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标题：A Comparison of the Solubility Products of Layered Me(II)–Al(III) Hydroxides Based on Sorption Studies with Ni(II), Zn(II), Co(II), Fe(II), and Mn(II)
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作者：Lasita Bhattacharya ; Evert J. Elzinga
期刊名称：Soil Systems
电子版ISSN：2571-8789
出版年度：2018
卷号：2
期号：2
页码：20-34
DOI：10.3390/soilsystems2020020
出版社：MDPI AG
摘要：The precipitation of mixed metal–aluminum-layered double hydroxides (Me(II)–Al(III)-LDH)) may be an important control of the solubility of Mn(II), Fe(II), Ni(II), Zn(II), and Co(II) in soils, but assessment of this process is hindered by a lack of thermodynamic data. Here, we determined the solubility products (Ksp) of the Me(II)–Al(III)-LDHs formed by these metals based on long-term Me(II)–γAl2O3 sorption studies complemented with X-ray absorption spectroscopy (XAS) measurements. The LDH phases had the chemical formula Me(II)2/3Al1/3(OH)2Cl1/3. Solubility products were derived as Ksp = (Me2+)aq2/3(Al3+)aq1/3(OH−)aq2(Cl−)aq1/3, where brackets represent aqueous activity values determined from the equilibrium solution chemistry of the sorption samples. The Ksps are metal-dependent, with values increasing by two orders of magnitude in the order Ni(II) < Zn(II) < Co(II) < Fe(II) < Mn(II). Comparison to the solubility of β-Me(OH)2 suggests considerable thermodynamic preference of Me(II)–Al(III)-LDH over β-Me(OH)2 in soil environments and reveals a linear relation between the log-transformed Ksp values of Me(II)–Al(III)-LDH and β-Me(OH)2. Solubility plots suggest that Ni(II)–, Zn(II)–, and Co(II)–Al(III)-LDH may form in metal-polluted soils. Fe(II)–Al(III)-LDH may occur in riparian soils undergoing reduction, but precipitation of Mn(II)–Al(III)-LDH appears unlikely as it requires [Mn2+]aq much higher than commonly encountered in reducing soils. Additional thermodynamic and field studies are needed to further assess the importance of Me(II)–Al(III)-LDHs in soils and related geochemical systems.
关键词：trace metals; layered double hydroxides; sorption; precipitation; solubility; aluminum trace metals ; layered double hydroxides ; sorption ; precipitation ; solubility ; aluminum