TY - JOUR
T1 - Theoretical isotopic fractionation between structural boron in carbonates and aqueous boric acid and borate ion
AU - Balan, Etienne
AU - Noireaux, Johanna
AU - Mavromatis, Vasileios
AU - Saldi, Giuseppe D.
AU - Montouillout, Valérie
AU - Blanchard, Marc
AU - Pietrucci, Fabio
AU - Gervais, Christel
AU - Rustad, James R.
AU - Schott, Jacques
AU - Gaillardet, Jérôme
PY - 2018/2/1
Y1 - 2018/2/1
N2 - The 11B/10B ratio in calcite and aragonite is an important proxy of oceanic water pH. However, the physico-chemical mechanisms underpinning this approach are still poorly known. In the present study, we theoretically determine the equilibrium isotopic fractionation properties of structural boron species in calcium carbonates, BO33−, BO2(OH)2− and B(OH)4− anions substituted for carbonate groups, as well as those of B(OH)4− and B(OH)3 species in vacuum. Significant variability of equilibrium isotopic fractionation properties is observed among these structural species which is related to their contrasted coordination state, B–O bond lengths and atomic-scale environment. The isotopic composition of structural boron does not only depend on its coordination number but also on its medium range environment, i.e. farther than its first coordination shell. The isotopic fractionation between aqueous species and their counterparts in vacuum are assessed using previous investigations based on similar quantum-mechanical modeling approaches. At 300 K, the equilibrium isotope composition of structural trigonal species is 7–15‰ lighter than that of aqueous boric acid molecules, whereas substituted tetrahedral borate ions are heavier than their aqueous counterparts by 10–13‰. Although significant uncertainties are known to affect the theoretical prediction of fractionation factors between solids and solutions, the usually assumed lack of isotopic fractionation during borate incorporation in carbonates is challenged by these theoretical results. The present theoretical equilibrium fractionation factors between structural boron and aqueous species differ from those inferred from experiments which may indicate that isotopic equilibrium, unlike chemical equilibrium, was not reached in most experiments. Further research into the isotopic fractionation processes at the interface between calcium carbonates and aqueous solution as well as long duration experiments aimed at investigating the kinetics of equilibration of boron environment and isotopic composition are therefore required to refine our understanding of boron coprecipitation in carbonates and thus the theory behind the use of boron isotopes as an ocean pH proxy.
AB - The 11B/10B ratio in calcite and aragonite is an important proxy of oceanic water pH. However, the physico-chemical mechanisms underpinning this approach are still poorly known. In the present study, we theoretically determine the equilibrium isotopic fractionation properties of structural boron species in calcium carbonates, BO33−, BO2(OH)2− and B(OH)4− anions substituted for carbonate groups, as well as those of B(OH)4− and B(OH)3 species in vacuum. Significant variability of equilibrium isotopic fractionation properties is observed among these structural species which is related to their contrasted coordination state, B–O bond lengths and atomic-scale environment. The isotopic composition of structural boron does not only depend on its coordination number but also on its medium range environment, i.e. farther than its first coordination shell. The isotopic fractionation between aqueous species and their counterparts in vacuum are assessed using previous investigations based on similar quantum-mechanical modeling approaches. At 300 K, the equilibrium isotope composition of structural trigonal species is 7–15‰ lighter than that of aqueous boric acid molecules, whereas substituted tetrahedral borate ions are heavier than their aqueous counterparts by 10–13‰. Although significant uncertainties are known to affect the theoretical prediction of fractionation factors between solids and solutions, the usually assumed lack of isotopic fractionation during borate incorporation in carbonates is challenged by these theoretical results. The present theoretical equilibrium fractionation factors between structural boron and aqueous species differ from those inferred from experiments which may indicate that isotopic equilibrium, unlike chemical equilibrium, was not reached in most experiments. Further research into the isotopic fractionation processes at the interface between calcium carbonates and aqueous solution as well as long duration experiments aimed at investigating the kinetics of equilibration of boron environment and isotopic composition are therefore required to refine our understanding of boron coprecipitation in carbonates and thus the theory behind the use of boron isotopes as an ocean pH proxy.
KW - Ab initio modeling
KW - Boron pH-proxy
KW - Calcium carbonates
KW - Theoretical isotopic fractionation factors
UR - http://www.scopus.com/inward/record.url?scp=85032888201&partnerID=8YFLogxK
U2 - 10.1016/j.gca.2017.10.017
DO - 10.1016/j.gca.2017.10.017
M3 - Article
AN - SCOPUS:85032888201
SN - 0016-7037
VL - 222
SP - 117
EP - 129
JO - Geochimica et Cosmochimica Acta
JF - Geochimica et Cosmochimica Acta
ER -