New observational constraints for atmospheric hydroxyl on global and hemispheric scales

Dramatic declines in emissions of methyl chloroform (1,1, 1-trichloroethane) resulting from the Montreal Protocol provide an unprecedented opportunity to improve our understanding of the oxidizing power of Earth's atmosphere. Atmospheric observations of this industrial gas during the late 1990s yield new insights into the global burden and distribution of the hydroxyl radical. Our results set firm upper limits on the global and Southern Hemispheric lifetimes of methyl chloroform and confirm the predominance of hydroxyl in the tropics. Our analysis suggests a global lifetime for methyl chloroform of 5.2 (+0.2, -0.3) years, a Southern Hemispheric lifetime of 4.9 (+0.2, -0.3) years, and mean annual concentrations of OH that are 15 +/- 10% higher south of the intertropical convergence zone than those north of this natural mixing boundary between the hemispheres.     

Volcanic gases in the april 1979 soufriere eruption

Six gas samples from the 17 April 1979 Soufriere eruption plume were analyzed for carbonyl sulfide, carbon disulfide, carbon monoxide, carbon dioxide, methane, nitrous oxide, fluorocarbon-11, fluorocarbon-12, methyl chloroform, and carbon tetrachloride. Only carbon monoxide, carbon dioxide, carbonyl sulfide, and carbon disulfide were found to have increased mixing ratios as compared with those in clean tropospheric air, but the increases were not sufficient to contribute greatly to the global budgets of these four components.     

Rate constants for the reactions of hydroxyl and hydroperoxyl radicals with ozone

Chain decomposition of ozone by hydroxyl and hydroperoxyl radicals has been observed. The rate constant at 3000 degrees K for OH + O(3)-->HO(2) + O(2) is 8 x 10(-14) cubic centimeters per second. The rate constant for HO(2) + O(3)--> OH + 2O(2), is 3 x 10(-15) cubic centimeters per second. These results have implications concerning stratospheric ozone.     

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 trends in methylchloroform and the global average for the hydroxyl radical

Frequent atmospheric measurements of the anthropogenic compound methylchloroform that were made between 1978 and 1985 indicate that this species is continuing to increase significantly around the world. Reaction with the major atmospheric oxidant, the hydroxyl radical (OH), is the principal sink for this species. The observed mean trends for methylchloroform are 4.8, 5.4, 6.4, and 6.9 percent per year at Aldrigole (Ireland) and Cape Meares (Oregon), Ragged Point (Barbados), Point Matatula (American Samoa), and Cape Grim (Tasmania), respectively, from July 1978 to June 1985. These measured trends, combined with knowledge of industrial emissions, were used in an optimal estimation inversion scheme to deduce a globally averaged methylchloroform atmospheric lifetime of 6.3 (+ 1.2, -0.9) years (1sigma uncertainty) and a globally averaged tropospheric hydroxyl radical concentration of (7.7 +/- 1.4) x 10(5) radicals per cubic centimeter (1sigma uncertainty). These 7 years of gas chromatographic measurements, which comprise about 60,000 individual calibrated real-time air analyses, provide the most accurate estimates yet of the trends and lifetime of methylchloroform and of the global average for tropospheric hydroxyl radical levels. Accurate determination of hydroxyl radical levels is crucial to understanding global atmospheric chemical cycles and trends in the levels of trace gases such as methane.     

Chloride methylation by plant pectin: an efficient environmentally significant process

Atmospheric chloromethane (CH3Cl) plays an important role in stratospheric ozone destruction, but many uncertainties exist regarding the strengths of its sources and sinks and particularly regarding the processes generating this naturally occurring gas. Evidence is presented here that CH3Cl is produced in many terrestrial environments by a common mechanism. Abiotic conversion of chloride to CH3Cl occurs readily in plant material, with the widespread plant component pectin acting as a methyl donor. Significant CH3Cl emissions from senescent and dead leaves were observed at ambient temperatures; those emissions rose dramatically when temperatures increased. This ubiquitous process acting in terrestrial ecosystems and during biomass burning could contribute the bulk of atmospheric CH3Cl.     

Carbon Dioxide Transport by Ocean Currents at 25{degrees}N Latitude in the Atlantic Ocean

Measured concentrations of CO(2), O(2), and related chemical species in a section across the Florida Straits and in the open Atlantic Ocean at approximately 25 degrees N, have been combined with estimates of oceanic mass transport to estimate both the gross transport of CO(2) by the ocean at this latitude and the net CO(2) flux from exchange with the atmosphere. The northward flux was 63.9 x 10(6) moles per second(mol/s); the southward flux was 64.6 x 10(6) mol/s. These values yield a net CO(2) flux of 0.7 x 10(6) mol/s (0.26 +/- 0.03 gigaton of C per year) southward. The North Atlantic Ocean has been considered to be a strong sink for atmospheric CO(2), yet these results show that the net flux in 1988 across 25 degrees N was small. For O(2) the equivalent signal is 4.89 x 10(6) mol/s northward and 6.97 x 10(6) mol/s southward, and the net transport is 2.08 x 10(6) mol/s or three times the net CO(2) flux. These data suggest that the North Atlantic Ocean is today a relatively small sink for atmospheric CO(2), in spite of its large heat loss, but a larger sink for O(2) because of the additive effects of chemical and thermal pumping on the CO(2) cycle but their near equal and opposite effects on the CO(2) cycle.     

Titan's atmospheric temperatures, winds, and composition

Temperatures obtained from early Cassini infrared observations of Titan show a stratopause at an altitude of 310 kilometers (and 186 kelvin at 15 degrees S). Stratospheric temperatures are coldest in the winter northern hemisphere, with zonal winds reaching 160 meters per second. The concentrations of several stratospheric organic compounds are enhanced at mid- and high northern latitudes, and the strong zonal winds may inhibit mixing between these latitudes and the rest of Titan. Above the south pole, temperatures in the stratosphere are 4 to 5 kelvin cooler than at the equator. The stratospheric mole fractions of methane and carbon monoxide are (1.6 +/- 0.5) x 10(-2) and (4.5 +/- 1.5) x 10(-5), respectively.     

Carbon dioxide supersaturation in the surface waters of lakes

Data on the partial pressure of carbon dioxide (CO(2)) in the surface waters from a large number of lakes (1835) with a worldwide distribution show that only a small proportion of the 4665 samples analyzed (less than 10 percent) were within +/-20 percent of equilibrium with the atmosphere and that most samples (87 percent) were supersaturated. The mean partial pressure of CO(2) averaged 1036 microatmospheres, about three times the value in the overlying atmosphere, indicating that lakes are sources rather than sinks of atmospheric CO(2). On a global scale, the potential efflux of CO(2) from lakes (about 0.14 x 10(15) grams of carbon per year) is about half as large as riverine transport of organic plus inorganic carbon to the ocean. Lakes are a small but potentially important conduit for carbon from terrestrial sources to the atmospheric sink.     

Atmospheric residence time of CH3Br estimated from the junge spatial variability relation

The atmospheric residence time for methyl bromide (CH3Br) has been estimated as 0.8 +/- 0.1 years from its empirical spatial variability relative to C2H6, C2Cl4, CHCl3, and CH3Cl. This evaluation of the atmospheric residence time, based on Junge's 1963 general proposal, provides an estimate for CH3Br that is independent of source and sink estimates. Methyl bromide from combined natural and anthropogenic sources furnishes about half of the bromine that enters the stratosphere, where it plays an important role in ozone destruction. This residence time is consistent with the 0.7-year value recently calculated for CH3Br from the combined strength estimates for its known significant sinks.     

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.     

Venus: atmospheric motion and structure from mariner 10 pictures

The Mariner 10 television camieras imaged the planet Venus in the visible and near ultraviolet for a period of 8 days at resolutions ranging from 100 meters to 130 kilometers. Tle general pattern of the atmospheric circulation in the upper tropospheric/lower stratospheric region is displayed in the pictures. Atmospheric flow is symmetrical between north and south hemispheres. The equatorial motions are zonal (east-west) at approxiimnately 100 meters per second, consistent with the previously inferred 4-day retrograde rotation. Angular velocity increases with latitude. The subsolar region, and the region downwind from it, show evidence of large-scale convection that persists in spite of the main zonal motion. Dynamical interaction between the zonal motion and the relatively stationary region of convection is evidenced by bowlike waves.     

The impact of agricultural soil erosion on the global carbon cycle

Agricultural soil erosion is thought to perturb the global carbon cycle, but estimates of its effect range from a source of 1 petagram per year(-1) to a sink of the same magnitude. By using caesium-137 and carbon inventory measurements from a large-scale survey, we found consistent evidence for an erosion-induced sink of atmospheric carbon equivalent to approximately 26% of the carbon transported by erosion. Based on this relationship, we estimated a global carbon sink of 0.12 (range 0.06 to 0.27) petagrams of carbon per year(-1) resulting from erosion in the world's agricultural landscapes. Our analysis directly challenges the view that agricultural erosion represents an important source or sink for atmospheric CO2.     

The Tunguska Explosion of 1908: Discovery of Meteoritic Debris near the Explosion Site and at the South Pole

Submillimeter-sized metallic spheres extracted from soil in the Tunguska region of central Siberia contain noble metals in cosmic proportions. The trace element composition and geographical distribution of these spheres suggest that they are from the 30 June 1908 Tunguska explosion and not meteoritic ablation products falling continuously on the earth. Debris from this explosion was also discovered in a South Pole ice core; this discovery indicates that the Tunguska object exploded in the atmosphere with subsequent stratospheric injection and transport of the debris. The celestial body that exploded over Tunguska weighed more than 7 million tons, was more than 0.16 kilometer in diameter, and may well have been a stony meteorite. This discovery offers a new precision time marker in polar ice strata for the year 1909. The steady-state influx of cosmic matter at the South Pole is estimated to be 1.8 x 10(-8) grams per square centimeter per year, which corresponds to a global influx of 4 x l0(5) tons per year.     

Emission of methyl bromide from biomass burning

Bromine is, per atom, far more efficient than chlorine in destroying stratospheric ozone, and methyl bromide is the single largest source of stratospheric bromine. The two main previously known sources of this compound are emissions from the ocean and from the compound's use as an agricultural pesticide. Laboratory biomass combustion experiments showed that methyl bromide was emitted in the smoke from various fuels tested. Methyl bromide was also found in smoke plumes from wildfires in savannas, chaparral, and boreal forest. Global emissions of methyl bromide from biomass burning are estimated to be in the range of 10 to 50 gigagrams per year, which is comparable to the amount produced by ocean emission and pesticide use and represents a major contribution ( approximately 30 percent) to the stratospheric bromine budget.     

The charnockite geotherm

Charnockite, a hypersthene-bearing granite, and other associated rocks of the charnockite series have a global distribution. These rocks, according to evidence from mineral-chemical and experimental phase equilibrium relations, formed or recrystallized at temperatures between 800 degrees and 900 degrees C and at relatively shallow depths of 6 to 12 kilometers. This evidence indicates the existence of geothermal gradients of 70 degrees to 100 degrees C per kilometer probably at various times, the latest being around 1300 x 10(6) years ago.     

Coupling of nitrous oxide and methane by global atmospheric chemistry

Nitrous oxide (N(2)O) and methane (CH(4)) are chemically reactive greenhouse gases with well-documented atmospheric concentration increases that are attributable to anthropogenic activities. We quantified the link between N(2)O and CH(4) emissions through the coupled chemistries of the stratosphere and troposphere. Specifically, we simulated the coupled perturbations of increased N(2)O abundance, leading to stratospheric ozone (O(3)) depletion, altered solar ultraviolet radiation, altered stratosphere-to-troposphere O(3) flux, increased tropospheric hydroxyl radical concentration, and finally lower concentrations of CH(4). The ratio of CH(4) per N(2)O change, -36% by mole fraction, offsets a fraction of the greenhouse effect attributable to N(2)O emissions. These CH(4) decreases are tied to the 108-year chemical mode of N(2)O, which is nine times longer than the residence time of direct CH(4) emissions.     

The hydroperoxyl radical in atmospheric chemical dynamics: reaction with carbon monoxide

From measurements of the photochemical rate of production of CO(2)(16,18) and CO(2)(16,16), produced from the low intensity photolysis of mixtures of CO, H(2)O, Ar, and O(2)(18,18), the rate constant for the reaction HO(2) + CO --> CO(2) + OH has been determined at 300 degrees K to be less than or equal to 10(-20) cubic centimeter per molecule per second. These measurements indicate that the reaction of thermalized HO(2) is of negligible importance as a sink mechanism for converting CO to CO(2) in either the troposphere or the stratosphere.     

Air containing nitrogen-15 ammonia: foliar absorption by corn seedlings

Thirty-day-old corn seedlings, grown in the greenhouse with different concentrations of supplemental nitrate nitrogen, were moved to a constant-temperature growth chamber and sealed in a 560-liter tent made of polyvinyl chloride. The plants were exposed to air containing ammonia labeled with nitrogen-15 (1, 10, and 20 parts per million) for 24 hours and then harvested. The nitrogen-15 content of the tops and roots showed that at 1 part per million 43 percent of the ammonia was absorbed, whereas at 10 and 20 parts per million, 30 percent of the ammonia was absorbed. The results demonstrate that growing plants may be a natural sink for atmospheric ammonia.     

Stratospheric nitrogen dioxide in the vicinity of soufriere, st. Vincent

In April 1979, measurements of nitrogen dioxide in the upper atmosphere were made near Soufriere Volcano by twilight optical-absorption techniques. The derived value of 5 x 10(15) molecules per square centimeter column implies an enhancement of 25 percent over earlier abundances measured in the same latitudinal regions. This enhancement may represent the normal stratospheric variability of nitrogen dioxide in the equatorial region but in any case may be considered an upper limit to the volcano's effect on the total nitrogen dioxide abundance.