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NASA NTRS2013

Subsurface Salts in Antarctic Dry Valley Soils

The distribution of water-soluble ions, major and minor elements, and other parameters were examined to determine the extent and effects of chemical weathering on cold desert soils. Patterns at the study sites support theories of multiple salt forming processes, including marine aerosols and chemical weathering of mafic minerals. Periodic solar-mediated ionization of atmospheric nitrogen might also produce high nitrate concentrations found in older sediments. Chemical weathering, however, was the major contributor of salts in Antarctic Dry Valleys. The Antarctic Dry Valleys represent a unique analog for Mars, as they are extremely cold and dry desert environments. Similarities in the climate, surface geology, and chemical properties of the Dry Valleys to that of Mars imply the possible presence of these soil formation mechanisms on Mars, other planets and icy satellites.

Englert, P.↗

NASA NTRS2019

Perchlorate on Mars - Overview and Implications

Perchlorate was first detected on Mars by the Wet Chemistry Laboratory (WCL) instrument on the Phoenix lander at a concentration of ~0.5 wt% in northern plains soils. Since that initial detection, perchlorate (and likely chlorate) have been detected on Mars by both surface and orbital instruments. Perchlorate (ClO4-) is an oxidized chlorine compound and salts of perchlorate are kinetically stable (though very reactive at high temperature), very soluble, deliquescent, and have low eutectic temperature (which decreases the temperature for stable liquids on Mars). Chlorate (ClO3-) salts are similar, though they are less kinetically stable than perchlorates. Because many of the analytical signatures of perchlorate and chlorate are similar to the instruments we have used on Mars, we cannot always determine which species is present, so we will use the more generic term “oxychlorine” when referring to perchlorate and/or chlorate.

Archer, P. D.↗

NASA NTRS1984

High-Flow Asymmetric Reverse-Osmosis Membranes

Water-soluble polymer membrane insolubilized by transition-metal salt. Thin layer of lower permeability material joined with thicker layer of highpermeability material. Two layers chemically identical or chemically distinct. They differ in density, compactness or other respects. Used to purify or desalinate seawater, brackish water, or industrial or domestic wastewater.

Katz, M. C.↗

NASA NTRS1993

Mars aqueous chemistry experiment

The Mars Aqueous Chemistry Experiment (MACE) is designed to conduct a variety of measurements on regolith samples, encompassing mineral phase analyses, chemical interactions with H2O, and physical properties determinations. From these data, much can be learned or inferred regarding the past weathering environment, the contemporaneous soil micro-environments, and the general chemical and physical state of the Martian regolith. By analyzing both soil and duricrust samples, the nature of the latter may become more apparent. Sites may be characterized for comparative purposes and criteria could be set for selection of high priority materials on future sample return missions. Progress for the first year MACE PIDDP is reported in two major areas of effort: (1) fluids handling concepts, definition, and breadboard fabrication and (2) aqueous chemistry ion sensing technology and test facility integration. A fluids handling breadboard was designed, fabricated, and tested at Mars ambient pressure. The breadboard allows fluid manipulation scenarios to be tested under the reduced pressure conditions expected in the Martian atmosphere in order to validate valve operations, orchestrate analysis sequences, investigate sealing integrity, and to demonstrate efficacy of the fluid handling concept. Additional fluid manipulation concepts have also been developed based on updated MESUR spacecraft definition. The Mars Aqueous Chemistry Experiment Ion Selective Electrode (ISE) facility was designed as a test bed to develop a multifunction interface for measurements of chemical ion concentrations in aqueous solution. The interface allows acquisition of real time data concerning the kinetics and heats of salt dissolution, and transient response to calibration and solubility events. An array of ion selective electrodes has been interfaced and preliminary calibration studies performed.

Clark, Benton C.↗

NASA NTRS1994

Oligonucleotides as probes for studying polymerization reactions in dilute aqueous solution

We have prepared a [32P]-labled oligonucleotide probe carrying a free primary amine at its 3'-terminus. This probe is used to initiate polymerization of aziridine (ethyleneimine) in aqueous solution. The nature of the oligomeric products and the kinetics of their formation are then monitored by gel electrophoresis. Our results are generally consistent with those obtained using conventional techniques. We have also investigated the effect of polyanionic templates on the rate of oligomerization of aziridine. We find that water-soluble polyanions generally accelerate the polymerization. The sodium salt of polymethacrylic acid is the most effective of the templates that we studied. The methods introduced in this paper should be applicable to a variety of polymerization reactions in aqueous solution. They should greatly simplify the screening of potentially prebiotic polymerization reactions.

NASA Discipline Exobiology↗

NASA NTRS1976

Effects of subfornical organ extracts on salt-water balance in the rat

The subfornical organ (SFO) is a circumventricular structure located at the junction of the lamina terminalis and the tela choroidea of the third cerebral ventricle. SFO is histologically regarded as a neurosecretory structure, although the physiological effects or biochemical nature of such secretions are not yet ascertained. Results are presented for an experimental study designed to determine whether SFO extracts alter parameters associated with salt-water balance in the rat. The data obtained support the conclusion that SFO contains some water-soluble substance(s), easily released by incubation, dialyzable and heat stable, which influences the salt-water balance after injection into ventricular cerebrospinal fluid. Whether other brain tissues or plasma contains the same or similar material is not yet convincingly established. The observation that one or more active constituents are easily released from SFO upon incubation in potassium-enriched medium may be of value.

Summy-Long, J. Y.↗

NASA NTRS1992

Coupling plant growth and waste recycling systems in a controlled life support system (CELSS)

The development of bioregenerative systems as part of the Controlled Ecological Life Support System (CELSS) program depends, in large part, on the ability to recycle inorganic nutrients, contained in waste material, into plant growth systems. One significant waste (resource) stream is inedible plant material. This research compared wheat growth in hydroponic solutions based on inorganic salts (modified Hoagland's) with solutions based on the soluble fraction of inedible wheat biomass (leachate). Recycled nutrients in leachate solutions provided the majority of mineral nutrients for plant growth, although additions of inorganic nutrients to leachate solutions were necessary. Results indicate that plant growth and waste recyling systems can be effectively coupled within CELSS based on equivalent wheat yield in leachate and Hoagland solutions, and the rapid mineralization of waste organic material in the hydroponic systems. Selective enrichment for microbial communities able to mineralize organic material within the leachate was necessary to prevent accumulation of dissolved organic matter in leachate-based solutions. Extensive analysis of microbial abundance, growth, and activity in the hydroponic systems indicated that addition of soluble organic material from plants does not cause excessive microbial growth or 'biofouling', and helped define the microbially-mediated flux of carbon in hydroponic solutions.

Garland, Jay L.↗

NASA NTRS2000

The Effects of Thermal History on Nucleation of Tetragonal Lysozyme Crystals, or Hot Protein and Cold Nucleation

Chicken egg white lysozyme has a well characterized thermally driven phase transition. Between pH 4.2 and 5.2, the transition temperature, as defined by the point where the tetragonal and orthorhombic solubilities are equal, is a function of the pH, salt (precipitant) type and concentration, and most likely of the buffer concentration as well. This phase transition can be carried out with protein solution alone, prior to addition of precipitant solution. Warming a lysozyme solution above the phase transition point, then cooling it back below this point, has been shown to affect the subsequent nucleation rate, as determined by the numbers and size of crystals formed, but not the growth rate for the tetragonal crystal form . We have now measured the kinetics of this process and investigated its reversibility. The transition effects are progressive with temperature, having a half time of about 1 hour at 37C at pH 4.8. After holding a lysozyme solution at 37C (prior to addition of precipitant) for 16 hours, then cooling it back to 4C no return to the pre-warmed nucleation kinetics are observed after at least 4 weeks. Orthorhombic lysozyme crystals apparently do not undergo the flow-induced growth cessation of tetragonal lysozyme crystals. Putting the protein in the orthorhombic form does not affect the averaged face growth kinetics, only nucleation, for tetragonal crystals. This differential behaviour may be exploited to elucidate how and where flow affects the lysozyme crystal growth process. The presentation will focus on the results of these and ongoing studies in this area.

Burke, Michael↗

NASA NTRS2000

Does Warming a Lysozyme Solution Cook Ones Data?

Chicken egg white lysozyme has a well characterized thermally driven phase transition. Between pH 4.0 and 5.2, the transition temperature, as defined by the point where the tetragonal and orthorhombic solubility are equal, is a function of the pH, salt (precipitant) type and concentration, and most likely of the buffer concentration as well. This phase transition can be carried out with protein solution alone, prior to the initiation of the crystallization process. We have now measured the kinetics of this process and investigated its reversibility. An aliquot of a stock protein solution is held at a given temperature, and at periodic intervals used to set up batch crystallization experiments. The batch solutions were incubated at 20 C until macroscopic crystals were obtained, at which point the number of crystals in each well were counted. The transition effects increased with temperature, slowly falling off at 30 C with a half time (time to approx. 1/2 the t = 0 number of crystals) of approx. 5 hours, and an estimated half time of approx. 0.5 hours at 43 C. Further, the process was not reversible by simple cooling. After holding a lysozyme solution at 37 C (prior to addition of precipitant) for 16 hours, then cooling and holding it at 4 C, no return to the pre-warmed nucleation kinetics are observed after at least 4 weeks. Thus every thermal excursion above the phase transition point results in a further decrease in the nucleation rate of that solution, the extent being a function of the time and temperature. Orthorhombic lysozyme crystals apparently do not undergo the flow-induced growth cessation of tetragonal lysozyme crystals. We have previously shown that putting the protein in the orthorhombic form does not affect the averaged face growth kinetics, only nucleation, for tetragonal crystals. We may be able to use this differential behavior to elucidate how flow affects tile lysozyme crystal growth process.

Pusey, Marc↗

NASA NTRS2006

Fossils of Prokaryotic Microorganisms in the Orgueil Meteorite

The Orgueil CII meteorite, which fell in southern France on the evening of May 14, 1864, has been one of the most extensively studied of all known carbonaceous meteorites. Field Emission Scanning Electron Microscopy (FESEM) studies of freshly fractured interior surfaces of the Orgueil meteorite have resulted in the detection of the fossilized remains of a large and diverse population of filamentous prokaryotic microorganisms. The taphonomy and the diverse modes of the preservation of these remains ,are diverse. Some of the remains exhibit carbonization of a hollow sheath and in other cases the remains are permineralized with water-soluble evaporite minerals, such as magnesium sulfate or ammonium salts. After the sample is fractured and the interior surfaces are exposed to the atmospheric moisture, some of these friable remains have been observed to exhibit significant alterations in appearance with time. Images are presented to document the changes that have been observed in some forms within the past two years. Images and EDS spectral data will also be presented to document the studies carried out on abiotic forms to search for possible nonbiological interpretations of the indigenous filamentous microstructures that have been found in the Orgueil meteorite. Images and EDS data will be presented showing the size, size range, morphology and chemical compositions of abiotic microstructures found in native crystalline and fibrous Epsomites from Poison Lake, Washington, USA and Catalayud, Zaragoza, Aragon, Spain. Many of these embedded forms are consistent in size and microstructure with cyanobacteria morphotypes. Some of the forms are exhibit known characteristics differentiation of cells, and reproductive structures of filamentous trichomic prokaryotes (bacteria and cyanobacteria) and the degraded remains of microfibrils associated with sheaths of cyanobacteria. In this paper, recently obtained comparative images and EDS data will be presented for the mineralized remains found in the Orgueil meteorite and these forms will be compared with known cyanobacteria of the family Oscillatoriaceae. Many of the indigenous filamentous microstructures found in Orgueil filaments are dramatically different from the abiotic microstructures found in the fibrous epsomites and these forms are interpreted as the molds, casts and the well preserved permineralized remains (microfossils) of filamentous prokaryotes that are embedded in and indigenous to the matrix of the Orgueil CI1 carbonaceous meteorite.

Hoover, Richard B.↗

NASA NTRS2017

Impact-Facilitated Hydrothermal Alteration in the Rim of Endeavour Crater, Mars

Endeavour crater, a Noachian-aged, 22 km diameter impact structure on Meridiani Planum, Mars, has been investigated by the Mars Exploration Rover Opportunuity for over 2000 sols (Mars days). The rocks of the western rim region (oldest to youngest) are: (i) the pre-impact Matijevic fm.; (ii) rim-forming Shoemaker fm. polymict impact breccias; (iii) Grasberg fm., fine-grained sediments draping the lower slopes; and (iv) Burns fm., sulfate-rich sandstones that onlap the Grasberg fm. The rim is segmented and transected by radial fracture zones. Evidence for fluid-mediated alteration includes m-scale detections of phyllosilicates from orbit, and cm-scale variations in rock/soil composition/mineralogy documented by the Opportunity instrument suite. The m-scale phyllosilicate detections include Fe(3+)-Mg and aluminous smectites that occur in patches in the Matijevic and Shoemaker fms. Rock compositions do not reveal substantial differences for smectite-bearing compared to smectite-free rocks. Interpretation: large-scale hydrothermal alteration powered by impact-deposited heat acting on limited water supplies engendered mineralogic transfomations under low water/rock, near-isochemical conditions. The cm-scale alterations, localized in fracture zones, occurred at higher water/rock as evidenced by enhanced Si and Al contents through leaching of more soluble elements, and deposition of Mg, Ni and Mn sulphates and halogen salts in soils. Visible/near infrared reflectance of narrow curvilinear red zones indicate higher nanophase ferric oxide contents and possibly hydration compared to surrounding outcrops. Broad fracture zones on the rim have reflectance features consistent with development of ferric oxide minerals. Interpretation: water fluxing through the fractures in a hydrothermal system resulting from the impact engendered alteration and leaching under high water/rock conditions. Late, localized alteration is documented by Ca-sulfate-rich veins that are not confined to fracture zones; some cross-cut the Grasberg fm. Interpretation: late fluid mobilization of soluble elements, likely in a later alteration event.

Mittlefehldt, D. W.↗

NASA NTRS1989

Chemical model for Viking biology experiments - Implications for the composition of the Martian regolith

The labelled-release and the gas-exchange experiments of the 1976 Mars Viking biology experiment program detected, respectively, C-14 labelled gases and O2 gas. A chemical model is proposed here for these experiments in which the reactants are an inorganic nitrate salt which has been partly photolyzed by ultraviolet light and a sparingly soluble metal carbonate such as calcite. The model reproduces the main effects seen, indicating that nitrates are present in the Martian regolith as well as calcite (or some other carbonate with similar solubility).

Plumb, Robert C.↗

NASA NTRS1993

Protein crystal growth in low gravity

This Final Technical Report for NASA Grant NAG8-774 covers the period from April 27, 1989 through December 31, 1992. It covers five main topics: fluid flow studies, the influence of growth conditions on the morphology of isocitrate lyase crystals, control of nucleation, the growth of lysozyme by the temperature gradient method and graphoepitaxy of protein crystals. The section on fluid flow discusses the limits of detectability in the Schlieren imaging of fluid flows around protein crystals. The isocitrate lyase study compares crystals grown terrestrially under a variety of conditions with those grown in space. The controlling factor governing the morphology of the crystals is the supersaturation. The lack of flow in the interface between the drop and the atmosphere in microgravity causes protein precipitation in the boundary layer and a lowering of the supersaturation in the drop. This lowered supersaturation leads to improved crystal morphology. Preliminary experiments with lysozyme indicated that localized temperature gradients could be used to nucleate crystals in a controlled manner. An apparatus (thermonucleator) was designed to study the controlled nucleation of protein crystals. This apparatus has been used to nucleate crystals of materials with both normal (ice-water, Rochelle salt and lysozyme) and retrograde (horse serum albumin and alpha chymotrypsinogen A) solubility. These studies have lead to the design of an new apparatus that small and more compatible with use in microgravity. Lysozyme crystals were grown by transporting nutrient from a source (lysozyme powder) to the crystal in a temperature gradient. The influence of path length and cross section on the growth rate was demonstrated. This technique can be combined with the thermonucleator to control both nucleation and growth. Graphoepitaxy utilizes a patterned substrate to orient growing crystals. In this study, silicon substrates with 10 micron grooves were used to grow crystals of catalase, lysozyme and canavalin. In all cases, the crystals grew oriented to the substrate. The supersaturation needed for nucleation and growth was lower on the patterned substrates. In some cases, isolated, large crystals were grown.

Feigelson, Robert S.↗

NASA NTRS1977

Intumescent coatings based on 4,4 prime-dinitrosulfanilide

Nitroaromatic amine-based intumescent coatings which offer improved thermal protection to a substrate by reducing the backface temperature rise have been developed. The intumescent monomer agent is 4,4 prime-dinitrosulfanilide. This agent has an intumescent temperature of 220 deg C, compared with 300 deg C for the ammonium salt of 1,4-nitroaniline-2-sulfonic acid and offers a twelve-fold reduction in water solubility over this compound. On the basis of differential thermal analysis and screening tests, a chlorinated polyolifin epoxy-reactive butadiene acrylonitrile rubber blend was selected as a flame quenching binder.

Sawko, P. M.↗

NASA NTRS1992

Controlling nucleation in protein solutions

A simple one-step technique for controlling the nucleation stage in protein solutions without the use of a seed crystal was developed using a specially designed apparatus in which the nucleation and growth processes can be separated. The method can be applied only to species that have a temperature-dependent solubility. The effectiveness of this 'thermonucleating' device was demonstrated with the nucleation and growth of ice, Rochelle salt, and lysozyme.

Demattei, R. C.↗

NASA NTRS1992

Amyotrophic lateral sclerosis: increased solubility of skin collagen

We studied the solubility of skin collagen from six patients with amyotrophic lateral sclerosis (ALS) and six controls. The amount of collagen extracted with neutral salt solution was significantly greater in patients with ALS than in controls. In addition, there was a statistically significant increase in the proportion of collagen extracted from ALS patients with increased duration of illness. The collagen solubilized by pepsin and cyanogen bromide treatments was significantly higher in ALS patients than in controls, and its proportion was positively and significantly associated with duration of illness in ALS patients. These results indicate that the metabolism of skin collagen may be affected in the disease process of ALS, causing an increase in immature soluble collagen in the tissue, which is the opposite to that which occurs in the normal aging process.

NASA Discipline Musculoskeletal↗

NASA NTRS1994

The effects of temperature and NaCl concentration on tetragonal lysozyme face growth rates

Measurements were made of the (110) and (101) face growth rates of the tetragonal form of hen egg white lysozyme at 0.1M sodium acetate buffer, pH 4.0, from 4 to 22 C and with 3.0%, 5.0%, and 7.0% NaCl used as the precipitating salt. The data were collected at supersaturation ratios ranging from approximately 4 to approximately 63. Both decreasing temperature and increasing salt concentrations shifted plots of the growth rate versus C/C(sat) to the right, i.e. higher supersaturations were required for comparable growth rates. The observed trends in the growth data are counter to those expected from the solubility data. If tetragonal lysozyme crystal growth is by addition of ordered aggregates from the solution, then the observed growth data could be explained as a result of the effects of lowered temperature and increased salt concentration on the kinetics and equilibrium processes governing protein-protein interactions in solution. The data indicate that temperature would be a more tractable means of controlling the growth rate for tetragonal lysozyme crystals contrary to the usual practice in, e.g., vapor diffusion protein crystal growth, where both the precipitant and protein concentrations are simultaneously increased. However, the available range for control is dependent upon the protein concentration, with the greatest growth rate control being at the lower concentration.

Forsythe, Elizabeth↗

NASA NTRS2016

Radiative Effect of Springtime Biomass-Burning Aerosols over Northern Indochina During 7-SEAS Baseline 2013 Campaign

The direct aerosol radiative effects of biomass-burning (BB) aerosols over northern Indochina were estimated by using aerosol properties (physical, chemical, and optical) along with the vertical profile measurements from ground-based measurements with integration of an optical and a radiative transfer model during the Seven South East Asian Studies Biomass-Burning Aerosols Stratocumulus Environment: Lifecycles Interactions Experiment (7-SEASBASELInE) conducted in spring 2013. Cluster analysis of backward trajectories showed the air masses arriving at mountainous background site (Doi Ang Khang; 19.93degN, 99.05degE, 1536 m above mean sea level) in northern Indochina, mainly from near-source inland BB activities and being confined in the planetary boundary layer. The PM(sub10) and black carbon (BC)mass were 87 +/- 28 and 7 +/- 2 micrograms m(exp -3), respectively. The aerosol optical depth (AOD (sub 500) was found to be 0.26--1.13 (0.71 +/- 0.24). Finer (fine mode fraction is approximately or equal to 0.95, angstrom-exponent at 440-870 nm is approximately or equal to 1.77) and significantly absorbing aerosols(single scattering albedo is approximately or equal to 0.89, asymmetry-parameter is approximately or equal to 0.67, and absorption AOD 0.1 at 440 nm) dominated over this region. BB aerosols (water soluble and BC) were the main contributor to the aerosol radiative forcing (ARF), while others (water insoluble, sea salt and mineral dust) were negligible mainly due to their low extinction efficiency. BC contributed only 6 to the surface aerosol mass but its contribution to AOD was 12 (2 times higher). The overall mean ARF was 8.0 and -31.4 W m(exp -2) at top-of-atmosphere (TOA) and at the surface (SFC), respectively. Likely, ARF due to BC was +10.7 and -18.1 W m(exp -2) at TOA and SFC, respectively. BC imposed the heating rate of +1.4 K d(exp -1) within the atmosphere and highlighting its pivotal role in modifying the radiation budget. We propose that to upgrade our knowledge on BB aerosol radiative effects in BB source region, the long-term and extensive field measurements are needed.

aerosol optical properties↗