Atmospheric Prebiotic Chemistry and Organic Hazes

Earth's atmospheric composition at the time of the origin of life is not known, but it has often been suggested that chemical transformation of reactive species in the atmosphere was a significant source of pre biotic organic molecules. Experimental and theoretical studies over the past half century have shown that atmospheric synthesis can yield molecules such as amino acids and nucleobases, but these processes are very sensitive to gas composition and energy source. Abiotic synthesis of organic molecules is more productive in reduced atmospheres, yet the primitive Earth may not have been as reducing as earlier workers assumed, and recent research has reflected this shift in thinking. This work provides a survey of the range of chemical products that can be produced given a set of atmospheric conditions, with a particular focus on recent reports. Intertwined with the discussion of atmospheric synthesis is the consideration of an organic haze layer, which has been suggested as a possible ultraviolet shield on the anoxic early Earth. Since such a haze layer - if formed - would serve as a reservoir for organic molecules, the chemical composition of the aerosol should be closely examined. The results highlighted here show that a variety of products can be formed in mildly reducing or even neutral atmospheres, demonstrating that contributions of atmospheric synthesis to the organic inventory on early Earth should not be discounted. This review intends to bridge current knowledge of the range of possible atmospheric conditions in the prebiotic environment and pathways for synthesis under such conditions by examining the possible products of organic chemistry in the early atmosphere

Nitrogen Incorporation in CH_4-N_2 Photochemical Aerosol Produced by Far Ultraviolet Irradiation

Nitrile incorporation into Titan aerosol accompanying hydrocarbon chemistry is thought to be driven by extreme UV wavelengths (λ120 nm is presently unaccounted for in atmospheric photochemical models. We suggest that reaction with CH radicals produced from CH_4 photolysis may provide a mechanism for incorporating N into the molecular structure of the aerosol. Further work is needed to understand the chemistry involved, as these processes may have significant implications for how we view prebiotic chemistry on early Earth and similar planets. Key Words: Titan—Photochemical aerosol—CH_4-N_2 photolysis—Far UV—Nitrogen activation

Influence of Benzene on the Optical Properties of Titan Haze Laboratory Analogs in the Mid-Visible

The Cassini Ion and Neutral Mass Spectrometer (Waite, Jr., et al., 2007) and the Composite Infrared Spectrometer (Coustenis, A., et al., 2007) have detected benzene in the upper atmosphere and stratosphere of Titan. Photochemical reactions involving benzene in Titan's atmosphere may influence polycyclic aromatic hydrocarbon formation, aerosol formation, and the radiative balance of Titan's atmosphere. We measure the effect of benzene on the optical properties of Titan analog particles in the laboratory. Using cavity ring-down aerosol extinction spectroscopy, we determine the real and imaginary refractive index at 532 nm of particles formed by benzene photolysis and Titan analog particles formed with ppm-levels of benzene. These studies are compared to the previous study by Hasenkopf, et a1. (2010) of Titan analog particles formed by methane photolysis

Stable Isotope Chemistry in Titan Haze Aerosol

Titan, a moon of Saturn, has a thick atmosphere made up of nitrogen and a few percent methane, with a surface pressure of 1.5x that of Earth. Titan’s atmosphere is believed to be that similar to that of early Earth before the rise of O2. One significant source of information on the history and evolution of the atmosphere is the measurement of stable isotopes of elements in the molecules of major gases such as nitrogen, methane, and higher order hydrocarbons. The fractionation associated with the formation of Titan aerosol analogs are explored in the laboratory as a function of environmental parameters. Gas mixtures were flowed into a reaction chamber, where they underwent UV-irradiation via a deuterium lamp. The resulting aerosol samples were collected and analyzed using isotope-ratio mass spectrometry (IRMS). This project focused on pyridine (C5H5N) and nitrogen mixtures, with and without methane, as a function of pressure

Titan Aerosol Analogs from Aromatic Precursors: Comparisons to Cassini CIRS Observations in the Thermal Infrared

Since Cassini's arrival at Titan, ppm levels of benzene (C6H6) as well as large positive ions, which may be polycyclic aromatic hydrocarbons (PAHs). have been detected in the atmosphere. Aromatic molecules. photolytically active in the ultraviolet, may be important in the formation of the organic aerosol comprising the Titan haze layer even when present at low mixing ratios. Yet there have not been laboratory simulations exploring the impact of these molecules as precursors to Titan's organic aerosol. Observations of Titan by the Cassini Composite Infrared Spectrometer (CIRS) in the far-infrared (far-IR) between 560 and 20/cm (approx. 18 to 500 microns) and in the mid-infrared (mid-IR) between 1500 and 600/cm (approx. 7 to 17 microns) have been used to infer the vertical variations of Titan's aerosol from the surface to an altitude of 300 km in the far-IR and between 150 and 350 km in the mid-IR. Titan's aerosol has several observed emission features which cannot be reproduced using currently available optical constants from laboratory-generated Titan aerosol analogs, including a broad far-IR feature centered approximately at 140/cm (71 microns)

Metatheme Analysis: A Qualitative Method for Cross-Cultural Research

In recent years, there has been a florescence of cross-cultural research using ethnographic and qualitative data. This cutting-edge work confronts a range of significant methodological challenges, but has not yet addressed how thematic analysis can be modified for use in cross-cultural ethnography. Thematic analysis is widely used in qualitative and mixed-methods research, yet is not currently well-adapted to cross-cultural ethnographic designs. We build on existing thematic analysis techniques to discuss a method to inductively identify metathemes (defined here as themes that occur across cultures). Identifying metathemes in crosscultural research is important because metathemes enable researchers to use systematic comparisons to identify significant patterns in cross-cultural datasets and to describe those patterns in rich, contextually-specific ways. We demonstrate this method with data from a collaborative cross-cultural ethnographic research project (exploring weight-related stigma) that used the same sampling frame, interview protocol, and analytic process in four cross-cultural research sites in Samoa, Paraguay, Japan, and the United States. Detecting metathemes that transcend data collected in different languages, cultures, and sites, we discuss the benefits and challenges of qualitative metatheme analysis

Noble gases and stable isotopes track the origin and early evolution of the Venus atmosphere

The composition the atmosphere of Venus results from the integration of many processes entering into play over the entire geological history of the planet. Determining the elemental abundances and isotopic ratios of noble gases (He, Ne, Ar, Kr, Xe) and stable isotopes (H, C, N, O, S) in the Venus atmosphere is a high priority scientific target since it could open a window on the origin and early evolution of the entire planet. This chapter provides an overview of the existing dataset on noble gases and stable isotopes in the Venus atmosphere. The current state of knowledge on the origin and early and long-term evolution of the Venus atmosphere deduced from this dataset is summarized. A list of persistent and new unsolved scientific questions stemming from recent studies of planetary atmospheres (Venus, Earth and Mars) are described. Important mission requirements pertaining to the measurement of volatile elements in the atmosphere of Venus as well as potential technical difficulties are outlined.Comment: 40 pages, 10 figures, 1 tabl

Investigating the relationship between language and picture understanding in children with autism spectrum disorder

Previous studies report that minimally verbal children with autism spectrum disorder show impaired picture comprehension when matched to typically developing controls on language comprehension. Here, we compare both picture comprehension and picture production abilities in linguistically delayed children with autism spectrum disorder and typically developing controls matched on language comprehension and language production. Participants were 20 children with autism spectrum disorder (M age: 11.2 years) and 20 typically developing children (M age: 4.4 years) matched on age equivalents for receptive language (autism spectrum disorder, M: 4.6 years; typically developing, M: 4.5 years) and expressive language (autism spectrum disorder, M: 4.4 years; typically developing, M: 4.5 years). Picture comprehension was assessed by asking children to identify the three-dimensional referents of line drawings. Picture production was assessed by asking children to create representational drawings of unfamiliar objects and having raters identify their referents. The results of both picture tasks revealed statistically equivalent performance for typically developing children and children with autism spectrum disorder, and identical patterns of performance across trial types. These findings suggest that early deficits in pictorial understanding displayed by minimally verbal individuals may diminish as their expressive language skills develop. Theoretically, our study indicates that development in linguistic and pictorial domains may be inter-related for children with autism spectrum disorder (as is the case for typical development)

Nitrogen Incorporation in CH4-N2 Photochemical Aerosol Produced by Far UV Irradiation

Nitrile incorporation into Titan aerosol accompanying hydrocarbon chemistry is thought to be driven by extreme UV wavelengths (lambda 120 nm is presently unaccounted for in atmospheric photochemical models. We suggest that reaction with CH radicals produced from CH4 photolysis may provide a mechanism for incorporating N into the molecular structure of the aerosol. Further work is needed to understand the chemistry involved, as these processes may have significant implications for prebiotic chemistry on the early Earth and similar planets

Aromatic Structure in Simulates Titan Aerosol

Observations of Titan by the Cassini Composite Infrared Spectrometer (CIRS) between 560 and 20 per centimeter (approximately 18 to 500 micrometers) have been used to infer the vertical variations of Titan's ice abundances, as well as those of the aerosol from the surface to an altitude of 300 km [1]. The aerosol has a broad emission feature centered approximately at 140 per centimeter (71 micrometers). As seen in Figure 1, this feature cannot be reproduced using currently available optical constants from laboratory-generated Titan aerosol analogs [2]. The far-IR is uniquely qualified for investigating low-energy vibrational motions within the lattice structures of COITIDlex aerosol. The feature observed by CIRS is broad, and does not likely arise from individual molecules, but rather is representative of the skeletal movements of macromolecules. Since Cassini's arrival at Titan, benzene (C6H6) has been detected in the atmosphere at ppm levels as well as ions that may be polycyclic aromatic hydrocarbons (PAHs) [3]. We speculate that the feature may be a blended composite that can be identified with low-energy vibrations of two-dimensional lattice structures of large molecules, such as PAHs or nitrogenated aromatics. Such structures do not dominate the composition of analog materials generated from CH4 and N2 irradiation. We are performing studies forming aerosol analog via UV irradiation of aromatic precursors - specifically C6H6 - to understand how the unique chemical architecture of the products will influence the observable aerosol characteristics. The optical and chemical properties of the aromatic analog will be compared to those formed from CH4/N2 mixtures, with a focus on the as-yet unidentified far-IR absorbance feature. Preliminary results indicate that the photochemically-formed aromatic aerosol has distinct chemical composition, and may incorporate nitrogen either into the ring structure or adjoined chemical groups. These compositional differences are demonstrated in the aerosol mass spectra shown in Figure 2. The aromatic aerosol also demonstrates strong chemical reactivity when exposed to laboratory air, indicating substantial stored chemical potential. Oxidatoin and solubility studies wil be presented and implicatoins for prebiotic chemistry o nTitan will be discussed