The U.S. National Aeronautics and Space Administration in partnership with Korea’s National Institute of Environmental Research embarked on the Korea-United States Air Quality (KORUS-AQ) study to address air quality issues over the Korean peninsula. Underestimation of volatile organic compound (VOC) emissions from various large facilities on South Korea’s northwest coast may contribute to this problem, and this study focuses on quantifying top-down emissions of formaldehyde (CH2O) and VOCs from the largest of these facilities, the Daesan petrochemical complex, and comparisons with the latest emission inventories. To accomplish this and additional goals discussed herein, this study employed a number of measurements acquired during KORUS-AQ onboard the NASA DC-8 aircraft during three Daesan overflights on June 2, 3, and 5, 2016, in conjunction with a mass balance approach. The measurements included fast airborne measurements of CH2O and ethane from an infrared spectrometer, additional fast measurements from other instruments, and a suite of 33 VOC measurements acquired by the whole air sampler. The mass balance approach resulted in consistent top-down yearly Daesan VOC emission flux estimates, which averaged (61 ± 14) × 103 MT/year for the 33 VOC compounds, a factor of 2.9 ± 0.6 (±1.0) higher than the bottom-up inventory value. The top-down Daesan emission estimate for CH2O and its four primary precursors averaged a factor of 4.3 ± 1.5 (± 1.9) times higher than the bottom-up inventory value. The uncertainty values in parentheses reflect upper limits for total uncertainty estimates. The resulting averaged top-down Daesan emission estimate for sulfur dioxide (SO2) yielded a ratio of 0.81–1.0 times the bottom-up SO2 inventory, and this provides an important cross-check on the accuracy of our mass balance analysis.

Abstract. Glyoxal (CHOCHO), the simplest dicarbonyl in the troposphere, is a potential precursor for secondary organic aerosol (SOA) and brown carbon (BrC) affecting air quality and climate. The airborne measurement of CHOCHO concentrations during the KORUS-AQ (KORea–US Air Quality study) campaign in 2016 enables detailed quantification of loss mechanisms pertaining to SOA formation in the real atmosphere. The production of this molecule was mainly from oxidation of aromatics (59 %) initiated by hydroxyl radical (OH). CHOCHO loss to aerosol was found to be the most important removal path (69 %) and contributed to roughly ∼ 20 % (3.7 µg sm−3 ppmv−1 h−1, normalized with excess CO) of SOA growth in the first 6 h in Seoul Metropolitan Area. A reactive uptake coefficient (γ) of ∼ 0.008 best represents the loss of CHOCHO by surface uptake during the campaign. To our knowledge, we show the first field observation of aerosol surface-area-dependent (Asurf) CHOCHO uptake, which diverges from the simple surface uptake assumption as Asurf increases in ambient condition. Specifically, under the low (high) aerosol loading, the CHOCHO effective uptake rate coefficient, keff,uptake, linearly increases (levels off) with Asurf; thus, the irreversible surface uptake is a reasonable (unreasonable) approximation for simulating CHOCHO loss to aerosol. Dependence on photochemical impact and changes in the chemical and physical aerosol properties “free water”, as well as aerosol viscosity, are discussed as other possible factors influencing CHOCHO uptake rate. Our inferred Henry's law coefficient of CHOCHO, 7.0×108 M atm−1, is ∼ 2 orders of magnitude higher than those estimated from salting-in effects constrained by inorganic salts only consistent with laboratory findings that show similar high partitioning into water-soluble organics, which urges more understanding on CHOCHO solubility under real atmospheric conditions.

Large industrial facilities, such as petrochemical complexes, have decisive effects on regional air quality: directly due to their own hazardous volatile organic compounds (VOCs) emissions and indirectly due to their contribution to secondary air pollution. In South Korea, pronounced ozone and particulate matter issues have been reported in industrial areas. In this study, we develop a new top-down VOC emission rate estimation method using in situ airborne formaldehyde (HCHO) observations in the downwind plume of the Daesan Petrochemical Complex (DPC) in South Korea during the 2016 Korea–United States Air Quality (KORUS-AQ) mission. On May 22, we observed a peak HCHO mole fraction of 12 ppb after a transport time of 2.5 h (distance approximately 36 km) under conditions where the HCHO photochemical lifetime was 1.8 h. Box model calculations indicate that this elevated HCHO is mainly due to secondary production (more than 90% after 2 h of plume aging) from various VOC precursors including ethene, propene, and 1,3-butadiene. We estimate a lower limit for yearly DPC VOC emissions of 31 (±8.7) × 103 MT/year for HCHO precursors and 53 (±15) × 103 MT/year for all measured primary VOCs. These estimates are 1.5–2.5 times higher than the latest Korean emission inventories, KORUSv5. This method is beneficial not only by tracking the sources, sinks, and evolution of HCHO but also by validating existing emission inventories.