Skip to main content
SpringerLink
Log in

γ-ray radiolysis of dihydroxyurea in nitric acid and its radiolytic products

  • Published:
Journal of Radioanalytical and Nuclear Chemistry Aims and scope Submit manuscript

Abstract

Dihydroxyurea (DHU) is a new salt-free reducing agent applied for the separation of Pu and Np from U in spent fuel reprocessing. This paper reports on the γ-ray radiolysis of DHU in HNO3 and its radiolytic products. DHU is relatively stable against radiation at the dose supposed to be absorbed in the separation of Pu and Np from U. The main radiolytic products are H2, CO2, N2O and \({\text{NH}}_{{4}}^{ + }\). The volume fraction of H2 increases with the dose, but decreases with increasing HNO3 concentration. The quantity of CO2, N2O and \({\text{NH}}_{{4}}^{ + }\) increases with the HNO3 concentration and the dose.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Natarajan R (2017) Reprocessing of spent nuclear fuel in India: present challenges and future programme. Prog Nucl Energy 101:118–132

    Article  CAS  Google Scholar 

  2. Choppin GR, Morgenstern AJ (2000) Radionuclide separations in radioactive waste disposal. J Radioanal Nucl Chem 243:45–51

    Article  CAS  Google Scholar 

  3. Schlea CS, Caverly MR, Henry HE, et al. (1963) Uranium (IV) nitrate as a reducing agent for plutonium (IV) in the Purex process. DP-808:1–20

  4. Sze YK, Clegg LJ, Gerwing AF et al (1982) Oxidation of Pu (III) by nitric acid in tri-n-butyl phosphate solutions. Part I. Kinetics of the reaction and its effect on plutonium losses in countercurrent liquid-liquid extraction. Nucl Technol 56:527–534

    Article  CAS  Google Scholar 

  5. Sze YK, Gosselin JA (1983) Oxidation of Pu (III) by nitric acid in tri-n-butyl phosphate solutions. Part II. Chemical methods for the suppression of oxidation to improve plutonium separation in contactor operation. Nucl Technol 63:431–441

    Article  CAS  Google Scholar 

  6. McKibben JM, Bercaw JE (1971) Hydroxylamine nitrate as a plutonium reductant in the purex solvent extraction process. No. DP-1248:1–22

  7. Zheng WF, Zhang ZF, Lin ZJ et al (2001) Study on separation of Np from U by acetohydroxamic acid in purex process. Chin J Nucl Sci Eng 21:369–374 ((in Chinese))

    Google Scholar 

  8. Ochsenfeld W, Petrich G, Schmidt HJ et al (1983) Neptunium decontamination in a uranium purification cycle of a spent fuel reprocessing plant. Sep Sci Technol 18:1685–1698

    Article  CAS  Google Scholar 

  9. Biddle P, Miles JH (1968) Rate of reaction of nitrous acid with hydrazine and with sulphamic acid: its application to nitrous acid control in two-phase industrial systems. J Inorg Nucl Chem 30:1291–1297

    Article  CAS  Google Scholar 

  10. Ye GA (2004) Application analysis of organic salt-free reagents in Purex process. Natl Ann Conf Nuclear Chem Chem Eng 02:152–158 ((in Chinese))

    Google Scholar 

  11. Taylor RJ, May I, Koltunov VS et al (1998) Kinetic and solvent extraction studies of the selective reduction of Np (VI) by new salt-free reducing agents. Radiochim Acta 81:149–156

    Article  CAS  Google Scholar 

  12. Ye GA (2004) Review on the study and application of organic salt-free reagent in purex process. Atom Energy Sci Technol 38:152–158 ((in Chinese))

    CAS  Google Scholar 

  13. Wang JH, Cao XJ, Li C et al (2015) Effect of HNO3 on the γ radiolysis and radiolytic liquid products of N, N-Dimethylhydroxylamine. Acta Phys Chim Sin 31:559–565

    Article  Google Scholar 

  14. Zhang AY, Hu JX, Zhang XY et al (2001) Hydroxylamine derivative in PUREX process. VI. Study on the partition of uranium/neptunium and uranium/plutonium with N, N-diethylhydroxylamine in the purification cycle of uranium contactor. Solvent Extr Ion Exch 19:965–979

    Article  CAS  Google Scholar 

  15. Miles JH (1989) Stabilization of an element against oxidation. UK Patent: 2216886

  16. Zhu ZW (2003) Study on the application of hydroxyurea-a salt-free agents in the Purex process. China Institute of Atomic Energy (in Chinese)

  17. Wang JL, Yan TH (2020) Development of distribution behavior of technetium in purex process. J Nuclear Radiochem 42:10–19 ((in Chinese))

    Google Scholar 

  18. Li Q (2013)γRadiation Stability and Radiolysis Products of Acetohydroxamic Acid and Dihydroxyurea. Shanghai University (in Chinese)

  19. Yan TH, Zhen WF, Ye GA et al (2009) Synthesis of dihydroxyurea and its application to the U/Pu split in the PUREX process. J Radioanal Nucl Chem 279:293–299

    Article  CAS  Google Scholar 

  20. Fishbein WN (1968) A simple, sensitive, and specific colorimetric assay for dihydroxyurea. Anal Chim Acta 40:269–275

    Article  CAS  Google Scholar 

  21. Zhang B, Wang JH, Bao BR et al (2006) Qualitative and quantitative analysis of hydrogen and carbon monoxide produced from radiolysis of acetohydroxamic acid in aqueous solution. J Shanghai Univ 12:408–411 (in Chinese)

    CAS  Google Scholar 

  22. Chen CH, Wu YB (2004) Determination of ammonium by ion chromatography for spectrophotometry. Modern Sci Instrum 5:64–65 (in Chinese)

    Google Scholar 

  23. Editorial board of water and wastewater detection and analysis methods by State Environmental Protection Administration (2002) In: Water and wastewater monitoring and analysis methods, 4rd edn. China Environment publishing house, Beijing

  24. Li HB, Su Zh, Cong HF et al (2012) α and γ irradiation stability of 30% TBP-Kerosene-HNO3 systems. J Nucl Radiochem 34:281–285 (in Chinese)

    CAS  Google Scholar 

  25. Karraker DG (2002) Radiation chemistry of acetohydroxamic acid in the Urex process, WSRC-TR-2002–00283:1–8

  26. Le CS (2011) Water radiolysis: influence of oxide surfaces on H2 production under ionizing radiation. Water 3:235–253

    Article  Google Scholar 

  27. Spinks JWT, Woods RJ (1976) An introduction to radiation chemistry, 2nd edn. A Wiley-Interscience Publication. John Wiley & Sons, New York, pp 247–295

    Google Scholar 

  28. Jiang PY, Nagaishi R, Yotsuyanagi T et al (1994) γ-Radiolysis study of concentrated nitric acid solutions. J Chem Soc Faraday Trans 90:93–95

    Article  CAS  Google Scholar 

  29. Balcerzyk AE et al (2012) Picosecond pulse radiolysis study of highly concentrated nitric acid solutions: formation mechanism of NO3· radical. J Phys Chem 116:7302–7307

    Article  CAS  Google Scholar 

  30. Katsumura Y, Jiang PY, Nagaishi R et al (1991) Pulse radiolysis study of aqueous nitric acid solutions: formation mechanism, yield, and reactivity of NO3 radical. J Phys Chem 95:4435–4439

    Article  CAS  Google Scholar 

  31. King S (2003) The nitric oxide producing reactions of hydroxyurea. Curr Med Chem 10:437–452

    Article  CAS  Google Scholar 

  32. Ohno K, Kishimoto N, Iwamoto T, et al (2017) Global exploration of isomers and isomerization channels on the quantum chemical potential energy surface of H3CNO3. J Comput Chem, 1–19

  33. Lefort M, Tarrago X (1961) Significance and function of NH2 in the ionizing radiolysis of hydroxylamine aqueous solution. J Inorg Nucl Chem 16:169–189

    Article  CAS  Google Scholar 

  34. Simic M, Hayon E (1971) Intermediates produced from the one-electron oxidation and reduction of hydroxylamines. Acid-base properties of the amino, hydroxyamino, and methoxyamino radicals. J Amer Chem Soc 93(23):5982–5986

    Article  CAS  Google Scholar 

  35. Miranda KM (2005) The chemistry of nitroxyl (HNO) and implications in biology. Coord Chem Rev 249:433–455

    Article  CAS  Google Scholar 

  36. Miranda KM, Paolocci N, Katori T et al (2003) A biochemical rationale for the discrete behavior of nitroxyl and nitric oxide in the cardiovascular system. Proc Natl Acad Sci USA 100:9196–9201

    Article  CAS  Google Scholar 

  37. Bonner FT, Hughes MN (1989) The aqueous solution chemistry of nitrogen in low positive oxidation states. ChemInform 7:215–234

    Google Scholar 

  38. Cheng YG (1992) hydroxylamine and salt. Fire Explos 6:52–57 (in Chinese)

    Google Scholar 

  39. Horne GP, Grimes TS, Bauer WF et al (2019) Effect of ionizing radiation on the redox chemistry of penta-and hexavalent Americium. Inorg Chem 58:8551–8559

    Article  CAS  Google Scholar 

  40. Nagaishi R (2001) A model for radiolysis of nitric acid and its application to the radiation chemistry of uranium ion in nitric acid medium. Radiat Phys Chem 60:369–375

    Article  CAS  Google Scholar 

  41. Horne GP, Gregson CR, Sims HE et al (2017) Plutonium and americium alpha radiolysis of nitric acid solutions. J Phys Chem B 121:883–889

    Article  CAS  Google Scholar 

  42. Kazanjian AR, Miner FJ, Brown AK et al (1970) Radiolysis of nitric acid solution: l.e.t. effects. Trans Faraday Soc 66:2192–2198

    Article  CAS  Google Scholar 

  43. Mincher BJ, Precek M, Mezyk SP et al (2013) The redox chemistry of neptunium in γ-irradiated aqueous nitric acid. Radiochim Acta 101:259–266

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. School of Environmental and Chemical Engineering, Shanghai University, 99 Shangda Road, Shanghai, 200444, China

    X. Y. Zhao, J. H. Wang, Q. Li & M. H. Wu

  2. Radiochemistry Department, China Institute of Atomic Energy, P.O. Box 275, Beijing, 102413, China

    W. F. Zheng & H. He

Authors
  1. X. Y. Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. J. H. Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Q. Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. M. H. Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. W. F. Zheng
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. H. He
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to J. H. Wang.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhao, X.Y., Wang, J.H., Li, Q. et al. γ-ray radiolysis of dihydroxyurea in nitric acid and its radiolytic products. J Radioanal Nucl Chem 331, 3517–3524 (2022). https://doi.org/10.1007/s10967-022-08388-w

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10967-022-08388-w

Keywords

Search

Navigation