@article{fdi:010062004,
  title = {{F}irst-principles modeling of sulfate incorporation and {S}-34/{S}-32 isotopic fractionation in different calcium carbonates},
  author = {{B}alan, {E}tienne and {B}lanchard, {M}. and {P}inilla, {C}. and {L}azzeri, {M}.},
  editor = {},
  language = {{ENG}},
  abstract = {{I}ncorporation mechanism of sulfate groups in major calcium carbonates (calcite, aragonite and vaterite) is investigated using first-principles quantum-mechanical calculations. {F}or each mineral, the stable structure of the substituted site is determined. {I}n calcite and aragonite, a tilting of the sulfate-group with respect to the orientation of planar carbonate groups is observed. {T}he theoretical vibrational properties of the sulfate-bearing carbonates are determined together with those of anhydrite ({C}a{SO}4) and isolated {SO}2 molecule. {C}omparison with experimental data supports the substitution of sulfate for carbonate groups in carbonate minerals. {T}he energetic of sulfate incorporation is increasingly unfavorable in the order vaterite, calcite, and aragonite. {R}egarding isotopic fractionation properties, our calculations suggest that the equilibrium {S}-34/{S}-32 isotopic fractionation factor between vaterite and calcite is small (similar to 0.5% at 0 degrees {C}). {A} slightly larger fractionation factor (similar to 1% at 0 degrees {C}) is expected between aragonite and calcite; whereas a negative fractionation (similar to-1.5% at 0 degrees {C}) is expected between anhydrite and calcite. {F}inally, it is suggested that the isotopic fractionation between calcite and aqueous sulfate is smaller than 4%.},
  keywords = {{CAS} ; {A}b initio ; {S}ulfur isotope fractionation},
  booktitle = {},
  journal = {{C}hemical {G}eology},
  volume = {374},
  numero = {},
  pages = {84--91},
  ISSN = {0009-2541},
  year = {2014},
  DOI = {10.1016/j.chemgeo.2014.03.004},
  URL = {https://www.documentation.ird.fr/hor/fdi:010062004},
}