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 (CH 2 O) 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 CH 2 O 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) × 10 3 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 CH 2 O 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 (SO 2 ) yielded a ratio of 0.81–1.0 times the bottom-up SO 2 inventory, and this provides an important cross-check on the accuracy of our mass balance analysis.

The Korea-United States Air Quality Study (KORUS-AQ) took place in spring 2016 to better understand air pollution in Korea. In support of KORUS-AQ, 2554 whole air samples (WAS) were collected aboard the NASA DC-8 research aircraft and analyzed for 82 C 1 –C 10 volatile organic compounds (VOCs) using multi-column gas chromatography. Together with fast-response measurements from other groups, the air samples were used to characterize the VOC composition in Seoul and surrounding regions, determine which VOCs are major ozone precursors in Seoul, and identify the sources of these reactive VOCs. (1) The WAS VOCs showed distinct signatures depending on their source origins. Air collected over Seoul had abundant ethane, propane, toluene and n -butane while plumes from the Daesan petrochemical complex were rich in ethene, C 2 –C 6 alkanes and benzene. Carbonyl sulfide (COS), CFC-113, CFC-114, carbon tetrachloride (CCl 4 ) and 1,2-dichloroethane were good tracers of air originating from China. CFC-11 was also elevated in air from China but was surprisingly more elevated in air over Seoul. (2) Methanol, isoprene, toluene, xylenes and ethene were strong individual contributors to OH reactivity in Seoul. However methanol contributed less to ozone formation based on photochemical box modeling, which better accounts for radical chemistry. (3) Positive Matrix Factorization (PMF) and other techniques indicated a mix of VOC source influences in Seoul, including solvents, traffic, biogenic, and long-range transport. The solvent and traffic sources were roughly equal using PMF, and the solvents source was stronger in the KORUS-AQ emission inventory. Based on PMF, ethene and propene were primarily associated with traffic, and toluene, ethylbenzene and xylenes with solvents, especially non-paint solvents for toluene and paint solvents for ethylbenzene and xylenes. This suggests that VOC control strategies in Seoul could continue to target vehicle exhaust and paint solvents, with additional regulations to limit the VOC content in a variety of non-paint solvents.

The Seoul Metropolitan Area (SMA) has a population of 24 million and frequently experiences unhealthy levels of ozone (O 3 ). In this work, measurements taken during the Korea-United States Air Quality Study (KORUS-AQ, 2016) are used to explore regional gradients in O 3 and its chemical precursors, and an observationally-constrained 0-D photochemical box model is used to quantify key aspects of O 3 production including its sensitivity to precursor gases. Box model performance was evaluated by comparing modeled concentrations of select secondary species to airborne measurements. These comparisons indicate that the steady state assumption used in 0-D box models cannot describe select intermediate species, highlighting the importance of having a broad suite of trace gases as model constraints. When fully constrained, aggregated statistics of modeled O 3 production rates agreed with observed changes in O 3 , indicating that the box model was able to represent the majority of O 3 chemistry. Comparison of airborne observations between urban Seoul and a downwind receptor site reveal a positive gradient in O 3 coinciding with a negative gradient in NO x , no gradient in CH 2 O, and a slight positive gradient in modeled rates of O 3 production. Together, these observations indicate a radical-limited (VOC-limited) O 3 production environment in the SMA. Zero-out simulations identified C 7+ aromatics as the dominant VOC contributors to O 3 production, with isoprene and anthropogenic alkenes making smaller but appreciable contributions. Simulations of model sensitivity to decreases in NO x produced results that were not spatially uniform, with large increases in O 3 production predicted for urban Seoul and decreases in O 3 production predicted for far-outlying areas. The policy implications of this work are clear: Effective O 3 mitigation strategies in the SMA must focus on reducing local emissions of C 7+ aromatics, while reductions in NO x emissions may increase O 3 in some areas but generally decrease the regional extent of O 3 exposure.