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新型吡虫啉-蒙脱石表面配合物结构的研究进展

New insights on the structure of the picloram-montmorillonite surface complexes.

机构信息

Departamento de Química Inorgánica, Analítica y Química Física e INQUIMAE, FCEN, UBA, Ciudad Universitaria, Pabellón II, C1428EHA Buenos Aires, Argentina.

Université Catholique de Louvain, Institute of Condensed Matter and Nanosciences (IMCN), Division Solids, Molecules and Reactivity (MOST), Croix du Sud 2/L7.05.17, B-1348 Louvain-la-Neuve, Belgium.

出版信息

J Colloid Interface Sci. 2015 Apr 15;444:115-22. doi: 10.1016/j.jcis.2014.12.045. Epub 2014 Dec 26.

Abstract

HYPOTHESIS

The environmental mobility and bioavailability of Picloram (PCM) are determined by the amine and carboxylate chemical groups interaction with the soils mineral phases. Clay particles, such as montmorillonite (Mt), and the pH value of the media could play an important role in adsorption processes. Thus, the study of the role of soil components other than organic matter deserves further investigation for a more accurate assessment of the risk of groundwater contamination.

EXPERIMENTS

Samples with PCM adsorbed on Mt dispersions were prepared at pH 3-9. Subsequently, the dispersions were separated, washed, centrifuged and stored at room temperature. Picloram (PCM) herbicide interaction with surface groups of montmorillonite (Mt) was studied using XRD, DTA, FTIR and XPS techniques.

FINDINGS

The entrance of PCM into the Mt basal space, in two different arrangements, perpendicular and planar, is proposed and the final arrangement depends on PCM concentration. The interaction of PCM with Mt surface sites through the nitrogen of the pyridine ring and carboxylic group of PCM, forming bidentate and bridge inner-sphere complexes was confirmed by FTIR and XPS analysis. The acidity constant of the PCM adsorbed on the Mt surface was calculated.

摘要

假设

百草枯(PCM)的环境迁移性和生物可利用性取决于胺基和羧酸盐化学基团与土壤矿物相的相互作用。粘土颗粒,如蒙脱石(Mt)和介质的 pH 值,可能在吸附过程中发挥重要作用。因此,除了有机物之外,研究土壤成分的作用值得进一步研究,以便更准确地评估地下水污染的风险。

实验

在 pH 值为 3-9 的条件下,在 Mt 分散体上吸附 PCM 的样品。随后,将分散体分离、洗涤、离心并在室温下储存。使用 XRD、DTA、FTIR 和 XPS 技术研究了百草枯(PCM)除草剂与蒙脱石(Mt)表面基团的相互作用。

结果

提出了 PCM 以两种不同的排列方式(垂直和平面)进入 Mt 基面空间的设想,最终的排列方式取决于 PCM 浓度。通过 FTIR 和 XPS 分析证实了 PCM 通过吡啶环的氮和 PCM 的羧酸基团与 Mt 表面位点的相互作用,形成了双齿和桥内球络合物。计算了吸附在 Mt 表面上的 PCM 的酸度常数。

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