To investigate the secondary organic aerosol (SOA) formation in Beijing, fine particle (PM2.5) samples were collected at an urban site (Peking University, PKU) and a rural site (Yufa) during CAREBEITING 2008 summer intensive field campaign. Several approaches were used to estimate SOA concentrations, including tracer-yield method, non-primary organic carbon method (receptor model, Chemical Mass Balance model), non-biomass burning water soluble organic carbon (WSOC) method and EC tracer OC/EC ratio method. To develop non-biomass burning WSOC method, simulation of typical Chinese biomass burning was conducted to obtain the important parameters. The average WSOC/OC ratio in Chinese biomass burning is 0.48 +/- 0.04. This ratio can be used in non-biomass burning WSOC method to estimate SOC of China. The results from different methods all indicated secondary formation has become major contributor to organic aerosols in Beijing, accounting for 50% or more of the total OC. A closure study was made by combination of CMB model and tracer-yield method. Five primary sources, including vegetative detritus, biomass burning, coal burning, gasoline engines and diesel engines, and four secondary organic aerosols derived from isoprene, alpha-pinene, beta-caryophyllene and toluene were apportioned. To the current knowledge, about 20%similar to 27% of the OC sources still remain unknown. Applicability of these SOC methods in China was tested by comparing the different methods. Tracer-yield method, CMB model and EC tracer OC/EC ratio method can be used to estimate SOC in China. However, non-biomass burning WSOC method can only be used to estimate water-soluble SOC. Uncertainty analysis was conducted to help researchers to determine the proper method to estimate SOC in China. Tracer-yield method underestimates total SOC, because it can only estimate SOCs from several precursors. Similarly, non-biomass burning WSOC method also underestimate SOC. Non-primary OC method overestimates SOC due to unapportioned primary OC, especially in urban area where the particle sources are complicated. The uncertainty of EC-tracer OC/EC ratio method is mainly from the primary OC/EC ratio. The largest overestimation and underestimation of single point value can be 54% and 64%.

Nitrous acid (HONO), as a primary precursor of OH radicals, has been considered one of the most important nitrogen-containing 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, P (OH)(HONO)(net), was on average (from 05:00 to 19:00 h) 7.1 x 10(6) molecule/(cm(3) s), 2.7 times higher than from O-3 photolysis. This production rate demonstrates the important role of HONO in the atmospheric chemistry of megacity Beijing. An unknown HONO source (P (unknown)) with an average of 7.3 x 10(6) molecule/(cm(3) s) was derived from the budget analysis during daytime. P (unknown) provided four times more HONO than the reaction of NO with OH did. The diurnal variation of P (unknown) showed an apparent photo-enhanced feature with a maximum around 12:00 h, 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 P (unknown). In this study, these mechanisms were validated against the observation-constraint P (unknown). The reaction of exited NO2 accounted for only 6% of P (unknown), and P (unknown) 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.

As the world's second largest economy, China has experienced severe haze pollution, with fine particulate matter ( PM) recently reaching unprecedentedly high levels across many cities, and an understanding of the PM formation mechanism is critical in the development of efficient mediation policies to minimize its regional to global impacts. We demonstrate a periodic cycle of PM episodes in Beijing that is governed by meteorological conditions and characterized by two distinct aerosol formation processes of nucleation and growth, but with a small contribution from primary emissions and regional transport of particles. Nucleation consistently precedes a polluted period, producing a high number concentration of nano-sized particles under clean conditions. Accumulation of the particle mass concentration exceeding several hundred micrograms per cubic meter is accompanied by a continuous size growth from the nucleation-mode particles over multiple days to yield numerous larger particles, distinctive from the aerosol formation typically observed in other regions worldwide. The particle compositions in Beijing, on the other hand, exhibit a similarity to those commonly measured in many global areas, consistent with the chemical constituents dominated by secondary aerosol formation. Our results highlight that regulatory controls of gaseous emissions for volatile organic compounds and nitrogen oxides from local transportation and sulfur dioxide from regional industrial sources represent the key steps to reduce the urban PM level in China.

Understanding the particle number size distributions in diversified atmospheric environments is important in order to design mitigation strategies related to submicron particles and their effects on regional air quality, haze and human health. In this study, we conducted 15 different field measurement campaigns between 2007 and 2011 at 13 individual sites in China, including five urban sites, four regional sites, three coastal/background sites and one ship cruise measurement along eastern coastline of China. Size resolved particles were measured in the 15-600 nm size range. The median particle number concentrations (PNCs) were found to vary in the range of 1.1-2.2 x 10(4) cm(-3) at urban sites, 0.8-1.5 x 10(4) cm(-3) at regional sites, 0.4-0.6 x 10(4) cm(-3) at coastal/background sites, and 0.5 x 10(4) cm(-3) during cruise measurement. Peak diameters at each of these sites varied greatly from 24 to 115 nm. Particles in the 15-25 nm (nucleation mode), 25-100 nm (Aitken mode) and 100-600 nm (accumulation mode) range showed different characteristics at each sites, indicating the features of primary emissions and secondary formation in these diversified atmospheric environments. Diurnal variations show a build-up of accumulation mode particles belt at regional sites, suggesting the contribution of regional secondary aerosol pollution. Frequencies of new particle formation (NPF) events were much higher at urban and regional sites than at coastal sites and during cruise measurement. The average growth rates (GRs) of nucleation mode particles were 8.0-10.9 nm h(-1) at urban sites, 7.4-13.6 nm h(-1) at regional sites and 2.8-7.5 nm h(-1) at coastal sites and during cruise measurement. The high gaseous precursors and strong oxidation at urban and regional sites not only favored the formation of particles, but also accelerated the growth rate of the nucleation mode particles. No significant difference in condensation sink (CS) during NPF days were observed among different site types, suggesting that the NPF events in background areas were more influenced by the pollutant transport. In addition, average contributions of NPF events to potential cloud condensation nuclei (CCN) at 0.2% super-saturation in the afternoon of all sampling days were calculated as 11% and 6% at urban sites and regional sites, respectively. On the other hand, NPF events at coastal sites and during cruise measurement had little impact on potential production of CCN. This study provides a large data set of particle size distribution in diversified atmosphere of China, improving our general understanding of emission, secondary formation, new particle formation and corresponding CCN activity of submicron aerosols in Chinese environments.

Nitrous acid (HONO), as a primary precursor of OH radicals, has been considered one of the most important nitrogen-containing 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, P (OH)(HONO)(net), was on average (from 05:00 to 19:00 h) 7.1 x 10(6) molecule/(cm(3) s), 2.7 times higher than from O-3 photolysis. This production rate demonstrates the important role of HONO in the atmospheric chemistry of megacity Beijing. An unknown HONO source (P (unknown)) with an average of 7.3 x 10(6) molecule/(cm(3) s) was derived from the budget analysis during daytime. P (unknown) provided four times more HONO than the reaction of NO with OH did. The diurnal variation of P (unknown) showed an apparent photo-enhanced feature with a maximum around 12:00 h, 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 P (unknown). In this study, these mechanisms were validated against the observation-constraint P (unknown). The reaction of exited NO2 accounted for only 6% of P (unknown), and P (unknown) 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.

Understanding the particle number size distributions in diversified atmospheric environments is important in order to design mitigation strategies related to submicron particles and their effects on regional air quality, haze and human health. In this study, we conducted 15 different field measurement campaigns between 2007 and 2011 at 13 individual sites in China, including five urban sites, four regional sites, three coastal/background sites and one ship cruise measurement along eastern coastline of China. Size resolved particles were measured in the 15-600 nm size range. The median particle number concentrations (PNCs) were found to vary in the range of 1.1-2.2 x 10(4) cm(-3) at urban sites, 0.8-1.5 x 10(4) cm(-3) at regional sites, 0.4-0.6 x 10(4) cm(-3) at coastal/background sites, and 0.5 x 10(4) cm(-3) during cruise measurement. Peak diameters at each of these sites varied greatly from 24 to 115 nm. Particles in the 15-25 nm (nucleation mode), 25-100 nm (Aitken mode) and 100-600 nm (accumulation mode) range showed different characteristics at each sites, indicating the features of primary emissions and secondary formation in these diversified atmospheric environments. Diurnal variations show a build-up of accumulation mode particles belt at regional sites, suggesting the contribution of regional secondary aerosol pollution. Frequencies of new particle formation (NPF) events were much higher at urban and regional sites than at coastal sites and during cruise measurement. The average growth rates (GRs) of nucleation mode particles were 8.0-10.9 nm h(-1) at urban sites, 7.4-13.6 nm h(-1) at regional sites and 2.8-7.5 nm h(-1) at coastal sites and during cruise measurement. The high gaseous precursors and strong oxidation at urban and regional sites not only favored the formation of particles, but also accelerated the growth rate of the nucleation mode particles. No significant difference in condensation sink (CS) during NPF days were observed among different site types, suggesting that the NPF events in background areas were more influenced by the pollutant transport. In addition, average contributions of NPF events to potential cloud condensation nuclei (CCN) at 0.2% super-saturation in the afternoon of all sampling days were calculated as 11% and 6% at urban sites and regional sites, respectively. On the other hand, NPF events at coastal sites and during cruise measurement had little impact on potential production of CCN. This study provides a large data set of particle size distribution in diversified atmosphere of China, improving our general understanding of emission, secondary formation, new particle formation and corresponding CCN activity of submicron aerosols in Chinese environments.