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Gas-phase flowrate effect on disintegrating cryogenic liquid-jets

Two phase liquid and gaseous nitrogen flow in a pneumatic two fluid atomizer was investigated. Characteristic dropsize for cryogenic sprays were measured with a scattered light scanning instrument developed at NASA-Lewis. Tests were conducted primarily in the aerodynamic stripping regime of liquid jet atomization. At a sampling distance of bar-x=1.3 cm, the Sauter mean, D(sub 32), and volume median, D(sub v.5), drop diameters were measured and correlated with nitrogen gas flowrate, W(sub n), to give the following expressions: D sub 32 to the -1=210W(sub n) to the -1.33 and D(sub v.5) to the -1=150 W(sub n to the -1.33, where reciprocal diameters and gas flowrate are in cm (-1) and g/sec, respectively. The exponent 1.33 for nitrogrn gas flowrate, W(sub n), is the same as that predicted by atomization theory for liquid-jet breakup in high velocity gasflow. When the spray was sampled at axial distances of bar-x=2.5 and 4.5 cm downstream of the atomizer, the exponent decreased to 1.2 and 0.9, respectively. This was attributed to the loss of small droplets due to their rapid vaporization.

Ingebo, Robert D.↗

Human skeletal muscle protein breakdown during spaceflight

Human spaceflight is associated with a loss of body protein. Excretion of 3-methylhistidine (3-MH) in the urine is a useful measurement of myofibrillar protein breakdown. Bed rest, particularly with 6 degrees head-down tilt, is an accepted ground-based model for human spaceflight. The objectives of this report were to compare 3-MH excretion from two Life Sciences shuttle missions (duration 9.5 and 15 days, n = 9) and from 17 days of bed rest (n = 7) with 6 degrees head-down tilt. The bed rest study was designed to mimic an actual Life Sciences spaceflight and so incorporated an extensive battery of physiological tests focused on the musculoskeletal system. Results showed that nitrogen retention, based on excretion of nitrogen in the urine, was reduced during both bed rest [from 22 +/- 1 to 1 +/- 5 mg N x kg(-1) x day(-1) (n = 7; P < 0.05)] and spaceflight [from 57 +/- 9 to 19 +/- 3 mg N x kg(-1) x day(-1) (n = 9; P < 0.05)]. 3-MH excretion was unchanged with either bed rest [pre-bed rest 5.30 +/- 0.29 vs. bed rest 5.71 +/- 0.30 micromol 3-MH x kg(-1) x day(-1), n = 7; P = not significant (NS)] or spaceflight [preflight 4.98 +/- 0.37 vs. 4.59 +/- 0.39 micromol 3-MH x kg(-1) x day(-1) in-flight, n = 9; P = NS]. We conclude that 1) 3-MH excretion was unaffected by spaceflight on the shuttle or with bed rest plus exercise, and 2) because protein breakdown (elevated 3-MH) was increased on Skylab but not on the shuttle, it follows that muscle protein breakdown is not an inevitable consequence of spaceflight.

STS-58 Shuttle Project↗

Northern Hemisphere Atmospheric Influence of the Solar Proton Events and Ground Level Enhancement in January 2005

Solar eruptions in early 2005 led substantial barrage of charged particles on the Earth's atmosphere during the January 16-21 period. Proton fluxes were greatly increased during these several days and led to the production ofHO(x)(H, OH, BO2)and NO(x)(N, NO, NO2), which then caused the destruction of ozone. We focus on the Northern polar region, where satellite measurements and simulations with the Whole Atmosphere Community Climate Model (WACCM3) showed large enhancements in mesospheric HO(x) and NO(x) constituents, and associated ozone reductions, due 10 these solar proton events (SPEs). The WACCM3 simulations show enhanced short-lived OH throughout the mesosphere in the 60-82.5degN latitude band due to the SPEs for most days in the Jan.16-2l,2005 period, in reasonable agreement with the Aura Microwave Limb Sounder (MLS) measurements. Mesospheric HO2 is also predicted to be increased by the SPEs, however, the modeled HO2 results are somewhat larger than the MLS measurements. These HO(x) enhancements led to huge predicted and MLS-measured ozone decreases of greater than 40% throughout most of the Northern polar mesosphere during the SPE period. Envisat Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) measurements of hydrogen peroxide (H2O2) show increases throughout the stratosphere with highest enhancements of about 60 ppt y in the lowermost mesosphere over the Jan. 16-18, 2005 period due to the solar protons. WACCM3 predictions indicate H2O2 enhancements over the same time period of more than twice that amount. Measurements of nitric acid (HNO3) by both MLS and MIPAS show an increase of about 1 ppbv above background levels in the upper stratosphere during January 16-29, 2005. WACCM3 simulations show only minuscule HNO3 changes in the upper stratosphere during this time period. However due to the small loss rates during winter, polar mesospheric enhancements of NO(x) are computed to be greater than 50 ppbv during the SPE period. Computed NO(x)increases, which were statistically significant at the 95% level, lasted about a month past the SPEs. The SCISAT-I Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) NO(x) measurements and MIPAS NO, measurements for the polar Northern Hemisphere are in reasonable agreement with these predictions. An extremely large ground level enhancement (GLE) occurred during the SPE period on January 20, 2005. We find that protons of energies 300 to 20,000 MeV, not normally included in our computations, led to enhanced lower stratospheric odd nitrogen concentrations of less than 0.1% as a result of this GLE.

Jackman, C. H.↗

Gravitational Effects on Cellular Flame Structure

An experimental investigation has been conducted of the effect of gravity on the structure of downwardly propagating, cellular premixed propane-oxygen-nitrogen flames anchored on a water-cooled porous-plug burner. The flame is subjected to microgravity conditions in the NASA Lewis 2.2-second drop tower, and flame characteristics are recorded on high-speed film. These are compared to flames at normal gravity conditions with the same equivalence ratio, dilution index, mixture flow rate, and ambient pressure. The results show that the cellular instability band, which is located in the rich mixture region, changes little under the absence of gravity. Lifted normal-gravity flames near the cellular/lifted limits, however, are observed to become cellular when gravity is reduced. Observations of a transient cell growth period following ignition point to heat loss as being an important mechanism in the overall flame stability, dominating the stabilizing effect of buoyancy for these downwardly-propagating burner-anchored flames. The pulsations that are observed in the plume and diffusion flame generated downstream of the premixed flame in the fuel rich cases disappear in microgravity, verifying that these fluctuations are gravity related.

Dunsky, C. M.↗

Carbon Fiber Reinforced/Silicon Carbide Turbine Blisk Testing in the SIMPLEX Turbopump

A program designed to implement a ceramic matrix composite integrally bladed disk (blisk) into rocket engine style turbomachinery has successfully completed testing. The Marshall Space Flight Center (MSFC) program, utilizing the MSFC turbomachinery design, analysis, and testing capabilities along with materials development capabilities from both Glenn Research Center (GRC) and MSFC, has tested two carbon fiber reinforced silicon carbide blisks in the Simplex Turbopump at MSFC's Test Stand 500. One blisk contained a polar woven fiber preform, while the second blisk tested utilized a quasi-isotropic preform. Vhile earlier papers have chronicled the program's design, material testing, and torque testing efforts, this paper focuses on the testing of the blisks in the Simplex turbopump. Emphasis will be placed on the actual condition of the blisks before and after the testing test program design methodology, and conclusions that can be drawn from the test data and blisk final conditions. The program performed three separate test series. The first series was needed to validate that the Simplex turbopump was correctly re-built following a major incident to the turbopump. The turbopump had two major differences from the original design. The most obvious difference was the sleeve required throughout the bore of the main housing. The second major difference was modifications to the pump diffuser to improve performance. Several areas were burnt during the incident and were either repaired by weld repair (pump inlet housing) or simply smoothed out (turbine nozzle discharge). The test series was designed to weed out any turbopump design and manufacturing flaws or fatigue issues prior to putting the C/SiC blisks into it. The second and third series were the C/SiC blisk test series. The primary goal of these series was to expose the blisks to as much fatigue causing dynamic stress as possible to examine the material's capability. Initially, the test plan was to put equal time on the two blisks, however, as the test series progressed, the funding allowed additional testing to occur. The additional test time was placed on the polar weave blisk. The total test time accrued on the polar blisk was 2550 seconds with 860 seconds near the turbopump design speed of 25,000 rpm. This testing included 6 tests / 775 seconds pumping liquid nitrogen and 7 tests / 1775 seconds pumping liquid oxygen. The drive gas for all of the tests was gaseous nitrogen due to the lack of hot gas source for the Simplex turbopump. The quasi-isotropic blisk was tested for XX total tests and XXXX seconds with X tests/XXXX seconds pumping liquid nitrogen and X tests/XXXX seconds pumping liquid \oxygen.During the test series, the blisks were inspected following each test. Inspections initially were viewed from the downstream side of the blisks only. Midway through the testing, a method of borescoping the leading edges of the blades was devised, and subsequently, both sides of the blades were inspected following each test. The leading and trailing edges of the polar blisk held up better than the quasi-isotropic blisk. This was a known possibility due to the varying fiber direction in the blades as the rectangular preform weave is cut in a circular pattern. The surprising fact about the testing was that there was no measurable performance loss due to the inaccuracies in the blade manufacturing in the C/SiC blisks, the surface roughness C/SiC of the blades, or the loss of the material in the polar blisk. A performance shift was seen in the quasi-isotropic blisk as portions of the leading and trailing edges were lost. After the testing was completed, detailed inspections of the blisks were performed. The largest surprise was the polar blisk had a obvious crack in a single blade that was located nearly midspan which was not detected in test. The crack ran completely through the blade circumferenciary and through the radial length of the blade. However, the crack does not appear to extend into the blisk hub. Although the cause of the crack is still under investigation, the material appears to be tolerant of this crack, and other hairline cracks discovered under higher magnification. This bodies well for eventual use of this material in actual flight turbopumps where monolithic fracture toughness issues limit its use.

Genge, Gary G.↗

Nitrogen isotopic components in the early solar system

It is quite common to take the terrestrial atmospheric value of (15)N/(14)N (0.00366) as typical of nitrogen in the early solar system, but in fact there is little reason to suppose that this value had a nebula-wide significance. Indeed, it is not clear that there was a unique solar-system-wide (15)N/(14)N ratio, of whatever value. Here we review what is known about the distribution of the nitrogen isotopes among those solar-system objects that have been sampled so far and conclude that those isotopes reveal widespread inhomogeneity in the early solar system. Whether the isotopically distinct primordial components implied by this analysis were solid or gaseous or a mixture of both is not known. The isotopic composition of N in the Earth's mantle is controversial: estimates range from a 1.1 percent depletion in (15)N to a 1.4 percent enrichment. (Isotopic compositions will be expressed throughout as percent deviations from the terrestrial atmospheric value.) The present-day Martian atmosphere is characterized by a value of plus 62 percent but this enrichment in (15)N is attributed to selective loss of (14)N from the Martian exosphere. Modelling of this fractionation leads to an estimated primordial composition similar to the terrestrial atmospheric value, through the precision of this model-dependent result is unclear.

Kerridge, J. F.↗

Soil Carbon and Nutrient Changes Associated with Deforestation for Pasture in Southern Costa Rica

We assessed the effects of deforestation on soil carbon (C) and nutrient stocks in the premontane landscape near Las Cruces Biological Station in southern Costa Rica, where forests were cleared for pasture in the mid-1960s. We excavated six soil pits to a depth of 1 m in both pasture and primary forest, and found that C stocks were ~20 kg C per square meters in both settings. Nevertheless, soil delta C-13 suggests ~50 percent of the forest-derived soil C above 40 cm depth has turned over since deforestation. Soil nitrogen (N) and phosphorus (P) stocks derived from the soil pits were not significantly different between land uses (P = 0.43 and 0.61, respectively). At a larger spatial scale, however, the ubiquity of ruts produced by cattle-induced erosion indicates that there are substantial soil effects of grazing in this steep landscape. Ruts averaged 13 cm deep and covered ~45 percent of the landscape, and thus are evidence of the removal of 0.7 Mg C/ ha/yr, and 70, 9 and 40 kg/ha/yr of N, P and potassium (K), respectively. Subsoils in this region are ~10 times less C- and N-rich, and ~2 times less P- and K-rich than the topsoil. Thus, rapid topsoil loss may lead to a decline in pasture productivity in the coming decades. These data also suggest that the soil C footprint of deforestation in this landscape may be determined by the fate of soil C as it is transported downstream, rather than C turnover in situ.

soil carbon↗

Observations and theories related to Antarctic ozone changes

In 1985, there was a report of a large, sudden, and unanticipated decrease in the abundance of springtime Antarctic ozone over the last decade. By 1987, ozone decreases of more than 50 percent in the total column, and 95 percent locally between 15 and 20 km, had been observed. The scientific community quickly rose to the challenge of explaining this remarkable discovery; theoreticians soon developed a series of chemical and dynamical hypotheses to explain the ozone loss. Three basic theories were proposed to explain the springtime ozone hole. (1) The ozone hole is caused by the increasing atmospheric loadings of manmade chemicals containing chlorine (chlorofluorocarbons (CFC's) and bromine (halons)). These chemicals efficiently destroy ozone in the lower stratosphere in the Antarctic because of the special geophysical conditions, of an isolated air mass (polar vortex) with very cold temperatures, that exist there. (2) The circulation of the atmosphere in spring has changed from being predominantly downward over Antarctica to upward. This would mean that ozone poor air from the troposphere, instead of ozone rich air from the upper stratosphere, would be transported into the lower Antarctic stratosphere. (3) The abundance of the oxides of nitrogen in the lower Antarctic stratosphere is periodically enhanced by solar activity. Nitrogen oxides are produced in the upper mesosphere and thermosphere and then transported downward into the lower stratosphere in Antarctica, resulting in the chemical destruction of ozone. The climatology and trends of ozone, temperature, and polar stratospheric clouds are discussed. Also, the transport and chemical theories for the Antarctic ozone hole are presented.

Hartmann, D.↗

Long Term Degradation of Polyimide Composites

The durability of polymer matrix composites exposed to harsh environments is a major concern. Surface degradation and damage are observed in polyimide composites used in air at 125-300 C. It is believed that diffusion of oxygen into the material and oxidative chemical reactions are responsible. Previous work has characterized and modeled diffusion behavior, and thermogravimetric analyses (TGAS) have been carried out in nitrogen, air, and oxygen to provide quantitative information on thermal and oxidative reactions. However, the model developed using these data did not successfully extrapolate TGA data down to conditions seen in service. A test program that focuses on lower temperatures and makes use of isothermal tests was undertaken to achieve a better understanding of the degradation reactions under use conditions. A new, low-cost technique was developed to collect chemical degradation data for isothermal tests lasting over 200 hours in the temperature range 125-300 C. Results indicate complex behavior not captured by the previous model, including the presence of weight-adding reactions. Weight gain reactions dominated in the 125-225 C temperature range, while weight loss reactions dominated beyond 225 C. The data obtained from isothermal tests and earlier TGAs is used to develop an advanced model of the material behavior.

Patekar, Kaustubh A.↗

Analysis of particulates of comet nucleus samples: Possible use of olivine as indicator phase

The electron microprobe is a proven instrument for particulate analysis and modifications are possible for in situ analysis of particulates in ice at temperatures near that of liquid nitrogen. Present sample requirements allow for polished samples with 0.25 x 0.25 dimensions to be maintained in the sample chamber of a modern electron probe (CAMECA SX-50) at a temperature of -150 C; larger samples are possible but at higher temperatures as determined by thermal conductivity. The major problem is transport and insertion of samples into the instrument through vacuum interlocks. The manufacturer of the above microprobe has designed an exchange mechanism to allow storage and transport of samples previously prepared for their sample holder which attaches to their instrument allowing extraction and insertion of samples while maintaining -150 C temperature. An important test will be the capability of preparing polished surfaces of an ice-particulate sample without loss of particles and at low temperatures. While thin sections of water ice are routine, these are not examined for particulate material and are prepared at temperatures easily obtained in room-size volumes. Anticipated problems include rounding of small grains in the relatively soft ice matrix and the technical problem of dry polishing.

Steele, I. M.↗

Cassini-Huygens Probe Gas Chromatograph Mass Spectrometer (GCMS) Experiment: First Results

The Huygens Probe of the Cassini Huygens Mission entered the atmosphere of the moon Titan on January 14, 2005. The GCMS was part of the instrument complement on the probe to measure in situ the chemical composition of the atmosphere during the probe descent and to support the Aerosol Collector Pyrolyzer (ACP) experiment by serving as detector for the pyrolization products. The GCMS collected data from an altitude of 146 km to ground impact for a time interval of 2hours and 37minutes. The Probe and the GCMS survived the ground impact and collected data for 1hour and 9 minutes on the surface in the near surface environment until signal loss by the orbiter. The major constituents of the lower atmosphere were found to be N2 and CH4. The methane-mixing ratio was found to increase below the turbopause, about 35 km altitude, monotonically toward the surface to levels near saturation. After surface impact a steep increase of the mixing ratio was observed suggesting evaporation of surface condensed methane due to heating by the GCMS sample inlet heater. Other constituents were found to be in very low concentrations, below ppm levels. The presence of Argon 40 was confirmed. The results for the other noble gases are still being evaluated. Other hydrocarbons and nitriles were also observed and quantitative evaluation is in progress. Preliminary ratios for the major carbon and nitrogen isotopes were computed from methane and molecular nitrogen measurements. The instrument collected 5634 mass spectra during descent and 2692 spectra on the ground over a range of m/z from 2 to 141. Eight gas chromatograph samples were taken during the descent and two on the ground.

Niemann, H.↗

Characterization of simulated small-droplet fuel sprays

A two-fluid pneumatic atomizer operating at relatively high liquid and gas pressures produced water sprays that simulated small-droplet clouds of liquid fuel for use in studying vaporization and fuel-air mixing effects on combustor performance and emissions. To characterize the sprays, a scattered-light scanning instrument was developed and measurements of volume median or volume mean diameter, D sub V.5, were correlated with D sub O, W sub w, and W sub n, i.e., orifice diameter, water, and nitrogen gas flow rates, respectively, to give the general expression: D sub v.5 approx. (D sub o sup 0.2) (W sub w sup m) (W sub n sup n), which yields D sub v.5 = 45 (D sub o sup 0.2) (W sub w sup 0.2) (W sub w sup - 1.2). Values of D sub o, W sub w, and W sub n are in centimeters and grams/second, respectively. Farther downstream at an axial distance of 6.7 cm, exponent m increased from 0.2 to 0.4 and exponent n decreased from -1.2 to -1.0 and at a distance of 25 cm downstream of the atomizer, n decreased to -0.8. The increase in exponent m and decrease in exponent n was attributed to a loss of very small droplets from the spray due primarily to vaporization and diffusion effects on clouds of small droplets traveling a distance of 25 cm.

Ingebo, R. D.↗

Characterization of simulated small-droplet fuel sprays

A two-fluid pneumatic atomizer operating at relatively high liquid and gas pressures produced water sprays that simulated small-droplet clouds of liquid fuel for use in studying vaporization and fuel-air mixing effects on combustor performance and emissions. To characterize the sprays, a scattered-light scanning instrument was developed and measurements of volume median or volume mean diameter, D sub V.5, were correlated with D sub O, W sub w, and W sub n, i.e., orifice diameter, water, and nitrogen gas flow rates, respectively, to give the general expression: D sub v.5 approx. (D sub O sup 0.2) (W sub w sup m) (W sub n sup n), which yields D sub v.5 = 45 (D sub o sup 0.2) (W sub w sup 0.2) (W sub w sup -1.2). Values of D sub 0, W sub w, and W sub n are in centimeters and grams/second, respectively. Farther downstream at an axial distance of 6.7 cm, exponent m increased from 0.2 to 0.4 and exponent n decreased from -1.2 to -1.0 and at a distance of 25 cm downstream of the atomizer, n decreased to -0.8. The increase in exponent m and decrease in exponent n was attributed to a loss of very small droplets from the spray due primarily to vaporization and diffusion effects on clouds of small droplets traveling a distance of 25 cm.

Ingebo, R. D.↗

Fast Airborne Aerosol Size and Chemistry Measurements with the High Resolution Aerosol Mass Spectrometer during the MILAGRO Campaign

The concentration, size, and composition of non-refractory submicron aerosol (NR-PM(sub l)) was measured over Mexico City and central Mexico with a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) onboard the NSF/NCAR C-130 aircraft as part of the MILAGRO field campaign. This was the first aircraft deployment of the HR-ToF-AMS. During the campaign the instrument performed very well, and provided 12 s data. The aerosol mass from the AMS correlates strongly with other aerosol measurements on board the aircraft. Organic aerosol (OA) species dominate the NR-PM(sub l) mass. OA correlates strongly with CO and HCN indicating that pollution (mostly secondary OA, SOA) and biomass burning (BB) are the main OA sources. The OA to CO ratio indicates a typical value for aged air of around 80 microg/cubic m (STP) ppm(exp -1). This is within the range observed in outflow from the Northeastern US, which could be due to a compensating effect between higher BB but lower biogenic VOC emissions during this study. The O/C atomic ratio for OA is calculated from the HR mass spectra and shows a clear increase with photochemical age, as SOA forms rapidly and quickly overwhelms primary urban OA, consistent with Volkamer et al. (2006) and Kleinman et al. (2008). The stability of the OA/CO while O/C increases with photochemical age implies a net loss of carbon from the OA. BB OA is marked by signals at m/z 60 and 73, and also by a signal enhancement at large m/z indicative of larger molecules or more resistance to fragmentation. The main inorganic components show different spatial patterns and size distributions. Sulfate is regional in nature with clear volcanic and petrochemical/power plant sources, while the urban area is not a major regional source for this species. Nitrate is enhanced significantly in the urban area and immediate outflow, and is strongly correlated with CO indicating a strong urban source. The importance of nitrate decreases with distance from the city likely due to evaporation. BB does not appear to be a strong source of nitrate despite its high emissions of nitrogen oxides, presumably due to low ammonia emissions. NR-chloride often correlates with HCN indicating a fire source, although other sources likely contribute as well. This is the first aircraft study of the regional evolution of aerosol chemistry from a tropical megacity.

DeCarlo, P. F.↗

Long Term Degradation of Resin for High Temperature Composites

The durability of polymer matrix composites exposed to harsh environments is a major concern. Surface degradation and damage are observed in polyimide composites used in air at 125 to 300 C. It is believed that diffusion of oxygen into the material and oxidative chemical reactions in the matrix are responsible. Previous work has characterized and modeled diffusion behavior, and thermogravimetric analyses (TGAs) have been carried out in nitrogen, air, and oxygen to provide quantitative information on thermal and oxidative reactions. However, the model developed using these data was not able to capture behavior seen in isothermal tests, especially those of long duration. A test program that focuses on lower temperatures and makes use of isothermal tests was undertaken to achieve a better understanding of the degradation reactions under use conditions. A new low-cost technique was developed to collect chemical degradation data for isothermal tests lasting over 200 hr in the temperature range 125 to 300 C. Results indicate complex behavior not captured by the previous TGA tests, including the presence of weight-adding reactions. Weight gain reactions dominated in the 125 to 225 C temperature range, while weight loss reactions dominated beyond 225 C. The data obtained from isothermal tests was used to develop a new model of the material behavior. This model was able to fully capture the behavior seen in the tests up to 275 C. Correlation of the current model with both isothermal data at 300 C and high rate TGA test data is mediocre. At 300 C and above, the reaction mechanisms appear to change. Attempts (which failed) to measure non-oxidative degradation indicate that oxidative reactions dominate the degradation at low temperatures. Based on this work, long term isothermal testing in an oxidative atmosphere is recommended for studying the degradation behavior of this class of materials.

Patekar, Kaustubh A.↗

The Coupling of ClONO2, ClO, and NO2 in the Lower Stratosphere From in Situ Observations Using the NASA ER-2 Aircraft

The first in situ measurements of ClONO2 in the lower stratosphere, acquired using the NASA ER-2 aircraft during the Polar Ozone Loss in the Arctic Region in Summer (POLARIS) mission, are combined with simultaneous measurements of ClO, NO2, temperature, pressure, and the calculated photolysis rate coefficient (J(sub ClONO2)) to examine the balance between production and loss of ClONO2. The observations demonstrate the ClONO2 photochemical steady state measurement, [ClONO2](sup PSS) = k[ClO][No2]/J(sub ClONO2), is in good agreement with the direct measurement, [ClONO2](sup MEAS). For the bulk of the data (80%), where T > 220 K and latitudes > 45 N, [ClONO2](sup PPS) = 1.15 +/- 0.36(1-sigma)[ClONO2](sup MEAS), while for T< 220 K and latitudes < 45 N, the result is somewhat less at 1.01 +/- 0.30. The cause of the temperature and/or latitude trend is unidentified. These results are independent of solar zenith angle and air density, thus there is no evidence in support of a pressure-dependent quantum yield for photodissociation of ClONO2 at wavelengths > 300 nm. These measurements confirm the mechanism by which active nitrogen (NOx = NO + NO2) controls the abundance of active chlorine (Clx = ClO + Cl) in the stratosphere.

Stimpfle, R. E.↗

Revisiting the Effectiveness Of HCHO/NO2 Ratios for Inferring Ozone Sensitivity to Its Precursors Using High Resolution Airborne Remote Sensing Observations in A High Ozone Episode During the KORUS-AQ Campaign

The nonlinear chemical processes involved in ozone production (P(O3)) have necessitated using proxy indicators to convey information about the primary dependence of P(O3) on volatile organic compounds (VOCs) or nitrogen oxides (NOx). In particular, the ratio of remotely sensed columns of formaldehyde (HCHO) to nitrogen dioxide (NO2) has been widely used for studying O3 sensitivity. Previous studies found that the errors in retrievals and the incoherent relationship between the column and the near-surface concentrations are a barrier in applying the ratio in a robust way. In addition to these obstacles, we provide calculational-observational evidence, using an ensemble of 0-D photochemical box models constrained by DC-8 aircraft measurements on an ozone event during the Korea-United States Air Quality (KORUS-AQ) campaign over Seoul, to demonstrate the chemical feedback of NO2 on the formation of HCHO is a controlling factor for the transition line between NOx-sensitive and NOx-saturated regimes. A fixed value (~2.7) of the ratio of the chemical loss of NOx (LNOx) to the chemical loss of HO2+RO2 (LROx) perceptibly differentiates the regimes. Following this value, data points with a ratio of HCHO/NO2 less than 1 can be safely classified as NOx-saturated regime, whereas points with ratios between 1 and 4 fall into one or the other regime. We attribute this mainly to the HCHO-NO2 chemical relationship causing the transition line to occur at larger (smaller) HCHO/NO2 ratios in VOC-rich (VOC-poor) environments. We then redefine the transition line to LNOx/LROx~2.7 that accounts for the HCHO-NO2 chemical relationship leading to HCHO = 3.7 × (NO2 – 1.14 × 1016 molec.cm-2). Although the revised formula is locally calibrated (i.e., requires for readjustment for other regions), its mathematical format removes the need for having a wide range of thresholds used in HCHO/NO2 ratios that is a result of the chemical feedback. Therefore, to be able to properly take the chemical feedback into consideration, the use of HCHO = a × (NO2 – b) formula should be preferred to the ratio in future works. We then use the Geostationary Trace gas and Aerosol Sensor Optimization (GeoTASO) airborne instrument to study O3 sensitivity in Seoul. The unprecedented spatial (250 × 250 m2) and temporal (~every 2 h) resolutions of HCHO and NO2 observations form the sensor enhance our understanding of P(O3) in Seoul; rather than providing a crude label for the entire city, more in-depth variabilities in chemical regimes are observed that should be able to inform mitigation strategies correspondingly.

KORUS-AQ; formaldehyde; NOx; VOC; OMI; GeoTASO; oz↗

Spectroscopic Evidence Against Nitric Acid Trihydrate in Polar Stratospheric Clouds

Heterogeneous reactions on polar stratospheric clouds (PSC's) play a key role in the photochemical mechanism thought to be responsible for ozone depletion in the Antarctic and Arctic. Reactions of PSC particles activate chlorine to forms that are capable of photochemical ozone destruction, and sequester nitrogen oxides (NOx) that would otherwise deactivate the chlorine. Although the heterogeneous chemistry is now well established, the composition of the clouds themselves is uncertain. It is commonly thought that they are composed of nitric acid trihydrate, although observations have left this question unresolved. Here we reanalyse infrared spectra of type 1 PSCs obtained in Antarctica in September 1987, using recently measured optical constants of the various compounds that might be present in PSCs. We find these PSCs were not composed of nitric acid trihydrate but instead had a more complex compositon, perhaps that of a ternary solution. Because cloud formation is sensitive to their composition, this finding will alter our understanding of the locations and conditions in which PSCs form. In addition, the extent of ozone loss depends on the ability of the PSCs to remove NOx permanently through sedimentation, The sedimentation rates depend on PSC particle size which in turn is controlled by the composition and formation mechanism.

Toon, Owen B.↗