Nonlinear responses of particulate nitrate to NO_x emission controls in the megalopolises of China

Nitrate is an increasingly important component of fine particulate matter (PM2.5) in Chinese cities. The production of nitrate is not only related to the abundance of its precursor, but also supported by atmospheric photochemical oxidants. The control of nitrogen oxides (NOx) emissions may thereby lead to nonlinear changes of nitrate concentrations, raising a new challenge to the current emission control actions in China. This paper uses comprehensive measurements and a regional meteorology-chemistry model with optimized mechanisms to establish the nonlinear responses between particulate nitrate and NOx emission controls in the megalopolises of China. Nitrate is an essential component of PM2.5 in eastern China, accounting for 9.4–15.5 % and 11.5–32.1 % of the PM2.5 mass for the warm and cold seasons. The hypothetical NOx emission reduction scenarios (−10 %~−80 %) during summer-autumn result in almost linearly lower PM2.5 by −2.65 % in Beijing-Tianjin-Hebei (BTH) and −2.79 % in Yangtze River Delta (YRD) per 10 % cut of NOx emissions, whereas they increase the oxidant levels and lead to a rather complicated response of PM components in winter. Wintertime nitrate is found to increase by 4.28 % in BTH and 4.60 % in YRD, with higher dinitrogen pentoxide (N2O5) intermediate products produced from increased ozone introduced by lower NOx emissions. An inflexion point appears at 40–50 % NOx emission reduction, and a further cut in NOx emission is predicted to cause −8.74 % reduction of nitrate for BTH and −10.59 % for YRD per 10 % cut of NOx emissions. In addition, the 2012–2016 NOx control strategy actually leads to no change or even increase of nitrate in some areas (8.82 % in BTH and 14.41 % in YRD) during winter. This paper helps understand the nonlinear aerosol and photochemistry feedbacks, and defines the effectiveness of proposed mitigations for the increasingly serious nitrate pollution in China.

Urban inland wintertime N₂O₅ and ClNO₂ influenced by snow-covered ground, air turbulence, and precipitation

The atmospheric multiphase reaction of dinitrogen pentoxide (N2O5) with chloride-containing aerosol particles produces nitryl chloride (ClNO2), which has been observed across the globe. The photolysis of ClNO2 produces chlorine radicals and nitrogen dioxide (NO2), which alter pollutant fates and air quality. However, the effects of local meteorology on near-surface ClNO2 production are not yet well understood, as most observational and modeling studies focus on periods of clear conditions. During a field campaign in Kalamazoo, Michigan from January–February 2018, N2O5 and ClNO2 were measured using chemical ionization mass spectrometry, with simultaneous measurements of atmospheric particulate matter and meteorological parameters. We examine the impacts of atmospheric turbulence, precipitation (snow, rain) and fog, and ground cover (snow-covered and bare ground) on the abundances of ClNO2 and N2O5. N2O5 mole ratios were lowest during periods of lower turbulence and were not statistically significantly different between snow-covered and bare ground. In contrast, ClNO2 mole ratios were highest, on average, over snow-covered ground, due to saline snowpack ClNO2 production. Both N2O5 and ClNO2 mole ratios were lowest, on average, during rainfall and fog because of scavenging, with N2O5 scavenging by fog droplets likely contributing to observed increased particulate nitrate concentrations. These observations, specifically those during active precipitation and with snow-covered ground, highlight important processes, including N2O5 and ClNO2 wet scavenging, fog nitrate production, and snowpack ClNO2 production, that govern the variability in observed atmospheric chlorine and nitrogen chemistry and are missed when considering only clear conditions.

Winter observations of ClNO₂ in northern China: Spatiotemporal variability and insights into daytime peaks

Nitryl chloride (ClNO2) is an important chlorine reservoir in the atmosphere that affects the oxidation of volatile organic compounds (VOCs) and the production of ROx radicals and ozone (O3). This study presents measurements of ClNO2 and related compounds at urban, rural, and mountain sites in the winter of 2017–2018 over the North China Plain (NCP). The nocturnal concentrations of ClNO2 were lower at the urban and rural sites but higher at the mountain site. The winter concentrations of ClNO2 were generally lower than the summer concentrations that were previously observed at these sites, which was due to the lower nitrate radical (NO3) production rate (P(NO3) and the smaller N2O5 uptake coefficients (γ(N2O5)) in winter, despite the higher dinitrogen pentoxide (N2O5) to NO3 ratios in winter. Significant daytime peaks of ClNO2 were observed at all the sites during the winter campaigns, with ClNO2 mixing ratios of up to 1.3 ppbv. Vertical transport of ClNO2 from the residual layers and prolonged photochemical lifetime of ClNO2 in winter may explain the elevated daytime concentrations. The daytime-averaged chlorine radical (Cl) production rates (P(Cl)) from the daytime ClNO2 were 0.17, 0.11, and 0.12 ppbv h−1 at the rural, urban, and mountain sites, respectively, which were approximately 3–4 times higher than the campaign-averaged conditions. Box model calculations showed that the Cl atoms liberated during the daytime peaks of ClNO2 increased the ROx levels by up to 27–37 % and increased the daily O3 productions by up to 13–18 %.

Nitration of aromatics with dinitrogen pentoxide in a liquefied 1,1,1,2-tetrafluoroethane medium

A green, safe, and economical method for the production of nitroaromatics is developed. The method comprises the use of the eco-friendly nitrating agent, dinitrogen pentoxide, and liquefied 1,1,1,2-tetrafluoroethane as the reusable reaction medium.

3,3-Dinitratooxetane – an important leap towards energetic oxygen-rich monomers and polymers

3,3-Dinitratooxetane was prepared by the addition of dinitrogen pentoxide to oxetan-3-one and a crystal structure was obtained. Hot plate test of 3,3-dinitratooxetane (1).

Synthesis of Chiral N-Nitro-oxazolidin-2-ones and O-(β-Nitraminoalkyl) Carbamates in Liquefied 1,1,1,2-Tetrafluoroethane Medium

A convenient synthesis of chiral N-nitro-oxazolidin-2-ones by nitration of α-amino acid derived 1,3-oxazolidin-2-ones containing one or two stereogenic centers with dinitrogen pentoxide in liquefied 1,1,1,2-tetrafluoroethane medium has been developed. The obtained N-nitroheterocycles were converted into enantiomerically pure O-(β-nitraminoalkyl) carbamates by treatment with ammonia or amines in the same solvent. The synthesized N-nitro compounds are slightly toxic in vitro to Human Embryonic Kidney 293 (HEK293) cells.

Nitrate radical generation via continuous generation of dinitrogen pentoxide in a laminar flow reactor coupled to an oxidation flow reactor

Oxidation flow reactors (OFRs) are an emerging tool for studying the formation and oxidative aging of organic aerosols and other applications. The majority of OFR studies to date have involved the generation of the hydroxyl radical (OH) to mimic daytime oxidative aging processes. In contrast, the use of the nitrate radical (NO3) in modern OFRs to mimic nighttime oxidative aging processes has been limited due to the complexity of conventional techniques that are used to generate NO3. Here, we present a new method that uses a laminar flow reactor (LFR) to continuously generate dinitrogen pentoxide (N2O5) in the gas phase at room temperature from the NO2 + O3 and NO2 + NO3 reactions. The N2O5 is then injected into a dark Potential Aerosol Mass (PAM) OFR and decomposes to generate NO3; hereafter, this method is referred to as “OFR-iN2O5” (where “i” stands for “injected”). To assess the applicability of the OFR-iN2O5 method towards different chemical systems, we present experimental and model characterization of the integrated NO3 exposure, NO3:O3, NO2:NO3, and NO2:O2 as a function of LFR and OFR conditions. These parameters were used to investigate the fate of representative organic peroxy radicals (RO2) and aromatic alkyl radicals generated from volatile organic compound (VOC) + NO3 reactions, and VOCs that are reactive towards both O3 and NO3. Finally, we demonstrate the OFR-iN2O5 method by generating and characterizing secondary organic aerosol from the β-pinene + NO3 reaction.

Intercomparison of nitrogen monoxide and nitrogen dioxide measurements in the atmosphere simulation chamber SAPHIR during the MetNO2 campaign

<p>Nitrogen dioxide (NO<sub>2</sub>) and nitrogen monoxide (NO) govern the photochemical processes in the troposphere. Although nitrogen oxides have been measured for decades, their quantification remains challenging. The MetNO2 (Metrology for Nitrogen Dioxide) project of the European Metrology Programme for Innovation and Research (EMPIR) aims to improve the accuracy of NO<sub>2</sub> measurements.</p><p>In total 15 instruments were intercompared at the World Calibration Centre for nitrogen oxides (WCC-NOx) in Jülich in autumn 2019 within the project. In addition to chemiluminescence detectors (CLD), the instruments encompassed Quantum Cascade Laser Absorption Spectrometers (QCLAS), Iterative CAvity-enhanced Differential optical absorption spectrometers (ICAD) and Cavity Attenuated Phase Shift (CAPS) spectrometers.</p><p>During the campaign, air from a gas phase titration unit, air from the environmental chamber SAPHIR or outside air was provided to the instruments via a common inlet line. The participants calibrated their instruments prior and after the campaign with their own calibration procedures. During the campaign, the common inlet line was used for daily calibration to compare standards, calibration techniques and sensitivity drifts of the instruments. NO<sub>2</sub> for calibration was provided either by gas phase titration from NO, from permeation tubes or from gas mixtures produced within the MetNO2 project.</p><p>It was observed that measurements by chemiluminescence or CAPS instruments are prone to interferences from humidity and ozone. However, in most cases data can be corrected. Alkyl nitrates and reactive alkenes were also observed to cause interferences in some instruments, while isobutyl nitrite was found to be photolyzed by photolytic converters.</p><p>Finally, measurements in ambient air were compared. The nitrogen oxide observations were accompanied with measurements of hydroxyl radical (OH) reactivity and reactive nitrogen species as nitrous acid (HONO), dinitrogen pentoxide (N<sub>2</sub>O<sub>5</sub>), and chloryl nitrate (ClNO<sub>2</sub>). Detailed results of the intercomparison will be presented.</p>

Nitrate radical generation via continuous generation of dinitrogen pentoxide in a laminar flow reactor coupled to an oxidation flow reactor

Oxidation flow reactors (OFRs) are an emerging tool for studying the formation and oxidative aging of organic aerosols and other applications. The majority of OFR studies to date involved generation of the hydroxyl radical (OH) to mimic daytime oxidative aging processes. On the other hand, use of the nitrate radical (NO3) in modern OFRs to mimic nighttime oxidative aging processes has been limited due to the complexity of conventional techniques that are used to generate NO3. Here, we present a new method that uses a laminar flow reactor (LFR) to continuously generate dinitrogen pentoxide (N2O5) in the gas phase at room temperature from the NO2 + O3 and NO2 + NO3 reactions. The N2O5 is then injected into a dark Potential Aerosol Mass OFR and decomposes to generate NO3; hereafter, this method is referred to as OFR-iN2O5 (i = injected). To assess the applicability of the OFR-iN2O5 method towards different chemical systems, we present experimental and model characterization of the integrated NO3 exposure, NO3:O3, NO2:NO3, and NO2:O2 as a function of LFR and OFR conditions. These parameters were used to investigate the fate of representative organic peroxy radicals (RO2) and aromatic alkyl radicals generated from volatile organic compound (VOC) + NO3 reactions, and VOCs that are reactive towards both O3 and NO3. Finally, we demonstrate the OFR-iN2O5 method by generating and characterizing secondary organic aerosol from the β-pinene + NO3 reaction.