Browsing by Subject "Sorption"
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Item Open Access Effects of laser ablated silver nanoparticles on Lemna minor(Elsevier, 2014) Üçüncü, E.; Özkan, A. D.; Kurşungöz, C.; Ülger, Z. E.; Ölmez, T. T.; Tekinay, T.; Ortaç, B.; Tunca E.Item Open Access Efficient removal of polycyclic aromatic hydrocarbons and heavy metals from water by electrospun nanofibrous polycyclodextrin membranes(American Chemical Society, 2019) Çelebioğlu, Aslı; Topuz, Fuat; Yıldız, Zehra İrem; Uyar, TamerHere, a highly efficient membrane based on electrospun polycyclodextrin (poly-CD) nanofibers was prepared and exploited for the scavenging of various polycyclic aromatic hydrocarbons (PAHs) and heavy metals from water. The poly-CD nanofibers were produced by the electrospinning of CD molecules in the presence of a cross-linker (i.e., 1,2,3,4-butanetetracarboxylic acid), followed by heat treatment to obtain an insoluble poly-CD nanofibrous membrane. The membrane was used for the removal of several PAH compounds (i.e., acenaphthene, fluorene, fluoranthene, phenanthrene, and pyrene) and heavy metals (i.e., Pb2+, Ni2+, Mn2+, Cd2+, Zn2+, and Cu2+) from water over time. Experiments were made on the batch sorption of PAHs and heavy metals from contaminated water to explore the binding affinity of PAHs and heavy metals to the poly-CD membrane. The equilibrium sorption capacity (qe) of the poly-CD nanofibrous membrane was found to be 0.43 ± 0.045 mg/g for PAHs and 4.54 ± 0.063 mg/g for heavy metals, and the sorption kinetics fitted well with the pseudo-second-order model for both types of pollutants. The membrane could be recycled after treatment with acetonitrile or a 2% nitric acid solution and reused up to four times with similar performance. Further, dead-end filtration experiments showed that the PAH removal efficiencies were as high as 92.6 ± 1.6 and 89.9 ± 4.8% in 40 s for the solutions of 400 and 600 μg/L PAHs, respectively. On the other hand, the removal efficiencies for heavy metals during the filtration were 94.3 ± 5.3 and 72.4 ± 23.4% for 10 and 50 mg/L solutions, respectively, suggesting rapid and efficient filtration of heavy metals and PAHs by the nanofibrous poly-CD membrane.Item Open Access Migration behaviour of Barium and Strontium in Granite(De Gruyter Oldenbourg, 1994-12-01) Hatipoğlu, S.; Göktürk, H.; Erten, H. N.The sorption behaviour of Ba2+ and Sr2+ cations on granite have been studied under flowing and static conditions in column and batch experiments. 133Ba, 90Sr and 3H were used as radio tracers. The retardation factors, R1, and distribution ratios, Rd, of barium and strontium in column experiments were found to be smaller than those from batch experiments. In both techniques barium was sorbed more strongly on granite than strontium. Sorption energies were found to be in good agreement with literature val-ues.Item Open Access Migration behaviour of barium and strontium through colemanite(De Gruyter Oldenbourg, 1996) Hatipoǧlu, S.; Göktürk, H.; Erten, H. N.Column and batch experiments were performed to study the migration behaviour of Ba and Sr in colemanite matrix. 133Ba. 90Sr and 3H were used as tracers. The retardation factors and the distribution ratios of Ba and Sr in column experiments were found to be smaller than those obtained in batch experiments. Sorption Ra values of Ba were higher than those of Sr determined by both techniques. Sorption energies calculated from batch experiments are in good agreement with the literature values.Item Open Access Poly-cyclodextrin cryogels with aligned porous structure for removal of polycyclic aromatic hydrocarbons (PAHs) from water(Elsevier, 2017-08) Topuz, F.; Uyar, TamerCyclodextrins (CDs) are sugar-based cyclic oligosaccharides, which form inclusion complexes with small guest molecules through their hydrophobic cavity. Here we successfully synthesized highly porous poly-cyclodextrin (poly-CD) cryogels, which were produced under cryogenic conditions by the cross-linking of amine-functional CDs with PEG-based diepoxide cross-linker. The poly-CD cryogels showed aligned porous network structures owing to the directional freezing of the matrix, of which the pore size and architecture exposed variations depending on the composition of the reactants. The cryogels were employed for the removal of genotoxic polycyclic aromatic hydrocarbons (PAHs) from aqueous solutions. They reached PAH sorption capacities as high as 1.25 mg PAH per gram cryogel. This high sorption performance is due to interactions between PAHs and the complete swollen network, and thus, is not restricted by interfacial adsorption. Given that the hydrophilic nature of the components, the sorption performance could only be attributed to the inclusion complex formation of CDs with PAH molecules. The poly-CD cryogels could be recycled with an exposure to ethanol and reused without any significant loss in the sorption capacity of PAHs.Item Open Access Radiochemical and spectroscopic studies of cesium, barium, and cobalt sorption on some natural clays(Bilkent University, 2000-08) Shahwan, TalalThe wide growth in the nuclear activities results in an increasing subsequent influx of radioactive wastes into the environment. This problem has manifested a great deal of interest aiming at finding out ways through which those wastes can be harmlessly isolated from the human environment. Geological disposal is considered as one of the most promising solutions that ensures a safe storage of radioactive wastes as long as their activities are above the accepted levels. Clay minerals are proposed as backfill buffering materials in the geological repositories that can delay the migration of the radionuclides through sorption and thus decrease the contamination of underground waters. The extent of retardation of the radionuclide migration is dependent on factors like time of contact, pH and Eh of groundwater, concentration, temperature and grain size of the mineral particles. In this study radiochemical, spectroscopic (ToF-SIMS, XPS), and X-ray diffraction techniques were applied to examine different aspects of the sorption behavior of cesium, barium and cobalt on three natural clay minerals containing primarily kaolinite, illite-chlorite, and bentonite. The elements cesium (Z=55), barium (Z=56), and cobalt (Z=27) have the radioactive isotopes superscript 137 Cs (half-life=30.17 years), superscript 140 Ba (half-life=12.79 days), and superscript 60 Co (half-life=5.3 y) which are important in radioactive waste management. The first two radionuclides are produced in high yields in nuclear fission, whereas the third is an activation product. The natural clay samples that were used in this study originated from natural mineralogical beds at Sindırgı, Afyon, and Giresun regions in Turkey. The characterization of these clay samples showed that the primary clay minerals were kaolinite in Sındırgı clay, chlorite and illite in Afyon clay, and montmorillonite in Giresun clay. Each of these clays possesses different structural properties that result in different sorption capabilities. Radiochemical batch experiments were carried out to examine the effects of time, concentration, and temperature on the sorption of cesium, barium and cobalt on clays. Solutions of these cations spiked with several microliters of the radionuclides 137 CS (half-life=30.1 y), 133 Ba (half-life=10.7 y), and 60 Co (half-life=5.3 y) were monitored using gamma-ray spectroscopy prior to and after each sorption experiment. These results showed that equilibrium is achieved within two days in all cases. The sorption data was adequately described by Freundlich and Dubinin-Radushkevich isotherm models. Based on the parameters of those isotherm models, it was found that sorption was nonlinear, and that bentonite showed the highest sorption affinity and sorption capacity towards the sorbed ions. The thermodynamic parameters indicated that while sorption of cesium and barium on the three clays is exothermic that of cobalt is endothermic. The obtained values of Gibbs free energy change, Delta G degrees, were generally in the 8-16 (kJ/mol) energy range that corresponds to ion exchange type sorption mechanism. Since sorption is mainly a surface phenomenon, part of our sorption studies were carried out using the surface sensitive techniques; Time of Flight- Secondary Ion Mass Spectroscopy (ToF-SIMS) and X-ray Photoelectron Spectroscopy (XPS). In addition, depth profiling up to 70 angstroms was performed using ToF-SIMS to investigate cesium, barium and cobalt concentrations through the clay surface. ToF-SIMS and XPS studies were helpful in figuring out the surface composition of different clays prior to and after sorption. Quantification of the depletion of different alkali and alkaline-earth metals initially contained within the analyzed clay surface showed that ion exchange plays a primary role in the sorption process. In addition, X-Ray Diffraction (XRD) technique was applied to figure out the mineralogical composition of the clay minerals used and examine any structural change a accompanying the sorption process. XRD spectra of the clay samples after sorption showed that -apart from some intensity reductions in some clay features-, no primary changes were detected in the sorption cases of cesium and cobalt. In barium sorption, however, features belonging to barium carbonate were present in the spectra corresponding to sorption on chlorite-illite and bentonite.Item Open Access Sorption behavior of radioiodine on organic rich soil, alumina and clay minerals(Bilkent University, 1992) Assemi, ShoelehSorption behavior of radioiodine on organic rich soil, alumina, chlorite- illite clay mixture, kaolinite and bentonite have bc;en studied using the batch method. was used as tracer. Characterization of samples were done by FTIR, X-ray diffraction spectrometry and particle size distribution by Andreason pipette method. The grain size of the samples used were all below 38/xm and the experiments were performed at room temperature. The aqxreos phase used in all experiments were synthetic ground water with a composition similar to the underground waters of the regions where the samples were obtained. Stock solutions containing tracer, were prepared using synthetic ground- water. Initial concentration of inactive iodide ion in the solutions ranged from 10~®to 10“^ mmole/ml. The influence of contact time, solution/solid ratio, pH of synthetic ground- water, biomass of soil and I~ ion concentration on the sorption of radioiodine on the organic rich soil were investigated. The effect of I~ ion concentration and complexing agents on the sorption behavior of radioiodine on alumina and clay minerals were also studied. A rather slow kinetics was observed for tlie adsor])tion of radioiodine on the organic rich soil, tending saturation within 14 da.ys. It was observed that distribution ratio increased with increasing ratio of the volume of solution to the mass of soil(V/m ratio) and reached a platee.u after V/m=50. Distribution ratio did not change very much by changing the pH of the solution. Comparison of Eh-pH behavior of the solutions with the standard Eh-pH graph of iodine-water system indicated that in the whole pH rcinge, iodine is mostly preseirt in I~ form. To observe the effect of soil biomass soil samples were sterilized by heat and gamma-ray source and the results were found to be much lower than the control sample. Increasing the concentration of iodide ion in the .solution, caused a decrease in Rd. values. Desorption Wcvs ol)served only for low initial iodine concentrations < 1 X I0~^7nmol/ml), for organic rich soil which suggests that at least two sites and/or mechanisms are involved in the sorption. The sorption data were fitted to Freundlich and Dubinin-Radushkevich isotherms. The slope of Freundlich isotherm was found to be less than 1 which indicates the non-linearity of the isotherm. The mean free energy of adsorption was calculated from the slope of Dubinin-Radushkevich isotherm and was found as about 11 k.J/mol. The distribution of sites on organic rich soil was calculated using the Freundlich and Dubinin-Radushkevich constants, considering Cl~ as the competing ion with I~ in the solution. The affinities of sites were found to be about three times higher for Cl~ than I~. Among the clay minerals, the highest Rd value was found for chlorite-illite cla}^ mixture but tlie Rd values found for alumina and the other sanrples were well below those found for the organic rich soil. The sorption data were fitted to Freundlich and Dubinin-Radushkevich isotherms. All the Freundlich isotherms were non-linear (slopeItem Open Access Sorption of cesium and strontium on montmorillonite and kaolinite(De Gruyter Oldenbourg, 1988) Erten, H. N.; Aksoyoglu, S.; Hatipoglu, S.; Göktürk, H.Sorption characteristics of Cs+ and Sr++on montmorillonite and kaolinite type clays and soil fractions from various regions of Turkey were studied using the batch method. 137Cs and 90Sr were used as tracers. Concentrations of Cs+ and Sr++ ions ranged from 10-8to 10-2 mol/1; natural groundwater was used and the grain size of the solid particles was < 20 yμm. Equilibrium was reached in 4 - 7 days for Cs+and 7 - 11 days for Sr++. The distribution coefficient, RD, increased with decreasing grain size, suggesting mainly a surface phenomenon. The sorption isotherms were non-linear suggesting at least two different sorption processes. The sorption was found to be predominantly reversible. Cs+ was sorbed much stronger than Sr++in all samples. © 1988, Walter de Gruyter. All rights reserved.Item Open Access Sorption of Cs+ and Ba2+ on magnesite(Cambridge University Press, 1998) Shahwan, Talal; Süzer, Şefik; Erten, Hasan N.Sorption behavior of Cs and Ba ions on magnesite was studied using the radiotracer method complemented by X-ray photoelectron spectroscopy. Cs and Ba were used as radiotracers. The sorption of Cs is seen to be temperature dependent, whereas Ba sorption is not much affected by temperature changes. It was found that Freundlich type isotherms provide an adequate description of the sorption process. The magnitude of the free energy of sorption are seen to be within the 8-16 kj/mol range. It can be remarked that the sorption of Cs and Ba on magnesite is a fast process suggesting an ion exchange type mechanism, mainly taking place at the surface of mineral particles.Item Open Access Sorption studies of cesium and barium on magnesite using radiotracer and x-ray photoelectron spectroscopy(Bilkent University, 1997-06) Shahwan, TalalAs the consumption of the radioactive materials is continuously increasing, the problem of disposing the resulting v^^astes safely is becoming more challenging. One way through which these radioactive wastes could be isolated from the biological environment is by disposing them in deep geological formations. Clay minerals are proposed as backfill buffering materials that can delay the migration of the radionuclides and thus decrease the contamination of underground waters. The extent of retardation of the radionuclide migration is dependent on factors like time of contact, pH and Eh of groundwater, concentration, temperature and grain size of the mineral particles. Up to now, several studies were carried out to examine the effect of such parameters on the sorption behavior of different radionuclides on various kinds of minerals. This study was conducted to investigate the effects of time, concentration and temperature on the sorption behavior of cesium and barium ions on magnesite. Cesium 137 140 and barium have the radioactive isotopes Cs (t^^^ = 30.1 y) and Ba (t^^^ = 12.8 d) 1/2 produced in high yields during the fission process which are important in radioactive waste considerations. Magnesite is a mineral composed mainly of magnesium carbonate 2+ together with minor amounts of quartz and has a single exchangeable cation. Mg . The radiotracer method and x-ray photoelectron spectroscopy, which is a powerful surface sensitive tool, were used in this study. The results obtained from both methods complemented each others and were in good agreement. Kinetic studies of the sorption process show that equilibrium was approached within one day of contact for both of cesium and barium ions. The data of the sorption of both cations using different concentrations at various temperatures were most adequately described by the Freundlich type isotherms which correspond to multilayer adsorption on heterogeneous surfaces. The values of the Freundlich constants k and n imply that barium ions have slightly larger adsorption affinity and adsorption intensity than cesium ions. The adsorption data at low concentrations were also observed to obey the Dubinin-Radushkevich type isotherms which describe monolayer adsorption on heterogeneous or homogeneous surfaces. The adsorption data were very poorly described by the Langmuir type isotherms. Thermodynamic parameters such as enthalpy change, AH°, entropy change, AS° and free energy change of adsorption, AG°, were calculated from the sorption data of cesium and barium ions at different temperatures. The values obtained for AH° and AS° were -37 kJ/moL, -0.09 kJ/moL.K and -13 kJ/moL, -0.009 kJ/moL.K for cesium and barium ions respectively. The negative AH° values indicate the exothermic nature of adsorption which means that low temperatures are favored. The decrease in entropy upon adsorption implied by the negative AS° values is indicative of the stability of adsorption for both cations. The values of AG° at different temperatures were all negative indicating the spontaneity of the adsorption process for both cesium and barium ions. The magnitudes of AG° were seen to be within the 8-16 kJ/moL range which is the energy range of ion- exchange type processes.Item Open Access Sorption studies of Cs+, Ba2+, and Co2+ ions on bentonite using radiotracer, ToF-SIMS, and XRD techniques(De Gruyter Oldenbourg, 2001) Shahwan, T.; Erten H. N.The sorption behaviour of Cs+, Ba2+, and Co2+ ions on bentonite were investigated using the radiotracer method, Time of Flight-Secondary Ion Mass Spectroscopy (ToF-SIMS), and X-Ray Diffraction (XRD). The sorption of Cs+ and Ba2+ were exothermic while sorption of Co2+ was endothermic. The sorption data were well described by Freundlich and Dubinin-Radushkevich isotherms. According to ToF-SIMS results Na+ and Mg2+ were the primary exchanging ions in bentonite. The XRD spectra showed that no structural changes were associated with the sorption of Cs+ and Co2+, and BaCO3 precipitate was formed upon the sorption of Ba2+ on bentonite.Item Open Access Surface spectroscopic studies of Cs+, and Ba2+ sorption on chlorite-illite mixed clay(De Gruyter Oldenbourg, 2000) Shahwan, T.; Sayan, S.; Erten, H. N.; Black, L.; Hallam, K. R.; Allen, G. C.The sorption behavior of Cs+, and Ba2+ on natural clay was investigated using ToF-SIMS, XPS, and XRD. The natural clay was composed mainly of chlorite and illite in addition to quartz and calcite. Depth profiling up to 70 Å was performed at 10 Å steps utilizing ToF-SIMS to study the amount of sorbed Cs+ and Ba2+ as a function of depth in the clay matrix. The results suggest that Cs+ and Ba2+ ions were sorbed primarily by ion exchange coupled with hydrolytic sorption. According to ToF-SIMS and XPS results, the total sorbed amount of Ba2+ was larger than that of Cs+. Quantitative determination of the primary cations within the analyzed clay before and after sorption indicated that for Ba2+ sorption, Ca2+, Mg2+ and for Cs+ sorption Ca2+, K+ were the major exchanging ions. The XRD spectra of Ba-sorbed clay contained new peaks that were identified as BaCO3.Item Open Access ToF-SIMS depth profiling analysis of the uptake of Ba2+ and Co2+ ions by natural kaolinite clay(Academic Press, 2004) Shahwan, T.; Erten, H. N.; Black, L.; Allen, G. C.The sorption behavior of Ba2+ and Co2+ ions on a natural clay sample rich in kaolinite was studied using time-of-flight secondary ion mass spectrometry (ToF-SIMS). Depth profiling at 10-Å steps was performed up to a 70-Å matrix depth of the clay prior to and following sorption. The results showed that Co2+ is sorbed in slightly larger quantities than Ba2+, with significant numbers of ions fixed on the outermost surface of the clay. Depletion of the ions K+, Mg 2+, and Ca2+ from the clay lattice was observed to accompany enrichment with Co2+ and Ba2+ ions. The data obtained using X-ray powder diffraction (XRPD) and scanning electron microscopy (SEM) indicated insignificant structural and morphological changes in the lattice of the clay upon sorption of both Ba2+ and Co2+ ions. Analysis using energy dispersive X-ray spectroscopy (EDS) showed that the average atomic percentage (±S.D.) of Ba and Co on kaolinite surface were 0.49±0.11 and 0.61±0.19, respectively, indicating a limited uptake capacity of natural kaolinite for both ions. © 2004 Elsevier Inc. All rights reserved.Item Open Access TOF-SIMS study of Cs+ sorption on natural kaolinite(Elsevier, 1999) Shahwan, T.; Erten, H. N.; Black, L.; Allen, G. C.The sorption of Cs+ on natural kaolinite has been studied using time-of-flight secondary ion mass spectrometry (TOF-SIMS). Depth profiling up to 70 Å was performed to study the change in the amount of sorbed Cs+ as a function of depth in the kaolinite matrix. Quantitative determination of the amounts of primary cations in the kaolinite structure before and after sorption of Cs+ ions was carried out to identify which cations are possibly taking part in the sorption process. The experimental results showed that large amounts of Cs+ are sorbed onto the surface of kaolinite and that sorption decreases sharply over the first 10-Å depth. The fact that kaolinite surface was negatively charged under the operating pH indicates that physisorption has an important contribution to the sorption process. The results also showed that Na+, K+, Li+, Ca2+, Mg2+ and Fe3+ were involved in the sorption process with Cs+ and that the total decrease in the amounts of these cations is close to the amount of sorbed Cs+, suggesting that ion exchange is the dominant sorption mechanism. Copyright (C) 1999 Elsevier Science B.V. 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