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Webster, C. R.

Publications and source records attributed to Webster, C. R..

At least 73 records · Page 4

In Situ Measurements of the ClO/HCl Ratio: Heterogeneous Processing on Sulfate Aerosols and Polar Stratospheric Clouds

Simultaneous in situ measurements of stratospheric ClO and HCl have been made for the first time, during numerous flights of the ER-2 aircraft covering latitudes 24-90 deg. N from October 1991 through March 1992. The ClO/HCl ratio is identified as a key indicator of heterogeneous processing both outside and within the Arctic polar vortex. For ClO mixing ratios below about 120 pptv, remarkably constant ClO/HCl values of about 15% characterize the lower stratosphere. The observed values are significantly higher than those derived from a 2-D model using either gas phase photochemistry alone (2%), or including heterogeneous sulfate chemistry (5-10%). During the Arctic early spring, after conversion of HCl into reactive chlorine has taken place, the vortex edge is poorly defined by ClO levels. Loss of HCl and its slow recovery following low-temperature polar heterogeneous chemistry distinguishes HCl as a new and unique dynamical tracer of PSC-processed air.

Webster, C. R.

In Situ Measurements of the ClO/HCl Ratio: Heterogeneous Processing on Sulfate Aerosols and Polar Stratospheric Clouds

Simultaneous in situ measurements of stratospheric ClO and HCl have been made for the first time, during numerous flights of the ER-2 aircraft covering latitudes 24-90 deg N from October 1991 through March 1992. The ClO/HCl ratio is identified as a key indicator of heterogeneous processing both outside and within the Arctic polar vortex. For ClO mixing ratios below about 120 pptv, remarkably constant ClO/HCl values of about 15% characterize the lower stratosphere. The observed values are significantly higher than those derived from a 2-D model using either gas phase photochemistry alone (2%), or including heterogeneous sulfate chemistry (5-10%). During the Arctic early spring, after conversion of HCl into reactive chlorine has taken place, the vortex edge is poorly defined by ClO levels. Loss of HCl and its slow recovery following low-temperature polar heterogeneous chemistry distinguishes HCl as a new and unique dynamical tracer of PSC-processed air.

Webster, C. R.

A Case Study of the Mountain Lee Wave Event of January 6, 1992

A mountain wave event, observed at the southern tip of Greenland on January 6, 1992, was corroborated by three experiments: the Meteorological Measurement System (MMS), the Microwave Temperature Profiler (MTP), and the Reactive Nitrogen Instrument (NO/NO(y)). Gravity wave signatures with classical phase relationship between wind and temperature were observed on both the outbound and inbound legs at different altitudes. The waves showed both vertically propagating and evanescent properties. Characteristics of the dominant wave mode are: wavelength approximately equals 35 km, vertical displacement approximately equals 0.8 km, and peak-to-peak vertical wind approximately equals 6 ms-1. With the prevailing wind at approximately equals 37 m/s, the stratospheric temperature was reduced by 6 K to 195.5 K within 8 minutes. The implication and potential impact of mountain lee waves on the formation of polar stratospheric clouds (PSC's) are discussed.

Chan, K. R.

Chlorine chemistry on polar stratospheric cloud particles in the Arctic winter

Simultaneous in situ measurements of hydrochloric acid (HCl) and chlorine monoxide (ClO) in the Arctic winter vortex showed large HCl losses of up to 1 ppbv, which were correlated with high ClO levels of up to 1.4 ppbv. Air parcel trajectory analysis identified that this conversion of inorganic chlorine occurred at air temperatures of less than 196 -/+ 4 kelvin. High ClO was always accompanied by loss of HCl mixing ratios equal to 1/2(ClO+ 2Cl2O2). These data indicate that the heterogeneous reaction HCl + ClONO2 - Cl2 + HNO3 on particles of polar stratospheric clouds establishes the chlorine partitioning, which, contrary to earlier notions, begins with an excess of ClONO2, not HCl.

Webster, C. R.

Chemical Loss of Ozone in the Arctic Polar Vortex in the Winter of 1991-1992

In situ measurements of chlorine monoxide, bromine monoxide, and ozone are extrapolated globally, with the use of meteorological tracers, to infer the loss rates for ozone in the Arctic lower stratosphere during the Airborne Arctic Stratospheric Expedition II (AASE II) in the winter of 1991-1992. The analysis indicates removal of 15 to 20 percent of ambient ozone because of elevated concentrations of chlorine monoxide and bromine monoxide. Observations during AASE II define rates of removal of chlorine monoxide attributable to reaction with nitrogen dioxide (produced by photolysis of nitric acid) and to production of hydrochloric acid. Ozone loss ceased in March as concentrations of chlorine monoxide declined. Ozone losses could approach 50 percent if regeneration of nitrogen dioxide were inhibited by irreversible removal of nitrogen oxides (denitrification), as presently observed in the Antarctic, or without denitrification if inorganic chlorine concentrations were to double.

Salawitch, R. J.

Intercomparison of haloe and ER-2 aircraft H2O and CH4 observations collected during the second Airborne Arctic Stratospheric Experiment (AASE-II)

HALOE observations of H2O and CH4 are compared with in situ techniques aboard the ER-2 aircraft during the northern winter of 1991/92, in particular for the dates 911208, 920108, 920217, 920222, and 920320 when the spatial coincidences are close, within +/- 1 deg latitude and +/- 12 deg longitude. The results reveal the limitations of comparing high resolution in situ aircraft data with a remote sounding limb scanner. Of the five comparison dates, three had HALOE/ER-2 coincidences which occurred near the edge of the Arctic vortex; the vertical variability in the HALOE results and the horizontal variability in the ER-2 observations on these days show that the vortex edge is not a region where exact agreement can be expected except by chance. On a 4th comparison date, there was substantial overlap away from the vortex edge, although for some species the aircraft data show considerable variability near the coincidence point. On the 5th comparison date, the ER-2 had no overlap in altitude with the lowest HALOE observations; however, a short linear interpolation over about 1 km altitude results in smooth composite profiles. Generally speaking the agreement between HALOE and the ER-2 at overlap altitudes is about 12 percent in the case of water vapor, which shows low horizontal and vertical variability. The agreement for methane, with limited data having altitude overlap, is better than 6 percent.

Tuck, A. F.

The BLISS measurements of NO2 - Some new insights

The present study compares the diurnal variation of NO2 measured near 30 km by the BLISS in situ laser spectrometer with calculations from a photochemical model that includes a detailed description of multiple scattering. Even better agreement is found between the data and the model, both at sunset and during the day. The conclusions of an earlier study that the high-resolution in situ measurements of NO2 facilitated validation of the understanding of the diurnal chemistry of NO2 are confirmed.

Pyle, J. A.

Theoretical interpretation of N2O5 measurements

Recent measurements by Webster et al. (1990) have confirmed quantitatively the chemistry controlling the nighttime decay of NO2. Simple equations describing the nighttime behavior of NO2 and N2O5 are presented here. With measurements of the nighttime ozone and NO2 concentrations, these equations can be used to predict the amount of N2O5 produced at any time during the night. In this way, the N2O5 nighttime emission measurement of Roscoe (1982), Kunde et al. (1988) and sunrise measurements of the ATMOS experiment are all used to test theory. The measurements are found to be both self consistent and confirm the present understanding of nighttime NO2 conversion to N2O5. The variation of N2O5 by a factor of two between measurements is found to be consistent with theory.

Toumi, R.

Aircraft laser infrared absorption spectrometer (ALIAS) for polar ozone studies

The ALIAS instrument is a very high resolution (0.0003/cm) scanning, tunable diode laser spectrometer designed to make direct, simultaneous measurements of NO2, HNO3, HCl, CH4, and either O3 or N2O (including vertical profiles of CH4 and N2O) in the polar stratosphere at sub-part-per-billion level sensitivities over integration times from 3 to 30 s. Unique features include a sample inlet/throttle system designed to achieve near-isokinetic sampling, in PSC events, an in-flight wavelength reference cell rack, mechanical fringe-spoilers, a four-laser/four-detector dewar with 24-hr hold-time operating at a fixed temperature without electrical regulation, and in-flight fast correlation routines for spectral drift compensation prior to spectral addition. Instrument design and test flight results are discussed in the light of ALIAS's role in the Winter 1991 Arctic aircraft stratospheric ozone campaigns out of Fairbanks, Alaska, and Bangor, Maine.

Webster, C. R.

Laboratory measurements of NO2 line parameters near 1600/cm for the interpretation of stratospheric spectra

Tunable diode laser laboratory measurements of infrared spectral parameters of selected NO2 lines near 1600/cm have been made to assess the contribution of uncertainties in these parameters to stratospheric measurements of NO2 made using the Balloon-Borne Laser In-Situ Sensor (BLISS) tunable diode laser spectrometer. Relative line intensities are measured to accuracies of better than 2 percent, with a root-sum-squared uncertainty in the absolute linestrengths of 4.5 percent. Air-broadening coefficients have been determined from measurements at total pressures in the range 20-100 Torr, at temperatures of 293 K and 214 K. These results are also discussed in the light of the discrepancies between infrared instruments flown in the 1982 and 1983 Balloon Intercomparison Campaigns.

May, R. D.

In situ stratospheric measurements of HNO3 and HCl near 30 km using the balloon-borne laser in situ sensor tunable diode laser spectrometer

In situ stratospheric measurements of the concentrations of the reservoir species HNO3 and HCl made during two flights of the high-resolution (0.0005/cm) balloon-borne laser in situ sensor instrument from Palestine, Texas, are reported. A measured HNO3 volume mixing ratio of 4.3 parts per billion by volume (ppbv) at 31 km altitude is about 1 ppbv larger than previously reported measurements at 32 deg N. An HCl mixing ratio of 1.6 ppbv at 29 km is in agreement with values obtained from earlier remote sensing techniques within the experimental uncertainties. Upper limits at 31 km of 0.4 ppbv for H2O2 and 0.2 ppbv for HOCl are also derived from analyses of spectra recorded near 1252/cm.

May, R. D.

Frequency stability of a tunable diode laser mounted in a compact Stirling cycle cooler

A tunable diode laser (TDL) has been operated with a compact lightweight closed-cycle Stirling cooler. The laser linewidth has been measured near 80 K and found to be about half of that when using more massive closed-cycle coolers. Novel applications include balloon-borne and aircraft-adapted instruments, where size, weight, and power requirements place stringent demands on necessary TDL cooling systems.

Durso, Santo S.

Tunable diode laser measurements of HO2NO2 absorption coefficients near 12.5 microns

A tunable diode laser spectrometer has been used to measure absorption coefficients of peroxynitric acid (HO2NO2) near the 803/cm Q branch. HO2NO2 concentrations in a low-pressure flowing gas mixture were determined from chemical titration procedures and UV absorption spectroscopy. The diode laser measured absorption coefficients, at a spectral resolution of better than 0.001/cm, are about 10 percent larger than previous Fourier transform infrared measurements made at a spectral resolution of 0.06/cm.

May, R. D.

Brewster-Plate Spoiler for Laser Spectrometer

Oscillating Brewster plate reduces effects of unwanted interference fringes on absorption-spectroscopic measurements obtained with tuned diode lasers. Plate modulates optical-path length past several resonance peaks causing interference fringes to pass by rapidly and become blurred. Thus, fringe effects averaged out over time. Technique used at other wavelengths from ultraviolet to infrared and in spectrometers with short or long optical paths, including those with retroreflectors or multipass cells.

Webster, C. R.

Discharge cell for optogalvanic spectroscopy having orthogonal relationship between the probe laser and discharge axis

A method and apparatus for an optogalvanic spectroscopy system are disclosed. Orthogonal geometry exists between the axis of a laser probe beam and the axis of a discharge created by a pair of spaced apart and longituduinally aligned high voltage electrodes. The electrodes are movable to permit adjustment of the location of a point in the discharge which is to irradiated by a laser beam crossing the discharge region. The cell dimensions are selected so that the cross section of the discharge region is substantly comparable in size to the cross section of the laser beam passing orthogonally through the discharge region.

Webster, C. R.

Tracking System for Infrared Spectrometer

Visible laser tracking system for infrared laser spectometer keeps probe infrared laser beam aimed at moving reflector, thereby keeping reflector image and return laser beam within spectrometer field of view. System includes tracking mirror tilted by stepping motors under microprocessor control to deflect beams toward continually changing reflector position.

Johnson, R. A.

Tunable diode laser Stark modulation spectroscopy for rotational assignment of the HNO3 7.5-micron band

The technique of Stark modulation spectroscopy for unraveling and assigning rotationally resolved dense molecular spectra has been employed using a tunable diode laser (TDL) source. Doppler-limited absorption and Stark modulation spectra of the HNO3 7.5-micron band near the 1326/cm band origin are presented with preliminary values of the excited-state rovibrational constants derived from both TDL and Bomem Fourier transform IR spectra.

Webster, C. R.