Returnability as a criterion of disequilibrium in atmospheric reactions networks

The concept of network returnability is reformulated as an equilibrium constant for a reaction network. Using this concept we study the atmospheric reaction networks of Earth, Mars, Venus and Titan. We found that the reaction network in the Earth’s atmosphere has the largest disequilibrium, followed by that of Titan which is still far from the most returnable atmospheres of Mars and Venus. We find that the chemical species with null or very low returnability are those in the highest disequilibrium in their respective atmospheres mainly due to physical, biogenic and/or anthropogenic mechanisms.     

Laboratory studies of photochemistry and gas phase radical reaction kinetics relevant to planetary atmospheres

This review seeks to bring together a selection of recent laboratory work on gas phase photochemistry, kinetics and reaction dynamics of radical species relevant to the understanding of planetary atmospheres other than that of Earth. A majority of work focuses on the rich organic chemistry associated with photochemically initiated reactions in the upper atmospheres of the giant planets. Reactions relevant to Titan, the largest moon of Saturn and with a nitrogen/methane dominated atmosphere, have also received much focus due to potential to explain the chemistry of Earth's prebiotic atmosphere. Analogies are drawn between the approaches of terrestrial and non-terrestrial atmospheric chemistry.     

Photoinduced mechanism of formation and growth of polycyclic aromatic hydrocarbons in low-temperature environments via successive ethynyl radical additions

A novel ethynyl addition mechanism (EAM) has been established computationally as a practicable alternative to high-temperature hydrogen-abstraction-C2H2-addition (HACA) sequences to form polycyclic aromatic hydrocarbon (PAH) -like species under low-temperature conditions in the interstellar medium and in hydrocarbon-rich atmospheres of planets and their moons. Initiated by an addition of the ethynyl radical (C2H) to the ortho-carbon atom of the phenylacetylene (C6H5C2H) molecule, the reactive intermediate loses rapidly a hydrogen atom, forming 1,2-diethynylbenzene. The latter can react with a second ethynyl molecule via addition to a carbon atom of one of the ethynyl side chains. A consecutive ring closure of the intermediate leads to an ethynyl-substituted naphthalene core. Under single-collision conditions as present in the interstellar medium, this core loses a hydrogen atom to form ethynyl-substituted 1,2-didehydronaphthalene. However, under higher pressures as present, for example, in the atmosphere of Saturn's moon Titan, three-body reactions can lead to a stabilization of this naphthalene-core intermediate. We anticipate this mechanism to be of great importance to form PAH-like structures in the interstellar medium and also in hydrocarbon-rich, low-temperature atmospheres of planets and their moons such as Titan. If the final ethynyl addition to 1,2-diethynylbenzene is substituted by a barrierless addition of a cyano (CN) radical, this newly proposed mechanism can even lead to the formation of cyano-substituted naphthalene cores in the interstellar medium and in planetary atmospheres.     

CO2对790nm附近水线的压力加宽和位移

采用高灵敏的激光光腔衰荡光谱技术研究了CO2对160水分子v^2＋3v^3振动带跃迁线的压力诱导效应．为了抑制水的自碰撞效应,水的压力在实验中低于0．5Torr．基于铷原子吸收线和超稳法布里-珀罗标准确定了跃迁谱线高达10^-5cm^-1精度的绝对频率．采用软碰撞模型对吸收线进行模拟,获得了对应的线形参数．     

Vibrational quenching of CO2(010) by collisions with O(3P) at thermal energies: a quantum-mechanical study

The CO(2)(010)-O((3)P) vibrational energy transfer (VET) efficiency is a key input to aeronomical models of the energy budget of the upper atmospheres of Earth, Venus, and Mars. This work addresses the physical mechanisms responsible for the high efficiency of the VET process at the thermal energies existing in the terrestrial upper atmosphere (150 K相似文献   

Microchip capillary electrophoresis instrumentation for in situ analysis in the search for extraterrestrial life

The search for signs of life on extraterrestrial planetary bodies is among NASA's top priorities in Solar System exploration. The associated pursuit of organics and biomolecules as evidence of past or present life demands in situ investigations of planetary bodies for which sample return missions are neither practical nor affordable. These in situ studies require instrumentation capable of sensitive chemical analyses of complex mixtures including a broad range of organic molecules. Instrumentation must also be capable of autonomous operation aboard a robotically controlled vehicle that collects data and transmits it back to Earth. Microchip capillary electrophoresis (μCE) coupled to laser-induced fluorescence (LIF) detection provides this required sensitivity and targets a wide range of relevant organics while offering low mass, volume, and power requirements. Thus, this technology would be ideally suited for in situ studies of astrobiology targets, such as Mars, Europa, Enceladus, and Titan. In this review, we introduce the characteristics of these planetary bodies that make them compelling destinations for extraterrestrial astrobiological studies, and the principal groups of organics of interest associated with each. And although the technology we describe here was first developed specifically for proposed studies of Mars, by summarizing its evolution over the past decade, we demonstrate how μCE-LIF instrumentation has become an ideal candidate for missions of exploration to all of these nearby worlds in our Solar System.     

Prebiotic-like chemistry on Titan

Titan, the largest satellite of Saturn, is the only one in the solar system with a dense atmosphere. Mainly composed of dinitrogen with several % of methane, this atmosphere experiences complex organic processes, both in the gas and aerosol phases, which are of prebiotic interest and within an environment of astrobiological interest. This tutorial review presents the different approaches which can be followed to study such an exotic place and its chemistry: observation, theoretical modeling and experimental simulation. It describes the Cassini-Huygens mission, as an example of observational tools, and gives the new astrobiologically oriented vision of Titan which is now available by coupling the three approaches. This includes the many analogies between Titan and the Earth, in spite of the much lower temperature in the Saturn system, the complex organic chemistry in the atmosphere, from the gas to the aerosol phases, but also the potential organic chemistry on Titan's surface, and in its possible internal water ocean.     

Comparative study of carbon dioxide and nitrogen atmospheric effects on the chemical structure changes during pyrolysis of phenol-formaldehyde spheres

The effect of CO(2) atmosphere on the chemical structure changes of resol-type phenol-formaldehyde spheres during pyrolysis was investigated, in comparison with that of N(2) atmosphere, using FT-IR, TGA, and elemental analysis techniques. It was found that, in contrast to the expectation that CO(2) may act as an oxidizing agent at high temperature, it behaves very similar to N(2) during pyrolysis of PF spheres up to 700 degree C, but results in a somewhat different extent of some specific reactions. That is, although the reactions occurring up to 700 degree C were dominated by crosslinking and/or polyaromatization under both CO(2) and N(2) atmospheres, fewer alkyl-phenolic ether bonds were formed under CO(2) than under N(2). As a consequence, the samples carbonized under CO(2) at 700 degree C were found to have more pendant groups on the edge carbon atoms of carbon in the carbonized samples than those prepared under N(2) atmosphere.     

Gas chromatography in space.

Gas chromatography has proven to be a very useful analytical technique for in situ analysis of extraterrestrial environments as demonstrated by its successful operation on spacecraft missions to Mars and Venus. The technique is also one of the six scientific instruments aboard the Huygens probe to explore Titan's atmosphere and surface. A review of gas chromatography in previous space missions and some recent developments in the current environment of fiscal constraints and payload size limitations are presented.     

Identification of the D(3h) isomer of carbon trioxide (CO3) and its implications for atmospheric chemistry.

The CO3 molecule is considered an important reaction intermediate in the atmospheres of Earth and Mars for quenching electronically excited oxygen atoms and in contributing to the anomalous 18O isotope enrichment. The geometry of the CO3 intermediate plays an important role in explaining these effects; however, only the cyclic (C(2v)) isomer has been experimentally confirmed so far. Here, we report on the first spectroscopic detection of the acyclic (D(3h)) isomer of carbon trioxide (12C16O3) via its nu1 and nu2 vibrational modes centered around 1165 cm(-1) under matrix isolation conditions; the identification of the 12C18O3, 13C16O3, 13C18O3, 16O12C18O2, and 18O12C16O2 isotopomers of the acyclic isomer confirms the assignments.     

Elementary reactions of N atoms with hydrocarbons: first steps towards the formation of prebiotic N-containing molecules in planetary atmospheres

Gas-phase reactions involving atomic nitrogen in the ground (4)S and first excited (2)D electronic states with simple hydrocarbons or hydrocarbon radicals lead to the formation of prebiotic N-containing organic molecules. These reactions are now active in the upper atmosphere of Titan (a massive moon of Saturn) and might have played an important role in nitrogen fixation in the primitive upper terrestrial atmosphere, assuming that it is similar to the present atmosphere of Titan. The products of these reactions (nitriles, imines and radicals) are the precursors of larger N-containing molecules, which form the dense haze aerosols that completely cover the moon of Saturn. If anything similar to Titan's haze has ever existed on our planet, it is reasonable to imagine that, once deposited on the surface of the oceans, further chemical evolution might have transformed these molecules into aminoacids and nucleobases, the molecular building blocks of living entities. The experimental techniques necessary to investigate these reactions in detail are presented and the main results reviewed.     

Spectroscopic detection and theoretical confirmation of the role of Cr2(CO)5(C5R5)2 and .Cr(CO)2(ketene)(C5R5) as intermediates in carbonylation of N=N=CHSiMe3 to O=C=CHSiMe3 by .Cr(CO)3(C5R5) (R = H, CH3)

Conversion of N=N=CHSiMe3 to O=C=CHSiMe3 by the radical complexes .Cr(CO)3C5R5 (R = H, CH3) derived from dissociation of [Cr(CO)3(C5R5)]2 have been investigated under CO, Ar, and N2 atmospheres. Under an Ar or N2 atmosphere the reaction is stoichiometric and produces the Cr[triple bond]Cr triply bonded complex [Cr(CO)2(C5R5)]2. Under a CO atmosphere regeneration of [Cr(CO)3(C5R5)]2 (R = H, CH3) occurs competitively and conversion of diazo to ketene occurs catalytically as well as stoichiometrically. Two key intermediates in the reaction, .Cr(CO)2(ketene)(C5R5) and Cr2(CO)5(C5R5)2 have been detected spectroscopically. The complex .Cr(13CO)2(O=13C=CHSiMe3)(C5Me5) has been studied by electron spin resonance spectroscopy in toluene solution: g(iso) = 2.007; A(53Cr) = 125 MHz; A(13CO) = 22.5 MHz; A(O=13C=CHSiMe3) = 12.0 MHz. The complex Cr2(CO)5(C5H5)2, generated in situ, does not show a signal in its 1H NMR and reacts relatively slowly with CO. It is proposed to be a ground-state triplet in keeping with predictions based on high level density functional theory (DFT) studies. Computed vibrational frequencies are also in good agreement with experimental data. The rates of CO loss from 3Cr2(CO)5(C5H5)2 producing 1[Cr(CO)2(C5H5)]2 and CO addition to 3Cr2(CO)5(C5H5)2 producing 1[Cr(CO)3(C5H5)]2 have been measured by kinetics and show DeltaH approximately equal 23 kcal mol(-1) for both processes. Enthalpies of reduction by Na/Hg under CO atmosphere of [Cr(CO)n(C5H5)]2 (n = 2,3) have been measured by solution calorimetry and provide data for estimation of the Cr[triple bond]Cr bond strength in [Cr(CO)2(C5H5)]2 as 72 kcal mol(-1). The complex [Cr(CO)2(C5H5)]2 does not readily undergo 13CO exchange at room temperature or 50 degrees C implying that 3Cr2(CO)5(C5H5)2 is not readily accessed from the thermodynamically stable complex [Cr(CO)2(C5H5)]2. A detailed mechanism for metalloradical based conversion of diazo and CO to ketene and N2 is proposed on the basis of a combination of experimental and theoretical data.     

BOOK REVIEWS

Book reviewed in this article:
Chemistry of Atmospheres, An introduction to the chemistry of the atmospheres of Earth, the planets and their satellites .Edited by Richard P. Wayne
Advances in Photochemistry , vol.13 Edited by D. H. Volman, K. Gollnick and G. S. Hammond.
Multiple Photon Infrared Laser Photophysics and Photochemistry . V. N. Bagratashvili, V. S. Leto-khov, A. A. Makarov and E. A. Ryabov.     

A macro-engineering concept to maintain desirable planetary biospheres

Current terraforming concepts do not comprehensively encompass active biosphere protection measures for tomorrow's expensively developed extraterrestrial real estate. Already tailored for Earth, Rodoman-ALPS is an extant protection system concept easily duplicated and installable around a technologically made-over Mars. Ongoing active control systems, including multiple Rodoman-ALPS installations, will be needed to keep a hominized Earth and all newly terraformed planets the way we would like them to be.     

Solar UV irradiation conditions on the surface of Mars

The UV radiation environment on planetary surfaces and within atmospheres is of importance in a wide range of scientific disciplines. Solar UV radiation is a driving force of chemical and organic evolution and serves also as a constraint in biological evolution. In this work we modeled the transmission of present and early solar UV radiation from 200 to 400 nm through the present-day and early (3.5 Gyr ago) Martian atmosphere for a variety of possible cases, including dust loading, observed and modeled O3 concentrations. The UV stress on microorganisms and/or molecules essential for life was estimated by using DNA damaging effects (specifically bacteriophage T7 killing and uracil dimerization) for various irradiation conditions on the present and ancient Martian surface. Our study suggests that the UV irradiance on the early Martian surface 3.5 Gyr ago may have been comparable with that of present-day Earth, and though the current Martian UV environment is still quite severe from a biological viewpoint, we show that substantial protection can still be afforded under dust and ice.     

Combustion characteristics and kinetics of DPR Korea’s anthracite in O2/N2 and O2/CO2 atmosphere

Journal of Thermal Analysis and Calorimetry - In O2/N2 and O2/CO2 atmospheres with oxygen concentrations of 21%, 30%, and 50%, combustion characteristics index, apparent activation energy, and...     

THIS: a tuneable heterodyne infrared spectrometer

With the Cologne Tuneable Heterodyne Infrared Spectrometer (THIS) we present a newly developed setup of a transportable heterodyne receiver. Competitiveness with regard to sensitivity, was reached for the first time with a semiconductor laser pumped system. Frequency tuneability of the local oscillator (LO) laser over a wide range of wavelengths is thus provided. This allows a variety of molecules, e.g. O3, NH3, CH4, N2O,.... in the earth's atmosphere, in planetary atmospheres or even in interstellar space to be observed with very high frequency resolution either from aboard the Stratospheric Observatory For Infrared Astronomy (SOFIA) or other ground based telescopes. Besides the good results with tuneable lead salt laser (TDL) operation there's room to improve: the power provided by such devices is not sufficient for a sensitivity close to the quantum limit. Therefore, first tests with recently developed high power quantum-cascade lasers (QCL) were carried out and further substantial improvement of the system noise temperature seems to be in reach.     

质谱检测技术在火星探测中的应用

火星探测对人类寻找地外生命、探索行星产生和演化机制具有重要的科学意义.质谱技术已经在火星探测方面得到了实际应用,获得的数据正在改写着人类对火星的基本认识.本文综述了国内外质谱技术在火星探测任务中的应用现状,特别是我国学者的研究进展、存在问题和应对策略.     

Fragmentation Pathways of Singly- and Doubly-charged Ions in the Mass Spectra of Si-, N- and C-Substituted 1,3-Dioxa-6-aza-2-silacyclooctanes

The fragmentation pathways of singly- and doubly-charged ions in the mass spectra of Si-, N-, and C-substituted 1,3-dioxa-6-aza-2-silacyclooctanes upon electron impact have been studied. The directions for the fragmentation of the singly- and doubly-charged molecular ions differ markedly. All the doubly-charged fragmentation ions are formed by the loss of neutral molecules from M⁺⁺ and contain nitrogen and silicon atoms.     

Mass spectrometry in the U.S. space program: Past, present, and future

Recent years have witnessed significant progress on the miniaturization of mass spectrometers for a variety of field applications. This article describes the development and application of mass spectrometry (MS) instrumentation to support of goals of the U.S. space program. Its main focus is on the two most common space-related applications of MS: studying the composition of planetary atmospheres and monitoring air quality on manned space missions. Both sets of applications present special requirements in terms of analytical performance (sensitivity, selectivity, speed, etc.), logistical considerations (space, weight, and power requirements), and deployment in perhaps the harshest of all possible environments (space). The MS instruments deployed on the Pioneer Venus and Mars Viking Lander missions are reviewed for the purposes of illustrating the unique features of the sample introduction systems, mass analyzers, and vacuum systems, and for presenting their specifications which are impressive even by today's standards. The various approaches for monitoring volatile organic compounds (VOCs) in cabin atmospheres are also reviewed. In the past, ground-based GC/MS instruments have been used to identify and quantify VOCs in archival samples collected during the Mercury, Apollo, Skylab, Space Shuttle, and Mir missions. Some of the data from the more recent missions are provided to illustrate the composition data obtained and to underscore the need for instrumentation to perform such monitoring in situ. Lastly, the development of two emerging technologies, Direct Sampling Ion Trap Mass Spectrometry (DSITMS) and GC/Ion Mobility Spectrometry (GC/IMS), will be discussed to illustrate their potential utility for future missions.