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Mechanism and multi-step kinetic modelling of Cr(VI) adsorption, reduction and complexation by humic acid, humin and kerogen from different sources

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Abstract

Humin (HM) and kerogen (KG) are widespread in soils and sediments, which have strong retention effects on the migration and transformation of Cr(VI) in subsurface environment. Previous studies mainly focused on the interaction between Cr(VI) and soluble organic matter, such as humic acid (HA); however, the adsorption and reduction mechanism for Cr(VI) by insoluble HM and KG are still unclear, the processes of which might be quite different from HA due to their different sources and humification degrees. Consequently, in this study, HA, HM and KG extracted from different sources were used to explore the adsorption, reduction and complexation mechanisms of Cr(VI) in soils and sediments, based on which a multi-step kinetic model of Cr(VI) was carried out. According to the results, the retention of Cr(VI) by humus was found to obey a coupling mechanism of “adsorption-reduction-complexation”, where Cr(VI) adsorption was by complexation with carboxylic groups by ligand exchange. The phenolic and hydroxylic groups were determined to be the main electron donor for Cr(VI) reduction. Notably, the Cr(III) produced was found to be adsorbed on the surface of humus by complexation on phenolic and hydroxylic groups, and the excesses were released into the liquid phase after the saturation of complexation sites. Based on the revealed mechanism, a multi-step kinetic model for simultaneously describing Cr(VI) adsorption and reduction and behaviour of Cr(III) was proposed producing a better fitting performance (R2 ≥ 0.984) than the first-order and second-order kinetic models (R2 ≤ 0.84 and 0.87, respectively) and hence could provide more factual understanding of Cr(VI) transformation in soils and sediments enriched in various types of humus.

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The data and materials used in this study are available in the supplementary material. Further requests can be made through the corresponding author.

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Funding

This work was financially supported by the National Natural Science Foundation of China (41977172, 41672239) and the China Geological Survey (1212011121173).

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Contributions

SB wrote the introduction, conducted the humus extraction and kinetic experiments of the study and analysed the data thereof. JZ developed the multi-step kinetic model. PAO wrote a discussion on inter-correlations between Cr(VI) adsorption and humus characteristics. AED wrote a discussion on inter-correlations between Cr(VI) reduction and humus characteristics. CDA provided relevant literature and information on the types and behaviour kerogen samples used in this study. LX conducted the titration and zeta potential experiments of humus samples. HC supervised this study and a contributor in writing the manuscript.

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Correspondence to Jia Zhang.

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Barnie, S., Zhang, J., Obeng, P.A. et al. Mechanism and multi-step kinetic modelling of Cr(VI) adsorption, reduction and complexation by humic acid, humin and kerogen from different sources. Environ Sci Pollut Res 28, 38985–39000 (2021). https://doi.org/10.1007/s11356-021-13519-z

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