IJAMSC  Vol.1 No.1 , September 2013
Separation Behavior of U(VI) and Th(IV) on a Mixed Ion Exchange Column Using 2,6-Pyridine Dicarboxylic Acid as a Complexing Agent and Determination of Trace Level Thorium in Uranium Matrix Employing High Performance Ion Chromatography
ABSTRACT

Retention behavior of U(VI) and Th(IV) as their 2, 6-pyridine dicarboxylic acid (PDCA) complexes on reversed phase and ion exchange (cation, anion and mixed ion exchange) columns was studied and based on the results, a simple ion chromatography method for the determination of trace level thorium in uranium oxide using 0.075mM 2, 6-pyridine dicarboxylic acid (PDCA) and 1M KNO3 in 1.2M HNO3 as eluent (flow rate 1 mL/min)was proposed. The advantage of the developed method is that the separation of uranium matrix is not required prior to the ion chromatographic determination of trace Th. Separation was carried out on a mixed ion exchange stationary phase and a 10?4 M arsenazo (III) solution was used as post column reagent for detecting the separated metal ions. The separation of Th from uranium using PDCA in the present investigation is attributed through cation exchange mechanism. A calibration plot was constructed by following the standard addition method over the concentration range of 0.25 to 10 ppm of Th in the presence of uranium matrix, which resulted in a linear regression coefficient of 0.9978. The precision of the method was better than 5% and the LOD for Th was found to be 0.1ppm (S/N=3). The method has been validated by comparing the results with the results obtained from ICP-MS analysis where the This separated from the uranium matrix. The proposed method is simple, rapid, accurate and cost effective compared to techniques like ICP-MS or ICP-AES and is suitable for the routine kind of analysis.


Cite this paper
V. Raut, V. , P. Roy, S. , K. Das, M. , Jeyakumar, S. and L. Ramakumar, K. (2013) Separation Behavior of U(VI) and Th(IV) on a Mixed Ion Exchange Column Using 2,6-Pyridine Dicarboxylic Acid as a Complexing Agent and Determination of Trace Level Thorium in Uranium Matrix Employing High Performance Ion Chromatography. International Journal of Analytical Mass Spectrometry and Chromatography, 1, 61-71. doi: 10.4236/ijamsc.2013.11008.
References
[1]   H. J. Bhabha and N. B. Prasad, “A Study of the Contribution of Atomic Energy to a Power Programme in India,” Proceedings of the Second United Nations International Conference on the Peaceful Uses of Atomic Energy, Geneva, Vol. 1, September 1958, pp. 89-101.

[2]   M. Dayal, S. R. Paranjape, B. Singh and N. B. Prasad, “Study of Fuel Cycles with Reference to a Power Programme,” Proceedings of the Second United Nations International Conference on the Peaceful Uses of Atomic Energy, Geneva, Vol. 13, September 1958, pp. 184-194.

[3]   T. K. Mukherjee, “Characterization and Quality Control of Nuclear Fuels (CQCNF-2002),” Allied Publishers, New Delhi, 2003.

[4]   IAEA-TECDOC-1450, “Thorium Fuel Cycle-Potential Benefits and Challenges”, IAEA, Austria, 2005, pp. 68- 69.

[5]   V. Venugopal, “Chemical Quality Control of Nuclear Materials,” Indian Association for Nuclear Scientists and Allied Chemists (IANCAS) Bulletin, Vol. 4, Mumbai, 2005.

[6]   S. Joannon, P. Telouk, C. Pin, “Determination of U and Th at Ultra-Trace Levels by Isotope Dilution Inductively Coupled Plasma Mass Spectrometry Using a Geyser- Type Ultrasonic Nebulizer: Application to Geological Samples,” Spectrochimica Acta B, Vol. 52, No. 12, 1997. pp. 1783-1789. http://dx.doi.org/10.1016/S0584-8547(97)00072-4

[7]   A. G. Adriaens, J. D. Fassett, W. R. Kelly, D. S. Simons and F. C. Adams, “Determination of Uranium and Thorium Concentrations in Soils: Comparison of Isotope Dilution-Secondary Ion Mass Spectrometry and Isotope Dilution-Thermal Ionization Mass Spectrometry,” Analy- tical Chemistry, Vol. 64, No. 23, 1992, pp. 2945-2950. http://dx.doi.org/10.1021/ac00047a012

[8]   E. H. Borai and A. S. Mady, “Separation and Quantification of 238U, 232Th and Rare Earths in Monazite Samples by Ion Chromatography Coupled with On-Line Flow Scintillation Detector,” Applied Radiation and Isotopes, Vol. 57, No. 4, 2002. pp. 463-469. http://dx.doi.org/10.1016/S0969-8043(02)00089-1

[9]   S. B. Deb, M. K. Saxena, B. K. Nagar and K. L. Rama-kumar, “Determination of Trace Amounts of Thorium in a Uranium Matrix by Inductively Coupled Plasma Mass Spectrometry and Validation of the Separation Procedure by Standard Addition and Tracer Techniques,” Atomic Spectroscopy, Vol. 29, No. 2, 2008, pp. 39-44.

[10]   F. Hao, B. Paull and P. R. Haddad, “Determination of Thorium and Uranyl in Nitrophosphate Solution by OnLine Matrix-Elimination Reversed-Phase Chromatography,” Chromatographia, Vol. 42, No. 11-12, 1996, pp. 690-696. http://dx.doi.org/10.1007/BF02267703

[11]   F. Hao, B. Paull and P. R. Haddad, “Determination of Trace Levels of Thorium(IV) and Uranyl by Reversed- Phase Chromatography with On-Line Preconcentration and Ligand Exchange,” Journal of Chromatography A, Vol. 749, No. 1-2,1996, pp. 103-113. http://dx.doi.org/10.1016/0021-9673(96)00450-5

[12]   R. M. Cassidy, “Determination of Rare-Earth Elements in Rocks by Liquid Chromatography,” Chemical Geology, Vol. 67, No. 3-4, 1998. pp. 185-195. http://dx.doi.org/10.1016/0009-2541(88)90127-1

[13]   P. E. Jackson, J. Carnevale, H. Fuping and P. R. Haddad, “Determination of Thorium and Uranium in Mineral Sands by Ion Chromatography,” Journal of Chromatography A, Vol. 671, No. 1-2, 1996, pp. 181-191. http://dx.doi.org/10.1016/0021-9673(94)80237-8

[14]   R. M. C Sutton, S. J. Hill, P. Jones, A. Sanz-Medel and J. I. Garcia-Alonso, “Comparison of the Retention Behaviour of Uranium and Thorium on High-Efficiency Resin Substrates Impregnated or Dynamically Coated with Metal Chelating Compounds,” Journal of Chromatography A, Vol. 816, No. 2, 1998, pp. 286-291. http://dx.doi.org/10.1016/S0021-9673(98)00496-8

[15]   R. M. Cassidy and M. Fraser, “Equilibria Effects in the Dynamic Ion-Exchange Separation of Metal Ions,” Chromatographia, Vol. 18, No. 7, 1984, pp. 369-373. http://dx.doi.org/10.1007/BF02262483

[16]   P. Jones and P. N. Nesterenko, “High-Performance Chelation Ion Chromatography a New Dimension in the Separation and Determination of Trace Metals,” Journal of Chromatography A, Vol. 789, No. 1-2, 1997, pp. 413-435. http://dx.doi.org/10.1016/S0021-9673(97)00824-8

[17]   Ch. S. K. Raju, M. S. Subramanian, N. Sivaraman, T. G. Srinivasan and P. R. Vasudeva Rao, “Retention Studies on Uranium, Thorium and Lanthanides with Amide Modified Reverse Phase Support and Its Applications,” Journal of Chromatography A, Vol. 1156, No. 1-2, 2007, pp. 340-347. http://dx.doi.org/10.1016/j.chroma.2007.01.010

[18]   M. Akhila Maheswari, D. Prabhakaran, M. S. Subramanian, N. Sivaraman, T. G. Srinivasan and P. R. Vasudeva Rao, “High Performance Liquid Chromatographic Studies on Lanthanides, Uranium and Thorium on Amide Modified Reversed Phase Supports,” Talanta, Vol. 72, No. 2, 2007, pp. 730-740. http://dx.doi.org/10.1016/j.talanta.2006.12.003

[19]   F. Hao, B. Paull and P. R. Haddad, “Retention Behaviour of Thorium(IV) and Uranyl on a Reversed-Phase Column with Glycolate and Mandelate as Eluents,” Journal of Chromatography A, Vol. 739, No. 1-2, 1996, pp. 151-161. http://dx.doi.org/10.1016/0021-9673(96)81462-2

[20]   M. J. Shaw, S. J. Hill and P. Jones, “Chelation Ion Chromatography of Metal Ions Using High Performance Substrates Dynamically Modified with Heterocyclic Carboxylic Acids,” Analytica Chimica Acta, Vol. 401, No. 1-2, 1999, pp. 65-71. http://dx.doi.org/10.1016/S0003-2670(99)00495-X

[21]   P. Jones, “Major Sensitivity Improvements in Ion Chromatography Determinations Involving Post-Column Spectrophotometric Reaction Detectors through Elimination of Pump Noise Using a Dual Wavelength Monitoring Procedure,” Analyst, Vol. 125, No. 5, 2000, pp. 803-806. http://dx.doi.org/10.1039/b001826k

[22]   M. J. Shaw, S. J. Hill, P. Jones and P. N. Nesterenko, “Determination of Uranium in Environmental Matrices by Chelation Ion Chromatography Using a High Performance Substrate Dynamically Modified with 2,6-Pyridinedi- carboxylic Acid,” Chromatographia, Vol. 51, No. 11-12, 2000, pp. 695-700. http://dx.doi.org/10.1007/BF02505407

[23]   S. Jeyakumar, V. G. Mishra, M. K. Das, V. V. Raut, R. M. Sawant and K. L. Ramakumar, “Separation Behavior of U(VI) and Th(IV) on a Cation Exchange Column Using 2,6-Pyridine Dicarboxylic Acid as a Complexing Agent and Its Application for the Rapid Separation and Determination of U and Th by Ion Chromatography,” Journal of Separation Science, Vol. 34, No. 6, 2011, pp. 609-616. http://dx.doi.org/10.1002/jssc.201000907

[24]   J. Cowan, M. J. Shaw, E. P. Achterberg, P. Jones and P. N. Nesterenko, “The Ion Chromatographic Separation of High Valence Metal Cations Using a Neutral Polystyrene Resin Dynamically Modified with Dipicolinic Acid,” Analyst, Vol.125, No. 12, 2000, pp. 2157-2159. http://dx.doi.org/10.1039/b008235j

[25]   “Determiantion of Uranium and Thorium in Complex Matrices Using Chelation Ion Chromatography,” Dionex Application Note, No. 79, 1998, LPN 034670-01.

[26]   A. W. Al-Shawi and R. Dahl, “Determination of Thorium and Uranium in Nitrophosphate Fertilizer Solution by Ion Chromatography,” Journal of Chromatography A, Vol. 706, No. 1-2, 1995. pp. 175-181. http://dx.doi.org/10.1016/0021-9673(95)00006-9

[27]   M. P. Harrold, A. Siriraks and J. Riviello, “High-Performance Ion Chromatographic Separation of Uranium and Thorium in Natural Waters and Geological Materials,” Journal of Chromatography A, Vol. 602, No. 1-2, 1992, pp. 119-125. http://dx.doi.org/10.1016/0021-9673(92)80071-2

[28]   F. Nelson, T. Murase and K. A. Kraus, “Ion Exchange Procedures. I. Cation Exchange in Concentration HCl and HClO4 Solutions,” Journal of Chromatography A, Vol. 13, 1964, pp. 503-535. http://dx.doi.org/10.1016/S0021-9673(01)95146-5

[29]   H. Hojabri, A. G. Lavin, G. G. Wallace and J. M. Riviello, “Determination of Metal Ions Using Ion Chromatography and Indirect Amperometric Detection,” Analytical Che- mistry, Vol. 59, No. 1, 1987, pp. 54-57. http://dx.doi.org/10.1021/ac00128a011

[30]   Y. S. Park, S. H. Han, K. S. Joe, T. Y. Eom and G. Lee, “Retention Behaviour of Transition Metal Ions with Some Complexing Agents on Cation Exchanger,” Bulletin of the Korean Chemical Society, Vol. 14, No. 6, 1993. pp. 692-696.

[31]   N. Cardellicchio, P. Ragone, S. Cavalli and J. Riviello, “Use of Ion Chromatography for the Determination of Transition Metals in the Control of Sewage-Treatment- Plant and Related Waters,” Journal of Chromatography A, Vol. 770, No. 1-2, 1997, pp. 185-193. http://dx.doi.org/10.1016/S0021-9673(97)00086-1

[32]   E. H. Borai, M. A. Eid and H. F. Aly, “Determination of REEs Distribution in Monazite and Xenotime Minerals by Ion Chromatography and ICP-AES,” Analytical and Bioanalytical Chemistry, Vol. 372, No. 4, 2002, pp. 537- 541. http://dx.doi.org/10.1007/s00216-001-1204-8

[33]   L. Perna, F. Bocci, L. Aldave de las Heras, J. De Pablob and M. Betti, “Studies on Simultaneous Separation and Determination of Lanthanides and Actinides by Ion Chromatography Inductively Coupled Plasma Mass Spectrometry Combined with Isotope Dilution Mass Spectrometry,” Journal of Analytical Atomic Spectrometry, Vol. 17, 9, 2002, pp. 1166-1171. http://dx.doi.org/10.1039/b202451a

[34]   P. Janvion, S. Motellier and H. Pitsch, “Ion-Exchange Mechanisms of Some Transition Metals on A Mixed-Bed Resin with a Complexing Eluent,” Journal of Chromatography A, Vol. 715, No. 1, 1995, pp. 105-115. http://dx.doi.org/10.1016/0021-9673(95)00576-9

[35]   M. Xavier, P. R. Nair, K. V. Lohithakshan, S. G. Marathe and H. C. Jain, “Determination of Uranium in the Presence of Iron and Plutonium by Ti(III) Reduction and Biamperometric Titration,” Journal of Radioanalytical and Nuclear Chemistry, Vol. 148, No. 2, 1991, pp. 251- 256. http://dx.doi.org/10.1007/BF02060358

[36]   L. G. Sillen and A. E. Martell, “Stability Constants of Metal Ion Complexes, spl,” Chemical Society, London, 1964, p. 545.

[37]   P. R. Haddad and R. C. Foley, “Modelling of Cation Retention in Ion Chromatography Using Fixed-Site and Dynamically Coated Ion-Exchange Columns,” Journal of Chromatography A, Vol. 500, 1990, pp. 301-312. http://dx.doi.org/10.1016/S0021-9673(00)96073-4

[38]   A. E. Martell and R. M. Smith “Critical Stability Constants,” Vol. I, Amino Acids, Plenum, New York, 1974, p. 377.

[39]   “DAE-Interlaboratory Comparison Experiment (ILCE) for Trace Metal Assay of Uranium,” Phase 2, Document, BARC, India, 2002.

[40]   V. R. Bhandiwad, R. Swarup and S. K. Patil, “Extraction of Actinides by Quaternary Amines from Hydrochloric Acid Medium,” Journal of Radioanalytical Chemistry, Vol. 52, No. 1, 1979, pp. 5-14. http://dx.doi.org/10.1007/BF02517694

 
 
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