The Characteristics and Biological Relevance of Inorganic Amorphous Calcium Carbonate (ACC) Precipitated from Seawater

TY - JOUR

T1 - The Characteristics and Biological Relevance of Inorganic Amorphous Calcium Carbonate (ACC) Precipitated from Seawater

AU - Evans, David

AU - Webb, Paul B.

AU - Penkman, Kirsty

AU - Kröger, Roland

AU - Allison, Nicola

N1 - © 2019 American Chemical Society. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details.

PY - 2019/7/3

Y1 - 2019/7/3

N2 - The importance of amorphous calcium carbonate (ACC) as a precursor phase in the biomineralization of marine calcifiers is increasingly being reported, particularly as the presence of ACC has been observed or inferred in several major groups. Here, we investigate the structure of ACC and the conditions required for its precipitation from seawater-based solutions, with an emphasis on the coinfluence of the carbonate system (pH, dissolved inorganic carbon (DIC) concentration), seawater Mg/Ca ratio, and presence of amino acids. We find that Mg2+ and the presence of aspartic acid, glutamic acid, and glycine strongly inhibit ACC precipitation. Moreover, we were unable to precipitate ACC from seawater with a carbonate chemistry within the range of that thought to characterize the calcification site of certain marine calcifiers (i.e., DIC < 6 mM, pH < 9.3), although substantial modification of the seawater Mg/Ca ratio (Mg/Casw) allowed precipitation at a reduced DIC with the implication that this could be an important component of utilizing an ACC pathway. In addition, the degree to which Mg/Casw and the presence of amino acids influences the structure of ACC and the necessary seawater [CO3 2-] for precipitation is strongly pH dependent. At lower, more biologically relevant pH than that typical of much inorganic work, decreasing Mg/Casw can result in greater long-range order and less water of crystallization but facilitates precipitation at a considerably lower [CO3 2-] than at higher pH.

AB - The importance of amorphous calcium carbonate (ACC) as a precursor phase in the biomineralization of marine calcifiers is increasingly being reported, particularly as the presence of ACC has been observed or inferred in several major groups. Here, we investigate the structure of ACC and the conditions required for its precipitation from seawater-based solutions, with an emphasis on the coinfluence of the carbonate system (pH, dissolved inorganic carbon (DIC) concentration), seawater Mg/Ca ratio, and presence of amino acids. We find that Mg2+ and the presence of aspartic acid, glutamic acid, and glycine strongly inhibit ACC precipitation. Moreover, we were unable to precipitate ACC from seawater with a carbonate chemistry within the range of that thought to characterize the calcification site of certain marine calcifiers (i.e., DIC < 6 mM, pH < 9.3), although substantial modification of the seawater Mg/Ca ratio (Mg/Casw) allowed precipitation at a reduced DIC with the implication that this could be an important component of utilizing an ACC pathway. In addition, the degree to which Mg/Casw and the presence of amino acids influences the structure of ACC and the necessary seawater [CO3 2-] for precipitation is strongly pH dependent. At lower, more biologically relevant pH than that typical of much inorganic work, decreasing Mg/Casw can result in greater long-range order and less water of crystallization but facilitates precipitation at a considerably lower [CO3 2-] than at higher pH.

UR - http://www.scopus.com/inward/record.url?scp=85070681094&partnerID=8YFLogxK

U2 - 10.1021/acs.cgd.9b00003

DO - 10.1021/acs.cgd.9b00003

M3 - Article

AN - SCOPUS:85070681094

SN - 1528-7483

JO - CRYSTAL GROWTH DESIGN

JF - CRYSTAL GROWTH DESIGN

ER -