Anthropogenic Sulfur Perturbations on Biogenic Oxidation: Impacts of Sulfur Dioxide Additions on Bulk Gas Phase OH Oxidation Products of Alpha and Beta Pinene.

Abstract:

The evolution of biogenic volatile organic compounds (BVOCs) in the atmosphere is impacted by concurrent emissions of anthropogenic pollutants, such as sulfur dioxide (SO₂) and nitrogen oxides (NO_x), which can impact air quality and SOA formation in regions of biogenic and anthropogenic influence. We present the impacts of anthropogenic perturbations in the form of sulfur dioxide on the oxidation systems of α- and β-pinene. An oxidative flow reactor simulated atmospheric aging by OH oxidation on the order of days, and high-resolution time-of-flight mass spectrometry (HR-TOF-CIMS) was utilized to identify gas-phase oxidation products and changes to the ensemble system as a function of the SO₂ perturbation. Results show that the SO₂ perturbation impacted the oxidation systems of α- and β-pinene, and that these perturbations affected the oxidation systems of α- and β-pinene differently. Bulk analysis comparing the perturbed system to the unperturbed system indicated a change in oxidation pathway or mechanism leading to an ensemble of products with a lesser degree of oxygenation, on the order of a 30% decrease in the bulk oxidation state and a 10% decrease in the bulk O:C ratio for both BVOC systems. Increasing the relative humidity in the oxidative flow reactor was found to dampen the impact of the perturbation. Experiments involving other anthropogenic emissions, such as NOx, as well as other pairs of BVOC structural isomers, were conducted to investigate if changes in the oxidation system were due to the BVOC structure or the specific anthropogenic pollutant.