Engineering topics

Loeffler, Mark J.

Publications and source records attributed to Loeffler, Mark J..

14 records

DOE OSTI2021

Solar wind contributions to Earth’s oceans

The isotopic composition of water in Earth’s oceans is challenging to recreate using a plausible mixture of known extraterrestrial sources such as asteroids—an additional isotopically light reservoir is required. The Sun’s solar wind could provide an answer to balance Earth’s water budget. Here, we used atom probe tomography to directly observe an average ~1 mol% enrichment in water and hydroxyls in the solar-wind-irradiated rim of an olivine grain from the S-type asteroid Itokawa. We also experimentally confirm that H + irradiation of silicate mineral surfaces produces water molecules. These results suggest that the Itokawa regolith could contain ~20 l m -3 of solar-wind-derived water and that such water reservoirs are probably ubiquitous on airless worlds throughout our Galaxy. The production of this isotopically light water reservoir by solar wind implantation into fine-grained silicates may have been a particularly important process in the early Solar System, potentially providing a means to recreate Earth’s current water isotope ratios.

79 ASTRONOMY AND ASTROPHYSICS↗

NASA NTRS2020

Testing Densities and Refractive Indices of Extraterrestrial Ice Components Using Molecular Structures - Organic Compounds and Molar Refractions

The use of infrared spectra to determine molecular abundances of icy astronomical objects and to study their chemistry requires laboratory measurements of reference spectra and related quantities, such as the index of refraction (n) and density (p) of candidate ices. Here we present new n and p measurements on ices involving over 30 C-, H-, and O-containing compounds, both acyclic and cyclic, representing seven chemical families. We examine the results in a way that is rare in the astrochemical literature, namely one in which data from an ice formed from molecules of a particular chemical family are compared to measurements on another member of the same family, such as of a homologous series or a pair of isomers. Apart from the intrinsic usefulness of the n and data, a structure-based comparison can help establish trends and identify possibly spurious results. As liquid-phase data sometimes are used in low-temperature astrochemical work in the absence of solid-phase measurements, we compare our new ice results to those for the corresponding room-temperature liquids. We emphasize the use of our n and p data to compute the molar refraction (RM) for each of our ices, and how the resulting RM values compare to those expected from molecular structures. The use of calculated RM values and measured n values to calculate ice densities, in the absence of direct measurements, is also addressed.

Hudson, Reggie L.↗

NASA NTRS2017

Coloring Jupiter's Clouds: Radiolysis of Ammonium Hydrosulfide (NH4SH)

Here we present our recent studies on the color and spectral reflectance changes induced by approximately 0.9 megaelectronvolts proton irradiation of ammonium hydrosulfide, NH4SH, a compound predicted to be an important tropospheric cloud component of Jupiter and other giant planets. Ultraviolet-visible spectroscopy was used to observe and identify reaction products in the ice sample and digital photography was used to document the corresponding color changes at 10-160 degrees Kelvin. Our experiments clearly show that the resulting color of the sample depends not only on the irradiation dose but also the irradiation temperature. Furthermore, unlike in our most recent studies of irradiation of NH4SH at 120 degrees Kelvin, which showed that higher irradiation doses caused the sample to appear green, the lower temperature studies now show that the sample becomes red after irradiation. However, comparison of these lower temperature spectra over the entire spectral range observed by HST (Hubble Space Telescope) shows that even though the color and spectrum resemble the color and spectrum of the GRS (Jupiter’s Great Red Spot), there is still enough difference to suggest that another component may be needed to adequately fit spectra of the GRS and other red regions of Jupiter's clouds. Regardless, the presence of NH4SH in the atmosphere of Jupiter and other gas giants, combined with this compound's clear alteration via radiolysis, suggests that its contribution to the ultraviolet-visible spectra of any of these object's clouds is significant.

ultraviolet-visible spectroscopy↗

NASA NTRS2016

What is Eating Ozone? Thermal Reactions between SO2 And O3: Implications for Icy Environments

Laboratory studies are presented, showing for the first time that thermally driven reactions in solid H2O+SO2+O3 mixtures can occur below 150 K, with the main sulfur-containing product being bisulfate (HSO4(-)). Using a technique not previously applied to the low-temperature kinetics of either interstellar or solar system ice analogs, we estimate an activation energy of 32 kJ per mol for HSO4(-) formation. These results show that at the temperatures of the Jovian satellites, SO2 and O3 will efficiently react making detection of these molecules in the same vicinity unlikely. Our results also explain why O3 has not been detected on Callisto and why the SO2 concentration on Callisto appears to be highest on that world's leading hemisphere. Furthermore, our results predict that the SO2 concentration on Ganymede will be lowest in the trailing hemisphere, where the concentration of O3 is the highest. Our work suggests that thermal reactions in ices play a much more important role in surface and sub-surface chemistry than generally appreciated, possibly explaining the low abundance of sulfur-containing molecules and the lack of ozone observed in comets and interstellar ices.

Loeffler, Mark J.↗

NASA NTRS2016

Environmental Temperature Effect on the Far-Infrared Absorption Features of Aromatic-Based Titan's Aerosol Analogs

Benzene detection has been reported in Titans atmosphere both in the stratosphere at ppb levels by remote sensing and in the thermosphere at ppm levels by the Cassini's Ion and Neutral Mass Spectrometer. This detection supports the idea that aromatic and heteroaromatic reaction pathways may play an important role in Titans atmospheric chemistry, especially in the formation of aerosols. Indeed, aromatic molecules are easily dissociated by ultraviolet radiation and can therefore contribute significantly to aerosol formation. It has been shown recently that aerosol analogs produced from a gas mixture containing a low concentration of aromatic and/or heteroaromatic molecules (benzene, naphthalene, pyridine, quinoline and isoquinoline) have spectral signatures below 500/cm, a first step towards reproducing the aerosol spectral features observed by Cassini's Composite InfraRed Spectrometer (CIRS) in the far infrared. In this work we investigate the influence of environmental temperature on the absorption spectra of such aerosol samples, simulating the temperature range to which aerosols, once formed, are exposed during their transport through Titans stratosphere. Our results show that environmental temperature does not have any major effect on the spectral shape of these aerosol analogs in the far-infrared, which is consistent with the CIRS observations.

Gautier, Thomas↗

NASA NTRS2016

The Spectrum of Jupiter's Great Red Spot: The Case for Ammonium Hydrosulfide (NH4SH)

Here we present new ultraviolet-visible spectra of irradiated ammonium hydrosulﬁde (NH4SH), a reported Jovian atmospheric cloud component, for a range of temperatures and radiation doses and make assignments to the spectral features. We show that the combination of radiolysis and thermal annealing of NH4SH causes the originally featureless ultraviolet-visible reﬂectance spectrum to evolve into one that absorbs in the ultraviolet-visible region. Furthermore, we ﬁnd that our laboratory spectra resemble HST (Hubble Space Telescope) spectra below 500 nanometers, suggesting that the more stable reaction products of NH4SH radiolysis are likely an important component of the Great Red Spot.

Jupiter's Great Red Spot (GRS)↗

NASA NTRS2016

The Spectrum of Jupiters Great Red Spot: the Case for Ammonium Hydrosulfide (NH4SH)

Jupiter Atmosphere↗

NASA NTRS2015

Giant-Planet Chemistry: Ammonium Hydrosulfide (NH4SH), Its IR Spectra and Thermal and Radiolytic Stabilities

Here we present our recent studies of proton-irradiated and unirradiated ammonium hydrosulfide, NH4SH, a compound predicted to be an important tropospheric cloud component of Jupiter and other giant planets. We irradiated both crystalline and amorphous NH4SH at 10-160 K and used IR spectroscopy to observe and identify reaction products in the ice, specifically NH3 and long-chained sulfur-containing ions. Crystalline NH4SH was amorphized during irradiation at all temperatures studied with the rate being the fastest at the lowest temperatures. Irradiation of amorphous NH4SH at approximately 10-75 K showed that 60-80% of the NH4 + remained when equilibrium was reached, and that NH4SH destruction rates were relatively constant within this temperature range. Irradiations at higher temperatures produced different dose dependence and were accompanied by pressure outbursts that, in some cases, fractured the ice. The thermal stability of irradiated NH4SH was found to be greater than that of unirradiated NH4SH, suggesting that an irradiated giant-planet cloud precipitate can exist at temperatures and altitudes not previously considered.

Jupiter↗

NASA NTRS2014

Titan Aerosol Analog Absorption Features Produced from Aromatics in the Far Infrared

We present results on the formation of Titan aerosol analogs produced via far-UV irradiation of five aromatic precursors: benzene, naphthalene, pyridine, quinoline and isoquinoline. This is the first reported evidence of far-IR emission features observed below 200 per cm in laboratory-created Titan aerosols. These laboratory studies were motivated by recent analyses of Cassini Composite Infrared Spectrometer (CIRS) spectra that show a broad aerosol emission feature in the far-IR spectral region centered near 140 per cm, which is unique to Titan's photochemically-produced aerosol. We find that all three of the aerosol analogs formed from nitrogen-containing aromatics have similar broad emission features near that of the observed CIRS far-IR aerosol spectral feature. In addition, the inclusion of 1.5% methane to that of trace amounts of benzene also gives rise to an aerosol with a weak far-IR emission feature located below 200 per cm.

atmosphere↗

NASA NTRS2012

Thermal Reactions of H2O2 on Icy Satellites and Small Bodies: Descent with Modification?

Magnetospheric radiation drives surface and near-surface chemistry on Europa, but below a few meters Europa's chemistry is hidden from direct observation . As an example, surface radiation chemistry converts H2O and SO2 into H2O2 and (SO4)(sup 2-), respectively, and these species will be transported downward for possible thermally-driven reactions. However, while the infrared spectra and radiation chemistry of H2O2-containing ices are well documented, this molecule's thermally-induced solid-phase chemistry has seldom been studied. Here we report new results on thermal reactions in H2O + H2O2 + SO2 ices at 50 - 130 K. As an example of our results, we find that warming H2O + H2O2 + SO2 ices promotes SO2 oxidation to (SO4)(sup 2-). These results have implications for the survival of H2O2 as it descends, with modification, towards a subsurface ocean on Europa. We suspect that such redox chemistry may explain some of the observations related to the presence and distribution of H2O2 across Europa's surface as well as the lack of H2O2 on Ganymede and Callisto.

Hudson, Reggie L.↗

NASA NTRS2012

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).

Trainer, Melissa G.↗

NASA NTRS2012

Infrared Spectral Studies of the Thermally-Driven Chemistry Present on Icy Satellites

Remote sensing of Jupiters icy satellites has revealed that even though their surfaces arc composed mostly of water ice, molecules such as SO2, CO2, H2O2. O2, and O3 also are present. On Europa, a high radiation flux is believed to play a role in the formation of many of the minor species detected, and numerous laboratory studies have been devoted to explore this hypothesis. In this presentation we will discuss some of our recent research on another alteration pathway, thermally-driven chemical reactions, which are also important for understanding the chemical evolution of Europa's surface and sub-surface ices. We will focus on the infrared spectra of and reactions between H2O, SO2 and H2O2, at 80 - 130 K.

Loeffler, Mark J.↗

NASA NTRS2012

Thermal Regeneration of Sulfuric Acid Hydrates after Irradiation

In an attempt to more completely understand the surface chemistry of the jovian icy satellites, we have investigated the effect of heating on two irradiated crystalline sulfuric acid hydrates, H2SO4 4H2O and H2SO4 H2O. At temperatures relevant to Europa and the warmer jovian satellites, post-irradiation heating recrystallized the amorphized samples and increased the intensities of the remaining hydrate's infrared absorptions. This thermal regeneration of the original hydrates was nearly 100% efficient, indicating that over geological times, thermally-induced phase transitions enhanced by temperature fluctuations will reform a large fraction of crystalline hydrated sulfuric acid that is destroyed by radiation processing. The work described is the first demonstration of the competition between radiation-induced amorphization and thermally-induced recrystallization in icy ionic solids relevant to the outer Solar System.

Loeffler, Mark J.↗

NASA NTRS2011

Thermally-Induced Chemistry and the Jovian Icy Satellites: A Laboratory Study of the Formation of Sulfur Oxyanions

Laboratory experiments have demonstrated that magnetospheric radiation in the Jovian system drives reaction chemistry in ices at temperatures relevant to Europa and other icy satellites. Here we present new results on thermally-induced reactions at 50-100 K in solid H2O-SO2 mixtures, reactions that take place without the need for a high-radiation environment. We find that H2O and SO2 react to produce sulfur Oxyanions, such as bisulfite, that as much as 30% of the SO2 can be consumed through this reaction, and that the products remain in the ice when the temperature is lowered, indicating that these reactions are irreversible. Our results suggest that thermally-induced reactions can alter the chemistry at temperatures relevant to the icy satellites in the Jovian system.

Loeffler, Mark J.↗