Organic Nitrate Formation Research Articles

Effect of NOx and SO2 on the photooxidation of methylglyoxal: Implications in secondary aerosol formation

Methylglyoxal (CH3COCHO, MG), which is one of the most abundant α-dicarbonyl compounds in the atmosphere, has been reported as a major source of secondary organic aerosol (SOA). In this work, the reaction of MG with hydroxyl radicals was studied in a 500 L smog chamber at (293 ± 3) K, atmospheric pressure, (18 ± 2)% relative humidity, and under different NOx and SO2. Particle size distribution was measured by using a scanning mobility particle sizer (SMPS) and the results showed that the addition of SO2 can promote SOA formation, while different NOx concentrations have different influences on SOA production. High NOx suppressed the SOA formation, whereas the particle mass concentration, particle number concentration and particle geometric mean diameter increased with the increasing NOx concentration at low NOx concentration in the presence of SO2. In addition, the products of the OH-initiated oxidation of MG and the functional groups of the particle phase in the MG/OH/SO2 and MG/OH/NOx/SO2 reaction systems were detected by gas chromatography mass spectrometry (GC-MS) and attenuated total reflection fourier transformed infrared spectroscopy (ATR-FTIR) analysis. Two products, glyoxylic acid and oxalic acid, were detected by GC-MS. The mechanism of the reaction of MG and OH radicals that follows two main pathways, H atom abstraction and hydration, is proposed. Evidence is provided for the formation of organic nitrates and organic sulfate in particle phase from IR spectra. Incorporation of NOx and SO2 influence suggested that SOA formation from anthropogenic hydrocarbons may be more efficient in polluted environment.

Effect of changing NO<sub><i>x</i></sub> lifetime on the seasonality and long-term trends of satellite-observed tropospheric NO<sub>2</sub> columns over China

Abstract. Satellite observations of tropospheric NO2 columns are extensively used to infer trends in anthropogenic emissions of nitrogen oxides (NOx≡NO+NO2), but this may be complicated by trends in NOx lifetime. Here we use 2004–2018 observations from the Ozone Monitoring Instrument (OMI) satellite-based instrument (QA4ECV and POMINO v2 retrievals) to examine the seasonality and trends of tropospheric NO2 columns over central–eastern China, and we interpret the results with the GEOS-Chem chemical transport model. The observations show a factor of 3 increase in NO2 columns from summer to winter, which we explain in GEOS-Chem as reflecting a longer NOx lifetime in winter than in summer (21 h versus 5.9 h in 2017). The 2005–2018 summer trends of OMI NO2 closely follow the trends in the Multi-resolution Emission Inventory for China (MEIC), with a rise over the 2005–2011 period and a 25 % decrease since. We find in GEOS-Chem no significant trend of the NOx lifetime in summer, supporting the emission trend reported by the MEIC. The winter trend of OMI NO2 is steeper than in summer over the entire period, which we attribute to a decrease in NOx lifetime at lower NOx emissions. Half of the NOx sink in winter is from N2O5 hydrolysis, which counterintuitively becomes more efficient as NOx emissions decrease due to less titration of ozone at night. The formation of organic nitrates also becomes an increasing sink of NOx as NOx emissions decrease but emissions of volatile organic compounds (VOCs) do not.

Characterization of a chemical amplifier for peroxy radical measurements in the atmosphere

Peroxy radicals (HO2 and RO2) are key species in atmospheric chemistry. They are produced during the oxidation of volatile organic compounds (VOCs) and are involved in the formation of photochemical pollutants such as ozone (O3) and secondary organic aerosols (SOA). However, ambient measurements of these reactive species are still challenging and only a few techniques can achieve both a good selectivity and a detection limit that is low enough for ambient measurements. In this publication we present the characterization of a Chemical Amplifier (CA) using two different approaches for ambient measurements of peroxy radicals, including the PEroxy Radical Chemical Amplifier (PERCA) and the Ethane based CHemical AMPlification (ECHAMP). At 50% Relative Humidity (RH), the experimental Chain Length (CL) for PERCA was found to be higher by approximately a factor of 3.7 compared to ECHAMP. The RH-dependence of the CL was also found to be larger for PERCA by a factor of 1.12. Box modeling of the chemistry taking place in the instrument highlighted that the formation of HNO3 from the HO2+NO reaction has a strong impact on the CL for both approaches. In addition, experiments conducted to quantify the RO2–to-HO2 conversion efficiency for a large range of organic peroxy radicals confirmed that it mainly depends on the organic nitrate (RONO2) formation yield, while the alkyl nitrite (RONO) yield is not limiting the CL in most cases. Ambient measurements using the PERCA approach are shown to illustrate the performances of this new instrument.

Interaction of long-lived reactive species from cold atmospheric pressure plasma with polymers: Chemical modification by ozone and reactive oxygen-nitrogen species

Atmospheric pressure plasma (APP) sources are able to generate a variety of reactive species that have different effects on materials, such as functionalization, etching, and deposition. In this article, the authors study the effect of long-lived reactive neutral species on polymers using a model plasma-surface interaction system that consists of ultrathin (∼10 nm) polystyrene (PS) films and a surface microdischarge (SMD) reactor operated with various N2/O2 working gas mixtures. The authors characterized and quantified the reactive species generated by SMD using IR and UV absorption, and they found that O3, N2O5, N2O, and HNO3 are the dominant long-lived reactants near the target surface. When exposing PS films to these reactive species, the authors observed material responses including film thickness expansion, surface and bulk oxidation, and surface organic nitrate formation. The quantity of these changes varied with the N2/O2 working gas composition. By correlating material response with gas phase species, the authors find that the chemical modification of PS strongly depends on the density of O3 in the gas phase, which is indicative of an essential role of O3 in the remote APP treatment of polymers. Authors’ results show that O3 causes polymer surface oxidation, participates in the diffusion-reaction process in the polymer bulk, and results in aromatic ring cleavage and the formation of carbonyl groups. In contrast, they did not find a correlation between surface organic nitrate and individual long-lived reactive species mentioned above. This indicates that the organic nitrate formation on polymer surfaces might result from the interaction of multiple species, including O3 and nitrogen containing reactive species. A model for the interphase mass transfer of reactive species from gas to solid was also described.

Vapor-pressure pathways initiate but hydrolysis products dominate the aerosol estimated from organic nitrates.

Organic nitrates contribute significantly to the total organic aerosol burden. However, the formation and loss mechanisms of particulate organic nitrates (PONs) remain poorly understood. In this study, with the CMAQ modeling system, we implement a detailed biogenic volatile organic carbon gas phase oxidation mechanism and an explicit representation of multiphase organic nitrate formation and loss, including both aqueous-phase uptake and vapor-pressure driven partitioning into organic aerosol as well as condensed-phase reactions. We find vapor-pressure dependent partitioning is the leading mechanism for formation of PONs and hydrolysis is a major loss mechanism for PON resulting in substantial amounts of organic aerosol that originate as an organic nitrate. Partitioning and hydrolysis together can produce high concentrations (up to 5 μg/m3) of PON-derived aerosols over the southeast United States. The main source of PON-derived aerosols is monoterpene nitrates that have been chemically processed to lose their nitrate functionality through aqueous chemistry. In contrast, the major portion of aqueous aerosol and in-cloud PON, which retains its nitrate moiety, are soluble isoprene nitrates. We evaluate the model using the observations from the Southern Oxidant and Aerosol Study (SOAS) campaign in the Southeast US in summer 2013 and show implementing aerosol-phase pathways for organic nitrates dramatically improves the magnitude of total alkyl nitrates (ANs) in CMAQ. The contribution of PONs to the total ANs at the SOAS site is estimated to be ~20%, a value in the range of the measurements. The predicted AN composition is shifted from monoterpene to isoprene and anthropogenic organic nitrates.

Characterization of nighttime formation of particulate organic nitrates based on high-resolution aerosol mass spectrometry in an urban atmosphere in China

Abstract. Organic nitrates are important atmospheric species that significantly affect the cycling of NOx and ozone production. However, characterization of particulate organic nitrates and their sources in polluted atmosphere is a big challenge and has not been comprehensively studied in Asia. In this study, an aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was deployed at an urban site in China from 2015 to 2016 to characterize particulate organic nitrates in total nitrates with a high time resolution. Based on the cross-validation of two different data processing methods, organic nitrates were effectively quantified to contribute a notable fraction of organic aerosol (OA), namely 9 %–21 % in spring, 11 %–25 % in summer, and 9 %–20 % in autumn, while contributing a very small fraction in winter. The good correlation between organic nitrates and fresh secondary organic aerosol (SOA) at night, as well as the diurnal trend of size distribution of organic nitrates, indicated a key role of nighttime local secondary formation of organic nitrates. Furthermore, theoretical calculations of nighttime SOA production of NO3 reactions with volatile organic compounds (VOCs) measured during the spring campaign were performed, resulting in three biogenic VOCs (α-pinene, limonene, and camphene) and one anthropogenic VOC (styrene) identified as the possible key VOC precursors to particulate organic nitrates. The comparison with similar studies in the literature implied that nighttime particulate organic nitrate formation is highly relevant to NOx levels. This study proposes that unlike the documented cases in the United States and Europe, modeling nighttime particulate organic nitrate formation in China should incorporate not only biogenic VOCs but also anthropogenic VOCs for urban air pollution, which needs the support of relevant smog chamber studies in the future.

Secondary organic aerosol formation from the OH-initiated oxidation of guaiacol under different experimental conditions

Guaiacol (2-methoxyphenol) has a high emission rate from wood burning and mainly exists in the gas phase, but the formation potential of secondary organic aerosol (SOA) from the atmospheric oxidation of guaiacol has not been well determined yet. In this work, SOA formation from the gas-phase reaction of guaiacol with OH radicals was investigated using an oxidation flow reactor (OFR) under different experimental conditions. The results showed that SOA yield was dependent on guaiacol concentration, OH exposure, and the presence of SO2 and NO2. SOA yield firstly increased and then decreased as a function of OH exposure. The maximum SOA yield (0.28–0.54) obtained at different guaiacol concentrations could be well-expressed by a one-product model. The SOA oxidation degree was represented by the carbon oxidation state (OSC) and f44/f43 (the ratio of organic mass fractions of m/z 44 to m/z 43), which both increased linearly and significantly with the increase of OH exposure. In addition, SO2 and NO2 promoted SOA formation, for which the maximum yield enhancements were 13.38% and 10.69%, respectively. The N/C ratio (0.034–0.045) indicated that NO2 participated in the OH-initiated reaction of guaiacol, consequently resulting in the formation of organic nitrates. The experimental results would be helpful to further the understanding of SOA formation from the atmospheric oxidation of guaiacol and its subsequent impacts on air quality and climate.

Nighttime secondary organic aerosol formation from unburned fuel vapors

Nighttime secondary organic aerosol (SOA) formation was investigated for unburned vapors of three different fuels (Fuel #1, Fuel #2, and Fuel #3) in the presence of NO and ozone. Fuel #1 and Fuel #2 contained gasoline-range components with Fuel #1 being rich in aromatics and Fuel #2 being rich in olefins. Fuel #3 contained diesel-range components. The SOA formation from Fuel #1 and Fuel #3 showed a continuous increase in the aerosol mass loading as a function of initial NO concentration. However, for Fuel #2, while the aerosol mass loading increased at higher NO concentrations, the results from this study indicated they were initially suppressed by the presence of olefins that can rapidly react with nitrate radicals. The evolution of the mass spectra of the formed aerosols indicated that their chemical composition continued to change even after termination of aerosol formation due to additional oxidation reactions during the aging process. Off-line Direct Analysis in Real Time Mass Spectrometry (DART-MS) was conducted on the formed SOA collected on filters and the analysis indicated that the SOA was mainly composed of highly oxidized compounds. It is hypothesized that olefins could interact with NO3∙ leading to the formation of heavier organic nitrates through addition or oligomerization reactions. Insights from the current study may help to improve regional air quality control policies and methodologies for future multi-day modeling studies.

Dynamic changes in optical and chemical properties of tar ball aerosols by atmospheric photochemical aging

Abstract. Following wood pyrolysis, tar ball aerosols were laboratory generated from wood tar separated into polar and nonpolar phases. Chemical information of fresh tar balls was obtained from a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and single-particle laser desorption/resonance enhanced multiphoton ionization mass spectrometry (SP-LD-REMPI-MS). Their continuous refractive index (RI) between 365 and 425 nm was retrieved using a broadband cavity enhanced spectroscopy (BBCES). Dynamic changes in the optical and chemical properties for the nonpolar tar ball aerosols in NOx-dependent photochemical process were investigated in an oxidation flow reactor (OFR). Distinct differences in the chemical composition of the fresh polar and nonpolar tar aerosols were identified. Nonpolar tar aerosols contain predominantly high-molecular weight unsubstituted and alkyl-substituted polycylic aromatic hydrocarbons (PAHs), while polar tar aerosols consist of a high number of oxidized aromatic substances (e.g., methoxy-phenols, benzenediol) with higher O : C ratios and carbon oxidation states. Fresh tar balls have light absorption characteristics similar to atmospheric brown carbon (BrC) aerosol with higher absorption efficiency towards the UV wavelengths. The average retrieved RI is 1.661+0.020i and 1.635+0.003i for the nonpolar and polar tar aerosols, respectively, with an absorption Ångström exponent (AAE) between 5.7 and 7.8 in the detected wavelength range. The RI fits a volume mixing rule for internally mixed nonpolar/polar tar balls. The RI of the tar ball aerosols decreased with increasing wavelength under photochemical oxidation. Photolysis by UV light (254 nm), without strong oxidants in the system, slightly decreased the RI and increased the oxidation state of the tar balls. Oxidation under varying OH exposure levels and in the absence of NOx diminished the absorption (bleaching) and increased the O : C ratio of the tar balls. The photobleaching via OH radical initiated oxidation is mainly attributed to decomposition of chromophoric aromatics, nitrogen-containing organics, and high-molecular weight components in the aged particles. Photolysis of nitrous oxide (N2O) was used to simulate NOx-dependent photochemical aging of tar balls in the OFR. Under high-NOx conditions with similar OH exposure, photochemical aging led to the formation of organic nitrates, and increased both oxidation degree and light absorption for the aged tar ball aerosols. These observations suggest that secondary organic nitrate formation counteracts the bleaching by OH radical photooxidation to eventually regain some absorption of the aged tar ball aerosols. The atmospheric implication and climate effects from tar balls upon various oxidation processes are briefly discussed.

Computational study on the mechanism and kinetics of NO3-initiated atmosphere oxidation of vinyl acetate

It is known the NO3 radical contributes to the oxidation of volatile organic compounds in the atmosphere in the night, leading to the formation of carbonyl compounds and organic nitrates. The mechanistic and kinetic properties of NO3-initiated oxidative degradation of vinyl acetate (VAC), a typical unsaturated ester, have been studied using density functional method. According to the computational results, two types of primary reactions were identified: NO3-addition and H-abstraction. The NO3-addition reaction especially the Cβ-addition pathway dominates the entrance channel of NO3 into VAC while the H-abstraction reaction is negligible. Further reactions of the two adducts were discussed in the presence of O2/NOx. The rate constants were estimated by using the MultiWell software. The overall rate constant of NO3-initiated oxidation of VAC was about 7.30 × 10−15 cm3 molecule−1 s−1 at 298.15 K and atmospheric pressure, in good agreement with the experimental value of (7.30 ± 1.8) × 10−15 cm3 molecule−1 s−1. The atmospheric lifetime of VAC reacting with NO3 radicals (5.0 × 108 molecule cm−3) is about 76.1 h under atmospheric conditions.

Direct measurements of NO<sub>3</sub> reactivity in and above the boundary layer of a mountaintop site: identification of reactive trace gases and comparison with OH reactivity

Abstract. We present direct measurements of the summertime total reactivity of NO3 towards organic trace gases, kOTGNO3, at a rural mountain site (988 m a.s.l.) in southern Germany in 2017. The diel cycle of kOTGNO3 was strongly influenced by local meteorology with high reactivity observed during the day (values of up to 0.3 s−1) and values close to the detection limit (0.005 s−1) at night when the measurement site was in the residual layer and free troposphere. Daytime values of kOTGNO3 were sufficiently large that the loss of NO3 due to reaction with organic trace gases competed with its photolysis and reaction with NO. Within experimental uncertainty, monoterpenes and isoprene accounted for all of the measured NO3 reactivity. Averaged over the daylight hours, more than 25 % of NO3 was removed via reaction with biogenic volatile organic compounds (BVOCs), implying a significant daytime loss of NOx and the formation of organic nitrates due to NO3 chemistry. Ambient NO3 concentrations were measured on one night and were comparable to those derived from a stationary-state calculation using measured values of kOTGNO3. We present and compare the first simultaneous, direct reactivity measurements for the NO3 and OH radicals. The decoupling of the measurement site from ground-level emissions resulted in lower reactivity at night for both radicals, though the correlation between OH and NO3 reactivity was weak as would be anticipated given their divergent trends in rate constants with many organic trace gases.

Insights into the degradation of (CF3)2CHOCH3 and its oxidative product (CF3)2CHOCHO & the formation and catalytic degradation of organic nitrates

In this work, a systematic investigation of the atmospheric oxidation mechanism of (CF3)2CXOCH3 and their oxidative products (CF3)2CXOCHO (X = H, F) initiated by OH radical or Cl atom is performed by density functional theory. This study reveals that the introduction of NO and O2 promotes the formation of organic nitrates, which are hygroscopic and are inclined to form secondary organic aerosols (SOA) and can affect the air quality. The rate constants of the individual reactions are found to be in agreement with the experimental results. One of the intriguing findings of this work is that the peroxynitrite of (CF3)2CHOCH2OONO formed from the subsequent reactions of (CF3)2CHOCH3 is more favorable to isomerize to organic nitrate (CF3)2CHOCH2ONO2 than to dissociate into alkoxy radical (CF3)2CHOCH2O and NO2 because of the lower energy barrier of isomerization. The second significant observation is that the organic nitrate can be degraded more favorably with the presence of NH3, CH3NH2, and CH3NHCH3 than its naked decomposition reaction (CF3)2CHOCH2ONO2→(CF3)2CHOCHO + HONO. The ammonium salt, a vital part of haze, is harmful to human health and can be formed in the existence of the NH3, CH3NH2, and CH3NHCH3. In addition, the toxic substance of peroxyalkyl nitrate (CF3)2CHOC(O)ONO2 which can reduce the visibility of the atmosphere is produced as the primary subsequent oxidation product of (CF3)2CHOCHO in a NO-rich environment. The main species detected experimentally are confirmed by this study. The computational results are crucial to risk assessment and pollution prevention of the volatile organic compounds (VOCs).

A chamber study of alkyl nitrate production formed by terpene ozonolysis in the presence of NO and alkanes

Organic nitrates are relatively long-lived species and have been shown to have a potential impact on atmospheric chemistry on local, regional, and even global scales. However, the significance of these compounds in the indoor environment remains to be seen. This work describes an impinger-based sampling and analysis technique for organic nitrate species, focusing on formation via terpene ozonolysis in the presence of nitric oxide (NO). Experiments were conducted in a Teflon film environmental chamber to measure the formation of alkyl nitrates produced from α-pinene ozonolysis in the presence of NO and alkanes using gas chromatography with an electron capture detector. For the different concentrations of NO and O3 analyzed, the concentration ratio of [O3]/[NO] around 1 was found to produce the highest organic nitrate concentration, with [O3] = 100 ppb & [NO] = 105 ppb resulting in the most organic nitrate formation, roughly 5 ppb. The experiments on α-pinene ozonolysis in the presence of NO suggest that organic nitrates have the potential to form in indoor air between infiltrated ozone/NO and terpenes from household and consumer products.

Day and night-time formation of organic nitrates at a forested mountain site in south-west Germany

Abstract. We report in situ measurements of total peroxy nitrates (ΣPNs) and total alkyl nitrates (ΣANs) in a forested–urban location at the top of the Kleiner Feldberg mountain in south-west Germany. The data, obtained using thermal dissociation cavity ring-down spectroscopy (TD-CRDS) in August–September 2011 (PARADE campaign) and July 2015 (NOTOMO campaign), represent the first detailed study of ΣPNs and ΣANs over continental Europe. We find that a significant fraction of NOx (up to 75 %) is sequestered as organics nitrates at this site. Furthermore, we also show that the night-time production of alkyl nitrates by reaction of NO3 with biogenic hydrocarbons is comparable to that from daytime OH-initiated oxidation pathways. The ΣANs ∕ ozone ratio obtained during PARADE was used to derive an approximate average yield of organic nitrates at noon from the OH initiated oxidation of volatile organic compounds (VOCs) of ∼ 7 % at this site in 2011, which is comparable with that obtained from an analysis of VOCs measured during the campaign. A much lower AN yield, < 2 %, was observed in 2015, which may result from sampling air with different average air mass ages and thus different degrees of breakdown of assumptions used to derive the branching ratio, but it may also reflect a seasonal change in the VOC mixture at the site.

Nitrate radicals and biogenic volatile organic compounds: oxidation, mechanisms, and organic aerosol.

Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO3) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO3-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain. These include an incomplete understanding of the rates, mechanisms, and organic aerosol yields for NO3-BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO3 radical, the difficulty of characterizing the spatial distributions of BVOC and NO3 within the poorly mixed nocturnal atmosphere, and the challenge of constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry–climate models.This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first half of the review summarizes the current literature on NO3-BVOC chemistry, with a particular focus on recent advances in instrumentation and models, and in organic nitrate and secondary organic aerosol (SOA) formation chemistry. Building on this current understanding, the second half of the review outlines impacts of NO3-BVOC chemistry on air quality and climate, and suggests critical research needs to better constrain this interaction to improve the predictive capabilities of atmospheric models.

Ozone sensitivity to isoprene chemistry and emissions and anthropogenic emissions in central California

Ozone formation in California in year 2017 was simulated using three chemical mechanisms: the Statewide Air Pollution Research Center 2007 mechanism with updated toxics and isoprene chemistry (S07TIC); the Carbon Bond 6, revision 2 (CB6r2) mechanism; a modified CB6r2 mechanism with increased hydroxyl radical (OH) production from isoprene oxidation at low nitrogen oxide (NOx) concentrations (CB6r2OH). The simulations with a photochemical grid model (PGM) showed little difference in ozone between CB6r2 and CB6r2OH. Further analysis with a box model found little sensitivity of ozone to OH production in the isoprene chemistry of all three mechanisms under conditions representative of California. The S07TIC generally predicts greater ozone than the CB6r2, and the difference in the predicted concentrations exceeds the uncertainty estimated from uncertainties in the emissions inventory. The sensitivity of ozone to anthropogenic volatile organic compound (VOC), NOx and carbon monoxide (CO) emissions and to isoprene emissions was also calculated with the PGM. Accounting for uncertainties in the emissions inventory, the sensitivity to NOx emissions is significantly different between S07TIC and CB6r2 in central and northern California; the sensitivity to isoprene emissions is significantly different in southern California. All mechanisms give a negative sensitivity of ozone to isoprene emissions in areas of northern California where NOx emissions are small. The CB6r2 and S07TIC differ in the sensitivity of ozone to organic nitrate (ON) formation from isoprene oxidation, likely because all ONs recycle to NOx in the S07TIC mechanism but only first-generation ONs do so in the CB6r2. For current California conditions, uncertainties in OH production from isoprene have little impact on ozone, but the extent to which isoprene ONs recycle NOx does impact ozone concentration and ozone sensitivity to NOx emissions.

Organic Nitrate Contribution to New Particle Formation and Growth in Secondary Organic Aerosols from α-Pinene Ozonolysis.

The chemical kinetics of organic nitrate production during new particle formation and growth of secondary organic aerosols (SOA) were investigated using the short-lived radioactive tracer (13)N in flow-reactor studies of α-pinene oxidation with ozone. Direct and quantitative measurements of the nitrogen content indicate that organic nitrates accounted for ∼40% of SOA mass during initial particle formation, decreasing to ∼15% upon particle growth to the accumulation-mode size range (>100 nm). Experiments with OH scavengers and kinetic model results suggest that organic peroxy radicals formed by α-pinene reacting with secondary OH from ozonolysis are key intermediates in the organic nitrate formation process. The direct reaction of α-pinene with NO3 was found to be less important for particle-phase organic nitrate formation. The nitrogen content of SOA particles decreased slightly upon increase of relative humidity up to 80%. The experiments show a tight correlation between organic nitrate content and SOA particle-number concentrations, implying that the condensing organic nitrates are among the extremely low volatility organic compounds (ELVOC) that may play an important role in the nucleation and growth of atmospheric nanoparticles.

Organic nitrate chemistry and its implications for nitrogen budgets in an isoprene- and monoterpene-rich atmosphere: constraints from aircraft (SEAC4RS) and ground-based (SOAS) observations in the Southeast US.

Formation of organic nitrates (RONO2) during oxidation of biogenic volatile organic compounds (BVOCs: isoprene, monoterpenes) is a significant loss pathway for atmospheric nitrogen oxide radicals (NOx), but the chemistry of RONO2 formation and degradation remains uncertain. Here we implement a new BVOC oxidation mechanism (including updated isoprene chemistry, new monoterpene chemistry, and particle uptake of RONO2) in the GEOS-Chem global chemical transport model with ∼25 × 25 km2 resolution over North America. We evaluate the model using aircraft (SEAC4RS) and ground-based (SOAS) observations of NOx, BVOCs, and RONO2 from the Southeast US in summer 2013. The updated simulation successfully reproduces the concentrations of individual gas- and particle-phase RONO2 species measured during the campaigns. Gas-phase isoprene nitrates account for 25-50% of observed RONO2 in surface air, and we find that another 10% is contributed by gas-phase monoterpene nitrates. Observations in the free troposphere show an important contribution from long-lived nitrates derived from anthropogenic VOCs. During both campaigns, at least 10% of observed boundary layer RONO2 were in the particle phase. We find that aerosol uptake followed by hydrolysis to HNO3 accounts for 60% of simulated gas-phase RONO2 loss in the boundary layer. Other losses are 20% by photolysis to recycle NOx and 15% by dry deposition. RONO2 production accounts for 20% of the net regional NOx sink in the Southeast US in summer, limited by the spatial segregation between BVOC and NOx emissions. This segregation implies that RONO2 production will remain a minor sink for NOx in the Southeast US in the future even as NOx emissions continue to decline.

Modeling the Current and Future Roles of Particulate Organic Nitrates in the Southeastern United States.

Organic nitrates are an important aerosol constituent in locations where biogenic hydrocarbon emissions mix with anthropogenic NOx sources. While regional and global chemical transport models may include a representation of organic aerosol from monoterpene reactions with nitrate radicals (the primary source of particle-phase organic nitrates in the Southeast United States), secondary organic aerosol (SOA) models can underestimate yields. Furthermore, SOA parametrizations do not explicitly take into account organic nitrate compounds produced in the gas phase. In this work, we developed a coupled gas and aerosol system to describe the formation and subsequent aerosol-phase partitioning of organic nitrates from isoprene and monoterpenes with a focus on the Southeast United States. The concentrations of organic aerosol and gas-phase organic nitrates were improved when particulate organic nitrates were assumed to undergo rapid (τ = 3 h) pseudohydrolysis resulting in nitric acid and nonvolatile secondary organic aerosol. In addition, up to 60% of less oxidized-oxygenated organic aerosol (LO-OOA) could be accounted for via organic nitrate mediated chemistry during the Southern Oxidants and Aerosol Study (SOAS). A 25% reduction in nitrogen oxide (NO + NO2) emissions was predicted to cause a 9% reduction in organic aerosol for June 2013 SOAS conditions at Centreville, Alabama.

Investigating the links between ozone and organic aerosol chemistry in a biomass burning plume from a prescribed fire in California chaparral

Abstract. Within minutes after emission, complex photochemistry in biomass burning smoke plumes can cause large changes in the concentrations of ozone (O3) and organic aerosol (OA). Being able to understand and simulate this rapid chemical evolution under a wide variety of conditions is a critical part of forecasting the impact of these fires on air quality, atmospheric composition, and climate. Here we use version 2.1 of the Aerosol Simulation Program (ASP) to simulate the evolution of O3 and secondary organic aerosol (SOA) within a young biomass burning smoke plume from the Williams prescribed fire in chaparral, which was sampled over California in November 2009. We demonstrate the use of a method for simultaneously accounting for the impact of the unidentified intermediate volatility, semi-volatile, and extremely low volatility organic compounds (here collectively called "SVOCs") on the formation of OA (using the Volatility Basis Set – VBS) and O3 (using the concept of mechanistic reactivity). We show that this method can successfully simulate the observations of O3, OA, NOx, ethylene (C2H4), and OH to within measurement uncertainty using reasonable assumptions about the average chemistry of the unidentified SVOCs. These assumptions were (1) a reaction rate constant with OH of ~ 10-11 cm3 s−1; (2) a significant fraction (up to ~ 50 %) of the RO2 + NO reaction resulted in fragmentation, rather than functionalization, of the parent SVOC; (3) ~ 1.1 molecules of O3 were formed for every molecule of SVOC that reacted; (4) ~ 60 % of the OH that reacted with the unidentified non-methane organic compounds (NMOC) was regenerated as HO2; and (5) that ~ 50 % of the NO that reacted with the SVOC peroxy radicals was lost, presumably to organic nitrate formation. Additional evidence for the fragmentation pathway is provided by the observed rate of formation of acetic acid (CH3COOH), which is consistent with our assumed fragmentation rate. However, the model overestimates peroxyacetyl nitrate (PAN) formation downwind by about 50 %, suggesting the need for further refinements to the chemistry. This method could provide a way for classifying different smoke plume observations in terms of the average chemistry of their SVOCs, and could be used to study how the chemistry of these compounds (and the O3 and OA they form) varies between plumes.