An experimental study on Fischer‐Tropsch catalysis: Implications for impact phenomena and nebular chemistry

Abstract— Fischer‐Tropsch catalysis, by which CO and H₂ are converted to CH₄ on the surface of transition metals, has been considered to be one of the most important chemical reactions in many planetary processes, such as the formation of the solar and circumplanetary nebulae, the expansion of vapor clouds induced by cometary impacts, and the atmospheric re‐entry of vapor condensate due to asteroidal impacts. However, few quantitative experimental studies have been conducted for the catalytic reaction under conditions relevant to these planetary processes. In this study, we conduct Fischer‐Tropsch catalytic experiments at low pressures (1.3 times 10^?4 bar ≤ P ≤ 5.3 times 10^?1 bar) over a wide range of H₂/CO ratios (0.25–1000) using pure iron, pure nickel, and iron‐nickel alloys. We analyze what gas species are produced and measure the CH₄ formation rate. Our results indicate that the CH₄ formation rate for iron catalysts strongly depends on both pressure and the H₂/CO ratio, and that nickel is a more efficient catalyst at lower pressures and lower H₂/CO ratios. This difference in catalytic properties between iron and nickel may come from the reaction steps concerning disproportionation of CO, hydrogenation of surface carbon, and the poisoning of the catalyst. These results suggest that nickel is important in the atmospheric re‐entry of impact condensate, while iron is efficient in circumplanetary subnebulae. Our results also indicate that previous numerical models of iron catalysis based on experimental data at 1 bar considerably overestimate CH₄ formation efficiency at lower pressures, such as the solar nebula and the atmospheric re‐entry of impact condensate.     

Micro Raman spectroscopy of amphiboles and pyroxenes in the martian meteorites Zagami and Lewis Cliff 88516

Abstract— We studied micro Raman spectroscopy of amphiboles and pyroxenes in the martian meteorites Zagami and Lewis Cliff (LEW) 88516. The obtained Raman spectra of the amphiboles are similar to those of kaersutite, reconfirming the previous studies that they are kaersutitic amphiboles enriched in Ca, Al, and Ti. Even though actinolite belongs to the same amphibole group (calcic amphibole) as kaersutite, the Raman spectra of terrestrial actinolite are distinct from those of kaersutite, probably reflecting complex amphibole crystal structures. The Al‐Ti‐rich pyroxene observed in the magmatic inclusions within LEW 88516 olivine is compositionally similar to kaersutite but shows Raman spectra nearly identical to the regular pyroxene rather than amphibole. In contrast to amphibole, this will be due to relatively simple crystal structures of pyroxene. Thus, the Raman spectra of Al‐Ti‐rich phases in the martian meteorites are distinct between kaersutite and Al‐Ti‐rich pyroxene, and this study demonstrates that micro Raman spectroscopy is one of the best tools to perform mineralogical characterization of mineral phases in martian meteorites.     

Mineralogy and petrology of the Dar al Gani 476 martian meteorite: Implications for its cooling history and relationship to other shergottites

Abstract— Dar al Gani 476, the 13th martian meteorite, was recovered from the Sahara in 1998. It is a basaltic shergottitic rock composed of olivine megacrysts reaching 5 mm (24 vol%) set in a finegrained groundmass of pyroxene (59 vol%) and maskelynitized plagioclase (12 vol%) with minor amounts of accessory phases (spinel, merrillite, ilmenite). Dar al Gani 476 is similar to lithology A of Elephant Moraine A79001 (EETA79001) in petrography and mineralogy, but is distinct in several aspects. Low‐Ca pyroxenes in the Dar al Gani 476 groundmass are more magnesian (En₇₆Fs₂₁ Wo₃～En₅₈Fs₃₀Wo₁₂) than those in lithology A of EETA79001 (En₇₃Fs₂₂Wo₅～En₄₅Fs₄₃Wo₁₂), rather similar to pyroxenes in lherzolitic martian meteorites (En₇₆Fs₂₁ Wo₃～En₆₃Fs₂₂Wo₁₅). Dar al Gani 476 olivine is less magnesian and shows a narrower compositional range (Fo_76‐58) than EETA79001 olivine (Fo_81‐53), and is also similar to olivines in lherzolitic martian meteorites (Fo_74‐65). The orthopyroxene‐olivine‐chromite xenolith typical in the lithology A of EETA79001 is absent in Dar al Gani 476. It seems that Dar al Gani 476 crystallized from a slightly more primitive mafic magma than lithology A of EETA79001 and several phases (olivine, pyroxene, chromite, and ilmenite) in Dar al Gani 476 may have petrogenetic similarities to those of lherzolitic martian meteorites. Olivine megacrysts in Dar al Gani 476 are in disequilibrium with the bulk composition. The presence of fractured olivine grains in which the most Mg‐rich parts are in contact with the groundmass suggests that little diffusive modification of original olivine compositions occurred during cooling. This observation enabled us to estimate the cooling rates of Dar al Gani 476 and EETA79001 olivines, giving similar cooling rates of 0.03‐3 °C/h for Dar al Gani 476 and 0.05‐5 °C/h for EETA79001. This suggests that they were cooled near the surface (burial depth shallower than about 3 m at most), probably in lava flows during crystallization of groundmass. As is proposed for lithology A of EETA79001, it may be possible to consider that Dar al Gani 476 has an impact melt origin, a mixture of martian lherzolite and other martian rock (Queen Alexandra Range 94201, nakhlites?).     

Altitude variation of ultraviolet oxygen night airglow

Night airglow of oxygen 130.4 and 135.6 nm emissions was measured by a spectrophotometer aborad an S520 sounding rocket, launched at 19:50 JST (10:50 UT) on 14 February, 1982 from Kagoshima, Japan. The altitude variation of the emissions was obtained from 110 to 266 km at zenith angles of 35.5°±4°. The emission intensity around 260 km was about 160R and is roughly compatible with model calculations taking account of O⁺+e ^– radiative recombination as well as O⁺–O^– mutual neutralization. Some excess of about 50R, compared to the model calculation, was observed around 200 km. Possible explanations of the excess are: (i) remnant oxygen ions during the transition period from day to night and (ii) diffuse radiation from the background sky. Model calculations taking account of remnant oxygen ions were also performed by adding an excess electron density to the original density profile. However, it was found that an unreasonably large electron density is required around 200 km (5×10⁵ cm^–3) to produce the observed intensity. It is also probable that some contribution from the background sky is present in the observed intensity.     

Phase relations of pumpellyite-actinolite facies metabasites in the Sanbagawa metamorphic belt in central Shikoku, Japan

Sanbagawa metabasites metamorphosed at conditions near the upper limit of the pumpellytic-actinolite facies were examined in terms of phase equilibria in the five component system Al₂O₃---Fe₂O₃---CaO---MgO---FeO. The Fe³⁺ content of epidote measured as X^Ep_Fe (=Fe/(Fe + Al) of epidote) in the assemblage epidote-chlorite-actinolite-pumpellyite decreases gradually towards the higher-grade, pumpellyite-free areas. The progressive change in X_Fe^Ep can be detected within one metabasite bed 200 meters thick near the upper limit of the pumpellyite-actinolite facies. The Mg---Fe²⁺ substitution, as expressed by variation of Fe/(Fe + Mg) in chlorite (0.40–0.55) has little effect on the Fe³⁺ + Al) ratios of epidote and pumpellyite in the above-mentioned assemblage. The lowet X_Fe^Ep in the pumpellite-bearing assemblage is 0.15 and hence the upper limit of the pumpellyite-actinolite facies is defined by the appearance of an epidote-chlorite-actinolite assemblage with X^Ep_Fc = C.15     

Interannual Variability of Antarctic Hydrographic Structure and Frontal Zones along Meridional Sections between Syowa Station and Southern Africa

Six years of quasi-meridional crossings of the Antarctic Ocean from Antarctica to southern Africa between 4°W and 16°E longitude are analyzed, with emphasis on temperature and salinity distributions. Data are sparse, but (particularly in the southern part of the sections) adequate to show significant variations in the latitude/depth distributions and T-S characteristics of the principal water masses. In particular, the cross-sectional area occupied by Warm Deep Water (Weddell Deep Water) dropped by about one third in 1968. Positions of major features associated with the Antarctic Divergence varied by up to 5 degrees of latitude. The surface temperature gradient often observed at the Antarctic Divergence appears to be the surface expression of a shallow (possibly seasonal) thermocline which sometimes slopes upward to intersect the sea surface. There is a clear need for more closely spaced and consistently planned data from Antarctic cruises, particularly those on which physical oceanography is an ancillary activity. As a bare minimum, much more closely spaced surface temperature (and if possible also salinity) measurements would be useful.     

Seasonal Variations in Abundance and Size Composition of the Lobate Ctenophore Bolinopsis Mikado (Moser) in Tokyo Bay, Central Japan

Surveys of the abundance and size composition of the ctenophore Bolinopsis mikado were conducted in Tokyo Bay over a 5-year period from 1990 to 1994. B. mikado appeared throughout the year, and its mass occurrence was observed between August and November; annual maximum abundance ranged from 19 to 91 ind. m^–2. Water temperature seems to influence the seasonal variation of B. mikado abundance. Environmental conditions (e.g. rough waters due to a typhoon) and predation by the beroid ctenophore Beroe cucumis appear to affect annual variations of B. mikado abundance. Size frequency distributions of B. mikado indicated that its reproduction was most active in summer and fall but occurred throughout the year in Tokyo Bay. A sharp decline of the copepod population in August 1990 was probably due to predation by B. mikado which was very abundant at that time; its predatory impact was estimated to be 24 % day^–1.     

Intrusion events of the intermediate Oyashio Water into Sagami Bay, Japan

Intermediate intrusion of low salinity water (LSW) into Sagami Bay was investigated on the basis of CTD data taken in Sagami Bay and off the Boso Peninsula in 1993–1994. In October 1993, water of low temperature (<7.0°C), low salinity (<34.20 psu) and high dissolved oxygen concentration (>3.5 ml I⁻¹) intruded along the isopycnal surface of {ie29-1} at depths of 320–500 m from the Oshima East Channel to the center of the bay. On the other hand, the LSW was absent in Sagami Bay in the period of September–November 1994, though it was always found to the south off the Boso Peninsula. Salinity and dissolved oxygen distributions on relevant isopycnal surfaces and water characteristics of LSW cores revealed that the LSW intruded from the south off the Boso Peninsula to Sagami Bay through the Oshima East Channel. The LSW cores were distributed on the continental slope along 500–1000 m isobaths and its onshore-offshore scales were two to three times the internal deformation radius. Initial phosphate concentrations in the LSW revealed its origin in the northern seas. These facts suggest that the observed LSW is the submerged Oyashio Water and it flows southwestward along the continental slope as a density current in the rotating fluid. The variation of the LSW near the center of Sagami Bay is closely related to the Kuroshio flow path. The duration of LSW in Sagami Bay is 0.5 to 1.5 months.     

Magnetic detection of heated soils at paleolithic sites in Japan

We present a methodological approach to detect heated soil on ancient sites, using magnetic measurements. The method is based on changes in magnetic signals of soil by heating. The following three types of soil were used for testing the method: silty soil (SS), weathered volcanic ash (WVA, = loam) and fairly fresh volcanic ash (VA) called Odori tephra. On heating above 250–600°C, the magnetic susceptibility and remanent magnetization intensity increased for the SS and WVA samples, reflecting chemical alteration of magnetic minerals (from goethites to magnetites through hematites). The VA sample showed no susceptibility change suggesting the absence of goethites within it. On heating below 250°C, only the intensities of all the samples increased. This is possibly due to acquisition of thermal remanent magnetization. The largest change of the magnetic signals was identified for the SS sample and the smallest one was seen for the VA sample. Therefore, the in situ susceptibility measurement, which is the nondestructive and indirect method, seems to be effective to detect heated soil for sites of aqueous deposits as the SS. On the other hand, for sites of aeolian deposits as the WVA (loam) and VA, the intensity measurement of collected soils seems to be the most reliable method to detect evidence of heating. The degree of the magnetic stability (coercivity) against progressive alternating-field demagnetization was also an important parameter, indicating whether the investigated soils were heated or unheated. © 1999 John Wiley & Sons, Inc.