Engineering topics

Iraci, Laura T.

Publications and source records attributed to Iraci, Laura T..

At least 37 records · Page 2

NASA NTRS2016

Airborne Observations of Ozone and Other Trace Gases Upwind of National Parks in California and Nevada

The Alpha Jet Atmospheric eXperiment (AJAX) is a research project based at Moffett Field, CA, which collects airborne measurements of ozone, carbon dioxide, methane, water vapor, and formaldehyde, as well as 3-D winds, temperature, pressure, and location. Since its first science flight in 2011, AJAX has developed a wide a variety of mission types, combining vertical profiles (from approximately 8 km to near surface), boundary layer legs, and plume sampling as needed. With an ongoing five-year data set, the team has sampled over 160 vertical profiles, a dozen wildfires, and numerous stratospheric ozone intrusions. Our largest data collection includes 55 vertical profiles at Railroad Valley, NV, approximately 100 miles southwest of Great Basin National Park, and many of those flights include comparisons to surface monitors in the Nevada Rural Ozone Initiative network. We have also collected a smaller set of measurements northwest of Joshua Tree National Park, and are looking to develop partnerships that can put this data to use to assess or improve air quality in nearby Parks. AJAX also studies the plumes emitted by wildfires in California, as most emissions inventories are based on prescribed fires. We have sampled a dozen fires, and results will be presented from several, including the Rim (2013), Soberanes and Cedar (2016) Fires.

Ozone↗

NASA NTRS2016

Airborne In-Situ Measurements of Formaldehyde Over California: First Results from the Compact Formaldehyde Fluorescence Experiment (COFFEE) Instrument

Formaldehyde (HCHO) is one of the most abundant oxygenated volatile organic compounds (VOCs) in the atmosphere, playing a role multiple atmospheric processes. Measurements of HCHO can be used to help quantify convective transport, the abundance of VOCs, and ozone production in urban environments. The Compact Formaldehyde FluorescencE Experiment (COFFEE) instrument uses Non-Resonant Laser Induced Fluorescence (NR-LIF) to detect trace concentrations of HCHO as part of the Alpha Jet Atmospheric eXperiment (AJAX) payload. Developed at NASA GSFC, COFFEE is a small, low maintenance instrument with a sensitivity of 100 pptv and a quick response time (1 sec). The COFFEE instrument has been customized to fit in an external wing pod on the Alpha Jet aircraft based at NASA ARC. The instrument can operate over a broad range of altitudes, from boundary layer to lower stratosphere, making it well suited for the Alpha Jet, which can access altitudes from the surface up to 40,000 ft. Results of the first COFFEE science flights preformed over the California's Central Valley will be presented. Boundary layer measurements and vertical profiles in the tropospheric column will both be included. This region is of particular interest, due to its elevated levels of HCHO, revealed in satellite images, as well as its high ozone concentrations. In addition to HCHO, the AJAX payload includes measurements of atmospheric ozone, methane, and carbon dioxide. Formaldehyde is one of the few urban pollutants that can be measured from space. Plans to compare in-situ COFFEE data with satellite-based HCHO observations such as those from OMI (Aura) and OMPS (SuomiNPP) will also be presented.

ozone↗

NASA NTRS2016

Consistent Evaluation of ACOS-GOSAT, BESD-SCIAMACHY, CarbonTracker, and MACC Through Comparisons to TCCON

Consistent validation of satellite CO2 estimates is a prerequisite for using multiple satellite CO2 measurements for joint flux inversion, and for establishing an accurate long-term atmospheric CO2 data record. Harmonizing satellite CO2 measurements is particularly important since the differences in instruments, observing geometries, sampling strategies, etc. imbue different measurement characteristics in the various satellite CO2 data products. We focus on validating model and satellite observation attributes that impact flux estimates and CO2 assimilation, including accurate error estimates, correlated and random errors, overall biases, biases by season and latitude, the impact of coincidence criteria, validation of seasonal cycle phase and amplitude, yearly growth, and daily variability. We evaluate dry-air mole fraction (X(sub CO2)) for Greenhouse gases Observing SATellite (GOSAT) (Atmospheric CO2 Observations from Space, ACOS b3.5) and SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY) (Bremen Optimal Estimation DOAS, BESD v2.00.08) as well as the CarbonTracker (CT2013b) simulated CO2 mole fraction fields and the Monitoring Atmospheric Composition and Climate (MACC) CO2 inversion system (v13.1) and compare these to Total Carbon Column Observing Network (TCCON) observations (GGG2012/2014). We find standard deviations of 0.9, 0.9, 1.7, and 2.1 parts per million vs. TCCON for CT2013b, MACC, GOSAT, and SCIAMACHY, respectively, with the single observation errors 1.9 and 0.9 times the predicted errors for GOSAT and SCIAMACHY, respectively. We quantify how satellite error drops with data averaging by interpreting according to (error(sup 2) equals a(sup 2) plus b(sup 2) divided by n (with n being the number of observations averaged, a the systematic (correlated) errors, and b the random (uncorrelated) errors). a and b are estimated by satellites, coincidence criteria, and hemisphere. Biases at individual stations have year-to-year variability of 0.3 parts per million, with biases larger than the TCCON predicted bias uncertainty of 0.4 parts per million at many stations. We find that GOSAT and CT2013b under-predict the seasonal cycle amplitude in the Northern Hemisphere (NH) between 46 and 53 degrees North latitude, MACC over-predicts between 26 and 37 degrees North latitude, and CT2013b under-predicts the seasonal cycle amplitude in the Southern Hemisphere (SH). The seasonal cycle phase indicates whether a data set or model lags another data set in time. We find that the GOSAT measurements improve the seasonal cycle phase substantially over the prior while SCIAMACHY measurements improve the phase significantly for just two of seven sites. The models reproduce the measured seasonal cycle phase well except for at Lauder_125HR (CT2013b) and Darwin (MACC). We compare the variability within 1 day between TCCON and models in June-July-August; there is correlation between 0.2 and 0.8 in the NH, with models showing 10-50 percent the variability of TCCON at different stations and CT2013b showing more variability than MACC. This paper highlights findings that provide inputs to estimate flux errors in model assimilations, and places where models and satellites need further investigation, e.g., the SH for models and 45-67 degrees North latitude for GOSAT and CT2013b.

ACOS-GOSAT↗

NASA NTRS2016

Airborne In-Situ Measurements of Formaldehyde over California: First Results from the Compact Formaldehyde Fluorescence Experiment (COFFEE) Instrument

coffee↗

NASA NTRS2016

Investigating Ozone Sources in California Using AJAX Airborne Measurements and Models: Implications for Stratospheric Intrusion and Long Range Transport

High ozone concentrations at low altitudes near the surface were detected from airborne Alpha Jet Atmospheric eXperiment (AJAX) measurements on May 30, 2012. We investigate the causes of the elevated ozone concentrations using the airborne measurements and various models. GEOSchem and WRF-STILT model simulations show that the contribution from local sources is small. From MERRA reanalysis, it is found that high potential vorticity (PV) is observed at low altitudes. This high PV appears to be only partially coming through the stratospheric intrusions because the air inside the high PV region is moist, which shows that mixing appears to be enhanced in the low altitudes. Considering that diabatic heating can also produce high PV in the lower troposphere, high ozone is partially coming through stratospheric intrusion, but this cannot explain the whole ozone concentration in the target areas of the western U.S. A back-trajectory model is utilized to see where the air masses originated. The air masses of the target areas came from the lower stratosphere (LS), upper (UT), mid- (MT), and lower troposphere (LT). The relative number of trajectories coming from LS and UT is low (7.7% and 7.6%, respectively) compared to that from LT (64.1%), but the relative ozone concentration coming from LS and UT is high (38.4% and 20.95%, respectively) compared to that from LT (17.7%). The air mass coming from LT appears to be mostly coming from Asia. Q diagnostics show that there is sufficient mixing along the trajectory to indicate that ozone from the different origins is mixed and transported to the western U.S. This study shows that high ozone concentrations can be detected by airborne measurements, which can be analyzed by integrated platforms such as models, reanalysis, and satellite data.

gas composition↗

NASA NTRS2015

Investigation of Ozone Sources in California Using AJAX Airborne Measurements and Models: Implications for Stratospheric Intrusion and Long Range Transport

High ozone concentrations at low altitudes near the surface were detected from airborne Alpha Jet Atmospheric eXperiment (AJAX) measurements on May 30, 2012. We investigate the causes of the elevated ozone concentrations using the airborne measurements and various models. GEOS-chem and WRF-STILT model simulations show that the contribution from local sources is small. From MERRA reanalysis, it is found that high potential vorticity (PV) is observed at low altitudes. This high PV appears to be only partially coming through the stratospheric intrusions because the air inside the high PV region is moist, which shows that mixing appears to be enhanced in the low altitudes. Considering that diabatic heating can also produce high PV in the lower troposphere, high ozone is partially coming through stratospheric intrusion, but this cannot explain the whole ozone concentration in the target areas of the western U.S. A back-trajectory model is utilized to see where the air masses originated. The air masses of the target areas came from the lower stratosphere (LS), upper (UT), mid- (MT), and lower troposphere (LT). The relative number of trajectories coming from LS and UT is low (7.7 and 7.6, respectively) compared to that from LT (64.1), but the relative ozone concentration coming from LS and UT is high (38.4 and 20.95, respectively) compared to that from LT (17.7). The air mass coming from LT appears to be mostly coming from Asia. Q diagnostics show that there is sufficient mixing along the trajectory to indicate that ozone from the different origins is mixed and transported to the western U.S. This study shows that high ozone concentrations can be detected by airborne measurements, which can be analyzed by integrated platforms such as models, reanalysis, and satellite data.

low altitude↗

NASA NTRS2015

Airborne Observations of Carbon Dioxide and Methane Emission Ratios from the Yosemite Rim Wildfire, California

This paper presents airborne in situ measurements of carbon dioxide (CO2) and methane (CH4) downwind of an exceptionally large wildfire, the Rim Fire, near Yosemite, California, during two flights. Data analyses are discussed in terms of emission ratios (ER) and emission factors (EF) and are compared to previous studies. CH4 ER’s were 7.5-7.9 parts per billion (ppb) CH4 for every 1 part per million (ppm) of CO2 (ppb CH4 (ppm CO2)(exp.-1)) on 29 August 2013 and 14.2-16.7 ppb CH4 (ppm CO2)(exp. -1) on 10 September 2013. This study measured only CO2 and CH4; however, estimated emission factors (EEF’s) are used as rough estimates of EF’s of CO2 and CH4 and are in close agreement with EF’s reported in previous studies. In the western US, wildfires dominate over prescribed fires, contributing to atmospheric trace gas budgets and regional and local air pollution. Limited sampling of emissions from wildfires means western US emission estimates rely largely on data from prescribed fires, which may not be a suitable proxy for wildfire emissions. Given the magnitude of the Yosemite Rim wildfire, the impacts it had on regional air quality and the limited sampling of wildfire emissions in the western US to date, this study provides a valuable measurement dataset and may have important implications for forestry and regional air quality management.

Yates, Emma L.↗

NASA NTRS2014

Airborne In-Situ Trace Gas Measurements of Multiple Wildfires in California (2013-2014)

Biomass burning emissions are an important source of a wide range of trace gases and particles that can impact local, regional and global air quality, climate forcing, biogeochemical cycles and human health. In the western US, wildfires dominate over prescribed fires, contributing to atmospheric trace gas budgets and regional and local air pollution. Limited sampling of emissions from wildfires means western US emission estimates rely largely on data from prescribed fires, which may not be a suitable proxy for wildfire emissions.We report here in-situ measurements of carbon dioxide, methane, ozone and water vapor from the plumes of a variety of wildfires sampled in California in the fire seasons of 2013 and 2014. Included in the analysis are the Rim Fire (August October 2013, near Yosemite National Park), the Morgan Fire (September 2013, near Clayton, CA), and the El Portal Fire (July August 2014, in Yosemite National Park), among others. When possible, fires were sampled on multiple days.Emission ratios and estimated emission factors will be presented and discussed in the context of fuel composition, plume structure, and fire phase. Correlations of plume chemical composition to MODISVIIRS Fire Radiative Power (FRP) and other remote sensing information will be explored. Furthermore, the role of plumes in delivery of enhanced ozone concentrations to downwind municipalities will be discussed.

Gas↗

NASA NTRS2014

Up in the Air: Methane and Ozone over California

The Alpha Jet Atmospheric eXperiment (AJAX) at NASA Ames Research Center measures in-situ carbon dioxide, methane, and ozone concentrations in the Earth's atmosphere several times each month. The AJAX team studies local photochemical smog production, provides data for long-term studies of trans-Pacific transport of pollution, and supports the observation of greenhouse gases from satellites. The aircraft is stationed at Moffett Field and is outfitted with scientific instruments to measure trace gas concentrations and 3-D wind speeds. Vertical profiles from near the surface up to approximately 27,000 ft are routinely collected over locations such as: Merced, Edwards Air Force Base, Railroad Valley, NV, and over the Pacific Ocean. In addition, boundary layer measurements scout for surface sources such as fires, oil gas infrastructure, livestock, and urban pollution. This talk will focus on recent observations over dairy operations, fossil fuel infrastructure, and wildfires.

Trace Gas Concentrations↗

NASA NTRS2013

Analyzing Carbon Dioxide and Methane Emissions in California Using Airborne Measurements and Model Simulations

Greenhouse gas (GHG) concentrations have increased over the past decades and are linked to global temperature increases and climate change. These changes in climate have been suggested to have varying effects, and uncertain consequences, on agriculture, water supply, weather, sea-level rise, the economy, and energy. To counteract the trend of increasing atmospheric concentrations of GHGs, the state of California has passed the California Global Warming Act of 2006 (AB-32). This requires that by the year 2020, GHG (e.g., carbon dioxide (CO2) and methane (CH4)) emissions will be reduced to 1990 levels. To quantify GHG fluxes, emission inventories are routinely compiled for the State of California (e.g., CH4 emissions from the California Greenhouse Gas Emissions Measurement (CALGEM) Project). The major sources of CO2 and CH4 in the state of California are: transportation, electricity production, oil and gas extraction, cement plants, agriculture, landfills/waste, livestock, and wetlands. However, uncertainties remain in these emission inventories because many factors contributing to these processes are poorly quantified. To alleviate these uncertainties, a synergistic approach of applying air-borne measurements and chemical transport modeling (CTM) efforts to provide a method of quantifying local and regional GHG emissions will be performed during this study. Additionally, in order to further understand the temporal and spatial distributions of GHG fluxes in California and the impact these species have on regional climate, CTM simulations of daily variations and seasonality of total column CO2 and CH4 will be analyzed. To assess the magnitude and spatial variation of GHG emissions and to identify local “hot spots”, airborne measurements of CH4 and CO2 were made by the Alpha Jet Atmospheric eXperiment (AJAX) over the San Francisco Bay Area (SFBA) and San Joaquin Valley (SJV) in January and February 2013 during the Discover-AQ-CA study. High mixing ratios of GHGs were observed in-flight with a high degree of spatial variability. To provide an additional method to quantify GHG emissions, and analyze AJAX measurement data, the GEOS-Chem CTM is used to simulate SFBA/SJV GHG measurements. A nested-grid version of GEOS-Chem will be applied and utilizes varying emission inventories and model parameterizations to simulate GHG fluxes/emissions. The model considers CO2 fluxes from fossil fuel use, biomass/biofuel burning, terrestrial and oceanic biosphere exchanges, shipping and aviation, and production from the oxidation of carbon monoxide, CH4, and non-methane volatile organic carbons. The major sources of CH4 simulated in GEOS-Chem are domesticated animals, rice fields, natural gas leakage, natural gas venting/flaring (oil production), coal mining, wetlands, and biomass burning. Preliminary results from the comparison between available observations (e.g., AJAX and CALGEM CH4 emission maps) and GEOS-Chem results will be presented, along with a discussion of CO2 and CH4 source apportionment and the use of the GEOS-Chem-adjoint to perform inverse GHG modeling.

Johnson, Matthew S.↗

NASA NTRS2012

The United States' Next Generation of Atmospheric Composition and Coastal Ecosystem Measurements: NASA's Geostationary Coastal and Air Pollution Events (GEO-CAPE) Mission

The Geostationary Coastal and Air Pollution Events (GEO-CAPE) mission was recommended by the National Research Council's (NRC's) Earth Science Decadal Survey to measure tropospheric trace gases and aerosols and coastal ocean phytoplankton, water quality, and biogeochemistry from geostationary orbit, providing continuous observations within the field of view. To fulfill the mandate and address the challenge put forth by the NRC, two GEO-CAPE Science Working Groups (SWGs), representing the atmospheric composition and ocean color disciplines, have developed realistic science objectives using input drawn from several community workshops. The GEO-CAPE mission will take advantage of this revolutionary advance in temporal frequency for both of these disciplines. Multiple observations per day are required to explore the physical, chemical, and dynamical processes that determine tropospheric composition and air quality over spatial scales ranging from urban to continental, and over temporal scales ranging from diurnal to seasonal. Likewise, high-frequency satellite observations are critical to studying and quantifying biological, chemical, and physical processes within the coastal ocean. These observations are to be achieved from a vantage point near 95deg-100degW, providing a complete view of North America as well as the adjacent oceans. The SWGs have also endorsed the concept of phased implementation using commercial satellites to reduce mission risk and cost. GEO-CAPE will join the global constellation of geostationary atmospheric chemistry and coastal ocean color sensors planned to be in orbit in the 2020 time frame.

Atmospheric composition↗

NASA NTRS2011

NASA Science in the Middle of Nowhere: Measuring Greenhouse Gases in Railroad Valley, NV

In June 2011, scientists from NASA's Ames Research Center joined a multi-institute team of researchers to investigate carbon dioxide and methane gas emissions from a dry lake bed and the neighboring environment in Railroad Valley, Nevada. Measurements were taken from the ground and onboard two aircraft, and the data will be compared to those measured by the GOSAT satellite. During the campaign, the Ames team conducted a series of flights with an unmanned aircraft system (UAS) known as SIERRA and with a modified Alpha Jet. Methane emissions were also measured from hot and cold springs in the area, and soil microbiology was explored to determine the origin of the methane. This talk will describe the instrumentation and airborne platforms used, as well as preliminary results.

Iraci, Laura T.↗

NASA NTRS2006

Uptake and Dissolution of Gaseous Ethanol in Sulfuric Acid

The solubility of gas-phase ethanol (ethyl alcohol, CH3CH2OH, EtOH) in aqueous sulfuric acid solutions was measured in a Knudsen cell reactor over ranges of temperature (209-237 K) and acid composition (39-76 wt % H2SO4). Ethanol is very soluble under these conditions: effective Henry's law coefficients, H*, range from 4 x 10(exp 4) M/atm in the 227 K, 39 wt % acid to greater than 10(exp 7) M/atm in the 76 wt % acid. In 76 wt % sulfuric acid, ethanol solubility exceeds that which can be precisely determined using the Knudsen cell technique but falls in the range of 10(exp 7)-10(exp 10) M/atm. The equilibrium concentration of ethanol in upper tropospheric/lower stratospheric (UT/LS) sulfate particles is calculated from these measurements and compared to other small oxygenated organic compounds. Even if ethanol is a minor component in the gas phase, it may be a major constituent of the organic fraction in the particle phase. No evidence for the formation of ethyl hydrogen sulfate was found under our experimental conditions. While the protonation of ethanol does augment solubility at higher acidity, the primary reason H* increases with acidity is an increase in the solubility of molecular (i.e., neutral) ethanol.

Michelsen, Rebecca R.↗

NASA NTRS2005

Uptake of Hypobromous Acid (HOBr) by Aqueous Sulfuric Acid Solutions: Low-Temperature Solubility and Reaction

Hypobromous acid (HOBr) is a key species linking inorganic bromine to the chlorine and odd hydrogen chemical families. We have measured the solubility of HOBr in 45 - 70 wt% sulfuric acid solutions representative of upper tropospheric and lower stratospheric aerosol composition. Over the temperature range 201 - 252 K, HOBr is quite soluble in sulfuric acid, with an effective Henry's law coefficient, H* = 10(exp 4) - 10(exp 7) mol/L/atm. H* is inversely dependent on temperature, with Delta H = -46.2 kJ/mol and Delta S = -106.2 J/mol/K for 55 - 70 wt% H2SO4 solutions. Our study includes temperatures which overlap both previous measurements of HOBr solubility. For uptake into aqueous 45 wt% H2SO4, the solubility can be described by log H* = 3665/T - 10.63. For 55 - 70 wt% H2SO4, log H* = 2412/T - 5.55. At temperatures colder than approx. 213 K, the solubility of HOBr in 45 wt% H2SO4 is noticeably larger than in 70 wt% H2SO4. The solubility of HOBr is comparable to that of HBr, indicating that upper tropospheric and lower stratospheric aerosols should contain equilibrium concentrations of HOBr which equal or exceed those of HBr. Our measurements indicate chemical reaction of HOBr upon uptake into aqueous sulfuric acid in the presence of other brominated gases followed by evolution of gaseous products including Br2O and Br2, particularly at 70 wt% H2SO4.

Iraci, Laura T.↗

NASA NTRS2004

Environment Partitioning and Reactivity of Polybrominated Diphenylethers

Polybrominated diphenyl ethers (PBDEs) are an important class of flame retardants. Annual global demand for these compounds was over 67,000 metric tons in 2001. PBDEs have recently been extensively investigated as environmental contaminants because they have been detected in air, sediment, and tissue samples from urban and remote areas. Important issues include quantifying PBDE partitioning in various environmental compartments, and elucidating transformation pathways. The partitioning of PBDE congeners to aerosols was estimated for 16 sites in the United States, Canada, and Mexico. The aerosol particles were PM2.5, the total suspended particle (TSP) concentration varied between 3.0 - 55.4 micro g/cubic meter, and the organic fraction ranged from 11 - 41%; these data are published values for each site. It is estimated that the largest fraction of each PBDE associated with the aerosol particles occurs in Mexico City, and the smallest fraction in Colorado Plateau. Although the organic fraction in Mexico City is about 60% of that observed in the Colorado Plateau, the TSP is larger by a factor of about 18.5, and it is the difference in TSP that strongly influences the fraction of particle-bound PBDE in this case. PBDE partitioning to PM2.5 particles also varies seasonally because of temperature variations. For the less brominated congeners the percentage that is particle-bound is relatively low, regardless of air temperature. In contrast, the heavier congeners exhibit a significant temperature dependence: as the temperature decreases (fall, winter) the percentage of PBDE that is particle-bound increases. The partitioning calculations complement experimental data indicating that decabromodiphenyl ether (DBDE) dissolved in hexane transforms very rapidly when irradiated with solar light. DBDE is the most highly brominated PBDE congener (10 bromine atoms) and occurs in the commercial formulation which is subject to the largest global demand.

Hua, Inez↗

NASA NTRS2004

Solubility of HOBr in Acidic Solution and Implications for Liberation of Halogens Via Aerosol Processing

Halogen species are known to catalytically destroy ozone in several regions of the atmosphere. In addition to direct catalytic losses, bromine compounds can indirectly enhance ozone loss through coupling to other radical families. Hypobromous acid (HOBr) is a key species in the linkage of BrOx to ClOx and HOx. The aqueous- phase coupling reaction HOBr + HCI (right arrow) BrCl + H2O may provide a pathway for chlorine activation on sulfate aerosols at temperatures warmer than those required for polar stratospheric cloud formation. We have measured t h e solubility of HOBr in 45 - 70 wt% sulfuric acid solutions. Over the temperature range 201 - 252 K, HOBr is quite soluble in sulfuric acid, H* = 10(exp 4) - 10(exp 7) mol dm(exp -3) atm(exp -1). The expected inverse dependence of H* on temperature was observed, but only a weak dependence on acidity was found. The solubility of HOBr is comparable to that of HBr, indicating that equilibrium concentrations of HOBr could equal or exceed those of HBr in upper tropospheric and lower stratospheric aerosols. Despite the high solubility of HOBr, aerosol volumes are not large enough to sequester a significant fraction of inorganic bromine from the gas phase. Our measurements of HOBr uptake in aqueous sulfuric acid in the presence of other brominated gases show the evolution of gaseous products including Br2O and Br2.

Iraci, Laura T.↗

NASA NTRS2001

Solubility of methanol in low-temperature aqueous sulfuric acid and implications for atmospheric particle composition

Using traditional Knudsen cell techniques, we find well-behaved Henry's law uptake of methanol in aqueous 45 - 70 wt% H2SO4 solutions at temperatures between 197 and 231 K. Solubility of methanol increases with decreasing temperature and increasing acidity, with an effective Henry's law coefficient ranging from 10(exp 5) - 10(exp 8) M/atm. Equilibrium uptake of methanol into sulfuric acid aerosol particles in the upper troposphere and lower stratosphere will not appreciably alter gas-phase concentrations of methanol. The observed room temperature reaction between methanol and sulfuric acid is too slow to provide a sink for gaseous methanol at the temperatures of the upper troposphere and lower stratosphere. It is also too slow to produce sufficient quantities of soluble reaction products to explain the large amount of unidentified organic material seen in particles of the upper troposphere.

Iraci, Laura T.↗

NASA NTRS2001

Heterogeneous Uptake and Conversion of HOBr on H2SO4 at Upper Tropospheric and Stratospheric Temperatures (255 - 210 K)

Halogen species are known to catalytically destroy ozone in several different regions of the atmosphere. In addition to directly destroying ozone, bromine compounds can indirectly enhance ozone loss through coupling to other radical families. Hypobromous acid (HOBr), a key species in the linkage of BrOx to ClOx and HOx, is produced by the hydrolysis of BrONO2 on sulfate aerosols, and thus the heterogeneous behavior of HOBr must be understood. We have measured the solubility of HOBr in 45 to 70 percent by weight sulfuric acid solutions. Over the temperature range 208 to 255 K, HOBr is very soluble in sulfuric acid, H(*) = 10(exp 4) to 10(exp 8) M/atm. The solubility is temperature dependent, and our results agree well with those of Waschewsky and Abbott for 60 percent by weight H2SO4. HOBr is nearly as soluble as HBr, indicating that equilibrium concentrations of HOBr could approach those of HBr in sulfuric acid aerosols. Despite the high solubility of HOBr, stratospheric aerosol volumes are not large enough to sequester a significant fraction of inorganic bromine from the gas phase. Uptake of HOBr was nearly always accompanied by reaction, producing Br2O and possibly Br2. The effect of this bromine conversion pathway on the HOx and ClOx families, particularly at temperatures as warm as 255 K, will be considered.

Iraci, Laura T.↗