Fungal Electrochemical Remediation of Herbicide-contaminated Soil: Preliminary Study on Degradation Kinetics

doi:10.13560/j.cnki.biotech.bull.1985.2023-0895

Abstract

Abstract:

【Objective】 Microbial fuel cell（MFC）, which produces electricity while removing pollutants, is a promising means of ecological restoration. We aim to construct a fungal-augmented MFC device, compare the effects, advantages and disadvantages of electrokinetic（EK）, fungal and MFC remediation against herbicides in the polluted soil, and explored the application potential of MFC in the remediation of organic pollutants. 【Method】 A novel MFC with fungal bioaugmentation was designed. The contaminated soil by two herbicides was remediated by three methods of EK, fungi and MFC remediations, and the screened and domesticated Talaromyces dalianensis and Myrothecium verrucaria strains were implemented in the latter two approaches. The effect of fungal augmentation on the removal of herbicides was studied. Soil pH, electrical conductivity, herbicide removal, and MFC electrical performance were quantified, and degradation products of two herbicides were identified by gas chromatography-mass spectrometry. 【Result】 In EK remediation, when simulated electrolyte, carbon fiber and 10 V were applied for 7 d, the removal rate of florpyrauxifen-benzyl（F）and haloxyfop-P（H）was 71% and 38%, respectively. Compared with H, F was more easily degraded, and fungal and MFC treatments completely removed it. Compared with T. dalianensis, M. verrucaria strain had better degradation capacity to both herbicides. MFC based on two fungi had the removal rate of 62.5% and 24.1% respectively toward H. The degradation product of F and H was halauxifen and 4-methoxybenzyl acetate, respectively, and the degradation pathways and kinetics were speculated. The degradation of F by three methods and the degradation of H by EK followed the first-order kinetic reaction, while the degradation of H by fungi and MFC followed the second-order reaction. 【Conclusion】 Compared with EK and fungal remediations, MFC remediation had a better effect, which can remediate the soil without the need for additional power supply, making it a cost-effective self-sustaining remediation strategy.

Key words: electrochemical remediation, microbial fuel cell, Talaromyces dalianensis DJTU-SJ5, Myrothecium verrucaria DJTU-sh7, soil remediation

HAO Da-cheng, ZHENG Yu-wei, WANG Fan, HAN Lei, ZHANG Ze. Fungal Electrochemical Remediation of Herbicide-contaminated Soil: Preliminary Study on Degradation Kinetics[J]. Biotechnology Bulletin, 2024, 40(3): 261-272.

Figures/Tables 9

Fig. 1 Chemical structures of herbicides A: Florpyrauxifen-benzyl, C20H14Cl2F2N2O3; B: haloxyfop-P, C15H11ClF3NO4

Table 1 Degradation scheme of fungi and MFC

分组Group	土壤中污染物含量 Pollutant content in soil	菌液Composition
（1）F	97.14 mg/kg F	不添加菌液No fungal addition
（2）F+T	97.14 mg/kg F	20 mL F+ 20 mL T
（3）F+M	97.14 mg/kg F	20 mL F+20 mL M
（4）F+T+M	97.14 mg/kg F	20 mL F+ 10 mL T + 10 mL M
（5）H	245.71 mg/kg H	不添加菌液No fungal addition
（6）H+T	245.71 mg/kg H	20 mL H+ 20 mL T
（7）H+M	245.71 mg/kg H	20 mL H+ 20 mL M
（8）H+T+M	245.71 mg/kg H	20 mL H+ 10 mL T + 10 mL M

Fig. 2 Methods of EK degradation A: EK remediation device. B: After the counter electrode is connected with the reference electrode, 1 is connected with the steel mesh cathode 3, and the working electrode 2 is connected with the carbon felt anode 4. C: Profile of the sampling sites; 1 is 2 cm from the anode, 2 is 4 cm from the anode, and 3 is 6 cm from the anode（near the cathode）

Fig. 3 Methods of MFC degradation A: MFC device. B: The anode and the cathode are placed horizontally. The anode is located directly above the cathode, with an interval of 3.5 cm, and the top of the soil is 2 cm from the upper edge of the container. C: At the bottom of the MFC device, a small hole is provided to facilitate the contact between the cathode and the air. D: Profile of MFC device（1: anode; 2: cathode; A: the anode sampling point; C: the cathode sampling point）

Fig. 4 Results of EK remediation F groups: F1 and F2（+ carbon fiber 2 g）are control groups without electricity; F3, F4, F5, F6（+ carbon fiber 2 g）are subject to voltage 5 V, 10 V, 10 V, 10 V, respectively; deionized water rather than electrolyte is applied in F5 group. The grouping of H is similar to that of F. A: Soil pH changes of F groups. 0, no electrode. B: Soil pH changes of H groups. C: Changes of soil electrical conductivity in F groups. 0, no electrode. D: Changes of soil electrical conductivity in H groups. E: The change of current density in F groups, and the upper right inset shows the changes of charge. F: The change of current density in H groups. G: Removal rate of F. H: Removal rate of H. Different lowercase letters represent the significant differences（P < 0.05）between different treatment groups of the same layer, the same below

Fig. 5 Fungal remediation A: Soil pH changes of F groups. B: Soil pH changes of H groups. C: Changes of soil electrical conductivity in F groups. D: Changes of soil electrical conductivity in H groups. E: Removal rate of F. F: Removal rate of H. Different lowercase letters indicate the significant differences（P < 0.05）between different treatment groups of the same duration

Fig. 6 Results of MFC remediation A: Anode; C: cathode. MFC performance of F groups: A: Day 2. B: Day 15. C: Day 30. MFC performance of H groups: D: Day 2. E: Day 15. F: Day 30. G: Changes of soil pH in F groups. H: Changes of soil pH in H groups. I: Changes of soil electrical conductivity in F groups. J: Changes of soil electrical conductivity in H groups. K: Removal rate of F. L: Removal rate of H

Fig. 7 Degradation products of herbicides A: Mass spectrum of F degradation products. B: Mass spectrum of H degradation products. C: Full scan ion fragment diagram of halauxifen. D: Full scan ion fragment diagram of 4-methoxybenzyl acetate. E: Full scan ion fragment diagram of haloxyfop-methyl. F: Degradation pathway of F. G: Degradation pathway of H

Table 2 Degradation kinetics of herbicides

处理 Treatment	氯氟吡啶酯 Florpyrauxifen-benzyl（F）				高效氟吡甲禾灵Haloxyfop-P（H）
处理 Treatment	反应 Reaction	降解速率常数 Degradation rate constant	R²	半衰期Half-life/d	反应 Reaction	降解速率常数 Degradation rate constant	R²	半衰期 Half-life/d
EK处理 EK treatment	一级反应First order reaction	0.248 ± 0.009	0.993 01	2.8	一级反应First order reaction	0.053 ± 0.002	0.991 44	13.0
微生物处理 Microbial treatment	一级反应First order reaction	0.054 ± 0.001	0.946 30	12.7	二级反应Second order reaction	1.968×10-4 ± 4.979×10-7	0.999 99	50.6
MFC处理 MFC treatment	一级反应First order reaction	0.136 ± 0.001	0.998 16	5.1	二级反应Second order reaction	5.921×10-4 ± 9.888×10-7	0.999 99	16.8

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