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At least 91 records · Page 5

Copernicus observational searches for OH and H2O in diffuse clouds

An intensive search for OH and H2O in the directions of Sigma Sco, Alpha Cam, and Omicron Per was undertaken with the Copernicus satellite. Multiple scans were carried out over the wavelength region for the expected absorption features due to the OH D-X and H2O C-X transitions. The feature due to OH was possibly detected toward Sigma Sco, and only an upper limit can be given toward Alpha Cam. H2O was not detected in any of the stars at the signal level accumulated. The OH abundance toward Sigma Sco and the respective lower limits for the OH/H2O ratios are discussed with regard to the extant models for the steady-state abundances of OH and H2O, and shown not to be inconsistent with ion-molecule schemes.

Smith, W. H.↗

Copernicus observational searches for OH and H2O in diffuse clouds

An intensive search for OH and H2O in the directions of sigma Sco, alpha Cam, and micron Per was undertaken with the Copernicus satellite. Multiple scans were carried out over the wavelength region for the expected absorption features due to the OH D-X and H2O C-X transitions. The feature due to OH was detected marginally towards sigma Sco, and only an upper limit can be given towards alpha Cam. H2O was not detected in any of the stars at the signal level accumulated. The OH abundance towards sigma Sco and the respective lower limits for the OH/H2O ratios are discussed with regard to the extant models for the steady state abundances of OH and H2O, and shown not to be inconsistent with ion-molecule schemes.

Smith, W. H.↗

Observations of far-infrared transitions between excited states of OH

In observations of the Kleinmann-Low Nebula were detected of Orion 84.42 and 84.60 micron transitions between the P-2 sub 3/2 and Pi-2 sub 3/2 (J = 5/2) levels of OH with respective fluxes of 1.0 + or - 0.3 to the minus 17th power and 1.4 + or - 0.4 x 10 to the minus 17th power W cm/sq. When compared to 119 micron flux levels of OH and 153 micron flux levels of these radicals by Viscuso, these results suggest appreciable self-absorption of OH line radiation within the Nebula. It is probable that the CO emission due to the J = 31 yields 30 rotational transition at 84.411 micron makes a substantial contribution to the observed 84.42 micron flux, and that it also is at least partially absorbed at the 84.42 micron OH transition frequency. The 88.55 and 88.78 micron (J = 9/2 to 7/2) transitions of CH also were sought, but yielded only to upper limits of 3 x 10 to the minus 18th power W /sq cm each. A search of W3-IRS5 yields upper limits to the 84.42 micron OH and 87.19 micron CO (J = 30 to 29) transitions of 2 x 10 minus 18th power W cm/2.

Viscuso, P. J.↗

Observation of far-infrared transitions between excited states of OH

Spectra of the Kleinmann-Low nebula in Orion detected the 84.42 and 84.60 micron transitions between the 2Pi(3/2) J = 7/2 and 2Pi(3/2) J = 5/2 levels of OH with respective fluxes of 1 x 10 to the -17th and 1.4 x 10 to the -17th W/sq cm. When compared to the 119 micron flux levels of OH discussed by Watson (1982) and the 163 micron flux levels of OH by Viscuso et al. (1985), these results suggest appreciable self-absorption of OH line radiation within the nebula. The CO emission due to the J = 31 to 30 rotational transition at 84.411 microns makes a substantial contribution to the observed 84.22 micron flux, and is probably at least partially absorbed at the 84.42 micron OH transition frequency.

Viscuso, P. J.↗

Atmospheric CH4, CO and OH from 1860 to 1985

Studies have shown that atmospheric methane, CO and the gaseous OH radical are interdependent: if CH4, CO or OH is perturbed, background concentrations of the other two constituents are affected. Perturbations to OH alter photooxidation rates of numerous natural and anthropogenic trace gases and affect lifetimes of those species that pass from the earth's surface to the free troposphere and stratosphere. It is now known that global atmospheric methane concentrations are increasing; less definite data suggest that carbon monoxide is also increasing. Even before the measurements reported in nine literature references, modeling studies of CH4-CO-OH coupling had led to predictions (Chameides, Liu and Ciceronne, 1977; Sze, 1977; and Hameed, Pinto and Stewart 1979) of future increases of CH4 and CO. A photochemical model is used to look backwards in time by simulating the trace-gas composition of the unpolluted troposphere at the start of the industrial era (taken as 1860) and at intervals up to 1985. It is found that the OH concentration in the background troposphere has decreased significantly and O3 has increased due to increases of CH4 and CO; calculated changes depend on temporal trends of NOx (NOx = NO + NO2), for which no historical data are available. The calculations allow recent trace-gas trends affecting background chemistry and climate to be viewed in a longer-term context.

Thompson, A. M.↗

6 CM OH absorption in megamaser galaxies

Absorption in the 2Pi sub 1/2 J = 1/2 Lambda doublet transitions of OH, 182 K above the ground state, is detected in the megamaser galaxies IC 4553 (Arp 220), MK 231, MK 273, MGC 3690, and IRAS 17208-0014. The 4660, 4751, and 4766 MHz lines have intensity ratios moderately deviating from the LTE values (1:2:1). The OH rotational temperatures appear to be close to the temperature of the dust, approx. 60 K. The common characteristics of these galaxies (absence of 6 cm inversion, the optical depths, the infrared properties, the systematic trends in the line parameters, and the rotational temperatures) all suggest that the same pump process is responsible for the 18 cm line inversion in the five megamaser sources. The inversion is probably not due to an excitation mechanism involving collisions with HI or H2. While excitation via photodissociation of H2O cannot entirely be ruled out, the most likely mechanism is considered to be to be a combination of the intense FIR field (populating higher excited OH rotational states) and the non-thermal radiation from the nuclei of the parent galaxies (affecting the excitation within the Lambda -doublets). According to an LVG model of the OH excitation of IC4553, the OH-cloud(s) have to be located close, within 200 to 300 pc, to the center of the galaxy. The excitation of the individual 18 cm lines depends critically on the effective background radiation field and hence on the galactocentric distance of the masing clump. With increasing distance first the 1720 MHz and then the 18 cm main line inversion is quenched, while 1612 MHz inversion is obtained up to approx. 600 pc. The 1612 MHz satellite line is predicted to be more intense than the 1720 MHz line. A critical test for our excitation model is to observe the 2 Pi 3/2 J = 5/2 Lambda-doublet transitions which are predicted to be detectable in absorption.

Henkel, C.↗

OH detection by Ford Motor Company

Two different methods for detection of OH are presented: a low pressure flow cell system and a frequency modulation absorption measurement. Using conventional absorption spectroscopy, detection limits were quoted of 1,000,000 OH molecules per cu cm using a 30-minute averaging time on the ground, and a 3-hour averaging time in the air for present apparatus in use. With the addition of FM spectroscopy at 1 GHz, a double-beam machine should permit detectable absorption of and an OH limit of 100,000 per cu cm in a 30-minute averaging time. In the low pressure system on which experiments are ongoing nonexponential time behavior was observed after the decay had progressed to about 0.3 of its original level; this was attributed to ion emission in the photomultiplier. A flame source with OH present at high concentration levels was used as a calibration. It was estimated that within the sampling chamber, 400,000 OH could be measured. With a factor-of-2 loss at the sampling orifice, this means detectability of 5 to 8 x 100,000 cu cm at the present time. This could be reduced by a factor of 2 in one hour averaging time; improvements in laser bandwidth and energy should provide another factor of 2 in sensitivity.

Wang, Charles C.↗

OH-transition metal bonding

The bonding in both CuOH and AgOH has a covalent component that leads to a bent structure. The larger electrostatic stabilization in CuOH leads to a larger D(e) (2.83 eV) compared with AgOH (2.20 eV). Using Ni5OH to model chemisorption of OH on a Ni surface, it is found that OH adsorption in the fourfold hollow of Ni(100) leads to an OH normal to the surface, while adsorption directly above a Ni atom leads to a tilted OH. These qualitative Ni5OH calculations allow for speculation on the observed variation of OH on metal surfaces.

Bauschlicher, Charles W., Jr.↗

Observations of the rotational transitions of OH from the Orion molecular cloud

A summary of observed rotationally excited, far infrared OH line emissions from Orion-KL made using the Kuiper Airborne Observatory is given, together with a list of the resulting publications, talks, and lectures based on this data. In addition, a paper is appended, particularly addressing the (16)OH and (18)OH emission from Orion-KL. The first detections of the (16)OH (2)pi(1/2) to (2)pi(3/2) J = 3/2(-) to 3/2(+) rotational cross-ladder transition (53.351 micrometer) and the (18)OH (2)pi(3/2) J = 5/2(+) to 3/2(-) rotational ground-state transition (120.1719 micrometer). It is found that both of these lines exhibit a P-Cygni profile.

Melnick, Gary J.↗

Velocity measurement in rocket exhaust and general aerodynamic flows by photolysis of H2O and laser induced fluorescence of OH

A 'tagging' approach in which the photolysis of H2O by an excimer laser creates a zone of enhanced OH concentration, while a second, pulsed-UV laser detects tagged-zone convection via time-delayed excitation of OH fluorescence, depends on the photodissociation process and the kinetics of OH decay (relative to velocity). For application to the fuel-rich, high supersonic Mach number exhaust flow of the SSME, the detection of OH is being accomplished with either a pulsed narrowband UV dye laser or a tunable XeCl excimer laser for excitation of an OH 0-0 band transition, while the two-photon photolysis of H2O is conducted by focusing an injection-locked KrF excimer laser into the flow.

Boedeker, Laurence R.↗

Collisional effects in laser detection of tropospheric OH

The use of laser-induced fluorescence to measure OH in the troposphere is discussed. It is noted that quantitative laser detection of OH requires knowledge of collisional processes affecting the measurements and interference effects due to OH generated by laser photolytic processes. Collisions induce quenching of the excited A-state, as well as vibrational and rotational energy transfer in the excited and ground states. It is noted that the state-specific nature of these processes is important, especially the rotational level dependence of quenching and vibrational transfer in excited OH. Also important is the temperature dependence according to which quenching cross sections sharply increase with decreasing temperature. Laboratory experiments studying these collisional processes are described, and their implications for laser detection of tropospheric OH are examined.

Crosley, David R.↗

Warm neutral halos around molecular clouds. V - OH (1665 and 1667 MHz) observations

Ten strip maps of 1665- and 1667-MHz OH emission, traversing the outer boundaries of five molecular clouds, were made. The OH emission is found to be significantly extended relative to CO, from which it inferred that OH is to be found in abundance in the shell of partly atomic, partly molecular gas surrounding the dense molecular clouds. The fractional OH abundance is calculated using existing H I and CO observations, and detailed source models which include a complete chemistry network and a radiative transfer code. It is concluded that the extended OH is formed, not by the exothermic reaction of O with H3(+), but by the endothermic reaction, H(+) + O yields H + O(+).

Wannier, Peter G.↗

Absolute determination of local tropospheric OH concentrations

Long path absorption (LPA) according to Lambert Beer's law is a method to determine absolute concentrations of trace gases such as tropospheric OH. We have developed a LPA instrument which is based on a rapid tuning of the light source which is a frequency doubled dye laser. The laser is tuned across two or three OH absorption features around 308 nm with a scanning speed of 0.07 cm(exp -1)/microsecond and a repetition rate of 1.3 kHz. This high scanning speed greatly reduces the fluctuation of the light intensity caused by the atmosphere. To obtain the required high sensitivity the laser output power is additionally made constant and stabilized by an electro-optical modulator. The present sensitivity is of the order of a few times 10(exp 5) OH per cm(exp 3) for an acquisition time of a minute and an absorption path length of only 1200 meters so that a folding of the optical path in a multireflection cell was possible leading to a lateral dimension of the cell of a few meters. This allows local measurements to be made. Tropospheric measurements have been carried out in 1991 resulting in the determination of OH diurnal variation at specific days in late summer. Comparison with model calculations have been made. Interferences are mainly due to SO2 absorption. The problem of OH self generation in the multireflection cell is of minor extent. This could be shown by using different experimental methods. The minimum-maximum signal to noise ratio is about 8 x 10(exp -4) for a single scan. Due to the small size of the absorption cell the realization of an open air laboratory is possible in which by use of an additional UV light source or by additional fluxes of trace gases the chemistry can be changed under controlled conditions allowing kinetic studies of tropospheric photochemistry to be made in open air.

Armerding, Wolfgang↗

High-Altitude Aircraft and Balloon-Borne Observations of OH, HO2, ClO, BrO, NO2, ClONO2, ClOOCl, H2O, and O3 in Earth's Stratosphere

Using observations from balloon-borne instruments and aircraft-borne instruments the investigation arrived at the following developments.: (1) Determination of the dominant catalytic cycles that destroy ozone in the lower stratosphere; (2) The partial derivatives of the rate limiting steps are observables in the lower stratosphere; (3) Recognition that the "Low NOx" condition is the regime that holds the greatest potential for misjudgement of Ozone loss rates; (4) Mapping of the Bromine radical contribution to the ozone destruction rate in the lower stratosphere; (5) Observation of OH, HO2 and ClO in the plume of the Concorde SST in the stratosphere; (6) Determination of the diurnal behavior of OH in the lower stratosphere; (7) Observed OH and H02 in the Troposphere and the interrelationship between Ozone and OH, HO2, CO and NO; (8) Analysis of the Catalytic Production of Ozone and Reactions that Couple OH and H02 in the Troposphere; (9) The continuing development of the understanding of the Tropopause temperatures, water vapor mixing ratios, and vertical advection and the mixing in of mid-latitude air; (10) Performed Multiple Tracer Analyses as a diagnostic of water vapor intrusion into the "Middle World" (i.e., the lowermost stratsophere); (11) Flight testing of a new instrument for the In Situ detection of ClON02 from the ER-2; (12) Laser induced fluorescence detection of NO2. There is included an in depth discussion of each of these developments and observations.

Anderson, James G.↗

Experimental and Computational Study fo CH, CH*, and OH* in an Axisymmetric Laminar Diffusion Flame

In this study, we extend the results of previous combined numerical and experimental investigations of an axisymmetric laminar diffusion flame in which difference Raman spectroscopy, laser-induced fluorescence (LIF), and a multidimensional flame model were used to generate profiles of the temperature and major and minor species. A procedure is outlined by which the number densities of ground-state CH (X(sup 2)II) excited-state CH (A(sup 2)Delta, denoted CH*), and excited-state OH (A(sup 2)Sigma, denoted OH*) are measured and modeled. CH* and OH* number densities are deconvoluted from line-of-sight flame-emission measurements. Ground-state CH is measured using linear LIF. The computations are done with GRI Mech 2.11 as well as an alternate hydrocarbon mechanism. In both cases, additional reactions for the production and consumption of CH* and OH* are added from recent kinetic studies. Collisional quenching and spontaneous emission are responsible for the de-excitation of the excited-state radicals. As with our previous investigations, GRI Mech 2.11 continues to produce very good agreement with the overall flame length observed in the experiments, while significantly under predicting the flame lift-off height. The alternate kinetic scheme is much more accurate in predicting lift-off height but overpredicts the over-all flame length. Ground-state CH profiles predicted with GRI Mech 2.11 are in excellent agreement with the corresponding measurements, regarding both spatial distribution and absolute concentration (measured at 4 ppm) of the CH radical. Calculations of the excited-state species show reasonable agreement with the measurements as far as spatial distribution and overall characteristics are concerned. For OH*, the measured peak mole fraction, 1.3 x 10(exp -8), compared well with computed peaks, while the measured peak level for CH*, 2 x 10(exp -9), was severely underpredicted by both kinetic schemes, indicating that the formation and destruction kinetics associated with excited-state species in flames require further research.

Walsh, K. T.↗

The NO(x)-HNO3 System in the Lower Stratosphere: Insights from In Situ Measurements and Implications of the J(HNO3)-[OH] Relationship

During the 1997 Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) mission, simultaneous in situ observations of NOx and HOx radicals, their precursors, and the radiation field were obtained in the lower stratosphere. We use these observations to evaluate the primary mechanisms that control NOx-HNO3 exchange and to understand their control over the partitioning between NO2 and HNO3 in regions of continuous sunlight. We calculate NOx production (PNOx) and loss (LNOx) in a manner directly constrained by the in situ measurements and current rate constant recommendations, using approaches for representing albedo, overhead O3 and [OH] that reduce model uncertainty. We find a consistent discrepancy of 18% between modeled rates of NOx production and loss (LNOx = 1.18P(sub NOx)), which is within the measurement uncertainty of +/- 27%. The partitioning between NOx production processes is [HNO3 + OH (41 +/- 2)%; HNO3 + hv (59 +/- 2)%] and between NOx loss processes is [NO2 + OH, 90% to >97%; BrONO2 + H2O, 10% to <3%]. The steady-state description of NOx-HNO3 exchange reveals the significant influence of the tight correlation between the photolysis rate of HNO3 and [OH] established by in situ measurements throughout the lower stratosphere. Parametrizing this relationship, we find: (1) the steady-state value of [NO2](sub 24h-avg)/[HNO3] in the continuously sunlit, lower stratosphere is a function only of temperature and number density; and (2) the partitioning of NOx production between HNO3 + OH and HNO3 + hv is nearly constant throughout most of the lower stratosphere. We describe a methodology (functions of latitude, day, temperature, and pressure) for accurately predicting the steady-state value of [NO2](sub 24h-avg)/[HNO3] and the partitioning of NOx production within these regions. The results establish a metric to compare observations of [NO2](sub 24h-avg)/[HNO3] within the continuously sunlit region and provide a simple diagnostic for evaluating the accuracy of models that attempt to describe the coupled NOx-HOx photochemistry in the lower stratosphere.

Perkins, K. K.↗

Establishing the Dependence of [HO2]/[OH] on Temperature, Halogen Loading, O3, and NO(x) Based on in Situ Measurements from the NASA ER-2

In situ observations of OH and HO2 from the Airborne Southern Hemisphere Ozone Experiment/Measurements for Assessing the Effects of Stratospheric Aircraft (ASHOE/MAESA), Stratospheric TRacers of Atmospheric Transport (STRAT), and Polar Ozone Loss in the Arctic Region in Summer (POLARIS) NASA ER-2 field campaigns are used to examine the partitioning of HO(x) in the lower stratosphere (tropopause to approx.21 km) and upper troposphere (approx.10 km to tropopause). These measurements span a latitude range from 70degS to 90degN and a variety of atmospheric conditions as a result of seasonal changes and altitude. The response of the observed [HO2]/[OH] to changes in temperature, [03], [CO], [NO], [CIO], and [BrO] is investigated. The measured ratio is accurately described (approx.+/-10%) by a steady-state model constrained by the measured mixing ratios of O3, CO, NO, CIO, and BrO, where the model is valid for conditions of HO(x) cycling much faster than HO(x) production and loss. The concentration of HO2 depends on [OH], which, to first order, has been observed to be a simple function of the solar zenith angle in the lower stratosphere. The partitioning between OH and HO2 is controlled by the local chemistry between the HO, radicals and O3, CO, NO, CIO, and BrO. The response of [HO(x)] to changes in [NO(x)] and [O3] is demonstrated. Further observations are necessary to illustrate the response of HO(x) to changes in halogen concentrations. A quantitative understanding of [HO2]/[OH] is important, since many of the reactions that control this ratio are directly involved in catalytic removal of O3 in the lower stratosphere and production of O3 in the upper troposphere.

Lanzendorf, E. J.↗

Vector-averaged gravity-induced changes in cell signaling and vitamin D receptor activity in MG-63 cells are reversed by a 1,25-(OH)2D3 analog, EB1089

Skeletal unloading in an animal hindlimb suspension model and microgravity experienced by astronauts or as a result of prolonged bed rest causes site-specific losses in bone mineral density of 1%-2% per month. This is accompanied by reductions in circulating levels of 1,25-(OH)(2)D(3), the active metabolite of vitamin D. 1,25-(OH)(2)D(3), the ligand for the vitamin D receptor (VDR), is important for calcium absorption and plays a role in differentiation of osteoblasts and osteoclasts. To examine the responses of cells to activators of the VDR in a simulated microgravity environment, we used slow-turning lateral vessels (STLVs) in a rotating cell culture system. We found that, similar to cells grown in microgravity, MG-63 cells grown in the STLVs produce less osteocalcin, alkaline phosphatase, and collagen Ialpha1 mRNA and are less responsive to 1,25-(OH)(2)D(3). In addition, expression of VDR was reduced. Moreover, growth in the STLV caused activation of the stress-activated protein kinase pathway (SAPK), a kinase that inhibits VDR activity. In contrast, the 1,25-(OH)(2)D(3) analog, EB1089, was able to compensate for some of the STLV-associated responses by reducing SAPK activity, elevating VDR levels, and increasing expression of osteocalcin and alkaline phosphatase. These studies suggest that, not only does simulated microgravity reduce differentiation of MG-63 cells, but the activity of the VDR, an important regulator of bone metabolism, is reduced. Use of potent, less calcemic analogs of 1,25-(OH)(2)D(3) may aid in overcoming this defect. Copyright 2002 Elsevier Science Inc.

Foton Project↗