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Relative contributions of direct molecular elimination and radical disproportionation reactions to formation of nonrandomized nitrogen in photolysis of hydrazine
Results of isotopic measurements on an unusual stony-iron meteorite named Bencubbin, which was found in Western Australia in 1930, are reported. Nitrogen from both the metallic and stony parts of the Bencubbin meteorite was analyzed, and in both materials large excesses of (15)N were found, resulting in values of the (14)N/(15)N abundance ratios as low as 137. That is, (15)N is enriched in Bencubbin by about a factor of two relative to terrestrial nitrogen. This is the largest (15)N enrichment of any known natural material. The effect is so large that chemical processes are probably inadequate to account for it. Nuclear processes which may be responsible for the anomalous isotope abundance are discussed.
It is quite common to take the terrestrial atmospheric value of (15)N/(14)N (0.00366) as typical of nitrogen in the early solar system, but in fact there is little reason to suppose that this value had a nebula-wide significance. Indeed, it is not clear that there was a unique solar-system-wide (15)N/(14)N ratio, of whatever value. Here we review what is known about the distribution of the nitrogen isotopes among those solar-system objects that have been sampled so far and conclude that those isotopes reveal widespread inhomogeneity in the early solar system. Whether the isotopically distinct primordial components implied by this analysis were solid or gaseous or a mixture of both is not known. The isotopic composition of N in the Earth's mantle is controversial: estimates range from a 1.1 percent depletion in (15)N to a 1.4 percent enrichment. (Isotopic compositions will be expressed throughout as percent deviations from the terrestrial atmospheric value.) The present-day Martian atmosphere is characterized by a value of plus 62 percent but this enrichment in (15)N is attributed to selective loss of (14)N from the Martian exosphere. Modelling of this fractionation leads to an estimated primordial composition similar to the terrestrial atmospheric value, through the precision of this model-dependent result is unclear.
We present the first N 2 profile for Venus’ deep lower atmosphere (<15 km) and a constrained isotopic composition for cloud N 2 [1]. This work directly addresses unresolved questions for Venus using legacy observations. Prior to this work, there were no reported measurements for N 2 abundances at <15 km and the isotopic composition remained unconstrained [2]. The N 2 parameters are critical to understanding the evolution and thermal properties of the atmosphere [3-7]. Our N 2 results were obtained by re-analysis of data acquired in 1978 by the Pioneer Venus Large Probe Neutral Mass Spectrometer (LNMS) [8]. The archived mass spectra from 64.2 to 0.2 km were treated using the analytical procedures specifically developed for the LNMS [9-11]. Judicious peak fitting permitted disambiguation of (A) N 2 + and CO + at 28 u and (B) 14 N 15 N+, 13 CO + , and C 2 H 5 + at 29 u. Quality controls included comparing the (A) LNMS CO + /CO 2 + ratios to the NIST database and literature and (B) fitted counts for CO + to the expected counts of CO + calculated from C 18 O + and 13 CO + using the LNMS 16 O/ 18 O and 12 C/ 13 C ratios (obtained from CO 2 ). Our results show that N 2 is uniformly mixed across the deep lower atmosphere between ~0.2 and 15 km (2.49 ± 0.10 v%). In contrast, N 2 is non-uniformly mixed across the sub-cloud atmosphere and clouds (~15–59 km), where N 2 abundances increase by ~ 2-fold between ~15 km (2.45 ± 0.32 v%) and ~59-51 km (5.21 ± 0.18 v%). Using the cloud data, we also obtained a constrained 15 N/ 14 N ratio (2.93×10 -3 ± 0.13×10 -3 ) and δ 15 N value (-204 ± 35‰). Thus, the LNMS results [1] suggest that (A) the atmosphere is unstable at <15 km, (B) N 2 is not well-mixed >15 km, and (C) the cloud δ 15 N falls between Earth and the solar wind [12, 13]. Comparisons of the N 2 abundances and isotopic compositions for nitrogen, carbon, and oxygen to other Venus measurements will be discussed.
The Composite Infrared Spectrometer (CIRS) on the Cassini spacecraft made infrared observations of Jupiter's atmosphere during the flyby in December 2000 to January 2001. The unique database in the 600-1400/cm region with 0.53 and 2.8/cm spectral resolutions obtained from the observations permits retrieval of global maps of the thermal structure and composition of Jupiter's atmosphere including the distributions of (14)NH3 and (15)NH3. Analysis of Jupiter's ammonia distributions from three isolated (15)NH3 spectral lines in eight latitudes is presented for evaluation of the nitrogen isotopic ratio. The nitrogen isotopic ratio (14)N/(15)N (or (15)N/(14)N) in Jupiter's atmosphere in this analysis is calculated to be: 448 +/- 62 ((2.23 +/- 0.31) x 10(exp -3)). This value of the ratio determined from CIRS data is found to be in very close agreement with the value previously obtained from the measurements by the Galileo Probe Mass Spectrometer. Some possible mechanisms to account for the variation of Jupiter's observed isotopic ratio relative to various astrophysical environments are discussed.
Research based on ERTS-1 MSS imagery and field work in the southern Basin-Range Province of California, Nevada and Arizona has shown regional tectonic control of volcanism, plutonism, mineralization and faulting. This paper covers an area centered on the Colorado River between 34 15' N and 36 45' N. During the mid-Tertiary, the area was the site of plutonism and genetically related volcanism fed by fissure systems now exposed as dike swarms. Dikes, elongate plutons, and coeval normal faults trend generally northward and are believed to have resulted from east-west crustal extension. In the extensional province, gold silver mineralization is closely related to Tertiary igneous activity. Similarities in ore, structural setting, and rock types define a metallogenic district of high potential for exploration. The ERTS imagery also provides a basis for regional inventory of small faults which cut alluvium. This capability for efficient regional surveys of Recent faulting should be considered in land use planning, geologic hazards study, civil engineering and hydrology.
A Monte Carlo simulation of the sputtering of the upper atmosphere of Mars by the solar wind was performed. The calculated sputtering yields imply loss rates (molecules/cm square - sec escaping the planet) for carbon dioxide, carbon, and oxygen of R(CO2) = 2.6 X 1000000/cm square - sec, R(C) = 6.6 X 1000000/cm square - sec, and R(O) = 7.7 X 1000000/cm - sec. The total mass loss by sputtering is only about 10% of that due to chemical and photo-chemical processes, but sputtering provides a major exospheric sink for carbon. The erosion process described here preferentially removes the lighter components of the atmosphere. Calculations based on a Monte Carlo simulation suggest that for a model atmosphere, 97% of the N2 and 33% of the CO2 originally present may have been sputtered away over 4.5 X 10 to the 9th power y. In the same length of time the (15)N/(14)N isotopic ratio for the bulk atmosphere would have increased by a factor 1.7.
The SAGE satellite system was used to make measurements on the optical extinction produced by stratospheric aerosols from the Mount St. Helens eruption. Two periods of observation were analyzed. In the first period (May 21 to 31, 1980), SAGE moved southward from latitude 60 N, and crossed the United States approximately one week after the May 18th eruption. Enhancements in stratospheric extinction were confined to latitudes between about 55 N and 25 N and longitudes between 10 W and 140 W. Individual layers were observed up to altitudes of 23 km. The geographical location of these layers corresponded closely to that expected on the basis of high-altitude meteorological data. During June and much of July, SAGE was, by reason of its geographical position and other orbital characteristics, unable to make further measurements on the northern hemisphere. Between July 19th and August 12th a second southward pass over the northern hemisphere occurred and further observations were made. The volcanic aerosol in the stratosphere was now found to be widely distributed over the hemisphere, the maximum concentrations being north of 50 N. The aerosol showed considerable inhomogeneity and had reached as far south as 15 N but little, if any, had crossed the equator into the southern hemisphere. Individual layers at different heights were still distinguishable. The total stratospheric aerosol loading on this occasion appeared to be greater than in May and corresponded to an increase in global stratospheric mass of between 50 and 100 percent.
Nitrogen and noble gases have been measured in samples of a glass inclusion and its surrounding basaltic matrix in an Antarctic shergottite meteorite (EETA 79001). The nitrogen component was found trapped in the glass, but not the matrix, having a value of delta 15-N = +190 per mil. Ratios between abundances of Ar-40 and N-14, N-15 and N-14 in the glass are consistent with the dilution of a Martian atmospheric component. The trapped noble gases in the glass are similar to elemental and isotopic compositions measured in Mars atmosphere by the Viking lander, and are in general agreement with previous measurements. It is suggested that a sample of Martian atmosphere has been caught in the EETA 79001 glass, and that other shergottite, nakhilite, and chassignite meteorites with similar features probably also originated on Mars. A table is presented which lists the abundances of nitrogen and the noble gases found in the non-glassy matrix and in the EETA 79001 glass.
Friction and wear behavior of Fe and Ni sliding on aluminum oxide in aerated sulfuric acid and hydrochloric acid were investigated. The results show that the concentration of acid is an important factor in controlling the metal loss caused by wear corrosion processes in the acids. At very dilute acid concentration (10 to the -4 N), Fe behaves differently from Ni. Fe develops a soft, friable deposit, while Ni develops no corrosion layer. The formation and removal of the corrosion deposit on Fe resulted in high metal loss and coefficient of friction, as compared to the relatively low metal loss and coefficient of friction observed for Ni. At slightly higher acid concentration (10 to the -3 and 10 to the -2 N), no corrosion products were produced on both Fe and Ni. Wear of Fe and Ni was generally at a minimum. At higher acid concentration (10 to the -1 N and above), loss of Fe and Ni increased as the acid concentration increased. In sulfuric acid the maximum loss of both Fe and Ni was at 7.5 N (30%) concentration, and the metal losses of both Fe and Ni dropped markedly at 15 N (50%) and above. In hydrochloric acid, however, the Fe loss continued to increase with the increase of acid concentration, and the maximum Fe loss occurred in the most concentrated acid (12.1 N, 37%). There were variations in loss with Ni from specimen to specimen examined in hydrochloric acids (10 to the -1 N and above). The coefficient of friction for Ni increased slightly with an increase in acid concentration up to 10 to the -2 N. When corrosion started to dominate in the wear-corrosion process, the coefficient of friction decreased in both sulfuric and hydrochloric acids at 10 to the -1 N and above.
Friction and wear behavior of Fe and Ni sliding on aluminum oxide in aerated sulfuric acid and hydrochloric acid were investigated. The results show that the concentration of acid is an important factor in controlling the metal loss caused by wear corrosion processes in the acids. At very dilute acid concentration (10 to the -4 N), Fe behaves differently from Ni. Fe develops a soft, friable deposit, while Ni develops no corrosion layer. The formation and removal of the corrosion deposit on Fe resulted in high metal loss and coefficient of friction, as compared to the relatively low metal loss and coefficient of friction observed for Ni. At slightly higher acid concentration (10 to the -3 and 10 to the -2 N), no corrosion products were produced on both Fe and Ni. Wear of Fe and Ni was generally at a minimum. At higher acid concentration (10 to the -1 N and above), loss of Fe and Ni increased as the acid concentration increased. In sulfuric acid the maximum loss of both Fe and Ni was at 7.5 N (30 percent) concentration, and the metal losses of both Fe and Ni dropped markedly at 15 N (50 percent) and above. In hydrochloric acid, however, the Fe loss continued to increase with the increase of acid concentration, and the maximum Fe loss occurred in the most concentrated acid (12.1 N, 37 percent). There were variations in loss with Ni from specimen to specimen examined in hydrochloric acids (10 to the -1 N and above). The coefficient of friction for Ni increased slightly with an increase in acid concentration up to 10 to the -2 N. When corrosion started to dominate in the wear-corrosion process, the coefficient of friction decreased in both sulfuric and hydrochloric acids at 10 to the -1 N and above.
Scientific goals include a better determination of the basic physical characteristics of cometary nuclei, a more complete understanding of the complex processes in the comae, a survey of abundances and gas/dust ratios in a large number of comets, and measurement of primordial (12)C/(13)C and (14)N/(15)N ratios. The program also includes the observation of Pluto-Charon mutual eclipses to derive dimensions. Reduction and analysis of extensive narrowband photometry of Comet Halley from Cerro Tololo Inter-American Observatory, Perth Observatory, Lowell Observatory, and Mauna Kea Observatory were completed. It was shown that the 7.4-day periodicity in the activity of Comet Halley was present from late February through at least early June 1986, but there is no conclusive evidence of periodic variability in the preperihelion data. Greatly improved NH scalelengths and lifetimes were derived from the Halley data which lead to the conclusion that the abundance of NH in comets is much higher than previously believed. Simultaneous optical and thermal infrared observations were obtained of Comet P/Temple 2 using the MKO 2.2 m telescope and the NASA IRTF. Preliminary analysis of these observations shows that the comet's nucleus is highly elongated, very dark, and quite red.
Information is given in viewgraph form on the Artemis Program Rover/Mobility Systems Workshop results. Topics covered include an outpost site survey and resource assessment for Mare Tranquillitatis (15 n, 22 E). Viable mobility systems appear to be capable of supporting a 1997 launch. Achieving the defined mission objectives within a 65 kg payload appears to be possible, although with limited capability.
Solar gases have been recently reported in Parsa, an EH3 chondrite. In an effort to check whether solar gases are uniformly distributed throughout Parsa or they are located in specific phases, we analyzed two additional samples of bulk Parsa and one aubritic nodule for N and noble gases. Nitrogen studies are intended for the understanding of the nitrogen components distribution in E-chondrites. The N-systematics of the nodule are entirely different from the bulk samples. The higher N contents in this nodule, as well as its complex delta(sup 15)N structure, as compared to the normal aubrites, is suggestive that the nodule is not a genuine aubrite.
Nitrogen and noble gases are important tracers in geochemistry and chosmochemistry. Compared to noble gases, however, physicochemical properties of nitrogen, such as solubility in melt or melt/silicate partition, are not well known. Solubility of nitrogen in basalt melt depends on redox condition of the atmosphere. For example, solubility of nitrogen in E chondrite melt under reducing conditions is as high as 2 mol percent at 1500 C, suggesting that nitrogen is chemically dissolved in silicate melts, i.e., being dissolved as free anions or replacing oxygen sites in silicate network. However, the solubility and the dissolution mechanism of nitrogen under oxidizing conditions are not well investigated. To obtain nitrogen solubility in silicate melts under various redox conditions and to understand its mechanism, we are conducting experiments by using (15)N(15)N-labeled nitrogen gas. This makes it easy to distinguish dissolved nitrogen from later contamination of atmospheric nitrogen, and hence enables us to measure the nitrogen solubility accurately. As a preliminary experiment, we have measured solubility of nitrogen in basalt melt under the atmospheric oxygen pressure.
We present a model to compute flourescence spectra of the stable isotopes of CN in the comae of comets. The effects of collisions are included and shown to be significant as a mechanism secondary to the flourescence process in the calculations. Our computed spectra are compared with high-resolution spectra of the B2 sigma(+)-X2 sigma(+) (0-0) band for comets Halley, Austin, and Levy. This comparison shows that collisonal effects are observable in the CN spectra of relatively high production rate comets, such as Halley and Levy. Moreover, the model confirms that the overall structure of the CN spectra in comets results predominantly from pure flourescence governed by the Swings effect. The primary goal of our model is to provide a methodology to compute accurate rotational line flourescence efficiencies for the stable isotopes of CN: (12)C(14)N, (13)C(14)N, and (12)C(15)N. The flourescence efficiencies are required to convert observed isotope line intensity ratios to isotope abundance ratios of carbons and nitrogen in comets.
About fifty percent of all hurricanes in the Atlantic Ocean form within African easterly waves (AEW). Many previous studies have indicated that these waves result from combined barotropic-baroclinic instability of the African Easterly Jet (AEJ). The AEJ is in turn believed to be due to the strong temperature gradient between the very warm Sahara Desert and the cooler Sahel and Gulf of Guinea to the south. Zonally averaged latitude-pressure cross-sections of summertime zonal winds over Africa show the AEJ as a 8-12 m/s jet centered at 600-700 mb near 15 N. Such cross-sections also show a weaker southern hemisphere easterly jet near 5-150S, monsoonal westerlies centered beneath the AEJ, and upper tropospheric features such as the Tropical Easterly Jet (TEJ) near 30N and the subtropical westerly jet near 35ON . Thomcroft and Blackburn performed zonally symmetric simulations that showed that the effect of thermal wind balance over the observed low level meridional temperature gradient over northern Africa is particularly important in the formation of the AEJ. They also found that in order to reproduce some of the other aforementioned features of the summertime climatological wind field over Africa it is necessary to include the effects of Inter-Tropical Convergence Zone (ITCZ) convective heating. While the diabatic effects of Saharan and ITCZ heating tend to strengthen the AEJ, AEW remove energy from the AEJ, thereby weakening it. In this study we take the next step towards understanding the maintenance of the AEJ by including the effects of AEW.
The impact of ship emissions on marine boundary layer (MBL) NO(x) and SO2 levels over the Pacific Ocean has been explored by comparing predictions (with and without ships) from a global chemical transport model (GCTM) against compiled airborne observations of MBL NO(x) and SO2. For latitudes above 15 N, which define that part of the Pacific having the heaviest shipping, this analysis revealed significant model over prediction for NOx and a modest under prediction for SO2 when ship emissions were considered. Possible reasons for the difference in NO(x) and SO2 were explored using a full-chemistry box model. These results revealed that for an actual plume setting the NO(x) lifetime could be greatly shortened by chemical processes promoted by ship plume emissions themselves. Similar chemical behavior was not found for SO2.