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Simmonds, P. G.

Publications and source records attributed to Simmonds, P. G..

At least 19 records

Global trends and annual releases of CCl3F and CCl2F2 estimated from ALE/GAGE and other measurements from July 1978 to June 1991

Thirteen years of Atmospheric Lifetime Experiment/Global Atmospheric Gases Experiment CCl3F and CCl2F2 measurements at five remote, surface, globally distributed sites are analyzed. Comparisons are made against shipboard measurements by the Scripps Institution of Oceanography (SIO) group and archived air samples collected at Cape Grim, Tasmania, since 1978. CCl3F in the lower troposphere was increasing at an average rate of 9.2 ppt/yr over the period July 1978 to June 1988. CCl2F2 was increasing at an average 17.3 ppt/yr in the lower troposphere over the same period. However, between July 1988 and June 1991 the increases of CCl3F and CCl2F2 in this region have averaged just 7.0 ppt/yr and 15.7 ppt/yr, respectively. The rate of increase has been decreasing 2.4 ppt/yr(exp 2) and 2.9 ppt/yr(exp 2) over this 3-year period. Based on a recent scenario of the global releases of these compounds and using the new calibration scale SIO 1993, the equilibrium lifetimes are estimated to be 44 +17/-10 and 180 +820/-81 years for CCl3F and CCl2F2, respectively. Using these lifetime estimates and a two-dimensional model, it is estimated that global releases of these two chlorofluorocarbons in 1990 were 249 +/- 28 x 10(exp 6) kg for CCl3F and 366 +/- 30 x 10(exp 6) kg for CCl2F2. It is also estimated that combined releases of these chlorofluorocarbons in 1990 were 21 +/- 5% less than those in 1986.

Cunnold, D. M.

Atmospheric lifetime and annual release estimates for CFCl3 and CF2Cl2 from 5 years of ALE data

CFCl3 and CF2Cl2 data for the 5-year period from July 1978-June 1983 are analyzed. The lifetime estimates are updated using the trend technique and the annual global release rates of the gases are derived. The effects of release uncertainties on lifetime estimates are examined by studying fluorocarbon data. It is observed that in 1981 the mixing ratios for CFCl3 and CF2Cl2 displayed increases of 8.8. and 15.3 pptv/year respectively, and the trend lifetime for CFCl13 is 74 + 31 or - 17 years and for CF2Cl2 111 + 222 or - 44 years.

Cunnold, D. M.

The atmospheric lifetime experiment. I - Introduction, instrumentation, and overview

The Atmospheric Lifetime Experiment is designed to determine accurately the atmospheric concentrations of the four halocarbons CFCl3, CF2Cl2, CCl4, and CH3CCl3, and also of N2O with emphasis on measurement of their long-term trends in the atmosphere. Comparison of these concentrations and trends for the four halocarbons with estimates of their industrial emission rates then enables calculations of their global circulation rates and globally averaged atmospheric lifetimes. The experiment utilizes automated dual-column electron-capture gas chromatographs which sample the background air about 4 times daily at the following globally distributed sites: Adrigole, Ireland, Cape Meares, Oregon; Ragged Point, Barbados; Point Matatula, American Samoa, and Cape Grim, Tasmania. The climatology of these 'clean air' sites and their ability to describe the global air mass are reviewed. The instrumentation and methods for data acquisition and processing are then described. An overview of the data obtained and the trends derived during the 3-year period from July 1978 through June 1981 for each of the five species being measured is presented.

Prinn, R. G.

The atmospheric lifetime experiment. III - Lifetime methodology and application to three years of CFCL3 data

Observations of the chlorofluorocarbon CFCl3 obtained several times daily over the period July 1978 to June 1981 at Adrigole, Ireland; Ragged Point, Barbados; Point Matatula, American Samoa; and Cape Grim, Tasmania are reported. In addition, observations at Cape Meares, Oregon are given for the period January 1980 to June 1981. On January 1, 1980, the average mixing ratio of CFCl3 in the lower troposphere is esimated to have been 168 pptv, and this is calculated to have been increasing 5.7 percent annually. Assuming that the only destruction of CFCl3 occurs in the stratosphere, the lifetime, on January 1, 1980, estimated by a trend technique is 83 + 73, or -27 years; the lifetime estimated from the global inventory of CFCl3 is to + 89 or -25 years. The maximum likelihood current lifetime estimate obtained by combining the estimates from both analysis techniques is 78 years.

Cunnold, D. M.

The Atmospheric Lifetime Experiment. IV - Results for CF2Cl2 based on three years data

Observations of dichlorodifluoromethane obtained several times daily over the period July 1978 to June 1981 at Adrigole, Ireland (52 deg N, 10 deg W), Ragged Point, Barbados (13 deg N, 59 deg W), Point Matatula, American Samoa (14 deg S, 171 deg W), and Cape Grim, Tasmania (41 deg S, 145 deg E), are reported. Observations at Cape Meares, Oregon (45 deg N, 124 deg W), are also given for the period November 1980 to June 1981. On January 1, 1980, the average mixing ratio of dichlorodifluoromethane in the lower troposphere is estimated to have been 285 pptv and to have been increasing at 6.0 percent/year. The atmospheric lifetime of this compound is estimated from this data by adjusting its destruction rate in a two-dimensional model of the atmosphere so as to provide the best fit to the observations. Assuming destruction of CF2Cl2 in the stratosphere only, the lifetime estimate for January 1, 1980, by the inventory technique is 69 + 36 or - 18 years. The trend technique principally provides a lower limit to the lifetime of 81 years. The results suggest a need for further assessment of dichlorodifluoromethane release estimates, particularly those from the USSR and eastern Europe.

Cunnold, D. M.

The search for organic substances and inorganic volatile compounds in the surface of Mars

A total of four Martian samples, one surface and one subsurface sample at each of the two Viking landing sites, Chryse Planitia and Utopia Planitia, have been analyzed for organic compounds by a gas chromatograph-mass spectrometer. In none of these experiments could organic material of Martian origin be detected at detection limits generally of the order of parts per billion and for a few substances closer to parts per million. The evolution of water and carbon dioxide, but not of other inorganic gases, was observed upon heating the sample to temperatures of up to 500 C. The absence of organic compounds seems to preclude their production on the planet at rates that exceed the rate of their destruction. It also makes it unlikely that living systems that behave in a manner similar to terrestrial biota exist, at least at the two Viking landing sites.

Biemann, K.

Search for organic and volatile inorganic compounds in two surface samples from the Chryse Planitia region of Mars

Two surface samples collected from the Chryse Planitia region of Mars were heated to temperatures up to 500 C, and the volatiles that they evolved were analyzed with a gas chromatograph-mass spectrometer. Only water and carbon dioxide were detected. This implies that organic compounds have not accumulated to the extent that individual components could be detected at levels of a few parts per billion by weight in the samples. Proposed mechanisms for the accumulation and destruction of organic compounds are discussed in the light of this limit.

Biemann, K.

Gas chromatographic column for the Viking 1975 molecular analysis experiment

A gas chromatographic column has been developed for use in the remote analysis of the Martian surface. The column, which utilizes a liquid-modified organic adsorbent (Tenax) as the stationary phase, provides efficient transmission and resolution of nanogram quantities of organic materials in the presence of millionfold excesses of water and carbon dioxide.

Novotny, M.

Compact hydrogenator

The development and characteristics of a hydrogenating apparatus are described. The device consists of a reaction chamber which is selectively permeable to atomic hydrogen and catalytically active to a hydrogenating reaction. In one device, hydrogen is pumped out of the reaction chamber while the reactant remains inside to remove molecular hydrogen so that more atomic hydrogen can pass through the walls. In another device, the reactant is pumped through the reaction chamber, and the hydrogen is removed from the material leaving the chamber. The reactant is then cycled through the chamber.

Simmonds, P. G.

Pyrolysis of amino acids - Mechanistic considerations

Pyrolysis of several structurally different amino acids in a column at 500 C showed differences in the mechanisms and final products. The aliphatic protein amino acids decompose mainly by simple decarboxylation and condensation reactions, while the beta amino acids undergo deamination to unsaturated acids. Alpha amino acids with alpha alkyl substituents undergo an unusual intramolecular SN1 reaction with the formation of an intermediate alpha lactone which decomposes to yield a ketone. The alpha alkyl substituents appear to stabilize the developing negative charge formed by partial heterolytic cleavage of the alpha carbon - NH3 bond. The gamma and delta amino acids give 2-pyrrolidinone and 2-piperidone respectively, while the epsilon acids yield mixed products.

Ratcliff, M. A., Jr.

Gas-operated actuator: A concept

Recyclable actuator does depend on valves for its operation. Palladium cathode tube in electrochemical cell is used to generate hydrogen by electrolysis. Hydrogen pressure generated inside tube causes expansion of bellows, which raises load. Bellows can be retracted by reversing electrical connections to cell electrodes.

Simmonds, P. G.

A portable self-contained gas chromatograph.

The design and fabrication of a completely portable, self-contained gas chromatograph is described. This instrument utilizes a closed-loop hydrogen carrier gas flow as maintained by a hydrogen generator-separator. It employs an auxiliary hydrogen generator to keep a positive flow of hydrogen through the detector. The detector is an ionization cross section detector. The only maintenance required is the addition of water (5-15 cc/day) to the auxiliary hydrogen generator. Lower limit of detection for the present system is of the order of 1-10 ppm ethane.

Stevens, M. R.