Heterogeneous interactions and transformations of dibasic esters with indoor relevant surfaces.

Abstract

Dibasic esters (DBEs) have recently become emerging indoor air pollutants due to their usage as a solvent for mixtures of paints and coatings. In this study, we explored the adsorption/desorption kinetics, heterogeneous interactions, and chemical transformations of dimethyl succinate (DMS, C6H10O4), a component of commercial dibasic ester solvent mixtures, on indoor relevant surfaces using transmission Fourier-transform infrared (FTIR) spectroscopy and high-resolution mass spectrometry (HRMS). Silica (SiO2) and rutile (TiO2) were used as proxies for window glass, and an active component in paint and self-cleaning surfaces, respectively. FTIR spectroscopy of these surfaces shows that DMS can interact with SiO2 and TiO2 through hydrogen bonding between the carbonyl oxygen and surface hydroxyl groups. The kinetics show fast adsorption of DMS onto these surfaces followed by slow desorption. Furthermore, new products formed observed on TiO2 surfaces in addition to molecularly adsorbed DMS. In particular, succinate (C5H7O) was observed binding to the surface in a bidentate chelating coordination mode as indicated by the appearance of νas(COO-) and νs(COO-) bands in the FTIR spectra. These absorption bands grow in intensity over time and the resulting product remains strongly adsorbed on the surface. The formation of adsorbed succinate is a result of a reaction with DMS on Lewis acid sites of the TiO2 surface. Overall, the slow desorption of these adsorbed species indicates that indoor surfaces can become long term reservoirs for dibasic esters and their surface products. Moreover, in the presence of ∼50% relative humidity, water displaces outer layers of adsorbed DMS on SiO2 and TiO2, while having no impact on the more strongly bound surface species.