Nitrate Chemodenitrification by Iron Sulfides to Ammonium under Mild Conditions and Transformation Mechanism.

Autotrophic denitrification utilizing iron sulfides as electron donors has been well studied, but the occurrence and mechanism of abiotic nitrate (NO3-) chemodenitrification by iron sulfides have not yet been thoroughly investigated. In this study, NO3- chemodenitrification by three types of iron sulfides (FeS, FeS2, and pyrrhotite) at pH 6.37 and ambient temperature of 30 °C was investigated. FeS chemically reduced NO3- to ammonium (NH4+), with a high reduction efficiency of 97.5% and NH4+ formation selectivity of 82.6%, but FeS2 and pyrrhotite did not reduce NO3- abiotically. Electrochemical Tafel characterization confirmed that the electron release rate from FeS was higher than that from FeS2 and pyrrhotite. Quenching experiments and density functional theory calculations further elucidated the heterogeneous chemodenitrification mechanism of NO3- by FeS. Fe(II) on the FeS surface was the primary site for NO3- reduction. FeS possessing sulfur vacancies can selectively adsorb oxygen atoms from NO3- and water molecules and promote water dissociation to form adsorbed hydrogen, thereby forming NH4+. Collectively, these findings suggest that the NO3- chemodenitrification by iron sulfides cannot be ignored, which has great implications for the nitrogen, sulfur, and iron cycles in soil and water ecosystems.

Citation

Huanhuan Hu, Yang Bai, Chong Wen Zhou, Weihang Jia, Piet N L Lens, Zhenhu Hu, David Caffrey, Xinmin Zhan. Nitrate Chemodenitrification by Iron Sulfides to Ammonium under Mild Conditions and Transformation Mechanism. Environmental science & technology. 2024 Jun 04;58(22):9804-9814

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PMID: 38771927

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