# Anthropogenic-Biogenic Interactions at Night: Enhanced Formation of Secondary Aerosols and Particulate Nitrogen- and Sulfur-Containing Organics from beta-Pinene Oxidation

Li Xu, Zhaomin Yang, Narcisse Tsona, Xinke Wang, Christian George, Lin Du

► To cite this version:

Li Xu, Zhaomin Yang, Narcisse Tsona, Xinke Wang, Christian George, et al.. Anthropogenic-Biogenic Interactions at Night: Enhanced Formation of Secondary Aerosols and Particulate Nitrogen- and Sulfur-Containing Organics from beta-Pinene Oxidation. Environmental Science and Technology, 2021, 55 (12), pp.7794-7807. 10.1021/acs.est.0c07879. hal-03300495

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# Anthropogenic–Biogenic Interactions at Night: Enhanced Formation of Secondary Aerosols and Particulate Nitrogen- and Sulfur-Containing Organics from β-Pinene Oxidation

Li Xu, Zhaomin Yang, Narcisse T. Tsona, Xinke Wang, Christian George, and Lin Du*

**ABSTRACT:** The oxidative photo-dehydrogenation of glycerol to produce H2 and other valuable chemicals was studied using different materials. In particular, Pt nanoparticles were deposited on microemulsion-synthesized TiO2 via surface organometallic chemistry (SOMC) and compared with photocatalysts obtained using more conventional methods. Well-defined Pt(II) single-site titania-grafted were prepared reacting the surface hydroxyl groups of TiO2 nano-oxides with the organometallic Pt(COD)Me2 complex. Sample reduction under H2 generated ultrafine Pt nanoparticles well-dispersed on titania surface. Its performance under simulated solar light showed superior activity when compared to analogous Pt-containing catalysts prepared by other methods. Improved dispersion of Pt metal on titania surface was among the primary reasons of a better overall activity, providing relatively high rates of hydrogen productivity. Moreover, an increase of glyceraldehyde productivity in liquid phase was observed with the increase of Pt dispersion, demonstrating that the metal dispersion can strongly affect the selectivity of chemicals produced in the reaction. Comparison with state of the art shows that the present material exhibits excellent performance for a combined positive effect of the high specific surface area of titania prepared by microemulsion, giving access to the increased densities of active sites and the high dispersion of Pt nanoparticles given by the SOMC technique.

**KEYWORDS:** β-pinene, secondary aerosol, anthropogenic–biogenic interactions, organic nitrates, nitrooxy organosulfates, night time ozonolysis

## 1. INTRODUCTION

Aerosol particles in the atmosphere have negative impacts on regional air quality, climate change, and human health.<sup>1,2</sup> Secondary aerosols produced during the oxidation of volatile organic compounds (VOCs) or inorganic precursors, for example, NO<sub>x</sub>/SO<sub>2</sub>/NH<sub>3</sub>, represent a large fraction of the total aerosol particle mass.<sup>3,4</sup> Biogenic VOCs (BVOCs) are globally the main precursors for the secondary organic aerosol (SOA) budget due to their relatively high emission rates (about ten times higher than anthropogenic VOCs) and high reactivity toward atmospheric major oxidants.<sup>5–7</sup> When BVOCs mix with anthropogenic emissions, the oxidation of BVOCs and their SOA formation potential can be altered as highlighted by many field observations.<sup>8–12</sup> However, anthropogenic–biogenic interactions during SOA formation are more complex than their current representation in models, and consequently, uncertainties in the predicted SOA budget might be induced.<sup>13–16</sup>

Nitrogen-containing and sulfur-containing compounds derived from BVOCs are key species in biogenic SOA. They can form via anthropogenic–biogenic interactions as anthropogenic pollutants, for example, NO<sub>x</sub>/SO<sub>2</sub>/NH<sub>3</sub>/sulfate can serve as precursors to their formation.<sup>17–19</sup> NO<sub>x</sub> may impact organic nitrates and total SOA formation by either influencing the local oxidation capacity, especially during night time through the NO<sub>3</sub><sup>-</sup> radicals or by facilitating the formation of condensable organic nitrates.<sup>20–22</sup> Modeled or field-observed correlations between NO<sub>x</sub> and biogenic SOA formation are however still elusive as the decrease in NO<sub>x</sub> can either decrease or increase biogenic SOA formation.<sup>23</sup> Particulate organosulfates, which are usually formed through the reactions involving VOC oxidation products and acidic sulfate, could be a potential source of “missing SOA” that is not yet implemented in current atmospheric models.<sup>24,25</sup> Indeed,
<table><caption>Table 1. Summary of Experimental Conditions</caption><thead><tr><th>exp. no.<sup>a</sup></th><th>[β-pinene]<sub>0</sub> (ppb)</th><th>[O<sub>3</sub>]<sub>0</sub> (ppb)</th><th>[NO<sub>2</sub>]<sub>0</sub> (ppb)</th><th>[SO<sub>2</sub>]<sub>0</sub> (ppb)</th><th>[NH<sub>3</sub>]<sub>0</sub> (ppb)</th><th>T (K)</th><th>RH (%)</th><th>aerosol mass (µg m<sup>-3</sup>)</th><th>aerosol yield</th></tr></thead><tbody><tr><td>βO<sup>b</sup></td><td>154</td><td>624</td><td>0</td><td></td><td></td><td>300</td><td>22</td><td>156.4 ± 2.9</td><td>0.18 ± 0.01</td></tr><tr><td>βON.1</td><td>154</td><td>567</td><td>32</td><td></td><td></td><td>298</td><td>33</td><td>290.8 ± 12.4</td><td>0.33 ± 0.01</td></tr><tr><td>βON.2</td><td>154</td><td>575</td><td>78</td><td></td><td></td><td>298</td><td>37</td><td>524.4 ± 13.5</td><td>0.60 ± 0.03</td></tr><tr><td>βON.3</td><td>154</td><td>606</td><td>116</td><td></td><td></td><td>299</td><td>29</td><td>711.3 ± 18.6</td><td>0.82 ± 0.05</td></tr><tr><td>βON.4<sup>b</sup></td><td>154</td><td>596</td><td>141</td><td></td><td></td><td>299</td><td>29</td><td>762.3 ± 20.6</td><td>0.87 ± 0.05</td></tr><tr><td>βON.5</td><td>156</td><td>564</td><td>347</td><td></td><td></td><td>300</td><td>31</td><td>1088.7 ± 27.0</td><td>1.25 ± 0.07</td></tr><tr><td>βOS.1</td><td>156</td><td>543</td><td></td><td>39</td><td></td><td>297</td><td>31</td><td>281.8 ± 6.2</td><td>0.32 ± 0.02</td></tr><tr><td>βOS.2</td><td>155</td><td>606</td><td></td><td>59</td><td></td><td>296</td><td>31</td><td>313.0 ± 13.1</td><td>0.36 ± 0.02</td></tr><tr><td>βOS.3</td><td>156</td><td>614</td><td></td><td>100</td><td></td><td>297</td><td>30</td><td>415.5 ± 6.5</td><td>0.48 ± 0.02</td></tr><tr><td>βOS.4<sup>b</sup></td><td>156</td><td>608</td><td></td><td>134</td><td></td><td>298</td><td>28</td><td>659.8 ± 10.7</td><td>0.76 ± 0.04</td></tr><tr><td>βOS.5</td><td>157</td><td>612</td><td></td><td>198</td><td></td><td>299</td><td>25</td><td>676.4 ± 10.7</td><td>0.78 ± 0.04</td></tr><tr><td>βOA.1</td><td>152</td><td>599</td><td></td><td></td><td>48</td><td>296</td><td>25</td><td>186.4 ± 13.2</td><td>0.21 ± 0.02</td></tr><tr><td>βOA.2<sup>b</sup></td><td>155</td><td>591</td><td></td><td></td><td>98</td><td>297</td><td>29</td><td>178.4 ± 5.4</td><td>0.20 ± 0.01</td></tr><tr><td>βOA.3</td><td>156</td><td>609</td><td></td><td></td><td>147</td><td>297</td><td>27</td><td>205.6 ± 13.1</td><td>0.24 ± 0.01</td></tr><tr><td>βOA.4</td><td>156</td><td>591</td><td></td><td></td><td>196</td><td>296</td><td>28</td><td>214.3 ± 5.0</td><td>0.25 ± 0.01</td></tr><tr><td>βONS.1</td><td>155</td><td>615</td><td>78</td><td>104</td><td></td><td>297</td><td>25</td><td>597.0 ± 17.0</td><td>0.68 ± 0.04</td></tr><tr><td>βONS.2<sup>b</sup></td><td>154</td><td>602</td><td>134</td><td>102</td><td></td><td>297</td><td>31</td><td>795.5 ± 10.0</td><td>0.91 ± 0.05</td></tr><tr><td>βOSA.1</td><td>156</td><td>550</td><td></td><td>103</td><td>49</td><td>296</td><td>30</td><td>437.1 ± 7.1</td><td>0.50 ± 0.03</td></tr><tr><td>βOSA.2<sup>b</sup></td><td>155</td><td>631</td><td></td><td>105</td><td>98</td><td>295</td><td>22</td><td>375.6 ± 2.3</td><td>0.43 ± 0.02</td></tr><tr><td>βOSA.3</td><td>151</td><td>551</td><td></td><td>108</td><td>190</td><td>297</td><td>29</td><td>323.5 ± 11.8</td><td>0.37 ± 0.02</td></tr></tbody></table>

<sup>a</sup>Abbreviations in experimental codes represent the reactants introduced into the chamber; that is, “β” represents β-pinene, “O” represents ozone, “N” represents nitrogen dioxide, “S” represents sulfur dioxide, and “A” represents ammonia. The number represents experiments with the same reactants but different concentrations. <sup>b</sup>Experiments were repeated under comparable conditions (Table S2 in the Supporting Information) to collect aerosol particles for offline composition analysis by UPLC/Q-Exactive-Focus HRMS.

BVOC-derived organosulfates have been widely observed from clean to polluted regions.<sup>8,10,17,24,26,27</sup> Nitrooxy organosulfates (NOSs), the formation of which is related to both NO<sub>x</sub> and sulfates, could also be produced with some diurnal trends. While daytime photooxidation was proposed to be the dominant source of biogenic NOSs in south China and northwest Europe, the enhanced NOS formation at night in Beijing and northeastern Germany was attributed to NO<sub>3</sub> and sulfate chemistry.<sup>24,26-29</sup> Understanding the precursors and formation pathways of these nitrogen- and sulfur-containing products not only requires field observations but also more laboratory experiments exploring BVOC oxidation and aerosol composition under various mixed conditions.

O<sub>3</sub> and NO<sub>3</sub> radicals are two main atmospheric oxidants at night and their relative dominance depends on the NO<sub>x</sub> levels.<sup>30</sup> In contrast to “traditional” studies where biogenic SOA formation from either O<sub>3</sub> or NO<sub>3</sub> was investigated separately, some recent studies directly explored those processes in the presence of O<sub>x</sub> (O<sub>3</sub> + NO<sub>2</sub>). Different effects of NO<sub>2</sub> have been characterized for different precursors as increasing NO<sub>2</sub> decreased α-pinene SOA yield but increased β-pinene, limonene, and γ-terpinene SOA formation.<sup>31-34</sup> Sulfates usually act as seeds to alter the SOA mass and composition.<sup>35-37</sup> Some studies directly introduced SO<sub>2</sub> during BVOCs ozonolysis and showed that SO<sub>2</sub> enhanced limonene and α-cedrene SOA but had a minor effect on α-pinene SOA.<sup>38,39</sup> Whether enhanced functionalization could compensate for the reduced oligomerization likely determines the SO<sub>2</sub> effects on final SOA yields.<sup>38</sup>

NH<sub>3</sub> is another gaseous inorganic pollutant that has been observed to correlate well with the peak level of secondary particle pollution.<sup>40,41</sup> Laboratory studies showed that NH<sub>3</sub> tended to enhance SOA mass yield of α-pinene and limonene ozonolysis by forming nitrogen-containing compounds, but no clear associations of NH<sub>3</sub> with isoprene SOA were

observed.<sup>42-46</sup> It has been predicted that 50% reduction in NH<sub>3</sub> together with a 15% reduction in NO<sub>x</sub> and SO<sub>2</sub> could result in a decrease of particulate matter by 11–17% in China.<sup>47</sup> While increasing attention has been paid to the synergistic effects of NH<sub>3</sub> with SO<sub>2</sub> or with NO<sub>2</sub> in the photooxidation of some anthropogenic VOCs, such interactions in biogenic particle formation should be further investigated.<sup>48-51</sup>

β-pinene with a global annual emission rate of 18.9 Tg contributes to about 17% of monoterpene in the atmosphere.<sup>7,52</sup> Its atmospheric abundance and exocyclic double bond make it a common representative of exocyclic monoterpenes.<sup>53</sup> The ozonolysis of β-pinene at night has been observed to have a significant contribution to nocturnal nucleation.<sup>54,55</sup> In the present study, laboratory experiments were conducted to explore the effects of inorganic pollutants on aerosol formation initiated by nucleation during β-pinene ozonolysis in the absence of seed particles. First, we characterized particle formation when one single gas (NO<sub>2</sub>, SO<sub>2</sub>, or NH<sub>3</sub>) and its mixtures (NO<sub>2</sub> and SO<sub>2</sub> or SO<sub>2</sub> and NH<sub>3</sub>) were present in the reaction system. Then, the chemical compositions of β-pinene SOA formed under different conditions were analyzed by infrared spectroscopy and high-resolution mass spectrometry. Accordingly, formation pathways of the specific particulate products, including nitrogen- and sulfur-containing compounds, were proposed to further reveal the effects of NO<sub>2</sub>, SO<sub>2</sub>, and NH<sub>3</sub> on aerosol composition.

## 2. EXPERIMENTAL METHODS

### 2.1. Controlled Chamber Experiments.
Aerosol particle formation during β-pinene ozonolysis under various conditions was studied in a 1 m<sup>3</sup> Teflon chamber, which was suspended in a stainless-steel enclosure that enables dark conditions. Before the start of each experiment, the chamber was flushed with
purified, dried air until the background particle concentrations were lower than 10 cm⁻³. Six groups of experiments were designed (Table 1). One group was pure β-pinene ozonolysis that was denoted as βO experiments. The other five groups that were performed with the presence of NO₂, SO₂, NH₃, and the coexistence of NO₂ and SO₂, SO₂ and NH₃ were coded as βON, βOS, βOA, βONS, and βOSA, respectively. The concentrations of β-pinene and O₃ in the experiments were higher than those in the real atmosphere to keep the particle production significant enough for accurate measurements while ratios of inorganic gases (NO₂, SO₂, NH₃) to O₃ and to β-pinene were in the range of 0–0.6 and 0–2.2, respectively. These ratios can partly represent relatively clean to relatively polluted atmospheric conditions, making comparisons between experimental conditions informative to aerosol generation in the atmosphere suffering different degrees of anthropogenic–biogenic interactions.<sup>15,55–62</sup>

Experiments were carried out in three consecutive steps. The first step was the introduction of reactants into the chamber. First, β-pinene (Aladdin, >99%) and cyclohexane (Aladdin, >99%) with a concentration ratio of 1:220 were evaporated into the chamber by a flow of zero air. With such an excessive amount of cyclohexane, more than 95% of OH radicals formed from β-pinene ozonolysis were expected to be scavenged, giving the rate constants of OH reactions with β-pinene ($k_{OH + β-pinene} = 7.43 \times 10^{-11} \text{ cm}^3 \text{ molecule}^{-1} \text{ s}^{-1}$) and with cyclohexane ($k_{OH + cyclohexane} = 6.97 \times 10^{-12} \text{ cm}^3 \text{ molecule}^{-1} \text{ s}^{-1}$).⁶³ Subsequently, based on the experimental design, known amounts of NO₂, SO₂, and/or NH₃ stored in respective calibrated cylinders (490 ppm balanced in N₂ for NO₂ and NH₃, 973 ppm balanced in N₂ for SO₂, YuyanGas, China) were added into the chamber by flow controllers. Then, the chamber was allowed to equilibrate for about 20 min before the addition of ozone that started the reaction (i.e., reaction time = 0 min).

The second step was the particle formation and growth that lasted for about 3 h after the addition of O₃. Particles were initially formed by homogeneous nucleation of products from β-pinene ozonolysis due to the lack of seed particles that would influence the particle composition. The initial amount of O₃ was 3–4 times higher than that of β-pinene, so that β-pinene could be consumed to a negligible level, as measured by a gas chromatograph coupled with a flame ionization detector (7890B, Agilent Technologies, USA) with a DB-624 capillary column (30 m × 0.32 mm, 1.8 mm film thickness) when particle sampling started. During this period, particle size distribution, volume, and number concentrations were monitored continually by a scanning mobility particle sizer with a differential mobility analyzer (Model 3082, TSI Inc., USA) and a condensation particle counter (Model 3776, TSI Inc., USA). The mixing ratios of NO₂ and SO₂ were monitored by a NO–NO₂–NOₓ analyzer (model 42i, Thermo Scientific, USA) and SO₂ analyzer (model 43i, Thermo Scientific, USA), respectively. The concentration of NH₃ was not monitored and its initial concentration was obtained according to the volume of the chamber and its added amount. When the aerosol mass concentration stopped increasing, the experiment entered the third step where the generated aerosol particles were collected onto aluminum foil pieces by a 13-stage Dekati low-pressure impactor (DLPI+, DeKati Ltd, Finland) for offline chemical analysis. More detailed information about the particle measurement and sampling is provided in the Supporting Information.

## 2.2. Aerosol Yield Calculation and Correction.
Aerosol yield (Y) is defined as the aerosol particle mass change ($\Delta M$, µg m⁻³) relative to the consumption of β-pinene ($\Delta[\beta-pinene]$, µg m⁻³): $Y = \Delta M/\Delta[\beta-pinene]$. Aerosol particle mass concentrations were calculated based on the volume concentration measured by a scanning mobility particle sizer and the assumed 1.2 g cm⁻³ aerosol density.⁶⁴ Inorganic salts formed during β-pinene ozonolysis would increase aerosol density, hereby underestimating the aerosol yield by less than 8% in SO₂-involved experiments when the density of inorganic salts was assumed to be 1.58 g cm⁻³ (see the Supporting Information).⁶⁵ The size-dependent wall loss rate of ammonium sulfate ($k_{dp} = 4.15 \times 10^{-7} \times D_p$), 1.89 + 1.39 × $D_p^{-0.88}$, $D_p$ is particle diameter in the unit of nm) was applied to the correction of particle mass concentration.⁶⁶ Details about this correction have been described in previous studies.³⁴,⁶⁷ Another factor that would influence the quantification of aerosol mass is the wall loss of organic vapors.⁶⁸,⁶⁹ Chamber walls and suspended particle surfaces compete for the deposition of organic vapors.⁷⁰ Accelerating reaction rates by employing an excessive amount of oxidant was reported to be one efficient way to suppress organic vapor wall loss because the fast formed particles could provide a significant sink for organic vapors to partition.³⁶,⁵³,⁷¹ The evaluation of the rate constants of vapor wall-loss and particle-loss in our reaction system indicates that organic vapors condensed to particles much faster than to the chamber walls (details are given in the Supporting Information). Therefore, the organic vapor wall loss has a minor effect on the SOA yield calculation and comparison.⁷⁰,⁷²

## 2.3. Chemical Composition Characterization.
To get details about the functional group and chemical bond information of particle-forming compounds, particles collected onto aluminum foil pieces were analyzed by an attenuated total reflectance coupled to a Fourier transform infrared spectrometer (Vertex 70, Bruker, Germany). It was operated with a scan resolution of 4 cm⁻¹ for the spectral range of 4000–600 cm⁻¹. The spectra of blank aluminum foil pieces as backgrounds were subtracted from each sample measurement and the spectra baseline were corrected via the rubberband method (64 baseline points and 20 iterations).

Inorganic composition in secondary aerosol samples was further measured by means of ion chromatography (IC, Dionex ICS-600, Thermo Fisher, USA). Aluminum foil pieces were first dissolved in 4 mL of ultrapure water (Milli-Q, Millipore, France), followed by sonication for 30 min. Then, a Teflon membrane syringe filter (25 mm diameter, 0.22 µm pore, Jinteng, China) was used to remove insoluble species. Inorganic sulfate and ammonium in the prepared solution were measured with a Dionex IonPac CS12A analytical column (4 × 250 mm) and Dionex IonPac AS19 analytical column (4 × 250 mm) associated with their guard-column (4 × 50 mm), respectively. The eluents were potassium hydroxide and methanesulfonic acid solutions, with a flow rate of 1.0 mL min⁻¹ for the separation of anions and cations, respectively.

To further characterize the aerosol organic composition, aerosol samples formed under different conditions (Table S1) were prepared and analyzed by ultraperformance liquid chromatography (UPLC, Ultimate 3000, Thermo Scientific, USA)/electrospray ionization Q-Exactive-Focus high-resolution mass spectrometry (ESI-Q-Exactive-Focus HRMS, Thermo Scientific, USA). Organic compounds in sample extracts (sample extraction procedures are provided in the
<figure><img src="image_2.png" /></figure>

<figure><img src="image_3.png" /></figure>

<figure><img src="image_4.png" /></figure>

<figure><img src="image_5.png" /><figcaption>**Figure 1.** (a) SOA yield, particle mode diameter, and reaction time at the maximal SOA mass concentration ($M_0$) as a function of the $[\beta$-pinene]$_0$/[$NO_2]$$_0$ ratios. (b) Particle size distribution in the first 5 min of reactions with different $[\beta$-pinene]$_0$/[$NO_2]$$_0$ ratios. (c) SOA yield as a function of the initial mixing ratios of $SO_2$ ($[SO_2]$$_0$) and $NH_3$ ($[NH_3]$$_0$), (d) Comparison of the yield of aerosol formed in the presence of a single pollutant or mixed pollutants ($NO_2$ + $SO_2$ and $SO_2$ + $NH_3$). Experimental details are listed in Table 1.</figcaption></figure>

Supporting Information) were separated using an Atlantis T3 C18 column (100 Å, 3 µm particle size, 2.1 mm × 150 mm, Waters, USA). The mass spectrometer was operated in both negative and positive ionization modes with the mass range of m/z 50–750. Based on the full scan MS information, the most intense precursor ions were fragmented by a higher-energy collision-induced dissociation to get the MS/MS scan. The details about the chromatographic elution program and mass spectrometric parameters are described in the Supporting Information.

### 3. RESULTS AND DISCUSSION

**3.1. NO₂, SO₂, and NH₃ Influenced β-Pinene SOA Formation.** Experiments βON.1–5 were designed to study the effects of initial NO₂ mixing ratios ($[NO_2]$$_0$) on β-pinene SOA formation. As shown in Figure 1a, the decrease in $[\beta$-pinene]$_0$/[$NO_2]$$_0$ (ppbC/ppb) ratios not only increased the SOA yield but also reduced the time for reaching the maximal aerosol mass concentration. Indeed, the particle size increase was accelerated by NO₂ after the onset of the reaction (Figure 1b). RH variation in these experiments may induce uncertainties in the particle growth and SOA yield, but the NO₂ enhancements in SOA formation can still be observed

when excluding one experiment (βON.2) conducted under relatively high RH.⁷³,⁷⁴ Though NO₂ could perturb gas chemistry via its reaction with peroxy radicals, the thermally unstable peroxy nitrates are generally insignificant in SOA formation.⁷⁵,⁷⁶ NO₃ radicals, which could be quickly formed via NO₂ + O₃ reaction, are more likely to explain such an enhancing NO₂ effect on particle formation rate and final mass due to its 5 orders of magnitude higher reactivity with β-pinene and higher SOA formation potential compared with β-pinene ozonolysis.³³,⁷⁷⁻⁸⁰

The enhanced β-pinene oxidation by NO₃ at high $[NO_2]$$_0$ and subsequent product (e.g., organic nitrates with low volatility) condensation and/or particle coagulation would grow particles to larger sizes.¹⁴,⁸¹,⁸² When the particle mass reached its maximum, as shown in Figure 1b, particle mode diameter ($D_{pm}$) was 109 nm with no NO₂, while much larger particles were formed under higher $[NO_2]$$_0$ conditions (e.g., $D_{pm}$ = 429 nm when $[\beta$-pinene]$_0$/[$NO_2]$$_0$ = 4.5). The enhanced SOA yields and particle size explained by NO₃ chemistry are supported by the results from previous studies, for which SOA yields of similar aerosol mass and $D_{pm}$ in NO₃-induced β-pinene oxidation ($Y$ = 1.34, $D_{pm}$ = ~450 nm) are comparable to those observed here.¹⁴,⁸³ The much higher β-
pinene SOA formation potential at high NO₂ condition is consistent with model predictions in the area near Houston, where NO₃ oxidation of β-pinene alone was suggested to be the second-largest SOA source.⁸⁴ In many NOₓ-polluted regions, enhanced night time SOA formation via NO₃ oxidation of monoterpenes has been demonstrated.¹⁶,¹⁸,¹⁹,²⁶ Our results also suggest that β-pinene could be an important contributor to the enhanced SOA formation at night in these places with high anthropogenic NOₓ emissions.

For β-pinene ozonolysis in experiments βOS.1–5, higher particle volume and number concentration as well as SOA yield (calculated by subtracting inorganic sulfate from the total aerosol as described in the Supporting Information and Table S2) were observed when [SO₂]₀ was high (Figures 1c and S1), in line with the previously reported role of SO₂ in the ozonolysis of limonene and butyl vinyl ether.³⁸,⁶⁶ The enhancement effect of SO₂ on SOA yield is smaller than that of NO₂. For example, with similar initial β-pinene concentrations, the presence of 100 ppb SO₂ increased the SOA yield by 0.24 while 78 ppb NO₂ increased SOA yield by 0.42. Different from the direct competition between NO₃ and O₃ for β-pinene caused by NO₂, one way for SO₂ to affect SOA formation is by reacting with stabilized Criegee intermediates (sCIs), forming SO₃ and finally sulfuric acid that is generally known to contribute to new particle formation and acid-catalyzed SOA formation.⁸⁵⁻⁸⁷ The formation of sulfate was confirmed by IC measurements. It is worth noting that the reaction between SO₂ and O₃ can be ruled out as the loss rates of SO₂ were comparable and negligible regardless of whether or not O₃ was present. The consumption of SO₂ increased with increasing [SO₂]₀ but decreased with [NO₂]₀ when NO₂ was also added (Figure S2). This is expected because the consumption of β-pinene by NO₃ that is derived from the NO₂ + O₃ reaction would lead to less sCI formation via β-pinene ozonolysis. Additionally, using formic acid (10 ppm) as the sCI scavenger in an additional experiment with similar reactant conditions to those of the βOS.2 experiment, the SO₂ consumption was nearly half compared to that in the absence of formic acid. This evidence suggests that the reaction between sCIs and SO₂ is an important sink of SO₂, which has been proposed to be a significant source of atmospheric H₂SO₄, especially in forest regions.⁸⁸⁻⁹⁰

The increased SO₂ consumption with increasing [SO₂]₀ leads to a linear (R² = 0.97) increase of the fraction of sulfate in enhanced aerosol mass (Figure S3). Considering that the hydrolysis of organosulfates during sample extraction may have a minor contribution to sulfate detected by IC, this fraction would be less than 0.4 when SO₂ decay reached 80 ppb. This significant difference suggests that besides the direct contribution of nucleated sulfate, other SO₂-induced channels, such as the role of condensed sulfuric acid as seeds for capturing more SOA-forming vapors into the particle phase, acid-catalyzed heterogeneous reactions might also contribute to the enhanced particle formation.²⁵,⁹¹⁻⁹³

SOA yields increased with NH₃ but the degree was much weaker than those of NO₂ and SO₂ (Figure 1c). The largest enhancement in SOA yield was observed to be 39% when the initial NH₃ mixing ratio approached 196 ppb. The maximal particle number concentration (Nₘₐₓ) and particle geometric mean diameter (Dₚₘ, max) were also higher with NH₃ present (Figure S4d). These NH₃ effects on particle formation have also been reported during α-pinene and limonene ozonolysis.⁴²⁻⁴⁴ Ammonium salts of low volatility formed through the

gas-phase reaction between NH₃ and organic acids (e.g., pinic acid, pinonic acid, norpinic acid, and norpinonic acid) were suggested to account for the enhanced α-pinene/limonene SOA. The yield of organic acids was reported to be 4.2–17.2% of β-pinene + O₃ reactions and many of these organic acids can be produced during the α-pinene ozonolysis through similar reaction pathways.⁹⁴⁻⁹⁶ The vapor pressure of products from the NH₃ + organic acid reaction were reported to be orders of magnitude lower than those of the corresponding acids.⁹⁷ Thus, it is expected that the acid–base reaction yielding condensable salts might be responsible for the enhanced β-pinene SOA formation in the presence of NH₃.

## 3.2. Joint Effects of NO₂ and SO₂ on Secondary Aerosol Formation.
As discussed above, the presence of NO₂ tends to produce larger particles with lower number concentrations, while SO₂ efficiently magnifies the particle number concentrations by forming relatively smaller particles. Mixed NO₂ and SO₂ seem to neutralize the single effect of NO₂ and SO₂ on particle formation, but SO₂ appears to be more effective in modifying particle size and number development. In the βONS.1 experiment with [NO₂]₀ = 78 ppb, [SO₂]₀ = 104 ppb, the stabilized Dₚₘ, max at the end of the experiment was 67 nm lower than that in the βON.2 case ([NO₂]₀ = 78 ppb) but only 15 nm larger than in βOS.3 case ([SO₂]₀ = 100 ppb)) (Figure S4b,c,e). Compared to the βON experiments, the presence of SO₂ in the mixed NO₂ + SO₂ cases compensated for the reduction of Nₚₘ caused by NO₂, making it at least 10 times higher in the latter than in the former case. Conversely, compared to the βOS experiments, the presence of NO₂ reduced Nₚₘ by about 0.8 times.

Unlike the neutralizing effects of NO₂ and SO₂ on the progression of particle size and number concentration, the coexistence of NO₂ and SO₂ shows a synergetic effect on the aerosol yield. As shown in Figure 1d, aerosol yields in βONS experiments were higher than in the corresponding βON or βOS experiments. The addition of NO₂, on the one hand, introduces NO₃, which could efficiently oxidize β-pinene and enhance SOA mass production. On the other hand, SO₂ consumption is reduced likely due to the suppressed sCI formation via β-pinene ozonolysis (Figure S2). However, certain amounts of SO₂ could still be oxidized and it is already efficient in modifying particle size distribution and number concentration. Hence, SO₂-related enhancive effects, such as promoting the generation of small particles that could act as condensation sinks and heterogeneous reactions may also assist the particle mass production, leading to a higher aerosol yield in βONS experiments than in βON experiments.

## 3.3. Joint Effects of SO₂ and NH₃ on Secondary Aerosol Formation.
To study the combined effects of SO₂ and NH₃ on aerosol particle formation, three experiments were performed with [SO₂]₀ of about 110 ppb but varying [NH₃]₀ (βOSA.1–3). In these experiments, the increase of [NH₃]₀ led to a slight decrease of aerosol yields (Figure 1d). Interestingly, the aerosol yield in βOSA.1 ([SO₂]₀ = 103 ppb, [NH₃]₀ = 49 ppb) was a little higher than that of βOS.3 ([SO₂]₀ = 100 ppb). However, when [NH₃]₀ was elevated to 98 ppb or 190 ppb, the aerosol yields decreased and were lower than that in the βOS.3 experiment. The SO₂ consumptions in these experiments had a minor difference (Figure S2), suggesting the unlikeliness of NH₃ to directly change the fate of SO₂. However, NH₃ would be absorbed onto the generated particles and acid–base neutralization reaction would occur between NH₃ and H₂SO₄.⁴⁹,⁹⁸ The produced ammonium sulfate
(Figure S5) that could offer surface layers for condensation is crucial to particle formation.<sup>49,50,99,100</sup> However, acid-related heterogeneous processes, which contribute to about 70% of the enhanced particle mass in the βOS.3 reaction, may be suppressed due to the neutralization reaction induced by NH<sub>3</sub>. Both the aerosol pH value (ranging from -2.5 to 1.2) modeled using the Extended Aerosol Inorganics Model (E-AIM model II, http://www.aim.env.uea.ac.uk/aim/aim.php) and the aerosol neutralization degree (0.4-0.9) calculated as the molar ratio of ammonium to sulfate ([NH<sub>4</sub><sup>+</sup>]/(2 × [SO<sub>4</sub><sup>2-</sup>]) increased with [NH<sub>3</sub>]<sub>0</sub> (see the Supporting Information).<sup>101,102</sup> No clear correlation between liquid water contents calculated by E-AIM model II and initial NH<sub>3</sub> mixing ratios or aerosol yields could be observed. Therefore, the promoting effects derived from ammonium sulfate may not be enough to compensate for the mitigated acid catalytic effect and finally lead to the reduced aerosol yields with the increase of [NH<sub>3</sub>]<sub>0</sub>. It should be noted that ammonia depletion is not characterized by the appropriate instrument in the present study. Hence, more experiments are required to give deeper insights into the disturbed aerosol formation mechanism of β-pinene ozonolysis in the presence of both NH<sub>3</sub> and SO<sub>2</sub>.

**3.4. Composition Analysis. 3.4.1. Identification of Functional Groups.** A typical set of infrared spectra of the particles formed under different conditions is shown in Figure 2, and the spectral assignment is summarized in Table S3.

<figure><img src="image_6.png" /><figcaption>**Figure 2.** Infrared spectra of secondary aerosol particles generated from β-pinene ozonolysis under different experimental conditions. Experimental details are listed in Table 1.</figcaption></figure>

When there were no inorganic gas pollutants present during β-pinene ozonolysis (βO), the main absorption band peaks were observed at approximately 1710 cm<sup>-1</sup>, representing the stretching vibration of C=O in carbonyl compounds.<sup>103,104</sup> The absorbance in the 1490-1350, 1335-1105, and 990-820 cm<sup>-1</sup> regions are the C—O—H in plane bending (and/or C—H bending), C—O stretching, and O—H deformation vibrations (and/or carboxylic C—O—H out-of-plane bending), respectively.<sup>43,104-107</sup> The broad bands range over 3680-3000 and 3000-2780 cm<sup>-1</sup> are O—H stretching in alcohols or acids and C—H stretching absorption in the saturated carbon ring, respectively.<sup>105</sup>

When NO<sub>2</sub> was added into β-pinene ozonolysis (βON and βONS), the formation of organic nitrates can be evidenced by the strong absorption bands at 1634 (NO<sub>2</sub> asymmetric stretching), 1281 (NO<sub>2</sub> symmetric stretching), and 856 cm<sup>-1</sup> (NO symmetric stretching).<sup>76,108</sup> The weak peak at 752 cm<sup>-1</sup> also corresponds to organic nitrates.<sup>76,109</sup> The dominant C=O absorption in the βO experiment is replaced by organic nitrates. The presence of SO<sub>2</sub> induced new absorption bands located at 1412, 1086, and 615 cm<sup>-1</sup>, which represent characteristic absorption of RO—SO<sub>2</sub>—OR' in organosulfates, symmetric S—O stretching in organic or inorganic sulfates, and the absorption of inorganic sulfate, respectively.<sup>110-112</sup> Both characteristic absorption peaks of organic nitrates and sulfates can be observed in βONS experiments, consistent with NO<sub>3</sub> chemistry and sCI-induced sulfate chemistry discussed above. For aerosol particles formed in the presence of NH<sub>3</sub>, very weak absorption peaks featuring at 870, 756, and 681 cm<sup>-1</sup> (Figure S6) likely match the vibrations of the —NH<sub>2</sub> group in the βOA experiment.<sup>106,113,114</sup> The weaker IR absorption of nitrogen-containing species is somewhat in agreement with its slight SOA yield elevation, both of which indicate that NH<sub>3</sub> likely has a minor effect on particle-forming product generation. The coexistence of SO<sub>2</sub> and NH<sub>3</sub> introduced both sulfur-containing and nitrogen-containing compounds and the absorptions at 681, 756, and 1543 cm<sup>-1</sup> (N—H bending and/or C—N stretching) were enhanced, indicating that the joint effect of SO<sub>2</sub> and NH<sub>3</sub> may occur in the βOSA experiment.

**3.4.2. Identification of Nitrogen- and Sulfur-Containing Organic Compounds.** The main identified particle-phase products in the series have been summarized in Table S4 and Figure 3. For single β-pinene ozonolysis (βO), a range of multifunctional products containing various combinations of carboxyl, carbonyl, and hydroxyl groups have been tentatively identified using high-resolution ESI(+) and/or ESI(-) mass spectrometry.<sup>94</sup> As shown in Figure S7, β-pinene ozonolysis occurs via the formation of a cyclic primary ozonide, the cycloversion of which produces a C9-Criegee intermediate with formaldehyde and a C1-Criegee intermediate with nopinone, with the former channel being much more favored than the latter.<sup>94,96,115,116</sup> The unimolecular reaction of the C9-Criegee intermediate via the hydroperoxide channel and the following series of radical reactions are responsible for the formation of the C8- and C9-monomers observed in the particle phase. In a previous study, organic acids, including pinic acid (MW = 186), pinalic-3-acid (MW = 170), and 4-hydroxypinalic-3-acid (MW = 186), have been observed in the early stage of β-pinene SOA growth.<sup>96</sup> These condensed acids were tentatively identified in the present study and they could partially explain the initial particle growth after the onset of the reaction.<sup>96,117</sup> Dimers form another important set of nucleating agents for SOA particle formation.<sup>118,119</sup> Reactions of sCIs with carbonyls to form secondary ozonides or with carboxylic acid to form peroxide ester and reactions between hydroperoxide and carbonyls to form peroxyhemiacetals (Figure S7) could account for a portion of dimer formation observed in the particle phase.<sup>120,121</sup>

For aerosol particles generated from β-pinene ozonolysis in the presence of NO<sub>2</sub>, several organic nitrates were measured in positive ion mode as listed in Table S4. Their UPLC/Q-Exactive-Focus HRMS extracted ion chromatograms (EICs) are shown in Figure S8. Four organic nitrates [C<sub>10</sub>H<sub>17</sub>O<sub>4</sub>N (MW = 215), C<sub>10</sub>H<sub>15</sub>O<sub>5</sub>N (MW = 229), C<sub>10</sub>H<sub>17</sub>O<sub>5</sub>N (MW = 231), C<sub>10</sub>H<sub>15</sub>O<sub>6</sub>N (MW = 245)] were identified, following the
<figure><img src="image_7.png" /><figcaption>**Figure 3.** Summarized reaction scheme and products of β-pinene ozonolysis under different experimental conditions. For brevity, only one isomer of each compound is shown. Organic nitrates generated with the presence of NO₂, organosulfates generated with the presence of SO₂, nitrooxy organosulfates generated with the coexistence of NO₂ and SO₂, organic ammonium generated with the presence of NH₃, and the coexistence of SO₂ and NH₃ are colored in pink, blue, orange, green, and yellow, respectively. Detailed potential formation mechanism for organic nitrates, organosulfates, and nitrooxy organosulfates are provided in Figures S9 and S11.</figcaption></figure>

NO₃ oxidation mechanisms proposed in the literature (Figure S9),¹⁴,¹²² consistent with our explanation that NO₂ increases the efficiency of β-pinene SOA production via its transformation to NO₃. C10 compounds including those with the following chemical formulas, that is, C₁₀H₁₇O₄N, C₁₀H₁₅O₅N, and C₁₀H₁₇O₅N, have been observed in many ambient aerosol samples.²⁰,⁵⁶,⁵⁷,¹²³ Field observations showed that they account for more particle mass during night time than during daytime.²⁰,²²,⁵⁶ The appearance of C10 organic nitrates in SOA samples produced under βON conditions illustrates that night time β-pinene oxidation can be one of their potential sources. Two C9 organic nitrates (C₉H₁₄O₄N with MW = 199 and C₉H₁₃O₆N with MW = 231) were also detected in positive ion mode. They might be produced via the reaction between NO₂ and reactive intermediates such as alkoxy radicals since NO₂ mixing ratios on the order of about 40 ppb were still present in the reaction mixture at the end of this experiment.¹²⁴,¹²⁵

β-Pinene has been evidenced to be an important organosulfate precursor from both field and laboratory investigations.²⁵,²⁶,²⁹,⁵⁸,¹²⁶ Acidic seed conditions are usually needed to transform β-pinene oxidation products to organosulfates through heterogeneous reactions.²⁵,³⁷,⁵⁸,¹²⁷ Though there were no acid seed particles added directly in the chamber during β-pinene ozonolysis, sulfuric acid produced via the

reaction of sClS with SO₂ potentially created acidic conditions for some heterogeneous reactions. Organosulfates in aerosol particles from the βOS experiment were identified based on their exact masses (i.e., ΔM/M within ±5 ppm) and the characteristic fragments of the sulfate group, including HSO₄⁻ (m/z 97), •OSO₃⁻ (m/z 96), HSO₃⁻(m/z 81), and •SO₃⁻ (m/z 80), were shown in the high-resolution tandem MS/MS spectra. The EICs and MS/MS spectra for these organosulfates are displayed in Figure S10. Organosulfates detected as [M-H]⁻ ions with m/z 249, 263, and 283 were identified to be C₁₀H₁₇O₅S⁻, C₁₀H₁₅O₆S⁻, and C₁₀H₁₉O₇S⁻, respectively, consistent with those detected in particles generated from β-pinene ozonolysis in the presence of acidic sulfate seed particles.³⁷,¹²⁷ Ion formulas with m/z 279 and 281 were assigned to C₁₀H₁₇O₇S⁻ and C₁₀H₁₉O₇S⁻, respectively. They have been previously observed in aerosols generated from α-pinene, limonene, and α-terpinene oxidation and β-pinene photooxidation in the presence of acidic seeds.²⁵,¹²⁸ Indeed, all of these five organosulfates have a certain abundance in ambient particles collected from urban, forest, and marine regions in Asia, Europe, and the US.¹⁰,²⁵,²⁸,²⁹,⁵⁸,¹²⁹ Our results demonstrate the potential contribution of β-pinene to these organosulfates, especially to C₁₀H₁₈O₇S and C₁₀H₂₀O₇S via the night time ozonolysis in the presence SO₂. Besides the C10 organosulfates, two C9 compounds (m/z 233 and m/z 249)
<figure><img src="image_8.png" /><figcaption>**Figure 4.** UPLC/Q-Exactive-Focus HRMS EICs and MS/MS spectra for *m/z* 294, 310, 324, 326, 342 ions (negative ion mode) in secondary aerosols generated from β-pinene ozonolysis with the coexistence of NO₂ and SO₂ (experimental details are listed in Table S2 in the Supporting Information). The maximal tolerance of mass error for all the precursor ions and product ions was set at 5 ppm.</figcaption></figure>

were tentatively identified to organosulfates ($C_9H_{13}O_5S^-$ and $C_9H_{13}O_6S^-$, Figure S10). While the reaction between sulfuric acid and 3-hydroxynopinone that is generated from the Criegee channel might explain the formation of the

$C_9H_{13}O_5S^-$ ion, the formation mechanism for $C_9H_{13}O_6S^-$ is still unknown and needs to be further investigated.

The formation of the C10 organosulfates suggests that some C10 precursors, which could not be produced via the Criegee mechanism that leads to the fracture of the C10 skeleton in β-
pinene to produce molecules containing less than nine carbons, should be produced through alternative reaction channels.²⁹,³⁷ As suggested in the literature, ozone tends to form an oxygen carbon σ-bond with one of the unsaturated carbon atoms of β-pinene (Figure S11). This σ-complex then undergoes decomposition, likely leading to a β-pinene oxide and myrtenol. While bicyclic organosulfates (m/z 249) are most likely formed through the direct attack of HSO₄⁻ on the protonated epoxide or its nucleophilic addition to the carbocation formed from the decomposition of protonated epoxide, a four-carbon ring-opened organosulfate (m/z 249) was also reported to derive from the rearranged carbocation.¹⁰,⁷,¹²⁶,¹³⁰,¹³¹ Myrtenol can be further oxidized by ozone and, after a series of reactions, finally produces some C10 compounds (C₁₀H₁₆O₃, C₁₀H₁₆O₄, C₁₀H₁₈O₄) containing the hydroxyl group. These C10 products can be detected in aerosol particles generated from the β-O experiment in the absence of SO₂ in the present study and in the literature.³⁷ They possibly act as precursors for the formation of sulfate esters with m/z 263, 279, 281, 283 via the esterification reaction of the alcohol group with sulfuric acid.²⁵,⁹²,¹²⁶

When NO₂ and SO₂ were present during the reaction, five NOSs with *m/z* 294, 310, 324, 326, and 342 in negative ion mode were characterized. In addition to the extract mass of the parent NOSs ions, the prominent fragment ions from the sulfate group and product ions of NO₃⁻ (*m/z* 62) from a nitrooxy group can be observed in their MS/MS spectra (Figure 4), confirming the coexistence of nitrooxy and sulfate groups in their structures. Consequently, the [M - H]⁻ ion formulas were C₁₀H₁₆NO₇S⁻, C₁₀H₁₆NO₈S⁻, C₁₀H₁₃NO₉S⁻, C₁₀H₁₅NO₉S⁻, and C₁₀H₁₆NO₁₀S⁻ for *m/z* 294, 310, 324, 326, and 342, respectively. Apart from the *m/z* 324 compound that is observed for the first time in the present study, other four NOS ions could also be formed from β-pinene photooxidation in the presence of acidic seed particles.²⁵ With acidic seed particles, NO₃⁻-initiated α-pinene oxidation was reported to produce NOSs ions at *m/z* 294 and 310.²⁵ In the present study, with the absence of acidic seed particles, NOSs are proposed to be formed via the NO₃⁻-initiated β-pinene oxidation, followed by alcohol sulfate esterification reactions (Figure S9). These reaction pathways are expected because, as discussed above, NO₂ and SO₂ can influence the formation of NO₃⁻ and sulfuric acid. Not only these NOSs have been widely observed in ambient particles, but *m/z* 294, 310, 326 NOSs generally have higher concentrations at night as observed in Shanghai and Beijing (China), California (US), Antwerp (Belgium), K-pusza (Hungary), northeastern Bavaria (German).¹⁰,¹⁷,²⁶,²⁸,²⁹,⁵⁸,¹³²⁻¹³⁴ Our results suggest that interactions between β-pinene, O₃, NO₂, and SO₂ may enhance the formation of the five NOSs. Though the ratios of reactant concentrations used in the present study are comparable to that in the real atmosphere, whether or not these ambient NOSs could originate from β-pinene night time chemistry in addition to α-pinene NO₃⁻-chemistry and monoterpane photo-oxidation in the presence of acidic sulfate particles should be further considered by a comprehensive analysis of specific atmospheric conditions. Future laboratory quantification of the yields of these nitrogen- and sulfur-containing products formed under typical atmospheric conditions is also needed to further illustrate their importance in the real atmosphere.

For NH₃-involved β-pinene ozonolysis in the presence or absence of SO₂, two organic ammonium carboxylates (C₉H₁₇O₃N and C₈H₁₇O₅N) were tentatively identified and

their EICs are shown in Figure S12. These organic ammonium salts may be formed via the reaction between organic acids and NH₃ in the gas-phase, followed by the partition to the particle-phase, similar to the way of ammoniated product generation in NH₃-involved α-pinene ozonolysis and photooxidation.⁴²,⁴⁵

## 4. ATMOSPHERIC IMPLICATION

Currently, levels of O₃ and NH₃ in the atmosphere have been increasing over many regions of the earth.¹³⁵,¹³⁶ Though anthropogenic emissions of SO₂ and NO₂ have declined, their concentrations can still be above 100 ppb during severe haze pollution episodes.¹³⁷,¹³⁸ Anthropogenic-biogenic interactions occurring between β-pinene and these pollutants have been systematically investigated in the present study for the first time. It is demonstrated that NO₂ and SO₂ efficiently enhanced SOA formation, while NH₃ exhibited minor effects. The distinctly different responses of particle generation to mixed pollutants (SO₂ + NO₂ and SO₂ + NH₃) from that to the single one suggest that considering only the separate impacts of these pollutants likely induces bias prediction of secondary aerosol production. The observations here may be important for the accurate prediction of aerosol formation potential in regions with both anthropogenic and biogenic influences. The detection of particulate organic nitrates, organosulfates, as well as nitrooxy organosulfates pointed to the reaction channel leading to their formation even without any additional acidic seed particles. The increase of O₃ may further strengthen the importance of night time ozonolysis in the production of particulate nitrogen- and sulfur-containing compounds. These species have significant atmospheric impacts as organic nitrates could serve as permanent NOₓ sinks to influence NOₓ and O₃ cycling and organosulfates might affect the hygroscopicity of aerosol particles and cloud condensation nuclei properties.⁴,¹⁹,¹²⁶ Though the naturally emitted BVOCs cannot be controlled directly, our results show that a fraction of biogenic SOA, such as these nitrogen- and sulfur-containing organics, can be controlled by mitigating anthropogenic pollutants, particularly NO₂ and SO₂. Future research considering a better representation of chemically detailed anthropogenic-biogenic interactions in models is warranted to help to evaluate controllable SOA budget and reduce uncertainties in predicting the impacts of aerosol particles on air quality, climate, and human health.

## ASSOCIATED CONTENT

<figure><img src="image_9.png" /></figure>

### Supporting Information

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.est.0c07879.

Additional experimental details; acidity calculation; assignment of ATR-FTIR absorption bands and compounds detected by UPLC/Q-Exactive-Focus HRMS; SO₂ consumption and particle size distribution under different experimental conditions; IC measurement of aerosol-phase sulfate and ammonium; UPLC/Q-Exactive-Focus HRMS EICs for organic nitrates, organosulfates, and organic ammonium; β-pinene ozonolysis and organic nitrates; and organosulfate formation mechanisms (PDF)
# AUTHOR INFORMATION

## Corresponding Author

Lin Du - Environment Research Institute, Shandong University, Qingdao 266237, China; orcid.org/0000-0001-8208-0558; Email: lindu@sdu.edu.cn

## Authors

Li Xu - Environment Research Institute, Shandong University, Qingdao 266237, China; orcid.org/0000-0003-0573-9296

Zhaomin Yang - Environment Research Institute, Shandong University, Qingdao 266237, China

Narcisse T. Tsona - Environment Research Institute, Shandong University, Qingdao 266237, China; orcid.org/0000-0002-6023-1850

Xinke Wang - Université Lyon, Université Claude Bernard Lyon 1, CNRS, IRCELYON, F-69626 Villeurbanne, France

Christian George - School of Environmental Science and Engineering, Shandong University, Qingdao 266237, China; Université Lyon, Université Claude Bernard Lyon 1, CNRS, IRCELYON, F-69626 Villeurbanne, France; orcid.org/0000-0003-1578-7056

## Notes

The authors declare no competing financial interest.

# ACKNOWLEDGMENTS

This work was supported by the National Natural Science Foundation of China (91644214, 21876098), Youth Innovation Program of Universities in Shandong Province (2019KJD007), and Fundamental Research Fund of Shandong University (2020QNQT012). This project has received funding from the European Union's Horizon 2020 research and innovation program under grant agreement no 690958.

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