Wall losses of oxygenated volatile organic compounds from oxidation of toluene: Effects of chamber volume and relative humidity

Vapor wall losses can affect the yields of secondary organic aerosol. The effects of surface-to-volume (S/V) ratio and relative humidity (RH) on the vapor-wall interactions were investigated in this study. The oxygenated volatile organic compounds (OVOCs) were generated from toluene-H₂O₂ irradiations. The average gas to wall loss rate constant (k_gw) of OVOCs in a 400 L reactor (S/V = 7.5 m⁻¹) is 2.47 (2.41 under humid conditions) times higher than that in a 5000 L reactor (S/V = 3.6 m⁻¹) under dry conditions. In contrast, the average desorption rate constant (k_wg) of OVOCs in 400 L reactor is only 1.37 (1.20 under humid conditions) times higher than that in 5000 L reactor under dry conditions. It shows that increasing the S/V ratio can promote the wall losses of OVOCs. By contrast, the RH effect on k_gw is not prominent. The average k_gw value under humid conditions is almost the same as under dry conditions in the 400 L (5000 L) reactor. However, increasing RH can decrease the desorption rates. The average k_wg value under dry conditions is 1.45 (1.27) times higher than that under humid conditions in the 400 L (5000 L) reactor. The high RH can increase the partitioning equilibrium timescales and enhance the wall losses of OVOCs.     

Cars on crutches: How much abatement do smog check repairs actually provide?

Not as much abatement as has been presumed. Smog check programs aim to curb tailpipe emissions from in-use vehicles by requiring repairs whenever emissions, measured at regular time intervals, exceed a certain threshold. Using data from California, we estimate that on average 41% of the initial emissions abatement from repairs is lost by the time of the subsequent inspection, normally two years later. Our estimates imply that the cost per pound of pollution avoided is an order of magnitude greater for smog check repairs than alternative policies such as new-vehicle standards or emissions trading among industrial point sources.     

汽车公害及其综合防治办法

论述了汽车公害的危害性及减少汽车污染的各种综合防治方法－排气净化，革新燃烧系统及发动机等，并展望未来将采用的低污染代用燃料及低污染发动机或无污染动力源．     

Characterization of a new smog chamber for evaluating SAPRC gas-phase chemical mechanism

A new state-of-the-art indoor smog chamber facility (CAPS-ZJU) has been constructed and characterized at Zhejiang University, which is designed for chemical mechanism evaluation under well-controlled conditions. A series of characterization experiments were performed to validate the well-established experimental protocols, including temperature variation pattern, light spectrum and equivalent intensity (J_NO2), injection and mixing performance, as well as gases and particle wall loss. In addition, based on some characterization experiments, the auxiliary wall mechanism has been setup and examined. Fifty chamber experiments were performed across a broad range of experimental scenarios, and we demonstrated the ability to utilize these chamber data for evaluating SAPRC chemical mechanism. It was found that the SAPRC-11 can well predict the O₃ formation and NO oxidation for almost all propene runs, with 6 hr Δ(O₃ – NO) model error of –3% ± 7%, while the final O₃ was underestimated by ~20% for isoprene experiments. As for toluene and p-xylene experiments, it was confirmed that SAPRC-11 has significant improvement on aromatic chemistry than earlier version of SAPRC-07, although the aromatic decay rate was still underestimated to some extent. The model sensitivity test has been carried out, and the most sensitive parameters identified are the initial concentrations of reactants and the light intensity as well as HONO offgasing rate and O₃ wall loss rate. All of which demonstrated that CAPS-ZJU smog chamber could derive high quality experimental data, and could provide insights on chamber studies and chemical mechanism development.     

Exploring the formation potential and optical properties of secondary organic aerosol from the photooxidation of selected short aliphatic ethers

Secondary organic aerosol (SOA) formation potential for six kinds of short aliphatic ethers has been studied. The size distribution, mass concentration, and yield of SOA formed by ethers photooxidation were determined under different conditions. The results showed that all six ethers can generate SOA via reaction with OH radicals even under no seed and NO_x-free condition. The mass concentration for six seedless experiments was less than 10 µg/m³ and the SOA yields were all below 1%. The strong increase in the SOA formation was observed when the system contained ammonium sulfate seed particles, while SOA yield decreased under the high-NO_x condition. SOA composition was analyzed using offline methods. Infrared spectra indicated that there are complex components in the particle-phase including carbonyls acid and aldehydes species. Moreover, the aqueous filter extracts were analyzed using ultraviolet-visible spectrometer and fluorescence spectrophotometer. For the fresh methyl n-butyl ether SOA, the largest absorption peak occurs at 280 nm and there exists slightly absorption in the 300–400 nm. Excitation-emission matrices display the distinct peak at excitation/emission = 470 nm/480 nm according to the fluorescence spectrum. These findings are important considerations of formation for ether SOA that can eventually be included in atmospheric models.     

Reactor characterization and primary application of a state of art dual-reactor chamber in the investigation of atmospheric photochemical processes

Increasing attention has been paid to the air pollution more recently. Smog chamber has been proved as a necessary and effective tool to study atmospheric processes, including photochemical smog and haze formation. A novel smog chamber was designed to study the atmospheric photochemical reaction mechanism of typical volatile organic compounds (VOCs) as well as the aging of aerosols. The smog chamber system includes an enclosure equipped with black lights as the light source, two parallel reactors (2 m³ of each) with separate control of light source and temperature, with a series of coupled instruments for online monitoring of gas phase and particle phase reactants and products. Chamber characterization, including air source stability, effective light intensity, temperature stability, as well as gas phase and particle phase wall losses, were carried out before further research. The results showed that our smog chamber systems developed by other domestic and international groups. It was also observed that the wall loss of aromatic VOCs varied with different functional groups as well as the isomerism. The results of preliminary simulation experiment from styrene-NO_x demonstrated that the chamber can be well utilized to simulate gas-particle conversion progresses in the atmosphere.     

Characteristics of ozone pollution and the sensitivity to precursors during early summer in central plain, China

In this study, we conducted an observation experiment from May 1 to June 30, 2018 in Zhengzhou, a major city in central China, where ground ozone (O₃) pollution has become serious in recent years. The concentrations of O₃ and its precursors, as well as H₂O₂ and meteorological data were obtained from the urban site (Yanchang, YC), suburban (Zhengzhou University, ZZU) and background sites (Ganglishuiku, GLSK). Result showed that the rates of O₃ concentration exceeded Chinese National Air Quality Standard Grade II (93.3 ppbv) were 59.0%, 52.5%, and 55.7% at the above three sites with good consistency, respectively, indicating that O₃ pollution is a regional problem in Zhengzhou. The daily peak O₃ appeared at 15:00–16:00, which was opposite to VOCs, NO_x, and CO and consistent with H₂O₂. The exhaustive statistical analysis of meteorological factors and chemical effects on O₃ formation at YC was advanced. The high concentration of precursors, high temperature, low relative humidity, and moderately high wind speed together with the wind direction dominated by south and southeast wind contribute to urban O₃ episodes in Zhengzhou. O₃ formation analysis showed that reactive alkenes such as isoprene and cis-2-butene contributed most to O₃ formation. The VOCs/NO_x ratio and smog production model were used to determine O₃-VOC-NO_x sensitivity. The O₃ formation in Zhengzhou during early summer was mainly under VOC-limited and transition regions alternately, which implies that the simultaneous emission reduction of alkenes and NO_x is effective in reducing O₃ pollution in Zhengzhou.     

Verteilung und Abnahme von bodennahem Ozon in st?dtischen und l?ndlichen Regionen

Zusammenfassung  Eine Zusammenstellung der Ozon-Me?werte der Luftme?stationnetze in Hessen und NRW ergab für die Jahresmittelwerte von 1990–1998 im Durchschnitt eine schwache Abnahme der Ozonkonzentrationen. Dabei lagen die Jahresmittelwerte der Ozonkonzentrationen über Waldstationen doppelt so hoch wie über Stadtstationen. Die Ozonkonzentrationen verhalten sich im regionalen Vergleich umgekehrt proportional zur Verkehrsdichte. In der Zahl der überschreitungen der gesetzlich festgelegten Grenzwerte von ≥180 μg Ozon/m³ pro Jahr lagen die Waldstationen mit dem 2–3 fachen Wert über den Stadtstationen. Lediglich die j?hrlichen Maximalwerte der stündlich gemessenen Ozonwerte n?hern sich einander. Die hohen Ozonwerte über den Waldstationen stehen im Zusammenhang mit den niedrigen Konzentrationen von NOx. Nachts reduziert sich das Ozon über den Waldstationen durch Rückreaktion mit vergleichsweise geringen Konzentrationen von NO nur bis ca. 50%, w?hrend der Ozongehalt über Stadtstationen bis nahe Null absinkt. Dieser Vorgang über den Stadtstationen wird auch durch Photolyse des in hohen Konzentrationen vorliegenden NO₂ und die dadurch erfolgende erh?hte Bildung von Ozon w?hrend des Tages nicht wieder kompensiert. Für die hier dargestellten Ergebnisse gibt es prinzipiell keine Unterschiede zwischen den Ozonverh?ltnissen in Hessen und NRW.      

Compilation of reaction kinetics parameters determined in the Key Development Project for Air Pollution Formation Mechanism and Control Technologies in China

A compilation of new advances made in the research field of laboratory reaction kinetics in China's Key Development Project for Air Pollution Formation Mechanism and Control Technologies was presented. These advances are grouped into six broad, interrelated categories, including volatile organic compound (VOC) oxidation, secondary organic aerosol (SOA) formation, new particle formation (NPF) and gas-particle partitioning, ozone chemistry, model parameters, and secondary inorganic aerosol (SIA) formation, highlighting the laboratory work done by Chinese researchers. For smog chamber applications, the current knowledge gained from laboratory studies is reviewed, with emphasis on summarizing the oxidation mechanisms of long-chain alkanes, aromatics, alkenes, aldehydes/ketones in the atmosphere, SOA formation from anthropogenic emission sources, and oxidation of aromatics, isoprene, and limonene, as well as SIA formation. For flow tube applications, atmospheric oxidation mechanisms of toluene and methacrolein, SOA formation from limonene oxidation by ozone, gas-particle partitioning of peroxides, and sulfuric acid-water (H₂SO₄-H₂O) binary nucleation, methanesulfonic acid-water (MSA-H₂O) binary nucleation, and sulfuric acid-ammonia-water (H₂SO₄-NH₃-H₂O) ternary nucleation are discussed.     

广州地区SO2转化规律及其形成气溶胶特征的研究

为探明广州地区的酸沉降和细粒子气溶胶污染来源,在该地区用室外烟雾箱进行了环境空气中SO₂反应实验研究,其结果表明:影响SO₂转化速率的主要因素是SO₂起始浓度、太阳光强度、相对湿度和空气中颗粒物。SO₂转化速率与箱内凝结核(简称CNC)气溶胶最大浓度密切相关。气态污染物转化是该地区的细粒子空气污染的一个重要来源。