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Davis, D. D.

Publications and source records attributed to Davis, D. D..

At least 37 records · Page 2

Aqueous-phase source of formic acid in clouds

The coupled gas- and aqueous-phase cloud chemistry of HCOOH were examined for controlling factors in the acidity of cloud and rainwater. Attention was given to the aqueous OH/HO2 system that yields an OH species that is highly reactive with other species, notably SO2 and the formaldehyde/formic acid complex. A numerical model was developed to simulate the cloud chemistry in the remote troposphere, with considerations given to CH4-CO-NO(x)-O3-H(x)O(y) system. It was determined that aqueous phase OH radicals can produce and destroy formic acid droplets in daylight conditions, as well as control formic acid levels in rainwater. It is sugested that the same types of reactions may be involved in the control of acetic acid and other organic acids.

Chameides, W. L.↗

The free radical chemistry of cloud droplets and its impact upon the composition of rain

Calculations are presented that simulate the free radical chemistries of the gas phase and aqueous phase within a warm cloud during midday. It is demonstrated that in the presence of midday solar fluxes, the heterogeneous scavenging of OH and HO2 from the gas phase by cloud droplets can represent a major source of free radicals to cloud water, provided the accommodation or sticking coefficient for these species impinging upon water droplets is not less than 0.0001. The aqueous-phase of HO2 radicals are found to be converted to H2O2 by aqueous-phase chemical reactions at a rate that suggests that this mechanism could produce a significant fraction of the H2O2 found in cloud droplets. The rapid oxidation of sulfur species dissolved in cloudwater by this free-radical-produced H2O2 as well as by aqueous-phase OH radicals could conceivably have a significant impact upon the chemical composition of rain.

Chameides, W. L.↗

H2O2 levels in rainwater collected in south Florida and the Bahama Islands

Measurements of H2O2 in rainwater collected in Miami, Florida, and the Bahama Islands area indicate the presence of H2O2 concentration levels ranging from 100,000 to 700,000 M. No systematic trends in H2O2 concentration were observed during an individual storm, in marked contrast to the behavior of other anions for example, NO3(-), SO4(-2), and Cl(-). The data suggest that a substantial fraction of the H2O2 found in precipitation is generated by aqueous-phase reactions within the cloudwater rather than via rainout and washout of gaseous H2O2.

Zika, R.↗

Unprecented syntonization and syncronization accuracy via simultaneous viewing with GPS receivers: Construction characteristics of an NBS/GPS receiver

The National Bureau of Standards/Global Positioning System (NBS/GPS) receiver is discussed. It is designed around the concept of obtaining high accuracy, low cost time and frequency comparisons between remote frequency standards and clocks with the intent to aid international time and frequency coordination. Preliminary tests of this comparison technique between Boulder, CO and Washington, D.C indicate the ability to do accurate time transfer to better that 10 ns, and frequency measurements to better than 1 part in 10 to the 14th power. The hardware and software of the receiver is detailed. The receiver is fully automatic with a built-in 0.1 ns resolution time interval counter. A microprocessor does data processing. Satellite signal stabilities are routinely at the 5 ns level for 15 s averages, and the internal receiver stabilities are at the 1 ns level.

Davis, D. D.↗

A theoretical assessment of the O3/H2O interference problem in the detection of natural levels of OH via laser induced fluorescence

Theoretical calculations are presented which estimate the possible magnitude of the O3/H2O derived OH interference signal resulting from the use of the laser-induced fluorescence technique in measuring natural levels of tropospheric OH. Critical to this new assessment has been the measurement of the nascent OH quantum state distribution resulting from the reaction O(1D) + H2O yields 2OH, and an assessment of the subsequent rotational relaxation of the OH species when formed in high k levels.

Davis, D. D.↗

Construction and performance characteristics of a prototype NBS/GPS receiver

The construction and performance characteristics of a low-cost, high-accuracy GPS C/A receiver are reviewed. The receiver takes advantage of a simultaneous common view of the same satellites, which could allow time transfer with accuracies on the order of 10 ns or less for baselines as large as 3000 km. Frequency can be measured to better than one part in 10 to the 14th. The software and the receiver are configured to be fully automatic with a Z80A microprocessor setting the amplitude for the lock loops of the receiver and setting the synthesizer with corrects for Doppler shift. The microprocessor can calibrate a 0.1 ns built-in time interval counter.

Davis, D. D.↗

Iodine - Its possible role in tropospheric photochemistry

A detailed study of the photochemistry of iodine and its oxides indicates that iodine species may play an important role in the tropospheric photochemical system. Methyl iodide, often observed in the marine troposphere with an average concentration of 5-10 ppt, is photolyzed and thereby produces I atoms. Chemical interactions with O3, HxOy, and NOx cause I to be converted to other inorganic compounds such as IO, HOI, IONO2, and I2. The production of these species and their subsequent recycling back to I can lead to the catalytic removal of tropospheric O3, the enhancement of the NO2/NO ratio, the destruction of HxOy free radicals, and the conversion of HO2 to OH. Ultimately, tropospheric inorganic iodine is removed by heterogeneous processes. Calculations using a numerical model to simulate tropospheric photochemistry indicate that iodine may have a strong impact upon the atmospheric O3-NOx-HxOy system. The magnitude of these effects is dependent upon the value of several uncertain rate constants and the primary source distributions of CH3I and other organic and inorganic iodine compounds.

Chameides, W. L.↗

Photofragmentation-laser induced fluorescence - A new method for detecting atmospheric trace gases

A new method for the in situ detection of nonfluorescing molecular species is proposed: photofragmentation-laser induced fluorescence (PF-LIF). In this approach, the species to be detected is first laser photolyzed at a wavelength lambda (1), producing one or more vibrationally excited photofragments. Before vibrational relaxation occurs, one of these photofragments is pumped into a bonding excited state by a second laser pulse centered at wavelength lambda (2). Fluorescence is sampled at a wavelength lambda (3), where lambda (3) is less then lambda (2) and lambda (1). This pumping configuration thus permits massive discrimination against Rayleigh and Raman scattering as well as white noise fluorescence from the laser wavelengths lambda (1) and lambda (2). The technique should be both highly sensitive and selective for numerous atmospheric trace gases. Specific sampling schemes for detecting NO2, NO3, and HNO2 are proposed. Various noise sources and chemical interferences are discussed. Specific calculations that estimate the sensitivity of the PF-LIF system for detecting NO2, NO3, and HNO2 are given.

Rodgers, M. O.↗

Infrared laser photolysis - A new tool for the study of prebiotic chemistry

Infrared laser induced dielectric breakdown and multiphoton absorption experiments on CH4/NH3 'atmospheres' are described. It is found that HCN, a central intermediate in prebiotic chemistry, is a principal product. This, combined with the fact that dielectric breakdown appears to have much in common with ordinary electric sparks, suggests that the laser could be a useful tool in studies of prebiotic chemistry. Several possible experiments in this vein are suggested.

Davis, D. D.↗

Airborne laser induced fluorescence system for measuring OH and other trace gases in the parts-per-quadrillion to parts-per-trillion range

Described in detail is a laser induced fluorescence system which has been successfully interfaced with two aircraft sampling platforms (i.e., Sabreliner jet and an L-188C Electra). This system, which has been under development for four years, presently consists of the following major components: (1) a Nd-Yag laser driven oscillator-amplifier dye laser; (2) a sampling manifold with associated fluorescence detection optics; (3) an OH calibration chamber; (4) a laser beam steering assembly; and (5) sampling electronics and data processing hardware. During the last three years, this system has been flown some 50,000 air miles making tropospheric OH radical measurements over the latitude range of 70 N to 57 S. OH concentrations measured during these flights have ranged from 30 parts-per-quadrillion (3.7 x 10 to the 5th molecules/sq cm) at altitudes of 6 km to 0.8 parts-per-trillion (2.0 x 10 to the 7th molecules/sq cm) at 0.5 km. Computations have been completed which indicate that the existing aircraft system with modest modifications should also be capable of detecting natural tropospheric levels of NO, SO2, CH2O, NO2, HNO2, NO3, H2O2 and CS2 by using both conventional laser-induced fluorescence methodology and multiphoton techniques.

Davis, D. D.↗

Boundary layer measurements of the OH radical in the vicinity of an isolated power plant plume - SO2 and NO2 chemical conversion times

Direct measurements of the OH radical in the vicinity of an isolated power plant plume are reported. These measurements were used to estimate the conversion time of SO2 to H2SO4-sulfate aerosol via the initiating step OH + SO2 + M yields HSO3. Using the near-high-noon measured value of OH (9.5 million per cu cm), resulted in a 1/e conversion time of 1.4 days. The latter lifetime would correspond to a conversion rate of about 2%/hr. When the lifetime calculation was modified to take into consideration the OH diurnal cycle, the 1/e conversion time for SO2 was found to be 4.4 days, giving an apparent overall rate of conversion of about 0.7%/hr. Similar calculations carried out for the conversion of NO2 to NHO3 resulted in 1/e lifetimes for NO2 of 2-3 h for midday time periods.

Davis, D. D.↗

Time recovery measurements using operational GOES and transit satellites

Results of regular monitoring of both the GOES and TRANSIT timing signals over a number of months at the National Bureau of Standards (NBS), Boulder, Colorado are presented. The TRANSIT results include an analysis of how received timing accuracy and stability are affected by: (1) averaging over varying numbers of satellite passes; (2) averaging over different combinations of the five available satellites; (3) using several independent receivers of the same type; and (4) application of published corrections to the received data. Based on monitoring experience to date at NBS, some pros and cons of using each of the available operational systems are discussed. Updated information on recent improvements incorporated into the GOES time code generation and monitoring system at Wallops Island, Virginia is also included.

Beehler, R. E.↗

Two-Way Time Transfer via Geostationary Satellites NRC/NBS, NRC/USNO and NBS/USNO via Hermes and NRC/LPTF (France) via Symphonie

In most of the experiments, 1 pps pulses of the station atomic clocks were exchanged between the partners, and a cubic equation was fitted to the 1000 to 2000 second measurements. The equations were exchanged and substracted to obtain the time difference of the stations. The standard deviation in the fit of the equations varied, depending on conditions, from 1.5 ns to 16 ns. For the last month of the Hermes experiment, a 1 MHz signal was used, giving a standard deviation of 0.18 ns. The comparison of the time scales via satellite and via Loran-C (BIH Circular D) show clearly that some Loran-C links are very good, but that the NBS link varies by 1 micron s. Via the satellite the frequencies of the time scales can be compared with an accuracy of 2 x 10 to the minus 14 power.

Costain, C.↗

A kinetics investigation of several reactions involving chlorine containing compounds

The technique of flash photolysis-resonance fluorescence was utilized to study nine reactions of stratospheric importance. The tropospheric degradation reactions of seven halogenated hydrocarbons were studied to assess their possible influx into the stratosphere. There are reactions of either Cl, OH, or O(3P) species with hydrogenated species, O3 or chlorinated compounds. Apart from the kinetic measurements, the quantum yield for the production of O(1D) from O3 in the crucial wavelength region of 293 to 316.5 nm was studied by utilizing a narrow wavelength laser as the photolysis source. The product formation was monitored by measuring the fluorescence of NO2 formed through O(1D) reaction with N2O followed by NO reaction with O3 to give NO2.

Davis, D. D.↗

An aircraft compatible laser induced fluorescence system - In situ and remote measurements of trace gases

The laser-induced fluorescence technique for obtaining direct measurements of atmospheric OH and other gases is described. A narrow-band UV laser is tuned to one or more of the electronic absorption bands of a specified molecule so as to cause fluorescence from a bonding excited electronic state. The monitored wavelength is longer than the laser wavelength. Equipment, specifics for OH detection, data processing, and interference are discussed, and application of the technique to the detection of NO, SO2, and CH2O is considered.

Davis, D. D.↗

A quantum yield determination of O/1D/ production from ozone via laser flash photolysis

The quantum yield of electronically excited atomic oxygen produced from ozone photolysis was measured at 298 K from wavelengths of 293.0 to 316.5 nm. The reaction of the atomic oxygen with N2O to form excited NO2 was used to monitor the O production; a frequency-doubled flashlamp-pumped dye laser which provided tunable ultraviolet in the desired spectral region with 0.1-nm linewidth served as the photolysis source. The atomic oxygen quantum yield was found to be constant below 300 nm, with a sharp decrease centered at 308 nm and a diminution to less than one tenth of the constant value by 313.5 nm.

Philen, D. L.↗