Search results for: advanced oxidation processes

Authors: Loai Ben Naji, Osama M. Ibrahim, Khaled J. Al-Fadhalah

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The objective of this paper is to investigate the formation and adhesion of a protective aluminum-oxide (Al₂O₃, alumina) layer on the surface of Iron-Chromium-Aluminum Alloy (Fe-Cr-Al) sintered-metal-fibers. The oxide-scale layer was developed via multi-stage thermal oxidation at 930 ^oC for 1 hour, followed by 1 hour at 960 ^oC, and finally at 990 ^oC for 2 hours. Scanning Electron Microscope (SEM) images show that the multi-stage thermal oxidation resulted in the formation of predominantly Al₂O₃ platelets-like and whiskers. SEM images also reveal non-uniform oxide-scale growth on the surface of the fibers. Furthermore, peeling/spalling of the alumina protective layer occurred after minimum handling, which indicates weak adhesion forces between the protective layer and the base metal alloy.  Energy Dispersive Spectroscopy (EDS) analysis of the heat-treated Fe-Cr-Al sintered-metal-fibers confirmed the high aluminum content on the surface of the protective layer, and the low aluminum content on the exposed base metal alloy surface. In conclusion, the failure of the oxide-scale protective layer exposes the base metal alloy to further oxidation, and the fragile non-uniform oxide-scale is not suitable as a support for catalysts.

Keywords: high-temperature oxidation, iron-chromium-aluminum alloy, alumina protective layer, sintered-metal-fibers

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Authors: A. Kabir, D. Boulainine, I. Bouanane, N. Benslim, B. Boudjema, C. Sedrati

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SnO₂ is an n-type semiconductor with a direct gap of about 3.6 eV. It is largely used in several domains such as nanocrystalline photovoltaic cells. Due to its interesting physic-chemical properties, this material was elaborated in thin film forms using different deposition techniques. It was found that SnO₂ properties were directly affected by the deposition method parameters. In this work, the RGTO method (Rheotaxial Growth and Thermal Oxidation) was used to deposit elaborate SnO₂ thin films. This technique consists on thermal oxidation of the Sn films deposited onto a substrate heated to a temperature close to Sn melting point (232°C). Such process allows the preparation of high porosity tin oxide films which are very suitable for the gas sensing. The films structural, morphological and optical properties pre and post thermal oxidation were studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), UV-Visible spectroscopy and Fourier transform infrared spectroscopy (FTIR) respectively. XRD patterns showed a polycrystalline structure of the cassiterite phase of SnO₂. The grain growth was found affected by the oxidation temperature. This grain size evolution was confronted to existing grain growth models in order to understand the growth mechanism. From SEM images, the as deposited Sn film was formed of difference diameter spherical agglomerations. As a function of the oxidation temperature, these spherical agglomerations shape changed due to the introduction of oxygen ions. The deformed spheres started to interconnect by forming bridges between them. The volume porosity, determined from the UV-Visible reflexion spectra, Changes as a function of the oxidation temperature. The variation of the crystalline fraction, determined from FTIR spectra, correlated with the variation of both the grain size and the volume porosity.

Keywords: tin oxide, RGTO, grain growth, volume porosity, crystalline fraction

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Authors: Ahmed Ait Hou

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The wing leading edge and nose cone of the space shuttle are fabricated from a reinforced carbon/carbon material. This material attains its durability from a diffusion coating of silicon carbide (SiC) and a glass sealant. During re-entry into the atmosphere, this material is subject to an oxidizing high-temperature environment. The use of thermochemical calculations resulting at the HSC CHEMISTRY software and its database allows us to interpret the phenomena of oxidation and chloridation observed on the wing leading edge and nose cone of the space shuttle during its mission in space. First study is the monitoring of the oxidation reaction of SiC. It has been demonstrated that thermal oxidation of the SiC gives the two compounds SiO₂(s) and CO(g). In the extreme conditions of very low oxygen partial pressures and high temperatures, there is a reaction between SiC and SiO₂, leading to SiO(g) and CO(g). We had represented the phase stability diagram of Si-C-O system calculated by the use of the HSC Chemistry at 1300°C. The principal characteristic of this diagram of predominance is the line of SiC + SiO₂ coexistence. Second study is the monitoring of the chloridation reaction of SiC. The other problem encountered in addition to oxidation is the phenomenon of chloridation due to the presence of NaCl. Indeed, after many missions, the leading edge wing surfaces have exhibited small pinholes. We have used the HSC Chemistry database to analyze these various reactions. Our calculations concorde with the phenomena we announced in research work resulting in NASA LEWIS Research center.

Keywords: thermochchemicals calculations, HSC software, oxidation and chloridation, wings in space

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Authors: Deniz Sahin

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Growing concern for the presence and contamination of heavy metals in our water supplies has steadily increased over the last few years. A number of specialized technologies including precipitation, coagulation/flocculation, ion exchange, cementation, electrochemical operations, have been developed for the removal of heavy metals from wastewater. However, these technologies have many limitations in the application, such as high cost, low separation efficiency, Recently, numerous approaches have been investigated to overcome these difficulties and membrane filtration, advanced oxidation technologies (AOPs), and UV irradiation etc. are sufficiently developed to be considered as alternative treatments. Many factors come into play when selecting wastewater treatment technology, such as type of wastewater, operating conditions, economics etc. This study describes these various treatment technologies employed for heavy metal removal. Advantages and disadvantages of these technologies are also compared to highlight their current limitations and future research needs. For example, we investigated the applicability of the ultrafiltration technology for treating of heavy metal ions (e.g., Cu(II), Pb(II), Cd(II), Zn(II)) from synthetic wastewater solutions. Results shown that complete removal of metal ions, could be achieved.

Keywords: heavy metal, treatment methodologies, water, water treatment

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Authors: Reda Dzingelevičienė, Vytautas Abromaitis, Nerijus Dzingelevičius, Kęstutis Baranauskis, Saulius Raugelė, Malgorzata Mlynska-Szultka, Sergej Suzdalev, Reza Pashaei, Sajjad Abbasi, Boguslaw Buszewski

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A unique hybrid technology was developed for the removal of COVID-19 specific contaminants from wastewater. Reactor testing was performed using model water samples contaminated with COVID-19 pharmaceuticals and microplastics. Different hydraulic retention times, concentrations of pollutants and dissolved ozone were tested. Liquid Chromatography-Mass Spectrometry, solid phase extraction, surface area and porosity, analytical tools were used to monitor the treatment efficiency and remaining sorption capacity of the spent adsorbent. The combination of advanced oxidation and adsorption processes was found to be the most effective, with the highest 90-99% and 89-95% molnupiravir and microplastics contaminants removal efficiency from the model wastewater. The research has received funding from the European Regional Development Fund (project No 13.1.1-LMT-K-718-05-0014) under a grant agreement with the Research Council of Lithuania (LMTLT), and it was funded as part of the European Union’s measure in response to the COVID-19 pandemic.

Keywords: adsorption, hybrid reactor system, pharmaceuticals-microplastics, wastewater

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Authors: Bhairi Lakshminarayana, Surajit Sarker, Ch. Subrahmanyam

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The present study reports the development of noble metal free nano catalysts for low-temperature CO oxidation and water gas shift reaction. Mn-substituted CeO2 solid solution catalysts were synthesized by co-precipitation, combustion and hydrothermal methods. The formation of solid solution was confirmed by XRD with Rietveld refinement and the percentage of carbon and nitrogen doping was ensured by CHNS analyzer. Raman spectroscopic confirmed the oxygen vacancies. The surface area, pore volume and pore size distribution confirmed by N2 physisorption analysis, whereas, UV-visible diffuse reflectance spectroscopy and XPS data confirmed the oxidation state of the Mn ion. The particle size and morphology (spherical shape) of the material was confirmed using FESEM and HRTEM analysis. Ce0.8Mn0.2O2-δ was calcined at 400 °C, 600 °C and 800 °C. Raman spectroscopy confirmed that the catalyst calcined at 400 °C has the best redox properties. The activity of the designed catalysts for CO oxidation (0.2 vol%), carried out with GHSV of 21,000 h-1 and it has been observed that co-precipitation favored the best active catalyst towards CO oxidation and water gas shift reaction, due to the high surface area, improved reducibility, oxygen mobility and highest quantity of surface oxygen species. The activation energy of low temperature CO oxidation on Ce0.8Mn0.2O2- δ (combustion) was 5.5 kcal.K-1.mole-1. The designed catalysts were tested for water gas shift reaction. The present study demonstrates that Mn ion substituted ceria at 400 °C calcination temperature prepared by co-precipitation method promise to revive a green sustainable energy production approach.

Keywords: Ce0.8Mn0.2O2-ð, CO oxidation, physicochemical characterization, water gas shift reaction (WGS)

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Authors: Sandip Sharma, Jayesh Ruparelia

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The present work focuses on the comparative study of ozone based advanced oxidation processes (AOPs): O3, O3/UV and O3/UV/Persulfate for mineralization of synthetic wastewater containing Reactive Black5 (RB5) dye. The effect of various parameters: pH, ozone flow rate, initial concentration of dye and intensity of UV light was analyzed to access performance efficiency of AOPs. The performance of all the three AOPs was evaluated on the basis of decolorization, % TOC removal and ozone consumption. The highest mineralization rate of 86.83% was achieved for O3/UV/Persulfate followed by 71.53% and 66.82 % for O3/UV and O3 respectively. This is attributed to the fact that Persulfate ions (S2O82-) upon activation produce sulfate radical (SO4-●) which is very strong oxidant capable of degrading a wide variety of recalcitrant organic compounds, moreover to enhance the performance of Persulfate it is activated using UV irradiation. On increasing the intensity of UV irradiation from 11W to 66W, TOC removal efficiency is increased by 59.04%. Ozone based AOPs gives better mineralization on basic conditions, at pH 12 it gives 68.81%, 60.01% and 40.32% TOC removal for O3/UV/Persulfate, O3/UV and O3 process respectively. The result also reveals that decolorization of 98.95%, 95.17% and 94.71% was achieved by O3/UV/Persulfate, O3/UV and O3 process respectively. In addition to above, ozone consumption was also considerably decreased by 17% in case of O3/UV/Persulfate, as efficiency of process is enhanced by means of activation of persulfate through UV irradiation. Thus study reveals that mineralization follows: O3/UV/Persulfate> O3/UV> O3.

Keywords: AOP, mineralization, TOC, recalcitrant organic compounds

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Authors: Stefan Andersson, Balram Panjwani, Bernd Wittgens, Jan Erik Olsen

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Polycyclic Aromatic hydrocarbons are organic compounds consisting of only hydrogen and carbon aromatic rings. PAH are neutral, non-polar molecules that are produced due to incomplete combustion of organic matter. These compounds are carcinogenic and interact with biological nucleophiles to inhibit the normal metabolic functions of the cells. Norways, the most important sources of PAH pollution is considered to be aluminum plants, the metallurgical industry, offshore oil activity, transport, and wood burning. Stricter governmental regulations regarding emissions to the outer and internal environment combined with increased awareness of the potential health effects have motivated Norwegian metal industries to increase their efforts to reduce emissions considerably. One of the objective of the ongoing industry and Norwegian research council supported "SCORE" project is to reduce potential PAH emissions from an off gas stream of a ferroalloy furnace through controlled combustion. In a dedicated combustion chamber. The sizing and configuration of the combustion chamber depends on the combined properties of the bulk gas stream and the properties of the PAH itself. In order to achieve efficient and complete combustion the residence time and minimum temperature need to be optimized. For this design approach reliable kinetic data of the individual PAH-species and/or groups thereof are necessary. However, kinetic data on the combustion of PAH are difficult to obtain and there is only a limited number of studies. The paper presents an evaluation of the kinetic data for some of the PAH obtained from literature. In the present study, the oxidation is modelled for pure PAH and also for PAH mixed with process gas. Using a perfectly stirred reactor modelling approach the oxidation is modelled including advanced reaction kinetics to study influence of residence time and temperature on the conversion of PAH to CO2 and water. A Chemical Reactor Network (CRN) approach is developed to understand the oxidation of PAH inside the combustion chamber. Chemical reactor network modeling has been found to be a valuable tool in the evaluation of oxidation behavior of PAH under various conditions.

Keywords: PAH, PSR, energy recovery, ferro alloy furnace

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Authors: Jin Lin, Shouxiang Lu, Kim Meow Liew

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The requirement for the long-term mission of the submarine and spacecraft has made the removal of CO₂ and trace CO the critical technology to ensure the health and life of the crews. In this work, CuMnCe, a metal oxide catalyst, supporting K₂CO₃ sorbent was prepared by the wet-solid state impregnation method to realize the integrated CO and CO₂ removal, which might also reduce the volume/mass load of the purification units in the limited space. The as-prepared samples with different addition amount of K₂CO₃ were tested using the fixed bed reactor to reveal the CO oxidation and CO₂ absorption behavior. And the regeneration and stability experiments were also conducted. The results showed that the samples realized the catalyst and sorbent integration to capture CO and CO₂ at the same time. The addition amount of the sorbent had a weak influence on the CO oxidation performance. While the addition amount affected the CO₂ sorption efficiency and capacity significantly. Meanwhile, the presence of water vapor could reduce the CO oxidation activity of the samples similarly, whether with K2CO3 sorbent addition or not. Furtherly, regeneration and stability experiment results showed that the samples after 3-5 times regeneration exhibited almost the same performance of CO and CO₂ removal. Summarily, CuMnCe catalyst supporting K₂CO₃ sorbent could be a good attempt to control CO and CO₂ pollutants generated from the daily equipment running and staff breathing in the confined space such as submarine and spacecraft.

Keywords: CO oxidation, CO₂ absorptio, potassium carbonate, CuMnCe metal oxide, confined space

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Authors: H. Selcuk Halkacı, Mevlüt Türköz, Ekrem Öztürk, Murat Dilmec

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Various attempts concerning the low formability issue for lightweight materials like aluminium and magnesium alloys are being investigated in many studies. Advanced forming processes such as hydroforming is one of these attempts. In last decades sheet hydroforming process has an increasing interest, particularly in the automotive and aerospace industries. This process has many advantages such as enhanced formability, the capability to form complex parts, higher dimensional accuracy and surface quality, reduction of tool costs and reduced die wear compared to the conventional sheet metal forming processes. There are two types of sheet hydroforming. One of them is hydromechanical deep drawing (HDD) that is a special drawing process in which pressurized fluid medium is used instead of one of the die half compared to the conventional deep drawing (CDD) process. Another one is sheet hydroforming with die (SHF-D) in which blank is formed with the act of fluid pressure and it takes the shape of die half. In this study, transition of cup height according to cup diameter between the processes was determined by performing simulation of the processes in Finite Element Analysis. Firstly SHF-D process was simulated for 40 mm cup diameter at different cup heights chancing from 10 mm to 30 mm and the cup height to diameter ratio value in which it is not possible to obtain a successful forming was determined. Then the same ratio was checked for a different cup diameter of 60 mm. Then thickness distributions of the cups formed by SHF-D and HDD processes were compared for the cup heights. Consequently, it was found that the thickness distribution in HDD process in the analyses was more uniform.

Keywords: finite element analysis, HDD, hydroforming sheet metal forming, SHF-D

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Authors: Ahmed A. Abdel-Khalek, Reham A. Mohamed

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The kinetics of oxidation of the cobalt (II) complexes, [CoII(ADA)(Gly)(H2O)2]-, (ADA = N-(2-acetamido) iminodi-acetic acid and (Gly = Glycine) by periodate in aqueous acetate medium to cobalt (III) have been studied spectrophotometrically at 530 nm over the 30–50°C and a variety pH 4.57-5.25 range and I = 0.50 mol dm-3 under pseudo first order condition by taking large excess of oxidant [IO4-] and it obeys the following rate law: Rate=[CoII(ADA)(Gly)(H2O)2]-[H5IO6]{k4K6+(k5K7K5/[H+])}. Also, the kinetics of oxidation of the cobalt(II) complexes, [CoII(ADA)(Val)(H2O)2]- (ADA = N-(2-acetamido) iminodi-acetic acid and (Val = valine) by periodate in aqueous medium to cobalt (III) have been studied spectrophotometrically at 580 nm over the 30–50°C and a variety pH 4.3-5.12 range and I = 0.50 mol dm-3 under pseudo first order condition by taking large excess of oxidant [IO4-] and it obeys the following rate law: Rate=[CoII(ADA)(Val)(H2O)2]-[H5IO6]{k4K6+(k5K7K5/[H+])}

Keywords: periodate, oxidation, cobalt (II), glycine, valine acid, n-(2-acetamido imino-diacetato)

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Authors: S. Trafela, X. Xua, K. Zuzek Rozmana

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In this study, we used an accurate and precise method to measure the electrochemically active surface areas (Aecsa) of nickel electrodes. Calculated Aecsa is really important for the evaluation of an electro-catalyst’s activity in electrochemical reaction of different organic compounds. The method involves the electrochemical formation of Ni(OH)₂ and NiOOH in the presence of adsorbed oxalate in alkaline media. The studies were carried out using cyclic voltammetry with polycrystalline nickel as a reference material and electrodeposited nickel nanowires, homogeneous and heterogeneous nickel films. From cyclic voltammograms, the charge (Q) values for the formation of Ni(OH)₂ and NiOOH surface oxides were calculated under various conditions. At sufficiently fast potential scan rates (200 mV s⁻¹), the adsorbed oxalate limits the growth of the surface hydroxides to a monolayer. Although the Ni(OH)₂/NiOOH oxidation peak overlaps with the oxygen evolution reaction, in the reverse scan, the NiOOH/ Ni(OH)₂ reduction peak is well-separated from other electrochemical processes and can be easily integrated. The values of these integrals were used to correlate experimentally measured charge density with an electrochemically active surface layer. The Aecsa of the nickel nanowires, homogeneous and heterogeneous nickel films were calculated to be Aecsa-NiNWs = 4.2066 ± 0.0472 cm², Aecsa-homNi = 1.7175 ± 0.0503 cm² and Aecsa-hetNi = 2.1862 ± 0.0154 cm². These valuable results were expanded and used in electrochemical studies of formaldehyde oxidation. As mentioned nickel nanowires, heterogeneous and homogeneous nickel films were used as simple and efficient sensor for formaldehyde detection. For this purpose, electrodeposited nickel electrodes were modified in 0.1 mol L⁻¹ solution of KOH in order to expect electrochemical activity towards formaldehyde. The investigation of the electrochemical behavior of formaldehyde oxidation in 0.1 mol L⁻¹ NaOH solution at the surface of modified nickel nanowires, homogeneous and heterogeneous nickel films were carried out by means of electrochemical techniques such as cyclic voltammetric and chronoamperometric methods. From investigations of effect of different formaldehyde concentrations (from 0.001 to 0.1 mol L⁻¹) on electrochemical signal - current we provided catalysis mechanism of formaldehyde oxidation, detection limit and sensitivity of nickel electrodes. The results indicated that nickel electrodes participate directly in the electrocatalytic oxidation of formaldehyde. In the overall reaction, formaldehyde in alkaline aqueous solution exists predominantly in form of CH₂(OH)O⁻, which is oxidized to CH₂(O)O⁻. Taking into account the determined (Aecsa) values we have been able to calculate the sensitivities: 7 mA mol L⁻¹ cm⁻² for nickel nanowires, 3.5 mA mol L⁻¹ cm⁻² for heterogeneous nickel film and 2 mA mol L⁻¹ cm⁻² for heterogeneous nickel film. The detection limit was 0.2 mM for nickel nanowires, 0.5 mM for porous Ni film and 0.8 mM for homogeneous Ni film. All of these results make nickel electrodes capable for further applications.

Keywords: electrochemically active surface areas, nickel electrodes, formaldehyde, electrocatalytic oxidation

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Authors: Yousef Naserzadeh, Niloufar Mahmoudi

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Oxidation resistance is one of the important parameters in maintaining the quality of olive oil during its storage. Ensuring the stability of the quality of olive oil is one of the important concerns of the producers and consumers. Prooxidants such as iron and copper accelerate the oxidation reaction, and also anti-oxidants and chelating compounds delay it. In this study, chelating effect of tea extract which contains significant amounts of tannic acid is investigated in comparison with citric acid. To do it, 0.1 ppm copper was added to these four kinds of oil, sunflower, olive, canola, and tallow, and then chelating effect of citric acid (0.01%), tannic acid (0.01%) and tea extract (0.1%) were measured by adding to this composition. To this end, the resistance time of the oils against oxidation was measured at 120 °C and an air flow of 20 liters per hour. And the value of peroxide was measured by oven test in six periods of 24 hours at 105 °C. The results showed that citric acid, tannic acid and tea extract had chelating property and increased the resistance time of the studied oils. As a result, considering chelating property and increasing resistance of oil, tannic acid showed better effect than tea extract and tea extract had better effect than citric acid.

Keywords: tannic acid, chelate, edible oils, black tea extract, TBHQ

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Authors: Abdelrahman Abdelazim

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Most industries are looking for technologies that are easy to use, efficient and fast to accomplish. To implement these, factories tend to use advanced systems that could alter complicity to simplicity and rudimentary to advancement. Cloud Manufacturing is a new movement that aims to mirror and integrate cloud computing into manufacturing. Amongst cloud manufacturing various advantages are decreasing the human involvements and increasing the dependency on automated machines, which in turns decreases human errors and increases efficiency. A reliable and extraordinary performance processes with minimum errors are highly desired factors of today’s manufacturers. At the glance it seems to be the best alternative, however, the implementation of a cloud system can be very challenging. This work investigates cloud manufacturing in details, it outlines its advantages and disadvantages by converting a local factory in Kuwait to a cloud-ready system. Initially the flow of the factory’s manufacturing process has been analyzed identifying the bottlenecks and illustrating how cloud manufacturing can eliminate them. Following this an automation process has been analyzed and implemented. A comparison between the process before and after the adaptation has been carried out showing the effects on the cost, the output and the efficiency of the process.

Keywords: cloud manufacturing, automation, Kuwait industrial sector, advanced digital manufacturing

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Authors: Moustafa Elhamouly, Masayuki Shimada

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The production of competent oocytes is essential for reproductivity in mammals. Maintenance of mitochondrial efficiency is required to supply the ATP necessary for granulosa cell proliferation during the follicular development process. Treatment with Pyrroloquinoline quinone (PQQ) has been reported to increase the number of ovulated oocytes and pups per delivery in mice by maintaining healthy mitochondrial function. This study aimed to elucidate how PQQ maintains mitochondrial function during ovarian follicle growth. To do this, both in vitro and in vivo experiments were performed with granulosa cells from superovulated immature (3-week-old) mice that were pretreated with or without PQQ. The effects of PQQ on beta-oxidation, mitochondrial function, mitophagy, and mitochondrial biogenesis were examined. PQQ increased beta-oxidation-related genes and CPT1 protein content in granulosa cells and this was associated with a decreased phosphorylation of P38 signaling protein. Using the fatty acid oxidation assay on the flux analyzer, PQQ increased the reliance of beta-oxidation on the endogenous fatty acids and was associated with a mild UCP-dependant mitochondrial uncoupling, ATP production, mitophagy, and mitochondrial biogenesis. PQQ also increased the expression of endogenous antioxidant enzymes. Thus, PQQ induced beta-oxidation in growing granulosa cells relying on endogenous fatty acids. And reduced the Reactive oxygen species (ROS) production by inducing a mild mitochondrial uncoupling with keeping high mitochondrial function. Damaged mitochondria were recycled by the induced mitophagy and replaced by the increased mitochondrial biogenesis. Collectively, PQQ may enhance reproductivity by maintaining the efficiency of mitochondria to produce enough ATP required for normal folliculogenesis.

Keywords: granulosa cells, mitochondrial uncoupling, mitophagy, pyrroloquinoline quinone (PQQ), reactive oxygen species (ROS).

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Authors: Emine Yılmaz, Serap Fındık

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Baker’s yeast industry uses molasses as a raw material. Molasses is end product of sugar industry. Wastewater from molasses processing presents large amount of coloured substances that give dark brown color and high organic load to the effluents. The main coloured compounds are known as melanoidins. Melanoidins are product of Maillard reaction between amino acid and carbonyl groups in molasses. Dark colour prevents sunlight penetration and reduces photosynthetic activity and dissolved oxygen level of surface waters. Various methods like biological processes (aerobic and anaerobic), ozonation, wet air oxidation, coagulation/flocculation are used to treatment of baker’s yeast effluent. Before effluent is discharged adequate treatment is imperative. In addition to this, increasingly stringent environmental regulations are forcing distilleries to improve existing treatment and also to find alternative methods of effluent management or combination of treatment methods. Sonochemical oxidation is one of the alternative methods. Sonochemical oxidation employs ultrasound resulting in cavitation phenomena. In this study, decolorization of baker’s yeast effluent was investigated by using ultrasound. Baker’s yeast effluent was supplied from a factory which is located in the north of Turkey. An ultrasonic homogenizator used for this study. Its operating frequency is 20 kHz. TiO2-ZnO catalyst has been used as sonocatalyst. The effects of molar proportion of TiO2-ZnO, calcination temperature and time, catalyst amount were investigated on the decolorization of baker’s yeast effluent. The results showed that prepared composite TiO2-ZnO with 4:1 molar proportion treated at 700°C for 90 min provides better result. Initial decolorization rate at 15 min is 3% without catalyst, 14,5% with catalyst treated at 700°C for 90 min respectively.

Keywords: baker’s yeast effluent, decolorization, sonocatalyst, ultrasound

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Authors: Saja M. Nabat Al-Ajrash, Charles Browning, Rose Eckerle, Li Cao, Robyn L. Bradford, Donald Klosterman

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An additive manufacturing process and subsequent pyrolysis cycle were used to fabricate SiC matrix/carbon fiber hybrid composites. The matrix was fabricated using a mixture of preceramic polymer and acrylate monomers, while polyacrylonitrile (PAN) precursor was used to fabricate fibers via electrospinning. The precursor matrix and reinforcing fibers at 0, 2, 5, or 10 wt% were printed using digital light processing, and both were simultaneously pyrolyzed to yield the final ceramic matrix composite structure. After pyrolysis, XRD and SEAD analysis proved the existence of SiC nanocrystals and turbostratic carbon structure in the matrix, while the reinforcement phase was shown to have a turbostratic carbon structure similar to commercial carbon fibers. Thermogravimetric analysis (TGA) in the air up to 1400 °C was used to evaluate the oxidation resistance of this material. TGA results showed some weight loss due to oxidation of SiC and/or carbon up to about 900 °C, followed by weight gain to about 1200 °C due to the formation of a protective SiO2 layer. Although increasing carbon fiber content negatively impacted the total mass loss for the first heating cycle, exposure of the composite to second-run air revealed negligible weight chance. This is explained by SiO2 layer formation, which acts as a protective film that prevents oxygen diffusion. Oxidation of SiC and the formation of a glassy layer has been proven to protect the sample from further oxidation, as well as provide healing of surface cracks and defects, as revealed by SEM analysis.

Keywords: silicon carbide, carbon fibers, additive manufacturing, composite

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Authors: V. Veena, Suguna Yesodharan, E. P. Yesodharan

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Two Advanced Oxidation Processes (AOP) i.e., sono- and photo-catalysis mediated by semiconductor oxide catalyst, ZnO has been found effective for the removal of trace amounts of the toxic dye pollutant Indigocarmine (IC) from water. The effect of various reaction parameters such as concentration of the dye, catalyst dosage, temperature, pH, dissolved oxygen etc. as well as the addition of oxidisers and presence of salts in water on the rate of degradation has been evaluated and optimised. The degradation follows variable kinetics depending on the concentration of the substrate, the order of reaction varying from 1 to 0 with increase in concentration. The reaction proceeds through a number of intermediates and many of them have been identified using GCMS technique. The intermediates do not affect the rate of degradation significantly. The influence of anions such as chloride, sulphate, fluoride, carbonate, bicarbonate, phosphate etc. on the degradation of IC is not consistent and does not follow any predictable pattern. Phosphates and fluorides inhibit the degradation while chloride, sulphate, carbonate and bicarbonate enhance. Adsorption studies of the dye in the absence as well as presence of these anions show that there may not be any direct correlation between the adsorption of the dye on the catalyst and the degradation. Oxidants such as hydrogen peroxide and persulphate enhance the degradation though the combined effect and it is less than the cumulative effect of individual components. COD measurements show that the degradation proceeds to complete mineralisation. The results will be presented and probable mechanism for the degradation will be discussed.

Keywords: AOP, COD, indigocarmine, photocatalysis, sonocatalysis

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Authors: Kalyani Mer

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Hydrogen peroxide (H₂O₂) is one of the most efficient and commonly used oxidants in in-situ chemical oxidation (ISCO) of organic contaminants. In the present study, we investigated the activation of H₂O₂ by heavy metal (nickel and lead metal ions) loaded biochar for phenol degradation in an aqueous solution (concentration = 100 mg/L). It was found that H₂O₂ can be effectively activated by biochar, which produces hydroxyl (•OH) radicals owing to an increase in the formation of persistent free radicals (PFRs) on biochar surface. Ultrasound treated (30s duration) biochar, chemically activated by 30% phosphoric acid and functionalized by diethanolamine (DEA) was used for the adsorption of heavy metal ions from aqueous solutions. It was found that modified biochar could remove almost 60% of nickel in eight hours; however, for lead, the removal efficiency reached up to 95% for the same time duration. The heavy metal loaded biochar was further used for the degradation of phenol in the absence and presence of H₂O₂ (20 mM), within 4 hours of reaction time. The removal efficiency values for phenol in the presence of H₂O₂ were 80.3% and 61.9%, respectively, by modified biochar loaded with nickel and lead metal ions. These results suggested that the biochar loaded with nickel exhibits a better removal capacity towards phenol than the lead loaded biochar when used in H₂O₂ based oxidation systems. Meanwhile, control experiments were set in the absence of any activating biochar, and the removal efficiency was found to be 19.1% when only H₂O₂ was added in the reaction solution. Overall, the proposed approach serves a dual purpose of using biochar for heavy metal ion removal and treatment of organic contaminants by further using the metal loaded biochar for H₂O₂ activation in ISCO processes.

Keywords: biochar, ultrasound, heavy metals, in-situ chemical oxidation, chemical activation

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Authors: Changde Zhang, Qiang Zhang, Shilong Zheng, Jiawang Liu, Shanchun Guo, Qiu Zhong, Guangdi Wang

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Fulvestrant was approved by FDA to treat breast cancer as a selective estrogen receptor downregulator (SERD) with intramuscular injection administration. ZB716, a fulvestarnt-3 boronic acid, is an SERD with comparable anticancer effect to fulvestrant, but could produce good pharmacokinetic properties under oral administration with mice or rat models. To understand why ZB716 produced much better oral bioavailability, it was proposed that the boronic acid blocked the phase II direct biotransformation with the hydroxyl group on the 3 position of the aromatic ring on fulvestrant. In this study, ZB716 or fulvestrant was incubated with human liver microsome and oxidation cofactor NADPH in vitro. Their metabolites after oxidation were profiled with the Q-Exactive, a high-resolution mass spectrometer. The result showed that ZB716 blocked the forming of hydroxyl groups on its benzene ring except for the oxidation of C-B bond forming fulvestrant in its metabolites, and the concentration of fulvestrant with one more hydroxyl group found in the metabolites from incubation with fulvestrant was about 34 fold high as that formed from incubation with ZB716. Compared to fulvestrant, ZB716 is expected to be much difficult to be further bio-transformed into more hydrophilic compounds, to be difficult excreted out of blood system, and to have longer residence time in blood, which can lead to higher oral bioavailability. This study provided evidence to explain the high bioavailability of ZB716 after oral administration from the perspective of its difficulty of oxidation, a phase I biotransformation, on positions on its aromatic ring.

Keywords: biotransformation, fulvestrant, metabolite profiling, ZB716

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Authors: Jinge Liu, Shuyuan Min, Bingchuan Liu, Bangzhao Yin, Bo Peng, Peng Wen, Yun Tian

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WE43 magnesium alloy can be additively manufactured via laser powder bed fusion (LPBF) for biodegradable applications, but the as-built WE43 exhibits an excessively rapid corrosion rate. High-temperature oxidation (HTO) was performed on the as-built WE43 to improve its biodegradation behavior. A sandwich structure including an oxide layer at the surface, a transition layer in the middle, and the matrix was generated influenced by the oxidation reaction and diffusion of RE atoms when heated at 525 ℃for 8 hours. The oxide layer consisted of Y₂O₃ and Nd₂O₃ oxides with a thickness of 2-3 μm. The transition layer is composed of α-Mg and Y₂O₃ with a thickness of 60-70 μm, while Mg24RE5 could be observed except α-Mg and Y₂O₃. The oxide layer and transition layer appeared to have an effective passivation effect. The as-built WE43 lost 40% weight after the in vitro immersion test for three days and finally broke into debris after seven days of immersion. The high-temperature oxidation samples kept the structural integrity and lost only 6.88 % weight after 28-day immersion. The corrosion rate of HTO samples was significantly controlled, which improved the biocompatibility of the as-built WE43 at the same time. The samples after HTO had better osteogenic capability according to ALP activity. Moreover, as built WE43 performed unqualified in cell adhesion and hemolytic test due to its excessively rapid corrosion rate. While as for HTO samples, cells adhered well, and the hemolysis ratio was only 1.59%.

Keywords: laser powder bed fusion, biodegradable metal, high temperature oxidation, biodegradation behavior, WE43

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Authors: Kooshan Nayebzadeh, Maryam Enteshari

Abstract:

In this study, the oxidative stability of soybean oil under different storage temperatures (4 and 25 ˚C) and during 6-month shelf-life was investigated by various analytical methods and headspace-liquid phase microextraction (HS-LPME) coupled to gas chromatography-mass spectrometry (GC-MS). Oxidation changes were monitored by analytical parameters consisted of acid value (AV), peroxide value (PV), p-Anisidine value (p-AV), thiobarbituric acid value (TBA), fatty acids profile, iodine value (IV) and oxidative stability index (OSI). In addition, concentrations of hexanal and heptanal as secondary volatile oxidation compounds were determined by HS-LPME/GC-MS technique. Rate of oxidation in soybean oil which stored at 25 ˚C was so higher. The AV, p-AV, and TBA were gradually increased during 6 months, while the amount of unsaturated fatty acids, IV, and OSI decreased. Other parameters included concentrations of both hexanal and heptanal, and PV exhibited increasing trend during primitive months of storage; then, at the end of third and fourth months a sudden decrement was understood for the concentrations of hexanal and heptanal and the amount of PV, simultaneously. The latter parameters increased again until the end of shelf-time. As a result, the temperature and time were effective factors in oxidative stability of soybean oil. Also intensive correlations were found for soybean oil at 4 ˚C between AV and TBA (r2=0.96), PV and p-AV (r2=0.9), IV and TBA (-r2=0.9), and for soybean oil stored at 4 ˚C between p-AV and TBA (r2=0.99).

Keywords: headspace-liquid phase microextraction, oxidation, shelf-life, soybean oil

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Authors: D. Tassalit, N. Chekir, O. Benhabiles, N. A. Laoufi, F. Bentahar

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In the setting of the waters purification, some molecules appear recalcitrant to the traditional treatments. The exploitation of the properties of some catalysts permits to amplify the oxidization performances with ultraviolet radiance and to remove this pollution by a non biological way. This study was conducted to investigate the effect of a photocatalysis oxidation system for organic pollutants treatment using a new reactor design and ZnO/TiO2 as a catalyst under UV light. Oxidative degradation of tylosin by hydroxyl radicals (OH°) was studied in aqueous medium using suspended forms of ZnO and TiO2. The results improve that the treatment was affected by many factors such as flow-rate of solution, initial pollutant concentration and catalyst concentration. The rate equation for the tylosin degradation followed first order kinetics and the rate-constants were determined. The reaction rate fitted well with Langmuir–Hinshelwood model and the removed ratio of tylosin was 97 % in less than 60 minutes. To determine the optimum catalyst loading, a series of experiments were carried out by varying the amount of catalyst from 0.05 to 0.5 g/L. The results demonstrate that the rate of photodegradation is optimum with catalyst loading of 0.1 g/L, reaction flow rate of 3.79 mL/s and solution natural pH. The rate was found to increase with the decrease in tylosin concentration from 30 to 5 mg/L. Therefore, this simple photoreactor design for the removal of organic pollutants has the potential to be used in wastewater treatment.

Keywords: advanced oxidation, photocatalysis, TiO2, ZnO, UV light, pharmaceuticals pollutants, Spiramycin, tylosin, wastewater treatment

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Authors: Khosro Ghazvinian, Touba Khodaeian

Abstract:

To improve the oxidative stability of meat products, the use of dietary form of antioxidants can extend the shelf life and acceptability of muscle food during exposition or storage condition. As shown, this method is more effective than adding direct preservatives due to uniform incorporation of dietary additives into sub cellular membrane and therefore, they can properly inhibit the oxidative reaction at their localized sites. Furthermore, postmortem addition of antioxidants to meat cannot directly inhibit the oxidation in membrane phospholipids. Therefore, this study was designed to evaluate the effects of feed supplementation with Melissa officinalis leaves on lipid peroxidation of chicken breast fillets during refrigerated storage. In this study, 72 one-day old Ross 308 broilers distributed in four groups with six replicates (3 chickens each) were fed a basal diet (CONT) or basal diet supplemented with 5, 10, and 15 gr/Kg M.officinalis, for 6 weeks. Following slaughter, fillets from breast were stored at 4 °C in the dark for 12 days, and lipid oxidation was assessed on the basis of thiobarbituric acid reactive substances (TBARS) formed. Results showed that incorporation of M.officinalis in broiler diets delayed lipid oxidation in raw breast meat during refrigerated storage comparative with CONT(p<0.05). In this regard, TBARS levels of breast samples containing higher concentrations (10 and 15 gr/Kg) of M. officinalis (625.43 and 504.32 µg/kg MDA equivalents, respectively )were significantly lower than those of control and 5g/kg samples (872.75 and 841.32 µg/kg MDA equivalents, respectively) (p<0.05). Therefore, M. officinalis might be utilized in novel applications as a nutritional supplement or a functional food component.

Keywords: breast fillet, lipid oxidation, Melissa officinalis, TBARS assay

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Authors: J. Bolobajev, M. Trapido, A. Goi

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The practical application of the Fenton-based treatment method for organic compounds-contaminated water purification is limited mainly because of the large amount of ferric sludge formed during the treatment, where ferrous iron (Fe(II)) is used as the activator of the hydrogen peroxide oxidation processes. Reuse of ferric sludge collected from clarifiers to substitute Fe(II) salts allows reducing the total cost of Fenton-type treatment technologies and minimizing the accumulation of hazardous ferric waste. Dissolution of ferric iron (Fe(III)) from the sludge to liquid phase at acidic pH and autocatalytic transformation of Fe(III) to Fe(II) by phenolic compounds (tannic acid, lignin, phenol, catechol, pyrogallol and hydroquinone) added or present as water/wastewater constituents were found to be essentially involved in the Fenton-based oxidation mechanism. Observed enhanced formation of highly reactive species, hydroxyl radicals, resulted in a substantial organic contaminant degradation increase. Sludge reuse at acidic pH and in the presence of ferric iron reductants is a novel strategy in the Fenton-based treatment application for organic compounds-contaminated water purification.

Keywords: ferric sludge recycling, ferric iron reductant, water treatment, organic pollutant

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Authors: A. Masek, M. Zaborski

Abstract:

Electrochemical oxidation of dodecyl gallate (lauryl gallate), the main monomer flavanol found in green tea, was investigated on platinum electrodes using cyclic voltammetry (CV) and differential pulse (DPV) methods. The rate constant, electron transfer coefficient and diffusion coefficients were determined for dodecyl gallate electrochemical oxidation. The oxidation mechanism proceeds in sequential steps related to the hydroxyl groups in the aromatic ring of dodecyl gallate. Confirmed antioxidant activity of lauryl gallate verified its use in polymers as an environment-friendly stabiliser to improve the resistance to aging of the elastomeric materials. Based on the energy change of the deformation, cross-linking density and time of the oxygen induction with the TG method, we confirmed the high antioxidant activity of lauryl gallate in polymers. Moreover, the research on biodegradation confirmed the environment-friendly influence of the antioxidant by increasing the susceptibility of the elastomeric materials to disintegration by mildew mushrooms.

Keywords: polymers, flavonoids, stabilization, ageing

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Authors: Khaled S. Al Salhen

Abstract:

Aldehyde oxidase is molybdo-flavoenzyme involved in the oxidation of hundreds of endogenous and exogenous and N-heterocyclic compounds and environmental pollutants. Uncharged N-heterocyclic aromatic compounds such phenanthridine are commonly distributed pollutants in soil, air, sediments, surface water and groundwater, and in animal and plant tissues. Phenanthridine as uncharged N-heterocyclic aromatic compound was incubated with partially purified aldehyde oxidase from rainbow trout fish liver. Reversed-phase HLPC method was used to separate the oxidation products from phenanthridine and the metabolite was identified. The 6(5H)-phenanthridinone was identified the major metabolite by partially purified aldehyde oxidase from fish liver. Kinetic constant for the oxidation reactions were determined spectrophotometrically and showed that this substrate has a good affinity (Km = 78 ± 7.6 µM) for hepatic aldehyde oxidase, coupled with a relatively high oxidation rate (0.77± 0.03 nmol/min/mg protein). In addition, the kinetic parameters of hepatic fish aldehyde oxidase towards the phenanthridine substrate indicate that in vitro biotransformation by hepatic fish aldehyde oxidase will be a significant pathway. This study confirms that partially purified aldehyde oxidase from fish liver is indeed the enzyme responsible for the in vitro production 6(5H)-phenanthridinone metabolite as it is a major metabolite by mammalian aldehyde oxidase.

Keywords: aldehyde oxidase, fish, phenanthridine, specificity

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Authors: Vidula Shevade, B. J. Nagare, Sajeev Chacko

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First principles simulation, meaning density functional theory (DFT) calculations with plane waves and pseudopotential, has become a prized technique in condensed matter theory. Nanoparticles (NP) have been known to possess good catalytic activities, especially for molecules such as CO, O₂, etc. Among the metal NPs, Aluminium based NPs are also widely known for their catalytic properties. Aluminium metal is a lightweight, excellent electrical, and thermal abundant chemical element in the earth’s crust. Aluminium NPs, when added to solid rocket fuel, help improve the combustion speed and considerably increase combustion heat and combustion stability. Adding aluminium NPs into normal Al/Al₂O₃ powder improves the sintering processes of the ceramics, with high heat transfer performance, increased density, and enhanced thermal conductivity of the sinter. We used VASP and Gaussian 0₃ package to compute the geometries, electronic structure, and bonding properties of Al₁₂Ni as well as its interaction with O₂ and CO molecules. Several MD simulations were carried out using VASP at various temperatures from which hundreds of structures were optimized, leading to 24 unique structures. These structures were then further optimized through a Gaussian package. The lowest energy structure of Al₁₂Ni has been reported to be a singlet. However, through our extensive search, we found a triplet state to be lower in energy. In our structure, the Ni atom is found to be on the surface, which gives the non-zero magnetic moment. Incidentally, O2 and CO molecules are also triplet in nature, due to which the Al₁₂-Ni cluster is likely to facilitate the oxidation process of the CO molecule. Our results show that the most favourable site for the CO molecule is the Ni atom and that for the O₂ molecule is the Al atom that is nearest to the Ni atom. Al₁₂Ni-O₂ and Al₁₂-Ni-CO structures we extracted using VMD. Al₁₂Ni nanocluster, due to in triplet electronic structure configuration, indicates it to be a potential candidate as a catalyst for oxidation of CO molecules.

Keywords: catalyst, gaussian, nanoparticles, oxidation

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Authors: Ildiko Fekete-Kertesz, Jade Chaker, Sylvain Berthelot, Viktoria Feigl, Monika Molnar, Lidia Favier

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There has been growing concern about emerging micropollutants in recent years, because of the possible environmental and health risk posed by these substances, which are released into the environment as a consequence of anthropogenic activities. Among them pharmaceuticals are currently not considered under water quality regulations; however, their potential effect on the environment have become more frequent in recent years. Due to the fact that these compounds can be detected in natural water matrices, it can be concluded, that the currently applied water treatment processes are not efficient enough for their effective elimination. To date, advanced oxidation processes (AOPs) are considered as highly competitive water treatment technologies for the removal of those organic micropollutants not treatable by conventional techniques due to their high chemical stability and/or low biodegradability. AOPs such as (photo)chemical oxidation and heterogeneous photocatalysis have proven their potential in degrading harmful organic compounds from aqueous matrices. However, some of these technologies generate reaction by-products, which can even be more toxic to aquatic organisms than the parent compounds. Thus, target compound removal does not necessarily result in the removal of toxicity. Therefore, to evaluate process efficiency the determination of the toxicity and ecotoxicity of the reaction intermediates is crucial to estimate the environmental risk of such techniques. In this context, the present study investigates the effectiveness of TiO2 assisted photodegradation for the removal of emerging water contaminants. Two drugs named losartan (used in high blood pressure medication) and levetiracetam (used to treat epilepsy) were considered in this work. The photocatalytic reactions were carried out with a commercial catalyst usually employed in photocatalysis. Moreover, the toxicity of the by-products generated during the process was assessed with various ecotoxicological methods applying aquatic test organisms from different trophic levels. A series of experiments were performed to evaluate the toxicity of untreated and treated solutions applying the Aliivibrio fischeri bioluminescence inhibition test, the Tetrahymena pyriformis proliferation inhibition test, the Daphnia magna lethality and immobilization tests and the Lemna minor growth inhibition test. The applied ecotoxicological methodology indicated sensitively the toxic effects of the treated and untreated water samples, hence the applied test battery is suitable for the ecotoxicological characterization of TiO2 based photocatalytic water treatment technologies and the indication of the formation of toxic by-products from the parent chemical compounds. Obtained results clearly showed that the TiO2 assisted photodegradation was more efficient in the elimination of losartan than levetiracetam. It was also observed that the treated levetiracetam solutions had more severe effect on the applied test organisms. A possible explanation would be the production of levetiracetam by-products, which are more toxic than the parent compound. The increased toxicity and the risk of formation of toxic metabolites represent one possible limitation to the implementation of photocatalytic treatment using TiO2 for the removal of losartan and levetiracetam. Our results proved that, the battery of ecotoxicity tests used in this work can be a promising investigation tool for the environmental risk assessment of photocatalytic processes.

Keywords: aquatic micropollutants, ecotoxicology, nano titanium dioxide, photocatalysis, water treatment

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Authors: Pratima Kumari, Sukha Ranjan Samadder

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This research aims to contribute to the sustainable production of graphene materials by exploring the extraction of graphite from spent primary and secondary batteries. The increasing demand for graphene materials, a versatile and high-performance material, necessitates environmentally friendly methods for its synthesis. The process involves a well-planned methodology, beginning with the gathering and categorization of batteries, followed by the disassembly and careful removal of graphite from anode structures. The use of environmentally friendly solvents and mechanical techniques ensures an efficient and eco-friendly extraction of graphite. Advanced approaches such as the modified Hummers' method and chemical reduction process are utilized for the synthesis of graphene materials, with a focus on optimizing parameters. Various analytical techniques such as Fourier-transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, and Raman spectroscopy were employed to validate the quality and structure of the produced graphene materials. The major findings of this study reveal the successful implementation of the methodology, leading to the production of high-quality graphene materials suitable for advanced material applications. Thorough characterization using various advanced techniques validates the structural integrity and purity of the graphene. The economic viability of the process is demonstrated through a comprehensive economic analysis, highlighting the potential for large-scale production. This research contributes to the field of sustainable production of graphene materials by offering a systematic methodology that efficiently transforms spent batteries into valuable graphene resources. Furthermore, the findings not only showcase the potential for upcycling electronic waste but also address the pressing need for environmentally conscious processes in advanced material synthesis.

Keywords: spent primary batteries, spent secondary batteries, graphite extraction, advanced material synthesis, circular economy approach

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