Characterizing isotopic compositions of TC-C, NO3−-N, and NH4+-N in PM2.5 in South Korea: Impact of China's winter heating

Park, Yu-Mi; Park, Kwang‐Su; Kim, Hyuk; Yu, Seok-Min; Noh, Seam; Kim, Min-Seob; Kim, Jee-young; Ahn, Joonyoung; Lee, Mindo; Seok, Kwang-Seol; Kim, Young‐Hee

doi:10.1016/j.envpol.2017.10.072

Cited by 69 publications

(28 citation statements)

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“…As discussed in section 1.1, the δ 15 N-NO3reflects the δ 15 N of the source NOx plus any isotopic fractionation imparted from NO/NO2 cycling or NOx to NO3conversion. Similar to previous studies, we surmise that NOx equilibrium fractionation is unlikely to be relevant in our system, as NOx concentrations are significantly lower than O3 concentrations (Elliott, et al, 2007;Morin, et al, 2009;Park, et al, 2018). Typical O3 concentrations observed at coastal sites in Antarctica are on the order of 20 ppbv (Nadzir, et al, 2018), whereas the sum of NO and NO2 rarely exceeds 40 pptv (Jones, et al, 2000;Weller, et al, 2002;Bauguitte, et al, 2012).…”

Section: 2) Interpretation Of Natural Nox Sources Using the N Isotopic Composition Of Atmospheric No3 -supporting

confidence: 90%

The importance of alkyl nitrates and sea ice emissions to atmospheric NOx sources and cycling in the summertime Southern Ocean marine boundary layer

Burger

Granger

Joyce

et al. 2021

Preprint

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Abstract. Atmospheric nitrate originates from the oxidation of nitrogen oxides (NOx = NO + NO2) and impacts both tropospheric chemistry and climate. NOx sources, cycling, and NOx to nitrate formation pathways are poorly constrained in remote marine regions, especially the Southern Ocean where pristine conditions serve as a useful proxy for the preindustrial atmosphere. Here, we measured the isotopic composition (δ15N and δ18O) of atmospheric nitrate in coarse-mode (> 1 μm) aerosols collected in the summertime marine boundary layer of the Atlantic Southern Ocean from 34.5° S to 70° S, and across the northern edge of the Weddell Sea. The δ15N-NO3− decreased with latitude from −2.7 ‰ to −43.1 ‰. The decline in δ15N with latitude is attributed to changes in the dominant NOx sources: lightning at the low latitudes, oceanic alkyl nitrates at the mid latitudes, and photolysis of nitrate in snow at the high latitudes. There is no evidence of any influence from anthropogenic NOx sources or equilibrium isotopic fractionation. Using air mass back trajectories and an isotope mixing model, we calculate that oceanic alkyl nitrate emissions have a δ15N signature of −22.0 ‰ ± 7.5 ‰. Given that measurements of alkyl nitrate contributions to remote nitrogen budgets are scarce, this may be a useful tracer for detecting their contribution in other oceanic regions. The δ18O-NO3− was always less than 70 ‰, indicating that daytime processes involving OH are the dominant NOx oxidation pathway during summer. Unusually low δ18O-NO3− values (less than 31 ‰) were observed at the western edge of the Weddell Sea. The air mass history of these samples indicates extensive interaction with sea ice covered ocean, which is known to enhance peroxy radical production. The observed low δ18O-NO3− is therefore attributed to increased exchange of NO with peroxy radicals, which have a low δ18O, relative to ozone, which has a high δ18O. This study reveals that the mid- and high-latitude surface ocean may serve as a more important NOx source than previously thought, and that the ice-covered surface ocean impacts the reactive nitrogen budget as well as the oxidative capacity of the marine boundary layer.

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Section: 2) Interpretation Of Natural Nox Sources Using the N Isotopic Composition Of Atmospheric No3 -supporting

confidence: 90%

The importance of alkyl nitrates and sea ice emissions to atmospheric NOx sources and cycling in the summertime Southern Ocean marine boundary layer

Burger

Granger

Joyce

et al. 2021

Preprint

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“…indicating that NH4 + in cloudwater is primarily derived from particulate NH4 + instead of NH3 absorption. ) and NH4 + in precipitation (Fang et al, 2011;Leng et al, 2018;Yang et al, 2014;Zhang et al, 2008), cloudwater (this study), PM2.5 (particulate matter with aerodynamic diameter less than 2.5 μm; (Lin et al, 2016;Park et al, 2018;Proemse et al, 2012;Smirnoff et al, 2012), and TSP (particulate matter with aerodynamic diameter less than 100 μm (Kundu et al, 2010;Savard et al, 2018;Yeatman et al, 2001) are shown. 245…”

Section: Page 11supporting

confidence: 48%

Isotopic Constraints on the Atmospheric Sources and Formation of Nitrogenous Species in Biomass-Burning-Influenced Clouds

Chang

Zhang

et al. 2018

Preprint

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The interpretation of tropospheric cloud formation rests on understanding the sources and processes affecting aerosol constituents of the atmosphere that are preserved in cloudwater. 25 However, this challenge is difficult to be quantitatively addressed based on the sole use of bulk chemical properties. Nitrogenous aerosols, mainly ammonium (NH4 + ) and nitrate (NO3 -), play an important role in tropospheric cloud formation. Here we collected cloudwater samples at the summit of Mt. Tai (1545 m above sea level) in Eastern China during a long-lasting biomass burning (BB) event, and measured for the first time the isotopic compositions (mean ± 1σ) of 30 cloudwater nitrogen species (δ 15 N-NH4 + = -6.53 ± 4.96‰, δ 15 N-NO3 -= -2.35 ± 2.00‰, δ 18 O-NO3 -= 57.80 ± 4.23‰), allowing insights into their sources and potential transformation mechanism within the clouds. Large contributions of BB to the cloudwater NH4 + (32.9 ± 4.6%) and NO3 -(28.2 ± 2.7%) inventories were confirmed through a Bayesian isotopic mixing model, coupled with our newly-developed computational quantum chemistry module. Despite an overall reduction in total 35 anthropogenic NOx emission due to effective emission control actions and stricter emission standards for vehicles, the observed cloud δ 15 N-NO3values suggest that NOx emissions from transportation may have exceeded emissions from coal combustion. δ 18 O-NO3values imply that the reaction of OH with NO2 is the dominant pathway of NO3formation (57 ± 11%), yet the Atmos. Chem. Phys. Discuss., https://doi.

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“…By explicitly considering the uncertainty associated with the isotopic signatures of any given source, as well as isotope fractionation during the formation of various components of a mixture, the application of Bayesian methods to stable isotope mixing models generates robust probability estimates of source proportions and is often more appropriate when targeting natural systems than simple linear mixing models (Chang et al, 2016a). Here the Bayesian model MixSIR (a stable isotope mixing model using sampling, importance and resampling) was used to disentangle multiple NO x sources by generating potential solutions of source apportionment as true probability distributions, which has been widely applied in a number of fields (e.g., Parnell et al, 2013;Phillips et al, 2014;Zong et al, 2017). Details on the model frame and computing methods are given in Sect.…”

Section: Bayesian Isotope Mixing Modelmentioning

confidence: 99%

Nitrogen isotope fractionation during gas-to-particle conversion of NOx to NO3− in the atmosphere – implications for isotope-based NOx source apportionment

et al. 2018

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Abstract. Atmospheric fine-particle (PM2.5) pollution is frequently associated with the formation of particulate nitrate (pNO3−), the end product of the oxidation of NOx gases (NO + NO2) in the upper troposphere. The application of stable nitrogen (N) (and oxygen) isotope analyses of pNO3− to constrain NOx source partitioning in the atmosphere requires knowledge of the isotope fractionation during the reactions leading to nitrate formation. Here we determined the δ15N values of fresh pNO3− (δ15N–pNO3−) in PM2.5 at a rural site in northern China, where atmospheric pNO3− can be attributed exclusively to biomass burning. The observed δ15N–pNO3− (12.17±1.55 ‰; n = 8) was much higher than the N isotopic source signature of NOx from biomass burning (1.04±4.13 ‰). The large difference between δ15N–pNO3− and δ15N–NOx (Δ(δ15N)) can be reconciled by the net N isotope effect (εN) associated with the gas–particle conversion from NOx to NO3−. For the biomass burning site, a mean εN( ≈ Δ(δ15N)) of 10.99±0.74 ‰ was assessed through a newly developed computational quantum chemistry (CQC) module. εN depends on the relative importance of the two dominant N isotope exchange reactions involved (NO2 reaction with OH versus hydrolysis of dinitrogen pentoxide (N2O5) with H2O) and varies between regions and on a diurnal basis. A second, slightly higher CQC-based mean value for εN (15.33±4.90 ‰) was estimated for an urban site with intense traffic in eastern China and integrated in a Bayesian isotope mixing model to make isotope-based source apportionment estimates for NOx at this site. Based on the δ15N values (10.93±3.32 ‰; n = 43) of ambient pNO3− determined for the urban site, and considering the location-specific estimate for εN, our results reveal that the relative contribution of coal combustion and road traffic to urban NOx is 32 % ± 11 % and 68 %± 11 %, respectively. This finding agrees well with a regional bottom-up emission inventory of NOx. Moreover, the variation pattern of OH contribution to ambient pNO3− formation calculated by the CQC module is consistent with that simulated by the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem), further confirming the robustness of our estimates. Our investigations also show that, without the consideration of the N isotope effect during pNO3− formation, the observed δ15N–pNO3− at the study site would erroneously imply that NOx is derived almost entirely from coal combustion. Similarly, reanalysis of reported δ15N–NO3− data throughout China and its neighboring areas suggests that NOx emissions from coal combustion may be substantively overestimated (by > 30 %) when the N isotope fractionation during atmospheric pNO3− formation is neglected.

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Characterizing isotopic compositions of TC-C, NO3−-N, and NH4+-N in PM2.5 in South Korea: Impact of China's winter heating

Cited by 69 publications

References 50 publications

The importance of alkyl nitrates and sea ice emissions to atmospheric NO<sub>x</sub> sources and cycling in the summertime Southern Ocean marine boundary layer

The importance of alkyl nitrates and sea ice emissions to atmospheric NO<sub>x</sub> sources and cycling in the summertime Southern Ocean marine boundary layer

Isotopic Constraints on the Atmospheric Sources and Formation of Nitrogenous Species in Biomass-Burning-Influenced Clouds

Nitrogen isotope fractionation during gas-to-particle conversion of NO<sub><i>x</i></sub> to NO<sub>3</sub><sup>−</sup> in the atmosphere – implications for isotope-based NO<sub><i>x</i></sub> source apportionment

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Characterizing isotopic compositions of TC-C, NO3−-N, and NH4+-N in PM2.5 in South Korea: Impact of China's winter heating

Cited by 69 publications

References 50 publications

The importance of alkyl nitrates and sea ice emissions to atmospheric NO&lt;sub&gt;x&lt;/sub&gt; sources and cycling in the summertime Southern Ocean marine boundary layer

The importance of alkyl nitrates and sea ice emissions to atmospheric NO&lt;sub&gt;x&lt;/sub&gt; sources and cycling in the summertime Southern Ocean marine boundary layer

Isotopic Constraints on the Atmospheric Sources and Formation of Nitrogenous Species in Biomass-Burning-Influenced Clouds

Nitrogen isotope fractionation during gas-to-particle conversion of NO&lt;sub&gt;&lt;i&gt;x&lt;/i&gt;&lt;/sub&gt; to NO&lt;sub&gt;3&lt;/sub&gt;&lt;sup&gt;−&lt;/sup&gt; in the atmosphere – implications for isotope-based NO&lt;sub&gt;&lt;i&gt;x&lt;/i&gt;&lt;/sub&gt; source apportionment

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The importance of alkyl nitrates and sea ice emissions to atmospheric NO<sub>x</sub> sources and cycling in the summertime Southern Ocean marine boundary layer

The importance of alkyl nitrates and sea ice emissions to atmospheric NO<sub>x</sub> sources and cycling in the summertime Southern Ocean marine boundary layer

Nitrogen isotope fractionation during gas-to-particle conversion of NO<sub><i>x</i></sub> to NO<sub>3</sub><sup>−</sup> in the atmosphere – implications for isotope-based NO<sub><i>x</i></sub> source apportionment