Experimental evidence for kinetic effects on B/Ca in synthetic calcite: Implications for potential B(OH)4− and B(OH)3 incorporation

Abstract

The boron to calcium ratio (B/Ca) in biogenic CaCO3 is being increasingly utilized as a proxy for past ocean carbonate chemistry. However, B/Ca of cultured and core-top foraminifers show dependence on multiple physicochemical seawater properties and only a few of those have been inorganically tested for their impacts. Accordingly, our understanding of the controls on foraminiferal B/Ca and thus how to interpret B/Ca in fossil shells is incomplete. To gain a clearer understanding of the B incorporation mechanism, we performed inorganic calcite precipitation experiments using a pH-stat system. As previously reported, we confirm that B/Ca in calcite increases with both fluid pH and total B concentration (denoted as [BT], where [BT]=[B(OH)3]+[B(OH)4−]). We provide the first evidence that B/Ca also increases with the concentration of total dissolved inorganic carbon (DIC) and calcium ion. With the exception of the [BT] experiments, these chemical manipulations were accompanied by an increase in calcite saturation, and accordingly precipitation rate (denoted as R). But when pH and [Ca2+] were jointly varied at a fixed saturation level to maintain relatively constant R at different pH and [Ca2+] combinations, B/Ca was insensitive to both pH and [Ca2+] changes. These experimental results unequivocally suggest kinetic effects related to R on B/Ca. Furthermore, with a suite of chemical manipulations we found that the B/Ca variability is explicable by just R and the [BT]/[DIC] ratio in the parent fluids. This observation was particularly robust for relatively rapidly precipitated samples, whereas for relatively slowly precipitated samples, it was somewhat ambiguous whether the [BT]/[DIC] or [B(OH)4−]/[HCO3−] ratio provides a better fit to the experimental data. Nonetheless, our experimental results can be considered as indirect evidence for incorporation of both B(OH)4− and B(OH)3 into calcite. We propose a simple mathematical expression to describe the mode of B incorporation into synthetic calcite that depends only on the fluid [BT]/[DIC] ratio and the precipitation rate R. This novel finding has important implications for future calibrations and applications of the B/Ca proxy as well as the δ11B paleo-pH proxy.