Interpretation of NO₃–N₂O₅ observation via steady state in high aerosol air mass: The impact of equilibrium coefficient in ambient conditions

Steady state approximation for interpreting NO3 and N2O5 has large uncertainty under complicated ambient conditions and could even produces incorrect results unconsciously. To provide an assessment and solution to the dilemma, we formulate data sets based on in-situ observations to reassess the applicability of the method. In most of steady state cases, we find a prominent discrepancy between Keq (equilibrium coefficient for reversible reactions of NO3 and N2O5) and correspondingly simulated [N2O5]/([NO2]×[NO3]), especially in wintertime high aerosol conditions. This gap reveals the accuracy of Keq has a critical impact on the steady state analysis in polluted region. In addition, the accuracy of γ(N2O5) derived by steady state fit depends closely on the reactivity of NO3 (kNO3) and N2O5 (kN2O5). Based on a complete set of simulations, air mass of kNO3 less than 0.01 s−1 with high aerosol and temperature higher than 10 °C is suggested to be the best suited for steady state analysis of NO3–N2O5 chemistry. Instead of confirming the validity of steady state by numerical modeling for every case, this work directly provides concentration ranges appropriate for accurate steady state approximation, with implications for choosing suited methods to interpret nighttime chemistry in high aerosol air mass.

Increase of nitrooxy organosulfates in firework-related urban aerosols during Chinese New Year's Eve

Little is known about the formation processes of nitrooxy organosulfates (OSs) by nighttime chemistry. Here we characterize nitrooxy OSs at a molecular level in firework-related aerosols in urban Beijing during Chinese New Year. High-molecular-weight nitrooxy OSs with relatively low H / C and O / C ratios and high unsaturation are potentially aromatic-like nitrooxy OSs. They considerably increased during New Year's Eve, affected by the firework emissions. We find that large quantities of carboxylic-rich alicyclic molecules possibly formed by nighttime reactions. The sufficient abundance of aliphatic-like and aromatic-like nitrooxy OSs in firework-related aerosols demonstrates that anthropogenic volatile organic compounds are important precursors of urban secondary organic aerosols (SOAs). In addition, more than 98 % of those nitrooxy OSs are extremely low-volatility organic compounds that can easily partition into and consist in the particle phase and affect the volatility, hygroscopicity, and even toxicity of urban aerosols. Our study provides new insights into the formation of nitrooxy organosulfates from anthropogenic emissions through nighttime chemistry in the urban atmosphere.

Formation of condensable organic vapors from anthropogenic and biogenic VOCs is strongly perturbed by NO_x in eastern China

Oxygenated organic molecules (OOMs) are the crucial intermediates linking volatile organic compounds (VOCs) to secondary organic aerosol (SOA) in the atmosphere, but understandings on the characteristics of OOMs and their formations from VOCs are very limited. Ambient observations of OOMs using recently developed mass spectrometry techniques are still limited, especially in polluted urban atmosphere where VOCs and oxidants are extremely variable and complex. Here, we investigate OOMs, measured by a nitrate-ion-based chemical ionization mass spectrometer at Nanjing in eastern China, through performing positive matrix factorization on binned mass spectra (binPMF). The binPMF analysis reveals three factors about anthropogenic VOCs (AVOCs) daytime chemistry, three isoprene-related factors, three factors about biogenic VOCs (BVOCs) nighttime chemistry, and three factors about nitrated phenols. All factors are influenced by NOx in different ways and to different extents. Over 1000 non-nitro molecules have been identified and then reconstructed from the selected solution of binPMF, and about 72 % of the total signals are contributed by nitrogen-containing OOMs, mostly regarded as organic nitrates formed through peroxy radicals terminated by nitric oxide or nitrate-radical-initiated oxidations. Moreover, multi-nitrates account for about 24 % of the total signals, indicating the significant presence of multiple generations, especially for isoprene (e.g., C5H10O8N2 and C5H9O10N3). Additionally, the distribution of OOMs concentration on carbon number confirm their precursors driven by AVOCs mixed with enhanced BVOCs during summer. Our results highlight the decisive role of NOx on OOMs formation in densely populated areas, and encourage more studies on the dramatic interactions between anthropogenic and biogenic emissions.

Impact of firework on nitrooxy-organosulfates in urban aerosols during Chinese New Year Eve

Little is known about the formation processes of nitrooxy-organosulfates (nitrooxy-OSs) by nighttime chemistry. Here we characterize nitrooxy-OSs at a molecular level in firework-related aerosols in urban Beijing during Chinese New Year. High-molecular-weight nitrooxy-OSs with relatively low H / C and O / C ratios and high unsaturation, which are potentially aromatic-like nitrooxy-OSs, considerably increased during the New Year’s Eve. We find that large quantities of carboxylic-rich alicyclic molecules possibly formed by nighttime reactions. The sufficient abundance of aliphatic-like and aromatic-like nitrooxy-OSs demonstrates that both anthropogenic and biogenic volatile organic compounds are essential precursors of urban secondary organic aerosols (SOA). Besides, more than 98 % of nitrooxy-OSs were extremely low-volatile organic compounds that could easily partition into and consist in the particle phase, and affected the volatility, hygroscopicity, and even toxicity of urban aerosols. Our study provides new insights into the formation of nitrooxy-organosulfates from anthropogenic emissions through nighttime chemistry in the urban atmosphere.

Formation of (nitrooxy)organosulfates from organic peroxides and S(IV) via daytime and nighttime chemistry

<p>Sulfur and nitrogen containing organic compounds, such as organosulfates (OSs) and nitrooxy organosulfates (NOSs), are recognized to be ubiquitously present in secondary organic aerosol (SOA). However, little is known about the chemical mechanisms or the required conditions for the formation of these compounds in the ambient atmosphere. Earlier studies have commonly suggested that OSs are predominantly formed through the reaction of organic gaseous epoxides with acidic sulfate particles. However, this epoxide pathway often fails to explain the formation of (N)OSs from monoterpenes. Moreover, recent studies highlight the potential role of gas-phase SO<sub>2</sub> and organic peroxides for the formation of OSs, which might serve as predominant precursors for OSs and NOSs from atmospheric monoterpene oxidation.</p><p>Here, we conducted a series of chamber experiments to elucidate the formation mechanisms of (N)OSs from α-pinene oxidation during daytime and nighttime conditions. In particular, we focused on the role of organic peroxides and S(IV) (i.e., gas-phase SO<sub>2</sub> and particulate SO<sub>3</sub><sup>2–</sup>) in contrast to organic epoxides and isotope-labelled particulate sulfate (i.e., S(VI)). SOA particles were analyzed online by extractive electrospray ionization coupled with high-resolution Orbitrap mass spectrometry (EESI-Orbitrap MS) allowing an unambiguous identification of OS and NOS species with a high time resolution. Additionally, filter samples were collected and analyzed by liquid chromatography (LC) coupled with Orbitrap MS to determine the presence of isomeric compounds.</p><p>Consistently, online and offline Orbitrap MS analysis showed that particulate sulfate played a minor role in the formation of OSs and NOSs. In contrast, (N)OSs were rapidly formed upon addition of either gaseous SO<sub>2</sub> or particulate SO<sub>3</sub><sup>2–</sup>, suggesting S(IV) to react with organic peroxides that were formed through monoterpene oxidation. Based on these experiments, we identified specific NOS species that are formed only through either daytime or nighttime chemistry, and thus, might serve as marker molecules. Moreover, we present complete formation pathways for these species. Our study indicates that in contrast to previous work, the formation of OSs and NOSs does not require acidic sulfate particles, but rather involves the reaction of organic peroxides with S(IV) in the gas phase or the particle phase.</p>

Molecular Characterization of Firework-Related Urban Aerosols using FT-ICR Mass Spectrometry

<p>Firework (FW) emissions have strong impacts on air quality and public health. However, little is known about the molecular composition of FW-related aerosols especially the organic fraction. Here we describe the detailed molecular composition of Beijing aerosols collected before, during, and after a FW event in New Year's Eve evening. Subgroups of CHO, CHNO, CHOS, and CHNOS were characterized using ultrahigh resolution Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometry. We found that high molecular weight compounds with relatively low H/C and O/C ratios and high degree of unsaturation were greatly enhanced during the New Year’s Eve, which are likely to be aromatic-like compounds. They plausibly contributed to the formation of brown carbon and affect the light absorption properties of atmospheric aerosols. Moreover, the number concentration of sulfur-containing compounds especially the nitrooxy-organosulfate was increased dramatically by the FW event, suggesting the important effect of nighttime chemistry on their formation. But, the number concentration of CHO and CHON doubled after the event with photooxidation. The co-variation of these subgroups was suggested to be associated with multiple atmospheric aging processes of aerosols including the multiphase redox chemistry driven by NO<sub>x</sub>, O<sub>3</sub>, and <sup>·</sup>OH. Our study provides new insights into the anthropogenic emissions for urban SOA formation.</p>

Cavity enhanced spectroscopy for measurement of nitrogen oxides in the Anthropocene: results from the Seoul tower during MAPS 2015

Cavity enhanced spectroscopy, CES, is a high sensitivity direct absorption method that has seen increasing utility in the last decade, a period also marked by increasing requirements for understanding human impacts on atmospheric composition. This paper describes the current NOAA six channel cavity ring-down spectrometer (CRDS, the most common form of CES) for measurement of nitrogen oxides and O3. It further describes the results from measurements from a tower 300 m above the urban area of Seoul in late spring of 2015. The campaign demonstrates the performance of the CRDS instrument and provides new data on both photochemistry and nighttime chemistry in a major Asian megacity. The instrument provided accurate, high time resolution data for N2O5, NO, NO2, NOyand O3, but suffered from large wall loss in the sampling of NO3, illustrating the requirement for calibration of the NO3inlet transmission. Both the photochemistry and nighttime chemistry of nitrogen oxides and O3were rapid in this megacity. Sustained average rates of O3buildup of 10 ppbv h−1during recurring morning and early afternoon sea breezes led to a 50 ppbv average daily O3rise. Nitrate radical production rates,P(NO3), averaged 3–4 ppbv h−1in late afternoon and early evening, much greater than contemporary data from Los Angeles, a comparable U. S. megacity. TheseP(NO3) were much smaller than historical data from Los Angeles, however. Nighttime data at 300 m above ground showed considerable variability in high time resolution nitrogen oxide and O3, likely resulting from sampling within gradients in the nighttime boundary layer structure. Apparent nighttime biogenic VOC oxidation rates of several ppbv h−1were also likely influenced by vertical gradients. Finally, daytime N2O5mixing ratios of 3–35 pptv were associated with rapid daytimeP(NO3) and agreed well with a photochemical steady state calculation.