Spectroscopic determination of hypochlorous acid, in chloride brine solutions, featuring 5MeV proton beam line experiments

Hartmann, Thomas; Paviet-Hartmann, Patricia; Wetteland, C. J.; Lu, Norman

doi:10.1016/s0969-806x(02)00407-3

Cited by 8 publications

(7 citation statements)

References 18 publications

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“…Similarly, Hartmann, et al [90] showed production of hypochlorous acid and hypochlorite in 3.7 M MgCl 2 ·H 2 O at pH 4.4; and in a mixed brine solution at pH 7.1 using 5 MeV proton irradiation to simulate α-particles. The α-irradiation of pH 12 NaCl solutions exposed to 238 Pu resulted in increasing amounts of OCl − with both increasing salt concentration and absorbed dose [91].…”

Section: Effects On Actinide Oxidation States In Salt Brinementioning

confidence: 92%

Radiation chemical effects on radiochemistry: A review of examples important to nuclear power

Mincher¹,

Mezyk

2009

Radiochimica Acta

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Radiolysis / Linear energy transfer / Redox reactions / Ligand degradation / Free radicals / Solvent extractionSummary. Radiochemistry deals with the chemistry of the radioactive elements. In the nuclear industry successful fuel reprocessing, high-level waste treatment, and long-term storage of spent fuel depend on an understanding of the radiochemistry of actinides and fission products in these settings. Radiation chemistry is concerned with the chemical effects of ionizing radiation, with the most common types of radiation encountered by the radiochemist being low linear energy transfer (LET) β − and γ radiation, and higher LET α radiation. These radiations can have profound and important effects on radiochemistry, including changes in metal oxidation states and degradation of the organic ligands designed to complex radioelements. This may occur by direct action of the incident radiation on compounds present with high abundance or by reaction with radiolytically produced reactive species for trace components, such as the complexing agents. This review examines the role of reactive species created in irradiated aqueous and organic solution and their effects on radiochemistry. The sources and nature of these reactive species are discussed. Examples of radiation chemical effects are provided related to solvent extraction of the actinides from acidic solution, metal complexation and technetium redox chemistry in alkaline tank waste, and the corrosion of spent fuel stored in repository brine.

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Section: Effects On Actinide Oxidation States In Salt Brinementioning

confidence: 92%

Radiation chemical effects on radiochemistry: A review of examples important to nuclear power

Mincher¹,

Mezyk

2009

Radiochimica Acta

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“…Very little information exists on the nature of the stable chemical products produced by the passage of ionizing radiation in solid chloride salts despite the importance of these materials in the storage of radioactive materials. Solid-state radiolytic effects such as the production of F, H, or V centers have long been examined in a number of chloride salts, especially NaCl. , A variety of studies have also been performed on salt brines, but as shown later there is very little relationship between the radiation chemistry of brine and a solid salt. − Pyrochemical processing of plutonium in chloride salt media has been proceeding for many decades. Significant amounts of plutonium-containing materials have accumulated that are often associated with large quantities of potassium, sodium, magnesium, and calcium chloride salts. − Salt content can be from about 8 to 20 wt %, depending on the degree of calcination.…”

Section: Introductionmentioning

confidence: 99%

“…No consensus on the formation or yield of Cl 2 in the radiolysis of solid chloride salts has emerged. On the other hand, excellent spectroscopic studies have been performed recently on various chlorine species following the radiolysis of aqueous solutions of NaCl, MgCl 2 , and multicomponent brines. , The formation of chlorine species may lead to the oxidiation of actinide species (Pu, Am, Cm, Np, and U) to higher oxidation states if they are present. , …”

Section: Introductionmentioning

confidence: 99%

“…1,2 A variety of studies have also been performed on salt brines, but as shown later there is very little relationship between the radiation chemistry of brine and a solid salt. [3][4][5][6][7][8][9][10][11][12][13][14][15] Pyrochemical processing of plutonium in chloride salt media has been proceeding for many decades. Significant amounts of plutoniumcontaining materials have accumulated that are often associated with large quantities of potassium, sodium, magnesium, and calcium chloride salts.…”

Section: Introductionmentioning

confidence: 99%

“…On the other hand, excellent spectroscopic studies have been performed recently on various chlorine species following the radiolysis of aqueous solutions of NaCl, MgCl 2 , and multicomponent brines. 15,32 The formation of chlorine species may lead to the oxidiation of actinide species (Pu, Am, Cm, Np, and U) to higher oxidation states if they are present. 10,33 In this work, the formation of gaseous H ions (R-particles) in order to examine the effect due to the linear energy transfer (LET ) stopping power, -dE/dx) of the radiation and to mimic the conditions in mixed storage with high concentration of γ-emitting actinides (Am, Np, etc.)…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

H₂ and Cl₂ Production in the Radiolysis of Calcium and Magnesium Chlorides and Hydroxides

LaVerne

Tandon

2005

J. Phys. Chem. A

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The production of H2 has been examined in the gamma-ray and 5 MeV He ion radiolysis of CaCl2.2H2O, CaCl2.6H2O, Ca(OH)2, MgCl2.2H2O, MgCl2.6H2O, and Mg(OH)2. The highest yield for the formation of H2 is observed in the gamma-radiolysis of MgCl2.2H2O (0.72 molecule/(100 eV), 75 nmol/J), but the yield decreases with dose due to the relative instability of the dihydrate. The H2 yields with the other compounds range from 0.04 to 0.2 molecule/(100 eV) (4.2-21 nmol/J), which is lower than that from pure water or 2 M chloride solutions. There appears to be no relationship between the results for H2 from waters of hydration with that from aqueous salt brines. No particular trend is observed in the radiation chemical yields of H2 with respect to the cation or the degree of hydration. The production of Cl2 is found only in the gamma-radiolysis of CaCl2 with a few weight percent of excess water. No Cl2 was found in the 5 MeV He ion radiolysis of identical systems. None of the other compounds examined here showed detectable amounts of Cl2 formation.

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The catalase activity of diiron adenine deaminase

et al. 2011

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Adenine deaminase (ADE) from the amidohydrolase superfamily (AHS) of enzymes catalyzes the conversion of adenine to hypoxanthine and ammonia. Enzyme isolated from Escherichia coli was largely inactive toward the deamination of adenine. Molecular weight determinations by mass spectrometry provided evidence that multiple histidine and methionine residues were oxygenated. When iron was sequestered with a metal chelator and the growth medium supplemented with Mn 21 before induction, the post-translational modifications disappeared. Enzyme expressed and purified under these conditions was substantially more active for adenine deamination. Apo-enzyme was prepared and reconstituted with two equivalents of FeSO 4 . Inductively coupled plasma mass spectrometry and Mö ssbauer spectroscopy demonstrated that this protein contained two high-spin ferrous ions per monomer of ADE. In addition to the adenine deaminase activity, [ ]-ADE underwent more than 100 turnovers with H 2 O 2 before the enzyme was inactivated due to oxygenation of histidine residues critical for metal binding. The iron in the inactive enzyme was high-spin ferric with g ave 5 4.3 EPR signal and no evidence of antiferromagnetic spin-coupling. A model is proposed for the disproportionation of H 2 O 2 by [Fe II /Fe II ]-ADE that involves the cycling of the binuclear metal center between the di-ferric and di-ferrous oxidation states. Oxygenation of active site residues occurs via release of hydroxyl radicals. These findings represent the first report of redox reaction catalysis by any member of the AHS.

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Spectroscopic determination of hypochlorous acid, in chloride brine solutions, featuring 5MeV proton beam line experiments

Cited by 8 publications

References 18 publications

Radiation chemical effects on radiochemistry: A review of examples important to nuclear power

Radiation chemical effects on radiochemistry: A review of examples important to nuclear power

H₂ and Cl₂ Production in the Radiolysis of Calcium and Magnesium Chlorides and Hydroxides

The catalase activity of diiron adenine deaminase

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Spectroscopic determination of hypochlorous acid, in chloride brine solutions, featuring 5MeV proton beam line experiments

Cited by 8 publications

References 18 publications

Radiation chemical effects on radiochemistry: A review of examples important to nuclear power

Radiation chemical effects on radiochemistry: A review of examples important to nuclear power

H2 and Cl2 Production in the Radiolysis of Calcium and Magnesium Chlorides and Hydroxides

The catalase activity of diiron adenine deaminase

Contact Info

Product

Resources

About

H₂ and Cl₂ Production in the Radiolysis of Calcium and Magnesium Chlorides and Hydroxides