Atmospheric Benzene Observations from an Oil and Gas Field in the Denver Julesburg Basin in July and August 2014

High time resolution measurements of volatile organic compounds (VOCs) were collectedusing a proton-transfer-reaction quadrupole mass spectrometry (PTR-QMS) instrument at the PlattevilleAtmospheric Observatory (PAO) in Colorado to investigate how oil and natural gas (ONG) developmentimpacts air quality within the Wattenburg Gas Field (WGF) in the Denver-Julesburg Basin. The measurementswere carried out in July and August 2014 as part of NASAs Deriving Information on Surface Conditions fromColumn and Vertically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) field campaign. ThePTR-QMS data were supported by pressurized whole air canister samples and airborne vertical and horizontalsurveys of VOCs. Unexpectedly high benzene mixing ratios were observed at PAO at ground level (meanbenzene 0.53 ppbv, maximum benzene 29.3 ppbv), primarily at night (mean nighttime benzene 0.73ppbv). These high benzene levels were associated with southwesterly winds. The airborne measurementsindicate that benzene originated from within the WGF, and typical source signatures detected in the canistersamples implicate emissions from ONG activities rather than urban vehicular emissions as primary benzenesource. This conclusion is backed by a regional toluene-to-benzene ratio analysis which associated southerlyflow with vehicular emissions from the Denver area. Weak benzene-to-CO correlations confirmed that trafficemissions were not responsible for the observed high benzene levels. Previous measurements at the BoulderAtmospheric Observatory (BAO) and our data obtained at PAO allow us to locate the source of benzeneenhancements between the two atmospheric observatories. Fugitive emissions of benzene from ONGoperations in the Platteville area are discussed as the most likely causes of enhanced benzene levels at PAO

An online air-sea exchange model framework for trace gases powered by machine- learning

The ocean emits a wide range of trace gases, such as volatile organic compounds, or sulfur-,nitrogen-, and halogen-containing compounds. Many of these gases play critical roles in the atmosphere, including aerosol and cloud formation, tropospheric and stratospheric ozone budget, as well as the self-cleaning capacity of the atmosphere. Most chemistry-climate models use prescribed oceanic emissions (often derived from observations). These prescribed (offline) emissions generally do not respond to changes in local conditions. A process-level representation of the bi-directional oceanic emissions of trace gases remains challenging, mainly because the ocean biogeochemicalprocesses controlling the natural synthesis of these compounds in the seawater remain poorly understood. We present a new online air-sea exchange framework for the NCAR CESM2, with an observationally trained machine-learning emulator to couple the ocean biogeochemistry with the air-sea exchange. This machine-learning based approach so far has been tested for a number of important trace gases, including dimethyl sulfide (DMS), acetone, bromoform (CHBr 3 ), and dibromomethane (CH 2 Br 2 ), and the preliminary results are evaluated with observations around the globe. This new model framework is more skillful than the widely used top-down approaches for representing the seasonal/spatial variations and the annual means of atmospheric concentrations. The new approach improves the model predictability for the coupled earth system model, and can be used as a basis for investigating the future ocean emissions and feedbacks under climate change.Fil: Wang, Siyuan. National Center for Atmospheric Research; Estados UnidosFil: Emmons, Louisa K.. National Center for Atmospheric Research; Estados UnidosFil: Tilmes, Simone. National Center for Atmospheric Research; Estados UnidosFil: Kinnison, Douglas E.. National Center for Atmospheric Research; Estados UnidosFil: Long, Mateo C.. National Center for Atmospheric Research; Estados UnidosFil: Lamarque, Jean Francoise. National Center for Atmospheric Research; Estados UnidosFil: Apel, Eric C.. National Oceanic & Atmospheric Administration, Esrl; Estados UnidosFil: Hornbrook, Rebecca S.. Centro Nacional de Investigación Atmosférica; Estados UnidosFil: Montzka, Stephen. National Ocean And Atmospheric Administration; Estados UnidosFil: Saiz López, Alfonso. Consejo Superior de Investigaciones Científicas; EspañaFil: Fernandez, Rafael Pedro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza; Argentina. Universidad Tecnológica Nacional. Facultad Regional de Mendoza; ArgentinaAmerican Geophysical Union Fall MeetingSan FranciscoEstados UnidosAmerican Geophysical Unio

Bimodal distribution of free tropospheric ozone over the tropical western Pacific revealed by airborne observations

A recent airborne field campaign over the remote western Pacific obtained the first intensive in situ ozone sampling over the warm pool region from oceanic surface to 15-km altitude (near 360-K potential temperature level). The new data set quantifies ozone in the tropical tropopause layer under significant influence of convective outflow. The analysis further reveals a bimodal distribution of free tropospheric ozone mixing ratio. A primary mode, narrowly distributed around 20-ppbv, dominates the troposphere from the surface to 15-km. A secondary mode, broadly distributed with a 60-ppbv modal value, is prominent between 3 and 8-km (320-K to 340-K potential temperature levels). The latter mode occurs as persistent layers of ozone-rich drier air and is characterized by relative humidity under 45%. Possible controlling mechanisms are discussed. These findings provide new insight into the physical interpretation of the >S>-shaped mean ozone profiles in the tropics.Peer Reviewe

Heterogeneous N2O5 Uptake During Winter: Aircraft Measurements During the 2015 WINTER Campaign and Critical Evaluation of Current Parameterizations

Nocturnal dinitrogen pentoxide (N2O5) heterogeneous chemistry impacts regional air quality and the distribution and lifetime of tropospheric oxidants. Formed from the oxidation of nitrogen oxides, N2O5 is heterogeneously lost to aerosol with a highly variable reaction probability, γ(N2O5), dependent on aerosol composition and ambient conditions. Reaction products include soluble nitrate (HNO3 or NO3−) and nitryl chloride (ClNO2). We report the first‐ever derivations of γ(N2O5) from ambient wintertime aircraft measurements in the critically important nocturnal residual boundary layer. Box modeling of the 2015 Wintertime INvestigation of Transport, Emissions, and Reactivity (WINTER) campaign over the eastern United States derived 2,876 individual γ(N2O5) values with a median value of 0.0143 and range of 2 × 10−5 to 0.1751. WINTER γ(N2O5) values exhibited the strongest correlation with aerosol water content, but weak correlations with other variables, such as aerosol nitrate and organics, suggesting a complex, nonlinear dependence on multiple factors, or an additional dependence on a nonobserved factor. This factor may be related to aerosol phase, morphology (i.e., core shell), or mixing state, none of which are commonly measured during aircraft field studies. Despite general agreement with previous laboratory observations, comparison of WINTER data with 14 literature parameterizations (used to predict γ(N2O5) in chemical transport models) confirms that none of the current methods reproduce the full range of γ(N2O5) values. Nine reproduce the WINTER median within a factor of 2. Presented here is the first field‐based, empirical parameterization of γ(N2O5), fit to WINTER data, based on the functional form of previous parameterizations

Wet scavenging of soluble gases in DC3 deep convective storms using WRF-Chem simulations and aircraft observations

We examine wet scavenging of soluble trace gases in storms observed during the Deep Convective Clouds and Chemistry (DC3) field campaign. We conduct high-resolution simulations with the Weather Research and Forecasting model with Chemistry (WRF-Chem) of a severe storm in Oklahoma. The model represents well the storm location, size, and structure as compared with Next Generation Weather Radar reflectivity, and simulated CO transport is consistent with aircraft observations. Scavenging efficiencies (SEs) between inflow and outflow of soluble species are calculated from aircraft measurements and model simulations. Using a simple wet scavenging scheme, we simulate the SE of each soluble species within the error bars of the observations. The simulated SEs of all species except nitric acid (HNO_3) are highly sensitive to the values specified for the fractions retained in ice when cloud water freezes. To reproduce the observations, we must assume zero ice retention for formaldehyde (CH_2O) and hydrogen peroxide (H_2O_2) and complete retention for methyl hydrogen peroxide (CH_3OOH) and sulfur dioxide (SO_2), likely to compensate for the lack of aqueous chemistry in the model. We then compare scavenging efficiencies among storms that formed in Alabama and northeast Colorado and the Oklahoma storm. Significant differences in SEs are seen among storms and species. More scavenging of HNO_3 and less removal of CH_3OOH are seen in storms with higher maximum flash rates, an indication of more graupel mass. Graupel is associated with mixed-phase scavenging and lightning production of nitrogen oxides (NO_x), processes that may explain the observed differences in HNO_3 and CH_3OOH scavenging

Validation of formaldehyde products from three satellite retrievals (OMI SAO, OMPS-NPP SAO, and OMI BIRA) in the marine atmosphere with four seasons of ATom aircraft observations

Formaldehyde (HCHO) in the atmosphere is an intermediate product from the oxidation of methane and non-methane volatile organic compounds. In remote marine regions, HCHO variability is closely related to atmospheric oxidation capacity and modeled HCHO in these regions is usually added as a global satellite HCHO background. Thus, it is important to understand and validate the levels of satellite HCHO over the remote oceans. Here we intercompare three satellite retrievals of total HCHO columns (OMI-SAO (v004), OMPS-NPP SAO, and OMI BIRA) and validate them against in situ observations from the NASA Atmospheric Tomography Mission (ATom) mission. All retrievals are correlated with ATom integrated columns over remote oceans, with OMI SAO (v004) showing the best agreement. Three satellite HCHO retrievals and in situ ATom columns all generally captured the spatial and seasonal distributions of HCHO in the remote ocean atmosphere. Retrieval bias varies by latitude and season, but a persistent low bias is found in all products at high latitudes and the general low bias is most severe for the OMI BIRA product. Examination of retrieval components reveals slant column corrections have a larger impact on the retrievals over remote marine regions while AMFs play a smaller role. This study informs that the potential latitude-dependent biases in the retrievals require further investigation for improvement and should be considered when using marine HCHO satellite data, and vertical profiles from in situ instruments are crucial for validating satellite retrievals

Sources and characteristics of summertime organic aerosol in the Colorado Front Range: perspective from measurements and WRF-Chem modeling

Abstract. The evolution of organic aerosols (OAs) and their precursors in the boundary layer (BL) of the Colorado Front Range during the Front Range Air Pollution and Photochemistry Éxperiment (FRAPPÉ, July–August 2014) was analyzed by in situ measurements and chemical transport modeling. Measurements indicated significant production of secondary OA (SOA), with enhancement ratio of OA with respect to carbon monoxide (CO) reaching 0.085±0.003 µg m−3 ppbv−1. At background mixing ratios of CO, up to  ∼  1.8 µg m−3 background OA was observed, suggesting significant non-combustion contribution to OA in the Front Range. The mean concentration of OA in plumes with a high influence of oil and natural gas (O&G) emissions was  ∼  40 % higher than in urban-influenced plumes. Positive matrix factorization (PMF) confirmed a dominant contribution of secondary, oxygenated OA (OOA) in the boundary layer instead of fresh, hydrocarbon-like OA (HOA). Combinations of primary OA (POA) volatility assumptions, aging of semi-volatile species, and different emission estimates from the O&G sector were used in the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) simulation scenarios. The assumption of semi-volatile POA resulted in greater than a factor of 10 lower POA concentrations compared to PMF-resolved HOA. Including top-down modified O&G emissions resulted in substantially better agreements in modeled ethane, toluene, hydroxyl radical, and ozone compared to measurements in the high-O&G-influenced plumes. By including emissions from the O&G sector using the top-down approach, it was estimated that the O&G sector contributed to  <  5 % of total OA, but up to 38 % of anthropogenic SOA (aSOA) in the region. The best agreement between the measured and simulated median OA was achieved by limiting the extent of biogenic hydrocarbon aging and consequently biogenic SOA (bSOA) production. Despite a lower production of bSOA in this scenario, contribution of bSOA to total SOA remained high at 40–54 %. Future studies aiming at a better emissions characterization of POA and intermediate-volatility organic compounds (IVOCs) from the O&G sector are valuable

Ozone depletion due to dust release of iodine in the free troposphere

Iodine is an atmospheric trace element emitted from oceans that efficiently destroys ozone (O3). Low O3 in airborne dust layers is frequently observed but poorly understood. We show that dust is a source of gas-phase iodine, indicated by aircraft observations of iodine monoxide (IO) radicals inside lofted dust layers from the Atacama and Sechura Deserts that are up to a factor of 10 enhanced over background. Gas-phase iodine photochemistry, commensurate with observed IO, is needed to explain the low O3 inside these dust layers (below 15 ppbv; up to 75% depleted). The added dust iodine can explain decreases in O3 of 8% regionally and affects surface air quality. Our data suggest that iodate reduction to form volatile iodine species is a missing process in the geochemical iodine cycle and presents an unrecognized aeolian source of iodine. Atmospheric iodine has tripled since 1950 and affects ozone layer recovery and particle formation.Fil: Koenig, Theodore K.. State University of Colorado at Boulder; Estados Unidos. Cooperative Institute for Research in Environmental Sciences; Estados UnidosFil: Volkamer, Rainer. State University of Colorado at Boulder; Estados Unidos. Cooperative Institute for Research in Environmental Sciences; Estados UnidosFil: Apel, Eric C.. National Center for Atmospheric Research; Estados UnidosFil: Bresch, James F.. National Center for Atmospheric Research; Estados UnidosFil: Cuevas, Carlos A.. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaFil: Dix, Barbara. State University of Colorado at Boulder; Estados Unidos. Cooperative Institute for Research in Environmental Sciences; Estados UnidosFil: Eloranta, Edwin W.. University of Wisconsin; Estados UnidosFil: Fernandez, Rafael Pedro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto Interdisciplinario de Ciencias Básicas. - Universidad Nacional de Cuyo. Instituto Interdisciplinario de Ciencias Básicas; ArgentinaFil: Hall, Samuel R.. National Center for Atmospheric Research; Estados UnidosFil: Hornbrook, Rebecca S.. National Center for Atmospheric Research; Estados UnidosFil: Pierce, R. Bradley. National Environmental Satellite, Data, and Information Service; Estados UnidosFil: Reeves, J. Michael. National Center for Atmospheric Research; Estados UnidosFil: Saiz López, Alfonso. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaFil: Ullmann, Kirk. National Center for Atmospheric Research; Estados Unido

Constraining emissions of volatile organic compounds from western US wildfires with WE-CAN and FIREX-AQ airborne observations

The impact of biomass burning (BB) on the atmospheric burden of volatile organic compounds (VOCs) is highly uncertain. Here we apply the GEOS-Chem chemical transport model (CTM) to constrain BB emissions in the western US at ~25 km resolution. Across three BB emission inventories widely used in CTMs, the total of 14 modeled BB VOC emissions in the western US agree with each other within 30&ndash;40 %. However, emissions for individual VOC differ by up to a factor of 5 (i.e., lumped &ge; C4 alkanes), driven by the regionally averaged emission ratios (ERs) among inventories. We further evaluate GEOS-Chem simulations with aircraft observations made during WE-CAN (Western Wildfire Experiment for Cloud Chemistry, Aerosol Absorption, and Nitrogen) and FIREX-AQ (Fire Influence on Regional to Global Environments and Air Quality) field campaigns. Despite being driven by different global BB inventories or applying various injection height assumptions, GEOS-Chem simulations underpredict observed vertical profiles by a factor of 3&ndash;7. The model shows small-to-no bias for most species in low/no smoke conditions. We thus attribute the negative model biases mostly to underestimated BB emissions in these inventories. Tripling BB emissions in the model reproduces observed vertical profiles for primary compounds, i.e., CO, propane, benzene, and toluene. However, it shows no-to-less significant improvements for oxygenated VOCs, particularly formaldehyde, formic acid, acetic acid, and lumped &ge; C3 aldehydes, suggesting the model is missing secondary sources of these compounds in BB-impacted environments. The underestimation of primary BB emissions in inventories is likely attributable to underpredicted amounts of effective dry matter burned, rather than errors in fire detection, injection height, or ERs. We cannot rule out potential sub-grid uncertainties (i.e., not being able to fully resolve fire plumes) in the nested GEOS-Chem which could explain the model negative bias partially, though the back-of-the-envelope calculation and evaluation using longer-term ground measurements help increase the argument of the dry matter burned underestimation. The ERs of the 14 BB VOCs implemented in GEOS-Chem account for about half of the total 161 measured VOCs (~75 versus 150 ppb ppm-1). This reveals a significant amount of missing reactive organic carbon in widely-used BB emission inventories. Considering both uncertainties in effective dry matter burned and unmodeled VOCs, we infer that BB contributed up to 10 % in 2019 and 45 % in 2018 (240 and 2040 GgC) of the total VOC primary emission flux in the western US during these two fire seasons, compared to only 1&ndash;10 % in the standard GEOS-Chem.</p