M.S. Subramanian

A new chelating sorbent for metal ion extraction under high saline conditions

A new chelating polymeric sorbent was developed by functionalizing Amberlite XAD-16 with 1,3-dimethyl-3-aminopropan-1-ol via a simple condensation mechanism. The newly developed chelating matrix offered a high resin capacity and faster sorption kinetics for the metal ions such as Mn(II), Pb(II), Ni(II), Co(II), Cu(II), Cd(II) and Zn(II). Various physio-chemical parameters like pH-effect, kinetics, eluant volume and flow rate, sample breakthrough volume, matrix interference effect on the metal ion sorption have been studied. The optimum pH range for the sorption of the above mentioned metal ions were 6.0-7.5, 6.0-7.0, 8.0-8.5, 7.0-7.5, 6.5-7.5, 7.5-8.5 and 6.5-7.0, respectively. The resin capacities for Mn(II), Pb(II), Ni(II), Co(II), Cu(II), Cd(II) and Zn(II) were found to be 0.62, 0.23, 0.55, 0.27, 0.46, 0.21 and 0.25 mmol g(-1) of the resin, respectively. The lower limit of detection was 10 ng ml(-1) for Cd(II), 40 ng ml(-1) for Mn(II) and Zn(II), 32 ng ml(-1) for Ni(II), 25 ng ml(-1) for Cu(II) and Co(II) and 20 ng ml(-1) for Pb(II). A high preconcentration value of 300 in the case of Mn(II), Co(II), Ni(II), Cu(II),Cd(II) and a value of 500 and 250 for Pb(II) and Zn(II), respectively, were achieved. A recovery of >98% was obtained for all the metal ions with 4 M HCl as eluting agent except in the case of Cu(II) where in 6 M HCl was necessary. The chelating polymer showed low sorption behavior to alkali and alkaline earth metals and also to various inorganic anionic species present in saline matrix. The method was applied for metal ion determination from water samples like seawater, well water and tap water and also from green leafy vegetable, from certified multivitamin tablets and steel samples.

Selective enrichment of U(VI), Th(IV) and La(III) from high acidic streams using a new chelating ion-exchange polymeric matrix.

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 26cm(3)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 0.5M (NH(4))(2)CO(3) solution. The method was highly sensitive with lower limits of detections to be 10, 20 and 15ngcm(-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.

A COLUMN SYSTEM FOR THE SELECTIVE EXTRACTION OF U(VI) AND TH(IV) USING A NEW CHELATING SORBENT

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 (t(1/2)) 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.

Selective extraction of U(VI) over Th(IV) from acidic streams using di-bis(2-ethylhexyl) malonamide anchored chloromethylated polymeric matrix

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 (13 )C 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 resins metal extractive behavior were studied by both static and dynamic method. Batch extraction studies performed over a wide range of solution acidity (0.01-10M) revealed that selective extraction of U(VI) could be achieved even up to 4M acidity with distribution ratios (D) in the order of approximately 10(3). The phase exchange kinetics studies performed for U(VI) and Th(IV) revealed that time duration of <15min 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 60min. The metal sorption studies performed for U(VI) and Th(IV) at 5M HNO(3) was found to be 62.5 and 38.2mgg(-1),respectively. Extraction efficiency in the presence of inferring electrolyte species and inorganic cations were also examined. Metal ion desorption was effective using 10-15mL of 1M (NH(4))(2)CO(3) or 0.5M alpha-hydroxy isobutyric acid (HIBA). Extraction studies performed on a chromatographic column at 5M 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%.

DAPPA grafted polymer: an efficient solid phase extractant for U(VI), Th(IV) and La(III) from acidic waste streams and environmental samples.

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, (31)P and (13)C-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 0.54mmolg(-1) for U(VI), 1.98, 0.63 and 0.42mmolg(-1) for Th(IV) and 1.22, 0.39 and 0.39mmolg(-1) for La(III) under optimum pH, HNO(3) and HCl concentration, respectively. The grafted polymer shows faster phase exchange kinetics (<5min 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 1M (NH(4))(2)CO(3), 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.

Extraction chromatographic method for the separation of actinides and lanthanides using EDHBA grafted AXAD-16 polymer

A new extraction chromatographic method has been developed by grafting chloromethylated polymer support with 4-ethoxy-N,N-dihexylbutanamide (EDHBA), for the selective extraction of U(VI), Th(IV), La(III) and Nd(III) from highly acidic matrices. The developed grafted polymer has been characterized using (13)C-CPMAS NMR spectroscopy, FT-NIR spectroscopy and also by CHN elemental analysis. The water regaining capacity of the grafted polymer is studied by TGA measurements and the active participation of the amide moiety towards metal ion complexation has been confirmed by Far IR spectroscopy. For the quantitative extraction of metal ions to the resin phase, various physio-chemical parameters are optimized by both static and dynamic methods. The developed amide grafted polymeric matrix shows good distribution ratio values even at high acidities, with the maximum metal sorption capacity values being 0.36, 0.69, 0.32 and 0.42mmolg(-1) for U(VI), Th(IV), La(III) and Nd(III), respectively, at 6M HNO(3) medium. The kinetics of metal ion phase equilibration is found to be moderately fast, with t(1/2) values of <6min, for all the analytes of interest. The limits of analyte quantification (LOQ) using the developed method are in the range of 15-30mugL(-1). Moreover, the sequential separation of the sorbed actinides and lanthanides could be achieved by first eluting with 100mL of distilled water (for actinides) followed by elution with 20mL of 0.1M EDTA (for lanthanides). The selectivity behavior and the practical applicability of the developed resin are tested using synthetic low level nuclear reprocessing mixtures and also with monazite sand. The analytical data are within 3.8% relative standard deviation, reflecting the reproducibility and reliability of the developed method.

New Multi‐Dentate Ion‐Selective AXAD‐16‐MOPPA Polymer for the Preconcentration and Sequential Separation of U(VI), Th(IV) from Rare Earth Matrix

Abstract A new class of multi‐dentate ligand anchored polymeric resin has been synthesized by grafting Amberlite XAD‐16 with [2‐(1‐Methyl‐3‐oxo‐2‐phenyl‐2, 3‐dihydro‐1H‐pyrazol‐4‐ylcarbamoyl)‐ethyl]‐phosphinic acid (AXAD‐16‐MOPPA). The modification steps involved during the grafting process are characterized by FT‐IR spectroscopy, 31P and 13C‐CPMAS (cross‐polarized magic angle spin) NMR spectroscopy, CHNPS elemental analysis and thermogravimetric analysis. The influence of various physio‐chemical parameters on the quantitative extraction of metal ions by the resin phase are studied and optimized by both static and dynamic methods. The developed grafted polymer shows greater selectivity for actinide ions like U(VI) and Th(IV) when compared to the lanthanides with greater distribution ratio values in highly acidic matrices. However, the lanthanides compete for the active sites in near neutral conditions. But the sorbed actinide ions and lanthanide elements can be separated by the sequential elution methodology. Moreover, the polymer exhibits faster metal ion phase exchange kinetics, where with a high sample flow rate of 25 mL min−1 quantitative analyte sorption is achievable during the extraction chromatographic column operation for all the analytes. It also offers good ion‐selectivity and greater preconcentration factor values of 400 for U(VI) and 333 for Th(IV) in 4M HNO3 conditions. The resin shows very high sorption capacity values of 1.45 mmol g−1 for U(VI), 1.39 mmol g−1 for Th(IV), and 1.31 mmol g−1 for La(III) at near neutral conditions. Finally, the developed grafted resin has been successfully applied in extracting Th(IV) from matrix monazite sand which comprises large rare earth matrix, U(VI) from seawater and also U(VI) and Th(IV) from simulated nuclear spent fuel mixtures. The analytical data obtained from triplicate measurements are within 3.5% rsd, reflecting the reproducibility and reliability of the developed method.

Enhanced metal extractive behavior using dual mechanism bifunctional polymer: an effective metal chelatogen

A new class of chelating polymers using Amberlite XAD-16 (AXAD-16) modified with (N-(3,4-dihydroxy)benzyl)-4-amino,3-hydroxynapthalene-1-sulphonic acid has been developed based on dual mechanism bifunctional polymers, for the extraction of transition and post-transition metal ions. The optimum pH conditions for the quantitative sorption of metal ions were studied. The developed method showed superior extraction qualities with high metal loading capacities of 71, 85, 182, 130 and 46 mg g(-1) for Ni(II), Cd(II), Pb(II), Cu(II) and Co(II), respectively. The rate of metal ion uptake i.e. kinetics studies performed under optimum levels showed a time duration of <5 min except for Co(II) which required 20 min, for complete metal ion saturation. Desorption of metal ions were effective with 15 ml of 2 M HCl/HNO(3) prior to detection using flame atomic absorption spectrophotometer. The chelating polymer was highly ion-selective in nature even in the presence of large concentrations of alkali and alkaline earth metal ions, with a high preconcentrating ability for the metal ions of interest. The developed chelating matrix was tested on its utility with synthetic and real samples like river/sea/tap/well water samples and also with multivitamin/mineral tablets, showed R.S.D. values of <2.5% reflecting on the accuracy and reproducibility of data using the newly developed resin matrix.

New Multidentate Ion‐Selective Grafted Polymer for Preconcentration of Lanthanides and Actinides

Abstract A new chelating ion‐exchange multidentate grafted polymer has been developed by anchoring 6,6,6‐trifluoro‐2,5‐dioxo‐4‐(thiophene‐2‐carbonyl) hexyl phosphinic acid (TDHCHPA), a multidonor ligand moiety to polystyrene divinylbenzene copolymer beads (Amberlite XAD‐16) and characterized by various spectroscopic techniques. An extraction chromatographic method is preferred for the separations of lanthanides and actinides from samples of both high acidity and near neutrality. It exhibits superior sorption capacities, with high distribution ratio values of >103 even in 3M acidities. Dual mechanism bifunctionality of the polymer enables fast exchange kinetics. Its practical utility has been tested using simulated nuclear spent fuel mixtures, monazite sand, and seawater samples (4.1% rsd, triplicate measurements).

Synthesis, Characterization, and Metal Extractive Behavior of Functionalized AXAD-16 Polymeric Matrix Using Oxyacetone Acetamide

Abstract A new metal chelating polymer has been synthesized using Amberlite XAD‐16 (AXAD‐16) polymer matrix, chemically modified using oxyacetone acetamide as the functional group. The resin was characterized by Fourier transform‐infra red (FT‐IR) studies, elemental analysis, and thermogravimetric analysis. The metal extractive efficiency of the functionalized resin matrix was examined and it was found that the synthesized resin showed high selectivity and preconcentrating ability toward trace heavy metal ions. Various physiochemical and kinetic factors operating on the quantitative metal ion extraction were studied and optimized. It was found that quantitative metal ion sorption was possible in the pH range of 5.0–7.0, 3.0–4.0, 5.0, and 6.0–7.0 for U(VI), Th(IV), Pb(II), and Cd(II), respectively. The developed resin showed faster exchange rates and a high metal exchange capacity value of 202, 185, 179, and 86 mg g−1 for U(VI), Th(IV), Pb(II), and Cd(II), respectively. The newly synthesized resin possesses improved metal extraction efficiency as revealed by the flow rate and kinetic studies, with complete metal ion saturation effective in <15 min, with a t 1/2 value of <5 min, for all the metal ions of interest. The ion‐selective behavior of developed resin was tested using various interfering electrolyte and metal ion species and was found to have greater tolerance toward these matrix species in the process of quantitative trace metal ion recovery down to the parts per billion ppb level. A high preconcentration factor value of 400 was achieved for U(VI), Th(IV), and Cd(II), respectively, and 500 in the case of Pb(II). The developed method was tested on its metal preconcentration ability, using synthetic and real samples. The system showed reproducibility and reliability in analytical data, with an rsd value of <4.1% on triplicate measurements.