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At least 145 records · Page 8

Ar-39/Ar-40 systematics of Allende inclusions

A laser microprobe was used to measure the Ar isotopic contents of individual mineral grains in four neutron-irradiated Allende samples: two coarse-grained Ca-Al-rich inclusions; one fine-grained Ca-Al-rich inclusion; and one sample with matrix and miscellaneous chondrules. The following K-Ar ages (G.y.) were obtained after degassing low Ar retentive sites by preheating the samples for one hour at 675 C: matrix, 3.5 + or - 0.2; three miscellaneous chondrules, 4.4 + or - 0.1, 4.0 + or - 0.1, and 4.4 + or - 0.1; and the fine-grained inclusion, 4.5 + or - 0.2. The minerals in the coarse-grained Ca-Al-rich inclusions have ubiquitous chlorine, less than 10 ppm K and apparent ages ranging upwards from 4.6 G.y. to well over 10 G.y. Possible explanations for these apparent ages are atmospheric contamination, the decay of K-40 prior to the formation of the solar system, and the trapping of radiogenic Ar-40 lost by the matrix.

Herzog, G. F.↗

Ar-40/Ar-39 laser-probe dating of diamond inclusions from the Premier kimberlite

The results of Ar-40/Ar-39 laser-probe analyses of individual eclogitic clinopyroxene inclusions from Premier diamonds are reported which yield a mean age of 1198 + or - 14 Myr. This age agrees well with Sm-Nd and Ar-40/Ar-39 analyses on similar Premier inclusions and is indistinguishable from the inferred time of emplacement of the host kimberlite, which implies that diamond formation was essentially synchronous with kimberlite generation. The extrapolated nonradiogenic Ar-40/Ar-36 ratio of 334 + or - 102 is similar to the present-day atmospheric composition. This value is inconsistent with Sr and Nd isotopic signatures from Premier eclogite inclusions, which suggest a depleted mantle source. Preentrapment equilibration of the inclusions with an Ar-36-rich fluid is the most probable explanation for the low nonradiogenic composition.

Phillips, D.↗

On the origin of (4)He and (40)Ar in natural gold

In a first report on our investigations of noble gases in native gold we demonstrated that placer gold contains an excess of radiogenic (4)He and (40)Ar relative to the concentrations expected from in situ decay of U, Th, and K, respectively, during the geologic age of about 30 Ma of the samples. We also showed that the U/Th-(4)He age of 36 Ma of vein-type gold from the Southern Alps agrees with its K-Ar formation age derived from associated muscovite and biotite. We now studied the question of the origin of the (4)He and (40)Ar excesses of placer gold. We conclude that gold contains two components of noble gases, a low-temperature component from fluid inclusions or phases which release noble gases at less than 800 C and a high-temperature component released when gold melts (1064 C). In some samples extremely high U and K concentrations or an unreasonably high formation age would be required to explain the observed (4)He abundances. Thus, trapped (4)He and (40)Ar must be present in gold.

Eugster, O.↗

The infrared spectra of nitriles and related compounds frozen in Ar and H2O

We present the 2320-2050 cm-1 (4.31-4.88 micrometers) infrared spectra of 16 solid-state nitriles, isonitriles, and related compounds in order to facilitate the assignment of absorption features in a spectral region now becoming accessible to astronomers for the first time through the Infrared Space Observatory (ISO). This frequency range spans the positions of the strong C triple bond N stretching vibration of these compounds and is inaccessible from the ground due to absorption by CO2 in the terrestrial atmosphere. Band positions, profiles, and intrinsic strengths (A values) were measured for compounds frozen in Ar and H2O matrices at 12 K. The molecular species examined included acetonitrile, benzonitrile (phenylcyanide), 9-anthracenecarbonitrile, dimethylcyanamide, isopropylnitrile (isobutyronitrile), methylacrylonitrile, crotononitrile, acrylonitrile (vinyl cyanide), 3-aminocrotononitrile, pyruvonitrile, dicyandiamide, cyanamide, n-butylisocyanide, methylisocyanoacetate, diisopropylcarbodiimide, and hydrogen cyanide. The C triple bond N stretching bands of the majority of nitriles fall in the 2300-2200 cm-1 (4.35-4.55 micrometers) range and have similar positions in both Ar and H2O matrices, although the bands are generally considerably broader in the H2O matrices. In contrast, the isonitriles and a few exceptional nitriles and related species produce bands at lower frequencies spanning the 2200-2080 cm-1 (4.55-4.81 micrometers) range. These features also have similar positions in both Ar and H2O matrices, and the bands are broader in the H2O matrices. Three of the compounds (pyruvonitrile, dicyandiamide, and cyanamide) show unusually large shifts of their C triple bond N stretching frequencies when changing from Ar to H2O matrices. We attribute these shifts to the formation of H2O:nitrile complexes with these compounds. The implications of these results for the identification of the 2165 cm-1 (4.62 micrometers) "XCN" interstellar feature and the 4550 cm-1 (2.2 micrometers) feature of various objects in the solar system are discussed.

NASA Center ARC↗

Ar-40/Ar-39 Ages of Maskelynite Grains from ALHA 77005

We present Ar-40/Ar-39 measurements for twelve small (20-60 micro-g) maskelynite samples from the heavily shocked martian meteorite ALHA 77005. The reported modal composition for ALHA 77005 is 50-60% olivine (Fa28), 30-40% pyroxene (Wo5Fs23En72), approx.8% maskelynite (An53), and approx.2% opaques by volume [1]). The meteorite is usually classified as a lherzolite. Previous Studies - Ar-40/Ar-39 results from previous work display disturbed release spectra [2,3]. In study [2], Ar-40/Ar-39 measurements on a 52-mg whole-rock sample produced an extremely disturbed release spec-trum, with all calculated apparent ages > 1 Ga, (Fig. 1). In a subsequent study [3], a light and a dark phase were analyzed. A 2.3-mg sample of the light, relatively low-K phase produced a disturbed release spectrum. For the first 20% of the Ar-39(sub K), most of the apparent ages exceeded >1 Ga; the remaining 80% yielded ages between 0.3-0.5 Ga. The integrated age for this phase is 0.9 Ga.

Turrin, B.↗

Field-Scale Testing of a High-Efficiency Membrane Reactor (MR)—Adsorptive Reactor (AR) Process for H2 Generation and Pre-Combustion CO2 Capture

The study objective was to field-validate the technical feasibility of a membrane- and adsorption-enhanced water gas shift reaction process employing a carbon molecular sieve membrane (CMSM)-based membrane reactor (MR) followed by an adsorptive reactor (AR) for pre-combustion CO2 capture. The project was carried out in two different phases. In Phase I, the field-scale experimental MR-AR system was designed and constructed, the membranes, and adsorbents were prepared, and the unit was tested with simulated syngas to validate functionality. In Phase II, the unit was installed at the test site, field-tested using real syngas, and a technoeconomic analysis (TEA) of the technology was completed. All project milestones were met. Specifically, (i) high-performance CMSMs were prepared meeting the target H2 permeance (>1 m3/(m2.hbar) and H2/CO selectivity of >80 at temperatures of up to 300 °C and pressures of up to 25 bar with a <10% performance decline over the testing period; (ii) pelletized adsorbents were prepared for use in relevant conditions (250 °C < T < 450 °C, pressures up to 25 bar) with a working capacity of >2.5 wt.% and an attrition rate of <0.2; (iii) TEA showed that the MR-AR technology met the CO2 capture goals of 95% CO2 purity at a cost of electricity (COE) 30% less than baseline approaches.

42 ENGINEERING↗

The Monomeric Alanediyl : AlAr i Pr8 (Ar i Pr8 = C 6 H-2,6-(C 6 H 2 -2,4,6-Pr i 3 ) 2 -3,5-Pr i 2 ): An Organoaluminum(I) Compound with a One-Coordinate Aluminum Atom

Reduction of the aluminum iodide AlI 2 Ar i Pr8 ( 1 ; Ar i Pr8 = C 6 H-2,6-(C 6 H 2 -2,4,6-Pr i 3 ) 2 -3,5-Pr i 2 ) with 5% w/w Na/NaCl in hexanes gave a dark red solution from which the monomeric alanediyl : AlAr i Pr8 ( 2 ) was isolated in ca. 28% yield as yellow-orange crystals. Compounds 1 and 2 were characterized by X-ray crystallography, electronic and NMR spectroscopy, and theoretical calculations. The Al atom in 2 is one-coordinate, and the compound displays two absorptions in its electronic spectrum at 354 and 455 nm. It reacts with H 2 under ambient conditions to give the aluminum hydride {AlH(μ-H)Ar i Pr8 } 2 , probably via a weakly bound dimer of 2 as an intermediate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Isotope study of the nonlinear pressure shifts of 85 Rb and 87 Rb hyperfine resonances in Ar, Kr, and Xe buffer gases

Measurements of the 0–0 hyperfine resonant frequencies of ground-state 85 Rb atoms show a nonlinear dependence on the pressure of the buffer gases Ar, Kr, and Xe. The nonlinearities are similar to those previously observed with 87 Rb and 133 Cs and presumed to come from alkali-metal–noble-gas van der Waals molecules. However, the shape of the nonlinearity observed for Xe conflicts with previous theory, and the nonlinearities for Ar and Kr disagree with the expected isotopic scaling of previous 87 Rb results. Improving the modeling alleviates most of these discrepancies by treating rotation quantum mechanically and considering additional spin interactions in the molecules. Including the dipolar-hyperfine interaction allows simultaneous fitting of the linear and nonlinear shifts of both 85 Rb and 87 Rb in either Ar, Kr, or Xe buffer gases with a minimal set of shared, isotope-independent parameters. To the limit of experimental accuracy, the shifts in He and N 2 were linear with pressure. Further, the results are of practical interest to vapor-cell atomic clocks and related devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Calculation of ion–ion mutual neutralization rate constants using Landau–Zener theory coupled with trajectory simulations for Ar + –Cl − , Br − , I −

In this computational study, we self-consistently calculate the rate constants of mutual neutralization reactions by incorporating the electron transfer probability, using Landau–Zener state transition theory with inputs derived from ab initio quantum chemistry calculations, into classical trajectory simulations. Electronic structure calculations are done using correlation consistent basis sets with multi-reference configuration interaction to map all the molecular electronic states below the ion-dissociation limit as a function of the distance between the reacting species. Our electronic structure calculations have been significantly improved from our previous work through improved selection of molecular electronic configurations maintaining a fine grid of 1a 0 over a wide range of bond lengths and accurate treatment of spin–orbit couplings. Non-adiabatic coupling matrix elements are calculated with the three-point central difference method near each avoided crossing to estimate the exact crossing point R x and coupling parameter H if , which are inputs to the multi-channel Landau–Zener theory to calculate the electron transition probability. Our approach is applied to estimate the mutual neutralization rate constants for the following ion pairs: Ar + –Cl − , Ar + –Br − , Ar + –I − at ∼133 Pa. Furthermore, our predictions are compared against the experimental data reported. It is seen that the improvement in the electronic structure calculation results in excellent agreement between the simulation results and the available experimental data to within a factor of ∼2 or ∼±50%.

Complete-active space self-consistent field↗

The very high n Rydberg series of Ar 16+ in Alcator C-Mod tokamak plasmas

We report x-ray transitions of the very high-n Rydberg series in Ar 16+ have been observed from Alcator C-Mod tokamak plasmas. Individual emission lines up to 1s16p-1s 2 have been resolved and the central chord line brightnesses with principal quantum number n between 7 and 16 are generally found to decay as 1/n α , with α slightly larger than 3. In the plasma periphery, emission from 1s9p-1s 2 and 1s10p-1s 2 are found to be significantly enhanced relative to this decrease, indicative of selected population of these levels through charge exchange between background neutral deuterium in the ground state and Ar 17+ . An unresolved feature between the wavelengths of 1s27p-1s 2 and 1s30p-1s 2 is also present, which arises through charge exchange with neutral deuterium in the n* = 3 excited state. The brightnesses of transitions populated by charge exchange are spatially up/down asymmetric, with an excess on the side of the magnetic surface X-point. The relative brightness of the unresolved very high-n feature compared to 1s7p-1s 2 is found to increase with electron temperature and decrease with electron density. Simulations of line emission just on the long wavelength side of the Ar 16+ ionization limit indicate that the principal quantum number decay exponent is closer to α = 4 at very high n. The brightness dependence on n below 16 is in excellent agreement with calculations from the flexible atomic code package.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Search for Nova Presolar Grains: $γ$-Ray Spectroscopy of 34 Ar and its Relevance for the Astrophysical 33 Cl($p,γ$) Reaction

The discovery of presolar grains in primitive meteorites has launched a new era of research in the study of stellar nucleosynthesis. However, the accurate classification of presolar grains as being of specific stellar origins is particularly challenging. Recently, it has been suggested that sulfur isotopic abundances may hold the key to definitively identifying presolar grains with being of nova origins and, in this regard, the astrophysical Cl 33 ( p , γ ) Ar 34 reaction is expected to play a decisive role. As such, we have performed a detailed γ -ray spectroscopy study of Ar 34 . Excitation energies have been measured with high precision and spin-parity assignments for resonant states, located above the proton threshold in Ar 34 , have been made for the first time. Uncertainties in the Cl 33 ( p , γ ) reaction have been dramatically reduced and the results indicate that a newly identified ℓ = 0 resonance at E r = 396.9 ( 13 ) keV dominates the entire rate for T = 0.25 – 0.40 GK . Furthermore, nova hydrodynamic simulations based on the present work indicate an ejected S 32 / S 33 abundance ratio distinctive from type-II supernovae and potentially compatible with recent measurements of a presolar grain.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Air Exchange Rate Impact on Activity Equilibrium Factors and Inhalation Fractional Equilibrium Factors for Rn, Xe, Kr, Ar, Ne, and Their Progeny in Vapor Intrusion, Risk, and Dose Models

Exposure to the radioactive noble gasses, especially radon, is of high concern and poses a significant risk to humans in an indoor air environment as the second leading cause of lung cancer in the United States. To evaluate and minimize the risks posed by these gasses, it is important to understand their radiological and physical properties. The EPA’s Radon Vapor Intrusion Screening Level (RVISL) calculator calculates indoor air RVISLs based on target working levels (WLs), target excess lifetime cancer risk (ELCR), and annual dose limits for the actinon (Rn-219), thoron (Rn-220), and radon (Rn-222) decay series. The RVISLs are based on inhalation and submersion in gas cloud exposure routes for residential and commercial settings. The RVISLs are analogous to preliminary remediation goals (PRGs) and dose compliance concentrations (DCCs), where the isotope-specific values are in units of activity concentration (activity per unit volume). If the concentration of a parent isotope of radon or its progeny is found to exceed the RVISL, then further action to ensure cleanup of the contaminant may be necessary. In residential and commercial settings, the RVISLs will vary based on the air exchange rate present. The EPA’s Radionuclide PRG and DCC Calculators also assess the risk/dose from noble gases in the air due to household use of water like showering. In this study, a computational method in MATLAB was developed to determine the impact of the air exchange rate on the activity equilibrium factor (A eq ) and the inhalation fractional equilibrium factor (F eq ). Both factors are values that reflect the equilibrium concentrations of progeny to their parent in the air. These factors have a direct impact on the RVISL, PRG, and DCC calculations of WL, ELCR, and annual dose, respectively. This study builds on a previous report that only focused on actinon, thoron, and radon by revisiting the original A eq and F eq calculation methods, as well as including the values for the Rn-207, Rn-209, Rn-210, Rn-211, Rn-215, Rn-216, Rn-217, Rn-218, Rn-223, Ne-24, Ar-42, Ar-43, Ar-44, Kr-74, Kr-75, Kr-76, Kr-77, Kr-88, Kr-89, Xe-120, Xe-121, Xe-122, Xe-123, Xe-135m, and Xe-138 decay chains, which are not currently available in literature. The EPA’s RVISL calculator will be updated to include the new A eq and F eq values for the actinon, thoron, and radon decay chains, while the rest of the calculators will incorporate all the new A eq and F eq values as appropriate.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗

The Very High n Rydberg Series of Ar^16+ in Alcator C-Mod Tokamak Plasmas

X-ray transitions of the very high-n Rydberg series in Ar^16+ have been observed from Alcator C-Mod tokamak plasmas. Individual emission lines up to 1s16p - 1s^2 have been resolved and the central chord line brightnesses with principal quantum number n between 7 and 16 are generally found to decay as 1/n^alpha, with alpha slightly larger than 3. In the plasma periphery, emission from 1s9p - 1s^2 and 1s10p - 1s^2 are found to be significantly enhanced relative to this decrease, indicative of selected population of these levels through charge exchange between background neutral deuterium in the ground state and Ar^17+. An unresolved feature between the wavelengths of 1s27p - 1s^2 and 1s30p - 1s^2 is also present, which arises through charge exchange with neutral deuterium in the n^* = 3 excited state. The brightnesses of transitions populated by charge exchange are spatially up/down asymmetric, with an excess on the side of the magnetic surface X-point. The relative brightness of the unresolved very high-n feature compared to 1s7p - 1s^2 is found to increase with electron temperature and decrease with electron density. Simulations of line emission just on the long wavelength side of the Ar^16$ ionization limit indicate that the principal quantum number decay exponent is closer to alpha = 4 at very high n. The brightness dependence on n below 16 is in excellent agreement with calculations from the Flexible Atomic Code package.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Spatial distribution of Ar-40/Ar-39 ages in lunar breccia 14301.

The distribution of stable and radioactive argon isotopes in a lunar breccia has been measured in situ by laser probe mass spectrometry. This new technique determines the spatial distribution of Ar-40/Ar-39 ages on less than .1 milligram of material. Calculated Ar-40/Ar-39 ages of clasts within this breccia are 3.7 and 2.9 b.y. Parentless radiogenic Ar-40 exists within the fine-grained matrix and appears to have been trapped simultaneously with solar argon. This 'atmosphere' of ambient gas appears to have been incorporated into the rock by an impact event not more than 3 b.y. ago.

Megrue, G. H.↗

Studies of K-Ar dating and xenon from extinct radioactivities in breccia 14318; implications for early lunar history

The lunar breccia 14318 is one of three Apollo-14 breccias containing substantial amounts of parentless xenon from the spontaneous fission of extinct Pu-244. The argon and xenon contained in this breccia were studied by stepwise heating of pristine and neutron-irradiated samples. The isotopic composition of xenon from fission, determined by an improved method, is shown to be from Pu-244. Concentrations of this fissiogenic xenon are in substantial excess (15-fold) of what could be produced by spontaneous fission of U-238. The breccia is found to contain abundant trapped argon with an Ar-40/Ar-36 ratio of roughly 14. Otherwise, the argon is radiogenic and gives a convincing K-Ar age of 3.69 plus or minus 0.09 b.y. by the stepwise Ar-40/Ar-39 method, nearly in agreement with ages for other Apollo-14 breccias.

Reynolds, J. H.↗

Ar-40/Ar-39 chronology and cosmic ray exposure ages of the Apollo 15 samples

The Ar-40*/Ar-39* thermal release patterns of igneous soil fragments, rake basalts, and large crystalline rocks are by and large well defined. Shock deformations of up to moderate intensities have no observable effects on the Ar-40*/Ar-39* release patterns. Neither do the Ar-40* diffusion losses have any relationship with the shock intensities. The peak of the magnetic activity in Palus Putredinis occurred at 3.33 plus or minus 0.02 Gy, lava flows continuing up to 3.13 Gy but at much reduced intensity. No correlation between the crystallization ages and the petrographic rock types was observed. The cosmic ray exposure gas indicate a mature regolith around the Hadley Rille-Apennine Front region. The exposure ages of the Apollo 15 samples cannot reliably be used to obtain the time of prominent cratering events at this site.

Husain, L.↗

Titanium spallation cross sections between 30 and 584 MeV and Ar-39 activities on the moon

The production cross sections of Ar-39 for Ti spallation at 45-, 319-, 433-, and 584-MeV proton energies were measured to be 0.37 + or - 09, 12.4 + or - 3.7, 9.1 + or - 2.7, and 17.8 + or - 6.2 mb, respectively. Normalized Ar-39 production rates and activities are also derived for protons above 40 Mev and for three differential proton spectra. It is concluded that even for samples of high-Ti content, Ti spallation by solar protons below 200-MeV energy does not contribute significantly to their Ar-39 radioactivity.

Steinbrunn, F.↗

Ar-40 intercept values and young apparent /K-40/-/Ar-40/ ages of five Apollo 15 fines

Correlations between Ar-40 and Ar-36 from size fractions of three Apollo 15 fines (15071, 15421, 15501) have been obtained. The Ar-40 intercept values of these fines and of 15091 and 15601 are generally lower than what one would expect for fines resulting from the comminution of rocks having ages of about 3.3 billion yr, typical for basalts of the landing site. This is interpreted to be the result of contamination by ray material from the Copernican age (equal or less than about 1 billion yr) craters, Autolycus and Aristillus, north of the landing site.

Jordan, J. L.↗