Characterization of boron incorporation and speciation in calcite and aragonite from co-precipitation experiments under controlled pH, temperature and precipitation rate

About 20 years ago, the boron isotopic composition of marine carbonates was proposed as a proxy of ancient seawater pH. Since that time, a large body of studies has used boron isotopes in carbonates to reconstruct seawater paleo-pH and atmospheric paleo-CO2 concentration. To date, however, no systematic investigation of the physicochemical parameters that control boron incorporation in calcite and aragonite (pH, temperature, precipitation rate, etc.) has been performed. To fill this gap, we have experimentally investigated the inorganic co-precipitation of boron with calcite and aragonite at 5 and 25 degrees C in the presence and absence of seed crystals and over the pH(NBS) range 7.4 < pH < 9.5 in 0.1 or 0.2 M NaCl solutions. The boron partition coefficient, D-B, between CaCO3 and the fluid is defined as: D-B = (X-B/X-CO3)(CaCO3)/[B]/[CO32-])(fluid) with X-i and [i] standing for the mole fraction and molality of the ith species in the solid and fluid, respectively. D-B measured in this study are very small (D-B <= 10(-3) and <= 10(-4) for aragonite and calcite, respectively) and exhibit a strong dependence on the solution pH and the calcium carbonate precipitation rate. High field B-11 MAS NMR analyses of the precipitated carbonates show that boron in aragonite is mostly in the form of tetragonal B (>= 85% B-[IV]) but that both trigonal and tetragonal B are present in calcite. A significant amount of tetragonal boron in calcite may be in non-lattice (defect) sites, in addition to the structural site. The relative abundance of B-[III] and B-[IV] in calcite is independent of the parent solution pH but appears to decrease with increasing precipitation rate. The change in boron coordination during its incorporation in calcite and its distribution in, at least, two different sites strongly suggest that the mechanisms controlling B incorporation in this mineral are more complex than for aragonite. It follows that calcite-based calibrations may be less reliable than aragonite calibrations for ocean paleo-pH reconstructions. (C) 2014 Elsevier Ltd. All rights reserved.