Mass-Dependent and Mass-Independent Isotope Effects of Zinc in a Redox Reaction

Fujii, Toshiyuki; Moynier, Frédéric; Uehara, Akihiro; Abe, Masahide; Yin, Qing‐Zhu; Nagai, Takayuki; Yamana, Hideaki

doi:10.1021/jp904882d

Cited by 27 publications

(24 citation statements)

References 84 publications

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“…The results using the spectrum of the more recent Chesser and Axe (1974) study are reported in Table 2 as a function of temperature. Fujii et al (2009) assume a reduced partition function ratio for the liquid zinc phase in their experiments of 0, in effect assuming the extracted Zn(II) is in equilibrium with an atomic zinc vapor. The results here suggest that if isotopic partitioning into liquid zinc is analogous to hcp-zinc, the reduced partition function ratio is equal to b 66=64 Zn ðsÞ ÀZn ðgÞ $ 0:16 at 650°C (923 K).…”

Section: Speciation Of Aqueous Zincmentioning

confidence: 99%

“…Elevated levels of zinc in the environment can be directly linked to anthropogenic sources such as industrial processing , with estimates for anthropogenic emissions of zinc to the environment in the 1980s almost 40 times the natural flux (Callender, 2004). Recent experimental studies of zinc stable isotope fractionation during electro-reduction reactions have shown that stable isotope signatures are large and vary as a function of the reaction kinetics (Kavner et al, 2008;Black et al, 2009;Fujii et al, 2009;Black et al, 2010). Fig.…”

Section: Introductionmentioning

confidence: 99%

“…The structural form of zinc in high ionic strength solutions is of particular interest in modeling the speciation of zinc in industrial processes, such as electrowinning and extractive metallurgy (Wang and Dreisinger, 1998;Guerra and Bestetti, 2006). Few studies have focused on determining reduced partition function ratios for specific zinc species, with the exception of some recently published calculated reduced partition function ratios for a few aquoand chloro-zinc complexes from ab initio frequency calculations (Fujii et al, 2009(Fujii et al, , 2010) and a reconnaissance theoretical study of mineral/solution fractionation (Schauble, 2003). No other detailed examination of the reduced partition function ratios for isotopic partitioning between aqueous and crystalline zinc species has been published to our knowledge, and these calculations are a necessary compliment to understanding and interpreting the stable isotope distribution of zinc in both natural samples and experimental solutions.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Calculation of equilibrium stable isotope partition function ratios for aqueous zinc complexes and metallic zinc

Black

Kavner

Schauble

2011

Geochimica et Cosmochimica Acta

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Section: Speciation Of Aqueous Zincmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Calculation of equilibrium stable isotope partition function ratios for aqueous zinc complexes and metallic zinc

Black

Kavner

Schauble

2011

Geochimica et Cosmochimica Acta

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“…Anomalous light isotope enrichments of U(IV), U(VI), Pb(II) and Tl(I) relative to U(III), U(IV), Pb 0 and Tl 0 were found (Schauble 2007;Abe et al 2008aAbe et al , b, 2010Fujii et al 2011aFujii et al , 2013Yang and Liu 2015). In addition, zinc (Fujii et al 2009c and nickel isotopes (Fujii et al 2011b) were studied both experimentally and theoretically. However, the NFSE was found to be much smaller than the conventional mass-dependent effects for their cases.…”

Section: Nfse In Gaseous and Small Liquid Speciesmentioning

confidence: 99%

Nuclear field shift effects on stable isotope fractionation: a review

Yang

Liu

2016

Acta Geochim

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An anomalous isotope effect exists in many heavy element isotope systems (e.g., Sr, Gd, Zn, U). This effect used to be called the ''odd-even isotope effect'' because the odd mass number isotopes behave differently from the even mass number isotopes. This mass-independent isotope fractionation driving force, which originates from the difference in the ground-state electronic energies caused by differences in nuclear size and shape, is currently denoted as the nuclear field shift effect (NFSE). It is found that the NFSE can drive isotope fractionation of some heavy elements (e.g., Hg, Tl, U) to an astonishing degree, far more than the magnitude caused by the conventional mass-dependent effect (MDE). For light elements, the MDE is the dominant factor in isotope fractionation, while the NFSE is neglectable. Furthermore, the MDE and the NFSE both decrease as temperatures increase, though at different rates. The MDE decreases rapidly with a factor of 1/T 2 , while the NFSE decreases slowly with a factor of 1/T. As a result, even at high temperatures, the NFSE is still significant for many heavy element isotope systems. In this review paper, we begin with an introduction of the basic concept of the NSFE, including its history and recent progress, and follow with the potential implications of the inclusion of the NFSE into the kinetic isotope fractionation effect (KIE) and heavy isotope geochronology.Keywords Isotope fractionation Á Mass-dependent effect Á Nuclear field shift effect Á Mass-independent fractionation Á Nuclear volume effect Á Nuclear shape effect

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“…Now theoretical calculation of nuclear volume term is widely applied to various isotopes [14][15][16][17].…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study of Isotope Enrichment Caused by Nuclear Volume Effect

Abe

Hada

Suzuki

et al. 2014

J. Comput. Chem. Jpn.

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Isotope separation is important in industry, such as uranium enrichment. It is also very important in geochemistry and cosmo-chemistry because heavy and light isotopes are gradually fractionated in global equilibrium processes. For isotopes of heavy elements such as uranium and gadolinium, this fractionation occurs mainly owing to the difference of nuclear charge radii between the isotopes. This is because electronic states of isotopologues are different because of the difference of nuclear charge radii. Nuclear volume terms (lnKnv) in the equilibrium constants of isotope fractionations can be calculated from the electronic energy difference of isotopologues, obtained by relativistic quantum chemical calculations with finite-size nuclear models. In this review, we summarize our theoretical results in uranium isotope separations, using U (III)-U (IV) and U (IV)-U (VI) redox reaction systems. Calculated nuclear volume term (lnKnv) is reasonably close to the ones estimated from experimental analysis of temperature dependence in equilibrium constants.We used the four-component Dirac-Coulomb Hartree-Fock method with the Fermi and Gaussian-type nuclear models in our calculations. We also briefly mention how the nuclear volume effect is important in geochemistry or cosmochemistry referring to recent relevant works.

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Mass-Dependent and Mass-Independent Isotope Effects of Zinc in a Redox Reaction

Cited by 27 publications

References 84 publications

Calculation of equilibrium stable isotope partition function ratios for aqueous zinc complexes and metallic zinc

Calculation of equilibrium stable isotope partition function ratios for aqueous zinc complexes and metallic zinc

Nuclear field shift effects on stable isotope fractionation: a review

Theoretical Study of Isotope Enrichment Caused by Nuclear Volume Effect

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