Based on the observation by a Regional Air Quality Monitoring Network including 16 monitoring stations, temporal and spatial variations of ozone(O3), NO2and total oxidant(Ox) were analyzed by both linear regression and cluster analysis. A fast increase of regional O3concentrations of 0.86 ppbV/yr was found for the annual averaged values from 2006 to 2011 in Guangdong, China. Such fast O3increase is accompanied by a correspondingly fast NOx reduction as indicated by a fast NO2 reduction rate of 0.61 ppbV/yr. Based on a cluster analysis, the monitoring stations were classified into two major categories – rural stations(non-urban) and suburban/urban stations. The O3concentrations at rural stations were relatively conserved while those at suburban/urban stations showed a fast increase rate of 2.0 ppbV/yr accompanied by a NO2 reduction rate of 1.2 ppbV/yr. Moreover, a rapid increase of the averaged O3 concentrations in springtime(13%/yr referred to 2006 level) was observed, which may result from the increase of solar duration, reduction of precipitation in Guangdong and transport from Eastern Central China. Application of smog production algorithm showed that the photochemical O3production is mainly volatile organic compounds(VOC)-controlled. However, the photochemical O3production is sensitive to both NOx and VOC for O3pollution episode. Accordingly, it is expected that a combined NOx and VOC reduction will be helpful for the reduction of the O3 pollution episodes in Pearl River Delta while stringent VOC emission control is in general required for the regional O3 pollution control.
Nitrous acid(HONO),as a primary precursor of OH radicals,has been considered one of the most important nitrogencontaining species in the atmosphere.Up to 30%of primary OH radical production is attributed to the photolysis of HONO.However,the major HONO formation mechanisms are still under discussion.During the Campaigns of Air Quality Research in Beijing and Surrounding Region(CAREBeijing2006)campaign,comprehensive measurements were carried out in the megacity Beijing,where the chemical budget of HONO was fully constrained.The average diurnal HONO concentration varied from 0.33 to 1.2 ppbv.The net OH production rate from HONO,POH(HONO)net,was on average(from 05:00 to 19:00)7.1×106 molecule/(cm3 s),2.7 times higher than from O3 photolysis.This production rate demonstrates the important role of HONO in the atmospheric chemistry of megacity Beijing.An unknown HONO source(Punknown)with an average of 7.3×106molecule/(cm3 s)was derived from the budget analysis during daytime.Punknown provided four times more HONO than the reaction of NO with OH did.The diurnal variation of Punknown showed an apparent photo-enhanced feature with a maximum around 12:00,which was consistent with previous studies at forest and rural sites.Laboratory studies proposed new mechanisms to recruit NO2 and J(NO2)in order to explain a photo-enhancement of of Punknown.In this study,these mechanisms were validated against the observation-constraint Punknown.The reaction of exited NO2 accounted for only 6%of Punknown,and Punknown poorly correlated with[NO2](R=0.26)and J(NO2)[NO2](R=0.35).These results challenged the role of NO2 as a major precursor of the missing HONO source.
