Investigation of cesium uptake from aqueous solutions using new titanium phosphates ion-exchangers

The uptake of cesium from aqueous solutions (pH 5) using titanium phosphates was investigated in the absence and presence of background electrolyte (0.1 M NaNO₃) using a batch technique. The determination of cesium was performed by gamma spectroscopy using ¹³⁷Cs as tracer. The obtained sorption isotherms could be satisfactorily reproduced by a Langmuir sorption equation. The maximum uptake capacity values (q _max) calculated fitting the experimental data by this equation were 167 and 118 mg/g for solutions of initial pH 5 in the absence and presence of background electrolyte. Kinetics data obtained at 293, 308 and 323 K could satisfactorily reproduced by the pseudo-second order equation. It was demonstrated that the new synthesized materials can remove considerable amounts of cesium from aqueous solutions and ion exchange is considered to be the principal mechanism for cesium removal. Toxicity characteristic leaching procedure and desorption tests provided data about the application of the sorbents in environmental remediation.     

Uranium removal from aqueous solutions by raw and modified thermal power plant ash

The U(VI) removal from aqueous solutions (concentration range 125–2,000 mg/L, pH 3) by raw and NaOH-modified power plant ash was investigated by means of a batch method under the following experimental conditions: NaOH concentration 5 M, contact time 1 h, respectively 4 h, temperature 70, 90 °C. The amount of sorbed uranium was determined spectrophotometricaly using the Arsenazo III method. The sorbents were examined prior and after the sorption experiments by scanning electron microscopy/energy dispersive spectroscopy. Typical sorption isotherms were calculated and modeled by the Langmuir and Freundlich equations. The experimental data showed that all materials can remove considerable amounts of uranium from acidic aqueous solutions. The maximum removal efficiency (q _max) values obtained, are 126 mg U/g for raw ash and 206 mg U/g for NaOH-modified. Sorption kinetics measurements were performed at 298, 308 and 323 K and thermodynamic parameters were calculated. The kinetic data obey a pseudo-second order equation.     

Sorption separation of Eu and As from single-component systems by Fe-modified biochar: kinetic and equilibrium study

The utilization of carbonaceous materials in separation processes of radionuclides, heavy metals and metalloids represents a burning issue in environmental and waste management. The main objective of this study was to characterize the effect of chemical modification of corncob-derived biochar by Fe-impregnations on sorption efficiency of Eu and As as a model compounds of cationic lanthanides and anionic metalloids. The biochar sample produced in slow pyrolysis process at 500 °C before (BC) and after (IBC) impregnation process was characterized by elemental, FTIR, SEM-EDX analysis to confirm the effectiveness of Fe-impregnation process. The basic physico-chemical properties showed differences in surface area and pH values of BC- and IBC-derived sorbents. Sorption processes of Eu and As by BC and IBC were characterized as a time- and initial concentration of sorbate-dependent processes. The sorption equilibrium was reached for both sorbates in 24 h of contact time. Batch equilibrium experiments revealed the increased maximum sorption capacities (Q _max) of IBC for As about more than 20 times (Q _max BC 0.11 and Q _max IBC 2.26 mg g^?1). Our study confirmed negligible effect of Fe-impregnation on sorption capacity of biochar for Eu (Q _max BC 0.89 and Q _max IBC 0.98 mg g^?1). The iron-impregnation of biochar-derived sorbents can be utilized as a valuable treatment method to produce stable and more effective sorption materials for various xenobiotics separation from liquid wastes and aqueous solutions.     

Sorption of levulinic acid onto weakly basic anion exchangers: equilibrium and kinetic studies

The equilibrium and dynamics of levulinic acid sorption on two weakly basic anion exchangers, in free base form, in single-component aqueous solutions were investigated. Adsorption isotherms such as Langmuir, Sips, Radke-Prausnitz, and Toth were applied to correlate the experimental data in the temperature range 285-315 K. Modeling results showed that the Toth model is the best one to correlate the sorption isotherms. The resulting Toth equations were used with the Clausius-Clapeyron equation to determine the isosteric heat of sorption. The sorption kinetics was experimentally measured via a completely stirred finite-bath batch experiment under different initial concentrations and at varying solution temperatures. The pseudo-second-order kinetic model and the Elovich equation were used to represent the kinetic data and the equation parameter values were also evaluated. The pseudo-second-order equation cannot simulate the experimental kinetic data, while the Elovich equation fitted the sorption dynamic data very well under all the operating conditions studied. Finally, the apparent activation energy of sorption was also determined.     

Traces of self-organisation and long-range memory in variations of environmental radon in soil: comparative results from monitoring in Lesvos Island and Ileia (Greece)

This paper addresses issues of self-affinity, long-memory and self-organisation in variations of radon in soil recorded in Lesvos Island, Greece. Several techniques were employed, namely (a) power-law wavelet spectral fractal analysis, (b) estimation of Hurst exponents through (b1) rescaled-range, (b2) roughness-length, (b3) variogram and (a), (c) detrended fluctuation analysis, (d) investigation of fractal dimensions and (e) analysis of five block entropies: (e1) Shannon entropy, (e2) Shannon entropy per letter, (e3) conditional entropy, (e4) Tsallis entropy, and (e5) normalised Tsallis entropy. Long-lasting antipersistency was identified during a period of anomalous radon variations following fractional Brownian modelling. Remaining variations did not exhibit analogous behaviour and followed fractional Gaussian modelling. Antipersistent power-law-beta-exponent-values between 1.5 and 2.0 were detected during anomalies. Persistent values were also found. Hurst exponents were mainly within 0 < H < 0.5. Some persistent exponents (0.5 < H < 1) were also observed. Fractal dimensions were within 1.5 < D < 2. Radon anomalies presented lower fractal dimensions. Shannon entropy ranged between 0.77 ≤ H(n) ≤ 2.38, Shannon entropy per letter, between 0.19 ≤ h ⁽ⁿ⁾ ≤ 0.59, conditional entropy, between 0.01 ≤ h _(n) ≤ 0.58, Tsallis entropy, between 0.55 ≤ S _q  ≤ 1.01 and normalised Tsallis entropy between, 0.98 ≤  $\hat{S}$  ≤ 5.42 (block-size n = 4). Entropies were lower during anomalies, indicating strong self-organisation. Persistency–antipersistency switching was observed, consistent with long-memory dynamics. Potential geological sources were discussed. The asperity-model was proposed. Findings were compared to results obtained under analogous methodologies in Ileia, Greece.     

Removal of cobalt and strontium from groundwater by sorption onto fishbone

Fishbone as a main backfill material of permeable reactive barrier to remediate groundwater contaminated with Co and Sr was investigated through single- and bi-solute competitive sorptions. The single-solute sorption data were fitted by Freundlich, Langmuir and Dubinin-Radushkevich models. The coefficients of determination (R ² > 0.91) indicated that all models fitted well. Maximum sorption capacities (q _mL ) of Co and Sr predicted by the Langmuir model were 0.55 mmol/g and 0.50 mmol/g, respectively. The bi-solute competitive sorption of the metals was analyzed by the Langmuir, competitive Langmuir, Sheindorf-Rebhun-Sheintuch (SRS) and P-factor models. The sorbed amount of one solute in bi-solute system decreased due to competition with the other solute. Langmuir model parameters for single- (q _mL and b _L ) and bi-solute (q _mL ^* and b _L ^* ) competitive sorptions were compared to analyze the effect of competition between the metals. The competitive Langmuir, SRS and P-factor models predicted the bi-solute competitive sorption data well (R ² > 0.93).     

Water-insoluble β-cyclodextrin polymer crosslinked by citric acid: synthesis and adsorption properties toward phenol and methylene blue

Water-insoluble β-cyclodextrin polymer (β-CDP) crosslinked by citric acid was obtained with a yield of 65% through an environment friendly synthesis procedure. FT-IR spectra disclosed that the hydroxyl groups of β-CD had reacted and condensated with the carboxyl groups of citric acid, and at the same time the structural characteristics of β-CD were essentially maintained in β-CDP. The β-CDP exhibited notable adsorption capability toward phenol (q _max = 13.8 mg g^?1) and especially large adsorption capability toward methylene blue (q _max = 105 mg g^?1). The concentration of methylene blue in water could be reduced to 0.11 mg L^?1 by the β-CDP, indicating the excellent adsorption sensitivity of β-CDP toward methylene blue. The adsorption results disclosed that the interior cavity and inclusion property of β-CD were maintained in the synthesized β-CDP.     

Removal of iodide from aqueous solutions by polyethylenimine-epichlorohydrin resins

The iodide removal from aqueous solutions (initial I^?-concentration: 300–5,000 mg/L) by a low and a high molecular weight polyethylenimine-epichlorohydrin resin was investigated both in absence and presence of background electrolytes (NaCl and Na₂SO₄, ionic strength due to background electrolyte 0.1 M) using a batch technique, ¹³¹I as radioactive tracer and high-resolution γ-ray spectrometry. The experiments in absence of background electrolyte were performed using solutions of initial pH 3 and 7, whereas those in presence using solutions of initial pH 3. The results, which demonstrated the high iodide-removal efficiency of both resins, were modeled using the Langmuir and Freundlich isotherm equations. The experimental data were better reproduced using the Langmuir equation. Using this equation maximum sorption capacity values (Q _max) of 638.8 and 603.3 mg/g were obtained for the high molecular weight resin from solutions of initial pH 3 and 7 respectively, whereas the corresponding values for the low molecular weight one were slightly lower (552.4 and 507.5 mg/g respectively). The iodide uptake by the resins strongly depended on the presence of competing anions and especially of sulfates. The examination of sections of the I-loaded resins grains by scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) revealed that iodine was evenly distributed throughout the bulk of the resins and not only bound to their surface.     

Adsorptive properties of X zeolites modified by transition metal cation exchange

The ionic exchange of the NaX zeolite by Ni²⁺ and Cr³⁺ cations was progressively driven and studied by adsorption of nitrogen and carbon dioxide. For each cation-exchanged X zeolite sample, the development of characteristics such as profile of isotherms, RI criterion, isosteric adsorption heat and microporous volume using both the Dubinin–Radushkevich (DR) equation and the t-plot, was followed through the nitrogen adsorption. Results show that the cationic exchange process, in the case of Cr³⁺ introduced at middle degree, is accompanied by a textural damage for Cr(x)X, in contrast to Ni²⁺-exchanged X zeolites. This degradation occurs without significant presence of mesopores, because the RI criterion values were found to be much lower than 2.2. The CO₂ adsorption isotherms were measured at intervals of 30 K from 273 K and the equilibrium pressures ranged from 0.5 to 600 Torr. The experimental data were correlated by the Toth model. The associated three adjustable parameters were estimated by nonlinear least-squares analysis. The effect of temperature on the model parameters and the Henry’s law slope, K _H , represented by the product of Toth parameters, are discussed.     

Monitoring 60Co activity for the characterization of the sorption process of Co2+ ions in municipal activated sludge

In large volumes produced activated sludges from wastewater treatment plants (WWTPs) with low concentrations of heavy metals can be utilized as agricultural fertilizers and soil conditioners. Increased contents of toxic xenobiotics are limiting factors that affect the utilization of these heterogeneous wastes. The main aim of our paper was to show the utilization of dried activated sludge (DAS) from municipal WWTP as potential Co²⁺ ions sorbent i.e. for non-agricultural purposes. The radio indicator method by radionuclide ⁶⁰Co and γ-spectrometry for characterization DAS sorption properties was used. DAS soluble and solid fractions were characterized by biochemical, ETAAS and CEC analysis. The sorption of Co²⁺ ions by DAS was rapid process and equilibrium was reached within 2 h. Sorption capacity of DAS (Q) increased with the initial concentration of CoCl₂ in the range from 100 to 4,000 μmol l^?1, reaching 20 and 160 μmol g^?1. Obtained Q values were depent on pH value from 2.0 to 8.0. The maximum sorption capacity (Q _max) of DAS at pH 6 calculated from mathematical model of Langmuir adsorption isotherm was 175 ± 9 μmol g^?1. FT-IR analyses showed the crucial role of carboxyl functional groups of DAS surfaces on cobalt uptake. For confirmation ion-exchange mechanism in sorption process of Co²⁺ ions by DAS scanning electron microscopy and EDX analysis were used.     

Sorption of uranium on lead hydroxyapatite

The uranium sorption from diluted aqueous solution onto lead hydroxyapatite was studied by using a batch-mode technique and the fluorimetric determination of uranium mass concentration. Partially crystallised lead hydroxyapatite [Pb₁₀(PO₄)₆(OH)₂] was obtained by direct precipitation and mild heating. This material presents very high specific surface, which is the key factor in the sorption of uranium from diluted solution. This material has a high ability to remove uranium (K _d,max from 5,661 to 18,833 ml/g, at 4 and 60 °C, respectively) in the chosen setup conditions (initial concentration of uranium 5 × 10^?6 M and pH 5.65).     

Effective adsorption of U(VI) from aqueous solution using magnetic chitosan nanoparticles grafted with maleic anhydride: equilibrium,kinetic and thermodynamic studies

The in situ formed magnetite nanoparticles was encapsulated by maleated chitosan to synthesize a novel magnetic chitosan nano-sorbent (MCN-MA) for the effective sorption of uranium. The sorption kinetics could be described by the pseudo-second-order model, whereas the sorption isotherms could be fitted to the Langmuir model (q _m = 187.9 mg/g). The MCN-MA showed higher U(VI) sorption capacities (compared to MCN) due to high affinity of carboxylate groups introduced from grafting maleic anhydride. Thermodynamic parameters indicate that U(VI) sorption is endothermic and feasible. The nano-size and magnetic property of the MCN-MA allow its efficient U(VI) sorption and facile magnetic separation from wastewaters.     

Carbon dioxide and nitrogen adsorption on porous copolymers of divinylbenzene and acrylic acid

Porous copolymers of divinylbenzene (DVB) and acrylic acid (AA) having DVB:AA ratios of 6:4, 8:2 and 9:1 were prepared following a distillation-precipitation method, using toluene as the porogenic agent. The materials thus obtained, which showed specific surface area in the range of 380–600 m² g^?1 and pore volume in the range of 0.14–0.18 cm³ g^?1, were investigated as possible adsorbents for CO₂ capture from the flue gas of coal-fired power stations. For that purpose, the isosteric heat of adsorption (and CO₂ adsorption capacity) was analysed from N₂ and CO₂ adsorption equilibrium isotherms obtained over a temperature range. For CO₂, q _st resulted to be in the range of 27–31 kJ mol^?1 (the highest value corresponding to the 6:4 sample), while for N₂ a value of q _st ≈ 12 kJ mol^?1 was obtained. Equilibrium adsorption capacity for CO₂ (at ambient temperature and pressure) showed the value of about 1.35 mmol g^?1. These results are discussed in the broader context of corresponding literature data for CO₂ capture using protonic zeolites.     

Acid–Base Properties, Solubility, Activity Coefficients and Na+ Ion Pair Formation of Complexons in NaCl(aq) at Different Ionic Strengths

The protonation constants and solubilities of three complexons [ethylenediamine-N,N′-disuccinic acid (EDDS), ethylene glycol bis(2-aminoethyl ether)-N,N,N′,N′-tetraacetic acid (EGTA) and 1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid (CDTA)] are reported in aqueous solutions of NaCl with different ionic strength values (0 ≤ I ≤ 4.8 mol·L^?1) and, in the case of CDTA, in (CH₃)₄NCl (0.1 ≤ I ≤ 2.7 mol·L^?1). The dependence on ionic strength of the protonation constants of these three complexons and four other complexons that were previously reported (NTA, EDTA, DTPA and TTHA), is analyzed in NaCl solution; the ionic strength influences quite strongly the protonation constants (as an example for CDTA, log₁₀ K ₁ = 10.54 and 9.25 at I = 0.1 and 1 mol·L^?1, respectively), while the effect of (CH₃)₄NCl concentration is lower. Based on the total solubility S ^T and the protonation constant data at different salt concentrations, the solubility of the neutral species S ⁰ and the solubility products K _S0 are obtained. The Setschenow coefficients k _m and the solubility values S ₀ ⁰ in pure water are also reported (S ₀ ⁰  = 0.55, 0.21 and 0.75 mmol·kg^?1 for EDDS, EGTA and CDTA, respectively). The dependence of the protonation constants on ionic strength is also interpreted in terms of ion pair formation, and the formation constants of Na⁺ species are reported.     

Carbamate Formation and Amine Protonation Constants in 2-Amino-1-Butanol–CO<Subscript>2</Subscript>–H<Subscript>2</Subscript>O System and Their Temperature Dependences

The apparent protonation constant of an amino butanol (AB) and its carbamate formation constant in the CO₂–H₂O–AB system were determined at T = 298.15–328.15 K, and at various ionic strengths up to 0.2 mol·L^?1 by potentiometric titration. The Debye–Hückel equation was used to extrapolate the protonation constants to zero ionic strength. The variation of the thermodynamic equilibrium constant for carbamate formation with temperature was modeled according to the relationship of log₁₀ K₁ = 280.91/T ? 0.1105, while the temperature dependency of the amine protonation constant was correlated by log₁₀ K₂ = 1926.53/T + 2.9482. Van’t Hoff type plots of the pK values showed linear relationships indicating that the standard enthalpy changes of reaction are constant over this range of temperatures. Hence, our current findings are crucial for designing efficient unit operations involving separation of CO₂ from natural or flue gases.     

Adsorption properties and behavior of the platinum group metals onto a silica-based (Crea + TOA)/SiO2–P adsorbent from simulated high level liquid waste of PUREX reprocessing

To separate platinum group metals (PGMs) from high level liquid waste (HLLW), a novel silica-based (Crea + TOA)/SiO₂–P adsorbent was synthesized by impregnating Crea (N′,N′-di-n-hexyl-thiodiglycolamide) and TOA (trioctylamine) two extractants into the macroporous SiO₂–P support with a mean diameter of 60 μm. Adsorption properties and behavior of PGMs from simulated HLLW onto the novel silica-based (Crea + TOA)/SiO₂–P adsorbent were investigated by batch method. It was found that (Crea + TOA)/SiO₂–P adsorbent exhibited good adsorption selectivity for PGMs over the other tested fission product element in a wide HNO₃ concentration. This adsorbent showed strong affinity to Pd(II) but almost no adsorption for rare earth elements. Adsorption process of PGMs could be expressed by Langmuir monomolecular layer adsorption mode and be governed by the chemisorption process. In addition, the adsorption isotherms and thermodynamic parameters of tested elements were calculated by Langmuir equation, Freundlich equation and van’t Hoff equation, respectively.     

Solubility of Icariin in a Binary Solvent System of Ethanol and Water

The solubility of icariin in the binary solvent system of ethanol and water was measured by UV–Vis spectrophotometry from 288.2 to 328.2 K. The solubility of icariin in the system increased with increasing temperature. A synergistic effect appeared at x ₂ = 0.4 (equivalent to 68.34 % ethanol, v/v) binary mixture. Solubility data were correlated with the modified Apelblat equation. The enthalpy and entropy of solution were evaluated using van’t Hoff plots.     

Adsorptive removal of U(VI) and Th(IV) from aqueous solutions using polymer-based electrospun PEO/PLLA fibrous membranes

Fibrous membranes based on poly(ethylene oxide) and poly(l-lactide) fabricated by electrospinning were evaluated for the first time as substrates for the adsorption of tetravalent thorium (Th(IV)) and hexavalent uranium (U(VI)) from aqueous media. The membranes consisted of microfibers with diameters of approximately 2 μm as revealed by scanning electron microscopy. The adsorption of Th(IV) and U(VI) on the membrane was investigated as a function of pH, ionic strength and initial metal concentration under normal atmospheric conditions. The experimental data indicated increased affinity of the membrane for Th(IV) and U(VI), which was pH depended and reaches maximum values (>90 %) for Th(IV) and U(VI) at pH 3 and pH 6.5, respectively. The maximum adsorption capacity (q _max) at optimum conditions was evaluated from the Langmuir isotherm and was found to amount 50.08 and 9.3 mmol kg^?1 for Th(IV) and U(VI), respectively. In addition, studies on the effect of ionic strength on the adsorption efficiency did not show any significant effect indicating that the adsorption of Th(IV) and U(VI) on the membrane was most probably based on specific interactions and the formation of inner-sphere surface complexes. The significantly higher adsorption efficiency of the membrane for Th(IV) in acidic media (pH ≤ 3) could be utilized for a pH-triggered, selective separation of Th(IV) from U(VI) from aqueous media.     

A Comparison Between Shaker and Bioreactor Performance Based on the Kinetic Parameters of Xanthan Gum Production

Xanthan gum production was studied using sugarcane broth as the raw material and batch fermentation by Xanthomonas campestris pv. campestris NRRL B-1459. The purpose of this study was to optimize the variables of sucrose, yeast extract, and ammonium nitrate concentrations and to determine the kinetic parameters of this bioreaction under optimized conditions. The effects of yeast extract and ammonium nitrate concentrations for a given sucrose concentration (12.1–37.8 g L^?1) were evaluated by central composite design to maximize the conversion efficiency. In a bioreactor, the maximum conversion efficiency was achieved using 27.0 g L^?1 sucrose, 2.7 g L^?1 yeast extract, and 0.9 g L^?1 NH₄NO₃. This point was assayed in a shaker and in a bioreactor to compare bioreaction parameters. These parameters were estimated by the unstructured kinetic model of Weiss and Ollis (Biotechnol Bioeng 22:859–873, 1980) to determinate the yields (Y _P/S), the maximum growth specific rate (μ _max), and the saturation cellular concentration (X*). The parameters of the model (μ _max, X*, m, λ, α, and β) were obtained by nonlinear regression. For production of xanthan gum in a shaker, the values of μ _max and Y _P/S obtained were 0.119 h^?1 and 0.34 g g^?1, respectively, while in a bioreactor, they were 0.411 h^?1 and 0.63 g g^?1, respectively.     

Photochemical synthesis and electronic spectra of fulminene ([6]phenacene)

Facile synthesis of fulminene ([6]phenacene) was achieved through the Mallory reaction of 1-(1-naphthyl)-2-(1-phenanthryl)ethene or the 9-fluorenone-sensitized photo-ring-closure of 1-(1-naphthyl)-2-(1-phenanthryl)ethane. The electronic spectral properties of fulminene were investigated for the first time using photoluminescence as well as transient absorption spectroscopy. The spectral features were compared with those of a series of lower phenacene homologs such as phenanthrene ([3]phenacene), chrysene ([4]phenacene), and picene ([5]phenacene). For the [n]phenacene series, both the fluorescence and phosphorescence bands linearly red-shifted with an increase in the number of the benzene rings (n). Trends in the energy levels of the excited singlet (E _S) and the triplet (E _T) states were expressed as E _s = ?2.6n + 89.1 (kcal mol^?1) and E _T = ?1.8n + 66.2 (kcal mol^?1), respectively. In the case of fulminene, laser flash photolysis displayed a transient spectrum with an absorption maximum (λ _max ^T–T ) at 675 nm, which was assigned as the triplet fulminene excited state. The λ _max ^T–T values for the [n]phenacene series showed a linear correlation as a function of the ring number n, given by an equation, λ _max ^T–T  = 60n + 318 (nm).