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Title: Kinetic Isotopic Fractionation During Diffusion of Ionic Speciesin Water

Journal Article · · Geochimica et Cosmochimica Acta
OSTI ID:891030

Experiments specifically designed to measure the ratio of the diffusivities of ions dissolved in water were used to determine D{sub Li}/D{sub K}, D{sub 7{sub Li}}/D{sub 6{sub Li}}, D{sub 25{sub Mg}}/D{sub 24{sub Mg}}, D{sub 26{sub Mg}}/D{sub 25{sub Mg}}, and D{sub 37{sub Cl}}/D{sub 35{sub Cl}}. The measured ratio of the diffusion coefficients for Li and K in water (D{sub Li}/D{sub K} = 0.6) is in good agreement with published data, providing evidence that the experimental design being used resolves the relative mobility of ions with adequate precision to also be used for determining the fractionation of isotopes by diffusion in water. In the case of Li we found measurable isotopic fractionation associated with the diffusion of dissolved LiCl (D{sub 7{sub Li}}/D{sub 6{sub Li}} = 0.99772 {+-} 0.00026). This difference in the diffusion coefficient of {sup 7}Li compared to {sup 6}Li is significantly less than reported in an earlier study, a difference we attribute to the fact that in the earlier study Li diffused through a membrane separating the water reservoirs. Our experiments involving Mg diffusing in water found no measurable isotopic fractionation (D{sub 25{sub Mg}}/D{sub 24{sub Mg}} = 1.00003 {+-} 0.00006). Cl isotopes were fractionated during diffusion in water (D{sub 37{sub Cl}}/D{sub 35{sub Cl}} = 0.99857 {+-} 0.00080) whether or not the co-diffuser (Li or Mg) was isotopically fractionated. The isotopic fractionation associated with the diffusion of ions in water is much smaller than values we found previously for the isotopic fractionation of Li and Ca isotopes by diffusion in molten silicate liquids. A major distinction between water and silicate liquids is that water, being a polar liquid, surrounds dissolved ions with hydration shells, which very likely play an important but still poorly understood role in reducing isotopic fractionation associated with diffusion.

Research Organization:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Director. Office of Science. Office of Basic EnergySciences
DOE Contract Number:
DE-AC02-05CH11231
OSTI ID:
891030
Report Number(s):
LBNL-58268; GCACAK; R&D Project: 468210; BnR: KC0303020; TRN: US200621%%53
Journal Information:
Geochimica et Cosmochimica Acta, Vol. 70, Issue 2; Related Information: Journal Publication Date: 01/15/2006; ISSN 0016-7037
Country of Publication:
United States
Language:
English

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