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Prinn, R. G.

Publications and source records attributed to Prinn, R. 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.

Ozone response to a CO2 doubling - Results from a stratospheric circulation model with heterogeneous chemistry

A spectral 3D model of the stratosphere has been used to study the sensitivity of polar ozone with respect to a carbon dioxide increase. The lower stratospheric cooling associated with an imposed CO2 doubling may increase the probability of polar stratospheric cloud (PSC) formation and this affect ozone. The ozone perturbation obtained with the inclusion of a simple parameterization for heterogeneous chemistry on PSCs is compared to that relative to a pure homogeneous chemistry. In both cases the temperature perturbation is determined by a CO2 doubling, while the total chlorine content is kept at the present level. It is shown that the lower temperature may increase the depth and the extension of the ozone hole by extending the area amenable to PSC formation. It may be argued that this effect, coupled with an increasing amount of chlorine, may produce a positive feedback on the ozone destruction.

Pitari, G.

Earth System science

Recent research has solidified a view of the Earth as a global-scale interactive system with complex chemical, physical, biological and dynamical processes that link the ocean, atmosphere, land (soils, ice, snow) and marine and terrestrial living organisms. These processes both within and between the major parts of the system help determine global and regional climate and control the biogeochemical and hydrologic cycles essential to life. The study of the Earth System requires measurements ranging from the scales of the smallest processes to the global scale. An ambitious satellite observational program, the Earth Observing System (EOS), carried out along with the complementary and ongoing World Climate Research Program (WCRP) and International Geosphere-Biosphere Program (IGBP) represents a major international effort to understand this System and predict its future changes. The complex and intriguing nature of the Earth System is discussed along with a number of closely coupled processes occurring within it. These are: clouds, precipitation and vegetation; ocean circulation, sea-surface temperature and phytoplankton; coupled oceanic and atmospheric circulation (the Southern Oscillation); biological activity, atmospheric chemistry and climate; and biological emissions and the ozone layer.

Prinn, R. G.

Biogenic and anthropogenic trace gases in the atmosphere

This paper illustrates the importance of biogenic and anthropogenic trace gases for the global environment and for the climate system. The paper briefly reviews the currently available estimates of sources and strengths of the biogenic and anthropogenic gases on the global scale. One of the major concerns for the global environment is the rapid increase in the concentration of long-lived trace gases such as CO2, CH4, N2O and the chlorofluorocarbons. The trend in the carbon dioxide concentration, as a result of fossil-fuel burning, is of the order of 0.4 percent per year, and this trend is related to the CO2 uptake by the ocean and by terrestrial ecosystems, which are likely to be modified if the planet warms up in the forthcoming decades. The concentrations of methane and nitrous oxide are increasing by 0.9 and 0.25 percent per year, respectively. In the case of the most widely used chlorofluorocarbons, trends as large as 10 percent per year or more are being measured.

Brasseur, G. P.

Tropospheric chemical models

The differences in atmospheric composition over the globe and the short- and long-term variations in this composition are the net effect of several atmospheric and biospheric processes: biospheric emissions, atmospheric circulation, atmospheric chemical transformations and finally deposition back to the surface. Accurate and realistic atmospheric chemistry and circulation models are essential to interpret the observed global distributions and trends of atmospheric species in terms of these underlying processes. Comparisons between model predictions and observations test current understanding of these processes and models used in conjunction with inverse methods allow deductions of the rates of these processes from the observations. With the planned inclusion of at least CO and CH4 observations on the Earth Observing System (EOS) satellites, together with the large global data set expected from in situ observations under the International Global Atmospheric Chemistry (IGAC) Project, the further development of global three-dimensional high-resolution atmospheric chemistry and circulation models in order to interpret this new data is a high-priority endeavor.

Prinn, R. G.

Venus volcanism: Rate estimates from laboratory studies of sulfur gas-solid reactions

Thermochemical reactions between sulfur-bearing gases in the atmosphere of Venus and calcium-, iron-, magnesium-, and sulfur-bearing minerals on the surface of Venus are an integral part of a hypothesized cycle of thermochemical and photochemical reactions responsible for the maintenance of the global sulfuric acid cloud cover on Venus. SO2 is continually removed from the Venus atmosphere by reaction with calcium bearing minerals on the planet's surface. The rate of volcanism required to balance SO2 depletion by reactions with calcium bearing minerals on the Venus surface can therefore be deduced from a knowledge of the relevant gas-solid reaction rates combined with reasonable assumptions about the sulfur content of the erupted material (gas + magma). A laboratory program was carried out to measure the rates of reaction between SO2 and possible crustal minerals on Venus. The reaction of CaCO3(calcite) + SO2 yields CaSO4 (anhydrite) + CO was studied. Brief results are given.

Ehlers, K.

Biospheric traumas caused by large impacts and predicted relics in the sedimentary record

When a large asteroid or comet impacts the Earth the supersonic plume ejected on impact causes severe shock heating and chemical reprocessing of the proximal atmosphere. The resultant NO is converted rapidly to NO2, foliage damage due to exposure to NO2 and HNO3, toxicosis resulting from massive mobilization of soil trace metals, and faunal asphyxiation due to exposure to NO2. One class of relic evidence for the above effects arises because extinction of species caused by these chemically induced traumas would be selective. A second class of relic evidence arises because the acid rain will cause massive weathering of continental rocks and soils characterized by large ratios of the relatively insoluble metals, to the more soluble metals. This weathering would be best recorded in fossils in unperturbed deltaic, neritic, or limnetic sediments and for metals with very long oceanic residence times in deep ocean sediments as well. This evidence is discussed.

Prinn, R. G.

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.

A global three-dimensional model of the circulation and chemistry of CFCl3, CF2Cl2, CH3CCl3, CCl4, and N2O

The use of a three-dimensional spectral model to study the tropospheric and stratospheric circulation, chemistry, and photochemistry of the CFCl3, CF2Cl2, CH3CCl3, CCl4, and N2O atmospheric species is examined. The components of the model are described. Lifetime, regional, and global trends and budgets for the species are evaluated. Calculated horizontal, vertical, and temporal distributions of the atmospheric species are compared with observations; good correlation is detected. The differences observed between calculated and observed surface distributions of CH3CCl3 and the vertical distribution of CCl4 are analyzed. The calculated global atmospheric lifetimes of CFCl3, CF2Cl2, CCl4, and N2O are 73, 210, 48, and 182 years, respectively.

Golombek, A.

Chemical effects of large impacts on the earth's primitive atmosphere

The production of HCN and H2CO by large impacts on the earth's primitive atmosphere is modelled using thermochemical equilibrium and chemical kinetic calculations of the composition of shocked air parcels for a wide range of temperatures, pressures, and initial compositions. For atmospheres with C/O of one or more, the results suggest that bolide impacts cause HCN volume mixing ratios of approximately 10 to the -3rd to -5th in the impact region and global average ratios of 10 to the -5th to the -12th. The corresponding H2CO mixing ratios in the impact region are 10 to the -7th to -9th; nonglobal mixing can occur, however, as H2CO is rapidly destroyed or rained out of the atmosphere within days to hours. Rainout to the oceans of 3-15 percent of the HCN produced can provide 3-14 x 10 to the 11th mol HCN per year.

Fegley, B., Jr.

Composition and chemistry of Saturn's atmosphere

A comprehensive discussion and review is presented of the chemistry and composition of Saturn as determined by earth-based, earth-orbital, and Voyager 1 and 2 spectroscopic observations. The observations imply that there are important differences between the actual composition of Saturn's atmosphere and that predicted for a homogeneous solar-composition planet. The H2, He, Ch4, NH3, and PH3 volume mixing ratios differ from the expected solar composition ratios, implying that during its formation Saturn accreted a significant amount of ice and rock. The depletion of He in the visible atmosphere suggests that this element has preferentially differentiated toward the center of the planet. The D to H ratio is similar to that on Jupiter and has important cosmological implications. Volume mixing ratios for C2H6 and C2H2 are consistent with the theoretically expected photochemical sources for these gases.

Prinn, R. G.

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.

Chemical consequences of major impact events on earth

Violent cometary or asteroidal impact events comparable to that which terminated the Cretaceous era must produce large amounts of nitrogen oxides, sufficient to provide NOx mole fractions much larger than 100 ppm over areas of millions of square kilometers. Rapid production of NO2, and subsequent rainout of HNO3 and other strong acids can acidify surface waters, selectively destroying CaCO3 shells. This scenario holds the promise of explaining both the scope of Cretaceous biological extinctions and their extraordinary selectivity.

Lewis, J. S.

Kinetic inhibition of CO and N2 reduction in circumplanetary nebulae - Implications for satellite composition

In contrast to the solar nebula, the conversion of CO to CH4 and of N2 to NH3 in the circumplanetary nebulae of the Jovian planets is fast enough relative to radial mixing and nebula cooling rates that CO and N2 are minor constituents in the circumplanetary nebulae. Thus, although the Jovian planets may have accreted carbon and nitrogen from the solar nebula mainly in the form of CO and N2, these species were then reprocessed within the circumplanetary nebulae to form mainly CH4 and NH3. Satellites of the Jovian planets which accreted in sufficiently cool parts of their circumplanetary nebula are therefore predicted to retain large amounts of NH3 and CH4 in the form of clathrate hydrates and also very small but chemically important amounts of HCN.

Prinn, R. G.

Kinetic inhibition of CO and N2 reduction in the solar nebula

It is shown that the conversion of CO to methane and of N2 to ammonia in the primitive solar nebula was probably so slow relative to radial mixing rates or nebula evolutionary rates that only small amounts of NH3 and CH4 could have been present. Thus most of the nitrogen was present as N2 and most of the carbon as CO and CO2 throughout the nebula. The consequences of this kinetic effect upon the composition of cometary ices and of the Jovian planets, the melting and outgassing behavior of ice rich planetary satellites, and the abundance of carbon in the terrestrial planets are briefly discussed.

Lewis, J. S.

Preliminary calculations concerning the maintenance of the zonal mean ozone distribution in the Northern Hemisphere

Results from a three-dimensional photochemical-dynamical model of ozone are presented and a qualitative description of the maintenance of the ozone distribution and its seasonal variations below 1 mb is given. The transition between photochemical and transport control of the ozone distribution is emphasized. Between 1 and 10 mb, transport by the eddies seems to play only a minor role at mid-latitudes in producing the observed ozone distribution despite the zero correlation between ozone and temperature which occurs in that region. In the lower stratosphere, mean and eddy contributions to ozone change generally strongly offset one another. The buildup and decay of the springtime ozone maximum is discussed. Emphasis is given to the mechanism of ozone transport by the mid-latitude eddies, which play an important role in the springtime accumulation of ozone.

Cunnold, D. M.