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The availability of formaldehyde (HCHO) (a proxy for volatile organic compound reactivity) and nitrogen dioxide (NO2) (a proxy for nitrogen oxides) tropospheric columns from ultraviolet–visible (UV–Vis) satellites has motivated many to use their ratios to gain some insights into the near-surface ozone sensitivity. Strong emphasis has been placed on the challenges that come with transforming what is being observed in the tropospheric column to what is actually in the planetary boundary layer (PBL) and near the surface; however, little attention has been paid to other sources of error such as chemistry, spatial representation, and retrieval uncertainties. Here we leverage a wide spectrum of tools and data to quantify those errors carefully. Concerning the chemistry error, a well-characterized box model constrained by more than 500 h of aircraft data from NASA's air quality campaigns is used to simulate the ratio of the chemical loss of HO2 + RO2 (LROx) to the chemical loss of NOx (LNOx). Subsequently, we challenge the predictive power of HCHO/NO2 ratios (FNRs), which are commonly applied in current research, in detecting the underlying ozone regimes by comparing them to LROx/LNOx. FNRs show a strongly linear (R2=0.94) relationship with LROx/LNOx, but only on the logarithmic scale. Following the baseline (i.e., ln(LROx/LNOx) = −1.0 ± 0.2) with the model and mechanism (CB06, r2) used for segregating NOx-sensitive from VOC-sensitive regimes, we observe a broad range of FNR thresholds ranging from 1 to 4. The transitioning ratios strictly follow a Gaussian distribution with a mean and standard deviation of 1.8 and 0.4, respectively. This implies that the FNR has an inherent 20 % standard error (1σ) resulting from not accurately describing the ROx–HOx cycle. We calculate high ozone production rates (PO3) dominated by large HCHO × NO2 concentration levels, a new proxy for the abundance of ozone precursors. The relationship between PO3 and HCHO × NO2 becomes more pronounced when moving towards NOx-sensitive regions due to nonlinear chemistry; our results indicate that there is fruitful information in the HCHO × NO2 metric that has not been utilized in ozone studies. The vast amount of vertical information on HCHO and NO2 concentrations from the air quality campaigns enables us to parameterize the vertical shapes of FNRs using a second-order rational function permitting an analytical solution for an altitude adjustment factor to partition the tropospheric columns into the PBL region. We propose a mathematical solution to the spatial representation error based on modeling isotropic semivariograms. Based on summertime-averaged data, the Ozone Monitoring Instrument (OMI) loses 12 % of its spatial information at its native resolution with respect to a high-resolution sensor like the TROPOspheric Monitoring Instrument (TROPOMI) (> 5.5 × 3.5 km2). A pixel with a grid size of 216 km2 fails at capturing ∼ 65 % of the spatial information in FNRs at a 50 km length scale comparable to the size of a large urban center (e.g., Los Angeles). We ultimately leverage a large suite of in situ and ground-based remote sensing measurements to draw the error distributions of daily TROPOMI and OMI tropospheric NO2 and HCHO columns. At a 68 % confidence interval (1σ), errors pertaining to daily TROPOMI observations, either HCHO or tropospheric NO2 columns, should be above 1.2–1.5 × 1016 molec. cm−2 to attain a 20 %–30 % standard error in the ratio. This level of error is almost non-achievable with the OMI given its large error in HCHO. The satellite column retrieval error is the largest contributor to the total error (40 %–90 %) in the FNRs. Due to a stronger signal in cities, the total relative error (< 50 %) tends to be mild, whereas areas with low vegetation and anthropogenic sources (e.g., the Rocky Mountains) are markedly uncertain (> 100 %). Our study suggests that continuing development in the retrieval algorithm and sensor design and calibration is essential to be able to advance the application of FNRs beyond a qualitative metric.

The availability of formaldehyde (HCHO) (a proxy for volatile organic compound reactivity) and nitrogen dioxide (NO2) (a proxy for nitrogen oxides) tropospheric columns from Ultraviolet-Visible (UV-Vis) satellites has motivated many to use their ratios to gain some insights into the near-surface ozone sensitivity. Strong emphasis has been placed on the challenges that come with transforming what is being observed in the tropospheric column to what is actually in the planetary boundary layer (PBL) and near to the surface; however, little attention has been paid to other sources of error such as chemistry, spatial representation, and retrieval uncertainties. Here we leverage a wide spectrum of tools and data to carefully quantify those errors. Concerning the chemistry error, a well-characterized box model constrained by more than 500 hours of aircraft data from NASA’s air quality campaigns is used to simulate the ratio of the chemical loss of HO2+RO2 (LROx) to the chemical loss of NOx (LNOx). Subsequently, we challenge the predictive power of HCHO / NO2 ratios (FNRs), which are commonly applied in current research, at detecting the underlying ozone regimes by comparing them to LROx / LNOx. FNRs show a strongly linear (R2=0.94) relationship to LROx / LNOx in the log-log scale. Following the baseline (i.e., ln(LROx / LNOx) = -1.0±0.2) with the model and mechanism (CB06, r2) used for segregating NOx-sensitive from VOC-sensitive regimes, we observe a broad range of FNR thresholds ranging from 1 to 4. The transitioning ratios strictly follow a Gaussian distribution with a mean and standard deviation of 1.8 and 0.4, respectively. This implies that FNR has an inherent 20 % standard error (1-sigma) resulting from not being able to fully describe the ROx-HOx cycle. We calculate high ozone production rates (PO3) dominated by large HCHO×NO2 concentration levels, a new proxy for the abundance of ozone precursors. The relationship between PO3 and HCHO×NO2 becomes more pronounced when moving towards NOx-sensitive regions due to non-linear chemistry; our results indicate that there is fruitful information in the HCHO×NO2 metric that has not been utilized in ozone studies. The vast amount of vertical information on HCHO and NO2 concentration from the air quality campaigns enables us to parameterize the vertical shapes of FNRs using a second-order rational function permitting an analytical solution for an altitude adjustment factor to partition the tropospheric columns to the PBL region. We propose a mathematical solution to the spatial representation error based on modeling isotropic semivariograms. With respect to a high-resolution sensor like TROPOspheric Monitoring Instrument (TROPOMI) (>5.5×3.5 km2), Ozone Monitoring Instrument (OMI) loses 12 % of spatial information at its native resolution. A pixel with a grid size of 216 km2 fails at capturing ~65 % of the spatial information in FNRs at a 50 km length scale comparable to the size of a large urban center (e.g., Los Angeles). We ultimately leverage a large suite of in-situ and ground-based remote sensing measurements to draw the error distributions of daily TROPOMI and OMI tropospheric NO2 and HCHO columns. At 68 % confidence interval (1 sigma) errors pertaining to daily TROPOMI observations, either HCHO or tropospheric NO2 columns should be above 1.2–1.5×1016 molec.cm-2 to attain 20–30 % standard error in the ratio. This level of error is almost non-achievable with OMI given its large error in HCHO. The satellite column retrieval error is the largest contributor to the total error (40–90 %) in the FNRs. Due to a stronger signal in cities, the total relative error (100 %). Our study suggests that continuing development in the retrieval algorithm and sensor design and calibration is essential to be able to advance the application of FNRs beyond a qualitative metric.

We describe the characteristics and performances of our newly built broadband cavity-enhanced absorption spectrometer for measurements of nitrate radical (NO3), nitrogen dioxide (NO2), and water vapor (H2O). A customized vibration-resistance cavity layout incorporated with N2 purging on high-reflection mirror surfaces was implemented with a red light-emitting diode (LED) as a light source. In general, this system achieved over 40 km (up to 101.5 km) of effective light path length at 662 nm from a 0.52 m long cavity. For accurate NO3 measurement, the measured absorption spectrum of H2O was used for simultaneous concentration retrievals with the other species instead of being treated as interferences to be removed or corrected prior to NO3 detection. Synthesized N2O5 crystals under atmospheric pressure were used for performance tests of linear response and transmission efficiency. From the standard injection experiments of NO3, NO2, and H2O, high linearities were observed (R2≥0.9918). The total NO3 transmission efficiency through the system was determined to be 81.2 % (±2.9, 1σ) within the residence time of 2.59 s. The precisions (1σ) of NO3, NO2, and H2O in 1 Hz measurement from a single pixel on the charge-coupled device (CCD) were 1.41 pptv, 6.92 ppbv, and 35.0 ppmv with uncertainties of 10.8 %, 5.2 %, and ≥20.5 %, respectively, mainly from the errors in the literature absorption cross-section. The instrument was successfully deployed aboard the Korean icebreaker R/V Araon for an expedition conducted in the remote marine boundary layer in the Arctic Ocean during the summer of 2021.

Tropospheric ozone (O

Living in an era of government allocated carbon dioxide (CO2) emissions, knowing the accurate amount of human-induced CO2 becomes very critical. To this end, an in-depth understanding of CO2 emissions in urban areas where human activities are concentrated will be of practical help. With this motivation, we quantify CO2 emission strengths of individual urban activities (i.e. vehicle, industry, heat generation, etc.) based on direct observations of vertical CO2 exchanges at urban-atmosphere interface using Eddy-Covariance (EC) method at Gwangju, Korea (2017.11–2018.08). Day of week difference analysis, together with varying wind sector, grounded from carefully designed measurement set-up, enables us to assess CO2 emission factors (EFs) free from seasonal bias (i.e. heating and urban vegetation); evaluated EFs of traffic from day of week difference was 0.017(±0.011) μmol m-2 s-1 car-1 which is more than 10 times larger than that from simple relation (0.0012 ± 0.0011 μmol m-2 s-1 car-1) between CO2 flux and traffic counts. The CO2 emissions due to the car manufacturing industry within the fetch and heating when air temperatures were lower than 18 °C were quantified as 103.25(±42.18) μmol m-2 s-1 and 2.41(±1.71) μmol m-2 s-1 °C-1, respectively. Urban vegetation uptake was estimated as -1.72 kg C m-2 yr-1 only with EFs traffic inferred from day of week difference indicating possible erroneous estimation in simple relation unless it properly reflects representative seasonal changes in a year. Even though our estimations are conservative EFs due to limitations in corrections of horizontal seepage and vertical storage, we found that both EFs for traffic and heat in latest emission inventory were more than 2.5 times lower than our estimations which indicate the urgency in bottom-up inventory validations.

Glyoxal (CHOCHO), the simplest dicarbonyl in the troposphere, is an important 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), of which glyoxal forming mechanisms are relatively well constrained. 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 hr−1, normalized with excess CO) of SOA growth in the first 6 hours in Seoul Metropolitan Area. To our knowledge, we show the first field observation of aerosol surface-area (Asurf)-dependent 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. Dependency of photochemical impact, 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, which urges more understanding on CHOCHO solubility under real atmospheric conditions.

As nitrous acid (HONO) photolysis is an important source of hydroxyl radical (OH), apportionment of the ambient HONO sources is necessary to better understand atmospheric oxidation. Based on the data HONO-related species and various parameters measured during the one-month campaign at Wangdu (a rural site in North China plain) in summer 2014, a box model was adopted with input of current literature parametrizations for various HONO sources (nitrogen dioxide heterogeneous conversion, photoenhanced conversion, photolysis of adsorbed nitric acid and particulate nitrate, acid displacement, and soil emission) to reveal the relative importance of each source at the rural site. The simulation results reproduced the observed HONO production rates during noontime in general but with large uncertainty from both the production and destruction terms. NO2 photoenhanced conversion and photolysis of particulate nitrate were found to be the two major mechanisms with large potential of HONO formation but the associated uncertainty may reduce their importance to be nearly negligible. Soil nitrite was found to be an important HONO source during fertilization periods, accounted for (80 ± 6)% of simulation HONO during noontime. For some episodes of the biomass burning, only the NO2 heterogeneous conversion to HONO was promoted significantly. In summary, the study of the HONO budget is still far from closed, which would require a significant effort on both the accurate measurement of HONO and the determination of related kinetic parameters for its production pathways.

Biomass burning (BB) is a large source of reactive compounds in the atmosphere. While the daytime photochemistry of BB emissions has been studied in some detail, there has been little focus on nighttime reactions despite the potential for substantial oxidative and heterogeneous chemistry. Here, we present the first analysis of nighttime aircraft intercepts of agricultural BB plumes using observations from the NOAA WP-3D aircraft during the 2013 Southeast Nexus (SENEX) campaign. We use these observations in conjunction with detailed chemical box modeling to investigate the formation and fate of oxidants (NO3, N2O5, O3, and OH) and BB volatile organic compounds (BBVOCs), using emissions representative of agricultural burns (rice straw) and western wildfires (ponderosa pine). Field observations suggest NO3 production was approximately 1 ppbv hr-1, while NO3 and N2O5 were at or below 3 pptv, indicating rapid NO3/N2O5 reactivity. Model analysis shows that >99% of NO3/N2O5 loss is due to BBVOC + NO3 reactions rather than aerosol uptake of N2O5. Nighttime BBVOC oxidation for rice straw and ponderosa pine fires is dominated by NO3 (72, 53%, respectively) but O3 oxidation is significant (25, 43%), leading to roughly 55% overnight depletion of the most reactive BBVOCs and NO2.

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.

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.

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.

We report enhancements of glyoxal and methylglyoxal relative to carbon monoxide and formaldehyde in agricultural biomass burning plumes intercepted by the NOAA WP-3D aircraft during the 2013 Southeast Nexus and 2015 Shale Oil and Natural Gas Nexus campaigns. Glyoxal and methylglyoxal were measured using broadband cavity enhanced spectroscopy, which for glyoxal provides a highly selective and sensitive measurement. While enhancement ratios of other species such as methane and formaldehyde were consistent with previous measurements, glyoxal enhancements relative to carbon monoxide averaged 0.0016 ± 0.0009, a factor of 4 lower than values used in global models. Glyoxal enhancements relative to formaldehyde were 30 times lower than previously reported, averaging 0.038 ± 0.02. Several glyoxal loss processes such as photolysis, reactions with hydroxyl radicals, and aerosol uptake were found to be insufficient to explain the lower measured values of glyoxal relative to other biomass burning trace gases, indicating that glyoxal emissions from agricultural biomass burning may be significantly overestimated. Methylglyoxal enhancements were three to six times higher than reported in other recent studies, but spectral interferences from other substituted dicarbyonyls introduce an estimated correction factor of 2 and at least a 25% uncertainty, such that accurate measurements of the enhancements are difficult.

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, NOyand O3, but suffered from large wall loss in the sampling of NO3, illustrating the requirement for calibration of the NO3inlet transmission. Both the photochemistry and nighttime chemistry of nitrogen oxides and O3were rapid in this megacity. Sustained average rates of O3buildup of 10 ppbv h−1during recurring morning and early afternoon sea breezes led to a 50 ppbv average daily O3rise. Nitrate radical production rates,P(NO3), averaged 3–4 ppbv h−1in late afternoon and early evening, much greater than contemporary data from Los Angeles, a comparable U. S. megacity. TheseP(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−1were also likely influenced by vertical gradients. Finally, daytime N2O5mixing ratios of 3–35 pptv were associated with rapid daytimeP(NO3) and agreed well with a photochemical steady state calculation.

We apply a high-resolution chemical transport model (GEOS-Chem CTM) with updated treatment of volatile organic compounds (VOCs) and a comprehensive suite of airborne datasets over North America to i) characterize the VOC budget, and ii) test the ability of current models to capture the distribution and reactivity of atmospheric VOCs, over this region. Biogenic emissions dominate the North American VOC budget in the model, accounting for 70 % and 95 % of annually emitted VOC-carbon and reactivity, respectively. Based on current inventories anthropogenic emissions have declined to the point where biogenic emissions are the dominant summertime source of VOC reactivity even in most major North American cities. Methane oxidation is a 2× larger source of non-methane VOCs (via production of formaldehyde and methyl hydroperoxide) over North America in the model than are anthropogenic emissions. However, anthropogenic VOCs account for over half the ambient VOC loading over the majority of the region owing to their longer aggregate lifetime. Fires can be a significant VOC source episodically but are small on average. In the planetary boundary layer (PBL), the model exhibits skill in capturing observed variability in total VOC-abundance (R2 = 0.36) and reactivity (R2 = 0.54). The same is not true in the free troposphere (FT), where skill is low and there is a persistent low model bias (~ 60 %), with most (27 of 34) model VOCs underestimated by more than a factor of 2. A comparison of PBL : FT concentration ratios over the southeastern US points to a misrepresentation of PBL ventilation as a contributor to these model FT biases. We also find that a relatively small number of VOCs (acetone, methanol, ethane, acetaldehyde, formaldehyde, isoprene + oxidation products, methyl hydroperoxide) drive a large fraction of total ambient VOC reactivity and associated model biases; research to improve understanding of their budgets is thus warranted. A source tracer analysis suggests a current overestimate of biogenic sources for hydroxyacetone, methyl ethyl ketone and glyoxal, an underestimate of biogenic formic acid sources, and an underestimate of peroxyacetic acid production across biogenic and anthropogenic precursors. Future work to improve model representations of vertical transport and to address the VOC biases discussed are needed to advance predictions of ozone and SOA formation.

The Southeast United States (US) might not have warmed as much as the rest of the country over the past 50-100 years. Providing an improved understanding of this potential anomaly, and specifically the roles played by aerosols, was one of the main goals for the Southeast Atmosphere Study (SAS). Natural emissions of ozone-and-aerosol-precursor gases such as isoprene and monoterpenes are high in the southeast of the US. In addition, anthropogenic emissions are significant inthe Southeast US and summertime photochemistry is rapid. The NOAA-led SENEX (Southeast Nexus) aircraft campaign was one of the major components of the SAS studyand was focused on studying the interactions between biogenic and anthropogenic emissions to form secondary pollutants. During SENEX, the NOAA WP-3D aircraft conducted 20 research flights between 27 May and 10 July 2013 based out of Smyrna, TN. Here we describe the experimental approach, the science goals and early results of the NOAA SENEX campaign. The aircraft, its capabilities and standard measurements are described. The instrument payload is summarized including detection limits, accuracy, precision and time resolutions for all gas-and-aerosol phase instruments. The inter-comparisons of compounds measured with multiple instruments on the NOAA WP-3D are presented and were almost all within the stated uncertainties. The SENEX flights included day- and nighttime flights in the Southeast as well as flights over areas with intense shale gas extraction (Marcellus, Fayetteville and Haynesville shale). We present one example flight on 16 June 2013, which was a daytime flight over the Atlanta region, where several crosswind transects of plumes from the city and nearby point sources, such as power plants, paper mills and landfills, were flown. The area around Atlanta has large biogenic isoprene emissions, which provided an excellent case for studying the interactions between biogenic and anthropogenic emissions. In this example flight, chemistry in and outside the Atlanta plumes was observed for several hours after emission. The analysis of this flight showcases the strategies implemented to answer some of the main SENEX science questions.

We use a 0-D photochemical box model and a 3-D global chemistry-climate model, combined with observations from the NOAA Southeast Nexus (SENEX) aircraft campaign, to understand the sources and sinks of glyoxal over the Southeast United States. Box model simulations suggest a large difference in glyoxal production among three isoprene oxidation mechanisms (AM3ST, AM3B, and MCM v3.3.1). These mechanisms are then implemented into a 3-D global chemistry-climate model. Comparison with field observations shows that the average vertical profile of glyoxal is best reproduced by AM3ST with an effective reactive uptake coefficient γglyx of 2 × 10−3, and AM3B without heterogeneous loss of glyoxal. The two mechanisms lead to 0–0.8 μg m−3 secondary organic aerosol (SOA) from glyoxal in the boundary layer of the Southeast U.S. in summer. We consider this to be the lower limit for the contribution of glyoxal to SOA, as other sources of glyoxal other than isoprene are not included in our model. In addition, we find that AM3B shows better agreement on both formaldehyde and the correlation between glyoxal and formaldehyde (RGF = [GLYX]/[HCHO]), resulting from the suppression of δ-isoprene peroxy radicals (δ-ISOPO2). We also find that MCM v3.3.1 may underestimate glyoxal production from isoprene oxidation, in part due to an underestimated yield from the reaction of IEPOX peroxy radicals (IEPOXOO) with HO2. Our work highlights that the gas-phase production of glyoxal represents a large uncertainty in quantifying its contribution to SOA.

The sources and distribution of tropospheric nitrous acid (HONO) were examined using airborne measurements over the Southeast U.S. during the Southeast Nexus Experiment in June and July 2013. HONO was measured once per second using a chemical ionization mass spectrometer on the NOAA WP-3D aircraft to assess sources that affect HONO abundance throughout the planetary boundary layer (PBL). The aircraft flew at altitudes between 0.12 and 6.4 km above ground level on 18 research flights that were conducted both day and night, sampling emissions from urban and power plant sources that were transported in the PBL. At night, HONO mixing ratios were greatest in plumes from agricultural burning, where they exceeded 4 ppbv and accounted for 2–14% of the reactive nitrogen emitted by the fires. The HONO to carbon monoxide ratio in these plumes from flaming stage fires ranged from 0.13 to 0.52%. Direct HONO emissions from coal-fired power plants were quantified using measurements at night, when HONO loss by photolysis was absent. These direct emissions were often correlated with total reactive nitrogen with enhancement ratios that ranged from 0 to 0.4%. HONO enhancements in power plant plumes measured during the day were compared with a Lagrangian plume dispersion model, showing that HONO produced solely from the gas phase reaction of OH with NO explained the observations. Outside of recently emitted plumes from known combustion sources, HONO mixing ratios measured several hundred meters above ground level were indistinguishable from zero within the 15 parts per trillion by volume measurement uncertainty. The results reported here do not support the existence of a ubiquitous unknown HONO source that produces significant HONO concentrations in the lower troposphere.

The snap cure NCP(non-conducive paste) adhesive material is essentially required for the high productivity flip chip bonding process. In this study, the accessibility of DEA(dielectric analysis) method for the evaluation of snap cure behavior was investigated with comparison to the isothermal DSC(differential scanning calorimetry) method. NCP adhesive was mainly formulated with epoxy resin and imidazole curing agent. Even though there were some noise in the dielectric loss factor curve measured by DEA, the cure start and completion points could be specified clearly through the data processing of cumulation and deviation method. Degree of cure by DEA method which was measured from the variation of the dielectric loss factor of adhesive material was corresponded to about 80% of the degree of cure by DSC method which was measured from the heat of curing reaction. Because the adhesive joint cured to the degree of 80% in the view point of chemical reaction reveals the sufficient mechanical strength, DEA method is expected to be used effectively in the estimation of the high speed curing behavior of snap cure type NCP adhesive material for flip chip bonding.

The yield of formaldehyde (HCHO) and glyoxal (CHOCHO) from oxidation of volatile organic compounds (VOCs) depends on precursor VOC structure and the concentration of NOx (NOx = NO + NO2). Previous work has proposed that the ratio of CHOCHO to HCHO (RGF) can be used as an indicator of precursor VOC speciation, and absolute concentrations of the CHOCHO and HCHO as indicators of NOx. Because this metric is measurable by satellite, it is potentially useful on a global scale; however, absolute values and trends in RGF have differed between satellite and ground-based observations. To investigate potential causes of previous discrepancies and the usefulness of this ratio, we present measurements of CHOCHO and HCHO over the southeastern United States (SE US) from the 2013 SENEX (Southeast Nexus) flight campaign, and compare these measurements with OMI (Ozone Monitoring Instrument) satellite retrievals. High time-resolution flight measurements show that high RGF is associated with monoterpene emissions, low RGF is associated with isoprene oxidation, and emissions associated with oil and gas production can lead to small-scale variation in regional RGF. During the summertime in the SE US, RGF is not a reliable diagnostic of anthropogenic VOC emissions, as HCHO and CHOCHO production are dominated by isoprene oxidation. Our results show that the new CHOCHO retrieval algorithm reduces the previous disagreement between satellite and in situ RGF observations. As the absolute values and trends in RGF observed during SENEX are largely reproduced by OMI observations, we conclude that satellite-based observations of RGF can be used alongside knowledge of land use as a global diagnostic of dominant hydrocarbon speciation.

Ethanol made from corn now constitutes approximately 10% of the fuel used in gasoline vehicles in the U.S. The ethanol is produced in over 200 fuel ethanol refineries across the nation. We report airborne measurements downwind from Decatur, Illinois, where the third largest fuel ethanol refinery in the U.S. is located. Estimated emissions are compared with the total point source emissions in Decatur according to the 2011 National Emissions Inventory (NEI-2011), in which the fuel ethanol refinery represents 68.0% of sulfur dioxide (SO2), 50.5% of nitrogen oxides (NOx = NO + NO2), 67.2% of volatile organic compounds (VOCs), and 95.9% of ethanol emissions. Emissions of SO2 and NOx from Decatur agreed with NEI-2011, but emissions of several VOCs were underestimated by factors of 5 (total VOCs) to 30 (ethanol). By combining the NEI-2011 with fuel ethanol production numbers from the Renewable Fuels Association, we calculate emission intensities, defined as the emissions per ethanol mass produced. Emission intensities of SO2 and NOx are higher for plants that use coal as an energy source, including the refinery in Decatur. By comparing with fuel-based emission factors, we find that fuel ethanol refineries have lower NOx, similar VOC, and higher SO2 emissions than from the use of this fuel in vehicles. The VOC emissions from refining could be higher than from vehicles, if the underestimated emissions in NEI-2011 downwind from Decatur extend to other fuel ethanol refineries. Finally, chemical transformations of the emissions from Decatur were observed, including formation of new particles, nitric acid, peroxyacyl nitrates, aldehydes, ozone, and sulfate aerosol.

UV경화형 2-ethylhexyl acrylate(2-EHA)/acrylic acid(AA) 점착제의 점착특성에 대한 경화제 함량의 영향에 대해 조사하였다. 0.01 wt%의 극소량의 MMT가 도입된 아크릴 단량체 혼합물에 각각 0, 0.05, 0.1, 0.3 wt%의 1,6-hexanediol diacrylate(HDDA)를 경화제로 첨가하고 UV조사를 실시하여 점착제를 제조하였다. MMT 도입이 공중합체의 경화 거동과 점착제의 표면 특성에 미치는 영향은 매우 낮았으나, 점착특성의 경우 MMT의 도입으로 분자 사슬의 유연성이 제한되면서 응집파괴(cohesive failure)가 억제되는 것을 확인하였다. 그러나 0.3 wt%의 경화제가 도입된 점착제는 사슬 경직성이 크게 증가하면서 MMT의 첨가가 오히려 점착특성을 저하시키는 것으로 추측되었다. 결과를 토대로 2-EHA/AA 점착제의 경우 0.05 wt%의 낮은 함량의 경화제와 극소량의 MMT의 도입이 박리 시 응집파괴 없이 균형적인 점착특성을 부여하는 것으로 판단된다.

Pressure sensitive adhesive (PSA) based on 2-ethylhexyl acrylate (2-EHA)/acrylic acid (AA) copolymer was synthesized using different photoinitiators. Results showed that PSA with Irgacure ® 651 (benzyldimethylketal) and Irga- cure ® 184(1-hydroxy-cyclohexylphenyl ketone) proved to be good for adhesion properties. This may be attributed to strong absorption near 350 nm wavelength and also high solubility in monomer mixtures. The addition of Irgacure ® 819, bisacylphosphine oxides as a photoinitiator caused cohesive failure with high loading in a peel test owing to the addi- tional radical formation. It is assumed that the insoluble photoinitiator reacts with oxygene, which may act as a hydrogen donor.

Exchange of NOx (NO+NO2) between the atmosphere and biosphere is important for air quality, climate change, and ecosystem nutrient dynamics. There are few direct ecosystem-scale measurements of the direction and rate of atmosphere–biosphere exchange of NOx. As a result, a complete description of the processes affecting NOx following emission from soils and/or plants as they transit from within the plant/forest canopy to the free atmosphere remains poorly constrained and debated. Here, we describe measurements of NO and NO2 fluxes and vertical concentration gradients made during the Biosphere Effects on AeRosols and Photochemistry EXperiment 2009. In general, during daytime we observe upward fluxes of NO and NO2 with counter-gradient fluxes of NO. We find that NOx fluxes from the forest canopy are smaller than calculated using observed flux–gradient relationships for conserved tracers and also smaller than measured soil NO emissions. We interpret these differences as primarily due to chemistry converting NOx to higher nitrogen oxides within the forest canopy, which might be part of a mechanistic explanation for the "canopy reduction factor" applied to soil NOx emissions in large-scale models.

The San Joaquin Valley (SJV) experiences some of the worst ozone air quality in the US, frequently exceeding the California 8 h standard of 70.4 ppb. To improve our understanding of trends in the number of ozone violations in the SJV, we analyze observed relationships between organic reactivity, nitrogen oxides (NO[subscript x]), and daily maximum temperature in the southern SJV using measurements made as part of California at the Nexus of Air Quality and Climate Change in 2010 (CalNex-SJV). We find the daytime speciated organic reactivity with respect to OH during CalNex-SJV has a temperature-independent portion with molecules typically associated with motor vehicles being the major component. At high temperatures, characteristic of days with high ozone, the largest portion of the total organic reactivity increases exponentially with temperature and is dominated by small, oxygenated organics and molecules that are unidentified. We use this simple temperature classification to consider changes in organic emissions over the last and next decade. With the CalNex-SJV observations as constraints, we examine the sensitivity of ozone production (PO[subscript 3]) to future NO[subscript x] and organic reactivity controls. We find that PO[subscript 3] is NO[subscript x]-limited at all temperatures on weekends and on weekdays when daily maximum temperatures are greater than 29 °C. As a consequence, NO[subscript x] reductions are the most effective control option for reducing the frequency of future ozone violations in the southern SJV., California Environmental Protection Agency. Air Resources Board (Contract CARB 08-316), United States. National Aeronautics and Space Administration (Grant NNX10AR36G)

Glyoxal (CHOCHO) is produced in the atmosphere by oxidation of volatile organic compounds (VOCs). It is measurable from space by solar backscatter along with formaldehyde (HCHO), another oxidation product of VOCs. Isoprene emitted by vegetation is the dominant source of CHOCHO and HCHO in most of the world. We use aircraft observations of CHOCHO and HCHO from the SENEX campaign over the Southeast US in summer 2013 to better understand the time-dependent yields from isoprene oxidation, their dependences on nitrogen oxides (NOx ≡ NO + NO2), the behaviour of the CHOCHO-HCHO relationship, the quality of OMI satellite observations, and the implications for using satellite CHOCHO observations as constraints on isoprene emission. We simulate the SENEX and OMI observations with the GEOS-Chem chemical transport model featuring a new chemical mechanism for CHOCHO formation from isoprene. The mechanism includes prompt CHOCHO formation under low-NOx conditions following the isomerization of the isoprene peroxy radical (ISOPO2). The SENEX observations provide support for this prompt CHOCHO formation pathway, and are generally consistent with the GEOS-Chem mechanism. Boundary layer CHOCHO and HCHO are strongly correlated in the observations and the model, with some departure under low-NOx conditions due to prompt CHOCHO formation. SENEX vertical profiles indicate a free tropospheric CHOCHO background that is absent from the model. The OMI CHOCHO data provide some support for this free tropospheric background and show Southeast US enhancements consistent with the isoprene source but a factor of 2 too low. Part of this OMI bias is due to excessive surface reflectivities assumed in the retrieval. The OMI CHOCHO and HCHO seasonal data over the Southeast US are tightly correlated and provide redundant proxies of isoprene emission. Higher temporal resolution in future geostationary satellite observations may enable detection of the prompt CHOCHO production under low-NOx conditions apparent in the SENEX data.

[1] Limitations in the chemical characterization of tropospheric organic aerosol (OA) continue to impede attempts to fully understand its chemical sources and sinks. To assess the role of organic nitrates in OA, we used a new thermal dissociation-laser induced fluorescence-based (TD-LIF) technique to obtain a high-time-resolution record of total aerosol organic nitrates (hereafter ΣANsaer) at the Bakersfield, CA supersite during the 2010 CalNex campaign. The TD-LIF measurements compare well with Fourier transform infrared measurements from collocated filter samples. These measurements show that ΣANs are a ubiquitous component of the OA with the –ONO2 subunit comprising on average 4.8% of the OA mass. Scaling this fraction by an estimate of the organic backbone mass yields an estimate that 17–23% of OA molecules contain nitrate functional groups. Measurements of both total ΣAN (gas + aerosol) and ΣANaer show that on average 21% of ΣANs are in the condensed phase, suggesting atmospheric organic nitrates have similar volatilities to analogous non-nitrate oxidized organic compounds. The fraction of ΣAN that is in the condensed phase increases with total OA concentration, providing direct evidence from the atmosphere that absorptive partitioning into OA has some control over the ΣAN phase partitioning. The specific molecular identity of the ΣAN is incompletely understood. Both biogenic hydrocarbons and long chain alkanes are calculated to be significant sources of low volatility nitrates in Bakersfield, and ultra performance liquid chromatography coupled to an electrospray ionization high-resolution quadrupole time-of-flight mass spectrometer measurements confirm the existence of particulate nitrooxy organosulfates derived from gas-phase oxidation of both isoprene and monoterpenes.