Atmospheric Environment 225 (2020) 117375

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Atmospheric Environment
journal homepage: http://www.elsevier.com/locate/atmosenv

NOx enhances secondary organic aerosol formation from nighttime

γ-terpinene ozonolysis
Li Xu a, Narcisse T. Tsona b, Bo You a, Yingnan Zhang a, Shuyan Wang a, Zhaomin Yang a,
Likun Xue a, Lin Du a, *
a
Environment Research Institute, Shandong University, Qingdao, 266237, China
b
School of Life Science, Shandong University, Qingdao, 266237, China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

� Ozonolysis of γ-terpinene is not an

important SOA source in NOx-isolated
regions.
� SOA size and yields from γ-terpinene
ozonolysis increase with the increasing
NOx.
� Organic nitrates are important compo­
nents of SOA from NOx-involved
ozonolysis.
� Nitrate radical contributes to nighttime
γ-terpinene oxidation.

A R T I C L E I N F O A B S T R A C T

Keywords: As an important component of anthropogenic emissions, nitrogen oxides (NOx) are well known to interfere with
γ-Terpinene daytime oxidation of biogenic volatile organic compounds (BVOCs) and secondary organic aerosol (SOA) for­
Ozonolysis mation. Nighttime chemistry is highly related to O3 and NOx level but, NOx effects on SOA formation from the
Secondary organic aerosol
ozonolysis of BVOCs, especially polyolefinic monoterpenes, have not been well understood. In the present study,
Nighttime
Anthropogenic-biogenic interactions
SOA formation from pure and NOx-involved γ-terpinene ozonolysis was studied in a smog chamber under dark
conditions. At atmospherically relevant particle mass loading of 10 μg m 3, the SOA yield from pure ozonolysis is
estimated by a two-product model to be 8.6%. When NOx were incorporated into γ-terpinene ozonolysis, both
the particle size and SOA yields increased simultaneously with elevated NOx mixing ratios. SOA yields doubled
(from 0.38 to 0.77) when the system moved from NOx-free to [γ-terpinene]0/[NOx]0 ¼ 3.5 (ppbC/ppb). The
characteristic absorption of organic nitrates was detected by Fourier transform infrared (FTIR) spectroscopy and
the fraction of organic nitrates increased with increasing NOx mixing ratios. Identification of the new constit­
uents in SOA from NOx-involved γ-terpinene ozonolysis and their formation channels suggest that the formation
of organic nitrates follows NO3 chemistry. NOx affects γ-terpinene ozonolysis via the enhanced generation of NO3
at high NOx and its subsequent more favored consumption of γ-terpinene than O3. The first-generation products
from NO3 oxidation of γ-terpinene could be further oxidized by ozone, forming more oxidized products that
contribute to SOA formation. Our investigation suggests that at night with high NOx levels, γ-terpinene may be a
significant source of SOA and organic nitrates through anthropogenic-biogenic interactions.

* Corresponding author.
E-mail address: lindu@sdu.edu.cn (L. Du).

https://doi.org/10.1016/j.atmosenv.2020.117375
Received 18 October 2019; Received in revised form 21 February 2020; Accepted 24 February 2020
Available online 27 February 2020
1352-2310/© 2020 Elsevier Ltd. All rights reserved.
L. Xu et al.
1. Introduction
The oxidation of volatile organic compounds (VOCs) generates
products that undergo chemical transformation and condensation to
form secondary organic aerosols (SOA) (Jimenez et al., 2009; Zhang
et al., 2007). SOA contribute to a major fraction of submicron atmo­
spheric aerosols, which are highly linked to the visibility reduction,
Earth’s radiation balance and regional climate change as well as human
respiratory and cardiovascular diseases (Hallquist et al., 2009; Jimenez
et al., 2009; Kavouras et al., 1998; Mauderly and Chow, 2008; Zaveri
et al., 2018). Biogenic VOCs (BVOCs) emitted by vegetation comprises
90% of the global VOC emissions (Guenther et al., 1995). Biogenic SOA
(BSOA) derived from BVOCs oxidation are estimated to be more than
one order of magnitude larger than SOA formed from anthropogenic
VOCs (Sakulyanontvittaya et al., 2008; Virtanen et al., 2010). The
importance of anthropogenic emissions in SOA formation is reflected in
their modulation of BVOCs oxidation and consequent BSOA formation as
many field observations and modeling predictions suggested (Budisu­
listiorini et al., 2015; Han et al., 2016; Liu et al., 2018; Shrivastava et al.,
2017; Spracklen et al., 2011).
Nitrogen oxides (NOx) are important anthropogenic pollutants that
are mainly emitted from combustion-related activities (Draper et al.,
2015; Reis et al., 2009). They have been receiving significant attention
due to their effects on the chemical evolution of BVOCs and SOA for­
mation (Berkemeier et al., 2016; Ng et al., 2017; Renbaum and Smith,
2009; Wildt et al., 2014). Recently, while many model studies showed
the increase of BSOA with decreased NOx, some studies demonstrated
that NOx reduction may result in the decrease of BSOA formation (Lane
et al., 2008; Matsui et al., 2014; Pye et al., 2013; Zhang et al., 2017). For
example, based on semi-volatile partitioning mechanism for SOA for­
mation modeled by Community Multiscale Air Quality model, BSOA
increased by 5% when NOx was reduced by 25% in Southeastern
America (Pye et al., 2013). A NOx reduction of 50% resulted in a limited
SOA reduction of 0.9–5.6% on a global scale as modeled by Community
Atmospheric Model version 4 with chemistry (Zheng et al., 2015). These
multifaceted effects of NOx on BSOA formation in the atmosphere are
related to the specific atmospheric conditions and parent precursors (Liu
et al., 2018).
BVOC oxidation induced by nitrate radical (NO3) is deemed as one of
the anthropogenic-biogenic interactions because nighttime NO3 radicals
formation occurs predominantly via the reaction of NOx with ozone
(Brown and Stutz, 2012; Kiendler-Scharr et al., 2016). In the USA, it was
estimated that monoterpene oxidation by the NO3 radical may lead to
more than half of the SOA derived from monoterpene oxidation (Pye
et al., 2015). Other studies showed that the nighttime contribution of
organic nitrates (4%–8%) to the total organic aerosol particle was higher
than that during the daytime (2%–4%) (Lee et al., 2016; Rollins et al.,
2012). Laboratory experiments usually use N2O5 as the source of NO3
radicals to study SOA and organic nitrates formation from NO3-initiated
BVOCs oxidation (Boyd et al., 2015; Fry et al., 2014; Griffin et al., 1999;
Moldanova and Ljungstro €m, 2000; Perraud et al., 2010). In fewer studies
NOx and ozone were introduced into the chamber to study NOx effects
on the dark ozonolysis of BVOCs. NOx effects on SOA formation from the
ozonolysis of several commonly studied monoterpenes have been found
to be different (Draper et al., 2015; Nojgaard et al., 2006; Presto et al.,
2005b). In α-pinene ozonolysis under dark conditions, characterized by
[VOC]0/[NOx]0 ratio varying from ~1 to ~300, the SOA yield from 150
to 200 ppb α-pinene ozonolysis remained constant (~0.30) for
[VOC]0/[NOx]0 > 15 and it decreased to be lower than 0.01 for
[VOC]0/[NOx]0 ¼ 0.65 (Presto et al., 2005b). With [O3]/[NO2] ranging
from 1:0.5 to 1:4 and [NO2]/[VOC] ranging from 1:1 to 2:1, β-pinene
and Δ3-carene produced fewer particles while limonene yielded higher
aerosol number and mass concentrations at high NOx levels (Draper
et al., 2015). The varied SOA formation behavior of these monoterpenes
may be related to their different isomeric structures (e.g., α-pinene
contains one endocyclic double bond and β-pinene contains one
2
Atmospheric Environment 225 (2020) 117375
exocyclic double bond) (Zhao et al., 2015). To the best of our knowl­
edge, NOx effects on dark ozonolysis of other monoterpenes (e.g. with
two endocyclic double bonds) have been rarely studied.
γ–Terpinene is one of monoterpenes with two substituted endocyclic
double bonds. Measurements in a tropical cloudy forest in Costa Rica
showed that γ–terpinene mixing ratio is up to 1.5 ppb in October, higher
than those of β-pinene (0.4 ppb) and limonene (1.3 ppb) (Esqui­
vel-Herna �ndez et al., 2011). In a rural mixed forest in northern Michi­
gan, the simulated formation of organic nitrates from the reaction of
γ–terpinene with NO3 was comparable to those of limonene, α-pinene,
and β-pinene (Pratt et al., 2012). While SOA formation from α-pinene,
β-pinene and limonene oxidation have been widely studied under
various conditions, γ–terpinene oxidation has received less attention
(Friedman and Farmer, 2018; Griffin et al., 1999; Slade et al., 2017).
SOA yields from γ–terpinene photooxidation were measured to be
0.10–0.16 within the aerosol mass range of 21.3–65.9 μg cm 3 (Griffin
et al., 1999). Using N2O5 as NO3 radicals precursor, γ–terpinene
oxidation produced a total organic nitrates yield of 14% and SOA yield
up to 10% under an atmospherically relevant aerosol mass loading of 10
μg cm 3 (Slade et al., 2017). These studies suggest that γ–terpinene can
be an important BSOA contributor, especially in regions with high
γ–terpinene emission rates, such as Midwest USA where γ–terpinene
makes up ~5% of the monoterpene emissions (Geron et al., 2000).
In this study, we investigated SOA formation from γ–terpinene ozo­
nolysis and the yield data were fitted by a two-product model. NOx ef­
fects on SOA yield and size distribution from γ–terpinene ozonolysis
were first examined in the present study. The chemical composition of
SOA formed under different NOx conditions was also explored with
Fourier transform infrared spectrum and high-resolution mass spec­
trometry. Considering that the nighttime atmospheric oxidation capac­
ity is highly related to O3 and NOx level, we used the NOx/O3 ratio of
0–0.7 that is relevant to the nighttime ambient conditions to assess the
SOA formation potential of γ–terpinene through anthropogenic-biogenic
interactions at night.
2. Experimental methods
2.1. SOA generation
All experiments were carried out in a collapsible 1 m3 Teflon
chamber under dark conditions and ambient pressure. The initial
experimental conditions are summarized in Table 1. Based on the
different experimental purposes, these experiments can be grouped into
three categories: pure ozonolysis of γ–terpinene (Exp.1-8), NOx-
involved ozonolysis with initial ~153 ppb of γ–terpinene
([γ–terpinene]0 ¼ ~153 ppb, Exp.9-15) and initial ~302 ppb of
γ–terpinene ([γ–terpinene]0 ¼ 302 ppb, Exp.16-26). The temperature
and relative humidity (RH) inside the chamber were monitored with a
hygrometer (Model 645, Testo AG, Germany). Before each experiment,
the chamber was flushed continuously with zero air that was generated
by a zero air supply (111-D3N, Thermo Scientific, USA) until the particle
number concentrations were less than 10 cm 3.
The introduction order of reagents was γ–terpinene, cyclohexane,
NOx (in NOx-involved experiments) and ozone. A known volume of
liquid γ–terpinene (Aldrich, 97%) was first injected into a stream of zero
air and evaporated into the chamber directly. Then, an excess amount of
cyclohexane (Aladdin, 99.5%) was flushed into the chamber by zero air
so that more than 90% of the OH radical formed by ozone reaction with
γ–terpinene reaction could be scavenged (Lee et al., 2006; Nah et al.,
2016). In experiments where NOx were involved, an expected amount of
NO or NO2 from the calibrated cylinder (490 ppm, YuyanGas®, China)
was introduced into the chamber with a gas-tight syringe. These gas
components were allowed to stabilize for 20 min before the injection of
ozone that was produced by an ozone generator (WH-H-Y5Y, Wohuan,
China). The reaction in the chamber was initiated by ozone and pro­
ceeded for two hours before the collection of SOA particles. Control
L. Xu et al. Atmospheric Environment 225 (2020) 117375

experiments showed negligible effects of cyclohexane on NOx chemistry
and SOA formation.
A set of real-time instruments were employed to characterize the gas-
phase and particle-phase components. The concentrations of NOx and
ozone were continuously measured by the NO–NO2-NOx analyzer
(Model 42i, Thermo Scientific, USA), and O3 analyzer (Model 49i,
Thermo Scientific, USA), respectively. Their sampling flow rate was 0.7
L min 1. No air was added into the chamber to avoid dilution and to
maintain a relatively stable chamber condition during the reaction. The
γ-terpenene concentration that was detected at 30 min interval by a gas
chromatography-flame ionization detector (GC-FID, 7890B, Agilent
Technologies, USA) with a DB-624 capillary column (30 m � 0.32 mm,
1.8 mm film thickness) could not be detected when SOA sampling
started. The particle number concentration and size distribution were
monitored throughout each experiment using the scanning mobility
particle sizer (SMPS, model 3080, TSI Inc., USA). SMPS was operated
with a sheath flow of 3 L min 1 and aerosol flow of 0.3 L min 1. Particle
sizes from 13.6 to 736.5 nm were recorded with a scanning cycle of 5
min. Since these experiments were performed in the absence of seed
particles that can provide surfaces for vapors to condense onto, the
initial particles formation in the chamber was driven by nucleation of
oxidation products.
The mass concentration of SOA generated in each reaction system
was also detected by SMPS with an estimated aerosol density of 1.2 g
cm 3. The mass-dependent SOA yield, representative of SOA formation
potential of a parent hydrocarbon, is defined as the consumption of
γ-terpinene (Δ[γ-terpinene], μg m 3) that is converted to SOA mass
(ΔM, μg m 3). It should be noted that both vapor and particles could be
lost to the chamber wall and influence SOA yields (Krechmer et al.,
2016; Ye et al., 2016; Zhang et al., 2015). The wall loss rate constants for
NOx, ozone and γ-terpinene were measured to be 1.72 � 10 7, 2.24 �
10 6, 6.8 � 10 7 s 1, respectively. These wall losses were less than 3%
in the first two hours. Although neglecting organic vapor wall loss may
cause an underestimation of SOA yields, the wall loss of organic vapor in
the present study may be mitigated by the use of excess oxidant con­
centrations. The quick ozonolysis and nucleation products would pro­
vide surfaces for vapors to partition onto, therefore reducing the vapor
wall loss (Nah et al., 2016; Stirnweis et al., 2017). Particle number and
mass concentrations in the first two hours were corrected for wall loss
based on the size-dependent particle loss rates in each experiment (Chen
et al., 2019a; Chu et al., 2016; Takekawa et al., 2003). Details about this
method are described in Fig. S1 in the supplementary material. Wall
effect in the particle collection period has not been evaluated as it would
have minor effect on the SOA composition analysis.
2.2. SOA collection and composition analysis
Sampling started after two hours after the reaction was initiated. The
remaining ~0.8 m3 mixture in the chamber was enough for approxi­
mately 1 h sampling at 10 L min 1 flow rate, during which some re­
actions might still proceed. SOA particles generated in experiments with
initial ~302 ppb γ–terpinene (Exp. 16-24) were collected onto
aluminum foil pieces by a 13-stage Dekati low-pressure impactor
(DLPIþ, DeKati Ltd, Finland). Functional groups and bond information
of particle-phase products were analyzed using attenuated total reflec­
tance coupled to the Fourier transform infrared spectroscopy (ATR-
FTIR, Vertex 70, Bruker, Germany). The sample spectra in the range of
4000-600 cm 1 were scanned by placing the aluminum foil pieces
directly onto the ATR crystal with the resolution of 4 cm 1 and 64 scans
were averaged. To ensure a clean background, the ATR crystal was
thoroughly cleaned after each sample spectrum acquisition, and the
aluminum foil spectrum as the background was subtracted. The spectra
baseline was corrected using the rubberband method (20 iterations and
64 baseline points) in OPUS software.

Table 1
Experimental conditions.
Exp. [γ-terpinene]0 [O3]0 [NOx]0 [γ-terpinene]0/[NOx]0 Temperature RH SOA
Yield
No. (ppb) (ppb) (ppb) (ppbC/ppb) (K) (%)

1a 31 123 0 – 297 34 0.14

2a 60 216 0 – 297 30 0.25
3a 76 304 0 – 300 27 0.29
4a 122 488 0 – 298 29 0.35
5a 154 629 0 – 299 30 0.38
6a 183 709 0 – 297 30 0.48
7a 215 763 0 – 298 31 0.55
8a 276 983 0 – 298 30 0.56

9b 154 565 37 40.6 300 29 0.40

10b 153 557 55 27.8 298 30 0.49
11b 155 602 76 20.3 301 25 0.52
12b 153 578 86 17.8 298 29 0.55
13b 152 609 144 10.7 297 36 0.65
14b 154 610 310 5.0 299 24 0.67
15b 153 590 441 3.5 299 30 0.77

16c 302 1236 0 – 292 17 0.55

17c 302 942 28 107.9 297 21 0.61
18c 302 1141 59 51.4 294 19 0.72
19c 302 992 145 20.8 293 20 0.82
20c 302 1250 238 12.7 294 19 0.92
21c 302 1430 461 6.6 294 20 0.97
22c 302 1475 550 5.5 295 22 1.09
23c 302 1611 603 5.0 294 19 1.18
24c 302 1780 780 3.9 294 23 1.30

25d 302 937 0 – 295 21 –

26d 302 935 547 5.5 293 22 –
a
Experiments aiming at studying SOA yields from pure ozonolysis.
b
Experiments aiming at studying SOA size and yields in NOx-involved ozonolysis: NO2 was added.
c
SOA size and yield in NOx-involved ozonolysis and particles were collected onto aluminum foil for composition analysis by FTIR: NO was added. The addition of O3
was adjusted with the mixing ratio of NO to compensate the quick consumption of O3 by NO.
d
Particles were collected onto PTFE filters for composition analysis by UPLC/ESI-HR-Q-TOFMS.

3
L. Xu et al. Atmospheric Environment 225 (2020) 117375

SOA composition characterization was also performed using an

ultra-performance liquid chromatography (UPLC, Ultimate 3000,
Thermo scientific, USA) system coupled to the electrospray ionization
high-resolution quadrupole time-of-flight mass spectrometry (ESI-HR-Q-
TOFMS, Bruker Impact HD, Germany). SOA (Exp. 25-26) were collected
onto polytetrafluoroethylene (PTFE) filters (0.22 μm pore size, 47 mm
dimeter, TJMF50, Jinteng, China) by a stainless steel 47 mm inline filter
holder (Sartorius 16254, Sartorius Stedim Biotech GmbH, Germany).
PTFE samples were first extracted with 5 mL methanol (Optima® LC/MS
grade, Fisher Scientific) by sonication for 30 min. Then the extracts were
filtered through a 25 mm diameter, 0.22 μm pore PTFE membrane sy­
ringe filter (Jinteng, China) to remove insoluble material. After the
extracted solution was concentrated to almost dryness under a gentle
stream of nitrogen, the extract residues were reconstituted with 500 μL
of 50:50 (v/v) solvent mixture of 0.1% formic acid (Optima® LC/MS
grade, Fisher Scientific) in methanol and 0.1% formic acid in ultrapure
water (Milli-Q, Millipore, France). The blank controls of filters were
handled and analyzed as samples to avoid the interference of PTFE filter
artifacts on composition analysis. Finally, these prepared samples were
analyzed by UPLC/ESI-HR-Q-TOFMS that was operated in negative
ionization mode with a mass range of m/z 50-1000. Chromatographic
separations were performed using an Atlantis T3 C18 column (100 Å, 3
μm particle size, 2.1 mm � 150 mm, Waters, USA). The mobile phases
consisted of (A) 0.1% formic acid in water and (B) 0.1% formic acid in Fig. 1. Time evolution of wall-loss corrected SOA size (aerodynamic diameter)
methanol. The applied 60 min gradient elution program, with the flow and mass concentration obtained from γ-terpinene/O3 experiment (Exp. 6).
rate of 200 μL min 1 and injection volume of 5 μL, was as follows: 3% B
for the first 3 min, increased linearly to 50% B from 3 to 25 min, and
increased from 50% to 90% B for another 18 min, decreased back to 3%
B from 43 to 48 min, and then held at 3% B from 48 to 60 min
(Kourtchev et al., 2015).

3. Results and discussion

3.1. γ-Terpinene ozonolysis

SOA formation from γ–terpinene ozonolysis was firstly investigated

at different initial γ–terpinene concentrations. The time evolution pro­
file of particle wall loss corrected SOA number concentration and total
mass concentration are plotted in Fig. 1 (Exp. 6). Particle formation is
observed by the burst of the particle number in the first few minutes of
ozone injection. These fast-formed small particles grow quickly to be
larger than 100 nm within 20 min with a decrease in number concen­
tration, which may appear if the coagulation between these small par­
ticles and/or the partitioning of gas-phase products to particle-phase
exceed the new particle formation through homogeneously nucleation
(Friedman and Farmer, 2018). The SOA mass concentration reaches its
maximum at about one hour after the initiation of the reaction. In the Fig. 2. SOA yields of γ-terpinene ozonolysis as a function of SOA mass con­
absence of seeds, the supersaturation of condensable products that have centrations (ΔM) (Exp.1-8). The experimental data are fitted with the two-
extremely low volatility was suggested to drive the initial nucleation product model. The mass-dependent yield data of α-pinene, β-pinene, and
(Donahue et al., 2013). The formation of extremely low volatility limonene ozonolysis reported in previous studies were normalized to density ¼
organic compounds (ELVOCs) was observed within the first minute after 1.2 g cm 3 for comparison. The experimental conditions for these ozonolysis
the injection of ozone to monoterpenes ozonolysis systems (Jokinen experiments are summarized in Table S1.
et al., 2015). Endocyclic BVOCs were thus concluded to be efficient
precursors for ELVOCs formation through ozonolysis. The burst of X αi Kom;i
nanoparticles in γ-terpinene/O3 system at the initial few minutes may Y ¼ M0
1 þ Kom;i M0
also result from the quick formation of ELVOCs and their homogeneous i

nucleation. While the formation and nucleation of ELVOCs may explain

where αi is the mass-based stoichiometric fraction of product i and Kom,i
the primary increase of SOA mass loadings, semi-volatile organic com­
(m3 μg 1) is the gas–particle partitioning equilibrium constant. In this
pounds (SVOCs) probably begin to contribute more through absorptive
model, one group of parameters (α1 and Kom,1) represents the ensemble
partitioning at higher SOA mass loadings (~10 μg m 3) (Ehn et al.,
of products with relatively low volatility and the other group of pa­
2014).
rameters (α2 and Kom,2) designates the ensemble of products with rela­
SOA yields increase with the increasing total SOA mass loadings as
tively high volatility. The experimental values of SOA yields versus mass
shown in Fig. 2. This correlation can be expressed by a semi-empirical
concentrations can be well reproduced by the two-product model as the
model, which is built on the basis of the absorptive gas-particle parti­
well-fitted curve (R2 ¼ 0.99) shown in Fig. 2. The final fitting parameters
tioning of produced SVOCs (Odum et al., 1996).
are α1 ¼ 0.77, Kom,1 ¼ 7.64 � 10 4, α2 ¼ 0.23, and Kom,2 ¼ 0.05. Taking

4
L. Xu et al.
a typical 10 μg m 3 of aerosol mass loading in regions affected by BSOA
into consideration, the simulated SOA yield is 8%. At such a lower
aerosol mass loading, the rapid SOA yield increase is most likely caused
by the partitioning of the lowest volatility products. When the aerosol
mass loading is larger than 500 μg m 3, which is relevant to heavily
polluted environments, the SOA yield reaches 0.47. The SOA yield
change became slower at high SOA mass concentrations, suggesting the
partitioning of relative volatile species.
The ozonolysis of some other monoterpenes has been well studied
previously (Griffin et al., 1999; Lee et al., 2006; Saathoff et al., 2009;
Song et al., 2007; von Hessberg et al., 2009). For comparison of SOA
formation potential of different isomeric monoterpenes, the results from
α-pinene, β-pinene, and limonene ozonolysis conducted under compa­
rable conditions are also plotted in Fig. 2, while their experimental
conditions are summarized in Table S1. As shown in Fig. 2, the reaction
between limonene and ozone (293 K, dry, Saathoff et al.) has the highest
yields, including when temperature and RH effects are considered (the
~5 K higher temperature may cause the SOA yield to decrease by 5%
and humidity was suggested to have little effect on SOA yields from
limonene ozonolysis) (Presto et al., 2005a; Saathoff et al., 2009; von
Hessberg et al., 2009). SOA yields from α-pinene ozonolysis that was
performed with RH < 2% by Song et al. are also higher than that in
γ-terpinene ozonolysis under RH ¼ ~30% (Song et al., 2007). The higher
α-pinene SOA yield is still expected even under similar humidity con­
dition because humidity would not influence SOA formation from
α-pinene ozonolysis (Saathoff et al., 2009). β-Pinene ozonolysis that was
conducted under dry conditions by Hessberg et al. exhibited lowest SOA
yields compared to limonene, α-pinene, and γ-terpinene (von Hessberg
et al., 2009). Considering that RH would suppress β-pinene SOA for­
mation, SOA yields from the γ-terpinene þ O3 reaction are expected to
be comparable to β-pinene ozonolysis in low aerosol mass loading and
much larger when the aerosol mass loading is greater than 100 μg m 3
(Moortgat, 2002).
Different SOA formation potential from isomeric monoterpenes can
be attributed to their different structures (Griffin et al., 1999; Zhao et al.,
2015). It has been suggested that the ozonolysis of monoterpenes with
endocyclic double bonds, such as α-pinene, produced ELVOCs very
rapidly with much greater molar yields than monoterpenes with
exocyclic double bonds, such as β-pinene (Jokinen et al., 2015). Limo­
nene has one endocyclic and one exocyclic double bond in its structure.
The unsaturated first-generation products can further react with O3 to
form highly oxidized products with high molecular weight that can
easily condense onto the particle phase. Hence, the SOA yields from
limonene ozonolysis are the highest (Saathoff et al., 2009). Despite the
two endocyclic double bonds in γ-terpinene, the SOA yields from its
ozonolysis are lower than in that of limonene. Because the ozonolysis of
the second double bond in γ-terpinene may cause the dissociation of the
carbon skeleton, the consequent products with smaller molecular weight
might be more volatile and thus the SOA yield would be lower (Lee et al.,
2006).
3.2. Effect of NOx on γ-terpinene ozonolysis
3.2.1. Effect of NOx on SOA size distribution and yields
The size distribution of particles from different [γ-terpinene]0/
[NOx]0 (ppbC/ppb) systems at 1 h after the initiation of the reaction is
shown in Fig. 3. In two cases with different initial γ-terpinene mixing
ratios, the decrease of [γ-terpinene]0/[NOx]0 ratios reduced particle
number concentrations compared with pure ozonolysis, concurrent with
a shift of particle number mode diameter to larger ones. For experiments
with initial ~15 ppb γ-terpinene, the number mode diameter of particles
increased from 131 nm in pure ozonolysis reaction to 163 nm when
[γ-terpinene]0/[NOx]0 ratio reached 5.0. A similar effect of NOx on the
particle size distribution was also observed from the ozonolysis of
α-pinene (~50 ppb) and d-limonene (~50 ppb). The presence of 50 ppb
NO2 leads the particle mode diameter to increase by 20 nm for α-pinene
5
Atmospheric Environment 225 (2020) 117375
Fig. 3. Size distributions of SOA particles generated under different NOx levels
at 1 h after the initiation of the reaction.
and 11 nm for d-limonene compared to pure ozonolysis, and the particle
number concentration decreased in both α-pinene and d-limonene cases
(Nojgaard et al., 2006). It was explained that introducing NOx into the
reaction system resulted in less O3 available for the oxidation of parent
compounds and, thus, to the decreased particle number concentration.
However, this might not be the case for γ-terpinene ozonolysis because
ozone is in excess in our experiments. The presence of NOx tends to
affect the gas-phase reaction mechanism in different ways among which,
one is to react with organic peroxy radicals (RO2). The RO2 þ NO re­
action is insignificant in the present study because the pre-existing NO
can be rapidly converted to NO2 once excessive ozone is injected into the
chamber. RO2 reacts with NO2 to produce peroxy nitrates (RO2NO2),
which are thermally labile under ambient conditions and less likely to
contribute to SOA formation (Atkinson, 2007; Berkemeier et al., 2016;
Hallquist et al., 1999). Another fate of NOx in our experiments is to form
NO3 radicals by the reaction between O3 and NO2. Monoterpenes
oxidation by NO3 radical is potentially efficient for SOA and organic
nitrates formation (Fry et al., 2014; Ng et al., 2017). If products from
quick oxidation of γ-terpinene by NO3 radical and/or following sec­
ondary reactions (e.g. the further ozonolysis of the first-generation
products) are much easier to partition into the particle-phase, the par­
ticle formation would be promoted. The following particle growth
through coagulation can result in the increase of particle size and
decrease of particle number concentration.
SOA yields from γ-terpinene ozonolysis at varying [γ-terpinene]0/
[NOx]0 ratios are plotted in Fig. 4. They vary quite dramatically as the
reaction system moves from low NOx to high NOx mixing ratios.
Compared to pure ozonolysis where the SOA yield is 0.38, the SOA yield
increases to 0.77 when NOx level is elevated to [γ-terpinene]0/[NOx]0
¼ 3.5 in experiments with initial ~ 153 ppb γ-terpinene. Even for similar
[γ-terpinene]0/[NOx]0 ratios, significantly higher SOA yields are
observed in experiments with initial higher γ-terpinene mixing ratios
(~302 ppb). Positive effects of precursor concentrations on SOA yields
were found in NOx associated α-pinene ozonolysis. With a [VOC]0/
[NO2]0 ratio of ~15, the SOA yields of 0.3 and only 0.08 were observed
for experiments with incipiently higher (150–200 ppb) and lower
(15–30 ppb) α-pinene mixing ratios, respectively (Presto et al., 2005b).
However, NOx exhibit quite different effects on SOA yields from
α-pinene ozonolysis and γ-terpinene ozonolysis. While NOx obviously
enhance γ-terpinene SOA formation over the [γ-terpinene]0/[NOx]0
range studied, previous studies suggested that increasing NOx concen­
tration substantially deplete SOA formation from α-pinene ozonolysis
(Draper et al., 2015; Presto et al., 2005b). Such a negative NOx effect on
α-pinene ozonolysis was attributed to high volatile products and near
L. Xu et al. Atmospheric Environment 225 (2020) 117375

Fig. 4. SOA yields from NOx-involved γ-terpinene ozonolysis (Exp. 9-24). Fig. 5. Time series of γ-terpinene consumption by O3 or NO3 under different
NOx conditions (Exp. 11 and Exp.14).

zero SOA yield from NO3 oxidation (Fry et al., 2014). The effects of NOx
on SOA formation from the ozonolysis of β-pinene, Δ3-carene and making the γ-terpinene consumption to shift from O3-dominated to
limonene have been investigated using a dark flow through a chamber NO3-dominated oxidation. Thereby, the particle size and SOA yields
by Draper et al. and it was found that by keeping O3 mixing ratio con­ increase can be caused by the increased NO3 radical contribution as
stant and varying NOx mixing ratio, SOA yields from β-pinene and expected (Figs. 3 and 4).
Δ3-carene ozonolysis were comparable over the range of oxidation
conditions ([O3]/[NO2] ¼ 2–0.5, [NO2]/[VOC] ¼ 0.5–1) while limo­
3.3. Effect of NOx on SOA composition
nene SOA yield increased with NOx concentration (Draper et al., 2015).
The later observation was explained by increased multifunctional
NO3-induced BVOC oxidation is a potentially efficient pathway for
organic nitrates and oligomers fraction in SOA at higher NOx.
the formation of organic nitrates, which can partition into the condensed
The increased SOA yields with NOx mixing ratios may result from the
phase and contribute to SOA formation and growth (Faxon et al., 2018;
enhanced competition between NO3- and O3-initiated γ-terpinene
Ng et al., 2017). In the presence of NOx, NO3 radical formation and its
oxidation. To quantify the relative contributions of NO3 radical and O3
further competition with O3 are expected to produce particle-phase
to γ-terpinene consumption under different NOx conditions, we built up
organic nitrates. To get detailed information about functional groups
a simple kinetic box model (Draper et al., 2015; Fry et al., 2009; Noj­
in particle-phase products, SOA collected onto aluminum foil pieces
gaard et al., 2006). The concentration evolution of γ-terpinene and its
(Exp. 16-24) were analyzed by ATR-FTIR. Some typical infrared spectra
loss ascribed to the O3/NO3 reaction were estimated. The model was
of SOA generated from three NOx level experiments (NOx-free, [γ-ter­
initialized with the observed O3, NOx and the mass of γ-terpinene
pinene]0/NOx]0 ¼ 20.8, and [γ-terpinene]0/NOx]0 ¼ 3.9) are shown in
injected and constrained with the known reaction rates. Reactions and
Fig. 6. All SOA samples exhibit strong absorption at 1713 cm 1, which is
corresponding rate constants incorporated in this model are summarized
attributed to the stretching vibration of the carbonyl moiety (Allen et al.,
in Table S2. The rate constant of the gas-phase reaction between O3 and
1994; Presto et al., 2005b). When NOx were present in the γ-terpinene
NO2 at 298 K is 3.2 � 10 17 cm3 molec 1 s 1, about four times lower
ozonolysis system, three new strong absorption peaks appeared at 1635,
than the rate constant (1.4 � 10 16 cm3 molec 1 s 1) of the reaction
between O3 and γ-terpinene (Atkinson et al., 1990; Sander et al., 2011).
This shows that the NO3 radical formation may be not favored until the
mixing ratio of NOx is about four times higher than that of γ-terpinene
during the reaction process. The initial consumption of γ-terpinene is
dominated by ozonolysis, especially in experiments with lower NOx
mixing ratios. As modeled results show (Fig. 5), O3 is the dominant
oxidant when the initial NOx mixing ratio is 76 ppb ([γ-terpinene]0/­
NOx]0 ¼ 20.3). When NOx concentration is elevated to 310 ppb
([γ-terpinene]0/NOx]0 ¼ 5.0), the competition between O3 and NO3
radical for γ-terpinene shifts from O3-dominated to NO3-dominated
oxidation at ~10 min after the initiation of the reaction. The SOA yield
at this [γ-terpinene]0/NOx]0 ratio is 0.67, 0.29 higher than that in pure
ozonolysis (Exp.5). In a previous study, the homogeneous nucleation
potential of monoterpenes, especially endocyclic monoterpenes, was
suggested to be much higher during ozonolysis than in oxidations by
NO3 or OH radicals (Bonn and Moorgat, 2002). The initial consumption
of γ-terpinene by O3 is thus expected to be primarily responsible for new
particle formation. The products from oxidations by NO3 radical and O3
would be both incorporated into SOA growth through condensation
(Perraud et al., 2012). As NOx concentration increases, the decreased
γ-terpinene consumption by O3 results in more reactant for NO3 radical, Fig. 6. Infrared spectra of SOA generated under different NOx conditions (Exp.
16, 19, 24).

6
L. Xu et al.
1281 and 854 cm 1, corresponding to the asymmetric stretching of NO2,
symmetric stretching of NO2, and symmetric stretching of NO, respec­
tively (Bruns et al., 2010; Hallquist et al., 1999). Besides these three
prominent organonitrate peaks, two other weaker absorptions at 696
and 752 cm 1 could also be assigned to the characteristic absorption of
organic nitrates according to the infrared spectra of 2-ethylhexyl nitrate
(Day et al., 2010). The wide absorption shoulder from 985 to 1243 cm 1
is assigned to C–O and C–O–O groups while the smaller absorption at
957 cm 1 matches the O–O group (Jia and Xu, 2018). The coexistence of
multiple functional groups in the infrared spectrum illustrates that
multifunctional organic nitrates may be an important component of
SOA.
The infrared spectra of SOA from γ-terpinene ozonolysis are char­
acterized by the dominated absorption of carbonyl group, which grad­
ually lost its superiority as NOx levels were elevated. To further evaluate
the trends of organic nitrates production with varying initial NOx con­
ditions, infrared peak heights of organic nitrates (1635, 1281, 854 and
752 cm 1) are normalized with respect to the carbonyl group at 1713
cm 1 (Fig. 7). Clearly, the relative peak heights for organic nitrates in­
crease with the increasing NOx mixing ratios. It is estimated that adding
organic nitrate functional groups to hydrocarbons can reduce the equi­
librium saturated vapor pressure by 2–3 orders of magnitude (Lee et al.,
2016). The increased organic nitrates fraction in SOA samples may
partially explain the dramatic increase of SOA yields at higher NOx
conditions (Fig. 4). Under lower NOx levels, for example, [γ-terpine­
ne]0/[NOx]0 ¼ 51. (Exp.18), the normalized peak heights for organic
nitrates at 1635, 1230, 854 cm 1 are 0.58, 0.65, and 0.35, respectively,
lower than the carbonyl absorbance at 1713 cm 1. The SOA yield at this
NOx mixing ratio is 0.17 higher than that from pure ozonolysis (Exp.16).
Peak height ratios of organic nitrates to the carbonyl, namely
1635/1713, 1230/1713, 854/1713, reach 1.8, 1.6 and 1.3 when
[γ-terpinene]0/[NOx]0 decreases to 3.9 (Exp.24). Compared with pure
ozonolysis, the SOA yield increases by 0.75. Enhanced organic nitrates
formation at higher NOx is consistent with NO3 radical formation.
Combining with increased SOA yields, products containing the organic
nitrate moiety may be less volatile than species formed from NOx-free
conditions. Organic nitrates were also observed to be important SOA
components from limonene ozonolysis. With varying NO2 concentra­
tions, organic nitrates produced by NO3-induced limonene oxidation
accounted for about 30% of the total SOA mass (Draper et al., 2015; Fry
et al., 2011). Organic nitrates in γ-terpinene SOA indicate that γ-terpi­
nene is also an important source of organic nitrates in regions with
Fig. 7. Peak height ratio of organic nitrates (1635, 1280, 854, 752 cm 1) to
carbonyl (1713 cm 1) for SOA generated under different NOx conditions (Exp.
16, 18, 19, 21, 24).
7
Atmospheric Environment 225 (2020) 117375
elevated NOx levels.
The SOA composition from pure and NOx-involved γ-terpinene
ozonolysis (Exp. 25 and 26) was further examined by UPLC/ESI-HR-Q-
TOFMS operated in the negative ionization mode. Due to the presence
of ozone in NOx-free and NOx-involved experiments, the ozonolysis of
γ-terpinene occurred in both cases. As shown in Fig. 8, most commonly
shared mass spectrum peaks could be the products from γ-terpinene
ozonolysis. In the pure ozonolysis of γ-terpinene, where O3 is the only
oxidant, four Criegee intermediates (CIs) are likely to form considering
similar character of the two double bonds (Fig. S2). The subsequent
reactions of these CIs may be responsible for the species detected in the
particle-phase. Based on the accurate m/z values in the negative ioni­
zation mass spectra, compounds in SOA that can be formed through CIs
reactions are tentatively identified and the possible formation channels
are proposed (Fig. 9). Unimolecular reactions of excited CIs lead to
various products, including organic acids, aldehydes, and carbonyls
(Tobias and Ziemann, 2001). Most of these species are in the mid mass
range of 160 < m/z < 250. Products with larger molecular weight (m/z
> 250) in the particle phase can be formed via bimolecular reactions of
collisionally stabilized CIs with organic acids, carbonyls or some other
reactions (e.g. hemi-acetal and aldol condensations) (Heaton et al.,
2007; Kundu et al., 2012; Mackenzie-Rae et al., 2018). For example, m/z
313 and 329 product ions are detected in the SOA sample with high
relative intensity (>8%). Corresponding elemental compositions are
identified as C16H26O6 and C16H26O7 (ΔM/M < 10 5), respectively.
These two secondary ozonides can be formed through the reaction of
stabilized CIs with carbonyl compounds (Heaton et al., 2007). Due to the
presence of two double bonds in γ-terpinene, the ozonolysis of the sec­
ond double bond produces species with smaller molecular weight. Some
of these second-generation products can partition into the particle-phase
as observed in the mass spectra. For example, products ions of m/z 127,
129,145 can be formed via the subsequent reaction of a C6 CI that is
generated by the ozonolysis of first-generation products. Overall, the
nucleation, absorptive partitioning of ozonolysis products between the
gas and particle phases and coagulation promote γ-terpinene SOA for­
mation and growth.
In NOx-involved γ-terpinene ozonolysis, some new peaks appear
with relatively high intensities (Fig. 8). NOx affect the SOA composition
in two different channels as discussed above. NO3 chemistry is expected
to be the efficient way to influence SOA composition (Draper et al.,
2015). Following NO3 radical oxidation mechanism, some new peaks are
tentatively identified as organic nitrates based on the accurate mass
(ΔM/M < 10 5) and their absence in the pure-ozonolysis.
Fig. 8. The ESI mass spectrum (negative ionization mode) of SOA form pure
(Exp. 25) and NOx-involved (Exp. 26) γ-terpinene ozonolysis. Ion peaks with
relative intensity greater than 3% of the strongest peak are shown.
L. Xu et al. Atmospheric Environment 225 (2020) 117375

Fig. 9. Proposed formation mechanisms for compounds in SOA from γ-terpinene ozonolysis (pink structures). The pink structures are tentatively identified based on
the negative ionization mode ESI mass spectrum from UPLC/ESI-HR-Q-TOFMS detection. The partial formation pathway for high molecular weight products (m/z ¼
313, 329) via the reaction between stabilized CIs and carbonyl is shown in the dotted box. The formation of some second-generation products from the ozonolysis of
the first-generation products (m/z ¼ 127, 129, 145) is shown in the solid box. Other reaction pathways and isomers are possible but are not shown here for clarity.
(For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)

Corresponding reaction pathways are proposed in Fig. 10. Note that
ozone and NO3 radical are simultaneously present as oxidants in the
reaction system with NOx, first-generation products from γ-terpinene
oxidation by NO3 radical could be further oxidized by ozone to form
second-generation products. The observation of most of new peaks (e.g.,
m/z ¼ 278, 346, 266, 262) could be explained by these
second-generation multifunctional organic nitrates. The dominant new
peaks are in the region m/z > 250, which comprises a greater fraction of
total ion intensity than in pure ozonolysis. The organic nitrates identi­
fied here are in line with the strong absorbance of organic nitrates in the
infrared spectrum. Hence, the most important pathway for NOx to affect
SOA yields and composition is to be converted to NO3 radical that can
oxidize γ-terpinene directly. Both the first and subsequent
second-generation products contribute substantially to SOA growth and
SOA yield.
4. Conclusions
The nighttime atmospheric oxidation capacity is highly relevant to
NOx levels. In relatively clean regions that are isolated from NOx
emission sources, O3 is the dominant oxidant for BVOCs oxidation.
When NOx are transported to densely forested areas with high BVOC
emissions or vice versa, the dominance of O3 for BVOC oxidation can be
altered (Chen et al., 2019b). In the present study, nighttime SOA for­
mation from γ-terpinene ozonolysis and NOx effects on this process were
both studied under dark conditions. With varying initial γ-terpinene
mixing ratios, a set of SOA yields (0.14–0.55) were obtained in the
aerosol mass loading ranging from 25 to 660 μg m 3. The yield data
could be well fitted by a two-product model. The relatively low SOA
yield under atmospherically relevant SOA mass loadings suggests that
γ-terpinene may not be an important SOA precursor in regions that are
less affected by NOx emissions.
NOx effects on γ-terpinene ozonolysis were studied with varying NOx
conditions. The [NOx]0/[O3]0 ratio ranged approximately from 0 to 0.7
and [γ-terpinene]0/[NOx]0 varied in a relatively larger range ([γ-terpi­
nene]0/[NOx]0 ¼ 4-100). These conditions can be representative of
relative clean or NOx polluted night atmospheric environments in some
regions (Chen et al., 2019b; Millet et al., 2016). When different levels of
NOx were considered in the γ-terpinene ozonolysis system, we found
that this process produced particles with larger mode diameter at rela­
tively higher NOx levels. Meanwhile, SOA yields increased markedly
with the decreasing [γ-terpinene]0/[NOx]0 ratios. The SOA composition
analysis by ATR-FTIR showed that the fraction of organic nitrates in­
creases with increasing NOx concentrations. The characterization of
chemical components by UPLC/ESI-HR-Q-TOFMS and the mechanism
analysis suggested that multifunctional organic nitrates with high mo­
lecular mass (m/z > 250) can be formed in NOx-involved γ-terpinene
ozonolysis.
The enhancement effect of NOx on SOA yields and organic nitrates
formation can be mainly explained by the generation of NO3 radical and
its competition with O3. The first-generation products from γ-terpinene
oxidation by NO3 radical could be further oxidized by O3, forming
multifunctional organic nitrates that can contribute to SOA formation.
In regions with high NOx levels, the more favored γ-terpinene oxidation
by NO3 radical is likely to greatly accelerate γ-terpinene consumption,
limit its atmospheric lifetime and most importantly, strengthen organic

8
L. Xu et al.
Fig. 10. Proposed formation mechanisms for compounds in SOA generated in NOx-involved γ-terpinene ozonolysis. The pink structures are tentatively identified as
organic nitrates based on the negative ionization mode ESI mass spectrum from UPLC/ESI-HR-Q-TOFMS detection. (For interpretation of the references to colour in
this figure legend, the reader is referred to the Web version of this article.)
nitrates fraction in SOA.
Organic nitrates contribute substantially to nighttime organic aero­
sol as many recent field observations suggested (Kiendler-Scharr et al.,
2016; Sobanski et al., 2017; Yu et al., 2019). Our study corroborates the
important role of NOx on nighttime γ-terpenene oxidation, suggests also
that γ-terpinene is an important BVOC precursor that can contribute to
particle-phase organic nitrates and SOA formation in the nighttime.
Models that are used to predict regional or global SOA mass loadings of
organic nitrates formation should take into account γ-terpinene oxida­
tion, especially in regions influenced by both anthropogenic pollutants
and high γ-terpinene emissions.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
CRediT authorship contribution statement
Li Xu: Conceptualization, Methodology, Investigation, Writing -
original draft. Narcisse T. Tsona: Writing - review & editing, Visuali­
zation. Bo You: Investigation. Yingnan Zhang: Methodology, Software.
Shuyan Wang: Investigation. Zhaomin Yang: Investigation. Likun
Xue: Methodology, Software. Lin Du: Conceptualization, Funding
acquisition, Project administration, Resources, Supervision,
Visualization.
9
Atmospheric Environment 225 (2020) 117375
Acknowledgements
This work was supported by National Natural Science Foundation of
China (91644214), Shandong Natural Science Fund for Distinguished
Young Scholars (JQ201705), and Fundamental Research Fund of
Shandong University (2020QNQT012).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.atmosenv.2020.117375.
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