Water Formation and Destruction by 'Super' X-ray Flares from a T-Tauri Star in a Protoplanetary Disk

NASA Astrophysics Data System (ADS)

Waggoner, Abygail R.; Cleeves, L. Ilsedore

2018-01-01

We present models of H2O chemistry is protoplanetary disks in the presence of 'super' X-ray flares emitted by a T-Tauri star. We examine the time-evolving chemistry of H2O at radial locations from 1 to 20 AU at various vertical heights from the mid-plane to the surface of the disk. We find the gas-phase H2O abundance can be enhanced in the surface (Z/R ≥ 0.3) by more than a factor of approximately 3 - 5 by strong flares, i.e., those that increase the ionization rate by a factor of 100. Dissociative recombination of H3O+ , H2O adsorption onto grain, and photolysis of H2O are found to be the three dominant processes leading to a change in H2O abundance. We find X-ray flares have predominantly short- term (days) effects on gaseous H2O abundance, but some regions show a long-term (for the duration of the test about 15 days) decrease in gaseous H2O due to adsorption onto grains, which results in an increase (up to 200%) in ice H2O in regions where ice H2O is < 10-9 abundance with respect to H atom. In regions where ice H2 O is > 10-8 abundance no are response in the ice is observed.Thanks to the National Science Foundation for funding this research as a part of the Smithsonian Astrophysical Observatory Research Experience for Undergraduates (SAO REU).

Detection and monitoring of H2O and CO2 ice clouds on Mars

USGS Publications Warehouse

Bell, J.F.; Calvin, W.M.; Ockert-Bell, M. E.; Crisp, D.; Pollack, James B.; Spencer, J.

1996-01-01

We have developed an observational scheme for the detection and discrimination of Mars atmospheric H2O and CO2 clouds using ground-based instruments in the near infrared. We report the results of our cloud detection and characterization study using Mars near IR images obtained during the 1990 and 1993 oppositions. We focused on specific wavelengths that have the potential, based on previous laboratory studies of H2O and CO2 ices, of yielding the greatest degree of cloud detectability and compositional discriminability. We have detected and mapped absorption features at some of these wavelengths in both the northern and southern polar regions of Mars. Compositional information on the nature of these absorption features was derived from comparisons with laboratory ice spectra and with a simplified radiative transfer model of a CO2 ice cloud overlying a bright surface. Our results indicate that both H2O and CO2 ices can be detected and distinguished in the polar hood clouds. The region near 3.00 ??m is most useful for the detection of water ice clouds because there is a strong H2O ice absorption at this wavelength but only a weak CO2 ice band. The region near 3.33 ??m is most useful for the detection of CO2 ice clouds because there is a strong, relatively narrow CO2 ice band at this wavelength but only broad "continuum" H2O ice absorption. Weaker features near 2.30 ??m could arise from CO2 ice at coarse grain sizes, or surface/dust minerals. Narrow features near 2.00 ??m, which could potentially be very diagnostic of CO2 ice clouds, suffer from contamination by Mars atmospheric CO2 absorptions and are difficult to interpret because of the rather poor knowledge of surface elevation at high latitudes. These results indicate that future ground-based, Earth-orbital, and spacecraft studies over a more extended span of the seasonal cycle should yield substantial information on the style and timing of volatile transport on Mars, as well as a more detailed understanding of the role of CO2 condensation in the polar heat budget. Copyright 1996 by the American Geophysical Union.

Coloration and darkening of methane clathrate and other ices by charged particle irradiation - Applications to the outer solar system

NASA Technical Reports Server (NTRS)

Thompson, W. Reid; Murray, B. G. J. P. T.; Khare, B. N.; Sagan, Carl

1987-01-01

The results of laboratory experiments simulating the irradiation of hydrocarbon-H2O or hydrocarbon-H2O/NH3 clathrates by charged particles in the outer solar system are reported. Ices produced by condensing and boiling liquid CH4 on an H2O frost surface at 100 K or by cocondensing frosts from gaseous mixtures were exposed to coronal-discharge electron irradiation at 77 K, and the spectral properties of the irradiated surfaces were determined. Significant darkening of the initially white ices was observed at doses of 1 Gerg/sq cm, corresponding to 8-500 yrs of irradiation by Uranian magnetospheric electrons on the surfaces of the principal Uranian satellites, or to total destruction of CH4 in the upper 1 mm of the satellite surfaces after 0.05-3.0 Myr. It is estimated that 10 m or more of icy satellite or comet surfaces would be radiation-hardened to a CH4-free ice-tholin mixture over 4 Gyr.

SIZE AND SURFACE AREA OF ICY DUST AGGREGATES AFTER A HEATING EVENT AT A PROTOPLANETARY NEBULA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sirono, Sin-iti

2013-03-01

The activity of a young star rises abruptly during an FU Orionis outburst. This event causes a temporary temperature increase in the protoplanetary nebula. H{sub 2}O icy grains are sublimated by this event, and silicate cores embedded inside the ice are ejected. During the high-temperature phase, the silicate grains coagulate to form silicate core aggregates. After the heating event, the temperature drops, and the ice recondenses onto the aggregates. I determined numerically the size distribution of the ice-covered aggregates. The size of the aggregates exceeds 10 {mu}m around the snow line. Because of the migration of the ice to largemore » aggregates, only a small fraction of the silicate core aggregate is covered with H{sub 2}O ice. After the heating event, the surface of an ice-covered aggregate is totally covered by silicate core aggregates. This might reduce the fragmentation velocity of aggregates when they collide. It is possible that the covering silicate cores shield the UV radiation field which induces photodissociation of H{sub 2}O ice. This effect may cause the shortage of cold H{sub 2}O vapor observed by Herschel.« less

Near-Infrared Band Strengths of Molecules Diluted in N2 and H20 Ice Mixtures Relevant to Interstellar and Planetary Ices

NASA Technical Reports Server (NTRS)

Richey, C. R.; Richey, Christina R.

2012-01-01

In order to determine the column density of a component of an ice from its infrared absorption features, the strengths of these features must be known. The peak positions, widths, profiles, and strengths of a certain ice component's infrared absorption features are affected be the overall composition of the ice. Many satellites within the solar system have surfaces that are dominated by H2O or N2 and ices in the interstellar medium (ISM) are primarily composed of H2O. The experiments presented here focus on the near-infrared absorption features of CO, CO2, CH4, and NH3 (nu=10,000-4,000/cm, lambda=1-2.5 microns) and the effects of diluting these molecules in N2 or H2O ice (mixture ratio of 5:1). This is a continuation of previous results published by our research group.

Pluto and Charon: Surface Colors and Compositions - A Hypothesis

NASA Technical Reports Server (NTRS)

Cruikshank, D. P.

2016-01-01

The surface of Pluto displays an array of colors ranging from yellow to red to brown, while the surface of Charon is largely gray with a north polar zone of red color similar to regions on Pluto. Pluto's surface shows layers of intensely colored material in tilted and transported blocks, and fractured geo-graphical units. This arrangement suggests episodes of formation or deposition of that material interspersed with episodes of emplacement of ices having little or no color. The ices identified on the surfaces of these two bodies (N2, CH4, CO, C2H6, H2O on Pluto, and H2O and NH3 on Charon) are colorless, as are nearly all ices in a powdery state. The colors on Pluto probably arise from the in situ formation of a macro-molecular carbonaceous material generated by energetic processing of the ices on the surface. Laboratory experiments producing refractory tholins particularly relevant to Pluto explored the chemistry of both UV and low-energy electron bombardment of a mix of Pluto ices (N2:CH4:CO = 100:1:1). We can term this Pluto ice tholin PIT. Water ice in the crystalline state characterizes Charon's surface, and while most of Charon's surface is neutral in color, with geometric albedo approximately 0.38, the polar zone and a light cover of fainter but similar reddish color over some surface regions suggest a common origin with the colored material on Pluto. NH3 or NH3 x nH2O was identified from disk-integrated Earth-based spectra, and a few concentrated NH3 exposures have been found in the New Horizons spectral images.

Atomistic and infrared study of CO-water amorphous ice onto olivine dust grain

NASA Astrophysics Data System (ADS)

Escamilla-Roa, Elizabeth; Moreno, Fernando; López-Moreno, J. Juan; Sainz-Díaz, C. Ignacio

2017-01-01

This work is a study of CO and H2O molecules as adsorbates that interact on the surface of olivine dust grains. Olivine (forsterite) is present on the Earth, planetary dust, in the interstellar medium (ISM) and in particular in comets. The composition of amorphous ice is very important for the interpretation of processes that occur in the solar system and the ISM. Dust particles in ISM are composed of a heterogeneous mixture of amorphous or crystalline silicates (e.g. olivine) organic material, carbon, and other minor constituents. These dust grains are embedded in a matrix of ices, such as H2O, CO, CO2, NH3, and CH4. We consider that any amorphous ice will interact and grow faster on dust grain surfaces. In this work we explore the adsorption of CO-H2O amorphous ice onto several (100) forsterite surfaces (dipolar and non-dipolar), by using first principle calculations based on density functional theory (DFT). These models are applied to two possible situations: i) adsorption of CO molecules mixed into an amorphous ice matrix (gas mixture) and adsorbed directly onto the forsterite surface. This interaction has lower adsorption energy than polar molecules (H2O and NH3) adsorbed on this surface; ii) adsorption of CO when the surface has previously been covered by amorphous water ice (onion model). In this case the calculations show that adsorption energy is low, indicating that this interaction is weak and therefore the CO can be desorbed with a small increase of temperature. Vibration spectroscopy for the most stable complex was also studied and the frequencies were in good agreement with experimental frequency values.

Infrared Spectral Studies of the Thermally-Driven Chemistry Present on Icy Satellites

NASA Technical Reports Server (NTRS)

Loeffler, Mark J.; Hudson, Reggie L.

2012-01-01

Remote sensing of Jupiters icy satellites has revealed that even though their surfaces arc composed mostly of water ice, molecules such as SO2, CO2, H2O2. O2, and O3 also are present. On Europa, a high radiation flux is believed to play a role in the formation of many of the minor species detected, and numerous laboratory studies have been devoted to explore this hypothesis. In this presentation we will discuss some of our recent research on another alteration pathway, thermally-driven chemical reactions, which are also important for understanding the chemical evolution of Europa's surface and sub-surface ices. We will focus on the infrared spectra of and reactions between H2O, SO2 and H2O2, at 80 - 130 K.

Descent without Modification? The Thermal Chemistry of H2O2 on Europa and Other Icy Worlds.

PubMed

Loeffler, Mark J; Hudson, Reggie L

2015-06-01

The strong oxidant H2O2 is known to exist in solid form on Europa and is suspected to exist on several other Solar System worlds at temperatures below 200 K. However, little is known of the thermal chemistry that H2O2 might induce under these conditions. Here, we report new laboratory results on the reactivity of solid H2O2 with eight different compounds in H2O-rich ices. Using infrared spectroscopy, we monitored compositional changes in ice mixtures during warming. The compounds CH4 (methane), C3H4 (propyne), CH3OH (methanol), and CH3CN (acetonitrile) were unaltered by the presence of H2O2 in ices, showing that exposure to either solid H2O2 or frozen H2O+H2O2 at cryogenic temperatures will not oxidize these organics, much less convert them to CO2. This contrasts strongly with the much greater reactivity of organics with H2O2 at higher temperatures, and particularly in the liquid and gas phases. Of the four inorganic compounds studied, CO, H2S, NH3, and SO2, only the last two reacted in ices containing H2O2, NH3 making NH4+ and SO2 making SO(4)2- by H+ and e- transfer, respectively. An important astrobiological conclusion is that formation of surface H2O2 on Europa and that molecule's downward movement with H2O-ice do not necessarily mean that all organics encountered in icy subsurface regions will be destroyed by H2O2 oxidation.

Descent Without Modification? The Thermal Chemistry of H2O2 on Europa and Other Icy Worlds

NASA Technical Reports Server (NTRS)

Loeffler, Mark Josiah; Hudson, Reggie Lester

2015-01-01

The strong oxidant H2O2 is known to exist in solid form on Europa and is suspected to exist on several other Solar System worlds at temperatures below 200 K. However, little is known of the thermal chemistry that H2O2 might induce under these conditions. Here, we report new laboratory results on the reactivity of solid H2O2 with eight different compounds in H2O-rich ices. Using infrared spectroscopy, we monitored compositional changes in ice mixtures during warming. The compounds CH4 (methane), C3H4 (propyne), CH3OH (methanol), and CH3CN (acetonitrile) were unaltered by the presence of H2O2 in ices, showing that exposure to either solid H2O2 or frozen H2O+H2O2 at cryogenic temperatures will not oxidize these organics, much less convert them to CO2. This contrasts strongly with the much greater reactivity of organics with H2O2 at higher temperatures, and particularly in the liquid and gas phases. Of the four inorganic compounds studied, CO, H2S, NH3, and SO2, only the last two reacted in ices containing H2O2, NH3 making NHþ 4 and SO2 making SO2 4 by H+ and e - transfer, respectively. An important astrobiological conclusion is that formation of surface H2O2 on Europa and that molecule's downward movement with H2O-ice do not necessarily mean that all organics encountered in icy subsurface regions will be destroyed by H2O2 oxidation.

Physical State and Distribution of Materials at the Surface of Pluto from New Horizons LEISA Imaging Spectrometer

NASA Technical Reports Server (NTRS)

Schmitt, B.; Philippe, S.; Grundy, W. M.; Reuter, D. C.; Cote, R.; Quirico, E.; Protopappa, S.; Young, L. A.; Binzel, R. P.; Cook, J. C.;

Physical state and distribution of materials at the surface of Pluto from New Horizons LEISA imaging spectrometer

NASA Astrophysics Data System (ADS)

Schmitt, B.; Philippe, S.; Grundy, W. M.; Reuter, D. C.; Côte, R.; Quirico, E.; Protopapa, S.; Young, L. A.; Binzel, R. P.; Cook, J. C.; Cruikshank, D. P.; Dalle Ore, C. M.; Earle, A. M.; Ennico, K.; Howett, C. J. A.; Jennings, D. E.; Linscott, I. R.; Lunsford, A. W.; Olkin, C. B.; Parker, A. H.; Parker, J. Wm.; Singer, K. N.; Spencer, J. R.; Stansberry, J. A.; Stern, S. A.; Tsang, C. C. C.; Verbiscer, A. J.; Weaver, H. A.; New Horizons Science Team

2017-05-01

From Earth based observations Pluto is known to be the host of N2, CH4 and CO ices and also a dark red material. Very limited spatial distribution information is available from rotational visible and near-infrared spectral curves obtained from hemispheric measurements. In July 2015 the New Horizons spacecraft reached Pluto and its satellite system and recorded a large set of data. The LEISA spectro-imager of the RALPH instruments are dedicated to the study of the composition and physical state of the materials composing the surface. In this paper we report a study of the distribution and physical state of the ices and non-ice materials on Pluto's illuminated surface and their mode and degree of mixing. Principal Component analysis as well as various specific spectral indicators and correlation plots are used on the first set of 2 high resolution spectro-images from the LEISA instrument covering the whole illuminated face of Pluto at the time of the New Horizons encounter. Qualitative distribution maps have been obtained for the 4 main condensed molecules, N2, CH4, CO, H2O as well as for the visible-dark red material. Based on specific spectral indicators, using either the strength or the position of absorption bands, these 4 molecules are found to indicate the presence of 3 different types of ices: N2-rich:CH4:CO ices, CH4-rich(:CO:N2?) ices and H2O ice. The mixing lines between these ices and with the dark red material are studied using scatter plots between the various spectral indicators. CH4 is mixed at the molecular level with N2, most probably also with CO, thus forming a ternary molecular mixture that follows its phase diagram with low solubility limits. The occurrence of a N2-rich - CH4-rich ices mixing line associated with a progressive decrease of the CO/CH4 ratio tells us that a fractionation sublimation sequence transforms one type of ice to the other forming either a N2-rich - CH4-rich binary mixture at the surface or an upper CH4-rich ice crust that may hide the N2-rich ice below. The strong CH4-rich - H2O mixing line witnesses the subsequent sublimation of the CH4-rich ice lag left behind by the N2:CO sublimation (N spring-summer), or a direct condensation of CH4 ice on the cold H2O ice (S autumn). The weak mixing line between CH4-containing ices and the dark red material and the very sharp spatial transitions between these ices and this non-volatile material are probably due to thermal incompatibility. Finally the occurrence of a H2O ice - red material mixing line advocates for a spatial mixing of the red material covering H2O ice, with possibly a small amount intimately mixed in water ice. From this analysis of the different materials distribution and their relative mixing lines, H2O ice appears to be the substratum on which other ices condense or non-volatile organic material is deposited from the atmosphere. N2-rich ices seem to evolve to CH4-dominated ices, possibly still containing traces of CO and N2, as N2 and CO sublimate away. The spatial distribution of these materials is very complex. The high spatial definition of all these composition maps, as well as those at even higher resolution that will be soon available, will allow us to compare them with Pluto's geologic features observed by LORRI panchromatic and MVIC multispectral imagers to better understand the geophysical processes in action at the surface of this astonishingly active frozen world.

The volume- and surface-binding energies of ice systems containing CO, CO2, and H2O

NASA Technical Reports Server (NTRS)

Sandford, Scott A.; Allamandola, Louis J.

1990-01-01

Laboratory-measured, temperature-dependent sticking efficiencies are presently used to derive the surface-binding energies of CO and CO2 on H2O-rich ices, with a view to determining the condensation and vaporization properties of these systems as well as to the measured energies' implications for both cometary behavior and the evolution of interstellar ices. The molecular volume and the surface binding energies are not found to be necessarily related on the basis of simple nearest-neighbor scaling in surface and bulk sites; this may be due to the physical constraints associated with matrix structure-associated physical constraints, which sometimes dominate the volume-binding energies.

The condensation and vaporization behavior of ices containing SO2, H2S, and CO2: Implications for Io

NASA Technical Reports Server (NTRS)

Sandford, Scott A.; Allamandola, Louis J.

1993-01-01

In an extension of previously reported work on ices containing CO, CO2, H2O, CH3OH, NH3, and H2, measurements of the physical and infrared spectral properties of ices containing molecules relevant to Jupiter's moon Io are presented. These include studies on ice systems containing SO2, H2S, and CO2. The condensation and sublimation behaviors of each ice system and surface binding energies of their components are discussed. The surface binding energies can be used to calculate the residence times of the molecules on a surface as a function of temperature and thus represent important parameters for any calculation that attempts to model the transport of these molecules on Io's surface. The derived values indicate that SO2 frosts on Io are likely to anneal rapidly, resulting in less fluffy, 'glassy' ices and that H2S can be trapped in the SO2 ices of Io during night-time hours provided that SO2 deposition rates are on the order of 5 micrometers/hr or larger.

The Search for Pluto Water

NASA Astrophysics Data System (ADS)

Cook, Jason C.; Cruikshank, Dale P.; Dalle Ore, Cristina M.; Ennico, Kimberly; Grundy, William M.; Olkin, Cathy B.; Protopapa, Silvia; Stern, S. Alan; Weaver, Harold A.; Young, Leslie A.

2015-11-01

On July 14, 2015, the New Horizons spacecraft made its closest approach to Pluto at about ~12,000 km from Pluto's surface. The LEISA (Linear Etalon Imaging Spectral Array) component of the Ralph instrument (Reuter, D.C., Stern, S.A., Scherrer, J., et al. 2008, Space Sci. Rev. 140, 129) obtained spatially resolved near infrared spectra at scales as small as 3 km/pix. LEISA covers the wavelength range 1.25 to 2.5 μm at a spectral resolution (λ/Δλ) of 240, and the 2.1 to 2.25 μm range at a resolution of 560. The observations from this instrument are being used to map the distribution of Pluto's known ices such as N2, CH4, CO and C2H6 as well as search for H2O-ice. To date, H2O-ice has evaded detection from Earth bound observatories. Observations based on LORRI, the LOng Range Reconnaissance Imager, suggest H2O-ice is a major component of several mountain ranges around the western perimeter of the landmass informally named Tombaugh Regio. If true, H2O-ice may be found in small isolated regions around Pluto. We will present our analysis of all LESIA data of Pluto in hand to search for and understand the distribution of H2O-ice. If found, we will also discuss limits on crystalline vs. amorphous H2O-ice and temperature measurements based on the 1.65 µm crystalline H2O-ice feature. This work was supported by NASA's New Horizons project.

Saturn's satellites: Predictions for Cassini

NASA Astrophysics Data System (ADS)

Delitsky, M. L.; Hibbitts, C. A.

2004-11-01

Saturn's satellites are subjected to a variety of energy inputs (from photons, magnetospheric and solar ions and electrons) which will affect their surface composition. The Saturn magnetosphere contains an assortment of ions, including O+ and H+ from sputtering of water ice on the inner satellites and N+ from sputtering of Titan's atmosphere. Implantation of these ions onto the surfaces of the satellites may produce compounds possibly detectable by Cassini instruments. The satellites contain water ice and carbon dioxide ice (and possibly organics, on Phoebe). In Delitsky and Lane (2002), chemistry resulting from nitrogen ion implantation into water ice and carbon dioxide ice was outlined. From deposition of N+ ions into H2O/CO2, a complicated C-H-N-O chemistry may result, including formation of isocyanates, nitriles, nitrogen oxides and amino acids. Upon irradiation, H2O/CO2 mixtures will yield esters, ketones, alcohols, carboxylic acids and other interesting compounds. Cassini's infrared instruments CIRS and VIMS have spectral ranges that can detect many bands of these compounds. VIMS spectral range is 0.35 - 5.1 microns; CIRS covers the spectral range 7 - 100 microns, although its Mid-IR interferometer portion (7 -16 microns) is where organic materials are particularly spectrally active. Weak features are present in the short IR for NO (1.91 microns), NO2 (1.95), NH3 (2.00, 2.24), CH3OH (2.27, 2.34), and CO2 (1.965, 2.01) [Quirico et al.,1999]. Some molecules have stronger absorption features at these wavelengths: [CO2: 4.25 - 4.27 microns; NH3: 3 microns and 9.2 microns (important because the 3 micron band can be masked by water); H2CO3: 3.88 microns (weak); HCOOH: 8.2 microns; O2: 9.7 microns]. These molecules may exist as ices, or as molecules trapped in the surface. CH- and CN-containing molecules absorb at 3.2 - 3.4 microns, and 4.6 microns, respectively. H2O2, detected on Europa by its 3.5 micron band, may exist in the icy surfaces of the Saturn satellites as well.

Correlation of Comet 67P/CG'S Morphology with the Occurrence of Exposed Water Ice Patches

NASA Astrophysics Data System (ADS)

Arnold, G.; Weller, D.; Zeilinger, G.; Kappel, D.; Hviid, S.; Kührt, E.; Moroz, L. V.; Markus, K.; Henckel, D.; Capaccioni, F.; Filacchione, G.; Erard, S.; Bockelee-Morvan, D.

2017-04-01

Introduction: Comet 67P's surface is quite homogeneously covered by dark refractory materials rich in organics [1,2]. Rare water ice expo- sures on the surface, most likely originating from sub-surface layers, have recently been discovered [3,4]. Such H2O ice patches on 67P's Imhotep region in the pre-perihelion phase were ex- amined and related to the local morphology to understand the exposure mechanisms [5]. Methods: H2O ice was identified in two study areas using characteristic H2O spectral features observed by the VIRTIS-M instrument [1]: absorption bands at 1.04, 1.25, 1.52, 2.02, 2.96 μm, and the VIS spectral slope (0.5-0.8 μm). Corresponding normalized spectral indicators were projected onto a 3D digital shape model (DSM) of 67P [6], along with high spatial resolution images acquired by OSIRIS [7] for morphological context. Results and conclusions: The 2.0-μm absorption band proved to be the most sensitive H2O indicator in the IR. Flat (bluer) normalized VIS slopes correlate very well with depths of H2O ice absorption bands. The DSM projections show a significant spatial correlation between spectral H2O indicators and morphological features. H2O ice deposits were identified in two areas, each extending over hundreds of square meters. Both are located at the bases of steep-sloped (>60°) walls of Consolidated Cometary Material (CCM) on debris falls that came to rest on moderately inclined (20°-30°) terrain, pointing towards gravitational lows. Both deposits are located in poorly illuminated areas due to shadowing from close-by steep walls. The morphological and photometrical properties of these deposits appear to be stable over months. Spectral modeling [3,4] indicated the presence of large (mm-sized) H2O ice grains. Such grains form through vapor diffusion in ice-rich colder layers or by sintering and are exposed by erosion [3]. The CCM in both study areas was fractured and weakened by thermal fatigue and sublimation, leading to the collapse of overhangs in one single event or in small steps over a longer time. For study area 1 this interpretation is supported by a small remnant H2O ice patch in the upper part of the steep wall indicating the original location of the collapse overhang. Sinkhole-structures on the CCM in study area 2 indicate sub-surface activity connected to ice sublimation, thermal stress, and occasional outbursts. Even though the nucleus structure probably is mostly homogeneous and primordial, the variable size and irregular distribution of sink-holes and erosional features strongly imply a highly active and heterogeneous sub-surface layer of at least tens of meters [8,9]. References: [1] Capaccioni F. et al. (2015) Sci- ence, 347, 628. [2] Quirico E. et al. (2016) Ica- rus, 272, 32-47. [3] Filacchione G. et al. (2016) Nature, 529, 368-372. [4] Barucci A. et al. (2016) A&A, 595, A102. [5] Weller D. (2016) Master thesis, University of Potsdam. [6] Preusker F. et al. (2015) A&A, 583, A33. [7] Keller H. et al. (2007) Space Sci. Rev., 128(1), 433-506. [8] Thomas N. et al. (2015) Science, 347, 440. [9] Vincent J.B. et al. (2015) Nature, 523, 63-66.

Triple Isotope Water Measurements of Lake Untersee Ice using Off-Axis ICOS

NASA Astrophysics Data System (ADS)

Berman, E. S.; Huang, Y. W.; Andersen, D. T.; Gupta, M.; McKay, C. P.

2015-12-01

Lake Untersee (71.348°S, 13.458°E) is the largest surface freshwater lake in the interior of the Gruber Mountains of central Queen Maud Land in East Antarctica. The lake is permanently covered with ice, is partly bounded by glacier ice and has a mean annual air temperature of -10°C. In contrast to other Antarctic lakes the dominating physical process controlling ice-cover dynamics is low summer temperatures and high wind speeds resulting in sublimation rather than melting as the main mass-loss process. The ice-cover of the lake is composed of lake-water ice formed during freeze-up and rafted glacial ice derived from the Anuchin Glacier. The mix of these two fractions impacts the energy balance of the lake, which directly affects ice-cover thickness. Ice-cover is important if one is to understand the physical, chemical, and biological linkages within these unique, physically driven ecosystems. We have analyzed δ2H, δ18O, and δ17O from samples of lake and glacier ice collected at Lake Untersee in Dec 2014. Using these data we seek to answer two specific questions: Are we able to determine the origin and history of the lake ice, discriminating between rafted glacial ice and lake water? Can isotopic gradients in the surface ice indicate the ablation (sublimation) rate of the surface ice? The triple isotope water analyzer developed by Los Gatos Research (LGR 912-0032) uses LGR's patented Off-Axis ICOS (Integrated Cavity Output Spectroscopy) technology and incorporates proprietary internal thermal control for high sensitivity and optimal instrument stability. This analyzer measures δ2H, δ18O, and δ17O from water, as well as the calculated d-excess and 17O-excess. The laboratory precision in high performance mode for both δ17O and δ18O is 0.03 ‰, and for δ2H is 0.2 ‰. Methodology and isotope data from Lake Untersee samples are presented. Figure: Ice samples were collected across Lake Untersee from both glacial and lake ice regions for this study.

Nanowire Ice of Phase VI and Distorted VII in Mesoporous Silica Nanotorus Superlattice

NASA Astrophysics Data System (ADS)

Zhu, Jinlong; Zhang, Jianzhong; Zhao, Yusheng

2014-03-01

The motivation of nano H2O realization and characterization is the highly polarized nature of H2O molecules and the spatial hydrogen bonded networks both in liquid and solid form. The hydrogen bonding character of water molecules results in a remarkably rich phase diagram in the pressure-temperature space. Water/Ice confined in nanochannels showed novel structures and properties as results of hydrophobic and hydrophilic interactions and hydrogen bonding interaction between water molecule and the surface of nanochannel. Studies on nano H2O can provide potential pathway to understand the complicated structure evolutions of ice in the P- T space, because the interplay between nano-confinement and strong intermolecular hydrogen interactions can lead to even richer ice structures which were not found in the none-confined bulk form. The high pressure experiment indicated that the pressure of nanowire ice VI and VII shifted up to 1.7 GPa and 2.5 GPa, and about ~ 0.65 GPa and 0.4 GPa higher than that of normal ice. The nano size effect and the strength of mesoporous silica nanotorus are responsible for the pressure shifts of ice phase regions. More pronounced, the cubic ice VII changed into a tetragonal distorted ``psuedocubic'' structure of the nanowire ice when confined in the mesoporous tubes. The degree of tetragonality increased with increasing pressure, which is resulted from the uniaxial pressure nanowire ice felt, and the anisotropic hydrogen bonding interactions including the H2O-H2O hydrogen bonds in the bulk of the ice and the H2O-silica -OH hydrogen bonds between the interface of nanowire ice and mesoporous silica. The experimental work has benefited from the use of CHESS at Cornell University, which is supported by the NSF award DMR-0936384.

CHEMICAL PROCESSING OF PURE AMMONIA AND AMMONIA-WATER ICES INDUCED BY HEAVY IONS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bordalo, V.; Da Silveira, E. F.; Lv, X. Y.

Cosmic rays are possibly the main agents to prevent the freeze-out of molecules onto grain surfaces in cold dense clouds. Ammonia (NH{sub 3}) is one of the most abundant molecules present in dust ice mantles, with a concentration of up to 15% relative to water (H{sub 2}O). FTIR spectroscopy is used to monitor pure NH{sub 3} and NH{sub 3}-H{sub 2}O ice samples as they are irradiated with Ni and Zn ion beams (500-600 MeV) at GANIL/France. New species, such as hydrazine (N{sub 2}H{sub 4}), diazene (N{sub 2}H{sub 2} isomers), molecular hydrogen (H{sub 2}), and nitrogen (N{sub 2}) were identified aftermore » irradiation of pure NH{sub 3} ices. Nitrous oxide (N{sub 2}O), nitrogen oxide (NO), nitrogen dioxide (NO{sub 2}), and hydroxylamine (NH{sub 2}OH) are some of the products of the NH{sub 3}-H{sub 2}O ice radiolysis. The spectral band at 6.85 {mu}m was observed after irradiation of both types of ice. Besides the likely contribution of ammonium (NH{sub 4}{sup +}) and amino (NH{sub 2}) radicals, data suggest a small contribution of NH{sub 2}OH to this band profile after high fluences of irradiation of NH{sub 3}-H{sub 2}O ices. The spectral shift of the NH{sub 3} ''umbrella'' mode (9.3 {mu}m) band is parameterized as a function of NH{sub 3}/H{sub 2}O ratio in amorphous ices. Ammonia and water destruction cross-sections are obtained, as well as the rate of NH{sub 3}-H{sub 2}O (1:10) ice compaction, measured by the OH dangling bond destruction cross-section. Ammonia destruction is enhanced in the presence of H{sub 2}O in the ice and a power law relationship between stopping power and NH{sub 3} destruction cross-section is verified. Such results may provide relevant information for the evolution of molecular species in dense molecular clouds.« less

Pluto and Charon Seen with the New Horizons Spacecraft

NASA Technical Reports Server (NTRS)

Cruikshank, D. P.; Stern, S. A.; Weaver, H. A.; Young, L. A.; Ennico, K.; Olkin, C. B.

2016-01-01

After nearly a decade en route, New Horizons flew through the Pluto system in July 2015. The encounter hemisphere of Pluto shows ongoing surface geological activity centered on a vast basin (Sputnik Planum [SP]*) containing a thick layer of volatile ices with a crater retention age no greater than approximately 10 Ma. Surrounding terrains show active glacial flow, apparent transport and rotation of large buoyant water-ice crustal blocks, and pitting, likely by sublimation erosion and/or collapse. Also seen are constructional mounds with central depressions, and ridges with complex bladed textures. Pluto has ancient cratered terrains up to approximately 4 Ga old that are fractured and mantled, and perhaps eroded by glacial processes. Charon does not appear to be currently active, but experienced major tectonism and resurfacing nearly 4 Ga ago. Imaging spectrometer observations of Pluto reveal the encounter hemisphere to be dominated by volatile ices of N2, CO, and CH4, along with non-volatile components that include H2O and tholins. The most volatile of Pluto's ices (N2 and CO) are especially prevalent in the western half of Tombaugh Regio (TR), and the strikingly flat Sputnik Planum basin, which lies a few km below surrounding elevations. The high mobility of N2 and CO ices enables SP's surface to refresh itself sufficiently rapidly that no impact craters are seen there. This likely occurs through a combination of solid state convective overturning and sublimation/ condensation that produces regular patterns of pits and ridges on scales of 102 to 103 m. In many areas, CH4 appears to favor topographically high regions. Its propensity to condense on ridges could play a role in forming the bladed terrain seen in Tartarus Dorsa. H2O can be discerned across much of Cthulhu Regio, and also in a few isolated spots. In many regions, H2O ice is associated with reddish tholin coloration. Pluto's atmosphere was probed with the radio science experiment (REX) and the Alice UV spectrometer, as well as imaging at high phase angles. The surface pressure, due mostly to N2, is approximately 11 microbars. Extensive multiple haze layers are seen in the images. Alice has detected hydrocarbons in addition to CH4 in the atmosphere. Since both are inert, H2O ice and tholin could have similar geological behaviors on Pluto, possibly including aeolian transport or mobilization by volatile ice glaciation. While Pluto's H2O ice is sculpted and at least partially veiled by more volatile ices, Charon's heavily cratered H2O ice is exposed globally. H2O ice spectral bands characteristic of crystalline ice are seen everywhere on the encounter hemisphere. Charon's north polar region is strikingly red, possibly the result of the unique thermal environment of Charon's poles, which become exceptionally cold during the long, dark winters. Extremely cold regions on Charon' could cold trap gases expanding outward from Pluto as ices, and thereby subject them to rapid radiolytic processing. Charon also exhibits a weak NH3 absorption band over most or all of its surface, with small local concentrations. Detailed results of the radio science, small satellite, particles and plasma, and atmosphere investigations are in press.

High pressure Raman spectroscopy of H2O-CH3OH mixtures.

PubMed

Hsieh, Wen-Pin; Chien, Yu-Hsiang

2015-02-23

Complex intra-molecular interactions and the hydrogen-bonding network in H2O-volatile mixtures play critical roles in many dynamics processes in physical chemistry, biology, and Earth and planetary sciences. We used high pressure Raman spectroscopy to study the pressure evolution of vibrational frequencies and bonding behavior in H2O-CH3OH mixtures. We found that the presence of low CH3OH content in H2O increases the transition pressure where water crystallizes to ice VI, but does not significantly change the pressure where ice VI transforms to ice VII. Furthermore, the stiffening rates of C-H stretching frequencies dω/dP in CH3OH significantly decrease upon the crystallization of water, and the softening rates of the O-H stretching frequencies of ice VII are suppressed over a narrow pressure range, after which the frequencies of these modes shift with pressure in ways similar to pure CH3OH and ice VII, respectively. Such complex pressure evolution of Raman frequencies along with pronounced variations in Raman intensities of CH3OH within the sample, and the hysteresis of the water-ice VI phase transition suggest pressure-induced segregation of low content CH3OH from ice VII. These findings indicate the significant influence of volatiles on the crystallization of sub-surface ocean and thermal evolution within large icy planets and satellites.

Ice Chemistry in Starless Molecular Cores

NASA Astrophysics Data System (ADS)

Kalvāns, J.

2015-06-01

Starless molecular cores are natural laboratories for interstellar molecular chemistry research. The chemistry of ices in such objects was investigated with a three-phase (gas, surface, and mantle) model. We considered the center part of five starless cores, with their physical conditions derived from observations. The ice chemistry of oxygen, nitrogen, sulfur, and complex organic molecules (COMs) was analyzed. We found that an ice-depth dimension, measured, e.g., in monolayers, is essential for modeling of chemistry in interstellar ices. Particularly, the H2O:CO:CO2:N2:NH3 ice abundance ratio regulates the production and destruction of minor species. It is suggested that photodesorption during the core-collapse period is responsible for the high abundance of interstellar H2O2 and O2H and other species synthesized on the surface. The calculated abundances of COMs in ice were compared to observed gas-phase values. Smaller activation barriers for CO and H2CO hydrogenation may help explain the production of a number of COMs. The observed abundance of methyl formate HCOOCH3 could be reproduced with a 1 kyr, 20 K temperature spike. Possible desorption mechanisms, relevant for COMs, are gas turbulence (ice exposure to interstellar photons) or a weak shock within the cloud core (grain collisions). To reproduce the observed COM abundances with the present 0D model, 1%-10% of ice mass needs to be sublimated. We estimate that the lifetime for starless cores likely does not exceed 1 Myr. Taurus cores are likely to be younger than their counterparts in most other clouds.

Ices on Charon: Distribution of H2O and NH3 from New Horizons LEISA observations

NASA Astrophysics Data System (ADS)

Dalle Ore, C. Morea; Protopapa, S.; Cook, J. C.; Grundy, W. M.; Cruikshank, D. P.; Verbiscer, A. J.; Ennico, K.; Olkin, C. B.; Stern, S. A.; Weaver, H. A.; Young, L. A.; New Horizons Science Team

2018-01-01

Charon, the largest moon of Pluto, appeared as a fairly homogeneous, gray, icy world to New Horizons during closest approach on July 14th, 2015. Charon's sub-Pluto hemisphere was scanned by the Ralph/LEISA near-IR spectrograph providing an unprecedented opportunity to measure its surface composition. We apply a statistical clustering tool to identify spectrally distinct terrains and a radiative transfer approach to study the variations of the 2.0-μm H2O ice band. We map the distribution of the ices previously reported to be present on Charon's surface, namely H2O and the products of NH3 in H2O. We find that H2O ice is mostly in the crystalline phase, confirming previous studies. The regions with the darkest albedos show the strongest signature of amorphous-phase ice, although the crystalline component is still strong. The brighter albedo regions, often corresponding to crater ejecta blankets, are characterized by larger H2O grains, possibly an indication of a younger age. We observe two different behaviors for the two absorption bands representing NH3 in H2O. The 2.21-μm band tends to cluster more in the northern areas compared to the ∼2.01-μm band. Both bands are present in the brighter crater rays, but not all craters show both bands. The 2.21-μm band is also clearly present on the smaller moons Hydra and Nix. These results hint that different physical conditions may determine the appearance or absence of these two different forms of NH3 in H2O ice in the Pluto system. We also investigate the blue slope affecting the spectrum at wavelengths longer than ∼1.8 μm previously reported by several authors. We find that the slope is common among the objects in the Pluto system, Charon, the smaller moons Nix and Hydra, and the darkest terrains on Pluto. It also characterizes the analog ice tholin obtained from irradiation of Pluto-specific materials (a mixture of N2, CH4, and CO ices) in the laboratory. Our modeling results show that Pluto ice tholins are widespread almost uniformly on Charon suggesting a common distribution possibly part of the original reservoir of materials that made up Charon. This was irradiated over the years to yield the gray color characteristic of Charon today. On top of the 'primordial' Pluto ice tholin there is the redder component produced by irradiation of the CH4 provided by Pluto's atmospheric contribution as illustrated by Grundy et al. (2016a).

Where's the Water in (Salty) Ice?

NASA Astrophysics Data System (ADS)

Kahan, T.; Malley, P.

2017-12-01

Solutes can have large effects on reactivity in ice and at ice surfaces. Freeze concentration ("the salting out effect") forms liquid regions containing high solute concentrations surrounded by relatively solute-free ice. Thermodynamics can predict the fraction of ice that is liquid for a given temperature and (pre-frozen) solute concentration, as well as the solute concentration within these liquid regions, but they do not inform on the spatial distribution of the solutes and the liquid regions within the ice. This leads to significant uncertainty in predictions of reaction kinetics in ice and at ice surfaces. We have used Raman microscopy to determine the location of liquid regions within ice and at ice surface in the presence of sodium chloride (NaCl). Under most conditions, liquid channels are observed at the ice surface and throughout the ice bulk. The fraction of the ice that is liquid, as well as the widths of these channels, increases with increasing temperature. Below the eutectic temperature (-21.1 oC), no liquid is observed. Patches of NaCl.2H2O ("hydrohalite") are observed at the ice surface under these conditions. These results will improve predictions of reaction kinetics in ice and at ice surfaces.

Saturn's satellites: Potential for organic chemistry

NASA Astrophysics Data System (ADS)

Delitsky, M. L.; Lane, A. L.; Henry-Riyad, H.; Tidwell, T. T.

2003-05-01

The surfaces of the Saturnian satellites are subjected to irradiation from solar wind ions, photons, and magnetospheric ions and electrons. This bombardment will transform the chemical nature of the surfaces. At present, only water ice has been detected on their surfaces. Further studies by the Cassini spacecraft may reveal other molecules. If CO2 ice is found there, a whole panoply of new species may be detected. As nitrogen ions in the magnetosphere are thought to be an important species bombarding the satellites, Delitsky and Lane (2002) outlined the nitrogen oxides chemistry that may result from implantation of N+ into the water ice surfaces. Sittler et al (2002) showed that N+ ions originating from Titan will be enriched in the magnetospheric ion population as they move inwards towards Saturn, making the nitrogen oxides chemistry more likely. If CO2 is present, a complicated C-H-N-O chemistry may result from deposition of the N+ into a H2O/CO2 mixed ice, including nitriles, isocyanates, polymers, and amino acids. The combination of H2O/CO2 upon irradiation may also yield a complex mixture of hydrocarbons, esters, alcohols, organic acids and ketones. Possible chemical pathways and computations of their energetics will be presented. -Ref:- 1. Delitsky and Lane, Saturn's inner satellites: Ice chemistry and magnetosphere effects, JGR (Planets), Nov 2002, 3-1;; 2. Sittler et al., Energetic nitrogen ions within the inner magnetosphere of Saturn, Fall AGU meeting, Dec 2002, abstracts, pg F858, P21B-0379

The Dependence of the Ice-Albedo Feedback on Atmospheric Properties

PubMed Central

Selsis, F.; Kitzmann, D.; Rauer, H.

2013-01-01

Abstract Ice-albedo feedback is a potentially important destabilizing effect for the climate of terrestrial planets. It is based on the positive feedback between decreasing surface temperatures, an increase of snow and ice cover, and an associated increase in planetary albedo, which then further decreases surface temperature. A recent study shows that for M stars, the strength of the ice-albedo feedback is reduced due to the strong spectral dependence of stellar radiation and snow/ice albedos; that is, M stars primarily emit in the near IR, where the snow and ice albedo is low, and less in the visible, where the snow/ice albedo is high. This study investigates the influence of the atmosphere (in terms of surface pressure and atmospheric composition) on this feedback, since an atmosphere was neglected in previous studies. A plane-parallel radiative transfer model was used for the calculation of planetary albedos. We varied CO2 partial pressures as well as the H2O, CH4, and O3 content in the atmosphere for planets orbiting Sun-like and M type stars. Results suggest that, for planets around M stars, the ice-albedo effect is significantly reduced, compared to planets around Sun-like stars. Including the effects of an atmosphere further suppresses the sensitivity to the ice-albedo effect. Atmospheric key properties such as surface pressure, but also the abundance of radiative trace gases, can considerably change the strength of the ice-albedo feedback. For dense CO2 atmospheres of the order of a few to tens of bar, atmospheric rather than surface properties begin to dominate the planetary radiation budget. At high CO2 pressures, the ice-albedo feedback is strongly reduced for planets around M stars. The presence of trace amounts of H2O and CH4 in the atmosphere also weakens the ice-albedo effect for both stellar types considered. For planets around Sun-like stars, O3 could also lead to a very strong decrease of the ice-albedo feedback at high CO2 pressures. Key Words: Atmospheric compositions—Extrasolar terrestrial planets—Snowball Earth—Planetary atmospheres—Radiative transfer. Astrobiology 13, 899–909. PMID:24111995

Heterogeneous reactions of chlorine nitrate and hydrogen chloride on type I polar stratospheric clouds

NASA Technical Reports Server (NTRS)

Leu, Ming-Taun; Moore, Steven B.; Keyser, Leon F.

1991-01-01

A fast-flow reactor coupled with a quadrupole mass spectrometer was used to study the heterogeneous reactions ClONO2 + HCl yields Cl2 + HNO3 (1) and ClONO2 + H2O yields HOCl + HNO3 (2) on vapor-deposited HNO3-H2O ice substrates. It was found that the sticking coefficient of HCl on these substrates was a strong function of the substrate composition, ranging from about 2 x 10 exp -5 at nitric acid trihydrate composition to 6 x 10 exp -3 at 45 wt pct HNO3. The HNO3-H2O ice substrates were found to have large internal surface areas, and corrections for gas-phase diffusion within the porous ices were applied to observed loss rates.

Observing Physical and Biological Drivers of pH and O2 in a Seasonal Ice Zone in the Ross Sea Using Profiling Float Data

NASA Astrophysics Data System (ADS)

Briggs, E.; Martz, T. R.; Talley, L. D.; Mazloff, M. R.

2015-12-01

Ice cover has strong influence over gas exchange, vertical stability, and biological production which are critical to understanding the Southern Ocean's central role in oceanic biogeochemical cycling and heat and carbon uptake under a changing climate. However the relative influence of physical versus biological processes in this hard-to-study region is poorly understood due to limited observations. Here we present new findings from a profiling float equipped with biogeochemical sensors in the seasonal ice zone of the Ross Sea capturing, for the first time, under-ice pH profile data over a two year timespan from 2014 to the present. The relative influence of physical (e.g. vertical mixing and air-sea gas exchange) and biological (e.g. production and respiration) drivers of pH and O2 within the mixed layer are explored during the phases of ice formation, ice cover, and ice melt over the two seasonal cycles. During the austral fall just prior to and during ice formation, O2 increases as expected due to surface-layer undersaturation and enhanced gas exchange. A small increase in pH is also observed during this phase, but without a biological signal in accompanying profiling float chlorophyll data, which goes against common reasoning from both a biological and physical standpoint. During the phase of ice cover, gas exchange is inhibited and a clear respiration signal is observed in pH and O2 data from which respiration rates are calculated. In the austral spring, ice melt gives rise to substantial ice edge phytoplankton blooms indicated by O2 supersaturation and corresponding increase in pH and large chlorophyll signal. The influence of the duration of ice cover and mixed layer depth on the magnitude of the ice edge blooms is explored between the two seasonal cycles.

ION IRRADIATION OF ETHANE AND WATER MIXTURE ICE AT 15 K: IMPLICATIONS FOR THE SOLAR SYSTEM AND THE ISM

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barros, A. L. F. de; Silveira, E. F da; Fulvio, D.

2016-06-20

Solid water has been observed on the surface of many different astronomical objects and is the dominant ice present in the universe, from the solar system (detected on the surface of some asteroids, planets and their satellites, trans-Neptunian objects [TNOs], comets, etc.) to dense cold interstellar clouds (where interstellar dust grains are covered with water-rich ices). Ethane has been detected across the solar system, from the atmosphere of the giant planets and the surface of Saturn’s satellite Titan to various comets and TNOs. To date, there were no experiments focused on icy mixtures of C{sub 2}H{sub 6} and H{sub 2}Omore » exposed to ion irradiation simulating cosmic rays, a case study for many astronomical environments in which C{sub 2}H{sub 6} has been detected. In this work, the radiolysis of a C{sub 2}H{sub 6}:H{sub 2}O (2:3) ice mixture bombarded by a 40 MeV{sup 58}Ni{sup 11+} ion beam is studied. The chemical evolution of the molecular species existing in the sample is monitored by a Fourier transform infrared spectrometer. The analysis of ethane, water, and molecular products in solid phase was performed. Induced chemical reactions in C{sub 2}H{sub 6}:H{sub 2}O ice produce 13 daughter molecular species. Their formation and dissociation cross sections are determined. Furthermore, atomic carbon, oxygen, and hydrogen budgets are determined and used to verify the stoichiometry of the most abundantly formed molecular species. The results are discussed in the view of solar system and interstellar medium chemistry. The study presented here should be regarded as a first step in laboratory works dedicated to simulate the effect of cosmic radiation on multicomponent mixtures involving C{sub 2}H{sub 6} and H{sub 2}O.« less

Clathrate hydrates of oxidants in the ice shell of Europa.

PubMed

Hand, Kevin P; Chyba, Christopher F; Carlson, Robert W; Cooper, John F

2006-06-01

Europa's icy surface is radiolytically modified by high-energy electrons and ions, and photolytically modified by solar ultraviolet photons. Observations from the Galileo Near Infrared Mapping Spectrometer, ground-based telescopes, the International Ultraviolet Explorer, and the Hubble Space Telescope, along with laboratory experiment results, indicate that the production of oxidants, such as H2O2, O2, CO2, and SO2, is a consequence of the surface radiolytic chemistry. Once created, some of the products may be entrained deeper into the ice shell through impact gardening or other resurfacing processes. The temperature and pressure environments of regions within the europan hydrosphere are expected to permit the formation of mixed clathrate compounds. The formation of carbon dioxide and sulfur dioxide clathrates has been examined in some detail. Here we add to this analysis by considering oxidants produced radiolytically on the surface of Europa. Our results indicate that the bulk ice shell could have a approximately 1.7-7.6% by number contamination of oxidants resulting from radiolysis at the surface. Oxidant-hosting clathrates would consequently make up approximately 12-53% of the ice shell by number relative to ice, if oxidants were entrained throughout. We examine, in brief, the consequences of such contamination on bulk ice shell thickness and find that clathrate formation could lead to substantially thinner ice shells on Europa than otherwise expected. Finally, we propose that double occupancy of clathrate cages by O2 molecules could serve as an explanation for the observation of condensed-phase O2 on Europa. Clathrate-sealed, gas-filled bubbles in the near surface ice could also provide an effective trapping mechanism, though they cannot explain the 5771 A (O2)2 absorption.

Experimental Studies on the Formation of D2O and D2O2 by Implantation of Energetic D+ Ions into Oxygen Ices

NASA Astrophysics Data System (ADS)

Bennett, Chris J.; Ennis, Courtney P.; Kaiser, Ralf I.

2014-02-01

The formation of water (H2O) in the interstellar medium is intrinsically linked to grain-surface chemistry; thought to involve reactions between atomic (or molecular) hydrogen with atomic oxygen (O), molecular oxygen (O2), and ozone (O3). Laboratory precedent suggests that H2O is produced efficiently when O2 ices are exposed to H atoms (~100 K). This leads to the sequential generation of the hydroxyperoxyl radical (HO2), then hydrogen peroxide (H2O2), and finally H2O and a hydroxyl radical (OH); despite a barrier of ~2300 K for the last step. Recent detection of the four involved species toward ρ Oph A supports this general scenario; however, the precise formation mechanism remains undetermined. Here, solid O2 ice held at 12 K is exposed to a monoenergetic beam of 5 keV D+ ions. Products formed during the irradiation period are monitored through FTIR spectroscopy. O3 is observed through seven archetypal absorptions. Three additional bands found at 2583, 2707, and 1195 cm -1 correspond to matrix isolated DO2 (ν1) and D2O2 (ν1, ν5), and D2O (ν2), respectively. During subsequent warming, the O2 ice sublimates, revealing a broad band at 2472 cm-1 characteristic of amorphous D2O (ν1, ν3). Sublimating D2, D2O, D2O2, and O3 products were confirmed through their subsequent detection via quadrupole mass spectrometry. Reaction schemes based on both thermally accessible and suprathermally induced chemistries were developed to fit the observed temporal profiles are used to elucidate possible reaction pathways for the formation of D2-water. Several alternative schemes to the hydrogenation pathway (O2→HO2→H2O2→H2O) were identified; their astrophysical implications are briefly discussed.

Constraints on mechanisms for the growth of gully alcoves in Gasa crater, Mars, from two-dimensional stability assessments of rock slopes

USGS Publications Warehouse

Okubo, C.H.; Tornabene, L.L.; Lanza, N.L.

2011-01-01

The value of slope stability analyses for gaining insight into the geologic conditions that would facilitate the growth of gully alcoves on Mars is demonstrated in Gasa crater. Two-dimensional limit equilibrium methods are used in conjunction with high-resolution topography derived from stereo High Resolution Imaging Science Experiment (HiRISE) imagery. These analyses reveal three conditions that may produce observed alcove morphologies through slope failure: (1) a ca >10m thick surface layer that is either saturated with H2O ground ice or contains no groundwater/ice at all, above a zone of melting H2O ice or groundwater and under dynamic loading (i.e., seismicity), (2) a 1-10m thick surface layer that is saturated with either melting H2O ice or groundwater and under dynamic loading, or (3) a >100m thick surface layer that is saturated with either melting H2O ice or groundwater and under static loading. This finding of three plausible scenarios for slope failure demonstrates how the triggering mechanisms and characteristics of future alcove growth would be affected by prevailing environmental conditions. HiRISE images also reveal normal faults and other fractures tangential to the crowns of some gully alcoves that are interpreted to be the result of slope instability, which may facilitate future slope movement. Stability analyses show that the most failure-prone slopes in this area are found in alcoves that are adjacent to crown fractures. Accordingly, crown fractures appear to be a useful indicator of those alcoves that should be monitored for future landslide activity. ?? 2010.

Dynamics and unsteady morphologies at ice interfaces driven by D2O–H2O exchange

PubMed Central

Holmes-Cerfon, Miranda; Kohn, Robert V.

2017-01-01

The growth dynamics of D2O ice in liquid H2O in a microfluidic device were investigated between the melting points of D2O ice (3.8 °C) and H2O ice (0 °C). As the temperature was decreased at rates between 0.002 °C/s and 0.1 °C/s, the ice front advanced but retreated immediately upon cessation of cooling, regardless of the temperature. This is a consequence of the competition between diffusion of H2O into the D2O ice, which favors melting of the interface, and the driving force for growth supplied by cooling. Raman microscopy tracked H/D exchange across the solid H2O–solid D2O interface, with diffusion coefficients consistent with transport of intact H2O molecules at the D2O ice interface. At fixed temperatures below 3 °C, the D2O ice front melted continuously, but at temperatures near 0 °C a scalloped interface morphology appeared with convex and concave sections that cycled between growth and retreat. This behavior, not observed for D2O ice in contact with D2O liquid or H2O ice in contact with H2O liquid, reflects a complex set of cooperative phenomena, including H/D exchange across the solid–liquid interface, latent heat exchange, local thermal gradients, and the Gibbs–Thomson effect on the melting points of the convex and concave features. PMID:29042511

Formation of interstellar methanol ice prior to the heavy CO freeze-out stage

NASA Astrophysics Data System (ADS)

Qasim, D.; Chuang, K.-J.; Fedoseev, G.; Ioppolo, S.; Boogert, A. C. A.; Linnartz, H.

2018-04-01

Context. The formation of methanol (CH3OH) on icy grain mantles during the star formation cycle is mainly associated with the CO freeze-out stage. Yet there are reasons to believe that CH3OH also can form at an earlier period of interstellar ice evolution in CO-poor and H2O-rich ices. Aims: This work focuses on CH3OH formation in a H2O-rich interstellar ice environment following the OH-mediated H-abstraction in the reaction, CH4 + OH. Experimental conditions are systematically varied to constrain the CH3OH formation yield at astronomically relevant temperatures. Methods: CH4, O2, and hydrogen atoms are co-deposited in an ultrahigh vacuum chamber at 10-20 K. OH radicals are generated by the H + O2 surface reaction. Temperature programmed desorption - quadrupole mass spectrometry (TPD-QMS) is used to characterize CH3OH formation, and is complemented with reflection absorption infrared spectroscopy (RAIRS) for CH3OH characterization and quantitation. Results: CH3OH formation is shown to be possible by the sequential surface reaction chain, CH4 + OH → CH3 + H2O and CH3 + OH → CH3OH at 10-20 K. This reaction is enhanced by tunneling, as noted in a recent theoretical investigation Lamberts et al. (2017, A&A, 599, A132). The CH3OH formation yield via the CH4 + OH route versus the CO + H route is approximately 20 times smaller for the laboratory settings studied. The astronomical relevance of the new formation channel investigated here is discussed.

CANDIDATE WATER VAPOR LINES TO LOCATE THE H{sub 2}O SNOWLINE THROUGH HIGH-DISPERSION SPECTROSCOPIC OBSERVATIONS. I. THE CASE OF A T TAURI STAR

DOE Office of Scientific and Technical Information (OSTI.GOV)

Notsu, Shota; Ishimoto, Daiki; Nomura, Hideko

2016-08-20

Inside the H{sub 2}O snowline of protoplanetary disks, water evaporates from the dust-grain surface into the gas phase, whereas it is frozen out onto the dust in the cold region beyond the snowline. H{sub 2}O ice enhances the solid material in the cold outer part of a disk, which promotes the formation of gas-giant planet cores. We can regard the H{sub 2}O snowline as the surface that divides the regions between rocky and gaseous giant planet formation. Thus observationally measuring the location of the H{sub 2}O snowline is crucial for understanding the planetesimal and planet formation processes, and the originmore » of water on Earth. In this paper, we find candidate water lines to locate the H{sub 2}O snowline through future high-dispersion spectroscopic observations. First, we calculate the chemical composition of the disk and investigate the abundance distributions of H{sub 2}O gas and ice, and the position of the H{sub 2}O snowline. We confirm that the abundance of H{sub 2}O gas is high not only in the hot midplane region inside the H{sub 2}O snowline but also in the hot surface layer of the outer disk. Second, we calculate the H{sub 2}O line profiles and identify those H{sub 2}O lines that are promising for locating the H{sub 2}O snowline: the identified lines are those that have small Einstein A coefficients and high upper state energies. The wavelengths of the candidate H{sub 2}O lines range from mid-infrared to sub-millimeter, and they overlap with the regions accessible to the Atacama Large Millimeter/sub-millimeter Array and future mid-infrared high-dispersion spectrographs (e.g., TMT/MICHI, SPICA).« less

Radiative habitable zones in martian polar environments.

PubMed

Córdoba-Jabonero, Carmen; Zorzano, María-Paz; Selsis, Franck; Patel, Manish R; Cockell, Charles S

2005-06-01

The biologically damaging solar ultraviolet (UV) radiation (quantified by the DNA-weighted dose) reaches the martian surface in extremely high levels. Searching for potentially habitable UV-protected environments on Mars, we considered the polar ice caps that consist of a seasonally varying CO2 ice cover and a permanent H2O ice layer. It was found that, though the CO2 ice is insufficient by itself to screen the UV radiation, at approximately 1 m depth within the perennial H2O ice the DNA-weighted dose is reduced to terrestrial levels. This depth depends strongly on the optical properties of the H2O ice layers (for instance snow-like layers). The Earth-like DNA-weighted dose and Photosynthetically Active Radiation (PAR) requirements were used to define the upper and lower limits of the northern and southern polar Radiative Habitable Zone (RHZ) for which a temporal and spatial mapping was performed. Based on these studies we conclude that photosynthetic life might be possible within the ice layers of the polar regions. The thickness varies along each martian polar spring and summer between approximately 1.5 and 2.4 m for H2O ice-like layers, and a few centimeters for snow-like covers. These martian Earth-like radiative habitable environments may be primary targets for future martian astrobiological missions. Special attention should be paid to planetary protection, since the polar RHZ may also be subject to terrestrial contamination by probes. c2004 Elsevier Inc. All rights reserved.

Polycrystalline methane hydrate: Synthesis from superheated ice, and low-temperature mechanical properties

USGS Publications Warehouse

Stern, L.A.; Kirby, S.H.; Durham, W.B.

1998-01-01

We describe a new and efficient technique to grow aggregates of pure methane hydrate in quantities suitable for physical and material properties testing. Test specimens were grown under static conditions by combining cold, pressurized CH4 gas with granulated H2O ice, and then warming the reactants to promote the reaction CH4(g) + 6H2O(s???1) ??? CH4??6H2O (methane hydrate). Hydrate formation evidently occurs at the nascent ice/liquid water interface on ice grain surfaces, and complete reaction was achieved by warming the system above the ice melting point and up to 290 K, at 25-30 MPa, for approximately 8 h. The resulting material is pure, cohesive, polycrystalline methane hydrate with controlled grain size and random orientation. Synthesis conditions placed the H2O ice well above its melting temperature while reaction progressed, yet samples and run records showed no evidence for bulk melting of the unreacted portions of ice grains. Control experiments using Ne, a non-hydrate-forming gas, showed that under otherwise identical conditions, the pressure reduction and latent heat associated with ice melting are easily detectable in our fabrication apparatus. These results suggest that under hydrate-forming conditions, H2O ice can persist metastably to temperatures well above its ordinary melting point while reacting to form hydrate. Direct observations of the hydrate growth process in a small, high-pressure optical cell verified these conclusions and revealed additional details of the hydrate growth process. Methane hydrate samples were then tested in constant-strain-rate deformation experiments at T = 140-200 K, Pc = 50-100 MPa, and ?? = 10-4 10-6 s-1. Measurements in both the brittle and ductile fields showed that methane hydrate has measurably different strength than H2O ice, and work hardens to an unusually high degree compared to other ices as well as to most metals and ceramics at high homologous temperatures. This work hardening may be related to a changing stoichiometry under pressure during plastic deformation; X-ray analyses showed that methane hydrate undergoes a process of solid-state disproportionation or exsolution during deformation at conditions well within its conventional stability field.

Compositional analysis of Hyperion with the Cassini Visual and Infrared Mapping Spectrometer

NASA Astrophysics Data System (ADS)

Brad Dalton, J.; Cruikshank, Dale P.; Clark, Roger N.

2012-08-01

Compositional mapping of the surface of Hyperion using Cassini Visual and Infrared Mapping Spectrometer (VIMS) observations reveals a heterogeneous surface dominated by water ice accompanied by additional materials. Carbon dioxide, as evidenced by a prominent absorption band centered at 4.26 μm, is distributed over most of the surface, including icy regions. This does not represent exposures of pure CO2 ice, but concentrations of CO2 molecules adsorbed on other materials or complexed in H2O, perhaps as a clathrate (Cruikshank, D.P., Meyer, A.W., Brown, R.H., Clark, R.N., Jaumann, R., Stephan, K., Hibbitts, C.A., Sandford, S.A., Mastrapa, R., Filacchione, G., Dalle Ore, C.M., Nicholson, P.D., Buratti, B.J., McCord, T.B., Nelson, R.M., Dalton, J.B., Baines, K.H., Matson, D.L., The VIMS Team [2010]. Icarus 206, 561-572). Localized deposits of low-albedo material in subcircular depressions exhibit spectral absorptions indicative of C-H in aromatic (3.29 μm) and aliphatic (3.35-3.50 μm) hydrocarbons. An absorption band at 2.42 μm that is also seen on other saturnian satellites, tentatively identified as H2 (Clark, R.N. et al. [2011]. In: Proc. AAS-DPS Meeting, 43, 1563; Clark et al., in preparation, 2012) adsorbed on dark material grains, is also prominent. Our best spectral models included H2O and CO2 ice, with small amounts of nanophase Fe and Fe2O3. Weaker and more spatially scattered absorption features are also found at 4.48, 4.60, and 4.89 μm, although no clear molecular identifications have yet been made. While strongest in the low-albedo deposits, the CO2, hydrocarbon and putative H2 bands vary in strength throughout the icy regions, as do the 4.48-, 4.60- and 4.89-μm bands, suggesting that this background ice is laced with a complex mixture of non-ice compounds.

The Chemistry of Pluto and its Satellites

NASA Technical Reports Server (NTRS)

Cruikshank, Dale P.

2017-01-01

Pluto's bulk composition and the composition of the surface layers hold clues to the origin and evolution of a number of other Solar System bodies of comparable size in the region beyond Neptune. The July 14, 2015 flyby of the Pluto system with the New Horizons spacecraft afforded the opportunity to corroborate and greatly improve discoveries about the planet and its satellites derived Earth-based studies. It also revealed extraordinary details of the surface and atmosphere of Pluto, as well as the geology and composition of Charon and two smaller satellites. With a mean density of 1.86 g/sq cm, the bulk composition of Pluto is about two-thirds anhydrous solar composition rocky material and one-third volatiles (primarily H2O in liquid and solid states) by mass, the surface is a veneer of ices dominated by N2, with smaller amounts of CH4 and CO, as well as limited exposures of H2O ice (considered to be "bedrock"). N2, CH4, and CO occur as solid solutions at temperature-dependent mutual concentrations, each component being soluble in the others. Frozen C2H6 as a minor component has also been identified. Sublimation and recondensation of N2, CH4, and CO over seasonal (248 y) and Milankovich-type megaseasons (approx. 3 My) result in the redistribution of these ices over time and with latitude control. Solid N2 is found in glaciers originating in higher elevations and flowing at the present time into a basin structure larger than the State of Texas, forming a convecting lens of N2 that overturns on a timescale of order 10 My. The varied colors of Pluto's landscape arise from the energetic processing of the surface ices in processes that break the simple molecules and reassemble complex organic structures consisting of groups of aromatic rings connected by aliphatic chains. When synthesized in the laboratory by UV or electron irradiation of a Pluto mix of ice, this material, called tholin, has colors closely similar to Pluto. The Pluto ice tholin analog contains carboxylic acids, urea, ketones, aldehydes, amines, and some nitriles. The largest satellite, Charon has density 1.70 g/sq cm and it is about 3/5 anhydrous solar composition rock, with the remainder in H2O ice. The surface H2O ice is infused in some way with NH3, probably as a hydrate, distributed nonuniformly, but to some degree related to geological structures. Pluto's atmosphere is N2, CH4, with CO, C2-hydrocarbons, HCN, and other molecules in trace but detectable amounts. The atmosphere supports a complex haze structure with about 20 discrete layers, and suspected clouds. The haze is presumed to be made of aggregates of complex hydrocarbons (tholins) produced by photolysis of the atmospheric gases, and with similar composition to the ice tholins made on the planet's surface. Urea and a suite of carboxylic acids are of interest for prebiotic and biological chemistries.

The spectral albedo of sea ice and salt crusts on the tropical ocean of Snowball Earth: 1. Laboratory measurements

NASA Astrophysics Data System (ADS)

Light, Bonnie; Carns, Regina C.; Warren, Stephen G.

2016-07-01

The ice-albedo feedback mechanism likely contributed to global glaciation during the Snowball Earth events of the Neoproterozoic era (1 Ga to 544 Ma). This feedback results from the albedo contrast between sea ice and open ocean. Little is known about the optical properties of some of the possible surface types that may have been present, including sea ice that is both snow-free and cold enough for salts to precipitate within brine inclusions. A proxy surface for such ice was grown in a freezer laboratory using the single salt NaCl and kept below the eutectic temperature (-21.2°C) of the NaCl-H2O binary system. The resulting ice cover was composed of ice and precipitated hydrohalite crystals (NaCl · 2H2O). As the cold ice sublimated, a thin lag-deposit of salt formed on the surface. To hasten its growth in the laboratory, the deposit was augmented by addition of a salt-enriched surface crust. Measurements of the spectral albedo of this surface were carried out over 90 days as the hydrohalite crust thickened due to sublimation of ice, and subsequently over several hours as the crust warmed and dissolved, finally resulting in a surface with puddled liquid brine. The all-wave solar albedo of the subeutectic crust is 0.93 (in contrast to 0.83 for fresh snow and 0.67 for melting bare sea ice). Incorporation of these processes into a climate model of Snowball Earth will result in a positive salt-albedo feedback operating between -21°C and -36°C.

High Pressure Cosmochemistry of Major Planetary Interiors: Laboratory Studies of the Water-rich Region of the System Ammonia-water

NASA Technical Reports Server (NTRS)

Nicol, M.; Johnson, M.; Koumvakalis, A. S.

1985-01-01

The behavior of gas-ice mixtures in major planets at very high pressures was studied. Some relevant pressure-temperature-composition (P-T-X) regions of the hydrogen (H2)-helium (He)-water (H2O-ammonia (NH3)-methane (CH4) phase diagram were determined. The studies, and theoretical model, of the relevant phases, are needed to interpret the compositions of ice-gas systems at conditions of planetary interest. The compositions and structures of a multiphase, multicomponent system at very high pressures care characterized, and the goal is to characterize this system over a wide range of low and high temperatures. The NH3-H2O compositions that are relevant to planetary problems yet are easy to prepare were applied. The P-T surface of water was examined and the corresponding surface for NH3 was determined. The T-X diagram of ammonia-water at atmospheric pressure was studied and two water-rich phases were found, NH3-2H2O (ammonia dihydrate), which melts incongruently, and NH3.H2O (ammonia monohydrate), which is nonstoichiometric and melts at a higher temperature than the dihydrate. It is suggested that a P-T surface at approximately the monohydrate composition and the P-X surface at room temperature is determined.

First Principles Simulations of Ice Nucleation at Metal Surfaces

NASA Astrophysics Data System (ADS)

Michaelides, Angelos

2005-03-01

Ice nucleation at solid surfaces is of relevance to countless scientific and technological processes. In particular the nucleation of ice nano-crystals on metal surfaces is often a key first step in cloud formation and corrosion [1]. Yet unfortunately this remains one of the most poorly understood natural phenomena; severely lacking in atomic level understanding. Here, we discuss detailed density functional theory studies aimed at putting our understanding of ice nucleation at metals on a much firmer footing. Specifically the properties of H2O hexamers - the smallest `building blocks' of ice - adsorbed on a number of close-packed transition metal surfaces have been examined. We find that the competing influences of substrate reactivity and hexamer-substrate epitaxial mismatch conspire to yield a rich variety of (novel) hexameric ice structures, some of which have been observed by recent scanning tunnelling microscopy experiments [2]. [1] H.R. Pruppacher and J.D. Klett, Microphysics of Clouds and Precipitation, (Kluwer, Dordrecht, 2003). [2] K. Morgenstern, et al., (To be published).

Radiolysis of astrophysical ice analogs by energetic ions: the effect of projectile mass and ice temperature.

PubMed

Pilling, Sergio; Duarte, Eduardo Seperuelo; Domaracka, Alicja; Rothard, Hermann; Boduch, Philippe; da Silveira, Enio F

2011-09-21

An experimental study of the interaction of highly charged, energetic ions (52 MeV (58)Ni(13+) and 15.7 MeV (16)O(5+)) with mixed H(2)O : C(18)O(2) astrophysical ice analogs at two different temperatures is presented. This analysis aims to simulate the chemical and the physicochemical interactions induced by cosmic rays inside dense, cold astrophysical environments, such as molecular clouds or protostellar clouds as well at the surface of outer solar system bodies. The measurements were performed at the heavy ion accelerator GANIL (Grand Accelerateur National d'Ions Lourds) in Caen, France. The gas samples were deposited onto a CsI substrate at 13 K and 80 K. In situ analysis was performed by a Fourier transform infrared (FTIR) spectrometer at different fluences. Radiolysis yields of the produced species were quantified. The dissociation cross section at 13 K of both H(2)O and CO(2) is about 3-4 times smaller when O ions are employed. The ice temperature seems to affect differently each species when the same projectile was employed. The formation cross section at 13 K of molecules such as C(18)O, CO (with oxygen from water), and H(2)O(2) increases when Ni ions are employed. The formation of organic compounds seems to be enhanced by the oxygen projectiles and at lower temperatures. In addition, because the organic production at 13 K is at least 4 times higher than the value at 80 K, we also expect that interstellar ices are more organic-rich than the surfaces of outer solar system bodies.

Ice in the lunar polar regions

NASA Technical Reports Server (NTRS)

Arnold, J. R.

1979-01-01

The idea that ice and other trapped volatiles exist in permanently shadowed regions near the lunar poles was proposed by Watson, Murray, and Brown (1961). It is reexamined in the present paper, in the light of the vast increase of lunar knowledge. The stability of the traps and the trapping mechanism are verified. Four potential sources of lunar H2O, namely (1) solar wind reduction of Fe in the regolith, (2) H2O-containing meteoroids, (3) cometary impact, and (4) (the least certain) degassing of the interior, can supply amounts of trapped H2O estimated in the range of 10 to the 16th to 10 to the 17th g. Two important destructive mechanisms have been identified: photodissociation of H2O molecules adsorbed on the sunlit surface and sputtering or decomposition of trapped H2O by solar wind particles. The effect of impact gardening is mainly protective. The question of the presence of H2O in the traps remains open; it can be settled by experiment.

Reconstructing the history of water ice formation from HDO/H2O and D2O/HDO ratios in protostellar cores

NASA Astrophysics Data System (ADS)

Furuya, K.; van Dishoeck, E. F.; Aikawa, Y.

2016-02-01

Recent interferometer observations have found that the D2O/HDO abundance ratio is higher than that of HDO/H2O by about one order of magnitude in the vicinity of low-mass protostar NGC 1333-IRAS 2A, where water ice has sublimated. Previous laboratory and theoretical studies show that the D2O/HDO ice ratio should be lower than the HDO/H2O ice ratio, if HDO and D2O ices are formed simultaneously with H2O ice. In this work, we propose that the observed feature, D2O/HDO > HDO/H2O, is a natural consequence of chemical evolution in the early cold stages of low-mass star formation as follows: 1) majority of oxygen is locked up in water ice and other molecules in molecular clouds, where water deuteration is not efficient; and 2) water ice formation continues with much reduced efficiency in cold prestellar/protostellar cores, where deuteration processes are highly enhanced as a result of the drop of the ortho-para ratio of H2, the weaker UV radiation field, etc. Using a simple analytical model and gas-ice astrochemical simulations, which traces the evolution from the formation of molecular clouds to protostellar cores, we show that the proposed scenario can quantitatively explain the observed HDO/H2O and D2O/HDO ratios. We also find that the majority of HDO and D2O ices are likely formed in cold prestellar/protostellar cores rather than in molecular clouds, where the majority of H2O ice is formed. This work demonstrates the power of the combination of the HDO/H2O and D2O/HDO ratios as a tool to reveal the past history of water ice formation in the early cold stages of star formation, and when the enrichment of deuterium in the bulk of water occurred. Further observations are needed to explore if the relation, D2O/HDO > HDO/H2O, is common in low-mass protostellar sources.

The physical and infrared spectral properties of CO2 in astrophysical ice analogs

NASA Technical Reports Server (NTRS)

Sandford, S. A.; Allamandola, L. J.

1990-01-01

Results of measurements of the infrared spectroscopic and condensation-vaporization properties of CO2 in pure and mixed ices are presented. Detailed examination of five infrared CO2 bands, 2.20, 2.78, 4.27, 15.2, and 4.39 microns, shows that the peak position, FWHM, and profile of the bands provide important information about the composition, formation, and subsequent thermal history of the ices. Absorption coefficients and their temperature dependence for all five CO2 bands are determined. The temperature dependence variation is found to be less than 15 percent from 10 to 150 K, i.e., the temperature at which H2O ice sublimes. The number of parameters associated with the physical behavior of CO2 in CO2- and H2O-rich ices, including surface binding energies, and condensation and sublimation temperatures, are determined under experimental conditions. The implications of the data obtained for cometary models are considered.

The Ortho-to-para Ratio of Water Molecules Desorbed from Ice Made from Para-water Monomers at 11 K

NASA Astrophysics Data System (ADS)

Hama, Tetsuya; Kouchi, Akira; Watanabe, Naoki

2018-04-01

Water has two nuclear-spin isomers: ortho- and para-H2O. Some observations of interstellar space and cometary comae have reported the existence of gaseous H2O molecules with anomalous ortho-to-para ratios (OPRs) less than the statistical value of three. This has been often used to estimate the formation temperature of ice on dust, which is inferred to be below 50 K. The relation between the nuclear-spin dynamics of H2O in ice at low temperatures and the OPR of gaseous H2O desorbed from the ice has yet to be explored in a laboratory. Consequently, the true meaning of the observed OPRs remains debated. We measure the OPR of H2O photodesorbed from ice made from para-H2O monomers at 11 K, which was prepared by the sublimation of Ne from a para-H2O/Ne matrix. The photodesorbed H2O molecules from the ice have the statistical OPR value of three, demonstrating the immediate nuclear-spin-state mixing of H2O toward the statistical value of ice even at 11 K. The OPR of H2O thermally desorbed from the ice also shows the expected statistical value. Our results indicate that the OPR of H2O desorbed from interstellar ice should be the statistical value regardless of the formation process of the ice, which cannot be used to deduce the ice-formation temperature. This study highlights the importance of interstellar gas-phase processes in understanding anomalous abundance ratios of nuclear-spin isomers of molecules in space.

Cosmic ion bombardment of the icy moons of Jupiter

NASA Astrophysics Data System (ADS)

Strazzulla, G.

2011-05-01

A large number of experiments have been performed in many laboratories in the world with the aim to investigate the physico-chemical effects induced by fast ions irradiating astrophysical relevant materials. The laboratory in Catania (Italy) has given a contribution to some experimental works. In this paper I review the results of two class of experiments performed by the Catania group, namely implantation of reactive (H+, C+, N+, O+ and S+) ions in ices and the ion irradiation induced synthesis of molecules at the interface between water ice and carbonaceous or sulfurous solid materials. The results, discussed in the light of some questions concerning the surfaces of the Galilean moons, contribute to understand whether minor molecular species (CO2, SO2, H2SO4, etc.) observed on those objects are endogenic i.e. native from the satellite or are produced by exogenic processes, such as ion implantation.The results indicate that:C-ion implantation is not the dominant formation mechanism of CO2 on Europa, Ganimede and Callisto.Implantation of sulfur ions into water ice produces hydrated sulfuric acid with high efficiency such to give a very important contribution to the sulfur cycle on the surface of Europa and other satellites.Implantation of protons into carbon dioxide produces some species containing the projectile (H2CO3, and O-H in poly-water).Implantation of protons into sulfur dioxide produces SO3, polymers, and O3 but not H-S bonds.Water ice has been deposited on refractory carbonaceous materials: a general finding is the formation of a noteworthy quantity of CO2. We suggest that this is the primary mechanism to explain the presence of carbon dioxide on the surfaces of the Galilean satellites.Water ice has been deposited on refractory sulfurous materials originating from SO2 or H2S irradiation. No evidence for an efficient synthesis of SO2 has been found.

Possible fossil H2O liquid-ice interfaces in the Martian crust

USGS Publications Warehouse

Soderblom, L.A.; Wenner, D.B.

1978-01-01

Throughout the northern equatorial region of Mars, extensive areas have been uniformly stripped, roughly to a constant depth. These terrains vary widely in their relative ages. A model is described here to explain this phenomenon as reflecting the vertical distribution of H2O liquid and ice in the crust. Under present conditions the Martian equatorial regions are stratified in terms of the stability of water ice and liquid water. This arises because the temperature of the upper 1 or 2 km is below the melting point of ice and liquid is stable only at greater depth. It is suggested here that during planetary outgassing earlier in Martian history H2O was injected into the upper few kilometers of the crust by subsurface and surface volcanic eruption and lateral migration of the liquid and vapor. As a result, a discontinuity in the physical state of materials developed in the Martian crust coincident with the depth of H2O liquid-ice phase boundary. Material above the boundary remained pristine; material below underwent diagenetic alteration and cementation. Subsequently, sections of the ice-laden zone were erosionally stripped by processes including eolian deflation, gravitational slump and collapse, and fluvial transport due to geothermal heating and melting of the ice. The youngest plains which display this uniform stripping may provide a minimum stratigraphic age for the major period of outgassing of the planet. Viking results suggest that the total amount of H2O outgassed is less than half that required to fill the ice layer, hence any residual liquid eventually found itself in the upper permafrost zone or stored in the polar regions. Erosion stopped at the old liquid-ice interface due to increased resistance of subjacent material and/or because melting of ice was required to mobilize the debris. Water ice may remain in uneroded regions, the overburden of debris preventing its escape to the atmosphere. Numerous morphological examples shown in Viking and Mariner 9 images suggest interaction of impact, volcanic, and gravitational processes with the ice-laden layer. Finally, volcanic eruptions into ice produces a highly oxidized friable amorphous rock, palagonite. Based on spectral reflectance properties, these materials may provide the best analog to Martian surface materials. They are easily eroded, providing vast amounts of eolian debris, and have been suggested (Toulmin et al., 1977) as possible source rocks for the materials observed at the Viking landing sites. ?? 1978.

Composition and stability of the condensate observed at the Viking Lander 2 site on Mars

NASA Astrophysics Data System (ADS)

Hart, H. M.; Jakosky, B. M.

1986-04-01

Surface energy balance and near-surface temperature data from the Viking Lander 2 site taken during the first winter that condensated were observed and analyzed to determine the relative stability of CO2 and H2O frosts. The CO2 frost stability is calculated with an equilibrium surface energy balance model, i.e., the total energy incident on a frost surface is compared with the blackbody energy emitted by the surface. The energy sources considered were IR emission from the atmosphere, sunlight, and the sensible heat flux from the atmosphere. H2O stability was examined as a function of buoyant diffusion and turbulent mixing processes which could remove saturated near-surface gases. The CO2 frost is found to be sufficiently unstable at the time the condensate was observed on the ground, so all CO2 ice deposited at night would boil away in a few hours of sunlight. CO2 ice would not form during a dust storm. Water frost would be stable during the condensate observations, since sublimation would occur at a rate below 1 micron/day. A stable winter thickness of 10 microns is projected for the water ice.

Composition and stability of the condensate observed at the Viking Lander 2 site on Mars

NASA Technical Reports Server (NTRS)

Hart, H. M.; Jakosky, B. M.

1986-01-01

Surface energy balance and near-surface temperature data from the Viking Lander 2 site taken during the first winter that condensated were observed and analyzed to determine the relative stability of CO2 and H2O frosts. The CO2 frost stability is calculated with an equilibrium surface energy balance model, i.e., the total energy incident on a frost surface is compared with the blackbody energy emitted by the surface. The energy sources considered were IR emission from the atmosphere, sunlight, and the sensible heat flux from the atmosphere. H2O stability was examined as a function of buoyant diffusion and turbulent mixing processes which could remove saturated near-surface gases. The CO2 frost is found to be sufficiently unstable at the time the condensate was observed on the ground, so all CO2 ice deposited at night would boil away in a few hours of sunlight. CO2 ice would not form during a dust storm. Water frost would be stable during the condensate observations, since sublimation would occur at a rate below 1 micron/day. A stable winter thickness of 10 microns is projected for the water ice.

The ultraviolet reflectance of Enceladus: Implications for surface composition

NASA Astrophysics Data System (ADS)

Hendrix, Amanda R.; Hansen, Candice J.; Holsclaw, Greg M.

2010-04-01

The reflectance of Saturn's moon Enceladus has been measured at far ultraviolet (FUV) wavelengths (115-190 nm) by Cassini's Ultraviolet Imaging Spectrograph (UVIS). At visible and near infrared (VNIR) wavelengths Enceladus' reflectance spectrum is very bright, consistent with a surface composed primarily of H 2O ice. At FUV wavelengths, however, Enceladus is surprisingly dark - darker than would be expected for pure water ice. Previous analyses have focused on the VNIR spectrum, comparing it to pure water ice (Cruikshank, D.P., Owen, T.C., Dalle Ore, C., Geballe, T.R., Roush, T.L., de Bergh, C., Sandford, S.A., Poulet, F., Benedix, G.K., Emery, J.P. [2005] Icarus, 175, 268-283) or pure water ice plus a small amount of NH 3 (Emery, J.P., Burr, D.M., Cruikshank, D.P., Brown, R.H., Dalton, J.B. [2005] Astron. Astrophys., 435, 353-362) or NH 3 hydrate (Verbiscer, A.J., Peterson, D.E., Skrutskie, M.F., Cushing, M., Helfenstein, P., Nelson, M.J., Smith, J.D., Wilson, J.C. [2006] Icarus, 182, 211-223). We compare Enceladus' FUV spectrum to existing laboratory measurements of the reflectance spectra of candidate species, and to spectral models. We find that the low FUV reflectance of Enceladus can be explained by the presence of a small amount of NH 3 and a small amount of a tholin in addition to H 2O ice on the surface. The presence of these three species (H 2O, NH 3, and a tholin) appears to satisfy not only the low FUV reflectance and spectral shape, but also the middle-ultraviolet to visible wavelength brightness and spectral shape. We expect that ammonia in the Enceladus plume is transported across the surface to provide a global coating.

Interaction of acetonitrile with the surfaces of amorphous and crystalline ice

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schaff, J.E.; Roberts, J.T.

1999-10-12

The adsorption of acetonitrile (CH{sub 3}CN) on ultrathin films of ice under ultrahigh vacuum was investigated with temperature-programmed desorption ass spectrometry (TPD) and Fourier transform infrared reflection absorption spectroscopy (FTIRAS). Two types of film were studied, amorphous and crystalline. On the amorphous films, two sates of adsorbed acetonitrile were observed by TPD and FTIRAS. One of the states is attributed to acetonitrile that is hydrogen bonded to agree OH group at the ice surface; the other state is assigned to acetonitrile that is purely physiorbed. Evidence for the hydrogen-bonded state is two-fold. First, there is a large kinetic isotope effectmore » for desorption from H{sub 2}O-and D{sub 2}O-ice: the desorption temperatures from ice-h{sub 2} and ice-d{sub 2} are {approximately}161 and {approximately}176 K, respectively. Second, the C{triple{underscore}bond}N stretching frequency (2,265 cm{sup {minus}1}) is 16 cm{sup {minus}1} is greater than that of physisorbed acetonitrile, and it is roughly equal to that of acetonitrile which is hydrogen bonded to an OH group at the air-liquid water interface. On the crystalline films, there is no evidence for a hydrogen-bonded state in the TPD spectra. The FTIRAS spectra do show that some hydrogen-bonded acetonitrile is present but at a maximum coverage that is roughly one-sixth of that on the amorphous surface. The difference between the amorphous and crystalline surfaces cannot be attributed to a difference n surface areas. Rather, this work provides additional evidence that the surface chemical properties of amorphous ice are different from those of crystalline ice.« less

RADIOLYSIS OF NITROGEN AND WATER-ICE MIXTURE BY FAST IONS: IMPLICATIONS FOR KUIPER BELT OBJECTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barros, A. L. F. de; Silveira, E. F da; Bergantini, A.

The participation of condensed nitrogen in the surface chemistry of some objects in the outer solar system, such as Pluto and Triton, is very important. The remote observation of this species using absorption spectroscopy is a difficult task because N{sub 2} is not IR active in the gas phase. Water is also among the most abundant molecules in the surface of these objects; chemical reactions between N{sub 2} and H{sub 2}O induced by cosmic rays are therefore expected. Although pure N{sub 2} ice is hardly identified by IR spectroscopy, the species produced through the processing of the surface ice bymore » cosmic rays may give relevant clues indicating how abundant the N{sub 2} is in the outside layers of the surface of trans-Neptunian objects (TNOs). The objective of this work is to investigate the formation of nitrogenated species induced by cosmic-ray analogs in an ice mixture containing nitrogen and water. Experiments were performed in the GANIL Laboratory by bombarding N{sub 2}:H{sub 2}O (10:1) ice at 15 K with 40 MeV {sup 58}Ni{sup 11+} ions. Evolution of precursor and daughter species was monitored by Fourier transform infrared spectrometry. The main produced species are the nitrogen oxides NO{sub k} (k = 1–3), N{sub 2}O{sub j} (j = 1–5), N{sub 3}, and O{sub 3}. Among them, the N{sub 2}O and N{sub 3} are the most abundant, representing ∼61% of the total column density of the daughter molecules at 10{sup 13} ions cm{sup −2} fluence; the current results indicate that the yield of daughter species from this mixture is low, and this may be one of the reasons why N{sub i}O{sub j} molecules are not usually observed in TNOs.« less

Photodesorption of H2O, HDO, and D2O ice and its impact on fractionation

NASA Astrophysics Data System (ADS)

Arasa, Carina; Koning, Jesper; Kroes, Geert-Jan; Walsh, Catherine; van Dishoeck, Ewine F.

2015-03-01

The HDO/H2O ratio measured in interstellar gas is often used to draw conclusions on the formation and evolution of water in star-forming regions and, by comparison with cometary data, on the origin of water on Earth. In cold cores and in the outer regions of protoplanetary disks, an important source of gas-phase water comes from photodesorption of water ice. This research note presents fitting formulae for implementation in astrochemical models using previously computed photodesorption efficiencies for all water ice isotopologues obtained with classical molecular dynamics simulations. The results are used to investigate to what extent the gas-phase HDO/H2O ratio reflects that present in the ice or whether fractionation can occur during the photodesorption process. Probabilities for the top four monolayers are presented for photodesorption of X (X = H, D) atoms, OX radicals, and X2O and HDO molecules following photodissociation of H2O, D2O, and HDO in H2O amorphous ice at ice temperatures from 10-100 K. Significant isotope effects are found for all possible products: (1) H atom photodesorption probabilities from H2O ice are larger than those for D atom photodesorption from D2O ice by a factor of 1.1; the ratio of H and D photodesorbed upon HDO photodissociation is a factor of 2. This process will enrich the ice in deuterium atoms over time; (2) the OD/OH photodesorption ratio upon D2O and H2O photodissociation is on average a factor of 2, but the OD/OH photodesorption ratio upon HDO photodissociation is almost constant at unity for all ice temperatures; (3) D atoms are more effective in kicking out neighbouring water molecules than H atoms. However, the ratio of the photodesorbed HDO and H2O molecules is equal to the HDO/H2O ratio in the ice, therefore, there is no isotope fractionation when HDO and H2O photodesorb from the ice. Nevertheless, the enrichment of the ice in D atoms due to photodesorption can over time lead to an enhanced HDO/H2O ratio in the ice, and, when photodesorbed, also in the gas. The extent to which the ortho/para ratio of H2O can be modified by the photodesorption process is discussed briefly as well. Appendices are available in electronic form at http://www.aanda.orgCompiled simulation data and raw data are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (ftp://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/575/A121

Ikaite crystals in melting sea ice - implications for pCO2 and pH levels in Arctic surface waters

NASA Astrophysics Data System (ADS)

Rysgaard, S.; Glud, R. N.; Lennert, K.; Cooper, M.; Halden, N.; Leakey, R. J. G.; Hawthorne, F. C.; Barber, D.

2012-03-01

A major issue of Arctic marine science is to understand whether the Arctic Ocean is, or will be, a source or sink for air-sea CO2 exchange. This has been complicated by the recent discoveries of ikaite (CaCO3·6H2O) in Arctic and Antarctic sea ice, which indicate that multiple chemical transformations occur in sea ice with a possible effect on CO2 and pH conditions in surface waters. Here we report on biogeochemical conditions, microscopic examinations and x-ray diffraction analysis of single crystals from an actively melting 1.7 km2 (0.5-1 m thick) drifting ice floe in the Fram Strait during summer. Our findings show that ikaite crystals are present throughout the sea ice but with larger crystals appearing in the upper ice layers. Ikaite crystals placed at elevated temperatures gradually disintegrated into smaller crystallites and dissolved. During our field campaign in late June, melt reduced the ice flow thickness by ca. 0.2 m per week and resulted in an estimated 1.6 ppm decrease of pCO2 in the ocean surface mixed layer. This corresponds to an air-sea CO2 uptake of 11 mmol m-2 sea ice d-1 or to 3.5 ton km-2 ice floe week-1.

Ikaite crystals in melting sea ice - implications for pCO2 and pH levels in Arctic surface waters

NASA Astrophysics Data System (ADS)

Rysgaard, S.; Glud, R. N.; Lennert, K.; Cooper, M.; Halden, N.; Leakey, R. J. G.; Hawthorne, F. C.; Barber, D.

2012-08-01

A major issue of Arctic marine science is to understand whether the Arctic Ocean is, or will be, a source or sink for air-sea CO2 exchange. This has been complicated by the recent discoveries of ikaite (a polymorph of CaCO3·6H2O) in Arctic and Antarctic sea ice, which indicate that multiple chemical transformations occur in sea ice with a possible effect on CO2 and pH conditions in surface waters. Here, we report on biogeochemical conditions, microscopic examinations and x-ray diffraction analysis of single crystals from a melting 1.7 km2 (0.5-1 m thick) drifting ice floe in the Fram Strait during summer. Our findings show that ikaite crystals are present throughout the sea ice but with larger crystals appearing in the upper ice layers. Ikaite crystals placed at elevated temperatures disintegrated into smaller crystallites and dissolved. During our field campaign in late June, melt reduced the ice floe thickness by 0.2 m per week and resulted in an estimated 3.8 ppm decrease of pCO2 in the ocean surface mixed layer. This corresponds to an air-sea CO2 uptake of 10.6 mmol m-2 sea ice d-1 or to 3.3 ton km-2 ice floe week-1. This is markedly higher than the estimated primary production within the ice floe of 0.3-1.3 mmol m-2 sea ice d-1. Finally, the presence of ikaite in sea ice and the dissolution of the mineral during melting of the sea ice and mixing of the melt water into the surface oceanic mixed layer accounted for half of the estimated pCO2 uptake.

Evidence From Hydrogen Isotopes in Meteorites for a Martian Permafrost

NASA Technical Reports Server (NTRS)

Usui, T.; Alexander, C. M. O'D.; Wang, J.; Simon, J. I.; Jones, J. H.

2014-01-01

Fluvial landforms on Mars suggest that it was once warm enough to maintain persistent liquid water on its surface. The transition to the present cold and dry Mars is closely linked to the history of surface water, yet the evolution of surficial water is poorly constrained. We have investigated the evolution of surface water/ ice and its interaction with the atmosphere by measurements of hydrogen isotope ratios (D/H: deuterium/ hydrogen) of martian meteorites. Hydrogen is a major component of water (H2O) and its isotopes fractionate significantly during hydrological cycling between the atmosphere, surface waters, ground ice, and polar cap ice. Based on in situ ion microprobe analyses of three geochemically different shergottites, we reported that there is a water/ice reservoir with an intermediate D/H ratio (delta D = 1,000?2500 %) on Mars. Here we present the possibility that this water/ice reservoir represents a ground-ice/permafrost that has existed relatively intact over geologic time.

Laboratory Spectra of CO2 Vibrational Modes in Planetary Ice Analogs

NASA Technical Reports Server (NTRS)

White, Douglas; Mastrapa, Rachel M.; Sandford, Scott

2012-01-01

Laboratory spectra have shown that CO2 is a powerful diagnostic tool for analyzing infrared data from remote observations, as it has been detected on icy moons in the outer Solar System as well as dust grain surfaces in the interstellar medium (ISM). IR absorption band profiles of CO2 within ice mixtures containing H2O and CH3OH change with respect to temperature and mixture ratios. In this particular study, the CO2 asymmetric stretching mode near 4.3 m (2350 cm (exp-1)), overtone mode near 1.97 m (5080 cm (exp-1)), and the combination bands near 2.7 m (3700 cm (exp-1)), 2.8 m (3600 cm (exp-1)), and 2.02 m (4960 cm (exp -1)), are systematically observed in different mixtures with H2O and CH3OH in temperature ranges from 15K to 150 K. Additionally, some high-temperature deposits (T greater than 50 K) of H2O, CH3OH, and CO2 ice mixtures were performed. These data may then be used to interpret infrared observational data obtained from icy surfaces in the outer Solar System and beyond.

H2O grain size and the amount of dust in Mars' residual north polar cap

NASA Technical Reports Server (NTRS)

Kieffer, Hugh H.

1990-01-01

In Mars' north polar cap, the probable composition of material residual from the annual condensation cycle is a mixture of fine dust and H2O grains of comparable size and abundance. However, metamorphism of such material will gradually lower its albedo by increasing the size of the H2O grains only. If the cap is undergoing net annual sublimation (as inferred from water vapor observations), late summer observations should be of old ice with H2O grain sizes of 100 microns or more. Ice of this granularity containing 30 percent fine dust has a reflectivity similar to that of dust alone; the observed albedo and computed ice grain size imply dust concentrations of 1 part per 1000 or less. The brightness of the icy areas conflicts with what would be expected for a residual cap deposited by an annual cycle similar to that observed by Viking and aged for thousands of years. The residual cap surface cannot be 'old dirty' ice. It could be old, coarse, and clean; or it could be young, fine, and dirty. This brings into question both the source of the late summer water vapor and the formation rate of laminated terrain.

H2O grain size and the amount of dust in Mars' residual North polar cap

USGS Publications Warehouse

Kieffer, H.H.

1990-01-01

In Mars' north polar cap the probable composition of material residual from the annual condensation cycle is a mixture of fine dust and H2O grains of comparable size and abundance. However, metamorphism of such material will gradually lower its albedo by increasing the size of the H2O grains only. If the cap is undergoing net annual sublimation (as inferred from water vapor observations), late summer observations should be of old ice with H2O grain sizes of 100 ??m or more. Ice of this granularity containing 30% fine dust has a reflectivity similar to that of dust alone; the observed albedo and computed ice grain size imply dust concentrations of 1 part per 1000 or less. The brightness of the icy areas conflicts with what would be expected for a residual cap deposited by an annual cycle similar to that observed by Viking and aged for thousands of years. The residual cap surface cannot be "old dirty' ice. It could be old, coarse, and clean; or it could be young, fine, and dirty. This brings into question both the source of the late summer water vapor and the formation rate of laminated terrain. -Author

Studies of proton irradiated H2O + CO2 and H2O + CO ices and analysis of synthesized molecules

NASA Technical Reports Server (NTRS)

Moore, M. H.; Khanna, R.; Donn, B.

1991-01-01

Infrared spectra of H2O + CO2 and H2O + CO ices before and after proton irradiation showed that a major reaction in both mixtures was the interconversion of CO2 yields CO. Radiation synthesized organic compounds such as carbonic acid were identified in the H2O + CO2 ice. Different chemical pathways dominate in the H2O + CO ice in which formaldehyde, methanol, ethanol, and methane were identified. Sublimed material was also analyzed using a mass spectrometer. Implications of these results are discussed in reference to comets.

Systematic Variations in CO2/H2O Ice Abundance Ratios in Nearby Galaxies Found with AKARI Near-infrared Spectroscopy

NASA Astrophysics Data System (ADS)

Yamagishi, M.; Kaneda, H.; Ishihara, D.; Oyabu, S.; Onaka, T.; Shimonishi, T.; Suzuki, T.

2015-07-01

We report CO2/H2O ice abundance ratios in seven nearby star-forming galaxies based on the AKARI near-infrared (2.5-5.0 μm) spectra. The CO2/H2O ice abundance ratios show clear variations between 0.05 and 0.2 with the averaged value of 0.14 ± 0.01. The previous study on M82 revealed that the CO2/H2O ice abundance ratios strongly correlate with the intensity ratios of the hydrogen recombination Brα line to the polycyclic aromatic hydrocarbon (PAH) 3.3 μm feature. In the present study, however, we find no correlation for the seven galaxies as a whole due to systematic differences in the relation between CO2/H2O ice abundance and Brα/PAH 3.3 μm intensity ratios from galaxy to galaxy. This result suggests that there is another parameter that determines the CO2/H2O ice abundance ratios in a galaxy in addition to the Brα/PAH 3.3 μm ratios. We find that the CO2/H2O ice abundance ratios positively correlate with the specific star formation rates of the galaxies. From these results, we conclude that CO2/H2O ice abundance ratios tend to be high in young star-forming galaxies.

Bacterial Ice Nucleation in Monodisperse D2O and H2O-in-Oil Emulsions.

PubMed

Weng, Lindong; Tessier, Shannon N; Smith, Kyle; Edd, Jon F; Stott, Shannon L; Toner, Mehmet

2016-09-13

Ice nucleation is of fundamental significance in many areas, including atmospheric science, food technology, and cryobiology. In this study, we investigated the ice-nucleation characteristics of picoliter-sized drops consisting of different D2O and H2O mixtures with and without the ice-nucleating bacteria Pseudomonas syringae. We also studied the effects of commonly used cryoprotectants such as ethylene glycol, propylene glycol, and trehalose on the nucleation characteristics of D2O and H2O mixtures. The results show that the median freezing temperature of the suspension containing 1 mg/mL of a lyophilized preparation of P. syringae is as high as -4.6 °C for 100% D2O, compared to -8.9 °C for 100% H2O. As the D2O concentration increases every 25% (v/v), the profile of the ice-nucleation kinetics of D2O + H2O mixtures containing 1 mg/mL Snomax shifts by about 1 °C, suggesting an ideal mixing behavior of D2O and H2O. Furthermore, all of the cryoprotectants investigated in this study are found to depress the freezing phenomenon. Both the homogeneous and heterogeneous freezing temperatures of these aqueous solutions depend on the water activity and are independent of the nature of the solute. These findings enrich our fundamental knowledge of D2O-related ice nucleation and suggest that the combination of D2O and ice-nucleating agents could be a potential self-ice-nucleating formulation. The implications of self-nucleation include a higher, precisely controlled ice seeding temperature for slow freezing that would significantly improve the viability of many ice-assisted cryopreservation protocols.

ELECTRON IRRADIATION AND THERMAL PROCESSING OF MIXED-ICES OF POTENTIAL RELEVANCE TO JUPITER TROJAN ASTEROIDS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mahjoub, Ahmed; Poston, Michael J.; Hand, Kevin P.

In this work we explore the chemistry that occurs during the irradiation of ice mixtures on planetary surfaces, with the goal of linking the presence of specific chemical compounds to their formation locations in the solar system and subsequent processing by later migration inward. We focus on the outer solar system and the chemical differences for ice mixtures inside and outside the stability line for H{sub 2}S. We perform a set of experiments to explore the hypothesis advanced by Wong and Brown that links the color bimodality in Jupiter's Trojans to the presence of H{sub 2}S in the surface ofmore » their precursors. Non-thermal (10 keV electron irradiation) and thermally driven chemistry of CH{sub 3}OH–NH{sub 3}–H{sub 2}O (“without H{sub 2}S”) and H{sub 2}S–CH{sub 3}OH–NH{sub 3}–H{sub 2}O (“with H{sub 2}S”) ices were examined. Mid-IR analyses of ice and mass spectrometry monitoring of the volatiles released during heating show a rich chemistry in both of the ice mixtures. The “with H{sub 2}S” mixture experiment shows a rapid consumption of H{sub 2}S molecules and production of OCS molecules after a few hours of irradiation. The heating of the irradiated “with H{sub 2}S” mixture to temperatures above 120 K leads to the appearance of new infrared bands that we provisionally assign to SO{sub 2}and CS. We show that radiolysis products are stable under the temperature and irradiation conditions of Jupiter Trojan asteroids. This makes them suitable target molecules for potential future missions as well as telescope observations with a high signal-to-noise ratio. We also suggest the consideration of sulfur chemistry in the theoretical modeling aimed at understanding the chemical composition of Trojans and KOBs.« less

Influence of isotopic disorder on solid state amorphization and polyamorphism in solid H2O -D2O solutions

NASA Astrophysics Data System (ADS)

Gromnitskaya, E. L.; Danilov, I. V.; Lyapin, A. G.; Brazhkin, V. V.

2015-10-01

We present a low-temperature and high-pressure ultrasonic study of elastic properties of isotopic H2O-D2O solid solutions, comparing their properties with those of the isotopically pure H2O and D2O ices. Measurements were carried out for solid state amorphization (SSA) from 1h to high-density amorphous (HDA) ice upon compression up to 1.8 GPa at 77 K and for the temperature-induced (77 -190 K ) u-HDA (unrelaxed HDA) → e-HDA (expanded HDA) → low-density amorphous (LDA )→1 c cascade of ice transformations near room pressure. There are many similarities in the elasticity behaviour of H2O ,D2O , and H2O-D2O solid solutions, including the softening of the shear elastic modulus as a precursor of SSA and the HDA →LDA transition. We have found significant isotopic effects during H/D substitution, including elastic softening of H2O -D2O solid solutions with respect to the isotopically pure ices in the case of the bulk moduli of ices 1c and 1h and for both bulk and shear elastic moduli of HDA ice at high pressures (>1 GPa ) . This softening is related to the configurational isotopic disorder in the solid solutions. At low pressures, the isotope concentration dependence of the elastic moduli of u-HDA ice changes remarkably and becomes monotonic with pronounced change of the bulk modulus (≈20 %) .

Magnetospheric ion sputtering and water ice grain size at Europa

NASA Astrophysics Data System (ADS)

Cassidy, T. A.; Paranicas, C. P.; Shirley, J. H.; Dalton, J. B., III; Teolis, B. D.; Johnson, R. E.; Kamp, L.; Hendrix, A. R.

2013-03-01

We present the first calculation of Europa's sputtering (ion erosion) rate as a function of position on Europa's surface. We find a global sputtering rate of 2×1027 H2O s-1, some of which leaves the surface in the form of O2 and H2. The calculated O2 production rate is 1×1026 O2 s-1, H2 production is twice that value. The total sputtering rate (including all species) peaks at the trailing hemisphere apex and decreases to about 1/3rd of the peak value at the leading hemisphere apex. O2 and H2 sputtering, by contrast, is confined almost entirely to the trailing hemisphere. Most sputtering is done by energetic sulfur ions (100s of keV to MeV), but most of the O2 and H2 production is done by cold oxygen ions (temperature ∼ 100 eV, total energy ∼ 500 eV). As a part of the sputtering rate calculation we compared experimental sputtering yields with analytic estimates. We found that the experimental data are well approximated by the expressions of Famá et al. for ions with energies less than 100 keV (Famá, M., Shi, J., Baragiola, R.A., 2008. Sputtering of ice by low-energy ions. Surf. Sci. 602, 156-161), while the expressions from Johnson et al. fit the data best at higher energies (Johnson, R.E., Burger, M.H., Cassidy, T.A., Leblanc, F., Marconi, M., Smyth, W.H., 2009. Composition and Detection of Europa's Sputter-Induced Atmosphere, in: Pappalardo, R.T., McKinnon, W.B., Khurana, K.K. (Eds.), Europa. University of Arizona Press, Tucson.). We compare the calculated sputtering rate with estimates of water ice regolith grain size as estimated from Galileo Near-Infrared Mapping Spectrometer (NIMS) data, and find that they are strongly correlated as previously suggested by Clark et al. (Clark, R.N., Fanale, F.P., Zent, A.P., 1983. Frost grain size metamorphism: Implications for remote sensing of planetary surfaces. Icarus 56, 233-245.). The mechanism responsible for the sputtering rate/grain size link is uncertain. We also report a surface composition estimate using NIMS data from an area on the trailing hemisphere apex. We find a high abundance of sulfuric acid hydrate and radiation-resistant hydrated salts along with large water ice regolith grains, all of which are consistent with the high levels of magnetospheric bombardment at the trailing apex.

Novel two-step laser ablation and ionization mass spectrometry (2S-LAIMS) of actor-spectator ice layers: Probing chemical composition of D{sub 2}O ice beneath a H{sub 2}O ice layer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Rui, E-mail: ryang73@ustc.edu; Gudipati, Murthy S., E-mail: gudipati@jpl.nasa.gov

2014-03-14

In this work, we report for the first time successful analysis of organic aromatic analytes imbedded in D{sub 2}O ices by novel infrared (IR) laser ablation of a layered non-absorbing D{sub 2}O ice (spectator) containing the analytes and an ablation-active IR-absorbing H{sub 2}O ice layer (actor) without the analyte. With these studies we have opened up a new method for the in situ analysis of solids containing analytes when covered with an IR laser-absorbing layer that can be resonantly ablated. This soft ejection method takes advantage of the tenability of two-step infrared laser ablation and ultraviolet laser ionization mass spectrometry,more » previously demonstrated in this lab to study chemical reactions of polycyclic aromatic hydrocarbons (PAHs) in cryogenic ices. The IR laser pulse tuned to resonantly excite only the upper H{sub 2}O ice layer (actor) generates a shockwave upon impact. This shockwave penetrates the lower analyte-containing D{sub 2}O ice layer (spectator, a non-absorbing ice that cannot be ablated directly with the wavelength of the IR laser employed) and is reflected back, ejecting the contents of the D{sub 2}O layer into the vacuum where they are intersected by a UV laser for ionization and detection by a time-of-flight mass spectrometer. Thus, energy is transmitted from the laser-absorbing actor layer into the non-absorbing spectator layer resulting its ablation. We found that isotope cross-contamination between layers was negligible. We also did not see any evidence for thermal or collisional chemistry of PAH molecules with H{sub 2}O molecules in the shockwave. We call this “shockwave mediated surface resonance enhanced subsurface ablation” technique as “two-step laser ablation and ionization mass spectrometry of actor-spectator ice layers.” This method has its roots in the well-established MALDI (matrix assisted laser desorption and ionization) method. Our method offers more flexibility to optimize both the processes—ablation and ionization. This new technique can thus be potentially employed to undertake in situ analysis of materials imbedded in diverse media, such as cryogenic ices, biological samples, tissues, minerals, etc., by covered with an IR-absorbing laser ablation medium and study the chemical composition and reaction pathways of the analyte in its natural surroundings.« less

Computational Study of Interstellar Glycine Formation Occurring at Radical Surfaces of Water-ice Dust Particles

NASA Astrophysics Data System (ADS)

Rimola, Albert; Sodupe, Mariona; Ugliengo, Piero

2012-07-01

Glycine is the simplest amino acid, and due to the significant astrobiological implications that suppose its detection, the search for it in the interstellar medium (ISM), meteorites, and comets is intensively investigated. In the present work, quantum mechanical calculations based on density functional theory have been used to model the glycine formation on water-ice clusters present in the ISM. The removal of either one H atom or one electron from the water-ice cluster has been considered to simulate the effect of photolytic radiation and of ionizing particles, respectively, which lead to the formation of OH• radical and H3O+ surface defects. The coupling of incoming CO molecules with the surface OH• radicals on the ice clusters yields the formation of the COOH• radicals via ZPE-corrected energy barriers and reaction energies of about 4-5 kcal mol-1 and -22 kcal mol-1, respectively. The COOH• radicals couple with incoming NH=CH2 molecules (experimentally detected in the ISM) to form the NHCH2COOH• radical glycine through energy barriers of 12 kcal mol-1, exceedingly high at ISM cryogenic temperatures. Nonetheless, when H3O+ is present, one proton may be barrierless transferred to NH=CH2 to give NH2=CH2 +. This latter may react with the COOH• radical to give the NH2CH2COOH+• glycine radical cation which can then be transformed into the NH2CHC(OH)2 +• species (the most stable form of glycine in its radical cation state) or into the NH2CHCOOH• neutral radical glycine. Estimated rate constants of these events suggest that they are kinetically feasible at temperatures of 100-200 K, which indicate that their occurrence may take place in hot molecular cores or in comets exposed to warmer regions of solar systems. Present results provide quantum chemical evidence that defects formed on water ices due to the harsh-physical conditions of the ISM may trigger reactions of cosmochemical interest. The relevance of surface H3O+ ions to facilitate chemical processes by proton transfer (i.e., acting as acidic catalysts) is highlighted, and plausible ways of their formation at the water-ice surface in the ISM are also discussed.

Fourier transform infrared studies of the interaction of HCl with model polar stratospheric cloud films

NASA Technical Reports Server (NTRS)

Koehler, Birgit G.; Mcneill, Laurie S.; Middlebrook, Ann M.; Tolbert, Margaret A.

1993-01-01

Heterogeneous reactions involving hydrochloric acid adsorbed on the surfaces of polar stratospheric clouds (PSCs) are postulated to contribute to polar ozone loss. Using FTIR spectroscopy to probe the condensed phase, we have examined the interaction of HCl with ice and nitric acid trihydrate (NAT) films representative of types II and I PSCs, respectively. For HCl pressures in the range of 10 exp -7 to 10 exp -5 Torr, our FTIR studies show that a small amount of crystalline HCl-6H2O formed on or in ice at 155 K. However, for higher HCl pressures, we observed that the entire film of ice rapidly converted into an amorphous 4:1 H2O:HCl mixture. From HCl-uptake experiments with P(HCl) = 8 x 10 exp -7 Torr, we estimate roughly that the diffusion coefficient of HCl in ice is around 2 x 10 exp -12 sq cm/s at 158 K. For higher temperatures more closely approximating those found in the stratosphere, we were unable to detect bulk HCl uptake by ice. Indirect evidence suggests that HCl adsorption onto the surface of model PSC films inhibited the evaporation of both ice and NAT by 3-5 K.

Observed ices in the Solar System

USGS Publications Warehouse

Clark, Roger N.; Grundy, Will; Carlson, Robert R.; Noll, Keith; Gudipati, Murthy; Castillo-Rogez, Julie C.

2013-01-01

Ices have been detected and mapped on the Earth and all planets and/or their satellites further from the sun. Water ice is the most common frozen volatile observed and is also unambiguously detected or inferred in every planet and/or their moon(s) except Venus. Carbon dioxide is also extensively found in all systems beyond the Earth except Pluto although it sometimes appears to be trapped rather than as an ice on some objects. The largest deposits of carbon dioxide ice is on Mars. Sulfur dioxide ice is found in the Jupiter system. Nitrogen and methane ices are common beyond the Uranian system. Saturn’s moon Titan probably has the most complex active chemistry involving ices, with benzene (C6H6) and many tentative or inferred compounds including ices of Cyanoacetylene (HC3N), Toluene (C7H8), Cyanogen (C2N2), Acetonitrile (CH3CN), H2O, CO2, and NH3. Confirming compounds on Titan is hampered by its thick smoggy atmosphere. Ammonia was predicted on many icy moons but is notably absent among the definitively detected ices with the possible exception of Enceladus. Comets, storehouses of many compounds that could exist as ices in their nuclei, have only had small amounts of water ice definitively detected on their surfaces. Only one asteroid has had a direct detection of surface water ice, although its presence can be inferred in others. This chapter reviews some of the properties of ices that lead to their detection, and surveys the ices that have been observed on solid surfaces throughout the Solar System.

Detection of Deuterium in Icy Surfaces and the D/H Ratio of Icy Objects

NASA Astrophysics Data System (ADS)

Clark, Roger Nelson; Brown, Robert H.; Swayze, Gregg A.; Cruikshank, Dale P.

2017-10-01

Water ice in crystalline or amorphous form is orientationally disordered, which results in very broad absorptions. Deuterium in trace amounts goes into an ordered position, so is not broadened like H2O absorptions. The D-O stretch is located at 4.13 microns with a width of 0.027 micron. Laboratory spectral measurements on natural H2O and deuterium doped ice show the absorption is slightly asymmetric and in reflectance the band shifts from 4.132 to 4.137 microns as abundance decreases. We derive a preliminary absorption coefficient of ~ 80,000 cm^-1 for the D-O stretch compared to about 560 cm^-1 in H2O ice at 4.13 microns, enabling the detection of deuterium at levels less than Vienna Standard Mean Ocean Water (VSMOW), depending on S/N. How accurate the D/H ratios can be derived will require additional lab work and radiative transfer modeling to simultaneously derive the grain size distribution, the abundance of any contaminants, and deuterium abundance. To first order, the grain size distribution can be compensated by computing the D-O stretch band depth to 2-micron H2O ice band depth ratio, which we call Dratio. Colorado fresh water (~80% of VSMOW) has a Dratio of 0.036, at a D/H = 0.0005, the Dratio = 0.15, and at a D/H = 0.0025, the Dratio = 0.42. The VSMOW Dratio is ~ 0.045.We have used VIMS data from the Cassini spacecraft to compute large spectral averages to detect the deuterium in the rings and on the icy satellite surfaces. A B-ring, 21,882 pixel average, at 640 ms/pixel, or 3.89 hours of integration time, shows a 3.5% O-D stretch band depth and a Dratio = 0.045, indicating deuterium abundance equal to VSMOW. Rhea, using 1.89 hours of integration time shows Dratio = 0.052, or slightly higher than VSMOW. Phoebe has an unusually deep O-D stretch band of 1.85% considering the high abundance of dark material suppressing the ice absorptions. We measure a Dratio = 0.11, an enhancement of ~2.4 over VSMOW, but detailed radiative transfer modeling is needed to derive a more accurate ratio. The enhancement is consistent with previous studies that suggest Phoebe's origin might be external to the Saturn system. More satellites and radiative transfer modeling results will be shown at the meeting.

Constraining the processes modifying the surfaces of the classical Uranian satellites

NASA Astrophysics Data System (ADS)

Cartwright, Richard J.; Emery, Joshua P.

2016-10-01

Near-infrared (NIR) observations of the classical Uranian moons have detected relatively weak H2O ice bands, mixed with a spectrally red, low albedo constituent on the surfaces of their southern hemispheres (sub-observer lat. ~10 - 75°S). The H2O bands and the degree of spectral reddening are greatest on the leading hemispheres of these moons. CO2 ice bands have been detected in spectra collected over their trailing hemispheres, with stronger CO2 bands on the moons closest to Uranus. Our preferred hypotheses to explain the distribution of CO2, H2O, and dark material are: bombardment by magnetospherically-embedded charged particles, primarily on the trailing hemispheres of these moons, and bombardment by micrometeorites, primarily on their leading hemispheres.To test these complementary hypotheses, we are constraining the distribution and spectral characteristics of surface constituents on the currently observable northern hemispheres (sub-observer lat. ~20 - 35°N) to compare with existing southern hemisphere data. Analysis of northern hemisphere data shows that CO2 is present on their trailing hemispheres, and H2O bands and the degree of spectral reddening are strongest on their leading hemispheres, in agreement with the southern hemisphere data. This longitudinal distribution of constituents supports our preferred hypotheses.However, tantalizing mysteries regarding the distribution of constituents remain. There has been no detection of CO2 on Miranda, and H2O bands are stronger on its trailing hemisphere. NIR slope measurements indicate that the northern hemisphere of Titania is redder than Oberon, unlike the spectral colors of their southern hemispheres. There are latitudinal variations in H2O band strengths on these moons, with stronger H2O bands at northern latitudes compared to southern latitudes on Umbriel and Titania. Several Miranda and Ariel spectra potentially include weak and unconfirmed NH3-hydrate bands, which could be tracers of cryovolcanic emplacement. We will present work related to our goals of constraining the processes modifying the surfaces of the classical Uranian moons.

Surface chemistry in photodissociation regions

NASA Astrophysics Data System (ADS)

Esplugues, G. B.; Cazaux, S.; Meijerink, R.; Spaans, M.; Caselli, P.

2016-06-01

Context. The presence of dust can strongly affect the chemical composition of the interstellar medium. We model the chemistry in photodissociation regions (PDRs) using both gas-phase and dust-phase chemical reactions. Aims: Our aim is to determine the chemical compositions of the interstellar medium (gas/dust/ice) in regions with distinct (molecular) gas densities that are exposed to radiation fields with different intensities. Methods: We have significantly improved the Meijerink PDR code by including 3050 new gas-phase chemical reactions and also by implementing surface chemistry. In particular, we have included 117 chemical reactions occurring on grain surfaces covering different processes, such as adsorption, thermal desorption, chemical desorption, two-body reactions, photo processes, and cosmic-ray processes on dust grains. Results: We obtain abundances for different gas and solid species as a function of visual extinction, depending on the density and radiation field. We also analyse the rates of the formation of CO2 and H2O ices in different environments. In addition, we study how chemistry is affected by the presence/absence of ice mantles (bare dust or icy dust) and the impact of considering different desorption probabilities. Conclusions: The type of substrate (bare dust or icy dust) and the probability of desorption can significantly alter the chemistry occurring on grain surfaces, leading to differences of several orders of magnitude in the abundances of gas-phase species, such as CO, H2CO, and CH3OH. The type of substrate, together with the density and intensity of the radiation field, also determine the threshold extinction to form ices of CO2 and H2O. We also conclude that H2CO and CH3OH are mainly released into the gas phase of low, far-ultraviolet illuminated PDRs through chemical desorption upon two-body surface reactions, rather than through photodesorption.

Condensation and vaporization studies of CH3OH and NH3 ices: Major implications for astrochemistry

NASA Technical Reports Server (NTRS)

Sandford, Scott A.; Allamandola, Louis J.

1993-01-01

In an extension of previously reported work on ices containing H2O, CO, CO2, SO2, H2S, and H2, we present measurements of the physical and infrared spectral properties of ices containing CH3OH and NH3. The condensation and sublimation behavior of these ice systems is discussed and surface binding energies are presented for all of these molecules. The surface binding energies can be used to calculate the residence times of the molecules on grain surfaces as a function of temperature. It is demonstrated that many of the molecules used to generate radio maps of and probe conditions in dense clouds, for example CO and NH3, will be significantly depleted from the gas phase by condensation onto dust grains. Attempts to derive total column densities solely from radio maps that do not take condensation effects into account may vastly underestimate the true column densities of any given species. Simple CO condensation onto and vaporization off of grains appears to be capable of explaining the observed depletion of gas phase CO in cold, dense molecular cores. This is not the case for NH3, however, where thermal considerations alone predict that all of the NH3 should be condensed onto grains. The fact that some gas phase NH3 is observed indicates that additional desorption processes must be involved. The surface binding energies of CH3OH, in conjunction with this molecule's observed behavior during warm up in H2O-rich ices, is shown to provide an explanation of the large excess of CH3OH seen in many warm, dense molecular cores. The near-infrared spectrum and associated integrated band strengths of CH3OH-containing ice are given, as are middle infrared absorption band strengths for both CH3OH and NH3.

Photochemistry of Polycyclic Aromatic Hydrocarbons in Cosmic Water Ice: The Role of PAH Ionization and Concentration

NASA Astrophysics Data System (ADS)

Cook, Amanda M.; Ricca, Alessandra; Mattioda, Andrew L.; Bouwman, Jordy; Roser, Joseph; Linnartz, Harold; Bregman, Jonathan; Allamandola, Louis J.

2015-01-01

Infrared spectroscopic studies of ultraviolet (UV) irradiated, water-rich, cosmic ice analogs containing small polycyclic aromatic hydrocarbons (PAHs) are described. The irradiation studies of anthracene:H2O, pyrene:H2O, and benzo[ghi]perylene:H2O ices (14 K) at various concentrations reported by Bouwman et al. are extended. While aromatic alcohols and ketones have been reported in residues after irradiated PAH:H2O ices were warmed to 270 K, it was not known if they formed during ice irradiation or during warm-up when reactants interact as H2O sublimes. Recent work has shown that they form in low temperature ice. Using DFT computed IR spectra to identify photoproducts and PAH cations, we tentatively identify the production of specific alcohols [PAH(OH) n ] and quinones [PAH(O) n ] for all PAH:H2O ices considered here. Little evidence is found for hydrogenation at 14 K, consistent with the findings of Gudipati & Yang. Addition of O and OH to the parent PAH is the dominant photochemical reaction, but PAH erosion to smaller PAHs (producing CO2 and H2CO) is also important. DFT spectra are used to assess the contribution of PAH-related species to interstellar absorption features from 5 to 9 μm. The case is made that PAH cations are important contributors to the C2 component and PAH(OH) n and PAH(O) n to the C5 component described by Boogert et al. Thus, interstellar ices should contain neutral and ionized PAHs, alcohols, ketones and quinones at the ~2%-4% level relative to H2O. PAHs, their photoproducts, and ion-mediated processes should therefore be considered when modeling interstellar ice processes.

The radiation stability of the RNA base uracil in H2O-ice and CO2-ice: in-situ laboratory measurements with applications to comets, Europa, and Mars

NASA Astrophysics Data System (ADS)

Gerakines, Perry A.; Frail, Sarah; Hudson, Reggie L.

2017-10-01

Planetary bodies of astrobiological interest, such as Mars, are often exposed to harsh incident radiation, which will influence the times that molecules can survive on them. Some or all of these bodies may well contain biologically-important organic molecules, some may even have supported life at some point in their history, and some may support life today. Future searches for organic molecules likely will include sampling the martian subsurface or a cometary surface sample return mission, where organics may be frozen in ices dominated by either H2O or CO2, which provide some protection from ionizing radiation.Recently, our research group has published studies of the radiation stability of amino acids, with a focus on glycine - in both undiluted form and in mixtures with H2O and CO2. Here, we present a similar study that focuses on the radiation-chemical kinetics of the RNA base uracil. We compare results for uracil decay for dilution in both H2O and CO2 ices. Moreover, we compare these new results with those for glycine. For each sample, we measured uracil’s destruction rate constant and half-life dose due to irradiation by 0.9-MeV protons. All measurements were made in situ at the temperature of irradiation using IR spectroscopy. Trends with dilution (up to ~300:1) and temperature (up to ~150 K) are considered, and results are discussed in the context of icy planetary surfaces.Acknowledgment: Our work is supported in part by the NASA Emerging Worlds Program and by the NASA Astrobiology Institute through the Goddard Center for Astrobiology.

0.2 to 10 keV electrons interacting with water ice: Radiolysis, sputtering, and sublimation

NASA Astrophysics Data System (ADS)

Galli, A.; Vorburger, A.; Wurz, P.; Pommerol, A.; Cerubini, R.; Jost, B.; Poch, O.; Tulej, M.; Thomas, N.

2018-06-01

We present new laboratory experiments investigating various water ice samples, ranging from thin ice films to porous thick ice layers, that are irradiated with electrons. The molecules leaving the ice are monitored with a pressure gauge and a mass spectrometer. Most particles released from the ice are H2 and O2, the observed ratio of 2:1 is consistent with H2O being radiolysed into H2 + 1/2 O2 upon irradiation. H2O2 is likely a minor contribution of radiolysis, amounting to 0.001 ± 0.001 of the total gas release from the ice sample. Neither the physical properties of the ice, nor the energy, nor the electron impact angle have any obvious effect on the relative abundances of the radiolysis products. The absolute sputtering yield (i.e., the ratio of produced O2 or destroyed H2O per impacting electron) increases with energy until a few 100 eV. For higher energies up to 10 keV the yield remains roughly constant, once the saturation dose of the ice is reached. This indicates that ongoing irradiation eventually releases the radiolysis products from the water ice even for penetration depths of several micrometers.

New Optical Constants for Amorphous and Crystalline H2O-ice and H2O-mixtures.

NASA Technical Reports Server (NTRS)

Mastrapa, Rachel; Bernstein, Max; Sandford, Scott

2006-01-01

We will present the products of new laboratory measurements of ices relevant to Trans-Neptunian Objects. We have calculated the real and imaginary indices of refraction for amorphous and crystalline H2O-ice and also H2O-rich ices containing other molecular species. We create ice samples by condensing gases onto a cold substrate. We measure the thickness of the sample by reflecting a He-Ne laser off of the sample and counting interference fringes as it grows. We then collect transmission spectra of the samples in the wavelength range from 0.7-22 micrometers. Using the thickness and the transmission spectra of the ice we calculate the imaginary part of the index of refraction. We then use a Kramers-Kronig calculation to calculate the real part of the index of refraction (Berland et al. 1994; Hudgins et al. 1993). These optical constants can then be used to create model spectra for comparison to spectra from Solar System objects, including TNOs. We will summarize the difference between the amorphous and crystalline H2O-ice spectra. These changes include weakening of features and shifting of features to shorter wavelength. One important result is that the 2 pm feature is stronger in amorphous H2O ice than it is in crystalline H2O-ice. We will also discuss the changes seen when H2O is mixed with other components, including CO2, CH4, HCN, and NH3 (Bernstein et al. 2005; Bernstein et al. 2006).

Study of the photon-induced formation and subsequent desorption of CH3OH and H2CO in interstellar ice analogs

NASA Astrophysics Data System (ADS)

Martín-Doménech, R.; Muñoz Caro, G. M.; Cruz-Díaz, G. A.

2016-05-01

Context. Methanol and formaldehyde are two simple organic molecules that are ubiquitously detected in the interstellar medium, in both the solid and gaseous phases. An origin in the solid phase and a subsequent nonthermal desorption into the gas phase is often invoked to explain their abundances in some of the environments where they are found. Experimental simulations under astrophysically relevant conditions have been carried out in the past four decades in order to find a suitable mechanism for that process. Aims: In particular, photodesorption from pure methanol ice (and presumably from pure formaldehyde ice) has been found to be negligible in previous works, probably because both molecules are very readily dissociated by vacuum-UV photons. Therefore, we explore the in situ formation and subsequent photon-induced desorption of these species, studying the UV photoprocessing of pure ethanol ice, and a more realistic binary H2O:CH4 ice analog. Methods: Experimental simulations were performed in an ultra-high vacuum chamber. Pure ethanol and binary H2O:CH4 ice samples deposited onto an infrared transparent window at 8 K were UV-irradiated using a microwave-discharged hydrogen flow lamp. Evidence of photochemical production of these two species and subsequent UV-photon-induced desorption into the gas phase were searched for by means of a Fourier transform infrared spectrometer and a quadrupole mass spectrometer, respectively. After irradiation, ice samples were warmed up to room temperature until complete sublimation was attained for detection of volatile products. Results: Formation of CH3OH was only observed during photoprocessing of the H2O:CH4 ice analog, accounting for ~4% of the initial CH4 ice column density, but no photon-induced desorption was detected. Photochemical production of H2CO was observed in both series of experiments. Formation of formaldehyde accounted for ≤45% conversion of the initial ethanol ice, but it could not be quantified during irradiation of the binary H2O:CH4 ice analogs. Photochemidesorption of formaldehyde, I.e., photon-induced formation on the ice surface and inmediate desorption, was observed, with a yield of ~6 × 10-5 (molecules/incident photon) in the case of the pure ethanol ice experiments, and ~4.4 × 10-5 (molecules/incident photon) when the H2O:CH4 ice analogs were photoprocessed. Photoprocessing of the ice analogs lead to formation of other species. Some of them were also found to desorb upon UV irradiation. Conclusions: While certain C-bearing species, in particular H2CO, were found to desorb upon irradiation, nonthermal desorption of CH3OH was not observed. So far, there is no experimental evidence of any efficient CH3OH desorption induced by UV photons. On the other hand, the observed photon-induced desorption of H2CO could account for the total formaldehyde abundance observed in the Horsehead photodissociation-dominated region.

SYSTEMATIC VARIATIONS IN CO{sub 2}/H{sub 2}O ICE ABUNDANCE RATIOS IN NEARBY GALAXIES FOUND WITH AKARI NEAR-INFRARED SPECTROSCOPY

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yamagishi, M.; Kaneda, H.; Ishihara, D.

2015-07-01

We report CO{sub 2}/H{sub 2}O ice abundance ratios in seven nearby star-forming galaxies based on the AKARI near-infrared (2.5–5.0 μm) spectra. The CO{sub 2}/H{sub 2}O ice abundance ratios show clear variations between 0.05 and 0.2 with the averaged value of 0.14 ± 0.01. The previous study on M82 revealed that the CO{sub 2}/H{sub 2}O ice abundance ratios strongly correlate with the intensity ratios of the hydrogen recombination Brα line to the polycyclic aromatic hydrocarbon (PAH) 3.3 μm feature. In the present study, however, we find no correlation for the seven galaxies as a whole due to systematic differences in themore » relation between CO{sub 2}/H{sub 2}O ice abundance and Brα/PAH 3.3 μm intensity ratios from galaxy to galaxy. This result suggests that there is another parameter that determines the CO{sub 2}/H{sub 2}O ice abundance ratios in a galaxy in addition to the Brα/PAH 3.3 μm ratios. We find that the CO{sub 2}/H{sub 2}O ice abundance ratios positively correlate with the specific star formation rates of the galaxies. From these results, we conclude that CO{sub 2}/H{sub 2}O ice abundance ratios tend to be high in young star-forming galaxies.« less

Thermal Reactions Between Sulfur Dioxide and H202 and Their Relevance to the Jovian Icy Satellites and Other Small Bodies

NASA Technical Reports Server (NTRS)

Loefler, Mark J.; Hudson, Reggie L.

2011-01-01

Laboratory experiments have demonstrated that magnetospheric radiation in the Jovian system drives reaction chemistry in ices at temperatures relevant to Europa and other icy satellites. Here we present new results on thermally-induced reactions occurring between 50 and 130 K in solid H2O + H2O2 + SO2 samples. In our studies, we find that warming our three component mixtures induces a thermal reaction that produces SO4(2-), and this reaction appears to consume equal amounts of H2O2 and SO2. We suspect that the results may explain some of the observations related to the presence and distribution H2O2 across Europa's surface as well as the lack of H2O2 on Ganymede and Callisto. If other molecules prove to be reactive with H2O2 at these or at even lower temperatures, then it may also explain why H2O2 has been absent from surfaces of many of the small icy bodies that are known to be exposed to ionizing radiation.

The GEM-Mars general circulation model for Mars: Description and evaluation

NASA Astrophysics Data System (ADS)

Neary, L.; Daerden, F.

2018-01-01

GEM-Mars is a gridpoint-based three-dimensional general circulation model (GCM) of the Mars atmosphere extending from the surface to approximately 150 km based on the GEM (Global Environmental Multiscale) model, part of the operational weather forecasting and data assimilation system for Canada. After the initial modification for Mars, the model has undergone considerable changes. GEM-Mars is now based on GEM 4.2.0 and many physical parameterizations have been added for Mars-specific atmospheric processes and surface-atmosphere exchange. The model simulates interactive carbon dioxide-, dust-, water- and atmospheric chemistry cycles. Dust and water ice clouds are radiatively active. Size distributed dust is lifted by saltation and dust devils. The model includes 16 chemical species (CO2, Argon, N2, O2, CO, H2O, CH4, O3, O(1D), O, H, H2, OH, HO2, H2O2 and O2(a1Δg)) and has fully interactive photochemistry (15 reactions) and gas-phase chemistry (31 reactions). GEM-Mars provides a good simulation of the water and ozone cycles. A variety of other passive tracers can be included for dedicated studies, such as the emission of methane. The model has both a hydrostatic and non-hydrostatic formulation, and together with a flexible grid definition provides a single platform for simulations on a variety of horizontal scales. The model code is fully parallelized using OMP and MPI. Model results are evaluated by comparison to a selection of observations from instruments on the surface and in orbit, relating to atmosphere and surface temperature and pressure, dust and ice content, polar ice mass, polar argon, and global water and ozone vertical columns. GEM-Mars will play an integral part in the analysis and interpretation of data that is received by the NOMAD spectrometer on the ESA-Roskosmos ExoMars Trace Gas Orbiter. The present paper provides an overview of the current status and capabilities of the GEM-Mars model and lays the foundations for more in-depth studies in support of the NOMAD mission.

Processing of ammonia-containing ices by heavy ions and its relevance to outer Solar System surfaces

NASA Astrophysics Data System (ADS)

Pilling, Sergio; Seperuelo Duarte, Eduardo; da Silveira, Enio F.; Domaracka, Alicja; Balanzat, Emmanuel; Rothard, Hermann; Boduch, Philippe

Ammonia-containing ices have been detected or postulated as important components of the icy surfaces of planetary satellites (e.g. Enceladus, Miranda), in the outer Solar System objects (e.g. Charon, Quaoar) and in Oort cloud comets. We present experimental studies of the interaction of heavy, highly-charged, and energetic ions with ammonia-containing ices (pure NH3 ; NH3 :CO; NH3 :H2 O and NH3 :H2 O:CO) in an attempt to simulate the physical chemistry induced by heavy-ion cosmic rays and heavy-ion solar wind particles at outer Solar System surfaces. The measurements were performed inside a high vacuum chamber at the heavy-ion accelerator GANIL (Grand Accelerateur National d'Ions Lourds) in Caen, France. The gas samples were deposited onto a polished CsI substrate previously cooled to 13 K. In-situ analysis was performed by a Fourier transform infrared spectrometer (FTIR) at different ion fluences. The dissociation cross-section and sputtering yield of ammonia and other ice compounds have been determined. Half-life of frozen ammonia due to heavy ion bombardment at different Solar System surfaces has been estimated. Radiolysis products have been identified and their implications for the chemistry on outer Solar System surfaces are discussed.

The Formation of Complex Organic Compounds in Astrophysical Ices and their Implications for Astrobiology

NASA Technical Reports Server (NTRS)

Sandford, Scott A.

2015-01-01

Ices in astrophysical environments are generally dominated by very simple molecules like H2O, CH3OH, CH4, NH3, CO, CO2, etc, although they likely contain PAHs as well. These molecules, particularly H2O, are of direct interest to astrobiology in-and-of themselves since they represent some of the main carriers of the biogenic elements C, H, O, and N. In addition, these compounds are present in the dense interstellar clouds in which new stars and planetary systems are formed and may play a large role in the delivery of volatiles and organics to the surfaces of new planets. However, these molecules are all far simpler than the more complex organic compounds found in living systems.

Surface chemical properties of eutectic and frozen NaCl solutions probed by XPS and NEXAFS.

PubMed

Křepelová, Adéla; Huthwelker, Thomas; Bluhm, Hendrik; Ammann, Markus

2010-12-17

We study the surface of sodium chloride-water mixtures above, at, and below the eutectic temperature using X-ray photoelectron spectroscopy (XPS) and electron-yield near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The NaCl frozen solutions are mimicking sea-salt deposits in ice or snow. Sea-salt particles emitted from the oceans are a major contributor to the global aerosol burden and can act as a catalyst for heterogeneous chemistry or as cloud condensation nuclei. The nature of halogen ions at ice surfaces and their influence on surface melting of ice are of significant current interest. We found that the surface of the frozen solution, depending on the temperature, consists of ice and different NaCl phases, that is, NaCl, NaCl·2H(2)O, and surface-adsorbed water.

Laboratory Studies of Solid Carbon Dioxide in Planetary and Interstellar Ices

NASA Technical Reports Server (NTRS)

White, Douglas; Sandford, Scott A.; Mastrapa, Rachel M.

2012-01-01

Laboratory spectra have shown that CO2. is a powerful diagnostic tool for analyzing infrared data from remote observations, as it has been detected on icy moons in the outer solar system as well as dust grain surfaces in the interstellar medium. IR absorption profiles of CO2 wi thin ice mixtures containing H2O and CH30H change with respect to tem perature and mixture ratios. In this particular study, the CO2 stretch mode around 235O cm (exp -1) (4.3 rricrons) is systematically observ ed in different mixtures with H2O and CH30H in temperature ranges from 15K to 150 K, as well as vibrational modes in the near-IR such as th e combination bands near 3700 cm (exp -1) (2.7 microns) and 5080 (exp -1) (2.0 microns). Additionally, some high?temperature deposits (T > 50 K) of H2O, CH30H, and CO2 ice mixtures were performed to determine the maximum temperatures at which CO2 will deposit on the sample win dow. These data may then be used to interpret spectra obtained from remote IR observations. This research was sponsored by Oak Ridge Associ ated Universities (ORAU) through the NASA Postdoctoral Program (NPP) as well as Ames Research Center and the SETI institute who provided fa cilities and equipment.

Ceres: predictions for near-surface water ice stability and implications for plume generating processes

USGS Publications Warehouse

Titus, Timothy N.

2015-01-01

This paper will constrain the possible sources and processes for the formation of recently observed H2O vapor plumes above the surface of the dwarf planet Ceres. Two hypotheses have been proposed: (1) cryovolcanism where the water source is the mantle and the heating source is still unknown or (2) comet-like sublimation where near-surface water ice is vaporized by seasonally increasing solar insolation. We test hypothesis #2, comet-like near-surface sublimation, by using a thermal model to examine the stability of water-ice in the near surface. For a reasonable range of physical parameters (thermal inertia, surface roughness, slopes), we find that water ice is only stable at latitudes higher than ~40-60 degrees. These results indicate that either (a) the physical properties of Ceres are unlike our expectations or (b) an alternative to comet-like sublimation, such as the cryovolcanism hypothesis, must be invoked.

Photoionization in Ultraviolet Processing of Astrophysical Ice Analogs at Cryogenic Temperatures

NASA Technical Reports Server (NTRS)

Woon, David E.

2004-01-01

Two recent experimental studies have demonstrated that amino acids or amino acid precursors are generated when astrophysical ice analogs are subjected to ultraviolet (UV) irradiation at cryogenic temperatures. Understanding the complete phenomenology of photoprocessing is critical to elucidating chemical reaction mechanisms that can function within an ice matrix under very cold conditions. Pushing beyond the much better characterized study of photolytic dissociation of chemical bonds through electronic excitation, this work explored the ability of UV radiation present in the interstellar medium to ionize small molecules embedded in ices. Quantum chemical calculations, including bulk solvation effects, were used to study the ionization of hydrogen (H2), water, and methanol (CH3OH) bound in small clusters of water. Ionization potentials were found to be much smaller in the condensed phase than in the gas phase; even a small cluster can account for large changes in the ionization potentials in ice, as well as the known formation of an OH--H3O+ pair in the case of H2O photoionization. To gauge the impact of photoionization on subsequent grain chemistry, the reaction between OH and CO in the presence of H3O+ was studied and compared with the potential energy surface without hydronium present, which is relevant to chemistry following photolysis. The differences indicate that the reaction is somewhat more likely to proceed to products (H + CO2) in the case of photoionization.

Ices on Mercury: Chemistry of volatiles in permanently cold areas of Mercury's north polar region

NASA Astrophysics Data System (ADS)

Delitsky, M. L.; Paige, D. A.; Siegler, M. A.; Harju, E. R.; Schriver, D.; Johnson, R. E.; Travnicek, P.

2017-01-01

Observations by the MESSENGER spacecraft during its flyby and orbital observations of Mercury in 2008-2015 indicated the presence of cold icy materials hiding in permanently-shadowed craters in Mercury's north polar region. These icy condensed volatiles are thought to be composed of water ice and frozen organics that can persist over long geologic timescales and evolve under the influence of the Mercury space environment. Polar ices never see solar photons because at such high latitudes, sunlight cannot reach over the crater rims. The craters maintain a permanently cold environment for the ices to persist. However, the magnetosphere will supply a beam of ions and electrons that can reach the frozen volatiles and induce ice chemistry. Mercury's magnetic field contains magnetic cusps, areas of focused field lines containing trapped magnetospheric charged particles that will be funneled onto the Mercury surface at very high latitudes. This magnetic highway will act to direct energetic protons, ions and electrons directly onto the polar ices. The radiation processing of the ices could convert them into higher-order organics and dark refractory materials whose spectral characteristics are consistent with low-albedo materials observed by MESSENGER Laser Altimeter (MLA) and RADAR instruments. Galactic cosmic rays (GCR), scattered UV light and solar energetic particles (SEP) also supply energy for ice processing. Cometary impacts will deposit H2O, CH4, CO2 and NH3 raw materials onto Mercury's surface which will migrate to the poles and be converted to more complex Csbnd Hsbnd Nsbnd Osbnd S-containing molecules such as aldehydes, amines, alcohols, cyanates, ketones, hydroxides, carbon oxides and suboxides, organic acids and others. Based on lab experiments in the literature, possible specific compounds produced may be: H2CO, HCOOH, CH3OH, HCO, H2CO3, CH3C(O)CH3, C2O, CxO, C3O2, CxOy, CH3CHO, CH3OCH2CH2OCH3, C2H6, CxHy, NO2, HNO2, HNO3, NH2OH, HNO, N2H2, N3, HCN, Na2O, NaOH, CH3NH2, SO, SO2, SO3, OCS, H2S, CH3SH, even BxHy. Three types of radiation processing mechanisms may be at work in the ices: (1) Impact/dissociation, (2) Ion implantation and (3) Nuclear recoil (hot atom chemistry). Magnetospheric energy sources dominate the radiation effects. Total energy fluxes of photons, SEPs and GCRs are all around two or more orders of magnitude less than the fluxes from magnetospheric energy sources (in the focused cusp particles). However, SEPs and GCRs cause chemical processing at greater depths than other particles leading to thicker organic layers. Processing of polar volatiles on Mercury would be somewhat different from that on the Moon because Mercury has a magnetic field while the Moon does not. The channeled flux of charged particles through these magnetospheric cusps is a chemical processing mechanism unique to Mercury as compared to other airless bodies.

Physical chemistry of the H2SO4/HNO3/H2O system - Implications for polar stratospheric clouds

NASA Technical Reports Server (NTRS)

Molina, M. J.; Zhang, R.; Wooldridge, P. J.; Mcmahon, J. R.; Kim, J. E.; Chang, H. Y.; Beyer, K. D.

1993-01-01

Polar stratospheric clouds (PSCs) play a key role in stratospheric ozone depletion. Surface-catalyzed reactions on PSC particles generate chlorine compounds that photolyze readily to yield chlorine radicals, which in turn destroy ozone very efficiently. The most prevalent PSCs form at temperatures several degrees above the ice frost point and are believed to consist of HNO3 hydrates; however, their formation mechanism is unclear. Results of laboratory experiments are presented which indicate that the background stratospheric H2SO4/H2O aerosols provide an essential link in this mechanism: These liquid aerosols absorb significant amounts of HNO3 vapor, leading most likely to the crystallization of nitric acid trihydrate (NAT). The frozen particles then grow to form PSCs by condensation of additional amounts of HNO3 and H2O vapor. Furthermore, reaction probability measurements reveal that the chlorine radical precursors are formed readily at polar stratospheric temperatures not just on NAT and ice crystals, but also on liquid H2SO4 solutions and on solid H2SO4 hydrates. These results imply that the chlorine activation efficiency of the aerosol particles increases rapidly as the temperature approaches the ice frost point regardless of the phase or composition of the particles.

Experimentally Determined Binding Energies of Astrophysically Relevant Hydrocarbons in Pure and H2O-Layered Ices

NASA Astrophysics Data System (ADS)

Behmard, Aida; Graninger, Dawn; Fayolle, Edith; Oberg, Karin I.

2017-01-01

Small hydrocarbons represent an important organic reservoir in a variety of interstellar environments. Constraints on desorption temperatures and binding energies of hydrocarbons are thus necessary for accurate predictions of where and in which phase these molecules exist. Through a series of temperature programmed desorption experiments, we determined binding energies of 1, 2, and 3-carbon interstellar hydrocarbons (CH4, C2H2, C2H4, C2H6, C3H4, C3H6, and C3H8) in pure ices and in relation to water ice, the dominant ice constituent during star and planet formation. These empirically determined values can be used to inform observations and models of the molecular spatial distribution in protoplanetary disks, thus providing insight into planetesimal composition. In addition, knowledge of hydrocarbon binding energies will refine simulations of grain surface chemistry, allowing for better predictions of the chemical conditions that lead to the production of complex organic molecules vital for life.

Ion Irradiation of Sulfuric Acid: Implications for its Stability on Europa

NASA Technical Reports Server (NTRS)

Loeffler, M. J.; Hudson, R. L.; Moore, M. H.

2010-01-01

The Galileo near-infrared mapping spectrometer (NIMS) detected regions on Europa's surface containing distorted H2O bands. This distortion likely indicates that there are other molecules mixed with the water ice. Based on spectral comparison, some of the leading possibilities are sulfuric acid, salts. or possibly H3O(+). Previous laboratory studies have shown that sulfuric acid can be created by irradiation of H2OSO2 mixtures, and both molecules are present on Europa. In this project, we were interested in investigating the radiation stability of sulfuric acid (H2SO4) and determining its lifetime on the surface of Europa.

Thermal desorption of formamide and methylamine from graphite and amorphous water ice surfaces

NASA Astrophysics Data System (ADS)

Chaabouni, H.; Diana, S.; Nguyen, T.; Dulieu, F.

2018-04-01

Context. Formamide (NH2CHO) and methylamine (CH3NH2) are known to be the most abundant amine-containing molecules in many astrophysical environments. The presence of these molecules in the gas phase may result from thermal desorption of interstellar ices. Aims: The aim of this work is to determine the values of the desorption energies of formamide and methylamine from analogues of interstellar dust grain surfaces and to understand their interaction with water ice. Methods: Temperature programmed desorption (TPD) experiments of formamide and methylamine ices were performed in the sub-monolayer and monolayer regimes on graphite (HOPG) and non-porous amorphous solid water (np-ASW) ice surfaces at temperatures 40-240 K. The desorption energy distributions of these two molecules were calculated from TPD measurements using a set of independent Polanyi-Wigner equations. Results: The maximum of the desorption of formamide from both graphite and ASW ice surfaces occurs at 176 K after the desorption of H2O molecules, whereas the desorption profile of methylamine depends strongly on the substrate. Solid methylamine starts to desorb below 100 K from the graphite surface. Its desorption from the water ice surface occurs after 120 K and stops during the water ice sublimation around 150 K. It continues to desorb from the graphite surface at temperatures higher than160 K. Conclusions: More than 95% of solid NH2CHO diffuses through the np-ASW ice surface towards the graphitic substrate and is released into the gas phase with a desorption energy distribution Edes = 7460-9380 K, which is measured with the best-fit pre-exponential factor A = 1018 s-1. However, the desorption energy distribution of methylamine from the np-ASW ice surface (Edes = 3850-8420 K) is measured with the best-fit pre-exponential factor A = 1012 s-1. A fraction of solid methylamine monolayer of roughly 0.15 diffuses through the water ice surface towards the HOPG substrate. This small amount of methylamine desorbs later with higher binding energies (5050-8420 K) that exceed that of the crystalline water ice (Edes = 4930 K), which is calculated with the same pre-exponential factor A = 1012 s-1. The best wetting ability of methylamine compared to H2O molecules makes CH3NH2 molecules a refractory species for low coverage. Other binding energies of astrophysical relevant molecules are gathered and compared, but we could not link the chemical functional groups (amino, methyl, hydroxyl, and carbonyl) with the binding energy properties. Implications of these high binding energies are discussed.

Dione and Rhea seasonal exospheres revealed by Cassini CAPS and INMS

NASA Astrophysics Data System (ADS)

Teolis, B. D.; Waite, J. H.

2016-07-01

A Dione O2 and CO2 exosphere of similar composition and density to Rhea's is confirmed by Cassini spacecraft Ion Neutral Mass Spectrometer (INMS) flyby data. INMS results from three Dione and two Rhea flybys show exospheric spatial and temporal variability indicative of seasonal exospheres, modulated by winter polar gas adsorption and desorption at the equinoxes. Cassini Plasma Spectrometer (CAPS) pickup ion fluxes also show exospheric structure and evolution at Rhea consistent with INMS, after taking into consideration the anticipated charge exchange, electron impact, and photo-ionization rates. Data-model comparisons show the exospheric evolution to be consistent with polar frost diffusion into the surface regolith, which limits surface exposure and loss of the winter frost cap by sputtering. Implied O2 source rates of ∼45(7) × 1021 s-1 at Dione(Rhea) are ∼50(300) times less than expected from known O2 radiolysis yields from ion-irradiated pure water ice measured in the laboratory, ruling out secondary sputtering as a major exospheric contributor, and implying a nanometer scale surface refractory lag layer consisting of concentrated carbonaceous impurities. We estimate ∼30:1(2:1) relative O2:CO2 source rates at Dione(Rhea), consistent with a stoichiometric bulk composition below the lag layer of 0.01(0.13) C atoms per H2O molecule, deriving from endogenic constituents, implanted micrometeoritic organics, and (in particular at Dione) exogenous H2O delivery by E-ring grains. Impact deposition, gardening and vaporization may thereby control the global O2 source rates by fresh H2O ice exposure to surface radiolysis and trapped oxidant ejection.

PHOTOCHEMISTRY OF POLYCYCLIC AROMATIC HYDROCARBONS IN COSMIC WATER ICE: THE ROLE OF PAH IONIZATION AND CONCENTRATION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cook, Amanda M.; Mattioda, Andrew L.; Roser, Joseph

2015-01-20

Infrared spectroscopic studies of ultraviolet (UV) irradiated, water-rich, cosmic ice analogs containing small polycyclic aromatic hydrocarbons (PAHs) are described. The irradiation studies of anthracene:H{sub 2}O, pyrene:H{sub 2}O, and benzo[ghi]perylene:H{sub 2}O ices (14 K) at various concentrations reported by Bouwman et al. are extended. While aromatic alcohols and ketones have been reported in residues after irradiated PAH:H{sub 2}O ices were warmed to 270 K, it was not known if they formed during ice irradiation or during warm-up when reactants interact as H{sub 2}O sublimes. Recent work has shown that they form in low temperature ice. Using DFT computed IR spectra to identify photoproducts andmore » PAH cations, we tentatively identify the production of specific alcohols [PAH(OH) {sub n} ] and quinones [PAH(O) {sub n} ] for all PAH:H{sub 2}O ices considered here. Little evidence is found for hydrogenation at 14 K, consistent with the findings of Gudipati and Yang. Addition of O and OH to the parent PAH is the dominant photochemical reaction, but PAH erosion to smaller PAHs (producing CO{sub 2} and H{sub 2}CO) is also important. DFT spectra are used to assess the contribution of PAH-related species to interstellar absorption features from 5 to 9 μm. The case is made that PAH cations are important contributors to the C2 component and PAH(OH) {sub n} and PAH(O) {sub n} to the C5 component described by Boogert et al. Thus, interstellar ices should contain neutral and ionized PAHs, alcohols, ketones and quinones at the ∼2%-4% level relative to H{sub 2}O. PAHs, their photoproducts, and ion-mediated processes should therefore be considered when modeling interstellar ice processes.« less

Thermal infrared and visual observations of a water ice lag in the Mars southern summer

USGS Publications Warehouse

Titus, T.N.

2005-01-01

We present thermal infrared and visual evidence for the existence of water ice lags in the early southern summer. The observed H2O-ice lags lay in and near a chasma and appears to survive between 6-8 sols past the sublimation of the CO2. Possible sources of the H2O that compose the lag are (1) atmospheric H2O that is incorporated into the seasonal cap during condensation, (2) cold trapping of atmospheric water vapor onto the surface of the cap in the spring, or (3) a combination of the 2 processes where water is released from the sublimating cap only to be transported back over the cap edge and cold trapped. We refer to this later process as the "Houben" effect which may enrich the amount of water contained in the seasonal cap at 85??S by as much as a factor of 15. This phenomenon, which has already been identified for the northern retreating cap, may present an important water transport mechanism in the Southern Hemisphere.

Radiolysis and Photolysis of Icy Satellite Surfaces: Experiments and Theory

NASA Technical Reports Server (NTRS)

Cassidy, T.; Coll, P.; Raulin, F.; Carlson, R. W.; Hand, K. P.; Johnson, R. E.; Loeffler, M. J.; Baragiola, R. A.

2010-01-01

The transport and exchange of material between bodies in the outer solar system is often facilitated by their exposure to ionizing radiation. With this in mind we review the effects of energetic ions, electrons and UV photons on materials present in the outer solar system. We consider radiolysis, photolysis, and sputtering of low temperature solids. Radiolysis and photolysis are the chemistry that follows the bond breaking and ionization produced by incident radiation, producing, e.g., O2 and H2 from irradiated H2O ice. Sputtering is the ejection of molecules by incident radiation. Both processes are particularly effective on ices in the outer solar system. Materials reviewed include H2O ice, sulfur-containing compounds (such as S02 and S8), carboncontajning compounds (such as CH4), nitrogen-containing compounds (such as NH3 and N2), and mixtures of those compounds. We also review the effects of ionizing radiation on a mixture of N2 and CH4 gases, as appropriate to Titan's upper atmosphere, where radiolysis and photolysis produce complex organic compounds (tholins).

Large-scale volcano-ground ice interactions on Mars

USGS Publications Warehouse

Squyres, S. W.; Wilhelms, D.E.; Moosman, A.C.

1987-01-01

The process of volcano-ground ice interaction on Mars is investigated by thermodynamic calculations and observations of Viking Orbiter images. We develop a numerical model of volcano-ground ice interaction that includes heat transport by conduction, radiation from the surface, heat transfer to the atmosphere, and H2O phase changes in an ice-rich permafrost. We consider eruption of lava flows over permafrost, and intrusion of sills into permafrost. For eruption of lava over permafrost, most of the heat in the flow is lost by radiation and atmospheric effects. The amount of H2O liquid and vapor produced is small, and its removal would not be sufficient to cause collapse that would lower the surface of the lava flow below the surrounding terrain. For intrusion of a sill, most of the heat in the sill eventually goes into H2O phase changes, producing much larger amounts of water that could have profound geomorphic and geochemical effects. Approximate meltwater discharge rates are calculated for both extrusive and intrusive interactions. We examine two large regions of large-scale volcano-ground ice interactions. Near Aeolis Mensae, intrusion of a complex of dikes and sills into ice-rich ground has produced substantial melting, with mobilization and flow of material. This interaction probably also produced large quantities of palagonite tuff and breccia. Morphologic evidence for progressive fluidization implies that meltwater was stored beneath the surface for some time, and that most of the release of water and volcanic mudflow took place late in the interaction. Northeast of Hellas, several large channels emanate from the area near the volcano Hadriaca Patera. If genetically related to the volcanic activity, large collapse features at the sources of some channels must have originated due to heat from large buried magma bodies. A channel emerging directly from the base of Hadriaca Patera may have originated from release of heat from thick extruded material. Other small channels in the region results from heat released from surface lava flows. Inferred channel discharges may be compared to discharge rates calculated for lava-ground ice interactions. Such comparisons show that meltwater probably accumulated beneath the surface and then was released rapidly, with a discharge rate limited by soil permeability. Volcano-ground ice interaction has been a widespread and important geologic process on Mars, and may be the primary source of palagonites making up the ubiquitous Martian dust. ?? 1987.

Detecting Isotopic Signatures and Measuring Isotopic Ratios on Solid Icy Surfaces:Implications for Origin and Evolution

NASA Astrophysics Data System (ADS)

Clark, R. N.; Brown, R. H.; Swayze, G. A.; Cruikshank, D. P.

2017-12-01

Infrared spectroscopy has long been used to detect isotopes in planetaryatmospheres and in the galaxy. Given sufficient spectral resolution,or large enough changes in mass, isotopes are also detectable in solids.Gas absorption lines can be quite narrow, but in some solids, e.g. H2Oice, absorptions are very broad with little to no fine structure. H2O icehas broad absorptions due to its orientationally disordered structure butmany ices, minerals, and other compounds display sufficiently narrowabsorptions to enable detection of isotopes with small mass changes atmoderate spectral resolution.D2O ice and HDO ice also show orientationally-disordered spectra withvery broad absorption bands. But as deuterium decreases to low levelsdeuterium apparently goes into ordered sites in the H2O ice structure,producing narrow absorptions and shifting to longer wavelengths.Trace D2O condensed on basalt at 80 Kelvin shows an O-D stretch at 4.0microns, but at D/H 0.1 or less in H2O ice, the D-O stretch occursnear 4.13 microns with a width in reflectance decreasing to 0.027 micronas D/H decreases. The narrow D-O stretch absorption shows an absorptioncoefficient of 80,000 cm^-1 enabling detection below Vienna Standard MeanOcean Water (VSMOW) with achievable S/N in the lab and from spacecraft.Isotopes of carbon have been detected in CO2 on Saturn's satelliteswith 16 nm FWHM using the VIMS instrument on the Cassini spacecraft.Deuterium has been detected at close to terrestrial levels in Saturn'srings and on Rhea, and an apparent enhancement on Phoebe using VIMSdata. The ocean world Enceladus is currently being analyzed. We alsodetect an enhancement in 13C on Phoebe, but not on Iapetus or Rhea,consistent with the suggestion from previous studies that suggest Phoebe'sorigin might be external to the Saturn system. The MISE instrumenton the Europa Clipper mission has the capability to detect deuteriumand carbon isotopes in the Jupiter system. The higher temperaturesin the Jupiter system may result in more fractionation, depending upona given isotope and the physical processes involved, potentially withimplications for origin and evolution.

Geographic Distribution of N2, CH4, CO2, and H2O Ices on Triton from Near-IR Spectroscopic Monitoring

NASA Astrophysics Data System (ADS)

Grundy, W. M.; Young, L. A.; Young, E. F.; Buie, M. W.; Spencer, J. R.

2004-11-01

We present new 0.8 to 2.4 μ m spectral observations of Neptune's satellite Triton, obtained at IRTF\\slash SpeX between 2001 and 2004 as part of an ongoing search for time-variable phenomena associated with Triton's seasonal volatile transport processes, and also perhaps with reported shorter-term "reddening" events. The ability to detect spectral changes on these time scales depends critically on accurate characterization of any cyclic variations resulting from Triton's 5.877 day rotation period. We will report on our observations of periodic variations of Triton's near-IR absorption bands of N2, CH4, and H2O ices, but not of CO2 ice, in this initial stage of our Triton monitoring program. The observed variations (or lack thereof) give an indication of how these four ice species are distributed in longitude. The most heterogeneously distributed ice is N2, which shows nearly twice as much absorption on Triton's Neptune-facing hemisphere as on the anti-Neptune hemisphere. Comparison with Voyager-era, visual wavelength imaging of Triton's surface suggest that the observed N2 ice is concentrated on low-latitude regions of Triton's polar cap, which are predominantly located on the Neptune-facing hemisphere. Non-volatile H2O ice seems to be slightly concentrated on Triton's leading hemisphere. Despite being highly diluted in N2 ice, the longitudinal distribution of Triton's CH4 ice differs from that of Triton's N2 ice, being slightly concentrated on Triton's trailing hemisphere. Triton's CO2 ice shows the least longitudinal variation, suggesting that it is either very uniformly distributed or that it is confined to high latitudes. This work was supported by NASA's Planetary Astronomy and Planetary Geology &\\ Geophysics programs, and by NSF's Planetary Astronomy program. \\hangindent=0.3truein Grundy, W.M., and L.A. Young (2004) Near infrared spectral monitoring of Triton with IRTF\\slash SpeX I: Establishing a baseline. Icarus (in press).

Partial phase diagram for the system NH3-H2O - The water-rich region

NASA Technical Reports Server (NTRS)

Johnson, M. L.; Schwake, A.; Nicol, M.

1984-01-01

Phase boundaries of the H2O-NH3 system for (NH3)/x/(H2O)/1-x/ have been determined with diamond-anvil cells for mixtures in two composition ranges: (1) for x in the range from 0 to 0.3, at pressures up to 4 GPa at 21 C, and (2) for x in the range from 0.46 to 0.50, at pressures up to 5 GPa from 150 to 400 K. Phases were identified visually with a microscope and polarized optics. The NH3.2(H2O) phase is strongly anisotropic with a much smaller refractive index than that of ice VII and cracks in two nonperpendicular networks. NH3.H2O has a refractive index closer to that of Ice VII and does not appear to form cracks. Both phases are colorless. Phase boundaries were determined on both increasing and decreasing pressures, and compositions of the ammonia ices were determined by estimating relative amounts of water and ammonia ices at known overall compositions. For low-ammonia compositions (x equal to or less than 0.15), the following assemblages succedd one another as pressure increases: liquid; liquid and Ice VI (at 1.0 + GPa); liquid and Ice VII (at 2.1 GPa); Ice VII and NH3.H2O (at 3.5 GPa). For x in the range from 0.15 to 0.30, the water ice and liquid fields are replaced by the NH3.2(H2O) and liquid field at pressures down to 1.0 GPa and lower.

PAH-Mineral Interactions. A Laboratory Approach to Astrophysical Catalysis

NASA Astrophysics Data System (ADS)

Adolfo Cruz Diaz, Gustavo; Mattioda, Andrew

2017-06-01

Polycyclic Aromatic Hydrocarbon (PAH) molecules carry the infrared emission features which dominate the spectra of most galactic and extragalactic sources. Our study investigates the chemical evolution, chemical properties, physical properties, thermal stability, and photostability of samples produced from the UV-irradiation of simulated mineral dust grains coated with aromatics and astrobiologically relevant ices, using infrared spectroscopy. We investigate the chemical evolution of aromatic organics via anhydrous (no H2O ice) and hydrous (H2O ice) mechanisms. The anhydrous mechanism involves UV-induced catalytic reactions between organics and dense-cloud mineral grains, whereas the hydrous mechanism incorporates H2O-rich ice mixtures with the minerals and organics. These investigations identify the chemical and physical interactions occurring between the organic species, the dust grains and water-rich ices.These laboratory simulations also generate observable IR spectroscopic parameters for future astronomical observations with infrared telescopes such as SOFIA and JWST as well as provide empirical parameters for input into astronomical models of the early stages of planetary formation. These studies give us a deeper understanding of the potential catalytic pathways mineral surfaces provide and a deeper understanding of the role of ice-organic compositions in the chemical reaction pathways and how these processes fit into the formation of new planetary systems.In order to achieve these goals we use the Harrick ‘Praying Mantis’ Diffuse Reflectance Accessory (DRIFTS), which allows FTIR measurements of dust samples under ambient conditions by measuring the light scattered by the dust sample. We have also incorporated a low -temperature reaction chamber permitting the DRIFTS measurements at low temperatures and high-vacuum. This set-up permits the analysis of the solid particles surfaces revealing the chemical species adsorbed as well as their chemical evolution via the introduction of reactant gases, UV irradiation, temperature change, etc.

Flow of ices in the Ammonia-Water System

NASA Technical Reports Server (NTRS)

Durham, W. B.; Kirby, S. H.; Stern, L. A.

1993-01-01

We have fabricated in the laboratory and subsequently deformed crystalline hydrates and partial melts of the water-rich end of the NH3-H2O system, with the aim of improving our understanding of physical processes occurring in icy moons of the outer solar system. Deformation experiments were carried out at constant strain rate. The range of experimental variables are given. Phase relationships in the NH3-H2O system indicate that water ice and ammonia dihydrate, NH3-2H2O, are the stable phases under our experiment conditions. X-ray diffraction of our samples usually revealed these as the dominant phases, but we have also observed an amorphous phase (in unpressurized samples only) and occasionally significant ammonia monohydrate, NH3-H2O. The onset of partial melting at the peritectic temperature at about 176 K appeared as a sharp transition in strength observed in samples of x(sub NH3) = 0.05 and 0.01, the effect of melt was less pronounced. For any given water ice + dihydrate alloy in the subsolidus region, we observed one rheological law over the entire temperature range from 175 K to about 140 K. Below 140 K, a shear instability similar to that occurring in pure water ice under the same conditions limited our ability to measure ductile flow. The rheological laws for the several alloys vary systematically from that of pure ice to that of dihydrate. Pure dihydrate is about 4 orders of magnitude less viscous than water ice just below the peritectic temperature, but because of a very pronounced temperature dependence in dihydrate (100 kJ/mol versus 43 kJ/mol for water ice) the viscosity of dihydrate equals or exceeds that of water ice at T less than 140 K. The large variation in viscosity of dihydrate with relatively small changes in temperature may be helpful in explaining the rich variety of tectonic and volcanic features seen on the surfaces of icy moons in the outer solar system.

Observation of Sea Ice Surface Thermal States Under Cloud Cover

NASA Technical Reports Server (NTRS)

Nghiem, S. V.; Perovich, D. K.; Gow, A. J.; Kwok, R.; Barber, D. G.; Comiso, J. C.; Zukor, Dorothy J. (Technical Monitor)

2001-01-01

Clouds interfere with the distribution of short-wave and long-wave radiations over sea ice, and thereby strongly affect the surface energy balance in polar regions. To evaluate the overall effects of clouds on climatic feedback processes in the atmosphere-ice-ocean system, the challenge is to observe sea ice surface thermal states under both clear sky and cloudy conditions. From laboratory experiments, we show that C-band radar (transparent to clouds) backscatter is very sensitive to the surface temperature of first-year sea ice. The effect of sea ice surface temperature on the magnitude of backscatter change depends on the thermal regimes of sea ice thermodynamic states. For the temperature range above the mirabilite (Na2SO4.10H20) crystallization point (-8.2 C), C-band data show sea ice backscatter changes by 8-10 dB for incident angles from 20 to 35 deg at both horizontal and vertical polarizations. For temperatures below the mirabilite point but above the crystallization point of MgCl2.8H2O (-18.0 C), relatively strong backwater changes between 4-6 dB are observed. These backscatter changes correspond to approximately 8 C change in temperature for both cases. The backscattering mechanism is related to the temperature which determines the thermodynamic distribution of brine volume in the sea ice surface layer. The backscatter is positively correlated to temperature and the process is reversible with thermodynamic variations such as diurnal insolation effects. From two different dates in May 1993 with clear and overcast conditions determined by the Advanced Very High Resolution Radiometer (AVHRR), concurrent Earth Resources Satellite 1 (ERS-1) C-band ice observed with increases in backscatter over first-year sea ice, and verified by increases in in-situ sea ice surface temperatures measured at the Collaborative-Interdisciplinary Cryosphere Experiment (C-ICE) site.

Olivine-respiring bacteria isolated from the rock-ice interface in a lava-tube cave, a Mars analog environment.

PubMed

Popa, Radu; Smith, Amy R; Popa, Rodica; Boone, Jane; Fisk, Martin

2012-01-01

The boundary between ice and basalt on Earth is an analogue for some near-surface environments of Mars. We investigated neutrophilic iron-oxidizing microorganisms from the basalt-ice interface in a lava tube from the Oregon Cascades with perennial ice. One of the isolates (Pseudomonas sp. HerB) can use ferrous iron Fe(II) from the igneous mineral olivine as an electron donor and O(2) as an electron acceptor. The optimum growth temperature is ∼12-14°C, but growth also occurs at 5°C. Bicarbonate is a facultative source of carbon. Growth of Pseudomonas sp. HerB as a chemolithotrophic iron oxidizer with olivine as the source of energy is favored in low O(2) conditions (e.g., 1.6% O(2)). Most likely, microbial oxidation of olivine near pH 7 requires low O(2) to offset the abiotic oxidation of iron. The metabolic capabilities of this bacterium would allow it to live in near-surface, icy, volcanic environments of Mars in the present or recent geological past and make this type of physiology a prime candidate in the search for life on Mars.

Icy Islands reveal similar volatile behavior on Pluto and Mars

NASA Astrophysics Data System (ADS)

Sori, M.; Bapst, J.; Byrne, S.

2017-12-01

Ice deposits on planetary surfaces may hold paleoclimate records and elucidate important geologic processes involving volatiles, atmospheres, topography, and climate. Sputnik Planitia on Pluto and the well-studied north and south polar layered deposits (NPLD and SPLD) of Mars are examples. Ice peripheral to these main deposits may be even more sensitive to climatic changes. At northern martian latitudes, 18 outlying H2O ice mounds have previously been mapped within impact craters (Fig. 1a) near the NPLD. Here, we use remote sensing observations from New Horizons and Mars orbital spacecraft to study similar features in craters near Sputnik Planitia and the SPLD. We identify tens of outlying topographic mounds in craters near the SPLD (Fig. 1b) and five bright albedo features in craters near Sputnik Planitia (Fig. 1c). We assess the possibility that these deposits are analogous to the H2O ice mounds at northern martian polar latitudes. The southern martian deposits are physically diverse, but always include convex topography and host craters >15 km in diameter. We interpret at least some of them to be composed of H2O ice like their northern counterparts. The five features on Pluto are located in similarly sized craters and have corresponding spectral detections of N2 ice. One (Fig. 1c) has topography very similar to martian ice mounds, including a convex shape up to 160 m thick. We conclude it is an N2 ice mound, equivalent to Mars' H2O ice mounds in that crater topography provides a favorable microclimate for volatiles. The mound may preserve a paleoclimate record that would be erased in Sputnik Planitia by convection. Using a finite element model, we estimate flow velocities of this N2 ice mound to be 1 cm/yr, implying it may be younger than the other four which could have topography subdued by viscous relaxation. We compare the properties and possible formation mechanisms of these features to test the hypothesis that Pluto's ice cycle is similar to Mars' in certain periods of its orbital history. Figure 1. THEMIS images of ice mounds in the martian craters (a) Louth and (b) Deseado near the NPLD and SPLD, with extracted MOLA topographic profiles. (c) New Horizons base map of the five outlying volatile deposits in craters on Pluto, with extracted topographic profile from crater 3 and corresponding ice flow simulation.

Physical Constraints on the Ices present on Triton's Surface

NASA Astrophysics Data System (ADS)

Merlin, Frederic; Lellouch, Emmanuel; Quirico, Eric; Schmitt, Bernard

2017-10-01

Triton is the largest distant satellite of the solar system and was probably captured from the Transneptunian population by Neptune. It is mainly covered by N2 , CO, CO2 , CH4 and H2O in solid state and, except for H2O and CO2 , these species are also present in gas phase (with a thin N2 rich atmosphere, with CH4 and CO traces, see Lellouch et al., 2011, for instance). Sublimation and recondensation of the volatile species could lead to geographical and temporal variation, and could participate to the formation of complex chemical compounds formed from photochemistry occurring in the atmosphere (Krasnopolsky and Cruikshank, 1999) or from irradiation of N2 :CH4 :CO layers (Moore and Hudson, 2003).We present new analyses based on observations that have been performed in the near Infrared at the VLT-ESO with SINFONI from 2010 to 2013 at a spectral resolution ranging from 1500 to 4000, in order to give new constraints on the chemical and physical properties of the surface. Several models based on the Hapke theory (Hapke, 1993) have also been tested in order to constrain the abundance, the grain size and the state of the major ices (N2 , CH4 , CO, CO2 , H2O) as well as an attempt to identify other species. For this purpose, we use new optical constants of CO2 performed at 35 and 54K.We confirm the presence of deep N2 layers in which CO and CH4 are diluted. Our models highly support the presence of pure CH4 ice that can explain the enhancement of the CH4/N2 gas ratio in the atmosphere over what would be expected from ideal mixing. Our results also suggest significant smaller particles of CO2 and H2O than that reported in Quirico et al. (1999). H2O is expected to be present in its crystalline phase and CO2 spectral bands are compatible with a highly crystalline structure. Our models also suggest that CO2 is probably spread over a large area of the Triton surface. Our analyses do not support the presence of higher order hydrocarbons, such as those reported by Merlin (2015) on the surface of Pluto.

Kinetics of hydrogen/deuterium exchanges in cometary ices

NASA Astrophysics Data System (ADS)

Faure, Mathilde; Quirico, Eric; Faure, Alexandre; Schmitt, Bernard; Theulé, Patrice; Marboeuf, Ulysse

2015-11-01

The D/H composition of volatile molecules composing cometary ices brings key constraints on the origin of comets, on the extent of their presolar heritage, as well as on the origin of atmospheres and hydrospheres of terrestrial planets. Nevertheless, the D/H composition may have been modified to various extents in the nucleus when a comet approaches the Sun and experiences deep physical and chemical modifications in its subsurface. We question here the evolution of the D/H ratio of organic species by proton exchanges with water ice. We experimentally studied the kinetics of D/H exchanges on the ice mixtures H2O:CD3OD, H2O:CD3ND2 and D2O:HCN. Our results show that fast exchanges occur on the -OH and -NH2 chemical groups, which are processed through hydrogen bonds exchanges with water and by the molecular mobility triggered by structural changes, such as glass transition or crystallization. D/H exchanges kinetic is best described by a second-order kinetic law with activation energies of 4300 ± 900 K and 3300 ± 100 K for H2O:CD3OD and H2O:CD3ND2 ice mixtures, respectively. The corresponding pre-exponential factors ln(A(s-1)) are 25 ± 7 and 20 ± 1, respectively. No exchange was observed in the case of HCN trapped in D2O ice. These results strongly suggest that upon thermal heating (1) -OH and -NH2 chemical groups of any organic molecules loose their primordial D/H composition and equilibrate with water ice, (2) HCN does not experience proton transfer and keeps a primordial D/H composition and (3) C-H chemical groups are not isotopically modified.

Freezing and melting of salt hydrates next to solid surfaces probed by infrared-visible sum frequency generation spectroscopy.

PubMed

Anim-Danso, Emmanuel; Zhang, Yu; Dhinojwala, Ali

2013-06-12

Understanding the freezing of salt solutions near solid surfaces is important in many scientific fields. Here we use sum frequency generation (SFG) spectroscopy to study the freezing of a NaCl solution next to a sapphire substrate. During cooling we observe two transitions. The first corresponds to segregation of concentrated brine next to the sapphire surface as we cool the system down to the region where ice and brine phases coexist. At this transition, the intensity of the ice-like peak decreases, suggesting the disruption of hydrogen-bonding by sodium ions. The second transition corresponds to the formation of NaCl hydrates with abrupt changes in both the SFG intensity and the sharpness of spectral peaks. The similarity in the position of the SFG peaks with those observed using IR and Raman spectroscopy indicates the formation of NaCl·2H2O crystals next to the sapphire substrate. The melting temperatures of the hydrates are very similar to those reported for bulk NaCl·2H2O. This study enhances our understanding of nucleation and freezing of salt solutions on solid surfaces and the effects of salt ions on the structure of interfacial ice.

Longitudinal sound velocities, elastic anisotropy, and phase transition of high-pressure cubic H2O ice to 82 GPa

NASA Astrophysics Data System (ADS)

Kuriakose, Maju; Raetz, Samuel; Hu, Qing Miao; Nikitin, Sergey M.; Chigarev, Nikolay; Tournat, Vincent; Bulou, Alain; Lomonosov, Alexey; Djemia, Philippe; Gusev, Vitalyi E.; Zerr, Andreas

2017-10-01

Water ice is a molecular solid whose behavior under compression reveals the interplay of covalent bonding in molecules and forces acting between them. This interplay determines high-pressure phase transitions, the elastic and plastic behavior of H2O ice, which are the properties needed for modeling the convection and internal structure of the giant planets and moons of the solar system as well as H2O -rich exoplanets. We investigated experimentally and theoretically elastic properties and phase transitions of cubic H2O ice at room temperature and high pressures between 10 and 82 GPa. The time-domain Brillouin scattering (TDBS) technique was used to measure longitudinal sound velocities (VL) in polycrystalline ice samples compressed in a diamond anvil cell. The high spatial resolution of the TDBS technique revealed variations of VL caused by elastic anisotropy, allowing us to reliably determine the fastest and the slowest sound velocity in a single crystal of cubic H2O ice and thus to evaluate existing equations of state. Pressure dependencies of the single-crystal elastic moduli Ci j(P ) of cubic H2O ice to 82 GPa have been obtained which indicate its hardness and brittleness. These results were compared with ab initio calculations. It is suggested that the transition from molecular ice VII to ionic ice X occurs at much higher pressures than proposed earlier, probably above 80 GPa.

Sources of Sulfate Found in Mounds and Lakes at the Lewis Cliffs Ice Tongue, Transantarctic

NASA Technical Reports Server (NTRS)

Socki, Richard; Sun, Tao; Harvey, Ralph P.; Bish, David L.; Tonui, Eric; Bao, Huiming; Niles, Paul B.

2012-01-01

Massive but highly localized Na-sulfate mounds (mirabilite, Na2SO4.10H2O) have been found at the terminal moraine of the Lewis Cliffs Ice Tongue (LCIT), Antarctica. (Sigma)34S and (Sigma)18O values of LCIT mirabilite range from +48.8 to +49.3% (CDT), and -16.6 to -17.1% (V-SMOW), respectively, while (Delta)17O average -0.37% (V-SMOW). LCIT mirabilite mounds are isotopically different from other mirabilite mounds found in coastal regions of Antarctica, which have isotope values close to seawater compositions. (Sigma)18O and (Delta)17O values suggest the incorporation of isotopically light glacial water. Data point to initial sulfate formation in an anoxic water body, either as a stratified anoxic deep lake on the surface, a sub-glacial water reservoir, or a sub-glacial lake. Several surface lakes of varying size are also present within this region of the LCIT, and in some cases are adjacent to the mirabilite mounds. O and D isotope compositions of surface lakes confirm they are derived from a mixture of glacial ice and snow that underwent moderate evaporation. (Sigma)18O and (Sigma)D (V-SMOW) values of snow, ice, and lake water range from -64.2 to -29.7%, and -456.0 to -231.7%, respectively. However, the isotope chemistry of these surface lakes is extremely different from the mounds. Dissolved SO4-2 (Sigma)34S and (Sigma)18O values range from +12.0 to +20.0% and -12.8 to -22.2% (the most negative (Sigma)18O of terrestrial sulfate ever reported), respectively, with sulfate (Delta)17O ranging from +0.93 to 2.24%. Ion chromatography data show that lake water is fresh to brackish in origin, with TDS less than 1500 ppm, and sulfate concentration less than 431 ppm. Isotope and chemical data suggest that these lakes are unlikely the source of the mirabilite mounds. We suggest that lake water sulfate is potentially composed of a mixture of atmospheric sulfate and minor components of sulfate of weathering origin, much like the sulfate in the polar plateau soils of the McMurdo Dry Valleys. A simple model explains mirabilite mound formation at the LCIT. Sulfur redox processes could occur sub-glacially as a result of liquid-water-based glacial conditions (Alpine style glacier), most likely formed by pressure melting of overlying ice (Aharon, GCA, 52, 2321-2331). We suggest that the aqueous base of the LCIT contains dissolved SO42- and is anoxic where sulfate reduction to H2S, HS-, or native sulfur takes place. Sulfide is removed by either precipitation as sulfide minerals or by escape of H2S (neither of which have been observed). Mirabilite precipitation is likely the result of evaporation or freezing of sulfate-rich brines as they reach the surface where they manifest themselves as mounds. Pressure from the overlying ice contributing to a pressure-melting scenario that creates the sub-glacial aqueous environment also contributes to the mechanism of upward transport of the sulfate-rich fluids. Further evidence to support this upward transport model comes from the nature of ice motion at the LCIT. Cassidy et al (Meteoritics, 27, 490-525, 1992) pointed out that it is the vertical ice motion in this area that creates the meteorite-stranding surface that could also account for upward transport of sulfate-rich fluids. Alternatively, mirabilite was deposited in a similar condition as present-day coastal Antarctica when the LCIT was wetter and warmer

The Surfaces of Pluto and Charon

NASA Technical Reports Server (NTRS)

Cruikshank, Dale P.; Roush, Ted L.; Moore, Jeffrey M.; Sykes, Mark V.; Owen, Tobias C.; Bartholomew, Mary Jane; Brown, Robert H.; Tryka, Kimberly A.

1996-01-01

Much of the surface of Pluto consists of high-albedo regions covered to an unknown depth by Beta-N2, contaminated with CH4, CO, and other molecules. A portion of the exposed surface appears to consist of solid H2O. The remainder is covered by lower albedo material of unknown composition. The N2 ice may occur as polar caps of large extent, leaving ices and other solids of lower volatility in the equatorial regions. The low-albedo material found primarily in the equatorial regions may consist in part of solid hydrocarbons and nitriles produced from N2 and CH4 in the atmosphere or in the surface ices. Alternatively, it may arise from deposition from impacting bodies and/or the chemistry of the impact process itself. Charon's surface is probably more compositionally uniform than that of Pluto, and is covered by H2O ice with possible contaminants or exposures of other materials that are as yet unidentified. The molecular ices discovered on Pluto and Charon have been identified from near-infrared spectra obtained with Earth-based telescopes. The quantitative interpretation of those data has been achieved through the computation of synthetic spectra using the Hapke scattering theory and the optical constants of various ices observed in the laboratory. Despite limitations imposed by the availability of laboratory data on ices in various mixtures, certain specific results have been obtained. It appears that CH4 and CO are trace constituents, and that some fraction of the CH4 (and probably the CO) on Pluto is dissolved in the matrix of solid N2. Pure CH4 probably also occurs on Pluto's surface, allowing direct access to the atmosphere. Study of the nitrogen absorption band at 2.148 micrometers shows that the temperature of the N2 in the present epoch is 40 +/-2 K. The global temperature regime of Pluto can be modeled from observations of the thermal flux at far-infrared and millimeter wavelengths. The low-albedo equatorial regions must be significantly warmer than the polar regions covered by N2 (at T = 40 K) to account for the total thermal flux measured. At the present season, the diurnal skin depth of the insolation-driven thermal wave is small, and the observed mm-wave fluxes may arise from a greater depth. Alternatively, the mm-wave flux may arise from the cool, sublimation source region. The surface microstructure in the regions covered by N2 ice is likely governed by the sintering properties of this highly volatile material. The observed nitrogen infrared band strength requires that expanses of the surface be covered with cm-sized crystals of N2. Grains of H2O ice on Charon, in contrast, are probably of order 50 micrometers in size, and do not metamorphose into larger grains at a significant rate. Because of the similarities in size, density, atmosphere and surface composition between Pluto and Neptune's satellite Triton, the surface structures observed by Voyager on Triton serve as a plausible paradigm for what might be expected on Pluto. Such crater forms, tectonic structures, aeolian features, cryovolcanic structures, and sublimation-degraded topography as are eventually observed on Pluto and Charon by spacecraft will give information on their interior compositions and structures, as well as on the temperature and wind regimes over the planet's extreme seasonal cycle.

Vacuum ultraviolet photoabsorption of prime ice analogues of Pluto and Charon

NASA Astrophysics Data System (ADS)

Pavithraa, S.; Lo, J.-I.; Rahul, K.; Raja Sekhar, B. N.; Cheng, B.-M.; Mason, N. J.; Sivaraman, B.

2018-02-01

Here we present the first Vacuum UltraViolet (VUV) photoabsorption spectra of ice analogues of Pluto and Charon ice mixtures. For Pluto the ice analogue is an icy mixture containing nitrogen (N2), carbon monoxide (CO), methane (CH4) and water (H2O) prepared with a 100:1:1:3 ratio, respectively. Photoabsorption of icy mixtures with and without H2O were recorded and no significant changes in the spectra due to presence of H2O were observed. For Charon a VUV photoabsorption spectra of an ice analogue containing ammonia (NH3) and H2O prepared with a 1:1 ratio was recorded, a spectrum of ammonium hydroxide (NH4OH) was also recorded. These spectra may help to interpret the P-Alice data from New Horizons.

Computational studies of atmospherically-relevant chemical reactions in water clusters and on liquid water and ice surfaces.

PubMed

Gerber, R Benny; Varner, Mychel E; Hammerich, Audrey D; Riikonen, Sampsa; Murdachaew, Garold; Shemesh, Dorit; Finlayson-Pitts, Barbara J

2015-02-17

CONSPECTUS: Reactions on water and ice surfaces and in other aqueous media are ubiquitous in the atmosphere, but the microscopic mechanisms of most of these processes are as yet unknown. This Account examines recent progress in atomistic simulations of such reactions and the insights provided into mechanisms and interpretation of experiments. Illustrative examples are discussed. The main computational approaches employed are classical trajectory simulations using interaction potentials derived from quantum chemical methods. This comprises both ab initio molecular dynamics (AIMD) and semiempirical molecular dynamics (SEMD), the latter referring to semiempirical quantum chemical methods. Presented examples are as follows: (i) Reaction of the (NO(+))(NO3(-)) ion pair with a water cluster to produce the atmospherically important HONO and HNO3. The simulations show that a cluster with four water molecules describes the reaction. This provides a hydrogen-bonding network supporting the transition state. The reaction is triggered by thermal structural fluctuations, and ultrafast changes in atomic partial charges play a key role. This is an example where a reaction in a small cluster can provide a model for a corresponding bulk process. The results support the proposed mechanism for production of HONO by hydrolysis of NO2 (N2O4). (ii) The reactions of gaseous HCl with N2O4 and N2O5 on liquid water surfaces. Ionization of HCl at the water/air interface is followed by nucleophilic attack of Cl(-) on N2O4 or N2O5. Both reactions proceed by an SN2 mechanism. The products are ClNO and ClNO2, precursors of atmospheric atomic chlorine. Because this mechanism cannot result from a cluster too small for HCl ionization, an extended water film model was simulated. The results explain ClNO formation experiments. Predicted ClNO2 formation is less efficient. (iii) Ionization of acids at ice surfaces. No ionization is found on ideal crystalline surfaces, but the process is efficient on isolated defects where it involves formation of H3O(+)-acid anion contact ion pairs. This behavior is found in simulations of a model of the ice quasi-liquid layer corresponding to large defect concentrations in crystalline ice. The results are in accord with experiments. (iv) Ionization of acids on wet quartz. A monolayer of water on hydroxylated silica is ordered even at room temperature, but the surface lattice constant differs significantly from that of crystalline ice. The ionization processes of HCl and H2SO4 are of high yield and occur in a few picoseconds. The results are in accord with experimental spectroscopy. (v) Photochemical reactions on water and ice. These simulations require excited state quantum chemical methods. The electronic absorption spectrum of methyl hydroperoxide adsorbed on a large ice cluster is strongly blue-shifted relative to the isolated molecule. The measured and calculated adsorption band low-frequency tails are in agreement. A simple model of photodynamics assumes prompt electronic relaxation of the excited peroxide due to the ice surface. SEMD simulations support this, with the important finding that the photochemistry takes place mainly on the ground state. In conclusion, dynamics simulations using quantum chemical potentials are a useful tool in atmospheric chemistry of water media, capable of comparison with experiment.

New Optical Constants for Amorphous and Crystalline H2O-ice

NASA Technical Reports Server (NTRS)

Mastrapa, Rachel; Bernstein, Max; Sandford, Scott

2006-01-01

We have used the infrared spectra of laboratory ices to calculate the real and imaginary indices of refraction for amorphous and crystalline H2O-ice. We create H2O-ice samples in vacuum (approx. 10(exp ^-8)Torr). We measure the thickness of the sample by reflecting a He-Ne laser off of the sample and counting interference fringes as it grows and then collect transmission spectra of the samples in the wavelength range 1.25-22 micrometers. Using the ice thickness and transmission spectrum we calculate the imaginary part of the index of refraction. A Kramers-Kronig calculation is then used to calculate the real part of the index of refraction (Berland et al. 1994; Hudgins et al. 1993). These optical constants can be used to create model spectra for comparison to spectra from Solar System objects. We will summarize the differences between the amorphous and crystalline H2O-ice spectra. These include weakening of features and shifting of features to shorter wavelength in amorphous H,O-ice spectra. We will also discuss methods of using band area ratios to quickly estimate the fraction of amorphous to crystalline H2O-ice. We acknowledge financial support from the NASA Origins of the Solar System Program, the NASA Planetary Geology and Geophysics Program, and the NASA Postdoctoral Program.

Photochemistry of polycyclic aromatic hydrocarbons in cosmic water ice. II. Near UV/VIS spectroscopy and ionization rates

NASA Astrophysics Data System (ADS)

Bouwman, J.; Cuppen, H. M.; Steglich, M.; Allamandola, L. J.; Linnartz, H.

2011-05-01

Context. Mid-infrared emission features originating from polycyclic aromatic hydrocarbons (PAHs) are observed towards photon dominated regions in space. Towards dense clouds, however, these emission features are quenched. Observations of dense clouds show that many simple volatile molecules are frozen out on interstellar grains, forming thin layers of ice. Recently, observations have shown that more complex non-volatile species, presumably including PAHs, also freeze out and contribute to the ongoing solid-state chemistry. Aims: The study presented here aims at obtaining reaction rate data that characterize PAH photochemistry upon vacuum ultraviolet (VUV) irradiation in an interstellar H2O ice analogue to explore the potential impact of PAH:H2O ice reactions on overall interstellar ice chemistry. To this end, the experimental results are implemented in a chemical model under simple interstellar cloud conditions. Methods: Time-dependent near-UV/VIS spectroscopy on the VUV photochemistry of anthracene, pyrene, benzo[ghi]perylene and coronene containing interstellar H2O ice analogs is performed at 25 and 125 K, using an optical absorption setup. Results: Near-UV/VIS absorption spectra are presented for these four PAHs and their photoproducts including cationic species trapped in H2O ice. Oscillator strengths of the cation absorption bands are derived relative to the oscillator strength of the neutral parent PAH. The loss of the parent and growth of PAH photoproducts are measured as a function of VUV dose, yielding solid state reaction constants. The rate constants are used in an exploratory astrochemical model, to assess the importance of PAH:H2O ice photoprocessing in UV exposed interstellar environments, compared with the timescales in which PAH molecules are incorporated in interstellar ices. Conclusions: All four PAHs studied here are found to be readily ionized upon VUV photolysis when trapped in H2O ice and exhibit similar rates for ionization at astronomically relevant temperatures. Depending on the relative efficiency of H2O photodesorption and PAH photoionization in H2O ice, the latter may trigger a charge induced aromatic solid state chemistry, in which PAH cations play a central role.

Band Formation and Ocean-Surface Interaction on Europa and Ganymede

NASA Astrophysics Data System (ADS)

Howell, Samuel M.; Pappalardo, Robert T.

2018-05-01

Geologic activity in the outer H2O ice shells of Europa and Ganymede, Galilean moons of Jupiter, may facilitate material exchange between global water oceans and the icy surface, fundamentally affecting potential habitability and the future search for life. Spacecraft imagery reveals surfaces rich with tectonic bands, predominantly attributed to the extension of brittle ice overlaying a convecting ice layer. However, the details of band-forming processes and links to potential ocean-surface exchange have remained elusive. We simulate ice shell faulting and convection with two-dimensional numerical models and track the movement of "fossil" ocean material frozen into the base of the ice shell and deformed through geologic time. We find that distinct band types form within a spectrum of extensional terrains correlated to lithosphere strength, governed by lithosphere thickness and cohesion. Furthermore, we find that smooth bands formed in weak lithosphere promote exposure of fossil ocean material at the surface.

High Pressure and High Temperature State of Oxygen Enriched Ice

NASA Astrophysics Data System (ADS)

LI, M.; Zhang, S.; Jeanloz, R.; Militzer, B.

2016-12-01

Interior models for Uranus and Neptune include a hydrogen/helium/water outer envelope and a core of rock and metal at the center, with superionic water-rich ice proposed as comprising an intermediate layer. Here we consider an oxygen-enriched ice, such as H2O2 hydrogen peroxide (± water), that could form through chemical reaction between water-rich and underlying rocky (i.e., oxygen-rich) layers. As oxygen and its compounds (e.g., H2O, SiO2) form metallic fluids at pressures above 100-150 GPa, the problem amounts to considering oxygen alloying of semiconducting or metallic water. The density of H2O2 is 1.45 g/cc at ambient pressure and 0° C, increasing to 1.71 g/cc in the solid state at about -20° C. There are no Hugoniot data beyond 30 GPa, so we estimated Hugoniots for H2O2 with different initial densities, using both a mixing model based on Hugoniot data for H2O2 and 1/2 O2 (molar volume summation under pressure) and ab initio calculations for unreacted H2O2. The results agree with each other to pressures of about 200 GPa, and the ab initio calculations show evidence of a superionic state at temperatures as low as 500 K, much lower than for water ice. Hydrogen peroxide is expected to be liquid along planetary isentropes for Uranus and Neptune, suggesting that H2O2 may not be present as a pure compound in these planets. Instead, oxygen-enriched H2O ice may be the relevant form of water and oxygen, and might be produced in the laboratory by way of dynamic compression of H2O2 or laser-heating of statically compressed H2O + O2 and/or H2O2.

In situ observations of a high-pressure phase of H2O ice

USGS Publications Warehouse

Chou, I.-Ming; Blank, J.G.; Goncharov, A.F.; Mao, Ho-kwang; Hemley, R.J.

1998-01-01

A previously unknown solid phase of H2O has been identified by its peculiar growth patterns, distinct pressure-temperature melting relations, and vibrational Raman spectra. Morphologies of ice crystals and their pressure-temperature melting relations were directly observed in a hydrothermal diamond-anvil cell for H2O bulk densities between 1203 and 1257 kilograms per cubic meter at temperatures between -10??and 50??C. Under these conditions, four different ice forms were observed to melt: two stable phases, ice V and ice VI, and two metastable phases, ice IV and the new ice phase. The Raman spectra and crystal morphology are consistent with a disordered anisotropic structure with some similarities to ice VI.

Interstellar Ice Chemistry: From Water to Complex Organics

NASA Astrophysics Data System (ADS)

Oberg, Karin I.; Fayolle, E.; Linnartz, H.; van Dishoeck, E.; Fillion, J.; Bertin, M.

2013-06-01

Molecular cloud cores, protostellar envelopes and protoplanetary disk midplanes are all characterized by freeze-out of atoms and molecules (other than H and H2) onto interstellar dust grains. On the grain surface, atom addition reactions, especially hydrogenation, are efficient and H2O forms readily from O, CH3OH from CO etc. The result is an icy mantle typically dominated by H2O, but also rich in CO2, CO, NH3, CH3OH and CH4. These ices are further processed through interactions with radiation, electrons and energetic particles. Because of the efficiency of the freeze-out process, and the complex chemistry that succeeds it, these icy grain mantles constitute a major reservoir of volatiles during star formation and are also the source of much of the chemical evolution observed in star forming regions. Laboratory experiments allow us to explore how molecules and radicals desorb, dissociate, diffuse and react in ices when exposed to different sources of energy. Changes in ice composition and structure is constrained using infrared spectroscopy and mass spectrometry. By comparing ice desorption, segregation, and chemistry efficiencies under different experimental conditions, we can characterize the basic ice processes, e.g. diffusion of different species, that underpin the observable changes in ice composition and structure. This information can then be used to predict the interstellar ice chemical evolution. I will review some of the key laboratory discoveries on ice chemistry during the past few years and how they have been used to predict and interpret astronomical observations of ice bands and gas-phase molecules associated with ice evaporation. These include measurements of thermal diffusion in and evaporation from ice mixtures, non-thermal diffusion efficiencies (including the recent results on frequency resolved UV photodesorption), and the expected temperature dependencies of the complex ice chemistry regulated by radical formation and diffusion. Based on these examples I will argue that the combination of laboratory experiments and observations is crucial to formulate and to test hypotheses on key processes that regulate the interstellar ice chemistry.

Irradiation Enhanced Adsorption and Trapping of O2 on Microporous Water Ice

NASA Astrophysics Data System (ADS)

Shi, Jianming; Teolis, B. D.; Baragiola, R. A.

2007-10-01

The condensed O2 found on Ganymede and Europa, and its relationship to tenuous O2 atmospheres have long been a puzzle considering the instability of solid oxygen at the relative high temperatures of the satellites. We report on the discovery that ion irradiation of microporous water ice exposed to gaseous oxygen enhances adsorption and retention of O2. We investigated how the irradiation history of ice with and without ambient O2 influences the O2 adsorption on ice. Irradiation by 100 KeV Ar+ or 50 KeV H+ ions in vacuum was found to compact the ice, in agreement with Raut et al. [(2007), J. Chem. Phys., 126, 244511]. This was revealed in a subsequent oxygen exposure which resulted in no O2 adsorption. When ice was irradiated at an ambient O2 pressure of 5.5x10-7 torr, O2 adsorption was enhanced by a factor as high as 5.5 compared to unirradiated ice. The enhanced amount of adsorbed O2 increased with decreasing ion flux. A uniform oxygen concentration of 3% was achieved throughout the ion penetration depth for a low flux limit. After simultaneous irradiation and oxygen exposure, the adsorbed O2 could be retained in the ice when the ambient O2 pressure was removed. The experimental results show that the ion induced enhancement of adsorption and retention of oxygen may explain the difference in the amount of condensed oxygen on the leading vs. trailing sides of Ganymede and Europa [Spencer et. al. (1995), J. Geophys. Res., 100, 19049]. The results also indicate that re-adsorption of atmospheric O2 can not be neglected in exosphere models, since significant amounts of adsorbed O2 could occur in regions with surfaces colder than 50 K or those areas under low flux ion bombardment.

A Model Study of the Thermal Evolution of Astrophysical Ices

NASA Technical Reports Server (NTRS)

Loeffler, M. J.; Teolis, B. D.; Baragiola, R. A.

2006-01-01

We address the question of the evolution of ices that have been exposed to radiation from stellar sources and cosmic rays. We studied in the laboratory the thermal evolution of a model ice sample: a mixture of water, hydrogen peroxide, dioxygen, and ozone produced by irradiating solid H2O2 with 50 keV H(+) at 17 K. The changes in composition and release of volatiles during warming to 200 K were monitored by infrared spectroscopy, mass spectrometry, and microbalance techniques. We find evidence for voids in the water component from the infrared bands due to dangling H bonds. The absorption from these bands increases during heating and can be observed at temperatures as high as approx. 155 K. More O2 is stored in the radiolyzed film than can be retained by codeposition of O2 and H2O. This O2 remains trapped until approx. 155 K, where it desorbs in an outburst as water ice crystallizes. Warming of the ice also drastically decreases the intrinsic absorbance of O2 by annealing defects in the ice. We also observe loss of O3 in two stages during heating, which correlates with desorption and possibly chemical reactions with radicals stored in the ice, triggered by the temperature increase.

Interior and its implications for the atmosphere. [effects of Titan interior structure on its atmospheric composition

NASA Technical Reports Server (NTRS)

Lewis, J. S.

1974-01-01

The bulk composition and interior structure of Titan required to explain the presence of a substantial methane atmosphere are shown to imply the presence of solid CH4 - 7H2O in Titan's primitive material. Consideration of the possible composition and structure of the present atmosphere shows plausible grounds for considering models with total atmospheric pressures ranging from approximately 20 mb up to approximately 1 kb. Expectations regarding the physical state of the surface and its chemical composition are strongly conditioned by the mass of atmosphere believed to be present. A surface of solid CH4, liquid CH4 solid, CH4 hydrate, H2O ice, aqueous NH3 solution, or even a non-surface of supercritical H2O-NH3-CH4 fluid could be rationalized.

Photochemistry of coronene in cosmic water ice analogs at different concentrations.

PubMed

de Barros, A L F; Mattioda, A L; Ricca, A; Cruz, G; Allamandola, L J

2017-10-20

This work presents the photochemistry of ultraviolet (UV) irradiated coronene in water ices at 15 K, studied using mid-infrared Fourier transform (FTIR) spectroscopy for C 24 H 12 :H 2 O at concentrations of (1:50), (1:150), (1:200), (1:300) and (1:400). Previous UV irradiation studies of anthracene:H 2 O, pyrene:H 2 O and benzo[ghi]perylene:H 2 O ices at 15 K have shown that aromatic alcohols and ketones, as well as CO 2 and H 2 CO are formed at very low temperatures. Like-wise, here, in addition to the coronene cation, hydroxy-, keto-, and protonated coronene (coronene-H + ) are formed. The rate constants for the decay of neutral coronene and for the formation of photoproducts have been derived. It is shown that PAHs and their UV-induced PAH:H 2 O photoproducts have mid-infrared spectroscopic signatures in the 5-8 μ m region that can contribute to the interstellar ice components described by Boogert et al. (2008) as C1-C5. Our results suggest that oxygenated and hydrogenated PAHs could be in UV-irradiated regions of the ISM where water-rich ices are important.

Photochemistry of Coronene in Cosmic Water Ice Analogs at Different Concentrations

NASA Astrophysics Data System (ADS)

de Barros, A. L. F.; Mattioda, A. L.; Ricca, A.; Cruz-Diaz, G. A.; Allamandola, L. J.

2017-10-01

This work presents the photochemistry of ultraviolet (UV) irradiated coronene in water ices at 15 K studied using mid-infrared Fourier transform (FTIR) spectroscopy for C24H12:H2O at concentrations of (1:50), (1:150), (1:200), (1:300), and (1:400). Previous UV irradiation studies of anthracene:H2O, pyrene:H2O, and benzo[ghi]perylene:H2O ices at 15 K have shown that aromatic alcohols and ketones, as well as CO2 and H2CO, are formed at very low temperatures. Likewise, here, in addition to the coronene cation, hydroxy-, keto-, and protonated coronene (coronene H+) are formed. The rate constants for the decay of neutral coronene and for the formation of photoproducts have been derived. It is shown that Polycyclic Aromatic Hydrocarbons (PAHs) and their UV induced PAH:H2O photoproducts have mid-infrared spectroscopic signatures in the 5-8 μm region that can contribute to the interstellar ice components described by Boogert et al. as C1-C5. Our results suggest that oxygenated and hydrogenated PAHs could be in UV-irradiated regions of the interstellar medium where water-rich ices are important.

Vacuum ultraviolet photoabsorption of prime ice analogues of Pluto and Charon.

PubMed

Pavithraa, S; Lo, J-I; Rahul, K; Raja Sekhar, B N; Cheng, B-M; Mason, N J; Sivaraman, B

2018-02-05

Here we present the first Vacuum UltraViolet (VUV) photoabsorption spectra of ice analogues of Pluto and Charon ice mixtures. For Pluto the ice analogue is an icy mixture containing nitrogen (N 2 ), carbon monoxide (CO), methane (CH 4 ) and water (H 2 O) prepared with a 100:1:1:3 ratio, respectively. Photoabsorption of icy mixtures with and without H 2 O were recorded and no significant changes in the spectra due to presence of H 2 O were observed. For Charon a VUV photoabsorption spectra of an ice analogue containing ammonia (NH 3 ) and H 2 O prepared with a 1:1 ratio was recorded, a spectrum of ammonium hydroxide (NH 4 OH) was also recorded. These spectra may help to interpret the P-Alice data from New Horizons. Copyright © 2017 Elsevier B.V. All rights reserved.

The lunar thermal ice pump

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schorghofer, Norbert; Aharonson, Oded, E-mail: norbert@hawaii.edu

2014-06-20

It has long been suggested that water ice can exist in extremely cold regions near the lunar poles, where sublimation loss is negligible. The geographic distribution of H-bearing regolith shows only a partial or ambiguous correlation with permanently shadowed areas, thus suggesting that another mechanism may contribute to locally enhancing water concentrations. We show that under suitable conditions, water molecules can be pumped down into the regolith by day-night temperature cycles, leading to an enrichment of H{sub 2}O in excess of the surface concentration. Ideal conditions for pumping are estimated and found to occur where the mean surface temperature ismore » below 105 K and the peak surface temperature is above 120 K. These conditions complement those of the classical cold traps that are roughly defined by peak temperatures lower than 120 K. On the present-day Moon, an estimated 0.8% of the global surface area experiences such temperature variations. Typically, pumping occurs on pole-facing slopes in small areas, but within a few degrees of each pole the equator-facing slopes are preferred. Although pumping of water molecules is expected over cumulatively large areas, the absolute yield of this pump is low; at best, a few percent of the H{sub 2}O delivered to the surface could have accumulated in the near-surface layer in this way. The amount of ice increases with vapor diffusivity and is thus higher in the regolith with large pore spaces.« less

Discovery of moganite in a lunar meteorite as a trace of H2O ice in the Moon’s regolith

PubMed Central

Seto, Yusuke; Miyake, Akira; Sekine, Toshimori; Tomeoka, Kazushige; Matsumoto, Megumi; Kobayashi, Takamichi

2018-01-01

Moganite, a monoclinic SiO2 phase, has been discovered in a lunar meteorite. Silica micrograins occur as nanocrystalline aggregates of mostly moganite and occasionally coesite and stishovite in the KREEP (high potassium, rare-earth element, and phosphorus)–like gabbroic-basaltic breccia NWA 2727, although these grains are seemingly absent in other lunar meteorites. We interpret the origin of these grains as follows: alkaline water delivery to the Moon via carbonaceous chondrite collisions, fluid capture during impact-induced brecciation, moganite precipitation from the captured H2O at pH 9.5 to 10.5 and 363 to 399 K on the sunlit surface, and meteorite launch from the Moon caused by an impact at 8 to 22 GPa and >673 K. On the subsurface, this captured H2O may still remain as ice at estimated bulk content of >0.6 weight %. This indicates the possibility of the presence of abundant available water resources underneath local sites of the host bodies within the Procellarum KREEP and South Pole Aitken terranes. PMID:29732406

H-implantation in SO 2 and CO 2 ices

NASA Astrophysics Data System (ADS)

Garozzo, M.; Fulvio, D.; Gomis, O.; Palumbo, M. E.; Strazzulla, G.

2008-07-01

Ices in the solar system are observed on the surface of planets, satellites, comets and asteroids where they are continuously subordinate at particle fluxes (cosmic ions, solar wind and charged particles caught in the magnetosphere of the planets) that deeply modify their physical and structural properties. Each incoming ion destroys molecular bonds producing fragments that, by recombination, form new molecules also different from the original ones. Moreover, if the incoming ion is reactive (H +, O n+ , S n+ , etc.), it can concur to the formation of new molecules. Those effects can be studied by laboratory experiments where, with some limitation, it is possible to reproduce the astrophysical environments of planetary ices. In this work, we describe some experiments of 15-100 keV H + and He + implantation in pure sulfur dioxide (SO 2) at 16 and 80 K and carbon dioxide (CO 2) at 16 K ices aimed to search for the formation of new molecules. Among other results we confirm that carbonic acid (H 2CO 3) is formed after H-implantation in CO 2, vice versa H-implantation in SO 2 at both temperatures does not produce measurable quantity of sulfurous acid (H 2SO 3). The results are discussed in the light of their relevance to the chemistry of some solar system objects, particularly of Io, the innermost of Jupiter's Galilean satellites, that exhibits a surface very rich in frost SO 2 and it is continuously bombarded with H + ions caught in Jupiter's magnetosphere.

Infrared spectroscopy of Triton and Pluto ice analogs: the case for saturated hydrocarbons.

PubMed

Bohn, R B; Sandford, S A; Allamandola, L J; Cruikshank, D P

1994-09-01

The infrared transmission spectra and photochemical behavior of various organic compounds isolated in solid N2 ices, appropriate for applications to Triton and Pluto, are presented. It is shown that excess absorption in the surface spectra of Triton and Pluto, i.e., absorption not explained by present models incorporating molecules already identified on these bodies (N2, CH4, CO, and CO2), that starts near 4450 cm-1 (2.25 micrometers) and extends to lower frequencies, may be due to alkanes (C(n)H2n+2) and related molecules frozen in the nitrogen. Branched and linear alkanes may be responsible. Experiments in which the photochemistry of N2:CH4 and N(2):CH4:CO ices was explored demonstrate that the surface ices of Triton and Pluto may contain a wide variety of additional species containing H, C, O, and N. Of these, the reactive molecule diazomethane, CH2N2, is particularly important since it may be largely responsible for the synthesis of larger alkanes from CH4 and other small alkanes. Diazomethane would also be expected to drive chemical reactions involving organics in the surface ices of Triton and Pluto toward saturation, i.e., to reduce multiple CC bonds. The positions and intrinsic strengths (A values) of many of the infrared absorption bands of N2 matrix-isolated molecules of relevance to Triton and Pluto have also been determined. These can be used to aid in their search and to place constraints on their abundances. For example, using these A values the abundance ratios CH4/N2 approximately 1.3 x 10(-3), C2H4/N2 < or = 9.5 x 10(-7) and H2CO/N2 < or = 7.8 x 10(-7) are deduced for Triton and CH4/N2 approximately 3.1 x 10(-3), C2H4/N2 < or = 4.1 x 10(-6), and H2CO/N2 < or = 5.2 x 10(-6) deduced for Pluto. The small amounts of C2H4 and H2CO in the surface ices of these bodies are in disagreement with the large abundances expected from many theoretical models.

The Compositions, Particle Sizes, and Distributions of Ice Aerosols in the Mars Mesosphere from 2009-2016 CRISM Visible-NearIR Limb Spectra

NASA Astrophysics Data System (ADS)

Clancy, R. T.; Smith, M. D.; Wolff, M. J.; Toigo, A. D.; Seelos, K. D.; Murchie, S. L.

2016-12-01

Since 2009, the CRISM visible-nearIR imaging spectrometer onboard the Mars Reconnaissance Orbiter (MRO) has returned over 70 orbits of Mars limb image scans over the 0-130 km altitude range. Pole-to-pole latitudinal coverage is obtained from the near-polar, sun-synchronous (LT 3pm) MRO orbit for a limited set of surface longitudes centered on Tharsis, Valles Mariners, Meridioni, and Hellas regions. Seasonal coverage extends over the full seasonal range (Ls=0-360°), as accumulated over 2009-2016 (MY 29-33), supporting a range of aerosol and airglow studies (Smith et al., 2013; Clancy et al., 2012, 2013). The 0.4-4.0 μm wavelength range of these CRISM limb observations proves particularly suitable to characterizing aerosol composition and particle sizes, particularly for the Mars mesosphere (z=50-100 km), which has only recently been observed with any dedication by MCS (Sefton-Nash et al, 2013) and CRISM limb measurements. Dust and H2O, CO2 ice aerosols are clearly distinguished by their distinct scattering and absorption behaviors over the key 2-4 μm wavelength region, and their particle sizes are well determined by the 0.4-3 μm wavelength region. Several key attributes are determined for Mars mesospheric aerosols. Dust aerosols are largely undetected, and are apparently injected to such heights only during global dust storms (Clancy et al, 2010). Ice clouds are generally common at 55-75 km altitudes, although in separate halves of the Mars year. CO2 and H2O ice clouds are most prominent during the aphelion and perihelion portions of the Mars orbit, respectively. CO2 ice clouds, which occur at low latitudes over specific surface longitudes, present distinct particle size populations ranging from 0.5 to 1.5 μm (Reff). Mesospheric H2O ice clouds exhibit somewhat smaller particle sizes (Reff=0.3-1 μm) and extend over low to mid latitudes. This orbital dependence for mesospheric ice aerosol composition indicates extreme annual (orbital) variation in mesospheric water vapor.

The role of the geothermal gradient in the emplacement and replenishment of ground ice on Mars

NASA Technical Reports Server (NTRS)

Clifford, Stephen M.

1993-01-01

Knowledge of the mechanisms by which ground ice is emplaced, removed, and potentially replenished, are critical to understanding the climatic and hydrologic behavior of water on Mars, as well as the morphologic evolution of its surface. Because of the strong temperature dependence of the saturated vapor pressure of H2O, the atmospheric emplacement or replenishment of ground ice is prohibited below the depth at which crustal temperatures begin to monotonically increase due to geothermal heating. In contrast, the emplacement and replenishment of ground ice from reservoirs of H2O residing deep within the crust can occur by at least three different thermally-driven processes, involving all three phases of water. In this regard, Clifford has discussed how the presence of a geothermal gradient as small as 15 K/km can give rise to a corresponding vapor pressure gradient sufficient to drive the vertical transport of 1 km of water from a reservoir of ground water at depth to the base of the cryosphere every 10(exp 6) - 10(exp 7) years. This abstract expands on this earlier treatment by considering the influence of thermal gradients on the transport of H2O at temperatures below the freezing point.

What is Eating Ozone? Thermal Reactions between SO2 And O3: Implications for Icy Environments

NASA Technical Reports Server (NTRS)

Loeffler, Mark J.; Hudson, Reggie L.

2016-01-01

Laboratory studies are presented, showing for the first time that thermally driven reactions in solid H2O+SO2+O3 mixtures can occur below 150 K, with the main sulfur-containing product being bisulfate (HSO4(-)). Using a technique not previously applied to the low-temperature kinetics of either interstellar or solar system ice analogs, we estimate an activation energy of 32 kJ per mol for HSO4(-) formation. These results show that at the temperatures of the Jovian satellites, SO2 and O3 will efficiently react making detection of these molecules in the same vicinity unlikely. Our results also explain why O3 has not been detected on Callisto and why the SO2 concentration on Callisto appears to be highest on that world's leading hemisphere. Furthermore, our results predict that the SO2 concentration on Ganymede will be lowest in the trailing hemisphere, where the concentration of O3 is the highest. Our work suggests that thermal reactions in ices play a much more important role in surface and sub-surface chemistry than generally appreciated, possibly explaining the low abundance of sulfur-containing molecules and the lack of ozone observed in comets and interstellar ices.

The behavior of N2 and O2 in pure, mixed or layered CO ices

NASA Astrophysics Data System (ADS)

Bisschop, Suzanne E.; Fraser, Helen J.; Fuchs, Guido; Öberg, Karin I.; Acharyya, Kinsuk; van Broekhuizen, Fleur; Schlemmer, Stephan; van Dishoeck, Ewine F.

N2 and O2 are molecules that are predicted to be abundant in dense molecular clouds. Both molecules are difficult to detect as neither has a dipole moment. The chemical abundance of N2 is mostly inferred from its daughter species N2H+, but was recently detected in the ISM for the first time, with an abundance of 3.3 × 10-7 (Knauth et al 2004). Searches for the submillimeter lines of O2 have given upper limits for the abundance of ≤ 2.6 10-7 for star forming clouds and ≤ 3 10-6 for cold dark clouds (Goldsmith et al. 2000). Pontoppidan et al. (2003) deduced from the CO line profile that CO is present in both H2O poor and H2O rich ice layers, so it follows that N2 is likely to be present in a H2O poor ice layer. In many cold and protostellar cores N2H+ is found to anti-correlate with HCO+ and CO (Bergin et al. 2001; Jørgensen et al. 2004). Models by, for example Bergin & Langer (1997), assume this is due to the balance between freeze-out and evaporation, where ratios for the binding energy for N2 compared to CO of 0.50-0.70 are used. To model these processes, and reproduce the observed abundances of each species it is important to determine empirically the binding energies, sticking probabilities and desorption kinetics of model ice systems containing CO, N2 and O2. It seems that these quantities depend on the degree to which N2 and O2 mix with CO. Therefore, CO and N2 ices were studied extensively in a Ultra High Vacuum (UHV) experiment (P ~ 1 × 10-10 Torr) (Oberg et al. 2005; Bisschop et al submitted)). Ice samples were deposited at 14 K on a polycrystalline gold sample, mounted in the UHV chamber, covering morphologies from pure CO and N2, and 1:1 mixtures, to 1/1 layers of both CO over N2 and N2 over CO, and layers of 40 L of CO (1 L ≈ 1 monolayer) covered with 5 to 50 L of N2. The ices were studied using a combination of Reflection Absorption Infrared Spectroscopy (RAIRS) and Temperature Programmed Desorption (TPD), at a ramp-rate of 0.1 K min-1. The TPD data were modeled to accurately determine the binding energies and desorption kinetics o each system, using information from the RAIR spectra to develop the model. Sticking probabilities were calculated from a comparison between the molecular load at the mass spectrometer during dosing onto a hot and cold sample surface. The experiments show that N2 desorption from pure N2 ice gives a slightly lower binding energy for N2-N2 than CO-CO, 790 ± 25 K and 855 ± 25 K respectively, resulting in a ratio RBE = 0.923 ± 0.003. The TPD data for the mixtures and layers (see Figure 1) show that N2 can also completely mix in with the CO ice. A fraction of the N2 molecules that have mixed into the CO-ice, desorb with CO, giving them an effective binding energy of 855 ± 25 K (RBE=1). In either case, this ratio is much closer to unity than that used in models by (for example) Bergin & Langer (1997).

Olivine-Respiring Bacteria Isolated from the Rock-Ice Interface in a Lava-Tube Cave, a Mars Analog Environment

PubMed Central

Smith, Amy R.; Popa, Rodica; Boone, Jane; Fisk, Martin

2012-01-01

Abstract The boundary between ice and basalt on Earth is an analogue for some near-surface environments of Mars. We investigated neutrophilic iron-oxidizing microorganisms from the basalt-ice interface in a lava tube from the Oregon Cascades with perennial ice. One of the isolates (Pseudomonas sp. HerB) can use ferrous iron Fe(II) from the igneous mineral olivine as an electron donor and O2 as an electron acceptor. The optimum growth temperature is ∼12–14°C, but growth also occurs at 5°C. Bicarbonate is a facultative source of carbon. Growth of Pseudomonas sp. HerB as a chemolithotrophic iron oxidizer with olivine as the source of energy is favored in low O2 conditions (e.g., 1.6% O2). Most likely, microbial oxidation of olivine near pH 7 requires low O2 to offset the abiotic oxidation of iron. The metabolic capabilities of this bacterium would allow it to live in near-surface, icy, volcanic environments of Mars in the present or recent geological past and make this type of physiology a prime candidate in the search for life on Mars. Key Words: Extremophiles—Mars—Olivine—Iron-oxidizing bacteria—Redox. Astrobiology 12, 9–18. PMID:22165996

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lazauskas, A., E-mail: Algirdas.LAZAUSKAS@stud.ktu.lt; Guobienė, A., E-mail: Asta.GUOBIENE@ktu.lt; Prosyčevas, I., E-mail: IGORPROS@mail.ru

This work investigates water droplet behavior on superhydrophobic (water contact angle value of 162 ± 1°) SiO{sub 2} nanocomposite films subjected to repetitive icing/deicing treatments, changes in SiO{sub 2} nanocomposite film surface morphology and their non-wetting characteristics. During the experiment, water droplets on SiO{sub 2} nanocomposite film surface are subjected to a series of icing and deicing cycles in a humid (∼ 70% relative humidity) atmosphere and the resulting morphological changes are monitored and characterized using atomic force microscopy (AFM) and contact angle measurements. Our data show that the formation of the frozen or thawed water droplet, with no furthermore » shape change, on superhydrophobic SiO{sub 2} nanocomposite film, is obtained faster within each cycle as the number of the icing/deicing cycles increases. After 10 icing and deicing cycles, the superhydrophobic SiO{sub 2} nanocomposite film had a water contact angle value of 146 ± 2° which is effectively non-superhydrophobic. AFM analysis showed that the superhydrophobic SiO{sub 2} nanocomposite film surface area under the water droplet undergoes gradual mechanical damage during the repetitive icing/deicing cycles. We propose a possible mechanism of the morphological changes to the film surface that take place during the consecutive icing/deicing experiments. - Highlights: • Superhydrophobic film is subjected to repetitive icing/deicing treatments. • Water droplet shape transition is recorded and characterized thereafter. • Atomic force microscopy and contact angle measurements are performed. • The surface undergoes gradual mechanical damage during repetitive icing/deicing. • Mechanism for the observed surface morphological changes is suggested.« less

Diffusion and Clustering of Carbon Dioxide on Non-porous Amorphous Solid Water

DOE Office of Scientific and Technical Information (OSTI.GOV)

He, Jiao; Emtiaz, Shahnewaj M.; Vidali, Gianfranco

2017-03-01

Observations by ISO and Spitzer toward young stellar objects showed that CO{sub 2} segregates in the icy mantles covering dust grains. Thermal processing of the ice mixture was proposed as being responsible for the segregation. Although several laboratories studied thermally induced segregation, a satisfying quantification is still missing. We propose that the diffusion of CO{sub 2} along pores inside water ice is the key to quantify segregation. We combined Temperature Programmed Desorption and Reflection Absorption InfraRed Spectroscopy to study how CO{sub 2} molecules interact on a non-porous amorphous solid water (np-ASW) surface. We found that CO{sub 2} diffuses significantly onmore » an np-ASW surface above 65 K and clusters are formed at well below one monolayer. A simple rate equation simulation finds that the diffusion energy barrier of CO{sub 2} on np-ASW is 2150 ± 50 K, assuming a diffusion pre-exponential factor of 10{sup 12} s{sup −1}. This energy should also apply to the diffusion of CO{sub 2} on the wall of pores. The binding energy of CO{sub 2} from CO{sub 2} clusters and CO{sub 2} from H{sub 2}O ice has been found to be 2415 ± 20 K and 2250 ± 20 K, respectively, assuming the same prefactor for desorption. CO{sub 2}–CO{sub 2} interaction is stronger than CO{sub 2}–H{sub 2}O interaction, in agreement with the experimental finding that CO{sub 2} does not wet the np-ASW surface. For comparison, we carried out similar experiments with CO on np-ASW, and found that the CO–CO interaction is always weaker than CO–H{sub 2}O. As a result, CO wets the np-ASW surface. This study should be of help to uncover the thermal history of CO{sub 2} on the icy mantles of dust grains.« less

Condensation and Vaporization Studies of CH3OH and NH3 Ices: Major Implications for Astrochemistry

NASA Technical Reports Server (NTRS)

Sandford, Scott A.; Allamandola, Louis J.

1993-01-01

In an extension of previously reported work on ices containing H20, CO, CO2, SO2, H2S, and H2, We present measurements of the physical and infrared spectral properties of ices containing CH30H and NH3.The condensation and sublimation behavior of these ice systems is discussed and surface binding energies are presented for all of these molecules. The surface binding energies can be used to calculate the residence times of the molecules on grain surfaces as a function of temperature. It is demonstrated that many of the molecules used to generate radio maps of and probe conditions in dense clouds, for example CO and NH3, will be significantly depleted from the gas phase by condensation onto dust grains. Attempts to derive total column densities solely from radio maps that do not take condensation effects into account may vastly underestimate the true column densities of any given species. Simple CO condensation onto and vaporization off of grains appears to be capable of explaining the observed 87 of gas phase CO in cold, dense molecular cores. This is not the case for NH3, however, where thermal considerations alone predict that all of the NH3 should be condensed onto grains. The fact that some gas phase NH3 is observed indicates that additional desorption processes must be involved. The surface binding energies of CH3OH, in conjunction with this molecule's observed behavior during warm up in H2O-rich ices, is shown to provide an explanation of the large excess of CH3OH seen in many warm, dense molecular cores. The near-infrared spectrum and associated integrated band strengths of CH3OH-containing ice are given, as are middle infrared absorption band strengths for both CH3OH and NH3.

New horizons mapping of Europa and Ganymede.

PubMed

Grundy, W M; Buratti, B J; Cheng, A F; Emery, J P; Lunsford, A; McKinnon, W B; Moore, J M; Newman, S F; Olkin, C B; Reuter, D C; Schenk, P M; Spencer, J R; Stern, S A; Throop, H B; Weaver, H A

2007-10-12

The New Horizons spacecraft observed Jupiter's icy satellites Europa and Ganymede during its flyby in February and March 2007 at visible and infrared wavelengths. Infrared spectral images map H2O ice absorption and hydrated contaminants, bolstering the case for an exogenous source of Europa's "non-ice" surface material and filling large gaps in compositional maps of Ganymede's Jupiter-facing hemisphere. Visual wavelength images of Europa extend knowledge of its global pattern of arcuate troughs and show that its surface scatters light more isotropically than other icy satellites.

Destruction of C2H4O2 isomers in ice-phase by X-rays: Implication on the abundance of acetic acid and methyl formate in the interstellar medium

NASA Astrophysics Data System (ADS)

Rachid, Marina G.; Faquine, Karla; Pilling, S.

2017-12-01

The C2H4O2 isomers methyl formate (HCOOCH3), acetic acid (CH3COOH) and glycoaldehyde (HOCH2CHO) have been detected in molecular clouds in the interstellar medium, as well as, hot cores, hot corinos and around protostellar objects. However, their abundances are very different, being methyl formate more abundant than the other two isomers. This fact may be related to the different destruction by ionizing radiation of these molecules. The goal of this work is experimentally study the photodissociation processes of methyl formate and acetic acid ices when exposed to broadband soft X-ray from 6 up to 2000 eV. The experiments were performed coupled to the SGM beamline in the Brazilian Synchrotron Light Source (LNLS/CNPEM) at Campinas, Brazil. The simulated astrophysical ices (12 K) were monitored throughout the experiment using infrared vibrational spectroscopy (FTIR). The analysis of processed ices allowed the determination of the effective destruction cross sections of the parent molecules as well as the effective formation cross section of daughter molecular species such as CO, CO2, H2O, CH4 and H2CO (only for methyl formate) and the hydrocarbons C2H6 and C5H10 (only for acetic acid). The half-lives of molecules at ices toward young stellar objects (YSOs) and inside molecular clouds (e.g. Sgr B2 and W51) due to the presence of incoming soft X-rays were estimated. We determined the effective formation rate and the branching ratios for assigned daughter species after the establishment of a chemical equilibrium. The main product from photodissociation of both methyl formate and acetic acid is CO, that can be formed by recombination of ions, formed during the photodissociation, in the ice surface. The relative abundance between methyl formate and acetic acid (NCH3COOH/NHCOOCH3) in different astronomical scenarios and their column density evolution in the presence of X-rays were calculated. Our results suggest that such radiation field can be one of the factors that explain the difference in the C2H4O2 isomers abundances.

Evidence of calcium carbonates in coastal (Talos Dome and Ross Sea area) East Antarctica snow and firn: Environmental and climatic implications

NASA Astrophysics Data System (ADS)

Sala, M.; Delmonte, B.; Frezzotti, M.; Proposito, M.; Scarchilli, C.; Maggi, V.; Artioli, G.; Dapiaggi, M.; Marino, F.; Ricci, P. C.; De Giudici, G.

2008-07-01

Micrometre-sized aeolian dust particles stored in Antarctic firn and ice layers are a useful tool for reconstructing climate and environmental changes in the past. The mineral content, particle concentration and chemical composition of modern dust in firn cores from the peripherycal dome (Talos Dome) and coastal area of East Antarctica (Ross Sea sector) were investigated. During analyses there was a considerable decrease in microparticle concentrations within a few hours of ice sample melting, accompanied by a systematic increase in the concentration of calcium ions (Ca 2+) in solution. Based on mineralogical phase analyses, which reveal the presence of anhydrous and hydrous calcium carbonates such as calcite (CaCO 3), monohydrocalcite (CaCO 3·H 2O) and ikaite (CaCO 3·6H 2O, hexahydrate calcium carbonate), the observed variations in concentrations are ascribed to the partial dissolution of the carbonate content of samples. Soluble carbonate compounds are thus primary aerosols included into the samples along with insoluble aluminosilicate minerals. We hypothesize hydrous carbonates may derive from the sea ice surface, where ikaite typically forms at the early stages of sea ice formation. Back trajectory calculations show that favourable events for air mass advection from the sea ice surface to Talos Dome are rare but likely to occur.

Comparison of two stable hydrogen isotope-ratio measurement techniques on Antarctic surface-water and ice samples

USGS Publications Warehouse

Hopple, J.A.; Hannon, J.E.; Coplen, T.B.

1998-01-01

A comparison of the new hydrogen isotope-ratio technique of Vaughn et al. ([Vaughn, B.H., White, J.W.C., Delmotte, M., Trolier, M., Cattani, O., Stievenard, M., 1998. An automated system for hydrogen isotope analysis of water. Chem. Geol. (Isot. Geosci. Sect.), 152, 309-319]; the article immediately preceding this article) for the analysis of water samples utilizing automated on-line reduction by elemental uranium showed that 94% of 165 samples of Antarctic snow, ice, and stream water agreed with the ??2H values determined by H2-H2O platinum equilibration, exhibiting a bias of +0.5??? and a 2 - ?? variation of 1.9???. The isotopic results of 10 reduction technique samples, however, gave ??2H values that differed by 3.5??? or more, and were too negative by as much as 5.4??? and too positive by as much as 4.9??? with respect to those determined using the platinum equilibration technique.

Photochemistry of Coronene in Cosmic Water Ice Analogs at Different Concentrations

DOE Office of Scientific and Technical Information (OSTI.GOV)

De Barros, A. L. F.; Mattioda, A. L.; Ricca, A.

This work presents the photochemistry of ultraviolet (UV) irradiated coronene in water ices at 15 K studied using mid-infrared Fourier transform (FTIR) spectroscopy for C{sub 24}H{sub 12}:H{sub 2}O at concentrations of (1:50), (1:150), (1:200), (1:300), and (1:400). Previous UV irradiation studies of anthracene:H{sub 2}O, pyrene:H{sub 2}O, and benzo[ghi]perylene:H{sub 2}O ices at 15 K have shown that aromatic alcohols and ketones, as well as CO{sub 2} and H{sub 2}CO, are formed at very low temperatures. Likewise, here, in addition to the coronene cation, hydroxy-, keto-, and protonated coronene (coronene H{sup +}) are formed. The rate constants for the decay of neutralmore » coronene and for the formation of photoproducts have been derived. It is shown that Polycyclic Aromatic Hydrocarbons (PAHs) and their UV induced PAH:H{sub 2}O photoproducts have mid-infrared spectroscopic signatures in the 5–8 μ m region that can contribute to the interstellar ice components described by Boogert et al. as C1–C5. Our results suggest that oxygenated and hydrogenated PAHs could be in UV-irradiated regions of the interstellar medium where water-rich ices are important.« less

Three separate classes of bacterial ice nucleation structures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Turner, M.A.; Arellano, F.; Kozloff, L.M.

1990-05-01

Studies of the properties of the ice nucleation structure exposed on the surfaces of various bacteria such as Pseudomonas syringae, Erwinia herbicola, or various strains of Ice+ recombinant Escherichia coli have shown that there are clearly three major related but chemically distinct types of structures on these cells. First, the ability of Ice+ cells to nucleate super-cooled D2O has been examined, and it has been found that this ability (relative to the ability of the same cells to nucleate super-cooled H2O) exhibited three characteristic nucleating patterns. The rarest structure, called class A, is found on only a small fraction ofmore » cells in a culture, nucleates H2O at temperatures above -4.4 degrees C, and is an effective nucleator of super-cooled D2O. A second class of structure, called class B, is found on a larger portion of the cells, nucleates H2O between -4.8 and -5.7 degrees C, and is a relatively poor nucleator of super-cooled D2O. The class C structure is found on almost all cells and nucleates at -7.6 degrees C or colder. These three classes of structures were also differentiated by their sensitivities to low concentrations of water-miscible organic solvents such as dioxane or dimethyl sulfoxide. Depending on the specific bacterial strain, the addition of these solvents to bacterial suspensions lowered the nucleation activity of the class A structure by 1,000-fold or more. The nucleation activities of class B structures in the same culture were highly resistant to these compounds and were lowered only by 20 to 40%.« less

Changes in the morphology of interstellar ice analogues after hydrogen atom exposure.

PubMed

Accolla, Mario; Congiu, Emanuele; Dulieu, François; Manicò, Giulio; Chaabouni, Henda; Matar, Elie; Mokrane, Hakima; Lemaire, Jean Louis; Pirronello, Valerio

2011-05-07

The morphology of water ice in the interstellar medium is still an open question. Although accretion of gaseous water could not be the only possible origin of the observed icy mantles covering dust grains in cold molecular clouds, it is well known that water accreted from the gas phase on surfaces kept at 10 K forms ice films that exhibit a very high porosity. It is also known that in the dark clouds H(2) formation occurs on the icy surface of dust grains and that part of the energy (4.48 eV) released when adsorbed atoms react to form H(2) is deposited in the ice. The experimental study described in the present work focuses on how relevant changes of the ice morphology result from atomic hydrogen exposure and subsequent recombination. Using the temperature-programmed desorption (TPD) technique and a method of inversion analysis of TPD spectra, we show that there is an exponential decrease in the porosity of the amorphous water ice sample following D-atom irradiation. This decrease is inversely proportional to the thickness of the ice and has a value of ϕ(0) = 2 × 10(16) D-atoms cm(-2) per layer of H(2)O. We also use a model which confirms that the binding sites on the porous ice are destroyed regardless of their energy depth, and that the reduction of the porosity corresponds in fact to a reduction of the effective area. This reduction appears to be compatible with the fraction of D(2) formation energy transferred to the porous ice network. Under interstellar conditions, this effect is likely to be efficient and, together with other compaction processes, provides a good argument to believe that interstellar ice is amorphous and non-porous. This journal is © the Owner Societies 2011

Virulence profiling and quantification of verocytotoxin-producing Escherichia coli O145:H28 and O26:H11 isolated during an ice cream-related hemolytic uremic syndrome outbreak.

PubMed

Buvens, Glenn; Possé, Björn; De Schrijver, Koen; De Zutter, Lieven; Lauwers, Sabine; Piérard, Denis

2011-03-01

In September-October 2007, a mixed-serotype outbreak of verocytotoxin-producing Escherichia coli (VTEC) O145:H28 and O26:H11 occurred in the province of Antwerp, Belgium. Five girls aged between 2 and 11 years developed hemolytic uremic syndrome, and seven other coexposed persons with bloody diarrhea were identified. Laboratory confirmation of O145:H28 infection was obtained for three hemolytic uremic syndrome patients, one of whom was coinfected with O26:H11. The epidemiological and laboratory investigations revealed ice cream as the most likely source of the outbreak. The ice cream was produced at a local dairy farm using pasteurized milk. VTEC of both serotypes with indistinguishable pulsed-field gel electrophoresis patterns were isolated from patients, ice cream, and environmental samples. Quantitative analysis of the ice cream indicated concentrations of 2.4 and 0.03 CFU/g for VTEC O145 and O26, respectively. Virulence typing revealed that the repertoire of virulence genes carried by the O145:H28 outbreak strain was comparable to that of O157 VTEC and more exhaustive as compared to the O26:H11 outbreak strain and nonrelated clinical strains belonging to these serotypes. Taken together, these data suggest that O145:H28 played the most important role in this outbreak.

The Martian paleoclimate and enhanced atmospheric carbon dioxide

NASA Technical Reports Server (NTRS)

Cess, R. D.; Owen, T.; Ramanathan, V.

1980-01-01

Current evidence indicates that the Martian surface is abundant with water presently in the form of ice, while the atmosphere was at one time more massive with a past surface pressure of as much as 1 atm of CO2. In an attempt to understand the Martian paleoclimate, a past CO2-H2O greenhouse was modeled and global temperatures which are consistent with an earlier presence of liquid surface water are found in agreement with the extensive evidence for past fluvial erosion. An important aspect of the CO2-H2O greenhouse model is the detailed inclusion of CO2 hot bands. For a surface pressure of 1 atm of CO2, the present greenhouse model predicts a global mean surface temperature of 294 K, but if the hot bands are excluded, a surface temperature of only 250 K is achieved.

Loss of Water to Space from Mars: Processes and Implications

NASA Astrophysics Data System (ADS)

Kass, D. M.

2001-12-01

One of the major sinks for water on Mars is the loss to space. This occurs via a complex series of processes that transport the individual atoms to the upper atmosphere, where several escape mechanisms remove them. Hydrogen and deuterium are lost primarily by Jeans escape. Non-thermal processes also remove H and D, but are only important in determining D loss at solar minimum under modern conditions. The present H loss rate is equivalent to the loss of 10-3~pr-\\micron~yr-1 of water. The loss of oxygen is more complicated. The three main processes are indirect (or ionospheric) sputtering, solar wind pickup of O+, and O2+ dissociative recombination. Their relative importance has varied over the history of Mars. The combined effect of the O loss processes is to remove a ~ 50~m global layer of water over the last 3.5 Gyr. Based on photochemical modeling, the loss of oxygen and hydrogen are balanced (over geological timescales) by a feedback process. During the early history of Mars, impact erosion and hydrodynamic blow-off may have removed significant water. But, it is difficult to estimate their quantitative effects. The transport of individual H, D and O atoms to the exosphere where they can escape is not completely understood. It occurs primarily via intermediate species, H2, HD, O2 and CO2. The H2 and HD are formed by photolysis of water and the odd hydrogen photochemistry. One open issue is the mechanism regulating the partitioning of D between HDO and HD (which controls the supply of D available for escape from the exosphere). The various loss processes isotopically enrich Martian water since the exospheric escape source region is depleted. Jeans escape and the transport from the lower atmosphere further fractionate hydrogen, the most useful isotopic system. Based on recent observations, the D/H fractionation factor, F ~ 0.02. Measurements of atmospheric water vapor indicate it is enriched in deuterium, with a D/H ratio ~ 5 times the terrestrial value. Since most of the water on Mars is likely to be in the form of ice, it is presumably further fractionated by ~ 0.8 due to ice/water vapor interactions. This yields an effective D/H enrichment of ~ 7 for reservoirs in equilibrium with the atmosphere. From a loss to space point of view, Martian water can be divided into three reservoirs. The first is the thin, 10 pr-\\micron, atmospheric water. The second is a global exchangeable reservoir in long term isotopic equilibrium with the atmosphere. This probably encompasses the polar caps, ice in polar layered deposits and any other near surface ice or adsorbed water. The third, more speculative, reservoir is a non-exchanging reservoir (a deep sub-surface cryosphere). In addition, due to the small size of the atmospheric reservoir, difficulty in isotopically equilibrating it with the entire exchangeable reservoir, and the relatively rapid H2 loss rate, there is also an intermediate exchangeable reservoir of ~ 4~mm. This is probably either a surface layer on the polar caps or near surface ice deposits. By assuming an initial terrestrial D/H ratio for Martian water (based on condritic meteorites) and a loss to space of ~ 50~m (based on the total O loss), the size of the exchangeable reservoir can be estimated. Two conceptual models are possible, depending on whether or not the non-exchangeable reservoir replenishes the exchangeable one. Quantitatively, the two models yield almost identical reservoir sizes, ~ 9~m (about the size of the northern polar cap). If, due to slow rate of isotopic diffusion in ice, the exchangeable reservoir actually has the same isotopic enrichment as the atmosphere, it would contain ~ 12~m of water.

Experimental Simulation of Cryomagmatic Processes. Water Ice, Clathrates and Salts

NASA Astrophysics Data System (ADS)

Muñoz-Iglesias, V.; Prieto-Ballesteros, O.; López, I.

2018-06-01

Study of diverse cryomagmatic processes based on the system H2O-CO2-MgSO4 with application to Europa. The type of the crystals formed is related to volume-temperature changes, while their morphology is associated with surface geological features.

Formation of model polar stratospheric cloud films

NASA Technical Reports Server (NTRS)

Middlebrook, Ann M.; Koehler, Birgit G.; Mcneill, Laurie S.; Tolbert, Margaret A.

1992-01-01

Fourier transform infrared spectroscopy was used to examine the competitive growth of films representative of polar stratospheric clouds. These experiments show that either crystalline nitric acid trihydrate (beta-NAT) or amorphous films with H2O:HNO3 ratios close to 3:1 formed at temperatures 3-7 K warmer than the ice frost point under stratospheric pressure conditions. In addition, with higher HNO3 pressure, we observed nitric acid dihydrate (NAD) formation at temperatures warmer than ice formation. However, our experiments also show that NAD surfaces converted to beta-NAT upon exposure to stratospheric water pressures. Finally, we determined that the net uptake coefficient for HNO3 on beta-NAT is close to unity, whereas the net uptake coefficient for H2O is much less.

Surface materials on unusual planetary object Chiron

NASA Technical Reports Server (NTRS)

Hartmann, W. K.; Cruikshank, D. P.; Degewij, J.; Capps, R. W.

1981-01-01

JHK near-infrared colorimetry of the surface of the planetary object 2060 Chiron has yielded colors consistent with those of outer solar system asteroids, which have: (1) albedos of only a few percent, (2) C-, RD-, or DM-type spectra, and (3) no known H2O ice absorption features. The colors are also in keeping with theoretical colors for certain size distributions of dirty ice grains. Along with VJHK colorimetric data, results suggest that the spectrally dominant surface is probably dark, carbonaceous-like silicate dust with a possible, microscale admixture of ice grains. It is concluded that, if Chiron has the low albedo common to such materials on known interplanetary bodies, its diameter may lie in the 310-400 km range and therefore place it among the eight largest asteroids.

The effect of rock particles and D2O replacement on the flow behaviour of ice.

PubMed

Middleton, Ceri A; Grindrod, Peter M; Sammonds, Peter R

2017-02-13

Ice-rock mixtures are found in a range of natural terrestrial and planetary environments. To understand how flow processes occur in these environments, laboratory-derived properties can be extrapolated to natural conditions through flow laws. Here, deformation experiments have been carried out on polycrystalline samples of pure ice, ice-rock and D 2 O-ice-rock mixtures at temperatures of 263, 253 and 233 K, confining pressure of 0 and 48 MPa, rock fraction of 0-50 vol.% and strain-rates of 5 × 10 -7 to 5 × 10 -5  s -1 Both the presence of rock particles and replacement of H 2 O by D 2 O increase bulk strength. Calculated flow law parameters for ice and H 2 O-ice-rock are similar to literature values at equivalent conditions, except for the value of the rock fraction exponent, here found to be 1. D 2 O samples are 1.8 times stronger than H 2 O samples, probably due to the higher mass of deuterons when compared with protons. A gradual transition between dislocation creep and grain-size-sensitive deformation at the lowest strain-rates in ice and ice-rock samples is suggested. These results demonstrate that flow laws can be found to describe ice-rock behaviour, and should be used in modelling of natural processes, but that further work is required to constrain parameters and mechanisms for the observed strength enhancement.This article is part of the themed issue 'Microdynamics of ice'. © 2016 The Author(s).

Rapid changes in surface water carbonate chemistry during Antarctic sea ice melt

NASA Astrophysics Data System (ADS)

Jones, Elizabeth M.; Bakker, Dorothee C. E.; Venables, Hugh J.; Whitehouse, Michael J.; Korb, Rebecca E.; Watson, Andrew J.

2010-11-01

ABSTRACT The effect of sea ice melt on the carbonate chemistry of surface waters in the Weddell-Scotia Confluence, Southern Ocean, was investigated during January 2008. Contrasting concentrations of dissolved inorganic carbon (DIC), total alkalinity (TA) and the fugacity of carbon dioxide (fCO2) were observed in and around the receding sea ice edge. The precipitation of carbonate minerals such as ikaite (CaCO3.6H2O) in sea ice brine has the net effect of decreasing DIC and TA and increasing the fCO2 in the brine. Deficits in DIC up to 12 +/- 3 μmol kg-1 in the marginal ice zone (MIZ) were consistent with the release of DIC-poor brines to surface waters during sea ice melt. Biological utilization of carbon was the dominant processes and accounted for 41 +/- 1 μmol kg-1 of the summer DIC deficit. The data suggest that the combined effects of biological carbon uptake and the precipitation of carbonates created substantial undersaturation in fCO2 of 95 μatm in the MIZ during summer sea ice melt. Further work is required to improve the understanding of ikaite chemistry in Antarctic sea ice and its importance for the sea ice carbon pump.

Interannual observations and quantification of summertime H2O ice deposition on the Martian CO2 ice south polar cap

USGS Publications Warehouse

Brown, Adrian J.; Piqueux, Sylvain; Titus, Timothy N.

2014-01-01

The spectral signature of water ice was observed on Martian south polar cap in 2004 by the Observatoire pour l'Mineralogie, l'Eau les Glaces et l'Activite (OMEGA) ( Bibring et al., 2004). Three years later, the OMEGA instrument was used to discover water ice deposited during southern summer on the polar cap ( Langevin et al., 2007). However, temporal and spatial variations of these water ice signatures have remained unexplored, and the origins of these water deposits remains an important scientific question. To investigate this question, we have used observations from the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) instrument on the Mars Reconnaissance Orbiter (MRO) spacecraft of the southern cap during austral summer over four Martian years to search for variations in the amount of water ice. We report below that for each year we have observed the cap, the magnitude of the H2O ice signature on the southern cap has risen steadily throughout summer, particularly on the west end of the cap. The spatial extent of deposition is in disagreement with the current best simulations of deposition of water ice on the south polar cap (Montmessin et al., 2007). This increase in water ice signatures is most likely caused by deposition of atmospheric H2O ice and a set of unusual conditions makes the quantification of this transport flux using CRISM close to ideal. We calculate a ‘minimum apparent‘ amount of deposition corresponding to a thin H2O ice layer of 0.2 mm (with 70% porosity). This amount of H2O ice deposition is 0.6–6% of the total Martian atmospheric water budget. We compare our ‘minimum apparent’ quantification with previous estimates. This deposition process may also have implications for the formation and stability of the southern CO2 ice cap, and therefore play a significant role in the climate budget of modern day Mars.

Tropical sea surface temperature variability near the Oligocene - Miocene boundary

NASA Astrophysics Data System (ADS)

Zhang, Y.; Pagani, M.

2010-12-01

The Oligocene/Miocene (O-M) boundary is characterized by a period of rapid and intense glaciation labeled Mi-1 at ~ 23.1 Ma. An abrupt 1.5‰ increase in the benthic foraminifera oxygen isotope composition that characterizes Mi-1 may indicate a (1) significant deep-water temperature decrease; (2) major ice-sheet expansion, or the combination of both. Current coarse Mg/Ca-based temperature estimations for the early Miocene suggests that deep-ocean temperatures were ~2°C warmer than Today [1, 2]. However, Mg/Ca based temperatures can also be influenced by changes in the carbonate ion concentration, vital effects, and diagenesis. In particular, recent evidence from mid-ocean ridge flank carbonate veins shows dramatic seawater Mg/Ca ratio changes during the Neogene (Mg/Ca from ~2.2 to 5.3, [3]), which further challenges the application of Mg/Ca thermometry. Owing to poor temperature constraints, current ice volume estimations for the late Oligocene/early Miocene range from 125% of the present-day East Antarctic Ice Sheet (EAIS) to a nearly complete collapse of the Antarctic glaciers [4]. Here we present tropical sea surface temperatures (SSTs) records based on TEX86 and alkenone UK37 near the O-M boundary. Sediment samples from Ocean Drilling Program (ODP) Site 926 in the Ceara Rise (tropical Atlantic) and Site 1148 in the South China Sea (tropical Pacific) were subject to lipid extraction, separation, gas chromatography, and liquid chromatography-mass spectrometry analysis. TEX86-based SST indicates that the tropics were ~3-4°C warmer than today and relatively stable during Mi-1. This suggests that ice-sheet dynamics, rather than temperature, might be responsible for the observed oxygen isotope changes during the O-M boundary. Further, O-M boundary averaged temperatures recorded at site 926 is ~ 0.5°C higher relative to the late Eocene from site 925 (a nearby site [5]). Given late Oligocene benthic δ18O that suggests at least 1‰ enrichment relative to the late Eocene (e.g. ODP 1218 [2]), our records suggest major Antarctic ice build-up in the Oligocene. Additional work across high-latitude sites is necessary to evaluate how the extratropics responded to climate change during Mi-1, as well as modeling efforts to quantitatively resolve ice volume from temperature. [1] K. Billups, D.P. Schrag, Paleotemperatures and ice volume of the past 27 Myr revisited with paired Mg/Ca and 18O/16O measurements on bethic foraminifera, Paleoceanography 17(2002). [2] C.H. Lear, Y. Rosenthal, H.K. Coxall, P.A. Wilson, Late Eocene to early Miocene ice sheet dynamics and the global carbon cycle, Paleoceanography 19(2004). [3] R.M. Coggon, D.A.H. Teagle, C.E. Smith-Duque, J.C. Alt, M.J. Copper, Reconstructing past seawater Mg/Ca and Sr/Ca from Mid-Ocean Ridge flank calcium carbonate veins, Science 327(2010) 1141-1147. [4] S.F. Pekar, R.M. DeConto, High-resolution ice-volume estimates for the early Miocene: Evidence for a dynamic ice sheet in Antarctica, Palaeogeogr. Palaeoclimatol. Palaeoecol. 231(2006) 101-109. [5] Z. Liu, M. Pagani, D. Zinniker, R. DeConto, M. Huber, H. Brinkhuis, S.R. Shah, R.M. Leckie, A. Pearson, Global Cooling During the Eocene-Oligocene Climate Transition, Science 323(2009) 1187-1190.

Synthesis of polycrystalline methane hydrate, and its phase stability and mechanical properties at elevated pressure

USGS Publications Warehouse

Stern, L.A.; Kirby, S.H.; Durham, W.B.

1997-01-01

Test specimens of methane hydrate were grown under static conditions by combining cold, pressurized CH4 gas with H2O ice grains, then warming the system to promote the reaction CH4 (g) + 6H2O (s???l) ??? CH4??6H2O. Hydrate formation evidently occurs at the nascent ice/liquid water interface, and complete reaction was achieved by warming the system above 271.5 K and up to 289 K, at 25-30 MPa, for approximately 8 hours. The resulting material is pure methane hydrate with controlled grain size and random texture. Fabrication conditions placed the H2O ice well above its melting temperature before reaction completed, yet samples and run records showed no evidence for bulk melting of the ice grains. Control experiments using Ne, a non-hydrate-forming gas, verified that under otherwise identical conditions, the pressure reduction and latent heat associated with ice melting is easily detectable in our fabrication apparatus. These results suggest that under hydrate-forming conditions, H2O ice can persist metastably at temperatures well above its melting point. Methane hydrate samples were then tested in constant-strain-rate deformation experiments at T= 140-200 K, Pc= 50-100 MPa, and ????= 10-4-10-6 s-1. Measurements in both the brittle and ductile fields showed that methane hydrate has measurably different strength than H2O ice, and work hardens to a higher degree compared to other ices as well as to most metals and ceramics at high homologous temperatures. This work hardening may be related to a changing stoichiometry under pressure during plastic deformation; x-ray analyses showed that methane hydrate undergoes a process of solid-state disproportionation or exsolution during deformation at conditions well within its conventional stability field.

Seasonal evolution of the Martian cryptic region: influence of the atmospheric opacity

NASA Astrophysics Data System (ADS)

Portyankina, G.; Markiewicz, W. J.; Kossacki, K. J.

2005-08-01

Mars Orbiter Camera (MOC) performed repeated observations of chosen areas in polar regions to monitor seasonal and/or annual changes. Images E09-00028 and R08-01730 centered at 82.5°S, 41°E were taken in years 2001 and 2003 respectively. They show the same morphological features, however differ significantly in surface albedo, the image from 2001 shows a lower albedo than the one from 2003. Imaged areas lie inside the cryptic region and show spider patterns. The observed interannual variability may be related to the global dust storm that happened in 2001 and finished around Ls=230°, i.e. just before image E09-00028 was taken. Here we model the seasonal ice sublimation/condensation cycle to show that the evolution of this particular area of the cryptic region was affected by the dust storm during year 2001. The model used for the present work has been described in Kossacki and Markiewicz, (2004). It includes self-consistent treatment of the sublimation and condensation of CO2 and H2O ices, and was used to calculate surface temperatures and thicknesses of CO2 and H2O ice layers for the corresponding conditions of these two years. Our modelling shows that the dust storm lowered surface temperatures, and thus caused later than usual seasonal sublimation of both CO2 and water ices. It also considerably decreased surface albedo and these two important effects almost cancel: the solar flux is reduced during a dust storm but at the same time the dust that precipitates onto the surface reduces the albedo and thus allows a bigger fraction of the solar radiation to be absorbed. The surface temperature stays at about 146K for almost half of the Martian year, both during 2001 and 2003. We also considered impact of the surface roughness: it results in some smoothing of the average temperature rise that is associated with the defrosting of the surface.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Honda, M.; Kudo, T.; Terada, H.

We made near-infrared multicolor imaging observations of a disk around Herbig Be star HD 100546 using Gemini/NICI. K (2.2 μm), H{sub 2}O ice (3.06 μm), and L′ (3.8 μm) disk images were obtained and we found a 3.1 μm absorption feature in the scattered light spectrum, likely due to water ice grains at the disk surface. We compared the observed depth of the ice absorption feature with the disk model based on Oka et al., including the water ice photodesorption effect by stellar UV photons. The observed absorption depth can be explained by both the disk models with and without themore » photodesorption effect within the measurement accuracy, but the model with photodesorption effects is slightly more favored, implying that the UV photons play an important role in the survival/destruction of ice grains at the Herbig Ae/Be disk surface. Further improvement to the accuracy of the observations of the water ice absorption depth is needed to constrain the disk models.« less

Organic Compounds Produced by Photolysis of Realistic Interstellar and Cometary Ice Analogs Containing Methanol

NASA Astrophysics Data System (ADS)

Bernstein, Max P.; Sandford, Scott A.; Allamandola, Louis J.; Chang, Sherwood; Scharberg, Maureen A.

1995-11-01

The infrared (IR) spectra of ultraviolet (UV) and thermally processed, methanol-containing interstellar/ cometary ice analogs at temperatures from 12 to 300 K are presented. Infrared spectroscopy, 1H and 13C nuclear magnetic resonance (NMR) spectroscopy, and gas chromatography-mass spectrometry indicate that CO (carbon monoxide), CO2 (carbon dioxide), CH4 (methane), HCO (the formyl radical), H2CO (formaldehyde), CH3CH2OH (ethanol), HC(=O)NH2 (formamide), CH3C(=O)NH2 (acetamide), and R-C=-N (nitriles) are formed. In addition, the organic materials remaining after photolyzed ice analogs have been warmed to room temperature contain (in rough order of decreasing abundance), (1) hexamethylenetetramine (HMT, C6H12N4), (2) ethers, alcohols, and compounds related to polyoxymethylene {POM, ( CH2O )n}, and (3) ketones {R-C(=O)-R'} and amides {H2NC(=O)-R}. Most of the carbon in these residues is thought to come from the methanol in the original ice. Deuterium and 13C isotopic labeling demonstrates that methanol is definitely the source of carbon in HMT. High concentrations of HMT in interstellar and cometary ices could have important astrophysical consequences. The ultraviolet photolysis of HMT frozen in H2O ice readily produces the "XCN" band observed in the spectra of protostellar objects and laboratory ices, as well as other nitriles. Thus, HMT may be a precursor of XCN and a source of CN in comets and the interstellar medium. Also, HMT is known to hydrolyze under acidic conditions to yield ammonia, formaldehyde, and amino acids. Thus, HMT may be a significant source of prebiogenic compounds on asteroidal parent bodies. A potential mechanism for the radiative formation of HMT in cosmic ices is outlined.

Synthesis of complex organic molecules in simulated methane rich astrophysical ices

NASA Astrophysics Data System (ADS)

Esmaili, Sasan; Bass, Andrew D.; Cloutier, Pierre; Sanche, Léon; Huels, Michael A.

2017-12-01

It has been proposed that organic molecules required for life on earth may be formed by the radiation processing of molecular ices in space environments, e.g., within our solar system. Such processes can be studied in the laboratory with surface science analytical techniques and by using low-energy electron (LEE) irradiation to simulate the effects of the secondary electrons that are generated in great abundance whenever ionizing radiation interacts with matter. Here we present new measurements of 70 eV LEE irradiation of multilayer films of CH4, 18O2, and CH4/18O2 mixtures (3:1 ratio) at 22 K. The electron stimulated desorption (ESD) yields of cations and anions have been recorded as a function of electron fluence. At low fluence, the prompt desorption of more massive multi-carbon or C—O containing cationic fragments agrees with our earlier measurements. However, new anion ESD signals of C2-, C2H-, and C2H2- from CH4/18O2 mixtures increase with fluence, indicating the gradual synthesis (and subsequent electron-induced fragmentation) of new, more complex species containing several C and possibly O atoms. Comparisons between the temperature programed desorption (TPD) mass spectra of irradiated and unirradiated films show the electron-induced formation of new chemical species, the identities of which are confirmed by reference to the NIST database of electron impact mass spectra and by TPD measurements of films composed of the proposed products. New species observed in the TPD of irradiated mixture films include C3H6, C2H5OH, and C2H6. Furthermore, X-ray photoelectron spectroscopy of irradiated films confirms the formation of C—O, C=O, and O=C—O— bonds of newly formed molecules. Our experiments support the view that secondary LEEs produced by ionizing radiation drive the chemistry in irradiated ices in space, irrespective of the radiation type.

Fe embedded in ice: The impacts of sublimation and energetic particle bombardment

NASA Astrophysics Data System (ADS)

Frankland, Victoria L.; Plane, John M. C.

2015-05-01

Icy particles containing a variety of Fe compounds are present in the upper atmospheres of planets such as the Earth and Saturn. In order to explore the role of ice sublimation and energetic ion bombardment in releasing Fe species into the gas phase, Fe-dosed ice films were prepared under UHV conditions in the laboratory. Temperature-programmed desorption studies of Fe/H2O films revealed that no Fe atoms or Fe-containing species co-desorbed along with the H2O molecules. This implies that when noctilucent ice cloud particles sublimate in the terrestrial mesosphere, the metallic species embedded in them will coalesce to form residual particles. Sputtering of the Fe-ice films by energetic Ar+ ions was shown to be an efficient mechanism for releasing Fe into the gas phase, with a yield of 0.08 (Ar+ energy=600 eV). Extrapolating with a semi-empirical sputtering model to the conditions of a proton aurora indicates that sputtering by energetic protons (>100 keV) should also be efficient. However, the proton flux in even an intense aurora will be too low for the resulting injection of Fe species into the gas phase to compete with that from meteoric ablation. In contrast, sputtering of the icy particles in the main rings of Saturn by energetic O+ ions may be the source of recently observed Fe+ in the Saturnian magnetosphere. Electron sputtering (9.5 keV) produced no detectable Fe atoms or Fe-containing species. Finally, it was observed that Fe(OH)2 was produced when Fe was dosed onto an ice film at 140 K (but not at 95 K). Electronic structure theory shows that the reaction which forms this hydroxide from adsorbed Fe has a large barrier of about 0.7 eV, from which we conclude that the reaction requires both translationally hot Fe atoms and mobile H2O molecules on the ice surface.

Effects of Water Amount on the Surface Environment of Terrestrial Planets: High Pressure Ice and Carbon Cycle

NASA Astrophysics Data System (ADS)

Nakayama, Akifumi; Abe, Yutaka

2015-12-01

Terrestrial planets with several wt% of H2O in extrasolar planetary systems are theoretically predicted in the habitable zone [Raymond et al., 2004]. Such planets are expected to be covered by an ocean entirely (called as “ocean planets”). Amount of atmospheric CO2 (PCO2) is important for surface environment because CO2 is a strong greenhouse gas. PCO2 is determined by a race between degassing and sink through weathering on carbon cycle. On an ocean planet, seafloor weathering is important because continental weathering can’t work [Abbot et al., 2012]. In addition, ocean planets with large water amount may have high-pressure (HP) ice on the seafloor [Leger et al., 2004]. Since the ocean floor is covered by ice in such case, it has been thought that any weathering processes will not work and PCO2 will be extremely high. When plate tectonics works, heat flow from oceanic crust decreases with distance from the mid ocean ridge. Therefore, HP ice near the mid ocean ridge will be kept solid-liquid coexistent state at the melting point because of high heat flow. Seafloor weathering works in this region. The seafloor weathering under this condition efficiently works because weathering temperature is kept melting point regardless of surface temperature. Thus, our aim is to clarify the relationship between water amount and surface environment focusing seafloor environment. We develop a carbon cycle model considering the seafloor weathering. Our major assumptions are following; 1) Earth-sized ocean planets with various water amount, 2) Degassing rate is depended on the total amount of carbon and total carbon inventory is proportional to the surface water amount. We investigated thermal state of HP ice and determined effective weathering region where HP ice is coexistent with water, then we investigated the PCO2 in equilibrium state where degassing and regassing are balanced. As a result, forming of HP ice may cause snowball state due to high weathering rate. When solar incident flux and heat flow from mantle are the present Earth’s value and a ratio of CO2 / H2O inventory is carbonaceous chondrite composition, a planet with large ocean which is larger than 90 Earth’s ocean mass lapses into snowball state. It was previously believed that forming of HP ice supports warm climate; rather, forming of HP ice could cause snowball state.

Desorption induced by solar wind electrons analogs in methanol ice

NASA Astrophysics Data System (ADS)

Bergantini, A. S.; Pilling, Sergio; Andrade, Diana; Boechat-Roberty, Heloisa Maria; Rocco, Maria Luiza M.

2012-07-01

Methanol (CH _{3}OH) has been detected in several environments in space, such as comets, asteroids, grains of interstellar dust and protostars forming regions such as W33A and RAFGL 7009. CH _{3}OH is the most abundant molecule (after H _{2}O) found in solid state in these objects. The action of ionizing agents in such environments induces changes in methanol ice which lead to the formation ionic species, reactive radicals and new compounds. In this experiment, frozen methanol (142 K) was irradiated with an electron beam (energies from 650 to 1500 eV) inside an ultra-high vacuum chamber (˜ 1×10^{-10} mbar), at the Surface Chemistry Laboratory of Federal University of Rio de Janeiro (LaQuiS/ UFRJ). The beam simulates the action of electrons from solar wind in frozen surfaces like as comets, asteroids and moons. Results show the desorption of several new ionized species such as (CH _{3}OH)H ^{+}, H _{2}COH ^{+}, C _{2}H _{3} ^{+}, HCO ^{+}, CO ^{+}, O ^{+}, C ^{+}, H ^{+}. The individual desorbed ion rate was calculated. The determined half-life of frozen methanol in Earth orbit due to the electron bombardment was about 4.2 yr. The ionic desorption rate is an important parameter in surface chemistry, since these parameters are often approximated in chemical evolution models of astrophysical environments, due to the lack of laboratory data.

Proton and deuteron position preferences in water clusters: an ab initio study.

PubMed

Anick, David J

2005-12-22

In order to explore the effect of H-to-D substitution on the zero-point energy (ZPE) of water clusters, Hessians were computed for a database of 53 optimized (H2O)n clusters, 5 < or = n < or = 21, at the B3LYP6-311 + + G** level. The 53 clusters contained 1524 protons, which were sorted into 18 categories according to the type of their donor O and (if not free) acceptor O. Letting deltaZPE[H]* denote the change in ZPE when the proton H* is replaced by D, mean values for deltaZPE[H*] for the H-bonded categories ranged from -2172 cal mol(-1) for H* in a DDAA-DDAA bond to -2118 for H* in a DAA-DDA bond. Mean value for H* free on DAA (respectively, DA) was -2018 (respectively, -1969). For DAA-DDA bonds, and for short H bonds in general, there was a strong inverse correlation between /deltaZPE[H*]/ and the O-H* distance. deltaZPE for multiple H-to-D substitutions was additive, except for a cooperativity effect of -13.7 to -19.7 cal mol(-1) when two substituted protons were in the same H2O unit and a much smaller cooperativity when one proton's donor was the other's acceptor. Implications of these data include a relative preference for D to occupy H bonded rather than free positions in finite water clusters, a value of 3.82 for the disproportionation equilibrium constant of mixed ice at 150 K, increased occupation by H at surface positions of mixed ice, and a larger average coordination number for liquid D2O than for liquid H2O.

Mechanisms for Incorporation of Hydrogen in and on the Lunar Surface

NASA Astrophysics Data System (ADS)

Dyar, M. D.; Hibbitts, C.; Liu, Y.; Taylor, L. A.; Rossman, G. R.; Orlando, T. M.; Seaman, S. J.; Tucker, J. M.; Pieters, C. M.

2009-12-01

Absorption features near 3-microns that are diagnostic of OH/ H2O have been observed on many bodies in our solar system, including Mars, the Moon, and asteroids. We examine laboratory data that support ten different mechanisms by which OH/ H2O may be incorporated in or on a planetary surface, some of which may be appropriate for the Moon. These mechanisms can be broadly grouped in two categories: OH/ H2O in the interiors of minerals and glasses (#1-5 below), and OH/ H2O on their surfaces (#6-10). 1) Olivine, pyroxene, feldspar, and many other “nominally-anhydrous” silicates commonly incorporate OH, either during crystallization or through diffusion from a hydrous magma.2) Hydrous minerals, like amphiboles and clay minerals, contain structural OH. 3) Hydrated minerals such as zeolites contain structural H2O. 4) Minerals that crystallize in water-rich environments may contain fluid inclusions of H2O, indicating the presence of H during crystallization. 5) OH and/or H2O may be dissolved in silicate glasses with variable speciation depending on crystallization history and composition. Recent SIMS analyses of lunar volcanic glasses shows the presence of H at ppm levels (Saal et al., 2009). Our work suggests OH may be present (near detection levels) in agglutinate glasses as well. Such OH/ H2O could represent either primary magmatic H or solar-wind H interacting with the melt on the surface. 6) Liquid water (H2O) occurs at present only on the surface of Earth. 7) Surface ice (H2O) occurs on the surfaces of many terrestrial planets, may exist only in the cold portions of the permanently-shadowed portions of the lunar polar craters (e.g., Spudis, 2003). 8) Water can adsorb onto a mineral surface and then dissociate to form OH (e.g., Lane et al., 2007). 9) H2O may be physically adsorbed onto a mineral surface. 10) Interactions between solar wind particles and oxygen of mineral and/or glass surfaces may form OH (e.g., Zeller et al., 1970) with potential abundances on the order of a monolayer or a few layers. Detailed spectroscopic, crystal-chemical, and petrogenetic data are needed to distinguish between the above mechanisms; all of the above except #4 and #6 may well be viable on the Moon. Further laboratory work is needed to facilitate quantification of absorption features associated with these different mechanisms, as well as to constrain the mobility, stability, and possible dependence of OH/H2O adsorption on mineral and glass composition and grain size.

Laboratory studies on low-energy electron penetration depths into amorphous ice - consequence to astrobiology on icy surfaces

NASA Astrophysics Data System (ADS)

Gudipati, M. S.; Li, I.; Lignell, A. A.

2009-12-01

Penetration of electrons through icy surfaces plays an important role in radiation processing of solar system icy bodies. However, to date, there is no quantitative data available on the penetration depths of electrons through cryogenic water-ices. Penetration of high-energy incident electrons also results in the in-situ formation of secondary low-energy electrons, such as on the surface of Europa (Herring-Captain et al., 2005; Johnson et al., 2004). Low-energy electrons can also be produced through photoionization process such as on comet surfaces, or through bombardment by solar wind on icy surfaces (Bodewits et al., 2004). Present models use the laboratory penetration data of high-energy (>10 keV) electrons through silicon as a proxy for the ice (Cooper et al., 2001), normalized by the density of the medium. So far no laboratory studies have been conducted that deal with the penetration of electrons through amorphous or crystalline ices. In order to address this issue, we adopted a new experimental strategy by using aromatic molecules as probes. To begin with, we carried out systematic studies on the penetration depths of low-energy electrons (5 eV - 2 keV) through amorphous ice films of defined thickness at cryogenic temperatures (5 - 30 K). The results of these experiments will be analyzed and their relevance to survival of organic material on solar system icy surfaces will be presented. References: Bodewits, D., et al., 2004. X-ray and Far-Ultraviolet emission from comets: Relevant charge exchange processes. Physica Scripta. 70, C17-C20. Cooper, J. F., et al., 2001. Energetic ion and electron irradiation of the icy Galilean satellites. Icarus. 149, 133-159. Herring-Captain, J., et al., 2005. Low-energy (5-250 eV) electron-stimulated desorption of H+, H2+, and H+(H2O)nfrom low-temperature water ice surfaces. Physical Review B. 72, 035431-10. Johnson, R. E., et al., Radiation Effects on the Surfaces of the Galilean Satellites. In: F. Bagenal, et al., Eds.), Jupiter - The Planet, Satellites and Magnetosphere. Cambridge University Press, 2004, pp. 485-512.

An Investigation of Mineral Dynamics in Sea Ice by Solubility Measurements

NASA Astrophysics Data System (ADS)

Butler, B.; Kennedy, H.; Papadimitriou, S.

2016-02-01

Sea ice is a composite material with a sponge-like structure. The framework of the structure is composed of pure ice, and within the pores exists a concentrated seawater brine. When the temperature is reduced, the volume of this residual brine decreases, while its salinity increases. As a result of the paired changes to temperature and salinity, the brine becomes supersaturated with respect to a mineral at several points when cooling sea ice towards -30°C, creating a sequence of minerals that precipitate. The presence of countless microscopic salt crystals encapsulated within the ice, coupled with changes in brine volume associated with their precipitation/dissolution, results in changes to the optical and structural properties of the medium that contribute to the surface energy balance in sea ice environments. Furthermore, attainment of mineral equilibrium can result in abrupt changes in brine composition and osmotic conditions in the isolated brine pockets, imposing challenging conditions upon the biota that habitat the sea ice environment. Mirabilite (Na2SO4.10H2O), gypsum (CaSO4.2H2O) and hydrohalite (NaCl.2H2O) each represent minerals that are understood to exist within sea ice. Previous research has focused upon mineral extraction/detection, and the specific temperature for the onset of each minerals precipitation in sea ice; rather than the overarching dynamics. For this reason, solubility measurements of mirabilite, gypsum and hydrohalite in conditions representative of equilibrium sea ice brines were carried between 0 and -28°C, covering a range of undersaturated and supersaturated conditions for each mineral. Results provide accurate data for the onset of each minerals formation in sea ice, as well as important information on the way in which precipitation and dissolution reactions are affected when sea ice warms or cools. By incorporating the solubility data into a model that simluates the temperature-salinity profiles of first-year sea ice, the spatial and temporal distrubtion of each mineral throughout periods of ice growth and melt have been estimated for the first time. This information highlights the ubiquitous presence of minerals in the sea ice system, which have remained relatively elusive due to the nature of the complex structure and extreme environment that they exist in.

Remote Sensing Observations and Numerical Simulation for Martian Layered Ejecta Craters

NASA Astrophysics Data System (ADS)

Li, L.; Yue, Z.; Zhang, C.; Li, D.

2018-04-01

To understand past Martian climates, it is important to know the distribution and nature of water ice on Mars. Impact craters are widely used ubiquitous indicators for the presence of subsurface water or ice on Mars. Remote sensing observations and numerical simulation are powerful tools for investigating morphological and topographic features on planetary surfaces, and we can use the morphology of layered ejecta craters and hydrocode modeling to constrain possible layering and impact environments. The approach of this work consists of three stages. Firstly, the morphological characteristics of the Martian layered ejecta craters are performed based on Martian images and DEM data. Secondly, numerical modeling layered ejecta are performed through the hydrocode iSALE (impact-SALE). We present hydrocode modeling of impacts onto targets with a single icy layer within an otherwise uniform basalt crust to quantify the effects of subsurface H2O on observable layered ejecta morphologies. The model setup is based on a layered target made up of a regolithic layer (described by the basalt ANEOS), on top an ice layer (described by ANEOS equation of H2O ice), in turn on top of an underlying basaltic crust. The bolide is a 0.8 km diameter basaltic asteroid hitting the Martian surface vertically at a velocity of 12.8 km/s. Finally, the numerical results are compared with the MOLA DEM profile in order to analyze the formation mechanism of Martian layered ejecta craters. Our simulations suggest that the presence of an icy layer significantly modifies the cratering mechanics, and many of the unusual features of SLE craters may be explained by the presence of icy layers. Impact cratering on icy satellites is significantly affected by the presence of subsurface H2O.

Noachian Martian Volcanics a Water Source

NASA Technical Reports Server (NTRS)

Zent, A. P.; Glaze, L. S.; Baloga, S. M.; Fonda, Mark (Technical Monitor)

2002-01-01

H2O was supplied to the Noachian atmosphere by eruptions, or in association with large impacts. Most water outgassed into an extremely cold atmosphere, and condensate deposits were inevitable. High heat flow could lead to subglacial melting only if ice thicknesses were greater than 500-1000m, which is extremely unlikely. Subareal melting and flow is contingent upon temperatures periodically exceeding 273 K, and retarding evaporative loss of the flow. In still air, evaporation into a dry atmosphere is in the free convection regime, and a stream with 2 cu m/s discharge, flowing 1 m/s could persist for hundreds of days and cover distances greater than any valley reach. The zero-wind-shear condition is considered implausible however. We investigate the possibility that evaporation rates were suppressed because the atmosphere was regionally charged with H2O as it moved over snow/ice fields. Our initial concern is precipitation from volcanic plumes. A Kilauea-style eruption on the martian surface would cover a 10km circular deposit with 10cm of H2O, if all H2O could be precipitated near the vent. The characteristics of the eruption at the vent, (vent size, temperature, H2O content, etc.) are independent of the environmental conditions. The subsequent behavior of the plume, including precipitation of ash and H2O condensate depends strongly on the environment. Hence, the proximal fate of volcanic H2O is amenable to treatment in a model. A simple bulk thermodynamic model of the rise of an H2O plume through a stably stratified CO2 atmosphere, with only adiabatic cooling, produces runaway plume rise. A more complex treatment includes the effects of latent heat release, wind shear along the plume, divergence of ash and H2O, and will yield more realistic estimates of H2O transport in eruptive plumes. Results of these simulations will be presented.

[H2O ortho-para spin conversion in aqueous solutions as a quantum factor of Konovalov paradox].

PubMed

Pershin, S M

2014-01-01

Recently academician Konovalov and co-workers observed an increase in electroconductivity and biological activity simultaneously with diffusion slowing (or nanoobject diameter increasing) and extremes of other parameters (ζ-potential, surface tension, pH, optical activity) in low concentration aqueous solutions. This phenomenon completely disappeared when samples were shielded against external electromagnetic fields by a Faraday cage. A conventional theory of water and water solutions couldn't explain "Konovalov paradox" observed in numerous experiments (representative sampling about 60 samples and 7 parameters). The new approach was suggested to describe the physics of water and explain "Konovalov paradox". The proposed concept takes into account the quantum differences of ortho-para spin isomers of H2O in bulk water (rotational spin-selectivity upon hydration and spontaneous formation of ice-like structures, quantum beats and spin conversion induced in the presence of a resonant electromagnetic radiation). A size-dependent self-assembly of amorphous complexes of H2O molecules more than 275 leading to the ice Ih structure observed in the previous experiments supports this concept.

Infrared spectoscopy of Triton and Pluto ice analogs: The case for saturated hydrocarbons

NASA Technical Reports Server (NTRS)

Bohn, Robert B.; Sandford, Scott A.; Allamandola, Louis J.; Cruikshank, Dale P.

1994-01-01

The infrared transmission spectra and photochemical behavior of various organic compounds isolated in solid N2 ices, appropriate for applications to Triton ad Pluto, are presented. It is shown that excess absorption in the surface spectra of Triton and Pluto, i.e., absorption not explained by present models incorporating molecules already identified on these bodies (N2, CH4, CO, and CO2), that starts near 4450/cm (2.25 microns) and extends to lower frequencies, may be due to alkanes (C(n)H(2n+2)) and related molecules frozen in the nitrogen. Branched and linear alkanes may be responsible. Experiments in which the photochemstry of N2: CH4 and N2: CH4: CO ices was explored demonsrtrate that the surface ices of Triton and Pluto may contain a wide variety of additional species containing H, C, O, and N. Of these, the reactive molecule diazomethane, CH2N2, is particularly important since it may be largely responsible for the synthesis of larger alkanes from CH4 and other small alkanes. Diazomethane would also be expected to drive chemical reactions involving organics in the surface ices of Triton and Pluto toward saturation, i.e., to reduce multiple CC bonds. The positions and intrinsic strengths (A values) of many of the infrared absorption bands of N2 matrix-isolated molecules of relevance to Triton and Pluto have also been determined. These can be used to aid in their search and to place constraints on their abundances.

Pluto: Fluidized Transport of Tholins by Heating of the Subsurface

NASA Technical Reports Server (NTRS)

Cruikshank, Dale P.; Spohrer, Steven; Grundy, William M.; Moore, Jeffrey M.; Umurhan, Orkan M.; White, Oliver L.; Beyer, Ross A.; Dalle Ore, Cristina M.; Stern, S. A.; Young, Leslie;

The ice VII-ice X phase transition with implications for planetary interiors

NASA Astrophysics Data System (ADS)

Aarestad, B.; Frank, M. R.; Scott, H.; Bricker, M.; Prakapenka, V.

2008-12-01

A significant amount of research on the high pressure polymorphs of H2O have detailed the lattice structure and density of these phases, namely ice VI, ice VII, and ice X. These high pressure ices are noteworthy as they may comprise a considerable part of the interior of large icy planets and satellites. However, there is a dearth of data on how the incorporation of an impurity, charged or non-charged, affects the ice VII-ice X transition. This study examined the ice VII-ice X transition that occurs at approximately 62 GPa with a pure system and two select impure systems. Solutions of pure H2O, 1.6 mole percent NaCl in H2O, and 1.60 mole percent CH3OH in H2O were compressed in a diamond anvil cell (DAC). The experiments were performed at the GSECARS 13-BM-D beam line at the Advanced Photon Source at Argonne National Laboratory. Powder diffraction data of the ice samples were collected using monochromatic X-ray radiation, 0.2755 Å, and a MAR 345 online imaging system at intervals of approximately 2 GPa up to ~71.5, ~74.5, and ~68 GPa, respectively. Analyses of the data provided volume-pressure relations (at 298 K) which were used to detail the ice VII-ice X phase transition. The pressure of the phase transition, based upon an interpretation of the X-ray diffraction data, was found to vary as a function of the impurity type. Thus, the depth of the ice VII-ice X phase transition within an ice-rich planetary body can be influenced by trace-level impurities.

The Photochemistry of Pyrimidine in Pure H2O Ice Subjected to Different Radiation Environments and the Formation of Uracil

NASA Technical Reports Server (NTRS)

Nuevo, M.; Chen, Y.-J.; Materese. C. K..; Hu, W.-J.; Qiu, J.-M.; Wu, S.-R.; Fung, H.-S.; Sandford, S. A.; Chu, C.-C.; Yih, T.-S.;

Salt partitioning between water and high-pressure ices. Implication for the dynamics and habitability of icy moons and water-rich planetary bodies

NASA Astrophysics Data System (ADS)

Journaux, Baptiste; Daniel, Isabelle; Petitgirard, Sylvain; Cardon, Hervé; Perrillat, Jean-Philippe; Caracas, Razvan; Mezouar, Mohamed

2017-04-01

Water-rich planetary bodies including large icy moons and ocean exoplanets may host a deep liquid water ocean underlying a high-pressure icy mantle. The latter is often considered as a limitation to the habitability of the uppermost ocean because it would limit the availability of nutrients resulting from the hydrothermal alteration of the silicate mantle located beneath the deep ice layer. To assess the effects of salts on the physical properties of high-pressure ices and therefore the possible chemical exchanges and habitability inside H2O-rich planetary bodies, we measured partitioning coefficients and densities in the H2O-RbI system up to 450 K and 4 GPa; RbI standing as an experimentally amenable analog of NaCl in the H2O-salt solutions. We measured the partitioning coefficient of RbI between the aqueous fluid and ices VI and VII, using in-situ Synchrotron X-ray Fluorescence (XRF). With in-situ X-ray diffraction, we measured the unit-cell parameters and the densities of the high-pressure ice phases in equilibrium with the aqueous fluid, at pressures and temperatures relevant to the interior of planetary bodies. We conclude that RbI is strongly incompatible towards ice VI with a partitioning coefficient Kd(VI-L) = 5.0 (± 2.1) ṡ10-3 and moderately incompatible towards ice VII, Kd(VII-L) = 0.12 (± 0.05). RbI significantly increases the unit-cell volume of ice VI and VII by ca. 1%. This implies that RbI-poor ice VI is buoyant compared to H2O ice VI while RbI-enriched ice VII is denser than H2O ice VII. These new experimental results might profoundly impact the internal dynamics of water-rich planetary bodies. For instance, an icy mantle at moderate conditions of pressure and temperature will consist of buoyant ice VI with low concentration of salt, and would likely induce an upwelling current of solutes towards the above liquid ocean. In contrast, a deep and/or thick icy mantle of ice VII will be enriched in salt and hence would form a stable chemical boundary layer on top of the silicate mantle. Such a contrasted dynamics in the aqueous-ice VI-ice VII system would greatly influence the migration of nutrients towards the uppermost liquid ocean, thus controlling the habitability of moderate to large H2O-rich planetary bodies in our solar system (e.g., Ganymede, Titan, Calisto) and beyond.

Oxidation in Enceladus' Ocean

NASA Astrophysics Data System (ADS)

Ray, C.; Waite, J. H., Jr.; Glein, C.; Teolis, B. D.

2017-12-01

The detection of molecular hydrogen in the plume of Saturn's icy moon Enceladus reports that there is positive chemical affinity for methanogenesis, the reaction of hydrogen with carbon dioxide to form methane and water [Waite et al., 2017]. Methanogenesis, however, is just one of many possible metabolic pathways that could be utilized. While some of the oxidants involved in these metabolic pathways have already been detected in the plume (i.e. carbon dioxide), sulfate, which could play an important role in several of these reactions, has not yet been observed. To constrain the amount of sulfate and other oxidants that could be present to support these metabolisms, we present a geochemical model of Enceladus' ocean based on detections made by the Cassini INMS instrument [Waite et. al, 2017]. We use a model of radiolysis on the surface of Enceladus to estimate the amount of molecular oxygen (O2) contained in the ice. We calculate the delivery rate of O2 from the surface ice to the ocean using previous estimates of the rate of ice deposition on the south polar region [Kempf et al., 2010], and the meteoritic gardening rate for the older surface of the moon. Assuming this activity has occurred over 4.5 billion years, we obtain an upper limit of > 1020 moles of O2 delivered to the ocean over Enceladus' lifetime. This large amount of oxygen could react with sulfides, reduced iron, or organic materials to produce sulfate, ferric oxyhydroxides, or carbon dioxide/carboxylic acids, respectively. We calculate upper limits on the amounts of these materials using a mineralogical model of Enceladus' core [Waite et al., 2017]. We find that the abiotic oxidation of pyrrhotite, which is the most likely pathway for sulfate production, could yield a sulfate concentration > 4 mol/(kg H2O). We suggest that oxidants should be abundant in the ocean and plume unless they are being consumed by life, the rate of ice deposition on the surface is much smaller than what has been predicted, or the duration of activity delivering O2 to the ocean is much shorter than the age of the solar system. References: [1] J. H. Waite, et al., Cassini finds molecular hydrogen in the Enceladus plume: Evidence for hydrothermal processes, Science 357, 6349 (2017). [2] S. Kempf, et al., How the Enceladus dust plume feeds Saturn's E ring, Icarus 206, 2 (2010)

Temporal Evolution of Ice Spots on the Nucleus of Comet 67P/Churyumov-Gerasimenko as Observed by Rosetta

NASA Astrophysics Data System (ADS)

Barucci, M. A.; Fornasier, S.; Filacchione, G.; Deshapriya, J. D. P.; Raponi, A.; Tosi, F.; Feller, C.; Ciarniello, M.; Fulchignoni, M.; Sierks, H.; Capaccioni, F.:

2017-04-01

During more than two years of observations on board of Rosetta spacecraft orbiting close to the comet 67P/Churyumov-Gerasimenko, the OSIRIS (Optical, Spectroscopic, and Infrared Remote Imaging System) camera acquired a huge quantity of resolved images of the comet, producing the most detailed maps at the highest spatial resolution ever made of a cometary nucleus surface. Comet 67P shows a body with a dark, dehydrated surface, rich in hetereogeneous geological structures [1]. The morphologically complex surface shows color and albedo variations with local time and perihelion distance. Numerous bright spots of different size with high visible albedo and flat visible slope have been identified by OSIRIS high resolution images [2, 3, 4, 5]. The detected bright spots are mostly situated on consolidated dust free areas distributed on the two lobes of 67P in locations which stay longer in shadow, mostly concentrated at equatorial latitudes Some of them have been observed also by VIRTIS (Visible InfraRed Thermal Imaging Spectrometer) which has detected the diagnostic absorption bands of ice in at 1.5 and 2.05 μm [6, 7]. Comparing the image data with near- infrared spectra and modeling the spectra as a mixture of H2O ice and the ubiquitious "Dark Material" associated to complex organic material present on the nucleus' surface [8, 9], we were able to study at the same time the morphological, thermal and compositional properties of these areas. With this complementary study we are able to confirm the presence of H2O ice on many brighter areas distributed on the two lobes of 67P. We analysed in detail the OSIRIS images in the areas where the spots have been identified. The majority of the detected H2O ice spots are located in the vicinity of previously detected cometary outbursts source areas. We investigated all the available observations of the selected areas to evaluate the lifetime of the ice spots. Some spots are stable for several months and others show temporal changes connected to diurnal and seasonal variations. The temporal variation of these spots will be presented and discussed as well as their stability in general, well corroborated by the temperature retrieved at the surface. References: [1] Sierks H. et al. (2015) Science, 347, 1044. [2] Pommerol A. et al. (2015) A&A, 583, A25. [3] Barucci M. A. et al. (2016) A&A., 595, A102. [4] Oklay N. et al. (2016) MNRAS, in press. [5] Fornasier S. et al. (2016) Science in press, DOI : 10.1126/science.aag2671. [6] Filacchione et al. (2016) Nature, 529, 368. [7] Filacchione et al. (2016) Icarus 274, 334- 349. [8] Capaccioni F. et al. (2015) Science, 347, 0628. [9] Quirico, E. et al. (2016) Icarus, 272, 32.

Modeling CO, CO2, and H2O Ice Abundances in the Envelopes of Young Stellar Objects in the Magellanic Clouds

NASA Astrophysics Data System (ADS)

Pauly, Tyler; Garrod, Robin T.

2018-02-01

Massive young stellar objects (MYSOs) in the Magellanic Clouds show infrared absorption features corresponding to significant abundances of CO, CO2, and H2O ice along the line of sight, with the relative abundances of these ices differing between the Magellanic Clouds and the Milky Way. CO ice is not detected toward sources in the Small Magellanic Cloud, and upper limits put its relative abundance well below sources in the Large Magellanic Cloud and the Milky Way. We use our gas-grain chemical code MAGICKAL, with multiple grain sizes and grain temperatures, and further expand it with a treatment for increased interstellar radiation field intensity to model the elevated dust temperatures observed in the MCs. We also adjust the elemental abundances used in the chemical models, guided by observations of H II regions in these metal-poor satellite galaxies. With a grid of models, we are able to reproduce the relative ice fractions observed in MC MYSOs, indicating that metal depletion and elevated grain temperature are important drivers of the MYSO envelope ice composition. Magellanic Cloud elemental abundances have a subgalactic C/O ratio, increasing H2O ice abundances relative to the other ices; elevated grain temperatures favor CO2 production over H2O and CO. The observed shortfall in CO in the Small Magellanic Cloud can be explained by a combination of reduced carbon abundance and increased grain temperatures. The models indicate that a large variation in radiation field strength is required to match the range of observed LMC abundances. CH3OH abundance is found to be enhanced in low-metallicity models, providing seed material for complex organic molecule formation in the Magellanic Clouds.

Nucleobases and Prebiotic Molecules in Organic Residues Produced from the Ultraviolet Photo-Irradiation of Pyrimidine in NH3 and H2O+NH3 Ices

NASA Technical Reports Server (NTRS)

Nuevo, Michel; Milam, Stefanie N.; Sandford, Scott

2012-01-01

Although not yet identified in the interstellar medium (ISM), N-heterocycles including nucleobases the information subunits of DNA and RNA are present in carbonaceous chondrites, which indicates that molecules of biological interest can be formed in non-terrestrial environments via abiotic pathways. Recent laboratory experiments and ab-initio calculations have already shown that the irradiation of pyrimidine in pure H2O ices leads to the formation of a suite of oxidized pyrimidine derivatives, including the nucleobase uracil. In the present work, NH3:pyrimidine and H2O:NH3:pyrimidine ice mixtures with different relative proportions were irradiated with UV photons under astrophysically relevant conditions. Liquid- and gas-chromatography analysis of the resulting organic residues has led to the detection of the nucleobases uracil and cytosine, as well as other species of prebiotic interest such as urea and small amino acids. The presence of these molecules in organic residues formed under abiotic conditions supports scenarios in which extraterrestrial organics that formed in space and were subsequently delivered to telluric planets via comets and meteorites could have contributed to the inventory of molecules that triggered the first biological reactions on their surfaces.

Laboratory Studies of Atmospheric Heterogeneous Chemistry

NASA Technical Reports Server (NTRS)

Keyser, L. F.; Leu, M-T.

1993-01-01

In the laboratory, ice films formed by freezing from the liquid or more frequently by deposition from the vapor phase have been used to simulate stratospheric cloud surfaces for measurements of reaction and uptake rates. To obtain intrinsic surface reaction probabilities that can be used in atmospheric models, the area of the film surface that actually takes part in the reaction must be known. It is important to know not only the total surface area but also the film morphology in order to determine where and how the surface is situated and, thus, what fraction of it is available for reaction. Information on the structure of these ice films has been obtained by using several experimental methods. In the sections that follow, these methods will be discussed, then the results will be used to construct a working model of the ice films, and finally the model will be applied to an experimental study of HC1 uptake by H_2O ice.

Cassini Visual and Infrared Mapping Spectrometer observations of Iapetus: Detection of CO2

USGS Publications Warehouse

Buratti, B.J.; Cruikshank, D.P.; Brown, R.H.; Clark, R.N.; Bauer, J.M.; Jaumann, R.; McCord, T.B.; Simonelli, D.P.; Hibbitts, C.A.; Hansen, G.B.; Owen, T.C.; Baines, K.H.; Bellucci, G.; Bibring, J.-P.; Capaccioni, F.; Cerroni, P.; Coradini, A.; Drossart, P.; Formisano, V.; Langevin, Y.; Matson, D.L.; Mennella, V.; Nelson, R.M.; Nicholson, P.D.; Sicardy, B.; Sotin, Christophe; Roush, T.L.; Soderlund, K.; Muradyan, A.

2005-01-01

The Visual and Infrared Mapping Spectrometer (VIMS) instrument aboard the Cassini spacecraft obtained its first spectral map of the satellite lapetus in which new absorption bands are seen in the spectra of both the low-albedo hemisphere and the H2O ice-rich hemisphere. Carbon dioxide is identified in the low-albedo material, probably as a photochemically produced molecule that is trapped in H2O ice or in some mineral or complex organic solid. Other absorption bands are unidentified. The spectrum of the low-albedo hemisphere is satisfactorily modeled with a combination of organic tholin, poly-HCN, and small amounts of H2O ice and Fe 2O3. The high-albedo hemisphere is modeled with H 2O ice slightly darkened with tholin. The detection of CO2 in the low-albedo material on the leading hemisphere supports the contention that it is carbon-bearing material from an external source that has been swept up by the satellite's orbital motion. ?? 2005. The American Astronomical Society. All rights reserved.

Organic Compounds Produced by Photolysis of Realistic Interstellar and Cometary Ice Analogs Containing Methanol

NASA Technical Reports Server (NTRS)

Bernstein, Max P.; Sandford, Scott A.; Allamandola, Louis J.; Chang, Sherwood; Scharberg, Maureen A.

1995-01-01

The InfraRed (IR) spectra of UltraViolet (UV) and thermally processed, methanol-containing interstellar / cometary ice analogs at temperatures from 12 to 300 K are presented. Infrared spectroscopy, H-1 and C-13 Nuclear Magnetic Resonance (NMR) spectroscopy, and gas chromatography-mass spectrometry indicate that CO (carbon monoxide), CO2 (carbon dioxide), CH4 (methane), HCO (the formyl radical), H2CO (formaldehyde), CH3CH2OH (ethanol), HC([double bond]O)NH2 (formamide), CH3C([double bond]O)NH2 (acetamide), and R[single bond]C[triple bond]N (nitriles) are formed. In addition, the organic materials remaining after photolyzed ice analogs have been warmed to room temperature contain (in rough order of decreasing abundance), (1) hexamethylenetetramine (HMT, C6H12N4), (2) ethers, alcohols, and compounds related to PolyOxyMethylene (POM, ([single bond]CH2O[single bond](sub n)), and (3) ketones (R[single bond]C([double bond]O)[single bond]R') and amides (H2NC([double bond]O)[single bond]R). Most of the carbon in these residues is thought to come from the methanol in the original ice. Deuterium and C-13 isotopic labeling demonstrates that methanol is definitely the source of carbon in HMT. High concentrations of HMT in interstellar and cometary ices could have important astrophysical consequences. The ultraviolet photolysis of HMT frozen in H2O ice readily produces the 'XCN' band observed in the spectra of protostellar objects and laboratory ices, as well as other nitriles. Thus, HMT may be a precursor of XCN and a source of CN in comets and the interstellar medium. Also, HMT is known to hydrolyze under acidic conditions to yield ammonia, formaldehyde, and amino acids. Thus, HMT may be a significant source of prebiogenic compounds on asteroidal parent bodies. A potential mechanism for the radiative formation of HMT in cosmic ices is outlined.

Adsorption of CO on oxide and water ice surfaces - Implications for the Martian atmosphere

NASA Technical Reports Server (NTRS)

Leu, M.-T.; Blamont, J. E.; Anbar, A. D.; Keyser, L. F.; Sander, S. P.

1992-01-01

The adsorption of carbon monoxide (CO) on water ice and on the oxides Fe2O3, Fe3O4, Al2O3, SiO2, CaO, MgO, and TiO2 (rutile and anatase) has been investigated in a flow reactor. A mass spectrometer was employed as a detector to monitor the temporal concentrations of CO. Adsorption coefficients as large as 1 x 10 exp -4 were measured for CO on TiO2 solids in helium at 196 K. The fractional surface coverage for CO on TiO2 solids in helium was also determined to be approximately 10 percent at 196 K. The upper limits of the fractional surface coverage for the other oxides (Fe2O3, Fe3O4, Al2O3, SiO2, CaO, and MgO) and water ice were also measured to be less than 1 percent. The implications for the stability of CO2 in the Martian atmosphere and the 'CO hole' observed by the Phobos/ISM experiment are discussed.

Robust Anti-Icing Performance of a Flexible Superhydrophobic Surface.

PubMed

Wang, Lei; Gong, Qihua; Zhan, Shihui; Jiang, Lei; Zheng, Yongmei

2016-09-01

A material with superhydrophobic and anti-ice/de-icing properties, which has a micro-/nanostructured surface, is produced by a straightforward method. This material comprises a poly(dimethylsiloxane) (PDMS) microstructure with ZnO nanohairs and shows excellent water and ice repellency even at low temperatures (-20 °C) and relatively high humidity (90%) for over three months. These results are expected to be helpful for designing smart, non-wetting materials that can be adapted to low-temperature environments for the development of anti-icing systems. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rosetta/VIRTIS investigation of the chemistry and activity of comet 67P/Churyumov-Gerasimenko

NASA Astrophysics Data System (ADS)

Bockelee-Morvan, Dominique; Drossart, Pierre; Piccioni, Giuseppe; Migliorini, Alessandra; Erard, Stéphane; Capaccioni, Fabrizio; Filacchione, Gianrico; Fougere, Nicolas; Leyrat, Cedric; Crovisier, Jacques; Capaccioni, Fabrizio

2016-07-01

The composition of cometary ices inside cometary nuclei provides clues to the chemistry of the protoplanetary disk where they formed, 4.6 Gyr ago. These ices sublimate when the body approches the Sun, so that the coma molecular species give insights on the nucleus surface and sub-surface composition. So far, most investigations of the coma chemical composition were performed from telescopic observations from the ground or space plateforms. Since August 2014, the ESA/Rosetta spacecraft has been investigating the nucleus and inner coma of 67P/Churyumov-Gerasimenko. This talk will present an overview of the results obtained by the Visual and Infrared Thermal Imaging Spectrometer (VIRTIS) instrument onboard Rosetta, focussing on observations of molecular species. VIRTIS is composed of two channels. The VIRTIS-M channel is a spectro-imager covering the 0.27-5.1 microns range, which allowed us to map the spatial distribution of H2O and CO2 (Migliorini et al. 2016, A&A in press). VIRTIS-H is a high-spectral resolution spectrometer covering the 2-5 microns range. Spectra obtained with VIRTIS-H show signatures of H2O, CO2 (both fundamental and hot bands), 13CO2, CH4 and other C-H bearing species (Bockelee-Morvan et al. A&A, 583, A6,2015). VIRTIS is a key instrument to investigate regional, diurnal and seasonal variations of the comet outgassing.

Ultraviolet spectrophotometry of Comet Giacobini-Zinner during the ICE encounter. [International Cometary Explorer

NASA Technical Reports Server (NTRS)

Mcfadden, Lucy A.; Ahearn, Michael F.; Feldman, Paul D.; Boehnhardt, Hermann; Rahe, Juergen; Festou, Michel C.; Brandt, John C.; Maran, Stephen P.; Niedner, Malcolm B.; Smith, Andrew M.

1987-01-01

The IUE's UV spectrophotometer was used to monitor Comet Giacobini-Zinner's H2O production rate from June to October, 1985, in support of the International Cometary Explorer (ICE) mission. Observation results for the spatial and temporal variation and the abundance or upper limits of C, CO, CO(+), CO2(+), CS, H, Mg(+), O, OH, and S, between September 9 and 12, included the time of the ICE encounter: at this time, the H2O production rate obtained was consistent with a number of gas production rates derived indirectly from the ICE experiments. A comparison of the CO2(+) ion abundance with the total electron density measured by the plasma electron and radio science experiments on ICE implies an ion deficiency relative to electrons, so that the satisfaction of charge balance criteria requires the presence of a major ion population not detected by remote sensing.

Skating on thin ice: surface chemistry under interstellar conditions

NASA Astrophysics Data System (ADS)

Fraser, H.; van Dishoeck, E.; Tielens, X.

Solid CO2 has been observed towards both active star forming regions and quiescent clouds (Gerakines et. al. (1999)). The high abundance of CO2 in the solid phase, and its low abundance in the gas phase, support the idea that CO2 is almost exclusively formed in the solid state. Several possible formation mechanisms have been postulated (Ruffle &Herbst (2001): Charnley &Kaufman (2000)), and the detection of CO2 towards quiescent sources such as Elias 16 (Whittet et. al. (1998)) clearly suggests that CO2 can be produced in the absence of UV or electron mediated processes. The most likely route is via the surface reactions between O atoms, or OH radicals, and CO. The tools of modern surface- science offer us the potential to determine many of the physical and chemical attributes of icy interstellar grain mantles under highly controlled conditions, that closely mimic interstellar environments. The Leiden Surface Reaction Simulation Device ( urfreside) combines UHV (UltraS High Vacuum) surface science techniques with an atomic beam to study chemical reactions occurring on the SURFACE and in the BULK of interstellar ice grain mimics. By simultaneously combining two or more surface analysis techniques, the chemical kinetics, reaction mechanisms and activation energies can be determined directly. The experiment is aimed at identifying the key barrierless reactions and desorption pathways on and in H2 O and CO ices under interstellar conditions. The results from traditional HV (high vacuum) and UHV studies of the CO + O and CO + OH reactions will be presented in this paper. Charnley, S.B., & Kaufman, M.J., 2000, ApJ, 529, L111 Gerakines, P.A., 1999, ApJ, 522, 357 Ruffle, D.P., & Herbst, E., 2001, MNRAS, 324, 1054 Whittet, D.C.B., et.al., 1998, ApJ, 498, L159

Near-Infrared Band Strengths of Molecules Diluted in N2 and H2O Ice Mixtures Relevant to Interstellar and Planetary Ices

NASA Technical Reports Server (NTRS)

Richey, Christina Rae; Gerakines, P.A.

2012-01-01

The relative abundances of ices in astrophysical environments rely on accurate laboratory measurements of physical parameters, such as band strengths (or absorption intensities), determined for the molecules of interest in relevant mixtures. In an extension of our previous study on pure-ice samples, here we focus on the near-infrared absorption features of molecules in mixtures with the dominant components of interstellar and planetary ices, H2O and N2. We present experimentally measured near-infrared spectral information (peak positions, widths, and band strengths) for both H2O- and N2-dominated mixtures of CO (carbon monoxide), CO2 (carbon dioxide), CH4 (methane), and NH3 (ammonia). Band strengths were determined during sample deposition by correlating the growth of near-infrared features (10,000-4000 per centimeter, 1-2.5 micrometers) with better-known mid-infrared features (4000-400 per centimeter, 2.5-25 micrometers) at longer wavelengths.

Synthesis of formamide and isocyanic acid after ion irradiation of frozen gas mixtures

NASA Astrophysics Data System (ADS)

Kaňuchová, Z.; Urso, R. G.; Baratta, G. A.; Brucato, J. R.; Palumbo, M. E.; Strazzulla, G.

2016-01-01

Context. Formamide (NH2HCO) and isocyanic acid (HNCO) have been observed as gaseous species in several astronomical environments such as cometary comae and pre- and proto-stellar objects. A debate is open on the formation route of those molecules, in particular if they are formed by chemical reactions in the gas phase and/or on grains. In this latter case it is relevant to understand if the formation occurs through surface reactions or is induced by energetic processing. Aims: We present arguments that support the formation of formamide in the solid phase by cosmic-ion-induced energetic processing of ices present as mantles of interstellar grains and on comets. Formamides, along with other molecules, are expelled in the gas phase when the physical parameters are appropriate to induce the desorption of ices. Methods: We have performed several laboratory experiments in which ice mixtures (H2O:CH4:N2, H2O:CH4:NH3, and CH3OH:N2) were bombarded with energetic (30-200 keV) ions (H+ or He+). FTIR spectroscopy was performed before, during, and after ion bombardment. In particular, the formation of HNCO and NH2HCO was measured quantiatively. Results: Energetic processing of ice can quantitatively reproduce the amount of NH2HCO observed in cometary comae and in many circumstellar regions. HNCO is also formed, but additional formation mechanisms are requested to quantitatively account for the astronomical observations. Conclusions: We suggest that energetic processing of ices in the pre- and proto-stellar regions and in comets is the main mechanism to produce formamide, which, once it is released in the gas phase because of desorption of ices, is observed in the gas phase in these astrophysical environments.

FTIR study of CO2 and H2O/CO2 nanoparticles and their temporal evolution at 80 K.

PubMed

Taraschewski, M; Cammenga, H K; Tuckermann, R; Bauerecker, S

2005-04-21

Fourier transform infrared (FTIR) spectroscopy combined with a long-path collisional cooling cell was used to investigate the temporal evolution of CO2 nanoparticles and binary H2O/CO2 nanocomposites in the aerosol phase at 80 K. The experimental conditions for the formation of different CO2 particle shapes as slab, shell, sphere, cube, and needle have been studied by comparison with calculated data from the literature. The H2O/CO2 nanoparticles were generated with a newly developed multiple-pulse injection technique and with the simpler flow-in technique. The carbon dioxide nu3-vibration band at 2360 cm(-1) and the water ice OH-dangling band at 3700 cm(-1) were used to study the evolution of structure, shape, and contact area of the nanocomposites over 150 s. Different stages of binary nanocomposites with primary water ice cores were identified dependent on the injected CO2 portion: (a) disordered (amorphous) CO2 slabs on water particle surfaces, (b) globular crystalline CO2 humps sticking on the water cores, and (c) water cores being completely enclosed in bigger predominantly crystalline CO2 nanoparticles. However, regular CO2 shell structures on primary water particles showing both longitudinal (LO) and transverse (TO) optical mode features of the nu3-vibration band could not be observed. Experiments with reversed nucleation order indicate that H2O/CO2 composite particles with different initial structures evolve toward similar molecular nanocomposites with separated CO2 and H2O regions.

Thermochemical Kinetics of H2O and HNO3 on crystalline Nitric Acid Hydrates (alpha-, beta-NAT, NAD) in the range 175-200 K

NASA Astrophysics Data System (ADS)

Rossi, Michel J.; Iannarelli, Riccardo

2015-04-01

The growth of NAT (Nitric Acid Trihydrate, HNO3x3H2O) and NAD (Nitric Acid Dihydrate, HNO3x2H2O) on an ice substrate, the evaporative lifetime of NAT and NAD as well as the interconversion of alpha- and beta-NAT competing with evaporation and growth under UT/LS conditions depends on the interfacial kinetics of H2O and HNO3 vapor on the condensed phase. Despite the existence of some literature results we have embarked on a systematic investigation of the kinetics using a multidiagnostic experimental approach enabled by the simultaneous observation of both the gas (residual gas mass spectrometry) as well as the condensed phase (FTIR absorption in transmission). We report on thermochemically consistent mass accommodation coefficients alpha and absolute evaporation rates Rev/molecule s-1cm-3 as a function of temperature which yields the corresponding vapor pressures of both H2O and HNO3 in equilibrium with the crystalline phases, hence the term thermochemical kinetics. These results have been obtained using a stirred flow reactor (SFR) using a macroscopic pure ice film of 1 micron or so thickness as a starting substrate mimicking atmospheric ice particles and are reported in a phase diagram specifically addressing UT (Upper Troposphere)/LS (Lower Stratosphere) conditions as far as temperature and partial pressures are concerned. The experiments have been performed either at steady-state flow conditions or in transient supersaturation using a pulsed solenoid valve in order to generate gas pulses whose decay were subsequently monitored in real time. Special attention has been given to the effect of the stainless-steel vessel walls in that Langmuir adsorption isotherms for H2O and HNO3 have been used to correct for wall-adsorption of both probe gases. Typically, the accommodation coefficients of H2O and HNO3 are similar throughout the temperature range whereas the rates of evaporation Rev of H2O are significantly larger than for HNO3 thus leading to the difference in vapor pressure revealed in the phase diagram. A noteworthy effect seems to be that the accommodation coefficients obtained in pulsed gas admission experiments (transient supersaturation) lead to significantly lower values owing to surface saturation, especially in the case of the thermodynamically stable beta-NAT substrate.

Probing the water and CO snow lines in the young protostar NGC 1333-IRAS4B

NASA Astrophysics Data System (ADS)

Anderl, Sibylle; Maret, Sébastien; André, Philippe; Maury, Anaëlle; Belloche, Arnaud; Cabrit, Sylvie; Codella, Claudio; Lefloch, Bertrand

2015-08-01

Today, we believe that the onset of life requires free energy, water, and complex, probably carbon-based chemistry. In the interstellar medium, complex organic molecules seem to mostly form in reactions happening on the icy surface of dust grains, such that they are released into the gas phase when the dust is heated. The resulting “snow lines”, marking regions where ices start to sublimate, play an important role for planet growth and bulk composition in protoplanetary disks. However, they can already be observed in the envelopes of the much younger, low-mass Class 0 protostars that are still in their early phase of heavy accretion. The information on the sublimation regions of different kinds of ices can be used to understand the chemistry of the envelope, its temperature and density structure, and may even hint at the history of the accretion process. Accordingly, it is a crucial piece of information in order to get the full picture of how organic chemistry evolves already at the earliest stages of the formation of sun-like stars. As part of the CALYPSO Large Program (http://irfu.cea.fr/Projets/Calypso/), we have obtained observations of C18O, N2H+ and CH3OH towards the Class 0 protostar NGC 1333-IRAS4B with the IRAM Plateau de Bure interferometer at sub-arcsecond resolution. Of these we use the methanol observations as a proxy for the water snow line, assuming methanol is trapped in water ice. The observed anti-correlation of C18O and N2H+, with N2H+ forming a ring around the centrally peaked C18O emission, reveals for the first time the CO snow line in this protostellar envelope, with a radius of ~300 AU. The methanol emission is much more compact than that of C18O, and traces the water snow line with a radius of ~40 AU. We have modeled the emission using a chemical model coupled with a radiative transfer module. We find that the CO snow line appears further inwards than expected from the binding energy of pure CO ices. This may hint at CO being frozen out in H2O or CO2 dominated ices. Our observations can thereby yield clues on the widely unknown composition of interstellar ices, being the initial seeds of complex organic chemistry.

Pluto's Paleoglaciation: Processes and Bounds

NASA Astrophysics Data System (ADS)

Umurhan, Orkan; Howard, Alan D.; White, Oliver L.; Moore, Jeffrey M.; Grundy, William M.; Schenk, Paul M.; Beyer, Ross A.; McKinnon, William B.; Singer, Kelsi N.; Lauer, Tod R.; Cheng, Andrew F.; Stern, S. Alan; Weaver, Harold A.; Young, Leslie; Ennico, Kimberly; Olkin, Catherine; New Horizons Science Team

2017-10-01

New Horizons imaging of Pluto’s surface shows eroded landscapes reminiscent of assorted glaciated terrains found on the Earth such as alpine valleys, dendritic networks and others. For example, LORRI imaging of fluted craters show radially oriented ridging which also resembles Pluto’s washboard terrain. Digital elevation modeling indicates that these down-gradient oriented ridges are about 3-4 km spaced apart with depths ranging from 0.2-0.5 km. Present day glaciation on Pluto is characterized by moving N2 ice blocks presumably riding over a H2O ice bedrock substrate. Assuming Pluto’s ancient surface was sculpted by N2 glaciation, what remains a mystery is the specific nature of the glacial erosion mechanism(s) responsible for the observed features.To better resolve this puzzle, we perform landform evolution modeling of several glacial erosion processes known from terrestrial H2O ice glaciation studies. These terrestrial processes, which depend upon whether or not the glacier’s base is wet or dry, include quarrying/plucking and fluvial erosion. We also consider new erosional processes (to be described in this presentation) which are unique to the highly insulating character of solid N2 including both phase change induced hydrofracture and geothermally driven basal melt. Until improvements in our knowledge of solid N2’s rheology are made available (including its mechanical behavior as a binary/trinary mixture of CH4 and CO), it is difficult to assess with high precision which of the aforementioned erosion mechanisms are responsible for the observed surface etchings.Nevertheless, we consider a model crater surface and examine its erosional development due to flowing N2 glacial ice as built up over time according to N2 deposition rates based on GCM modeling of Pluto’s ancient atmosphere. For given erosional mechanism our aim is to determine the permissible ranges of model input parameters (e.g., ice strength, flow rates, grain sizes, quarrying rates, etc.) that best reproduces the observed length scales found on the observed fluted craters. As of the writing of this abstract, both the processes of quarrying and phase change induced hydrofracture appear to be most promising at explaining the fluted crater ridging.

Pluto's Paleoglaciation: Processes and Bounds.

NASA Astrophysics Data System (ADS)

Umurhan, O. M.; Howard, A. D.; White, O. L.; Moore, J. M.; Grundy, W. M.; Schenk, P.; Beyer, R. A.; McKinnon, W. B.; Singer, K. N.; Lauer, T.; Cheng, A. F.; Stern, A.; Weaver, H. A., Jr.; Young, L. A.; Ennico Smith, K.; Olkin, C.

2017-12-01

New Horizons imaging of Pluto's surface shows eroded landscapes reminiscent of assorted glaciated terrains found on the Earth such as alpine valleys, dendritic networks and others. For example, LORRI imaging of fluted craters show radially oriented ridging which also resembles Pluto's washboard terrain. Digital elevation modeling indicates that these down-gradient oriented ridges are about 3-4 km spaced apart with depths ranging from 0.2-0.5 km. Present day glaciation on Pluto is characterized by moving N2 ice blocks presumably riding over a H2O ice bedrock substrate. Assuming Pluto's ancient surface was sculpted by N2 glaciation, what remains a mystery is the specific nature of the glacial erosion mechanism(s) responsible for the observed features. To better resolve this puzzle, we perform landform evolution modeling of several glacial erosion processes known from terrestrial H2O ice glaciation studies. These terrestrial processes, which depend upon whether or not the glacier's base is wet or dry, include quarrying/plucking and fluvial erosion. We also consider new erosional processes (to be described in this presentation) which are unique to the highly insulating character of solid N2 including both phase change induced hydrofracture and geothermally driven basal melt. Until improvements in our knowledge of solid N2's rheology are made available (including its mechanical behavior as a binary/trinary mixture of CH4 and CO), it is difficult to assess with high precision which of the aforementioned erosion mechanisms are responsible for the observed surface etchings. Nevertheless, we consider a model crater surface and examine its erosional development due to flowing N2 glacial ice as built up over time according to N2 deposition rates based on GCM modeling of Pluto's ancient atmosphere. For given erosional mechanism our aim is to determine the permissible ranges of model input parameters (e.g., ice strength, flow rates, grain sizes, quarrying rates, etc.) that best reproduces the observed length scales found on the observed fluted craters. As of the writing of this abstract, both the processes of quarrying and phase change induced hydrofracture appear to be most promising at explaining the fluted crater ridging.

CO Diffusion and Desorption Kinetics in CO2 Ices

NASA Astrophysics Data System (ADS)

Cooke, Ilsa R.; Öberg, Karin I.; Fayolle, Edith C.; Peeler, Zoe; Bergner, Jennifer B.

2018-01-01

The diffusion of species in icy dust grain mantles is a fundamental process that shapes the chemistry of interstellar regions; yet, measurements of diffusion in interstellar ice analogs are scarce. Here we present measurements of CO diffusion into CO2 ice at low temperatures (T = 11–23 K) using CO2 longitudinal optical phonon modes to monitor the level of mixing of initially layered ices. We model the diffusion kinetics using Fick’s second law and find that the temperature-dependent diffusion coefficients are well fit by an Arrhenius equation, giving a diffusion barrier of 300 ± 40 K. The low barrier along with the diffusion kinetics through isotopically labeled layers suggest that CO diffuses through CO2 along pore surfaces rather than through bulk diffusion. In complementary experiments, we measure the desorption energy of CO from CO2 ices deposited at 11–50 K by temperature programmed desorption and find that the desorption barrier ranges from 1240 ± 90 K to 1410 ± 70 K depending on the CO2 deposition temperature and resultant ice porosity. The measured CO–CO2 desorption barriers demonstrate that CO binds equally well to CO2 and H2O ices when both are compact. The CO–CO2 diffusion–desorption barrier ratio ranges from 0.21 to 0.24 dependent on the binding environment during diffusion. The diffusion–desorption ratio is consistent with the above hypothesis that the observed diffusion is a surface process and adds to previous experimental evidence on diffusion in water ice that suggests surface diffusion is important to the mobility of molecules within interstellar ices.

Optical-cell evidence for superheated ice under gas-hydrate-forming conditions

USGS Publications Warehouse

Stern, L.A.; Hogenboom, D.L.; Durham, W.B.; Kirby, S.H.; Chou, I.-Ming

1998-01-01

We previously reported indirect but compelling evidence that fine-grained H2O ice under elevated CH4 gas pressure can persist to temperatures well above its ordinary melting point while slowly reacting to form methane clathrate hydrate. This phenomenon has now been visually verified by duplicating these experiments in an optical cell while observing the very slow hydrate-forming process as the reactants were warmed from 250 to 290 K at methane pressures of 23 to 30 MPa. Limited hydrate growth occurred rapidly after initial exposure of the methane gas to the ice grains at temperatures well within the ice subsolidus region. No evidence for continued growth of the hydrate phase was observed until samples were warmed above the equilibrium H2O melting curve. With continued heating, no bulk melting of the ice grains or free liquid water was detected anywhere within the optical cell until hydrate dissociation conditions were reached (292 K at 30 MPa), even though full conversion of the ice grains to hydrate requires 6-8 h at temperatures approaching 290 K. In a separate experimental sequence, unreacted portions of H2O ice grains that had persisted to temperatures above their ordinary melting point were successfully induced to melt, without dissociating the coexisting hydrate in the sample tube, by reducing the pressure overstep of the equilibrium phase boundary and thereby reducing the rate of hydrate growth at the ice-hydrate interface. Results from similar tests using CO2 as the hydrate-forming species demonstrated that this superheating effect is not unique to the CH4-H2O system.

Spectroscopic analyses of Fe and water in clays: A Martian surface weathering study

NASA Technical Reports Server (NTRS)

Bishop, J. L.; Pieters, Carle M.; Edwards, J. O.; Coyne, L. M.; Chang, S.

1991-01-01

Martian surface morphology suggests the presence of liquid H2O on Mars in the past. Reflectance spectra of the Martian surface include features which correspond to the crystal field transitions of iron, as well as features supporting the presence of ice and minerals containing structural OH and surface water. Researchers initiated further spectroscopic studies of surface iron and water and structural OH in clays in order to determine what remotely obtained spectra can indicate about the presence of clays on Mars based on a clearer understanding of the factors influencing the spectral features. Current technology allows researchers to better correlate the low frequency fundamental stretching and bending vibrations of O-H bonds with the diagnostic near infrared overtone and combination bands used in mineral characterization and identification.

The fate of meteoric metals in ice particles: Effects of sublimation and energetic particle bombardment

NASA Astrophysics Data System (ADS)

Mangan, T. P.; Frankland, V. L.; Murray, B. J.; Plane, J. M. C.

2017-08-01

The uptake and potential reactivity of metal atoms on water ice can be an important process in planetary atmospheres and on icy bodies in the interplanetary and interstellar medium. For instance, metal atom uptake affects the gas-phase chemistry of the Earth's mesosphere, and has been proposed to influence the agglomeration of matter into planets in protoplanetary disks. In this study the fate of Mg and K atoms incorporated into water-ice films, prepared under ultra-high vacuum conditions at temperatures of 110-140 K, was investigated. Temperature-programmed desorption experiments reveal that Mg- and K-containing species do not co-desorb when the ice sublimates, demonstrating that uptake on ice particles causes irreversible removal of the metals from the gas phase. This implies that uptake on ice particles in terrestrial polar mesospheric clouds accelerates the formation of large meteoric smoke particles (≥1 nm radius above 80 km) following sublimation of the ice. Energetic sputtering of metal-dosed ice layers by 500 eV Ar+ and Kr+ ions shows that whereas K reacts on (or within) the ice surface to form KOH, adsorbed Mg atoms are chemically inert. These experimental results are consistent with electronic structure calculations of the metals bound to an ice surface, where theoretical adsorption energies on ice are calculated to be -68 kJ mol-1 for K, -91 kJ mol-1 for Mg, and -306 kJ mol-1 for Fe. K can also insert into a surface H2O to produce KOH and a dangling H atom, in a reaction that is slightly exothermic.

Recent Advances in TiO2 -Based Nanostructured Surfaces with Controllable Wettability and Adhesion.

PubMed

Lai, Yuekun; Huang, Jianying; Cui, Zequn; Ge, Mingzheng; Zhang, Ke-Qin; Chen, Zhong; Chi, Lifeng

2016-04-27

Bioinspired surfaces with special wettability and adhesion have attracted great interest in both fundamental research and industry applications. Various kinds of special wetting surfaces have been constructed by adjusting the topographical structure and chemical composition. Here, recent progress of the artificial superhydrophobic surfaces with high contrast in solid/liquid adhesion has been reviewed, with a focus on the bioinspired construction and applications of one-dimensional (1D) TiO2-based surfaces. In addition, the significant applications related to artificial super-wetting/antiwetting TiO2-based structure surfaces with controllable adhesion are summarized, e.g., self-cleaning, friction reduction, anti-fogging/icing, microfluidic manipulation, fog/water collection, oil/water separation, anti-bioadhesion, and micro-templates for patterning. Finally, the current challenges and future prospects of this renascent and rapidly developing field, especially with regard to 1D TiO2-based surfaces with special wettability and adhesion, are proposed and discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ikaite crystal distribution in Arctic winter sea ice and implications for CO2 system dynamics

NASA Astrophysics Data System (ADS)

Rysgaard, S.; Søgaard, D. H.; Cooper, M.; Pućko, M.; Lennert, K.; Papakyriakou, T. N.; Wang, F.; Geilfus, N. X.; Glud, R. N.; Ehn, J.; McGinnnis, D. F.; Attard, K.; Sievers, J.; Deming, J. W.; Barber, D.

2012-12-01

The precipitation of ikaite (CaCO3·6H2O) in polar sea ice is critical to the efficiency of the sea ice-driven carbon pump and potentially important to the global carbon cycle, yet the spatial and temporal occurrence of ikaite within the ice is poorly known. We report unique observations of ikaite in unmelted ice and vertical profiles of ikaite abundance and concentration in sea ice for the crucial season of winter. Ice was examined from two locations: a 1 m thick land-fast ice site and a 0.3 m thick polynya site, both in the Young Sound area (74° N, 20° W) of NE Greenland. Ikaite crystals, ranging in size from a few µm to 700 µm were observed to concentrate in the interstices between the ice platelets in both granular and columnar sea ice. In vertical sea-ice profiles from both locations, ikaite concentration determined from image analysis, decreased with depth from surfaceice values of 700-900 µmol kg-1 ice (~ 25 × 106 crystals kg-1) to bottom-layer values of 100-200 µmol kg-1 ice (1-7 × 106 kg-1), all of which are much higher (4-10 times) than those reported in the few previous studies. Direct measurements of total alkalinity (TA) in surface layers fell within the same range as ikaite concentration whereas TA concentrations in bottom layers were twice as high. This depth-related discrepancy suggests interior ice processes where ikaite crystals form in surface sea ice layers and partly dissolved in bottom layers. From these findings and model calculations we relate sea ice formation and melt to observed pCO2 conditions in polar surface waters, and hence, the air-sea CO2 flux.

An observational search for CO2 ice clouds on Mars

NASA Technical Reports Server (NTRS)

Bell, James F., III; Calvin, Wendy M.; Pollack, James B.; Crisp, David

1993-01-01

CO2 ice clouds were first directly identified on Mars by the Mariner 6 and 7 infrared spectrometer limb scans. These observations provided support for early theoretical modeling efforts of CO2 condensation. Mariner 9 IRIS temperature profiles of north polar hood clouds were interpreted as indicating that these clouds were composed of H2O ice at lower latitudes and CO2 ice at higher latitudes. The role of CO2 condensation on Mars has recently received increased attention because (1) Kasting's model results indicated that CO2 cloud condensation limits the magnitude of the proposed early Mars CO2/H2O greenhouse, and (2) Pollack el al.'s GCM results indicated that the formation of CO2 ice clouds is favorable at all polar latitudes during the fall and winter seasons. These latter authors have shown that CO2 clouds play an important role in the polar energy balance, as the amount of CO2 contained in the polar caps is constrained by a balance between latent heat release, heat advected from lower latitudes, and thermal emission to space. The polar hood clouds reduce the amount of CO2 condensation on the polar caps because they reduce the net emission to space. There have been many extensive laboratory spectroscopic studies of H2O and CO2 ices and frosts. In this study, we use results from these and other sources to search for the occurrence of diagnostic CO2 (and H2O) ice and/or frost absorption features in ground based near-infrared imaging spectroscopic data of Mars. Our primary goals are (1) to try to confirm the previous direct observations of CO2 clouds on Mars; (2) to determine the spatial extent, temporal variability, and composition (H2O/CO2 ratio) of any clouds detected; and (3) through radiative transfer modeling, to try to determine the mean particle size and optical depth of polar hood clouds, thus, assessing their role in the polar heat budget.

A Search for Volatiles and Spectral Variation on the Surfaces of Trojan Asteroids

NASA Astrophysics Data System (ADS)

Emery, Joshua P.; Ness, R. G.; Lucas, M. P.

2013-10-01

Trojan asteroids comprise a substantial population of primitive bodies confined to Jupiter’s stable Lagrange regions. Because they likely became trapped in these orbits at the end of the initial phase of planetary formation and subsequent migration, the compositions of Trojans provide unique perspectives on chemical and dynamical processes that shaped the Solar System. Ices and organics are of particular interest for understanding Trojan histories. Published near-infrared (0.7 to 4.0 μm) spectra of Trojans show no absorption bands due to H2O or organics. However, if the Trojan asteroids formed at or beyond their present heliocentric distance of 5.2 AU and never spent significant amounts of time closer to the Sun, they should contain H2O ice. Low densities of two Trojan multiple asteroid systems (Patroclus and Hektor) are consistent with the presence of ice. Similarly, cosmochemical and surface irradiation arguments have been used to explain the red spectral slope of Trojans as due to the presence of complex organic molecules. We present near infrared spectra of four Trojan asteroids (3451 Mentor, 3317 Paris, 627 Hektor, and 911 Agamemnon). All objects were observed at the NASA InfraRed Telescope Facility using the SpeX medium resolution spectrograph. Spectra of Mentor and Paris cover the wavelength range 0.7 to 4.0 μm. These observations were designed primarily to look for H2O and organic absorptions in the 3 - 4 μm region. We see no evidence for any absorptions in the spectra of Mentor or Paris. Spectra of Hektor and Agamemnon cover the wavelength range 0.7 to 2.5 μm and span significant fractions of their respective rotation periods. No rotational variability is evident in the spectrum of Hektor. The spectra of Agamemnon may exhibit a very small amount of variability in spectral slope, but analysis is ongoing. We will discuss the implications of these results in terms of Trojan surface compositions.

Slope Gullies on Devon Island, Canadian Arctic: Possible Analogs for Gullies on Mars and Evidence for Recent Transient Environmental Change on Mars.

NASA Astrophysics Data System (ADS)

Lee, P.

2002-12-01

The origin and evolution of the relatively youthful slope gully features on Mars first reported by Malin and Edgett (2000) remain enigmatic. Two prevailing hypotheses concerning their formation involve the discharge of subsurface H2O at the gully sites: groundwater seepage (1) and/or the melting of ground-ice (2, 3). In the course of geologic field investigations on Devon Island, Canadian Arctic, we have identified morphologic and contextual analogs for the martian gullies that result from a radically different mechanism of formation (4). The gullies on Devon result mainly from the episodic melting of transient surface snow and ice deposits, with little contribution from subsurface H2O reservoirs. Timescales for gully formation on Devon Island are ­š104 years (5). The gullies on Devon suggest that the formation of gully features on Mars might not necessarily have involved discharges of subsurface H2O at the gully sites. Instead, gullies on Mars might be the result of transient surface snow and ice melting, which in turn might be the result of short-term changes in regional surface environmental conditions (on time-scales of ­š105-108 years?) possibly in association with high obliquity-induced climate change (6, 7) and/or volcanic activity. Acknowledgements: This research was conducted under the auspices of the NASA Haughton-Mars Project (HMP) with support from NASA and the National Geographic Society. References: (1) Malin, M. C. and K. S. Edgett 2000. Science 288, 2330-2335. (2) Mellon, M. T. and R. J. Phillips 2001. J. Geophys. Res. 106, 23165-23179. (3) Costard, F. et al. 2002. Science 295, 110-112. (4) Lee, P. et al. 2001. LPSC. XXXII, Houston, TX, Mar 12-16, 2001. (5) Lee, P, et al. 2002. LPSC XXXIII, Houston, TX, Mar 11-15, 2002. (6) Ward, W. R. (1973) Science 181, 260-262. (7) Touma, J. and J. Wisdom (1993) Science 259, 1294-1296.

Laboratory IR Studies and Astrophysical Implications of C2H2-Containing Binary Ices

NASA Technical Reports Server (NTRS)

Knez, C.; Moore, M.; Ferrante, R.; Hudson, R.

2012-01-01

Studies of molecular hot cores and protostellar environments have shown that the observed abundance of gas-phase acetylene (C2H2) cannot be matched by chemical models without the inclusion of C2H2 molecules subliming from icy grain mantles. Searches for infrared (IR) spectral features of solid-phase acetylene are under way, but few laboratory reference spectra of C2H2 in icy mixtures, which are needed for spectral fits to observational data, have been published. Here, we report a systematic study of the IR spectra of condensed-phase pure acetylene and acetylene in ices dominated by carbon monoxide (CO), carbon dioxide (CO2), methane (CH4), and water (H2O). We present new spectral data for these ices, including band positions and intrinsic band strengths. For each ice mixture and concentration, we also explore the dependence of acetylene's nu5-band position (743 cm-1, 13.46 micrometers) and FWHM on temperature. Our results show that the nu5 feature is much more cleanly resolved in ices dominated by non-polar and low-polarity molecules, specifically CO, CO2, and CH4, than in mixtures dominated by H2O-ice. We compare our laboratory ice spectra with observations of a quiescent region in Serpens.

Calculations of electric currents in Europa

NASA Technical Reports Server (NTRS)

Colburn, D. S.; Reynolds, R. T.

1986-01-01

Electrical currents should flow in the Galilean satellite, Europa, because it is located in Jupiter's corotating magnetosphere. The possible magnitudes of these currents are calculated by assuming that Europa is a differentiated body consisting of an outer H2O layer and a silicate core. Two types of models are considered here: one in which the water is completely frozen and a second in which there is an intermediate liquid layer. For the transverse electric mode (eddy currents), the calculated current density in a liquid layer is approximately 10 to the -5/Am. For the transverse magnetic mode (unipolar generator), the calculated current density in the liquid is severely constrained by the ice layer to a range of only 10 to the -10 to -11th power/ Am, for a total H2O thickness of 100 km, provided that neither layer is less than 4 km thick. The current density is less for a completely frozen H2O layer. If transient cracks were to appear in the ice layer, thereby exposing liquid, the calculated current density could rise to a range of 10 to the -6 to 10 to the -5/Am, depending on layer thicknesses, which would require an exposed area of 10 to the -9 to 10 to the -8 of the Europa surface. The corresponding total current of 2.3x10 to the 5th power A could in 1 yr. electrolyze 7x10 to the 5th power kg of water (and more if the cells were in series), and thereby store up to 10 the 8th power J of energy, but it is not clear how electrolysis can take place in the absence of suitable electrodes. Electrical heating would be significant only if the ice-layer thickness were on the order of 1 m, such as might occur if an exposed liquid surface were to freeze over; the heating under this condition could hinder the thickening of the ice layer.

Optical spectrophotometry of Comet P/Giacobini-Zinner and emission profiles of H2O+

NASA Technical Reports Server (NTRS)

Strauss, M. A.; Mccarthy, P. J.; Spinrad, H.

1986-01-01

Two-dimensional CCD spectrograms were obtained of Comet P/Giacobini-Zinner (1984e) on five occasions between July and October 1985. Spatial emission profiles of H2O+ were extracted at 6198 angstroms (the strongest ionic line in the visible spectrum). This emission line traces the extent of the ion, or plasma, tail. The spectrographic slit was placed approximately along the trajectory of the ICE spacecraft on September 11, 1985; the resulting H2O+ profile has a full-width-half-maximum of about 5700 km, about three times that of the plasma density profile measured by ICE, and has a full-width-zero-intensity of about 30,000 km, very similar to the ICE values. H2O production rates for the comet are derived and compared with those of Comet P/Halley (1982i).

Adsorption and reactions of atmospheric constituents and pollutants on ice particles: an FTIR study

NASA Astrophysics Data System (ADS)

Rudakova, A. V.; Marinov, I. L.; Poretskiy, M. S.; Tsyganenko, A. A.

2009-04-01

Processes on icy particles attract much attention due to their importance for atmospheric science, ecology and astrophysics. In this work, adsorption and ecologically important reactions of some molecules on pure and mixed water icy films by means of FTIR spectroscopy have been investigated. The cell for spectral studies of adsorbed molecules at variable temperatures (55-370 K), described elsewhere1, enables one to run the spectra in the presence of gaseous adsorbate, and even to perform adsorption from the solution in some cryogenic solvents. For the studies of ice films, it was equipped with a device for water vapour sputtering from the heated capillaries and deposition onto the inner BaF2 or ZnSe windows of the cell, cooled by liquid nitrogen. Lower temperatures were obtained by pumping off evaporating nitrogen from the coolant volume. The estimated specific surface area of freshly deposited at 77 K water ice film was about 160 m2/g and decreases on raising the temperature together with the diminishing intensity of the bands of dangling OH (OD) groups at 3696 (2727) cm-1 until the latter disappear at 130 - 160 K when the changes of bulk absorption provide evidence for a phase transition from amorphous to polycrystalline ice. CO adsorption at 77 K results in two bands at 2153 and 2137 cm-1 assigned to molecules forming weak H-bond with the dangling hydroxyl groups and bound to unsaturated surface oxygen atoms, respectively2. The band of dangling hydroxyl groups moves to lower wavenumbers on adsorption of different molecules (hydrogen, nitrogen, methane, ozone, NO, ethane or chlorinated ethenes, etc.). The shift value depends on the nature of adsorbate. Besides this shift, spectra of adsorbed nitrogen and methane registered at 55 K reveal the adsorption intensity decrease at ~ 2650 cm-1 at the high-frequency slope of bulk adsorption, and increase at about 25 cm-1 below. We interpret this perturbation as a strengthening of H-bonds between surface water molecules, which act as adsorption sites either as a proton-donor or as a donor of the lone pair of electrons. Such adsorption-induced relaxation explains the dependence of physico-chemical properties of icy particles on the presence of atmospheric gases. Spectra HCN/D2O and ND3/D2O mixed icy films with low (1:10) dopant/water ratios do not manifest any changes in the acidic or basic properties of dangling hydroxyl groups or surface oxygen atoms, but reveal a difference in the proportion between the concentrations of these sites as compared with that for pure water ice. For high dopant concentrations (1:1), the dangling hydroxyls were not observed; the dominant adsorption sites for CO are likely to be the unsaturated oxygen atoms, while serious structural changes occur in the bulk of ices. Ecologically important reactions of atmospheric pollutants such as ozonolysis of ethene, chlorinated ethenes, hydrogen cyanide, and methyl bromide adsorbed on water ice film as well as the influence of UV radiation on this process have been studied in 77 - 200 K temperature range by FTIR spectroscopy. Ozone co-adsorption with ethene or C2H3Cl readily leads to ozonolysis reaction, which also starts for C2H2Cl2 isomers but only at temperatures elevated up to 120 - 150 K. Co-adsorption of O3 with HCN or CH3Br molecules in the dark does not lead to any noticeable spectral changes. Irradiation of HCN or CH3Br deposited on ice films in the presence of ozone leads to appearance of new bands revealing the formation of ozonolysis products. The same "synergetic effect" of simultaneous action of ozone and UV radiation at 77 K, was found for C2H2Cl2 isomers and C2Cl4, which are resistant against O3 even at higher temperatures. The obtained spectral dependence of photo-ozonolysis of C2Cl4 and HCN at 77 K shows that photoexcitation or photodissociation of ozone, evidently, accounts for the observed processes. The surface of ice particles, thus, plays the role of a condenser of atmospheric pollutants and acts as a micro- photoreactor in the atmospheric chemistry. Acknowledgments. The work was supported by INTAS (grant 03-51-5698) and RFBR (grants 06-03-32836 and 06-05-64646). 1. Otero Areán С., Manoilova O.V., Tsyganenko A.A., Turnes Palomino G., Peñarroya Mentruit M., Geobaldo F., Garrone E. Eur. J. Inorg. Chem., 2001, No 7, 1739. 2. Rudakova A.V., Sekushin V.N., Marinov I.L., Tsyganenko A.A. Langmuir, 25 (2009) 000.

On liquid phases in cometary nuclei

NASA Astrophysics Data System (ADS)

Miles, Richard; Faillace, George A.

2012-06-01

In this paper we review the relevant literature and investigate conditions likely to lead to melting of H2O ice, methanol (CH3OH) ice, ethane (C2H6) ice and other volatile ices in cometary nuclei. On the basis of a heat balance model which takes account of volatiles loss, we predict the formation of occasional aqueous and hydrocarbon liquid phases in subsurface regions at heliocentric distances, rh of 1-3 AU, and 5-12 AU, respectively. Low triple-point temperatures and low vapour pressures of C2H6, C3H8, and some higher-order alkanes and alkenes, favour liquid phase formation in cometary bodies at high rh. Microporosity and the formation of a stabilization crust occluding the escape of volatiles facilitate liquid-phase formation. Characteristics of the near-surface which favour subsurface melting include; low effective surface emissivity (at low rh), high amorphous carbon content, average pore sizes of ˜10 μm or less, presence of solutes (e.g. CH3OH), mixtures of C2-C6 hydrocarbons (for melting at high rh), diurnal thermal cycling, and slow rotation rate. Applying the principles of soil mechanics, capillary forces are shown to initiate pre-melting phenomena and subsequent melting, which is expected to impart considerable strength of ˜104 Pa in partially saturated layers, reducing porosity and permeability, enhancing thermal conductivity and heat transfer. Diurnal thermal cycling is expected to have a marked effect on the composition and distribution of H2O ice in the near-surface leading to frost heave-type phenomena even where little if any true melting occurs. Where melting does take place, capillary suction in the wetted zone has the potential to enhance heat transfer via capillary wetting in a low-gravity environment, and to modify surface topography creating relatively smooth flat-bottomed features, which have a tendency to be located within small depressions. An important aspect of the "wetted layer" model is the prediction that diurnal melt-freeze cycles alter the mixing ratio vs. depth of solutes present, or of other miscible components, largely through a process of fractional crystallization, but also potentially involving frost heave. Wetted layers are potentially durable and can involve significant mass transport of volatile materials in the near-surface, increasing in extent over many rotations of the nucleus prior to and just after perihelion passage, and causing stratification and trapping of the lowest-melting mixtures at depths of several metres. A possible mechanism for cometary outbursts is proposed involving a heat pulse reaching the liquid phase in the deepest wetted zone, leading to supersaturation and triggering the sudden release under pressure of dissolved gases, in particular CO2, CO, CH4 or N2, contained beneath a consolidated near-surface layer. This study indicates that liquid water can persist for long periods of time in the near-surface of some intermediate-sized bodies (102-103 km radius) within protoplanetary discs.

Hydrated states of MgSO4 at equatorial latiudes on Mars

USGS Publications Warehouse

Feldman, W.C.; Mellon, M.T.; Maurice, S.; Prettyman, T.H.; Carey, J.W.; Vaniman, D.T.; Bish, D.L.; Fialips, C.I.; Chipera, S.J.; Kargel, J.S.; Elphic, R.C.; Funsten, H.O.; Lawrence, D.J.; Tokar, R.L.

2004-01-01

The stability of water ice, epsomite, and hexahydrite to loss of H 2O molecules to the atmosphere at equatorial latitudes of Mars was studied to determine their potential contributions to the measured abundance of water-equivalent hydrogen (WEH). Calculation of the relative humidity based on estimates of yearly averages of water-vapor pressures and temperatures at the Martian surface was used for this purpose. Water ice was found to be sufficiently unstable everywhere within 45?? of the equator that if the observed WEH is due to water ice, it requires a low-permeability cover layer near the surface to isolate the water ice below from the atmosphere above. In contrast, epsomite or hexahydrite may be stable in many near-equatorial locations where significant amounts of WEH are observed. Copyright 2004 by the American Geophysical Union.

Interstellar grain chemistry and organic molecules

NASA Technical Reports Server (NTRS)

Allamandola, L. J.; Sandford, S. A.

1990-01-01

The detection of prominant infrared absorption bands at 3250, 2170, 2138, 1670 and 1470 cm(-1) (3.08, 4.61, 4.677, 5.99 and 6.80 micron m) associated with molecular clouds show that mixed molecular (icy) grain mantles are an important component of the interstellar dust in the dense interstellar medium. These ices, which contain many organic molecules, may also be the production site of the more complex organic grain mantles detected in the diffuse interstellar medium. Theoretical calculations employing gas phase as well as grain surface reactions predict that the ices should be dominated only by the simple molecules H2O, H2CO, N2, CO, O2, NH3, CH4, possibly CH3OH, and their deuterated counterparts. However, spectroscopic observations in the 2500 to 1250 cm(-1)(4 to 8 micron m) range show substantial variation from source reactions alone. By comparing these astronomical spectra with the spectra of laboratory-produced analogs of interstellar ices, one can determine the composition and abundance of the materials frozen on the grains in dense clouds. Experiments are described in which the chemical evolution of an interstellar ice analog is determined during irradiation and subsequent warm-up. Particular attention is paid to the types of moderately complex organic materials produced during these experiments which are likely to be present in interstellar grains and cometary ices.

Production of O2 on icy satellites by electronic excitation of low-temperature water ice.

PubMed

Sieger, M T; Simpson, W C; Orlando, T M

1998-08-06

The signature of condensed molecular oxygen has been reported in recent optical-reflectance measurements of the jovian moon Ganymede, and a tenuous oxygen atmosphere has been observed on Europa. The surfaces of these moons contain large amounts of water ice, and it is thought that O2 is formed by the sputtering of ice by energetic particles from the jovian magnetosphere. Understanding how O2 might be formed from low-temperature ice is crucial for theoretical and experimental simulations of the surfaces and atmospheres of icy bodies in the Solar System. Here we report laboratory measurements of the threshold energy, cross-section and temperature dependence of O2 production by electronic excitation of ice in vacuum, following electron-beam irradiation. Molecular oxygen is formed by direct excitation and dissociation of a stable precursor molecule, rather than (as has been previously thought) by diffusion and chemical recombination of precursor fragments. The large cross-section for O2 production suggests that electronic excitation plays an important part in the formation of O2 on Ganymede and Europa.

The catalytic role of water in the photochemistry of ammonia ice: from diluted to concentrated phase

NASA Astrophysics Data System (ADS)

Jonusas, Mindaugas; Krim, Lahouari

2017-10-01

Using infrared spectroscopy as an in situ probe for reactions occurring in the solid phase, we investigated the influence of water molecules on the photochemistry of ammonia ices. Experiments were carried out in diluted and concentrated phases and between 3 and 130 K. We showed that the photolysis of NH3-H2O (2 per cent of H2O) ices using continuous radiation from 115 to 400 nm produces NH2OH as the main photoproduct, but also that such a photoinduced reaction strongly depends on both the initial ice temperature and the environment where the primary reactants NH3 and H2O are trapped. Our experimental results highlight the catalytic role played by H2O molecules in enhancing the formation yield of NH2 during the photolysis process through the NH3 + OH → NH2 + H2O hydrogen abstraction reaction, which is only favored at low temperatures in the range of 3-60 K. During heating of such irradiated ammonia-water ices, the amount of NH2OH keeps rising while that of NH2, is greatly reduced only from 70 K onwards. These behaviours are attributed to the competition that occurs between NH2 formation from the NH3 + OH reaction and its consumption from the NH2 + OH radical recombination. These results might explain the variable abundances of NH2 and NH3 provided by previous astronomical observations, where the NH2/NH3 ratio ranges from 0.02 to 0.5 depending on the regions of the interstellar medium that were analysed.

Possible fossil H2O liquid-ice interfaces in the Martian crust

NASA Technical Reports Server (NTRS)

Soderblom, L. A.; Wenner, D. B.

1978-01-01

The extensive chaotic and fretted terrains in the equatorial regions of Mars are explained on the basis of the vertical distribution of H2O liquid and ice which once existed in the crust. This account assumes that below the permafrost containing water ice, there was a second zone in which liquid water resided for at least a time. Diagenetic alteration and cementation characterized the material in the subpermafrost zone; above, pristine fragmented material with various ice concentrations was found. Later, the ice-laden zone was stripped away by a number of erosional processes, exposing the former ice-liquid water interface.

Exogenic and endogenic Europa minerals

NASA Astrophysics Data System (ADS)

Maynard-Casely, H. E.; Brand, H. E. A.; Wilson, S. A.

2016-12-01

The Galileo Near Infrared Mapping Spectrometer (NIMS) identified a significant `non-ice' component upon the surface of Jupiter's moon Europa. Current explanations invoke both endogenic and exogenic origins for this material. It has long been suggested that magnesium and sodium sulfate minerals could have leached from the rock below a putative ocean (endogenic) 1 and that sulfuric acid hydrate minerals could have been radiologically produced from ionised sulfur originally from Io's volcanoes (exogenic) 2. However, a more recent theory proposes that the `non-ice' component could be radiation damaged NaCl leached from Europa's speculative ocean 3. What if the minerals are actually from combination of both endogenic and exogenic sources? To investigate this possibility we have focused on discovering new minerals that might form in the combination of the latter two cases, that is a mixture of leached sulfates hydrates with radiologically produced sulfuric acid. To this end we have explored a number of solutions in the MgSO4-H2SO4-H2O and Na2SO4-H2SO4-H2O systems, between 80 and 280 K with synchrotron x-ray powder diffraction. We report a number of new materials formed in this these ternary systems. This suggests that it should be considered that the `non-ice' component of the Europa's surface could be a material derived from endogenic and exogenic components. 1 Kargel, J. S. Brine volcanism and the interior structures of asteroids and icy satellites. Icarus 94, 368-390 (1991). 2 Carlson, R. W., Anderson, M. S., Mehlman, R. & Johnson, R. E. Distribution of hydrate on Europa: Further evidence for sulfuric acid hydrate. Icarus 177, 461-471, doi:10.1016/j.icarus.2005.03.026 (2005). 3 Hand, K. P. & Carlson, R. W. Europa's surface color suggests an ocean rich with sodium chloride. Geophysical Research Letters, 2015GL063559, doi:10.1002/2015gl063559 (2015).

Evolution of Interstellar Ices

NASA Astrophysics Data System (ADS)

Allamandola, Louis J.; Bernstein, Max P.; Sandford, Scott A.; Walker, Robert L.

1999-10-01

Infrared observations, combined with realistic laboratory simulations, have revolutionized our understanding of interstellar ice and dust, the building blocks of comets. Ices in molecular clouds are dominated by the very simple molecules H2O, CH3OH, NH3, CO, CO2, and probably H2CO and H2. More complex species including nitriles, ketones, and esters are also present, but at lower concentrations. The evidence for these, as well as the abundant, carbon-rich, interstellar, polycyclic aromatic hydrocarbons (PAHs) is reviewed. Other possible contributors to the interstellar/pre-cometary ice composition include accretion of gas-phase molecules and in situ photochemical processing. By virtue of their low abundance, accretion of simple gas-phase species is shown to be the least important of the processes considered in determining ice composition. On the other hand, photochemical processing does play an important role in driving dust evolution and the composition of minor species. Ultraviolet photolysis of realistic laboratory analogs readily produces H2, H2CO, CO2, CO, CH4, HCO, and the moderately complex organic molecules: CH3CH2OH (ethanol), HC(=O)NH2 (formamide), CH3C(=O)NH2 (acetamide), R-CN (nitriles), and hexamethylenetetramine (HMT, C6H12N4), as well as more complex species including amides, ketones, and polyoxymethylenes (POMs). Inclusion of PAHs in the ices produces many species similar to those found in meteorites including aromatic alcohols, quinones and ethers. Photon assisted PAH-ice deuterium exchange also occurs. All of these species are readily formed and are therefore likely cometary constituents.

Radiation Effects in Hydrogen-Laden Porous Water Ice Films: Implications for Interstellar Ices

NASA Astrophysics Data System (ADS)

Raut, Ujjwal; Baragiola, Raul; Mitchell, Emma; Shi, Jianming

H _{2} is the dominant gas in the dense clouds of the interstellar medium (ISM). At densities of 10 (5) cm (-3) , an H _{2} molecule arrives at the surface of a 0.1 mum-sized, ice-covered dust grain once every few seconds [1]. At 10 K, H _{2} can diffuse into the pores of the ice mantle and adsorb at high-energy binding sites, loading the ice with hydrogen over the lifetime of the cloud. These icy grains are also impacted by galactic cosmic rays and stellar winds (in clouds with embedded protostar). Based on the available cosmic proton flux spectrum [2], we estimate a small impact rate of nearly 1 hit per year on a 0.1 μm sized grain, or 10 (-7) times the impact frequency of the neutral H _{2}. The energy deposited by such impacts can release the adsorbed H _{2} into the gas phase (impact desorption or sputtering). Recently, we have reported on a new process of ion-induced enhanced adsorption, where molecules from the gas phase are incorporated into the film when irradiation is performed in the presence of ambient gas [3]. The interplay between ion-induced ejection and adsorption can be important in determining the gas-solid balance in the ISM. To understand the effects of cosmic rays/stellar winds impacts on interstellar ice immersed in H _{2} gas, we have performed irradiation of porous amorphous ice films loaded with H _{2} through co-deposition or adsorption following growth. The irradiations were performed with 100 keV H (+) using fluxes of 10 (10) -10 (12) H (+) cm (-2) s (-1) at 7 K, in presence of ambient H _{2} at pressures ranging from 10 (-5) to 10 (-8) Torr. Our initial results show a net loss in adsorbed H _{2} during irradiation, from competing ion-induced ejection and adsorption. The H _{2} loss per ion decreases exponentially with fluence, with a cross-section of 10 (-13) cm (2) . In addition to hydrogen removal, irradiation also leads to trapping of H _{2} in the ice film, from closing of the pores during irradiation [4]. As a result, 2.6 percent H _{2} molar remains trapped in the ice even upon removal of ambient gas-phase H _{2}, and is stable to 170 K, where the ice film desorbs. We will describe the dependence of net loss of adsorbed hydrogen on important parameters such as ice film thickness and the ratio of ion flux (f) to H _{2} flux (F _{H}). Both fluxes are higher by orders of magnitude than interstellar values. However, the information obtained from these experiments, especially the behavior in the limit of low flux (f << F _{H}) should be relevant to the interstellar case. Furthermore, we will discuss the effects of the presence of H _{2} in radiation chemistry of water ice, in particular, the observed suppression in H _{2}O _{2} synthesis. References: 1.Tielens, A.G.G.M., The Physics and Chemistry of the Interstellar Medium. 2005: Cambridge University Press. 2.Webber, W.R. and S.M. Yushak, A measurement of the energy spectra and relative abundance of the cosmic-ray H and He isotopes over a broad energy range. Astrophysical Journal, 1983. 275: p. 391-404. 3.Shi, J., B.D. Teolis, and R.A. Baragiola, Irradiation-enhanced adsorption and trapping of O2 on nanoporous water ice. Physical Review B, 2009. 79(23): p. 235422. 4.Raut, U., et al., Compaction of microporous amorphous solid water by ion irradiation. Journal of Chemical Physics, 2007. 126(24): p. 244511.

Outbursts of H2O in Comet P/Halley

NASA Astrophysics Data System (ADS)

Larson, H. P.; Hu, H.-Y.; Mumma, M. J.; Weaver, H. A.

1990-07-01

Comet Halley gas-production monitoring efforts in March 1986 with the NASA Kuiper Airborne Observatory's Fourier transform spectrometer have indicated rapid temporal variations in H2O emissions; a continuous record of an H2O outburst was thus obtained. The event, in which H2O brightness increased by a factor of 2.2 in less than 10 min, is ascribable to an energetic process in the nucleus whose character may have been that of amorphous H2O ice crystallization, chemical explosion, thermal stress, or a compressed gas pocket. The timing and energy of the event appear to require an internal energy source; amorphous ice crystallization is held to be most consistent with compositional and thermal models of cometary nuclei as well as the observations.

Brief communication: ikaite (CaCO3*6H2O) discovered in Arctic sea ice

NASA Astrophysics Data System (ADS)

Dieckmann, G. S.; Nehrke, G.; Uhlig, C.; Göttlicher, J.; Gerland, S.; Granskog, M. A.; Thomas, D. N.

2010-02-01

We report for the first time on the discovery of calcium carbonate crystals as ikaite (CaCO3*6H2O) in sea ice from the Arctic (Kongsfjorden, Svalbard). This finding demonstrates that the precipitation of calcium carbonate during the freezing of sea ice is not restricted to the Antarctic, where it was observed for the first time in 2008. This finding is an important step in the quest to quantify its impact on the sea ice driven carbon cycle and should in the future enable improvement parametrization sea ice carbon models.

Ultrafast photochemistry of methyl hydroperoxide on ice particles

PubMed Central

Kamboures, M. A.; Nizkorodov, S. A.; Gerber, R. B.

2009-01-01

Simulations show that photodissociation of methyl hydroperoxide, CH3OOH, on water clusters produces a surprisingly wide range of products on a subpicosecond time scale, pointing to the possibility of complex photodegradation pathways for organic peroxides on aerosols and water droplets. Dynamics are computed at several excitation energies at 50 K using a semiempirical PM3 potential surface. CH3OOH is found to prefer the exterior of the cluster, with the CH3O group sticking out and the OH group immersed within the cluster. At atmospherically relevant photodissociation wavelengths the OH and CH3O photofragments remain at the surface of the cluster or embedded within it. However, none of the 25 completed trajectories carried out at the atmospherically relevant photodissociation energies led to recombination of OH and CH3O to form CH3OOH. Within the limited statistics of the available trajectories the predicted yield for the recombination is zero. Instead, various reactions involving the initial fragments and water promptly form a wide range of stable molecular products such as CH2O, H2O, H2, CO, CH3OH, and H2O2. PMID:19846778

Electron-stimulated reactions in layered CO/H2O films: Hydrogen atom diffusion and the sequential hydrogenation of CO to methanol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrik, Nikolay G.; Monckton, Rhiannon J.; Koehler, Sven

Low-energy (100 eV) electron-stimulated reactions in layered H2O/CO/H2O ices are investigated. For CO trapped within approximately 50 ML of the vacuum interface in the amorphous solid water (ASW) films, both oxidation and reduction reactions are observed. However for CO buried more deeply in the film, only the reduction of CO to methanol is observed. Experiments with layered films of H2O and D2O show that the hydrogen atoms participating in the reduction of the buried CO originate in region from ~10 – 40 ML below the surface of the ASW films and subsequently diffuse through the film. For deeply buried COmore » layers, the CO reduction reactions quickly increase with temperature above ~60 K. We present a simple chemical kinetic model that treats the diffusion of hydrogen atoms in the ASW and sequential hydrogenation of the CO to methanol that accounts for the observations.« less

Quantum chemical protocols for modeling reactions and spectra in astrophysical ice analogs: the challenging case of the C⁺ + H₂O reaction in icy grain mantles.

PubMed

Woon, David E

2015-11-21

Icy grain mantles that accrete on refractory dust particles in the very cold interstellar medium or beyond the snow line in protoplanetary disks serve as minute incubators for heterogeneous chemistry. Ice mantle chemistry can differ significantly from the gas phase chemistry that occurs in these environments and is often richer. Modeling ices and their chemistry is a challenging task for quantum theoretical methods, but theory promises insight into these systems that is difficult to attain with experiments. Density functional theory (DFT) is predominately employed for modeling reactions in icy grain mantles due to its favorable scalability, but DFT has limitations that risk undercutting its reliability for this task. In this work, basic protocols are proposed for identifying the degree to which DFT methods are able to reproduce experimental or higher level theoretical results for the fundamental interactions upon which ice mantle chemistry depends, including both reactive interactions and non-reactive scaffolding interactions. The exemplar of this study is the reaction of C(+) with H2O, where substantial methodological differences are found in the prediction of gas phase relative energetics for stationary points (about 10 kcal mol(-1) for the C-O bond energy of the H2OC(+) intermediate), which in turn casts doubt about employing it to treat the C(+) + H2O reaction on an ice surface. However, careful explorations demonstrate that B3LYP with small correlation consistent basis sets performs in a sufficiently reliable manner to justify using it to identify plausible chemical pathways, where the dominant products were found to be neutral HOC and the CO(-) anion plus one and two H3O(+) cations, respectively. Predicted vibrational and electronic spectra are presented that would serve to verify or disconfirm the pathways; the latter were computed with time-dependent DFT. Conclusions are compared with those of a recent similar study by McBride and coworkers (J. Phys. Chem. A, 2014, 118, 6991).

Peeling the astronomical onion.

PubMed

Rosu-Finsen, Alexander; Marchione, Demian; Salter, Tara L; Stubbing, James W; Brown, Wendy A; McCoustra, Martin R S

2016-11-23

Water ice is the most abundant solid in the Universe. Understanding the formation, structure and multiplicity of physicochemical roles for water ice in the cold, dense interstellar environments in which it is predominantly observed is a crucial quest for astrochemistry as these are regions active in star and planet formation. Intuitively, we would expect the mobility of water molecules deposited or synthesised on dust grain surfaces at temperatures below 50 K to be very limited. This work delves into the thermally-activated mobility of H 2 O molecules on model interstellar grain surfaces. The energy required to initiate this process is studied by reflection-absorption infrared spectroscopy of small quantities of water on amorphous silica and highly oriented pyrolytic graphite surfaces as the surface is annealed. Strongly non-Arrhenius behaviour is observed with an activation energy of 2 kJ mol -1 on the silica surface below 25 K and 0 kJ mol -1 on both surfaces between 25 and 100 K. The astrophysical implication of these results is that on timescales shorter than that estimated for the formation of a complete monolayer of water ice on a grain, aggregation of water ice will result in a non-uniform coating of water, hence leaving bare grain surface exposed. Other molecules can thus be formed or adsorbed on this bare surface.

New Equations for the Sublimation Pressure and Melting Pressure of H2O Ice Ih

NASA Astrophysics Data System (ADS)

Wagner, Wolfgang; Riethmann, Thomas; Feistel, Rainer; Harvey, Allan H.

2011-12-01

New reference equations, adopted by the International Association for the Properties of Water and Steam (IAPWS), are presented for the sublimation pressure and melting pressure of ice Ih as a function of temperature. These equations are based on input values derived from the phase-equilibrium condition between the IAPWS-95 scientific standard for thermodynamic properties of fluid H2O and the equation of state of H2O ice Ih adopted by IAPWS in 2006, making them thermodynamically consistent with the bulk-phase properties. Compared to the previous IAPWS formulations, which were empirical fits to experimental data, the new equations have significantly less uncertainty. The sublimation-pressure equation covers the temperature range from 50 K to the vapor-liquid-solid triple point at 273.16 K. The ice Ih melting-pressure equation describes the entire melting curve from 273.16 K to the ice Ih-ice III-liquid triple point at 251.165 K. For completeness, we also give the IAPWS melting-pressure equation for ice III, which is slightly adjusted to agree with the ice Ih melting-pressure equation at the corresponding triple point, and the unchanged IAPWS melting-pressure equations for ice V, ice VI, and ice VII.

Geology and Composition of Pluto and Charon from New Horizons

NASA Astrophysics Data System (ADS)

Spencer, John R.; Stern, S. Alan; Moore, Jeffrey M.; Grundy, W. M.; McKinnon, William B.; Cruikshank, Dale P.; Weaver, Harold A.; Olkin, Catherine B.; Young, Leslie; Ennico, Kimberly; New Horizons Geology/Geophysics and Composition Theme Teams

2016-10-01

Data gathered by New Horizons during its July 2015 flyby has revolutionized our understanding of the geology and surface composition of Pluto and Charon. While much of Pluto's ice shell is ancient and rigid, as evinced by locally high crater densities and deep graben, much of the surface has been reworked, up to the present day, by a bewildering variety of geological processes. These include deposition and erosion of kilometers of mantle material, sublimation, apparent cryovolcanism, chaotic breakup of the crust to form rugged mountains, erosion and creation of channel networks by probable glacial action, and active glaciation. Pluto's anti-Charon hemisphere is dominated by 1000 km wide field of actively convecting nitrogen and other ices, informally called Sputnik Planum, occupying a large depression of probable impact origin. Color and composition is very varied, and is dominated by dark red tholins and N2, CH4, and CO ices, with H2O ice bedrock also exposed in many places. Apart from Sputnik Planum, color and composition is strongly correlated with latitude, showing the importance of insolation in controlling ice distribution. Charon shows pervasive extensional tectonism and locally extensive cryovolcanic resurfacing, both dating from early in solar system history. Its color and surface composition, dominated by H2O ice plus NH3 hydrate, is remarkably uniform apart from a thin deposit of dark red material near the north pole which may be due to cold-trapping and radiolysis of hydrocarbons escaping from Pluto. Neither Pluto nor Charon is likely to have experienced tidal heating during the period when observable landforms were created. Charon's surface shows resurfacing comparable in extent and age to many Saturnian and Uranian satellites such as Dione or Ariel, suggesting that observed activity on these satellites may not necessarily be tidally-driven. Pluto demonstrates that resurfacing on small volatile-rich icy bodies can be powered for at least 4.5 Ga by ongoing radiogenic and residual early heat alone, though the fact that Triton shows much more pervasive resurfacing than Pluto provides some evidence that Triton, unlike Pluto, has access to an additional heat source, presumably tidal.

Effects of glacial meltwater inflows and moat freezing on mixing in an ice-covered antarctic lake as interpreted from stable isotope and tritium distributions

USGS Publications Warehouse

Miller, L.G.; Aiken, G.R.

1996-01-01

Perennially ice-covered lakes in the McMurdo Dry Valleys have risen several meters over the past two decades due to climatic warming and increased glacial meltwater inflow. To elucidate the hydrologic responses to changing climate and the effects on lake mixing processes we measured the stable isotope (??18O and ??D) and tritium concentrations of water and ice samples collected in the Lake Fryxell watershed from 1987 through 1990. Stable isotope enrichment resulted from evaporation in stream and moat samples and from sublimation in surface lake-ice samples. Tritium enrichment resulted from exchange with the postnuclear atmosphere in stream and moat samples. Rapid injection of tritiated water into the upper water column of the make and incorporation of this water into the ice cover resulted in uniformly elevated tritium contents (> 3.0 TU) in these reservoirs. Tritium was also present in deep water, suggesting that a component of bottom water was recently at the surface. During summer, melted lake ice and stream water forms the moat. Water excluded from ice formation during fall moat freezing (enriched in solutes and tritium, and depleted in 18O and 2H relative to water below 15-m depth) may sink as density currents to the bottom of the lake. Seasonal lake circulation, in response to climate-driven surface inflow, is therefore responsible for the distribution of both water isotopes and dissolved solutes in Lake Fryxell.

Release of N 2, CH 4, CO 2, and H 2O from surface ices on Enceladus

NASA Astrophysics Data System (ADS)

Hodyss, Robert; Goguen, Jay D.; Johnson, Paul V.; Campbell, Colin; Kanik, Isik

2008-09-01

We vapor deposit at 20 K a mixture of gases with the specific Enceladus plume composition measured in situ by the Cassini INMS [Waite, J.H., Combi, M.R., Ip, W.H., Cravens, T.E., McNutt, R.L., Kasprzak, W., Yelle, R., Luhmann, J., Niemann, H., Gell, D., Magee, B., Fletcher, G., Lunine, J., Tseng, W.L., 2006. Science 311, 1419-1422] to form a mixed molecular ice. As the sample is slowly warmed, we monitor the escaping gas quantity and composition with a mass spectrometer. Pioneering studies [Schmitt, B., Klinger, J., 1987. Different trapping mechanisms of gases by water ice and their relevance for comet nuclei. In: Rolfe, E.J., Battrick, B. (Eds.), Diversity and Similarity of Comets. SP-278. ESA, Noordwijk, The Netherlands, pp. 613-619; Bar-Nun, A., Kleinfeld, I., Kochavi, E., 1988. Phys. Rev. B 38, 7749-7754; Bar-Nun, A., Kleinfeld, I., 1989. Icarus 80, 243-253] have shown that significant quantities of volatile gases can be trapped in a water ice matrix well above the temperature at which the pure volatile ice would sublime. For our Enceladus ice mixture, a composition of escaping gases similar to that detected by Cassini in the Enceladus plume can be generated by the sublimation of the H 2O:CO 2:CH 4:N 2 mixture at temperatures between 135 and 155 K, comparable to the high temperatures inferred from the CIRS measurements [Spencer, J.R., Pearl, J.C., Segura, M., Flasar, F.M., Mamoutkine, A., Romani, P., Buratti, B.J., Hendrix, A.R., Spilker, L.J., Lopes, R.M.C., 2006. Science 311, 1401-1405] of the Enceladus "tiger stripes." This suggests that the gas escape phenomena that we measure in our experiments are an important process contributing to the gases emitted from Enceladus. A similar experiment for ice deposited at 70 K shows that both the processes of volatile trapping and release are temperature dependent over the temperature range relevant to Enceladus.

Extenstional terrain formation in icy satellites: Implications for ocean-surface interaction

NASA Astrophysics Data System (ADS)

Howell, Samuel M.; Pappalardo, Robert T.

2017-10-01

Europa and Ganymede, Galilean satellites of Jupiter, exhibit geologic activity in their outer H2O ice shells that might convey material from water oceans within the satellites to their surfaces. Imagery from the Voyager and Galileo spacecraft reveal surfaces rich with tectonic deformation, including dilational bands on Europa and groove lanes on Ganymede. These features are generally attributed to the extension of a brittle ice lithosphere overlaying a possibly convecting ice asthenosphere. To explore band formation and interaction with interior oceans, we employ fully visco-elasto-plastic 2-D models of faulting and convection with complex, realistic pure ice rheologies. In these models, material entering from below is tracked and considered to be “fossilized ocean,” ocean material that has frozen into the ice shell and evolves through geologic time. We track the volume fraction of fossil ocean material in the ice shell as a function of depth, and the exposure of both fresh ice and fossil ocean material at the ice shell surface. To explore the range in extensional terrains, we vary ice shell thickness, fault localization, melting-temperature ice viscosity, and the presence of pre-existing weaknesses. Mechanisms which act to weaken the ice shell and thin the lithosphere (e.g. vigorous convection, thinner shells, pre-existing weaknesses) tend to plastically yield to form smooth bands at high strains, and are more likely to incorporate fossil ocean material in the ice shell and expose it at the surface. In contrast, lithosphere strengthened by rapid fault annealing or increased viscosity, for example, exhibits large-scale tectonic rifting at low strains superimposed over pre-existing terrains, and inhibits the incorporation and delivery of fossil ocean material to the surface. Thus, our results identify a spectrum of extensional terrain formation mechanisms as linked to lithospheric strength, rather than specific mechanisms that are unique to each type of band, and discuss where in this spectrum ocean material incorporated at the bottom of the ice shell may be exposed on the satellite surface.

Extensional terrain formation on Europa and Ganymede: Implications for ocean-surface interaction

NASA Astrophysics Data System (ADS)

Howell, S. M.; Pappalardo, R. T.

2017-12-01

Europa and Ganymede, Galilean satellites of Jupiter, exhibit geologic activity in their outer H2O ice shells that might convey material from water oceans within the satellites to their surfaces. Imagery from the Voyager and Galileo spacecraft reveal surfaces rich with tectonic deformation, including dilational bands on Europa and groove lanes on Ganymede. These features are generally attributed to the extension of a brittle ice lithosphere overlaying a possibly convecting ice asthenosphere. To explore band formation and interaction with interior oceans, we employ fully visco-elasto-plastic 2-D models of faulting and convection with complex, realistic pure ice rheologies. In these models, material entering from below is tracked and considered to be "fossilized ocean," ocean material that has frozen into the ice shell and evolves through geologic time. We track the volume fraction of fossil ocean material in the ice shell as a function of depth, and the exposure of both fresh ice and fossil ocean material at the ice shell surface. We vary ice shell thickness, fault localization, melting-temperature ice viscosity, and the presence of pre-existing weaknesses. Mechanisms which act to weaken the ice shell and thin the lithosphere (e.g. vigorous convection, thinner shells, pre-existing weaknesses) tend to plastically yield to form smooth bands at high strains, and are more likely to incorporate fossil ocean material in the ice shell and expose it at the surface. In contrast, lithosphere strengthened by rapid fault annealing or increased viscosity, for example, exhibits large-scale tectonic rifting at low strains superimposed over pre-existing terrains, and inhibits the incorporation and delivery of fossil ocean material to the surface. Thus, our results identify a spectrum of extensional terrain formation mechanisms as linked to lithospheric strength, rather than any specific mechanism being unique to each type of band, and where in this spectrum ocean material incorporated at the bottom of the ice shell may be exposed on the satellite surface.

Modeling the processing of interstellar ices by energetic particles

NASA Astrophysics Data System (ADS)

Kalvāns, J.; Shmeld, I.

2013-06-01

Context. Interstellar ice is the main form of metal species in dark molecular clouds. Experiments and observations have shown that the ice is significantly processed after the freeze-out of molecules onto grains. The processing is caused by cosmic-ray particles and cosmic-ray-induced UV photons. These transformations are included in current astrochemical models only to a very limited degree. Aims: We aim to establish a model of the "cold" chemistry in interstellar ices and to evaluate its general impact on the composition of interstellar ices. Methods: The ice was treated as consisting of two layers - the surface and the mantle (or subsurface) layer. Subsurface chemical processes are described with photodissociation of ice species and binary reactions on the surfaces of cavities inside the mantle. Hydrogen atoms and molecules can diffuse between the layers. We also included deuterium chemistry. Results: The modeling results show that the content of chemically bound H is reduced in subsurface molecules by about 30% on average. This promotes the formation of more hydrogen-poor species in the ice. The enrichment of ice molecules with deuterium is significantly reduced by the subsurface processes. On average, it follows the gas-phase atomic D/H abundance ratio, with a delay. The delay produced by the model is on the order of several Myr. Conclusions: The processing of ice may place new constraints on the production of deuterated species on grains. In a mantle with a two-layer structure the upper layer (CO) should be processed substantially more intensively than the lower layer (H2O). Chemical explosions in interstellar ice might not be an important process. They destroy the structure of the mantle, which forms over long timescales. Besides, ices may lack the high radical content needed for the explosions.

Radiolysis of Sulfuric Acid, Sulfuric Acid Monohydrate, and Sulfuric Acid Tetrahydrate and Its Relevance to Europa

NASA Technical Reports Server (NTRS)

Loeffler, M. J.; Hudson, R. L.; Moore, M. H.; Carlson, R. W.

2011-01-01

We report laboratory studies on the 0.8 MeV proton irradiation of ices composed of sulfuric acid (H2SO4), sulfuric acid monohydrate (H2SO4 H2O), and sulfuric acid tetrahydrate (H2SO4 4H2O) between 10 and 180 K. Using infrared spectroscopy, we identify the main radiation products as H2O, SO2, (S2O3)x, H3O+, HSO4(exp -), and SO4(exp 2-). At high radiation doses, we find that H2SO4 molecules are destroyed completely and that H2SO4 H2O is formed on subsequent warming. This hydrate is significantly more stable to radiolytic destruction than pure H2SO4, falling to an equilibrium relative abundance of 50% of its original value on prolonged irradiation. Unlike either pure H2SO4 or H2SO4 H2O, the loss of H2SO4 4H2O exhibits a strong temperature dependence, as the tetrahydrate is essentially unchanged at the highest irradiation temperatures and completely destroyed at the lowest ones, which we speculate is due to a combination of radiolytic destruction and amorphization. Furthermore, at the lower temperatures it is clear that irradiation causes the tetrahydrate spectrum to transition to one that closely resembles the monohydrate spectrum. Extrapolating our results to Europa s surface, we speculate that the variations in SO2 concentrations observed in the chaotic terrains are a result of radiation processing of lower hydration states of sulfuric acid and that the monohydrate will remain stable on the surface over geological times, while the tetrahydrate will remain stable in the warmer regions but be destroyed in the colder regions, unless it can be reformed by other processes, such as thermal reactions induced by diurnal cycling.

Radiolysis of Amino Acids in Outer Solar-System Ice Analogs

NASA Technical Reports Server (NTRS)

Gerakines, Perry A.; Hudson, Reggie L.

2011-01-01

Amino acids have been found in cometary dust particles and in the organic component of meteorites. These molecules, important for pre-biotic chemistry and for active biological systems, might be formed in cold planetary or interstellar environments and then delivered to H20-rich surfaces in the outer solar system. Many models for the availability of organic species on Earth and elsewhere depend on the ability of these molecules to survive in radiation-rich space environments. This poster presents results of O.8-MeV proton radiolysis of ice films at lS-140K. using infrared spectroscopy, the destruction rates of glycine, alanine, and phenylalanine have been determined for both pure films and those containing amino acids diluted in H2o. our results are discussed in terms of the survivability of these molecules in the icy surfaces present in the outer solar system and the possibility of their detection by instruments on board the New Horizons spacecraft

Laboratory Spectroscopy of Ices of Astrophysical Interest

NASA Technical Reports Server (NTRS)

Hudson, Reggie; Moore, M. H.

2011-01-01

Ongoing and future NASA and ESA astronomy missions need detailed information on the spectra of a variety of molecular ices to help establish the identity and abundances of molecules observed in astronomical data. Examples of condensed-phase molecules already detected on cold surfaces include H2O, CO, CO2, N2, NH3, CH4, SO2, O2, and O3. In addition, strong evidence exists for the solid-phase nitriles HCN, HC3N, and C2N2 in Titan's atmosphere. The wavelength region over which these identifications have been made is roughly 0.5 to 100 micron. Searches for additional features of complex carbon-containing species are in progress. Existing and future observations often impose special requirements on the information that comes from the laboratory. For example, the measurement of spectra, determination of integrated band strengths, and extraction of complex refractive indices of ices (and icy mixtures) in both amorphous and crystalline phases at relevant temperatures are all important tasks. In addition, the determination of the index of refraction of amorphous and crystalline ices in the visible region is essential for the extraction of infrared optical constants. Similarly, the measurement of spectra of ions and molecules embedded in relevant ices is important. This laboratory review will examine some of the existing experimental work and capabilities in these areas along with what more may be needed to meet current and future NASA and ESA planetary needs.

Ultraviolet Irradiation of Naphthalene in H2O Ice: Implications for Meteorites and Biogenesis

NASA Technical Reports Server (NTRS)

Bernstein, Max P.; Dworkin, Jason; Sandford, Scott A.; Allamandola, Louis J.; DeVincenzi, Donald L. (Technical Monitor)

2000-01-01

The polycyclic aromatic hydrocarbon (PAH) naphthalene was exposed to ultraviolet radiation in H2O ice under astrophysical conditions, and the products were analyzed using infrared spectroscopy and high performance liquid chromatography. As we found in our earlier studies on the photoprocessing of coronene in H2O ice, aromatic alcohols and ketones (quinones) were formed. The regiochemistry of the reactions is described and leads to specific predictions of the relative abundances of various oxidized naphthalenes that should exist in meteorites if interstellar ice photochemistry influenced their aromatic inventory. Since oxidized PAHs are present in carbon-rich meteorites and interplanetary dust particles (IDPs), and ubiquitous in and fundamental to biochemistry, the delivery of such extraterrestrial molecules to the early Earth may have played a role in the origin and evolution of life.

A model for the hydrologic and climatic behavior of water on Mars

NASA Technical Reports Server (NTRS)

Clifford, Stephen M.

1993-01-01

An analysis is carried out of the hydrologic response of a water-rich Mars to climate change and to the physical and thermal evolution of its crust, with particular attention given to the potential role of the subsurface transport, assuming that the current models of insolation-driven change describe reasonably the atmospheric leg of the planet's long-term hydrologic cycle. Among the items considered are the thermal and hydrologic properties of the crust, the potential distribution of ground ice and ground water, the stability and replenishment of equatorial ground ice, basal melting and the polar mass balance, the thermal evolution of the early cryosphere, the recharge of the valley networks and outflow, and several processes that are likely to drive the large-scale vertical and horizontal transport of H2O within the crust. The results lead to the conclusion that subsurface transport has likely played an important role in the geomorphic evolution of the Martian surface and the long-term cycling of H2O between the atmosphere, polar caps, and near-surface crust.

Observation of CO2 in Comet C/2012 K5 LINEAR

NASA Astrophysics Data System (ADS)

McKay, Adam; Kelley, Michael; DiSanti, Michael; Chanover, Nancy

2012-12-01

The study of cometary composition is important to understanding the formation and evolution of our solar system. Comets have undergone very little thermal evolution in their lifetimes, which results in their near pristine composition. The nucleus of a comet is very rarely detected directly. Instead, we observe the coma that surrounds the nucleus. Physical and chemical processes in the coma affect its composition, and therefore coma composition is not a direct representation of nuclear composition. An important trend is the observed variation of coma composition with heliocentric distance, most likely influenced by the volatility of the main surface ices, H2O, CO2, and CO. Infrared studies of these molecules are complicated by telluric features, so often daughter molecules of these species such as OH are observed instead. A potentially effective tracer for these primary ices is atomic oxygen in the coma. However, the relationship between these ices and atomic oxygen is only understood at a qualitative level. We propose to use Spitzer observations in IRAC's 4.5 micron band pass to observe the CO2 v3 band at 4.26 microns in comet C/2012 K5 LINEAR. These observations will be coordinated with observations of atomic oxygen obtained at Apache Point Observatory and observations of H2O at Keck. These near simultaneous observations of H2O, CO2, and atomic oxygen in a cometary coma will increase our understanding of the link between these primary ices and atomic oxygen. With a complete understanding of the relationship between atomic oxygen and the primary ices on the nucleus, observations of atomic oxygen can serve as a powerful proxy for the production of these primary volatiles and aid our understanding of the variation in coma composition as a function of heliocentric distance, and therefore the composition of the nucleus and how our solar system was formed.

Room-temperature NaI/H2O compression icing: solute-solute interactions.

PubMed

Zeng, Qingxin; Yao, Chuang; Wang, Kai; Sun, Chang Q; Zou, Bo

2017-10-11

In situ Raman spectroscopy revealed that transiting the concentrated NaI/H 2 O solutions to an ice VI phase and then into an ice VII phase at 298 K proceeds in a way different from that activated by the solute type. Unlike the solute type that raises both the critical pressures P C1 and P C2 , for the liquid-VI, the VI-VII transition simultaneously occurs in the Hofmeister series order: I > Br > Cl > F ∼ 0; concentration increase raises the P C1 faster than the P C2 that remains almost constant at higher NaI/H 2 O molecular number ratios. Concentration increase moves the P C1 along the liquid-VI phase boundary and it finally merges with P C2 at the triple-phase junction featured at 350 K and 3.05 GPa. The highly-deformed H-O bond is less sensitive to the concentration because of the involvement of anion-anion repulsion that weakens the electric field in the hydration shells. Observations confirm that the salt solvation lengthens the O:H nonbond and softens its phonon but relaxes the H-O bond contrastingly. Compression, however, has the opposite effect from that of salt solvation. Therefore, compression recovers the polarization-deformed O:H-O bond first and then proceeds to the phase transitions. The anion-anion interaction discriminates the effect of NaI/H 2 O concentration from that of the solute type at an identical concentration on the phase transitions.

TES mapping of Mars' north seasonal cap

USGS Publications Warehouse

Kieffer, H.H.; Titus, T.N.

2001-01-01

The Mars Global Surveyor thermal emission spectrometer has made observations of Mars' north polar region for nearly a full martian year. Measurements of bolometric emission and reflectance, as well as brightness temperatures in specific bands synthesized from thermal radiance spectra, are used to track the behavior of surface and atmospheric temperatures, the distribution of condensed CO2 and H2O, and the occurrence of dust storms. CO2 grain size in the polar night is variable in space and time, and is influenced by atmospheric conditions. Some specific locations display concentration of H2O frost and indicate the presence of long-term water-ice near the surface. Annual budgets of solid CO2 range up to 1500 kg m-2; preliminary analysis suggests significant transport of energy into latitudes near 70?? N during the polar night. ?? 2001 Elsevier Science.

The condensation and vaporization behavior of ices containing SO2, H2S, and CO2 - Implications for Io

NASA Astrophysics Data System (ADS)

Sandford, Scott A.; Allamandola, Louis J.

1993-12-01

The present compilation of measurements of the physical and IR spectral properties of ices whose molecular compositions are relevant to the case of Io encompasses ice systems containing SO2, H2S, and CO2. Surface-binding energies used to calculate the residence times of molecules on a surface as a function of temperature furnish crucially important parameters for models attending to the transport of such molecules to the surface of Io. The values thus derived show that SO2 frosts anneal rapidly.

Compositional Trends on the Large Moons of Uranus: Evidence for System-Wide Modification

NASA Astrophysics Data System (ADS)

Cartwright, R.; Emery, J. P.

2017-12-01

Previous near-infrared (NIR) observations centered over southern latitudes ( 5 - 30°S) of the classical Uranian moons have detected H2Oww ice bands, mixed with a spectrally neutral and low albedo constituent. The strengths of the detected H2O bands are greater on the leading hemispheres of these moons compared to their trailing hemispheres, with a reduction in leading/trailing H2O band strengths with distance from Uranus. CO2 ice bands have been detected in spectra collected over the trailing hemispheres of the classical Uranian satellites, with stronger CO2 bands on the moons closest to Uranus. Our preferred hypotheses to explain the hemispherical and planetocentric trends in the distribution of CO2 and the strength of detected H2O bands are: bombardment by magnetospherically-embedded charged particles, primarily on the trailing hemispheres of these moons, and bombardment by dust particles, primarily on their leading hemispheres. To test these complementary hypotheses, we are constraining the distribution and spectral characteristics of surface constituents on the currently observable northern hemispheres (sub-observer lat. 20 - 35°N) of these moons with new NIR observations. Analysis of northern hemisphere data shows that CO2 is present on their trailing hemispheres, and H2O bands are strongest on their leading hemispheres, in agreement with the southern hemisphere data. This longitudinal distribution of constituents supports our preferred hypotheses. Tantalizing mysteries regarding the distribution of constituents on these moons remain. There has been no detection of CO2 on Miranda, and H2O bands are subtly stronger on its trailing hemisphere compared to its leading hemisphere, counter to the hemispherical trends displayed on the other classical satellites. Some Uranian satellite spectra display a subtle absorption feature near 2.2 µm, which could result from the presence of NH3-hydrates on these moons. The presence of this volatile constituent could indicate recent cryovolcanic emplacement and/or recent exposure of NH3-hydrates via mass wasting, tectonism, or impact events. We will present work related to our goals of constraining the processes modifying the surfaces of the classical Uranian moons.

Hydrocarbon Emission Rings in Protoplanetary Disks Induced by Dust Evolution

NASA Astrophysics Data System (ADS)

Bergin, Edwin A.; Du, Fujun; Cleeves, L. Ilsedore; Blake, G. A.; Schwarz, K.; Visser, R.; Zhang, K.

2016-11-01

We report observations of resolved C2H emission rings within the gas-rich protoplanetary disks of TW Hya and DM Tau using the Atacama Large Millimeter Array. In each case the emission ring is found to arise at the edge of the observable disk of millimeter-sized grains (pebbles) traced by submillimeter-wave continuum emission. In addition, we detect a C3H2 emission ring with an identical spatial distribution to C2H in the TW Hya disk. This suggests that these are hydrocarbon rings (I.e., not limited to C2H). Using a detailed thermo-chemical model we show that reproducing the emission from C2H requires a strong UV field and C/O > 1 in the upper disk atmosphere and outer disk, beyond the edge of the pebble disk. This naturally arises in a disk where the ice-coated dust mass is spatially stratified due to the combined effects of coagulation, gravitational settling and drift. This stratification causes the disk surface and outer disk to have a greater permeability to UV photons. Furthermore the concentration of ices that transport key volatile carriers of oxygen and carbon in the midplane, along with photochemical erosion of CO, leads to an elemental C/O ratio that exceeds unity in the UV-dominated disk. Thus the motions of the grains, and not the gas, lead to a rich hydrocarbon chemistry in disk surface layers and in the outer disk midplane.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bergin, Edwin A.; Du, Fujun; Schwarz, K.

We report observations of resolved C{sub 2}H emission rings within the gas-rich protoplanetary disks of TW Hya and DM Tau using the Atacama Large Millimeter Array. In each case the emission ring is found to arise at the edge of the observable disk of millimeter-sized grains (pebbles) traced by submillimeter-wave continuum emission. In addition, we detect a C{sub 3}H{sub 2} emission ring with an identical spatial distribution to C{sub 2}H in the TW Hya disk. This suggests that these are hydrocarbon rings (i.e., not limited to C{sub 2}H). Using a detailed thermo-chemical model we show that reproducing the emission frommore » C{sub 2}H requires a strong UV field and C/O > 1 in the upper disk atmosphere and outer disk, beyond the edge of the pebble disk. This naturally arises in a disk where the ice-coated dust mass is spatially stratified due to the combined effects of coagulation, gravitational settling and drift. This stratification causes the disk surface and outer disk to have a greater permeability to UV photons. Furthermore the concentration of ices that transport key volatile carriers of oxygen and carbon in the midplane, along with photochemical erosion of CO, leads to an elemental C/O ratio that exceeds unity in the UV-dominated disk. Thus the motions of the grains, and not the gas, lead to a rich hydrocarbon chemistry in disk surface layers and in the outer disk midplane.« less

Molecular dynamics simulation of water at mineral surfaces: Structure, dynamics, energetics and hydrogen bonding

NASA Astrophysics Data System (ADS)

Kalinichev, A. G.; Wang, J.; Kirkpatrick, R.

2006-05-01

Fundamental molecular-level understanding of the properties of aqueous mineral interfaces is of great importance for many geochemical and environmental systems. Interaction between water and mineral surfaces substantially affects the properties of both phases, including the reactivity and functionality of the substrate surface, and the structure, dynamics, and energetics of the near surface aqueous phase. Experimental studies of interfacial water structure and dynamics using surface-sensitive techniques such as sum-frequency vibrational spectroscopy or X-ray and neutron reflectivity are not always possible for many practically important substrates, and their results often require interpretation concerning the atomistic mechanisms responsible for the observed behavior. Molecular computer simulations can provide new insight into the underlying molecular- level relationships between the inorganic substrate structure and composition and the structure, ordering, and dynamics of interfacial water. We have performed a series of molecular dynamics (MD) computer simulations of aqueous interfaces with several silicates (quartz, muscovite, and talc) and hydroxides (brucite, portlandite, gibbsite, Ca/Al and Mg/Al double hydroxides) to quantify the effects of the substrate mineral structure and composition on the structural, transport, and thermodynamic properties of water on these mineral surfaces. Due to the prevalent effects of the development of well-interconnected H-bonding networks across the mineral- water interfaces, all the hydroxide surfaces (including a fully hydroxylated quartz surface) show very similar H2O density profiles perpendicular to the interface. However, the predominant orientations of the interfacial H2O molecules and their detailed 2-dimensional near-surface structure and dynamics parallel to the interface are quite different reflecting the differences in the substrate structural charge distribution and the density and orientations of the surface OH groups. The H2O density profiles and other structural and dynamic characteristics of water at the two siloxane surfaces are very different from each other and from the hydroxide surfaces, since the muscovite surface is negatively charged and hydrophilic, while the talc surface is electrostatically neutral and hydrophobic. In general, at hydrophilic neutral surfaces both donating and accepting H-bonds from the H2O molecules are contributing to the development of the interfacial H-bond network, whereas at hydrophilic but charged surfaces only accepting or donating H-bonds with H2O molecules are possible. At the hydrophobic talc surface H-bonds among H2O molecules dominate the interfacial H-bond network and the water-surface interactions are very weak. The first water layer at all substrates is well ordered parallel to the surface, reflecting substrate crystal structures and indicating the reduced translational and orientational mobility of interfacial H2O molecules. At longer time scale (~100ps) their dynamics can be decomposed into a slow, virtually frozen, regime due to the substrate- bound H2O and a faster regime of almost free water reflecting the dynamics far from the surface. At shorter times (>10ps) the two dynamical regimes are superimposed. The much higher ordering of interfacial water (compared to bulk liquid) can not be adequately described as simply "ice-like". To some extent, it rather resembles the behavior of supercooled water.

Aqueous origins of bright salt deposits on Ceres

NASA Astrophysics Data System (ADS)

Zolotov, Mikhail Yu.

2017-11-01

Bright materials have been reported in association with impact craters on Ceres. The abundant Na2CO3 and some ammonium salts, NH4HCO3 and/or NH4Cl, were detected in bright deposits within Occator crater with Dawn near infrared spectroscopy. The composition and appearance of the salts suggest their aqueous mobilization and emplacement after formation of the crater. Here we consider origins of the bright deposits through calculation of speciation in the H-C-N-O-Na-Cl water-salt type system constrained by the mass balance of observed salts. Calculations of chemical equilibria show that initial solutions had the pH of ∼10. The temperature and salinity of solutions could have not exceeded ∼273 K and ∼100 g per kg H2O, respectively. Freezing models reveal an early precipitation of Na2CO3·10H2O followed by minor NaHCO3. Ammonium salts precipitate near eutectic from brines enriched in NH4+, Cl- and Na+. A late-stage precipitation of NaCl·2H2O is modeled for solution compositions with added NaCl. Calculated eutectics are above 247 K. The apparently unabundant ammonium and chloride salts in Occator's deposits imply a rapid emplacement without a compositional evolution of solution. Salty ice grains could have deposited from post-impact ballistic plumes formed through low-pressure boiling of subsurface solutions. Hydrated and ammonium salts are unstable at maximum temperatures of Ceres' surface and could decompose through space weathering. Occator's ice-free salt deposits formed through a post-depositional sublimation of ice followed by dehydration of Na2CO3·10H2O and NaHCO3 to Na2CO3. In other regions, excavated and exposed bright materials could be salts initially deposited from plumes and accumulated at depth via post-impact boiling. The lack of detection of sulfates and an elevated carbonate/chloride ratio in Ceres' materials suggest an involvement of compounds abundant in the outer solar system.

Drivers of inorganic carbon dynamics in first-year sea ice: A model study

NASA Astrophysics Data System (ADS)

Moreau, Sébastien; Vancoppenolle, Martin; Delille, Bruno; Tison, Jean-Louis; Zhou, Jiayun; Kotovitch, Marie; Thomas, David N.; Geilfus, Nicolas-Xavier; Goosse, Hugues

2015-01-01

Sea ice is an active source or a sink for carbon dioxide (CO2), although to what extent is not clear. Here, we analyze CO2 dynamics within sea ice using a one-dimensional halothermodynamic sea ice model including gas physics and carbon biogeochemistry. The ice-ocean fluxes, and vertical transport, of total dissolved inorganic carbon (DIC) and total alkalinity (TA) are represented using fluid transport equations. Carbonate chemistry, the consumption, and release of CO2 by primary production and respiration, the precipitation and dissolution of ikaite (CaCO3·6H2O) and ice-air CO2 fluxes, are also included. The model is evaluated using observations from a 6 month field study at Point Barrow, Alaska, and an ice-tank experiment. At Barrow, results show that the DIC budget is mainly driven by physical processes, wheras brine-air CO2 fluxes, ikaite formation, and net primary production, are secondary factors. In terms of ice-atmosphere CO2 exchanges, sea ice is a net CO2 source and sink in winter and summer, respectively. The formulation of the ice-atmosphere CO2 flux impacts the simulated near-surface CO2 partial pressure (pCO2), but not the DIC budget. Because the simulated ice-atmosphere CO2 fluxes are limited by DIC stocks, and therefore <2 mmol m-2 d-1, we argue that the observed much larger CO2 fluxes from eddy covariance retrievals cannot be explained by a sea ice direct source and must involve other processes or other sources of CO2. Finally, the simulations suggest that near-surface TA/DIC ratios of ˜2, sometimes used as an indicator of calcification, would rather suggest outgassing.

Drivers of inorganic carbon dynamics in first-year sea ice: A model study

NASA Astrophysics Data System (ADS)

Moreau, Sébastien; Vancoppenolle, Martin; Delille, Bruno; Tison, Jean-Louis; Zhou, Jiayun; Kotovich, Marie; Thomas, David; Geilfus, Nicolas-Xavier; Goosse, Hugues

2015-04-01

Sea ice is an active source or a sink for carbon dioxide (CO2), although to what extent is not clear. Here, we analyze CO2 dynamics within sea ice using a one-dimensional halo-thermodynamic sea ice model including gas physics and carbon biogeochemistry. The ice-ocean fluxes, and vertical transport, of total dissolved inorganic carbon (DIC) and total alkalinity (TA) are represented using fluid transport equations. Carbonate chemistry, the consumption and release of CO2 by primary production and respiration, the precipitation and dissolution of ikaite (CaCO3•6H2O) and ice-air CO2 fluxes, are also included. The model is evaluated using observations from a 6-month field study at Point Barrow, Alaska and an ice-tank experiment. At Barrow, results show that the DIC budget is mainly driven by physical processes, wheras brine-air CO2 fluxes, ikaite formation, and net primary production, are secondary factors. In terms of ice-atmosphere CO2 exchanges, sea ice is a net CO2 source and sink in winter and summer, respectively. The formulation of the ice-atmosphere CO2 flux impacts the simulated near-surface CO2 partial pressure (pCO2), but not the DIC budget. Because the simulated ice-atmosphere CO2 fluxes are limited by DIC stocks, and therefore < 2 mmol m-2 day-1, we argue that the observed much larger CO2 fluxes from eddy covariance retrievals cannot be explained by a sea ice direct source and must involve other processes or other sources of CO2. Finally, the simulations suggest that near surface TA/DIC ratios of ~2, sometimes used as an indicator of calcification, would rather suggest outgassing.

Evidence of amino acid precursors: C-N bond coupling in simulated interstellar CO2/NH3 ices

NASA Astrophysics Data System (ADS)

Esmaili, Sasan

2015-08-01

Low energy secondary electrons are abundantly produced in astrophysical or planetary ices by the numerous ionizing radiation fields typically encountered in space environments and may thus play a role in the radiation processing of such ices [1]. One approach to determine their chemical effect is to irradiate nanometer thick molecular solids of simple molecular constituents, with energy selected electron beams and to monitor changes in film chemistry with the surface analytical techniques [2].Of particular interest is the formation of HCN, which is a signature of dense gases in interstellar clouds, and is ubiquitous in the ISM. Moreover, the chemistry of HCN radiolysis products such as CN- may be essential to understand of the formation of amino acids [3] and purine DNA bases. Here we present new results on the irradiation of multilayer films of CO2 and NH3 with 70 eV electrons, leading to CN bond formations. The electron stimulated desorption (ESD) yields of cations and anions are recorded as a function of electron fluence. The prompt desorption of cationic reaction/scattering products [4], is observed at low fluence (~4x1013 electrons/cm2). Detected ions include C2+, C2O2+, C2O+, CO3+, C2O3+ or CO4+ from pure CO2, and N+, NH+, NH2+, NH3+, NH4+, N2+, N2H+ from pure NH3, and NO+, NOH+ from CO2/NH3 mixtures. Most saliently, increasing signals of negative ion products desorbing during prolonged irradiation of CO2/NH3 films included C2-, C2H-, C2H2-, as well as CN-, HCN- and H2CN-. The identification of particular product ions was accomplished by using 13CO2 and 15NH3 isotopes. The chemistry induced by electrons in pure films of CO2 and NH3 and mixtures with composition ratios (3:1), (1:1), and (1:3), was also studied by X-ray photoelectron spectroscopy (XPS). Irradiation of CO2/NH3 mixed films at 22 K produces species containing the following bonds/functional groups identified by XPS: C=O, O-H, C-C, C-O, C=N and N=O. (This work has been funded by NSERC).

Effect of pressure on infrared spectra of ice 7

NASA Technical Reports Server (NTRS)

Holzapfel, W. B.; Seiler, B.; Nicol, M.

1983-01-01

The effect of pressure on the infrared spectra of H2O and D2O ice VII was studied at room temperature and pressures between 2 and 15 GPa with a Fourier transform infrared spectrometer and a diamond anvil high pressure cell. Two librational modes, one bending mode, and various overtone bands are well resolved. The stretching modes, nu sub 1 and nu sub 3 are poorly resolved due to overlap with diamond window absorption. Differences between the spectra of H2O and D2O are discussed.

Unraveling the 10 micron "silicate" feature of protostars: the detection of frozen interstellar ammonia

NASA Technical Reports Server (NTRS)

Lacy, J. H.; Faraji, H.; Sandford, S. A.; Allamandola, L. J.

1998-01-01

We present infrared spectra of four embedded protostars in the 750-1230 cm-1 (13.3-8.1 microns) range. For NGC 7538 IRS 9, a new band is reported at 1110 cm-1 (9.01 microns, and several others may be present near 785, 820, 900, 1030, and 1075 cm-1 (12.7, 12.2, 11.1, 9.71, and 9.30 microns). The band 1110 cm-1 is attributed to frozen NH3. Its position and width imply that the NH3 is frozen in a polar, H2O-rich interstellar ice component. The NH3/H2O ice ratio inferred for NGC 7538 IRS 9 is 0.1, making NH3 as important a component as CH3OH and CO2 in the polar ices along this line of sight. At these concentrations, hydrogen bonding between the NH3 and H2O can account for much of the enigmatic low-frequency wing on the 3240 cm-1 (3.09 microns) H2O interstellar ice band. The strength of the implied NH3 deformation fundamental at 1624 cm-1 (6.158 microns) can also account for the absorption at this position reported by ISO.

Spectroscopy from Space

NASA Astrophysics Data System (ADS)

Clark, R. N.; Swayze, G. A.; Carlson, R.; Grundy, W.; Noll, K.

2014-01-01

This chapter reviews detection of materials on solid and liquid (lakes and ocean) surfaces in the solar system using ultraviolet to infrared spectroscopy from space, or near space (high altitude aircraft on the Earth), or in the case of remote objects, earth-based and earth-orbiting telescopes. Point spectrometers and imaging spectrometers have been probing the surfaces of our solar system for decades. Spacecraft carrying imaging spectrometers are currently in orbit around Mercury, Venus, Earth, Mars, and Saturn, and systems have recently visited Jupiter, comets, asteroids, and one spectrometer-carrying spacecraft is on its way to Pluto. Together these systems are providing a wealth of data that will enable a better understanding of the composition of condensed matter bodies in the solar system. Minerals, ices, liquids, and other materials have been detected and mapped on the Earth and all planets and/or their satellites where the surface can be observed from space, with the exception of Venus whose thick atmosphere limits surface observation. Basaltic minerals (e.g., pyroxene and olivine) have been detected with spectroscopy on the Earth, Moon, Mars and some asteroids. The greatest mineralogic diversity seen from space is observed on the Earth and Mars. The Earth, with oceans, active tectonic and hydrologic cycles, and biological processes, displays the greatest material diversity including the detection of amorphous and crystalline inorganic materials, organic compounds, water and water ice. Water ice is a very common mineral throughout the Solar System and has been unambiguously detected or inferred in every planet and/or their moon(s) where good spectroscopic data has been obtained. In addition to water ice, other molecular solids have been observed in the solar system using spectroscopic methods. Solid carbon dioxide is found on all systems beyond the Earth except Pluto, although CO2 sometimes appears to be trapped in other solids rather than as an ice on some objects. The largest deposits of carbon dioxide ice are found on Mars. Sulfur dioxide ice is found in the Jupiter system. Nitrogen and methane ices are common beyond the Uranian system. Saturn's moon Titan probably has the most complex active extra-terrestrial surface chemistry involving organic compounds. Some of the observed or inferred compounds include ices of benzene (C6H6), cyanoacetylene (HC3N), toluene (C7H8), cyanogen (C2N2), acetonitrile (CH3CN), water (H2O), carbon dioxide (CO2), and ammonia (NH3). Confirming compounds on Titan is hampered by its thick smoggy atmosphere, where in relative terms the atmospheric interferences that hamper surface characterization lie between that of Venus and Earth. In this chapter we exclude discussion of the planets Jupiter, Saturn, Uranus, and Neptune because their thick atmospheres preclude observing the surface, even if surfaces exist. However, we do discuss spectroscopic observations on a number of the extra-terrestrial satellite bodies. Ammonia was predicted on many icy moons but is notably absent among the definitively detected ices with possible exceptions on Charon and possible trace amounts on some of the Saturnian satellites. Comets, storehouses of many compounds that could exist as ices in their nuclei, have only had small amounts of water ice definitively detected on their surfaces from spectroscopy. Only two asteroids have had a direct detection of surface water ice, although its presence can be inferred in others.

Potassium alum and aluminum sulfate micro-inclusions in polar ice from Dome Fuji, East Antarctica

NASA Astrophysics Data System (ADS)

Ohno, Hiroshi; Iizuka, Yoshinori; Horikawa, Shinichiro; Sakurai, Toshimitsu; Hondoh, Takeo; Motoyama, Hideaki

2014-03-01

Water-soluble trace constituents affect the physicochemical properties of polar ice. Their structural distribution provides important insights into the formation history of ice and inclusions. We report the first finding of KAl(SO4)2·12H2O (potassium alum) and Al2(SO4)3·nH2O (aluminum sulfate) micro-inclusions in the Dome Fuji ice core, East Antartica, using a micro-Raman technique. Eutectic temperatures of these water-soluble species determined using thermal analysis were -0.4 °C for potassium alum and -8.0 °C for aluminum sulfate. Although the formation process of the aluminum-bearing sulfates remains unclear, the occurrence of these salts largely depends on ice depth.

Mid- and far-infrared spectroscopic studies of the influence of temperature, ultraviolet photolysis and ion irradiation on cosmic-type ices.

PubMed

Moore, M H; Hudson, R L; Gerakines, P A

2001-03-15

Infrared (IR) studies of laboratory ices can provide information on the evolution of cosmic-type ices as a function of different simulated space environments involving thermal, ultraviolet (UV), or ion processing. Laboratory radiation experiments can lead to the formation of complex organic molecules. However, because of our lack of knowledge about UV photon and ion fluxes, and exposure lifetimes, it is not certain how well our simulations represent space conditions. Appropriate laboratory experiments are also limited by the absence of knowledge about the composition, density, and temperature of ices in different regions of space. Our current understanding of expected doses due to UV photons and cosmic rays is summarized here, along with an inventory of condensed-phase molecules identified on outer solar system surfaces, comets and interstellar grains. Far-IR spectra of thermally cycled H2O are discussed since these results reflect the dramatic difference between the amorphous and crystalline phases of H2O ice, the most dominant condensed-phase molecule in cosmic ices. A comparison of mid-IR spectra of products in proton-irradiated and UV-photolyzed ices shows that few differences are observed for these two forms of processing for the simple binary mixtures studied to date. IR identification of radiation products and experiments to determine production rates of new molecules in ices during processing are discussed. A new technique for measuring intrinsic IR band strengths of several unstable molecules is presented. An example of our laboratory results applied to Europa observations is included.

The radiation stability of glycine in solid CO2 - In situ laboratory measurements with applications to Mars

NASA Astrophysics Data System (ADS)

Gerakines, Perry A.; Hudson, Reggie L.

2015-05-01

The detection of biologically important, organic molecules on Mars is an important goal that may soon be reached. However, the current small number of organic detections at the martian surface may be due to the harsh UV and radiation conditions there. It seems likely that a successful search will require probing the subsurface of Mars, where penetrating cosmic rays and solar energetic particles dominate the radiation environment, with an influence that weakens with depth. Toward the goal of understanding the survival of organic molecules in cold radiation-rich environments on Mars, we present new kinetics data on the radiolytic destruction of glycine diluted in frozen carbon dioxide. Rate constants were measured in situ with infrared spectroscopy, without additional sample manipulation, for irradiations at 25, 50, and 75 K with 0.8-MeV protons. The resulting half-lives for glycine in CO2-ice are compared to previous results for glycine in H2O-ice and show that glycine in CO2-ice is much less stable in a radiation environment, with destruction rate constants ∼20-40 times higher than glycine in H2O-ice. Extrapolation of these results to conditions in the martian subsurface results in half-lives estimated to be less than 100-200 Myr even at depths of a few meters.

H2O2 Synthesis Induced by Irradiation of H2O with Energetic H(+) and Ar(+) Ions at Various Temperatures

NASA Technical Reports Server (NTRS)

Baragiola, R. A.; Loeffler, M. J.; Raut, U.; Vidal, R. A.; Carlson, R. W.

2004-01-01

The detection of H2O2 on Jupiter's icy satellite Europa by the Galileo NIMS instrument presented a strong evidence for the importance of radiation effects on icy surfaces. A few experiments have investigated whether solar flux of protons incident on Europa ice could cause a significant if any H2O2 production. These published results differ as to whether H2O2 can be formed by ions impacting water at temperatures near 80 K, which are appropriate to Europa. This discrepancy may be a result of the use of different incident ion energies, different vacuum conditions, or different ways of processing the data. The latter possibility comes about from the difficulty of identifying the 3.5 m peroxide OH band on the long wavelength wing of the much stronger water 3.1 m band. The problem is aggravated by using straight line baselines to represent the water OH band with a curvature, in the region of the peroxide band, that increases with temperature. To overcome this problem, we use polynomial baselines that provide good fits to the water band and its derivative.

Alteration of the UV-visible reflectance spectra of H2O ice by ion bombardment

NASA Technical Reports Server (NTRS)

Sack, N. J.; Boring, J. W.; Johnson, R. E.; Baragiola, R. A.; Shi, M.

1991-01-01

Satellite in the Jovian and Saturnian system exhibit differences in reflectivity between their 'leading' and 'trailing' surfaces which can affect the local vapor pressure. Since these differences are thought to be due to differences in the flux of bombarding magnetospheric ions, the influence of ion impact on the UV-visible reflectance of water ice surfaces (20-90 K) by keV ion bombardment was studied. An observed decrease in reflectance in the UV is attributed to rearrangement processes that affect the physical microstructure and surface 'roughness'. The ratio in reflectance of bombarded to freshly deposited films is compared to the ratio of the reflectance of the leading and trailing hemispheres for Europa and Ganymede.

Deuterium enrichment of polycyclic aromatic hydrocarbons by photochemically induced exchange with deuterium-rich cosmic ices

NASA Technical Reports Server (NTRS)

Sandford, S. A.; Bernstein, M. P.; Allamandola, L. J.; Gillette, J. S.; Zare, R. N.

2000-01-01

The polycyclic aromatic hydrocarbon (PAH) coronene (C24H12) frozen in D2O ice in a ratio of less than 1 part in 500 rapidly exchanges its hydrogen atoms with the deuterium in the ice at interstellar temperatures and pressures when exposed to ultraviolet radiation. Exchange occurs via three different chemical processes: D atom addition, D atom exchange at oxidized edge sites, and D atom exchange at aromatic edge sites. Observed exchange rates for coronene (C24H12)-D2O and d12-coronene (C24D12)-H2O isotopic substitution experiments show that PAHs in interstellar ices could easily attain the D/H levels observed in meteorites. These results may have important consequences for the abundance of deuterium observed in aromatic materials in the interstellar medium and in meteorites. These exchange mechanisms produce deuteration in characteristic molecular locations on the PAHs that may distinguish them from previously postulated processes for D enrichment of PAHs.

IR Spectroscopy and Photo-Chemistry of Extraterrestrial Ices

NASA Technical Reports Server (NTRS)

Bernstein, Max P.; Mastrapa, Rachel; Elsila, Jamie; Sandford, Scott

2005-01-01

Dense molecular clouds from which planetary systems form and the outer Solar System are both cold environments dominated by ices. Infrared (IR) spectroscopy is used to probe these ices, but the IR absorptions of molecules depend on the conditions. As a result appropriate lab data is needed to correctly fit spectra of extraterrestrial ices. Such fits have shown that most of these ices are composed primarily of H2O, but also contain 1-10 percent of other simple molecules such as CO2, CO, CH4, & NH3;. We shall present near IR spectra of ice mixtures of relevance to icy outer Solar System bodies and show that they still hold surprises, such as the Cheshire cat-like CO2 (2v3) overtone near 2.134 micrometers (4685 cm-1) that is absent from spectra of pure CO2 but present in H2O-CO2 mixtures.

Infrared Spectra and Thermodynamic Properties of Co2/Methanol Ices

NASA Astrophysics Data System (ADS)

Maté, Belén; Gálvez, Óscar; Herrero, Víctor J.; Escribano, Rafael

2009-01-01

Ices of mixtures of carbon dioxide and methanol have been studied in a range of temperatures relevant for star-forming regions, comets, polar caps of planets and satellites, and other solar system bodies. We have performed temperature-programmed desorption measurements and recorded IR spectra of various types of samples. The presence of two slightly different structures of CO2 is manifest. A distorted CO2 structure is characterized by bandshifts between 5 cm-1 (ν3) and 10 cm-1 (ν2) with respect to normal CO2. If the samples are heated above 130 K, the distorted CO2 sublimates and only the normal structure remains. The latter can stay trapped until the sublimation of crystalline methanol (150 K). The desorption energy (E d ~ 20 kJ mol-1) of CO2 from methanol ice, and the specific adsorption surface area (6 m2 g-1) of amorphous CH3OH ice, have been determined. CO2 does not penetrate into crystalline ice. Whereas the desorption energy is similar to that of CO2/H2O samples, the specific surface of methanol is much smaller than that of amorphous solid water (ASW). The interaction of CO2 molecules with water and methanol is similar but ices of CH3OH are much less porous than ASW. The inclusion of CO2 into previously formed ices containing these two species would take place preferentially into ASW. However, in processes of simultaneous deposition, methanol ice can admit a larger amount of CO2 than water ice. CO2/CH3OH ices formed by simultaneous deposition admit two orders of magnitude more CO2 than sequentially deposited ices. These findings can have direct relevance to the interpretation of observations from protostellar environments (e.g., RAFGL7009S) and comet nuclei.

Ikaite crystal distribution in winter sea ice and implications for CO2 system dynamics

NASA Astrophysics Data System (ADS)

Rysgaard, S.; Søgaard, D. H.; Cooper, M.; Pućko, M.; Lennert, K.; Papakyriakou, T. N.; Wang, F.; Geilfus, N. X.; Glud, R. N.; Ehn, J.; McGinnis, D. F.; Attard, K.; Sievers, J.; Deming, J. W.; Barber, D.

2013-04-01

The precipitation of ikaite (CaCO3 ⋅ 6H2O) in polar sea ice is critical to the efficiency of the sea ice-driven carbon pump and potentially important to the global carbon cycle, yet the spatial and temporal occurrence of ikaite within the ice is poorly known. We report unique observations of ikaite in unmelted ice and vertical profiles of ikaite abundance and concentration in sea ice for the crucial season of winter. Ice was examined from two locations: a 1 m thick land-fast ice site and a 0.3 m thick polynya site, both in the Young Sound area (74° N, 20° W) of NE Greenland. Ikaite crystals, ranging in size from a few μm to 700 μm, were observed to concentrate in the interstices between the ice platelets in both granular and columnar sea ice. In vertical sea ice profiles from both locations, ikaite concentration determined from image analysis, decreased with depth from surface-ice values of 700-900 μmol kg-1 ice (~25 × 106 crystals kg-1) to values of 100-200 μmol kg-1 ice (1-7 × 106 crystals kg-1) near the sea ice-water interface, all of which are much higher (4-10 times) than those reported in the few previous studies. Direct measurements of total alkalinity (TA) in surface layers fell within the same range as ikaite concentration, whereas TA concentrations in the lower half of the sea ice were twice as high. This depth-related discrepancy suggests interior ice processes where ikaite crystals form in surface sea ice layers and partly dissolve in layers below. Melting of sea ice and dissolution of observed concentrations of ikaite would result in meltwater with a pCO2 of <15 μatm. This value is far below atmospheric values of 390 μatm and surface water concentrations of 315 μatm. Hence, the meltwater increases the potential for seawater uptake of CO2.

Solidification and microstructures of binary ice-I/hydrate eutectic aggregates

USGS Publications Warehouse

McCarthy, C.; Cooper, R.F.; Kirby, S.H.; Rieck, K.D.; Stern, L.A.

2007-01-01

The microstructures of two-phase binary aggregates of ice-I + salt-hydrate, prepared by eutectic solidification, have been characterized by cryogenic scanning electron microscopy (CSEM). The specific binary systems studied were H2O-Na2SO4, H2O-MgSO4, H2O-NaCl, and H2O-H2SO4; these were selected based on their potential application to the study of tectonics on the Jovian moon Europa. Homogeneous liquid solutions of eutectic compositions were undercooled modestly (??T - 1-5 ??C); similarly cooled crystalline seeds of the same composition were added to circumvent the thermodynamic barrier to nucleation and to control eutectic growth under (approximately) isothermal conditions. CSEM revealed classic eutectic solidification microstructures with the hydrate phase forming continuous lamellae, discontinuous lamellae, or forming the matrix around rods of ice-I, depending on the volume fractions of the phases and their entropy of dissolving and forming a homogeneous aqueous solution. We quantify aspects of the solidification behavior and microstructures for each system and, with these data articulate anticipated effects of the microstructure on the mechanical responses of the materials.

Kinetic Monte Carlo simulations of water ice porosity: extrapolations of deposition parameters from the laboratory to interstellar space.

PubMed

Clements, Aspen R; Berk, Brandon; Cooke, Ilsa R; Garrod, Robin T

2018-02-21

Dust grains in cold, dense interstellar clouds build up appreciable ice mantles through the accretion and subsequent surface chemistry of atoms and molecules from the gas. These mantles, of thicknesses on the order of 100 monolayers, are primarily composed of H 2 O, CO, and CO 2 . Laboratory experiments using interstellar ice analogues have shown that porosity could be present and can facilitate diffusion of molecules along the inner pore surfaces. However, the movement of molecules within and upon the ice is poorly described by current chemical kinetics models, making it difficult either to reproduce the formation of experimental porous ice structures or to extrapolate generalized laboratory results to interstellar conditions. Here we use the off-lattice Monte Carlo kinetics model MIMICK to investigate the effects that various deposition parameters have on laboratory ice structures. The model treats molecules as isotropic spheres of a uniform size, using a Lennard-Jones potential. We reproduce experimental trends in the density of amorphous solid water (ASW) for varied deposition angle, rate and surface temperature; ice density decreases when the incident angle or deposition rate is increased, while increasing temperature results in a more-compact water ice. The models indicate that the density behaviour at higher temperatures (≥80 K) is dependent on molecular rearrangement resulting from thermal diffusion. To reproduce trends at lower temperatures, it is necessary to take account of non-thermal diffusion by newly-adsorbed molecules, which bring kinetic energy both from the gas phase and from their acceleration into a surface binding site. Extrapolation of the model to conditions appropriate to protoplanetary disks, in which direct accretion of water from the gas-phase may be the dominant ice formation mechanism, indicate that these ices may be less porous than laboratory ices.

Structural incorporation of MgCl2 into ice VII at room temperature

NASA Astrophysics Data System (ADS)

Watanabe, Mao; Komatsu, Kazuki; Noritake, Fumiya; Kagi, Hiroyuki

2017-05-01

Raman spectra and X-ray diffraction patterns were obtained from 1:100 and 1:200 \\text{MgCl}2:\\text{H}2\\text{O} solutions (in molar ratio) at pressures up to 6 GPa using diamond anvil cells (DACs) and compared with those of pure water. The O-H stretching band from ice VII crystallized from the 1:200 solution was approximately 10 cm-1 higher than that of pure ice VII. The phase boundaries between ice VII and VIII crystallized from the MgCl2 solutions at 4 GPa were 2 K lower than those of pure ice VII and VIII. These observations indicate that ice VII incorporates MgCl2 into its structure. The unit cell volumes of ice VII crystallized from pure water and the two solutions coincided with each other within the experimental error, and salt incorporation was not detectable from the cell volume. Possible configurations of ion substitution and excess volume of ice VIII were simulated on the basis of density functional theory (DFT) calculations.

Remote-Raman and Micro-Raman Studies of Solid CO2, CH4, Gas Hydrates and Ice

NASA Technical Reports Server (NTRS)

Sharma, S. K.; Misra, A. K.; Lucey, P. G.; Exarhos, G. J.; Windisch, C. F., Jr.

2004-01-01

It is well known that on Mars CO2 is the principal constituent of the thin atmosphere and on a seasonal basis CO2 snow and frost coats the polar caps. Also over 25% of the Martian atmosphere freezes out and sublimes again each year. The Mars Odyssey Emission Imaging system (THEMIS) has discovered water ice exposed near the edge of Mars southern perennials cap. In recent years, it has been suggested that in Martian subsurface CO2 may exist as gas hydrate (8CO2 + 44 H2O) with melting temperature of 10C. Since the crust of Mars has been stable for enough time there is also a possibility that methane formed by magmatic processes and/or as a byproduct of anaerobic deep biosphere activity to have raised toward the planet s surface. This methane would have been captured and stored as methane hydrate, which concentrates methane and water. Determination of abundance and distribution of these ices on the surface and in the near surface are of fundamental importance for understanding Martian atmosphere, and for future exploration of Mars. In this work, we have evaluated feasibility of using remote Raman and micro-Raman spectroscopy as potential nondestructive and non-contact techniques for detecting solid CO2, CH4 gas, and gas hydrates as well as water-ice on planetary surfaces.

Quaoar: New, Longitudinaly Resolved, Spectroscopic Characterization of Its Surface

NASA Technical Reports Server (NTRS)

Ore, C. M. Dalle; Barucci, M. A.; Cruikshank, D. P.; Alunni, Antonella

2014-01-01

(50000) Quaoar, one of the largest Trans-neptunian objects, is comparable in size to Pluto's moon Charon. However, while Charon's surface is rich almost exclusively in H2O ice, Quaoar's surface characterized by ices of CH4, N2, as well as C2H6, a product of irradiation of CH4 (Dalle Ore et al. 2009). Because of its distance from the Sun, Quaoar is expected to have preserved, to a degree, its original composition, however, its relatively small size did not make it a prime candidate for presence of volatile ices in the study by Schaller and Brown (2007). Furthermore, based on the Brown et al. (2011) study (Brown, Schaller, & Fraser, 2011. A Hypothesis for the Color Diversity of the Kuiper Belt. ApJL, 739, L60) its red coloration points to CH3OH as the ice which, when irradiated, might have produced the red material. We present new visible to near-infrared (0.3-2.48 micrometers) spectro-photometric data obtained with the XSHOOTER (Vernet et al. 2011, A&A, 536A, 105 ) instrument at the VLT-ESO facility at four different longitudes on the surface of Quaoar. The data are complemented by previously published photometric observations obtained in the near-infrared (3.6, 4.5 micrometers) with the Spitzer Space Telescope, which provide an extra set of constraints in the model calculation process in spite of the different observing times that preclude establishing the spatial consistency between the two sets. For each of the four spectra we perform spectral modeling of the entire wavelength range -from 0.3 to 4.5 micrometers- by means of a code based on the Shkuratov radiative transfer formulation of the slab model. We obtain spatially resolved compositional information for the surface of Quaoar supporting the presence of CH4 and C2H6, as previously reported, along with evidence for N2 and NH3OH. The albedo at the two Spitzer bands indicates the likely presence of CO and CO2. CH3OH, predicted on the basis of Quaoar's coloration (Brown et al. 2011), is not found at any of the four longitudes, implying that the presence of this ice is a sufficient, but not necessary condition for reddening of TNO surfaces. Other ices, in particular CH4 (Brunetto et al. 2006), have been shown to be plausible precursors for reddening of TNO surfaces.

Release of Oxidized Bromine Species From Diatoms: Implication for the Polar Troposphere and Oceanic Polyhalomethane Production

NASA Astrophysics Data System (ADS)

Manley, S. L.; Hill, V. L.

2006-12-01

Marine and ice diatoms are known producers of polybromomethanes. These trace gases produced from ice algae have been implicated as a source of photochemically active bromine involved in polar surface ozone depletion events. A more dominant source of reactive bromine, however, has been attributed to the reaction on ice particles and in sea spray aerosols of atmospherically derived HOBr with bromide and chloride to produce the dihalogens Br2 and BrCl. We have measured the release of oxidized bromine species (Brox = HOBr, Br2, Br3-1) from polar and temperate diatoms. The highest rates were measured from Porosira glaciales (CCMP 651). Release rates are range from 0.84 to 180 fmoles bromine/hour/cell depending on the species or an approximate maximum of 950 nmoles bromine/mg chl a/hr (P. glaciales). The flux from the diatoms is 0.1 to 7.5 nmoles bromine/cm2 diatom surface/hr. This release occurs from an extracellular bromoperoxidase when a suitable organic substrate is absent. At 0.84 mM bromide (average seawater concentration), the optimal pH for Brox release is 6.5, which is the putative pH of the apoplastic space, and the optimal H2O2 concentration is 250 nM. Based on these results, it is estimated that the amount of bromine released from ice algae as Brox is 10 to 200 times greater than the release of bromine as bromoform from ice algae. The Brox so produced could participate in the abiotic formation of dihalogens in sea ice. Also, Brox released from diatoms may react with specific components of DOC, if present, to indirectly produce polybromomethanes both in sea ice and seawater. The amount of polyhalomethanes produced is not only dependent on the algal species present but also on the composition of DOC.

The 2140 cm(exp -1) (4.673 Microns) Solid CO Band: The Case for Interstellar O2 and N2 and the Photochemistry of Non-Polar Interstellar Ice Analogs

NASA Technical Reports Server (NTRS)

Elsila, Jamie; Allamandola, Louis J.; Sandford, Scott A.; Witteborn, Fred C. (Technical Monitor)

1996-01-01

The infrared spectra of CO frozen in non-polar ices containing N2, CO2, O2, and H2O, and the ultraviolet photochemistry of these interstellar/precometary ice analogs are reported. The spectra are used to test the hypothesis that the narrow 2140/cm (4.673 micrometer) interstellar absorption feature attributed to solid CO might be produced by CO frozen in ices containing non-polar species such as N2 and O2. It is shown that mixed molecular ices containing CO, N2, O2, and CO2 provide a very good match to the interstellar band at all temperatures between 12 and 30 K both before and after photolysis. The optical constants (real and imaginary parts of the index of refraction) in the region of the solid CO feature are reported for several of these ices.

Simutaneous adsorption of CO2 and H2O under Mars-like conditions and application to the evolution of the Martian climate

NASA Technical Reports Server (NTRS)

Zent, Aaron P.; Quinn, Richard C.

1995-01-01

The Martian regolith is the most substantial volatile reservoir on the planet; estimates of its adsorbed inventory have been based on simple measurements of the adsorption of either water or CO2 in isolation. Under some conditions, H2O can poison adsorbate surfaces, such that CO2 uptake is greatly reduced. We have made the first measurements of the simultaneous adsorption of CO2 and H2O under conditions appropriate to the Martian regolith and have found that at H2O monolayer coverage above about 0.5, CO2 begins to be displaced into the gas phase. We have developed an empirical expression that describes our co-adsorption data and have applied it to standard models of the Martian regolith. We find that currently, H2O does not substantially displace CO2, implying that the adsorbate inventories previously derived may be accurate, not more than 3-4 kPa (30-40 mbar). No substantial increase in atmospheric pressure is predicted at higher obliquities because high-latitude ground ice buffers the partial pressure of H2O in the pores, preventing high monolayer coverages of H2O from displacing CO2. The peak atmospheric pressure at high obliquity does increase as the total inventory of exchangeable CO2 increases.

Spectra and Photochemistry of Relevance to Icy Outer Solar System Objects

NASA Technical Reports Server (NTRS)

Bernstein, M. P.; Sandford, S. A.; Allamandola, L. J.; Fonda, Mark (Technical Monitor)

2003-01-01

The Astrochemistry Lab at NASA Ames (www.astrochem.org) has an interest in the organic photochemistry of extraterrestrial ices, having traditionally performed experiments under interstellar conditions. We have recently embarked on projects for PG\\&G to measure spectra and elucidate the photochemistry of ices relevant to outer Solar System objects. 1) We will report on the determination of real and imaginary indicies of refraction of H2O and N2 dominated ices containing simple, common, extraterrestrial molecules such as NH3, HCN, formaldehyde, \\& methanol. 2) We will compare and contrast the photochemistry of H2O ices containing organic molecules at 100 K with previously reported work at 15 K.

Simultaneous adsorption of CO2 and H2O under Mars-like conditions and application to the evolution of the Martian climate

NASA Technical Reports Server (NTRS)

Zent, Aaron, P.; Quinn, Richard C.

1995-01-01

The Martian regolith is the most substantial volatile reservoir on the planet; estimates of its adsorbed inventory have been based on simple measurements of the adsorption of either water or CO2 in isolation. Under some conditions, H2O can poison adsorbate surfaces, such that CO2 uptake is greatly reduced. We have made the first measurements of the simultaneous adsorption of CO2 and H2O under conditions appropriate to the Martian regolith and have found that at H2O monolayer coverage above about 0.5, CO2 begins to be displaced into the gas phase. We have developed an empirical expression that describes our co-adsorption data and have applied it to standard models of the Martian regolith. We find that currently, H2O does not substantially displace CO, implying that the adsorbate inventories previously derived may be accurate, not more than 3-4 kPa (30-40 mbar). No substantial increase in atmospheric pressure is predicted at higher obliquities because high-latitude ground ice buffers the partial pressure of H2O in the pores, preventing high monolayer coverages of H2O from displacing CO2. The peak atmospheric pressure at high obliquity does increase as the total inventory of exchangeable CO2 increases.

Heat of solution: A new source of thermal energy in the subsurface of cometary nuclei and the gas-exsolution mechanism driving outbursts of Comet 29P/Schwassmann‒Wachmann and other comets

NASA Astrophysics Data System (ADS)

Miles, Richard

2016-07-01

This paper is a continuation of Miles et al. (2015) [Icarus] and Miles (2015b) [Icarus], which detail new observations of Comet 29P/Schwassmann‒Wachmann, characterise its rotational period (∼57 d), and identify the presence of discrete sources of outburst on its nucleus: the latter ruling out amorphous-to-crystalline H2O ice transitions as the cause of its outbursts. Summary data are presented for 29P and a further 16 non-fragmenting comets which exhibit outbursts of >2 magnitudes. A comprehensive physicochemical mechanism is postulated to account for major outbursts based on melting of cometary ices and the exothermic dissolution of gases, especially CO and CO2 at pressures of 10‒200 kPa. The thermodynamics of enthalpy heating are described and heats of solution are calculated from gas-liquid solubility data yielding -6 kJ mol-1 for CO in CH4, and -15 kJ mol-1 for CO2 in CH3OH close to their freezing point. Heats of solution are ∼6 times greater (per mole) than the enthalpy of fusion of the pure CH4 and CH3OH ices, enabling gas pressures of >∼80 kPa to continually melt these ices. Supervolatile O2 and N2 gases may also participate by dissolving exothermically in liquid CH4 and other hydrocarbons potentially reaching high mixing ratios. H2S and NH3 gases dissolve exothermically in CH3OH liberating up to 20 kJ mol-1 and 13 kJ mol-1, respectively, and all three hydrophilic species facilitate sintering of H2O ice in the near-surface of comets. Localised melting and consolidation is favoured in slowly-rotating cometary nuclei of intermediate dust/gas ratios, at pressures of ∼1 kPa, and temperatures as low as 50‒65 K where O2 and N2 are abundant. Nyctogenic processes on the night-time side of the nucleus restock desiccated surface layers, reseal the crust, enabling fractionation of solutes in sub-crustal liquid phases via fractional sublimation/distillation of non-polar, hydrophobic CH4 and other hydrocarbons; and by fractional crystallisation of polar, hydrophilic phases rich in aqueous CH3OH and other organic oxygenates, e.g. CH2O, able to form low melting point eutectic mixtures. A generalised outburst mechanism is described involving the containment of gases as solutes in cryomagma beneath consolidated surface crustal regions. Disruption of the crust and associated pressure loss render the cryomagma supersaturated, and the concomitant explosive exsolution of gases provokes a cometary outburst. The CO gas-exsolution mechanism operates at ∼65 to 95 K and accounts for activity of 29P and other distant comets up to rh = ∼15 AU. A similar mechanism can operate at ∼150 to 200 K driven by CO2 in aqueous CH3OH and may account for rare outbursts of Jupiter-family comets such as 17P/Holmes. At least 10-15% of all periodic comets may be subject to gas-exsolution outbursts, the majority of which are weak and go undetected. Possible surface morphologies of the nucleus of Comet 29P are discussed. The mechanism may also explain the phenomenon of strong cometary outbursts triggering secondary events, as observed for 17P, 29P and 41P.

Inference of Surface Parameters from Near-Infrared Spectra of Crystalline H2O Ice with Neural Learning

NASA Astrophysics Data System (ADS)

Zhang, Lili; Merényi, Erzsébet; Grundy, William M.; Young, Eliot F.

2010-07-01

The near-infrared spectra of icy volatiles collected from planetary surfaces can be used to infer surface parameters, which in turn may depend on the recent geologic history. The high dimensionality and complexity of the spectral data, the subtle differences between the spectra, and the highly nonlinear interplay between surface parameters make it often difficult to accurately derive these surface parameters. We use a neural machine, with a Self-Organizing Map (SOM) as its hidden layer, to infer the latent physical parameters, temperature and grain size from near-infrared spectra of crystalline H2O ice. The output layer of the SOM-hybrid machine is customarily trained with only the output from the SOM winner. We show that this scheme prevents simultaneous achievement of high prediction accuracies for both parameters. We propose an innovative neural architecture we call Conjoined Twins that allows multiple (k) SOM winners to participate in the training of the output layer and in which the customization of k can be limited automatically to a small range. With this novel machine we achieve scientifically useful accuracies, 83.0 ± 2.7% and 100.0 ± 0.0%, for temperature and grain size, respectively, from simulated noiseless spectra. We also show that the performance of the neural model is robust under various noisy conditions. A primary application of this prediction capability is planned for spectra returned from the Pluto-Charon system by New Horizons.

The Postshock Chemical Lifetimes of Outflow Tracers and a Possible New Mechanism to Produce Water Ice Mantles

NASA Technical Reports Server (NTRS)

Bergin, Edwin A.; Melnick, Gary J.; Neufeld, David A.

1998-01-01

We have used a coupled time-dependent chemical and dynamical model to investigate the lifetime of the chemical legacy in the wake of C-type shocks. We concentrate this study on the chemistry of H2O and O2, two molecules which are predicted to have abundances that are significantly affected in shock-heated gas. Two models are presented: (1) a three-stage model of preshock, shocked, and postshock gas; and (2) a Monte Carlo cloud simulation where we explore the effects of stochastic shock activity on molecular gas over a cloud lifetime. For both models we separately examine the pure gas-phase chemistry as well as the chemistry including the interactions of molecules with grain surfaces. In agreement with previous studies, we find that shock velocities in excess of 10 km/s are required to convert all of the oxygen not locked in CO into H2O before the gas has an opportunity to cool. For pure gas phase models the lifetime of the high water abundances, or "H2O legacy," in the postshock gas is approximately (4-7) x 10(exp 5) yr, independent of the gas density. A density dependence for the lifetime of H2O is found in gas-grain models as the water molecules deplete onto grains at the depletion timescale. Through the Monte Carlo cloud simulation we demonstrate that the time-average abundance of H2O, the weighted average of the amount of time gas spends in preshock, shock, and postshock stages, is a sensitive function of the frequency of shocks. Thus we predict that the abundance of H2O, and to a lesser extent O2, can be used to trace the history of shock activity in molecular gas. We use previous large-scale surveys of molecular outflows to constrain the frequency of 10 km/s shocks in regions with varying star formation properties and discuss the observations required to test these results. We discuss the postshock lifetimes for other possible outflow tracers (e.g., SiO and CH3OH) and show that the differences between the lifetimes for various tracers can produce potentially observable chemical variations between younger and older outflows. For gas-grain models we find that the abundance of water-ice on grain surfaces can be quite large and is comparable to that observed in molecular clouds. This offers a possible alternative method to create water mantles without resorting to grain surface chemistry: gas heating and chemical modification due to a C-type shock and subsequent depletion of the gas-phase species onto grain mantles.

Ice chemistry of acetaldehyde reveals competitive reactions in the first step of the Strecker synthesis of alanine: formation of HO-CH(CH3)-NH2 vs. HO-CH(CH3)-CN

NASA Astrophysics Data System (ADS)

Fresneau, Aurélien; Danger, Grégoire; Rimola, Albert; Duvernay, Fabrice; Theulé, Patrice; Chiavassa, Thierry

2015-08-01

The understanding of compound formation in laboratory simulated astrophysical environments is an important challenge in obtaining information on the chemistry occurring in these environments. We here investigate by means of both laboratory experiments and quantum chemical calculations the ice-based reactivity of acetaldehyde (CH3CHO) with ammonia (NH3) and hydrogen cyanide (HCN) in excess of water (H2O) promoted by temperature. A priori, this study should give information on alanine (2HN-CH(CH3)-COOH) formation (the simplest chiral amino acid detected in meteorites), since these reactions concern the first steps of its formation through the Strecker synthesis. However, infrared spectroscopy, mass spectrometry with HC14N or HC15N isotopologues and B3LYP-D3 results converge to indicate that an H2O-dominated ice containing CH3CHO, NH3 and HCN not only leads to the formation of α-aminoethanol (2HN-CH(CH3)-OH, the product compound of the first step of the Strecker mechanism) and its related polymers (2HN-(CH(CH3)-O)n-H) due to reaction between CH3CHO and NH3, but also to the 2-hydroxypropionitrile (HO­-CH(CH3)-CN) and its related polymers (H-(O-CH(CH3))n-CN) from direct reaction between CH3CHO and HCN. The ratio between these two species depends on the initial NH3/HCN ratio in the ice. Formation of α-aminoethanol is favoured when the NH3 concentration is larger than HCN. We also show that the presence of water is essential for the formation of HO­-CH(CH3)-CN, contrarily to 2HN-CH(CH3)-OH whose formation also takes place in absence of H2O ice. As in astrophysical ices NH3 is more abundant than HCN, formation of α-aminoethanol should consequently be favoured compared to 2-hydroxypropionitrile, thus pointing out α-aminoethanol as a plausible intermediate species for alanine synthesis through the Strecker mechanism in astrophysical ices.

Following the south polar cap recession as viewed by OMEGA/MEX using automatic detection of H2O and CO2 ices.

NASA Astrophysics Data System (ADS)

Schmidt, F.; Doute, S.; Schmitt, B.

In order to understand Mars' current climate it is necessary to detect, characterize and monitor CO2 and H2O at the surface (permanent and seasonal icy deposits) and in the atmosphere (vapor and clouds). Here we will focus on the South Seasonal Polar Cap (SSPC) whose recession was previously observed with different techniques : from earth in the visible range with HST [James 1996], or from MGS spacecraft with MOC images [Benson 2005], in the thermal IR range by the TES [Kieffer 2000], in the near infrared by OMEGA/MEX [Langevin submitted]. The time and space evolutions of the SSPC is a major annual climatic signal both at the global and the regional scales. In particular the measurement of the temporal and spatial distributions of CO2 constrains exchange processes between both surface and atmosphere. This exchange may involve preponderant species : H2O, CO2 and dust. In this work we will apply a new detection technique : "wavanglet" in order to follow the recession of the SSPC thanks to OMEGA/MEX observations. This method was especially developed in the goal to classify a huge dataset, such OMEGA ones. We propose to use "wavanglet" as a supervised automatic classification method that identifies spectral features and classifies the image in spectrally homogeneous units. Additionally we will evaluate quantitative detection limits of "wavanglet" based on synthetic dataset simulating OMEGA spectra in typical situation of the SSPC. This detection limit will be discussed in terms of abundance for H2O and CO2 ices in order to improve the interpretation of the classification. Finally we will present the recession of the SSPC using "wavanglet" and we will compare the results with those of earlier investigation. An interpretation of the similarities and disagreements between those maps will be done.

The kinetics of H2O vapor condensation and evaporation on different types of ice in the range 130-210 K.

PubMed

Pratte, Pascal; van den Bergh, Hubert; Rossi, Michel J

2006-03-09

The kinetics of condensation (kc) and the evaporation flux (J(ev)) of H2O on ice were studied in the range 130-210 K using pulsed-valve and steady-state techniques in a low-pressure flow reactor. The uptake coefficient gamma was measured for different types of ice, namely, condensed (C), bulk (B), single crystal (SC), snow (S), and cubic ice (K). The negative temperature dependence of gamma for C, B, SC, and S ice reveals a precursor-mediated adsorption/desorption process in agreement with the proposal of Davy and Somorjai.(1) The non-Arrhenius behavior of the rate of condensation, kc, manifests itself in a discontinuity in the range 170-190 K depending on the type of ice and is consistent with the precursor model. The average of the energy of sublimation DeltaH(S) degrees is (12.0 +/- 1.4) kcal/mol for C, B, S, and SC ice and is identical within experimental uncertainty between 136 and 210 K. The same is true for the entropy of sublimation DeltaS(S). In contrast, both gamma and the evaporative flux J(ev) are significantly different for different ices. In the range 130-210 K, J(ev) of H2O ice was significantly smaller than the maximum theoretically allowed value. This corroborates gamma values significantly smaller than unity in that T range. On the basis of the present kinetic parameters, the time to complete evaporation of a small ice particle of radius 1 mum is approximately a factor of 5 larger than that previously thought.

Measurement of the accumulation of water ice on optical components in cryogenic vacuum environments

NASA Astrophysics Data System (ADS)

Moeller, Trevor M.; Montgomery Smith, L.; Collins, Frank G.; Labello, Jesse M.; Rogers, James P.; Lowry, Heard S.; Crider, Dustin H.

2012-11-01

Standard vacuum practices mitigate the presence of water vapor and contamination inside cryogenic vacuum chambers. However, anomalies can occur in the facility that can cause the accumulation of amorphous water ice on optics and test articles. Under certain conditions, the amorphous ice on optical components shatters, which leads to a reduction in signal or failure of the component. An experiment was performed to study and measure the deposition of water (H2O) ice on optical surfaces under high-vacuum cryogenic conditions. Water was introduced into a cryogenic vacuum chamber, via a hydrated molecular sieve zeolite, through an effusion cell and impinged upon a quartz-crystal microbalance (QCM) and first-surface gold-plated mirror. A laser and photodiode setup, external to the vacuum chamber, monitored the multiple-beam interference reflectance of the ice-mirror configuration while the QCM measured the mass deposition. Data indicates that water ice, under these conditions, accumulates as a thin film on optical surfaces to thicknesses over 45 microns and can be detected and measured by nonintrusive optical methods which are based upon multiple-beam interference phenomena. The QCM validated the interference measurements. This experiment established proof-of-concept for a miniature system for monitoring ice accumulation within the chamber.

Young surface of Pluto's Sputnik Planitia caused by viscous relaxation

NASA Astrophysics Data System (ADS)

Wei, Q.; Hu, Y.; Liu, Y.; Lin, D. N. C.; Yang, J.; Showman, A. P.

2017-12-01

The young surface of Pluto's Sputnik Planitia (SP) is one of the most prominent features observed by the New Horizon mission (Moore et al., 2016; Stern et al., 2015). No crater has been confirmed on the heart-shaped SP basin, in contrast to more than 5000 identified over comparable areas elsewhere (Robbins et al., 2016). The SP basin is filled with mostly N2 ice and small amount of CH4 and CO ice (Protopapa et al., 2017). Previous studies suggested that the SP surface might be renewed through vigorous thermal convection (McKinnon et al., 2016), and that the surface age may be as young as 500,000 years. In this paper, we present numerical simulations demonstrating that craters can be removed by rapid viscous relaxation of N2 ice over much shorter timescales. The crater retention age is less than 1000 years if the N2-ice thickness is several kilometers. McKinnon, W. B., Nimmo, F., Wong, T., Schenk, P. M., White, O. L., Roberts, J., . . . Umurhan, O. (2016). Convection in a volatile nitrogen-ice-rich layer drives Pluto's geological vigour. Nature, 534(7605), 82-85. Moore, J. M., McKinnon, W. B., Spencer, J. R., Howard, A. D., Schenk, P. M., Beyer, R. A., . . . White, O. L. (2016). The geology of Pluto and Charon through the eyes of New Horizons. Science, 351(6279), 1284-1293. Protopapa, S., Grundy, W. M., Reuter, D. C., Hamilton, D. P., Dalle Ore, C. M., Cook, J. C., . . . Young, L. A. (2017). Pluto's global surface composition through pixel-by-pixel Hapke modeling of New Horizons Ralph/LEISA data. Icarus, Volume 287, 218-228. doi:http://dx.doi.org/10.1016/j.icarus.2016.11.028Robbins, S. J., Singer, K. N., Bray, V. J., Schenk, P., Lauer, T. R., Weaver, H. A., . . . Porter, S. (2016). Craters of the Pluto-Charon system. Icarus. Stern, S. A., Bagenal, F., Ennico, K., Gladstone, G. R., Grundy, W. M., McKinnon, W. B., . . . Zirnstein, E. (2015). The Pluto system: Initial results from its exploration by New Horizons. Science, 350(6258), aad1815.

Orbitally-Induced, Quasi-Periodic Climate Change on Mars: Modelling Changes in the Global Cycling of Water and Carbon Dioxide

NASA Astrophysics Data System (ADS)

Mischna, M. A.; Richardson, M. I.; Wilson, R. J.

2002-12-01

Mars' orbital parameters (obliquity, eccentricity and argument of perihelion) are thought to have varied substantially on time scales >105 years. Such variations, especially in obliquity, may drastically affect the circulation of the atmosphere and volatile cycling. In this study, we focus on the response of the water and carbon dioxide cycles to changes in these orbital parameters, chiefly obliquity. The study employs the Geophysical Fluid Dynamics Laboratory Mars General Circulation Model, conducting simulations over a range of orbital states to examine changes in the cycling and deposition of these volatiles. This model contains full 3D accounting of atmospheric water and carbon dioxide as well as a basic dust cycle. The present martian obliquity is 25°, though it is believed to have recently varied between 15 and 45 degrees. Our simulations look at present martian conditions, only with obliquity varying between 5 and 60 degrees. Simulations are run out until water and carbon dioxide budgets have reached equilibrium--typically 30-40 years. As expected, volatile cycling on Mars increases with obliquity, as the polar caps are exposed to increased insolation, leading to greater seasonal ice caps and ultimately development of surface water ice in the now thermally favorible low latitudes. By 45°, water ice is stable in a broad band just north of the equator. Such an ice distribution has potential implications for the surface wind pattern through the ice-albedo effect on surface heating. Permanent polar CO2 caps are not stable under present conditions, but we find CO2 cap growth and corresponding atmospheric deflation to be evident at very low obliquities. We find that for most choices of orbital conditions, the northern hemisphere remains the stable pole for water ice, a result of the martian topographic dichotomy. We have begun to look at the impact of desorbed CO2 and H2O ice from the regolith on climatic conditions. Present estimates of the volatile abundance in the regolith vary greatly, but recent Mars Odyssey results hint at large abundances of water ice in the martian high-latitude regolith. The results of this study should better define models of polar volatile evolution, specifically those of layered terrain formation. The radiative feedback effects of increased atmospheric CO2 and H2O from the polar caps and regoliths has yet to be examined. Future plans include more accurate representations of dust injection and radiative transfer to tackle this problem.

Before the Ring: synthesis of linear organic molecules in astrophysical ices by low energy electron impact

NASA Astrophysics Data System (ADS)

Huels, Michael A.; Bass Andrew, D.; Mirsaleh-Kohan, Nasrin; Sanche, Leon

The question of the origin for the building blocks of life, either synthesized here on earth, or in space [1], has been the subject of much debate, experimental investigation, or astronomical observation, much of it stimulated by the early experiments of Miller [2], and subsequent space radiation related variations thereof [3-5]. And while the precise details of the formation of even the simplest biomolecules that make up life on earth still remain shrouded inmystery, one of the notions that persist throughout the debate is that the building blocks of life, such as amino-acids, or even the cyclic components of RNA and DNA, or other cyclic hydrocarbons (e.g. PHAs), where synthesized via radiolysis [6] either in the earths proto-atmosphere, its early oceans, or in the near interstellar space surrounding the early earth. Here we provide experimental evidence for the hypothesis that interactions of low energy secondary electrons and ions, formed during the radiolysis of matter, with atoms and molecules in the medium, may have played, and may still play an important role in the chemical transformation of astrophysical or planetary surface ices [7], where they lead to the synthesis of more complex chemical species from less complex, naturally occurring components. We report the synthesis and desorption of new chemical species from simple molecular surface ices, containing CH4 / CD4 , C2 D2 , O2 , CO, CO2 , or N2 in various combination mixtures, irradiated by low energy (<60 eV) electrons. For example, for CD4 ices we observe the formation and desorption of energetic ions such as D3 + , CD5 + , and C2 Dn + (n = 2-5), as well as three carbon containing chains, that are also observed to desorb from C2 D2 films; for oxygen rich methane ices we observe the synthesis and desorption of H2 O+ , H3 O+ , as well as formaldehyde type cations, viz., Hn CO+ (n = 1-3), among others. The formation of all these linear, pre-biotic molecular species, produced here by electron initiated cation-reactions in simple molecular films, suggests that similar mechanisms likely precede the synthesis of life's most basic cyclic molecular components in planetary, or astrophysical surface ices that are continuously subjected to the types of space radiations (UV, X-or -ray, or heavy ions) that can generate such low energy secondary electrons. [Funded by NSERC and Canadian Space Agency] [1] P. Ehrenfreund, S. Rasmussen, J. Cleaves, L. Chen, Astrobiology 6 (2006) 490. [2] (a) S.L. Miller, Science 117 (1953) 528; (b) S.L. Miller, J. Am. Chem. Soc. 77 (1955) 2351. [3] (a) M.H. Morre, R.L. Hudson, Icarus 140 (1999) 451; (b) M.H. Morre, R.L. Hudson, Icarus 145 (2000) 282. [4] M.H. Moore, R.L. Hudson, P.A. Gerakines, Spectrochim. Acta A 57 (2001) 843. [5] M.P. Bernstein, S.A. Sandford, L.J. Allamandola, Sci. Am. (July) (1999) (and references cited therein). [6] J. Vergne, L. Dumas, J.-L. Decout, M.-C. Maurel, Planet. Space Sci. 48 (2000) 1139. [7] T.E. Madey, R.E. Johnson, T.M. Orlando, Surf. Sci. 500 (2002) 838.

Low temperature self-cleaning properties of superhydrophobic surfaces

NASA Astrophysics Data System (ADS)

Wang, Fajun; Shen, Taohua; Li, Changquan; Li, Wen; Yan, Guilong

2014-10-01

Outdoor surfaces are usually dirty surfaces. Ice accretion on outdoor surfaces could lead to serious accidents. In the present work, the superhydrophobic surface based on 1H, 1H, 2H, 2H-Perfluorodecanethiol (PFDT) modified Ag/PDMS composite was prepared to investigate the anti-icing property and self-cleaning property at temperatures below freezing point. The superhydrophobic surface was deliberately polluted with activated carbon before testing. It was observed that water droplet picked up dusts on the cold superhydrophobic surface and took it away without freezing at a measuring temperature of -10 °C. While on a smooth PFDT surface and a rough surface base on Ag/PDMS composite without PFDT modification, water droplets accumulated and then froze quickly at the same temperature. However, at even lower temperature of -12 °C, the superhydrophobic surface could not prevent the surface water from icing. In addition, it was observed that the frost layer condensed from the moisture pay an important role in determining the low temperature self-cleaning properties of a superhydrophobic surface.

Can xenon in water inhibit ice growth? Molecular dynamics of phase transitions in water-Xe system.

PubMed

Artyukhov, Vasilii I; Pulver, Alexander Yu; Peregudov, Alex; Artyuhov, Igor

2014-07-21

Motivated by recent experiments showing the promise of noble gases as cryoprotectants, we perform molecular dynamics modeling of phase transitions in water with xenon under cooling. We follow the structure and dynamics of xenon water solution as a function of temperature. Homogeneous nucleation of clathrate hydrate phase is observed and characterized. As the temperature is further reduced we observe hints of dissociation of clathrate due to stronger hydrophobic hydration, pointing towards a possible instability of clathrate at cryogenic temperatures and conversion to an amorphous phase comprised of "xenon + hydration shell" Xe·(H2O)21.5 clusters. Simulations of ice-xenon solution interface in equilibrium and during ice growth reveal the effects of xenon on the ice-liquid interface, where adsorbed xenon causes roughening of ice surface but does not preferentially form clathrate. These results provide evidence against the ice-blocker mechanism of xenon cryoprotection.

The Formation of N- and O-Heterocycles from the Irradiation of Benzene and Naphthalene in H2O/NH3- Containing Ices

NASA Technical Reports Server (NTRS)

Sandford, S. A.; Materese, C. K.; Nuevo, M.

2015-01-01

Aromatic hydrocarbons are an important class of molecules for both astrochemistry and astrobiology (Fig. 1). Within this class of molecules, polycyclic aromatic hydrocarbons (PAHs) are known to be ubiquitous in many astrophysical environments, and are likely present in interstellar clouds and protostellar disks. In dense clouds, PAHs are expected to condense onto grains as part of mixed molecular ice mantles dominated by small molecules like H2O,CH3OH, NH3, CO, and CO2. These ices are exposed to ionizing radiation in the form of cosmic rays and ambient high-energy X-ray and UV photons.

Isotopic composition of ice cores and meltwater from upper fremont glacier and Galena Creek rock glacier, Wyoming

USGS Publications Warehouse

DeWayne, Cecil L.; Green, J.R.; Vogt, S.; Michel, R.; Cottrell, G.

1998-01-01

Meltwater runoff from glaciers can result from various sources, including recent precipitation and melted glacial ice. Determining the origin of the meltwater from glaciers through isotopic analysis can provide information about such things as the character and distribution of ablation on glaciers. A 9.4 m ice core and meltwater were collected in 1995 and 1996 at the glacigenic Galena Creek rock glacier in Wyoming's Absaroka Mountains. Measurements of chlorine-36 (36Cl), tritium (3H), sulphur-35 (35S), and delta oxygen-18 (??18O) were compared to similar measurements from an ice core taken from the Upper Fremont Glacier in the Wind River Range of Wyoming collected in 1991-95. Meltwater samples from three sites on the rock glacier yielded 36Cl concentrations that ranged from 2.1 ?? 1.0 X 106 to 5.8??0.3 X 106 atoms/l. The ice-core 36Cl concentrations from Galena Creek ranged from 3.4??0.3 X 105 to 1.0??0.1 X 106 atoms/l. Analysis of an ice core from the Upper Fremont Glacier yielded 36Cl concentrations of 1.2??0.2 X 106 and 5.2??0.2 X 106 atoms/l for pre- 1940 ice and between 2 X 106 and 3 X 106 atoms/l for post-1980 ice. Purdue's PRIME Lab analyzed the ice from the Upper Fremont Glacier. The highest concentration of 36Cl in the ice was 77 ?? 2 X 106 atoms/l and was deposited during the peak of atmospheric nuclear weapons testing in the late 1950s. This is an order of magnitude greater than the largest measured concentration from both the Upper Fremont Glacier ice core that was not affected by weapons testing fallout and the ice core collected from the Galena Creek rock glacier. Tritium concentrations from the rock glacier ranged from 9.2??0.6 to 13.2??0.8 tritium units (TU) in the meltwater to -1.3??1.3 TU in the ice core. Concentrations of 3H in the Upper Fremont Glacier ice core ranged from 0 TU in the ice older than 50 years to 6-12 TU in the ice deposited in the last 10 years. The maximum 3H concentration in ice from the Upper Fremont Glacier deposited in the early 1960s during peak weapons testing fallout for this isotope was 360 TU. One meltwater sample from the rock glacier was analyzed for 35S with a measured concentration of 5.4??1.0 millibecquerel per liter (mBeq/l). Modern precipitation in the Rocky Mountains contains 35S from 10 to 40 mBeq/L. The ??18O results in meltwater from the Galena Creek rock glacier (-17.40??0.1 to -17.98??0.1 per mil) are similar to results for modern precipitation in the Rocky Mountains. Comparison of these isotopic concentrations from the two glaciers suggest that the meltwater at the Galena Creek site is composed mostly of melted snow and rain that percolates through the rock debris that covers the glacier. Additionally, this water from the rock debris is much younger (less than two years) than the reported age of about 2000 years for the subsurface ice at the mid-glacier coring site. Thus the meltwater from the Galena Creek rock glacier is composed primarily of melted surface snow and rain water rather than melted glacier ice, supporting previous estimates of slow ablation rates beneath the surface debris of the rock glacier.

Brief Communication: Ikaite (CaCO3·6H2O) discovered in Arctic sea ice

NASA Astrophysics Data System (ADS)

Dieckmann, G. S.; Nehrke, G.; Uhlig, C.; Göttlicher, J.; Gerland, S.; Granskog, M. A.; Thomas, D. N.

2010-05-01

We report for the first time on the discovery of calcium carbonate crystals as ikaite (CaCO3·6H2O) in sea ice from the Arctic (Kongsfjorden, Svalbard) as confirmed by morphology and indirectly by X-ray diffraction as well as XANES spectroscopy of its amorophous decomposition product. This finding demonstrates that the precipitation of calcium carbonate during the freezing of sea ice is not restricted to the Antarctic, where it was observed for the first time in 2008. This observation is an important step in the quest to quantify its impact on the sea ice driven carbon cycle.

The Mid-Infrared Absorption Spectra of Neutral PAHs in Dense Interstellar Clouds

NASA Technical Reports Server (NTRS)

Bernstein, M. P.; Sandford, S. A.; Allamandola, L. J.

2005-01-01

Polycyclic aromatic hydrocarbons (PAHs) are common throughout the universe and are expected to be present in dense interstellar clouds. In these environments, some P.4Hs may be present in the gas phase, but most should be frozen into ice mantles or adsorbed onto dust grains and their spectral features are expected to be seen in absorption. Here we extend our previous work on the infrared spectral properties of the small PAH naphthalene (C10H8) in several media to include the full mid-infrared laboratory spectra of 11 other PAHs and related aromatic species frozen in H2O ices. These include the molecules 1,2-dihydronaphthalene, anthracene, 9,1O-dihydroanthracene, phenanthrene, pyrene, benzo[e]pyrene, perylene, benzo(k)fluoranthene, pentacene, benzo[ghi]perylene, and coronene. These results demonstrate that PAHs and related molecules, as a class, show the same spectral behaviors as naphthalene when incorporated into H2O-rich matrices. When compared to the spectra of these same molecules isolated in inert matrices (e.g., Ar or N2), the absorption bands produced when they are frozen in H2O matrices are broader (factors of 3-10), show small position shifts in either direction (usually < 4/cm, always < 10/cm), and show variable changes in relative band strengths (typically factors of 1-3). There is no evidence of systematic increases or decreases in the absolute strengths of the bands of these molecules when they are incorporated in H2O matrices. In H2O-rich ices, their absorption bands are relatively insensitive to concentration over the range of 10 < H2O/PAH < 200): The absorption bands of these molecules are also insensitive to temperature over the 10 K < T < 125 K range, although the spectra can show dramatic changes as the ices are warmed through the temperature range in which amorphous H2O ice converts to its cubic and hexagonal crystalline forms (T > 125 Kj. Given the small observed band shifts cause by H2O, the current database of spectra from Ar matrix-isolated neutral PAHs and related molecules should be useful for the search for these species in dense clouds on the basis of observed absorption band positions. Furthermore, these data permit determination of column densities to better than a factor of 3 for PAHs in dense clouds. Column density determination of detected aromatics to better than a factor of 3 will, however, require good knowledge about the nature of the matrix in which the PAH is embedded and laboratory studies of relevant samples.

740,000-year Deuterium Record in an Ice Core from Dome C, Antarctica

DOE Data Explorer

Jouzel, Jean [Laboratoire des Sciences du Climat et de l'Environnement

2004-01-01

Because isotopic fractions of the heavier oxygen-18 (18O) and deuterium (2H) in snowfall are temperature-dependent and a strong spatial correlation exists between the annual mean temperature and the mean isotopic fraction of 18O or 2H in precipitation, it is possible to derive temperature records from the records of those isotopes in ice cores.

Ice nucleation efficiency of AgI: review and new insights

NASA Astrophysics Data System (ADS)

Marcolli, Claudia; Nagare, Baban; Welti, André; Lohmann, Ulrike

2016-07-01

AgI is one of the best-investigated ice-nucleating substances. It has relevance for the atmosphere since it is used for glaciogenic cloud seeding. Theoretical and experimental studies over the last 60 years provide a complex picture of silver iodide as an ice-nucleating agent with conflicting and inconsistent results. This review compares experimental ice nucleation studies in order to analyze the factors that influence the ice nucleation ability of AgI. The following picture emerges from this analysis: the ice nucleation ability of AgI seems to be enhanced when the AgI particle is on the surface of a droplet, which is indeed the position that a particle takes when it can freely move in a droplet. The ice nucleation by particles with surfaces exposed to air depends on water adsorption. AgI surfaces seem to be most efficient at nucleating ice when they are exposed to relative humidity at or even above water saturation. For AgI particles that are completely immersed in water, the freezing temperature increases with increasing AgI surface area. Higher threshold freezing temperatures seem to correlate with improved lattice matches as can be seen for AgI-AgCl solid solutions and 3AgI·NH4I·6H2O, which have slightly better lattice matches with ice than AgI and also higher threshold freezing temperatures. However, the effect of a good lattice match is annihilated when the surfaces have charges. Also, the ice nucleation ability seems to decrease during dissolution of AgI particles. This introduces an additional history and time dependence for ice nucleation in cloud chambers with short residence times.

Geological Evidence for Recent Ice Ages on Mars

NASA Astrophysics Data System (ADS)

Head, J. W.; Mustard, J. F.; Kreslavsky, M. A.; Milliken, R. E.; Marchant, D. R.

2003-12-01

A primary cause of ice ages on Earth is orbital forcing from variations in orbital parameters of the planet. On Mars such variations are known to be much more extreme. Recent exploration of Mars has revealed abundant water ice in the near-surface at high latitudes in both hemispheres. We outline evidence that these near-surface, water-ice rich mantling deposits represent a mixture of ice and dust that is layered, meters thick, and latitude dependent. These units were formed during a geologically recent major martian ice age, and were emplaced in response to the changing stability of water ice and dust on the surface during variations in orbital parameters. Evidence for these units include a smoothing of topography at subkilometer baselines from about 30o north and south latitudes to the poles, a distinctive dissected texture in MOC images in the +/-30o-60o latitude band, latitude-dependent sets of topographic characteristics and morphologic features (e.g., polygons, 'basketball' terrain texture, gullies, viscous flow features), and hydrogen concentrations consistent with the presence of abundant ice at shallow depths above 60o latitude. The most equatorward extent of these ice-rich deposits was emplaced down to latitudes equivalent to Saudi Arabia and the southern United States on Earth during the last major martian ice age, probably about 0.4-2.1 million years ago. Mars is currently in an inter-ice age period and the ice-rich deposits are presently undergoing reworking, degradation and retreat in response to the current stability relations of near-surface ice. Unlike Earth, martian ice ages are characterized by warmer climates in the polar regions and the enhanced role of atmospheric water ice and dust transport and deposition to produce widespread and relatively evenly distributed smooth deposits at mid-latitudes during obliquity maxima.

Evolution of Interstellar Grains

NASA Technical Reports Server (NTRS)

Allamandola, Lou J.; DeVincenzi, Donald L. (Technical Monitor)

1998-01-01

During the past two decades observations combined with laboratory simulations, have revolutionized our understanding of interstellar ice and dust, the raw materials from which planets, comets and stars form. Most interstellar material is concentrated in large molecular clouds where simple molecules are formed by dust-grain and gas-phase reactions. Gaseous species striking the cold (10K) dust stick, forming an icy grain mantle. This accretion, coupled with UV photolysis, produces a complex chemical mixture containing volatile, non-volatile, and isotopically fractionated species. Ices in molecular clouds contain the very simple molecules H2O, CH3OH, CO, CO2, H2, and perhaps some NH3 and H2CO, as well as more complex species. The evidence for these compounds, as well as carbon-rich materials, will be reviewed and the possible connections with comets and meteorites will be presented in the first part of the talk . The second part of the presentation will focus on interstellar/precometary ice photochemical evolution and the species likely to be found in comets. The chemical composition and photochemical evolution of realistic interstellar/pre-cometary ice analogs will be discussed. Ultraviolet photolysis of these ices produces H2, H2CO, CO2, CO, CH4, HCO, and more complex molecules. When ices representative of interstellar grains and comets are exposed to UV radiation at low temperature a series of moderately complex organic molecules are formed in the ice including: CH3CH2OH (ethanol), HC(=O)NH2 (formamide), CH3C(=O)NH2 (acetamide), and R-C=N (nitriles). Several of these are already known to be in the interstellar medium, and their presence indicates the importance of grain processing. After warming to room temperature an organic residue remains. This is composed primarily of hexamethylenetetramine (HMT, C6H12N4), with lesser amounts of polyoxymethylene-related species (POMs), amides, and ketones. This is in sharp contrast to the organic residues produced by irradiating unrealistic interstellar ice analogs or thermally promoted polymerization-type reactions in unirradiated realistic ice mixtures.

Uptake of HNO3 on water-ice and coadsorption of HNO3 and HCl in the temperature range 210-235 K

NASA Astrophysics Data System (ADS)

Hynes, Robert G.; Fernandez, Miguel A.; Cox, R. Anthony

2002-12-01

The uptake of HNO3 on water-ice films was investigated in a coated wall flow reactor under tropospheric temperature conditions. Experiments were performed in the "ice" region of the HNO3-H2O phase diagram. With HNO3 partial pressures in the range of (0.3-2.0) × 10-6 Torr, continuous uptake was observed below 215 K; whereas above 215 K, the uptake was time dependent. Using the geometric surface area of the ice film, the surface coverage at 218 K was 3.0 × 1014 molecules/cm2, decreasing to 1.5 × 1014 molecules/cm2 at 233 K; the timescales for saturation were 700 and 800 s at 218 and 233 K, respectively. The surface coverage was found to change by a factor of 2 over a 10-fold change in HNO3 partial pressure. By assuming that the surface coverage can be represented by a Langmuir isotherm for dissociative adsorption, the enthalpy of adsorption of HNO3 onto ice was found to be -(54.0 ± 2.6) kJ/mol. At a constant HNO3 partial pressure, the maximum uptake coefficients, γ, were measured as a function of temperature, decreasing from 0.03 at 215 K down to 0.006 at 235 K. The uptake coefficients at 218 K were not significantly affected by changes in HNO3 partial pressure. The uptake of HCl at 218 K on ice surfaces previously dosed with HNO3 was found to be reversible, and the coadsorption of HNO3 with HCl indicates that HCl is displaced from surface sites by HNO3 molecules. Uptake of HNO3 on HCl-dosed surfaces showed that HNO3 molecules displace ˜1013 molecules/cm3 of HCl. The efficiency of cirrus clouds in scavenging HNO3 is discussed, as well as the implications for chlorine activation reactions under tropospheric temperature conditions.

Surface temperatures and retention of H2O frost on Ganymede and Callisto

NASA Technical Reports Server (NTRS)

Squyres, S. W.

1980-01-01

Surface temperatures and ice evaporation rates are calculated for Ganymede and Callisto as functions of latitude, time of day, and albedo, according to a model that uses surface thermal properties determined by eclipse radiometry and albedos determined from photometrically decalibrated Voyager images. The difference in temperature between Ganymede and Callisto is not great enough to account for the lack of bright polar caps on Callisto, which seems instead to reflect a real deficiency in the amount of available water frost relative to Ganymede. The temperature difference between Ganymede's grooved and cratered terrains also cannot account for the high concentration of bright ray craters in the former, suggesting that an internal geologic process has enriched the grooved terrain in ice content relative to the cratered terrain.

X-ray-induced dissociation of H.sub.2O and formation of an O.sub.2-H.sub.2 alloy at high pressure

DOEpatents

Mao, Ho-kwang [Washington, DC; Mao, Wendy L [Washington, DC

2011-11-29

A novel molecular alloy of O.sub.2 and H.sub.2 and a method of producing such a molecular alloy are provided. When subjected to high pressure and extensive x-radiation, H.sub.2O molecules cleaved, forming O--O and H--H bonds. In the method of the present invention, the O and H framework in ice VII was converted into a molecular alloy of O.sub.2 and H.sub.2. X-ray diffraction, x-ray Raman scattering, and optical Raman spectroscopy demonstrate that this crystalline solid differs from previously known phases.

Ozone Production in Irradiated Laboratory Ices Relevant to Europa and Ganymede

NASA Astrophysics Data System (ADS)

Cooper, P. D.; Moore, M. H.; Hudson, R. L.

2005-08-01

Observations suggest ozone (O3) is present on the icy surfaces of Ganymede (1), and Rhea and Dione (2). Molecular oxygen (O2) has also been observed on Europa (3) and Ganymede (4). The formation and trapping of such molecules in ice and their subsequent transportation to a sub-surface ocean may be potentially important for sustaining astrobiological life (5). It is assumed that ozone is produced in these icy surfaces by the addition of an oxygen atom to molecular oxygen, with the latter formed by prior irradiation of the water ice. The infrared absorption band of ozone in ice at 1037 cm-1 is strong and thus makes ozone a good tracer for the presence of molecular oxygen which is difficult to detect. We will present results of water/oxygen ices irradiated with 800 keV protons and show the band position and growth of ozone with increasing radiation dose. The thermal stability of this radiolytically-produced ozone has also been measured and comparisons made to the Jovian satellites. P. Cooper is grateful for the support from the National Academies Research Associateship Program. (1) Noll, K.S., Johnson, R.E., Lane, A.L., Domingue, D.L., Weaver, H.A., Science, 273, 341-343, (1996). (2) Noll, K.S., Roush, T.L., Cruikshank, D.P., Johnson, R.E., Pendleton, Y.J., Nature, 388, 45-47, (1997). (3) Spencer, J.R., Calvin, W.M., Astron. J., 124, 3400-3403, (2002). (4) Spencer, J.R., Calvin, W.M., Person, M. J., J. Geo. Res. 100 (E9), 19049-19056 (1995). (5) Chyba, C.F., Hand, K.P., Science, 292, 2026-2027, (2001).

Structure, spectroscopy and dynamics of layered H2O and CO2 ices

USGS Publications Warehouse

,; Plattner, Nuria; Meuwly, Markus

2012-01-01

Molecular dynamics simulations of structural, spectroscopic and dynamical properties of mixed water–carbon dioxide (H2O–CO2) ices are discussed over temperature ranges relevant to atmospheric and astrophysical conditions. The simulations employ multipolar force fields to represent electrostatic interactions which are essential for spectroscopic and dynamical investigations. It is found that at the water/CO2 interface the water surface acts as a template for the CO2 component. The rotational reorientation times in both bulk phases agree well with experimental observations. A pronounced temperature effect on the CO2 reorientation time is observed between 100 K and 200 K. At the interface, water reorientation times are nearly twice as long compared to water in the bulk. The spectroscopy of such ices is rich in the far-infrared region of the spectrum and can be related to translational and rotational modes. Furthermore, spectroscopic signatures mediated across the water/CO2 interface are found in this frequency range (around 440 cm−1). These results will be particularly important for new airborne experiments such as planned for SOFIA.

Electron and Ion Reactions in Molecular Solids: from astrochemistry to radiobiology

NASA Astrophysics Data System (ADS)

Huels, Michael A.

2001-05-01

Wherever ionizing radiation interacts with matter, it initiates reaction cascades involving ions, radicals, and ballistic secondary electrons; these reactions occur on fs time-scales, and may lead to substantial physical and chemical modifications of a medium. Here I present measurements of 0-80 eV electron and ion reactions in condensed films ranging from simple to complex, and astrophysical to biological in nature. Targets contain either: small molecules, hydrocarbons of increasing complexity (incl. bases, sugars, single/double stranded DNA), molecules on rare gas matrices, or mixed cryogenic films resembling astrophysical or planetary surface ices containing O2, H2O, methane, and aromatic hydrocarbons. The basic electron or ion reaction mechanisms and pathways are found to be fundamentally universal, but are modulated by the physical and chemical nature of the medium; depending on the latter, a reaction cascade may lead to different end-points, e.g. a decrease in molecular complexity via molecular fragmentations, or increases in complexity via secondary ion collision induced synthesis of larger molecules in hydrocarbon rich surface ices.

Searching for Clues to the Processes and Conditions of Past Martian Environments: The Roles of Episodic Solutions, Analog Sites and Fe-O(-H) Phases

NASA Astrophysics Data System (ADS)

King, P. L.; De Deckker, P.

2012-12-01

On Mars, limited solutions (water/brine) were likely present episodically. Gradients in solution abundance may have caused salt precipitation and re-solution, brine reflux, pH gradients, and cycling of anions and cations; we provide an example of such processes in a playa lake. We propose that on Mars, the limited, episodic solutions, pH and abundant Fe-O(-H) phases are significant factors in salt precipitation and in promoting adsorption/desorption of anions and cations. FACTORS LEADING TO EPISODIC SOLUTIONS: Episodic movement of solutions may be driven by punctuated processes that 1) remove surface materials (e.g., impact and sedimentary mass wasting and deflation); 2) add surface materials (e.g., impact, volcanic and sedimentary processes); and 3) increase temperature and/or decrease atmospheric pressure (e.g., seasons, diurnal cycles, variation in obliquity). Removal and addition of surface materials results in topographic gradients that change pressure gradients of any potential groundwater, films, or buried ground ice. For example, episodic fluid flow and salt precipitation/re-solution may occur at topographic discontinuities like craters/basins, channel walls, mounds and dunes. Such areas provide the opportunity to sample multiple fluid sources (with different pH, Eh and total dissolved solids, TDS) and they may be the foci of subsurface solution flow and surface transport. EARTH ANALOG: Interplay of the three processes above is seen in Lake Tyrrell (playa), western Victoria, Australia (McCumber, P, 1991 http://vro.dpi.vic.gov.au). During wetter periods, springs from the regional groundwater (low pH, oxidized, mod-high TDS) mix with lake waters and saline 'reflux' brines (mod. pH, reduced, high TDS) at the lake edge at the base of higher ground. The Br/Cl of the reflux brines indicates mineral re-solution. Gypsum and Fe-O(-H) phases precipitate near the lake edge. During hot, dry climate episodes the lake precipitates gypsum and carbonate, efflorescent salts are common, and these salts may form eolian dunes with fine particles. We may expect similar processes and mineral and chemical gradients in craters/basins on Mars like Gale Crater, the site of the Mars Science Laboratory mission. ROLE OF Fe-O(-H) PHASES: Nanophase Fe-O(-H)-phases are abundant on Mars and their precipitation results in an Fe-poor solution and salts (like Lake Tyrrell). Fe-O(-H) phases precipitate most readily at near-neutral pH; however, the high Fe of Mars' surface allows for pH>1. Nanophase Fe-O(-H)-phases have surface species that promote adsorption; which may be important in dry conditions like Mars. If we take goethite (FeO(OH)), the surface species and aqueous ions in solution are Fe3+ (pH<~2); Fe(OH)2+ (pH~2-3.5); Fe(OH)2+ (pH~3.5-~8); and FeOH4- (pH>~8). Other Fe-O(-H) phases have slightly different pH limits. Thus, at pH<~8, Fe-O(-H) surfaces sequester anions in surface complexes or in Fe-bearing salts (e.g. Fe3+-phosphate and sulfates, especially at pH<4). PO43- species have high adsorption affinity, followed by SO42-, Cl-(O) and Br-(O) species. At pH>~8, adsorption and exchange of cations are likely. These chemical variations may provide us with clues of the past pH on Mars.

Space Weathering on Icy Satellites in the Outer Solar System

NASA Technical Reports Server (NTRS)

Clark, R. N.; Perlman, Z.; Pearson, N.; Cruikshank, D. P.

2014-01-01

Space weathering produces well-known optical effects in silicate minerals in the inner Solar System, for example, on the Moon. Space weathering from solar wind and UV (ultraviolet radiation) is expected to be significantly weaker in the outer Solar System simply because intensities are low. However, cosmic rays and micrometeoroid bombardment would be similar to first order. That, combined with the much higher volatility of icy surfaces means there is the potential for space weathering on icy outer Solar System surfaces to show optical effects. The Cassini spacecraft orbiting Saturn is providing evidence for space weathering on icy bodies. The Cassini Visible and Infrared Mapping Spectrometer (VIMS) instrument has spatially mapped satellite surfaces and the rings from 0.35-5 microns and the Ultraviolet Imaging Spectrograph (UVIS) instrument from 0.1 to 0.2 microns. These data have sampled a complex mixing space between H2O ice and non-ice components and they show some common spectral properties. Similarly, spectra of the icy Galilean satellites and satellites in the Uranian system have some commonality in spectral properties with those in the Saturn system. The UV absorber is spectrally similar on many surfaces. VIMS has identified CO2, H2 and trace organics in varying abundances on Saturn's satellites. We postulate that through the spatial relationships of some of these compounds that they are created and destroyed through space weathering effects. For example, the trapped H2 and CO2 observed by VIMS in regions with high concentrations of dark material may in part be space weathering products from the destruction of H2O and organic molecules. The dark material, particularly on Iapetus which has the highest concentration in the Saturn system, is well matched by space-weathered silicates in the .4 to 2.6 micron range, and the spectral shapes closely match those of the most mature lunar soils, another indicator of space weathered material.

Methanol Formation via Oxygen Insertion Chemistry in Ices

NASA Astrophysics Data System (ADS)

Bergner, Jennifer B.; Öberg, Karin I.; Rajappan, Mahesh

2017-08-01

We present experimental constraints on the insertion of oxygen atoms into methane to form methanol in astrophysical ice analogs. In gas-phase and theoretical studies this process has previously been demonstrated to have a very low or nonexistent energy barrier, but the energetics and mechanisms have not yet been characterized in the solid state. We use a deuterium UV lamp filtered by a sapphire window to selectively dissociate O2 within a mixture of O2:CH4 and observe efficient production of CH3OH via O(1D) insertion. CH3OH growth curves are fit with a kinetic model, and we observe no temperature dependence of the reaction rate constant at temperatures below the oxygen desorption temperature of 25 K. Through an analysis of side products we determine the branching ratio of ice-phase oxygen insertion into CH4: ˜65% of insertions lead to CH3OH, with the remainder leading instead to H2CO formation. There is no evidence for CH3 or OH radical formation, indicating that the fragmentation is not an important channel and that insertions typically lead to increased chemical complexity. CH3OH formation from O2 and CH4 diluted in a CO-dominated ice similarly shows no temperature dependence, consistent with expectations that insertion proceeds with a small or nonexistent barrier. Oxygen insertion chemistry in ices should therefore be efficient under low-temperature ISM-like conditions and could provide an important channel to complex organic molecule formation on grain surfaces in cold interstellar regions such as cloud cores and protoplanetary disk midplanes.

Physical state and temporal evolution of icy surfaces in the Mars South Pole

NASA Astrophysics Data System (ADS)

Douté, S.; Pilorget, C.

2017-09-01

On Mars H2O and CO2 ices can be found as seasonal or perennial deposits notably in the polar regions. Their bidirectional reflectance factor (BRF) is a tracer of their evolution which is still not completely understood. It is a key parameter for characterizing the composition and the physical state, as well as for calculating the bolometric albedo, the energy balance of the icy surfaces, and thus their impact on the martian climate. The BRF is potentially accessible thanks to the near-simultaneous multi-angle, hyperspectral observations of the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) implying 11 viewing angles in visible and infrared ranges. In previous research (Ceamanos2013, Doute2015) we put forward the Multi-angle Approach for Retrieval of Surface Reflectance from CRISM Observations (MARS-ReCO), an algorithm that characterizes and corrects the aerosol scattering effects. The aerosol optical depth (AOD) and the BRF of surface materials are retrieved conjointly and coherently as a function of wavelength. In this work, we apply MARS-ReCO on time series of CRISM sequences over different regions of interest in the outskirts of the south permanent polar cap. The time series span from mid-spring to late summer (Ls=210-320*) during which the CO2 ice sublimates sometimes revealing H2O frost and defrosted terrains. Thanks to the atmospheric correction, we are able to identify various classes of spectrophotometric behavior. We also note a regular increase of the directional-hemispherical surface albedo during the period of the time.

Radiolytic Gas-Driven Cryovolcanism in the Outer Solar System

NASA Technical Reports Server (NTRS)

Cooper, John F.; Cooper, Paul D.; Sittler, Edward C.; Sturner, Steven J.; Rymer, Abigail M.; Hill, Matthew E.

2007-01-01

Water ices in surface crusts of Europa, Enceladus, Saturn's main rings, and Kuiper Belt Objects can become heavily oxidized from radiolytic chemical alteration of near-surface water ice by space environment irradiation. Oxidant accumulations and gas production are manifested in part through observed H2O2 on Europa. tentatively also on Enceladus, and found elsewhere in gaseous or condensed phases at moons and rings of Jupiter and Saturn. On subsequent chemical contact in sub-surface environments with significant concentrations of primordially abundant reductants such as NH3 and CH4, oxidants of radiolytic origin can react exothermically to power gas-driven cryovolcanism. The gas-piston effect enormously amplifies the mass flow output in the case of gas formation at basal thermal margins of incompressible fluid reservoirs. Surface irradiation, H2O2 production, NH3 oxidation, and resultant heat, gas, and gas-driven mass flow rates are computed in the fluid reservoir case for selected bodies. At Enceladus the oxidant power inputs are comparable to limits on nonthermal kinetic power for the south polar plumes. Total heat output and plume gas abundance may be accounted for at Enceladus if plume activity is cyclic in high and low "Old Faithful" phases, so that oxidants can accumulate during low activity phases. Interior upwelling of primordially abundant NH3 and CH4 hydrates is assumed to resupply the reductant fuels. Much lower irradiation fluxes on Kuiper Belt Objects require correspondingly larger times for accumulation of oxidants to produce comparable resurfacing, but brightness and surface composition of some objects suggest that such activity may be ongoing.

Calcium carbonate as ikaite crystals in Antarctic sea ice

NASA Astrophysics Data System (ADS)

Dieckmann, Gerhard S.; Nehrke, Gernot; Papadimitriou, Stathys; Göttlicher, Jörg; Steininger, Ralph; Kennedy, Hilary; Wolf-Gladrow, Dieter; Thomas, David N.

2008-04-01

We report on the discovery of the mineral ikaite (CaCO3.6H2O) in sea-ice from the Southern Ocean. The precipitation of CaCO3 during the freezing of seawater has previously been predicted from thermodynamic modelling, indirect measurements, and has been documented in artificial sea ice during laboratory experiments but has not been reported for natural sea-ice. It is assumed that CaCO3 formation in sea ice may be important for a sea ice-driven carbon pump in ice-covered oceanic waters. Without direct evidence of CaCO3 precipitation in sea ice, its role in this and other processes has remained speculative. The discovery of CaCO3.6H2O crystals in natural sea ice provides the necessary evidence for the evaluation of previous assumptions and lays the foundation for further studies to help elucidate the role of ikaite in the carbon cycle of the seasonally sea ice-covered regions

UV Signatures of Ices: Moons in the Solar System

NASA Astrophysics Data System (ADS)

Hendrix, A. R.; Hansen, C. J.; Retherford, K. D.; Vilas, F.

2017-12-01

Using Earth-orbiting telescopes such as the International Ultraviolet Explorer and the Hubble Space Telescope, significant advances have been made in the area of ultraviolet observations of solar system objects. More in-depth studies have been made using interplanetary probes such as Galileo, Cassini and Lunar Reconnaissance Orbiter (LRO). While the UV spectral range has traditionally been used to study atmospheric and auroral processes, there is much to be learned by examining solid surfaces in the UV, including surface composition, weathering processes and effects, and the generation of thin atmospheres. Here we focus on moons in the solar system, including Earth's moon and the Saturnian satellites. The diagnostic UV signature of H2O is used to study ice in the lunar polar regions as well as hydration at lower latitudes, in observations from LRO LAMP. The water ice signature is nearly ubiquitous in the Saturn system; Cassini UVIS datasets are used to study grain sizes, exogenic processes/effects and non-ice species.

Pathways to Oxygen-Bearing Molecules in the Interstellar Medium and in Planetary Atmospheres: Cyclopropenone (c-C3H2O) and Propynal (HCCCHO)

NASA Astrophysics Data System (ADS)

Zhou, Li; Kaiser, Ralf I.; Gao, Li Gyun; Chang, Agnes H. H.; Liang, Mao-Chang; Yung, Yuk L.

2008-10-01

We investigated the formation of two C3H2O isomers, i.e., cyclopropenone (c-C3H2O) and propynal (HCCCHO), in binary ice mixtures of carbon monoxide (CO) and acetylene (C2H2) at 10 K in an ultrahigh vacuum machine on high-energy electron irradiation. The chemical evolution of the ice samples was followed online and in situ via a Fourier transform infrared spectrometer and a quadrupole mass spectrometer. The temporal profiles of the cyclopropenone and propynal isomers suggest (pseudo-) first-order kinetics. The cyclic structure (c-C3H2O) is formed via an addition of triplet carbon monoxide to ground-state acetylene (or vice versa); propynal (HCCCHO) can be synthesized from a carbon monoxide-acetylene complex via a [HCO...CCH] radical pair inside the matrix cage. These laboratory studies showed for the first time that both C3H2O isomers can be formed in low-temperature ices via nonequilibrium chemistry initiated by energetic electrons as formed in the track of Galactic cosmic ray particles penetrating interstellar icy grains in cold molecular clouds. Our results can explain the hitherto unresolved gas phase abundances of cyclopropenone in star-forming regions via sublimation of c-C3H2O as formed on icy grains in the cold molecular cloud stage. Implications for the heterogeneous oxygen chemistry of Titan and icy terrestrial planets and satellites suggest that the production of oxygen-bearing molecules such as C3H2O may dominate on aerosol particles compared to pure gas phase chemistry.

Limits to Ice on Asteroids (24) Themis and (65) Cybele

NASA Astrophysics Data System (ADS)

Jewitt, David; Guilbert-Lepoutre, Aurelie

2012-01-01

We present optical spectra of (24) Themis and (65) Cybele, two large main-belt asteroids on which exposed water ice has recently been reported. No emission lines, expected from resonance fluorescence in gas sublimated from the ice, were detected. Derived limits to the production rates of water are lsim400 kg s-1 (5σ) for each object, assuming a cometary H2O/CN ratio. We rule out models in which a large fraction of the surface is occupied by high-albedo ("fresh") water ice because the measured albedos of Themis and Cybele are low (~0.05-0.07). We also rule out models in which a large fraction of the surface is occupied by low-albedo ("dirty") water ice because dirty ice would be warm and would sublimate strongly enough for gaseous products to have been detected. If ice exists on these bodies it must be relatively clean (albedo gsim0.3) and confined to a fraction of the Earth-facing surface lsim10%. By analogy with impacted asteroid (596) Scheila, we propose an impact excavation scenario, in which 10 m scale projectiles have exposed buried ice. If the ice is even more reflective (albedo gsim0.6), then the timescale for sublimation of an optically thick layer can rival the ~103 yr interval between impacts with bodies this size. In this sense, exposure by impact may be a quasi steady-state feature of ice-containing asteroids at 3 AU.

Freezing of perchlorate and chloride brines under Mars-relevant conditions

NASA Astrophysics Data System (ADS)

Primm, K. M.; Gough, R. V.; Chevrier, V. F.; Tolbert, M. A.

2017-09-01

Perchlorate and chloride salts on Mars could readily absorb water vapor and deliquesce into aqueous solutions. The deliquescence relative humidity (RH) as well as the efflorescence (recrystallization) RH of several Mars-relevant salts are now well known; however, the conditions that could cause a brine to freeze are not well established. It is often assumed that ice formation will occur whenever the saturation with respect to ice, Sice, of the system is greater than or equal to unity; however, ice nucleation is often hindered due to a kinetic barrier. For ice to form, a critical cluster of the ice crystal must first be achieved, often requiring Sice > 1. Here we use a Raman microscope and an environmental cell to examine the RH and temperature conditions required for Mg(ClO4)2 and MgCl2 brines to freeze into ice. By examining the salt phase present both optically and spectrally under different low temperature conditions, it is found that both salts exhibit Sice values much greater than unity, meaning that supersaturation readily occurs and brines can persist under conditions previously thought to lead to freezing. The RH range of ice formation for Mg(ClO4)2 from 218 to 245 K is 83-95%, respectively, corresponding to Sice = 1.30-1.54. The RH of ice formation for MgCl2 ranges from 80 to 100% for temperatures between 221 and 252 K, corresponding to Sice = 1.30-1.35. In addition to ice nucleation, the deliquescence and efflorescence relative humidity values for MgCl2 were determined. Two hydrates for MgCl2 were observed, and exhibited different deliquescence relative humidity (DRH) values. The DRH for MgCl2·4H2O was found to be 12.8 ± 0.3% at 243 K with slightly increasing DRH as temperature decreased. The DRH for MgCl2·6H2O was found to be 31.3 ± 0.6% at 242 K with little temperature dependence. The DRH of MgCl2·6H2O was measured below the previously reported eutectic, 240 K, suggesting that the eutectic might be incorrect or that there is a different relevant hydration state. The aqueous solutions of MgCl2 recrystallized to the tetrahydrate at low RH in the range of 3-9% RH at temperatures 265-235 K. Together, the ice nucleation, DRH, and efflorescence relative humidity (ERH) results show that Mg(ClO4)2 and MgCl2 brines on present day Mars may have the ability to exist for up to 2 h longer than previously predicted.

Water Structure and Dynamics in Smectites: X-ray Diffraction and 2 H NMR Spectroscopy of Mg–, Ca–, Sr–, Na–, Cs–, and Pb–Hectorite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reddy, U. Venkateswara; Bowers, Geoffrey M.; Loganathan, Narasimhan

2016-04-06

Variable-temperature X-ray diffraction and 2H NMR spectroscopy of the smectite mineral, hectorite, containing interlayer Na +, K +, Cs +, Mg 2+, Ca 2+, Sr 2+, and Pb 2+ equilibrated at 43% relative humidity (RH) and mixed with 2H 2O to form a paste provide a comprehensive picture of the structural environments and dynamics of interlayer 2H 2O and the relationships of these properties to interlayer hydration state, the hydration energy and polarizability of the cation, temperature, and the formation of ice-1h in the interparticle pores. The variation in basal spacing shown by the XRD data correlates well with themore » 2H NMR behavior, and the XRD data show for the first time in hectorites that crystallization of interparticle ice-1h causes a decrease in the interlayer spacing, likely due to removal of interlayer 2H 2O. The variation of the 2H NMR behavior of all the samples with decreasing temperature reflects decreasing frequencies of motion for the rotation of the 2H 2O molecules around their dipoles, reorientation of the 2H 2O molecules, and exchange of the 2H 2O molecules between interlayer sites coordinated to and not coordinated to the cations.« less

Radar images of Mars

NASA Technical Reports Server (NTRS)

Muhleman, Duane O.; Butler, Bryan J.; Grossman, Arie W.; Slade, Martin A.

1991-01-01

VLA radar-reflected flux-density mappings have yielded full disk images of Mars which reveal near-surface features, including a region in the Tharsis volcano area that displayed no echo to the very low level of the radar-system noise. This feature is interpreted as a deposit of dust or ash whose density is less than about 0.5 g/cu cm; it must be several meters thick, and may be much deeper. The most strongly reflecting geological feature was the south polar ice cap, which is interpretable as arising from nearly-pure CO2 or H2O ice, with less than 2 vol pct Martian dust. Only one anomalous reflecting feature was identified outside the Tharsis region.

The role of water in gas hydrate dissociation

USGS Publications Warehouse

Circone, S.; Stern, L.A.; Kirby, S.H.

2004-01-01

When raised to temperatures above the ice melting point, gas hydrates release their gas in well-defined, reproducible events that occur within self-maintained temperature ranges slightly below the ice point. This behavior is observed for structure I (carbon dioxide, methane) and structure II gas hydrates (methane-ethane, and propane), including those formed with either H2O- or D2O-host frameworks, and dissociated at either ambient or elevated pressure conditions. We hypothesize that at temperatures above the H2O (or D2O) melting point: (1) hydrate dissociation produces water + gas instead of ice + gas, (2) the endothermic dissociation reaction lowers the temperature of the sample, causing the water product to freeze, (3) this phase transition buffers the sample temperatures within a narrow temperature range just below the ice point until dissociation goes to completion, and (4) the temperature depression below the pure ice melting point correlates with the average rate of dissociation and arises from solution of the hydrate-forming gas, released by dissociation, in the water phase at elevated concentrations. In addition, for hydrate that is partially dissociated to ice + gas at lower temperatures and then heated to temperatures above the ice point, all remaining hydrate dissociates to gas + liquid water as existing barriers to dissociation disappear. The enhanced dissociation rates at warmer temperatures are probably associated with faster gas transport pathways arising from the formation of water product.

Evolution of CO2, CH4, and OCS abundances relative to H2O in the coma of comet 67P around perihelion from Rosetta/VIRTIS-H observations

NASA Astrophysics Data System (ADS)

Bockelée-Morvan, Dominique; Crovisier, J.; Erard, S.; Capaccioni, F.; Leyrat, C.; Filacchione, G.; Drossart, P.; Encrenaz, T.; Biver, N.; de Sanctis, M.-C.; Schmitt, B.; Kührt, E.; Capria, M.-T.; Combes, M.; Combi, M.; Fougere, N.; Arnold, G.; Fink, U.; Ip, W.; Migliorini, A.; Piccioni, G.; Tozzi, G.

2016-11-01

Infrared observations of the coma of 67P/Churyumov-Gerasimenko were carried out from 2015 July to September, I.e. around perihelion (2015 August 13), with the high-resolution channel of the Visible and Infrared Thermal Imaging Spectrometer instrument onboard Rosetta. We present the analysis of fluorescence emission lines of H2O, CO2, 13CO2, OCS, and CH4 detected in limb sounding with the field of view at 2.7-5 km from the comet centre. Measurements are sampling outgassing from the illuminated Southern hemisphere, as revealed by H2O and CO2 raster maps, which show anisotropic distributions, aligned along the projected rotation axis. An abrupt increase of water production is observed 6 d after perihelion. In the meantime, CO2, CH4, and OCS abundances relative to water increased by a factor of 2 to reach mean values of 32, 0.47, and 0.18 per cent, respectively, averaging post-perihelion data. We interpret these changes as resulting from the erosion of volatile-poor surface layers. Sustained dust ablation due to the sublimation of water ice maintained volatile-rich layers near the surface until at least the end of the considered period, as expected for low thermal inertia surface layers. The large abundance measured for CO2 should be representative of the 67P nucleus original composition, and indicates that 67P is a CO2-rich comet. Comparison with abundance ratios measured in the Northern hemisphere shows that seasons play an important role in comet outgassing. The low CO2/H2O values measured above the illuminated Northern hemisphere are not original, but the result of the devolatilization of the uppermost layers.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bolmatov, Dima; Zhernenkov, Mikhail; Zav’yalov, Dmitry

Here in this work we report on terahertz phononic excitations in 2D gold nanoparticle arrays in a water matrix through a series of large-scale molecular dynamics simulations. For the first time, we observe acoustic Dirac-like crossings in H (H 2O) atomic (molecular) networks which emerge due to an intraband phononic scattering. These crossings are the phononic fingerprints of ice-like arrangements of H (H 2O) atomic (molecular) networks at nanometer scale. We reveal how phononic excitations in metallic nanoparticles and the water matrix reciprocally impact on one another providing the mechanism for the THz phononics manipulation via structural engineering. In addition,more » we show that by tuning the arrangement of 2D gold nanoparticle assemblies the Au phononic polarizations experience sub-terahertz hybridization (Kohn anomaly) due to surface electron-phonon relaxation processes. This opens the way for the sound control and manipulation in soft matter metamaterials at nanoscale.« less

Arctic Marine Water Isotope Characteristics: In-situ, Continuous Surface and Water Column Isoscapes (δ18O and δ2H) and Linkages into the Marine Food Web

NASA Astrophysics Data System (ADS)

Welker, J. M.; Klein, E. S.; Collins, E.; Iken, K.; Hopcroft, R. R.; Norcross, B.

2016-12-01

The Arctic is under going rapid and profound sea ice, temperature, food web, ocean current, precipitation and synoptic weather changes. Delineating these changes requires a suite of tools, especially those that have the ability to depict the interactive nature of the marine system. Understanding the marine water isotope cycle is paramount to recognizing the unique isotopic properties of this region and to characterize possibly the reorganization of the Arctic. The Arctic marine water isotope system has been primarily examined with shore-based stations and or episodic station sampling; without continuous surface water sampling in combination with station-specific water column and organismic measurements. New technologies that allow in situ and continuous water isotope measurements (vapor and liquid) and the integration of inorganic and organic water isotope geochemistry provide a means to reveal in more detail the fundamental traits of the Arctic marine water isotope system. In July and August of 2016, we are measuring seawater surface (8 m depth) isotopes (δ18O and δ2H) in-situ and continuously (Picarro CWS system) along a research transect (60oN to 77oN) from the Gulf of Alaska to the Arctic Ocean Basin. These continuous surface water isotope measurements are being combined with periodic water column isotope profiling and corresponding organic δ18O and δ2H measurements of pelagic and benthic organisms (microbes to fish) to depths of up to 2600m. We measured surface seawater δ18O that from -1‰ to -6‰; while seawater profiles followed vertical separation in the water column; possibly reflecting divergent currents of the Arctic. Station based δ18O and δ2H values of surface water did not vary by more than 1‰ δ18O over the course of our 24-36 hour sampling periods. The δ18O and δ2H values of marine organism throughout the water column and by trophic level will be analyzed and a seawater-food web model will be developed in addition to surface and water column isoscapes. Our Arctic marine water isotope cycle research is providing the most detailed depiction ever of the western Arctic and sub-Arctic surface water, water column and marine food web O/H isotope properties. Our findings will provide an important new understanding of the Arctic and the high definition of its water isotope cycle.

Hydration of polar and nonpolar molecules at the surface of amorphous solid water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Souda, Ryutaro

2004-10-15

On the basis of time-of-flight secondary ion mass spectrometry, properties of amorphous solid water above the glass transition temperature (136 K) and the hydration of polar (HCOOH,C{sub 3}H{sub 7}OH) and nonpolar (C{sub 6}H{sub 14},C{sub 6}F{sub 14}) molecules on the D{sub 2}O-ice surface have been investigated. No evidence was obtained for the irreversible transition of the amorphous solid water into the crystalline phase: the self-diffusion of water molecules occurs above 140 K irrespective of the preparation temperatures of the water-ice film ranging from 15 K to 165 K, whereas the morphology of the film changes drastically at 165 K due tomore » the evolution of liquidlike water. It is also demonstrated that the change in conformation of the hydrated HCOOH molecule, as well as the occurrence of hydrophilic/hydrophobic hydration of the C{sub 3}H{sub 7}OH molecule, can be analyzed successfully from the temperature evolutions of the secondary-ion intensities. These polar molecules basically stay on the surface and tend to quench the morphological change of the water film due to the reduction of surface tension. The nonpolar C{sub 6}H{sub 14} and C{sub 6}F{sub 14} molecules readily dissolve in the D{sub 2}O layer below 100 K and dehydration of the incorporated molecules occurs at 165 K concomitantly with the evolution of the liquidlike water. It is thus concluded that the hydrophobic hydration of nonpolar molecules is intimately related to the properties of water films.« less

Glycine's radiolytic destruction in ices: first in situ laboratory measurements for Mars.

PubMed

Gerakines, Perry A; Hudson, Reggie L

2013-07-01

We report new laboratory studies of the radiation-induced destruction of glycine-containing ices for a range of temperatures and compositions that allow extrapolation to martian conditions. In situ infrared spectroscopy was used to study glycine decay rates as a function of temperature (from 15 to 280 K) and initial glycine concentrations in six mixtures whose compositions ranged from dry glycine to H2O+glycine (300:1). Results are presented in several systems of units, with cautions concerning their use. The half-life of glycine under the surface of Mars is estimated as an extrapolation of this data set to martian conditions, and trends in decay rates are described as are applications to Mars' near-surface chemistry.

Characterizing of a Mid-Latitude Ice-Rich Landing Site on Mars to Enable in Situ Habitability Studies

NASA Technical Reports Server (NTRS)

Heldmann, J.; Schurmeier, L. R.; Wilhelm, M.; Stoker, C.; McKay, C.; Davila, A.; Marinova, M.; Karcz, J.; Smith, H.

2012-01-01

We suggest an ice-rich landing site at 188.5E 46.16N within Amazonis Planitia as a candidate location to support a Mars lander mission equipped to study past habitability and regions capable of preserving the physical and chemical signs of life and organic matter. Studies of the ice-rich subsurface on Mars are critical for several reasons. The subsurface environment provides protection from radiation to shield organic and biologic compounds from destruction. The ice-rich substrate is also ideal for preserving organic and biologic molecules and provides a source of H2O for biologic activity. Examination of martian ground ice can test several hypotheses such as: 1) whether ground ice supports habitable conditions, 2) that ground ice can preserve and accumulate organic compounds, and 3) that ice contains biomolecules evident of past or present biological activity on Mars. This Amazonis site, located near the successful Viking Lander 2, shows indirect evidence of subsurface ice (ubiquitous defined polygonal ground, gamma ray spectrometer hydrogen signature, and numerical modeling of ice stability) and direct evidence of exposed subsurface ice. This site also provides surface conditions favorable to a safe landing including no boulders, low rock density, minimal rough topography, and few craters.

Origin, Bulk Chemical Composition and Physical Structure of the Galilean Satellites of Jupiter: A Post-Galileo Analysis

NASA Technical Reports Server (NTRS)

Prentice, A. J. R.

1999-01-01

The origin of Jupiter and the Galilean satellite system is examined in the light of the new data that has been obtained by the NASA Galileo Project. In particular, special attention is given to a theory of satellite origin which was put forward at the start of the Galileo Mission and on the basis of which several predictions have now been proven successful. These predictions concern the chemical composition of Jupiter's atmosphere and the physical structure of the satellites. According to the proposed theory of satellite origin, each of the Galilean satellites formed by chemical condensation and gravitational accumulation of solid grains within a concentric family of orbiting gas rings. These rings were cast off equatorially by the rotating proto-Jovian cloud (PJC which contracted gravitationally to form Jupiter some 4 1/2 billion years ago. The PJC formed from the gas and grains left over from the gas ring that had been shed at Jupiter's orbit by the contracting proto-solar cloud (PSC Supersonic turbulent convection provides the means for shedding discrete gas rings. The temperatures T (sub n) of the system of gas rings shed by the PSC and PJC vary with their respective mean orbital radii R (sub n) (n = 0, 1,2,...) according as T (sub n) proportional to R (sub n) (exp -0.9). If the planet Mercury condenses at 1640 K, so accounting for the high density of that planet via a process of chemical fractionation between iron and silicates, then T (sub n) at Jupiter's orbit is 158 K. Only 35% of the water vapour condenses out. Thus fractionation between rock and ice, together with an enhancement in the abundance of solids relative to gas which takes place through gravitational sedimentation of solids onto the mean orbit of the gas ring, ensures nearly equal proportions of rock and ice in each of Ganymede and Callisto. Io and Europa condense above the H20 ice point and consist solely of hydrated rock (h-rock). The Ganymedan condensate consists of h-rock and H20 ice. For Callisto, NH3 ice makes up -5% of the condensate mass next to h-rock (approximately 50%) and H2O ice (approximately 45%). Detailed thermal and structural models for each of Europa, Ganymede and Callisto are constructed on the basis of the above initial bulk chemical compositions. For Europa (E), a predicted 2-zone model consisting of a dehydrated rock core of mass 0.912 M (sub E) and a 150 km thick frozen mantle of salty H2O yields a moment-of-inertia coefficient which matches the Galileo Orbiter gravity measurement. For Ganymede (G), a 3-zone model possessing an inner core of solid FeS and mass approximately 0.116 M (sub G), and an outer H2O ice mantle of mass approximately 0.502 M (sub G) is needed to explain the gravity data. Ganymede's native magnetic field was formed by thermoremanent magnetization of Fe3O4. A new Callisto (C) model is proposed consisting of a core of mass 0.826 M (sub C) containing a uniform mixture of h-rock (60% by mass) and H2O and NH3 ices, and capped by a mantle of pure ice. This model may have the capacity to yield a thin layer of liquid NH3 (raised dot) 2H2O at the core boundary, in line with Galileo's discovery of an induced magnetic field.

High pressure ices.

PubMed

Hermann, Andreas; Ashcroft, N W; Hoffmann, Roald

2012-01-17

H(2)O will be more resistant to metallization than previously thought. From computational evolutionary structure searches, we find a sequence of new stable and meta-stable structures for the ground state of ice in the 1-5 TPa (10 to 50 Mbar) regime, in the static approximation. The previously proposed Pbcm structure is superseded by a Pmc2(1) phase at p = 930 GPa, followed by a predicted transition to a P2(1) crystal structure at p = 1.3 TPa. This phase, featuring higher coordination at O and H, is stable over a wide pressure range, reaching 4.8 TPa. We analyze carefully the geometrical changes in the calculated structures, especially the buckling at the H in O-H-O motifs. All structures are insulating--chemistry burns a deep and (with pressure increase) lasting hole in the density of states near the highest occupied electronic levels of what might be component metallic lattices. Metallization of ice in our calculations occurs only near 4.8 TPa, where the metallic C2/m phase becomes most stable. In this regime, zero-point energies much larger than typical enthalpy differences suggest possible melting of the H sublattice, or even the entire crystal.

Anti-icing properties of superhydrophobic ZnO/PDMS composite coating

NASA Astrophysics Data System (ADS)

Yang, Chao; Wang, Fajun; Li, Wen; Ou, Junfei; Li, Changquan; Amirfazli, Alidad

2016-01-01

We present the excellent anti-icing performance for a superhydrophobic coating surface based on ZnO/polydimethylsiloxane (ZnO/PDMS) composite. The superhydrophobic ZnO/PDMS coating surface was prepared by a facile solution mixing, drop coating, room-temperature curing and surface abrading procedure. The superhydrophobic ZnO/PDMS composite coating possesses a water contact angle of 159.5° and a water sliding angle of 8.3° at room temperature (5 °C). The anti-icing properties of the superhydrophobic coating were investigated by continuously dropping cold-water droplets (about 0 °C) onto the pre-cooled surface using a home-made apparatus. The sample was placed at different tilting angle (0° and 10°) and pre-cooled to various temperatures (-5, -10 and -15 °C) prior to measure. The pure Al surface was also studied for comparison. It was found that icing accretion on the surface could be reduced apparently because the water droplets merged together and slid away from the superhydrophobic surface at all of the measuring temperatures when the surface is horizontally placed. In addition, water droplet slid away completely from the superhydrophobic surface at -5 and -10 °C when the surface is tilted at 10°, which demonstrates its excellent anti-icing properties at these temperatures. When the temperature decreased to -15 °C, though ice accretion on the tilted superhydrophobic coating surface could not be avoided absolutely, the amount of ice formed on the surface is very small, which indicated that the coating surface with superhydrophobicity could significantly reduce ice accumulation on the surface at very low temperature (-15 °C). Importantly, the sample is also stable against repeated icing/deicing cycles. More meaningfully, once the superhydrophobic surface is damaged, it can be repaired easily and rapidly.

Transient responses of SFG spectra of D 2O ice/CO/Pt(1 1 1) interface with irradiation of ultra-short NIR pump pulses

NASA Astrophysics Data System (ADS)

Kubota, Jun; Wada, Akihide; Domen, Kazunari; Kano, Satoru S.

2002-08-01

The behavior of D 2O ice on CO/Pt(1 1 1) and Pt(1 1 1) under the irradiation of near-IR pulses (NIR) was studied by sum-frequency generation (SFG) spectroscopy. The peaks assigned to the O-D stretching modes of ice were obtained for the first 30 molecular layers on Pt(1 1 1). When the D2O/ CO/ Pt(1 1 1) was irradiated, the signal of D 2O was weakened after 500 ps, but that of CO was weakened immediately after the pumping. A similar time response was observed for the D 2O peak in D2O/ Pt(1 1 1) . The weakening of SFG is attributed to the broadening of bands due to thermal excitation. This indicates that the energy of the pump pulse is deposited on the Pt(1 1 1) surface and diffused into the layers of D 2O ice in the 500 ps timescale.

A calorimetric study on the low temperature dynamics of doped ice V and its reversible phase transition to hydrogen ordered ice XIII.

PubMed

Salzmann, Christoph G; Radaelli, Paolo G; Finney, John L; Mayer, Erwin

2008-11-07

Doped ice V samples made from solutions containing 0.01 M HCl (DCl), HF (DF), or KOH (KOD) in H(2)O (D(2)O) were slow-cooled from 250 to 77 K at 0.5 GPa. The effect of the dopant on the hydrogen disorder --> order transition and formation of hydrogen ordered ice XIII was studied by differential scanning calorimetry (DSC) with samples recovered at 77 K. DSC scans of acid-doped samples are consistent with a reversible ice XIII <--> ice V phase transition at ambient pressure, showing an endothermic peak on heating due to the hydrogen ordered ice XIII --> disordered ice V phase transition, and an exothermic peak on subsequent cooling due to the ice V --> ice XIII phase transition. The equilibrium temperature (T(o)) for the ice V <--> ice XIII phase transition is 112 K for both HCl doped H(2)O and DCl doped D(2)O. From the maximal enthalpy change of 250 J mol(-1) on the ice XIII --> ice V phase transition and T(o) of 112 K, the change in configurational entropy for the ice XIII --> ice V transition is calculated as 2.23 J mol(-1) K(-1) which is 66% of the Pauling entropy. For HCl, the most effective dopant, the influence of HCl concentration on the formation of ice XIII was determined: on decreasing the concentration of HCl from 0.01 to 0.001 M, its effectiveness is only slightly lowered. However, further HCl decrease to 0.0001 M drastically lowered its effectiveness. HF (DF) doping is less effective in inducing formation of ice XIII than HCl (DCl) doping. On heating at a rate of 5 K min(-1), kinetic unfreezing starts in pure ice V at approximately 132 K, whereas in acid doped ice XIII it starts at about 105 K due to acceleration of reorientation of water molecules. KOH doping does not lead to formation of hydrogen ordered ice XIII, a result which is consistent with our powder neutron diffraction study (C. G. Salzmann, P. G. Radaelli, A. Hallbrucker, E. Mayer, J. L. Finney, Science, 2006, 311, 1758). We further conjecture whether or not ice XIII has a stable region in the water/ice phase diagram, and on a metastable triple point where ice XIII, ice V and ice II are in equilibrium.

Production and optical constraints of ice tholin from charged particle irradiation of (1:6) C2H6/H2O at 77 K

NASA Astrophysics Data System (ADS)

Khare, B. N.; Thompson, W. R.; Cheng, L.; Chyba, C.; Sagan, C.; Arakawa, E. T.; Meisse, C.; Tuminello, P. S.

1993-06-01

Fifty separate irradiations of a 6:1 mixture of H2O/C2H6 ice conducted over a 5-month period have yielded sufficient tholin for the determination of its physical constants in the 0.06 to 40 micron range. While the imaginary part of the refractive index k was obtained by transmission measurements on thin-film samples and Kramers-Kronig analysis (KKA), the real part of the refractive index was obtained by KKA and ellipsometry; these data may prove useful in cometary and outer solar system spectrometric interpretation.

Photosynthesis of Carbon Dioxide from Carbon Surfaces Coated with Oxygen: Implications for Interstellar Molecular Clouds and the Outer Solar System

NASA Astrophysics Data System (ADS)

Fulvio, D.; Raut, U.; Baragiola, R. A.

2012-06-01

We investigate via infrared spectroscopy the synthesis of CO2 by ultraviolet irradiation (6.41 eV) of amorphous carbon covered with solid O2 at 21 K. Oxidation occurs at the O2-carbon interface promoted by photon excitation or dissociation of O2 molecules. The CO2 production is linear with photon fluence with a yield of 3.3 ± 0.3 × 10-5 CO2 photon-1 the yield does not decrease at high fluences (at least up to 2 × 1019 photons cm-2) since CO2 is not photodissociated at this photon energy. Replacing oxygen with water ice did not produce CO2 since H2O does not dissociate at this photon energy. The CO2 synthesis process discussed in this Letter does not require H2O or CO and may be important in cold astrophysical environments where O2 could be locally segregated on carbonaceous grains, such as in molecular clouds and icy objects in the outer solar system.

Ion-Ice Astrochemistry: Barrierless Low-Energy Deposition Pathways to HCOOH, CH3OH, and CO2 on Icy Grain Mantles from Precursor Cations

NASA Technical Reports Server (NTRS)

Woon, David E.

2011-01-01

A new family of very favorable reaction pathways is explored involving the deposition of ions on icy grain mantles with very low energies. Quantum chemical cluster calculations at the MP2/6-31+G** level in 4H2O clusters and at the B3LYP/6-31+G** level in 17H2O clusters indicate that HCO+ and CH3 + are able to react spontaneously with one of the water molecules in the cluster to form protonated formic acid (HCOOH2 +) and protonated methanol (CH3OH2 +), respectively. It is furthermore found that these initial adducts spontaneously transfer their excess protons to the cluster to form neutral formic acid and methanol, plus solvated hydronium, H3O+. In the final case, if a CO molecule is bound to the surface of the cluster, OH+ may react with it to form protonated carbon dioxide (HCO2 +), which then loses its proton to yield CO2 and H3O+. In the present model, all of these processes were found to occur with no barriers. Discussion includes the analogous gas phase processes, which have been considered in previous studies, as well as the competitive abstraction pathway for HCO(+) + H2O.

Facile Generation and Storage of Polycyclic Aromatic Hydrocarbon Ions in Astrophysical Ices

NASA Technical Reports Server (NTRS)

Gudipati, Murthy S.; Allamandola, Louis J.

2003-01-01

In situ ultraviolet-visible absorption and emission studies of vacuum ultraviolet (VUV) irradiated water-rich, cosmic ice analogs containing polycyclic aromatic hydrocarbons (PAHs) are described. W V irradiation of 12 K water ices containing the PAHs naphthalene (H2O/C10H8 = 200) and 4-methylpyrene (H2O/C17H12 > 500) readily converts the PAHs into their cation form (PAH(+)). Under these conditions, PAH photoionization is the predominant reaction. These ions are trapped and stored in the ices at temperatures between 10 and 50 K, a temperature domain common to ices throughout interstellar clouds and the solar system. Unlike the approx.15% ionization typical after W V irradiation of PAHs isolated in rare-gas matrices, in water ice, PAH photoionization and storage proceed efficiently and almost quantitatively with a greater than 70% ionization yield. As the temperature is increased from 50 to 150 K, the PAH ion bands slowly diminish as the PAH ions ultimately react to form more complex organic species involving the water host. The chemical, spectroscopic, and physical properties of these ion-rich ices can be important in icy objects such as molecular clouds, comets, and planets. Several astrophysical applications are presented.

A warmer and wetter solution for early Mars and the challenges with transient warming

NASA Astrophysics Data System (ADS)

Ramirez, Ramses M.

2017-11-01

The climate of early Mars has been hotly debated for decades. Although most investigators believe that the geology indicates the presence of surface water, disagreement has persisted regarding how warm and wet the surface must have been and how long such conditions may have existed. Although the geologic evidence is most easily explained by a persistently warm climate, the perceived difficulty that climate models have in generating warm surface conditions has seeded various models that assume a cold and glaciated early Mars punctuated by transient warming episodes. However, I use a single-column radiative convective climate model to show that it is relatively more straightforward to satisfy warm and relatively non-glaciated early Mars conditions, requiring only ∼1% H2 and 3 bar CO2 or ∼20% H2 and 0.55 bar CO2. In contrast, the reflectivity of surface ice greatly increases the difficulty to transiently warm an initially frozen surface. Surface pressure thresholds required for warm conditions increase ∼10 - 60% for transient warming models, depending on ice cover fraction. No warm solution is possible for ice cover fractions exceeding 40%, 70%, and 85% for mixed snow/ice and 25%, 35%, and 49% for fresher snow/ice at H2 concentrations of 3%, 10%, and 20%, respectively. If high temperatures (298-323 K) were required to produce the observed surface clay amounts on a transiently warm early Mars (Bishop et al), I show that such temperatures would have required surface pressures that exceed available paleopressure constraints for nearly all H2 concentrations considered (1-20%). I then argue that a warm and semi-arid climate remains the simplest and most logical solution to Mars paleoclimate.

Saturn's Icy satellites: The Role of Sub-Micron Ice Particles and Nano-sized Contaminants (Invited)

NASA Astrophysics Data System (ADS)

Clark, R. N.; Cruikshank, D. P.; Dalle Ore, C. M.; Jaumann, R.; Brown, R. H.; Stephan, K.; Buratti, B. J.; Filacchione, G.; Baines, K. H.; Nicholson, P.

2010-12-01

The Visual and Infrared Mapping Spectrometer (VIMS) has obtained spatially resolved imaging spectroscopy data on numerous satellites of Saturn. The spectral trends on individual satellites and as compositional gradients within the Saturn system show systematic trends that indicate variable ice grain sizes and contaminants. Compositional mapping shows that the satellite surfaces are composed largely of H2O ice, with small amounts of CO2, trace organics, bound water or OH-bearing minerals, and possible signatures of ammonia, H2O or OH-bearing minerals, and dark, fine-grained materials. The E-ring coats the inner satellites with sub-micron ice particles. The Cassini Rev 49 Iapetus fly-by on September 10, 2007, provided imaging spectroscopy data on both the dark material and the transition zone between the dark material and the visually bright ice on the trailing side. The dark material has very low albedo with a linear increase in reflectance with wavelength, a 3-micron water absorption, and a CO2 absorption. The only reflectance models that can explain the trends include highly absorbing sub-micron materials that create Rayleigh absorption. Radiative transfer models that include diffraction from Rayleigh scattering and Rayleigh absorption are necessary to match observed data. The dark material is well matched by a high component of fine-grained metallic iron plus a small component of nano-phase hematite. Spatially resolved Iapetus data show mixing of dark material with ice and the mixtures display a blue scattering peak and a UV absorption. The blue scattering peak and UV-Visible absorption is observed in spectra of all satellites at some locations where dark material is mixed with the ice. Rayleigh scattering and Rayleigh absorption have also been observed in spectral properties of the Earth's moon. Rayleigh absorption requires high absorption coefficient nano-sized particles, which is also consistent with metallic iron. The UV absorber appears to have increased strength on satellite surfaces close to Saturn, with a corresponding decrease in metallic iron signature. Possible explanations are that the iron is oxidized closer to Saturn by oxygen in the extended atmosphere of Saturn's rings, or coverage by sub-micron E-ring ice particles, or a combination of both.

Pressure-Induced Melting of Confined Ice.

PubMed

Sotthewes, Kai; Bampoulis, Pantelis; Zandvliet, Harold J W; Lohse, Detlef; Poelsema, Bene

2017-12-26

The classic regelation experiment of Thomson in the 1850s deals with cutting an ice cube, followed by refreezing. The cutting was attributed to pressure-induced melting but has been challenged continuously, and only lately consensus emerged by understanding that compression shortens the O:H nonbond and lengthens the H-O bond simultaneously. This H-O elongation leads to energy loss and lowers the melting point. The hot debate survived well over 150 years, mainly due to a poorly defined heat exchange with the environment in the experiment. In our current experiment, we achieved thermal isolation from the environment and studied the fully reversible ice-liquid water transition for water confined between graphene and muscovite mica. We observe a transition from two-dimensional (2D) ice into a quasi-liquid phase by applying a pressure exerted by an atomic force microscopy tip. At room temperature, the critical pressure amounts to about 6 GPa. The transition is completely reversible: refreezing occurs when the applied pressure is lifted. The critical pressure to melt the 2D ice decreases with temperature, and we measured the phase coexistence line between 293 and 333 K. From a Clausius-Clapeyron analysis, we determine the latent heat of fusion of two-dimensional ice at 0.15 eV/molecule, being twice as large as that of bulk ice.

Self-diffusion of protons in H{sub 2}O ice VII at high pressures: Anomaly around 10 GPa

DOE Office of Scientific and Technical Information (OSTI.GOV)

Noguchi, Naoki, E-mail: noguchi-n@okayama-u.ac.jp; Okuchi, Takuo

2016-06-21

The self-diffusion of ice VII in the pressure range of 5.5–17 GPa and temperature range of 400–425 K was studied using micro Raman spectroscopy and a diamond anvil cell. The diffusion was monitored by observing the distribution of isotope tracers: D{sub 2}O and H{sub 2}{sup 18}O. The diffusion coefficient of hydrogen reached a maximum value around 10 GPa. It was two orders of magnitude greater at 10 GPa than at 6 GPa. Hydrogen diffusion was much faster than oxygen diffusion, which indicates that protonic diffusion is the dominant mechanism for the diffusion of hydrogen in ice VII. This mechanism ismore » in remarkable contrast to the self-diffusion in ice I{sub h} that is dominated by an interstitial mechanism for the whole water molecule. An anomaly around 10 GPa in ice VII indicates that the rate-determining process for the proton diffusion changes from the diffusion of ionic defects to the diffusion of rotational defects, which was suggested by proton conductivity measurements and molecular dynamics simulations.« less

Surface evolution of two-component stone/ice bodies in the Jupiter region

NASA Astrophysics Data System (ADS)

Hartmann, W. K.

1980-11-01

Observational and theoretical data converge on the conclusion that planetesimals in Jupiter's region of the solar nebula were initially composed predominantly of a mixture of roughly 39-70% H2O ice by volume, and 30-61% dark stony material resembling carbonaceous chondrites. Recent observations emphasize a division of most asteroid and satellite surfaces in this region into two distinct groups: bright icy material and dark stony material. The present model accounts for these by two main processes: an impact-induced buildup of a dark stony regolith in the absence of surface thermal disturbance, and thermal-disturbance-induced eruption of 'water magmas' that create icy surfaces. 'Thermal disturbances' include tidal and radiative effects caused by nearness of a planet. A correlation of crater density and albedo, Ganymede's dark-ray craters, and other observed phenomena (listed in the summary) appear consistent with the model discussed here.

High-Albedo Salt Crusts on the Tropical Ocean of Snowball Earth: Measurements and Modeling

NASA Astrophysics Data System (ADS)

Carns, R.; Light, B.; Warren, S. G.

2014-12-01

During a Snowball Earth event, almost all of the ocean surface first freezes as sea ice. As in modern sea ice, trapped inclusions of liquid brine permeate the ice cover. As the ice grows and cools, salt crystals precipitate within the inclusions. At -23C, the most abundant salt in seawater, sodium chloride, begins to precipitate as the dihydrate mineral hydrohalite (NaCl·2H2O). Crystals of hydrohalite within the sea ice scatter light. Measurements of cold, natural sea ice show a broadband albedo increase of 10-20% when salt precipitates. Such snow-free natural sea ice with a surface temperature below -23C is rare on modern Earth, but would have been common in tropical regions of a Snowball Earth where evaporation exceeded precipitation. The persistent cold and lack of summer melt on the Snowball ocean surface, combined with net evaporation, is hypothesized to yield lag deposits of hydrohalite crystals on the ice surface. To investigate this process, we prepared laboratory-grown sea ice in a 1000 liter tank in a walk-in freezer laboratory. The ice was cooled below -23 C and the surface sprayed with a 23% NaCl solution to create a layer of hydrohalite-enriched ice, a proxy for lag deposits that would have formed over long periods of surface sublimation. We have developed a novel technique for measuring the spectral albedo of ice surfaces in the laboratory; this technique was used to monitor the evolution of the surface albedo of our salt crust as the ice matrix sublimated away leaving a layer of fine-grained hydrohalite crystals. Measurements of this hydrohalite surface crust show a very high albedo, comparable to fresh snow at visible wavelengths and significantly larger than fresh snow at near infrared wavelengths. Broadband albedos are 0.55 for bare artificial sea ice at -30C, 0.75 for ice containing 25% hydrohalite by volume, 0.84 after five days of desiccation and 0.93 after 47 days of desiccation. Using our laboratory measurements, along with estimates of grain size and crust optical depth, as inputs to Mie scattering and radiative transfer models allowed us to infer the imaginary refractive index of hydrohalite. The model can calculate albedo for pure hydrohalite crusts of varying thickness and for mixtures of ice and hydrohalite. A parameterization is presented for albedo as a function of the thickness of the hydrohalite crust.

Water Ice on Triton

NASA Technical Reports Server (NTRS)

Cruikshank, Dale P.; Roush, Ted L.; Owen, Tobias C.; Schmitt, Bernard; Quirico, Eric; Geballe, Thomas R.; deBergh, Catherine; Bartholomew, Mary Jane; DalleOre, Cristina M.; Doute, Sylvain

1999-01-01

We report the spectroscopic detection of H2O ice on Triton, evidenced by the broad absorptions in the near infrared at 1.55 and 2.04 micron. The detection on Triton confirms earlier preliminary studies (D. P. Cruikshank, R. H. Brown, and R. N. Clark, Icarus 58, 293-305, 1984). The spectra support the contention that H2O ice on Triton is in a crystalline (cubic or hexagonal) phase. Our spectra (1.87-2.5 micron) taken over an interval of nearly 3.5 years do not show any significant changes that might relate to reports of changes in Triton's spectral reflectance (B. Buratti, M. D. Hicks, and R. L. Newburn, Jr., Nature 397, 219, 1999), or in Triton's volatile inventory (J. L. Elliot et al., Nature 393, 765-767, 1998).

Observations of CO2 in Comets C/2012 S1 ISON and C/2012 K1 PANSTARRS

NASA Astrophysics Data System (ADS)

McKay, Adam; Kelley, Michael; DiSanti, Michael; Cochran, Anita; Dello Russo, Neil; Lisse, Carey; Chanover, Nancy

2013-10-01

Comets have undergone very little thermal evolution in their lifetimes, resulting in a primitive composition. This primitive composition makes observations of comets very important tools for understanding the origin of the Solar System. The ices H2O, CO2, and CO are the primary ices present in cometary nuclei, and constraining their abundances has tremendous implications for the formation and evolutionary history of comets. Of these ices, H2O and CO can be observed from the ground, while CO2 cannot. A potentially effective tracer for CO2 in comets that is accessible from the ground is atomic oxygen. However, the relationship between these ices and atomic oxygen is only understood at a qualitative level. We propose to use Spitzer observations in IRAC's 4.5 micron band pass to observe the CO2 v3 band at 4.26 microns in comets C/2012 S1 ISON and C/2012 K1 PANSTARRS. These observations will be coordinated with observations of atomic oxygen obtained at Apache Point Observatory and McDonald Observatory and observations of H2O and CO at Keck and IRTF. These observations of H2O, CO2, and atomic oxygen in a cometary coma will increase our understanding of the link between these primary ices and atomic oxygen. With a complete understanding of the relationship between atomic oxygen and the primary ices on the nucleus, observations of atomic oxygen can serve as a powerful proxy for the production of CO2. In addition, ISON is the target of an extensive observing campaign led by NASA, and the proposed Spitzer observations fill a vital niche as the only observatory that can observe CO2 during both the near-perihelion time frame and significantly (months) after perihelion. Understanding the evolution of the CO2 abundance over the apparition is a key piece to understanding how the volatile compostion of the comet changes over the apparition.

Pluto's Nonvolatile Chemical Compounds

NASA Astrophysics Data System (ADS)

Grundy, William M.; Binzel, Richard; Cook, Jason C.; Cruikshank, Dale P.; Dalle Ore, Cristina M.; Earle, Alissa M.; Ennico, Kimberly; Jennings, Donald; Howett, Carly; Kaiser, Ralf-Ingo; Linscott, Ivan; Lunsford, A. W.; Olkin, Catherine B.; Parker, Alex Harrison; Parker, Joel Wm.; Philippe, Sylvain; Protopapa, Silvia; Quirico, Eric; Reuter, D. C.; Schmitt, Bernard; Singer, Kelsi N.; Spencer, John R.; Stansberry, John A.; Stern, S. Alan; Tsang, Constantine; Verbiscer, Anne J.; Weaver, Harold A.; Weigle, G. E.; Young, Leslie

2016-10-01

Despite the migration of Pluto's volatile ices (N2, CO, and CH4) around the surface on seasonal timescales, the planet's non-volatile materials are not completely hidden from view. They occur in a variety of provinces formed over a wide range of timescales, including rugged mountains and chasms, the floors of mid-latitude craters, and an equatorial belt of especially dark and reddish material typified by the informally named Cthulhu Regio. NASA's New Horizons probe observed several of these regions at spatial resolutions as fine as 3 km/pixel with its LEISA imaging spectrometer, covering wavelengths from 1.25 to 2.5 microns. Various compounds that are much lighter than the tholin-like macromolecules responsible for the reddish coloration, but that are not volatile at Pluto surface temperatures such as methanol (CH3OH) and ethane (C2H6) have characteristic absorption bands within LEISA's wavelength range. This presentation will describe their geographic distributions and attempt to constrain their origins. Possibilities include an inheritance from Pluto's primordial composition (the likely source of H2O ice seen on Pluto's surface) or ongoing production from volatile precursors through photochemistry in Pluto's atmosphere or through radiolysis on Pluto's surface. New laboratory data inform the analysis.This work was supported by NASA's New Horizons project.

The Transition from Hydrogen Bonding to Ionization in (HCI)n(NH3)n and (HCI)n(H2O)n Clusters: Consequences for Anharmonic Vibrational Spectroscopy

NASA Technical Reports Server (NTRS)

Chaban, Galina M.; Gerber, R. Benny; Janda, Kenneth C.; Kwak, Dochan (Technical Monitor)

2001-01-01

Anharmonic vibrational frequencies and intensities are calculated for 1:1 and 2:2 (HCl)(sub n)(NH3)(sub n) and (HCl)(sub n)(H2O)(sub n) complexes, employing the correlation-corrected vibrational self-consistent field method with ab initio potential surfaces at the MP2/TZP computational level. In this method, the anharmonic coupling between all vibrational modes is included, which is found to be important for the systems studied. For the 4:4 (HCl)(sub n)(H2O)(sub n) complex, the vibrational spectra are calculated at the harmonic level, and anharmonic effects are estimated. Just as the (HCl)(sub n)(NH3)(sub n) structure switches from hydrogen-bonded to ionic for n=2, the (HCl)(sub n)(H2O)(sub n) switches to ionic structure for n=4. For (HCl)2(H2O)2, the lowest energy structure corresponds to the hydrogen-bonded form. However, configurations of the ionic form are separated from this minimum by a barrier of less than an O-H stretching quantum. This suggests the possibility of experiments on ionization dynamics using infrared excitation of the hydrogen-bonded form. The strong cooperative effects on the hydrogen bonding, and concomitant transition to ionic bonding, makes an accurate estimate of the large anharmonicity crucial for understanding the infrared spectra of these systems. The anharmonicity is typically of the order of several hundred wave numbers for the proton stretching motions involved in hydrogen or ionic bonding, and can also be quite large for the intramolecular modes. In addition, the large cooperative effects in the 2:2 and higher order (HCl(sub n)(H2O)(sub n) complexes may have interesting implications for solvation of hydrogen halides at ice surfaces.

Laboratory measurements of HDO/H2O isotopic fractionation during ice deposition in simulated cirrus clouds.

PubMed

Lamb, Kara D; Clouser, Benjamin W; Bolot, Maximilien; Sarkozy, Laszlo; Ebert, Volker; Saathoff, Harald; Möhler, Ottmar; Moyer, Elisabeth J

2017-05-30

The stable isotopologues of water have been used in atmospheric and climate studies for over 50 years, because their strong temperature-dependent preferential condensation makes them useful diagnostics of the hydrological cycle. However, the degree of preferential condensation between vapor and ice has never been directly measured at temperatures below 233 K (-40 °C), conditions necessary to form cirrus clouds in the Earth's atmosphere, routinely observed in polar regions, and typical for the near-surface atmospheric layers of Mars. Models generally assume an extrapolation from the warmer experiments of Merlivat and Nief [Merlivat L, Nief G (1967) Tellus 19:122-127]. Nonequilibrium kinetic effects that should alter preferential partitioning have also not been well characterized experimentally. We present here direct measurements of HDO/H 2 O equilibrium fractionation between vapor and ice ([Formula: see text]) at cirrus-relevant temperatures, using in situ spectroscopic measurements of the evolving isotopic composition of water vapor during cirrus formation experiments in a cloud chamber. We rule out the recent proposed upward modification of [Formula: see text], and find values slightly lower than Merlivat and Nief. These experiments also allow us to make a quantitative validation of the kinetic modification expected to occur in supersaturated conditions in the ice-vapor system. In a subset of diffusion-limited experiments, we show that kinetic isotope effects are indeed consistent with published models, including allowing for small surface effects. These results are fundamental for inferring processes on Earth and other planets from water isotopic measurements. They also demonstrate the utility of dynamic in situ experiments for studying fractionation in geochemical systems.

Antarctic Mirabilite Mounds as Mars Analogs: The Lewis Cliffs Ice Tongue Revisited

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Sun, Tao; Niles, Paul B.; Harvey, Ralph P.; Bish, David L.; Tonui, Eric

2012-01-01

It has been proposed, based on geomorphic and geochemical arguments, that subsurface water has played an important role in the history of water on the planet Mars [1]. Subsurface water, if present, could provide a protected and long lived environment for potential life. Discovery of gullies [2] and recurring slopes [3] on Mars suggest the potential for subsurface liquid water or brines. Recent attention has also focused on small (< approx. 1km dia.) mound-like geomorphic features discovered within the mid to high latitudes on the surface of Mars which may be caused by eruptions of subsurface fluids [4, 5]. We have identified massive but highly localized Na-sulfate deposits (mirabilite mounds, Na2SO4 .10H2O) that may be derived from subsurface fluids and may provide insight into the processes associated with subsurface fluids on Mars. The mounds are found on the end moraine of the Lewis Cliffs Ice Tongue (LCIT) [6] in the Transantarctic Mountains, Antarctica, and are potential terrestrial analogs for mounds observed on the martian surface. The following characteristics distinguish LCIT evaporite mounds from other evaporite mounds found in Antarctic coastal environments and/or the McMurdo Dry Valleys: (1) much greater distance from the open ocean (approx.500 km); (2) higher elevation (approx.2200 meters); and (3) colder average annual temperature (average annual temperature = -30 C for LCIT [7] vs. 20 C at sea level in the McMurdo region [8]. Furthermore, the recent detection of subsurface water ice (inferred as debris-covered glacial ice) by the Mars Reconnaissance Orbiter [9] supports the use of an Antarctic glacial environment, particularly with respect to the mirabilite deposits described in this work, as an ideal terrestrial analog for understanding the geochemistry associated with near-surface martian processes. S and O isotopic compositions.

The mid-IR Absorption Cross Sections of α- and β-NAT (HNO3 · 3H2O) in the range 170 to 185 K and of metastable NAD (HNO3 · 2H2O) in the range 172 to 182 K

NASA Astrophysics Data System (ADS)

Iannarelli, R.; Rossi, M. J.

2015-11-01

Growth and Fourier transform infrared (FTIR) absorption in transmission of the title nitric acid hydrates have been performed in a stirred flow reactor (SFR) under tight control of the H2O and HNO3 deposition conditions affording a closed mass balance of the binary mixture. The gas and condensed phases have been simultaneously monitored using residual gas mass spectrometry and FTIR absorption spectroscopy, respectively. Barrierless nucleation of the metastable phases of both α-NAT (nitric acid trihydrate) and NAD (nitric acid dihydrate) has been observed when HNO3 was admitted to the SFR in the presence of a macroscopic thin film of pure H2O ice of typically 1 µm thickness. The stable β-NAT phase was spontaneously formed from the precursor α-NAT phase through irreversible thermal rearrangement beginning at 185 K. This facile growth scheme of nitric acid hydrates requires the presence of H2O ice at thicknesses in excess of approximately hundred nanometers. Absolute absorption cross sections in the mid-IR spectral range (700-4000 cm-1) of all three title compounds have been obtained after spectral subtraction of excess pure ice at temperatures characteristic of the upper troposphere/lower stratosphere. Prominent IR absorption frequencies correspond to the antisymmetric nitrate stretch vibration (ν3(NO3-)) in the range 1300 to 1420 cm-1 and the bands of hydrated protons in the range 1670 to 1850 cm-1 in addition to the antisymmetric O-H stretch vibration of bound H2O in the range 3380 to 3430 cm-1 for NAT.

Energy, chemical disequilibrium, and geological constraints on Europa.

PubMed

Hand, Kevin P; Carlson, Robert W; Chyba, Christopher F

2007-12-01

Europa is a prime target for astrobiology. The presence of a global subsurface liquid water ocean and a composition likely to contain a suite of biogenic elements make it a compelling world in the search for a second origin of life. Critical to these factors, however, may be the availability of energy for biological processes on Europa. We have examined the production and availability of oxidants and carbon-containing reductants on Europa to better understand the habitability of the subsurface ocean. Data from the Galileo Near-Infrared Mapping Spectrometer were used to constrain the surface abundance of CO(2) to 0.036% by number relative to water. Laboratory results indicate that radiolytically processed CO(2)-rich ices yield CO and H(2)CO(3); the reductants H(2)CO, CH(3)OH, and CH(4) are at most minor species. We analyzed chemical sources and sinks and concluded that the radiolytically processed surface of Europa could serve to maintain an oxidized ocean even if the surface oxidants (O(2), H(2)O(2), CO(2), SO(2), and SO(4) (2)) are delivered only once every approximately 0.5 Gyr. If delivery periods are comparable to the observed surface age (30-70 Myr), then Europa's ocean could reach O(2) concentrations comparable to those found in terrestrial surface waters, even if approximately 10(9) moles yr(1) of hydrothermally delivered reductants consume most of the oxidant flux. Such an ocean would be energetically hospitable for terrestrial marine macrofauna. The availability of reductants could be the limiting factor for biologically useful chemical energy on Europa.

Laboratory Analysis Of Water, Hydrocarbon And Ammonia Ice Mixtures Exposed To High-energy Electron Irradiation

NASA Astrophysics Data System (ADS)

Hand, Kevin P.; Carlson, R. W.; Tsapin, A. I.

2006-09-01

Irradiation of low temperature ices in the laboratory provides insight into processes that may be occurring on icy bodies in the solar system. Here we report on results from high-energy (10keV) electron irradiation of thin ice films at 1e-8 torr and 70-120K. Mixtures include water with CO2, C3H8, C3H6, C4H10 (butane and isobutane), C4H8,(1-butene and cis/trans-2-butene), and NH3. During irradiation of H2O + alkane films at 80K, CO2 and CH4 production is observed and both species are retained in the ice, possibly trapped in clathrates. The -CH3 infrared bands initially present are seen to decrease with increasing dose. Bands associated with -CH2- persist, indicating polymerization of the initial short-chain hydrocarbons. In alkenes a similar evolution toward polymerization is observed, however the first step appears to be the destruction of the C=C bond. Upon warming of the film, mass spectra data compliment the mid-infrared data and indicate the production of H2CO, however glycolic acid is not explicitly seen in the mass spectra. When warmed to 300K, residues remained for all irradiated films except that of the H2O + CO2 mixtures. Residues were analyzed with Matrix Assisted Laser Desorption/Ionization Mass Spectrometry (MALDI). Results show the production of large aliphatic, very refractory, hydrocarbons (with m/z up to 2500). Mid-infrared spectra of the residues indicate carbonyls and alcohols, likely due to polymerized aldehydes and carboxylic acids. Films of H2O + C3H8 + NH3 at 70K show the production of OCN- (cyanate ion), formamide, along with other possible amides and hydrocarbons. HPLC results indicate the production of racemic alanine. Finally, results of abiotic experiments are compared to results from the irradiation of bacterial spores in ice. The application to Europa and Enceladus is discussed.

Pluto's surface composition and atmosphere

NASA Astrophysics Data System (ADS)

Young, L. A.; Gladstone, R.; Summers, M. E.; Strobel, D. F.; Kammer, J.; Hinson, D. P.; Grundy, W. M.; Cruikshank, D. P.; Protopapa, S.; Schmitt, B.; Stern, A.; Weaver, H. A., Jr.; Olkin, C.; Ennico Smith, K.

2017-12-01

New Horizons studied Pluto's N2-dominated neutral atmosphere through radio (at 4.2 cm with the REX radio experiment), solar and stellar occultations and airglow (at 52-187 nm with the Alice ultraviolet spectrograph), and imaging (with the LORRI and MVIC visible-wavelength cameras). It studied the plasma environment and solar wind interaction with in situ instruments (PEPPSI and SWAP). Contemporaneous observations of Pluto's atmosphere from Earth included a ground-based stellar occultation and ALMA observations of gaseous CO and HCN. Joint analysis of these datasets reveal a variable boundary layer; a stable lower atmosphere; radiative heating and cooling; haze production and hydrocarbon chemistry; diffusive equilibrium; and slower-than-expected escape. New Horizons studied Pluto's surface composition with the LEISA near-infrared spectral imager from 1.25 to 2.5 micron. Additional compositional information at higher spatial resolution came from the MVIC 4-channel color imager, which included a channel centered at 0.89 micron specifically designed to detect solid CH4. These instruments allow mapping of the volatiles N2, CO, and CH4, the surface expression of the H2O bedrock, and the dark, reddish material presumed to be tholins. These observations reveal a large equatorial basin (informally named Sptunik Planitia), filled with N2 ice with minor amounts of CO and CH4, surrounded by hills of CH4 and H2O ice. Broadly speaking, composition outside of Sptunik Planitia follows latitudinal banding, with dark, mainly volatile free terrains near the equator, with N2, CO, and CH4 at mid-northern latitudes, and mainly CH4 at high northern latitudes. Deviations from these broad trends are seen, and point to complex surface-atmosphere interactions at diurnal, seasonal, perennial, and million-year timescales.

INFRARED STUDY OF UV/EUV IRRADIATION OF NAPHTHALENE IN H2O+NH3 ICE

NASA Astrophysics Data System (ADS)

Chen, Y.-J.; Nuevo, M.; Yeh, F.-C.; Yih, T.-S.; Sun, W.-H.; Ip, W.-H.; Fung, H.-S.; Lee, Y.-Y.; Wu, C.-Y. R.

We have carried out photon irradiation study of naphthalene (C10H8), the smallest polycyclic aromatic hydrocarbon (PAH) in water and ammonia ice mixtures. Photons provided by a synchrotron radiation light source in two broad-band energy ranges in the ultraviolet/near extreme ultraviolet (4-20 eV) and the extreme ultraviolet (13-45 eV) ranges were used for the irradiation of H2O+NH3+C10H8 = 1:1:1 ice mixtures at 15K. We could identify several photo-products, namely CH4, C2H6, C3H8, CO, CO2, HNCO, OCN-, and probably quinoline (C9H7N) and phenanthridine (C13H9N). We found that the light hydrocarbons are preferably produced for the ice mixture subjected to 4-20 eV photons. However, the production yields of CO, CO2, and OCN- species seem to be higher for the mixture subjected to EUV photons (13-45 eV). Therefore, naphthalene and its photo-products appear to be more efficiently destroyed when high energy photons (E > 20 eV) are used. This has important consequences on the photochemical evolution of PAHs in astrophysical environments.

The effect of rock particles and D2O replacement on the flow behaviour of ice

PubMed Central

Grindrod, Peter M.

2017-01-01

Ice–rock mixtures are found in a range of natural terrestrial and planetary environments. To understand how flow processes occur in these environments, laboratory-derived properties can be extrapolated to natural conditions through flow laws. Here, deformation experiments have been carried out on polycrystalline samples of pure ice, ice–rock and D2O-ice–rock mixtures at temperatures of 263, 253 and 233 K, confining pressure of 0 and 48 MPa, rock fraction of 0–50 vol.% and strain-rates of 5 × 10−7 to 5 × 10−5 s−1. Both the presence of rock particles and replacement of H2O by D2O increase bulk strength. Calculated flow law parameters for ice and H2O-ice–rock are similar to literature values at equivalent conditions, except for the value of the rock fraction exponent, here found to be 1. D2O samples are 1.8 times stronger than H2O samples, probably due to the higher mass of deuterons when compared with protons. A gradual transition between dislocation creep and grain-size-sensitive deformation at the lowest strain-rates in ice and ice–rock samples is suggested. These results demonstrate that flow laws can be found to describe ice–rock behaviour, and should be used in modelling of natural processes, but that further work is required to constrain parameters and mechanisms for the observed strength enhancement. This article is part of the themed issue ‘Microdynamics of ice’. PMID:28025298

27-day solar forcing of mesospheric temperature, water vapor and polar mesospheric clouds from the AIM SOFIE and CIPS satellite experiments

NASA Astrophysics Data System (ADS)

Thomas, Gary; Thurairajah, Brentha; von Savigny, Christian; Hervig, Mark; Snow, Martin

2016-04-01

Solar cycle variations of ultraviolet radiation have been implicated in the 11-year and 27-day variations of Polar Mesospheric Cloud (PMC) properties. Both of these variations have been attributed to variable solar ultraviolet heating and photolysis, but no definitive studies of the mechanisms are available. The solar forcing issue is critical toward answering the broader question of whether PMC's have undergone long-term changes, and if so, what is the nature of the responsible long-term climate forcings? One of the principal goals of the Aeronomy of Ice in the Mesosphere satellite mission was to answer the question: "How does changing solar irradiance affect PMCs and the environment in which they form?" We describe an eight-year data set from the AIM Solar Occultation for Ice Experiment (SOFIE) and the AIM Cloud Imaging and Particle Size (CIPS) experiment. Together, these instruments provide high-precision measurements of high-latitude summertime temperature (T), water vapor (H2O), and PMC ice properties for the period 2007-present. The complete temporal coverage of the summertime polar cap region for both the primary atmospheric forcings of PMC (T and H2O), together with a continually updated time series of Lyman-alpha solar irradiance, allows an in-depth study of the causes and effects of 27-day PMC variability. The small responses of these variables, relative to larger day-to-day changes from gravity waves, tides, inter-hemispheric coupling, etc. require a careful statistical analysis to isolate the solar influence. We present results for the 27-day responses of T, H2O and PMC for a total of 15 PMC seasons, (30 days before summer solstice to 60 days afterward, for both hemispheres). We find that the amplitudes and phase relationships are not consistent with the expected mechanisms of solar UV heating and photolysis - instead we postulate a primarily dynamical response, in which a periodic vertical wind heats/cools the upper mesosphere, and modulates PMC properties via the strong T and H2O sensitivity of ice microphysics. We propose that the wind acting on the strong H2O gradient in the 80-85 km region causes water vapor to be vertically transported, amplifying the temperature effect. Supporting evidence of a ~27-day mode of oscillation will be presented. PMC height is also shown to have a 27-day periodicity, presumably a result of rising/falling of pressure surfaces. Implications of these results for the 11-year variability of PMC will be presented.

Methanol Formation via Oxygen Insertion Chemistry in Ices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bergner, Jennifer B.; Öberg, Karin I.; Rajappan, Mahesh

We present experimental constraints on the insertion of oxygen atoms into methane to form methanol in astrophysical ice analogs. In gas-phase and theoretical studies this process has previously been demonstrated to have a very low or nonexistent energy barrier, but the energetics and mechanisms have not yet been characterized in the solid state. We use a deuterium UV lamp filtered by a sapphire window to selectively dissociate O{sub 2} within a mixture of O{sub 2}:CH{sub 4} and observe efficient production of CH{sub 3}OH via O({sup 1}D) insertion. CH{sub 3}OH growth curves are fit with a kinetic model, and we observemore » no temperature dependence of the reaction rate constant at temperatures below the oxygen desorption temperature of 25 K. Through an analysis of side products we determine the branching ratio of ice-phase oxygen insertion into CH{sub 4}: ∼65% of insertions lead to CH{sub 3}OH, with the remainder leading instead to H{sub 2}CO formation. There is no evidence for CH{sub 3} or OH radical formation, indicating that the fragmentation is not an important channel and that insertions typically lead to increased chemical complexity. CH{sub 3}OH formation from O{sub 2} and CH{sub 4} diluted in a CO-dominated ice similarly shows no temperature dependence, consistent with expectations that insertion proceeds with a small or nonexistent barrier. Oxygen insertion chemistry in ices should therefore be efficient under low-temperature ISM-like conditions and could provide an important channel to complex organic molecule formation on grain surfaces in cold interstellar regions such as cloud cores and protoplanetary disk midplanes.« less

Ferroelectricity in high-density H 2O ice

DOE PAGES

Caracas, Razvan; Hemley, Russell J.

2015-04-01

The origin of longstanding anomalies in experimental studies of the dense solid phases of H 2O ices VII, VIII, and X is examined using a combination of first-principles theoretical methods. We find that a ferroelectric variant of ice VIII is energetically competitive with the established antiferroelectric form under pressure. The existence of domains of the ferroelectric form within anti-ferroelectric ice can explain previously observed splittings in x-ray diffraction data. The ferroelectric form is stabilized by density and is accompanied by the onset of spontaneous polarization. Here, the presence of local electric fields triggers the preferential parallel orientation of the watermore » molecules in the structure, which could be stabilized in bulk using new high-pressure techniques.« less

Calculation of the vapor-saturated liquidus for the NaCl-CO2-H2O system

USGS Publications Warehouse

Barton, P.B.; I-Ming, C.

1993-01-01

The polybaric liquidus surface for the H2O-rich corner of the NaCl-CO2-H2O ternary is calculated, relying heavily on 1. (1) a Henry's law equation for CO2 in brines (modified from Drummond, 1981), 2. (2) the assumption that the contributions of dissolved NaCl and CO2 in lowering the activity of H2O are additive, and 3. (3) data on the CO2 clathrate solid solution (nominally CO2 ?? 7.3H2O, but ranging from 5.75 to 8 or 9 H2O) from Bozzo et al. (1975). The variation with composition of the activity of CO2??7.3H2O, or any other composition within the clathrate field, is small, thereby simplifying the calculations appreciably. Ternary invariant points are 1. (1) ternary eutectic at -21.5??C, with ice + clathrate + hydrohalite NaCl-??H2O + brine mNaCl = 5.15, mco2 = 0.22 + vapor Ptotal ??? Pco2 = 5.7 atm; 2. (2) peritectic at -9.6??C, with clathrate + hydrohalite + liquid CO2 + brine mNaCl = 5.18, mco2 = 0.55 + vapor (Ptotal ??? Pco2 = 26.47 atm); and 3. (3) peritectic slightly below +0.1 ??C, with halite + hydrohalite + liquid CO2 + brine (mNaCl ??? 5.5, mco2 ??? 0.64) + vapor (Ptotal ??? Pco2 ??? 34 atm). CO2 isobars have been contoured on the ternary liquidus and also on the 25??C isotherm. An important caveat regarding the application of this information to the interpretation of the freezing-thawing behavior of fluid inclusions is that metastable behavior is a common characteristic of the clathrate. ?? 1993.

Investigation of Martian H2O and CO2 via gamma-ray spectroscopy

NASA Technical Reports Server (NTRS)

Squyres, Steven W.; Evans, Larry G.

1987-01-01

The evolution and present state of water and carbon dioxide on Mars are discussed. Researchers wished to determine how effectively questions regarding the distribution of water and carbon dioxide on Mars may be addressed with orbital gamma ray spectrometer data. Several simple, multi-layer models of the Martian surface were formulated to address problems such as the ice/dust ratio of layered deposits; the distribution, depth and concentration of ground ice; the thickness of north polar perennial ice; the thickness of the carbon dioxide layer over the south polar cap; the thickness of the seasonal carbon dioxide frost cap; and the water content of the seasonal frost cap. The results indicate that the Mars Observer gamma ray spectrometer will be a powerful tool for investigating the distribution and stratigraphy of volatiles on Mars.

Kinetics of electron-induced decomposition of CF2Cl2 coadsorbed with water (ice): A comparison with CCl4

NASA Astrophysics Data System (ADS)

Faradzhev, N. S.; Perry, C. C.; Kusmierek, D. O.; Fairbrother, D. H.; Madey, T. E.

2004-11-01

The kinetics of decomposition and subsequent chemistry of adsorbed CF2Cl2, activated by low-energy electron irradiation, have been examined and compared with CCl4. These molecules have been adsorbed alone and coadsorbed with water ice films of different thicknesses on metal surfaces (Ru; Au) at low temperatures (25 K; 100 K). The studies have been performed with temperature programmed desorption (TPD), reflection absorption infrared spectroscopy (RAIRS), and x-ray photoelectron spectroscopy (XPS). TPD data reveal the efficient decomposition of both halocarbon molecules under electron bombardment, which proceeds via dissociative electron attachment (DEA) of low-energy secondary electrons. The rates of CF2Cl2 and CCl4 dissociation increase in an H2O (D2O) environment (2-3×), but the increase is smaller than that reported in recent literature. The highest initial cross sections for halocarbon decomposition coadsorbed with H2O, using 180 eV incident electrons, are measured (using TPD) to be 1.0±0.2×10-15 cm2 for CF2Cl2 and 2.5±0.2×10-15 cm2 for CCl4. RAIRS and XPS studies confirm the decomposition of halocarbon molecules codeposited with water molecules, and provide insights into the irradiation products. Electron-induced generation of Cl- and F- anions in the halocarbon/water films and production of H3O+, CO2, and intermediate compounds COF2 (for CF2Cl2) and COCl2, C2Cl4 (for CCl4) under electron irradiation have been detected using XPS, TPD, and RAIRS. The products and the decomposition kinetics are similar to those observed in our recent experiments involving x-ray photons as the source of ionizing irradiation.

Experimental Demonstration of the Formation of Liquid Brines under Martian Polar Conditions in the Michigan Mars Environmental Chamber

NASA Astrophysics Data System (ADS)

Fischer, Erik; Martinez, German; Elliott, Harvey; Borlina, Caue; Renno, Nilton

2014-05-01

Liquid water is one of the necessary ingredients for the development of life as we know it. The behavior of various liquid states of H2O such as liquid brine, undercooled liquid interfacial water, subsurface melt water and ground water [1] needs to be understood in order to address the potential habitability of Mars for microbes and future human exploration. It has been shown thermodynamically that liquid brines can exist under Martian polar conditions [2, 3]. We have developed the Michigan Mars Environmental Chamber (MMEC) to simulate the entire range of Martian surface and shallow subsurface conditions with respect to temperature, pressure, relative humidity, solar radiation and soil wetness at equatorial and polar latitudes. Our experiments in the MMEC show that deliquescence of NaClO4, Mg(ClO4)2 and Ca(ClO4)2 occurs diurnally under the environmental conditions of the Phoenix landing site when these salts get in contact with water ice. Since Phoenix detected these salts and water ice at the landing site, including frost formation, it is extremely likely that deliquescence occurs at the Phoenix landing site. By layering NaClO4, Mg(ClO4)2 or Ca(ClO4)2 on top of a pure water ice slab at 800 Pa and 190 K and raising the temperature stepwise across the eutectic temperature of the perchlorate salts, we observe distinct changes in the Raman spectra of the samples when deliquescence occurs. When crossing the eutectic temperatures of NaClO4 (236 K), Mg(ClO4)2 (205 K) and Ca(ClO4)2 (199 K) [4, 5], the perchlorate band of the Raman spectrum shows a clear shift from 953 cm-1 to 936 cm-1. Furthermore, the appearance of a broad O-H vibrational stretching spectrum between 3244 cm-1 and 3580 cm-1 is another indicator of deliquescence. This process of deliquescence occurs on the order of seconds when the perchlorate salt is in contact with water ice. On the contrary, when the perchlorate salt is only subjected to water vapor in the Martian atmosphere, deliquescence was not observed within the Martian diurnal cycle. This greatly diminishes the possibility of liquid brine formation without water ice contact and has strong implications on future robotic and manned missions searching for liquid water on Mars. Acknowledgement: This research is supported by a grant from the NASA Astrobiology Program: Exobiology and Evolutionary Biology. Award #09-EXOB09-0050. References: [1] Martínez, G. M. and Renno, N. O. (2013), Water and Brines on Mars: Current Evidence and Implications for MSL, Space Sci. Rev., 175, 29-51. [2] Rennó, N. O., et al. (2009), Possible physical and thermodynamical evidence for liquid water at the Phoenix landing site, J. Geophys. Res., 114, E00E03. [3] Zorzano, M.-P., et al., Stability of liquid saline water on present day Mars, Geophys. Res. Lett., 36, L20201. [4] Hanley, J. et al. (2009), Low Temperature Aqueous Perchlorate Solutions on the Surface of Mars, Proceedings 40th Lunar and Planetary Sciences Conference, The Woodlands, TX, USA. [5] Marion, G. M. et al. (2010), Modeling Aqueous Perchlorate Chemistries with Applications to Mars, Icarus, 207, 675-685.

Outer planets and icy satellites

NASA Technical Reports Server (NTRS)

Drobyshevski, E. M.

1991-01-01

The resources offered by the outer bodies in the Solar System, starting with the main belt asteroids and Jovian System, are not only larger and more diverse but may even be easier to reach than, say, those of Mars. The use of their material, including water and organic matter, depends exclusively on the general strategy of exploration of the Solar System. Of major interest in this respect are the large ice satellites - Titan, Ganymede, and Callisto. Motion through the planetary magnetospheres excites in their ice envelopes megampere currents which, in the presence of rocky, etc., inclusions with electronic conduction should lead to the bulk electrolysis of ice and accumulation in it of 2H2 + O2 in the form of a solid solution. With the concentration of 2H2 + O2 reaching about 15 wt. percent, the solution becomes capable of detonation by a strong meteoritic impact. An explosion of Ganymede's ice envelope about 0.5 By ago could account for the formation of the Trojans and irregular satellites, all known differences between Ganymede and Callisto, and many other things. The explosion of a small icy planet with M approx less than 0.5 Moon created the asteroid belt. Two to three explosions occurred on Io, and two on Europa. The specific features of the longperiod comets close to Saturn's orbit permit dating Titan's envelope explosion as 10,000 yr ago, which produced its thick atmosphere, young Saturn's rings, as well as a reservoir of ice fragments saturated by 2H2 + O2, i.e., cometary nuclei between the orbits of Jupiter and Saturn. Thus these nuclei should contain, besides organic matter, also 2H2 + O2, which could be used for their transportation as well as for fuel for spaceships. Ices of such composition can reside deep inside Deimos, the Trojans, C-asteroids, etc. The danger of a future explosion of Callisto's electrolyzed ices, which would result in a catastrophic bombardment of the Earth by comets, may be high enough to warrant a revision of the priorities and strategy of space exploration.

Outer planets and icy satellites

NASA Astrophysics Data System (ADS)

Drobyshevski, E. M.

The resources offered by the outer bodies in the Solar System, starting with the main belt asteroids and Jovian System, are not only larger and more diverse but may even be easier to reach than, say, those of Mars. The use of their material, including water and organic matter, depends exclusively on the general strategy of exploration of the Solar System. Of major interest in this respect are the large ice satellites - Titan, Ganymede, and Callisto. Motion through the planetary magnetospheres excites in their ice envelopes megampere currents which, in the presence of rocky, etc., inclusions with electronic conduction should lead to the bulk electrolysis of ice and accumulation in it of 2H2 + O2 in the form of a solid solution. With the concentration of 2H2 + O2 reaching about 15 wt. percent, the solution becomes capable of detonation by a strong meteoritic impact. An explosion of Ganymede's ice envelope about 0.5 By ago could account for the formation of the Trojans and irregular satellites, all known differences between Ganymede and Callisto, and many other things. The explosion of a small icy planet with M approx less than 0.5 Moon created the asteroid belt. Two to three explosions occurred on Io, and two on Europa. The specific features of the longperiod comets close to Saturn's orbit permit dating Titan's envelope explosion as 10,000 yr ago, which produced its thick atmosphere, young Saturn's rings, as well as a reservoir of ice fragments saturated by 2H2 + O2, i.e., cometary nuclei between the orbits of Jupiter and Saturn. Thus these nuclei should contain, besides organic matter, also 2H2 + O2, which could be used for their transportation as well as for fuel for spaceships. Ices of such composition can reside deep inside Deimos, the Trojans, C-asteroids, etc. The danger of a future explosion of Callisto's electrolyzed ices, which would result in a catastrophic bombardment of the Earth by comets, may be high enough to warrant a revision of the priorities and strategy of space exploration.

Characteristics of the horizontal and vertical distributions of dimethyl sulfide throughout the Amundsen Sea Polynya.

PubMed

Kim, Intae; Hahm, Doshik; Park, Keyhong; Lee, Youngju; Choi, Jung-Ok; Zhang, Miming; Chen, Liqi; Kim, Hyun-Cheol; Lee, SangHoon

2017-04-15

We investigated horizontal and vertical distributions of DMS in the upper water column of the Amundsen Sea Polynya and Pine Island Polynya during the austral summer (January-February) of 2016 using a membrane inlet mass spectrometer (MIMS) onboard the Korean icebreaker R/V Araon. The surface water concentrations of DMS varied from <1 to 400nM. The highest DMS (up to 300nM) were observed in sea ice-polynya transition zones and near the Getz ice shelf, where both the first local ice melting and high plankton productivity were observed. In other regions, high DMS concentration was generally accompanied by higher chlorophyll and ΔO 2 /Ar. The large spatial variability of DMS and primary productivity in the surface water of the Amundsen Sea seems to be attributed to melting conditions of sea ice, relative dominance of Phaeocystis Antarctica as a DMS producer, and timing differences between bloom and subsequent DMS productions. The depth profiles of DMS and ΔO 2 /Ar were consistent with the horizontal surface data, showing noticeable spatial variability. However, despite the large spatial variability, in contrast to the previous results from 2009, DMS concentrations and ΔO 2 /Ar in the surface water were indistinct between the two major domains: the sea ice zone and polynya region. The discrepancy may be associated with inter-annual variations of phytoplankton assemblages superimposed on differences in sea-ice conditions, blooming period, and spatial coverage along the vast surface area of the Amundsen Sea. Copyright © 2017 Elsevier B.V. All rights reserved.

Nanowire-nanoparticle conjugate photolytic devices for renewable hydrogen production

NASA Astrophysics Data System (ADS)

Maclaskey, Sean Kelly

A clean energy driven economy requires renewable production of zero--emission fuels, such as hydrogen (H2). Photocatalytic generation of H2 is one such method to fulfill this demand. Photocatalytic water splitting is an electrochemical process driven by solar energy to produce H2. Although there have been many investigations on photocatalytic water splitting, the number of concepts utilizing visible light is limited. In the present study, H2 evolution from water splitting is demonstrated using the novel concept of nanowire--nanoparticle (NW--NP) conjugate devices irradiated by visible light. Photolytic nanodevice suspensions are fabricated via sol--gel synthesis of vanadium oxyhydrate (V3O 7·H2O) NWs, followed by solution chemistry with HAuCl 4 for reduction of gold (Au) NPs on the NW surfaces. Characterization of nanodevices was performed via TEM, SEM, and optical spectroscopy. Products of photolysis were quantified and analyzed by Gas Chromatography (GC). The performance of the nanowire--nanoparticle conjugate devices was compared with previous photolytic device designs by the use of quantum and internal conversion efficiencies (QE and ICE, respectively). The present thesis demonstrates photocatalytic production of H2 using V3O7·H 2O NW -- Au NP conjugate devices under 470 nm excitation. The "photolytic nanodevice suspension in water" concept poses the potential for scalable H2 production, in addition to the provision for a low--cost technique due to fabrication by sol--gel synthesis and solution chemistry. The V3O7·H2O aerogel, a recently discovered semiconductor material, is found to be a suitable photoanode due to its narrow band gap energy of 2.18 eV, and its stability during photolysis. The diameters of the V3O7·H2O NWs are found to be 12 nm (+/- 2.4 nm) from SEM images. The decoration of NWs with Au NPs is verified by TEM imaging and Au NPs are estimated to be 7.5 nm (+/- 2.2 nm) in size. After decoration of NWs by Au NPs, a near--field enhancement effect on optical absorption by NWs was observed by UV--visible spectroscopy. Further, the emergence of new optical absorbance peaks indicates possible coupling of incident light into waveguide modes of the NWs. QE and ICE values for the NW--NP conjugate devices are found to be 19.28% and 8.98%, respectively, for the first hour of photolysis.

Water ice clouds observations with PFS on Mars Express

NASA Astrophysics Data System (ADS)

Moroz, V. I.; Zasova, L. V.; Formisano, V.; Grassi, D.; Ignatiev, N. I.; Giuranna, M.; Maturilli, A.; Pfs Team

The water ice cloud observation is one of the scientific goals of PFS. Presence and properties of the ice particles are identified from absorption features, observed in both spectral ranges of PFS. Being in the near perihelion condition, the temperature of the Martian atmosphere is pretty high and ice clouds exist only in some places, for example, related to topography or at north high latitudes et etc. The ice clouds are observed often above the tops of the volcanoes. We have found the ice clouds above Olympus (orbit 37) and Ascraeus Mons (orbit 68). Effective radius of particles according to the thermal IR is preliminary estimated of 1 μ m, which leads to the visual opacity of 0.2 -0.3 above Olympus and of maximum of 0.6 above Ascraeus Mons. In the case of Ascraeus Mons the ice clouds are observed on the south slope near the top of the volcano. The maximum surface temperature, observed there, results in the upward flux of warm air, which, cooling, provides the condensation of H2O. We will present a detailed analysis of the ice clouds, observed over the planet in the IR spectral range.

Rosetta Images of Comet 67P/CHURYUMOV-GERASIMENKO: Inferences from its Terrain and Structure

NASA Astrophysics Data System (ADS)

Wallis, Max; Wickramasinghe, N. Chandra

The Rosetta mission has given us remarkable images of comet 67P/C-G both from the orbiter, and recently from the Philae lander during its brief days before running out of power. Though its crust is very black, there are several indicators of an underlying icy morphology. Comet 67P displays smooth, planar `seas' (the largest 600 m × 800 m) and flat-bottomed craters, both features seen also on Comet Tempel-1. Comet 67P's surface is peppered with mega-boulders (10-70 km) like Comet Hartley-2, while parallel furrowed terrain appears as a new ice feature. The largest sea (`Cheops' Sea, 600 m × 800 m) curves around one lobe of the 4 km diameter comet, and the crater lakes extending to ~150 m across are re-frozen bodies of water overlain with organic-rich debris (sublimation lag) of order 10 cm. The parallel furrows relate to flexing of the asymmetric and spinning two-lobe body, which generates fractures in an underlying body of ice. The mega-boulders are hypothesised to arise from bolide impacts into ice. In the very low gravity, boulders ejected at a fraction of 1 m/s would readily reach ~100 m from the impact crater and could land perched on elevated surfaces. Where they stand proud, they indicate stronger refrozen terrain or show that the surface they land on (and crush) sublimates more quickly. Outgassing due to ice-sublimation was already evident in September at 3.3 AU, with surface temperature peaks of 220-230 K, which implies impure ice mixtures with less strongly-bound H2O. Increasing rates of sublimation as Rosetta follows comet 67P around its 1.3 AU perihelion will further reveal the nature and prevalence of near-surface ices.

Dust Density Distribution and Imaging Analysis of Different Ice Lines in Protoplanetary Disks

NASA Astrophysics Data System (ADS)

Pinilla, P.; Pohl, A.; Stammler, S. M.; Birnstiel, T.

2017-08-01

Recent high angular resolution observations of protoplanetary disks at different wavelengths have revealed several kinds of structures, including multiple bright and dark rings. Embedded planets are the most used explanation for such structures, but there are alternative models capable of shaping the dust in rings as it has been observed. We assume a disk around a Herbig star and investigate the effect that ice lines have on the dust evolution, following the growth, fragmentation, and dynamics of multiple dust size particles, covering from 1 μm to 2 m sized objects. We use simplified prescriptions of the fragmentation velocity threshold, which is assumed to change radially at the location of one, two, or three ice lines. We assume changes at the radial location of main volatiles, specifically H2O, CO2, and NH3. Radiative transfer calculations are done using the resulting dust density distributions in order to compare with current multiwavelength observations. We find that the structures in the dust density profiles and radial intensities at different wavelengths strongly depend on the disk viscosity. A clear gap of emission can be formed between ice lines and be surrounded by ring-like structures, in particular between the H2O and CO2 (or CO). The gaps are expected to be shallower and narrower at millimeter emission than at near-infrared, opposite to model predictions of particle trapping. In our models, the total gas surface density is not expected to show strong variations, in contrast to other gap-forming scenarios such as embedded giant planets or radial variations of the disk viscosity.

Gypsum and hydrohalite dynamics in sea ice brines

NASA Astrophysics Data System (ADS)

Butler, Benjamin M.; Papadimitriou, Stathys; Day, Sarah J.; Kennedy, Hilary

2017-09-01

Mineral authigenesis from their dissolved sea salt matrix is an emergent feature of sea ice brines, fuelled by dramatic equilibrium solubility changes in the large sub-zero temperature range of this cryospheric system on the surface of high latitude oceans. The multi-electrolyte composition of seawater results in the potential for several minerals to precipitate in sea ice, each affecting the in-situ geochemical properties of the sea ice brine system, the habitat of sympagic biota. The solubility of two of these minerals, gypsum (CaSO4 ·2H2O) and hydrohalite (NaCl · 2H2O), was investigated in high ionic strength multi-electrolyte solutions at below-zero temperatures to examine their dissolution-precipitation dynamics in the sea ice brine system. The gypsum dynamics in sea ice were found to be highly dependent on the solubilities of mirabilite and hydrohalite between 0.2 and - 25.0 ° C. The hydrohalite solubility between - 14.3 and - 25.0 ° C exhibits a sharp change between undersaturated and supersaturated conditions, and, thus, distinct temperature fields of precipitation and dissolution in sea ice, with saturation occurring at - 22.9 ° C. The sharp changes in hydrohalite solubility at temperatures ⩽-22.9 °C result from the formation of an ice-hydrohalite aggregate, which alters the structural properties of brine inclusions in cold sea ice. Favourable conditions for gypsum precipitation in sea ice were determined to occur in the region of hydrohalite precipitation below - 22.9 ° C and in conditions of metastable mirabilite supersaturation above - 22.9 ° C (investigated at - 7.1 and - 8.2 ° C here) but gypsum is unlikely to persist once mirabilite forms at these warmer (>-22.9 °C) temperatures. The dynamics of hydrohalite in sea ice brines based on its experimental solubility were consistent with that derived from thermodynamic modelling (FREZCHEM code) but the gypsum dynamics derived from the code were inconsistent with that indicated by its experimental solubility in this system. Incorporation of hydrohalite solubility into a 1D thermodynamic model of the growth of first-year Arctic sea ice showed its precipitation to initiate once the incoming shortwave radiation dropped to 0 W m-2, and that it can reach concentrations of 9.9 g kg-1 within the upper and coldest layers of the ice pack. This suggests a limited effect of hydrohalite on the albedo of sea ice. The insights provided by the solubility measurements into the behaviour of gypsum and hydrohalite in the ice-brine system cannot be gleaned from field investigations at present.

Atmospheric H2O2 measurement: comparison of cold trap method with impinger bubbling method

NASA Technical Reports Server (NTRS)

Sakugawa, H.; Kaplan, I. R.

1987-01-01

Collection of atmospheric H2O2 was performed by a cold trap method using dry ice-acetone as the refrigerant. The air was drawn by a pump into a glass gas trap immersed in the dry ice-acetone slush in a dewar flask at a flow rate of 2.5 l min-1 for approximately 2 h. Collection efficiency was > 99% and negligible interferences by O3, SO2 or organic matter with the collected H2O2 in the trap were observed. This method was compared with the air impinger bubbling method which has been previously described (Kok et al., 1978a, b, Envir. Sci. Technol. 12, 1072-1080). The measured total peroxide (H2O2 + organic peroxide) values in a series of aim samples collected by the impinger bubbling method (0.06-3.7 ppb) were always higher than those obtained by the cold trap method (0.02-1.2 ppb). Laboratory experiments suggest that the difference in values between the two methods probably results from the aqueous phase generation of H2O2 and organic peroxide in the impinger solution by a reaction of atmospheric O3 with olefinic and aromatic compounds. If these O3-organic compound reactions which occur in the impinger also occur in aqueous droplets in the atmosphere, the process could be very important for aqueous phase generation of H2O2 in clouds and rainwater.

The impact of ice I rheology on interior models of Ganymede: The elastic vs. the visco-elastic case

NASA Astrophysics Data System (ADS)

Steinbrügge, Gregor; Hussmann, Hauke; Sohl, Frank; Oberst, Jürgen

2015-04-01

Many investigations on key processes of icy satellites are driven by the rheological behavior of planetary ices. Future missions to Jupiter's icy moons (e.g. JUICE / Europa clipper) aimed at constraining the thickness of the outer ice shell using radio science and/or laser altimetry will have to address this problem. We investigate for the case of Ganymede under which conditions the ice I viscosity could be constrained by measuring the phase-lag of the tidal response using laser altimetry. In the absence of seismic data, interior structure models are constrained by the satellite's mean density and mean moment-of-inertia factor. One key observable to reduce the ambiguity of the corresponding structural models is the measurement of the dynamic response of the satellite's outer ice shells to tidal forces exerted by Jupiter and characterized by the body tide surface Love numbers h2 and k2. The Love number k2 measures the variation of the gravitational potential due to tidally induced internal redistribution of mass and can be inferred from radio science experiments. The Love number h2 is a measure for the tide-induced radial displacement of the satellite's surface. It is an advantage that Ganymede's surface displacement Love number h2 can be expected to be measured with a high accuracy using laser altimetry (Steinbrügge et al., 2014). However, the determination of the resulting ice thickness further depends on the possible existence of a liquid subsurface water ocean and on the tidally effective rheology of the outer ice shell (Moore and Schubert, 2003). Here, we distinguish between an elastic, visco-elastic or even fluid behavior in the sense of the Maxwell model and alternative rheological models. In the case of Ganymede the fluid case would imply high ice temperatures which are at odds with thermal equilibrium models calculated by Spohn and Schubert (2003). However the visco-elastic case is still possible. Laboratory measurements of ice I (e.g. Sotin et al., 1998) suggest that the rigidity can be constrained and the ambiguity left by the structural model can be recovered by the simultaneous determination of the linear combination 1+k2-h2 (Wahr et al., 2006). However, the less well known viscosity can play a major role when inferring the thickness of the outer ice shell. Limits for measurements by laser altimetry will be discussed. References: Moore, W.B. and Schubert, G., "The tidal response of Ganymede and Callisto with and without liquid water oceans", Icarus, vol. 16, p. 223-226, 2003 Sotin, C., Grasset, O. and Beauchesne, S., "Thermodynamic properties of high pressure ices: Implications for the dynamics and internal structure of large icy satellites" in "Solar system ices", p. 79-96, Springer Netherlands, 1998, doi:10.1007/97894-011-5252-54 Spohn, T. and Schubert, G., "Oceans in the icy Galilean satellites of Jupiter?", Icarus, vol. 161, p. 456-467, 2003, doi: 10.1016/S0019-1035(02)00048-9 Steinbrügge, G., Hussmann, H., Stark, A., and Oberst, J., "Measuring Ganymede's tidal deformation by laser altimetry: application to the GALA Experiment", EGU General Assembly 2014, Abstract 3761 Wahr, J. M., Zuber, M. T., Smith, D. E., and Lunine, J. I., "Tides on Europa, and the thickness of Europa's icy shell" Journal of Geophysical Research: Planets, vol. 11, 2006. doi: 10.1029/2006JE002729

Magnesium and calcium sulfate stabilities and the water budget of Mars

USGS Publications Warehouse

Chou, I.-Ming; Seal, R.R.

2007-01-01

Magnesium sulfate probably plays a dominant role in the water cycle of Mars away from the polar ice caps through hydration and dehydration reactions. This prominence is due to its abundance, its occurrence in numerous hydration states, and its ability to hydrate and dehydrate rapidly. New experimental studies on the metastable reaction between hexahydrite (MgSO4??6H2O) and starkeyite (MgSO4-4H2O) as a function of temperature and relative humidity, supplemented by recent investigations of the stable reaction between epsomite (MgSO4??7H2O) and hexahydrite and by phase equilibrium calculations, suggest that the most important magnesium sulfate phases involved in the Martian water cycle are MgSO4??11 H2O, epsomite, starkeyite, and possibly kieserite (MgSO4??H2O). Hexahydrite is not predicted to be stable on the surface of Mars. During diurnal variations in temperature and relative humidity, 1 kg of MgSO4 can release or remove from the atmosphere 1.5 kg of H2O by cycling between kieserite and MgSO4??11 H2O. Despite subequal abundances of calcium sulfate, calcium sulfates are not likely to be important in the water cycle of the planet because of sluggish rates of hydration and dehydration and a more limited range of H2O concentrations per kilogram of CaSO4 (0.00 to 0.26 kg kg-1). Modern or recent erosion on Mars attributed to liquid water may be due to the dehydration Of MgSO4??11 H2O because of the inferred abundance and likelihood of occurrence of this phase and its limited stability relative to known variations in temperature and relative humidity.

Laboratory Studies on the Formation of Three C2H4O Isomers-Acetaldehyde (CH3CHO), Ethylene Oxide (c-C2H4O), and Vinyl Alcohol (CH2CHOH)-in Interstellar and Cometary Ices

NASA Astrophysics Data System (ADS)

Bennett, Chris J.; Osamura, Yoshihiro; Lebar, Matt D.; Kaiser, Ralf I.

2005-11-01

Laboratory experiments were conducted to unravel synthetic routes to form three C2H4O isomers-acetaldehyde (CH3CHO), ethylene oxide (c-C2H4O), and vinyl alcohol (CH2CHOH)-in extraterrestrial ices via electronic energy transfer processes initiated by electrons in the track of MeV ion trajectories. Here we present the results of electron irradiation on a 2:1 mixture of carbon dioxide (CO2) and ethylene (C2H4). Our studies suggest that suprathermal oxygen atoms can add to the carbon-carbon π bond of an ethylene molecule to form initially an oxirene diradical (addition to one carbon atom) and the cyclic ethylene oxide molecule (addition to two carbon atoms) at 10 K. The oxirene diradical can undergo a [1, 2]-H shift to the acetaldehyde molecule. Both the ethylene oxide and the acetaldehyde isomers can be stabilized in the surrounding ice matrix. To a minor amount, suprathermal oxygen atoms can insert into a carbon-hydrogen bond of the ethylene molecule, forming vinyl alcohol. Once these isomers have been synthesized inside the ice layers of the coated grains in cold molecular clouds, the newly formed molecules can sublime as the cloud reaches the hot molecular core stage. These laboratory investigations help to explain astronomical observations by Nummelin et al. and Ikeda et al. toward massive star-forming regions and hot cores, where observed fractional abundances of these isomers are higher than can be accounted for by gas-phase reactions alone. Similar synthetic routes could help explain the formation of acetaldehyde and ethylene oxide in comet C/1995 O1 (Hale-Bopp) and also suggest a presence of both isomers in Titan's atmosphere.

Cassini finds an oxygen-carbon dioxide atmosphere at Saturn's icy moon Rhea.

PubMed

Teolis, B D; Jones, G H; Miles, P F; Tokar, R L; Magee, B A; Waite, J H; Roussos, E; Young, D T; Crary, F J; Coates, A J; Johnson, R E; Tseng, W-L; Baragiola, R A

2010-12-24

The flyby measurements of the Cassini spacecraft at Saturn's moon Rhea reveal a tenuous oxygen (O(2))-carbon dioxide (CO(2)) atmosphere. The atmosphere appears to be sustained by chemical decomposition of the surface water ice under irradiation from Saturn's magnetospheric plasma. This in situ detection of an oxidizing atmosphere is consistent with remote observations of other icy bodies, such as Jupiter's moons Europa and Ganymede, and suggestive of a reservoir of radiolytic O(2) locked within Rhea's ice. The presence of CO(2) suggests radiolysis reactions between surface oxidants and organics or sputtering and/or outgassing of CO(2) endogenic to Rhea's ice. Observations of outflowing positive and negative ions give evidence for pickup ionization as a major atmospheric loss mechanism.

On the Formation and Isomer Specific Detection of Propenal (C2H3CHO) and Cyclopropanone (c-C3H4O) in Interstellar Model Ices - A Combined FTIR and Reflectron Time-of-Flight Mass Spectroscopic Study

NASA Astrophysics Data System (ADS)

Abplanalp, Matthew J.; Borsuk, Aleca; Jones, Brant M.; Kaiser, Ralf I.

2015-11-01

The formation routes of two structural isomers—propenal (C2H3CHO) and cyclopropanone (c-C3H4O)—were investigated experimentally by exposing ices of astrophysical interest to energetic electrons at 5.5 K thus mimicking the interaction of ionizing radiation with interstellar ices in cold molecular clouds. The radiation-induced processing of these ices was monitored online and in situ via Fourier Transform Infrared spectroscopy and via temperature programmed desorption exploiting highly sensitive reflectron time-of-flight mass spectrometry coupled with single photon ionization in the post irradiation phase. To selectively probe which isomer(s) is/are formed, the photoionization experiments were conducted with 10.49 and 9.60 eV photons. Our studies provided compelling evidence on the formation of both isomers—propenal (C2H3CHO) and cyclopropanone (c-C3H4O)—in ethylene (C2H4)—carbon monoxide (CO) ices forming propenal and cyclopropanone at a ratio of (4.5 ± 0.9):1. Based on the extracted reaction pathways, the cyclopropanone molecule can be classified as a tracer of a low temperature non-equilibrium chemistry within interstellar ices involving most likely excited triplet states, whereas propenal can be formed at ultralow temperatures, but also during the annealing phase via non-equilibrium as well as thermal chemistry (radical recombination). Since propenal has been detected in the interstellar medium and our laboratory experiments demonstrate that both isomers originated from identical precursor molecules our study predicts that the hitherto elusive second isomer—cyclopropanone—should also be observable toward those astronomical sources such as Sgr B2(N) in which propenal has been detected.

Fourier transform-infrared studies of thin H2SO4/H2O films: Formation, water uptake, and solid-liquid phase changes

NASA Technical Reports Server (NTRS)

Middlebrook, Ann M.; Iraci, Laura T.; Mcneill, Laurie S.; Koehler, Birgit G.; Wilson, Margaret A.; Saastad, Ole W.; Tolbert, Margaret A.; Hanson, David R.

1993-01-01

Fourier transform-infrared (FTIR) spectroscopy was used to examine films representative of stratospheric sulfuric acid aerosols. Thin films of sulfuric acid were formed in situ by the condensed phase reaction of SO3 with H2O. FTIR spectra show that the sulfuric acid films absorb water while cooling in the presence of water vapor. Using stratospheric water pressures, the most dilute solutions observed were greater than 40 wt % before simultaneous ice formation and sulfuric acid freezing occurred. FTIR spectra also revealed that the sulfuric acid films crystallized mainly as sulfuric acid tetrahydrate (SAT). Crystallization occurred either when the composition was about 60 wt% H2SO4 or after ice formed on the films at temperatures 1-4 K below the ice frost point. Finally, we determined that the melting point for SAT depended on the background water pressure and was 216-219 K in the presence of 4 x 10(exp -4) Torr H2O. Our results suggest that once frozen, sulfuric acid aerosols in the stratosphere are likely to melt at these temperatures, 30 K colder than previously thought.

Are Makemake and Eris Sputnik Planets?

NASA Astrophysics Data System (ADS)

Grundy, William M.; Umurhan, Orkan M.

2017-10-01

Makemake and Eris have high albedos (Sicardy et al. 2011; Ortiz et al. 2012) and show strong spectral absorption by CH4 ice (Licandro et al. 2006; Brown et al. 2007; Dumas et al. 2007). Energetic space radiation breaks C-H bonds in CH4 producing fragments that recombine into dark, red macromolecular materials (tholins, e.g., Johnson et al. 1987; Thompson et al. 1987; Strazzulla et al. 1991). This fact, coupled with Pluto's strong CH4 ice absorption bands and high albedo led Stern (1988) to pose the question "why is Pluto bright?". New Horizons has confirmed that Pluto refreshes its surface via seasonal volatile transport (e.g., Stern et al. 2015). However, one part of Pluto refreshes itself in a different way, too. This is the informally named Sputnik Planitia, a vast plain of volatile ice partly filling a probable impact basin. The ice is thick enough to act as a barrier to internal radiogenic heat flow, which drives convective overturning on 105 to 106 year timescales (e.g., McKinnon et al. 2016; Trowbridge et al 2016). Vigorous convection in Sputnik mixes radiolytic products from the surface down into the bulk of the ice, diluting it, and thus maintaining the high albedo of the surface.We propose that the surfaces of Eris and Makemake are similarly refreshed by convection in deep volatile ice deposits, perhaps covering the majority of their surfaces, unlike Pluto's Sputnik, which only covers a small fraction. The local fluxes of energetic radiation dictate production rates for tholin. Assuming steady-state production over the age of the solar system and mixing into the volatile ice, the colors and albedos of the bodies can be used to estimate the thickness of the volatile ice into which the tholin has been diluted through convective mixing. Likewise, for plausible radiogenic internal heat production, lower limits can be set on the thickness of the ice, to support convective mixing. We don't know the rheological properties of mixed N2+CH4 ice, let alone what happens when plausible additional contaminants, such as CO, Ar, C2H2, C2H4, C2H6, etc. are added, but bounding cases for N2-dominated and CH4-dominated ice compositions can be calculated.

Measurements of reflectance spectra of ion-bombarded ice and application to surfaces in the outer solar system

NASA Technical Reports Server (NTRS)

O'Shaughnessy, D. J.; Boring, J. W.; Johnson, R. E.

1988-01-01

The first results of laboratory measurements of the wavelength dependence of the alternation of the visible reflectance of H2O ice irradiated by keV ions are presented. When the implanted species is chemically neutral, absorption is slightly enhanced below 0.55 micron. For an incident species containing sulfur, a strong absorption feature is produced at 0.4 micron, probably corresponding to S3. This occurs at too large a wavelength to account for the absorption feature observed at Europa by Voyager and therefore casts doubt on the recent interpretation of the reflectance data of Europa.

Quantifying atom addition reactions on amorphous solid water: a review of recent laboratory advances

NASA Astrophysics Data System (ADS)

He, Jiao; Vidali, Gianfranco

2018-06-01

Complex organic molecules found in space are mostly formed on and in the ice mantle covering interstellar dust grains. In clouds where ionizing irradiation is insignificant, chemical reactions on the ice mantle are dominated by thermal processes. Modeling of grain surface chemistry requires detailed information from the laboratory, including sticking coefficients, binding energies, diffusion energy barriers, mechanism of reaction, and chemical desorption rates. In this talk, recent laboratory advances in obtaining these information would be reviewed. Specifically, this talk will focus on the efforts in our group in: 1) Determining the mechanism of atomic hydrogen addition reactions on amorphous solid water (ASW); 2) Measuring the chemical desorption coefficient of H+O3-->O2+OH using the time-resolved scattering technique; and 3) Measuring the diffusion energy barrier of volatile molecules on ASW. Further laboratory studies will be suggested.This research was supported by NSF Astronomy & Astrophysics Research Grant #1615897.

Hydrocarbon ices in extra-red TNOs and Centaurs

NASA Astrophysics Data System (ADS)

Dalle Ore, C. M.; Barucci, M.; Emery, J. P.; Cruikshank, D. P.; Merlin, F.; Perna, D.

2012-12-01

We present an analysis of the reddest trans-neptunian objects (TNOs) and Centaurs - those belonging to the RR taxon. The RR class contains more than ¼ of the population of TNOs for which photometric colors are available, including a variety of dynamically different objects. The available data cover the spectral range from 0.3 to 2.2 μm. Previous work investigated possible relations between spectral characteristics and other physical and dynamical parameters. The distribution of ices on TNOs has been analyzed as a function of the object absolute magnitude, taxonomy and dynamical class. In a sample of 76 objects for which visible and near-IR spectroscopic measurements are available, CH3OH ice was detected only on three objects belonging to the RR taxonomic class (5145 Pholus, 55638 2002 VE95 and 90377 Sedna). These three objects are among the reddest, they belong to different dynamical classes, and they have different dimensions. However, all three have similar compositions with Sedna showing a more significant heterogeneity in the kind of hydrocarbon ices found on its surface than the others. To further investigate the presence of hydrocarbon ices, and in particular CH3OH, as part of the composition of the RR taxon we used Spitzer IRAC data available for a subgroup of nine objects. Both methanol and methane have a strong absorption at 3.6 μm, the first of the Spitzer IRAC channels, and a much higher albedo at the following channel at 4.5 μm. This albedo pattern is characteristic of some hydrocarbon ices and is very different from H2O ice that shows instead very low albedos at both channels. Our technique makes use of a large database of models including H2O, CH3OH, CH4, and N 2 ices combined with tholins, amorphous carbon, hydrogenated amorphous carbon, serpentine and olivine in different combinations of relative abundances and grain sizes. We automatically extract the models that match the observations at all color wavelengths therefore obtaining for each object a set of compositions that are consistent with its colors. We detect hydrocarbon ices on most objects in our sample. The presence of methanol, or more generally hydrocarbons, on these extra red objects could imply that they exhibit an almost primordial surface. In fact, laboratory experiments of irradiation of compounds rich in methanol show strong reddening. The reddening effect on a Centaur or TNO depends on the composition of the object and on the irradiation history while the thickness of the organic crust depends on the irradiation dose. These objects, following the hypothesis of Brown et al (2011) that objects that formed farther away might be able to retain their methanol ice, have the surface composition and colors set by formation-location-dependent volatile loss in the early solar system. The results of the current work also support the hypothesis that a substantial mixing has occurred after the TNOs formation but cannot exclude the hypothesis of initial heterogeneity.

Screening of plant resources with anti-ice nucleation activity for frost damage prevention.

PubMed

Suzuki, Shingo; Fukuda, Satoshi; Fukushi, Yukiharu; Arakawa, Keita

2017-11-01

Previous studies have shown that some polyphenols have anti-ice nucleation activity (anti-INA) against ice-nucleating bacteria that contribute to frost damage. In the present study, leaf disk freezing assay, a test of in vitro application to plant leaves, was performed for the screening of anti-INA, which inhibits the ice nucleation activity of an ice-nucleating bacterium Erwinia ananas in water droplets on the leaf surfaces. The application of polyphenols with anti-INA, kaempferol 7-O-β-glucoside and (-)-epigallocatechin gallate, to the leaf disk freezing assay by cooling at -4--6 °C for 3 h, revealed that both the compounds showed anti-INAs against E. ananas in water droplets on the leaf surfaces. Further, this assay also revealed that the extracts of five plant leaves showed high anti-INA against E. ananas in water droplets on leaf surfaces, indicating that they are the candidate resources to protect crops from frost damage.

Temperature- and pressure-dependent structural transformation of methane hydrates in salt environments

NASA Astrophysics Data System (ADS)

Shin, Donghoon; Cha, Minjun; Yang, Youjeong; Choi, Seunghyun; Woo, Yesol; Lee, Jong-Won; Ahn, Docheon; Im, Junhyuck; Lee, Yongjae; Han, Oc Hee; Yoon, Ji-Ho

2017-03-01

Understanding the stability of volatile species and their compounds under various surface and subsurface conditions is of great importance in gaining insights into the formation and evolution of planetary and satellite bodies. We report the experimental results of the temperature- and pressure-dependent structural transformation of methane hydrates in salt environments using in situ synchrotron X-ray powder diffraction, solid-state nuclear magnetic resonance, and Raman spectroscopy. We find that under pressurized and concentrated brine solutions methane hydrate forms a mixture of type I clathrate hydrate, ice, and hydrated salts. Under a low-pressure condition, however, the methane hydrates are decomposed through a rapid sublimation of water molecules from the surface of hydrate crystals, while NaCl · 2H2O undergoes a phase transition into a crystal growth of NaCl via the migration of salt ions. In ambient pressure conditions, the methane hydrate is fully decomposed in brine solutions at temperatures above 252 K, the eutectic point of NaCl · 2H2O.

Measurements of Vertical Profiles of Turbulence, Temperature, Ozone, Aerosols, and BrO over Sea Ice and Tundra Snowpack during BROMEX

NASA Astrophysics Data System (ADS)

Shepson, P.; Caulton, D.; Cambaliza, M. L.; Dhaniyala, S.; Fuentes, J. D.; General, S.; Halfacre, J. W.; Nghiem, S. V.; Perez Perez, L.; Peterson, P. K.; Platt, U.; Pohler, D.; Pratt, K. A.; Simpson, W. R.; Stirm, B.; Walsh, S. J.; Zielcke, J.

2012-12-01

During the BROMEX field campaign of March 2012, we conducted measurements of boundary layer structure, ozone, BrO and aerosol, from a light, twin-engine aircraft during eleven flights originating from Barrow, AK. Flights were conducted over the sea ice in the Beaufort and Chukchi Seas, and over the tundra from Barrow to the Brooks Range, with vertical profiles covering altitudes from the surface to 3.5km in the free troposphere. Flights over the course of one month allowed a variety of sea ice conditions, including open water, nilas, first year sea ice, and frost flowers, to be examined over the Chukchi Sea. Atmospheric turbulence was measured using a calibrated turbulence probe, which will enable characterization of both the structure and turbulence of the Arctic boundary layer. Ozone was measured using a 2B UV absorption instrument. A GRIMM optical particle counter was used to measure 0.25-4 μm sized aerosol particles. The MAX-DOAS instrument enabled measurements of BrO vertical profiles. The aircraft measurements can be used to connect the surface measurements of ozone and BrO from the "Icelander" buoys, and the surface sites at Barrow, with those measured on the aircraft. Here we will discuss the spatial variability/coherence in these data. A major question that will be addressed using these data is the extent to which bromine is activated through reactions at the snowpack/ice surface versus the surface of aerosols. Here we will present a preliminary analysis of the relationships between snow/ice surface types, aerosol size-resolved number concentrations, and the vertical profiles of ozone and BrO.

Raman spectroscopic study of hydrogen ordered ice XIII and of its reversible phase transition to disordered ice V.

PubMed

Salzmann, Christoph G; Hallbrucker, Andreas; Finney, John L; Mayer, Erwin

2006-07-14

Raman spectra of recovered ordered H(2)O (D(2)O) ice XIII doped with 0.01 M HCl (DCl) recorded in vacuo at 80 K are reported in the range 3600-200 cm(-1). The bands are assigned to the various types of modes on the basis of isotope ratios. On thermal cycling between 80 and 120 K, the reversible phase transition to disordered ice V is observed. The remarkable effect of HCl (DCl) on orientational ordering in ice V and its phase transition to ordered ice XIII, first reported in a powder neutron diffraction study of DCl doped D(2)O ice V (C. G. Salzmann, P. G. Radaelli, A. Hallbrucker, E. Mayer, J. L. Finney, Science, 2006, 311, 1758), is demonstrated by Raman spectroscopy and discussed. The dopants KOH and HF have only a minor effect on hydrogen ordering in ice V, as shown by the Raman spectra.

Improvement of Mars surface snow albedo modeling in LMD Mars GCM with SNICAR

NASA Astrophysics Data System (ADS)

Singh, D.; Flanner, M.; Millour, E.

2017-12-01

The current version of Laboratoire de Météorologie Dynamique (LMD) Mars GCM (original-MGCM) uses annually repeating (prescribed) albedo values from the Thermal Emission Spectrometer observations. We integrate the Snow, Ice, and Aerosol Radiation (SNICAR) model with MGCM (SNICAR-MGCM) to prognostically determine H2O and CO2 ice cap albedos interactively in the model. Over snow-covered regions mean SNICAR-MGCM albedo is higher by about 0.034 than original-MGCM. Changes in albedo and surface dust content also impact the shortwave energy flux at the surface. SNICAR-MGCM model simulates a change of -1.26 W/m2 shortwave flux on a global scale. Globally, net CO2 ice deposition increases by about 4% over one Martian annual cycle as compared to original-MGCM simulations. SNICAR integration reduces the net mean global surface temperature, and the global surface pressure of Mars by about 0.87% and 2.5% respectively. Changes in albedo also show a similar distribution as dust deposition over the globe. The SNICAR-MGCM model generates albedos with higher sensitivity to surface dust content as compared to original-MGCM. For snow-covered regions, we improve the correlation between albedo and optical depth of dust from -0.91 to -0.97 with SNICAR-MGCM as compared to original-MGCM. Using new diagnostic capabilities with this model, we find that cryospheric surfaces (with dust) increase the global surface albedo of Mars by 0.022. The cryospheric effect is severely muted by dust in snow, however, which acts to decrease the planet-mean surface albedo by 0.06.

Interaction of D2 with H2O amorphous ice studied by temperature-programmed desorption experiments.

PubMed

Amiaud, L; Fillion, J H; Baouche, S; Dulieu, F; Momeni, A; Lemaire, J L

2006-03-07

The gas-surface interaction of molecular hydrogen D2 with a thin film of porous amorphous solid water (ASW) grown at 10 K by slow vapor deposition has been studied by temperature-programmed-desorption (TPD) experiments. Molecular hydrogen diffuses rapidly into the porous network of the ice. The D2 desorption occurring between 10 and 30 K is considered here as a good probe of the effective surface of ASW interacting with the gas. The desorption kinetics have been systematically measured at various coverages. A careful analysis based on the Arrhenius plot method has provided the D2 binding energies as a function of the coverage. Asymmetric and broad distributions of binding energies were found, with a maximum population peaking at low energy. We propose a model for the desorption kinetics that assumes a complete thermal equilibrium of the molecules with the ice film. The sample is characterized by a distribution of adsorption sites that are filled according to a Fermi-Dirac statistic law. The TPD curves can be simulated and fitted to provide the parameters describing the distribution of the molecules as a function of their binding energy. This approach contributes to a correct description of the interaction of molecular hydrogen with the surface of possibly porous grain mantles in the interstellar medium.

Chemical desorption and diffusive dust chemistry

NASA Astrophysics Data System (ADS)

Dulieu, Francois; Pirronello, Valerio; Minissale, Marco; Congiu, Emanuele; Baouche, Saoud; Chaabouni, Henda; Moudens, Audrey; Accolla, Mario; Cazaux, Stephanie; Manicò, Giulio

In molecular clouds, gaseous species can accrete efficiently on the cold surfaces of dust grains. As for radical-radical reactions, the surface of the grains acts as a third body, and changes dramatically the efficiency of the reactions (i.e., H2 formation), or lowers considerably the barrier to formation (i.e., H2O synthesis) in comparison with gas phase reaction processes. These properties make dust grains efficient catalytic templates. However, the chemical role of dust grains depends on the diffusive properties of the reactive partners. Over the last years, we have developed experimental tools and methods to explore the chemistry occurring on cold (6-50K) surfaces. We have obtained some hints about the diffusivity of H on amorphous ice, and studied in detail the diffusion of O atoms. The latter species appears to have a hopping rate in the range 0.01-100 hops/sec. The diffusion rate of O atoms is dependent on the surface morphology and on the surface temperature. The diffusion law is compatible with a diffusion dominated by quantum tunnelling rather than classical thermal hopping. Using H, O, N atoms and, indirectly, OH and HCO radicals, we have begun to explore many chemical reactive networks. In this presentation, I will focus on the formation of H2O and CO2, and will propose many possible formation routes to obtain these chemical traps. The molecules formed on surfaces have a certain probability of desorbing upon their formation. This non-thermal desorption mechanism, or chemical desorption, has been proposed to explain why some molecules can be detected in the gas phase of those region where they were believed to be part of the icy mantles covering dust grains. We have shown that this process can be very efficient, but is very sensitive to the substrate and the surroundings of the reaction site, is dependent on the kind of molecule formed and its chemical pathway. In my presentation I will present how the surface coverage and the type of reaction can play a major role in the chemical desorption process. I will discuss of possible key parameters that rule this process.

Planetary Ice-Oceans: Numerical Modeling Study of Ice-Shell Growth in Convecting Two-Phase Systems

NASA Astrophysics Data System (ADS)

Allu Peddinti, Divya; McNamara, Allen

2017-04-01

Several icy bodies in the Solar system such as the icy moons Europa and Enceladus exhibit signs of subsurface oceans underneath an ice-shell. For Europa, the geologically young surface, the presence of surface features and the aligned surface chemistry pose interesting questions about formation of the ice-shell and its interaction with the ocean below. This also ties in with its astrobiological potential and implications for similar ice-ocean systems elsewhere in the cosmos. The overall thickness of the H2O layer on Europa is estimated to be 100-150 km while the thickness of the ice-shell is debated. Additionally, Europa is subject to tidal heating due to interaction with Jupiter's immense gravity field. It is of interest to understand how the ice-shell thickness varies in the presence of tidal internal heating and the localization of heating in different regions of the ice-shell. Thus this study aims to determine the effect of tidal internal heating on the growth rate of the ice-shell over time. We perform geodynamic modeling of the ice-ocean system in order to understand how the ice-shell thickness changes with time. The convection code employs the ice Ih-water phase diagram in order to model the two-phase convecting ice-ocean system. All the models begin from an initial warm thick ocean that cools from the top. The numerical experiments analyze three cases: case 1 with no tidal internal heating in the system, case 2 with constant tidal internal heating in the ice and case 3 with viscosity-dependent tidal internal heating in the ice. We track the ice-shell thickness as a function of time as the system cools. Modeling results so far have identified that the shell growth rate changes substantially at a point in time that coincides with a change in the planform of ice-convection cells. Additionally, the velocity vs depth plots indicate a shift from a conduction dominant to a convection dominant ice regime. We compare the three different cases to provide a comprehensive understanding of the temporal variation in the ice-shell thickness due to the addition of heating in the ice.

Five-Year (2004-2009)Observations of Upper Tropospheric Water Vapor and Cloud Ice from MLS and Comparisons with GEOS-5 Analyses

NASA Technical Reports Server (NTRS)

Jiang, Jonathan H.; Su, Hui; Pawson, Steven; Liu, Hui-Chun; Read, William; Waters, Joe W.; Santee, Michelle; Wu, Dong L.; Schwartz, Michael; Lambert, Alyn;

The stability of ground ice in the equatorial region of Mars

NASA Technical Reports Server (NTRS)

Clifford, S. M.; Hillel, D.

1983-01-01

The lifetime of an unreplenished layer of ground ice lying within 30 deg of the Martian equator was examined within the context of the existing data base on Martian regolith and climate. Data on the partial pressure of H2O in the Martian atmosphere and the range of mean annual temperatures indicated the ground ice would be restricted to latitudes poleward of 40 deg. However, the ground ice near the poles may be a relic from early Martian geologic times held in place by a thin layer of regolith. Consideration of twelve model pore size distributions, similar to silt- and clay-type earth soils, was combined with a parallel pore model of gaseous diffusion to calculate the flux of H2O molecules escaping from the subsurface ground ice layer. Martian equatorial ground ice was found to be influenced by the soil structure, the magnitude of the geothermal gradient, the climatic desorption of CO2 from the regolith. It is concluded that equatorial ground ice is present on Mars only if a process of replenishment is active.

Terasonic Excitations in 2D Gold Nanoparticle Arrays in a Water Matrix as Revealed by Atomistic Simulations

DOE PAGES

Bolmatov, Dima; Zhernenkov, Mikhail; Zav’yalov, Dmitry; ...

2016-08-19

Here in this work we report on terahertz phononic excitations in 2D gold nanoparticle arrays in a water matrix through a series of large-scale molecular dynamics simulations. For the first time, we observe acoustic Dirac-like crossings in H (H 2O) atomic (molecular) networks which emerge due to an intraband phononic scattering. These crossings are the phononic fingerprints of ice-like arrangements of H (H 2O) atomic (molecular) networks at nanometer scale. We reveal how phononic excitations in metallic nanoparticles and the water matrix reciprocally impact on one another providing the mechanism for the THz phononics manipulation via structural engineering. In addition,more » we show that by tuning the arrangement of 2D gold nanoparticle assemblies the Au phononic polarizations experience sub-terahertz hybridization (Kohn anomaly) due to surface electron-phonon relaxation processes. This opens the way for the sound control and manipulation in soft matter metamaterials at nanoscale.« less

Mechanisms of the Formation of Adenine, Guanine, and Their Analogues in UV-Irradiated Mixed NH3:H2O Molecular Ices Containing Purine

NASA Astrophysics Data System (ADS)

Bera, Partha P.; Stein, Tamar; Head-Gordon, Martin; Lee, Timothy J.

2017-08-01

We investigated the formation mechanisms of the nucleobases adenine and guanine and the nucleobase analogues hypoxanthine, xanthine, isoguanine, and 2,6-diaminopurine in a UV-irradiated mixed 10:1 H2O:NH3 ice seeded with precursor purine by using ab initio and density functional theory computations. Our quantum chemical investigations suggest that a multistep reaction mechanism involving purine cation, hydroxyl and amino radicals, together with water and ammonia, explains the experimentally obtained products in an independent study. The relative abundances of these products appear to largely follow from relative thermodynamic stabilities. The key role of the purine cation is likely to be the reason why purine is not functionalized in pure ammonia ice, where cations are promptly neutralized by free electrons from NH3 ionization. Amine group addition to purine is slightly favored over hydroxyl group attachment based on energetics, but hydroxyl is much more abundant due to higher abundance of H2O. The amino group is preferentially attached to the 6 position, giving 6-aminopurine, that is, adenine, while the hydroxyl group is preferentially attached to the 2 position, leading to 2-hydroxypurine. A second substitution by hydroxyl or amino group occurs at either the 6 or the 2 position depending on the first substitution. Given that H2O is far more abundant than NH3 in the experimentally studied ices (as well as based on interstellar abundances), xanthine and isoguanine are expected to be the most abundant bi-substituted photoproducts.

Nonlinear Spectral Mixture Modeling to Estimate Water-Ice Abundance of Martian Regolith

NASA Astrophysics Data System (ADS)

Gyalay, Szilard; Chu, Kathryn; Zeev Noe Dobrea, Eldar

2017-10-01

We present a novel technique to estimate the abundance of water-ice in the Martian permafrost using Phoenix Surface Stereo Imager multispectral data. In previous work, Cull et al. (2010) estimated the abundance of water-ice in trenches dug by the Mars Phoenix lander by modeling the spectra of the icy regolith using the radiative transfer methods described in Hapke (2008) with optical constants for Mauna Kea palagonite (Clancy et al., 1995) as a substitute for unknown Martian regolith optical constants. Our technique, which uses the radiative transfer methods described in Shkuratov et al. (1999), seeks to eliminate the uncertainty that stems from not knowing the composition of the Martian regolith by using observations of the Martian soil before and after the water-ice has sublimated away. We use observations of the desiccated regolith sample to estimate its complex index of refraction from its spectrum. This removes any a priori assumptions of Martian regolith composition, limiting our free parameters to the estimated real index of refraction of the dry regolith at one specific wavelength, ice grain size, and regolith porosity. We can then model mixtures of regolith and water-ice, fitting to the original icy spectrum to estimate the ice abundance. To constrain the uncertainties in this technique, we performed laboratory measurements of the spectra of known mixtures of water-ice and dry soils as well as those of soils after desiccation with controlled viewing geometries. Finally, we applied the technique to Phoenix Surface Stereo Imager observations and estimated water-ice abundances consistent with pore-fill in the near-surface ice. This abundance is consistent with atmospheric diffusion, which has implications to our understanding of the history of water-ice on Mars and the role of the regolith at high latitudes as a reservoir of atmospheric H2O.

A simulation of ice cloud particle size, humidity, and temperature measurements from the TWICE CubeSat.

PubMed

Jiang, Jonathan H; Yue, Qing; Su, Hui; Reising, Steven C; Kangaslahti, Pekka P; Deal, William R; Schlecht, Erich T; Wu, Longtao; Evans, K Franklin

2017-08-01

This paper describes a forward radiative transfer model and retrieval system (FMRS) for the Tropospheric Water and cloud ICE (TWICE) CubeSat instrument. We use the FMRS to simulate radiances for the TWICE's 14 millimeter- and submillimeter-wavelength channels for a tropical atmospheric state produced by a Weather Research and Forecasting model simulation. We also perform simultaneous retrievals of cloud ice particle size, ice water content (IWC), water vapor content (H 2 O), and temperature from the simulated TWICE radiances using the FMRS. We show that the TWICE instrument is capable of retrieving ice particle size in the range of ~50-1000 μm in mass mean effective diameter with approximately 50% uncertainty. The uncertainties of other retrievals from TWICE are about 1 K for temperature, 50% for IWC, and 20% for H 2 O.

A simulation of ice cloud particle size, humidity, and temperature measurements from the TWICE CubeSat

PubMed Central

Yue, Qing; Su, Hui; Reising, Steven C.; Kangaslahti, Pekka P.; Deal, William R.; Schlecht, Erich T.; Wu, Longtao; Evans, K. Franklin

2017-01-01

Abstract This paper describes a forward radiative transfer model and retrieval system (FMRS) for the Tropospheric Water and cloud ICE (TWICE) CubeSat instrument. We use the FMRS to simulate radiances for the TWICE's 14 millimeter‐ and submillimeter‐wavelength channels for a tropical atmospheric state produced by a Weather Research and Forecasting model simulation. We also perform simultaneous retrievals of cloud ice particle size, ice water content (IWC), water vapor content (H2O), and temperature from the simulated TWICE radiances using the FMRS. We show that the TWICE instrument is capable of retrieving ice particle size in the range of ~50–1000 μm in mass mean effective diameter with approximately 50% uncertainty. The uncertainties of other retrievals from TWICE are about 1 K for temperature, 50% for IWC, and 20% for H2O. PMID:29104900

Physical and Biological Drivers of Biogeochemical Tracers Within the Seasonal Sea Ice Zone of the Southern Ocean From Profiling Floats

NASA Astrophysics Data System (ADS)

Briggs, Ellen M.; Martz, Todd R.; Talley, Lynne D.; Mazloff, Matthew R.; Johnson, Kenneth S.

2018-02-01

Here we present initial findings from nine profiling floats equipped with pH, O2, NO3-, and other biogeochemical sensors that were deployed in the seasonal ice zone (SIZ) of the Southern Ocean in 2014 and 2015 through the Southern Ocean Carbon and Climate Observations and Modelling (SOCCOM) project. A large springtime phytoplankton bloom was observed that coincided with sea ice melt for all nine floats. We argue this bloom results from a shoaling of the mixed layer depth, increased vertical stability, and enhanced nutrient and light availability as the sea ice melts. This interpretation is supported by the absence of a springtime bloom when one of the floats left the SIZ in the second year of observations. During the sea ice covered period, net heterotrophic conditions were observed. The rate of uptake of O2 and release of dissolved inorganic carbon (derived from pH and estimated total alkalinity) and NO3- is reminiscent of biological respiration and is nearly Redfieldian for the nine floats. A simple model of mixed layer physics was developed to separate the physical and biological components of the signal in pH and O2 over one annual cycle for a float in the Ross Sea SIZ. The resulting annual net community production suggests that seasonal respiration during the ice covered period of the year nearly balances the production in the euphotic layer of up to 5 mol C m-2 during the ice free period leading to a net of near zero carbon exported to depth for this one float.

Solar wind ion impacts into ice surfaces: A molecular-dynamics study using the REAX force field

NASA Astrophysics Data System (ADS)

Anders, Christian; Urbassek, Herbert M.

2017-01-01

Molecular dynamics simulation is used to study the effects of solar-wind ion irradiation on an ice target, focusing on the effects of nuclear energy deposition. A reactive force field (REAX) interatomic interaction potential is employed that allows us to model the breaking and formation of molecular bonds and hence to follow the chemistry occurring in the target. As ions we study H and He ions as typical constituents of the solar wind, and Ne as an example of a heavier ion; they impact at the speed of maximum flux in the solar wind, 400 km/s. The ice consists of a mixture of H2O, CO2, CH3OH and NH3. We find that molecular dissociations occur within 0.2 ps after ion impact and new products are formed up to a time of 1 ps; only water has a slower dynamics, due to highly mobile H atoms allowing for late recombinations. The number of dissociations, and hence also of product molecules increases from H over He to Ne ion projectiles and can be quantified by the amount of energy deposited in the target by these ions. The most abundant products formed include CO, OH and NH2. Reaction products are most complex for Ne impact, and include H3O, formaldehyde (H2CO), HO2, and NO. Formaldehyde is important as it is formed relatively frequently and is known as a precursor in the formation of sugars. In addition, molecules containing all CHON elements are formed, among which are CH2NO, CONH, methanolamine (CH5NO), and ethyne (C2H2). Repeated impacts generate novel, and more complex product species; we found CN, CH4, CH3NO, methylamine (CH3NH2), and acetamide (CH3CONH2), among others; the complex species are formed less frequently than the simple fragments. Sputtering occurs for all projectiles, even H. The ejecta are either original molecules - in particular CO2 - or simple fragments; only few product molecules are emitted.

New experimental capability to investigate the hypervelocity micrometeoroid bombardment of cryogenic surfaces

NASA Astrophysics Data System (ADS)

Nelson, Andrew Oakleigh; Dee, Richard; Gudipati, Murthy S.; Horányi, Mihály; James, David; Kempf, Sascha; Munsat, Tobin; Sternovsky, Zoltán; Ulibarri, Zach

2016-02-01

Ice is prevalent throughout the solar system and beyond. Though the evolution of many of these icy surfaces is highly dependent on associated micrometeoroid impact phenomena, experimental investigation of these impacts has been extremely limited, especially at the impactor speeds encountered in space. The dust accelerator facility at the Institute for Modeling Plasmas, Atmospheres, and Cosmic Dust (IMPACT) of NASA's Solar System Exploration Research Virtual Institute has developed a novel cryogenic system that will facilitate future study of hypervelocity impacts into ice and icy regolith. The target consists of a copper block, cooled by liquid nitrogen, upon which layers of vapor-deposited ice, pre-frozen ice, or icy regolith can be built in a controlled and quantifiable environment. This ice can be grown from a variety of materials, including H2O, CH3OH, NH3, and slurries containing nanophase iron. Ice temperatures can be varied between 96 K and 150 K and ice thickness greater than 150 nm can be accurately measured. Importantly, the composition of ion plumes created during micrometeoroid impacts onto these icy layers can be measured even in trace amounts by in situ time-of-flight mass spectroscopy. In this paper, we present the fundamental design components of the cryogenic target chamber at IMPACT and proof-of-concept results from target development and from first impacts into thick layers of water ice.

Geological Mapping of Pluto and Charon Using New Horizons Data

NASA Astrophysics Data System (ADS)

Moore, J. M.; Spencer, J. R.; McKinnon, W. B.; Howard, A. D.; White, O. M.; Umurhan, O. M.; Schenk, P. M.; Beyer, R. A.; Singer, K.; Stern, S. A.; Weaver, H. A.; Young, L. A.; Ennico Smith, K.; Olkin, C.; Horizons Geology, New; Geophysics Imaging Team

2016-06-01

Pluto and Charon exhibit strikingly different surface appearances, despite their similar densities and presumed bulk compositions. Systematic mapping has revealed that much of Pluto's surface can be attributed to surface-atmosphere interactions and the mobilization of volatile ices by insolation. Many mapped valley systems appear to be the consequence of glaciation involving nitrogen ice. Other geological activity requires or required internal heating. The convection and advection of volatile ices in Sputnik Planum can be powered by present-day radiogenic heat loss. On the other hand, the prominent mountains at the western margin of Sputnik Planum, and the strange, multi-km-high mound features to the south, probably composed of H2O, are young geologically as inferred by light cratering and superposition relationships. Their origin, and what drove their formation so late in Solar System history, is under investigation. The dynamic remolding of landscapes by volatile transport seen on Pluto is not unambiguously evident in the mapping of Charon. Charon does, however, display a large resurfaced plain and globally engirdling extensional tectonic network attesting to its early endogenic vigor.

The Geology of Pluto and Charon as Revealed by New Horizons

NASA Astrophysics Data System (ADS)

Moore, Jeffrey M.; Spencer, John R.; McKinnon, William B.; Stern, S. Alan; Young, Leslie A.; Weaver, Harold A.; Olkin, Cathy B.; Ennico, Kim; New Horizons GGI Team

2016-04-01

NASA's New Horizons spacecraft has revealed that Pluto and Charon exhibit strikingly different surface appearances, despite their similar densities and presumed bulk compositions. Much of Pluto's surface can be attributed to surface-atmosphere interactions and the mobilization of volatile ices by insolation. Many valley systems appear to be the consequence of glaciation involving nitrogen ice. Other geological activity requires or required internal heating. The convection and advection of volatile ices in Sputnik Planum can be powered by present-day radiogenic heat loss. On the other hand, the prominent mountains at the western margin of Sputnik Planum, and the strange, multi-km-high mound features to the south, probably composed of H2O, are young geologically as inferred by light cratering and superposition relationships. Their origin, and what drove their formation so late in Solar System history, is under investigation. The dynamic remolding of landscapes by volatile transport seen on Pluto is not unambiguously evident on Charon. Charon does, however, display a large resurfaced plain and globally engirdling extensional tectonic network attesting to its early endogenic vigor.

The Geology of Pluto and Charon as Revealed by New Horizons

NASA Technical Reports Server (NTRS)

Moore, Jeffrey M.; Spencer, John R.; McKinnon, William B.; Stern, S. Alan; Young, Leslie A.; Weaver, Harold A.; Olkin, Cathy B.; Ennico, Kim

2016-01-01

NASA's New Horizons spacecraft has revealed that Pluto and Charon exhibit strikingly different surface appearances, despite their similar densities and presumed bulk compositions. Much of Pluto's surface can be attributed to surface-atmosphere interactions and the mobilization of volatile ices by insolation. Many valley systems appear to be the consequence of glaciation involving nitrogen ice. Other geological activity requires or required internal heating. The convection and advection of volatile ices in Sputnik Planum can be powered by present-day radiogenic heat loss. On the other hand, the prominent mountains at the western margin of Sputnik Planum, and the strange, multi-km-high mound features to the south, probably composed of H2O, are young geologically as inferred by light cratering and superposition relationships. Their origin, and what drove their formation so late in Solar System history, is under investigation. The dynamic remolding of landscapes by volatile transport seen on Pluto is not unambiguously evident on Charon. Charon does, however, display a large resurfaced plain and globally engirdling extensional tectonic network attesting to its early endogenic vigor.

H2-rich interstellar grain mantles: An equilibrium description

NASA Technical Reports Server (NTRS)

Dissly, Richard W.; Allen, Mark; Anicich, Vincent G.

1994-01-01

Experiments simulating the codeposition of molecular hydrogen and water ice on interstellar grains demonstrate that amorphous water ice at 12 K can incorporate a substantial amount of H2, up to a mole ratio of H2/H2O = 0.53. We find that the physical behavior of approximately 80% of the hydrogen can be explained satisfactorily in terms of an equilibrium population, thermodynamically governed by a wide distribution of binding site energies. Such a description predicts that gas phase accretion could lead to mole fractions of H2 in interstellar grain mantles of nearly 0.3; for the probable conditions of WL5 in the rho Ophiuchi cloud, an H2 mole fraction of between 0.05 and 0.3 is predicted, in possible agreement with the observed abundance reported by Sandford, Allamandola, & Geballe. Accretion of gas phase H2 onto grain mantles, rather than photochemical production of H2 within the ice, could be a general explanation for frozen H2 in interstellar ices. We speculate on the implications of such a composition for grain mantle chemistry and physics.

Formation of Hydroxylamine from Ammonia and Hydroxyl Radicals

NASA Astrophysics Data System (ADS)

Krim, Lahouari; Zins, Emilie-Laure

2014-06-01

In the interstellar medium, as well as in icy comets, ammonia may be a crucial species in the first step toward the formation of amino-acids and other prebiotic molecules such as hydroxylamine (NH2OH). It is worth to notice that the NH3/H2 ratio in the ISM is 3 10-5 compared the H2O/H2 one which is only 7 10-5. Using either electron-UV irradiations of water-ammonia ices or successive hydrogenation of solid nitric oxide, laboratory experiments have already shown the feasibility of reactions that may take place on the surface of ice grains in molecular clouds, and may lead to the formation of this precursor. Herein is proposed a new reaction pathway involving ammonia and hydroxyl radicals generated in a microwave discharge. Experimental studies, at 3 and 10 K, in solid phase as well as in neon matrix have shown that this reaction proceed via a hydrogen abstraction, leading to the formation of NH2 radical, that further recombine with hydroxyl radical to form hydroxylamine, under non-energetic conditions.

Investigating the correlations between water coma emissions and active regions in comet 67P/ Churyumov-Gerasimenko

NASA Astrophysics Data System (ADS)

Migliorini, Alessandra; Filacchione, Gianrico; Capaccioni, Fabrizio; Piccioni, Giuseppe; Bockelee-Morvan, Dominique; Érard, Stéphane; Leyrat, Cedric; Combi, Michael R.; Fougere, Nicolas; Rinaldi, Giovanna; VIRTIS Team

2016-10-01

Vibrational emission lines of H2O and CO2 at 2.67 and 4.27 μm, respectively, were identified by the VIRTIS spectrometer (Bockelée-Morvan et al., 2015; Migliorini et al., 2016; Fink et al., 2016) and mapped from the surface up to about 10 km altitude with a spatial resolution on the order of tens of meters per pixel (Migliorini et al., 2016).Data acquired in April 2015 with the VIRTIS spectrometer on board the Rosetta mission, provided information on the possible correlation between the H2O emission in the inner coma and the exposed water deposits detected in the Hapi region on the 67P/Churyumov-Gerasimenko surface (Migliorini et al., 2106; De Sanctis et al., 2015). Further bright spots attributed to exposed water ice have been identified in other regions by OSIRIS at visible wavelengths (Pommerol, et al., 2015) and confirmed in the infrared by VIRTIS-M in the Imothep region (Filacchione et al., 2016). The small dimensions of these icy spots - approximately 100x100 m (Filacchione et al., 2016) - and the relatively small amount of water ice (about 5%) make uncertain the correlation with the strong emissions in the coma.However, VIRTIS data show that the distribution of jet-like emissions seems to follow the distribution of cliffs and exposed areas identified in the North hemisphere with OSIRIS camera (Vincent et al., 2015). These areas are mainly concentrated in correspondence of comet's rough terrains, while a lack of active regions is observed in the comet's neck. Nevertheless, strong H2O emission is observed above the neck with VIRTIS. This might be a consequence of gas jets that are originated in the surrounding of the neck but converging towards the neck itself. This gaseous activity is the main driver of the dust upwelling (Migliorini et al, 2016; Rinaldi et al., in preparation)In this paper, we investigate the relationship between H2O vapour observed with VIRTIS within 5 km from the 67P/C-G nucleus and the exposed regions identified by OSIRIS on the surface (in the timeframe March to April 2015) with an attempt to address possible variations with the heliocentric distance.

Interstellar/Precometary Organic Material and the Photochemical Evolution of Complex Organics

NASA Technical Reports Server (NTRS)

Allamandola, Lou J.; Bernstein, Max; Sandford, Scott; Witteborn, Fred (Technical Monitor)

1996-01-01

During the past two decades ground-, air-, and space-based infrared spectroscopic observations, combined with realistic laboratory simulations, have revolutionized our understanding of interstellar ice and dust, the raw materials from which planets, comets and stars form. Most interstellar material is concentrated in Large molecular clouds where simple molecules are formed by dust grain and gas phase reactions. Gaseous species striking the cold (10 K) dust will stick, forming an icy grain mantle. This accretion, coupled with energetic particle bombardment and UV photolysis, will produce a complex chemical mixture containing volatile, non-volatile, and isotopically fractionated species. Ices in molecular clouds contain the very simple molecules H2O, CH3OH, CO, CO2, H2, and perhaps some NH3 and H2CO, as well as more complex species including nitriles and ketones or esters. The evidence for these compounds as well as carbon rich materials such as polycyclic aromatic hydrocarbons (PAHs), microdiamonds, and amorphous carbon will be reviewed and the possible connections with comets and meteorites will be presented in the first part of the talk. The second part of the presentation will focus on interstellar/precometary ice photochemical evolution. The chemical composition and photochemical evolution of realistic interstellar/pre-cometary ice analogs containing methanol will be discussed. ultraviolet photolysis of these ices produces H2, H2CO, CO2, CO, CH4, HCO, and more complex molecules. Infrared spectroscopy, H-1 and C-13 nuclear magnetic resonance (NMR) spectroscopy, and gas chromatography-mass spectrometry demonstrate that when ices representative of interstellar grains and comets are exposed to UV radiation at low temperature a series of moderately complex organic molecules are formed in the ice including: CH3CH2OH (ethanol), HC(=O)NH2 (formamide), CH3C(=O)NH2 (acetamide), and R-C(integral)N (nitriles). Several of these are already known to be in the interstellar medium, and their presence indicates the importance of grain processing. After warming to room temperature what remains is an organic residue composed primarily of Hexamethylenetetramine (HMT, C6H12N4), with lesser amounts of polyoxymethylene related species (POMs), amides, and ketones. This is in sharp contrast to the organic residues produced by irradiating ices which do not contain methanol (unrealistic interstellar ice analogs) or thermally promoted polymerization-type reactions in unirradiated realistic ice mixtures. Here HMT is only a minor product in a residue dominated by a mixture of polyoxymethylene related species. The implications, for infrared astronomy and astrochemistry, of high concentrations of HMT in interstellar and cometary ices may be profound. The ultraviolet photolysis of HMT frozen in H20 ice produces the "XCN" band observed in the spectra of protostellar objects and laboratory ices, as well as carbon oxides and other nitriles. Thus, HMT may be a precursor of XCN in protostellar objects and a source of CN and CO in the tail of comets. Also, HMT is known to hydrolyze under acidic conditions to yield ammonia and formaldehyde as well as amino acids. Thus, HMT may have been a source of organic material delivered to the early earth by comets.

Analysis of reactive bromine production and ozone depletion in the Arctic boundary layer using 3-D simulations with GEM-AQ: inference from synoptic-scale patterns

NASA Astrophysics Data System (ADS)

Toyota, K.; McConnell, J. C.; Lupu, A.; Neary, L.; McLinden, C. A.; Richter, A.; Kwok, R.; Semeniuk, K.; Kaminski, J. W.; Gong, S.-L.; Jarosz, J.; Chipperfield, M. P.; Sioris, C. E.

2011-04-01

Episodes of high bromine levels and surface ozone depletion in the springtime Arctic are simulated by an online air-quality model, GEM-AQ, with gas-phase and heterogeneous reactions of inorganic bromine species and a simple scheme of air-snowpack chemical interactions implemented for this study. Snowpack on sea ice is assumed to be the only source of bromine to the atmosphere and to be capable of converting relatively stable bromine species to photolabile Br2 via air-snowpack interactions. A set of sensitivity model runs are performed for April 2001 at a horizontal resolution of approximately 100 km×100 km in the Arctic, to provide insights into the effects of temperature and the age (first-year, FY, versus multi-year, MY) of sea ice on the release of reactive bromine to the atmosphere. The model simulations capture much of the temporal variations in surface ozone mixing ratios as observed at stations in the high Arctic and the synoptic-scale evolution of areas with enhanced BrO column amount ("BrO clouds") as estimated from satellite observations. The simulated "BrO clouds" are in modestly better agreement with the satellite measurements when the FY sea ice is assumed to be more efficient at releasing reactive bromine to the atmosphere than on the MY sea ice. Surface ozone data from coastal stations used in this study are not sufficient to evaluate unambiguously the difference between the FY sea ice and the MY sea ice as a source of bromine. The results strongly suggest that reactive bromine is released ubiquitously from the snow on the sea ice during the Arctic spring while the timing and location of the bromine release are largely controlled by meteorological factors. It appears that a rapid advection and an enhanced turbulent diffusion associated with strong boundary-layer winds drive transport and dispersion of ozone to the near-surface air over the sea ice, increasing the oxidation rate of bromide (Br-) in the surface snow. Also, if indeed the surface snowpack does supply most of the reactive bromine in the Arctic boundary layer, it appears to be capable of releasing reactive bromine at temperatures as high as -10 °C, particularly on the sea ice in the central and eastern Arctic Ocean. Dynamically-induced BrO column variability in the lowermost stratosphere appears to interfere with the use of satellite BrO column measurements for interpreting BrO variability in the lower troposphere but probably not to the extent of totally obscuring "BrO clouds" that originate from the surface snow/ice source of bromine in the high Arctic. A budget analysis of the simulated air-surface exchange of bromine compounds suggests that a "bromine explosion" occurs in the interstitial air of the snowpack and/or is accelerated by heterogeneous reactions on the surface of wind-blown snow in ambient air, both of which are not represented explicitly in our simple model but could have been approximated by a parameter adjustment for the yield of Br2 from the trigger.

H-atom addition and abstraction reactions in mixed CO, H2CO and CH3OH ices - an extended view on complex organic molecule formation

NASA Astrophysics Data System (ADS)

Chuang, K.-J.; Fedoseev, G.; Ioppolo, S.; van Dishoeck, E. F.; Linnartz, H.

2016-01-01

Complex organic molecules (COMs) have been observed not only in the hot cores surrounding low- and high-mass protostars, but also in cold dark clouds. Therefore, it is interesting to understand how such species can be formed without the presence of embedded energy sources. We present new laboratory experiments on the low-temperature solid state formation of three complex molecules - methyl formate (HC(O)OCH3), glycolaldehyde (HC(O)CH2OH) and ethylene glycol (H2C(OH)CH2OH) - through recombination of free radicals formed via H-atom addition and abstraction reactions at different stages in the CO→H2CO→CH3OH hydrogenation network at 15 K. The experiments extend previous CO hydrogenation studies and aim at resembling the physical-chemical conditions typical of the CO freeze-out stage in dark molecular clouds, when H2CO and CH3OH form by recombination of accreting CO molecules and H-atoms on ice grains. We confirm that H2CO, once formed through CO hydrogenation, not only yields CH3OH through ongoing H-atom addition reactions, but is also subject to H-atom-induced abstraction reactions, yielding CO again. In a similar way, H2CO is also formed in abstraction reactions involving CH3OH. The dominant methanol H-atom abstraction product is expected to be CH2OH, while H-atom additions to H2CO should at least partially proceed through CH3O intermediate radicals. The occurrence of H-atom abstraction reactions in ice mantles leads to more reactive intermediates (HCO, CH3O and CH2OH) than previously thought, when assuming sequential H-atom addition reactions only. This enhances the probability to form COMs through radical-radical recombination without the need of UV photolysis or cosmic rays as external triggers.

To determine ice layer thickness of Europa by high energy neutrino

NASA Astrophysics Data System (ADS)

Shoji, D.; Kurita, K.; Tanaka, H. K.

2010-12-01

Europa, the second closest Galilean satellite is one of the targets which are suspected to have an internal ocean. Detection and characterization of the internal ocean is one of the main subjects for Europa orbiter exploration. Although the gravitational data has shown the thickness of the surface H2O layer of 80-170km[1], it can not determine the phase of H2O. The variations in the magnetic field associated with the induced current in the internal ocean can determine the thickness of the layer of ice if satellite's orbits satisfy the required conditions. Observations of tidal amplitude forced by Jupiter can also resolve the thickness of the surface lithosphere[2]. At moment because of the lack of observational constraints there exist two contrasting models:thick ice layer model and thin model. Here we propose new method to detect the ocean directly based on the radiation by high energy neutrino interacted with matter. Schaefer et al[3] have proposed a similar method to determine ice layer thickness. We will focus on the detection of internal ocean for Europa and present the method is suitable for actual situations of Europa exploration by numerical simulations. Neutrino is famous for its traveling at long distance without any interaction with matter. When high energy neutrinos traverse in Europa hadronic showers are produced by the weak interaction with the nucleons that makes the body of Europa. These hadronic showers induces excess electrons. Because of these excess electrons, Cherenkov photons are emitted. When this radiation occurs in the ice layer, radiations whose wave length is over 10cm should be coherent because the scale of the shower becomes small (a few cm) in the ice, which is called as Askaryan effect[3]. Thus, the intensity of the radiation whose frequency is a few GHz should be enhanced. Since ice has a much longer attenuation length than water, the radiations which occur in the surface ice layer could be detected by the antenna outside Europa but those which occur in the internal ocean can not be detected. Difference in the photon flux produced by this effect is expected for different thickness of the ice layer. In the presentation we show the results by simulation on the interaction of high energy neutrinos with Europa by JULIeT, which is the simulation software for neutrino propagation developed by Chiba University[5]. We assume homogeneous flux of high energy neutrino(10^19 eV) and calculate induced radiations. By using the antenna of m^2, a remarkable difference in number of radiation observed up to ice layer of 15km. References [1] Anderson et al. (1998), Europa's Differentiated Internal Structure: Inferences from Four Galileo Encounters, Science, 281, 2019-2022 [2] Hussmann et al. (2010), Measuring tidal deformation at Europa’s surface, Advance in Space Research [3] Schaefer et al. (2009), AN INSTRUMENT FOR MEASURING ICE THICKNESS ON EUROPA, Synergistic Science & Instrument Poster Abstracts Europa Jupiter System Mission Instrument Workshop, pp 38 [4] Askar'yan. (1962), Excess Negative Charge of an Electron-Photon Shower and Its Coherent, JETP, 14, 441-443 [5] Ishibashi et al. JULIeT Users Manual Version 3.3,http://www.ppl.phys.chiba-u.jp/JULIeT/manual/manual.pdf

Gemini NorthNIRI Spectra of Pluto and Charon: Simultaneous Analysis of the Surface and Atmosphere

NASA Technical Reports Server (NTRS)

Cook, Jason C.; Cruikshank, Dale P.; Young, Leslie A.

2014-01-01

94035We report on our analysis of blended Pluto and Charon spectra over the wavelength range 1.4 to 2.5 m as obtained by the NIRI instrument on Gemini North on June 25-28, 2004. The data have a resolving power () around 1500 and a SNR around 200 per pixel. The observed blended spectra are compared to models that combine absorption from the solid ice on the surface using Hapke theory, and absorption from the gaseous atmosphere. We assume the spectrum is a combination of several spatially separate spectral units: a CH4-rich ice unit, a volatile unit (an intimate mixture of N2, CH4 and CO), and a Charon unit (H2O, ammonia hydrate and kaolinite). We test for the presence of hydrocarbons (i.e. C2H6) and nitriles (i.e. HCN) and examine cases where additional ices are present as either pure separate spatial units, mixed with the CH4-rich unit or part of the volatile unit. We conclude that 2-4 of Plutos surface is covered with pure-C2H6 and our identification of C2H6 is significantly strengthened when absorption due to gaseous CH4 is included. The inclusion of Plutos atmosphere demonstrates that low-resolution, high-SNR observations are capable of detecting Plutos atmosphere during a time when Plutos atmosphere may have been undergoing rapid changes (1988-2002) and no high-resolution spectra were obtained. In particular, we identify features at 1.665 and 2.317 m as the Q-branch of the 23 and 3+4 bands of gaseous CH4, respectively. The later band is also evident in many previously published spectra of Pluto. Our analysis finds it is unnecessary to include 13CO to explain the depth of the 2.405 m, which has been previously suggested to be a spectral blended with C2H6, but we cannot definitively rule out its presence. Funding for this work (Cook) has been provided by a NASA-PATM grant.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cooke, Ilsa R.; Fayolle, Edith C.; Öberg, Karin I., E-mail: irc5zb@virginia.edu

CO{sub 2} ice is an important reservoir of carbon and oxygen in star- and planet-forming regions. Together with water and CO, CO{sub 2} sets the physical and chemical characteristics of interstellar icy grain mantles, including desorption and diffusion energies for other ice constituents. A detailed understanding of CO{sub 2} ice spectroscopy is a prerequisite to characterize CO{sub 2} interactions with other volatiles both in interstellar ices and in laboratory experiments of interstellar ice analogs. We report laboratory spectra of the CO{sub 2} longitudinal optical (LO) phonon mode in pure CO{sub 2} ice and in CO{sub 2} ice mixtures with H{submore » 2}O, CO, and O{sub 2} components. We show that the LO phonon mode position is sensitive to the mixing ratio of various ice components of astronomical interest. In the era of the James Webb Space Telescope , this characteristic could be used to constrain interstellar ice compositions and morphologies. More immediately, LO phonon mode spectroscopy provides a sensitive probe of ice mixing in the laboratory and should thus enable diffusion measurements with higher precision than has been previously possible.« less

Radiolytic Cryovolcanism Revisited

NASA Astrophysics Data System (ADS)

Cooper, J. F.; Cooper, P. D.; Sittler, E. C.; Wesenberg, R. P.

2013-12-01

Active geysers of water vapor and ice grains from the south pole of Enceladus are not yet definitively explained in terms of energy sources and processes. Other instances of hot (Io) and cold (Mars, Triton) volcanism beyond Earth are known if not fully understood. We revisit, in comparison to other models, the 'Old Faithful' theory of radiolytic gas-driven cryovolcanism first proposed by Cooper et al. [Plan. Sp. Sci. 2009]. In the energetic electron irradiation environment of Enceladus within Saturn's magnetosphere, a 10-percent duty cycle could be maintained for current geyser activity driven by gases from oxidation of ammonia to N2 and methane to CO2 in the thermal margins of a south polar sea. Much shorter duty cycles down to 0.01 percent would be required to account for thermal power output up to 16 GW, Steady accumulation of oxidant energy over four billion years could have powered all Enceladus emissions over the past four hundred thousand to four hundred million years. There could be separate energy sources driving mass flow and thermal emission over vastly different time scales. Since episodic tidal dissipation on 10 Myr time scales at 0.1 - 1 Gyr intervals [O'Neill and Nimmo, Nature 2010], and thus duty cycles 1 - 10 percent, could heat the polar sea to the current level, the radiolytic energy source could easily power and modulate the geyser mass flow on million-year time scales. Maximum thermal emission temperature 223 K [Abramov and Spencer, Icarus 2009] hints at thermal buffering in the basal and vent wall layers by a 1:1 H2O:H2O2 radiolytic eutectic, assuming deep ice crust saturation with H2O2 from long cumulative surface irradiation and downward ice convection. Due to density stratification the peroxide eutectic and salt water layers could separate, so that the denser peroxide layer (1.2 g/cc) descends to the polar sea while the lighter salt water (1.05 g/cc) rises along separate channels. Methane reservoirs could be found dissolved into the polar sea, or else trapped in hydrates [Kieffer et al., Science 2006] along flow paths and at the walls of the polar sea at surface depths below 20 km [Fortes, Icarus 2007]. Driver gas production for cryovolcanism could occur wherever these two layers come into contact under requisite temperature and pressure conditions, e.g. from 220 K and 10 bar at the 10-km basal layer of the overlying ice crust to 647 K and 220 bars at the liquid water limit, above the core-mantle boundary at 460 bars [Fortes, Icarus 2007]. We expect H2O2 oxidation to ignite at high temperatures but metallic minerals could catalyze reactions at lower temperatures nearer the basal layer. Pressure effects on oxidation rates are uncertain. Definitive modeling of Enceladus cryovolcanism likely involves synthesis of key processes from multiple models: Cold Faithful [Porco et al., Science 2006], Frigid Faithful [Keiffer et al., Science 2006], Frothy Faithful [Fortes, Icarus 2007], Old Faithful, and 'Perrier Ocean' recirculation [Matson et al., Icarus 2012].

Raman scattering investigation of VOCs in interaction with ice particles

NASA Astrophysics Data System (ADS)

Facq, Sébastien; Oancea, Adriana; Focsa, Cristian; Chazallon, Bertrand

2010-05-01

Cirrus clouds that form in the Earth's upper troposphere (UT) are known to play a significant role in the radiation budget and climate [1]. These clouds that cover about 35% of the Earth's surface [2] are mainly composed of small ice particles that can provide surfaces for trace gas interactions [3]. Volatile Organic Compounds (VOCs) are present in relative high abundance in the UT [4][5]. They promote substantial sources of free OH radicals that are responsible for driving photochemical cycles in the atmosphere. Their presence can both influence the oxidizing capacity and the ozone budget of the atmosphere. VOCs can interact with ice particles via different trapping processes (adsorption, diffusion, freezing, and co-deposition, i.e., incorporation of trace gases during growing ice conditions) which can result in the perturbation of the chemistry and photochemistry of the UT. Knowledge of the incorporation processes of VOCs in ice particles is important in order to understand and predict their impact on the ice particles structure and reactivity and more generally on the cirrus cloud formation. This proceeds via the in-situ characterization of the ice condensed phase in a pressure and temperature range of the UT. An important mechanism of UT cirrus cloud formation is the heterogeneous ice freezing process. In this study, we examine and characterize the interaction of a VOC, i.e., ethanol (EtOH) with ice particles during freezing. Vibrational spectra of water O-H and EtOH C-H spectral regions are analysed using confocal micro-Raman spectroscopy. Information at the molecular level on the surface structure can be derived from accompanying changes observed in band shapes and vibrational mode frequencies. Depending of the EtOH content, different crystalline phases have been identified and compared to hydrates previously reported for the EtOH-water system. Particular attention is paid on the effect of EtOH aqueous solutions cooling rate and droplet sizes on the phases formed. These results are finally compared with those obtained by co-deposition trapping process. [1] K. Liou, "Influence of Cirrus Clouds on Weather and Climate Processes: A Global Perspective," Monthly Weather Review, vol. 114, Juin. 1986, pp. 1167-1199. [2] A. Heymsfield and R. Sabin, "Cirrus crystal nucleation by homogeneous freezing of solution droplets," Journal of the Atmospheric Sciences, vol. 46, 1989, pp. 2252-2264. [3] J.P.D. Abbatt, "Interactions of Atmospheric Trace Gases with Ice Surfaces: Adsorption and Reaction," Chemical Reviews, vol. 103, Déc. 2003, pp. 4783-4800. [4] H. Singh, Y. Chen, A. Staudt, D. Jacob, D. Blake, B. Heikes, et J. Snow, "Evidence from the Pacific troposphere for large global sources of oxygenated organic compounds," Nature, vol. 410, Avr. 2001, pp. 1078-1081. [5] H.B. Singh, M. Kanakidou, P.J. Crutzen, and D.J. Jacob, "High concentrations and photochemical fate of oxygenated hydrocarbons in the global troposphere," Nature, vol. 378, Nov. 1995, pp. 50-54.

Active layer hydrology in an arctic tundra ecosystem: quantifying water sources and cycling using water stable isotopes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Throckmorton, Heather M.; Newman, Brent D.; Heikoop, Jeffrey M.

Climate change and thawing permafrost in the Arctic will significantly alter landscape hydro-geomorphology and the distribution of soil moisture, which will have cascading effects on climate feedbacks (CO 2 and CH 4) and plant and microbial communities. Fundamental processes critical to predicting active layer hydrology are not well understood. This study applied water stable isotope techniques (δ 2H and δ 18O) to infer sources and mixing of active layer waters in a polygonal tundra landscape in Barrow, Alaska (USA), in August and September of 2012. Results suggested that winter precipitation did not contribute substantially to surface waters or subsurface activemore » layer pore waters measured in August and September. Summer rain was the main source of water to the active layer, with seasonal ice melt contributing to deeper pore waters later in the season. Surface water evaporation was evident in August from a characteristic isotopic fractionation slope (δ 2H vs δ 18O). Freeze-out isotopic fractionation effects in frozen active layer samples and textural permafrost were indistinguishable from evaporation fractionation, emphasizing the importance of considering the most likely processes in water isotope studies, in systems where both evaporation and freeze-out occur in close proximity. The fractionation observed in frozen active layer ice was not observed in liquid active layer pore waters. Such a discrepancy between frozen and liquid active layer samples suggests mixing of meltwater, likely due to slow melting of seasonal ice. In conclusion, this research provides insight into fundamental processes relating to sources and mixing of active layer waters, which should be considered in process-based fine-scale and intermediate-scale hydrologic models.« less

Active layer hydrology in an arctic tundra ecosystem: quantifying water sources and cycling using water stable isotopes

DOE PAGES

Throckmorton, Heather M.; Newman, Brent D.; Heikoop, Jeffrey M.; ...

2016-04-16

Climate change and thawing permafrost in the Arctic will significantly alter landscape hydro-geomorphology and the distribution of soil moisture, which will have cascading effects on climate feedbacks (CO 2 and CH 4) and plant and microbial communities. Fundamental processes critical to predicting active layer hydrology are not well understood. This study applied water stable isotope techniques (δ 2H and δ 18O) to infer sources and mixing of active layer waters in a polygonal tundra landscape in Barrow, Alaska (USA), in August and September of 2012. Results suggested that winter precipitation did not contribute substantially to surface waters or subsurface activemore » layer pore waters measured in August and September. Summer rain was the main source of water to the active layer, with seasonal ice melt contributing to deeper pore waters later in the season. Surface water evaporation was evident in August from a characteristic isotopic fractionation slope (δ 2H vs δ 18O). Freeze-out isotopic fractionation effects in frozen active layer samples and textural permafrost were indistinguishable from evaporation fractionation, emphasizing the importance of considering the most likely processes in water isotope studies, in systems where both evaporation and freeze-out occur in close proximity. The fractionation observed in frozen active layer ice was not observed in liquid active layer pore waters. Such a discrepancy between frozen and liquid active layer samples suggests mixing of meltwater, likely due to slow melting of seasonal ice. In conclusion, this research provides insight into fundamental processes relating to sources and mixing of active layer waters, which should be considered in process-based fine-scale and intermediate-scale hydrologic models.« less

Testing Migration of the Jupiter Trojan Asteroids in the Lab

NASA Astrophysics Data System (ADS)

Poston, Michael; Blacksberg, Jordana; Brown, Mike; Carey, Elizabeth; Carlson, Robert; Ehlmann, Bethany; Eiler, John; Hand, Kevin; Hodyss, Robert; Mahjoub, Ahmed; Wong, Ian

2015-11-01

Today’s Jupiter Trojan asteroids may have orininated in the Kuiper Belt (eg. Morbidelli et al. Nature 2005, Nesvorny et al. ApJ 2013) and migrated to capture at their present locations. If this is the case, it is expected that their surfaces will contain chemical traces of this history. No distinct spectral bands have been conclusively identified in the literature, however, visible and near-infrared spectra of Kuiper Belt, Centaur, and Trojan populations each show two sub-populations distinguished by their spectral slopes (Brown et al. ApJL 2011; Emery et al. AJ 2011). The slopes are all positive (or “red”), steepest in the Kuiper Belt, and least steep in the Trojan population. Here we test the hypothesis that the asteroids formed spanning a stability line for a critical substance; in this case we test sulfur, as H2S. The hypothesis is that irradiating mixed ices containing H2S will result in a refractory residue of steeper slope than the same composition without the H2S. We have simulated this history in the Minos chamber at the Icy Worlds Simulation Laboratory at NASA’s Jet Propulsion Laboratory. Ices that will be discussed include a 3:3:3:1 mixture of H2S: NH3: CH3OH: H2O and a 3:3:1 mixture of NH3: CH3OH: H2O. After deposition at 50 K, the ices were irradiated with a beam of 10 keV electrons to form the refractory crust. The ices were then warmed (while continuing irradiation) to 120 K and observed for several days. Reflectance spectra were collected throughout the experiment in the visible and infrared. The spectral slope increased dramatically after irradiation of the mixture containing H2S, while the spectral slope for the mixture without any sulfur changed very little. This is consistent with sulfur being the critical component determining which of the spectral populations an object belongs to in the present inventory of outer solar system objects. Quantitative analysis is underway.This work has been supported by the Keck Institute for Space Studies (KISS). The research described here was carried out at the Jet Propulsion Laboratory, Caltech, under a contract with the National Aeronautics and Space Administration (NASA) and at the Caltech Division of Geological and Planetary Sciences.

Sea surface temperatures in the North Atlantic Ocean from 30ka to 10ka

NASA Astrophysics Data System (ADS)

Barrack, Kerr; Greenop, Rosanna; Burke, Andrea; Barker, Stephen; Chalk, Thomas; Crocker, Anya

2016-04-01

Some of the most striking features of the Late Pleistocene interval are the rapid changes in climate between warmer interstadial and cold stadial periods which, when coupled, are termed Dansgaard-Oeschger (D-O) events. This shift between warm and cold climates has been interpreted to result from changes in the thermohaline circulation (Broecker et al., 1985) triggered by, for instance, freshwater input from the collapse of the Laurentide ice sheet (Zahn et al., 1997). However, a recent study suggests that major ice rafting events cannot be the 'trigger' for the centennial to millennial scale cooling events identified over the past 500kyr (Barker at al., 2015). Polar planktic foraminiferal and lithogenic/terrigenous grain counts reveal that the southward migration of the polar front occurs before the deposition of ice rafted debris and therefore the rafting of ice during stadial periods. Based upon this evidence, Barker et al. suggest that the transition to a stadial state is a non-linear response to gradual cooling in the region. In order to test this hypothesis, our study reconstructs sea surface temperature across D-O events and the deglaciation in the North Atlantic between 30ka and 10ka using Mg/ Ca paleothermometry in Globigerina bulloides at ODP Sites 980 and 983 (the same sites as used in Barker et al., 2015) with an average sampling resolution of 300 years. With our new record we evaluate the timing of surface ocean temperature change, frontal shift movement, and ice rafting to investigate variations in the temperature gradient across the polar front over D-O events. References: Barker, S., Chen, J., Gong, X., Jonkers, L., Knorr, G., Thornalley, D., 2015. Icebergs not the trigger for North Atlantic cold events. Nature, 520(7547), pp.333-336. Broecker, W.S., Peteer, D.M., Rind, D., 1985. Does the ocean-atmosphere system have more than one stable mode of operation? Nature, 315 (6014), pp.21-26. Zahn, R., Schönfeld, J., Kudrass, H.-R., Park, M.-H., Erlenkeuser, H., Grootes, P, 1997. Thermohaline instability in the North Atlantic during meltwater events: Stable isotope and ice-rafted detritus records from Core SO75-26KL, Portuguese Margin. Paleoceanography, 12(5), pp.696-710.

A facile method of fabricating mechanical durable anti-icing coatings based on CeO2 microparticles

NASA Astrophysics Data System (ADS)

Wang, Pengren; Peng, Chaoyi; Wu, Binrui; Yuan, Zhiqing; Yang, Fubiao; Zeng, Jingcheng

2015-07-01

Compromising between hydrophobicity and mechanical durability may be a feasible approach to fabricating usable anti-icing coatings. This work improves the contact angle of current commercial anti-icing coatings applied to wind turbine blades dramatically and keeps relatively high mechanical durability. CeO2 microparticles and diluent were mixed with fluorocarbon resin to fabricate high hydrophobic coatings on the glass fiber reinforced epoxy composite substrates. The proportion of CeO2 microparticles and diluent influences the contact angles significantly. The optimum mass ratio of fluorocarbon resin to CeO2 microparticles to diluent is 1:1.5:1, which leads to the highest contact angle close to 140°. The microscopy analysis shows that the CeO2 microparticles form nano/microscale hierarchical structure on the surface of the coatings.

Dust Density Distribution and Imaging Analysis of Different Ice Lines in Protoplanetary Disks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pinilla, P.; Pohl, A.; Stammler, S. M.

Recent high angular resolution observations of protoplanetary disks at different wavelengths have revealed several kinds of structures, including multiple bright and dark rings. Embedded planets are the most used explanation for such structures, but there are alternative models capable of shaping the dust in rings as it has been observed. We assume a disk around a Herbig star and investigate the effect that ice lines have on the dust evolution, following the growth, fragmentation, and dynamics of multiple dust size particles, covering from 1 μ m to 2 m sized objects. We use simplified prescriptions of the fragmentation velocity threshold,more » which is assumed to change radially at the location of one, two, or three ice lines. We assume changes at the radial location of main volatiles, specifically H{sub 2}O, CO{sub 2}, and NH{sub 3}. Radiative transfer calculations are done using the resulting dust density distributions in order to compare with current multiwavelength observations. We find that the structures in the dust density profiles and radial intensities at different wavelengths strongly depend on the disk viscosity. A clear gap of emission can be formed between ice lines and be surrounded by ring-like structures, in particular between the H{sub 2}O and CO{sub 2} (or CO). The gaps are expected to be shallower and narrower at millimeter emission than at near-infrared, opposite to model predictions of particle trapping. In our models, the total gas surface density is not expected to show strong variations, in contrast to other gap-forming scenarios such as embedded giant planets or radial variations of the disk viscosity.« less

Short-term sea ice forecasting: An assessment of ice concentration and ice drift forecasts using the U.S. Navy's Arctic Cap Nowcast/Forecast System

NASA Astrophysics Data System (ADS)

Hebert, David A.; Allard, Richard A.; Metzger, E. Joseph; Posey, Pamela G.; Preller, Ruth H.; Wallcraft, Alan J.; Phelps, Michael W.; Smedstad, Ole Martin

2015-12-01

In this study the forecast skill of the U.S. Navy operational Arctic sea ice forecast system, the Arctic Cap Nowcast/Forecast System (ACNFS), is presented for the period February 2014 to June 2015. ACNFS is designed to provide short term, 1-7 day forecasts of Arctic sea ice and ocean conditions. Many quantities are forecast by ACNFS; the most commonly used include ice concentration, ice thickness, ice velocity, sea surface temperature, sea surface salinity, and sea surface velocities. Ice concentration forecast skill is compared to a persistent ice state and historical sea ice climatology. Skill scores are focused on areas where ice concentration changes by ±5% or more, and are therefore limited to primarily the marginal ice zone. We demonstrate that ACNFS forecasts are skilful compared to assuming a persistent ice state, especially beyond 24 h. ACNFS is also shown to be particularly skilful compared to a climatologic state for forecasts up to 102 h. Modeled ice drift velocity is compared to observed buoy data from the International Arctic Buoy Programme. A seasonal bias is shown where ACNFS is slower than IABP velocity in the summer months and faster in the winter months. In February 2015, ACNFS began to assimilate a blended ice concentration derived from Advanced Microwave Scanning Radiometer 2 (AMSR2) and the Interactive Multisensor Snow and Ice Mapping System (IMS). Preliminary results show that assimilating AMSR2 blended with IMS improves the short-term forecast skill and ice edge location compared to the independently derived National Ice Center Ice Edge product.

Atmospheric Hydroperoxides in West Antarctica: Links to Stratospheric Ozone and Atmospheric Oxidation Capacity

NASA Technical Reports Server (NTRS)

Frey, Markus M.; Stewart, Richard W.; McConnell, Joseph R.; Bales, Roger C.

2005-01-01

The troposphere above the West Antarctic Ice Sheet (WAIS) was sampled for hydroperoxides at 21 locations during 2-month-long summer traverses from 2000 to 2002, as part of US ITASE (International Transantarctic Scientific Expedition). First time quantitative measurements using an HPLC method showed that methylhydroperoxide (MHP) is the only important organic hydroperoxide occurring in the Antarctic troposphere, and that it is found at levels ten times those previously predicted by photochemical models. During three field seasons, means and standard deviations for hydrogen peroxide (H2O2) were 321+/-158 pptv, 650+/-176 pptv and 330+/-147 pptv. While MHP was detected, but not quantified in December 2000, levels in summer 2001 and 2002 were 317+128 pptv and 304+/-172.2 pptv. Results from firn air experiments and diurnal variability of the two species showed that atmospheric H2O2 is significantly impacted by a physical snow pack source between 76 and 90degS, whereas MHP is not. We show strong evidence of a positive feedback between stratospheric ozone and H2O2 at the surface. Between November-27 and December-12 in 2001, when ozone column densities dropped below 220 DU (means in 2000 and 2001 were 318 DU and 334 DU, respectively), H2O2 was 1.7 times that observed in the same period in 2000 and 2002, while MHP was only 80% of the levels encountered in 2002. Photochemical box model runs suggest that NO and OH levels on WAIS are closer to coastal values, while Antarctic Plateau levels are higher, confirming that region to be a highly oxidizing environment. The modeled sensitivity of H2O2 and particularly MHP to NO offers the potential to use atmospheric hydroperoxides to constrain the NO background and thus estimate the past oxidation capacity of the remote atmosphere. Index Terms: 0365 Atmospheric Composition and Structure: Troposphere: composition and chemistry; 0322 Atmospheric Composition and Structure: Constituent sources and sinks; 1610 Global Change: Atmosphere (03 15,0325); 0736 Cryosphere: Snow (1827, 1863); 0724 Cryosphere: Ice Cores (4932) Keywords: hydrogen peroxide, methylhydroperoxide, Antarctica, air-snow exchange, stratospheric ozone, atmospheric oxidation capacity

HiRISE observations of gas sublimation-driven activity in Mars' southern polar regions: III. Models of processes involving translucent ice

USGS Publications Warehouse

Portyankina, G.; Markiewicz, W.J.; Thomas, N.; Hansen, C.J.; Milazzo, M.

2010-01-01

Enigmatic surface features, known as 'spiders', found at high southern martian latitudes, are probably caused by sublimation-driven erosion under the seasonal carbon dioxide ice cap. The Mars Reconnaissance Orbiter (MRO) High Resolution Imaging Science Experiment (HiRISE) has imaged this terrain in unprecedented details throughout southern spring. It has been postulated [Kieffer, H.H., Titus, T.N., Mullins, K.F., Christensen, P.R., 2000. J. Geophys. Res. 105, 9653-9700] that translucent CO2 slab ice traps gas sublimating at the ice surface boundary. Wherever the pressure is released the escaping gas jet entrains loose surface material and carries it to the top of the ice where it is carried downslope and/or downwind and deposited in a fan shape. Here we model two stages of this scenario: first, the cleaning of CO2 slab ice from dust, and then, the breaking of the slab ice plate under the pressure built below it by subliming ice. Our modeling results and analysis of HiRISE images support the gas jet hypothesis and show that outbursts happen very early in spring. ?? 2009 Elsevier Inc. All rights reserved.

PALOMA : an isotope analyzer using static mass spectrometry, coupled with cryogenic and chemical trapping, for the MSL mission to Mars

NASA Astrophysics Data System (ADS)

Chassefiere, E.; Jambon, A.; Berthelier, J.-J.; Goulpeau, G.; Leblanc, F.; Montmessin, F.; Sarda, P.; Agrinier, P.; Fouchet, T.; Waite, H.

The technique of GCMS analysis has to be completed by static mass spectrometry for precise in-situ measurements of the isotopic composition of planetary atmospheres (noble gases, stable isotopes), and volatile outgassed products from solid sample pyrolysis. Static mass spectrometry, coupled with gas separation by cryo-separation and gettering, is commonly used in the laboratory to study volatiles extracted from terrestrial and meteoritic samples. Such an instrument (PALOMA) is presently developed in our laboratories, and it will be coupled with a Pyr-GCMS analyzer (MACE), built by a US consortium of science laboratories and industrials (University of Michigan, Southwest Research Institute, JPL, Ball Aerospace). The MACE/PALOMA experiment will be proposed on the NASA Mars Science Laboratory mission, planned to be launched in 2009. The scientific objectives of PALOMA, coupled with MACE, may be listed as follows : (i) search for isotopic signatures of past life in atmosphere, rock, dust and ice samples, with emphasis on carbon, nitrogen and hydrogen; (ii) accurately measure isotopic composition of atmospheric noble gases, and stable isotopes, in order to better constrain past escape, surface interaction, outgassing history and climate evolution; (iii) precisely measure diurnal/ seasonal variations of isotopic ratios of H2O, CO2, and N2, for improving our understanding of present and past climate, and of the role of water cycle. Main measurement objectives are : (i) C, H, O, N isotopic composition in both organic evolved samples (provided by MACE pyrolysis system) and atmosphere with high accuracy (a few per mil at 1-s level); (ii) noble gas (He, Ne, Ar, Kr, Xe) and stable (C, H, O, N) isotope composition in atmosphere with high accuracy (a few per mil at 1-s level); (iii) molecular and isotopic composition of inorganic evolved samples (salts, hydrates, nitrates, {ldots}), including ices; (iv) diurnal and seasonal monitoring of D/H in water vapor, and water ice.

White Mars: A New Model for Mars' Surface and Atmosphere Based on CO 2

NASA Astrophysics Data System (ADS)

Hoffman, Nick

2000-08-01

A new model is presented for the Amazonian outburst floods on Mars. Rather than the working fluid being water, with the associated difficulties in achieving warm and wet conditions on Mars and on collecting and removing the water before and after the floods, instead this model suggests that CO 2 is the active agent in the "floods." The flow is not a conventional liquid flood but is instead a gas-supported density flow akin to terrestrial volcanic pyroclastic flows and surges and at cryogenic temperatures with support from degassing of CO 2-bearing ices. The flows are not sourced from volcanic vents, but from the collapse of thick layered regolith containing liquid CO 2 to form zones of chaotic terrain, as shown by R. St. J. Lambert and V. E. Chamberlain (1978, Icarus34, 568-580; 1992, Workshop on the Evolution of the Martian Atmosphere). Submarine turbidites are also analagous in the flow mechanism, but the martian cryogenic flows were both dry and subaerial, so there is no need for a warm and wet epoch nor an ocean on Mars. Armed with this new model for the floods we review the activity of volatiles on the surface of Mars in the context of a cold ice world—"White Mars." We find that many of the recognized paradoxes about Mars' surface and atmosphere are resolved. In particular, the lack of carbonates on Mars is due to the lack of liquid water. The CO 2 of the primordial atmosphere and the H 2O inventory remain largely sequestered in subsurface ices. The distribution of water ice on modern Mars is also reevaluated, with important potential consequences for future Mars exploration. The model for collapse of terrain due to ices that show decompression melting, and the generation of nonaqueous flows in these circumstances may also be applicable to outer Solar System bodies, where CO 2, SO 2, N 2, and other ices are stable.

ON THE FORMATION AND ISOMER SPECIFIC DETECTION OF PROPENAL (C{sub 2}H{sub 3}CHO) AND CYCLOPROPANONE (c-C{sub 3}H{sub 4}O) IN INTERSTELLAR MODEL ICES—A COMBINED FTIR AND REFLECTRON TIME-OF-FLIGHT MASS SPECTROSCOPIC STUDY

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abplanalp, Matthew J.; Borsuk, Aleca; Jones, Brant M.

2015-11-20

The formation routes of two structural isomers—propenal (C{sub 2}H{sub 3}CHO) and cyclopropanone (c-C{sub 3}H{sub 4}O)—were investigated experimentally by exposing ices of astrophysical interest to energetic electrons at 5.5 K thus mimicking the interaction of ionizing radiation with interstellar ices in cold molecular clouds. The radiation-induced processing of these ices was monitored online and in situ via Fourier Transform Infrared spectroscopy and via temperature programmed desorption exploiting highly sensitive reflectron time-of-flight mass spectrometry coupled with single photon ionization in the post irradiation phase. To selectively probe which isomer(s) is/are formed, the photoionization experiments were conducted with 10.49 and 9.60 eV photons.more » Our studies provided compelling evidence on the formation of both isomers—propenal (C{sub 2}H{sub 3}CHO) and cyclopropanone (c-C{sub 3}H{sub 4}O)—in ethylene (C{sub 2}H{sub 4})—carbon monoxide (CO) ices forming propenal and cyclopropanone at a ratio of (4.5 ± 0.9):1. Based on the extracted reaction pathways, the cyclopropanone molecule can be classified as a tracer of a low temperature non-equilibrium chemistry within interstellar ices involving most likely excited triplet states, whereas propenal can be formed at ultralow temperatures, but also during the annealing phase via non-equilibrium as well as thermal chemistry (radical recombination). Since propenal has been detected in the interstellar medium and our laboratory experiments demonstrate that both isomers originated from identical precursor molecules our study predicts that the hitherto elusive second isomer—cyclopropanone—should also be observable toward those astronomical sources such as Sgr B2(N) in which propenal has been detected.« less

Isoscapes of δ18O and δ2H reveal climatic forcings on Alaska and Yukon precipitation

NASA Astrophysics Data System (ADS)

Lachniet, Matthew S.; Lawson, Daniel E.; Stephen, Haroon; Sloat, Alison R.; Patterson, William P.

2016-08-01

Spatially extensive Arctic stable isotope data are sparse, inhibiting the climatic understanding required to interpret paleoclimate proxy records. To fill this need, we constrained the climatic and physiographic controls on δ18O and δD values of stream waters across Alaska and the Yukon to derive interpolated isoscape maps. δ18O is strongly correlated to winter temperature parameters and similarity of the surface water line (δ2H = 8.0 × δ18O + 6.4) to the Global Meteoric Water Line suggests stream waters are a proxy for meteoric precipitation. We observe extreme orographic δ18O decreases and a trans-Alaskan continental gradient of -8.3‰ 1000 km-1. Continental gradients are high in coastal zones and low in the interior. Localized δ18O increases indicate inland air mass penetration via topographic lows. Using observed δ18O/temperature gradients, we show that δ18O decreases in a ˜24 ka permafrost ice wedge relative to the late Holocene indicate mean annual and coldest quarter temperature reductions of 8.9 ± 1.7°C and 17.2 ± 3.2°C, respectively.

The Effect of Broadband Soft X-Rays in SO2-Containing Ices: Implications on the Photochemistry of Ices toward Young Stellar Objects

NASA Astrophysics Data System (ADS)

Pilling, S.; Bergantini, A.

2015-10-01

We investigate the effects produced mainly by broadband soft X-rays up to 2 keV (plus fast (˜keV) photoelectrons and low-energy (˜eV) induced secondary electrons) in the ice mixtures containing H2O:CO2:NH3:SO2 (10:1:1:1) at two different temperatures (50 and 90 K). The experiments are an attempt to simulate the photochemical processes induced by energetic photons in SO2-containing ices present in cold environments in the ices surrounding young stellar objects (YSO) and in molecular clouds in the vicinity of star-forming regions, which are largely illuminated by soft X-rays. The measurements were performed using a high-vacuum portable chamber from the Laboratório de Astroquímica e Astrobiologia (LASA/UNIVAP) coupled to the spherical grating monochromator beamline at the Brazilian Synchrotron Light Source (LNLS) in Campinas, Brazil. In situ analyses were performed by a Fourier transform infrared spectrometer. Sample processing revealed the formation of several organic molecules, including nitriles, acids, and other compounds such as H2O2, H3O+, SO3, CO, and OCN-. The dissociation cross section of parental species was on the order of (2-7) × 10-18 cm2. The ice temperature does not seem to affect the stability of SO2 in the presence of X-rays. Formation cross sections of new species produced were also determined. Molecular half-lives at ices toward YSOs due to the presence of incoming soft X-rays were estimated. The low values obtained employing two different models of the radiation field of YSOs (TW Hydra and typical T-Tauri star) reinforce that soft X-rays are indeed a very efficient source of molecular dissociation in such environments.

The electrolytical processes in dirty ices: implications for origin and chemistry of minor bodies and related objects.

PubMed

Drobyshevski, E M; Chesnakov, V A; Sinitsyn, V V

1995-01-01

Many moonlike bodies (M approximately or = 1 Moon) beyond the Martian orbit contain large amounts of dirty ice (approximately 50%) forming thick mantle with the solid phase thermal convection. When a body moves through the inter- or nearplanetary magnetized plasma, electric current is generated in the body and its environment. The current passing through a dirty ice containing up to 10% of organic admixtures produces a lot of electrochemical effects which have a profound impact on its composition. At this stage one can hardly say something definite concerning changes experienced by organics. The changes must occur inevitably and can be of a rather unexpected and far-reaching nature, so deserving a close study. Another obvious effect is a volumetric electrolysis of ice containing alien inclusions. The electrolysis products accumulate in ice in the form of a solid solution which is capable of detonation at 15-20 wt.% of 2H2 + O2. If M > or = 1 Moon (Galilean satellites, Titan), the body loses in explosion a part of its mass in the form of vapor and ice fragments (=short-period comet nuclei), whereas if M < or = 0.2 Moon, the body breaks up totally (the Main Belt asteroids origin approximately 3.9 Byr ago). 2H2 + O2 containing cometary nuclei are capable of burning or suffer new explosions when receiving an additional energy. The combustion in the sublimation products containing also light organics and 2H2 + O2 explains unexpected energetics and nearnuclear chemistry of Comet P/Halley (e.g. great abundances of negative and positive ions, atomic carbon, CO over CO2, origin of CHON particles etc) and its distant outbursts correlated, possibly, with the Solar activity. Thus the electrochemical processes in the dirty ice with organics, along with its subsequent thermal, radiative etc. processing, open up new potentials for explanation and prediction of quite unexpected discoveries.

The effect of volume phase changes, mass transport, sunlight penetration, and densification on the thermal regime of icy regoliths

NASA Technical Reports Server (NTRS)

Fanale, Fraser P.; Salvail, James R.; Matson, Dennis L.; Brown, Robert H.

1990-01-01

The present quantitative modeling of convective, condensational, and sublimational effects on porous ice crust volumes subjected to solar radiation encompasses the effect of such insolation's penetration of visible bandpass-translucent light, but opaque to the IR bandpass. Quasi-steady-state temperatures, H2O mass fluxes, and ice mass-density change rates are computed as functions of time of day and ice depth. When the effects of latent heat and mass transport are included in the model, the enhancement of near-surface temperature due to the 'solid-state greenhouse effect' is substantially diminished. When latent heat, mass transport, and densification effects are considered, however, a significant solid-state greenhouse effect is shown to be compatible with both morphological evidence for high crust strengths and icy shell decoupling from the lithosphere.

DFT studies on H 2O adsorption and its effect on CO oxidation over spinel Co 3O 4 (110) surface

NASA Astrophysics Data System (ADS)

Xu, Xiang Lan; Li, Jun Qian

2011-12-01

Adsorption of H2O and its effect on CO oxidation over spinel Co3O4 (110) surface were studied by density functional theory calculations. H2O is adsorbed favorably at the octahedral cobalt (Cooct) site through O atom on the surface. Hydrogen bonding interaction between 1s orbitals of H atoms in H2O and the 2p orbitals of surface active oxygen sites plays a key role for H2O adsorption. The inhibition effect of H2O adsorption on the CO oxidation over the surfaces is attributed to the competition between H2O and CO molecules for the surface twofold coordinated oxygen site.

The Present Near-Surface Inventory of Water on Mars: How Well Does it Constrain the Past Inventory and the Existence of a Former Ocean?

NASA Astrophysics Data System (ADS)

Clifford, S.; McCubbin, F.

2015-10-01

Over the past 40 years, estimates of the total outgassed inventory of water on Mars have ranged from a global equivalent layer (GEL) ~7-1000 m deep [1, 2]. However, Carr and Head [3] have recently argued that it is not the total inventory of outgassed water that is important, but the amount that exists in climatically exchangeable surface and near- surface reservoirs - suggesting that any exchange with water in the deep subsurface is precluded by the existence of a thick cryosphere, at least during the Amazonian and Hesperian. Based on this assumption, and their estimate of the present day near-surface inventory of H2O (~34 m GEL, stored as ice in the polar layered deposits (PLD), lobate debris aprons, ice-rich latitude dependent mantles, and as shallow ground ice), they then extrapolate the evolution of this inventory backward in time, taking into account the introduction of new water by volcanism and outflow channel activity and the loss of water by exospheric escape. They conclude that, at the end of the Noachian, Mars had a near-surface water inventory of ~24 m and ~62 m by the end of the Hesperian - inventories that Carr and Head [3] argue were incompatible with the existence of a former ocean.

Fabrication of bismuth superhydrophobic surface on zinc substrate

NASA Astrophysics Data System (ADS)

Yu, Tianlong; Lu, Shixiang; Xu, Wenguo; He, Ge

2018-06-01

The dendritic Bi/Bi2O3/ZnO superhydrophobic surface (SHPS) was facilely obtained on zinc substrate via etching in 0.5 mol L-1 HCl solution for 2 min, immersing in 2 mmol L-1 Bi(NO3)3/0.1 mol L-1 HNO3 solution for 2.5 min and annealing treatment at 180 °C for 2 h. The wetting property results demonstrated that the superhydrophobic sample had excellent water-repellency with a static water contact angle of 160° and sliding angle of 0° under the optimum condition, which can be visually confirmed by the impacting droplet could rebound back immediately and roll off the horizontally placed sample. Moreover, it exhibited remarkable self-cleaning ability, buoyancy, desired stability in long-term storage in air, corrosion resistance in 3.5 wt% NaCl solution, ice-over delay at - 16 °C and durability in lab-simulated abrasion test.

The Formation of Nucleobases from the Irradiation of Purine in Astophysical Ices and Comparisons with Meteorites.

NASA Technical Reports Server (NTRS)

Sandford, S. A.; Materese, C. K.; Nuevo, M.

2016-01-01

N-heterocycles have been identified in meteorites and their extraterrestrial origins are suggested by isotopic ratio measurements. Although small N- heterocycles have not been detected in the interstellar medium (ISM), recent experiments in our lab have shown that the irradiation of the aromatic molecules like benzene (C6H6) and naphthalene (C10H8) in mixed molecular ices leads to the formation of O- and N-heterocyclic molecules. Among the class of N-heterocycles are the nucleobases, which are of astrobiological interest because they are the information bearing units of DNA and RNA. Nucleobases have been detected in meteorites [3-5], with isotopic signatures that are also consistent with an extraterrestrial origin. Three of the biologically relevant nucleobases (uracil, cytosine, and guanine) have a pyrimidine core structure while the remaining two (adenine and guanine) possess a purine core. Previous experiments in our lab have demonstrated that all of the bio-logical nucleobases (and numerous other molecules) with a pyrimidine core structure can be produced by irradiating pyrimidine in mixed molecular ices of several compositions [6-8]. In this work, we study the formation of purine-based molecules, including the nucleobases adenine, and guanine, from the ultraviolet (UV) irradiation of purine in ices consisting mixtures of H2O and NH3 at low temperature. The experiments are designed to simulate the astrophysical conditions under which these species may be formed in dense molecular clouds, protoplanetary disks, or on the surfaces of icy bodies in planetary systems.

Heating of Porous Icy Dust Aggregates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sirono, Sin-iti

At the beginning of planetary formation, highly porous dust aggregates are formed through coagulation of dust grains. Outside the snowline, the main component of an aggregate is H{sub 2}O ice. Because H{sub 2}O ice is formed in amorphous form, its thermal conductivity is extremely small. Therefore, the thermal conductivity of an icy dust aggregate is low. There is a possibility of heating inside an aggregate owing to the decay of radionuclides. It is shown that the temperature increases substantially inside an aggregate, leading to crystallization of amorphous ice. During the crystallization, the temperature further increases sufficiently to continue sintering. Themore » mechanical properties of icy dust aggregates change, and the collisional evolution of dust aggregates is affected by the sintering.« less

Formation of Nucleobases from the UV Irradiation of Pyrimidine in Interstellar Ice Analogs

NASA Technical Reports Server (NTRS)

Milam, Stefanie N.; Nuevo, Michel; Sandford, Scott A.; Elsila, Jamie E.; Dworkin, Jason P.

2010-01-01

Previous laboratory simulations showed that complex molecules, including prebiotic compounds/can be formed under interstellar conditions from the vacuum UV irradiation of interstellar ice analogs containing H2O, CO, NH3 etc. Although some complex prebiotic species have not been confirmed In the interstellar medium, they are known to be present in meteorites. Nucleobases, the building blocks of DNA and RNA, have also been detected in meteorites. Here, we present a study of the formation of pyrimidine-based compounds from the UV irradiation of pyrimidine in H2O- and/or NH3-ices at 20-30 K, Our results show that various derivatives, induding the nucleobases uracil and cytosine, are formed under these conditions.

Side Group Addition to the Polycyclic Aromatic Hydrocarbon Coronene by Proton Irradiation in Cosmic Ice Analogs

NASA Astrophysics Data System (ADS)

Bernstein, Max P.; Moore, Marla H.; Elsila, Jamie E.; Sandford, Scott A.; Allamandola, Louis J.; Zare, Richard N.

2003-01-01

Ices at ~15 K consisting of the polycyclic aromatic hydrocarbon coronene (C24H12) condensed either with H2O, CO2, or CO in the ratio of 1:100 or greater have been subjected to MeV proton bombardment from a Van de Graaff generator. The resulting reaction products have been examined by infrared transmission-reflection-transmission spectroscopy and by microprobe laser-desorption laser-ionization mass spectrometry. Just as in the case of UV photolysis, oxygen atoms are added to coronene, yielding, in the case of H2O ices, the addition of one or more alcohol (OH) and ketone (>CO) side chains to the coronene scaffolding. There are, however, significant differences between the products formed by proton irradiation and the products formed by UV photolysis of coronene containing CO and CO2 ices. The formation of a coronene carboxylic acid (COOH) by proton irradiation is facile in solid CO but not in CO2, the reverse of what was previously observed for UV photolysis under otherwise identical conditions. This work presents evidence that cosmic-ray irradiation of interstellar or cometary ices should have contributed to the formation of aromatics bearing ketone and carboxylic acid functional groups in primitive meteorites and interplanetary dust particles.

Probing the CO and methanol snow lines in young protostars. Results from the CALYPSO IRAM-PdBI survey

NASA Astrophysics Data System (ADS)

Anderl, S.; Maret, S.; Cabrit, S.; Belloche, A.; Maury, A. J.; André, Ph.; Codella, C.; Bacmann, A.; Bontemps, S.; Podio, L.; Gueth, F.; Bergin, E.

2016-06-01

Context. So-called snow lines, indicating regions where abundant volatiles freeze out onto the surface of dust grains, play an important role for planet growth and bulk composition in protoplanetary disks. They can already be observed in the envelopes of the much younger, low-mass Class 0 protostars, which are still in their early phase of heavy accretion. Aims: We aim to use the information on the sublimation regions of different kinds of ices to understand the chemistry of the envelope, its temperature and density structure, and the history of the accretion process. This information is crucial to get the full picture of the early protostellar collapse and the subsequent evolution of young protostars. Methods: As part of the CALYPSO IRAM Large Program, we have obtained observations of C18O, N2H+, and CH3OH towards nearby Class 0 protostars with the IRAM Plateau de Bure interferometer at sub-arcsecond resolution. For four of these sources, we have modeled the emission using a chemical code coupled with a radiative transfer module. Results: We observe an anti-correlation of C18O and N2H+ in NGC 1333-IRAS4A, NGC 1333-IRAS4B, L1157, and L1448C, with N2H+ forming a ring (perturbed by the outflow) around the centrally peaked C18O emission. This emission morphology, which is due to N2H+ being chemically destroyed by CO, reveals the CO and N2 ice sublimation regions in these protostellar envelopes with unprecedented resolution. We also observe compact methanol emission towards three of the sources. Based on our chemical model and assuming temperature and density profiles from the literature, we find that for all four sources the CO snow line appears further inwards than expected from the binding energy of pure CO ices (~855 K). The emission regions of models and observations match for a higher value of the CO binding energy of 1200 K, corresponding to a dust temperature of ~24 K at the CO snow line. The binding energy for N2 ices is modeled at 1000 K, also higher than for pure N2 ices. Furthermore, we find very low CO abundances inside the snow lines in our sources, about an order of magnitude lower than the total CO abundance observed in the gas on large scales in molecular clouds before depletion sets in. Conclusions: The high CO binding energy may hint at CO being frozen out in a polar ice environment like amorphous water ice or in non-polar CO2-rich ice. The low CO abundances are comparable to values found in protoplanetary disks, which may indicate an evolutionary scenario where these low values are already established in the protostellar phase. Based on observations carried out under project number U052 with the IRAM Plateau de Bure Interferometer. IRAM is supported by INSU/CNRS (France), MPG (Germany) and IGN (Spain).

North-south comparison of springtime dark slope structures on Mars, and the possibility of liquid water

NASA Astrophysics Data System (ADS)

Kereszturi, A.; Berczi, Sz.; Horvath, A.; Ganti, T.; Kuti, A.; Pocs, T.; Sik, A.; Szathmary, E.

2008-09-01

Introduction Various polar seasonal surface albedo structures were analyzed by several authors in the past [1, 2, 3, 4, 5, 6, 7, 8, 8, 9], partly in connection with the possibility of liquid water. In our previous work [10] we identified two groups of slope streaks emanating form Dark Dune Spots of polar dunes, which grow in size and number during spring with the advancement of the season. The diffuse shaped group appears earlier and formed probably by CO2 geysers [8]. The confine shaped group appears in a later seasonal phase, when the temperature is higher. They are probably connected with exposed water-ice on the surface, and may formed by the seepage of undercooled interfacial water on microscopic scale [11]. Methods For the analysis of northern slope structures we used MGS MOC, MRO HiRISE images, and MRG TES data [12] using the "vanilla" software. Temperature data show annual trend, and were derived for daytime. Note that the surface temperature values have spatial resolution around 3 km, and they can be taken only as a rough approach of the surface temperature of the whole dune complex, and not different parts of it. Discussion The target area of the analysis was (84N 233E) in the northern circumpolar sand sea, with 300-500 m diameter overlapping dunes. We searched for springtime confined and elongated dark slope streaks, similar to those, which we observed at south. Basic similarities between northern and southern structures are: 1. streaks always emanate from Dark Dune Spots in downward direction, 2. streaks are present in local spring, when the temperature is above the CO2 buffered level, suggesting there are parts of the surface without CO2 ice, where possibly H2O ice is exposed (Fig. 1.), 4. the streaks show branching pattern (Fig. 2.). Basic differences between the northern and southern structures: 1. at north there is a dark annulus around the Dark Dune Spots, which is absent at south, 2. there are fewer and fainter diffuse streaks of gas jet activity at north, 3. there are fewer pond-like accumulated structures at the streaks' end at north. Conclusion The branching dark pattern suggests the movement of liquid-like material, while the temperature data suggest these dark features are formed possibly in connection with H2O ice. The moving material may be composed of dry or adsorbed water [13] lubricated grains also. Based on the probably presence of waterice, and the model of adsorbed water, northern DDSslope structures may be the result of seepage by interfacial water around solar heated dune grains, as well as the southern ones. This situation may have astrobiological consequences [14] too. Acknowledgment This work was supported by the ESA ECS-project No. 98004 and the Pro Renovanda Cultura Hungariae Foundation. References [1] Kieffer H. et al. (2000) 2nd Conf. Mars Pol. Sci. 93., [2] Ness & Orme JBIS (2002) 55, 85-109. [3] Piqueux S. et al. (2003) JGR 108, 5084. [4] Christensen et al. (2005) AGU, Fall Meeting #P23C- 04. [5] Malin M.C. et al., (1998) Science 279, 1681-1685. [6] Malin M.C. and Edgett K.S. (2000) XXXIth LPSC #1056. [7] Zuber T.M. (2003) Science 302, 1694-1695. [8] Kieffer H.H. et al.

A First Principles Study of H2 Adsorption on LaNiO3(001) Surfaces

PubMed Central

Pan, Changchang; Chen, Yuhong; Wu, Na; Zhang, Meiling; Yuan, Lihua; Zhang, Cairong

2017-01-01

The adsorption of H2 on LaNiO3 was investigated using density functional theory (DFT) calculations. The adsorption sites, adsorption energy, and electronic structure of LaNiO3(001)/H2 systems were calculated and indicated through the calculated surface energy that the (001) surface was the most stable surface. By looking at optimized structure, adsorption energy and dissociation energy, we found that there were three types of adsorption on the surface. First, H2 molecules completely dissociate and then tend to bind with the O atoms, forming two –OH bonds. Second, H2 molecules partially dissociate with the H atoms bonding to the same O atom to form one H2O molecule. These two types are chemical adsorption modes; however, the physical adsorption of H2 molecules can also occur. When analyzing the electron structure of the H2O molecule formed by the partial dissociation of the H2 molecule and the surface O atom, we found that the interaction between H2O and the (001) surface was weaker, thus, H2O was easier to separate from the surface to create an O vacancy. On the (001) surface, a supercell was constructed to accurately study the most stable adsorption site. The results from analyses of the charge population; electron localization function; and density of the states indicated that the dissociated H and O atoms form a typical covalent bond and that the interaction between the H2 molecule and surface is mainly due to the overlap-hybridization among the H 1s, O 2s, and O 2p states. Therefore, the conductivity of LaNiO3(001)/H2 is stronger after adsorption and furthermore, the conductivity of the LaNiO3 surface is better than that of the LaFeO3 surface. PMID:28772396

Dynamics of Permafrost Associated Methane Hydrate in Response to Climate Change

NASA Astrophysics Data System (ADS)

You, K.; Flemings, P. B.

2014-12-01

The formation and melting of methane hydrate and ice are intertwined in permafrost regions. A shortage of methane supply leads to formation of hydrate only at depth, below the base of permafrost. We consider a system with the ground surface initially at 0 oC with neither ice nor hydrate present. We abruptly decrease the temperature from 0 to -10 oC to simulate the effect of marine regression/ global cooling. A low methane supply rate of 0.005 kg m-2 yr-1 from depth leads to distinct ice and hydrate layers: a 100 m continuous hydrate layer is present beneath 850 m at 80 k.y.. However, a high methane supply rate of 0.1 kg m-2 yr-1 leads to 50 m ice-bonded methane hydrate at the base of permafrost, and the hydrate layer distributes between the depth of 350 and 700 m at 80 k.y.. We apply our model to illuminate future melting of hydrate at Mallik, a known Arctic hydrate accumulation. We assume a 600 m thick ice saturated (average 90%) layer extending downward from the ground surface. We increase the surface temperature linearly from -6 to 0 oC for 300 yr and then keep the surface temperature at 0 oC to reflect future climate warming caused by doubling of CO2. Hydrate melting is initiated at the base of the hydrate layer after 15 k.y.. Methane gas starts to vent to the atmosphere at 38 k.y. with an average flux of ~ 0.35 g m-2 yr-1. If the 600 m thick average ice saturation is decreased to half (45%) (or to zero), methane gas starts to vent to the atmosphere at 29 k.y. (or at 20 k.y.) with the same average flux. These results are found by a newly-developed fully-coupled multiphase multicomponent fluid flow and heat transport model. Our thermodynamic equilibrium-based model emphasizes the role of salinity in both ice and hydrate dynamics.

The Surface Compositions of Triton, Pluto, and Charon

NASA Technical Reports Server (NTRS)

Cruikshank, Dale P.; Roush, Ted L.; Owen, Tobias C.; Quirico, Eric; DeBergh, Catherine

1995-01-01

Neptune's satellite Triton, and the planet-satellite binary Pluto and Charon, are the most distant planetary bodies on which ices have been directly detected. Triton and Pluto have very similar dimensions and mean densities, suggesting a similar or common origin. Through earth-based spectroscopic observations in the near-infrared, solid N2, CH4, and CO have been found on both bodies, with the additional molecule C02 on Triton. N2 dominates both surfaces, although the coverage is not spatially uniform. On Triton, the CH4 and CO are mostly or entirely frozen in the N2 matrix, while CO2 may be spatially segregated. On Pluto, some CH4 and the CO are frozen in the N2 matrix, but there is evidence for additional CH4 in a pure state, perhaps lying as a lag deposit on a subsurface layer of N2. Despite their compositional and dimensional similarities, Pluto and Triton are quite different from one another in detail. Additional hydrocarbons and other volatile ices have been sought spectroscopically but not yet have been detected. The only molecule identified on Pluto's satellite Charon is solid H2O, but the spectroscopic data are of low precision and admit the presence of other ices such as CH4.

Inactivation of Nonpathogenic Escherichia coli, Escherichia coli O157:H7, Salmonella enterica Typhimurium, and Listeria monocytogenes in Ice Using a UVC Light-Emitting Diode.

PubMed

Murashita, Suguru; Kawamura, Shuso; Koseki, Shigenobu

2017-07-01

Ice, widely used in the food industry, is a potential cause of food poisoning resulting from microbial contamination. Direct microbial inactivation of ice is necessary because microorganisms may have been present in the source water used to make it and/or may have been introduced due to poor hygiene during production or handling of the ice. Nonthermal and nondestructive microbial inactivation technologies are needed to control microorganisms in ice. We evaluated the applicability of a UVC light-emitting diode (UVC-LED) for microbial inactivation in ice. The effects of UV intensity and UV dose of the UVC-LED on Escherichia coli ATCC 25922 and a comparison of UVC-LED with a conventional UV lamp for effective bacterial inactivation in distilled water and ice cubes were investigated to evaluate the performance of the UVC-LED. Finally, we assessed the effects of the UVC-LED on pathogens such as E. coli O157:H7, Salmonella Typhimurium, and Listeria monocytogenes in ice cubes. The results indicated that UVC-LED effectiveness depended on the UV dose at all UV intensity conditions (0.084, 0.025, 0.013, 0.007, and 0.005 mW/cm 2 ) in ice and that UVC-LED could more efficiently inactivate E. coli ATCC 25922 in distilled water and ice than the UV lamp. At a UV dose of 2.64 mJ/cm 2 , E. coli in distilled water was decreased by 0.90 log CFU/mL (UV lamp) and by more than 7.0 log CFU/mL (UVC-LED). At 15.2 mJ/cm 2 , E. coli in ice was decreased by 3.18 log CFU/mL (UV lamp) and by 4.45 CFU/mL (UVC-LED). Furthermore, UVC-LED irradiation reduced the viable number of pathogens by 6 to 7 log cycles at 160 mJ/cm 2 , although the bactericidal effect was somewhat dependent on the type of bacteria. L. monocytogenes in ice was relatively more sensitive to UVC irradiation than were E. coli O157:H7 and Salmonella Typhimurium. These results demonstrate that UVC-LED irradiation could contribute to the safety of ice in the food industry.

How Well Does the Present Surface Inventory of Water on Mars Constrain the Past?

NASA Technical Reports Server (NTRS)

Clifford, S. M.; McCubbin, F. M.

2016-01-01

Over the past 40 years, estimates of the total outgassed inventory of water on Mars have ranged from a global equivalent layer (GEL) approximately 7-1000 m deep. However, Carr and Head have recently argued that it is not the total inventory of outgassed water that is important, but the amount that exists in climatically exchangeable surface and near surface reservoirs - suggesting that any exchange with water in the deep subsurface is precluded by the existence of a thick cryosphere, at least during the Amazonian and Hesperian. Based on this assumption and their estimate of the present day near-surface inventory of H2O (approximately 34 m GEL, stored as ice in the polar layered deposits (PLD), lobate debris aprons, ice-rich latitude dependent mantles, and as shallow ground ice), they extrapolate the evolution of this inventory backward in time, taking into account the introduction of new water by volcanism, outflow channel activity, and the loss of water by exospheric escape. They conclude that, at the end of the Noachian, Mars had a near-surface water inventory of approximately 24 m and approximately 62 m by the end of the Hesperian - inventories that Carr and Head argue were incompatible with the existence of a former ocean.

Antiferroquadrupolar correlations in the quantum spin ice candidate Pr2Zr2O7

NASA Astrophysics Data System (ADS)

Petit, S.; Lhotel, E.; Guitteny, S.; Florea, O.; Robert, J.; Bonville, P.; Mirebeau, I.; Ollivier, J.; Mutka, H.; Ressouche, E.; Decorse, C.; Ciomaga Hatnean, M.; Balakrishnan, G.

2016-10-01

We present an experimental study of the quantum spin ice candidate pyrochlore compound Pr2Zr2O7 by means of magnetization measurements, specific heat, and neutron scattering up to 12 T and down to 60 mK. When the field is applied along the [111 ] and [1 1 ¯0 ] directions, k =0 field-induced structures settle in. We find that the ordered moment rises slowly, even at very low temperature, in agreement with macroscopic magnetization. Interestingly, for H ∥[1 1 ¯0 ] , the ordered moment appears on the so-called α chains only. The spin excitation spectrum is essentially inelastic and consists in a broad flat mode centered at about 0.4 meV with a magnetic structure factor which resembles the spin ice pattern. For H ∥[1 1 ¯0 ] (at least up to 2.5 T), we find that a well-defined mode forms from this broad response, whose energy increases with H , in the same way as the temperature of the specific-heat anomaly. We finally discuss these results in the light of mean field calculations and propose an interpretation where quadrupolar interactions play a major role, overcoming the magnetic exchange. In this picture, the spin ice pattern appears shifted up to finite energy because of those interactions. We then propose a range of acceptable parameters for Pr2Zr2O7 that allow to reproduce several experimental features observed under field. With these parameters, the actual ground state of this material would be an antiferroquadrupolar liquid with spin-ice-like excitations.

Distance-dependent radiation chemistry: Oxidation versus hydrogenation of CO in electron-irradiated H2O/CO/H2O ices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrik, Nikolay G.; Monckton, Rhiannon J.; Koehler, Sven

Electron-stimulated oxidation of CO in layered H2O/CO/H2O ices was investigated with infrared reflection-absorption spectroscopy (IRAS) as function of the distance of the CO layer from the water/vacuum interface. The results show that while both oxidation and reduction reactions occur within the irradiated water films, there are distinct regions where either oxidation or reduction reactions are dominant. At depths less than ~ 15 ML, CO oxidation dominates over the sequential hydrogenation of CO to methanol (CH3OH), and CO2 is the major product of CO oxidation, consistent with previous observations. At its highest yield, CO2 accounts for ~45% of all the reactedmore » CO. Another oxidation product is identified as the formate anion (HCO2-). In contrast, for CO buried more than ~ 35 ML below the water/vacuum interface, the CO-to-methanol conversion efficiency is close to 100%. Production of CO2 and formate are not observed for the more deeply buried CO layers, where hydrogenation dominates. Experiments with CO dosed on pre-irradiated ASW samples suggest that OH radicals are primarily responsible for the oxidation reactions. Possible mechanisms of CO oxidation, involving primary and secondary processes of water radiolysis at low temperature, are discussed. The observed distance-dependent radiation chemistry results from the higher mobility of hydrogen atoms that are created by the interaction of the 100 eV electrons with the water films. These hydrogen atoms, which are primarily created at or near the water/vacuum interface, can desorb from or diffuse into the water films, while the less-mobile OH radicals remain in the near-surface zone resulting in preferential oxidation reactions there. The diffusing hydrogen atoms are responsible for the hydrogenation reactions that are dominant for the more deeply buried CO layers.« less

Sputtering of ices in the outer solar system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, R.E.

1996-01-01

Exploration of the outer solar system has led to studies in a new area of physics: electronically induced sputtering of low-temperature, condensed-gas solids (ices). Many of the icy bodies in the outer solar system were found to be bombarded by relatively intense fluxes of ions and electrons, causing both changes in their optical reflectance and ejection (sputtering) of molecules from their surfaces. The small cohesive energies of the condensed-gas solids afford relatively large sputtering rates from the electronic excitations produced in the solid by fast ions and electrons. Such sputtering produces an ambient gas about an icy body, often themore » source of the local plasma. This colloquium outlines the physics of the sputtering of ices and its relevance to several outer-solar-system phenomena: the sputter-produced plasma trapped in Saturn{close_quote}s magnetosphere; the O{sub 2} atmosphere on Europa; and optical absorption features such as SO{sub 2} in the surface of Europa and O{sub 2} and, possibly, O{sub 3} in the surface of Ganymede. {copyright} {ital 1996 The American Physical Society.}« less

Compact-Nanobox Engineering of Transition Metal Oxides with Enhanced Initial Coulombic Efficiency for Lithium-Ion Battery Anodes.

PubMed

Zhu, Yanfei; Hu, Aiping; Tang, Qunli; Zhang, Shiying; Deng, Weina; Li, Yanhua; Liu, Zheng; Fan, Binbin; Xiao, Kuikui; Liu, Jilei; Chen, Xiaohua

2018-03-14

A novel strategy is proposed to construct a compact-nanobox (CNB) structure composed of irregular nanograins (average diameter ≈ 10 nm), aiming to confine the electrode-electrolyte contact area and enhance initial Coulombic efficiency (ICE) of transition metal oxide (TMO) anodes. To demonstrate the validity of this attempt, CoO-CNB is taken as an example which is synthesized via a carbothermic reduction method. Benefiting from the compact configuration, electrolyte can only contact the outer surface of the nanobox, keeping the inner CoO nanograins untouched. Therefore, the solid electrolyte interphase (SEI) formation is reduced. Furthermore, the internal cavity leaves enough room for volume variation upon lithiation and delithiation, resulting in superior mechanical stability of the CNB structure and less generation of fresh SEI. Consequently, the SEI remains stable and spatially confined without degradation, and hence, the CoO-CNB electrode delivers an enhanced ICE of 82.2%, which is among the highest values reported for TMO-based anodes in lithium-ion batteries. In addition, the CoO-CNB electrode also demonstrates excellent cyclability with a reversible capacity of 811.6 mA h g -1 (90.4% capacity retention after 100 cycles). These findings open up a new way to design high-ICE electrodes and boost the practical application of TMO anodes.

Radical-induced chemistry from VUV photolysis of interstellar ice analogues containing formaldehyde

NASA Astrophysics Data System (ADS)

Butscher, Teddy; Duvernay, Fabrice; Danger, Grégoire; Chiavassa, Thierry

2016-09-01

Surface processes and radical chemistry within interstellar ices are increasingly suspected to play an important role in the formation of complex organic molecules (COMs) observed in several astrophysical regions and cometary environments. We present new laboratory experiments on the low-temperature solid state formation of complex organic molecules - glycolaldehyde, ethylene glycol, and polyoxymethylene - through radical-induced reactivity from VUV photolysis of formaldehyde in water-free and water-dominated ices. Radical reactivity and endogenous formation of COMs were monitored in situ via infrared spectroscopy in the solid state and post photolysis with temperature programmed desorption (TPD) using a quadripole mass spectrometer. We show the ability of free radicals to be stored when formed at low temperature in water-dominated ices, and to react with other radicals or on double bonds of unsaturated molecules when the temperature increases. It experimentally confirms the role of thermal diffusion in radical reactivity. We propose a new pathway for formaldehyde polymerisation induced by HCO radicals that might explain some observations made by the Ptolemy instrument on board the Rosetta lander Philae. In addition, our results seem to indicate that H-atom additions on H2CO proceed preferentially through CH2OH intermediate radicals rather than the CH3O radical.

Effects of insolation on habitability and the isotopic history of Martian water

NASA Astrophysics Data System (ADS)

Moores, John

Three aspects of the Habitability of the Northern Plains of Mars to organics and terrestrial-like microbial life were assessed. (1) Protection offered by small surface features and; (2) the breakdown of rocks to form soils were examined using a radiative transfer computer model. Two separate sublimation experiments provided a basis to improve; (3) estimates of the amount of available water today and in the past by determining the fractionation of HDO between present-day reservoirs. (1) UV radiation sterilizes the hardiest of terrestrial organisms within minutes on the Martian surface. Small surface features including pits, trenches, flat faces and overhangs may create "safe havens" for organisms by blocking much of the UV flux. In the most favorable cases, this flux is sufficiently reduced such that organic in-fall could accumulate beneath overhanging surfaces and in pits and cracks while terrestrial microorganisms could persist for several tens of martian years. (2) The production of soils on the surface is considered by analogy with the arid US Southwest. Here differential insolation of incipient cracks of random orientations predicts crack orientation distributions consistent with field observations by assuming that only crack orientations which shield their interiors, minimizing their water loss, can grow, eventually disrupting the clast. (3) Disaggregated water ice to simulate the polar caps was produced by flash freezing in liquid nitrogen and crushing. When dust was added to the mixtures, the D/H ratio of the sublimate gas was seen to decrease with time from the bulk ratio. The more dust was added to the mixture, the more pronounced was this effect. The largest fractionation factor observed during these experiments was 2.5. Clean ice was also prepared and overlain by dust to simulate ground ice. Here, the movement of water vapor was modeled using an effective diffusivity that incorporated both adsorption on grains and diffusion. For low temperatures (<-55°C) a significant difference between the diffusivities of H 2 O and HDO was observed. This suggests adsorptive-control within the regolith as energies of interaction are 60-70kJmol -1 . This ability of the martian regolith to preferentially adsorb HDO decouples the ice table and polar caps from the atmosphere and allows for geographic variations in the D/H ratio on Mars.

Evolution of Planetary Ice-Ocean Systems: Effects of Salinity

NASA Astrophysics Data System (ADS)

Allu Peddinti, D.; McNamara, A. K.

2015-12-01

Planetary oceanography is enjoying renewed attention thanks to not only the detection of several exoplanetary ocean worlds but also due to the expanding family of ocean worlds within our own star system. Our solar system is now believed to host about nine ocean worlds including Earth, some dwarf planets and few moons of Jupiter and Saturn. Amongst them, Europa, like Earth is thought to have an ice Ih-liquid water system. However, the thickness of the Europan ice-ocean system is much larger than that of the Earth. The evolution of this system would determine the individual thicknesses of the ice shell and the ocean. In turn, these thicknesses can alter the course of evolution of the system. In a pure H2O system, the thickness of the ice shell would govern if heat loss occurs entirely by conduction or if the shell begins to convect as it attains a threshold thickness. This switch between conduction-convection regimes could determine the longevity of the subsurface ocean and hence define the astrobiological potential of the planetary body at any given time. In reality, however, the system is not pure water ice. The detected induced magnetic field infers a saline ocean layer. Salts are expected to act as an anti-freeze allowing a subsurface ocean to persist over long periods but the amount of salts would determine the extent of that effect. In our current study, we use geodynamic models to examine the effect of salinity on the evolution of ice-ocean system. An initial ocean with different salinities is allowed to evolve. The effect of salinity on thickness of the two layers at any time is examined. We also track how salinity controls the switch between conductive-convective modes. The study shows that for a given time period, larger salinities can maintain a thick vigorously convecting ocean while the smaller salinities behave similar to a pure H2O system leading to a thick convecting ice-shell. A range of salinities identified can potentially predict the current state and possibly the intermediate states of the ice-ocean system as it evolved over time. This could help constrain the endogenic contribution of salts to the surface chemistry.

Microwave properties of solid CO2. [for Mars surface study

NASA Technical Reports Server (NTRS)

Simpson, R. A.; Howard, H. T.; Fair, B. C.

1980-01-01

Measurements over the range of 2.2 to 12.0 GHz show that CO2 snow is a slightly lossy dielectric whose constant varies with density following the Rayleigh formula to 1.27 g/cu cm. It is independent of frequency and does not vary with temperature in the 113 to 183 K range; frequency independence and agreement with the Rayleigh fit are obtained from measurements on dry block ice. The dielectric constant of solid CO2 in block form is lower than that of solid water ice or solid rock; in powder form, the constant for CO2 is also lower than that of H2O (snow) or soils. These measurements may be useful in limiting the interpretations of the Viking radio reflection experiment; a radio value of 3.0 for the dielectric constant near the North Pole would be strong evidence against the presence of cm thicknesses of CO2 in that region.

Natural antioxidant ice cream acutely reduces oxidative stress and improves vascular function and physical performance in healthy individuals.

PubMed

Sanguigni, Valerio; Manco, Melania; Sorge, Roberto; Gnessi, Lucio; Francomano, Davide

2017-01-01

The formation of reactive oxygen species (ROS) contributes to the pathogenesis and progression of several diseases. Polyphenols have been shown to be beneficial against ROS. The aim of this study was to evaluate the effects of a natural antioxidant ice cream on oxidative stress, vascular function, and physical performance. In this controlled, single-blind, crossover study, 14 healthy individuals were randomized to consume 100 g of either antioxidant ice cream containing dark cocoa powder and hazelnut and green tea extracts or milk chocolate ice cream (control ice cream). Participants were studied at baseline and 2 h after ingesting ice cream. Serum polyphenols, antioxidant status (ferric-reducing ability of plasma [FRAP]), nitric oxide (NOx) bioavailability, markers of oxidative stress (determination of reactive oxygen metabolites [d-ROMs] and hydrogen peroxide [H 2 O 2 ]), endothelium function (flow-mediated dilation [FMD] and reactive hyperemia index [RHI]), and exercise tolerance (stress test) were assessed, and the double product was measured. Serum polyphenols (P < 0.001), NOx (P < 0.001), FRAP (P < 0.005), FMD (P < 0.001), and RHI (P < 0.05) increased significantly, oxidative stress decreased (d-Roms, P < 0.001; H 2 O 2 , P < 0.001), and the double product (P < 0.001) was improved only after antioxidant ice cream ingestion. No changes were found after control ice cream ingestion. To our knowledge, this is the first study to demonstrate that a natural ice cream rich in polyphenols acutely improved vascular function and physical performance in healthy individuals through a reduction in oxidative stress. Copyright © 2016 Elsevier Inc. All rights reserved.

Laboratory measurements of HDO/H2O isotopic fractionation during ice deposition in simulated cirrus clouds

PubMed Central

Lamb, Kara D.; Clouser, Benjamin W.; Bolot, Maximilien; Sarkozy, Laszlo; Ebert, Volker; Saathoff, Harald; Möhler, Ottmar; Moyer, Elisabeth J.

2017-01-01

The stable isotopologues of water have been used in atmospheric and climate studies for over 50 years, because their strong temperature-dependent preferential condensation makes them useful diagnostics of the hydrological cycle. However, the degree of preferential condensation between vapor and ice has never been directly measured at temperatures below 233 K (−40 °C), conditions necessary to form cirrus clouds in the Earth’s atmosphere, routinely observed in polar regions, and typical for the near-surface atmospheric layers of Mars. Models generally assume an extrapolation from the warmer experiments of Merlivat and Nief [Merlivat L, Nief G (1967) Tellus 19:122–127]. Nonequilibrium kinetic effects that should alter preferential partitioning have also not been well characterized experimentally. We present here direct measurements of HDO/H2O equilibrium fractionation between vapor and ice (αeq) at cirrus-relevant temperatures, using in situ spectroscopic measurements of the evolving isotopic composition of water vapor during cirrus formation experiments in a cloud chamber. We rule out the recent proposed upward modification of αeq, and find values slightly lower than Merlivat and Nief. These experiments also allow us to make a quantitative validation of the kinetic modification expected to occur in supersaturated conditions in the ice–vapor system. In a subset of diffusion-limited experiments, we show that kinetic isotope effects are indeed consistent with published models, including allowing for small surface effects. These results are fundamental for inferring processes on Earth and other planets from water isotopic measurements. They also demonstrate the utility of dynamic in situ experiments for studying fractionation in geochemical systems. PMID:28495968

Computational Recreation of Carbon Dioxide Hydrates at Habitable Planetary Conditions

NASA Astrophysics Data System (ADS)

Recio, J. M.; Izquierdo-Ruiz, F.; Prieto-Ballesteros, O.

2017-12-01

Gas clathrate hydrates are proposed as constituents of the icy moons of the giant planets in the Solar System [1]. Carbon dioxide has been detected on the surface of the moons of Jupiter, supposedly originated by internal degasification. In Ganymede, an aqueous ocean is proposed to exist under a thick ice crust in coexistence with several forms of ice, with pressure reaching up to 1.3 GPa [2]. Due to the limited available data on these systems under these conditions, we propose a combination of computational and experimental studies to describe microscopically and macroscopically the structural and chemical behavior of CO2@H2O polymorphs. This will allow us to understand how their presence affects the geophysical structure and activity and their impact on the habitability of the icy moon. A transition from the sI cubic structure to a high pressure phase at around 0.7 GPa has been found for CO2@H2O. In spite of different attempts to characterize the new structure, a definite answer has not been provided yet. A MH-III Filled Ice Structure type was proposed after neutron diffraction experiments in contrast with an alternative structure similar to the hexagonal C0 type for H2 hydrates [3]. It has an estimated hydration level ratio up to 2H2O:1CO2 and 6 water molecules per unit cell. In the figure below, our optimized unit cell based on this hexagonal C0 structure is displayed. Ab initio calculations using the XDM approximation to include van der Waals effects are performed in our search for the pressure evolution of the equilibrium geometries of the C0-CO2@H2O phase and those of a close related structure to this one called Ih-C0, with 8 water molecules per unit cell. We obtain occupation energies at different hydration ratios, densities, equations of state parameters, and stability energies with respect to decomposition. Raman and IR frequencies are also computed in the 0-2 GPa range. High pressure experiments are also being done in a newly designed chamber able to reach 1 GPa. It is equipped with a sapphire window to allow the measurements of Raman spectra. We believe that these results may throw light into gas hydrates of the habitable bodies of our Solar System. [1] Buffet B. A., Ann. Rev. Earth Plan. Sci. 28, 477, 2010. [2] Bland, M.T. et al. Icarus 200, 207, 2009. [3] Smirnov G. S. et al., J. Phys. Chem. Lett., 2013, 4, 3560

Radiolysis of astrophysical ices by heavy ion irradiation: Destruction cross section measurement

NASA Astrophysics Data System (ADS)

de Barros, A. L. F.; Boduch, P.; Domaracka, A.; Rothard, H.; da Silveira, E. F.

2012-08-01

Many solar system objects, such as planets and their satellites, dust grains in rings, and comets, are known to either be made of ices or to have icy surfaces. These ices are exposed to ionizing radiation including keV, MeV and GeV ions from solar wind or cosmic rays. Moreover, icy dust grains are present in interstellar space and, in particular, in dense molecular clouds. Radiation effects include radiolysis (the destruction of molecules leading to formation of radicals), the formation of new molecules following radiolysis, the desorption or sputtering of atoms or molecules from the surface, compaction of porous ices, and phase changes. This review discusses the application of infrared spectroscopy FTIR to study the evolution of the chemical composition of ices containing the most abundant molecular species found in the solar system and interstellar medium, such as H2O, CO, CO2 and hydrocarbons. We focus on the evolution of chemical composition with ion fluence in order to deduce the corresponding destruction and formation cross sections. Although initial approach focused on product identification, it became increasingly necessary to work toward a comprehensive understanding of ice chemistry. The abundances of these molecules in different phases of ice mantles provide important clues to the chemical processes in dense interstellar clouds, and therefore it is of importance to accurately measure the quantities such as dissociation and formation cross sections of the infrared features of these molecules. We also are able to obtain the scaling of these cross sections with deposited energy.

Processing of analogues of plume fallout in cold regions of Enceladus by energetic electrons

NASA Astrophysics Data System (ADS)

Bergantini, A.; Pilling, S.; Nair, B. G.; Mason, N. J.; Fraser, H. J.

2014-10-01

Context. Enceladus, a small icy moon of Saturn, is one of the most remarkable bodies in the solar system. This moon is a geologically active object, and despite the lower temperatures on most of its surface, the geothermally heated south polar region presents geysers that spouts a plume made of water (~90%), carbon dioxide, methane, ammonia, and methanol, among other molecules. Most of the upward-moving particles do not have the velocity to escape from the gravitational influence of the moon and fall back to the surface. The molecules in the ice are continuously exposed to ionizing radiation, such as UV and X-rays photons, cosmic rays, and electrons. Over time, the ionizing radiation promotes molecular bond rupture, destroying and also forming molecules, radicals, and fragments. Aims: We analyse the processing of an ice mixture analogue to the Enceladus fallout ice in cold resurfaced areas (north pole) by 1 keV electrons. The main goal is to search for complex species that have not yet been detected in this moon, and to determine relevant physico-chemical parameters, such as destruction and formation cross-sections and the half-life of the studied molecules in the ice. Methods: The experiment consisted of the electron irradiation of an Enceladus-like ice mixture (H2O:CO2:CH4:NH3:CH3OH) in an ultra-high vacuum chamber at 20 K. The analysis was made by infrared spectrometry in the mid-infrared region (4000-800 cm-1 or 2.5-12.5 μm). Results: The absolute dissociation cross-sections of the parent molecules, the formation cross-section of daughter species, and the half-life of the parental species in a simulated Enceladus irradiation scenario were determined. Among the produced species, CO (carbon monoxide), OCN- (cyanate anion), HCONH2 (formamide), and H2CO (formaldehyde) were tentatively detected.

An extremely high-altitude plume seen at Mars' morning terminator.

PubMed

Sánchez-Lavega, A; Muñoz, A García; García-Melendo, E; Pérez-Hoyos, S; Gómez-Forrellad, J M; Pellier, C; Delcroix, M; López-Valverde, M A; González-Galindo, F; Jaeschke, W; Parker, D; Phillips, J; Peach, D

2015-02-26

The Martian limb (that is, the observed 'edge' of the planet) represents a unique window into the complex atmospheric phenomena occurring there. Clouds of ice crystals (CO2 ice or H2O ice) have been observed numerous times by spacecraft and ground-based telescopes, showing that clouds are typically layered and always confined below an altitude of 100 kilometres; suspended dust has also been detected at altitudes up to 60 kilometres during major dust storms. Highly concentrated and localized patches of auroral emission controlled by magnetic field anomalies in the crust have been observed at an altitude of 130 kilometres. Here we report the occurrence in March and April 2012 of two bright, extremely high-altitude plumes at the Martian terminator (the day-night boundary) at 200 to 250 kilometres or more above the surface, and thus well into the ionosphere and the exosphere. They were spotted at a longitude of about 195° west, a latitude of about -45° (at Terra Cimmeria), extended about 500 to 1,000 kilometres in both the north-south and east-west directions, and lasted for about 10 days. The features exhibited day-to-day variability, and were seen at the morning terminator but not at the evening limb, which indicates rapid evolution in less than 10 hours and a cyclic behaviour. We used photometric measurements to explore two possible scenarios and investigate their nature. For particles reflecting solar radiation, clouds of CO2-ice or H2O-ice particles with an effective radius of 0.1 micrometres are favoured over dust. Alternatively, the plume could arise from auroral emission, of a brightness more than 1,000 times that of the Earth's aurora, over a region with a strong magnetic anomaly where aurorae have previously been detected. Importantly, both explanations defy our current understanding of Mars' upper atmosphere.

The Saturnian satellite Rhea as seen by Cassini VIMS

USGS Publications Warehouse

Stephan, K.; Jaumann, R.; Wagner, R.; Clark, R.N.; Cruikshank, D.P.; Giese, B.; Hibbitts, C.A.; Roatsch, T.; Matz, K.-D.; Brown, R.H.; Filacchione, G.; Cappacioni, F.; Scholten, F.; Buratti, B.J.; Hansen, G.B.; Nicholson, P.D.; Baines, K.H.; Nelson, R.M.; Matson, D.L.

2012-01-01

Since the arrival of the Cassini spacecraft at Saturn in June 2004, the Visual and Infrared Mapping Spectrometer has obtained new spectral data of the icy satellites of Saturn in the spectral range from 0.35 to 5.2 ??m. Numerous flybys were performed at Saturn's second largest satellite Rhea, providing a nearly complete coverage with pixel-ground resolutions sufficient to analyze variations of spectral properties across Rhea's surface in detail. We present an overview of the VIMS observations obtained so far, as well as the analysis of the spectral properties identified in the VIMS spectra and their variations across its surface compared with spatially highly resolved Cassini ISS images and digital elevation models. Spectral variations measured across Rhea's surface are similar to the variations observed in the VIMS observations of its neighbor Dione, implying similar processes causing or at least inducing their occurrence. Thus, magnetospheric particles and dust impacting onto the trailing hemisphere appear to be responsible for the concentration of dark rocky/organic material and minor amounts of CO 2 in the cratered terrain on the trailing hemisphere. Despite the prominent spectral signatures of Rhea's fresh impact crater Inktomi, radiation effects were identified that also affect the H 2O ice-rich cratered terrain of the leading hemisphere. The concentration of H 2O ice in the vicinity of steep tectonic scarps near 270??W and geologically fresh impact craters implies that Rhea exhibits an icy crust at least in the upper few kilometers. Despite the evidence for past tectonic events, no indications of recent endogenically powered processes could be identified in the Cassini data. ?? 2011 Elsevier Ltd. All rights reserved.

Distillation of H2O from hard-frozen Martian permafrost

NASA Technical Reports Server (NTRS)

Zent, A. P.; Gwynne, O.

1991-01-01

The authors present a method for distillation of hard-frozen Martian permafrost. A cable-tool is drilled into hard frozem permafrost to a depth of 10 to 20 m. They calculate that a 10 m hole could be drilled in a few days. A 10 m shaft with a diameter equal to the bore is inserted into the hole, and a air tight tent-like structure is erected over the borehole. Photovoltaic cells mounted on the tent supply electrical energy that is dissipated in the shaft. Drilling power can be supplied by other sources. With 1000 watts, the shaft can be heated to near 350 K, producing relatively high temperatures in the vicinity of the borehole. Surrounding H2O is vaporized and diffuses up through the regolith. The authors calculate that a tent of a radius of no more than a few meters would intercept most of the H2O as it diffused to the surface. Calculations suggest that it would require perhaps 30 days to extract H2O from most of the volume drained by this technique. Assuming that the hard frozen regolith is no more than 10 percent ice, the author's calculate that that about 2890 kg of H2O could be extracted in 30 days. Since the nominal requirement for each crew member is about 5 kg/day, one such borehole might be expected to supply enough H2O to maintain a crew of 5 for perhaps 100 days. Additional engineering studies will be done to attempt to improve the capacity or efficiency of this method.

Heterogeneous kinetics of H2O, HNO3 and HCl on HNO3 hydrates (α-NAT, β-NAT, NAD) in the range 175-200 K

NASA Astrophysics Data System (ADS)

Iannarelli, Riccardo; Rossi, Michel J.

2016-09-01

Experiments on the title compounds have been performed using a multidiagnostic stirred-flow reactor (SFR) in which the gas phase as well as the condensed phase has been simultaneously investigated under stratospheric temperatures in the range 175-200 K. Wall interactions of the title compounds have been taken into account using Langmuir adsorption isotherms in order to close the mass balance between deposited and desorbed (recovered) compounds. Thin solid films at 1 µm typical thickness have been used as a proxy for atmospheric ice particles and have been deposited on a Si window of the cryostat, with the optical element being the only cold point in the deposition chamber. Fourier transform infrared (FTIR) absorption spectroscopy in transmission as well as partial and total pressure measurement using residual gas mass spectrometry (MS) and sensitive pressure gauges have been employed in order to monitor growth and evaporation processes as a function of temperature using both pulsed and continuous gas admission and monitoring under SFR conditions. Thin solid H2O ice films were used as the starting point throughout, with the initial spontaneous formation of α-NAT (nitric acid trihydrate) followed by the gradual transformation of α- to β-NAT at T > 185 K. Nitric acid dihydrate (NAD) was spontaneously formed at somewhat larger partial pressures of HNO3 deposited on pure H2O ice. In contrast to published reports, the formation of α-NAT proceeded without prior formation of an amorphous HNO3 / H2O layer and always resulted in β-NAT. For α- and β-NAT, the temperature-dependent accommodation coefficient α(H2O) and α(HNO3), the evaporation flux Jev(H2O) and Jev(HNO3) and the resulting saturation vapor pressure Peq(H2O) and Peq(HNO3) were measured and compared to binary phase diagrams of HNO3 / H2O in order to afford a thermochemical check of the kinetic parameters. The resulting kinetic and thermodynamic parameters of activation energies for evaporation (Eev) and standard heats of evaporation ΔHev0 of H2O and HNO3 for α- and β-NAT, respectively, led to an estimate for the relative standard enthalpy difference between α- and β-NAT of -6.0 ± 20 kJ mol-1 in favor of β-NAT, as expected, despite a significantly larger value of Eev for HNO3 in α-NAT. This in turn implies a substantial activation energy for HNO3 accommodation in α- compared to β-NAT where Eacc(HNO3) is essentially zero. The kinetic (α(HCl), Jev(HCl)) and thermodynamic (Peq(HCl)) parameters of HCl-doped α- and β-NAT have been determined under the assumption that HCl adsorption did not significantly affect α(H2O) and α(HNO3) as well as the evaporation flux Jev(H2O). Jev(HCl) and Peq(HCl) on both α- and β-NAT are larger than the corresponding values for HNO3 across the investigated temperature range but significantly smaller than the values for pure H2O ice at T < 200 K.

Ketene Formation in Interstellar Ices: A Laboratory Study

NASA Technical Reports Server (NTRS)

Hudson, Reggie L.; Loeffler, Mark Josiah

2013-01-01

The formation of ketene (H2CCO, ethenone) in polar and apolar ices was studied with in situ 0.8 MeV proton irradiation, far-UVphotolysis, and infrared spectroscopic analyses at 10-20 K. Using isotopically enriched reagents, unequivocal evidencewas obtained for ketene synthesis in H2O-rich and CO2-rich ices, and several reaction products were identified. Results from scavenging experiments suggested that ketene was formed by free-radical pathways, as opposed to acid-base processes or redox reactions. Finally, we use our results to draw conclusions about the formation and stability of ketene in the interstellar medium.

Gas-grain chemical models of star-forming molecular clouds as constrained by ISO and SWAS observations

NASA Astrophysics Data System (ADS)

Charnley, S. B.; Rodgers, S. D.; Ehrenfreund, P.

2001-11-01

We have investigated the gaseous and solid state molecular composition of dense interstellar material that periodically experiences processing in the shock waves associated with ongoing star formation. Our motivation is to confront these models with the stringent abundance constraints on CO2, H2O and O2, in both gas and solid phases, that have been set by ISO and SWAS. We also compare our results with the chemical composition of dark molecular clouds as determined by ground-based telescopes. Beginning with the simplest possible model needed to study molecular cloud gas-grain chemistry, we only include additional processes where they are clearly required to satisfy one or more of the ISO-SWAS constraints. When CO, N2 and atoms of N, C and S are efficiently desorbed from grains, a chemical quasi-steady-state develops after about one million years. We find that accretion of CO2 and H2O cannot explain the [CO2/H2O]ice ISO observations; as with previous models, accretion and reaction of oxygen atoms are necessary although a high O atom abundance can still be derived from the CO that remains in the gas. The observational constraints on solid and gaseous molecular oxygen are both met in this model. However, we find that we cannot explain the lowest H2O abundances seen by SWAS or the highest atomic carbon abundances found in molecular clouds; additional chemical processes are required and possible candidates are given. One prediction of models of this type is that there should be some regions of molecular clouds which contain high gas phase abundances of H2O, O2 and NO. A further consequence, we find, is that interstellar grain mantles could be rich in NH2OH and NO2. The search for these regions, as well as NH2OH and NO2 in ices and in hot cores, is an important further test of this scenario. The model can give good agreement with observations of simple molecules in dark molecular clouds such as TMC-1 and L134N. Despite the fact that S atoms are assumed to be continously desorbed from grain surfaces, we find that the sulphur chemistry independently experiences an ``accretion catastrophe''. The S-bearing molecular abundances cease to lie within the observed range after about 3 x 106 years and this indicates that there may be at least two efficient surface desorption mechanisms operating in dark clouds - one quasi-continous and the other operating more sporadically on this time-scale. We suggest that mantle removal on short time-scales is mediated by clump dynamics, and by the effects of star formation on longer time-scales. The applicability of this type of dynamical-chemical model for molecular cloud evolution is discussed and comparison is made with other models of dark cloud chemistry.

Self-sustaining Mars colonies utilizing the North Polar Cap and the Martian atmosphere.

PubMed

Powell, J; Maise, G; Paniagua, J

2001-01-01

A revolutionary new concept for the early establishment of robust, self-sustaining Martian colonies is described. The colonies would be located on the North Polar Cap of Mars and utilize readily available water ice and the CO2 Martian atmosphere as raw materials to produce all of the propellants, fuel, air, water, plastics, food, and other supplies needed by the colony. The colonists would live in thermally insulated large, comfortable habitats under the ice surface, fully shielded from cosmic rays. The habitats and supplies would be produced by a compact, lightweight (~4 metric tons) nuclear powered robotic unit termed ALPH (Atomic Liberation of Propellant and Habitat), which would land 2 years before the colonists arrived. Using a compact, lightweight 5 MW (th) nuclear reactor/steam turbine (1 MW(e)) power source and small process units (e.g., H2O electrolyzer, H2 and O2 liquefiers, methanator, plastic polymerizer, food producer, etc.) ALPH would stockpile many hundreds of tons of supplies in melt cavities under the ice, plus insulated habitats, to be in place and ready for use when the colonists landed. With the stockpiled supplies, the colonists would construct and operate rovers and flyers to explore the surface of Mars. ALPH greatly reduces the amount of Earth supplied material needed and enables large permanent colonies on Mars. It also greatly reduces human and mission risks and vastly increases the capability not only for exploration of the surrounding Martian surface, but also the ice cap itself. The North Polar Cap is at the center of the vast ancient ocean that covered much of the Martian Northern Hemisphere. Small, nuclear heated robotic probes would travel deep (1 km or more) inside the ice cap, collecting data on its internal structure, the composition and properties of the ancient Martian atmosphere, and possible evidence of ancient life forms (microfossils, traces of DNA, etc.) that were deposited either by wind or as remnants of the ancient ocean. Details of the ALPH system, which is based on existing technology, are presented. ALPH units could be developed and demonstrated on Earth ice sheets within a few years. An Earth-Mars space transport architecture is described, in which Mars produced propellant and supplies for return journeys to Earth would be lifted with relatively low DeltaV to Mars orbit, and from there transported back to Earth orbit, enabling faster and lower cost trips from Earth to Mars. The exploration capability and quality of life in a mature Martian colony of 500 persons located on the North Polar Cap is outlined. c2001 International Astronautical Federation. Published by Elsevier Science Ltd.

Studies of solid carbon dioxide in interstellar ice analogs subject to thermal processing

NASA Astrophysics Data System (ADS)

White, Douglas W.

2010-09-01

Solid CO2 has been detected in many lines of sight in the interstellar medium from infrared observatories. Spectral profiles from space-based observatories have suggested that CO2 on icy grain mantles is mixed with other common molecules such as H2O and CH 3OH in interstellar regions and that thermal annealing has occurred. The vibrational mode at 658 cm-1 (15.2 mum) is suspected to be a powerful diagnostic tool as to the composition of species on icy grain mantles as well as thermal histories. However, previous studies have not systematically investigated ice composition and temperature. Laboratory spectra of interstellar ice analogs have been created in this study order to better understand the physical properties of solid CO2 in these interstellar environments. Existing databases of ice composition studies and effects of ice thermal history were updated in this study to include a more systematic approach. The 658 cm-1 (15.2 mum) bending mode feature of CO2 is examined here and the subsequent astrophysical implications stated. In the first set of experiments, 47 mixtures of H2O,CH3OH, andCO2 were slowly warmed and mid-infrared absorption spectra were recorded at 5K intervals. The second set of experiments involved examining the CO2 bending mode feature of 10 different CO2-containing ice mixtures at different temperatures where ice segregation was suspected. In these experiments, the ice mixtures were slowly heated to the desired temperature for increasing time intervals before cooling down and recording mid-IR absorption spectra. These studies may be used to analyze IR data from space-based observatories such as the Spitzer Space Telescope Infrared Spectrograph as well other future IR observations of the interstellar medium. Finally, mass spectroscopy measurements were taken from temperature programmed desorption (TPD) experiments performed on several binary mixtures of H2O + CO2 and CH 3OH + CO2. Physical properties such as desorption energy of CO2 can be determined from the TPD traces of these experiments. The work provided here addresses the physical properties of solid CO 2 thermally processed in ice mixtures in interstellar environments by laboratory simulations spectroscopically analyzed by mid-infrared absorption profiles and TPD.

Infrared Observations of Hot Gas and Cold Ice Toward the Low Mass Protostar Elias 29

NASA Technical Reports Server (NTRS)

Boogert, A. C. A.; Tielens, A. G. G. M.; Ceccarelli, C.; Boonman, A. M. S.; vanDishoeck, E. F.; Keane, J. V.; Whittet, D. C. B.; deGraauw, T.

2000-01-01

We have obtained the full 1-200 micrometer spectrum of the low luminosity (36 solar luminosity Class I protostar Elias 29 in the rho Ophiuchi molecular cloud. It provides a unique opportunity to study the origin and evolution of interstellar ice and the interrelationship of interstellar ice and hot core gases around low mass protostars. We see abundant hot CO and H2O gas, as well as the absorption bands of CO, CO2, H2O and "6.85 micrometer" ices. We compare the abundances and physical conditions of the gas and ices toward Elias 29 with the conditions around several well studied luminous, high mass protostars. The high gas temperature and gas/solid ratios resemble those of relatively evolved high mass objects (e.g. GL 2591). However, none of the ice band profiles shows evidence for significant thermal processing, and in this respect Elias 29 resembles the least evolved luminous protostars, such as NGC 7538 : IRS9. Thus we conclude that the heating of the envelope of the low mass object Elias 29 is qualitatively different from that of high mass protostars. This is possibly related to a different density gradient of the envelope or shielding of the ices in a circumstellar disk. This result is important for our understanding of the evolution of interstellar ices, and their relation to cometary ices.

Normalized fluctuations, H2O vs n-hexane: Site-correlated percolation

NASA Astrophysics Data System (ADS)

Koga, Yoshikata; Westh, Peter; Sawamura, Seiji; Taniguchi, Yoshihiro

1996-08-01

Entropy, volume and the cross fluctuations were normalized to the average volume of a coarse grain with a fixed number of molecules, within which the local and instantaneous value of interest is evaluated. Comparisons were made between liquid H2O and n-hexane in the range from -10 °C to 120 °C and from 0.1 MPa to 500 MPa. The difference between H2O and n-hexane in temperature and pressure dependencies of these normalized fluctuations was explained in terms of the site-correlated percolation theory for H2O. In particular, the temperature increase was confirmed to reduce the hydrogen bond probability, while the pressure appeared to have little effect on the hydrogen bond probability. According to the Le Chatelier principle, however, the putative formation of ``ice-like'' patches at low temperatures due to the site-correlated percolation requirement is retarded by pressure increases. Thus, only in the limited region of low pressure (<300 MPa) and temperature (<60 °C), the fluctuating ice-like patches are considered to persist.

The gas phase origin of complex organic molecules precursors in prestellar cores

NASA Astrophysics Data System (ADS)

Bacmann, A.; Faure, A.

2015-05-01

Complex organic molecules (COMs) have long been observed in the warm regions surrounding nascent protostars. The recent discovery of oxygen-bearing COMs like methyl formate or dimethyl ether in prestellar cores (Bacmann et al. [2]), where gas and dust temperatures rarely exceed 10-15 K, has challenged the previously accepted models according to which COM formation relied on the diffusion of heavy radicals on warm (˜30 K) grains. Following these detections, new questions have arisen: do non-thermal processes play a role in increasing radical mobility or should new gas-phase routes be explored? The radicals involved in the formation of the aforementioned COMs, HCO and CH3O represent intermediate species in the grain-surface synthesis of methanol which proceeds via successive hydrogenations of CO molecules in the ice. We present here observations of methanol and its grain-surface precursors HCO, H2CO, CH3O in a sample of prestellar cores and derive their relative abundances. We find that the relative abundances HCO:H2CO:CH3O:CH3OH are constant across the core sample, close to 10:100:1:100. Our results also show that the amounts of HCO and CH3O are consistent with a gas-phase synthesis of these species from H2CO and CH3OH via radical-neutral or ion-molecule reactions followed by dissociative recombinations. Thus, while grain chemistry is necessary to explain the abundances of the parent volatile CH3OH, and possibly H2CO, the reactive species HCO and CH3O might be daughter molecules directly produced in the gas-phase.

Bright Fans in Mars Cryptic Region Caused by Adiabatic Cooling of CO2 Gas Jets.

NASA Astrophysics Data System (ADS)

Titus, T. N.; Kieffer, H. H.; Langevin, Y.; Murchie, S.; Seelos, F.; Vincendon, M.

2007-12-01

Over the last decade, observations of the retreat of the southern seasonal cap of Mars have revealed the presence of exotic processes within an area now informally referred to as the cryptic region. The appearance of dark spots, fans, blotches, and halos have been a "hot" topic of scientific discussion since they were first observed by the Mars Global Surveyor (MGS) Mars Orbiter Camera (MOC) [Malin et al., 1998]. Further observations by the Mars Odyssey (ODY) Thermal Emission Imaging System (THEMIS) showed that the dark features remained cold throughout the early-to-mid spring, suggesting that these features were either CO2 ice or were in thermal contact with CO2 ice [Kieffer et al., 2006]. In this paper, we present observations in the near-infrared at spatial resolutions that have previously been unavailable. We present further evidence that many of these features in the cryptic region are the result of cold jets, as first described by Kieffer [2000, 2007]. The adiabatic cooling of gas spewing downwind from the jets produces CO2 frost, thus forming the bright fans. The bright fans appear to be devoid of H2O ice, thus further supporting the hypothesis that they are formed from the downwind settling of CO2 frost. In some areas, the bright fans are adjacent to dark fans and appear to start from common vertices, while in other areas, bright fan-like deposits occur without the strong presence of dark fans. References: Kieffer, H.H. (2000) Annual Punctuated CO2 Slab-Ice and Jets on Mars, International Conference on Mars Polar Science and Exploration, p. 93. Kieffer, H.H. et al. (2006) Nature, 442,793-796. Kieffer, H.H. (2007) JGR, in press. Malin, M.C., M.H. Carr, G.E. Danielson, M.E. Davies, W.K. Hartmann, A.P. Ingersoll, P.B. James, H. Masursky, A.S. McEwen, L.A. Soderblom, P. Thomas, J. Veverka, M.A. Caplinger, M.A. Ravine, and T.A. Soulanille (1998) Early views of the Martian surface from the Mars orbiter camera of Mars global surveyor, Science, 279, 1681-1685.

Ab initio theoretical calculations of the electronic excitation energies of small water clusters.

PubMed

Tachikawa, Hiroto; Yabushita, Akihiro; Kawasaki, Masahiro

2011-12-14

A direct ab initio molecular dynamics method has been applied to a water monomer and water clusters (H(2)O)(n) (n = 1-3) to elucidate the effects of zero-point energy (ZPE) vibration on the absorption spectra of water clusters. Static ab initio calculations without ZPE showed that the first electronic transitions of (H(2)O)(n), (1)B(1)←(1)A(1), are blue-shifted as a function of cluster size (n): 7.38 eV (n = 1), 7.58 eV (n = 2) and 8.01 eV (n = 3). The inclusion of the ZPE vibration strongly affects the excitation energies of a water dimer, and a long red-tail appears in the range of 6.42-6.90 eV due to the structural flexibility of a water dimer. The ultraviolet photodissociation of water clusters and water ice surfaces is relevant to these results.

Neutral O2 and Ion O2+ Sources from Rings into the Inner Magnetosphere

NASA Astrophysics Data System (ADS)

Elrod, M. K.; Johnson, R. E.; Cassidy, T. A.; Wilson, R. J.; Tseng, W.; Ip, W.

2009-12-01

The primary source of neutral O2 for Saturn’s magnetosphere is due to solar UV photons protons that produce O2 from H2O ice decomposition over the main rings as well as the tenuous F and G rings resulting in a tenuous O2 atmosphere (Johnson et. al. 2006). The O2 atmosphere is very thin to the point of being nearly collisionless. Our model of the atmosphere predict that as it interacts with the ring particles, the O2 is adsorbed and desorbed from the rings causing changes in the trajectories, which in turn, allows for a distribution of O2 from the rings throughout the magnetosphere (Tokar et. al. 2005; Tseng et. al. 2009). Predominately through photo-ionization and ion-exchange these O2 neutrals from the ice grains become a source for O2+ ions in the inner magnetosphere. Once the O2 becomes ionized to become O2+ the ions then follow the field lines. The ions interact with the ice particles in the rings to stick to the ring particles effectively reducing the ion density. As a result the ion density is greater over the Cassini Division and the area between the F and G ring where the optical depth due to the ice grain is less. Accordingly, the neutral O2 densities would tend to be high over the higher optical depth of the B and A main rings where the source rates are higher. Models of the neutral densities have shown high densities over the main rings, with a tail through the magnetosphere. Analysis of the CAPS (Cassini Plasma Spectrometer) data from the Saturn Orbit Insertion (SOI) in 2004 shows a peak in density over the Cassini Division and a higher peak in O2+ ion density between the F and G rings. References: Johnson, R.E., J.G. Luhmann, R.L. Tokar, M. Bouhram, J.J. Berthelier, E.C. Siler, J.F. Cooper, T.W. Hill, H.T. Smith, M. Michael, M. Liu, F.J. Crary, D.T. Young, "Production, Ionization and Redistribution of O2 Saturn's Ring Atmosphere" Icarus 180, 393-402 (2006).(pdf) Tokar, R.L., and 12 colleagues, 2005. Cassini Observations of the Thermal Plasma in the Vicinity of Saturn’s Main Rings and the F and G Rings. Geophys. Res. Lett. 32, doi:10.1029/2005GL022690. L14S04. Martens, H. R., Reisenfeld, D. B., Williams, J. D., Johnson, R.E., Smith H. T., “Observations of molecular oxygen ions in Saturn’s inner magnetosphere”. Geophy. Res. Lett. 2009. W.-L. Tseng, Ip, W.-H., Johnson, R. E., Cassidy, T. A., Elrod, M. K., “The Structure and Time Variability of the Ring atmosphere and ionosphere”. Geophy. Res. Lett. 2009.

The photoexcitation of crystalline ice and amorphous solid water: A molecular dynamics study of outcomes at 11 K and 125 K.

PubMed

Crouse, J; Loock, H-P; Cann, N M

2015-07-21

Photoexcitation of crystalline ice Ih and amorphous solid water at 7-9 eV is examined using molecular dynamics simulations and a fully flexible water model. The probabilities of photofragment desorption, trapping, and recombination are examined for crystalline ice at 11 K and at 125 K and for amorphous solid water at 11 K. For 11 K crystalline ice, a fully rigid water model is also employed for comparison. The kinetic energy of desorbed H atoms and the distance travelled by trapped fragments are correlated to the location and the local environment of the photoexcited water molecule. In all cases, H atom desorption is found to be the most likely outcome in the top bilayer while trapping of all photofragments is most probable deeper in the solid where the likelihood for recombination of the fragments into H2O molecules also rises. Trajectory analysis indicates that the local hydrogen bonding network in amorphous solid water is more easily distorted by a photodissociation event compared to crystalline ice. Also, simulations indicate that desorption of OH radicals and H2O molecules are more probable in amorphous solid water. The kinetic energy distributions for desorbed H atoms show a peak at high energy in crystalline ice, arising from photoexcited water molecules in the top monolayer. This peak is less pronounced in amorphous solid water. H atoms that are trapped may be displaced by up to ∼10 water cages, but migrate on average 3 water cages. Trapped OH fragments tend to stay near the original solvent cage.

Interstellar Alcohols

NASA Technical Reports Server (NTRS)

Charnley, S. B.; Kress, M. E.; Tielens, A. G. G. M.; Millar, T. J.

1995-01-01

We have investigated the gas-phase chemistry in dense cores where ice mantles containing ethanol and other alcohols have been evaporated. Model calculations show that methanol, ethanol, propanol, and butanol drive a chemistry leading to the formation of several large ethers and esters. Of these molecules, methyl ethyl ether (CH3OC2H5) and diethyl ether (C2H5)2O attain the highest abundances and should be present in detectable quantities within cores rich in ethanol and methanol. Gas-phase reactions act to destroy evaporated ethanol and a low observed abundance of gas-phase C,H,OH does not rule out a high solid-phase abundance. Grain surface formation mechanisms and other possible gas-phase reactions driven by alcohols are discussed, as are observing strategies for the detection of these large interstellar molecules.

Experimental determination of surface heat transfer coefficient in a dry ice-ethanol cooling bath using a numerical approach.

PubMed

Santos, M V; Sansinena, M; Zaritzky, N; Chirife, J

BACKGROUND: Dry ice-ethanol bath (-78 degree C) have been widely used in low temperature biological research to attain rapid cooling of samples below freezing temperature. The prediction of cooling rates of biological samples immersed in dry ice-ethanol bath is of practical interest in cryopreservation. The cooling rate can be obtained using mathematical models representing the heat conduction equation in transient state. Additionally, at the solid cryogenic-fluid interface, the knowledge of the surface heat transfer coefficient (h) is necessary for the convective boundary condition in order to correctly establish the mathematical problem. The study was to apply numerical modeling to obtain the surface heat transfer coefficient of a dry ice-ethanol bath. A numerical finite element solution of heat conduction equation was used to obtain surface heat transfer coefficients from measured temperatures at the center of polytetrafluoroethylene and polymethylmetacrylate cylinders immersed in a dry ice-ethanol cooling bath. The numerical model considered the temperature dependence of thermophysical properties of plastic materials used. A negative linear relationship is observed between cylinder diameter and heat transfer coefficient in the liquid bath, the calculated h values were 308, 135 and 62.5 W/(m 2 K) for PMMA 1.3, PTFE 2.59 and 3.14 cm in diameter, respectively. The calculated heat transfer coefficients were consistent among several replicates; h in dry ice-ethanol showed an inverse relationship with cylinder diameter.

Why Interstellar Ices Can Be Considered As Precursors For Prebiotic Chemistry

NASA Astrophysics Data System (ADS)

Hendecourt, Louis Le Sergeant d.; de Marcellus, Pierre; Meinert, Cornelia; Myrgorodska, Iuliia; Nahon, Laurent; Modica, Paola; Buhse, Thomas; Meierhenrich, Uwe J.

2015-08-01

Interstellar ices made of simple molecules (H2O, CO, CO2, CH3OH, NH3, CH4…) are abundant species observed in molecular clouds where stars and planetary systems form. Since the constitutive elements (H, O, C, N, S, P) are the most cosmically abundant and condensible, they favor the making of ices on grains. In the mantles formed, a rich organic chemistry develops, thanks to the protective nature of the grains. This chemistry leads to a high complexity. Radical chemistry generated by photo/thermo-chemical processes on the surfaces, leaves to the formation of organic residues as those produced in our laboratory using ice templates, and further studied, using methods that pertain mostly to analytical chemistry. The organic material formed may resemble the Soluble Organic Matter observed in pristine meteorites. From numerous amino acids [1], aldehydes and sugars [2] detected in these residues to chiral molecules and enantiomeric excesses produced by Vacuum Ultra-Violet Circularly Polarized Light from synchrotron radiation [3], one might seriously ask whether the chemistry of molecular clouds out of which stars, planetary systems and debris form, may not be seriously considered as the precursor of prebiotic chemistry in a given environment such as the surface of a telluric planet. I will present the general frame of these experiments in relation to the possibillity of feeding of the necessary prebiotic chemistry for the origin of life. Certainly, prebiotic chemistry is very different in itself than astrochemistry but the starting bricks issued from astrochemistry may well be necessary for the possibility of the emergence of life on planets under certain assumptions I will briefly discuss.REFERENCES[1] Meinert, C., Filippi, J.-J., de Marcellus, P., Le Sergeant d’Hendecourt, L. and Meierhenrich, U.J., ChemPlusChem, 77, 186-191 (2012).[2] de Marcellus, P., Meinert, C., Myrgorodska, I., Nahon, L., Buhse, T., Le Sergeantd’Hendecourt, L., Meierhenrich, U.J., PNAS, January 12th, 2015[3] Modica, P., Meinert, C. de Marcellus, Nahon, L., Meierhenrich, U.J., Le Sergeant d’Hendecourt, L. Astrophys.J, 788, 79

Dynamic ikaite production and dissolution in sea ice - control by temperature, salinity and pCO2 conditions

NASA Astrophysics Data System (ADS)

Rysgaard, S.; Wang, F.; Galley, R. J.; Grimm, R.; Lemes, M.; Geilfus, N.-X.; Chaulk, A.; Hare, A. A.; Crabeck, O.; Else, B. G. T.; Campbell, K.; Papakyriakou, T.; Sørensen, L. L.; Sievers, J.; Notz, D.

2013-12-01

Ikaite is a hydrous calcium carbonate mineral (CaCO3 · 6H2O). It is only found in a metastable state, and decomposes rapidly once removed from near-freezing water. Recently, ikaite crystals have been found in sea ice and it has been suggested that their precipitation may play an important role in air-sea CO2 exchange in ice-covered seas. Little is known, however, of the spatial and temporal dynamics of ikaite in sea ice. Here we present evidence for highly dynamic ikaite precipitation and dissolution in sea ice grown at an out-door pool of the Sea-ice Environmental Research Facility (SERF). During the experiment, ikaite precipitated in sea ice with temperatures below -3 °C, creating three distinct zones of ikaite concentrations: (1) a mm to cm thin surface layer containing frost flowers and brine skim with bulk concentrations of > 2000 μmol kg-1, (2) an internal layer with concentrations of 200-400 μmol kg-1 and (3) a~bottom layer with concentrations of < 100 μmol kg-1. Snowfall events caused the sea ice to warm, dissolving ikaite crystals under acidic conditions. Manual removal of the snow cover allowed the sea ice to cool and brine salinities to increase, resulting in rapid ikaite precipitation. The modeled (FREZCHEM) ikaite concentrations were in the same order of magnitude as observations and suggest that ikaite concentration in sea ice increase with decreasing temperatures. Thus, varying snow conditions may play a key role in ikaite precipitation and dissolution in sea ice. This will have implications for CO2 exchange with the atmosphere and ocean.

Super-Hydrophobic/Icephobic Coatings Based on Silica Nanoparticles Modified by Self-Assembled Monolayers.

PubMed

Liu, Junpeng; Janjua, Zaid A; Roe, Martin; Xu, Fang; Turnbull, Barbara; Choi, Kwing-So; Hou, Xianghui

2016-12-02

A super-hydrophobic surface has been obtained from nanocomposite materials based on silica nanoparticles and self-assembled monolayers of 1 H ,1 H ,2 H ,2 H -perfluorooctyltriethoxysilane (POTS) using spin coating and chemical vapor deposition methods. Scanning electron microscope images reveal the porous structure of the silica nanoparticles, which can trap small-scale air pockets. An average water contact angle of 163° and bouncing off of incoming water droplets suggest that a super-hydrophobic surface has been obtained based on the silica nanoparticles and POTS coating. The monitored water droplet icing test results show that icing is significantly delayed by silica-based nano-coatings compared with bare substrates and commercial icephobic products. Ice adhesion test results show that the ice adhesion strength is reduced remarkably by silica-based nano-coatings. The bouncing phenomenon of water droplets, the icing delay performance and the lower ice adhesion strength suggest that the super-hydrophobic coatings based on a combination of silica and POTS also show icephobicity. An erosion test rig based on pressurized pneumatic water impinging impact was used to evaluate the durability of the super-hydrophobic/icephobic coatings. The results show that durable coatings have been obtained, although improvement will be needed in future work aiming for applications in aerospace.

High Resolution 4.7 Micron Keck/NIRSPEC Spectra of Protostars. 1; Ices and Infalling Gas in the Disk of L1489 IRS

NASA Technical Reports Server (NTRS)

Boogert, A. C. A.; Hogerheijde, M. R.; Blake, G. A.

2001-01-01

We explore the infrared M band (4.7 micron) spectrum of the class I protostar L1489 IRS in the Taurus Molecular Cloud. This is the highest resolution wide coverage spectrum at this wavelength of a low mass protostar observed to date (R =25,000; (Delta)v =12 km s(exp -1). A large number of narrow absorption lines of gas phase (12)CO, (13)CO, and C(sup 18)O are detected, as well as a prominent band of solid (12)CO. The gas phase (12)CO lines have red shifted absorption wings (up to 100 km s(exp -1)), which likely originate from warm disk material falling toward the central object. Both the isotopes and the extent of the (12)CO line wings are successfully fitted with a contracting disk model of this evolutionary transitional object. This shows that the inward motions seen in millimeter wave emission lines continue to within approx. 0.1 AU from the star. The amount of high velocity infalling gas is however overestimated by this model, suggesting that only part of the disk is infalling, e.g. a hot surface layer or hot gas in magnetic field tubes. The colder parts of the disk are traced by the prominent CO ice band. The band profile results from CO in 'polar' ices (CO mixed with H2O), and CO in 'apolar' ices. At the high spectral resolution, the 'apolar' component is, for the first time, resolved into two distinct components, likely due to pure CO and CO mixed with CO2, O2 and/or N2. The ices have probably experienced thermal processing in the upper disk layer traced by our pencil absorption beam: much of the volatile 'apolar' ices has evaporated, the depletion factor of CO onto grains is remarkably low (approx. 7%), and the CO2 traced in the CO band profile was possibly formed energetically. This study shows that high spectral resolution 4.7 micron observations provide important and unique information on the dynamics and structure of protostellar disks and the origin and evolution of ices in these disks.

O and C stable isotopes in cryogenic cave calcite (CCC) - possible proxy for past climate changes

NASA Astrophysics Data System (ADS)

-Andreea, Badaluta Carmen; Ersek, Vasile; Piotrowska, Natalia; Persoiu, Aurel

2017-04-01

Perennial ice deposits in caves host various proxies of past climate variability, most notable, the isotopic composition of ice, which has been shown to reflect, generally, the temperature outside the cave during the formation of ice (usually, autumn though spring). This ice forms by the freezing of water, water that contains large amounts of dissolved calcium carbonate. The freezing is accompanied by degassing of CO2, and precipitation of cryogenic cave calcite (CCC) under strong kinetic conditions. These kinetic processes could lead to the alteration of the original putative climatic signal carried by the isotopic composition of CCC. Here, we present a possibly climatic explanation of the isotopic composition of CCC from a 1000 years old cave ice deposit from Scărișoara Ice Cave (SIC) in Romania, Eastern Europe. In a 7 m core from the Great Hall of SIC we have analyzed the isotopic composition of the water (oxygen and hydrogen) and CCC (oxygen and carbon) from individual ice layers in the core, as well as that of precipitation , outside the cave. The isotopic composition of precipitation from the cave area varies between -3.6 ‰ for δˡ⁸O and -22 ‰ for δ2H in summer, and -17.8 ‰ for δˡ⁸O and -22 ‰ for δ2H in winter, with mean values of -9.1 ‰ for δˡ⁸O and -62 ‰ for δ2H. A positive correlation between air temperature and the isotopic composition of precipitation, as well as drip water in the cave has been found. The mean values in the ice core during the past 1000 years are -10.3‰ for δ18O and -71 ‰ for δ2H. The water isotopic values in the ice core show low values up to 900 AD, higher values between 900 and 1300 AD (Medieval Warm Period, MWP), and again lower values after 1300 AD (Little Ice Age, LIA), reaching their minimum after 1800 AD. The isotopic composition of CCC shows slightly higher values in the MWP and lower in LIA, possibly suggesting a climatic influence. Modern observations are too short to be able to calibrate this putative signal. Further, clumped isotope thermometry has shown that the kinetic fractionation that dominates during the freezing of water leads to unusual reconstructed formative temperature: +20°C. However, δˡ3C and δˡ⁸O values in CCC have higher values for samples from the MWP than those from the LIA. CCC results from the deposition of CaCO3 from Ca(CO3)2. The main source of CO2 to form carbonic acid is soil CO2, produced by root respiration. Previous studies have shown that δˡ⁸O of this CO2 is in equilibrium with the δˡ⁸O of water, so that the higher (lower) δˡ⁸O values of CCC could reflect warmer (colder) conditions during the MPW (LIA). The interpretation of δˡ3C values of CCC is less straightforward. Higher δˡ3C values in soil CO2 are determined by moisture limitation on plants, either due to low moisture or higher evaporative conditions. While the MWP was warmer in the study area, conflicting data exists on precipitation, with studies suggesting both drier and wetter conditions, so that is difficult to interpret our carbon isotope data. Apart from the direct climatic influence, the depth of soil could have also played a part, as deeper soils, as expected under birch forests that dominated during the MWP, would have had more enrichment in the heavy isotopes with depth, than the thiner soils of the LIA (formed under mostly spruce forests). Further, drought/higher temperatures could also influence the kinetics of the reaction, which can be large enough to overprint any soil signal in δˡ3C.

Surface science studies of ethene containing model interstellar ices

NASA Astrophysics Data System (ADS)

Puletti, F.; Whelan, M.; Brown, W. A.

2011-05-01

The formation of saturated hydrocarbons in the interstellar medium (ISM) is difficult to explain only by taking into account gas phase reactions. This is mostly due to the fact that carbonium ions only react with H_2 to make unsaturated hydrocarbons, and hence no viable route to saturated hydrocarbons has been postulated to date. It is therefore likely that saturation processes occur via surface reactions that take place on interstellar dust grains. One of the species of interest in this family of reactions is C_2H_4 (ethene) which is an intermediate in several molecular formation routes (e.g. C_2H_2 → C_2H_6). To help to understand some of the surface processes involving ethene, a study of ethene deposited on a dust grain analogue surface (highly oriented pyrolytic graphite) held under ultra-high vacuum at 20 K has been performed. The adsorption and desorption of ethene has been studied both in water-free and water-dominated model interstellar ices. A combination of temperature programmed desorption (TPD) and reflection absorption infrared spectroscopy (RAIRS) have been used to identify the adsorbed and trapped species and to determine the kinetics of the desorption processes. In all cases, ethene is found to physisorb on the carbonaceous surface. As expected water has a very strong influence on the desorption of ethene, as previously observed for other model interstellar ice systems.

Filamentous phages prevalent in Pseudoalteromonas spp. confer properties advantageous to host survival in Arctic sea ice

PubMed Central

Yu, Zi-Chao; Chen, Xiu-Lan; Shen, Qing-Tao; Zhao, Dian-Li; Tang, Bai-Lu; Su, Hai-Nan; Wu, Zhao-Yu; Qin, Qi-Long; Xie, Bin-Bin; Zhang, Xi-Ying; Yu, Yong; Zhou, Bai-Cheng; Chen, Bo; Zhang, Yu-Zhong

2015-01-01

Sea ice is one of the most frigid environments for marine microbes. In contrast to other ocean ecosystems, microbes in permanent sea ice are space confined and subject to many extreme conditions, which change on a seasonal basis. How these microbial communities are regulated to survive the extreme sea ice environment is largely unknown. Here, we show that filamentous phages regulate the host bacterial community to improve survival of the host in permanent Arctic sea ice. We isolated a filamentous phage, f327, from an Arctic sea ice Pseudoalteromonas strain, and we demonstrated that this type of phage is widely distributed in Arctic sea ice. Growth experiments and transcriptome analysis indicated that this phage decreases the host growth rate, cell density and tolerance to NaCl and H2O2, but enhances its motility and chemotaxis. Our results suggest that the presence of the filamentous phage may be beneficial for survival of the host community in sea ice in winter, which is characterized by polar night, nutrient deficiency and high salinity, and that the filamentous phage may help avoid over blooming of the host in sea ice in summer, which is characterized by polar day, rich nutrient availability, intense radiation and high concentration of H2O2. Thus, while they cannot kill the host cells by lysing them, filamentous phages confer properties advantageous to host survival in the Arctic sea ice environment. Our study provides a foremost insight into the ecological role of filamentous phages in the Arctic sea ice ecosystem. PMID:25303713

Comparison of Mars Northern Cap Edge Advance and Recession Rates over the Last 6 Mars Years

NASA Astrophysics Data System (ADS)

Titus, T. N.; Cushing, G. E.; Langevin, Y.; Brown, A. J.; Themis Science Team; CRISM Science Team

2011-12-01

The most observable parameter that describes the Mars polar seasonal caps is their size, which has been measured since the days of Herschel. The advance and retreat of the polar cap from year to year may exhibit many clues to help elucidate little understood physical processes. For example, summertime heat storage in the regolith could delay the onset of seasonal CO2 cap formation. The evolution of the seasonal cap could also be directly affected by the thermal inertia of the near-surface regolith and place constraints on the depth of the ice table. Parameterizations of the seasonal cap edges provide useful constraints on atmospheric GCMs and mesoscale models. Longitudinally resolving the cap edges as they advance and retreat constrains the times when zonal means are appropriate and when longitudinal asymmetries make zonal means invalid. These same kinds of parameterizations can also be used when modeling other data that have low spatial resolutions, such as Gamma Ray Spectrometer (GRS )and Neutron Spectrometer (NS) data. By knowing where the cap edge should be, coarse spatial data can correct for subpixel mixing caused by large point-spread functions including both frosted and frost-free areas. The northern cap exhibits a near symmetric retreat, which has been well characterized at visible wavelengths by both telescopic and spacecraft observations. However, the advance of the cap has not been well characterized until the 21st century. Kieffer and Titus (2001) have used zonal means to observe surface temperature and visible bolometric albedo variations with season using MGS/TES. The TES thermal observations show an almost perfectly symmetrical advance; i.e., condensation at consistent latitude across all longitudes, with the most northern edge of the seasonal cap occurring between longitudes 245°E to 265°E and the most southern edge of the seasonal cap occurring between 280°E and 30°E. The advance of the northern cap typically leads the advance of the edge of polar night by 10° of latitude. The northern spring retreat is also nearly symmetric in both visual and thermal observations, and follows the same small asymmetries as seen in the advance. In addition to four Mars years of seasonal observations by TES and MOC, the northern seasonal cap was observed in detail by OMEGA in 2004 and 2006. The bright ring at intermediate temperatures (~ 180 K) observed by TES (Kieffer and Titus, 2001) in early spring is confirmed by OMEGA as resulting from H2O ice frost, with a sublimation front which lags by up to 4° in latitude south of the CO2 ice sublimation front. H2O ice contamination of CO2 ice is ubiquitous in the northern seasonal cap at all stages of its evolution. H2O ice dominates the spectral signatures over most of the seasonal cap after mid-spring. This paper will compare the inter-annual variations in the advance and recession of the Mars northern polar cap over the last 6 Mars years using TES, THEMIS, OMEGA, and CRISM.

Mass accommodation coefficient measurements for HNO3, HCl and N2O5 on water, ice and aqueous sulfuric acid droplet surfaces

NASA Technical Reports Server (NTRS)

Worsnop, Douglas; Zahniser, Mark; Kolb, Charles; Watson, Lyn; Vandoren, Jane; Jayne, John; Davidovits, Paul

1988-01-01

Preliminary results are reported of the direct measurement of accommodation coefficients for HNO3, N2O5 and HCl on water drops, aqueous sulfuric acid drops and ice particles. The heterogeneous chemistry of these species together with ClONO2 has been implicated in the ozone depletion observed in the Antarctic stratosphere during the spring in the last eight years. The most plausible chemical mechanism involves the removal of nitrogen oxide species via condensation on ice particles in polar stratospheric clouds resulting in a increase in the active chlorine species responsible for the ozone depletion. The observation of low NO2 and high ClO densities in the Antarctic stratosphere last summer appear to be consistent with such a mechanism.

Influence of hydroxyapatite nanoparticles on the viscosity of dimethyl sulfoxide-H2O-NaCl and glycerol-H2O-NaCl ternary systems at subzero temperatures.

PubMed

Yi, Jingru; Tang, Heyu; Zhao, Gang

2014-10-01

The viscosity, at subzero temperatures, of ternary solutions commonly used in cryopreservation is tremendously important for understanding ice formation and molecular diffusion in biopreservation. However, this information is scarce in the literature. In addition, to the best of our knowledge, the effect of nanoparticles on the viscosity of these solutions has not previously been reported. The objectives of this study were thus: (i) to systematically measure the subzero viscosity of two such systems, dimethyl sulfoxide (Me2SO)-H2O-NaCl and glycerol-H2O-NaCl; (ii) to explore the effect of hydroxyapatite (HA) nanoparticles on the viscosity; and (iii) to provide models that precisely predict viscosity at multiple concentrations of cryoprotective agent (CPA) in saline solutions at subzero temperatures. Our experiments were performed in two parts. We first measured the viscosity at multiple CPA concentrations [0.3-0.75 (w/w)] in saline solution with and without nanoparticles at subzero temperatures (0 to -30°C). The data exhibited a good fit to the Williams-Landel-Ferry (WLF) equation. We then measured the viscosity of residual unfrozen ternary solutions with and without nanoparticles during equilibrium freezing. HA nanoparticles made the solution more viscous, suggesting applications for these nanoparticles in preventing cell dehydration, ice nucleation, and ice growth during freezing and thawing in cryopreservation. Copyright © 2014 Elsevier Inc. All rights reserved.

Adsorption-induced conformational changes of antifreeze glycoproteins at the ice/water interface.

PubMed

Uda, Yukihiro; Zepeda, Salvador; Kaneko, Fumitoshi; Matsuura, Yoshiki; Furukawa, Yoshinori

2007-12-27

The conformation of antifreeze glycoprotein (AFGP) molecules adsorbed at the ice/water interface was studied by attenuated total reflection (ATR)-FTIR spectroscopy. Measurements were carried out for AFGP/D2O solution films formed on the surface of an ATR prism as a function of temperature. Using the FTIR spectrum from the O-D stretching band of D2O molecules, we monitored the supercooled and frozen states of the film and measured the thickness of the quasi-liquid layer (QLL) at the ice/prism interfaces. The AFGP structure was determined for the liquid, supercooled, and frozen states of the solution film using the amide I band spectra. No noticeable differences in conformation were observed in the solution conformation from room temperature down to the 15 K supercooling studied, whereas the alpha-helical content of AFGP suddenly increased when the supercooled solution film froze at -15 degrees C. This change in conformation can increase the overall interaction between the AFGP molecules and ice surface and allow a stronger adsorption. In contrast, the alpha-helical content of AFGP in the frozen film gradually decreased with increasing temperature and finally returned to its solution-state level at the melting point of D2O ice. This gradual decrease in the alpha-helix content directly correlates with the measured increase in QLL thickness. Finally, we conclude that the differences in the alpha-helix signals between the frozen and supercooled states indicate the conformational change of AFGP molecules upon adsorption at the ice/water interface, emphasizing the importance of the structure-function relationship, even for this highly flexible antifreeze.

Ab initio Quantum Chemical Studies of Reactions in Astrophysical Ices. Reactions Involving CH3OH, CO2, CO, HNCO in H2CO/NH3/H2O Ices

NASA Technical Reports Server (NTRS)

Woon, David E.

2006-01-01

While reactions between closed shell molecules generally involve prohibitive barriers in the gas phase, prior experimental and theoretical studies have demonstrated that some of these reactions are significantly enhanced when confined within an icy grain mantle and can occur efficiently at temperatures below 100 K with no additional energy processing. The archetypal case is the reaction of formaldehyde (H2CO) and ammonia (NH3) to yield hydroxymethylamine (NH2CH2OH). In the present work we have characterized reactions involving methanol (CH3OH), carbon dioxide (CO2), carbon monoxide (CO), and isocyanic acid (HNCO) in search of other favorable cases. Most of the emphasis is on CH3OH, which was investigated in the two-body reaction with one H2CO and the three-body reaction with two H2CO molecules. The addition of a second H2CO to the product of the reaction between CH3OH and H2CO was also considered as an alternative route to longer polyoxymethylene polymers of the -CH2O- form. The reaction between HNCO and NH3 was studied to determine if it can compete against the barrierless charge transfer process that yields OCN(-) and NH4(+). Finally, the H2CO + NH3 reaction was revisited with additional benchmark calculations that confirm that little or no barrier is present when it occurs in ice.

Bright ice spots on the nucleus of comet 67P/Churyumov-Gerasimenko as observed by Rosetta OSIRIS and VIRTIS instruments

NASA Astrophysics Data System (ADS)

Barucci, Maria Antonietta; Fulchignoni, Marcello; Pommerol, Antoine; Erard, Stéphane; Oklay, Nilda; Tosi, Federico; Capaccioni, Fabrizio; Sierks, Holger; Filacchione, Gianrico; Bockelee-Morvan, Dominique; Guettler, Carsten; Fornasier, Sonia; Raponi, Andrea; Deshapriya, J. D. P.; Feller, Clement; Ciarniello, Mauro; Leyrat, Cedric

2016-07-01

Since the Rosetta mission arrived at the comet 67P/Churyumov-Gerasimenko (67/P C-G) on August 2014, the comet nucleus has been mapped by both OSIRIS (Optical, Spectroscopic, and Infrared Remote Imaging System), and VIRTIS (Visible Infrared Thermal Imaging Spectrometer) acquiring a huge quantity of surface's images and spectra, producing the most detailed maps at the highest spatial resolution of a cometary nucleus. The OSIRIS imaging system (NAC & WAC) has a set of filters at different wavelengths from the ultraviolet (269 nm) to the near-infrared (989 nm). The OSIRIS imaging system has been the first instrument with the capability to map a comet surface at a high resolution reaching a maximum resolution of 11cm/px during the closest fly-by on February 14, 2015 at a distance of about 6 km from the nucleus surface while the VIRTIS spectro-imager (with two channels M and H) operates from 0.25 to 5m with medium and high spectral resolution. The spectral analysis on global scale from the VIRTIS data indicates that the nucleus presents different terrains covered by a very dark and dehydrated organic-rich material [1]. OSIRIS images indicate a morphologically complex and dark surface with a variety of terrain types and several intricate features [2]. The surface shows albedo variation and from the spectrophotometric analysis a large heterogeneity on the surface properties [3, 4, 5]. Limited evidences of exposed H2O ice have been found on the surface of 67/P C-G up to now [6, 7, 8], even though ices are considered to be a major constituent of cometary nuclei. The aim of this work is, taking advantage of the high resolution of the OSIRIS images, i) to detect the bright spots at all dimensions by albedo and spectral slope analyses, ii) to select those spots which could be resolved by VIRTIS and iii ) to deeply analyse the corresponding spectra. The OSIRIS analysis has been carried out on the colours and spectrophotometry of the whole 67/P C-G nucleus from images acquired since the first Rosetta bound orbits in August 2014 up to the end of 2015. The bright spots are spread everywhere on the surface. The analysis of the VIRTIS spectra on the selected positions by OSIRIS allowed us to detect eight spots with positive H2O ice signatures detection. The obtained results with the computed models will be presented and discussed. References : [1] Capaccioni et al. 2015. Science 347, DOI: 10.1126/science.aaa0628 [2] Sierks et al. 2015. Science 347, DOI: 10.1126/science.aaa1044 [3] Fornasier et al. 2015. A&A, 583, A30 [4] Ciarniello et al., 2015, A&A, 583, A31 [5] Oklay et al. 2016. A&A 586, A80 [6] Pommerol et al. 2015. A&A, 583, A25 [7] De Sanctis et al. 2015. Nature 525, 500 [8] Filacchione et al. 2016. Nature 529, 368.

AKARI Near-infrared Spectroscopic Observations of Interstellar Ices in the Edge-on Starburst Galaxy NGC 253

NASA Astrophysics Data System (ADS)

Yamagishi, Mitsuyoshi; Kaneda, Hidehiro; Ishihara, Daisuke; Oyabu, Shinki; Onaka, Takashi; Shimonishi, Takashi; Suzuki, Toyoaki

2011-04-01

We present the spatially resolved near-infrared (2.5-5.0 μm) spectra of the edge-on starburst galaxy NGC 253 obtained with the Infrared Camera on board AKARI. Near the center of the galaxy, we clearly detect the absorption features of interstellar ices (H2O: 3.05 μm, CO2: 4.27 μm, and XCN: 4.62 μm) and the emission of polycyclic aromatic hydrocarbons (PAHs) at 3.29 μm and the hydrogen recombination line Brα at 4.05 μm. We find that the distributions of the ices differ from those of the PAH and gas. We calculate the column densities of the ices and derive the abundance ratios of N(CO2)/N(H2O) = 0.17 ± 0.05. They are similar to those obtained around the massive young stellar objects in our Galaxy (0.17 ± 0.03), although a much stronger interstellar radiation field and higher dust temperature are expected near the center of NGC 253.

McCall Glacier record of Arctic climate change: Interpreting a northern Alaska ice core with regional water isotopes

NASA Astrophysics Data System (ADS)

Klein, E. S.; Nolan, M.; McConnell, J.; Sigl, M.; Cherry, J.; Young, J.; Welker, J. M.

2016-01-01

We explored modern precipitation and ice core isotope ratios to better understand both modern and paleo climate in the Arctic. Paleoclimate reconstructions require an understanding of how modern synoptic climate influences proxies used in those reconstructions, such as water isotopes. Therefore we measured periodic precipitation samples at Toolik Lake Field Station (Toolik) in the northern foothills of the Brooks Range in the Alaskan Arctic to determine δ18O and δ2H. We applied this multi-decadal local precipitation δ18O/temperature regression to ∼65 years of McCall Glacier (also in the Brooks Range) ice core isotope measurements and found an increase in reconstructed temperatures over the late-20th and early-21st centuries. We also show that the McCall Glacier δ18O isotope record is negatively correlated with the winter bidecadal North Pacific Index (NPI) climate oscillation. McCall Glacier deuterium excess (d-excess, δ2H - 8*δ18O) values display a bidecadal periodicity coherent with the NPI and suggest shifts from more southwestern Bering Sea moisture sources with less sea ice (lower d-excess values) to more northern Arctic Ocean moisture sources with more sea ice (higher d-excess values). Northern ice covered Arctic Ocean McCall Glacier moisture sources are associated with weak Aleutian Low (AL) circulation patterns and the southern moisture sources with strong AL patterns. Ice core d-excess values significantly decrease over the record, coincident with warmer temperatures and a significant reduction in Alaska sea ice concentration, which suggests that ice free northern ocean waters are increasingly serving as terrestrial precipitation moisture sources; a concept recently proposed by modeling studies and also present in Greenland ice core d-excess values during previous transitions to warm periods. This study also shows the efficacy and importance of using ice cores from Arctic valley glaciers in paleoclimate reconstructions.

The Nature of Carbon Dioxide Bearing Ices in Quiescent Molecular Clouds

NASA Astrophysics Data System (ADS)

Whittet, D. C. B.; Cook, A. M.; Chiar, J. E.; Pendleton, Y. J.; Shenoy, S. S.; Gerakines, P. A.

2009-04-01

The properties of the ices that form in dense molecular clouds represent an important set of initial conditions in the evolution of interstellar and preplanetary matter in regions of active star formation. Of the various spectral features available for study, the bending mode of solid CO2 near 15 μm has proven to be a particularly sensitive probe of physical conditions, especially temperature. We present new observations of this absorption feature in the spectrum of Q21-1, a background field star located behind a dark filament in the Cocoon Nebula (IC 5146). We show the profile of the feature to be consistent with a two-component (polar + nonpolar) model for the ices, based on spectra of laboratory analogs with temperatures in the range 10-20 K. The polar component accounts for ~85% of the CO2 in the line of sight. We compare for the first time 15 μm profiles in three widely separated dark clouds (Taurus, Serpens, and IC 5146), and show that they are indistinguishable to within observational scatter. Systematic differences in the observed CO2/H2O ratio in the three clouds have little or no effect on the 15 μm profile. The abundance of elemental oxygen in the ices appears to be a unifying factor, displaying consistent behavior in the three clouds. We conclude that the ice formation process is robust and uniformly efficient, notwithstanding compositional variations arising from differences in how the O is distributed between the primary species (H2O, CO2, and CO) in the ices.

Modeling of Particulate Emissions

DTIC Science & Technology

2011-12-01

Concern Local Air Quality - A Continuing Concern Ground Level Troposphere Ozone Layer Depletion • H2O Ozone Depletion (ice formation) 5 Modeling... Ozone & Smog Formation Health Effects Local Air Quality 33,000-58,000 ft• NOx •Traffic Growth • CO2* • NOx O3* • NOx Reduces CH4 • H2O Vapor...Particulates • SOx Cloud Formation Global Warming * - Greenhouse Gases Ozone Layer Depletion - Not an Immediate Concern Global Warming - An Emerging

Ice under cover: Using bulk spatial and physical properties of probable ground ice driven mass wasting features on Ceres to better understand its surface

NASA Astrophysics Data System (ADS)

Hughson, K.; Russell, C.; Schmidt, B. E.; Chilton, H.; Scully, J. E. C.; Castillo, J. C.; Combe, J. P.; Ammannito, E.; Sizemore, H.; Platz, T.; Byrne, S.; Nathues, A.; Raymond, C. A.

2016-12-01

NASA's Dawn spacecraft arrived at Ceres on March 6, 2015, and has been studying the dwarf planet through a series of successively lower orbits, obtaining morphological and topographical image, mineralogical, elemental composition, and gravity data (Russell et al., 2016). Images taken by Dawn's Framing Camera show a multitude of flow features that were broadly interpreted as ground ice related structures either similar to ice cored/ice cemented flows (as seen on Earth and Mars), long run-out landslides, or fluidized ejecta (as seen on Mars) by Schmidt et al. (2016a and 2016b) and Buczkowski et al. (2016). The aforementioned ice cored/ice cemented-like flows are present only at high latitudes. Results from Dawn's Gamma Ray and Neutron Detector (GRaND) indicate a shallow ice table on Ceres above 45-50°N/S, which supports the interpretation that these flows are ice-rich (Prettyman et al., 2016). A near coincident spectral detection of H2O ice with one of these ice cored/ice cemented-like flows in Oxo crater by Dawn's Visual and Infrared spectrometer (VIR) further bolsters this claim (Combe et al., 2016). We use aggregate spatial and physical properties of these ice attributed cerean flows, such as flow orientation, inclination, preference for north or south facing slopes, drop height to run-out length ratio, geographical location, and areal number density to better understand the rheology and distribution of ground ice in Ceres' uppermost layer. By combining these data with local spectroscopic, global elemental abundance, experimentally derived physical properties of cerean analogue material, and other morphological information (such as the morphologies of flow hosting craters) we intend to further test the ground ice hypothesis for the formation of these flows and constrain the global distribution of near surface ground ice on Ceres to a higher fidelity than what would be possible using GRaND and VIR observations alone. References: Buczkowski et al., (2016) Science, AcceptedCombe, J-P., et al. (2016) Science, AcceptedPrettyman, T. H., et al. (2016) LPSC XVII, Abstract #2228 Russell, et al. (2016) Science, AcceptedSchmidt, B. E., et al. (2016a) LPSC XVII, Abstract #2677 Schmidt, B. E., et al. (2016b), Nature Geoscience, In Review

THE EFFECT OF BROADBAND SOFT X-RAYS IN SO{sub 2}-CONTAINING ICES: IMPLICATIONS ON THE PHOTOCHEMISTRY OF ICES TOWARD YOUNG STELLAR OBJECTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pilling, S.; Bergantini, A., E-mail: sergiopilling@pq.cnpq.br

2015-10-01

We investigate the effects produced mainly by broadband soft X-rays up to 2 keV (plus fast (∼keV) photoelectrons and low-energy (∼eV) induced secondary electrons) in the ice mixtures containing H{sub 2}O:CO{sub 2}:NH{sub 3}:SO{sub 2} (10:1:1:1) at two different temperatures (50 and 90 K). The experiments are an attempt to simulate the photochemical processes induced by energetic photons in SO{sub 2}-containing ices present in cold environments in the ices surrounding young stellar objects (YSO) and in molecular clouds in the vicinity of star-forming regions, which are largely illuminated by soft X-rays. The measurements were performed using a high-vacuum portable chamber from themore » Laboratório de Astroquímica e Astrobiologia (LASA/UNIVAP) coupled to the spherical grating monochromator beamline at the Brazilian Synchrotron Light Source (LNLS) in Campinas, Brazil. In situ analyses were performed by a Fourier transform infrared spectrometer. Sample processing revealed the formation of several organic molecules, including nitriles, acids, and other compounds such as H{sub 2}O{sub 2}, H{sub 3}O{sup +}, SO{sub 3}, CO, and OCN{sup −}. The dissociation cross section of parental species was on the order of (2–7) × 10{sup −18} cm{sup 2}. The ice temperature does not seem to affect the stability of SO{sub 2} in the presence of X-rays. Formation cross sections of new species  produced were also determined. Molecular half-lives at ices toward YSOs due to the presence of incoming soft X-rays were estimated. The low values obtained employing two different models of the radiation field of YSOs (TW Hydra and typical T-Tauri star) reinforce that soft X-rays are indeed a very efficient source of molecular dissociation in such environments.« less

Critical Role of Water and Oxygen Defects in C-O Scission during CO2 Reduction on Zn2GeO4(010).

PubMed

Yang, Jing; Li, Yanlu; Zhao, Xian; Fan, Weiliu

2018-03-27

Exploration of catalyst structure and environmental sensitivity for C-O bond scission is essential for improving the conversion efficiency because of the inertness of CO 2 . We performed density functional theory calculations to understand the influence of the properties of adsorbed water and the reciprocal action with oxygen vacancy on the CO 2 dissociation mechanism on Zn 2 GeO 4 (010). When a perfect surface was hydrated, the introduction of H 2 O was predicted to promote the scission step by two modes based on its appearance, with the greatest enhancement from dissociative adsorbed H 2 O. The dissociative H 2 O lowers the barrier and reaction energy of CO 2 dissociation through hydrogen bonding to preactivate the C-O bond and assisted scission via a COOH intermediate. The perfect surface with bidentate-binding H 2 O was energetically more favorable for CO 2 dissociation than the surface with monodentate-binding H 2 O. Direct dissociation was energetically favored by the former, whereas monodentate H 2 O facilitated the H-assisted pathway. The defective surface exhibited a higher reactivity for CO 2 decomposition than the perfect surface because the generation of oxygen vacancies could disperse the product location. When the defective surface was hydrated, the reciprocal action for vacancy and surface H 2 O on CO 2 dissociation was related to the vacancy type. The presence of H 2 O substantially decreased the reaction energy for the direct dissociation of CO 2 on O 2c1 - and O 3c2 -defect surfaces, which converts the endoergic reaction to an exoergic reaction. However, the increased decomposition barrier made the step kinetically unfavorable and reduced the reaction rate. When H 2 O was present on the O 2c2 -defect surface, both the barrier and reaction energy for direct dissociation were invariable. This result indicated that the introduction of H 2 O had little effect on the kinetics and thermodynamics. Moreover, the H-assisted pathway was suppressed on all hydrated defect surfaces. These results provide a theoretical perspective for the design of highly efficient catalysts.