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NASA NTRS1999

Origin, Bulk Chemical Composition and Physical Structure of the Galilean Satellites of Jupiter: A Post-Galileo Analysis

The origin of Jupiter and the Galilean satellite system is examined in the light of the new data that has been obtained by the NASA Galileo Project. In particular, special attention is given to a theory of satellite origin which was put forward at the start of the Galileo Mission and on the basis of which several predictions have now been proven successful. These predictions concern the chemical composition of Jupiter's atmosphere and the physical structure of the satellites. According to the proposed theory of satellite origin, each of the Galilean satellites formed by chemical condensation and gravitational accumulation of solid grains within a concentric family of orbiting gas rings. These rings were cast off equatorially by the rotating proto-Jovian cloud (PJC which contracted gravitationally to form Jupiter some 4 1/2 billion years ago. The PJC formed from the gas and grains left over from the gas ring that had been shed at Jupiter's orbit by the contracting proto-solar cloud (PSC Supersonic turbulent convection provides the means for shedding discrete gas rings. The temperatures T (sub n) of the system of gas rings shed by the PSC and PJC vary with their respective mean orbital radii R (sub n) (n = 0, 1,2,...) according as T (sub n) proportional to R (sub n) (exp -0.9). If the planet Mercury condenses at 1640 K, so accounting for the high density of that planet via a process of chemical fractionation between iron and silicates, then T (sub n) at Jupiter's orbit is 158 K. Only 35% of the water vapour condenses out. Thus fractionation between rock and ice, together with an enhancement in the abundance of solids relative to gas which takes place through gravitational sedimentation of solids onto the mean orbit of the gas ring, ensures nearly equal proportions of rock and ice in each of Ganymede and Callisto. Io and Europa condense above the H20 ice point and consist solely of hydrated rock (h-rock). The Ganymedan condensate consists of h-rock and H20 ice. For Callisto, NH3 ice makes up -5% of the condensate mass next to h-rock (approximately 50%) and H2O ice (approximately 45%). Detailed thermal and structural models for each of Europa, Ganymede and Callisto are constructed on the basis of the above initial bulk chemical compositions. For Europa (E), a predicted 2-zone model consisting of a dehydrated rock core of mass 0.912 M (sub E) and a 150 km thick frozen mantle of salty H2O yields a moment-of-inertia coefficient which matches the Galileo Orbiter gravity measurement. For Ganymede (G), a 3-zone model possessing an inner core of solid FeS and mass approximately 0.116 M (sub G), and an outer H2O ice mantle of mass approximately 0.502 M (sub G) is needed to explain the gravity data. Ganymede's native magnetic field was formed by thermoremanent magnetization of Fe3O4. A new Callisto (C) model is proposed consisting of a core of mass 0.826 M (sub C) containing a uniform mixture of h-rock (60% by mass) and H2O and NH3 ices, and capped by a mantle of pure ice. This model may have the capacity to yield a thin layer of liquid NH3 (raised dot) 2H2O at the core boundary, in line with Galileo's discovery of an induced magnetic field.

Prentice, A. J. R.↗
NASA NTRS1996

Comet Shoemaker-Levy 9, Jupiter, and Impact Shock Chemistry

Four years ago this month, a hitherto unknown comet in loose orbit around Jupiter passed so near the giant planet that it was torn apart into 20 fragments by tides. One orbit later, two years ago this month, the fragments of doomed comet P/Shoemaker Levy (SL9) fell into Jupiter. The enormous energies of these impacts (the largest fragments were nearly 1 km across and, hitting at 60 km/s, released some 2-4 x 10(exp 27) ergs) produced enormous explosions. Several of the ejecta plumes were imaged towering 3000 km above Jupiter's limb. The heat released when the plumes fell was considerable and easily observed on Earth. The impacts produced strong shocks, both promptly at the impact site and again, later, and over thousands of kilometers, when the ejecta plume reentered the atmosphere. The focus of this talk will be to discuss what the SL9 impacts taught us about impact shock chemistry - the processes, the ingredients, the results - and what inferences we may draw for impacts on early Earth. Shock chemistry generates a suite of molecules not usually seen on Jupiter. The most surprising report was of a huge amount of diatomic sulfur S2 at the site of the G impact. Other unusual products include CS, CS2, OCS, H2S, SO2, HCN, CO, and H2O; although H2S and H2O are doubtless abundant below the visible clouds. Hot or enhanced CH4 and NH3 were also detected. A general rule of shock chemistry is that CO forms until either C or O is exhausted. If O greater than C, the other products are oxidized, and excess O goes to H2O. If C greater than O, the other products are reduced, and excess C goes to HCN, C2H2, and a wide variety of more complicated organics. Ultimately, given time, the carbon would react all the way to graphite, but in practice the reactions are incomplete. The dark ejecta debris were probably composed in part of carbonaceous particles generated by the shocks. In a sense, the SL9 impacts performed the famous Miller-Urey experiment on a grand scale, with one result being the production of a lot of complex brown organic solids (called "tholins"). We use, a straightforward chemical kinetics model for the H, N, C, O, S system to follow the nonequilibrium chemistry behind the shocks. The model traces the evolving chemical composition of a parcel of gas by directly integrating the web of chemical reactions. Pressure and temperature histories of the parcels are patterned after those calculated by numerical hydrodynamic simulations of the ejecta plume. A given plume parcel is generally shocked twice; t.e a parcel shocked near the impact site is ejected at high velocity and is shocked again when it reenters the atmosphere. The final state of the gas depends mostly on the second shock, provided that the latter is hot enough. The chemical evidence is ambiguous, but most indications are that C greater than O in the shocked, reacting gas. Telltale signatures of abundant oxygen - SO2, SO, CO2, O2 - were not seen, while signatures of abundant carbon - CS, CS2, and HCN - were. On the other hand, abundant H2O would appear to require O greater than C, and two other observed sulfur species, S2 and OCS, appear to form more easily in a somewhat oxidized gas, presumable vaporized from the comet itself. Since on general principles one expects the -comet to have had a more-or-less cosmic composition, i.e. O greater than C, the production of CS, CS2, and HCN probably requires C greater than O in the shocked jovian air. This in turn implies that even the largest fragments released the bulk of their energy above the jovian water table, in all likelihood above 5 bars . There is no evidence in favor of the proposition that a significant amount of wet jovian air was shocked strongly enough to coax water to react; i.e. wet jovian air saw only temperatures significantly below 2000 K.

Zahnle, Kevin↗
NASA NTRS2004

Quantitative Analysis of Spectral Interference of Spontaneous Raman Scattering in High-Pressure Fuel-Rich H2-Air Combustion

We present a theoretical study of the spectral interferences in the spontaneous Raman scattering spectra of major combustion products in 30-atm fuel-rich hydrogen-air flames. An effective methodology is introduced to choose an appropriate line-shape model for simulating Raman spectra in high-pressure combustion environments. The Voigt profile with the additive approximation assumption was found to provide a reasonable model of the spectral line shape for the present analysis. The rotational/vibrational Raman spectra of H2, N2, and H2O were calculated using an anharmonic-oscillator model using the latest collisional broadening coefficients. The calculated spectra were validated with data obtained in a 10-atm fuel-rich H2-air flame and showed excellent agreement. Our quantitative spectral analysis for equivalence ratios ranging from 1.5 to 5.0 revealed substantial amounts of spectral cross-talk between the rotational H2 lines and the N2 O-/Q-branch; and between the vibrational H2O(0,3) line and the vibrational H2O spectrum. We also address the temperature dependence of the spectral cross-talk and extend our analysis to include a cross-talk compensation technique that removes the nterference arising from the H2 Raman spectra onto the N2, or H2O spectra.

Kojima, Jun↗
NASA NTRS2005

Competitive Oxidation and Hydration During Aqueous Alteration of Asteroids

Introduction: Studies of chondrites show that incorporation of H2O ice during formation of asteroids followed by radioactive heating caused partial oxidation and hydration of primary reduced and anhydrous rocks. Oxidation of kamacite, phosphides, troilite and organic polymers occurred through consumption of water s oxygen and release of H2. Hydration caused formation of serpentine, saponite, chlorite, talc and hydrated salts. Since H2O was the major reactant in oxidation and hydration, these processes could have been competitive. Redox reactions in asteroids should have been closely connected to hydration (dehydration) during aqueous alteration and thermal metamorphism. For example, dehydration and reduction release H2O that can be consumed in oxidation and hydration, respectively. We model asteroidal processes in order to quantify the fate of H2O and water s oxygen in major redox and hydration/dehydration reactions. Model: Equilibrium compositions in the gas-solid-liquid

Zolotov, M. Y.↗
NASA NTRS2006

A Comparison of Coolant Options for Brayton Power Conversion Heat Rejection Systems

This paper describes potential heat rejection design concepts for Brayton power conversion systems. Brayton conversion systems are currently under study by NASA for Nuclear Electric Propulsion (NEP) and surface power applications. The Brayton Heat Rejection Subsystem (HRS) must dissipate waste heat generated by the power conversion system due to inefficiencies in the thermal-to-electric conversion process. Sodium potassium (NaK) and H2O are two coolant working fluids that have been investigated in the design of a pumped loop and heat pipe space HRS. In general NaK systems are high temperature (300 to 1000 K) low pressure systems, and H2O systems are low temperature (300 to 600 K) high pressure systems. NaK is an alkali metal with health and safety hazards that require special handling procedures. On the other hand, H2O is a common fluid, with no health hazards and no special handling procedures. This paper compares NaK and H20 for the HRS pumped loop coolant working fluid. A detailed Microsoft Excel (Microsoft Corporation, Redmond, WA) analytical model, HRS_Opt, was developed to evaluate the various HRS design parameters. It is capable of analyzing NaK or H2O coolant, parallel or series flow configurations, and numerous combinations of other key parameters (heat pipe spacing, diameter and radial flux, radiator facesheet thickness, fluid duct system pressure drop, system rejected power, etc.) of the HRS. This paper compares NaK against water for the HRS coolant working fluid with respect to the relative mass, performance, design and implementation issues between the two fluids.

Mason, Lee S.↗
NASA NTRS2007

Antarctic Circumpolar Current Transport Variability during 2003-05 from GRACE

Gravity Recovery and Climate Experiment (GRACE) gravity data spanning January 2003-November 2005 are used as proxies for ocean bottom pressure (BP) averaged over 1 month, spherical Gaussian caps 500 km in radius, and along paths bracketing the Antarctic Circumpolar Current's various fronts. The GRACE BP signals are compared with those derived from the Estimating the Circulation and Climate of the Ocean (ECCO) ocean modeling-assimilation system, and to a non-Boussinesq version of the Regional Ocean Model System (ROMS). The discrepancy found between GRACE and the models is 1.7 cm H2O (1 cm H2O approx. 1 hPa), slightly lower than the 1.9 cmH2O estimated by the authors independently from propagation of GRACE errors. The northern signals are weak and uncorrelated among basins. The southern signals are strong, with a common seasonality. The seasonal cycle GRACE data observed in the Pacific and Indian Ocean sectors of the ACC are consistent, with annual and semiannual amplitudes of 3.6 and 0.6 cmH2O (1.1 and 0.6 cm H2O with ECCO), the average over the full southern path peaks (stronger ACC) in the southern winter, on days of year 197 and 97 for the annual and semiannual components, respectively; the Atlantic Ocean annual peak is 20 days earlier. An approximate conversion factor of 3.1 Sv (Sv equiv 10(exp 6)cu m/s) of barotropic transport variability per cm H2O of BP change is estimated. Wind stress data time series from the Quick Scatterometer (QuikSCAT), averaged monthly, zonally, and over the latitude band 40(deg)- 65(deg)S, are also constructed and subsampled at the same months as with the GRACE data. The annual and semiannual harmonics of the wind stress peak on days 198 and 82, respectively. A decreasing trend over the 3 yr is observed in the three data types.

Gravity Recovery and Climate Experiment (GRACE)↗
NASA NTRS2008

Characterization of MJO-Related Upper Tropospheric Hydrological Processes using MLS

This study quantifies Madden-Julian Oscillation (MJO)- related hydrological variability in the upper troposphere/ lower stratosphere (UT/LS) using Aura Microwave Limb Sounder (MLS) cloud ice water content (IWC) and water vapor (H2O). In a composite of six boreal-winter MJO events, the UT/LS IWC anomaly is strongly positively correlated with the convection (TRMM rainfall) anomaly. IWC anomalies range from +/-2 mg/cu m at 215 hPa to +/-0.08 mg/cu m at 100 hPa. The UT/LS H2O anomaly has an eastward-tilting structure similar to the previous-documented temperature structure, but the H2O maximum lags the temperature maximum by about a week. The H2O anomaly is positively correlated with the convection anomaly in the UT (261 hPa) and LS (68 hPa) but negatively correlated with the convection anomaly near the tropopause (100 hPa). This analysis provides a multi-parameter construct useful in validating and improving the parameterization of convection, clouds and cloud microphysics in MJO modeling.

Atmospheric Infrared Sounder (AIRS)↗
NASA NTRS2007

Mesospheric Water Vapor Retrieved from SABER/TIMED Measurements

The SABER instrument on board the TIMED satellite is a limb scanning infrared radiometer designed to measure temperature and minor constituent vertical profiles and energetics parameters in the mesosphere and lower thermosphere (MLT) The H2O concentrations are retrieved from 6.3 micron band radiances. The interpretation of this radiance requires developing a non-LTE H2O model that includes energy exchange processes with the system of O3 and O2 vibrational levels populated at the daytime through a number of photoabsorption and photodissociation processes. We developed a research model base on an extended H2O non-LTE model of Manuilova coupled with the novel model of the electronic kinetics of the O2 and O3 photolysis products suggested by Yankosvky and Manuilova. The performed study of this model helped u to develop and test an optimized operational model for interpretation of SABER 6.3 micron band radiances. The sensitivity of retrievals to the parameters of the model is discussed. The H2O retrievals are compared to other measurements for different seasons and locations.

Feofilov, Arte, G.↗
NASA NTRS2008

Cassini/CIRS Observations of Water Vapor in Titan's Stratosphere

The Composite Infrared Spectrometer (CIRS) on the Cassini spacecraft has obtained spectra of Titan during most of the 44 flybys of the Cassini prime mission. Water vapor on Titan was first detected using whole-disk observations from the Infrared Space Observatory (Coustenis et al 1998, Astron. Astrophys. 336, L85-L89). CIRS data permlt the retrieval of the latitudinal variation of water on Titan and some limited information on its vertical profile. Emission lines of H2O on Titan are very weak in the CIRS data. Thus, large spectral averages as well as improvements in calibration are necessary to detect water vapor. Water abundances were retrieved in nadir spectra at 55 South, the Equator, and at 19 North. Limb spectra of the Equator were also modeled to constrain the vertical distribution of water. Stratospheric temperatures in the 0.5 - 4.0 mbar range were obtained by inverting spectra of CH4 in the v4 band centered at 1304/cm. The temperature in the lower stratosphere (4 - 20 mbar) was derived from fitting pure rotation lines of CH4 between 80 and 160/cm. The origin of H2O and CO2 is believed to be from the ablation of micrometeorites containing water ice, followed by photochemistry. This external source of water originates either within the Saturn system or from the interplanetary medium. Recently, Horst et al (J. Geophys. Res. 2008, in press) developed a photochemical model of Titan in which there are two external sources of oxygen. Oxygen ions (probably from Enceladus) precipitate into Titan's atmosphere to form CO at very high altitudes (1100 km). Water ice ablation at lower altitudes (700 km) forms H2O and subsequent chemistry produces CO2. CIRS measurements of CO, CO2, and now of H2O will provide valuable constraints to these photochemical models and - improve our understanding of oxygen chemistry on Titan.

Bjoraker, Gordon L.↗
NASA NTRS2011

Small Scale Trace Contaminant Testing of SA9T at Ambient and Reduced Pressure Conditions

A principle concern for air revitalization technology in a closed loop system is the capability to control carbon dioxide (CO2) and humidity (H2O). An amine based sorbent technology, SA9T, has long been evaluated for use in this application and several programs are evaluating it for use in both a cabin as well as space suit applications. While the CO2 and H2O performance of the sorbent has been tested extensively, the question of how trace contaminants impact performance requires further evaluation. This paper presents experimental results of small scale SA9T testing that was performed over a variety of test conditions and with a variety of trace contaminants. Testing evaluated the ability of SA9T media to sufficiently remove CO2 and H2O after exposure to a fully saturated trace contaminant at ambient conditions. Testing also evaluated the impact of CO2 and H2O removal performance at suit loop pressures during cyclic operation with a constant inlet contaminant load. In addition, testing evaluated the performance of SA9T at ambient conditions in a continuous 30-day test with a mixed trace contaminant stream.

Broerman, Craig↗
NASA NTRS2010

Ultraviolet Irradiation of Pyrimidine in Interstellar Ice Analogs: Formation and Photo-Stability of Nucleobases

Astrochemistry laboratory experiments recently showed that molecules of prebiotic interest can potentially form in space, as supported by the detection of amino acids in organic residues formed by the UV photolysis of ices simulating interstellar and cometary environments (H2O, CO, CO2, CH3OH, NH3, etc.). Although the presence of amino acids in the interstellar medium (ISM) is still under debate, experiments and the detection of amino acids in meteorites both support a scenario in which prebiotic molecules could be of extraterrestrial origin, before they are delivered to planets by comets, asteroids, and interplanetary dust particles. Nucleobases, the informational subunits of DNA and RNA, have also been detected in meteorites, although they have not yet been observed in the ISM. Thus, these molecules constitute another family of prebiotic compounds that can possibly form via abiotical processes in astrophysical environments. Nucleobases are nitrogen-bearing cyclic aromatic species with various functional groups attached, which are divided into two classes: pyrimidines (uracil, cytosine, and thymine) and purines (adenine and guanine). In this work, we study how UV irradiation affects pyrimidine mixed in interstellar ice analogs (H2O, NH3, CH3OH). In particular, we show that the UV irradiation of H2O:pyrimidine mixtures leads to the production of oxidized compounds including uracil, and show that both uracil and cytosine are formed upon irradiation of H2O:NH3:pyrimidine mixtures. We also study the photostability of pyrimidine and its photoproducts formed during these experiments.

Nuevo, Michel↗
NASA NTRS2011

Bench-Scale Trace Contaminant Testing of SA9T at Ambient and Reduced Pressure Conditions

A principal concern for air revitalization technology in a closed loop system is the capability to control carbon dioxide (CO2) and humidity (H2O). An amine based sorbent technology, SA9T, has been evaluated for use in this application and several programs are evaluating it for use in both cabin and space suit applications. While the CO2 and H2O performance of the sorbent has been tested extensively, the question of how trace contaminants impact performance requires further evaluation. This paper presents experimental results of bench-scale SA9T testing that was performed under a variety of test conditions and with several different trace contaminants. Tests were conducted to determine if the capacity of the SA9T media to sufficiently remove CO2 and H2O is compromised after exposure to a fully saturated trace contaminant at ambient conditions. Tests also were conducted to evaluate the performance of SA9T at ambient conditions in a continuous 30-day test with a mixed trace contaminant stream. In addition, testing also evaluated the impact of CO2 and H2O removal performance at suit loop pressures (29.6 KPa/4.3 psia) during cyclic operation with a constant inlet contaminant load.

Broerman, Craig↗
NASA NTRS2012

Water Planetary and Cometary Atmospheres: H2O/HDO Transmittance and Fluorescence Models

We developed a modern methodology to retrieve water (H2O) and deuterated water (HDO) in planetary and cometary atmospheres, and constructed an accurate spectral database that combines theoretical and empirical results. Based on a greatly expanded set of spectroscopic parameters, we built a full non-resonance cascade fluorescence model and computed fluorescence efficiencies for H2O (500 million lines) and HDO (700 million lines). The new line list was also integrated into an advanced terrestrial radiative transfer code (LBLRTM) and adapted to the CO2 rich atmosphere of Mars, for which we adopted the complex Robert-Bonamy formalism for line shapes. We then retrieved water and D/H in the atmospheres of Mars, comet C/2007 WI, and Earth by applying the new formalism to spectra obtained with the high-resolution spectrograph NIRSPEC/Keck II atop Mauna Kea (Hawaii). The new model accurately describes the complex morphology of the water bands and greatly increases the accuracy of the retrieved abundances (and the D/H ratio in water) with respect to previously available models. The new model provides improved agreement of predicted and measured intensities for many H2O lines already identified in comets, and it identifies several unassigned cometary emission lines as new emission lines of H2O. The improved spectral accuracy permits retrieval of more accurate rotational temperatures and production rates for cometary water.

Villanueva, G. L.↗
NASA NTRS2011

Radiolysis of Sulfuric Acid, Sulfuric Acid Monohydrate, and Sulfuric Acid Tetrahydrate and Its Relevance to Europa

We report laboratory studies on the 0.8 MeV proton irradiation of ices composed of sulfuric acid (H2SO4), sulfuric acid monohydrate (H2SO4 H2O), and sulfuric acid tetrahydrate (H2SO4 4H2O) between 10 and 180 K. Using infrared spectroscopy, we identify the main radiation products as H2O, SO2, (S2O3)x, H3O+, HSO4(exp -), and SO4(exp 2-). At high radiation doses, we find that H2SO4 molecules are destroyed completely and that H2SO4 H2O is formed on subsequent warming. This hydrate is significantly more stable to radiolytic destruction than pure H2SO4, falling to an equilibrium relative abundance of 50% of its original value on prolonged irradiation. Unlike either pure H2SO4 or H2SO4 H2O, the loss of H2SO4 4H2O exhibits a strong temperature dependence, as the tetrahydrate is essentially unchanged at the highest irradiation temperatures and completely destroyed at the lowest ones, which we speculate is due to a combination of radiolytic destruction and amorphization. Furthermore, at the lower temperatures it is clear that irradiation causes the tetrahydrate spectrum to transition to one that closely resembles the monohydrate spectrum. Extrapolating our results to Europa s surface, we speculate that the variations in SO2 concentrations observed in the chaotic terrains are a result of radiation processing of lower hydration states of sulfuric acid and that the monohydrate will remain stable on the surface over geological times, while the tetrahydrate will remain stable in the warmer regions but be destroyed in the colder regions, unless it can be reformed by other processes, such as thermal reactions induced by diurnal cycling.

Loeffler, M. J.↗
NASA NTRS2011

On the Formation of Interstellar Water Ice: Constraints from a Search for Hydrogen Peroxide Ice in Molecular Clouds

Recent surface chemistry experiments have shown that the hydrogenation of molecular oxygen on interstellar dust grains is a plausible formation mechanism, via hydrogen peroxide (H2O2), for the production of water (H2O) ice mantles in the dense interstellar medium. Theoretical chemistry models also predict the formation of a significant abundance of H2O2 ice in grain mantles by this route. At their upper limits, the predicted and experimental abundances are sufficiently high that H2O2 should be detectable in molecular cloud ice spectra. To investigate this further, laboratory spectra have been obtained for H2O2/H2O ice films between 2.5 and 200 micron, from 10 to 180 K, containing 3%, 30%, and 97% H2O2 ice. Integrated absorbances for all the absorption features in low-temperature H2O2 ice have been derived from these spectra. For identifying H2O2 ice, the key results are the presence of unique features near 3.5, 7.0, and 11.3 micron. Comparing the laboratory spectra with the spectra of a group of 24 protostars and field stars, all of which have strong H2O ice absorption bands, no absorption features are found that can definitely be identified with H2O2 ice. In the absence of definite H2O2 features, the H2O2 abundance is constrained by its possible contribution to the weak absorption feature near 3.47 micron found on the long-wavelength wing of the 3 micron H2O ice band. This gives an average upper limit for H2O2, as a percentage of H2O, of 9% +/- 4%. This is a strong constraint on parameters for surface chemistry experiments and dense cloud chemistry models.

Smith, R. G.↗
NASA NTRS2013

Variability in the Speed of the Brewer-Dobson Circulation as Observed by Aura/MLS

We use Aura/MLS stratospheric water vapour (H2O) measurements as tracer for dynamics and infer interannual variations in the speed of the Brewer-Dobson circulation (BDC) from 2004 to 2011. We correlate one-year time series of H2O in the lower stratosphere at two subsequent pressure levels (68 hPa, approx.18.8 km and 56 hPa, approx 19.9 km at the Equator) and determine the time lag for best correlation. The same calculation is made on the horizontal on the 100 hPa (approx 16.6 km) level by correlating the H2O time series at the Equator with the ones at 40 N and 40 S. From these lag coefficients we derive the vertical and horizontal speeds of the BDC in the tropics and extra-tropics, respectively. We observe a clear interannual variability of the vertical and horizontal branch. The variability reflects signatures of the Quasi Biennial Oscillation (QBO). Our measurements confirm the QBO meridional circulation anomalies and show that the speed variations in the two branches of the BDC are out of phase and fairly well anti-correlated. Maximum ascent rates are found during the QBO easterly phase. We also find that transport of H2O towards the Northern Hemisphere (NH) is on the average two times faster than to the Southern Hemisphere (SH) with a mean speed of 1.15m/s at 100 hPa. Furthermore, the speed towards the NH shows much more interannual variability with an amplitude of about 21% whilst the speed towards the SH varies by only 10 %. An amplitude of 21% is also observed in the variability of the ascent rate at the Equator which is on the average 0.2mm/s.

Brewer-Dobson circulation↗
NASA NTRS2014

Effects on Calculated Half-Widths and Shifts from the Line Coupling for Asymmetric-Top Molecules

The refinement of the Robert-Bonamy formalism by considering the line coupling for linear molecules developed in our previous studies [Q. Ma, C. Boulet, and R. H. Tipping, J. Chem. Phys. 139, 034305 (2013); 140, 104304 (2014)] have been extended to asymmetric-top molecules. For H2O immersed in N2 bath, the line coupling selection rules applicable for the pure rotational band to determine whether two specified lines are coupled or not are established. Meanwhile, because the coupling strengths are determined by relative importance of off-diagonal matrix elements versus diagonal elements of the operator -iS1 -S2, quantitative tools are developed with which one is able to remove weakly coupled lines from consideration. By applying these tools, we have found that within reasonable tolerances, most of the H2O lines in the pure rotational band are not coupled. This reflects the fact that differences of energy levels of the H2O states are pretty large. But, there are several dozen strongly coupled lines and they can be categorized into different groups such that the line couplings occur only within the same groups. In practice, to identify those strongly coupled lines and to confine them into sub-linespaces are crucial steps in considering the line coupling. We have calculated half-widths and shifts for some groups, including the line coupling. Based on these calculations, one can conclude that for most of the H2O lines, it is unnecessary to consider the line coupling. However, for several dozens of lines, effects on the calculated half-widths from the line coupling are small, but remain noticeable and reductions of calculated half-widths due to including the line coupling could reach to 5%. Meanwhile, effects on the calculated shifts are very significant and variations of calculated shifts could be as large as 25%.

formalism↗
NASA NTRS2015

Water in the Lithospheric Mantle Beneath a Phanerozoic Continental Belt: FTIR Analyses of Alligator Lake Xenoliths (Yukon, Canada)

Water in the mantle influences melting, metasomatism, viscosity and electrical conductivity. The Alligator Lake mantle xenolith suite is one of three bimodal peridotite suites from the northern Canadian Cordillera brought to the surface by alkali basalts, i.e., it consists of chemically distinct lherzolites and harzburgites. The lherzolites have equilibration temperatures about 50 C lower than the harzburgites and are thought to represent the fertile upper mantle of the region. The harzburgites might have come from slightly deeper in the mantle and/or be the result of a melting event above an asthenospheric upwelling detected as a seismic anomaly at 400-500 km depth. Major and trace element data are best interpreted as the lherzolite mantle having simultaneously experienced 20-25% partial melting and a metasomatic event to create the harzburgites. Well-characterized xenoliths are being analyzed for water by FTIR. Harzburgites contain 29-52 ppm H2O in orthopyroxene (opx) and (is) approximately140 ppm H2O in clinopyroxene (cpx). The lherzolites have H2O contents of 27-150 ppm in opx and 46-361 ppm in cpx. Despite correlating with enrichments in LREE, the water contents of the harzburgite pyroxenes are low relative to those of typical peridotite xenoliths, suggesting that the metasomatic agents were water-poor, contrarily to what has been suggested before. The water content of cpx is about double that of opx indicating equilibrium. Olivine water contents are low ((is) less than 5 ppm H2O) and out of equilibrium with those of opx and cpx, which may be due to H loss during xenolith ascent. This is consistent with olivines containing more water in their cores than their rims. Olivines exclusively exhibit water bands in the 3400-3000 cm-1 range, which may be indicative of a reduced environment.

Gelber, McKensie↗