Comparative analysis of organophosphorus esters, novel brominated flame retardants, and organic pesticides on soil eco-enzymatic activity

Yu Yang, Hui Huang, Haixia Tian, Yuanwei Wu, Peimei Guan, Ruiyue Lu, Ziquan Wang, Megharaj Mallavarapu, Wenxiang He
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Abstract

To evaluate the ecological risks of emerging contaminants (ECs) in soils, we systematically investigated the effects of 28 ECs, including organophosphorus esters (OPEs), novel brominated flame retardants (NBFRs), and organic pesticides on five key soil enzyme activities: β-glucosidase, urease, alkaline phosphatase, arylsulfatase (ARS), and fluorescein diacetate hydrolase (FDA-H). Among the enzymes tested, ARS activity was enhanced by nearly half of the ECs (13 out of 28), especially by OPEs. However, enzyme kinetic analyses revealed that reduced substrate affinity offsets the increased maximal reaction velocity, resulting in unchanged or even reduced catalytic efficiency. In contrast, FDA-H activity was generally inhibited, exhibiting the greatest response ratio (0.115), indicating that it was the most sensitive enzyme to pollutant exposure. Notably, 2,4,6-tribromophenol inhibited ARS via linear mixed inhibition mechanism, with ecological dose (ED10) values ranging from 7.53 to 13.9 mg kg−1, whereas isoprocarb suppressed FDA-H via competitive inhibition, with ED10 values of 3.97–6.58 mg kg−1. Based on the average magnitude of effects on soil enzymatic activities (mean score: 0.113) and the functional index (0.148), NBFRs potentially pose greater ecological risks to overall soil functionality than OPEs or the evaluated organic pesticides. These findings highlight the significant and diverse impacts of ECs on critical soil microbial functions and emphasize the urgent need for further investigation into the ecological effects of NBFRs in terrestrial environments.

有机磷酯、新型溴化阻燃剂和有机农药对土壤生态酶活性的比较分析
为了评估土壤中新出现污染物(ECs)的生态风险,我们系统地研究了28种新出现污染物(ECs),包括有机磷酯(OPEs)、新型溴化阻燃剂(NBFRs)和有机农药对5种关键土壤酶活性的影响:β-葡萄糖苷酶、脲酶、碱性磷酸酶、芳基硫酸盐酶(ARS)和荧光素二乙酸水解酶(FDA-H)。在测试的酶中,近一半的ECs(28个中的13个)增强了ARS活性,特别是OPEs。然而,酶动力学分析显示,底物亲和力的降低抵消了最大反应速度的增加,导致催化效率不变甚至降低。相反,FDA-H活性普遍受到抑制,反应比最大(0.115),表明其对污染物暴露最敏感。值得注意的是,2,4,6-三溴苯酚通过线性混合抑制机制抑制ARS,其生态剂量(ED10)值为7.53 ~ 13.9 mg kg - 1,而异丙威通过竞争抑制机制抑制FDA-H, ED10值为3.97 ~ 6.58 mg kg - 1。基于对土壤酶活性的平均影响程度(平均得分为0.113)和功能指数(0.148),NBFRs对土壤整体功能的潜在生态风险高于有机磷农药或所评价的有机农药。这些发现强调了生物多样性对关键土壤微生物功能的重要和多样化影响,并强调迫切需要进一步研究生物多样性在陆地环境中的生态效应。
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