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PubMed2003

Mars Surveyor Program '01 Mars Environmental Compatibility Assessment wet chemistry lab: a sensor array for chemical analysis of the Martian soil.

The Mars Environmental Compatibility Assessment (MECA) instrument was designed, built, and flight qualified for the now canceled MSP (Mars Surveyor Program) '01 Lander. The MECA package consisted of a microscope, electrometer, material patch plates, and a wet chemistry laboratory (WCL). The primary goal of MECA was to analyze the Martian soil (regolith) for possible hazards to future astronauts and to provide a better understanding of Martian regolith geochemistry. The purpose of the WCL was to analyze for a range of soluble ionic chemical species and electrochemical parameters. The heart of the WCL was a sensor array of electrochemically based ion-selective electrodes (ISE). After 20 months storage at -23 degrees C and subsequent extended freeze/thawing cycles, WCL sensors were evaluated to determine both their physical durability and analytical responses. A fractional factorial calibration of the sensors was used to obtain slope, intercept, and all necessary selectivity coefficients simultaneously for selected ISEs. This calibration was used to model five cation and three anion sensors. These data were subsequently used to determine concentrations of several ions in two soil leachate simulants (based on terrestrial seawater and hypothesized Mars brine) and four actual soil samples. The WCL results were compared to simulant and soil samples using ion chromatography and inductively coupled plasma optical emission spectroscopy. The results showed that flight qualification and prolonged low-temperature storage conditions had minimal effects on the sensors. In addition, the analytical optimization method provided quantitative and qualitative data that could be used to accurately identify the chemical composition of the simulants and soils. The WCL has the ability to provide data that can be used to "read" the chemical, geological, and climatic history of Mars, as well as the potential habitability of its regolith.

Anions↗
PubMed1989

The case for planetary sample return missions. 2. History of Mars.

Principal science goals for exploration of Mars are to establish the chemical, isotopic, and physical state of Martian material, the nature of major surface-forming processes and their time scales, and the past and present biological potential of the planet. Many of those goals can only be met by detailed analyses of atmospheric gases and carefully selected samples of fresh rocks, weathered rocks, soils, sediments, and ices. The high-fidelity mineral separations, complex chemical treatments, and ultrasensitive instrument systems required for key measurements, as well as the need to adapt analytical strategies to unanticipated results, point to Earth-based laboratory analyses on returned Martian samples as the best means for meeting the stated objectives.

Chemical Phenomena↗
PubMed1991

Composition of solar flare noble gases preserved in meteorite parent body regolith.

The isotopic composition (long-term average) of solar flare (SF) Ne has been determined by three isotope correlation techniques applied to data measured on chemically etched pyroxene separates prepared from the Kapoeta meteorite, which is known to contain implanted solar gases. The SF 20Ne/22Ne ratio obtained is 11.6 +/- 0.2 and confirms previous determinations of this SF ratio in lunar and meteoritic samples. The same SF Ne composition is also obtained by applying an ordinate intercept technique to the same data set. The ordinate intercept technique was also applied to the Ar and He data, on which the three-isotope correlation technique cannot be applied. The isotopic composition of SF Ar and SF He so obtained are SF 36Ar/38Ar = 4.9 +/- 0.1 and SF 4He/3He = 3800 +/- 200, which are significantly different from the solar wind (SW) Ar and SW He values of approximately 5.35 and approximately 2500, respectively. Correlation between 20Ne/22Ne and 36Ar/38Ar for the same data set also gives a similar SF 36Ar/38Ar ratio of 4.8 +/- 0.2. The determined SF He, Ne and Ar isotopic ratios differ from those in SW by 52%, 17% and 9%, respectively, but the elemental compositions of 4He/36Ar and 20Ne/36Ar do not show obvious differences between SF and SW. The concentration of the SF component in Kapoeta pyroxenes is approximately 20% that of the SW component, which is orders of magnitude higher than expected from SW and SF proton flux measurements. Variations in elemental and isotopic composition of He, Ne and Ar in SF relative to SW are found to correlate well with a (Z/A)2 dependence, indicating a rigidity-dependent particle spectrum in solar flares.

Argon↗
PubMed1992

Volatiles in interplanetary dust particles: a review.

The paper presents a review of the volatiles found within interplanetary dust particles. These particles have been shown to represent primitive material from early in the solar system's formation and also may contain records of stellar processes. The organogenic elements (i.e., H, C, N, O, and S) are among the most abundant elements in our solar system, and their abundances, distributions, and isotopic compositions in early solar system materials permit workers to better understand the processes operating early in the evolutionary history of solar system materials. Interplanetary dust particles have a range of elemental compositions, but generally they have been shown to be similar to carbonaceous chondrites, the solar photosphere, Comet Halley's chondritic cores, and matrix materials of chondritic chondrites. Recovery and analysis of interplanetary dust particles have opened new opportunities for analysis of primitive materials, although interplanetary dust particles represent major challenges to the analyst because of their small size.

Aluminum↗
PubMed1992

Airburst origin of dark shadows on Venus.

A simple analytic model for the catastrophic disruption and deceleration of impactors in a thick atmosphere is used to (1) reproduce observed Venusian cratering statistics and (2) generate radar-dark disks by the impact of atmospheric shock waves with the surface. When used as input to Monte Carlo simulations of Venusian cratering, the model nicely reproduces the observed low diameter cutoff. Venusian craters are found to be more consistent with an asteroidal rather than a cometary source. The radar-dark "shadows" of the title are surface features, usually circular, that have been attributed to airbursting impactors. A typical craterless airburst is the equivalent of a approximately 10(6) megaton explosion. The airburst is treated as a massive, extended explosion using a thin-shell, isobaric cavity approximation. The strong atmospheric shock waves excited by the airbust are then coupled to surface rock using the usual impedance matching conditions. Peak shock pressures experienced by surface rock typically exceed 0.2 GPa for distances 15-30 km from ground zero (the place on the surface immediately beneath the site of the airburst), and 1 GPa for 10-20 km. These high shock pressures are felt to considerable depth, often more than a kilometer. Beneath the airburst the shock could reduce surface rocks to fine rubble, while at greater distance the weaker shock would leave fields of broken blocks, perhaps in part accounting for radar-bright halos that often surround the dark shadows.

Astronomy↗
PubMed1995

A slightly more massive young Sun as an explanation for warm temperatures on early Mars.

The valley network channels on the heavily cratered ancient surface of Mars suggest the presence of liquid water approximately 3.8 Gyr ago. However, the implied warm climate is difficult to explain in the context of the standard solar model, even allowing for the maximum CO2 greenhouse heating. In this paper we investigate the astronomical and planetary implications of a nonstandard solar model in which the zero-age, main-sequence Sun had a mass of 1.05 +/- 0.02 M solar. The excess mass was subsequently lost in a solar wind during the first 1.2(-0.2, +0.4) Gyr of the Sun's main sequence phase. The implied mass-loss rate of 4(+3, -2) x 10(-11) M solar yr-1, or about 10(3)x that of the current Sun, may be detectable in several nearby young solar type stars.

Astronomy↗
PubMed1995

Spectrophotometry and organic matter on Iapetus. 1. Composition models.

Iapetus shows a greater hemispheric albedo asymmetry than any other body in the solar system. Hapke scattering theory and optical constants measured in the laboratory are used to identify possible compositions for the dark material on the leading hemisphere of Iapetus. The materials considered are poly-HCN, kerogen, Murchison organic residue, Titan tholin, ice tholin, and water ice. Three-component mixtures of these materials are modeled in intraparticle, particle, and areal mixtures. In a computer grid search of approximately 2 x 10(7) models, an intraparticle mixture of 25% poly-HCN, 10% Murchison residue, and 65% water ice is found to best fit the spectrum, albedo, and phase behavior of the dark material. The Murchison residue and/or water ice can be replaced by kerogen and ice tholin, respectively, and still produce very good fits. Areal and particle mixtures of poly-HCN, Titan tholin, and either ice tholin or Murchison residue are also possible models. Poly-HCN is a necessary component in almost all good models. The presence of poly-HCN can be further tested by high-resolution observations near 4.5 micrometers.

Astronomy↗
PubMed1995

Photochemistry of Triton's atmosphere and ionosphere.

The photochemistry of 32 neutral and 21 ion species in Triton's atmosphere is considered. Parent species N2, CH4, and CO (with a mixing ratio of 3 x 10(-4) in our basic model) sublime from the ice with rates of 40, 208, and 0.3 g/cm2/b.y., respectively. Chemistry below 50 km is driven mostly by photolysis of methane by the solar and interstellar medium Lyman-alpha photons, producing hydrocarbons C2H4, C2H6, and C2H2 which form haze particles with precipitation rates of 135, 28, and 1.3 g/cm2/b.y., respectively. Some processes are discussed which increase the production of HCN (by an order of magnitude to a value of 29 g/cm2/b.y.) and involve indirect photolysis of N2 by neutrals. Reanalysis of the measured methane profiles gives an eddy diffusion coefficient K = 4 x 10(3) cm2/s above the tropopause and a more accurate methane number density near the surface, (3.1 +/- 0.8) x 10(11) cm-3. Chemistry above 200 km is driven by the solar EUV radiation (lambda < 1000 angstroms) and by precipitation of magnetospheric electrons with a total energy input of 10(8) W (based on thermal balance calculations). The most abundant photochemical species are N, H2, H, O, and C. They escape with the total rates of 7.7 x 10(24) s-1, 4.5 x 10(25) s-1, 2.4 x 10(25) s-1, 4.4 x 10(22) s-1, and 1.1 x 10(24) s-1, respectively. Atomic species are transported to a region of 50-200 km and drive the chemistry there. Ionospheric chemistry explains the formation of an E region at 150-240 km with HCO+ as a major ion, and of an F region above 240 km with a peak at 320 km and C+ as a major ion. The ionosphere above 500 km consists of almost equal densities of C+ and N+ ions. The model profiles agree with the measured atomic nitrogen and electron density profiles. A number of other models with varying rate coefficients of some reactions, differing properties of the haze particles (chemically passive or active), etc., were developed. These models show that there are four basic unknown values which have strong impacts on the composition and structure of the atmosphere and ionosphere. These values and their plausible ranges are the CO mixing ratio fco = 10(-4)-10(-3), the magnetospheric electron energy input (1 +/- 0.5) x 10(8) W, the rate coefficient of charge-exchange reaction N2(+) + C k = 10(-11)-10(-10) cm3/s, and the ion escape velocity Vi approximately equal to 150 cm/s.

Atmosphere↗
PubMed1995

Alteration of volatile inventories by polar clathrate formation on Mars.

Recent models of chaotic variation in the Martian obliquity suggest that CO2 could be released during times of high obliquity and then recaptured in the polar caps as ice or clathrate during times of lower obliquity (Jakosky, et al., 1995). A natural implication of clathrate trapping is that other species in the Martian atmosphere, including noble gases, must incorporate in the water ice structure as well, in varying amounts according to the size and polarizability of the molecules as well as their atmospheric abundances. For nominal estimates of cap volume and amount of incorporated CO2 , we find that the current atmospheric inventory of noble gases is not representative of the bulk inventory in the Martian surface-atmosphere system. In particular, xenon and krypton are underrepresented in the present atmosphere. Models of source regions for Martian volatiles, which are constrained by noble gas abundances, must be modified to take these fractionation effects into account if indeed evidence for large amounts of polar clathrates is found.

Atmosphere↗
PubMed1996

Mechanism of cyanoacetylene photochemistry at 185 and 254 nm.

The role of cyanoacetylene (HC3N) in the atmospheric photochemistry of Titan and its relevance to polymer formation are discussed. Investigation of the relative light absorption of HC3N, acetylene (C2H2), and diacetylene (C4H2) revealed that HC3N is an important absorber of UV light in the 205- to 225-nanometer wavelength region in Titan's polar regions. Laboratory studies established that photolysis of C2H2 initiates the polymerization of HC3N even though the HC3N is not absorbing the UV light. Quantum yield measurements establish that HC3N is 2-5 times as reactive as C2H2 for polymer formation. Photolysis of HC3N with 185-nanometer light in the presence of N2, H2, Ar, or CF4 results in a decrease in the yield of 1,3,5-tricyanobenzene (1,3,5-tcb), while photolysis in the presence of CH4, C2H6, or n-C4H10 results in an increase in 1,3,5-tcb. The rate of loss of HC3N is increased by all gases except H2, where it is unchanged. It was not possible to detect 1,3,5-tcb as a photoproduct when the partial pressure of HC3N was decreased to 1 torr. Photolysis of HC3N with 254-nanometer light in the presence of H2 or N2 results in the formation of 1,2,4-tcb, while photolysis in the presence of CH4, C2H6, or n-C4H10 results in the formation of increasing amounts of 1,3,5-tcb. Mechanisms for the formation of polymers are presented.

Acetylene↗
PubMed1996

Ground-based detectability of terrestrial and Jovian extrasolar planets: observations of CM Draconis at Lick Observatory.

The detection of terrestrial-sized extrasolar planets from the ground has been thought to be virtually impossible due to atmospheric scintillation limits. However, we show that this is not the case especially selected (but nevertheless main sequence) stars, namely small eclipsing binaries. For the smallest of these systems, CM Draconis, several months to a few years of photometric observations with 1-m-class telescopes will be sufficient to detect the transits of any short-period planets of sizes > or = 1.5 Earth radii (RE), using cross-correlation analysis with moderately good photometry. Somewhat larger telescopes will be needed to extend this detectability to terrestrial planets in larger eclipsing binary systems. (We arbitrarily define "terrestrial planets" herein as those whose disc areas are closer to that of Earth's than Neptune's i.e., less than about 2.78 RE.) As a "spin-off" of such observations, we will also be able to detect the presence of Jovian-mass planets without transits using the timing of the eclipse minima. Eclipse minima will drift in time as the binary system is offset by a sufficiently massive planet (i.e., one Jupiter mass) about the binary/giant-planet barycenter, causing a periodic variation in the light travel time to the observer. We present here an outline of present observations taking place at the University of California Lick Observatory using the Crossley 0.9-m telescope in collaboration with other observatories (in South Korea, Crete, France, Canary Islands, and New York) to detect or constrain the existence of terrestrial planets around main sequence eclipsing binary star systems, starting with CM Draconis. We demonstrate the applicability of photometric data to the general detection of gas giant planets via eclipse minima timings in many other small-mass eclipsing binary systems as well.

Astronomy↗
PubMed1997

Hydrothermal hydration of Martian crust: illustration via geochemical model calculations.

If hydrothermal Systems existed on Mars, hydration of crustal rocks may have had the potential to affect the water budget of the planet. We have conducted geochemical model calculations to investigate the relative roles of host rock composition, temperature, water-to-rock ratio, and initial fluid oxygen fugacity on the mineralogy of hydrothermal alteration assemblages, as well as the effectiveness of alteration to store water in the crust as hydrous minerals. In order to place calculations for Mars in perspective, models of hydrothermal alteration of three genetically related Icelandic volcanics (a basalt, andesite, and rhyolite) are presented, together with results for compositions based on SNC meteorite samples (Shergotty and Chassigny). Temperatures from 150 degrees C to 250 degrees C, water-to-rock ratios from 0.1 to 1000, and two initial fluid oxygen fugacities are considered in the models. Model results for water-to-rock ratios less than 10 are emphasized because they are likely to be more applicable to Mars. In accord with studies of low-grade alteration of terrestrial rocks, we find that the major controls on hydrous mineral production are host rock composition and temperature. Over the range of conditions considered, the alteration of Shergotty shows the greatest potential for storing water as hydrous minerals, and the alteration of Icelandic rhyolite has the lowest potential.

Evolution, Planetary↗
PubMed1997

Absorption and scattering properties of the Martian dust in the solar wavelengths.

A new wavelength-dependent model of the single-scattering properties of the Martian dust is presented. The model encompasses the solar wavelengths (0.3 to 4.3 micrometers at 0.02 micrometer resolution) and does not assume a particular mineralogical composition of the particles. We use the particle size distribution, shape, and single-scattering properties at Viking Lander wavelengths presented by Pollack et al. [1995]. We expand the wavelength range of the aerosol model by assuming that the atmospheric dust complex index of refraction is the same as that of dust particles in the bright surface geologic units. The new wavelength-dependent model is compared to observations taken by the Viking Orbiter Infrared Thermal Mapper solar channel instrument during two dust storms. The model accurately matches afternoon observations and some morning observations. Some of the early morning observations are much brighter than the model results. The increased reflectance can be ascribed to the formation of a water ice shell around the dust particles, thus creating the water ice clouds which Colburn et al. [1989], among others, have predicted.

Atmosphere↗
PubMed1997

Organic degradation under simulated Martian conditions.

We report on laboratory experiments which simulate the breakdown of organic compounds under Martian surface conditions. Chambers containing Mars-analog soil mixed with the amino acid glycine were evacuated and filled to 100 mbar pressure with a Martian atmosphere gas mixture and then irradiated with a broad spectrum Xe lamp. Headspace gases were periodically withdrawn and analyzed via gas chromatography for the presence of organic gases expected to be decomposition products of the glycine. The quantum efficiency for the decomposition of glycine by light at wavelengths from 2000 to 2400 angstroms was measured to be 1.46 +/- 1.0 x 10(-6) molecules/photon. Scaled to Mars, this represents an organic destruction rate of 2.24 +/- 1.2 x 10(-4) g of C m-2 yr-1. We compare this degradation rate with the rate that organic compounds are brought to Mars as a result of meteoritic infall to show that organic compounds are destroyed on Mars at rates far exceeding the rate that they are deposited by meteorites. Thus the fact that no organic compounds were found on Mars by the Viking Lander Gas Chromatograph Mass Spectrometer experiment can be explained without invoking the presence of strong oxidants in the surface soils. The organic destruction rate may be considered as an upper bound for the globally averaged biomass production rate of extant organisms at the surface of Mars. This upper bound is comparable to the slow growing cryptoendolithic microbial communities found in dry Antarctica deserts. Finally, comparing these organic destruction rates to recently reported experiments on the stability of carbonate on the surface of Mars, we find that organic compounds may currently be more stable than calcite.

Argon↗
PubMed1998

The composition of the Jovian atmosphere as determined by the Galileo probe mass spectrometer.

The Galileo probe mass spectrometer determined the composition of the Jovian atmosphere for species with masses between 2 and 150 amu from 0.5 to 21.1 bars. This paper presents the results of analysis of some of the constituents detected: H2, He, Ne, Ar, Kr, Xe, CH4, NH3, H2O, H2S, C2 and C3 nonmethane hydrocarbons, and possibly PH3 and Cl. 4He/H2 in the Jovian atmosphere was measured to be 0.157 +/- 0.030. 13C/C12 was found to be 0.0108 +/- 0.0005, and D/H and 3He/4He were measured. Ne was depleted, < or = 0.13 times solar, Ar < or = 1.7 solar, Kr < or = 5 solar, and Xe < or = 5 solar. CH4 has a constant mixing ratio of (2.1 +/- 0.4) x 10(-3) (12C, 2.9 solar), where the mixing ratio is relative to H2. Upper limits to the H2O mixing ratio rose from 8 x 10(-7) at pressures <3.8 bars to (5.6 +/- 2.5) x 10(-5) (16O, 0.033 +/- 0.015 solar) at 11.7 bars and, provisionally, about an order of magnitude larger at 18.7 bars. The mixing ratio of H2S was <10(-6) at pressures less than 3.8 bars but rose from about 0.7 x 10(-5) at 8.7 bars to about 7.7 x 10(-5) (32S, 2.5 solar) above 15 bars. Only very large upper limits to the NH3 mixing ratio have been set at present. If PH3 and Cl were present, their mixing ratios also increased with pressure. Species were detected at mass peaks appropriate for C2 and C3 hydrocarbons. It is not yet clear which of these were atmospheric constituents and which were instrumentally generated. These measurements imply (1) fractionation of 4He, (2) a local, altitude-dependent depletion of condensables, probably because the probe entered the descending arm of a circulation cell, (3) that icy planetesimals made significant contributions to the volatile inventory, and (4) a moderate decrease in D/H but no detectable change in (D + 3He)/H in this part of the galaxy during the past 4.6 Gyr.

Atmosphere↗
PubMed1987

Determination of O2(a1 delta g) and O2(b1 sigma+ g) yields in the reaction O + ClO --> Cl + O2: implications for photochemistry in the atmosphere of Venus.

A discharge flow apparatus with chemiluminescence detector has been used to study the reaction O + ClO --> Cl + O2, where O2 = O2(a1 delta g) or O2(b1 sigma+ g). The measured quantum yields for producing O2(a1 delta g) and O2(b1 sigma+ g) in the above reaction are less than 2.5 x 10(-2) and equal to (4.4 +/- 1.1) x 10(-4), respectively. The observed O2(a1 delta g) airglow of Venus cannot be explained in the context of standard photochemistry using our experimental results and those reported in recent literature. The possibility of an alternative source of O atoms derived from SO2 photolysis in the mesosphere of Venus is suggested.

Atmosphere↗
PubMed1989

Triton: stratospheric molecules and organic sediments.

Hydrocarbons and nitriles are produced in Triton's stratosphere by energetic electrons from Neptune's magnetosphere and other charged particle sources. Laboratory plasma experiments reported here show a substantial yield of molecules from low pressure flows of 10(-3) CH4 in N2 appropriate to Triton if both CH4 and N2 are saturated at the surface. An active magnetosphere similar to that of Uranus would result in a flux approximately 0.3 erg cm-2 s-1 of 0.1-1 MeV electrons in Triton's stratosphere; molecular production rates are then 10(6)-10(8) cm-2 s-1 for NH3, C2H2, HCN, and NCCN; tens of hundreds of gm cm-2 of these compounds per 10(9) yr (and lesser quantities of at least eight other molecules experimentally detected) would freeze to fine-grained white condensates in the lower stratosphere and sediment to the surface. Along with dark/colored organic haze produced in the stratosphere and other heteropolymers produced at the surface, these condensates are subjects to redistribution by aeolian processes and may appear as lag deposits and/or sediment layers. A simple eddy diffusion model indicates abundances approximately 10(19) molec cm-2 for HCN and C2H2, and > 10(17) molec cm-2 for NCCN, CH3CCH, CH2CCH2, and CH3CN in the stratosphere; these and other organic molecules will be detectable by IRIS if the stratosphere is (as expected) heated through ultraviolet and visible light absorption by the haze.

Atmosphere↗