Validating HONO as an Intermediate Tracer of the External Cycling of Reactive Nitrogen in the Background Atmosphere.

In the urban atmosphere, nitrogen oxide (NOx═NO + NO2)-related reactions dominate the formation of nitrous acid (HONO). Here, we validated an external cycling route of HONO and NOx, i.e., formation of HONO resulting from precursors other than NOx, in the background atmosphere. A chemical budget closure experiment of HONO and NOx was conducted at a background site on the Tibetan Plateau and provided direct evidence of the external cycling. An external daytime HONO source of 100 pptv h-1 was determined. Both soil emissions and photolysis of nitrate on ambient surfaces constituted likely candidate mechanisms characterizing this external source. The external source dominated the chemical production of NOx with HONO as an intermediate tracer. The OH production was doubled as a result of the external cycling. A high HONO/NOx ratio (0.31 ± 0.06) during the daytime was deduced as a sufficient condition for the external cycling. Literature review suggested the prevalence of high HONO/NOx ratios in various background environments, e.g., polar regions, pristine mountains, and forests. Our analysis validates the prevalence of external cycling in general background atmosphere and highlights the promotional role of external cycling regarding the atmospheric oxidative capacity.

The association of chemical composition particularly the heavy metals with the oxidative potential of ambient PM2.5 in a megacity (Guangzhou) of southern China.

Atmospheric fine particulate matters (PM2.5) can cause adverse health effects through the generation of reactive oxygen species (ROS), which is normally characterized by the oxidative potential (OP). However, the particulate components that are mainly responsible for the ROS-induced OP remain controversial and warrant further investigation, especially in megacities where high exposure exists and particulate composition is complex. In this study, we measured the OP of PM2.5 using the dithiothreitol (DTT) assay with and without chelation of metals in a megacity in southern China, Guangzhou, in January and April. We explored the correlations between OP and various chemical components in PM2.5, including water-soluble ions, organic carbon (OC), elemental carbon (EC), and metal elements. There are strong correlations between OPDTTv (volume-normalized) and concentrations of PM2.5, OC, and EC, while the correlations between OPDTTm (mass-normalized) and mass-normalized water-soluble ions, OC, EC or metal elements are weak. The OP values with chelation were reduced by ∼90%, indicating that water-soluble heavy metals were the major contributors to OP of PM2.5 in Guangzhou. On the other hand, correlations between OPDTTm and OC improved significantly after the chelation of heavy metals, implying that OC explains the variance of OPDTTm although its contribution to OP is much smaller than that of heavy metals. We postulate that there might be synergetic effects between water-soluble heavy metals (which contribute most to OP) and OC (which explains the variance of OP) in ROS generation by PM2.5. The findings of the current study provide a better understanding on the critical components in PM2.5 and potential synergism that might be responsible for health effects in urban areas.