An Approach to the Estimation of Adsorption Enthalpies of Polycyclic Aromatic Hydrocarbons on Particle Surfaces

Abstract

Current atmospheric models incorporate the values of vaporization enthalpies, ΔHvap, obtained for neat standards, thus disregarding the matrix effects on volatilization. To test the adequacy of this approximation, this study measured enthalpies of vaporization for five polycyclic aromatic hydrocarbons (PAHs) in the form of neat standards (ΔHvap) as well as adsorbed on the surface of silica, graphite, and graphene particles (ΔHvap(eff)), by using simultaneous thermogravimetry-differential scanning calorimetry (TGA-DSC). Measurement of the corresponding activation energy values, Ea(vap) and Ea vap(eff), by TGA using a derivative method was shown to be the most reliable and practical way to assess ΔHvap and ΔHvap(eff). Enthalpies of adsorption (ΔHads) were then calculated from the differences between Ea(vap) and Ea vap(eff), thus paving a way to modeling the solid-gas phase partitioning in atmospheric particulate matter (PM). The PAH adsorption on silica particle surfaces (representing n-π* interactions) resulted in negative values of ΔHads, indicating significant interactions. For graphite particles, positive ΔHads values were obtained; i.e., PAHs did not interact with the particle surface as strongly as observed for PM. PAHs on the surface of graphene particles evaporated in two stages, with the bulk of the mass loss occurring at temperatures lower than those with the neat standard, just as on graphite. Yet, unlike graphite, a small PAH fraction did not evaporate until higher temperatures compared to case of the neat standards and other particle surfaces (37.4-145.7 K), signifying negative, more PM-relevant values of ΔHads, apparently reflecting π-π* interactions and ranging between -7.6 and +32.6 kJ mol(-1), i.e., even larger than for silica, -3.3 to +8.3 kJ mol(-1). Thus, current atmospheric models may underestimate the partitioning of organic species in the particle phase unless matrix adsorption is taken into account.

Characteristic Variation of Particulate Matter-Bound Polycyclic Aromatic Hydrocarbons (PAHs) during Asian Dust Events, Based on Observations at a Japanese Background Site, Wajima, from 2010 to 2021

“…This difference was probably due to the low accumulation of PAHs on AD particles. Previous laboratory studies have pointed out that the active groups on AD particle surfaces tend to accumulate polar components, such as inorganic gases or water-soluble inorganic ions, while weakly adsorbing nonpolar PAHs, and the adsorption of water vapor to AD particles further inhibits the accumulation of PAHs [45][46][47][48]. The kinetic model study also proved this because of the extremely slow absorption rate of PAHs [49].…”