Mercury isotope fractionation during liquid–vapor evaporation experiments

Estrade, Nicolas; Carignan, Jean; Sonke, Jeroen E.; Donard, Olivier F. X.

doi:10.1016/j.gca.2009.01.024

Cited by 246 publications

(285 citation statements)

References 57 publications

(107 reference statements)

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“…Combined with the equilibrium mass-dependent fractionation (−0.2 ± 0.1‰) estimated from lattice-dynamics models (19), the net theoretical fractionation of −1.1‰ to −0.7‰ closely matches recent liquid-vapor equilibration experiments [−1.5‰ to −1.0‰ (19); −0.9 ± 0.2‰ (18)]. Oddisotope mass-independent signatures (Δ 199 Hg and Δ 201 Hg) are also in good agreement with experiment, if the compilation of nuclear charge radii of ref.…”

Section: Methodssupporting

confidence: 78%

“…However, the all-electron relativistic electronic structure calculations that form the basis for these studies are computationally intensive, requiring self-consistent solutions for four-component wave functions involving typically thousands of basis functions. As a result, these studies are limited to modeling systems with ∼20 or fewer atoms, even though some of the most interesting observations of mass-independent isotope effects are in aqueous solutions (3,7,9), liquid metals (2,18,19), and solids (e.g., refs. 20 and 21).…”

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confidence: 99%

“…Recent observations of mass-independent fractionation have been attributed to field shift effects in all three elements (2,18,19,30,31); Cd-and Hg-isotope fractionation between liquid metal and the vapor phase are of particular interest (2,18,19). Tin is also the heaviest element in a recent DFT-PAW Möss-bauer calibration study (28) and has been the focus of other calibration studies (e.g., refs.…”

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confidence: 99%

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Modeling nuclear volume isotope effects in crystals

Schauble

2013

Proc. Natl. Acad. Sci. U.S.A.

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Mass-independent isotope fractionations driven by differences in volumes and shapes of nuclei (the field shift effect) are known in several elements and are likely to be found in more. All-electron relativistic electronic structure calculations can predict this effect but at present are computationally intensive and limited to modeling small gas phase molecules and clusters. Density functional theory, using the projector augmented wave method (DFT-PAW), has advantages in greater speed and compatibility with a three-dimensional periodic boundary condition while preserving information about the effects of chemistry on electron densities within nuclei. These electron density variations determine the volume component of the field shift effect. In this study, DFT-PAW calculations are calibrated against all-electron, relativistic DiracHartree-Fock, and coupled-cluster with single, double (triple) excitation methods for estimating nuclear volume isotope effects. DFT-PAW calculations accurately reproduce changes in electron densities within nuclei in typical molecules, when PAW datasets constructed with finite nuclei are used. Nuclear volume contributions to vapor-crystal isotope fractionation are calculated for elemental cadmium and mercury, showing good agreement with experiments. The nuclear-volume component of mercury and cadmium isotope fractionations between atomic vapor and montroydite (HgO), cinnabar (HgS), calomel (Hg 2 Cl 2 ), monteponite (CdO), and the CdS polymorphs hawleyite and greenockite are calculated, indicating preferential incorporation of neutron-rich isotopes in more oxidized, ionically bonded phases. Finally, field shift energies are related to Mössbauer isomer shifts, and equilibrium massindependent fractionations for several tin-bearing crystals are calculated from 119 Sn spectra. Isomer shift data should simplify calculations of mass-independent isotope fractionations in other elements with Mössbauer isotopes, such as platinum and uranium.Mössbauer spectroscopy | nuclear field shift | mass independent fractionation A mong the various causes of mass-independent isotope fractionation discovered over the past 40 years, the nuclear field shift effect (1) is unique in that it is an equilibrium thermodynamic phenomenon (and may also impart an identifiable and distinct signature in disequilibrium conditions) (2, 3). It has also proven amenable to prediction by electronic structure methods, at least in simple molecular systems (e.g., refs. 4-7). The goal of the present study is to extend the scope of systems that can be modeled to include condensed phases and crystals, and to speed up calculations for complex materials while retaining enough accuracy to be useful.Nuclear field shift effects result from the finite volume and sometimes nonspherical shapes of atomic nuclei, which are slightly different from one isotope to another. These differences in size and shape affect the coulomb potential felt by bound electrons, and thus the electronic structures of atoms and molecules. Nuclear field shifts have lo...

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Section: Methodssupporting

confidence: 78%

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confidence: 99%

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confidence: 99%

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Modeling nuclear volume isotope effects in crystals

Schauble

2013

Proc. Natl. Acad. Sci. U.S.A.

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“…The data points either greater than the upper quartile + 1.5 IQR or less than the lower quartile-1.5 IQR are considered to be extreme values. Data sources: coal (Biswas et al, 2008;Lefticariu et al, 2011;Sherman et al, 2012;Sun et al, 2013Sun et al, , 2014aSun et al, , 2014bYin et al, 2014a); oil ; cinnabar (Cooke et al, 2013;Foucher et al, 2009;Gehrke et al, 2011;Smith et al, 2005Smith et al, , 2008Stetson et al, 2009;Yin et al, 2013); Commercial liquid Hg 0 Estrade et al, 2009;Foucher et al, 2009;Laffont et al, 2011;Mead et al, 2013;Sonke et al, 2008); Zn ores (Smith, 2010;Sonke et al, 2010); Au ores (Smith, 2010); silicate rocks (Blum and Anbar, 2010;North, 2011;Sun et al, 2014b;Zhang et al, 2013Zhang et al, , 2014; limestone (sampled from Huainan Basin, China, this study); volcanic gases (this study; Zambardi et al, 2009 144 sector/fuel/technology combinations for combustion sources are designated to coal combustion, and all these combinations have their corresponding Hg species emission characteristics. Here, we improve the previous estimates on isotope composition of speciated Hg from coal combustion as follows: 1) APCDs are divided into five types: cyclone, scrubber, fiber filter (FF), electrostatic precipitator (ESP), flue gas desulfurization (FGD).…”

Section: Methods Descriptionmentioning

confidence: 99%

Historical (1850–2010) mercury stable isotope inventory from anthropogenic sources to the atmosphere

Sun

Streets

Horowitz

et al. 2016

Elementa: Science of the Anthropocene

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162

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Mercury (Hg) stable isotopes provide a new tool to trace the biogeochemical cycle of Hg. An inventory of the isotopic composition of historical anthropogenic Hg emissions is important to understand sources and post-emission transformations of Hg. We build on existing global inventories of anthropogenic Hg emissions to the atmosphere to develop the first corresponding historical Hg isotope inventories for total Hg (THg) and three Hg species: gaseous elemental Hg (GEM), gaseous oxidized Hg (GOM) and particulate-bound Hg (PBM). We compile d

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“…Estrade et al (2009) and Ghosh et al (2013) conducted liquid-vapor evaporation experiments in the absence of light for mercury. They both concluded that the nuclear field shift effects are the dominant cause of equilibrium stable isotope fractionation in the absence of light.…”

Section: Liquid-vapor Evaporation Experimentsmentioning

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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Mercury isotope fractionation during liquid–vapor evaporation experiments

Cited by 246 publications

References 57 publications

Modeling nuclear volume isotope effects in crystals

Modeling nuclear volume isotope effects in crystals

Historical (1850–2010) mercury stable isotope inventory from anthropogenic sources to the atmosphere

Nuclear field shift effects on stable isotope fractionation: a review

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