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RESEARCH ARTICLE
Contents Vol 6(4)

Molecular modeling of iron and arsenic interactions with carboxy groups in natural biomass

Gabriela C. Silva A , Igor F. Vasconcelos B , Regina P. de Carvalho A C , Maria Sylvia S. Dantas A and Virginia S. T. Ciminelli A D
+ Author Affiliations
- Author Affiliations

A Department of Metallurgical and Materials Engineering, Universidade Federal de Minas Gerais, Avenida Antônio Carlos 6627 – CEP 31270-901, Belo Horizonte MG, Brazil.

B Department of Metallurgical and Materials Engineering, Universidade Federal do Ceará, Campus do Pici Bloco 714 – CEP 60455-760, Fortaleza CE, Brazil.

C Microscopy Centre, Universidade Federal de Minas Gerais, Avenida Antônio Carlos 6627 – CEP 31270-901, Belo Horizonte MG, Brazil.

D Corresponding author. Email: ciminelli@demet.ufmg.br

Environmental Chemistry 6(4) 350-356 https://doi.org/10.1071/EN09031
Submitted: 10 March 2009  Accepted: 19 June 2009   Published: 25 August 2009

Environmental context. Arsenic has been considered one of the most important global environmental pollutants. Its occurrence in water systems is a result of natural processes and anthropogenic activities. In view of their high toxicity and the consequent health problems associated with human exposure to contaminated waters and food, there is an increasing interest in the study of the specific interactions of arsenic species with organic matter. Here, specific interactions among arsenic, iron and a vegetable biomass are investigated with a view to demonstrate how these interactions can affect arsenic mobility in the environment.

Abstract. The interaction of iron and arsenic with dried lettuce leaves was investigated using a combination of spectroscopic techniques. Iron binding to carboxy groups is indicated by a decrease of 84% in iron loading after esterification. According to extended X-ray absorption fine structure (EXAFS) analysis, FeIII is coordinated by six oxygen atoms (Fe–O distance of 1.98 Å), two carbon atoms (Fe–C distance of 2.85 Å) in a bidentate mononuclear form, and 0.5 or 1 arsenic atoms (Fe–As distance of 2.93–2.94 Å). Arsenic is sorbed only when the biomass has been previously loaded with iron. AsV is coordinated by four oxygen atoms (As–O distance of 1.71 Å) and one iron atom in a bidentate mononuclear form or two iron atoms (As–Fe distance of 2.93–2.94 Å) in a bidentate binuclear form. In conclusion, the results demonstrate that carboxylic acid groups can affect AsV mobility in the environment so long as iron is available for bridging.

Additional keywords: arsenic, biomass, carboxyl, EXAFS, iron.


Acknowledgements

The authors thank Professor Wander L. Vasconcelos for the FTIR analysis. Financial support for this research was provided by Fapemig, Capes and CNPq. X-ray absorption spectroscopy was performed at the Laboratório Nacional de Luz Síncrotron (LNLS/Campinas/Brazil). The contributions from anonymous reviewers are also gratefully acknowledged The authors are members of the National Institute of Science and Technology – Acqua.


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Accessory publication

Examples of the iron sorption raw data and arsenic isotherm are available from the author or from the Environmental Chemistry website at http://publish.csiro.au/?act=view_file&file_id=EN09031_AC.pdf.