2O nanoparticles due to the fast recombination rate of electron/hole pairs remains a significant challenge in their photocatalytic applications. This, in turn, leads to mismatching of the effective bandgap separation, tending to reduce the photocatalytic activity of the desired organic waste (MB). To overcome these limitations, graphene has been combined with cuprous oxides, resulting in cuprous oxide/graphene nanocomposite as a promising photocatalyst. Objective: In this study, Cu2O/graphene nanocomposite was synthesized and evaluated for its photocatalytic performance of methylene blue (MB) dye degradation. Method: Cu2O/graphene nanocomposites were synthesized from graphite powder and copper nitrate using the facile sol-gel method. Batch experiments have been conducted to assess the applications of the nanocomposites for MB degradation. Parameters such as contact time, catalyst dosage, and pH of the solution were optimized for maximum MB degradation. The prepared nanocomposites were characterized by using UV-Vis, FTIR, XRD, and SEM. The photocatalytic performance of Cu2O/graphene nanocomposites was compared against Cu2O nanoparticles for cationic MB dye degradation. Results: Cu2O/graphene nanocomposite exhibits higher photocatalytic activity for MB degradation (with a degradation efficiency of 94%) than pure Cu2O nanoparticles (67%). This has been accomplished after 180 min of irradiation under visible light. The kinetics of MB degradation by Cu2O/graphene composites can be demonstrated by the second-order kinetic model. The synthesized nanocomposite can be used for more than three cycles of photocatalytic MB degradation. Conclusion: This work indicated new insights into Cu2O/graphene nanocomposite as high-performance in photocatalysis to degrade MB, playing a great role in environmental protection in relation to MB dye.

Keywords: methylene blue, photocatalysis, cuprous oxide, graphene nanocomposite

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Authors: Shivam Dubey, Vinit Srivastava, Abhay Singh Thakur, Rahul Vaish

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The presence of organic dyes in water is a critical issue that poses a significant threat to the environment and human health. We have investigated the use of corona discharge as a potential method for degrading organic dyes in water. Methylene Blue dye was exposed to corona discharge, and its photo-absorbance was measured over time to determine the extent of degradation. The results depicted a decreased absorbance for the dye and the loss of the characteristic colour of methylene blue. The effects of various parameters, including current, voltage, gas phase, salinity, and electrode spacing, on the reaction rates, were investigated. The highest reaction rates were observed at the highest current and voltage (up to 10kV), lowest salinity, smallest electrode spacing, and an environment containing enhanced levels of oxygen. These findings have possible applications for science education curriculum. By investigating the use of corona discharge for destroying organic dyes, we can provide students with a practical application of scientific principles that they can apply to real-world problems. This research can demonstrate the importance of understanding the chemical and physical properties of organic dyes and the effects of corona discharge on their degradation and provide a holistic understanding of the applications of scientific research. Moreover, our study also emphasizes the importance of considering the various parameters that can affect reaction rates. By investigating the effects of current, voltage, matter phase, salinity, and electrode spacing, we can provide students with an opportunity to learn about the importance of experimental design and how to evade constraints that can limit meaningful results. In conclusion, this study has the potential to provide valuable insights into the use of corona discharge for destroying organic dyes in water and has significant implications for science education. By highlighting the practical applications of scientific principles, experimental design, and the importance of considering various parameters, this research can help students develop critical thinking skills and prepare them for future careers in science and engineering.

Keywords: dye degradation, corona discharge, science education, hands-on learning, chemical education

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Authors: Thanaa Abdel Moghny, Mohamed Keshawy, Mahmoud Fathy, Abdul-Raheim M. Abdul-Raheim, Khalid I. Kabel, Ahmed F. El-Kafrawy, Mahmoud Ahmed Mousa, Ahmed E. Awadallah

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Ecological pollution is of great concern for human health and the environment. Numerous organic and inorganic pollutants usually discharged into the water caused carcinogenic or toxic effect for human and different life form. In this respect, this work aims to treat water contaminated by organic and inorganic waste using sorbent based on polystyrene. Therefore, two different series of adsorbent material were prepared; the first one included the preparation of polymeric sorbent from the reaction of styrene acrylate ester and alkyl acrylate. The second series involved syntheses of composite ion exchange resins of waste polystyrene and   amorphous carbon thin film (WPS/ACTF) by solvent evaporation using micro emulsion polymerization. The produced ACTF/WPS nanocomposite was sulfonated to produce cation exchange resins ACTF/WPSS nanocomposite. The sorbents of the first series were characterized using FTIR, ¹H NMR, and gel permeation chromatography. The thermal properties of the cross-linked sorbents were investigated using thermogravimetric analysis, and the morphology was characterized by scanning electron microscope (SEM). The removal of organic pollutant was determined through absorption tests in a various organic solvent. The chemical and crystalline structure of nanocomposite of second series has been proven by studies of FTIR spectrum, X-rays, thermal analysis, SEM and TEM analysis to study morphology of resins and ACTF that assembled with polystyrene chain. It is found that the composite resins ACTF/WPSS are thermally stable and show higher chemical stability than ion exchange WPSS resins. The composite resin was evaluated for calcium hardness removal. The result is evident that the ACTF/WPSS composite has more prominent inorganic pollutant removal than WPSS resin. So, we recommend the using of nanocomposite resin as new potential applications for water treatment process.

Keywords: nanocomposite, sorbent materials, waste water, waste polystyrene

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Authors: Janeth Chepkemoi, Richard Onwonga, Noel Templer, Elkana Kipkoech, Angela Gitau

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Conventional agriculture is one of the leading causes of land degradation, threatening the sustainability of food production. Organic farming promotes practices that have the potential of feeding the world while also promoting ecological health. A study was therefore carried out with the aim of conceptualizing how such farming systems are contributing to ecological health in Trans Nzoia County. 71 farmers were interviewed and data was collected on parameters such as land preparation, agroforestry, soil fertility management, soil and water conservation, and pests and diseases. A soil sample was also collected from each farm for laboratory analysis. Data collected were analyzed using Microsoft Excel and SPSS version 21. Results showed that 66% of the respondents practiced organic farming whereas 34% practiced conventional farming. Intercropping and crop rotations were the most common cropping systems and the most preferred land preparation tools among both organic and conventional farmers were tractors and hand hoes. Organic farms fared better in agroforestry, organic soil amendments, land and water conservation, and soil chemical properties. Pests and disease, however, affected organic farms more than conventional. The average nitrogen (%), K (Cmol/ kg and P (ppm) of organic soils were 0.26, 0.7 and 26.18 respectively, conventional soils were 0.21, 0.66 and 22.85. Soil organic carbon content of organic farms averaged a higher percentage of 2.07% as compared to 1.91 for the conventional. In conclusion, most farmers in Trans Nzoia County had transitioned into ecologically friendly farming practices that improved the quality and health of the soil and therefore promoted its sustainability.

Keywords: organic farming, conventional farming, ecological health, soil health

Procedia PDF Downloads 124