Decomposition of electron ionization mass spectra for space application using a Monte-Carlo approach.

RATIONALE: Quadrupole mass spectrometers equipped with an electron ionization (EI) sources have been widely used in space exploration to investigate the composition of planetary surfaces and atmospheres. However, the complexity of the samples and the minimal calibration for the fragmentation of molecules in the ionization chambers have prevented the deconvolution of the majority of the mass spectra obtained at different targets, thus limiting the determination of the exact composition of the samples analyzed. We propose a Monte-Carlo approach to solve this issue mathematically. METHODS: We decomposed simulated mass spectra of mixtures acquired with unit resolving power mass spectrometers and EI sources into the sum of the single components fragmentation patterns weighted by their relative concentration using interior-point least-square fitting. To fit compounds with poorly known fragmentation patterns, we used a Monte-Carlo method to vary the intensity of individual fragment ions. We then decomposed the spectrum thousands of times to obtain a statistical distribution. RESULTS: By performing the deconvolution on a mixture of seven different molecules with interfering fragmentation patterns (H2 O, O2 , CH4 , Ar, N2 , C2 H4 , and C2 H6 ) we show that this approach retrieves the mixing ratio of the individual components more accurately than regular mass spectra decomposition methods that rely on fragmentation patterns from general databases. It also provides the probability density function for each species's mixing ratio. CONCLUSIONS: By removing the solution degeneracy in the decomposition of mass spectra, the method described herein could significantly increase the scientific retrieval from archived space flight mass spectrometry data, where calibration of the ionization source is no longer an option.

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 prebiotic 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.

Primordial argon isotope fractionation in the atmosphere of Mars measured by the SAM instrument on Curiosity and implications for atmospheric loss.

[1] The quadrupole mass spectrometer of the Sample Analysis at Mars (SAM) instrument on Curiosity rover has made the first high-precision measurement of the nonradiogenic argon isotope ratio in the atmosphere of Mars. The resulting value of 36Ar/38Ar = 4.2 ± 0.1 is highly significant for it provides excellent evidence that "Mars" meteorites are indeed of Martian origin, and it points to a significant loss of argon of at least 50% and perhaps as high as 85-95% from the atmosphere of Mars in the past 4 billion years. Taken together with the isotopic fractionations in N, C, H, and O measured by SAM, these results imply a substantial loss of atmosphere from Mars in the posthydrodynamic escape phase.

Isotopes of nitrogen on Mars: Atmospheric measurements by Curiosity's mass spectrometer.

[1] The Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) measured a Mars atmospheric14N/15N ratio of 173 ± 11 on sol 341 of the mission, agreeing with Viking's measurement of 168 ± 17. The MSL/SAM value was based on Quadrupole Mass Spectrometer measurements of an enriched atmospheric sample, with CO2 and H2O removed. Doubly ionized nitrogen data at m/z 14 and 14.5 had the highest signal/background ratio, with results confirmed by m/z 28 and 29 data. Gases in SNC meteorite glasses have been interpreted as mixtures containing a Martian atmospheric component, based partly on distinctive14N/15N and40Ar/14N ratios. Recent MSL/SAM measurements of the40Ar/14N ratio (0.51 ± 0.01) are incompatible with the Viking ratio (0.35 ± 0.08). The meteorite mixing line is more consistent with the atmospheric composition measured by Viking than by MSL.

Selection and Analytical Performances of the Dragonfly Mass Spectrometer Gas Chromatographic Columns to Support the Search for Organic Molecules of Astrobiological Interest on Titan.

Titan is a key planetary body for astrobiology, with the presence of a subsurface ocean and a dense atmosphere, in which complex chemistry is known to occur. Approximately 1-Titan-year after the Cassini-Huygens mission arrived in the saturnian system, Dragonfly rotorcraft will land on Titan's surface by 2034 for an exhaustive geophysical and chemical investigation of the Shangri-La organic sand sea region. Among the four instruments onboard Dragonfly, the Dragonfly Mass Spectrometer (DraMS) is dedicated to analyze the chemical composition of surface samples and noble gases in the atmosphere. One of the DraMS analysis modes, the Gas Chromatograph-Mass Spectrometer (GC-MS), is devoted to the detection and identification of organic molecules that could be involved in the development of a prebiotic chemistry or even representative of traces of past or present life. Therefore, DraMS-GC subsystem should be optimized to detect and identify relevant organic compounds to meet this objective. This work is focused on the experimental methods employed to select the chromatographic column to be integrated in DraMS-GC, to assess the analytical performances of the column selected, and also to assess the performances of the second DraMS-GC column, which is devoted to the separation of organic enantiomers. Four different stationary phases have been tested to select the most relevant one for the separation of the targeted chemical species. The results show that the stationary phase composed of polymethyl (95%) diphenyl (5%) siloxane is the best compromise in terms of efficiency, robustness, and retention times of the molecules. The combination of the general and the chiral columns in DraMS is perfectly suited to in situ chemical analysis on Titan and for the detection of expected diverse and complex organic compounds.

Strategies for Detecting Biological Molecules on Titan.

Saturn's moon Titan has all the ingredients needed to produce "life as we know it." When exposed to liquid water, organic molecules analogous to those found on Titan produce a range of biomolecules such as amino acids. Titan thus provides a natural laboratory for studying the products of prebiotic chemistry. In this work, we examine the ideal locales to search for evidence of, or progression toward, life on Titan. We determine that the best sites to identify biological molecules are deposits of impact melt on the floors of large, fresh impact craters, specifically Sinlap, Selk, and Menrva craters. We find that it is not possible to identify biomolecules on Titan through remote sensing, but rather through in situ measurements capable of identifying a wide range of biological molecules. Given the nonuniformity of impact melt exposures on the floor of a weathered impact crater, the ideal lander would be capable of precision targeting. This would allow it to identify the locations of fresh impact melt deposits, and/or sites where the melt deposits have been exposed through erosion or mass wasting. Determining the extent of prebiotic chemistry within these melt deposits would help us to understand how life could originate on a world very different from Earth. Key Words: Titan-Prebiotic chemistry-Solar system exploration-Impact processes-Volcanism. Astrobiology 18, 571-585.

Background levels of methane in Mars' atmosphere show strong seasonal variations.

Variable levels of methane in the martian atmosphere have eluded explanation partly because the measurements are not repeatable in time or location. We report in situ measurements at Gale crater made over a 5-year period by the Tunable Laser Spectrometer on the Curiosity rover. The background levels of methane have a mean value 0.41 ± 0.16 parts per billion by volume (ppbv) (95% confidence interval) and exhibit a strong, repeatable seasonal variation (0.24 to 0.65 ppbv). This variation is greater than that predicted from either ultraviolet degradation of impact-delivered organics on the surface or from the annual surface pressure cycle. The large seasonal variation in the background and occurrences of higher temporary spikes (~7 ppbv) are consistent with small localized sources of methane released from martian surface or subsurface reservoirs.

The Pale Orange Dot: The Spectrum and Habitability of Hazy Archean Earth.

Recognizing whether a planet can support life is a primary goal of future exoplanet spectral characterization missions, but past research on habitability assessment has largely ignored the vastly different conditions that have existed in our planet's long habitable history. This study presents simulations of a habitable yet dramatically different phase of Earth's history, when the atmosphere contained a Titan-like, organic-rich haze. Prior work has claimed a haze-rich Archean Earth (3.8-2.5 billion years ago) would be frozen due to the haze's cooling effects. However, no previous studies have self-consistently taken into account climate, photochemistry, and fractal hazes. Here, we demonstrate using coupled climate-photochemical-microphysical simulations that hazes can cool the planet's surface by about 20 K, but habitable conditions with liquid surface water could be maintained with a relatively thick haze layer (τ ∼ 5 at 200 nm) even with the fainter young Sun. We find that optically thicker hazes are self-limiting due to their self-shielding properties, preventing catastrophic cooling of the planet. Hazes may even enhance planetary habitability through UV shielding, reducing surface UV flux by about 97% compared to a haze-free planet and potentially allowing survival of land-based organisms 2.7-2.6 billion years ago. The broad UV absorption signature produced by this haze may be visible across interstellar distances, allowing characterization of similar hazy exoplanets. The haze in Archean Earth's atmosphere was strongly dependent on biologically produced methane, and we propose that hydrocarbon haze may be a novel type of spectral biosignature on planets with substantial levels of CO2. Hazy Archean Earth is the most alien world for which we have geochemical constraints on environmental conditions, providing a useful analogue for similar habitable, anoxic exoplanets. Key Words: Haze-Archean Earth-Exoplanets-Spectra-Biosignatures-Planetary habitability. Astrobiology 16, 873-899.

13C and 15N fractionation of CH4/N2 mixtures during photochemical aerosol formation: Relevance to Titan.

The ratios of the stable isotopes that comprise each chemical species in Titan's atmosphere provide critical information towards understanding the processes taking place within its modern and ancient atmosphere. Several stable isotope pairs, including 12C/13C and 14N/15N, have been measured in situ or probed spectroscopically by Cassini-borne instruments, space telescopes, or through ground-based observations. Current attempts to model the observed isotope ratios incorporate fractionation resulting from atmospheric diffusion, hydrodynamic escape, and primary photochemical processes. However, the effect of a potentially critical pathway for isotopic fractionation - organic aerosol formation and subsequent deposition onto the surface of Titan - has not been considered due to insufficient data regarding fractionation during aerosol formation. To better understand the nature of this process, we have conducted a laboratory study to measure the isotopic fractionation associated with the formation of Titan aerosol analogs, commonly referred to as 'tholins', via far-UV irradiation of several methane (CH4) and dinitrogen (N2) mixtures. Analysis of the δ13C and δ15N isotopic signatures of the photochemical aerosol products using an isotope ratio mass spectrometer (IRMS) show that fractionation direction and magnitude are dependent on the initial bulk composition of the gas mixture. In general, the aerosols showed enrichment in 13C and 14N, and the observed fractionation trends can provide insight into the chemical mechanisms controlling photochemical aerosol formation.

Haze aerosols in the atmosphere of early Earth: manna from heaven.

An organic haze layer in the upper atmosphere of Titan plays a crucial role in the atmospheric composition and climate of that moon. Such a haze layer may also have existed on the early Earth, providing an ultraviolet shield for greenhouse gases needed to warm the planet enough for life to arise and evolve. Despite the implications of such a haze layer, little is known about the organic material produced under early Earth conditions when both CO(2) and CH(4) may have been abundant in the atmosphere. For the first time, we experimentally demonstrate that organic haze can be generated in different CH(4)/CO(2) ratios. Here, we show that haze aerosols are able to form at CH(4) mixing ratios of 1,000 ppmv, a level likely to be present on early Earth. In addition, we find that organic hazes will form at C/O ratios as low as 0.6, which is lower than the predicted value of unity. We also show that as the C/O ratio decreases, the organic particles produced are more oxidized and contain biologically labile compounds. After life arose, the haze may thus have provided food for biota.

Abundance and isotopic composition of gases in the martian atmosphere from the Curiosity rover.

Volume mixing and isotope ratios secured with repeated atmospheric measurements taken with the Sample Analysis at Mars instrument suite on the Curiosity rover are: carbon dioxide (CO2), 0.960(±0.007); argon-40 ((40)Ar), 0.0193(±0.0001); nitrogen (N2), 0.0189(±0.0003); oxygen, 1.45(±0.09) × 10(-3); carbon monoxide, < 1.0 × 10(-3); and (40)Ar/(36)Ar, 1.9(±0.3) × 10(3). The (40)Ar/N2 ratio is 1.7 times greater and the (40)Ar/(36)Ar ratio 1.6 times lower than values reported by the Viking Lander mass spectrometer in 1976, whereas other values are generally consistent with Viking and remote sensing observations. The (40)Ar/(36)Ar ratio is consistent with martian meteoritic values, which provides additional strong support for a martian origin of these rocks. The isotopic signature δ(13)C from CO2 of ~45 per mil is independently measured with two instruments. This heavy isotope enrichment in carbon supports the hypothesis of substantial atmospheric loss.

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 (λ<120 nm) or magnetospheric electrons in the outer reaches of the atmosphere. Far UV radiation (120-200 nm), which is transmitted down to the stratosphere of Titan, is expected to affect hydrocarbon chemistry only and not initiate the formation of nitrogenated species. We examined the chemical properties of photochemical aerosol produced at far UV wavelengths, using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), which allows for elemental analysis of particle-phase products. Our results show that aerosol formed from CH(4)/N(2) photochemistry contains a surprising amount of nitrogen, up to 16% by mass, a result of photolysis in the far UV. The proportion of nitrogenated organics to hydrocarbon species is shown to be correlated with that of N(2) in the irradiated gas. The aerosol mass greatly decreases when N(2) is removed, which indicates that N(2) plays a major role in aerosol production. Because direct dissociation of N(2) is highly improbable given the immeasurably low cross section at the wavelengths studied, the chemical activation of N(2) must occur via another pathway. Any chemical activation of N(2) at wavelengths >120 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.

The formation of sulfate and elemental sulfur aerosols under varying laboratory conditions: implications for early earth.

The presence of sulfur mass-independent fractionation (S-MIF) in sediments more than 2.45 × 10(9) years old is thought to be evidence for an early anoxic atmosphere. Photolysis of sulfur dioxide (SO(2)) by UV light with λ < 220 nm has been shown in models and some initial laboratory studies to create a S-MIF; however, sulfur must leave the atmosphere in at least two chemically different forms to preserve any S-MIF signature. Two commonly cited examples of chemically different sulfur species that could have exited the atmosphere are elemental sulfur (S(8)) and sulfuric acid (H(2)SO(4)) aerosols. Here, we use real-time aerosol mass spectrometry to directly detect the sulfur-containing aerosols formed when SO(2) either photolyzes at wavelengths from 115 to 400 nm, to simulate the UV solar spectrum, or interacts with high-energy electrons, to simulate lightning. We found that sulfur-containing aerosols form under all laboratory conditions. Further, the addition of a reducing gas, in our experiments hydrogen (H(2)) or methane (CH(4)), increased the formation of S(8). With UV photolysis, formation of S(8) aerosols is highly dependent on the initial SO(2) pressure; and S(8) is only formed at a 2% SO(2) mixing ratio and greater in the absence of a reductant, and at a 0.2% SO(2) mixing ratio and greater in the presence of 1000 ppmv CH(4). We also found that organosulfur compounds are formed from the photolysis of CH(4) and moderate amounts of SO(2). The implications for sulfur aerosols on early Earth are discussed. Key Words: S-MIF-Archean atmosphere-Early Earth-Sulfur aerosols.

Reduction in haze formation rate on prebiotic Earth in the presence of hydrogen.

Recent attempts to resolve the faint young Sun paradox have focused on an early Earth atmosphere with elevated levels of the greenhouse gases methane (CH(4)) and carbon dioxide (CO(2)) that could have provided adequate warming to Earth's surface. On Titan, the photolysis of CH(4) has been shown to create a thick haze layer that cools its surface. Unlike Titan, however, early Earth's atmosphere likely contained high amounts of CO(2) and hydrogen (H(2)). In this work, we examine haze formation in an early Earth atmosphere composed of CO(2), H(2), N(2), and CH(4), with a CO(2)/CH(4) ratio of 10 and a H(2)/CO(2) ratio of up to 15. To initiate aerosol formation, a broad-spectrum ultraviolet (UV) energy source with emission at Lyman-alpha was used to simulate the solar spectrum. Aerosol composition and total aerosol mass produced as a function of reagent gas were measured with an aerosol mass spectrometer (AMS). Results show an order of magnitude decrease in haze production with the addition of H(2), with no significant change in the chemical composition of the haze. We calculate that the presence of H(2) on early Earth could thus have favored warmer surface temperatures and yet allowed photochemical haze formation to deliver complex organic species to early Earth's surface.

Organic haze on Titan and the early Earth.

Recent exploration by the Cassini/Huygens mission has stimulated a great deal of interest in Saturn's moon, Titan. One of Titan's most captivating features is the thick organic haze layer surrounding the moon, believed to be formed from photochemistry high in the CH(4)/N(2) atmosphere. It has been suggested that a similar haze layer may have formed on the early Earth. Here we report laboratory experiments that demonstrate the properties of haze likely to form through photochemistry on Titan and early Earth. We have used a deuterium lamp to initiate particle production in these simulated atmospheres from UV photolysis. Using a unique analysis technique, the aerosol mass spectrometer, we have studied the chemical composition, size, and shape of the particles produced as a function of initial trace gas composition. Our results show that the aerosols produced in the laboratory can serve as analogs for the observed haze in Titan's atmosphere. Experiments performed under possible conditions for early Earth suggest a significant optical depth of haze may have dominated the early Earth's atmosphere. Aerosol size measurements are presented, and implications for the haze layer properties are discussed. We estimate that aerosol production on the early Earth may have been on the order of 10(14) g.year(-1) and thus could have served as a primary source of organic material to the surface.