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.     

Recent advances in special morphologic photocatalysts for NOx removal

● Systematic information of recent progress in photocatalytic NO _x removal is provided. ● The photocatalysts with special morphologies are reviewed and discussed. ● The morphology and photocatalytic NO _x removal performance is related. The significant increase of NO_x concentration causes severe damages to environment and human health. Light-driven photocatalytic technique affords an ideal solution for the removal of NO_x at ambient conditions. To enhance the performance of NO_x removal, 1D, 2D and 3D photocatalysts have been constructed as the light absorption and the separation of charge carriers can be manipulated through controlling the morphology of the photocatalyst. Related works mainly focused on the construction and modification of special morphologic photocatalyst, including element doping, heterostructure constructing, crystal facet exposing, defect sites introducing and so on. Moreover, the excellent performance of the photocatalytic NO_x removal creates great awareness of the application, which has promising practical applications in NO_x removal by paint (removing NO_x indoor and outdoor) and pavement (degrading vehicle exhausts). For these considerations, recent advances in special morphologic photocatalysts for NO_x removal was summarized and commented in this review. The purpose is to provide insights into understanding the relationship between morphology and photocatalytic performance, meanwhile, to promote the application of photocatalytic technology in NO_x degradation.     

Precise regulation of acid pretreatment for red mud SCR catalyst: Targeting on optimizing the acidity and reducibility

• The optimum SCR activity was realized by tuning the acid pretreatment. • Optimized catalysts showed NO_x conversion above 90%. • The NH₃ and NO adsorption capacity of Al-O₃-Fe is stronger than Fe-O₃-Fe. • The formation of almandine consumes Fe³⁺ and Al³⁺ and weakens their interaction. Red mud (RM), as an alkaline waste, was recently proved to be a promising substitute for the SCR catalyst. Dealkalization could improve the acidity and reducibility of red mud, which were critical for SCR reaction. However, the dealkalization effect depended on the reaction between acid solution and red mud. In this study, we realized the directional control of the chemical state of active sites through tuning the acid pretreatment (dealkalization) process. The pretreatment endpoint was controlled at pH values of 3–5 with diluted nitric acid. When the pH values of red mud were 3 and 5 (CRM-3 and CRM-5), activated catalysts showed NO_x conversion above 90% at 275°C–475°C. The high initial reaction rate, Ce³⁺/(Ce³⁺ + Ce⁴⁺) ratio, and surface acidity accounted for the excellent SCR performance of CRM-5 catalyst. Meanwhile, more Fe³⁺ on the CRM-3 surface improved the NH₃ adsorption. There was a strong interaction between Al and Fe in both CRM-5 and CRM-3 catalysts. DFT results showed that the adsorption capacity of the Al-O₃-Fe for NH₃ and NO is stronger than that of Fe-O₃-Fe, which enhanced the NO_x conversion of the catalyst. However, the almandine was formed in CRM-4, consumed part of Fe³⁺ and Al³⁺, and the interaction between Al and Fe was weakened. Also, deposited almandine on the catalyst surface covered the active sites, thus leading to lower NH₃-SCR activity.     

In situ electron-induced reduction of NOx via CNTs activated by DBD at low temperature

• An in situ electron-induced deNO_x process with CNT activated by DBD was achieved. • Carbon atoms on CNT surface were verified to be excited by plasma in DBD-CNT system. • Reactions between NO_x and excited C result in synergistic effect of DBD-CNT system. In this study, a new in situ electron-induced process is presented with carbon nanotubes (CNTs) as a reduction agent activated by dielectric barrier discharge (DBD) for nitrogen oxide (NO_x) abatement at low temperature (<407 K). Compared with a single DBD system and a DBD system with activated carbon (DBD-AC), a DBD system with carbon nanotubes (DBD-CNT) showed a significant promotion of NO_x removal efficiency and N₂ selectivity. Although the O₂ content was 10%, the NO_x conversion and N₂ selectivity in the DBD-CNT system still reached 64.9% and 81.9% at a specific input energy (SIE) of 1424 J/L, and these values decreased to 16.8%, 31.9% and 43.2%, 62.3% in the single DBD system and the DBD-AC system, respectively. X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were utilized to investigate surface changes in the CNTs after activation by DBD to explore the NO_x reduction abatement mechanism of this new process. Furthermore, the outlet gas components were also observed via Fourier transform infrared spectroscopy (FTIR) to help reveal the NO_x reduction mechanism. Experimental results verified that carbon atoms excited by DBD and the structure of CNTs contributed to the synergistic activity of the DBD-CNT system. The new deNO_x process was accomplished through in situ heterogenetic reduction reactions between the NO_x and carbon atoms activated by the plasma on the CNTs. In addition, further results indicated that the new deNO_x process exhibited acceptable SO₂ tolerance and water resistance.     

Enhancement of the polynomial functions response surface model for real-time analyzing ozone sensitivity

• The calculation process and algorithm of response surface model (RSM) were enhanced. • The prediction errors of RSM in the margin and transition areas were greatly reduced. • The enhanced RSM was able to analyze O₃-NO_x-VOC sensitivity in real-time. • The O₃ formations were mainly sensitive to VOC, for the two case study regions. Quantification of the nonlinearities between ambient ozone (O₃) and the emissions of nitrogen oxides (NO_x) and volatile organic compound (VOC) is a prerequisite for an effective O₃ control strategy. An Enhanced polynomial functions Response Surface Model (Epf-RSM) with the capability to analyze O₃-NO_x-VOC sensitivities in real time was developed by integrating the hill-climbing adaptive method into the optimized Extended Response Surface Model (ERSM) system. The Epf-RSM could single out the best suited polynomial function for each grid cell to quantify the responses of O₃ concentrations to precursor emission changes. Several comparisons between Epf-RSM and pf-ERSM (polynomial functions based ERSM) were performed using out-of-sample validation, together with comparisons of the spatial distribution and the Empirical Kinetic Modeling Approach diagrams. The comparison results showed that Epf-RSM effectively addressed the drawbacks of pf-ERSM with respect to over-fitting in the margin areas and high biases in the transition areas. The O₃ concentrations predicted by Epf-RSM agreed well with Community Multi-scale Air Quality simulation results. The case study results in the Pearl River Delta and the north-western area of the Shandong province indicated that the O₃ formations in the central areas of both the regions were more sensitive to anthropogenic VOC in January, April, and October, while more NO_x-sensitive in July.     

CeO2 doping boosted low-temperature NH3-SCR activity of FeTiOx catalyst: A microstructure analysis and reaction mechanistic study

• CeO₂ doping significantly improved low-temperature NH₃-SCR activity on FeTiO_x. • The crystallinity of FeTiO_x was decreased dramatically after CeO₂ doping. • Unique Ce-O-Fe structure in FeCe_0.2TiO_x accounted for its superior redox property. • Facile activation of NH₃ to-NH₂ on FeCe_0.2TiO_x promoted the DeNO_x efficiency. FeTiO_x has been recognized as an environmental-friendly and cost-effective catalyst for selective catalytic reduction (SCR) of NO_x with NH₃. Aimed at further improving the low-temperature DeNO_x efficiency of FeTiO_x catalyst, a simple strategy of CeO₂ doping was proposed. The low-temperature (<250℃) NH₃-SCR activity of FeTiO_x catalyst could be dramatically enhanced by CeO₂ doping, and the optimal composition of the catalyst was confirmed as FeCe_0.2TiO_x, which performed a NO_x conversion of 90% at ca. 200℃. According to X-ray diffraction (XRD), Raman spectra and X-ray absorption fine structure spectroscopy (XAFS) analysis, FeCe_0.2TiO_x showed low crystallinity, with Fe and Ce species well mixed with each other. Based on the fitting results of extended X-ray absorption fine structure (EXAFS), a unique Ce-O-Fe structure was formed in FeCe_0.2TiO_x catalyst. The well improved specific surface area and the newly formed Ce-O-Fe structure dramatically contributed to the improvement of the redox property of FeCe_0.2TiO_x catalyst, which was well confirmed by H₂-temperature-programmed reduction (H₂-TPR) and in situ XAFS experiments. Such enhanced redox capability could benefit the activation of NO and NH₃ at low temperatures for NO_x removal. The detailed reaction mechanism study further suggested that the facile oxidative dehydrogenation of NH₃ to highly reactive-NH₂ played a key role in enhancing the low-temperature NH₃-SCR performance of FeCe_0.2TiO_x catalyst.     

Impacts of emissions and meteorological changes on China’s ozone pollution in the warm seasons of 2013 and 2017

O₃ increment is mainly caused by changes in meteorology rather than emissions. Emission reduction is effective to reduce O₃ nationwide, especially in summer. Strengthened NO_x controls are necessary to meet the ambient O₃ standard. We have quantified the impacts of anthropogenic emissions reductions caused by the Air Pollution Control Action Plan and changes in meteorological fields between 2013 and 2017 on the warm-season O₃ concentration in China using a regional 3D chemical transport model. We found that the impact on daily maximum eight-hour (MDA8) O₃ concentration by the meteorological variation that mostly increased O₃ was greater than that from emission reduction, which decreased O₃. Specifically, the control measures implemented since 2013 in China have reduced SO₂, NO_x, PM_2.5, and VOC emissions by 33%, 25%, 30%, and 4% in 2017, while NH₃ emissions have increased by 7%. The changes in anthropogenic emissions lowered MDA8 O₃ by 0.4–3.7 ppb (0.8%–7.6%, varying by region and month), although MDA8 O₃ was increased slightly in some urban areas (i.e. North China) at the beginning/end of warm seasons. Relative to 2013, the average 2 m temperature in 2017 shows increments in North, North-east, East, and South China (0.34℃–0.83℃) and decreases in Central China (0.24℃). The average solar radiation shows increments in North, North-east, and South China (7.0–9.7 w/m²) and decreases in Central, South-west, and North-west China (4.7–10.3 w/m²). The meteorological differences significantly change MDA8 O₃ by -3.5–8.5 ppb (-8.2%–18.8%) with large temporal variations. The average MDA8 O₃ was slightly increased in North, North-east, East, and South China. The response surface model suggests that the O₃ formation regime transfers from NO_x-saturated in April to NO_x-limited in July on average in China.     

Homogeneous and heterogeneous photolysis of nitrate in the atmosphere: state of the science,current research needs,and future prospects

● Recent advances in the photolysis of nitrate/HNO₃ are reviewed. ● Mechanisms and key factors affecting the photolysis of nitrate/HNO₃ are summarized. ● Atmospheric implications and future research recommendations are provided. Nitrate is an important component of atmospheric particulate matter and affects air quality, climate, human health, and the ecosystem. Nitrate was previously considered a permanent sink for nitrogen oxides (NO_x). However, this viewpoint has been challenged in recent years because growing research evidence has shown the transformation of nitrate into NO_x (i.e., renoxification). The photolysis of nitrate/HNO₃, especially in the particulate phase or adsorbed on particles, can be a significant renoxification process in the atmosphere. The formation and photolysis of nitrate in aerosol not only change the diurnal variation of NO_x, but also provide long-distance transport of NO_x in the form of nitrate, which affects local and regional atmospheric chemistry and air quality. This review summarizes recent advances in the fundamental understanding of the photolysis of nitrate/HNO₃ under various atmospheric conditions, with a focus on mechanisms and key factors affecting the process. The atmospheric implications are discussed and future research is recommended.     

PM-support interfacial effect and oxygen mobility in Pt,Pd or Rh-loaded (Ce,Zr,La)O2 catalysts

• Pt/CZL exhibits the optimum catalytic performance for HC and NO_x elimination. • The strong PM-Ce interaction favors the oxygen mobility and DOSC. • Pd/CZL shows higher catalytic activity for CO conversion due to more O_latt species. • Great oxygen mobility at high temperature broadens the dynamic operation window. • The relationship between DOSC and catalytic performance is revealed. The physicochemical properties of Pt-, Pd- and Rh- loaded (Ce,Zr,La)O₂ (shorted for CZL) catalysts before/after aging treatment were systematically characterized by various techniques to illustrate the relationship of the dynamic oxygen storage/release capacity and redox ability with their catalytic performances for HC, NO_x and CO conversions. Pt/CZL catalyst exhibits the optimum catalytic performance for HC and NO_x elimination, which mainly contribute to its excellent redox ability and dynamic oxygen storage/release capacity (DOSC) at lower temperature due to the stronger PM (precious metals)-support interaction. However, the worse stability of Pt-O-Ce species and volatile Pt oxides easily result in the dramatical decline in catalytic activity after aging. Pd/CZL shows higher catalytic activity for CO conversion by reason of more O_latt species as the active oxygen for CO oxidation reaction. Rh/CZL catalyst displays the widest dynamic operation window for NO_x elimination as a result of greater oxygen mobility at high temperature, and the ability to retain more Rh-O-Ce species after calcined at 1100°C effectively restrains sintering of active RhO_x species, improving the thermal stability of Rh/CZL catalyst.     

Tailoring the simultaneous abatement of methanol and NOx on Sb-Ce-Zr catalysts via copper modification

● Cu addition enhances CH₃OH oxidation and alleviates its inhibitory effect on SCR. ● Cu addition improves the activation of SCR reactants in the presence of methanol. ● Damaged structure by more Cu addition decreases specific surface area and acidity. ● Excessive Cu addition would lead to the narrowing of SCR temperature window. Simultaneously removal of NO_x and VOCs over NH₃-SCR catalysts have attracted lots of attention recently. However, the presence of VOCs would have negative effect on deNO_x efficiency especially at low temperature. In this study, copper modification onto Sb_0.5CeZr₂O_x (SCZ) catalyst were performed to enhance the catalytic performance for simultaneous control of NO_x and methanol. It was obtained that copper addition could improve the low-temperature activity of both NO_x conversion and methanol oxidation, where the optimal catalyst (Cu_0.05SCZ) exhibited a deNO_x activity of 96% and a mineralization rate of 97% at 250 °C, which are around 10% higher than that of Cu free sample. The characterization results showed that copper addition could obviously enhance the redox capacity of the catalysts. As such, the inhibition effect of methanol incomplete oxidation on NO adsorption and NH₃ activation were then lessened and the conversion of surface formamide species were also accelerated, resulting in the rising of NO_x conversion at low temperature. However, excessive copper addition would damage the Sb-Ce-Zr oxides solid solution structure owing to Cu-Ce strong interactions, decreasing the surface area and acidity. Meanwhile, due to easier over-oxidation of NH₃ with more Cu addition, the temperature window for NO_x conversion would become quite narrow. These findings could provide useful guidelines for the synergistic removal of VOCs over SCR catalyst in real application.     

Impacts of methanol fuel on vehicular emissions: A review

● Methanol effectively reduces CO, HC, CO₂, PM, and PN emissions of gasoline vehicles. ● Elemental composition of methanol directly affects the reduction of emissions. ● Several physicochemical properties of methanol help reduce vehicle emissions. The transport sector is a significant energy consumer and a major contributor to urban air pollution. At present, the substitution of cleaner fuel is one feasible way to deal with the growing energy demand and environmental pollution. Methanol has been recognized as a good alternative to gasoline due to its good combustion performance. In the past decades, many studies have investigated exhaust emissions using methanol-gasoline blends. However, the conclusions derived from different studies vary significantly, and the explanations for the effects of methanol blending on exhaust emissions are also inconsistent. This review summarizes the characteristics of CO, HC, NO_x, CO₂, and particulate emissions from methanol-gasoline blended fuels and pure methanol fuel. CO, HC, CO₂, particle mass (PM), and particle number (PN) emissions decrease when methanol-blended fuel is used in place of gasoline fuel. NO_x emission either decreases or increases depending on the test conditions, i.e., methanol content. Furthermore, this review synthesizes the mechanisms by which methanol-blended fuel influences pollutant emissions. This review provides insight into the pollutant emissions from methanol-blended fuel, which will aid policymakers in making energy strategy decisions that take urban air pollution, climate change, and energy security into account.     

Is atmospheric oxidation capacity better in indicating tropospheric O3 formation?

● This study summarizes and evaluates different approaches that indicate O₃ formation. ● Isopleth and sensitivity methods are useful but have many prerequisites. ● AOC is a better indicator of photochemical reactions leading to O₃ formation. Tropospheric ozone (O₃) concentration is increasing in China along with dramatic changes in precursor emissions and meteorological conditions, adversely affecting human health and ecosystems. O₃ is formed from the complex nonlinear photochemical reactions from nitrogen oxides (NO_x = NO + NO₂) and volatile organic compounds (VOCs). Although the mechanism of O₃ formation is rather clear, describing and analyzing its changes and formation potential at fine spatial and temporal resolution is still a challenge today. In this study, we briefly summarized and evaluated different approaches that indicate O₃ formation regimes. We identify that atmospheric oxidation capacity (AOC) is a better indicator of photochemical reactions leading to the formation of O₃ and other secondary pollutants. Results show that AOC has a prominent positive relationship to O₃ in the major city clusters in China, with a goodness of fit (R²) up to 0.6. This outcome provides a novel perspective in characterizing O₃ formation and has significant implications for formulating control strategies of secondary pollutants.     

Development of highly active coated monolith SCR catalyst with strong abrasion resistance for low-temperature application

Monolith SCR catalysts coated with V₂O₅-WO₃/TiO₂ were prepared by varying binder and coating thickness. Comparing with a monolith extruded with 100% V₂O₅-WO₃/TiO₂ powder, a coated monolith with a catalyst-coating layer of 260 μm in thickness exhibited the similar initial NO_x reduction activity at 250°C. After 4 h abrasion (attrition) in an air stream containing 300 g·m⁻³ fine sands (50–100 μm) at a superficial gas velocity of 10 m·s⁻¹, the catalyst still has the activity as a 100% molded monolith does in a 24-h activity test and it retains about 92% of its initial activity at 250°C. Estimation of the equivalent durable hours at a fly ash concentration of 1.0 g·m⁻³ in flue gas and a gas velocity of 5 m·s⁻¹ demonstrated that this coated monolith catalyst is capable of resisting abrasion for 13 months without losing more than 8% of its initial activity. The result suggests the great potential of the coated monolith for application to de-NO_x of flue gases with low fly ash concentrations from, such as glass and ceramics manufacturing processes.     

Insight into the promotion mechanism of activated carbon on the monolithic honeycomb red mud catalyst for selective catalytic reduction of NOx

• Activated carbon was proposed to be an efficient accelerant for molded red mud catalyst. • The surface acidity and reducibility were highly improved, as well as the pore structure. • The enrichment of the surface Fe²⁺ and the adsorbed oxygen account for the improvement. Our previous study proved that the acid-pretreatment process could efficiently activate red mud (RM) for the selective catalytic reduction (SCR) of NO_x. However, in terms of the molding process, which is the key step determining whether it can be applied in large-scale industrial, the surface acidity and reducibility of catalyst always decreased dramatically, and part of surface area and pore structure were lost. In this study, we prepared monolithic honeycomb red mud (MHRM) catalysts with activated carbon (AC) as an accelerant and investigated the effect of AC on the MHRM. The results showed that the MHRM with 3 wt.% of AC (MHRM-AC3) exhibited the best SCR performance, and kept more than 80% NO_x conversion in the range of 325°C–400°C. Compared with the MHRM, MHRM-AC1, and HMRM-AC5, the MHRM-AC3 has more mesoporous and macroporous structures, which can provide more adsorption active sites. The AC significantly improved NH₃ adsorption and surface reducibility, which was mainly due to the increase of the surface acid sites (especially the Brönsted acid sites), the concentration of Fe(II), and the surface adsorbed oxygen. The presence of more Fe(II) enriched the surface oxygen vacancies, as well as the surface adsorbed oxygen, due to the charge imbalance and unsaturated chemical bond. And surface adsorbed oxygen exhibited more active than lattice oxygen owing to its higher mobility, which was conducive to NO_x reduction in the SCR reaction.     

Chemical poison and regeneration of SCR catalysts for NOx removal from stationary sources

Selective catalytic reduction (SCR) of NO_x with NH₃ is an effective technique to remove NO_x from stationary sources, such as coal-fired power plant and industrial boilers. Some of elements in the fly ash deactivate the catalyst due to strong chemisorptions on the active sites. The poisons may act by simply blocking active sites or alter the adsorption behaviors of reactants and products by an electronic interaction. This review is mainly focused on the chemical poisoning on V₂O₅-based catalysts, environmental-benign catalysts and low temperature catalysts. Several common poisons including alkali/alkaline earth metals, SO₂ and heavy metals etc. are referred and their poisoning mechanisms on catalysts are discussed. The regeneration methods of poisoned catalysts and the development of poison-resistance catalysts are also compared and analyzed. Finally, future research directions in developing poisoning resistance catalysts and facile efficient regeneration methods for SCR catalysts are proposed.     

Electro-catalytic activity of CeOx modified graphite felt for carbamazepine degradation via E-peroxone process

•CeO_x/GF-EP process had the better degradation efficiency than GF-EP process. •CeO_x/GF-EP process had the flexible application in the pH range from 5.0 to 9.0. •CeO_x could enhance surface hydrophilicity and reduce the charge-transfer resistance. •The interfacial electron transfer process was revealed. E-peroxone (EP) was one of the most attractive AOPs for removing refractory organic compounds from water, but the high energy consumption for in situ generating H₂O₂ and its low reaction efficiency for activating O₃ under acidic conditions made the obstacles for its practical application. In this study, cerium oxide was loaded on the surface of graphite felt (GF) by the hydrothermal method to construct the efficient electrode (CeO_x/GF) for mineralizing carbamazepine (CBZ) via EP process. CeO_x/GF was an efficient cathode, which led to 69.4% TOC removal in CeO_x/GF-EP process with current intensity of 10 mA in 60 min. Moreover, CeO_x/GF had the flexible application in the pH range from 5.0 to 9.0, TOC removal had no obvious decline with decrease of pH. Comparative characterizations showed that CeO_x could enhance surface hydrophilicity and reduce the charge-transfer resistance of GF. About 5.4 mg/L H₂O₂ generated in CeO_x/GF-EP process, which was 2.1 times as that in GF-EP process. The greater ozone utility was also found in CeO_x/GF-EP process. More O₃ was activated into hydroxyl radicals, which accounted for the mineralization of CBZ. An interfacial electron transfer process was revealed, which involved the function of oxygen vacancies and Ce³⁺/Ce⁴⁺ redox cycle. CeO_x/GF had the good recycling property in fifth times’ use.     

Precursors and potential sources of ground-level ozone in suburban Shanghai

• Air masses from Zhejiang Province is the major source of O₃ in suburban Shanghai. • O₃ formation was in VOC-sensitive regime in rural Shanghai. • O₃ formation was most sensitive to propylene in rural Shanghai. A high level of ozone (O₃) is frequently observed in the suburbs of Shanghai, the reason for this high level remains unclear. To obtain a detailed insight on the high level of O₃ during summer in Shanghai, O₃ and its precursors were measured at a suburban site in Shanghai from July 1, 2016 to July 31, 2016. Using the Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model and concentration weighted trajectories (CWT), we found that Zhejiang province was the main potential source of O₃ in suburban Shanghai. When the sampling site was controlled by south-western winds exceeding 2 m/s, the O₃-rich air masses from upwind regions (such as Zhejiang province) could be transported to the suburban Shanghai. The propylene-equivalent concentration (PEC) and ozone formation potential (OFP) were further calculated for each VOC species, and the results suggested that propylene, (m+p)-xylene, and toluene played dominant roles in O₃ formation. The Ozone Isopleth Plotting Research (OZIPR) model was used to reveal the impact of O₃ precursors on O₃ formation, and 4 base-cases were selected to adjust the model simulation. An average disparity of 18.20% was achieved between the simulated and observed O₃ concentrations. The O₃ isopleth diagram illustrated that O₃ formation in July 2016 was in VOC-sensitive regime, although the VOC/NO_x ratio was greater than 20. By introducing sensitivity (S), a sensitivity analysis was performed for O₃ formation. We found that O₃ formation was sensitive to propylene, (m+p)-xylene, o-xylene and toluene. The results provide theoretical support for O₃ pollution treatment in Shanghai.     

δ15N-stable isotope analysis of NHx: An overview on analytical measurements,source sampling and its source apportionment

• Challenges in sampling of NH₃ sources for d¹⁵N analysis are highlighted. • Uncertainties in the isotope-based source apportionment of NH₃ and NH₄⁺ are outlined. • Characterizing dynamic isotopic fractionation may reduce uncertainties of NH_x science. Agricultural sources and non-agricultural emissions contribute to gaseous ammonia (NH₃) that plays a vital role in severe haze formation. Qualitative and quantitative contributions of these sources to ambient PM_2.5 (particulate matter with an aerodynamic equivalent diameter below 2.5 µm) concentrations remains uncertain. Stable nitrogen isotopic composition (δ¹⁵N) of NH₃ and NH₄⁺ (δ¹⁵N(NH₃) and δ¹⁵N(NH₄⁺), respectively) can yield valuable information about its sources and associated processes. This review provides an overview of the recent progress in analytical techniques for δ¹⁵N(NH₃) and δ¹⁵N(NH₄⁺) measurement, sampling of atmospheric NH₃ and NH₄⁺ in the ambient air and their sources signature (e.g., agricultural vs. fossil fuel), and isotope-based source apportionment of NH₃ in urban atmosphere. This study highlights that collecting sample that are fully representative of emission sources remains a challenge in fingerprinting δ¹⁵N(NH₃) values of NH₃ emission sources. Furthermore, isotopic fractionation during NH₃ gas-to-particle conversion under varying ambient field conditions (e.g., relative humidity, particle pH, temperature) remains unclear, which indicates more field and laboratory studies to validate theoretically predicted isotopic fractionation are required. Thus, this study concludes that lack of refined δ¹⁵N(NH₃) fingerprints and full understanding of isotopic fractionation during aerosol formation in a laboratory and field conditions is a limitation for isotope-based source apportionment of NH₃. More experimental work (in chamber studies) and theoretical estimations in combinations of field verification are necessary in characterizing isotopic fractionation under various environmental and atmospheric neutralization conditions, which would help to better interpret isotopic data and our understanding on NH_x (NH₃ + NH₄⁺) dynamics in the atmosphere.     

Contributions of adsorption,bioreduction and desorption to uranium immobilization by extracellular polymeric substances

● EPS immobilizes U(VI) via adsorption, bioreduction and desorption. ● This work provides a framework to quantify the three immobilization processes. ● The non-equilibrium adsorption of U follows pseudo-second-order kinetics. ● The equilibrium adsorption of U followed Langmuir and Freundlich isotherms. Hexavalent uranium (U(VI)) can be immobilized by various microbes. The role of extracellular polymeric substances (EPS) in U(VI) immobilization has not been quantified. This work provides a model framework to quantify the contributions of three processes involved in EPS-mediated U(VI) immobilization: adsorption, bioreduction and desorption. Loosely associated EPS was extracted from a pure bacterial strain, Klebsiella sp. J1, and then exposed to H₂ and O₂ (no bioreduction control) to immobilize U(VI) in batch experiments. U(VI) immobilization was faster when exposed to H₂ than O₂ and stabilized at 94% for H₂ and 85% for O₂, respectively. The non-equilibrium data from the H₂ experiments were best simulated by a kinetic model consisting of pseudo-second-order adsorption (k_a = 2.87 × 10⁻³ g EPS·(mg U)⁻¹·min⁻¹), first-order bioreduction (k_b = 0.112 min⁻¹) and first-order desorption (k_d = 7.00 × 10⁻³ min⁻¹) and fitted the experimental data with R² of 0.999. While adsorption was dominant in the first minute of the experiments with H₂, bioreduction was dominant from the second minute to the 50^th min. After 50 min, adsorption was negligible, and bioreduction was balanced by desorption. This work also provides the first set of equilibrium data for U(VI) adsorption by EPS alone. The equilibrium experiments with O₂ were well simulated by both the Langmuir isotherm and the Freundlich isotherm, suggesting multiple mechanisms involved in the interactions between U(VI) and EPS. The thermodynamic study indicated that the adsorption of U(VI) onto EPS was endothermic, spontaneous and favorable at higher temperatures.     

Heavy-metal adsorption by non-living biomass

The adsorption of some heavy metals onto the walls of harvested, washed, and dried non-living biomass cells of different Pseudomonas strains was studied at optimum experimental conditions using a simplified single component system. The Langmuir adsorption model was found to be a suitable approach to describe the system via multi-step processes. Isotherms measured at 30.0°C and pH 5.5 with [M]_total = 10-100 mM for tight, reversible Cr⁶⁺(aq), Ni²⁺(aq), Cu²⁺(aq) and Cd²⁺(aq) binding by the cell walls of the investigated biomass fit the Langmuir model and give the pH-independent stoichiometric site capacities ν_i and equilibrium constants K_i for metal binding at specific biomass sites i = A, B, C, and D. Tight binding sites A, B, and D of the non-living biomass are occupied by Cr^VI, sites A and C by Ni^II, sites A and D by Cd^II, and only site B by Cu^II. It is concluded that ν_i is a stoichiometric parameter that is independent of the magnitude of K_i for binding site i and that the studied heavy metals selectively and tightly bind at different biomass sites.