Abstract

Iron species have essential influence on the environmental/geochemical behaviors of arsenic species in water and soil. Colloidal ferric hydroxide (CFH) induces photooxidation of arsenite (As(III)) to arsenate (As(V)) in water at neutral pH through surface complexation and ligand-to-metal charge transfer (LMCT). However, the effect of the co-existing natural organic matter (NOM) on the complexation-photolysis in this process has remained unclear. In the present work, the photooxidation of As(III) induced by CFH was investigated in the presence of various carboxylic acids and polyphenols as simple model compounds of NOM. Two different light sources of ultraviolet A (UVA) (λmax = 365 nm) and ultraviolet B (UVB) (λmax = 313 nm) were used for photooxidation treatment of the experimental ternary system and the control binary system respectively. The obtained results demonstrated that all investigated NOM inhibited the photooxidation of As(III) in the As(III)/CFH system at pH 7. Moreover, the correlation analysis between the pseudo-first order rate constant kobs and various property parameters of NOM showed that the stable constant for the complexation between Fe(III) and NOM (logKFe-NOM) as well as the molecular weight of NOM and the percentages of total acidity of NOM exhibited significant correlations. A simple quantitative structure-activity relationship (QSAR) model was established between kobs and these three parameters utilizing a multiple linear regression method, which can be employed to estimate the photooxidation efficiency of As(III) in the presence of ferric iron and NOM. Thus, the present work contributes to the understanding of the environmental interactions between NOM and iron.

Highlights

  • Arsenic is a toxic substance exhibiting carcinogenic properties

  • Employing a panel of various carboxylic acids and polyphenols as the model compounds for natural organic matter (NOM), we established that 10 M of NOM inhibited the photooxidation efficiency of As(III) in the presence of ferric iron in the form of colloidal ferric hydroxide in water at circumneutral pH

  • The predominant property parameters affecting the process were in the order of logKFe-NOM > molecular weight > total acidity%

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Summary

Introduction

Arsenic is a toxic substance exhibiting carcinogenic properties. Arsenic primarily exists in inorganic oxyacid forms, including arsenite (As(III)) and arsenate (As(V)) (Cullen and Reimer, 1989). It is widely known that As(III) is more mobile and displays higher toxicity than As(V). The process of oxidative conversion of the former to As(V) is of significance. The adsorption and oxidation of various metals and their oxides, ones of iron, aluminium, and manganese, affect the form and migration of arsenic in the environment (Oscarson et al, 1981). Our previous study investigated the photochemical oxidation of As(III) on nascent colloidal ferric hydroxide (CFH) in aqueous solutions at pH 6, revealing the mechanism of the transformation of As(III) to

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