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Chapter 6
Organic Nitrates and Secondary Organic Aerosol (SOA) Formation from Oxidation of Biogenic Volatile Organic Compounds M. Takeuchi1 and N. L. Ng2,3,* 1School of Civil and Environmental Engineering, Georgia Institute of Technology, 790 Atlantic Dr. NW, Atlanta, Georgia 30332, United States 2School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Dr. NW, Atlanta, Georgia 30332, United States 3School of Earth and Atmospheric Sciences, Georgia Institute of Technology, 311 Ferst Dr. NW, Atlanta, Georgia 30332, United States *E-mail:
[email protected] Organic nitrates (ON) originating from biogenic volatile organic compounds (BVOC) are ubiquitous in the atmosphere and play an important role in NOx recycling, ozone, and secondary organic aerosol (SOA) formation, though a fundamental understanding on their formation and fates remains largely unexplored. This chapter reviews the current knowledge of BVOC-derived ON chemistry. Topics range from ON formation mechanisms, yields, fates, measurement techniques, implication on SOA formation, field observations, and recommendations for future research.
Introduction Organic aerosols (OA) constitute a substantial fraction of fine particulate matter (PM2.5) in the atmosphere and have important impacts on climate, visibility, and human health (1, 2). Primary OA (POA) are directly emitted into the atmosphere as PM; secondary OA (SOA) are formed in the atmosphere from the oxidation of gas-phase compounds followed by gas-particle partitioning. Ambient field studies have found that SOA contribute a significant fraction of OA and often dominate over POA even in urban areas (3–7). A detailed understanding
© 2018 American Chemical Society Hunt et al.; Multiphase Environmental Chemistry in the Atmosphere ACS Symposium Series; American Chemical Society: Washington, DC, 2018.
of the formation and evolution of SOA is vital to assess the effects of PM on climate and health. Owing to their high emissions and high reactivity with the major atmospheric oxidants, such as ozone, hydroxyl radical (OH) and nitrate radical (NO3), the oxidation of biogenic volatile organic compounds (BVOC) emitted by vegetation, such as isoprene (C5H8), monoterpenes (C10H16), and sesquiterpenes (C15H24), is a dominant contributor to global SOA budget (1). In recent years, it has been increasingly recognized that anthropogenic emissions play a critical role in biogenic SOA formation in ambient environments (8–10). A key mechanism that couples anthropogenic emissions with biogenic emissions is the effect of nitrogen oxides (NOx = NO + NO2) on biogenic SOA production. In clean or moderately polluted environments, higher NOx will result in more oxidant formation which can enhance SOA production from BVOC. In the presence of NOx, OH oxidation and NO3 oxidation of BVOC can lead to the formation of organic nitrates (ON), a major component of reactive oxidized nitrogen. ON formation represents a large instantaneous sink of NOx that effectively couples the HOx and NOx cycles and impacts ozone and SOA production. The formation of ON removes NOx from the atmosphere and directly suppresses ozone production near source regions (11). Transportation and subsequent chemical reactions of ON can release NOx and promote ozone formation in locations far away from the initial NOx emissions. Owing to their semi-volatile/low-volatility nature, ON can also undergo gas-particle partitioning and contribute to SOA. Results from ambient field measurements have revealed that particulate ON contribute a large fraction of OA at multiple sites around the world (12). The ubiquitous presence of ON highlights the importance of understanding their formation and fates to accurately evaluate their roles in NOx recycling, ozone, and SOA production. This chapter serves an overview of recently published reviews by Perring et al. (11), Ng et al. (12), and Wennberg et al. (13) and specifically reviews ON chemistry from oxidation of BVOC, with a focus on the role of ON in SOA formation. We refer the readers to the aforementioned review articles for comprehensive discussions related to this chemistry. Here, we outline the formation and fates of ON, methods for measuring gas-phase and particle-phase ON, the relationships between ON and SOA production, ambient observations of particulate ON, and conclude with recommendations for future research.
Sources of Organic Nitrates: Formation Mechanism and Yield Atmospheric ON are typically formed via secondary reactions in the ambient air as direct emissions account for a minor fraction. There are two major gasphase sources of ON from the oxidations of BVOC: OH oxidation of BVOC in the presence of nitric oxide (NO) and NO3 oxidation of BVOC. OH Oxidation in the Presence of NO OH oxidation of BVOC is one of the major oxidation pathways in the ambient air during daytime. In general, OH initiates the chain of radical reactions by either 106 Hunt et al.; Multiphase Environmental Chemistry in the Atmosphere ACS Symposium Series; American Chemical Society: Washington, DC, 2018.
abstracting a hydrogen atom or attacking a double bond (if present). Owing to the olefinic nature of most BVOC, the majority of OH oxidation proceeds with the attack of OH on a double bond. The intermediate radical immediately reacts with an oxygen molecule to form a peroxy radical (RO2) which can follow various chemical pathways depending on the conditions of the ambient environment. In the presence of higher levels of NOx, such as in urban areas, RO2 preferentially reacts with NO, leading to the formation of hydroxy ON or decomposed products (alkoxy radical and NO2), as shown in Figure 1. Although the formation of ON is a minor channel of the two, the relative importance of the ON channel varies depending on the identity of the parent BVOC, temperature, and pressure (11, 14).
Figure 1. Generic formation mechanism of ON from OH oxidation of BVOC in the presence of NO.
The detailed and simplified formation mechanisms of major BVOC-derived ON from OH oxidation in the presence of NO have been reported in a number of prior studies (15, 16). Shown in Figure 2 is the schematic of the simplified ON formation mechanism from OH oxidation of isoprene in the presence of NO that is currently implemented in the global chemical transport model (GEOS-Chem) (17). For more detailed isoprene oxidation chemistry, readers are directed to the recently published review by Wennberg et al. (13). In many studies, the yield of ON is defined as the amount of either gaseous or total ON produced per parent VOC reacted on a molar basis and, thus, the ON yield can be also considered as the branching ratio of the RO2+NO reaction leading to the formation of ON, as shown in Figure 1. While there has been an extensive number of studies on isoprene hydroxy nitrate yields reporting a range of 0.04-0.15, Wennberg et al. (13) discussed that the reported lower yields could be inaccurate due to differences in experimental conditions (i.e., pressure) and issues in instrument sensitivities, providing a recommended yield of 0.13. Nonetheless, due to the high sensitivity of ozone to changes in the isoprene ON yield (18), further investigations are needed to reduce uncertainty in the isoprene ON yield. On the other hand, studies on other BVOC are scarce or not in agreement with each other when available (11, 13). For instance, the measured gaseous ON yields from the OH oxidation of α-pinene greatly vary, ranging from 0.01 to 0.26 (19–21). To our best knowledge, there are no experimental data on the ON yields from OH oxidation of other monoterpenes or sesquiterpenes to date. 107 Hunt et al.; Multiphase Environmental Chemistry in the Atmosphere ACS Symposium Series; American Chemical Society: Washington, DC, 2018.
Figure 2. Schematic of simplified ON formation mechanism from isoprene OH oxidation in the presence of NO. (Reproduced with permission from reference (17). Copyright 2016, the authors.)
NO3 Oxidation The initial oxidation of BVOC at night can be quite distinct from that of daytime. With the absence of solar radiation at night, the concentration of NO3 is sufficient to be one of the dominant oxidation pathways along with the oxidation by ozone. Different from OH, NO3 has low H abstraction efficiency such that NO3 oxidation dominantly proceeds by attacking a double bond. Due to ubiquitous 108 Hunt et al.; Multiphase Environmental Chemistry in the Atmosphere ACS Symposium Series; American Chemical Society: Washington, DC, 2018.
presence of double bonds in BVOC, NO3 oxidation is therefore considered an important oxidation pathway at night. Detailed formation mechanisms of major BVOC-derived ON from NO3 oxidation have been reported only for a few BVOC (12, 22–24). Shown in Figure 3 are the schematics of the isoprene and β-pinene ON formation mechanisms. As evident from Figure 3, a nitrate functional group is formed in the initial oxidation step and it either remains or leaves depending on the fate of RO2 and further chemistry.
Figure 3. Schematics of ON formation mechanisms from isoprene and β-pinene NO3 oxidation. (Adapted with permission from reference (12). Copyright 2017, the authors.)
The higher yield of ON with NO3 oxidation (0.62-0.8; Table 1) than with OH oxidation in the presence of NO (0.13) is reported for isoprene owing to the direct addition of a nitrate functional group to a double bond in the initial step (25). The ON yields from NO3 oxidation for other BVOC are also high (except for α-pinene) (12). Table 1 summarizes the ON yields as well as other important results from NO3 oxidation of various BVOC (12). 109 Hunt et al.; Multiphase Environmental Chemistry in the Atmosphere ACS Symposium Series; American Chemical Society: Washington, DC, 2018.
Table 1. ON and SOA mass yields from NO3 oxidation of various BVOC BVOC
ON yield
SOA mass yield
isoprene
0.62-0.80
0.02-0.24
α-pinene
0.10-0.29
0-0.16
β-pinene
0.22-0.74
0.07-1.04
Δ-carene
0.68-0.77
0.12-0.65
d-limonene
0.30-0.72
0.14-1.74
β-caryophyllene
N/A
0.86-1.46
SOURCE: Reproduced with permission from reference (12). authors.
Copyright 2017, the
Ozonolysis is another important oxidation process in the atmosphere. Studies on the ON formation and yields from ozonolysis of BVOC are even more scarce due in part to the difficulty in controlling the fate of RO2 in laboratory experiments because NO can be quickly consumed by ozone. To our knowledge, there do not exist studies on ON yields from ozonolysis of BVOC. A recent study investigated the production of ON from α-pinene ozonolysis in the presence of NOx but concluded that the majority of observed ON stemmed from RO2 formed by α-pinene reacting with secondary OH generated from ozonolysis (26). In the atmosphere, since ozone and NO coexist in non-negligible amounts, further studies are required to explore the potential formation of ON from BVOC ozonolysis.
Fates of Organic Nitrates Owing to their semi-/low-volatile nature, BVOC-derived ON exist in both gas and particle phases in the atmosphere. The loss mechanisms vary from further oxidation, photolysis, particle-phase chemical processing, deposition, and thermal loss. Figure 4 illustrates the various fates of atmospheric ON. The following two sub-sections will discuss major fates of BVOC-derived ON in gas and particle phases.
Figure 4. Potentially important fates of atmospheric ON derived from BVOC. 110 Hunt et al.; Multiphase Environmental Chemistry in the Atmosphere ACS Symposium Series; American Chemical Society: Washington, DC, 2018.
Fates of Gas-Phase Organic Nitrates Gaseous ON can undergo a variety of chemical and physical processes: partitioning to particle phase, dissolution in aerosol water, further oxidation by oxidants (such as OH and NO3), photolysis reaction, and deposition to the ground. The availability of synthetic standards has allowed for measurements of rate constants for the reactions of OH, ozone, and NO3 with various isoprene hydroxy nitrates, carbonyl nitrates, and hydroperoxy nitrates. In general, the reaction rate constants are on the order of 1x10-11, 1x10-14, and 1x10-19 cm3 molecule-1 s-1, for OH, ozone, and NO3 reactions, respectively (13). Recent studies shed important insights on the role of photolysis as a sink of gaseous ON. Carbonyl ON derived from isoprene is found to undergo much faster photolysis than previously expected (27, 28). However, the dependence on the structure and proximity of other functional groups to a nitrate group warrants further studies. In terms of deposition, rapid deposition fluxes of both isoprene nitrates and monoterpene nitrates have been observed (29). The photolysis and photochemical oxidation of ON formed from monoterpenes and sesquiterpenes are largely unknown. Fates of Particle-Phase Organic Nitrates As with gaseous ON, particulate ON can undergo a variety of chemical and physical processes: evaporation due to dilution and/or temperature change, aqueous reactions, such as hydrolysis, and deposition to the ground. Hydrolysis in aerosol water has been proposed as a dominant particle-phase ON fate from field and laboratory studies (30, 31). To date, there have been several laboratory experiments exploring the rate of ON hydrolysis from BVOC oxidation systems. Representative α-pinene derived ON via OH oxidation in the presence of NO has been shown to undergo fast hydrolysis on the order of minutes to hours depending on the aerosol pH (32). Another study has also found that the decay rate of α-pinene derived ON via OH oxidation in the presence of NO, attributed to hydrolysis, is as fast as 3.4 h-1 (33). On the other hand, little hydrolysis has been observed for ON formed via NO3 oxidation of β-pinene and limonene (23, 34). The difference in overall hydrolysis rates of particulate ON is attributed to the structural difference of ON formed via OH oxidation and NO3 oxidation. Previous studies using bulk solutions reported the dependence of ON hydrolysis rate on the site to which a nitrate group is attached (35, 36). Tertiary ON, in which a nitrate functional group is attached to a tertiary carbon, undergoes fast hydrolysis, while primary ON does not. However, unsaturated ON, such as first-generation isoprene hydroxy nitrates, are found to undergo hydrolysis on the order of minutes to hours regardless of the site of a nitrate functional group due to allylic stabilization of the cationic intermediates (37). Thus, the representativeness of results from these recent studies for other monoterpene and sesquiterpene systems requires further work. A striking difference in the behaviors of α- and β-pinene derived particulate ON upon photochemical aging (i.e., photolysis + OH oxidation) has been observed, as shown in Figure 5 (34). While α-pinene derived particulate ON from NO3 oxidation evaporated upon photochemical aging, β-pinene derived 111 Hunt et al.; Multiphase Environmental Chemistry in the Atmosphere ACS Symposium Series; American Chemical Society: Washington, DC, 2018.
particle-phase ON from NO3 oxidation did not undergo such changes. The distinct behaviors are attributed to the difference in ON products formed from the different BVOC precursors, though the effect of OH oxidation and photolysis cannot be separated. Another study observed similar degradation of α-pinene derived particulate ON from NO3 oxidation upon photochemical aging in the aqueous solution (38). However, the relative importance of photolysis and OH aging in releasing NO2 remains unknown.
Online Measurement Methods for Organic Nitrates An endeavor to develop analytical instruments capable of detecting and quantifying gaseous and particulate ON had commenced in order to resolve the unanswered question of “missing NOy”. This missing NOy problem had been observed during multiple field measurements in which the total NOy concentration, measured as NO via catalytic conversion of all the NOy species to NO, always appeared greater than the sum of individually measured NOy species, such as NO, NO2, HNO3, HONO, particulate nitrate, peroxyacetyl nitrate (PAN) (39–41). A wide range of analytical instruments has been applied in field measurements and laboratory experiments. Several decades of work by various research groups have enabled detection and quantification of gaseous and particulate ON, though analytical challenges still remain to date. Here, the measurement approaches are divided into two major categories: gas-phase ON and particle-phase ON measurements. A comprehensive discussion of the current available ON measurement techniques has been presented in a recent review on NO3 oxidation of BVOC by Ng et al. (12) Gas-Phase ON Measurement Early attempts to identify and quantify individual gaseous ON relied on chromatographic techniques, such as gas chromatography (GC) and liquid chromatography (LC), coupled with various detectors, such as electron capture detection and electron impact mass spectrometry. Although these techniques allow both detecting individual gaseous ON and quantifying them, the major disadvantage is in the measurement of multi-functional ON, which are traditionally difficult to efficiently sample and separate. Mass spectrometry (MS) without an initial separation stage, including chemical ionization MS (CIMS) and proton transfer reaction MS (PTR-MS), provides capabilities of measuring multi-functional ON, though the challenge of quantification of such individual ON remains (42, 43). Another distinct approach is to measure the sum of all ON without speciated information utilizing the thermal properties of nitrate functional groups attached to organic compounds. Initiated by the development and successful implementation of this technique by thermal dissociation laser induced fluorescence (TD-LIF) (44), the TD inlet has been coupled to other NO2 detectors, such as cavity ring-down spectroscopy (TD-CRDS) (45) and cavity attenuated phase shift spectroscopy (TD-CAPS) (46). 112 Hunt et al.; Multiphase Environmental Chemistry in the Atmosphere ACS Symposium Series; American Chemical Society: Washington, DC, 2018.
Figure 5. High resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) measurements of the β-pinene (panels a, c, e, and g) and α-pinene (panels b, d, f, and h) reactions. Panels (a) and (b): Time series of AMS organic and nitrate mass concentrations normalized to the sulfate mass concentration of the SOA. Panels (c) and (d): Time series of major AMS organic families (CH, CHO1, and CHOgt1) normalized to the sulfate mass concentration of the SOA. Panels (e) and (f): Time series of H/C, O/C, and N/C ratios of the SOA. Panels (g) and (h): Time series of AMS nitrate mass concentration normalized to the organic mass concentration of the SOA. (Adapted with permission from reference (34). Copyright 2016 American Chemical Society.)
113 Hunt et al.; Multiphase Environmental Chemistry in the Atmosphere ACS Symposium Series; American Chemical Society: Washington, DC, 2018.
Particle-Phase ON Measurement Some approaches presented in the gas-phase ON measurement section above are also capable of measuring particulate ON with modifications in the inlet. TD-LIF equipped with an activated charcoal denuder that selectively scrubs gas-phase ON has been demonstrated to measure particulate ON (47, 48). A special filter inlet to collect and subsequently desorb aerosols has been coupled to high resolution time-of-flight CIMS (FIGAERO-HR-ToF-CIMS) and has demonstrated specifically the capability of measuring particle-phase ON in field and laboratory studies (34, 43). Aside from the aforementioned instruments, the high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) that has been extensively utilized for field and laboratory studies is capable of estimating ON concentration based on three approaches (49, 50). First, owing to significant fragmentations of analytes due to flash evaporation and hard ionization, nitrate groups are mainly detected as NO+ or NO2+. The ratio of the two ions in the HR-ToF-AMS mass spectra varies depending on the origin of nitrates (i.e., inorganic or organic nitrates), which allows apportioning the amount of nitrate signals to inorganic and organic origins (51). Second, by co-locating an instrument that is capable of measuring inorganic nitrate, such as an ion chromatograph, one can also estimate the concentration of particulate ON by subtracting the inorganic nitrate concentration from the total nitrate concentration measured by HR-ToF-AMS. Finally, one can conduct positive matrix factorization (PMF) analysis on organic mass spectra together with NO+ and NO2+ ions to obtain insights into the relative contribution of organic and inorganic nitrates.
Organic Nitrate and Secondary Organic Aerosol (SOA) Formation OH Oxidation in the Presence of NO The presence and abundance of NO not only affect the yields of ON but also influence the properties and yields of bulk SOA. Traditionally, the effect of NOx level on the SOA yield was studied as a binary approach, namely, by comparing high and low NOx conditions (where RO2+NO and RO2+HO2 reactions, respectively, dominate). There is a general understanding that OH oxidation under high-NOx condition produces lower SOA yields for isoprene and monoterpenes, while the opposite has been observed for sesquiterpenes (52, 53). For isoprene, multiple studies have demonstrated the non-linear nature of NO effect on SOA yields (52, 54–59). Shown in Figure 6 is the dependence of SOA yield on the NO level parametrized in terms of a ratio of NO to isoprene. The non-linear NO effect is typically attributed to difference in RO2 fates or oxidant levels (52). At a very low and high concentration of NO, the fate of RO2 is dominated by the reaction with HO2 and NO, respectively, whereas RO2 chemistry can be rather complex in a condition where RO2+HO2 and RO2+NO compete with each other. Also, the level of NOx affects the OH concentration 114 Hunt et al.; Multiphase Environmental Chemistry in the Atmosphere ACS Symposium Series; American Chemical Society: Washington, DC, 2018.
in a non-linear manner owing to the close coupling of HOx and NOx cycling. At a low NOx level, HO2 preferentially undergoes a radical termination process by reacting with RO2 or HO2, leading to less OH production via the reaction HO2 with NO. As the NOx level increases, the HO2+NO reaction becomes more important, leading to a higher concentration of OH. However, at a high NOx level, the formation of HNO3 via the reaction of OH with NO2 accelerates such that the loss of OH becomes faster than its production, leading to a low concentration of OH. A recent study suggested that the non-linear effects of NOx on the SOA yield mainly stems from the variation in OH concentration (60). Further studies are needed to systematically investigate the role of NOx on SOA formation both in terms of the impact on RO2 fates as well as on the level of oxidants.
Figure 6. (A) Effect of NOx level on SOA yield from isoprene OH oxidation experiments. (B) Approximate concentrations of the sum of non-N-containing C5 compounds and of alkyl nitrate compounds plotted with the sum of both quantities and the AMS-measured total OA mass concentration. (Reproduced with permission from reference (59). Copyright 2016 American Chemical Society.)
Volatility of bulk SOA, one of the important physical properties of SOA, can also be influenced by the level of NO. It has been shown that isoprene SOA formed in the presence of NO is less volatile than that formed in the absence of NO in laboratory chamber experiments up to certain NO level (58, 61). As with the SOA yield, the bulk SOA property also behaves in a non-linear manner in response to the level of NO as shown in Figure 7. While the particulate ON and total SOA masses formed from the OH oxidation of isoprene also showed a non-linear trend with increasing NO, the fraction of particulate ON to total SOA mass has been found to monotonically increase as the level of NO increases, though the rate of increase varies for different NO levels (61). In other words, even though there is less total SOA mass at a high NO level, more of the mass is in the form of ON. It is interesting to observe such dependence on NO and indicates the importance of considering the yield of total ON not just as a function of parent BVOC identity but also as a function of both BVOC concentration and NO level. 115 Hunt et al.; Multiphase Environmental Chemistry in the Atmosphere ACS Symposium Series; American Chemical Society: Washington, DC, 2018.
Figure 7. Non-linear behavior of the bulk SOA volatility expressed as volume fraction remaining (VFR) formed via isoprene OH oxidation at varying NO levels. (Reproduced with permission from reference (58). Copyright 2014 American Chemical Society.)
NO3 Oxidation of BVOC Recent studies have revealed high SOA formation efficiency from NO3 oxidation of BVOC. Table 1 summarizes the SOA mass yield from various BVOC in NO3 oxidation. Except for α-pinene, other monoterpenes and sesquiterpenes have high SOA mass yield up to 1.74, highlighting the importance of NO3 oxidation of BVOC not only in the formation of ON but also in the bulk SOA (12, 62). Note that SOA mass yields above 1 are possible because of the addition of oxygen and nitrogen to the parent BVOC precursors. Figure 8 illustrates the SOA mass yield as a function of organic mass loading for NO3 oxidation of β-pinene (23). The SOA mass yield remains high even at a low organic mass loading, implying the low-volatility nature of SOA formed via NO3 oxidation of β-pinene. The same study also investigated the effect of relative humidity (RH) and RO2 fates on the SOA yields from NO3 oxidation of β-pinene but found no significant effects.
Field Observations of Particulate Organic Nitrates Results from various field studies have demonstrated that particulate ON are ubiquitous across the U.S. and Europe and contribute to a substantial fraction of submicron organic aerosols by up to 77%, as shown in Figure 9 (12). Online, advanced analytical techniques in measuring particulate ON, such as TD-LIF, HR-ToF-AMS, and FIGAERO-CIMS, have provided new insights into the importance of NO3 oxidation of BVOC, whereas the co-location of such instruments capable of independently measuring ON confirmed the substantial contribution of ON aerosols. 116 Hunt et al.; Multiphase Environmental Chemistry in the Atmosphere ACS Symposium Series; American Chemical Society: Washington, DC, 2018.
Figure 8. SOA mass yield as a function of organic mass loading for NO3 oxidation of β-pinene. (Reproduced with permission from reference (23). Copyright 2015, the authors.)
A prominent example of successful ON measurements is the Southern Oxidant and Aerosol Study (SOAS) that took place in the southeastern U.S. in 2013. A total of five independent approaches to quantify particulate ON from TD-LIF, HR-ToF-AMS, and FIGAERO-CIMS have revealed the important contribution of NO3 oxidation of monoterpenes to aerosol ON (43, 49). As with the SOAS campaign, many field studies conducted in BVOC-rich environments have observed the particulate ON peaking after midnight, confirming the important role of monoterpene-derived ON via nighttime chemistry (63). Spatially extensive AMS data sets from two field measurements across various countries in Europe (i.e., EUCAARI and EMEP) also provided evidence of substantial particle-phase ON formation via oxidations of BVOC (50). High concentrations of particulate ON are usually observed in areas that are in proximity to NOx emission sources during the night, while remote regions with less anthropogenic impacts during daytime have experienced low levels of particulate ON.
117 Hunt et al.; Multiphase Environmental Chemistry in the Atmosphere ACS Symposium Series; American Chemical Society: Washington, DC, 2018.
Figure 9. Mass-based fraction of particle-phase ON to submicron total organic aerosols, indicated by light blue (print in color) or light gray (print in grayscale) in pie charts. (Adapted with permission from reference (12). Copyright 2017, the authors.)
Future Research Needs Recent advances in measurements of gaseous and particulate ON have demonstrated their ubiquitous presence in the atmosphere. One of the largest uncertainties in our understanding of ON chemistry is the extent to which ON act as a permanent versus temporary sink of NOx. This will depend on their formation yields and fates as they can either retain or release NOx upon further reactions. Such knowledge is imperative in improving regional and global model simulations of NOx budget, ozone, and SOA formation. The synthesis of ON formed from first-generation isoprene chemistry has led to substantial advancement in the quantification of their formation yields and gas-phase oxidation chemistry. Nevertheless, more studies are needed to further constrain the ON yields from isoprene chemistry. Much less is known regarding organic nitrogen chemistry of monoterpenes and sesquiterpenes. There is a critical need to measure the formation yields of ON from monoterpenes and sesquiterpenes oxidations under different reaction conditions, including the dependence on NOx levels (RO2 fates), temperature, and pressure. The photolysis and photochemical oxidation of ON formed from BVOC are poorly understood. The rates and products of these reactions for larger multifunctional ON (containing more than five carbon atoms) and whether NO2 is released in photochemical aging of gas and particulate ON are generally not known. Specifically, whether 118 Hunt et al.; Multiphase Environmental Chemistry in the Atmosphere ACS Symposium Series; American Chemical Society: Washington, DC, 2018.
ON act as a permanent or temporary sink for NOx can be highly dependent on the BVOC precursor. It is imperative to not only conduct experiments to investigate ON formation from different BVOC oxidation pathways, but also how gas and particulate ON evolve over their lifetimes and whether they return or retain NOx upon photochemical aging by photolysis and/or OH reactions. Beyond gas-phase chemistry, future research needs to investigate the loss ON via interactions with aqueous aerosols and cloud droplets. The solubility of multifunctional ON and the extent and rate to which hydrolysis proceeds in aerosol water warrant future studies. The effect of particle acidity on ON hydrolysis should also be considered. Owing to a lack of fundamental laboratory data, monoterpene and sesquiterpene organic nitrogen chemistry are largely incomplete and missing in current atmospheric models. Future laboratory and field studies and advancement in measurement techniques will allow for better constraints on the formation and fates of ON. A fundamental and quantitative understanding of the formation mechanisms, yields, gas-particle partitioning, and fates of ON from BVOC oxidations is critical to accurately predict their impacts on NOx cycling, oxidation capacity, and ozone formation as NOx emissions continue to decrease throughout the U.S.
Acknowledgments The authors acknowledged support from US Environmental Protection Agency STAR RD-83540301 and National Science Foundation AGS-1555034 (CAREER). This publication’s contents are solely the responsibility of the grantee and do not necessarily represent the official views of the US EPA. Further, US EPA does not endorse the purchase of any commercial products or services mentioned in the publication.
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