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At least 73 records · Page 4

Isotopic analysis of basaltic fragments from lunar breccia 14321 - Chronology and petrogenesis of pre-Imbrium mare volcanism

Internal (mineral) Rb-Sr isochrons were determined for six Apollo 14 mare basalts of lunar breccia 14321. The ages of these fragments, which represent the time of crystallization of the respective mafic lavas, range from about 4.05 to 4.24, and, possibly, to 4.33 Ga and are among the oldest dates reported for mare basalts. For three of the fragments, internal Sm-Nd isochron data were collected and initial Nd isotopic composition was determined. The results are discussed with reference to the original source of these different basaltic fragments.

Dasch, E. J.↗

Stable isotope analysis using tunable diode laser spectroscopy

Ratios of C-12/C-13 in CO2 have been measured using a tunable diode laser (TDL) spectrometer to an accuracy of better than 0.4 percent. These results were made possible by the use of state-of-the-art high-temperature TDLs, an etalon and wavenumber calibration technique, high-speed assembly language controlled data acquisition, and the ratioing of absorbances from simultaneously acquired sample and reference data scans. The dual beam spectrometer that is employed uses the sweep integration technique in a spectral region where adjacent spectral lines are of approximately equal absorbance at the expected isotopic abundances.

Becker, Joseph F.↗

Earth's early atmosphere as seen from carbon and nitrogen isotopic analysis of Archean sediments

The origin and evolution of the Earth's early atmosphere has long been a topic of great interest but determination of actual compositions over geologic time is a difficult problem. However, recent systematic studies of stromatolite deposits (Precambrian Paleobiology Research Group) has extended our knowledge of Archean ecosystems. It has been shown that many stromatolite deposits have undergone negligible alteration since their time of formation. The discovery of primary fluid inclusions within unaltered 3.5 b.y. old Archiean sediments and the observation that the 3.3 b.y. old Barberton cherts have remained closed to argon loss and have not been subjected to thermal metamorphism suggests that an opportunity exists for the direct measurement of the volatile constituents present at their time of formation. Of primary interest to this study was the possibility that the stromatolites and other Archean sediments might retain a vestige of the atmosphere and thus afford an indication of the variations in carbon dioxide and nitrogen isotopic compositions with time. A suite of essentially unaltered Archean stromatolites and the cherts of different ages and geologic sites have been analyzed for their trapped carbon dioxide and nitrogen compositions by the stepped combustion extraction tech nique utilizing static mass spectrometers for the isotope measurements.

Gibson, E. K., Jr.↗

Ion microprobe magnesium isotope analysis of plagioclase and hibonite from ordinary chondrites

Ion and electron microprobes were used to examine Mg-26 excesses from Al-26 decay in four Al-rich objects from the type 3 ordinary hibonite clast in the Dhajala chondrite. The initial Al-26/Al-27 ratio was actually significantly lower than Al-rich inclusions in carbonaceous chondrites. Also, no Mg-26 excesses were found in three plagioclase-bearing chondrules that were also examined. The Mg-26 excesses in the hibonite chondrites indicated a common origin for chondrites with the excesses. The implied Al-26 content in a proposed parent body could not, however, be confirmed as a widespread heat source in the early solar system.

Hinton, R. W.↗

Extraction and isotopic analysis of medium molecular weight hydrocarbons from Murchison using supercritical carbon dioxide

The large variety of organic compounds present in carbonaceous chondrites poses particular problems in their analysis not the least of which is terrestrial contamination. Conventional analytical approaches employ simple chromatographic techniques to fractionate the extractable compounds into broad classes of similar chemical structure. However, the use of organic solvents and their subsequent removal by evaporation results in the depletion or loss of semi-volatile compounds as well as requiring considerable preparative work to assure solvent purity. Supercritical fluids have been shown to provide a powerful alternative to conventional liquid organic solvents used for analytical extractions. A sample of Murchison from the Field Museum was analyzed. Two interior fragments were used; the first (2.85 g) was crushed in an agate pestel and mortar to a grain size of ca. 50-100 micron, the second (1.80 g) was broken into chips 3-8 mm in size. Each sample was loaded into a stainless steel bomb and placed in the extraction chamber of an Isco supercritical fluid extractor maintained at 35 C. High purity (99.9995 percent) carbon dioxide was used and was pressurized using an Isco syringe pump. The samples were extracted dynamically by flowing CO2 under pressure through the bomb and venting via a 50 micron fused filica capillary into 5 mls of hexane used as a collection solvent. The hexane was maintained at a temperature of 0.5 C. A series of extractions were done on each sample using CO2 of increasing density. The principal components extracted in each fraction are summarized.

Gilmour, Iain↗

Mars Molecular and Isotopic Analysis Research Study

Recently, the Martian atmosphere and surface constituents have become of great interest. The Viking in situ gas chromatograph mass spectrometer experiment contributed greatly to our knowledge of the composition of the Martian atmosphere. However, important questions remain such as the abundance of water on Mars. The Viking experiment employed solid reagents to enhance their carbon measurements. Techniques of chemical conversion using simple solid reagents have advanced considerably in the past 20 years. In this investigation we researched the advancements in techniques to reversibly adsorb and desorb water and focused on the techniques potentially useful for the temperatures and pressures on the Martian surface. During the granting period from June 15, 1998 to August 14, 1998, a literature study of the material appropriate for use in a chemical conversion device and the availability of these materials were undertaken. The focus of this investigation was searching for methods and materials potentially useful in enhancing the measurements of water. Three different methods were considered for the means to extract water from a given gas sample. These methods included adsorption in a desiccant, adsorption on a clean metal surface, and adsorption in a carbon molecular sieve or zeolite. Each method was evaluated with feasibility and reversibility in mind. By far the simplest and perhaps cheapest way to remove water from a gaseous sample is by means of a bulk desiccant. Desiccants are commercially available from many companies including those that supply chemicals. The main feature of a desiccant is its ability to rapidly bind or absorb water from the atmosphere. Calcium chloride, for example, is frequently incorporated into drying tubes by organic chemists when reactions require the absence of water. Other desiccants include sodium hydroxide, calcium hydride, and commercial products such as Drierite, available from Aldrich Chemical. The disadvantage to most desiccants is a direct consequence of what makes them so advantageous. Desiccants rapidly and strongly bind water, often reacting chemically with it. This strong binding makes reversibly desorbing the water from the desiccant very difficult. The third method by which to absorb water from a gas sample involves the use of molecular sieves of other ziolites.

Manning, Heidi L. K.↗

Chemical and Isotopic Analysis of Trace Organic Matter on Meteorites and Interstellar Dust Using a Laser Microprobe Instrument

Polycyclic Aromatic Hydrocarbons (PAHs) are of considerable interest today because they are ubiquitous on Earth and in the interstellar medium (ISM). In fact, about 20% of cosmic carbon in the galaxy is estimated to be in the form of PAHs. Investigation of these species has obvious uses for determining the cosmochemistry of the solar system. Work in this laboratory has focused on four main areas: 1) Mapping the spatial distribution of PAHs in a variety of meteoritic samples and comparing this distribution with mineralogical features of the meteorite to determine whether a correlation exists between the two. 2) Developing a method for detection of fullerenes in extraterrestrial samples using microprobe Laser Desorption Ionization Mass Spectroscopy and utilizing this technique to investigate fullerene presence, while exploring the possibility of spatially mapping the fullerene distribution in these samples through in situ detection. 3) Investigating a possible formation pathway for meteoritic and ancient terrestrial kerogen involving the photochemical reactions of PAHs with alkanes under prebiotic and astrophysically relevant conditions. 4) Studying reaction pathways and identifying the photoproducts generated during the photochemical evolution of PAH-containing interstellar ice analogs as part of an ongoing collaboration with researchers at the Astrochemistry Lab at NASA Ames. All areas involve elucidation of the solar system formation and chemistry using microprobe Laser Desorption Laser Ionization Mass Spectrometry. A brief description of microprobe Laser Desorption Ionization Mass Spectroscopy, which allows selective investigation of subattomole levels of organic species on the surface of a sample at 10-40 micrometer spatial resolution, is given.

Zare, Richard N.↗

Chemical and isotopic study of extraterrestrial particles from the ocean floor

An Rb-Sr isotopic analysis of deep-sea spherules (DSS) from the Pacific, vesicular iridium-rich glassy objects (VIRGO) from an Antarctic-Ocean diatomaceous-ooze core, and equigranular objects (EGO) associated with or included in VIRGO, is reported. The techniques of sample collection, preparation, chemical analysis, and isotopic analysis (by mass spectrometry) are described in detail, and the results are presented in tables. The Sr-87/Sr-86 determination has a precision of 1-2 percent in microsamples of 2-8 x 10 to the 11th Sr atoms. The DSS are found to have Sr concentrations and Sr-87/Sr-86 (0.730-0.757) typical of chondritic meteorites. Extreme Rb depletion is attributed to volatization during meteoroid atmospheric heating. The VIRGO, while having major-element compositions like that of meteorites and high Ir levels suggesting extraterrestrial origin, have Sr-87/Sr-86 = 0.703-0.705; and the associated EGO has Sr-87/Sr-86 = 0.701 + or - 0.001, typical of MORB or basaltic achondrites. Hence their extraterrestrial origin is not proved, and some lithic component other than the EGO must be the source of the high Ir concentration.

Papanastassiou, D. A.↗

Large-Volume Injection and Assessment of Reference Standards for n -Alkane δD and δ 13 C Analysis via Gas Chromatography Isotope Ratio Mass Spectrometry

Compound-specific stable isotope analysis of hydrogen (δD) and carbon (δ 13 C) in organic compounds is a valuable tool in biogeochemical research. A key limitation of this method is the relatively large amount of sample required to achieve desirable precision. We developed a large-volume (20 μL) injection method that allows for high throughput analysis of less concentrated samples and tested it for δ 13 C and δD measurements of n-alkanes. We also conducted a comparison of reference standards and assessed several methods to normalize and correct n-alkane δD and δ13C measurements. The mean precision of the δD method based on 233 environmental n-alkane samples (two to three replications per sample) is 4.0‰ (1σ, estimated from the weighted mean of the pooled unbiased standard deviations) and 0.46‰ (1σ) for δ 13 C from 37 environmental samples (two to three replications per sample). The evaluation of reference standards shows that the use of n-alkane standards with large offsets in δD values in adjacent n-alkane chains can lead to biases in measurement correction. The large-volume injection method shows good reproducibility of δ 13 C and δD measurements of n-alkanes and reduces the required sample concentration by about 80%. We propose that for δD measurements, a reference standard set should be used in which each reference standard has a limited range of δD values and no adjacent n-alkane chains, to minimize memory effects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrocyclone/Filter for Concentrating Biomarkers from Soil

The hydrocyclone-filtration extractor (HFE), now undergoing development, is a simple, robust apparatus for processing large amounts of soil to extract trace amounts of microorganisms, soluble organic compounds, and other biomarkers from soil and to concentrate the extracts in amounts sufficient to enable such traditional assays as cell culturing, deoxyribonucleic acid (DNA) analysis, and isotope analysis. Originally intended for incorporation into a suite of instruments for detecting signs of life on Mars, the HFE could also be used on Earth for similar purposes, including detecting trace amounts of biomarkers or chemical wastes in soils.

Ponce, Adrian↗

The Nature of Insoluble Organic Matter in Sutter’s Mill and Murchison Carbonaceous Chondrites: Testing the Effect of X-ray Computed Tomography (XCT) and Exploring Parent Body Organic Molecular Evolution

This study analyzed samples of the Murchison and Sutter’s Mill carbonaceous chondrite meteorites in support of the future analysis of samples returned from the asteroid (10155) Bennu by the OSIRIS-REx (Origins, Spectral Interpretation, Resource Identification, and Security–Regolith Explorer) mission. Focusing specifically on the insoluble organic matter (IOM), this study establishes that a total of 1.3 g of bulk sample from a single chondritic meteorite is sufficient to obtain a wide range of cosmochemical information, including light element analysis (H, C, and N), isotopic analysis (D/H, 13 C/ 12 C, and 15 N/ 14 N), and X-ray fluorescence spectroscopy for major elemental abundances. IOM isolated from the bulk meteorite samples was analyzed by light element and isotopic analysis as described above, 1 H and 13 C solid-state nuclear magnetic resonance spectroscopy, Raman spectroscopy, and complete noble gas analyses (abundances and isotopes). The samples studied included a pair from Murchison (CM2), one of which had been irradiated with high-energy X-rays in the course of computed tomographic imaging. No differences between the irradiated and non-irradiated Murchison samples were observed in the many different chemical and spectroscopic analyses, indicating that any X-ray–derived sample damage is below levels of detection. Elemental, isotopic, and molecular spectroscopic data derived from IOM isolated from the Sutter’s Mill sample reveals evidence that this meteorite falls into the class of heated CM chondrites.

planetary science↗

Particle signal considerations for isotope ratio analysis with single particle multi-collector inductively coupled plasma mass spectrometry

Particle analysis has benefitted from the advent of single particle inductively coupled plasma-mass spectrometry (spICP-MS) due to its robustness, sensitivity, and high-throughput nature. Previous methods of spICP-MS have typically utilized quadrupole or time-of-flight mass analyzers and therefore employ electron multiplier-based detectors (such as secondary electron multipliers or microchannel plates). However, to obtain precise measurements on elemental or isotopic ratios within individual particles, multi-collector ICP-MS (MC-ICP-MS) can be used. Here, we investigate Ce isotope ratios, specifically 142 Ce/ 140 Ce, by spMC-ICP-MS using an all-Faraday cup collector array. Using 1 μm (diameter) cerium dioxide particles, integration times of the Faraday cup detectors were varied from 50–500 ms. The signal from the cerium isotopes in the particles was used to determine isotope ratios, which closely matched the expected natural isotopic abundances. Due to the signal decay response from the Faraday cups, the signal from particles lasts much longer than the expected 1–2 ms (up to 100 s of ms). To explore this effect on isotope ratio analysis, multiple ratio analysis methods were used to determine how to obtain optimal precision and accuracy. Relative differences were around 2% for methods that calculated isotope ratios from summing the total signal of an individual particle before calculating the ratio (rather than using every data point individually). It was found that summing all data points per particle, or integrating under the signal peak, yielded both accurate and precise isotope ratios within the particle population. Particles were also sampled off a solid substrate via microextraction, and isotope ratios were determined with relative differences of 0.13% to 9%. This demonstrates the ability to use spMC-ICP-MS to obtain isotope ratios on particles, with little to no relative difference in comparison to the expected ratio, even when operating Faraday detectors at fast 50 ms integration times.

Szakas, Sarah E. [Oak Ridge National Laboratory (O↗