UV photolysis of quinoline in interstellar ice analogs

Abstract— The polycyclic aromatic nitrogen heterocycle (PANH) quinoline (C₉H₇N) was frozen at 20 K in interstellar ice analogs containing either pure water or water mixed with methanol or methane and exposed to ultraviolet (UV) radiation. Upon warming, the photolysis products were analyzed by high‐performance liquid chromatography and nanoscale liquid chromatography‐electrospray ionization mass spectrometry. A suite of hydroxyquinolines, which were formed by the addition of oxygen atoms to quinoline, was observed as the primary product in all the ices. Quinoline N oxide was not formed, but five hydroxyquinoline isomers were produced with no clear dominance of one isomer. Reduction products, formed by hydrogen atom addition, were also created. Ices created at 20 K with H₂O: quinoline ratios of 10:1 to 100:1 showed similar product distributions to those at 122 K, with no apparent temperature or concentration dependence. Increasing the UV dose led to a decrease in overall yield, indicating that quinoline and its products may be photo‐destroyed. Methylquinolines were formed upon photolysis of the methanol‐ and methane‐containing ices. In addition, possible methoxyquinolines or quinoline methylene alcohols were formed in the methanol‐containing ice, while methylhydroxyquinolines were created in the methane‐containing ice. This work indicates that oxidation of PANHs could occur in icy extraterrestrial environments and suggests that a search for such compounds in carbonaceous meteorites could illuminate the possible link between interstellar ice chemistry and meteoritic organics. Given the importance of oxidized and alkylated PANHs to biochemistry, the formation and delivery of such molecules to the early Earth may have played a role in the origin and evolution of life.     

Assessment of the interstellar processes leading to deuterium enrichment in meteoritic organics

Abstract— The presence of isotopic anomalies is the most unequivocal demonstration that meteoritic material contains circumstellar or interstellar components. In the case of organic compounds in meteorites and interplanetary dust particles (IDPs), the most useful isotopic tracer has been deuterium (D). We discuss four processes that are expected to lead to D enrichment in interstellar materials and describe how their unique characteristics can be used to assess their relative importance for the organics in meteorites. These enrichment processes are low‐temperature gas phase ion‐molecule reactions, low‐temperature gas‐grain reactions, gas phase unimolecular photodissociation, and ultraviolet photolysis in D‐enriched ice mantles. Each of these processes is expected to be associated with distinct regiochemical signatures (D placement on the product molecules, correlation with specific chemical functionalities, etc.), especially in the molecular population of polycyclic aromatic hydrocarbons (PAHs). We describe these differences and discuss how they may be used to delineate the various interstellar processes that may have contributed to meteoritic D enrichments. We also briefly discuss how these processes may affect the isotopic distributions in C, O, and N in the same compounds.     

Ultraviolet photolysis and proton irradiation of astrophysical ice analogs containing hydrogen cyanide

Hydrogen cyanide (HCN) has been identified in the gas phase of the interstellar medium as well as in the comae of several comets. Terrestrially, HCN is a key component in the synthesis of biologically important molecules such as amino acids. In this paper, we report the results of low-temperature (18 K) ice energetic processing experiments involving pure HCN and mixtures of HCN with H₂O and NH₃. Ice films, 0.1 to several microns in thickness, were exposed to either ultraviolet photons (110-250 nm) or 0.8-MeV protons to simulate the effects of space environments. Observed products include HCNO (isocyanic acid), NH₄⁺ (ammonium ion), CN⁻ (cyanide ion), OCN⁻ (cyanate ion), HCONH₂ (formamide), and species spectrally similar to HCN polymers. Product formation rates and HCN destruction rates were determined where possible. Results are discussed in terms of astrophysical situations in the ISM and the Solar System where HCN would likely play an important role in prebiotic chemistry. These results imply that if HCN is present in icy mixtures representative of the ISM or in comets, it will be quickly converted into other species in energetic environments; pure HCN seems to be polymerized by incident radiation.     

Ultraviolet irradiation of naphthalene in H2O ice: Implications for meteorites and biogenesis

Abstract— 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.     

Retraction Note: Exoplanet Habitability: Potential O2/O3 Biosignatures in the Ultraviolet

Solar System Research - The authors have retracted this article [1], because Figures 1 and 2 were reused by them without permission and were not properly credited and because portions of text...     

Ultraviolet photolysis of amino acids in a 100 K water ice matrix: Application to the outer Solar System bodies

We report the rates of decomposition by ultraviolet (UV) photolysis of four amino acids in millimeter-thick crystalline water ice matrices at 100 K to constrain the survivability of these important organic molecules within ice lying near the surfaces of outer Solar System bodies. We UV-irradiated crystalline ice samples containing known concentrations of the amino acids glycine, aspartic acid, glutamic acid, and phenylalanine, then we measured the surviving concentrations using high performance liquid chromatography (HPLC) with fluorescence detection. From these experiments, we determine photolytic decomposition rates and half-lives. The half-life varies linearly with the ice thickness for all acids studied here. For example, glycine is the most resistant to photolytic destruction with a half-life of 50, 12, and 3.7 h in 1.6, 0.28, and 0.14 mm thick ices, respectively. We explain this linear variation of half-life with thickness as a consequence of extinction, mostly due to scattering, within these macroscopically thick ice samples. Applied to low latitude surface ice on Jupiter's satellite Europa, this analysis indicates that the concentration of any of these amino acids within the top meter of similar ice will be halved within a ∼10 year timescale.     

Detection of interstellar ethylene oxide (c-C2H4O)

We report the identification of 10 transitions that support the detection of the small cyclic molecule ethylene oxide (c-C2H4O) in Sgr B2N. Although one of these transitions is severely blended, so that an accurate intensity and line width could not be determined, and two other lines are only marginally detected, we have done Gaussian fits to the remaining seven lines and have performed a rotation diagram analysis. Our results indicate a rotation temperature T(rot) = 18 K and a molecular column density N(c-C2H4O) = 3.3 x 10(14) cm-2, corresponding to a fractional abundance relative to molecular hydrogen of order 6 x 10(-11). This is a factor of more than 200 higher than the abundance for this molecule suggested by the "new standard" chemistry model of Lee, Bettens, & Herbst. This result suggests that grain chemistry might play an effective role in the production of c-C2H4O. No transitions of this molecule were detected in either Sgr B2M or Sgr B2NW.     

Collisional excitation of interstellar molecule due to H2

Collision induced vibrational rates of SiO due to H₂ are computed using the normalized perturbative, semiclassical approach as described in Paper I (Mehrotra, 1980). The rates are very small as compared to the rates for rotational excitation and are more sensitive to temperature.     

Ultraviolet absorption studies of H2O and other species in comet comae with satellite telescope-spectrometers

Ultraviolet absorption by H₂O and other species in the comae of comets could be detected by studying, with satellite telescope-spectrometers, the occultation of hot stars by comets. Such observations could produce the first direct detection of H₂O, the fundamental parent molecule in comet comae, and give measures of molecular level populations. The first instrument suitable for such observations will be the High Resolution Spectrograph on Space Telescope and, therefore, we consider its capabilities. We have used a Haser model to estimate the molecular column densities and to predict equivalent widths for lines of H₂O, OH, CO, and O as functions of time and angular distance from a comet with a high H₂O production rate. We have determined the minimum detectable equivalent widths, and therefore, the maximum angular separation from such a comet at which H₂O, OH, and CO could be studied. A conservative, statistical estimate shows that comets with high water production rates should pass near enough to about 10 to 100 stars suitable for absorption studies of the $\text{C}\text{}\text{X}$ band of H₂O (1240 Å). Estimated equivalent widths for CO, OH, and the resonance lines of C and O indicate that these species may also be detected.     

H2O maser pumping: The effect of quasi-resonance energy transfer in collisions between H2 and H2O molecules

The effect of quasi-resonance energy transfer in collisions between H₂ and H₂O molecules in H₂O maser sources is investigated. New data on the state-to-state rate coefficients for collisional transitions for H₂O and H₂ molecules are used in the calculations. The results of ortho-H₂O level population inversion calculations for the 22.2-, 380-, 439-, and 621-GHz transitions are presented. The ortho-H₂O level population inversion is shown to depend significantly on the population distribution of the para-H₂ J = 0 and 2 rotational levels. The possibility of quasi-resonance energy transfer in collisions between H₂ molecules at highly excited rotational-vibrational levels and H₂O molecules is considered. The quasi-resonance energy transfer effect can play a significant role in pumping H₂O masers in the central regions of active galactic nuclei and in star-forming regions.     

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

Both laboratory measurements and theory indicate that CO2 should be a common component in interstellar ices. We show that the exact band position, width, and profile of the solid-state 12CO2 infrared bands near 3705, 3600, 2340, and 660 cm-1 (2.70, 2.78, 4.27, and 15.2 micrometers) and the 13CO2 band near 2280 cm-1 (4.39 micrometers) are dependent on the matrix in which the CO2 is frozen. Measurements of these bands in astronomical spectra can be used to determine column densities of solid-state CO2 and provide important information on the physical conditions present in the ice grains of which the CO2 is a part. Depending on the composition of the ice, the CO2 asymmetric stretching band was observed to vary from 2328.7 to 2346.0 cm-1 and have full widths at half-maxima (FWHMs) ranging from 4.7 to 29.9 cm-1. The other CO2 bands showed similar variations. Both position and width are also concentration dependent. Absorption coefficients were determined for the five CO2 bands. These were found to be temperature independent for CO2 in CO and CO2 matrices but varied slightly with temperature for CO2 in H2O-rich ices. For all five bands this variation was found to be less than 15% from 10 to 150 K, the temperature at which H2O ice sublimes. A number of parameters associated with the physical behavior of CO2 in CO2- and H2O-rich ices were also determined. The CO2-CO2 surface binding energy in pure CO2 ices is found to be (delta Hs/k) = 2690 +/- 50 K. CO2-H2O and CO-H2O surface binding energies were determined to be (delta Hs/k) = 2860 +/- 200 K and 1740 +/- 100 K, respectively. Under our experimental conditions, CO2 condenses in measurable quantities into H2O-rich ices at temperatures up to 100 K, only slightly higher than the temperature at which pure CO2 condenses. Once frozen into an H2O-rich ice, the subsequent loss of CO2 upon warming is highly dependent on concentration. For ices with H2O/CO2 > 20, the CO is physically trapped within the H2O lattice, and little CO2 is lost until the sublimation temperature of the H2O matrix is reached. In contrast, in ices having H2O/CO2 < 5, the CO2 remains only to temperatures of about 90 K. Above this point the CO2 readily diffuses out of the H2O matrix. These results suggest that two different forms of H2O lattice are produced. The implications of these data for cometary models and our understanding of cometary formation are considered.     

H2 in interstellar and extragalactic ices: infrared characteristics, ultraviolet production, and implications

H2 is the most abundant molecule in the universe. We demonstrate that this molecule may be an important component of interstellar and possibly intergalactic ices, both because it can be formed in situ, within the ices, and because gas phase H2 can freeze out onto dust grains in some astrophysical environments. The condensation-sublimation and infrared spectral properties of ices containing H2 are presented. We show that solid H2 in H20-rich ices can be detected by an infrared absorption band at 4137 cm-1 (2.417 micrometers). The surface binding energy of H2 to H2O ice was measured to the delta Hs/k = 555 +/- 35 K. Surface binding energies can be used to calculate the residence times of H2 on grain surfaces as a function of temperature. Some of the implications of these results are considered.     

Solar cycle variations in ice acidity at the end of the last ice age: Possible marker of a climatically significant interstellar dust incursion

Hammer et al. (Climatic Change 35 (1997) 1) report the presence of regularly spaced acidity peaks (H⁺,F^-,Cl^-) in the Byrd Station, Antarctica ice core. The event has a duration of about one century and falls at the beginning of the deglacial warming. Volcanism appears to be an unlikely cause since the total acid deposition of this event was about 18 fold greater than the largest known volcanic eruption, and since volcanic eruptions are not known to recur with such regularity. We show that the recurrence period of these peaks averages to 11.5±2.4 years, which approximates the solar cycle period, and suggest that this feature may have an extraterrestrial origin. We propose that this material may mark a period of enhanced interstellar dust and gas influx modulated by the solar cycle. The presence of this material could have made the Sun more active and have been responsible for initiating the warming that ended the last ice age.     

Heterogeneous distribution of H2O in the Martian interior: Implications for the abundance of H2O in depleted and enriched mantle sources

We conducted a petrologic study of apatite within 12 Martian meteorites, including 11 shergottites and one basaltic regolith breccia. These data were combined with previously published data to gain a better understanding of the abundance and distribution of volatiles in the Martian interior. Apatites in individual Martian meteorites span a wide range of compositions, indicating they did not form by equilibrium crystallization. In fact, the intrasample variation in apatite is best described by either fractional crystallization or crustal contamination with a Cl‐rich crustal component. We determined that most Martian meteorites investigated here have been affected by crustal contamination and hence cannot be used to estimate volatile abundances of the Martian mantle. Using the subset of samples that did not exhibit crustal contamination, we determined that the enriched shergottite source has 36–73 ppm H₂O and the depleted source has 14–23 ppm H₂O. This result is consistent with other observed geochemical differences between enriched and depleted shergottites and supports the idea that there are at least two geochemically distinct reservoirs in the Martian mantle. We also estimated the H₂O, Cl, and F content of the Martian crust using known crust‐mantle distributions for incompatible lithophile elements. We determined that the bulk Martian crust has ~1410 ppm H₂O, 450 ppm Cl, and 106 ppm F, and Cl and H₂O are preferentially distributed toward the Martian surface. The estimate of crustal H₂O results in a global equivalent surface layer (GEL) of ~229 m, which can account for at least some of the surface features on Mars attributed to flowing water and may be sufficient to support the past presence of a shallow sea on Mars' surface.     

H2O + ions in comets: models and observations

An improved magnetohydrodynamic (MHD) model with chemistry is presented. The analysis of the source and sink terms for H₂O ⁺ shows that for small comets up to 11% of water molecules are finally ionized. For large comets (such as Halley) this fraction decreases to less than 3%. From the MHD scaling laws a similarity law for the individual ion densities is deduced which takes into account that the mother molecules are depleted by dissociation. This is applied to H₂O ⁺ ions. Radial density profiles from model calculations, observations by Giotto near comet Halley, and ground based observations of three comets confirm this scaling law for H₂O ⁺ ions. From the similarity law for the density a scaling law for the column density is derived which is more convenient to apply for ground based observations. From these scaling laws methods are derived which allow the determination of the water production rate from the ground based images of the H₂O ⁺ ions. Finally, the two dimensional images of model column densities are compared with observations.     

Theoretical approach to study the formation of C_2H_4O_2 isomers in interstellar medium through reaction between interstellar formaldehyde molecules

The three isomers of C_2H_4O_2, viz., glycolaldehyde(HCOCH_2 OH), acetic acid(CH_3 COOH) and methyl formate(HCOOCH3), have been detected in copious amounts in the interstellar medium(ISM). The possibility for formation of these molecules through interstellar formaldehyde(HCHO) has been explored by using the quantum chemical approach described by density functional theory(DFT) and second order Moller-Plesset perturbation(MP2) theory with a 6–311 G(d,p) basis set in the gas phase as well as in icy grains. The associated molecule-molecule interactions have been discussed to study the formation of isomers of C_2H_4O_2 in ISM. The reactions of two formaldehyde molecules exhibit a considerable potential barrier but due to quantum tunneling, these reactions could be possible in ISM. The chemical pathway is exothermic, which gives rise to a high probability for the formation of all three isomers, viz. glycolaldehyde,methyl formate and acetic acid, in interstellar space. Anharmonic rotational vibration, centrifugal distortion constants and coupling constants are also calculated and results suggest that the vibrations are harmonic in nature.     

Why HOC+ is detectable in interstellar clouds: the rate of the reaction between HOC+ and H2

The recent confirmation by Ziurys and Apponi of the detection of HOC+ toward Sgr B2 (OH), and their identification of the ion in Orion-KL and several other sources show that HOC+ is far more abundant than predicted by previous ion-molecule models. In these models, the reaction HOC(+) + H2 --> HCO(+) + H2 is assumed to rapidly destroy HOC+, based on the results of a prior calculation. We have recalculated the rate of this reaction as a function of temperature using a new ab initio potential surface and a phase space approach to the dynamics which includes tunneling. The newly calculated rate is small (< or = 1 x 10(-10) cm3 s-1) at temperatures under 100 K.     

The 2.5-5.0 micrometers spectra of Io: evidence for H2S and H2O frozen in SO2

Infrared spectra of Io in the region 2.5-5.0 micrometers, including new observational data, are analyzed using detailed laboratory studies of plausible surface ices. Besides the absorption bands attributable to sulfur dioxide frosts, four infrared spectral features of Io are shown to be unidentified. These unidentified features show spatial and temporal band strength variations. One pair is centered around 3.9 micrometers (3.85 and 3.91 micrometers) and the second pair is centered around 3.0 micrometers (2.97 and 3.15 micrometers). These absorptions fall close to the fundamental stretching modes in H2S and H2O, respectively. The infrared absorption spectra of an extensive set of laboratory ices ranging from pure materials, to binary mixtures of H2S and H2O (either mixed at different concentrations or layered), to H2O:H2S:SO2 mixtures are discussed. The effects of ultraviolet irradiation (120 and 160 nm) and temperature variation (from 9 to 130 K) on the infrared spectra of the ices are examined. This comparative study of Io reflectance spectra with the laboratory mixed ice transmission data shows the following: (1) Io's surface most likely contains H2S and H2O mixed with SO2. The 3.85- and 3.91-micrometers bands in the Io spectra can be accounted for by the absorption of the S-H stretching vibration (nu 1) in H2S clusters and isolated molecules in an SO2-dominated ice. The weak 2.97- and 3.15-micrometers bands which vary spatially and temporally in the Io spectra coincide with the nu 3 and nu 1 O-H stretching vibrations of clusters of H2O molecules complexed, through hydrogen bonding and charge transfer interactions, with SO2. (2) The observations are well matched qualitatively by the transmission spectra of SO2 ices containing about 3% H2S and 0.1% H2O which have been formed by the condensation of a mixture of the gases onto a 100 K surface. (3) No new features are produced in the region 2.5 to 5.0 micrometers in the spectrum of these ices under prolonged ultraviolet irradiation or temperature variation up to 120 K. (4) Comparison of the Io spectra to transmission spectra of both mixed molecular ices and layered ices indicates that only the former can explain the shifts and splitting of the absorption bands seen in the Io spectrum and additionally can account for the fact that solid H2S is observed in the surface material of Io at temperature and pressure conditions above the sublimation point of pure H2S.     

Collisional excitation of interstellar molecules due to H2: Linear molecules CO,OCS, SiO,HCN and HC3N in1Σstate

Using a normalized perturbative, semi-classical approach, collision-induced rotational excitation rates of CO, OCS, SiO, HCN, HC₃N due to H₂ are computed. The calculated excitation rates for CO–H₂ and OCS–H₂ systems at 100 K are in good agreement with the results of close coupling approximation at low values ofJ, whereJ is the rotational quantum number. The rates are found to be very sensitive with respect to ortho and para states of H₂.     

Remote sensing D/H ratios in methane ice: Temperature-dependent absorption coefficients of CH3D in methane ice and in nitrogen ice

The existence of strong absorption bands of singly deuterated methane (CH₃D) at wavelengths where normal methane (CH₄) absorbs comparatively weakly could enable remote measurement of D/H ratios in methane ice on outer Solar System bodies. We performed laboratory transmission spectroscopy experiments, recording spectra at wavelengths from 1 to 6 μm to study CH₃D bands at 2.47, 2.87, and 4.56 μm, wavelengths where ordinary methane absorption is weak. We report temperature-dependent absorption coefficients of these bands when the CH₃D is diluted in CH₄ ice and also when it is dissolved in N₂ ice, and describe how these absorption coefficients can be combined with data from the literature to simulate arbitrary D/H ratio absorption coefficients for CH₄ ice and for CH₄ in N₂ ice. We anticipate these results motivating new telescopic observations to measure D/H ratios in CH₄ ice on Triton, Pluto, Eris, and Makemake.