Wintertime N2O5 uptake coefficients over the North China Plain

The heterogeneous hydrolysis of dinitrogen pentoxide(N2O5)plays an important role in regulating NOx.The N2O5 uptake coefficient,γ(N2O5),was determined using an iterative box model that was constrained to observational data obtained in suburban Beijing from February to March 2016.The box model determined 2289 individualγ(N2O5)values that varied from<0.001 to 0.02 with an average value of 0.0046±0.0039(and a median value of 0.0032).We found the derived winterγ(N2O5)values in Beijing were relatively low as compared to values reported in previous field studies conducted during winter in Hong Kong(average value of 0.014)and the eastern U.S.coast(median value of 0.0143).In our study,field evidence of the suppression ofγ(N2O5)values due to pNO3-content,organics and the enhancement by aerosol liquid water content(ALWC)is in line with previous laboratory study results.Low ALWC,high pNO3-content,and particle morphology(inorganic core with an organic shell)accounted for the lowγ(N2O5)values in the North China Plain(NCP)during wintertime.The field-derivedγ(N2O5)values are well reproduced by a revised parameterization method,which includes the aerosol size distribution,ALWC,nitrate and organic coating,suggesting the feasibility of comprehensive parameterization in the NCP during wintertime.

Measurements of HO2 uptake coefficient on aqueous（NH4）2SO4 aerosol using aerosol flow tube with LIF system

Laboratory studies of HO2 uptake coefficients,γ(HO2),were conducted at room temperature using an aerosol flow tube coupled with a laser induced fluorescence(LIF) system.The measurement was conducted with atmospherically relevant HO2 concentrations(~1×10^9 molecule/cm^3) at 51% RH.The measured γ(HO2) onto aqueous(NH4)2 SO4 aerosol was 0.001±0.0007,which was consistent with the relatively low first-order loss rate of HO2 onto aqueous(NH4)2 SO4 aerosol.Theγ(HO2) was elevated with increase of Cu(Ⅱ) concentrations in aqueous(NH4)2 SO4 aerosol.The threshold of Cu(Ⅱ) concentration was10^-3 mol/L for the dramatic increase of γ(HO2).It was found that γ(HO2) reached 0.1 when Cu(Ⅱ)concentration in aerosol was larger than 10^-3 mol/L,suggesting that γ(HO2) is very sensitive to concentration of transition metal ions in aerosol.

Heterogeneous uptake of nitrogen dioxide on Chinese mineral dust

Mineral dust is one of the major aerosols in the atmosphere.To assess its impact on trace atmospheric gases,in this work we present a laboratory study of the effect of temperature on the heterogeneous reaction of NO2 on the surface of ambient Chinese dust over the temperature range from 258 to 313 K.The results suggest that nitrogen dioxide could mainly be adsorbed on these types of Chinese mineral dust reversibly with little temperature dependence.Similar to a previous study on NO2 uptake on mineral aerosols,the uptake coefficients are mainly on the order of 10^（-6） for the Chinese dust,when BET areas are taken into account.HONO was observed as a product,and its formation and decomposition on Chinese mineral dust during the uptake processes were also studied.The complete dataset from this study was compiled with previous literature determinations.Atmospheric implications of the heterogeneous reaction between NO2 and mineral dust are also discussed,in an effort to understand this important heterogeneous process.

Heterogeneous uptake of NO_2 on soils under variable temperature and relative humidity conditions

Heterogeneous reactions of nitrogen dioxide （NO2） on soils collected from Dalian （S 1） and Changsha （S2） were investigated over the relative humidity （RH） range of 5%-80% and temperature range of 278-328 K using a horizontal coated-wall flow tube. The initial uptake coefficients of NO2 on S2 exhibited a decreasing trend from （10 ± 1.3） × 10-8 to （3.1 ± 0.5） x 10-8 with the relative humidity increasing from 5% to 80%. In the temperature effect studies, the initial uptake coefficients of S1 and S2 decreased from （10± 1.2） × 10-8 to （3.8 ± 0.5） × 10-8 and from （16± 2.2） × 10-8 to （3.8 ±0.4） × 10-8 when temperature increased from 278 to 288 K for S1 and from 278 to 308 K for S2, respectively. As the temperature continued to increase, the initial uptake coefficients of S1 and S2 returned to （7.9 ± 1.1）× 10-8 and （20 ± 3.1） × 10-8 at 313 and 328 K, respectively. This study shows that relative humidity could influence the uptake kinetics of NO2 on soil and temperature would impact the heterogeneous chemistry of NO2.

Knudsen cell and smog chamber study of the heterogeneous uptake of sulfur dioxide on Chinese mineral dust

The heterogeneous uptake processes of sulfur dioxide on two types of Chinese mineral dust（Inner Mongolia desert dust and Xinjiang sierozem） were investigated using both Knudsen cell and smog chamber system. The temperature dependence of the uptake coefficients was studied over a range from 253 to 313 K using the Knudsen cell reactor, the initial uptake coefficients decreased with the increasing of temperature for these two mineral dust samples, whereas the steady state uptake coefficients of the Xinjiang sierozem increased with the temperature increasing, and these temperature dependence functions were obtained for the first time. In the smog chamber experiments at room temperature, the steady state uptake coefficients of SO2 decreased evidently with the increasing of sulfur dioxide initial concentration from 1.72 × 1012 to 6.15 × 1012mol/cm3. Humid air had effect on the steady state uptake coefficients of SO2 onto Inner Mongolia desert dust.Consequences about the understanding of the uptake processes onto mineral dust samples and the environmental implication were also discussed.

Uptake of isoprene, methacrylic acid and methyl methacrylate into aqueous solutions of sulfuric acid and hydrogen peroxide

Multiphase acid-catalyzed oxidation by hydrogen peroxide has been suggested to be a potential route to secondary organic aerosol formation from isoprene and its gas-phase oxidation products, but the lack of kinetics data significantly limited the evaluation of this process in the atmosphere. Here we report the first measurement of the uptake of isoprene, methacrylic acid and methyl methacrylate into aqueous solutions of sulfuric acid and hydrogen peroxide. Isoprene cannot readily partition into the solution because of its high volatility and low solubility, which hinders its further liquid-phase oxidation. Both methacrylic acid and methyl methacrylate can enter the solutions and be oxidized by hydrogen peroxide, and steady-state uptake was observed with the acidity of solution above 30 wt.% and 70 wt.%, respectively. The steady-state uptake coefficient of methacrylic acid is much larger than that of methyl methacrylate for a solution with same acidity. These observations can be explained by the different reactivity of these two compounds caused by the different electron-withdrawing conjugation between carboxyl and ester groups. The atmospheric lifetimes were estimated based on the calculated steady-state uptake coefficients. These results demonstrate that the multiphase acid-catalyzed oxidation of methacrylic acid plays a role in secondary organic aerosol formation, but for isoprene and methyl methacrylate, this process is not important in the troposphere.

Measurement of heterogeneous uptake of NO2 on inorganic particles, sea water and urban grime

Heterogeneous reactions of NO2 on different surfaces play an important role in atmospheric NOxremoval and HONO formation,having profound impacts on photochemistry in polluted urban areas.Previous studies have suggested that the NO2 uptake on the ground or aerosol surfaces could be a dominant source for elevated HONO during the daytime.However,the uptake behavior of NO2 varies with different surfaces,and different uptake coefficients were used or derived in different studies.To obtain a more holistic picture of heterogeneous NO2 uptake on different surfaces,a series of laboratory experiments using different flow tube reactors was conducted,and the NO2 uptake coefficients(γ)were determined on inorganic particles,sea water and urban grime.The results showed that heterogeneous reactions on those surfaces were generally weak in dark conditions,with the measuredγvaried from<10-8 to 3.2×10-7 under different humidity.A photo-enhanced uptake of NO2 on urban grime was observed,with the obvious formation of HONO and NO from the heterogeneous reaction.The photo-enhancedγwas measured to be 1.9×10-6 at 5%relative humidity(RH)and 5.8×10-6 at 70%RH on urban grime,showing a positive RH dependence for both NO2 uptake and HONO formation.The results demonstrate an important role of urban grime in the daytime NO2-to-HONO conversion,and could be helpful to explain the unknown daytime HONO source in the polluted urban area.

Heterogeneous uptake of NO_(2) by sodium acetate droplets and secondary nitrite aerosol formation

The high NO_(3)^(−)concentration in fine particulate matters(PM_(2.5))during heavy haze events has attracted much attention,but the formation mechanism of nitrates remains largely uncertain,especially concerning heterogeneous uptake of NOX by aqueous phase.In this work,the heterogeneous uptake of NO_(2) by sodium acetate(NaAc)droplets with different NO_(2) concentrations and relative humidity(RH)conditions is investigated by microscopic Fourier transform infrared spectrometer(micro-FTIR).The IR feature changes of aqueous droplets indicate the acetate depletion and nitrite formation in humid environment.This implies that acetate droplets can provide the alkaline aqueous circumstances caused by acetate hydrolysis and acetic acid(HAc)volatilization for nitrite formation during the NO_(2) heterogeneous uptake.Meanwhile,the nitrite formation will exhibit a pH neutralizing effect on acetate hydrolysis,further facilitating HAc volatilization and acetate depletion.The heterogeneous uptake coefficient increases from 5.2×10^(−6) to 1.27×10^(−5) as RH decreases from 90%to 60%due to the enhanced HAc volatilization.Furthermore,no obvious change in uptake coefficient with different NO_(2) concentrations is observed.This work may provide a new pathway for atmospheric nitrogen cycling and secondary nitrite aerosol formation.

Heterogeneous uptake of gaseous hydrogen peroxide on mineral dust

The heterogeneous uptake processes of hydrogen peroxide on Arizona test dust and two types of authentic Chinese mineral dusts, i.e., Inner Mongolia desert dust and Xinjiang calciferous dust, were investigated using a Knudsen cell reactor coupled with a quadrupole mass spectrometer. The uptake coefficients were measured as a function of the initial concentration of H_2O_2 from 2.6 × 10^（11） to 1.2 × 10^（12）molecules/cm^3, and the temperature dependence of the uptake coefficients was investigated over a range from 253 to 313 K. The concentration of H_2O_2 showed little effect on the uptake coefficients of these heterogeneous processes. As a function of temperature, the initial uptake coefficients decrease with increasing temperature, whereas the steady state uptake coefficients of Arizona test dust and Inner Mongolia desert dust increase with increasing temperature. Implications for the understanding of the uptake processes onto mineral dust samples were also discussed.

Heterogeneous reaction of NO_2 on the surface of montmorillonite particles

The studies on heterogeneous reactions over montmorillonite, which is a typical 2：1 layered aluminosilicate, will benefit to the Understanding of heterogeneous reactions on clay minerals. Montmorillonite can be classified as sodium montmorillonite or calcium montmorillonite depending on the cation presented between the different layers. Using diffuse reflectance infrared Fourier transform spectroscopy （DRIFTS）, the heterogeneous reaction mechanism of NO2 on the surface of montmorillonite was firstly investigated. Results showed that the reaction of NO2 on the surface of sodium and calcium montmorillonite fit a first-order kinetics, and the reaction duration of calcium montmorillonite was longer than that of sodium montmorillonite under the dry condition. For either sodium or calcium montmorillonite, the uptake coefficient decreased as humidity increased.

Acid-catalyzed heterogeneous reaction of 3-methyl-2-buten-1-ol with hydrogen peroxide

Acid-catalyzed heterogeneous oxidation with hydrogen peroxide（H2O2） has been suggested to be a potential pathway for secondary organic aerosol（SOA） formation from isoprene and its oxidation products. However, knowledge of the chemical mechanism and kinetics for this process is still incomplete. 3-Methyl-2-buten-1-ol（MBO321）, an aliphatic alcohol structurally similar to isoprene, is emitted by pine forests and widely used in the manufacturing industries. Herein the uptake of MBO321 into H2SO4-H2O2mixed solution was investigated using a flow-tube reactor coupled to a mass spectrometer. The reactive uptake coefficients（γ） were acquired for the first time and were found to increase rapidly with increasing acid concentration. Corresponding aqueous-phase reactions were performed to further study the mechanism of this acid-catalyzed reaction. MBO321 could convert to 2-methyl-3-buten-2-ol（MBO232） and yield isoprene in acidic media. Organic hydroperoxides（ROOHs） were found to be generated through the acid-catalyzed route,which could undergo a rearrangement reaction and result in the formation of acetone and acetaldehyde. Organosulfates, which have been proposed to be SOA tracer compounds in the atmosphere, were also produced during the oxidation process. These results suggest that the heterogeneous acid-catalyzed reaction of MBO321 with H2O2 may contribute to SOA mass under certain atmospheric conditions.