Role of deep cloud convection in the ozone budget of the troposphere.

Convective updrafts in thunderstorms prolong the lifetime of ozone (O(3)) and its anthropogenic precursor NOx [nitric oxide (NO) + nitrogen dioxide (NO(2))] by carrying these gases rapidly upward from the boundary layer into a regime where the O(3) production efficiency is higher, chemical destruction is slower, and surface deposition is absent. On the other hand, the upper troposphere is relatively rich in O(3) and NOx from natural sources such as downward transport from the stratosphere and lightning; convective overturning conveys the O(3) and NOx toward the Earth's surface where these components are more efficiently removed from the atmosphere. Simulations with a three-dimensional global model suggest that the net result of these counteractive processes is a 20 percent overall reduction in total tropospheric O(3). However, the net atmospheric oxidation efficiency is enhanced by 10 to 20 percent.

Biomass burning in the tropics: impact on atmospheric chemistry and biogeochemical cycles.

Biomass burning is widespread, especially in the tropics. It serves to clear land for shifting cultivation, to convert forests to agricultural and pastoral lands, and to remove dry vegetation in order to promote agricultural productivity and the growth of higher yield grasses. Furthermore, much agricultural waste and fuel wood is being combusted, particularly in developing countries. Biomass containing 2 to 5 petagrams of carbon is burned annually (1 petagram = 10(15) grams), producing large amounts of trace gases and aerosol particles that play important roles in atmospheric chemistry and climate. Emissions of carbon monoxide and methane by biomass burning affect the oxidation efficiency of the atmosphere by reacting with hydroxyl radicals, and emissions of nitric oxide and hydrocarbons lead to high ozone concentrations in the tropics during the dry season. Large quantities of smoke particles are produced as well, and these can serve as cloud condensation nuclei. These particles may thus substantially influence cloud microphysical and optical properties, an effect that could have repercussions for the radiation budget and the hydrological cycle in the tropics. Widespread burning may also disturb biogeochemical cycles, especially that of nitrogen. About 50 percent of the nitrogen in the biomass fuel can be released as molecular nitrogen. This pyrdenitrification process causes a sizable loss of fixed nitrogen in tropical ecosystems, in the range of 10 to 20 teragrams per year (1 teragram = 10(12) grams).

Solar proton events: stratospheric sources of nitric oxide.

The production of nitric oxide (NO) in the stratosphere during each of the solar proton events of November 1960, September 1966, and August 1972 is calculated to have been comparable to or larger than the total average annual production of NO by the action of galactic cosmic rays. It is therefore very important to consider the effect of solar proton events on the temporal and spatial distribution of ozone in the stratosphere. A study of ozone distribution after such events may be particularly important for validating photochemical-diffusion models.

Aerosols, climate, and the hydrological cycle.

Human activities are releasing tiny particles (aerosols) into the atmosphere. These human-made aerosols enhance scattering and absorption of solar radiation. They also produce brighter clouds that are less efficient at releasing precipitation. These in turn lead to large reductions in the amount of solar irradiance reaching Earth's surface, a corresponding increase in solar heating of the atmosphere, changes in the atmospheric temperature structure, suppression of rainfall, and less efficient removal of pollutants. These aerosol effects can lead to a weaker hydrological cycle, which connects directly to availability and quality of fresh water, a major environmental issue of the 21st century.

Solar proton event: influence on stratospheric ozone.

Large-scale reductions in the ozone content of the middle and upper stratosphere over the polar cap regions were associated with the major solar proton event of 4 August 1972. This reduction, which was determined from measurements with the backscattered ultraviolet experiment on the Nimbus 4 satellite, is interpreted as being due to the catalytic destruction of ozone by odd-nitrogen compounds (NO(x)) produced by the event.

A Reevaluation of the Ozone Budget with HALOE UARS Data: No Evidence for the Ozone Deficit.

Recently, additional ozone production mechanisms have been proposed to resolve the ozone deficit problem, which arises from greater ozone destruction than production in several photochemical models of the upper stratosphere and lower mesosphere. A detailed ozone model budget analysis was performed with simultaneous observations of O(3), HCl, H(2)O, CH(4), NO, and NO(2) from the Halogen Occultation Experiment (HALOE) on the Upper Atmosphere Research Satellite (UARS) under conditions with the strongest photochemical control of ozone. The results indicate that an ozone deficit may not exist. On the contrary, the use of currently recommended photochemical parameters leads to insufficient ozone destruction in the model.

Termites: a potentially large source of atmospheric methane, carbon dioxide, and molecular hydrogen.

Termites may emit large quantities of methane, carbon dioxide, and molecular hydrogen into the atmosphere. Global annual emissions calculated from laboratory measurements could reach 1.5 x 10(14) grams of methane and 5 x 10(16) grams of carbon dioxide. As much as 2 x 10(14) grams of molecular hydrogen may also be produced. Field measurements of methane emissions from two termite nests in Guatemala corroborated the laboratory results. The largest emissions should occur in tropical areas disturbed by human activities.

The Indian Ocean experiment: widespread air pollution from South and Southeast Asia.

The Indian Ocean Experiment (INDOEX) was an international, multiplatform field campaign to measure long-range transport of air pollution from South and Southeast Asia toward the Indian Ocean during the dry monsoon season in January to March 1999. Surprisingly high pollution levels were observed over the entire northern Indian Ocean toward the Intertropical Convergence Zone at about 6 degrees S. We show that agricultural burning and especially biofuel use enhance carbon monoxide concentrations. Fossil fuel combustion and biomass burning cause a high aerosol loading. The growing pollution in this region gives rise to extensive air quality degradation with local, regional, and global implications, including a reduction of the oxidizing power of the atmosphere.

Relationship of peroxyacetyl nitrate to active and total odd nitrogen at northern high latitudes: influence of reservoir species on NOx and O3.

Measurements of peroxyacetyl nitrate (PAN), NO, NO2, HNO3, NOy (total odd nitrogen), and O3 were made in the high-latitude troposphere over North America and Greenland (35 degrees to 82 degrees N) during the Arctic Boundary Layer Expedition (ABLE 3A) (July-August 1988) throughout 0-to 6-km altitudes. These data are analyzed to quantitatively describe the relationships between various odd nitrogen species and assess their significance to global tropospheric chemistry. In the free troposphere, PAN was as much as 25 times more abundant than NOx. PAN to NOx ratio increased with increasing altitude and latitude. PAN was found to be the single most abundant reactive nitrogen species in the free troposphere and constituted a major fraction of NOy, PAN to NOy ratios were about 0.1 in the boundary layer and increased to 0.4 in the free troposphere. A 2-D global photochemical model with C1-C3 hydrocarbon chemistry is used to compare model predictions with measured results. A sizable portion (approximately 50%) of the gaseous reactive nitrogen budget is unaccounted for, and unknown organic nitrates and pernitrates are expected to be present. Model calculations (August 1, 70 degrees N) show that a major fraction of the observed NOx (50 to 70% of median) may find its source in the available PAN reservoir. PAN and the unknown reservoir species may have the potential to control virtually the entire NOx availability of the high latitude troposphere. It is predicted that the summer NOx and O3 mixing ratios in the Arctic/sub-Arctic troposphere would be considerably lower in the absence of the ubiquitous PAN reservoir. Conversely, this PAN reservoir may be responsible for the observed temporal increase in tropospheric O3 at high latitudes.

The position dependent 15N enrichment of nitrous oxide in the stratosphere.

The position dependent 15N fractionation of nitrous oxide (N2O), which cannot be obtained from mass spectrometric analysis on molecular N2O itself, can be determined with high precision using isotope ratio mass spectrometry on the NO+ fragment that is formed on electron impact in the source of an isotope ratio mass spectrometer. Laboratory UV photolysis experiments show that strong position dependent 15N fractionations occur in the photolysis of N2O in the stratosphere, its major atmospheric sink. Measurements on the isotopic composition of stratospheric N2O indeed confirm the presence of strong isotope enrichments, in particular the difference in the fractionation constants for 15N14NO and 14N15NO. The absolute magnitudes of the fractionation constants found in the stratosphere are much smaller, however, than those found in the lab experiments, demonstrating the importance of dynamical and also additional chemical processes like the reaction of N2O with O(1D).

Mass extinctions and supernova explosions.

In a recent contribution to this journal Ellis and Schramm [Ellis, J. & Schramm, D. N. (1995) Proc. Natl. Acad. Sci. USA 92, 235-238] claim that supernova explosions can cause massive biological extinctions as a result of strongly enhanced stratospheric NOx (NO + NO2) production by accompanying galactic cosmic rays. They suggested that these NOx productions which would last over several centuries and occur once every few hundred million years would result in ozone depletions of about 95%, leading to vastly increased levels of biologically damaging solar ultraviolet radiation. Our detailed model calculations show, however, substantially smaller ozone depletions ranging from at most 60% at high latitudes to below 20% at the equator.

Volcanic Bishop's ring: evidence for a sulfuric acid tetrahydrate particle aureole.

Following the massive 1883 Krakatoa volcanic eruption, a new atmospheric optical phenomeon was identified by Rev. S. E. Bishop. This inconspicuous one-ringed corona, or aureole, was immediately linked to the global spread of volcanic debris injected into the stratosphere, but little refinement in the mechanisms responsible for Bishop's ring has since been made. On the basis of our combined studies of sulfuric acid droplet-freezing theory and polarization (0.694-µm) lidar measurements of Bishop's ring aerosols from the June 1991 Mt. Pinatubo eruption that show average linear depolarization ratios of ;~0.05, it appears that this solar diffraction phenomenon is caused by accumulations of nonspherical sulfuric acid tetrahydrate (SAT) particles. The diffraction-theory aureole-derived SAT particle radius of ~0.8 µm is consistent with the freezing of the large mode of volcanic acid droplets created by coagulation, which, according to theory, is necessary for concentrating a sufficient insoluble mass to promote het rogeneous drop freezing at temperatures below approximately -65 °C.

Global air pollution crossroads over the Mediterranean.

The Mediterranean Intensive Oxidant Study, performed in the summer of 2001, uncovered air pollution layers from the surface to an altitude of 15 kilometers. In the boundary layer, air pollution standards are exceeded throughout the region, caused by West and East European pollution from the north. Aerosol particles also reduce solar radiation penetration to the surface, which can suppress precipitation. In the middle troposphere, Asian and to a lesser extent North American pollution is transported from the west. Additional Asian pollution from the east, transported from the monsoon in the upper troposphere, crosses the Mediterranean tropopause, which pollutes the lower stratosphere at middle latitudes.

Observations of air composition in Brazil between the Equator and 20°s during the dry season

Field measurement programs in Brazil during the dry season months of August and September in 1979 and 1980 have demonstrated the great importance of the continental tropics in global air chemistry. Especially in the mixed layer, the air composition over land is much different from that over the ocean and the land areas are clearly longe scale sources of many inportant trace gases. During the dry season much biomass, burning takes place especially in the cerrado regions leading to substantial emission of air pollutants, such as CO, NOx, N2O, CH4 and other hydrocarbons. Ozone concentrations are alsoenhanced due to photochemical reactions. Biogenic organic emissions from tropical forests play likewise an important role in the photochemistry of the atmosphere. Carbon monoxide was found to be present in high concentrations in the boundary layer of the tropical forest, but ozone concentrations were much lower than in the cerrado.

Programa de medidas de campo no Brasil nas estações secas de 1979 e 1980, durante os meses de agosto e setembro, demonstraram a grande importância das regiões tropicais continentais na química atmosférica global. Especialmente na camada de mistura, a composição do ar sobre o continente e oceano é muito diferente e as regiões terrestres são fontes de produção em grande escala de muitos gases-traço importantes. Queimas de blomassa ocorrem durante a estação seca, especialmente nos cerrados, causando emissões substanciais de poluentes atmosféricos tais como CO, HOx, H2O, CH4, e outros hidrocarbonetos. Concentrações de ozônio são tombém aumentadas devido a reações fotoquímicas. Emissões orgânicas biogênicas de florestas tropicais tem um papel importante na fitoquímica da atmosfera. O monóxido de carbono mostrou-se presente em altas concentrações na camada limite da floresta tropical e as concentrações de ozônio foram muito inferiores no cerrado.