Notice: This is an archived and unmaintained page. For current information, please browse astrobiology.nasa.gov.
NAI
Login
NASA: National Aeronautics and Space Administration

nai
You are here: Home » Annual Science Reports » Team » Report

2012 Annual Science Report

University of Hawaii, Manoa Reporting  |  SEP 2011 – AUG 2012

Ice Chemistry of the Solar System

Project Summary

We are currently in the process of establishing a research program at the University of Hawai’i at Manoa to investigate the evolution of Solar System and interstellar ices; these grains are chemically processed continuously by radiation from either our Sun, or galactic cosmic radiation (GCR). The nature of the chemistry that occurs here is an important component of understanding the origin of complex biomolecules that could have seeded the primordial Earth, helping to kick-start the origin of life. We have constructed one of the leading laboratory facilities in the world capable of carrying out this research, and we focus on establishing the underlying chemical pathways.

4 Institutions
3 Teams
17 Publications
0 Field Sites
Field Sites

Project Progress

We have conducted experiments on the effects of energetic electrons on ice mixtures of carbon dioxide (CO2) and chlorine (Cl2) ices in an attempt to understand the potential origin of perchlorate (ClO4) found on both Earth and Mars. We studied the products formed through both Fourier Transform Infrared spectroscopy (FTIR) and quadruple mass spectrometry (QMS) and thus identified the formation of several key chlorine oxides (ClxOy). We are now working with collaborator Sushil K. Atreya to help incorporate our results into chemical models.

Recent results from the W.M. Keck Research Laboratory in astrochemistry include the formation of high molecular weight hydrocarbons upon interaction with ionizing radiation starting from pure, simple saturated hydrocarbon ices such as methane (CH4), ethane (C2H6), propane (C3H8), and n-butane (C4H10). The species are detected – in addition to FTIR, Raman, and UV-Visible spectroscopy – using a novel application of reflection time-of-flight (ReTOF) mass spectrometry coupled with soft vacuum ultraviolet photoionization at 10.5 eV. In particular, results from ReTOF spectroscopy with soft vacuum ultraviolet photoionization of the subliming products of processed methane ice indicate that over 50 molecules with distinct m/z ratios and sublimation temperatures are formed easily under conditions relevant astrophysical environments. Despite, the numerous previous experimental investigations probing the effect of ionizing radiation on simple hydrocarbon astrophysical ice analogs, our results suggest that there is still a vast unknown molecular composition synthesized upon exposure of these ices to ionizing radiation.

Since water-bearing sulfates have been identified on the Martian surface and implicated on Jupiter’s moons Europa and Ganymede, we have begun studying the specific hydration states of these minerals by a technique that could be used in real space missions to identify these species. Raman spectroscopy is ideally suited to this purpose, since the degree of hydrogenation of each species gives a unique Raman fingerprint. Here, we have developed a novel instrument to study the degree of hydration of minerals in situ by combining an acoustic levitator, pressure compatible process chamber, and Raman spectroscopy capable of working under daylight conditions. Minerals studied so far include magnesium sulfate (MgSO4 ∙ nH2O; n = 7, 6, . . ., 0), gypsum (CaSO4 ∙ 2H2O), bassanite (CaSO4 ∙ 0.5H2O), and anhydrite (CaSO4).

Finally, we have found conclusive evidence on the formation of two proteinogenic dipeptides-Gly–Gly and Leu–Ala-formed via electron-irradiation of interstellar model ices followed by annealing the irradiated samples to 300 K. Our results indicate that the radiation-induced, non-enzymatic formation of proteinogenic dipeptides in interstellar ice analogs is possibility. Furthermore, once synthesized and incorporated into the “building material” of solar systems, biomolecules at least as complex as dipeptides could have been delivered to habitable planets such as early Earth by meteorites and comets, thus seeding the necessary components for life as we know it.

Publications

  • Bennett, C. J., Brotton, S. J., Jones, B. M., Misra, A. K., Sharma, S. K., & Kaiser, R. I. (2013). High-Sensitivity Raman Spectrometer To Study Pristine and Irradiated Interstellar Ice Analogs. Anal. Chem., 85(12), 5659–5665. doi:10.1021/ac303259y

  • Brotton, S. J., & Kaiser, R. I. (2013). In Situ Raman Spectroscopic Study of Gypsum (CaSO 4 ·2H 2 O) and Epsomite (MgSO 4 ·7H 2 O) Dehydration Utilizing an Ultrasonic Levitator. The Journal of Physical Chemistry Letters, 4(4), 669–673. doi:10.1021/jz301861a

  • Ennis, C. P., Bennett, C. J., & Kaiser, R. I. (2011). On the formation of ozone in oxygen-rich solar system ices via ionizing radiation. Physical Chemistry Chemical Physics, 13(20), 9469. doi:10.1039/c1cp20434c

  • Ennis, C., & Kaiser, R. I. (2012). ON THE FORMATION OF OZONE IN SOLAR SYSTEM OXYGEN ICES EXPOSED TO HEAVY IONS. The Astrophysical Journal, 745(2), 103. doi:10.1088/0004-637x/745/2/103

  • Ennis, C., Bennett, C. J., Jones, B. M., & Kaiser, R. I. (2011). FORMATION OF D 2 -WATER AND D 2 -CARBONIC ACID IN OXYGEN-RICH SOLAR SYSTEM ICES VIA D + 2 IRRADIATION. The Astrophysical Journal, 733(2), 79. doi:10.1088/0004-637x/733/2/79

  • Ennis, C., Yuan, H., Sibener, S. J., & Kaiser, R. I. (2011). On the chemical processing of hydrocarbon surfaces by fast oxygen ions. Physical Chemistry Chemical Physics, 13(39), 17870. doi:10.1039/c1cp21800j

  • Jones, B. M., Bennett, C. J., & Kaiser, R. I. (2011). MECHANISTICAL STUDIES ON THE PRODUCTION OF FORMAMIDE (H 2 NCHO) WITHIN INTERSTELLAR ICE ANALOGS. The Astrophysical Journal, 734(2), 78. doi:10.1088/0004-637x/734/2/78

  • Kaiser, R. I., Stockton, A. M., Kim, Y. S., Jensen, E. C., & Mathies, R. A. (2013). ON THE FORMATION OF DIPEPTIDES IN INTERSTELLAR MODEL ICES. The Astrophysical Journal, 765(2), 111. doi:10.1088/0004-637x/765/2/111

  • Kayi, H., Kaiser, R. I., & Head, J. D. (2011). A computational study on the structures of methylamine–carbon dioxide–water clusters: evidence for the barrier free formation of the methylcarbamic acid zwitterion (CH3NH2+COO−) in interstellar water ices. Physical Chemistry Chemical Physics, 13(23), 11083. doi:10.1039/c0cp01962c

  • Kayi, H., Kaiser, R. I., & Head, J. D. (2011). A theoretical investigation of the low energy conformers of the isomers glycine and methylcarbamic acid and their role in the interstellar medium. Physical Chemistry Chemical Physics, 13(35), 15774. doi:10.1039/c1cp20656g

  • Kayi, H., Kaiser, R. I., & Head, J. D. (2012). A theoretical investigation of the relative stability of hydrated glycine and methylcarbamic acid—from water clusters to interstellar ices. Physical Chemistry Chemical Physics, 14(14), 4942. doi:10.1039/c2cp23798a

  • Kim, Y. S., & Kaiser, R. I. (2012). ELECTRON IRRADIATION OF KUIPER BELT SURFACE ICES: TERNARY N 2 -CH 4 -CO MIXTURES AS A CASE STUDY. The Astrophysical Journal, 758(1), 37. doi:10.1088/0004-637x/758/1/37

  • Kim, Y. S., Wo, K. P., Maity, S., Atreya, S. K., & Kaiser, R. I. (2013). Radiation-Induced Formation of Chlorine Oxides and Their Potential Role in the Origin of Martian Perchlorates. Journal of the American Chemical Society, 135(13), 4910–4913. doi:10.1021/ja3122922

  • Kim, Y. S., Zhang, F., & Kaiser, R. I. (2011). Laboratory simulation of Kuiper belt object volatile ices under ionizing radiation: CO–N2 ices as a case study. Physical Chemistry Chemical Physics, 13(35), 15766. doi:10.1039/c1cp20658c

  • Zheng, W., Kim, Y. S., & Kaiser, R. I. (2011). Formation of nitric oxide and nitrous oxide in electron-irradiated H218O/N2 ice mixtures—evidence for the existence of free oxygen atoms in interstellar and solar system analog ices. Physical Chemistry Chemical Physics, 13(35), 15749. doi:10.1039/c1cp20528e

  • Bennett, C.J., Ennis, C. & Kaiser, R.I.  (2012, Submitted).  Experimental Studies on the Interaction of the Solar Wind with Oxygen Ices: Formation of D2O and D2O2 in O2 Ices via Irradiation with 5 keV D+ Ions.  The Astrophysical Journal.
  • PROJECT INVESTIGATORS:
  • PROJECT MEMBERS:
    Chris Bennett
    Project Investigator

    Ralf Kaiser
    Project Investigator

    Sushil Atreya
    Collaborator

    Shiv Sharma
    Collaborator

    Stephen Brotton
    Postdoc

    Courtney Ennis
    Postdoc

    Brant Jones
    Postdoc

    Anupam Misra
    Postdoc

    Surajit Sinha
    Postdoc

    Seol Kim
    Research Staff

  • RELATED OBJECTIVES:
    Objective 1.1
    Formation and evolution of habitable planets.

    Objective 2.2
    Outer Solar System exploration

    Objective 3.1
    Sources of prebiotic materials and catalysts

    Objective 3.2
    Origins and evolution of functional biomolecules

    Objective 3.3
    Origins of energy transduction

    Objective 4.1
    Earth's early biosphere.

    Objective 7.1
    Biosignatures to be sought in Solar System materials

    Objective 7.2
    Biosignatures to be sought in nearby planetary systems