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NASA NTRS2012

Examination of Surface Residuals Obtained During Re-Lubrication of the International Space Station (ISS) Solar Alpha Rotary Joint (SARJ)

The starboard SARJ mechanism on the ISS suffered a premature lubrication failure, resulting in widespread loss of the nitride case layer on its 10.3 meter circumference, 15-5PH steel race ring [1, 2]. To restore functionality, vacuum-stable grease was applied on-orbit, first to the port SARJ mechanism to save it from the damage suffered by the starboard mechanism. After 3 years of greased operation, telemetry indicated that the port mechanism required relubrication, so part of that process included sampling each of the three race ring surfaces to evaluate any wear debris recovered and the state of the originally applied grease. Extensive microscopic examination was conducted, which directed subsequent microanalysis of particulate. Since the SARJ mechanism operates in the vacuum of space, a sampling method and tool had to be developed for use by astronauts while working in the extravehicular mobility unit (EMU). The sampling tool developed was a cotton terry-cloth mitt for the EMU glove, with samples taken by swiping each of the three port SARJ race-ring surfaces. The sample mitts for each surface were folded inward after sampling to preserve sample integrity, for return and ground analysis. The sample mitt for what is termed the outer canted surface of the SARJ race-ring is shown in Figure 1. Figure 1 also demonstrates how increasing levels of magnification were used to survey the contamination removed in sampling, specifically looking for signs of wear debris or other features which could be further evaluated using Scanning Electron Microscopy (SEM) methods. The most surprising overall result at this point in the analysis was the relatively small amounts of grease recovered during sampling. It is clear that the mechanism was not operating with surplus lubricant. Obviously, evidence of molybdenum disulfide (MoS2), a major component in the grease applied, was prevalent in the analysis conducted. But a small amount of mechanism wear debris was observed. Figure 2 shows an example of a region of concentrated wear debris. Although some MoS2 is observed, most of the contaminant in this location is nitrided 15-5PH steel, as verified by the associated chemical analysis. High oxygen content was also observed which, when associated with the apparent friable nature of the steel material, suggests that this contaminant could be quite old, perhaps even associated with the mechanism s original manufacture and acceptance testing. Additional microscopic

Martinez, J. E.↗

NASA NTRS2013

The Mineralogical and Chemical Case for Habitability at Yellowknife Bay, Gale Crater, Mars

Sediments of the Yellowknife Bay formation (Gale crater) include the Sheepbed member, a mudstone cut by light-toned veins. Two drill samples, John Klein and Cumberland, were collected and analyzed by the CheMin XRD/XRF instrument and the Sample Analysis at Mars (SAM) evolved gas and isotopic analysis suite of instruments. Drill cuttings were also analyzed by the Alpha Particle X-ray Spectrometer (APXS) for bulk composition. The CheMin XRD analysis shows that the mudstone contains basaltic minerals (Fe-forsterite, augite, pigeonite, plagioclase), as well as Fe-oxide/hydroxides, Fe-sulfides, amorphous materials, and trioctahedral phyllosilicates. SAM evolved gas analysis of higher-temperature OH matches the CheMin XRD estimate of ~20% clay minerals in the mudstone. The light-toned veins contain Ca-sulfates; anhydrite and bassanite are detected by XRD but gypsum is also indicated from Mastcam spectral mapping. These sulfates appear to be almost entirely restricted to late-diagenetic veins. The sulfate content of the mudstone matrix itself is lower than other sediments analyzed on Mars. The presence of phyllosilicates indicates that the activity of water was high during their formation and/or transport and deposition (should they have been detrital). Lack of chlorite places limits on the maximum temperature of alteration (likely <100 C). The presence of Ca-sulfates rather than Mg- or Fe-sulfates suggests that the pore water pH was near-neutral and of relatively low ionic strength (although x-ray amorphous Mg-and Fe- sulfates could be present and undetectable by CheMin). The presence of Fe and S in both reduced and oxidized states represents chemical disequilibria that could have been utilized by chemolithoautotrophic biota, if present. When compared to the nearby Rocknest sand shadow mineralogy or the normative mineralogy of Martian soil, both John Klein and Cumberland exhibit a near-absence of olivine and a surplus of magnetite (7-9% of the crystalline component). The magnetite is interpreted as an authigenic product formed when olivine was altered to phyllosilicate. Saponitization of olivine (a process analogous to serpentinization) could have produced H2 in situ. Indeed, early diagenetic hollow nodules ("minibowls") present in the Cumberland mudstone are interpreted by some as forming when gas bubbles accumulated in the unconsolidated mudstone. Lastly, all of these early diagenetic features appear to have been preserved with minimal alteration since their formation, as indicated by the ease of drilling (weak lithification, lack of cementing phases), the presence of 20-30% amorphous material, and the late-stage fracturing with emplacement of calcium sulfate veins and minibowl infills, where they were intersected by veins. A rough estimate of the minimum duration of the lacustrine environment is provided by the minimum thickness of the Sheepbed member. Given 1.5 meters, and applying a mean sediment accumulation rate for lacustrine strata of 1 m/1000 yrs yields a duration of 1,500 years. If the aqueous environments represented by overlying strata are considered, such as Gillespie Lake and Shaler, then this duration increases. The Sheepbed mudstone meets all the requirements of a habitable environment: Aqueous deposition at clement conditions of P, T, pH, Eh and ionic strength, plus the availability of sources of chemical energy.

Blake, David Frederick↗

NASA NTRS1998

Sympathetic activation in exercise is not dependent on muscle acidosis. Direct evidence from studies in metabolic myopathies

Muscle acidosis has been implicated as a major determinant of reflex sympathetic activation during exercise. To test this hypothesis we studied sympathetic exercise responses in metabolic myopathies in which muscle acidosis is impaired or augmented during exercise. As an index of reflex sympathetic activation to muscle, microneurographic measurements of muscle sympathetic nerve activity (MSNA) were obtained from the peroneal nerve. MSNA was measured during static handgrip exercise at 30% of maximal voluntary contraction force to exhaustion in patients in whom exercise-induced muscle acidosis is absent (seven myophosphorylase deficient patients; MD [McArdle's disease], and one patient with muscle phosphofructokinase deficiency [PFKD]), augmented (one patient with mitochondrial myopathy [MM]), or normal (five healthy controls). Muscle pH was monitored by 31P-magnetic resonance spectroscopy during handgrip exercise in the five control subjects, four MD patients, and the MM and PFKD patients. With handgrip to exhaustion, the increase in MSNA over baseline (bursts per minute [bpm] and total activity [%]) was not impaired in patients with MD (17+/-2 bpm, 124+/-42%) or PFKD (65 bpm, 307%), and was not enhanced in the MM patient (24 bpm, 131%) compared with controls (17+/-4 bpm, 115+/-17%). Post-handgrip ischemia studied in one McArdle patient, caused sustained elevation of MSNA above basal suggesting a chemoreflex activation of MSNA. Handgrip exercise elicited an enhanced drop in muscle pH of 0.51 U in the MM patient compared with the decrease in controls of 0.13+/-0.02 U. In contrast, muscle pH increased with exercise in MD by 0.12+/-0.05 U and in PFKD by 0.01 U. In conclusion, patients with glycogenolytic, glycolytic, and oxidative phosphorylation defects show normal muscle sympathetic nerve responses to static exercise. These findings indicate that muscle acidosis is not a prerequisite for sympathetic activation in exercise.

NASA Discipline Cardiopulmonary↗

NASA NTRS1987

Long-term acid-induced wall extension in an in-vitro system

When frozen-thawed Avena sativa L. coleoptile and Cucumis sativa L. hypocotyl sections, under tension, are acid-treated, they undergo rapid elongation (acid-extension). The acid-extension response consists of two concurrent phases: a burst of extension which decays exponentially over 1-2 h (ExE), and a constant rate of extension (CE) which can persist for at least 6h. The extension (delta L) is closely represented by the equation: delta L = a-a e(-kt) + C t where a is the total extension of the exponential phase, k is the rate constant for ExE, and c is the rate of linear extension (CE). Low pH and high tension increased a and c, whereas temperature influenced k. The magnitude of the CE (over 50% extension/10 h), the similarity in its time course to auxin-induced growth, and the apparent yield threshold for CE indicate that CE is more likely than ExE to be the type of extension which cell walls undergo during normal auxin-induced growth.

Non-NASA Center↗

NASA NTRS1982

The importance of ozone in the oxidation of sulfur dioxide in nonurban tropospheric clouds

In studies of the various possible mechanisms which contribute to the conversion of atmospheric sulfur dioxide to sulfate aerosol in the atmosphere, oxidation within the aqueous, droplet phase of tropospheric clouds has been identified as a major contributor. It has appeared that possibly much of this oxidation is by hydrogen peroxide, with the contribution from ozone being only minimal. The present investigation is concerned with the relative importance of O3 and H2O2 oxidation as a function of pH. The results of a new experimental study of the O3-S(IV) reaction in aqueous solution are presented, and potential S(IV) oxidation rates by O3 in cloud water are compared with those predicted for H2O2. The investigation indicates the potential importance of O3 as a contributor to the overall oxidative conversion of SO2 within typical nonpolluted tropospheric clouds.

Maahs, H. G.↗

NASA NTRS1979

The correlation and quantification of airborne spectroradiometer data to turbidity measurements at Lake Powell, Utah

A water sampling program was accomplished at Lake Powell, Utah, during June 1975 for correlation to multispectral data obtained with a 500-channel airborne spectroradiometer. Field measurements were taken of percentage of light transmittance, surface temperature, pH and Secchi disk depth. Percentage of light transmittance was also measured in the laboratory for the water samples. Analyses of electron micrographs and suspended sediment concentration data for four water samples located at Hite Bridge, Mile 168, Mile 150 and Bullfrog Bay indicated differences in the composition and concentration of the particulate matter. Airborne spectroradiometer multispectral data were analyzed for the four sampling locations. The results showed that: (1) as the percentage of light transmittance of the water samples decreased, the reflected radiance increased; and (2) as the suspended sediment concentration (mg/l) increased, the reflected radiance increased in the 1-80 mg/l range. In conclusion, valuable qualitative information was obtained on surface turbidity for the Lake Powell water spectra. Also, the reflected radiance measured at a wavelength of 0.58 micron was directly correlated to the suspended sediment concentration.

Merry, C. J.↗

NASA NTRS1998

Effect of land-use practice on soil moisture variability for soils covered with dense forest vegetation of Puerto Rico

Little is known about the landuse management effect on soil moisture and soil pH distribution on a landscape covered with dense tropical forest vegetation. This study was conducted at three locations where the history of the landuse management is different. Soil moisture was measured using a 6-cm three-rod Time Domain Reflectometery (TDR) probe. Disturbed soil samples were taken from the top 5-cm at the up, mid, and foothill landscape position from the same spots where soil moisture was measured. The results showed that soil moisture varies with landscape position and depth at all three locations. Soil pH and moisture variability were found to be affected by the change in landuse management and landscape position. Soil moisture distribution usually expected to be relatively higher in the foothill (P3) area of these forests than the uphill (P1) position. However, our results indicated that in the Luquillo and Guanica site the surface soil moisture was significantly higher for P1 than P3 position. These suggest that the surface and subsurface drainage in these two sites may have been poor due to the nature of soil formation and type.

Tsegaye, T.↗

NASA NTRS2005

Fundamental Mvssbauer Parameters of Hydrous Iron Sulfates

Hydrous iron sulfates, which form as alteration products of sulfides, are rare on Earth. On Mars, the low temperature and pH found in the martian permafrost create ideal conditions for the formation of this group of minerals [1], which includes such phases as coquimbite (Fe2(SO4) 9H2O) and amarantite (FeSO4(OH) 3H2O). Viking, Mars Pathfinder, MER and OMEGA data [e.g., [2]] have all indicated the presence of high sulfur contents on the surface of Mars, but the mineralogy of the sulfur-rich phases has not been well constrained. Recent work by [3] suggests that hydrous iron sulfates might satisfy the Martian thermal emission, vis-near IR, and M ssbauer spectra. These data suggest that sulfide and sulfate minerals might be significant contributors to all types of spectra acquired on the Martian surface.

Rothstein, Y.↗

NASA NTRS1988

Characterization of 15 selected coccal bacteria isolated from Antarctic rock and soil samples from the McMurdo-Dry Valleys (South-Victoria Land)

Approximately 1500 cultures of microorganisms were isolated from rocks and soils of the Ross Desert (McMurdo-Dry Valleys). From these, 15 coccoid strains were chosen for more detailed investigation. They were characterized by morphological, physiological and chemotaxonomical properties. All isolates were Gram-positive, catalase-positive and nonmotile. Six strains showed red pigmentation and could be identified as members of the genera Micrococcus (M. roseus, M. agilis) or Deinococcus. In spite of their coccoid morphology, the remaining nine strains had to be associated with coryneform bacteria (Arthrobacter, Brevibacterium), because of their cell wall composition and G+C ratios. Most of the strains were psychrotrophic, but one strain was even obligately psychrophilic, with a temperature maximum below 20 degrees C. Red cocci had in vitro pH optima above 9.0 although they generally originated from acid samples. Most isolates showed a preference for sugar alcohols and organic acids, compounds which are commonly known to be released by lichens, molds and algae, the other components of the cryptoendolithic ecosystem. These properties indicate that our strains are autochthonous members of the natural Antarctic microbial population.

NASA Program Exobiology↗

NASA NTRS2001

Ectomycorrhizal fungal associates of Pinus contorta in soils associated with a hot spring in Norris Geyser Basin, Yellowstone National Park, Wyoming

Molecular methods and comparisons of fruiting patterns (i.e., presence or absence of fungal fruiting bodies in different soil types) were used to determine ectomycorrhizal (EM) associates of Pinus contorta in soils associated with a thermal soil classified as ultra-acidic to extremely acidic (pH 2 to 4). EM were sampled by obtaining 36 soil cores from six paired plots (three cores each) of both thermal soils and forest soils directly adjacent to the thermal area. Fruiting bodies (mushrooms) were collected for molecular identification and to compare fruiting body (above-ground) diversity to below-ground diversity. Our results indicate (i) that there were significant decreases in both the level of EM infection (130 +/- 22 EM root tips/core in forest soil; 68 +/- 22 EM root tips/core in thermal soil) and EM fungal species richness (4.0 +/- 0.5 species/core in forest soil; 1.2 +/- 0.2 species/core in thermal soil) in soils associated with the thermal feature; (ii) that the EM mycota of thermal soils was comprised of a small set of dominant species and included very few rare species, while the EM mycota of forest soils contained a few dominant species and several rare EM fungal species; (iii) that Dermocybe phoenecius and a species of Inocybe, which was rare in forest soils, were the dominant EM fungal species in thermal soils; (iv) that other than the single Inocybe species, there was no overlap in the EM fungal communities of the forest and thermal soils; and (v) that the fungal species forming the majority of the above-ground fruiting structures in thermal soils (Pisolithus tinctorius, which is commonly used in remediation of acid soils) was not detected on a single EM root tip in either type of soil. Thus, P. tinctorius may have a different role in these thermal soils. Our results suggest that this species may not perform well in remediation of all acid soils and that factors such as pH, soil temperature, and soil chemistry may interact to influence EM fungal community structure. In addition, we identified at least one new species with potential for use in remediation of hot acidic soil.

Pinus/microbiology↗

NASA NTRS1981

Factors influencing the rate of non-enzymatic activation of carboxylic and amino acids by ATP

The nonenzymatic formation of adenylate anhydrides of carboxylic and amino acids is discussed as a necessary step in the origin of the genetic code and protein biosynthesis. Results of studies are presented which have shown the rate of activation to depend on the pKa of the carboxyl group, the pH of the medium, temperature, the divalent metal ion catalyst, salt concentration, and the nature of the amino acid. In particular, it was found that of the various amino acids investigated, phenylalanine had the greatest affinity for the adenine derivatives adenosine and ATP. Results thus indicate that selective affinities between amino acids and nucleotides were important during prebiotic chemical evolution, and may have played a major role in the origin of protein synthesis and genetic coding.

Mullins, D. W., Jr.↗

NASA NTRS1989

Polyamine binding to proteins in oat and Petunia protoplasts

Previous work (A Apelbaum et al. [1988] Plant Physiol 88: 996-998) has demonstrated binding of labeled spermidine (Spd) to a developmentally regulated 18 kilodalton protein in tobacco tissue cultures derived from thin surface layer explants. To assess the general importance of such Spd-protein complexes, we attempted bulk isolation from protoplasts of Petunia and oat (Avena sativa). In Petunia, as in tobacco, fed radioactive Spd is bound to protein, but in oat, Spd is first converted to 1,3,-diaminopropane (DAP), probably by polyamine oxidase action. In oat, binding of DAP to protein depends on age of donor leaf and conditions of illumination and temperature, and the extraction of the DAP-protein complex depends upon buffer and pH. The yield of the DAP-protein complex was maximized by extraction of frozen-thawed protoplasts with a pH 8.8 carbonate buffer containing SDS. Its molecular size, based on Sephacryl column fractionation of ammonium sulfate precipitated material, exceeded 45 kilodaltons. Bound Spd or DAP can be released from their complexes by the action of Pronase, but not DNAse, RNAse, or strong salt solutions, indicating covalent attachment to protein.

NASA Discipline Plant Biology↗

NASA NTRS2009

Efficacy of Various Chemical Disinfectants on Biofilms Formed in Spacecraft Potable Water System Component

As the provision of potable water is critical for successful habitation of the International Space Station (ISS), life support systems were installed in December 2008 to recycle both humidity from the atmosphere and urine to conserve available water in the vehicle. Pre-consumption testing from the dispensing needle at the Potable Water Dispenser (PWD) indicated that bacterial concentrations exceeded the current ISS specifications of 50 colony forming units (CFU) per ml. Subsequent investigations revealed that a corrugated stainless steel flex hose upstream of the dispensing needle in the PWD was filled with non-sterile water and left at room temperature for over one month before launch. To simulate biofilm formation that was suspected in the flight system, sterile flex hoses were seeded with a consortium of bacterial isolates previously recovered from other ISS water systems, which included Ralstonia pickettii, Burkholderia multivorans, Caulobacter vibrioides., and Cupriavidus pauculus. After 5 days of incubation, these hoses were challenged with various chemical disinfectants including hydrogen peroxide, colloidal silver, and buffered pH solutions to determine the ability of the disinfectants to decrease and maintain bacterial concentrations below ISS specifications. Disinfection efficacy over time was measured by collecting daily heterotrophic plate counts following exposure to the disinfectants. A single flush with either 6% hydrogen peroxide solution or a mixture of 3% hydrogen peroxide and 400 ppb colloidal silver effectively reduced the bacterial concentrations to less than 1 CFU/ml for a period of up to 2 months. Testing results indicated that hydrogen peroxide and mixtures of hydrogen peroxide and colloidal silver have tremendous potential as alternative disinfectants for ISS water systems.

Wong, Willy↗

NASA NTRS1981

Cloud water chemistry and the production of sulfates in clouds

Measurements are presented of the pH and ionic content of water collected in clouds over western Washington and the Los Angeles Basin. Evidence for sulfate production in some of the clouds is presented. Not all of the sulfur in the cloud water was in the form of sulfate. However, the measurements indicate that the production of sulfate in clouds is of considerable significance in the atmosphere. Comparison of field measurements with model results show reasonable agreement and suggest that the production of sulfate in cloud water is a consequence of more than one conversion mechanism.

Hegg, D. A.↗

NASA NTRSDate not supplied

Advancing Satellite-Constrained Modeled Air-Sea CO 2 Fluxes With a Focus on the Strength of the Southern Ocean Carbon Sink

Challenge and Motivation: The ocean plays a critical role in mitigating climate change by removing approximately a quarter of annual anthropogenic CO 2 emissions from the atmosphere. Model-based estimates point to the Southern Ocean as a key marine region, responsible for approximately 40 % of the anthropogenic carbon uptake by the global ocean. However, the contemporary strength of the Southern Ocean carbon sink has recently come into question. On the one hand, airborne-based observations of atmospheric CO 2 gradients indicate that the Southern Ocean represents a strong net sink of atmospheric CO 2 , consistent in magnitude with atmospheric inversion estimates and surface-ocean partial pressure of CO 2 (pCO 2 )-based products. On the other hand, estimates of pCO 2 based on in situ pH measurements taken by biogeochemical profiling floats yield strong wintertime outgassing fluxes that greatly reduce the Southern Ocean’s annually integrated CO 2 uptake. This uncertainty in the strength of the Southern Ocean air-sea CO 2 flux and its role in the global carbon cycle hinders our ability to constrain global carbon fluxes, one of the major goals of NASA’s Carbon Monitoring System (CMS). Opportunity: The NASA Ocean Biogeochemical Model (NOBM) produces near-global pCO 2 and air-sea CO 2 flux estimates that are currently included into the NASA’s Goddard Earth Observing System (GEOS) models in support of the CMS effort to monitor global carbon fluxes. The NOBM assimilates ocean color data to improve the representation of biogeochemical fluxes and overcome spatial and temporal gaps in the space-based retrievals. Here, we propose to advance the satellite-constrained flux estimates by investigating the uncertainties in the Southern Ocean air-sea CO 2 flux produced by the NOBM, and assess the value that remote sensing ocean color data can have in providing improved estimates of carbon fluxes in the ocean. Our proposed work includes the delivery of refined in situ float-based carbon fluxes to serve as a constraint on the model-based estimates. Taking advantage of the model’s integration of satellite ocean color data to represent multiple phytoplankton groups, we propose to deliver maps of biogenic carbon export specific to each modeled phytoplankton type and investigate the role of ecological plankton complexity in regulating marine carbon uptake and export. Goals: (a) Delivery of seasonally-adjusted float-based Southern Ocean air-sea CO 2 fluxes: We will produce updated and improved float-based air-sea CO 2 fluxes that will serve as a bias-reduced float-based constraint to evaluate our model-based estimates of the NOBM. (b) Investigation of uncertainties in Southern Ocean air-sea CO 2 flux from the NOBM: Modeled air-sea carbon fluxes will be evaluated against the updated float product as well as ship- and airborne-based data to identify uncertainties and potential model deficiencies. (c) Delivery of model-based carbon export partitioning by phytoplankton functional types (PFTs): We will produce depth-resolved maps of particulate organic export production integrated for all phytoplankton groups and allocated to each individual PFT in the model. The expected significance of this goal is to quantify the role that the functional-oriented diversity in phytoplankton groups represented in the NOBM plays in regulating air-sea CO 2 fluxes in the Southern Ocean.

Lionel A. Arteaga↗

NASA NTRS2005

Assessment of Microbiologically Influenced Corrosion Potential in the International Space Station Internal Active Thermal Control System Heat Exchanger Materials: A 6-Momths Study

The fluid in the Internal Active Thermal Control System (IATCS) of the International Space Station (ISS) is water based. The fluid in the ISS Laboratory Module and Node 1 initially contained a mix of water, phosphate (corrosion control), borate (pH buffer), and silver sulfate (Ag2SO4) (microbial control) at a pH of 9.5+/-0.5. Over time, the chemistry of the fluid changed. Fluid changes included a pH drop from 9.5 to 8.3 due to diffusion of carbon dioxide (CO2) through Teflon(reistered Trademark) (DuPont) hoses, increases in dissolved nickel (Ni) levels, deposition of silver (Ag) to metal surfaces, and precipitation of the phosphate (PO4) as nickel phosphate (NiPO4). The drop in pH and unavailability of a antimicrobial has provided an environment conducive to microbial growth. Microbial levels in the fluid have increased from >10 colony-forming units (CFUs)/100 ml to 10(exp 6) CFUs/100 ml. The heat exchangers in the IATCS loops are considered the weakest point in the loop because of the material thickness (=7 mil). It is made of a Ni-based braze filler/CRES 347. Results of a preliminary test performed at Hamilton Sundstrand indicated the possibility of pitting on this material at locations where Ag deposits were found. Later, tests have confirmed that chemical corrosion of the materials is a concern for this system. Accumulation of micro-organisms on surfaces (biofilm) can also result in material degradation and can amplify the damage caused by the chemical corrosion, known as microbiologically influenced corrosion (MIC). This paper will discuss the results of a 6-mo test performed to characterize and quantify the damage from microbial accumulation on the surface of the ISS/ATCS heat exchanger materials. The test was designed to quantify the damage to the materials under worst-case conditions with and without micro-organisms present at pH 8.3 and 9.5.

Roman, Monsi C.↗

NASA NTRS1991

Nucleotides as nucleophiles: reactions of nucleotides with phosphoimidazolide activated guanosine

An earlier study of the reaction of phosphoimidazolide activated nucleosides (ImpN) in aqueous phosphate buffers indicated two modes of reaction of the phosphate monoanion and dianion. The first mode is catalysis of the hydrolysis of the P-N bond in ImpN's which leads to imidazole and nucleoside 5'-monophosphate. The second represents a nucleophilic substitution of the imidazole to yield the nucleoside 5'-diphosphate. This earlier study thus served as a model for the reaction of ImpN with nucleoside monophosphates (pN) because the latter can be regarded as phosphate derivatives. In the present study we investigated the reaction of guanosine 5'-phosphate-2-methylimidazolide, 2-MeImpG, in the presence of pN (N = guanosine, adenosine and uridine) in the range 6.9 less than or equal to pH less than or equal to 7.7. We observed that pN's do act as nucleophiles to form NppG, and as general base to enhance the hydrolysis of the P-N bond in 2-MeImpG, i.e. pN show the same behavior as inorganic phosphate. The kinetic analysis yields the following rate constants for the dianion pN2-: knpN = 0.17 +/- 0.02 M-1 h-1 for nucleophilic attack and khpN = 0.11 +/- 0.07 M-1 h-1 for general base catalysis of the hydrolysis. These rate constants which are independent of the nucleobase compare with kp.2 = 0.415 M-1 h-1 and khp2. = 0.217 M-1 h-1 for the reactions of HPO4(2-). In addition, this study shows that under conditions where pN presumably form stacks, the reaction mechanism remains unchanged although in quantitative terms stacked pN are somewhat less reactive. Attack by the 2'-OH and 3'-OH groups of the ribose moiety in amounts greater than or equal to 1% is not observed; this is attributed to the large difference in nucleophilicity in the neutral pH range between the phosphate group and the ribose hydroxyls. This nucleophilicity rank is not altered by stacking.

NASA Discipline Exobiology↗

NASA NTRS1982

A non-catastrophist explanation for the iridium anomaly at the Cretaceous/Tertiary boundary

The iridium (Ir) anomaly at the Cretaceous/Tertiary (C/T) boundary can be explained by dissolution of normal pelagic limestones producing an insoluble clay residue containing Ir-rich meteoritic material. Further concentration of Ir and other trace metals in the clay can be explained by deposition under reducing conditions. Clay-mineral analyses indicate that the boundary clay is similar to locally derived clays in the limestones above and below the boundary, and contains no detectable exotic components. This supports a terrestrial origin for the boundary clay. The genesis of the boundary clay is attributed to changes in ocean chemistry (pH and oxygenation), leading to an interval of widespread dissolution of carbonate sequences in the oceans, and culminating in the development of submarine pyritic hardgrounds and a disconformity of global extent.

Rampino, M. R.↗