Enhanced Nitrite Production from the Aqueous Photolysis of Nitrate in the Presence of Vanillic Acid and Implications for the Roles of Light-Absorbing Organics.

A prominent source of hydroxyl radicals (•OH), nitrous acid (HONO) plays a key role in tropospheric chemistry. Apart from direct emission, HONO (or its conjugate base nitrite, NO2-) can be formed secondarily in the atmosphere. Yet, how secondary HONO forms requires elucidation, especially for heterogeneous processes involving numerous organic compounds in atmospheric aerosols. We investigated nitrite production from aqueous photolysis of nitrate for a range of conditions (pH, organic compound, nitrate concentration, and cation). Upon adding small oxygenates such as ethanol, n-butanol, or formate as •OH scavengers, the average intrinsic quantum yield of nitrite [Φ(NO2-)] was 0.75 ± 0.15%. With near-UV-light-absorbing vanillic acid (VA), however, the effective Φ(NO2-) was strongly pH-dependent, reaching 8.0 ± 2.1% at a pH of 8 and 1.5 ± 0.39% at a more atmospherically relevant pH of 5. Our results suggest that brown carbon (BrC) may greatly enhance the nitrite production from the aqueous nitrate photolysis through photosensitizing reactions, where the triplet excited state of BrC may generate solvated electrons, which reduce nitrate to NO2 for further conversion to nitrite. This photosensitization process by BrC chromophores during nitrate photolysis under mildly acidic conditions may partly explain the missing HONO in urban environments.

Emission Inventories and Particulate Matter Air Quality Modeling over the Pearl River Delta Region.

The Pearl River Delta (PRD) region is located on the southeast coast of mainland China and it is an important economic hub. The high levels of particulate matter (PM) in the atmosphere, however, and poor visibility have become a complex environmental problem for the region. Air quality modeling systems are useful to understand the temporal and spatial distribution of air pollution, making use of atmospheric emission data as inputs. Over the years, several atmospheric emission inventories have been developed for the Asia region. The main purpose of this work is to evaluate the performance of the air quality modeling system for simulating PM concentrations over the PRD using three atmospheric emission inventories (i.e., EDGAR, REAS and MIX) during a winter and a summer period. In general, there is a tendency to underestimate PM levels, but results based on the EDGAR emission inventory show slightly better accuracy. However, improvements in the spatial and temporal disaggregation of emissions are still needed to properly represent PRD air quality. This study's comparison of the three emission inventories' data, as well as their PM simulating outcomes, generates recommendations for future improvements to atmospheric emission inventories and our understanding of air pollution problems in the PRD region.