In situ planetary mineralogy using simultaneous time resolved fluorescence and Raman spectroscopy

Micro-Raman spectroscopy is one of the primary methods of mineralogical analysis in the laboratory, and more recently in the field. Because of its versatility and ability to interrogate rocks in their natural form (Figure 1), it is one of the frontrunners for the next generation of in situ instruments designed to explore adiverse set of solar system bodies (e.g. Mars, Venus, the Moon, and other primitive bodies such as asteroids and the Martian moons Phobos and Deimos), as well as for pre-selection of rock and soil samples for cache and return missions

Response of a delta-doped charge-coupled device to low energy protons and nitrogen ions

We present the results of a study of the response of a delta-doped charge-coupled device (CCD) exposed to ions with energies less than 10 keV10keV. The study of ions in the solar wind, the majority having energies in the 1–5 keV1–5keV range, has proven to be vital in understanding the solar atmosphere and the near Earth space environment. Delta-doped CCD technology has essentially removed the dead layer of the silicon detector. Using the delta-doped detector, we are able to detect H+H+ and N+N+ ions with energies ranging from 1 to 10 keV1to10keV in the laboratory. This is a remarkable improvement in the low energy detection threshold over conventional solid-state detectors, such as those used in space sensors, one example being the solar wind ion composition spectrometer (SWICS) on the Advanced Composition Explorer spacecraft, which can only detect ions with energies greater than 30 keV30keV because of the solid-state detector’s minimum energy threshold. Because this threshold is much higher than the average energy of the solar wind ions, the SWICS instrument employs a bulky high voltage postacceleration stage that accelerates ions above the 30 keV30keV detection threshold. This stage is massive, exposes the instrument to hazardous high voltages, and is therefore problematic both in terms of price and its impact on spacecraft resources. Adaptation of delta-doping technology in future space missions may be successful in reducing the need for heavy postacceleration stages allowing for miniaturization of space-borne ion detectors.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/87896/2/053301_1.pd

Miniaturized time-resolved Raman spectrometer for planetary science based on a fast single photon avalanche diode detector array

We present recent developments in time-resolved Raman spectroscopy instrumentation and measurement techniques for in situ planetary surface exploration, leading to improved performance and identification of minerals and organics. The time-resolved Raman spectrometer uses a 532 nm pulsed microchip laser source synchronized with a single photon avalanche diode array to achieve sub-nanosecond time resolution. This instrument can detect Raman spectral signatures from a wide variety of minerals and organics relevant to planetary science while eliminating pervasive background interference caused by fluorescence. We present an overview of the instrument design and operation and demonstrate high signal-to-noise ratio Raman spectra for several relevant samples of sulfates, clays, and polycyclic aromatic hydrocarbons. Finally, we present an instrument design suitable for operation on a rover or lander and discuss future directions that promise great advancement in capability

Electron Irradiation and Thermal Processing of Mixed-ices of Potential Relevance to Jupiter Trojan Asteroids

In this work we explore the chemistry that occurs during the irradiation of ice mixtures on planetary surfaces, with the goal of linking the presence of specific chemical compounds to their formation locations in the solar system and subsequent processing by later migration inward. We focus on the outer solar system and the chemical differences for ice mixtures inside and outside the stability line for H_2S. We perform a set of experiments to explore the hypothesis advanced by Wong & Brown that links the color bimodality in Jupiter's Trojans to the presence of H_2S in the surface of their precursors. Non-thermal (10 keV electron irradiation) and thermally driven chemistry of CH_3OH–NH_3–H_2O ("without H_2S") and H_2S–CH_3OH–NH_3–H_2O ("with H_2S") ices were examined. Mid-IR analyses of ice and mass spectrometry monitoring of the volatiles released during heating show a rich chemistry in both of the ice mixtures. The "with H_2S" mixture experiment shows a rapid consumption of H_2S molecules and production of OCS molecules after a few hours of irradiation. The heating of the irradiated "with H_2S" mixture to temperatures above 120 K leads to the appearance of new infrared bands that we provisionally assign to SO_2 and CS. We show that radiolysis products are stable under the temperature and irradiation conditions of Jupiter Trojan asteroids. This makes them suitable target molecules for potential future missions as well as telescope observations with a high signal-to-noise ratio. We also suggest the consideration of sulfur chemistry in the theoretical modeling aimed at understanding the chemical composition of Trojans and KOBs

Visible Near-infrared Spectral Evolution of Irradiated Mixed Ices and Application to Kuiper Belt Objects and Jupiter Trojans

Understanding the history of Kuiper Belt Objects and Jupiter Trojans will help to constrain models of solar system formation and dynamical evolution. Laboratory simulations of a possible thermal and irradiation history of these bodies were conducted on ice mixtures while monitoring their spectral properties. These simulations tested the hypothesis that the presence or absence of sulfur explains the two distinct visible near-infrared spectral groups observed in each population and that Trojans and KBOs share a common formation location. Mixed ices consisting of water, methanol, and ammonia, in mixtures both with and without hydrogen sulfide, were deposited and irradiated with 10 keV electrons. Deposition and initial irradiation were performed at 50 K to simulate formation at 20 au in the early solar system, then heated to Trojan-like temperatures and irradiated further. Finally, irradiation was concluded and resulting samples were observed during heating to room temperature. Results indicated that the presence of sulfur resulted in steeper spectral slopes. Heating through the 140–200 K range decreased the slopes and total reflectance for both mixtures. In addition, absorption features at 410, 620, and 900 nm appeared under irradiation, but only in the H_2S-containing mixture. These features were lost with heating once irradiation was concluded. While the results reported here are consistent with the hypothesis, additional work is needed to address uncertainties and to simulate conditions not included in the present work

Complex organosulfur molecules on comet 67P: Evidence from the ROSINA measurements and insights from laboratory simulations.

The ROSINA (Rosetta Orbiter Spectrometer for Ion and Neutral Analysis) instrument aboard the Rosetta mission revolutionized our understanding of cometary material composition. One of Rosetta's key findings is the complexity of the composition of comet 67P/Churyumov-Gerasimenko. Here, we used ROSINA data to analyze dust particles that were volatilized during a dust event in September 2016 and report the detection of large organosulfur species and an increase in the abundances of sulfurous species previously detected in the coma. Our data support the presence of complex sulfur-bearing organics on the surface of the comet. In addition, we conducted laboratory simulations that show that this material may have formed from chemical reactions that were initiated by the irradiation of mixed ices containing H2S. Our findings highlight the importance of sulfur chemistry in cometary and precometary materials and the possibility of characterizing organosulfur materials in other comets and small icy bodies using the James Webb Space Telescope

Electron Irradiation and Thermal Processing of Mixed-ices of Potential Relevance to Jupiter Trojan Asteroids

In this work we explore the chemistry that occurs during the irradiation of ice mixtures on planetary surfaces, with the goal of linking the presence of specific chemical compounds to their formation locations in the solar system and subsequent processing by later migration inward. We focus on the outer solar system and the chemical differences for ice mixtures inside and outside the stability line for H_2S. We perform a set of experiments to explore the hypothesis advanced by Wong & Brown that links the color bimodality in Jupiter's Trojans to the presence of H_2S in the surface of their precursors. Non-thermal (10 keV electron irradiation) and thermally driven chemistry of CH_3OH–NH_3–H_2O ("without H_2S") and H_2S–CH_3OH–NH_3–H_2O ("with H_2S") ices were examined. Mid-IR analyses of ice and mass spectrometry monitoring of the volatiles released during heating show a rich chemistry in both of the ice mixtures. The "with H_2S" mixture experiment shows a rapid consumption of H_2S molecules and production of OCS molecules after a few hours of irradiation. The heating of the irradiated "with H_2S" mixture to temperatures above 120 K leads to the appearance of new infrared bands that we provisionally assign to SO_2 and CS. We show that radiolysis products are stable under the temperature and irradiation conditions of Jupiter Trojan asteroids. This makes them suitable target molecules for potential future missions as well as telescope observations with a high signal-to-noise ratio. We also suggest the consideration of sulfur chemistry in the theoretical modeling aimed at understanding the chemical composition of Trojans and KOBs

Visible Near-infrared Spectral Evolution of Irradiated Mixed Ices and Application to Kuiper Belt Objects and Jupiter Trojans

Understanding the history of Kuiper Belt Objects and Jupiter Trojans will help to constrain models of solar system formation and dynamical evolution. Laboratory simulations of a possible thermal and irradiation history of these bodies were conducted on ice mixtures while monitoring their spectral properties. These simulations tested the hypothesis that the presence or absence of sulfur explains the two distinct visible near-infrared spectral groups observed in each population and that Trojans and KBOs share a common formation location. Mixed ices consisting of water, methanol, and ammonia, in mixtures both with and without hydrogen sulfide, were deposited and irradiated with 10 keV electrons. Deposition and initial irradiation were performed at 50 K to simulate formation at 20 au in the early solar system, then heated to Trojan-like temperatures and irradiated further. Finally, irradiation was concluded and resulting samples were observed during heating to room temperature. Results indicated that the presence of sulfur resulted in steeper spectral slopes. Heating through the 140–200 K range decreased the slopes and total reflectance for both mixtures. In addition, absorption features at 410, 620, and 900 nm appeared under irradiation, but only in the H_2S-containing mixture. These features were lost with heating once irradiation was concluded. While the results reported here are consistent with the hypothesis, additional work is needed to address uncertainties and to simulate conditions not included in the present work

Production of Sulfur Allotropes in Electron Irradiated Jupiter Trojans Ice Analogs

In this paper, we investigate sulfur chemistry in laboratory analogs of Jupiter Trojans and Kuiper Belt Objects (KBOs). Electron irradiation experiments of CH_3OH–NH_3–H_2O and H_2S–CH_3OH–NH_3–H_2O ices were conducted to better understand the chemical differences between primordial planetesimals inside and outside the sublimation line of H_2S. The main goal of this work is to test the chemical plausibility of the hypothesis correlating the color bimodality in Jupiter Trojans with sulfur chemistry in the incipient solar system. Temperature programmed desorption (TPD) of the irradiated mixtures allows the detection of small sulfur allotropes (S_3 and S_4) after the irradiation of H2S containing ice mixtures. These small, red polymers are metastable and could polymerize further under thermal processing and irradiation, producing larger sulfur polymers (mainly S_8) that are spectroscopically neutral at wavelengths above 500 nm. This transformation may affect the spectral reflectance of Jupiter Trojans in a different way compared to KBOs, thereby providing a useful framework for possibly differentiating and determining the formation and history of small bodies. Along with allotropes, we report the production of organo-sulfur molecules. Sulfur molecules produced in our experiment have been recently detected by Rosetta in the coma of 67P/Churyumov–Gerasimenko. The very weak absorption of sulfur polymers in the infrared range hampers their identification on Trojans and KBOs, but these allotropes strongly absorb light at UV and Visible wavelengths. This suggests that high signal-to-noise ratio UV–Vis spectra of these objects could provide new constraints on their presence