Frost grain size metamorphism: Implications for remote sensing of planetary surfaces

An understanding of the rates of frost grain growth is essential to the goal of relating spectral data on surface mineralogy to the physical history of a planetary surface. Models of grain growth kinetics have been constructed for various frosts based on their individual thermodynamic properties and on the difference in binding energy between molecules on plane vs curved faces. A steady state situation can occur on planetary surfaces in which thermal elimination of small grains competes with their creation, usually by meteorite impact. We utilize predicted grain growth rates to explain telescopic spectral data on condensate surfaces throughout the solar system. On Pluto, predicted CH₄ ice grain growth rates are very high despite the low temperature, resulting in a multicentimeter optical path. This explains the strong CH₄ absorption band depths, which otherwise would require large amounts of CH₄ gas. On the Uranian and Saturnian satellites, extremely slow grain growth rates are predicted because of the low vapor pressure of H₂O at the existing average surface temperatures. This may explain evidence for fine grain size and peculiar microstructure. On Io, ordinary thermal exchange is more effective than sputtering in promoting grain growth because of the properties of SO₂. Over much of Io's disk, submicron size grains of SO₂ could plausibly reconfigure into a surface glaze on a timescale comparable to the resurfacing rate. This may explain the relatively strong SO₂ signature in Io's infrared absorption spectrum as opposed to its weaker manifestation in the visible spectrum. In spite of lower sputtering fluxes, sputtering plays a more important role in grain growth for Europa, Ganymede, and Callisto than on Io. This is a result of high rates of thermally activated grain growth and resurfacing on Io. The sequence of H₂O-ice absorption band depths (related to the mean grain size) is J₂(T) ～ J₃(T) > J₂(L) > J₃(L) ～ J₄(T) ～ J₄(L), where L = leading and T = trailing. This is to be expected if sputtering were dominant. The calculations show, however, that neither thermalized exchange fluxes nor sputtering exchange fluxes can produce the implied grain growth or the ordering by ice absorption band depths of the six satellite hemispheres. Only sputtering control by simple ejection of H₂O from the satellites, as the dominant cause of shorter mean lifetimes for smaller exposed grains, can satisfactorily explain the data. Some observations, which suggest that there are vertical grain size gradients, may result from a steady state balance between intense near surface production of fine frost by comminution, coupled with ongoing ubiquitous grain growth in the vertical column. In certain cases, e.g., Europa and Enceladus, the possibility exists that endogenic activity as well as comminution could affect grain size—at least locally. It is concluded that not only ice identification and mapping, but ice grain size mapping is an important experiment to be conducted on future missions.     

Heterogeneous distributions of amino acids provide evidence of multiple sources within the Almahata Sitta parent body,asteroid 2008 TC3

Abstract– Two new fragments of the Almahata Sitta meteorite and a sample of sand from the related strewn field in the Nubian Desert, Sudan, were analyzed for two to six carbon aliphatic primary amino acids by ultrahigh performance liquid chromatography with UV‐fluorescence detection and time‐of‐flight mass spectrometry (LC‐FT/ToF‐MS). The distribution of amino acids in fragment #25, an H5 ordinary chondrite, and fragment #27, a polymict ureilite, were compared with results from the previously analyzed fragment #4, also a polymict ureilite. All three meteorite fragments contain 180–270 parts‐per‐billion (ppb) of amino acids, roughly 1000‐fold lower than the total amino acid abundance of the Murchison carbonaceous chondrite. All of the Almahata Sitta fragments analyzed have amino acid distributions that differ from the Nubian Desert sand, which primarily contains l ‐α‐amino acids. In addition, the meteorites contain several amino acids that were not detected in the sand, indicating that many of the amino acids are extraterrestrial in origin. Despite their petrological differences, meteorite fragments #25 and #27 contain similar amino acid compositions; however, the distribution of amino acids in fragment #27 was distinct from those in fragment #4, even though both are polymict ureilites from the same parent body. Unlike in CM2 and CR2/3 meteorites, there are low relative abundances of α‐amino acids in the Almahata Sitta meteorite fragments, which suggest that Strecker‐type chemistry was not a significant amino acid formation mechanism. Given the high temperatures that asteroid 2008 TC₃ appears to have experienced and lack of evidence for aqueous alteration on the asteroid, it is possible that the extraterrestrial amino acids detected in Almahata Sitta were formed by Fischer‐Tropsch/Haber‐Bosch type gas‐grain reactions at elevated temperatures.     

The effect of ocean mixed layer depth on climate in slab ocean aquaplanet experiments

The effect of ocean mixed layer depth on climate is explored in a suite of slab ocean aquaplanet simulations with different mixed layer depths ranging from a globally uniform value of 50–2.4 m. In addition to the expected increase in the amplitude of the seasonal cycle in temperature with decreasing ocean mixed layer depth, the simulated climates differ in several less intuitive ways including fundamental changes in the annual mean climate. The phase of seasonal cycle in temperature differs non-monotonically with increasing ocean mixed layer depth, reaching a maximum in the 12 m slab depth simulation. This result is a consequence of the change in the source of the seasonal heating of the atmosphere across the suite of simulations. In the shallow ocean runs, the seasonal heating of the atmosphere is dominated by the surface energy fluxes whereas the seasonal heating is dominated by direct shortwave absorption within the atmospheric column in the deep ocean runs. The surface fluxes are increasingly lagged with respect to the insolation as the ocean deepens which accounts for the increase in phase lag from the shallow to mid-depth runs. The direct shortwave absorption is in phase with insolation, and thus the total heating comes back in phase with the insolation as the ocean deepens more and the direct shortwave absorption dominates the seasonal heating of the atmosphere. The intertropical convergence zone follows the seasonally varying insolation and maximum sea surface temperatures into the summer hemisphere in the shallow ocean runs whereas it stays fairly close to the equator in the deep ocean runs. As a consequence, the tropical precipitation and region of high planetary albedo is spread more broadly across the low latitudes in the shallow runs, resulting in an apparent expansion of the tropics relative to the deep ocean runs. As a result, the global and annual mean planetary albedo is substantially (20 %) higher in the shallow ocean simulations which results in a colder (7C) global and annual mean surface temperature. The increased tropical planetary albedo in the shallow ocean simulations also results in a decreased equator-to-pole gradient in absorbed shortwave radiation and drives a severely reduced (≈50 %) meridional energy transport relative to the deep ocean runs. As a result, the atmospheric eddies are weakened and shifted poleward (away from the high albedo tropics) and the eddy driven jet is also reduced and shifted poleward by 15° relative to the deep ocean run.     

A propensity for n‐ω‐amino acids in thermally altered Antarctic meteorites

Abstract– Asteroids and their fragments have impacted the Earth for the last 4.5 Gyr. Carbonaceous meteorites are known to contain a wealth of indigenous organic molecules, including amino acids, which suggests that these meteorites could have been an important source of prebiotic organic material during the origins of life on Earth and possibly elsewhere. We report the detection of extraterrestrial amino acids in thermally altered type 3 CV and CO carbonaceous chondrites and ureilites recovered from Antarctica. The amino acid concentrations of the thirteen Antarctic meteorites ranged from 300 to 3200 parts‐per‐billion (ppb), generally much less abundant than in amino acid‐rich CI, CM, and CR carbonaceous chondrites that experienced much lower temperature aqueous alteration on their parent bodies. In contrast to low‐temperature aqueously altered meteorites that show complete structural diversity in amino acids formed predominantly by Strecker–cyanohydrin synthesis, the thermally altered meteorites studied here are dominated by small, straight‐chain, amine terminal (n‐ω‐amino) amino acids that are not consistent with Strecker formation. The carbon isotopic ratios of two extraterrestrial n‐ω‐amino acids measured in one of the CV chondrites (δ¹³C approximately ?25‰) are consistent with ¹³C‐depletions observed previously in hydrocarbons produced by Fischer‐Tropsch type reactions. The predominance of n‐ω‐amino acid isomers in thermally altered meteorites hints at cosmochemical mechanisms for the preferential formation and preservation of a small subset of the possible amino acids.     

Unusual nonterrestrial l‐proteinogenic amino acid excesses in the Tagish Lake meteorite

Abstract– The distribution and isotopic and enantiomeric compositions of amino acids found in three distinct fragments of the Tagish Lake C2‐type carbonaceous chondrite were investigated via liquid chromatography with fluorescence detection and time‐of‐flight mass spectrometry and gas chromatography isotope ratio mass spectrometry. Large l ‐enantiomeric excesses (l _ee ～ 43–59%) of the α‐hydrogen aspartic and glutamic amino acids were measured in Tagish Lake, whereas alanine, another α‐hydrogen protein amino acid, was found to be nearly racemic (d ≈ l ) using both techniques. Carbon isotope measurements of d ‐ and l ‐aspartic acid and d ‐ and l ‐alanine in Tagish Lake fall well outside of the terrestrial range and indicate that the measured aspartic acid enantioenrichment is indigenous to the meteorite. Alternate explanations for the l ‐excesses of aspartic acid such as interference from other compounds present in the sample, analytical biases, or terrestrial amino acid contamination were investigated and rejected. These results can be explained by differences in the solid–solution phase behavior of aspartic acid, which can form conglomerate enantiopure solids during crystallization, and alanine, which can only form racemic crystals. Amplification of a small initial l ‐enantiomer excess during aqueous alteration on the meteorite parent body could have led to the large l ‐enrichments observed for aspartic acid and other conglomerate amino acids in Tagish Lake. The detection of nonterrestrial l ‐proteinogenic amino acid excesses in the Tagish Lake meteorite provides support for the hypothesis that significant enantiomeric enrichments for some amino acids could form by abiotic processes prior to the emergence of life.     

Compound‐specific carbon,nitrogen, and hydrogen isotopic ratios for amino acids in CM and CR chondrites and their use in evaluating potential formation pathways

Abstract– Stable hydrogen, carbon, and nitrogen isotopic ratios (δD, δ¹³C, and δ¹⁵N) of organic compounds can reveal information about their origin and formation pathways. Several formation mechanisms and environments have been postulated for the amino acids detected in carbonaceous chondrites. As each proposed mechanism utilizes different precursor molecules, the isotopic signatures of the resulting amino acids may indicate the most likely of these pathways. We have applied gas chromatography with mass spectrometry and combustion isotope ratio mass spectrometry to measure the compound‐specific C, N, and H stable isotopic ratios of amino acids from seven CM and CR carbonaceous chondrites: CM1/2 Allan Hills (ALH) 83100, CM2 Murchison, CM2 Lewis Cliff (LEW) 90500, CM2 Lonewolf Nunataks (LON) 94101, CR2 Graves Nunataks (GRA) 95229, CR2 Elephant Moraine (EET) 92042, and CR3 Queen Alexandra Range (QUE) 99177. We compare the isotopic compositions of amino acids in these meteorites with predictions of expected isotopic enrichments from potential formation pathways. We observe trends of decreasing δ¹³C and increasing δD with increasing carbon number in the α‐H, α‐NH₂ amino acids that correspond to predictions made for formation via Strecker‐cyanohydrin synthesis. We also observe light δ¹³C signatures for β‐alanine, which may indicate either formation via Michael addition or via a pathway that forms primarily small, straight‐chain, amine‐terminal amino acids (n‐ω‐amino acids). Higher deuterium enrichments are observed in α‐methyl amino acids, indicating formation of these amino acids or their precursors in cold interstellar or nebular environments. Finally, individual amino acids are more enriched in deuterium in CR chondrites than in CM chondrites, reflecting different parent‐body chemistry.     

International borders, ground water flow, and hydroschizophrenia

A substantial body of research has been conducted on transboundary water, transboundary water law, and the mitigation of transboundary water conflict. However, most of this work has focused primarily on surface water supplies. While it is well understood that aquifers cross international boundaries and that the base flow of international river systems is often derived in part from ground water, transboundary ground water and surface water systems are usually managed under different regimes, resulting in what has been described as "hydroschizophrenia." Adding to the problem, the hydrologic relationships between surface and ground water supplies are only known at a reconnaissance level in even the most studied international basins, and thus even basic questions regarding the territorial sovereignty of ground water resources often remain unaddressed or even unasked. Despite the tensions inherent in the international setting, riparian nations have shown tremendous creativity in approaching regional development, often through preventive diplomacy, and the creation of "baskets of benefits," which allow for positive-sum, integrative allocations of joint gains. In contrast to the notion of imminent water wars, the history of hydropolitical relations worldwide has been overwhelmingly cooperative. Limited ground water management in the international arena, coupled with the fact that few states or countries regulate the use of ground water, begs the question: will international borders serve as boundaries for increased "flows" of hydrologic information and communication to maintain strategic aquifers, or will increased competition for shared ground water resources lead to the potential loss of strategic aquifers and "no flows" for both ground water users?     

Iron-oxide crystallinity increases during soil redox oscillations

An Inceptisol A-horizon from Hawaii was subjected to a series of reduction-oxidation cycles—14 d cycle length over a 56 d duration—across the “soil-Fe” [Fe(OH)₃.Fe²⁺_(aq), log K^o = 15.74] equilibrium in triplicate redox-stat reactors. Each reducing event simulated the flush of organic C and diminished O₂ that accompanies a rainfall-induced leaching of bioavailable reductants from the forest floor into mineral soil. The soil contained considerable amounts of short-range ordered (SRO) minerals (e.g., nano-goethite and allophane) and organic matter (11% org-C). Room temperature and cryogenic ⁵⁷Fe Mössbauer spectroscopy showed that the iron-bearing minerals were dominated by nano- to micro-scale goethite, and that ferrihydrite was not present. Over the four full cycles, fluctuations in E_h (from 200 to 700 mV) and pFe²⁺ (from 2.5 to 5.5) were inversely correlated with those of pH (5.5 to 4). Here, we focus on the solubility dynamics of the framework elements (Si, Fe, Ti, and Al) that constitute 35% of the oxygen-free soil dry mass. Intra-cycle oscillations in dissolved (<3 kDa) metals peaked during the reduction half-cycles. Similar intra-cycle oscillations were observed in the HCl and acid ammonium oxalate (AAO) extractable pools. The cumulative response of soil solids during multiple redox oscillations included: (1) a decrease in most HCl and AAO extractable metals and (2) a transformation of SRO Fe (as nano-goethite) to micro-crystalline goethite and micro-crystalline hematite. This may be the first direct demonstration that Fe oxide crystallinity increases during redox oscillations—an a priori unexpected result.     

Numerical Simulation of Mesoscale Circulations in a Region of Contrasting Soil Types

Mesoscale processes that form due to changes in surface characteristics play a dominant role in the development of the planetary boundary layer structure and the formation of convection. In this study, effects of the Sandhills region of North and South Carolina on mesoscale processes are examined. Climatological analyses indicate increased convective precipitation in this location as compared to the surrounding region. This is believed to be due to enhanced convection induced by horizontal heat flux gradients caused by sharp changes in soil type and hence the heat capacity of the soil. Simulations using a non-hydrostatic mesoscale model (MM5 version 3.3) were made for a non-precipitation case with a 5-km resolution domain centered over the Carolinas from August 15, 2000 to August 18, 2000. The results showed the existence of a mesoscale circulation over the Sandhills region. Differential heating induced by contrasting soil types dividing the Coastal Plain from the central Piedmont causes this circulation. Sea-breeze circulation often combines with the Sandhills circulation to initiate convection in this region. Diurnal variations are handled well by the model indicating that the thermodynamic structure of the atmosphere is well simulated.