Photochemical reactions of 1,3-butadiene with nitrogen oxide in different matrices: Kinetic behavior, humidity effect, product and mechanisms.

Understanding the photochemical reaction process between VOCs and co-pollutants in the troposphere is crucial for controlling the haze. The photochemical reactions of 1,3-butadiene (1,3-BD) with NO were carried out at 308K for up to 96h in clean air with various relative humidity (RH) values, and actual haze atmosphere. In the haze, the representative pseudo-first-order kinetic rate constants of the 1,3-BD-NO system was 1.53 time higher than those in dry clean air. The effect of the RH (0%-80%) on the conversion behavior of the 1,3-BD-NO system in clean air was studied, revealing that increasing RH promoted the photochemical reaction in the low range of 0%-40% but retarded it in the high range of 40%-80%. Interestingly, OH radicals were directly detected under different RH values, and the strongest OH signal was obtained at an RH of 40%. Multiple macromolecular products with carbon numbers of 10-36 were identified. Unexpectedly, richer products and extended unsaturation range were detected at an RH of 40% than 0%. The photochemical products were also analyzed using ion chromatography. A reaction mechanism was proposed from the detected NO2, O3, OH, HNO2, HNO3, organic acids and macromolecular products.