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NASA NTRS2017

Fe-Containing Allophane and Hisingerite Dissolution and Implications for Gale Crater, Mars

The mass-normalized dissolution rates measured in this study demonstrate that hisingerite and Fe-substituted allophane dissolve rapidly, much faster than crystalline phyllosilicates such as nontronite and kaolinite that have similar compositions. In addition, hisingerite dissolves more rapidly than allophane. Future work will focus on measuring dissolution rates at other pH values, so that dissolution rate laws for allophane and hisingerite can be derived. Results will be used to interpret data from Gale Crater. These initial experiments suggest that, if the liquid water present in Gale Crater was highly acidic, it was likely present for only a short time, allowing some amorphous soil-material similar to allophane to persist. Further experiments will enable us to constrain the timescales over which liquid water was present in Gale Crater and provide insight into its pH. This information is essential to assessing the potential habitability of ancient Mars.

Ralston, S. J.↗

NASA NTRSDate not supplied

Acid Alteration of Clay Minerals With Implication for Mars’ Surface Processes

The co-occurrence of phyllosilicates (clays) and sulfate stratigraphies at many locations on Mars are associated with a sharp change in surface conditions from neutral/alkaline pH during the Noachian (4.1-3.7 Ga) which favored the formation of clays to acidic conditions during the Hesperian (3.7-2.9 Ga) which favored the formation of sulfates. Yet, if these two contrasting geosystems were temporarily sequential, it is unknown how the Hesperian acidic conditions altered the previously formed clay units. We performed laboratory batch experiments to fingerprint the diagnostic features produced during interactions of Mars-analog clays and acidic solutions. Two clays, and silicon (IV) oxide, were reacted with solution of either sulfuric acid or filtered natural acid rock drainage (ARD) in plastic bottles. The solutions were adjusted at four pH values (1, 3, 5, and 7) and reacted at 4, 30, and 80°C for 3, 7, and 14 days. At the end of the experiments, the filtered supernatants were analyzed by ICP-MS while the solids were characterized by X-Ray Diffraction; Energy-Dispersive X-Ray Fluorescence analyses; Raman and Short-Wave Infrared spectroscopies and Scanning Electron Microscopy. Results show that the solution chemistry played a key role in the evolution of the clay-solution systems. In H2SO4 systems, the solution pH steadily increased due to partial clay dissolution with no secondary phase formation detected. Contrary, in the ARD systems, the pH decreased due to the ample presence of Fe which controlled both the reactivity of clays by the growth of protecting surface coatings and the solution pH by the precipitation of Fe nanophases; secondary phase detected included goethite, jarosite, gypsum, and siderite. These results indicate that, on Mars, the chemical interaction between clays and acidic solutions was complex and dependent on the solution chemistry. Acidic, sulfate-rich solutions have a high dissolution capacity and could have induced widespread clay disintegration. Notably, if Fe-rich ARD was involved, the clays on Mars could have remained stable during acidic Hesperian period due to formation of protective coatings. Comparison of our results with martian observations will be performed to determine how acidic conditions could potentially affect clays in sedimentary settings, including the Gale crater.

L. Lefticariu↗

NASA NTRS1982

Effects of environment on microhardness of magnesium oxide

Micro-Vickers hardness measurements of magnesium oxide single crystals were conducted in various environments. These environments included air, nitrogen gas, water, mineral oil with or without various additives, and aqueous solutions with various pH values. Indentations were made on the (100) plane with the diagonals of the indentation in the (100) direction. The results indicate that a sulfur containing additve in mineral oil increased hardness, a chlorine containing additive in mineral oil decreased hardness, and aqueous solutions of hydrogen chloride decreased hardness. Other environments were found to have little effect on hardness. Mechanically polished surfaces showed larger indentation creep than did as-cleaved surfaces.

Ishigaki, H.↗

NASA NTRS1986

Treatment for hydrazine-containing waste water solution

The treatment for waste solutions containing hydrazine is presented. The invention attempts oxidation and decomposition of hydrazine in waste water in a simple and effective processing. The method adds activated charcoal to waste solutions containing hydrazine while maintaining a pH value higher than 8, and adding iron salts if necessary. Then, the solution is aerated.

Yade, N.↗

NASA NTRS1988

Optical monitoring of protein crystal growth

The possibility of using various optical techniques for detecting the onset of nucleation in protein crystal growth was investigated. Direct microscopy, general metrologic techniques, light scattering, ultraviolet absorption, and interferometry are addressed along with techniques for determining pH value. The necessity for collecting basic data on the optical properties of the growth solution as a prerequisite to the evaluation of monitoring techniques is pointed out.

Choudry, A.↗

NASA NTRS1990

Generation rates and chemical compositions of waste streams in a typical crewed space habitat

A judicious compilation of generation rates and chemical compositions of potential waste feed streams in a typical crewed space habitat was made in connection with the waste-management aspect of NASA's Physical/Chemical Closed-Loop Life Support Program. Waste composition definitions are needed for the design of waste-processing technologies involved in closing major life support functions in future long-duration human space missions. Tables of data for the constituents and chemical formulas of the following waste streams are presented and discussed: human urine, feces, hygiene (laundry and shower) water, cleansing agents, trash, humidity condensate, dried sweat, and trace contaminants. Tables of data on dust generation and pH values of the different waste streams are also presented and discussed.

Wydeven, Theodore↗

NASA NTRS1991

Waste streams in a crewed space habitat

Wydeven, T.↗

NASA NTRS1993

Effect of iodine disinfectant source and water quality parameters on soluble iodine speciation

Investigations of iodine species distribution of various aqueous solutions of iodine disinfectants and water from equilibrated suspensions of triodide and pentaiodide resins were done at the University of Colorado for the Center for Space Environmental Health during 1992 and 1993. Direct measurements of three individual iodine species: I(-), I2 and I3(-), were made. In addition three measures of total titratable iodine species were used. It has been found that I2 and I3(-) solutions produce a significant fraction of the non-disinfecting species iodine I(-), ranging from 50 to 80% of added iodine, respectively, at pH values of approximately 5. Correspondingly, I2 solutions produce more than twice the concentration of disinfecting iodine species per mass iodine dose than I3(-) solutions. Both I(-) and I2 species were found in aqeuous extracts of pentaiodide resin, although no soluble species were detected with triiodide resin.

Silverstein, Joann↗

NASA NTRS1998

Studies of Protein Solution Properties Using Osmotic Pressure Measurements

Examination of the protein crystallization process involves investigation of the liquid and solid state and a protein's properties in these states. Liquid state studies such as protein self association in solution by light scattering methods or other methods have been used to examine a protein Is properties and therefore its crystallization process and conditions. Likewise can osmotic pressure data be used to examine protein properties and various published osmotic pressure studies were examined by us to correlate osmotic pressure to protein solution properties. The solution behavior of serum albumin, alpha - chymotrypsin, beta - lactoglobulin and ovalbumin was examined over a range of temperatures, pH values and different salt types and concentrations. Using virial expansion and a local composition model the non ideal solution behavior in form of the activity coefficients (thermodynamic) was described for the systems. This protein activity coefficient data was related to a protein's solubility behavior and this process and the results will be presented.

Agena, S.↗

NASA NTRS2004

Did the Pre-RNA World Rest Upon DNA Molecules?

The isolation of a DNA sequence that catalyzes the ligation of oligodeoxynucleotides via the formation of 3' - 5' phosphodiester linkage significance in selection experiments has been reported. Ball recently used this to discuss the possibility that natural DNA molecules may have formed in the primitive Earth leading to the origin of life. As noted by Ferris and Usher, if metabolic pathways evolved backwards, it could be argued that the biosynthesis of 2-deoxyribose from ribose suggests that RNA came from DNA. As summarized elsewhere, there are several properties of deoxyribose which could be interpreted to support the possibility that DNA-like molecules arose prior to the RNA world. For example, 2-deoxyribose is slightly more soluble than ribose (which may have been an advantage in a drying pool scenario), may have been more reactive under possible prebiotic conditions (it forms a nucleoside approx. 150 times faster than ribose with the alternative base urazole at 25 C), while it decomposes in solution (approximately 2.6 times more slowly than ribose at 100 C). Other advantages of DNA over RNA are that it has one fewer chiral center, has a greater stability at the 8.2 pH value of the current oceans, and does not has the 2'5' and 3'5' ambiguity in polymerizations. Yet, there is strong molecular biological and biochemical evidence that RNA was featured in the biology well before the last common ancestor. The presence of sugar acids, including both ribo- and deoxysugar acids, in the 4.6 Ga old Murchison meteorite suggest that both may have been available in the primitive Earth, derived from the accretion of extraterrestrial sources and/or from endogenous processes involving formaldehyde and its derivatives. However, the abiotic synthesis of deoxyribose, ribose, and other sugars from glyceraldehyde and acetaldehyde under alkaline conditions is inefficient and unespecific. Although sugars are labile compounds, the role of cyanamide or borate minerals in the stabilization of the cyclic forms of ribose and other pentoses has recently been demonstrated. Nonetheless, the assumption either RNA or DNA was the first genetic material needs to be supplemented by laboratory models demonstrating that the prebiotic synthesis of activated beta-D-(deoxy)ribonucleotides and their polymers was feasible. As of today such evidence is lacking, and there is no convincing synthesis of any nucleotide, since all model experiments produce complex mixtures of products in which there is no preferential synthesis of chiral D-nucleotides. This strongly suggests that both DNA and RNA may have been preceded by pairing structures much simpler than extant nucleic acids. It is doubtful that DNA molecules, or indeed other (de0xy)ribofuranoid oligonucleotides formed the basis of these as yet undescribed pre-RNA worlds.

Lazcano, Antonio↗

NASA NTRS2000

Extremophiles in astrobiology: per Ardua ad Astra

As we consider the possibilities of finding life on other planets, it behooves us to evaluate what we know about the limits for life on planet Earth. In our continued exploration of Earth, we are finding microbes in a variety of unexpected habitats. In geothermal hot springs, we have discovered organisms thriving at temperatures near the boiling point of water and at pH values down to 0.5; in the deepest parts of the oceans, those that grow optimally at pressures above 1000 bars and die at pressures below 500 bars; and at the poles, those that grow below the freezing point of water and die at temperatures above 10 degrees C. All of these organisms are living proof that the biochemical "machinery" of life can be adapted to conditions that, from our anthropocentric perspective, appear to be extreme. By studying the molecular adaptations of extremophiles, we begin to identify the critical cellular components that expand the envelope for life. As an example, I will discuss what we have learned about the role of the proteins we call "heat shock proteins" in pushing the upper temperature limit of life and how our studies have provided a new perspective on the function of these proteins.

Chaperonin 60/physiology↗

NASA NTRS1984

Cell wall pH and auxin transport velocity

According to the chemiosmotic polar diffusion hypothesis, auxin pulse velocity and basal secretion should increase with decreasing cell wall pH. Experiments were designed to test this prediction. Avena coleoptile sections were preincubated in either fusicoccin (FC), cycloheximide, pH 4.0, or pH 8.0 buffer and subsequently their polar transport capacities were determined. Relative to controls, FC enhanced auxin (IAA) uptake while CHI and pH 8.0 buffer reduced IAA uptake. Nevertheless, FC reduced IAA pulse velocity while cycloheximide increased velocity. Additional experiments showed that delivery of auxin to receivers is enhanced by increased receiver pH. This phenomenon was overcome by a pretreatment of the tissue with IAA. Our data suggest that while acidic wall pH values facilitate cellular IAA uptake, they do not enhance pulse velocity or basal secretion. These findings are inconsistent with the chemiosmotic hypothesis for auxin transport.

Plant Growth Regulators/metabolism↗

NASA NTRS1999

Water transport by the bacterial channel alpha-hemolysin

This study is an investigation of the ability of the bacterial channel alpha-hemolysin to facilitate water permeation across biological membranes. alpha-Hemolysin channels were incorporated into rabbit erythrocyte ghosts at varying concentrations, and water permeation was induced by mixing the ghosts with hypertonic sucrose solutions. The resulting volume decrease of the ghosts was followed by time-resolved optical absorption at pH 5, 6, and 7. The average single-channel permeability coefficient of alpha-hemolysin for water ranged between 1.3x10-12 cm/s and 1.5x10-12 cm/s, depending on pH. The slightly increased single-channel permeability coefficient at lower pH-values was attributed to an increase in the effective pore size. The activation energy of water transport through the channel was low (Ea=5.4 kcal/mol), suggesting that the properties of water inside the alpha-hemolysin channel resemble those of bulk water. This conclusion was supported by calculations based on macroscopic hydrodynamic laws of laminar water flow. Using the known three-dimensional structure of the channel, the calculations accurately predicted the rate of water flow through the channel. The latter finding also indicated that water permeation data can provide a good estimate of the pore size for large channels.

Non-NASA Center↗

NASA NTRS2009

High-Efficiency Artificial Photosynthesis Using a Novel Alkaline Membrane Cell

A new cell designed to mimic the photosynthetic processes of plants to convert carbon dioxide into carbonaceous products and oxygen at high efficiency, has an improved configuration using a polymer membrane electrolyte and an alkaline medium. This increases efficiency of the artificial photosynthetic process, achieves high conversion rates, permits the use of inexpensive catalysts, and widens the range of products generated by this type of process. The alkaline membrane electrolyte allows for the continuous generation of sodium formate without the need for any additional separation system. The electrolyte type, pH, electrocatalyst type, and cell voltage were found to have a strong effect on the efficiency of conversion of carbon dioxide to formate. Indium electrodes were found to have higher conversion efficiency compared to lead. Bicarbonate electrolyte offers higher conversion efficiency and higher rates than water solutions saturated with carbon dioxide. pH values between 8 and 9 lead to the maximum values of efficiency. The operating cell voltage of 2.5 V, or higher, ensures conversion of the carbon dioxide to formate, although the hydrogen evolution reaction begins to compete strongly with the formate production reaction at higher cell voltages. Formate is produced at indium and lead electrodes at a conversion efficiency of 48 mg of CO2/kilojoule of energy input. This efficiency is about eight times that of natural photosynthesis in green plants. The electrochemical method of artificial photosynthesis is a promising approach for the conversion, separation and sequestration of carbon dioxide for confined environments as in space habitats, and also for carbon dioxide management in the terrestrial context. The heart of the reactor is a membrane cell fabricated from an alkaline polymer electrolyte membrane and catalyst- coated electrodes. This cell is assembled and held in compression in gold-plated hardware. The cathode side of the cell is supplied with carbon dioxide-saturated water or bicarbonate solution. The anode side of the cell is supplied with sodium hydroxide solution. The solutions are circulated past the electrodes in the electrochemical cell using pumps. A regulated power supply provides the electrical energy required for the reactions. Photovoltaic cells can be used to better mimic the photosynthetic reaction. The current flowing through the electrochemical cell, and the cell voltage, are monitored during experimentation. The products of the electrochemical reduction of carbon dioxide are allowed to accumulate in the cathode reservoir. Samples of the cathode solution are withdrawn for product analysis. Oxygen is generated on the anode side and is allowed to vent out of the reservoir.

Narayan, Sri↗

NASA NTRS2010

McMurdo Dry Valleys, Antarctica - A Mars Phoenix Mission Analog

The Phoenix mission (PHX; May 25 - Nov. 2, 2008) studied the north polar region of Mars (68deg N) to understand the history of water and potential for habitability. Phoenix carried with it a wet chemistry lab (WCL) capable of determining the basic solution chemistry of the soil and the pH value, a thermal and evolved-gas analyzer capable of determining the mineralogy of the soil and detecting ice, microscopes capable of seeing soil particle shapes, sizes and colors at very high resolution, and a soil probe (TECP) capable of detecting unfrozen water in the soil. PHX coincided with an international effort to study the Earth s polar regions named the International Polar Year (IPY; 2007-2008). The best known Earth analog to the Martian high-northern plains, where Phoenix landed, are the McMurdo Dry Valleys (MDV), Antarctica (Fig. 1). Thus, the IPY afforded a unique opportunity to study the MDV with the same foci - history of water and habitability - as PHX. In austral summer 2007, our team took engineering models of WCL and TECP into the MDV and performed analgous measurements. We also collected sterile samples and analyzed them in our home laboratories using state-of-the-art tools. While PHX was not designed to perform biologic analyses, we were able to do so with the MDV analog samples collected.

Tamppari, L. K.↗

NASA NTRS2011

Analysis of Mars Analogue Soil Samples Using Solid-Phase Microextraction, Organic Solvent Extraction and Gas Chromatography/Mass Spectrometry

Polycyclic aromatic hydrocarbons (PAHs) are robust and abundant molecules in extraterrestrial environments. They are found ubiquitously in the interstellar medium and have been identified in extracts of meteorites collected on Earth. PAHs are important target molecules for planetary exploration missions that investigate the organic inventory of planets, moons and small bodies. This study is part of an interdisciplinary preparation phase to search for organic molecules and life on Mars. We have investigated PAH compounds in desert soils to determine their composition, distribution and stability. Soil samples (Mars analogue soils) were collected at desert areas of Utah in the vicinity of the Mars Desert Research Station (MDRS), in the Arequipa region in Peru and from the Jutland region of Denmark. The aim of this study was to optimize the solid-phase microextraction (SPME) method for fast screening and determination of PAHs in soil samples. This method minimizes sample handling and preserves the chemical integrity of the sample. Complementary liquid extraction was used to obtain information on five- and six-ring PAH compounds. The measured concentrations of PAHs are, in general, very low, ranging from 1 to 60 ng g(sup -1). The texture of soils is mostly sandy loam with few samples being 100% silt. Collected soils are moderately basic with pH values of 8-9 except for the Salten Skov soil, which is slightly acidic. Although the diverse and variable microbial populations of the samples at the sample sites might have affected the levels and variety of PAHs detected, SPME appears to be a rapid, viable field sampling technique with implications for use on planetary missions.

Orzechowska, G. E.↗

NASA NTRS2019

Saponite Dissolution Experiments and Implications for Mars

Recent work suggests that the mineralogical sequence of the Murray formation at Gale crater may have resulted from diagenetic alteration after sedimentation, or deposition in a stratified lake with oxic surface and anoxic bottom waters. Fe-containing clay minerals are common both at Gale crater, and throughout the Noachian-aged terrains on Mars. These clay minerals are primarily ferric (Fe3+), and previous work suggests that these ferric clay minerals may result from alteration of ferrous (Fe2+) smectites that were oxidized after deposition. The detection of trioctahedral smectites at Gale crater by CheMin suggests Fe2+ smectite was also deposited during the early Hesperian. However, due to their sensitivity to oxygen, Fe2+ smectites are difficult to analyze on Earth and very few saponite dissolution rates exist in the literature. To the best of our knowledge, no experiments have measured the dissolution rates of ferrous saponites under oxidizing and reducing conditions. In order to better understand the characteristics of water-rock interaction at Gale crater, particularly the oxidation state, we report our results to date on ongoing syntheses of ferrous and magnesium saponites and dissolution experiments of natural saponite under ambient conditions. Future experiments will include the dissolution of synthetic ferric, ferrous, and magnesium saponites under oxidizing and anoxic conditions at a range of pH values.

Luu, N. C.↗

NASA NTRS2020

Source Apportionment of Aerosol at a Coastal Site and Relationships with Precipitation Chemistry: A Case Study over the Southeast United States

This study focuses on the long-term aerosol and precipitation chemistry measurements from colocated monitoring sites in Southern Florida between 2013 and 2018. A positive matrix factorization (PMF) model identified six potential emission sources impacting the study area. The PMF model solution yielded the following source concentration profiles: (i) combustion; (ii) fresh sea salt; (iii) aged sea salt; (iv) secondary sulfate; (v) shipping emissions; and (vi) dust. Based on these results, concentration-weighted trajectory maps were developed to identify sources contributing to the PMF factors. Monthly mean precipitation pH values ranged from 4.98 to 5.58, being positively related to crustal species and negatively related to SO42−. Sea salt dominated wet deposition volume-weighted concentrations year-round without much variability in its mass fraction in contrast to stronger seasonal changes in PM2.5 composition where fresh sea salt was far less influential. The highest mean annual deposition fluxes were attributed to Cl−, NO3−, SO42−, and Na+ between April and October. Nitrate is strongly correlated with dust constituents (unlike sea salt) in precipitation samples, indicative of efficient partitioning to dust. Interrelationships between precipitation chemistry and aerosol species based on long-term surface data provide insight into aerosol–cloud–precipitation interactions.

positive matrix factorization↗