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Multiplex gas chromatography: an alternative concept for gas chromatographic analysis of planetary atmospheres.

Gas chromatography (GC) is a powerful technique for analyzing gaseous mixtures. Applied to the earth's atmosphere, GC can be used to determine the permanent gases--such as carbon dioxide, nitrogen, and oxygen--and to analyze organic pollutants in air. The U.S. National Aeronautics and Space Administration (NASA) has used GC in spacecraft missions to Mars (the Viking Biology Gas Exchange Experiment [GEX] and the Viking Gas Chromatograph-Mass Spectrometer [GC-MS]) and to Venus (the Pioneer Venus Gas Chromatograph [PVGC] on board the Pioneer Venus sounder probe) for determining the atmospheric constituents of these two planets. Even though conventional GC was very useful in the Viking and Pioneer missions, spacecraft constraints and limitations intrinsic to the technique prevented the collection of more samples. With the Venus probe, for instance, each measurement took a relatively long time to complete (10 min), and successive samples could not be introduced until the previous samples had left the column. Therefore, while the probe descended through the Venusian atmosphere, only three samples were acquired at widely separated altitudes. With the Viking mission, the sampling rate was not a serious problem because samples were acquired over a period of one year. However, the detection limit was a major disadvantage. The GC-MS could not detect simple hydrocarbons and simple alcohols below 0.1 ppm, and the GEX could not detect them below 1 ppm. For more complex molecules, the detection limits were at the parts-per-billion level for both instruments. Finally, in both the Viking and Pioneer missions, the relatively slow rate of data acquisition limited the number of analyses, and consequently, the amount of information returned. Similar constraints are expected in future NASA missions. For instance, gas chromatographic instrumentation is being developed to collect and analyze organic gases and aerosols in the atmosphere of Titan (one of Saturn's satellites). The Titan-Cassini entry probe, which is being jointly planned by NASA and the European Space Agency (ESA), might be launched as early as 1994. As in the Pioneer mission, limited time--perhaps only 3-4 h--will be available for the completion of all analyses while the probe descends through the atmosphere. A conventional GC or GC-MS system would be able to analyze no more than two aerosol and two gas samples during the probe's descent. Conventional GC also is limited by the sensitivity of the detector and by the sample volume. For the Titan mission, the sensitivity problems will be worse because the atmospheric pressure at the time of instrument deployment is expected to be < 3 torr. Consequently, the sample volume might not be large enough to satisfy the detector sensitivity requirements. Because of such limitations, alternative GC analysis techniques have been investigated for future NASA missions. Multiplex gas chromatography has been investigated as a possible candidate for chemical analysis within a spacecraft or other restricted environment, and chemical modulators have been developed and used when needed with this technique to reduce the size and weight of the instrumentation. Also, several new multiplex techniques have been developed for use in specific applications.

Atmosphere↗

A review of interstellar rocketry fundamentals.

To reach even the nearest stars in a human lifetime requires a ship speed that is a substantial fraction of the speed of light. This means an enormous kinetic energy investment in the ship and suggests that maximizing the efficiency may be more important than minimizing the mass ratio. This paper develops the pertinent relativistic rocket equations and finds the conditions for high kinematic efficiency. Using the limiting efficiency of 100%, the minimum energy needed for one-way and for round trip voyages, and to explore all "good" suns out to a given distance, using pre-fueled rockets, is determined. Savings due to refueling the rocket (and reloading propellant) at the destination and in flight are both somewhat greater than 2:1.

Mathematics↗

Status of the NASA SETI Sky Survey microwave observing project.

The Sky Survey observing program is one of two complementary strategies that NASA plans to use in its microwave Search for Extraterrestrial Intelligence (SETI). The primary objective of the Sky Survey is to search the entire sky over the frequency range 1000-10,000 MHz for evidence of narrow band signals of extraterrestrial, intelligent origin. Spectrum analyzers with upwards of 10 million channels and data rates in excess of 10 gigabits per second are required to complete the survey in less than 7 years. To lay the foundation for the operational SETI Sky Survey, a prototype system has been built to test and refine real time signal detection algorithms, to test scan strategies and observatory control functions, and to test algorithms designed to reject radio frequency interference. This paper presents a high level description of the prototype hardware and software and reports on the preparations to deploy the system to the 34-m antenna at the research and development station of NASA's Deep Space Communication Complex, Goldstone, California.

Communication↗

Probing the structure of cometary ice.

Computer simulations of bulk and vapor deposited amorphous ices are presented. The structure of the bulk low density amorphous ice is in good agreement with experiments on pressure disordered amorphous ice. Both the low density bulk ice and the vapor deposited ices exhibit strong ordering. Vapor deposition of hot (300 K) water molecules onto a cold (77 K) substrate yields less porous ices than deposition of cold (77 K) water molecules onto a cold substrate. Both vapor deposited ices are more porous than the bulk amorphous ice. The structure of bulk high density amorphous ice is only in fair agreement with experimental results. Attempts to simulate high density amorphous ice via vapor deposition were not successful. Electron diffraction results on vapor deposited amorphous ice indicate that the temperature of the nucleation of the cubic phase depends upon the amount of time between the deposition and the onset of crystallization, suggesting that freshly deposited ice layers reconstruct on times of the order of hours. The temperature dependence of the microporosity of the vapor deposited amorphous ices might affect laboratory experiments that are aimed at simulating astrophysical ices in the context of the origin of prebiotic organic material and its transport to the Earth.

Computer Simulation↗

Germination and growth of wheat in simulated Martian atmospheres.

One design for a manned Mars base incorporates a bioregenerative life support system based upon growing higher plants at a low atmospheric pressure in a greenhouse on the Martian surface. To determine the concept's feasibility, the germination and initial growth of wheat (Triticum aestivum) was evaluated at low atmospheric pressures in simulated Martian atmosphere (SMA) and in SMA supplemented with oxygen. Total atmospheric pressures ranged from 10 to 1013 mb. No seeds germinated in pure SMA, regardless of atmospheric pressure. In SMA plus oxygen at 60 mb total pressure, germination and growth occurred but were lower than in the Earth atmosphere controls.

Atmospheric Pressure↗

Evolution of the biosynthesis of the branched-chain amino acids.

The origin of the biosynthetic pathways for the branched-chain amino acids cannot be understood in terms of the backwards development of the present acetolactate pathway because it contains unstable intermediates. We propose that the first biosynthesis of the branched-chain amino acids was by the reductive carboxylation of short branched chain fatty acids giving keto acids which were then transaminated. Similar reaction sequences mediated by nonspecific enzymes would produce serine and threonine from the abundant prebiotic compounds glycolic and lactic acids. The aromatic amino acids may also have first been synthesized in this way, e.g. tryptophan from indole acetic acid. The next step would have been the biosynthesis of leucine from alpha-ketoisovaleric acid. The acetolactate pathway developed subsequently. The first version of the Krebs cycle, which was used for amino acid biosynthesis, would have been assembled by making use of the reductive carboxylation and leucine biosynthesis enzymes, and completed with the development of a single new enzyme, succinate dehydrogenase. This evolutionary scheme suggests that there may be limitations to inferring the origins of metabolism by a simple back extrapolation of current pathways.

Acetolactate Synthase↗

The stability of amino acids at submarine hydrothermal vent temperatures.

It has been postulated that amino acid stability at hydrothermal vent temperatures is controlled by a metastable thermodynamic equilibrium rather than by kinetics. Experiments reported here demonstrate that the amino acids are irreversibly destroyed by heating at 240 degrees C and that quasi-equilibrium calculations give misleading descriptions of the experimental observations. Equilibrium thermodynamic calculations are not applicable to organic compounds under high-temperature submarine vent conditions.

Alanine↗

Mineral induced formation of sugar phosphates.

Glycolaldehyde phosphate, sorbed from highly dilute, weakly alkaline solution into the interlayer of common expanding sheet structure metal hydroxide minerals, condenses extensively to racemic aldotetrose-2,4-diphosphates and aldohexose-2,4,6-triphosphates. The reaction proceeds mainly through racemic erythrose-2,4-phosphate, and terminates with a large fraction of racemic altrose-2,4,6-phosphate. In the absence of an inductive mineral phase, no detectable homogeneous reaction takes place in the concentration- and pH range used. The reactant glycolaldehyde phosphate is practically completely sorbed within an hour from solutions with concentrations as low as 50 micrometers; the half-time for conversion to hexose phosphates is of the order of two days at room temperature and pH 9.5. Total production of sugar phosphates in the mineral interlayer is largely independent of the glycolaldehyde phosphate concentration in the external solution, but is determined by the total amount of GAP offered for sorption up to the capacity of the mineral. In the presence of equimolar amounts of rac-glyceraldehyde-2-phosphate, but under otherwise similar conditions, aldopentose-2,4,-diphosphates also form, but only as a small fraction of the hexose-2,4,6-phosphates.

Acetaldehyde↗

Preferential uptake of ammonium ions by zinc ferrocyanide.

The concentration of ammonia from dilute aqueous solution could have facilitated many prebiotic reactions. This may be especially true if this concentration involves incorporation into an organized medium. We have shown that (unlike iron(III) ferrocyanide) zinc ferrocyanide,Zn2Fe(CN)6 xH2O, preferentially takes up ammonium ions from 0.01 M NH4Cl to give the known material Zn3(NH4)2[Fe(CN)6]2 xH2O, even in the presence of 0.01 M KCl. KCl alone gave Zn3K2[Fe(CN)6]2 xH2O. Products were characterized by elemental (CHN) analysis and powder X-ray diffraction (XRD). We attribute the remarkable specificity for the ammonium ion to the open framework of the product, which offers enough space for hydrogen-bonded ammonium ions, and infer that other inorganic materials with internal spaces rich in water may show a similar preference.

Ammonia↗

Chemical evolution and the origin of life: cumulative keyword subject index 1970-1986.

This cumulative subject index encompasses the subject indexes of the bibliographies on Chemical Evolution and the Origin of Life that were first published in 1970 and have continued through publication of the 1986 bibliography supplement. Early bibliographies focused on experimental and theoretical material dealing directly with the concepts of chemical evolution and the origin of life, excluding the broader areas of exobiology, biological evolution, and geochemistry. In recent years, these broader subject areas have also been incorporated as they appear in literature searches relating to chemical evolution and the origin of life, although direct attempts have not been made to compile all of the citations in these broad areas. The keyword subject indexes have also undergone an analogous change in scope. Compilers of earlier bibliographies used the most specific term available in producing the subject index. Compilers of recent bibliographies have used a number of broad terms relating to the overall subject content of each citation and specific terms where appropriate. The subject indexes of these 17 bibliographies have, in general, been cumulatively compiled exactly as they originally appeared. However, some changes have been made in an attempt to correct errors, combine terms, and provide more meaningful terms.

Exobiology↗

Planetary Protection Policy (U.S.A.).

Through existing treaty obligations of the United States, NASA is committed to exploring space while avoiding biological contamination of the planets, and to the protection of the Earth against harm from materials returned from space. Because of the similarities between Mars and Earth, plans for the exploration of Mars evoke discussions of these Planetary Protection issues. US Planetary Protection Policy will be focused on the preservation of these goals in an arena that will change with the growth of scientific knowledge about the martian environment. Early opportunities to gain the appropriate data will be used to guide later policy implementation. Because human presence on Mars will result in the end of Earth's separation from the martian environment, it is expected that precursor robotic missions will address critical planetary protection concerns before humans arrive.

Containment of Biohazards↗

A consensus approach to planetary protection requirements: recommendations for Mars lander missions.

Over the last several years, the nature of the surface conditions on the planet Mars, our knowledge of the growth capabilities of Earth organisms under extreme conditions, and future opportunities for Mars exploration have been under extensive review in the United States and elsewhere. As part of these examinations, in 1992 the US Space Studies Board made a series of recommendations to NASA on the requirements that should be implemented on future missions that will explore Mars. In particular, significant changes were recommended in the requirements for Mars landers, changes that significantly alleviated the burden of planetary protection implementation for these missions. In this paper we propose a resolution implementing this new set of recommendations, for adoption by COSPAR at its 30th meeting in Hamburg. We also discuss future directions and study areas for planetary protection, in light of changing plans for Mars exploration.

Consensus Statements as Topic↗

A simple procedure for constructing 5'-amino-terminated oligodeoxynucleotides in aqueous solution.

A rapid method for the synthesis of oligodeoxynucleotides (ODNs) terminated by 5'-amino-5'-deoxythymidine is described. A 3'-phosphorylated ODN (the donor) is incubated in aqueous solution with 5'-amino- 5'-deoxythymidine in the presence of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC), extending the donor by one residue via a phosphoramidate bond. Template- directed ligation of the extended donor and an acceptor ODN, followed by acid hydrolysis, yields the acceptor ODN extended by a single 5'-amino-5'-deoxythymidine residue at its 5'terminus.

Base Sequence↗

The space life sciences strategy for the 21st century.

In the past, space life sciences has focused on gaining an understanding of physiological tolerance to spaceflight, but, for the last 10 years, the focus has evolved to include issues relevant to extended duration missions. In the 21st century, NASA's long-term strategy for the exploration of the solar system will combine the assurance of human health and performance for long periods in space with investigations aimed at searching for traces of life on other planets and acquiring fundamental scientific knowledge of life processes. Implementation of this strategy will involve a variety of disciplines including radiation health, life support, human factors, space physiology and countermeasures, medical care, environmental health, and exobiology. It will use both ground-based and flight research opportunities such as those found in current on-going programs, on Spacelab and unmanned biosatellite flights, and during Space Station Freedom missions.

Aerospace Medicine↗

Use of Martian resources in a Controlled Ecological Life Support System (CELSS).

The exploration of Mars has long been considered as a major goal in the exploration of the Solar system. The Space Station Freedom will make such missions feasible because it will provide a site for the assembly and launch of the large vehicles required. Interest in manned visits to Mars often focus on the possibility of collecting information about the origin of that planet, & hence of the solar system, including the Earth. Interest also involves the history of the planet, its past record of geological and fluvial activity, atmospheric and thermal history and surface chemical activity. The latter is of particular interest to exobiologists who would like to seek evidence of pre-biological physical and chemical activity involving organic molecules. Finally, there is interest in the possibility of planetary ecosynthesis, i.e. specific intervention in the evolution of Mars that could result in the development of a second habitable planet in the solar system. The scenarios for visits and the establishment of bases on Mars are being developed now. The intent of this paper is to consider various possibilities for crew life support on Mars and particularly to explore the use of Martian resources as life support materials.

Carbon Dioxide↗