# Oxidation pathways and emission sources of atmospheric particulate nitrate in Seoul: based on δ15N and Δ17O measurements

Saehee Lim, Meehye Lee, Joel Savarino, Paolo Laj

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Saehee Lim, Meehye Lee, Joel Savarino, Paolo Laj. Oxidation pathways and emission sources of atmospheric particulate nitrate in Seoul: based on δ15N and Δ17O measurements. Atmospheric Chemistry and Physics, 2022, 22, pp.5099-5115. 10.5194/acp-22-5099-2022. insu-03706382

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Submitted on 28 Jun 2022

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# Oxidation pathways and emission sources of atmospheric particulate nitrate in Seoul: based on δ¹⁵N and Δ¹⁷O measurements

Saehee Lim<fnref n="1" />, Meehye Lee<fnref n="1" />, Joel Savarino<fnref n="2" />, and Paolo Laj<fnref n="2" />

**Correspondence:** Meehye Lee (meehye@korea.ac.kr)

Received: 10 June 2021 – Discussion started: 19 July 2021

Revised: 4 January 2022 – Accepted: 25 January 2022 – Published: 19 April 2022

**Abstract.** PM₂.₅ haze pollution driven by secondary inorganic NO₃⁻ has been a great concern in East Asia. It is, therefore, imperative to identify its sources and oxidation processes, for which nitrogen and oxygen stable isotopes are powerful tracers. Here, we determined the δ¹⁵N (NO₃⁻) and Δ¹⁷O (NO₃⁻) of PM₂.₅ in Seoul during the summer of 2018 and the winter of 2018–2019 and estimated quantitatively the relative contribution of oxidation pathways for particulate NO₃⁻ and investigated major NOₓ emission sources. In the range of PM₂.₅ mass concentration from 7.5 µg m⁻³ (summer) to 139.0 µg m⁻³ (winter), the mean δ¹⁵N was -0.7‰ ± 3.3‰ and 3.8‰ ± 3.7‰, and the mean Δ¹⁷O was 23.2‰ ± 2.2‰ and 27.7‰ ± 2.2‰ in the summer and winter, respectively. While OH oxidation was the dominant pathway for NO₃⁻ during the summer (87%), nighttime formation via N₂O₅ and NO₃⁻ was relatively more important (38%) during the winter, when aerosol liquid water content (ALWC) and nitrogen oxidation ratio (NOR) were higher. Interestingly, the highest Δ¹⁷O was coupled with the lowest δ¹⁵N and highest NOR during the record-breaking winter PM₂.₅ episodes, revealing the critical role of photochemical oxidation process in severe winter haze development. For NOₓ sources, atmospheric δ¹⁵N (NOₓ) estimated from measured δ¹⁵N (NO₃⁻) considering isotope fractionation effects indicates vehicle emissions as the most important emission source of NOₓ in Seoul. The contribution from biogenic soil and coal combustion was slightly increased in summer and winter, respectively. Our results built on a multiple-isotope approach provide the first explicit evidence for NO₃⁻ formation processes and major NOₓ emission sources in the Seoul megacity and suggest an effective mitigation measure to improve PM₂.₅ pollution.

## 1 Introduction

In northeast Asia, air pollution characterized by high PM₂.₅ (particulate matter with aerodynamic diameter smaller than 2.5 µm) and ozone concentrations has received significant attention due to its serious effects on human health (Lelieveld et al., 2015; Xie et al., 2019). As a result of extensive efforts by East Asian countries to improve the ambient air quality, anthropogenic emissions of SOₓ, NOₓ, and CO have been significantly reduced, particularly in China (Cheng et al., 2019). Nonetheless, the number of severe haze events and

the duration have been increased, which is not understood clearly.

It is also noteworthy that there are common chemical and meteorological characteristics in the occurrence of the PM₂.₅ haze pollution in northeast Asia, such as inorganic-species-dominated chemical composition (Liu et al., 2018; Shao et al., 2018; Wang et al., 2019a) and transboundary transport of haze aerosol depending on the synoptic atmospheric circulation (Quan et al., 2020; Shi et al., 2020; Zheng et al., 2019). Overall, approximately 40% of PM₂.₅ consists of NO₃⁻, SO₄<fnref n="2" />⁻, and NH₄⁺ (secondary inorganic aerosol, SIA) in both urban and background sites in China (Liu et al., 2018)

<footnote n="1">¹Department of Earth and Environmental Sciences, Korea University, Seoul 02841, South Korea</footnote>

<footnote n="2">²Institute of Environmental Geosciences (IGE), Univ. Grenoble Alpes, CNRS, IRD, Grenoble INP, 38000 Grenoble, France</footnote>
for the period of 2012–2013. The mass contribution of SIA was further augmented up to 69% at urban Beijing and island sites (Changdao) in the North China Plain (NCP) during the 2016 spring (Lim et al., 2020). A large increase in SIA mass is particularly associated with efficient formation of $NO_3^-$ in cold months (most frequently in December to March), leading to a rapid increase in PM$_{2.5}$ concentration and developing a persistent haze pollution on a regional scale (Li et al., 2018; Xu et al., 2019). Recent studies suggest that the regional occurrence of the PM$_{2.5}$ haze events derived by $NO_3^-$ across the Asian continent has been associated with long-range transport of air pollutants promoted by cold fronts and their intrusion in downward regions by the development of the atmospheric boundary layer (Kang et al., 2019; Lee et al., 2019). However, scientific understanding is still limited because the rapid increase of fine-aerosol $NO_3^-$ is the result of the complex interplay of oxidation and transformation mechanisms producing $NO_3^-$ from various fossil and non-fossil sources of $NO_x$ with micro-to-synoptic meteorology creating the conditions for $NO_3^-$ formation. In addition, considering that $NO_x$ emissions from bottom-up emission inventory are smaller than top-down estimates by satellites (e.g., Goldberg et al., 2019), our understanding of $NO_x$ emissions is poor.

In order to better understand processes of $NO_3^-$ formation including $NO_x$ emission sources in East Asia, a growing number of recent studies have suggested nitrogen and oxygen stable-isotope-based measurement as a robust and useful tool for providing important clues for $NO_3^-$ formation as well as $NO_x$ emission sources (He et al., 2018; Lim et al., 2019, 2020; Song et al., 2019; Zong et al., 2017, 2020). The isotopic composition is expressed in parts per thousand (‰) and reported as $δ(‰) = (R_{sample}/R_{standard} - 1) \times 1000$ with R being the ratio of the heavy isotope over the light isotope (e.g., $^{15}$N/$^{14}$N, $^{18}$O/$^{16}$O, $^{17}$O/$^{16}$O) in a sample ($R_{sample}$) and in the international standard ($R_{standard}$). The international standards are the Vienna Standard Mean Ocean Water (VSMOW) and atmospheric N$_2$ for oxygen and nitrogen ratios. In terms of $NO_x$ emission sources, the major $NO_x$ sources are distinguished in their nitrogen isotopic compositions: biogenic soil (driven by fertilizer use; -35.1‰ ± 10.2‰) (Felix and Elliott, 2014; Li and Wang, 2008; Yu and Elliott, 2017), biomass burning (1.8‰ ± 1.8‰) (Fibiger and Hastings, 2016), vehicle emissions (-2.5‰ ± 1.5‰) (Walters et al., 2015), and coal combustion (14.2‰ ± 4.5‰) (Felix et al., 2012; Heaton, 1990). Despite evidence that $δ^{15}$N ($NO_x$) can serve as a useful tracer of $NO_x$ emission sources, during $NO_y$ photochemical cycling and its loss processes, the $δ^{15}$N of initial $NO_x$ can be significantly altered by both kinetic and equilibrium isotopic fractionation effects ($ε_N$), complicating the link between $δ^{15}$N ($NO_3^-$) and $δ^{15}$N ($NO_x$) (Freyer et al., 1993; Li et al., 2020).

The formation processes of $HNO_3$ in the atmosphere consist of $NO-NO_2$ photochemical cycle Reactions (R1)–(R3) and post $NO_2$ oxidation Reactions (R4)–(R8). During the $NO_x$ cycling, nitrogen isotopic fractionation is affected by

unidirectional reactions of the Leighton cycle and $NO_x$ isotope exchange equilibrium. A recent laboratory experiment has shown that the Leighton cycle isotope effect (LCIE) associated solely with $O_3$ Reaction (R1) and equilibrium isotope effect (EIE) were -10‰ and 28.9‰ at room temperature, respectively (Li et al., 2020). The relative importance of these two effects on $δ^{15}$N ($NO_2$) also depends on $NO_x$ levels, leading to an increase (decrease) in $δ^{15}$N ($NO_2$) relative to $δ^{15}$N ($NO_x$) values at high (low) $NO_x$ conditions (Kamezaki et al., 2019; Li et al., 2020; Walters et al., 2018). Overall, the nitrogen isotope exchange equilibrium has been suggested to be the dominant fractionation process in $NO-NO_2$ cycling at urban atmosphere (Freyer et al., 1993) and oxidation reactions forming nitric acid ($HNO_3$) and particulate $NO_3^-$ (Savarino et al., 2013).

$$NO + O_3 \rightarrow NO_2 + O_2, \qquad (R1)$$

$$NO + RO_2(HO_2) \rightarrow NO_2 + RO(OH), \qquad (R2)$$

$$NO_2 + hv \rightarrow NO + O(^3P), \qquad (R3)$$

$$NO_2 + OH \rightarrow HNO_3, \qquad (R4)$$

$$NO_2 + O_3 \rightarrow NO_3 + O_2, \qquad (R5)$$

$$NO_2 + NO_3 + \overset{M}{\rightleftharpoons} N_2O_5, \qquad (R6)$$

$$N_2O_5 + H_2O \xrightarrow{aerosol} 2HNO_3(aq), \qquad (R7)$$

$$NO_3 + RH \rightarrow HNO_3 + R, \qquad (R8)$$

where M is an unreactive third body and R is any organic group.

The kinetic fractionation effect during daytime oxidation of $NO_2$ to $HNO_3$ Reaction (R4) is relatively minor, being estimated to be -3‰ (Freyer, 1991). During the nighttime when most NO is oxidized to $NO_2$ without $NO_x$ photolysis, the isotopic equilibrium between $NO_2$, $NO_3$, and $N_2O_5$ should be achieved (Reaction R6). The nighttime thermal equilibrium likely favors the partitioning of $^{15}$N into $N_2O_5$ relative to $NO_2$ and consequently induces a large isotopic fractionation effect of 25.5‰ (Reactions R5–R6; Walters and Michalski, 2015). On the other hand, the nitrogen partitioning between $NO_2$ and $NO_3$ Reaction (R5) may induce a fractionation effect of about -18‰ (Walters and Michalski, 2015). These N isotope fractionation effects should be first evaluated to explore $NO_x$ source contributions, which should be based on combining with a robust tracer for the contributions of $NO_3^-$ oxidation pathways.

Lately, $δ^{17}$O ($NO_3^-$) has been used for tracing $NO_3^-$ oxidation pathways (Alexander et al., 2009, 2020; Morin et al., 2009; Savarino et al., 2007, 2013). Earlier researches observed that atmospheric $NO_3^-$ is anomalously enriched in $^{17}$O (Michalski et al., 2003), which stems from $O_3$ formation reactions, where a rare isotope effect leads to excess $^{17}$O enrichment relative to what is expected based on the $^{18}$O enrichments (Thiemens, 1999, 2006). This enrichment is quantified by $δ^{17}$O notation ($^{17}$O excess, defined as $δ^{17}$O - 0.52 × $δ^{18}$O). Since non-zero $δ^{17}$O strictly reflects
a photochemical effect, $NO_3^-$ produced by denitrification in soils should have $\Delta^{17}O$ of zero. The mass-independent $\Delta^{17}O$ signature of $O_3$ is transferred to $NO_x$, in which the number of oxygen atoms from $O_3$ is involved in $NO_x$. In this way, the $\Delta^{17}O$ ($NO_3^-$) is served as a conservative marker to track the chemical formation of atmospheric $NO_3^-$: Photochemical formation by peroxy radicals ($HO_2$ and $RO_2$) leads to a relatively low $\Delta^{17}O$ ($NO_3^-$), whereas nighttime formation through $N_2O_5$ and $NO_3$ results in high $\Delta^{17}O$ (Michalski et al., 2003; Morin et al., 2009; Savarino et al., 2007). Consequently, the difference in $\Delta^{17}O$ ($NO_3^-$) suggests approaching a proportional contribution of daytime and nighttime oxidation of $NO_3^-$.

To date, few field studies have coupled $\Delta^{17}O$ ($NO_3^-$) and $\delta^{15}N$ ($NO_3^-$) to investigate $NO_x$-to-$NO_3^-$ oxidation processes and emission sources of $NO_x$, e.g., field researches in Japan (Nelson et al., 2018); West Virginia, USA (Rose et al., 2019); Shanghai, China (He et al., 2020); and Beijing, China (He et al., 2018; Song et al., 2020).

In this study, we present the measurement results of $\delta^{15}N$ and $\Delta^{17}O$ of $NO_3^-$ in Seoul during the summer of 2018 and the winter of 2018–2019, when we encountered the record-breaking PM$_{2.5}$ concentrations. Then, the $\delta^{15}N$ and $\Delta^{17}O$ measurements are used to evaluate seasonally distinct atmospheric oxidation pathways of $NO_3^-$ and to explore major $NO_x$ source contributions in the study region.

# 2 Measurements and methods

## 2.1 Sampling

We collected PM$_{2.5}$ filter samples on the rooftop of the six-story Asan science building at the Korea University campus located in northeast Seoul, the capital of South Korea (37.59° N, 127.02° E; Fig. 1) during the summer of 2018 (26 May to 22 August; $n = 13$) and the winter of 2018–2019 (27 December to 8 March; $n = 18$). Seoul is a metropolitan area with a population of 9.77 million and known to be influenced by heavy road traffic all around. The PM$_{2.5}$ particulates were collected on quartz filters (20 cm × 25 cm; Pallflex Products, Putnam, USA) at a nominal flow rate of 96 m$^3$ hr$^{-1}$ for 1 to 3 d using a high-volume air sampler (3000 series, Ecotech, Australia). Filters were analyzed for water-soluble ions, carbonaceous compounds, total nitrogen (TN) and carbon (TC), and stable nitrogen and oxygen isotopic ratios. Reactive gases including $O_3$, NO, $NO_2$, $SO_2$, and CO and a meteorological suite including air temperature, relative humidity, and wind speed and direction were measured hourly at the nearby monitoring sites run by the National Institute of Environmental Research (NIER) and the Korea Meteorological Administration (KAM), respectively. These data were averaged daily for comparison with filter-based chemical composition data, if necessary.

## 2.2 Chemical analyses

Filters were stored in a freezer pending chemical analysis. Chemical composition of PM$_{2.5}$ was determined for eight water-soluble ions ($Cl^-$, $NO_3^-$, $SO_4^{2-}$, $Na^+$, $NH_4^+$, $K^+$, $Ca^{2+}$, and $Mg^{2+}$) by ion chromatography (IC; Eco IC, Metrohm, Switzerland), organic carbon (OC) and elemental carbon (EC) by an OC-EC analyzer (Sunset Laboratory Inc., US) using the thermo-optical transmittance method (NIOSH870), and TC and total nitrogen (TN) by an elemental analyzer (EA, Fisons NA-1500NC, Thermo, Waltham, MA, USA). Mass concentrations of these constituents were corrected for laboratory and field blanks. The detection limit, determined as 3 standard deviations (SD) above blank concentrations, was <0.1 ppm for ionic species, 0.5 µg cm$^{-3}$ for TC (the sum of OC and EC), and 0.8 g µgN and 0.5 µgC per punched filter area for TN and TC, respectively. Details of the analytical methods can be found elsewhere (Lim et al., 2020).

Following the bacterial denitrifier method (Casciotti et al., 2002; McIlvin and Casciotti, 2011), the $\Delta^{17}O$ of $NO_3^-$ was measured simultaneously with $\delta^{18}O$ and $\delta^{15}N$ coupled with an isotope ratio mass spectrometry (IRMS) measurement using an in-house peripheral system at the Université Grenoble Alpes (Morin et al., 2009). In brief, $NO_3^-$ of samples was converted to $N_2O$ via bacterial denitrification, and the $N_2O$ was further converted into $O_2$ and $N_2$, which were separated via a gas chromatography column before being introduced to the IRMS system (Thermo Finnigan MAT 253 isotope ratio mass spectrometer). Samples were measured in batch with reference materials following strictly the identical treatment principles, including the same water matrix for standards and samples. Together with samples, a subset of international nitrate reference materials (US Geological Survey 32, 34, and 35, as well as their mixtures) was measured for correction and calibration of $\Delta^{17}O$ and $\delta^{18}O$ values relative to VSMOW and $\delta^{15}N$ values relative to air $N_2$. The overall accuracy of the method is estimated as the reduced standard deviation of the residuals from the linear regression between the measured reference materials and their expected values (Morin et al., 2009). For these sets of analyses, the obtained uncertainties ($1\sigma$) were 0.4‰ and 0.3‰ for $\Delta^{17}O$ ($NO_3^-$) and $\delta^{15}N$ ($NO_3^-$), respectively. The analytical procedure used in this study strictly followed the method described in Morin et al. (2009), which adheres to the new standard bacterial method coupled with the gold catalyst for the thermal decomposition of $N_2O$ into $N_2$ and $O_2$ (Kaiser et al., 2007).

## 2.3 Quantifying isotope fractionation effects

### 2.3.1 Isotope fractionation effects of $NO_2$ oxidation to atmospheric particulate $NO_3^-$: $\delta^{15}N$ ($NO_3^-$)

The $HNO_3$ forms through three major pathways including (i) OH pathway, (ii) $O_3$ pathway associated with $N_2O_5$, and (iii) $O_3$ pathway associated with $NO_3$.
a)

<figure><img src="image_4.png" /><figcaption>Figure 1. Location of the study region. (a) Seoul metropolitan area in South Korea; the map was generated using the open-source software R (http://www.R-project.org/, last access: 2 February 2021). (b) Sampling site of the Korea University campus in the northeast Seoul; the map was taken from © Kakao maps (https://map.kakao.com/, last access: 29 December 2021).</figcaption></figure>

b)

<figure><img src="image_5.png" /></figure>

## OH pathway

When NO and NO₂ coexist in similar quantities due to the Leighton cycle, ¹⁵N is preferentially partitioned into NO₂ via the equilibrium isotope effect, leading to higher δ¹⁵N in NO₂ relative to NO and NOₓ (Freyer et al., 1993; Walters et al., 2016). Considering the comparable concentrations of NO and NO₂ over a year in Seoul (Fig. S1 in the Supplement), the N isotope effects on δ¹⁵N (NO₃⁻) should be significantly affected by NOₓ photochemical interactions. The relative importance of EIE and LCIE to δ¹⁵N(NO₂) can be assessed by comparing lifetimes of NO₂ with respect to isotope exchange with NO (τ exchange) and photolysis (τ NO₂+hv). In this regard, the “A” factor was defined as τ exchange / τ NO₂+hv = j NO₂ / k₁ × [NO] (k₁ = 8.14 × 10⁻¹⁴ cm³ s⁻¹, Sharma et al., 1970) by Li et al. (2020, 2021). These studies demonstrated that A was as small as 0.01–0.5 in the EIE-dominated regime with NOₓ >20 ppbv and the ratio of NO₂/NOₓ <0.6. In Seoul, to simply evaluate the relative importance of EIE and LCIE only (not for ¹⁵N correction), the A factor was estimated to be 0.08 ± 0.20 (median ± SD) and 0.60 ± 0.51 during the winter and summer months, respectively, indicating the significant influence of the equilibrium isotope effect on NO–NO₂ isotopic fractionation. The time series jNO₂ was calculated using the Master Chemical Mechanism (MCM) model (Saunders et al., 2003).

After NOₓ photochemical cycling, NO₂ is oxidized by the reaction with OH radical to form atmospheric HNO₃ (HNO₃ Reaction R4 pathway). The N fractionation effect of particulate NO₃⁻ produced via the HNO₃ Reaction (R4) pathway (ε₁, unit in %) can be expressed as the following, neglecting kinetic isotope effects associated with the HNO₃ Reaction (R4) pathway (Walters and Michalski, 2016):

$$ \delta^{15}\text{N}(\text{HNO}_3)(\text{R4}) = \delta^{15}\text{N}(\text{NO}_2) = \delta^{15}\text{N}(\text{NO}_x) + \varepsilon_1, \quad (1a) $$

$$ \varepsilon_1 = \left( \left( {}^{15}\alpha_{\text{NO}_2/\text{NO}-1} \right) (1 - f_{\text{NO}_2}) \right) / \left( (1 - f_{\text{NO}_2}) + \left( {}^{15}\alpha_{\text{NO}_2/\text{NO}} \times f_{\text{NO}_2} \right) \right), \quad (1b) $$

where fNO₂ is the fraction of NO₂ relative to the total NOₓ, and ¹⁵αNO₂/NO is the temperature-dependent isotope equilibrium exchange fractionation factor for NO₂/NO (Walters et al., 2016). In the present study, the measured fNO₂ was used individually for summer samples, and a seasonal mean fNO₂ (0.69) was applied to winter samples due to the lack of availability of continuous NO–NO₂ measurement data.

Oxidation of NOₓ to HNO₃ is regarded as the formation pathway of particulate NO₃⁻ via the HNO₃ Reaction (R4) pathway due to the unconstrained isotope fractionation effect between HNO₃ and NO₃⁻, resulting in the following equation:

$$ \delta^{15}\text{N}(\text{HNO}_3)(\text{R4}) = \delta^{15}\text{N}(\text{NO}_3^-)(\text{R4}). \quad (1c) $$

## O₃ pathways associated with N₂O₅ and NO₃

During the nighttime when NO is oxidized into NO₂ without photolyzing back to NO and fresh emissions of NO are negligible, NOₓ exists almost as NO₂, and thus δ¹⁵N (NO₂) should be reflective of the δ¹⁵N of NOₓ sources. If NO₂ is oxidized to N₂O₅, the isotopic equilibrium is likely to be achieved between NO₂, NO₃, and N₂O₅ by chemical equilibrium Reaction (R6), and the δ¹⁵N values of N₂O₅ and NO₃ will reflect the isotope equilibrium fractionation factors relative to NO₂ (i.e., ¹⁵αN₂O₅/NO₂ and ¹⁵αNO₃/NO₂; values were adopted from the Supplement Table S5 in Walters
and Michalski, 2016). Finally, δ¹⁵N of particulate NO₃⁻ produced from dark pathways can be expressed as the following, neglecting currently unconstrained kinetic isotopic fractionation associated with Reactions (R7) and (R8) (Walters and Michalski, 2016):

$$ \delta^{15}\text{N}(\text{HNO}_3)(\text{R}7) = \delta^{15}\text{N}(\text{N}_2\text{O}_5) = \delta^{15}\text{N}(\text{NO}_2) + \varepsilon_2, \quad (2a) $$

$$ \varepsilon_2 = \left( \frac{15 \alpha_{\text{N}_2\text{O}_5/\text{NO}_2-1}}{\text{NO}_3^-} \right), \quad (2b) $$

$$ \delta^{15}\text{N}(\text{HNO}_3)(\text{R}7) = \delta^{15}\text{N}(\text{NO}_3^-)(\text{R}7), \quad (2c) $$

$$ \delta^{15}\text{N}(\text{HNO}_3)(\text{R}8) = \delta^{15}\text{N}(\text{NO}_3) = \delta^{15}\text{N}(\text{NO}_2) + \varepsilon_3, \quad (3a) $$

$$ \varepsilon_3 = \left( \frac{15 \alpha_{\text{NO}_3/\text{NO}_2-1}}{\text{NO}_3^-} \right), \quad (3b) $$

$$ \delta^{15}\text{N}(\text{HNO}_3)(\text{R}8) = \delta^{15}\text{N}(\text{NO}_3^-)(\text{R}8). \quad (3c) $$

Therefore, the δ¹⁵N (NOₓ) in the atmosphere can be expressed using measured δ¹⁵N (NO₃⁻) and the net N isotope fractionation effect, εN.

$$ \delta^{15}\text{N}(\text{NO}_x)_{\text{atmosphere}} = \delta^{15}\text{N}(\text{NO}_3^-)_{\text{measured}} - \varepsilon_N, \quad (4a) $$

$$ \varepsilon_N = \varepsilon_1 \times f_1 + \varepsilon_2 \times f_2 + \varepsilon_3 \times f_3, \quad (4b) $$

where ε₁, ε₂, and ε₃ are the abovementioned N isotope fractionation effect of pathways (i), (ii), and (iii), respectively, and the proportional contributions (f₁, f₂, and f₃) of the three NO₃⁻ formation pathways were estimated from Δ¹⁷O measurements (Sect. 2.3.2).

## 2.3.2 Proportional contributions of three formation pathways to atmospheric particulate NO₃⁻: Δ¹⁷O (NO₃⁻)

Due to its mass-independent nature, Δ¹⁷O of particulate NO₃⁻ is a conservative tracer of photochemical NO₃⁻ formation (Michalski et al., 2003, 2004). At photochemical steady state, the Δ¹⁷O of NO₂ is determined by the relative production rate of NO₂ via O₃ oxidation Reaction (R1) in NO₂ production Reactions (R1) and (R2) (f₀₃) and the mass-independent Δ¹⁷O anomaly transferred from O₃ during Reaction (R1) (Δ¹⁷O–O₃*):

$$ \Delta^{17}\text{O}(\text{NO}_2)(\%_o) = f_{\text{O}_3} \times \Delta^{17}\text{O}-\text{O}_3^*. \quad (5) $$

f₀₃ was adopted from a previous study conducted in Beijing (Wang et al., 2019b), where the seasonal mean was 0.858 and 0.918 for summer and winter, respectively. Δ¹⁷O–O₃* can be approximated as 1.5 × Δ¹⁷O–O₃ because of the isotopic asymmetry of O₃ (Michalski and Bhattacharya, 2009). In this study, the Δ¹⁷O–O₃* is 37.5‰ ± 2.2‰ (mean ± SD) averaged from literature sources as the isotopic composition of ozone shows a remarkable stability in the lower troposphere (Ishino et al., 2017; Vicars et al., 2012; Vicars and Savarino, 2014)

The Δ¹⁷O of particulate NO₃⁻ produced via the three formation pathways can be predicted by distinct Δ¹⁷O transfer functions as the following (Morin et al., 2011):

$$ \begin{aligned} \Delta^{17}\text{O}(\text{NO}_3^-)(\text{R}4)(\%_o) &= 2/3\Delta^{17}\text{O}(\text{NO}_2) \\ &= 2/3 f_{\text{O}_3} \times \Delta^{17}\text{O}-\text{O}_3^*, \end{aligned} \quad (6a) $$

$$ \begin{aligned} \Delta^{17}\text{O}(\text{NO}_3^-)(\text{R}7)(\%_o) &= 5/6\Delta^{17}\text{O}(\text{N}_2\text{O}_5) \\ &= 1/3\Delta^{17}\text{O}(\text{NO}_2) + 1/2\Delta^{17}\text{O}(\text{NO}_3) \\ &= 1/6\Delta^{17}\text{O}-\text{O}_3^*(4f_{\text{O}_3} + 1), \end{aligned} \quad (6b) $$

$$ \begin{aligned} \Delta^{17}\text{O}(\text{NO}_3^-)(\text{R}8)(\%_o) &= \Delta^{17}\text{O}(\text{NO}_3) \\ &= 2/3\Delta^{17}\text{O}(\text{NO}_2) + 1/3\Delta^{17}\text{O}-\text{O}_3^* \\ &= 1/3\Delta^{17}\text{O}-\text{O}_3^*(2f_{\text{O}_3} + 1). \end{aligned} \quad (6c) $$

Finally, the Δ¹⁷O (NO₃⁻) can be expressed as the following:

$$ \begin{aligned} \Delta^{17}\text{O}(\text{NO}_3^-)_{\text{measured}} &= \Delta^{17}\text{O}(\text{NO}_3^-)(\text{R}4) \times f_1 \\ &\quad + \Delta^{17}\text{O}(\text{NO}_3^-)(\text{R}7) \times f_2 \\ &\quad + \Delta^{17}\text{O}(\text{NO}_3^-)(\text{R}8) \times f_3, \end{aligned} \quad (7) $$

where Δ¹⁷O (NO₃⁻) measured is the measured value in this study, and the three endmember values of Δ¹⁷O (NO₃⁻) Reaction (R4), Δ¹⁷O (NO₃⁻) Reaction (R7), and Δ¹⁷O (NO₃⁻) Reaction (R8) are calculated using Eqs. (6a)–(6c). The proportional contributions of the three NO₃⁻ formation pathways (f₁ + f₂ + f₃ = 1) were estimated by the Stable Isotope Analysis in R (SIAR) model (Sect. 2.5) for the winter and the summer months.

## 2.4 Estimation of PM₂.₅ aerosol liquid water content (ALWC) and aerosol pH

ISORROPIA II is a thermodynamic equilibrium model for the Cl⁻, NO₃⁻, SO₄²⁻, Na⁺, NH₄⁺, K⁺, Ca²⁺, Mg²⁺, and H₂O aerosol system (Fountoukis and Nenes, 2007). In the present study, the model was run as a forward and metastable mode to calculate aerosol liquid water content (ALWC) and pH. The detailed information of the model is found in Fountoukis and Nenes (2007). As input parameters, the concentrations of water-soluble ions that were measured by NIER and ambient RH and temperature were used for the model.

## 2.5 Bayesian stable isotope mixing model (stable isotope analysis in R, SIAR)

For quantifying proportional contribution of three NO₃⁻ formation pathways (f₁, f₂, and f₃ in Eq. 4b), we used the Bayesian stable isotope mixing model (Parnell et al., 2013) implemented in the simmr package in R software, which is available at https://cran.r-project.org/web/packages/simmr/
index.html (last access: 10 March 2021). The Bayesian Markov chain Monte Carlo approach is adequate to provide the relative contribution of the endmembers. Detailed information of the SIAR can be found in Parnell et al. (2010). As input data, measured $\Delta^{17}O(\text{NO}_3^-)$ and estimated $\Delta^{17}O(\text{NO}_3^-)$ endmember values of each pathway were treated in the SIAR model. Similar use of the SIAR model can be found elsewhere (Song et al., 2020; Wang et al., 2019b).

## 2.6 Backward air mass trajectory

Two-day air mass backward trajectories were analyzed using the HYSPLIT (Hybrid Single-Particle Lagrangian Integrated Trajectory) model with meteorological input from the global data assimilation system (a regular 1° × 1° longitude–latitude grid) (Stein et al., 2015; https://ready.arl.noaa.gov/HYSPLIT.php, last access: 27 May 2020). The trajectories were calculated every 6 h at an elevation of 500 m a.s.l. The potential source contribution function (PSCF) was then applied to calculate the probable source location (latitude *i* and longitude *j*), which is determined here as the ratio of the number of trajectory end points associated with measured $\delta^{15}N(\text{NO}_3^-)$ values higher than a threshold value (set to the 95th percentile of $\delta^{15}N(\text{NO}_3^-)$ ($m_{ij}$) to the total number of points ($n_{ij}$) in the *ij*th grid cell). The PSCF calculation and the determination of the gridded trajectory frequencies were made in the openair R package (https://cran.r-project.org/web/packages/openair/index.html, last access: 4 January 2021) (Carslaw and Ropkins, 2012).

# 3 Results and discussion

## 3.1 Seasonal characteristics of PM<sub>2.5</sub> concentration, δ<sup>15</sup>N (NO<sub>3</sub><sup>-</sup>), and Δ<sup>17</sup>O (NO<sub>3</sub><sup>-</sup>)

PM<sub>2.5</sub> mass concentration varied from 7.5 to 139.0 µg m<sup>-3</sup> for the whole sampling period. According to the typical synoptic weather patterns of East Asia (Kim et al., 2007), the measurements are divided into summer (May–August) and winter (October–March) groups. A clear seasonal difference in PM<sub>2.5</sub> concentration and its composition were observed with significantly higher concentrations of mass and inorganic constituent in the winter than in the summer (Table 1 and Fig. S1).

During the summer, PM<sub>2.5</sub> concentration ranged from 7.5 to 34.5 µg m<sup>-3</sup> with a mean of 22.7 ± 6.9 µg m<sup>-3</sup>. The mean concentration of TC and TN was 4.6 ± 1.4 µg C m<sup>-3</sup> and 1.9 ± 1.0 µg N m<sup>-3</sup>, respectively, resulting in the mean TC / TN ratio of 2.7 ± 2.0. The mass concentrations of all measured species were much higher in the winter, during which PM<sub>2.5</sub> concentration was raised up to 139.0 from 10.6 µg m<sup>-3</sup> with a mean of 61.7 ± 39.2 µg m<sup>-3</sup>. Accordingly, the mean of TC and TN was 15.2 ± 4.5 µg C m<sup>-3</sup> and 11.8 ± 7.7 µg N m<sup>-3</sup>, respectively, and the mean TC / TN ratio of 0.9 ± 0.7 was noticeably lower than that of the summer.

For the entire experiment, the mean mass fraction against PM<sub>2.5</sub> was the highest for $\text{NO}_3^-$ (26% ± 23%), followed by $\text{SO}_4^{2-}$ (20% ± 1%) and $\text{NH}_4^+$ (14% ± 1%), highlighting the contribution of SIA to PM<sub>2.5</sub> mass. The $\text{NO}_3^-$ mass concentration varied from 0.2 to 69.3 µg m<sup>-3</sup> with a mean of 17.6 ± 22.1 µg m<sup>-3</sup>. Seasonally, the $\text{NO}_3^-$ concentration was significantly higher in the winter (29.7 ± 22.1 µg m<sup>-3</sup>) than summer (0.8 ± 0.9 µg m<sup>-3</sup>). TN existed completely as inorganic N from both $\text{NO}_3^-$ and $\text{NH}_4^+$ during the winter (regression slope of 1.0). During the summer, $\text{NO}_3^-$ and $\text{NH}_4^+$ comprised 67% of TN, and the rest (33%) was assumed to be organic nitrogen (ON) components. In contrast, the mass fraction of $\text{SO}_4^{2-}$ against PM<sub>2.5</sub> was higher in the summer (23%) than winter (19%). The seasonal characteristics of chemical composition imply the significant role of inorganic nitrogen species in PM<sub>2.5</sub> mass increase in winter and ON and sulfate in summer.

Both $\delta^{15}N(\text{NO}_3^-)$ and $\Delta^{17}O(\text{NO}_3^-)$ exhibited an inverse correlation with ambient temperature ($r = -0.87$ and $r = -0.55$, respectively). The $\delta^{15}N(\text{NO}_3^-)$ exhibited higher values in winter with a weight mean of $-0.7\text{‰} \pm 3.3\text{‰}$ and $3.8\text{‰} \pm 3.7\text{‰}$ in the summer and the winter, respectively. This seasonal pattern of $\delta^{15}N(\text{NO}_3^-)$ has been typically observed in East Asia regions (Li et al., 2019; Song et al., 2019; Zong et al., 2020). Analysis of backward air mass trajectory indicates that the lower and the upper bound of $\delta^{15}N(\text{NO}_3^-)$ were associated with air masses from the ocean by southerly and easterly winds in the summer and from Siberia by northerly winds in winter, respectively (Fig. S3 in the Supplement). In comparison with urban China (Fig. 2a), averaged summer $\delta^{15}N(\text{NO}_3^-)$ values were comparable between Seoul and all urban Chinese sites reported here, whereas in winter, $\delta^{15}N(\text{NO}_3^-)$ of Seoul was similar to that of Shanghai and Guangzhou rather than $\delta^{15}N(\text{NO}_3^-)$ of Beijing, which was higher than $10\text{‰}$. Another observation at a mountain station in Taiwan shows that the highest $\delta^{15}N(\text{NO}_3^-)$ was found in spring when the level of anthropogenic constituents was elevated (Guha et al., 2017). These observations over East Asia may suggest to some extent that the seasonal pattern of $\delta^{15}N(\text{NO}_3^-)$ is basically associated with a synoptic meteorological condition that controls the type and strength of emission sources, where low and high $\delta^{15}N(\text{NO}_3^-)$ values indicate biogenic soil emissions and fossil combustion, respectively (Elliott et al., 2019).

Along with nitrogen isotope, heavier oxygen isotopes were also enriched in $\text{NO}_3^-$ during the winter compared to the summer, when the weight-mean values of $\delta^{17}O$, $\delta^{18}O$, and $\Delta^{17}O$ in $\text{NO}_3^-$ were $70.4\text{‰} \pm 5.4\text{‰}$, $82.0\text{‰} \pm 6.2\text{‰}$, and $27.7\text{‰} \pm 2.2\text{‰}$ for the winter and $57.3\text{‰} \pm 4.9\text{‰}$, $65.7\text{‰} \pm 6.2\text{‰}$, and $23.2\text{‰} \pm 2.2\text{‰}$ for the summer. These results of high winter and low summer $\Delta^{17}O(\text{NO}_3^-)$ were consistent with previous observations at urban Beijing (He et al., 2018; Wang et al., 2019b; Fig. 2b), indicative of relatively greater contribution of nighttime oxidation pathways
<table><caption>**Table 1.** Measurement summary of PM<sub>2.5</sub> chemical constituents and isotopic compositions in Seoul during the sampling period of May 2018–March 2019. Arithmetic mean ± 1 SD (mass fraction, %) for mass concentrations and concentration-weighted mean ± 1 SD for isotope ratios.</caption><thead><tr><th>Constituents</th><th>Summer (n = 13)</th><th>Winter (n = 18)</th></tr></thead><tbody><tr><td>PM<sub>2.5</sub> (µg m<sup>-3</sup>)</td><td>22.7 ± 6.9</td><td>61.7 ± 39.2</td></tr><tr><td>TC</td><td>4.6 ± 1.4 (20 %)</td><td>15.2 ± 4.5 (25 %)</td></tr><tr><td>TN</td><td>1.9 ± 1.0 (8 %)</td><td>11.8 ± 7.7 (19 %)</td></tr><tr><td>NO<sub>3</sub><sup>-</sup></td><td>0.8 ± 0.9 (4 %)</td><td>29.7 ± 22.1 (48 %)</td></tr><tr><td>NH<sub>4</sub><sup>+</sup></td><td>1.9 ± 0.8 (8 %)</td><td>11.7 ± 8.4 (19 %)</td></tr><tr><td>SO<sub>4</sub><sup>2-</sup></td><td>5.3 ± 2.1 (23 %)</td><td>11.5 ± 9.2 (19 %)</td></tr><tr><td>[NH<sub>4</sub><sup>+</sup>] / ([SO<sub>4</sub><sup>2-</sup>]+[NO<sub>3</sub><sup>-</sup>]) equiv. ratio</td><td>0.83 ± 0.08</td><td>0.94 ± 0.09</td></tr><tr><td>δ<sup>15</sup>N (NO<sub>3</sub><sup>-</sup>)</td><td>-0.7 ± 3.3</td><td>3.8 ± 3.7</td></tr><tr><td>δ<sup>17</sup>O</td><td>57.3 ± 4.9</td><td>70.4 ± 5.4</td></tr><tr><td>δ<sup>18</sup>O</td><td>65.7 ± 6.2</td><td>82.0 ± 6.2</td></tr><tr><td>Δ<sup>17</sup>O</td><td>23.2 ± 2.2</td><td>27.7 ± 2.2</td></tr></tbody></table>

<figure><img src="image_6.png" /><figcaption>**Figure 2.** (a) δ<sup>15</sup>N (NO<sub>3</sub><sup>-</sup>) and (b) Δ<sup>17</sup>O (NO<sub>3</sub><sup>-</sup>) PM<sub>2.5</sub> observed in northeast Asia are compared: Seoul in this study (red); Beijing (brown), Shanghai (orange), and Guangzhou (light) in China; and Rishiri (green) and Sapporo (blue) in Japan during summer (circle) and winter (square). Annual ranges were presented for Rishiri and Sapporo. Marker indicates mean value (concentration-weighted average for Seoul samples of the present study), and lower and upper whiskers denote minimum and maximum values (this study; He et al., 2018; Lim et al., 2020; Nelson et al., 2018), mean ± SD (Song et al., 2019; Wang et al., 2019b), or 25th and 75th percentiles (Zong et al., 2020). Different marker shapes indicate different seasons.</figcaption></figure>

in winter. It is also noteworthy that our summer and winter Δ<sup>17</sup>O (NO<sub>3</sub><sup>-</sup>) values were similar to annual Δ<sup>17</sup>O (NO<sub>3</sub><sup>-</sup>) values of an urban (Sapporo) and a rural (Rishiri) site in Japan, respectively (Nelson et al., 2018). It is likely suggestive that the winter Δ<sup>17</sup>O value in Seoul has undergone a considerable atmospheric processing on a regional scale.

Given that PM<sub>2.5</sub> concentrations reflect the seasonality, atmospheric chemical composition and meteorological properties were examined in relation to PM<sub>2.5</sub> concentrations (Fig. 3). Clearly, for the winter samples with PM<sub>2.5</sub> concentration greater than 40 µg m<sup>-3</sup>, meteorological conditions varied relative to low PM<sub>2.5</sub> samples; relatively high temperature and RH staying at 0 to 10° and 45% to 65%, respectively, and a low wind speed of 1 to 2 m s<sup>-1</sup>, representing the meteorological characteristics of winter PM<sub>2.5</sub>

episodes. Particularly in winter, a strong linearity of PM<sub>2.5</sub> was found with most chemical constituents considered in this study, such as SIA species, TN, NOR, and SOR (sulfur oxidation ratio). However, although elevated in level, NO<sub>2</sub> and O<sub>3</sub> mixing ratios showed non-linearity with PM<sub>2.5</sub> concentrations. Isotope ratios were correlated either linearly or inversely with PM<sub>2.5</sub> concentrations. In winter, Δ<sup>17</sup>O (NO<sub>3</sub><sup>-</sup>) showed the best correlation with PM<sub>2.5</sub> concentrations, but δ<sup>15</sup>N (NO<sub>3</sub><sup>-</sup>) was inversely related with PM<sub>2.5</sub> level.

## 3.2 Graphical representation of dual isotopes: Δ<sup>17</sup>O and δ<sup>15</sup>N of NO<sub>3</sub><sup>-</sup>

The isotope ratios of source endmembers are scarce in the study region and in the aerosol measurements, and the iso-
<figure><img src="image_7.png" /><figcaption>**Figure 3.** Relationships of PM<sub>2.5</sub> mass concentration with meteorological parameters (a–c), concentrations of reactive gases (d–f, k) and aerosol chemical constituents (g–j, l–n), and N and O isotopic compositions (o–q) measured in Seoul during the summer (open circle) and the winter (blue ribbon).</figcaption></figure>
tope fractionation effect during gas-to-particle conversion is often estimated with thermodynamic constants and reasonable assumptions. In this regard, the graphical representation of dual isotopes enables the complex signatures of atmospheric samples to be distinguished and allows their oxidation processes to be constrained. Figure 4 displays measured $\delta^{15}$N (NO$_3^-$) and $\Delta^{17}$O (NO$_3^-$) coordinates with related chemical parameters in colors.

In Fig. 4a and b, the range of $\Delta^{17}$O (NO$_3^-$) endmembers for the three NO$_3^-$ oxidation pathways calculated in Sect. 2.3.2 is presented by black dotted boxes, which are successfully distinguished. The $\Delta^{17}$O (NO$_3^-$) values of all samples fell into the predicted ranges of the $\Delta^{17}$O endmembers but were separated into seasonal groups. Most of summer $\Delta^{17}$O (NO$_3^-$) values indicate the NO$_3^-$ Reaction (R4) pathway. It is in accordance with what has been reported in temperate areas during summer (Alexander et al., 2009; Michalski et al., 2003). In field measurements of $\delta^{15}$N (NO$_3^-$) and $\delta^{18}$O (NO$_3^-$) in Chinese cities, the proportional contribution of the OH-oxidation pathway was significantly correlated with latitudes (Zong et al., 2020), confirming the evidence of the NO$_3^-$ formation through OH oxidation depending on UV radiation intensity.

In comparison, more than half of winter samples are located in the domains indicating NO$_3^-$ Reactions (R7) and (R8) pathways. In particular, for winter samples with NO$_3^-$ mass concentration higher than ~30 µg m$^{-3}$, $\Delta^{17}$O (NO$_3^-$) values clearly represent the Reaction (R7) pathway. The winter $\Delta^{17}$O (NO$_3^-$) was proportional to the NOR (Fig. 4c), which is indicative of the efficient conversion of NO$_x$ to NO$_3^-$ via O$_3$ oxidation pathways. In the summer periods when NO$_3^-$ concentrations were relatively high (above ~3 µg m$^{-3}$), the contributions of O$_3$ oxidation pathways became elevated, which is a similar pattern to what was observed in the winter. This result suggests that the O$_3$ oxidation pathways are likely to be responsible for the rapid conversion of particulate NO$_3^-$ observed during winter and summer PM$_{2.5}$ episodes in the study region.

The formation of N$_2$O$_5$ Reaction (R6) is dependent on both NO$_2$ and O$_3$, which are reciprocally correlated in source regions. The equilibrium of Reaction (R6) shifts to N$_2$O$_5$ at low temperature, and its lifetime against photolysis is long under the low sunlight. For these reasons, the dark formation of NO$_3^-$ Reaction (R7) would be favorable in urban outflows in winter. The hydrolysis of N$_2$O$_5$ on aerosol surface Reaction (R7) is highly dependent on RH, aerosol liquid water content (ALWC), and chemical composition (Hallquist et al., 2003; Wahner et al., 1998). To evaluate the $\Delta^{17}$O (NO$_3^-$) signature observed, we calculated ALWC and acidity of aerosol, pH, using the ISORROPIA II model (Sect. 2.4). Given the high concentration of nano-particles from various sources in the urban areas, it is assured that aerosol surface is enough for the NO$_3^-$ Reaction (R7) pathway. The calculated ALWC was higher by 90% (19.1 ± 22.8 µg m$^{-3}$) in the winter and lower by 21% (7.8 ± 5.2 µg m$^{-3}$) in the

summer relative to the annual mean of the 2 years. When NO$_3^-$ mass concentrations were greater than ~3 µg m$^{-3}$ in the summer and ~30 µg m$^{-3}$ in the winter, ALWC was 14.3 and 31.7 µg m$^{-3}$, respectively, which were greater by 166% and 183% than the seasonal mean, respectively (Fig. 4d). Furthermore, the high $\Delta^{17}$O (NO$_3^-$) and ALWC coincided with the lower bound (about 4) of winter pH varying from 4 to 6, whereas aerosol pH was 2–3 during the summer. The low aerosol pH concurrent with the high $\Delta^{17}$O (NO$_3^-$) and ALWC is coherent with the aqueous-phase HNO$_3$ formation on liquid aerosol through Reaction (R7).

While $\Delta^{17}$O (NO$_3^-$) allows insights into the oxidation pathway of NO$_3^-$, $\delta^{15}$N (NO$_3^-$) values are affected by various factors, most of which are not well constrained due to the complicated chemistry of nitrogen oxides in the Earth’s environment. In this study, $\delta^{15}$N (NO$_3^-$) variability versus PM$_{2.5}$ concentration resembled the variability of NO$_2$ versus PM$_{2.5}$ concentration (Fig. 3f and o), implying a close link between NO$_2$ oxidation and $\delta^{15}$N (NO$_3^-$). Therefore, in addition to the role of $\Delta^{17}$O (NO$_3^-$) as a tracer of an NO$_3^-$ oxidation pathway, we evaluated whether a variation of $\delta^{15}$N (NO$_3^-$) indicates NO$_x$ oxidation efficiency between NO and NO$_2$ (Freyer et al., 1993; Nelson et al., 2018; Walters et al., 2016). A possible effect on $\delta^{15}$N during NO$_x$ photochemical cycling cannot be predicted in the same way under varying conditions of NO, NO$_2$, and O$_3$ abundances. The shift in $\delta^{15}$N (NO$_2$) relative to $\delta^{15}$N (NO$_x$) in the atmosphere will change depending on $f_{NO_2}$ and temperature-dependent $\alpha_{NO_2/NO}$ (Freyer et al., 1993; Li et al., 2020; Walters et al., 2016). When O$_3$ mixing ratio is high, NO is almost completely oxidized to NO$_2$, leading to an increasing $f_{NO_2}$ value, and the $\delta^{15}$N (NO$_2$) should correspond to the $\delta^{15}$N of NO$_x$ sources (Freyer et al., 1993).

In the dual isotope coordinates of $\delta^{15}$N (NO$_3^-$) and $\Delta^{17}$O (NO$_3^-$) (Fig. 4), it is evident that the samples taken during a record-breaking winter’s PM$_{2.5}$ pollution events are associated with the lower bound values of $\delta^{15}$N (NO$_3^-$) (-1‰ to 4‰) and the highest $\Delta^{17}$O (NO$_3^-$) values (28‰ to 31‰). Simultaneous measurements of PM$_1$ chemical composition in Seoul and Beijing demonstrated that the regionally processed air masses were long-range transported to Seoul within approximately 2d during these episodes (H. Kim et al., 2020). Their NO$_2$/O$_3$ ratio (1 to 2) was clearly lower with higher $f_{NO_2}$ (0.7 to 0.8) compared to the other winter samples (Fig. 4g and h). This result implies that O$_3$ level was high enough to efficiently oxidize NO to NO$_2$ during the severe PM$_{2.5}$ pollution events. In this condition, the shift in $\delta^{15}$N (NO$_2$) relative to $\delta^{15}$N (NO$_x$) is insignificant, and, consequently, $\delta^{15}$N (NO$_2$) would be lower than those of other winter samples unless both emission sources and $\alpha_{NO_2/NO}$ changed significantly. Considering that NO$_3^-$ is the key driver of the high PM$_{2.5}$ in Seoul, the higher degree of NO$_x$ oxidation efficiency is worth highlighting, in conjunction with a strong linear relationship between $\Delta^{17}$O (NO$_3^-$) and NOR (Fig. 4c) revealing an efficient
<figure><img src="image_8.png" /></figure>

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**Figure 4.** Relationship of measured δ<sup>15</sup>N (NO<sub>3</sub><sup>-</sup>) and Δ<sup>17</sup>O (NO<sub>3</sub><sup>-</sup>) values with key parameters during the summer (open circle) and winter (closed ribbon). The predicted Δ<sup>17</sup>O (NO<sub>3</sub><sup>-</sup>) values are presented as dotted rectangles for the three major NO<sub>3</sub><sup>-</sup> formation pathways (Reactions R4, R7, and R8; see Sect. 2.3.2 for details) in (a) summer and (b) winter. Data are color coded by (a, b) nitrate concentrations, (c) NOR, (d) ALWC, (e) pH, (f) [NH<sub>4</sub><sup>+</sup>]/([SO<sub>4</sub><sup>2-</sup>] + [NO<sub>3</sub><sup>-</sup>]) equivalent ratio, (g) NO<sub>2</sub>/O<sub>3</sub> ratio, and (h) f<sub>NO<sub>2</sub></sub>. Marker size is proportional to PM<sub>2.5</sub> concentration ranging from 10 to 100 µg m<sup>-3</sup>.
conversion of NO₂ to NO₃⁻ through NO₃⁻ pathway Reactions (R5)+(R6)+(R7)+(R8) via O₃.

### 3.3 Contributions of major HNO₃ oxidation pathways

Combining the Δ¹⁷O (NO₃⁻) measurements and the calculation of Δ¹⁷O transferred from O₃ to HNO₃, the contributions of three major NO₃⁻ formation pathways were quantitatively accounted for, despite the inherent uncertainties in the calculation (Sect. 2.5).

NO₃⁻ pathway Reaction (R4) dominated the total NO₃⁻ formation (87% ± 6%) in summer. In contrast, the nighttime pathways through N₂O₅ and NO₃⁻ (pathways Reactions R7 and R8) were responsible for 24% and 14% of the NO₃⁻ formation in the winter, respectively. The contributions increased further to 40% and 30%, respectively, on haze days when PM₂.₅ concentration exceeded 75 µg m⁻³, the “very bad” alert of the national air quality standard. The significant nighttime oxidation of NO₃⁻ has been observed broadly at urban sites in northeast Asia. The results of this study are consistent with those conducted in Beijing, showing low Δ¹⁷O values in summertime (about 17‰ to 25‰) and substantially high Δ¹⁷O values (about 25‰ to 34‰) in winter-time when NO₃⁻-driven PM₂.₅ haze pollution occurred (He et al., 2018; Song et al., 2020; Wang et al., 2019b). In general, nighttime pathways accounted for more than 60% and up to 97% in Beijing (He et al., 2018; Song et al., 2020; Wang et al., 2019b). From a global perspective, the chemical transport model demonstrated that N₂O₅ heterogeneous hydrolysis was of comparable importance to NO₂ + OH (41%) for NO₃⁻ formation at below 1 km altitude (Alexander et al., 2020).

It is noteworthy that although the seasonal patterns are similar in northeast Asia, the average proportional contributions estimated from Δ¹⁷O (NO₃⁻) are highly sensitive to input parameters (i.e., fO₃ and Δ¹⁷O–O³*). In this study, the seasonal fO₃ was assumed to be equal to those estimated for Beijing and set to 0.858 ± 0.05 and 0.918 ± 0.05 for the warm and cold months, respectively (Wang et al., 2019b), which are comparable to other estimates for Beijing (0.86) and Shanghai (0.97) (He et al., 2018, 2020) and the annual mean of 0.85 in a global model (Alexander et al., 2020).

The uncertainty associated with Δ¹⁷O–O³* has been recognized as the largest source of uncertainty in estimating NO₃⁻ production pathways from Δ¹⁷O (NO₃⁻) (Alexander et al., 2009, 2020). In this study, the Δ¹⁷O–O³* of 37.5‰ ± 2.2‰ was averaged from previous observations, corresponding to Δ¹⁷O-bulk O₃ of 25‰ (Ishino et al., 2017; Vicars et al., 2012; Vicars and Savarino, 2014). Our mean Δ¹⁷O–O³* of 37.5‰ was 2.8‰ higher and 1.5‰ lower than what was used in the field studies (Song et al., 2020; Wang et al., 2019b) and other studies (He et al., 2018, 2020), respectively, for urban Beijing and Shanghai. When a sensitivity test was conducted for the proportional contribution of the three oxidation pathways, a 2.8‰ change in Δ¹⁷O–O³*

value caused a 1.6‰, 2.1‰, and 2.5‰ change in the endmember for the pathways for Reactions (R4), (R7), and (R8), respectively. As a result, the average contribution of the nighttime pathways, including NO₃⁻ Reaction (R7) and NO₃⁻ Reaction (R8), increased to 23% in summer and 65% in winter. This suggests that a proper use of key parameters driving endmember values is a prerequisite for more realistic quantification of NO₃⁻ oxidation pathway contributions.

### 3.4 Major NOₓ emission sources

To investigate major emission sources of atmospheric NOₓ in Seoul, δ¹⁵N (NOₓ) in the atmosphere (δ¹⁵N (NOₓ)atmosphere) was estimated from measured δ¹⁵N (NO₃⁻) considering nitrogen isotopic fractionation effects (εN) based on a dual isotopes approach (Δ¹⁷O and δ¹⁵N). Estimated εN values were 5.9‰ ± 1.5‰ and 12.2‰ ± 0.5‰, and accordingly the δ¹⁵N (NOₓ)atmosphere was −8.7‰ ± 3.3‰ and −5.8‰ ± 4.2‰ in summer and winter, respectively. The larger winter εN reveals the enhanced contribution of the nighttime oxidation pathway via N₂O₅. As a result, a seasonal difference in δ¹⁵N (NOₓ)atmosphere was as small as 2.9‰ on average, which is suggestive of little seasonal difference in major NOₓ emission sources in Seoul.

Figure 5 displays the measured δ¹⁵N (NO₃⁻) and estimated δ¹⁵N (NOₓ)atmosphere of individual samples together with δ¹⁵N (NOₓ) domains of emission source endmembers reported in literature: biogenic soil (driven by fertilizer use, −35.1‰ ± 10.2‰; Felix and Elliott, 2014; Li and Wang, 2008; Yu and Elliott, 2017), biomass burning (1.8‰ ± 1.8‰; Fibiger and Hastings, 2016), vehicle emissions (−2.5‰ ± 1.5‰; Walters et al., 2015), and coal combustion (14.2‰ ± 4.5‰; Felix et al., 2012; Heaton, 1990). Both in summer and winter, δ¹⁵N (NOₓ)atmosphere values are the closest to the domain of vehicle emissions δ¹⁵N (NOₓ), highlighting the largest contribution of vehicle emissions to NOₓ in Seoul (Fig. 5). However, the winter δ¹⁵N (NO₃⁻) without isotope fractionation effect apparently points to coal emissions, which could lead to misleading conclusions about major NOₓ sources. This result is supported by a better correlation of NO₂ with CO than with SO₂ for both seasons. According to an (anthropogenic) bottom-up emissions inventory, the Clean Air Policy Support System (CAPSS), total mobile sources account for about two-thirds of NOₓ emissions in Korea, followed by combustion sources such as energy and manufacturing industries (33%). The highest NO₂ column densities are distinct in Seoul metropolitan areas, which is mostly due to the emissions from transportation (H. C. Kim et al., 2020). Our results of the isotope measurements are in fairly good agreement with the national emission inventories and satellite observations, highlighting the largest contribution of vehicle emissions to NOₓ sources in Seoul.

Other than vehicle emissions, the lower bound summer δ¹⁵N (NOₓ)atmosphere and the upper bound win-
<figure><img src="image_16.png" /><figcaption>**Figure 5.** Variations in measured $\delta^{15}\text{N}(\text{NO}_3^-)$ (open) and estimated $\delta^{15}\text{N}(\text{NO}_x)_{\text{atmosphere}}$ (closed) in Seoul during the summer (circle) and winter (triangle). The $\delta^{15}\text{N}(\text{NO}_x)$ range (mean $\pm$ 1 SD) of source endmembers is distinguished by dotted boxes in different colors: coal combustion (14.2‰$\pm$4.5‰; Felix et al., 2012; Heaton, 1990), biomass burning (1.8‰$\pm$1.8‰; Fibiger and Hastings, 2016), vehicle emissions (−2.5‰$\pm$1.5‰; Walters et al., 2015), and biogenic soil emissions (−35.1‰$\pm$10.2‰; Felix and Elliott, 2014; Li and Wang, 2008; Yu and Elliott, 2017).</figcaption></figure>

ter $\delta^{15}\text{N}(\text{NO}_x)_{\text{atmosphere}}$ were relatively closer to the $\delta^{15}\text{N}(\text{NO}_x)$ of fertilized soil emissions and coal combustion, respectively. These seasonally distinct contributions from soil emissions and coal combustion were consistent with the results from previous studies conducted in China, revealing common seasonal emission characteristics on a regional scale in East Asia. It was evident that the upper bound winter $\delta^{15}\text{N}(\text{NO}_x)_{\text{atmosphere}}$ coincided with an elevated $\text{SO}_4^{2-}/\text{NO}_3^-$ mass ratio by 2–3 times. During these periods, trajectory analysis indicates that air masses originated from cold regions in northeastern China, such as Liaoning province, where heavy and coal-fired industries are located. In Beijing, located in northeastern China, coal combustion is an important fossil-fuel source as the highest contribution source to atmospheric $\text{NO}_x$ emissions during winter, about 30% to 40%, regardless of approaches used for estimating $\text{NO}_3^-$ oxidation pathways, either $\Delta^{17}\text{O}$ or $\delta^{18}\text{O}$ (Li et al., 2019; Song et al., 2019, 2020; Zong et al., 2020). Thus, in this study, the upper bound winter $\delta^{15}\text{N}(\text{NO}_x)_{\text{atmosphere}}$ suggests enhanced contributions of coal combustion to atmospheric $\text{NO}_x$ emissions. It is particularly noteworthy that the lower winter $\delta^{15}\text{N}(\text{NO}_3^-)$ and thus relatively lower contribution of coal combustion of the present study confirms the recent trend that emissions from coal combustion have been reduced in China (Cheng et al., 2019; Tong et al., 2018). Our study was conducted in later years (2018–2019) than their studies (2013–2017), in which $\delta^{15}\text{N}(\text{NO}_3^-)$ values were rather comparable

to the winter mean $\delta^{15}\text{N}(\text{NO}_3^-)$ observed in Seoul during January 2014 to February 2016 (11.9‰$\pm$2.5‰; Park et al., 2018). The lower bound of winter $\delta^{15}\text{N}(\text{NO}_3^-)$ values associated with the highest $\text{NO}_3^-$ and $\text{PM}_{2.5}$ concentrations (Figs. 3 and 4) was considered a result of complex effects of isotopic fractionation, as discussed above.

This study region is under the influence of various biomass burning sources throughout a year, such as agricultural combustion in the vicinities of Seoul and over eastern China from spring to fall (Chen et al., 2017; Zhao et al., 2017), wild fires over Siberia and the Russian Far East in summer (van der Werf et al., 2010), and residential biomass combustion for heating over east Asia in winter. Some winter $\delta^{15}\text{N}(\text{NO}_x)_{\text{atmosphere}}$ values fell in the $\delta^{15}\text{N}(\text{NO}_x)$ range of biomass burning endmembers (Fibiger and Hastings, 2016; Fig. 5). When assessing contributions of biomass burning based on few endmember $\delta^{15}\text{N}(\text{NO}_x)$, however, caution should be exerted considering the fact that $\delta^{15}\text{N}(\text{NO}_x)$ varied among biomass types from −7‰ to 12‰ (Fibiger and Hastings, 2016), and there is currently a lack of understanding of biomass combustion that could potentially affect air quality in Seoul.
## 4 Conclusions and outlook

Our $\delta^{15}$N- and $\Delta^{17}$O-based study confirms that vehicle emissions are the main source of $NO_3^-$ in PM$_{2.5}$ in Seoul during the summer and the winter. In addition, the qualitative estimates of $NO_x$ emission sources provide suggestive evidence for enhanced contributions from coal combustion and biogenic soil emissions in the winter and the summer, respectively. Moreover, severe winter haze events with daily PM$_{2.5}$ exceeding 100 $\mu g m^{-3}$ were mainly driven by $NO_3^-$ (up to ~60% in PM$_{2.5}$). Reducing $NO_x$ emissions from vehicles is, therefore, essential for an effective mitigation measure to improve fine aerosol pollution in the study region. In particular, the highest PM$_{2.5}$ was concurrent with the lowest $\delta^{15}$N ($NO_3^-$) and the highest $\Delta^{17}$O ($NO_3^-$) and NOR, revealing the efficient NO-to-NO$_2$ conversion and heterogeneous conversion of $HNO_3$ to particulate $NO_3^-$ through the $O_3$ oxidation pathway during the winter haze episodes. The multiple-isotope signatures of particulate $NO_3^-$, including $^{17}$O, $^{18}$O, and $^{15}$N, highlight the secondary nature of fine aerosol pollution intimately coupled with the photochemical oxidation process.

While our results demonstrate that $\delta^{15}$N and $\Delta^{17}$O are robust tracers for major $NO_x$ sources, quantitative source apportionment using the isotope method requires further elaboration of isotope equilibrium and/or kinetic fractionation effects involved in photochemical cycling of nitrogen oxides and $\delta^{15}$N of $NO_x$ source endmembers representing local or regional emissions in East Asia. In well-designed field studies, the $\delta^{15}$N and $\Delta^{17}$O measurements of multiphase and their vertical structures allow us to test the isotope fractionation effects suggested by laboratory experiments and theoretical calculations, as well as to characterize the atmospheric processing that influences them. In addition, there is an urgent need to document the $\delta^{15}$N ($NO_x$) values of emissions from vehicles with/without selective catalytic reduction (SCR) and from biomass combustion as a function of biomass type and combustion conditions. Consequently, a comprehensive and quantitative understanding of the oxidation pathways and emission sources of nitrogen oxides using $\delta^{15}$N and $\Delta^{17}$O measurements will be able to elucidate the detailed mechanisms driving severe haze development in megacities of northeast Asia, including Seoul.

**Data availability.** Data used in this study are available upon request to the corresponding author.

**Supplement.** The supplement related to this article is available online at: https://doi.org/10.5194/acp-22-5099-2022-supplement.

**Author contributions.** SL and ML conceived the project and carried out the aerosol sampling and the analysis of aerosol chemical

compositions. SL conceptualized and wrote the article. ML supervised the study and wrote the article. JS conducted stable isotope analysis on the samples and helped SL in interpreting the results. The results of the study were discussed by all authors but especially by PL.

**Competing interests.** The contact author has declared that neither they nor their co-authors have any competing interests.

**Disclaimer.** Publisher's note: Copernicus Publications remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

**Special issue statement.** This article is part of the special issue "Effect of Megacities on the Transport and Transformation of Pollutants at Regional and Global Scales (EMeRGe) (ACP/AMT inter-journal SI)". It is not associated with a conference.

**Acknowledgements.** This research was supported by the National Strategic Project Fine Particle of the National Research Foundation of Korea (NRF), funded by the Ministry of Science and ICT (MSIT), Ministry of Environment (ME), and Ministry of Health and Welfare (MOHW) (grant no. 2017M3D8A1092015). Funding to Saehee Lim was provided by the National Research Foundation of Korea (NRF) from the Ministry of Science and ICT (grant no. 2018R1D1A1B07050849). Meehye Lee thanks for the support from NRF (grant no. 2020R1A2C3014592). Joel Savarino thanks the French National Research Agency (Investissements d'avenir grant no. ANR-15-IDEX-02) and the INSU program LEFE-CHAT for supporting the stable isotope laboratory. This is publication 4 of PANDA platform on which isotope analyses were performed. The authors especially thank Nicolas Caillon for performing the analysis of the ammonium–nitrogen isotope ratio. The authors thank the Korea National Institute of Environmental Research (NIER) and Korea Meteorological Administration (KMA) for their monitoring data used in this study.

**Financial support.** This research has been supported by the National Research Foundation of Korea (grant nos. 2017M3D8A1092015, 2018R1D1A1B07050849, and 2020R1A2C3014592).

**Review statement.** This paper was edited by Manabu Shiraiwa and reviewed by two anonymous referees.

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