Probing molecular-level transformations of dissolved organic matter: insights on photochemical degradation and protozoan modification of DOM from electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Molecular-level characterization of natural organic matter (NOM) has been elusive due to the inherent complexity of natural organic mixtures and to the fact that individual components are often polar and macromolecular. Electrospray ionization (ESI) is a “soft” ionization technique that ionizes polar compounds from aqueous solution prior to injection into a mass spectrometer. The highest resolution and mass accuracy of compounds within NOM have been achieved when ESI is combined with an ultrahigh-resolution mass spectrometer such as the Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS). With this technique, individual molecules within a variety of natural organic mixtures can be detected and their elemental composition can be determined. At low mass-to-charge (m/z) ratio, the resolution is high enough to assign exact molecular formulas allowing specific components of these mixtures to be identified. In addition to molecular identification, we can now use ESI FT-ICR MS to examine molecular-level changes in different organic mixtures as a function of relevant geo-processes, such as microbial alterations and photochemistry. Here we present the results from the application of ESI FT-ICR MS to two geochemical questions: (1) the effect of photoirradiation on the molecular composition of fulvic acids and (2) the role of protozoan grazers in the modification of DOM in aquatic systems.     

Transport of ionizing radiation in terrestrial-like exoplanet atmospheres

The propagation of ionizing radiation through model atmospheres of terrestrial-like exoplanets is studied for a large range of column densities and incident photon energies using a Monte Carlo code we have developed to treat Compton scattering and photoabsorption. Incident spectra from parent star flares, supernovae, and gamma-ray bursts are modeled and compared to energetic particles in importance. Large irradiation events with fluences of 10⁶-10⁹ erg cm⁻² at the conventional habitable zone can occur at a rate from many per day (flares from young low-mass parent stars) to ∼100 per Gyr (supernovae and gamma-ray bursts). We find that terrestrial-like exoplanets with atmospheres thinner than about 100 g cm⁻² block nearly all X-rays, but transmit and reprocess a significant fraction of incident γ-rays, producing a characteristic, flat surficial spectrum. Thick atmospheres (?100 g cm⁻²) efficiently block even γ-rays, but nearly all the incident energy is redistributed into diffuse UV and visible aurora-like emission, increasing the effective atmospheric transmission by many orders of magnitude. Depending on the presence of molecular UV absorbers and atmospheric thickness, up to 10% of the incident energy can reach the surface as UV reemission. For the Earth, between 2×10⁻³ and 4×10⁻² of the incident flux reaches the ground in the biologically effective 200-320 nm range, depending on O₂/O₃ shielding. For atmospheres thicker than ∼50 g cm⁻² in the case of pure Rayleigh scattering and ∼100 g cm⁻² in the case of O₂/O₃ absorption, the UV reemission exceeds the surficial transmitted ionizing radiation. We also discuss the effects of angle of incidence and derive a modified two-stream approximation solution for the UV transfer. Finally, we suggest that transient atmospheric ionization layers can be frequently created at altitudes lower than the equilibrium layers that result from steady irradiation and winds from the parent star. We suggest that these events can produce frequent fluctuations in atmospheric ionization levels and surficial UV fluxes on terrestrial-like planets.     

Reactions of nitriles in ices relevant to Titan, comets, and the interstellar medium: formation of cyanate ion, ketenimines, and isonitriles

Motivated by detections of nitriles in Titan's atmosphere, cometary comae, and the interstellar medium, we report laboratory investigations of the low-temperature chemistry of acetonitrile, propionitrile, acrylonitrile, cyanoacetylene, and cyanogen (CH₃CN, CH₃CH₂CN, CH₂CHCN, HCCCN, and NCCN, respectively). A few experiments were also done on isobutyronitrile and trimethylacetonitrile ((CH₃)₂CHCN and (CH₃)₃CCN, respectively). Trends were sought, and found, in the photo- and radiation chemical products of these molecules at 12-25 K. In the absence of water, all of these molecules isomerized to isonitriles, and CH₃CN, CH₃CH₂CN, and (CH₃)₂CHCN also formed ketenimines. In the presence of H₂O, no isonitriles were detected but rather the cyanate ion (OCN⁻) was seen in all cases. Although isonitriles, ketenimines, and OCN⁻ were the main focus of our work, we also describe cases of hydrogen loss, to make smaller nitriles, and hydrogen addition (reduction), to make larger nitriles. HCN formation also was seen in most experiments. The results are presented in terms of nitrile ice chemistry on Titan, in cometary ice, and in the interstellar medium. Possible connections to prebiotic chemistry are briefly discussed.     

The shielding effect of small-scale martian surface geometry on ultraviolet flux

The atmosphere of Mars does little to attenuate incoming ultraviolet (UV) radiation. Large amounts of UV radiation sterilize the hardiest of terrestrial organisms within minutes, and chemically alter the soil such that organic molecules at or near the surface are rapidly destroyed. Thus the survival of any putative martian life near the surface depends to a large extent on how much UV radiation it receives. Variations in small-scale geometry of the surface such as pits, trenches, flat faces and overhangs can have a significant effect on the incident UV flux and may create “safe havens” for organisms and organic molecules. In order to examine this effect, a 1-D radiative transfer sky model with 836 meshed points (plus the Sun) was developed which includes both diffuse and direct components of the surface irradiance. This model derives the variation of UV flux with latitude and an object's Geometric Shielding Ratio (a ratio which describes the geometry of each situation). The best protection is offered by overhangs with flux reduced to a factor of 1.8±0.2×10⁻⁵ of the unprotected value, a reduction which does not vary significantly by latitude. Pits and cracks are less effective with a reduction in UV flux of only up to 4.5±0.5×10⁻³ for the modeled scenarios; however, they are more effective for the same geometric shielding ratio than overhangs at high latitudes due to the low height of the Sun in the sky. Lastly, polar faces of rocks have the least effective shielding geometry with at most a 1.1±0.1×10⁻¹ reduction in UV flux. Polar faces of rocks are most effective at mid latitudes where the Sun is never directly overhead, as at tropical latitudes, and never exposes the back of the rock, as at polar latitudes. In the most favorable cases, UV flux is sufficiently reduced such that organic in-fall could accumulate beneath overhanging surfaces and in pits and cracks. As well, hardy terrestrial microorganisms such as Bacillus pumilus could persist for up to 100 sols on the outer surfaces of typical spacecraft or several tens of martian years in the most shielded surface niches.     

Carbon dioxide segregation in 1:4 and 1:9 CO2:H2O ices

The mid-infrared spectra of mixed vapor deposited ices of CO₂ and H₂O were studied as a function of both deposition temperature and warming from 15 to 100 K. The spectra of ices deposited at 15 K show marked changes on warming beginning at 60 K. These changes are consistent with CO₂ segregating within the ice matrix into pure CO₂ domains. Ices deposited at 60 and 70 K show a greater degree of segregation, as high as 90% for 1:4 CO₂:H₂O ice mixtures deposited at 70 K. As the ice is warmed above 80 K, preferential sublimation of the segregated CO₂ is observed. The kinetics of the segregation process is also examined. The segregation of the CO₂ as the ice is warmed corresponds to temperatures at which the structure of the water ice matrix changes from the high density amorphous phase to the low density amorphous phase. We show how these microstructural changes in the ice have a profound effect on the photochemistry induced by ultraviolet irradiation. These experimental results provide a framework in which observations of CO₂ on the icy bodies of the outer Solar System can be considered.     

Production and detection of carbon dioxide on Iapetus

Cassini VIMS detected carbon dioxide on the surface of Iapetus during its insertion orbit. We evaluated the CO₂ distribution on Iapetus and determined that it is concentrated almost exclusively on Iapetus’ dark material. VIMS spectra show a 4.27-μm feature with an absorption depth of 24%, which, if it were in the form of free ice, requires a layer 31 nm thick. Extrapolating for all dark material on Iapetus, the total observable CO₂ would be 2.3 × 10⁸ kg.Previous studies note that free CO₂ is unstable at 10 AU over geologic timescales. Carbon dioxide could, however, be stable if trapped or complexed, such as in inclusions or clathrates. While complexed CO₂ has a lower thermal volatility, loss due to photodissociation by UV radiation and gravitational escape would occur at a rate of 2.6 × 10⁷ kg year⁻¹. Thus, Iapetus’ entire inventory of surface CO₂ could be lost within a few decades.The high loss/destruction rate of CO₂ requires an active source. We conducted experiments that generated CO₂ by UV radiation of simulated icy regolith under Iapetus-like conditions. The simulated regolith was created by flash-freezing degassed water, crushing it into sub-millimeter sized particles, and then mixing it with isotopically labeled amorphous carbon (¹³C) dust. These samples were placed in a vacuum chamber and cooled to temperatures between 50 K and 160 K. The samples were irradiated with UV light, and the products were measured using a mass spectrometer, from which we measured ¹³CO₂ production at a rate of 2.0 × 10¹² mol s⁻¹. Extrapolating to Iapetus and adjusting for the solar UV intensity and Iapetus’ surface area, we calculated that CO₂ production for the entire surface would be 1.1 × 10⁷ kg year⁻¹, which is only a factor of two less than the loss rate. As such, UV photochemical generation of CO₂ is a plausible source of the detected CO₂.     

Monte Carlo modeling of neutral gas and dust in the coma of Comet 1P/Halley

The neutral gas environment of a comet is largely influenced by dissociation of parent molecules created at the surface of the comet and collisions of all the involved species. We compare the results from a kinetic model of the neutral cometary environment with measurements from the Neutral Mass Spectrometer and the Dust Impact Detection System onboard the Giotto spacecraft taken during the fly-by at Comet 1P/Halley in 1986. We also show that our model is in good agreement with contemporaneous measurements obtained by the International Ultraviolet Explorer, sounding rocket experiments, and various ground based observations.The model solves the Boltzmann equation with a Direct Simulation Monte Carlo technique (Tenishev, V., Combi, M., Davidsson, B. [2008]. Astrophys. J. 685, 659-677) by tracking trajectories of gas molecules and dust grains under the influence of the comet’s weak gravity field with momentum exchange among particles modeled in a probabilistic manner. The cometary nucleus is considered to be the source of dust and the parent species (in our model: H₂O, CO, H₂CO, CO₂, CH₃OH, C₂H₆, C₂H₄, C₂H₂, HCN, NH₃, and CH₄) in the coma. Subsequently our model also tracks the corresponding dissociation products (H, H₂, O, OH, C, CH, CH₂, CH₃, N, NH, NH₂, C₂, C₂H, C₂H₅, CN, and HCO) from the comet’s surface all the way out to 10⁶ km.As a result we are able to further constrain cometary the gas production rates of CO (13%), CO₂ (2.5%), and H₂CO (1.5%) relative to water without invoking unknown extended sources.     

The structure of the natural stratosphere and the impact of chlorofluoromethanes on the ozone layer investigated in a 2-D time dependent model

two-dimensional time dependent model of the stratosphere incorporating the major interactions between radiative-photochemical and dynamical processes is described. The main prognostic equations considered are the thermodynamic equation and the general conservation equation for the minor chemical constituents representing the odd oxygen (O _x =O+('D)+O₃), odd hydrogen (HO _x =HO+HO₂), N₂O, odd nitrogen (NO _x =NO+NO₂+HNO₃), CF₂Cl₂, CFCl₃ and odd chlorine (Cl _x =Cl+ClO+HCl). The zonal wind and mean meridional circulations are determined diagnostically by the integration of the thermal wind equation and the stream function equation in the meridional plane espectively. The large scale eddy processes are parameterized in terms of zonal mean quantities using the generalized diffusion formulation on a sloping surface. The radiative heating and cooling and the hotochemical sources and sinks are incorporated in a form which allows for the major interactions among the minor trace constituents, temperature and mean circulation.Two integrations consisting of natural stratosphere and a stratosphere contaminated by the chlorofluoromethanes through lower boundary fluxes are carried out for 23 model years by changing the declination of the sun every day and using 6-hour time step. The model simulations of temperature, mean circulation, ozone, HO _x , N₂O and NO _x in the meridional plane for the normal stratosphere, show satisfactory agreement with the available observations. Based on the results of second integration it is found that the injection of chlorofluoromethanes in the atmosphere at the estimated current production rates can lead to significant changes in the meridional distribution of ozone, temperature and NO _x in the middle and upper stratosphere. The results also indicate that the percentage total ozone depletion increases from tropics to high latitudes and from summer to winter high latitudes. Also discussed are the results of additional experiments incorporating the reaction of HO₂ with NO and the reactions involving ClNO₃.