Strong water isotopic anomalies in the martian atmosphere: probing current and ancient reservoirs.

We measured maps of atmospheric water (H2O) and its deuterated form (HDO) across the martian globe, showing strong isotopic anomalies and a significant high deuterium/hydrogen (D/H) enrichment indicative of great water loss. The maps sample the evolution of sublimation from the north polar cap, revealing that the released water has a representative D/H value enriched by a factor of about 7 relative to Earth's ocean [Vienna standard mean ocean water (VSMOW)]. Certain basins and orographic depressions show even higher enrichment, whereas high-altitude regions show much lower values (1 to 3 VSMOW). Our atmospheric maps indicate that water ice in the polar reservoirs is enriched in deuterium to at least 8 VSMOW, which would mean that early Mars (4.5 billion years ago) had a global equivalent water layer at least 137 meters deep.

The formation heritage of Jupiter Family Comet 10P/Tempel 2 as revealed by infrared spectroscopy.

We present spectral and spatial information for major volatile species in Comet 10P/Tempel 2, based on high-dispersion infrared spectra acquired on UT 2010 July 26 (heliocentric distance R h = 1.44 AU) and September 18 (R h = 1.62 AU), following the comet's perihelion passage on UT 2010 July 04. The total production rate for water on July 26 was (1.90 ± 0.12) × 1028 molecules s-1, and abundances of six trace gases (relative to water) were: CH3OH (1.58% ± 0.23%), C2H6 (0.39% ± 0.04%), NH3 (0.83% ± 0.20%), and HCN (0.13% ± 0.02%). A detailed analysis of intensities for water emission lines provided a rotational temperature of 35 ± 3 K. The mean OPR is consistent with nuclear spin populations in statistical equilibrium (OPR = 3.01 ± 0.18), and the (1σ) lower bound corresponds to a spin temperature >38 K. Our measurements were contemporaneous with a jet-like feature observed at optical wavelengths. The spatial profiles of four primary volatiles display strong enhancements in the jet direction, which favors release from a localized vent on the nucleus. The measured IR continuum is much more sharply peaked and is consistent with a dominant contribution from the nucleus itself. The peak intensities for H2O, CH3OH, and C2H6 are offset by ~200 km in the jet direction, suggesting the possible existence of a distributed source, such as the release of icy grains that subsequently sublimed in the coma. On UT September 18, no obvious emission lines were present in our spectra, nevertheless we obtained a 3σ upper limit Q(H2O) < 2.86 × 1027 molecules s-1.

Organic composition of C/1999 S4 (LINEAR): a comet formed near Jupiter?

In the current paradigm, Oort cloud comets formed in the giant planets' region of the solar nebula, where temperatures and other conditions varied greatly. The measured compositions of four such comets (Halley, Hyakutake, Hale-Bopp, and Lee) are consistent with formation from interstellar ices in the cold nebular region beyond Uranus. The composition of comet C/1999 S4 (LINEAR) differs greatly, which suggests that its ices condensed from processed nebular gas, probably in the Jupiter-Saturn region. Its unusual organic composition may require reevaluation of the prebiotic organic material delivered to the young Earth by comets.

Identification of two sources of carbon monoxide in comet Hale-Bopp.

The composition of ices in comets may reflect that of the molecular cloud in which the Sun formed, or it may show evidence of chemical processing in the pre-planetary accretion disk around the proto-Sun. As carbon monoxide (CO) is ubiquitous in molecular clouds, its abundance with respect to water could help to determine the degree to which pre-cometary material was processed, although variations in CO abundance may also be influenced by the distance from the Sun at which comets formed. Observations have not hitherto provided an unambiguous measure of CO in the cometary ice (native CO). Evidence for an extended source of CO associated with comet Halley was provided by the Giotto spacecraft, but alternative interpretations exist. Here we report observations of comet Hale-Bopp which show that about half of the CO in the comet comes directly from ice stored in the nucleus. The abundance of this CO with respect to water (12 per cent) is smaller than in quiescent regions of molecular clouds, but is consistent with that measured in proto-stellar envelopes, suggesting that the ices underwent some processing before their inclusion into Hale-Bopp. The remaining CO arises in the coma, probably through thermal destruction of more complex molecules.

Detection of atomic deuterium in the upper atmosphere of Mars.

High-resolution spectroscopy of Mars' atmosphere with the Hubble Space Telescope revealed the deuterium Lyman alpha line at an intensity of 23 +/- 6 rayleighs. This measured intensity corresponds to HD/H2 = 1.5 +/- 0.6 x 10(-4), which is smaller by a factor of 11 than HDO/H2O. This indicates that fractionation of HD/H2 relative to that of HDO/H2O is not kinetically controlled by the rates of formation and destruction of H2 and HD but is thermodynamically controlled by the isotope exchange HD + H2O left and right arrow HDO + H2. Molecular hydrogen is strongly depleted in deuterium relative to water on Mars because of the very long lifetime of H2 (1200 years). The derived isotope fractionation corresponds to an estimate of a planetwide reservoir of water ice about 5 meters thick that is exchangeable with the atmosphere.

Detection of soft X-rays and a sensitive search for noble gases in comet Hale-Bopp.

An image of comet Hale-Bopp (C/1995 O1) in soft x-rays reveals a central emission offset from the nucleus, as well as an extended emission feature that does not correlate with the dust jets seen at optical wavelengths. Neon was found to be depleted in the cometary ice by more than a factor of 25 relative to solar abundance, which suggests that ices in Hale-Bopp formed at (or later experienced) temperatures higher than 25 kelvin. A helium line emission at a wavelength of 584 angstroms was detected and may be attributable to charge transfer of solar wind alpha particles in the cometary coma. Ionized oxygen and another helium line contribute to an emission observed at 538 angstroms.

Detection of abundant ethane and methane, along with carbon monoxide and water, in comet C/1996 B2 Hyakutake: evidence for interstellar origin.

The saturated hydrocarbons ethane (C2H6) and methane (CH4) along with carbon monoxide (CO) and water (H2O) were detected in comet C/1996 B2 Hyakutake with the use of high-resolution infrared spectroscopy at the NASA Infrared Telescope Facility on Mauna Kea, Hawaii. The inferred production rates of molecular gases from the icy, cometary nucleus (in molecules per second) are 6.4 X 10(26) for C2H6, 1.2 X 10(27) for CH4, 9.8 X 10(27) for CO, and 1.7 X 10(29) for H2O. An abundance of C2H6 comparable to that of CH4 implies that ices in C/1996 B2 Hyakutake did not originate in a thermochemically equilibrated region of the solar nebula. The abundances are consistent with a kinetically controlled production process, but production of C2H6 by gas-phase ion molecule reactions in the natal cloud core is energetically forbidden. The high C2H6/CH4 ratio is consistent with production of C2H6 in icy grain mantles in the natal cloud, either by photolysis of CH4-rich ice or by hydrogen-addition reactions to acetylene condensed from the gas phase.

Blocked impurity band detectors applied to tunable diode laser spectroscopy in the 8- to 28-microm range.

A novel tunable diode laser spectrometer operating at 8 < lambda < 28 microm is described. A blocked impurity band Si:As chip is employed as detector. This device operates in this wavelength range with high detectivity and adequate frequency response for the high-sensitivity techniques used. A combination of sweep averaging and second-harmonic detection at 22 kHz yielded signal-to-noise ratios of 1200 at lambda > 20 microm. The sensitivity and spectral resolution achieved are 1 order of magnitude better than those of Fourier instruments in this range, with an improvement in instrument time response of ~ 3000. Several molecular bands of CO(2) and N(2)O are observed for what is, to our knowledge, the first time with this instrument. Examples of spectral line measurements are presented.

The heliocentric evolution of cometary infrared spectra: results from an organic grain model.

Observations of Comets Halley and Wilson reveal an emission feature peaking near 3.4 micrometers, characteristic of C-H stretching in hydrocarbons. We have previously (Chyba and Sagan 1987a, Nature (London) 330, 350-353) fit this feature with a simple two-component thermal emission model for dust in the cometary coma (one component corresponding to large, cool, optically thick particles, the other due to smaller, hotter, organic grains) by employing laboratory spectra of the organic residue produced by the irradiation of carbon-bearing ices. This procedure yields optical depths in agreement with limits from spacecraft data. One remarkable result of such modeling is that at approximately 1 AU emission features at wavelengths longer than 3.4 micrometers are largely overwhelmed (or "diluted") by continuum emission. The large particle optical depth is approximately 10(2) times that of the emitting organics, so that, relative to the continuum, only near the continuum minimum can the emitting organics make a significant contribution. At approximately 1 AU, the 3.4-micrometers feature is the sole feature near that minimum, lying at the intersection of the curves for particle thermal emission and scattered sunlight. Thus, since as a comet moves away from perihelion the intersection of the scattered solar spectrum and the comet's thermal emission spectrum will move to longer wavelengths, we predicted (Chyba and Sagan 1987a) that the 3.4-micrometers feature is diluted while those at longer wavelengths are progressively revealed--so long as the comet retains its coma. We now quantitatively develop this model and find agreement with observational data for Comet Halley for certain plausible values of optical constants. Thus the observed heliocentric evolution of the 3.4-micrometers feature provides information on the composition, and perhaps structure, of the organic grains in Comet Halley. In addition, we argue that the heliocentric evolution of organic features will differ in the cases of thermal emission from small grains and gas-phase fluorescence. Therefore observations of cometary spectral evolution can in principle distinguish between solid or gas-phase origins for these features.

Detection of Water Vapor in Halley's Comet.

Gaseous, neutral H(2)O was detected in the coma of comet Halley on 22.1 and 24.1 December 1985 Universal Time. Nine spectral lines of thev(3) band (2.65 micrometers) were found by means of a Fourier transform spectrometer (lambda/triangle uplambda approximately 10(5)) on the NASA-Kuiper Airborne Observatory. The water production rate was approximately 6 x 10(28) molecules per second on 22.1 December and 1.7 x 10(29) molecules per second on 24.1 December UT. The numbers of spectral lines and their intensities are in accord with nonthermal-equilibrium cometary models. Rotational populations are derived from the observed spectral line intensities and excitation conditions are discussed. The ortho-para ratio was found to be 2.66+/-0.13, corresponding to a nuclear-spin temperature of 32 K (+5 K, -2 K), possibly indicating that the observed water vapor originated from a low-temperature ice.

Is there any chlorine monoxide in the stratosphere?

A ground-based search for stratospheric chlorine monoxide was carried out during May and October 1981 with an infrared heterodyne spectrometer in the solar absorption mode. Lines due to stratospheric nitric acid and tropospheric carbonyl sulfide were detected at about 0.2 percent absorptance levels, but the expected 0.1 percent lines of chlorine monoxide in this same region were not seen. Stratospheric chlorine monoxide is less abundant by at least a factor of 7 than is indicated by in situ measurements, and the upper limit for the integrated vertical column density of chlorine monoxide is 2.3 x 10(13) molecules per square centimeter at the 95 percent confidence level. These results imply that the release of chlorofluorocarbons may be significantly less important for the destruction of stratospheric ozone than is currently thought.

Tunable diode-laser heterodyne spectrometer for remote observations near 8 microm.

A diode-laser based ultrahigh resolution IR heterodyne spectrometer for laboratory and field use has been developed for operation between 7.5 and 8.5 microm. The local oscillator is a PbSe tunable diode laser kept continuously at operating temperatures of 12-60 K using a closed-cycle cooler. The laser output frequency is controlled and stabilized using a high-precision diode current supply, constant temperature controller, and a shock isolator mounted between the refrigerator cold tip and the diode mount. The system largely employs reflecting optics to minimize losses from internal reflection and absorption and to eliminate chromatic effects. Spectral analysis of the diode-laser output between 0 and 1 GHz reveals excess noise at many diode current settings, which limits the IR spectral regions over which useful heterodyne operation can be achieved. Observations have been made of atmospheric N(2)O, O(3), and CH(4) between 1170 and 1200 cm(-1) using both a single-frequency swept IF channel and a 64-channel rf spectral line receiver with a total IF coverage of 1600 MHz.

Discovery of natural gain amplification in the 10-micrometer carbon dioxide laser bands on Mars: a natural laser.

Fully resolved intensity profiles of various lines in the carbon dioxide band at 10.4 micrometers have been measured on Mars with an infrared heterodyne spectrometer. Analysis of the line shapes shows that the Mars atmosphere exhibits positive gain in these lines. The detection of natural optical gain amplification enables identification of these lines as a definite natural laser.

Precision measurements of NH(3) spectral lines near 11 microm using the infrared heterodyne technique.

Absolute line-center frequencies for eleven lines of ammonia in near coincidence with CO(2)-laser transitions have been determined to accuracies of +/-3 MHz by infrared heterodyne detection. These results were obtained by heterodyning a blackbody with a stable, grating-tuned CO(2) gas laser. A discussion of the apparatus and method of calculation, including error analysis, is presented. With these accurately determined line-center positions, the ammonia molecule will be a useful secondary-frequency standard for diode-laser spectroscopy in the 11-microm wavelength region.

Sensitivity limits of an infrared heterodyne spectrometer for astrophysical applications.

The sensitivity of an ideal heterodyne spectrometer approaches the quantum detection limit provided the local oscillator power is sufficiently large and the shot noise dominates all other sources of noise. The postintegration minimum-detectable-number of photons/sec for an ideal heterodyne system is (B/tau)((1/2)), where B is the IF bandwidth, and tau is the integration time. For astronomical observations, however, a number of factors (Delta(i)) tend to degrade the sensitivity, a fact that becomes significant particularly when the laser power is insufficient. A discussion and an evaluation of the degradation in sensitivity are given for a heterodyne spectrometer employing a HgCdTe photodiode mixer and tunable diode lasers. The minimum detectable source brightness is considered as a function of the mixer parameters, transmission coefficient of the beam splitter, and local oscillator emission powers. The degradation in the minimum detectable line source brightness that results from the bandwidth being a fraction of the line width is evaluated and plotted as a function of the wavelength and bandwidth for various temperature to mass ratios. It is shown that the minimum achievable degradation [pi(i)(Delta(i))] in the sensitivity of a practical astronomical heterodyne spectrometer is ~30. Estimates of SNR's with which ir line emission from astronomical sources of interest may be detected are given.