Nonmethane volatile organic compounds (NMVOCs) result in ozone and aerosol production that adversely affects the environment and human health. For modeling purposes, anthropogenic NMVOC emissions have been typically compiled using the “bottom-up” approach. To minimize uncertainties of the bottom-up emission inventory, “top-down” NMVOC emissions can be estimated using formaldehyde (HCHO) observations. In this study, HCHO vertical column densities (VCDs) obtained from the Geostationary Trace gas and Aerosol Sensor Optimization spectrometer during the Korea–United States Air Quality campaign were used to constrain anthropogenic volatile organic compound (AVOC) emissions in South Korea. Estimated top-down AVOC emissions differed from those of the up-to-date bottom-up inventory over major anthropogenic source regions by factors of 1.0 ± 0.4 to 6.9 ± 3.9. Our evaluation using a 3D chemical transport model indicates that simulated HCHO mixing ratios using the top-down estimates were in better agreement with observations onboard the DC-8 aircraft during the campaign relative to those with the bottom-up emission, showing a decrease in model bias from –25% to –13%. The top-down analysis used in this study, however, has some limitations related to the use of HCHO yields, background HCHO columns, and AVOC speciation in the bottom-up inventory, resulting in uncertainties in the AVOC emission estimates. Our attempt to constrain diurnal variations of the AVOC emissions using the aircraft HCHO VCDs was compromised by infrequent aircraft observations over the same source regions. These limitations can be overcome with geostationary satellite observations by providing hourly HCHO VCDs.

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.

The cryosphere, which comprises a large portion of Earth’s surface, is rapidly changing as a consequence of global climate change. Ice, snow, and frozen ground in the polar and alpine regions of the planet are known to directly impact atmospheric composition, which for example is observed in the large influence of ice and snow on polar boundary layer chemistry. Atmospheric inputs to the cryosphere, including aerosols, nutrients, and contaminants, are also changing in the anthropocene thus driving cryosphere-atmosphere feedbacks whose understanding is crucial for understanding future climate. Here, we present the Cryosphere and ATmospheric Chemistry initiative (CATCH) which is focused on developing new multidisciplinary research approaches studying interactions of chemistry, biology, and physics within the coupled cryosphere – atmosphere system and their sensitivity to environmental change. We identify four key science areas: (1) micro-scale processes in snow and ice, (2) the coupled cryosphere-atmosphere system, (3) cryospheric change and feedbacks, and (4) improved decisions and stakeholder engagement. To pursue these goals CATCH will foster an international, multidisciplinary research community, shed light on new research needs, support the acquisition of new knowledge, train the next generation of leading scientists, and establish interactions between the science community and society.

We examine O 3 production and its sensitivity to precursor gases and boundary layer mixing in Korea by using a 3-D global chemistry transport model and extensive observations during the KORea-US cooperative Air Quality field study in Korea, which occurred in May–June 2016. During the campaign, observed aromatic species onboard the NASA DC-8 aircraft, especially toluene, showed high mixing ratios of up to 10 ppbv, emphasizing the importance of aromatic chemistry in O 3 production. To examine the role of VOCs and NO x in O 3 chemistry, we first implement a detailed aromatic chemistry scheme in the model, which reduces the normalized mean bias of simulated O 3 mixing ratios from –26% to –13%. Aromatic chemistry also increases the average net O 3 production in Korea by 37%. Corrections of daytime PBL heights, which are overestimated in the model compared to lidar observations, increase the net O 3 production rate by ~10%. In addition, increasing NO x emissions by 50% in the model shows best performance in reproducing O 3 production characteristics, which implies that NO x emissions are underestimated in the current emissions inventory. Sensitivity tests show that a 30% decrease in anthropogenic NO x emissions in Korea increases the O 3 production efficiency throughout the country, making rural regions ~2 times more efficient in producing O 3 per NO x consumed. Simulated O 3 levels overall decrease in the peninsula except for urban and other industrial areas, with the largest increase (~6 ppbv) in the Seoul Metropolitan Area (SMA). However, with simultaneous reductions in both NO x and VOCs emissions by 30%, O 3 decreases in most of the country, including the SMA. This implies the importance of concurrent emission reductions for both NO x and VOCs in order to effectively reduce O 3 levels in Korea.

We present measurements of CO mole fraction and CO stable isotopes (δ 13 CO and δC 18 O) in air during the winters of 2013–14 and 2014–15 at tall tower sampling sites in and around Indianapolis, USA. A tower located upwind of the city was used to quantitatively remove the background CO signal, allowing for the first unambiguous isotopic characterization of the urban CO source and yielding 13 CO of –27.7 ± 0.5‰ VPDB and C 18 O of 17.7 ± 1.1‰ VSMOW for this source. We use the tower isotope measurements, results from a limited traffic study, as well as atmospheric reaction rates to examine contributions from different sources to the Indianapolis CO budget. Our results are consistent with earlier findings that traffic emissions are the dominant source, suggesting a contribution of 96% or more to the overall Indianapolis wintertime CO emissions. Our results are also consistent with the hypothesis that emissions from a small fraction of vehicles without functional catalytic systems dominate the Indianapolis CO budget.

A twelve-station tower-based observation network measuring CO 2 , CH 4 , and CO was deployed in and around the Indianapolis, IN metropolitan area as part of the Indianapolis Flux Experiment (INFLUX). Measurements began in 2010 and the full network was deployed by 2013. Observations were made at heights ranging from 39 to 136 m above ground level using existing communication towers. Several towers in the network had multiple measurement levels. Cavity ring-down spectrometers (CRDS) were used at all twelve sites and at least one calibrated reference tank was sampled daily at each site. Real time data communications were performed via cellular modems and data were transmitted daily for processing and quality assurance checks. Data quality control procedures were utilized to ensure compatibility within the INFLUX tower network and with global standards. For example, field target/calibration tanks were used to detect long-term instrument drift and instrument failure. Network-wide round robin tests were performed every 1–2 years to detect possible target tank drift and ensure network-wide comparability between measurements. NOAA flask packages were deployed at six of the INFLUX towers to provide a flask to in-situ direct comparison of the atmospheric samples. Results from these activities demonstrate that the compatibility of the CO 2 , CH 4 , and CO INFLUX in-situ tower-based measurements are less than or equal to 0.18 ppm CO 2 , 1.0 ppb for CH 4 , and 6 ppb for CO.

Large spatial and temporal uncertainties for landfill CH 4 emissions remain unresolved by short-term field campaigns and historic greenhouse gas (GHG) inventory models. Using four field methods (aircraft-based mass balance, tracer correlation, vertical radial plume mapping, static chambers) and a new field-validated process-based model (California Landfill Methane Inventory Model, CALMIM 5.4), we investigated the total CH 4 emissions from a central Indiana landfill as well as the partitioned emissions inclusive of methanotrophic oxidation for the various cover soils at the site. We observed close agreement between whole site emissions derived from the tracer correlation (8 to 13 mol s –1 ) and the aircraft mass balance approaches (7 and 17 mol s –1 ) that were statistically indistinguishable from the modeling result (12 ± 2 mol s –1 inclusive of oxidation). Our model calculations indicated that approximately 90% of the annual average CH 4 emissions (11 ± 1 mol s –1 ; 2200 ± 250 g m –2 d –1 ) derived from the small daily operational area. Characterized by a thin overnight soil cover directly overlying a thick sequence of older methanogenic waste without biogas recovery, this area constitutes only 2% of the 0.7 km 2 total waste footprint area. Because this Indiana landfill is an upwind source for Indianapolis, USA, the resolution of m 2 to km 2 scale emissions at various temporal scales contributes to improved regional inventories relevant for addressing GHG mitigation strategies. Finally, our comparison of measured to reported CH 4 emissions under the US EPA National GHG Reporting program suggests the need to revisit the current IPCC ( 2006 ) GHG inventory methodology based on CH 4 generation modeling. The reasonable prediction of emissions at individual U.S. landfills requires incorporation of both cover-specific landfill climate modeling (e.g., soil temperature/moisture variability over a typical annual cycle driving CH 4 transport and oxidation rates) as well as operational issues (e.g., cover thickness/properties, extent of biogas recovery).

To effectively address climate change, aggressive mitigation policies need to be implemented to reduce greenhouse gas emissions. Anthropogenic carbon emissions are mostly generated from urban environments, where human activities are spatially concentrated. Improvements in uncertainty determinations and precision of measurement techniques are critical to permit accurate and precise tracking of emissions changes relative to the reduction targets. As part of the INFLUX project, we quantified carbon dioxide (CO 2 ), carbon monoxide (CO) and methane (CH 4 ) emission rates for the city of Indianapolis by averaging results from nine aircraft-based mass balance experiments performed in November-December 2014. Our goal was to assess the achievable precision of the aircraft-based mass balance method through averaging, assuming constant CO 2 , CH 4 and CO emissions during a three-week field campaign in late fall. The averaging method leads to an emission rate of 14,600 mol/s for CO 2 , assumed to be largely fossil-derived for this period of the year, and 108 mol/s for CO. The relative standard error of the mean is 17% and 16%, for CO 2 and CO, respectively, at the 95% confidence level (CL), i.e. a more than 2-fold improvement from the previous estimate of ~40% for single-flight measurements for Indianapolis. For CH 4 , the averaged emission rate is 67 mol/s, while the standard error of the mean at 95% CL is large, i.e. ±60%. Given the results for CO 2 and CO for the same flight data, we conclude that this much larger scatter in the observed CH 4 emission rate is most likely due to variability of CH 4 emissions, suggesting that the assumption of constant daily emissions is not correct for CH 4 sources. This work shows that repeated measurements using aircraft-based mass balance methods can yield sufficient precision of the mean to inform emissions reduction efforts by detecting changes over time in urban emissions.