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1.
Praveen RS  Metilda P  Daniel S  Rao TP 《Talanta》2005,67(5):960-967
A new chelating polymeric sorbent has been developed using Merrifield chloromethylated resin anchored with quinoline-8-ol (HQ). The modified polymeric resin was characterized by FT-IR spectroscopy and elemental analysis. The HQ anchored resin showed superior binding affinity for U(VI) over Th(IV) and La(III). The influence of various physicochemical parameters on the recovery of U(VI) were optimized by both static and dynamic methods. The phase exchange kinetic studies performed for U(VI) revealed that <5 min was sufficient for reaching equilibrium metal ion sorption. The maximum sorption capacity of HQ anchored resin for U(VI) was found to be 120.30 mg g−1 of resin which is higher than other solid phase extraction sorbents reported so far excepting N,N-dibutyl, N′-benzoyl thiourea sorbed Amberlite XAD-16. The developed HQ anchored polymeric resin is highly selective as none of the extraneous species were found to have any deleterious effect. Solid phase extraction (SPE) studies performed using HQ anchored polymeric resin offered enrichment factor of 100 and the lowest concentration below which recoveries become non-quantitative is 5 μg l−1. The accuracy of the developed SPE method in conjunction with Arsenazo III procedure was tested by analyzing marine sediment (MESS-3) and soil (IAEA–Soil 7) reference materials. Furthermore, the above procedure has been successfully employed for the analysis of real soil and sediment samples.  相似文献   

2.
A new method has been developed using (bis-3,4-dihydroxy benzyl)p-phenylene diamine functionalized to XAD-16 (a polystyrene divinyl benzene copolymer) matrix, to preconcentrate mainly U(VI) and Th(IV) from synthetic and real samples. The developed method is free from matrix interference due to alkali and alkaline metal ions and preconcentrates the actinides with a high degree of selectivity, with consistent trace recoveries. The new chelating resin provides dramatic improvement in metal exchange rate, with half value saturation time (t1/2) of less than 1.6 min. The developed method was superior in its metal loading capacity for U(VI) and Th(IV), with values of 0.666 and 0.664 mmol g−1, respectively. Various physio-chemical properties like effect of solution pH, kinetic studies, resin loading capacity, sample breakthrough volume, matrix effects etc., on metal ion sorption to sorbent phase, were studied using both batch and column method. The new chelatogen was applied to extract U(VI) from near neutral real water samples. Preconcentration and separation of metal ions were possible through pH variation and also by varying the eluant concentration. A high preconcentration factor value of 350 with a lower limit of detection of 20 and 30 ng cm−3 was obtained for U(VI) and Th(IV), respectively. The practical applicability of the developed resin was examined using synthetic and real samples such as sea/well water samples. The method provides low relative standard deviation values of <3.5% for all analytical measurements, reflecting on the reproducibility and accuracy of the developed method. The new resin is quite durable with recycling time >35 cycles, without any major change in its quantitative metal uptake nature.  相似文献   

3.
A new class of polymeric resin has been synthesized by grafting Merrifield chloromethylated resin with (dimethyl amino-phosphono-methyl)-phosphonic acid (MCM-DAPPA), for the preconcentration of U(VI), Th(IV) and La(III) from both acidic wastes and environmental samples. The various chemical modification steps involved during grafting process are characterized by FT-IR spectroscopy, 31P and 13C-CPMAS (cross-polarized magic angle spin) NMR spectroscopy and CHNS/O elemental analysis. The water regain capacity data for the grafted polymer are obtained from thermo-gravimetric (TG) analysis. The influence of various physico-chemical parameters during the quantitative extraction of metal ions by the resin phase are studied and optimized by both static and dynamic methods. The significant feature of this grafted polymer is its ability to extract both actinides and lanthanides from high-level acidities as well as from near neutral conditions. The resin shows very high sorption capacity values of 2.02, 0.89 and 0.54 mmol g−1 for U(VI), 1.98, 0.63 and 0.42 mmol g−1 for Th(IV) and 1.22, 0.39 and 0.39 mmol g−1 for La(III) under optimum pH, HNO3 and HCl concentration, respectively. The grafted polymer shows faster phase exchange kinetics (<5 min is sufficient for 50% extraction) and greater preconcentration ability, with reusability exceeding 20 cycles. During desorption process, all the analyte ions are quantitatively eluted from the resin phase with >99.5% recovery using 1 M (NH4)2CO3, as eluent. The developed grafted resin has been successfully applied in extracting Th(IV) from high matrix monazite sand, U(VI) from sea water and also U(VI) and Th(IV) from simulated nuclear spent fuel mixtures. The analytical data obtained from triplicate measurements are within 3.9% R.S.D. reflecting the reproducibility and reliability of the developed method.  相似文献   

4.
Bentonite has been studied extensively because of its strong sorption and complexation ability. Herein, GMZ bentonite from Gaomiaozi county (Inner Mongolia, China) was investigated as the candidate of backfill material for the removal of Th(IV) ions from aqueous solutions. The results indicate that the sorption of Th(IV) is strongly dependent on pH and ionic strength at pH < 5, and independent of ionic strength at pH > 5. Outer-sphere surface complexation or ion-exchange are the main mechanism of Th(IV) sorption on GMZ bentonite at low pH values, whereas the sorption of Th(IV) at pH > 5 is mainly dominated by inner-sphere surface complexation or surface precipitation. Soil fulvic acid (FA) and humic acid (HA) have a positive influence on the sorption of Th(IV) on bentonite at pH < 5. The different addition sequences of HA and Th(IV) to GMZ bentonite suspensions have no obvious effect on Th(IV) sorption to HA-bentonite hybrids. The high sorption capacity of Th(IV) on GMZ bentonite suggests that the GMZ bentonite can remove Th(IV) ions from large volumes of aqueous solutions in real work.  相似文献   

5.
A new chelating polymeric sorbent is developed using Merrifield chloromethylated resin anchored with calix[4]arene-o-vanillinsemicarbazone for simultaneous separation and solid phase extractive preconcentration of U(VI) and Th(IV). The “upper-rim” functionalized calix[4]arene-o-vanillinsemicarbazone was covalently linked to Merrifield resin and characterized by FT-IR and elemental analysis. The synthesized chelating polymeric sorbent shows superior binding affinity towards U(VI) and Th(IV) under selective pH conditions. Various physico-chemical parameters that influence the quantitative extraction of metal ions were optimized. The optimum pH range and flow rates for U(VI) and Th(IV) were 6.0-7.0 and 1.0-4.0 ml min−1 and 3.5-4.5 and 1.5-4.0 ml min−1, respectively. The total sorption capacity found for U(VI) and Th(IV) was 48734 and 41175 μg g−1, respectively. Interference studies carried out in the presence of diverse ions and electrolyte species showed quantitative analyte recovery (98-98.5%) with lower limits of detection, 6.14 and 4.29 μg l−1 and high preconcentration factors, 143 and 153 for U(VI) and Th(IV), respectively. The uptake and stripping of these metal ions on the resin were fast, indicating a better accessibility of the metal ions towards the chelating sites. The analytical applicability of the synthesized polymeric sorbent was tested with some synthetic mixtures for the separation of U(VI) and Th(IV) from each other and also from La(III), Cu(II) and Pb(II) by varying the pH and sequential acidic elution. The validity of the proposed method was checked by analyzing these metal ions in natural water samples, monazite sand and standard geological materials.  相似文献   

6.
Bentonite has been studied extensively because of its strong sorption and complexation ability. In this study, GMZ bentonite (China) was studied as a potential sorbent for the removal of Th(IV) from aqueous solutions. The results indicate that the sorption of Th(IV) is strongly dependent on pH and ionic strength at pH <5, and is independent of ionic strength at pH >5. Outer-sphere surface complexation or ion exchange in inter-layer sites of the montmorillonite fraction of the GMZ bentonite may be the main sorption mechanism of Th(IV) onto GMZ bentonite at low pH values, whereas the sorption of Th(IV) at pH >5 is mainly dominated by inner-sphere surface complexation or surface precipitation. The presence of soil fulvic acid has a positive influence on the sorption of Th(IV) on GMZ bentonite at pH <5. The competition between Th(IV) with aqueous or surface adsorbed cation ions (e.g., herein Li+, Na+ and K+) and surface functional groups of GMZ bentonite is important for Th(IV) sorption on GMZ bentonite. The results of high sorption of Th(IV) suggest that the GMZ bentonite is a suitable backfill material in nuclear waste management.  相似文献   

7.
A new chelating polymeric sorbent has been developed using Merrifield chloromethylated resin anchored with di-bis (2-ethylhexyl) malonamide (DB2EHM). The modified resin was characterized by CPMAS NMR spectroscopy, FT-NIR-FIR spectroscopy, CHN elemental analysis and also by thermo gravimetric analysis. The fabricated sorbent showed superior binding affinity for U(VI) over Th(IV) and other diverse ions, even under high acidities. Various physio-chemical parameters, like solution acidity, phase exchange kinetics, metal sorption capacity, electrolyte tolerance studies, etc., influencing the resin’s metal extractive behavior were studied by both static and dynamic method. Batch extraction studies performed over a wide range of solution acidity (0.01-10 M) revealed that selective extraction of U(VI) could be achieved even up to 4 M acidity with distribution ratios (D) in the order of ∼103. The phase exchange kinetics studies performed for U(VI) and Th(IV) revealed that time duration of <15 min was sufficient for >99.5% extraction. But similar studies when preformed for trivalent lanthanides gave very low D values (<50), with the extraction time extending up to 60 min. The metal sorption studies performed for U(VI) and Th(IV) at 5 M HNO3 was found to be 62.5 and 38.2 mg g−1,respectively. Extraction efficiency in the presence of inferring electrolyte species and inorganic cations were also examined. Metal ion desorption was effective using 10-15 mL of 1 M (NH4)2CO3 or 0.5 M α-hydroxy isobutyric acid (HIBA). Extraction studies performed on a chromatographic column at 5 M acidity were found to give enrichment factor values of 310 and 250 for U(VI) and Th(IV), respectively. The practical utility of the fabricated chelating sorbent and its efficiency to extract actinides from acidic waste streams was tested using a synthetic nuclear spent fuel solution. The R.S.D. values obtained on triplicate measurements (n = 3) were within 5.2%.  相似文献   

8.
The nanocrystalline mordenite (MOR) type zeolite materials with initial chemical composition Na(2)O:Al(2)O(3):10SiO(2):48H(2)O have been synthesized under hydrothermal conditions. MOR1 and MOR2 are spherically shaped nanocrystals, whereas MOR3 and MOR4 have rod-like morphology. This paper reports the sorption characteristics of MOR analogues for Th(IV) and Eu(III) removal from aqueous nuclear waste. Sorption of Th(IV) and Eu(III) on MOR1, MOR2, MOR3 and MOR4 in a single component system with varying initial metal ion concentration, solution pH, contact times, sorbent dose and temperatures has also been investigated. Further, the Langmuir and Freundlich sorption models have been applied to describe equilibrium isotherms at different temperatures. The adsorption capacity increases largely with increasing solution pH and temperature of the system. Specific surface area and pore volume have been investigated by Brunauer-Emmett-Teller (BET) method. The N(2) adsorption isotherm presents a type IV isotherm with narrow hysteresis loop which indicates the presence of mesopores related to inter-particle voids. Thermodynamic results indicate that the sorption follows an endothermic physisorption process. It has been found that these exchangers have good sorption capacity and out of which MOR4 has highest sorption capacity. Thus, nanocrystalline MOR4 is proved to be good sorbent for both Th(IV) and Eu(III).  相似文献   

9.
Olive cake as low-cost abundantly available sorbent has been characterized by N2 at 77 K adsorption, porosity analysis, elemental analysis and IR spectra and has been used for preconcentrating of uranium(VI) and thorium(IV) ions prior to their determination spectrophotometrically. The optimum pH values for quantitative sorption of U(VI) and Th(IV) are 4–7 and 3–7, respectively. The enrichment factor for the preconcentration of U(VI) and Th(IV) were found to be 125 and 75 in the given order. The sorption capacity of olive cake is in the range of 2,260–15,000 μg g−1 for Th(IV) and in the range of 1,090–17,000 μg g−1 for U(VI) at pH 3–7. The sorbent exhibits good reusability and the uptake and stripping of the studied ions were fairly rapid. The elution of U(VI) and Th(IV) was performed with 0.3–1 M HCl/1–2 M HNO3 and 0.3–0.8 M HCl/1 M HNO3, respectively. The precision of the method was 1.8 RSD% for U(VI) and 2.5 RSD% for Th(IV) in a concentration of 1.00 μg mL−1 for 10 replicate analysis. The influence of some electrolytes and cations as interferents was discussed. Separation of U(VI) and Th(IV) from other metal ions in synthetic solution was achieved.  相似文献   

10.
An off-line extraction chromatographic technique has been developed using Amberlite XAD-16 (AXAD-16)-N,N-dihexylcarbamoylmethyl phosphonic acid, as the stationary phase for the extraction of uranium, thorium and lanthanum from nuclear spent fuels as well as from geological and natural water resources. The chemical modifications of the polymeric matrix were monitored using FT-IR spectroscopy, CHNPS elemental analysis and also by thermo gravimetric analysis for water regain measurements. Various physio-chemical parameters influencing the quantitative metal ion extraction by the resin phase were optimized by both static and dynamic methods. The developed resin matrix showed good distribution ratio values under wide concentrations of acidity and pH conditions. Moreover, the sequential separation of analytes is also possible at sample pH 6.5. Also, the polymeric matrix showed superior metal sorption capacities and rapid metal exchange kinetics with a high sample flow rate value of 26 cm3 min−1 for all the three analytes. Thus, reducing the time of analyte extraction from large number of samples anticipated in nuclear waste management programs. The quantitative metal ion recovery of >99.8% was effected with 0.5 M (NH4)2CO3 solution. The method was highly sensitive with lower limits of detections to be 10, 20 and 15 ng cm−3 for U(VI), Th(IV) and La(III), respectively, with a better pre-concentration values of 333 for U(VI) and Th(IV) and 400 for La(III), respectively paving way for its applicability in pre-concentrating trace analytes from large sample volumes. The analytical data were within 4.2% R.S.D. reflecting the reproducibility and reliability of the developed method.  相似文献   

11.
A novel polymeric sorbent for selective extraction of U(VI) and Th(IV) from highly acidic wastes was prepared by modifying Merrifield chloromethylated resin with N,N,N′,N′-tetrahexylmalonamide. The functionalized resin was characterized by FT-IR spectroscopy, CPMAS NMR spectroscopy, CHN elemental analysis and thermo-gravimetric analysis. Various physiochemical parameters responsible for quantitative extraction of metal ions were studied by static and dynamic methods. The resin exhibited very good extractability over a wide range of acidity (0.01–10 M) with a faster exchange rate (saturation possible within 20 min) and high sorption capacities (0.645 and 0.558 mmol g−1) for U(VI) and Th(IV), respectively. Quantitative metal desorption was achieved by using 0.5 M (NH4)2CO3 for both analytes. The significant feature of the resin is the possibility of sequential separation and the ability to elute only U(VI) with water, thus offering the possibility of sequential separation of U(VI) and Th(IV). Interference studies with commonly encountered metal ions, rare earth ions and electrolytes were conducted. Enrichment factors of 400 and 350 with a limit of quantification of 20 ng mL−1 and 50 ng mL−1 were achieved for the two analytes. All the analytical data were within 3.8% RSD, reflecting the reproducibility and reliability of the method.  相似文献   

12.
A new chelating resin (glycidyl methacrylate/divinylbenzene/pentaethylenehexamine (GMA/DVB/PEHA)) for uranium(VI) and thorium(IV) has been developed by functionalizing GMA/DVB with PEHA. The adsorption of U(VI) and Th(IV) ions onto the functionalized GMA/DVB/PEHA were investigated as a function of pH value, contact time, and temperature using batch adsorption technique. The results showed that U(VI) and Th(IV) adsorption onto GMA/DVB/PEHA was strongly dependent on pH. Kinetic studies revealed that the adsorption process achieved equilibrium within 15 and 90 minutes for Th(IV) and U(VI), respectively, and followed a pseudo-second-order rate equation. The isothermal data correlated with the Langmuir model better than the Freundlich model. Thermodynamic data indicated the spontaneous and endothermic nature of the process. The maximum adsorption capacity of U(VI) and Th(IV) were found to be 114 and 78 mg/g, respectively. Quantitative recovery of uranium and thorium were achieved by desorbing the loaded GMA/DVB/PEHA with 0.5 M HNO3   相似文献   

13.
Nakayama M  Itoh K  Chikuma M  Sakurai H  Tanaka H 《Talanta》1984,31(4):269-274
A functional resin for the collection of selenium(IV) has been prepared simply by the conversion of a common ion-exchange resin with bismuthiol-II which has three functional properties, namely the capabilities of selective reaction with selenium(IV), ion-exchange reaction with ion-exchange resin and strong physical sorption to the ion-exchange resin matrix. The binding ratio of selenium(IV) to bismuthiol-II on the resin was confirmed to be 1:4. The reaction was represented as follows: 4RSH + H(2)SeO(3)--> R-S-Se-S-R + R-S-S-R + 3H(2)O. Highly selective sorption of selenium(IV) was achieved, based on the formation of stable selenotrisulphide on the resin. Selenium(IV) sorbed on bismuthiol-II resin was eluted effectively with 8-13M nitric acid or some thiols, such as cysteine and penicillamine. In the cases of thiols, the elution of selenium was found to be also based on the formation of selenotrisulphide, and the bismuthiol-II resin was regenerated. Satisfactory results were obtained when this resin was applied to the determination of selenium(IV) in river, estuarine or sea water samples.  相似文献   

14.
A new adsorbent, modified mesoporous lanthanum(III) silicate, has been prepared with various molar ratios of Si/La (10, 20, 40, 80) and cethyltrimethylammonium bromide (CTAB) as structure directing agent. XRD, nitrogen sorption, SEM, IR, thermogravimetry and sorption of radionuclides and toxic metal ions have been studied. The results show that adsorption amount of some element such as Pb(II) and Th(IV) has been increased significantly by incorporation of lanthanum ions in the framework of adsorbent. Separation of Co(II)‐Th(IV), Co(II)‐U(VI) and Mo(VI)‐U(VI) has been developed on columns of this adsorbent.  相似文献   

15.
Graphene oxide (GO) is one of the most important carbon nano-materials. In this paper, GO was synthesized from flake graphite and characterized by transmission electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy. The sorption of Th(IV) on GO was investigated as a function of contact time, solid-to-liquid ratio, pH, ionic strength, and in the presence of fulvic acid (FA) and humic acid (HA) by batch experiments. The sorption percentage of Th(IV) on GO decreased with increasing ionic strength and decreasing solid-to-liquid ratio. The sorption edge of Th(IV) in the presence of FA/HA is much lower than that in the absence of FA/HA. Furthermore, the sorption processes of Th(IV) can be described by a pseudo-second order rate model. Based on the Langmuir model, the maximum sorption capacities (Csmax) of Th(IV) were about 5.80 × 10?4 mol/L. From thermodynamic investigation, sorption of Th(IV) on GO is spontaneous and endothermic in nature. The rapid sorption rate and high sorption capacity suggest that GO is a promising adsorbent for Th(IV).  相似文献   

16.
1-(2-氨乙基)吡咯烷树脂的合成及其对贵金属的吸附   总被引:4,自引:0,他引:4  
研究了试剂摩尔比、反应温度、反应时间对1-(2-氨乙基)吡咯烷树脂合成的影响规律.此树脂的功能基含量2.74 mmol/g树脂,对Au(Ⅲ)、Os(Ⅳ)、Pt(Ⅳ)、Ir(Ⅳ)、Ru(Ⅲ)、Pd(Ⅱ)的吸附容量分别高达950、520、436、418、314、302 mg/g树脂.FT-IR、元素分析表征了树脂结构.测定了吸附速率曲线,配位比,表观吸附活化能△E_(Au)=6.4、△E_(Pt)=33.7kJ/mol.XPS研究了吸附机理.  相似文献   

17.
A new grafted polymer has been developed by the chemical modification of Amberlite XAD-16 (AXAD-16) polymeric matrix with [(2-dihydroxyarsinoylphenylamino)methyl]phosphonic acid (AXAD-16-AsP). The modified polymer was characterized by a combination of 13C CPMAS and 31P solid-state NMR, Fourier transform-NIR-FIR-Raman spectroscopy, CHNPS elemental analysis, and thermogravimetric analysis (TGA). The distribution studies for the extraction of U(VI), Th(IV), and La(III) from acidic solutions were performed using an AXAD-16-AsP-packed chromatographic column. The influences of various physiochemical parameters on analyte recovery were optimized by both static and dynamic methods. Accordingly, even under high acidities (>4 M), good distribution ratio (D) values (102–104) were achieved for all the analytes. Metal ion desorption was effective using 1 mol L–1 (NH4)2CO3. From kinetic studies, a time duration of <15 min was sufficient for complete metal ion saturation of the resin phase. The maximum metal sorption capacities were found to be 0.25, 0.13, and 1.49 mmol g–1 for U(VI); 0.47, 0.39, and 1.40 mmol g–1 for Th(IV); and 1.44, 1.48, and 1.12 mmol g–1 for La(III), in the presence of 2 mol L–1 HNO3, 2 mol L–1 HCl, and under pH conditions, respectively. The analyte selectivity of the grafted polymer was tested in terms of interfering species tolerance studies. The system showed an enrichment factor of 365, 300, and 270 for U(VI), Th(IV), and La(III), and the limit of analyte detection was in the range of 18–23 ng mL–1. The practical applicability of the polymer was tested with synthetic nuclear spent fuel and seawater mixtures, natural water, and geological samples. The RSD of the total analytical procedure was within 4.9%, thus confirming the reliability of the developed method.  相似文献   

18.
A new polystyrene-divinylbenzene resin containing 1-(2-thiazolylazo)-2-naphthol (TAN) functional group was synthesized and its sorption behavior for 19 metal ions including Zr(IV), Hf(IV) and U(VI) was investigated by batch and column experiments. The chelating resin showed a high sorption affinity for Zr(IV) and Hf(IV) at pH 2. Some parameters affecting the sorption of the metal ions are detailed. The breakthrough and overall capacities were measured under optimized conditions. The overall capacities of Zr(IV) and Hf(IV) that were higher than those of the other metal ions were 0.92 and 0.87 mmol/g, respectively. The elution order of metal ions at pH 4 was evaluated as: Zr(IV)>Hf(IV)>Th(IV)>V(V)>Nb(V)>Cu(II)>U(VI)>Ta(V)>Mo(VI)>Cr(III)>Sn(IV)>W(VI). Quantitative recovery of most metal ions except Zr(IV) was achieved using 2 M HNO3. Desorption and recovery of Zr(IV) was successfully performed with 2 M HClO4 and 2 M HCl.  相似文献   

19.
A novel glycidyl methacrylate chelating resin has been synthesized through copolymerization of glycidyl methacrylate (GMA) in the presence of divinylbenzene (DVB), the resulting resin was immobilized with 3,4,5-trihydroxybenzoic acid (THBA) to give GMA/DVB/THBA chelating resin. The adsorption of Th(IV) and U(VI) on GMA/DVB/THBA adsorbent was studied as a function of initial concentration, pH, shaking time and temperature. The novel chelating resin shows a high capacity for Th(IV) and U(VI), maximum adsorption of Th(IV) and U(VI) were 56 and 83.6 mg/g, respectively. Kinetic studies showed that the adsorption follows the pseudo second order model referring to the influence of the textural properties of the resin on the rate of adsorption. Thermodynamic parameters such as ?H° and ?S° were studied and indicated an endothermic process.  相似文献   

20.
Sorption of thorium (IV) on goethite was investigated as a function of contact time, pH, ionic strength, anions, solid-to-liquid ratio (m/V) and Th(IV) concentration using batch technique. The results showed that the sorption of Th(IV) was strong pH-dependence, and increased from ~10 to ~100% over the pH range of 2.0–4.0, and then kept a constant level in the higher pH range. The sorption of Th(IV) increased with increasing m/V and independent of ionic strength. It was clear that phosphate and FA significantly enhanced Th(IV) sorption on goethite. The sorption and desorption isotherms were investigated at pH 2.90 ± 0.05 and analyzed with Freundlich and Langmuir models, respectively. Compared to Langmuir model, Freundlich model could fit the experimental data better, according to the high relative coefficients.  相似文献   

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