Isotopic fractionation of Mg2+(aq), Ca2+(aq), and Fe2+(aq) with carbonate minerals

Rustad, James R.; Casey, William H.; Yin, Qing-Zhu; Bylaska, Eric J.; Felmy, Andrew R.; Bogatko, Stuart A.; Jackson, Virgil E.; Dixon, David A.

doi:10.1016/j.gca.2010.08.018

Isotopic fractionation of Mg²⁺(aq), Ca²⁺(aq), and Fe²⁺(aq) with carbonate minerals

Journal Article · Sat Aug 21 00:00:00 EDT 2010 · Geochimica et Cosmochimica Acta

DOI:https://doi.org/10.1016/j.gca.2010.08.018· OSTI ID:2544386

Rustad, James R. ^[1]; Casey, William H. ^[1]; Yin, Qing-Zhu ^[1]; Bylaska, Eric J. ^[2]; Felmy, Andrew R. ^[2]; Bogatko, Stuart A. ^[3]; Jackson, Virgil E. ^[4]; Dixon, David A. ^[4]

University of California, Davis, CA (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
University of California, San Diego, La Jolla, CA (United States)
University of Alabama, Tuscaloosa, AL (United States)

Density-functional electronic structure calculations are used to compute the equilibrium constants for ²⁶Mg/²⁴Mg and ⁴⁴Ca/⁴⁰Ca isotope exchange between carbonate minerals and uncomplexed divalent aquo ions. The most reliable calculations at the B3LYP/6-311++G(2d,2p) level predict equilibrium constants K, reported as 10³ln (K) at 25 °C, of –5.3, –1.1, and +1.2 for ²⁶Mg/²⁴Mg exchange between calcite (CaCO₃), magnesite (MgCO₃), and dolomite (Ca_0.5Mg_0.5CO₃), respectively, and Mg²⁺(aq), with positive values indicating enrichment of the heavy isotope in the mineral phase. For ⁴⁴Ca/⁴⁰Ca exchange between calcite and Ca²⁺(aq) at 25 °C, the calculations predict values of +1.5 for Ca²⁺(aq) in 6-fold coordination and +4.1 for Ca²⁺(aq) in 7-fold coordination. We find that the reduced partition function ratios can be reliably computed from systems as small as M(CO₃)₆^10– and M(H₂O)₆²⁺ embedded in a set of fixed atoms representing the second-shell (and greater) coordination environment. We find that the aqueous cluster representing the aquo ion is much more sensitive to improvements in the basis set than the calculations on the mineral systems, and that fractionation factors should be computed using the best possible basis set for the aquo complex, even if the reduced partition function ratio calculated with the same basis set is not available for the mineral system. Here, the new calculations show that the previous discrepancies between theory and experiment for Fe³⁺–hematite and Fe²⁺–siderite fractionations arise from an insufficiently accurate reduced partition function ratio for the Fe³⁺(aq) and Fe²⁺(aq) species.

View Accepted Manuscript (DOE)

Research Organization:: University of California, Davis, CA (United States)

Sponsoring Organization:: National Aeronautics and Space Administration (NASA); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: FG02-05ER15693

OSTI ID:: 2544386

Alternate ID(s):: OSTI ID: 2507297
OSTI ID: 994030

Journal Information:: Geochimica et Cosmochimica Acta, Journal Name: Geochimica et Cosmochimica Acta Journal Issue: 22 Vol. 74; ISSN 0016-7037

Publisher:: Elsevier; The Geochemical Society; The Meteoritical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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