Ambient volatile organic compounds in the Seoul metropolitan area of South Korea: Chemical reactivity, risks and source apportionment.

The chemical reactivity, contribution of emission sources, and risk assessment of volatile organic compounds (VOCs) in the atmosphere of the Seoul metropolitan area (SMA) were analyzed. Datasets collected from 6 photochemical assessment monitoring stations (PAMS) of SMA from 2018 to 2021 were used. Alkenes and aromatics contributed significantly to ozone formation relative to the emission concentrations, and aromatics accounted for most of the secondary organic aerosols (SOA) formation in the SMA. The contributions of ozone and SOA formation were found to be notably higher at measurement stations in residential areas such as Guwol (GW) and Sosabon (SS) compared to other measurement stations. From the results of an emission source analysis, it was confirmed that anthropogenic sources such as combustion sources, vehicle exhaust, fuel evaporation, and solvent use had a significant effect at all measurement stations. Assessing the health risk, non-carcinogenic compounds were at acceptable level at all measurement stations. On the other hand, carcinogenic compounds were approaching risk level (10-4), thereby demanding immediate attention. The level of exposure to carcinogenic compounds increased by age group, and male was more vulnerable than female. It was found that SS had the highest level of exposure to carcinogens in the atmosphere of the population ages 60 or older. The health threat of the SMA population is expected due to direct exposure from inhalation of ambient toxic compounds and indirect exposure from ozone and PM2.5 formations through oxidation of VOCs. This study emphasizes the importance of addressing specific emission sources within the metropolitan area and developing comprehensive regional strategies to mitigate VOCs.

Two Decades of Changes in Summertime Ozone Production in California's South Coast Air Basin.

Tropospheric ozone (O3) continues to be a threat to human health and agricultural productivity. While O3 control is challenging, tracking underlying formation mechanisms provides insights for regulatory directions. Here, we describe a comprehensive analysis of the effects of changing emissions on O3 formation mechanisms with observational evidence. We present a new approach that provides a quantitative metric for the ozone production rate (OPR) and its sensitivity to precursor levels by interpreting two decades of in situ observations of the six criteria air pollutants(2001-2018). Applying to the South Coast Air Basin (SoCAB), California, we show that by 2016-2018, the basin was at the transition region between nitrogen oxide (NOx)-limited and volatile organic compound (VOC)-limited chemical regimes. Assuming future weather conditions are similar to 2016-2018, we predict that NOx-focused reduction is required to reduce the number of summer days the SoCAB is in violation of the National Ambient Air Quality Standard (70 ppbv) for O3. Roughly, ∼40% (∼60%) NOx reductions are required to reduce the OPR by ∼1.8 ppb/h (∼3.3 ppb/h). This change would reduce the number of violation days from 28 to 20% (10%) in a year, mostly in summertime. Concurrent VOC reductions which reduce the production rate of HOx radicals would also be beneficial.

The Korea-United States Air Quality (KORUS-AQ) field study.

The Korea-United States Air Quality (KORUS-AQ) field study was conducted during May-June 2016. The effort was jointly sponsored by the National Institute of Environmental Research of South Korea and the National Aeronautics and Space Administration of the United States. KORUS-AQ offered an unprecedented, multi-perspective view of air quality conditions in South Korea by employing observations from three aircraft, an extensive ground-based network, and three ships along with an array of air quality forecast models. Information gathered during the study is contributing to an improved understanding of the factors controlling air quality in South Korea. The study also provided a valuable test bed for future air quality-observing strategies involving geostationary satellite instruments being launched by both countries to examine air quality throughout the day over Asia and North America. This article presents details on the KORUS-AQ observational assets, study execution, data products, and air quality conditions observed during the study. High-level findings from companion papers in this special issue are also summarized and discussed in relation to the factors controlling fine particle and ozone pollution, current emissions and source apportionment, and expectations for the role of satellite observations in the future. Resulting policy recommendations and advice regarding plans going forward are summarized. These results provide an important update to early feedback previously provided in a Rapid Science Synthesis Report produced for South Korean policy makers in 2017 and form the basis for the Final Science Synthesis Report delivered in 2020.

Regional characteristics of NO2 column densities from Pandora observations during the MAPS-Seoul campaign.

Vertical column density (VCD) of nitrogen dioxide (NO2) was measured using Pandora spectrometers at six sites on the Korean Peninsula during the Megacity Air Pollution Studies-Seoul (MAPS-Seoul) campaign from May to June 2015. To estimate the tropospheric NO2 VCD, the stratospheric NO2 VCD from the Ozone Monitoring Instrument (OMI) was subtracted from the total NO2 VCD from Pandora. European Centre for Medium-Range Weather Forecasts (ECMWF) reanalysis wind data was used to analyze variations in tropospheric NO2 VCD caused by wind patterns at each site. The Yonsei/SEO site was found to have the largest tropospheric NO2 VCD (1.49 DU on average) from a statistical analysis of hourly tropospheric NO2 VCD measurements. At rural sites, remarkably low NO2 VCDs were observed. However, a wind field analysis showed that trans-boundary transport and emissions from domestic sources lead to an increase in tropospheric NO2 VCD at NIER/BYI and KMA/AMY, respectively. At urban sites, high NO2 VCD values were observed under conditions of low wind speed, which were influenced by local urban emissions. Tropospheric NO2 VCD at HUFS/Yongin increases under conditions of significant transport from urban area of Seoul according to a correlation analysis that considers the transport time lag. Significant diurnal variations were found at urban sites during the MAPS-Seoul campaign, but not at rural sites, indicating that it is associated with diurnal patterns of NO2 emissions from dense traffic.

Cavity enhanced spectroscopy for measurement of nitrogen oxides in the Anthropocene: results from the Seoul tower during MAPS 2015.

Cavity enhanced spectroscopy, CES, is a high sensitivity direct absorption method that has seen increasing utility in the last decade, a period also marked by increasing requirements for understanding human impacts on atmospheric composition. This paper describes the current NOAA six channel cavity ring-down spectrometer (CRDS, the most common form of CES) for measurement of nitrogen oxides and O3. It further describes the results from measurements from a tower 300 m above the urban area of Seoul in late spring of 2015. The campaign demonstrates the performance of the CRDS instrument and provides new data on both photochemistry and nighttime chemistry in a major Asian megacity. The instrument provided accurate, high time resolution data for N2O5, NO, NO2, NOy and O3, but suffered from large wall loss in the sampling of NO3, illustrating the requirement for calibration of the NO3 inlet transmission. Both the photochemistry and nighttime chemistry of nitrogen oxides and O3 were rapid in this megacity. Sustained average rates of O3 buildup of 10 ppbv h-1 during recurring morning and early afternoon sea breezes led to a 50 ppbv average daily O3 rise. Nitrate radical production rates, P(NO3), averaged 3-4 ppbv h-1 in late afternoon and early evening, much greater than contemporary data from Los Angeles, a comparable U. S. megacity. These P(NO3) were much smaller than historical data from Los Angeles, however. Nighttime data at 300 m above ground showed considerable variability in high time resolution nitrogen oxide and O3, likely resulting from sampling within gradients in the nighttime boundary layer structure. Apparent nighttime biogenic VOC oxidation rates of several ppbv h-1 were also likely influenced by vertical gradients. Finally, daytime N2O5 mixing ratios of 3-35 pptv were associated with rapid daytime P(NO3) and agreed well with a photochemical steady state calculation.

OH reactivity in urban and suburban regions in Seoul, South Korea - an East Asian megacity in a rapid transition.

South Korea has recently achieved developed country status with the second largest megacity in the world, the Seoul Metropolitan Area (SMA). This study provides insights into future changes in air quality for rapidly emerging megacities in the East Asian region. We present total OH reactivity observations in the SMA conducted at an urban Seoul site (May-June, 2015) and a suburban forest site (Sep, 2015). The total OH reactivity in an urban site during the daytime was observed at similar levels (∼15 s(-1)) to those previously reported from other East Asian megacity studies. Trace gas observations indicate that OH reactivity is largely accounted for by NOX (∼50%) followed by volatile organic compounds (VOCs) (∼35%). Isoprene accounts for a substantial fraction of OH reactivity among the comprehensive VOC observational dataset (25-47%). In general, observed total OH reactivity can be accounted for by the observed trace gas dataset. However, observed total OH reactivity in the suburban forest area cannot be largely accounted for (∼70%) by the trace gas measurements. The importance of biogenic VOC (BVOCs) emissions and oxidations used to evaluate the impacts of East Asian megacity outflows for the regional air quality and climate contexts are highlighted in this study.

Observational insights into aerosol formation from isoprene.

Atmospheric photooxidation of isoprene is an important source of secondary organic aerosol (SOA) and there is increasing evidence that anthropogenic oxidant emissions can enhance this SOA formation. In this work, we use ambient observations of organosulfates formed from isoprene epoxydiols (IEPOX) and methacrylic acid epoxide (MAE) and a broad suite of chemical measurements to investigate the relative importance of nitrogen oxide (NO/NO2) and hydroperoxyl (HO2) SOA formation pathways from isoprene at a forested site in California. In contrast to IEPOX, the calculated production rate of MAE was observed to be independent of temperature. This is the result of the very fast thermolysis of MPAN at high temperatures that affects the distribution of the MPAN reservoir (MPAN / MPA radical) reducing the fraction that can react with OH to form MAE and subsequently SOA (F(MAE formation)). The strong temperature dependence of F(MAE formation) helps to explain our observations of similar concentrations of IEPOX-derived organosulfates (IEPOX-OS; ~1 ng m(-3)) and MAE-derived organosulfates (MAE-OS; ~1 ng m(-3)) under cooler conditions (lower isoprene concentrations) and much higher IEPOX-OS (~20 ng m(-3)) relative to MAE-OS (<0.0005 ng m(-3)) at higher temperatures (higher isoprene concentrations). A kinetic model of IEPOX and MAE loss showed that MAE forms 10-100 times more ring-opening products than IEPOX and that both are strongly dependent on aerosol water content when aerosol pH is constant. However, the higher fraction of MAE ring opening products does not compensate for the lower MAE production under warmer conditions (higher isoprene concentrations) resulting in lower formation of MAE-derived products relative to IEPOX at the surface. In regions of high NOx, high isoprene emissions and strong vertical mixing the slower MPAN thermolysis rate aloft could increase the fraction of MPAN that forms MAE resulting in a vertically varying isoprene SOA source.

Organosulfates as tracers for secondary organic aerosol (SOA) formation from 2-methyl-3-buten-2-ol (MBO) in the atmosphere.

2-Methyl-3-buten-2-ol (MBO) is an important biogenic volatile organic compound (BVOC) emitted by pine trees and a potential precursor of atmospheric secondary organic aerosol (SOA) in forested regions. In the present study, hydroxyl radical (OH)-initiated oxidation of MBO was examined in smog chambers under varied initial nitric oxide (NO) and aerosol acidity levels. Results indicate measurable SOA from MBO under low-NO conditions. Moreover, increasing aerosol acidity was found to enhance MBO SOA. Chemical characterization of laboratory-generated MBO SOA reveals that an organosulfate species (C(5)H(12)O(6)S, MW 200) formed and was substantially enhanced with elevated aerosol acidity. Ambient fine aerosol (PM(2.5)) samples collected from the BEARPEX campaign during 2007 and 2009, as well as from the BEACHON-RoMBAS campaign during 2011, were also analyzed. The MBO-derived organosulfate characterized from laboratory-generated aerosol was observed in PM(2.5) collected from these campaigns, demonstrating that it is a molecular tracer for MBO-initiated SOA in the atmosphere. Furthermore, mass concentrations of the MBO-derived organosulfate are well correlated with MBO mixing ratio, temperature, and acidity in the field campaigns. Importantly, this compound accounted for an average of 0.25% and as high as 1% of the total organic aerosol mass during BEARPEX 2009. An epoxide intermediate generated under low-NO conditions is tentatively proposed to produce MBO SOA.

Ozone deposition to an orange orchard: Partitioning between stomatal and non-stomatal sinks.

Orange trees are widely cultivated in regions with high concentrations of tropospheric ozone. Citrus absorb ozone through their stomata and emit volatile organic compounds (VOC), which, together with soil emissions of NO, contribute to non-stomatal ozone removal. In a Valencia orange orchard in Exeter, California, we used fast sensors and eddy covariance to characterize water and ozone fluxes. We also measured meteorological parameters necessary to model other important sinks of ozone deposition. We present changes in magnitude of these ozone deposition sinks over the year in response to environmental parameters. Within the plant canopy, the orchard constitutes a sink for ozone, with non-stomatal ozone deposition larger than stomatal uptake. In particular, soil deposition and reactions between ozone, VOC and NO represented the major sinks of ozone. This research aims to help the development of metrics for ozone-risk assessment and advance our understanding of citrus in biosphere-atmosphere exchange.

Sesquiterpenoid emissions from agricultural crops: correlations to monoterpenoid emissions and leaf terpene content.

Emissions of biogenic volatile organic compounds (BVOCs) are important precursors to both ozone and secondary organic aerosol formation. In this study, we identify and quantify volatile (C(10)) and intermediate-volatility (C(15)) BVOCs stored in and emitted from 22 prominent woody and herbaceous crops with a particular focus on sesquiterpenoids (SQTs), which have presented measurement challenges in previous studies. Monoterpenoids (MNTs) and SQTs were simultaneously emitted from all the crops studied; there were significant correlations between emission rates and leaf content for both MNTs and SQTs and additional correlations between MNTs and SQTs in both emissions and leaf content. Our results suggest that species with high concentrations of stored terpenoids in their leaves, such as those grown commercially for their essential oil content, are likely high BVOC emitters. Emissions from agricultural species were dominated by SQTs at low MNT emission rates (on the order of several tens of ng/(g(DM)*h)), while at higher MNT levels (on the order of several hundreds of ng/(g(DM)*h)), SQT emissions were approximately equivalent. Based on our empirical correlations, we estimate that global SQT emissions are similar to MNT emissions and on the order of 100 Tg yr(-1), which justifies the need for better representation of SQTs in both BVOC emission and atmospheric models.