An empirical re-evaluation of the boron isotope/pH proxy in marine carbonates

The boron isotopic composition measured in marine carbonates is considered to be a tracer of seawater pH. However, an accurate application of this proxy has been hampered by our lack of intimate understanding of chemical kinetics and thermodynamic isotope exchange between the two dominant boron-bearing species in seawater: boric acid B(OH)3o and borate ions B(OH)4-, as well as their subsequent partitioning into a carbonate lattice. In this dissertation I have taken on a task of a systematic empirical re-evaluation of the fundamental parameters and assumptions on which the boron isotope paleo-pH proxy is based. As a result of this research strikingly different values of the boron isotope exchange constant in solution (Klochko et al., 2006) and boron speciation and partitioning in carbonates (Klochko et al., 2009) were determined, suggesting that the most parameters and assumptions that were believed to be previously constrained and have been widely applied to the 11B-pH reconstructions were incorrect. Recognizing that both biological and inorganic processes may potentially affect boron speciation and isotopic composition in carbonates, to isolate purely inorganic effects on the boron isotope co-precipitation with carbonates, we have designed a series of pH-controlled 11B calibration experiments of inorganic calcite and inorganic aragonite. Results to date reveal that precipitates from our experiments at pH = 8.7 fall exactly along the borate ion 11B curve predicted by our empirically determined boron isotope fractionation factor (Byrne et al., 2005; Klochko et al., 2006). Extending these experiments to wider range of pH conditions will provide the necessary inorganic baseline for paleo-studies of inorganic carbonate and future investigations of the purely biological effects on the boron isotope distributions in carbonates