Sorption kinetics of uranium-238 and neptunium-237 on a glacial sediment

Studies of uptake of radionuclides by natural materials have shown that sorption may occur via fast equilibrium exchange and/or slow kinetic processes, which can be described using a series of box models. This paper describes the use of such models to evaluate the solid-solution partitioning of ²³⁸U and ²³⁷Np on a clay rich sediment. Experimental data are obtained using the batch sorption technique, which are then analysed using 1, 2, and 3 box kinetic models. Uptake of ²³⁸U is initially rapid, with approximately 90% sorbed within the first 30 minutes. Sorption continues, but at a slower rate. Uptake of ²³⁷Np is initially slower than U, with approximately 30% sorbed within the first 30 minutes. Sorption again continues, at a slower rate. Analysis of the experimental data indicates that sorption can be described using 2 and 3 box kinetic models. The results demonstrate that sorption of uranium and neptunium on clay rich sediments occurs via equilibrium and kinetically controlled pathways, with neptunium being controlled by kinetics to a greater extent than uranium. The 2 or 3 box model can describe sorption of neptunium, uranium requires the 3 box model.     

Equilibrium surface segregation of dissolved nonmetal atoms on iron(100) faces

At elevated temperatures equilibria of surface segregation X (dissolved) = X (adsorbed) have been studied for the nonmetal atoms X = C, N and S. Iron single crystals with (100)orientation have been doped with different concentrations of solute atoms (in the range about 10–100 wt ppm). The samples were introduced into the UHV chamber, cleaned and then heated to temperatures in the α-solid solution range. The surface concentration of the segregated nonmetal atoms was observed by AES for different bulk concentrations in dependence of the temperature. The LEED pattern was also observed during segregation equilibrium at temperatures up to about 750° C. The LEED patterns indicate a c(2 × 2) structure for carbon and nitrogen as well as for sulfur. The temperature dependence of the surface concentration for carbon on Fe(100) can be described by a Langmuir-McLean equation, an average segregation enthalpy of ?85 kJ/mol°C is obtained. Since N₂ desorption occurs the nitrogen segregation is in virtual equilibrium only at temperatures <500°C. The equilibrium surface concentration of sulfur on α-iron is virtually independent of the solute concentration and the temperature: there is always a saturated layer of sulfur on the (100) faces, even at small bulk concentrations. Since the thermodynamic activity of the nonmetal atoms is well defined in the segregation studies (except nitrogen at higher temperatures) , the results can be correlated with studies in gas atmospheres at atmospheric pressure. The relations to the kinetics of the carburization and the nitrogenation of iron are discussed and the influence of sulfur on these reactions.     

Sorption kinetics of aqueous benzene for attached bacteria on sorbents

In this study we investigated the effect of bacteria attached onto the surfaces of two sorbents e.g., activated carbon and alginate bead, on the sorption kinetics of aqueous benzene. Kinetic sorption experiments were performed to obtain time-dependent data of aqueous concentration subjected to sorption at an initial concentration. The kinetic sorption data were fitted with two-site sorption model that consists of fast (equilibrium type) sorption site and limited slow (nonequilibrium or kinetic type) sorption site. Experimental results showed that both fast sorption and biodegradation was associated with removal of benzene for alginate bead, but only fast sorption for activated carbon for either case of bacterial treatment. Much lower sorption for attached case of carbon can be explained by the fact that bacteria inhibited sorption of aqueous benzene by filling them in the cavities of carbon surface. Modeling study revealed that sorption process for activated carbon followed two-site kinetic with unlimited slow sorption but the one for bead was described by two-site kinetic with limited slow sorption model since a significant amount of aqueous benzene was present in aqueous phase due to lower sorbing capacity.     

Investigation of sorption phenomena by solid phase extraction and liquid chromatography for the determination of some ether derivatives of tetrabromobisphenol A

Observed sorption and chromatographic behaviour served as a starting point for the examination of four ether derivatives of the flame retardant tetrabromobisphenol A (TBBPA): dihydroxyethyl (DHEE), dimethyl (DMe), diallyl (DAE) and dibromopropyl (DBPE). To date, there is little or no information about these compounds in the scientific literature. The targets in the present study had calculated log K_ow values of 6.0–10. A broad range of different types of solvents were used in order to elucidate the mechanisms of sorption onto silica (glass) and two solid phase extraction cartridges based on polystyrene divinylbenzene polymers, hydroxylated (Isolute ENV+) and vinylpyrrolidone (Oasis HLB) containing units. Also, three chromatographic columns (C18, C8 and dual C18‐based, i.e. a polar ligand together with C18 on a silica surface) were evaluated. The following were observed: desorption of the targets from silica surface by 1‐propanol showed the best results and the yields were further improved by silylation of the surface. Regardless of the experimental test conditions applied, the lowest recovery was seen for the DMe derivative, followed by TBBPA itself, which had calculated log K_ow values in between the other targets. A washing solution containing up to 70% methanol could be used without elution of the targets from the solid phase extraction cartridge . The dihydroxethyl ether derivative of TBBPA is most probably not affected by environmental relevant pH due to a likely high pK_a (ca 15). Also, this study shows that the polar character of the dual‐phase column was not as pronounced as asserted by the manufacturer. Copyright © 2009 John Wiley & Sons, Ltd.     

Influence of Molecular Structure and Packing on Sorption and Transport Properties of Dichloromethane in Polyetherimides

The effects of thermal history on dichloromethane vapor sorption and transport properties of polyetherimides were studied. Films were prepared by solution casting at room temperature and heat treated for 24 h at different temperatures below the corresponding glass transition temperature of each material. Changes of the transport properties due to heat treatment were observed and are correlated to changes in density, free volume, and thermal transitions. Deviation from Fick's and Henry's laws was observed for all the samples studied. Without heat treatment and at low activities of the penetrant, the materials studied show sorption kinetics similar to the Fickian behavior. On the other hand, sorption measurements tests for the heat‐treated films at high activities of dichloromethane show kinetics similar to Case II diffusion. Equilibrium sorption data obtained at different penetrant concentrations show deviation from Henry's law behavior depending on the thermal history of the sample.     

The influence of treatment temperature on the acidity of MWCNT oxidized by HNO3 or a mixture of HNO3/H2SO4

The nature of multi-walled carbon nanotubes (MWCNTs) varies with the change in oxidation conditions. In this work, the effect of treatment temperatures on the acidity of MWCNTs was studied. Oxidation was performed by refluxing the MWCNTs in nitric acid or mixtures of sulfuric acid and nitric acid at different temperatures. After oxidative treatment, a quantitative characterization of o-MWCNTs has been performed using acid-base titrations which show that the number of surface acidic functional groups increased by increasing the treatment temperatures. Energy dispersive X-ray (EDX) measurements show that the oxygen content increased with increasing treatment temperatures. Fourier transform infrared absorption spectroscopy (FTIR) was used for qualitative characterization. It has been demonstrated that the acidity is a function of the type of oxidizing agent used and the treatment temperatures. Due to the importance in attachment strategies and functionalization, this study adds to the global discussion of the possibility of controlling the MWCNTs’ surface chemistry which plays a crucial role in determining its reactivity.     

Quantitative high-resolution on-line NMR spectroscopy in reaction and process monitoring

On-line nuclear magnetic resonance spectroscopy (on-line NMR) is a powerful technique for reaction and process monitoring. Different set-ups for direct coupling of reaction and separation equipment with on-line NMR spectroscopy are described. NMR spectroscopy can be used to obtain both qualitative and quantitative information from complex reacting multicomponent mixtures for equilibrium or reaction kinetic studies. Commercial NMR probes can be used at pressures up to 35 MPa and temperatures up to 400 K. Applications are presented for studies of equilibria and kinetics of complex formaldehyde-containing mixtures as well as homogeneously and heterogeneously catalyzed esterification kinetics. Direct coupling of a thin-film evaporator is described as an example for the benefits of on-line NMR spectroscopy in process monitoring.     

二维相关吸收光谱法研究多壁碳纳米管与腐植酸吸光组分间非均相吸附行为

溶解性有机质（DOM）是水环境中一类复杂的溶解性有机混合物,不仅可影响污染物归趋及生物有效性,且DOM自身属于消毒副产物（DBPs）前驱体。为此,如何高效去除水中DOM已成为当前环境污染控制与治理技术研究的热点问题之一。以商品化腐植酸（HA）为DOM典型代表物质,利用紫外可见吸收光谱结合二维相关光谱法（2D-COS）从动力学、吸附等温线及热力学等角度研究了原始多壁碳纳米管（MWCNT）、羟基化MWCNT及羧基化MWCNT与HA吸光组分间吸附行为。2D-COS提高了HA一维吸收光谱分辨率,经二维相关吸收光谱图分析显示3种MWCNTs对HA吸光组分的吸附变化顺序均为275 nm→400 nm,表明MWCNTs与HA吸光组分间为非均相吸附行为。动力学结果显示MWCNTs与275 nm处HA吸光组分间吸附速率高于MWCNTs与400 nm处HA吸光组分间吸附速率,表明275 nm处HA吸光组分可优先吸附至三种MWCNTs上。在25和35 ℃条件下,MWNCTs与HA吸光组分间吸附等温线表现为非线性,且Freundlich模型拟合决定系数R2大于Langmuir模型拟合决定系数,表明Freundlich吸附等温模型比Langmuir吸附等温模型更有利于描述MWCNTs与HA吸光组分间吸附等温线。275 nm处HA吸光组分的饱和吸附容量（q_max）及相同给定平衡浓度下单点吸附系数K_d高于400 nm处HA吸光组分,进一步表明MWCNTs与HA吸光组分间为非均相吸附。此外,当给定平衡浓度（c_e=0.5 cm-1和c_e=1.5 cm-1）越低,MWCNTs与HA吸光组分间结合能力越大,即HA吸光组分浓度较低时更易与MWCNTs上高能吸附位点相结合。相同平衡浓度下MWCNTs与特定HA吸光组分间吸附能力顺序表现为MWCNT8>MWCNT8-OH>MWCNT8-COOH,表明功能化基团可影响MWCNTs与HA吸光组分间吸附特性。另外,相同条件下单点吸附系数K_d与MWCNTs比表面积间无显著相关性（p>0.05）,表明比表面积不是造成MWCNTs与特定HA吸光组分间结合能力差异的主要因素;K_d与MWCNTs中孔孔隙度间呈显著正相关（p<0.05）而与微孔孔隙度间无显著相关性（p>0.05）,这主要是由于HA吸光组分可进入MWCNTs中孔而难以通过MWCNTs微孔。最后热力学分析结果显示Gibbs自由能变（ΔG0）<0、焓变（ΔH0）>0和熵变（ΔS0）>0,表明MWCNTs吸附HA吸光组分的过程为吸热反应,可自发进行,升温可促进MWCNTs对HA吸光组分的吸附,且吸附过程中固液界面的无序性增加。相同温度及吸光组分下,MWCNT8的ΔG0值小于MWCNT8-OH及MWCNT8-COOH,进一步表明MWCNT8与特定HA吸光组分结合能力强于MWCNT8-OH及MWCNT8-COOH。证明了2D-COS可识别HA中具有不同吸附行为的吸光组分,二维相关吸收光谱技术可作为研究MWCNTs与DOM间非均相吸附行为的有效工具。同时,有助于更好地理解MWCNTs与DOM间相互作用特性及机理,不仅可为水环境中DOM去除研究提供基础数据及新的研究思路,且有利于更好地预测自然环境中MWCNTs及DOM迁移传输及环境归趋。     

Ultrasound-assisted removal of malachite green from aqueous solution by dead pine needles

The dead needles of Aleppo pine (Pinus halepensis) were tested as a possible sorbent for the removal of malachite green from aqueous solutions in the absence and presence of ultrasound. Batch process was employed for sorption kinetic and equilibrium studies. Sorption experiments indicated that the sorption capacity was dependent of operating variables. Both the rate and the amount of malachite green sorption are markedly increased in the presence of the ultrasonic field. The dye removal with the assistance of ultrasound was enhanced with the increase of sorbate initial concentration and temperature, and with the decrease of sorbent dosage and ionic strength. The combination of stirring and ultrasound leads to an improvement of the removal of dye. The sorption kinetics was controlled by the intraparticle diffusion. The intraparticle diffusion coefficient increased 1.7 times in the presence of ultrasound and up to 3.6 times in the combined process. The sorption capacity, estimated according to the Freundlich model, indicates that ultrasound enhanced the sorption properties of the sorbent. The effect of ultrasound on the improvement of dye sorption is due to a variety of physical and mechanical effects as well as to thermal properties. The combination of ultrasound and stirring for the sorption process was shown to be of interest for the treatment of wastewaters contaminated with malachite green.     

Relaxation of non-equilibrium states of myoglobin studied by Mössbauer spectroscopy

A metastable Fe(II) low-spin myoglobin complex with H₂O at the sixth coordination place has been produced by X-ray irradiation of metmyoglobin at 80 K. The relaxation into the equilibrium state of deoxymyoglobin was investigated as a function of temperature. It starts at temperatures above 140 K and cannot be understood by assuming one well-defined activation energy. The relaxation is, however, well described by assuming a Gaussian barrier height distribution.     

Sorption and diffusion behaviours of strontium in sodium-type bentonite bed

Sorption and diffusion of Sr were examined using a typical Japanese bentonite. The experimental results showed that Sr sorption on the bentonite had linear relationship between the equilibrium Sr concentration and Sr sorption amount, i.e., Henry’s type of sorption, in wide initial Sr concentration from 1.1 × 10^?9 to 1.1 × 10^?4 mol L^?1 at pH 10. The Sr sorption also indicated pH dependence in pH range between 2 and 12. Sorption modelling calculation indicated that cation-exchange reactions contributed to Sr sorption in the pH range studied and a surface complexation reaction was predominant above pH 8. Diffusion of Sr in loosely compacted bentonite bed was described by pore and surface diffusion and surface complexation of Sr. Chemical-transport calculations reproduce the diffusion data at pH 5 using the cation-exchange parameters obtained in the analysis of the batch sorption experiment.     

Impurity transport in a dual-porosity medium with sorption

A nonstationary model of impurity transport in a dual-porosity (fractured porous) medium with sorption is proposed. It is shown that the equilibrium between dissolved and adsorbed phases is absent for a prolonged time, which leads to the development of nonclassical impurity transport regimes. Parameter values are found for which the behavior of the system cannot be described using the conventional model of equilibrium sorption even at large times for which the equilibrium between dissolved and adsorbed components should be established.     

Temperature effect on the sorption of cholate anions on calcined LDH

Layered Double Hydroxides are a class of materials that can be described as positively charged layers of divalent and trivalent cations in the centre of edge-sharing octahedra. Cholesterol derivatives such as cholic acid are substances that play an important role in the digestion of fat components by the organism. This work presents a study on the intercalation of cholate anions in calcined MgAl-CO₃-HDL. Isotherm experiments were performed at three different temperatures to evaluate the capacity of anion removal by sorption in the calcined LDH. The plateau was reached in all conditions. Increasing temperature results in decreasing cholate sorption. Characteristic peaks of LDH regenerated with OH⁻ anions were observed at lower cholate concentrations. A peak in 2θ equals to 7.5° and peaks between 15° and 20° are observed. Those peaks are the same as the ones observed in the pure sodium cholate PXRD. At higher cholate concentrations the sorbed solids present PXRD related to an additional layered phase, which is related to intercalation of cholate anions with basal spacing equal to 34.3 Å. Thus, the cholate anions are also intercalated with a bilayer molecular arrangement at equilibrium concentrations at the isotherms plateau.     

Characterization of aluminum-carbon composites obtained via mechanical activation of aluminum and carbon nanotubes

The relaxation of structural defects of aluminum-multiwall carbon nanotubes (MWCNT) composite materials obtained via mechanical activation is studied in situ by X-ray diffraction using synchrotron radiation. Mechanically activated Al-MWCNT mixtures are annealed at temperatures of up to 600°C in an inert gas flow and X-ray diffraction patterns are simultaneously registered with a position-sensitive X-ray detector. It is demonstrated that mechanically activated samples of pure Al and composites with large-diameter MWCNTs (～20 nm) begin to experience the relaxation of defects accumulated during mechanical activation at temperatures as low as 100–150°C, while samples with small-diameter MWCNTs (～10 nm) exhibit thermal stability of structural defects up to 500°C.     

The use of calcination in exposing the entrapped Fe particles from multi-walled carbon nanotubes grown by chemical vapour deposition

Multi-walled carbon nanotubes (MWCNTs) were synthesized a by chemical vapour deposition method. The effect of calcination at temperatures ranging from 300 to 550°C in exposing the metal nanoparticles within the nanotube bundles was studied. The degree of degradation of the structural integrity of the MWCNTs during the thermal process was studied by Raman spectroscopy, X-ray diffraction analysis, field-emission scanning electron microscopy, and transmission electron microscopy. The thermal behaviour of the as-prepared and calcined samples was investigated by thermogravimetric analysis. Calcination in air, at 400°C for 1 h, was found to be an efficient and simple method to extract metallic impurities from the amorphous carbon shells with minimal damage to the tube walls and lengths. The nanotubes were observed to be damaged at temperatures higher than 450°C.     

Sorption and diffusion behaviours of strontium in sodium-type bentonite bed

Sorption and diffusion of Sr were examined using a typical Japanese bentonite. The experimental results showed that Sr sorption on the bentonite had linear relationship between the equilibrium Sr concentration and Sr sorption amount, i.e., Henry’s type of sorption, in wide initial Sr concentration from 1.1×10⁻⁹ to 1.1×10⁻⁴ mol L⁻¹ at pH 10. The Sr sorption also indicated pH dependence in pH range between 2 and 12. Sorption modelling calculation indicated that cation-exchange reactions contributed to Sr sorption in the pH range studied and a surface complexation reaction was predominant above pH 8. Diffusion of Sr in loosely compacted bentonite bed was described by pore and surface diffusion and surface complexation of Sr. Chemical-transport calculations reproduce the diffusion data at pH 5 using the cation-exchange parameters obtained in the analysis of the batch sorption experiment.     

Sorption and Diffusion of Supercritical Carbon Dioxide in a Biodegradable Polymer

A gravimetric method was used to study the sorption and diffusion of supercritical carbon dioxide in a temperature range from 40°C to 80°C and a pressure range from 8.0 to 18.0 MPa in a biodegradable polymer, namely poly(butylene adipate-co-terephthalate) (PBAT). The PBAT presented Fickian behavior and Fick's diffusion model was applied to determine the amount of carbon dioxide present in the samples after a predetermined exposure time as well as the diffusion coefficients. The variations of diffusion coefficients of CO₂ for the sorption under supercritical conditions and desorption at ambient conditions as well as equilibrium sorption amounts of CO₂ with variations of pressure and temperature were determined and compared.     

Effect of reaction parameters on the growth of MWCNTs using mesoporous Sb/MCM-41 by chemical vapour deposition

Mesoporous Si-MCM-41 molecular sieve was synthesized hydrothermally and different wt.% of Sb (1.0, 2.0, 3.0, 5.0, 10.0, 15.0 and 20.0) was loaded on it by wet impregnation method. The Sb/MCM-41 materials were characterized by various physico-chemical techniques such as XRD, TGA and TEM. The TEM image showed a honeycomb structure of the host material. They were used as catalytic templates for the growth of MWCNTs by CVD method with different temperatures at 700, 800, 900 and 1000 °C using acetylene as a carbon precursor. The reaction temperature was optimized for the better formation of MWCNTs and they were purified and then characterized by XRD, SEM, HR-TEM and Raman spectroscopy techniques. The formation of MWCNTs with diameter in the range of 4−6 nm was observed from HR-TEM. The good thermal stability and high productivity of catalyst observed in this study revealed that the 2 wt.% Sb loaded MCM-41 could be a promising support for the catalytic synthesis of MWCNTs at 800 °C by CVD method.     

Aspect ratio control of acid modified multiwalled carbon nanotubes

This study examined the effects of acid treatments on the length of multiwalled carbon nanotubes (MWCNTs) as well as the influence of the aspect ratio of the MWCNTs on the electrical percolation threshold. In particular, the length distribution, intensity ratio of the G and D Raman peaks, BET surface area, and maximum decomposition temperatures of the MWCNTs were investigated. The MWCNTs showed different electrical percolation thresholds depending on the aspect ratio. The higher aspect ratio MWCNTs had lower electrical percolation thresholds than those with smaller ratios due to their ease of contact with other MWCNTs. In terms of the electrical behavior of a MWCNT film, many more short MWCNTs were necessary to reach the electrical percolation threshold than long MWCNTs. These results demonstrate the need to control the aspect ratio of MWCNTs in order for them to be used efficiently in electrical applications.