Studies of proton-irradiated cometary-type ice mixtures

Radiation synthesis has been proposed as a mechanism for changing the nature of the outer few meters of ice in a comet stored 4.6 billion years in the Oort cloud and may explain some of the differences observed between new and more evolved comets. Cometary-type ice mixtures were studied in a laboratory experiment designed to approximately simulate the expected temperature, pressure, and radiation environment of the interstellar Oort cloud region. The 2.5- to 15-μm infrared absorption features of thin ice films were analyzed near 20°K before and after 1 MeV proton irradiation. Various ice mixtures included the molecules H₂O, NH₃, CH₄, N₂, C₃H₈, CO, and CO₂. All experiments confirm the synthesis of new molecular species in solid phase mixtures at 20°K. The synthesized molecules, identified by their infrared signatures, are C₂H₆, CO₂, CO, N₂O, NO, and CH₄ (weak). Synthesized molecules, identified by gas chromatographic (GC) analysis of the volatile fraction of the warmed irradiated ice mixture, are C₂H₄ or C₂H₆, and C₃H₈. When CH₄ is present in the irradiated ice mixture, long-chained volatile hydrocarbons and CO₂ are synthesized along with high-molecular-weight carbon compounds present in the room temperature residue. Irradiated mixtures containing CO and H₂O synthesize CO₂ and those CO₂ and H₂O synthesize CO. Due to radiation synthesis, ～1% of the ice was converted into a nonvolatile residue containing complicated carbon compounds not present in blank samples. These results suggest that irrespective of the composition of newly accreted comets, initial molecular abundances can be altered and new species created as a result of radiation synthesis. Irradiated mixtures exhibited thermoluminescence and pressure enhancements during warming; these phenomena suggest irradiation synthesis of reactive species. Ourbursts in new comets resulting from similar radiation induced exothermic activity would be expected to occur beginning at distances of the order of 100 AU.     

Experimental impact shock chemistry on planetary icy satellites

We present new experimental results on impact shock chemistry into icy satellites of the outer planets. Icy mixtures of pure water ice with CO₂, Na₂CO₃, CH₃OH, and CH₃OH/(NH₄)₂SO₄ at 77 K were ablated with a powerful pulsed laser—a new technique used to simulate shock processes which can occur during impacts. New products were identified by GC-MS and FTIR analyses after laser ablation. Our results show that hydrogen peroxide is formed in irradiated H₂O/CO₂ ices with a final concentration of 0.23%. CO and CH₃OH were also detected as main products. The laser ablation of frozen H₂O/Na₂CO₃ generates only CO and CO₂ as destruction products from the salt. Pulsed irradiation of water ice containing methanol leads also to the formation of CO and CO₂, generates methane and more complex molecules containing carbonyl groups like acetaldehyde, acetone, methyl formate, and a diether, dimethyl formal. The last three compounds are also produced when adding ammonium sulfate to H₂O/CH₃OH ice, but acetone is more abundant. The formation of two hydrocarbons, CH₄ and C₂H₆ is observed as well as the production of three nitrogen compounds, nitrous oxide, hydrogen cyanide, and acetonitrile.     

Infrared study of ion-irradiated N2-dominated ices relevant to Triton and Pluto: formation of HCN and HNC

Infrared spectra and radiation chemical behavior of N₂-dominated ices relevant to the surfaces of Triton and Pluto are presented. This is the first systematic IR study of proton-irradiated N₂-rich ices containing CH₄ and CO. Experiments at 12 K show that HCN, HNC, and diazomethane (CH₂N₂) form in the solid phase, along with several radicals. NH₃ is also identified in irradiated N₂ + CH₄ and N₂ + CH₄ + CO. We show that HCN and HNC are made in irradiated binary ice mixtures having initial N₂/CH₄ ratios from 100 to 4, and in three-component mixtures have an initial N₂/(CH₄ + CO) ratio of 50. HCN and HNC are not detected in N₂-dominated ices when CH₄ is replaced with C₂H₆, C₂H₂, or CH₃OH.The intrinsic band strengths of HCN and HNC are measured and used to calculate G(HCN) and G(HNC) in irradiated N₂ + CH₄ and N₂ + CH₄ + CO ices. In addition, the HNC/HCN ratio is calculated to be ∼1 in both icy mixtures. These radiolysis results reveal, for the first time, solid-phase synthesis of both HCN and HNC in N₂-rich ices containing CH₄.We examine the evolution of spectral features due to acid-base reactions (acids such as HCN, HNC, and HNCO and a base, NH₃) triggered by warming irradiated ices from 12 K to 30-35 K. We identify anions (OCN⁻, CN⁻, and N3−) in ices warmed to 35 K. These ions are expected to form and survive on the surfaces of Triton and Pluto. Our results have astrobiological implications since many of these products (HCN, HNC, HNCO, NH₃, NH₄OCN, and NH₄CN) are involved in the syntheses of biomolecules such as amino acids and polypeptides.     

Effects of low concentrations of O2 and CO on the ion-clustering reactions in the lower ionosphere of Mars

It is demonstrated that under conditions which approximate those of the Martian ionosphere traces of CO and O₂ can be effectively incorporated in ion clusters via ion-molecule reaction schemes initiated by the CO₂⁺ ion. For example, when 0.3 % CO is added to CO₂, (CO)₂⁺ and [(CO)₂CO₂]⁺ appear as the major cations (584 Å radiation, 300°K). In mixtures containing O₂ in addition to CO₂ (CO₂. O₂)⁺ and [(CO₂)₂O₂]⁺ are important species. A recently proposed mechanism to account for the low abundance of CO and O₂ in the Martian atmosphere is discussed in the light of these observations.     

Formation of methane in comet impacts: implications for Earth, Mars, and Titan

We calculate the amount of methane that may form via reactions catalyzed by metal-rich dust that condenses in the wake of large cometary impacts. Previous models of the gas-phase chemistry of impacts predicted that the terrestrial planets' atmospheres should be initially dominated by CO/CO₂, N₂, and H₂O. CH₄ was not predicted to form in impacts because gas-phase reactions in the explosion quench at temperatures ∼2000 K, at which point all of the carbon is locked in CO. We argue that the dust that condenses out in the wake of a large comet impact is likely to have very effective catalytic properties, opening up reaction pathways to convert CO and H₂ to CH₄ and CO₂, at temperatures of a few hundred K. Together with CO₂, CH₄ is an important greenhouse gas that has been invoked to compensate for the lower luminosity of the Sun ∼4 Gyr ago. Here, we show that heterogeneous (gas-solid) reactions on freshly-recondensed dust in the impact cloud may provide a plausible nonbiological mechanism for reducing CO to CH₄ before and during the emergence of life on Earth, and perhaps Mars as well. These encouraging results emphasize the importance of future research into the kinetics and catalytic properties of astrophysical condensates or “smokes” and also more detailed models to determine the conditions in impact-generated dust clouds.     

Prebiotic organic synthesis in early Earth and Mars atmospheres: Laboratory experiments with quantitative determination of products formed in a cold plasma flow reactor

The goal of this study was to explore prebiotic chemistry in a range of plausible early Earth and Mars atmospheres. To achieve this laboratory continuous flow plasma irradiation experiments were performed on N₂/H₂/CO/CO₂ gas mixtures chosen to represent mildly reducing early Earth and Mars atmospheres derived from a secondary volcanic outgassing of volatiles in chemical equilibrium with magmas near present day oxidation state. Under mildly reducing conditions (91.79% N₂, 5.89% H₂, 2.21% CO, and 0.11% CO₂), simple nitriles are produced in the gas phase with yield (G in molecules per 100 eV), for the key prebiotic marker molecule HCN at G∼1×¹⁰⁻³ (0.1 nmol J⁻¹). In this atmosphere localized HCN concentrations possibly could approach the 10⁻² M needed for HCN oligomerization. Yields under mildly oxidizing conditions (45.5% N₂, 0.1% H₂, 27.2% CO, 27.2% CO₂) are significantly less as expected, with HCN at G∼3×¹⁰⁻⁵ (). Yields in a Triton atmosphere which can be plausibly extrapolated to represent what might be produced in trace CH₄ conditions (99.9% N₂, 0.1% CH₄) are significant with HCN at G∼1×¹⁰⁻² (1 nmol J⁻¹) and tholins produced. Recently higher methane abundance atmospheres have been examined for their greenhouse warming potential, and higher abundance hydrogen atmospheres have been proposed based on a low early Earth exosphere temperature. A reducing (64.04% N₂, 28.8% H₂, 3.60% CO₂, and 3.56% CH₄), representing a high CH₄ and H₂ abundance early Earth atmosphere had HCN yields of G∼5×¹⁰⁻³ (0.5 nmol J⁻¹). Tholins generated in high methane hydrogen gas mixtures is much less than in a similar mixture without hydrogen. The same mixture with the oxidizing component CO₂ removed (66.43% N₂, 29.88% H₂, 0% CO₂, and 3.69% CH₄) had HCN yields of G∼1×¹⁰⁻³ (0.1 nmol J⁻¹) but more significant tholin yields.     

Reflectance and transmittance spectra (2.2-2.4 μm) of ion irradiated frozen methanol

We present near-IR (2.2-2.4 μm) reflectance and transmittance spectra of frozen (16 and 77 K) methanol (CH₃OH) and water-methanol (1:1) mixtures before and after irradiation with 30 keV He⁺ and 200 keV H⁺ ions. Spectra of other simple hydrocarbons (CH₄, C₂H₂, C₂H₄, C₂H₆) and CO have also been obtained both to help in the identification of the new molecules formed after ion irradiation of methanol-rich ices, and to get insight into the question of the presence of simple frozen hydrocarbons on the surface of some objects in the outer Solar System. The results confirm what obtained by studies performed in different spectral ranges, namely the ion-induced formation of CO and CH₄, and, for the first time, evidence a strong decrease of the intensity of the methanol band at about 2.34 μm in comparison with that at 2.27 μm. The results are discussed in view of their relevance for icy objects in the Solar System (namely comets, Centaurs, and Kuiper belt objects) where CH₃OH has been observed or suggested to be present.     

Density and refractive index of binary CH4, N2 and CO2 ice mixtures

In this work we present the results of a series of laboratory experiments performed to obtain the density and the real part of the refractive index of binary mixtures of ices of astrophysical interest. Densities of CO₂:CH₄ mixtures obey the expected weighted mean and the other binary mixtures have densities up to 20% lower than expected. Refractive index for all the binary mixtures deviates up to 5% from the theoretical, obtaining higher values than expected for CO₂:CH₄ and lower values than predicted for CO₂:N₂ and CH₄:N₂.     

Trapping and release of gases by water ice and implications for icy bodies

The trapping and release of H₂, CO, CO₂, CH₄, Ar, Ne, and N₂ by amorphous water ice was studied experimentally under dynamic conditions, at low temperatures starting at 16°K, with gas pressure of 5 × 10^?8?10^?6 Torr. CO, CH₄, Ar, and N₂ were found to be released in three or four distinct temperature ranges, each resulting from a different trapping mechanism: (a) 30–55°K, where the gas frozen on the water ice evaporates; (b) 135–155°K, where gas is squeezed out of the water ice during the transformation of amorphous ice to cubic ice; (c) 165–190°K, where gas and water are released simultaneously, probably by the evaporation of a clathrate hydrate, and, occasionally (d) 160–175°K, where deeply buried gas is released during the transformation of cubic ice to hexagonal ice. If the third range is indeed due to clathrate formation, CO was found to form this compound. CO₂ did not form a clathrate under the experimental conditions. Excess hydrogen did not affect the occlusion of other gases. Hydrogen itself was trapped only at 16°K. Neon was not trapped at 25°K. With cubic ice, the only trapping mechanism is freezing of gas on the ice surface. No fractionation between the gas phase and the ice was observed with a mixture of CO and Ar. Massive ejection of ice grains was observed during the evaporation of the gas in three (a,c,d) out of the four ranges. The experimental results are used to explain several cometary phenomena, especially those occurring at large heliocentric distances, and are applied also to Titan's atmospheric composition and to the possible ejection of ice grains from Enceladus.     

Extreme Ultraviolet Photon-Induced Chemical Reactions in the C2H2-H2O Mixed Ices at 10 K

Experimental results on the spectral identification of new infrared absorption features and the changes of their absorbances produced through vacuum ultraviolet-extreme ultraviolet (VUV-EUV) photon-induced chemical reactions in the C₂H₂-H₂O mixed ices at 10 K are obtained. To the best of our knowledge, this is the first time that EUV photons have been employed in the study of the photolysis of ice analogues. Two different compositions, i.e., C₂H₂:H₂O=1:4 and 1:1, were investigated in this work. A tunable intense synchrotron radiation light source available at the Synchrotron Radiation Research Center, Hsinchu, Taiwan, was employed to provide the required VUV-EUV photons. In this study, the photon wavelengths selected to irradiate the icy samples corresponded to the prominent solar hydrogen, helium, and helium ion lines at 121.6 nm, 58.4 nm, and 30.4 nm, respectively. The photon dosages used were typically in the range of 1×10¹⁵ to 2×10¹⁷ photons. Molecular species produced and identified in the ice samples at 10 K resulting from VUV-EUV photon irradiation are mainly CO, CO₂, CH₄, C₂H₆, CH₃OH, and H₂CO. In addition to several unidentified features, we have tentatively assigned several absorption features to HCO, C₃H₈, and C₂H₅OH. While new molecular species were formed, the original reactants, i.e., H₂O and C₂H₂, were detectably depleted due to their conversion to other species. The new chemical species produced by irradiation of photons at 30.4 nm and 58.4 nm can be different from those produced by the 121.6-nm photolysis. In general, the product column density of CO reaches saturation at a lower photon dosage than that of CO₂. Furthermore, the production yield of CO is higher than that of CO₂ in the photon irradiation. In the present study, we also observe that the photon-induced chemical reaction yields are high using photons at 30.4 and 58.4 nm. The results presented in this work are essential to our understanding of chemical synthesis in ice analogues, e.g., the cometary-type ices and icy satellites of planetary systems.     

Carbon dioxide segregation in 1:4 and 1:9 CO2:H2O ices

The mid-infrared spectra of mixed vapor deposited ices of CO₂ and H₂O were studied as a function of both deposition temperature and warming from 15 to 100 K. The spectra of ices deposited at 15 K show marked changes on warming beginning at 60 K. These changes are consistent with CO₂ segregating within the ice matrix into pure CO₂ domains. Ices deposited at 60 and 70 K show a greater degree of segregation, as high as 90% for 1:4 CO₂:H₂O ice mixtures deposited at 70 K. As the ice is warmed above 80 K, preferential sublimation of the segregated CO₂ is observed. The kinetics of the segregation process is also examined. The segregation of the CO₂ as the ice is warmed corresponds to temperatures at which the structure of the water ice matrix changes from the high density amorphous phase to the low density amorphous phase. We show how these microstructural changes in the ice have a profound effect on the photochemistry induced by ultraviolet irradiation. These experimental results provide a framework in which observations of CO₂ on the icy bodies of the outer Solar System can be considered.     

Spectral reflectance change and luminescence of selected salts during 2–10 KeV proton bombardment: Implications for Io

Radiation damage and luminescence, caused by magnetospheric charged particles, have been suggested by several authors as mechanisms for explaining some of the peculiar spectral/albedo features of Io. We have pursued this possibility by measuring the uv-visual spectral reflectance and luminescent efficiency of several proposed Io surface constituents during 2 to 10-keV proton irradiation at room temperature and at low temperature (120 < T < 140°K). The spectral reflectance of NaCl and KCl during proton irradiation exhibits the well-known F-center absorption bands at 4580 and 5560 Å. Na₂SO₄ shows a generalized darkening which increases toward longer wavelengths. NaNO₃ shows a spectral reflectance change indicative of the partial alteration of NaNo₃ to NaNo₂. NaNO₂ shows no change. The luminescent efficiencies of NaCl and KCl are ～10^?4 at 300°K and increase by one-half order of magnitude at ～130°K. The efficiencies of K₂CO₃, Na₂CO₃, Na₂SO₄, and NaNO₃ are 10^?4, 10^?4, 10^?5 and 10^?6, respectively, at 300°K and they all decrease by one-half order of magnitude at ～130°K. These results indicate that magnetospheric proton irradiation of Io could cause spectral features in its observed ultraviolet and visible reflection spectrum if salts such as those studied here are present on its surface. However, because the magnitude of these spectral effects is dependent on competing factors such as surface temperature, incident particle energy flux, solar bleaching effects, and trace element abundance, we are unable at this time to make a quantitative estimate of the strength of these spectral effects on Io. The luminescent efficiencies of pure samples that we have studied in the laboratory suggest that charged-particle induced luminescence from Io's surface might be observable by a spacecraft such as Voyager when viewing Io's dark side.     

Thermal desorption of CH4 retained in CO2 ice

CO₂ ices are known to exist in different astrophysical environments. In spite of this, its physical properties (structure, density, refractive index) have not been as widely studied as those of water ice. It would be of great value to study the adsorption properties of this ice in conditions related to astrophysical environments. In this paper, we explore the possibility that CO₂ traps relevant molecules in astrophysical environments at temperatures higher than expected from their characteristic sublimation point. To fulfil this aim we have carried out desorption experiments under High Vacuum conditions based on a Quartz Crystal Microbalance and additionally monitored with a Quadrupole Mass Spectrometer. From our results, the presence of CH₄ in the solid phase above the sublimation temperature in some astrophysical scenarios could be explained by the presence of several retaining mechanisms related to the structure of CO₂ ice.     

Oxidation of CO on surface hematite in high CO2 atmospheres

We propose a mechanism for the oxidation of gaseous CO into CO₂ occurring on the surface mineral hematite (Fe₂O₃(s)) in hot, CO₂-rich planetary atmospheres, such as Venus. This mechanism is likely to constitute an important source of tropospheric CO₂ on Venus and could at least partly address the CO₂ stability problem in Venus’ stratosphere, since our results suggest that atmospheric CO₂ is produced from CO oxidation via surface hematite at a rate of 0.4 petagrammes (Pg) CO₂ per (Earth) year on Venus which is about 45% of the mass loss of CO₂ via photolysis in the Venusian stratosphere. We also investigated CO oxidation via the hematite mechanism for a range of planetary scenarios and found that modern Earth and Mars are probably too cold for the mechanism to be important because the rate-limiting step, involving CO(g) reacting onto the hematite surface, proceeds much slower at lower temperatures. The mechanism may feature on extrasolar planets such as Gliese 581c or CoRoT-7b assuming they can maintain solid surface hematite which, e.g. starts to melt above about 1200 K. The mechanism may also be important for hot Hadean-type environments and for the emerging class of hot Super-Earths with planetary surface temperatures between about 600 and 900 K.     

Dependence of the effective rate constants for the hydrogenation of CO on the temperature and composition of the surface

Experiments on the hydrogenation of CO on pure CO and CO-H₂O mixed ice have been performed at temperatures between 8 and 20 K. We obtained temperature and compositional dependence of the effective reaction rate constants. Results indicate that hydrogenation proceeds efficiently on pure solid CO and CO-H₂O mixed ice at temperatures below 10 and 20 K, respectively. Rate constants for pure CO decreased significantly at 12 K compared to those obtained with CO-H₂O mixed ice. Hydrogenation of CO at temperatures greater than 12 K were catalyzed by the H₂O adjacent to the CO. The importance of the experimental results for some relevant astrophysical environments has also been outlined.     

Recombination rates of O and CO on solid CO2: Implications for the composition of the martian atmosphere

An atomic oxygen flow system and a C¹⁴ radiochemical technique have been used to show that the reactions O + CO → CO₂ and O + O → O₂, are heterogeneously catalysed by solid CO₂ at 77 K.The O-CO recombination is first order in CO and inhibited by O, whereas the O-O recombination is first order in O and weakly inhibited by CO. Assuming simple first order kinetics, recombination coefficients γ_co = 1.3(±0.9) × 10^?5 and γ_O = 0.05± 0.02 are determined. A recombination mechanism involving an intermediate adsorbed CO₃ is proposed. If the kinetic results are assumed to apply under Martian surface conditions, then conversion of CO to CO₂ by reaction on the solid CO₂ at the polar caps occurs at ~10 times the total column recombination rates for homogeneous reactions previously proposed; night-side CO₂ ice clouds would also constitute an important recombination surface.     

CO2 production by ion irradiation of H2O ice on top of carbonaceous materials and its relevance to the Galilean satellites

In this work we report on new experiments of ion irradiation of water ice deposited on top of solid carbonaceous materials to study the production of CO₂ at the interface ice/refractory material and discuss the possibility that this mechanism accounts for the quantity of CO₂ ice detected on the surfaces of the Galilean satellites. The used experimental technique has been in situ infrared spectroscopy. We have irradiated thin films of H₂O frost on carbonaceous layers with 200 keV of He⁺ and Ar⁺, and 30 keV of He⁺ at 16 and 80 K. The used carbonaceous layers have been asphaltite, a natural bitumen, and solid organic residues obtained by irradiation of frozen benzene. In both cases the results show that CO₂ is produced very efficiently after irradiation obtaining a maximum quantity of the order of . These results are, also quantitatively similar, to those recently obtained for water ice deposited on amorphous carbon films [Mennella, V., Palumbo, M.E., Baratta, G.A., 2004. Formation of CO and CO₂ molecules by ion irradiation of water ice covered hydrogenated carbon grains. Astrophys. J. 615, 1073-1080]. Thus we suggest that, whatever is the carbonaceous residue, CO₂ will be produced efficiently by the studied process. These results have interest in the context of the surfaces of the icy Galilean satellites in which CO₂ has been detected mainly trapped in the non-ice material, not in the pure water ice. We suggest that radiolysis of mixtures of water ice and refractory carbonaceous materials is the primary formation mechanism responsible for the CO₂ formation on the surfaces of the Galilean satellites.     

Evolution of CO on Titan

The early evolution of Titan's atmosphere is expected to produce enrichment in the heavy isotopomers of CO, ¹³CO and C¹⁸O, relative to ¹²C¹⁶O. However, the original isotopic signatures may be altered by photochemical reactions. This paper explains why there is no isotopic enrichment in C in Titan's atmosphere, despite significant enrichment of heavy H, N, and O isotopes. We show that there is a rapid exchange of C atoms between the CH₄ and CO reservoirs, mediated by the reaction ¹CH₂+*CO→¹*CH₂+CO, where *C is ¹³C. Based on recent laboratory measurements, we estimate the rate coefficient for this reaction to be 3.2×10⁻¹² cm³ s⁻¹ at the temperature appropriate for the upper atmosphere of Titan. We investigate the isotopic dilution of CO using the Caltech/JPL one-dimensional photochemical model of Titan. Our model suggests that the time constant for isotopic exchange through the above reaction is about 800 Myr, which is significantly shorter than the age of Titan, and therefore any original isotopic enhancement of ¹³C in CO may have been diluted by the exchange process. In addition, a plausible model for the evolution history of CO on Titan after the initial escape is proposed.     

Spectroscopy of Comet Hale-Bopp in the infrared

High resolution infrared spectra of Comet C/1995 O1 (Hale-Bopp) were obtained during 2-5 March 1997 UT from the NASA Infrared Telescope Facility on Mauna Kea, Hawaii, when the comet was at r≈1.0 AU from the Sun pre-perihelion. Emission lines of CH₄, C₂H₆, HCN, C₂H₂, CH₃OH, H₂O, CO, and OH were detected. The rotational temperature of CH₄ in the inner coma was T_rot=110±20 K. Spatial profiles of CH₄, C₂H₆, and H₂O were consistent with release solely from the nucleus. The centroid of the CO emission was offset from that of the dust continuum and H₂O. Spatial profiles of the CO lines were much broader than those of the other molecules and asymmetric. We estimate the CO production rate using a simplified outflow model: constant, symmetric outflow from the peak position. A model of the excitation of CO that includes optical depth effects using an escape probability method is presented. Optical depth effects are not sufficient to explain the broad spatial extent. Using a parent+extended-source model, the broad extent of the CO lines can be explained by CO being produced mostly (∼90% on 5 March) from an extended source in the coma. The CO rotational temperature was near 100 K. Abundances relative to H₂O (in percent) were 1.1±0.3 (CH₄), 0.39±0.10 (C₂H₆), 0.18±0.04 (HCN), 0.17±0.04 (C₂H₂), 1.7±0.5 (CH₃OH), and 37-41 (CO, parent+extended source). These are roughly comparable to those obtained for other long-period comets also observed in the infrared, though CO appears to vary.     

Global atmospheric monitoring with SCIAMACHY

SCIAMACHY (SCanning Imaging Absorption spectrometer for Atmospheric CHartographY) is a space based spectrometer designed to measure sunlight transmitted, reflected and scattered by the Earth atmosphere or surface. It is a contribution to the Envisat-1 satellite to be launched in late 1999.SCIAMACHY measurements will provide amounts and distribution of 0₃, BrO, OCl0, ClO, S0₂, H₂CO, N0₂, CO, CO₂, CH₄, H₂O, N₂0, pressure, temperature, aerosol, radiation, cloud cover and cloud top height from atmospheric measurements in nadir, limb and occultation geometry.By the combination of the near simultaneous limb and nadir observations SCIAMACHY is one of a limited number of instruments which is able to detect tropospheric column amounts of 0₃, N0₂, CO, CH₄, H₂O, N₂0, S0₂, H₂CO, and BrO down to the planetary boundary layer under cloud free conditions.