A large-scale outdoor atmospheric simulation smog chamber for studying atmospheric photochemical processes: Characterization and preliminary application

Understanding the formation mechanisms of secondary air pollution is very important for the formulation of air pollution control countermeasures in China. Thus, a large-scale outdoor atmospheric simulation smog chamber was constructed at Chinese Research Academy of Environmental Sciences (the CRAES Chamber), which was designed for simulating the atmospheric photochemical processes under the conditions close to the real atmospheric environment. The chamber consisted of a 56-m³ fluorinated ethylene propylene (FEP) Teflon film reactor, an electrically-driven stainless steel alloy shield, an auxiliary system, and multiple detection instrumentations. By performing a series of characterization experiments, we obtained basic parameters of the CRAES chamber, such as the mixing ability, the background reactivity, and the wall loss rates of gaseous compounds (propene, NO, NO₂, ozone) and aerosols (ammonium sulfate). Oxidation experiments were also performed to study the formation of ozone and secondary organic aerosol (SOA), including α-pinene ozonolysis, propene and 1,3,5-trimethylbenzene photooxidation. Temperature and seed effects on the vapor wall loss and SOA yields were obtained in this work: higher temperature and the presence of seed could reduce the vapor wall loss; SOA yield was found to depend inversely on temperature, and the presence of seed could increase SOA yield. The seed was suggested to be used in the chamber to reduce the interaction between the gas phase and chamber walls. The results above showed that the CRAES chamber was reliable and could meet the demands for investigating tropospheric chemistry.     

Kinetics of the gas-phase reactions of NO3 radicals with ethyl acrylate,n-butyl acrylate,methyl methacrylate and ethyl methacrylate

The relative rate method has been used to determine the rate constants for the gas-phase reactions of NO₃ radicals with a series of acrylate esters: ethyl acrylate (k₁), n-butyl acrylate (k₂), methyl methacrylate (k₃) and ethyl methacrylate (k₄) at 298 ± 1 K and 760 Torr. The obtained rate constants are k₁ = (1.8 ± 0.25) × 10⁻¹⁶ cm³ molecule⁻¹ s⁻¹, k₂ = (2.1 ± 0.33) × 10⁻¹⁶ cm³ molecule⁻¹ s⁻¹, k₃ = (3.6 ± 1.2) × 10⁻¹⁵ cm³ molecule⁻¹ s⁻¹, k₄ = (4.9 ± 1.7) × 10⁻¹⁵ cm³ molecule⁻¹ s⁻¹. The experimental rate constants are in good agreement with theoretical rate constants calculated by an algorithm of the correlation between the rate constants and the orbital energies for the reactions of unsaturated VOCs with NO₃ radicals. In addition, the atmospheric lifetimes of the compound against NO₃ attack are estimated and the results show that NO₃ reactions contribute little to the atmospheric losses of acrylate esters except in polluted regions.     

Adsorption of heavy metal ions from aqueous solution by carboxylated cellulose nanocrystals

A novel nanoadsorbent for the removal of heavy metal ions is reported.Cotton was first hydrolyzed to obtain cellulose nanocrystals(CNCs).CNCs were then chemically modified with succinic anhydride to obtain SCNCs.The sodic nanoadsorbent(NaSCNCs) was further prepared by treatment of SCNCs with saturated NaHCO 3 aqueous solution.Batch experiments were carried out with SCNCs and NaSCNCs for the removal of Pb 2+ and Cd 2+.The effects of contact time,pH,initial adsorption concentration,coexisting ions and the regeneration performance were investigated.Kinetic studies showed that the adsorption equilibrium time of Pb 2+ and Cd 2+ was reached within 150 min on SCNCs and 5 min on NaSCNCs.The adsorption capacities of Pb 2+ and Cd 2+ on SCNCs and NaSCNCs increased with increasing pH.The adsorption isotherm was well fitted by the Langmuir model.The maximum adsorption capacities of SCNCs and NaSCNCs for Pb 2+ and Cd 2+ were 367.6 mg/g,259.7 mg/g and 465.1 mg/g,344.8 mg/g,respectively.SCNCs and NaSCNCs showed high selectivity and interference resistance from coexisting ions for the adsorption of Pb 2+.NaSCNCs could be efficiently regenerated with a mild saturated NaCl solution with no loss of capacity after two recycles.The adsorption mechanisms of SCNCs and NaSCNCs were discussed.     

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.     

Measurement of atmospheric nanoparticles: Bridging the gap between gas-phase molecules and larger particles

Atmospheric nanoparticles are crucial components contributing to fine particulate matter (PM_2.5), and therefore have significant effects on visibility, climate, and human health. Due to the unique role of atmospheric nanoparticles during the evolution process from gas-phase molecules to larger particles, a number of sophisticated experimental techniques have been developed and employed for online monitoring and characterization of the physical and chemical properties of atmospheric nanoparticles, helping us to better understand the formation and growth of new particles. In this paper, we firstly review these state-of-the-art techniques for investigating the formation and growth of atmospheric nanoparticles (e.g., the gas-phase precursor species, molecular clusters, physicochemical properties, and chemical composition). Secondly, we present findings from recent field studies on the formation and growth of atmospheric nanoparticles, utilizing several advanced techniques. Furthermore, perspectives are proposed for technique development and improvements in measuring atmospheric nanoparticles.     

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.     

Kinetic and mechanism studies of the ozonolysis of three unsaturated ketones

Reaction rate constants and products of 1-octen-3-one, 3-octen-2-one and 4-hexen-3-one with ozone were studied in a 100-L fluorinated ethylene propylene (FEP) Teflon film bag using absolute rate method at 298 ± 1 K and atmospheric pressure. The rate constants were (1.09 ± 0.12) × 10^?17, (3.48 ± 0.36) × 10^?17 and (5.70 ± 0.60) × 10^?17 cm³/(molecule?sec), respectively. According to the obtained rate constants, the effects of carbonyl were discussed. The carbonyl group in β position has a net withdrawing effect with respect to an olefinic bond, then causing the decline of rate constants. The quantum chemical calculation was used to explain the results of rate constants. The products of ozonolysis were mainly aldehydes, which have significant influence on the formation of SOA, and hence play an important role in the atmosphere. In this work, we detected the main products of reaction and proposed the reaction mechanism by combining the results of quantum chemical calculations. Atmospheric lifetime for three unsaturated ketones reacted with ozone was 36.4, 11.4 and 6.9 hr for 1-octen-3-one, 3-octen-2-one and 4-hexen-3-one, respectively.     

Reaction mechanism and kinetics of Criegee intermediate and hydroperoxymethyl formate

The reaction mechanism and kinetics of the simplest Criegee intermediate CH₂OO reaction with hydroperoxymethyl formate (HPMF) was investigated at high-level quantum chemistry calculations. HPMF has two reactive functional groups, -C(O)OH and -OOH. The calculated results of thermodynamic data and rate constants indicated that the insertion reactions of CH₂OO with –OOH group of HPMF were more favorable than the reactions of CH₂OO with -C(O)OH group. The calculated overall rate constant was 2.33 × 10^?13 cm³/(molecule?sec) at 298 K and the rate constants decreased as the temperature increased from 200 to 480 K. In addition, we also proved the polymerization reaction mechanism between CH₂OO and -OOH of HPMF. This theoretical study interpreted the previous experimental results, and supplied the structures of the intermediate products that couldn't be detected during the experiment.     

Kinetic study of the gas-phase reaction of O3 with three unsaturated alcohols

Rate constants for the reactions of ozone with 1-octen-3-ol, 1-nonen-3-ol and 1-nonen-4-ol have been determined at 298 ± 1 K and atmospheric pressure for the first time. The experiments were performed in a 100-L FEP Teflon film bag using absolute rate method; the rate constants were(1.91 ± 0.19) × 10~(-17),(1.89 ± 0.20) × 10~(-17), and(0.83 ± 0.08) × 10~(-17)cm~3/(molecule·sec) for 1-octen-3-ol, 1-nonen-3-ol, and 1-nonen-4-ol, respectively. The rate constants have been compared with those of unsaturated alcohols structural homologs, and used to estimate the reaction reactivity. The electronegativity of carbon–carbon double bond was calculated by atomic charges analysis. The calculated results show that the electronic effect of the lone pair electrons of hydroxyl oxygen is the main cause of the difference in rate coefficient. According to the obtained rate constants, the atmospheric lifetimes of studied unsaturated alcohols were also estimated, which indicates that the reaction with ozone is an important loss pathway in the atmosphere, especially in polluted areas.     

Water uptake of multicomponent organic mixtures and their influence on hygroscopicity of inorganic salts

The hygroscopic behaviors of atmospherically relevant multicomponent water soluble organic compounds(WSOCs) and their effects on ammonium sulfate(AS) and sodium chloride were investigated using a hygroscopicity tandem differential mobility analyzer(HTDMA) in the relative humidity(RH) range of 5%–90%. The measured hygroscopic growth was compared with predictions from the Extended-Aerosol Inorganics Model(E-AIM) and Zdanovskii–Stokes–Robinson(ZSR) method. The equal mass multicomponent WSOCs mixture containing levoglucosan, succinic acid, phthalic acid and humic acid showed gradual water uptake without obvious phase change over the whole RH range. It was found that the organic content played an important role in the water uptake of mixed particles.When organic content was dominant in the mixture(75%), the measured hygroscopic growth was higher than predictions from the E-AIM or ZSR relation, especially under high RH conditions. For mass fractions of organics not larger than 50%, the hygroscopic growth of mixtures was in good agreement with model predictions. The influence of interactions between inorganic and organic components on the hygroscopicity of mixed particles was related to the salt type and organic content. These results could contribute to understanding of the hygroscopic behaviors of multicomponent aerosol particles.