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At least 55 records · Page 3

Radio observation of comet Meier /1978f/ in 18-cm OH lines

Observations of 18-cm OH spectral lines in comet Meier (1978f) with the 1000-ft. Arecibo telescope show spatial resolution of the OH coma by the 2.9 arcmin beam (=3.7 x 10 to the 5th km). The data agree with predictions of the solar Fraunhofer spectrum-pumping theory of comet OH excitation. On the assumption that the OH parent molecule (e.g., H2O) has a Haser-model scale length of about 1.0 x 10 to the 5th km at heliocentric distance 1 AU, an OH scale length of less than 10 to the 6th km, and probably near 1.0 x 10 to the 5th km is derived. Assuming a recently calculated value of the OH lifetime and the solar radiative pumping model, the results indicate an OH production rate of 10 to the 29th Kayser at heliocentric distance 2 AU.

Giguere, P. T.↗

The two-dimensional diagnostic model for tropospheric OH - An uncertainty analysis

Tropospheric OH is believed to play a major role in atmospheric photochemistry, and, via its chemical interactions OH ultimately may affect the climate, stratospheric ozone levels, and the pH of rain. A valuable tool for predicting the global OH abundance as a function of latitude and altitude is the two-dimensional diagnostic model for tropospheric OH. This model can also be applied to budget studies of species which interact with OH, such as CH4, CO, and O3. In addition to laboratory-obtained kinetic data, important variables include the rate constants for several reactions, the rate of heterogeneous removal of soluble species, and the global abundance and spatial variability in H2O, O3, CO, and NOx. The uncertainties in these parameters imply over a factor of 3 variability in the calculated global OH concentration as well as significant uncertainties in the latitudinal and vertical OH distribution.

Chameides, W. L.↗

OH radio observations of Comet Halley

Results of OH observations of P/Halley obtained with the NRAO 43 m antenna between July 1985 and May 1986 are presented. Using Radio Model 1986a, the OH production rate derived from these data follows an rh(-2) law for heliocentric distances in the range 0.6 to 2.1 AU. Comparison of radio OH production rates to those estimated by UV techniques continues to show that the radio technique finds systematically lower production rates. Observations of the OH line shape show that the line width increases as the comet approaches perihelion, and that the broader line widths persist after perihelion out to at least rh = 1AU. Modeling of the profiles suggest that this may be accounted for through an increase in the velocity of the OH parent. The mean velocity of the OH emission (after correction for the OH Greenstein effect) is slightly blue shifted compared to the nucleus velocity and suggests that the outgassing from the nucleus is largely directed sunward.

Schloerb, F. Peter↗

Chemistry of OH in remote clouds and its role in the production of formic acid and peroxymonosulfate

The chemistry of OH in nonprecipitating tropospheric clouds was studied using a coupled gas phase/aqueous phase chemical model. The simulation takes into account the radial dependence of the concentrations of short lived aqueous phase species, in particular, O3(aq) OH(aq). Formic acid is shown to be rapidly produced by the aqueous phase reaction between H2C(OH)2 and OH, but HCOO(-) and OH, but HCOO(-) is in turn rapidly oxidized by OH(aq). The HCOOH concentration in cloud is shown to be strongly dependent on the pH of the cloud water; clouds with pH greater than 5 are not efficient HCOOH sources. A novel mechanism is proposed for the oxidation of S(IV) by OH(aq), with the main product predicted to be peroxymonosulfate, HSO5(-). The latter could contribute significantly to total cloud water sulfur.

Jacob, D. J.↗

In situ detection of tropospheric OH, HO2, NO2, and NO by laser-induced fluorescence in detection chambers at reduced pressures

For detection of OH and HO2, we have met or exceeded most of the goals of the proposal for this grant. We have succeeded in building a prototype instrument for the detection of OH and HO2 that has a detection sensitivity of about 2 x 10 exp 4 (OH molecules/cc)/(ct/s), about five times greater than proposed. The current minimum detectable OH of 1.4 x 10 exp 5 OH molecules/cc (S/N=2; 30 second integration) is less than half that proposed, and will be much lower once scattered light levels are reduced. The instrument displays other important properties. First, interfering signals from other gases and OH losses on the inlet appear to be small under laboratory and field conditions. Second, three different calibration methods, two external to the inlet, give similar results, to within 30 percent. Third, the chemical conversion efficiency of HO2 to OH by addition of reagent NO is better than 90 percent. All of these factors give us great confidence that this technique works. The instrument has gone through several variations that have not affected its potential performance but have affected its use. We were able to undergo the first field trials away from State College in June 1992, when we were able to participate informally in the ROSE experiment in rural Alabama, a year ahead of the proposed schedule for field studies. Because this field experiment was our first and the data analysis was complicated by instrument instabilities, we have not yet released the observations. None-the-less, we have gained insight into instrument design. We have not yet completed all of the proposed work. The calibration systems need to be improved to reduce the 50 percent to 100 percent uncertainties to less than 30 percent. Interference signals from ambient gases and possible losses on the inlet under field conditions need to be quantified. Finally, the detection of NO2 and NO with laser induced fluorescence is only now being seriously pursued.

Brune, William H.↗

In situ detection of tropospheric OH and HO2 by laser-induced fluorescence in a detection chamber at low pressure

Just as in the method of Hard and O'Brien, ambient air is pulled through an approximately 1 mm diameter inlet into a detection chamber that is maintained at a pressure of 2.4 torr. The ambient air stream travels through the detection chamber with a velocity of greater than 100 m sec(exp -1) in a narrow stream, constrained by the addition of an inert gas flow (0.4 torr). The OH molecule is both excited and detected in the A(exp 2)Sigma (v' = 0) yields X(exp 2)II (v'' = 0) transition at 308 nm. Light from a copper vapor-pumped dye laser (rep. rate = 10kHz; pulse length = 20 ns; linewidth = .1 cm(exp -1), and average power = 15 mW), resonant with the Q(sub 1)(3) transition, is multipassed through a White cell and intercepts the air stream as 24 non-overlapping 2mm by 5mm beams. A fast microchannel plate detector is turned off during the laser pulse to prevent saturation of the detector due to Rayleigh and chamber scattering. It is turned on 30-100 nsec after the end of the laser pulse for 300 ns to collect resonance fluorescence from OH. HO2 is detected by chemical conversion to OH by reaction with reagent NO, followed by OH detection. Both the detection sensitivity and the inlet characteristics must be understood for any in situ instrument. For the calibration of the detection sensitivity, OH is produced quantitatively by the fast H + NO2 yields OH + NO reaction in a low pressure, flowing discharge tube connected to the detection chamber. The inlet transmission of OH inlet is calibrated separately.

Brune, William H.↗

Measurement of tropospheric OH by laser long-path absorption spectroscopy

OH-radicals are measured by laser long-path absorption spectroscopy. A tunable Nd:YAG/dye laser system provides broadbanded light at 308 nm. The beam is expanded to 0.3 m and pointed to an array of retroreflectors placed at a distance of 2800 m. The returning beam is separated from the outgoing beam and focused into a spectrometer of 0.3 pm resolution. A 1024 element diode array is used as a detector. The signal is digitized by a 14 bit analog to digital converter. The ultimate aim is a detection limit of 10(exp 5) molecules cm(exp -3) of OH. However the measurements in 1991 allowed only the recognition of OH absorptions corresponding to 3 x 10(exp 6) OH cm(exp -3) with a signal to noise ratio of two. Improvements of the instrument are under way. The advantages of the DOAS method are: the accuracy of detection is guaranteed because loss of OH radicals within the device is avoided, the rate of OH production by the device is negligible, and absorptions of other trace gases could be corrected for; and the calibration procedure for the device is fast and easy. The disadvantages of the system are: time resolution is about minutes because about ten spectra had to be added to keep the noise level down, the OH concentration is averaged along the whole light path, weight (500 kg) and size (4x4 m) of the device; and approximately 10 l/min of coolant and supply of 8 kW electrical power are necessary.

Kraft, Michael↗

Measurement of tropospheric OH and HO2 by laser-induced fluorescence at low pressure

The hydroxyl radical (OH) is the primary oxidant in the atmosphere, responsible for many photochemical reactions that affect both regional air quality and global climate change. Because of its high reactivity, abundances of OH in the troposphere are less than 1 part per trillion by volume (pptv) and thus difficult to measure accurately. This paper describes an instrument for the sensitive detection of OH in the troposphere using low-pressure laser-induced fluorescence. Ambient air is expanded into a low pressure detection chamber, and OH is both excited and detected using the A(sup 2) Epsilon(+)(v prime = 0) yields X(sup 2)Pi(v double prime = 0) transition near 308 nm. An injector upstream of the detection axis allows for the addition of reagent NO to convert ambient HO2 to OH using the fast reaction HO2 + NO yields OH + NO2. Using recent advances in laser and detector technologies, this prototype instrument is able to detect less than 1 x 10(exp 5) molecules/cu cm (0.004 pptv) of OH with an integration time of 30 s with negligible interferences.

Stevens, P. S.↗

Study of the rotational-level and temperature dependence of the quenching rate of OH fluorescence due to collisions with water molecules

The importance of the OH radical as an intermediate in many combustion reactions and in atmospheric photochemistry has led many researchers to use it as a diagnostic tool in these processes. The amount of data that has been acquired over the years for this radical is quite considerable. However, the quenching rate of OH with water molecules as a function of temperature and the rotational level of the excited state is not very well understood. The motivation of the studies undertaken is to bridge the gap between the low temperature measurements and the high temperature ones reported in the literature. The technique generally employed in these diagnostics is laser-induced fluorescence (LIF), through which rotational state selective excitation of the radical is possible. Furthermore, in a combustion medium, water is produced in abundance so that knowledge of the quenching rate of OH due to water molecules plays a crucial role in interpreting the data. In general, the precursor to an understanding of the collisional quenching rates of OH involves a characterization of the mode in which the radical is produced; the resulting rotational and translational distribution, followed by a measurement of the OH temperature; and ultimately obtaining the rate constants from the pressure dependence of the fluorescence signal. The experimental implementation of these measurements therefore involved, as a first step, the production of the OH radicals in a microwave discharge cell using water vapor as the source, wherein a hydrogen atom is abstracted from H2O. The second step involved the absorption of photons from the frequency-doubled output of a pulsed amplified, single-frequency cw ring dye laser. By tuning the laser to the peak of the transition and observing the fluorescence decay after the laser pulse, the lifetime of the OH in a particular rotational electronic state was determined (tau = 1.4 microseconds for Q(sub 1)(3)). Knowledge of this parameter led to a determination of the quenching rate. By varying the water vapor pressure in the cell and measuring the lifetime as a function of pressure a linear plot of the quenching rate as a function of pressure was obtained. Using this plot, the quenching cross section was deduced. It has therefore been possible to measure the local translational temperature and the quenching cross section with one laser system.

Koker, Edmond B.↗

Laboratory Kinetic Studies of OH and CO2 Relevant to Upper Atmospheric Radiation Balance

The purpose of this project was to quantify the rates of two processes which are crucial to our understanding of radiative energy balance in the upper atmosphere. The first process is radiative emission from vibrationally hot OH radicals following the H + O3 reaction in the upper mesosphere. The importance of this process depends strongly on the OH radiative emission coefficients. Our goal was to measure the OH permanent dipole moment in excited vibrational states and to use these measurements to construct an improved OH dipole moment function and improved radiative emission coefficients. Significant progress was made on these experiments including the construction of a supersonic jet source for vibrationally excited OH radicals. Unfortunately, our efforts to transport the OH radicals into a second lower pressure vacuum chamber were not successful, and we were unable to make improved dipole moment measurements for OH. The second key kinetic process which we attempted to quantify during this project is the rate of relaxation of bend-excited CO2 by oxygen atoms. Since excitation of the bending vibrational mode of CO2 is the major cooling mechanism in the upper mesosphere/lower thermosphere, the cooling rate of this region depends crucially on the rate of energy transfer out of this state. It is believed that the most efficient transfer mechanism is via atomic oxygen but the rate for this process has not been directly measured in the laboratory at appropriate temperatures and even the room temperature rate remains controversial. We attempted to directly measure the relaxation rate Of CO2 (010) by oxygen atoms using the discharge flow technique. This experiment was set up at Aerodyne Research. Again, significant progress was achieved in this experiment. A hot CO2 source was set up, bend excited CO2 was detected and the rate of relaxation of bend excited CO2 by He atoms was measured. Unfortunately, the project ran out of time before the oxygen atom kinetic studies could be implemented.

Nelson, David D.↗

Observation of Night OH in the Mesosphere

Satellite measurements from the Aura MLS instrument show a layer of OH near 82 km in the night. This layer confirms earlier measurements by ground-based LIDAR. The MLS and LIDAR observations measure OH in the lowest vibrational state and are distinct, but related chemically, from vibrationally-excited emission from the OH Meinel bands in the near infrared. The Caltech 1-D model has been extended to include vibrational dependence of OH reactions and shows good agreement with MLS OH data and with observations of the Meinel bands. The model shows a chemical lifetime of HO(x) that increases from less than a day at 80 km to over a month at 87 km. Above this altitude transport processes become an important part of HOx chemistry. The model predicts that ground state OH represents 99% of the total OH up to 84 km.

hydroxyl↗

Characterization of Reactant Refill and Detonation Wave Dynamics in a GOx/Natural-gas RDRE Using Simultaneous High Repetition-Rate OH-PLIF and Chemiluminescence

The potential application of rotating detonation engines (RDEs) in rocket combustors hinges on a fundamental understanding of detonation wave structure and injector characteristics with fuel and oxidizer compositions relevant in rocket systems. Simultaneous 300 kHz-rate broadband OH* chemiluminescence and OH-PLIF imaging is employed in a fully optically accessible Natural Gas-GOx rotating detonation rocket engine (RDRE) to visualize reactant refill dynamics and detonation wave structure. A custom-built KTP-type optical parametric oscillator (OPO) is coupled with a nanosecond high-repetition-rate burst-mode laser to output284 nm light and target excitation of the Q1(9) transition in the OH radical. Significant deflagrative burning is observed throughout the chamber as a consequence of the oxygen-rich environment. Trailing Azimuthal Reflected Shock Combustion (ARSC) system, similar to those in a H2-air RDE are observed, burning unburned reactants in the region immediately following the primary detonation wave. Contact burning, as indicated in this study, does not seem to be a primary loss mechanism. The simultaneous measurement of OH and OH* show that axial locations exist in the refill process where OH radicals are present, and produced due to shear layer induced deflagration, however, these zones do not produce excited state OH*. While a deeper understanding of the underlying physics in RDRE systems requires further investigation, this work highlights a first-of-its-kind visualization of the turbulent combustion product field and reactant refill characteristics in this highly unsteady environment.

Propulsion↗

OH in the Tropical Upper Troposhere and Its Relationships to Solar Radiation and Reactive Nitrogen

In situ measurements of [OH], [HO2] (square brackets denote species concentrations), and other chemical species were made in the tropical upper troposphere (TUT). [OH] showed a robust correlation with solar zenith angle. Beyond this dependence, however, [HOx] ([OH] + [HO2]) only weakly responds to variations in its source and sink species. For example, at a given SZA, [HOx] was broadly independent of the product of [O3] and [H2O]. This suggests that [OH] is heavily buffered in the TUT. One important exception to this result is found in regions with very low [O3], [NO], and [NOy], where [OH] is highly suppressed, pointing to the critical role of NO in sustaining OH in the TUT.

Tropical upper troposphere↗

Changes in Global Tropospheric OH Expected as a Result of Climate Change Over the Last Several Decades

The oxidizing capacity of the troposphere is controlled primarily by the abundance of hydroxyl radical (OH). The global mean concentration of OH, [OH]_GLOBAL, inferred from measurements of methyl chloroform, has remained relatively constant during the past several decades, despite rising levels of CH4 that should have led to a steady decline. Here we examine other factors that may have affected [OH]_GLOBAL, such as the changing overhead burden of stratospheric O3 using observations from OMI, TOMS and SBUV; rising tropospheric H2O using observations from AIRS and reanalysis fields from MERRA; and widening of the climatological tropics using widening rate estimates from the literature and global OH fields from the GEOS Chemistry-Climate Model. Our analysis suggests these factors may have contributed a positive trend to [OH]_GLOBAL large enough to counter the decrease due to CH4.

Climate Change↗

Upper bound and probable value of the rate constant of the reaction OH + HO2 yields H2O + O2

Discharge-flow experiments at 295 K of the OH + HO2 reaction are described in which excess O3 is added to OH through a movable injector; OH concentration is measured downstream by resonance fluorescence with and without addition of excess NO just upstream of the detector so that both OH concentration and OH concentration + HO2 concentration are determined independently. The data are compared with a computer model involving 12 reaction steps. A simple sensitivity analysis is carried out to establish how errors in the other 'known' rate constants affect the data fit. Best agreement is obtained between computer calculations and experiments when k1 for the OH + HO2 reaction is in the range 2-3 x 10 to the -11th cu cm/s. Values above about 5 x 10 to the -11th are very unlikely whereas those below about 1 x 10 to the -11th are less strongly excluded.

Chang, J. S.↗

A flash photolysis resonance fluorescence investigation of the reaction OH + CH3CCl3 yields H2O + CH2CCl3

The absolute rate constant for the reaction OH + CH3CCl3 yields H2O + CH2CCl3 was determined by the flash photolysis resonance fluorescence method from 253 to 363K. The use of the Arrhenius equation with atmospheric observational data on methyl chloroform nearly doubles the predicted tropospheric OH reaction sink strength for the removal of atmospheric gases whose lifetimes are controlled by OH. The increased use of methyl chloroform instead of the restricted trichloroethylene focused attention to its role in stratospheric ozone depletion, producing modeling analyses to determine the amount of released methyl chloroform which reaches the stratosphere. Since the primary atmospheric loss of CH3CCl3 is considered by reaction with OH radicals, these data are used to compute an average tropospheric OH concentration and the strength of the 'global tropospheric OH reaction sink'.

Kurylo, M. J.↗

Indirect determination of OH

Efforts are under way to develop indirect OH measurement techniques by utilizing tailor made reactive OH tracers to be employed in estimating OH abundance within air masses over a 100 to 1,000 km transport distance. By simultaneously releasing controlled quantities of reactive and inert tracers, both dispersion and OH abundance can be determined. When fully developed, the method will be used at all expected levels of atmospheric OH concentrations. A number of candidate reactive OH tracers were selected after a careful screening process. Laboratory work is now under way to affirm the applicability of the selected chemicals to real world conditions.

Singh, Hanwant B.↗

Measurements of OH(X2pi) in the stratosphere by high resolution UV spectroscopy

This paper reports the first results obtained using high spectral resolution imaging ultraviolet spectroscopy to observe multiple rotational lines of OH A2 Sigma-X2pi (0-0) band. A 9.2 A spectral segment from 3075.8 A to 3085.0 A is imaged at 0.08 A FWHM spectral resolution, allowing the simultaneous acquisition of six of the brightest OH resonance fluorescence emission lines. The high spectral resolution and low scattered light design of the instrument allows these lines to be detected above the Rayleigh scattered sunlight background. The technique permits remote sensing of stratospheric OH from a high altitude instrument. The instrument was flown to an altitude of 40 km on Aug. 25, 1983, and again on June 12, 1986, on scientific balloons from Palestine, TX. The OH profiles inverted from the limb scans made during these flights are reported here. These profiles represent the first measurements of the temporal variation of OH over an extended height range. The results demonstrate that the technique can be used to monitor OH from orbit.

Torr, D. G.↗