Isotopic fractionation of noble gases by diffusion in liquid water: Molecular dynamics simulations and hydrologic applications

Ian C. Bourg, Garrison Sposito

Research output: Contribution to journalArticlepeer-review

72 Scopus citations


Despite their great importance in low-temperature geochemistry, diffusion coefficients of noble gas isotopes in liquid water (D) have been measured only for the major isotopes of helium, neon, krypton and xenon. Data on the diffusion coefficients of minor noble gas isotopes are essentially non-existent and so typically have been estimated by a kinetic-theory model in which D varies as the inverse square root of the isotopic mass (m): D ∝ m-0.5. To examine the validity of the kinetic-theory model, we performed molecular dynamics (MD) simulations of the diffusion of noble gases in ambient liquid water. Our simulation results agree with available experimental data on the solvation structure and diffusion coefficients of the major noble gas isotopes and reveal for the first time that the isotopic mass-dependence of all noble gas self-diffusion coefficients has the power-law form D ∝ m with 0 < β < 0.2. Thus our results call into serious question the widespread assumption that the 'square-root' model can be applied to estimate the kinetic fractionation of noble gas isotopes caused by diffusion in ambient liquid water. To illustrate the importance of this finding, we used the diffusion coefficients determined in our MD simulations to reconsider the geochemical modeling of 20Ne/22Ne and 36Ar/40Ar isotopic ratios in three representative hydrologic studies. Our new modeling results indicate that kinetic isotopic fractionation by diffusion may play a significant role in noble gas transport processes in groundwater.

Original languageEnglish (US)
Pages (from-to)2237-2247
Number of pages11
JournalGeochimica et Cosmochimica Acta
Issue number9
StatePublished - May 1 2008
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Geochemistry and Petrology


Dive into the research topics of 'Isotopic fractionation of noble gases by diffusion in liquid water: Molecular dynamics simulations and hydrologic applications'. Together they form a unique fingerprint.

Cite this