Investigating the Role of Carbonate Ion Concentration on the Magnesium Content of Amorphous Calcium Carbonate
Abstract
The fields of biomineralization and carbonate geochemistry are undergoing a paradigm shift with the realization that the formation of calcite with diverse compositions and textures can be understood within the framework of multiple pathways to mineralization. Many organisms do not form their skeletons via the classical step-growth process, but instead mineralization occurs through a mesocrystal pathway that begins with the formation of amorphous calcium carbonate (ACC), which subsequently transforms to calcite. Little is known about factors that regulate this type of calcification because the last 50 years of research have focused almost entirely on step-growth processes. In particular, new findings indicate that the chemical signatures and properties of calcites that form via an amorphous pathway are significantly different. Variable temperature has been shown to influence the amount of magnesium that is incorporated into ACC, but the effect of alkalinity has not been constrained. Here, a flow-through method was developed to produce ACC within a geochemically relevant pH range and with a constant supersaturation, and to determine the effect of carbonate ion concentration on magnesium uptake. The experimental approach uses a high precision syringe pump to prepare ACC under specified and constant chemical conditions. This study used two syringes that contained: 1) 100 ml of MgCl2?6H2O and CaCl2?2H2O such that the Mg/Ca ratio is fixed at 5:1 (modern seawater), and 2) 100 ml of 60mM - 400mM NaHCO3. The initial sodium bicarbonate solutions were buffered to a pH of 9.75 using NaOH, and upon mixing with the 5:1 Mg/Ca solution the resulting pH range was 9.2 - 9.7. All experiments were performed at temperatures between 21.5 and 23 degrees Celsius. Solution and solids were collected on 0.20 micron filter paper with a vacuum pump running continuously. Experiments were typically conducted for an hour and a half and all samples were rinsed with distilled deionized water before collection. The final ACC samples were characterized using a combination of SEM, Raman Spectroscopy, and ICP-OES. Preliminary results indicate that the Mg content of ACC increases with the carbonate ion concentration of the input solution. This shift in composition corresponds with measurements of a smaller average particle size. Future work will determine if the ACC that forms at these different carbonate concentrations subsequently influences the composition and structure of the final crystalline products. Findings from this work may lead to better predictions of how biological calcification processes will respond to the shifts in carbonate chemistry that accompany ocean acidification.
- Publication:
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AGU Fall Meeting Abstracts
- Pub Date:
- December 2011
- Bibcode:
- 2011AGUFMPP41A1738B
- Keywords:
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- 1050 GEOCHEMISTRY / Marine geochemistry