|本期目录/Table of Contents|

[1]彭美淋,雷 蒙,郑 菲,等.相对湿度对铁锰氧化物表面甲基对硫磷降解行为的影响[J].武汉工程大学学报,2026,48(03):253-260.[doi:10.19843/j.cnki.CN42-1779/TQ.202510005]
　PENG Meilin,LEI Meng,ZHENG Fei,et al.Effect of relative humidity on the degradation behavior of methyl parathion on the surface of iron-manganese oxides[J].Journal of Wuhan Institute of Technology,2026,48(03):253-260.[doi:10.19843/j.cnki.CN42-1779/TQ.202510005]
点击复制

相对湿度对铁锰氧化物表面甲基对硫磷降解行为的影响
(/HTML)

《武汉工程大学学报》[ISSN:1674-2869/CN:42-1779/TQ]

卷:
48
期数:
2026年03期
页码:
253-260
栏目:
磷化工论坛
出版日期:
2026-06-30

文章信息/Info

Title:
Effect of relative humidity on the degradation behavior of methyl parathion on the surface of iron-manganese oxides
文章编号:
1674 - 2869（2026）03 - 0253 - 08
作者:

1. 武汉工程大学化学与环境工程学院，湖北 武汉 430205；
2. 磷矿及其共伴生资源绿色高效开发利用全国重点实验室，湖北 武汉 430205
Author(s):
PENG Meilin1;  LEI Meng1;  ZHENG Fei1;  HU Lisong1;  DONG Wanqiang1; 2;  LIAO Xiaoping*1
1. School of Chemical and Environmental Engineering, Wuhan Institute of Technology， Wuhan 430205， China；
2. State Key Laboratory of Green and Efficient Development of Phosphorus Resources, Wuhan 430205, China
关键词:
铁锰氧化物; 甲基对硫磷; 相对湿度; 降解行为
Keywords:
iron manganese oxide;  methyl parathion;  relative humidity;  degradation behavior
分类号:
X53；X131.3
DOI:
10.19843/j.cnki.CN42-1779/TQ.202510005
文献标志码:
A
摘要:
土壤中有机磷农药的污染问题引起了广泛的关注，探索有机磷农药在土壤铁锰氧化物表面的环境行为对厘清该类污染物在环境中的归宿至关重要。研究了水分有限条件下7种不同晶型铁、锰氧化物对甲基对硫磷的降解行为。结果表明，甲基对硫磷在铁氧化物和铁锰氧化物表面主要发生水解反应，锰氧化物表面同时发生水解和氧化反应。相对湿度在33%~76%时，铁氧化物对甲基对硫磷的水解速率最高（1.37×10-2 h-1）；锰氧化物对甲基对硫磷降解的速率（Kobs）与相对湿度之间呈现明显的负相关，相对湿度从5%升至100%时，Kobs值从0.66 h-1下降至0.31 h-1。此外，α-MnO2对甲基对硫磷降解的速率（0.276 h-1·m-2）比针铁矿（0.010 6 h-1·m-2）和铁锰氧化物（0.004 03 h-1·m-2）高2~3个数量级。铁氧化物和锰氧化物表面羟基和Lewis酸位点共同控制甲基对硫磷的水解行为；然而，铁锰氧化物对甲基对硫磷的水解仅受表面Lewis酸位点影响。本研究的结果强调水分有限条件下铁、锰氧化物对有机磷农药降解行为的影响，也揭示了该类污染物在土壤环境中可能被长期忽略的非生物转化行为。
Abstract:
The pollution of soil by organophosphorus pesticides (OPPs) has attracted widespread attention from researchers. Exploring the environmental behaviors of OPPs on the surface of soil iron-manganese oxides is crucial for clarifying the environmental fate of such pollutants. The degradation behaviors of methyl parathion (MP) by seven iron and manganese oxides with different crystal forms were investigated under limited moisture conditions. Results showed that MP mainly underwent hydrolysis on the surface of iron oxides and iron-manganese oxides, while both hydrolysis and oxidation reactions occurred simultaneously on the surface of manganese oxides. When the relative humidity (RH) was in the range of 33%-76%, the hydrolysis rate of MP by iron oxides reached the maximum (1.37×10-2 h-1). For manganese oxides, there was a significant negative correlation between the observed degradation rate (Kobs) of MP and RH. As RH increased from 5% to 100%, the Kobs value decreased from 0.66 h-1 to 0.31 h-1. In addition, the degradation rate of MP by α-MnO2 (0.276 h-1·m-2) was 2~3 orders of magnitude higher than that of goethite (0.010 6 h-1·m-2) and iron-manganese oxides (0.004 03 h-1·m-2). The hydrolysis of MP by iron oxides and manganese oxides was jointly controlled by surface hydroxyl groups and Lewis acid sites, while the hydrolysis by the iron-manganese oxide was governed exclusively by the surface Lewis acid sites. The findings of this study underscore the impact of limited moisture conditions on the catalytic transformation of OPPs by iron and manganese oxides, and also reveal the likely long-overlooked abiotic transformation behavior of such pollutants in the soil environment.

参考文献/References:

[ 1 ] SINGH B K. Organophosphorus-degrading bacteria: ecology and industrial applications [J]. Nature Reviews Microbiology, 2009, 7(2): 156-164.
[ 2 ] 张瑞福. 有机磷农药长期污染土壤的微生物分子生态效应[D]. 南京: 南京农业大学, 2004.
[ 3 ] KHAMMANEE N, QIU Y L, KUNGSKULNITI N, et al. Presence and health risks of obsolete and emerging pesticides in paddy rice and soil from Thailand and China [J]. International Journal of Environmental Research and Public Health, 2020, 17(11): 3786.
[ 4 ] CASTILHO J A A, FENZL N, GUILLEN S M, et al. Organochlorine and organophosphorus pesticide residues in the Atoya river basin, Chinandega, Nicaragua [J]. Environmental Pollution, 2000, 110(3): 523-533.
[ 5 ] MA J, XIAO R, LI J, et al. Determination of organophosphorus pesticides in underground water by SPE-GC-MS [J]. Journal of Chromatographic Science, 2009, 47(2): 110-115.
[ 6 ] 丁浩东, 万红友, 秦攀, 等. 环境中有机磷农药污染状况、来源及风险评价[J]. 环境化学, 2019, 38(3): 463-479.
[ 7 ] CELIK I, SUZEK H. The hematological effects of methyl parathion in rats [J]. Journal of Hazardous Materials, 2008, 153(3): 1117-1121.
[ 8 ] CORAL M N U, UCMAN S, HASAN Y, et al. Potential neoplastic effects of parathion-methyl on rat liver [J]. Journal of Environmental Sciences, 2009, 21(5): 696-699.
[ 9 ] M?KIE P, PERSSON P,?STERLUND L. Adsorp-tion of trimethyl phosphate and triethyl phosphate on dry and water pre-covered hematite, maghemite, and goethite nanoparticles [J]. Journal of Colloid and Interface Science, 2013, 392: 349-358.
[10] LU J X, GUO Z Z, WANG S, et al. Remove of triclosan from aqueous solutions by nanoflower MnO2: insight into the mechanism of oxidation and adsorption [J]. Chemical Engineering Journal, 2021, 426: 131319.
[11] ZHANG G S, LIU F D, LIU H J, et al. Respective role of Fe and Mn oxide contents for arsenic sorption in iron and manganese binary oxide: an X-ray absorption spectroscopy investigation [J]. Environmental Science & Technology, 2014, 48(17): 10316-10322.
[12] TORRENTS A, STONE A T. Hydrolysis of phenyl picolinate at the mineral/water interface [J]. Environmental Science & Technology, 1991, 25(1): 143-149.
[13] TORRENTS A, STONE A T. Catalysis of picolinate ester hydrolysis at the oxide/water interface: inhibition by coadsorbed species [J]. Environmental Science & Technology, 1993, 27(6): 1060-1067.
[14] LIAO X P, ZHANG C X, LIU Y, et al. Abiotic degradation of methyl parathion by manganese dioxide: kinetics and transformation pathway [J]. Chemosphere, 2016, 150: 90-96.
[15] HUSSAIN A, CLASSENS G, GUEVARA-ROZO S, et al. Spatial variation in soil available water holding capacity alters carbon mobilization and allocation to chemical defenses along jack pine stems [J]. Environmental and Experimental Botany, 2020, 171: 103902.
[16] NI J J, CHENG Y F, WANG Q H, et al. Effects of vegetation on soil temperature and water content: field monitoring and numerical modelling [J]. Journal of Hydrology, 2019, 571: 494-502.
[17] MITCHELL S M, ULLMAN J L, TEEL A L, et al. Hydrolysis of amphenicol and macrolide antibiotics: chloramphenicol, florfenicol, spiramycin, and tylosin [J]. Chemosphere, 2015, 134: 504-511.
[18] MINGELGRIN U, SALTZMAN S, YARON B. A possible model for the surface-induced hydrolysis of organophosphorus pesticides on kaolinite clays [J]. Soil Science Society of America Journal, 1977, 41(3): 519-523.
[19] SALTZMAN S, YARON B, MINGELGRIN U. The surface catalyzed hydrolysis of parathion on kaolinite [J]. Soil Science Society of America Journal, 1974, 38(2): 231-234.
[20] WU D D, HUANG S H, ZHANG X X, et al. Iron minerals mediated interfacial hydrolysis of chloramphenicol antibiotic under limited moisture conditions [J]. Environmental Science & Technology, 2021, 55(14): 9569-9578.
[21] JIN X, WU D D, LING J Y, et al. Hydrolysis of chloramphenicol catalyzed by clay minerals under nonaqueous conditions [J]. Environmental Science & Technology, 2019, 53(18): 10645-10653.
[22] LI T, ZHONG W, JING C Y, et al. Enhanced hydrolysis of p-nitrophenyl phosphate by iron (hydr)oxide nanoparticles: roles of exposed facets [J]. Environmental Science & Technology, 2020, 54(14): 8658-8667.
[23] NARIMANI-SABEGH S, NOROOZIAN E. Magnetic solid-phase extraction and determination of ultra-trace amounts of antimony in aqueous solutions using maghemite nanoparticles [J]. Food Chemistry, 2019, 287: 382-389.
[24] 廖小平. 江汉平原典型研究区有机磷农药分布特征及氧化还原机制研究[D]. 武汉: 中国地质大学, 2016.
[25] CAI G Y, LI L P, LI D K, et al. Rapid purification of As(III) in water using iron-manganese composite oxide coupled with sulfite: importance of the SO5 ?- radicals [J]. Water Research, 2022, 222: 118839.
[26] YE X, JIANG X, CHEN L, et al. Effect of manga-nese dioxide crystal structure on adsorption of SO2 by DFT and experimental study [J]. Applied Surface Science, 2020, 521: 146477.
[27] BALDWIN D S, BEATTIE J K, COLEMAN L M, et al. Hydrolysis of an organophosphate ester by manganese dioxide [J]. Environmental Science & Technology, 2001, 35(4): 713-716.
[28] SHENG F, LING J Y, WANG C, et al. Rapid hydrolysis of penicillin antibiotics mediated by adsorbed zinc on goethite surfaces [J]. Environ-mental Science & Technology,2019,53(18): 10705-10713.
[29] SHAYAN N N, MIRZAYI B. Adsorption and removal of asphaltene using synthesized maghemite and hematite nanoparticles [J]. Energy & Fuels, 2015, 29(3): 1397-1406.
[30] MARTIN G J, CUTTING R S, VAUGHAN D J, et al. Bulk and key surface structures of hematite, magnetite, and goethite: a density functional theory study [J]. American Mineralogist, 2009, 94(10): 1341-1350.
[31] WATANABE H, SETO J. The catalysis of maghemite and hematite on the aldol and the retro-aldol condensation of acetone [J]. Bulletin of the Chemical Society of Japan, 1991, 64(8): 2411-2415.
[32] ZHANG S H, Lü J T, HAN R X, et al. Sustained production of superoxide radicals by manganese oxides under ambient dark conditions [J]. Water Research, 2021, 196: 117034.
[33] WANG Z Q, JIA H Z, ZHAO H R, et al. Oxygen limitation accelerates regeneration of active sites on a MnO2 surface: promoting transformation of organic matter and carbon preservation [J]. Environmental Science & Technology, 2022, 56(13): 9806-9815.
[34] BUXTON G V, GREENSTOCK C L, HELMAN W P, et al. Critical review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (?OH/?O- in aqueous solution [J]. Journal of Physical and Chemical Reference Data, 1988, 17(2): 513-886.
[35] ZHANG J H, LI Y B, WANG L, et al. Catalytic oxidation of formaldehyde over manganese oxides with different crystal structures [J]. Catalysis Science & Technology, 2015, 5(4): 2305-2313.
[36] LIAO X P, ZHOU C Q, ZHENG F, et al. Methyl parathion degradation from the sulfite oxidation catalyzed by crystallographic manganese oxides: formation and role of singlet oxygen [J]. Separation and Purification Technology, 2025, 361: 131325.
[37] TORRENTS A, STONE A T. Oxide surface-catalyzed hydrolysis of carboxylate esters and phosphorothioate esters [J]. Soil Science Society of America Journal, 1994, 58(3): 738-745.


相似文献/References:

备注/Memo

备注/Memo:
收稿日期：2025-10-15
基金项目：国家自然科学基金（41702267）；武汉工程大学科学基金（K201935）；武汉工程大学研究生教育创新基金
（CX2022423）
作者简介：彭美淋，硕士研究生。Email：2468016652@qq.com
*通信作者：廖小平，博士，副教授。Email：xiaopingliao@wit.edu.cn
更新日期/Last Update: 2026-06-26