The photochemical formation and gas-particle partitioning of oxidation products of decamethyl cyclopentasiloxane and decamethyl tetrasiloxane in the atmosphere

Abstract

Decamethyl cyclopentasiloxane (D5) and decamethyl tetrasiloxane (MD2M) were injected into a smog chamber containing fine Arizona road dust particles (95% surface area <2.6 μM) and an urban smog atmosphere in the daytime. A photochemical reaction - gas-particle partitioning reaction scheme, was implemented to simulate the formation and gas-particle partitioning of hydroxyl oxidation products of D5 and MD2M. This scheme incorporated the reactions of D5 and MD2M into an existing urban smog chemical mechanism carbon bond IV and partitioned the products between gas and particle phase by treating gas-particle partitioning as a kinetic process and specifying an uptake and off-gassing rate. A photochemical model PKSS was used to simulate this set of reactions. A Langmuirian partitioning model was used to convert the measured and estimated mass-based partitioning coefficients (KP) to a molar or volume-based form. The model simulations indicated that >99% of all product silanol formed in the gas-phase partition immediately to particle phase and the experimental data agreed with model predictions. One product, D4TOH was observed and confirmed for the D5 reaction and this system was modeled successfully. Experimental data was inadequate for MD2M reaction products and it is likely that more than one product formed. The model set up a framework into which more reaction and partitioning steps can be easily added.