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All sourcesNASA NTRSDOE OSTI
NASA NTRS2010

Water in the Oceanic Lithosphere: Salt Lake Crater Xenoliths, Oahu, Hawaii

Water can be present in nominally anhydrous minerals of peridotites in the form of hydrogen bonded to structural oxygen. Such water in the oceanic upper mantle could have a significant effect on its physical and chemical properties. However, the water content of the MORB source has been inferred indirectly from the compositions of basalts. Direct determinations on abyssal peridotites are scarce because they have been heavily hydrothermally altered. Here we present the first water analyses of minerals from spinel peridotite xenoliths of Salt Lake Crater, Oahu, Hawaii, which are exceptionally fresh. These peridotites are thought to represent fragments of the Pacific oceanic lithosphere that was refertilized by alkalic Hawaiian melts. A few have unradiogenic Os and radiogenic Hf isotopes and may be fragments of an ancient (~2 Ga) depleted and recycled lithosphere. Water contents in olivine (Ol), orthopyroxene (Opx), and clinopyroxene (Cpx) were determined by FTIR spectrometry. Preliminary H_{2}O contents show ranges of 8-10 ppm for Ol, 151-277 ppm for Opx, and 337-603 ppm for Cpx. Reconstructed bulk rock H_{2}O contents range from 88-131 ppm overlapping estimates for the MORB source. Water contents between Ol minerals of the same xenolith are heterogeneous and individual OH infrared bands vary within a mineral with lower 3230 cm^{-1} and higher 3650-3400 cm^{-1} band heights from core to edge. This observation suggests disturbance of the hydrogen in Ol likely occurring during xenolith entrainment to the surface. Pyroxene water contents are higher than most water contents in pyroxenes from continental peridotite xenoliths and higher than those of abyssal peridotites. Cpx water contents decrease with increasing degree of depletion (e.g. increasing Fo in Ol and Cr# in spinel) consistent with an incompatible behavior of water. However Cpx water contents also show a positive correlation with LREE/HREE ratios and LREE concentrations consistent with refertilization. Opx water contents increase with increasing degree of depletion and decrease with LREE/HREE ratios which is inconsistent with the incompatible behavior of H. Calculated water contents of melts in equilibrium with Cpx or Opx range from 1.4 to 3.8 wt % which is higher than that of all Hawaiian lavas. Calculated melts in equilibrium with Cpx and Opx have variable but mostly high H_{2}O/Ce ratios (194 to 1146) consistent with those of rejuvenated stage lavas from Niihau and the South Arch volcanic field, but unlike the drier shield building stage tholeiites. Whether the high water contents recorded in Salt Lake Crater xenoliths were acquired before and/or during interaction of the oceanic lithosphere with the Hawaiian plume will be discussed.

Peslier, Anne H.↗
NASA NTRS1972

Ocean color determination through a scattering atmosphere

Measurements made of the surface level albedo for ocean water containing various concentrations of phytoplankton indicate a strong correlation between wavelength dependent albedo ratios and phytoplankton chlorophyll concentration. To sense surface level albedo ratios from space platforms it is necessary to correct for the scattering and absorption properties of the atmosphere for the wavelengths in question. Atmospheric scattering models were constructed to calculate corrections at two wavelengths, 0.46 and 0.54 millimicrons. Assuming a natural background uncertainty in the aerosol optical depth of 0.1, it is found that the chlorophyll concentration may be determined to within one standard deviation of from 0.5 to 2.5 milligrams per cubic meter. By remotely sensing the aerosol optical depth to a greater accuracy it appears feasible to detect chlorophyll concentrations to uncertainty approaching 0.1 milligram per cubic meter.

Curran, R. J.↗
NASA NTRS1985

Determination of nitrogen monoxide in high purity nitrogen gas with an atmospheric pressure ionization mass spectrometer

An atmospheric pressure ionization mass spectrometric (API-MS) method was studied for the determination of residual NO in high purity N2 gas. The API-MS is very sensitive to NO, but the presence of O2 interferes with the NO measurement. Nitrogen gas in cylinders as sample gas was mixed with NO standard gas and/or O2 standard gas, and then introduced into the API-MS. The calibration curves of NO and O2 has linearity in the region of 0 - 2 ppm, but the slopes changed with every cylinder. The effect of O2 on NO+ peak was additive and proportional to O2 concentration in the range of 0 - 0.5 ppm. The increase in NO+ intensity due to O2 was (0.07 - 0.13)%/O2, 1 ppm. Determination of NO and O2 was carried out by the standard addition method to eliminate the influence of variation of slopes. The interference due to O2 was estimated from the product of the O2 concentration and the ratio of slope A to Slope B. Slope A is the change in the NO+ intensity with the O2 concentration. Slope B is the intensity with O2 concentration.

Kato, K.↗
NASA NTRS2024

Volatiles in melt inclusions from lunar mare basalts: Bridging the gap in the H 2 O/Ce ratio between melt Inclusions in lunar pyroclastic sample 74220 and other mare samples

The H2O concentration and H 2 O/Ce ratio in olivine-hosted melt inclusions are high in lunar pyroclastic sample 74220 (H 2 O up to 1410 ppmw; H 2 O/Ce up to 77) but lower (H2O 10 to 430 ppmw; H 2 O/Ce 0.3 to 9.4) in all other lunar samples studied before this work. The difference in H 2 O concentration and in H 2 O/Ce ratio is absent for other volatile elements (F, S, and Cl) in melt inclusions in 74220 and other lunar samples. Because H 2 O (or H) is a critical volatile component with significant ramifications on the origin and evolution of the Moon, it is important to understand what causes such a large gap in H 2 O/Ce ratio between 74220 and other lunar samples. Two explanations have been advanced. One is that volcanic product in sample 74220 has the highest cooling rate and thus best preserved H 2 O in melt inclusions compared to melt inclusions in other samples. The other explanation is that sample 74220 comes from a localized heterogeneity enriched in some volatiles. To distinguish these two possibilities, here we present new data from two rapidly cooled lunar samples with glassy melt inclusions: olivine-hosted melt inclusions (OHMIs) in 79135 regolith breccia (unknown cooling rate but with glassy MIs similar in texture with those in 74220), and pyroxene-hosted melt inclusions (PHMIs) in 15597 pigeonite basalts (known high cooling rate, second only to 74220 and 15421). In addition, we also investigated new OHMIs in sample 74220. If the gap is due to the difference in cooling rates, samples with cooling rates between those of 74220 and other studied lunar samples should have preserved intermediate H2O concentrations and H 2 O/Ce ratios. Our results show that melt inclusions in 79135 and 15597 contain high H 2 O concentrations (up to 969 ppmw in 79135 and up to 793 ppmw in 15597) and high H 2 O/Ce ratios (up to 21 in 79135 and up to 13 in 15997), bridging the big gap in H 2 O/Ce ratio among 74220 and other lunar samples. Combined with literature data, we confirm that H 2 O/Ce ratios of different lunar samples are positively correlated to the cooling rates and independent of the type of mare basalts. We hence reinforce the interpretation that the lunar sample with the highest cooling rate best represents pre-eruptive volatiles in lunar basalts due to the least degassing. Based on Ce concentration in the primitive lunar mantle, we estimate that H 2 O concentration in the primitive lunar mantle (meaning bulk silicate Moon) is 121 ± 15 ppmw. Our new data also further constrain F/P, S/Dy and Cl/Ba ratios in lunar basalts and the lunar mantle. Estimated F, P, and S concentrations in the lunar primitive mantle are 4.4 ± 1.1 ppmw, 22 ± 8 ppmw, and 67 +67 −33 ppmw, respectively.

Xue Su↗
NASA NTRS1986

Origin of the earth's moon - Constraints from alkali volatile trace elements

Although the moon is depleted in volatile elements compared to the earth, these depletions are not in accord with simple volatility. For example, the Cs/Rb ratios of the earth and moon inferred from basalt are approximately one seventh and one half of the CI ratio, respectively. Volatility considerations alone predict that the lunar Cs/Rb ratio should be equal to or lower than the terrestrial ratio if the moon was derived entirely from earth mantle material. Thus hypotheses such as rotational fission which invoke derivation of lunar material entirely from the earth's mantle may be excluded. The collisional ejection hypothesis of lunar origin requires at least 18 percent of lunar material to be derived from a projectile with dehydrated CI composition to match the lunar Cs/Rb ratio, and 25-50 percent to match both the lunar Cs/Rb ratio and absolute concentrations of Cs and Rb. It remains to be demonstrated that this relatively large contribution of projectile material is consistent with other elemental abundances and element ratios in the moon.

Kreutzberger, M. E.↗
NASA NTRS1993

Osmium isotopes in Ivory Coast tektites: Confirmation of a meteoritic component and rhenium depletion

The sensitive negative thermal ionization mass spectrometry method was used for the measurement of concentrations and isotopic ratios of osmium and rhenium in four Ivory Coast tektites. These tektites have crustal major and trace element composition, as well as large negative epsilon(sub Nd)(-20) and positive epsilon(sub Sr)(+260 to +300) which are characteristic for old continental crust. Os concentrations ranging from 0.09 to 0.30 ppb were found, clearly much higher than average crustal values, Os-187/Os-186 ratios of about 1.2-1.7, and low Re-187/Os-186 ratios. These results show unambiguously the existence of a meteoritic component (on the order of 0.06%) in the Ivory Coast tektites. Low Re abundances are the result of fractionation of Re during the impact.

Koeberl, Christian↗
NASA NTRS2003

Early Archean Spherule Beds: Chromium Isotopes Confirm Origin through Multiple Impacts of Projectiles of Carbonaceous Chondrite Type: Comment and Reply

This is a exchange in the form of a comment and a reply in regards to an earlier article. The authors of the original article, consider it likely that virtually all of the projectile will condense with the silicate fraction, resulting in very little platinum group element fractionation in the final ejecta deposit. Further, we find no evidence in the commentator's, (i.e., Glikson), comment to support vapor fractionation. We note that the Pd/Ir ratios of published data on 2.56 Ga Hamersley Basin spherules are all greater than in chondrites, contrary to the assertion by Glikson. This is consistent with relatively high Pd concentrations (and Pd/Ir ratios) in crustal rocks.

Kyte, Frank T.↗
NASA NTRS2000

Comparison of Os and Cr Isotopic Methods for the Detection of Meteoritic Components in Impact Melt Rocks from the Morokweng and Vredefort Impact Structures, South Africa

The verification of an extraterrestrial component in impact-derived melt rocks or breccias can be of diagnostic value to provide confirming evidence for an impact origin of a geological structure. Geochemical methods are used to determine the presence of the traces of such a component. In the absence of actual meteorite fragments, it is necessary to search for traces of meteoritic material that is mixed in with the target rocks in breccias and melt rocks. Meteoritic components have been identified for just over 40 impact structures (out of more than 160 known on Earth), which reflects also the detail in which these structures were studied. The identification of a meteoritic component can be achieved by determining the concentrations and interelement ratios of siderophile elements, especially the platinum group elements (PGE), which are several orders of magnitude more abundant in meteorites than in terrestrial upper crustal rocks. The usage of platinum group element abundances and ratios avoids some of the ambiguities that may result if only common siderophile elements (e.g., Cr, Co, Ni) are considered. However, problems may arise if the target rocks have high abundances of siderophile elements, or if the siderophile element concentrations in the impactites are very low. In such cases, the Os and Cr isotopic systems have recently been used for establishing the presence of a meteoritic component in a number of impact melt rocks and breccias. In the past it was attempted to use PGE data to determine the type or class of meteorite for the impactor, but these attempts were not always successful. It is difficult to decide between chondrite types based on PGE abundances, which has led to conflicting identifications for a number of impact structures. Clearly, the identification of a meteoritic component in impactites is not a trivial problem. In this study, we are using a combination of trace element (PGE) analyses and the results from both, Os and Cr isotopic studies, to illustrate the pros and cons of each method on two case studies, namely the Vredefort and Morokweng impact structures. Additional information is contained in the original extended abstract.

Koeberl, Christian↗
NASA NTRS1981

Solute partitioning under continuous cooling conditions as a cooling rate indicator

A model of solute partitioning in a finite body under conditions of continuous cooling is developed for the determination of cooling rates from concentration profile data, and applied to the partitioning of zirconium between ilmenite and ulvospinel in the Apollo 15 Elbow Crater rocks. Partitioning in a layered composite solid is described numerically in terms of concentration profiles and diffusion coefficients which are functions of time and temperature, respectively; a program based on the model can be used to calculate concentration profiles for various assumed cooling rates given the diffusion coefficients in the two phases and the equilibrium partitioning ratio over a range of temperatures. In the case of the Elbow Rock gabbros, the cooling rates are calculated from measured concentration ratios 10 microns from the interphase boundaries under the assumptions of uniform and equilibrium initial conditions at various starting temperatures. It is shown that the specimens could not have had uniform concentrations profiles at the previously suggested initial temperature of 1350 K. It is concluded that even under conditions where the initial temperature, grain sizes and solute diffusion coefficients are not well characterized, the model can be used to estimate the cooling rate of a grain assemblage to within an order of magnitude.

Onorato, P. I. K.↗
NASA NTRS1988

Geochemical comparison of K-T boundaries from the Northern and Southern Hemispheres

Closely spaced (cm-scale) traverses through the K-T boundary at Stevns Klint (Denmark), Woodside Creek (New Zealand) and a new Southern Hemisphere site at Richards Bay (South Africa) were subjected to trace element and isotopic (C, O, Sr) investigation. Intercomparison between these data-sets, and correlation with the broad K-T database available in the literature, indicate that the chemistry of the boundary clays is not globally constant. Variations are more common than similarities, both of absolute concentrations, and interelement ratios. For example, the chondrite normalized platinum-group elements (PGE) patterns of Stevns Klint are not like those of Woodside Creek, with the Pt/Os ratios showing the biggest variation. These differences in PGE patterns are difficult to explain by secondary alteration of a layer that was originally chemically homogeneous, especially for elements of such dubious crustal mobility as Os and Ir. The data also show that enhanced PGE concentrations, with similar trends to those of the boundary layers, occur in the Cretaceous sediments below the actual boundary at Stevns Klint and all three the New Zealand localities. This confirms the observations of others that the geochemistry of the boundary layers apparently does not record a unique component. It is suggested that terrestrial processes, eg. an extended period of Late Cretaceous volcanism can offer a satisfactory explanation for the features of the K-T geochemical anomaly. Such models would probably be more consistent with the observed stepwise, or gradual, palaeontological changes across this boundary, than the instant catastrophe predicated by the impact theory.

Tredous, M.↗
NASA NTRS1998

A New Optical Aerosol Spectrometer

An optical particle spectrometer capable of measuring aerosol particle size distributions from 0.02 to 100 micrometers has been developed. This instrument combines several optical methods in one, in-situ configuration; it can provide continuous data collection to encompass the wide dynamic size ranges and concentrations found in studies of modeled planetary atmospheres as well as terrestrial air quality research. Currently, the system is incorporated into an eight liter capacity spherical pressure vessel that is appropriate both for flowthrough and for in-situ particle generation. The optical sizing methods include polarization ratio, The scattering, and forward scattering detectors, with illumination from a fiber-coupled, Argon-ion laser. As particle sizes increase above 0.1 micrometer, a customized electronics and software system automatically shifts from polarization to diffraction-based measurements as the angular scattering detectors attain acceptable signal-to-noise ratios. The number concentration detection limits are estimated to be in the part-per-trillion (ppT by volume) range, or roughly 1000 submicron particles per cubic centimeter. Results from static experiments using HFC134A (approved light scattering gas standard), flow-through experiments using sodium chloride (NaCl) and carbon particles, and dynamic 'Tholin' (photochemical produced particles from ultraviolet (UV)-irradiated acetylene and nitrogen) experiments have been obtained. The optical spectrometer data obtained with particles have compared well with particle sizes determined by electron microscopy. The 'Tholin' tests provided real-time size and concentration data as the particles grew from about 30 nanometers to about 0.8 micrometers, with concentrations ranging from ppT to ppB, by volume. Tests are still underway, to better define sizing accuracy and concentration limits, these results will be reported.

Fonda, Mark↗
NASA NTRS1986

Fugacity and concentration gradients in a gravity field

Equations are reviewed which show that at equilibrium fugacity and concentration gradients can exist in gravitational fields. At equilibrium, the logarithm of the ratio of the fugacities of a species at two different locations in a gravitational field is proportional to the difference in the heights of the two locations and the molecular weight of the species. An analogous relation holds for the concentration ratios in a multicomponent system. The ratio is calculated for a variety of examples. The kinetics for the general process are derived, and the time required to approach equilibrium is calculated for several systems. The following special topics are discussed: ionic solutions, polymers, multiphase systems, hydrostatic pressure, osmotic pressure, and solubility gradients in a gravity field.

May, C. E.↗
NASA NTRS2001

Soot Formation in Laminar Premixed Methane/Oxygen Flames at Atmospheric Pressure

Flame structure and soot formation were studied within soot-containing laminar premixed methanefoxygen flames at atmospheric pressure. The following measurements were made: soot volume fractions by laser extinction, soot temperatures by multiline emission, gas temperatures (where soot was absent) by corrected fine-wire thermocouples, soot structure by thermophoretic sampling and transmission electron microscope (TEM), major gas species concentrations by sampling and gas chromatography, and gas velocities by laser velocimetry. Present measurements of gas species concentrations were in reasonably good agreement with earlier measurements due to Ramer et al. as well as predictions based on the detailed mechanisms of Frenklach and co-workers and Leung and Lindstedt; the predictions also suggest that H atom concentrations are in local thermodynamic equilibrium throughout the soot formation region. Using this information, it was found that measured soot surface growth rates could be correlated successfully by predictions based on the hydrogenabstraction/carbon-addition (HACA) mechanisms of both Frenklach and co-workers and Colket and Hall, extending an earlier assessment of these mechanisms for premixed ethylene/air flames to conditions having larger H/C ratios and acetylene concentrations. Measured primary soot particle nucleation rates were somewhat lower than the earlier observations for laminar premixed ethylene/air flames and were significantly lower than corresponding rates in laminar diffusion flames, for reasons that still must be explained.

Xu, F.↗
NASA NTRS1998

Soot Formation in Laminar Premixed Methane/Oxygen Flames at Atmospheric Pressure

Flame structure and soot formation were studied within soot-containing laminar premixed mc1hane/oxygen flames at atmospheric pressure. The following measurements were made: soot volume fractions by laser extinction, soot temperatures by multiline emission, gas temperatures (where soot was absent) by corrected fine-wire thermocouples, soot structure by thermophoretic sampling and transmission electron microscope (TEM), major gas species concentrations by sampling and gas chromatography, and gas velocities by laser velocimetry. Present measurements of gas species concentrations were in reasonably good agreement with earlier measurements due to Ramer et al. as well as predictions based on the detailed mechanisms of Frenklach and co-workers and Leung and Lindstedt: the predictions also suggest that H atom concentrations are in local thermodynamic equilibrium throughout the soot formation region. Using this information, it was found that measured soot surface growth rates could be correlated successfully by predictions based on the hydrogen-abstraction/carbon-addition (HACA) mechanisms of both Frenklach and co-workers and Colket and Hall, extending an earlier assessment of these mechanisms for premixed ethylene/air flames to conditions having larger H/C ratios and acetylene concentrations. Measured primary soot particle nucleation rates were somewhat lower than the earlier observations for laminar premixed ethylene/air flames and were significantly lower than corresponding rates in laminar diffusion flames. for reasons that still must be explained.

Xu, F.↗
NASA NTRS2002

Combustion Sensors: Gas Turbine Applications

This report documents efforts to survey the current research directions in sensor technology for gas turbine systems. The work is driven by the current and future requirements on system performance and optimization. Accurate real time measurements of velocities, pressure, temperatures, and species concentrations will be required for objectives such as combustion instability attenuation, pollutant reduction, engine health management, exhaust profile control via active control, etc. Changing combustor conditions - engine aging, flow path slagging, or rapid maneuvering - will require adaptive responses; the effectiveness of such will be only as good as the dynamic information available for processing. All of these issues point toward the importance of continued sensor development. For adequate control of the combustion process, sensor data must include information about the above mentioned quantities along with equivalence ratios and radical concentrations, and also include both temporal and spatial velocity resolution. Ultimately these devices must transfer from the laboratory to field installations, and thus must become low weight and cost, reliable and maintainable. A primary conclusion from this study is that the optics-based sensor science will be the primary diagnostic in future gas turbine technologies.

Human, Mel↗
NASA NTRS2001

Laser Absorption Measurements of Equivalence Ratios Studied Along With Their Coupling to Pressure Fluctuations in Lean Premixed Prevaporized (LPP) Combustion

Concerns about damaging the Earth's ozone layer as a result of high levels of nitrogen oxides (known collectively as NOx) from high-altitude, high-speed aircraft have prompted the study of lean premixed prevaporized (LPP) combustion in aircraft engines. LPP combustion reduces NOx emissions principally by reducing the peak flame temperatures inside an engine. Recent advances in LPP technologies have realized exceptional reductions in pollutant emissions (single-digit ppm NOx for example). However, LPP combustion also presents major challenges: combustion instability and dynamic coupling effects between fluctuations in heat-release rate, dynamic pressure, and fuel pressure. These challenges are formidable and can literally shake an engine apart if uncontrolled. To better understand this phenomenon so that it can be controlled, we obtained real-time laser absorption measurements of the fuel vapor concentration (and equivalence ratio) simultaneously with the dynamic pressure, flame luminosity, and time-averaged gaseous emissions measurements in a research-type jet-A-fueled LPP combustor. The measurements were obtained in NASA Glenn Research Center's CE-5B optically accessible flame tube facility. The CE-5B facility provides inlet air temperatures and pressures similar to the actual operating conditions of real aircraft engines. The laser absorption measurements were performed using an infrared 3.39 micron HeNe laser in conjunction with a visible HeNe laser for liquid droplet scattering compensation.

Nguyen, Quang-Viet↗
NASA NTRS1976

Amino acids in modern and fossil woods

The amino acid composition and the extent of racemization in several modern and fossil woods are reported. The method of analysis is described, and data are presented on the total amino acid concentration, the amino acid ratios, and the enantiomeric ratios in each sample. It is found that the amino acid concentration per gram of dry wood decreases with age of the sample, that the extent of racemization increases with increasing age, and that the amounts of aspartic acid, threonine, and serine decrease relative to valine with increasing age. The relative racemization rates of amino acids in wood, bone, and aqueous solution are compared, and it is shown that racemization in wood is much slower than in bone or aqueous solution. Racemization results for woods from the Kalambo Falls area of Zambia are used to calculate a minimum age of 110,000 years for the transition between the Sangoan and Acheulian industries at that site. This result is shown to be consistent with numerous radiometric dates for older Acheulian sites in Africa and to compare well with geologically inferred dates for the beginning of the Eemian and the end of the Acheulian industry in southern Africa.

Lee, C.↗
NASA NTRS2003

Igneous and Aqueous Processes on Mars: Evidence from Measurements of K and Th by the Mars Odyssey Gamma Ray Spectrometer

We report preliminary measurements of the concentrations of K and Th on Mars. Concentrations of K and Th and the K/Th ratio vary across the surface. Concentrations are higher than in Martian meteorites, suggesting that most of the crust formed by partial melting of enriched mantle. The average Th concentration (1.1 ppm), if applicable to the entire crust, implies a maximum thickness of about 65 km. The variation in the K/Th ratio suggests that aqueous processes have affected the chemistry of the surface.

Taylor, G. Jeffrey↗