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.
Introduction
Secondary organic aerosols (SOAs) are essential components in atmospheric
aerosols that are related to climate change, air quality, and human health.
They are generated through not only daytime photooxidation, but also
nighttime chemical oxidation from both biogenic and anthropogenic volatile
organic compounds (VOCs) (Hallquist et al., 2009; Rollins et al., 2012;
Nozière et al., 2015; Huang et al., 2019). Nitrooxy organosulfates (OSs) with nitrooxy (–ONO2) and sulfate ester groups
(–OSO3H) (Surratt et al., 2008; Lin et al., 2012) substantially
participate in the formation of SOA (Tolocka and Turpin, 2012; Ng et al.,
2017; Bruggemann et al., 2020). Moreover, nitrooxy OSs can alter the surface
hygroscopicity of aerosol particles because of their water-soluble and
fat-soluble properties, promoting the production of cloud condensation
nuclei (Schindelka et al., 2013) and also increasing the light
absorption of organic aerosols (Nguyen et al., 2012).
Nitrooxy OSs can be generated from both biogenic (Iinuma et al., 2007b;
Surratt et al., 2007; Gómez-González et al., 2008; Surratt et al.,
2008) and anthropogenic VOCs (Tao et al., 2014; Riva et al., 2015). The
main precursors of biogenic nitrooxy OSs were isoprene, monoterpenes,
sesquiterpenes, and aldehyde, as previous studies observed biogenic
nitrooxy OSs in isoprene chamber experiments (Gómez-González
et al., 2008; Surratt et al., 2008), a forest (Iinuma et
al., 2007b), and urban aerosols (Lin et al., 2012). Compared to
biogenic nitrooxy OSs studies, few research activities have been carried out
focusing on anthropogenic nitrooxy OSs. Tao et al. (2014) found
that long-chain alkenes from traffic emissions are possible precursors of
long-chain alkyl nitrooxy OSs in urban aerosols in Shanghai. A recent study
reported the presence of nitrooxy OSs in the polar regions (Ye
et al., 2021).
The formation of nitrooxy OSs due to nighttime chemistry has been less understood
so far. Surratt et al. (2008) suggested that nitrooxy OSs can be
formed from the combination of organonitrates and sulfates under
acidification, while organonitrates are preferably produced by nighttime
NO3 radical oxidation than daytime photooxidation (Rollins et al.,
2012; Kiendler-Scharr et al., 2016; Huang et al., 2019). Iinuma et al. (2007a) reported that some monoterpene nitrooxy OSs (e.g.,
C10H17NO7S, C10H18N2O7S, and
C5H10N2O11S) were only detected in nighttime aerosols,
indicating the importance of NO3 radicals in nighttime chemistry.
Firework displays are frequently conducted as a traditional activity to celebrate
popular festivals, in particular New Year's Eve, emitting large
quantities of pollutants into the atmosphere (Vecchi et al., 2008; Huang
et al., 2012). It is found that lots of semi-volatile to volatile organic
compounds, such as n-alkanes and polycyclic aromatic hydrocarbons (PAHs),
released during firework-related events (Sarkar et al., 2010; Feng et
al., 2012), can be essential precursors of anthropogenic nitrooxy OSs in
aerosols (Tao et al., 2014; Riva et al., 2015). Even though the
knowledge of chemical and physical behaviors of nitrooxy OSs in
firework-related urban aerosols is very sparse, particularly for
high-molecular-weight (HMW, molecular weight more than 500 Da) compounds
because of their molecular complexity.
To fill this research gap, the molecular characterization of HMW
nitrooxy OSs in firework-related aerosols during nighttime is reported in
this study based on the measurements from Fourier transform ion cyclotron
resonance mass spectrometry (FT-ICR MS) with ultrahigh resolution and mass
accuracy. FT-ICR MS has been proven to be a powerful tool to reveal the
complicated organic matter in environmental samples at a molecular level
(Koch et al., 2007; Dzepina et al., 2015; Bao et al., 2018; Qi et al.,
2020, 2021; Su et al., 2021). Our study presents elemental
compositions and classifies the organic mixtures into different categories to
identify potential origins of nitrooxy OSs and to investigate their possible
chemical structures and precursors. The volatility of different nitrooxy OSs
is predicted and discussed as well.
MethodologyAerosol sampling
Daytime and nighttime aerosol samples (n= 6) were sampled from 21 to
23 January 2012 in an urban site at the Institute of Atmospheric
Physics, Chinese Academy of Sciences (39∘58′28′′ N,
116∘22′13′′ E), Beijing. The samples include NYE D (New
Year's Eve daytime before the fireworks), NYE N (New Year's Eve nighttime
during the fireworks), LNY D (lunar New Year's Day daytime after the
fireworks), LNY N (lunar New Year's Day nighttime), normal D (normal day
daytime), and normal N (normal day nighttime)
(Xie et al., 2020b). Detailed sample
information can be found in Table S1 in the Supplement. The total suspended particle (TSP)
samples were collected on prebaked quartz filters (20 cm × 25 cm,
Pallflex) using a high-volume air sampler (Kimoto, Japan) and then were
refrigerated at -20 ∘C until analysis. Field blank filters
were collected following the same procedure. Further, 2 d air mass
backward trajectories show that the air was primarily originated from the
clean northwest region during the sampling period.
FT-ICR MS analysis
The method to extract water-soluble organic carbon (WSOC) fractions from
each aerosol sample was taken from our previous studies (Xie et al.,
2020a, b). After being extracted with ultrapure Milli-Q water,
WSOC fractions were eluted from a solid-phase extraction cartridge (Oasis
HLB, Waters, USA) using methanol and were analyzed using a 15.0 T Bruker
Solarix FT-ICR MS (Bruker Daltonik, GmbH, Bremen, Germany) with the negative
electrospray ionization (ESI) mode. An average resolving power (m/Δm50 %) of over 400 000 at m/z∼ 400 was achieved
(Cao et al., 2015). The detection mass ranges were
180–1000 Da. The mass spectra were internally calibrated via data
analysis software. The mass accuracy was within 1 ppm, and peaks of the signal-to-noise ratio higher than 6 were assigned for further analysis. A molecular
formula calculator was used to calculate formulas with elemental
compositions up to 50 12C, 100 1H, 50 16O, 2 14N, and 1 32S atom. Several conservative rules were used as
further restrictions for the formula calculation (i.e., the elemental ratios
of H / C < 2.5, O / C < 1.2, and S / C < 0.2, and the N
rule for even electron ions) (Wozniak et al., 2008; Zhang et al., 2016).
Unambiguous molecular formula assignment was determined with the help of the
homologous series approach for multiple formula assignments (Koch et al.,
2007; Herzsprung et al., 2014). The isotopic peaks were removed in this
study.
The formulae containing C, H, N, O, and S atoms, namely CHONS compounds, in
WSOC fractions of urban aerosols were assigned from the ESI FT-ICR MS. The
number and the total intensity of CHONS compounds were attributed to 14 %–29 %
and 10 %–28 % of the total assigned compounds, respectively (Fig. S1). As
the predominant fraction occupying more than 85 %, CHONS compounds with
O / S ≥ 7 were tentatively deemed to be nitrooxy OSs in present work,
supporting the assignment of a –OSO3H group and a –ONO2 group in
molecules (Kuang et al., 2016; Wang et al., 2016). However, other
sulfur-containing compounds (e.g., sulfonates) might also be introduced and
impact the analysis due to lack of the structure information of ions from
tandem MS experiments (El Haddad et al., 2013; Riva et al., 2015).
Results and discussionGeneral molecular characterization of nitrooxy OSs
Table 1 shows that slightly higher compounds in number frequency were found
in normal nighttime samples (1094 in normal N) than in normal daytime (885
in normal D), similar for the comparison between LNY N (1113) and LNY D
(1097) samples, which is in agreement with previous studies (Pinxteren
et al., 2009; O'Brien et al., 2014; Wang et al., 2016). However, 690
nitrooxy OSs were observed in NYE D before the firework period, while it
considerably increased up to 2050 in NYE N during the firework period,
indicating a pronounced increment at night during the firework event. This was consistent with the concentration trend of water-soluble organic
nitrogen, which was significantly higher in the nighttime than that in the
daytime, particularly in NYE N (Table S1). This can be explained by
significant precursors emitted from fireworks (Kong et al., 2015) that
produce nitrooxy OSs via nighttime NO3 radical chemistry
(Riva et al., 2015). Meanwhile, the heavy emissions of nitrogen oxide
during the firework event could elevate the production rate of NO3
radicals (Ljungström and Hallquist, 1996; Kiendler-Scharr et al.,
2016), and a previous study showed a good correlation between NO3 and the
total concentration of nitrooxy OSs at night (Nguyen et al., 2014).
The concentrations of chemical components and the number
and elemental characteristics of nitrooxy OSs in the Beijing aerosol
samples.
The compound number and intensity of nitrooxy OSs in (a) samples NYE D and NYE N and (b) samples normal D and normal N. The common compounds in both daytime and nighttime samples are denoted by “Both”, along with a number. The percentage numbers represent the proportion of the unique ones in the total nitrooxy OSs of each sample.
Different from the detected compounds in NYE D, there were 1411 nitrooxy OSs
that were only detected in NYE N, which contributed 69 % of the total number
of nitrooxy OSs in the sample (Fig. 1). Moreover, their relative
intensities also accounted for nearly half of the total intensities in NYE N. These results
indicate that extensive burning of firecrackers offered many specific
precursors for the formation of new nitrooxy OSs.
Classification of nitrooxy OSs according to the numbers
of N, S, and O atoms in their molecules.
Nitrooxy OSs were identified as
N1O7S1–N1O13S1 and
N2O7S1–N2O14S1 species (Figs. 2 and S2).
Here, N1O7S1 compounds refer to formulae containing one
nitrogen, seven oxygen, and one sulfur element, and this was similar for the other
species. Their number concentrations decrease with the increase of oxygen
content in molecules. N1OnS1 species are the predominant
nitrooxy OSs; the number and the intensity of N1OnS1 species
occupied 65 %–82 % and 62 %–80 % of the total detected nitrooxy OSs,
respectively. During firework periods, up to 1300 species of
N1OnS1 were detected in NYE N, twice as many as other
samples. The effect of pyrotechnics on nitrooxy OSs becomes more substantial
with the increased oxygen atom number (Fig. 2). Similarly, the intensity
of N1OnS1 species doubled in NYE N compared to other samples.
N2OnS1 species may have other nitrogenous functional groups
(e.g., amino and nitro groups) in addition to the nitrate functional group.
During non-firework periods, there were an average of 300 species of
N2OnS1, but the number increased to 724 in NYE N. Moreover,
the contribution of fireworks to N2OnS1 species was higher
than that of N1OnS1 compounds, possibly because some released
amino acids and their derivatives react to form nitrooxy OSs with two
nitrogen-containing functional groups.
Typical Van Krevelen symbols for (a) NYE D and (b) NYE N. Dotted black lines show various AI value ranges, and black lines denote class identification. The size of the plots represents the relative intensities of nitrooxy OSs on a logarithmic scale. The colored bars of (a) and (b) reflect the DBE values. Bar diagrams of (c) and (d) show the number and
intensity contribution of major classes in different samples, respectively.
Table 1 and Fig. S3 present the arithmetic and weighted mean elemental
ratios of total nitrooxy OSs for each sample, respectively. The average
molecular weights rose from 411 ± 69 Da (normal D) to 417 ± 78 Da (normal N) and from 398 ± 69 Da (NYE D) to 449 ± 93 Da (NYE
N). The average molecular formulae are
C17H25O8.5N1.2S1.0 and
C18H24O8.6N1.3S1.0 for normal D and normal N and
C17H24O8.6N1.1S1.0 and
C21H26O9.1N1.4S1.0 for NYE D and NYE N,
respectively. Nitrooxy OSs in firework-related aerosols had relatively
higher C and O contents, indicating that many HMW compounds had a higher
extent of oxidation. Moreover, both O / C and H / C ratios of nitrooxy OSs
lessened in NYE N, along with increases of unsaturation parameters of
double-bone equivalent (DBE) values and DBE / C ratios. Similar trends were
found for the intensity-weighted average elemental ratios of compounds with
high DBEw values but low O / Cw and H / Cw ratios (Fig. S3).
Compared with other studies (Jiang et al., 2016; Lin et al., 2012), our
results suggested that there were more aromatic compounds in aerosol
samples. Additionally, lots of nitrooxy OSs with high DBE values (≥ 7)
were only detected in NYE N (Fig. 3). They were mostly located in the
region of aromatic index (AI) higher than 0.5, referring to their condensed
aromatic ring structure. From Table 1, it is seen that 21 and 38 compounds with AI > 0.5 were observed in normal D and normal N and 22 and 23
compounds in LNY D and LNY N, respectively. Compared with 16 of these compounds
in NYE D, there were up to 83 compounds in NYE N. These results possibly
indicate that pyrotechnic emissions have substantial impacts on the
formation of aromatic-like nitrooxy OSs.
Van Krevelen diagram division
The Van Krevelen (VK) diagram is widely applied to depict the evolution of
organic mixtures and to identify possible origins of organic aerosols by
differentiating major known categories of natural and anthropogenic
organic matter (Nozière et al., 2015; Bianco et al., 2018). Here, we
applied the VK to investigate nitrooxy OSs in firework-related aerosols. The
seven specific classification areas are shown in Figs. 3 and S4, and
their stoichiometric ranges are displayed in Table S2. The two most
populated regions correspond to carboxylic-rich alicyclic molecules
(CRAM-like)/lignin-like (49 %–66 % and 40 %–49 % of the total number
and intensity) and aliphatic-/peptide-like (21 %–33 % and 24 %–38 % of the total number and intensity) classes, which are followed by carbohydrate-like (6 %–12 % and 11 %–19 % of total number and
intensity) and tannin-like (4 %–7 % of total number and intensity)
classes. It is found that more than 98 % of nitrooxy OSs belong to these
four categories. Previous studies reported that the majority of WSOC
fractions were lignin-, lipid-, and aliphatic-/peptide-like classes in
aerosols and cloud water (Wozniak et al., 2008; Zhao et al., 2013; Bianco
et al., 2018). However, nitrooxy OSs in the present work had relatively high
O / C ratios, potentially because they were consistent with covalently bound
HSO4- (Romero and Oehme, 2005) in HMW sulfur-containing
compounds (Wozniak et al., 2008). In addition, nitrooxy OSs also
had high H / C ratios, indicating that sulfation, nitration, or
functionalization processes led to mostly saturated compounds.
Although the number of all seven types of nitrooxy OSs increased obviously
in NYE N compared with other samples, the impacts of fireworks on
nitrooxy OSs are different in categories. As for the most abundant
CRAM-like nitrooxy OSs, they were more abundant during the nighttime (620
in normal N) than daytime (375 in normal D). However, NYE N contained about
1354 CRAM-like compounds, which was 3 times more than NYE D. The
relative contribution of the number of these compounds was 60 % in NYE N,
substantially higher than that in NYE D (45 %). The total intensity of
such compounds in NYE N was about 8 times higher than of those in NYE D.
These observations demonstrate that nighttime oxidation is important in the
formation of CRAM-like nitrooxy OSs, especially in the presence of abundant
firework-related precursors. CRAMs contain the structures of carboxylated
alicyclic and large and fused nonaromatic rings with a high ratio of
substituted carboxyl groups (Bianco et al., 2018). However, some
CRAM-like nitrooxy OSs were located in the aromatic area (AI > 0.5).
Thus, there may exist some aromatic-like compounds with some degree of
alkylation that have been mistaken for a nonaromatic class (Kourtchev et
al., 2016; Tong et al., 2016). Also, it was worth noting that nitrooxy OSs
of aromatic region could be lignin-like compounds, which contains aromatic
rings in their chemical structures. The results are consistent with the high
unsaturation of compounds in the region as described above.
Aliphatic-/peptide-like nitrooxy OSs have low DBE values and H / C ratios,
indicating a high degree of saturation and long carbon lengths. Aliphatic-like
nitrooxy OSs (e.g., acyclic compounds) are mainly derived from alkanes,
alcohols, ethers, ketones, aldehydes, esters, etc., from anthropogenic and
natural emissions. Peptide-like nitrooxy OSs are primarily derived from
functionalized amino acids, peptides, and protein fragments. Unlike
CRAM-like compounds, average relative contributions of both the number and
the total intensity of aliphatic-/peptide-like nitrooxy OSs were more
abundant during daytime (∼ 40 %) than nighttime
(∼ 30 %). However, there are 427 species of
aliphatic-/peptide-like nitrooxy OSs in NYE N, which is twice as many as
other samples. The intensity of each compound was also higher in NYE N with
bigger symbol sizes (Fig. 3b), and the total intensity was about 3
times higher than other samples. These results demonstrate the importance of
anthropogenic precursors for the formation of aliphatic-/peptide-like
nitrooxy OSs, though they could be more susceptible to photochemical
reactions than nighttime chemistry from biogenic precursors.
Contrary to CRAM-like nitrooxy OSs, the carbohydrate-like nitrooxy OSs with high
intensity have high H / C and O / C ratios and saturation, indicating they are highly
oxidized and alkylated. The intensity of carbohydrate-like nitrooxy OSs was
significantly higher than that of sulfur-free compounds reported in previous
studies (Wozniak et al., 2008; Bianco et al., 2018). It is reasonable
because carbohydrates and their derivatives are polyhydroxy aldehydes,
polyhydroxy ketones, and organic compounds, which can be hydrolyzed to form
polyhydroxy aldehydes or polyhydroxy ketones, tending to generate OSs and
nitrooxy OSs (Passananti et al., 2016; Ogino, 2021). Moreover,
N2OnS1 species were more abundant than N1OnS1
species (Fig. S5), indicating a trend toward easily functionalization.
Although the number of carbohydrate-like compounds in NYE N was close to
other samples, the intensity of them increased, potentially indicating an
increase of the concentration of them. As for tannin-like classes, which
are also highly oxygenated organic compounds (Bianco et al.,
2018), their content in NYE N was also more abundant than other samples.
Considering the lipid-like nitrooxy OSs, unsaturated hydrocarbons, and aromatic
structure classes, only less than 1.5 % compounds are in these regions.
Lipid-like organics, containing monoglycerides, diglycerides, fats,
fat-soluble vitamins, and sterols, primarily originate from biogenic
materials and phospholipids (Gurganus et al., 2015; Bianco et
al., 2018), but most nitrooxy OSs are of secondary origin. Unsaturated
hydrocarbons compounds are mostly composed of carbon and hydrogen atoms,
while nitrooxy OSs have lots of heteroatoms. As for aromatic compounds, they
are mainly produced by combustion as the indicators of anthropogenic
origin. The limited number of nitrooxy OSs detected in this region may be
due to the tendency of some alkylated compounds to fall into other
categories (e.g., CRAM-like). In summary, all nitrooxy OS categories were
enhanced in NYE N, particularly for the lignin-like nitrooxy OSs. Moreover,
the intensity of carbohydrate-like nitrooxy OSs increased due to the
enhancement of nighttime chemistry.
Subgroups and potential precursors
Figure S6 showed that compared with NYE D, nitrooxy OSs (> 1500
compounds) were densely distributed with high DBE values (≥ 7) during
the firework event, especially for those in the HMW region. Most of the
nitrooxy OSs were aromatics with Xc higher than 2.5 (Yassine et
al., 2014) and lower O / C (≤ 0.5) and H / C (≤ 1.5) ratios. Additionally,
high intensities of these highly unsaturated compounds indicated their
sufficient contents in aerosols. From Figs. 4 and 5, it is demonstrated that the DBE values and C
numbers of N1OnS1 species of nitrooxy OSs in NYE N varied
separately within the range of 0–23 and 6–35, which were higher than the
average value of DBE (0–16) and C number (6–27) in other samples. Although
the abundance of nitrooxy OSs of DBE (4–10) and C number (10–20) in the
nighttime was higher than that during the daytime, the number of
nitrooxy OSs with DBE and C number in the range of 4–18 and 10–20 was even
higher in the NYE N. These highly unsaturated nitrooxy OSs are aromatics,
which may be originated from firework-related aromatic VOCs or PAHs
(Riva et al., 2015).
(a–f) DBE vs. C number for N1OnS1 species. The color bar shows the number of O atoms. The size of the plots denotes the relative intensities of nitrooxy OSs on a logarithmic scale.
(1)–(7) are proposed structures of some nitrooxy OSs,
among which (1) and (2) have been reported previously (Surratt et
al., 2008). Their relative intensities in each sample are shown in Table S3.
(g) The proposed potential formation mechanisms of various groups of
nitrooxy OSs.
Molecular formulae distributions of
N1O7S1–N1O12S1 and
N2O7S1–N2O12S1 class species. The C and DBE
number distributions of N1OnS1 and N2OnS1
class species in the NYE N sample. The size of the symbols reflects the
relative peak magnitudes of nitrooxy OSs on a logarithmic scale. The pink
arrows and molecular formulae in N1O8S1 and
N2O8S1 class species display the elemental composition of
compounds as an example for all classes.
Nitrooxy OSs have an extensive range of unsaturation, with DBE values ranging
from 0 to 23 (Fig. 4). Previous studies have reported that nitrooxy OSs
(e.g., C10H17NO7S (1), C9H15NO8S (2)) can be
formed from biogenic VOCs (e.g., α-pinene and limonene) (Iinuma et
al., 2007a; Surratt et al., 2008; Cai et al., 2020).
C10H17NO7S and C9H15NO8S (Fig. 4) have the
same degree of unsaturation as their precursors and show the strongest
intensity among all nitrooxy OSs, which demonstrate that α-pinene
and limonene are the primary precursors of biogenic nitrooxy OSs. A
continuous series of corresponding family series was also detected in
firework-related aerosols, namely CnH2n-3NO7S (n= 9–22) and
CnH2n-3NO8S (n= 9–24) (Fig. 5).
The nitrooxy OSs were divided into three main categories to illustrate the
molecular difference. Group A comprises aliphatic-like nitrooxy OSs (DBE ≤ 2), which is featured by long alkyl carbon chains with high
saturation; group B contains aromatic-like nitrooxy OSs (Xc> 2.5) with high unsaturation; group C represents the rest of the compounds similar to biogenic nitrooxy OSs with a moderate extent of
saturation. As for the aliphatic-like nitrooxy OSs, such as
C18H35NO9S (3) and C12H25NO7S (4) (Fig. 4),
they have saturated and long carbon chains, which may source from precursors
such as long-chain alkenes, alkanes, and fatty acids by photooxidation. Both
had relatively high intensities and consecutive family series, i.e., CnH2n-1NO9S (n= 9–22) and CnH2n+1NO7S
(n= 6–24), respectively (Fig. 5). These precursors may also produce
nitrooxy OSs under high NOx conditions or break double bonds to form
intermediate products through photooxidation and then form nitrooxy OSs
with sulfates. Some possible formation mechanisms are proposed in Fig. 4g. It is noted that, except for compounds (1) and (2), the intensity of
each aliphatic-like nitrooxy OS is higher than others in daytime samples,
highlighting the importance of photooxidation to their generation.
The number of the aromatic-like nitrooxy OSs was the most abundant among
all measured nitrooxy OSs. Figure S6d and h show that there were
slight differences between NYE D and NYE N for aliphatic and biogenic
nitrooxy OSs. Nonetheless, compared with the daytime, the number of
aromatic-like nitrooxy OSs was considerably enhanced in NYE N with the HMW compounds.
Riva et al. (2015), using side-by-side comparison experiments, proved
that the generation of OSs and sulfonates from PAHs was enhanced with the existence of acidified sulfate seed aerosols. Their results implied that
aromatic-like nitrooxy OSs might efficiently be generated through PAHs and
sulfate ions released from fireworks at night without the participation of
photochemistry. For instance, the aromatic-like nitrooxy OSs with multiple
benzenes can be generated from carboxyl compounds, which is an oxidation
product of pyrene (Juhasz and Naidu, 2000). Some possible structures,
such as C18H15NO11S (5), C16H13NO9S (6), and
C11H15NO8S (7), and proposed formation mechanisms are
displayed in Fig. 4. Their corresponding family series
(i.e., CnH2n-21NO11S (n= 17–28), CnH2n-19NO9S
(n= 15–29), and CnH2n-7NO8S (n= 8–29)) have more carbon
atoms than the biogenic and aliphatic nitrooxy OSs (Fig. 5), possibly
because they are formed via the polymerization process or derived from
aromatic compounds with high carbon content. In addition, it is noted that the
intensity of each aromatic-like nitrooxy OS was lower than the other two
groups and decreased with the increase of unsaturation (Fig. 4 and Table S3). This may be because the water solubility of aromatic-like nitrooxy OSs
decreases with the increasing unsaturation. However, these nitrooxy OSs are
possibly present in the non-WSOC fractions, which requires further
investigation.
Volatility characteristics and molecular corridors
Molecular corridors that are constrained by two boundary lines of sugar alcohols
CnH2n+2On with O / C = 1 and linear n-alkanes
CnH2n+2 with O / C = 0 are used for a better understanding of the
chemical and physical properties in SOA evolution (Shiraiwa et al., 2014;
Li et al., 2016; Shiraiwa et al., 2017). From Fig. 6a–b, it is shown that more than
98 % of nitrooxy OSs detected in the present study were located in the region
of extremely low-volatility organic compounds (ELVOCs) with saturation mass
concentration (C0) < 3 × 10-4µg m-3
(Donahue et al., 2011; Murphy et al., 2014) and a molar mass higher than
250 g mol-1. Moreover, the volatility varies among
N1OnS1 and N2OnS1 species because of the
differences in their molecular composition and structures. Compared with
N1OnS1, many of the N2OnS1 species have
lower volatility and a higher O / C ratio, nearing the sugar alcohol
CnH2n+2On line. Lots of these compounds with higher intensity
were found in NYE N than other samples, which suggests that highly oxidized
compounds are produced in large quantities via nighttime chemistry after
firework emissions. Moreover, the volatility of nitrooxy OSs potentially
decreased with the increase of molecular weight and unsaturation. Compared
with compounds in NYE D, numbers of nitrooxy OSs with low volatility were
only detected in NYE N, possibly because of the increase of HMW
aromatic-like nitrooxy OSs affected by firework emissions. Further, it was
worth noting that the volatility of nitrooxy OSs was lower than that of OSs
(Xie et al., 2020a), possibly because they are highly functionalized
compounds.
Molecular corridors and volatility characteristics for
nitrooxy OSs in (a) NYE D and (b) NYE N. (c) Comparison of nitrooxy OSs in the present work with those reported in urban aerosols (Lin et al., 2012; O'Brien et al., 2014), cloud water (Zhao et al., 2013), rain (Altieri et al., 2009), and fog (Mazzoleni et
al., 2010). The top right of (c) shows the characteristic reaction pathways with most probable kinetic regimes (1. aqueous-phase reaction; 2. simple gas-phase oxidation; 3. gas- or particle-phase autoxidation; and 4. particle-phase dimerization) (Shiraiwa et al., 2014). The
boundary lines denote sugar alcohols CnH2n+2On with O / C = 1 (red) and linear n-alkanes CnH2n+2 with O / C = 0 (purple). The small plots denote the individual nitrooxy OSs color-coded by O / C ratio, and
the larger ones show the surrogate nitrooxy OSs with the average values of
M and C0.
The molecular corridor includes three primary parts, consisting of low,
intermediate, and high O / C ratio corridors (LOC, IOC, and HOC)
(Shiraiwa et al., 2014). The plentiful gas-phase oxidation
products of alkanes fall into LOC, which is near the alkane line. Conversely,
the aqueous-phase reaction and autoxidation products were in HOC, close to
the sugar alcohol line. The IOC corridor is the area connecting LOC and
HOC. Nitrooxy OSs observed in this work are dominantly found in the IOC
molecular corridors. N1OnS1 species are closer to the LOC corridors,
while N2OnS1 species are closer to the HOC corridors. These results
suggest that most firework-related nitrooxy OSs were possibly gas- and/or
particle-phase autoxidation or dimerization products. For instance,
nitrooxy OS can be formed through hydroxynitrate gas-phase products
reactively uptaking onto acidified sulfate seed aerosols through the
esterification of the hydroxyl group with sulfuric acid (Surratt et
al., 2008). Jay and Stieglitz (1989) also found hydroxynitrates produced
by the oxidation of α-pinene induced by NO3 at night. Also,
several newly firework-related nitrooxy OSs with higher molecular weight
were possibly generated from dimerization and oligomerization in the
particle phase. These results demonstrate that the dimerization and
functionalization of nitrooxy OSs can be substantially enhanced in the
particle phase with rising pollutant concentrations and varying reaction
scenarios.
Although nitrooxy OSs have been frequently reported within aerosols (Lin
et al., 2012; O'Brien et al., 2014; Cai et al., 2020), deposited sediment
(Zhang et al., 2016), and atmospheric water such as cloud water
(Zhao et al., 2013), rain (Altieri et al., 2009), or
fog (Mazzoleni et al., 2010), they were different from those
in the present work because of the unique chemical reactions during the
fireworks (Fig. 6c). Organics in atmospheric water with aqueous-phase
reactions are highly oxidized and close to the sugar alcohol line. Although
a fraction of cloud-water nitrooxy OSs overlap with those in aerosols, the
firework-related nitrooxy OSs in our work showed a higher molar mass and
lower volatility than urban aerosols reported previously (Lin et al.,
2012; O'Brien et al., 2014), especially at NYE night, potentially because of
increased dimerization and oligomerization reactions.
Summary and perspective
The present study provides unique information about the important
contributions of anthropogenic precursors, as well as biogenic precursors,
to the formation of nitrooxy OSs in ambient aerosols during firework
events. Instead, numbers of nitrooxy OSs were potentially derived from
alkene, fatty acids, and aromatics and their derivatives compared to
biogenic-related nitrooxy OSs. The surfactant properties of ambient aerosol
particles may be influenced after coupling with hydrophilic functional
groups of nitrooxy and sulfate, which affect the formation of cloud
condensation nuclei. Furthermore, influenced by the firework emission, a lot
of organonitrates in the gas phase can partition into the particle phase by
forming nitrooxy OSs with low volatility as ELVOCs, thus participating in the
organic nitrogen cycle. In addition, they also affect the NOx cycle in the
atmosphere. Our results highlight the fact that firework emission considerably
contributes to the formation of nitrooxy OSs and will have an important
influence on atmospheric physical and chemical processes. Nevertheless,
nighttime chemistry of NO3 radicals is substantially involved in the
generation of nitrooxy OSs, particularly for aromatic-like compounds. Such
complex mechanisms warrant further investigation.
Data availability
The dataset for this paper is available upon request from the corresponding author (fupingqing@tju.edu.cn).
The supplement related to this article is available online at: https://doi.org/10.5194/acp-21-11453-2021-supplement.
Author contributions
PF, YX, YC, and QX designed the research. QX, SS, JC, SY, and DC conducted the laboratory analysis. YD, SY, HS, HT, WZ, LR, YL, YS, ZW, CQL, KK, GJ,
YC, and PF reviewed and commented on the paper. QX and PF wrote the paper.
Competing interests
The authors declare that they have no conflict of interest.
Disclaimer
Publisher’s note: Copernicus Publications remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Acknowledgements
The authors thank Lianfang Wei (Institute of Atmospheric Physics, Chinese Academy of Sciences, China) and Hong Ren (Tianjin University, China), for their helpful discussions.
Financial support
This research has been supported by the National Natural Science Foundation of China (grant nos. 41625014 and 41961130384).
Review statement
This paper was edited by Qiang Zhang and reviewed by two anonymous referees.
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