Abiotic reduction of Cr(VI) by humic acids derived from peat and lignite: kinetics and removal mechanism

Andrew B. Ross,Andrew W. Bray,Fiona L. Gill,Douglas I. Stewart,Ian T. Burke,Giannantonio Cibin,Michael E. Ries,Daniel L. Baker,Suha T. Aldmour

doi:10.1007/s11356-018-3902-1

Andrew B. Ross, Andrew W. Bray + Show 7 more

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https://doi.org/10.1007/s11356-018-3902-1

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Abstract

Hexavalent chromium contamination of groundwater is a worldwide problem caused by anthropogenic and natural processes. We report the rate of Cr(VI) removal by two humic acids (extracted from Miocene age lignite and younger peat soil) in aqueous suspensions across a pH range likely to be encountered in terrestrial environments. Cr(VI) was reduced to Cr(III) in a first-order reaction with respect Cr(VI) concentration, but exhibited a partial order (~ 0.5) with respect to [H+]. This reaction was more rapid with the peat humic acid, where Cr(VI) reduction was observed at all pH values investigated (3.7 ≤ pH ≤ 10.5). 13C NMR and pyrolysis GC-MS spectroscopy indicate that the reaction results in loss of substituted phenolic moieties and hydroxyl groups from the humic acids. X-ray absorption spectroscopy indicated that at all pH values the resulting Cr(III) was associated with the partially degraded humic acid in an inner-sphere adsorption complex. The reaction mechanism is likely to be controlled by ester formation between Cr(VI) and phenolic/hydroxyl moieties, as this initial step is rapid in acidic systems but far less favourable in alkaline conditions. Our findings highlight the potential of humic acid to reduce and remove Cr(VI) from solution in a range of environmental conditions.

Highlights

IntroductionChromium is a strategically important metal that is produced commercially from the chromite ore as sodium dichromate and similar chemicals (Wilbur et al 2000; Jacobs and Testa 2005; Kogel et al 2006)
Responsible editor: Céline GuéguenElectronic supplementary material The online version of this article contains supplementary material, which is available to authorized users.Chromium is a strategically important metal that is produced commercially from the chromite ore as sodium dichromate and similar chemicals (Wilbur et al 2000; Jacobs and Testa 2005; Kogel et al 2006)
Aldrich humic acid produces 10× more ash upon ignition than Peat humic acid (PHA) (27% and 2%)

Summary

Introduction

Chromium is a strategically important metal that is produced commercially from the chromite ore as sodium dichromate and similar chemicals (Wilbur et al 2000; Jacobs and Testa 2005; Kogel et al 2006). It is widely used in alloys, electroplating, leather tanning, timber treatment, wax, chromate pigments, refractories, ceramics, catalysts and organic acids (Barnhart 1997; Darrie 2001; Jacobs and Testa 2005; International Chromium Development Association 2016). Cr(VI) is toxic to plants (Chandra and Kulshreshtha 2004; Shanker et al 2005), animals and humans (Costa 1997) and is classified as a mutagenic and carcinogenic material (Leonard and Lauwerys 1980; Kondo et al 2003; Holmes et al 2008)

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