Absorption Coefficient, Molecular Composition, and Photodegradation of Different Types of Brown Carbon Aerosols

Abstract:

Atmospheric aerosols that absorb solar radiation have a direct effect on climate. Brown carbon (BrC) represents the type of carbonaceous aerosols characterized by large absorption coefficients in the near-UV range of the spectrum. BrC can be either directly emitted into the atmosphere from combustion sources, or be formed in the atmosphere through multi-phase reactions, such as aging of secondary organic aerosols (SOA) mediated by ammonium sulfate (AS). Under the conditions of exposure to solar radiation, both primary and secondary BrC can potentially change their molecular composition and optical properties as a result of photodegradation of chromophoric compounds. This presentation will discuss the molecular level composition, the absorption and fluorescence spectra, and the mechanism of photodegradation among several representative types of BrC. The primary BrC samples include aerosol produced by smoldering wood combustion. The secondary BrC samples include AS aged products of chamber-generated SOA, products of reaction between methylglyoxal and AS, and SOA produced by the hogh-NOx photooxdiation of aromatic compounds, such as naphthalene. This presentation will also include preliminary data on the absorption and fluorescence spectra of photo-degraded bioaerosols. In all cases, absorption spectra of extracted bulk samples are measured during irradiation by a known flux of UV or visible light. The molecular level composition of the fresh and photobleached samples are characterized by high-resolution electrospray ionization mass spectrometry (HR-ESI-MS). Photobleaching of BrC is found to occur over a range of atmospherically relevant time scales. In many cases, the molecular level composition of photobleached BrC exhibits only subtle changes suggesting that the optical and fluorescence properties of BrC are controlled by a few compounds present in low quantities. The observed fluorescence from non-biological BrC indicates potential issues in using fluorescence-based methods to detect bioaerosols. Overall, the results demonstrate a high degree of variability in optical properties and the highly dynamic nature of atmospheric BrC.