Chemical dynamics of triacetylene formation and implications to the synthesis of polyynes in Titan's atmosphere

For the last four decades, the role of polyynes such as diacetylene (HCCCCH) and triacetylene (HCCCCCCH) in the chemical evolution of the atmosphere of Saturn's moon Titan has been a subject of vigorous research. These polyacetylenes are thought to serve as an UV radiation shield in planetary environments; thus, acting as prebiotic ozone, and are considered as important constituents of the visible haze layers on Titan. However, the underlying chemical processes that initiate the formation and control the growth of polyynes have been the least understood to date. Here, we present a combined experimental, theoretical, and modeling study on the synthesis of the polyyne triacetylene (HCCCCCCH) via the bimolecular gas phase reaction of the ethynyl radical (CCH) with diacetylene (HCCCCH). This elementary reaction is rapid, has no entrance barrier, and yields the triacetylene molecule via indirect scattering dynamics through complex formation in a single collision event. Photochemical models of Titan's atmosphere imply that triacetylene may serve as a building block to synthesize even more complex polyynes such as tetraacetylene (HCCCCCCCCH)

A reassessment of Antarctic plateau reactive nitrogen based on ANTCI 2003 airborne and ground based measurements

The first airborne measurements of nitric oxide (NO) on the Antarctic plateau have demonstrated that the previously reported elevated levels of this species extend well beyond the immediate vicinity of South Pole. Although the current database is still relatively weak and critical laboratory experiments are still needed, the findings here suggest that the chemical uniqueness of the plateau may be substantially greater than first reported. For example, South Pole ground-based findings have provided new evidence showing that the dominant process driving the release of nitrogen from the snowpack during the spring/summer season (post-depositional loss) is photochemical in nature with evaporative processes playing a lesser role. There is also new evidence suggesting that nitrogen, in the form of nitrate, may undergo multiple recycling within a given photochemical season. Speculation here is that this may be a unique property of the plateau and much related to its having persistent cold temperatures even during summer. These conditions promote the efficient adsorption of molecules like HNO3 (and very likely HO2NO2) onto snow-pack surface ice where we have hypothesized enhanced photochemical processing can occur, leading to the efficient release of NOx to the atmosphere. In addition, to these process-oriented tentative conclusions, the findings from the airborne studies, in conjunction with modeling exercises suggest a new paradigm for the plateau atmosphere. The near-surface atmosphere over this massive region can be viewed as serving as much more than a temporary reservoir or holding tank for imported chemical species. It defines an immense atmospheric chemical reactor which is capable of modifying the chemical characteristics of select atmospheric constituents. This reactor has most likely been in place over geological time, and may have led to the chemical modulation of some trace species now found in ice cores. Reactive nitrogen has played a critical role in both establishing and in maintaining this reactor. © 2007 Elsevier Ltd. All rights reserved

Modeling the formation and growth of atmospheric molecular clusters : A review

Molecular clusters are ubiquitous constituents of the ambient atmosphere, that can grow into larger sizes forming new aerosol particles. The formation and growth of small clusters into aerosol particles remain one of the largest uncertainties in global climate predictions. This has made the modeling of atmospheric molecular clustering into an active field of research, yielding direct molecular level information about the formation mechanism. We review the present state of-the-art quantum chemical methods and cluster distribution dynamics models that are applied to study the formation and growth of atmospheric molecular clusters. We outline the current challenges in applying theoretical methods and the future directions to move the field forward.Peer reviewe

The Latest on the Venus Thermospheric General Circulation Model: Capabilities and Simulations

Venus has a complex and dynamic upper atmosphere. This has been observed many times by ground-based, orbiters, probes, and fly-by missions going to other planets. Two over-arching questions are generally asked when examining the Venus upper atmosphere: (1) what creates the complex structure in the atmosphere, and (2) what drives the varying dynamics. A great way to interpret and connect observations to address these questions utilizes numerical modeling; and in the case of the middle and upper atmosphere (above the cloud tops), a 3D hydrodynamic numerical model called the Venus Thermospheric General Circulation Model (VTGCM) can be used. The VTGCM can produce climatological averages of key features in comparison to observations (i.e. nightside temperature, O2 IR nightglow emission). More recently, the VTGCM has been expanded to include new chemical constituents and airglow emissions, as well as new parameterizations to address waves and their impact on the varying global circulation and corresponding airglow distributions

Chemical kinetics and modeling of planetary atmospheres

A unified overview is presented for chemical kinetics and chemical modeling in planetary atmospheres. The recent major advances in the understanding of the chemistry of the terrestrial atmosphere make the study of planets more interesting and relevant. A deeper understanding suggests that the important chemical cycles have a universal character that connects the different planets and ultimately link together the origin and evolution of the solar system. The completeness (or incompleteness) of the data base for chemical kinetics in planetary atmospheres will always be judged by comparison with that for the terrestrial atmosphere. In the latter case, the chemistry of H, O, N, and Cl species is well understood. S chemistry is poorly understood. In the atmospheres of Jovian planets and Titan, the C-H chemistry of simple species (containing 2 or less C atoms) is fairly well understood. The chemistry of higher hydrocarbons and the C-N, P-N chemistry is much less understood. In the atmosphere of Venus, the dominant chemistry is that of chlorine and sulfur, and very little is known about C1-S coupled chemistry. A new frontier for chemical kinetics both in the Earth and planetary atmospheres is the study of heterogeneous reactions. The formation of the ozone hole on Earth, the ubiquitous photochemical haze on Venus and in the Jovian planets and Titan all testify to the importance of heterogeneous reactions. It remains a challenge to connect the gas phase chemistry to the production of aerosols

Atmospheric Retrieval for Super-Earths: Uniquely Constraining the Atmospheric Composition with Transmission Spectroscopy

We present a retrieval method based on Bayesian analysis to infer the atmospheric compositions and surface or cloud-top pressures from transmission spectra of exoplanets with general compositions. In this study, we identify what can unambiguously be determined about the atmospheres of exoplanets from their transmission spectra by applying the retrieval method to synthetic observations of the super-Earth GJ 1214b. Our approach to infer constraints on atmospheric parameters is to compute their joint and marginal posterior probability distributions using the MCMC technique in a parallel tempering scheme. A new atmospheric parameterization is introduced that is applicable to general atmospheres in which the main constituent is not known a priori and clouds may be present. Our main finding is that a unique constraint of the mixing ratios of the absorbers and up to two spectrally inactive gases (such as N2 and primordial H2+He) is possible if the observations are sufficient to quantify both (1) the broadband transit depths in at least one absorption feature for each absorber and (2) the slope and strength of the molecular Rayleigh scattering signature. The surface or cloud-top pressure can be quantified if a surface or cloud deck is present. The mean molecular mass can be constrained from the Rayleigh slope or the shapes of absorption features, thus enabling to distinguish between cloudy hydrogen-rich atmospheres and high mean molecular mass atmospheres. We conclude, however, that without the signature of Rayleigh scattering--even with robustly detected infrared absorption features--there is no reliable way to tell if the absorber is the main constituent of the atmosphere or just a minor species with a mixing ratio of <0.1%. The retrieval method leads us to a conceptual picture of which details in transmission spectra are essential for unique characterizations of well-mixed atmospheres.Comment: 23 pages, 13 figures, accepted at ApJ, submitted to ApJ on Nov 4, 201

The NASA program on upper atmospheric research

The purpose of the NASA Upper Atmospheric Research Program is to develop a better understanding of the physical and chemical processes that occur in the earth's upper atmosphere with emphasis on the stratosphere

Measurements of Pollution in the Troposphere: MOPITT

This brochure gives a brief description of the science research that is being done with data from the MOPITT instrument flying onboard NASA's Terra satellite. It also identifies some of the data products, as well as gives some technical specifications. Note: this brochure was produced before the Terra launched; for the most recent information, go to http://terra.nasa.gov/. Educational levels: Undergraduate lower division, Undergraduate upper division, Graduate or professional

Stratospheric measurement requirements and satellite-borne remote sensing capabilities

The capabilities of specific NASA remote sensing systems to provide appropriate measurements of stratospheric parameters for potential user needs were assessed. This was used to evaluate the capabilities of the remote sensing systems to perform global monitoring of the stratosphere. The following conclusions were reached: (1) The performance of current remote stratospheric sensors, in some cases, compares quite well with identified measurement requirements. Their ability to measure other species has not been demonstrated. (2) None of the current, in-situ methods have the capability to satisfy the requirements for global monitoring and the temporal constraints derived from the users needs portion of the study. (3) Existing, non-remote techniques will continue to play an important role in stratospheric investigations for both corroboration of remotely collected data and in the evolutionary development of future remote sensors