Cassini spacecraft reveals global energy imbalance of saturn.

The global energy budget is pivotal to understanding planetary evolution and climate behaviors. Assessing the energy budget of giant planets, particularly those with large seasonal cycles, however, remains a challenge without long-term observations. Evolution models of Saturn cannot explain its estimated Bond albedo and internal heat flux, mainly because previous estimates were based on limited observations. Here, we analyze the long-term observations recorded by the Cassini spacecraft and find notably higher Bond albedo (0.41 ± 0.02) and internal heat flux (2.84 ± 0.20 Wm-2) values than previous estimates. Furthermore, Saturn's global energy budget is not in a steady state and exhibits significant dynamical imbalances. The global radiant energy deficit at the top of the atmosphere, indicative of the planetary cooling of Saturn, reveals remarkable seasonal fluctuations with a magnitude of 16.0 ± 4.2%. Further analysis of the energy budget of the upper atmosphere including the internal heat suggests seasonal energy imbalances at both global and hemispheric scales, contributing to the development of giant convective storms on Saturn. Similar seasonal variabilities of planetary cooling and energy imbalance exist in other giant planets within and beyond the Solar System, a prospect currently overlooked in existing evolutional and atmospheric models.

The Composition and Chemistry of Titan's Atmosphere.

In this review I summarize the current state of knowledge about the composition of Titan's atmosphere and our current understanding of the suggested chemistry that leads to that observed composition. I begin with our present knowledge of the atmospheric composition, garnered from a variety of measurements including Cassini-Huygens, the Atacama Large Millimeter/submillimeter Array, and other ground- and space-based telescopes. This review focuses on the typical vertical profiles of gases at low latitudes rather than global and temporal variations. The main body of the review presents a chemical description of how complex molecules are believed to arise from simpler species, considering all known "stable" molecules-those that have been uniquely identified in the neutral atmosphere. The last section of the review is devoted to the gaps in our present knowledge of Titan's chemical composition and how further work may fill those gaps.

Organic Input to Titan's Subsurface Ocean Through Impact Cratering.

Titan has an organic-rich atmosphere and surface with a subsurface liquid water ocean that may represent a habitable environment. In this work, we determined the amount of organic material that can be delivered from Titan's surface to its ocean through impact cratering. We assumed that Titan's craters produce impact melt deposits composed of liquid water that can founder in its lower-density ice crust and estimated the amount of organic molecules that could be incorporated into these melt lenses. We used known yields for HCN and Titan haze hydrolysis to determine the amount of glycine produced in the melt lenses and found a range of possible flux rates of glycine from the surface to the subsurface ocean. These ranged from 0 to 1011 mol/Gyr for HCN hydrolysis and from 0 to 1014 mol/Gyr for haze hydrolysis. These fluxes suggest an upper limit for biomass productivity of ∼103 kgC/year from a glycine fermentation metabolism. This upper limit is significantly less than recent estimates of the hypothetical biomass production supported by Enceladus's subsurface ocean. Unless biologically available compounds can be sourced from Titan's interior, or be delivered from the surface by other mechanisms, our calculations suggest that even the most organic-rich ocean world in the Solar System may not be able to support a large biosphere.

Cassini composite infrared spectrometer: correcting an offset error and refining the pointing parameters for the midinfrared detectors.

Based on preflight laboratory testing, an unexpectedly large positional offset between the two midinfrared (mid-IR) detector arrays in the Cassini composite infrared spectrometer (CIRS) instrument has been noted in the literature. A much smaller offset was measured in-flight. We investigate this discrepancy by estimating several spatial relationships among the detectors and comparing these results with three independent data sets. This enables us to infer the probable cause of this offset and to derive a new reduced value. We comment on the effect that this change could have on previously published results involving CIRS data. We also present a graphical display of the arrays projected on the sky as CIRS would see it.

Cassini composite infrared spectrometer: correcting an offset error and refining the pointing parameters for the midinfrared detectors: publisher's note.

This publisher's note serves to correct Appl. Opt.62, 5882 (2023).APOPAI0003-693510.1364/AO.491970.

Raman and UVN+LWIR LIBS detection system for in-situ surface chemical identification.

Laser Induced Breakdown Spectroscopy (LIBS) in the Ultra Violet/Visible/Near-IR (UVN) spectral range is a powerful analytical tool that facilitates the interpretation of Raman spectroscopic data by providing additional details in elemental chemistry. To acquire the complete information of molecular vibrations for more accurate and precise chemical bonding and structural analysis, an ideal in situ optical sensing facility should be able to rapidly probe the broad vibrational dipole and polarizability responses of molecules by acquiring both Raman scattering and mid-IR emission spectroscopic signatures. Recently, the research team at Brimrose has developed a novel optical technology, Long-Wave IR (LWIR) LIBS. Critical experimental approaches were made to capture the infrared molecular emission signatures from vibrationally excited intact samples excited by laser-induced plasma in a LIBS event. LWIR LIBS is the only fieldable mid-IR emission spectroscopic technique to-date that that offers the same instrumental and analytical advantages of both UVN LIBS and Raman spectroscopy in in-situ stand-off field applications and can perform rapid and comprehensive molecular structure analysis without any sample-preparation.•A single excitation laser pulse is used to trigger both UVN and LWIR spectrometers simultaneously.•Time-resolved UVN-LWIR LIBS measurements showed the evolution of both atomic and molecular signature emissions of target compounds in the laser-induced plasma.•The technique was applied to the characterization of mineral and organic compounds in planetary analog samples.

Spectroscopic characterization of samples from different environments in a Volcano-Glacial region in Iceland: Implications for in situ planetary exploration.

Raman spectroscopy and laser induced breakdown spectroscopy (LIBS) are complementary techniques that together can provide a comprehensive characterization of geologic environments. For landed missions with constrained access to target materials on other planetary bodies, discerning signatures of life and habitability can be daunting, particularly where the preservation of organic compounds that contain the building blocks of life is limited. The main challenge facing any spectroscopy measurements of natural samples is the complicated spectra that often contain signatures for multiple components, particularly in rocks that are composed of several minerals with surfaces colonized by microbes. The goal of this study was to use the combination of Raman spectroscopy and LIBS to discern different environmental regimes based on the identification of minerals and biomolecules in rocks and sediments. Iceland is a terrestrial volcano-glacial location that offers a range of planetary analog environments, including volcanically active regions, extensive lava fields, geothermal springs, and large swaths of ice-covered terrain that are relevant to both rocky and icy planetary bodies. We combined portable VIS (532 nm) and NIR (785 nm) Raman spectroscopy, VIS micro-Raman spectroscopic mapping, and UV/VIS/NIR (200 - 1000 nm) and Mid-IR (5.6 - 10 µm, 1785 - 1000 cm-1) laser induced breakdown spectroscopy (LIBS) to characterize the mineral assemblages, hydrated components, and biomolecules in rock and sediment samples collected from three main sites in the volcanically active Kverkfjöll-Vatnajökull region of Iceland: basalt and basalt-hosted carbonate rind from Hveragil geothermal stream, volcanic sediments from the base of Vatnajökull glacier at Kverkfjöll, and lava from the nearby Holuhraun lava field. With our combination of techniques, we were able to identify major mineral polytypes typical for each sample set, as well as a large diversity of biomolecules typical for lichen communities across all samples. The anatase we observed using micro-Raman spectroscopic mapping of the lava compared with the volcanic sediment suggested different formation pathways: lava anatase formed authigenically, sediment anatase could have formed in association with microbial weathering. Mn-oxide, only detected in the carbonate samples, seems to have two possible formation pathways, either by fluvial or microbial weathering or both. Even with our ability to detect a wide diversity of biomolecules and minerals in all of the samples, there was not enough variation between each set to distinguish different environments based on the limited measurements done for this study.

Extraction and Separation of Chiral Amino Acids for Life Detection on Ocean Worlds Without Using Organic Solvents or Derivatization.

In situ instrumentation that can detect amino acids at parts-per-billion concentration levels and distinguish an enantiomeric excess of either d- or l-amino acids is vital for future robotic life-detection missions to promising targets in our solar system. In this article, a novel chiral amino acid analysis method is described, which reduces the risk of organic contamination and spurious signals from by-products by avoiding organic solvents and organic additives. Online solid-phase extraction, chiral liquid chromatography, and mass spectrometry were used for automated analysis of amino acids from solid and aqueous environmental samples. Carbonated water (pH ∼3, ∼5 wt % CO2 achieved at 6 MPa) was used as the extraction solvent for solid samples at 150°C and as the mobile phase at ambient temperature for chiral chromatographic separation. Of 18 enantiomeric amino acids, 5 enantiomeric pairs were separated with a chromatographic resolution >1.5 and 12 pairs with a resolution >0.7. The median lower limit of detection of amino acids was 2.5 µg/L, with the lowest experimentally verified as low as 0.25 µg/L. Samples from a geyser site (Great Fountain Geyser) and a geothermal spring site (Lemon Spring) in Yellowstone National Park were analyzed to demonstrate the viability of the method for future in situ missions to Ocean Worlds.

The formation and evolution of Titan's winter polar vortex.

Saturn's largest moon Titan has a substantial nitrogen-methane atmosphere, with strong seasonal effects, including formation of winter polar vortices. Following Titan's 2009 northern spring equinox, peak solar heating moved to the northern hemisphere, initiating south-polar subsidence and winter polar vortex formation. Throughout 2010-2011, strengthening subsidence produced a mesospheric hot-spot and caused extreme enrichment of photochemically produced trace gases. However, in 2012 unexpected and rapid mesospheric cooling was observed. Here we show extreme trace gas enrichment within the polar vortex dramatically increases mesospheric long-wave radiative cooling efficiency, causing unusually cold temperatures 2-6 years post-equinox. The long time-frame to reach a stable vortex configuration results from the high infrared opacity of Titan's trace gases and the relatively long atmospheric radiative time constant. Winter polar hot-spots have been observed on other planets, but detection of post-equinox cooling is so far unique to Titan.

ALMA detection and astrobiological potential of vinyl cyanide on Titan.

Recent simulations have indicated that vinyl cyanide is the best candidate molecule for the formation of cell membranes/vesicle structures in Titan's hydrocarbon-rich lakes and seas. Although the existence of vinyl cyanide (C2H3CN) on Titan was previously inferred using Cassini mass spectrometry, a definitive detection has been lacking until now. We report the first spectroscopic detection of vinyl cyanide in Titan's atmosphere, obtained using archival data from the Atacama Large Millimeter/submillimeter Array (ALMA), collected from February to May 2014. We detect the three strongest rotational lines of C2H3CN in the frequency range of 230 to 232 GHz, each with >4σ confidence. Radiative transfer modeling suggests that most of the C2H3CN emission originates at altitudes of ≳200 km, in agreement with recent photochemical models. The vertical column densities implied by our best-fitting models lie in the range of 3.7 × 1013 to 1.4 × 1014 cm-2. The corresponding production rate of vinyl cyanide and its saturation mole fraction imply the availability of sufficient dissolved material to form ~107 cell membranes/cm3 in Titan's sea Ligeia Mare.

Aerosol influence on energy balance of the middle atmosphere of Jupiter.

Aerosols are ubiquitous in planetary atmospheres in the Solar System. However, radiative forcing on Jupiter has traditionally been attributed to solar heating and infrared cooling of gaseous constituents only, while the significance of aerosol radiative effects has been a long-standing controversy. Here we show, based on observations from the NASA spacecraft Voyager and Cassini, that gases alone cannot maintain the global energy balance in the middle atmosphere of Jupiter. Instead, a thick aerosol layer consisting of fluffy, fractal aggregate particles produced by photochemistry and auroral chemistry dominates the stratospheric radiative heating at middle and high latitudes, exceeding the local gas heating rate by a factor of 5-10. On a global average, aerosol heating is comparable to the gas contribution and aerosol cooling is more important than previously thought. We argue that fractal aggregate particles may also have a significant role in controlling the atmospheric radiative energy balance on other planets, as on Jupiter.

Strong temporal variation over one Saturnian year: from Voyager to Cassini.

Here we report the combined spacecraft observations of Saturn acquired over one Saturnian year (~29.5 Earth years), from the Voyager encounters (1980-81) to the new Cassini reconnaissance (2009-10). The combined observations reveal a strong temporal increase of tropic temperature (~10 Kelvins) around the tropopause of Saturn (i.e., 50 mbar), which is stronger than the seasonal variability (~a few Kelvins). We also provide the first estimate of the zonal winds at 750 mbar, which is close to the zonal winds at 2000 mbar. The quasi-consistency of zonal winds between these two levels provides observational support to a numerical suggestion inferring that the zonal winds at pressures greater than 500 mbar do not vary significantly with depth. Furthermore, the temporal variation of zonal winds decreases its magnitude with depth, implying that the relatively deep zonal winds are stable with time.

Active upper-atmosphere chemistry and dynamics from polar circulation reversal on Titan.

Saturn's moon Titan has a nitrogen atmosphere comparable to Earth's, with a surface pressure of 1.4 bar. Numerical models reproduce the tropospheric conditions very well but have trouble explaining the observed middle-atmosphere temperatures, composition and winds. The top of the middle-atmosphere circulation has been thought to lie at an altitude of 450 to 500 kilometres, where there is a layer of haze that appears to be separated from the main haze deck. This 'detached' haze was previously explained as being due to the co-location of peak haze production and the limit of dynamical transport by the circulation's upper branch. Here we report a build-up of trace gases over the south pole approximately two years after observing the 2009 post-equinox circulation reversal, from which we conclude that middle-atmosphere circulation must extend to an altitude of at least 600 kilometres. The primary drivers of this circulation are summer-hemisphere heating of haze by absorption of solar radiation and winter-hemisphere cooling due to infrared emission by haze and trace gases; our results therefore imply that these effects are important well into the thermosphere (altitudes higher than 500 kilometres). This requires both active upper-atmosphere chemistry, consistent with the detection of high-complexity molecules and ions at altitudes greater than 950 kilometres, and an alternative explanation for the detached haze, such as a transition in haze particle growth from monomers to fractal structures.

Upper limits for undetected trace species in the stratosphere of Titan.

In this paper we describe the first quantitative search for several molecules in Titan's stratosphere in Cassini CIRS infrared spectra. These are: ammonia (NH3), methanol (CH3OH), formaldehyde (H2CO), and acetonitrile (CH3CN), all of which are predicted by photochemical models but only the last of which has been observed, and not in the infrared. We find non-detections in all cases, but derive upper limits on the abundances from low-noise observations at 25 degrees S and 75 degrees N. Comparing these constraints to model predictions, we conclude that CIRS is highly unlikely to see NH3 or CH3OH emissions. However, CH3CN and H2CO are closer to CIRS detectability, and we suggest ways in which the sensitivity threshold may be lowered towards this goal.

12C/13C ratio in ethane on titan and implications for methane's replenishment.

The (12)C/(13)C abundance ratio in ethane in the atmosphere of Titan has been measured at 822 cm(-1) from high spectral resolution ground-based observations. The value, 89(8), coincides with the telluric standard and also agrees with the ratio seen in the outer planets. It is almost identical to the result for ethane on Titan found by the composite infrared spectrometer (CIRS) on Cassini. The (12)C/(13)C ratio for ethane is higher than the ratio measured in atmospheric methane by Cassini/Huygens GCMS, 82.3(1), representing an enrichment of (12)C in the ethane that might be explained by a kinetic isotope effect of approximately 1.1 in the formation of methyl radicals. If methane is being continuously resupplied to balance photochemical destruction, then we expect the isotopic composition in the ethane product to equilibrate at close to the same (12)C/(13)C ratio as that in the supply. The telluric value of the ratio in ethane then implies that the methane reservoir is primordial.

Infrared limb sounding of Titan with the Cassini Composite InfraRed Spectrometer: effects of the mid-IR detector spatial responses.

The composite infrared spectrometer (CIRS) instrument on board the Cassini Saturn orbiter employs two 1x10 HgCdTe detector arrays for mid-infrared remote sensing of Titan's and Saturn's atmospheres. In this paper we show that the real detector spatial response functions, as measured in ground testing before launch, differ significantly from idealized "boxcar" responses. We further show that neglecting this true spatial response function when modeling CIRS spectra can have a significant effect on interpretation of the data, especially in limb-sounding mode, which is frequently used for Titan science. This result has implications not just for CIRS data analysis but for other similar instrumental applications.

Dynamical implications of seasonal and spatial variations in Titan's stratospheric composition.

Titan's diverse inventory of photochemically produced gases can be used as tracers to probe atmospheric circulation. Since the arrival of the Cassini-Huygens mission in July 2004 it has been possible to map the seasonal and spatial variations of these compounds in great detail. Here, we use 3.5 years of data measured by the Cassini Composite InfraRed Spectrometer instrument to determine spatial and seasonal composition trends, thus providing clues to underlying atmospheric motions. Titan's North Pole (currently in winter) displays enrichment of trace species, implying subsidence is occurring there. This is consistent with the descending branch of a single south-to-north stratospheric circulation cell and a polar vortex. Lack of enrichment in the south over most of the observed time period argues against the presence of any secondary circulation cell in the Southern Polar stratosphere. However, a residual cap of enriched gas was observed over the South Pole early in the mission, which has since completely dissipated. This cap was most probably due to residual build-up from southern winter. These observations provide new and important constraints for models of atmospheric photochemistry and circulation.