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.

Apportioned primary and secondary organic aerosol during pollution events of DISCOVER-AQ Houston.

Understanding the drivers for high ozone (O3) and atmospheric particulate matter (PM) concentrations is a pressing issue in urban air quality, as this understanding informs decisions for control and mitigation of these key pollutants. The Houston, TX metropolitan area is an ideal location for studying the intersection between O3 and atmospheric secondary organic carbon (SOC) production due to the diversity of source types (urban, industrial, and biogenic) and the on- and off-shore cycling of air masses over Galveston Bay, TX. Detailed characterization of filter-based samples collected during Deriving Information on Surface Conditions from Column and VERtically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) Houston field experiment in September 2013 were used to investigate sources and composition of organic carbon (OC) and potential relationships between daily maximum 8 h average O3 and PM. The current study employed a novel combination of chemical mass balance modeling defining primary (i.e. POC) versus secondary (i.e. SOC) organic carbon and radiocarbon (14C) for apportionment of contemporary and fossil carbon. The apportioned sources include contemporary POC (biomass burning [BB], vegetative detritus), fossil POC (motor vehicle exhaust), biogenic SOC and fossil SOC. The filter-based results were then compared with real-time measurements by aerosol mass spectrometry. With these methods, a consistent urban background of contemporary carbon and motor vehicle exhaust was observed in the Houston metropolitan area. Real-time and filter-based characterization both showed that carbonaceous aerosols in Houston was highly impacted by SOC or oxidized OC, with much higher contributions from biogenic than fossil sources. However, fossil SOC concentration and fractional contribution had a stronger correlation with daily maximum 8 h average O3, peaking during high PM and O3 events. The results indicate that point source emissions processed by on- and off-shore wind cycles likely contribute to peak events for both PM and O3 in the greater Houston metropolitan area.

Identifying the Transcriptional Response of Cancer and Inflammation-Related Genes in Lung Cells in Relation to Ambient Air Chemical Mixtures in Houston, Texas.

Atmospheric pollution represents a complex mixture of air chemicals that continually interact and transform, making it difficult to accurately evaluate associated toxicity responses representative of real-world exposure. This study leveraged data from a previously published article and reevaluated lung cell transcriptional response induced by outdoor atmospheric pollution mixtures using field-based exposure conditions in the industrialized Houston Ship Channel. The tested hypothesis was that individual and co-occurring chemicals in the atmosphere relate to altered expression of critical genes involved in inflammation and cancer-related processes in lung cells. Human lung cells were exposed at an air-liquid interface to ambient air mixtures for 4 h, with experiments replicated across 5 days. Real-time monitoring of primary and secondary gas-phase pollutants, as well as other atmospheric conditions, was simultaneously conducted. Transcriptional analysis of exposed cells identified critical genes showing differential expression associated with both individual and chemical mixtures. The individual pollutant identified with the largest amount of associated transcriptional response was benzene. Tumor necrosis factor (TNF) and interferon regulatory factor 1 (IRFN1) were identified as key upstream transcription factor regulators of the cellular response to benzene. This study is among the first to measure lung cell transcriptional responses in relation to real-world, gas-phase air mixtures.

An automated common algorithm for planetary boundary layer retrievals using aerosol lidars in support of the U.S. EPA Photochemical Assessment Monitoring Stations Program.

A unique automated planetary boundary layer (PBL) retrieval algorithm is proposed as a common cross-platform method for use with commercially available ceilometers for implementation under the redesigned U.S. Environmental Protection Agency Photochemical Assessment Monitoring Stations program. This algorithm addresses instrument signal quality and screens for precipitation and cloud layers before the implementation of the retrieval methodology using the Haar wavelet covariance transform method. Layer attribution for the PBL height is supported with the use of continuation and time-tracking parameters, and uncertainties are calculated for individual PBL height retrievals. Commercial ceilometer retrievals are tested against radiosonde PBL height and cloud-base height during morning and late afternoon transition times, critical to air quality model prediction and when retrieval algorithms struggle to identify PBL heights. A total of 58 radiosonde profiles were used and retrievals for nocturnal stable layers, residual layers and mixing layers were assessed. Overall good agreement was found for all comparisons with one system showing limitations for the cases of nighttime surface stable layers and daytime mixing layer. It is recommended that nighttime shallow stable layer retrievals be performed with a recommended minimum height or with additional verification. Retrievals of residual layer heights and mixing layer comparisons revealed overall good correlations to radiosonde heights (correlation coefficients, r2, ranging from 0.89 - 0.96 and bias ranging from ~ -131 to +63 m, and r2 from 0.88 - 0.97 and bias from -119 to +101 m, respectively).

Climate change accelerates growth of urban trees in metropolises worldwide.

Despite the importance of urban trees, their growth reaction to climate change and to the urban heat island effect has not yet been investigated with an international scope. While we are well informed about forest growth under recent conditions, it is unclear if this knowledge can be simply transferred to urban environments. Based on tree ring analyses in ten metropolises worldwide, we show that, in general, urban trees have undergone accelerated growth since the 1960s. In addition, urban trees tend to grow more quickly than their counterparts in the rural surroundings. However, our analysis shows that climate change seems to enhance the growth of rural trees more than that of urban trees. The benefits of growing in an urban environment seem to outweigh known negative effects, however, accelerated growth may also mean more rapid ageing and shortened lifetime. Thus, city planners should adapt to the changed dynamics in order to secure the ecosystem services provided by urban trees.

Analysis of correlation between pediatric asthma exacerbation and exposure to pollutant mixtures with association rule mining.

OBJECTIVES: Traditional studies on effects of outdoor pollution on asthma have been criticized for questionable statistical validity and inefficacy in exploring the effects of multiple air pollutants, alone and in combination. Association rule mining (ARM), a method easily interpretable and suitable for the analysis of the effects of multiple exposures, could be of use, but the traditional interest metrics of support and confidence need to be substituted with metrics that focus on risk variations caused by different exposures. METHODS: We present an ARM-based methodology that produces rules associated with relevant odds ratios and limits the number of final rules even at very low support levels (0.5%), thanks to post-pruning criteria that limit rule redundancy and control for statistical significance. The methodology has been applied to a case-crossover study to explore the effects of multiple air pollutants on risk of asthma in pediatric subjects. RESULTS: We identified 27 rules with interesting odds ratio among more than 10,000 having the required support. The only rule including only one chemical is exposure to ozone on the previous day of the reported asthma attack (OR=1.14). 26 combinatory rules highlight the limitations of air quality policies based on single pollutant thresholds and suggest that exposure to mixtures of chemicals is more harmful, with odds ratio as high as 1.54 (associated with the combination day0 SO2, day0 NO, day0 NO2, day1 PM). CONCLUSIONS: The proposed method can be used to analyze risk variations caused by single and multiple exposures. The method is reliable and requires fewer assumptions on the data than parametric approaches. Rules including more than one pollutant highlight interactions that deserve further investigation, while helping to limit the search field.

Formaldehyde column density measurements as a suitable pathway to estimate near-surface ozone tendencies from space.

In support of future satellite missions that aim to address the current shortcomings in measuring air quality from space, NASA's Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) field campaign was designed to enable exploration of relationships between column measurements of trace species relevant to air quality at high spatial and temporal resolution. In the DISCOVER-AQ data set, a modest correlation (r 2 = 0.45) between ozone (O3) and formaldehyde (CH2O) column densities was observed. Further analysis revealed regional variability in the O3-CH2O relationship, with Maryland having a strong relationship when data were viewed temporally and Houston having a strong relationship when data were viewed spatially. These differences in regional behavior are attributed to differences in volatile organic compound (VOC) emissions. In Maryland, biogenic VOCs were responsible for ~28% of CH2O formation within the boundary layer column, causing CH2O to, in general, increase monotonically throughout the day. In Houston, persistent anthropogenic emissions dominated the local hydrocarbon environment, and no discernable diurnal trend in CH2O was observed. Box model simulations suggested that ambient CH2O mixing ratios have a weak diurnal trend (±20% throughout the day) due to photochemical effects, and that larger diurnal trends are associated with changes in hydrocarbon precursors. Finally, mathematical relationships were developed from first principles and were able to replicate the different behaviors seen in Maryland and Houston. While studies would be necessary to validate these results and determine the regional applicability of the O3-CH2O relationship, the results presented here provide compelling insight into the ability of future satellite missions to aid in monitoring near-surface air quality.

An Atmospheric Constraint on the NO2 Dependence of Daytime Near-Surface Nitrous Acid (HONO).

Recent observations suggest a large and unknown daytime source of nitrous acid (HONO) to the atmosphere. Multiple mechanisms have been proposed, many of which involve chemistry that reduces nitrogen dioxide (NO2) on some time scale. To examine the NO2 dependence of the daytime HONO source, we compare weekday and weekend measurements of NO2 and HONO in two U.S. cities. We find that daytime HONO does not increase proportionally to increases in same-day NO2, i.e., the local NO2 concentration at that time and several hours earlier. We discuss various published HONO formation pathways in the context of this constraint.

Atmospheric Mercury in the Barnett Shale Area, Texas: Implications for Emissions from Oil and Gas Processing.

Atmospheric mercury emissions in the Barnett Shale area were studied by employing both stationary measurements and mobile laboratory surveys. Stationary measurements near the Engle Mountain Lake showed that the median mixing ratio of total gaseous mercury (THg) was 138 ppqv (140 ± 29 ppqv for mean ± S.D.) during the June 2011 study period. A distinct diurnal variation pattern was observed in which the highest THg levels appeared near midnight, followed by a monotonic decrease until midafternoon. The influence of oil and gas (ONG) emissions was substantial in this area, as inferred from the i-pentane/n-pentane ratio (1.17). However, few THg plumes were captured by our mobile laboratory during a ∼3700 km survey with detailed downwind measurements from 50 ONG facilities. One compressor station and one natural gas condensate processing facility were found to have significant THg emissions, with maximum THg levels of 963 and 392 ppqv, respectively, and the emissions rates were estimated to be 7.9 kg/yr and 0.3 kg/yr, respectively. Our results suggest that the majority of ONG facilities in this area are not significant sources of THg; however, it is highly likely that a small number of these facilities contribute a relatively large amount of emissions in the ONG sector.

Potential role of stabilized Criegee radicals in sulfuric acid production in a high biogenic VOC environment.

We present field observations made in June 2011 downwind of Dallas-Fort Worth, TX, and evaluate the role of stabilized Criegee radicals (sCIs) in gaseous sulfuric acid (H2SO4) production. Zero-dimensional model calculations show that sCI from biogenic volatile organic compounds composed the majority of the sCIs. The main uncertainty associated with an evaluation of H2SO4 production from the sCI reaction channel is the lack of experimentally determined reaction rates for sCIs formed from isoprene ozonolysis with SO2 along with systematic discrepancies in experimentally derived reaction rates between other sCIs and SO2 and water vapor. In general, the maximum of H2SO4 production from the sCI channel is found in the late afternoon as ozone increases toward the late afternoon. The sCI channel, however, contributes minor H2SO4 production compared with the conventional OH channel in the mid-day. Finally, the production and the loss rates of H2SO4 are compared. The application of the recommended mass accommodation coefficient causes significant overestimation of H2SO4 loss rates compared with H2SO4 production rates. However, the application of a lower experimental value for the mass accommodation coefficient provides good agreement between the loss and production rates of H2SO4. The results suggest that the recommended coefficient for the H2O surface may not be suitable for this relatively dry environment.

From the Field to the Laboratory: Air Pollutant-Induced Genomic Effects in Lung Cells.

Current in vitro studies do not typically assess cellular impacts in relation to real-world atmospheric mixtures of gases. In this study, we set out to examine the feasibility of measuring biological responses at the level of gene expression in human lung cells upon direct exposures to air in the field. This study describes the successful deployment of lung cells in the heavily industrialized Houston Ship Channel. By examining messenger RNA (mRNA) levels from exposed lung cells, we identified changes in genes that play a role as inflammatory responders in the cell. The results show anticipated responses from negative and positive controls, confirming the integrity of the experimental protocol and the successful deployment of the in vitro instrument. Furthermore, exposures to ambient conditions displayed robust changes in gene expression. These results demonstrate a methodology that can produce gas-phase toxicity data in the field.

High winter ozone pollution from carbonyl photolysis in an oil and gas basin.

The United States is now experiencing the most rapid expansion in oil and gas production in four decades, owing in large part to implementation of new extraction technologies such as horizontal drilling combined with hydraulic fracturing. The environmental impacts of this development, from its effect on water quality to the influence of increased methane leakage on climate, have been a matter of intense debate. Air quality impacts are associated with emissions of nitrogen oxides (NOx = NO + NO2) and volatile organic compounds (VOCs), whose photochemistry leads to production of ozone, a secondary pollutant with negative health effects. Recent observations in oil- and gas-producing basins in the western United States have identified ozone mixing ratios well in excess of present air quality standards, but only during winter. Understanding winter ozone production in these regions is scientifically challenging. It occurs during cold periods of snow cover when meteorological inversions concentrate air pollutants from oil and gas activities, but when solar irradiance and absolute humidity, which are both required to initiate conventional photochemistry essential for ozone production, are at a minimum. Here, using data from a remote location in the oil and gas basin of northeastern Utah and a box model, we provide a quantitative assessment of the photochemistry that leads to these extreme winter ozone pollution events, and identify key factors that control ozone production in this unique environment. We find that ozone production occurs at lower NOx and much larger VOC concentrations than does its summertime urban counterpart, leading to carbonyl (oxygenated VOCs with a C = O moiety) photolysis as a dominant oxidant source. Extreme VOC concentrations optimize the ozone production efficiency of NOx. There is considerable potential for global growth in oil and gas extraction from shale. This analysis could help inform strategies to monitor and mitigate air quality impacts and provide broader insight into the response of winter ozone to primary pollutants.

Vertically resolved measurements of nighttime radical reservoirs in Los Angeles and their contribution to the urban radical budget.

Photolabile nighttime radical reservoirs, such as nitrous acid (HONO) and nitryl chloride (ClNO(2)), contribute to the oxidizing potential of the atmosphere, particularly in early morning. We present the first vertically resolved measurements of ClNO(2), together with vertically resolved measurements of HONO. These measurements were acquired during the California Nexus (CalNex) campaign in the Los Angeles basin in spring 2010. Average profiles of ClNO(2) exhibited no significant dependence on height within the boundary layer and residual layer, although individual vertical profiles did show variability. By contrast, nitrous acid was strongly enhanced near the ground surface with much smaller concentrations aloft. These observations are consistent with a ClNO(2) source from aerosol uptake of N(2)O(5) throughout the boundary layer and a HONO source from dry deposition of NO(2) to the ground surface and subsequent chemical conversion. At ground level, daytime radical formation calculated from nighttime-accumulated HONO and ClNO(2) was approximately equal. Incorporating the different vertical distributions by integrating through the boundary and residual layers demonstrated that nighttime-accumulated ClNO(2) produced nine times as many radicals as nighttime-accumulated HONO. A comprehensive radical budget at ground level demonstrated that nighttime radical reservoirs accounted for 8% of total radicals formed and that they were the dominant radical source between sunrise and 09:00 Pacific daylight time (PDT). These data show that vertical gradients of radical precursors should be taken into account in radical budgets, particularly with respect to HONO.

Deciphering the role of radical precursors during the Second Texas Air Quality Study.

The Texas Environmental Research Consortium (TERC) funded significant components of the Second Texas Air Quality Study (TexAQS II), including the TexAQS II Radical and Aerosol Measurement Project (TRAMP) and instrumented flights by a Piper Aztec aircraft. These experiments called attention to the role of short-lived radical sources such as formaldehyde (HCHO) and nitrous acid (HONO) in increasing ozone productivity. TRAMP instruments recorded daytime HCHO pulses as large as 32 parts per billion (ppb) originating from upwind industrial activities in the Houston Ship Channel, where in situ surface monitors detected HCHO peaks as large as 52 ppb. Moreover, Ship Channel petrochemical flares were observed to produce plumes of apparent primary HCHO. In one such combustion plume that was depleted of ozone by large emissions of oxides of nitrogen (NOx), the Piper Aztec measured a ratio of HCHO to carbon monoxide (CO) 3 times that of mobile sources. HCHO from uncounted primary sources or ozonolysis of underestimated olefin emissions could significantly increase ozone productivity in Houston beyond previous expectations. Simulations with the CAMx model show that additional emissions of HCHO from industrial flares or mobile sources can increase peak ozone in Houston by up to 30 ppb. Other findings from TexAQS II include significant concentrations of HONO throughout the day, well in excess of current air quality model predictions, with large nocturnal vertical gradients indicating a surface or near-surface source of HONO, and large concentrations of nighttime radicals (approximately30 parts per trillion [ppt] HO2). HONO may be formed heterogeneously on urban canopy or particulate matter surfaces and may be enhanced by organic aerosol of industrial or motor vehicular origin, such as through conversion of nitric acid (HNO3). Additional HONO sources may increase daytime ozone by more than 10 ppb. Improving the representation of primary and secondary HCHO and HONO in air quality models could enhance the simulated effectiveness of control strategies.