Emissions of methyl halides and methane from rice paddies.

Methyl halide gases are important sources of atmospheric inorganic halogen compounds, which in turn are central reactants in many stratospheric and tropospheric chemical processes. By observing emissions of methyl chloride, methyl bromide, and methyl iodide from flooded California rice fields, we estimate the impact of rice agriculture on the atmospheric budgets of these gases. Factors influencing methyl halide emissions are stage of rice growth, soil organic content, halide concentrations, and field-water management. Extrapolating our data implies that about 1 percent of atmospheric methyl bromide and 5 percent of methyl iodide arise from rice fields worldwide. Unplanted flooded fields emit as much methyl chloride as planted, flooded rice fields.

Atmospheric Methyl Bromide (CH3Br) from Agricultural Soil Fumigations.

The treatment of agricultural soils with CH(3)Br (MeBr) has been suggested to be a significant source of atmospheric MeBr which is involved in stratospheric ozone loss. A field fumigation experiment showed that, after 7 days, 34 percent of the applied MeBr had escaped into the atmosphere. The remaining 66 percent should have caused an increase in bromide in the soil; soil bromide increased by an amount equal to 70 percent of the applied MeBr, consistent with the flux measurements to within 4 percent. Comparison with an earlier experiment in which the escape of MeBr to the atmosphere was greater showed that higher soil pH, organic content and soil moisture, and deeper, more uniform injection of MeBr may in combination reduce the escape of MeBr.

Agricultural soil fumigation as a source of atmospheric methyl bromide.

Methyl bromide (MeBr) is used increasingly as a biocidal fumigant, primarily in agricultural soils prior to planting of crops. This usage carries potential for stratospheric ozone reduction due to Br atom catalysis, depending on how much MeBr escapes from fumigated soils to the atmosphere and on details of atmospheric chemical reactions. We present direct field measurements of MeBr escape; 87% of the applied MeBr was emitted within 7 days after a commercial fumigation. Covering the field with plastic sheets retarded MeBr escape somewhat but first-day losses were still 40%; thicker sections of sheets were relatively more effective than thin sections. We also measured gaseous MeBr concentrations versus depth in the soil column; these profiles display diffusion-like evolution. In soil, MeBr is partitioned among gas, liquid, and adsorbed solid phases. Calculated soil inventories agreed only roughly with applied amounts, probably due to nonequilibrium partitioning (during the first 30 min) and to uncertainties in partitioning coefficients. Fumigated fields may release less MeBr if they are covered by more gas-tight plastic films, if injection techniques are improved and injection is deeper, and if soil moistures, organic amounts, and densities are greater than in the soil studied here.

Reduced antarctic ozone depletions in a model with hydrocarbon injections.

Motivated by increased losses of Antarctic stratospheric ozone and by improved understanding of the mechanism, a concept is suggested for action to arrest this ozone loss: injecting the alkanes ethane or propane (E or P) into the Antarctic stratosphere. A numerical model of chemical processes was used to explore the concept. The model results suggest that annual injections of about 50,000 tons of E or P could suppress ozone loss, but there are some scenarios where smaller E or P injections could increase ozone depletion. Further, key uncertainties must be resolved, induding initial concentrations of nitrogen-oxide species in austral spring, and several poorly defined physical and chemical processes must be quantifed. There would also be major difficulties in delivering and distributing the needed alkanes.

Changes in stratospheric ozone.

The ozone layer in the upper atmosphere is a natural feature of the earth's environment. It performs several important functions, including shielding the earth from damaging solar ultraviolet radiation. Far from being static, ozone concentrations rise and fall under the forces of photochemical production, catalytic chemical destruction, and fluid dynamical transport. Human activities are projected to deplete substantially stratospheric ozone through anthropogenic increases in the global concentrations of key atmospheric chemicals. Human-induced perturbations may be occurring already.

Spectroscopic detection of stratospheric hydrogen cyanide.

A number of features have been identified as absorption lines of hydrogen cyanide in infrared spectra of stratospheric absorption obtained from a high-altitude aircraft. Column amounts of stratospheric hydrogen cyanide have been derived from spectra recorded on eight flights. The average vertical column amount above 12 kilometers is 7.1 +/- 0.8 x 10(14) molecules per square centimeter, corresponding to an average mixing ratio of 170 parts per trillion by volume.

Atmospheric carbon tetrafluoride: a nearly inert gas.

An analysis of existing thermodynamic, photochemical, and kinetic data indicates that the dominant sinks for atmospheric carbon tetrafluoride (CF(4)) are in and above the mesosphere. Theoretical calculations predict an atmospheric residence time for CF(4) of over 10,000 years, about 100 times that for dichlorodifluoromethane (CF(2)Cl(2)) and monofluorotrichloromethane (CFC1(3)). It is predicted that CF(4) will be well mixed through the stratosphere and mesosphere; only one or two parts of hydrogen fluoride in 10(12) are predicted in the high stratosphere as a result of the decomposition of CF(4). Although natural sources of CF(4) cannot be ruled out, there are several likely industrial sources that may account for its present concentration. The principal environmental effect of CF(4) could be the trapping of outgoing planetary infrared energy in its intense bands near 8 micrometers.

Local response-rate constancy on concurrent variable-interval schedules of reinforcement.

Concurrent variable-interval schedules were arranged with a main key that alternated in color and schedule assignment, along with a changeover key on which a small fixed ratio was required to changeover. Acceptable matching was observed with pigeons in two replications, but there was a tendency toward overmatching. Local response rates were found to differ for unequal schedules of a concurrent pair: local response rate was greater for the variable-interval schedule with the smaller average interreinforcement interval, but qualifications based on an interresponse-time analysis were discussed. In a second experiment, two 3-minute variable-interval schedules were arranged concurrently, and the experimental variable was the changeover procedure: either a changeover delay was incurred by each changeover or a small fixed ratio on a changeover key was required to complete a changeover. Changeover delays of 2 and 5 seconds were compared with a fixed-ratio changeover of five responses. The response output on the main key (associated with the variable-interval schedules) was greater when a changeover delay was arranged than when a fixed ratio was required to changeover. A detailed analysis of stripchart records showed that a 2-second delay generated an increased response rate for 3 seconds after a changeover, while the fixed-ratio requirement generated an increased rate during the first second only, followed by a depressed response rate for 2 seconds.

Preference for mixed versus constant delay of reinforcement.

Preference for constant and mixed delay of reinforcement was studied using concurrent equal variable-interval schedules. For four pigeons, pecking one key was reinforced following constant delays of 8 sec and mixed delays of 6 or 10 and 2 or 14 sec. Pecking a second key was reinforced following constant delays of 0, 8, 16, and 32 sec. For two additional pigeons, pecking one key was reinforced following delays of 30, 15 or 45, 5 or 55, and 0 or 60 sec. Reinforcements on the other key were delayed 30 sec. It was found that (a) pigeons preferred mixed relative to constant delay of reinforcement, and (b) preference for mixed delay of reinforcement increased as the range of delay interval variability increased.

Stratospheric ozone destruction by man-made chlorofluoromethanes.

Calculations indicate that chlorofluoromethanes produced by man can greatly affect the concentrations of stratospheric ozone in future decades. This effect follows the release of chlorine from these compounds in the stratosphere. Present usage levels of chlorofluoromethanes can lead to chlorine-catalyzed ozone destruction rates that will exceed natural sinks of ozone by 1985 or 1990.