Direct measurement of the boron isotope fractionation factor: Reducing the uncertainty in reconstructing ocean paleo-pH

The boron isotopic composition of calcium carbonate skeletons is a promising proxy method for reconstructing paleo-ocean pH and atmospheric CO₂ from the geological record. Although the boron isotope methodology has been used extensively over the past two decades to determine ancient ocean-pH, the actual value of the boron isotope fractionation factor (ε_B) between the two main dissolved boron species, ¹¹B(OH)₃ and ¹⁰B(OH)^-₄, has remained uncertain. Initially, ε_B values were theoretically computed from vibrational frequencies of boron species, resulting in a value of ~19‰. Later, spectrophotometric pH measurements on artificial seawater suggested a higher value of ~27‰. A few independent theoretical models also pointed to a higher ε_B value. Here we provide, for the first time, an independent empirical fractionation factor (ε_B=26.0±1.0‰25 °C), determined by direct measurements of B(OH)₃ in seawater and other solutions. Boric acid was isolated by preferential passage through a reverse osmosis membrane under controlled pH conditions. We further demonstrate that applying the Pitzer ion-interaction approach, combined with ion-pairing calculations, results in a more accurate determination of species distribution in aquatic solutions of different chemical composition, relative to the traditional two-species boron-system approach. We show that using the revised approach reduces both the error in simulating ancient atmospheric CO₂ (by up to 21%) and the overall uncertainty of applying boron isotopes for paleo-pH reconstruction. Combined, this revised methodology lays the foundation for a more accurate determination of ocean paleo-pH through time.