Membrane optode for uranium(VI) ions preconcentration and quantification based on a synergistic combination of 4-(2-thiazolylazo)-resorcinol with 8-hydroxyquinaldine.

A membrane optode was developed utilizing the 8-hydroxyquinaldine (HQ) facilitated preconcentration of UO(2)(2+) ions and subsequent colored complex formation of UO(2)(2+) with 4-(2-thiazolylazo)-resorcinol (TAR) in optode matrix. The composition of the membrane optode was optimized by scanning several extractants immobilized in different plasticized polymer matrices. It was observed that the chelating agent HQ along with an indicator TAR immobilized in the tri-(2-ethylhexyl)phosphate (TEHP) plasticized cellulose triacetate matrix (CTA) was best suited as an optode for the UO(2)(2+) ions in aqueous samples. On sorption of UO(2)(2+) in the optode matrix, TAR changes color of the optode from yellow to magenta having a maximum absorbance (lambda(max)) at 546 nm. The uptake of UO(2)(2+) ions in the optode was found to be pH dependent and was maximum (>90%) at pH above 3. The acetate buffer (0.1 mol L(-1) sodium acetate + 0.1 mol L(-1) acetic acid) was found to be necessary for the stable response. The optimum equilibration time for the optode (2 cm x 1 cm) was found to be 30 min in 10 mL aqueous sample containing acetate buffer (pH 4.75). The equilibration time was found to increase with increase in aqueous sample volume. The optode response was found to be linear in the UO(2)(2+) ions concentration range of 0.01-0.11 micromol L(-1) in tap water as well as aqueous solutions containing 0.1 mol L(-1) NaCl or NaNO(3). The tolerance to the presence of several cations and anions in the determination of UO(2)(2+) ion was studied. It was observed that the optode in the presence of buffer can tolerate presence of large amounts of interfering cations (Ce(4+), V(4+), Eu(3+), Al(3+), Fe(3+), Ni(2+), Cd(2+), Co(2+), Pb(2+), Hg(2+), Cu(2+) and Th(4+) ions) without hindering the sorption of UO(2)(2+) ions in the optode matrix. The present work indicated that 50 ppb UO(2)(2+) ions in 100 mL sample can easily be quantified using this optode. The optode was found to be fully reversible, can readily be regenerated by equilibrating it with 0.1 mol L(-1) HNO(3) and reusable up to three cycles. The applicability of the developed optode in real samples was studied by determining uranium in the ground water samples spiked with a known quantity of UO(2)(2+) ions.

Membrane optode for mercury(II) determination in aqueous samples.

A color changeable optode for Hg(II) was prepared by the immobilization of a dye 4-(2-pyridylazo)resorcinol (PAR) and a liquid ion-exchanger trioctylmethylammonium chloride (Aliquat-336) in the tri-(2-ethylhexyl) phosphate plasticized cellulose triacetate matrix. Hg(II) and CH(3)Hg(+) from aqueous samples could be quantitatively preconcentrated in this transparent optode producing a distinct color change (lambda(max)=520 nm) within 5 min equilibration time in bicarbonate aqueous medium or 30 min in natural water. Whereas optode sample without Aliquat-336 did not change its color corresponding to Hg-PAR complex on equilibrium with the same aqueous solution containing Hg(II) ions. The uptake of Hg(II) was found to be pH dependent with a maximum (>90%) at a pH 7.5. The uptake of ions like Cu(II), Fe(II), Zn(II) and Pb(II) was negligible in the optode where as the uptake of Cd(II) and Zn(II) ions was 10-15% at pH 7.5. The optode developed in the present work was studied for its analytical application for Hg(II) in the aqueous samples by spectrophotometry, radiotracer ((203)Hg), Energy Dispersive X-ray Fluorescence (EDXRF) analyses and Instrumental Neutron Activation Analysis (INAA). The minimum amount of Hg(II) required to produce detectable response by spectrophotometry, INAA and EDXRF were found to be 5.5, 1 and 12 microg, respectively. This optode showed a linear increase in the absorbance at lambda(max)=520 nm over a concentration range of 0.22-1.32 microg/mL of Hg(II) ions in aqueous solution for 5 min. The preconcentration of Hg(II) from large volume of aqueous solution was used to extend the lower limit of concentration range that can be quantified by the spectrophotometry of optode. It was observed that preconcentration of 11 microg Hg(II) in 100mL (0.11 microg/mL) in aqueous samples gives a distinct color change and absorbance above 3 sigma of the blank absorbance. The optode developed in the present work was found to be reusable.

Design of two-dimensional biomimetic uranyl optrode and its application to the analysis of natural waters.

A two-dimensional biomimetic optrode for the detection and quantification of uranium in natural waters was fabricated. The sensing element was designed by the inclusion of uranyl ion imprinted polymer particles into polymethyl methacrylate followed by casting a thin film on a glass slide without any plasticizer. The ion imprinted polymer material was prepared via covalent immobilization of the newly synthesised ligand 4-vinyl phenylazo-2-naphthol by thermal polymerization. Operational parameters such as pH, response time and the amount of sensing material were optimized. The response characteristics of the imprinted and the corresponding non-imprinted polymer inclusion optrodes of uranium were compared under optimum conditions. The imprinted polymer inclusion optrode responds linearly to uranium in the concentration range 0-1.0 microg mL(-1) with a detection limit of 0.18 microg mL(-1), which is much better than the solution studies using 4-vinyl phenylazo-2-naphthol (1.5 microg mL(-1)). Triplicate determinations of 100 microg of uranium(VI) present in 250 mL of solution gave a mean absorbance of 0.018 with a relative standard deviation of 8.33%. The superior sensitivity of imprinted polymer inclusion optrode is exemplified by lower detection limits and broader dynamic range over non-imprinted polymer inclusion optrode. The developed imprinted polymer inclusion optrode was found to give stable and precise response for 3 months and can be used without any loss in sensitivity. The applicability for analysing ground, lake and tap-water samples collected in the vicinity of uranium deposits was successfully demonstrated.

Dithiocarbamate functionalized or surface sorbed Merrifield resin beads as column materials for on line flow injection-flame atomic absorption spectrometry determination of lead.

This article describes the preparation of dithiocarbamate immobilized/functionalized and diethylammonium dithiocarbamate (DDTC) sorbed Merrifield Chloromethylated Resin (MCR) beads and comparison of these materials for on-line flow injection (FI)-flame atomic absorption spectrometry (FAAS) determination of lead. The above two materials enrich lead quantitatively over an identical optimal pH range (8.0-9.0), a preconcentration/loading time (up to 4 min) and elution with acidified methanol (a minimum of 0.01 molL(-1) HNO(3) in methanol). However, the detection limit for lead using dithiocarbamate functionalized MCR beads is 1.3 microgL(-1) compared to 3 microgL(-1) for DDTC sorbed MCR beads. Again, the sensitivity enhancement over direct FAAS signal is 48- and 27-fold, respectively. In addition, dithiocarbamate functionalized MCR beads offers better precision compared to DDTC sorbed MCR beads as the corresponding relative standard deviation (R.S.D.) values for five successive determinations of 0.20 microgmL(-1) are 1.44 and 4.36%, respectively. The accuracy of the developed on-line FI-FAAS procedure employing dithiocarbamate functionalized MCR beads as column material was tested by analyzing Certified Reference Material (CRM) of soil (IAEA soil-7) and marine sediment reference material (MESS-3) supplied by International Atomic Energy Agency (IAEA), Vienna and National Research Council (NRC), Canada, respectively. Furthermore, the developed procedure has been successfully tested for the analysis of surface, pond, ground and effluent water and soil samples collected from the vicinity of lead acid battery industry in India.

WITHDRAWN: Selective spectrophotometric determination of cobalt(II) in various environmental samples with 2-(chromen-2'-onyl)-5(4''-chlorophenyl)1,3,4-oxadiazole.

The present work describes a selective, rapid and economical spectrophotometric method for the determination of cobalt(II) in various environmental samples. The method is based on the formation of pink colored complex of a stoichiometric ratio 1:2 between cobalt(II) and 2-(chromen-2'-onyl)-5-(4''-chlorophenyl)1,3,4-oxadiazole at pH 6.0+/-0.2. The absorbance of the complex was measured spectrophotometrically at 542nm. Under the optical conditions, Beer's law was obeyed over the range of 0.5-14mugml(-1). The molar absorptivity and Sandell's sensitivity were 1.348x10(4)lmol(-1)cm(-1) and 0.004115mugcm(-2), respectively. The detailed study of various interferences made the method more selective. The method was successfully applied to the determination of cobalt(II) in various environmental samples. The performance of proposed method was evaluated in terms of Student's t-test and variance ratio f-test which indicates the significance of proposed method over reported method. Recoveries obtained revealed that the proposed procedure shows good accuracy at 98% confidence level.

Ion imprinted polymer based sensor for monitoring toxic uranium in environmental samples.

In view of the extreme toxicity of uranium and consequent stringent limits fixed by WHO and various national governments, it is essential to monitor the uranium content in the environment which is at ultratrace levels. Conventional ionophore based ion selective electrodes, barring a few, have limitations in terms of sensitivity and selectivity for the above mentioned purpose. We now propose an ion imprinted polymer (biomimetic) based potentiometric sensor by dispersing the uranyl ion imprinted polymer particles in 2-nitrophenyloctyl ether (plasticizer), which is embedded in polyvinyl chloride matrix. The sensor responds to uranyl ion over a wide concentration range of 2.0 x 10(-8) to 1.0 x 10(-2) M. The limit of detection was 2.0 x 10(-8) M. It showed a good selectivity for uranyl ion over alkali, alkaline earth, transition and heavy metal cations. The sensor is successfully tested for the monitoring of toxic uranium in tap and sea water samples.

Solid phase extraction vis-à-vis coprecipitation preconcentration of cadmium and lead from soils onto 5,7-dibromoquinoline-8-ol embedded benzophenone and determination by FAAS.

This article compares the solid phase extraction (SPE) and coprecipitative preconcentration of cadmium and lead from dilute aqueous solutions as a function of pH and weight of chelating agent. SPE enriches cadmium and lead over a wider pH range (6.0-8.0) and requires lower weight of DBQ chelate embedded benzophenone. Among the quinoline-8-ol and its dihaloderivatives, DBQ embedded benzophenone allows quantitative enrichment over a wide pH range (6.0-8.0) for both cadmium and lead unlike DCQ ( approximately 6.5 for Cd and 6.5-7.0 for Pb), DBQ was preferred. The calibration plots were rectilinear over the concentration range of 0.1-50 and 2.5-200mugl(-1) of cadmium and lead with detection limits of 0.1 and 2.0mugl(-1), respectively, which are 400 times lower than the direct FAAS method. The precision of the developed procedure is good as it provides relative standard deviation values of 2.20 and 2.45% during five replicate determinations of 2 and 25mugl(-1) of cadmium and lead, respectively. The accuracy of the developed procedure was tested by analyzing certified reference materials (CRM's) of soil and marine sediment samples supplied by IAEA, Italy and NRC, Canada, respectively. Furthermore, the developed procedure has been successfully used for the speciative determination of cadmium and lead in soil samples collected from the vicinity of industries in India.

Amberlite XAD-4 functionalized with succinic acid for the solid phase extractive preconcentration and separation of uranium(VI).

Amberlite XAD-4 resin has been functionalized with succinic acid by coupling it with dibromosuccinic acid after acetylation. The resulting resin has been characterized by FT-IR, elemental analysis and TGA and has been used for preconcentrative separation of uranium(VI) from host of other inorganic species prior to its determination by spectrophotometry. The optimum pH value for quantitative sorption of uranium(VI) in both batch and column modes is 4.5-8.0 and desorption can be achieved by using 5.0ml of 1.0moll(-1) HCl. The sorption capacity of functionalized resin is 12.3mgg(-1). Calibration graphs were rectilinear over the uranium(VI) concentrations in the range 5-200mugl(-1). Five replicate determinations of 50mug of uranium(VI) present in 1000ml of solution gave a mean absorbance of 0.10 with a relative standard deviation of 2.56%. The detection limit corresponding to three times the standard deviation of the blank was found to be 2mugl(-1). Various cationic and anionic species at 200-fold amounts do not interfere during the preconcentration of 5.0mug of uranium(VI) present in 1000ml (batch) or 100ml (column) of sample solution. Further, adsorption kinetic and isotherm studies were also carried out by a batch method to understand the nature of sorption of uranium(VI) with the succinic acid functionalized resin. The accuracy of the developed solid phase extractive preconcentration method in conjunction with Arsenazo III procedure was tested by analyzing marine sediment (MESS-3) and soil (IAEA soil-7) reference material. Further, the above procedure has been successfully employed for the analysis of soil and sediment samples.

Detection of lead in vegetables with new chromogenic reagent by spectrophotometry.

A new simple, rapid selective and highly sensitive chromogenic reagent dibromo-p-methyl-carboxyazo (DBMCA) was synthesized and studied in detail for the spectrophotometric detection of lead. In 0.25 M phosphoric acid medium, which greatly increases the selectivity, Lead reacts with DBMCA to form a 1:2 blue complex having a sensitivity absorption peak at 646 nm. Under optimal conditions, Beer's Law is obeyed over the range from 0.09 to 0.8 microg mL(-1) Pb (II) and the apparent molar absorptivity is 1.03 x 10(5) mL(-1) cm(-1). The detection limit and the variation coefficient were found to be 2.12 microg mL(-1) and 1.0% respectively. It is found that, except for Ca (II) and Ba (II) all foreign ions studied do not interfere with detection. The interference caused by Ca (II) and Ba (II) can be easily eliminated by prior extraction with potassiumiodide-methylisobutylketone. The proposed method has been applied successfully for to the detection of Lead in vegetable leaves with good results.

Preconcentrative separation of chromium(VI) species from chromium(III) by coprecipitation of its ethyl xanthate complex onto naphthalene.

A rapid, sensitive and selective method is described for the determination of chromium(VI) in presence of 100-fold amounts of chromium(III) by flame atomic absorption spectrometry (FAAS) in conjunction with coprecipitative preconcentration of its ethyl xanthate complex onto naphthalene. The solid mixture consisting of the chromium(VI) complex together with naphthalene is dissolved in 8.0ml of dimethyl formamide (DMF) and chromium(VI) content was established by FAAS. Calibration graphs were rectilinear over the chromium(VI) concentration in the range 0-200mugl(-1). Five replicate determinations of 20mug of chromium(VI) present in 1.0l of sample solution gave a relative standard deviation of 3.1%. The detection limit corresponding to three times the standard deviation of the blank was found to be 0.5mugl(-1). The developed procedure has been successfully utilized for the estimation of chromium(VI), chromium(total) (after oxidation with bromate) and chromium(III) (by subtracting chromium(VI) content from chromium(total) value contents of several tannery industries.

Analysis of samples of human serum with cataracts for zinc and iron by flame atomic absorption spectrometry.

Flame Atomic Absorption Spectrometer method has been used to determine Zinc and Iron in serum samples of humans with various cataracts. The method for the determination of Zinc includes the dilution of serum (1+9) with water soluble n-butanol 6% (v/v) and calibration with standards containing Zinc in 0.5%(v/v) HCl, diluted in the same way. The method for the determination of Iron includes deprotenization by diluting the serum (1+9) with trichloro acetic acid 5% (v/v). The values obtained for persons with several cataracts were compared with the values reported in the literature for normal persons. Further, the reliability of Flame Atomic Absorption Spectrometer method for the determination of Zinc and Iron in serum samples of humans with several cataracts was tested by inter-comparison with Inductively Coupled Plasma Atomic Emission Spectrometer.