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无定形碳酸钙镁体系中的溶解度研究。

Solubility investigations in the amorphous calcium magnesium carbonate system.

作者信息

Purgstaller Bettina, Goetschl Katja E, Mavromatis Vasileios, Dietzel Martin

机构信息

Institute of Applied Geosciences , Graz University of Technology , Rechbauerstrasse 12 , 8010 Graz , Austria . Email:

Géosciences Environnement Toulouse (GET) , CNRS , UMR 5563 , Observatoire Midi-Pyrénées , 14 Avenue Edouard Belin , 31400 Toulouse , France.

出版信息

CrystEngComm. 2019 Jan 7;21(1):155-164. doi: 10.1039/c8ce01596a. Epub 2018 Nov 20.

Abstract

Amorphous precursors are known to occur in the early stages of carbonate mineral formation in both biotic and abiotic environments. Although the Mg content of amorphous calcium magnesium carbonate (ACMC) is a crucial factor for its temporal stabilization, to date little is known about its control on ACMC solubility. Therefore, amorphous Ca Mg CO·HO solids with 0 ≤ ≤ 1 and 0.4 ≤ ≤ 0.8 were synthesized and dispersed in MgCl-NaHCO buffered solutions at 24.5 ± 0.5 °C. The chemical evolution of the solution and the precipitate clearly shows an instantaneous exchange of ions between ACMC and aqueous solution. The obtained ion activity product for ACMC (IAP = "solubility product") increases as a function of its Mg content ([Mg] = (1 - ) × 100 in mol%) according to the expression: log(IAP) = 0.0174 (±0.0013) × [Mg] - 6.278 (±0.046) ( = 0.98), where the log(IAP) shift from Ca (-6.28 ± 0.05) to Mg (-4.54 ± 0.16) ACMC endmember, can be explained by the increasing water content and changes in short-range order, as Ca is substituted by Mg in the ACMC structure. The results of this study shed light on the factors controlling ACMC solubility and its temporal stability in aqueous solutions.

摘要

已知无定形前体在生物和非生物环境中碳酸盐矿物形成的早期阶段都会出现。尽管无定形碳酸钙镁(ACMC)的镁含量是其时间稳定性的关键因素,但迄今为止,关于其对ACMC溶解度的控制知之甚少。因此,合成了0≤≤1且0.4≤≤0.8的无定形Ca Mg CO·HO固体,并将其分散在24.5±0.5°C的MgCl-NaHCO缓冲溶液中。溶液和沉淀物的化学演化清楚地表明ACMC与水溶液之间存在离子的瞬时交换。根据表达式,所获得的ACMC的离子活度积(IAP =“溶度积”)随其镁含量([Mg] =(1 - )×100,单位为mol%)的增加而增加:log(IAP) = 0.0174(±0.0013)×[Mg] - 6.278(±0.046)( = 0.98),其中log(IAP)从Ca(-6.28±0.05)向Mg(-4.54±0.16)ACMC端元的转变,可以通过ACMC结构中Ca被Mg取代导致的含水量增加和短程有序变化来解释。本研究结果揭示了控制ACMC在水溶液中溶解度及其时间稳定性的因素。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f769/6336086/fac8bb687b43/c8ce01596a-f1.jpg

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