成果 Publications

2013
Shen XL, Zhao Y, Z.M. Chen, Huang D. Heterogeneous reactions of volatile organic compounds in the atmosphere. Atmospheric Environment. 2013;68:297-314.Abstract
Volatile organic compounds (VOCs) are of central importance in the atmosphere because of their close relation to air quality and climate change. As a significant sink for VOCs, the fate of VOCs via heterogeneous reactions may explain the big gap between field and model studies. These reactions play as yet unclear but potentially crucial role in atmospheric processes. In order to better evaluate this reaction pathway, we present the first specific review for the progress of heterogeneous reaction studies on VOCs, including carbonyl compounds, organic acids, alcohols, and so on. Our review focuses on the processes for heterogeneous reactions of VOCs under varying experimental conditions, as well as their implications for trace gas and HOx budget, secondary organic aerosol (SOA) formation, physicochemical properties of aerosols, and human health. Finally, we propose the future direction for laboratory studies of heterogeneous chemistry of VOCs that should be carried out under more atmospherically relevant conditions, with a special emphasis on the effects of relative humidity and illumination, the multicomponent reaction systems, and reactivity of aged and authentic particles. In particular, more reliable uptake coefficients, based on the abundant elaborate laboratory studies, appropriate calibration, and logical choice criterion, are urgently required in atmospheric models.
Impacts of aerosols on the chemistry of atmospheric trace gases: a case study of peroxides and HO2 radicals
Liang H, Chen ZM, Huang D, Zhao Y, Li ZY. Impacts of aerosols on the chemistry of atmospheric trace gases: a case study of peroxides and HO2 radicals. Atmospheric Chemistry and Physics. 2013;13(22):11259-11276.Abstract
Field measurements of atmospheric peroxides were obtained during the summer on two consecutive years over urban Beijing, which highlighted the impacts of aerosols on the chemistry of peroxide compounds and hydroperoxyl radicals (HO2). The major peroxides were determined to be hydrogen peroxide (H2O2), methyl hydroperoxide (MHP), and peroxyacetic acid (PAA). A negative correlation was found between H2O2 and PAA in rainwater, providing evidence for a conversion between H2O2 and PAA in the aqueous phase. A standard gas phase chemistry model based on the NCAR Master Mechanism provided a good reproduction of the observed H2O2 profile on non-haze days but greatly overpredicted the H2O2 level on haze days. We attribute this overprediction to the reactive uptake of HO2 by the aerosols, since there was greatly enhanced aerosol loading and aerosol liquid water content on haze days. The discrepancy between the observed and modeled H2O2 can be diminished by adding to the model a newly proposed transition metal ion catalytic mechanism of HO2 in aqueous aerosols. This confirms the importance of the aerosol uptake of HO2 and the subsequent aqueous phase reactions in the reduction of H2O2. The closure of HO2 and H2O2 between the gas and aerosol phases suggests that the aerosols do not have a net reactive uptake of H2O2, because the conversion of HO2 to H2O2 on aerosols compensates for the H2O2 loss. Laboratory studies for the aerosol uptake of H2O2 in the presence of HO2 are urgently required to better understand the aerosol uptake of H2O2 in the real atmosphere.
Huang D, Chen ZM, Zhao. Y, Liang H. . Newly observed peroxides and the water effect on the formation and removal of hydroxyalkyl hydroperoxides in the ozonolysis of isoprene. Atmospheric Chemistry and Physics,. 2013;13(11):5671-5683.Abstract
The ozonolysis of alkenes is considered to be an important source of atmospheric peroxides, which serve as oxidants, reservoirs of HOx radicals, and components of secondary organic aerosols (SOAs). Recent laboratory investigations of this reaction identified hydrogen peroxide (H2O2) and hydroxymethyl hydroperoxide (HMHP) in ozonolysis of isoprene. Although larger hydroxyalkyl hydroperoxides (HAHPs) were also expected, their presence is not currently supported by experimental evidence. In the present study, we investigated the formation of peroxides in the gas phase ozonolysis of isoprene at various relative humidities on a time scale of tens of seconds, using a quartz flow tube reactor coupled with the online detection of peroxides. We detected a variety of conventional peroxides, including H2O2, HMHP, methyl hydroperoxide, bis-hydroxymethyl hydroperoxide, and ethyl hydroperoxide, and interestingly found three unknown peroxides. The molar yields of the conventional peroxides fell within the range of values provided in the literature. The three unknown peroxides had a combined molar yield of ~30% at 5% relative humidity (RH), which was comparable with that of the conventional peroxides. Unlike H2O2 and HMHP, the molar yields of these three unknown peroxides were inversely related to the RH. On the basis of experimental kinetic and box model analysis, we tentatively assigned these unknown peroxides to C2−C4 HAHPs, which are produced by the reactions of different Criegee intermediates with water. Our study provides experimental evidence for the formation of large HAHPs in the ozonolysis of isoprene (one of the alkenes). These large HAHPs have a sufficiently long lifetime, estimated as tens of minutes, which allows them to become involved in atmospheric chemical processes, e.g., SOA formation and radical recycling.
2012
Shen XL, Chen ZM, Zhao Y, Huang D. In situ FTIR studying the absorption and transformation of glyoxal on the surface of dust particles. Spectroscopy and Spectral Analysis. 2012;32(11):2946-2949.
Zhang X, He SZ, Chen ZM, Zhao Y, Hua W. Methyl hydroperoxide (CH3OOH) in urban, suburban and rural atmosphere: ambient concentration, budget, and contribution to the atmospheric oxidizing capacity. Atmospheric Chemistry and Physics. 2012;12(19):8951-8962.
Chen ZM, Zhao Y. Molecular spectroscopy for studying heterogeneous chemistry of atmospheric particles. Spectroscopy and Spectral Analysis. 2012;32(10, suppl.):47-48.
Zhu LH, Tao J, Chen ZM, Zhao Y, Zhang RJ, Cao JJ. Reconstructed ambient light extinction coefficient and its contribution factors in Beijing in January, 2010. Environmental Science. 2012;33(1):13-19.
Wang HL, Huang D, Zhang X, Zhao Y, Chen ZM. Understanding the aqueous phase ozonolysis of isoprene: distinct product distribution and mechanism from the gas phase reaction. Atmospheric Chemistry and Physics. 2012;12(15):7187-7198.
2011
Cheng YL, Liu Y, Huo MQ, Sun Q, Wang HX, Chen ZM. Chemical characteristics of precipitation at Nanping Mangdang Mountain in eastern China during spring. Journal of Environmental Sciences. 2011;23(8):1350-1358.
Zhao Y, Chen ZM, Shen XL, Huang D. Importance of atmospheric aging in reactivity of mineral dust aerosol: a case study of heterogeneous reaction of gaseous hydrogen peroxide on processed mineral particles. Atmospheric Chemistry and Physics Discussion. 2011;11(10):28563-28586.
Huang D, Zhang X, Chen ZM, Zhao Y, Shen XL. The kinetics and mechanism of an aqueous phase isoprene reaction with hydroxyl radical. Atmospheric Chemistry and Physics. 2011;11(15):7399-7415.
Zhao Y, Chen ZM, Shen XL, Zhang X. Kinetics and mechanisms of heterogeneous reaction of gaseous hydrogen peroxide on mineral oxide particles. Environmental Science & Technology. 2011;45(8):3317-3324.
He SZ, Chen ZM, Zhang X. Photochemical reactions of methyl and ethyl nitrates: A dual role of alkyl nitrates in the nitrogen cycle. Environmental Chemistry. 2011;8(6):529-542.
2010
Zhao Y, Chen ZM. Applications of FTIR spectroscopy in the study of atmospheric heterogeneous processes. Applied Spectroscopy Reviews. 2010;45(1):63-91.
Zhao Y, Chen ZM, Zhao JN. Heterogeneous reactions of methacrolein and methyl vinyl ketone on α-Al2O3 particles. Environmental Science & Technology,. 2010;44(6):2035-2041.
Li HJ, Zhu T, Zhang ZF, Zhao ZF, Chen ZM. Kinetics and mechanisms of heterogeneous reaction of NO2 on CaCO3 surfaces under dry and wet condition. Atmospheric Chemistry and Physics. 2010;10(2):463-474.
Zhang X, Chen ZM, Zhao Y. Laboratory simulation for the aqueous OH-oxidation of methyl vinyl ketone and methacrolein: Significance to the in-cloud SOA production. Atmospheric Chemistry and Physics. 2010;10(19): 9551-9561.
He SZ, Chen ZM, Zhang X, Zhao Y, Huang DM, Zhao JN, Zhu T, Hu M, Zeng LM. Measurement of atmospheric hydrogen peroxide and organic peroxides in Beijing before and during the 2008 Olympic Games: chemical and physical factors influencing their concentrations. Journal of Geophysical Research-Atmospheres. 2010;115:D17307.
Zhang X, Chen ZM, He SZ, Hua W, Li JL. Peroxyacetic acid in urban and rural atmosphere:concentration,feedback on PAN-NOx cycle and implication on radical chemistry. Atmospheric Chemistry and Physics. 2010;10(2):737-748.
Huang DM, Chen ZM. Reinvestigation of Henry's law constant for hydrogen peroxide with temperature and acidity variation. Journal of Environmental Sciences. 2010;22(4):570-574.

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