Ambient and cold-temperature infrared spectra and XRD patterns of ammoniated phyllosilicates and carbonaceous chondrite meteorites relevant to Ceres and other solar system bodies

Mg‐phyllosilicate‐bearing, dark surface materials on the dwarf planet Ceres have NH_4‐bearing materials, indicated by a distinctive 3.06 μm absorption feature. To constrain the identity of the Ceres NH_4‐carrier phase(s), we ammoniated ground particulates of candidate materials to compare their spectral properties to infrared data acquired by Dawn's Visible and Infrared (VIR) imaging spectrometer. We treated Mg‐, Fe‐, and Al‐smectite clay minerals; Mg‐serpentines; Mg‐chlorite; and a suite of carbonaceous meteorites with NH_4‐acetate to exchange ammonium. Serpentines and chlorites showed no evidence for ammoniation, as expected due to their lack of exchangeable interlayer sites. Most smectites showed evidence for ammoniation by incorporation of NH_4^+ into their interlayers, resulting in the appearance of absorptions from 3.02 to 3.08 μm. Meteorite samples tested had weak absorptions between 3.0 and 3.1 μm but showed little clear evidence for enhancement upon ammoniation, likely due to the high proportion of serpentine and other minerals relative to expandable smectite phases or to NH_4^+ complexing with organics or other constituents. The wavelength position of the smectite NH4 absorption showed no variation between IR spectra acquired under dry‐air purge at 25 °C and under vacuum at 25 °C to −180 °C. Collectively, data from the smectite samples show that the precise center wavelength of the characteristic ~3.05 μm v_3 absorption in NH_4 is variable and is likely related to the degree of hydrogen bonding of NH_4‐H_2O complexes. Comparison with Dawn VIR spectra indicates that the hypothesis of Mg‐saponite as the ammonium carrier phase is the simplest explanation for observed data, and that Ceres dark materials may be like Cold Bokkeveld or Tagish Lake but with proportionally more Mg‐smectite

Spectrally-resolved UV photodesorption of CH4 in pure and layered ices

Context. Methane is among the main components of the ice mantles of insterstellar dust grains, where it is at the start of a rich solid-phase chemical network. Quantification of the photon-induced desorption yield of these frozen molecules and understanding of the underlying processes is necessary to accurately model the observations and the chemical evolution of various regions of the interstellar medium. Aims. This study aims at experimentally determining absolute photodesorption yields for the CH4 molecule as a function of photon energy. The influence of the ice composition is also investigated. By studying the methane desorption from layered CH4:CO ice, indirect desorption processes triggered by the excitation of the CO molecules is monitored and quantified. Methods. Tunable monochromatic VUV light from the DESIRS beamline of the SOLEIL synchrotron is used in the 7 - 13.6 eV (177 - 91 nm) range to irradiate pure CH4 or layers of CH4 deposited on top of CO ice samples. The release of species in the gas phase is monitored by quadrupole mass spectrometry and absolute photodesorption yields of intact CH4 are deduced. Results. CH4 photodesorbs for photon energies higher than ~9.1 eV (~136 nm). The photodesorption spectrum follows the absorption spectrum of CH4, which confirms a desorption mechanism mediated by electronic transitions in the ice. When it is deposited on top of CO, CH4 desorbs between 8 and 9 eV with a pattern characteristic of CO absorption, indicating desorption induced by energy transfer from CO molecules. Conclusions. The photodesorption of CH4 from the pure ice in various interstellar environments is around 2.0 x 10^-3 molecules per incident photon. Results on CO-induced indirect desorption of CH4 provide useful insights for the generalization of this process to other molecules co-existing with CO in ice mantles

On the representation error in data assimilation

Representation, representativity, representativeness error, forward interpolation error, forward model error, observation operator error, aggregation error and sampling error are all terms used to refer to components of observation error in the context of data assimilation. This paper is an attempt to consolidate the terminology that has been used in the earth sciences literature and was suggested at a European Space Agency workshop held in Reading in April 2014. We review the state-of-the-art, and through examples, motivate the terminology. In addition to a theoretical framework, examples from application areas of satellite data assimilation, ocean reanalysis and atmospheric chemistry data assimilation are provided. Diagnosing representation error statistics as well as their use in state-of-the-art data assimilation systems is discussed within a consistent framework

A Deeper Analysis of Center-Finding Techniques for Tropical Cyclones in Mesoscale Models. Part I: Low-Wavenumber Analysis

AbstractA deeper analysis of possible errors and inconsistencies in the analysis of vortex asymmetries owing to the placement of centers of tropical cyclones (TCs) in mesoscale models is presented. Previous works have established that components of the 2D and 3D structure of these TCs—primarily radial wind and vertical tilt—can vary greatly depending on how the center of a model TC is defined. This work will seek to expand the previous research on this topic, but only for the 2D structure. To be specific, this work will present how low-wavenumber azimuthal Fourier analyses can vary with center displacement using idealized, parametric TC-like vortices. It is shown that the errors associated with aliasing the mean are sensitive primarily to the difference between the peak of vorticity inside the radius of maximum winds and the average vorticity inside the core. Tangential wind and vorticity aliasing occur primarily in the core; radial wind aliasing spans the whole of the vortex. It is also shown that, when adding low-wavenumber asymmetries, the aliasing is dependent on the placement of the center relative to the location of the asymmetries on the vortex. It is also shown that the primary concern for 2D analysis when calculating the center of a TC is correctly resolving azimuthal wavenumber 0 tangential wind, because errors here will alias onto all higher wavenumbers, the specific structures of which are dependent on the structure of the mean vortex itself

Dissolution geology of organic materials on Saturn’s moon Titan: alien analogs of terrestrial karst

Karst or dissolution geology can occur whenever a circulating fluid can dissolve a geological material. On Earth, the “classical” karst definition is for limestone (CaCO3) in water (H2O), but other material/solvent combinations can create terrestrial dissolution terrain as well. These include so-called “evaporite karst materials” such as halite (NaCl)/H2O or gypsum (CaSO4)/H2O, dolomite (CaMg(CO3)2)/H2O, and even silica (SiO2)/H2O [Ford and Williams, 2007].  On Mars, there has been the suggestion of kieserite (MgSO4)/H2O system that may have formed in an earlier, wetter environment [Baroni and Sgavetta, 2013]. Saturn’s moon Titan extends the definition of karst to include non-aqueous liquids dissolving a landscape made of organic materials. The Cassini mission has provided evidence that Titan’s 1.5 bar nitrogen atmosphrere and cryogenic 94 K surface temperature supports a hydrocarbon-based cycle on Titan similar to the terrestrial water cycle. These circulating liquids may be capable of dissolving some of the surface organic molecules derived from Titan’s complex atmospheric photochemistry. Although under a different gravity, temperature, materials and fluid regime, many of the features on Titan’s surface bear striking resemblances to terrestrial karst terrains. Our investigations have focused on the labyrinth terrains of Titan. These are elevated plateaux of organic materials that appear similar to polygonal karst, tower karst, and fluviokarst on Earth [Malaska et al., 2010; 2017]. Remote sensing data is consistent with these plateaux being constructed of low-dielectric organic materials [Janssen et al. 2009; 2016; Malaska et al, 2016b]. Theoretical calculations followed by cryogenic laboratory experiments have shown that organic materials found on Titan’s surface will dissolve when subjected to Titan’s rainfall of methane-rich fluids [Raulin, 1987; Lorenz and Lunine, 1996; Malaska et al., 2010; 2011; Malaska and Hodyss, 2014; Cornet et al., 2015] and preliminary modelling has been able to reproduce some of the morphologies observed on Titan [Cornet et al., 2017]. Titan’s labyrinth terrains may originate as mixed organic windblown sediments that are later lithified in a process similar to calcite-cemented sandstone on Earth. Organic molecules and sediments produced by Titan’s rich organic photochemistry include organic molecules such as acetylene (C2H2), ethylene (C2H4), hydrogen cyanide (HCN),  benzene (C2H6), acrylonitrile (C2H3CN), acetonitrile (CH3CN), cyanoacetylene (HC2CN), other alkynes and nitriles, and a complex refractory organic materials similar to laboratory tholins. Once uplifted, the saturation equilibrium and kinetics of dissolution for each material and fluid combination affecting the plateau may play key roles in determining how the karstic system will evolve [Malaska et al., 2011; Cornet et al., 2015]. Some of the Titan organic minerals will dissolve, while some will be left behind as an insoluble lag deposit. Advanced laboratory investigations of organic materials on Titan is underway to further understand how these geological structures evolve and compare them with the formation processes of terrestrial analogs. We suggest that karst is a general planetary process wherever circulating fluids are capable of dissolving materials and developing subsurface drainage

Deformation characteristics of solid-state benzene as a step towards understanding planetary geology

Small organic molecules, like ethane and benzene, are ubiquitous in the atmosphere and surface of Saturn’s largest moon Titan, forming plains, dunes, canyons, and other surface features. Understanding Titan’s dynamic geology and designing future landing missions requires sufficient knowledge of the mechanical characteristics of these solid-state organic minerals, which is currently lacking. To understand the deformation and mechanical properties of a representative solid organic material at space-relevant temperatures, we freeze liquid micro-droplets of benzene to form ~10 μm-tall single-crystalline pyramids and uniaxially compress them in situ. These micromechanical experiments reveal contact pressures decaying from ~2 to ~0.5 GPa after ~1 μm-reduction in pyramid height. The deformation occurs via a series of stochastic (~5-30 nm) displacement bursts, corresponding to densification and stiffening of the compressed material during cyclic loading to progressively higher loads. Molecular dynamics simulations reveal predominantly plastic deformation and densified region formation by the re-orientation and interplanar shear of benzene rings, providing a two-step stiffening mechanism. This work demonstrates the feasibility of in-situ cryogenic nanomechanical characterization of solid organics as a pathway to gain insights into the geophysics of planetary bodies

The effects of estimating a photoionization parameter within a physics-based model using data assimilation

Data assimilation (DA) is the process of merging information from prediction models with noisy observations to produce an estimate of the state of a physical system. In ionospheric physics-based models, the solar ionizing irradiance is commonly estimated from a solar index like F10.7. The goal of this work is to provide the fundamental understanding necessary to appreciate how a DA algorithm responds to estimating an external parameter driving the model’s interpretation of this solar ionizing irradiance. Therefore, in this work we allow the DA system to find the F10.7 value that delivers the degree of photoionization that leads to a predicted electron density field that best matches the observations. To this end, we develop a heuristic model of the ionosphere along the magnetic equator that contains physics from solar forcing and recombination/plasma diffusion, which allows us to explore the impacts of strongly forced system dynamics on DA. This framework was carefully crafted to be both linear and Gaussian, which allows us to use a Kalman filter to clearly see how: (1) while recombination acts as a sink on the information in the initial condition for ionospheric field variables, recombination does not impact the information in parameter estimates in the same way, (2) when solar forcing dominates the electron density field, the prior covariance matrix becomes dominated by its leading eigenvector whose structure is directly related to that of the solar forcing, (3) estimation of parameters for forcing terms leads to a time-lag in the state estimate relative to the truth, (4) the performance of a DA system in this regime is determined by the relative dominance of solar forcing and recombination to that of the smaller-scale processes and (5) the most impactful observations on the electron density field and on the solar forcing parameter are those observations on the sunlit side of the ionosphere. These findings are then illustrated in a full physics-based ionospheric model using an ensemble Kalman filter DA scheme

Hydrogen Bonding Constrains Free Radical Reaction Dynamics at Serine and Threonine Residues in Peptides

Free radical-initiated peptide sequencing (FRIPS) mass spectrometry derives advantage from the introduction of highly selective low-energy dissociation pathways in target peptides. An acetyl radical, formed at the peptide N-terminus via collisional activation and subsequent dissociation of a covalently attached radical precursor, abstracts a hydrogen atom from diverse sites on the peptide, yielding sequence information through backbone cleavage as well as side-chain loss. Unique free-radical-initiated dissociation pathways observed at serine and threonine residues lead to cleavage of the neighboring N-terminal C_α–C or N–C_α bond rather than the typical Cα–C bond cleavage observed with other amino acids. These reactions were investigated by FRIPS of model peptides of the form AARAAAXAA, where X is the amino acid of interest. In combination with density functional theory (DFT) calculations, the experiments indicate the strong influence of hydrogen bonding at serine or threonine on the observed free radical chemistry. Hydrogen bonding of the side-chain hydroxyl group with a backbone carbonyl oxygen aligns the singly occupied π orbital on the β-carbon and the N–C_α bond, leading to low-barrier β-cleavage of the N–C_α bond. Interaction with the N-terminal carbonyl favors a hydrogen-atom transfer process to yield stable c and z• ions, whereas C-terminal interaction leads to effective cleavage of the C_α–C bond through rapid loss of isocyanic acid. Dissociation of the C_α–C bond may also occur via water loss followed by β-cleavage from a nitrogen-centered radical. These competitive dissociation pathways from a single residue illustrate the sensitivity of gas-phase free radical chemistry to subtle factors such as hydrogen bonding that affect the potential energy surface for these low-barrier processes

Ambient and cold-temperature infrared spectra and XRD patterns of ammoniated phyllosilicates and carbonaceous chondrite meteorites relevant to Ceres and other solar system bodies

Mg‐phyllosilicate‐bearing, dark surface materials on the dwarf planet Ceres have NH_4‐bearing materials, indicated by a distinctive 3.06 μm absorption feature. To constrain the identity of the Ceres NH_4‐carrier phase(s), we ammoniated ground particulates of candidate materials to compare their spectral properties to infrared data acquired by Dawn's Visible and Infrared (VIR) imaging spectrometer. We treated Mg‐, Fe‐, and Al‐smectite clay minerals; Mg‐serpentines; Mg‐chlorite; and a suite of carbonaceous meteorites with NH_4‐acetate to exchange ammonium. Serpentines and chlorites showed no evidence for ammoniation, as expected due to their lack of exchangeable interlayer sites. Most smectites showed evidence for ammoniation by incorporation of NH_4^+ into their interlayers, resulting in the appearance of absorptions from 3.02 to 3.08 μm. Meteorite samples tested had weak absorptions between 3.0 and 3.1 μm but showed little clear evidence for enhancement upon ammoniation, likely due to the high proportion of serpentine and other minerals relative to expandable smectite phases or to NH_4^+ complexing with organics or other constituents. The wavelength position of the smectite NH4 absorption showed no variation between IR spectra acquired under dry‐air purge at 25 °C and under vacuum at 25 °C to −180 °C. Collectively, data from the smectite samples show that the precise center wavelength of the characteristic ~3.05 μm v_3 absorption in NH_4 is variable and is likely related to the degree of hydrogen bonding of NH_4‐H_2O complexes. Comparison with Dawn VIR spectra indicates that the hypothesis of Mg‐saponite as the ammonium carrier phase is the simplest explanation for observed data, and that Ceres dark materials may be like Cold Bokkeveld or Tagish Lake but with proportionally more Mg‐smectite