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NASA NTRS2016

Analysis of Summer-Time Ozone and Precursor Species in the Southeast United States

Ozone (O3) is a greenhouse gas and toxic pollutant which plays a major role in air quality and atmospheric chemistry. The understanding and ability to model the horizontal and vertical structure of O3 mixing ratios is difficult due to the complex formation/destruction processes and transport pathways that cause large variability of O3. The Environmental Protection Agency has National Ambient Air Quality Standards for O3 set at 75 ppb with future standards proposed to be as low as 65 ppb. These lower values emphasize the need to better understand/simulate the transport processes, emission sources, and chemical processes controlling precursor species (e.g., NOx, VOCs, and CO) which influence O3 mixing ratios. The uncertainty of these controlling variables is particularly large in the southeast United States (US) which is a region impacted by multiple different emission sources of precursor species (anthropogenic and biogenic) and transport processes resulting in complex spatio-temporal O3 patterns. During this work we will evaluate O3 and precursor species in the southeast US applying models, ground-based and airborne in situ data, and lidar observations. In the summer of 2013, the UAH O3 Differential Absorption Lidar (DIAL) (part of the Tropospheric Ozone Lidar Network (TOLNet)) measured vertical O3 profiles from the surface up to approximately 12 km. During this period, the lidar observed numerous periods of dynamic temporal and vertical O3 structures. In order to determine the sources/processes impacting these O3 mixing ratios we will apply the CTM GEOS-Chem (v9-02) at a 0.25 deg x 0.3125 deg resolution. Using in situ ground-based (e.g., SEARCH Network, CASTNET), airborne (e.g., NOAA WP-3D - SENEX 2013, DC-8 - SEAC4RS), and TOLNet lidar data we will first evaluate the model to determine the capability of GEOS-Chem to simulate the spatio-temporal variability of O3 in the southeast US. Secondly, we will perform model sensitivity studies in order to quantify which emission sources (e.g., anthropogenic, biogenic, lighting, wildfire) and transport processes (e.g., stratospheric, long-range, local scale) are contributing to these TOLNet-observed dynamic O3 patterns. Results from the evaluation of the model and the study of sources/processes impacting observed O3 mixing ratios will be presented.

Optical Radar↗

NASA NTRS2010

The Unique OMI HCHO/NO2 Feature During the 2008 Beijing Summer Olympics: Implications for Ozone Production Sensitivity

In preparation of the Beijing Summer Olympic and Paralympics Games, strict controls were imposed between July and September 2008 on motor vehicle traffic and industrial emissions to improve air quality for the competitors. We assessed chemical sensitivity of ozone production to these controls using Ozone Monitoring Instrument (OMI) column measurements of formaldehyde (HCHO) and nitrogen dioxide (NO2), where their ratio serves as a proxy for the sensitivity. During the emission controls, HCHO/NO2 increased and indicated a NOx-limited regime, in contrast to the same period in the preceding three years when the ratio indicates volatile organic carbon (VOC)-limited and mixed NOx-VOC-limited regimes. After the emission controls were lifted, observed NO2 and HCHO/NO2 returned to their previous values. The 2005-2008 OMI record shows that this transition in regimes was unique as ozone production in Beijing was rarely NOx-limited. OMI measured summertime increases in HCHO of around 13% in 2008 compared to prior years, the same time period during which MODIS vegetation indices increased. The OMI HCHO increase may be due to higher biogenic emissions of HCHO precursors, associated with Beijing's greening initiative for the Olympics. However, NO2 and HCHO were also found to be well-correlated during the summer months. This indicates an anthropogenic VOC contribution from vehicle emissions to OMI HCHO and is a plausible explanation for the relative HCHO minimum observed in August 2008, concurrent with a minimum in traffic emissions. We calculated positive trends in 2005-2008 OMI HCHO and NO2 of about +1 x 10(exp 14) Molec/ square M-2 and +3 x 10(exp 13) molec CM-2 per month, respectively. The positive trend in NO2 may be an indicator of increasing vehicular traffic since 2005, while the positive trend in HCHO may be due to a combined increase in anthropogenic and biogenic emissions since 2005.

Witte, J. C.↗

NASA NTRS2015

Formaldehyde Production from Isoprene Oxidation Across NOx Regimes

The chemical link between isoprene and formaldehyde (HCHO) is a strong, non-linear function of NOx (= 27 NO + NO2). This relationship is a linchpin for top-down isoprene emission inventory verification from orbital HCHO column observations. It is also a benchmark for overall mechanism performance with regard to VOC oxidation. Using a comprehensive suite of airborne in situ observations over the Southeast U.S., we quantify HCHO production across the urban-rural spectrum. Analysis of isoprene and its major first-generation oxidation products allows us to define both a "prompt" yield of HCHO (molecules of HCHO produced per molecule of freshly-emitted isoprene) and the background HCHO mixing ratio (from oxidation of longer-lived hydrocarbons). Over the range of observed NOx values (roughly 0.1 - 2 ppbv), the prompt yield increases by a factor of 3 (from 0.3 to 0.9), while background HCHO increases by more than a factor of 2 (from 1.5 to 3.3 ppbv). We apply the same method to evaluate the performance of both a global chemical transport model (AM3) and a measurement-constrained 0-D chemical box model. Both models reproduce the NOx dependence of the prompt HCHO yield, illustrating that models with updated isoprene oxidation mechanisms can adequately capture the link between HCHO and recent isoprene emissions. On the other hand, both models under-estimate background HCHO mixing ratios, suggesting missing HCHO precursors, inadequate representation of later-generation isoprene degradation and/or under-estimated hydroxyl radical concentrations. Moreover, we find that the total organic peroxy radical production rate is essentially independent of NOx, as the increase in oxidizing capacity with NOx is largely balanced by a decrease in VOC reactivity. Thus, the observed NOx dependence of HCHO mainly reflects the changing fate of organic peroxy radicals.

VOC↗

NASA NTRS2014

Revised (Mixed-Effects) Estimation for Forest Burning Emissions of Gases and Smoke, Fire/Emission Factor Typology, and Potential Remote Sensing Classification of Types for Ozone and Black-Carbon Simulation

We summarize recent progress (a) in correcting biomass burning emissions factors deduced from airborne sampling of forest fire plumes, (b) in understanding the variability in reactivity of the fresh plumes sampled in ARCTAS (2008), DC3 (2012), and SEAC4RS (2013) airborne missions, and (c) in a consequent search for remotely sensed quantities that help classify forest-fire plumes. Particle properties, chemical speciation, and smoke radiative properties are related and mutually informative, as pictures below suggest (slopes of lines of same color are similar). (a) Mixed-effects (random-effects) statistical modeling provides estimates of both emission factors and a reasonable description of carbon-burned simultaneously. Different fire plumes will have very different contributions to volatile organic carbon reactivity; this may help explain differences of free NOx(both gas- and particle-phase), and also of ozone production, that have been noted for forest-fire plumes in California. Our evaluations check or correct emission factors based on sequential measurements (e.g., the Normalized Ratio Enhancement and similar methods). We stress the dangers of methods relying on emission-ratios to CO. (b) This work confirms and extends many reports of great situational variability in emissions factors. VOCs vary in OH reactivity and NOx-binding. Reasons for variability are not only fuel composition, fuel condition, etc., but are confused somewhat by rapid transformation and mixing of emissions. We use "unmixing" (distinct from mixed-effects) statistics and compare briefly to approaches like neural nets. We focus on one particularly intense fire the notorious Yosemite Rim Fire of 2013. In some samples, NOx activity was not so suppressed by binding into nitrates as in other fires. While our fire-typing is evolving and subject to debate, the carbon-burned delta(CO2+CO) estimates that arise from mixed effects models, free of confusion by background-CO2 variation, should provide a solid base for discussion. (c) We report progress using promising links we find between emissions-related "fire types" and promising features deducible from remote observations of plumes, e.g., single scatter albedo, Angstrom exponent of scattering, Angstrom exponent of absorption, (CO column density)/(aerosol optical depth).

Remote sensing↗

NASA NTRS2017

Observations of VOC Emissions and Photochemical Products over US Oil- and Gas-Producing Regions Using High-Resolution H3O+ CIMS (PTR-ToF-MS)

VOCs (Volatile Organic Compounds) related to oil and gas extraction operations in the United States were measured by H3O (sup plus) chemical ionization time-of-flight mass spectrometry (H3O (sup plus) ToFCIMS/PTR-ToF-MS (Time of Flight Chemical Ionization Mass Spectrometry/Proton Transfer Reaction-Time of Flight-Mass Spectroscopy) from aircraft during the Shale Oil and Natural Gas Nexus (SONGNEX) campaign in March-April 2015. This work presents an overview of major VOC species measured in nine oil- and gas-producing regions, and a more detailed analysis of H3O (sup plus) ToF-CIMS measurements in the Permian Basin within Texas and New Mexico. Mass spectra are dominated by small photochemically produced oxygenates and compounds typically found in crude oil: aromatics, cyclic alkanes, and alkanes. Mixing ratios of aromatics were frequently as high as those measured downwind of large urban areas. In the Permian, the H3O (sup plus) ToF-CIMS measured a number of underexplored or previously unreported species, including aromatic and cycloalkane oxidation products, nitrogen heterocycles including pyrrole (C4H5N) and pyrroline (C4H7N), H2S, and a diamondoid (adamantane) or unusual monoterpene. We additionally assess the specificity of a number of ion masses resulting from H3O (sup plus) ion chemistry previously reported in the literature, including several new or alternate interpretations.

mass spectrometr↗

NASA NTRS2016

Significant Tropospheric O3 Production from Extratropical Forest Fires:When? When Not?

There is significant controversy on whether extratropical fires contribute importantly to widespread ozone productionabsent the addition of urban pollutant nitrogen oxides (Jaffe and Widger, 2012, Singh et al., 2012,2013). Wereport a significant range of O3 production early in the fire plume history and report controls on which notable O3production occurs. The current data set is the airborne observations made on board NASAs highly instrumentedDC-8 aircraft during the ARCTAS (2008) and SEAC4RS (2013) campaigns within the Western United States. Aclear analysis of fire emissions was aided considerably by MERET (a Mixed Effects Regressions Emissions Technique).This technique allows consistent emission factors and enhancement ratios for O3 for individual aircraftsamples largely free from uncertainties resulting from mixing and entrainment which plague many published estimates.(Yokelson et al, 2013, Chatfield and Andreae, 2016). We find support for the reasonable idea that the ratioof nitrogen oxides (NOx) to volatile organic carbon (VOC) emissions controls new O3 production. The evidence isfor significant O3 production from high-fuel-nitrogen fuels (as evidenced by acetonitrile) and extremely hot largefires (like the Yosemite Rim Fire of 2013 which we analyze), while others do not. VOC emissions factors varysignificantly from fire to fire (and from different samples in the Rim Fire). Relative CO production (aka modifiedcombustion efficiency) is only one factor describing VOC emissions factors.

Chatfield, R.↗

NASA NTRS2016

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 (r2 = 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 approx.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.

Surface Conditions from Column and Vertically Reso↗

NASA NTRS2004

Evaluation of GOME Satellite Measurements of Tropospheric NO2 and HCHO using Regional Data from Aircraft Campaigns in the Southeastern United States

We compare tropospheric measurements of nitrogen dioxide (NO2) and formaldehyde (HCHO) from the Global Ozone Monitoring Experiment (GOME) satellite instrument with in situ measurements over eastern Texas and the southeast United States. On aveiage, the GOME and in situ measurements of tropospheric NO2 and HCHO columns are consistent despite pronounced sampling differences. The geometric mean in situ to GOME ratios over the campaign are 1.08 for NO2 and 0.84 for HCHO, with corresponding geometric standard deviations of 1.27 and 1.38. The correlation of the observed column spatial variability between the two NO2 measurement sets is encouraging before (r2 = 0.54, n = 18) and after (r2 = 0.67, n = 18) correcting for a sampling bias. Mean relative vertical profiles of HCHO and NO2 calculated with a global three-dimensional model (GEOS-CHEM) and used in the GOME retrieval are highly consistent with in situ measurements; differences would affect the retrieved NO2 and HCHO columns by a few percent. GOME HCHO columns over eastern Texas include contributions from anthropogenic volatile organic compound (VOC) emissions but are dominated by biogenic VOC emissions at the regional scale in August-September when HCHO columns are within 20% of those over the southeastern United States. In situ measurements show that during summer the lowest 1500 m (the lower mixed layer) contains 75% of the tropospheric NO2 column over Houston and Nashville, and 60% of the HCHO column over Houston. Future validation of space-based measurements of tropospheric NO2 and HCHO columns over polluted regions should include coincident in situ measurements that span the entire satellite footprint, especially in the heterogeneous mixed layer.

Martin, R. V.↗