Greenhouse gases and recovery of the Earth’s ozone layer

A numerical 2-D zonally averaged dynamical radiative-photochemical model of the ozonosphere including aerosol physics is used to examine the role of the greenhouse gases CO₂, CH₄, and N₂O in the recovery of the Earth’s ozone layer after reduction of anthropogenic discharges of chlorine and bromine compounds into the atmosphere. A weakness in efficiencies of all catalytic cycles of the ozone destruction due to cooling of the stratosphere caused by greenhouse gases is shown to be a dominant mechanism of the impact of the greenhouse gases on the ozone layer. Numerical experiments show that the total ozone changes caused by greenhouse gases will be comparable in absolute value with the changes due to chlorine and bromine species in the middle of the 21st century. Continuous anthropogenic growth of CO₂ will lead to a significantly faster recovery of the ozone layer. In this case, the global total ozone in the latitude range from 60°S to 60°N will reach its undisturbed level of 1980 by about 2040. If the CO₂ growth stops, the global total ozone will reach this level only by the end of the century.     

The global distribution and variability of stratospheric constituents measured by LIMS

The purpose of the Nimbus 7 LIMS experiment was to sound the composition and structure of the upper atmosphere and provide data for study of photochemistry, radiation, and dynamics processes. Vertical profiles were measured of temperature and ozone (O₃) over the 10-km to 65-km range and water vapor (H₂O), nitrogen dioxide (NO₂), and nitric acid (HNO₃) over the 10-km to ～50-km range. Latitude coverage extended from 64°S to 84°N. Several general features of the atmosphere have emerged from data analyses thus far. Nitrogen dioxide exhibits rapid latitudinal variations in winter and shows hemispheric asymmetry with generally higher vertical column amount in the summer hemisphere. HNO₃ data show that this gas is highly variable with altitude, latitude, and season. Smallest mixing ratios occur in the tropics, and the largest values occur in the high latitude winter hemisphere. The results show that O₃, NO₂, and HNO₃ are strongly affected during a stratospheric warming. There is a persistently low water vapor mixing ratio in the tropical lower stratosphere (～2–3 ppmv), a poleward gradient at all times in the mission, and evidence of increasing mixing ratio with altitude at tropical and middle latitudes.     

Assessment of the ozone and temperature variability during 1979–1993 with the chemistry-climate model SOCOL

The chemistry-climate model SOCOL has been applied for the study of ozone and temperature anomalies during 1979–1993. Temperature and ozone anomalies have been obtained for a set of model runs forced by all major stratospheric forcing mechanisms. Forcings have been prescribed separately and together to assess their individual influence on stratospheric ozone and temperature. The results of these simulations have been compared to available satellite data. The model captures well ozone depletion and cooling in the upper stratosphere due to increases in the abundance of greenhouse gases and ozone depleting substances in the atmosphere. In the lower stratosphere, the model reproduces the warming over tropical and middle latitudes caused by the El-Chichon and Pinatubo eruptions. However, the simulated ozone response is overestimated in comparison with SAGE data. The best agreement with observations has been obtained for the run with all forcings included. This emphasizes the importance of the volcanic and solar forcings for the correct reproduction of observed trends. Comparison of near-global total ozone anomalies confirms an overestimation of ozone depletion just after volcanic eruptions, while the overall agreement with the model is fairly good.     

The influence of the several very large solar proton events in years 2000–2003 on the neutral middle atmosphere

Solar proton events (SPEs) are known to have caused changes in constituents in the Earth’s polar neutral middle atmosphere. The past four years, 2000–2003, have been replete with SPEs. Huge fluxes of high energy protons entered the Earth’s atmosphere in periods lasting 2–3 days in July and November 2000, September and November 2001 and October 2003. The highly energetic protons produce ionizations, excitations, dissociations and dissociative ionizations of the background constituents, which lead to the production of HO_x (H, OH, HO₂) and NO_y (N, NO, NO₂, NO₃, N₂O₅, HNO₃, HO₂NO₂, ClONO₂, BrONO₂). The HO_x increases lead to short-lived ozone decreases in the polar mesosphere and upper stratosphere due to the short lifetimes of the HO_x constituents. Large mesospheric ozone depletions (>70%) due to the HO_x enhancements were observed and modeled as a result of the very large July 2000 SPE. The NO_y increases lead to long-lived stratospheric ozone changes because of the long lifetime of the NO_y family in this region. Polar total ozone depletions >1% were simulated in both hemispheres for extended periods of time (several months) as a result of the NO_y enhancements due to the very large SPEs.     

Assessing the feasibility of involving gaseous products resulting from physicochemical oxidation of human liquid and solid wastes in the cycling of a bio-technical life support system

The study addresses the possible ways of involving gaseous products produced by “wet” incineration of human wastes mixed with H₂O₂ in an alternating electric field in the cycling of the physical model of a bio-technical life support system (BTLSS). The resulting gas mixture contains CO₂ and O₂, which are easily involved in the cycling in the closed ecosystem, and NH₃, which is unacceptable in the atmosphere of the BTLSS. NH₃ fixation has been proposed, which is followed by nitrification and involvement of the resulting products in the mass exchange of the closed system. Experiments have been performed to show that plants can be grown in the atmosphere resulting from the closing of the gas loop that includes a physicochemical installation and a growth chamber with plants representing the phototrophic compartment of the BTLSS. The results of the study suggest the conclusion that the proposed method of organic waste oxidation can be a useful tool in creating a physical model of a closed-loop integrated BTLSS.     

Statistical comparison of night-time NO2 observations in 2003–2006 from GOMOS and MIPAS instruments

GOMOS (Global Ozone Monitoring by Occultation of Stars) and MIPAS (Michelson Interferometer for Passive Atmospheric Sounding) are remote sensing instruments on board the European Space Agency’s Envisat satellite. GOMOS and MIPAS have been designed for observations of stratospheric and mesospheric constituents, including ozone and nitrogen dioxide. Both instruments have a good global coverage of observations and can provide data also from the polar regions. In this paper, we compare night-time NO₂ data from GOMOS with those from MIPAS. We present statistics of selected sets of data spanning from the year 2003 to 2006. The results for low-to-mid latitudes show that the two instruments are in a good agreement in the middle stratosphere, the differences being typically less than 5%. In the upper stratosphere, GOMOS observations generally show 15% higher values than those from MIPAS. The bias is in virtually all cases smaller than the combined systematic error of the measurements, giving great confidence in the GOMOS and MIPAS data quality. The result for high mesospheric NO₂ mixing ratios observed in the polar regions during winter times indicate a good agreement between GOMOS and MIPAS. In the mesosphere, the difference is less than 35% and smaller than the systematic error. Due to the high mesospheric signal, MIPAS sensitivity decreases in the stratosphere which results in larger differences between the two instruments.     

The variability of stratospheric nitrogen compounds observed by LIMS in the winter of 1978–1979

The LIMS experiment was launched on the Nimbus 7 satellite for the purpose of sounding the vertical structure of temperature and key upper atmosphere trace gases on a global scale. The technique of thermal infrared limb sounding was used to obtain measurements of O₃, H₂O, NO₂, and HNO₃. LIMS collected data almost continuously from late October to late May over the latitude range from 64°S to 84°N. Two of the gases, NO₂ and HNO₃, are important elements in the NO_x chain of chemical reactions leading to ozone destruction. We will describe results for these gases in terms of zonal mean profiles and latitudinal distributions. The period selected for study is January–May 1979, when a major stratospheric warming occurred.     

Thermally evolved gas analysis (TEGA) of hyperarid soils doped with microorganisms from the Atacama Desert in southern Peru: Implications for the Phoenix mission

TEGA, one of several instruments on board of the Phoenix Lander, performed differential scanning calorimetry and evolved gas analysis of soil samples and ice, collected from the surface and subsurface at a northern landing site on Mars. TEGA is a combination of a high temperature furnace and a mass spectrometer (MS) that was used to analyze samples delivered to the instrument via a robotic arm. The samples were heated at a programmed ramp rate up to 1000 °C. The power required for heating can be carefully and continuously monitored (scanning calorimetry). The evolved gases generated during the process can be analyzed with the evolved gas analyzer (a magnetic sector mass spectrometer) in order to determine the composition of gases released as a function of temperature. Our laboratory has developed a sample characterization method using a pyrolyzer integrated to a quadrupole mass spectrometer to support the interpretations of TEGA data. Here we examine the evolved gas properties of six types of hyperarid soils from the Pampas de La Joya in southern Peru (a possible analog to Mars), to which we have added with microorganisms (Salmonella typhimurium, Micrococcus luteus, and Candida albicans) in order to investigate the effect of the soil matrix on the TEGA response. Between 20 and 40 mg of soil, with or without ∼5 mg of lyophilized microorganism biomass (dry weight), were placed in the pyrolyzer and heated from room temperature to 1200 °C in 1 h at a heating rate of 20 °C/min. The volatiles released were transferred to a MS using helium as a carrier gas. The quadrupole MS was ran in scan mode from 10 to 200 m/z. In addition, ∼20 mg of each microorganism without a soil matrix were analyzed. As expected, there were significant differences in the gases released from microorganism samples with or without a soil matrix, under similar heating conditions. Furthermore, samples from the most arid environments had significant differences compared with less arid soils. Organic carbon released in the form of CO₂ (ion 44 m/z) from microorganisms evolved at temperatures of ∼326.0 ± 19.5 °C, showing characteristic patterns for each one. Others ions such as 41, 78 and 91 m/z were also found. Interestingly, during the thermal process, the release of CO₂ increased and ions previously found disappeared, demonstrating a high-oxidant activity in the soil matrix when it was subjected to high temperature. Finally, samples of soil show CO₂ evolved up to 650 °C consistent with thermal decomposition of carbonates. These results indicate that organics mixed with these hyperarid soils are oxidized to CO₂. Our results suggest the existence of at least two types of oxidants in these soils, a thermolabile oxidant which is highly oxidative and other thermostable oxidant which has a minor oxidative activity and that survives the heat-treatment. Furthermore, we find that the interaction of biomass added to soil samples gives a different set of breakdown gases than organics resident in the soil. The nature of oxidant(s) present in the soils from Pampas de La Joya is still unknown.     

Ozone variability related to several SEP events occurring during solar cycle no. 23

Data from geostationary operational environmental satellite (GOES) series were used to identify intense solar energetic particle (SEP) events occurred during the solar activity cycle no. 23. We retrieved O₃, NO, NO₂, HNO₃, OH, HCl and OHCl profiles coming from different satellite sensors (solar occultation and limb emission) and we looked for the mesospheric/stratospheric response to SEPs at high terrestrial latitudes. The chemistry of the minor atmospheric components is analysed to evaluate the associated odd nitrogen (NO_x) and odd hydrogen (HO_x) production, able to cause short (h) and medium (days) term ozone variations. We investigated the effects of SEPs on the polar atmosphere in three different seasons, i.e., January 2005, April 2002 and July 2000. The inter-hemispheric variability of the ozone, induced by the SEP series of January 2005, has been compared with the effects connected both to larger and quite similar events. We found that during SEP events: (i) solar illumination is the key factor driving SEP-induced effects on the chemistry of the polar atmosphere; (ii) even events with limited particle flux in the range 15–40 MeV are able to change the abundance of the minor constituents in the mesosphere and upper stratosphere.     

Stratospheric trace gas distributions observed in different seasons

A newly developed balloon-borne cryogenic sampler has been used to collect large air samples in the midlatitude stratosphere (44° N). The samples were analysed for their content of several longlived trace gases. The vertical profiles of N₂O, CH₄, and CF₂Cl₂ derived from two balloon flights in winter 1982 and, as part of the MAP Globus Project, in fall 1983 indicate variations that are caused by large scale dynamic processes. Significant features of the profiles are discussed and compared with averaged profiles that were derived from a series of balloon sampling flights performed previously over the same location during the summer season. The temporal variation of the individual profiles is more detailed than predicted by model calculations.     

Measurement of minor species (H2, Cl,O3, NO) in the earth's atmosphere by the occultation technique

The stellar occultation technique is a clean and powerful means of detecting and quantifying minor gases in the earth's atmosphere. The results obtained are totally insensitive to knowledge of the absolute flux of the star, and are not influenced by instrument calibration problems. Pioneering observations of nocturnal mesospheric ozone and thermospheric molecular oxygen by the stellar occultation technique were made in 1970 and 1971 with the Wisconsin stellar photometers on board the Orbiting Astronomical Observatory-2. A limb crossing geometry was used. The high resolution Princeton ultraviolet spectrometer aboard Copernicus was used in the summers of 1975, 1976 and 1977 to measure altitude profiles of molecular hydrogen, atomic chlorine and nitric oxide in addition to ozone and molecular oxygen. A limb grazing geometry was employed. The ozone densities show wide variation from orbit to orbit and particularly betewen the OAO-2 and Copernicus observations. A H₂ density of 1×10⁸ cm^?3 at 95 km, and a NO density less than 10⁶ cm^?3 for altitudes greater than 85 km were measured.     

Statistical global and regional atmospheric models of temperature and gas components over the northern hemisphere

Statistical mid-latitude models of altitude distribution of temperature, water vapor, ozone, carbon dioxide and trace gases (CO, CH₄, N₂O, NO, NO₂) are considered. The mean characteristics of altitude profiles of these parameters, as well as their time and space variability, have been taken into account. The statistical regional models were constructed using a temperature-humidy complex. The considered statistical mid-latitude models have been constructed as applied to solutions of the problems on remote sounding of the atmosphere and underlying surface from outer space.     

Influence of solar 11-year variability on chemical composition of the stratosphere and mesosphere simulated with a chemistry-climate model

An understanding of observed global chemistry and climate changes caused by solar activity changes is a high priority in modern geosciences. Here, we discuss the influence of the ultraviolet spectral irradiance variability during solar cycle on chemical composition of the stratosphere and mesosphere with chemistry-climate model that fully describes the interactions between chemical and thermo-dynamical processes. We have performed several 20-year long steady-state runs and found a significant influence of solar irradiation on the chemical composition in the stratosphere and mesosphere. An enhanced photolysis during solar maximum results in destruction of methane, nitrous oxide and CFCs providing an increase in the chemical activity of the atmosphere with more pronounced effects in the mesosphere. In the mesosphere, an increase of HO_x caused by more intensive water vapor photolysis results in significant ozone depletion there. More intensive methane oxidation gives statistically significant rise to the stratospheric humidity. The influence of dynamical perturbations has been identified over high latitude areas. The response of OH is found to be in a good agreement with observation data. The response of the other species is hard to validate, because of the lack of theoretical and observational studies.     

Model calculations of the dayside ionosphere of Venus

Model calculations of the dayside ionosphere of Venus are presented. The coupled continuity and momentum equations were solved for O₂⁺, O⁺, CO₂⁺, C⁺, N⁺, He⁺, and H⁺ density distributions, which are compared with measurements from the Pioneer Venus ion mass spectrometer. The agreement between the model results and the measurements is good for some species, such as O⁺, and rather poor for others, such as N⁺, indicating that our understanding of the dayside ion composition of Venus is incomplete. The coupled heat conduction equations for ions and electrons were solved and the calculated temperatures compared with Pioneer Venus measurements. It is shown that fluctuations in the magnetic field have a significant effect on the energy balance of the ionosphere.     

Vertical wavenumber spectra of atmospheric ozone measured from ozonesonde observations

Vertical profiles of ozone have been measured at balloon altitudes. Our purpose is to examine the character of vertical wavenumber spectra of ozone fluctuations, to assess the possible roles of gravity wave field in ozone fluctuations, and to determine dominant vertical wavelengths of ozone spectra. Vertical wavenumber spectra of 12 ozone fluctuations obtained during June–August 2003 are presented. Results indicate that mean spectral slopes in the wavenumber range from 4.69 × 10⁻⁴ to 2.50 × 10⁻³ cyc/m are about −2.91 in the troposphere and −2.87 in the lower stratosphere, which is close to the slope of −3 predicted by current gravity wave saturation models. The consistency of the observed spectral slopes with the value of −3 predicted by current gravity wave saturation models suggests that the observed ozone fluctuations are due primarily to atmospheric gravity waves. At m = 1/(1000 m) the mean spectral amplitude is over 30 times larger in the lower stratosphere than in the troposphere. Mean vertical wavenumber spectra in area-preserving form reveal dominant vertical wavelengths of ∼2.6 km in the troposphere and ∼2.7 km in the lower stratosphere, which is consistent with the values varying between 1.5 and 3.0 km estimated from the velocity field and temperature field at these heights.     

Air depression over south pole during Antarctic spring and its possible influence on ozone content in this region

Air depression during Antarctic spring, its long-term behaviour and connection with ozone content has been investigated on base of rocket data for polar regions and total ozone data sets for South pole (TOMS data) for 1979–1990. It was shown, that air pressure depression near South polar region in September in the lower stratosphere has a visible (about 5% per decade) negative trend similar to the tendency which total ozone records reveal. Rather high correlation (+0.82) between air pressure in the stratosphere and total ozone content for spring in Antarctica was found.     

Study of fast atoms in molecular gas plasma via emission spectroscopy

Fast atoms are generated in reactions of ions with the molecular gas in laboratory and astrophysical plasma. In hydrogen they are observed in the emission spectra via Excessive line broadening. Energetic atoms also occur in astrophysical plasma in hydrogen, nitrogen and oxygen. The proposal here is that low pressure discharges can be used to simulate the phenomena in certain space plasma. In this study, we have used a special configuration of the electrode system, to obtain energetic atoms in plasma of three types of diatomic gases (H₂, O₂, N₂). Emission spectroscopy was used to detect the atoms and measure their velocity. Energy analysis was performed to obtain atoms’ distributions and evaluate the mean energy of atoms. This was compared to the potential energy available from the electric field. The field acceleration model, previously established for hydrogen, was extended to nitrogen and oxygen. We suggest, that the same method of analysis can be applied for astrophysical plasma spectrum.     

Pressure,O2, and CO2, in aquatic Closed Ecological Systems

Pressure increased during net photosynthetic O₂ production in the light and decreased during respiratory O₂ uptake during the dark in aquatic Closed Ecological Systems (CESs) with small head gas volumes. Because most CO₂ will be in the liquid phase as bicarbonate and carbonate anions, and CO₂ is more soluble than O₂, volumes of gaseous CO₂ and gaseous O₂ will not change in a compensatory manner, leading to the development of pressure. Pressure increases were greatest with nutrient rich medium with NaHCO₃ as the carbon source. With more dilute media, pressure was greatest with NaHCO₃, and less with cellulose or no-added carbon. Without adequate turbulence, pressure measurements lagged dissolved O₂ concentrations by several hours and dark respiration would have been especially underestimated in our systems (250–1000 ml). With adequate turbulence (rotary shaker), pressure measurements and dissolved O₂ concentrations generally agreed during lights on/off cycles, but O₂ measurements provided more detail. At 20 °C, 29.9 times as much O₂ will distribute into the gas phase as in the liquid, per unit volume, as a result of the limited solubility of O₂ in water and according to Henry’s Law. Thus even a small head gas volume can contain more O₂ than a larger volume of water. When both dissolved and gaseous O₂ and CO₂ are summed, the changes in Total O₂ and CO₂ are in relatively close agreement when NaHCO₃ is the carbon source. These findings disprove an assumption made in some of Taub’s earlier research that aquatic CESs would remain at approximately atmospheric pressure because approximately equal molar quantities of O₂ and CO₂ would exchange during photosynthesis and respiration; this assumption neglected the distribution of O₂ between water and gas phases. High pressures can occur when NaHCO₃ is the carbon source in nutrient rich media and if head-gas volumes are small relative to the liquid volume; e.g., one “worse case” condition developed 800 mm Hg above atmospheric pressure and broke the glass container. Plastic screw cap closures are likely to leak at high pressures and should not be assumed to seal unless tested at appropriate pressures. Pressure can be reduced by having larger head-gas volumes and using less concentrated nutrient solutions. It is important that pressure changes be considered for both safety and closure, and if total O₂ is used as the measure of net photosynthesis and respiration, the O₂ in the gas phase must be added to the dissolved O₂.     

Temporal and spatial variations observed in the ionospheric composition of Venus: Implications for empirical modelling

In situ measurements of the thermal ion composition of the ionosphere of Venus have been obtained for a period of two Venus years from the Bennett rf ion mass spectrometer on the Pioneer Venus Orbiter. Ion measurements within an altitude interval of 160 to 300 kilometers, corresponding to an overall latitude interval of about ?4° to 34°N, are assembled from the interval December 1978 to March 1980. This time interval corresponds to two revolutions of Venus about the Sun, designated as two “diurnal cycles”. The distributions of several ion species in this data base have been sorted to identify temporal and spatial variations, and to determine the feasibility of an analytical representation of the experimental results. The first results from the sorting of several prominent ions including O⁺, O₂⁺, and H⁺ and several minor ions including CO₂⁺, C⁺, and H₂⁺ reveal significant diurnal variations, with superimposed modulation associated with solar activity and solar wind variations. The diurnal variation consists of strong day to night contrast in the ion concentrations, with differences of one to two orders of magnitude, depending upon ion mass and altitude. The concentrations of O₂⁺, O⁺, CO₂⁺ and C⁺ peak throughout the dayside decreasing sharply at the terminators to nightside levels, lower by one to two orders of magnitude relative to the dayside. The diurnal variations of the light ions H⁺ and H₂⁺ peak during the night, exhibiting asymmetric nightside bulges favoring the pre-dawn sector, near 0400 solar hour angle. Superimposed upon the diurnal distributions are modulation signatures which correlate well with modulation in the F_10.7 index, indicating a strong influence of solar variability on the ion production and distribution. The influence of solar wind perturbations upon the ion distributions are also indicated, by a significant increase in the scatter of the observations with increasing altitude as higher altitudes, approaching 300 kilometers, are sampled. Together, these temporal and spatial variations make the task of modelling the ionosphere of Venus both very interesting and challenging.     

A neutral gas mass spectrometer to measure the chemical composition of the stratosphere

The Polar Balloon Atmospheric Composition Experiment (P-BACE) is a new generation of neutral gas mass spectrometer based on the time-of-flight principle. P-BACE is the scientific experiment on the Mars Environment Analog Platform (MEAP) flown successfully on a balloon mission in summer 2008. The MEAP mission was flown with a 334,000 m³ helium balloon in the stratosphere on a semicircular trajectory from northern Sweden around the North Pole to Canada using the summer northern hemispheric wind current. The atmospheric conditions at an atmospheric altitude of 35–40 km are remarkably similar to those on the surface of Mars and thus the balloon mission was an ideal testbed for our mass spectrometer P-BACE. Originally this instrument was designed for in situ measurements of the chemical composition of the Martian atmosphere.P-BACE has a unique mass range from 0 to 1000 amu/q with a mass resolution m/Δm (FWHM) > 1000, and the dynamic range is at least six orders of magnitude. During this experiment, the acquisition of one mass spectrum is a sum of 65,535 single spectra, recorded in a time frame of 66 s.The balloon mission lasted 5 days and had successfully demonstrated the functionality of the P-BACE instrument during flight conditions. We had recorded more than 4500 mass spectra. With little modifications, P-BACE can be used on a planetary mission for Mars, but for example also for Venus or Mercury, if placed on a satellite.