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Estimates of ozone response to various combinations of NO(x) and VOC emission reductions in the eastern United States

There is increasing recognition that controls on NO(x) emissions may be necessary, in addition to existing and future Volatile Organic Compounds (VOC) controls, for the abatement of ozone (O3) over portions of the United States. This study compares various combinations of anthropogenic NO(x) and VOC emission reductions through a series of model simulations. A total of 6 simulations were performed with the Regional Oxidant Model (ROM) for a 9-day period in July 1988. Each simulation reduced anthropogenic NO(x) and VOC emissions across-the-board by different amounts. Maximum O3 concentrations for the period were compared between the simulations. Comparison of the simulations suggests that: (1) NO(x) controls may be more effective than VOC controls in reducing peak O3 over most of the eastern United States; (2) VOC controls are most effective in urban areas having large sources of emissions; (3) NO(x) controls may increase O3 near large point sources; and (4) the benefit gained from increasing the amount of VOC controls may lessen as the amount of NO(x) control is increased. This paper has been reviewed in accordance with the U.S. Environmental Protection Agency's peer and administrative review policies and approved for presentation and publication. Mention of trade names or commercial products does not constitute endorsement or recommendation for use.

Roselle, Shawn J.

Improved Assessment of Recent Trends in NOx and VOC Emissions and Ozone Production Sensitivity Regimes Using Satellite Data

This presentation highlights results from a NASA Aura Science Team and Atmospheric Composition Modeling and Analysis Program (ACMAP) project which study the capability to observe and model trends in ozone (O3) production regimes using spaceborne sensors. Ultraviolet– visible (UV–Vis) tropospheric column satellite retrievals of formaldehyde (HCHO) (a proxy for volatile organic compound [VOC] reactivity) and nitrogen dioxide (NO2) (a proxy for nitrogen oxides [NOx]) are frequently used to investigate the sensitivity of O3 production to emissions of NOx and VOCs. There are challenges that come from using satellite-derived ratios of HCHO and NO2 (FNR) to study O3 production sensitivity with the largest uncertainties associated with specific spaceborne sensor’s retrieval biases and errors. This study quantifies the differences and improvements in satellite retrievals of O3 production sensitivity regimes using FNRs when moving from legacy polar orbiting satellites such as the Ozone Monitoring Instrument (OMI) onboard NASA’s Aura satellite and Ozone Mapping and Profiler Suite Nadir Mapper (OMPS-NM) onboard the NASA/NOAA Suomi-NPP platform to newer, higher spatiotemporal resolution satellite sensors TROPOspheric Monitoring Instrument (TROPOMI) and eventually the recently launched NASA geostationary sensor Tropospheric Emissions: Monitoring of Pollution (TEMPO). Furthermore, we investigate how using retrievals of NO2 and HCHO from these different satellites to constrain model predictions impacts the ability to accurately simulate O3 chemistry including chemical production regimes. To this end, we have conducted inverse model simulations, using the WRF-CMAQ-DDM data assimilation system at 12 km × 12 km, to constrain emissions of NOx and VOCs over the contiguous United States (CONUS) when assimilating OMI and TROPOMI retrievals of NO2 and HCHO. Two advantages of this are that we a) account for each satellite’s errors/biases in the emission estimation and b) update the prior profile to ensure that only radiance information is used for optimizing the emissions. This presentation will demonstrate: a) the varying accuracy of different satellite retrieved FNRs and ability to capture known sub-annual emission trends (e.g., seasonal, weekend/weekday) and emission anomalies during the COVID-19 lockdown of 2020, b) the differences and improvements in top-down emission estimates of NOx and VOCs when constrained by newer satellite sensors compared to legacy systems, and c) multi-sensor optimized emission estimates of summer-time NOx and VOCs between 2019-2021.

Data

Quantifying VOC-Reaction Tracers, Ozone Production, and Continuing Aerosol Production Rates in Urban and Far-Downwind Atmospheres

We have found a surprisingly informative decomposition of the complex question of smoggy ozone production (basically, [HO2] in a more locally determined field of [NO]) in the process of linked investigations of modestly smoggy Eastern North America (by NASA aircraft, July 2004) and rather polluted Flushing, NYC (Queens College, July, 2001). In both rural and very polluted situations, we find that a simple contour graph parameterization of the local principal ozone production rate can be estimated using only the variables [NO] and j(sub rads) [HCHO]: Po(O3) = c (j(sub rads) [HCHO])(sup a) [HCHO](sup b). Here j(sub rads) is the photolysis of HCHO to radicals, presumably capturing many harder-UV photolytic processes and the principle ozone production is that due to HO2; mechanisms suggest that ozone production due to RO2 is closely correlated, often suggesting a limited range of different proportionality factors. The method immediately suggests a local interpretation for concepts of VOC limitation and NOx limitation. We believe that the product j(sub rads) [HCHO] guages the oxidation rate of observed VOC mixtures in a way that also provides [HO2] useful for the principle ozone production rate k [HO2] [NO], and indeed, all ozone chemical production. The success of the method suggests that dominant urban primary-HCHO sources may transition to secondary plume-HCHO sources in a convenient way. Are there other, simple, near-terminal oxidized VOC's which help guage ozone production and aerosol particle formation? Regarding particles, we report on, to the extent NASA Research resources allow, on appealing relationships between far-downwind (Atlantic PBL) HCHO and very fine aerosol (including sulfate. Since j(sub rads) [HCHO] provides a time-scale, we may understand distant-plume particle production in a more quantitative manner. Additionally we report on a statistical search in the nearer field for relationships between glyoxals (important near-terminal aromatic and isoprene reaction products) and aerosol production, looking for VOC's that might be most implicated. All three variables j(sub rads), [HCHO], and [NO] are relatively easily measured in widespread air pollution monitoring networks, and all are deducible form space-borne observations, though estimation of [NO] from [NO2] (the species observable from space) may require care. We report also on airborne and surface observations of HCHO, suggesting that concentrated (urban) and more diffuse (forest) sources may be distinguishable from space. The use of the 3.58 micron microwindow for HCHO remote sensing should allow much sharper resolution of HCHO than the UV. UV sensing requires large and expensive instruments, but even these seem justified since formaldehyde is so informative.

Chatfield, Robert

Application of OMI Observations to a Space-Based Indicator of NOx and VOC Controls on Surface Ozone Formation

We investigated variations in the relative sensitivity of surface ozone formation in summer to precursor species concentrations of volatile organic compounds (VOCs) and nitrogen oxides (NOx) as inferred from the ratio of the tropospheric columns of formaldehyde to nitrogen dioxide (the "Ratio") from the Aura Ozone Monitoring Instrument (OMI). Our modeling study suggests that ozone formation decreases with reductions in VOCs at Ratios less than 1 and NOx at Ratios greater than 2; both NOx and VOC reductions may decrease ozone formation for Ratios between 1 and 2. Using this criteria. the OMI data indicate that ozone formation became: 1. more sensitive to NOx over most of the United States from 2005 to 2007 because of the substantial decrease in NOx emissions, primarily from stationary sources, and the concomitant decrease in the tropospheric column of NO2. and 2. more sensitive to NOx with increasing temperature, in part because emissions of highly reactive, biogenic isoprene increase with temperature, thus increasing the total VOC reactivity. In cities with relatively low isoprene emissions (e.g .. Chicago). the data clearly indicate that ozone formation became more sensitive to NOx from 2005 to 2007. In cities with relatively high isoprene emissions (e.g ., Atlanta), we found that the increase in the Ratio due to decreasing NOx emissions was not obvious as this signal was convolved with variations in the Ratio associated with the temperature dependence of isoprene emissions and, consequently, the formaldehyde concentration.

Duncan, Bryan N.

Development of the Volatile Organic Compound (VOC) Removal System Final Report

The United States, along with other countries around the world, is preparing to return humankind to the Lunar surface. This endeavor will require the development of new technologies if a human presence beyond the Earth’s sphere of influence is to be maintained. Indeed, during the space race of the 20th century, a mere twelve astronauts traveled to the Moon and returned to Earth. Now, in the 21st century as we prepare to travel back to the Moon and on to Mars a more substantial effort will be needed to develop how astronauts can sustain themselves for long duration. Among the technologies that need further development are CO 2 and removal along with the removal of volatile organic compounds (VOCs). Long-term human exploration necessitates CO 2 and VOC removal systems which require little to no maintenance, i.e., no sorbent materials. Currently, NASA AMES is developing a CO 2 Deposition System (CDep) which does not rely on sorbent materials. Rather, by chilling the incoming air the system is able to “freeze-out” the CO 2 while allowing oxygen and nitrogen to pass through the system. However, this system in its current configuration is unable to filter out all VOCs. Therefore, it is necessary to further develop this system with the addition of a VOC removal element to provide a complete solution to the long-term problem of air revitalization in a safe and reliable manner.

Nilton De Oliveira Renno

The Sensitivity of U.S. Surface Ozone Formation to NOx, and VOCs as Viewed from Space

We investigated variations in the sensitivity of surface ozone formation in summer to precursor species concentrations of volatile organic compounds (VOCs) and nitrogen oxides (NO(x)) as inferred from the ratio of tropospheric columns of formaldehyde and nitrogen dioxide from the Aura Ozone Monitoring Instrument (OMI). The data indicate that ozone formation became: 1. more sensitive to NO(x) over most of the U.S, from 2005 to 2007 because of substantial decreases in NO(x) emissions primarily from stationary sources, and 2. more sensitive to NO(x) with increasing temperature, in part because emissions of highly reactive, biogenic isoprene increase with temperature, thus increasing the total VOC reactivity. Based on our interpretation of the data, current strategies implemented to reduce unhealthy levels of surface ozone should focus more on reducing NO(x) emissions, except in some downtown areas which have historically benefited from reductions in VOC emissions.

Duncan, Bryan N.

A Five-year Performance Study of Low VOC Coatings over Zinc Thermal Spray for the Protection of Carbon Steel at the Kennedy Space Center

The launch facilities at the Kennedy Space Center (KSC) are located approximately 1000 feet from the Atlantic Ocean where they are exposed to salt deposits, high humidity, high UV degradation, and acidic exhaust from solid rocket boosters. These assets are constructed from carbon steel, which requires a suitable coating to provide long-term protection to reduce corrosion and its associated costs. While currently used coating systems provide excellent corrosion control performance, they are subject to occupational, safety, and environmental regulations at the Federal and State levels that limit their use. Many contain high volatile organic compounds (VOCs), hazardous air pollutants, and other hazardous materials. Hazardous waste from coating operations include vacuum filters, zinc dust, hazardous paint related material, and solid paint. There are also worker safety issues such as exposure to solvents and isocyanates. To address these issues, top-coated thermal spray zinc coating systems were investigated as a promising environmentally friendly corrosion protection for carbon steel in an acidic launch environment. Additional benefits of the combined coating system include a long service life, cathodic protection to the substrate, no volatile contaminants, and high service temperatures. This paper reports the results of a performance based study to evaluate low VOC topcoats (for thermal spray zinc coatings) on carbon steel for use in a space launch environment.

Zinc Thermal Spray

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

Evaluation of Gas Chromatography/Mini-IMS to Detect VOCs

The Toxicology Laboratory at Johnson Space Center (JSC) has pioneered the use of gas chromatography-ion mobility spectrometry (GC/IMS) for measuring target volatile organic compounds (VOCs) aboard spacecraft. Graseby Dynamics, under contract to NASA/Wyle, has built several volatile organic analyzers (VOA) based on GC/IMS. Foremost among these have been the volatile organic analyzer-risk mitigation unit and the two flight VOA units for International Space Station (ISS). The development and evaluation of these instruments has been chronicled through presentations at the International Conference on Ion Mobility Spectrometry over the past three years. As the flight VOA from Graseby is prepared for operation on ISS at JSC, it is time to begin evaluations of technologies for the next generation VOA, Although the desired instrument characteristics for the next generation unit are the same as the current unit, the requirements are much more stringent. As NASA looks toward future missions beyond Earth environs, a premium will be placed upon small, light, reliable, autonomous hardware. It is with these visions in mind that the JSC Toxicology Laboratory began a search for the next generation VOA. One technology that is a candidate for the next generation VOA is GC/IMS. The recent miniaturization of IMS technology permits it to compete with other, inherently small, technologies such as chip-sized sensor arrays. This paper will discuss the lessons learned from the VOA experience and how that has shaped the design of a potential second generation VOA based upon GC/IMS technology. Data will be presented from preliminary evaluations of GC technology and the mini-IMS when exposed to VOCs likely to be detected aboard spacecraft. Results from the evaluation of an integrated GC/mini-IMS system will be shown if available.

Limero, Thomas

Silica-Titania Composite (STC)'s Performance in the Photocatalytic Oxidation of Polar VOCs

The objective of this paper is to determine the performance of a Silica-Titania Composite (STC) in the photocatalytic oxidation (PCO) of polar VOCs for potential applications in trace contaminant control within space habitats such as the ISS and CEV Orion. Tests were carried out in a bench scale STC-packed annular reactor under continuous illumination by either a UV-C germicidal lamp(lambda (sub max) = 254 nm) or UV-A fluorescent BLB (lambda(sub max) = 365 nm) for the removal of ethanol (a predominant polar VOC in the ISS cabin). The STC's performance was evaluated in terms of the ethanol mineralization rate, mineralization efficiency, and the extent of its oxidation intermediate (acetaldehyde) formation in response to the type of light source (photon energy and photon flux) and relative humidity (RH) implemented. Results demonstrated that acetaldehyde was the only quantifiable intermediate in the effluent under UV illumination, but was not found in the dark adsorption experiments. The mineralization rate increased with an increase in photon energy (UV-C greater than UV-A), even though both lamps were adjusted to emit the same incident photon flux, and also increased with increasing photon flux. However, photonic efficiency decreased as the photon flux increased. More importantly, a higher photon flux gave rise to a lower effluent acetaldehyde concentration. The effect of RH on PCO was complex and intriguing because it affected both physical adsorption and photocatalytic oxidation. In general, increasing RH caused a decrease in adsorption capacity for ethanol and reduced the mineralization efficiency with a concomitant higher acetaldehyde evolution rate. The effect of RH was less profound than that of photon flux.

Levine, Lanfang H.

Changes in the Ozone Chemical Regime Over the Contiguous United States Inferred By the Inversion of NOx and VOC Emissions Using Satellite Observation

To investigate changes in the ozone (O3) chemical production regime over the contiguous United States (CONUS) with accurate knowledge of concentrations of its precursors, we applied an inverse modeling technique with Ozone Monitoring Instrument (OMI) tropospheric nitrogen dioxide (NO2) and total formaldehyde (HCHO) retrieval products in the summers of 2011, 2014, and 2017, years in which United States National Emission Inventory were based. The inclusion of dynamic chemical lateral boundary conditions and lightning-induced nitric oxide emissions significantly account for the contribution of background sources in the free troposphere. Satellite-constrained nitrogen oxide (NOx) and non-methane volatile organic compounds (NMVOCs) emissions mitigate the discrepancy between satellite and modeled columns: the inversion suggested 2.33-2.84 (1.07-1.34) times higher NOx over the CONUS (over urban regions) and 0.28-0.81 times fewer NMVOCs emissions over the southeastern United States. The model-derived HCHO/NO2 column ratio shows gradual spatial changes in the O3 production regime near urban cores relative to previously defined threshold values representing NOx and VOC sensitive conditions. We also found apparent shifts from the NOx-saturated regime to the transition regime (or the transition regime to the NOx-limited regime) over the major cities in the western United States. In contrast, rural areas, especially in the east-southeastern United States, exhibit a decreased HCHO/NO2 column ratio by -1.30 ± 1.71 with a reduction in HCHO column primarily driven by meteorology, becoming sensitive to VOC emissions. Results show that incorporating satellite observations into numerical modeling could help policymakers implement appropriate emission control policies for O3 pollution.

HCHO/NO2 factorInverse modelingOzone chemical regi

Dynamic Sampling of Cabin VOCs during the Mission Operations Test of the Deep Space Habitat

The atmospheric composition inside spacecraft is dynamic due to changes in crew metabolism and payload operations. A portable FTIR gas analyzer was used to monitor the atmospheric composition of four modules (Core lab, Veggie Plant Atrium, Hygiene module, and Xhab loft) within the Deep Space Habitat '(DSH) during the Mission Operations Test (MOT) conducted at the Johnson Space Center. The FTIR was either physically relocated to a new location or the plumbing was changed so that a different location was monitored. An application composed of 20 gases was used and the FTIR was zeroed using N2 gas every time it was relocated. The procedures developed for operating the FTIR were successful as all data was collected and the FTIR worked during the entire MOT mission. Not all the 20 gases in the application sampled were detected and it was possible to measure dynamic VOC concentrations in each DSH location.

Monje, Oscar

Plasma Treatment of Volatile Organic Compounds (VOCs)

Plasma is an energetic source that has thermal and non-thermal chemistry applications. For this work, we pursued the investigation of plasma as a non-consumable based method of treating spacecraft volatile organic compounds (VOCs) in order to mitigate or eliminate potential hazards. This work focused on select compounds but also applied the technology to program-funded trash-to-gas (TtG) effluent gas.

Logistics Management

In-Situ Chemical Reduction and Oxidation of VOCs in Groundwater: Groundwater Treatability Studies

This paper presents NASA Marshall Space Flight Center's treatability studies for volatile organic compounds in groundwater. In-Situ groundwater treatment technologies include: 1) Chemical Reduction(Ferox); 2) Chemical Oxidation (Fenton Reagents, Permanganate, and Persulfate); and 3) Thermal (Dynamic Underground Stripping, Six-Phase Heating). This paper is presented in viewgraph form.

Keith, Amy

Fungal colonization of fiberglass insulation in the air distribution system of a multi-story office building: VOC production and possible relationship to a sick building syndrome

Complaints characteristic of those for sick building syndrome prompted mycological investigations of a modern multi-story office building on the Gulf coast in the Southeastern United States (Houston-Galveston area). The air handling units and fiberglass duct liner of the heating, ventilating and air conditioning system of the building, without a history of catastrophic or chronic water damage, demonstrated extensive colonization with Penicillium spp and Cladosporium herbarum. Although dense fungal growth was observed on surfaces within the heating-cooling system, most air samples yielded fewer than 200 CFU m-3. Several volatile compounds found in the building air were released also from colonized fiberglass. Removal of colonized insulation from the floor receiving the majority of complaints of mouldy air and continuous operation of the units supplying this floor resulted in a reduction in the number of complaints.

NASA Program Environmental Health