An intensive field campaign including measurements from the environmental monitoring network and from two super sites took place in the Pearl River Delta region in summer 2006.Using routinely measured O3 and NOx concentrations,the spatial and temporal variation of O3 and of the total oxidant concentrations was characterized.According to the spatial variability of NO2/NO,the two super sites were found to be representative of polluted urban and downwind suburban conditions.In addition,both sites were located in high O3 regions.In-depth diagnostic of photochemical ozone production processes and their key controlling factors are achieved with an observation-based model(OBM) to gain regional perspectives.Budget analysis and sensitivity model runs show that aldehyde and HONO chemistry had significant impacts on local photochemical ozone production rates.The analysis of calculated Relative Incremental Reactivities shows that photochemical ozone production rates are mainly sensitive to anthropogenic hydrocarbons(HCs) in the polluted urban areas.In the suburban areas,sensitivity to nitrogen oxide(NO) concentrations dominated.Key anthropogenic HCs in both areas are alkenes and aromatics.Significant differences of ozone production efficiencies are identified between the urban and suburban regions,consistent with the OBM diagnosed results.
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, Pon（HONO）net, was on average （from 05：00 to 19：00） 7.1 × 10^6 molecule/（cm^3 s）, 2.7 times higher than from 03 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 × 10^6 molecule/（cm^3 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 Puknown. In this study, these mechanisms were validated against the observation-constraint Punknown. The reaction of exited NO2 accounted for only 6% of Puknown, and Punk 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.
A new instrument for measuring atmospheric nitrous acid（HONO） was developed,consisting of a double-wall glass stripping coil sampler coupled with ion chromatography（SC-IC）.SC-IC is featured by small size（50 × 35 × 25 cm） and modular construction,including three independent parts：the sampling unit,the transfer and supporting unit,and the detection unit.High collection efficiency（〉 99%） was achieved with 25 μmol/L Na2CO3 as absorption solution even in the presence of highly acidic compounds.This instrument has a detection limit of 8 pptv at 15 min time resolution,with a measurement uncertainty of 7%.Potential interferences from NOx,NO2＋SO2,NO2＋VOCs,HONO＋O3,HNO3,peroxyacetyl nitrite（PAN） and particle nitrite were quantified in laboratory studies and were found to be insignificant under typical atmospheric conditions.Within the framework of the 3C-STAR project,inter-comparison between the SC-IC and LOPAP（long path liquid absorption photometer） was conducted at a rural site in the Pearl River Delta.Good agreement was achieved between the two instruments over three weeks.Both instruments determined a clear diurnal profile of ambient HONO concentrations from 0.1 to 2.5 ppbv.However,deviations were found for low ambient HONO concentrations（i.e.〈 0.3 ppbv）,which cannot be explained by previous investigated interference species.To accurately determine the HONO budget under illuminated conditions,more intercomparison of HONO measurement techniques is still needed in future studies,especially at low HONO concentrations.
