Removal of uranium (VI) from aqueous solution by adsorption of hematite

Hematite, a type of inorganic-sorptive medium, was used for the removal of U (VI) from aqueous solutions. Variables of the batch experiments including solution pH, contact time, initial concentration, temperature, calcium and magnesium ions were studied. The results indicated that the adsorption capacities are strongly affected by the solution pH, contact time and initial concentration. A higher pH favors higher U (VI) removal. The adsorption was also affected by temperature and calcium and magnesium ions, but the effect is very weak. The maximum adsorption capacity (q_m) only increased from 3.36 mg g⁻¹ to 3.54 mg g⁻¹ when the temperature was increased from 293 K to 318 K. A two-stage kinetic behavior was observed in the adsorption of uranium (VI): very rapid initial adsorption in a few minutes, followed by a long period of slower uptake. It was found that an increase in temperature resulted in a higher uranium (VI) loading per unit weight of the sorbent. The adsorption of uranium by hematite had good efficiency, and the equilibrium time of adsorbing uranium (VI) was about 6 h. The isothermal data were fitted with both Langmuir and Freundlich equations, but the data fitted the former better than the latter. The pseudo-first-order kinetic model, pseudo-second-order kinetic model and intraparticle diffusion model were used to describe the kinetic data, but the pseudo-second-order kinetic model was the best. The thermodynamic parameter ΔG⁰ were calculated, the negative ΔG⁰ values of uranium (VI) at different temperatures confirmed the adsorption processes were spontaneous.     

Removal of uranium(VI) from aqueous solutions and nuclear industry effluents using humic acid-immobilized zirconium-pillared clay

Removal of uranium [U(VI)] from aqueous solutions with humic acid-immobilized zirconium-pillared clay (HA-Zr-PILC) was investigated using a batch adsorption technique. The adsorbent was characterized using XRD, FTIR, SEM, TG/DTG, surface area analyzer and potentiometric titration. The effects of pH, contact time, initial concentration, adsorbent dose, and adsorption isotherm on the removal process were evaluated. A maximum removal of 97.6 ± 2.1 and 94.7 ± 3.3% was observed for an initial concentration of 50 and 100 mg L⁻¹, respectively at pH 6.0 and an adsorbent dose of 2.0 g L⁻¹. Equilibrium was achieved in approximately 180 min. The mechanism for the removal of U(VI) ions by HA-Zr-PILC was based on an ion exchange reaction. The experimental kinetic and isotherm data were analyzed using a second-order kinetic equation and Langmuir isotherm model, respectively. The monolayer adsorption capacity for U(VI) removal was found to be 132.68 ± 5.04 mg g⁻¹. An increase of temperature of the medium caused an increase in metal adsorption. Complete removal (≅100%) of U(VI) from 1.0 L of a simulated nuclear industry effluent sample containing 10.0 mg U(VI) ions was possible with 1.5 g of HA-Zr-PILC. The adsorbent was suitable for repeated use (over 4 cycles) without any noticeable loss of capacity.     

Biosorption of uranium (VI) by immobilized Aspergillus fumigatus beads

Biosorption of uranium (VI) ions by immobilized Aspergillus fumigatus beads was investigated in a batch system. The influences of solution pH, biosorbent dose, U (VI) concentration, and contact time on U (VI) biosorption were studied. The results indicated that the adsorption capacity was strongly affected by the solution pH, the biosorbent dose and initial U (VI) concentration. Optimum biosorption was observed at pH 5.0, biosrobent dose (w/v) 2.5%, initial U (VI) concentration 60 mg L⁻¹. Biosorption equilibrium was established in 120 min. The adsorption process conformed to the Freunlich and Temkin isothermal adsorption models. The dynamic adsorption model conformed to pseudo-second order model.     

Study of Ni adsorption on NKF-6 zeolite

The adsorption of ⁶³Ni from aqueous solutions using NKF-6 zeolite was investigated by a batch technique under ambient conditions. The adsorption was investigated as a function of contact time, pH, ionic strength, foreign ions, humic substances (FA/HA) and temperature. The kinetic adsorption was well described by the pseudo-second-order rate equation. The adsorption of ⁶³Ni on NKF-6 zeolite was strongly dependent on pH and ionic strength, and the adsorption of ⁶³Ni increased with increasing NKF-6 zeolite content. At low pH values, the presence of FA enhanced the adsorption of ⁶³Ni on NKF-6 zeolite, but the presence of HA had no drastic effect. At high pH values, the presence of FA or HA decreased the adsorption of ⁶³Ni on NKF-6 zeolite. The adsorption isotherms were well represented by the Langmuir model. The thermodynamic parameters (i.e., ΔH⁰, ΔS⁰and ΔG⁰) for the adsorption of ⁶³Ni were determined from the temperature dependent isotherms at 293.15, 313.15 and 333.15 °K, respectively, and the results indicate that the adsorption reaction was favored at high temperature. The results suggest that the adsorption process of ⁶³Ni on NKF-6 zeolite is spontaneous and endothermic.     

Adsorption of thorium from aqueous solutions by perlite

The use of expanded perlite for the adsorption of thorium from aqueous solution by batch technique is presented. The effects of particle size, pH of the solution, initial thorium concentration, shaking time, V/m ratio and temperature were determined. It was found that the adsorption capacity increases by the increase in the pH of the suspensions. The rate of thorium adsorption on expanded perlite was observed to be fast in the first hour of the reaction time. Adsorption isotherms were expressed by Langmuir and Freundlich adsorption models and the adsorption experiments conducted at 30 ± 1 °C showed that the adsorption isotherms correlated well with the Langmuir model. From the adsorption data, thermodynamic parameters such as ΔG^o, ΔH^o and ΔS^o were calculated as a function of temperature.     

Study on biosorption kinetics and thermodynamics of uranium by Citrobacter freudii

Biosorption has been developed as an effective and economic method to treat wastewater containing low concentrations of metal pollutants. In this study, a bacterium, Citrobacter freudii, was used as a biosorbent to adsorb uranium ions. The thermodynamics and kinetics of this adsorption, as well as its mechanism, were investigated. The results indicated that the biosorption rate could be better described by a pseudo 2nd-order model than a pseudo 1st-order model. The adsorption of U (VI) proceeded very rapidly in the first 30min and subsequently slowed down continuously for a long period. The biosorption isotherm of uranium by C. freudii could be described well by the Langmuir or Freundlich isotherm, and the latter was better. The thermodynamics parameters, DeltaH degrees , DeltaG degrees , and DeltaS degrees were calculated according to the results of the experiment, which showed this biosorption as being endothermic and spontaneous. The authors investigated the active sites of bacteria for biosorption and the results proved that carboxyl in the cell wall played an important role in biosorption.     

Impact of water quality parameters on the sorption of U(VI) onto hematite

In this study, the sorption of U(VI) from aqueous solution on hematite was studied as a function of various water quality parameters such as contact time, pH, ionic strength, soil humic acid (HA) or fulvic acid (FA), solid content and temperature by using a batch technique. The results demonstrated that the sorption of U(VI) was strongly dependent on ionic strength at pH < 6.0, and outer-sphere surface complexation may be the main sorption mechanism. The sorption was independent of ionic strength at pH > 6.0 and the sorption was mainly dominated by inner-sphere surface complexation. The presence of HA/FA increases U(VI) sorption at low pH, whereas decreases U(VI) sorption at high pH. The thermodynamic parameters (ΔH⁰, ΔS⁰, and ΔG⁰) were calculated from the temperature dependent sorption isotherms, and the results suggested that U(VI) sorption was a spontaneous and endothermic process. The results might be important for the application of hematite in U(VI) pollution management.     

Improved performance of a biomaterial-based cation exchanger for the adsorption of uranium(VI) from water and nuclear industry wastewater

The amine-modified polyhydroxyethylmethacrylate (poly(HEMA))-grafted biomaterial (tamarind fruit shell, TFS) carrying carboxyl functional groups at the chain end (PGTFS-COOH) was prepared and used as an adsorbent for the removal of uranium(VI) from water and nuclear industry wastewater. FTIR spectral analysis revealed that U(VI) ions and PGTFS-COOH formed a chelate complex. The adsorption process was relatively fast, requiring only 120 min to attain equilibrium. The adsorption kinetic data were best described by the pseudo-second-order equation. The equilibrium adsorption data were correlated with the Sips isotherm model. The maximum U(VI) ions uptake with PGTFS-COOH was estimated to be 100.79 mg/g. The complete removal of 10 mg/L U(VI) from simulated nuclear industry wastewater was achieved by 3.5 g/L PGTFS-COOH. The reusability of the adsorbent was demonstrated over 4 cycles using NaCl (1.0 M) + HCl (0.5 M) solution mixture to de-extract the U(VI). The results show that the PGTFS-COOH tested is very promising for the recovery of U(VI) from water and wastewater.     

Biosorption of uranium by chemically modified Rhodotorula glutinis

The present paper reports the biosorption of uranium onto chemically modified yeast cells, Rhodotorula glutinis, in order to study the role played by various functional groups in the cell wall. Esterification of the carboxyl groups and methylation of the amino groups present in the cells were carried out by methanol and formaldehyde treatment, respectively. The uranium sorption capacity increased 31% for the methanol-treated biomass and 11% for the formaldehyde-treated biomass at an initial uranium concentration of 140 mg/L. The enhancement of uranium sorption capacity was investigated by Fourier transform infrared (FTIR) spectroscopy analysis, with amino and carboxyl groups were determined to be the important functional groups involved in uranium binding. The biosorption isotherms of uranium onto the raw and chemically modified biomass were also investigated with varying uranium concentrations. Langmuir and Freundlich models were well able to explain the sorption equilibrium data with satisfactory correlation coefficients higher than 0.9.     

Redox chemistry of sulphate and uranium in a phosphogypsum tailings dump

The present study aims to assess the effect of redox conditions existing within the tailings dump on the stability of phosphogypsum (e.g. sulphate reduction) and uranium(VI). Phosphogypsum sampling and in-situ measurements were carried out at a coastal tailings dump in Vasiliko Cyprus, pH, E_H and solubility experiments were performed in simulated laboratory systems and thermodynamic calculations using MINTEQA2. Generally, in the open tailings dump oxidizing conditions predominate stabilizing sulphur and uranium in their hexavalent oxidation states. On the other hand, after the application of a soil/vegetative cover and in the presence of natural organic matter, anoxic conditions prevail (E_H < −70 mV) resulting in S(VI) and U(VI) reduction to S(−II) and U(IV), respectively. Although, the sulphide anion can form very insoluble compounds with heavy metal ions (e.g. Cd(II), Pb(II) etc.) and U(IV) oxide has very low solubility, partial reduction of sulphate to sulphide within gypsum may affect the stability of phosphogypsum resulting in enhanced erosion of the material by rain- and seawater and washing out of contaminants in particulate/colloidal form.     

Assessment of hydrothermally modified fly ash for the treatment of methylene blue dye in the textile industry wastewater

Dyes and pigments are one of the major water pollutants and if not discharged properly cause ecological disturbance. Considering this, the current study investigates the application of thermal power plant by-product, i.e., fly ash for the elimination of a hazardous methylene blue dye from its synthetic aqueous solution. Experiments were conducted in batch mode to study the effect of pH, temperature, adsorbent dose and contact time. Highest dye removal (94.3%) was achieved at pH 10 using adsorbent dose of 10 g/L in 90 min of contact time at 40 °C. However, for cost-effective operation at neutral pH and room temperature (30 °C), it yields 89.3% dye removal having similar dose and contact time. Equilibrium isotherms for adsorption were analyzed by Langmuir and Freundlich, Temkin and Dubinin–Radushkevich isotherm equations. The results revealed that the best fit model of adsorption closely followed Langmuir adsorption. Based on adsorption isotherm models, thermodynamics parameters ΔG, ΔH and ΔS were calculated. The negative value of ΔG and ΔH revealed that adsorption process was exothermic, spontaneous and physical. The present work suggests that through simple process hydrothermally modified fly ash has the potential to be used as cost-effective and efficient adsorbent for the treatment of wastewater from textile industries.     

Cadmium desorption in sand

Desorption of cadmium (Cd) from sand was studied by both batch and flow-through methods. Batch experiments were conducted at three pH values (5.5, 6.0 and 6.5). In each case, the amount of Cd desorbed was low compared with the quantity of Cd adsorbed previously. Desorption of Cd in the batch experiments can be described adequately by a Freundlich isotherm. The Freundlich isotherm coefficient, Kf, increased with pH. Hysteresis between the sorption/desorption isotherms was observed in all batch experiments. Flow-through experiments in soil columns were conducted for the same three pH values, with the results used to determine transport and sorption/desorption parameters. Again, the desorption isotherms bore little resemblance to the corresponding adsorption isotherms. The experimental breakthrough curves were well fitted by a nonequilibrium desorption model, however the time scale of the desorption process was much larger than measured in batch experiments. This model was therefore rejected as lacking realism. A simple linear retardation (including hysteresis) model that utilises different isotherms was found to simulate column breakthrough curves well. The Freundlich isotherm coefficients, Kf, in all batch and flow-through desorption experiments were different to values evaluated from the corresponding adsorption experiments. However, in contrast to adsorption, desorption in flow-through experiments was not noticeably affected by changes in pH. The effect of pore-water velocity on desorption was also studied at pH 6.0. No trend was established between flow velocity and the desorption coefficient.     

Adsorption and desorption of iodine by various Chinese soils: I. Iodate

In order to assess the adsorption of iodate by different soils from China, a series of batch experiments were conducted. It was found that soils rich in iron oxide had high affinity for iodate. Iodate adsorption isotherms could be well fitted with both Langmuir and Freundlich equations. Iodate adsorption by 20 different soils from China revealed that iodate adsorption was significantly correlated with soil organic matter negatively and positively with free iron oxide contents. At initial concentration of 4 mg I L(-1), iodate adsorption ranged between 9 and 34 mg kg(-1) soil. No correlation between iodate adsorption and cation exchange capacity and soil pH was found. For a single soil, there was a significant linear relationship between the amounts of iodate adsorbed and desorbed, but for a group of different soils, the relationship between the amounts of iodate adsorption and desorption followed a nonlinear relationship, the deviation mainly occurred at high adsorption side. The relationship between K(d) and free aluminum oxide and free iron oxide contents showed an exponential relationship for various soils with exception of the soil from Hetian in Xinjiang.     

Combating dye pollution using cocoa pod husks: a sustainable approach

The adsorptive potential of activated carbon prepared by chemical activation of Cocoa pod husk (CPHAA) to remove Congo red (CR) dye from its aqueous solution was investigated in this study. CPHAA was characterised using Energy Dispersive X-Ray, Scanning Electron Micrograph and Fourier Transform Infrared Spectroscopy techniques. The effects of contact time, initial dye concentration, pH and solution temperature were studied. Equilibrium data were fitted to Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherm models. The equilibrium data were best represented by Langmuir isotherm model, with maximum monolayer adsorption capacity of 43.67 mg/g. The kinetic data were fitted to Pseudo-first-order, Pseudo-second-order, Elovich and Intraparticle diffusion models; the pseudo-second-order kinetic model provided the best correlation. Thermodynamic parameters such as standard enthalpy (ΔH^o), standard entropy (ΔS^o) and standard free energy (ΔG^o) were evaluated. The thermodynamic study showed that the process is endothermic, spontaneous and feasible. The mean free energy of adsorption shows that the mechanism is by physisorption. CPHAA was found to be an effective adsorbent for the removal of CR dye from aqueous solution.     

Investigation of 85Sr adsorption on selected soils of different horizons

Studies on the mechanism of (90)Sr migration in soil require many processes to be considered. One of the most important is sorption on the surface of mineral components of the soil. In this study adsorption of (85)Sr on a variety of soil types from different horizons has been investigated. Adsorption isotherms show various affinities of (85)Sr, depending on soil type and to a lesser extent the horizon. An important effect of pH was found with a maximum in the range 5-7. The influence of calcium ions on the extent of adsorption of (85)Sr isotope on soil samples from surface horizons of four sites is presented. Depending on the soil type differing degrees of competitive adsorption of Sr and Ca were observed. Desorption of (85)Sr by distilled water as well as Ca(NO(3))(2) solution was also examined. Both methods resulted in the removal of a considerable proportion of the adsorbed isotope from the soil. Additionally the kinetics of the desorption process were studied.     

The interaction of heavy metals with urban soils: sorption behaviour of Cd, Cu, Cr, Pb and Zn with a typical mixed brownfield deposit

This study investigated the sorption characteristics and release of selected heavy metals (Cd, Cu, Cr, Pb and Zn) from a typical urban soil material from a derelict brownfield site in Western Scotland, UK. The study aimed to evaluate contaminant interactions with an urban substrate, comprising a mix of mineral soil and residue materials (e.g. brick, concrete, wood). This type of material has received little consideration in the literature to date. Soil samples were subject to a sequence of test involving batch equilibration and dynamic leaching, in single (non-competitive) and multi-element (competitive) solutions. The batch experiments were carried out in unadjusted and close to soil field pH conditions (pH 2 and 7, respectively). The equilibrium adsorption capacity for heavy metals was measured and extrapolated using the Langmuir isotherm. The parameters of the isotherms x(m) (the maximum amount adsorbed per unit mass of adsorbent (mg/g)) and b (adsorption constant (m(3)/g)) were calculated for Cd, Cu, Cr, Pb as single-element and multi-element solutions. The adsorption from the single-element solution was more effective than adsorption under multi-element conditions, due to competitive effects. For example, the adsorption of copper from a single-element solution was over four times greater than for a multi-element solution. In the case of Cr and Zn, migration of metal from soil to solution was observed. Adsorption capacity at pH 2 followed the order Cr>Cu>Pb>Cd and at pH 7 Cd>Zn, with precipitation affecting Cu and Pb behaviour. During the column leaching experiment, most of the heavy metals were irreversibly bound to the soil, but in the case of Cr some movement from soil into solution was observed. The results also showed that Cd, Cu, Pb and Zn were removed from the solution and adsorbed on the soil. No significant difference in the metal removal from single- and multi-element solutions was observed. Overall, the urban residue behaved in a similar manner to mineral soils despite a significant component of anthropogenic solid materials.     

Experimental and theoretical studies on physico-chemical parameters affecting the solubility of phosphogypsum

Phosphogypsum is a waste by-product of the phosphate fertilizer industry, which is usually disposed in the environment because of its restricted use in industrial applications. Physico-chemical conditions existing in stack fluids and leachates are of major importance and determine solubility and redox stability of phosphogypsum, as well as radionuclide release from stacks to terrestrial environments. The aim of this study is to assess the effect of key parameters (e.g. ionic strength, temperature, pH) on the solubility of phosphogypsum. Phosphogypsum sampling and in-situ measurements were carried out at a coastal stack in Cyprus, solubility experiments were performed in simulated laboratory systems and thermodynamic calculations by means of MINTEQA2, an equilibrium speciation model. Generally, increasing ionic strength and temperature leads to increased phosphogypsum solubility, with the former being much more effective. The increased solubility of phosphogypsum in saline solutions is attributed solely to ionic strength effects on the activity of ionic species in solution and no solid phase transformations could be observed. The effect of pH on phosphogypsum solubility seems to be insignificant at least in a pH range between 4 and 8. Regarding uranium levels, there is a strong correlation between salinity and uranium concentration and linear correlation between phosphogypsum solubility and uranium levels in stack solutions, indicating the incorporation of uranium into the gypsum lattice and the formation of a solid solution.     

Adsorption studies on coir pith for heavy metal removal

Biosorption efficiency of coir pith, a waste product from coir industry, was investigated in this study for the removal of metallic pollutants such as Ni, Cu and Zn from aqueous solutions. The disposal of coir pith is a major problem associated with the coir industries, especially working in the small-scale sector. The present study explores the effectiveness of utilization of coir pith, an accumulating waste, as a biosorbent for heavy metal removal. Batch mode studies were done to evaluate the efficiency of removal of metals under varying adsorption conditions of pH, metal concentration and contact time. Characterization studies of the biosorbent and SEM analysis were done. Kinetic modelling studies were tried using Lagergren pseudo-first-order and second-order models. Equilibrium studies were done using well-known Freundlich, Langmuir and D–R isotherm models. It was found that all isotherms are fitting well indicating the efficiency of coir pith as an adsorbent of heavy metals. The applicability of all the three isotherms to the sorption processes shows that both monolayer adsorption and heterogeneous energetic distribution of active sites on the surface of the adsorbent are possible. Due to the abundance and low cost of these materials, adsorption technologies developed can act as good sustainable options for the future in heavy metal removal from industrial effluents.     

Equilibrium,kinetics and thermodynamics studies on adsorptive removal of cobalt ions from wastewater using MIL-100(Fe)

This study describes experiments in which MIL-100(Fe) was used to remove Co²⁺ ions from the waste water. The synthesised adsorbent was characterised by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction, Brunauer–Emmett–Teller (BET) and scanning electron microscope. Statistical analysis was used to investigate the effects of different parameters. From the obtained results, the removal efficiency was enhanced with increasing contact time and pH but decreased with increasing cobalt initial concentration. The maximum removal efficiency of Co⁺² was 93.4% under optimum conditions. The equilibrium adsorption data were best fitted to linearly transformed Freundlich isotherm. Adsorption kinetic data followed the pseudo second-order kinetic model. The maximum adsorption capacity of Co⁺² on to the MIL-100(Fe) was found to be 119 mg g^?1. The results showed that ?G of adsorption was negative, while ?H was positive which showed that the adsorption process was spontaneous and endothermic. The positive value of ?S showed that disordering and randomness increased at the solid–solution interface of cobalt ions with MIL-100(Fe) particles.     

The removal of uranium from mining waste water using algal/microbial biomass

We describe a three step process for the removal of uranium (U) from dilute waste waters. Step one involves the sequestration of U on, in, and around aquatic plants such as algae. Cell wall ligands efficiently remove U(VI) from waste water. Growing algae continuously renew the cellular surface area. Step 2 is the removal of U-algal particulates from the water column to the sediments. Step 3 involves reducing U(VI) to U(IV) and transforming the ions into stable precipitates in the sediments. The algal cells provide organic carbon and other nutrients to heterotrophic microbial consortia to maintain the low E(H), within which the U is transformed. Among the microorganisms, algae are of predominant interest for the ecological engineer because of their ability to sequester U and because some algae can live under many extreme environments, often in abundance. Algae grow in a wide spectrum of water qualities, from alkaline environments (Chara, Nitella) to acidic mine drainage waste waters (Mougeotia, Ulothrix). If they could be induced to grow in waste waters, they would provide a simple, long-term means to remove U and other radionuclides from U mining effluents. This paper reviews the literature on algal and microbial adsorption, reduction, and transformation of U in waste streams, wetlands, lakes and oceans.