Corrigendum to "New constraints on kinetic isotope effects during CO2(aq) hydration and hydroxylation" : Revisiting theoretical and experimental data” [Geochim. Cosmochim. Acta 214 (2017) 246–265](S0016703717304593)(10.1016/j.gca.2017.07.035)

The authors regret an error in the derivation of the link between KFFs and isotopic rate constants of CO ₂ hydration (Section 2.2). Considering the subset of isotopologues, C ¹⁶O ¹⁶O, C ¹⁸O ¹⁶O, H ₂ ¹⁶O and H ₂ ¹⁸O, there are four possible forward reactions: (1) C ¹⁶O ¹⁶O + H ₂ ¹⁶O → H ₂C ¹⁶O ¹⁶O ¹⁶O,(2) C ¹⁸O ¹⁶O + H ₂ ¹⁶O → H ₂C ¹⁸O ¹⁶O ¹⁶O,(3) C ¹⁶O ¹⁶O + H ₂ ¹⁸O → H ₂C ¹⁸O ¹⁶O ¹⁶O,(4) C ¹⁸O ¹⁶O + H ₂ ¹⁸O → H ₂C ¹⁸O ¹⁸O ¹⁶O.Reaction (4) involves rare isotopologues of both CO ₂ and of H ₂O, forms a doubly substituted isotopologue, and was not included in the original paper. Indeed, backward reaction (4) may be neglected in the derivation of the link between KFFs and isotopic rate constants of H ₂CO ₃ dehydration. However, forward reaction (4) still should have been considered in the derivation of the link between KFFs and isotopic rate constants of CO ₂ hydration. Including reaction (4) in the derivations presented in Section 2.2 and Appendix A.1 results in the following relations, (5) [Formula presented],(6) [Formula presented], which are distinct from those originally reported in Table 2, [Formula presented] and [Formula presented]. Thus, the dependence of the KFFs on the isotope ratio of the reactants, which was discussed in the paper, may be neglected. We have corrected Table 2 accordingly. Additionally, Fig. 2 of the original paper is obviated, as is its discussion in the text (last paragraph in Section 2.2). In the rest of the paper, this mistake affects only the theoretical KFF values of CO ₂ (de)hydration calculated using the isotopic rate constants of Zeebe (2014). The corrected KFF values differ by 2–4‰ from those reported in the paper, and are slightly farther from the experimental estimates after Clark and Lauriol (1992). We present below the corrected KFF values in revised Tables 4 and 6 along with values unaffected by the change (changes are underlined). Finally, we have revised Tables 8 and 9 and Figs. 3A and 4B which make use of the corrected KFFs to describe calcite precipitation at the kinetic limit. We thank Chen Zhou, University of Science and Technology of China, Hefei, for pointing out this mistake. We apologise for any inconvenience caused.