Oxidation Mechanism and Toxicity Evolution of Linalool, a Typical Indoor Volatile Chemical Product.

ABSTRACT

Linalool, a high-reactivity volatile chemical product (VCP) commonly found in cleaning products and disinfectants, is increasingly recognized as an emerging contaminant, especially in indoor air. Understanding the gas-phase oxidation mechanism of linalool is crucial for assessing its impact on atmospheric chemistry and human health. Using quantum chemical calculations and computational toxicology simulations, we investigated the atmospheric transformation and toxicity evolution of linalool under low and high NO/HO2· levels, representing indoor and outdoor environments. Our findings reveal that linalool can undergo the novel mechanisms involving concerted peroxy (RO2·) and alkoxy radical (RO·) modulated autoxidation, particularly emphasizing the importance of cyclization reactions indoors. This expands the widely known RO2·-dominated H-shift-driven autoxidation and proposes a generalized autoxidation mechanism that leads to the formation of low-volatility secondary organic aerosol (SOA) precursors. Toxicological analysis shows that over half of transformation products (TPs) exhibited higher carcinogenicity and respiratory toxicity compared to linalool. We also propose time-dependent toxic effects of TPs to assess their long-term toxicity. Our results indicate that the strong indoor emission coupled with slow consumption rates lead to significant health risks under an indoor environment. The results highlight complex indoor air chemistry and health concerns regarding persistent toxic products during indoor cleaning, which involves the use of linalool or other VCPs.