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.     

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.     

Online single particle measurement of fireworks pollution during Chinese New Year in Nanning

Time-resolved single-particle measurements were conducted during Chinese New Year in Nanning, China. Firework displays resulted in a burst of SO_2, coarse mode, and accumulation mode(100–500 nm) particles. Through single particle mass spectrometry analysis, five different types of particles(fireworks-metal, ash, dust, organic carbon-sulfate(OC-sulfate), biomass burning) with different size distributions were identified as primary emissions from firework displays. The fireworks-related particles accounted for more than70% of the total analyzed particles during severe firework detonations. The formation of secondary particulate sulfate and nitrate during firework events was investigated on single particle level. An increase of sulfite peak(80SO_3~-) followed by an increase of sulfate peaks(97HSO_4~-+ 96SO_4~-) in the mass spectra during firework displays indicated the aqueous uptake and oxidation of SO_2 on particles. High concentration of gaseous SO_2, high relative humidity and high particle loading likely promoted SO_2 oxidation. Secondary nitrate formed through gas-phase oxidation of NO_2 to nitric acid, followed by the condensation into particles as ammonium nitrate. This study shows that under worm, humid conditions, both primary and secondary aerosols contribute to the particulate air pollution during firework displays.     

Heterogeneous reaction of SO2 on CaCO3 particles: Different impacts of NO2 and acetic acid on the sulfite and sulfate formation

Despite the heterogeneous reaction of sulfur dioxide (SO₂) on mineral dust particles significantly affects the atmospheric environment, the effect of acidic gases on the formation of sulfite and sulfate from this reaction is not particularly clear. In this work, using the in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) technique, we employed a mineral dust particle model (CaCO₃) combined with NO₂ and acetic acid to investigate their effects on the heterogeneous reaction of SO₂ on CaCO₃ particles. It was found that water vapor can promote the formation of sulfite and simulated radiation can facilitate the oxidation of sulfite to sulfate. The addition of NO₂ or acetic acid to the reaction system altered the production of sulfate and sulfite accordingly. There was a synergistic effect between NO₂ and SO₂ that promoted the oxidation of sulfite to sulfate, and a competitive effect between acetic acid and SO₂ that inhibited the formation of sulfite. Moreover, light and water vapor can also affect the heterogeneous reaction of SO₂ with the coexistence of multiple gases. These findings improve our understanding of the effects of organic and inorganic gases and environmental factors on the formation of sulfite and sulfate in heterogeneous reactions.     

Role of secondary aerosols in haze formation in summer in the Megacity Beijing

A field experiment from 18 August to 8 September 2006 in Beijing, China, was carried out. A hazy day was defined as visibility < l0 km and RH (relative humidity) < 90%. Four haze episodes, which accounted for ~ 60% of the time during the whole campaign, were characterized by increases of SNA (sulfate, nitrate, and ammonium) and SOA (secondary organic aerosol) concentrations. The average values with standard deviation of SO₄^2 −, NO₃⁻, NH₄⁺ and SOA were 49.8 (± 31.6), 31.4 (± 22.3), 25.8 (± 16.6) and 8.9 (± 4.1) μg/m³, respectively, during the haze episodes, which were 4.3, 3.4, 4.1, and 1.7 times those in the non-haze days. The SO₄^2 −, NO₃⁻, NH₄⁺, and SOA accounted for 15.8%, 8.8%, 7.3%, and 6.0% of the total mass concentration of PM₁₀ during the non-haze days. The respective contributions of SNA species to PM₁₀ rose to about 27.2%, 15.9%, and 13.9% during the haze days, while the contributions of SOA maintained the same level with a slight decrease to about 4.9%. The observed mass concentrations of SNA and SOA increased with the increase of PM₁₀ mass concentration, however, the rate of increase of SNA was much faster than that of the SOA. The SOR (sulfur oxidation ratio) and NOR (nitrogen oxidation ratio) increased from non-haze days to hazy days, and increased with the increase of RH. High concentrations of aerosols and water vapor favored the conversion of SO₂ to SO₄^2 − and NO₂ to NO₃⁻, which accelerated the accumulation of the aerosols and resulted in the formation of haze in Beijing.     

Heterogeneous uptake of NO2 on soils under variable temperature and relative humidity conditions

Heterogeneous reactions of nitrogen dioxide (NO₂) on soils collected from Dalian (S1) 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) × 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.     

Reactive uptake of NO2 on volcanic particles: A possible source of HONO in the atmosphere

The heterogeneous degradation of nitrogen dioxide (NO₂) on five samples of natural Icelandic volcanic particles has been investigated. Laboratory experiments were carried out under simulated atmospheric conditions using a coated wall flow tube (CWFT). The CWFT reactor was coupled to a blue light nitrogen oxides analyzer (NO_x analyzer), and a long path absorption photometer (LOPAP) to monitor in real time the concentrations of NO₂, NO and HONO, respectively. Under dark and ambient relative humidity conditions, the steady state uptake coefficients of NO₂ varied significantly between the volcanic samples probably due to differences in magma composition and morphological variation related with the density of surface OH groups. The irradiation of the surface with simulated sunlight enhanced the uptake coefficients by a factor of three indicating that photo-induced processes on the surface of the dust occur. Furthermore, the product yields of NO and HONO were determined under both dark and simulated sunlight conditions. The relative humidity was found to influence the distribution of gaseous products, promoting the formation of gaseous HONO. A detailed reaction mechanism is proposed that supports our experimental observations. Regarding the atmospheric implications, our results suggest that the NO₂ degradation on volcanic particles and the corresponding formation of HONO is expected to be significant during volcanic dust storms or after a volcanic eruption.     

Individual particle analysis of aerosols collected at Lhasa City in the Tibetan Plateau

To understand the composition and major sources of aerosol particles in Lhasa City on the Tibetan Plateau (TP), individual particles were collected from 2 February to 8 March, 2013 in Tibet University. The mean concentrations of both PM_2.5 and PM₁₀ during the sampling were 25.7 ± 21.7 and 57.2 ± 46.7 μg/m³, respectively, much lower than those of other cities in East and South Asia, but higher than those in the remote region in TP like Nam Co, indicating minor urban pollution. Combining the observations with the meteorological parameters and back trajectory analysis, it was concluded that local sources controlled the pollution during the sampling. Transmission electron microscopy (TEM) combined with energy-dispersive X-ray spectra (EDS) was used to study 408 particles sampled on four days. Based on the EDS analysis, a total of 8 different particle categories were classified for all 408 particles, including Si-rich, Ca-rich, soot, K-rich, Fe-rich, Pb-rich, Al-rich and other particles. The dominant elements were Si, Al and Ca, which were mainly attributed to mineral dust in the earth's crust such as feldspar and clay. Fe-, Pb-, K-, Al-rich particles and soot mainly originated from anthropogenic sources like firework combustion and biomass burning during the sampling. During the sampling, the pollution mainly came from mineral dust, while the celebration ceremony and religious ritual produced a large quantity of anthropogenic metal-bearing particles on 9 and 25 February 2013. Cement particles also had a minor influence. The data obtained in this study can be useful for developing pollution control strategies.     

Composition and source apportionment of dust fall around a natural lake

The aim of this study was to determine the source apportionment of dust fall around Lake Chini, Malaysia. Samples were collected monthly between December 2012 and March2013 at seven sampling stations located around Lake Chini. The samples were filtered to separate the dissolved and undissolved solids. The ionic compositions(NO-3, SO2-4, Cl-and NH+4) were determined using ion chromatography(IC) while major elements(K, Na, Ca and Mg) and trace metals(Zn, Fe, Al, Ni, Mn, Cr, Pb and Cd) were determined using inductively coupled plasma mass spectrometry(ICP-MS). The results showed that the average concentration of total solids around Lake Chini was 93.49 ± 16.16 mg/(m2·day). SO2-4, Na and Zn dominated the dissolved portion of the dust fall. The enrichment factors(EF) revealed that the source of the trace metals and major elements in the rain water was anthropogenic, except for Fe. Hierarchical agglomerative cluster analysis(HACA) classified the seven monitoring stations and 16 variables into five groups and three groups respectively. A coupled receptor model, principal component analysis multiple linear regression(PCA-MLR), revealed that the sources of dust fall in Lake Chini were dominated by agricultural and biomass burning(42%),followed by the earth's crust(28%), sea spray(16%) and a mixture of soil dust and vehicle emissions(14%).     

FTIR spectroscopic measurements of surface bond products of nitrogen oxides on aerosol surfaces—implications for heterogeneous HNO2 production

FTIR spectroscopy measurements have been made to investigate the products of heterogeneous reactions of nitrogen oxides like NO₂, N₂O₅ and HNO₂ in the presence of water vapour on artificial and natural aerosol surfaces. Surface species on NaCl particles differ significantly from those on urban aerosols or fly ash. Evidence for a nighttime production of NO₂⁻ on sea-salt surfaces from reactions of N₂O₅ and water vapour is given.     

Influences of anion concentration and valence on dispersion and aggregation of titanium dioxide nanoparticles in aqueous solutions

Dispersion and aggregation of nanoparticles in aqueous solutions are important factors for safe application of nanoparticles. In this study, dispersion and aggregation of nano-TiO₂ in aqueous solutions containing various anions were investigated. The influences of anion concentration and valence on the aggregation size, zeta potential and aggregation kinetics were individually investigated. Results showed that the zeta potential decreased from 19.8 to − 41.4 mV when PO₄^3 − concentration was increased from 0 to 50 mg/L, while the corresponding average size of nano-TiO₂ particles decreased from 613.2 to 540.3 nm. Both SO₄^2 − and NO₃⁻ enhanced aggregation of nano-TiO₂ in solution. As SO₄^2 − concentration was increased from 0 to 500 mg/L, the zeta potential decreased from 19.8 to 1.4 mV, and aggregate sizes increased from 613.2 to 961.3 nm. The trend for NO₃⁻ fluctuation was similar to that for SO₄^2 − although the range of variation for NO₃⁻ was relatively narrow. SO₄^2 − and NO₃⁻ accelerated the aggregation rapidly, while PO₄^3 − did so slowly. These findings facilitate the understanding of aggregation and dispersion mechanisms of nano-TiO₂ in aqueous solutions in the presence of anions of interest.     

Interactions of aerosols (ammonium sulfate,ammonium nitrate and ammonium chloride) and of gases (HCl,HNO3) with fogwater

The concentrations of aerosols (NH₄NO₃, (NH₄)₂SO₄ and NH₄Cl) and of gases (HCl_(g), HNO_3(g), NH_3(g) were determined by denuder methods under different conditions (in the absence of fog, before, during and after fog events). At this site situated in an urban region, high concentrations of the gaseous strong acids HCl_(g) and HNO_3(g) are observed. NH₄Cl and NH₄NO₃ aerosols represent a major fraction of the Cl⁻ and NO₃⁻ aerosols (<2.4 μm)collected by denuders. During a fog event, very high concentrations of SO₄²⁻ were found in small aerosols, which are attributed to the aqueous phase oxidation of SO₂ under the influence of high pH due to the presence of NH₃. Differences in SO₄²⁻ concentrations measured in aerosols (<2.4 μm) and in fog droplets were probably due to mass-transport limitations of the SO₂ oxidation. Ammonium sulfate aerosols represent in some cases a significant fraction of the total S present (SO_2(g) + SO₄²⁻. Soluble aerosols and gases contribute to the composition of fogwater and are released again after fog dissipation.     

VOCs源强不确定性对臭氧生成及污染防治影响的模拟分析

本文基于三维区域空气质量模式WRF-Chem,通过修改模式化学模块,量化输出过程量和诊断量,提供了一种定量分析挥发性有机化合物(VOCs)源强不确定性对O3生成影响的方法.为无法定量计算VOCs源强导致的臭氧生成率[P(O3)]偏差,以及由此对O3体积分数分布和污染控制相关联的VOCs敏感区和NOx 敏感区分布的误判提供了方法参考.采用标准统计参数对WRF-Chem模式的气象场与污染场模拟性能进行了评估,相关指标均优于前人结果.以INTEX-B(intercontinental chemical transport experiment-phase B)人为源、FINNv1(fire inventory from NCAR version 1)生物质燃烧源和 MEGAN(model of emissions of gases and aerosols from nature)生物源作为基准源,并以卫星观测数据作为约束,对排放源进行改进,评估了源改进前后臭氧生成率[P(O3)]、O3体积分数和O3控制敏感区指标(Ln/Q)的变化情况.仅人为VOCs(AVOCs)源增加68％后,P(O3)模拟峰值增升比例达13％～82％,以北京观测站点为例,P(O3)模拟月均峰值增加42％(22.5×10-9 h-1).对P(03)形成贡献比例最大的主要化学反应是HO2+NO(占比约68％),AVOCs源增加68％后,该反应贡献比例下降至65％.在改进源下,P(O3)普遍增加达到2×10-9～4×10-9h-O3各季节增幅较大的区域均主要集中在京津冀、长三角和珠三角中心城市及周边区域,与我国大型城市区基本都是VOCs敏感区的结论一致.整体而言,VOCs源强改进后,Nox敏感区O3体积分数增加幅度不大,不超过4×10-9,而部分VOCs敏感区增幅超过20 x10-9.VOCs源强的不确定性会影响O3形成过程中Nox和VOCs敏感区的判断,特别是VOCs源强明显低估会夸大VOCs敏感区的范围,从而降低O3调控对策的有效性.     

天津市高校夏季道路扬尘PM2.5中水溶性离子污染特征及来源

为研究天津市高校道路扬尘PM_2.5中水溶性离子的污染特征、来源及校内外差异，于2018年7—8月采集天津市9所高校道路扬尘样品，用离子色谱法对其中8种水溶性离子（Ca²⁺、K⁺、Mg²⁺、Na⁺、Cl^-、NH₄⁺、NO₃^-、SO₄^2-）进行分析.结果显示：①水溶性离子占PM_2.5的11.65%，PM_2.5中占比大于1%的离子有Ca²⁺和SO₄^2-，其中Ca²⁺最多，占到总水溶性无机离子的65.75%；②入校道路离子含量（12.76%）稍高于校内道路（11.11%），其中8种离子含量的差异均无统计学意义；CE/AE（阴阳离子当量浓度比）值为9.59（远大于1），PM_2.5呈较强碱性；③NH₄⁺与SO₄^2-、NO₃^-主要以（NH₄）₂SO₄和NH₄NO₃的形态结合；④NO₃^-/SO₄^2-的比值为0.45，说明固定源的贡献更大；⑤天津市高校道路扬尘PM_2.5主要来源于海盐粒子、燃煤、机动车尾气、建筑水泥尘等.     

Nitrate formation on sea-salt and mineral particles—A single particle approach

Heterogeneous reactions of NO₂ and HNO₃ at sub-ppm levels with individual sea-salt and mineral particles were investigated. Particles deposited on filters and on electron microscope grids placed in a Teflon reaction chamber, were exposed to NO₂ or HNO₃ under controlled conditions. Experiments were carried out under dark conditions and were repeated under u.v. radiation (solar simulation). Nitrates formed on the particles were determined by bulk and individual particle analyses. Individual sea-salt and mineral particles were observed in a transmission electron microscope for the presence of nitrate on the particle surface.The formation of nitrates on sea-salt particles under dark conditions, was in the range of 0.1–3.3 mg NO₃⁻ g⁻¹ NaCl. Higher values were obtained for mineral particles: 0.2–8.2 mg NO₃⁻ g⁻¹ aerosol ([NO₂] =0.18 and 0.54 ppm; [HNO₃] = 0.04 ppm; exposure time 1–7 days; relative humidity = 70%). The formation of nitrates on sea-salt particles increased from 3.0 to 16.1 mg NO₃⁻ g⁻ NaCl when u.v. radiation was added. Mineral particles did not show a significant increase in nitrate formation under u.v. radiation.Microscopy showed that about 50% of the soil particles reacted with NO₂ and HNO₃ to form mixed nitrate particles. Almost all sea-salt particles (above 95%) reacted with both gases, although the reaction was not complete and took place only on the particle surface.Application of electron microscopy and a specific microspot technique provided direct evidence for the formation of nitrate on sea-salt and mineral particles exposed to NO₂ and HNO₃.     

Coupling mechanism of activated carbon mixed with dust for flue gas desulfurization and denitrification

To clarify the effect of coking dust, sintering dust and fly ash on the activity of activated carbon for various industrial flue gas desulfurization and denitrification, the coupling mechanism of the mixed activated carbon and dust was investigated to provide theoretical reference for the stable operation. The results show that coking dust had 34% desulfurization efficiency and 10% denitrification efficiency; correspondingly, sintering dust and fly ash had no obvious desulfurization and denitrification activities. For the mixture of activated carbon and dust, the coking dust reduced the desulfurization and denitrification efficiencies by blocking the pores of activated carbon, and its inhibiting effect on activated carbon was larger than its own desulfurization and denitrification activity. The sintering dust also reduced the desulfurization efficiency on the activated carbon while enhancing the denitrification efficiency. Fly ash blocked the pores of activated carbon and reduced its reaction activity. The reaction activity of coking dust mainly came from the surface functional groups, similar to that of activated carbon. The reaction activity of sintering dust mainly came from the oxidative property of Fe₂O₃, which oxidized NO to NO₂ and promoted the fast selectively catalytic reduction (SCR) of NO to form N₂. Sintering dust was activated by the joint action of activated carbon, and both had a coupling function. Sintering dust enhanced the adsorption and oxidation of NO, and activated carbon further promoted the reduction of NO_x by NH₃; thus, the denitrification efficiency increased by 5%-7% on the activated carbon.     

Numerical evaluation of the effectiveness of NO2 and N2O5 generation during the NO ozonation process

Wet scrubbing combined with ozone oxidation has become a promising technology for simultaneous removal of SO₂ and NO_x in exhaust gas. In this paper, a new 20-species, 76-step detailed kinetic mechanism was proposed between O₃ and NO_x. The concentration of N₂O₅ was measured using an in-situ IR spectrometer. The numerical evaluation results kept good pace with both the public experiment results and our experiment results. Key reaction parameters for the generation of NO₂ and N₂O₅ during the NO ozonation process were investigated by a numerical simulation method. The effect of temperature on producing NO₂ was found to be negligible. To produce NO₂, the optimal residence time was 1.25 sec and the molar ratio of O₃/NO about 1. For the generation of N₂O₅, the residence time should be about 8 sec while the temperature of the exhaust gas should be strictly controlled and the molar ratio of O₃/NO about 1.75. This study provided detailed investigations on the reaction parameters of ozonation of NO_x by a numerical simulation method, and the results obtained should be helpful for the design and optimization of ozone oxidation combined with the wet flue gas desulfurization methods (WFGD) method for the removal of NO_x.     

Heterogeneous reaction of NO2 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.     

A case study of Asian dust storm particles: Chemical composition, reactivity to SO2 and hygroscopic properties

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 SO₂, and hygroscopic behavior were studied. The major components of Asian dust storm particles are aluminosilicate, SiO₂ and CaCO₃, with organic compounds and inorganic nitrate coated on the surface. It has a low reactivity towards SO₂ with a true uptake coefficient, 5.767×10^-6, which limits the conversion of SO₂ to sulfate during dust storm periods. The low reactivity also means that the heterogeneous reactions of SO₂ in both dry and humid air conditions have little effect on the hygroscopic behavior of the dust particles.     

Abatement of SO2–NOx binary gas mixtures using a ferruginous active absorbent: Part I. Synergistic effects and mechanism

A novel ferruginous active absorbent, prepared by fly ash, industrial lime and the additive Fe(VI), was introduced for synchronous abatement of binary mixtures of SO₂–NOx from simulated coal-fired flue gas. The synergistic action of various factors on the absorption of SO₂ and NOx was investigated. The results show that a strong synergistic effect exists between Fe(VI) dose and reaction temperature for the desulfurization. It was observed that in the denitration process, the synergy of Fe(VI) dose and Ca/(S + N) had the most significant impact on the removal of NO, followed by the synergy of Fe(VI) and reaction temperature, and then the synergy of reaction temperature and flue gas humidity. A scanning electron microscope (SEM) and an accessory X-ray energy spectrometer (EDS) were used to observe the surface characteristics of the raw and spent absorbent as well as fly ash. A reaction mechanism was proposed based on chemical analysis of sulfur and nitrogen species concentrations in the spent absorbent. The Gibbs free energy, equilibrium constants and partial pressures of the SO₂–NOx binary system were determined by thermodynamics.