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At least 19 records

Carbon and nitrogen biogeochemistry in the ocean: A study using stable isotope natural abundance

Determining the biogeochemical pathways traveled by carbon and nitrogen in the ocean is fundamental to the understanding of how the ocean participates in the cycling of these elements within the biosphere. Because biological production, metabolism, and respiration can significantly alter the natural abundance of C-13 and N-15, these abundances can provide important information about the nature of these biological processes and their variability in the marine environment. The research initially seeks to characterize the spatial and temporal patterns of stable isotope abundances in organic matter, and to relate these abundances to C and N biogeochemical processes within selected areas of the northeastern Pacific Ocean.

Rau, G. H.↗

Natural abundances of carbon isotopes in acetate from a coastal marine sediment

Measurements of the natural abundances of carbon isotopes were made in acetate samples isolated from the anoxic marine sediment of Cape Lookout Bight, North Carolina. The typical value of the total acetate carbon isotope ratio (delta 13C) was -16.1 +/- 0.2 per mil. The methyl and carboxyl groups were determined to be -26.4 +/- 0.3 and -6.0 +/- 0.3 per mil, respectively, for one sample. The isotopic composition of the acetate is thought to have resulted from isotopic discriminations that occurred during the cycling of that molecule. Measurements of this type, which have not been made previously in the natural environment, may provide information about the dominant microbial pathways in anoxic sediments as well as the processes that influence the carbon isotopic composition of biogenic methane from many sources.

NASA Discipline Exobiology↗

Rotating Molten Metallic Drops and Related Phenomena: A New Approach to the Surface Tension Measurement

Molten aluminum and tin drops were levitated in a high vacuum by controlled electric fields, and they were systematically rotated by applying by a rotating magnetic field. When the evolution of the drop shape was measured as a function of rotation frequency, it agreed quantitatively well with the Brown and Scriven's theoretical prediction. The normalized rotation frequencies at the bifurcation point agreed with the predicted value 0.559, within 2%. An anomalous phenomenon which totally deviated from the prediction was observed in rotating molten tin drops when they were kept in a high rotation rate for several hours. No anomaly was observed in aluminum drops when they underwent similar condition. It was speculated that under the strong centrifugal force in the drop the tin isotopes must be separating. Since Al-27 is essentially the only naturally abundant isotope in the aluminum drops, the same anomaly is not expected. Based on the shape deformation of a rotating drop, an alternate approach to the surface tension measurement was verified. This new surface tension measurement technique was applied to a glassforming alloy, Zr(41.2)Ti(13.8)Cu(12.5)Ni(10.0)Be(22.5) in its highly viscous states. Also demonstrated in the paper was a use of a molten aluminum drop to verify the Busse's prediction of the influence of the drop rotation on the drop oscillation frequency.

Rhim, Won-Kyu↗

Methane line parameters from 3700 to 4136/cm

The positions and strengths of about 1900 absorption lines of methane between 3700 and 4136/cm were measured experimentally to provide a reference line list for the identification of weak CH4 features in planetary spectra. The line parameters were obtained at room temperature with accuracies of 0.0002-0.003/cm for positions and + or - 3-40 percent for strengths using spectra recorded at 0.011/cm resolution (unapodized) with a Fourier transform spectrometer at Kitt Peak National Observatory/National Solar Observatory. Individual line strengths range from 0.00002-0.013/sq cm per atm at room temperature, and the sum of the observed strengths is 1.42/sq cm per atm at 297 K. All measurements are reported in natural isotopic abundance.

Brown, Linda R.↗

Determination of Silicon in Hydrazine

Inductively coupled plasma-mass spectrometry (ICP-MS) is a highly sensitive technique sometimes used for the trace determination of silicon at a mass-to-charge (m/z) ratio of 28, the most abundant natural isotope of silicon. Unfortunately, ICP-MS is unable to differentiate between other sources of m/z 28 and false positive results for silicon will result when other sources of m/z 28 are present. Nitrogen was a major source of m/z 28 and contributes to the m/z 28 signal when hydrazine sample or nitric acid preservative is introduced into the plasma. Accordingly, this work was performed to develop a sample preparation step coupled with an ICP-MS analysis that minimized non-silicon sources of m/z 28. In the preparatory step of this method, the hydrazine sample was first decomposed predominately to nitrogen gas and water with copper-catalyzed hydrogen peroxide. In the analysis step, ICP-MS was used without nitric acid preservative in samples or standards. Glass, a potential source of silicon contamination, was also avoided where possible. The method was sensitive, accurate, and reliable for the determination of silicon in monopropellant grade hydrazine (MPH) in AF-E-332 elastomer leaching tests. Results for silicon in MPH were comparable to those reported in the literature for other studies.

McClure, Mark B.↗

Carbon isotopic fractionation in heterotrophic microbial metabolism

Differences in the natural-abundance carbon stable isotopic compositions between products from aerobic cultures of Escherichia coli K-12 were measured. Respired CO2 was 3.4 percent depleted in C-13 relative to the glucose used as the carbon source, whereas the acetate was 12.3 percent enriched in C-13. The acetate C-13 enrichment was solely in the carboxyl group. Even though the total cellular carbon was only 0.6 percent depleted in C-13, intracellular components exhibited a significant isotopic heterogeneity. The protein and lipid fractions were -1.1 and -2.7 percent, respectively. Aspartic and glutamic acids were -1.6 and +2.7 percent, respectively, yet citrate was isotopically identical to the glucose. Probable sites of carbon isotopic fractionation include the enzyme, phosphotransacetylase, and the Krebs cycle.

Blair, N.↗

Infrared spectroscopy of stars

This paper reviews applications of IR techniques in stellar classification, studies of stellar photospheres, elemental and isotopic abundances, and the nature of remnant and ejected matter in near-circumstellar regions. Qualitative IR spectral classification of cool and hot stars is discussed, along with IR spectra of peculiar composite star systems and of obscured stars, and IR characteristics of stellar populations. The use of IR spectroscopy in theoretical modeling of stellar atmospheres is examined, IR indicators of stellar atmospheric composition are described, and contributions of IR spectroscopy to the study of stellar recycling of interstellar matter are summarized. The future of IR astronomy is also considered.

Merrill, K. M.↗

Measurement of the J = 0-1 rotational transitions of three isotopes of ArD(+)

The rotational transitions of all three isotopic species of ArD(+) in samples containing the Ar isotopes in their natural abundances have been measured by means of millimeter and submillimeter techniques that employ a magnetically enhanced abnormal glow discharge. All three transition frequency measurements were made from digitally averaged signals detected through a lock-in amplifier with a 10-msec time constant. The Ar-4OD(+) transition was easily visible in real time on an oscilloscope with SNR of about 15. It is noted that the observed transition of Ar-38D(+) is more than five orders of magnitude weaker than that due to HCO(+).

Bowman, W. C.↗

First in-situ Nitrogen Isotope Measurements in Martian Meteorites

The origin and timing of the accretion of volatile elements on the terrestrial planets remains a subject of controversy. Nitrogen and hydrogen isotopes are powerful tools to constrain the source(s) of primordial volatiles accreted by planetary bodies because their isotope ratios (15N/14N; D/H) differ significantly between different solar system reservoirs (e.g., solar, chondritic, cometary). Hf-W data of martian samples indicate that Mars accreted very rapidly in the inner solar system and reached half ofits size in 1.8 Myr [1]. Therefore, martian samples are key to understand the distribution of volatile elements in the inner solar system during the early stages of planetary formation. Since no space missions have yet returned samples from Mars, martian meteorites (Shergottites, Nakhlites, Chassignites) are unique samples to constrain the source(s) of volatiles present in the martian mantle. The goal of this study was to target pristine phases(e.g., melt inclusions, mesostasis) for in-situ measurements of their nitrogen content and isotopic ratios to access the most primitive melt of the Chassignites and Nakhlites reservoirs. Five different Nakhlites (Nakhla, NWA 998, MIL 03346, Y 000593,NWA 6148) and Chassigny were analysed [2] using a recent high-resolution analytical technique that allows constraining the nitrogen composition of both carbon-bearing and carbon-free phases in natural and synthetic samples. Nitrogen was measured in the form of 14N16O- and 15N16O- with the CAMECA 1280-HR2 at the CRPG [3]. A significant amount of nitrogen was detected in melt inclusions in Chassigny and in the mesostasis of Nakhla, Y000593, MIL 03346, and NWA 6148. Nitrogen isotope signatures of Chassigny and Nakhlites exhibit a heavy isotope enrichment compared to Earth's mantle, and are consistent with a carbonaceous chondrite-like source [4]. This suggests that Earth and Mars accreted nitrogen from different chondritic sources. Overall, our in-situ technique is a unique and powerful tool to characterize the nitrogen abundance and isotopic composition of natural samples.

C Deligny↗

Operation of a microchannel plate counting system in a mass spectrometer

A multiplier detector system has been developed as part of a mass spectrometer in an ion counting mode. During its operation ions striking a microchannel plate release pulses of electrons which are accelerated to a phosphor layer. The resulting flash of light is carried by a fiber-optic bundle to a photodiode array. The detector simultaneously counts ions throughout a mass spectrum covering more than 30 amu. It extends the mass spectrometer's operation toward low count rates for trace gas analysis. Each mass peak can be independently measured at count rates between 0.1 and 1000 counts/s. Higher rates on a few peaks do not blind the entire detector. The detector's capabilities have been demonstrated by measuring Kr and Xe isotopes in air at natural abundances. The mass spectrometer, detector, and readout electronics are sufficiently compact to permit use in a balloon-borne experiment.

Murphy, D. M.↗

Nitrogen isotopic analyses by isotope-ratio-monitoring gas chromatography/mass spectrometry

Amino acids containing natural-abundance levels of 15N were derivatized and analyzed isotopically using a technique in which individual compounds are separated by gas chromatography, combusted on-line, and the product stream sent directly to an isotope-ratio mass spectrometer. For samples of N2 gas, standard deviations of ratio measurement were better than 0.1% (Units for delta are parts per thousand or per million (%).) for samples larger than 400 pmol and better than 0.5% for samples larger than 25 pmol (0.1% 15N is equivalent to 0.00004 atom % 15N). Results duplicated those of conventional, batchwise analyses to within 0.05%. For combustion of organic compounds yielding CO2/N2 ratios between 14 and 28, in particular for N-acetyl n-propyl derivatives of amino acids, delta values were within 0.25% of results obtained using conventional techniques and standard deviations were better than 0.35%. Pooled data for measurements of all amino acids produced an accuracy and precision of 0.04 and 0.23%, respectively, when 2 nmol of each amino acid was injected on column and 20% of the stream of combustion products was delivered to the mass spectrometer.

Non-NASA Center↗

Stardust Abundance Variations among Interplanetary Dust Particles

Presolar grain abundances reflect the degree of processing primitive materials have experienced. This is evidenced by the wide range of silicate stardust abundances among primitive meteorites (~10 to 300 ppm) [1], attributable to parent body hydrothermal processing. Stardust abundance variations are also pronounced in anhydrous interplanetary dust particles (CPIDPs), that have not experienced parent body processing (300 to > 10,000 ppm) [2-4]. The large range in stardust abundances among CP IDPs thus reflect nebular processing. Here we present results of a systematic search for stardust among cluster CP IDPs. Our goals are to establish mineralogical trends among IDPs with different stardust abundances. This may shed light into the nature of isotopically normal presolar grains (GEMS grains?; 5) if their abundances vary similarly to that of isotopically exotic stardust grains.

Messenger, S.↗

The Doubly Labeled Water Method for Measuring Human Energy Expenditure: Adaptations for Spaceflight

It is essential to determine human energy requirements in space, and the doubly labeled water method has been identified as the most appropriate means of indirect calorimetry to meet this need. The method employs naturally occurring, stable isotopes of hydrogen (H-2, deuterium) and oxygen (O-18) which, after dosing, mix with body water. The deuterium is lost from the body as water while the O-18 is eliminated as both water and CO2. The difference between the two isotope elimination rates is therefore a measure of CO2 production and hence energy expenditure. Spaceflight will present a unique challenge to the application of the doubly labeled water method. Specifically, interpretation of doubly labeled water results assumes that the natural abundance or 'background' levels of the isotopes remain constant during the measurement interval. To address this issue, an equilibration model will be developed in an ongoing ground-based study. As energy requirements of women matched to counterparts in the Astronauts Corps are being determined by doubly labeled water, the baseline isotope concentration will be changed by consumption of 'simulated Shuttle water' which is artificially enriched. One group of subjects will be equilibrated on simulated Shuttle water prior to energy determinations by doubly labeled water while the others will consume simulated Shuttle water after dosing. This process will allow us to derive a prediction equation to mathematically model the effect of changing background isotope concentrations.

Schulz, Leslie O.↗

The carbon isotope biogeochemistry of methane production in anoxic sediments. 1: Field observations

The natural abundance C-13/C-12 ratio of methane from anoxic marine and freshwater sediments in temperate climates varies seasonally. Carbon isotopic measurements of the methanogenic precursors, acetate and dissolved inorganic carbon, from the marine sediments of Cape Lookout Bight, North Carolina were used to determine the sources of the seasonal variations at that site. Movement of the methanogenic zone over an isotopic gradient within the dissolved CO2 pool appears to be the dominant control of the methane C-13/C-12 ratio from February to June. The onset of acetoclastic methane-production is a second important controlling process during mid-summer. An apparent temperature dependence on the fractionation factor for CO2-reduction may have a significant influence on the isotopic composition of methane throughout the year.

Blair, Neal E.↗

Alfven wave scattering and the secondary to primary ratio

The cosmic ray abundances have traditionally been used to determine the elemental and isotopic nature of galactic ray sources and average measures of propagation conditions. Detailed studies of the physics of propagation are usually paired with relatively straightforward estimates of the secondary-to-primary (S/P) ratios. In the work reported here, calculations of elemental abundances are paired with a more careful treatment of the propagation process. It is shown that the physics of propagation does indeed leave specific traces of Galactic structure in cosmic ray abundances.

Bretthorst, G. L.↗

Isotopic Investigations of Nebular and Parent Body Processes with a High Sensitivity Ion Microprobe

NASA supported the development of the CAMECA ims 1270 ion microprobe at UCLA for applications in cosmochemistry. The primary investigations centered on measuring the microscopic distributions of key isotopic abundances in primitive meteoritic materials as a means of constraining the nature of important thermal and chemical processes in the solar nebula and the timescales associated with those processes. Our prior work on oxygen isotope anomalies in a wide variety of meteoritic materials had led us to a view of a spatially heterogeneous nebula, and in particular, a restricted region for CAI formation that is characterized by O-16-rich gas. Because of its production of CAIs in the energetic local environment near the protosun, the existence of a natural transport mechanism via bipolar outflows, and a general astrophysical plausibility, we were attracted to the fluctuating X-wind model which had been put forward by Frank Shu, Typhoon Lee, and colleagues. With our collaborators, we undertook a series of investigations to test the viability of this hypothesis; this work led directly to the discovery of live Be in CAIs and a clear demonstration of the existence of 160-rich condensates, which necessarily implies an O-16-rich gaseous reservoir in the nebula. Both of these observations fit well within the context of X-wind type models, i.e. formation of CAIs (or condensation of their precursors) in the reconnection ring sunward of the inner edge of the accretion disk, however much work remains to be done to test whether the physical parameters of the model can quantitatively predict not only the thermal histories of CAIs but also their radioactivity. The issue of spatial heterogeneity in the nebula, central to the X-wind model, is also at the heart of any chronology based on short-lived radioisotopes. In this work, we followed up on strong hints for presence of exireme:j: (53 day) short-lived Be-7, and have prepared a manuscript (in revision). We also measured A1-Mg systematics by a combined approach of high-precision multiple-collector SIMS analyses, traditional analyses on the UCLA ims 1270, and high-spatial resolution analyses using a NanoSIMS instrument. The data help to deconvolve effects due to partial resetting of the A1-Mg system by multiple thermal events. Finally, we initiated investigations related to nebular heterogeneity with a new initiative of in situ high-precision sulfur isotope analyses of sulfides from a wide variety of components of chondrites. The ultimate goal of all this work is to help develop a better understanding of the relationships between CAIs and chondrules, the astrophysical environments in which they formed, and the timescales of nebular processes. As detailed in Table 1, for the project period, 14 manuscripts were published and 17 abstracts were presented describing the work.

McKeegan, Kevin D.↗

Chronology of chrondrule and CAI formation: Mg-Al isotopic evidence

Details of the chondrule and Ca-Al-rich inclusion (CAI) formation during the earliest history of the solar system are imperfectly known. Because CAI's are more 'refractory' than ferromagnesian chondrules and have the lowest recorded initial Sr-87/Sr-86 ratios of any solar system materials, the expectation is that CAI's formed earlier than chondrules. But it is not known, for example, if CAI formation had stopped by the time chondrule formation began. Conventional (absolute) age-dating techniques cannot adequately resolve small age differences (less than 10(exp 6) years) between objects of such antiquity. One approach has been to look at systematic differences in the daughter products of short-lived radionuclides such as Al-26 and I-129. Unfortunately, neither system appears to be 'well-behaved.' One possible reason for this circumstance is that later secondary events have partially reset the isotopic systems, but a viable alternative continues to be large-scale (nebular) heterogeneity in initial isotopic abundances, which would of course render the systems nearly useless as chronometers. In the past two years the nature of this problem has been redefined somewhat. Examination of the Al-Mg isotopic database for all CAI's suggests that the vast majority of inclusions originally had the same initial Al-26/Al-27 abundance ratio, and that the ill-behaved isotopic systematics now observed are the results of later partial reequilibration due to thermal processing. Isotopic heterogeneities did exist in the nebula, as demonstrated by the existence of so-called FUN inclusions in CV3 chondrites and isotopically anomalous hibonite grains in CM2 chondrites, which had little or no live Al-26 at the time of their formation. But, among the population of CV3 inclusions at least, FUN inclusions appear to have been a relatively minor nebular component.

Macpherson, G. J.↗

Nebular and Interstellar Materials in a Giant Cluster IDP of Probable Cometary Origin

Comets contain a complex mixture of materials with presolar and Solar System origins. Chondritic porous interplanetary dust particles (CP-IDPs) are associated with comets by their fragile nature, unequilibrated anhydrous mineralogy and high abundances of circumstellar grains and isotopically anomalous organic materials. Comet 81P/Wild 2 samples returned by the Stardust spacecraft contain presolar materials as well as refractory 16O-rich Ca-Al-rich inclusion- (CAI), chondrule-, and AOA-like materials. We are conducting coordinated chemical, mineralogical, and isotopic studies of a giant cluster CP-IDP (U2-20-GCA) to determine the proportions of inner Solar System and interstellar materials. We previously found that this IDP contains abundant presolar silicates (approx. 1,800 ppm) and 15N-rich hotspots [6].

Messenger, S.↗