CLAST-LADEN MELT-ROCK FRAGMENT IN THE ADAMS COUNTY,COLORADO, H5 CHONDRITE

The Adams County, Colorado, H5 chondrite contains a lithic fragment, 1 cm in size, that is texturally and mineralogically quite different from the chondritic host. It is composed of: a groundmass of fine-grained euhedral to subhedral olivine (3–15 μm) and interstitial glass enclosing larger olivine and pyroxene grains (0.15-0.5 mm; about 15 vol %); an assemblage of enstatite grains (subfragment within) and an assemblage of olivine plus orthopyroxene (a second subfragment); and about 11 vol % grains of mixed troilite and nickel-iron metal. Analyses yielded these results: (i) olivine grains of the fragment groundmass have a compositional range (Fa_12–45) and most grains contain substantial CaO and Cr₂O₃ (～ 0.20 and 0.30 avg. wt%, respectively); interstitial glass has ～ 55 wt% SiO₂; (ii) larger olivine grains of the fragment are similarly high in CaO and Cr₂O₃ and also have a wide FeO/MgO range; one unusual pyroxene is an Mg-rich pigeonite; (iii) the metal is martensite in composition (11–14 wt% Ni); and (iv) major and trace element analyses by INAA indicate an H-group bulk composition for the entire 1 cm lithic fragment. On the basis of its texture and bulk and mineral compositions, the fragment is interpreted to represent unequilibrated H-group material that was partly melted by impact. The Ca- and Cr-enriched groundmass olivine and interstitial glass resulted from rapid crystallization of the chondritic melt. The Ca- and Cr-enriched larger silicate grains, including the enstatite sub-fragment and the pigeonite grain, are residual, unmelted clasts from the target material (this is supported by the presence of similar material in actual H3 chondrites). Further impact brecciation of the clast-laden melt material, and resultant impact-splashing accounts for the presence of the fragment in the H-group Adams County host and documents the coexistence of unequilibrated and equilibrated H-group material as surface regolith on one parent body.     

GENESIS OF THE CUMULATE EUCRITES SERRA DE MAGÉ AND MOORE COUNTY: A GEOCHEMICAL STUDY

Major, minor and trace element abundances have been determined by instrumental neutron activation analysis (INAA) in whole rock and plagioclase separates of Serra de Magé (SdM). The whole rock contains 52% normative plagioclase and its chondritic normalized REE abundance pattern shows a large Eu anomaly, dominated by the plagioclase REE distribution, and nearly unfractionated La-Sm and Sm-Lu abundances. The plagioclase separates contained ～ 6% pyroxenes and exhibited a typical plagioclase REE distribution. The REE abundances in the derivative equilibrium magmas from which SdM and Moore County (MC) plagioclases crystallized have been estimated from the plagioclase data and the plagioclase mineral/liquid partition coefficients. The REE distributions in possibly earlier parental magmas were calculated by assuming that various degrees of plagioclase and pigeonite (plagioclase/pigeonite = 1) fractional crystallization had been operative prior to the crystallization of SdM and MC. The calculated La/Sm and Sm/Yb ratios for the earlier magmas are essentially the same as the equilibrium magmas over a wide range (10–95%) of the assumed fractional crystallization. Considering the REE distributions and the Fe/Fe+Mg ratios, calculation shows that there is no simple genetic relationship between MC and SdM via fractional crystallization processes. A hypothesis for the derivation of these cumulate eucrites in the plutonic environment from residual diogenitic liquid, which was produced by the extensive partial melting of an eucritic source material followed by the crystallization of diogenite, also fails to account for the fractionated REE patterns calculated for the equilibrium and the possible parental magmas for either SdM or MC. Equilibrium non-modal partial melting calculations indicate that SdM and MC could be genetically related by a factor ～ 6 difference in the degrees of partial melting from a similar source material. However, this common source material which should contain > 30% high-Ca clinopyroxene and has a chondritic normalized La/Yb ～ 3, is different than that proposed for the non-cumulate eucrites.     

Water sorption on martian regolith analogs: Thermodynamics and near-infrared reflectance spectroscopy

The near-infrared reflectance spectra of the martian surface present strong absorption features attributed to hydration water present in the regolith. In order to characterize the relationships between this water and atmospheric vapor and decipher the physical state of water molecules in martian regolith analogs, we designed and built an experimental setup to measure near-IR reflectance spectra under martian atmospheric conditions. Six samples were studied that cover part of the diversity of Mars surface mineralogy: a hydrated ferric oxide (ferrihydrite), two igneous samples (volcanic tuff, and dunite sand), and three potential water rich soil materials (Mg-sulfate, smectite powder and a palagonitic soil, the JSC Mars-1 regolith stimulant). Sorption and desorption isotherms were measured at 243 K for water vapor pressure varying from 10⁻⁵ to ∼0.3 mbar (relative humidity: 10⁻⁴ to 75%). These measurements reveal a large diversity of behavior among the sample suite in terms of absolute amount of water adsorbed, shape of the isotherm and hysteresis between the adsorption and desorption branches. Simultaneous in situ spectroscopic observations permit a detailed analysis of the spectral signature of adsorbed water and also point to clear differences between the samples. Ferric (oxy)hydroxides like ferrihydrite or other phases present in palagonitic soils are very strong water adsorbent and may play an important role in the current martian water cycle by allowing large exchange of water between dust-covered regions and atmosphere at diurnal and seasonal scales.     

Accessory mineral U–Th–Pb ages and <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar eruption chronology,and their bearing on rhyolitic magma evolution in the Pleistocene Coso volcanic field,California

We determined Ar/Ar eruption ages of eight extrusions from the Pleistocene Coso volcanic field, a long-lived series of small volume rhyolitic domes in eastern California. Combined with ion-microprobe dating of crystal ages of zircon and allanite from these lavas and from granophyre geothermal well cuttings, we were able to track the range of magma-production rates over the past 650 ka at Coso. In ≤230 ka rhyolites we find no evidence of protracted magma residence or recycled zircon (or allanite) from Pleistocene predecessors. A significant subset of zircon in the ~85 ka rhyolites yielded ages between ~100 and 200 Ma, requiring that generation of at least some rhyolites involves material from Mesozoic basement. Similar zircon xenocrysts are found in an ~200 ka granophyre. The new age constraints imply that magma evolution at Coso can occur rapidly as demonstrated by significant changes in rhyolite composition over short time intervals (≤10’s to 100’s ka). In conjunction with radioisotopic age constraints from other young silicic volcanic fields, dating of Coso rhyolites highlights the fact that at least some (and often the more voluminous) rhyolites are produced relatively rapidly, but that many small-volume rhyolites likely represent separation from long-lived mushy magma bodies.     

Experimental calibration of oxygen isotope fractionation between quartz and zircon

We report the results of an experimental calibration of oxygen isotope fractionation between quartz and zircon. Data were collected from 700 to 1000 °C, 10–20 kbar, and in some experiments the oxygen fugacity was buffered at the fayalite–magnetite–quartz equilibrium. Oxygen isotope fractionation shows no clear dependence on oxygen fugacity or pressure. Unexpectedly, some high-temperature data (900–1000 °C) show evidence for disequilibrium oxygen isotope partitioning. This is based in part on ion microprobe data from these samples that indicate some high-temperature quartz grains may be isotopically zoned. Excluding data that probably represent non-equilibrium conditions, our preferred calibration for oxygen isotope fractionation between quartz and zircon can be described by:

This relationship can be used to calculate fractionation factors between zircon and other minerals. In addition, results have been used to calculate WR/melt–zircon fractionations during magma differentiation. Modeling demonstrates that silicic magmas show relatively small changes in δ¹⁸O values during differentiation, though late-stage mafic residuals capable of zircon saturation contain elevated δ¹⁸O values. However, residuals also have larger predicted melt–zircon fractionations meaning zircons will not record enriched δ¹⁸O values generally attributed to a granitic protolith. These results agree with data from natural samples if the zircon fractionation factor presented here or from natural studies is applied.     

A chemical and thermodynamic model of oil generation in hydrocarbon source rocks

Thermodynamic calculations and Gibbs free energy minimization computer experiments strongly support the hypothesis that kerogen maturation and oil generation are inevitable consequences of oxidation/reduction disproportionation reactions caused by prograde metamorphism of hydrocarbon source rocks with increasing depth of burial.These experiments indicate that oxygen and hydrogen are conserved in the process.Accordingly, if water is stable and present in the source rock at temperatures ?25 but ?100 °C along a typical US Gulf Coast geotherm, immature (reduced) kerogen with a given atomic hydrogen to carbon ratio (H/C) melts incongruently with increasing temperature and depth of burial to produce a metastable equilibrium phase assemblage consisting of naphthenic/biomarker-rich crude oil, a type-II/III kerogen with an atomic hydrogen/carbon ratio (H/C) of ∼1, and water. Hence, this incongruent melting process promotes diagenetic reaction of detritus in the source rock to form authigenic mineral assemblages.However, in the water-absent region of the system CHO (which is extensive), any water initially present or subsequently entering the source rock is consumed by reaction with the most mature kerogen with the lowest H/C it encounters to form CO₂ gas and a new kerogen with higher H/C and O/C, both of which are in metastable equilibrium with one another.This hydrolytic disproportionation process progressively increases both the concentration of the solute in the aqueous phase, and the oil generation potential of the source rock; i.e., the new kerogen can then produce more crude oil.Petroleum is generated with increasing temperature and depth of burial of hydrocarbon source rocks in which water is not stable in the system CHO by a series of irreversible disproportionation reactions in which kerogens with higher (H/C)s melt incongruently to produce metastable equilibrium assemblages consisting of crude oil, CO₂ gas, and a more mature (oxidized) kerogen with a lower H/C which in turn melts incongruently with further burial to produce more crude oil, CO₂ gas, and a kerogen with a lower H/C and so forth.The petroleum generated in the process progresses from heavy naphthenic crude oils at low temperatures to mature petroleum at ∼150 °C. For example, the results of Computer Experiment 27 (see below) indicate that the overall incongruent melting reaction in the water-absent region of the system C-H-O at 150 °C and a depth of ∼4.3 km of an immature type-II/III kerogen with a bulk composition represented by C₂₉₂H₂₈₈O_12(c) to produce a mature (oxidized) kerogen represented by C₁₂₈H₆₈O_7(c), together with a typical crude oil with an average metastable equilibrium composition corresponding to C_8.8H_16.9 (C_8.8H_16.9(l)) and CO₂ gas (CO_2(g)) can be described by writing

(A)     

Sediment transport at the network scale and its link to channel morphology in the braided Vjosa River system

In this article we apply the CASCADE network-scale sediment connectivity model to the Vjosa River in Albania. The Vjosa is one of the last unimpaired braided rivers in Europe and, at the same time, a data scarce environment, which limits our ability to model how this pristine river might respond to future human disturbance. To initialize the model, we use remotely sensed data and modeled hydrology from a regional model. We perform a reach-by-reach optimization of surface grain size distribution (GSD) and bedload transport capacity to ensure equilibrium conditions throughout the network. In order to account for the various sources of uncertainty in the calculation of transport capacity, we performed a global sensitivity analysis. The modeled GSD distributions generated by the sensitivity analysis generally match the six GSDs measured at different locations within the network. The modeled bedload sediment fluxes increase systematically downstream, and annual fluxes at the outlet of the Vjosa are well within an order of magnitude of fluxes derived from previous estimates of the annual suspended sediment load. We then use the modeled sediment fluxes as input to a set of theoretically derived functions that successfully discriminate between multi-thread and single-thread channel patterns. This finding provides additional validation of the model results by showing a clear connection between modeled sediment concentrations and observed river morphology. Finally, we observe that a reduction in sediment flux of about 50% (e.g., due to dams) would likely cause existing braided reaches to shift toward single thread morphology. The proposed method is widely applicable and opens a new avenue for application of network-scale sediment models that aid in the exploration of river stability to changes in water and sediment fluxes.     

S2O, polysulfuroxide and sulfur polymer on Io's surface?

To settle the question of disulfur monoxide and sulfur monoxide deposition and occurrence on Io's surface, we performed series of laboratory experiments reproducing the condensation of S₂O at low temperature. Its polymerization has been monitored by recording infrared spectra under conditions of temperature, pressure, mixing with SO₂ and UV-visible radiation simulating that of Io's surface. Our experiments show that S₂O condensates are not chemically stable under ionian conditions. We also demonstrate that SO and S₂O outgassed by Io's volcanoes and condensing on Io's surface should lead to yellow polysulfuroxide deposits or to white deposits of S₂O diluted in sulfur dioxide frost (i.e., S₂O/SO₂ < 0.1%). Thus S₂O condensation cannot be responsible for the red volcanic deposits on Io. Comparison of the laboratory infrared spectra of S₂O and polysulfuroxide with NIMS/Galileo infrared spectra of Io's surface leads us to discuss the possible identification of polysulfuroxide. We also recorded the visible transmission spectra of sulfur samples resulting from polysulfuroxide decomposition. These samples consist in a mixture of sulfur polymer and orthorhombic sulfur. Using the optical constants extracted from these measurements, we show that a linear combination of the reflectance spectra of our samples, the reflectance spectrum of orthorhombic S₈ sulfur and SO₂ reflectance spectrum, leads to a very good matching of Io's visible spectrum between 330 and 520 nm. We conclude then that Io's surface is probably mainly composed of sulfur dioxide and a mixture of sulfur S₈ and sulfur polymer. Some polysulfuroxide could also co-exist with these dominant components, but is probably restricted to some volcanic areas.     

The role of fog,orography, and seasonality on precipitation in a semiarid,tropical island

Isotopes of water (²H/¹H and ¹⁸O/¹⁶O) are commonly used to trace hydrological processes such as moisture recycling, evaporation loss, and moisture source region and often vary temporally in a given region. This study provides a first‐ever characterization of temporally variable precipitation mechanisms of San Cristóbal Island, Galápagos. We collected fog, rain, and throughfall samples over three field seasons to understand the mechanisms driving seasonal‐ and event‐based variability in the isotopic composition of precipitation in Galápagos. We establish that fog is a common phenomenon in San Cristóbal, especially during the dry season, and we found that fog, compared with cocollected rainfall, is consistently enriched. We further suggest that the relative contribution of fog formed via different mechanisms (orographic, advective, radiation) varied seasonally. We found that the source region is the most dominant control of the isotopic composition of rainfall in the Galápagos at both the seasonal and event scales, but subcloud evaporative processes (the nontraditional manifestation of the amount effect) became a dominant control on the isotopic composition of rainfall during the dry season. Overall, our findings suggest that understanding seasonally variable water‐generating mechanisms is required for effective water resource management in San Cristóbal Island and other semiarid island ecosystems under current and future regimes of climate change.