Sensitivity of Ozone Production to the Nmhc Composition,Aerosol Back-Scattering and High Chimney Emission

Abstract

In this paper, three sensitivity studies are designed to analyze the effect of the NMHC (Non-Methane HydroCarbon) composition, the aerosol back-scattering and the high chimney NO _x emission to the photochemical prodution of ozone by using a one-dimensional photochemistry-diffusion model under a favourable meteorological condition. Measurements of the NMHC composition in Taipei indicated that the percentage of iso-butene, cis-2-butene, trans-2-butene and benzene in a unit volume was much higher than of those observed in other major cities. the high ratio of benzene was directly linked to its high percentage in gasoline. As to the unusually high amount of iso-butene, cis-2-butene and trans-2-butene, more researches are needed to identify their source. Concerns are raised as to how productive is NMHC composition is to the photochemical production of the surface ozone. A rough estimate shows that the total reactivity of the Taipei NMHC composition is about 1.21 × 10^?9 cm³ s^?1 which is 1.6 times that of the Los Angeles (LA) NMHC composition, while the simulated noon peak will be different by 28 ppbv, i.e. 18% more than that simulated with a LA composition.

Meanwhile, high aerosol loading is a serious problem in Taipei. the attenuation of the UV radiation by aerosols cannot be ignored. A numerical simulation shows that the noon ozone level will decrease from 178 to 141ppbv, i. e. about 21% reduction, with deterioration of the visual range from 85 to 5 km.

In the southern Taiwan, industry parks are mixed with the populated Kaohsiung city, hence the large emission of NO _x from high chimneys cannot be ignored. in this study, NO _x is assumed to be emitted in the layer between 235–460 m high with an emission rate of 0.05 or 0.145 ppbv/sec. the results show that the NO _x emitted from the elevated stack lead to a considerable reduction of surface ozone. Such conclusion is obtained due to the fact that a one-dimensional model is used in this paper. Whereas, if a three-dimensional regional model was used, then a higher productivity of ozone downstream would be simulated.     

Characteristics of mass distributions of aerosol particle and its inorganic water-soluble ions in summer over a suburb farmland in Beijing

Agricultural activity is one of the most important sources of aerosol particles. To understand the mass distribution and sources of aerosol particles and their inorganic water-soluble ions in a suburb farmland of Beijing, particle samples were collected using a microorifice uniform deposit impactor (MOUDI) in the summer of 2004 in a suburb vegetable field. The distribution of the particles and their inorganic water-soluble ions in the diameter range of 0.18–18 μm were measured. The dominant fine particle ions were SO₄ ^2?, NO₃ ^?, and NH₄ ⁺. The association of day-to-day variation of the concentration of these ions with temperature, humidity, and solar radiation suggested that they are formed by the reaction of NH₃ released from the vegetable field with the acid species produced from photochemical reactions. Fine particle K⁺ is likely from vegetation emission and biomass burning. Coarse particles like Ca²⁺, Mg²⁺, NO₃ ^?, and SO₄ ^2? are suggested to come from the mechanical process by which the soil particle entered the atmosphere, and from the reaction of the acid species at the surface of the soil particle. The results show that fertilizer and soil are important factors determining the aerosol particle over agricultural fields, and vegetable fields in suburban Beijing contribute significantly to the aerosol particle.     

Selective catalytic reduction of NO x from exhaust of lean-burn engine over Ag-Al2O3/cordierite catalyst

A highly effective Ag-Al₂O₃ catalyst was prepared using the in-situ sol-gel method, and characterized by surface area using nitrogen adsorption, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) techniques. The catalyst performance was tested on a real lean-burn gasoline engine. Only unburned hydrocarbons and carbon monoxide in the exhaust were directly used as reductant (without any external reductant), the maximum NO _x conversion could only reach 40% at 450°C. When an external reductant, ethanol was added, the average NO _x conversion was greater than 60%. At exhaust gas temperature range of 350–500°C, the maximum NO _x conversion reached about 90%. CO and HC could be efficiently oxidized with Pt-Al₂O₃ oxidation catalyst placed at the end of SCR converter. However, NO _x conversion drastically decreased because of the oxidation of some intermediates to NO _x again. The possible reaction mechanism was proposed as two typical processes, nitration, and reduction in HC-SCR over Ag-Al₂O₃.     

Secondary aerosol formation in winter haze over the Beijing-Tianjin-Hebei Region,China

• Characteristics and interannual variation of aerosol pollution are illustrated. • Mechanisms of secondary aerosol formation in winter haze of North China are reviewed. • Directions in future studies of secondary aerosol formation are provided. Severe haze pollution occurs frequently in the winter over the Beijing-Tianjin-Hebei (BTH) region (China), exerting profound impacts on air quality, visibility, and human health. The Chinese Government has taken strict mitigation actions since 2013 and has achieved a significant reduction in the annual mean PM_2.5 concentration over this region. However, the level of secondary aerosols during heavy haze episodes showed little decrease during this period. During heavy haze episodes, the concentrations of secondary aerosol components, including sulfate, nitrate and secondary organics, in aerosol particles increase sharply, acting as the main contributors to aerosol pollution. To achieve effective control of particle pollution in the BTH region, the precise and complete secondary aerosol formation mechanisms have been investigated, and advances have been made about the mechanisms of gas phase reaction, nucleation and heterogeneous reactions in forming secondary aerosols. This paper reviews the research progress in aerosol chemistry during haze pollution episodes in the BTH region, lays out the challenges in haze formation studies, and provides implications and directions for future research.     

Permitted emissions of major air pollutants from coal-fired power plants in China based on best available control technology

Based on the activity level and technical information of coal-fired power-generating units (CFPGU) obtained in China from 2011 to 2015, we, 1) analyzed the time and spatial distribution of SO₂ and NO_x emission performance of CFPGUs in China; 2) studied the impact of installed capacity, sulfur content of coal combustion, and unit operation starting time on CFPGUs’ pollutant emission performance; and 3) proposed the SO₂ and NO_x emission performance standards for coal-fired power plants based on the best available control technology. Our results show that: 1) the larger the capacity of a CFPGU, the higher the control level and the faster the improvement; 2) the CFPGUs in the developed eastern regions had significantly lower SO₂ and NO_x emission performance values than those in other provinces due to better economic and technological development and higher environmental management levels; 3) the SO₂ and NO_x emission performance of the Chinese thermal power industry was significantly affected by the single-unit capacity, coal sulfur content, and unit operation starting time; and 4) based on the achievability analysis of best available pollution control technology, we believe that the CFPGUs’ SO₂ emission performance reference values should be 0.34 g/kWh for active units in general areas, 0.8 g/kWh for active units in high-sulfur coal areas, and 0.13 g/kWh for newly built units and active units in key areas. In addition, the NO_x emission performance reference values should be 0.35 g/kWh for active units in general areas and 0.175 g/kWh for new units and active units in key areas.

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Photochemical indicators of ozone sensitivity: application in the Pearl River Delta,China

Surface O₃ production has a highly nonlinear relationship with its precursors. The spatial and temporal heterogeneity of O₃-NO _x -VOC-sensitivity regimes complicates the control-decision making. In this paper, the indicator method was used to establish the relationship between O₃ sensitivity and assessment indicators. Six popular ratios indicating ozone-precursor sensitivity, HCHO/NO _y , H₂O₂/ HNO₃, O₃/NO _y , O₃/NO _z , O₃/HNO₃, and H₂O₂/NO _z , were evaluated based on the distribution of NO_x- and VOC-sensitive regimes. WRF-Chem was used to study a serious ozone episode in fall over the Pearl River Delta (PRD). It was found that the south-west of the PRD is characterized by a VOCsensitive regime, while its north-east is NO _x -sensitive, with a sharp transition area between the two regimes. All indicators produced good representations of the elevated ozone hours in the episode on 6 November 2009, with H₂O₂/HNO₃ being the best indicator. The threshold sensitivity levels for HCHO/NO_y, H₂O₂/HNO₃, O₃/NO _y , O₃/NO _z , O₃/HNO₃, and H₂O₂/NO _z were estimated to be 0.41, 0.55, 10.2, 14.0, 19.1, and 0.38, respectively. Threshold intervals for the indicators H₂O₂/HNO₃, O₃/NO _y , O₃/NO _z , O₃/HNO₃, and H₂O₂/NO _z were able to identify more than 95% of VOC- and NO _x -sensitive grids. The ozone episode on 16 November 16 2008 was used to independently verify the results, and it was found that only H₂O₂/HNO₃ and H₂O₂/NO _z were able to differentiate the ozone sensitivity regime well. Hence, these two ratios are suggested as the most appropriate indicators for identifying fall ozone sensitivity in the PRD. Since the species used for indicators have seasonal variation, the utility of those indicators for other seasons should be investigated in the future work.

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Modelling concentrations of airborne primary and secondary PM10 and PM2.5 with the BelEUROS-model in Belgium

The Eulerian Chemistry-Transport Model BelEUROS was used to calculate the concentrations of airborne PM₁₀ and PM_2.5 over Europe. Both primary as well as secondary particulate matter in the respirable size-range was taken into account. Especially PM_2.5 aerosols are often formed in the atmosphere from gaseous precursor compounds. Comprehensive computer codes for the calculation of gas phase chemical reactions and thermodynamic equilibria between compounds in the gas-phase and the particulate phase had been implemented into the BelEUROS-model. Calculated concentrations of PM₁₀ and PM_2.5 are compared to observations, including both the spatial and daily, temporal distribution of particulate matter in Belgium for certain monitoring locations and periods. The concentrations of the secondary compounds ammonium, nitrate and sulfate have also been compared to observed values. BelEUROS was found to reproduce the observed concentrations rather well. The model was applied to assess the contribution of emissions derived from the sector agriculture in Flanders, the northern part of Belgium, to PM₁₀- and PM_2.5-concentrations. The results demonstrate the importance of ammonia emissions in the formation of secondary particulate matter. Hence, future European emission abatement policy should consider more the role of ammonia in the formation of secondary particles.     

A chemical mechanism for dry deposition—the role of biogenic hydrocarbon (Terpene) emissions in the dry deposition of O3, SO2 and NOx in forest areas

Terpenes react quite rapidly with ambient ozone and lead via ozonides to highly oxidizing radicals and consecutive products forming aerosols. In the presence of SO₂ sulphur containing compounds, mainly as sulphate, are formed. By means of gas chromatography/mass spectrometry and by comparison with known spectra the main products of the reaction of ß‐pinene (as a model compound) with ozone and sulphur dioxide could be identified.

Reaction of terpenes with NO₃‐radicals, which build up in the atmosphere at night‐time, leads to the formation of organic nitrates that form aerosols. The kinetics as well as the products of the reaction between NO₃‐radicals and ß‐pinene have been studied by FTIR and MS.     

细颗粒物(PM_(2.5))主要组分模拟溶液对发光细菌的光抑制分析

为明确NH_4~+、 NO_3~-、SO_4~(2-)及金属等组分在水溶性提取液对发光细菌的光抑制过程中所起的作用,参照PM_(2.5)样品提取液浓度,模拟配制与3级以上PM_(2.5)样品提取液中主要组分:硫酸盐、硝酸盐、氨盐相同浓度的溶液,同时选取与PM_(2.5)可溶性提取液发光抑制率相关性较强的铅、锌,配制不同浓度级别模拟溶液,测试各单一组分对发光细菌的发光抑制率及其混合溶液对发光细菌的联合影响效应。基于毒性单位法(TU)、相加指数法(AI)和混合毒性指数法(MTI)评价了混合体系联合影响的作用类型。结果表明,与3~6级PM_(2.5)可溶性提取液中硫酸氨、硫酸氢氨、硝酸氨、硫酸锌和硝酸铅浓度相同的模拟溶液对发光细菌的发光没有抑制作用。不同的评价方法对PM_(2.5)主要组分混合体系联合效应评价结果具有较好的一致性,硫酸氨、硝酸氨、硫酸氢氨混合溶液中,对发光细菌的光抑制均为硫酸氢氨的独立作用,硫酸锌与硝酸铅的混合体系,锌和铅对发光细菌的联合影响效应表现为协同,硫酸氨、硝酸氨、硫酸氢氨与硫酸锌、硝酸铅的多元混合体系呈现协同作用。     

Improving simulations of sulfate aerosols during winter haze over Northern China: the impacts of heterogeneous oxidation by NO<Subscript>2</Subscript>

We implemented the online coupled WRF-Chem model to reproduce the 2013 January haze event in North China, and evaluated simulated meteorological and chemical fields using multiple observations. The comparisons suggest that temperature and relative humidity (RH) were simulated well (mean biases are–0.2K and 2.7%, respectively), but wind speeds were overestimated (mean bias is 0.5 m?s^–1). At the Beijing station, sulfur dioxide (SO₂) concentrations were overpredicted and sulfate concentrations were largely underpredicted, which may result from uncertainties in SO₂ emissions and missing heterogeneous oxidation in current model. We conducted three parallel experiments to examine the impacts of doubling SO₂ emissions and incorporating heterogeneous oxidation of dissolved SO₂ by nitrogen dioxide (NO₂) on sulfate formation during winter haze. The results suggest that doubling SO₂ emissions do not significantly affect sulfate concentrations, but adding heterogeneous oxidation of dissolved SO₂ by NO₂ substantially improve simulations of sulfate and other inorganic aerosols. Although the enhanced SO₂ to sulfate conversion in the HetS (heterogeneous oxidation by NO₂) case reduces SO₂ concentrations, it is still largely overestimated by the model, indicating the overestimations of SO₂ concentrations in the North China Plain (NCP) are mostly due to errors in SO₂ emission inventory.

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Primary NO2 emissions and their impact on air quality in traffic environments in Germany

Background

The decreasing NO_X concentrations at urban measurement stations in Germany are in agreement with the reduction of NO_X emissions from vehicular traffic. However, the measured NO₂ concentrations are stagnating nationwide. In 2010, at more than the half of the urban measurement stations in Germany, annual mean values for NO₂ exceeded the new Europe-wide limit value of 40 μg/m³ (20 ppbv) NO₂. Similar findings are reported from many other member states of the European Union.

Results

The observed trend of the airborne NO₂ concentrations has different reasons. Firstly, the NO₂/NO_x emission ratio has increased significantly during the last two decades. Furthermore, secondary NO₂, caused by the titration reactions of NO with ozone (O₃) and peroxy radicals (RO₂), is responsible for the major fraction (approximately 70%) of the measured NO₂. However, secondary NO₂ shows a highly nonlinear dependency on NO_x and thus, is decreasing much more slowly than expected from the decreasing NO_x levels. Based on the results from the present study, the increased NO₂/NO_X emission ratio can only explain a minor fraction of the observed high airborne NO₂ concentration in the city center.

Conclusions

A further reduction of primary NO₂ emissions, due to improved exhaust gas treatment, will not have a strong influence on urban NO₂ levels, and a further significant reduction of the NO_X emissions, in particular from vehicular traffic, is necessary in order to meet the annual mean limit value for NO₂ of about 20 ppb in the future.     

Synergistic effects of salinity,temperature and heavy metals on mortality and osmoregulation in marine and estuarine isopods (Crustacea)

The effects of cadmium (3CdSO₄·8H₂O), zinc (ZnSO₄·7H₂O) and lead [Pb (NO₃)₂] on mortality, and cadmium, zinc and mercury (HgCl₂) on osmoregulation, have been recorded for marine and estuarine species of isopods (Crustacea). The marine species studied were Idotea baltica, I. neglecta, I. emarginata and Eurydice pulchra, which were adapted to 100, 80, 60 and 40% sea water (SW) (100% SW э 34‰ S). The estuarine species used were Jaera albifrons sensu stricto and J. nordmanni, which were adapted to 100, 50, 10 and 1% SW. Both groups of isopods have low mortalities in 100% SW with 10 and 20 ppm of cadmium, zinc and lead, but a decrease in salinity caused an increase in the toxicities of these metals and reduced the LT₅₀ values (time, in hours, to 50% mortality). Mortalities at 10°C were generally higher than those recorded at 5°C. Cadmium had no significant effect on the osmoregulation of I. baltica and I. emarginata in 100 and 80% SW at 5°C, but this metal significantly lowered the blood osmotic concentration of I. neglecta in 80% SW. Zinc did not alter the haemolymph osmotic concentration of I. neglecta in 100 and 80% SW, but significantly lowered the blood osmotic concentration of I. baltica in 100% SW. Cadmium, zinc and mercury also significantly altered the osmoregulatory ability of J. albifrons in dilute saline.     

The effect of preparation conditions of Pt/Al2O3 on its catalytic performance for the H2-SCR in the presence of oxygen

Selective catalytic reduction of NO _x by H₂ in the presence of oxygen has been investigated over Pt/ Al₂O₃ catalysts pre-treated under different conditions. Catalyst preparation conditions exert significant influence on the catalytic performance, and the catalyst pre-treated by H₂ or H₂ then followed by O₂ is much more active than that pre-treated by air. The higher surface area and the presence of metallic Pt over Pt/Al₂O₃ pre-treated by H₂ or pretreated by H₂ then followed by O₂ can contribute to the formation of NO₂, which then promotes the reaction to proceed at low temperatures.     

Aerogels and metal–organic frameworks for environmental remediation and energy production

Environmental pollution and climate change are requiring new methods to clean pollutants and produce sustainable energy. Aerogels and metal organic frameworks are emerging as advanced porous materials with higher functionality, high surface area, high porosity and flexible chemistry. Aerogels are dried gels prepared using the sol–gel procedure, whereas metal organic frameworks are networks of organic ligands and metal ions connected by coordination bonds. Applications of aerogels include the removal of heavy metals, CO₂ capture and reduction, photodegradation of pollutants, air cleanup and water splitting. This article reviews the synthesis and types of aerogels and metal organic frameworks, and the application to pollutant removal, energy production including hydrogen, methane reforming, CO₂ conversion and NOx removal.     

The impact on tropospheric ozone formation on the implementation of a program for mobile emissions control: a case study in São Paulo,Brazil

The main sources of reactive hydrocarbons (RHC) and nitrogen oxides (NO_x), ozone precursors, in the Metropolitan Area of São Paulo (MASP) in the southeast of Brazil are emissions from vehicles fleets. Ambient surface ozone and particulate matter concentrations are air quality problem in the MASP. This study examined the impact that implementing a control program for mobile emissions has on ozone concentrations, An episode of high surface ozone concentrations occurring in the MASP during the March 13–15, 2000 period was used as a case study that was modeled for photochemical oxidants using the California Institute of Technology/Carnegie Mellon University three-dimensional photochemical model. Different scenarios were analyzed in relationship to the implementation of the Programa Nacional de Controle de Poluição por Veículos Automotores (PROCONVE, National Program to Control Motor Vehicle Pollution). Scenario 1 assumed that all vehicles were operating within PROCONVE guidelines. Scenarios 2 and 3 considered hypothetical situations in which the PROCONVE was not implemented. Scenario 2 set the premise that vehicles were using pre-1989 technology, whereas scenario 3 allowed for technological advances. A base case scenario, in which the official emission inventory for the year 2000 was employed, was also analyzed. The CIT model results show agreement with most measurements collected during 13–15 March 2000 modeling episode. Mean normalized bias for ozone, CO, RHC and NO _x are approximately 9.0, 6.0, ?8.3, 13.0%, respectively. Tropospheric ozone concentrations predicted for scenario 2 were higher than those predicted for scenarios 1, 3 and base case. This study makes a significant contribution to the evaluation of air quality improvement and provides data for use in evaluating the economic costs of implementing a program of motor vehicle pollution control aimed at protecting human health.     

Environmental modeling of uranium interstitial compositions of non-stoichiometric oxides: experimental and theoretical analysis

Study of uranium interstitial compositions of non-stoichiometric oxides UO_2+x (x ∈ 0.1–0.02) in gas and condense phases has been presented, using various soft-ionization mass spectrometric methods such as ESI-, APCI-, and MALDI-MS at a wide dynamic temperature gradient (∈ 25–300 °C). Linearly polarized vibrational spectroscopy has been utilized in order to assign unambiguously, the vibrational frequencies of uranium non-stoichiometric oxides. Experimental design has involved xUO_2.66·yUO_2.33, xUO_2.66·yUO_2.33/SiO₂, xUO_2.66·yUO_2.33/SiO₂ (NaOH) and SiO₂/x′NaOH·y′UO₂(NO₃)₂·6H₂O, multicomponent systems (x = 1, y ∈ 0.1–1.0 and x′ = 1, y′ ∈ 0.1–0.6) as well as phase transitions UO₂(NO₃)₂·6H₂O → {U₄O₉(UO_2.25)} → U₃O₇(UO_2.33) → U₃O₈(UO_2.66) → {UO₃}, thus ensuring a maximal representativeness to real environmental conditions, where diverse chemical, geochemical and biochemical reactions, including complexation and sorption onto minerals have occurred. Experimental factors such as UV-irradiation, pH, temperature, concentration levels, solvent types and ion strength have been taken into consideration, too. As far as uranium speciation represents a challenging analytical task in terms of chemical identification diverse coordination species, mechanistic aspects relating incorporation of oxygen into UO _2+x form the shown full methods validation significantly impacts the field of environmental radioanalytical chemistry. UO₂ is the most commonly used fuel in nuclear reactors around the globe; however, a large non-stoichiometric range ∈ UO_1.65–UO_2.25 has occurred due to radiolysis of water on UO₂ surface yielding to H₂O₂, OH^·, and more. Each of those compositions has different oxygen diffusion. And in this respect enormous effort has been concentrated to study the potential impact of hazardous radionuclide on the environment, encompassing from the reprocessing to the disposal stages of the fuel waste, including the waste itself, the processes in the waste containers, the clay around the containers, and geological processes. In a broader sense, thereby, this study contributes to field of environmental analysis highlighting the great ability of various soft-ionization MS methods, particularly, MALDI-MS one, for direct assay of complex multicomponent heterogeneous mixtures at fmol–attomol concentration ranges, along with it the great instrumental features allowing, not only meaningful quantitative, but also structural information of the analytes, thus making the method indispensable for environmental speciation of radionuclides, generally.     

Chemical deactivation of V2O5-WO3/TiO2 SCR catalyst by combined effect of potassium and chloride

V₂O₅-WO₃/TiO₂ catalyst was poisoned by impregnation with NH₄Cl, KOH and KCl solution, respectively. The catalysts were characterized by X-ray diffraction (XRD), inductively coupled plasma (ICP), N₂ physisorption, Raman, UV-vis, NH₃ adsorption, temperature-programmed reduction of hydrogen (H₂-TPR), temperature-programmed oxidation of ammonia (NH₃-TPO) and selective catalytic reduction of NO _x with ammonia (NH₃-SCR). The deactivation effects of poisoning agents follow the sequence of KCl>KOH?NH₄Cl. The addition of ammonia chloride enlarges the pore size of the titania support, and promotes the formation of highly dispersed V = O vanadyl which improves the oxidation of ammonia and the high-temperature SCR activity. K⁺ ions are suggested to interact with vanadium and tungsten species chemically, resulting in a poor redox property of catalyst. More importantly, potassium can reduce the Brønsted acidity of catalysts and decrease the stability of Brønsted acid sites significantly. The more severe deactivation of the KCl-treated catalyst can be mainly ascribed to the higher amount of potassium resided on catalyst.     

Bewertung der Umwelteffizienz moderner Autoantriebe – auf dem Weg vom Diesel-Pkw-Boom zu Elektroautos

Motorized traffic is among the biggest CO₂-emitting sources and is additionally dominating NO_x emission. Engine technology shifts are approaching, while automobiles developed in Germany and Europe are exported worldwide together with the European emission thresholds for cars. The Diesel car boom induced by EU commission, national EU governments and car industry is accordingly analyzed for sustainability and its effects on environment. German CO₂ emission reduction numbers by motorized traffic, as claimed by the government, are questioned. Radiative forcing by soot (black carbon) Diesel car emissions is added on the CO₂ emissions by fuel combustion. Diesel cars without particle filters are found to cause an atmospheric warming. Modelled and measured NO_x emission data are assessed to mismatch considerably. In spite of an ambitious national NO_x reduction plan there is excess NO_x emission by the German and European Diesel car boom. In this context environmental sustainability of battery electric vehicles (BEV) is investigated. Direct (by car) und indirect (by power plant) emissions (CO₂, NO_x, PM₁₀, SO₂) of cars with internal combustion engines (ICE) and BEVs, respectively, are calculated and compared. CO₂-ecoanalysis revealed advantages for BEVs even operated with current German electricity mix based on around 15?% renewable sources.     

Sensitivity of air quality model prediction to parameterization of vertical eddy diffusivity

This paper investigates the effects of vertical eddy diffusivities derived from the 3 different planetary boundary layer (PBL) schemes on predictions of chemical components in the troposphere of East Asia. Three PBL schemes were incorporated into a regional air quality model (RAQM) to represent vertical mixing process and sensitivity simulations were conducted with the three schemes while other options are identical. At altitudes <2km, all schemes exhibit similar skill for predicting SO₂ and O₃, but more difference in the predicted NO_x concentration. The Gayno–Seaman scheme produces the smallest vertical eddy diffusivity (Kz) among all schemes, leading to higher SO₂ and NO_x concentrations near the surface than that from the other 2 schemes. However, the effect of vertical mixing on O₃ concentration is complex and varies spatially due to chemistry. The Gayno–Seaman scheme predicts lower O₃ concentrations than the other two schemes in the parts of northern China (generally VOC-limited) and higher ones in most parts of southern China (NO_x-limited). The Byun and Dennis scheme produces the largest mixing depth in the daytime, which bring more NO_x into upper levels, and the mixing depth predicted by the Gayno–Seaman scheme is the smallest, leading to higher NO_x and lower O₃ concentrations near the surface over intensive emission regions.     

Promotion of transition metal oxides on the NH<Subscript>3</Subscript>-SCR performance of ZrO<Subscript>2</Subscript>-CeO<Subscript>2</Subscript> catalyst

Chromium oxide and manganese oxide promoted ZrO₂-CeO₂ catalysts were prepared by a homogeneous precipitation method for the selective catalytic reduction of NO _x with NH₃. A series of characterization including X-ray diffraction (XRD), high-resolution transmission electron microscope (HR-TEM), Brunauer–Emmett–Teller (BET) surface area analysis, H₂ temperatureprogrammed reduction (H₂-TPR), and X-ray photoelectron spectroscopy (XPS) were used to evaluate the influence of the physicochemical properties on NH₃-SCR activity. Cr-Zr-Ce and Mn-Zr-Ce catalysts are much more active than ZrO₂-CeO₂ binary oxide for the low temperature NH₃-SCR, mainly because of the high specific surface area, more surface oxygen species, improved reducibility derived from synergistic effect among different elements. Mn-Zr-Ce catalyst exhibited high tolerance to SO₂ and H₂O. Cr-Zr-Ce mixed oxide exhibited>80% NO _x conversion at a wide temperature window of 100°C–300°C. In situ DRIFT studies showed that the addition of Cr is beneficial to the formation of Bronsted acid sites and prevents the formation of stable nitrate species because of the presence of Cr^{6 +}. The present mixed oxide can be a candidate for the low temperature abatement of NO _x .

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