Simultaneous extraction and preconcentration of uranium and thorium in aqueous samples by new modified mesoporous silica prior to inductively coupled plasma optical emission spectrometry determination

A new synthesized modified mesoporous silica (MCM-41) using 5-nitro-2-furaldehyde (fural) was applied as an effective sorbent for the solid phase extraction of uranium(VI) and thorium(IV) ions from aqueous solution for the measurement by inductively coupled plasma optical emission spectrometry (ICP OES). The influences of some analytical parameters on the quantitative recoveries of the analyte ions were investigated in batch method. Under optimal conditions, the analyte ions were sorbed by the sorbent at pH 5.5 and then eluted with 1.0 mL of 1.0 mol L⁻¹ HNO₃. The preconcentration factor was 100 for a 100 mL sample volume. The limits of detection (LOD) obtained for uranium(VI) and thorium(IV) were 0.3 μg L⁻¹. The maximum sorption capacity of the modified MCM-41 was found to be 47 and 49 mg g⁻¹ for uranium(VI) and thorium(IV), respectively. The sorbent exhibited good stability, reusability, high adsorption capacity and fast rate of equilibrium for sorption/desorption of uranium and thorium ions. The applicability of the synthesized sorbent was examined using CRM and real water samples.     

Preconcentration of beryllium via octadecyl silica gel microparticles doped with aluminon, and its determination by flame atomic absorption spectrometry

A simple and sensitive method is presented for solid phase extraction (SPE) and preconcentration of trace quantities of beryllium using octadecyl silica gel modifed with aurin tricarboxylic acid (aluminon). Beryllium is then determined by flame atomic absorption spectroscopy. Parameters affecting SPE such as pH, sample solution and eluent flow rate, type, concentration and volume of eluent, interfering ions and breakthrough volume, were investigated. Under optimal conditions, the beryllium ions were retained on the sorbent at pH 6–6.7, while 3.0 mL of 0.05 mol L^?1 HNO₃ is sufficient to elute the ions. The limit of detection (LOD) based on 3σ was 0.8 µg L^?1 for 250 mL sample solution and 5 mL 0.05 mol L^?1 HNO₃ as eluent. The LOD can reach 0.1 µg L^?1 for 1 L sample solution and 3 mL of 0.05 mol L^?1 HNO₃. The accuracy and precision (RSD %) of the method is >90% and <10%, respectively. The method was applied to the determination of beryllium in aqueous samples.     

Electrochemical Sensing of Rutin Using an MCM-41 Modified Electrode

Abstract

MCM-41 was synthesized with uniform pore networks and then used to modify a carbon-paste electrode (CPE). The electrochemical behavior of rutin was investigated. Compared with the bare CPE, the MCM-41–modified CPE remarkably enhances the redox peak currents of rutin, attributed to large surface area, high sorption capacity, and specific mesopores. Based on this, a sensitive and convenient electrochemical method was developed for the analysis of rutin. The linear range is from 2.0 × 10^?8 to 1.0 × 10^?6 mol L^?1, and the limit of detection is 1.5 × 10^?8 mol L^?1. Finally, this method was employed to determine rutin in traditional Chinese medicines.     

Synthesis, characterization and application of a novel sorbent, glucamine-modified MCM-41, for the removal/preconcentration of boron from waters

A novel sorbent was prepared by the functionalization of an inorganic support material, MCM-41, with N-methylglucamine for the uptake of boron from aqueous solutions prior to its determination by inductively coupled plasma optical emission spectrometry (ICP-OES). Characterization of the newly synthesized material was performed using BET, XRD, TEM, SEM and DRIFTS techniques, in addition to its C and N elemental content. Sorption behavior of the novel sorbent for boron was also investigated and found to obey Freundlich and Dubinin-Radushkevich (D-R) isotherm models. The maximum amount of B (as H₃BO₃) that can be sorbed by the sorbent was calculated from the D-R isotherm and was found to be 0.8 mmol B g⁻¹ of sorbent. The applicability of the new sorbent for the removal/preconcentration of boron from aqueous samples was examined by batch method. It was found that the sorbent can take up 85% of boron in 5 min whereas quantitative sorption is obtained in 30 min. Any pH greater than 6 can be used for sorption. Desorption from the sorbent was carried out using 1.0 M HNO₃. The sorption efficiency of the new sorbent was also compared to that of Amberlite IRA 743, a commercial resin with N-methylglucamine functional groups. Within the experimental conditions employed, the new sorbent was found to have higher sorption efficiency than the commercial resin. For method validation, spike recovery tests were performed at various concentration levels in different water types and were found to be between 83-95 and 75-92% for ultra pure water and geothermal water, respectively.     

Removal of complexed mercury by dithiocarbamate grafted on mesoporous silica

Mesoporous silica (MCM-41) with d ₍₁₀₀₎ interplanar distance of 38 Å was prepared by a room temperature process through low surfactant templation technique. The surface of MCM-41 was functionalized with dithiocarbamate (dtc) ligand, named as MCM-41-dtc and this was characterized by X-ray diffraction, BET surface area, particle size analysis, ²⁹Si MAS NMR spectra and sulphur analysis. The sorption of mercury from 0.1M HCl solution by MCM-41-dtc was studied as a function of pH, [Hg²⁺], time and temperature. The sorption data obtained at various initial concentrations of mercury were fitted into Langmuir adsorption model. Mercury speciation in solution and the sorption capacity measurements indicated possible formation of a 1 : 1 square planar complex in the solid phase. A very rapid sorption of mercury was observed in the initial stages of equilibration, which can be attributed to the large surface area, wide porosity and fine particle size of MCM-41-dtc, facilitating facile accessibility of mercury into the inner pores of the sorbent. The enthalpy change accompanied by the sorption of mercury was found to decrease from 83.7 to 6.2 kJ/mol, when the initial concentration of mercury was increased from 5^.10^-4M to 1.5^.10^-3M.     

Attapulgite modified with 2-hydroxy-1-naphthaldehyde as selective solid-phase extractant for determination of copper(II) in environmental samples by ICP-OES

Attapulgite modified with 2-hydroxy-1-naphthaldehyde was prepared and applied to the separation, preconcentration and determination of Cu(II) in aqueous solutions by inductively coupled plasma optical emission spectrometry. Experimental conditions for effective adsorption of trace levels of Cu(II) were optimized using batch and column procedures. The optimum pH value for the separation of Cu(II) on the newly sorbent was 4.0 and complete elution of Cu(II) from the sorbent surface was carried out using 2 mL of 0.01 mol L^?1 HCl. The adsorption capacity for Cu(II) was 25.13 mg g^?1. The detection limits of the method defined by IUPAC were found to be 0.24 μg L^?1 with enrichment factor of 150. The method has been applied to the determination of Cu(II) in certified reference materials and natural water samples with satisfactory results.     

Synthesis,characterisation and application of mercapto- and polyaminophenol-bifunctionalised MCM-41 for dispersive micro solid phase extraction of Ni(II) prio to inductively coupled plasma-optical emission spectrometry (DMSPE-ICP-OES)

Highly ordered adsorbent mesoporous silica (MCM-41) was synthesised using a rapid method and its subsequent chemical modification with 3-mercaptopropyltrimethoxysilane (MPTMS) in toluene medium at 60°C was performed. The electro-reduction product of 4-nitrophenol (EP4NP), as a new kind of polyaminophenol-type chelating agent with a high affinity to Ni(II), was then incorporated into MPTMS-MCM-41. The resulting materials (MCM-41, MPTMS-MCM-41 and EP4NP-MPTMS-MCM-41) were characterised by scanning electron microscopy, powder X-ray diffraction, nitrogen gas sorption and Fourier transform-infrared spectrometry. The new modified adsorbent EP4NP-MPTMS-MCM-41 was then employed for preconcentration of ultra-trace amounts of Ni(II) by dispersive micro solid phase extraction prior to inductively coupled plasma-optical emission spectrometry. The effects of variables such as pH, mass of the chelating agent, the amount of EP4NP-MPTMS-MCM-41, stirring time of extraction step, HCl concentration and stirring time during elution were optimised and the calibration curve was plotted. The limits of detection and quantitation were 0.006 and 0.019 μg L^?1, respectively. The mean, standard error and relative standard deviation for five replicates of 0.5 μg L^?1 Ni(II) were calculated to be 0.48 μg L^?1, 4.0% and 3.2%, respectively. The proposed method was successfully applied for determination of Ni(II) in wastewater samples.     

A Ce3+-imprinted functionalized potassium tetratitanate whisker sorbent prepared by surface molecularly imprinting technique for selective separation and determination of Ce3+

A surface molecular imprinting technology was developed to adsorb Ce(III) ions that showed much higher adsorption affinity and selectivity for than for other metal ions. The batch adsorption process was studied with respect to effects of pH value, residence time, temperature, and initial concentration of Ce(III) ion. The maximum adsorption capacity is 43 mg g^?1 at an initial Ce(III) concentration of 300 mg L^?1 and at a sorbent dosage of 1.0 g L^?1. A Langmuir isotherm fits the experimental data. The imprinted sorbent exhibits a much higher separation and selectivity for the target imprinted ion than the non-imprinted polymer. Cerium ion can be desorbed with 1M hydrochloric acid solution which is also proven by scanning electron microoscopy and X-ray diffraction experiments. The limit of detection is 37 ng mL^?1. The sorbent has been applied to the determination of trace cerium in different environmental samples with satisfactory results.     

Removal of Th4+ ions from aqueous solutions by graphene oxide

The removal of Th⁴⁺ ions from aqueous solutions was investigated using single-layer graphene oxide (GO) as a sorbent which was prepared by the modified Hummers’ method through batch adsorption experiments at room temperature. Structural characterizations of the sorbent were also investigated. The influences of the pH value of solution, contact time, sorbent dose, ionic strength, the initial metal ion concentration and temperature on the adsorption of Th⁴⁺ were also investigated. These results indicated that the adsorption of Th⁴⁺ was dependent on the pH and independent on the ionic strength. The sorbent provided significant Th⁴⁺ removal (>98.7 %) at pH 3.0 and the adsorption equilibrium was achieved after only 10 min. The Langmuir adsorption isotherm fit the absorption profile very closely, and indicated that a maximum adsorption capacity of 1.77 mmol g^?1 of GO (411 mg g^?1) after 2 h. The thermodynamic parameters showed that this adsorption process was endothermic and spontaneous. Moreover, the desorption level of Th⁴⁺ from GO, by using 0.1 mol L^?1 H₂SO₄ as a stripping agent, was 84.2 ± 1.2 %, and that of 0.5 mol L^?1 HNO₃ as a stripping agent, was 79.8 ± 3.0 %.     

Solid phase extraction using silica gel functionalized with Sulfasalazine for preconcentration of uranium(VI) ions from water samples

Silica gel surface was chemically functionalized by reaction the silanol from the silica surface with 3-chloropropyltrimethoxysilane followed by reaction with Sulfasalazine. This new sorbent has been used for the preconcentration of low levels of U(VI) ions from an aqueous phase. Parameters involved in extraction efficiency such as pH, weight of the sorbent, volume of sample and eluent were optimized in batch and column methods prior to determination by spectrophotometry using arsenazo(III) reagent. The results showed that U(VI) ions can be sorbed at pH range of 5.0–6.0 in a minicolumn and quantitative recovery of U(VI) (>98.0?±?1.6%) was achieved by stripping with 2.5 mL of 0.1 mol L^?1 HCl. The sorption capacity of the functionalized silica gel was 1.15 mmol g^?1 of U(VI). A linear calibration graph was obtained over the concentration range of 0.02–27.0 μg mL^?1 with a limit of detection of 1 μg L^?1 in treatment with 1000 mL of the U(VI) solution in which the preconcentration factor was as high as 400. The method was employed to the preconcentration of U(VI) ions from spiked ground water and synthetic sea water samples.     

Immobilization of calix[6]arene bearing carboxylic acid and amide groups on aminopropyl silica gel and its sorption properties for Cr(VI)

An aminopropyl silica gel-immobilized calix[6]arene (C[6]APS) containing both amide and acid moieties was prepared from p-tert-butylcalix[6]arene hexacarboxylate derivative and aminopropyl silica gel in the presence of N,N′-diisopropyl carbodiimide coupling reagent. C[6]APS was used to evaluate the sorption properties of Cr(VI) as a sorbent material. In sorption studies, it was observed that C[6]APS was highly effective at pH 1.5 for Cr(VI). The effect of parameters such as pH, sorbent dosage, contact time, initial Cr(VI) concentration and temperature on Cr(VI) sorption; the sorption isotherms were also studied. Maximum sorption capacity was obtained as 3.1 mg g^?1 at pH 1.5 and 25 °C for 1 h and 10.4 mg L^?1 initial Cr(VI) concentration. Thermodynamic parameters such as change in free energy, enthalpy, and entropy were also determined. In the isotherm studies, Langmuir and Freundlich isotherm models were applied and it was found that the experimental data confirmed to Freundlich isotherm model, and the batch sorption capacity of C[6]APS was calculated as 37.66 mg g^?1.     

Study on sorption of U(VI) onto ordered mesoporous silicas

The mesoporous silicas (MCM-41 and MCM-48) are synthesized by hydrothermal method, which are characterized by XRD and BET techniques. The application of mesoporous silicas for the sorption of U(VI) from aqueous solution are studied by using batch technique under ambient condition. The effects of contact time, solid-to-liquid ratio (m/V), solution pH, ionic strength and temperature are determined, and the results indicate that the sorption of U(VI) to MCM-41 or MCM-48 are strongly dependent on pH values but independent of ionic strength. Compared with Langmuir model, the sorption isotherms can be simulated by Freundlich model well according to the high relative coefficients. The parameters for Langmuir and Freundlich sorption isotherms are calculated from the temperature at 298, 318 and 338 K, respectively, and the results suggest that the sorption of U(VI) on MCM-41 or MCM-48 is a spontaneous and exothermic process. In contrast to its sorption capacity for U(VI), MCM-48 is a suitable material for the preconcentration of U(VI) from large volumes of aqueous solutions.     

Biosorption of uranyl ions from aqueous solution by Saccharomyces cerevisiae cells immobilized on clinoptilolite

This study deals with the uptake of uranyl ions from aqueous solution using bio-modified natural clinoptilolite. The biosorption experiments were carried out in a batch system. Cell immobilization process and sorption of uranyl ions were confirmed by scanning electron microscopy and inductively coupled plasma-optical emission spectroscopy techniques, respectively. The adsorption equilibrium was reached in 4 h, the optimum pH was 4.5 and the temperature had no significant effect on the uranyl biosorption. The experimental data were well fitted with Langmuir isotherm and pseudo-second-order kinetic models. The maximum sorption capacity of cell immobilized clinoptilolite was 0.148 mmol ( \( {\text{UO}}_{2}^{2 + } \) ) g^?1 dry sorbent.     

An On-line Admicellar SPE-HPLC System Using CTAB-Modified Zeolite NaY as Sorbent for Determination of Carbamate Pesticides in Water

Zeolite NaY modified with cetyltrimethylammonium bromide (CTAB) was considered for extraction/preconcentration of carbamate pesticides using an on-line SPE-HPLC system. The simultaneous determination of carbamate pesticides, including aldicarb, carbofuran, carbaryl, isoprocarb, methiocarb and promecarb, was performed by HPLC–UV using a LichroCART RP-18 column with gradient elution of methanol and 0.1 % acetic acid. The sorbent presented admicelles of CTAB on its surfaces and exhibited a sorption capacity of 180–18,600 mg kg⁻¹ sorbent, which could be re-modified for at least five extraction cycles. The quantitative retention of target pesticides on the admicellar sorbent involved hydrophobic and π-cation interaction, while pesticides were eluted from the admicellar SPE column using only 750 μL of methanol. LODs and LOQs of the proposed method were 0.005–140 and 0.02–600 μg L⁻¹, respectively. The analytes were effectively concentrated with the enrichment factors between 5 and 551. The developed on-line admicellar SPE-HPLC system was successfully applied to the determination of carbamate pesticides in ten environmental water samples from different sources. Recoveries of spiked samples at a concentration of 0.1–5 mg L⁻¹ ranged from 77 to 111 %.

     

Solid phase extraction of hexavalent chromium by Mannich base polymer wrapped flower-like layered double hydroxide

In the present work, synthesis of polymer wrapped flower-like MgAl layered double hydroxide was done through condensation of 1,4 phenylenediamine and resorcinol by p-formaldehyde. The nanocomposite was characterised with X-ray diffraction analysis, fourier transform infrared spectroscopy, thermogravimetric analysis and field emission scanning electron microscopy techniques and employed for effective adsorption of Cr(VI) from aqueous solution prior to flame atomic absorption spectrometer determination. Optimum level of effective parameters (pH, reaction time and adsorbent dosage) and their interaction was determined by response surface methodology. To investigate applicability of method for trace heavy metal adsorption, the method was employed for preconcentration of Cr(VI) in water samples. At the optimum conditions, pH = 4.5, shaking time of 15 min and adsorbent dosage of 20 mg, analytical performance of the method was evaluated and results showed that calibration curve is linear in the concentration range of 2–100 μg L^?1. Moreover, limit of detection was 0.22 µg L^?1 and relative standard deviation of six replicate experiments at initial concentration of 0.1 mg L^?1 was 3.3%. Isotherm study showed that Freundlich model can better describe adsorption behaviour as well as the sorbent showed the adsorption capacity of 62.5 mg g^?1. Moreover, thermodynamic study revealed that chromate adsorption was spontaneous and followed the endothermic path. Regeneration of sorbent was performed using 1.0 mol L^?1 of NaOH solution. The sorbent was employed for Cr(VI) determination from food additives and seawater samples.     

Preconcentration of trace amounts of cobalt (II) ions in water and agricultural products samples using of 5-(4-dimethylaminobenzylidene) rhodanin modified SBA-15 sorbent prior to FAAS determination

In the present study, the ?5-(4-dimethylaminobenzylidene)rhodanin-modified SBA-15? was applied as stable solid sorbent for the separation and preconcentration of trace amounts of cobalt ions in aqueous solution. SBA-15 was modified by ?5-(4-dimethylaminobenzylidene)rhodanin reagent. The sorption of Co²⁺ ions was done onto modified sorbent in the pH range of 6.8–7.9 and desorption occurred in 5.0 mL of 3.0 mol L^?1 HNO₃. The results exhibit a linear dynamic range from 0.01 to 6.0 mg L^?1 for cobalt. Intra-day (repeatability) and inter-day (reproducibility) for 10 replicated determination of 0.06 mg L^?1 of cobalt was ±1.82% and ?±1.97%?. Detection limit was 4.2 µg L^?1 (3S_b, n = 5) and preconcentration factor was 80. The effects of the experimental parameters, including the sample pH, flow rates of sample and eluent solution, eluent type and interference ions were studied for the preconcentration of Co²⁺. The proposed method was applied for the determination of cobalt in standard samples, water samples and agricultural products.     

Adsorption of thorium(IV) from aqueous solution by non-living biomass of mangrove endophytic fungus Fusarium sp. #ZZF51

The adsorption of thorium(IV) from aqueous solution by mangrove endophytic fungus Fusarium sp. #ZZF51 is studied by using a batch experiments. The parameters that affect the thorium(IV) sorption, such as solution pH, initial thorium(IV) concentration, contact time, and biomass dose, are discussed in detail. The maximum biosorption of thorium(IV) and the equilibrium sorption capacity are found to be 91 ± 1 % and 11.35 mg g^?1 respectively at pH 3.0, contact time 20 min, initial thorium(IV) concentration 50 mg L^?1 and non-living biomass dose 4.0 g L^?1. Kinetics data follow the pseudo-second-order model and equilibrium data agree with the Temkin isotherm model very well. FT-IR analysis indicates that hydroxyl and carbonyl groups play an important role in the biosorption process.     

Sorption of plutonium from low level liquid waste using nano MnO2

Nano-crystalline MnO₂ has been synthesized by the method of alcoholic hydrolysis of KMnO₄ and its potential as a sorbent for plutonium present in the low level liquid waste (LLW) solutions was investigated. The kinetic studies on the sorption of Pu by MnO₂ reveal the attainment of equilibrium sorption in 15 h, however 90 % of sorption could be achieved within an hour. In the studies on optimization of the solution conditions for sorption, it was observed that the sorption increases with the pH of the aqueous solution, attains the maximum value of 100 % at pH = 3 and remains constant thereafter. The sorption was found to be nearly independent of the ionic strength (0.01–1.0 M) of the aqueous solutions maintained using NaClO₄, indicating the inner sphere complexation between the Pu⁴⁺ ions and the surface sites on MnO₂. Interference studies with different fission products, viz., Cs⁺, Sr²⁺ and Nd³⁺, revealed decrease in the percentage sorption with increasing pH of the suspension indicating the competition between the metal ions. However, at the metal ion concentrations prevalent in the low level liquid waste solutions, the decrease in the Pu sorption was only marginally decreased to 90 % at pH = 3, the decrease being more in the case of Nd³⁺ than that in the case of Cs⁺. This study, therefore, shows nano-crystalline MnO₂ can be used as a sorbent for separation of Pu from LLW solutions.     

Silica gel surface modified with sulfanilamide for selective solid-phase extraction of Cu(II), Zn(II) and Ni(II)

A new chelating matrix has been prepared by immobilising sulfanilamide (SA) on silica gel (SG) surface modified with 3-chloropropyltrimethoxysilane as a sorbent for the solid-phase extraction (SPE) Cu(II), Zn(II) and Ni(II). The determination of metal ions in aqueous solutions was carried out by inductively coupled plasma optical emission spectrometry (ICP-OES). Experimental conditions for effective sorption of trace levels of Cu(II), Zn(II) and Ni(II) were optimised with respect to different experimental parameters using the batch and column procedures. The presence of common coexisting ions does not affect the sorption capacities. The maximum sorption capacity of the sorbent at optimum conditions was found to be 34.91, 19.07 and 23.62 mg g^?1 for Cu(II), Zn(II) and Ni(II), respectively. The detection limit of the method defined by IUPAC was found to be 1.60, 0.50 and 0.61 µg L^?1 for Cu(II), Zn(II) and Ni(II), respectively. The relative standard deviation (RSD) of the method under optimum conditions was 4.0% (n = 8). The method was applied to the recovery of Cu(II), Zn(II) and Ni(II) from the certified reference material (GBW 08301, river sediment) and to the simultaneous determination of these cations in different water samples with satisfactory results.     

Adsorptive recovery of an essential rose oil component from aqueous solution by nanoporous carbon (CMK-3)

A nanoporous carbon (CMK-3) was synthesized and used to adsorb 2-phenylethanol (PEA) from aqueous solutions. The characterization of CMK-3 by N₂ adsorption isotherm revealed the formation of a nanoporous carbon with average pore diameter and surface area of 3.34 nm and 1268 m² g^?1, respectively. Column-like particle morphology of CMK-3 was observed from scanning electron microscope images. To evaluate the feasibility of CMK-3 as a potential PEA adsorbent, batch adsorption experiments were conducted for aqueous PEA solutions. The results showed that CMK-3 is an efficient sorbent for the separation of PEA from water. The optimized adsorbent doses were found to be 0.3 and 2.2 g L^?1 for 30 and 300 mg L^?1 PEA, respectively. Our studies about the effect of pH on CMK-3 adsorption capacity revealed that the adsorption capacity increased at lower pH due to the protonation of PEA. Three adsorption models, Langmuir, Freundlich and Temkin were used to describe the adsorption isotherms. Thermodynamic parameters such as ΔG ⁰, ΔH ⁰, and ΔS were also evaluated, and it was found that the sorption process was spontaneous, endothermic, and physical in nature. The adsorption kinetics was investigated in detail and the pseudo-second-order kinetic equation fitted the experimental data very well. The mechanistic study by Weber-Morris model revealed that the overall adsorption process was simultaneously governed by external mass transfer and intraparticle diffusion. Almost all (97 %) adsorbed PEA was successfully recovered into ethanol which is a common solvent in fragrance industry. CMK-3 was proved to be a promising adsorbent for the adsorption-recovery of PEA from aqueous solution.