Determination of the equilibrium magnesium isotope fractionation factors between brucite and aqueous inorganic and organic species

Magnesium (Mg) is a major element in seawater, rock-forming minerals, and biological systems. Stable Mg isotopes fractionate during silicate weathering and carbonate mineralization, and hence are a promis-ing tool to trace these processes. Magnesium can be present in natural aqueous solutions as a number of distinct inorganic and organic complexes including MgHCO3 +, MgCO30, MgSO40, Mg(OH)+, Mg(citrate)- and Mg(EDTA)2-, in addition to Mg(H2O)62+ commonly referred to as Mg2+. The formation of these species can significantly alter the fractionation of Mg isotopes between minerals and natural fluids. To quantify these effects, isotope exchange experiments were performed at bulk chemical equilibrium between brucite and aqueous solutions containing different organic (citrate, EDTA) and inorganic (SO4-) ligands at 25 degrees C. The three isotope' method was used to determine the equilibrium Mg isotope fractionation factors delta eq26Mg between brucite and several major aqueous magnesium species. The experimentally measured equilibrium Mg isotope fractionation factor between brucite and aqueous Mg2+ was found to be delta eq26Mgbrucite-Mg2+ =-0.35 +/- 0.39%degrees. First-principle calculations to retvieve the brucite p-factor were per-formed consistently with the calculations of Pinilla et al. (2015) for Mg2+(aq) p-factor. The combination of both studies yield values of delta eq26Mgbrucite-Mg2+ between +0.3 and +0.8 +/- 1.0%degrees, which is the lowest the-oretical estimate of this constant obtained to date. An average value delta eq 26Mgbrucite-MgSO4 0 = 0.48 +/- 0.16%degrees was retrieved from the experiments for the isotope fractionation between brucite and aqueous MgSO40. Mg isotope equilibrium fractionation factors between brucite and aqueous Mg(citrate)- and between brucite and aqueous Mg(EDTA)2-retrieved from the experiments performed in the presence of these organic ligands are delta eq26Mgbrucite-Mg(citrate)- = 0.35 +/- 0.21, and delta eq26Mgbrucite-Mg(EDTA)2-= 2.41 +/- 0.20%degrees. The experimental values determined in this study for delta eq26Mgbrucite-Mg2+ agree with the experimental values reported by Li et al. (2014). There is also an excellent agreement between the experimental values of this study and Li et al. (2014) with the density functional theory (DFT) estimates from Schott et al. (2016) for delta eq26MgMg2+-Mg(EDTA)2-. In contrast, the Mg isotope fractionation factor measured in this study between aqueous Mg2+ and both aqueous Mg sulphate or citrate species is significantly smaller than predictions from the ab initio calculations reported by Schott et al. (2016). The results of the present study confirm that the mineral-fluid equilibrium fractionation of Mg isotopes is strongly dependent on the identity of the inorganic or organic ligands present in the aqueous fluid and the nature of the complexes, (e.g. inner-sphere versus outer-sphere complexes), formed by magnesium with these ligands. Therefore, Mg speciation in natural fluids and the structure of aqueous Mg complexes have to be known for an accurate interpretation of Mg isotopic signatures in natural environments. (C) 2022 Elsevier Ltd. All rights reserved.

Automated summary

Magnesium isotopes serve as a promising tool to trace silicate weathering and carbonate mineralization processes. This study explores the different chemical forms of magnesium in aqueous solutions and their effects on isotope fractionation.