Search results for: organic zinc

Authors: Sisay Negash, Zebene Asfaw, Kibreselassie Daniel, Michael Zech

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A significant portion of the Ethiopian landscape features scattered trees that are deliberately managed in crop fields to enhance soil fertility and crop yield in which the compatibility of crops with these trees varies depending on location, tree species, and annual crop type. This study aimed to examine the effects of scattered Vachellia tortilis and Vachellia nilotica trees on selected physico-chemical properties of the soil, as well as the yield and yield components of sorghum in Ethiopia. Vachellia tortilis and Vachellia nilotica were selected on abundance occurrence and managed in crop fields. A randomized complete block design was used, with a distance from the tree canopy (middle, edge, and outside) as a treatment, and five trees of each species served as replications. Sorghum was planted up to 15 meters in the east, west, south, and north directions from the tree trunk to assess growth and yield. Soil samples were collected from the two tree species, three distance factors, three soil depths(0-20cm, 20-40cm, and 40-60cm), and five replications, totaling 45 samples for each tree species. These samples were analyzed for physical and chemical properties. The results indicated that both V. tortilis and V. nilotica significantly affected soil physico-chemical properties and sorghum yield. Specifically, soil moisture content, EC, total nitrogen, organic carbon, available phosphorus and potassium, CEC, sorghum plant height, panicle length, biomass, and yield decreased with increasing distance from the canopy. Conversely, bulk density and pH increased. Under the canopy, sorghum yield increased by 66.4% and 53.5% for V. tortilis and V. nilotica, respectively, due to higher soil moisture and nutrient availability. The study recommends promoting trees in crop fields, management options for new saplings, and further research on root decomposition and nutrient supply.

Keywords: canopy, crop yield, soil nutrient, soil organic matter, yield components

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Authors: Doris Fovwe Ogeleka, L. E. Tudararo-Aherobo, F. E. Okieimen

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The ecological effects of oil spill in the environment were studied in Warri riverine areas of Ubeji and Jeddo, Delta State. In the two communities, water and sediment samples were analysed for organics (polyaromatic hydrocarbon; total petroleum hydrocarbon (TPH)) and heavy metals (lead, copper, zinc, iron and chromium). The American Public Health Association (APHA) and the American Society for Testing and Materials (ASTM) methods were employed for the laboratory test. The results indicated that after a long period of oil spill (above one year), there were still significant concentrations (p<0.05) of organics indicating hydrocarbon pollution. Mean concentrations recorded for TPH in Ubeji and Jeddo waters were 23.60 ± 1.18 mg/L and 29.96 ± 0.14 mg/L respectively while total PAHs was 0.009 ± 0.002 mg/L and 0.008 ± 0.001 mg/L. Mean concentrations of TPH in the sediment was 48.83 ± 1.49 ppm and 1093 ± 74 ppm in the above order while total PAHs was 0.012 ± 0.002 ppm and 0.026 ± 0.004 ppm. Low concentrations were recorded for most of the heavy metals in the water and sediment. The observed concentrations of hydrocarbons in the study areas should provide the impetus for regulatory surveillance of oil discharged intentionally/unintentionally into the Warri riverine waters and sediment since hydrocarbon released into the environment sorb to the sediment particles where they cause harm to organisms in the sediment and overlying waters.

Keywords: crude oil, PAHs, TPH, oil spillage, water, sediment

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Authors: Siva Chander Chabattula, Piyush Kumar Gupta, Debashis Chakraborty, Rama Shanker Verma

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Green nanoparticles have gotten a lot of attention because of their potential applications in tissue regeneration, bioimaging, wound healing, and cancer therapy. The physical and chemical methods to synthesize metal oxide nanoparticles have an environmental impact, necessitating the development of an environmentally friendly green strategy for nanoparticle synthesis. In this study, we used Annona muricata plant leaf extract to synthesize Zinc Oxide nanoparticles (Am-ZnO NPs), which were evaluated using UV/Visible spectroscopy, FTIR spectroscopy, X-Ray Diffraction, DLS, and Zeta potential. Nanoparticles had an optical absorbance of 355 nm and a net negative surface charge of ~ - 2.59 mV. Transmission Electron Microscope characterizes the Shape and size of the nanoparticles. The obtained Am-ZnO NPs are biocompatible and hemocompatible in nature. These nanoparticles caused an anti-cancer therapeutic effect in MIA PaCa2 and MOLT4 cancer cells by inducing oxidative stress, and a change in mitochondrial membrane potential leads to programmed cell death. Further, we observed a reduction in the size of lung cancer spheroids (act as tumor micro-environment) with doxorubicin as a positive control.

Keywords: Biomaterials, nanoparticle, anticancer activity, ZnO nanoparticles

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Authors: M. Pacio, H. Juárez, R. Pérez-Cuapio E. Rosendo, T. Díaz, G. García

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In this study, zinc oxide (ZnO) quantum dots (QDs) have been prepared by a simple route. The growth parameters for ZnO QDs were systematically studied inside a SiO2 shell; this shell acts as a capping agent and also enhances stability of the nanoparticles in water. ZnO QDs in silica shell could be produced by initially synthesizing a ZnO colloid (containing ZnO nanoparticles in methanol solution) and then was mixed with 3-aminopropylsiloxane used as SiO2 precursor. ZnO QDs were deposited onto silicon substrates (100) orientation by spin-coating technique. ZnO QDs into a SiO2 shell were pre-heated at 300 °C for 10 min after each coating, that procedure was repeated five times. The films were subsequently annealing in air atmosphere at 500 °C for 2 h to remove the trapped fluid inside the amorphous silica cage. ZnO QDs showed hexagonal wurtzite structure and about 5 nm in diameter. The composition of the films at the surface and in the bulk was obtained by Secondary Ion Mass Spectrometry (SIMS), the spectra revealed the presence of Zn- and Si- related clusters associated to the chemical species in the solid matrix. Photoluminescence (PL) spectra under 325 nm of excitation only show a strong UV emission band corresponding to ZnO QDs, such emission is enhanced with annealing. Our results showed that the method is appropriate for the preparation of ZnO QDs films embedded in a SiO2 shell with high UV photoluminescence.

Keywords: ZnO QDs, sol gel, functionalization

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Authors: Wenjun Zhang, Thao Thi Le, Dongyup Shin, Jong Min Kim

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Electrochemical hydrogen peroxide (H₂O₂) synthesis holds significant promise for decentralized environmental remediation through the electro-Fenton process. However, challenges persist, such as the absence of robust electrocatalysts for the selective two-electron oxygen reduction reaction (2e⁻ ORR) and the high cost and sluggish kinetics of conventional electro-Fenton systems in treating highly concentrated wastewater. This study introduces an efficient water treatment system for removing substantial quantities of organic pollutants using an advanced electro-Fenton system coupled with a high-valent NiO catalyst. By employing a precipitation method involving crystal facet and cation vacancy engineering, a trivalent Ni (Ni³⁺)-rich NiO catalyst with a (111)-domain-exposed crystal facet, named {111}-NivO, was synthesized. This catalyst exhibited a remarkable 96% selectivity and a high mass activity of 59 A g⁻¹ for H₂O₂ production, outperforming all previously reported Ni-based catalysts. Furthermore, an advanced electro-Fenton system, integrated with a flow cell for electrochemical H₂O₂ production, was utilized to achieve 100% removal of 50 ppm bisphenol A (BPA) in 200 mL of wastewater under heavy-duty conditions, reaching a superior rapid degradation rate (4 min, k = 1.125 min⁻¹), approximately 102 times faster than the conventional electro-Fenton system. The hyper-efficiency is attributed to the continuous and appropriate supply of H₂O₂, the provision of O₂, and the timely recycling of the electrolyte under high current density operation. This catalyst also demonstrated a 93% removal of total organic carbon after 2 hours of operation and can be applied for efficient removal of highly concentrated phenol pollutants from aqueous systems, which opens new avenues for wastewater treatment.

Keywords: hydrogen peroxide production, nickel oxides, crystal facet and cation vacancy engineering, wastewater treatment, flow cell, electro-Fenton

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Authors: Ilze Dimanta, Zane Rutkovska, Vizma Nikolajeva, Janis Kleperis, Indrikis Muiznieks

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Majority of word’s steadily increasing energy consumption is provided by non-renewable fossil resources. Need to find an alternative energy resource is essential for further socio-economic development. Hydrogen is renewable, clean energy carrier with high energy density (142 MJ/kg, accordingly – oil has 42 MJ/kg). Biological hydrogen production is an alternative way to produce hydrogen from renewable resources, e.g. using organic waste material resource fermentation that facilitate recycling of sewage and are environmentally benign. Hydrogen gas is produced during the fermentation process of bacteria in anaerobic conditions. Bacteria are producing hydrogen in the liquid phase and when thermodynamic equilibrium is reached, hydrogen is diffusing from liquid to gaseous phase. Because of large quantities of available crude glycerol and the highly reduced nature of carbon in glycerol per se, microbial conversion of it seems to be economically and environmentally viable possibility. Such industrial organic waste product as crude glycerol is perspective for usage in feedstock for hydrogen producing bacteria. The process of biodiesel production results in 41% (w/w) of crude glycerol. The developed lab-scale test system (experimental bioreactor) with hydrogen micro-electrode (Unisense, Denmark) was used to determine hydrogen production yield and rate in the liquid phase. For hydrogen analysis in the gas phase the RGAPro-100 mass-spectrometer connected to the experimental test-system was used. Fermentative bacteria strains were tested for hydrogen gas production rates. The presence of hydrogen in gaseous phase was measured using mass spectrometer but registered concentrations were comparatively small. To decrease the hydrogen partial pressure in liquid phase reactor with a system for continuous bubbling with inert gas was developed. H2 production rate for the best producer in liquid phase reached 0,40 mmol H2/l, in gaseous phase - 1,32 mmol H2/l. Hydrogen production rate is time dependent – higher rate of hydrogen production is at the fermentation process beginning when concentration increases, but after three hours of fermentation, it decreases.

Keywords: bio-hydrogen, fermentation, experimental bioreactor, crude glycerol

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Authors: Kiurski S. Jelena, Ranogajec G. Jonjaua, Oros B. Ivana, Kecić S. Vesna

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The adsorption efficiency of fired clayey pellets of 5 and 8 mm diameter size for Cu(II) and Zn(II) ions removal from a waste printing developer was studied. In order to investigate the influence of contact time, adsorbent mass and pellet size on the adsorption efficiency the batch mode was carried out. Faster uptake of copper ions was obtained with the fired clay pellets of 5 mm diameter size within 30 minutes. The pellets of 8 mm diameter size showed the higher equilibrium time (60 to 75 minutes) for copper and zinc ions. The results pointed out that adsorption efficiency increases with the increase of adsorbent mass. The maximal efficiency is different for Cu(II) and Zn(II) ions due to the pellet size. Therefore, the fired clay pellets of 5 mm diameter size present an effective adsorbent for Cu(II) ions removal (adsorption efficiency is 63.6%), whereas the fired clay pellets of 8 mm diameter size are the best alternative for Zn(II) ions removal (adsorption efficiency is 92.8%) from a waste printing developer.

Keywords: adsorption efficiency, clayey pellet, metal ions, waste printing developer

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Authors: Marcin Zieliński, Marcin Dębowski, Mirosław Krzemieniewski

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The anaerobic degradation of substrates is limited especially by the rate and effectiveness of the first (hydrolytic) stage of fermentation. This stage may be intensified through pre-treatment of substrate aimed at disintegration of the solid phase and destruction of substrate tissues and cells. The most frequently applied criterion of disintegration outcomes evaluation is the increase in biogas recovery owing to the possibility of its use for energetic purposes and, simultaneously, recovery of input energy consumed for the pre-treatment of substrate before fermentation. Hydrodynamic cavitation is one of the methods for organic substrate disintegration that has a high implementation potential. Cavitation is explained as the phenomenon of the formation of discontinuity cavities filled with vapor or gas in a liquid induced by pressure drop to the critical value. It is induced by a varying field of pressures. A void needs to occur in the flow in which the pressure first drops to the value close to the pressure of saturated vapor and then increases. The process of cavitation conducted under controlled conditions was found to significantly improve the effectiveness of anaerobic conversion of organic substrates having various characteristics. This phenomenon allows effective damage and disintegration of cellular and tissue structures. Disintegration of structures and release of organic compounds to the dissolved phase has a direct effect on the intensification of biogas production in the process of anaerobic fermentation, on reduced dry matter content in the post-fermentation sludge as well as a high degree of its hygienization and its increased susceptibility to dehydration. A device the efficiency of which was confirmed both in laboratory conditions and in systems operating in the technical scale is a hydrodynamic generator of cavitation. Cavitators, agitators and emulsifiers constructed and tested worldwide so far have been characterized by low efficiency and high energy demand. Many of them proved effective under laboratory conditions but failed under industrial ones. The only task successfully realized by these appliances and utilized on a wider scale is the heating of liquids. For this reason, their usability was limited to the function of heating installations. Design of the presented cavitation generator allows achieving satisfactory energy efficiency and enables its use under industrial conditions in depolymerization processes of biomass with various characteristics. Investigations conducted on the laboratory and industrial scale confirmed the effectiveness of applying cavitation in the process of biomass destruction. The use of the cavitation generator in laboratory studies for disintegration of sewage sludge allowed increasing biogas production by ca. 30% and shortening the treatment process by ca. 20 - 25%. The shortening of the technological process and increase of wastewater treatment plant effectiveness may delay investments aimed at increasing system output. The use of a mechanical cavitator and application of repeated cavitation process (4-6 times) enables significant acceleration of the biogassing process. In addition, mechanical cavitation accelerates increases in COD and VFA levels.

Keywords: hydrodynamic cavitation, pretreatment, biomass, methane fermentation, Virginia fanpetals

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Authors: A. U. Adamu, Hamisu Abdu, A. A. Saidu

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The enzymatic synthesis of 3-O-β-D-glucopyranoside-betulinic acid using Novozyme-435 as a catalyst was studied. The effect of various parameters such as substrate molar ratio, reaction temperature, reaction time, re-used enzymes and amount of enzymes were investigated. The optimum rection conditions for the enzymatic glycosidation of betulinic acid in an organic solvent using Novozym-435 was found to be at 1:1.2 substrate molar ratio, 55oC, 24 h and 180 mg of enzymes with percentage conversion of 88.69 %.

Keywords: betulinic acid, glycosidation, novozyme-435, optimization

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Authors: Vesta Kohlmeier, George C. Dragan, Juergen Orasche, Juergen Schnelle-Kreis, Dietmar Breuer, Ralf Zimmermann

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Aerosols from hazardous semi-volatile organic compounds (SVOC) may occur in workplace air and can simultaneously be found as particle and gas phase. For health risk assessment, it is necessary to collect particles and gases separately. This can be achieved by using a denuder for the gas phase collection, combined with a filter and an adsorber for particle collection. The study focused on the suitability of carbonaceous monolithic multi-channel denuders, so-called Novacarb™-Denuders (MastCarbon International Ltd., Guilford, UK), to achieve gas-particle separation. Particle transmission efficiency experiments were performed with polystyrene latex (PSL) particles (size range 0.51-3 µm), while the time dependent gas phase collection efficiency was analysed for polar and nonpolar SVOC (mass concentrations 7-10 mg/m3) over 2 h at 5 or 10 l/min. The experimental gas phase collection efficiency was also compared with theoretical predictions. For n-hexadecane (C16), the gas phase collection efficiency was max. 91 % for one denuder and max. 98 % for two denuders, while for diethylene glycol (DEG), a maximal gas phase collection efficiency of 93 % for one denuder and 97 % for two denuders was observed. At 5 l/min higher gas phase collection efficiencies were achieved than at 10 l/min. The deviations between the theoretical and experimental gas phase collection efficiencies were up to 5 % for C16 and 23 % for DEG. Since the theoretical efficiency depends on the geometric shape and length of the denuder, flow rate and diffusion coefficients of the tested substances, the obtained values define an upper limit which could be reached. Regarding the particle transmission through the denuders, the use of one denuder showed transmission efficiencies around 98 % for 1-3 µm particle diameters. The use of three denuders resulted in transmission efficiencies from 93-97 % for the same particle sizes. In summary, NovaCarb™-Denuders are well applicable for sampling aerosols of polar/nonpolar substances with particle diameters ≤3 µm and flow rates of 5 l/min or lower. These properties and their compact size make them suitable for use in personal aerosol samplers. This work is supported by the German Social Accident Insurance (DGUV), research contract FP371.

Keywords: gas phase collection efficiency, particle transmission, personal aerosol sampler, SVOC

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Authors: Vishal Mahale, Jayashree Bijwe, Sujeet K. Sinha

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Range of thermal conductivity (TC) of Friction Materials (FMs) is a critical issue since lower TC leads to accumulation of frictional heat on the working surface, which results in excessive fade while higher TC leads to excessive heat flow towards back-plate resulting in boiling of brake-fluid leading to ‘spongy brakes’. This phenomenon prohibits braking action, which is most undesirable. Therefore, TC of the FMs across the brake pads should not be high while along the brake pad, it should be high. To enhance TC, metals in the forms of powder and fibers are used in the FMs. Apart from TC improvement, metals provide strength and structural integrity to the composites. Due to higher TC Copper (Cu) powder/fiber is a most preferred metallic ingredient in FM industry. However, Cu powders/fibers are responsible for metallic wear debris generation, which has harmful effects on aquatic organisms. Hence to get rid of a problem of metallic wear debris generation and to keep the positive effect of TC improvement, incorporation of Cu fabric in NAO brake-pads can be an innovative solution. Keeping this in view, two realistic multi-ingredient FM composites with identical formulations were developed in the form of brake-pads. Out of which one composite series consisted of a single layer of Cu fabric in the body of brake-pad and designated as C1 while double layer of Cu fabric was incorporated in another brake-pad series with designation of C2. Distance of Cu fabric layer from the back-plate was kept constant for C1 and C2. One more composite (C0) was developed without Cu fabric for the sake of comparison. Developed composites were characterized for physical properties. Tribological performance was evaluated on full scale inertia dynamometer by following JASO C 406 testing standard. It was concluded that Cu fabric successfully improved fade resistance by increasing conductivity of the composite and also showed slight improvement in wear resistance. Worn surfaces of pads and disc were analyzed by SEM and EDAX to study wear mechanism.

Keywords: brake inertia dynamometer, copper fabric, non-asbestos organic (NAO) friction materials, thermal conductivity enhancement

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Authors: Priyanka Govender, S. Mtshali, Theresa Moonsamy, Zanele Mkwanazi, L. Mthembu

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Chemically enhanced primary treatment (CEPT) can be used at wastewater works to improve the quality of the final effluent discharge, provided that the plant has spare anaerobic digestion capacity. CEPT can transfer part of the organic load to the digesters thereby effectively relieving the hydraulic loading on the plant and in this way can allow the plant to continue operating long after the hydraulic capacity of the plant has been exceeded. This can allow a plant to continue operating well beyond its original design capacity, requiring only fairly simple and inexpensive modifications to the primary settling tanks as well as additional chemical costs, thereby delaying or even avoiding the need for expensive capital upgrades. CEPT can also be effective at plants where high organic loadings prevent the wastewater discharge from meeting discharge standards, especially in the case of COD, phosphates and suspended solids. By increasing removals of these pollutants in the primary settling tanks, CEPT can enable the plant to conform to specifications without the need for costly upgrades. Laboratory trials were carried out recently at the Umbilo WWTW in Durban and these were followed by a baseline assessment of the current plant performance and a subsequent full scale trial on the Conventional plant i.e. West Plant. The operating conditions of the plant are described and the improvements obtained in COD, phosphate and suspended solids, are discussed. The PST and plant overall suspended solids removal efficiency increased by approximately 6% during the trial. Details regarding the effect that CEPT had on sludge production and the digesters are also provided. The cost implications of CEPT are discussed in terms of capital costs as well as operation and maintenance costs and the impact of Ferric chloride on the infrastructure was also studied and found to be minimal. It was concluded that CEPT improves the final quality of the discharge effluent, thereby improving the compliance of this effluent with the discharge license. It could also allow for a delay in upgrades to the plant, allowing the plant to operate above its design capacity. This will be elaborated further upon presentation.

Keywords: chemically enhanced, ferric, wastewater, primary

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Authors: Leila Tabrizi, Farnaz Dezhaboun

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In order to study the effect of plant nutrient source and different drying methods on physical and phytochemical characteristics of pot marigold (Calendula officinalis L., Asteraceae) flowers, a factorial experiment was conducted based on completely randomized design with three replications in Research Laboratory of University of Tehran in 2010. Different nutrient sources (vermicompost, municipal waste compost, cattle manure, mushroom compost and control) which were applied in a field experiment for flower production and different drying methods including microwave (300, 600 and 900 W), oven (60, 70 and 80oC) and natural-shade drying in room temperature, were tested. Criteria such as drying kinetic, antioxidant activity, total flavonoid content, total phenolic compounds and total carotenoid of flowers were evaluated. Results indicated that organic inputs as nutrient source for flowers had no significant effects on quality criteria of pot marigold except of total flavonoid content, while drying methods significantly affected phytochemical criteria. Application of microwave 300, 600 and 900 W resulted in the highest amount of total flavonoid content, total phenolic compounds and antioxidant activity, respectively, while oven drying caused the lowest amount of phytochemical criteria. Also, interaction effect of nutrient source and drying method significantly affected antioxidant activity in which the highest amount of antioxidant activity was obtained in combination of vermicompost and microwave 900 W. In addition, application of vermicompost combined with oven drying at 60oC caused the lowest amount of antioxidant activity. Based on results of drying trend, microwave drying showed a faster drying rate than those oven and natural-shade drying in which by increasing microwave power and oven temperature, time of flower drying decreased whereas slope of moisture content reduction curve showed accelerated trend.

Keywords: drying kinetic, medicinal plant, organic fertilizer, phytochemical criteria

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Authors: Sophio Kobauri, Tengiz Kantaria, Temur Kantaria, David Tugushi, Nina Kulikova, Ramaz Katsarava

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Nanosized environmentally responsive materials are of special interest for various applications, including targeted drug to a considerable potential for treatment of many human diseases. The important technological advantages of nanoparticles (NPs) usage as drug carriers (nanocontainers) are their high stability, high carrier capacity, feasibility of encapsulation of both hydrophilic or hydrophobic substances, as well as a high variety of possible administration routes, including oral application and inhalation. NPs can also be designed to allow controlled (sustained) drug release from the matrix. These properties of NPs enable improvement of drug bioavailability and might allow drug dosage decrease. The targeted and controlled administration of drugs using NPs might also help to overcome drug resistance, which is one of the major obstacles in the control of epidemics. Various degradable and non-degradable polymers of both natural and synthetic origin have been used for NPs construction. One of the most promising for the design of NPs are amino acid-based biodegradable polymers (AABBPs) which can clear from the body after the fulfillment of their function. The AABBPs are composed of naturally occurring and non-toxic building blocks such as α-amino acids, fatty diols and dicarboxylic acids. The particles designed from these polymers are expected to have an improved bioavailability along with a high biocompatibility. The present work deals with a systematic study of the preparation of NPs by cost-effective polymer deposition/solvent displacement method using AABBPs. The influence of the nature and concentration of surfactants, concentration of organic phase (polymer solution), and the ratio organic phase/inorganic (water) phase, as well as of some other factors on the size of the fabricated NPs have been studied. It was established that depending on the used conditions the NPs size could be tuned within 40-330 nm. As the next step of this research an evaluation of biocompatibility and bioavailability of the synthesized NPs has been performed, using two stable human cell culture lines – HeLa and A549. This part of study is still in progress now.

Keywords: amino acids, biodegradable polymers, nanoparticles (NPs), non-toxic building blocks

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Authors: Khairul Anuar, Wai Yee Lee, Daniel C. S. Bien, Hing Wah Lee, Ishak Azid

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This paper investigates the effect of ultrasonic treatment on ZnO nutrient solution prior to the growth of ZnO nanorods, where the seed layer is annealed at 50 and 100°C. The results show that the ZnO nanorods are successfully grown on the sample annealed at 50°C in the sonicated ZnO nutrient solution with a length and a diameter of approximately 8.025 µm and 92 nm, respectively. However, no ZnO nanorods structures are observed for the sample annealed at 50°C and grown in unsonicated ZnO nutrient solution. Meanwhile, the ZnO nanorods for the sample annealed at 100°C are successfully grown in both sonicated and unsonicated ZnO nutrient solutions. The length and diameter of the nanorods for the sample grown in the sonicated solution are 8.681 µm and 1.033 nm, whereas those for the sample grown in the unsonicated solution are 7.613 µm and 1.040 nm. This result shows that with ultrasonic treatment, the length of the ZnO nanorods increases by 14%, whereas their diameter is reduced by 0.7%, resulting in an increase of aspect ratio from 7:1 to 8:1. Electroconductivity and pH sensors are used to measure the conductivity and acidity level of the sonicated and unsonicated solutions, respectively. The result shows that the conductivity increases from 87 mS/cm to 10.4 mS/cm, whereas the solution pH decreases from 6.52 to 6.13 for the sonicated and unsonicated solutions, respectively. The increase in solution conductivity and acidity level elucidates the higher amount of zinc nutrient in the sonicated solution than in the unsonicated solution.

Keywords: ultrasonic treatment, low annealing temperature, ZnO nanostructure, nanorods

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Authors: Nidhi Gupta, Omita Nanda, Rakhi Grover, Kanchan Saxena

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Hybrid perovskite is new class of material which has gained much attention due to their different crystal structure and interesting optical and electrical properties. Easy fabrication, high absorption coefficient, and photoluminescence properties make them a strong candidate for various applications such as sensors, photovoltaics, photodetectors, etc. In perovskites, ions arrange themselves in a special type of crystal structure with chemical formula ABX3, where A is organic species like CH3NH3+, B is metal ion (e.g., Pb, Sn, etc.) and X is halide (Cl-, Br-, I-). In crystal structure, A is present at corner position, B at center of the crystal lattice and halide ions at the face centers. High stability and sensitivity of nanostructured perovskite make them suitable for chemical sensors. Researchers have studied sensing properties of perovskites for number of analytes such as 2,4,6-trinitrophenol, ethanol and other hazardous chemical compounds. Ammonia being highly toxic agent makes it a reason of concern for the environment. Thus the detection of ammonia is extremely important. Our present investigation deals with organic inorganic hybrid perovskite based ammonia sensor. Various methods like sol-gel, solid state synthesis, thermal vapor deposition etc can be used to synthesize Different hybrid perovskites. In the present work, a novel hybrid perovskite has been synthesized by a single step method. Ethylenediammnedihalide and lead halide were used as precursor. Formation of hybrid perovskite was confirmed by FT-IR and XRD. Morphological characterization of the synthesized material was performed using scanning electron microscopy (SEM). SEM analysis revealed the formation of one dimensional nanowire perovskite with mean diameter of 200 nm. Measurements for sensing properties of halide perovskite for ammonia vapor were carried out. Perovskite thin films showed a color change from yellow to orange on exposure of ammonia vapor. Electro-optical measurements show that sensor based on lead halide perovskite has high sensitivity towards ammonia with effective selectivity and reversibility. Sensor exhibited rapid response time of less than 20 seconds.

Keywords: hybrid perovskite, ammonia, sensor, nanostructure, thin film

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Authors: Tânia F. C. V. Silva, Eloísa S. S. Vieira, João Pinto da Costa, Rui A. R. Boaventura, Vitor J. P. Vilar

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Sanitary landfill leachates are characterized as a complex mixture of diverse organic and inorganic contaminants, which are usually removed by combining different treatment processes. Due to its simplicity, reliability, high cost-effectiveness and high nitrogen content (mostly under the ammonium form) inherent in this type of effluent, the activated sludge biological process is almost always applied in leachate treatment plants (LTPs). The purpose of this work is to assess the effect of the main nitrification and denitrification variables on the nitrogen's biological removal, from mature leachates. The leachate samples were collected after an aerated lagoon, at a LTP nearby Porto, presenting a high amount of dissolved organic carbon (1.0-1.3 g DOC/L) and ammonium nitrogen (1.1-1.7 g NH4+-N/L). The experiments were carried out in a 1-L lab-scale batch reactor, equipped with a pH, temperature and dissolved oxygen (DO) control system, in order to determine the reaction kinetic constants at unchanging conditions. The nitrification reaction rate was evaluated while varying the (i) operating temperature (15, 20, 25 and 30ºC), (ii) DO concentration interval (0.5-1.0, 1.0-2.0 and 2.0-4.0 mg/L) and (iii) solution pH (not controlled, 7.5-8.5 and 6.5-7.5). At the beginning of most assays, it was verified that the ammonium stripping occurred simultaneously to the nitrification, reaching up to 37% removal of total dissolved nitrogen. The denitrification kinetic constants and the methanol consumptions were calculated for different values of (i) volatile suspended solids (VSS) content (25, 50 and 100 mL of centrifuged sludge in 1 L solution), (ii) pH interval (6.5-7.0, 7.5-8.0 and 8.5-9.0) and (iii) temperature (15, 20, 25 and 30ºC), using effluent previously nitrified. The maximum nitrification rate obtained was 38±2 mg NH4+-N/h/g VSS (25ºC, 0.5-1.0 mg O2/L, pH not controlled), consuming 4.4±0.3 mg CaCO3/mg NH4+-N. The highest denitrification rate achieved was 19±1 mg (NO2--N+NO3--N)/h/g VSS (30ºC, 50 mL of sludge and pH between 7.5 and 8.0), with a C/N consumption ratio of 1.1±0.1 mg CH3OH/mg (NO2--N+NO3--N) and an overall alkalinity production of 3.7±0.3 mg CaCO3/mg (NO2--N+NO3--N). The denitrification process showed to be sensitive to all studied parameters, while the nitrification reaction did not suffered significant change when DO content was changed.

Keywords: mature sanitary landfill leachate, nitrogen removal, nitrification and denitrification parameters, lab-scale activated sludge biological reactor

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Authors: Mamdouh Omran, Timo Fabritius

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A growing interest in microwave heating has emerged recently. Many researchers have begun to pay attention to microwave energy as an alternative technique for processing various primary and secondary raw materials. Compared to conventional methods, microwave processing offers several advantages, such as selective heating, rapid heating, and volumetric heating. The present study gives a summary on our recent works related to the use of microwave energy for the recovery of valuable metals from primary and secondary raw materials. The research is mainly focusing on: Application of microwave for the recovery and recycling of metals from different metallurgical industries wastes (i.e. electric arc furnace (EAF) dust, blast furnace (BF), basic oxygen furnace (BOF) sludge). Application of microwave for upgrading and recovery of valuable metals from primary raw materials (i.e. iron ore). The results indicated that microwave heating is a promising and effective technique for processing primary and secondary steelmaking wastes. After microwave treatment of iron ore for 60 s and 900 W, about a 28.30% increase in grindability.Wet high intensity magnetic separation (WHIMS) indicated that the magnetic separation increased from 34% to 98% after microwave treatment for 90 s and 900 W. In the case of EAF dust, after microwave processing at 1100 W for 20 min, Zinc removal from 64 % to ~ 97 %, depending on mixture ratio and treatment time.

Keywords: dielectric properties, microwave heating, raw materials, secondary raw materials

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Authors: Abbas Hani

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In recent decades with the development of technology and lack of food sources, sewage sludge in production of human foods is inevitable. Various sources of municipal and industrial sewage sludge that is produced can provide the requirement of plant nutrients. Soils in arid, semi-arid climate of central Iran that most affected by water drainage, iron and zinc deficiencies, using of sewage sludge is helpful. Therefore, the aim of this study is investigation of sewage sludge and manure application on Ni and Zn uptake by Savory. An experiment in a randomized complete block design with three replications was performed. Sewage sludge treatments consisted of four levels, control, 15, 30, 80 tons per hectares, the manure was used in four levels of control, 20, 40 and 80 tons per hectare. Results showed that the wet and dry weights was not affected by sewage sludge using, while, manure has significant effect on them. The effect of sewage sludge on the cadmium and lead concentrations were significant. Interactions of sewage sludge and manure on dry weight values were not significant. Compare mean analysis showed that increasing the amount of sewage sludge had no significant effect on cadmium concentration and it reduced when sewage sludge usage increased. This is probably due to increased plant growth and reduced concentrations of these elements in the plant.

Keywords: savory, lead, cadmium, sewage sludge, manure

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Authors: Sarra K. Ikhlef, Onita Basu

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Natural organic matter (NOM) removal efficiency using drinking water treatment biological filters can be highly influenced by backwashing conditions. Backwashing has the ability to remove the accumulated biomass and particles in order to regenerate the biological filters' removal capacity and prevent excessive headloss buildup. A lab scale system consisting of 3 biological filters was used in this study to examine the implications of different backwash strategies on biological filtration performance. The backwash procedures were evaluated based on their impacts on dissolved organic carbon (DOC) removals, biological filters’ biomass, backwash water volume usage, and particle removal. Results showed that under nutrient limited conditions, the simultaneous use of air and water under collapse pulsing conditions lead to a DOC removal of 22% which was significantly higher (p>0.05) than the 12% removal observed under water only backwash conditions. Employing a bed expansion of 20% under nutrient supplemented conditions compared to a 30% reference bed expansion while using the same amount of water volume lead to similar DOC removals. On the other hand, utilizing a higher bed expansion (40%) lead to significantly lower DOC removals (23%). Also, a backwash strategy that reduced the backwash water volume usage by about 20% resulted in similar DOC removals observed with the reference backwash. The backwash procedures investigated in this study showed no consistent impact on biological filters' biomass concentrations as measured by the phospholipids and the adenosine tri-phosphate (ATP) methods. Moreover, none of these two analyses showed a direct correlation with DOC removal. On the other hand, dissolved oxygen (DO) uptake showed a direct correlation with DOC removals. The addition of the extended terminal subfluidization wash (ETSW) demonstrated no apparent impact on DOC removals. ETSW also successfully eliminated the filter ripening sequence (FRS). As a result, the additional water usage resulting from implementing ETSW was compensated by water savings after restart. Results from this study provide insight to researchers and water treatment utilities on how to better optimize the backwashing procedure for the goal of optimizing the overall biological filtration process.

Keywords: biological filtration, backwashing, collapse pulsing, ETSW

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Authors: Payman Davoodi-Nasab, Ahmad Rahbar-Kelishami, Jaber Safdari, Hossein Abolghasemi

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The high purity rare earth elements (REEs) have been vastly used in the field of chemical engineering, metallurgy, nuclear energy, optical, magnetic, luminescence and laser materials, superconductors, ceramics, alloys, catalysts, and etc. Neodymium is one of the most abundant rare earths. By development of a neodymium–iron–boron (Nd–Fe–B) permanent magnet, the importance of neodymium has dramatically increased. Solvent extraction processes have many operational limitations such as large inventory of extractants, loss of solvent due to the organic solubility in aqueous solutions, volatilization of diluents, etc. One of the promising methods of liquid membrane processes is emulsion liquid membrane (ELM) which offers an alternative method to the solvent extraction processes. In this work, a study on Nd extraction through multi-walled carbon nanotubes (MWCNTs) assisted ELM using response surface methodology (RSM) has been performed. The ELM composed of diisooctylphosphinic acid (CYANEX 272) as carrier, MWCNTs as nanoparticles, Span-85 (sorbitan triooleate) as surfactant, kerosene as organic diluent and nitric acid as internal phase. The effects of important operating variables namely, surfactant concentration, MWCNTs concentration, and treatment ratio were investigated. Results were optimized using a central composite design (CCD) and a regression model for extraction percentage was developed. The 3D response surfaces of Nd(III) extraction efficiency were achieved and significance of three important variables and their interactions on the Nd extraction efficiency were found out. Results indicated that introducing the MWCNTs to the ELM process led to increasing the Nd extraction due to higher stability of membrane and mass transfer enhancement. MWCNTs concentration of 407 ppm, Span-85 concentration of 2.1 (%v/v) and treatment ratio of 10 were achieved as the optimum conditions. At the optimum condition, the extraction of Nd(III) reached the maximum of 99.03%.

Keywords: emulsion liquid membrane, extraction of neodymium, multi-walled carbon nanotubes, response surface method

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Authors: Imen Blibech, Mohieddine Ksantini, Manohar Shete

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Bactrocera oleae is one of the most economically damaging insects of olive in Tunisia and other producing countries of olive trees. As a reliable alternative to synthetic chemical insecticides, botanical insecticides are considered natural control methods safe for the environment and human health. The certified botanical insecticide ULTRA-ACT® effectively on large scale of insects is approved per Indian and International organic standards certified organic pesticides. Olives with signs of olive fly infestation were collected from productive olive trees in three Sahel localities of Tunisia. Infested fruits were separated daily for larval stage control purposes, into new rearing boxes under microclimatic conditions at 75% R.H, 25 ± 3°C and 8 L-16D. Treatment with ULTRA-ACT® extract solutions was made by dipping methods; each fruit was pipetted in 5 mL of extract for 10 seconds then air- dried. Five doses of ULTRA-ACT® were used for a bioassay, plus a water-only control. A total of 200 infested olive fruits were treated in separate dishes with a proportion of 10 olives per dish. A total of 20 dishes were used for each concentration treatment as well as 20 dished utilized as control. The bioassay was conducted with 3 replicates. The development of the larval and pupal stages was recorded since the egg hatching until emergence of adults. It was determined that ULTRA-ACT® extracts on succeeding concentrations; 0.25, 0.5, 1 and 2% show significant effect on the biology of the pest. Increased concentration decreased significantly adult emergence from pupae and affect the egg hatchability percentage. Therefore, larval mortality increased insignificantly with the increase of the product concentration. The 2nd instar larvae were more susceptible to the product and after 72 hours the maximum mortality (75%) was observed with ULTRA-ACT® 2%. The present work aimed to give a possible and efficient alternative solution for B. oleae biological control with a promising botanical insecticide.

Keywords: Bactrocera oleae, olive insect pest, Ultra Act®, larval mortality, pupal emergency, biological control

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Authors: Muhammad Zaman Khan, Vijay Baheti, Jiri Militky

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The present study is focused on the development of multifunctional cotton fabric while having good physiological comfort properties. The functional properties developed include superhydrophobicity (Lotus effect) and UV protection. For this, TiO₂ nanoparticles along with fluorocarbon and organic-inorganic binder have been used to optimize the multifunctional properties. Deposition of TiO₂ nanoparticles with water repellent finish on cotton fabric has been carried out using the pad dry cure method at fix parameters. The morphology and elemental composition of as-deposited particles have been studied by using SEM and EDS. The chemical composition of nanoparticles was determined using energy dispersive spectroscopy. The treated samples exhibited excellent water repellency and UV protection factor. The study of the comfort properties of fabric showed that it had excellent physiological comfort properties. Optimized concentration of water repellent chemical (50g/l) was used in formulations with TiO₂ nanoparticles and organic-inorganic binder. Four formulations were prepared according to the design of the experiment. The formulations were applied to the cotton fabric by roller padding at room temperature (15–20°C). Surface morphology was investigated via SEM images. EDS analysis was also carried out to analyze the composition and atomic percentage of elements. The water contact angle (WCA) of cotton fabric increases with increase in TiO₂ nanoparticles concentration and reaches its maximum value (157°) when the concentration of TiO₂ is 20g/l. The water sliding angle (WSA) decreases and gains minimum value at the same concentration of TiO₂ at which WCA is highest. It was seen samples treated with formulations of TiO₂ nanoparticles exhibits excellent UPF, UV-A and UV-B blocking. However, there was no significant deterioration of air permeability. The water vapor permeability was also slightly decreased (4%) but is acceptable. It can be concluded that there is no significant change in both air and water vapor permeability after nanoparticles coating on the surface of the cotton fabric. The coated cotton fabric has little effect on the stiffness. The stiffness of coated samples was not increased significantly; thus comfort of cotton fabric is not decreased. This functionalized cotton fabric also exhibits good physiological comfort properties. ''The authors are also thankful to student grant competition 21312 provided at Technical University of Liberec''.

Keywords: comfort, functional, nanoparticles, UV protective

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Authors: Sophio Kobauri, Tengiz Kantaria, Temur Kantaria, David Tugushi, Nina Kulikova, Ramaz Katsarava

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Polymeric disperse systems such as nanoparticles (NPs) are of high interest for numerous applications in contemporary medicine and nanobiotechnology to a considerable potential for treatment of many human diseases. The important technological advantages of NPs usage as drug carriers (nanocontainers) are their high stability, high carrier capacity, feasibility of encapsulation of both hydrophilic or hydrophobic substances, as well as a high variety of possible administration routes, including oral application and inhalation. NPs can also be designed to allow controlled (sustained) drug release from the matrix. These properties of NPs enable improvement of drug bioavailability and might allow drug dosage decrease. The targeted and controlled administration of drugs using NPs might also help to overcome drug resistance, which is one of the major obstacles in the control of epidemics. Various degradable and non-degradable polymers of both natural and synthetic origin have been used for NPs construction. One of the most promising for the design of NPs are amino acid-based biodegradable polymers (AABBPs) which can clear from the body after the fulfillment of their function. The AABBPs are composed of naturally occurring and non-toxic building blocks such as α-amino acids, fatty diols and dicarboxylic acids. The particles designed from these polymers are expected to have an improved bioavailability along with a high biocompatibility. The present work deals with a systematic study of the preparation of NPs by cost-effective polymer deposition/solvent displacement method using AABBPs. The influence of the nature and concentration of surfactants, concentration of organic phase (polymer solution), and the ratio organic phase/inorganic(water) phase, as well as of some other factors on the size of the fabricated NPs have been studied. It was established that depending on the used conditions the NPs size could be tuned within 40-330 nm. At the next step of this research was carried out an evaluation of biocompability and bioavailability of the synthesized NPs using a stable human cell culture line – A549. It was established that the obtained NPs are not only biocompatible but they stimulate the cell growth.

Keywords: amino acids, biodegradable polymers, bioavailability, nanoparticles

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Authors: Boukrouh Soumaya, Cabaraux Jean-François, Avril Claire, Noutfia Ali, Chentouf Mouad

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The introduction of marginal leguminous forage species in the diet of ruminants are of great importance. Bitter vetch is a good source of proteins, highly resistant against drought and poor soil conditions. Accordingly; two years field trials (2018/2019 and 2019-2020) were conducted to determine the digestibility of straw and grains of 17 promising bitter vetch ecotypes(Vicia ervilia) in the north of Morocco. In vitro dry and organic matter digestibility, gas production, and kinetics of fermentation of grains and straw were evaluated using gas production technique, pepsin-cellulase enzymatic digestibility of DM (CDDM)and OM (CDOM), as well as protease enzymatic CP degradation (CPD) and in vitro true digestibility, were performed using DAISYII Incubator. In vitro digestibility was performed using gas production method of (Menke et al., 1979) improved by Menke and Steingass (1988). Samples were incubated in glass syringes that contained rumen fluid and incubation solution that conserved in water bath in 39°C during 72 hours. Gas production was recorded after 2, 4, 8, 12, 24, 48, and 72 hours. Studied digestibility parameters were dry and organic matter digestibility, microbial biomass production, partitioning factor, and volatile fatty acids. Enzymatic dry matter digestibility was different (p < 0.05) among grains and straw for all ecotypes. It varied from 804.1 to 957.7 g/kg DM and 270.4 to 412.3 g/kg DM for grains and straw, respectively. Metabolizable energy varied between 11.7 to 14.3 MJ/kg DM and 2.6 to 5.0 MJ/kg DM for grains and straw, respectively. Potential gas production (A), the rate constants (c and d), and lag times of grains and straws from different bitter vetch ecotypes were different (p > 0.05). The results emphasized that in any evaluation of bitter vetch ecotypes, where straw of this legume seed is used as an animal feed, not only seed yield but also yield and quality of straw should be taken into consideration, particularly in areas where straw from this legume is considered as an important feedstuff for ruminants. Enzymatic digestibility was lower than in vitro digestibility by gaz production and by the DAISYII method because rumen fluid contains bacteria than increase digestibility. There was no difference between in vitro digestibility by gaz production and the DAISY II method. The DAISY II method can be used to increase labor efficiency in the in vitro DM digestibility analysis if gaz production is not necessary for analysis.

Keywords: bitter vetch, grains, straw, ecotype, in vitro digestibility, gaz production, enzymatic digestibility

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Authors: Kamel A. Abd-Elsalam, Alexei R. Khokhlov

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Studies on bioefficacy (in vitro and in vivo) and mode of action of the nanocides against the most important plant diseases in Egypt and Russia might assist in the goal of sustainable agriculture. To our knowledge, few researchers have evaluated the combined antimicrobial effect of inorganic nanoparticles (NPs) with bioorganic pesticides for controlling plant pathogens in the greenhouse and open field, decontrol investigated synergistic effect. In the current project, we will develop eco-friendly alternative management strategies including the use of heavy nanometal-tolerant Trichoderma strains and the main effective material in conventional fungicides (curpic, sulfur, phosphorus and zinc) for controlling plant diseases. Studies on bioefficacy and the mechanism of the nanocides against the most important plant diseases in Egypt were evaluated. There is a growing need to establish mechanisms of action for nano bio and/or fungicides to assist the design of new compounds or combinations of compounds, in order to understand resistance mechanisms and to provide a focus for toxicological attention. Nanofungicides represent an emerging technological development that could offer a range of benefits including increased efficacy, durability, and a reduction in the amounts of active ingredients that need to be used.

Keywords: biohybrids, biocides, bioagent, plant pathogenic fungi

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Authors: Yasir Ali Arfat

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Composite films based on fish protein isolate (FPI) and fish skin gelatin (FSG) blend incorporated with 50 and 100% (w/w, protein) basil leaf essential oil (BEO) in the absence and presence of 3% (w/w, protein) ZnO nanoparticles (ZnONP) were prepared and characterised. Tensile strength (TS) decreased, whilst elongation at break (EAB) increased as BEO level increased (p < 0.05). However, ZnONP addition resulted in higher TS but lower EAB (p < 0.05). The lowest water vapour permeability (WVP) was observed for the film incorporated with 100% BEO and 3% ZnONP (p < 0.05). BEO and ZnONP incorporation decreased transparency of FPI/FSG films (p < 0.05). FTIR spectra indicated that films added with BEO exhibited higher hydrophobicity. Both BEO and ZnONP had a marked impact on thermal stability of the films. Microstructural study revealed that presence of ZnONP prevented bilayer formation of film containing 100% BEO. FPI/FSG films incorporated with 100% BEO, especially in combination with ZnONP, exhibited strong antibacterial activity against food pathogenic and spoilage bacteria and thus could be used as an active food packaging material to ensure safety and to extend the shelf-life of packaged foods.

Keywords: bionanocomposite, fish protein isolate, fish skin gelatin, basil essential oil, ZnO nanoparticles, antimicrobial packaging

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Authors: Jovana Nikolov, Natasa Todorovic, Ivana Stojkovic

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Monitoring of 222Rn in drinking or surface waters, as well as in groundwater has been performed in connection with geological, hydrogeological and hydrological surveys and health hazard studies. Liquid scintillation counting (LSC) is often preferred analytical method for 222Rn measurements in waters because it allows multiple-sample automatic analysis. LSC method implies mixing of water samples with organic scintillation cocktail, which triggers radon diffusion from the aqueous into organic phase for which it has a much greater affinity, eliminating possibility of radon emanation in that manner. Two direct LSC methods that assume different sample composition have been presented, optimized and evaluated in this study. One-phase method assumed direct mixing of 10 ml sample with 10 ml of emulsifying cocktail (Ultima Gold AB scintillation cocktail is used). Two-phase method involved usage of water-immiscible cocktails (in this study High Efficiency Mineral Oil Scintillator, Opti-Fluor O and Ultima Gold F are used). Calibration samples were prepared with aqueous 226Ra standard in glass 20 ml vials and counted on ultra-low background spectrometer Quantulus 1220TM equipped with PSA (Pulse Shape Analysis) circuit which discriminates alpha/beta spectra. Since calibration procedure is carried out with 226Ra standard, which has both alpha and beta progenies, it is clear that PSA discriminator has vital importance in order to provide reliable and precise spectra separation. Consequentially, calibration procedure was done through investigation of PSA discriminator level influence on 222Rn efficiency detection, using 226Ra calibration standard in wide range of activity concentrations. Evaluation of presented methods was based on obtained efficiency detections and achieved Minimal Detectable Activity (MDA). Comparison of presented methods, accuracy and precision as well as different scintillation cocktail’s performance was considered from results of measurements of 226Ra spiked water samples with known activity and environmental samples.

Keywords: 222Rn in water, Quantulus1220TM, scintillation cocktail, PSA parameter

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Authors: Fawad Ali, Muhammad Ateeq, Ikhtiar Khan

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Ground water, a major source of drinking water supply in Peshawar has been severely contaminated by leather tanning industry. Effluents from the tanneries contain high concentration of chromium besides several other chemical species. Release of untreated effluents from the tanning industry has severely damaged surface and ground water, agriculture soil as well as vegetables and crops. Chromium is a well-known carcinogenic and mutagenic agent. Once in the human food chain, it causes multiple problems to the exposed population including various types of cancer, skin dermatitis, and DNA damage. In order to assess the extent of chromium and other heavy metals contamination, water samples were analyzed for heavy metals using Graphite Furnace Atomic Absorption Spectrometer (GFAAS, Analyst 700, Perkin Elmer). Total concentration of chromium was above the permissible limit (0.048 mg/l) in 85% of the groundwater (drinking water) samples. The concentration of cobalt, manganese, cadmium, nickel, lead, zinc and iron was also determined in the ground water, surface water, agriculture soil, and vegetables samples from the affected area.

Keywords: heavy metals, soil, groundwater, tannery effluents, food chain

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Authors: Jun Sun, Tsz Tin Yu, Maryam Mirabediny, Matthew Lee, Adele Jones, Denis M. O’Carroll, Michael J. Manefield, Björn Åkermark, Biswanath Das, Naresh Kumar

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Reductive defluorination has emerged as a sustainable approach to clean water from Per and polyfluoroalkyl substances (PFASs), also known as forever organic containments. For last few decades, nano zero valent metals (nZVMs) have been intensively applied in the reductive remediation of groundwater contaminated with chlorinated organic compounds due to its low redox potential, easy application, and low production cost. However, there is inadequate information on the effective reductive defluorination of linear or branched PFAS using nZVMs as reductants because of the lack of suitable catalysts. CoII-5,10,15,20-Tetraphenyl-21H,23H-porphyrin (CoTPP) has been recently reported for effective catalyzing reductive defluorination of branched (br-) perfluorooctane sulfonate (PFOS) by using TiIII citrate as reductant. However, the low water solubility of CoTPP limited its applicability. Here, we explored a series of structurally related soluble cobalt porphyrin catalysts based on our previously reported best performing CoTPP. All soluble porphyrins [[meso-tetra(4-carboxyphenyl)porphyrinato]cobalt(III)]Cl·₇H₂O (CoTCPP), [[meso-tetra(4-sulfonatophenyl) porphyrinato]cobalt(III)]·9H2O (CoTPPS), and [[meso-tetra(4-N-methylpyridyl) porphyrinato]cobalt(II)](I)₄·₄H₂O (CoTMpyP) displayed better defluorination efficiencies than CoTPP. Especially, CoTMpyP presented the best defluorination efficiency for br-PFOS (94 %), branched perfluorooctanoic acid (PFOA) (89 %), and 3,7-Perfluorodecanoic acid (PFDA) (60 %) after 1 day at 70 0C. CoTMpyP-nZn0 system showed 88-164 times higher defluorination rate than VB12-nZn0 system in terms of all investigated br-PFASs. The CoTMpyP-nZn0 also performed effectively at room temperature, demonstrating the potential prospect for in-situ reductive systems. Based on the analysis of the intermediate products, the calculated bond dissociation energies (BDEs) and possible first interaction between CoTMpyP and PFAS, degradation pathways of 3,7-PFDA and 6-PFOS are proposed.

Keywords: cationic, soluble porphyrin, cobalt, vitamin b12, pfas, reductive defluorination

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