The Surface acidity of freshly synthesized microplastics particles in simple electrolyte

The surface chemistry of sub-micron microplastics (MP) particles, specifically, the pH-dependent surface charge (or surface acidity), plays a role on the transport, transformation, and effect of contaminants in the aquatic environment. Little is known on the origin of surface charge and the quantification of surface acidity of MP. In this study, the surface charge of submicron particles of six major polymers, including low-density polyethylene (LDPE), high-density polyethylene (HDPE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), and polyethylene terephthalate (PET), was characterized in inert electrolytes, namely, NaClO₄, NaCl, and NaNO₃ for the elucidation of surface acidity. IR absorbance revealed that oxygen-rich functional groups were introduced during the resynthesis of MP particles, whose surface chemical structure consists of three main functional groups, i.e., carboxylic/ester, ether/alcohol, and aliphatic. Results show clearly that the zeta potential of MP particles was negatively charged in simple electrolytes at pH greater than ca. 2.0. Hydroxide ions adsorption on the non-polar aliphatic sites, and deprotonation of surface hydroxy group on the polar carboxylic/ester and ether/alcohol sites, contributed to the negative charges on MP surface. The surface acidity of selected MP particles was established in terms of acid strength (intrinsic acidity constants) and capacity (total surface site concentration) for the three distinct surface sites. Results also show the surface acid site density increases with hydration/hydrolysis time with rate constants of the polar surface sites, i.e., carboxylic/ester and ether/alcohol being 2.3 times greater than that of the non-polar aliphatic group.