The chemistry and dry deposition of atmospheric nitrogen at a rural site in the northeastern United States

Measurements of N gas (HNO\sb3, NH\sb3) and aerosol (NO\sb3\sp-, NH\sb4\sp+) species were made between 1991-1995 to examine the nature of atmospheric N chemistry and to estimate the importance of N dry deposition to the Harvard Forest (Petersham, MA). This U.S. site was influenced by aged rural air masses advected from the northwest (NW) and fresh industrial emissions from the southwest (SW). Mean midday HNO\sb3 and aerosol N mixing ratios were four times higher in SW surface winds. Diel cycles provided evidence of the entrainment of HNO\sb3 and aerosol NO\sb3\sp- from aloft as the nocturnal inversion broke down. HNO\sb3 made up about 20% of NO\sb{\rm Y} at midday, while the sum of measured NO\sb{\rm Y} species accounted for 60-80% of NO\sb{\rm Y} suggesting that PAN and other organic nitrates were significant at this predominantly oak site. The deposition velocity (V\sb{\rm d} of HNO\sb3 was estimated using the modified-Bowen ratio (MBR) and an inferential method. Hourly averaged V\sb{\rm d} for HNO\sb3 ranged from $\approx$1 cm s\sp{-1} at night to $\approx$6 cm s\sp{-1} at midday. HNO\sb3 deposition was typically 3-4 times higher than the measured NO\sb{\rm Y} flux. Measurement bias, storage effects, and the flux of other NO\sb{\rm Y} species probably contributed to this discrepancy. NH\sb3 levels were suppressed by atmospheric SO\sb4\sp{2-} to mixing ratios of 200-300 pptv, below the NH\sb3 compensation point of the canopy. The SO\sb4\sp{2-} regulation of NH\sb{\rm X} (NH\sb3 + NH\sb4\sp+) partitioning changed exponentially as a function of air temperature. The bulk aerosol was as a mixture of submicron ammonium (bi)sulfate aerosols with smaller amounts of soil particles. Aerosols from the SW were rarely neutralized, especially when SO\sb4\sp{2-} concentrations were greater than $\approx$100 nmol m\sp{-3}, suggesting an upper limit for NH\sb{\rm X} emissions from this region. Aerosol NO\sb3\sp- was 4-8 times lower than NH\sb4\sp+, and associated with supermicron Ca\sp{2+}. The higher V\sb{\rm d} of coarse mode NO\sb3\sp- resulted in similar dry deposition fluxes of 1 kg N ha\sp{-1} yr\sp{-1} for both N aerosol species. These aerosol deposition fluxes were considerably smaller than measured N (NO\sb3\sp{-} + NH\sb4\sp+) wet deposition ($\approx$8 kg N ha\sp{-1} yr\sp{-1}) and estimates of HNO\sb3 inputs (1-7 kg N ha\sp{-1} yr\sp{-1}) to this forest ecosystem

Seasonal distributions of fine aerosol sulfate in the North American Arctic basin during TOPSE

We used the mist chamber/ion chromatography technique to quantify fine aerosol SO4=(\u3c2.7 μm) in the Arctic during the Tropospheric Ozone Production about the Spring Equinox Experiment (TOPSE) with about 2.5 min time resolution. Our effective sample area ranged from 50° to 86°N and 53° to 100°W. The seasonal evolution of fine aerosol sulfate in the Arctic troposphere during TOPSE was consistent with the phenomenon of Arctic haze. Arctic haze has been attributed to pollution from sources in the Arctic and pollution transported meridionally along stable isentropes into the Arctic in geographically broad but vertically narrow bands. These layers became more prevalent at higher altitudes as the season progressed toward summer, and the relevant isentropes are not held so close to the surface. Mean fine particle SO4= mixing ratios during TOPSE in February below 1000 m were elevated (112 pptv) and highly variable (between 28 and 290 pptv) but were significantly lower at higher altitudes (about 40 pptv). As the season progressed, elevated mixing ratios and higher variability were observed at higher altitudes, up to 7 km. In May, mixing ratios at the lowest altitudes declined but still remained higher than in February at all altitudes. The high variability in our measurements likely reflects the vertical heterogeneity of the wintertime Arctic atmosphere as the airborne sampling platform passed in and out of these layers. It is presumed that mixing ratios and variability will continue to decline at all altitudes into the summer as wet deposition processes become important in removing aerosol SO4= from the troposphere

Source attribution of ozone in Southeast Texas before and after the Deepwater Horizon accident using satellite, sonde, surface monitor, and air mass trajectory data

Since the summer of 2004, over 300 ozonesondes have been launched from Rice University (29.7 N, 95.4 W) or the University of Houston (29.7 N, 95.3 W), each \u3c 5 km from downtown Houston. The Texas Commission on Environmental Quality maintains a large database of hourly surface ozone observations in Southeast Texas. In this study, we identify the contributions to surface ozone pollution levels from natural and anthropogenic sources, both local and remote in nature. This source identification is performed two ways: 1) through an analysis of sonde data, including ozone concentrations, wind speed and direction, and relative humidity data, and 2) through an analysis that combines trajectory calculations with surface monitor data. We also examine regional changes in Ozone Monitoring Instrument (OMI) measurements of formaldehyde and ozone from 2004 – 2010. In particular, we compare the 2010 sonde, surface monitor, and satellite data after the Deepwater Horizon accident with data from previous years to determine the impact, if any, of the large source of hydrocarbons in the Gulf of Mexico on air quality in Southeast Texas

Stratospheric influence on the northern North American free troposphere during TOPSE: 7Be as a stratospheric tracer

We use 7Be, with HNO3 and O3, to identify air masses sampled from the NCAR C-130 during TOPSE that retained clear evidence of stratospheric influence. A total of 43 such air masses, spread fairly evenly across the February to May sampling period, and 40°N–86°N latitude range, were encountered. South of 55°N, nearly all clear stratospheric influence was restricted to altitudes above 6 km. At higher latitudes stratospherically influenced air masses were encountered as low as 2 km. Approximately 12% of all TOPSE sampling time at altitudes above 2 km was spent in stratospherically impacted air, above 6 km this increased to more than half of the time. Because it is not certain how much of this stratospherically influenced air irreversibly injected mass (and chemical compounds) into the troposphere, we estimate the stratospheric fraction of O3 in high latitude TOPSE samples based on a linear relationship to7Be and compare it to in situ O3. This analysis indicates that the stratospheric source can account for a dominant fraction (\u3e85%) of in situ O3 throughout TOPSE, but that the stratospheric contribution was nearly constant through the 4 month campaign. In February and March the 7Be based estimates of stratospheric O3 account for 10–15% more O3 than was measured, but by April and May there is up to about 10% more O3 than expected from the stratospheric source. This trend suggests that a seasonal transition from O3 depletion to photochemical production in the high latitude North American troposphere is the major cause of the springtime increase in O3

Comparison of Combustion Efficiency to In-Situ Atmospheric Ammonia Measurements from a Miniature Chemical Ionization Mass Spectrometer in the LA Basin

Atmospheric ammonia (NH3) has been shown to impact the environment and threaten both human and animal health, especially in heavily populated urban areas, yet to date there remains a paucity of direct measurements. Recent studies have suggested that ammonia may be generated as a byproduct of fossil fuel emissions due to highly active catalytic converters in light-duty gasoline vehicles. To investigate this relationship, an airborne miniature Chemical Ionization Mass Spectrometer (miniCIMS) was used to directly measure atmospheric ammonia and combustion reaction products in the Southern California LA Basin, during the 2015 NASA Student Airborne Research Program (SARP). The temporal variability in measured ammonia, and the relationship to combustion efficiency will be compared to mobile ground-based measurements from the NASA DISCOVER-AQ campaign, and implications of the findings will be discussed

Modeling chemistry in and above snow at Summit, Greenland – Part 2: Impact of snowpack chemistry on the oxidation capacity of the boundary layer

The chemical composition of the boundary layer in snow covered regions is impacted by chemistry in the snowpack via uptake, processing, and emission of atmospheric trace gases. We use the coupled one-dimensional (1-D) snow chemistry and atmospheric boundary layer model MISTRA-SNOW to study the impact of snowpack chemistry on the oxidation capacity of the boundary layer. The model includes gas phase photochemistry and chemical reactions both in the interstitial air and the atmosphere. While it is acknowledged that the chemistry occurring at ice surfaces may consist of a true quasi-liquid layer and/or a concentrated brine layer, lack of additional knowledge requires that this chemistry be modeled as primarily aqueous chemistry occurring in a liquid-like layer (LLL) on snow grains. The model has been recently compared with BrO and NO data taken on 10 June–13 June 2008 as part of the Greenland Summit Halogen-HOx experiment (GSHOX). In the present study, we use the same focus period to investigate the influence of snowpack derived chemistry on OH and HOx + RO2 in the boundary layer. We compare model results with chemical ionization mass spectrometry (CIMS) measurements of the hydroxyl radical (OH) and of the hydroperoxyl radical (HO2) plus the sum of all organic peroxy radicals (RO2) taken at Summit during summer 2008. Using sensitivity runs we show that snowpack influenced nitrogen cycling and bromine chemistry both increase the oxidation capacity of the boundary layer and that together they increase the midday OH concentrations. Bromine chemistry increases the OH concentration by 10–18 % (10 % at noon LT), while snow sourced NOx increases OH concentrations by 20–50 % (27 % at noon LT). We show for the first time, using a coupled one dimensional snowpack-boundary layer model, that air-snow interactions impact the oxidation capacity of the boundary layer and that it is not possible to match measured OH levels without snowpack NOx and halogen emissions. Model predicted HONO compared with mistchamber measurements suggests there may be an unknown HONO source at Summit. Other model predicted HOx precursors, H2O2 and HCHO, compare well with measurements taken in summer 2000, which had lower levels than other years. Over 3 days, snow sourced NOx contributes an additional 2 ppb to boundary layer ozone production, while snow sourced bromine has the opposite effect and contributes 1 ppb to boundary layer ozone loss

Ozone profile observations in Houston, Texas (1994 - 2010) from aircraft, balloons, and satellites

Houston, Texas has long been an urban area plagued with high levels of surface ozone, particularly in spring and late summer. The combination of a large commuter population and one of the largest concentrations of petrochemical plants in the world results in abundant and nearly co-located sources of NOx and hydrocarbons. The location of Houston on the South Coast of the United States in a subtropical climate results in meteorological conditions that favor ozone production. Using MOZAIC (1994 - 2004), ozonesonde (2000, 2004 - 2010), and TES (2005 – 2010) data, we examine the evolution of ozone profiles over Houston during a period in which various strategies have been implemented to alleviate the ozone pollution problem. Using meteorological data from associated soundings and analyses, we identify and evaluate influences on the ozone profiles from natural and anthropogenic sources, as well as local and remote sources. We further investigate how these various influences have changed with time

Detection of an SO2 plume over Sapporo, Japan from the eruption of Mt. Kasatochi using a balloon sounding technique

During the month of August 2008, 10 ozonesondes were launched from Hokkaido University in Sapporo, Japan as part of a study to examine regional pollution during the Olympic period. Seven of these soundings included a second instrument with a filter designed to remove SO2 from the intake air stream. SO2 interferes with the normal chemistry of the electrochemical cell (ECC) method for ozone detection, with the net result being that each molecule of SO2 registers as minus one molecule of O3. Thus the unfiltered sonde reports [O3] - [SO2] while the filtered sonde reports [O3]. Laboratory tests prior to launch indicate that the SO2 filter is ~87% effective, while destroying little to no O3. The difference between the filtered and unfiltered readings is ~[SO2]. We demonstrate the effectiveness of this technique in the lower and middle troposphere by examining profiles both with and without SO2 present. Ozone Monitoring Instrument (OMI) SO2 data (Krotkov et al., 2006, 2008) and trajectories from the NASA Goddard Trajectory model (Schoeberl & Sparling, 1995) connect the SO2 detected by our balloon borne instruments over Hokkaido, Japan 21 – 22 August to the plume from the volcanic eruption of Mt. Kasatochi 7 – 9 August

NASA’s New Wildland Fire Earth Observation Science & Applications Programmatic Developments

In 2021, the U.S. National Aeronautics & Space Administration (NASA) initiated new programmatic elements within the Science Mission Directorate (SMD) and the Aeronautics Research Mission Directorate (ARMD) focused on supporting wildland fire science and applications improvements, employing the vast array of NASA scientific knowledge, airborne and space-borne Earth Observations (EO) capabilities, technology development (sensor systems, etc.), and large framework modeling efforts. Within the Science Mission Directorate, the NASA Earth Science Division (ESD) will focus on improving our understanding of wildland fire through EO tools and applying rigorous-tested modeling and results of that research into operational use. The ESD Wildfire strategy is to invest in new technology and to better integrate NASA’s satellite, airborne, and ground-based observations with wildfire models to provide the wildfire stakeholders with the information they need to make informed decisions about the pre-, active-, and post-fire conditions. The Applied Science Program has restarted the Wildland Fire Applications Program with a focus on engaging wildland fire management and the fire science community in transitioning EO science efforts into routine use by land management entities at the local, state, national and international level. The NASA Aeronautics Research Mission Directorate will focus on arenas where their aeronautics science and engineering outcomes can benefit the fire management community as well, specifically in the innovative development of Uncrewed Aircraft systems, congested mixed-use platform airspace management issues, new platform configurations supporting wildland fire missions, and other aeronautics-related science/engineering capabilities which may benefit the fire management community. In total, these developments represent a major thrust forward, supporting the goals of utilizing NASA science to benefit humankind. This presentation will highlight the various wildland fire science focus areas identified through collaborations with the wildland fire science and management community and highlight the plans of this new NASA focus area

Measurements of pernitric acid at the South Pole during ISCAT 2000

The first measurements of pernitric acid at the South Pole were performed during the second Investigation of Sulfur Chemistry in the Antarctic Troposphere (ISCAT 2000). Observed HO2NO2 concentrations averaged 25 pptv. Simple steady-state calculations constrained by measurements show that the lifetime of pernitric acid was largely controlled by dry deposition, with thermal decomposition becoming increasingly important at warmer temperatures. We determined that the pernitric acid equilibrium constant is less uncertain than indicated in the literature. One consequence of pernitric acid deposition to the snow surface is that it is an important sink for both NOx and HOx. Another is that the photochemistry of HO2NO2 in the Antarctic snowpack may be a NOx source in addition to nitrate photolysis. This might be one of the important differences in snow photochemistry between the South Pole and warmer polar sites