超声-Fenton氧化三(2-氯乙基)磷酸酯的实验与DFT计算

李荣; 张路成; 张明青; 徐子惠

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中国环境科学 ›› 2026, Vol. 46 ›› Issue (2) : 797-808.

水污染与控制

超声-Fenton氧化三(2-氯乙基)磷酸酯的实验与DFT计算

李荣, 张路成, 张明青, 徐子惠

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Experiments and DFT calculations on ultrasonic-Fenton oxidation of tri(2-chloroethyl) phosphate

LI Rong, ZHANG Lu-cheng, ZHANG Ming-qing, XU Zi-hui

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摘要

建立了一种超声耦合Fenton氧化降解三(2-氯乙基)磷酸酯(TCEP)的技术,采用Box-Behnken响应面法优化反应参数,结合密度泛函理论(DFT)计算、液相色谱-质谱(LC-MS)分析及毒性软件(T.E.S.T.)评估,探究TCEP的降解路径与生态毒性变化.结果表明,在初始pH=3、超声功率360W、氧化剂投加量400mg/L的最佳条件下,超声-Fenton技术可有效降解TCEP,降解率达85.8%.体系中的羟基自由基等活性物质优先攻击TCEP分子中拉普拉斯键级(LBO)值较低(化学键较弱)、表面静电势(ESP)负值较高(电子云密度较大)以及反应能垒较低(反应更易发生)的反应位点(如P-O键断裂的反应能垒126.56kJ/mol、脱氯反应的反应能垒150.79kJ/mol);结合LC-MS分析证实TCEP降解的主要途径为P-O键断裂和脱氯反应.毒性评估显示,TCEP本身具有高生物累积性和诱变性,降解初期生成的羟化中间体毒性显著增强,其大鼠口服半数致死剂量(LD₅₀)达到T.E.S.T.定义的“有毒”级别(LD₅₀<50mg/kg),并可能引发发育毒性,而完全矿化后毒性显著降低.采用的模型预测方法为TCEP的降解途径和生态毒性评估提供了理论支撑.

Abstract

A technique combining ultrasonic-assisted Fenton oxidation for the degradation of tri(2-chloroethyl) phosphate (TCEP) was developed. The Box-Behnken response surface method was used to optimize the reaction parameters. The degradation pathways and ecological toxicity changes of TCEP were investigated using density functional theory (DFT) calculations, liquid chromatography-mass spectrometry (LC-MS) analysis, and toxicity software (T.E.S.T.). The results indicated that under optimal conditions (initial pH = 3, ultrasonic power of 360W, and oxidant dosage of 400mg/L), the ultrasonic-Fenton system was capable of effectively degrading TCEP, achieving a degradation rate of 85.8%. Reactive species in the system, such as hydroxyl radicals, preferentially attacked the reaction sites in the TCEP molecules with lower Laplace bond order (LBO) values (weaker chemical bonds), higher negative surface electrostatic potential (ESP) values (higher electron density), and lower reaction energy barriers (easier reaction occurrence), such as the P-O bond cleavage energy barrier of 126.56kJ/mol and the dechlorination reaction energy barrier of 150.79kJ/mol. LC-MS analysis confirmed that the primary degradation pathways of TCEP involved P-O bond cleavage and dechlorination. Toxicity assessment showed that TCEP itself exhibited high bioaccumulation potential and mutagenicity. Hydroxylated intermediates generated during the initial degradation phase exhibited significantly increased toxicity, with the oral LD₅₀ in rats reaching the “toxic” level defined by T.E.S.T. (LD₅₀<50mg/kg), and potential developmental toxicity. However, toxicity was significantly reduced after complete mineralization. The predictive modeling approach provided convenient and effective theoretical support for the degradation pathways and ecological toxicity evaluation of TCEP.

导出引用

李荣, 张路成, 张明青, 徐子惠. 超声-Fenton氧化三(2-氯乙基)磷酸酯的实验与DFT计算[J]. 中国环境科学. 2026, 46(2): 797-808

LI Rong, ZHANG Lu-cheng, ZHANG Ming-qing, XU Zi-hui. Experiments and DFT calculations on ultrasonic-Fenton oxidation of tri(2-chloroethyl) phosphate[J]. China Environmental Science. 2026, 46(2): 797-808

中图分类号： X703.1

参考文献

[1] Marklund A, Andersson B, Haglund P. Screening of organophosphorus compounds and their distribution in various indoor environments [J]. Chemosphere, 2003,53(9):1137-1146.
[2] Huo G, Wang Y. Research progress on synthesis and application of organophosphate flame retardants [J]. Plastics Additives, 2015,(5): 1-5,14.
[3] Van Der Veen I, De Boer J. Phosphorus flame retardants: Properties, production, environmental occurrence, toxicity and analysis [J]. Chemosphere, 2012,88(10):1119-1153.
[4] Sundkvist A M, Olofsson U, Haglund P. Organophosphorus flame retardants and plasticizers in marine and fresh water biota and in human milk [J]. Journal of Environmental Monitoring, 2010,12(4): 943-951.
[5] Wei G L, Li D Q, Zhuo M N, et al. Organophosphorus flame retardants and plasticizers: Sources, occurrence, toxicity and human exposure [J]. Environmental Pollution, 2015,196:29-46.
[6] Fries E, Puttmann W. Occurrence of organophosphate esters in surface water and ground water in Germany [J]. Journal of Environmental Monitoring, 2001,3(6):621-626.
[7] Martinez-carballo E, Gonzalez-barreiro C, SITKA A, et al. Determination of selected organophosphate esters in the aquatic environment of Austria [J]. Science of the Total Environment, 2007, 388(1-3):290-299.
[8] Meyer J, Bester K. Organophosphate flame retardants and plasticisers in wastewater treatment plants [J]. Journal of Environmental Monitoring, 2004,6(7):599-605.
[9] 雷慧慧,王孝飞,王超毅,等.超声增强热活化过硫酸盐降解氯代有机磷酸酯的机理探究[J].中国环境科学, 2024,44(9):4939-4947. Lei H H, Wang X F, Wang C Y, et al. Investigation into the mechanism of ultrasound-enhanced thermally activated persulfate degradation of chlorinated organophosphate esters [J]. Chinese Journal of Environmental Science, 2024,44(9):4939-4947.
[10] Rodil R, quintana J B, reemtsma T. Liquid chromatography-tandem mass spectrometry determination of nonionic organophosphorus flame retardants and plasticizers in wastewater samples [J]. Analytical Chemistry, 2005,77(10):3083-3089.
[11] Ingle M E, Watkins D, Rosario Z, et al. The association of urinary organophosphate ester metabolites and self-reported personal care and household product use among pregnant women in Puerto Rico [J]. Environmental Research, 2019,179:108756.
[12] 曾佳敏,钟仕花,钱伟,等.水环境中有机磷酸酯的污染现状及其生物毒性[J].中国环境科学, 2021,41(9):4388-4401. Zeng J M, Zhong S H, Qian W, et al. Current status of organophosphate pollution in aquatic environments and their biotoxicity [J]. Chinese Journal of Environmental Science, 2021,41(9): 4388-4401.
[13] 吴星悦,孙敦宇,季秋忆,等.氯代有机磷酸酯阻燃剂的去除技术研究进展[J].环境化学, 2022,41(3):1022-1034. Wu X Y, Sun D Y, Ji Q Y, et al. Research progress on removal technologies for chlorinated organophosphate flame retardants [J]. Environmental Chemistry, 2022,41(3):1022-1034.
[14] 罗雅嫣,汤蕙齐,李翼远,等.混合有机磷阻燃剂污染物的微生物降解特性及途径[J].中国环境科学, 2024,44(6):3434-3441. Luo Y Y, Tang H Q, Li Y Y, et al. Microbial degradation characteristics and pathways of mixed organophosphorus flame retardant pollutants [J]. Chinese Journal of Environmental Science, 2024,44(6):3434- 3441.
[15] 王俊欢.有机磷酸酯阻燃剂的微生物降解及机制研究[D].北京:中国农业科学院, 2022. Wang J H. Microbial degradation and mechanism study of organophosphate flame Retardants [D]. Beijing: Chinese Academy of Agricultural Sciences, 2022.
[16] Eslaminejad S, Rahimi R, Fayazi M. Sepiolite-metal organic framework-iron oxide catalyst for degradation of Rhodamine B using Fenton-like process [J]. Journal of the Taiwan Institute of Chemical Engineers, 2023,152:105181.
[17] Song Q Y, Feng Y P, Liu G G, et al. Degradation of the flame retardant triphenyl phosphate by ferrous ion-activated hydrogen peroxide and persulfate: Kinetics, pathways, and mechanisms [J]. Chemical Engineering Journal, 2019,361:929-936.
[18] Neves T de F, Cristale J, Camparotto N G, et al. Synergistic effect of ozonation and filtration with graphene-based membranes in the removal of flame retardants in multi-compound systems: Experimental and DFT study [J]. Journal of Environmental Chemical Engineering, 2025,13(1):114965.
[19] Cao H, Zhang W, Wang C, et al. Sonochemical degradation of poly- and perfluoroalkyl substances - A review [J]. Ultrasonics Sonochemistry, 2020,69.
[20] Peng L, Wang L, Hu X, et al. Ultrasound assisted, thermally activated persulfate oxidation of coal tar DNAPLs [J]. Journal of Hazardous Materials, 2016,318:497-506.
[21] Wang F, Sun Z, Xian S, et al. Mechanism analysis of hydroxypropyl guar gum degradation in fracture flowback fluid by homogeneous sono-Fenton process [J]. Ultrasonics Sonochemistry, 2023,93.
[22] Ma Y S, Sung C F, Lin J G. Degradation of carbofuran in aqueous solution by ultrasound and fenton processes: effect of system parameters and kinetic study [J]. Journal Of Hazardous Materials, 2010,178(1-3):320-325.
[23] Lin M, Ning X A, An T, et al. Degradation of polycyclic aromatic hydrocarbons (PAHs) in textile dyeing sludge with ultrasound and Fenton processes: Effect of system parameters and synergistic effect study [J]. Journal of Hazardous Materials, 2016,307:7-16.
[24] Fayazi M. Preparation and characterization of carbon nanotubes/pyrite nanocomposite for degradation of methylene blue by a heterogeneous Fenton reaction [J]. Journal of the Taiwan Institute of Chemical Engineers, 2021,120:229-235.
[25] Gonzalez Labrada K, Alcorta Cuello D R, Saborit Sanchez I, et al. Optimization of ciprofloxacin degradation in wastewater by homogeneous sono-Fenton process at high frequency [J]. Journal of Environmental Science And Health Part A-Toxic/Hazardous SUBSTANCES & Environmental Engineering, 2018,53(13):1139- 1148.
[26] Khataee A, Gholami P, Vahid B, et al. Heterogeneous sono-Fenton process using pyrite nanorods prepared by non-thermal plasma for degradation of an anthraquinone dye [J]. Ultrasonics Sonochemistry, 2016,32:357-370.
[27] Frisch M J, Trucks G W, Schlegel H B, et al. Gaussian 16, Revision C.01, Gaussian [Z]. Inc.: Wallingford CT, 2019.
[28] Zhang Y, Moores A, Liu J, et al. New insights into the degradation mechanism of perfluorooctanoic acid by persulfate from density functional theory and experimental data [J]. Environmental Science & Technology, 2019,53(15):8672-8681.
[29] Lu T, Chen F. Bond order analysis based on the laplacian of electron density in fuzzy overlap space [J]. The Journal of Physical Chemistry A, 2013,117(14):3100-3108.
[30] Lu T, Chen F. Multiwfn: A multifunctional wavefunction analyzer [J]. Journal of Computational Chemistry, 2012,33(5):580-592.
[31] Humphrey W, Dalke A, Schulten K. VMD: Visual molecular dynamics [J]. Journal of Molecular Graphics, 1996,14(1):33-38.
[32] Zhang L, Wang T, Zhang M, et al. Synergistic degradation of tris (2-chloroethyl) phosphate (TCEP) by US/fenton system: Experimental, DFT calculation and toxicity evaluation [J]. Environmental Science And Pollution Research, 2024,31(27):39120-39137.
[33] Zhang L, Wang T, Zhang M, et al. Ultrasonically activated persulfate process for the degradation of phenanthrene in soil-washing effluent: Experimental, DFT calculation and toxicity evaluation [J]. Journal of Environmental Chemical Engineering, 2024,12(3):113035.
[34] Zhang J H, Zou H Y, Ning X A, et al. Combined ultrasound with fenton treatment for the degradation of carcinogenic polycyclic aromatic hydrocarbons in textile dying sludge [J]. Environmental Geochemistry And Health, 2018,40(5):1867-1876.
[35] Wang X, Wei Y, Wang J, et al. The kinetics and mechanism of ultrasonic degradation of p-nitrophenol in aqueous solution with CCl4enhancement [J]. Ultrasonics Sonochemistry, 2012,19(1):32-37.
[36] Chen W S, Su Y C. Removal of dinitrotoluenes in wastewater by sono-activated persulfate [J]. Ultrasonics Sonochemistry, 2012,19(4): 921-927.
[37] 董梦,杨富,封东霞,等.基于响应面法优化生物捕收剂浮选铜离子的研究[J].矿业研究与开发, 2025,45(5):247-255. Dong M, Yang F, Feng D X, et al. Research on optimizing copper ion flotation using biological collectors based on response surface methodology [J]. Mining Research and Development, 2025,45(5):247- 255.
[38] Du L, Wang X, Wu J. Degradation of tri(2-chloroethyl)phosphate by a microwave enhanced heterogeneous Fenton process using iron oxide containing waste [J]. RSC Advances, 2018,8(32):18139-18145.