活化过硫酸盐降解土壤典型环境内分泌干扰物

doi:10.16085/j.issn.1000-6613.2024-0608

摘要/Abstract

摘要：

随着我国工农业的迅速发展，大量环境内分泌干扰物（EEDs）在自然或人为因素作用下迁移至土壤介质中。EEDs污染造成了土壤质量的下降，引发了系列生态安全和人体健康问题，制约了我国农业的进一步发展。过硫酸盐（PS）高级氧化技术具有成本低、周期短、效率高等优势。在EEDs污染土壤修复领域，热活化、过渡金属离子活化、碳材料活化是3种极具代表性的、广受关注的典型PS活化技术。本文介绍了土壤典型EEDs分类、应用、来源及危害，论述了典型活化技术的基本原理和优缺点，重点综述了典型活化技术在降解过程中的影响因素，阐述了土壤性质对降解的影响，最后对未来研究方向进行了展望，如土壤EEDs排放清单建立、因地制宜匹配工艺、二次污染防控、土壤质量保证等，以期为EEDs污染土壤修复的现场工程应用提供理论支持。

关键词: 土壤, 环境内分泌干扰物, 过硫酸盐, 降解, 污染

Abstract:

As China's industry and agriculture rapidly develop, a significant amount of environmental endocrine disruptors (EEDs) are transported into the soil matrix by natural or human-induced means. EEDs pollution has led to a decline in soil quality, posing a series of ecological safety and human health concerns and hindering the further development of agriculture in China. Persulfate (PS) advanced oxidation technology offers advantages such as low cost, short cycle, and high efficiency. In the field of EEDs contaminated soil remediation, researcher has selected and focused on three highly representative and widely-studied PS activation techniques: thermal activation, transition metal ion activation, and carbon material activation. This paper introduced the classification, application, sources, and hazards of typical soil EEDs, discussed the basic principles, the advantages and disadvantages of typical activation technologies, highlighted the influencing factors in the degradation process, elaborated on the impact of soil properties on degradation, and concluded with a perspective on future research directions, including the establishment of soil EEDs emission inventories, process customization based on local conditions, prevention and control of secondary pollution, and soil quality assurance, etc., aiming to provide theoretical support for on-site engineering applications in remediating EEDs contaminated soil.

Key words: soil, environmental endocrine disruptors, persulfate, degradation, contamination

中图分类号:

X703

牛经纬, 陈孝杨, 张健, 周育智, 陈敏. 活化过硫酸盐降解土壤典型环境内分泌干扰物[J]. 化工进展, 2025, 44(4): 2285-2296.

NIU Jingwei, CHEN Xiaoyang, ZHANG Jian, ZHOU Yuzhi, CHEN Min. Activated persulfate-induced degradation of typical environmental endocrine disruptors in soil[J]. Chemical Industry and Engineering Progress, 2025, 44(4): 2285-2296.

图/表 6

表1 土壤典型EEDs的应用、来源及危害

EEDs	分子式	实际应用	土壤来源	危害	参考文献
菲（PHE）	C₁₄H₁₀	用于树脂、植物生长激素、生物碱、鞣料、无烟火药稳定剂、纸浆防雾剂等的生产制备	由各种矿物燃料（煤、石油、天然气等）、木材、纸、其他含碳氢化合物的不完全燃烧或在还原条件下热解产生后释放到大气中，随后与各种类型的固体颗粒物、气溶胶进行结合，最后通过干、湿沉降进入土壤	具有强烈的致毒、致癌、致突变性；对人类生殖系统、神经系统、呼吸系统、免疫系统均会造成损伤	[16-20]
蒽（ANT）	C₁₄H₁₀	用于染料、荧光增白剂、医药、农药、涂料杀虫剂、杀菌剂、汽油阻凝剂等的生产制备
芘（Pry）	C₁₆H₁₀	用于树脂、分散性染料、工程塑料、杀虫剂等的生产制备
苯并[a]芘（BaP）	C₂₀H₁₂	在工业上无生产和使用价值，在生产过程中作为副产物被排放
萘（Naph）	C₁₀H₈	用于邻苯二甲酸酐、染料中间体、橡胶助剂、杀虫剂等的生产制备
荧蒽（FLA）	C₁₆H₁₀	作为非磁性金属表面探伤荧光剂；用于染料、医药等的生产制备
莠去津（ATZ）	C₈H₁₄ClN₅	用于农作物中杂草的去除	在对农田中的杂草进行施药的过程中，部分直接进入土壤表层；茎叶残留部分经雨水淋洗后进入土壤表层；土壤表层中部分随雨水进一步下渗	已被证明是一种致癌物；对生物体的繁殖、发育、免疫均有损伤；容易对大豆、小麦、水稻等敏感作物产生植物毒性	[21-23]
对硝基酚（PNP）	C₆H₅NO₃	用于医疗药物、农药、染料、杀虫剂、杀菌剂、皮革、纺织品等的生产制备，作为化学分析试剂、植物细胞赋活剂	在工业生产和产品使用的过程中被排放到土壤中	具有强烈的致毒、致癌、致突变性	[24-25]
四溴双酚A（TBBPA）	C₁₅H₁₂Br₄O₂	作为反应型阻燃剂	在电子垃圾拆解、TBBPA生产和TBBPA基材料加工的过程中被排放到土壤中	造成甲状腺激素水平紊乱；妨碍大脑和骨骼发育等	[26-27]
三氯生（TCS）	C₁₂H₇Cl₃O₂	被添加进牙膏、漱口水、洗手液、沐浴露、洗发水、肥皂、除臭剂、化妆品、医药等产品中，起到杀菌消毒的作用	产品使用后排入水中，污水处理厂净化废水后，TCS在生物固体中富集，结束后生物固体被排入土壤	致癌；造成内分泌紊乱；增加肥胖风险；导致细菌耐药性增加	[28-29]
全氟辛酸（PFOA）	C₈HF₁₅O₂	作为洗涤剂、清洁剂等产品中的去污成分；在氟橡胶、聚四氟乙烯的生产过程中作为分散剂，帮助粒子均匀分布；作为树脂、涂料、皮革防水防油处理剂、纺织材料、建筑胶黏剂等产品生产过程中的添加剂	通过生产加工排放、大气沉降、地表径流进入土壤	长期接触下，对发育和生殖产生危害；导致肝损伤；可能致癌	[30-31]
双对氯苯基三氯乙烷（DDT）	C₁₄H₉Cl₅	用于卫生害虫和农林害虫的防治	在对农作物进行施药的过程中，部分直接进入土壤表层；茎叶残留部分经雨水淋洗后进入土壤表层；土壤表层中部分随雨水进一步下渗	致癌；导致神经行为异常；造成生殖缺陷；对内分泌和免疫系统产生危害	[32-33]
五氯酚（PCP）	C₆HCl₅O	作为水稻田除草剂；作为纺织品、皮革、纸张、木材等的防腐剂和防霉剂	在工业生产和产品使用的过程中被排放到土壤中	长期吸入会对呼吸道、血液、肾脏、肝脏、免疫系统、眼睛、鼻子、皮肤等造成损害	[34]
十溴二苯醚（BDE-209）	C₁₂Br₁₀O	用于改善塑料产品、电子产品、橡胶制品、建筑材料等产品的阻燃性能	通过生产加工排放、固废填埋、大气沉降、地表径流进入土壤	干扰甲状腺激素；妨碍人类和动物脑部与中枢神经系统的正常发育	[35-36]
磺胺甲𫫇唑（SMX）	C₁₀H₁₁N₃O₃S	用于抑制细菌的生长繁殖	通过粪便施用进入土壤	在生态环境中长期暴露会诱导细菌产生耐药基因，导致耐药菌株出现	[37-38]
17β-雌二醇（17β-E2）	C₁₈H₂₄O₂	对机体生理过程起调节作用	通过粪便施用进入土壤	其浓度较高时可破坏神经内分泌系统和生殖内分泌系统的正常功能	[39-40]
双酚A（BPA）	C₁₅H₁₆O₂	用于聚碳酸酯、环氧树脂、聚砜树脂、聚苯醚树脂、不饱和聚酯树脂、增塑剂、阻燃剂、抗氧剂、热稳定剂、橡胶防老化剂、农药、涂料等的生产制备	在生产、运输、产品使用、垃圾填埋厂处置过程中释放到土壤中	长期接触下，可导致内分泌失调；可能导致肥胖、多动症等疾病；具有一定的致癌作用	[41-42]
苯酚（PhOH）	C₆H₆O	用于酚醛树脂、锦纶纤维、增塑剂、显影剂、防腐剂、杀虫剂、杀菌剂、染料、涂料、医药、香料、农药、炸药等的生产制备	通过生产加工排放、地表径流进入土壤	长期接触大剂量苯酚可导致肌肉无力、呼吸停止、呼吸困难、震颤和昏迷；其慢性作用可能导致体重突然减轻、眩晕、厌食、腹泻	[43-44]

表1 土壤典型EEDs的应用、来源及危害

EEDs	分子式	实际应用	土壤来源	危害	参考文献
菲（PHE）	C₁₄H₁₀	用于树脂、植物生长激素、生物碱、鞣料、无烟火药稳定剂、纸浆防雾剂等的生产制备	由各种矿物燃料（煤、石油、天然气等）、木材、纸、其他含碳氢化合物的不完全燃烧或在还原条件下热解产生后释放到大气中，随后与各种类型的固体颗粒物、气溶胶进行结合，最后通过干、湿沉降进入土壤	具有强烈的致毒、致癌、致突变性；对人类生殖系统、神经系统、呼吸系统、免疫系统均会造成损伤	[16-20]
蒽（ANT）	C₁₄H₁₀	用于染料、荧光增白剂、医药、农药、涂料杀虫剂、杀菌剂、汽油阻凝剂等的生产制备
芘（Pry）	C₁₆H₁₀	用于树脂、分散性染料、工程塑料、杀虫剂等的生产制备
苯并[a]芘（BaP）	C₂₀H₁₂	在工业上无生产和使用价值，在生产过程中作为副产物被排放
萘（Naph）	C₁₀H₈	用于邻苯二甲酸酐、染料中间体、橡胶助剂、杀虫剂等的生产制备
荧蒽（FLA）	C₁₆H₁₀	作为非磁性金属表面探伤荧光剂；用于染料、医药等的生产制备
莠去津（ATZ）	C₈H₁₄ClN₅	用于农作物中杂草的去除	在对农田中的杂草进行施药的过程中，部分直接进入土壤表层；茎叶残留部分经雨水淋洗后进入土壤表层；土壤表层中部分随雨水进一步下渗	已被证明是一种致癌物；对生物体的繁殖、发育、免疫均有损伤；容易对大豆、小麦、水稻等敏感作物产生植物毒性	[21-23]
对硝基酚（PNP）	C₆H₅NO₃	用于医疗药物、农药、染料、杀虫剂、杀菌剂、皮革、纺织品等的生产制备，作为化学分析试剂、植物细胞赋活剂	在工业生产和产品使用的过程中被排放到土壤中	具有强烈的致毒、致癌、致突变性	[24-25]
四溴双酚A（TBBPA）	C₁₅H₁₂Br₄O₂	作为反应型阻燃剂	在电子垃圾拆解、TBBPA生产和TBBPA基材料加工的过程中被排放到土壤中	造成甲状腺激素水平紊乱；妨碍大脑和骨骼发育等	[26-27]
三氯生（TCS）	C₁₂H₇Cl₃O₂	被添加进牙膏、漱口水、洗手液、沐浴露、洗发水、肥皂、除臭剂、化妆品、医药等产品中，起到杀菌消毒的作用	产品使用后排入水中，污水处理厂净化废水后，TCS在生物固体中富集，结束后生物固体被排入土壤	致癌；造成内分泌紊乱；增加肥胖风险；导致细菌耐药性增加	[28-29]
全氟辛酸（PFOA）	C₈HF₁₅O₂	作为洗涤剂、清洁剂等产品中的去污成分；在氟橡胶、聚四氟乙烯的生产过程中作为分散剂，帮助粒子均匀分布；作为树脂、涂料、皮革防水防油处理剂、纺织材料、建筑胶黏剂等产品生产过程中的添加剂	通过生产加工排放、大气沉降、地表径流进入土壤	长期接触下，对发育和生殖产生危害；导致肝损伤；可能致癌	[30-31]
双对氯苯基三氯乙烷（DDT）	C₁₄H₉Cl₅	用于卫生害虫和农林害虫的防治	在对农作物进行施药的过程中，部分直接进入土壤表层；茎叶残留部分经雨水淋洗后进入土壤表层；土壤表层中部分随雨水进一步下渗	致癌；导致神经行为异常；造成生殖缺陷；对内分泌和免疫系统产生危害	[32-33]
五氯酚（PCP）	C₆HCl₅O	作为水稻田除草剂；作为纺织品、皮革、纸张、木材等的防腐剂和防霉剂	在工业生产和产品使用的过程中被排放到土壤中	长期吸入会对呼吸道、血液、肾脏、肝脏、免疫系统、眼睛、鼻子、皮肤等造成损害	[34]
十溴二苯醚（BDE-209）	C₁₂Br₁₀O	用于改善塑料产品、电子产品、橡胶制品、建筑材料等产品的阻燃性能	通过生产加工排放、固废填埋、大气沉降、地表径流进入土壤	干扰甲状腺激素；妨碍人类和动物脑部与中枢神经系统的正常发育	[35-36]
磺胺甲𫫇唑（SMX）	C₁₀H₁₁N₃O₃S	用于抑制细菌的生长繁殖	通过粪便施用进入土壤	在生态环境中长期暴露会诱导细菌产生耐药基因，导致耐药菌株出现	[37-38]
17β-雌二醇（17β-E2）	C₁₈H₂₄O₂	对机体生理过程起调节作用	通过粪便施用进入土壤	其浓度较高时可破坏神经内分泌系统和生殖内分泌系统的正常功能	[39-40]
双酚A（BPA）	C₁₅H₁₆O₂	用于聚碳酸酯、环氧树脂、聚砜树脂、聚苯醚树脂、不饱和聚酯树脂、增塑剂、阻燃剂、抗氧剂、热稳定剂、橡胶防老化剂、农药、涂料等的生产制备	在生产、运输、产品使用、垃圾填埋厂处置过程中释放到土壤中	长期接触下，可导致内分泌失调；可能导致肥胖、多动症等疾病；具有一定的致癌作用	[41-42]
苯酚（PhOH）	C₆H₆O	用于酚醛树脂、锦纶纤维、增塑剂、显影剂、防腐剂、杀虫剂、杀菌剂、染料、涂料、医药、香料、农药、炸药等的生产制备	通过生产加工排放、地表径流进入土壤	长期接触大剂量苯酚可导致肌肉无力、呼吸停止、呼吸困难、震颤和昏迷；其慢性作用可能导致体重突然减轻、眩晕、厌食、腹泻	[43-44]

图1 ROS转化途径与淬灭反应[66]

表2 典型PS活化技术的优缺点

活化技术	优点	缺点	参考文献
热活化	工艺简单；操作简便；热能环保清洁；pH条件范围广；无金属离子浸出；无须考虑催化剂分散、回收、结垢失活问题；活化过程均匀温和，不会对土壤理化性质造成严重损害；催化性能良好；多应于现场工程项目	活化能耗较高；单一热活化对土壤中EEDs的去除效果仍有限	[67-69]
过渡金属离子活化	经济节能、操作简便；在常温、常压下即可进行，无须外加能量；催化剂用量少；环境适应性好；反应选择性高、反应时间短；催化性能良好	过渡金属离子浸出，存在二次污染可能；受土壤体系pH限制	[70-72]
碳材料活化	在常温、常压下即可进行；无须外加能量和过渡金属离子参与；选择性高；环境风险低；可通过调控表面结构、功能基团、持久性自由基，实现对PS的有效活化	部分碳材料价格昂贵；催化性能较低；回收较为困难	[73-75]

表3 热活化PS降解土壤中典型EEDs

EEDs	活化技术	反应条件	降解过程	参考文献
PHE	热+十二烷基磺酸钠（SDBS）	T=328K，C_SDBS=5g/L，C_PS=50mmol，t=5d	DR=98.56%，k=0.0715h^-1；PHE的降解率随PS浓度增加而增大；降解途径：羟基化、酮化、开环	[76]
ATZ	热	T=353K，C_ATZ=50mg/kg，C_SDBS=5g/L，C_PS=24mmol/L，t=60min	DR=100%，k=0.0535min^-1；ATZ的降解率随ATZ浓度增加而减小，随PS浓度增加先增大后减小，随温度的增高而增大；降解途径为脱烷基化、脱氯羟基化	[77]
Naph	热	T=353K，C_PS=1.0mol/L，t=60min	DR=96.5%，E_a=14.85kJ/mol，k=0.0523min^-1；Naph的降解率随PS浓度增加、辐照时间增长、微波温度升高而增加；降解途径为加成、苯环断裂、开环	[78]
PNP	热	T=333K，C_PNP=93mg/kg，C_PS=60mmol/kg，t=240min，水土比=1∶1	DR=100%，E_a=137.29kJ/mol，k=0.01419min^-1；PNP的降解率随温度、PS浓度增加而增大	[24]
TBBPA	热+Fe²⁺	T=328K，C_TBBPA=20mg/kg，C_PS=50mmol/L， $C F e 2 +$ =25mmol/L，t=12h	DR=100%，k=0.370h^-1；TBBPA的降解率随温度、PS浓度增加而增大	[79]
ATZ	热	T=323K，C_ATZ=50mg/kg，C_PS=16.6mmol，t=24h	DR=84%，E_a=102kJ/mol，k=0.370h^-1；ATZ的降解率随温度、PS浓度增加而增大，随ATZ浓度增加先增大后减小；降解途径为烷基链氧化、脱烷基化、脱氯、羟基化	[80]
BaP	热	T=333K，C_BaP=100mg/kg，C_PS=0.2mol/L，t=2h	DR=48.4%；BaP的降解率随温度、PS浓度增高而增大	[81]
TCS	热	T=323K，C_TCS=50mg/kg，C_PS=18.8mmol，t=360min	DR=80%，E_a=74.3kJ/mol，k=0.370h^-1；TCS的降解率随温度、PS浓度增加而增大；降解途径为羟基化	[82]
PFOA	热	T=373K，C_BaP=200μg/kg，C_PS=100g/kg，t=9h	DR=87.3%；PFOA的降解率随PS浓度增加而增大；降解途径为脱羧、氧化	[83]
DDT	热	T=323K，C_DDT=199mg/kg，C_PS=100mmol，t=7d	DR=92%~94%（厌氧），DR=69%~78%（好氧）	[68]

表3 热活化PS降解土壤中典型EEDs

EEDs	活化技术	反应条件	降解过程	参考文献
PHE	热+十二烷基磺酸钠（SDBS）	T=328K，C_SDBS=5g/L，C_PS=50mmol，t=5d	DR=98.56%，k=0.0715h^-1；PHE的降解率随PS浓度增加而增大；降解途径：羟基化、酮化、开环	[76]
ATZ	热	T=353K，C_ATZ=50mg/kg，C_SDBS=5g/L，C_PS=24mmol/L，t=60min	DR=100%，k=0.0535min^-1；ATZ的降解率随ATZ浓度增加而减小，随PS浓度增加先增大后减小，随温度的增高而增大；降解途径为脱烷基化、脱氯羟基化	[77]
Naph	热	T=353K，C_PS=1.0mol/L，t=60min	DR=96.5%，E_a=14.85kJ/mol，k=0.0523min^-1；Naph的降解率随PS浓度增加、辐照时间增长、微波温度升高而增加；降解途径为加成、苯环断裂、开环	[78]
PNP	热	T=333K，C_PNP=93mg/kg，C_PS=60mmol/kg，t=240min，水土比=1∶1	DR=100%，E_a=137.29kJ/mol，k=0.01419min^-1；PNP的降解率随温度、PS浓度增加而增大	[24]
TBBPA	热+Fe²⁺	T=328K，C_TBBPA=20mg/kg，C_PS=50mmol/L， $C F e 2 +$ =25mmol/L，t=12h	DR=100%，k=0.370h^-1；TBBPA的降解率随温度、PS浓度增加而增大	[79]
ATZ	热	T=323K，C_ATZ=50mg/kg，C_PS=16.6mmol，t=24h	DR=84%，E_a=102kJ/mol，k=0.370h^-1；ATZ的降解率随温度、PS浓度增加而增大，随ATZ浓度增加先增大后减小；降解途径为烷基链氧化、脱烷基化、脱氯、羟基化	[80]
BaP	热	T=333K，C_BaP=100mg/kg，C_PS=0.2mol/L，t=2h	DR=48.4%；BaP的降解率随温度、PS浓度增高而增大	[81]
TCS	热	T=323K，C_TCS=50mg/kg，C_PS=18.8mmol，t=360min	DR=80%，E_a=74.3kJ/mol，k=0.370h^-1；TCS的降解率随温度、PS浓度增加而增大；降解途径为羟基化	[82]
PFOA	热	T=373K，C_BaP=200μg/kg，C_PS=100g/kg，t=9h	DR=87.3%；PFOA的降解率随PS浓度增加而增大；降解途径为脱羧、氧化	[83]
DDT	热	T=323K，C_DDT=199mg/kg，C_PS=100mmol，t=7d	DR=92%~94%（厌氧），DR=69%~78%（好氧）	[68]

表4 过渡金属离子活化PS降解土壤中典型EEDs

EEDs	活化技术	反应条件	降解过程	参考文献
ATZ	Fe²⁺+CA	T=298K，C_ATZ=50mg/kg，C_PS=10g/L， $C F e S O 4$ =11.7g/L，C_CA=1.76g/L，t=24h	DR=73.6%；TBBPA的降解率随活化剂预加入时间增加先增大后减小，随PS浓度增加而增大	[91]
PCP	Fe²⁺/Fe⁰	T=298K，C_PCP=9.91mg/kg，C_PS=0.3mol/kg， $C F e 2 + / F e 0$ =0.09mol/kg，t=7d	$D R F e 2 +$ =76.7%， $D R F e 0$ =62.8%， $k F e 2 +$ =0.07265d^-1， $k F e 0$ =0.04042d^-1；PCP的降解率随PS浓度增加而增大，随Fe²⁺/Fe⁰浓度的增加先增大后减小	[92]
Naph PHE FLA BaP	Fe⁰	T=333K，C_Naph=77.85mg/kg，C_PHE=80.09mg/kg，C_FLA=79.96mg/kg，C_BaP=53.46mg/kg，C_PS=1mol/L， $C F e 0$ =0.5mol/L，t=36h	DR_Naph=98.15%，DR_PHE=78.41%，DR_FLA=93.47%，DR_BaP=97.64%，k_Naph=0.0231h^-1，k_PHE=0.0214h^-1，k_FLA=0.0269h^-1，k_BaP=0.0386h^-1；PCP的降解率随PS、Fe⁰浓度增加先增大后减小	[93]
低环/中环/高环PAHs	Fe²⁺+HA Fe²⁺+CA	T=298K，C_PAHs=196.34mg/kg，C_PS=0.5mmol/g， $C F e S O 4$ =0.5mmol/g，C_HA、CA=0.096g/g，t=16h	DR_PAHs=79.89%（Fe²⁺+HA）；DR_PAHs=70.92%（Fe²⁺+CA）；DR_L-PAHs=90%，DR_M-PAHs=71.88%，DR_H-PAHs=71.96%（Fe²⁺+HA）；PAHs降解效果呈现低环>中环>高环趋势	[94]
Pry	Fe²⁺ Co²⁺ Ag⁺	T=303K，C_Pry=76.4mg/kg，C_PS=2.5mmol/g， $C F e 2 + 、 C o 2 + 、 A g +$ =0.25mmol/g，t=2h	$D R F e 2 +$ =93.4%， $D R C o 2 +$ =91.3%， $D R A g +$ =92.7%（Na₂S₂O₈）； $D R F e 2 +$ =92.5%， $D R C o 2 +$ =97.0%， $D R A g +$ =92.7%（KHSO₄）； $k F e 2 +$ =0.0037min^-1， $k C o 2 +$ =0.0063min^-1， $k A g +$ =0.0029min^-1（Na₂S₂O₈）； $k F e 2 +$ =0.0031min^-1， $k C o 2 +$ =0.0054min^-1， $k A g +$ =0.0026min^-1（KHSO₄）	[95]
p,p'-DDT o,p'-DDT	Fe²⁺	T=298K，C_p_,_p_'-DDT=29.56mg/kg，C_o_,_p_'-DDT=5.02mg/kg，C_PS=0.16mol/L， $C F e 2 +$ =0.008mol/L，t=24h	DR_DDT=90%；DDT的降解率随PS浓度增加而增大，随Fe²⁺浓度增加先增大后减小	[96]
BDE-209	Fe⁰ S-Fe⁰ K@S-Fe⁰	T=303K，C_BDE-209=10mg/kg，C_PS=0.2mol/L， $C F e 0 、 S - F e 0 、 K @ S - F e 0$ =2g/kg，t=110min	$D R F e 0$ =48.39%， $D R S - F e 0$ =54.27%， $D R K @ S - F e 0$ =63.33%；BDE-209的降解率随PS浓度增加而增大，随K@S-Fe⁰浓度增加先增大后减小；降解途径为脱溴、苯环开环	[97]
BaP Pry PHE Naph	Fe⁰ BC₈₀₀ Fe⁰@BC₈₀₀	T=298K，C_BaP=26.99mg/kg，C_PS=0.5g/L， $C F e 0 、 B C 800 、 F e 0 @ B C 800$ =0.01g/g，t=60min	$D R F e 0$ =34.52%， $D R B C 800$ =57.80%， $D R F e 0 @ B C 800$ =73.91%， $k F e 0$ =0.0836min^-1， $k B C 800$ =0.1639min^-1， $k F e 0 @ B C 800$ =0.2650min^-1（BaP）；DR_Pry=84.85%，DR_PHE=79.25%，DR_Naph=37.80%（Fe⁰@BC₈₀₀）；BaP的降解率随Fe⁰@BC₈₀₀浓度增加而增大，随PS浓度增加先增大后减小；降解途径为裂解、开环	[98]
ATZ	FeNPs@BC	T=298K，C_ATZ=20.55mg/kg，C_AME=21.76mg/kg，C_TEA=22.56mg/kg，C_SIM=20.28mg/kg，C_PS=3mmol/L，C_FeNPs@BC=5g/L，t=10min	DR_ATZ=100%，k_ATZ=0.19023min^-1，DR_SIM>DR_TEA>DR_ATZ>DR_AME；ATZ的降解率随PS浓度增加而增大，随FeNPs@BC浓度增大先增大后减小；降解途径为脱乙基化、亲电亲核攻击	[99]
TBBPA	Fe⁰	T=298K，C_TBBPA=5mg/kg，C_PS=25mmol， $C F e 0$ =3g/kg，t=12h	DR_TBBPA=78.32%；TBBPA的降解率随PS浓度增加而增大，随着催化剂浓度增加先增加后减小；降解途径为脱溴、异丙基与苯环发生断裂	[70]

表4 过渡金属离子活化PS降解土壤中典型EEDs

EEDs	活化技术	反应条件	降解过程	参考文献
ATZ	Fe²⁺+CA	T=298K，C_ATZ=50mg/kg，C_PS=10g/L， $C F e S O 4$ =11.7g/L，C_CA=1.76g/L，t=24h	DR=73.6%；TBBPA的降解率随活化剂预加入时间增加先增大后减小，随PS浓度增加而增大	[91]
PCP	Fe²⁺/Fe⁰	T=298K，C_PCP=9.91mg/kg，C_PS=0.3mol/kg， $C F e 2 + / F e 0$ =0.09mol/kg，t=7d	$D R F e 2 +$ =76.7%， $D R F e 0$ =62.8%， $k F e 2 +$ =0.07265d^-1， $k F e 0$ =0.04042d^-1；PCP的降解率随PS浓度增加而增大，随Fe²⁺/Fe⁰浓度的增加先增大后减小	[92]
Naph PHE FLA BaP	Fe⁰	T=333K，C_Naph=77.85mg/kg，C_PHE=80.09mg/kg，C_FLA=79.96mg/kg，C_BaP=53.46mg/kg，C_PS=1mol/L， $C F e 0$ =0.5mol/L，t=36h	DR_Naph=98.15%，DR_PHE=78.41%，DR_FLA=93.47%，DR_BaP=97.64%，k_Naph=0.0231h^-1，k_PHE=0.0214h^-1，k_FLA=0.0269h^-1，k_BaP=0.0386h^-1；PCP的降解率随PS、Fe⁰浓度增加先增大后减小	[93]
低环/中环/高环PAHs	Fe²⁺+HA Fe²⁺+CA	T=298K，C_PAHs=196.34mg/kg，C_PS=0.5mmol/g， $C F e S O 4$ =0.5mmol/g，C_HA、CA=0.096g/g，t=16h	DR_PAHs=79.89%（Fe²⁺+HA）；DR_PAHs=70.92%（Fe²⁺+CA）；DR_L-PAHs=90%，DR_M-PAHs=71.88%，DR_H-PAHs=71.96%（Fe²⁺+HA）；PAHs降解效果呈现低环>中环>高环趋势	[94]
Pry	Fe²⁺ Co²⁺ Ag⁺	T=303K，C_Pry=76.4mg/kg，C_PS=2.5mmol/g， $C F e 2 + 、 C o 2 + 、 A g +$ =0.25mmol/g，t=2h	$D R F e 2 +$ =93.4%， $D R C o 2 +$ =91.3%， $D R A g +$ =92.7%（Na₂S₂O₈）； $D R F e 2 +$ =92.5%， $D R C o 2 +$ =97.0%， $D R A g +$ =92.7%（KHSO₄）； $k F e 2 +$ =0.0037min^-1， $k C o 2 +$ =0.0063min^-1， $k A g +$ =0.0029min^-1（Na₂S₂O₈）； $k F e 2 +$ =0.0031min^-1， $k C o 2 +$ =0.0054min^-1， $k A g +$ =0.0026min^-1（KHSO₄）	[95]
p,p'-DDT o,p'-DDT	Fe²⁺	T=298K，C_p_,_p_'-DDT=29.56mg/kg，C_o_,_p_'-DDT=5.02mg/kg，C_PS=0.16mol/L， $C F e 2 +$ =0.008mol/L，t=24h	DR_DDT=90%；DDT的降解率随PS浓度增加而增大，随Fe²⁺浓度增加先增大后减小	[96]
BDE-209	Fe⁰ S-Fe⁰ K@S-Fe⁰	T=303K，C_BDE-209=10mg/kg，C_PS=0.2mol/L， $C F e 0 、 S - F e 0 、 K @ S - F e 0$ =2g/kg，t=110min	$D R F e 0$ =48.39%， $D R S - F e 0$ =54.27%， $D R K @ S - F e 0$ =63.33%；BDE-209的降解率随PS浓度增加而增大，随K@S-Fe⁰浓度增加先增大后减小；降解途径为脱溴、苯环开环	[97]
BaP Pry PHE Naph	Fe⁰ BC₈₀₀ Fe⁰@BC₈₀₀	T=298K，C_BaP=26.99mg/kg，C_PS=0.5g/L， $C F e 0 、 B C 800 、 F e 0 @ B C 800$ =0.01g/g，t=60min	$D R F e 0$ =34.52%， $D R B C 800$ =57.80%， $D R F e 0 @ B C 800$ =73.91%， $k F e 0$ =0.0836min^-1， $k B C 800$ =0.1639min^-1， $k F e 0 @ B C 800$ =0.2650min^-1（BaP）；DR_Pry=84.85%，DR_PHE=79.25%，DR_Naph=37.80%（Fe⁰@BC₈₀₀）；BaP的降解率随Fe⁰@BC₈₀₀浓度增加而增大，随PS浓度增加先增大后减小；降解途径为裂解、开环	[98]
ATZ	FeNPs@BC	T=298K，C_ATZ=20.55mg/kg，C_AME=21.76mg/kg，C_TEA=22.56mg/kg，C_SIM=20.28mg/kg，C_PS=3mmol/L，C_FeNPs@BC=5g/L，t=10min	DR_ATZ=100%，k_ATZ=0.19023min^-1，DR_SIM>DR_TEA>DR_ATZ>DR_AME；ATZ的降解率随PS浓度增加而增大，随FeNPs@BC浓度增大先增大后减小；降解途径为脱乙基化、亲电亲核攻击	[99]
TBBPA	Fe⁰	T=298K，C_TBBPA=5mg/kg，C_PS=25mmol， $C F e 0$ =3g/kg，t=12h	DR_TBBPA=78.32%；TBBPA的降解率随PS浓度增加而增大，随着催化剂浓度增加先增加后减小；降解途径为脱溴、异丙基与苯环发生断裂	[70]

表5 碳材料活化PS降解土壤中典型EEDs

EEDs	活化技术	反应条件	降解过程	参考文献
中环/高环PAHs	Fe²⁺+GLU（单聚糖） Fe²⁺+SUC（双聚糖） Fe²⁺+Starch（多聚糖）	T=298K，C_PAHs=196.34mg/kg， $C F e S O 4$ =0.5mmol/g，C_PS=0.5mmol/g，C_HA、CA=0.096g/g，t=16h，水土比=0.6∶1	DR_PAHs=56.76%（Fe²⁺+GLU）；DR_PAHs=65.05%（Fe²⁺+SUC）；DR_PAHs=77.94%（Fe²⁺+Starch）；DR_M-PAHs=69.94%，DR_H-PAHs=84.37%（Fe²⁺+Starch）	[94]
SMX	BC_400/700 石墨（GP）	T=298K，C_SMX=20mg/kg，C_BC=5g/kg，C_PS=4.8g/kg，t=2h，水土比=1∶1	$D R B C 400$ =42.6%~53.8%， $D R B C 700$ =68.4%~90.7%，DR_GP=20.3%~50.6%；降解途径为去磺酰基、羟基化、开环、氧化	[102]
17β-E2	氧化钒改性碳纳米管（VO _X -CNT）	T=303K，C_SMX=20mg/kg， $C V O X - C N T$ =0.005g/g，n（17β-E2）/n（PDS）=1∶50，t=12h，水土比=2∶1	DR=86.06%；17β-E2的降解率随催化剂浓度、PS浓度的增大而增大；降解途径为羟基氧化、六元环碳碳键断裂	[103]
BPA	BC	T=298K，C_BPA=31.93mg/kg，C_BC=4g/kg，C_PS=18.4g/L，t=160min	DR=98.4%；BPA的降解率随BC浓度增大先增加后减小，随PS浓度增大而增大	[104]
PhOH	球磨胶体活性炭（CACBM）	T=298K，C_PhOH=5.63mmol/kg，C_CACBM=2.5mg/g，C_PS=5mmol，t=24h，水土比=5∶1	DR=91.4%；PhOH的降解率随CACBM浓度增加而增大，随PS浓度增加先增大后减小	[105]
ATZ	BC	C_ATZ=100mg/kg，C_BC=0.25g/g，C_PS=0.15g/g，t=2d，水土比=4∶5	DR=82.52%，k=0.04h^-1；ATZ的降解率随PS浓度增加而增大	[106]
BaP	BC	T=298K，C_BaP=42.6mg/kg，C_BC=0.15g/g，C_PS=9g/L，t=60min	DR=93.2%，k=0.04h^-1；BaP的降解率随BC剂量增加先增大后减小，随PS浓度增加而增大	[74]

表5 碳材料活化PS降解土壤中典型EEDs

EEDs	活化技术	反应条件	降解过程	参考文献
中环/高环PAHs	Fe²⁺+GLU（单聚糖） Fe²⁺+SUC（双聚糖） Fe²⁺+Starch（多聚糖）	T=298K，C_PAHs=196.34mg/kg， $C F e S O 4$ =0.5mmol/g，C_PS=0.5mmol/g，C_HA、CA=0.096g/g，t=16h，水土比=0.6∶1	DR_PAHs=56.76%（Fe²⁺+GLU）；DR_PAHs=65.05%（Fe²⁺+SUC）；DR_PAHs=77.94%（Fe²⁺+Starch）；DR_M-PAHs=69.94%，DR_H-PAHs=84.37%（Fe²⁺+Starch）	[94]
SMX	BC_400/700 石墨（GP）	T=298K，C_SMX=20mg/kg，C_BC=5g/kg，C_PS=4.8g/kg，t=2h，水土比=1∶1	$D R B C 400$ =42.6%~53.8%， $D R B C 700$ =68.4%~90.7%，DR_GP=20.3%~50.6%；降解途径为去磺酰基、羟基化、开环、氧化	[102]
17β-E2	氧化钒改性碳纳米管（VO _X -CNT）	T=303K，C_SMX=20mg/kg， $C V O X - C N T$ =0.005g/g，n（17β-E2）/n（PDS）=1∶50，t=12h，水土比=2∶1	DR=86.06%；17β-E2的降解率随催化剂浓度、PS浓度的增大而增大；降解途径为羟基氧化、六元环碳碳键断裂	[103]
BPA	BC	T=298K，C_BPA=31.93mg/kg，C_BC=4g/kg，C_PS=18.4g/L，t=160min	DR=98.4%；BPA的降解率随BC浓度增大先增加后减小，随PS浓度增大而增大	[104]
PhOH	球磨胶体活性炭（CACBM）	T=298K，C_PhOH=5.63mmol/kg，C_CACBM=2.5mg/g，C_PS=5mmol，t=24h，水土比=5∶1	DR=91.4%；PhOH的降解率随CACBM浓度增加而增大，随PS浓度增加先增大后减小	[105]
ATZ	BC	C_ATZ=100mg/kg，C_BC=0.25g/g，C_PS=0.15g/g，t=2d，水土比=4∶5	DR=82.52%，k=0.04h^-1；ATZ的降解率随PS浓度增加而增大	[106]
BaP	BC	T=298K，C_BaP=42.6mg/kg，C_BC=0.15g/g，C_PS=9g/L，t=60min	DR=93.2%，k=0.04h^-1；BaP的降解率随BC剂量增加先增大后减小，随PS浓度增加而增大	[74]

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