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Phosphate (U-Th)/He Thermochronology of Apollo 14 Melt Breccia 14311

Our ability to confidently characterize the impact history of the inner solar system is limited by discrepancies in radiometric dates and age interpretations for lunar rocks, impact melts, and recovered meteorites. It is therefore important to explore different thermally sensitive radiometric systems to unravel the timing and extent of the long term impact flux. Low-temperature thermochronology of lunar samples has the potential to provide more complementary geochronological datasets and further test dynamical models related to the evolution of the inner solar system (e.g., [1]). (U-Th)/He dating is based on the production of 4He atoms by radioactive alpha decay of U and Th (and to a lesser extent, Sm) in a crystal and the thermally activated volumetric diffusion of those 4He nuclides. At high temperatures, the crystal is an open system from which 4He can escape; at lower temperatures, 4He may be retained. This retention temperature depends on factors such as crystal structure and volume fraction of radiation damage in the crystal (e.g., [2, 3]), but is significantly lower for phosphate minerals compared to the diffusion of the radiogenic daughter products in other widely used chronometric systems (e.g., ~75°C in terrestrial apatite (U-Th)/He vs. ~500°C in apatite U-Th-Pb vs. ~900°C in zircon U-Th-Pb chronometry). Phosphate (U-Th)/He dating has been used to decipher peak temperatures and cooling rates related to terrestrial impact events (e.g., [4]). Pairing a low-temperature thermochronometer with higher-temperature approaches (i.e., a combined 207Pb-206Pb and (U-Th)/He approach), can therefore resolve multiple impact ages within a given sample or even grain. However, despite its potential, phosphate (U-Th)/He dating has not been reported on any lunar samples. Here we present the first lunar phosphate (U-Th)/He thermochronology on an Apollo 14 impact melt-breccia.

C A Diaz↗
NASA NTRS2024

Ubiquitous Presence of Sodium-Bearing Magnesium Phosphate in CI Chondritic Materials

The discovery that the asteroid Ryugu samples returned by the JAXA Hayabusa2 spacecraft are chemically and mineralogically nearly identical to CI chondrites has made us re-recognize the importance of CI chondrites in the early solar system [e.g., 1]. These CI chondritic materials have undergone strong aqueous alteration in their parent bodies, resulting in the formation of abundant Mg-Fe phyllosilicates along with other altered minerals such as carbonates, magnetite, and pyrrhotite. Initial and subsequent AO analyses of the Ryugu samples have found that they are brecciated on the mm~μm scale and that a small amount of forsterite and other primary minerals survive in some of the brecciated clasts with evidence of less degrees of aqueous alteration (“less altered clast”) [e.g., 1]. In addition, these less altered clasts contain a rare Na-bearing Mg phosphate that is still poorly characterized. Despite the analytical attempt to identify its mineral species, their identity has not been clarified yet. These rare Mg phosphates could be one of the key phases to understanding the evolution of CI chondritic bodies since a similar Na-bearing Mg phosphate has been reported from the asteroid Bennu sample returned by the NASA OSIRIS REx mission, and the importance of these materials has been suddenly highlighted. Since the initial analysis of the Ryugu sample, we have been paying attention to these Mg phosphates in CI chondrites as well as Ryugu samples, and here we report the present results on their mineralogical analysis.

T Mikouchi↗
NASA NTRS1972

Gadolinium-hydrogen ion exchange of zirconium phosphate

The Gd(+3)/H(+) ion exchange on a commercial zirconium phosphate ion exchanger was investigated in chloride, sulfate, and phosphate solutions of Gd(+3) at gadolinium concentrations of 0.001 to 1 millimole per cc and in the pH range of 0 to 3.5. Relatively low Gd(+3) capacities, in the range of 0.01 to 0.1 millimole per g of ion exchanger were found at room temperature. A significant difference in Gd(+3) sorption was observed, depending on whether the ion exchanger was converted from initial conditions of greater or lesser Gd(+3) sorption than the specific final conditions. Correlations were found between decrease in Gd(+3) capacity and loss of exchanger phosphate groups due to hydrolysis during washing and between increase in capacity and treatment with H3PO4. Fitting of the experimental data to ideal ion exchange equilibrium expressions indicated that each Gd(+3) ion is sorbed on only one site of the ion exchanger. The selectivity quotient was determined to be 2.5 + or - 0.4 at room temperature on gadolinium desorption in chloride solutions.

Liu, D. C.↗
NASA NTRS1973

Glycolytic intermediates and adenosine phosphates in rat liver at high altitude /3,800 m/.

Liver tissue obtained from adult rats exposed to 3800 m altitude for intervals ranging from 1.5 hr to 63 days was examined by enzymatic analysis. During the first 3 hr of exposure, an immediate decrease in rephosphorylation of high-energy phosphates led to reduced glycogenesis and eventual pileup of AMP, pyruvate, fructose 1,6-diphosphate, glucose 6-phosphate, and glucose. This was accompanied by a reduction of pentose phosphate pathway activity. After 3 to 6 hr, a secondary adjustment of substrate concentrations occurred along with the apparent facilitation of phosphofructokinase. This secondary adjustment appears to increase anaerobic production of ATP and represents a significant intracellular contribution to the acclimatization process at high altitude.

Cipriano, L. F.↗
NASA NTRS1977

The relationship between lunar metal particles and phosphate minerals

Phosphorus is often present in lunar rocks and soils in bulk concentrations in excess of 0.5 wt % P205. The minerals apatite and whitlockite account for most of the phosphorus. However, it may also be present in metal grains. The relations between metal particles and the phosphates commonly found adjacent to these particles are investigated, taking into account studies involving three Apollo 17 rocks. It appears that phosphorus in lunar metal particles is related to the phosphate minerals by a redox reaction. The independent phosphates probably formed over much of the cooling period of the rock. While the rock was at high temperature, however, phosphorus was free to diffuse and dissolve in the metal droplets providing conditions were sufficiently reducing. If the rock was partially molten, this process would take less than 1 hr. If cooling occurred slowly under less reducing conditions, some of the phosphorus in the metal particles would be oxidized to form whitlockite.

Friel, J. J.↗
NASA NTRS1985

Microanalysis of dissolved iron and phosphate in pore waters of hypersaline sediment

Diurnal fluctuations of reduced iron concentrations, expected to occur in reduced sediments in the photic zone, were studied. Iron concentration was compared to O2-H2S, a microcanalysis of sulfate reduction was performed, as well as an examination of diurnal concentration of dissolved phosphate and changes in interstitial CO2. The iron profiles suggest a strong correlation between iron remobilization and processes occurring in the light. Phosphate profiles suggest the removal of phosphate is strongly correlated with precipitation of oxidized iron in the upper 2 mm to 5 mm of the sediments. Pore water CO2 concentrations and carbon isotope ratios are presented. These data are from the analyses of minisediment cores collected from the 42 per mil salt pond and incubated in the laboratory under light and dark conditions.

Haddad, R.↗
NASA NTRS1984

Androgen-estrogen synergy in rat levator ani muscle Glucose-6-phosphate dehydrogenase

The effects of castration and hormone administration on the activity of glucose-6-phosphate dehydrogenase in the rat levator ani muscle were studied. Castration caused a decrease in enzyme activity and in wet weight of the levator ani muscle. Chronic administration of testosterone propionate increased glucose-6-phosphate dehydrogenase activity in the levator ani muscle of castrated rats; the magnitude of the recovery of enzyme activity was related to the length of time of exposure to testosterone propionate after castration as well as to the length of time the animals were castrated. The longer the period of castration before exposure to testosterone propionate, the greater the effect. This result may be related to previously reported castration-mediated increases in androgen receptor binding in muscle. Dihydrotestosterone was less effective than testosterone propionate in enhancing glucose-6-phosphate dehydrogenase activity in the levator ani muscle from castrated rats; estradiol-17-beta alone was ineffective. Combined treatment with estradiol-17-beta and dihydrotestosterone, however, was as effective as testosterone alone. Thus, androgens and estrogens may exert synergistic effects on levator ani muscle.

Max, S. R.↗
NASA NTRS1994

Long Term Dynamic Stream Nitrate and Phosphate Changes Following Watershed Wildfires

During and following the 1988 Yellowstone National Park wildfires, airborne remotely sensed data were collected in order to characterize various vegetative components, fire front movements and bum intensities. ER-2 derived Thematic Mapper Simulator (TMS) data were used in conjunction with water sampling and chemistry analysis to determine fire intensities in various watersheds and aquatic system condition changes. The airborne Daedalus multispectral TMS data allowed the characterization of various bum intensities in watersheds. Stream sampling was then conducted in those various burned watersheds to determine nitrate and phosphate concentration changes. Six stream watersheds were monitored for five years (1989-1993) during non-snow periods (May/June through September): Cache Creek (intensely burned), Blacktail Deer Creek (intensely burned), Snake River (moderately burned), Lamar River (mixed burning), Soda Butte Creek (lightly burned), and Amphitheatre Creek (unburned). One litre samples were collected from those streams with ISCO water samplers every 12 hours. The samples were removed every 14 days .(28 Samples), and water chemistry analysis was performed. Chemistry analysis indicated that nitrate and phosphate concentrations were elevated in moderately burned watersheds and significantly elevated in severely burned watersheds. The results during the five year study indicate that bum intensities regulate stream water nitrate and phosphate concentrations, and that remotely sensed data can be used effectively to predict watershed chemical changes which will affect aquatic conditions.

Ambrosia, Vincent G.↗
NASA NTRS2000

Interstitial pH, K(+), lactate, and phosphate determined with MSNA during exercise in humans

The purpose of the present study was to use the microdialysis technique to simultaneously measure the interstitial concentrations of several putative stimulators of the exercise pressor reflex during 5 min of intermittent static quadriceps exercise in humans (n = 7). Exercise resulted in approximately a threefold (P < 0.05) increase in muscle sympathetic nerve activity (MSNA) and 13 +/- 3 beats/min (P < 0.05) and 20 +/- 2 mmHg (P < 0.05) increases in heart rate and blood pressure, respectively. During recovery, all reflex responses quickly returned to baseline. Interstitial lactate levels were increased (P < 0.05) from rest (1.1 +/- 0.1 mM) to exercise (1. 6 +/- 0.2 mM) and were further increased (P < 0.05) during recovery (2.0 +/- 0.2 mM). Dialysate phosphate concentrations were 0.55 +/- 0. 04, 0.71 +/- 0.05, and 0.48 +/- 0.03 mM during rest, exercise, and recovery, respectively, and were significantly elevated during exercise. At the onset of exercise, dialysate K(+) levels rose rapidly above resting values (4.2 +/- 0.1 meq/l) and continued to increase during the exercise bout. After 5 min of contractions, dialysate K(+) levels had peaked with an increase (P < 0.05) of 0.6 +/- 0.1 meq/l and subsequently decreased during recovery, not being different from rest after 3 min. In contrast, H(+) concentrations rapidly decreased (P < 0.05) from resting levels (69.4 +/- 3.7 nM) during quadriceps exercise and continued to decrease with a mean decline (P < 0.05) of 16.7 +/- 3.8 nM being achieved after 5 min. During recovery, H(+) concentrations rapidly increased and were not significantly different from baseline after 1 min. This study represents the first time that skeletal muscle interstitial pH, K(+), lactate, and phosphate have been measured in conjunction with MSNA, heart rate, and blood pressure during intermittent static quadriceps exercise in humans. These data suggest that interstitial K(+) and phosphate, but not lactate and H(+), may contribute to the stimulation of the exercise pressor reflex.

Non-NASA Center↗
NASA NTRS2004

Molecular Data for a Biochemical Model of DNA Radiation Damage: Electron Impact Ionization and Dissociative Ionization of DNA Bases and Sugar-Phosphate Backbone

As part of the database for building up a biochemical model of DNA radiation damage, electron impact ionization cross sections of sugar-phosphate backbone and DNA bases have been calculated using the improved binary-encounter dipole (iBED) model. It is found that the total ionization cross sections of C3'- and C5'-deoxyribose-phospate, two conformers of the sugar-phosphate backbone, are close to each other. Furthermore, the sum of the ionization cross sections of the separate deoxyribose and phosphate fragments is in close agreement with the C3'- and C5'-deoxyribose-phospate cross sections, differing by less than 10%. Of the four DNA bases, the ionization cross section of guanine is the largest, then in decreasing order, adenine, thymine, and cytosine. The order is in accordance with the known propensity of oxidation of the bases by ionizing radiation. Dissociative ionization (DI), a process that both ionizes and dissociates a molecule, is investigated for cytosine. The DI cross section for the formation of H and (cytosine-Hl)(+), with the cytosine ion losing H at the 1 position, is also reported. The threshold of this process is calculated to be 17.1 eV. Detailed analysis of ionization products such as in DI is important to trace the sequential steps in the biochemical process of DNA damage.

Dateo, Christopher E.↗
NASA NTRS1997

Entropy and charge in molecular evolution--the case of phosphate

Biopoesis, the creation of life, implies molecular evolution from simple components, randomly distributed and in a dilute state, to form highly organized, concentrated systems capable of metabolism, replication and mutation. This chain of events must involve environmental processes that can locally lower entropy in several steps; by specific selection from an indiscriminate mixture, by concentration from dilute solution, and in the case of the mineral-induced processes, by particular effectiveness in ordering and selective reaction, directed toward formation of functional biomolecules. Numerous circumstances provide support for the notion that negatively charged molecules were functionally required and geochemically available for biopoesis. Sulfite ion may have been important in bisulfite complex formation with simple aldehydes, facilitating the initial concentration by sorption of aldehydes in positively charged surface active minerals. Borate ion may have played a similar, albeit less investigated role in forming charged sugar complexes. Among anionic species, oligophosphate ions and charged phosphate esters are likely to have been of even more wide ranging importance, reflected in the continued need for phosphate in a proposed RNA world, and extending its central role to evolved biochemistry. Phosphorylation is shown to result in selective concentration by surface sorption of compounds, otherwise too dilute to support condensation reactions. It provides protection against rapid hydrolysis of sugars and, by selective concentration, induces the oligomerization of aldehydes. As a manifestation of life arisen, phosphate already appears in an organic context in the oldest preserved sedimentary record.

NASA Discipline Exobiology↗
NASA NTRS2015

Recognizing Sulfate and Phosphate Complexes Adsorbed onto Nanophase Weathering Products on Mars

Nanophase weathering products (i.e., secondary phases that lack long-range atomic order) have been recognized on the martian surface via orbital observations and in-situ measurements from landed missions. Allophane, a poorly crystalline, hydrated aluminosilicate, has been identified at the regional scale in models of thermal-infrared (TIR) data from the Thermal Emission Spectrometer (TES) and at the local scale from visible/near-IR (VNIR) data from the Compact Reconnaissance Impact Spectrometer for Mars (CRISM) instrument and phase calculations of Alpha Particle X-ray Spectrometer (APXS) data of rocks encountered by the Mars Exploration Rovers (MER) Spirit and Opportunity. Nanophase iron oxides (npOx) have been recognized in rocks and soils measured by the Mössbauer Spectrometer on Spirit and Opportunity. Furthermore, analyses of X-ray diffraction data measured by the CheMin instrument onboard the Mars Science Laboratory rover Curiosity indicate rock and soil samples are comprised of approx. 20-50 wt.% X-ray amorphous materials. Chemical measurements by landed missions indicate the presence of sulfur and phosphorus in martian rocks in soils, and APXS data from Gusev crater demonstrate abundances of up to approx. 5 wt.% P2O5 and approx. 30 wt.% SO3. However, the speciation of phosphorus and sulfur is not always evident. On Earth, phosphate and sulfate anions can be chemisorbed onto the surfaces of nanophase weathering products. This process may also occur on Mars, and calculations of the composition of the amorphous component at Gale crater using CheMin mineral models and APXS data show that amorphous material is enriched in volatiles, including S. Here, we examine the ability to detect chemisorbed sulfate and phosphate complexes by analyzing sulfate- and phosphate-adsorbed nanophase weathering products using instruments similar to those on landed and orbital missions.

Rampe, E. B.↗
NASA NTRS2003

Decoupling of Iron and Phosphate in the Global Ocean

Iron is an essential micronutrient for marine phytoplankton, limiting their growth in high nutrient, low chlorophyll regions of the ocean. I use a hierarchy of ocean circulation and biogeochemistry models to understand controls on global iron distribution. I formulate a mechanistic model of iron cycling which includes scavenging onto sinking particles and complexation with an organic ligand. The iron cycle is coupled to a phosphorus cycling model. Iron's aeolian source is prescribed. In the context of a highly idealized multi-box model scheme, the model can be brought into consistency with the relatively sparse ocean observations of iron in the oceans. This biogeochemical scheme is also implemented in a coarse resolution ocean general circulation model. This model also successfully reproduces the broad regional patterns of iron and phosphorus. In particular, the high macronutrient concentrations of the Southern Ocean result from iron limitation in the model. Due to the potential ability of iron to change the efficiency of the carbon pump in the remote Southern Ocean, I study Southern Ocean surface phosphate response to increased aeolian dust flux. My box model and GCM results suggest that a global ten fold increase in dust flux can support a phosphate drawdown of 0.25-0.5 micromolar.

GLOBAL OCEAN MODEL↗
NASA NTRS1971

The role of phosphates in chemical evolution.

The hypohydrous thermal reaction between inorganic phosphates and nucleoside was investigated. The products of the reactions have been identified, and an attempt has been made to determine the mechanism. It was found that orthophosphates can be readily converted into condensed phosphates which are effective phosphorylating agents. Thermal polymerization of inorganic orthophosphates at moderate temperature as a general source of polyphosphates might have provided efficient phosphorylation and condensing agents for primordial syntheses.

Ponnamperuma, C.↗
NASA NTRS1972

Thermolabile triose phosphate isomerase in a psychrophilic Clostridium.

It was found that a psychrophilic Clostridium contains a triose phosphate isomerase which is very labile at moderate temperatures. An investigation showed that the optimal growth temperature of the psychrophile was between 15 and 20 deg C. No growth occurred at 25 deg C. The thermostability of the glycolytic enzymes in the cell-free extracts of Clostridium sp. strain 69 was studied. The data obtained show that the triose phosphate isomerase is quite labile at moderate temperatures. The instability of the enzyme is sufficient to explain the low maximum growth temperature of the psychrophile.

Shing, Y. W.↗
NASA NTRS1974

Prevention of bone mineral changes induced by bed rest: Modification by static compression simulating weight bearing, combined supplementation of oral calcium and phosphate, calcitonin injections, oscillating compression, the oral diophosphonatedisodium etidronate, and lower body negative pressure

The phenomenon of calcium loss during bed rest was found to be analogous to the loss of bone material which occurs in the hypogravic environment of space flight. Ways of preventing this occurrence are investigated. A group of healthy adult males underwent 24-30 weeks of continuous bed rest. Some of them were given an exercise program designed to resemble normal ambulatory activity; another subgroup was fed supplemental potassium phosphate. The results from a 12-week period of treatment were compared with those untreated bed rest periods. The potassium phosphate supplements prevented the hypercalciuria of bed rest, but fecal calcium tended to increase. The exercise program did not diminish the negative calcium balance. Neither treatment affected the heavy loss of mineral from the calcaneus. Several additional studies are developed to examine the problem further.

Schneider, V. S.↗
NASA NTRS1976

An experimental study of phosphate reduction and phosphorus-bearing lunar metal particles

Results are reported for two sets of experiments conducted to investigate the distribution and origin of phosphorus in lunar metal particles. The first set measured the equilibrium oxygen fugacity as a function of temperature for synthesized Fe-Ni and Fe-Ni-P alloys; the second set imposed various oxygen pressures so that the P distribution among the coexisting phases could be observed. The conditions of temperature, oxygen fugacity, and time necessary to produce P contents similar to those found in lunar metal particles are determined. The results show that: (1) the P distribution in lunar-type metal is controlled by oxygen fugacity, temperature, and bulk composition; (2) the P distribution is limited by the reaction rate at the metal surface and by the amount of phosphate in contact with the metal; (3) the nucleation and growth rate of phosphate controls the rate of P loss during oxidation; and (4) an oxygen fugacity of 10 to the -20th power atm at 950 C is required to saturate iron with P. It is concluded that a reducing species such as carbon may establish a local equilibrium and prevent oxygen communication with the surrounding rock.

Friel, J. J.↗
NASA NTRS1978

Analysis of surface tris (2,3-dibromopropyl) phosphate on chlorobutyl rubber SCAPE suits

Tris (2,30-dibromopropyl) phosphate was used to confer flame retardant properties on butyl rubber formulations used in protective clothing such as the self-contained atmospheric protective ensembles (SCAPE suits) worn at Kennedy Space Center in support of Apollo, Skylab, and Apollo-Soyuz missions since 1966. Because tris (2,3-dibromopropyl) phosphate is mutagenic, surface concentrations of the compound in SCAPE suits were investigated as were as potential methods of removing or isolating it. Analytical procedures for determining surface concentrations of the tris compound on non-porous materials are described. Soap-and-water washing is the most efficient method of removing the compound from fabricated SCAPE suits and unused material.

Schehl, T. A.↗