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Hill, Hugh G. M.

Publications and source records attributed to Hill, Hugh G. M..

Great New Insights from Failed Experiments, Unanticipated Results and Embracing Controversial Observations

Experimental data and observations, whether telescopic or analytical, are never wrong, though data derived from such sources can be misinterpreted or applied inappropriately to derive conclusions that are incorrect. Given that nature always behaves according to the laws of physics and chemistry, rather than according to currently popular models and theories, experimental results should always be considered correct even when the results are far from those that one might initially expect. We discuss a number of cases where the results of experiments, even one carried out as a simple calibration measure, produced wildly different results that generally required many years of effort or contemplation to understand. On the positive side, exploration of the circumstances that produced the errant results often led to new and interesting insights concerning processes that might occur in natural environments and that were well worth the effort involved. Specifically, we show how an experiment that "failed" due to a broken conductor led to experiments that made the first refractory oxide solids containing mass independently fractionated oxygen isotopes and to 1998 predictions of the oxygen isotopic composition of the sun that were confirmed by the analysis of Genesis samples in 2011. We describe a calibration experiment that unexpectedly produced single magnetic domain iron particles. We discuss how tracking down a persistent source of "contamination" in experiments intended to produce amorphous iron and magnesium silicate smokes led to a series of studies on the synthesis of carbonaceous grain coatings that turn out to be very efficient Fischer-Tropsch catalysts and have great potential for trapping the planetary noble gases found in meteorites. We describe how models predicting the instability of silicate grains in circumstellar environments spurred new measurements of the vapor pressure of SiO partially based on previous experiments showing unexpected but systematic non-equilibrium behavior instead of the anticipated equilibrium products resembling meteoritic minerals. We trace the process that led from observations of the presence of crystalline minerals detected in the comae of some comets to the 1999 prediction of large-scale circulation of materials from the hot, innermost regions of the solar nebula out to the cold dark nebular environments where comets form. This large-scale circulation was ultimately confirmed by analyses of highly refractory Stardust samples collected from the Kuiper Belt Comet Wild 2. Finally we discuss a modern and still unresolved conflict between the assumptions built into three well known processes: the CO Self Shielding Model for mass independent isotopic fractionation of oxygen in solar system solids, rapid and thorough mixing within the solar nebula, and the efficient conversion of CO into organic coatings and volatiles on the surfaces of nebular grains via Fischer-Tropsch-type processes.

controversial↗

CO Self-Shielding as a Mechanism to Make O-16 Enriched Solids in the Solar Nebula

Photochemical self-shielding of CO has been proposed as a mechanism to produce solids observed in the modern, O-16 depleted solar system. This is distinct from the relatively O-16 enriched composition of the solar nebula, as demonstrated by the oxygen isotopic composition of the contemporary sun. While supporting the idea that self-shielding can produce local enhancements in O-16 depleted solids, we argue that complementary enhancements of O-16 enriched solids can also be produced via CO-16 based, Fischer-Tropsch type (FTT) catalytic processes that could produce much of the carbonaceous feedstock incorporated into accreting planetesimals. Local enhancements could explain observed O-16 enrichment in calcium-aluminum-rich inclusions (CAIs), such as those from the meteorite, Isheyevo (CH/CHb), as well as in chondrules from the meteorite, Acfer 214 (CH3). CO selfshielding results in an overall increase in the O-17 and O-18 content of nebular solids only to the extent that there is a net loss of CO-16 from the solar nebula. In contrast, if CO-16 reacts in the nebula to produce organics and water then the net effect of the self-shielding process will be negligible for the average oxygen isotopic content of nebular solids and other mechanisms must be sought to produce the observed dichotomy between oxygen in the Sun and that in meteorites and the terrestrial planets. This illustrates that the formation and metamorphism of rocks and organics need to be considered in tandem rather than as isolated reaction networks.

Solar Nebula↗

Condensation Processes in Astrophysical Environments

Astrophysical systems present an intriguing set of challenges for laboratory chemists. Chemistry occurs in regions considered an excellent vacuum by laboratory standards and at temperatures that would vaporize laboratory equipment. Outflows around Asymptotic Giant Branch (AGB) stars have timescales ranging from seconds to weeks depending on the distance of the region of interest from the star and, on the way significant changes in the state variables are defined. The atmospheres in normal stars may only change significantly on several billion-year timescales. Most laboratory experiments carried out to understand astrophysical processes are not done at conditions that perfectly match the natural suite of state variables or timescales appropriate for natural conditions. Experimenters must make use of simple analog experiments that place limits on the behavior of natural systems, often extrapolating to lower-pressure and/or higher-temperature environments. Nevertheless, we argue that well-conceived experiments will often provide insights into astrophysical processes that are impossible to obtain through models or observations. This is especially true for complex chemical phenomena such as the formation and metamorphism of refractory grains under a range of astrophysical conditions. Data obtained in our laboratory has been surprising in numerous ways, ranging from the composition of the condensates to the thermal evolution of their spectral properties. None of this information could have been predicted from first principals and would not have been credible even if it had.

Nuth, Joseph A., III↗

Planetary Accretion, Oxygen Isotopes and the Central Limit Theorem

The accumulation of presolar dust into increasingly larger aggregates (CAIs and Chondrules, Asteroids, Planets) should result in a very drastic reduction in the numerical spread in oxygen isotopic composition between bodies of similar size, in accord with the Central Limit Theorem. Observed variations in oxygen isotopic composition are many orders of magnitude larger than would be predicted by a simple, random accumulation model that begins in a well-mixed nebula - no matter which size-scale objects are used as the beginning or end points of the calculation. This discrepancy implies either that some as yet unspecified process acted on the solids in the Solar Nebula to increase the spread in oxygen isotopic composition during each and every stage of accumulation or that the nebula was heterogeneous and maintained this heterogeneity throughout most of nebular history. Large-scale nebular heterogeneity would have significant consequences for many areas of cosmochemistry, including the application of some well-known isotopic systems to the dating of nebular events or the prediction of bulk compositions of planetary bodies on the basis of a uniform cosmic abundance.

Nuth, Joseph A., III↗

The Formation Age of Comets: Predicted Physical and Chemical Trends

Dust grains in Herbig Ae/Be stars are continuously replenished by infalling comets. The IR spectra of these cometary grains appear to evolve temporally from initially amorphous astronomical silicates in young protostars to crystalline olivine in much older sources. Crystalline olivine can only be produced from amorphous silicates on a time scale of months-to-years via thermal annealing at temperatures near 1000 K. Since such sustained high temperatures only occur near the central star, dust annealed at 1000 K in inner nebular regions must be continuously transported beyond the nebular snowline to be incorporated into the next generation of cometesimals. The average formation age of a comet can therefore be measured as a ratio of the annealed crystalline olivine dust component to the total dust content of the comet. Comets formed from nearly pristine interstellar materials early in the protostellar nebula stage will contain very little crystalline dust whereas comets formed towards the end of the accretion period will incorporate a much higher percentage of annealed silicate. It is unlikely that only dust grains circulate from the inner to the outer nebula; the gas associated with such dust should also find its way beyond the snowline. Since this gas and dust will have equilibrated in the higher pressure-temperature regime of the inner nebula, it will contain a much higher proportion of hydrocarbons and ammonia than more pristine interstellar ices. Therefore, in addition to a higher fraction of crystalline dust, later forming comets should also contain higher ratios of hydrocarbons to CO and ammonia to N2 than do those formed early in the history of the nebula.

Nuth, Joseph A., III↗

The Magnetic Properties Of Aggregate Polycrystalline Diamond: Implications For Carbonado Petrogenesis

Carbonados are a type of diamond, which are made up of many aggregrates of small crystalline diamonds or microdiamonds. The term "carbonado" comes from the Portuguese word carbonated. They are only found in sedimentary deposits in the Central African Republic (CAR) and the Bahia Province of Brazil. They were once the source of the world's supply of industrial diamonds. Their origin is uncertain but several mutually exclusive hypotheses have been proposed. This theories are: (1) extraterrestrial, that is they formed from the dust cloud of original solar nebulae; (2) produced by the high temperatures and pressures of the Earth's mantle; (3) or as the result of an extra-terrestrial impact into a carbon rich layer of sediment. Our study was done to further the understanding of their origin. We measured the magnetic properties on some twenty samples from the CAR. An earlier study was done on whole samples of carbonados and the "common" or kimberlitic diamond. Our work differed in that we started at the surface and subsequently removed the surface layers (by days of acid immersion) into the interior; measuring the magnetic properties at each interval. This procedure permits us to monitor the distribution of magnetic substances within the samples. Our results showed that the magnetic carriers are distributed on the surface including the open pores and that the carbonado interior is essentially non-magnetic. This result suggests that the initial formation environment was deficient in magnetic particles. Such a situation could indicate that their formation was the result of an extra-terrestrial body impacting carbon-rich sediment. Obviously, more work will be required on isotopic and chemical analyses before a more detailed ori-in can be determined.

Kleteschka, Gunther↗