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Updated: Jun 13, 2025

An Experimental Protocol for Studying Mineral Effects on Organic Hydrothermal Transformations
Published on: August 8, 2018
The reduction of nitrobenzene by Fe(II)-goethite-hematite heterogeneous systems: Insight from thermodynamic
Xin Li1, Aiyu Niu1, Shanshan Yang1
1Key Laboratory of Groundwater Conservation of MWR, China University of Geosciences (Beijing), Beijing, 100083, China; Beijing Key Laboratory of Water Resources and Environmental Engineering, China University of Geosciences (Beijing), Beijing, 100083, China.
Abstract:
Determining the contaminants reduction rate by dissolved ferrous iron (Fe(II)aq) bound to iron oxides is curial for evaluating the abiotic attenuation of contaminants in aquifers. However, few studies have assessed the contaminants reduction rate controlled by thermodynamic parameters in heterogeneous systems with different iron oxides. In this study, a linear free energy relationship (LFER) was established between the nitrobenzene reduction rate and the thermodynamic driving force (reduction potential (EH) and pH) in Fe(II)aq-goethite-hematite co-existing systems. Results showed that the reduction rate of nitrobenzene correlated with the EH of the heterogeneous system. The standard reduction potential (EH0mix) of the mixed iron oxides could be obtained by a proportionate linear combination of the single iron oxide system EH0. Based on this, the EH of the heterogeneous systems could be calculated theoretically by combining EH0mix and the Nernst equation. Furthermore, a parallel LFER with the slope of 1 was established to associate the nitrobenzene reduction rate with EH and pH. The intercept term was related to the adsorption capacity of different iron oxides towards Fe(II)aq. The Fe(II)aq saturation adsorption capacity of hematite was 1.5 times higher than that of goethite. After normalizing the nitrobenzene reduction rate to the Fe(II)aq saturation adsorption capacity, the maximum difference in intercept terms was reduced from 37% to 15%. These findings would provide an important and feasible methodological support for the quantitative evaluation of abiotic attenuation of contaminants in groundwater.
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