环境持久性自由基、活性氧在酚与Fe（Ⅲ）-SiO₂颗粒物的表面生成及其环境风险评估

Formation and Environmental Risk Assessment of Environmental Persistent Free Radicals and Reactive Oxygen Species on the Surfaces of Phenolic Compounds and Fe(III)-SiO₂ Particulates

摘要

环境持久性自由基（Environmental Persistent Free Radicals， EPFRs）是一类具有长寿命和多介质迁移特性的新型污染物，能够生成强氧化性的活性氧（Reactive Oxygen Species，ROS），引发机体氧化应激，进而诱发生物毒性并危害健康。因此，EPFRs 与 ROS 成为当前环境风险防控的重点关注对象。本研究选取邻苯二酚（Catechol，CT）和对叔丁基邻苯二酚（4-tert-butylcatechol，TBC）作为有机前体物，模拟其在Fe（Ⅲ）-SiO₂颗粒物表面生成EPFRs及ROS过程，揭示二者在颗粒物表面造成生态环境损害的致害机制。浓度梯度实验表明，随着酚类前体物浓度的升高，EPFRs及ROS生成量增加，且含强给电子基团的TBC生成能力强于CT，这表明前体物浓度和化学特性对EPFRs和ROS生成的重要影响；时间衰减实验表明，456 h后CT与TBC体系中生成的EPFRs仍具有较高的浓度，表明了EPFRs的环境持久性；毒性等量评估实验表明，CT与TBC体系生成的EPFRs在不同浓度梯度下分别等效于成年男性个体吸入3.8-4.0 支和 19.4-33.7 支香烟，TBC 表现出更强的健康风险。本研究阐明了 CT 和 TBC在含Fe（Ⅲ）颗粒物表面生成EPFRs和ROS的浓度水平和影响因素，研究了CT、TBC的环境行为和健康风险，为评估酚类污染物在颗粒物介质表面转化引发的生态环境风险提供理论依据。

Abstract

Environmental Persistent Free Radicals (EPFRs) are a class of novel pollutants with long lifespans and multi-medium migration characteristics. They can generate highly oxidative Reactive Oxygen Species (ROS), triggering oxidative stress in organisms and subsequently inducing toxicity and health hazards. Therefore, EPFRs and ROS have become key focal points in current environmental risk prevention and control. This study selects catechol (CT) and 4-tert-butylcatechol (TBC) as organic precursors, simulating the generation of EPFRs and ROS on the surface of Fe(Ⅲ)-SiO₂ particles, revealing the harmful mechanisms by which both contribute to ecological environmental damage. Concentration gradient experiments show that with the increase in the concentration of phenolic precursors, the amounts of EPFRs and ROS generated also increase. Furthermore, TBC, which contains strong electron-donating groups, has a higher generation capacity than CT, indicating the significant impact of precursor concentration and chemical properties on the generation of EPFRs and ROS. Time decay experiments show that after 456 hours, the EPFRs generated in the CT and TBC systems still maintain high concentrations, indicating the environmental persistence of EPFRs. Toxicity equivalence assessment experiments indicate that the EPFRs generated by the CT and TBC systems correspond to inhaling 3.8-4.0 and 19.4-33.7 cigarettes, respectively, for an adult male at different concentration gradients, with TBC demonstrating stronger health risks. This study clarifies the concentration levels and influencing factors of EPFR and ROS formation on Fe(III) -containing particulate matter surfaces by CT and TBC, investigates the environmental behavior and health risks of CT and TBC, and provides a theoretical basis for assessing the ecological and environmental risks caused by the transformation of phenolic pollutants on particulate matter surfaces.

关键词

颗粒物 / 环境持久性自由基 / 活性氧 / 邻苯二酚 / 对叔丁基邻苯二酚

Key words

Particulates / Environmental Persistent Free Radicals / Reactive Oxygen Species / Catechol / 4-tert-butylcatechol

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基金资助

国家自然科学基金(21677145)

中央高校自主部署项目专项资金(E0E48927X2)