As an important precursor of hydroxyl radical, nitrous acid (HONO) plays a key role in the chemistry of the lower atmosphere. Recent atmospheric measurements and model calculations show strong enhancement for HONO formation during daytime, while they are inconsistent with the known sources in the atmosphere, suggesting that current models are lacking important sources for HONO. In this article, heterogeneous photochemical reactions of nitric acid/nitrate anion and nitrogen oxide on various aerosols were reviewed and their potential contribution to HONO formation was also discussed. It is demonstrated that HONO can be formed by photochemical reaction on surfaces with deposited HNO3 , by photocatalytic reaction of NO2 on TiO2 or TiO2 -containing materials, and by photochemical reaction of NO2 on soot, humic acids or other photosensitized organic surfaces. Although significant uncertainties still exist in the exact mechanisms and the yield of HONO, these additional sources might explain daytime observations in the atmosphere.
Jinzhu MaYongchun LiuChong HanQingxin MaChang LiuHong He
In situ difflusion reflectance infrared Fourier transform spectroscopy was used to study the water adsorption on mineral oxides(SiO2,α-Al2O3,MgO,Fe2O3,TiO2).The results showed that all the water adsorption isotherms were well fitted with the Brunauer-EmmettTeller(BET)-Ⅲ type equation,with the calculated monolayers occurring at 24%-30% relative humidity.It showed that about 1-5 layers of water adsorbed on oxides surfaces in ambient relative humidity(20%-90%).The measured deliquescence relative humidity of NaCl was(74 ± 1)%,which demonstrated that DRIFTS is a useful method for the study the hygroscopic behavior of mineral dust.In addition,the limits of DRIFTS were also discussed.
Qingxin Ma,Hong He,Yongchun Liu State Key Laboratory of Environmental Chemistry and Ecotoxicology,Research Center for Eco-Environmental Sciences,Chinese Academy of Sciences,Beijing 100085,China.
Mineral dust comprises a great fraction of the global aerosol loading,but remains the largest uncertainty in predictions of the future climate due to its complexity in composition and physico-chemical properties.In this work,a case study characterizing Asian dust storm particles was conducted by multiple analysis methods,including SEM-EDS,XPS,FT-IR,BET,TPD/mass and Knudsen cell/mass.The morphology,elemental fraction,source distribution,true uptake coefficient for SO 2,and hygroscopic behavior were studied.The major components of Asian dust storm particles are aluminosilicate,SiO 2 and CaCO 3,with organic compounds and inorganic nitrate coated on the surface.It has a low reactivity towards SO 2 with a true uptake coefficient,5.767×10-6,which limits the conversion of SO 2 to sulfate during dust storm periods.The low reactivity also means that the heterogeneous reactions of SO 2 in both dry and humid air conditions have little effect on the hygroscopic behavior of the dust particles.
Smog chamber experiments were conducted to investigate the hygroscopicity of particles generated from photooxidation of α-pinene/NOx with diferent sulfate seed aerosols or oxidation conditions. Hygroscopicity of particles was measured by a tandem diferential mobility analyzer(TDMA) in terms of hygroscopic growth factor(Gf), with a relative humidity of 85%. With sulfate seed aerosols present, Gf of the aerosols decreased very fast before notable secondary organic aerosols(SOA) formation was observed, indicating a heterogeneous process between inorganic seeds and organic products might take place as soon as oxidation begins, rather than only happening after gas-aerosol partition of organic products starts. The final SOA-coated sulfate particles had similar or lower Gf than seed-free SOA. The hygroscopicity of the final particles was not dependent on the thickness but on the hygroscopicity properties of the SOA, which were influenced by the initial sulfate seed particles. In the two designed aging processes, Gf of the particles increased more significantly with introduction of OH radical than with ozone. However, the hygroscopicity of SOA was very low even after a long time of aging, implying that either SOA aging in the chamber was very slow or the Gf of SOA did not change significantly in aging. Using an aerosol composition speciation monitor(ACSM) and matrix factorization(PMF) method, two factors for the components of SOA were identified, but the correlation between SOA hygroscopicity and the proportion of the more highly oxidized factor could be either positive or negative depending on the speciation of seed aerosols present.
Aerosol phase reactions play a very important role on secondary organic aerosol （SOA） formation, and metal-containing aerosols are important components in the atmosphere. In this study, we tested the effects of two transition metal sulfate salts, manganese sulfate （MnSO4） and zinc sulfate （ZnSO4）, on the photochemical reactions of a toluene/NOx photooxidation system in a 2 m3 smog chamber. By comparing photochemical reaction products of experiments with and without transition metal sulfate seed aerosols, we evaluated the effects of transition metal sulfate seed aerosols on toluene consumption, NOx conversion and the formation of ozone and SOA. MnSO4 and ZnSO4 seed aerosols were found to have similar effects on photochemical reactions, both enhance the SOA production, while showing negligible effects on the gas phase compounds. These observations are consistent when varying metal sulfate aerosol concentrations. This is attributed to the catalytic effects of MnSO4 and ZnSO4 seed aerosols which may enhance the formation of condensable semivolatile compounds. Their subsequent partitioning into the aerosol phase leads to the observed SOA formation enhancement.
