Search results for: Cr(III)/Cr(VI) ions

Authors: Dhivya Arumugam, Kaliyappan Thananjeyan

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The monomer of (3-((4-(methacryloyloxy)phenylimino)methyl)-2-hydroxybenzoic acid) schiff base polymer was prepared by reacting methacryloyl chloride with imine compound derived from 3-formylsalisylic acid and 4- aminophenol. The monomer was polymerized in DMF at 70oC using benzoyl peroxide as free radical initiator. Polymer metal complex was obtained in DMF solution of polymer with aqueous solution of metal ions. The polymer and the polymer metal complex were characterized by elemental analysis and spectral studies. The elemental analysis data suggest that the metal to ligand ratio is 1:1 and hence, it acts as a binucleating compartmental ligand. The IR spectral data of these complexes suggest that the metals are coordinated through nitrogen of the imine group, the oxygen of carboxylate ion and the oxygen of the phenolic –OH group which also acts as the bridging ligand. The electronic spectra and magnetic moments of the polychelates shows that octahedral and square planar structure for Ni(II) and Cu(II) complexes respectively. X-ray diffraction studies revealed that polychelates are highly crystalline. The thermal and electrical properties, catalytic activity, structure property relationships are discussed. Further the synthesized polymer was used for metal uptake studies from waste water, which is one of the effective waste water treatment strategies. And also, the polymers and polychelates were investigated for antimicrobial activity with various microorganisms by using agar well diffusion method and the results have been discussed.

Keywords: acyclic compartmental ligands, binucleating ligand, 3-formylsalicylic acid, free radical polymerization, polluting ions, polychelate

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Authors: Šárka Hradilová, Aleš Panáček, Radek Zbořil

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Nanotechnologies are considered the most promising fields with high added value, brings new possibilities in various sectors from industry to medicine. With the growing of interest in nanomaterials and their applications, increasing nanoparticle production leads to increased exposure of people and environment with ‘human made’ nanoparticles. Nanoparticles (NPs) are clusters of atoms in the size range of 1–100 nm. Metal nanoparticles represent one of the most important and frequently used types of NPs due to their unique physical, chemical and biological properties, which significantly differ from those of bulk material. Biological properties including toxicity of metal nanoparticles are generally determined by their size, size distribution, shape, surface area, surface charge, surface chemistry, stability in the environment and ability to release metal ions. Therefore, the biological behavior of NPs and their possible adverse effect cannot be derived from the bulk form of material because nanoparticles show unique properties and interactions with biological systems just due to their nanodimensions. Silver and gold NPs are intensively studied and used. Both can be used for instance in surface enhanced Raman spectroscopy, a considerable number of applications of silver NPs is associated with antibacterial effects, while gold NPs are associated with cancer treatment and bio imaging. Antibacterial effects of silver ions are known for centuries. Silver ions and silver-based compounds are highly toxic to microorganisms. Toxic properties of silver NPs are intensively studied, but the mechanism of cytoxicity is not fully understood. While silver NPs are considered toxic, gold NPs are referred to as toxic but also innocuous for eukaryotic cells. Therefore, gold NPs are used in various biological applications without a risk of cell damaging, even when we want to suppress the growth of cancer cells. Thus, gold NPs are toxic or harmless. Because most studies comparing particles of various sizes prepared in various ways, and testing is performed on different cell lines, it is very difficult to generalize. The novelty and significance of our research is focused to the complex biological effects of silver and gold NPs prepared by the same method, have the same parameters and the same stabilizer. That is why we can compare the biological effects of pure nanometals themselves based on their chemical nature without the influence of other variable. Aim of our study therefore is to compare the cytotoxic effect of two types of noble metal NPs focusing on the mechanisms that contribute to cytotoxicity. The study was conducted on murine fibroblasts by selected common used tests. Each of these tests monitors the selected area related to toxicity and together provides a comprehensive view on the issue of interactions of nanoparticles and living cells.

Keywords: cytotoxicity, gold nanoparticles, mechanism of cytotoxicity, silver nanoparticles

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Authors: N. K. Ambujam, V. Sudha

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Reservoirs are being contaminated all around the world with point source and Non-Point Source (NPS) pollution. The most common NPS pollutants are sediments and nutrients. Krishnagiri Reservoir (KR) has been chosen for the present case study, which is located in the tropical semi-arid climatic zone of Tamil Nadu, South India. It is the main source of surface water in Krishnagiri district to meet the freshwater demands. The reservoir has lost about 40% of its water holding capacity due to sedimentation over the period of 50 years. Hence, from the research and management perspective, there is a need for a sound knowledge on the spatial and seasonal variations of KR water quality. The present study encompasses the specific objectives as (i) to investigate the longitudinal heterogeneity and seasonal variations of physicochemical parameters, nutrients and biological characteristics of KR water and (ii) to examine the extent of degradation of water quality in KR. 15 sampling points were identified by uniform stratified method and a systematic monthly sampling strategy was selected due to high dynamic nature in its hydrological characteristics. The physicochemical parameters, major ions, nutrients and Chlorophyll a (Chl a) were analysed. Trophic status of KR was classified by using Carlson's Trophic State Index (TSI). All statistical analyses were performed by using Statistical Package for Social Sciences programme, version-16.0. Spatial maps were prepared for Chl a using Arc GIS. Observations in KR pointed out that electrical conductivity and major ions are highly variable factors as it receives inflow from the catchment with different land use activities. The study of major ions in KR exhibited different trends in their values and it could be concluded that as the monsoon progresses the major ions in the water decreases or water quality stabilizes. The inflow point of KR showed comparatively higher concentration of nutrients including nitrate, soluble reactive phosphorus (SRP), total phosphors (TP), total suspended phosphorus (TSP) and total dissolved phosphorus (TDP) during monsoon seasons. This evidently showed the input of significant amount of nutrients from the catchment side through agricultural runoff. High concentration of TDP and TSP at the lacustrine zone of the reservoir during summer season evidently revealed that there was a significant release of phosphorus from the bottom sediments. Carlson’s TSI of KR ranged between 81 and 92 during northeast monsoon and summer seasons. High and permanent Cyanobacterial bloom in KR could be mainly due to the internal loading of phosphorus from the bottom sediments. According to Carlson’s TSI classification Krishnagiri reservoir was ranked in the hyper-eutrophic category. This study provides necessary basic data on the spatio-temporal variations of water quality in KR and also proves the impact of point and NPS pollution from the catchment area. High TSI warrants a greater threat for the recovery of internal P loading and hyper-eutrophic condition of KR. Several expensive internal measures for the reduction of internal loading of P were introduced by many scientists. However, the outcome of the present research suggests for the innovative algae harvesting technique for the removal of sediment nutrients.

Keywords: NPS pollution, nutrients, hyper-eutrophication, krishnagiri reservoir

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Authors: Juliana A. B. Silva, Caio H. T. L. Albuquerque, Leonardo L. dos Santos, Cristiane K. Oliveira, Ivani Malvestiti, Fernando Hallwass, Ricardo L. Longo

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Complexes with lanthanide ions have been extensively studied due to their applications as luminescent, magnetic and catalytic materials as molecular or extended crystals, thin films, glasses, polymeric matrices, ionic liquids, and in solution. NMR chemical shift data in solution have been reported and suggest fluxional structures in a wide range of coordination compounds with rare earth ions. However, the fluxional mechanisms for these compounds are still not established. This structural fluxionality may affect the photophysical, catalytic and magnetic properties in solution. Thus, understanding the structural interconversion mechanisms may aid the design of coordination compounds with, for instance, improved (electro)luminescence, catalytic and magnetic behaviors. The [Eu(btfa)₃bipy] complex, where btfa= 4,4,4-trifluoro-1-phenyl-1,3-butanedionate and bipy= 2,2’-bipiridyl, has a well-defined X-ray crystallographic structure and preliminary 1H NMR data suggested a structural fluxionality. Thus, we have investigated a series of coordination compounds with lanthanide ions [Ln(btfa)₃L], where Ln = La, Eu, Gd or Yb and L= bipy or phen (phen=1,10-phenanthroline) using a combined theoretical-experimental approach. These complexes were synthesized and fully characterized, and detailed NMR measurements were obtained. They were also studied by quantum chemical computational methods (DFT-PBE0). The aim was to determine the relevant factors in the structure of these compounds that favor or not the fluxional behavior. Measurements of the 1H NMR signals at variable temperature in CD₂Cl₂ of the [Eu(btfa)₃L] complexes suggest that these compounds have a fluxional structure, because the crystal structure has non-equivalent btfa ligands that should lead to non-equivalent hydrogen atoms and thus to more signals in the NMR spectra than those obtained at room temperature, where all hydrogen atoms of the btfa ligands are equivalent, and phen ligand has an effective vertical symmetry plane. For the [Eu(btfa)₃bipy] complex, the broadening of the signals at –70°C provides a lower bound for the coalescence temperature, which indicates the energy barriers involved in the structural interconversion mechanisms are quite small. These barriers and, consequently, the coalescence temperature are dependent upon the radii of the lanthanide ion as well as to their paramagnetic effects. The PBE0 calculated structures are in very good agreement with the crystallographic data and, for the [Eu(btfa)₃bipy] complex, this method provided several distinct structures with almost the same energy. However, the energy barrier for structural interconversion via dissociative pathways were found to be quite high and could not explain the experimental observations. Whereas the pseudo-rotation pathways, involving the btfa and bipy ligands, have very small activation barriers, in excellent agreement with the NMR data. The results also showed an increase in the activation barrier along the lanthanide series due to the decrease of the ionic radii and consequent increase of the steric effects. TD-DFT calculations showed a dependence of the ligand donor state energy with different structures of the complex [Eu(btfa)₃phen], which can affect the energy transfer rates and the luminescence. The energy required to promote the structural fluxionality may also enhance the luminescence quenching in solution. These results can aid in the design of more luminescent compounds and more efficient devices.

Keywords: computational chemistry, lanthanide-based compounds, NMR, structural fluxionality

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Authors: Neda Amidi Fazli, Farid Amidi Fazli

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Enriched fruits by minerals provide minerals which are needed to human body the minerals are used by body cells for daily activities. This paper indicates the result of mass transfer in fruit slices in 55% sucrose syrup in presence of calcium and phosphorus ions. Osmosis agent 55% (w/w) was prepared by solving sucrose in deionized water and adding calcium or phosphorus in 1 and 2% concentration. Dry matter, solid gain, water loss as well as weight reduction were calculated. Results showed that by increasing of calcium concentration in osmosis solution solid gain, water loss and weight reduction were increased in short experiment time in kiwi fruit but the parameters decreased in long experiment time by concentration increasing and rise of calcium concentration caused decrease of osmosis parameters in banana. In the case of phosphorus, increasing of ion concentration had adverse effect on all treatments, this may be due to different osmosis force that is created by two types of ions. The mentioned parameters decreased in all treatments by increasing of ion concentration. Highest mass transfer in kiwi fruit occurs when 1% calcium solution applied for 60 minutes, values obtained for solid gain, water loss and weight reduction were 42.60, 51.97, and 9.37 respectively. In the case of banana, when 2% phosphorus concentration was applied as osmosis agent for 60 minutes highest values for solid gain, water loss and weight reduction obtained as 21, 25.84, and 4.84 respectively.

Keywords: calcium, concentration, osmotic dehydration, phosphorus

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Authors: Omoruyi Gold Idemudia, Alexander P. Sadimenko

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The synthesis of N-heterocycles with novel properties, having broad spectrum biological activities that may become alternative medicinal drugs, have been attracting a lot of research attention due to the emergence of medicinal drug’s limitations such as disease resistance and their toxicity effects among others. Acylpyrazolones have been employed as pharmaceuticals as well as analytical reagent and their application as coordination complexes with transition metal ions have been well established. By way of a condensation reaction with amines acylpyrazolone ketones form a more chelating and superior group of compounds known as azomethines. 4-propyl-3-methyl-1-phenyl-2-pyrazolin-5-one was reacted with phenylhydrazine to get a new phenylhydrazone which was further reacted with aqueous solutions of palladium and platinum salts, in an effort towards the discovery of transition metal based synthetic drugs. The compounds were characterized by means of analytical, spectroscopic, thermogravimetric analysis TGA, as well as x-ray crystallography. 4-propyl-3-methyl-1-phenyl-2-pyrazolin-5-one phenylhydrazone crystallizes in a triclinic crystal system with a P-1 (No. 2) space group based on x-ray crystallography. The bidentate ON ligand formed a square planar geometry on coordinating with metal ions based on FTIR, electronic and NMR spectra as well as magnetic moments. Reported compounds showed antibacterial activities against the nominated bacterial isolates using the disc diffusion technique at 20 mg/ml in triplicates. The metal complexes exhibited a better antibacterial activity with platinum complex having an MIC value of 0.63 mg/ml. Similarly, ligand and complexes also showed antioxidant scavenging properties against 2, 2-diphenyl-1-picrylhydrazyl DPPH radical at 0.5mg/ml relative to ascorbic acid (standard drug).

Keywords: acylpyrazolone, antibacterial studies, metal complexes, phenylhydrazone, spectroscopy

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Authors: Ayla Roberta Galaco, Juliana Fonseca De Lima, Osvaldo Antonio Serra

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Coordination polymers, also known as metal-organic frameworks (MOFs) or lanthanoide organic frameworks (LOFs) have been reported due of their promising applications in gas storage, separation, catalysis, luminescence, magnetism, drug delivery, and so on. As a type of organic–inorganic hybrid materials, the properties of coordination polymers could be chosen by deliberately selecting the organic and inorganic components. LOFs have received considerable attention because of their properties such as porosity, luminescence, and magnetism. Methods such as solvothermal synthesis are important as a strategy to control the structural and morphological properties as well as the composition of the target compounds. In this work the first solvothermal synthesis was employed to obtain the compound [Y0.4,Yb0.4,Er0.2(dmf)(for)(H2O)(tft)], by using terephthalic acid (tft) and oxalic acid, decomposed in formate (for), as ligands; Yttrium, Ytterbium and, Erbium as metal centers, in DMF and water for 4 days under 160 °C. The semi-rigid terephthalic acid (dicarboxylic) coordinates with Ln3+ ions and also is possible to form a polyfunctional bridge. On the other hand, oxalate anion has no high-energy vibrational groups, which benefits the excitation of Yb3+ in upconversion process. It was observed that the compounds with water molecules in the coordination sphere of the lanthanoide ions cause lower crystalline properties and change the structure of the LOF (1D, 2D, 3D). In the FTIR, the bands at 1589 and 1500 cm-1 correspond to the asymmetric stretching vibration of –COO. The band at 1383 cm-1 is assigned to the symmetric stretching vibration of –COO. Single crystal X-ray diffraction study reveals an infinite 3D coordination framework that crystalizes in space group P21/c. The other three products, [TR(chel)(ofd)0,5(H2O)2], where TR= Eu3+, Y3, and Yb3+/Er3+ were obtained by using 1, 2-phenylenedioxydiacetic acid (ofd) and chelidonic acid (chel) as organic ligands. Thermal analysis shows that the lanthanoide organic frameworks do not collapse at temperatures below 250 °C. By the polycrystalline X-ray diffraction patterns (PXRD) it was observed that the compounds with Eu3+, Y3+, and Yb3+/Er3+ ions are isostructural. From PXRD patterns, high crystallinity can be noticed for the complexes. The final products were characterized by single X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), energy dispersive spectroscopy (EDS) and thermogravimetric analysis (TGA). The X-ray diffraction (XRD) is an effective method to investigate crystalline properties of synthesized materials. The solid crystal obtained in the synthesis show peaks at 2θ < 10°, indicating the MOF formation. The chemical composition of LOFs was also confirmed by EDS.

Keywords: isostructural, lanthanoids, lanthanoids organic frameworks (LOFs), metal organic frameworks (MOFs), thermogravimetry, X-Ray diffraction

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Authors: Lixin Zhao, Genmao Zhou

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Traditional acid in-situ leaching (ISL) is not suitable for the sandstone uranium deposit with low permeability and high content of carbonate minerals, because of the blocking of calcium sulfate precipitates. Another factor influences the uranium acid in-situ leaching is that the pyrite in ore rocks will react with oxidation reagent and produce lots of sulfate ions which may speed up the precipitation process of calcium sulphate and consume lots of oxidation reagent. Due to the advantages such as less chemical reagent consumption and groundwater pollution, CO₂+O₂ in-situ leaching method has become one of the important research areas in uranium mining. China is the second country where CO₂+O₂ ISL has been adopted in industrial uranium production of the world. It is shown that the CO₂+O₂ ISL in China has been successfully developed. The reaction principle, technical process, well field design and drilling engineering, uranium-bearing solution processing, etc. have been fully studied. At current stage, several uranium mines use CO₂+O₂ ISL method to extract uranium from the ore-bearing aquifers. The industrial application and development potential of CO₂+O₂ ISL method in China are summarized. By using CO₂+O₂ neutral leaching technology, the problem of calcium carbonate and calcium sulfate precipitation have been solved during uranium mining. By reasonably regulating the amount of CO₂ and O₂, related ions and hydro-chemical conditions can be controlled within the limited extent for avoiding the occurrence of calcium sulfate and calcium carbonate precipitation. Based on this premise, the demand of CO₂+O₂ uranium leaching has been met to the maximum extent, which not only realizes the effective leaching of uranium, but also avoids the occurrence and precipitation of calcium carbonate and calcium sulfate, realizing the industrial development of the sandstone type uranium deposit.

Keywords: CO₂+O₂ ISL, industrial production, well field layout, uranium processing

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Authors: Bienvenu Gael Fouda Mbanga

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This study reports a new approach of preparation of carbon nanoparticles coated cerium oxide nanorods (CNPs/CeONRs) nanocomposite and reusing the spent adsorbent of Cd2+- CNPs/CeONRs nanocomposite for latent fingerprint detection (LFP) after removing Cd2+ ions from aqueous solution. CNPs/CeONRs nanocomposite was prepared by using CNPs and CeONRs with adsorption processes. The prepared nanocomposite was then characterized by using UV-visible spectroscopy (UV-visible), Fourier transforms infrared spectroscopy (FTIR), X-ray diffraction pattern (XRD), scanning electron microscope (SEM), Transmission electron microscopy (TEM), Energy-dispersive X-ray spectroscopy (EDS), Zeta potential, X-ray photoelectron spectroscopy (XPS). The average size of the CNPs was 7.84nm. The synthesized CNPs/CeONRs nanocomposite has proven to be a good adsorbent for Cd2+ removal from water with optimum pH 8, dosage 0. 5 g / L. The results were best described by the Langmuir model, which indicated a linear fit (R2 = 0.8539-0.9969). The adsorption capacity of CNPs/CeONRs nanocomposite showed the best removal of Cd2+ ions with qm = (32.28-59.92 mg/g), when compared to previous reports. This adsorption followed pseudo-second order kinetics and intra particle diffusion processes. ∆G and ∆H values indicated spontaneity at high temperature (40oC) and the endothermic nature of the adsorption process. CNPs/CeONRs nanocomposite therefore showed potential as an effective adsorbent. Furthermore, the metal loaded on the adsorbent Cd2+- CNPs/CeONRs has proven to be sensitive and selective for LFP detection on various porous substrates. Hence Cd2+-CNPs/CeONRs nanocomposite can be reused as a good fingerprint labelling agent in LFP detection so as to avoid secondary environmental pollution by disposal of the spent adsorbent.

Keywords: Cd2+-CNPs/CeONRs nanocomposite, cadmium adsorption, isotherm, kinetics, thermodynamics, reusable for latent fingerprint detection

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Authors: Dimitra Das, Anuradha Mitra, Kalyan Kumar Chattopadhyay

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Organic polymers, constructed from light elements like carbon, hydrogen, nitrogen, oxygen, sulphur, and boron atoms, are the emergent class of non-toxic, metal-free, environmental benign advanced materials. Covalent triazine-based polymers with a functional triazine group are significant class of organic materials due to their remarkable stability arising out of strong covalent bonds. They can conventionally form hydrogen bonds, favour π–π contacts, and they were recently revealed to be involved in interesting anion–π interactions. The present work mainly focuses upon the development of a single-crystalline, highly cross-linked triazine-based nitrogen-rich organic polymer with nanodendritic morphology and significant thermal stability. The polymer has been synthesized through hydrothermal treatment of melamine and ethylene glycol resulting in cross-polymerization via condensation-polymerization reaction. The crystal structure of the polymer has been evaluated by employing Rietveld whole profile fitting method. The polymer has been found to be composed of monoclinic melamine having space group P21/a. A detailed insight into the chemical structure of the as synthesized polymer has been elucidated by Fourier Transform Infrared Spectroscopy (FTIR) and Raman spectroscopic analysis. X-Ray Photoelectron Spectroscopic (XPS) analysis has also been carried out for further understanding of the different types of linkages required to create the backbone of the polymer. The unique rod-like morphology of the triazine based polymer has been revealed from the images obtained from Field Emission Scanning Electron Microscopy (FESEM) and Transmission Electron Microscopy (TEM). Interestingly, this polymer has been found to selectively detect mercury (Hg²⁺) ions at an extremely low concentration through fluorescent quenching with detection limit as low as 0.03 ppb. The high toxicity of mercury ions (Hg²⁺) arise from its strong affinity towards the sulphur atoms of biological building blocks. Even a trace quantity of this metal is dangerous for human health. Furthermore, owing to its small ionic radius and high solvation energy, Hg²⁺ ions remain encapsulated by water molecules making its detection a challenging task. There are some existing reports on fluorescent-based heavy metal ion sensors using covalent organic frameworks (COFs) but reports on mercury sensing using triazine based polymers are rather undeveloped. Thus, the importance of ultra-trace detection of Hg²⁺ ions with high level of selectivity and sensitivity has contemporary significance. A plausible sensing phenomenon by the polymer has been proposed to understand the applicability of the material as a potential sensor. The impressive sensitivity of the polymer sample towards Hg²⁺ is the very first report in the field of highly crystalline triazine based polymers (without the introduction of any sulphur groups or functionalization) towards mercury ion detection through photoluminescence quenching technique. This crystalline metal-free organic polymer being cheap, non-toxic and scalable has current relevance and could be a promising candidate for Hg²⁺ ion sensing at commercial level.

Keywords: fluorescence quenching , mercury ion sensing, single-crystalline, triazine-based polymer

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Authors: Monu Verma, Hyunook Kim

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Heavy metals and organic dyes are the major sources of water pollution. Herein, a trifunctional β−cyclodextrin−ethylenediaminetetraacetic acid−chitosan (β−CD−EDTA−CS) polymer was synthesized using an easy and simple chemical route by the reaction of activated β−CD with CS through EDTA as a cross-linker (amidation reaction) for the removal of inorganic and organic pollutants from aqueous solution under different parameters such as pH, time effect, initial concentration, reusability, etc. The synthesized adsorbent was characterized using powder X-ray diffraction, Fourier transform infrared spectroscopy, field scanning electron microscopy, energy dispersive spectroscopy, Brunauer-Emmett-Teller (BET), thermogravimetric analyzer techniques to investigate their structural, functional, morphological, elemental compositions, surface area, and thermal properties, respectively. Two types of heavy metals, i.e., mercury (Hg²⁺) and cadmium (Cd²⁺), and three organic dyes, i.e., methylene blue (MB), crystal violet (CV), and safranin O (SO), were chosen as inorganic and organic pollutants, respectively, to study the adsorption capacity of β-CD-EDTA-CS in aqueous solution. The β-CD-EDTA-CS shows a monolayer adsorption capacity of 346.30 ± 14.0 and 202.90 ± 13.90 mg g−¹ for Hg²⁺ and Cd²⁺, respectively, and a heterogeneous adsorption capacity of 107.20 ± 5.70, 77.40 ± 5.30 and 55.30 ± 3.60 mg g−¹ for MB, CV and SO, respectively. Kinetics results followed pseudo-second order (PSO) kinetics behavior for both metal ions and dyes, and higher rate constants values (0.00161–0.00368 g mg−¹ min−¹) for dyes confirmed the cavitation of organic dyes (physisorption). In addition, we have also demonstrated the performance of β-CD-EDTA-CS for the four heavy metals, Hg²⁺, Cd²⁺, Ni²⁺, and Cu²⁺, and three dyes MB, CV, and SO in secondary treated wastewater. The findings of this study indicate that β-CD-EDTA-CS is simple and easy to synthesize and can be used in wastewater treatment.

Keywords: adsorption isotherms, adsorption mechanism, amino-β-cyclodextrin, heavy metal ions, organic dyes

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Authors: Mumtaz Khan, Adeel Shahid, Waqas Khan

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Heavy metals presence in water streams is a big danger for aquatic life and ultimately effects human health. Removal of copper (Cu) by ispaghula husk, maize fibre, and maize oil cake from synthetic solution in batch conditions was studied. Different experimental parameters such as contact time, initial solution pH, agitation rate, initial Cu concentration, biosorbent concentration, and biosorbent particle size has been studied to quantify the Cu biosorption. The rate of adsorption of metal ions was very fast at the beginning and became slow after reaching the saturation point, followed by a slower active metabolic uptake of metal ions into the cells. Up to a certain point, (pH=4, concentration of Cu = ~ 640 mg/l, agitation rate = ~ 400 rpm, biosorbent concentration = ~ 0.5g, 3g, 3g for ispaghula husk, maize fiber and maize oil cake, respectively) increasing the pH, concentration of Cu, agitation rate, and biosorbent concentration, increased the biosorption rate; however the sorption capacity increased by decreasing the particle size. At optimized experimental parameters, the maximum Cu biosorption by ispaghula husk, maize fibre and maize oil cake were 86.7%, 59.6% and 71.3%, respectively. Moreover, the results of the kinetics studies demonstrated that the biosorption of copper on ispaghula husk, maize fibre, and maize oil cake followed pseudo-second order kinetics. The results of adsorption were fitted to both the Langmuir and Freundlich models. The Langmuir model represented the sorption process better than Freundlich, and R² value ~ 0.978. Optimizations of physical and environmental parameters revealed, ispaghula husk as more potent copper biosorbent than maize fibre, and maize oil cake. The sorbent is cheap and available easily, so this study can be applied to remove Cu impurities on pilot and industrial scale after certain modifications.

Keywords: biosorption, copper, ispaghula husk, maize fibre, maize oil cake, purification

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Authors: Abhishek Kumar Gupta

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Atomistic Molecular Dynamics (MD) Simulations have been performed to study the effect of monovalent salt i.e. NaCl concentration (Cs) and chain degree of neutralization (f) on the structure and dynamics of anionic poly(methacrylic acid) (PMA) in dilute aqueous solutions. In the present study, the attention is to unveil the conformational structure, hydrogen-bonding, local polyion-counterion structure, h-bond dynamics, chain dynamics and thermodynamic enthalpy of solvation of a-PMA in dilute aqueous solutions as a function of salt concentration, Cs and f. The results have revealed that at low salt concentration, the conformational radius of gyration (Rg) increases and then decreases reaching a maximum in agreement with the reported light scattering experimental results. The Rg at f = 1 shows a continual decrease and acquire a plateau value at higher salt concentration in agreement with results obtained by light scattering experiments. The radial distribution functions between PMA, salt and water atoms has been computed with respect to atom and centre-of-mass to understand the intermolecular structure in detail. The results pertaining to PMA chain conformations and hydrogen bond autocorrelation function showcasing the h-bond dynamics will be presented. The results pertaining to chain dynamics will be presented. The results pertaining to counterion condensation on the PMA chain shows greater condensation of Na+ ions on to the carboxylate ions with increase in salt concentration. Moreover, the solvation enthalpy of the system as a function of salt concentration will be presented.

Keywords: conformations, molecular dynamics simulations, NaCl concentration, radial distribution functions

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Authors: Nipa Debnath, Harinarayan Das, Takahiko Kawaguchi, Naonori Sakamoto, Kazuo Shinozaki, Hisao Suzuki, Naoki Wakiya

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Nowadays spinel ferrite magnetic thin films have drawn considerable attention due to their interesting magnetic and electrical properties with enhanced chemical and thermal stability. Spinel ferrite magnetic films can be implemented in magnetic data storage, sensors, and spin filters or microwave devices. It is well established that the structural, magnetic and transport properties of the magnetic thin films are dependent on microstructure. Spinodal decomposition (SD) is a phase separation process, whereby a material system is spontaneously separated into two phases with distinct compositions. The periodic microstructure is the characteristic feature of SD. Thus, SD can be exploited to control the microstructure at the nanoscale level. In bulk spinel ferrites having general formula, MₓFe₃₋ₓ O₄ (M= Co, Mn, Ni, Zn), phase separation via SD has been reported only for cobalt ferrite (CFO); however, long time post-annealing is required to occur the spinodal decomposition. We have found that SD occurs in CoF thin film without using any post-deposition annealing process if we apply magnetic field during thin film growth. Dynamic Aurora pulsed laser deposition (PLD) is a specially designed PLD system through which in-situ magnetic field (up to 2000 G) can be applied during thin film growth. The in-situ magnetic field suppresses the recombination of ions in the plume. In addition, the peak’s intensity of the ions in the spectra of the plume also increases when magnetic field is applied to the plume. As a result, ions with high kinetic energy strike into the substrate. Thus, ion-impingement occurred under magnetic field during thin film growth. The driving force of SD is the ion-impingement towards the substrates that is induced by in-situ magnetic field. In this study, we report about the occurrence of phase separation through SD and evolution of microstructure after phase separation in spinel ferrite thin films. The surface morphology of the phase separated films show checkerboard like domain structure. The cross-sectional microstructure of the phase separated films reveal columnar type phase separation. Herein, the decomposition wave propagates in lateral direction which has been confirmed from the lateral composition modulations in spinodally decomposed films. Large magnetic anisotropy has been found in spinodally decomposed nickel ferrite (NFO) thin films. This approach approves that magnetic field is also an important thermodynamic parameter to induce phase separation by the enhancement of up-hill diffusion in thin films. This thin film deposition technique could be a more efficient alternative for the fabrication of self-organized phase separated thin films and employed in controlling of the microstructure at nanoscale level.

Keywords: Dynamic Aurora PLD, magnetic anisotropy, spinodal decomposition, spinel ferrite thin film

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Authors: Barbora Svechova, Monika Licbinska

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Geochemical modeling of mineralogical changes of various materials in contact with an aqueous solution is an important tool for predicting the processes and development of given materials at the site. The modeling focused on the mutual interaction of groundwater at the contact with the rock mass and its subsequent influence on concrete structures. The studied locality is located in Slovakia in the area of the Liptov Basin, which is a significant inter-mountain lowland, which is bordered on the north and south by the core mountains belt of the Tatras, where in the center the crystalline rises to the surface accompanied by Mesozoic cover. Groundwater in the area is bound to structures with complicated geological structures. From the hydrogeological point of view, it is an environment with a crack-fracture character. The area is characterized by a shallow surface circulation of groundwater without a significant collector structure, and from a chemical point of view, groundwater in the area has been classified as calcium bicarbonate with a high content of CO2 and SO4 ions. According to the European standard EN 206-1, these are waters with medium aggression towards the concrete. Three rock samples were taken from the area. Based on petrographic and mineralogical research, they were evaluated as calcareous shale, micritic limestone and crystalline shale. These three rock samples were placed in demineralized water for one month and the change in the chemical composition of the water was monitored. During the solution-rock interaction there was an increase in the concentrations of all major ions, except nitrates. There was an increase in concentration after a week, but at the end of the experiment, the concentration was lower than the initial value. Another experiment was the interaction of groundwater from the studied locality with a concrete structure. The concrete sample was also left in the water for 1 month. The results of the experiment confirmed the assumption of a reduction in the concentrations of calcium and bicarbonate ions in water due to the precipitation of amorphous forms of CaCO3 on the surface of the sample.Vice versa, it was surprising to increase the concentration of sulphates, sodium, iron and aluminum due to the leaching of concrete. Chemical analyzes from these experiments were performed in the PHREEQc program, which calculated the probability of the formation of amorphous forms of minerals. From the results of chemical analyses and hydrochemical modeling of water collected in situ and water from experiments, it was found: groundwater at the site is unsaturated and shows moderate aggression towards reinforced concrete structures according to EN 206-1a, which will affect the homogeneity and integrity of concrete structures; from the rocks in the given area, Ca, Na, Fe, HCO3 and SO4. Unsaturated waters will dissolve everything as soon as they come into contact with the solid matrix. The speed of this process then depends on the physicochemical parameters of the environment (T, ORP, p, n, water retention time in the environment, etc.).

Keywords: geochemical modeling, concrete , dissolution , PHREEQc

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Authors: Dongwoo Kang, Yunsung Yoo, Injun Kim, Jongin Lee, Jinwon Park

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Since industrial revolution, energy usage by human-beings has been drastically increased resulting in the enormous emissions of carbon dioxide into the atmosphere. High concentration of carbon dioxide is well recognized as the main reason for the climate change by breaking the heat equilibrium of the earth. In order to decrease the amount of carbon dioxide emission, lots of technologies have been developed. One of the methods is to capture carbon dioxide after combustion process using liquid type absorbents. However, for some nations, captured carbon dioxide cannot be treated and stored properly due to their geological structures. Also, captured carbon dioxide can be leaked out when crust activities are active. Hence, the method to convert carbon dioxide as stable and useful products were developed. It is usually called CCU, that is, Carbon Capture and Utilization. There are several ways to convert carbon dioxide into useful substances. For example, carbon dioxide can be converted and used as fuels such as diesel, plastics, and polymers. However, these types of technologies require lots of energy to make stable carbon dioxide into a reactive one. Hence, converting it into metal carbonates salts have been studied widely. When carbon dioxide is captured by alkanolamine-based liquid absorbents, it exists as ionic forms such as carbonate, carbamate, and bicarbonate. When adequate metal ions are added, metal carbonate salt can be produced by ionic reaction with fast reaction kinetics. However, finding metal sources can be one of the problems for this method to be commercialized. If natural resources such as calcium oxide were used to supply calcium ions, it is not thought to have the economic feasibility to use natural resources to treat carbon dioxide. In this research, high concentrated industrial wastewater produced from refined salt production facility have been used as metal supplying source, especially for calcium cations. To ensure purity of final products, calcium ions were selectively separated in the form of gypsum dihydrate. After that, carbon dioxide is captured using alkanolamine-based absorbents making carbon dioxide into reactive ionic form. And then, high purity calcium carbonate salt was produced. The existence of calcium carbonate was confirmed by X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM) images. Also, carbon dioxide loading curves for absorption, conversion, and desorption were provided. Also, in order to investigate the possibility of the absorbent reuse, reabsorption experiments were performed either. Produced calcium carbonate as final products is seemed to have potential to be used in various industrial fields including cement and paper making industries and pharmaceutical engineering fields.

Keywords: alkanolamine, calcium carbonate, climate change, seawater, industrial wastewater

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Authors: Prateek Goyal, Archini Paruthi, Superb K. Misra

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Contamination of water resources has been a major concern, which has drawn attention to the need to develop new material models for treatment of effluents. Existing conventional waste water treatment methods remain ineffective sometimes and uneconomical in terms of remediating contaminants like heavy metal ions (mercury, arsenic, lead, cadmium and chromium); organic matter (dyes, chlorinated solvents) and high salt concentration, which makes water unfit for consumption. We believe that nanotechnology based strategy, where we use nanoparticles as a tool to remediate a class of pollutants would prove to be effective due to its property of high surface area to volume ratio, higher selectivity, sensitivity and affinity. In recent years, scientific advancement has been made to study the application of photocatalytic (ZnO, TiO2 etc.) nanomaterials and magnetic nanomaterials in remediating contaminants (like heavy metals and organic dyes) from water/wastewater. Our study focuses on the synthesis and monitoring remediation efficiency of ZnO, Fe3O4 and Fe3O4 coated ZnO nanoparticulate system for the removal of heavy metals and dyes simultaneously. Multitude of ZnO nanostructures (spheres, rods and flowers) using multiple routes (microwave & hydrothermal approach) offers a wide range of light active photo catalytic property. The phase purity, morphology, size distribution, zeta potential, surface area and porosity in addition to the magnetic susceptibility of the particles were characterized by XRD, TEM, CPS, DLS, BET and VSM measurements respectively. Further on, the introduction of crystalline defects into ZnO nanostructures can also assist in light activation for improved dye degradation. Band gap of a material and its absorbance is a concrete indicator for photocatalytic activity of the material. Due to high surface area, high porosity and affinity towards metal ions and availability of active surface sites, iron oxide nanoparticles show promising application in adsorption of heavy metal ions. An additional advantage of having magnetic based nanocomposite is, it offers magnetic field responsive separation and recovery of the catalyst. Therefore, we believe that ZnO linked Fe3O4 nanosystem would be efficient and reusable. Improved photocatalytic efficiency in addition to adsorption for environmental remediation has been a long standing challenge, and the nano-composite system offers the best of features which the two individual metal oxides provide for nanoremediation.

Keywords: adsorption, nanocomposite, nanoremediation, photocatalysis

Procedia PDF Downloads 237

Authors: Waqas Hassan Tanveer, Yoon Ho Lee, Taehyun Park, Wonjong Yu, Yaegeun Lee, Yusung Kim, Suk Won Cha

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Nickel-Gadolinium Doped Ceria (Ni-GDC) cermet anodic thin films were prepared on Scandia Stabilized Zirconia (ScSZ) electrolyte supports by radio frequency (RF) sputtering, with a range of different sputtering powers (50 – 200W) and background Ar gas pressures (30 – 90mTorr). The effects of varying sputtering power and pressure on the properties of Ni-GDC films were studied using Focused Ion Beam (FIB), X-ray Photoelectron Spectroscopy (XPS), X-ray Diffraction (XRD), Energy Dispersive X-ray (EDX), and Atomic Force Microscopy (AFM) techniques. The Ni content was found to be always higher than the Ce content, at all sputtering conditions. This increased Ni content was attributed to significantly higher energy transfer efficiency of Ni ions as compared to Ce ions with Ar background sputtering gas. The solid oxide fuel cell configuration was completed by using lanthanum strontium manganite (LSM/YSZ) cathodes on the other side of ScSZ supports. Performance comparison of cells was done by Voltage-Current-Power (VIP) curves, while the resistances of various cell components were observed by nyquist plots. Initial results showed that anode films made by higher powered RF sputtering performed better than lower powered ones for a specific Ar pressure. Interestingly, however, anodes made at highest power and pressure, were not the ones that showed the maximum power output at an intermediate solid oxide fuel cell temperature of 800°C. Finally, an optimal sputtering condition was reported for high performance Ni-GDC anodes.

Keywords: intermediate temperature solid oxide fuel cells, nickel-cermet anodic thin films, nyquist plots, radio frequency sputtering

Procedia PDF Downloads 240

Authors: Khalil H. Al-Bayati, Khalid Omar Al-Baiti

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The energy expectation value for Li-like ions systems (Li, Be+ and Be2+) hasbeen calculated and examined within the ground state (1s2sα)^2 S and the excited state (1s3sα)^2 S in position space. The partitioning technique of Hartree-Fock (H-F) has been used for existing wavefnctions.

Keywords: energy expectation value, atomic systems, ground and excited states, Hartree-Fock approximation

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Authors: Ekaterina S. Marchenko, Gulsharat A. Baigonakova, Kirill M. Dubovikov, Igor A. Khlusov

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NiTi alloys combine biomechanical and biochemical properties. This makes them a perfect candidate for medical applications. However, there is a serious problem with these alloys, such as the release of Ni from the matrix. Ni ions are known to be toxic to living tissues and leach from the matrix into the surrounding implant tissues due to corrosion after prolonged use. To prevent the release of Ni ions, corrosive strong coatings are usually used. Titanium nitride-based coatings are perfect corrosion inhibitors and also have good bioactive properties. However, there is an opportunity to improve the biochemical compatibility of the surface by depositing another layer. This layer can consist of elements such as calcium and phosphorus. The Ca and P ions form different calcium phosphate phases, which are present in the mineral part of human bones. We therefore believe that these elements must promote osteogenesis and osteointegration. In view of the above, the aim of this study is to investigate the effect of crystallinity on the biocompatibility of a two-layer coating deposited on NiTi substrate by sputtering. The first step of the research, apart from the NiTi polishing, is the layer-by-layer deposition of Ti-Ni-Ti by magnetron sputtering and the subsequent synthesis of this composite in an N atmosphere at 900 °C. The total thickness of the corrosion resistant layer is 150 nm. Plasma assisted RF sputtering was then used to deposit a bioactive film on the titanium nitride layer. A Ca-P powder target was used to obtain such a film. We deposited three types of Ca-P layers with different crystallinity and compared them in terms of cytotoxicity. One group of samples had no Ca-P coating and was used as a control. We obtained different crystallinity by varying the sputtering parameters such as bias voltage, plasma source current and pressure. XRD analysis showed that all coatings are calcium phosphate, but the sample obtained at maximum bias and plasma source current and minimum pressure has the most intense peaks from the coating phase. SEM and EDS showed that all three coatings have a homogeneous and dense structure without cracks and consist of calcium, phosphorus and oxygen. Cytotoxic tests carried out on three types of samples with Ca-P coatings and a control group showed that the control sample and the sample with Ca-P coating obtained at maximum bias voltage and plasma source current and minimum pressure had the lowest number of dead cells on the surface, around 11 ± 4%. Two other types of samples with Ca-P coating have 40 ± 9% and 21 ± 7% dead cells on the surface. It can therefore be concluded that these two sputtering modes have a negative effect on the corrosion resistance of the whole samples. The third sputtering mode does not affect the corrosion resistance and has the same level of cytotoxicity as the control. It can be concluded that the most suitable sputtering mode is the third with maximum bias voltage and plasma source current and minimum pressure.

Keywords: calcium phosphate coating, cytotoxicity, NiTi alloy, two-layer coating

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Authors: X. Han, S. Duan, C. Liu, C. Zhou, W. Zhu, L. Kong

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The ionic imprinting technique refers to the three-dimensional rigid structure with the fixed pore sizes, which was formed by the binding interactions of ions and functional monomers and used ions as the template, it has a high level of recognition to the ionic template. The preparation of monolithic column by the in-situ polymerization need to put the compound of template, functional monomers, cross-linking agent and initiating agent into the solution, dissolve it and inject to the column tube, and then the compound will have a polymerization reaction at a certain temperature, after the synthetic reaction, we washed out the unread template and solution. The monolithic columns are easy to prepare, low consumption and cost-effective with fast mass transfer, besides, they have many chemical functions. But the monolithic columns have some problems in the practical application, such as low-efficiency, quantitative analysis cannot be performed accurately because of the peak shape is wide and has tailing phenomena; the choice of polymerization systems is limited and the lack of theoretical foundations. Thus the optimization of components and preparation methods is an important research direction. During the preparation of ionic imprinted monolithic columns, pore-forming agent can make the polymer generate the porous structure, which can influence the physical properties of polymer, what’ s more, it can directly decide the stability and selectivity of polymerization reaction. The compounds generated in the pre-polymerization reaction could directly decide the identification and screening capabilities of imprinted polymer; thus the choice of pore-forming agent is quite critical in the preparation of imprinted monolithic columns. This article mainly focuses on the research that when using different pore-forming agents, the impact of zinc ion imprinted monolithic column on the enrichment performance of zinc ion.

Keywords: high performance liquid chromatography (HPLC), ionic imprinting, monolithic column, pore-forming agent

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Authors: Biswajit Pal, Amit Mallik, Anil K. Barik

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Current years have witnessed a phenomenal growth in the research on the rare earth-doped transparent host materials, the essential components in optoelectronics that meet up the increasing demand for fabrication of high quality optical devices especially in telecommunication system. The combination of low phonon energy (because of fluoride environment) and high chemical durability with superior mechanical stability (due to oxide environment) makes the oxyfluoride glass–ceramics the promising and useful materials in optoelectronics. The present work reports on the undoped and doped (1 mol% Pr2O3) glass ceramics of composition 16.52 Al2O3•1.5AlF3• 12.65LaF3•4.33Na2O•64.85 SiO2 (mol%), prepared by melting technique initially that follows annealation at 450 ºC for 1 h. The glass samples so obtained were heat treated at constant 600 ºC with a variation in heat treatment schedule (10- 80 h). TEM techniques were employed to structurally characterize the glass samples. Pr2O3 affects the phase separation in the glass and delays the onset of crystallization in the glass ceramic. The modified crystallization mechanism is established from the analysis of advanced STEM/EDXS results. The phase separated droplets after annealing turn into 10-20 nm of LaF3 nano crystals those upon scrutiny are found to be dotted with the doped Pr3+ ions within the crystals themselves. The EDXS results also suggest that the inner LaF3 crystal core is swallowed by an Al enriched layer that follows a Si enriched surrounding shell as the outer core. This greatly increases the viscosity in the periphery of the crystals that restricts further crystal growth to account for the formation of nano sized crystals.

Keywords: advanced STEM/EDXS, crystallization mechanism, nano crystals, pr3+ ion doped glass and glass ceramic, structural characterization

Procedia PDF Downloads 185

Authors: Yi-An Liao, Lu-Wei Kuo, Yu-Jen Shih, Yao-Hui Huang

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Abstract—Imidacloprid (IMI, a widely used pesticide, iImidacloprid (IMI), a widely used pesticide, is known to affect the bee populations. A sulfate radical-based oxidation method was utilized to remove the commercial pesticide consisted of IMI, dimethylacetamide, N-methyl-2-pyrrolidone, and methanol (TOC0 = 497 ppm). The experimental results evidenced that sulfate radicals created by UV activation (254nm, 6.4 mW/cm2) of S2O82- could remove 97% of total organic carbon (TOC) from the synthetic wastewater in 4 h using 120 mM of oxidant dosage. The dose of oxidant, temperature and the light flux were the key factors to further improve the mineralization efficiency, while the ferrous ions decreased the efficacy of UV/S2O82- reaction due to the competition of UV-adsorption by complex formation of FeSO4+.s known to affect the bee populations. A sulfate radical-based oxidation method was utilized to remove the commercial pesticide consisted of IMI, dimethylacetamide, N-methyl-2-pyrrolidone, and methanol (TOC0 = 497 ppm). The experimental results evidenced that sulfate radicals created by UV activation (254nm, 6.4 mW/cm2) of S2O82- could remove 97% of total organic carbon (TOC) from the synthetic wastewater in 4 h using 120 mM of oxidant dosage. The dose of oxidant, temperature and the light flux were the key factors to further improve the mineralization efficiency, while the ferrous ions decreased the efficacy of UV/S2O82- reaction due to the competition of UV-adsorption by complex formation of FeSO4+.

Keywords: organic nitrogen, photochemical oxidation, imidacloprid, UV-persulfate, mineralization

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Authors: Hafida Ferfera-Harrar, Nacera Aiouaz, Nassima Dairi

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Super absorbents polymers received much attention and are used in many fields because of their superior characters to traditional absorbents, e.g., sponge and cotton. So, it is very important but challenging to prepare highly and fast-swelling super absorbents. A reliable, efficient and low-cost technique for removing heavy metal ions from waste water is the adsorption using bio-adsorbents obtained from biological materials, such as polysaccharides-based hydrogels super absorbents. In this study, novel multi-functional super absorbent composites type semi-interpenetrating polymer networks (Semi-IPNs) were prepared via graft polymerization of acrylamide onto chitosan backbone in presence of gelatin, CTS-g-PAAm/Ge, using potassium persulfate and N,N’ -methylenebisacrylamide as initiator and cross linker, respectively. These hydrogels were also partially hydrolyzed to achieve superabsorbents with ampholytic properties and uppermost swelling capacity. The formation of the grafted network was evidenced by Fourier Transform Infrared Spectroscopy (ATR-FTIR) and thermo gravimetric Analysis (TGA). The porous structures were observed by Scanning Electron Microscope (SEM). From TGA analysis, it was concluded that the incorporation of the Ge in the CTS-g-PAAm network has marginally affected its thermal stability. The effect of gelatin content on the swelling capacities of these super absorbent composites was examined in various media (distilled water, saline and pH-solutions).The water absorbency was enhanced by adding Ge in the network, where the optimum value was reached at 2 wt. % of Ge. Their hydrolysis has not only greatly optimized their absorption capacity but also improved the swelling kinetic. These materials have also showed reswelling ability. We believe that these super-absorbing materials would be very effective for the adsorption of harmful metal ions from waste water.

Keywords: chitosan, gelatin, superabsorbent, water absorbency

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Authors: Mohamed H. Sorour, Hayam F. Shaalan, Heba A. Hani, Mahmoud A. El-Toukhy

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This paper reports the results of nanofiltration (NF) polymeric membrane for the recovery of divalent ions (calcium and magnesium) from Red Seawater. Pilot plant experiments have been carried out using Alfa-Laval (NF 2517/48) membrane module. System was operated in both total recirculation mode (permeate and brine) and brine recirculation mode under hydraulic pressure of 15 bar. Impacts of some chelating agents on both flux and rejection have been also investigated. Results indicated that pure water permeability ranges from 17 to 85.5 L/m²h at 2-15 bar. Comparison with seawater permeability under the same operating pressure values reveals lower values of 8.9-31 L/m²h manifesting the effect of the osmotic pressure of seawater. Overall total dissolved solids (TDS) reduction was almost constant without incorporation of chelating agents. On the contrary of expectations, the use of chelating agents N-(2-hydroxyethyl) ethylene diamine-N,N´,N´-triacetic acid (HEDTA) and ethylene glycol bis (2-aminoethyl ether)-N,N,N´,N´-tetraacetic acid (EGTA) showed flux decline of about 3-15%. Analysis of rejection data of total recirculation mode showed reasonable rejection values of 35%, 59% and 90% for Ca, Mg and SO₄, respectively. Operating under brine recirculation mode only showed a decrease of rejection to 33%, 56% and 86% for Ca, Mg and SO₄, respectively. The use of chelating agents has no substantial effect on NF membrane performance except for increasing the total Ca rejection to 48 and 65% for EGTA and HEDTA, respectively. Results, in general, confirmed the powerful separation of NF technology for softening and recovery of divalent ions from seawater. It is anticipated that increasing operating pressure beyond the limits of our investigations would improve the rejection and flux values. A trade-off should be considered between operating cost (due to higher pressure and marginal benefits as manifested by expected improved performance). The experimental results fit well with the formulated rejection empirical correlations and the published ones.

Keywords: nanofiltration, seawater, recovery, calcium, magnesium

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Authors: Modreck Gomo

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The evolution of groundwater chemistry and its quality is largely controlled by hydrogeochemical processes and their understanding is therefore important for groundwater quality assessments and protection of the water resources. A study was conducted in Bloemfontein town of South Africa to assess and compare the groundwater chemistry and quality characteristics in an alluvial aquifer and single-plane fractured-rock aquifers. 9 groundwater samples were collected from monitoring boreholes drilled into the two aquifer systems during a once-off sampling exercise. Samples were collected through low-flow purging technique and analysed for major ions and trace elements. In order to describe the hydrochemical facies and identify dominant hydrogeochemical processes, the groundwater chemistry data are interpreted using stiff diagrams and principal component analysis (PCA), as complimentary tools. The fitness of the groundwater quality for domestic and irrigation uses is also assessed. Results show that the alluvial aquifer is characterised by a Na-HCO₃ hydrochemical facie while fractured-rock aquifer has a Ca-HCO₃ facie. The groundwater in both aquifers originally evolved from the dissolution of calcite rocks that are common on land surface environments. However the groundwater in the alluvial aquifer further goes through another evolution as driven by cation exchange process in which Na in the sediments exchanges with Ca²⁺ in the Ca-HCO₃ hydrochemical type to result in the Na-HCO₃ hydrochemical type. Despite the difference in the hydrogeochemical processes between the alluvial aquifer and single-plane fractured-rock aquifer, this did not influence the groundwater quality. The groundwater in the two aquifers is very hard as influenced by the elevated magnesium and calcium ions that evolve from dissolution of carbonate minerals which typically occurs in surface environments. Based on total dissolved levels (600-900 mg/L), groundwater quality of the two aquifer systems is classified to be of fair quality. The negative potential impacts of the groundwater quality for domestic uses are highlighted.

Keywords: alluvial aquifer, fractured-rock aquifer, groundwater quality, hydrogeochemical processes

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Authors: Simona Dostalova, Pavel Kopel, Marketa Vaculovicova, Vojtech Adam, Rene Kizek

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Protein apoferritin seems to be a very promising structure for use as a nanocarrier. It is prepared from intracellular ferritin protein naturally found in most organisms. The role of ferritin proteins is to store and transport ferrous ions. Apoferritin is a hollow protein cage without ferrous ions that can be prepared from ferritin by reduction with thioglycolic acid or dithionite. The structure of apoferritin is composed of 24 protein subunits, creating a sphere with 12 nm in diameter. The inner cavity has a diameter of 8 nm. The drug encapsulation process is based on the response of apoferritin structure to the pH changes of surrounding solution. In low pH, apoferritin is disassembled into individual subunits and its structure is “opened”. It can then be mixed with any desired cytotoxic drug and after adjustment of pH back to neutral the subunits are reconnected again and the drug is encapsulated within the apoferritin particles. Excess drug molecules can be removed by dialysis. The receptors for apoferritin, SCARA5 and TfR1 can be found in the membrane of both healthy and cancer cells. To enhance the specific targeting of apoferritin nanocarrier, it is possible to modify its surface with targeting moieties, such as antibodies. To ensure sterically correct complex, we used a a peptide linker based on a protein G with N-terminus affinity towards Fc region of antibodies. To connect the peptide to the surface of apoferritin, the C-terminus of peptide was made of cysteine with affinity to gold. The surface of apoferritin with encapsulated doxorubicin (ApoDox) was coated either with gold nanoparticles (ApoDox-Nano) or gold (III) chloride hydrate reduced with sodium borohydride (ApoDox-HAu). The applied amount of gold in form of gold (III) chloride hydrate was 10 times higher than in the case of gold nanoparticles. However, after removal of the excess unbound ions by electrophoretic separation, the concentration of gold on the surface of apoferritin was only 6 times higher for ApoDox-HAu in comparison with ApoDox-Nano. Moreover, the reduction with sodium borohydride caused a loss of doxorubicin fluorescent properties (excitation maximum at 480 nm with emission maximum at 600 nm) and thus its biological activity. Fluorescent properties of ApoDox-Nano were similar to the unmodified ApoDox, therefore it was more suited for the intended use. To evaluate the specificity of apoferritin modified with antibodies, we used ELISA-like method with the surface of microtitration plate wells coated by the antigen (goat anti-human IgG antibodies). To these wells, we applied ApoDox without targeting antibodies and ApoDox-Nano modified with targeting antibodies (human IgG antibodies). The amount of unmodified ApoDox on antigen after incubation and subsequent rinsing with water was 5 times lower than in the case of ApoDox-Nano modified with targeting antibodies. The modification of non-gold ApoDox with antibodies caused no change in its targeting properties. It can therefore be concluded that the demonstrated procedure allows us to create nanocarrier with enhanced targeting properties, suitable for nanomedicine.

Keywords: apoferritin, doxorubicin, nanocarrier, targeting antibodies

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Authors: A. J. Olatunji, Adebolu Temitope Johnson

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Groundwater samples were collected randomly from hand-dug wells and boreholes in parts of the Ado Ekiti metropolis and were subjected to quality assessment and characterization. Physicochemical analyses, which include the in-situ parameters (pH units, Turbidity, and Electrical Conductivity) and laboratory analysis of selected ionic concentrations, were carried out following standard methods. Hydrochemistry of the present study revealed relative mean concentrations of cations in the order Ca2+ > Na+ > Mg2+ > Cu2+> Fe > Mn2+ and that of anions: Cl- > NO3- > SO42- > F - respectively considering World Health Organisation Standard (WHO) range of values for potable water. The result shows that values of certain parameters (Total Dissolved Solid (TDS), Manganese, Calcium, Magnesium, Fluoride, and Sulphate) were below the Highest Desirable Level of the Standards, while values of some other parameters (pH Units, Electrical Conductivity, Turbidity, Alkalinity, Sodium, Copper, Chloride, and Total Hardness) were within the range of figures between Highest Desirable Level (HDL) and Maximum Permissible Level (MPL) of World Health Organization (WHO) drinking water Standards. The reduction in the mean concentration value of Total Dissolved Solids (TDS) of most borehole samples follows the fact that water had been allowed to settle in the overhead tanks before usage; we discussed and brainstormed in the course of sampling and agreed to take a sample that way because that represents what the people consume, it also shows an indication while there was slightly concentration increase of these soluble ions in hand-dug wells samples than borehole samples only with the exception of borehole sample seven BH7 because BH7 uses the mono-pumping system. These in-situ parameters and ionic concentrations were further displayed and or represented on bar charts along with the WHO standards for better pictorial clarifications. Deductions from field observation indices revealed the imprints of natural weathering, ion-exchange processes, and anthropogenic activities influencing groundwater quality. A strong degree of association was found to exist between sodium and chlorine ions in both hand-dug well and borehole groundwater samples through the use of Pearson’s correlation coefficient; this association can further be supported by the chemistry of the parent bedrock associated with the study area because the chemistry of groundwater is a replica of its host rock. The correlation of those two ions must have begun from the period of mountain building, indicating an identical source from which they were released to the groundwater. Moreover, considering the comparison of ionic species concentrations of all samples with the (WHO) standards, there were no anomalous increases or decreases in the laboratory analysis results; this simply reveals an insignificant state of pollution of the groundwater. The study and its sampling techniques were not set to target the likely area and extent of groundwater pollution but its portability. It could be said that the samples were safe for human consumption.

Keywords: groundwater, physicochemical, parameters ionic, concentrations, WHO standards

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Authors: W. Stawiński, A. Wegrzyn, O. M. Freitas, S. A. Figueiredo

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Water is a life supporting resource, crucial for humanity and essential for natural ecosystems, which have been endangered by developing industry and increasing human population. Dyes are common in effluents discharged by various industries such as paper, plastics, food, cosmetics, and textile. They produce toxic effects on animals and disturb natural biological processes in receiving waters. Having complex molecular structure and resistance to biological decomposition they are problematic and difficult to be treated by conventional methods. In the search of efficient and sustainable method, sorption has been getting more interest in application to wastewaters treatment. Clays are minerals that have a layer structure based on phyllosilicate sheets that may carry a charge, which is balanced by ions located between the sheets. These charge-balancing ions can be exchanged resulting in very good ion-exchange properties of the material. Modifications of clays enhance their properties, producing a good and inexpensive sorbent for the removal of pollutants from wastewaters. The presented work proves that the treatment of a clay, vermiculite, with nitric acid followed by washing in citric acid strongly increases the sorption of two cationic dyes, methylene blue (C.I. 52015) and astrazon red (C.I. 110825). Desorption studies showed that the best eluent for regeneration is a solution of NaCl in ethanol. Cycles of sorption and desorption in column system showed no significant deterioration of sorption capacity and proved that the material shows a very good performance as sorbent, which can be recycled and reused. The results obtained open new possibilities of further modifications on vermiculite and modifications of other materials in order to get very efficient sorbents useful for wastewater treatment.

Keywords: cationic dyestuffs, sorption and regeneration, vermiculite, wastewater treatment

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Authors: Jerina Majeed, Jayshree Ramkumar, S. Chandramouleeswaran, A. K. Tyagi

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Removal of various toxic species from aqueous streams is of great importance. Sorption is one of the important remediation procedures as it involves the use of cheap and easily available materials. Also the advantage of regeneration of the sorbent involves the possibility of using novel sorbents. Nanosorbents are very important as the removal is based on the surface phenomena and this is greatly affected by surface charge and area. Functionalization has been very important to bring about the removal of metal ions with greater selectivity.

Keywords: mercury, lead, thiol functionalization, ZnO NPs

Procedia PDF Downloads 339