Conversation of pesticide residues into ammonium nitrogen (NH₄⁺-N) through AOPs and its fertilization effect on lettuce growth

Abstract

Eliminating pesticide residues in soil through the Advanced Oxidation Processes (AOPs) has been attracted a lot of attention in recent years. However, the potential of converting them into small molecular nutrients such as ammonium nitrogen (NH₄⁺-N) has been significantly ignored. Herein, we systematically detected the transformation of clothianidin (CTD) into NH₄⁺-N through AOPs and the following effect on the growth of lettuce. Fe₃S₄-loaded biochar (BC@Fe₃S₄) was synthesized in one step through hydrothermal method, possessing excellent catalytic capacity to activate peroxymonosulfate (PMS). The results showed that the generated NH₄⁺-N could reach up to 3.029 mg L⁻¹ in soil–water system containing 20 mg L⁻¹ of CTD after the treatment of BC@Fe₃S₄ + PMS. However, when the concentration of CTD in soil was 20 mg kg⁻¹, the dry weight of lettuce was 17.3 mg/plant, and the dry weight of lettuce in CTD-contaminated soil with this concentration was 29.3 mg/plant after treatment by BC@Fe₃S₄ + PMS, and no CTD residue was detected. The results of lettuce cultivation showed that CTD in the system was converted to NH₄⁺-N after treatment with BC@Fe₃S₄ + PMS, which resulted in increased dry matter accumulation and decreased residue of lettuce seedlings. Meanwhile, LC–MS/MS analysis revealed three main degradation routes involved in the CTD degradation process. T.E.S.T-QSAR was carried out to simulate the toxicity of all degradation intermediates to Fathead minnow and T.pyriformis, manifesting that the CTD toxicity decreased after BC@Fe₃S₄ + PMS treatment. Further analysis indicated that the degradation of CTD and the formation of NH₄⁺-N occurred simultaneously, where •OH, ¹O₂ and SO₄^•− played a leading role in trigging those reactions. This work explains in detail the mechanism by which pesticides are converted into nutrients, providing feasible strategies and new perspectives for soil remediation.

Keywords

Nutrient conversion / Advanced oxidation process / Biochar / Soil remediation / Free radical / Neonicotinoid pesticides

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Funding

Distinguished Youth Foundation of Hunan Province(2022JJ10030)

Key R&D projects in Hunan Province(2022NK2044)

The Natural Science Foundation of Hunan Province, China(2021JJ40261)

The science and technology innovation Program of Hunan Province(2022WZ1022)

Hunan Provincial Cotton Industry Technology System Cultivation and Seed Breeding Post Expert Program(XIANGNONGFA (2022) No. 31)

The Hunan Provincial Department of Agriculture and Rural Affairs Project(XIANG CAI JIAN ZHI (2024) No. 162)

The Furong Plan Province enterprise science and technology innovation and entrepreneurship team support project(Hunan Talent Office [2024] No.08)

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The Author(s)