Structural model of arsenic(III) adsorbed on gibbsite based on DFT calculations

Augusto F. Oliveira; Ana Cláudia Q. Ladeira; Virgínia S.T. Ciminelli; Thomas Heine; Hélio A. Duarte

doi:10.1016/j.theochem.2005.08.038

Structural model of arsenic(III) adsorbed on gibbsite based on DFT calculations

Augusto F. Oliveira, Ana Cláudia Q. Ladeira, Virgínia S.T. Ciminelli, Thomas Heine, Hélio A. Duarte

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

34 Citations (Scopus)

Abstract

It is well known that As(III) has a higher mobility compared to As(V) in the environment. This fact is explained by the high reversibility of As(III) adsorption on minerals such as Al (hydr)oxides. Nevertheless, experimental results pointed out that adsorption of As(III) leads to inner-sphere complexes, which appears to be in conflict with the high mobility of these species as inner-sphere complexes should be strongly attached. In this work we used density functional methods and cluster models to study two different mechanisms for the H₃AsO₃ adsorption on gibbsite-γ-Al(OH)₃, one of the most abundant aluminum hydroxide minerals. Our results show that, differently from the As(V) case, As(III) is not adsorbed via an acid/base, but by a non-dissociative mechanism in which O-H bonds are not being broken. This non-dissociative mechanism also conciliates the high remobilization of As(III) with the apparently inconsistent formation of inner-sphere adsorption complexes.

Original language	English
Pages (from-to)	17-23
Number of pages	7
Journal	Journal of Molecular Structure: THEOCHEM
Volume	762
Issue number	1-3
DOIs	https://doi.org/10.1016/j.theochem.2005.08.038
Publication status	Published - 2006 Apr 2

Bibliographical note

Funding Information:
This work has been supported by the Millennium Science Initiative: Water a mineral approach and by the PROBRAL (CAPES/DAAD) program. The Brazilian agencies FAPEMIG (Fundação de Amparo a Pesquisa do Estado de Minas Gerais), CNPq (Conselho Nacional de Desenvolvimento Científico e Tecnológico) and CAPES (Coordenação de Aperfeiçoamento de Pessoal de Nível Superior) are gratefully acknowledged.

All Science Journal Classification (ASJC) codes

Biochemistry
Condensed Matter Physics
Physical and Theoretical Chemistry

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10.1016/j.theochem.2005.08.038

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title = "Structural model of arsenic(III) adsorbed on gibbsite based on DFT calculations",

abstract = "It is well known that As(III) has a higher mobility compared to As(V) in the environment. This fact is explained by the high reversibility of As(III) adsorption on minerals such as Al (hydr)oxides. Nevertheless, experimental results pointed out that adsorption of As(III) leads to inner-sphere complexes, which appears to be in conflict with the high mobility of these species as inner-sphere complexes should be strongly attached. In this work we used density functional methods and cluster models to study two different mechanisms for the H3AsO3 adsorption on gibbsite-γ-Al(OH)3, one of the most abundant aluminum hydroxide minerals. Our results show that, differently from the As(V) case, As(III) is not adsorbed via an acid/base, but by a non-dissociative mechanism in which O-H bonds are not being broken. This non-dissociative mechanism also conciliates the high remobilization of As(III) with the apparently inconsistent formation of inner-sphere adsorption complexes.",

author = "Oliveira, {Augusto F.} and Ladeira, {Ana Cl{\'a}udia Q.} and Ciminelli, {Virg{\'i}nia S.T.} and Thomas Heine and Duarte, {H{\'e}lio A.}",

note = "Funding Information: This work has been supported by the Millennium Science Initiative: Water a mineral approach and by the PROBRAL (CAPES/DAAD) program. The Brazilian agencies FAPEMIG (Funda{\c c}{\~a}o de Amparo a Pesquisa do Estado de Minas Gerais), CNPq (Conselho Nacional de Desenvolvimento Cient{\'i}fico e Tecnol{\'o}gico) and CAPES (Coordena{\c c}{\~a}o de Aperfei{\c c}oamento de Pessoal de N{\'i}vel Superior) are gratefully acknowledged.",

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AU - Oliveira, Augusto F.

AU - Ladeira, Ana Cláudia Q.

AU - Ciminelli, Virgínia S.T.

AU - Heine, Thomas

AU - Duarte, Hélio A.

N1 - Funding Information: This work has been supported by the Millennium Science Initiative: Water a mineral approach and by the PROBRAL (CAPES/DAAD) program. The Brazilian agencies FAPEMIG (Fundação de Amparo a Pesquisa do Estado de Minas Gerais), CNPq (Conselho Nacional de Desenvolvimento Científico e Tecnológico) and CAPES (Coordenação de Aperfeiçoamento de Pessoal de Nível Superior) are gratefully acknowledged.

PY - 2006/4/2

Y1 - 2006/4/2

N2 - It is well known that As(III) has a higher mobility compared to As(V) in the environment. This fact is explained by the high reversibility of As(III) adsorption on minerals such as Al (hydr)oxides. Nevertheless, experimental results pointed out that adsorption of As(III) leads to inner-sphere complexes, which appears to be in conflict with the high mobility of these species as inner-sphere complexes should be strongly attached. In this work we used density functional methods and cluster models to study two different mechanisms for the H3AsO3 adsorption on gibbsite-γ-Al(OH)3, one of the most abundant aluminum hydroxide minerals. Our results show that, differently from the As(V) case, As(III) is not adsorbed via an acid/base, but by a non-dissociative mechanism in which O-H bonds are not being broken. This non-dissociative mechanism also conciliates the high remobilization of As(III) with the apparently inconsistent formation of inner-sphere adsorption complexes.

AB - It is well known that As(III) has a higher mobility compared to As(V) in the environment. This fact is explained by the high reversibility of As(III) adsorption on minerals such as Al (hydr)oxides. Nevertheless, experimental results pointed out that adsorption of As(III) leads to inner-sphere complexes, which appears to be in conflict with the high mobility of these species as inner-sphere complexes should be strongly attached. In this work we used density functional methods and cluster models to study two different mechanisms for the H3AsO3 adsorption on gibbsite-γ-Al(OH)3, one of the most abundant aluminum hydroxide minerals. Our results show that, differently from the As(V) case, As(III) is not adsorbed via an acid/base, but by a non-dissociative mechanism in which O-H bonds are not being broken. This non-dissociative mechanism also conciliates the high remobilization of As(III) with the apparently inconsistent formation of inner-sphere adsorption complexes.

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Structural model of arsenic(III) adsorbed on gibbsite based on DFT calculations

Abstract

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