Abstract

Groundwater contamination by microplastic (MP) causes increasing concern about the critical factors that determine MP transport mechanisms in the vadose zone. Strong water repellency of native microplastic surfaces and respective attractive hydrophobic interactions with components of the soil matrix limits its mobility. However, adsorption of dissolved organic matter (DOM) onto microplastic surfaces can potentially make them more hydrophilic, enhancing their mobility. Consequently, the main objective of this study was to systematically determine the effects of DOM on both the surface properties and the mobility of polystyrene microplastic (PSP), and to use the extended DLVO theory (XDLVO) to predict PSP transport behavior with natural DOM for the first time. Breakthrough experiments were conducted in columns filled with quartz sand, through which PSP (1 µm) were percolated at either 0 or 5 mg/L dissolved organic carbon (DOC) derived from beech (Fagus sylvatica) litter at ionic strengths ranging from 0.5 to 2.5 mM CaCl2, since the cation background also affects wettability and mobility. Using sessile drop contact angle and zeta potential measurements, XDLVO interaction energy components including Lewis acid-base energies were approximated. Breakthrough curve analysis confirmed that DOM coming from natural sources strongly enhanced the mobility of PSP in the quartz sand matrix, in particular at higher ionic strength. At 2.5 mM CaCl2, the presence of DOM increased PSP breakthrough from 1 % to 60 %. Consequently, in the absence of DOM, laser microscope images showed much more pronounced formation of microplastic clusters on quartz grain surfaces than at co-percolation of PSP with DOM. This behavior could be clearly predicted with the XLDVO approach, which suggests at 0 mg/L DOC a deep primary energy minimum between individual PSP and between PSP and quartz surfaces. In contrast, repulsive hydrophilic interactions between the surfaces were predicted at 5 mg/L DOC. We conclude that even low concentrations of DOM, as usually found in subsoil, can significantly enhance the mobility of microplastic in soils via rendering the surfaces more hydrophilic. This implies potentially serious repercussions for the spread of this contaminant in the environment.

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