Multiphase Chemistry Controls Inorganic Chlorinated and Nitrogenated Compounds in Indoor Air during Bleach Cleaning

We report elevated levels of gaseous inorganic chlorinated and nitrogenated compounds in indoor air while cleaning with a commercial bleach solution during the House Observations of Microbial and Environmental Chemistry field campaign in summer 2018. Hypochlorous acid (HOCl), chlorine (Cl₂), and nitryl chloride (ClNO₂) reached part-per-billion by volume levels indoors during bleach cleaningseveral orders of magnitude higher than typically measured in the outdoor atmosphere. Kinetic modeling revealed that multiphase chemistry plays a central role in controlling indoor chlorine and reactive nitrogen chemistry during these periods. Cl₂ production occurred via heterogeneous reactions of HOCl on indoor surfaces. ClNO₂ and chloramine (NH₂Cl, NHCl₂, NCl₃) production occurred in the applied bleach via aqueous reactions involving nitrite (NO₂^–) and ammonia (NH₃), respectively. Aqueous-phase and surface chemistry resulted in elevated levels of gas-phase nitrogen dioxide (NO₂). We predict hydroxyl (OH) and chlorine (Cl) radical production during these periods (10⁶ and 10⁷ molecules cm^–3 s^–1, respectively) driven by HOCl and Cl₂ photolysis. Ventilation and photolysis accounted for <50% and <0.1% total loss of bleach-related compounds from indoor air, respectively; we conclude that uptake to indoor surfaces is an important additional loss process. Indoor HOCl and nitrogen trichloride (NCl₃) mixing ratios during bleach cleaning reported herein are likely detrimental to human health.