Nitrate Formation Research Articles

Haze caused by NOx oxidation under restricted residential and industrial activities in a mega city in the south of North China Plain

The formation of secondary aerosol species, including nitrate and sulfate, induces severe haze in the North China Plain. However, despite substantial reductions in anthropogenic pollutants due to severe restriction of residential and industrial activities in 2020 to stop the spread of COVID-19, haze still formed in Zhengzhou. We compared ionic compositions of PM2.5 during the period of the restriction with that immediately before the restriction and in the comparison period in 2019 to investigate the processes that caused the haze. The average concentration of PM2.5 was 83.9 μg m−3 in the restriction period, 241.8 μg m−3 before the restriction, and 94.0 μg m−3 in 2019. Nitrate was the largest contributor to the PM2.5 in all periods, with an average mass fraction of 24%–30%. The average molar concentration of total nitrogen compounds (NOx + nitrate) was 0.89 μmol m−3 in the restriction period, which was much lower than that in the non-restriction periods (1.85–2.74 μmol m−3). In contrast, the concentration of sulfur compounds (SO2 + sulfate) was 0.34–0.39 μmol m−3 in all periods. The conversion rate of NOx to nitrate (NOR) was 0.35 in the restriction period, significantly higher than that before the restriction (0.26) and in 2019 (0.25). NOR was higher with relative humidity in 40–80% in the restriction period than in the other two periods, whereas the conversion rate of SO2 to sulfate did not, indicating nitrate formation was more efficient during the restriction. When O3 occupied more than half of the oxidants (Ox = O3 + NO2), NOR increased rapidly with the ratio of O3 to Ox and was much higher in the daytime than nighttime. Therefore, haze in the restriction period was caused by increased NOx-to-nitrate conversion driven by photochemical reactions.

Sources and Formation of Atmospheric Nitrate Over China–Indochina Peninsula in Spring: A Perspective From Oxygen and Nitrogen Isotopic Compositions Based on Passive Air Samplers

The formation processes and potential sources of particulate nitrate can be revealed by nitrogen (δ15N-NO3−) and oxygen (δ18O-NO3−) isotopes; however, the linkage and comparative information over a large scale is limited. In this work, the feasibility of using quartz wool disk passive air samplers (Pas-QW) to identify and quantify the nitrate concentrations and their isotopic compositions was demonstrated. The results of a simultaneous sampling campaign from March to June showed that the NO3− concentration was largely attributed to the development of the regional economies. The regional distribution of δ15N-NO3− values was due to the source changes. The decreasing trend of δ18O-NO3− values with latitude from south to north was mainly a combination of oxygen isotopic fractionation of the oxidant induced by natural factors and anthropogenic changes in O3 concentrations. Coal combustion (CC) and mobile sources (MS) have a significant contribution to NOx in the typical urban agglomerations, while the high contribution from biomass burning (BB) and biogenic soil emission (BS) was mainly in areas with high natural productivity and intensive agricultural activities. By allowing simultaneous monitoring at multiple sites and over extended periods, passive sampling complements existing techniques for studying nitrate aerosol, and the results can provide a reference for the spatial distribution of its sources and formation in the China–Indochina Peninsula (CICP).

A diurnal story of Δ17O(rm{NO}_{3}^{-}) in urban Nanjing and its implication for nitrate aerosol formation

Inorganic nitrate production is critical in atmospheric chemistry that reflects the oxidation capacity and the acidity of the atmosphere. Here we use the oxygen anomaly of nitrate (Δ17O(rm{NO}_{3}^{-})) in high-time-resolved (3 h) aerosols to explore the chemical mechanisms of nitrate evolution in fine particles during the winter in Nanjing, a megacity of China. The continuous Δ17O(rm{NO}_{3}^{-}) observation suggested the dominance of nocturnal chemistry (NO3 + HC/H2O and N2O5 + H2O/Cl−) in nitrate formation in the wintertime. Significant diurnal variations of nitrate formation pathways were found. The contribution of nocturnal chemistry increased at night and peaked (72%) at midnight. Particularly, nocturnal pathways became more important for the formation of nitrate in the process of air pollution aggravation. In contrast, the contribution of daytime chemistry (NO2 + OH/H2O) increased with the sunrise and showed a highest fraction (48%) around noon. The hydrolysis of N2O5 on particle surfaces played an important role in the daytime nitrate production on haze days. In addition, the reaction of NO2 with OH radicals was found to dominate the nitrate production after nitrate chemistry was reset by the precipitation events. These results suggest the importance of high-time-resolved observations of Δ17O(rm{NO}_{3}^{-}) for exploring dynamic variations in reactive nitrogen chemistry.

Limitations in representation of physical processes prevent successful simulation of PM<sub>2.5</sub> during KORUS-AQ

Abstract. High levels of fine particulate matter (PM2.5) pollution in East Asia often exceed local air quality standards. Observations from the Korea–United States Air Quality (KORUS-AQ) field campaign in May and June 2016 showed that development of extreme pollution (haze) occurred through a combination of long-range transport and favorable meteorological conditions that enhanced local production of PM2.5. Atmospheric models often have difficulty simulating PM2.5 chemical composition during haze, which is of concern for the development of successful control measures. We use observations from KORUS-AQ to examine the ability of the GEOS-Chem chemical transport model to simulate PM2.5 composition throughout the campaign and identify the mechanisms driving the pollution event. At the surface, the model underestimates sulfate by −64 % but overestimates nitrate by +36 %. The largest underestimate in sulfate occurs during the pollution event, for which models typically struggle to generate elevated sulfate concentrations due to missing heterogeneous chemistry in aerosol liquid water in the polluted boundary layer. Hourly surface observations show that the model nitrate bias is driven by an overestimation of the nighttime peak. In the model, nitrate formation is limited by the supply of nitric acid, which is biased by +100 % against aircraft observations. We hypothesize that this is due to a large missing sink, which we implement here as a factor of 5 increase in dry deposition. We show that the resulting increased deposition velocity is consistent with observations of total nitrate as a function of photochemical age. The model does not account for factors such as the urban heat island effect or the heterogeneity of the built-up urban landscape, resulting in insufficient model turbulence and surface area over the study area that likely results in insufficient dry deposition. Other species such as NH3 could be similarly affected but were not measured during the campaign. Nighttime production of nitrate is driven by NO2 hydrolysis in the model, while observations show that unexpectedly elevated nighttime ozone (not present in the model) should result in N2O5 hydrolysis as the primary pathway. The model is unable to represent nighttime ozone due to an overly rapid collapse of the afternoon mixed layer and excessive titration by NO. We attribute this to missing nighttime heating driving deeper nocturnal mixing that would be expected to occur in a city like Seoul. This urban heating is not considered in air quality models run at large enough scales to treat both local chemistry and long-range transport. Key model failures in simulating nitrate, mainly overestimated daytime nitric acid, incorrect representation of nighttime chemistry, and an overly shallow and insufficiently turbulent nighttime mixed layer, exacerbate the model's inability to simulate the buildup of PM2.5 during haze pollution. To address the underestimate in sulfate most evident during the haze event, heterogeneous aerosol uptake of SO2 is added to the model, which previously only considered aqueous production of sulfate from SO2 in cloud water. Implementing a simple parameterization of this chemistry improves the model abundance of sulfate but degrades the SO2 simulation, implying that emissions are underestimated. We find that improving model simulations of sulfate has direct relevance to determining local vs. transboundary contributions to PM2.5. During the haze pollution event, the inclusion of heterogeneous aerosol uptake of SO2 decreases the fraction of PM2.5 attributable to long-range transport from 66 % to 54 %. Locally produced sulfate increased from 1 % to 25 % of locally produced PM2.5, implying that local emissions controls could have a larger effect than previously thought. However, this additional uptake of SO2 is coupled to the model nitrate prediction, which affects the aerosol liquid water abundance and chemistry driving sulfate–nitrate–ammonium partitioning. An additional simulation of the haze pollution with heterogeneous uptake of SO2 to aerosol and simple improvements to the model nitrate simulation results in 30 % less sulfate due to 40 % less nitrate and aerosol water, and this results in an underestimate of sulfate during the haze event. Future studies need to better consider the impact of model physical processes such as dry deposition and nighttime boundary layer mixing on the simulation of nitrate and the effect of improved nitrate simulations on the overall simulation of secondary inorganic aerosol (sulfate + nitrate + ammonium) in East Asia. Foreign emissions are rapidly changing, increasing the need to understand the impact of local emissions on PM2.5 in South Korea to ensure continued air quality improvements.

Heterogeneous Reaction of Peroxyacetyl Nitrate on Real-World PM2.5 Aerosols: Kinetics, Influencing Factors, and Atmospheric Implications.

The formation and decomposition of peroxyacetyl nitrate (PAN), an important atmospheric nitrogen oxide reservoir, can impact the level and cycling of free radicals and nitrogen compounds in the atmosphere. PAN sinks are poorly understood, highlighting the importance of elucidating the heterogeneous reaction of PAN on aerosol surfaces. Here, we report for the first time the uptake behavior, kinetics, and potential mechanism of PAN uptake on real-world aerosol PM2.5 using a flow tube system. The uptake coefficients (γ) of PAN increased non-linearly from (1.5 ± 0.7) × 10-5 at 0% relative humidity (RH) to (9.3 ± 2.0) × 10-5 at 80% RH. The γ decrease with increasing initial PAN concentration is consistent with the Langmuir-Hinshelwood mechanism. Organic components of aerosols may promote heterogeneous loss of PAN through redox reactions. Higher γ occurs with higher water content, lower pH, and lower ionic strength in the aqueous phase of aerosols. The present study suggests that heterogeneous reaction of PAN on ambient aerosols plays a non-negligible role in the atmospheric PAN budget and provides new insights into the role of PAN in promoting atmospheric oxidation capacity during hazy periods with cold and wet weather conditions.

Kinetics of processes initiated in a water cathode by the action of a direct current discharge at atmospheric pressure in air: simulation and experiment

The kinetics of the formation of hydrogen peroxide, nitrate and nitrite ions and the pH of the solution, which served as the cathode, were studied under the action of a direct current discharge at atmospheric pressure in air. A 0D kinetic model has been developed that describes the reactions occurring in solution. The model includes 28 components, 119 reactions between them, as well as fluxes of particles coming to the surface of the solution from the discharge. The particle fluxes were determined from the 0D model of a discharge in air based on the self-consistent solution of the Boltzmann equation, the equations of vibrational kinetics for the ground states of N2, O2, H2O, NO molecules, and the equations of chemical kinetics. The proposed model is semi-empirical, since it includes not only known experimental kinetic data, but also some assumptions that were made to match the calculation results with experiment. An analysis of the experimental data and calculations by the model showed that the main factors initiating reactions in solution are the bombardment of the surface by a flux of positive ions accelerated in the cathode potential drop and the flux of NO molecules from the discharge. Ion bombardment leads to the formation of hydrogen peroxide, during the decomposition of which OH radicals are formed, the subsequent reactions of which determine the composition of the particles of the solution. The source of nitrogen-containing particles is the flux of NO molecules from the discharge. Data are given on the kinetics of the concentrations of the main particles of the solution and the analysis of the mechanisms of the processes of their formation and decay. The results of calculations of the concentrations of H2O2, NO2 −, NO3 −, and pH agree with the experiment within the limits of the latter’s accuracy.

Size-segregated chemical compositions of particulate matter including PM0.1 in northern Vietnam, a highly polluted area where notable seasonal episodes occur

In October 2017 and June 2018, measurements of size-segregated atmospheric particles containing ultrafine particles (PM0.1) were carried out using a Nanosampler in northern Vietnam (urban, peri-urban and rural areas). This study shows that the variations of PM concentration at the three sites were very similar and that air pollution is widespread in northern Vietnam. However, a concentration difference between cities and a change of composition at high PM concentration were confirmed, and there were some characteristic regional, particle-size, and component trends. From the carbon-fraction distribution, the carbon components of atmospheric particles in Vietnam were affected by vehicles (OC3) and biomass combustion (OC3, EC1), and PM0.1 was affected strongly by vehicles (EC2). The water-soluble ionic component of fine particles in Vietnam is characterized by the highest amount of nitrate next to sulfate. The nitrate formation path is analyzed from the degree of neutralization with ammonium. In coarse and fine particles, particle formation of nitrate due to heterogeneous reaction is dominant, and the contribution of HNO3 adsorption by soil particles and N2O5 hydrolysis is high. For PM0.1, the formation of ammonium nitrate by a homogeneous reaction is the main production path. High-concentration events with increased nitrate were observed in late October, characterized by the effects of long-distance transportation and the promotion of nocturnal N2O5 hydrolysis with increased humidity. In June, when there was an increase in PM concentration derived from biomass combustion, PM0.1 indicated characteristic behavior, suggesting that it is possible to estimate local sources from PM0.1 components and variations.

Designing a Redox Heterojunction for Photocatalytic "Overall Nitrogen Fixation" under Mild Conditions.

Ammonia and nitrates are the most fundamental and significant raw ingredients in human society. Till now, industrial synthetic ammonia by Haber-Bosch process and industrial synthetic nitrates by the Ostwald process have encountered increasingly serious challenges, i.e., high energy consumption, high cost, and environment-harmful gas emissions. Therefore, developing alternative approaches to achieve nitrogen fixation to overcome the inherent deficiencies of the well-established Haber-Bosch and Ostwald processes has fascinated scientists for many years, especially the simultaneous formation of ammonia and nitrate directly from N2 molecules, which has been rarely studied. Herein, a heterojunction-based photocatalytic system is designed to successfully achieve "overall nitrogen fixation," a sustainable and simultaneous conversion of N2 molecules into ammonia and nitrate products under mild conditions. In this heterojunction, interfacial charge redistribution (ICR) promotes selective accumulations of photogenerated electrons and holes in the CdS and WO3 components. As a result, N2 molecules can be activated and reduced to ammonia products with yields of 35.8µmol h-1 g-1 by a multi-electron process, and synchronously oxidized into nitrate products with yields of 14.2µmol h-1 g-1 by a hole-induced oxidation coupling process. This work provides a novel insight and promising approach to realize artificial nitrogen fixation under mild condition.

Histochemical Evidence for Nitrogen-Transfer Endosymbiosis in Non-Photosynthetic Cells of Leaves and Inflorescence Bracts of Angiosperms.

Simple SummaryWe used light and confocal microscopy to visualize bacteria in leaf and bract cells of more than 30 species in 18 families of seed plants. We detected chemical exchanges between intracellular bacteria and plant cells. We found that endophytic bacteria that show evidence of the transfer of nitrogen to plants are present in non-photosynthetic cells of leaves and bracts of diverse plant species. Nitrogen transfer from bacteria was observed in epidermal cells, various filamentous and glandular trichomes, and other non-photosynthetic cells. The most efficient of the nitrogen-transfer endosymbioses were seen to involve glandular trichomes, as seen in hops (Humulus lupulus) and hemp (Cannabis sativa). Trichome chemistry is hypothesized to function to scavenge oxygen around bacteria to facilitate nitrogen fixation.We used light and confocal microscopy to visualize bacteria in leaf and bract cells of more than 30 species in 18 families of seed plants. Through histochemical analysis, we detected hormones (including ethylene and nitric oxide), superoxide, and nitrogenous chemicals (including nitric oxide and nitrate) around bacteria within plant cells. Bacteria were observed in epidermal cells, various filamentous and glandular trichomes, and other non-photosynthetic cells. Most notably, bacteria showing nitrate formation based on histochemical staining were present in glandular trichomes of some dicots (e.g., Humulus lupulus and Cannabis sativa). Glandular trichome chemistry is hypothesized to function to scavenge oxygen around bacteria and reduce oxidative damage to intracellular bacterial cells. Experiments to assess the differential absorption of isotopic nitrogen into plants suggest the assimilation of nitrogen into actively growing tissues of plants, where bacteria are most active and carbohydrates are more available. The leaf and bract cell endosymbiosis types outlined in this paper have not been previously reported and may be important in facilitating plant growth, development, oxidative stress resistance, and nutrient absorption into plants. It is unknown whether leaf and bract cell endosymbioses are significant in increasing the nitrogen content of plants. From the experiments that we conducted, it is impossible to know whether plant trichomes evolved specifically as organs for nitrogen fixation or if, instead, trichomes are structures in which bacteria easily colonize and where some casual nitrogen transfer may occur between bacteria and plant cells. It is likely that the endosymbioses seen in leaves and bracts are less efficient than those of root nodules of legumes in similar plants. However, the presence of endosymbioses that yield nitrate in plants could confer a reduced need for soil nitrogen and constitute increased nitrogen-use efficiency, even if the actual amount of nitrogen transferred to plant cells is small. More research is needed to evaluate the importance of nitrogen transfer within leaf and bract cells of plants.

Understanding the Water Effect for Selective Catalytic Reduction of NOx with NH3 over Cu-SSZ-13 Catalysts

The catalytic activity of commercial Cu-SSZ-13 monolith catalysts was measured in the presence and absence of water, which demonstrated an inhibiting role below 300 °C and a promoting role above 300 °C. Furthermore, temperature-programed desorption illustrated that hydrolysis of Z2Cu would take place to generate ZCuIIOH and [Cu(H2O)6]2+ species, which inhibited ammonia adsorption over Lewis acid sites but promoted nitrate formation and gaseous NO2 desorption. The temperature-programed surface reaction and in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS) were further performed to elucidate the influence of water on reaction mechanisms. Basically, the NH3-SCR reaction mainly took place at Cu centers acting as Lewis acid sites of Cu-SSZ-13 catalysts in the low-temperature regime. Water inhibited the reaction by occupying and blocking Lewis acid sites to prevent [Cu(NH3)2]2+ formation and NO oxidation from occurring, limiting the formation of NH4NO3 intermediates. In the high-temperature regime, gaseous NO2 could directly interact with NH4+ molecules adsorbed onto Brønsted acid sites. The addition of water could facilitate the production of gaseous NO2 decomposed by surface nitrates and further promote the NH3-SCR reaction rate at high temperatures.

Secondary PM<sub>2.5</sub> decreases significantly less than NO<sub>2</sub> emission reductions during COVID lockdown in Germany

Abstract. This study estimates the influence of anthropogenic emission reductions on the concentration of particulate matter with a diameter smaller than 2.5 µm (PM2.5) during the 2020 lockdown period in German metropolitan areas. After accounting for meteorological effects, PM2.5 concentrations during the spring 2020 lockdown period were 5 % lower compared to the same time period in 2019. However, during the 2020 pre-lockdown period (winter), PM2.5 concentrations with meteorology accounted for were 19 % lower than in 2019. Meanwhile, NO2 concentrations with meteorology accounted for dropped by 23 % during the 2020 lockdown period compared to an only 9 % drop for the 2020 pre-lockdown period, both compared to 2019. SO2 and CO concentrations with meteorology accounted for show no significant changes during the 2020 lockdown period compared to 2019. GEOS-Chem (GC) simulations with a COVID-19 emission reduction scenario based on the observations (23 % reduction in anthropogenic NOx emission with unchanged anthropogenic volatile organic compounds (VOCs) and SO2) are consistent with the small reductions of PM2.5 during the lockdown and are used to identify the underlying drivers for this. Due to being in a NOx-saturated ozone production regime, GC OH radical and O3 concentrations increased (15 % and 9 %, respectively) during the lockdown compared to a business-as-usual (BAU, no lockdown) scenario. Ox (equal to NO2+O3) analysis implies that the increase in ozone at nighttime is solely due to reduced NO titration. The increased O3 results in increased NO3 radical concentrations, primarily during the night, despite the large reductions in NO2. Thus, the oxidative capacity of the atmosphere is increased in all three important oxidants, OH, O3, and NO3. PM nitrate formation from gas-phase nitric acid (HNO3) is decreased during the lockdown as the increased OH concentration cannot compensate for the strong reductions in NO2, resulting in decreased daytime HNO3 formation from the OH + NO2 reaction. However, nighttime formation of PM nitrate from N2O5 hydrolysis is relatively unchanged. This results from the fact that increased nighttime O3 results in significantly increased NO3, which roughly balances the effect of the strong NO2 reductions on N2O5 formation. Ultimately, the only small observed decrease in lockdown PM2.5 concentrations can be explained by the large contribution of nighttime PM nitrate formation, generally enhanced sulfate formation, and slightly decreased ammonium. This study also suggests that high PM2.5 episodes in early spring are linked to high atmospheric ammonia concentrations combined with favorable meteorological conditions of low temperature and low boundary layer height. Northwest Germany is a hot-spot of NH3 emissions, primarily emitted from livestock farming and intensive agricultural activities (fertilizer application), with high NH3 concentrations in the early spring and summer months. Based on our findings, we suggest that appropriate NOx and VOC emission controls are required to limit ozone, and that should also help reduce PM2.5. Regulation of NH3 emissions, primarily from agricultural sectors, could result in significant reductions in PM2.5 pollution.

Fate of the nitrate radical at the summit of a semi-rural mountain site in Germany assessed with direct reactivity measurements

Abstract. The reactivity of NO3 plays an important role in modifying the fate of reactive nitrogen species at nighttime. High reactivity (e.g. towards unsaturated volatile organic compounds – VOCs) can lead to formation of organic nitrates and secondary organic aerosol, whereas low reactivity opens the possibility of heterogeneous NOx losses via the formation and uptake of N2O5 to particles. We present direct NO3 reactivity measurements (kNO3) that quantify the VOC-induced losses of NO3 during the TO2021 campaign at the summit of the Kleiner Feldberg mountain (825 m, Germany) in July 2021. kNO3 was on average ∼0.035 s−1 during the daytime, ∼0.015 s−1 for almost half of the nights and below the detection limit of 0.006 s−1 for the other half, which may be linked to sampling from above the nocturnal surface layer. NO3 reactivities derived from VOC measurements and the corresponding rate coefficient were in good agreement with kNO3, with monoterpenes representing 84 % of the total reactivity. The fractional contribution F of kNO3 to the overall NO3 loss rate (which includes an additional reaction of NO3 with NO and photolysis) were on average ∼16 % during the daytime and ∼50 %–60 % during the nighttime. The relatively low nighttime value of F is related to the presence of several tens of parts per trillion by volume (pptv) of NO on several nights. NO3 mixing ratios were not measured, but steady-state calculations resulted in nighttime values between <1 and 12 pptv. A comparison of results from TO2021 with direct measurements of NO3 during previous campaigns between 2008 and 2015 at this site revealed that NO3 loss rates were remarkably high during TO2021, while NO3 production rates were low. We observed NO mixing ratios of up to 80 pptv at night, which has implications for the cycling of reactive nitrogen at this site. With O3 present at levels of mostly 25 to 60 ppbv (parts per billion by volume), NO is oxidized to NO2 on a timescale of a few minutes. We find that maintaining NO mixing ratios of, e.g., 40 pptv requires a ground-level NO emission rate of 0.33 pptv s−1 (into a shallow surface layer of 10 m depth). This in turn requires a rapid deposition of NO2 to the surface (vdNO2∼0.15 cm s−1) to reduce nocturnal NO2 levels to match the observations.

Chemical Compositions in Winter PM2.5 in Changzhou of the Yangtze River Delta Region, China: Characteristics and Atmospheric Responses Along With the Different Pollution Levels

Changzhou, a typical industrial city located in the center of the Yangtze River Delta (YRD) region, has experienced serious air pollution in winter. However, Changzhou still receives less attention compared with other big cities in YRD. In this study, a four-month PM2.5sampling campaign was conducted in Changzhou, China from 1 November 2019, to 1 February 2020. The period covers the entire wintertime and includes first week of the Level 1 response stage of the lockdown period due to the outbreak of COVID-19. The mean PM2.5concentrations were 67.9 ± 29.0 μg m−3, ranging from 17.4 to 157.4 μg m−3. Secondary inorganic ions were the most abundant species, accounting for 37 and 50% during the low and high PM2.5pollution periods, respectively. Nitrogen oxidation ratio (NOR) during the high PM concentration level period was twice the low PM concentration period whereas sulfur oxidation ratio (SOR) showed a less significant increase. This represents that nitrate formation is potentially the predominant factor controlling the occurrence of PM pollution. The analysis of NOR, SOR as functions of relative humidity (RH) and ozone (O3) concentrations suggest that the sulfate formation was mainly through aqueous-phase reaction, while nitrate formation was driven by both photochemistry and heterogeneous reaction. And, excess ammonium could promote the formation of nitrate during the high PM period, indicating that ammonia gas played a critical role in regulating nitrate. Furthermore, a special period-Chinese New Year overlapping first week of COVID-19 lockdown period, offered a precious window to study the impact of human activity pattern changes on air pollution variation. During the special period, the average PM2.5mean concentration was 60.4 μg m−3, which did not show in a low value as expected. The declines in nitrogen oxide (NOx) emissions led to rapid increases in O3and atmospheric oxidizing capacity, as well as sulfate formation. The chemical profiles and compositions obtained during different periods provide a scientific basis for establishing efficient atmospheric governance policies in the future.

Synchrotron X-Ray-Driven Nitrogen Reduction on an AgCu Thin Film.

Nitrogen (N2 ) is an essential element for life, but kinetically stable N2 in the atmosphere needs to be reduced to biologically available forms as a nutrient for organisms. Abiotic nitrogen fixation is critical to the origin of life on the early Earth, which is due to lightning or mineral-based reduction. Here, synchrotron X-ray-induced silver nitrate formation on a silver copper (AgCu) thin-film is reported. Time-resolved X-ray diffraction measurements show that under intense X-ray exposure, initially formed silver oxides (AgOx) are quickly converted to silver nitrate (AgNO3 ). Interestingly, AgNO3 is first formed in its high-temperature phase with a space group of R3cH, which gradually transforms to the room temperature phase with a space group of Pbca under continuous X-ray irradiation. The result not only provides a new clue about the abiotic nitrogen reduction prior to life but also demonstrates a novel strategy of materials synthesis using synchrotron X-rays.

Selective catalytic reduction of NOx with NH3 over Ce-Mn oxide and Cu-SSZ-13 composite catalysts – Low temperature enhancement

A composite catalyst comprised of ceria-manganese oxide and Cu-SSZ-13 components represents a potential solution for improving selective catalytic reduction (SCR) of NOx by ammonia. Here, clarity is provided to the pathway of promotion on these catalysts at low temperatures (< 200 °C), and it is shown that improved performance comes solely from interaction of the oxide phase with Brønsted acid bound NH3. We demonstrate that at low temperatures, the catalytic components interact via oxide-derived nitrites/nitrite-precursors (e.g., HONO, N2O3) reacting with Brønsted acid bound NH3 from the zeolite. Then, only at elevated temperatures is the influence of the oxide phase on Cu redox in the Cu-SSZ-13 observed. Furthermore, we show how the oxide component has the great potential to circumvent NH4NO3 inhibition on Cu-SSZ-13 in the composite catalysts at low temperatures by bypassing the formation of nitrates from NO2 disproportionation, thus providing a practical solution to improving low temperature SCR reactivity.

Unbalanced emission reductions and adverse meteorological conditions facilitate the formation of secondary pollutants during the COVID-19 lockdown in Beijing.

During the coronavirus disease 2019 (COVID-19) lockdown in 2020, severe haze pollution occurred in the North China Plain despite the significant reduction in anthropogenic emissions, providing a natural experiment to explore the response of haze pollution to the reduction of human activities. Here, we study the characteristics and causes of haze pollution during the COVID-19 outbreak based on comprehensive field measurements in Beijing during January and February 2020. After excluding the Spring Festival period affected by fireworks activities, we found the ozone concentrations and the proportion of sulfate and nitrate in PM2.5 increased during the COVID-19 lockdown compared with the period before the lockdown, and sulfate played a more important role. Heterogeneous chemistry and photochemistry dominate the formation of sulfate and nitrate during the whole campaign, respectively, and the heterogeneous formation of nitrate at night was enhanced during the lockdown. The coeffects of more reductions in NOx than VOCs, weakened titration of NO, and increased temperature during the lockdown led to the increase in ozone concentrations, thereby promoting atmospheric oxidation capacity and photochemistry. In addition, the increase in relative humidity during the lockdown facilitated heterogeneous chemistry. Our results indicate that unbalanced emission reductions and adverse meteorological conditions induce the formation of secondary pollutants during the COVID-19 lockdown haze, and the formulation of effective coordinated emission-reduction control measures for PM2.5 and ozone pollution is needed in the future, especially the balanced control of NOx and VOCs.

СПРАВОЧНОЕ ОБЕСПЕЧЕНИЕ РАСЧЁТА ТЕПЛОВЫХ ЭФФЕКТОВ РЕАКЦИЙ

By calculation under standard conditions, the sign of the enthalpy of formation of a dimethylammonium ion in an aqueous solution at infinite dilution was specified, the heats of formation of methylammonium nitrate in water, the heats of dissolution of alkyl-substituted ammonium nitrates with the formation of an extremely dilute aqueous solution were calculated

Formation and evolution of secondary particulate matter during heavy haze pollution episodes in winter in a severe cold climate region of Northeast China.

The formation and evolution of sulfate (SO42-) and nitrate (NO3-) secondary contaminants under different stages of pollution episodes and different meteorological and emission conditions were compared, based on the simultaneous observation of fine particulate matter (PM2.5) and its chemical components in four heavy haze pollution episodes at 14 sampling sites in a severe cold climate region of Northeast China in winter from 2017 to 2019. The results yielded two main findings. (1) Nitrate formation during the day was mainly due to the combination of high emissions and high relative humidity (RH, 50-90%), high temperature (T, 0 to 5°C), high atmospheric oxidizability (ozone (O3) and nitrous acid (HONO) concentrations), and high ammonia (NH3) concentrations. Nitrate was formed by a gas-phase homogeneous reaction of the hydroxyl radical (OH·) with nitrogen dioxide (NO2), sulfur dioxide (SO2), and ammonia (NH3). (2) The main differences in SO42- formation between Northeast China and other regions were that the gas-phase oxidation process played an important role. This was mainly a result of the promotion of the gas-phase oxidation of SO42- due to the high oxidizing ability and the suppression of the aqueous reaction due to the low Ts in winter and low-sulfur coal emissions. Sulfate formation mostly occurred through an aqueous phase reaction in winter, but the highest yield and the fastest production capacity were produced by the gas-phase reaction.

Variations of PM2.5 sources in the context of meteorology and seasonality at an urban street canyon in Southwest Germany

In order to assess the factors controlling urban air pollution, we characterized fine particulate matter (PM2.5) at an urban street canyon in southwest Germany, in summer 2019 and winter 2020. The average mass concentration of PM2.5 was higher in dry and hot summer (7.0 ± 3.5 μg m−3) than in cold and humid winter (5.8 ± 2.8 μg m−3) with frequent wet scavenging. The non-refractory PM2.5 (NR-PM2.5) measured with an aerosol mass spectrometer (AMS) plus black carbon (BC) mostly consists of organic aerosol (OA) with 60% in summer and 44% in winter. The contributions of sulfate to NR-PM2.5 plus BC was higher in summer (18%) than in winter (13%), while that of nitrate was lower in summer (6%) than in winter (22%). During the entire measurement periods in both seasons, relatively flat diurnal variations of sulfate were found, suggesting that it was associated with regional transport. However, occasionally rapid increase of sulfate can be caused by the transport of upwind industrial sources and enhanced vertical mixing processes. Nitrate showed a peak at morning rush hours related to traffic emissions, and then subsequently decreased by evaporation processes during daytime with higher temperature. Positive matrix factorization analysis revealed that the total OA was dominated by secondary organic aerosol (SOA) over the primary traffic emissions with ∼82% in summer and ∼48% in winter. A detailed analysis of two pollution episodes clearly demonstrated the impact of meteorological conditions on secondary aerosol formation and accumulation. A summertime heatwave episode showed high contributions of SOA to PM2.5 mass, which formed locally through daytime photochemical oxidation as well as nighttime chemistry of biogenic precursors. A wintertime transitional episode occurred with significant shift from relatively warm and humid to cold and dry conditions. The fast formation of sulfate, nitrate, ammonium and SOA were found under the warm and humid period after receiving a local industrial emission plume. The cold and dry period was influenced by various sources including long-range transport of Saharan dust and anthropogenic emissions in central Europe. This study highlights the variations of urban PM2.5 sources under certain meteorological conditions such as summer heatwave and humid winter, which are expected high occurrence in future. Our results provide the implication on actual needs of mitigation actions to these pollution episodes in less-polluted western Europe cities.

Application and Development of Selective Catalytic Reduction Technology for Marine Low-Speed Diesel Engine: Trade-Off among High Sulfur Fuel, High Thermal Efficiency, and Low Pollution Emission

In recent years, the International Maritime Organization (IMO), Europe, and the United States and other countries have set up different emission control areas (ECA) for ship exhaust pollutants to enforce more stringent pollutant emission regulations. In order to meet the current IMO Tier III emission regulations, an after-treatment device must be installed in the exhaust system of the ship power plant to reduce the ship NOx emissions. At present, selective catalytic reduction technology (SCR) is one of the main technical routes to resolve excess NOx emissions of marine diesel engines, and is the only NOx emission reduction technology recognized by the IMO that can be used for various ship engines. Compared with the conventional low-pressure SCR system, the high-pressure SCR system can be applied to low-speed marine diesel engines that burn inferior fuels, but its working conditions are relatively harsh, and it can be susceptible to operational problems such as sulfuric acid corrosion, salt blockage, and switching delay during the actual ship tests and ship applications. Therefore, it is necessary to improve the design method and matching strategy of the high-pressure SCR system to achieve a more efficient and reliable operation. This article summarizes the technical characteristics and application problems of marine diesel engine SCR systems in detail, tracks the development trend of the catalytic reaction mechanism, engine tuning, and control strategy under high sulfur exhaust gas conditions. Results showed that low temperature is an important reason for the formation of ammonium nitrate, ammonium sulfate, and other deposits. Additionally, the formed deposits will directly affect the working performance of the SCR systems. The development of SCR technology for marine low-speed engines should be the compromise solution under the requirements of high sulfur fuel, high thermal efficiency, and low pollution emissions. Under the dual restrictions of high sulfur fuel and low exhaust temperature, the low-speed diesel engine SCR systems will inevitably sacrifice part of the engine economy to obtain higher denitrification efficiency and operational reliability.