Calcium Perchlorate Research Articles

The influence of oxychlorine phases on the flash pyrolysis of polycyclic aromatic hydrocarbons and implications for mars

A variety of chlorine-bearing hydrocarbons have been detected in the chemical analyses of soil and rock samples performed on Mars with the GCMS instruments onboard the Viking landers and the SAM instrument suite onboard the Curiosity rover. These aromatic and aliphatic chlorohydrocarbons are most likely produced by chemical reactions between salts (e.g., perchlorates, chlorates) and organic molecules of martian origin either during the thermal processing of the samples in flight or generated through radiation processes happening in Mars’ near surface. To understand the influence of salts on the organic molecules during pyrolysis and identify the potential precursors of the chlorohydrocarbons detected on Mars, we performed a systematic study and pyrolyzed three polycyclic aromatic hydrocarbons (PAHs)—naphthalene, phenanthrene, and benzanthracene—in the presence of six perchlorate and chlorate salts that have been identified or are most likely present on Mars—calcium perchlorate, iron perchlorate, sodium perchlorate, magnesium perchlorate, sodium chlorate, and potassium chlorate. Iron perchlorate had the strongest (oxy)chlorination power on the PAHs of all the salts tested whereas magnesium perchlorate and potassium chlorate were the most destructive ones. Despite the presence of these caustic salts, PAHs were highly chemically and thermally stable, suggesting they would likely be detectable natively if present in a martian sample. In addition, chlorohydrocarbons that are characteristic of the parent PAH were formed and could be used to help identify the nature of a PAH. This investigation underlines that PAHs could be the precursors of aromatic chlorohydrocarbons detected on Mars, but a definitive identification will require the detection of the parent PAHs and their respective pyrolyzates, molecules that were not yet detected on Mars likely because of the flight operating constraints of the SAM instrument.

Synthesis, Structural Characterization, Hirschfeld Surface Analysis, Density Functional Theory, and Photocatalytic CO2 Reduction Activity of a New Ca(II) Complex with a Bis-Schiff Base Ligand.

A new bis-Schiff base (L) Ca(II) complex, CaL, was synthesized by the reaction of calcium perchlorate tetrahydrate, 1,3-diamino-2-hydroxypropane, and 2-formyl phenoxyacetic acid in an ethanol-water (v:v = 2:1) solution and characterized by IR, UV-vis, TG-DTA, and X-ray single crystal diffraction analysis. The structural analysis indicates that the Ca(II) complex crystallizes in the monoclinic system, space group P121/n1, and the Ca(II) ions are six-coordinated with four O atoms (O8, O9, O11, O12, or O1, O2, O4, O6) and two N atoms (N1, N2, or N3, N4) of one bis-Schiff base ligand. The Ca(II) complex forms a tetramer by intermolecular O-H…O hydrogen bonds. The tetramer units further form a three-dimensional network structure by π-π stacking interactions of benzene rings. The Hirschfeld surface of the Ca(II) complex shows that the H…H contacts represent the largest contribution (41.6%) to the Hirschfeld surface, followed by O…H/H…O and C…H/H…C contacts with contributions of 35.1% and 18.1%, respectively. To understand the electronic structure of the Ca(II) complex, the DFT calculations were carried out. The photocatalytic CO2 reduction test of the Ca(II) complex exhibited a yield of 47.9 μmol/g (CO) and a CO selectivity of 99.3% after six hours.

Novel Solid Propellants Enabled Through In Situ Martian Perchlorates

With evidence for the native perchlorates existing in the Martian regolith, this paper examines the feasibility and performance of propellants formed from perchlorate salts reported to be present on Mars. Thermochemistry calculations indicate that the Martian perchlorate-based propellants provide less theoretical specific impulse than AP composite propellants but could still be viable propellants. Three propellants made from Martian perchlorates were manufactured and compared to a control propellant with AP as the oxidizer. Deflagration experiments were performed to obtain the burning rates as a function of pressure, with results comparable to AP baseline propellant. The propellant energy density was evaluated through bomb calorimetry. The propellant formulation with a similar perchlorate mixture to the distribution found in Martian soil was then subjected to thermal analysis, elemental analysis, and sensitivity testing to examine its combustion behavior and suitability for handling. Further characterization and development work would be needed to field these propellants, but initial conclusions indicate an in situ blend of calcium perchlorate and magnesium perchlorate could serve as a novel oxidizer for future safe, high-performing, and economical solid propellant rocket motors, offering an alternative to most current proposals for Martian ascent vehicle architectures.

Safe Explosion Works Promoted by 2D Graphene Structures Produced under the Condition of Self-Propagation High-Temperature Synthesis

The paper presents the results of a study on the effectiveness of few-layer graphene synthesized under SHS conditions from lignin as a modifying additive in creating composite pyrotechnic complexes based on porous silicon and calcium perchlorate. It was found that the addition of few-layer graphene (20–30 wt. %) could significantly increase the probability of the ignition of pyrotechnic compositions by laser diode (infrared) radiation (wavelength of 976 nm and power of 15 MW/m2) compared to the initial pyrotechnic compositions. Using few-layer graphene also leads to a sharp increase in sensitivity to infrared laser radiation and the initiation of explosive transformations in retrofitted pyrotechnic compositions compared to the initial pyrotechnic compositions. Due to the high productivity and low cost of the technique for synthesizing few-layer graphene, the use of composite pyrotechnic compositions modified with few-layer graphene is profitable in the actual industry. A phenomenological model of the formation mechanism of 2D graphene structures under the conditions of the SHS process is proposed.

Thermodynamic modeling of calcium or magnesium chloride, chlorate, and perchlorate ternary mixtures deliquescence at Mars-relevant temperatures

The definition of habitability on Mars is intimately linked to the stability of liquid water on the surface or near sub-surface. Brines provide the best pathway to stabilize liquid water, and form through deliquescence where a solid salt crystal transitions into an aqueous solution when exposed to a humid atmosphere. In a typical brine controlled by temperature and water relative humidity, ternary mixtures represent the best potential liquid brines. Here we modeled the deliquescence relative humidity (DRH) and the eutonic relative humidity (RH) of ternary salt mixtures. Chloride, chlorate, and perchlorate were modeled with either calcium or magnesium as the cation at temperatures ranging from 223 to 273 K. For the calcium ternary mixtures, the main salt composition precipitating at the DRH was dominated by calcium chloride, and by magnesium perchlorate in the magnesium ternary system. The hydration state of the precipitating salts systematically increased as temperature decreased. The eutonic RH for the calcium mixtures ranged from 14.24% at 273 K and increased to 43.54% by the coldest temperature of 223 K. The eutonic RH for the magnesium mixtures was significantly higher than the calcium counterpart, at 49.76% at 273 K and increased to 53.09% by 223 K. Calcium perchlorate was the predominate eutonic precipitate for the calcium mixtures, and magnesium chlorate for the magnesium mixtures., This study shows that ternary mixtures bring a slight improvement to the stability of brines on Mars compared to single salts or binary mixtures.

Effects of UV and Calcium Perchlorates on Uracil Deposited on Strontium Fluoride Substrates at Mars Pressure and Temperature.

Organic matter is actively searched on Mars with current and future space missions as it is a key to detecting potential biosignatures. Given the current harsh environmental conditions at the surface of Mars, many organic compounds might not be preserved over a long period as they are exposed to energetic radiation such as ultraviolet light, which is not filtered above 190 nm by the martian atmosphere. Moreover, the presence of strong oxidizing species in the regolith, such as perchlorate salts, might enhance the photodegradation of organic compounds of astrobiological interest. Because current space instruments analyze samples collected in the upper surface layer, it is necessary to investigate the stability of organic matter at the surface of Mars. Previous experimental studies have shown that uracil, a molecule relevant to astrobiology, is quickly photolyzed when exposed to UV radiation under the temperature and pressure conditions of the martian surface with an experimental quantum efficiency of photodecomposition (φexp) of 0.30 ± 0.26 molecule·photon-1. Moreover, the photolysis of uracil leads to the formation of more stable photoproducts that were identified as uracil dimers. The present work aims to characterize the additional effect of calcium perchlorate detected on Mars on the degradation of uracil. Results show that the presence of calcium perchlorate enhances the photodecomposition of uracil with φexp = 12.3 ± 8.3 molecule·photon-1. Although some of the photoproducts formed during these experiments are common to those formed from pure uracil only, the Fourier transformation infrared (FTIR) detection of previously unseen chemical functions such as alkyne C ≡ C or nitrile C ≡ N has shown that additional chemical species are formed in the presence of calcium perchlorate in the irradiated sample. This implies that the effect of calcium perchlorate on the photolysis of uracil is not only kinetic but also related to the nature of the photoproducts formed.

Laboratory Studies of Brine Growth Kinetics Relevant to Deliquescence on Mars

Although previous studies have shown that the near-surface environmental conditions on Mars may permit salt deliquescence and therefore brine production, there is significant uncertainty in the kinetics of the process. Indeed, experimental studies have shown that deliquescence is either very rapid or too slow to be relevant to Mars. To resolve this uncertainty, we performed laboratory experiments to investigate the growth rate of Mars-relevant calcium perchlorate brines over a range of temperatures (184–273 K) and water vapor pressures (0.2–220 Pa). We show that the brine growth is faster at higher water vapor pressures and lower temperatures and for smaller particles. From our data, we determined a temperature-dependent net uptake coefficient for gas phase water molecules colliding with a perchlorate brine surface in the range of 3.8 × 10−4 at 185 K to 4.2 × 10−6 at 273 K. These values suggest that deliquescence on Mars is likely to be slow even when conditions thermodynamically permit a brine to form. We find that along the Curiosity rover traverse at Gale Crater, the near-surface conditions would only allow particles <1 μm to fully deliquesce over a typical sol. At the higher-latitude Phoenix landing site, deliquescence may be 30% faster due to the higher water vapor pressures, but still, only micron-scale salt grains or coatings would be expected to deliquesce during a typical sol. These results suggest that brines formed via deliquescence on the surface of Mars are likely only present on small scales that may not be readily detected using conductivity or imaging techniques.

Partially‐Saturated Brines Within Basal Ice or Sediments Can Explain the Bright Basal Reflections in the South Polar Layered Deposits

AbstractStrong radar reflections have been previously mapped at the base of the Martian South Polar Layered Deposits. Here, we analyze laboratory measurements of dry and briny samples to determine the cause of this radar return. We find that liquid vein networks consisting of brines at the grain boundaries of ice crystals can greatly enhance the electrical conductivity, thereby causing strong radar reflections. A brine concentration of 2.7–6.0 vol% in ice is sufficient to match the electrical properties of the basal reflection as observed by Mars Advanced Radar for Subsurface and Ionospheric Sounding (MARSIS). When brine is mixed with sediments, the brine‐ice mixture in the pores must be 2–5 times more concentrated in salt, increasing the brine concentration to 6.3–29 vol%. Our best fit of the median observed MARSIS value suggests a salt‐bulk sample concentration of ∼6 wt%. Thus, salt enhancement mechanisms on the order of a magnitude greater than the Phoenix landing site are needed. To form brine, the basal reflector must reach a temperature greater than the eutectic temperature of calcium perchlorate of 197.3 ± 0.2 K, which may be possible if more complex thermal modeling is assumed. Colder metastable brines are possible, but stability over millions of years remains unclear. Conversely, gray hematite with a concentration of 33.2–59.0 vol% possess electrical properties that could cause the observed radar returns, but require concentrations 2–3 times larger than anywhere currently detected. We also argue that brines mixed with high‐surface‐area sediments, or dry red hematite, jarosite, and ilmenite cannot create the observed radar returns at low temperatures.

A possible perchlorate-enabled mechanism for forming thick near surface excess ice layers; in the Amazonian regolith of Mars

We use the freezing point depressing magnesium and calcium perchlorates in Martian regolith to redistribute ground ice by residual liquid water migration following the initial emplacement of ground ice by vapour deposition. This residual liquid water is moved by forces generated by periodic surface temperatures that decay with depth in conjunction with the geothermal vertical temperature gradient. We examine the period means of the bulk water speeds with depth and the mean divergence of the bulk water speeds, which relates to the rate of change in ice content in the regolith. Silt and clay rich regoliths behave differently. In silty regolith, for the short 1.88 a period and for longer 50 ka (precession) and 120 ka (obliquity) temperature cycles, there is a mean movement of liquid perchlorate aqueous solution that results in formation of near surface excess ice layers. The excess ice formed by the seasonal 1.88a period is confined at high latitudes to the upper meter of regolith. For the longer periods, there is a well-defined surface temperature region where near surface thick (≥40 m) excess ice layers form; (from 192 K to 210 K). For mean surface temperatures <192 K no near surface thick excess ice layers formed, but deeper layers are predicted and followed. The formation of excess ice layers in silt near the surface is controlled by the relationship between the temperature cycles, geothermal gradient and the eutectic temperature of the perchlorate (eg. ~198 K for Ca and ~ 205 K for Mg perchlorate). At a given depth if the periodic temperature is below the eutectic then there is nearly no liquid water left and what there is has much higher viscosity. The sudden change in the liquid water amount and viscosity with temperature generates net average water speeds in silts that are two orders larger than in clays.

Experimental Constraints on Deliquescence of Calcium Perchlorate Mixed with a Mars Regolith Analog

Hygroscopic salts within the Martian regolith may actively participate in the near-surface water cycle by exchanging water vapor via solid-state salt hydration and deliquescence. To elucidate this process, experimental work has constrained the phase diagram of Mars-relevant salts and the stability of the resultant brines. However, salt interactions with a Mars-like regolith, which itself can exchange water vapor with the atmosphere via adsorption, has not yet been well explored. Here, to better understand water exchange with a salty Mars-like regolith and, particularly, the potential to form brines, we have conducted a series of experiments using JSC Mars-1 regolith simulant mixed with calcium perchlorate in a Mars simulation chamber at a temperature <5°C and a relative humidity <20%. During the experiments, we measured the sample mass, as well as the temperature and relative humidity of the sample and the chamber. We found that the water uptake of a salty Mars-like regolith is about twice as fast as that of a salt-free regolith. Furthermore, we found evidence to suggest that deliquescence occurred; however, not all the salt within the sample may have entered solution. The amount of water in solution was small and did not lead to regolith darkening. Our results suggest that, under the tested experimental conditions, salt deliquescence and regolith adsorption can occur simultaneously.

Limited Stability of Multicomponent Brines on the Surface of Mars

The formation and stability of brines on the surface of present-day Mars remains an important question to resolve the astrobiological potential of the red planet. Although modeling and experimental work have constrained the processes controlling the stability of single-salt brines exhibiting low freezing temperatures, such as calcium perchlorate, the Martian regolith is far more complex because multiple salts coexist in various concentrations, leading to brines whose behavior remains untested. Here we modeled the stability of complex brines of compositions determined from the Phoenix lander’s Wet Chemistry Laboratory. We find that such brines would form in equilibrium with sodium and magnesium perchlorates, chlorides, and calcium chlorate, but never calcium perchlorate, which has been widely considered as the most likely to produce brines on Mars. Furthermore, we find that only chlorate-rich brines can potentially remain liquid, for small periods of time, at temperatures compatible with those measured by the Phoenix lander. Therefore, liquid brines remain overly unstable under present-day Martian conditions and are unlikely to contribute to surface geomorphological activity, such as recurring slope lineae. In these conditions, of cold and salty brines, the present-day Martian surface remains highly unhabitable.

Calcium Based All-Organic Dual-Ion Batteries with Stable Low Temperature Operability.

In response to the application requirements of secondary batteries at low temperature, an all-organic dual-ion battery with calcium perchlorate contained acetonitrile as the electrolyte (CAN-ODIB) is fabricated in this work. The electrochemical energy is stored in CAN-ODIB via the association and disassociation of calcium and perchlorate ions in perylene diimide-ethylene diamine/carbon black composite based anode and polytriphenylamine based cathode with highly reversible redox states. Benefiting from the energy storage mechanism, CAN-ODIB exhibits excellent electrochemical performances in tests with the temperature ranging from 25 to -50°C. Especially, CAN-ODIB at -50°C reserves ≈61% of the capacity at 25°C (83.4mA h g-1 ) with the current density of 0.2 A g-1 . CAN-ODIB also shows excellent cycling stability at low temperature by retaining 90.3% of the initial capacity at 1.0 A g-1 after 450 charge-discharge cycles at -30°C. The impedance analysis of CAN-ODIB at different temperatures indicates that the low temperature performance of CAN-ODIB depends more on the electrode materials than the electrolyte, which provides the important guidance for the further design of secondary batteries operable at low temperatures.

Deliquescence probability maps of Mars and key limiting factors using GCM model calculations

There may be a chance of small-scale ephemeral liquid water formation on present day Mars, even though the current climate does not support the existence of larger bodies of water. Through a process called deliquescence, hygroscopic salts can enter solution by absorbing water vapor directly from the atmosphere. Due to the absence of in-situ deliquescence experiments so far, the most reliable way to forecast deliquescence is through atmospherical modeling, however, the locations and times when salty liquid water could emerge are not yet well known. In this paper we present our results of likely brine formation on Mars, their proposed locations and seasons, as well as the possible limiting factors. For our calculations we used the data of Laboratoire de M\'et\'eorologie Dynamique Mars General Circulation Model version 5. The results show that from L$_s$ 35$^\circ$ - L$_s$ 160$^\circ$, between 9 PM and 11 PM there is a good chance for calcium perchlorate deliquescence above 30$^\circ$ N, while in this zone the ideal regions are concentrated mostly to Acidalia Planitia and Utopia Planitia between 1 AM and 3 AM. We found that in the Southern Hemisphere, between L$_s$ 195$^\circ$ and L$_s$ 320$^\circ$, there is a noticeable, but weaker band in the vicinity of 60$^\circ$ S, and both Argyre Planitia and Hellas Planitia show some chance for brine formation. According to our statistics the key limiting factor of deliquescence could be relative humidity in most cases. Our results suggest that during summer -- early fall seasons, there could be deliquescence in both hemispheres in specific areas from the late evening until the early morning hours. There are only few studies detailing the geological and temporal distribution of brine formation through deliquescence, thus this work could be used as a good guide for future landing site analysis or in choosing a specific location for further research.

Atmospheric, Geomorphological, and Compositional Analysis of Martian Asimov and Hale Craters: Implications for Recurring Slope Lineae

Recurring slope lineae (RSL) are small, dark, seasonal albedo features lengthening down “warm” Martian steep slopes. Their origin has been attributed to both liquid and dry processes, hence representing one of the major open science questions on present day Mars. In the present study, we report a catalog of previous literature and newly added RSL sites making a total of 940 sites globally on Mars along with the detailed geological and compositional investigation of the Hale and Asimov craters with their RSL features. We also estimate temperature and atmospheric water abundances in the study area, which are two of the main factors to explain the origin and formation of RSL. The study found that the Asimov crater’s local temperatures are high enough to allow either the melting of brines or deliquescence of calcium perchlorate and other salts during the HiRISE observation period and found the water vapor column to be nearly five times higher than those measured “before RSL appearance.” This supports the theory of deliquescence as one of the mechanisms for the regolith-atmosphere interaction and RSL formation in the studied crater, which suggests that minerals absorb moisture from the environment until the minerals dissolve in the absorbed water and yield a solution. We also used compact reconnaissance imaging spectrometer for Mars–derived browse products for a compositional study associated with RSL features hosting craters and surface characteristics of Mars.

Influence of Calcium Perchlorate on the Search for Martian Organic Compounds with MTBSTFA/DMF Derivatization.

N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide (MTBSTFA), mixed with the solvent N,N-dimethylformamide (DMF), is used as a derivatizing reagent by the Sample Analysis at Mars (SAM) experiment onboard NASA's Curiosity rover and will soon be utilized by the Mars Organic Molecule Analyzer experiment onboard the ESA/Roscosmos Rosalind Franklin rover. The pyrolysis products of MTBSTFA, DMF, and the MTBSTFA/DMF mixtures, obtained at different temperatures, were analyzed. Two different pyrolysis modes were studied, flash pyrolysis and ramp pyrolysis (35°C/min), to evaluate the potential influence of the sample heating speed on the production of products in space chromatographs. The effect of the presence of calcium perchlorate on the pyrolysis products of MTBSTFA/DMF was also studied to ascertain the potential effect of perchlorate species known to be present at the martian surface. The results show that MTBSTFA/DMF derivatization should be applied below 300°C when using flash pyrolysis, as numerous products of MTBSTFA/DMF were formed at high pyrolysis temperatures. However, when an SAM-like ramp pyrolysis was applied, the final pyrolysis temperature did not appear to influence the degradation products of MTBSTFA/DMF. All products of MTBSTFA/DMF pyrolysis are listed in this article, providing a major database of products for the analysis of martian analog samples, meteorites, and the in situ analysis of martian rocks and soils. In addition, the presence of calcium perchlorate does not show any obvious effects on the pyrolysis of MTBSTFA/DMF: Only chloromethane and TBDMS-Cl (chloro-tertbutyldimethylsilane) were detected, whereas chlorobenzene and other chlorine-bearing compounds were not detected. However, other chlorine-bearing compounds were detected after pyrolysis of the Murchison meteorite in the presence of calcium perchlorate. This result reinforces previous suggestions that chloride-bearing compounds could be reaction products of martian samples and perchlorate.

Structural Flexibility of Cyclosporine A Is Mediated by Amide Cis-Trans Isomerization and the Chameleonic Roles of Calcium.

Falling outside of Lipinski's rule of five, macrocyclic drugs have accessed unique binding sites of their target receptors unreachable by traditional small molecules. Cyclosporin(e) A (CycA), an extensively studied macrocyclic natural product, is an immunosuppressant with undesirable side effects such as electrolytic imbalances. In this work, a comprehensive view on the conformational landscape of CycA, its interactions with Ca2+, and host-guest interactions with cyclophilin A (CypA) is reported through exhaustive analyses that combine ion-mobility spectrometry-mass spectrometry (IMS-MS), nuclear magnetic resonance (NMR) spectroscopy, distance-geometry modeling, and NMR-driven molecular dynamics. Our IMS-MS data show that CycA can adopt extremely compact conformations with significantly smaller collisional cross sections than the closed conformation observed in CDCl3. To adopt these conformations, the macrocyclic ring has to twist and bend via cis-trans isomerization of backbone amides, and thus, we termed this family of structures the "bent" conformation. Furthermore, NMR measurements indicate that the closed conformation exists at 19% in CD3OD/H2O and 55% in CD3CN. However, upon interacting with Ca2+, in addition to the bent and previously reported closed conformations of free CycA, the CycA:Ca2+ complex is open and has all-trans peptide bonds. Previous NMR studies using calcium perchlorate reported only the closed conformation of CycA (which contains one cis peptide bond). Here, calcium chloride, a more biologically relevant salt, was used, and interestingly, it helps converting the cis-MeLeu9-MeLeu10 peptide bond into a trans bond. Last, we were able to capture the native binding of CycA and CypA to give forth evidence that IMS-MS is able to probe the solution-phase structures of the complexes and that the Ca2+:CycA complex may play an essential role in the binding of CycA to CypA.

Influence of Calcium Perchlorate on the Search for Organics on Mars with Tetramethylammonium Hydroxide Thermochemolysis.

The Mars Organic Molecule Analyzer (MOMA) and Sample Analysis at Mars (SAM) instruments onboard the Exomars 2022 and Mars Science Laboratory rovers, respectively, are capable of organic matter detection and differentiating potentially biogenic from abiotic organics in martian samples. To identify organics, both these instruments utilize pyrolysis-gas chromatography coupled to mass spectrometry, and the thermochemolysis agent tetramethylammonium hydroxide (TMAH) is also used to increase organic volatility. However, the reactivity and efficiency of TMAH thermochemolysis are affected by the presence of calcium perchlorate on the martian surface. In this study, we determined the products of TMAH pyrolysis in the presence and absence of calcium perchlorate at different heating rates (flash pyrolysis and SAM-like ramp pyrolysis with a 35°C·min-1 heating rate). The decomposition mechanism of TMAH pyrolysis in the presence of calcium perchlorate was studied by using stepped pyrolysis. Moreover, the effect of calcium perchlorate (at Mars-relevant concentrations) on the recovery rate of fatty acids with TMAH thermochemolysis was studied. Results demonstrate that flash pyrolysis yields more diversity and greater abundances of TMAH thermochemolysis products than does the SAM-like ramp pyrolysis method. There is no obvious effect of calcium perchlorate on TMAH degradation when the [ClO4-] is lower than 10 weight percent (wt %). Most importantly, the presence of calcium perchlorate does not significantly impact the recovery rate of fatty acids with TMAH thermochemolysis under laboratory conditions, which is promising for the detection of fatty acids via TMAH thermochemolysis with the SAM and MOMA instruments on Mars.

Laser Initiation of Energy-Saturated Composites Based on Nanoporous Silicon

The results of experiments on laser initiation of explosive transformations in energy-saturated composites based on nanoporous silicon have been presented. Calcium perchlorate has been used as an oxidizer. It has been shown that the additive of graphene-like powder material (20–30) wt % in the energy-saturated composite increases its sensitivity to infrared laser radiation and excites rapid exothermic reactions in it.

Challenging the agricultural viability of martian regolith simulants

As human space exploration extends farther from Earth, the cost and risk of resupplying a mission increases substantially. In situ resource utilization (ISRU) is the prospecting, extraction, storage, and exploitation of existing resources at the crew location, reducing cost and risk. Crucial to the development of ISRU solutions is the accurate characterization and modeling of regolith for a variety of applications, including as a substrate for food production at lunar or Martian sites. Previous studies have established the capacity of specific regolith simulants to support the growth of a variety of plants in the short term. However, the mineralogical and physical accuracy of these simulants as proxies for the sites on Mars is debatable, and any conclusion drawn from studies with these simulants must be considered with some degree of caution. For the purpose of studying ISRU food production, we present a systematic effort to evaluate the utility of three different Martian Regolith Simulants (MRSs): JSC-Mars-1A, Mars Mojave simulant (MMS), and Mars Global simulant (MGS-1). Our findings confirmed that none of these simulants are capable of supporting plant growth in the absence of nutrient supplementation. However, with the addition of a nutrient supplement, both JSC-Mars-1A and MMS were able to support the growth of both Arabidopsis thaliana and Lactuca sativa. However, the highly alkaline (pH > 9.0) MGS-1 simulant was unable to support growth even with additional nutrients. Acidification of MGS-1 nearly doubled the longevity of plants grown in this medium, suggesting this simulant may be further modified to eventually support plant growth as well. The addition of calcium perchlorate to each simulant, at concentrations intended to mimic those observed on the surface of Mars, rendered each simulant incapable of supporting plant growth, regardless of nutrient supplementation. These findings underscore that ISRU food solutions are likely at a lower technological readiness level than previously thought. We discuss these findings in the context of future efforts to develop off-world agricultural systems, approaches to developing future MRSs, and the immediate need to address perchlorate contamination as well as nitrogen deficiency for regolith-based food production.

Influence of Calcium Perchlorate on Organics Under SAM‐Like Pyrolysis Conditions: Constraints on the Nature of Martian Organics

AbstractMost of the organics detected on Mars so far are aliphatic and aromatic organo‐chlorine compounds. The smallest were first identified by the thermal treatment of the solid samples by Viking in 1976; although at the time, they were attributed to contamination. Since 2012, a larger variety of structures have been identified by the Sample Analysis at Mars experiment aboard the Curiosity rover. Evidence suggests that the chlorohydrocarbons formed during pyrolysis of sedimentary materials. Laboratory experiments show that heating of samples containing oxychlorines, such as chlorates (ClO3−) and perchlorates (ClO4−), along with organic matter present at Mars' surface is the logical source of these compounds. Nevertheless, this discovery of indigenous organic matter in the Mars regolith raises important questions: How do the oxychlorines influence the pyrolysis of organics? What are the organics precursors of the organo‐chlorinated molecules detected on Mars? Is there a way to identify the parent molecules in a sample after pyrolysis? This paper presents the results of systematic laboratory experiments of the products formed during the pyrolysis of organic compounds from three chemical families—polycyclic aromatic hydrocarbons, amino acids, and carboxylic acids—in presence of calcium perchlorates. Results show that the polycyclic aromatic hydrocarbon parent molecules and most of the carboxylic acids are still detectable after pyrolysis in presence of calcium perchlorate and that the degradation and/or evolution of all parent molecules mostly depends on their chemical nature. In addition, we demonstrate that the chlorohydrocarbons detected on Mars by the Sample Analysis at Mars instrument could come from the three chemical families studied.