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At least 19 records

Cycling phosphorus on the Archean Earth: Part I. Continental weathering and riverine transport of phosphorus

Phosphorus (P) is the key nutrient thought to limit primary productivity on geological timescales. Phosphate levels in Archean marine sediments are low, but quantification of the P cycle and how it changed through a billion years of recorded Archean history remain a challenge, hindering our understanding of the role played by P in biosphere/geosphere co-evolution on the early Earth. Here, we design kinetic and thermodynamic models to quantitatively assess one key component of the early P cycle – continental weathering – by considering the emergence and elevation of continents, as well as the evolution of climate, the atmosphere, and the absence of macroscopic vegetation during the Archean Eon. Our results suggest that the weathering rate of apatite, the major P-hosting mineral in the rocks, was at least five times higher in the Archean Eon than today, attributable to high levels of pCO2,g. Despite this, the weathering flux of P to the oceans was negligible in the early Archean Eon, increasing to a level comparable to or greater than the modern by the end of eon, a consequence of accelerating continental emergence. Furthermore, our thermodynamic calculations indicate high solubilities of primary and secondary P-hosting minerals in the acidic weathering fluids on land, linking to high Archean pCO2,g. Thus, weathering of P was both kinetically and thermodynamically favorable on the Archean Earth, and river water could transport high levels of dissolved P to the oceans, as also supported by the observed P-depletion in our new compilation of Archean paleosols. Lastly, we evaluated the relative rates of physical erosion and chemical weathering of silicates during the Archean Eon. The results suggest that continental weathering on the early and middle Archean Earth might have been transport-limited due to low erosion rates associated with limited subaerial emergence and low plateau elevations; by the late Archean, however, continental weathering would have transited to kinetically-limited state because of continental emergence, increased plateau elevation, and weakening weathering rates. Overall, our weathering calculations together with paleosol evidence indicate an increasing flux of bioavailable P to the oceans through time, associated with late Archean continental emergence, reaching levels comparable to or higher than modern values by the end of the eon. Increased P fluxes could have fueled increasing rates of primary production, including oxygenic photosynthesis, through time, facilitating the irreversible oxidation of the Earth’s atmosphere early in the Proterozoic Eon.

Phosphorus↗

Cycling phosphorus on the Archean Earth: Part II. Phosphorus limitation on primary production in Archean ecosystems

Several lines of evidence point to low rates of net primary production (NPP) in Archean oceans. However, whether Archean NPP was limited by electron donors or nutrients, particularly phosphorus (P), and how these factors might have changed over a billion years of recorded Archean history, remains contentious. One major challenge is to understand quantitatively the biogeochemical cycling of P on the early Earth. In Part I of this series (Hao et al., 2020), we estimated the weathering flux of P to the oceans as a function of temporally increasing continental emergence and elevation through Archean time. In Part II, we conduct thermodynamic and kinetic simulations to understand key processes of P cycling within the Archean ocean, including seafloor weathering, recycling of organic P, the solubility and precipitation of secondary phosphate minerals, and the burial diagenesis of P precipitates. Our calculations suggest low solubilities of apatite minerals in Archean seawater, primarily due to nearly neutral pH and high levels of Ca. This low solubility, in turn, implies a negligible contribution of apatite dissolution to P bioavailability in Archean seawater. We also simulate the solubility limits of common secondary P-bearing minerals, showing that vivianite would have been the least soluble P mineral in ferruginous Archean seawater (0.1–0.3 µM), even at moderate supersaturation states (Ω = 100 or 1000). If vivianite precipitation was kinetically favorable by microbial activities and mineral adsorption, the sinking flux of P as vivianite in Archean seawater could have reached the modern sinking flux, implying that vivianite precipitation was a potentially major sink for P in Archean oceans. During burial diagenesis, however, vivianite in porewater would have become less stable than Ca-phosphates of lower solubility. At elevated temperatures (>100 °C) associated with burial diagenesis and low-grade metamorphism, vivianite is predicted to react irreversibly with calcite to form apatite. Optimistic assumptions about the recycling efficiency of P on the Archean Earth lead us to estimate that by the end of the eon the total flux of P (continental weathering + recycling) could have supported NPP at levels up to 7% of the modern. The total flux of P would have been much lower on the early and middle Archean Earth, whereas fluxes of electron donors could have been higher, suggesting very low productivity and P-limitation of marine ecosystems during much of the eon. Comparing our estimates of NPP as limited by P supply with the estimate by Ward et al. (2019), in which NPP was limited by electron donors and metabolic efficiency, there could have been a transition between P-limited productivity in the early to middle Archean to electron donor-limitation closer to the eon’s end (assuming no oxygenic photosynthesis). Once oxygenic photosynthesis reached ecological significance, probably near the end of the Archean, our estimated flux of P would allow rapid oxidation of atmosphere.

Vivianite↗

A Quantitative NMR Analysis of Phosphorus in Carbonaceous and Ordinary Chondrites

Phosphorus is important in a number of biochemical molecules, from DNA to ATP. Early life may have depended on meteorites as a primary source of phosphorus as simple dissolution of crustal apatite may not produce the necessary concentration of phosphate. Phosphorus is found in several mineral phases in meteorites. Apatite and other Ca- and Mg phosphate minerals tend to be the dominant phosphorus reservoir in stony meteorites, whereas in more iron-rich or reduced meteorites, the phosphide minerals schreibersite, (Fe, Ni)3P, and perryite, (Ni, Fe)5(Si, P)2 are dominant. However, in CM chondrites that have experienced significant aqueous alteration, phosphorus has been detected in more exotic molecules. A series of phosphonic acids including methyl-, ethyl-, propyl- and butyl- phosphonic acids were observed by GC-MS in Murchison. Phosphorian sulfides are in Murchison and Murray. NMR spectrometry is capable of detecting multiple substances with one experiment, is non-destructive, and potentially quantitative, as discussed below. Despite these advantages, NMR spectrometry is infrequently applied to meteoritic studies due in large part to a lack of applicability to many compounds and the relatively high limit of detection requirements. Carbon-13 solid-state NMR has been applied to macromolecular carbon in Murchison. P-31 NMR has many advantages over aqueous carbon-13 NMR spectrometry. P-31 is the only isotope of phosphorus, and P-31 gives a signal approximately twice as strong as C-13. These two factors together with the relative abundances of carbon and phosphorus imply that phosphorus should give a signal approximately 20 as strong as carbon in a given sample. A discussion on the preparation of the quantitative standard and NMR studies are presented

Pasek, M. A.↗

Mode of incorporation of phosphorus in Hg(0.8)Cd(0.2)Te

Selim and Kroeger (1977) have studied the mode of incorporation of phosphorus in CdTe. According to their findings, phosphorus behaves amphoterically in CdTe acting as an acceptor interstitially and on Te lattice sites, and as a triple donor on Cd lattice sites. The present investigation is concerned with the role of phosphorus in Hg(0.8)Cd(0.2)Te, taking into account Hall-effect and mobility measurements on phosphorus-doped crystals quenched from a temperature in the range from 450 to 600 C subsequent to anneals in different partial pressures of Hg. It is found that the behavior of phosphorus in Hg(0.8)Cd(0.2)Te is similar to that established for CdTe, except that all the electrically active phosphorus defect centers in Hg(0.8)Cd(0.2)Te appear to be only singly ionized. At low Hg pressure, phosphorus is incorporated as a single donor occupying Hg lattice sites, and at high Hg pressure, as a single acceptor on interstitial sites and Te lattice sites.

Vydyanath, H. R.↗

Photoabsorption Study of Bacillus megaterium, DNA and Related Biological Materials in the Phosphorus K-edge Region

We have measured the x-ray transmission spectra of several biologically related samples in the phosphorus K-edge absorption region. These include elemental red phosphorus, hydrated sodium phosphate (Na3PO4.12H2O), deoxyribonucleic acid (DNA), adenosinetriphosphate (ATP), diolylphosphatidyl choline (DOPC), and Bacillus megaterium spores. Elemental red phosphorus essentially displays an edge-jump. All other spectra are similar in form and energy position. Each spectrum for these substances is dominated by a narrower, more intense first peak and a broader but less intense second peak. The corresponding K-edge absorption thresholds are shifted towards higher energy relative to that for elemental red phosphorus, as expected for increasing degrees of phosphorus oxidation. The B. megaterium spectrum has aspects common to both the phosphate and DNA spectra and is therefore interpreted as a composite of spectra arising from DNA/RNA and phosphates within the spore. The B. megaterium spore spectrum provides needed information for resonant radiation damage studies in the phosphorus K-edge absorption region by identifying candidate photoexcitations. In addition,the absorption spectra will be useful in macromolecular crystallography studies employing anomalous dispersion effects at the phosphorus K-edge.

Frigo, Sean P.↗

Photoabsorption study of Bacillus megaterium, DNA and Related Biological Materials in the Phosphorus K-edge Region

We have measured the x-ray transmission spectra of several biologically related samples in the phosphorus K-edge absorption region. These include red phosphorus, hydrated sodium phosphate (Na3PO4 12 H2O), deoxyribonucleic acid (DNA), adenosinetriphosphate (ATP), diolylphosphatidyl choline (DOPC), and Bacillus megaterium spores. Red phosphorus essentially displays an edge-jump. All other spectra are similar in form and energy position, where each is dominated by a narrower, more intense first peak and a broader but less intense second peak. The corresponding K-edge absorption thresholds are shifted towards higher energy relative to that for red phosphorus, as expected for increasing degrees of phosphorus oxidation. The B.meguterium spectrum has aspects common to both the phosphate and DNA spectra and is therefore interpreted as a composite of spectra arising from DNA/RNA and phosphates within the spore. The B. megaterium spore spectrum provides needed information for resonant radiation damage studies in the phosphorus K-edge absorption region by identifying candidate photoexcitations. In addition, the absorption spectra will be useful in macromolecular crystallography studies employing anomalous dispersion effects at the phosphorus K-edge.

Frigo, Sean P.↗

Phosphorus Equilibria Among Mafic Silicate Phases

Phosphorus incorporation in major rock-forming silicate minerals has the following implications: (1) Reactions between phosphorus-hosting major silicates and accessory phosphates, which are also major trace element carriers, may control the stability of the latter and thus may affect the amount of phosphorus and other trace elements released to the coexisting melt or fluid phase. (2) Less of a phosphate mineral is needed to account for the bulk phosphorus of planetaty mantles. (3) During partial melting of mantle mineral assemblages or equilibrium fractional crystallization of basaltic magmas, and in the absence or prior to saturation with a phosphate mineral, silicate melts may become enriched in phosphorus, especially in the geochemically important low melt fraction regime, Although the small differences in the ionic radii of IVp5+, IVSi4+, and IV Al3+ makes phosphoms incorporation into crystalline silicates perhaps unsurprising, isostructural silicate and phosphate crystalline solids do not readily form solutions, e.g., (Fe, Mg)2SiO4 vs. LiMgPO4, SiO)2 VS. AlPO4. Nonetheless, there are reports of, poorly characterized silico-phosphate phases in angrites , 2-4 wt% P2O5 in olivine and pyroxene grains in pallasites and reduced terestrial basalts which are little understood but potentially useful, and up to 17 wt% P2O5 in olivine from ancient slags. However, such enrichments are rare and only underscore the likelihood of phosphoms incorporation in silicate minerals. The mechanisms that allow phosphorus to enter major rock-forming silicate minerals (e.g., Oliv, Px, Gt) remain little understood and the relevant data base is limited. Nonetheless, old and new high-pressure (5-10 GPa) experimental data suggest that P2O5 wt% decreases from silica-poor to silica-rich compositions or from orthosilicate to chain silicate structures (garnet > olivine > orthopyroxene) which implies that phosphorus incorporation in silicates is perhaps more structure-than site-specific. The data also indicate that DXVliQP2O5 decrease in the same order, but DOVLiQP2O5 and DOpx/LiQP205 are likely constant, respectively equal to 0.08(3) and 0.007(4), in contrast, DG1ILiQP205 increases from 0.15(3) to 0.36(10) as garnet becomes majoritic, thus silica-enriched, and may also depend on liquid composition (SiO2, P2O5 and Na2O wt%).

Berlin, Jana↗

Phosphorus, a key to life on the primitive earth

The phosphorus of the primitive earth was present as phosphates. It is strongly probable that a portion of the phosphate was present as condensed phosphates. The primitive earth was highly deficient in the total available phosphorus until a sufficient quantity of phosphorus weathered from the igneous rocks in which it was entrapped. Approximately three billion years were required for the seas to become saturated. Until this time passed the seas acted as a giant sink for phosphorus, diluting it to the extent that all forms of life were deprived of the vital nutrient. When the seas became saturated, the rate of turnover of the phosphorus increased rapidly. As the seas pulsated, they left the excess precipitate phosphorus as sedimentary rock in locally rich deposits on which life could thrive.

Griffith, E. J.↗

Effect of a 30-day isolation stress on calcium, phosphorus and other excretory products in an unrestrained chimpanzee.

An unrestrained chimpanzee was studied in an isolation chamber and in his home cage environment. The study consisted of 49 urine collection days (14 days pre-, 5 days post- and 30 days of isolation), and then of 10 days in the home cage. Dietary intake, urine and fecal data were obtained. The effect of isolation on various excretory parameters was studied. Urine samples were analyzed for volume, osmolarity, creatinine, creatine, urea-N, 17-hydroxy corticosteroids, VMA, calcium and inorganic phosphorus. One way analyses of variance performed on the urinary excretion parameters showed all except creatinine excretion to vary significantly during periods of the study. The changes observed in calcium and phosphorus were highly significant. The data suggests that the calcium to phosphorus excretion ratio might serve as a physiological stress indicator of Selye's adaptation syndrome (period of resistance).

Sabbot, I. M.↗

Observations of interstellar chlorine and phosphorus

Copernicus observations of interstellar Cl I, Cl II, and P II UV lines toward 10 stars are reported. Column densities are estimated for each species, and upper limits are computed for HCl column densities. Derivation of the gas-phase abundances of chlorine and phosphorus indicates that the averages of both the chlorine and the phosphorus logarithmic abundances relative to hydrogen are between 5.0 and 5.1. It is suggested that interstellar chlorine may be depleted by about a factor of 3 relative to the solar abundance and that interstellar phosphorus is depleted by a factor of 2 to 3. The results are shown to support the prediction that chlorine is ionized in regions containing primarily atomic oxygen and is neutral in regions where there is a significant amount of molecular hydrogen. The photoionization rate of neutral chlorine toward 15 Mon is estimated, and it is concluded that most chlorine is contained within the gas phase.

Jura, M.↗

The role of phosphorus in the upper atmosphere of Jupiter

The reaction of elemental phosphorus and H atoms to form PH3 was observed and should be a major factor in the recycling of PH3 in the stratosphere of Jupiter. The formation of PH3 in this manner should predominate at high altitudes where, due to the very low temperatures, reactions that require higher activation energies than these atom reactions cannot occur. At lower altitudes, in the troposphere, the rapid formation of H atoms from the strong absorption of light by NH3 will contribute to phosphine production also in this same manner. Recent experiments have also shown that elemental phosphorus reacts readily with aqueous ammonia to form PH3. This reaction may also be important in the recycling of PH3 in the upper troposphere of Jupiter if water-ammonia clouds, as had been previously thought, exist. Considerations of the coloration of the Great Red Spot have been made based upon the nature of the phosphorus obtained by decomposition of the phosphine.

Howland, G. R.↗

The combined effects of ionizing radiation and weightlessness on calcium and phosphorus content in the mineral fraction of the calcified tissues in the rat skeleton

Phosphorus and calcium content in the ash from skeletal bones (ribs, scapula, vertebra, and crus) of 30 rats exposed to ionizing radiation (800 rads) on the flight of the Kosmos 690 biosatellite was studied. A 10 percent decrease in ash content coefficient and 29 percent decrease in phosphorus content was found immediately after the flight, and a 9 percent decrease in phosphorus content persisted after 26 days of readaptation to terrestrial conditions.

Prokhonchukov, A. A.↗

Flammability of Epoxy Resins Containing Phosphorus

As part of a program to develop fire-resistant exterior composite structures for future subsonic commercial and general aviation aircraft, flame-retardant epoxy resins are under investigation. Epoxies and their curing agents (aromatic diamines) containing phosphorus were synthesized and used to prepare epoxy formulations. Phosphorus was incorporated within the backbone of the epoxy resin and not used as an additive. The resulting cured neat epoxy formulations were characterized by thermogravimetric analysis, propane torch test, elemental analysis, microscale combustion calorimetry, and fire calorimetry. Several formulations showed excellent flame retardation with phosphorous contents as low as 1.5% by weight. The fracture toughness and compressive strength of several cured formulations showed no detrimental effect due to phosphorus content. The chemistry and properties of these new epoxy formulations are discussed.

Flammability studies↗

Importance of Sulfur for Phosphorus Mobility on the Martian Surface

Sulfur and phosphorus were mobile on the martian surface, and we present evidence that sulfate was likely a control on phosphate mobility. Mobility of the two elements on the martian surface is crucial for the habitability of Mars because their availability for biochemical reactions and biological structures is a major constraint on life. In the sedimentary rocks of Gale crater, the rover Curiosity has discovered evidence of mobile S and P with the alpha particle X-ray spectrometer (APXS). Sulfur-rich fluids are evident in ubiquitous Ca-sulfate veins that crosscut the bedrock. Compelling evidence of P mobility is in nodules, veins, crusts, and haloes with P2O5 enrichments (1.5-7.5 wt%) relative to the median bedrock (0.9-1.2 wt%) and average basaltic crust (~0.9 wt%). We have investigated phosphorus mobility in Hawaiian analogues, where the primary P2O5 (0.2-2.1 wt%) is contained in Ca-apatite. Four relevant processes have emerged: (1) In open-system, circumneutral regolith weathering profiles, we found up to 40% of the P was leached over 10s-100s ka. (2) Natural acid-sulfate alteration at the Maunakea summit resulted in the dissolution of apatite and mobilization of phosphate 10s-1000s µm to rock surfaces where it formed Al-phosphates and substituted into crystalline sulfates (alunite and jarosite). (3) Experimental results indicate that basaltic sediment chemisorbs phosphate (pH < 7). (4) In experimental systems containing water, basaltic sediment, and a starting pH = 2-7, phosphate has higher solubility in chloride-rich fluids, but significantly lower solubility in sulfate-rich fluids. For example, in water doped with phosphate (~100-500 mg/L), ~60-80% of the PO43- was removed from the sulfate-rich fluid, whereas ~20% of the PO43- was removed from the Cl-rich and pure water fluids (likely via adsorption). Gypsum precipitated from the sulfate-rich fluids; the fate of phosphate in the solid residue is unconfirmed. The potential for phosphate incorporation in martian sulfates is reflected in the enrichment of P2O5 in Gale Ca-sulfate veins, based on preliminary analyses of APXS data. Models for the mobility of phosphorus in Gale crater should consider these conflicting P characteristics: (1) P solubility may have been inhibited by sulfate and (2) P¬ is enriched in diagenetic features and was therefore mobile.

Jeff A. Berger↗

Partial pressures of oxygen, phosphorus and fluorine in some lunar lavas

Lunar sample 14310 is a feldspar-rich basalt which shows no evidence of shock deformation or recrystallization. Pyroxenes include Mg-rich orthopyroxene, pigeonite and augite; pyroxferroite occurs in the interstitial residuum. Plagioclase feldspars are zoned from An(96) to An(67), and variations in feldspar compositions do not necessarily indicate loss of Na during eruption of the lava. Opaque phases include ilmenite, ulvospinel, metallic iron, troilite, and schreibersite. Both whitlockite and apatite are present, and the interstitial residua contain baddeleyite, tranquillityite and barium-rich sanidine. Theoretical calculations provide estimates of partial pressures of oxygen, phosphorus, and fluorine in lunar magmas. In general, partial pressures of oxygen are restricted by the limiting assemblages of iron-wuestite and ilmenite-iron-rutile; phosphorus partial pressures are higher in lunar magmas than in terrestrial lavas. The occurrence of whitlockite indicates significantly lower fugacities of fluorine in lunar magmas than in terrestrial magmas.

Nash, W. P.↗

Tibial bone mineral distribution as influenced by calcium, phosphorus, and vitamin D feeding levels in the growing turkey

Roentgen signs, subperiosteal, endosteal, and trabecular bone growth are evaluated in turkeys fed phosphorus at the 0.5, 0.56, 0.68, 0.90, and 2.70 percent levels. Calcium levels of 0.30, 0.40, 0.60, 1.2, and 3.60 percent were also tested. Vitamin D levels of 0, 100, 300, 900 and 27,000 I.U. per day were likewise evaluated. Roentgen signs, bone mineral as measured by T-125 gamma ray absorption, and bone mineral growth patterns as shown by radiograph area projection are correlated with calcium, phosphorus, and vitamin D feeding levels. Differences in bone growth at the various feeding levels were observed which were not reflected by differences in other studied parameters.

Spurrell, F. A.↗

Non-mass-analyzed ion implantation from a solid phosphorus source

A phosphorus ion beam, extracted from a Freeman ion source charged with elemental phosphorus, has been investigated for use in solar cell fabrication. Mass spectroscopy of the beam indicates the absence of both minority-carrier lifetime degrading impurities and hydrogen. The ion beam, without mass analysis, was used for ion implantation of solar cells, and performance for all cells was found to be equivalent to mass-analyzed controls.

Spitzer, M. B.↗

The chemistry of phosphorus in dense interstellar clouds

Laboratory experiments show that the ion-molecule chemistry of phosphorus is significantly different from that of nitrogen in dense interstellar clouds. The PH3 molecule is not readily formed by gas-phase, ion-molecule reactions in these regions. Laboratory results used in a simple kinetic model indicate that the most abundant molecule containing phosphorus in dense clouds is PO.

Thorne, L. R.↗