Carbonyl Sulphide (OCS) Variability with Latitude in the Atmosphere

Abstract

Carbonyl sulphide (OCS) is an important precursor of sulphate aerosols and consequently a key species in stratospheric ozone depletion. The SPectromètre InfraRouge d'Absorption à Lasers Embarqués (SPIRALE) and shortwave infrared (SWIR) balloon-borne instruments have flown in the tropics and in the polar Arctic, and ground-based measurements have been performed by the Qualité de l'Air (QualAir) Fourier Transform Spectrometer in Paris. Partial and total columns and vertical profiles have been obtained to study OCS variability with altitude, latitude, and season. The annual total column variation in Paris reveals a seasonal variation with a maximum in April–June and a minimum in November–January. Total column measurements above Paris and from SWIR balloon-borne instrument are compared with several MkIV measurements, several Network for the Detection of Atmospheric Composition Change (NDACC) stations, aircraft, ship, and balloon measurements to highlight the OCS total column decrease from tropical to polar latitudes. OCS high-resolution in situ vertical profiles have been measured for the first time in the altitude range between 14 and 30?km at tropical and polar latitudes. OCS profiles are compared with Atmospheric Chemistry Experiment (ACE) satellite measurements and show good agreement. Using the correlation between OCS and N₂O from SPIRALE, the OCS stratospheric lifetime has been accurately determined. We find a stratospheric lifetime of 68?±?20 years at polar latitudes and 58?±?14 years at tropical latitudes leading to a global stratospheric sink of 49?±?14?Gg?S?y^?1.     

FT-IR measurements of cold C3H8 cross sections at 7–15 μm for Titan atmosphere

We present absorption cross sections of propane (C₃H₈) at temperatures from 145 K to 297 K in the 690–1550 cm⁻¹ region. Pure and N₂-broadened spectra were measured at pressures from 3 Torr to 742 Torr using a Bruker IFS125 FT-IR spectrometer at JPL. The gas absorption cell, developed at Connecticut College, was cooled by a closed-cycle helium refrigerator. The cross sections were measured and compiled for individual spectra recorded at various experimental conditions covering the planetary atmosphere and Titan. In addition to the cross sections, a propane pseudoline list with a frequency grid of 0.005 cm⁻¹, was fitted to the 34 laboratory spectra. Line intensities and lower state energies were retrieved for each line, assuming a constant width. Validation tests showed that the pseudoline list reproduces discrete absorption features and continuum, the latter contributed by numerous weak and hot band features, in most of the observed spectra within 3%. Based on the pseudoline list, the total intensity in the 690–1550 cm⁻¹ region was determined to be 52.93 (±3%) × 10⁻¹⁹ cm⁻¹/(molecule cm⁻²) at 296 K; this value is within 3% of the average from four earlier studies. Finally, the merit of the pseudoline approach is addressed for heavy polyatomic molecules in support of spectroscopic observation of atmospheres of Titan and other planets. The cold cross sections will be submitted to the HITRAN database (hitran.harvard.edu), and the list of C₃H₈ pseudolines will be available from a MK-IV website of JPL (http://mark4sun.jpl.nasa.gov/data/spec/Pseudo).     

Microphysical modeling of ethane ice clouds in titan’s atmosphere

A time-dependent microphysical model is used to study the evolution of ethane ice clouds in Titan’s atmosphere. The model simulates nucleation, condensational growth, evaporation, coagulation, and transport of particles. For a critical saturation of 1.15 (a lower limit, determined by laboratory experiments), we find that ethane clouds can be sustained between altitudes of 8 and 50 km. Growth due to coalescence is inefficient, limiting the peak in the size distribution (by number) to 10 μm. These clouds vary with a period of about 20 days. This periodicity disappears for higher critical saturation values where clouds remain subvisible. Rainout of ethane due to methane cloud formation raises the altitude of the ethane cloud bottom to near the tropopause and may eliminate ethane clouds entirely if methane cloud formation occurs up to 30 km. However, clouds formed above the troposphere from other gases in Titan’s atmosphere could be sustained even with rainout up to 30 km. Although the optical depth of ethane clouds above 20 km is typically low, short-lived clouds with optical depths of order 0.1-1 can be created sporadically by dynamically driven atmospheric cooling. Ethane cloud particles larger than 25 μm can fall to the surface before total evaporation. However, ethane clouds remain only a small sink for tholin particles. At the peak of their cycle, the optical depth of ethane clouds could be comparable to that of tholin in the near-infrared, resulting in a 5% increase in Titan’s albedo for wavelengths between 1 and 2 μm. A number of factors limit our ablility to predict the ethane cloud properties. These factors include the mixing time in the troposphere, the critical saturation ratio for ethane ice, the existence of a surface reservoir of ethane, the magnitude and timing of dynamically driven temperature perturbations, and the abundance and life cycle of methane clouds.     

Venus: Mesospheric hazes of ice,dust, and acid aerosols

We speculate on the origin and physical properties of haze in the upper atmosphere of Venus. It is argued that at least four distinct types of particles may be present. The densest and lowest haze, normally seen by spacecraft, probably consists of a submicron sulfuric acid aerosol which extends above the cloud tops (at ～70 km) up to ～80 km; this haze represents an extension of the upper cloud deck. Measurements of the temperature structure between 70 and 120 km indicate that two independent water ice layers may occasionally appear. The lower one can form between 80 and 100 km and is probably the detached haze layer seen in high-contrast limb photography. This ice layer is likely to be nucleated on sulfuric acid aerosols, and is analogous to the nacreous (stratospheric) clouds on Earth. At the Venus “mesopause” near 120 km, temperatures are frequently cold enough to allow ice nucleation on meteoric dust or ambient ions. The resulting haze (which is analogous to noctilucent clouds on Earth) is expected to be extremely tenous, and optically invisible. On both Earth and Venus, meteoric dust is present throughout the upper atmosphere and probably has similar properties.     

Correcting superconducting gravity time-series using rainfall modelling at the Vienna and Membach stations and application to Earth tide analysis

We demonstrate the possibility to improve the signal-to-noise ratio of superconducting gravity time-series by correcting for local hydrological effects. Short-term atmospheric events associated with heavy rain induce step-like gravity signals that deteriorate the frequency spectrum estimates. Based on 4D modeling constrained by high temporal resolution rain gauge data, rainfall admittances for the Vienna and Membach superconducting gravity stations are calculated. This allows routine correction for Newtonian rain water effects, which reduces the standard deviation of residuals after tidal parameter adjustment by 10%. It also improves the correction of steps of instrumental origin when they coincide with step-like water mass signals.     

CO2 Snow on Mars and Early Earth: Experimental Constraints

Greenhouse warming due to carbon dioxide atmospheres may be responsible for maintaining the early Earth's surface temperature above freezing and may even have allowed for liquid water on early Mars. However, the high levels of CO₂ required for such warming should have also resulted in the formation of CO₂ clouds. These clouds, depending on their particle size, could lead to either warming or cooling. The particle size in turn is determined by the nucleation and growth conditions. Here we present laboratory studies of the nucleation and growth of carbon dioxide on water ice under martian atmospheric conditions. We find that a critical saturation, S=1.34, is required for nucleation, corresponding to a contact parameter between solid water and solid carbon dioxide of m=0.95. We also find that after nucleation occurs, growth of CO₂ is very rapid, and we report the growth rates at a number of supersaturations. Because growth would be expected to continue until the CO₂ pressure is lowered to its vapor pressure, we expect particles larger than those being currently suggested for the present and past martian atmospheres. Using this information in a microphysical model described in a companion paper, we find that CO₂ clouds are best described as “snow,” having a relatively small number of large particles.     

The stratospheric sulfate aerosol layer: Processes,models, observations,and simulations

After briefly reviewing the observational data on the stratospheric sulfate aerosol layer, the chemical and physical processes that are likely to fix the properties of the layer are discussed. We present appropriate continuity equations for aerosol particles, and show how to solve the equations on a digital computer. Simulations of the unperturbed aerosol layer by various published models are discussed and the sensitivity of layer characteristics to variations in several aerosol model parameters is studied. We discuss model applications to anthropogenic pollution problems and demonstrate that moderate levels of aerospace activity (supersonic transport and space shuttle operations) will probably have only a negligible effect on global climate. Finally, we evaluate the possible climatic effect of a ten-fold increase in the atmospheric abundance of carbonyl sulfide.     

Large,solid particles in the clouds of Venus: Do they exist?

The discovery of large, solid particles in the clouds of Venus is one of the most significant findings of Pioneer Venus because it means that a substantial mass of the clouds is composed of a material other than sulfuric acid. The evidence which suggests that solid particles form a distinctive size mode is reexamined. The mode is defined by a discontinuity between two size ranges of the Pioneer Venus particle size spectrometer. This discontinuity could represent a real size mode. However, it could also be an artifact of the measurement technique. R. G. Knollenberg (1984) discusses several possible instrumental effects which might have caused this discontinuity. It is hypothesized herein that such effects did occur and that the large particles are really the tail of the mode 2 sulfuric acid particle size distribution and are not a separate mode of solid particles. Using such a revised size distribution, it is shown that all of the Pioneer Venus and Venera optical data from the lower clouds can be explained with sulfuric acid droplets without introducing any solid particles. As a by-product of this analysis, it is also found that the upper clouds of Venus must contain a material with a higher refractive index than sulfuric acid. A small quantity of sulfur could account for this observation.     

Stability of mid-latitude snowpacks on Mars

Christensen [2003. Nature 422, 45-48] suggested that runoff from melting snowpacks on martian slopes might be responsible for carving gullies. He also suggested that snowpacks currently exist on Mars, for example on the walls of Dao Valles (approximately 33° S). Such snowpacks were presumably formed during the last obliquity cycle, which occurred about 70,000 years ago. In this paper we investigate a specific scenario under conditions we believe are favorable for snowpack melting. We model the rate at which a snowpack located at 33° S on a poleward-facing slope sublimates and melts on Mars, as well as the temperature profile within the snowpack. Our model includes the energy and mass balance of a snowpack experiencing diurnal variations in insolation. Our results indicate that a dirty snowpack would quickly sublimate and melt under current martian climate conditions. For example a 1 m thick dusty snowpack of moderate density (550 kg/m³) and albedo (0.39) would sublimate in less than two seasons, producing a small amount of meltwater runoff. Similarly, a cleaner snowpack (albedo 0.53) would disappear in less than 9 seasons. These results suggest that the putative snowpack almost certainly could not have survived for 70,000 years. For most of the parameter settings snowpack interior temperatures at this latitude and slope do reach the melting point. Under most conditions melting occurs when the snowpack is less than 10 cm thick. The modeled snowpack will not melt if it is covered by a 1 cm dust lag. In general, these findings raise interesting possibilities regarding gully formation, but perhaps mostly during a past climate regime when snowfall was expected to have occurred. If there currently are exposed snowpacks on martian mid-latitude slopes, then these ice sheets cannot last long. Hence they might be time variable features on Mars and should be searched for.