Electron spin resonance study of puff-resolved free radical formation in mainstream cigarette smoke

Puff-by-puff resolved gas phase free radicals were measured in mainstream smoke from Kentucky 2R4F reference cigarettes using ESR spectroscopy. Three spin-trapping reagents were evaluated: PBN, DMPO and DEPMPO. Two procedures were used to collect gas phase smoke on a puff-resolved basis: i) the accumulative mode, in which all the gas phase smoke up to a particular puff was bubbled into the trap (i.e., the 5th puff corresponded to the total smoke from the 1st to 5th puffs). In this case, after a specified puff, an aliquot of the spin trap was taken and analysed; or, ii) the individual mode, in which the spin trap was analysed and then replaced after each puff. Spin concentrations were determined by double-integration of the first derivative of the ESR signal. This was compared with the integrals of known standards using the TEMPO free radical. The radicals trapped with PBN were mainly carbon-centred, whilst the oxygen-centred radicals were identified with DMPO and DEPMPO. With each spin trap, the puff-resolved radical concentrations showed a characteristic pattern as a function of the puff number. Based on the spin concentrations, the DMPO and DEPMPO spin traps showed better trapping efficiencies than PBN. The implication for gas phase free radical analysis is that a range of different spin traps should be used to probe complex free radical reactions in cigarette smoke.

Revisiting Asian monsoon formation and change associated with Tibetan Plateau forcing: II. Change

Data analysis based on station observations reveals that many meteorological variables averaged over the Tibetan Plateau (TP) are closely correlated, and their trends during the past decades are well correlated with the rainfall trend of the Asian summer monsoon. However, such correlation does not necessarily imply causality. Further diagnosis confirms the existence of a weakening trend in TP thermal forcing, characterized by weakened surface sensible heat flux in spring and summer during the past decades. This weakening trend is associated with decreasing summer precipitation over northern South Asia and North China and increasing precipitation over northwestern China, South China, and Korea. An atmospheric general circulation model, the HadAM3, is employed to elucidate the causality between the weakening TP forcing and the change in the Asian summer monsoon rainfall. Results demonstrate that a weakening in surface sensible heating over the TP results in reduced summer precipitation in the plateau region and a reduction in the associated latent heat release in summer. These changes in turn result in the weakening of the near-surface cyclonic circulation surrounding the plateau and the subtropical anticyclone over the subtropical western North Pacific, similar to the results obtained from the idealized TP experiment in Part I of this study. The southerly that normally dominates East Asia, ranging from the South China Sea to North China, weakens, resulting in a weaker equilibrated Sverdrup balance between positive vorticity generation and latent heat release. Consequently, the convergence of water vapor transport is confined to South China, forming a unique anomaly pattern in monsoon rainfall, the so-called “south wet and north dry.” Because the weakening trend in TP thermal forcing is associated with global warming, the present results provide an effective means for assessing projections of regional climate over Asia in the context of global warming.