Madhuri J. Kulkarni

Chemical separation and ICP–AES determination of 22 metallic elements in U and Pu matrices using cyanex-923 extractant and studies on stripping of U and Pu

Comprehensive studies have been carried out on the extraction behavior of uranium and plutonium matrices using cyanex-923 extractant. The near total extraction of U/Pu and quantitative separation of 22 metallic elements at trace levels has been established using inductively coupled plasma-atomic emission spectrometry (ICP-AES). The studies carried out on back extraction of U/Pu from organic phase have established the near total recovery of these matrices into the aqueous phase using 1 M Na(2)CO(3) and saturated oxalic acid, respectively.

Selective volatilisation of trace metals from refractory solids into an inductively coupled plasma

Abstract Feasibility studies have been carried out on the use of a graphite electrode assembly for the introduction of U3O8 solid samples into a continuously running low-powered argon inductively coupled plasma for the assay of trace metallic elements in uranium. The d.c. arc carrier distillation procedure has been adopted here for the selective volatilisation of analyte elements from the refractory matrix by injecting analyte vapours into the central zone of the plasma using Scribner-Mullin electrodes covered with a graphite lid having a central opening. The experimental parameters have been optimised for the direct determination of B, Be, Cd, Co, Cr, Cu, Fe, K, Li, Mn, Na, Ni and Pb in U3O8 powders. The analytical performance of the method has been checked by analysing spiked U3O8 samples and is seen to be comparable to or better than d.c. arc methods for these analytes. These results indicate that the carrier-distillation-ICP combination shows promise as a sensitive and precise method for analysis of trace metallic elements in a refractory matrix with a complex spectrum.

ICP-AES determination of silver after chemical separation from uranium matrix

The separation of silver from a uranium matrix has been carried out using Cyanex-471X (triisobutylphosphine sulphide) in xylene. The effects of various parameters such as the Cyanex-471X concentration, the nitric acid molarity, the contact time and the nitrate ion concentration on the extraction of silver have been studied. The silver metal ion species extracted into the organic phase was found to be Ag(NO(3)).2S (where S is Cyanex-471X). The stripping of silver into an aqueous medium was carried out with 5% NaHSO(3), followed by its determination using ICP-AES.

Carrier distillation-ICAP approach for trace metal assay of U3O8 powder

ZusammenfassungDas Trägerdestillationsverfahren zur selektiven Verdampfung von Spurenmetallen in U3O8 im Gleichstrombogen wurde mit induktiver Probeerhitzung für ICAP angepaßt. Die experimentellen Parameter wurden für die direkte Bestimmung von Cd, Cu, K, Na, Ni und Pb optimiert. Die Leistungsfähigkeit des Verfahrens wurde mit Hilfe von Proben mit bestimmten Zusätzen sowie mit zertifiziertem Referenzmaterial überprüft (Standardabweichung 2–9%). Durch die Verbindung der Vorteile von Trägerdestillation und ICAP bietet sich eine Methode von hoher Präzision.SummaryA new approach for the trace metal assay of U3O8 powder has been described. The carrier distillation technique used for selective volatilization of trace metals in U3O8 with d.c. arc excitation is adapted for the release of analytes from the solid sample into the ICAP source by inductively heating the sample. The experimental parameters have been optimised for the direct determination of Cd, Cu, K, Na, Ni and Pb. The performance of the method developed here is tested for the precision and accuracy of determinations by analysing spiked U3O8 samples and NBL U3O8 reference standards (standard deviation 2–9%). The method appears promising to be developed as a highly precise analytical optical emission spectrometric method as it adds to the ingenuity of the carrier distillation method, the advantages of ICAP.

Direct determination of beryllium, cadmium, lithium, lead and silver in thorium nitrate solution by electrothermal atomization atomic absorption spectrometry

Abstract An electrothermal atomization atomic absorption spectrometric (ET-AAS) method is developed for the direct determination of Ag,Be,Cd,Li and Pb in thorium nitrate solution. The method offers detection of sub-nanogram amounts of these analytes in 100 microgram thorium samples with a precision of around 10%. A number of spiked samples and pre-analysed Th02 samples have been analysed to evaluate the performance of the analytical methods developed here.

Trace metal assay of U3O8 powder by electrothermal AAS

Methods have been developed for the direct determination of Ag, Ca, K., Li, Mg, Na, Pb, Sn and Zn in U(3)O(8) powder samples by electrothermal AAS. Nanogram and lower amounts of these elements have been determined with a relative standard deviation of 6-16% in mg amounts of sample (either alone or mixed with an equal weight of graphite). The results for NBL reference samples were in reasonable agreement with the certified values. X-Ray diffraction studies on the residues left from the graphite mixtures after the atomization cycle, confirmed the formation of uranium carbide (UC(2)).

INTER-ELEMENT INTERFERENCE STUDIES IN THE DETERMINATION OF TRACE AMOUNTS OF PLUTONIUM BY INDUCTIVELY COUPLED PLASMA : ATOMIC EMISSION SPECTROMETRY

Abstract Trace amounts of plutonium in aqueous solutions have been determined by an inductively coupled argon plasma-atomic emission spectrometric (ICP-AES) technique. Extensive studies have been carried out on interelement interference effects for two plutonium lines, viz., 300.06 nm and 453.6 nm, due to the presence of uranium, thorium, lanthanides and other metallic elements in the sample solutions. The analytical range obtained in the present case is 0.1–100 μg/ml with a precision of better than 1% R.S.D. The method ie checked for accuracy by analyzing two wellcharacterizd reference rtandards.

Spectographic determination of trace metallic elements in uranium using a mixed carrier: Ga2O3 and SrF2

ZusammenfassungFür die spektrographische Bestimmung von metallischen Verunreinigungen einschließlich Silber in Uran wurde ein Ersatz für den AgCl-Träger gesucht. Bei diesen Untersuchungen wurden auch die Bogenplasmaparameter für verschiedene Träger bestimmt. Als optimal ergab sich eine Mischung mit 6% Ga2O3 und SrF2 im Verhältnis 2∶1. Eine Trägerdestillationsmethode für die Bestimmung von 23 Elementen in einer 50 mg-Probe wurde entsprechend standardisiert. Die Genauigkeit ist in den meisten Fällen besser als 18%.SummaryDetailed investigations have been carried out to find a suitable alternative to the AgCl carrier for the estimation of a wide range of trace metallic elements including silver in uranium. These studies also include determination of arc-plasma parameters for different carriers. Based on the results of these studies, a 6 % mixture of Ga2O3 and SrF2 in 2∶1 proportion has been found to be the best carrier. A “carrier distillation” emission spectrographic method has been standardised for estimation of twenty-three elements in uranium with 50 mg charge on the electrode using this carrier. The precision of the method is 18% or better for most of the elements.

Direct AAS determination of Co, Cr, Cu, Mn and Ni in U3O8 by electrothermal atomization

ZusammenfassungDas entwickelte AAS-Verfahren geht von pulverförmigen 5mg-Proben aus. Nanogramm-Mengen der genannten Elemente können mit einer Genauigkeit im Bereich von 7–12% bestimmt werden. Die durch U3O8 verursachte unspezifische Absorption ist zu vernachlässigen. Durch Graphitzusatz (in der gleichen oder doppelten Menge der Probe) wird die Empfindlichkeit der Bestimmung verbessert und die Lebensdauer des Atomizers verlängert.SummaryAn atomic absorption spectrometric method has been developed for the determination of chromium, cobalt, copper, manganese and nickel in U3O8 by electrothermal atomization of 5 mg powder samples. Nanogram amounts of all the elements can be estimated with a precision ranging between 7–12%. The non-specific absorption due to U3O8 for these measurements is negligible. The use of graphite powder with U3O8 in equal or double the sample amount improves sensitivity for the analyte element and prolongs the life of the atomizer.

Evaluation of terrestrial plants extracts for uranium sorption and characterization of potent phytoconstituents.

Abstract Sorption capacity of four plants (Funaria hygrometrica, Musa acuminata, Brassica juncea and Helianthus annuus) extracts/fractions for uranium, a radionuclide was investigated by EDXRF and tracer studies. The maximum sorption capacity, i.e., 100% (complete sorption) was observed in case of Musa acuminata extract and fractions. Carbohydrate, proteins, phenolics and flavonoids contents in the active fraction (having maximum sorption capacity) were also determined. Further purification of the most active fraction provided three pure molecules, mannitol, sorbitol and oxo-linked potassium oxalate. The characterization of isolated molecules was achieved by using FTIR, NMR, GC-MS, MS-MS, and by single crystal-XRD analysis. Of three molecules, oxo-linked potassium oxalate was observed to have 100% sorption activity. Possible binding mechanism of active molecule with the uranyl cation has been purposed.