Inorganic particulates in removal of toxic heavy metal ions

The removal behavior of amorphous aluminum hydroxide for Hg(II) ions from aqueous solutions was investigated by employing a radiotracer technique at micro down to trace level concentrations. The batch type experiments were performed to obtain various physico-chemical parameters, viz., effect of sorptive concentration, temperature and pH. It was observed that the increase in sorptive concentration (from 1·10⁻⁸ to 1·10⁻² mol·dm⁻³), temperature (from 303 to 333K) and pH (from 3.4 to 10.3) apparently favored the uptake of Hg(II) by this solid. Similarly, the presence of anions (six fold) viz., oxalate, phosphate, glycine and EDTA also enhanced the uptake behavior of aluminum hydroxide for Hg(II). Whereas, the added cations viz., Na⁺, K⁺, Ba²⁺, Sr²⁺, Mg²⁺, Cd²⁺ and Fe³⁺ more or less suppressed the removal behavior of the adsorbent. Further, the adsorption process followed the classical Freundlich adsorption isotherm and deductions of various thermodynamic data revealed that the uptake of Hg(II) on aluminum hydroxide followed the ion-exchange type mechanism and thermodynamically it was found to be endothermic in nature. Part IX: Rapid and efficient removal of Hg(II) by hydrous manganese and tin oxides, J. Coll. Interf. Sci., 279 (2004) 61.     

Removal of strontium ions by a crosslinked copolymer containing methacrylic acid functional groups</p> </p>

Summary A tail-made polymer matrix is proposed to remove strontium ions from aqueous solutions. The removal behavior of strontium ions on a crosslinked copolymer containing methacrylic acid as functional groups was investigated as a function of sorptive concentration, time, temperature and pH. It was observed that an increase of these parameters enhanced the removal of Sr(II) ions from aqueous solution. It is found that a maximum adsorption of Sr(II) ions can be obtained on the crosslinked copolymer after 30 minutes and at pH 8. The increase of Sr(II) ion concentration in the solution resulted in an increase in the amount of Sr(II) ions adsorbed on the crosslinked copolymer containing methacrylic acid as functional groups. However, after a maximum of Sr(II) concentration in the solution, the percentage of adsorbed Sr(II) ions decreased. The adsorption data are well represented by the Freundlich, Langmuir and Dubinin-Radushkevich (D-R) isotherms. The adsorption capacity of the copolymer and the free energy change were calculated by using the D-R isotherm. For the adsorption of Sr(II) ions on the crosslinked copolymer the thermodynamic parameters (DH°,DS° andDG°) were calculated.</p> </p>     

Inorganic particulates in removal of heavy metal toxic ions IX. Rapid and efficient removal of Hg(II) by hydrous manganese and tin oxides

Batch studies have been carried out in the removal of Hg(II) from aqueous solutions by using well-synthesized and -characterized hydrous manganese oxide (HMO) and hydrous tin oxide (HTO) employing a radiotracer technique. Results obtained reveal that increased sorptive concentration (10(-8)-10(-2) mol dm(-3)), temperature (298-328 K), and pH (ca. 2.0-10.5) enhance the removal efficiency of these solids. First-order uptake of Hg(II) on HMO and HTO follows the Freundlich adsorption isotherm for entire concentration range. Positive values of DeltaH0 for the uptake process on both solids indicate endothermic uptake and desorption experiments point to irreversible uptake. Radiation stability of the adsorbents has also been assessed using a 300-mCi (Ra-Be) neutron source having an integral neutron flux of 3.85 x 10(6) N cm(-2) s(-1) and associated with a nominal gamma-dose of ca. 1.72 Gy/h.     

Polysiloxane dizwitterionomers. III. Water sorption

The interaction of water with the various polysiloxane dizwitterionomers and the model compound 4,7-diazaheptyl-4,7-di(3-propane-sulfonate) heptamethyltrisiloxane was studied. The model compound is soluble in water but the polymers swell inhomogeneously when soaked in water. The initial sorption kinetics of these zwitterionomers indicate similar mechanisms of water uptake which is independent of ion concentration (D = 4.7 × 10^?7 cm²/sec). The sorption isotherms reveal the high sorptive capacity of these ionomers. Furthermore, the linear relationship between the water uptake and the concentration of ions over a large relative humidity range (0.22 ≤ P/P₀ ≤ 0.93) allowed us to treat each phase separately. It has been found that most of the absorbed water molecules are immobilized in the ionic domains. Their concentration in this phase is nearly identical to the sorptive capacity of the model compound.     

Biosorptive behavior of mango (<Emphasis Type="Italic">Mangifera indica</Emphasis>) and neem (<Emphasis Type="Italic">Azadirachta indica</Emphasis>) barks for <Superscript>134</Superscript>Cs from aqueous solutions: A radiotracer study

The role of dead biomasses viz., mango (Mangifera indica) and neem (Azadirachta indica) bark samples are assessed in the removal behavior of, one of important fission fragments, Cs(I) from aqueous solutions employing a radiotracer technique. The batch type studies were carried out to obtain various physico-chemical data. It is to be noted that the increase in sorptive concentration (from 1.0·10⁻⁸ to 1.0·10⁻² mol·dm⁻³), temperature (from 298 to 328 K) and pH (2.6 to 10.3) apparently favor the uptake of Cs(I) by these two bark samples. The concentration dependence data obeyed Freundlich adsorption isotherm and the uptake follows first order rate law. Thermodynamic data evaluation and desorption experiments reveal the adsorption to be irreversible and endothermic in nature proceeding through ion-exchange and surface complexation for both dead biomasses. Both bark samples showed a fairly good radiation stability in respect of adsorption uptake of Cs(I) when irradiated with a 300 mCi (Ra-Be) neutron source having an integral neutron flux of ∼3.85·10⁶ n·cm⁻²·s⁻¹ and associated with a nominal γ-dose of ∼1.72 Gy·h⁻¹.     

Competitive transport of toxic metal ions by polymer inclusion membranes

The paper gives a short overview of application of polymer inclusion membranes (PIMs) for separation and removal of metal ions. Investigation of the selective removal of toxic metal ions, i.e. Cr(VI), Cd(II), Zn(II) from acidic chloride aqueous solutions, as well as trace radionuclides, i.e., ¹³⁷Cs, ⁹⁰Sr and ⁶⁰Co from wastewaters using transport across polymer inclusion membranes was studied. The carriers, i.e., tri-n-octylamine for anionic metal species, as well as dibenzo-21-crown-7, tertbutyl-dibenzo-21-crown-7, and dinonylnaphtalenesulfonic acid for metal cations were incorporated into polymer inclusion membranes composed of cellulose triacetate as a support and o-nitrophenyl pentyl ether as a plasticizer. Selective transport of chromium(VI) over zinc(II) and cadmium(II) chloride complexes through PIMs was observed. Competitive transport of trace radionuclide ions, i.e., ¹³⁷Cs, ⁹⁰Sr, and ⁶⁰Co from NaNO₃ aqueous solutions across polymer inclusion membranes containing a mixture of dinonylnaphtalenesulfonic acid, and dibenzo-21-crown-7 as the carrier provide the selectivity order Cs(I)>Sr(II)>Co(II).     

Inorganic ion-exchangers in radioactive waste management</p> </p>

Summary The uptake of indigenously synthesized amorphous stannic and zirconium phosphate was assessed for, one of the important fission fragment, cesium from aqueous solutions using a radiotracer technique. A virtual increase in sorptive concentration (from 1.0 ^. 10^-8 to 1.0 ^. 10^-2 mol ^. dm^-3) and pH (from 2.4 to 10.2) and temperature (from 303 to 333 K) enhanced the uptake of cesium on stannic phosphate. However, the extremely high degree of uptake of cesium on zirconium phosphate was almost unaffected with the dilution beyond 10^-5 mol ^. dm^-3 and pH (i.e., from 2.4 to 10.2) and temperature (from 303 to 323 K). Irreversible uptake occurring for these solids follow the Freundlich adsorption isotherm and the presence of several complexing agents viz., sulphate, phosphate, glycine and EDTA did not affect appreciably the uptake of cesium on zirconium phosphate but it did affect for stannic phosphate system. Both these solids showed good radiation stability towards a 11.1 GBq Ra-Be neutron source having neutron flux ca. 3.2 ^. 10⁶ n ^. cm^{-2 .} s^-1 and associated with a nominalg-dose of ca. 1.72 Gy/h, at least for the uptake of cesium.</p> </p>     

Adsorption characteristics and radiation stability of a silica-based DtBuCH18C6 adsorbent for Sr(II) separation in HNO3 medium

A silica-based adsorbent, (DtBuCH18C6 + dodecanol)/SiO₂-P, which is used for selective separation of Sr(II) from high level liquid wastes, against temperature and gama-irradiation was investigated. The adsorption characteristics of Sr(II), Ba(II), La(III), Nd(III), Gd(III) and Dy(III) under varying nitric acid concentration at different temperatures were measured by batch method. The adsorbent showed higher distribution coefficients (K _d) for Sr(II) compared to other tested metal ions, and the K _d values of Sr(II) decreased with increasing temperature. Thermodynamic parameters of the adsorption process were calculated. The related parameters in adsorption isotherm models were obtained using a non-linear fitting. Uptake capacity from 0.38 to 0.43 mmol g^?1 was obtained for Sr(II) in the temperature range of 298–323 K by the Langmuir equation fitting. The leakage of total organic carbon was below 120 ppm at 298 K and 180 ppm at 323 K, respectively. The degradation of the adsorbent irradiated in 2 M HNO₃ was investigated. It is found that the adsorbed dose of γ-ray more than 50 KGy has a strong influence on K _d of Sr(II). The K _d values of Sr(II) decrease about 3 times ranged from 50 to 500 KGy.     

Inorganic particulates in removal of heavy metal toxic ions--part X: rapid and efficient removal of Hg(II) ions from aqueous solutions by hydrous ferric and hydrous tungsten oxides

A radiotracer technique has been used to study the removal of Hg(II) ions from aqueous solutions by synthesized and well-characterized hydrous ferric oxide (HFO) and hydrous tungsten oxide (HTO). Adsorptive concentration (10(-4)-10(-8) mol dm(-3)), pH (ca 4.0-10.0) and temperatures (303-333 K) were examined for assessing optimal conditions for removal of these ions. The uptake of Hg(II) ions, fitted well with the Freundlich isotherm, increased with increasing temperature. No significant desorption took place in the present temperature range. The presence of other anions and cations affected the uptake of Hg(II) markedly. Irradiation of hydrous ferric oxide and tungsten oxide by using a 11.1 x 10(9)Bq (Ra-Be) neutron source having a neutron flux of 3.9 x 10(6)cm(-2)s(-1) with the associated gamma-dose rate of 1.72 Gy h(-1) did not influence the extent of adsorption of Hg(II) significantly.     

Copper (II) adsorption from aqueous solution by herbaceous peat

In this research, the herbaceous peat collected from Gavurgolu peatlands, one of the biggest Turkish peatlands, was utilized as an adsorbent for the removal of copper (II) ions from aqueous solution. Adsorption experiments were conducted under various conditions, i.e., initial concentration, temperature, and pH. While the amount of Cu (II) adsorbed on the peat increased with increasing concentration of Cu (II) ions, it was not markedly affected by temperature and pH. Percentage removal was higher at lower concentration. For example, the maximum percentage removal of Cu (II) ions for initial concentration of 3 x 10(-4) M was 97.04% at 21 degrees C and pH 5.5. The adsorption capacity (Q(0)) of the peat was 4.84 mgg(-1) from Langmuir adsorption isotherm for the concentration range of 3 x 10(-4)-6 x 10(-4) M at 21 degrees C and pH 5.5. The equilibrium time of adsorption of Cu (II) ions was 150 min and independent of concentration and temperature. The amount of Cu (II) adsorbed at equilibrium time did not considerably change with temperature and pH. It was also determined that adsorption isotherm followed both Freundlich and Langmuir. Uptake mechanism of Cu (II) ions by the peat occurs via cation exchange (especially by means of Ca(2+) and Mg(2+)) as well as copper/peat complexation. Adsorption kinetic was consistent with the pseudo-second-order model.     

Influence of TBP on the extraction of uranium(VI) from nitric acid media by N,N-dibutyldecanamide

Natural zeolitic materials (sedimentary zeoliferous rocks) were organo-modified using polyhexamethyleneguanidine-chloride in order to enhance their anionic sorptive properties. The sorption of As(V)-anions from aqueous solutions [As(V) concentration range from 10 to 1000 mg/l] was investigated using radiochemical techniques. The samples exhibited an elevated tendency to sorb As(V)-anions (up to 6.73 mg/g) and the relative uptake was found to be much higher for solutions of low initial concentrations (up to 99.8% removal). The different As(V) species (mainly HAsO₄ ²⁻) are principally sorbed through ion-exchange reactions by the net of the polymeric, compound covering the mineral aggregates of the samples. The investigated materials could be considered for the removal of As(V) anionic species present in industrial or municipal wastewaters.     

Biosorption of mercury by carboxymethylcellulose and immobilized Phanerochaete chrysosporium

Phanerochaete chrysosporium basidiospores immobilized onto carboxymethylcellulose were used for the removal of mercury ions from aqueous solutions. The biosorption of Hg(II) ions onto carboxymethylcellulose and both immobilized live and heat-inactivated fungal mycelia of Phanerochaete chrysosporium was studied using aqueous solutions in the concentration range 30-700 mg l⁻¹. The biosorption of Hg(II) ions by the carboxymethylcellulose and both live and heat-inactivated immobilized preparations increased as the initial concentration of mercury ions increased in the medium. Maximum biosorption capacity for immobilized live and heat-inactivated fungal mycelia of Phanerochaete chrysosporium was found to be 83.10 and 102.15 mg Hg(II) g⁻¹, respectively, whereas the amount of Hg(II) ions adsorbed onto the plain carboxymethylcellulose beads was 39.42 mg g⁻¹. Biosorption equilibria were established in approximately 1 h and the correlation regression coefficients show that the adsorption process can be well defined by a Langmuir equation. Temperature changes between 15 and 45 °C did not affect the biosorption capacity. The effect of pH was also investigated and the maximum adsorption of Hg(II) ions onto the carboxymethylcellulose and both live and heat-inactivated immobilized fungal mycelia was observed at pH 6.0. The carboxymethylcellulose-fungus beads could be regenerated using 10 mM HCl, with up to 95% recovery. The biosorbents were used in three biosorption-desorption cycles and no significant loss in the biosorption capacity was observed.     

Extraction of thorium from aqueous nitric acid solution by bis-2-(butoxyethyl ether) (DBC)

The solvent extraction of thorium(IV) (4.3·10^–4M) from nitric acid solution by bis-2-(butoxyethyl ether) (butex or DBC) has been studied. It has been investigated as a function of nitric acid, extractant and metal ion concentration. The effect of equilibration time, diverse ions and salting-out agent on the extraction has also been examined. Among anions, fluoride, phosphate, oxalate and perchlorate have reduced the extraction. Cations such as Na(I), K(I), Ca(II), Zn(II), Al(III), Ti(IV), Zr(IV) except Sr(II) and Pb(II) do not interfere in the extraction. The extraction is enhanced upto 97% in three stages at 6M HNO₃ having 2.94M NaNO₃ as salting-out agent. The extraction is found to be independent of thorium concentration in the range studied (4.3·10^–4–4.3·10^–2M). The temperature (18–45°C) has an adverse effect on the extraction. A 1% solution of ammonium bifluoride is found to be a good stripping solution and recovery of thorium is >98%.     

Optical metal-organic framework sensor for selective discrimination of some toxic metal ions in water

This paper reports the development of a facile and effective approach, based on the use of Zr-based metal-organic frameworks (UiO-66) sensor with micropores geometry, shape and particle morphology for the visual detection and removal of ultra-traces of some toxic metal ions such as Bi(III), Zn(II), Pb(II), Hg(II) and Cd(II). UiO-66 was used as selective carriers for accommodating hydrophobic chromophore probes such as dithizone (DZ) without coupling agent for sensitive and selective discrimination of trace level of toxic analytes. The developed UiO-66 sensor was utilized for the detection of ultra-traces of some toxic metal ions with the naked eye. The new sensor displays high sensitivity and selectivity of a wide range of detectable metals analytes up to 10⁻¹⁰ mol dm⁻³ in solution, in a rapid analyte uptake response (seconds). The developed sensor is stable, cost effective, easy to prepare, and would be useful for rapid detection and removal of ultra-traces of toxic metal ions in water samples.     

Laterite clay-based geopolymer as a potential adsorbent for the heavy metals removal from aqueous solutions

This study is focused on the investigation of low iron lateritic clay-based geopolymer as a potential adsorbent for the higher uptake of Ni(II) and Co(II) ions from aqueous solutions. BET analysis revealed that the sieved geopolymer sample (SGS) was characterized by 17.441 m²/g of surface area, 0.005 cm³/g of pore volume, and 13.549 Å of pore diameter. SEM investigation confirmed the presence of pores and cavities onto the surface of SGS. XRD analysis showed that the geopolymer is semi-crystalline in nature. It was found that the adsorption ability of SGS remained 520 mg/g for Ni(II) ions and 500 mg/g for Co(II) ions when 0.5 M solutions were stirred with SGS for 60 min. The temperature and pH of the solution were maintained at 60 °C and 7.0, respectively. The adsorption data of both heavy metal (HM) ions fitted best in the pseudo-second-order kinetic model. The low activation energy value i.e. 2.507 kJ/mol for Ni(II) ions and 2.286 kJ/mol for Co(II) ions confirmed adsorption is physisorption. Adsorption data were tested with Langmuir and Freundlich models, the data showed comparatively better fitting in the Freundlich model. The greater value of monolayer adsorption capacity (Xm) for Ni(II) ions was found 1.77 × 10⁻² mol/g while for Co(II) ions it remained 1.69 × 10⁻² mol/g confirming the better interaction of metal ions with the adsorbent surface. Negative values of ΔG° confirmed the spontaneity of the process while the positive value of ΔS° showed the randomness of adsorbate particles. The positive value of ΔH° showed that the adsorption process remained endothermic for both HM ions. The experimental results confirmed the ability of laterite clay-based geopolymer for better removal of HM ions and hence can be employed for the wastewater treatment processes at low-cost adsorbent.     

Ion exchangers in radioactive waste management

Adsorption of strontium ions from aqueous solution of Sr(NO₃)₂ on synthetic sodium titanate [(NaO)_x(TiO)_y(OH)_z] powder has beet investigated as a function of contact time, Sr(II) concentration and temperature. X-ray diffraction studies indicated poor crystallinity of the synthetic sodium titanate, which became more crystalline after annealing at ca. 1173 K for 6 h in air. The adsorption of strontium ions on sodium titanate was favored at higher concentrations of the adsorbate and at lower temperatures. The kinetics of the process follows a first-order rate law with respect to adsorptive concentration and obeys the Freundlich isotherm in the entire range of adsorptive concentration. The process of adsorption in the present system has been found to be of the ion-exchange type.     

Use of amorphous zirconium phosphate for the treatment of radioactive waste

Ion-exchange experiments were carried out for the removal of¹³⁷Cs, and⁹⁰Sr/⁹⁰Y radioisotopes by different cationic forms of amorphous zirconium phosphate. The effect of temperature and concentration on the percent uptake and distribution coefficients (K _d ) values (milli-equivalents of ion per gram of exchanger/milli-equivalents of ion per ml of solution) were determined. Experiments were made in simulated pond water at pH 11.4.     

Adsorption/desorption of Cd(II), Cu(II) and Pb(II) using chemically modified orange peel: Equilibrium and kinetic studies

Waste materials from industries such as food processing may act as cost effective and efficient biosorbents to remove toxic contaminants from wastewater. This study aimed to establish an optimized condition and closed loop application of processed orange peel for metals removal. A comparative study of the adsorption capacity of the chemically modified orange peel was performed against environmentally problematic metal ions, namely, Cd²⁺, Cu²⁺ and Pb²⁺, from aqueous solutions. Chemically modified orange peel (MOP) showed a significantly higher metal uptake capacity compared to original orange peel (OP). Fourier Transform Infrared (FTIR) Spectra of peel showed that the carboxylic group peak shifted from 1637 to 1644 cm⁻¹ after Pb (II) ions binding, indicated the involvement of carboxyl groups in Pb(II) ions binding. The metals uptake by MOP was rapid and the equilibrium time was 30 min at constant temperature and pH. Sorption kinetics followed a second-order model. The mechanism of metal sorption by MOP gave good fits for Freundlich and Langmuir models. Desorption of metals and regeneration of the biosorbent was attained simultaneously by acid elution. Even after four cycles of adsorption-elution, the adsorption capacity was regained completely and adsorption efficiency of metal was maintained at around 90%.     

铜（II）离子对脱镁叶绿素-a荧光猝灭的研究

本文介绍了一种利用荧光熄灭定量的测定铜（II）的新方法。从新鲜菠菜中提取叶绿素-a,用高氯酸溶液处理,制得脱镁叶绿素-a。测量脱镁叶绿素-a的紫外-可见吸收光谱,观测到505和535nm处有特征吸收峰。在60 ℃水浴中,脱镁叶绿素-a的丙酮溶液与铜（II）离子水溶液混合,5分钟后发现混合液颜色变绿,505和535 nm处吸收峰消失。铜（II）离子水溶液与脱镁叶绿素-a的丙酮溶液混合后发生荧光猝灭现象,而类似浓度的其它生理离子在相同反应条件下对脱镁叶绿素-a的荧光猝灭现象不明显。 研究了铜（II）离子与脱镁叶绿素-a的反应时间,反应温度对荧光强度衰减的影响。并通过阿累尼乌斯经验关系估算铜（II）离子与脱镁叶绿素-a反应的活化能约为10 ±1kJ·mol-1。研究了铜（II）离子的浓度对脱镁叶绿素-a的丙酮溶液荧光强度的影响,在8.0×10-5 ～8.0×10-7 mol·dm-3范围内,铜（II）离子的浓度与混合液的荧光强度成线性衰减关系,检测限可达8.0×10-7 mol·dm-3。利用脱镁叶绿素-a的丙酮溶液的荧光强度变化测量,有望发展成为一种检测铜（II）离子的新方法。