Differences in Neonicotinoid and Metabolite Sorption to Activated Carbon Are Driven by Alterations to the Insecticidal Pharmacophore.
Differences in Neonicotinoid and Metabolite Sorption to Activated Carbon Are Driven by Alterations to the Insecticidal Pharmacophore.
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DOI：
10.1021/acs.est.0c04187
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发表时间：
2020-10
影响因子：
11.4
通讯作者：
Danielle T Webb;Matthew R. Nagorzanski;Megan M Powers;David M. Cwiertny;M. Hladik;Gregory H. LeFevre
中科院分区：
文献类型：
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作者：
Danielle T Webb;Matthew R. Nagorzanski;Megan M Powers;David M. Cwiertny;M. Hladik;Gregory H. LeFevre
类烟碱的广泛应用导致其在沃茨中的扩散。尽管类烟碱疏水性低，但我们先前的研究涉及颗粒活性炭（GAC）去除类烟碱。基于已知的受体结合特性，我们假设杀虫药效团影响类烟碱的吸附。我们的目标是照亮驱动程序的亲类烟碱（吡虫啉，噻虫胺，噻虫嗪，噻虫啉）和药效团改变的代谢产物（去硝基-吡虫啉和吡虫啉尿素）吸附到GAC，粉末活性炭，碳纳米管（CNT）。新烟碱吸附到GAC是广泛的，在很大程度上是不可逆的，与显着更大的吸附比去硝基吡虫啉的吡虫啉。吡虫啉和吡虫啉脲（电负性药效团）最广泛地吸附在非功能化碳纳米管上，而去硝基吡虫啉（正性药效团）最广泛地吸附在羧基碳纳米管上，这表明药效团和碳表面之间的电荷相互作用和/或氢键的重要性。水化学参数（温度，碱度，离子强度和腐殖酸）抑制整体类烟碱的吸附，表明药效团驱动的吸附在真实的沃茨可能会减少。对全规模饮用水处理厂GAC过滤器进水、出水和用过的GAC的分析首次将真实条件下的类烟碱/代谢物去除归因于GAC。我们的研究结果表明，类烟碱药效团不仅赋予杀虫剂的选择性，但也影响吸附行为，导致GAC过滤器在水处理中的代谢物的有效去除。
Widespread application of neonicotinoids has led to their proliferation in waters. Despite low neonicotinoid hydrophobicity, our prior studies implicated granular activated carbon (GAC) in neonicotinoid removal. Based on known receptor binding characteristics, we hypothesized that the insecticidal pharmacophore influences neonicotinoid sorption. Our objectives were to illuminate drivers of neonicotinoid sorption for parent neonicotinoids (imidacloprid, clothianidin, thiamethoxam, and thiacloprid) and pharmacophore-altered metabolites (desnitro-imidacloprid and imidacloprid urea) to GAC, powdered activated carbon, and carbon nanotubes (CNTs). Neonicotinoid sorption to GAC was extensive and largely irreversible, with significantly greater sorption of imidacloprid than desnitro-imidacloprid. Imidacloprid and imidacloprid urea (electronegative pharmacophores) sorbed most extensively to nonfunctionalized CNTs, whereas desnitro-imidacloprid (positive pharmacophore) sorbed most to COOH-CNTs, indicating the importance of charge interactions and/or hydrogen bonding between the pharmacophore and carbon surface. Water chemistry parameters (temperature, alkalinity, ionic strength, and humic acid) inhibited overall neonicotinoid sorption, suggesting that pharmacophore-driven sorption in real waters may be diminished. Analysis of a full-scale drinking water treatment plant GAC filter influent, effluent, and spent GAC attributes neonicotinoid/metabolite removal to GAC under real-world conditions for the first time. Our results demonstrate that the neonicotinoid pharmacophore not only confers insecticide selectivity but also impacts sorption behavior, leading to less effective removal of metabolites by GAC filters in water treatment.