Removal of cesium ions from aqueous solutions using various separation technologies

Cesium is the major fission product of uranium, which widely exists in radioactive wastewater. Radiocesium has potential adverse effects on human health and ecological environment. Different methods such as chemical precipitation, coagulation/co-precipitation, solvent extraction, membrane process, chemical reduction, and adsorption have been used to remove radioactive cesium from aqueous solution. However, the development of innovative technologies capable of selectively removing radioactive cesium is still imperative yet challenging. This review focused on cesium removal using various separation technologies, including chemical precipitation, solvent extraction, membrane separation, and adsorption. The key restraints for cesium removal, as well as the recent progress of these methods have also been discussed. Particular attention has been paid to the adsorption methods, which has been highlighted by introducing the latest advances in inorganic adsorbents (such as metal hexacyanoferrates, clay minerals, carbon-based-adsorbents, and ammonium molybdophosphate), organic adsorbents (such as ion exchange resin, metal–organic frameworks and supramolecular/indicator grafting adsorbents), and biosorbents (such as agroforestry wastes and microbial biomass). Adsorption-based methods are high efficient in separation of cesium ions from aqueous streams, and adsorption of cesium ions has been investigated intensively and even used in practical applications, there is still considerable scope for improvement in terms of adsorption capacity and selectivity.

     

Adsorption of heavy metal ion from aqueous single metal solution by chemically modified sugarcane bagasse

This work describes the preparation of new chelating materials derived from sugarcane bagasse for adsorption of heavy metal ions in aqueous solution. The first part of this report deals with the chemical modification of sugarcane bagasse with succinic anhydride. The carboxylic acid functions introduced into the material were used to anchor polyamines, which resulted in two yet unpublished modified sugarcane bagasse materials. The obtained materials were characterized by elemental analysis and infrared spectroscopy (IR). The second part of this reports features the comparative evaluation of the adsorption capacity of the modified sugarcane bagasse materials for Cu(2+), Cd(2+), and Pb(2+) ions in aqueous single metal solution by classical titration. Adsorption isotherms were studied by the Freundlich and Langmuir models.     

Removal of copper ions by the filamentous fungus, Rhizopus oryzae from aqueous solution

Removal of heavy metals present in wastewaters has been a major concern due to their non-biodegradability and toxicity. Removal of copper ion using NaOH treated Rhizopus oryzae biomass was investigated in a batch reactor. The copper uptake exhibited substantial enhancement both in terms of kinetics of uptake as well as the loading capacity. The copper biosorption by viable and pretreated fungal biomass fit well to a Lagergren's pseudo second order reaction in comparison to pseudo first order kinetics. Investigation on effect of pH indicated improved performance in the range of pH 4-6 in alkali treated biomass. Copper uptake exhibited by viable biomass was highest at 21 degrees C, unlike pretreated biomass that showed maximum uptake across the range of temperature 21-55 degrees C. The maximum copper loading capacity of the viable and pretreated biomass according to Langmuir isotherm was 19.4 and 43.7 mg/g, respectively. Distribution coefficient of pretreated biomass showed improvement at lower residual concentration, indicating a change in the nature of binding by the treated biomass. Copper uptake decreased with an increasing dose of biosorbent, although enhancement in the total metal ion removal was observed at higher dose.     

Removal of Fe(II) ions from aqueous solution by Calabrian pine bark wastes

The ability of Calabrian pine bark wastes (Pinus brutia Ten) for the removal of Fe(II) ions from aqueous solution at different concentrations and temperatures at a fixed pH was investigated. While the amounts of Fe(II) ions adsorbed onto the bark increased with increasing concentration, it increased slightly with increasing the temperature. Kinetics studies showed that adsorption process followed the first-order kinetic model as well as intra-particle diffusion kinetics. Adsorption isotherm followed both Langmuir and Freundlich models. And it was determined that the adsorption was favorable from a dimensionless factor, R(L). Furthermore, the thermodynamic parameters demonstrated that the removal of Fe(II) by the bark was a physical process.     

Removal of Zn(II) ions from aqueous solution using Moringa oleifera Lam. (horseradish tree) biomass

The removal of Zn(II) ions from aqueous solution using pure and chemically pretreated biomass of Moringa oleifera was investigated at 30 ± 1 °C in this study. The experimental results explored that the maximum pH (pH_max) for efficient sorption of Zn(II) was 7 ± 0.1 at which evaluated biosorbent dosage and biosorbent particle size, were 0.5 g/L, <0.255 mm, respectively. The cellular Zn(II) concentration increased with the concentrations of Zn(II) in solution. Pretreatment of M. oleifera biomass affected the sorption process and the uptake capacity (mg/g) of biomass for Zn(II) uptake was in following order: NaOH (45.76) > H₂SO₄ (45.00) > CTAB (42.80) > Ca(OH)₂ (42.60) > Triton X-100 (42.06) > H₃PO₄ (41.22) > Al(OH)₃ (41.06) > SDS (40.41) > HCl (37.00) > non-treated biomass (36.07). There was significant increase in uptake capacity of M. oleifera biomass, which suggested that affinity between metal and sorbent can be increased after some sort of pretreatment. Both Langmuir and Freundlich isotherm model fitted well to data of Zn(II) biosorption as represented by high value of their correlation coefficient (i.e. R² ≈ 1). Kinetic studies revealed that Zn(II) uptake was fast with 90% or more of uptake occurring with in 40 min of contact time and the equilibrium was reached in 50 min of contact time. The sorption rates were better described by a second order expression than by a more commonly applied Lagergren equation. Finally it was concluded that pretreatment of M. oleifera biomass can achieve superior Zn(II) uptake capacity in comparison to non-pretreated biomass.     

Removal of triton X-100 from aqueous solution using amberlite XAD-2.

Amberlite XAD-2 beads adsorb the nonionic detergent Triton X-100 over a wide range of conditions with a maximum capacity of 0.475 mmol/g dry weight. After treatment of protein solutions containing Triton X-100 with XAD-2 no interference by Triton with Folin assays was observed. Adsorption of Triton X-100 was favored by a free-energy change of ?835 cal/mol and by a positive entropy value. Adsorbed Triton could be completely desorbed and the XAD-2 regenerated with little loss in capacity by washing with propan-2-ol. Removal of Triton by XAD-2 was also successful in columns or bateh-wise on a pilot-plant scale.     

Improved adsorption of cadmium ions from aqueous solution using chemically modified apple pomace: Mechanism,kinetics, and thermodynamics

Apple pomace (AP), before and after chemical modification (CM), was assessed for the removal of cadmium (Cd²⁺) ions from aqueous solution by equilibrium, kinetics, and thermodynamics studies. The chemical modification of AP was done with succinic anhydride by a simple ring opening mechanism for providing a large surface area for cadmium adsorption. The surface area of chemically modified apple pomace (CMAP) increased about 18% after the treatment. The amount of CMAP required for cadmium removal was 50 times less than the unmodified AP. The Langmuir adsorption isotherm equation was found to be more suitable for the AP and CMAP adsorption experimental data with a correlation coefficient of r² = 0.99 than was the Freundlich isotherm. The FTIR spectra of CMAP, with or without cadmium loading, indicated that ester (–COO), carboxyl (–CO), and amine (–NH₂) groups were involved in the cadmium adsorption mechanism. The adsorption of cadmium ions onto AP and CMAP followed pseudo-second-order kinetics. The ΔG^° value, at different temperatures, was calculated by applying the Van't Hoff equation and found to be negative, indicating that the reaction is spontaneous in nature. The value of ΔH^° indicated that the adsorption was exothermic (−6.93 KJ mol⁻¹) and endothermic (3.171 KJ mol⁻¹) for AP and CMAP, respectively. CMAP could be reutilized for up to three cycles with a removal efficiency of 76.6%, while AP efficiency lessened significantly after a single cycle.     

Removal of urea from urea-rich protein samples using metal ions in a microfluidic device

Urea is commonly used to lyse cultured cells and solubilize proteins from a biological source. In this study, after extracting biomolecules using a lysis buffer that included urea for an effective cleaning of protein from a urea-rich protein sample, a five-flow microfluidic desalting system was applied using the metal ions of Mn²⁺, Zn²⁺ and Fe³⁺, which have urea affinity-capturing properties. This device effectively removed urea from the sample phase of the microfluidic channel via the diffusion, with a difference of the concentration from the sample flow to both sides of the buffer flow, and an affinity of metal ions into the urea between the buffer phase and the affinity phase. The removal efficiency for the urea was 67, 64, and 63%, with concentrations of 50 mM Mn²⁺, 10 mM Zn²⁺, and 5 mM Fe³⁺ metal ions in the affinity phase, respectively. In addition, protein after desalting with the microfluidic device was improved to more than 10% of the relative activity, with a significant improvement of the signal of mass spectrum shown by MALDI-MS.     

Removal of heavy metal ions from wastewater by chemically modified plant wastes as adsorbents: a review

The application of low-cost adsorbents obtained from plant wastes as a replacement for costly conventional methods of removing heavy metal ions from wastewater has been reviewed. It is well known that cellulosic waste materials can be obtained and employed as cheap adsorbents and their performance to remove heavy metal ions can be affected upon chemical treatment. In general, chemically modified plant wastes exhibit higher adsorption capacities than unmodified forms. Numerous chemicals have been used for modifications which include mineral and organic acids, bases, oxidizing agent, organic compounds, etc. In this review, an extensive list of plant wastes as adsorbents including rice husks, spent grain, sawdust, sugarcane bagasse, fruit wastes, weeds and others has been compiled. Some of the treated adsorbents show good adsorption capacities for Cd, Cu, Pb, Zn and Ni.     

The removal by crab shell of mixed heavy metal ions in aqueous solution

In order to examine the inhibition effect of other heavy metal ions on the removal by crab shell of heavy metal ions in aqueous solutions, three ions (Pb(2+), Cd(2+), Cr(3+)) were used in single, binary and ternary systems. In single heavy metal ion systems, the removals of Cr(3+) and Pb(2+) were much higher than that of Cd(2+). In binary heavy metal ions systems, Cd(2+) did not affect Pb(2+) removal while Cr(3+) had a severe inhibition effect on the removal of Pb(2+). Cd(2+) removal was slightly affected by the presence of Pb(2+); however, it was severely affected by the presence of Cr(3+). The inhibitory effect of Cd(2+) on Cr(3+) was relatively lower than that of Pb(2+).     

Adsorption of Hg2+, Cu2+ and Zn2+ ions from aqueous solution using formaldehyde cross-linked modified chitosan-thioglyceraldehyde Schiff's base

A chitosan-thioglyceraldehyde Schiff's base cross-linked magnetic resin (CSTG) was prepared and characterized using various instrumental methods. Then, the prepared resin was used for comparative studies on the removal of toxic metal ions like: Hg(2+), Cu(2+) and Zn(2+) from aqueous solutions. The effects of the initial pH value of the solution, contact time, the initial metal ion concentration and temperature on the adsorption capacity of the composite were investigated. The kinetics data were analyzed by pseudo-first order and pseudo-second order equations. The adsorption kinetics was well described by the pseudo-second order equation, and the adsorption isotherms were better fitted by the Langmuir equation. The maximum theoretical adsorption capacities of the CSTG resin for Hg(2+), Cu(2+) and Zn(2+) were found to be 98±2, 76±1 and 52±1 mg g(-1), respectively. The negative values of Gibbs free energy of adsorption (ΔG(ads°) indicated the spontaneity of the adsorption of all metal ions on the novel resin.     

Activated parthenium carbon as an adsorbent for the removal of dyes and heavy metal ions from aqueous solution

Parthenium hysterophorous (L) is a perennial weed distributed all over the country. Carbonized parthenium activated with conc. H2SO4 and ammonium persulphate was effective in the removal of dyes, heavy metals and phenols. Variation in the percentage removal of adsorbates was observed with increase in the contact time. Among the adsorbates tested, the affinity of the activated parthenium carbon was highest for Hg2+, Methylene Blue and Malachite Green.     

Removal of thallium from aqueous solutions by modified Aspergillus niger biomass

The present study involves an investigation of various treated fungal biomasses of Aspergillus niger for the removal of thallium from aqueous solutions. Batch pH and kinetic studies were carried out to examine the effects of pH and contact time on the adsorption process. Among various pH values studied, the optimum pH was found to be between 4 and 5. The equilibrium time for Tl adsorption was found to be 6h and the rate of Tl adsorption was rapid in the initial hours. Both Lagergren's pseudo first-order model and Ho's pseudo second-order model well described the reaction kinetics. Batch adsorption experiments conducted at room temperature (22+/-1 degrees C) showed that the adsorption pattern followed the Freundlich isotherm model. Column studies using iron oxide-coated immobilized fungal biomass showed lower adsorption capacities compared to batch studies.     

Removal of heavy metals from aqueous solution using Rhizopus delemar mycelia in free and polyurethane-bound form

This study assesses the ability of mycelia of Rhizopus delemar (both free and immobilized on polyurethane foam) to remove heavy metals from single-ion solutions as well as from a mixture of them. All experiments were conducted using 0.5-5 mm solutions of CuSO4 x 5H2O, CoCl2-6H2O and FeSO4 7H2O. Mycelia immobilized on polyurethane foam cells showed some times increase in uptake compared with that of free cells. Metal ions accumulation from a mixed solution was decreased slightly for cobalt and iron and considerable for copper ions. Heavy metal uptake was examined in the immobilized column experiments and more than 92% heavy metal removal (mg heavy metals removed/mg heavy metals added) from a mixed solution was achieved during the 5 cycles. During these experiments, the dry weight of the immobilized cells was decreased by only 2%. These results showed that immobilized mycelia of Rhizopus delemar can be used repeatedly for removal of heavy metals from aqueous solutions.     

Nonlinear modelisation of heavy metal removal from aqueous solution using Ulva lactuca algae

After extensive analysis, Ulva lactuca dried algae, collected from the Monastir coastal zone, was proven to be successful as an adsorbent for the removal of certain inorganic pollutants. The main objective of this study was the nonlinear modeling of heavy metal removal from an aqueous solution, using a freely available and well analyzed biomaterial, as well as the evaluation of its efficacy on various metal ion sorptions. Although relatively low specific surface area, compared to more conventional adsorbents, the selected biomaterial displays very interesting retention capacities when used with aqueous inorganic pollutants. The pseudo, first and second-order kinetic models were used to investigate the kinetic retention mechanism. Assuming the nonlinear form, the results indicate that the retention mechanism is diffusion controlled. Concerning the heavy metal uptake capacity, it was found that the selected biomaterial has a retention capacity of 67 mg g⁻¹ of Ni(II), 112 mg g⁻¹ of Cu(II), 127 mg g⁻¹of Cd(II) and 230 mg g⁻¹ of Pb(II).     

Coordination of thiouridine monophosphates with selected metal ions

Potentiometric and spectroscopic data obtained for the complexes of two thio-substituted uridine-monophosphates with Cu(2+), Ni(2+) and Cd(2+) ions have shown that both thionucleotide are more effective ligands than their nucleoside analogues. The basic binding site for all metal ions is the sulfur atom. The chelation by adjacent N(3) donor is also likely, although unfavorable four-membered chelate ring is formed.     

Removal of ammonium from aqueous solutions using alkali-modified biochars

Biochars converted from agricultural residuals can effectively remove ammonium from water. This work further improved the sorption ability of biochars to aqueous ammonium through alkali modification. Three modified biochars were prepared from agricultural residuals pre-treated with NaOH solution through low-temperature (300 °C) slow pyrolysis. The modified biochars effectively removed ammonium ions from water under various conditions with relatively fast adsorption kinetics (reached equilibrium within 10 h) and extremely high adsorption capacity (>200 mg/g). The Langmuir maximum capacity of the three modified biochars were between 313.9 and 518.9 mg/g, higher than many other ammonium adsorbents. Although the sorption of ammonium onto the modified biochar was affected by pH and temperature, it was high under all of the tested conditions. Findings from this work indicated that alkali-modified biochars can be used as an alternative adsorbent for the removal of ammonium from wastewater.