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Design, fabrication, and bench testing of a solar chemical receiver

Solar thermal energy can be effectively collected, transported, stored, and utilized by means of a chemical storage and transport system employing the reversible SO2 oxidation reaction. A solar chemical receiver for SO3 thermal decomposition to SO2 and oxygen was analyzed. Bench tests of a ten foot section of a receiver module were conducted with dissociated sulfuric acid (SO3 and H2O) in an electrical furnace. Measured percent conversion of SO3 was 85% of the equilibrium value. Methods were developed to fabricate and assemble a complete receiver module. These methods included applying an aluminide coating to certain exposed surfaces, assembling concentric tubes with a wire spacer, applying a platinum catalyst to the tubing wall, and coiling the entire assembly into the desired configuration.

Summers, W. A.↗

Studies of proton-irradiated SO2 at low temperatures Implications for Io

The infrared absorption spectrum from 3.3 to 27 microns of SO2 ice films has been measured at 20 and 88 K before and after 1-MeV proton irradiation. The radiation flux was chosen to simulate the estimated flux of Jovian magnetospheric 1-MeV protons incident on Io. After irradiation, SO3 is identified as the dominant molecule synthesized in the SO2 ice. This is also the case after irradiation of composite samples of SO2 with sulfur or disulfites. Darkening was observed in irradiated SO2 ice and in irradiated S8 pellets. Photometric and spectral measurements of the thermoluminescence of irradiated SO2 have been made during warming. The spectrum appears as a broad band with a maximum at 4450 A. Analysis of the luminescence data suggests that at Ionian temperatures irradiated SO2 ice would not be a dominant contributor to posteclipse brightening phenomena. After warming to room temperature, a form of SO3 remains along with a sulfate and S8. Based on these experiments, it is reasonable to propose that small amounts of SO3 may exist on the surface of Io as a result of irradiation synthesis in SO2 frosts.

Moore, M. H.↗

Sulfur Oxidation and Contrail Precursor Chemistry

Sulfuric acid (H2SO4), formed in commercial aircraft operations via fuel-S (goes to) SO2 (goes to) SO3 (goes to) H2SO4 plays an important role in the formation of contrails. It is believed that the first step occurs inside the combustor, the second step in the engine exit nozzle, and the third step in the exhaust plume. Thus, measurements of the sulfur oxidation rates are critical to the understanding of contrail formation. Field measurements of contrails formed behind commercial aircraft indicate that significantly greater conversion of fuel-bound sulfur to sulfate aerosol occurs than can be explained by our current knowledge of contrail physics and chemistry. The conversion of sulfur from S(IV) to S(VI) oxidation state, required for sulfate aerosol formation, is thermodynamically favored for the conditions that exist within jet engines but is kinetically disfavored. The principal reaction pathway is O+SO2+M (goes to) SO3+M. The rates of this reaction have never been measured in the temperature and pressure regimes available to aircraft operation. In the first year (FY02) of this project, we performed a series of experiments to elucidate the rate information for the O+SO2+M (goes to) SO3+M reaction. The work performed is described following the proposed work plan. Because we used the H2/O2 system for an O-atom source and rate coefficients were obtained via computer simulation, construction of a reaction mechanism and either recalculation or estimation of thermodynamic properties of H(x)SO(y) species are described first.

DeWitt, Kenneth J.↗

Sulfur Oxidation and Contrail Precursor Chemistry

Sulfuric acid (H2SO4), formed in commercial aircraft operations via Fuel-S (right arrow) SO2 + SO3 (right arrow) H2SO4, plays an important role in affecting the global climate change through atmospheric chemical reactions and radiative forcing. Measurement of the sulfur oxidation rates is critical to the understanding of the contrail formation. The principle reaction pathway is SO2 + O + M (right arrow) SO3 + M. Although there are many measurements for the rates of this reaction, it has never been measured in the temperature and pressure regime available to aircraft operation. In this investigation, a series of experiments were performed behind the reflected shock waves in a shock tube. OH radicals were produced in lean, shock heated SO2/H2/O2/Ar mixtures. The reaction progress was followed using OH absorption spectroscopy at 310 nm. The data were analyzed with the aid of computer modeling/simulation. The mean value of the rate coefficients of R21 determined is k(sub 21,0)/[M]= 3.9 x 10(exp 15) cm(sup 6) per square mole per second at T = 960 - 1150 K and rho = 16-30 micromole per cubic centimeter with uncertainty limits of plus or minus 30%. A non-Arrhenius fit to our data together with all existing data gives k(sub 21,0)/[M] = 1.3 x 10(exp 24) T (exp -2.5) exp(-2350 K/T) cm(sup 6) per square mole per second at T = 300 - 2500 K with the same uncertainty limits given above. The calculated conversion of S(IV)(SO2) to S(VI) (SO3 + H2SO4) was about 2% in our experimental conditions.

DeWitt, Kenneth↗

Solar Metal Sulfate-Ammonia Based Thermochemical Water Splitting Cycle for Hydrogen Production

Two classes of hybrid/thermochemical water splitting processes for the production of hydrogen and oxygen have been proposed based on (1) metal sulfate-ammonia cycles (2) metal pyrosulfate-ammonia cycles. Methods and systems for a metal sulfate MSO.sub.4--NH3 cycle for producing H2 and O2 from a closed system including feeding an aqueous (NH3)(4)SO3 solution into a photoctalytic reactor to oxidize the aqueous (NH3)(4)SO3 into aqueous (NH3)(2)SO4 and reduce water to hydrogen, mixing the resulting aqueous (NH3)(2)SO4 with metal oxide (e.g. ZnO) to form a slurry, heating the slurry of aqueous (NH4)(2)SO4 and ZnO(s) in the low temperature reactor to produce a gaseous mixture of NH3 and H2O and solid ZnSO4(s), heating solid ZnSO4 at a high temperature reactor to produce a gaseous mixture of SO2 and O2 and solid product ZnO, mixing the gaseous mixture of SO2 and O2 with an NH3 and H2O stream in an absorber to form aqueous (NH4)(2)SO3 solution and separate O2 for aqueous solution, recycling the resultant solution back to the photoreactor and sending ZnO to mix with aqueous (NH4)(2)SO4 solution to close the water splitting cycle wherein gaseous H2 and O2 are the only products output from the closed ZnSO4--NH3 cycle.

Huang, Cunping↗

Igneous and Sedimentary Compositions from Four Landing Sites on Mars from the Alpha Particle X-Ray Spectrometer (APXS)

The APXS - supported and promoted strongly by Heinrich Waenke - on all four Mars Rovers has returned compositional data from about 1000 rocks and soil targets along the combined traverses of over 60 kilometers. Providing precise and accurate bulk chemistry with typically 16 quantified elements, the APXS is a powerful and versatile tool that when combined with the ability to traverse to key rocks and soils has provided critical information needed to understand the geologic evolution of Mars. APXS data allow comparisons among landing sites, provide ground truth for orbiters and connections back to SNC meteorites. The soils and dust are basaltic in character and represent the average Mars composition similar to Adirondack basalts from Gusev crater but with unambiguous elevated and correlated S, Cl and Zn contents. At all four landing sites the APXS found several rocks with a felsic composition. The similarity is best assessed in a logarithmic ratio plot of rock normalized to the average soil composition (Fig.1). High alkaline, Al, and low Mg, Fe, low S, Cl and Ni, Zn as well as an Fe/Mn ratio of approximately 50 indicate a likely unaltered and igneous origin. Sediments, e.g. the Burns formation, with approximately 25 wt% SO3 at Meridiani Planum have been documented over 10s of kilometers (Fig. 2). This formation is compositionally homogeneous, but showing the removal of MgSO4 and a threefold increase in Cl downhill in 2 craters. The degraded rim of the Noachian crater Endeavour resembles average Mars crust, with local Ca, Mg and Fe sulfate alteration and elevated Mn, some felsic rocks, and high Al, Si and low Fe rocks, possibly indicating clays. Unusual soils at Gusev crater in the area surrounding Home Plate include some very rich in ferric sulfate salts (up to 35 wt% SO3) and some with 90% wt% SiO2, possibly indicating fumerolic activities. Rocks in the Columbia Hills show significant signs of alteration including elevated S, Cl and Br in the abraded interior. At Gale Crater, mudstones with approximately 20% clay, less than 1% SO3 and overall average Mars composition indicate a former habitable environment with low acidity. A remarkable diversity of compositions was found during Curiosity's traverses, which likely stems from material influx from the northern Gale rim. At Pahrump, the base of Mount Sharp, a homogeneous mudstone with lower Mg and Ca was encountered. The composition of this Murray unit can be traced over several kilometers with smooth trends of higher Fe/Mn and lower soluble trace elements Ni and Zn at higher elevation. The likely aeolian Stimson formation with average Mars crustal composition intersects in several places in sharp contact with the Murray formation. Both units show local alteration halos with highly elevated SiO2 of up to 75%, usually correlated with increase in Ti and often P.

Gellert, R.↗

Properties of clusters in the gas phase. V - Complexes of neutral molecules onto negative ions

Ion-molecules association reactions of the form A(-)(B)n-1 + B = A(-)(B)n were studied over a range of temperatures in the gas phase using high pressure mass spectrometry. Enthalpy and entropy changes were determined for the stepwise clustering reactions of (1) sulfur dioxide onto Cl(-), I(-), and NO2(-) with n ranging from one to three or four, and onto SO2(-) and SO3(-) with n equal to one; and (2) carbon dioxide onto Cl(-), I(-), NO2(-), CO3(-), and SO3(-) with n equal to one. From these data and earlier hydration results, the order of the magnitude of the enthalpy changes on the association of the first neutral for a series of negative ions was found to parallel the gas-phase basicity of those anions.

Keesee, R. G.↗

Sulfur trioxide in the lower atmosphere of Venus

Inconsistencies and ambiguities are noted by the present consideration of Pioneer Venus and Venera atmospheric composition measurement of Venus in the context of lower atmosphere thermodynamic equilibrium. Among the scenarios projected on the basis of assumed correctness for selected data subsets, the O2 and SO2 concentrations reported by the Pioneer Venus chromatograph and the H2O concentrations reported by Venera 11 suggest that large concentrations of SO3 are present in the lower atmosphere of Venus. Such SO3 concentrations lead, however, to difficulties in explaining the atmosphere at and above the cloud tops, and in addition require specific assumptions concerning chemical reaction rates at and near the surface.

Craig, R. A.↗

Chemical mechanisms and reaction rates for the initiation of hot corrosion of IN-738

Sodium-sulfate-induced hot corrosion of preoxidized IN-738 was studied at 975 C with special emphasis placed on the processes occurring during the long induction period. Thermogravimetric tests were run for predetermined periods of time, and then one set of specimens was washed with water. Chemical analysis of the wash solutions yielded information about water soluble metal salts and residual sulfate. A second set of samples was cross sectioned dry and polished in a nonaqueous medium. Element distributions within the oxide scale were obtained from electron microprobe X-ray micrographs. Evolution of SO was monitored throughout the thermogravimetric tests. Kinetic rate studies were performed for several pertinent processes; appropriate rate constants were obtained from the following chemical reactions: Cr2O3 + 2 Na2SO4(1) + 3/2 O2 yields 2 Na2CrO4(1) + 2 SO3(g)n TiO2 + Na2SO4(1) yields Na2O(TiO2)n + SO3(g)n TiO2 + Na2CrO4(1) yields Na2O(TiO2)n + CrO3(g).

Fryburg, G. C.↗

Achondrite ALHA77005 - Alteration of chromite and olivine

The olivine crystals of the 77005 achondrite are brown except for colorless shock lamellae, mottled patches, and grains adjacent to pools of impact melt. Sporadic dark alteration patches in brown olivine and Cr-rich spinel gave the following average electron-microprobe analyses: (olivine) P2O5 0.9, SiO2 57.9, TiO2 0, Al2O3 0.7, Cr2O3 0.4, V2O3 0, Fe2O3 (assumed oxidation state) 17.0, MgO 1.6, CaO 0.2, Na2O 0, K2O 1.8, SO3 (assumed oxidation state) 9.2, Cl 0.1, sum 89.8 wt pct; (spinel) P2O5 3.5, SiO2 2.1, TiO2 2.2, Al2O3 2.1, Cr2O3 13.4, V2O3 0.8, Fe2O3 40.7, MgO 0.9, CaO 0.1, Na2O 0, K2O 2.0, SO3 11.1, Cl 0.1, sum 79.0 wt pct. Ion-microprobe analyses revealed H in both. Rare orange patches in brown olivine from another area gave SiO2 33-35, FeO 30-28, MgO 28-32, sum 93 wt pct. Thermal metamorphism under dry oxidizing conditions is discussed as a possible alternative to shock-induced oxidation for generation of the brown olivine (McSween and Stoeffler, 1980). Because alteration patches transgress shock lamellae, and because sulfatic alteration occurs in fusion crusts of Antarctic meteorites (Gibson et al., 1983), alteration of the 77005 achondrite at the Antarctic surface is preferred to a complex series of processes needed for preterrestrial alteration.

Smith, J. V.↗

Corrosion of metals and alloys in sulfate melts at 750 C

The corrosion of Ni, Co, Ni-10Cr, Co-21Cr, and IN738 was studied at 750 C in the presence of molten sulfate mixtures (Na2SO4-Li2SO4 and Na2SO4-CoSO4) and in an atmosphere consisting of O2 + 0.12 percent SO2-SO3. The corrosion was observed to be similar for both Na2SO4-Li2SO4 and Na2SO4-CoSO4 melts. The corrosion of Ni and Co took place by the formation of a mixed oxide plus sulfide scale, very similar to the corrosion in SO2 or SO3 alone. The initial stage for the corrosion of Ni-10Cr involved the formation of a thick NiO + Ni3S2 duplex scale, and Cr sulfide was formed during the later stages. A pitting type of morphology was observed for both Co-21Cr and IN738. The pit was Cr sulfide at the beginning, and subsequently the sulfides oxidized to Cr2O3. A base-metal oxide layer was present above the pit, and this was observed to be formed very early in the corrosion process. A mechanism is proposed to explain this. In general, the formation of sulfides appears to be the primary mode of degradation in mixed sulfide melts.

Misra, A. K.↗

Soil crusts on Mars

Three distinct soillike materials sampled by the Viking landers (VL) on Mars are (in order of increasing strength): (1) drift; (2) crusty to cloddy; and (3) blocky. Relative strengths of these materials are manifested by footpad penetrations during landing (VL 1), depths of deep holes, motor currents during sampling, sampler backhoe penetrations, comminutor motor currents, impact pits, trench tailings, and successful acquisitions of the coarse fraction (only blocky material). Cementation by S Cl compounds probably contributes to the relative strengths. This is shown where the weight pct. of SO3 + Cl of each material is plotted against their relative strengths. A similar result is obtained using SO3 alone, but not with Cl which is deficient in VL 2 samples.

Moore, H. J.↗

Biospheric effects of a large extraterrestrial impact: Case study of the cretaceous/tertiary boundary crater

The Chicxulub impact crater, buried in the Yucatan carbonate platform in Mexico, is the site of the impact purported to have caused mass extinctions at the Cretaceous/Tertiary (K/T) boundary. A recently discovered Chicxulub ejecta deposit in Belize contains evidence of carbonate vaporization and precipitation from the vapor plume. Sulfate clasts are almost absent in the Belize ejecta, but are abundant in the coarse ejecta near the crater rim, hwich may reflect the greater abundance of sulfates deep in the target section. The absence of sulfate precipitates in Belize may indicate that most of the vaporized sulfur was deposited in the upper atmosphere. Hydrocode modeling of the impact indicates that between 0.4 to 7.0 x 10(exp 17) g of sulfur were vaporized by the impact in sulfates. Laser experiments indicate that SO2, SO3, and SO4 are produced, and that complex chemical reactions between plume constituents occur during condensation. The sulfur released as SO3 or SO4 converted rapidly into H2HO4 aerosol. A radiative transfer model coupled with a model of coagulation predicts that the aerosol prolonged the initial blackout period caused by impact dust only if it contained impurities. The sulfur released as SO2 converted to aerosol slowly due to the rate limiting oxidation of SO2. Radiative transfer calculations combined with rates of acid production, coagulation, and diffusion indicate that solar transmission was reduced to 10-20 percent of normal for a period of 8-13 years. This reduction produced a climate forcing (cooling) of -300 Wm(exp -2), which far exceeded the +8 Wm(exp -2) greenhouse warming caused by the CO2 released through the vaporization of carbonates, and therefore produced a decade of freezing and near-freezing temperatures. Several decades of moderate warming followed the decade of severe cooling due to the long residence time of CO2. The prolonged impact winter may have been a major cause of the K/T extinctions.

Pope, Kevin O.↗

H2O-H2SO4 system in Venus' clouds and OCS, CO, and H2SO4 profiles in Venus' troposphere

A coupled problem of diffusion and condensation is solved for the H2SO4-H2O system in Venus' cloud layer. The position of the lower cloud boundary and profiles of the H2O and H2SO4 vapor mixing ratios and of the H2O/H2SO4 ratio of sulfuric acid aerosol and its flux are calculated as functions of the column photochemical production rate of sulfuric acid, Phi(sub H2SO4). Variations of the lower cloud boundary are considered. Our basic model, which is constrained to yield f(sub H2O) (30 km) = 30 ppm (Pollack et al. 1993), predicts the position of the lower cloud boundary at 48.4 km coinciding with the mean Pioneer Venus value, the peak H2SO4 mixing ratio of 5.4 ppm, and the H2SO4 production rate Phi(sub H2SO4) = 2.2 x 10(exp 12)/sq cm/s. The sulfur to sulfuric acid mass flux ratio in the clouds is 1:27 in this model, and the mass loading ratio may be larger than this value if sulfur particles are smaller than those of sulfuric acid. The model suggests that the extinction coefficient of sulfuric acid particles with radius 3.7 micrometers (mode 3) is equal to 0.3/km in the middle cloud layer. The downward flux of CO is equal to 1.7 x 10(exp 12)/sq cm/s in this model. Our second model, which is constrained to yield f(sub H2O) = 10 ppm at the lower cloud boundary, close to the value measured by the Magellan radiooccultations, predicts the position of this boundary to be at 46.5 km, which agrees with the Magellan data; f(sub H2O) (30 km) = 90 ppm, close to the data of Moroz et al. (1983) at this altitude; Phi(sub H2SO4) = 6.4 x 10(exp 12)/sq cm/s; and Phi(sub co) = 4.2 x 10(exp 12)/sq cm/s. The S/H2SO4 flux mass ratio is 1:18, and the extinction coefficient of the mode 3 sulfuric acid particles is equal to 0.9 km in the middle cloud layer. A strong gradient of the H2SO4 vapor mixing ratio near the bottom of the cloud layer drives a large upward flux of H2SO4, which condenses and forms the excessive downward flux of liquid sulfuric acid, which is larger by a factor of 4-7 than the flux in the middle cloud layer. This is the mechanism of formation of the lower cloud layer. Variations of the lower cloud layer are discussed. Our modeling of the OCS and CO profiles in the lower atmosphere measured by Pollack et al. (1993) provides a reasonable explanation of these data and shows that the rate coefficient of the reaction SO3 + CO yields CO2 + SO2 is equal to 10(exp -11) exp(-(13,100 +/- 1000)/T) cc/s. The main channel of the reaction between SO3 and OCS is CO2 + (SO)2, and its rate coefficient is equal to 10(exp -11) exp(-(8900 +/- 500)/T) cc/s. In the conditions of Venus' lower atmosphere, (SO)2 is removed by the reaction (SO)2 + OCS yields CO + S2 + SO2. The model predicts an OCS mixing ratio of 28 ppm near the surface.

Krasnopolsky, V. A.↗

Modeling Macro- and Micro-Scale Turbulent Mixing and Chemistry in Engine Exhaust Plumes

Simulation of turbulent mixing and chemical processes in the near-field plume and plume-vortex regimes has been successfully carried out recently using a reduced gas phase kinetics mechanism which substantially decreased the computational cost. A detailed mechanism including gas phase HOx, NOx, and SOx chemistry between the aircraft exhaust and the ambient air in near-field aircraft plumes is compiled. A reduced mechanism capturing the major chemical pathways is developed. Predictions by the reduced mechanism are found to be in good agreement with those by the detailed mechanism. With the reduced chemistry, the computer CPU time is saved by a factor of more than 3.5 for the near-field plume modeling. Distributions of major chemical species are obtained and analyzed. The computed sensitivities of major species with respect to reaction step are deduced for identification of the dominant gas phase kinetic reaction pathways in the jet plume. Both the near field plume and the plume-vortex regimes were investigated using advanced mixing models. In the near field, a stand-alone mixing model was used to investigate the impact of turbulent mixing on the micro- and macro-scale mixing processes using a reduced reaction kinetics model. The plume-vortex regime was simulated using a large-eddy simulation model. Vortex plume behind Boeing 737 and 747 aircraft was simulated along with relevant kinetics. Many features of the computed flow field show reasonable agreement with data. The entrainment of the engine plumes into the wing tip vortices and also the partial detrainment of the plume were numerically captured. The impact of fluid mechanics on the chemical processes was also studied. Results show that there are significant differences between spatial and temporal simulations especially in the predicted SO3 concentrations. This has important implications for the prediction of sulfuric acid aerosols in the wake and may partly explain the discrepancy between past numerical studies (that employed parabolic or temporal approximations) and the measured data. Finally to address the major uncertainty in the near-field plume modeling related to the plume processing of sulfur compounds and advanced model was developed to evaluate its impact on the chemical processes in the near wake. A comprehensive aerosol model is developed and it is coupled with chemical kinetics and the axisymmetric turbulent jet flow models. The integrated model is used to simulate microphysical processes in the near-field jet plume, including sulfuric acid and water binary homogeneous nucleation, coagulation, non-equilibrium heteromolecular condensation, and sulfur-induced soot activation. The formation and evolution of aerosols are computed and analyzed. The computed results show that a large number of ultra-fine (0.3--0.6 nm in radius) volatile HSO4 - HO embryos are generated in the near-field plume. These embryos further grow in size by self coagulation and condensation. Soot particles can be activated by both heterogeneous nucleation and scavenging of H2SO4-H2O aerosols. These activated soot particles can serve as water condensation nuclei for contrail formation. Conditions under which ice contrails can form behind aircrafts are studied. The sensitivities of the threshold temperature for contrail formation with respect to aircraft propulsion efficiency, relative humidity, and ambient pressure are evaluated. The computed aerosol properties for different extent of fuel sulfur conversion to S(VI) (SO3 and H2SO4) in engine are examined and the results are found to be sensitive to this conversion fraction.

Menon, Suresh↗

Instrumentation Working Group Summary

The Instrumentation Working Group compiled a summary of measurement techniques applicable to gas turbine engine aerosol precursors and particulates. An assessment was made of the limits, accuracy, applicability, and technology readiness of the various techniques. Despite advances made in emissions characterization of aircraft engines, uncertainties still exist in the mechanisms by which aerosols and particulates are produced in the near-field engine exhaust. To adequately assess current understanding of the formation of sulfuric acid aerosols in the exhaust plumes of gas turbine engines, measurements are required to determine the degree and importance of sulfur oxidation in the turbine and at the engine exit. Ideally, concentrations of all sulfur species would be acquired, with emphasis on SO2 and SO3. Numerous options exist for extractive and non-extractive measurement of SO2 at the engine exit, most of which are well developed. SO2 measurements should be performed first to place an upper bound on the percentage of SO2 oxidation. If extractive and non-extractive techniques indicate that a large amount of the fuel sulfur is not detected as SO2, then efforts are needed to improve techniques for SO3 measurements. Additional work will be required to account for the fuel sulfur in the engine exhaust. Chemical Ionization Mass Spectrometry (CI-MS) measurements need to be pursued, although a careful assessment needs to be made of the sampling line impact on the extracted sample composition. Efforts should also be placed on implementing non-intrusive techniques and extending their capabilities by maximizing exhaust coverage for line-of-sight measurements, as well as development of 2-D techniques, where feasible. Recommendations were made to continue engine exit and combustor measurements of particulates. Particulate measurements should include particle size distribution, mass fraction, hydration properties, and volatile fraction. However, methods to ensure that unaltered samples are obtained need to be developed. Particulate speciation was also assigned a high priority for quantifying the fractions of carbon soot, PAH, refractory materials, metals, sulfates, and nitrates. High priority was also placed on performing a comparison of particle sizing instruments. Concern was expressed by the workshop attendees who routinely make particulate measurements about the variation in number density measured during in-flight tests by different instruments. In some cases, measurements performed by different groups of researchers during the same flight tests showed an order of magnitude variation. Second priority was assigned to measuring concentrations of odd hydrogen and oxidizing species. Since OH, HO2, H2O2, and O are extremely reactive, non-extractive measurements are recommended. A combination of absorption and fluorescence is anticipated to be effective for OH measurements in the combustor and at the engine exit. Extractive measurements of HO2 have been made in the stratosphere, where the ambient level of OH is relatively low. Use of techniques that convert HO2 to OH for combustor and engine exit measurements needs to be evaluated, since the ratio of HO2/OH may be 1% or less at both the combustor and engine exit. CI-MS might be a viable option for H2O2, subject to sampling line conversion issues. However, H2O2 is a low priority oxidizing species in the combustor and at the engine exit. Two candidates for atomic oxygen measurements are Resonance Enhanced Multi-Photon Ionization (REMPI) and Laser-Induced Fluorescence (LIF). Particulate measurement by simultaneous extractive and non-extractive techniques was given equal priority to the oxidizer measurements. Concern was expressed over the ability of typical ground test sampling lines to deliver an unaltered sample to a remotely located instrument. It was suggested that the sampling probe and line losses be checked out by attempting measurements using an optical or non-extractive technique immediately upstream of the sampling probe. This is a possible application for Laser Induced Incandescence (LII) as a check on the volume fraction of soot. Optical measurements of size distribution are not well developed for ultrafine particles less than about 20 nm in diameter, so a non-extractive technique for particulate size distribution cannot be recommended without further development. Carbon dioxide measurements need to be made to complement other extractive measurement techniques. CO2 measurements enable conversion of other species concentrations to emission indices. Carbon monoxide, which acts as a sink for oxidizing species, should be measured using non-extractive techniques. CO can be rapidly converted to CO2 in extractive probes, and a comparison between extractive and non-extractive measurements should be performed. Development of non-extractive techniques would help to assess the degree of CO conversion, and might be needed to improve the concentration measurement accuracy. Measurements of NO(x) will continue to be critical due to the role of NO and NO2 in atmospheric chemistry, and their influence on atmospheric ozone. Time-resolved measurements of temperature, velocity, and species concentrations were included on the list of desired measurement. Thermocouples are typically adequate for engine exit measurements. PIV and LDV are well established for obtaining velocity profiles. The techniques are listed in the accompanying table; are divided into extractive and non-extractive techniques. Efforts were made to include a measurement uncertainty for each technique. An assessment of the technology readiness was included.

Zaller, Michelle↗

Nonlinear Attitude Filtering Methods

The extended Kalman filter (EKF) is the workhorse of real-time spacecraft attitude estimation. Since the group SO3 of rotation matrices has dimension three, most attitude determination EKFs use lower- dimensional attitude parameterizations than the nine-parameter attitude matrix itself. The fact that all three- parameter representations of SO3 are singular or discontinuous for certain attitudes has led to extended discussions of constraints and attitude representations in EKFs. The most successful EKF uses a nonsingular parameterization for the global attitude, which necessarily has more than three parameters, while employing a three-component representation for the attitude errors. This filter has become known as the Multiplicative Extended Kalman Filter. These issues are now well understood, however, and the EKF has performed admirably in the vast majority of attitude determination applications. Nevertheless, poor performance or even divergence arising from the linearization implicit in the EKF has led to the development of nonlinear filters, most recently sigma point or unscented filters and particle filters.

Markley, F. Landis↗

Sulfur Isotopes in Gas-rich Impact-Melt Glasses in Shergottites

Large impact melt glasses in some shergottites contain huge amounts of Martian atmospheric gases and they are known as gas-rich impact-melt (GRIM) glasses. By studying the neutron-induced isotopic deficits and excesses in Sm-149 and Sm-150 isotopes resulting from Sm-149 (n,gamma) 150Sm reaction and 80Kr excesses produced by Br-79 (n,gamma) Kr-80 reaction in the GRIM glasses using mass-spectrometric techniques, it was shown that these glasses in shergottites EET79001 and Shergotty contain regolith materials irradiated by a thermal neutron fluence of approx.10(exp 15) n/sq cm near Martian surface. Also, it was shown that these glasses contain varying amounts of sulfates and sulfides based on the release patterns of SO2 (sulfate) and H2S (sulfide) using stepwise-heating mass-spectrometric techniques. Furthermore, EMPA and FE-SEM studies in basaltic-shergottite GRIM glasses EET79001, LithB (,507& ,69), Shergotty (DBS I &II), Zagami (,992 & ,994) showed positive correlation between FeO and "SO3" (sulfide + sulfate), whereas those belonging to olivine-phyric shergottites EET79001, LithA (,506, & ,77) showed positive correlation between CaO/Al2O3 and "SO3".

Rao, M. N.↗