Role of replacement in the genesis of anorthosite in the Boehls Butte area, Idaho.

USGS Publications Warehouse

Hietanen, A.

1986-01-01

In this area in N Idaho, three large and numerous small lenses of layered to massive anorthosite consisting of two, and locally three, types of plagioclase with minor hornblende and mica occur in aluminium silicate-rich garnet mica schist. In most of this anorthosite, megacrysts of andesine with bytownite inclusions are embedded in a fine-grained groundmass of bytownite or anorthite; locally, labradorite occurs rather than andesine. Some labradorite laths show Carlsbad twinning and rims of andesine around anorthite inclusions. Along the contacts, lenses of fine-grained bytownite anorthosite with some hornblende or garnet and quartz are common. These lenses could represent calcic parent rocks converted to two-plagioclase rocks by partial replacement of bytownite by andesine. -R.A.H.

Exploring high-strength glass-ceramic materials for upcycling of industrial wastes

NASA Astrophysics Data System (ADS)

Back, Gu-Seul; Park, Hyun Seo; Seo, Sung Mo; Jung, Woo-Gwang

2015-11-01

To promote the recycling of industrial waste and to develop value-added products using these resources, the possibility of manufacturing glass-ceramic materials of SiO2-CaO-Al2O3 system has been investigated by various heat treatment processes. Glass-ceramic materials with six different chemical compositions were prepared using steel industry slags and power plant waste by melting, casting and heat treatment. The X-ray diffraction results indicated that diopside and anorthite were the primary phases in the samples. The anorthite phase was formed in SiO2-rich material (at least 43 wt%). In CaO-rich material, the gehlenite phase was formed. By the differential scanning calorimetry analyses, it was found that the glass transition point was in the range of 973-1023 K, and the crystallization temperature was in the range of 1123-1223 K. The crystallization temperature increased as the content of Fe2O3 decreased. By the multi-step heat treatment process, the formation of the anorthite phase was enhanced. Using FactSage, the ratio of various phases was calculated as a function of temperature. The viscosities and the latent heats for the samples with various compositions were also calculated by FactSage. The optimal compositions for glass-ceramics materials were discussed in terms of their compressive strength, and micro-hardness.

Gehlenite and anorthite formation from fluid fly ash

NASA Astrophysics Data System (ADS)

Perná, Ivana; Šupová, Monika; Hanzlíček, Tomáš

2018-04-01

Fluid fly ash could be considered a waste, but, when well treated, it may also become a useful secondary source material. Its rather high content of calcium-containing phases along with thermally treated alumino-silicate residues resulting from coal combustion can lead to the formation of a stable system with newly formatted phases. The high temperature destroys the clay lattice and activates a new configuration of aluminum ions, changing their coordination to oxygen. The effect is accompanied by changes in charge in the surroundings, which are compensated for by calcium ions. The higher the temperature of the fluid ash treatment, the more pronounced the appearance of gehlenite and anorthite in the final mass. Both are natural materials and, together with mullite and anhydrite, they could ensure safety and protection even if exposed to open fire of up to 1150 °C.

Diffusion-controlled garnet growth in siliceous dolomites of the Adamello contact aureole, N-Italy

NASA Astrophysics Data System (ADS)

Muller, T.; Fiebich, E.; Foster, C. T.

2012-12-01

Texture forming processes are controlled by many factors, such as material transport through polycrystalline materials, surface kinetics, fluid flow, and many others. In metamorphic rocks, texture forming processes typically involve local reactions linked to net mass transfer which allows constraining the actual reaction path in more detail. In this study, we present geochemical data combined with textural modeling to constrain the conditions and reaction mechanism during contact metamorphic garnet growth in siliceous dolomites in the southern Adamello Massif, Italy. The metamorphic garnet porphyroblasts are poikiloblastic and idiomorphic in shape with a typical grain size ranging between 0.6-1 cm in diameter sitting in a matrix of calcite+diopside+anorthite+wollastonite. Inclusions in the grossular-rich garnets are almost uniquely diopside. On the hand specimen, garnets are surrounded by visible rims of about 0.6 mm indicating a diffusion-limited reaction mechanism to be responsible for the garnet formation. In the course of this study samples have been characterized by polarization microscopy, element x-ray maps using EMPA, cathodulominescence images and stable isotope analyses of carbon and oxygen of matrix carbonates. In addition, pseudosections have been calculated using the software package PerpleX (Connolly, 2005) based on the bulk chemistry of collected samples. Results indicate that the visible margin consists of a small rim (< 1 mm) purely consisting of recrystallized calcite adjacent to the garnet edge. The major part of the observed halo, however, is characterized by the absence of anorthite and wollastonite. The observed texture of garnet porphyroblasts growing and simultaneously forming an anorthite and wollastonite free margin can successfully be reproduced using the SEG program (Foster, 1993), which assumes diffusive mass transport. Therefore the model constrains the diffusive fluxes of Ca, Mg, Al and Si by mass balance and the local Gibbs-Duhem equations on the reaction site. Assuming that the pore fluid is not saturated in CO2, which is justified for the assumption of fluid-infiltration during contact metamorphism, the model predicts the wollastonite halo to be about the same size as the anorthite halo. Interestingly, the model also predicts the small diopside-free calcite margin surrounding the garnet interface, which is also observed in the thin section of the natural sample. Taken together, we interpret the garnet growth to be the consequence of the breakdown of anorthite + wollastonite + calcite at water-rich (XCO2 < 0.2) conditions around 600 °C. Preliminary modeling results suggest that the effective relative diffusion coefficients for Si, Mg and Al are not equal producing the diopside-free calcite rim surrounding the garnet edge. Connolly, J.A.D., 2005, Computation of phase equilibria by linear programming: A tool for geodynamic modeling and its application to subduction zone decarbonation. EPSL, 236 : p. 524-541. Foster, C.T., 1993, SEG93: A program to model metamorphic textures: Geological Society of America Abstracts with Programs, v. 25, no. 6, p. A264.

Shock compression of liquid silicates to 125 GPa: the anorthite-diopside join

NASA Astrophysics Data System (ADS)

Asimow, P. D.; Ahrens, T. J.

2008-12-01

Shock compression of pre-heated liquid silicates provides, at present, the only method for direct measurement of the equation of state of such liquids at lower mantle pressures. At previous AGU meetings we have reported the extension of the pre-heated Hugoniot of the anorthite-diopside eutectic composition Di64An36, initially at 1673 K, to 110 GPa, along with a determination of the density dependence of the Grüneisen parameter of this liquid composition. We have now completed this work by: (1) extending the Di64An36 data to 127 GPa; (2) measuring the diopside (CaMgSi2O6) end-member composition, initially at 1773 K, to 114 GPa; and (3) measuring the anorthite (CaAl2Si2O8) end-member composition, initially at 1923 K, to 125 GPa. For internal consistency we have also re-reduced all of the experiments reported by Rigden et al. (1984, 1988, 1989) as well as some unpublished data from that era, using the latest initial melt densities (Lange, 1997) and hot Mo equation of state (Asimow et al., 2008). We are now in a position to assess the compression behavior of each of these liquids and the model of linear mixing along the compositional join to all pressures relevant to the terrestrial mantle. The total data set for the Di64An36 and diopside compositions can be fit within error by straight line Hugoniots in particle velocity vs. shock velocity. This suggests that a 3rd order equation of state is adequate to describe compression of these liquids over large pressure ranges. Anorthite, on the other hand, clearly requires a more complex model, such as we require for MgSiO3 and Mg2SiO4 liquids (Mosenfelder, Asimow, and Ahrens; this meeting); we examine the 4th-order Birch-Murnaghan and Ghiorso equations of state as well as an explicit speciation model that accounts for continuous coordination change of Si and Al. The complexity of anorthite liquid compression causes an apparent failure of linear mixing, suggesting that calibration of a predictive model of the equation of state of any silicate liquid composition will require more than a small number of end-member determinations. We will discuss the implications of our new data and models for melting and crystallization in a whole mantle magma ocean or at the modern core-mantle boundary. Asimow, P.D., Sun, D. and Ahrens, T.J., 2008. Phys. Earth Planet. Int. 10.1016/j.pepi.2008.08.004. Lange, R.A., 1997. Contrib. Mineral. Petrol 130: 1-11. Rigden, S.M., Ahrens, T.J. and Stolper, E.M., 1984. Science 226(4678): 1071-1074. Rigden, S.M., Ahrens, T.J. and Stolper, E.M., 1988. J. Geophys. Res. 93(B1): 367-382. Rigden, S.M., Ahrens, T.J. and Stolper, E.M., 1989. J. Geophys. Res. 94(B7): 9508-9522.

Lunar mining of oxygen using fluorine

NASA Technical Reports Server (NTRS)

Burt, Donald M.

1992-01-01

An important aspect of lunar mining will be the extraction of volatiles, particularly oxygen, from lunar rocks. Thermodynamic data show that oxygen could readily be recovered by fluorination of abundant lunar anorthite, CaAl2Si2O8. Fluorine is the most reactive element, and the only reagent able to extract 100 percent of the oxygen from any mineral, yet it can safely be stored or reacted in nickel or iron containers. The general fluorination reaction, mineral + 2F2 = mixed fluorides = O2, has been used for more than 30 years at a laboratory scale by stable-isotope geochemists. For anorthite, metallic Al and Si may be recovered from the mixed fluorides by Na-reduction, and CaO via exchange with Na2O; the resulting NaF may be recycled into F2 and Na by electrolysis, using lanthanide-doped CaF2 as the inert anode.

Direct Determination of the Space Weathering Rates in Lunar Soils and Itokawa Regolith from Sample Analyses

NASA Technical Reports Server (NTRS)

Keller, L. P.; Berger, E. L.; Christoffersen, R.; Zhang, S.

2016-01-01

Space weathering effects on airless bodies result largely from micrometeorite impacts and solar wind interactions. Decades of research have provided insights into space weathering processes and their effects, but a major unanswered question still remains: what is the rate at which these space weathering effects are acquired in lunar and asteroidal regolith materials? To determine the space weathering rate for the formation of rims on lunar anorthite grains, we combine the rim width and type with the exposure ages of the grains, as determined by the accumulation of solar flare particle tracks. From these analyses, we recently showed that space weathering effects in mature lunar soils (both vapor-deposited rims and solar wind amorphized rims) accumulate and attain steady state in 10(sup 6)-10(sup 7) y. Regolith grains from Itokawa also show evidence for space weathering effects, but in these samples, solar wind interactions appear to dominate over impactrelated effects such as vapor-deposition. While in our lunar work, we focused on anorthite, given its high abundance on the lunar surface, for the Itokawa grains, we focused on olivine. We previously studied 3 olivine grains from Itokawa and determined their solar flare track densities and described their solar wind damaged rims]. We also analyzed olivine grains from lunar soils, measured their track densities and rim widths, and used this data along with the Itokawa results to constrain the space weathering rate on Itokawa. We observe that olivine and anorthite have different responses to solar wind irradiation.

Modelling of a Convecting, Crystallizing, and Replenished Diopside-Anorthite Axial Magma Chamber beneath Mid Ocean Ridges

NASA Astrophysics Data System (ADS)

Lowell, R. P.; Lata, C.

2016-12-01

The aim of this work is to model heat output from a cooling, convective, crystallizing, and replenished basaltic magma sill, representing an axial magma lens (AML) at mid oceanic ridges. As a simplified version of basaltic melt, we have assumed the melt to be a two-component eutectic system composed of diopside and anorthite. Convective vigor is expressed through the Rayleigh number and heat flux is scaled through a classical relationship between the Rayleigh number and Nusselt number, where the temperature difference driving the convective heat flux is derived from a "viscous" temperature scale reflecting the strong temperature dependent viscosity of the system. Viscosity is modeled as a function of melt composition and temperature using the Tammann-Vogel-Fulcher equation, with parameters fit to the values of observed viscosities along the diopside-anorthite liquidus. It was observed for the un-replenished case, in which crystals fall rapidly to the floor of the AML, model results show that the higher initial concentration of diopside, the more vigorous the convection and the faster the rate of crystallization and decay of heat output. Replenishment of the AML accompanied by modest thickening of the melt layer stabilizes the heat output at values similar to those observed at ridge-axis hydrothermal systems. This study is an important step forward in quantitative understanding of thermal evolution of the axial magma lens at a mid-ocean ridge and the corresponding effect on high-temperature hydrothermal systems. Future work could involve improved replenishment mechanisms, more complex melts, and direct coupling with hydrothermal circulation models.

Strain localization and fabric development in polycrystalline anorthite + melt by water diffusion in an axial deformation experiment

NASA Astrophysics Data System (ADS)

Fukuda, Jun-ichi; Muto, Jun; Nagahama, Hiroyuki

2018-01-01

We performed two axial deformation experiments on synthetic polycrystalline anorthite samples with a grain size of 3 μm and 5 vol% Si-Al-rich glass at 900 °C, a confining pressure of 1.0 GPa, and a strain rate of 10-4.8 s-1. One sample was deformed as-is (dry); in the other sample, two half-cut samples (two cores) with 0.15 wt% water at the boundary were put together in the apparatus. The mechanical data for both samples were essentially identical with a yield strength of 700 MPa and strain weakening of 500 MPa by 20% strain. The dry sample appears to have been deformed by distributed fracturing. Meanwhile, the water-added sample shows plastic strain localization in addition to fracturing and reaction products composed of zoisite grains and SiO2 materials along the boundary between the two sample cores. Infrared spectra of the water-added sample showed dominant water bands of zoisite. The maximum water content was 1500 wt ppm H2O at the two-core boundary, which is the same as the added amount. The water contents gradually decreased from the boundaries to the sample interior, and the gradient fitted well with the solution of the one-dimensional diffusion equation. The determined diffusion coefficient was 7.4 × 10-13 m2/s, which agrees with previous data for the grain boundary diffusion of water. The anorthite grains in the water-added sample showed no crystallographic preferred orientation. Textural observations and water diffusion indicate that water promotes the plastic deformation of polycrystalline anorthite by grain-size-sensitive creep as well as simultaneous reactions. We calculated the strain rate evolution controlled by water diffusion in feldspar aggregates surrounded by a water source. We assumed water diffusion in a dry rock mass with variable sizes. Diffused water weakens a rock mass with time under compressive stress. The calculated strain rate decreased from 10-10 to 10-15 s-1 with an increase in the rock mass size to which water is supplied from < 1 m to 1 km and an increase in the time of water diffusion from < 1 to 10,000 years. This indicates a decrease in the strain rate in a rock mass with increasing deformation via water diffusion.

Raman analysis of cobalt blue pigment in blue and white porcelain: A reassessment.

PubMed

Jiang, Xiaochenyang; Ma, Yanying; Chen, Yue; Li, Yuanqiu; Ma, Qinglin; Zhang, Zhaoxia; Wang, Changsui; Yang, Yimin

2018-02-05

Cobalt blue is a famous pigment in human history. In the past decade it is widely reported that the cobalt aluminate has been detected in ancient ceramics as blue colorant in glaze, yet the acquired Raman spectra are incredibly different from that of synthesised references, necessitating a reassessment of such contradictory scenario with more accurate analytic strategies. In this study, micro-Raman spectroscopy (MRS) and scanning electron microscopy (SEM) in association with energy dispersive spectrometry (EDS) were performed on under-glaze cobalt pigments from one submerged blue and white porcelain shard dated from Wanli reign (1573-1620CE) of Ming dynasty (1365-1644CE) excavated at Nan'ao I shipwreck off the southern coast of China. The micro-structural inspection reveals that the pigment particles have characteristics of small account, tiny size, heterogeneously distribution, and more importantly, been completely enwrapped by well-developed anorthite crystals in the glaze, indicating that the signals recorded in previous publications are probably not from cobalt pigments themselves but from outside thickset anorthite shell. The further spectromicroscopic analyses confirm this presumption when the accurate spectra of cobalt aluminate pigment and surrounding anorthite were obtained separately with precise optical positioning. Accordingly, we reassess and clarify the previous Raman studies dedicated to cobalt blue pigment in ancient ceramics, e.g. cobalt blue in celadon glaze, and in turn demonstrate the superiority and necessity of coupling spectroscopic analysis with corresponding structure observation, especially in the characterization of pigments from complicated physico-chemical environment like antiquities. Thus, this study promotes a better understanding of Raman spectroscopy study of cobalt blue pigments in art and archaeology field. Copyright © 2017 Elsevier B.V. All rights reserved.

Silicon self-diffusion in single-crystal natural quartz and feldspar

NASA Astrophysics Data System (ADS)

Cherniak, D. J.

2003-09-01

Silicon diffusion was measured in natural quartz and anorthitic feldspar under dry, low-pressure (0.1 MPa) conditions using a 30Si tracer. Sources of diffusant consisted of 30Si-enriched silica powder for experiments on quartz and microcrystalline 30Si-doped synthetic feldspar of composition comparable to the feldspar specimens. Distributions of 30Si were measured with Rutherford backscattering spectrometry and nuclear reaction analysis, using the reaction 30Si (p,γ) 31P. The following Arrhenius relations were obtained for anneals at 1 atm in air. For quartz: transport normal to c: Dqtz,⊥c=7.97×10 -6 exp (-447±31 kJ mol -1/ RT) m 2 s -1; transport parallel to c: Dqtz,∥c=6.40×10 -6 exp (-443±22 kJ mol -1/ RT) m 2 s -1. For anorthitic feldspar (An 93): DAn=3.79×10 -7 exp (-465±50 kJ mol -1/ RT) m 2 s -1. The few successful experiments on diffusion in plagioclase of more albitic compositions (An 67 and An 23) reveal Si diffusivities a few orders of magnitude faster than that in the anorthite. The results for these feldspars bracket the determination of CaAl-NaSi interdiffusion under dry conditions by Grove et al. [Geochim. Cosmochim. Acta 48 (1984) 2113-2121], suggesting that the rate-limiting process is indeed Si diffusion. Si diffusion in quartz under more reducing conditions (NNO) is slightly slower (by about half an order of magnitude) than diffusion in samples annealed in air. This is consistent with observations made in studies of synthetic quartz [Béjina and Jaoul, Phys. Earth Planet. Inter. 50 (1988) 240-250].

Raman analysis of cobalt blue pigment in blue and white porcelain: A reassessment

NASA Astrophysics Data System (ADS)

Jiang, Xiaochenyang; Ma, Yanying; Chen, Yue; Li, Yuanqiu; Ma, Qinglin; Zhang, Zhaoxia; Wang, Changsui; Yang, Yimin

2018-02-01

Cobalt blue is a famous pigment in human history. In the past decade it is widely reported that the cobalt aluminate has been detected in ancient ceramics as blue colorant in glaze, yet the acquired Raman spectra are incredibly different from that of synthesised references, necessitating a reassessment of such contradictory scenario with more accurate analytic strategies. In this study, micro-Raman spectroscopy (MRS) and scanning electron microscopy (SEM) in association with energy dispersive spectrometry (EDS) were performed on under-glaze cobalt pigments from one submerged blue and white porcelain shard dated from Wanli reign (1573-1620 CE) of Ming dynasty (1365-1644 CE) excavated at Nan'ao I shipwreck off the southern coast of China. The micro-structural inspection reveals that the pigment particles have characteristics of small account, tiny size, heterogeneously distribution, and more importantly, been completely enwrapped by well-developed anorthite crystals in the glaze, indicating that the signals recorded in previous publications are probably not from cobalt pigments themselves but from outside thickset anorthite shell. The further spectromicroscopic analyses confirm this presumption when the accurate spectra of cobalt aluminate pigment and surrounding anorthite were obtained separately with precise optical positioning. Accordingly, we reassess and clarify the previous Raman studies dedicated to cobalt blue pigment in ancient ceramics, e.g. cobalt blue in celadon glaze, and in turn demonstrate the superiority and necessity of coupling spectroscopic analysis with corresponding structure observation, especially in the characterization of pigments from complicated physico-chemical environment like antiquities. Thus, this study promotes a better understanding of Raman spectroscopy study of cobalt blue pigments in art and archaeology field.

Solar heating of common lunar minerals for the production of oxygen

NASA Technical Reports Server (NTRS)

Senior, C. L.

1991-01-01

The purpose of this work was to demonstrate the feasibility of vapor-phase reduction (pyrolysis) of lunar materials to produce oxygen. Solar furnace experiments were conducted on two common lunar minerals, ilmenite and anorthite. Thermodynamic equilibrium calculations predicted that ilmenite should show a larger pressure increase than anorthite under conditions of the experiments and this was confirmed by the experiments. The measured mass loss of the ilmenite sample was consistent with loss of oxygen by reduction of iron in the liquid phase; this result was also predicted from equilibrium calculations. Based on preliminary experiments and equilibrium calculations, the temperatures needed for pyrolysis are expected to be in the range of 2000 to 2500 K, giving total gas pressures of 0.01 to 1 torr. Bulk regolith can be used as a feedstock without extensive beneficiation. Further, selective condensation of metal-containing species from the gas phase may yield metallic iron and silicon as byproducts from the process.

Shock-wave properties and high-pressure equations of state of geophysically important materials. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Boslough, M. B.

1983-01-01

Shock wave (Hugoniot), shock temperature, and release data are presented for several geophysically important, refractory materials. A sensitive multichannel optical pyrometer was developed to measure shock temperatures (2500 to 5600 K at pressures from 48 to 117 GPa) in anorthite (CaAl2Si2O8) glass. Shock temperatures of 3750 to 6000 K at pressures from 140 to 182 GPa were measured in calcium oxide (CaO). Temperature data were used to constrain the energetics of the B1-B2 phase transition at 70 GPa in CaO, and to construct a finite strain equation of state for CaO consistent with previous Hugoniot data. The CaO equation of state was used with equation of state parameters of other oxides to construct a theoretical mixed oxide Hugoniot of anorthite, which is in agreement with new Hugoniot data above about 50 GPa, determined using experimental techniques developed. The mixed oxide model, however, overestimates the shock temperatures, and does not accurately predict measured release paths.

Physical heterogeneity control on effective mineral dissolution rates

NASA Astrophysics Data System (ADS)

Jung, Heewon; Navarre-Sitchler, Alexis

2018-04-01

Hydrologic heterogeneity may be an important factor contributing to the discrepancy in laboratory and field measured dissolution rates, but the governing factors influencing mineral dissolution rates among various representations of physical heterogeneity remain poorly understood. Here, we present multiple reactive transport simulations of anorthite dissolution in 2D latticed random permeability fields and link the information from local grid scale (1 cm or 4 m) dissolution rates to domain-scale (1m or 400 m) effective dissolution rates measured by the flux-weighted average of an ensemble of flow paths. We compare results of homogeneous models to heterogeneous models with different structure and layered permeability distributions within the model domain. Chemistry is simplified to a single dissolving primary mineral (anorthite) distributed homogeneously throughout the domain and a single secondary mineral (kaolinite) that is allowed to dissolve or precipitate. Results show that increasing size in correlation structure (i.e. long integral scales) and high variance in permeability distribution are two important factors inducing a reduction in effective mineral dissolution rates compared to homogeneous permeability domains. Larger correlation structures produce larger zones of low permeability where diffusion is an important transport mechanism. Due to the increased residence time under slow diffusive transport, the saturation state of a solute with respect to a reacting mineral approaches equilibrium and reduces the reaction rate. High variance in permeability distribution favorably develops large low permeability zones that intensifies the reduction in mixing and effective dissolution rate. However, the degree of reduction in effective dissolution rate observed in 1 m × 1 m domains is too small (<1% reduction from the corresponding homogeneous case) to explain several orders of magnitude reduction observed in many field studies. When multimodality in permeability distribution is approximated by high permeability variance in 400 m × 400 m domains, the reduction in effective dissolution rate increases due to the effect of long diffusion length scales through zones with very slow reaction rates. The observed scale dependence becomes complicated when pH dependent kinetics are compared to the results from pH independent rate constants. In small domains where the entire domain is reactive, faster anorthite dissolution rates and slower kaolinite precipitation rates relative to pH independent rates at far-from-equilibrium conditions reduce the effective dissolution rate by increasing the saturation state. However, in large domains where less- or non-reactive zones develop, higher kaolinite precipitation rates in less reactive zones increase the effective anorthite dissolution rates relative to the rates observed in pH independent cases.

Amoeboid olivine aggregates with low-Ca pyroxenes: a genetic link between refractory inclusions and chondrules?

NASA Astrophysics Data System (ADS)

Krot, Alexander N.; Petaev, Michail I.; Yurimoto, Hisayoshi

2004-04-01

Amoeboid olivine aggregates (AOAs) in primitive (unmetamorphosed and unaltered) carbonaceous chondrites are uniformly 16O-enriched (Δ 17O ˜ -20‰) and consist of forsterite (Fa <2), FeNi-metal, and a refractory component (individual CAIs and fine-grained minerals interspersed with forsterite grains) composed of Al-diopside, anorthite, ±spinel, and exceptionally rare melilite (Åk <15); some CAIs in AOAs have compact, igneous textures. Melilite in AOAs is replaced by a fine-grained mixture of spinel, Al-diopside, and anorthite. Spinel is corroded by anorthite or by Al-diopside. In ˜10% of > 500 AOAs studied in the CR, CV, CM, CO, CH, CB, and ungrouped carbonaceous chondrites Acfer 094, Adelaide, and LEW85332, forsterite is replaced to a various degree by low-Ca pyroxene. There are three major textural occurrences of low-Ca pyroxene in AOAs: (i) thin (<10 μm) discontinuous layers around forsterite grains or along forsterite grain boundaries in AOA peripheries; (ii) haloes and subhedral grains around FeNi-metal nodules in AOA peripheries, and (iii) thick (up to 70 μm) continuous layers with abundant tiny inclusions of FeNi-metal grains around AOAs. AOAs with low-Ca pyroxene appear to have experienced melting of various degrees. In the most extensively melted AOA in the CV chondrite Leoville, only spinel grains are relict; forsterite, anorthite and Al-diopside were melted. This AOA has an igneous rim of low-Ca pyroxene with abundant FeNi-metal nodules and is texturally similar to Type I chondrules. Based on these observations and thermodynamic analysis, we conclude that AOAs are aggregates of relatively low temperature solar nebular condensates originated in 16O-rich gaseous reservoir(s), probably CAI-forming region(s). Some of the CAIs were melted before aggregation into AOAs. Many AOAs must have also experienced melting, but of a much smaller degree than chondrules. Before and possibly after aggregation, melilite and spinel reacted with the gaseous SiO and Mg to form Ca-Tschermakite (CaAl 2SiO 6)-diopside (CaMgSi 2O 6) solid solution and anorthite. Solid or incipiently melted olivine in some AOAs reacted with gaseous SiO in the CAI- or chondrule-forming regions to form low-Ca pyroxene: Mg 2SiO 4 + SiO (g) + H 2O (g) = Mg 2Si 2O 6 + H 2(g). Some low-Ca pyroxenes in AOAs may have formed by oxidation of Si-bearing FeNi-metal: Mg 2SiO 4 + Si (in FeNi) + 2H 2O (g) = Mg 2Si 2O 6 + 2H 2(g) and by direct gas-solid condensation: Mg (g) + SiO (g) +H 2O (g) = Mg 2Si 2O 6(s) + H 2(g) from fractionated (Mg/Si ratio < solar) nebular gas. Although bulk compositions of AOAs are rather similar to those of Type I chondrules, on the projection from spinel onto the plane Ca 2SiO 4-Mg 2SiO 4-Al 2O 3, these objects plot on different sides of the anorthite-forsterite thermal divide, suggesting that Type I chondrules cannot be produced from AOAs by an igneous fractionation. Formation of low-Ca pyroxene by reaction of AOAs with gaseous SiO and by melting of silica-rich dust accreted around AOAs moves bulk compositions of the AOAs towards chondrules, and provide possible mechanisms of transformation of refractory materials into chondrules or chondrule precursors. The rare occurrences of low-Ca pyroxene in AOAs may indicate that either AOAs were isolated from the hot nebular gas before condensation of low-Ca pyroxene or that condensation of low-Ca pyroxene by reaction between forsterite and gaseous SiO was kinetically inhibited. If the latter is correct, then the common occurrences of pyroxene-rich Type I chondrules may require either direct condensation of low-Ca pyroxenes or SiO 2 from fractionated nebular gas or condensation of gaseous SiO into chondrule melts.

Anorthite sputtering by H + and Ar q+ (q = 1-9) at solar wind velocities

DOE PAGES

Hijazi, Hussein Dib; Bannister, Mark E.; Meyer, III, Harry M.; ...

2014-10-16

Here, we report sputtering measurements of anorthite-like material, taken to be representative of soils found in the lunar highlands, impacted by singly and multicharged ions representative of the solar wind. The ions investigated include protons, as well as singly and multicharged Ar ions (as proxies for the nonreactive heavy solar wind constituents), in the charge state range +1 to +9, at fixed solar wind-relevant impact velocities of 165 and 310 km/s (0.25 keV/amu and 0.5 keV/amu). A quartz microbalance approach (QCM) for determination of total sputtering yields was used. The goal of the measurements was to determine the sputtering contributionmore » of the heavy, multicharged minority solar wind constituents in comparison to that due to the dominant H + fraction. The QCM results show a yield increase of a factor of about 80 for Ar + versus H + sputtering and an enhancement by a factor of 1.67 between Ar 9+ and Ar +, which is a clear indication of a potential sputtering effect.« less

Production of oxygen from lunar soil by molten salt electrolysis

NASA Technical Reports Server (NTRS)

Keller, Rudolf

1989-01-01

A simple approach to utilizing lunar resources proposes to dissolve lunar soil, without or with little beneficiation, in a suitable molten salt and to electrolyze the oxides to oxygen and a metal byproduct. The envisioned process and the required technological advances are discussed. Promising electrolysis conditions have been identified in a recent experimental program to manufacture silicon and aluminum from anorthite.

A Comprehensive Study of Pristine, Fine-grained, Spinel-rich Inclusions from the Leoville and Efremovka CV3 Chondrites. 1; Petrology

NASA Technical Reports Server (NTRS)

MacPherson, G. J.; Krot, A. N.; Ulyanov, A. A.; Hicks, T.

2002-01-01

Fine-grained spinel-rich CAI from Efremovka and Leoville lack the overprint of Na and Fe metasomatism seen in Allende. They contain spinel, pyroxene, anorthite, and melilite; most have a zoned structure with spinel-rich cores, melilite-rich mantles. Additional information is contained in the original extended abstract.

Laboratory simulation of infrared astrophysical features. [Terrestrial silicate, meteoritic and lunar soil 10-micron spectral comparisons with comets Bennet and Kohoutek

NASA Technical Reports Server (NTRS)

Rose, L. A.

1979-01-01

Laboratory infrared emission and absorption spectra have been taken of terrestrial silicates, meteorites, and lunar soils in the form of micrometer and submicrometer grains. The emission spectra were taken in a way that imitates telescopic observations. The purpose was to see which materials best simulate the 10-micron astrophysical feature. The emission spectra of dunite, fayalite, and Allende give a good fit to the 10-micron broadband emission feature of comets Bennett and Kohoutek. A study of the effect of grain size on the presence of the 10-micron emission feature of dunite shows that for particles larger than 37 microns no feature is seen. The emission spectrum of the Murray meteorite, a Type 2 carbonaceous chrondrite, is quite similar to the intermediate-resolution spectrum of comet Kohoutek in the 10-micron region. Hydrous silicates or amorphous magnesium silicates in combination with high-temperature condensates, such as olivine or anorthite, would yield spectra that match the intermediate-resolution spectrum of comet Kohoutek in the 10-micron region. Glassy olivine and glassy anorthite in approximately equal proportions would also give a spectrum that is a good fit to the cometary 10-micron feature.

Mineralogy, textures and mode of formation of a hibonite-bearing Allende inclusion

NASA Technical Reports Server (NTRS)

Allen, J. M.; Grossman, L.; Davis, A. M.; Hutcheon, I. D.

1978-01-01

The origin of a Type A, hibonite-rich, coarse-grained inclusion is investigated with the electron microprobe and petrographic and scanning electron microscopes. The primary phases are hibonite, rhonite, Ti-Al-pyroxene, spinel, perovskite and melilite. Evidence for the crystallization of the bulk of the primary phases, hibonite and melilite, from a melt is lacking, suggesting that they may have condensed directly from a solar nebular gas instead. Primary phases were intensely altered during a later condensation event which deposited grossular, anorthite, nepheline and wollastonite in veins and cavities. Four or five condensate rims were deposited as successive layers on the outside of the inclusion. From inside to outside, they consist of perovskite + spinel, nepheline + anorthite, Ti-Al-pyroxene + diopside, hedenbergite + or - wollastonite + or - andradite and, finally, prisms of diopside and hedenbergite with wollastonite and andradite. Reverse zoning in melilite; alteration phases and rim phases, which are not stable condensates from a gas of solar composition; and details of the sequence of rim condensates all suggest that the entire condensation history of this inclusion was interrupted by changes in pressure and/or temperature and/or gas phase composition.

On the nature of the excess heat capacity of mixing

NASA Astrophysics Data System (ADS)

Benisek, Artur; Dachs, Edgar

2011-03-01

The excess vibrational entropy (Δ S {vib/ex}) of several silicate solid solutions are found to be linearly correlated with the differences in end-member volumes (Δ V i ) and end-member bulk moduli (Δκ i ). If a substitution produces both, larger and elastically stiffer polyhedra, then the substituted ion will find itself in a strong enlarged structure. The frequency of its vibration is decreased because of the increase in bond lengths. Lowering of frequencies produces larger heat capacities, which give rise to positive excess vibrational entropies. If a substitution produces larger but elastically softer polyhedra, then increase and decrease of mean bond lengths may be similar in magnitude and their effect on the vibrational entropy tends to be compensated. The empirical relationship between Δ S {vib/ex}, Δ V i and Δκ i , as described by Δ S {vib/ex} = (Δ V i + mΔκ i ) f, was calibrated on six silicate solid solutions (analbite-sanidine, pyrope-grossular, forsterite-fayalite, analbite-anorthite, anorthite-sanidine, CaTs-diopside) yielding m = 0.0246 and f = 2.926. It allows the prediction of Δ S {vib/ex} behaviour of a solid solution based on its volume and bulk moduli end-member data.

Effects of Different Calcium Compounds on the Corrosion Resistance of Andalusite-Based Low-Cement Castables in Contact with Molten Al-Alloy

NASA Astrophysics Data System (ADS)

Adabifiroozjaei, Esmaeil; Saidi, Ali; Monshi, Ahmad; Koshy, Pramod

2011-04-01

Andalusite containing low-cement castables (LCCs) have been used in aluminum casthouses for several decades. CaF2 is commonly added to the refractory to improve its corrosion resistance mainly because of its role in the formation of anorthite (CaAl2Si2O8); the latter has been reported to decrease the penetration of molten aluminum alloys into refractories. This article investigates the effect of the addition of different calcium containing compounds (CaO, CaCO3, CaSO4, CaF2, Clinker white cement, calcia feldspar, wollastonite, and Ca3(PO4)2) on reactions with the refractory constituents to form anorthite as well as the effect of the additives on both the subsequent physical properties and the corrosion resistance of andalusite LCC refractories. Corrosion tests using the Alcoa cup test at temperatures (1123 K [850 °C] for 150 hours and 1433 K [1160 °C] for 72 hours) were conducted to determine the extent of penetration, whereas immersion tests in boiling water were conducted to determine the extent of open porosity in the material. Scanning electron microscopy coupled with energy dispersive spectrometer, optical microscopy, and X-ray diffraction techniques were employed to characterize the phase formations in the materials after the tests. The study demonstrated that both calcia feldspar and clinker white cement had the potential to be used as new additives for decreasing the penetration of molten Al-alloy into the refractory materials. Anorthite formation (in the refractory matrix), along with the absence of glassy phases, were responsible for the improvement in the corrosion resistance of the castables containing calcia feldspar. However, in the sample containing cement, the presence of calcium silicate phases were observed to resist reactions with molten aluminum. The observed results were validated using thermodynamic calculations, which indicated that tricalcium silicates (3CaO.SiO2) and dicalcium silicate (2CaO.SiO2) phases were more resistant than wollastonite (CaSiO3) for applications involving contact with molten aluminum.

High precision Al-Mg systematics of forsterite-bearing Type B CAIs from CV3 chondrites

NASA Astrophysics Data System (ADS)

MacPherson, G. J.; Bullock, E. S.; Tenner, T. J.; Nakashima, D.; Kita, N. T.; Ivanova, M. A.; Krot, A. N.; Petaev, M. I.; Jacobsen, S. B.

2017-03-01

In order to further elucidate possible temporal relationships between different varieties of calcium-, aluminum-rich inclusions (CAIs), we measured the aluminum-magnesium isotopic systematics of seven examples of the rare type known as forsterite-bearing Type B (FoB) inclusions from four different CV3 carbonaceous chondrites: Allende, Efremovka, NWA 3118, and Vigarano. The primary phases (forsterite, Al-Ti-rich diopside, spinel, melilite, and anorthite) in each inclusion were analyzed in situ using high-precision secondary ion mass-spectrometry (SIMS). In all cases, minerals with low Al/Mg ratios (all except anorthite) yield well-defined internal Al-Mg isochrons, with a range of initial 26Al/27Al ratios [(26Al/27Al)0] ranging from (5.30 ± 0.22) × 10-5 down to (4.17 ± 0.43) × 10-5. Anorthite in all cases is significantly disturbed relative to the isochrons defined by the other phases in the same CAIs, and in several cases contains no resolved excesses of radiogenic 26Mg (δ26Mg∗) even at 27Al/24Mg ratios greater than 1000. The fact that some FoBs preserve (26Al/27Al)0 of ∼5.2 × 10-5, close to the canonical value of (5.23 ± 0.13) × 10-5 inferred from bulk magnesium-isotope measurements of CV CAIs (B. Jacobsen et al., 2008), demonstrates that FoBs began forming very early, contemporaneous with other more-refractory CAIs. The range of (26Al/27Al)0 values further shows that FoBs continued to be reprocessed over ∼200,000 years of nebular history, consistent with results obtained for other types of igneous CAIs in CV chondrites. The absence of any correlation between of CAI + FoB formation or reprocessing times with bulk composition or CAI type means that there is no temporal evolutionary sequence between the diverse CAI types. The initial δ26Mg∗ value in the most primitive FoB (SJ101) is significantly lower than the canonical solar system value of -0.040 ± 0.029‰.

Numerical Study on Stress Heterogeneity Development in Two-Phase Rocks with Large Rheological Contrast and Implications in the Lower Crust

NASA Astrophysics Data System (ADS)

Xu, Junshan; Zhang, Baohua

2018-03-01

Development of stress heterogeneity in two-phase rocks was investigated via a finite element method at 1000-1200 K and 100 MPa. Two groups of rock models were considered: anorthite-diopside and anorthite-clinopyroxene, with a phase volume ratio of 1:1 in each group and different dislocation creep rates between phases ( 4-8 orders of magnitude). Our numerical results indicate that the stress inside the model can be several times higher than the differential stress applied to the model and stress will tend to concentrate in hard phase, especially near the sharp boundaries with soft phase. Moreover, large stress gradient in hard phase and nearly homogeneous stress in soft phase will lead to the initialization of localized dynamic recrystallization or fracture. These numerical observations suggest that the rheological contrast between two phases plays a crucial role in stress heterogeneity rather than other factors (such as grain size, the boundary conditions or mesh density), which may eventually accelerate development of stress heterogeneity in the lower crust. Our study provides new insights into the dynamic processes of grain size reduction in the lower crust, which may cause the transformation from dislocation creep to diffusion creep and enable the weakened shear zones.

Pulmonary epithelial response in the rat lung to instilled Montserrat respirable dusts and their major mineral components.

PubMed

Housley, D G; Bérubé, K A; Jones, T P; Anderson, S; Pooley, F D; Richards, R J

2002-07-01

The Soufriere Hills, a stratovolcano on Montserrat, started erupting in July 1995, producing volcanic ash, both from dome collapse pyroclastic flows and phreatic explosions. The eruptions/ash resuspension result in high concentrations of suspended particulate matter in the atmosphere, which includes cristobalite, a mineral implicated in respiratory disorders. To conduct toxicological studies on characterised samples of ash, together with major components of the dust mixture (anorthite, cristobalite), and a bioreactive mineral control (DQ12 quartz). Rats were challenged with a single mass (1 mg) dose of particles via intratracheal instillation and groups sacrificed at one, three, and nine weeks. Acute bioreactivity of the particles was assessed by increases in lung permeability and inflammation, changes in epithelial cell markers, and increase in the size of bronchothoracic lymph nodes. Data indicated that respirable ash derived from pyroclastic flows (20.1% cristobalite) or phreatic explosion (8.6% cristobalite) had minimal bioreactivity in the lung. Anorthite showed low bioreactivity, in contrast to pure cristobalite, which showed progressive increases in lung damage. Results suggests that either the percentage mass of cristobalite particles present in Montserrat ash was not sufficient as a catalyst in the lung environment, or its surface reactivity was masked by the non-reactive volcanic glass components during the process of ash formation.

CMAS-Resistant Plasma Sprayed Thermal Barrier Coatings Based on Y2O3-Stabilized ZrO2 with Al3+ and Ti4+ Solute Additions

NASA Astrophysics Data System (ADS)

Senturk, Bilge S.; Garces, Hector F.; Ortiz, Angel L.; Dwivedi, Gopal; Sampath, Sanjay; Padture, Nitin P.

2014-04-01

The higher operating temperatures in gas-turbine engines made possible by thermal barrier coatings (TBCs) are engendering a new problem: environmentally ingested airborne silicate particles (sand, ash) melt on the hot TBC surfaces and form calcium-magnesium-alumino-silicate (CMAS) glass deposits. The molten CMAS glass degrades the TBCs, leading to their premature failure. Here, we demonstrate the use of a commercially manufactured feedstock powder, in conjunction with air plasma spray process, to deposit CMAS-resistant yttria-stabilized zirconia-based TBCs containing Al3+ and Ti4+ in solid solution. Results from the characterization of these new TBCs and CMAS/TBCs interaction experiments are presented. The CMAS mitigation mechanisms in these new TBCs involve the crystallization of the anorthite phase. Raman microscopy is used to generate large area maps of the anorthite phase in the CMAS-interacted TBCs demonstrating the potential usefulness of this method for studying CMAS/TBCs interactions. The ubiquity of airborne sand/ash particles and the ever-increasing demand for higher operating temperatures in future high efficiency gas-turbine engines will necessitate CMAS resistance in all hot-section components of those engines. In this context, the versatility, ease of processing, and low cost offered by the process demonstrated here could benefit the development of these new CMAS-resistant TBCs.

Pulmonary epithelial response in the rat lung to instilled Montserrat respirable dusts and their major mineral components

PubMed Central

Housley, D; Berube, K; Jones, T; Anderson, S; Pooley, F; Richards, R

2002-01-01

Background: The Soufriere Hills, a stratovolcano on Montserrat, started erupting in July 1995, producing volcanic ash, both from dome collapse pyroclastic flows and phreatic explosions. The eruptions/ash resuspension result in high concentrations of suspended particulate matter in the atmosphere, which includes cristobalite, a mineral implicated in respiratory disorders. Aims: To conduct toxicological studies on characterised samples of ash, together with major components of the dust mixture (anorthite, cristobalite), and a bioreactive mineral control (DQ12 quartz). Methods: Rats were challenged with a single mass (1 mg) dose of particles via intratracheal instillation and groups sacrificed at one, three, and nine weeks. Acute bioreactivity of the particles was assessed by increases in lung permeability and inflammation, changes in epithelial cell markers, and increase in the size of bronchothoracic lymph nodes. Results: Data indicated that respirable ash derived from pyroclastic flows (20.1% cristobalite) or phreatic explosion (8.6% cristobalite) had minimal bioreactivity in the lung. Anorthite showed low bioreactivity, in contrast to pure cristobalite, which showed progressive increases in lung damage. Conclusion: Results suggests that either the percentage mass of cristobalite particles present in Montserrat ash was not sufficient as a catalyst in the lung environment, or its surface reactivity was masked by the non-reactive volcanic glass components during the process of ash formation. PMID:12107295

FT-IR characterization of articulated ceramic bricks with wastes from ceramic industries

NASA Astrophysics Data System (ADS)

Nirmala, G.; Viruthagiri, G.

The 30 ceramic test samples with the kaolinitic clay and ceramic rejects (in the as-received state and sintered at temperatures 900-1200 °C) were investigated through spectral studies in order to elucidate the possibility of recycling the wastes from the government ceramic industry of Vriddhachalam, Tamilnadu state, South India. A detailed attribution of all the spectroscopic frequencies in the spectra recorded in the 4000-400 cm-1 region was attempted and their assignment to different minerals was accomplished. X-ray diffraction analysis was performed to demonstrate the reliability of IR attributions. The indication of well-ordered kaolinite is by the band at 1115 cm-1 in the raw samples which tends to shift towards 1095 cm-1 in all the fired samples. The peaks at 563 cm-1 and 795 cm-1 can be assigned to anorthite and dickite respectively. The presence of quartz and anorthite is confirmed both by XRD and FTIR. The microstructural observations were done through the SEM images which visualized the vitrification of the fired bricks at higher temperatures. The refractory properties of the samples found through the XRF analysis are also appreciable. The present work suggests that the incorporation of the rejects into the clay mixture will be a valid route for the ceramic industries to reduce the costs of the ceramic process.

Lunar and Planetary Science XXXV: Viewing the Lunar Interior Through Titanium-Colored Glasses

NASA Technical Reports Server (NTRS)

2004-01-01

The session"Viewing the Lunar Interior Through Titanium-Colored Glasses" included the following reports:Consequences of High Crystallinity for the Evolution of the Lunar Magma Ocean: Trapped Plagioclase; Low Abundances of Highly Siderophile Elements in the Lunar Mantle: Evidence for Prolonged Late Accretion; Fast Anorthite Dissolution Rates in Lunar Picritic Melts: Petrologic Implications; Searching the Moon for Aluminous Mare Basalts Using Compositional Remote-Sensing Constraints II: Detailed analysis of ROIs; Origin of Lunar High Titanium Ultramafic Glasses: A Hybridized Source?; Ilmenite Solubility in Lunar Basalts as a Function of Temperature and Pressure: Implications for Petrogenesis; Garnet in the Lunar Mantle: Further Evidence from Volcanic Glasses; Preliminary High Pressure Phase Relations of Apollo 15 Green C Glass: Assessment of the Role of Garnet; Oxygen Fugacity of Mare Basalts and the Lunar Mantle. Application of a New Microscale Oxybarometer Based on the Valence State of Vanadium; A Model for the Origin of the Dark Ring at Orientale Basin; Petrology and Geochemistry of LAP 02 205: A New Low-Ti Mare-Basalt Meteorite; Thorium and Samarium in Lunar Pyroclastic Glasses: Insights into the Composition of the Lunar Mantle and Basaltic Magmatism on the Moon; and Eu2+ and REE3+ Diffusion in Enstatite, Diopside, Anorthite, and a Silicate Melt: A Database for Understanding Kinetic Fractionation of REE in the Lunar Mantle and Crust.

Carbonation of Rock Minerals by Supercritical Carbon Dioxide at 250 degrees C.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sugama, T.; Ecker, L.; Butcher, T.

2010-06-01

Wet powder-samples of five rock minerals, granite, albite, hornblende, diorite, and biotite mica, were exposed in supercritical carbon dioxide (scCO2) for 3 days at 250 C under 17.23 MPa pressure, and then the susceptibility of the various crystalline phases present in these mineral structures to reactions with hot scCO2 was investigated by XRD and FT-IR. The anorthite present in diorite was identified as the most vulnerable phase to carbonation. In contrast, biotite displayed a great resistance, although its phase was transformed hydrothermally to sanidine and quartz. Granite comprised of two phases, anorthoclase-type albite and quartz. The carbonation of former phasemore » led to the formation of amorphous sodium and potassium carbonates coexisting with the clay-like by-products of the carbonation reaction. The reactivity of quartz to scCO2 was minimal, if any. Among these rock minerals, only hornblende formed crystalline carbonation products, such as calcite and magnesite after exposure, reflecting the likelihood of an increase in its volume. Based upon the feldspar ternary diagram, the carbonation rate of various different minerals in the plagioclase feldspar family depended primarily on the amount of anorthite. On the other hand, alkali feldspar minerals involving anorthoclase-type albite and sanidine had a lower reactivity with scCO2, compared with that of plagioclase feldspar minerals.« less

Melting in feldspar-bearing systems to high pressures and the structures of aluminosilicate liquids

NASA Astrophysics Data System (ADS)

Boettcher, Art; Guo, Qiti; Bohlen, Steve; Hanson, Brooks

1984-04-01

To test the possibility that aluminosilicate liquids exhibit pressure-induced transformations, particularly involving changes in the coordination of aluminum, we determined melting relationships for the feldspar-bearing systems NaAlSi3O8-SiO2, KAlSi3O8-SiO2, and CaAl2Si2O8-SiO2 from 1 atm to 25 kbar. Albite and anorthite behave similarly in that they, and presumably liquids of these compositions, transform at high pressures to jadeite, kyanite, corundum, and other structures with aluminum in six-fold coordination, releasing SiO2 component. This results in a large increase in the activity of SiO2 component in the liquid (alqz), which is manifested by a significant decrease in the melting-point depression of albite and of anorthite by the addition of quartz at pressures above ˜15 kbar. In contrast, sanidine does not transform to denser phases at pressures below at least 100 kbar, but it melts incongruently to leucite + SiO2-rich liquid up to ˜ 15 kbar. This produces a relatively large alqz and a small freezing-point depression by quartz below this pressure; the opposite holds above ˜15 kbar. These results support the concept that significant structural changes, including coordination changes in aluminum, occur in magmas in the upper mantle.

FT-IR characterization of articulated ceramic bricks with wastes from ceramic industries.

PubMed

Nirmala, G; Viruthagiri, G

2014-05-21

The 30 ceramic test samples with the kaolinitic clay and ceramic rejects (in the as-received state and sintered at temperatures 900-1200°C) were investigated through spectral studies in order to elucidate the possibility of recycling the wastes from the government ceramic industry of Vriddhachalam, Tamilnadu state, South India. A detailed attribution of all the spectroscopic frequencies in the spectra recorded in the 4000-400cm(-1) region was attempted and their assignment to different minerals was accomplished. X-ray diffraction analysis was performed to demonstrate the reliability of IR attributions. The indication of well-ordered kaolinite is by the band at 1115cm(-1) in the raw samples which tends to shift towards 1095cm(-1) in all the fired samples. The peaks at 563cm(-1) and 795cm(-1) can be assigned to anorthite and dickite respectively. The presence of quartz and anorthite is confirmed both by XRD and FTIR. The microstructural observations were done through the SEM images which visualized the vitrification of the fired bricks at higher temperatures. The refractory properties of the samples found through the XRF analysis are also appreciable. The present work suggests that the incorporation of the rejects into the clay mixture will be a valid route for the ceramic industries to reduce the costs of the ceramic process. Copyright © 2014 Elsevier B.V. All rights reserved.

Grosnaja ABCs: Magnesium isotope compositions

NASA Technical Reports Server (NTRS)

Goswami, J. N.; Srinivasan, G.; Ulyanov, A. A.

1993-01-01

Three CAI's from the Grosnaja CV3 chondrite were analyzed for their magnesium isotopic compositions by the ion microprobe. The selected CAI's represent three distinct types: GR4(compact Type A), GR7(Type B) and GR2(Type C). Petrographic studies indicate that all three Grosnaja inclusions were subjected to secondary alterations. The Type A CAI GR4 is primarily composed of melilite with spinel and pyroxene occurring as minor phases. The rim of the inclusion does not exhibit distinct layered structure and secondary alteration products (garnet, Fe-rich olivine and Na-rich plagioclase) are present in some localized areas near the rim region. The average major element compositions of different mineral phases in GR4 are given. Preliminary REE data suggest a depletion of HREE relative to LREE by about a factor of 3 without any clear indication of interelement fractionation. The CAI GR7 has textural and minerological characteristics similar to Type B inclusions. The REE data show a pattern that is similar to Group 6 with enrichment in Eu and Yb. In addition, a depletion of HREE compared to LREE is also evident in this object. Melilite composition shows a broad range of akermanite content (Ak(sub 15-55)). Detailed petrographic study is in progress. GR2 is a anorthite-rich Type C inclusion with large plagioclase laths intergrown with Ti-rich pyroxene. The average plagioclase composition is close to pure anorthite (An99).

Silicate Liquid Equations of State from Molten Shock Experiments

NASA Astrophysics Data System (ADS)

Asimow, P. D.; Ahrens, T. J.

2005-12-01

Over the past 20 years the Caltech shockwave lab has pioneered the direct measurement of equations of state of silicate liquids by shockwave experiments on targets preheated to 1250-1700 °C. A glass of the desired composition is welded into a Mo capsule; the capsule is heated by induction to above the liquidus of the sample. Upon impact with a gun-launched flyer plate, a planar shockwave is driven into the molten sample. Passage of the shock through the sample and capsule cover is measured with a high-speed streak camera; impactor velocity is measured with a double-exposure flash X-ray. Initial sample density is inferred from measured temperature and known 1 bar density and thermal expansion data. Previously, a 40 mm single-stage gun launched 80 g projectiles carrying 1.5 mm thick flyers at up to 2.7 km/s. Maximum pressures in the range of 25 to 45 GPa were achieved in diopside, anorthite, the diopside-anorthite eutectic, komatiite, MORB, and fayalite. Results of prior work are briefly reviewed. Also revisited are arguments that, although the silicate liquids achieve their relaxed hydrostatic states, crystallization does not occur on the timescale of the experiment. Densities of the compositions studied appear to converge in the 20-40 GPa range to that expected for a mixture of dense oxide phases of equal composition and temperature. Previous data, however, do not test whether, with further compression, the liquids can become denser than the equivalent solid oxide mixes. In the case of the diopside-anorthite eutectic, earlier experiments showed anomalous stiffening above 25 GPa. We have improved the technique in several ways that allow us to extend measurements to pressures exceeding the core-mantle boundary in the Earth. These improvements include a higher writing-rate image converter streak camera, high-temperature shorting pins to trigger the image converter camera, digital profiling of pre-shot capsule shape, pyrometry (in place of thermocouples) to measure pre-shot temperature, better heating coil design for more uniform heating, initiation of a program to extent Hugoniot data on hot Mo, and (most importantly) adaptation to Caltech's 25 mm two-stage light gas gun for impact speeds up to 7.5 km/s. We intend to apply this technique to characterize a suite of liquid compositions up to core-mantle boundary pressure in order to constrain melting relationships and dynamics of partial melts under magma ocean and ultra-low velocity zone conditions. Such large compressions will also clearly test whether the hot dense oxide mix model is useful for extrapolating liquid properties beyond the mid-mantle. Initial results have revisited the anomalous compression of diopside-anorthite eutectic composition above 25 GPa. A single experiment reaching 42 GPa clearly lies on the extension of the low pressure Hugoniot and shows, at the 10 sigma level, that the anomalous compression of this composition is not repeatable. An error-weighted fit to all the data on this composition is consistent with a linear Us-Up Hugoniot. We expect that shockwave studies of silicate liquids will constitute a key element of a renewed effort in the broader community to determine physical properties of liquids at all mantle pressures and to apply this knowledge to understanding the differentiation and current state of the Earth.

Elasticity of plagioclase feldspars

NASA Astrophysics Data System (ADS)

Brown, J. Michael; Angel, Ross J.; Ross, Nancy L.

2016-02-01

Elastic properties are reported for eight plagioclase feldspars that span compositions from albite (NaSi3AlO8) to anorthite (CaSi2Al2O8). Surface acoustic wave velocities measured using Impulsive Stimulated Light Scattering and compliance sums from high-pressure X-ray compression studies accurately determine all 21 components of the elasticity tensor for these triclinic minerals. The overall pattern of elasticity and the changes in individual elastic components with composition can be rationalized on the basis of the evolution of crystal structures and chemistry across this solid-solution join. All plagioclase feldspars have high elastic anisotropy; a* (the direction perpendicular to the b and c axes) is the softest direction by a factor of 3 in albite. From albite to anorthite the stiffness of this direction undergoes the greatest change, increasing twofold. Small discontinuities in the elastic components, inferred to occur between the three plagioclase phases with distinct symmetry (C1>¯, I1>¯, and P1>¯), appear consistent with the nature of the underlying conformation of the framework-linked tetrahedra and the associated structural changes. Measured body wave velocities of plagioclase-rich rocks, reported over the last five decades, are consistent with calculated Hill-averaged velocities using the current moduli. This confirms long-standing speculation that previously reported elastic moduli for plagioclase feldspars are systematically in error. The current results provide greater assurance that the seismic structure of the middle and lower crusts can be accurately estimated on the basis of specified mineral modes, chemistry, and fabric.

Origin of minor and trace element compositional diversity in anorthitic feldspar phenocrysts and melt inclusions from the Juan de Fuca Ridge

USGS Publications Warehouse

Adams, David T.; Nielsen, Roger L.; Kent, Adam J.R.; Tepley, Frank J.

2011-01-01

Melt inclusions trapped in phenocryst phases are important primarily due to their potential of preserving a significant proportion of the diversity of magma composition prior to modification of the parent magma array during transport through the crust. The goal of this investigation was to evaluate the impact of formational and post-entrapment processes on the composition of melt inclusions hosted in high anorthite plagioclase in MORB. Our observations from three plagioclase ultra-phyric lavas from the Endeavor Segment of the Juan de Fuca Ridge document a narrow range of major elements and a dramatically greater range of minor and trace elements within most host plagioclase crystals. Observed host/inclusion partition coefficients for Ti are consistent with experimental determinations. In addition, observed values of DTi are independent of inclusion size and inclusion TiO2 content of the melt inclusion. These observations preclude significant effects from the re-homogenization process, entrapment of incompatible element boundary layers or dissolution/precipitation. The observed wide range of TiO2 contents in the host feldspar, and between bands of melt inclusions within individual crystals rule out modification of TiO contents by diffusion, either pre-eruption or due to re-homogenization. However, we do observe comparatively small ranges for values of K2O and Sr compared to P2O5 and TiO2 in both inclusions and crystals that can be attributed to diffusive processes that occurred prior to eruption.

Experimental calibration of Forsterite-Anorthite-Ca-Tschermak-Enstatite (FACE) geobarometer for mantle peridotites

NASA Astrophysics Data System (ADS)

Fumagalli, P.; Borghini, G.; Rampone, E.; Poli, S.

2017-06-01

The crystallization of plagioclase-bearing assemblages in mantle rocks is witness of mantle exhumation at shallow depth. Previous experimental works on peridotites have found systematic compositional variations in coexisting minerals at decreasing pressure within the plagioclase stability field. In this experimental study we present new constraints on the stability of plagioclase as a function of different Na2O/CaO bulk ratios, and we present a new geobarometer for mantle rocks. Experiments have been performed in a single-stage piston cylinder at 5-10 kbar, 1050-1150 °C at nominally anhydrous conditions using seeded gels of peridotite compositions (Na2O/CaO = 0.08-0.13; X Cr = Cr/(Cr + Al) = 0.07-0.10) as starting materials. As expected, the increase of the bulk Na2O/CaO ratio extends the plagioclase stability to higher pressure; in the studied high-Na fertile lherzolite (HNa-FLZ), the plagioclase-spinel transition occurs at 1100 °C between 9 and 10 kbar; in a fertile lherzolite (FLZ) with Na2O/CaO = 0.08, it occurs between 8 and 9 kbar at 1100 °C. This study provides, together with previous experimental results, a consistent database, covering a wide range of P- T conditions (3-9 kbar, 1000-1150 °C) and variable bulk compositions to be used to define and calibrate a geobarometer for plagioclase-bearing mantle rocks. The pressure sensitive equilibrium: Mg_{2}SiO_{4}^Ol\\limits_{Forsterite} + CaAl_{2}Si_{2}O_{8}^{Pl\\limits_{Anorthite} = CaAl_{2}SiO_{6}^{Cpx}\\limits_{Ca-Tschermak} + Mg_{2}Si_{2}O_{6}^{Opx}\\limits_{Enstatite}, has been empirically calibrated by least squares regression analysis of experimental data combined with Monte Carlo simulation. The result of the fit gives the following equation: P=7.2( ± 2.9)+0.0078( ± 0.0021)T{{ }}+0.0022( ± 0.0001)T ln K, {R^2}=0.93, where P is expressed in kbar and T in kelvin. K is the equilibrium constant K = a CaTs × a en/ a an × a fo, where a CaTs, a en, a an and a fo are the activities of Ca-Tschermak in clinopyroxene, enstatite in orthopyroxene, anorthite in plagioclase and forsterite in olivine. The proposed geobarometer for plagioclase peridotites, coupled to detailed microstructural and mineral chemistry investigations, represents a valuable tool to track the exhumation of the lithospheric mantle at extensional environments.

Forsterite-Anorthite-CaTschermak-Enstatite (FACE): A geobarometer for plagioclase-bearing peridotites

NASA Astrophysics Data System (ADS)

Fumagalli, P.; Borghini, G.; Rampone, E.; Poli, S.

2017-12-01

Plagioclase peridotites can be the result of either metamorphic recrystallization, or diffuse melt-rock interactions. Although they represent an important geodynamic marker of shallow mantle exhumation, the accurate estimation of their barometric evolution is poorly constrained. Systematic correlations between pressure and composition of coexisting minerals within the plagioclase stability field have been reported in previous experimental studies. In this experimental study we present new constraints on the stability of plagioclase as a function of different Na2O/CaO bulk ratios, and we present a new geobarometer for mantle rocks. Experiments have been performed in a single-stage piston cylinder at 5-10 kbar, 1050-1150 °C at nominally anhydrous conditions using seeded gels of peridotite compositions (Na2O/CaO = 0.08-0.13; XCr = Cr/(Cr + Al) = 0.07-0.10). As expected, the increase of the bulk Na2O/CaO extends the plagioclase stability to higher pressure; in the Na2O enriched fertile lherzolite the plagioclase-spinel transition occurs between 9 and 10 kbar, 1100 °C; in the fertile lherzolite with Na2O/CaO = 0.08, it occurs between 8 and 9 kbar, 1100 °C. The present data together with previous experimental results provide a consistent database, covering a wide range of P-T conditions (3-9 kbar, 1000-1150 °C) and variable bulk compositions to be used to define and calibrate a geobarometer for plagioclase-bearing mantle rocks. We have empirically calibrated by least squares regression analysis of experimental data combined with MonteCarlo simulation the following pressure sensitive equilibrium: Mg2SiO4 Ol + CaAl2Si2O8 Pl = CaAl2SiO6 Cpx + Mg2Si2O6 OpxForsterite Anorthite Ca-Tschermak Enstatite We derive the following equation: P = 7.2 (±2.9) + 0.0078 (±0.0021) T + 0.0022 (±0.0001) T lnK R2= 0.93 where P is expressed in kbar and T in kelvin. K is the equilibrium constant K = aCa-Ts*aen / aan *afo, where aCaTs, aen, aan and afo are the activities of Ca-Tschermak in clinopyroxene, enstatite in orthopyroxene, anorthite in plagioclase and forsterite in olivine. The proposed geobarometer for plagioclase peridotites, coupled to detailed microstructural and mineral chemistry investigations, represents a valuable tool to track the exhumation of the lithospheric mantle at extensional environments.

High-Temperature Thermal Diffusivity Measurements of Silicate Glasses

NASA Astrophysics Data System (ADS)

Pertermann, M.; Hofmeister, A. M.; Whittington, A. G.; Spera, F. J.; Zayac, J.

2005-12-01

Transport of heat in geologically relevant materials is of great interest because of its key role in heat transport, magmatism and volcanic activity on Earth. To better understand the thermal properties of magmatic materials at high temperatures, we measured the thermal diffusivity of four synthetic end-member silicate glasses with the following compositions: albite (NaAlSi3O8), orthoclase (KAlSi3O8), anorthite (CaAl2Si2O8), and diopside (CaMgSi2O6). Thermal diffusivity measurements were conducted with the laser-flash technique and data were acquired from room temperature to a maximum temperature near 1100°C, depending on the glass transition temperature. The presence of sub-mm sized bubbles in one of the orthoclase samples had no discernable effect on measured diffusivities. At room temperature, the three feldspar-type glasses have thermal diffusivity (D) values of 0.58-0.61 mm2/s, whereas the diopside glass has 0.52 mm2/s. With increasing temperature, D decreases by 5-10% (relative) for all samples and becomes virtually constant at intermediate temperatures. At higher temperatures, the anorthite and diopside glasses exhibit significant drops in thermal diffusivity over a 50-100°C interval, correlating with previously published heat capacity changes near the glass transition for these compositions. For anorthite, D (in mm2/s) decreases from 0.48 at 750-860°C to 0.36 at 975-1075°C; for diopside, D changes from 0.42 at 630-750°C to 0.30 at 850-910°C, corresponding to relative drops of 24 and 29%, respectively. Albite and orthoclase glasses do not exhibit this change and also lack significant changes in heat capacity near the glass transition. Instead, D is constant at 400-800°C for albite, and for orthoclase values go through a minimum at 500-600°C before increasing slightly towards 1100°C but it never exceeds the room temperature D. Our data on thermal diffusivity correlate closely with other thermophysical properties. Thus, at least in case of simple compositions, measurement of thermal diffusivity of glasses above the glass transition may closely approximate the behavior of magmatic liquids. For the orthoclase composition, our new data show that the thermal diffusivity of glass in the range of 20-1100°C is clearly lower than that of orthoclase single crystals (Hoefer and Schilling, 2002, Phys Chem Minerals, 29, 571-584).

Enriched Shergottite NWA 5298 As An Evolved Parent Melt: Trace Element Inventory

NASA Technical Reports Server (NTRS)

Hui, Hejiu; Peslier, Anne H.; Lapen, Thomas J.; Shafer, John; Brandon, Alan; Irving, Anthony

2010-01-01

Martian meteorite Northwest Africa 5298 is a basaltic shergottite that was found near Bir Gandouz (Morocco). Its martian origin was confirmed by oxygen isotopes [1], as well as Mn/Fe ratios in the pyroxenes and K/anorthite ratios in the plagioclases [2]. Here we present a petrographic and geochemical study of NWA 5298. Comparison of mineralogical and geochemical characteristics of this meteorite with other Martian rocks shows that NWA 5298 is not likely paired with any other known shergottites, but it has similarities to another basaltic shergottite Dhofar 378.

Some petrological aspects of Imbrium stratigraphy

NASA Technical Reports Server (NTRS)

Ridley, W. I.

1977-01-01

Descriptions are given of the petrochemistry of two Apennine Front breccias, both ejected to the surface during excavation of Spur Crater. The first clast type is breccia number 15445, a spinel pyroxenite whose mineralogy and petrochemistry are consistent with the original rock type being a garnet pyroxenite. The second rock, breccia 15459, is plutonic norite, in which coarsely exsolved inverted pigeonite is associated with anorthitic plagioclase. Application of mineral geothermometers indicates crystallization of these rocks below 1100 C; hence their textures probably developed largely by solid state recrystallization during impact-metamorphism.

Mineral dissolution and precipitation during CO 2 injection at the Frio-I Brine Pilot: Geochemical modeling and uncertainty analysis

DOE PAGES

Ilgen, A. G.; Cygan, R. T.

2015-12-07

During the Frio-I Brine Pilot CO 2 injection experiment in 2004, distinct geochemical changes in response to the injection of 1600 tons of CO 2 were recorded in samples collected from the monitoring well. Previous geochemical modeling studies have considered dissolution of calcite and iron oxyhydroxides, or release of adsorbed iron, as the most likely sources of the increased ion concentrations. We explore in this modeling study possible alternative sources of the increasing calcium and iron, based on the data from the detailed petrographic characterization of the Upper Frio Formation “C”. Particularly, we evaluate whether dissolution of pyrite andmore » oligoclase (anorthite component) can account for the observed geochemical changes. Due to kinetic limitations, dissolution of pyrite and anorthite cannot account for the increased iron and calcium concentrations on the time scale of the field test (10 days). However, dissolution of these minerals is contributing to carbonate and clay mineral precipitation on the longer time scales (1000 years). The one-dimensional reactive transport model predicts carbonate minerals, dolomite and ankerite, as well as clay minerals kaolinite, nontronite and montmorillonite, will precipitate in the Frio Formation “C” sandstone as the system progresses towards chemical equilibrium during a 1000-year period. Cumulative uncertainties associated with using different thermodynamic databases, activity correction models (Pitzer vs. B-dot), and extrapolating to reservoir temperature, are manifested in the difference in the predicted mineral phases. Furthermore, these models are consistent with regards to the total volume of mineral precipitation and porosity values which are predicted to within 0.002%.« less

Assimilation by lunar mare basalts: Melting of crustal material and dissolution of anorthite

NASA Astrophysics Data System (ADS)

Finnila, A. B.; Hess, P. C.; Rutherford, M. J.

1994-07-01

We discuss techniques for calculating the amount of crustal assimilation possible in lunar magma chambers and dikes based on thermal energy balances, kinetic rates, and simple fluid mechanical constraints. Assuming parent magmas of picritic compositions, we demonstrate the limits on the capacity of such magmas to melt and dissolve wall rock of anorthitic, troctolitic, noritic, and KREEP (quartz monzodiorite) compositions. Significant melting of the plagioclase-rich crustal lithologies requires turbulent convection in the assimilating magma and an efficient method of mixing in the relatively buoyant and viscous new melt. Even when this occurs, the major element chemistry of the picritic magmas will change by less than 1-2 wt %. Diffusion coefficients measured for Al2O3 from an iron-free basalt and an orange glass composition are 10-12 sq m/s at 1340 C and 10-11 sq m/s at 1390 C. These rates are too slow to allow dissolution of plagioclase to significantly affect magma compositions. Picritic magmas can melt significant quantities of KREEP, which suggests that their trace element chemistry may still be affected by assimilation processes; however, mixing viscous melts of KREEP composition with the fluid picritic magmas could be prohibitively difficult. We conclude that only a small part of the total major element chemical variation in the mare basalt and volcanic glass collection is due to assimilation/fractional crystallization processes near the lunar surface. Instead, most of the chemical variation in the lunar basalts and volcanic glasses must result from assimilation at deeper levels or from having distinct source regions in a heterogeneous lunar mantle.

Assimilation by lunar mare basalts: Melting of crustal material and dissolution of anorthite

NASA Technical Reports Server (NTRS)

Finnila, A. B.; Hess, P. C.; Rutherford, M. J.

1994-01-01

We discuss techniques for calculating the amount of crustal assimilation possible in lunar magma chambers and dikes based on thermal energy balances, kinetic rates, and simple fluid mechanical constraints. Assuming parent magmas of picritic compositions, we demonstrate the limits on the capacity of such magmas to melt and dissolve wall rock of anorthitic, troctolitic, noritic, and KREEP (quartz monzodiorite) compositions. Significant melting of the plagioclase-rich crustal lithologies requires turbulent convection in the assimilating magma and an efficient method of mixing in the relatively buoyant and viscous new melt. Even when this occurs, the major element chemistry of the picritic magmas will change by less than 1-2 wt %. Diffusion coefficients measured for Al2O3 from an iron-free basalt and an orange glass composition are 10(exp -12) sq m/s at 1340 C and 10(exp -11) sq m/s at 1390 C. These rates are too slow to allow dissolution of plagioclase to significantly affect magma compositions. Picritic magmas can melt significant quantities of KREEP, which suggests that their trace element chemistry may still be affected by assimilation processes; however, mixing viscous melts of KREEP composition with the fluid picritic magmas could be prohibitively difficult. We conclude that only a small part of the total major element chemical variation in the mare basalt and volcanic glass collection is due to assimilation/fractional crystallization processes near the lunar surface. Instead, most of the chemical variation in the lunar basalts and volcanic glasses must result from assimilation at deeper levels or from having distinct source regions in a heterogeneous lunar mantle.

Visible/near-infrared spectra of experimentally shocked plagioclase feldspars

USGS Publications Warehouse

Johnson, J. R.; Horz, F.

2003-01-01

High shock pressures cause structural changes in plagioclase feldspars such as mechanical fracturing and disaggregation of the crystal lattice at submicron scales, the formation of diaplectic glass (maskelynite), and genuine melting. Past studies of visible/ near-infrared spectra of shocked feldspars demonstrated few spectral variations with pressure except for a decrease in the depth of the absorption feature near 1250-1300 nm and an overall decrease in reflectance. New visible/near-infrared spectra (400-2500 nm) of experimentally shocked (17-56 GPa) albite- and anorthite-rich rock powders demonstrate similar trends, including the loss of minor hydrated mineral bands near 1410, 1930, 2250, and 2350 nm. However, the most interesting new observations are increases in reflectance at intermediate pressures, followed by subsequent decreases in reflectance at higher pressures. The amount of internal scattering and overall sample reflectance is controlled by the relative proportions of micro-fractures, submicron grains, diaplectic glass, and melts formed during shock metamorphism. We interpret the observed reflectance increases at intermediate pressures to result from progressively larger proportions of submicron feldspar grains and diaplectic glass. The ensuing decreases in reflectance occur after diaplectic glass formation is complete and the proportion of genuine melt inclusions increases. The pressure regimes over which these reflectance variations occur differ between albite and anorthite, consistent with thermal infrared spectra of these samples and previous studies of shocked feldspars. These types of spectral variations associated with different peak shock pressures should be considered during interpretation and modeling of visible/near-infrared remotely sensed spectra of planetary and asteroidal surfaces.

Optical and chemical analysis of iron in Luna 20 plagioclase.

NASA Technical Reports Server (NTRS)

Bell, P. M.; Mao, H. K.

1973-01-01

Review of analytical data on the iron content of Luna 20 anorthitic plagioclase, obtained by a highly sensitive technique for measuring polarized absorption related to crystal-field splittings and by automated electron microprobe analysis of oriented single crystals. The iron content is found to range from a few hundredths to a few tenths of a weight per cent from crystal to crystal. The optical and chemical properties of the iron appear to be caused by postcrystallization migration and exsolution. Postcrystallization effects may obscure evidence of the original oxidation state and iron concentration of these crystals.

Assimilation by Lunar Mare Basalts: Melting of Crustal Material and Dissolution of Anorthite

NASA Technical Reports Server (NTRS)

Finnila, A. B.; Hess, P. C.; Rutherford, M. J.

1994-01-01

We discuss techniques for calculating the amount of crustal assimilation possible in lunar magma chambers and dikes based on thermal energy balances, kinetic rates, and simple fluid mechanical constraints. Assuming parent magmas of picritic compositions, we demonstrate the limits on the capacity of such magmas to melt and dissolve wall rock of anorthitic, troctolitic, noritic, and KREEP (quartz monzodiorite) compositions. Significant melting of the plagioclase-rich crustal lithologies requires turbulent convection in the assimilating magma and an efficient method of mixing in the relatively buoyant and viscous new melt. Even when this occurs, the major element chemistry of the picritic magmas will change by less than 1-2 wt %. Diffusion coefficients measured for Al2O3 from an iron-free basalt and an orange glass composition are 10(exp -12) m(exp 2) s(exp -1) at 1340 C and 10(exp -11) m(exp 2) s(exp -1) at 1390 C. These rates are too slow to allow dissolution of plagioclase to significantly affect magma compositions. Picritic magmas can melt significant quantities of KREEP, which suggests that their trace element chemistry may still be affected by assimilation processes; however, mixing viscous melts of KREEP composition with the fluid picritic magmas could be prohibitively difficult. We conclude that only a small part of the total major element chemical variation in the mare basalt and volcanic glass collection is due to assimilation/fractional crystallization processes near the lunar surface. Instead, most of the chemical variation in the lunar basalts and volcanic glasses must result from assimilation at deeper levels or from having distinct source regions in a heterogeneous lunar mantle.

Dynamism or Disorder at High Pressures?

NASA Astrophysics Data System (ADS)

Angel, R. J.; Bismayer, U.; Marshall, W. G.

2002-12-01

Phase transitions in minerals at elevated temperatures typically involve dynamics as a natural consequence of the increase in thermal energy available to the system. Classic examples include quartz, cristobalite, and carbonates in which the high-temperature, high symmetry phase is dynamically disordered. This disorder has important thermodynamic consequences, including displacement and curvature of phase boundaries (e.g. calcite-aragonite). In other minerals such as clinopyroxenes and anorthite feldspar, the dynamic behaviour is restricted to the neighbourhood of the phase transition. The fundamental question is whether increasing pressure generally suppresses such dynamic behaviour (as in anorthite; Angel, 1988), or not. In the latter case it must be included in thermodynamic models of high-pressure phase equilibria and seismological modelling of the mantle; the potential dynamics and softening in stishovite may provide the critical observational constraint on the presence or otherwise of free silica in the lower mantle. We have continued to use the lead phosphate as a prototype ferroelastic in which to understand dynamic behaviour, simply because its dynamics and transition behaviour is far better characterised than any mineral. Furthermore, the phase transition is at a pressure where experimental difficulties do not dominate the experimental results. Our previous neutron diffraction study (Angel et al., 2001) revealed that some disorder, either dynamic or static, is retained in the high-symmetry, high-pressure phase just above the phase transition. New neutron diffraction data on the pure material now suggests that this disorder slowly decreases with increasing pressure until at twice the transition pressure it is ordered. Further data for doped material provides insights into the nature of this disorder. Angel (1988) Amer. Mineral. 73:1114. Angel et al (2001) J PhysC 13: 5353.

A new model for the origin of Type-B and Fluffy Type-A CAIs: Analogies to remelted compound chondrules

NASA Astrophysics Data System (ADS)

Rubin, Alan E.

2012-06-01

In the scenario developed here, most types of calcium-aluminum-rich inclusions (CAIs) formed near the Sun where they developed Wark-Lovering rims before being transported by aerodynamic forces throughout the nebula. The amount of ambient dust in the nebula varied with heliocentric distance, peaking in the CV-CK formation location. Literature data show that accretionary rims (which occur outside the Wark-Lovering rims) around CAIs contain substantial 16O-rich forsterite, suggesting that, at this time, the ambient dust in the nebula consisted largely of 16O-rich forsterite. Individual sub-millimeter-size Compact Type-A CAIs (each surrounded by a Wark-Lovering rim) collided in the CV-CK region and stuck together (in a manner similar to that of sibling compound chondrules); the CTAs were mixed with small amounts of 16O-rich mafic dust and formed centimeter-size compound objects (large Fluffy Type-A CAIs) after experiencing minor melting. In contrast to other types of CAIs, centimeter-size Type-B CAIs formed directly in the CV-CK region after gehlenite-rich Compact Type-A CAIs collided and stuck together, incorporated significant amounts of 16O-rich forsteritic dust (on the order of 10-15%) and probably some anorthite, and experienced extensive melting and partial evaporation. (Enveloping compound chondrules formed in an analogous manner.) In those cases where appreciably higher amounts of 16O-rich forsterite (on the order of 25%) (and perhaps minor anorthite and pyroxene) were incorporated into compound Type-A objects prior to melting, centimeter-size forsterite-bearing Type-B CAIs (B3 inclusions) were produced. Type-B1 inclusions formed from B2 inclusions that collided with and stuck to melilite-rich Compact Type-A CAIs and experienced high-temperature processing.

High temperature gas-solid reactions in calc-silicate Cu-Au skarn formation; Ertsberg, Papua Province, Indonesia

NASA Astrophysics Data System (ADS)

Henley, Richard W.; Brink, Frank J.; King, Penelope L.; Leys, Clyde; Ganguly, Jibamitra; Mernagh, Terrance; Middleton, Jill; Renggli, Christian J.; Sieber, Melanie; Troitzsch, Ulrike; Turner, Michael

2017-12-01

The 2.7-3 Ma Ertsberg East Skarn System (Indonesia), adjacent to the giant Grasberg Porphyry Copper deposit, is part of the world's largest system of Cu -Au skarn deposits. Published fluid inclusion and stable isotope data show that it formed through the flux of magma-derived fluid through contact metamorphosed carbonate rock sequences at temperatures well above 600° C and pressures of less than 50 MPa. Under these conditions, the fluid has very low density and the properties of a gas. Combining a range of micro-analytical techniques, high-resolution QEMSCAN mineral mapping and computer-assisted X-ray micro-tomography, an array of coupled gas-solid reactions may be identified that controlled reactive mass transfer through the 1 km3 hydrothermal skarn system. Vacancy-driven mineral chemisorption reactions are identified as a new type of reactive transport process for high-temperature skarn alteration. These gas-solid reactions are maintained by the interaction of unsatisfied bonds on mineral surfaces and dipolar gas-phase reactants such as SO2 and HCl that are continuously supplied through open fractures and intergranular diffusion. Principal reactions are (a) incongruent dissolution of almandine-grossular to andradite and anorthite (an alteration mineral not previously recognized at Ertsberg), and (b) sulfation of anorthite to anhydrite. These sulfation reactions also generate reduced sulfur with consequent co-deposition of metal sulfides. Diopside undergoes similar reactions with deposition of Fe-enriched pyroxene in crypto-veins and vein selvedges. The loss of calcium from contact metamorphic garnet to form vein anhydrite necessarily results in Fe-enrichment of wallrock, and does not require Fe-addition from a vein fluid as is commonly assumed.

Diversity in the Visible-NIR Absorption Band Characteristics of Lunar and Asteroidal Plagioclase

NASA Technical Reports Server (NTRS)

Hiroi, T.; Kaiden, H.; Misawa, K.; Kojima, H.; Uemoto, K.; Ohtake, M.; Arai, T.; Sasaki, S.; Takeda, H.; Nyquist, L. E.;

Experimental petrology and origin of Fra Mauro rocks and soil

NASA Technical Reports Server (NTRS)

Walker, D.; Longhi, J.; Hays, J. F.

1972-01-01

Melting experiments over the pressure range 0 to 20 kilobars were conducted on Apollo 14 igneous rocks 14310 and 14072 and on comprehensive fines 14259. The mineralogy and textures of rocks 14310 and 14072 are presumed to be the result of near-surface crystallization. The chemical compositions of the samples show special relationships to multiply-saturated liquids in the system: anorthite-forsterite-fayalite-silica at low pressure. Partial melting of a lunar crust consisting largely of plagioclase, low calcium pyroxene, and olivine, followed by crystal fractionation at the lunar surface is proposed as a mechanism for the production of the igneous rocks and soil glasses sampled by Apollo 14.

Petrologic characteristics of the 1982 and pre-1982 eruptive products of El Chichon volcano, Chiapas, Mexico.

USGS Publications Warehouse

McGee, J.J.; Tilling, R.I.; Duffield, W.A.

1987-01-01

Studies on a suite of rocks from this volcano indicate that the juvenile materials of the 1982 and pre-1982 eruptions of the volcano have essentially the same mineralogy and chemistry. Data suggest that chemical composition changed little over the 0.3 m.y. sample period. Modally, plagioclase is the dominant phenocryst, followed by amphibole, clinopyroxene and minor phases including anhydrite. Plagioclase phenocrysts show complex zoning: the anorthite-rich zones are probably the result of changing volatile P on the magma and may reflect the changes in the volcano's magma reservoir in response to repetitive, explosive eruptive activity.-R.E.S.

Laboratory simulation of infrared astrophysical features. Ph.D. Thesis; [emission spectra of comets

NASA Technical Reports Server (NTRS)

Rose, L. A.

1977-01-01

Intermediate resolution emission spectroscopy was used to study a group of 9 terrestrial silicates, 1 synthetic silicate, 6 meteorites and 2 lunar soils; comparisons were made with the intermediate resolution spectra of Comet Kohoutek in order to determine which materials best simulate the 10um astrophysical feature. Mixtures of silicates which would yield spectra matching the spectrum of the comet in the 10um region include: (1) A hydrous layer lattice silicate in combination with a high temperature condensate; (2) an amorphous magnesium silicate in combination with a high temperature condensate and (3) glassy olivine and glassy anorthite in approximately equal proportions.

Experimental approach to form anorthositic melts: phase relations in the system CaAl2Si2O8 - CaMgSi2O6 - Mg2SiO4 at 6 wt.% H2O

NASA Astrophysics Data System (ADS)

Zirner, Aurelia Lucretia Katharina; Ballhaus, Chris; Fonseca, Raúl; Müncker, Carsten

2014-05-01

Massive anorthosite dykes are documented for the first time from the Limassol Forest Complex (LFC) of Cyprus, the LFC being a deformed equivalent of the Troodos ultramafic massif. Both the Troodos and LFC complexes are part of the Tethyan realm consisting of Cretaceous oceanic crust that formed within a backarc basin 90 Ma ago and was obduced during late Miocene. From crosscutting relations with the sheeted dyke complex, it follows that the anorthosites belong to one of the latest magmatic events on Cyprus. In hand specimen, the rocks appear massive and unaltered, although in thin section magmatic plagioclase (An93) is partially replaced by albite and thomsonite (zeolite). Where magmatic textures are preserved, plagioclase forms cm-sized, acicular, radially arranged crystal aggregates that remind of spinifex textures. Six major types of anorthosite occurrences have previously been described, none of them matching with the above described anorthosite dykes [1]. The origin of these anorthosite dykes remains poorly understood. Even though they occur as intrusive dykes, it is evident that they cannot represent liquidus compositions, at least under dry conditions. Whole-sale melting of pure An93 would require temperatures in excess of 1450 °C, which is a quite unrealistic temperature of the modern Earth's crust. The working hypothesis is that boninitic melts with approximately 4 wt.% H2O, as found in the cyprian upper pillow lavas (UPL), could produce such rocks by olivine-pyroxene fractionation. Indeed, experiments indicate that such lithologies can be generated by medium-pressure fractional crystallization of hydrous basaltic melts followed by decompression-degassing. High pH2O stabilizes olivine but tends to suppress plagioclase as the highest polymerized phase. Hence the An component is accumulated in the (late-stage) melt. When such a system experiences sudden decompression, the aqueous phase will exsolve and will trigger massive precipitation of anorthite. Experiments at various temperatures are being performed in the ol-cpx-plag-H2O system, with olivine from a xenolith (Fo95) and anorthite and diopside glasses as starting materials. The materials are ground and mixed in the desired proportions, then equilibrated with 6 wt. % H2O at 0.5 GPa total pressure in a piston-cylinder press. A phase diagram of the Fo-Di-An-H2O system at 0.5 GPa will be constructed to outline the precise phase relations and fractionation paths are high H2O partial pressure. Aim is to delineate the anorthite saturation field in the ol-cpx-plag-H2O system, and to assess to which extent plagioclase can be suppressed as a liquidus phase when a basaltic melt fractionates under hydrous conditions. [1] Ashwal, L. D. (1993). Anorthosites, Springer-Verlag.

The Effect of Acidity Coefficient on Crystallization Behavior of Blast Furnace Slag Fibers

NASA Astrophysics Data System (ADS)

Tian, Tie-Lei; Zhang, Yu-Zhu; Xing, Hong-wei; Li, Jie; Zhang, Zun-Qian

2018-01-01

The chemical structure of mineral wool fiber was investigated by using Fourier Transform Infrared Spectroscopy (FTIR). Next, the glass transition temperature and the crystallization temperature of the fibers were studied. Finally, the crystallization kinetics of fiber was studied. The results show that the chemical bond structure of fibers gets more random with the increase of acidity coefficient. The crystallization phases of the fibers are mainly melilites, and also a few anorthites and diopsides. The growth mechanism of the crystals is three dimensional. The fibers with acidity coefficient of 1.2 exhibit the best thermal stability and is hard to crystallize as it has the maximum aviation energy of crystallization kinetics.

Melting behavior and phase relations of lunar samples

NASA Technical Reports Server (NTRS)

Hays, J. F.

1976-01-01

An attempt was made to show that feldspar would float during melting. Large anorthite crystals were placed beneath a silicate glass representative of liquid in which plagioclase accumulation is thought to have occurred. In less than 3 hours at 1,300 C, the crystals rose to the top in a Pt crucible 3 cm deep equilibrated in air and in a Mo crucible 1.5 cm deep equilibrated in an H2/CO2 gas stream of log PO2 = -10.9 (below Fe/FeO). These results suggest that lunar crustal formation by feldspar flotation is possible without special recourse to differential sinking of plagioclase versus mafic minerals or selective elutriation of plagioclase.

The Role of KREEP in the Production of Mg-Suite Magmas and Its Influence on the Extent of Mg-Suite Magmatism in the Lunar Crust

NASA Technical Reports Server (NTRS)

Elardo, S. M.; Shearer, C. K.; McCubbin, F. M.

2017-01-01

The lunar magnesian-suite, or Mg-suite, is a series of ancient plutonic rocks from the lunar crust. They have received a considerable amount of attention from lunar scientists since their discovery for three primary reasons: 1) their ages and geochemistry indicate they represent pristine magmatic samples that crystallized very soon after the formation of the Moon; 2) their ages often overlap with ages of the ferroan anorthosite (FAN) crust; and 3) planetary-scale processes are needed in formation models to account for their unique geochemical features. Taken as a whole, the Mg-suite samples, as magmatic cumulate rocks, approximate a fractional crystallization sequence in the low-pressure forsterite-anorthite-silica system, and thus these samples are generally thought to be derived from layered mafic intrusions which crystallized very slowly from magmas that intruded the anorthositic crust. However, no direct linkages have been established between different Mg-suite samples based either on field relationships or geochemistry.The model for the origin of the Mg-suite, which best fits the limited available data, is one where Mg-suite magmas form from melting of a hybrid cumulate package consisting of deep mantle dunite, crustal anorthosite, and KREEP (potassium-rare earth elements-phosphorus) at the base of the crust under the Procellarum KREEP Terrane (PKT). In this model, these three LMO (Lunar Magma Ocean) cumulate components are brought into close proximity by the cumulate overturn process. Deep mantle dunitic cumulates with an Mg number of approximately 90 rise to the base of the anorthositic crust due to their buoyancy relative to colder, more dense Fe- and Ti-rich cumulates. This hybridized source rock melts to form Mg-suite magmas, saturated in Mg-rich olivine and anorthitic plagioclase, that have a substantial KREEP component.

Crystal residence times from trace element zoning in plagioclase reveal changes in magma transfer dynamics at Mt. Etna during the last 400 years

NASA Astrophysics Data System (ADS)

Viccaro, Marco; Barca, Donatella; Bohrson, Wendy A.; D'Oriano, Claudia; Giuffrida, Marisa; Nicotra, Eugenio; Pitcher, Bradley W.

2016-04-01

Trace element zoning in plagioclase of selected alkaline lavas from the historic (1607-1892 AD) and recent (1983-2013 AD) activity of Mt. Etna volcano has been used to explore the possible role that volcano-tectonics exert on magma transfer dynamics. The observed textural characteristics of crystals include near-equilibrium textures (i.e., oscillatory zoning) and textures with variable extent of disequilibrium (patchy zoning, coarse sieve textures and dissolved cores). Historic crystals exhibit lower K concentrations at lower anorthite contents, a feature in agreement with the general more potassic character of the recent lavas if compared to the historic products. Historic plagioclases have statistically higher Ba and lower Sr concentrations than the recent crystals, which result in different Sr/Ba ratios for the two suites of plagioclase. Variations in the anorthite content along core-to-rim profiles obtained on crystals with different types of textures for both the historic and recent eruptive periods were evaluated particularly versus Sr/Ba. At comparable average An contents, crystals characterized by oscillatory zoning, which are representative of near-equilibrium crystallization from the magma, display distinct Sr/Ba ratios. We suggest that these features are primarily related to recharge of a new, geochemically-distinct magma into the storage and transport system of the volcano. In addition to distinct trace element and textural characteristics of plagioclase, Sr diffusion modeling for plagioclase suggests that residence times are generally shorter for crystals found in recently erupted lavas (25-77 years, average 43 years) compared to those of the historic products (43-163 years, average 99 years). Shorter residences times correlate with gradual increases in eruption volume and eruption frequency rates through time. We attribute these features to an increasing influence, since the 17th century, of extensional tectonic structures within the upper 10 km of the Etnean crust, which have promoted shorter residence times and higher eruption frequency.

The origin of groundwater composition in the Pampeano Aquifer underlying the Del Azul Creek basin, Argentina.

PubMed

Zabala, M E; Manzano, M; Vives, L

2015-06-15

The Pampean plain is the most productive region in Argentina. The Pampeano Aquifer beneath the Pampean plain is used mostly for drinking water. The study area is the sector of the Pampeano Aquifer underlying the Del Azul Creek basin, in Buenos Aires province. The main objective is to characterize the chemical and isotopic compositions of groundwater and their origin on a regional scale. The methodology used involved the identification and characterization of potential sources of solutes, the study of rain water and groundwater chemical and isotopic characteristics to deduce processes, the development of a hydrogeochemical conceptual model, and its validation by hydrogeochemical modelling with PHREEQC. Groundwater samples come mostly from a two-depth monitoring network of the "Dr. Eduardo J. Usunoff" Large Plains Hydrology Institute (IHLLA). Groundwater salinity increases from SW to NE, where groundwater is saline. In the upper basin groundwater is of the HCO3-Ca type, in the middle basin it is HCO3-Na, and in the lower basin it is ClSO4-NaCa and Cl-Na. The main processes incorporating solutes to groundwater during recharge in the upper basin are rain water evaporation, dissolution of CO2, calcite, dolomite, silica, and anorthite; cationic exchange with Na release and Ca and Mg uptake, and clay precipitation. The main processes modifying groundwater chemistry along horizontal flow at 30 m depth from the upper to the lower basin are cationic exchange, dissolution of silica and anorthite, and clay precipitation. The origin of salinity in the middle and lower basin is secular evaporation in a naturally endorheic area. In the upper and middle basins there is agricultural pollution. In the lower basin the main pollution source is human liquid and solid wastes. Vertical infiltration through the boreholes annular space during the yearly flooding stages is probably the pollution mechanism of the samples at 30 m depth. Copyright © 2015 Elsevier B.V. All rights reserved.

Oxygen Isotope Measurements of a Rare Murchison Type A CAI and Its Rim

NASA Technical Reports Server (NTRS)

Matzel, J. E. P.; Simon, J. I.; Hutcheon, I. D.; Jacobsen, B.; Simon, S. B.; Grossman, L.

2013-01-01

Ca-, Al-rich inclusions (CAIs) from CV chondrites commonly show oxygen isotope heterogeneity among different mineral phases within individual inclusions reflecting the complex history of CAIs in both the solar nebula and/or parent bodies. The degree of isotopic exchange is typically mineral-specific, yielding O-16-rich spinel, hibonite and pyroxene and O-16-depleted melilite and anorthite. Recent work demonstrated large and systematic variations in oxygen isotope composition within the margin and Wark-Lovering rim of an Allende Type A CAI. These variations suggest that some CV CAIs formed from several oxygen reservoirs and may reflect transport between distinct regions of the solar nebula or varying gas composition near the proto-Sun. Oxygen isotope compositions of CAIs from other, less-altered chondrites show less intra-CAI variability and 16O-rich compositions. The record of intra-CAI oxygen isotope variability in CM chondrites, which commonly show evidence for low-temperature aqueous alteration, is less clear, in part because the most common CAIs found in CM chondrites are mineralogically simple (hibonite +/- spinel or spinel +/- pyroxene) and are composed of minerals less susceptible to O-isotopic exchange. No measurements of the oxygen isotope compositions of rims on CAIs in CM chondrites have been reported. Here, we present oxygen isotope data from a rare, Type A CAI from the Murchison meteorite, MUM-1. The data were collected from melilite, hibonite, perovskite and spinel in a traverse into the interior of the CAI and from pyroxene, melilite, anorthite, and spinel in the Wark-Lovering rim. Our objectives were to (1) document any evidence for intra-CAI oxygen isotope variability; (2) determine the isotopic composition of the rim minerals and compare their composition(s) to the CAI interior; and (3) compare the MUM-1 data to oxygen isotope zoning profiles measured from CAIs in other chondrites.

Three-Dimensional Modeling of the Reactive Transport of CO2 and Its Impact on Geomechanical Properties of Reservoir Rocks and Seals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nguyen, Ba Nghiep; Hou, Zhangshuan; Bacon, Diana H.

This article develops a novel multiscale modeling approach to analyze CO2 reservoirs using Pacific Northwest National Laboratory’s STOMP-CO2-R code that is interfaced with the ABAQUS® finite element package. The STOMP-CO2-R/ABAQUS® sequentially coupled simulator accounts for the reactive transport of CO2 causing mineral composition changes that modify the geomechanical properties of reservoir rocks and seals. Formation rocks’ elastic properties that vary during CO2 injection and govern the poroelastic behavior of rocks are modeled by an Eshelby-Mori-Tanka approach (EMTA) implemented in ABAQUS® via user-subroutines. The computational tool incorporates the change in rock permeability due to both geochemistry and geomechanics. A three-dimensional (3D)more » STOMP-CO2-R model for a model CO2 reservoir containing a vertical fault is built to analyze a formation containing a realistic geochemical reaction network with 5 minerals: albite, anorthite, calcite, kaolinite and quartz. A 3D ABAQUS® model that maps the above STOMP-CO2-R model is built for the analysis using STOMP-CO2-R/ABAQUS®. The results show that the changes in volume fraction of minerals include dissolution of anorthite, precipitation of calcite and kaolinite, with little change in the albite volume fraction. After a long period of CO2 injection the mineralogical and geomechanical changes significantly reduced the permeability and elastic modulus of the reservoir (between the base and caprock) in front of the fault leading to a reduction of the pressure margin to fracture at and beyond the injection location. The impact of reactive transport of CO2 on the geomechanical properties of reservoir rocks and seals are studied in terms of mineral composition changes that directly affect the rock stiffness, stress and strain distributions as well as the pressure margin to fracture.« less

A generalized garnet-forming reaction for metaigneous rocks in the Adirondacks

USGS Publications Warehouse

McLelland, J.M.; Whitney, P.R.

1980-01-01

A generalized reaction is presented to account for garnet formation in a variety of Adirondack metaigneous rocks. This reaction, which is the sum of five partial reactions written in aluminum-fixed frames of reference, is given by: 4(y+1+w)Anorthite+4 k(y+1+2 w)Olivine +4(1-k)(y+1+2 w)Fe-oxide+(8(y+1) -4 k(y+1+2 w))Orthopyroxene = 2(y+1)Garnet +2(y+1+2 w)Clinopyroxene+4 wSpinel where y is a function of plagioclase composition, k refers to the relative amounts of olivine and Fe-oxide participating in the reaction, and w is a measure of silicon mobility. When mass balanced for Mg and Fe, this reaction is found to be consistent with analyzed mineral compositions in a wide range of Adirondack metaigneous rocks. The reaction applies equally well whether the garnets were formed directly from the rectants given above or went through an intermadiate stage involving the formation of spinel, orthopyroxene, and clinopyroxene. The actual reactions which have produced garnet in both undersaturated and quartz-bearing rocks are special cases of the above general reaction. The most important special cases appear to be those in which the reactants include either olivine alone (k=1) or Fe-oxide alone (k=0). Silicon is relatively immobile (w =2) in olivine bearing, magnesium-rich rocks (k???1), and this correlates with the increased intensity in spinel clouding of plagioclase in these rocks. Silicon mobility apparently increases in the more iron-rich rocks, which also tend to contain clear or lightly clouded plagioclase. In all the rocks studied the most common composition of metamorphic plagioclase is close to An33 (i.e., y=1). Plagioclase of lower anorthite content may be too sodic to participate in garnet formation at the P-T conditions involved. ?? 1980 Springer-Verlag.

Lunar cement

NASA Technical Reports Server (NTRS)

Agosto, William N.

1992-01-01

With the exception of water, the major oxide constituents of terrestrial cements are present at all nine lunar sites from which samples have been returned. However, with the exception of relatively rare cristobalite, the lunar oxides are not present as individual phases but are combined in silicates and in mixed oxides. Lime (CaO) is most abundant on the Moon in the plagioclase (CaAl2Si2O8) of highland anorthosites. It may be possible to enrich the lime content of anorthite to levels like those of Portland cement by pyrolyzing it with lunar-derived phosphate. The phosphate consumed in such a reaction can be regenerated by reacting the phosphorus product with lunar augite pyroxenes at elevated temperatures. Other possible sources of lunar phosphate and other oxides are discussed.

Lunar cement and lunar concrete

NASA Technical Reports Server (NTRS)

Lin, T. D.

1991-01-01

Results of a study to investigate methods of producing cements from lunar materials are presented. A chemical process and a differential volatilization process to enrich lime content in selected lunar materials were identified. One new cement made from lime and anorthite developed compressive strengths of 39 Mpa (5500 psi) for 1 inch paste cubes. The second, a hypothetical composition based on differential volatilization of basalt, formed a mineral glass which was activated with an alkaline additive. The 1 inch paste cubes, cured at 100C and 100 percent humidity, developed compressive strengths in excess of 49 Mpa (7100 psi). Also discussed are tests made with Apollo 16 lunar soil and an ongoing investigation of a proposed dry mix/steam injection procedure for casting concrete on the Moon.

Alteration of Al-rich inclusions inside amoeboid olivine aggregates in the Allende meteorite

NASA Technical Reports Server (NTRS)

Hashimoto, Akihiko; Grossman, Lawrence

1987-01-01

The primary phases of Al-rich inclusions in amoeboid olivine aggregates have undergone alteration reactions with the solar nebular gas. The simplest interpretation of the present observations is that melilite was the first primary phase to disappear with falling temperature, and was replaced by grossular + anorthite + feldspathoids, followed by fassaite; spinel was the last phase to be altered. Thermodynamic calculations suggest that Na-rich phlogopite could have formed at about 470 K and chlorite at about 328 K at a water fugacity of 0.000001, which is that of a gas of solar composition in this temperature range. The olivine around Al-rich inclusions is not serpentized, indicating the cessation of gas-solid equilibrium above 274 K.

Experimental petrology and origin of rocks from the Descartes Highlands

NASA Technical Reports Server (NTRS)

Walker, D.; Longhi, J.; Grove, T. L.; Stolper, E.; Hays, J. F.

1973-01-01

Petrographic studies of Apollo 16 samples indicate that rocks 62295 and 68415 are crystallization products of highly aluminous melts. 60025 is a shocked, crushed and partially annealed plagioclase cumulate. 60315 is a recrystallized noritic breccia of disputed origin. 60335 is a feldspathic basalt filled with xenoliths and xenocrysts of anorthosite, breccia, and anorthite. The Fe/(Fe+Mg) of plagioclase appears to be a relative crystallization index. Low pressure melting experiments with controlled Po2 indicate that the igneous samples crystallized at oxygen fugacities well below the Fe/FeO buffer. Crystallization experiments at various pressures suggest that the 62295 and 68415 compositions were produced by partial or complete melting of lunar crustal materials, and not by partial melting of the deep lunar interior.

Formation and composition of the moon. [carbonaceous meteorites

NASA Technical Reports Server (NTRS)

Anderson, D. L.

1974-01-01

Many of the properties of the moon are discussed including the enrichment in Ca, Al, Ti, U, Th, Ba, Sr and the REE and the depletion in Fe, Rb, K, Na and other volatiles which could be understood if the moon represents a high temperature condensate from the solar nebula. Thermodynamic calculations show that Ca, Al and Ti rich compounds condense first in a cooling nebula. The initial high temperature mineralogy is gehlenite, spinel, perovskite, Ca-Al-rich pyroxenes and anorthite. Inclusions in Type III carbonaceous chondrites such as the Allende meteorite are composed primarily of these minerals and, in addition, are highly enriched in refractories such as REE relative to carbonaceous chondrites. These inclusions can yield basalt and anorthosite in the proportions required to eliminate the europium anomaly, leaving a residual spinel-melilite interior.

Crystal-chemical controls on the partitioning of Sr and Ba between plagioclase feldspar, silicate melts, and hydrothermal solutions

NASA Astrophysics Data System (ADS)

Blundy, Jonathan D.; Wood, Bernard J.

1991-01-01

The isothermal (750°C) experiments of LAGACHE and DUJON (1987) reveal that the partitioning of Sr between plagioclase feldspar and hydrothermal solutions is a funtion of the anorthite (An) content of the plagioclase, indicating that crystal chemistry may exert a powerful influence on trace element partitioning. In order to compare these results with those on trace element partitioning between plagioclase and silicate melts we have compiled from the literature a large dataset of experimental and volcanic distribution coefficients ( D's) for Sr (and Ba). These data, which span a compositional range from lunar basalt to high silica rhyolite and a temperature range of over 650°C, show a relationship between DSr (and DBa) and mole fraction An ( XAn) which is similar to that exhibited by the hydrothermal results obtained at constant temperature. Plots of In DSr and In DBa versus XAn are linear with negative slope, indicating that both elements are more compatible in albite than anorthite. In terms of molar distribution coefficients ( D Sr∗) the hydrothermal and silicate melt data display an identical linear relationship between RT In D Sr∗ (where T is the absolute temperature in K and R is the gas constant, 8.314 JK -1 mol -1) and XAn. We conclude therefore that crystal chemistry provides the dominant control on partitioning of Sr and Ba into plagioclase and that the effects of temperature, pressure, and fluid composition are minor. Apparent relationships between DSr (and DBa) and the reciprocal temperature (1/ T) are artefacts of the linear relationships between XAn and 1/ T in the experimental studies. By defining a Henry's law standard state for the silicate melts and hydrothermal solutions, and considering plagioclases to be ternary regular solutions, we are able to relate the observed relationships between RT In D i∗ (where i is Ba or Sr) and XAn to the excess free energies of the trace element partitioning reactions between plagioclase and melt or hydrothermal solution. The interaction parameters are consistent with simple models in which the larger Ba or Sr cations are accommodated by lattice strain in the host plagioclase lattice, which is assumed to be perfectly elastic and isotropic. Thus D i∗ is a function of the Young's modulus of the host crystal and the size mismatch between trace and host cations. The greater elasticity of albite relative to anorthite accounts for the observed preference of Sr and Ba for sodic plagioclases over calcic plagioclases. For geochemical purposes the weight fraction partition coefficient Di is of more value than its molar counterpart. Regression of the Di data versus XAn yields the semi-empirical relationships RTIn DSr = 26,800 - 26,700 · XAnRTIn DBa = 10,200 - 38,200 · XAn. Thus measurement of the An and trace element (Ba, Sr) contents of a magmatic plagioclase enables calculation of the Ba and Sr contents of the coexisting liquid, which can be extremely important in the deciphering of igneous processes. By reference to plagioclase fractionation in the simple An-Ab binary we show that failure to take into account the compositional dependence of DSr can result in erroneous interpretations of geochemical trends. We also consider applications to three natural igneous suites: the Aden Volcanics; the layered Kiglapait Intrusion, Labrador; and the southern Actamello Massif, Italy.

Preheated light gas gun shock experiments: hot Molybdenum and diopside-anorthite liquid Hugoniots revisited

NASA Astrophysics Data System (ADS)

Asimow, P. D.; Sun, D.; Ahrens, T. J.

2006-12-01

We have extended the techniques for pre-heated Hugoniot equation of state measurements for use on Caltech's 25 mm light gas gun at flyer velocities up to 7.5 km/s. Previous data on Mo at 1400°C and on a variety of silicate liquids were collected on a 40 mm propellant gun up to a maximum flyer velocity of 2.6 km/s. Higher impact velocities open up a range of new opportunities, including tests of previous extrapolations of low-pressure data and direct probing of the properties of molten silicates at lower mantle pressure. Our preheated liquid experiments are conducted in sealed Mo capsules and therefore we need to know the Hugoniot of Mo initially at elevated temperature, which may differ by several percent from the principal Hugoniot of Mo. Miller et al. [1] measured the Hugoniot EOS of Mo initially at 1400°C up to a particle velocity (Up) of 1.5 km/s and applied a linear fit with shock velocities slower than the principal Hugoniot in the measured range, but implying a crossover when extrapolated above 1.8 km/s (i.e., about 100 GPa pressure). Molodets [2] fit these data to a parameter-free theoretical form for the volume dependence of the Grüneisen parameter that predicts a concave-downward high-temperature Hugoniot that runs below and approaches parallel with the principal Hugoniot. Our data point at Up = 2.5 km/s (204 GPa) is coincident with Molodet's theory within error. However, our data point at Up = 3.24 km/s (302 GPa) is not; we are investigating this discrepancy. The silicate liquid composition consisting of 64 mol % anorthite and 36 mol % diopside is a simplified analogue for basalt and was chosen for study by Rigden et al. [3]. This earlier study found the expected linear Us-Up Hugoniot (with molar volume intermediate between anorthite and diopside end members) up to 25 GPa, followed by two data points that suggested a dramatic stiffening to a nearly incompressible Hugoniot. We now have three experiments at higher pressure (44, 81, and 110 GPa) that clearly show that this extrapolation was incorrect. All the data on this composition can be fit with a single linear Hugoniot. Although basaltic liquids of this composition are not expected in the lower mantle, the implication is that silicate liquids remain more compressible than solids at compressions approaching 50%. This is consistent with results from our laboratory on SiO2, MgSiO3, and Mg2SiO4 systems showing that melts in these systems become denser than coexisting solids at pressures similar to the base of the mantle. 1. Miller, G.H., T.J. Ahrens, and E.M. Stolper, The Equation of State of Molybdenum at 1400 °C. J. Appl. Phys., 1988. 63(9): p. 4469-4475. 2. Molodets, A.M., Shock compression of preheated molybdenum. High Pressure Research, 2005. 25(3): p. 211-216. 3. Rigden, S.M., T.J. Ahrens, and E.M. Stolper, Shock compression of molten silicate - results for a model basaltic composition. J. Geophys. Res., 1988. 93(B1): p. 367-382.

Size Matters: FTIR Spectral Analysis of Apollo Regolith Samples Exhibits Grain Size Dependence.

NASA Astrophysics Data System (ADS)

Martin, Dayl; Joy, Katherine; Pernet-Fisher, John; Wogelius, Roy; Morlok, Andreas; Hiesinger, Harald

2017-04-01

The Mercury Thermal Infrared Spectrometer (MERTIS) on the upcoming BepiColombo mission is designed to analyse the surface of Mercury in thermal infrared wavelengths (7-14 μm) to investigate the physical properties of the surface materials [1]. Laboratory analyses of analogue materials are useful for investigating how various sample properties alter the resulting infrared spectrum. Laboratory FTIR analysis of Apollo fine (<1mm) soil samples 14259,672, 15401,147, and 67481,96 have provided an insight into how grain size, composition, maturity (i.e., exposure to space weathering processes), and proportion of glassy material affect their average infrared spectra. Each of these samples was analysed as a bulk sample and five size fractions: <25, 25-63, 63-125, 125-250, and <250 μm. Sample 14259,672 is a highly mature highlands regolith with a large proportion of agglutinates [2]. The high agglutinate content (>60%) causes a 'flattening' of the spectrum, with reduced reflectance in the Reststrahlen Band region (RB) as much as 30% in comparison to samples that are dominated by a high proportion of crystalline material. Apollo 15401,147 is an immature regolith with a high proportion of volcanic glass pyroclastic beads [2]. The high mafic mineral content results in a systematic shift in the Christiansen Feature (CF - the point of lowest reflectance) to longer wavelength: 8.6 μm. The glass beads dominate the spectrum, displaying a broad peak around the main Si-O stretch band (at 10.8 μm). As such, individual mineral components of this sample cannot be resolved from the average spectrum alone. Apollo 67481,96 is a sub-mature regolith composed dominantly of anorthite plagioclase [2]. The CF position of the average spectrum is shifted to shorter wavelengths (8.2 μm) due to the higher proportion of felsic minerals. Its average spectrum is dominated by anorthite reflectance bands at 8.7, 9.1, 9.8, and 10.8 μm. The average reflectance is greater than the other samples due to a lower proportion of glassy material. In each soil, the smallest fractions (0-25 and 25-63 μm) have CF positions 0.1-0.4 μm higher than the larger grain sizes. Also, the bulk-sample spectra mostly closely resemble the 0-25 μm sieved size fraction spectrum, indicating that this size fraction of each sample dominates the bulk spectrum regardless of other physical properties. This has implications for surface analyses of other Solar System bodies where some mineral phases or components could be concentrated in a particular size fraction. For example, the anorthite grains in 67481,96 are dominantly >25 μm in size and therefore may not contribute proportionally to the bulk average spectrum (compared to the <25 μm fraction). The resulting bulk spectrum of 67481,96 has a CF position 0.2 μm higher than all size fractions >25 microns and therefore does not represent a true average composition of the sample. Further investigation of how grain size and composition alters the average spectrum is required to fully understand infrared spectra of planetary surfaces. [1] - Hiesinger H., Helbert J., and MERTIS Co-I Team. (2010). The Mercury Radiometer and Thermal Infrared Spectrometer (MERTIS) for the BepiColombo Mission. Planetary and Space Science. 58, 144-165. [2] - NASA Lunar Sample Compendium. https://curator.jsc.nasa.gov/lunar/lsc/

Redox History of Early Solar System Planetismals Recorded in the D;Orbigny Angrite

DOE Office of Scientific and Technical Information (OSTI.GOV)

King, P.L.; Sutton, S.R.; Spilde, M.N.

2012-04-02

Angrites are ancient basaltic meteorites ({approx}4.56 Ga) that preserve evidence of some of the solar system's earliest melting events. The volcanic-textured angrites such as D'Orbigny were rapidly crystallized and are relatively pristine; lacking shock, brecciation, and parent-body weathering textures. Thus, these angrites provide a unique 'window' into the petrogenesis of planetary bodies in the early solar system. Angrites may be formed by partial melting of CV chondrites under relatively oxidized sources compared to the eucrites, and therefore may document variations in fO{sub 2} conditions on carbonaceous chondrite parent bodies. Thus, understanding the intrinsic fO{sub 2} conditions of the angrites ismore » needed to determine how different early Solar System basalts form, to model separation of the core, mantle and crust, and to understand magnetic fields on planetary bodies. The D'Orbigny angrite contains a range of textures: (a) crystalline texture containing interlocking crystals of fassaite (pyroxene) with Ti-rich rims, anorthite, and Mg-olivine with Fe-rich rims; (b) cavities with protruding needle-like pyroxene and anorthite dusted by Ca-(Mg)-carbonate; (c) mesostasis with kirschsteinite, ilmenite, troilite, phosphates (e.g., merrilite, whitlockite and Casilicophosphate), rhonite and minor glass; (d) glasses ({approx} angrite composition) in vesicles, as inclusions and as beads, and also cross-cutting crystal-rich portions of the rock; (e) vesicles (e.g., {approx}1.4 vol. %, 0.0219-87.7 mm{sup 3}). Analysis of the textures and Fe{sup 3+}/Fetotal of the cavity pyroxene suggests that the oxygen fugacity (fO{sub 2}) increased in the D'Orbigny angrite perhaps due to introduction of a gas phase. Here we examine the detailed fO{sub 2} history using micro-analyses that allow us to avoid inclusions that may cause spurious results. We present analyses of both S- and V- oxidation states to complement other work using Fe-oxidation state and to avoid problems related to measuring low concentrations of Fe{sup 3+} and propagating errors when calculating fO{sub 2} in samples with low Fe{sup 3+} concentrations.« less

Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) with Raman Imaging Applied to Lunar Meteorites.

PubMed

Smith, Joseph P; Smith, Frank C; Booksh, Karl S

2018-03-01

Lunar meteorites provide a more random sampling of the surface of the Moon than do the returned lunar samples, and they provide valuable information to help estimate the chemical composition of the lunar crust, the lunar mantle, and the bulk Moon. As of July 2014, ∼96 lunar meteorites had been documented and ten of these are unbrecciated mare basalts. Using Raman imaging with multivariate curve resolution-alternating least squares (MCR-ALS), we investigated portions of polished thin sections of paired, unbrecciated, mare-basalt lunar meteorites that had been collected from the LaPaz Icefield (LAP) of Antarctica-LAP 02205 and LAP 04841. Polarized light microscopy displays that both meteorites are heterogeneous and consist of polydispersed sized and shaped particles of varying chemical composition. For two distinct probed areas within each meteorite, the individual chemical species and associated chemical maps were elucidated using MCR-ALS applied to Raman hyperspectral images. For LAP 02205, spatially and spectrally resolved clinopyroxene, ilmenite, substrate-adhesive epoxy, and diamond polish were observed within the probed areas. Similarly, for LAP 04841, spatially resolved chemical images with corresponding resolved Raman spectra of clinopyroxene, troilite, a high-temperature polymorph of anorthite, substrate-adhesive epoxy, and diamond polish were generated. In both LAP 02205 and LAP 04841, substrate-adhesive epoxy and diamond polish were more readily observed within fractures/veinlet features. Spectrally diverse clinopyroxenes were resolved in LAP 04841. Factors that allow these resolved clinopyroxenes to be differentiated include crystal orientation, spatially distinct chemical zoning of pyroxene crystals, and/or chemical and molecular composition. The minerals identified using this analytical methodology-clinopyroxene, anorthite, ilmenite, and troilite-are consistent with the results of previous studies of the two meteorites using electron microprobe analysis. To our knowledge, this is the first report of MCR-ALS with Raman imaging used for the investigation of both lunar and other types of meteorites. We have demonstrated the use of multivariate analysis methods, namely MCR-ALS, with Raman imaging to investigate heterogeneous lunar meteorites. Our analytical methodology can be used to elucidate the chemical, molecular, and structural characteristics of phases in a host of complex, heterogeneous geological, geochemical, and extraterrestrial materials.

Origin of coronas in metagabbros of the Adirondack mts., N. Y

USGS Publications Warehouse

Whitney, P.R.; McLelland, J.M.

1973-01-01

Metagabbros from two widely separated areas in the Adirondacks show development of coronas. In the Southern Adirondacks, these are cored by olivine which is enclosed in a shell of orthopyroxene that is partially, or completely, rimmed by symplectites consisting of clinopyroxene and spinel. Compositions of the corona phases have been determined by electron probe and are consistent with a mechanism involving three partial reactions, thus: (a) Olivine=Orthopyroxene+(Mg, Fe)++. (b) Plagioclase+(Mg, Fe)+++Ca++=Clinopyroxene+Spinel+Na+. (c) Plagioclase+(Mg, Fe)+++Na+=Spinel+more sodic plagioclase+Ca++. Reaction (a) occurs in the inner shell of the corona adjacent to olivine; reaction (b) in the outer shell; and (c) in the surrounding plagioclase, giving rise to the spinel clouding which is characteristic of the plagioclase in these rocks. Alumina and silica remain relatively immobile. These reactions, when balanced, can be generalized to account for the aluminous nature of the pyroxenes and for changing plagioclase composition. Summed together, the partial reactions are equivalent to: (d) Olivine + Anorthite = Aluminous orthopyroxene + Aluminous Clinopyroxene + Spinel (Kushiro and Yoder, 1966). In the Adirondack Highlands, coronas between olivine and plagioclase commonly have an outer shell of garnet replacing the clinopyroxene/spinel shell. The origin of the garnet can also be explained in terms of three partial reactions: (e) Orthopyroxene+Ca++=Clinopyroxene+(Mg, Fe)++. (f) Clinopyroxene+Spinel+Plagioclase+(Mg, Fe)++=Garnet+Ca+++Na+. (g) Plagioclase+(Mg, Fe)+++Na+=Spinel + more sodic plagioclase+Ca++. These occur in the inner and outer corona shell and the surrounding plagioclase, respectively, and involve the products of reactions (a)-(d). Alumina and silica are again relatively immobile. Balanced, and generalized to account for aluminous pyroxenes and variable An content of plagioclase, they are equivalent to: (h) Orthopyroxene+Anorthite+Spinel=Garnet (Green and Ringwood, 1967). Amphibole coronas about opaque oxides in rocks of both areas are the result of oxide/plagioclase reactions with addition of magnesium from coexisting olivine. Based on published experimental data, pressure and temperature at the time of corona formation were on the order of 8 kb and 800?? C for the garnet bearing coronas, with somewhat lower pressures indicated for the clinopyroxene/spinel coronas. ?? 1973 Springer-Verlag.

Precise new shock temperatures in forsterite and in silicate liquids: phase transitions and heat capacity at high pressure

NASA Astrophysics Data System (ADS)

Asimow, P. D.; Fat'yanov, O. V.; Su, C.; Ma, X. J.

2017-12-01

Shock temperature measurements in transparent samples provide key constraints on the phase transitions and thermodynamic properties of materials at high pressure and temperature. Such measurements are necessary, for example, to allow equation of state measurements taken along the Hugoniot to be translated to P-V-T space. We have recently completed a detailed study of the accuracy and reproducibility of calibration of our 6-channel fast pyrometer. We have also introduced improved analysis procedures of the time-dependent multi-wavelength radiance signal that avoid the need for a greybody assumption and therefore have better precision than earlier results. This has motivated (a) renewed study of the shock temperature of forsterite in the superheating, partial melting, and complete melting regimes, (b) pre-heated diopside-anorthite glass shock temperature experiments for comparison to pre-heated silicate liquid equation of state results, and (c) new soda-lime glass shock temperature experiments. Single-crystal synthetic forsterite samples were shocked along (100) to pressures between 120 and 210 GPa on the Caltech two-stage light gas gun. Uncertainties on most results are 50 K. Results above the onset of partial melting at 130 GPa are consistent with Lyzenga and Ahrens (1980) data and show a low P-T slope consistent with a partial melting interval. Complete melting may occur, given sufficient time, at about 210 GPa. The experiment at 120-130 GPa is anomalous, showing two-wave structure and time- and wavelength-dependent scattering suggesting a subsolidus phase transition behind the shock front. The amount of super-heating, if any, is far smaller than claimed by Holland and Ahrens (1997). Steady radiation profiles, high emissivity, and consistency from channel to channel provide high precision (±40 K) in diopside-anorthite liquid shocked from just above the glass transition to high pressure. Temperatures are colder than expected for a model with constant heat capacity, providing direct evidence that multicomponent silicate liquids show a major increase in heat capacity in the P-T range appropriate to terrestrial magma oceans (<150 GPa, <5000 K).

Petrology of Amoeboid Olivine Aggregates in Antarctic CR Chondrites: Comparison With Other Carbonaceous Chondrites

NASA Technical Reports Server (NTRS)

Komatsu, M.; Fagan, T. J.; Yamaguchi, A.; Mikouchi, T.; Zolensky, M. E.; Yasutake, M.

2016-01-01

Amoeboid olivine aggregates (AOAs) are important refractory components of carbonaceous chondrites and have been interpreted to represent solar nebular condensates that experienced high-temperature annealing, but largely escaped melting. In addition, because AOAs in primitive chondrites are composed of fine-grained minerals (forsterite, anorthite, spinel) that are easily modified during post crystallization alteration, the mineralogy of AOAs can be used as a sensitive indicator of metamorphic or alteration processes. AOAs in CR chondrites are particularly important because they show little evidence for secondary alteration. In addition, some CR AOAs contain Mn-enriched forsterite (aka low-iron, Mn-enriched or LIME olivine), which is an indicator of nebular formation conditions. Here we report preliminary results of the mineralogy and petrology of AOAs in Antarctic CR chondrites, and compare them to those in other carbonaceous chondrites.

'Fluffy' Type A Ca-, Al-rich inclusions in the Allende meteorite

NASA Technical Reports Server (NTRS)

Macpherson, G. J.; Grossman, L.

1984-01-01

Inclusions called 'fluffy' Type A's or FTA's in the Allende meteorite are examined as possible candidates for relict vapor-solid condensate grains, remaining from the original solar nebula. Type A inclusions are characterized by abundant melilite and absence of primary anorthite and titaniferous pyroxene. Fluffy Type A's were probably loosely bound clumps of crystals drifting in the solar nebula, analogous to dustballs or snowflakes. Polished thin sections of all samples were studied optically and with a JEOL JSM-35 scanning electron microscope. It is reasonably clear that neither whole FTA's nor constituent nodules of the coarser grained ones were ever molten. Despite solid-state recrystallization which has affected these inclusions to varying degrees, the coarser grained material remaining in many of them is probably a relic of vapor-solid condensation in the solar nebula.

Trace element and Pb isotope composition of plagioclase from dome samples from the 2004-2005 eruption of Mount St. Helens, Washington: Chapter 35 in A volcano rekindled: the renewed eruption of Mount St. Helens, 2004-2006

USGS Publications Warehouse

Kent, Adam J.R.; Rowe, Michael C.; Thornber, Carl R.; Pallister, John S.; Sherrod, David R.; Scott, William E.; Stauffer, Peter H.

2008-01-01

Plagioclase crystals from gabbronorite inclusions in three dacite samples have markedly different trace-element and Pbisotope compositions from those of plagioclase phenocrysts, despite having a similar range of anorthite contents. Inclusions show some systematic differences from each other but typically have higher Ti, Ba, LREE, and Pb and lower Sr and have lower 208Pb/206Pb and 207Pb/206Pb ratios than coexisting plagioclase phenocrysts. The compositions of plagioclase from inclusions cannot be related to phenocryst compositions by any reasonable petrologic model. From this we suggest that they are unlikely to represent magmatic cumulates or restite inclusions but instead are samples of mafic Tertiary basement from beneath the volcano.

A petrologic and ion microprobe study of a Vigarano Type B refractory inclusion - Evolution by multiple stages of alteration and melting

NASA Technical Reports Server (NTRS)

Macpherson, Glenn J.; Davis, Andrew M.

1993-01-01

A Type B Ca-, Al-rich 6-m-diam inclusion (CAI) found in the Vigarano C3V chondrite was inspected using optical and scanning electron microscopies and ion microprobe analyses. It was found that the primary constituents of the CAI inclusion are (in percent), melilite (52), fassaite, (20), anorthite (18), spinel (10), and trace Fe-Ni metal. It is noted that, while many of the properties of the inclusion indicate solidification from a melt droplet, the Al-26/Mg-26 isotopic systematics and some textural relationships are incompatible with single-stage closed system crystallization of a homogeneous molten droplet, indicating that the history of this inclusion must have been more complex than melt solidification alone. Moreover, there was unusually high content of Na in melilite, suggesting that the droplet did not form by melting of pristine high-temperature nebular condensates.

Study of recrystallization and devitrification of lunar glass

NASA Technical Reports Server (NTRS)

Ulrich, D. R.

1974-01-01

The technique of differential thermal analysis (DTA) was applied to the study of the Apollo 17 orange soil (74220,63) and the Apollo 16 glass coated anorthite (64455,21). These glasses show accentuated exotherms of strain relief in the annealing range which is indicative of rapid cooling. These are amenable to interpretation by comparison to the known history of synthetic glasses. Synthetic glasses were prepared whose similarity in behavior between the lunar glasses and their synthetic analogs is striking. Approximate rates of cooling of the lunar glasses were determined from comparative DTA of lunar and synthetic glasses and from the determination of the relation of strain relief in the annealing range to quench rate. At higher temperatures the glasses show exotherms of crystallization. The crystallization products associated with the exothermic reactions have been identified by X-ray diffraction and the surface morphologies developed by strain relief and crystallization have been characterized with scanning electron microscopy.

Cordierite-spinel troctolite, a new magnesium-rich lithology from the lunar highlands

NASA Technical Reports Server (NTRS)

Marvin, Ursula B.; Carey, J. William; Lindstrom, Marilyn M.

1989-01-01

A clast of spineltroctolite containing 8 percent cordierite (Mg2,Al4Si5O18) has been identified among the constituents of Apollo 15 regolith breccia 15295. The cordierite and associated anorthite, forsteritic olivine, and pleonaste spinel represent a new, Mg-rich lunar highlands lithology that formed by metamorphism of an igneous spinel cumulate. The cordierite-forsterite pair in the assemblage is stable at a maximum pressure of 2.5 kilobars, equivalent to a depth of 50 kilometers, or 10 kilometers above the lunar crust-mantle boundary. The occurrence of the clast indicates that spinel cumulates are a more important constituent of the lower lunar crust than has been recognized. The rarity of cordierite-spinel troctolite among lunar rock samples suggests that it is excavated only by large impact events, such as the one that formed the adjacent Imbrium Basin.

Cordierite-spinel troctolite, a new magnesium-rich lithology from the lunar highlands.

PubMed

Marvin, U B; Carey, J W; Lindstrom, M M

1989-02-17

A clast of spinel troctolite containing 8 percent cordierite (Mg(2)Al(4)Si(5)O(18)) has been identified among the constituents of Apollo 15 regolith breccia 15295. The cordierite and associated anorthite, forsteritic olivine, and pleonaste spinel represent a new, Mg-rich lunar highlands lithology that formed by metamorphism of an igneous spinel cumulate. The cordierite-forsterite pair in the assemblage is stable at a maximum pressure of 2.5 kilobars, equivalent to a depth of 50 kilometers, or 10 kilometers above the lunar crust-mantle boundary. The occurrence of the clast indicates that spinel cumulates are a more important constituent of the lower lunar crust than has been recognized. The rarity of cordierite-spinel troctolite among lunar rock samples suggests that it is excavated only by large impact events, such as the one that formed the adjacent Imbrium Basin.

The solubility of gold in silicate melts: First results

NASA Technical Reports Server (NTRS)

Borisov, A.; Palme, H.; Spettel, B.

1993-01-01

The effects of oxygen fugacity and temperature on the solubility of Au in silicate melts were determined. Pd-Au alloys were equilibrated with silicate of anorthite-diopside eutectic composition at different T-fO2 conditions. The behavior of Au was found to be similar to that of Pd reported recently. Au solubilities for alloys with 30 to 40 at. percent Au decrease at 1400 C from 12 ppm in air to 160 ppb at a log fO2 = -8.7. The slope of the log(Me-solubility) vs. log(fO2) curve is close to 1/4 for Au and the simultaneously determined Pd suggesting a formal valence of Au and Pd of 1+. Near the IW buffer Pd and Au solubilities become even less dependent on fO2 perhaps reflecting the presence of some metallic Au and Pd.

Investigation of mechanical and thermal properties of microwave-sintered lunar simulant materials using 2.45 GHz radiation

NASA Technical Reports Server (NTRS)

Meek, T. T.

1990-01-01

The mechanical and thermal properties of lunar simulant material were investigated. An alternative method of examining thermal shock in microwave-sintered lunar samples was researched. A computer code was developed that models how the fracture toughness of a thermally shocked lunar simulant sample is related to the sample hardness as measured by a micro-hardness indentor apparatus. This technique enables much data to be gathered from a few samples. Several samples were sintered at different temperatures and for different times at the temperatures. The melting and recrystallization characteristics of a well-studied binary system were also investigated to see if the thermodynamic barrier for the nucleation of a crystalline phase may be affected by the presence of a microwave field. The system chosen was the albite (sodium alumino silicate) anorthite system (calcium alumino silicate). The results of these investigations are presented.

Synchrotron Radiation XRD Analysis of Indialite in Y-82094 Ungrouped Carbonaceous Chondrite

NASA Technical Reports Server (NTRS)

Mikouchi, T.; Hagiya, K.; Sawa, N.; Kimura, M.; Ohsumi, K.; Komatsu, M.; Zolensky, M.

2016-01-01

Y-82094 is an ungrouped type 3.2 carbonaceous chondrite, with abundant chondrules making 78 vol.% of the rock. Among these chondrules, an unusual porphyritic Al-rich magnesian chondrule is reported that consists of a cordierite-like phase, Al-rich orthopyroxene, cristobalite, and spinel surrounded by an anorthitic mesostasis. The reported chemical formula of the cordierite-like phase is Na(0.19)Mg(1.95)Fe(0.02)Al(3.66)Si(5.19)O18, which is close to stoichiometric cordierite (Mg2Al3[AlSi5O18]). Although cordierite can be present in Al-rich chondrules, it has a high temperature polymorph (indialite) and it is therefore necessary to determine whether it is cordierite or indialite in order to better constrain its formation conditions. In this abstract we report on our synchrotron radiation X-ray diffraction (SR-XRD) study of the cordierite-like phase in Y-82094.

Magnetic Susceptibility Measurements for in Situ Characterization of Lunar Soil

NASA Technical Reports Server (NTRS)

Oder, R. R.

1992-01-01

Magnetic separation is a viable method for concentration of components of lunar soils and rocks for use as feedstocks for manufacture of metals, oxygen, and for recovery of volatiles such as He-3. Work with lunar materials indicates that immature soils are the best candidates for magnetic beneficiation. The magnetic susceptibility at which selected soil components such as anorthite, ilmenite, or metallic iron are separated is not affected by soil maturity, but the recovery of the concentrated components is. Increasing soil maturity lowers recovery. Mature soils contain significant amounts of glass-encased metallic iron. Magnetic susceptibility, which is sensitive to metallic iron content, can be used to measure soil maturity. The relationship between the ratio of magnetic susceptibility and iron oxide and the conventional maturity parameter, I(sub s)/FeO, ferromagnetic resonant intensity divided by iron oxide content is given. The magnetic susceptibilities were determined using apparatus designed for magnetic separation of the lunar soils.

Mineralogy and geochemistry of Eocene Helete formation , Adiyaman, Turkey

NASA Astrophysics Data System (ADS)

Choi, J.; Lee, I.; Yildirim, E.

2013-12-01

Helete formation is located at Adiyaman, Turkey which is in the Alpine-Himalayan orogeny belt. Helete formation is represented by andesitic, basaltic and gabbroic rocks cut by localized felsic intrusions and overlain by open-marine Nummulitic carbonate sediments. Electron microprobe analyses were conducted for 15 rocks samples of Helete formation. These rock samples are named as basalt, andesite, gabbro, diorite, dacite, and granite. Basalt and andesite samples are composed of clinopyroxene(augite), plagioclase(Ab98-96), carbonate, and hyaline. Gabbro samples have wide range of plagioclase composition from anorthite to albite(Ab92-16), and other minerals like clinopyroxene(augite) and amphibole(hornblende and actinolite). Diabase samples consist of epidote group minerals and sphene with plagioclase(Ab80), pyroxene and hornblende. Dacite samples are composed of dolomite and quartz. Granite samples are composed of quartz, chlorite, and plagioclase which range from albite to oligoclase in composition (Ab98-89).

Vitreous Anorthite (CaAl2Si2O8) at High Pressure: A First-Principles Molecular Dynamics Study

NASA Astrophysics Data System (ADS)

Ghosh, D. B.; Karki, B. B.

2017-12-01

Due to the high abundance of silicates and aluminosilicates inside the earth, their corresponding melts are likely to be one of the key transport agents in the chemical and thermal evolution of our planet and therefore, have long been the subject of investigations. Experimentally, in-situ melt properties of these materials, particularly at high pressure-temperature conditions are extremely difficult to constrain and the corresponding glass phases are considered as analogs. This, however, prohibits one-to-one comparison between the properties of silicate melt and its corresponding glass. With the aim to enable such comparison, we investigate the equation of state and structural properties of CaAl2Si2O8 glass at 300 K as a function of pressure up to 160 GPa from first principles molecular dynamics simulation results. Our results show that at ambient pressure: (i) Si's remain mostly (> 95%) under tetrahedral oxygen surroundings, (ii) unlike anorthite crystal, presence of high coordination (> 4) Al's with 30% abundance, (iii) and significant presence of both non bridging (8%) and triply (17%) coordinated oxygen. In the 0-10 GPa interval, mainly topological changes occur in the Si-O (also Al-O to some extent) surroundings in the cold compressed case in comparison to smooth increase in the average bond distance and coordination in the hot compressed case. Further compression results in gradual increases in: mean coordination, proportion of O-triclusters and increasing appearance of tetrahedral oxgyens, with Si-O (Al-O) reaching 6 (6.5) and O-T > 3 (T=Si and Al) at the highest compression. Due to the absence of kinetic barrier, the hot compressed glasses consistently produce greater densities and higher coordination numbers than the cold compression cases. Decompressed glasses show irreversible compaction along with retention of high coordination species when decompressed from > 10 GPa and degree of irreversibility depends on the peak pressure of decompression. These structural details suggest that the pressure response of the cold compressed glasses are not only inherently different in the 0 - 10 GPa interval, the density and the average coordination are consistently lower than the hot compressed glasses. Hot-compressed glasses may therefore be the better analog in the study of high-pressure silicate melts.

Volatile and light lithophile elements in high-anorthite plagioclase-hosted melt inclusions from Iceland

NASA Astrophysics Data System (ADS)

Neave, David A.; Hartley, Margaret E.; Maclennan, John; Edmonds, Marie; Thordarson, Thorvaldur

2017-05-01

Melt inclusions formed during the early stages of magmatic evolution trap primitive melt compositions and enable the volatile contents of primary melts and the mantle to be estimated. However, the syn- and post-entrapment behaviour of volatiles in primitive high-anorthite plagioclase-hosted melt inclusions from oceanic basalts remains poorly constrained. To address this deficit, we present volatile and light lithophile element analyses from a well-characterised suite of nine matrix glasses and 102 melt inclusions from the 10 ka Grímsvötn tephra series (i.e., Saksunarvatn ash) of Iceland's Eastern Volcanic Zone (EVZ). High matrix glass H2O and S contents indicate that eruption-related exsolution was arrested by quenching in a phreatomagmatic setting; Li, B, F and Cl did not exsolve during eruption. The almost uniformly low CO2 content of plagioclase-hosted melt inclusions cannot be explained by either shallow entrapment or the sequestration of CO2 into shrinkage bubbles, suggesting that inclusion CO2 contents were controlled by decrepitation instead. High H2O/Ce values in primitive plagioclase-hosted inclusions (182-823) generally exceed values expected for EVZ primary melts (∼ 180), and can be accounted for by diffusive H2O gain following the entrainment of primitive macrocrysts into evolved and H2O-rich melts a few days before eruption. A strong positive correlation between H2O and Li in plagioclase-hosted inclusions suggests that diffusive Li gain may also have occurred. Extreme F enrichments in primitive plagioclase-hosted inclusions (F/Nd = 51-216 versus ∼15 in matrix glasses) possibly reflect the entrapment of inclusions from high-Al/(Al + Si) melt pools formed by dissolution-crystallisation processes (as indicated by HFSE depletions in some inclusions), and into which F was concentrated by uphill diffusion since F is highly soluble in Al-rich melts. The high S/Dy of primitive inclusions (∼300) indicates that primary melts were S-rich in comparison with most oceanic basalts. Cl and B are unfractionated from similarly compatible trace elements, and preserve records of primary melt heterogeneity. Although primitive plagioclase-hosted melt inclusions from the 10 ka Grímsvötn tephra series record few primary signals in their volatile contents, they nevertheless record information about crustal magma processing that is not captured in olivine-hosted melt inclusions suites.

Organic-inorganic interactions at oil-water contacts: quantitative retracing of processes controlling the CO2 occurrence in Norwegian oil reservoirs

NASA Astrophysics Data System (ADS)

van Berk, Wolfgang; Schulz, Hans-Martin

2010-05-01

Crude oil quality in reservoirs can be modified by degradation processes at oil-water contacts (OWC). Mineral phase assemblages, composition of coexisting pore water, and type and amount of hydrocarbon degradation products (HDP) are controlling factors in complex hydrogeochemical processes in hydrocarbon-bearing siliciclastic reservoirs, which have undergone different degrees of biodegradation. Moreover, the composition of coexisting gas (particularly CO2 partial pressure) results from different pathways of hydrogeochemical equilibration. In a first step we analysed recent and palaeo-OWCs in the Heidrun field. Anaerobic decomposition of oil components at the OWC resulted in the release of methane and carbon dioxide and subsequent dissolution of feldspars (anorthite and adularia) leading to the formation of secondary kaolinite and carbonate phases. Less intensively degraded hydrocarbons co-occur with calcite, whereas strongly degraded hydrocarbons co-occur with solid solution carbonate phase (siderite, magnesite, calcite) enriched in δ13C. To test such processes quantitatively in a second step, CO2 equilibria and mass transfers induced by organic-inorganic interactions have been hydrogeochemically modelled in different semi-generic scenarios with data from the Norwegian continental shelf (acc. Smith & Ehrenberg 1989). The model is based on chemical thermodynamics and includes irreversible reactions representing hydrolytic disproportionation of hydrocarbons according to Seewald's (2006) overall reaction (1a) which is additionally applied in our modelling work in an extended form including acetic acid (1b): (1) R-CH2-CH2-CH3 + 4H2O -> R + 2CO2 + CH4 + 5H2, (2) R-CH2-CH2-CH3 + 4H2O -> R + 1.9CO2 + 0.1CH3COOH + 0.9CH4 + 5H2. Equilibrating mineral assemblages (different feldspar types, quartz, kaolinite, calcite) are based on the observed primary reservoir composition at 72 °C. Modelled equilibration and coupled mass transfer were triggered by the addition and reaction of different amounts of HDP. Modelled CO2 partial pressure values in a multicomponent gas phase equilibrated with K-feldspar, quartz, kaolinite, and calcite resemble measured data. Similar CO2 contents result from acetic acid addition (eq. 1b). Equilibration with albite or anorthite reduces the release of CO2 into the multicomponent gas phase dramatically, by 1 or 4 orders of magnitude compared with the equilibration with K-feldspar (van Berk et al., 2009). Third and based on data by Ehrenberg & Jakobsen (2001), the effects of organic-inorganic interactions at OWCs in Brent Group reservoir sandstones from the Gullfaks Oilfield (offshore Norway) have been hydrogeochemically modelled. Observed local changes in mineral phase assemblage compositions (content of different feldspar types, kaolinite, carbonate) and CO2 partial pressures are attributed to varying degrees of oil-biodegradation (up to more than 10 %; Horstadt et al. 1992). Modelling results are congruent with observations and indicate that (i) intense dissolution of anorthite, (ii) less intense dissolution of albite, (iii) minor dissolution of K-feldspar, (iv) intense precipitation of kaolinite and quartz, (v) less intense precipitation of carbonate, and (vi) formation of CO2 partial pressures are driven by the release of HDP. References Ehrenberg SN & Jakobsen KG (2001) Plagioclase dissolution related to biodegradation of oil in Brent Group sandstones (Middle Jurassic) of Gullfaks Field, northern North Sea. Sedimentology, 48, 703-721. Smith JT & Ehrenberg SN (1989) Correlation of carbon dioxide abundance with temperature in clastic hydrocarbon reservoirs: relationship to inorganic chemical equilibrium. Marine and Petroleum Geology, 6, 129-135. Seewald JS (2003) Organic-inorganic interactions in petroleum-producing sedimentary basins. Nature, 426, 327-333. van Berk, W, Schulz, H-M & Fu, Y (2009) Hydrogeochemical modelling of CO2 equilibria and mass transfer induced by organic-inorganic interactions in siliciclastic petroleum reservoirs. Geofluids, 9, 253-262.

Production of glass-ceramics from sewage sludge and waste glass

NASA Astrophysics Data System (ADS)

Rozenstrauha, I.; Sosins, G.; Petersone, L.; Krage, L.; Drille, M.; Filipenkov, V.

2011-12-01

In the present study for recycling of sewage sludge and waste glass from JSC "Valmieras stikla skiedra" treatment of them to the dense glass-ceramic composite material using powder technology is estimated. The physical-chemical properties of composite materials were identified - density 2.19 g/cm3, lowest water absorption of 2.5% and lowest porosity of 5% for the samples obtained in the temperature range of sintering 1120 - 1140 °C. Regarding mineralogical composition of glass-ceramics the following crystalline phases were identified by XRD analysis: quartz (SiO2), anorthite (CaAl2Si2O8) and hematite (Fe2O3), which could ensure the high density of materials and improve the mechanical properties of material - compressive strength up to 60.31±5.09 - 52.67±19.18 MPa. The physical-chemical properties of novel materials corresponds to dense glass-ceramics composite which eventually could be used as a building material, e.g. for floor covering, road pavement, exterior tiles etc.

Plasma vitrification and re-use of non-combustible fiber reinforced plastic, gill net and waste glass.

PubMed

Chu, J P; Chen, Y T; Mahalingam, T; Tzeng, C C; Cheng, T W

2006-12-01

Fiber reinforced plastic (FRP) composite material has widespread use in general tank, special chemical tank and body of yacht, etc. The purpose of this study is directed towards the volume reduction of non-combustible FRP by thermal plasma and recycling of vitrified slag with specific procedures. In this study, we have employed three main wastes such as, FRP, gill net and waste glass. The thermal molten process was applied to treat vitrified slag at high temperatures whereas in the post-heat treatment vitrified slags were mixed with specific additive and ground into powder form and then heat treated at high temperatures. With a two-stage heat treatment, the treated sample was generated into four crystalline phases, cristobalite, albite, anorthite and wollastonite. Fine and relatively high dense structures with desirable properties were obtained for samples treated by the two-stage heating treatment. Good physical and mechanical properties were achieved after heat treatment, and this study reveals that our results could be comparable with the commercial products.

Shock-induced transformations in the system NaAlSiO4-SiO2 - A new interpretation

NASA Technical Reports Server (NTRS)

Sekine, Toshimori; Ahrens, Thomas J.

1992-01-01

New internally consistent interpretations of the phases represented by the high pressure phase shock wave data for an albite-rich rock, jadeite, and nepheline in the system NaAlSiO4-SiO2, are obtained using the results of static high pressure investigations, and the recent discovery of the hollandite phase in a shocked meteorite. We conclude that nepheline transforms directly to the calcium ferrite structure, whereas albite transforms possibly to the hollandite structure. Shock Hugoniots for the other plagioclase and alkali feldspars also indicate that these transform to hollandite structures. The pressure-volume data at high pressure could alternatively represent the compression of an amorphous phase. Moreover, the shock Hugoniot data are expected to reflect the properties of the melt above shock stresses of 60-80 GPa. The third order Birch-Murnaghan equation of state parameters are given for the calcium ferrite type NaAlSiO4 and for albite-rich, orthoclase-rich, and anorthite-rich hollandites.

REE Partitioning in Lunar Minerals

NASA Technical Reports Server (NTRS)

Rapp, J. F.; Lapen, T. J.; Draper, D. S.

2015-01-01

Rare earth elements (REE) are an extremely useful tool in modeling lunar magmatic processes. Here we present the first experimentally derived plagioclase/melt partition coefficients in lunar compositions covering the entire suite of REE. Positive europium anomalies are ubiquitous in the plagioclase-rich rocks of the lunar highlands, and complementary negative Eu anomalies are found in most lunar basalts. These features are taken as evidence of a large-scale differentiation event, with crystallization of a global-scale lunar magma ocean (LMO) resulting in a plagioclase flotation crust and a mafic lunar interior from which mare basalts were subsequently derived. However, the extent of the Eu anomaly in lunar rocks is variable. Fagan and Neal [1] reported highly anorthitic plagioclase grains in lunar impact melt rock 60635,19 that displayed negative Eu anomalies as well as the more usual positive anomalies. Indeed some grains in the sample are reported to display both positive and negative anomalies. Judging from cathodoluminescence images, these anomalies do not appear to be associated with crystal overgrowths or zones.

Thermodynamic tabulations for selected phases in the system CaO-Al2O3-SiO2-H2 at 101.325 kPa (1 atm) between 273.15 and 1800 K

USGS Publications Warehouse

Haas, John L.; Robinson, Glipin R.; Hemingway, Bruch S.

1981-01-01

The standard thermodynamic properties of phases in the lime‐alumina‐silica‐ water system between 273.15 and 1800 K at 101.325 kPa (1 atm) were evalated from published experimental data. Phases included in the compilation are boehmite, diaspore, gibbsite, kaolinite, dickite, halloysite, andalusite, kyanite, sillimanite, Ca‐Al cliniopyroxene, anorthite, gehlenite, grossular, prehnite, zoisite, margarite, wollastonite, cyclowollastonite ( = pseudowollastonite), larnite, Ca olivine, hatrurite, and rankinite. The properties include heat capacity, entropy, relative enthalpy, and the Gibbs energy function of the phases and the enthalpies, Gibbs energies, and equilibrium constants for formation both from the elements and the oxides. Tabulated values are given at 50 K intervals with the 2‐sigma confidence limit at 250 K intervals. Summaries for each phase give the temperature‐ dependent functions for heat capacity, entropy, and relative enthalpy and the experimental data used in the final evaluation.

Mineralogy of ash of some American coals: variations with temperature and source

USGS Publications Warehouse

Mitchell, R.S.; Gluskoter, H.J.

1976-01-01

Ten samples of mineral-matter residue were obtained by the radio-frequency low-temperature ashing of subbituminous and bituminous coals. The low-temperature ash samples were then heated progressively from 400 ??C to 1400 ??C at 100 ??C intervals. Mineral phases present at each temperature interval were determined by X-ray diffraction analyses. The minerals originally present in the coals (quartz, kaolinite, illite, pyrite, calcite, gypsum, dolomite, and sphalerite) were all altered to higher temperature phases. Several of these phases, including kaolinite, metakaolinite, mullite, anhydrite, and anorthite, were found only in limited temperature ranges. Therefore the temperature of formation of the ashes in which they occur may be determined. Mineralogical differences were observed between coal samples from the Rocky Mountain Province, the Illinois Basin, and the Appalachians; and as a result of these mineralogical differences, different high-temperature phases resulted as the samples were heated. However, regional generalizations cannot be made until a greater number of samples have been studied. ?? 1976.

Structure, dynamics and stability of water/scCO2/mineral interfaces from ab initio molecular dynamics simulations.

PubMed

Lee, Mal-Soon; Peter McGrail, B; Rousseau, Roger; Glezakou, Vassiliki-Alexandra

2015-10-12

The boundary layer at solid-liquid interfaces is a unique reaction environment that poses significant scientific challenges to characterize and understand by experimentation alone. Using ab initio molecular dynamics (AIMD) methods, we report on the structure and dynamics of boundary layer formation, cation mobilization and carbonation under geologic carbon sequestration scenarios (T = 323 K and P = 90 bar) on a prototypical anorthite (001) surface. At low coverage, water film formation is enthalpically favored, but entropically hindered. Simulated adsorption isotherms show that a water monolayer will form even at the low water concentrations of water-saturated scCO2. Carbonation reactions readily occur at electron-rich terminal Oxygen sites adjacent to cation vacancies that readily form in the presence of a water monolayer. These results point to a carbonation mechanism that does not require prior carbonic acid formation in the bulk liquid. This work also highlights the modern capabilities of theoretical methods to address structure and reactivity at interfaces of high chemical complexity.

A geologic assessment of potential lunar ores

NASA Technical Reports Server (NTRS)

Mckay, D. S.; Williams, R. J.

1979-01-01

Although bulk lunar soil is not a suitable feedstock for extracting metals, certain minerals such as anorthite and ilmenite can be separated and concentrated. These minerals can be considered as potential ores of aluminum, silicon, titanium, andiron. A separation and metal extraction plant could also extract large amounts of oxygen and perhaps hydrogen from these minerals. Anorthie containing 19 percent aluminum and 20 percent silicon can be concentrated from some highland soils where it is present in amounts up to 60 percent. Ilmenite containing 32 percent titanium and 37 percent iron can be concentrated from some mare soils where it is present in amounts up to 10 percent. The ideal mining site would be located at the boundary between a high-titanium mare and a high-aluminum highlands. Such area may exist around the rims of some eastern maria, particularly Tranquilitatis. A location on Earth with raw materials as described above would be considered an economically valuable ore deposit if conventional terrestrial resources were not available.

The composition and origin of the moon

NASA Technical Reports Server (NTRS)

Anderson, D. L.

1972-01-01

A model is presented of the moon as a high temperature condensate from the solar nebula. The Ca, Al, and Ti rich compounds condense first in a cooling nebula. The initial high temperature mineralogy is gehlenite, spinel, perovskite, Ca-Al-rich pyroxenes, and anorthite. Type 3 carbonaceous chondrites such as the Allende meteorite are composed primarily of these minerals and are highly enriched in refractories. These inclusions can yield basalt and anorthosite in the proportions required to eliminate the europium anomaly, leaving a residual spinel-melilite interior. The inferred high U content of the lunar interior, both from the Allende analogy and the high heat flow, indicates a high temperature interior. The model is consistent with extensive early, shallow melting at 3 A.E., and with high deep internal temperatures. It is predicted that the outer 250 km is rich in plagioclase and FeO. The low iron content of the interior raises the interior temperatures estimated from electrical conductivity by some 800 C.

Structure, dynamics and stability of water/scCO 2/mineral interfaces from ab initio molecular dynamics simulations

DOE PAGES

Lee, Mal -Soon; Peter McGrail, B.; Rousseau, Roger; ...

2015-10-12

Here, the interface between a solid and a complex multi-component liquid forms a unique reaction environment whose structure and composition can significantly deviate from either bulk or liquid phase and is poorly understood due the innate difficulty to obtain molecular level information. Feldspar minerals, as typified by the Ca-end member Anorthite, serve as prototypical model systems to assess the reactivity and ion mobility at solid/water-bearing supercritical fluid (WBSF) interfaces due to recent X-ray based measurements that provide information on water-film formation, and cation vacancies at these surfaces. Using density functional theory based molecular dynamics, which allows the evaluation of reactivitymore » and condensed phase dynamics on equal footing, we report on the structure and dynamics of water nucleation and surface aggregation, carbonation and Ca mobilization under geologic carbon sequestration scenarios (T = 323 K and P = 90 bar). We find that water has a strong enthalpic preference for aggregation on a Ca-rich, O-terminated anorthite (001) surface, but entropy strongly hinders the film formation at very low water concentrations. Carbonation reactions readily occur at electron-rich terminal Oxygen sites adjacent to cation vacancies, when in contact with supercritical CO 2. Cation vacancies of this type can form readily in the presence of a water layer that allows for facile and enthalpicly favorable Ca 2+ extraction and solvation. Apart from providing unprecedented molecular level detail of a complex three component (mineral, water and scCO 2) system), this work highlights the ability of modern capabilities of AIMD methods to begin to qualitatively and quantitatively address structure and reactivity at solid-liquid interfaces of high chemical complexity. This work was supported by the US Department of Energy, Office of Fossil Energy (M.-S. L., B. P. M. and V.-A. G.) and the Office of Basic Energy Science, Division of Chemical Sciences, Geosciences and Biosciences (R.R.), and performed at the Pacific Northwest National Laboratory (PNNL). PNNL is a multi-program national laboratory operated for DOE by Battelle. Computational resources were provided by PNNL’s Platform for Institutional Computing (PIC), the W. R. Wiley Environmental Molecular Science Laboratory (EMSL), a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research located at PNNL and the National Energy Research Scientific Computing Center (NERSC) at Lawrence Berkeley National Laboratory.« less

Petrogenesis and tectonic implications of gabbro and plagiogranite intrusions in mantle peridotites of the Myitkyina ophiolite, Myanmar

NASA Astrophysics Data System (ADS)

Xu, Yang; Liu, Chuan-Zhou; Chen, Yi; Guo, Shun; Wang, Jian-Gang; Sein, Kyaing

2017-07-01

Centimeter-size intrusions of gabbros and plagiogranites occur in mantle peridotites of the Myitkyina ophiolite, Myanmar. The gabbros mainly consist of plagioclase and clinopyroxene, whereas orthopyroxene occasionally occurs. The plagiogranites are mainly composed of plagioclase, quartz and amphibole, with small amount of accessory minerals, such as zircon, apatite and rutile. Plagioclase in the gabbros varies from andesine to anorthite (An37-91), whereas plagioclase in the plagiogranites is less calcic (An1-40). Clinopyroxene in the gabbros is pervasively altered to hornblende. The gabbros contain 42.97-52.88 wt% SiO2, which show negative correlations with Al2O3, CaO and MgO, but positive correlations with Na2O, P2O5 and TiO2. Microtextural relations reveal the crystallization of clinopyroxene prior to plagioclase in the Myitkyina gabbros. This suggests that the gabbros were crystallized from hydrous melts, which is also supported by the occurrence of orthopyroxene and anorthitic plagioclase in some gabbros. The gabbros have slightly enriched Sr-Nd isotopes, with initial 87Sr/86Sr ratios of 0.703938-0.706609 and εNd(t) values of + 2.4-+7.2, and relatively variable Hf isotopes, with εHf(t) values of + 13.4-+24.9. A subduction component is required to explain the decoupled Nd-Hf isotopes of the gabbros. Binary mixing suggests that addition of ca 2% subducted sediments to a depleted mantle can account for the Nd-Hf decoupling. Therefore, both petrological and geochemical data of the gabbros support that the Myitkyina ophiolite was originated in a supra-subduction zone setting. The plagiogranites have compositions of tonalites and trondhjemites, containing 56.93-77.93 wt% SiO2, 1.27-10.79 wt% Na2O and 0.05-0.71 wt% K2O. They are slightly enriched in LREE over HREE and display positive anomalies in Eu, Zr, Hf but negative Nb anomalies. Very low TiO2 contents (0.03-0.2 wt%) of the plagiogranites suggest that they were not products of fractional crystallization of MORB but were generated by hydrous melting of gabbros. This process is also supported by the nearly constant contents of both La and Yb with increasing SiO2 of the plagiogranites. The Sr-Nd-Hf isotopes of the plagiogranites indicate the involvement of crustal component in their genesis. We proposed that the Myitkyina plagiogranites were generated by partial melting of the mafic protoliths in the subducted slab.

Thermal Barrier Coatings Resistant to Glassy Deposits

NASA Astrophysics Data System (ADS)

Drexler, Julie Marie

Engineering of alloys has for years allowed aircraft turbine engines to become more efficient and operate at higher temperatures. As advancements in these alloy systems have become more difficult, ceramic thermal barrier coatings (TBCs), often yttria (7 wt %) stabilized zirconia (7YSZ), have been utilized for thermal protection. TBCs have allowed for higher engine operating temperatures and better fuel efficiency but have also created new engineering problems. Specifically, silica based particles such as sand and volcanic ash that enter the engine during operation form glassy deposits on the TBCs. These deposits can cause the current industrial 7YSZ thermal barrier coatings to fail since the glass formed penetrates and chemically interacts with the TBC. When this occurs, coating failure may occur due to a loss of strain tolerance, which can lead to fracture, and phase changes of the TBC material. There have been several approaches used to stop calcium-magnesium aluminio-silcate (CMAS) glasses (molten sand) from destroying the entire TBC, but overall there is still limited knowledge. In this thesis, 7YSZ and new TBC materials will be examined for thermochemical and thermomechanical performance in the presence of molten CMAS and volcanic ash. Two air plasma sprayed TBCs will be shown to be resistant to volcanic ash and CMAS. The first type of coating is a modified 7YSZ coating with 20 mol% Al2O3 and 5 mol% TiO2 in solid solution (YSZ+20Al+5Ti). The second TBC is made of gadolinium zirconate. These novel TBCs impede CMAS and ash penetration by interacting with the molten CMAS or ash and drastically changing the chemistry. The chemically modified CMAS or ash will crystallize into an apatite or anorthite phase, blocking the CMAS or ash from further destroying the coating. A presented mechanism study will show these coatings are effective due to the large amount of solute (Gd, Al) in the zirconia structure, which is the key to creating the crystalline apatite or anorthite phases. In fact, it will be shown that if the industrial standard 7YSZ coatings contained more Y2O3 they would be very effective in stopping CMAS penetration. Lastly, thermal cyclic testing of 7YSZ and YSZ+20Al+5Ti TBCs reveals that partially CMAS-impregnated TBCs can survive mechanically if cycled in thermal gradient while in most isothermal tests they would fail. Since parts in a jet engine are in a thermal gradient, this type of testing should be performed on future CMAS resistant TBCs.

Hydrogeochemical tracing of mineral water in Jingyu County, Northeast China.

PubMed

Yan, Baizhong; Xiao, Changlai; Liang, Xiujuan; Wu, Shili

2016-02-01

The east Jilin Province in China, Jingyu County has been explored as a potential for enriching mineral water. In order to assess the water quality and quantity, it is of crucial importance to investigate the origin of the mineral water and its flow paths. In this study, eighteen mineral springs were sampled in May and September of 2012, May and September of 2013, and May 2014 and the environment, evolvement, and reaction mechanism of mineral water formation were analysed by hydrochemical data analysis, geochemical modelling and multivariate statistical analysis. The results showed that the investigated mineral water was rich in calcium, magnesium, potassium, sodium, bicarbonate, chloride, sulphate, fluoride, nitrate, total iron, silicate, and strontium, and mineral water ages ranged from 11.0 to more than 61.0 years. The U-shape contours of the mineral ages indicate a local and discrete recharge. The mineral compositions of the rocks were olivine, potassium feldspar, pyroxene, albite, and anorthite and were under-saturated in the mineral water. The origin of mineral water was from the hydrolysis of basalt minerals under a neutral to slightly alkaline and CO2-rich environment.

NaSi⇌CaAl exchange equilibrium between plagioclase and amphibole

NASA Astrophysics Data System (ADS)

Spear, Frank S.

1980-03-01

The exchange equilibrium between plagioclase and amphibole, 2 albite+tschermakite=2 anorthite+glaucophane, has been calibrated empirically using data from natural amphibolites. The partition coefficient, K D, for the exchange reaction is ( X an/ X ab)plag ·(Na, M4/Ca, M4)amph.. Partitioning is systematic between plagioclase and amphibole in suites collected from single exposures, but the solid solutions are highly non-ideal: values of In K D range from -3.0 at X an=0.30 to -1.0 at X an=0.90 in samples from a single roadcut. Changes in both K D and the topology of the ternary reciprocal exchange diagram occur with increasing metamorphic grade. Temperature dependence of In K D is moderate with Δ ¯H≃35 to 47 kcal at X an=0.25; pressure dependence is small with Δ ¯V≃ -0.24 cal/bar. Usefulness of this exchange equilibrium as a geothermometer is restricted by uncertainties in the calculation of the amphibole formula from a microprobe analysis, especially with regard to Na, M4 in amphibole, to approximately ±50 ° C.

Compositional controls on spinel clouding and garnet formation in plagioclase of olivine metagabbros, Adirondack Mountains, New York

USGS Publications Warehouse

McLelland, J.M.; Whitney, P.R.

1980-01-01

Olivine metagabbros from the Adirondacks usually contain both clear and spinel-clouded plagioclase, as well as garnet. The latter occurs primarily as the outer rim of coronas surrounding olivine and pyroxene, and less commonly as lamellae or isolated grains within plagioclase. The formation of garnet and metamorphic spinel is dependent upon the anorthite content of the plagioclase. Plagioclase more sodic than An38??2 does not exhibit spinel clouding, and garnet rarely occurs in contact with plagioclase more albitic than An36??4. As a result of these compositional controls, the distribution of spinel and garnet mimics and visually enhances original igneous zoning in plagioclase. Most features of the arrangement of clear (unclouded) plagioclase, including the shells or moats of clear plagioclase which frequently occur inside the garnet rims of coronas, can be explained on the basis of igneous zoning. The form and distribution of the clear zones may also be affected by the metamorphic reactions which have produced the coronas, and by redistribution of plagioclase in response to local volume changes during metamorphism. ?? 1980 Springer-Verlag.

Structure of shock compressed model basaltic glass: Insights from O K-edge X-ray Raman scattering and high-resolution 27Al NMR spectroscopy

NASA Astrophysics Data System (ADS)

Lee, Sung Keun; Park, Sun Young; Kim, Hyo-Im; Tschauner, Oliver; Asimow, Paul; Bai, Ligang; Xiao, Yuming; Chow, Paul

2012-03-01

The detailed atomic structures of shock compressed basaltic glasses are not well understood. Here, we explore the structures of shock compressed silicate glass with a diopside-anorthite eutectic composition (Di64An36), a common Fe-free model basaltic composition, using oxygen K-edge X-ray Raman scattering and high- resolution 27Al solid-state NMR spectroscopy and report previously unknown details of shock-induced changes in the atomic configurations. A topologically driven densification of the Di64An36 glass is indicated by the increase in oxygen K-edge energy for the glass upon shock compression. The first experimental evidence of the increase in the fraction of highly coordinated Al in shock compressed glass is found in the 27Al NMR spectra. This unambiguous evidence of shock-induced changes in Al coordination environments provides atomistic insights into shock compression in basaltic glasses and allows us to microscopically constrain the magnitude of impact events or relevant processes involving natural basalts on Earth and planetary surfaces.

The Microstructure and Physical Properties of Incinerated Paper-Cullet-Clay Ceramics

NASA Astrophysics Data System (ADS)

Sahar, M. R.; Hamzah, K.; Rohani, M. S.; Samah, K. A.; Razi, M. M.

A series of ceramic based on (x) incinerated recycle paper - (80-x) cullet - 20 Kaolin clay (where 10×45 wt%) has successfully been made by slip casting technique followed by sintering at 1000 °C. The actual composition of ceramic is analyzed using Energy Dispersive of X-Ray (EDAX) while the phase existence is determined using X-Ray Diffraction (XRD) technique. Their microstructural morphology is observed under Scanning Electron Microscope (SEM) and the physical properties are measured in term of their thermal shrinkage and hardness. It is found that the ceramic contain mostly of Silica and the phase is dominated by the existence of Quartz (SiO2), Wollastonite (CaSiO3) and Anorthite (Ca(Al2SiO8)). The SEM micrograph shows that the morphology is dominated by the existence of granular structure, and then become smoother as the cullet level is further increased. It is also found out that the thermal shrinkage is in the range 18% - 6.5% while the hardness is in the range of 152MPa- 1.463 GPa depending on composition.

A Low Viscosity Lunar Magma Ocean Forms a Stratified Anorthitic Flotation Crust With Mafic Poor and Rich Units

NASA Astrophysics Data System (ADS)

Dygert, Nick; Lin, Jung-Fu; Marshall, Edward W.; Kono, Yoshio; Gardner, James E.

2017-11-01

Much of the lunar crust is monomineralic, comprising >98% plagioclase. The prevailing model argues the crust accumulated as plagioclase floated to the surface of a solidifying lunar magma ocean (LMO). Whether >98% pure anorthosites can form in a flotation scenario is debated. An important determinant of the efficiency of plagioclase fractionation is the viscosity of the LMO liquid, which was unconstrained. Here we present results from new experiments conducted on a late LMO-relevant ferrobasaltic melt. The liquid has an exceptionally low viscosity of 0.22-0.19+0.11 to 1.45-0.82+0.46 Pa s at experimental conditions (1,300-1,600°C; 0.1-4.4 GPa) and can be modeled by an Arrhenius relation. Extrapolating to LMO-relevant temperatures, our analysis suggests a low viscosity LMO would form a stratified flotation crust, with the oldest units containing a mafic component and with very pure younger units. Old, impure crust may have been buried by lower crustal diapirs of pure anorthosite in a serial magmatism scenario.

Experimental Determination of Li, Be and B Partitioning During CAI Crystallization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ryerson, F J; Brenan, J M; Phinney, D L

2005-01-12

The main focus of the work is to develop a better understanding of the distribution of the elements B, Be and Li in melilite, fassaitic clinop clinopy-roxene, anorthite and spinel, which are the primary constituents of calcium-aluminum-rich inclusions (CAIs). These elements are the parent or decay products of short-lived nuclides (specifically, {sup 7}Be and {sup 10}Be) formed by cosmic ray spallation reactions on silicon and oxygen. Recent observations suggest that some CAIs contain ''fossil'' {sup 7}Be and {sup 10}Be in the form of ''excess'' amounts of their decay products (B and Li). The exact timing of {sup 7}Be and {supmore » 10}Be production is unknown, but if it occurred early in CAI history, it could constrain the birthplace of CAIs to be within a limited region near the infant sun. Other interpretations are possible, however, and bear little significance to early CAI genesis. In order to interpret the anomalies as being ''primary'', and thus originating at high temperature, information on the intermineral partitioning of both parent and daughter elements is required.« less

The diorite at West Warren, south-central Massachusetts

USGS Publications Warehouse

Pomeroy, John S.

1974-01-01

Follated, syntectonic, concordant intrusive bodies of mostly diorite and meladiorite with less abundant quartz diorite and norite have been mapped in the West Warren area of south-central Massachusetts. The rocks of the pluton range from a medium colored phase of diorite and quartz diorite to a dark colored phase of meladiorite and norite. Major minerals In the dioritic rocks are calcic andesine, green hornblende, brown biotite, and hypersthene. Igneous textures are dominant, and retrograde or deuteric effects are generally minor. Silica and alumina contents of the dioritic rocks are somewhat higher than for average diorites; conversely, the oxides of iron, magnesium, and calcium are generally lower. Normative quartz, albite, and anorthite are higher and orthoclase is lower in the samples than In the average diorite. Sizeable plutons of diorite-norite are uncommon in central Massachusetts. The West Warren body, roughly 26 km2 (10 square miles) in area, bears little petrochemical relation to adjacent rock units. The pluton can be construed as belonging to a belt of intrusive mafic rocks which stretches from southeastern New York to coastal Maine.

High Precision Isotope Analyses Using Multi-Collector SIMS: Applications to Earth and Planetary Science.

NASA Astrophysics Data System (ADS)

Kita, N. T.; Ushikubo, T.; Valley, J. W.

2008-05-01

The CAMECA IMS-1280 large radius, multicollector ion microprobe at the Wisc-SIMS National Facility is capable of high accuracy and precision for in situ analysis of isotope ratios. With improved hardware stability and software capability, high precision isotope analyses are routinely performed, typically 5 min per spot. We have developed analytical protocols for stable isotope analyses of oxygen, carbon, Mg, Si and Sulfur using multi-collector Faraday Cups (MCFC) and achieved precision of 0.1-0.2 ‰ (1SD) from a typically 10μm spot analyses. A number of isotopically homogeneous mineral standards have been prepared and calibrated in order to certify the accuracy of analyses in the same level. When spatial resolution is critical, spot size is reduced down to sub- μm for δ 18O to obtain better than 0.5‰ (1SD) precision by using electron multiplier (EM) on multi-collection system. Multi-collection EM analysis is also applied at 10 ppm level to Li isotope ratios in zircon with precision better than 2‰ (1SD). A few applications will be presented. (1) Oxygen three isotope analyses of chondrules in ordinary chondrites revealed both mass dependent and mass independent oxygen isotope fractionations among chondrules as well as within individual chondrules. The results give constraints on the process of chondrule formation and origin of isotope reservoirs in the early solar system. (2) High precision 26Al-26Mg (half life of 0.73 Ma) chronology is applied to zoned melilite and anorthite from Ca, Al-rich inclusions (CAI) in Leoville meteorite, and a well-defined internal isochron is obtained. The results indicate the Al- Mg system was remained closed within 40ky of the crystallization of melilite and anorthite in this CAI. (3) Sub- μm spot analyses of δ18O in isotopically zoned zircon from high-grade metamorphism reveals a diffusion profile of ~6‰ over 2μm, indicating slow diffusion of oxygen in zircon. This result also implies that old Archean detrital zircons (> 4Ga) might preserve their primary oxygen isotopic records, which allows us to trace the geological processes of the early earth [1]. Lithium isotope analyses of pre- 4Ga zircon from Jack Hills show high Li abundance and low δ 7Li, indicating existence of highly weathered crustal material as early as 4.3Ga. In conclusion, these new techniques allow us to study small natural variations of stable isotopes at μm-scale that permit exciting and fundamental research where samples are small, precious, or zoned. [1] Page FZ et al. (2007) Am Min 92, 1772-1775.

Novel thermal barrier coatings (TBCs) that are resistant to high temperature attack by calcium oxide-magnesium oxide-silicon oxide-aluminum oxide (CMAS) glassy deposits

NASA Astrophysics Data System (ADS)

Aygun, Aysegul

2008-10-01

Higher performance and durability requirements of gas-turbine engines will require a new generation of thermal barrier coatings (TBCs). This is particularly true of engines operated at higher temperatures, where TBCs are subjected to attack by CaO-MgO-Al2O3-SiO 2 (CMAS) glassy deposits. In this work, a new approach for mitigating CMAS attack on TBCs is introduced, where up to 20 mol% Al2O 3 and 5 mol% TiO2 in the form of a solid solution is incorporated into Y2O3-stabilized ZrO2 (YSZ) TBCs. The fabrication of such TBCs with engineered chemistries is made possible by the solution-precursor plasma spray (SPPS) process, which is uniquely suited for depositing coatings of metastable ceramics with extended solid-solubilities. In the current work, the TBC serves as a reservoir of Al and Ti solutes, which are incorporated into the molten CMAS glass that is in contact with the TBC. An accumulation of Al concentration in the CMAS glass as it penetrates the TBC shifts the glass composition from the difficult-to-crystallize psuedowollastonite field to the easy-to-crystallize anorthite field. The incorporation of Ti in the glass promotes crystallization of the CMAS glass by serving as a nucleating agent. This combined effect results in the near-complete crystallization of the leading edge of the CMAS front into anorthite, essentially arresting the front. Both of these phenomena will help crystallize the CMAS glass, making it immobile and ineffective in penetrating the TBC. It is shown that incorporation of both Al and Ti in the CMAS glass is essential for this approach to be effective. Additionally, incorporation of Al and Ti as solutes is expected to alleviate thermal-expansion and thermal-conductivity issues associated with crystalline second phases used before. Moreover, the metastable nature of the Al and Ti solutes will make them more readily available for incorporation in the molten CMAS glass. CMAS interactions with SPPS TBCs of various metastable compositions are compared with reference air plasma spray (APS) TBC. In this dissertation, results from characterization and testing of these new TBCs are presented, together with a discussion of mechanisms responsible for CMAS-attack mitigation. The penetration of CMAS causes a loss of strain tolerance of the coating. Delamination maps are used to demonstrate the combined effects of CMAS penetration, temperature gradient and cooling inhomogeneity on the coating. Evans and Hutchinson's model has been used to produce delamination maps and predict the durability of novel TBCs.

Composition of the Ultra-Low Velocity Zone from Shock Data

NASA Astrophysics Data System (ADS)

Ahrens, T. J.; Asimow, P. D.

2009-12-01

Composition of the Ultra-Low Velocity Zone from Shock Data Thomas J. Ahrens and Paul D. Asimow Recent models of the thermal structure of a putative magma ocean upon accretion of the Earth are derived from construction of isentropes centered at the core-mantle boundary (CMB) pressure and temperature (133 GPa and 4300 K). These models were motivated by the idea that the seismologically mapped ultra-low velocity zones (ULVZ) above the CMB are partially molten remnants of a basal magma ocean [1]. Magma ocean thermal models are derived from the observation of strongly increasing Grüneisen parameter (γ) upon compression of silicate liquids both in ab initio molecular dynamics modeling of MgSiO3 melt [2] and in new shock wave data on MgSiO3 phases reaching CMB conditions. Shock EOS (and limited Hugoniot radiative temperature) data for Mg2SiO4 (initially forsterite and wadsleyite) access perovskite (and post-perovskite) + periclase and melt regimes [3]. MgSiO3 (initially enstatite, perovskite, and glass) EOS and radiative temperature data in the perovskite, post-perovskite, and melt regimes, together with static P-V-T data, define the properties of these phases [4]. With recent Caltech Hugoniot radiative temperature measurements on pre-heated (1923 K) MgO [5], we have experimental constraints on melting temperatures of all major minerals in the MgO-SiO2 binary at lower-most mantle pressures. Recently extended (to 130 GPa) pre-heated (1673 K) Hugoniot data for molten and solid diopside - anorthite aggregate (64 mol % diopside, 36 mol % anorthite) also show the strong increase in γ, over the pressure range of the mantle, previously observed for ultramafic compositions. For long-term gravitational stability, the presumed molten silicate liquid of the ULVZ must be neutrally buoyant, or denser, than the ambient lowermost mantle. Surprisingly, unlike the situation in the upper mantle low-velocity zone, the density of even partially Fe-enriched, Di0.64An0.36 composition, ~5.1 g/cm3 , is much too low to be stable in the ambient, ~5.6 g/cm3, solid mineral assemblage at lower-most mantle conditions. In contrast, a molten magma of MgSiO3 composition, not necessarily requiring significant Fe enrichment, appears to approximately satisfy ULVZ constraints of melting temperature and density. [1] Labrosse, S., et al. (2007), Nature, 450, 866. [2] Stixrude, L., and B. Karki (2005), Science, 310, 297. [3] Mosenfelder, J. L., et al. (2007),, J. Geophys. Res., 112B, 6208. [4] Mosenfelder, J. L., et al. (2009), J. Geophys. Res., 114B,1203. [5] Fat’yanov O. V., et al. (2009), APS SCCM.

Crystal growth and disequilibrium distribution of oxygen isotopes in an igneous Ca-Al-rich inclusion from the Allende carbonaceous chondrite

NASA Astrophysics Data System (ADS)

Kawasaki, Noriyuki; Simon, Steven B.; Grossman, Lawrence; Sakamoto, Naoya; Yurimoto, Hisayoshi

2018-01-01

TS34 is a Type B1 Ca-Al-rich inclusion (CAI) from the Allende CV3 chondrite, consisting of spinel, melilite, Ti-Al-rich clinopyroxene (fassaite) and minor anorthite in an igneous texture. Oxygen and magnesium isotopic compositions were measured by secondary ion mass spectrometry in spots of known chemical composition in all major minerals in TS34. Using the sequence of formation from dynamic crystallization experiments and from chemical compositions of melilite and fassaite, the oxygen isotopic evolution of the CAI melt was established. Oxygen isotopic compositions of the constituent minerals plot along the carbonaceous chondrite anhydrous mineral line. The spinel grains are uniformly 16O-rich (Δ17O = -22.7 ± 1.7‰, 2SD), while the melilite grains are uniformly 16O-poor (Δ17O = -2.8 ± 1.8‰) irrespective of their åkermanite content and thus their relative time of crystallization. The fassaite crystals exhibit growth zoning overprinting poorly-developed sector zoning; they generally grow from Ti-rich to Ti-poor compositions. The fassaite crystals also show continuous variations in Δ17O along the inferred directions of crystal growth, from 16O-poor (Δ17O ∼ -3‰) to 16O-rich (Δ17O ∼ -23‰), covering the full range of oxygen isotopic compositions observed in TS34. The early-crystallized 16O-poor fassaite and the melilite are in oxygen isotope equilibrium and formed simultaneously. The correlation of oxygen isotopic compositions with Ti content in the fassaite imply that the oxygen isotopic composition of the CAI melt evolved from 16O-poor to 16O-rich during fassaite crystallization, presumably due to oxygen isotope exchange with a surrounding 16O-rich nebular gas. Formation of spinel, the liquidus phase in melts of this composition, predates crystallization of all other phases, so its 16O-rich composition is a relic of an earlier stage. Anorthite exhibits oxygen isotopic compositions between Δ17O ∼ -2‰ and -9‰, within the range of those of fassaite, indicating co-crystallization of these two minerals during the earliest to intermediate stage of fassaite growth. The melilite and fassaite yield an 26Al-26Mg mineral isochron with an initial value of (26Al/27Al)0 = (5.003 ± 0.075) × 10-5, corresponding to a relative age of 0.05 ± 0.02 Myr from the canonical Al-Mg age of CAIs. These data demonstrate that both 16O-rich and 16O-poor reservoirs existed in the solar nebula at least ∼0.05 Myr after the birth of the Solar System.

Surface chemistry of the Moon: New views from Chandrayaan-1 X-ray Spectrometer and future potentials

NASA Astrophysics Data System (ADS)

Narendranath, Shyama; Athiray, Subramania; Parameswaran, Sreekumar; Grande, Manuel

2015-04-01

X-ray remote sensing is an established technique for chemical mapping of atmosphere-less inner solar system bodies. Chandrayaan-1 X-ray Spectrometer (C1XS) [Grande et al, 2009], on-board the first Indian lunar mission Chandrayaan-1 [Bhandari et al, 2004], was flown with the objective [Crawford et al, 2009] of globally mapping the abundances of the major rock-forming elements Mg, Al, Si, Ca ,Ti and Fe with a spatial resolution of 25 km on the lunar surface. The instrument was developed by the Rutherford Appleton Laboratory (RAL), UK in collaboration with the Indian Space Research Organization (ISRO). X-ray fluorescence (XRF) observations measure the abundance irrespective of the mineral structure. XRF spectral analysis can uniquely identify and quantify elemental signatures from all commonly occurring elements. C1XS is one of the first instruments to unambiguously map the abundance of elements from Na to Fe at scales of tens of kilometers. Because of the exceptionally low solar activity in 2009, the strongest solar flare observed was of C3 class and hence global mapping could not be achieved. However from the available coverage of ~ 5%, we have determined elemental abundances accurately through a detailed calibration of the instrument and inversion methodology [Narendranath et al, 2010; Athiray et al, 2013]. The end-to-end capacity to derive independent and accurate global surface chemical abundances using x-ray signatures was clearly demonstrated with C1XS. We present results from a comprehensive analysis of all data from C1XS with emphasis on the new finding of enhanced sodium in the southern lunar highlands that suggests possible new lithologies [Narendranath et al, 2011; Athiray et al, 2014]. It is generally believed that lunar highlands are mainly composed of plagioclase feldspar with lower amounts of the mafic minerals. Plagioclase in lunar samples have been found to have an anorthite content as high as An98 with the average highlands estimated to be An95. Lower anorthite content (as low as An70) plagioclase grains have been found in lunar samples but is much rarer. C1XS measurements especially of Na, Al and Ca reveal larger regions of low An than previously thought of. We provide evidence for this from quantitative estimates of elemental abundances. Further, we present the development of Chandrayaan-2 Large Area Soft x-ray Spectrometer (CLASS) [Narendranath et al, 2014] to be flown on the second Indian lunar mission (~2018) which would continue from where C1XS left off but with a greater sensitivity and better spatial resolution.

Extraction processes for the production of aluminum, titanium, iron, magnesium, and oxygen and nonterrestrial sources

NASA Technical Reports Server (NTRS)

Rao, D. B.; Choudary, U. V.; Erstfeld, T. E.; Williams, R. J.; Chang, Y. A.

1979-01-01

The suitability of existing terrestrial extractive metallurgical processes for the production of Al, Ti, Fe, Mg, and O2 from nonterrestrial resources is examined from both thermodynamic and kinetic points of view. Carbochlorination of lunar anorthite concentrate in conjunction with Alcoa electrolysis process for Al; carbochlorination of lunar ilmenite concentrate followed by Ca reduction of TiO2; and subsequent reduction of Fe2O3 by H2 for Ti and Fe, respectively, are suggested. Silicothermic reduction of olivine concentrate was found to be attractive for the extraction of Mg becaue of the technological knowhow of the process. Aluminothermic reduction of olivine is the other possible alternative for the production of magnesium. The large quantities of carbon monoxide generated in the metal extraction processes can be used to recover carbon and oxygen by a combination of the following methods: (1) simple disproportionation of CO,(2) methanation of CO and electrolysis of H2O, and (3) solid-state electrolysis of gas mixtures containing CO, CO2, and H2O. The research needed for the adoption of earth-based extraction processes for lunar and asteroidal minerals is outlined.

Major and trace element chemistry of separated fragments from a hibonite-bearing Allende inclusion

NASA Technical Reports Server (NTRS)

Davis, A. M.; Grossman, L.; Allen, J. M.

1978-01-01

The major and trace elements of separated fragments and a bulk sample from CG-11, a hibonite-bearing inclusion in the Allende meteorite, were analyzed. Major element abundances were used to determine the minerology of separated fragments. The high degree of correlation between Eu/Sm ratios and Lu/Yb ratios for the samples studied indicates that their rare earth element (REE) distributions are governed by two components. One, Lu-, Eu-rich, is probably hibonite; the other, depleted in these elements, seems to be associated with the secondary alteration phases, grossular, nepheline and anorthite. The REE distribution in CG-11 precludes melting events after formation of the secondary alteration phases, but a melting event involving the primary minerals cannot be excluded. The enrichment of Lu with respect to other measured REE in hibonite can be explained by present REE condensation models. Two Hf-bearing components, most likely hibonite and perovskite, are necessary to account for variations in Sc/Hf ratios in the fragments studied. The lithophile volatiles Na, Mn, Fe, Zn, and probably Cr increase in the same order as the amount of secondary alteration minerals; the volatile siderophile elements Co and Au, however, do not.

Turning the Moon into a Solar Photovoltaic Paradise

NASA Technical Reports Server (NTRS)

Freundlich, Alex; Alemu, Andenet; Williams, Lawrence; Nakamura, Takashi; Sibille, Laurent; Curren, Peter

2006-01-01

Lunar resource utilization has focused principally on the extraction of oxygen from the lunar regolith. A number of schemes have been proposed for oxygen extraction from Ilmenite and Anorthite. Serendipitously, these schemes have as their by-products (or more directly as their "waste products"), materials needed for the fabrication of thin film silicon solar cells. Thus lunar surface possesses both the elemental components needed for the fabrication of silicon solar cells and a vacuum environment that allows for vacuum deposition of thin film solar cells directly on the surface of the Moon without the need for vacuum chambers. In support of the US space exploration initiative a new architecture for the production of thin film solar cells on directly on the lunar surface is proposed. The paper discusses experimental data on the fabrication and properties of lunar glass substrates, evaporated lunar regolith thin films (anti-reflect coatings and insulators), and preliminary attempts in the fabrication of thin film (silicon/II-VI) photovoltaic materials on lunar regolith glass substrates. A conceptual design for a solar powered robotic rover capable of fabricating solar cells directly on the lunar surface is provided. Technical challenges in the development of such a facility and strategies to alleviate perceived difficulties are discussed.

A Low Viscosity Lunar Magma Ocean Forms a Stratified Anorthitic Flotation Crust With Mafic Poor and Rich Units: Lunar Magma Ocean Viscosity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dygert, Nick; Lin, Jung-Fu; Marshall, Edward W.

Much of the lunar crust is monomineralic, comprising >98% plagioclase. The prevailing model argues the crust accumulated as plagioclase floated to the surface of a solidifying lunar magma ocean (LMO). Whether >98% pure anorthosites can form in a flotation scenario is debated. An important determinant of the efficiency of plagioclase fractionation is the viscosity of the LMO liquid, which was unconstrained. Here we present results from new experiments conducted on a late LMO-relevant ferrobasaltic melt. The liquid has an exceptionally low viscosity of 0.22more » $$+0.11\\atop{-0.19}$$to 1.45 $$+0.46\\atop{-0.82}$$ Pa s at experimental conditions (1,300–1,600°C; 0.1–4.4 GPa) and can be modeled by an Arrhenius relation. Extrapolating to LMO-relevant temperatures, our analysis suggests a low viscosity LMO would form a stratified flotation crust, with the oldest units containing a mafic component and with very pure younger units. Old, impure crust may have been buried by lower crustal diapirs of pure anorthosite in a serial magmatism scenario.« less

Nebula Models of Non-Equilibrium Mineralogy: Wark-Lovering Rims

NASA Technical Reports Server (NTRS)

Cuzzi, J. N.; Petaev, M.; Krot, A. N.

2005-01-01

Introduction: The meteorite record contains several examples of minerals that would not persist if allowed to come to equilibrium with a cooling gas of solar composition. This includes all minerals in CAIs and AOAs. Their survival is generally ascribed to physical removal of the object from the gas (isolation into a large parent object, or ejection by a stellar wind), but could also result from outward radial diffusion into cooler regions, which we discuss here. Accretion of CAIs into planetesimals has also been relied on to preserve them against loss into the sun. However, this suggestion faces several objections. Simple outward diffusion in turbulence has recently been modeled in some detail, and can preserve CAIs against loss into the sun [2]. Naturally, outward radial diffusion in turbulence is slower than immediate ejection by a stellar wind, which occurs on an orbital timescale. Here we ask whether these different transport mechanisms can be distinguished by nonequilibrium mineralogy, which provides a sort of clock. Our application here is to one aspect of CAI mineralogy - the Wark-Lovering rims (WLR); even more specifically, to alteration of one layer in the WLR sequence from melilite (Mel) to anorthite (An).

Northwest Africa 10758: A New CV3 Chondrite Bearing a Giant CAI with Hibonite-Rich Wark-Lovering Rim

NASA Technical Reports Server (NTRS)

Ross, D. K.; Simon, J. I.; Zolensky, M.

2017-01-01

Northwest Africa (NWA) 10758 is a newly identified carbonaceous chondrite that is a Bali-like oxidized CV3. The large Ca-Al rich inclusion (CAI) in this sample is approx. 2.4 x 1.4 cm. The CAI is transitional in composition between type A and type B, with interior mineralogy dominated by melilite, plus less abundant spinel and Al-Ti rich diopside, and only very minor anorthite (Fig. 1A). This CAI is largely free of secondary alteration in the exposed section we examined, with almost no nepheline, sodalite or Ca-Fe silicates. The Wark-Lovering (WL) rim on this CAI is dominated by hibonite, with lower abundances of spinel and perovskite, and with hibonite locally overlain by melilite plus perovskite (as in Fig. 1B). Note that the example shown in 1B is exceptional. Around most of the CAI, hibonite + spinel + perovskite form the WL rim, without overlying melilite. The WL rim can be unusually thick, ranging from approx.20 microns up to approx. 150 microns. A well-developed, stratified accretionary rim infills embayments of the CAI, and thins over protuberances in the convoluted CAI surface.

NWA10758: A New CV3 Chondrite Bearing a Giant CAI with Hibonite-Rich Wark-Lovering Rim

NASA Technical Reports Server (NTRS)

Ross, D. K.; Simon, J. I.; Zolensky, M.

2017-01-01

Northwest Africa (NWA) 10758 is a newly identified carbonaceous chondrite that is a Bali-like oxidized CV3. The large Ca-Al rich inclusion (CAI) in this sample is approx. 2.4 x 1.4 cm. The CAI is transitional in composition between type A and type B, with interior mineralogy dominated by melilite, plus less abundant spinel and Al-Ti rich diopside, and only very minor anorthite (Fig. 1A). This CAI is largely free of secondary alteration in the exposed section we examined, with almost no nepheline, sodalite or Ca-Fe silicates. The Wark-Lovering (WL) rim on this CAI is dominated by hibonite, with lower abundances of spinel and perovskite, and with hibonite locally overlain by melilite plus perovskite (as in Fig. 1B). Note that the example shown in 1B is exceptional. Around most of the CAI, hibonite + spinel + perovskite form the WL rim, without overlying melilite. The WL rim can be unusually thick, ranging from approx. 20 microns up to approx. 150 microns. A well-developed, stratified accretionary rim infills embayments of the CAI, and thins over protuberances in the convoluted CAI surface.

Exploration of geo-mineral compounds in granite mining soils using XRD pattern data analysis

NASA Astrophysics Data System (ADS)

Koteswara Reddy, G.; Yarakkula, Kiran

2017-11-01

The purpose of the study was to investigate the major minerals present in granite mining waste and agricultural soils near and away from mining areas. The mineral exploration of representative sub-soil samples are identified by X-Ray Diffractometer (XRD) pattern data analysis. The morphological features and quantitative elementary analysis was performed by Scanning Electron Microscopy-Energy Dispersed Spectroscopy (SEM-EDS).The XRD pattern data revealed that the major minerals are identified as Quartz, Albite, Anorthite, K-Feldspars, Muscovite, Annite, Lepidolite, Illite, Enstatite and Ferrosilite in granite waste. However, in case of agricultural farm soils the major minerals are identified as Gypsum, Calcite, Magnetite, Hematite, Muscovite, K-Feldspars and Quartz. Moreover, the agricultural soils neighbouring mining areas, the minerals are found that, the enriched Mica group minerals (Lepidolite and Illite) the enriched Orthopyroxene group minerals (Ferrosilite and Enstatite). It is observed that the Mica and Orthopyroxene group minerals are present in agricultural farm soils neighbouring mining areas and absent in agricultural farm soils away from mining areas. The study demonstrated that the chemical migration takes place at agricultural farm lands in the vicinity of the granite mining areas.

Petrographic Analysis and Geochemical Source Correlation of Pigeon Peak, Sutter Buttes, CA

NASA Astrophysics Data System (ADS)

Novotny, N. M.; Hausback, B. P.

2013-12-01

The Sutter Buttes are a volcanic complex located in the center of the Great Valley north of Sacramento. They are comprised of numerous inter-intruding andesite and rhyolite lava domes of varying compositions surrounded by a shallow rampart of associated tephras. The Pigeon Peak block-and-ash flow sequence is located in the rampart and made up of a porphyritic Biotite bearing Hornblende Andesite. The andesite blocks demonstrate a high degree of propylization in hornblende crystals, highly zoned plagioclase, trace olivine, and display a red to gray color gradation. DAR is an andesite dome located less than one mile from Pigeon Peak. Of the 15 to 25 andesite lava domes within four miles from Pigeon Peak, only DAR displays trace olivine, red to grey color stratification, low biotite content, and propylitized hornblende. These characteristic similarities suggest that DAR may be the source for Pigeon Peak. My investigation used microprobe analysis of the DAR and Pigeon Peak feldspar crystals to identify the magmatic history of the magma body before emplacement. Correlation of the anorthite zoning within the feldspars from both locations support my hypothesis that DAR is the source of the Pigeon Peak block-and-ash flow.

Fine resolution chronology based on initial Sr-87/Sr-86

NASA Technical Reports Server (NTRS)

Stewart, B. W.; Papanastassiou, D. A.; Capo, R. C.; Wasserburg, G. J.

1993-01-01

It has been recognized that small variations in initial Sr-87/Sr-86 (Sr(sub I)), can provide a fine scale relative chronology for the chemical fractionation of materials with low Rb/Sr from parent reservoirs with high Rb/Sr. Similarly, Sr(sub I), as determined for low Rb/Sr phases in meteorites, may permit a fine resolution chronology of the recrystallization or metamorphism of planetary materials. For the establishment of a primitive Sr-87/Sr-86 chronology, it is important to search for samples with extremely low Rb/Sr for which the measured Sr-87/Sr-86 is below BABI, in which case the primitive nature of the Sr can be directly established. Using the measured Rb/Sr to calculate an initial Sr-87/Sr-86 can introduce substantial uncertainty if the Rb-Sr are disturbed. We report Sr-87/Sr-86 in plagioclase from silicate pebbles from the Vaca Muerta mesosiderite on which we have reported Sm-147-Nd-143 and Ne-142 correlations. For the purpose of cross-calibration with our previous work we have performed extensive new measurements on Angra dos Reis and on anorthite from Moore County, which have very low Rb/Sr and primitive Sr-87/Sr-86.

First-principles molecular dynamics simulations of anorthite (CaAl2Si2O8) glass at high pressure

NASA Astrophysics Data System (ADS)

Ghosh, Dipta B.; Karki, Bijaya B.

2018-06-01

We report first-principles molecular dynamics study of the equation of state, structural, and elastic properties of CaAl2Si2O8 glass at 300 K as a function of pressure up to 155 GPa. Our results for the ambient pressure glass show that: (1) as with other silicates, Si atoms remain mostly (> 95%) under tetrahedral oxygen surroundings; (2) unlike anorthite crystal, presence of high-coordination (> 4) Al atoms with 30% abundance; (3) and significant presence of both non-bridging (8%) and triply (17%) coordinated oxygen. To achieve the glass configurations at various pressures, we use two different simulation schedules: cold and hot compression. Cold compression refers to sequential compression at 300 K. Compression at 3000 K and subsequent isochoric quenching to 300 K is considered as hot compression. At the initial stages of compression (0-10 GPa), smooth increase in bond distance and coordination occurs in the hot-compressed glass. Whereas in cold compression, Si (also Al to some extent) displays mainly topological changes (without significantly affecting the average bond distance or coordination) in this pressure interval. Further increase in pressure results in gradual increases in mean coordination, with Si-O (Al-O) coordination eventually reaching and remaining 6 (6.5) at the highest compression. Similarly, the ambient pressure Ca-O coordination of 5.9 increases to 9.5 at 155 GPa. The continuous pressure-induced increase in the proportion of oxygen triclusters along with the appearance and increasing abundance of tetrahedral oxygens results in mean O-T (T = Si and Al) coordination of > 3 from a value of 2.1 at ambient pressure. Due to the absence of kinetic barrier, the hot-compressed glasses consistently produce greater densities and higher coordination numbers than the cold compression cases. Decompressed glasses show irreversible compaction along with retention of high-coordination species when decompressed from pressure ≥ 10 GPa. The different density retention amounts (12, 17, and 20% when decompressed from 12, 40, and 155 GPa, respectively) signifies that the degree of irreversibility depends on the peak pressure of decompression. The calculated compressional and shear wave velocities (5 and 3 km/s at 0 GPa) for the cold-compressed case display sluggish pressure response in the 0-10 GPa interval as opposed to smooth increase in the hot-compressed one. Shear velocity saturates rather rapidly with a value of 5 km/s, whereas compressional wave velocity displays continuous increase, reaching/exceeding 12.5 km/s at 155 GPa. These structural details suggest that the pressure response of the cold-compressed glasses is not only inherently different at the 0-10 GPa interval, the density, coordination, and wave velocity data are consistently lower than the hot-compressed glasses. Hot-compressed glasses may, therefore, be the better analog in the study of high-pressure silicate melts.

The Thermal Expansion Of Feldspars

NASA Astrophysics Data System (ADS)

Hovis, G. L.; Medford, A.; Conlon, M.

2009-12-01

Hovis and others (1) investigated the thermal expansion of natural and synthetic AlSi3 feldspars and demonstrated that the coefficient of thermal expansion (α) decreases significantly, and linearly, with increasing room-temperature volume (VRT). In all such feldspars, therefore, chemical expansion limits thermal expansion. The scope of this work now has been broadened to include plagioclase and Ba-K feldspar crystalline solutions. X-ray powder diffraction data have been collected between room temperature and 925 °C on six plagioclase specimens ranging in composition from anorthite to oligoclase. When combined with thermal expansion data for albite (2,3,4) a steep linear trend of α as a function of VRT emerges, reflecting how small changes in composition dramatically affect expansion behavior. The thermal expansion data for five synthetic Ba-K feldspars ranging in composition from 20 to 100 mole percent celsian, combined with data for pure K-feldspar (3,4), show α-VRT relationships similar in nature to the plagioclase series, but with a slope and intercept different from the latter. Taken as a group all Al2Si2 feldspars, including anorthite and celsian from the present study along with Sr- (5) and Pb-feldspar (6) from other workers, show very limited thermal expansion that, unlike AlSi3 feldspars, has little dependence on the divalent-ion (or M-) site occupant. This apparently is due to the necessitated alternation of Al and Si in the tetrahedral sites of these minerals (7), which in turn locks the tetrahedral framework and makes the M-site occupant nearly irrelevant to expansion behavior. Indeed, in feldspar series with coupled chemical substitution it is the change away from a 1:1 Al:Si ratio that gives feldspars greater freedom to expand. Overall, the relationships among α, chemical composition, and room-temperature volume provide useful predictive tools for estimating feldspar thermal expansion and give insight into the controls of expansion behavior in this important mineral system. We thank the Earth Sciences Division of the National Science Foundation for support of this research via grant EAR-0408829, which has provided valuable learning experiences for the undergraduate coauthors of this abstract. We appreciate the cooperation of the Department of Mineral Sciences, Smithsonian Institution, which provided five of the plagioclase specimens. Thanks to Tony Abraham, Department of Earth Sciences, Cambridge University, who conducted a portion of the high-temperature X-ray experiments. The Ba-K feldspar crystalline solutions were synthesized and chemically characterized in the 1970's at Harvard University by our good friend, Dr. Jun Ito, now deceased. (1) Hovis, Morabito, Spooner, Mott, Person, Henderson, Roux and Harlov, 2008, American Mineralogist, (2) Stewart and von Limbach, 1967, American Journal of Science, (3) Hovis and Graeme-Barber, 1997, American Mineralogist, (4) Hovis, Brennan, Keohane, and Crelling, 1999, The Canadian Mineralogist, (5) Henderson, 1984, Progress in Experimental Petrology, NERC Report, Volume 6, (6) Benna, Tribaudino, and Bruno, 1999, American Mineralogist, (7) Lowenstein, 1954, American Mineralogist.

Thermodynamic parameters of bonds in glassy materials from viscosity-temperature relationships.

PubMed

Ojovan, Michael I; Travis, Karl P; Hand, Russell J

2007-10-17

Doremus's model of viscosity assumes that viscous flow in amorphous materials is mediated by broken bonds (configurons). The resulting equation contains four coefficients, which are directly related to the entropies and enthalpies of formation and motion of the configurons. Thus by fitting this viscosity equation to experimental viscosity data these enthalpy and entropy terms can be obtained. The non-linear nature of the equation obtained means that the fitting process is non-trivial. A genetic algorithm based approach has been developed to fit the equation to experimental viscosity data for a number of glassy materials, including SiO 2 , GeO 2 , B 2 O 3 , anorthite, diopside, xNa 2 O-(1-x)SiO 2 , xPbO-(1-x)SiO 2 , soda-lime-silica glasses, salol, and α-phenyl-o-cresol. Excellent fits of the equation to the viscosity data were obtained over the entire temperature range. The fitting parameters were used to quantitatively determine the enthalpies and entropies of formation and motion of configurons in the analysed systems and the activation energies for flow at high and low temperatures as well as fragility ratios using the Doremus criterion for fragility. A direct anti-correlation between fragility ratio and configuron percolation threshold, which determines the glass transition temperature in the analysed materials, was found.

Impact of naturally leaking carbon dioxide on soil properties and ecosystems in the Qinghai-Tibet plateau.

PubMed

Zhao, Xiaohong; Deng, Hongzhang; Wang, Wenke; Han, Feng; Li, Chunrong; Zhang, Hui; Dai, Zhenxue

2017-06-07

One of the major concerns for CO 2 capture and storage (CCS) is the potential risk of CO 2 leakage from storage reservoirs on the shallow soil property and vegetation. This study utilizes a naturally occurring CO 2 leaking site in the Qinghai-Tibet Plateau to analog a "leaking CCS site". Our observations from this site indicates that long-term CO 2 invasion in the vadose zone results in variations of soil properties, such as pH fluctuation, slight drop of total organic carbon, reduction of nitrogen and phosphorus, and concentration changes of soluble ions. Simultaneously, XRD patterns of the soil suggest that crystallization of soil is enhanced and mineral contents of calcite and anorthite in soil are increased substantially. Parts of the whole ecosystem such as natural wild plants, soil dwelling animals and microorganisms in shallow soil are affected as well. Under a moderate CO 2 concentration (less than 110000 ppm), wild plant growth and development are improved, while an intensive CO 2 flux over 112000 ppm causes adverse effects on the plant growth, physiological and biochemical system of plants, and crop quality of wheat. Results of this study provide valuable insight for understanding the possible environmental impacts associated with potential CO 2 leakage into shallow sediments at carbon sequestration sites.

The origin of garnet in the anorthosite-charnockite suite of the Adirondacks

USGS Publications Warehouse

McLelland, J.M.; Whitney, P.R.

1977-01-01

Detailed analysis of textural and chemical criteria in rocks of the anorthosite-charnockite suite of the Adirondack Highlands suggests that development of garnet in silica-saturated rocks of the suite occurs according to the reaction: {Mathematical expression}, where ?? is a function of the distribution of Fe and Mg between the several coexisting ferromagnesian phases. Depending upon the relative amounts of Fe and Mg present, quartz may be either a reactant or a product. Using an aluminum-fixed reference frame, this reaction can be restated in terms of a set of balanced partial reactions describing the processes occurring in spatially separated domains within the rock. The fact that garnet invariably replaces plagioclase as opposed to the other reactant phases indicates that the aluminum-fixed model is valid as a first approximation. This reaction is univariant and produces unzoned garnet. It differs from a similar equation proposed by de Waard (1965) for the origin of garnet in Adirondack metabasic rocks, i.e. 6 Orthopyroxene+2 Anorthite = Clinopyroxene+Garnet+2 Quartz, the principle difference being that iron oxides (ilmenite and/or magnetite) are essential reactant phases in the present reactions. The product assemblage (garnet+clinopyroxene+plagioclase ?? orthopyroxene ?? quartz) is characteristic of the clinopyroxene-almandine subfacies of the granulite facies. ?? 1977 Springer-Verlag.

Mesosiderites on Vesta: A Hyperspectral VIS-NIR Investigation

NASA Technical Reports Server (NTRS)

Palomba, E.; Longobardo, A.; DeSanctis, M. C.; Mittlefehldt, D. W.; Ammannito, E.; Capaccioni, F.; Capria, M. T.; Frigeri, A.; Tosi, F.; Zambon, F.;

Synthesis of inorganic polymers using fly ash and primary lead slag.

PubMed

Onisei, S; Pontikes, Y; Van Gerven, T; Angelopoulos, G N; Velea, T; Predica, V; Moldovan, P

2012-02-29

The present work reports on the synthesis and properties of inorganic polymers ("geopolymers") made of 100% fly ash from lignite's combustion, 100% primary lead slag and mixtures of the two. In the inorganic polymers with both fly ash and lead slag the main crystalline phases detected are wüstite, magnetite, sodium zinc silicate, quartz, anorthite, and gehlenite; litharge partially dissolves. FTIR analysis in these samples revealed that the main peaks and bands of end members also exist, along with a new amorphous reaction product. In terms of microstructure, both fly ash and lead slag dissolve and contribute in the binding phase whereas the larger particles act as aggregates. For an increasing lead slag in the composition, the binding phase is changing in chemistry and reaches PbO values higher than 50 wt.% for the 100% lead slag inorganic polymer. Regarding the properties of fly ash and lead slag inorganic polymers, compressive strength is higher than 35 MPa in all cases and water absorption diminishes as the lead slag content increases. A comparison of leaching results before and after polymerisation reveals that pH is an important factor as Pb is immobilised in the binding phase, unlike Zn and As. Copyright © 2011 Elsevier B.V. All rights reserved.

Cation Uptake and Allocation by Red Pine Seedlings under Cation-Nutrient Stress in a Column Growth Experiment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shi, Zhenqing; Balogh-Brunstad, Zsuzsanna; Grant, Michael R.

Background and Aims Plant nutrient uptake is affected by environmental stress, but how plants respond to cation-nutrient stress is poorly understood. We assessed the impact of varying degrees of cation-nutrient limitation on cation uptake in an experimental plant-mineral system. Methods Column experiments, with red pine (Pinus resinosa Ait.) seedlings growing in sand/mineral mixtures, were conducted for up to nine months under a range of Ca- and K-limited conditions. The Ca and K were supplied from both minerals and nutrient solutions with varying Ca and K concentrations. Results Cation nutrient stress had little impact on carbon allocation after nine months ofmore » plant growth and K was the limiting nutrient for biomass production. The Ca/Sr and K/Rb ratio results allowed independent estimation of dissolution incongruency and discrimination against Sr and Rb during cation uptake processes. The fraction of K in biomass from biotite increased with decreasing K supply from nutrient solutions. The mineral anorthite was consistently the major source of Ca, regardless of nutrient treatment. Conclusions Red pine seedlings exploited more mineral K in response to more severe K deficiency. This did not occur for Ca. Plant discrimination factors must be carefully considered to accurately identify nutrient sources using cation tracers.« less

Carbonatitic liquids and COH fluids from epidote-dolomite eclogites at 3.7 - 4.6 GPa: new perspectives on carbon transfer at subduction zones

NASA Astrophysics Data System (ADS)

Poli, S.

2013-12-01

Current knowledge on the solidus temperature for carbonate-bearing rocks suggests that carbonatitic liquids should not form in a subducted oceanic lithosphere, unless anomalous thermal relaxation occurs. For a mildly warm subduction path, COH-bearing basaltic eclogites are expected to loose all H2O component at epidote breakdown, located at approx. 2.8-3.0 GPa. Above this pressure limit, the solidus is that of a carbonated basaltic eclogite which shows a minimum temperature of 1020 °C at 4.0-4.5 GPa (Dasgupta et al. 2004). However, the oceanic crust includes a range of gabbroic rocks, altered on rifts and transforms, with large amounts of An-rich plagioclase. It has been shown that epidote disappearance with pressure depend on the normative anorthite content of the bulk composition considered (Poli et al. 2009); we therefore expect that altered gabbros might display a much wider pressure range where epidote persists, potentially affecting the solidus relationships. Notably, this applies to epidosite rocks formed in hydrothermal environments at oceanic settings, then recovered in high-pressure and ultra-high pressure terrains. New experimental data from 3.7 to 4.6 GPa, 750°C to 1000 °C are intended to unravel the effect of variable bulk and volatile compositions in model eclogites, enriched in the normative anorthite component (An37 and An45). Experiments are performed in piston cylinder and multianvil machines apparatus, using both single and, buffered, double capsule techniques. Garnet, clinopyroxene and coesite form in all syntheses. Lawsonite was found to persist at 3.7 GPa, 750 °C, with both dolomite and magnesite; at 3.8 GPa, 775-800 °C, fluid saturated conditions, epidote coexists with kyanite, dolomite and magnesite. The anhydrous assemblage garnet, omphacite, aragonite, kyanite is found at 4.2 GPa, 850 °C. At 900 °C, fluid-rich conditions, a silicate fluid/melt of granitoid composition, a carbonatitic melt and Na-carbonate are observed. Close to fluid-saturation, 3.8-4.2 GPa, 900 °C, garnet and Na-rich clinopyroxene coexist with a carbonatitic melt and dolomite. The carbonatitic melt is richer in Ca compared to dolomite, consistently with phase relationships in the model system MgCO3-FeCO3-CaCO3. In fluid-undersaturated compositions, fluid-absent melting of epidote + dolomite, enlarged in its pressure stability for An-rich gabbros, is expected to promote the generation of carbonatitic liquids. The subsolidus breakdown of epidote in the presence of carbonates at depths exceeding 120 km provides a major source of COH fluids at subarc depth. In warm subduction zones, the possibility of extracting carbonatitic liquids from a variety of gabbroic rocks and epidosites offers new scenarios on the metasomatic processes in the lithospheric wedge of subduction zones and a new mechanism for recycling carbon. Dasgupta R., Hirschmann M.M., Withers A. (2004) Earth Planet Sci Lett, 227: 73-85 Poli S., Franzolin E., Fumagalli P., Crottini A. (2009) Earth Planet Sci Lett, 278: 350-360

Recycling and utilisation of industrial solid waste: an explorative study on gold deposit tailings of ductile shear zone type in China.

PubMed

Liu, Rui; Huang, Fei; Du, Runxiang; Zhao, Chunming; Li, Yongli; Yu, Haoran

2015-06-01

Tailings are solid waste arising from mineral processing. This type of waste can cause severe damage to the environment during stockpiling as a result of the leaching of something harmful into the ecosystem. Gold deposit of ductile shear zone type is an important type of gold deposit, and the recycling of its tailings has been challenging researchers for a long time. In this article, the characteristics of this type of tailings were systematically studied by using modern technical means. Considering the characteristics of the tailings, clay was selected to make up for the shortcomings of the tailings and improve their performance. Water and raw materials were mixed to produce green bodies, which are subsequently sintered into ceramic bodies at 980 °C~1020 °C (sintering temperature). The results showed that some new kinds of mineral phases, such as mullite, anorthite and orthoclase, appear in ceramic bodies. Furthermore, the ceramic bodies have a surface hardness of 5 to 6 (Mohs scale), and their water absorption and modulus of rupture can meet some technical requirements of ceramic materials described in ISO 13006-2012 and GB 5001-1985. These gold mine tailings can be made into ceramic tiles, domestic ceramic bodies, and other kinds of ceramic bodies for commercial and industrial purposes after further improvements. © The Author(s) 2015.

Impact of naturally leaking carbon dioxide on soil properties and ecosystems in the Qinghai-Tibet plateau

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Xiaohong; Deng, Hongzhang; Wang, Wenke

One of the major concerns for CO 2 capture and storage (CCS) is the potential risk of CO 2 leakage from storage reservoirs on the shallow soil property and vegetation. This study utilizes a naturally occurring CO 2 leaking site in the Qinghai-Tibet Plateau to analog a “leaking CCS site”. Our observations from this site indicates that long-term CO 2 invasion in the vadose zone results in variations of soil properties, such as pH fluctuation, slight drop of total organic carbon, reduction of nitrogen and phosphorus, and concentration changes of soluble ions. Simultaneously, XRD patterns of the soil suggest thatmore » crystallization of soil is enhanced and mineral contents of calcite and anorthite in soil are increased substantially. Parts of the whole ecosystem such as natural wild plants, soil dwelling animals and microorganisms in shallow soil are affected as well. Under a moderate CO 2 concentration (less than 110000 ppm), wild plant growth and development are improved, while an intensive CO2 flux over 112000 ppm causes adverse effects on the plant growth, physiological and biochemical system of plants, and crop quality of wheat. Results of this study provide valuable insight for understanding the possible environmental impacts associated with potential CO 2 leakage into shallow sediments at carbon sequestration sites.« less

Impact of naturally leaking carbon dioxide on soil properties and ecosystems in the Qinghai-Tibet plateau

DOE PAGES

Zhao, Xiaohong; Deng, Hongzhang; Wang, Wenke; ...

2017-06-07

One of the major concerns for CO 2 capture and storage (CCS) is the potential risk of CO 2 leakage from storage reservoirs on the shallow soil property and vegetation. This study utilizes a naturally occurring CO 2 leaking site in the Qinghai-Tibet Plateau to analog a “leaking CCS site”. Our observations from this site indicates that long-term CO 2 invasion in the vadose zone results in variations of soil properties, such as pH fluctuation, slight drop of total organic carbon, reduction of nitrogen and phosphorus, and concentration changes of soluble ions. Simultaneously, XRD patterns of the soil suggest thatmore » crystallization of soil is enhanced and mineral contents of calcite and anorthite in soil are increased substantially. Parts of the whole ecosystem such as natural wild plants, soil dwelling animals and microorganisms in shallow soil are affected as well. Under a moderate CO 2 concentration (less than 110000 ppm), wild plant growth and development are improved, while an intensive CO2 flux over 112000 ppm causes adverse effects on the plant growth, physiological and biochemical system of plants, and crop quality of wheat. Results of this study provide valuable insight for understanding the possible environmental impacts associated with potential CO 2 leakage into shallow sediments at carbon sequestration sites.« less

Numerical simulation of plagioclase rim growth during magma ascent at Bezymianny Volcano, Kamchatka

NASA Astrophysics Data System (ADS)

Gorokhova, N. V.; Melnik, O. E.; Plechov, P. Yu.; Shcherbakov, V. D.

2013-08-01

Slow CaAl-NaSi interdiffusion in plagioclase crystals preserves chemical zoning of plagioclase in detail, which, along with strong dependence of anorthite content in plagioclase on melt composition, pressure, and temperature, make this mineral an important source of information on magma processes. A numerical model of zoned crystal growth is developed in the paper. The model is based on equations of multicomponent diffusion with diagonal cross-component diffusion terms and accounts for mass conservation on the melt-crystal interface and growth rate controlled by undercooling. The model is applied to the data of plagioclase rim zoning from several recent Bezymianny Volcano (Kamchatka) eruptions. We show that an equilibrium growth model cannot explain crystallization of naturally observed plagioclase during magma ascent. The developed non-equilibrium model reproduced natural plagioclase zoning and allowed magma ascent rates to be constrained. Matching of natural and simulated zoning suggests ascent from 100 to 50 MPa during 15-20 days. Magma ascent rate from 50 MPa to the surface varies from eruption to eruption: plagioclase zoning from the December 2006 eruption suggests ascent to the surface in less than 1 day, whereas plagioclase zoning from March 2000 and May 2007 eruptions are better explained by magma ascent over periods of more than 30 days). Based on comparison of diffusion coefficients for individual elements a mechanism of atomic diffusion during plagioclase crystallization is proposed.

Melt segregation during Poiseuille flow of partially molten rocks

NASA Astrophysics Data System (ADS)

Quintanilla-Terminel, A.; Dillman, A. M.; Kohlstedt, D. L.

2015-12-01

Studies of the dynamics of partially molten regions of the Earth's mantle provide the basis necessary for understanding the chemical and physical evolution of our planet. Since we cannot directly observe processes occurring at depth, we rely on models and experiments to constrain the rheological behavior of partially molten rocks. Here, we present the results of an experimental investigation of the role of viscous anisotropy on melt segregation in partially molten rocks through Poiseuille flow experiments. Partially molten rock samples with a composition of either forsterite or anorthite plus a few percent melt were prepared from vacuum sintered powders and taken to 1200ºC at 0.1 MPa. The partially molten samples were then extruded through a channel of circular cross section under a fixed pressure gradient at 1200o to 1500oC. The melt distribution in the channel was subsequently mapped through image analyses of optical and backscattered electron microscopy images. In these experiments, melt segregates from the center toward the outer radius of the channel with the melt fraction at the outer radius increasing to twice that at the center. These results are consistent with base-state melt segregation as predicted by Takei and Holtzman (JGR, 2009), Takei and Katz (JFM, 2013) and Allwright and Katz (GJI, 2014) for sheared partially molten rocks for which viscosity is anisotropic due to the stress-induced, grain-scale alignment of melt.

Correlation between magnetic susceptibility and mineral species along NWA-1 well, southern Tunisia: An overlap of the depositional environment, the climate, and the diagenesis

NASA Astrophysics Data System (ADS)

Mefteh, Samir; Essefi, Elhoucine; Yaich, Chokri; Jamoussi, Fakher; Medhioub, Mounir

2015-03-01

In order to distinguish the effects of diagenesis, the climate and the depositional environment, the magnetic properties were correlated with some minerals along the NWA-1 well, which crosses the southern subsurface from Cretaceous to Silurian successions. The MS along NWA-1 well shows major picks probably indicating a dramatic change of geochemical and mineralogical composition. Minor picks may be attributed to diagenetic transformations affecting some minerals. The mineralogical analysis shows the presence of illite, kaolinite with some traces of chlorite and smectite. Quartz, calcite, white feldspar, anorthite, dolomite, gypsum and pyrite are identified as associated minerals. The PCA of the different minerals and the magnetic susceptibility shows three different heterogeneous populations. In these populations, the traditional classification of magnetic minerals is not respected. For instance, diamagnetic minerals are positively correlated with MS. This correlation is through indirect causal relation extrapolating the temperature caused by the burial diagenesis. The aim is not totally reached because the handicap is twofold. The XRD diffraction is not able to identify the low amounts of magnetic minerals and the primary mineralogy and magnetic properties are radically modified by post-depositional processes. At the productive well of NWA-1, this overlap is further complicated by hydrocarbons, low grade metamorphism and remagnetization modifying the original magnetic signal.

Processing lunar soils for oxygen and other materials

NASA Technical Reports Server (NTRS)

Knudsen, Christian W.; Gibson, Michael A.

1992-01-01

Two types of lunar materials are excellent candidates for lunar oxygen production: ilmenite and silicates such as anorthite. Both are lunar surface minable, occurring in soils, breccias, and basalts. Because silicates are considerably more abundant than ilmenite, they may be preferred as source materials. Depending on the processing method chosen for oxygen production and the feedstock material, various useful metals and bulk materials can be produced as byproducts. Available processing techniques include hydrogen reduction of ilmenite and electrochemical and chemical reductions of silicates. Processes in these categories are generally in preliminary development stages and need significant research and development support to carry them to practical deployment, particularly as a lunar-based operation. The goal of beginning lunar processing operations by 2010 requires that planning and research and development emphasize the simplest processing schemes. However, more complex schemes that now appear to present difficult technical challenges may offer more valuable metal byproducts later. While they require more time and effort to perfect, the more complex or difficult schemes may provide important processing and product improvements with which to extend and elaborate the initial lunar processing facilities. A balanced R&D program should take this into account. The following topics are discussed: (1) ilmenite--semi-continuous process; (2) ilmenite--continuous fluid-bed reduction; (3) utilization of spent ilmenite to produce bulk materials; (4) silicates--electrochemical reduction; and (5) silicates--chemical reduction.

Mineralogical composition of boiler fouling and slagging deposits and their relation to fly ashes: the case of Kardia power plant.

PubMed

Kostakis, George

2011-01-30

Slagging and fouling deposits from a pulverized lignite fired steam generating unit of the Kardia power plant (West Macedonia, Greece) were mineralogically investigated. The structure and cohesion of these deposits varied, usually depending on the level height of the boiler unit where they were formed. Some of the deposits had complex phase composition. The dominant components of the deposits of the burner zone and of the lower and intermediate boiler zones were the amorphous, anhydrite and hematite, while those of the highest levels contained amorphous, and anhydrite. Furthermore, in deposits formed in various other boiler areas gehlenite, anorthite, diopside, quartz, Ca(2)SiO(4), brownmillerite and other crystalline phases were also identified, usually in low amounts or in traces. The major part of the phases constituting the deposits were formed in the boiler, since only a minor part derived from the unreacted minerals present in lignite. Anhydrite was generated from the reaction of SO(2) with CaO formed mainly by the calcination of calcite as well as from dehydration of gypsum contained in lignite, while hematite was produced mainly from the oxidation of pyrite. The calcium-containing silicates formed in the boiler were mainly the products of reactions between CaO and minerals contained in the lignite. Copyright © 2010 Elsevier B.V. All rights reserved.

Evaluation of lunar rocks and soils for resource utilization: Detailed image analysis of raw materials and beneficiated products

NASA Technical Reports Server (NTRS)

Taylor, Lawrence A.; Chambers, John G.; Patchen, Allan; Jerde, Eric A.; Mckay, David S.; Graf, John; Oder, Robin R.

1993-01-01

The rocks and soils of the Moon will be the raw materials for fuels and construction needs at a lunar base. This includes sources of materials for the generation of hydrogen, oxygen, metals, and other potential construction materials. For most of the bulk material needs, the regolith, and its less than 1 cm fraction, the soil, will suffice. But for specific mineral resources, it may be necessary to concentrate minerals from rocks or soils, and it is not always obvious which is the more appropriate feedstock. Besides an appreciation of site geology, the mineralogy and petrography of local rocks and soils is important for consideration of the resources which can provide feedstocks of ilmenite, glass, agglutinates, anorthite, etc. In such studies, it is very time-consuming and practically impossible to correlate particle counts (the traditional method of characterizing lunar soil petrography) with accurate modal analyses and with mineral associations in multi-mineralic grains. But x ray digital imaging, using x rays characteristic of each element, makes all this possible and much more (e.g., size and shape analysis). An application of beneficiation image analysis, in use in our lab (Oxford Instr. EDS and Cameca SX-50 EMP), was demonstrated to study mineral liberation from lunar rocks and soils. Results of x ray image analysis are presented.

Formation of a metastable hollandite phase from amorphous plagioclase: A possible origin of lingunite in shocked chondritic meteorites

NASA Astrophysics Data System (ADS)

Kubo, Tomoaki; Kono, Mari; Imamura, Masahiro; Kato, Takumi; Uehara, Seiichiro; Kondo, Tadashi; Higo, Yuji; Tange, Yoshinori; Kikegawa, Takumi

2017-11-01

We conducted high-pressure experiments in plagioclase with different anorthite contents at 18-27 GPa and 25-1750 °C using both a laser-heated diamond anvil cell and a Kawai-type multi-anvil apparatus to clarify the formation conditions of the hollandite phase in shocked chondritic and Martian meteorites. Lingunite (NaAlSi3O8-rich hollandite) was found first to crystallize from amorphous oligoclase as a metastable phase before decomposing into the final stable state. This process might account for the origin of lingunite found along with maskelynite in shocked chondritic meteorites. Metastable lingunite appeared at ∼20-24 GPa and ∼1100-1300 °C in laboratory tests lasting tens of minutes; however, it might also form at the higher temperatures and shorter time periods of shock events. In contrast, the hollandite phase was not observed during any stage of crystallization when using albite or labradorite as starting materials. The formation process of (Ca,Na)-hollandite in the labradorite composition found in Martian shergottites remains unresolved. The orthoclase contents of the hollandite phase both in shocked meteorites (2.4-8.2 mol%) and our oligoclase sample (3.9 mol%) are relatively high compared to the albite and labradorite samples (0.6 and 1.9 mol%, respectively). This might critically affect the crystallization kinetics of hollandite phase.

In-situ high-temperature Raman spectroscopic studies of aluminosilicate liquids

NASA Astrophysics Data System (ADS)

Daniel, Isabelle; Gillet, Philippe; Poe, Brent T.; McMillan, Paul F.

1995-03-01

We have measured in-situ Raman spectra of aluminosilicate glasses and liquids with albite (NaAlSi3 O8) and anorthite (CaAl2Si2O8) compositions at high temperatures, through their glass transition range up to 1700 and 2000 K, respectively. For these experiments, we have used a wire-loop heating device coupled with micro-Raman spectroscopy, in order to achieve effective spatial filtering of the extraneous thermal radiation. A major concern in this work is the development of methodology for reliably extracting the first and second order contributions to the Raman scattering spectra of aluminosilicate glasses and liquids from the high temperature experimental data, and analyzing these in terms of vibrational (anharmonic) and configurational changes. The changes in the first order Raman spectra with temperature are subtle. The principal low frequency band remains nearly constant with increasing temperature, indicating little change in the T-O-T angle, and that the angle bending vibration is quite harmonic. This is in contrast to vitreous SiO2, studied previously. Above Tg, intensity changes in the 560 590 cm-1 regions of both sets of spectra indicate configurational changes in the supercooled liquids, associated with formation of additional Al-O-Al linkages, or 3-membered (Al, Si)-containing rings. Additional intensity at 800 cm-1 reflects also some rearrangement of the Si-O-Al network.

Formation and composition of the moon

NASA Technical Reports Server (NTRS)

Anderson, D. L.

1977-01-01

Many of the properties of the Moon, including the enrichment in Ca, Al, Ti, U, Th, Ba, Sr, and the REE and the depletion in Fe, Rb, K, Na, and other volatiles can be understood if the Moon represents a high-temperature condensate from the solar nebula. Thermodynamic calculations show that Ca-, Al-, and Ti-rich compounds condense first in a cooling nebula. The initial high temperature mineralogy is gehlenite, spinel, perovskite, Ca-Al-rich pyroxenes, and anorthite. Inclusions in carbonaceous chondrites such as the Allende meteorite are composed primarily of these minerals and, in addition, are highly enriched in refractories such as REE relative to carbonaceous chondrites. These inclusions can yield basalt and anorthosite in the proportions required to eliminate the europium anomaly, leaving a residual spinel-melilite interior. A deep interior high in Ca-Al does not imply an unacceptable mean density or moment of inertia for the Moon. The inferred high-U content of the lunar interior, both from the Allende analog and the high heat flow, indicates a high-temperature interior. The model is consistent with extensive early melting, with shallow melting at 3 AE, and with presently high deep internal temperatures. It is predicted that the outer 250 km is rich in plagioclase and FeO. The low iron content of the interior in this model raises the interior temperatures estimated from electrical conductivity by some 800 C.

Angrites LEW 87051 and Asuka 881371: Similarities and Differences

NASA Astrophysics Data System (ADS)

Yanai, K.

1993-07-01

Both angrite meteorites Lewis Cliff (LEW) 87051 (U.S. collection) and Asuka (A) 881371 (Japanese collection) were collected from Antarctica. The collecting sites of the angrites are Lewis Cliff Ice Tongue, 84 degrees 17 minutes S and 161 degrees OO minutes E in the Transantarctic Mountains, and Asuka Station, 72 degrees 50 minutes S and 24 degrees 30 minutes E, in Queen Maud Land, respectively. Therefore the two localities are separated by almost 2500 km. LEW87051: LEW87051 is 0.6 g in original weight and 1 x 0. 7 x 0.5 cm in diameter; it is a tiny individual achondritic meteorite, completely covered with a black fusion crust [1]. Petrographically, this specimen shows the typical porphyritic texture of olivine with subequal amount of groundmass plagioclase laths and interstitial pyroxene with little opaque. Plagioclase laths, 0.02 x 0.3 mm, are in a subparallel arrangement (Fig. 1). Pyroxene is titanian fassaite showing weak pleochroic of purplish tint, the average composition of which is Wo50.2, containing 6-9% A1203 and 2-6% TiO2, and range En1-29, Fs21-55, and Wo44-53. Olivine contiains variable composition, average Fo21, and ranged Fo8-91 correspond with Fe-rich rim to Mg-rich core. Plagioclase is almost pure anorthite (An99-100). Asuka-881371: A-881371 is 11 g in original weight and 2.0 x 1.6 x 1.6 in diameter. It is a rounded stone almost completely covered with a dull black (not shiny) fusion crust. Pale green, relatively coarse olivine crystals can be seen on the exposed interior surface. Petrographyically, the Asuka angrite shows an unbrecciated and typical ophitic texture with less porphyritic olivine crystal (xenocryst?), and consists mostly of euhedral plagioclase, integranular fassaite, and olivine with traced opaque and spinel (Fig. 2). Pyroxene is titanium fassaite with pleochroic brown in the rim, which is average composition Wo52 containing high CaO (over 22%), A12O3 (3.5-9.9%) and TiO2 (1-5%), and ranged EnO-29, Fs18-50, and Wo48-55. Olivine contains variable composition ranged Fo2.8-90 with Fe-rich rim and extremely Mg-rich core; however, most of the olivine is in the range Fo57-72. Plagioclase is almost pure anorthite (An97-100). Conclusion: Macroscopically, LEW87051 and Asuka angrites are clearly recognized as individual specimens for they are completely covered with a black fusion crust. The great distance between the two localities strongly supports the fact. Therefore, it seems that both angrites have individually fallen on the Antarctic continent and they are not a pair. Nevertheless, both angrites are petrographically very similar, especially their mineralogy and chemical composition, except for some differences in their texture (Figs. 1 and 2). Two angrites LEW87051 and A-881371 seem to have a close genetic relationship on the parent body. LEW87051 and A-881371 angrites are quite difference from Angra dos Reis (ADOR) and LEW86010 angrites from their petrography, mineralogy, and compositions [2,3]. References: [1] Mason B. (1989) Antarctic Meteorite Newsletter 12, No. 1, 15. [2] Printz N. et al. (1977) EPSL, 35, 317-330. [3] Mason B. (1988) Antarctic Meteorite Newsletter 10, No. 2, 32 .

Principles of Thermal Expansion in Feldspars

NASA Astrophysics Data System (ADS)

Hovis, Guy; Medford, Aaron; Conlon, Maricate; Tether, Allison; Romanoski, Anthony

2010-05-01

Following the recent thermal expansion work of Hovis et al. (1) on AlSi3 feldspars, we have investigated the thermal expansion of plagioclase, Ba-K, and Ca-K feldspar crystalline solutions. X-ray powder diffraction data were collected between room temperature and 925 °C on six natural plagioclase specimens ranging in composition from anorthite to oligoclase, the K-exchanged equivalents of these plagioclase specimens, and five synthetic Ba-K feldspars with compositions ranging from 25 to 99 mol % BaAl2Si2O8. The resulting thermal expansion coefficients (α) for volume have been combined with earlier results for end-member Na- and K-feldspars (2,3). Unlike AlSi3 feldspars, Al2Si2 feldspars, including anorthite and celsian from the present study plus Sr- and Pb-feldspar from other workers (4,5), show essentially constant and very limited thermal expansion, regardless of divalent cation size. In the context of structures where the Lowenstein rule (6) requires Al and Si to alternate among tetrahedra, the proximity of bridging Al-O-Si oxygen ions to divalent neighbors (ranging from 0 to 2) produces short Ca-O (or Ba-O) bonds (7,8) that apparently are the result of local charge-balance requirements (9). Gibbs et al. (10) suggest that short bonds such as these have a partially covalent character. This in turn stiffens the structure. Thus, for feldspar series with coupled substitution the change away from a purely divalent M-site occupant gives the substituting (less strongly bonded) monovalent cations increasingly greater influence on thermal expansion. Overall, then, thermal expansion in the feldspar system is well represented on a plot of α against room-temperature volume, where one sees a quadrilateral bounded by data for (A) AlSi3 feldspars whose expansion behavior is controlled largely by the size of the monovalent alkali-site occupant, (B) Al2Si2 feldspars whose expansion is uniformly limited by partially-covalent bonds between divalent M-site occupants and bridging Al-O-Si oxygens, (C) plagioclase (11,12,13) and (D) Ba-K feldspars (12) where coupled substitution across the series produces expansion behavior that rapidly transitions from one control to the other. Generally, thermal expansion coefficients vary linearly as functions of room-temperature volume between the relevant end members. Thus, the thermal expansion of any feldspar can be estimated simply from knowledge of its chemical system and room-temperature volume. References cited: (1) Hovis, Morabito, Spooner, Mott, Person, Henderson, Roux & Harlov (2008) American Mineralogist 93, 1568-1573. (2) Hovis & Graeme-Barber (1997) American Mineralogist 82, 158-164. (3) Hovis, Brennan, Keohane & Crelling (1999) The Canadian Mineralogist 37, 701-709. (4) Henderson (1984) Progress in Experimental Petrology, N.E.R.C. Report 6, 78-83. (5) Benna, Tribaudino & Bruno (1999) American Mineralogist 84, 120-129. (6) Lowenstein (1954) American Mineralogist 39, 92 -96. (7) Megaw, Kempster & Radosolovich (1962) Acta Crystallographica 15, 1017-1035. (8) Newham & Megaw (1960) Acta Crystallographica 13, 303-312. (9) Pauling (1929) Journal of the American Chemical Society 51, 1010-1026. (10) Gibbs, Rosso, Cox & Boisen (2003) Physics and Chemistry of Minerals 30, 317-320. (11) Grundy & Brown (1974) In The Feldspars, Eds. MacKenzie & Zussman, 163-173. (12) Hovis, Medford, Conlon, Tether & Romanoski (in review) American Mineralogist. (13) Tribaudino, Angel, Camara, Nestola, Pasqual, & Margiolaki (in review) Contributions to Mineralogy and Petrology.

High-temperature rims around calcium-aluminum-rich inclusions from the CR, CB and CH carbonaceous chondrites

NASA Astrophysics Data System (ADS)

Krot, Alexander N.; Nagashima, Kazuhide; van Kooten, Elishevah M. M.; Bizzarro, Martin

2017-03-01

We describe the mineralogy, petrology and oxygen isotopic compositions of high-temperature rims around mineralogically pristine calcium-aluminum-rich inclusions (CAIs) from the CR, CB and CH carbonaceous chondrites. In CR chondrites, nearly all CAIs are surrounded by single- or multi-layered rims composed of CAI-like minerals; relict CAIs inside chondrules in which the rims were resorbed by the host chondrule melt (Aléon et al., 2002; Makide et al., 2009) are the only exception. A complete multi-layered rim sequence (from inside outward: spinel + hibonite + perovskite → melilite → anorthite replacing melilite → Al-diopside → forsterite) is rarely observed; Al-diopside ± forsterite rims are more common. The CR CAIs and all rim layers are uniformly 16O-rich (Δ17O ∼-24‰), indicating formation in a 16O-rich gaseous reservoir. The mineralogy, petrology and 16O-rich compositions of these rims suggest formation by evaporation/condensation, melting (?), and thermal annealing in the formation region of the host CAIs. We define such rims as the primordial Wark-Lovering (WL) rims. In CH chondrites, most CAIs are uniformly 16O-rich and surrounded by the primordial WL rims. One of the 16O-rich CAIs is surrounded by an anorthite-Al-diopside WL rim showing a range of Δ17O values, from ∼-24‰ to ∼-6‰; Δ17O decreases towards the CAI core. We infer that this rim experienced incomplete melting and O-isotope exchange in an 16O-poor nebular gas, most likely during chondrule formation. Most CAIs in CB chondrites and about 10% of CAIs in CH chondrites are uniformly 16O-depleted igneous inclusions; Δ17O values between individual CAIs vary from ∼-12‰ to ∼-5‰. These CAIs have diverse mineralogies (grossite-rich, hibonite-rich, melilite-rich, spinel-rich, and Al,Ti-diopside ± forsterite-rich), but are surrounded by the mineralogically similar igneous rims composed of ±melilite, Al-diopside and Ca-rich forsterite (0.5-1.4 wt% CaO). The igneous rims and the host igneous CAIs have identical (within uncertainties of our SIMS measurements) O-isotope compositions, suggesting that they crystallized from isotopically similar, but chemically distinct melts. We suggest that the uniformly 16O-depleted igneous rims around the uniformly 16O-depleted igneous CAIs in CB and CH chondrites formed during melting of pre-existing CAIs in an impact-generated plume invoked for the origin of CB chondrites (Krot et al., 2005), followed by O-isotope exchange with an 16O-poor plume gas (Δ17O ∼-2‰), condensation of gaseous SiO and Mg into CAI melt, and its subsequent crystallization. We conclude that high-temperature rims around CAIs from CR, CH and CB chondrites recorded thermal processing in gaseous reservoirs with different oxygen isotopic compositions. In contrast to the isotopically heterogeneous WL rims around CV CAIs, our data provide no evidence that CAIs were transported between 16O-rich and 16O-poor gaseous reservoirs multiple times. We suggest instead that oxygen-isotope heterogeneity in the CV WL rims resulted from a fluid-rock interaction on the CV parent asteroid.

Refractory materials in comet samples

NASA Astrophysics Data System (ADS)

Joswiak, D. J.; Brownlee, D. E.; Nguyen, A. N.; Messenger, S.

2017-08-01

Transmission electron microscope examination of more than 250 fragments, >1 μm from comet Wild 2 and a giant cluster interplanetary dust particle (GCP) of probable cometary origin has revealed four new calcium-aluminum-rich inclusions (CAIs), an amoeboid olivine aggregate (AOA), and an additional AOA or Al-rich chondrule (ARC) object. All of the CAIs have concentric mineral structures and are composed of spinel + anorthite cores surrounded by Al,Ti clinopyroxenes and are similar to two previous CAIs discovered in Wild 2. All of the cometary refractory objects are of moderate refractory character. The mineral assemblages, textures, and bulk compositions of the comet CAIs are similar to nodules in fine-grained, spinel-rich inclusions (FGIs) found in primitive chondrites and like the nodules may be nebular condensates that were altered via solid-gas reactions in the solar nebula. Oxygen isotopes collected on one Wild 2 CAI also match FGIs. The lack of the most refractory inclusions in the comet samples may reflect the higher abundances of small moderately refractory CAI nodules that were produced in the nebula and the small sample sizes collected. In the comet samples, approximately 2-3% of all fragments larger than 1 μm, by number, are CAIs and nearly 50% of all bulbous Stardust tracks contain at least one CAI. We estimate that 0.5 volume % of Wild 2 material and 1 volume % of GCP is in the form of CAIs. ARCs and AOAs account for <1% of the Wild 2 and GCP grains by number.

FIB-NanoSIMS-TEM Coordinated Study of a Wark-Lovering Rim in a Vigarano Type A CAI

NASA Technical Reports Server (NTRS)

Cai, A.; Ito, M.; Keller, L. P.; Ross, D. K.; Nakamura-Messenger, K.

2010-01-01

Wark-Lovering (WL) rims are thin multi layered mineral sequences that surround most Ca, Al-rich inclusions (CAIs). Unaltered WL rims are composed of the same primary high temperature minerals as CAIs, such as melilite, spinel, pyroxene, hibonite, perovskite, anorthite and olivine. It is still unclear whether the rim minerals represent a different generation formed by a separate event from their associated CAIs or are a byproduct of CAI formation. Several models have been proposed for the origins of WL rims including condensation, flashheating, reaction of a CAI with a Mg-Si-rich reservoir (nebular gas or solid); on the basis of mineralogy, abundances of trace elements, O and Mg isotopic studies. Detailed mineralogical characterizations of WL rims at micrometer to nanometer scales have been obtained by TEM observations, but so far no coordinated isotopic - mineralogical studies have been performed. Thus, we have applied an O isotopic imaging technique by NanoSIMS 50L to investigate heterogeneous distributions of O isotopic ratios in minerals within a cross section of a WL rim prepared using a focused ion beam (FIB) instrument. After the isotopic measurements, we determine the detailed mineralogy and microstructure of the same WL FIB section to gain insight into its petrogenesis. Here we present preliminary results from O isotopic and elemental maps by NanoSIMS and mineralogical analysis by FE-SEM of a FIB section of a WL rim in the Vigarano reduced CV3 chondrite.

Impact-melt origin for the Simondium, Pinnaroo, and Hainholz mesosiderites: implicatiions for impact processes beyond the Earth--Moon system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Floran, R J; Caulfield, J B.D.; Harlow, G E

The Simondium, Pinnaroo, and Hainholz mesosiderites are interpreted to be clast-laden impact melts that crystallized from immiscible silicate, metallic (Fe-FeS) liquids. The existence of silicate melts is shown by intergranular basaltic textures. Metallic melts are inferred on the basis of smooth boundaries between metal and troilite and the occurrence of troilite as anastomosing areas that radiate outward into the silicate fractions. These relations suggest that troilite crystallized after silicates, concentrating as a late-stage residuum. Evidence for impact melting includes: diversity and abundance of clast types (mineral, metal, lithic) in various stages of recrystallization and assimilation; differences in mineral chemistries betweenmore » clasts and igneous-textured matrix silicates; unusual metal plus silicate bulk composition. Silicate clasts consist primarily of orthopyroxene and minor olivine with a range of Fe/Fe + Mg ratios, anorthitic plagioclase, and rare orthopyroxenite (diogenite) fragments. Substantial amounts of Fe-Ni metal were melted during the impact events and minor amounts were incorporated into the melts as clasts. The clast populations suggest that at least four rock types were melted and mixed: (a) diogenite, (b) a plagioclase-rich source, possibly cumulate eucrite, (c) dunite, and (d) metal. Most orthopyroxene appears to have been derived from fragmentation of diogenites. Orthopyroxene (En/sub 82-61/) and olivine (Fo/sub 86-67/) clasts include much material unsampled as individual meteorites and probably represent a variety of source rocks.« less

Comparisons of Mineralogy Between Cumulate Eucrites and Lunar Meteorites Possibly from the Farside Anorsothitic Crust

NASA Technical Reports Server (NTRS)

Takeda, H.; Yamaguchi, A.; Hiroi, T.; Nyquist, L. E.; Shih, C.-Y.; Ohtake, M.; Karouji, Y.; Kobayashi, S.

2011-01-01

Anorthosites composed of nearly pure anorthite (PAN) at many locations in the farside highlands have been observed by the Kaguya multiband imager and spectral profiler [1]. Mineralogical studies of lunar meteorites of the Dhofar 489 group [2,3] and Yamato (Y-) 86032 [4], all possibly from the farside highlands, showed some aspects of the farside crust. Nyquist et al. [5] performed Sm-Nd and Ar-Ar studies of pristine ferroan anorthosites (FANs) of the returned Apollo samples and of Dhofar 908 and 489, and discussed implications for lunar crustal history. Nyquist et al. [6] reported initial results of a combined mineralogical/chronological study of the Yamato (Y-) 980318 cumulate eucrite with a conventional Sm-Nd age of 4567 24 Ma and suggested that all eucrites, including cumulate eucrites, crystallized from parental magmas within a short interval following differentiation of their parent body, and most eucrites participated in an event or events in the time interval 4400- 4560 Ma in which many isotopic systems were partially reset. During the foregoing studies, we recognized that variations in mineralogy and chronology of lunar anorthosites are more complex than those of the crustal materials of the HED parent body. In this study, we compared the mineralogies and reflectance spectra of the cumulate eucrites, Y-980433 and 980318, to those of the Dhofar 307 lunar meteorite of the Dhofar 489 group [2]. Here we consider information from these samples to gain a better understanding of the feldspathic farside highlands and the Vesta-like body.

A probabilistic approach to remote compositional analysis of planetary surfaces

USGS Publications Warehouse

Lapotre, Mathieu G.A.; Ehlmann, Bethany L.; Minson, Sarah E.

2017-01-01

Reflected light from planetary surfaces provides information, including mineral/ice compositions and grain sizes, by study of albedo and absorption features as a function of wavelength. However, deconvolving the compositional signal in spectra is complicated by the nonuniqueness of the inverse problem. Trade-offs between mineral abundances and grain sizes in setting reflectance, instrument noise, and systematic errors in the forward model are potential sources of uncertainty, which are often unquantified. Here we adopt a Bayesian implementation of the Hapke model to determine sets of acceptable-fit mineral assemblages, as opposed to single best fit solutions. We quantify errors and uncertainties in mineral abundances and grain sizes that arise from instrument noise, compositional end members, optical constants, and systematic forward model errors for two suites of ternary mixtures (olivine-enstatite-anorthite and olivine-nontronite-basaltic glass) in a series of six experiments in the visible-shortwave infrared (VSWIR) wavelength range. We show that grain sizes are generally poorly constrained from VSWIR spectroscopy. Abundance and grain size trade-offs lead to typical abundance errors of ≤1 wt % (occasionally up to ~5 wt %), while ~3% noise in the data increases errors by up to ~2 wt %. Systematic errors further increase inaccuracies by a factor of 4. Finally, phases with low spectral contrast or inaccurate optical constants can further increase errors. Overall, typical errors in abundance are <10%, but sometimes significantly increase for specific mixtures, prone to abundance/grain-size trade-offs that lead to high unmixing uncertainties. These results highlight the need for probabilistic approaches to remote determination of planetary surface composition.

The Reaction Titanite+Kyanite=Anorthite+Rutile and Titanite-Rutile Barometry in Eclogites

USGS Publications Warehouse

Manning, C.F.; Bohlen, S.R.

1991-01-01

Titanite and rutile are a common mineral pair in eclogites, and many equilibria involving these phases are potentially useful in estimating pressures of metamorphism. We have reversed one such reaction, {Mathematical expression} using a piston-cylinder apparatus. Titanite+kyanite is the high-pressure assemblage and our results locate the equilibrium between 15.5 15.9, 17.7-17.9, 18.8-19.0, and 20.0-20.2 kb at 900, 1000, 1050, and 1100??C, respectively. The experiments require a positive dP/dT of between 20.5 and 23.5 bars/??C for the reaction. We use the reversed equilibrium and two other reactions, {Mathematical expression} and {Mathematical expression} to calculate metamorphic conditions for three eclogite localities. Using these reactions in conjunction with garnet-clinopyroxene Fe2+-Mg exchange equilibria, conditions of metamorphism were 16 kb and 750??C for kyaniteeclogites from Glenelg, Scotland, 21 kb and 625??C for eclogite-facies mica schists from the Tauern Window, Austria, and 46 kb and 850??C for eclogite-facies biotite gneisses from the Kokchetav Massif, USSR. For the Scottish and Austrian eclogites, the pressures derived from the titanite-rutile reactions provide additional constraints on pressures for these localities, leading to precise estimates of metamorphic conditions. In the case of the Soviet Union eclogites, the results show that the silicate-oxide assemblage is consistent with the remarkable occurrence of diamond inclusions in the garnets. The results of this study suggest that titanite and rutile stably coexist in many eclogites and that titanite solid solutions are ideal or nearly so. ?? 1991 Springer-Verlag.

Comparisons of Mineralogy of Lunar Meteorites Possibly from the Farside and The Kaguya Remote Sensing Data to Reconstruct the Earliest Anorthositic Crust of the Moon

NASA Technical Reports Server (NTRS)

Takeda, H.; Nagaoka, H.; Ohtake, M.; Kobayashi, S.; Yamaguchi, A.; Morota, T.; Karouji, Y.; Haruyma, J.; Katou, M.; Hiroi, T.;

Heterogeneity in lunar anorthosite meteorites: implications for the lunar magma ocean model.

PubMed

Russell, Sara S; Joy, Katherine H; Jeffries, Teresa E; Consolmagno, Guy J; Kearsley, Anton

2014-09-13

The lunar magma ocean model is a well-established theory of the early evolution of the Moon. By this model, the Moon was initially largely molten and the anorthositic crust that now covers much of the lunar surface directly crystallized from this enormous magma source. We are undertaking a study of the geochemical characteristics of anorthosites from lunar meteorites to test this model. Rare earth and other element abundances have been measured in situ in relict anorthosite clasts from two feldspathic lunar meteorites: Dhofar 908 and Dhofar 081. The rare earth elements were present in abundances of approximately 0.1 to approximately 10× chondritic (CI) abundance. Every plagioclase exhibited a positive Eu-anomaly, with Eu abundances of up to approximately 20×CI. Calculations of the melt in equilibrium with anorthite show that it apparently crystallized from a magma that was unfractionated with respect to rare earth elements and ranged in abundance from 8 to 80×CI. Comparisons of our data with other lunar meteorites and Apollo samples suggest that there is notable heterogeneity in the trace element abundances of lunar anorthosites, suggesting these samples did not all crystallize from a common magma source. Compositional and isotopic data from other authors also suggest that lunar anorthosites are chemically heterogeneous and have a wide range of ages. These observations may support other models of crust formation on the Moon or suggest that there are complexities in the lunar magma ocean scenario to allow for multiple generations of anorthosite formation. © 2014 The Author(s) Published by the Royal Society. All rights reserved.

Uptake properties of Ni2+ by nCaO.Al2O3.2SiO2 (n=1-4) prepared from solid-state reaction of kaolinite and calcite.

PubMed

Jha, Vinay Kumar; Kameshima, Yoshikazu; Nakajima, Akira; Okada, Kiyoshi; MacKenzie, Kenneth J D

2005-08-31

A series of nCaO.Al2O3.2SiO2 samples (n=1-4) were prepared by solid-state reaction of mechanochemically treated mixtures of kaolinite and calcite fired at 600-1000 degrees C for 24 h. All the samples were X-ray amorphous after firing at 600-800 degrees C but had crystallized by 900 degrees C. The main crystalline phases were anorthite (n=1), gehlenite (n=2 and 3) and larnite (n=4). The uptake of Ni2+ by nCaO.Al2O3.2SiO2 samples fired at 800 and 900 degrees C was investigated at room temperature using solutions with initial Ni2+ concentrations of 0.1-50 mmol/l. Amorphous samples (fired at 800 degrees C) showed a higher Ni2+ uptake capacity than crystalline samples (fired at 900 degrees C). Ni2+ uptake was found to increase with increasing of CaO content. Amorphous 4CaO.Al2O3.2SiO2 showed the highest Ni2+ uptake capacity (about 9 mmol/g). The Ni2+ uptake abilities of the present samples are higher than those of other materials reported in the literature. Since the sorbed Ni2+/released Ca2+ ratios of these samples are close to unity, ion replacement of Ni2+ for Ca2+ is thought to be the principal mechanism of Ni2+ uptake by the present samples.

Heterogeneity in lunar anorthosite meteorites: implications for the lunar magma ocean model

PubMed Central

Russell, Sara S.; Joy, Katherine H.; Jeffries, Teresa E.; Consolmagno, Guy J.; Kearsley, Anton

2014-01-01

The lunar magma ocean model is a well-established theory of the early evolution of the Moon. By this model, the Moon was initially largely molten and the anorthositic crust that now covers much of the lunar surface directly crystallized from this enormous magma source. We are undertaking a study of the geochemical characteristics of anorthosites from lunar meteorites to test this model. Rare earth and other element abundances have been measured in situ in relict anorthosite clasts from two feldspathic lunar meteorites: Dhofar 908 and Dhofar 081. The rare earth elements were present in abundances of approximately 0.1 to approximately 10× chondritic (CI) abundance. Every plagioclase exhibited a positive Eu-anomaly, with Eu abundances of up to approximately 20×CI. Calculations of the melt in equilibrium with anorthite show that it apparently crystallized from a magma that was unfractionated with respect to rare earth elements and ranged in abundance from 8 to 80×CI. Comparisons of our data with other lunar meteorites and Apollo samples suggest that there is notable heterogeneity in the trace element abundances of lunar anorthosites, suggesting these samples did not all crystallize from a common magma source. Compositional and isotopic data from other authors also suggest that lunar anorthosites are chemically heterogeneous and have a wide range of ages. These observations may support other models of crust formation on the Moon or suggest that there are complexities in the lunar magma ocean scenario to allow for multiple generations of anorthosite formation. PMID:25114312

Advanced degradation of brominated epoxy resin and simultaneous transformation of glass fiber from waste printed circuit boards by improved supercritical water oxidation processes.

PubMed

Liu, Kang; Zhang, Zhiyuan; Zhang, Fu-Shen

2016-10-01

This work investigated various supercritical water oxidation (SCWO) systems, i.e. SCWO1 (only water), SCWO2 (water+H2O2) and SCWO3 (water+H2O2/NaOH), for waste printed circuit boards (PCBs) detoxification and recycling. Response surface methodology (RSM) was applied to optimize the operating conditions of the optimal SCWO3 systems. The optimal reaction conditions for debromination were found to be the NaOH of 0.21g, the H2O2 volume of 9.04mL, the time of 39.7min, maximum debromination efficiency of 95.14%. Variance analysis indicated that the factors influencing debromination efficiency was in the sequence of NaOH>H2O2>time. Mechanism studies indicated that the dissociated ions from NaOH in supercritical water promoted the debromination of brominated epoxy resins (BERs) through an elimination reaction and nucleophilic substitution. HO2, produced by H2O2 could induce the oxidation of phenol ring to open (intermediates of BERs), which were thoroughly degraded to form hydrocarbons, CO2, H2O and NaBr. In addition, the alkali-silica reaction between OH(-) and SiO2 induced the phase transformation of glass fibers, which were simultaneously converted into anorthite and albite. Waste PCBs in H2O2/NaOH improved SCWO system were fully degraded into useful products and simultaneously transformed into functional materials. These findings are helpful for efficient recycling of waste PCBs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Direct Measurement of the Wettability of Minerals Using Atomic Force Microscopy

NASA Astrophysics Data System (ADS)

Deng, Y.; Xu, L.; Lu, H.; Wang, H.; Shi, Y.

2016-12-01

The wettability of reservoir rock plays an essential role in affecting the states of fluids (water, oil, etc) in pores which are constructed with various minerals. The contact angle method, which is based on the optical microscope photographs of millimeter-sized droplets on a smooth mineral surface, is one of the most widely employed methods to evaluate the wettability of a rock. However, the real reservoir rocks are composed of several kinds of minerals and thus nonhomogeneous, which leads to different wettability at different location of the rock. The mineral grains are usually micrometer-sized so that the traditional optical contact angle method cannot obtain the wettability of different minerals in the rock. Here we used a tapping-mode atomic force microscopy (TM-AFM, MFP-3D-BIO, Asylum Research) to measure the contact angles of micrometer-sized water droplets on different minerals in a tight sand rock which is mainly composed of quartz, albite, potash feldspar and anorthite. The water droplets varied from submicron to several tens micron in diameter. With the optimization of tool and operation parameters, the AFM tip was well controlled so that the nanoscale morphology of the contact configuration between water film and the mineral surface can be obtained at high resolution without disturbing the liquid surface. The AFM results showed that the contact angles of water on quartz and albite were 30-40 ° and 37-45 °, respectively. The AFM method provides a new measure for the wettability evaluation of reservoir rocks, and it is with potential to be applied to oil and gas hydrate studies.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nguyen, Ba Nghiep; Hou, Zhangshuan; Bacon, Diana H.

This paper applies a multiscale hydro-geochemical-mechanical approach to analyze faulted CO 2 reservoirs using the STOMP-CO 2-R code that is coupled to the ABAQUS® finite element package. STOMP-CO 2-R models the reactive transport of CO 2 causing mineral volume fraction changes that are captured by an Eshelby-Mori-Tanka model implemented in ABAQUS®. A three-dimensional (3D) STOMP-CO 2-R model for a reservoir containing an inclined fault was built to analyze a formation containing a reaction network with 5 minerals: albite, anorthite, calcite, kaolinite and quartz. A 3D finite element mesh that exactly maps the STOMP-CO 2-R grid is developed for coupled hydro-geochemical-mechanicalmore » analyses. The model contains alternating sandstone and shale layers. The impact of reactive transport of CO 2 on the geomechanical properties of reservoir rocks and seals are studied in terms of mineral composition changes that affect their geomechanical responses. Simulations assuming extensional and compressional stress regimes with and without coupled geochemistry are performed to study the stress regime effect on the risk of hydraulic fracture. The tendency for the fault to slip is examined in terms of stress regime, geomechanical and geochemical-mechanical effects as well as fault inclination. The results show that mineralogical changes due to long-term injection of CO 2 reduce the permeability and elastic modulus of the reservoir, leading to increased risk of hydraulic fracture in the injection location and at the caprock seal immediately above the injection zone. Fault slip is not predicted to occur. However, fault inclination and stress regime have an important impact on the slip tendency factor.« less

Heated blends of phosphate waste: Microstructure characterization, effects of processing factors and use as a phosphorus source for alfalfa growth.

PubMed

Loutou, M; Hajjaji, M; Mansori, M; Favotto, C; Hakkou, R

2016-07-15

Microstructure of expandable lightweight aggregates (LWAs), which was composed of phosphate waste (PW), cement kiln dust (CKD) and raw clay (RC) was investigated, and the effects of processing factors (temperature, waste content, soaking time) on their physical properties were quantified by using response surface methodology (RSM). The potential use of LWAs as a phosphorus source was assessed through the use of seeds of alfalfa. It was found that the main minerals of the waste, namely carbonates and fluorapatite, were involved in the formation of labradorite/anorthite and melt respectively. Stability of mullite- the main constituent of CKD- was sensitive to the melt content. The assemblage of the identified phases was discussed based on the CaO-SiO2-Al2O3 phase diagram. The results of RSM showed that the change of compressive strength, firing shrinkage and water absorption of LWAs versus processing factors was well described with a polynomial model and the weights of the effects of the factors increased in the following order: sintering temperature > waste content (in the case of PW-RC) > soaking time. On the other hand, it was found that due to the release of phosphorus by soil-embedded pellets, the growth of alfalfa plants improved, and the rate enhanced in this order: PW-RC > PW-CKD > PW-CKD-RC. The absorbed quantity of phosphorus (0.12%) was still lower than the common uptake amount. Copyright © 2016 Elsevier Ltd. All rights reserved.

Formation of biogenic sheath-like Fe oxyhydroxides in a near-neutral pH hot spring: Implications for the origin of microfossils in high-temperature, Fe-rich environments

NASA Astrophysics Data System (ADS)

Peng, Xiaotong; Chen, Shun; Xu, Hengchao

2013-12-01

small hot spring that is informally called "Fe-waterfall spring" and is located in the Rehai geothermal area discharges hot (42 to 73°C), near-neutral (pH = 7.65) Fe-rich water. Submerged reddish precipitates are composed largely of ferrihydrite, goethite, lepidocrocite, opal-A, quartz, and anorthite, as revealed by X-ray diffraction (XRD) and Mössbauer spectroscopy. Molecular phylogenetic analysis demonstrates that the bacterial community in these precipitates is mainly composed of Cyanobacteria, Planctomycetes, β-proteobacteria, Deinococci-Thermus, and Chlorobi. Scanning electron microscopy and high-resolution transmission electron microscopy examinations show that abundant sheath-like Fe oxyhydroxides, which exhibit different morphologies and sizes, are present in Fe-rich precipitates. These sheath-like structures are composed of ferrihydrite rather than more crystalline lepidocrocite or goethite. Energy-dispersive X-ray spectrometer, scanning transmission electron microscopy, and nano secondary ion mass spectrometry reveal that they are mainly composed of Fe, Si, and O, together with some trace elements. Most of the sheath-like structures are not morphologically comparable to biogenic Fe oxyhydroxides produced by known chemolithotrophic Fe oxidizers, which is consistent with the fact that no chemolithotrophic Fe oxidizers were identified by molecular analysis in the precipitates. We suggest that the sheath-like Fe oxyhydroxides are formed through passive Fe sorption and nucleation onto the cell walls of various thermophiles rather than by the direct metabolic activities of chemolithotrophic Fe oxidizers. Biogenic sheath-like Fe oxyhydroxides in Fe-waterfall spring have important implications for geochemical cycles driven by microorganisms, the origin of microfossils, and the formation of banded iron formations (BIFs) in the Archean ocean.

Self-diffusion of Si and O in diopside-anorthite melt at high pressures

NASA Astrophysics Data System (ADS)

Tinker, David; Lesher, Charles E.; Hutcheon, Ian D.

2003-01-01

Self-diffusion coefficients for Si and O in Di 58An 42 liquid were measured from 1 to 4 GPa and temperatures from 1510 to 1764°C. Glass starting powders enriched in 18O and 28Si were mated to isotopically normal glass powders to form simple diffusion couples, and self-diffusion experiments were conducted in the piston cylinder device (1 and 2 GPa) and in the multianvil apparatus (3.5 and 4 GPa). Profiles of 18O/ 16O and 29,30Si/ 28Si were measured using secondary ion mass spectrometry. Self-diffusion coefficients for O (D(O)) are slightly greater than self-diffusion coefficients for Si (D(Si)) and are often the same within error. For example, D(O) = 4.20 ± 0.42 × 10 -11 m 2/s and D(Si) = 3.65 ± 0.37 × 10 -11 m 2/s at 1 GPa and 1662°C. Activation energies for self-diffusion are 215 ± 13 kJ/mol for O and 227 ± 13 kJ/mol for Si. Activation volumes for self-diffusion are -2.1 ± 0.4 cm 3/mol and -2.3 ± 0.4 cm 3/mol for O and Si, respectively. The similar self-diffusion coefficients for Si and O, similar activation energies, and small, negative activation volumes are consistent with Si and O transport by a cooperative diffusion mechanism, most likely involving the formation and disassociation of a high-coordinated intermediate species. The small absolute magnitudes of the activation volumes imply that Di 58An 42 liquid is close to a transition from negative to positive activation volume, and Adam-Gibbs theory suggests that this transition is linked to the existence of a critical fraction (˜0.6) of bridging oxygen.

Geochemistry and mineralogy of fly-ash from the Mae Moh lignite deposit, Thailand

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hart, B.R.; Powell, M.A.; Fyfe, W.S.

The concentration of 21 elements in fly ash from three boilers (75 MW, 150 MW, and 300 MW) at the EGAT power plant, Mae Moh, Thailand, were determined by INAA. The concentration of 10 major elements was determined by XRF. As, Co, Cr, Ni, Mo, and Sb generally increase in concentration going from bottom ash (BA) through the sequence of electrostatic precipitator ashes (ESPA) and reach maxima of As (352 ppm), Co (45 ppm), Cr (105 ppm), Mo (32 ppm), Ni (106 ppm), and Sb (15 ppm) in the ESPA. Ce, Cs, Fe, Hf, La, Sc, Ta, Tb, and Ybmore » did not exhibit concentration trends or are variable except in the case of one boiler, which showed an increase going from BA to ESPA. Only Br decreased in composition going from BA to ESPA. Rb, Sm, U, and Th showed marked variation in trends. The major elements identified by EDS were Al, Si, S, K, Ca, Fe, and Ba, with minor amounts of Mg, Na, Ti, Mn, and Sr. Al, Si, K, and Ca occur together and are present in most of the fly-ash particles. Ba was found as a major component with Ca, Al, and Si. Fe and Ca are usually associated with sulfur. Some small spheres (< 5 {mu}m) are comprised almost entirely of Fe (probably as oxide). Symplectite textures are noted in high-Fe phases. All elements except Br are significantly enriched in the fly ash relative to the coal, which contains 35% ash. Particle chemistry is consistent with the major mineral phases identified by XRD, which include: quartz, magnetite, mullite, gehlenite, anorthite, hematite, anhydrite, and clinopyroxene.« less

Feldspathic Meteorites MIL 090034 and 090070: Late Additions to the Lunar Crust

NASA Technical Reports Server (NTRS)

Nyquist, L. E.; Shirai, N.; Yamaguchi, A.; Shih, C.-Y.; Park, J.; Ebihara, M.

2016-01-01

Our studies of the Miller Range lunar meteorites MIL 090034, 090036, and 090070 show them to be a diverse suite of rocks from the lunar highlands hereafter referred to as MIL 34, MIL 36, and MIL 70, resp. MIL34 and MIL70, the focus of this work, are crystalline melt breccias. Plagioclase compositions in both peak sharply around An96-97. Mg numbers of olivine vary from 58-65 with a few higher values. MIL36 is a regolith breccia. MIL 34 and MIL 70 have some of the highest Al2O3 abundances of lunar highland meteorites, indicating that they have among the largest modal abundances of plagioclase for lunar meteorites. They have lower Sc and Cr abundances than nearly all lunar highland meteorites except Dho 081, Dho 489 and Dho 733. MIL34 and MIL70 also have similar cosmic ray exposure (CRE) ages of approximately 1-2 Ma indicating they are launch paired. (MIL36 has a larger CRE age approximately greater than 70 Ma). Park et al. found a variation in Ar-Ar ages among subsamples of MIL 34 and MIL70, but preferred ages of 3500+/-110 Ma for the "Dark" phase of MIL 34 anorthite and 3520+/-30 Ma for the "Light" phase of MIL70. Bouvier et al. reported a Pb-Pb age of 3894+/-39 Ma for a feldspathic clast of MIL 34 and a similar age for a melt lithology. Here we reexamine the Rb-Sr and Sm-Nd isotopic data, which show complexities qualitatively consistent with those of the Ar-Ar and Pb-Pb data. The Sm-Nd data in particular suggest that the feldspathic compositions of MIL 34 and MIL 70 formed during initial lunar geochemical differentiation, and REE modeling suggests a relatively late-stage formation.

40Ar/39Ar geochronology of subaerial lava flows of Barren Island volcano and the deep crust beneath the Andaman Island Arc, Burma Microplate

NASA Astrophysics Data System (ADS)

Ray, Jyotiranjan S.; Pande, Kanchan; Bhutani, Rajneesh

2015-06-01

Little was known about the nature and origin of the deep crust beneath the Andaman Island Arc in spite of the fact that it formed part of the highly active Indonesian volcanic arc system, one of the important continental crust forming regions in Southeast Asia. This arc, formed as a result of subduction of the Indian Plate beneath the Burma Microplate (a sliver of the Eurasian Plate), contains only one active subaerial magmatic center, Barren Island volcano, whose evolutional timeline had remained uncertain. In this work, we present results of the first successful attempt to date crustal xenoliths and their host lava flows from the island, by incremental heating 40Ar/39Ar method, in an attempt to understand the evolutionary histories of the volcano and its basement. Based on concordant plateau and isochron ages, we establish that the oldest subaerial lava flows of the volcano are 1.58 ± 0.04 (2σ) Ma, and some of the plagioclase xenocrysts have been derived from crustal rocks of 106 ± 3 (2σ) Ma. Mineralogy (anorthite + Cr-rich diopside + minor olivine) and isotopic compositions (87Sr/86Sr < 0.7040; ɛNd > 7.0) of xenoliths not only indicate their derivation from a lower (oceanic) crustal olivine gabbro but also suggest a genetic relationship between the arc crust and the ophiolitic basement of the Andaman accretionary prism. We speculate that the basements of the forearc and volcanic arc of the Andaman subduction zone belong to a single continuous unit that was once attached to the western margin of the Eurasian Plate.

Pressure-induced amorphization in plagioclase feldspars: A time-resolved powder diffraction study during rapid compression

NASA Astrophysics Data System (ADS)

Sims, M.; Jaret, S.; Carl, E. R.; Schrodt, N.; Rhymer, B.; Mohrholz, V.; Konopkova, Z.; Smith, J.; Liermann, H. P.; Glotch, T. D.; Ehm, L.

2017-12-01

Impact cratering is important in planetary body formation and evolution [1]. The pressure and temperature conditions during impacts are classified using systems [2] that stem from 1) petrographic features and 2) the presence of high pressure mineral phases observed in impactites. Maskelynite, amorphous plagioclase ((Na1-x Cax)Al1+x Si2-x O8), is a key indicator of petrographic type S5 (strongly shocked) and forms between 25 and 45 GPa. However, the formation pressure of maskelynite differs substantially depending on the experimental technique producing it. Shock experiments produce amorphization at > 10 GPa higher than static diamond anvil cell (DAC) experiments. We utilize a new technique, fast compression in combination with time-resolved powder diffraction, to study the effect of strain rate on plagioclase amorphization pressure. Anorthite and albite were compressed to 80 GPa at multiple rates from 0.05 GPa/s to 80 GPa/s, and we observed a decrease in amorphization pressure with increasing compression rate for strain rates of about 10-3 s-1. This decrease demonstrates negative strain rate sensitivity, which is likely caused by structural defects. Negative strain rate sensitivity implies that faster rates are more ductile and heterogeneous and slower rates are more brittle and homogeneous. Our results fit into the deformation framework proposed by Huffman and Reimold [3] and are consistent with the formation mechanism for maskelynite by "shear melting" proposed by Grady [4]. [1] Chao, E.C.T., Shock Metamorphism of Natural Materials., Baltimore, Md: Mono Book Corp, 1968; [2] Stöffler, D., J. Geophys. Res, 76(23), 5541, 1971; [3] Huffman, A.R. and W.U. Reimold, Tectonophysics, 256(1-4), 165-217, 1996; [4] Grady, D., J. Geophys. Res. Solid Earth, 85(B2), 913-924, 1980.

First-principles Calculations of Equilibrium Calcium Isotope Fractionation among Ca-bearing Minerals

NASA Astrophysics Data System (ADS)

Zhou, C.; Wang, W.; Kang, J.; Wu, Z.; Huang, F.

2016-12-01

Calcium isotope fractionation factors of Ca-bearing minerals are investigated with the first principle calculations based on density functional theory (DFT). The sequence of heavy Ca isotope enrichment is forsterite > grossular > butschliite > lime > fluorite > tremolite diopside > anhydrite dolomite titanite > anorthite > perovskite gehlenite aragonite richterite > akermanite > oldhamite. This order is consistent with variation of Ca-O bond lengths, indicating that Ca-O bond energy plays an overwhelming role on the fractionations of Ca isotopes. Our study provides important insights into the Ca isotopic data of meteorites. Our calculation predicts that oldhamites (CaS) are enriched in light Ca isotopes relative to silicate phase if they are in equilibrium, contrast with the observations in Valdes et al (2014). Therefore, oldhamite and silicate phase in the meteorites should be in disequilibrium for Ca isotopes. Our results can also be used to understand Ca isotopic composition of the Moon. Δ44/40Ca between olivine (with CaO content of 2.48 wt%) and diopside is up to 0.41‰ and Δ44/40Cagrossular-diopside is 0.26‰ at 1500K. Feng et al. (2014) calculated that Δ44/40Ca between opx with CaO content of 1.74 wt% and cpx is about 0.27‰ at 1500 K. According to the Lunar Magma Ocean (LMO) model, the modern Moon is chemically stratified (Snyder et al., 1992; Elardo et al., 2011). Assuming that the lower cumulate and upper residual melt are in isotopic equilibrium during the evolution of Lunar Magma Ocean where the cumulate may be mainly composed of olivine and orthopyroxene or garnet/spinel, δ44/40Ca of the Moon could be underestimated by 0.05‰ to 0.25‰ if the shallow lunar samples are used to represent the bulk Moon.

Impacts of CO2 Leakage on a Shallow Aquifer System: Laboratory Column Experiments and Reactive Transport Modeling

NASA Astrophysics Data System (ADS)

Ha, Jong Heon; Jeen, Sung-Wook

2017-04-01

Groundwater quality change due to the leakage of CO2 in a shallow aquifer system is an important aspect of environmental impact assessment in a carbon dioxide capture and storage (CCS) site. This study evaluated geochemical changes in a shallow aquifer system resulting from leakage of CO2 through laboratory column experiments and reactive transport modeling. In the column experiments, two columns were set up and filled with the sediment from the Environmental Impact Test (EIT) facility of the Korea CO2 Storage Environmental Management (K-COSEM) Research Center. Groundwater, also collected form the EIT site, was purged with CO2 or Ar gases, and was pumped into the columns with the pumping rates of 200-1000 mL day-1 (0.124-0.62 m day-1). Profile and time-series effluent samplings were conducted to evaluate the spatial and temporal geochemical changes in the aquifer materials upon contact with CO2. The experimental results showed that after injecting CO2-purged groundwater, the pH was decreased, and alkalinity, electrical conductivity (EC) and concentrations of major cations were increased. The spatial and temporal geochemical changes from the column experiments indicate that dissolution of aquifer materials in contact with dissolved CO2 is the major contributor to the changes in groundwater geochemistry. The reactive transport modeling has been conducted to reproduce these geochemical changes in the aquifer system by incorporating dissolution of the dominant aluminosilicate minerals in the aquifer such as microcline, anorthite, albite, and biotite. This study suggests that pH, alkalinity, EC and concentrations of major cations are important monitoring parameters for detecting CO2 leakage in a shallow groundwater aquifer system.

Petrology of Anomalous Eucrites

NASA Technical Reports Server (NTRS)

Mittlefehldt, D. W.; Peng, Z. X.; Ross, D. K.

2015-01-01

Most mafic achondrites can be broadly categorized as being "eucritic", that is, they are composed of a ferroan low-Ca clinopyroxene, high-Ca plagioclase and a silica phase. They are petrologically distinct from angritic basalts, which are composed of high-Ca, Al-Ti-rich clinopyroxene, Carich olivine, nearly pure anorthite and kirschsteinite, or from what might be called brachinitic basalts, which are composed of ferroan orthopyroxene and high-Ca clinopyroxene, intermediate-Ca plagioclase and ferroan olivine. Because of their similar mineralogy and composition, eucrite-like mafic achondrites formed on compositionally similar asteroids under similar conditions of temperature, pressure and oxygen fugacity. Some of them have distinctive isotopic compositions and petrologic characteristics that demonstrate formation on asteroids different from the parent of the HED clan (e.g., Ibitira, Northwest Africa (NWA) 011). Others show smaller oxygen isotopic distinctions but are otherwise petrologically and compositionally indistinguishable from basaltic eucrites (e.g., Pasamonte, Pecora Escarpment (PCA) 91007). The degree of uniformity in delta O-17 of eucrites and diogenites is one piece of evidence considered to favor of a magma-ocean scenario for their petrogenesis. Given that the O isotopic differences separating Pasamonte and PCA 91007 from other eucrites are small, and that there is an absence of other distinguishing characteristics, a legitimate question is: Did the HED parent asteroid fail to homogenize via a magma-ocean stage, thus explaining outliers like Pasamonte? We are initiating a program of study of anomalous eucrite-like achondrites as one part of our effort to seek a resolution of this issue. Here we present preliminary petrologic information on Asuka (A-) 881394, Elephant Moraine (EET) 87520 and EET 87542. We will have studied several more by conference time.

A heterogeneous lunar interior for hydrogen isotopes as revealed by the lunar highlands samples

NASA Astrophysics Data System (ADS)

Hui, Hejiu; Guan, Yunbin; Chen, Yang; Peslier, Anne H.; Zhang, Youxue; Liu, Yang; Flemming, Roberta L.; Rossman, George R.; Eiler, John M.; Neal, Clive R.; Osinski, Gordon R.

2017-09-01

Knowing the amount and timing of water incorporation into the Moon has fundamental implications for our understanding of how the Earth-Moon system formed. Water has been detected in lunar samples but its abundance, distribution and origin are debated. To address these issues, we report water concentrations and hydrogen isotope ratios obtained by secondary ion mass spectrometry (SIMS) of plagioclase from ferroan anorthosites (FANs), the only available lithology thought to have crystallized directly from the lunar magma ocean (LMO). The measured water contents are consistent with previous results by Fourier transform infrared spectroscopy (FTIR). Combined with literature data, δD values of lunar igneous materials least-degassed at the time of their crystallization range from -280 to + 310 ‰, the latter value being that of FAN 60015 corrected for cosmic ray exposure. We interpret these results as hydrogen isotopes being fractionated during degassing of molecular hydrogen (H2) in the LMO, starting with the magmatic δD value of primordial water at the beginning of LMO being about - 280 ‰, evolving to about + 310 ‰ at the time of anorthite crystallization, i.e. during the formation of the primary lunar crust. The degassing of hydrogen in the LMO is consistent with those of other volatile elements. The wide range of δD values observed in lunar igneous rocks could be due to either various degrees of mixing of the different mantle end members, or from a range of mantle sources that were degassed to different degrees during magma evolution. Degassing of the LMO is a viable mechanism that resulted in a heterogeneous lunar interior for hydrogen isotopes.

Closed system oxygen isotope redistribution in igneous CAIs upon spinel dissolution

NASA Astrophysics Data System (ADS)

Aléon, Jérôme

2018-01-01

In several Calcium-Aluminum-rich Inclusions (CAIs) from the CV3 chondrites Allende and Efremovka, representative of the most common igneous CAI types (type A, type B and Fractionated with Unknown Nuclear isotopic anomalies, FUN), the relationship between 16O-excesses and TiO2 content in pyroxene indicates that the latter commonly begins to crystallize with a near-terrestrial 16O-poor composition and becomes 16O-enriched during crystallization, reaching a near-solar composition. Mass balance calculations were performed to investigate the contribution of spinel to this 16O-enrichment. It is found that a back-reaction of early-crystallized 16O-rich spinel with a silicate partial melt having undergone a 16O-depletion is consistent with the O isotopic evolution of CAI minerals during magmatic crystallization. Dissolution of spinel explains the O isotopic composition (16O-excess and extent of mass fractionation) of pyroxene as well as that of primary anorthite/dmisteinbergite and possibly that of the last melilite crystallizing immediately before pyroxene. It requires that igneous CAIs behaved as closed-systems relative to oxygen from nebular gas during a significant fraction of their cooling history, contrary to the common assumption that CAI partial melts constantly equilibrated with gas. The mineralogical control on O isotopes in igneous CAIs is thus simply explained by a single 16O-depletion during magmatic crystallization. This 16O-depletion occurred in an early stage of the thermal history, after the crystallization of spinel, i.e. in the temperature range for melilite crystallization/partial melting and did not require multiple, complex or late isotope exchange. More experimental work is however required to deduce the protoplanetary disk conditions associated with this 16O-depletion.

Solar Flare Track Exposure Ages in Regolith Particles: A Calibration for Transmission Electron Microscope Measurements

NASA Technical Reports Server (NTRS)

Berger, Eve L.; Keller, Lindsay P.

2015-01-01

Mineral grains in lunar and asteroidal regolith samples provide a unique record of their interaction with the space environment. Space weathering effects result from multiple processes including: exposure to the solar wind, which results in ion damage and implantation effects that are preserved in the rims of grains (typically the outermost 100 nm); cosmic ray and solar flare activity, which result in track formation; and impact processes that result in the accumulation of vapor-deposited elements, impact melts and adhering grains on particle surfaces. Determining the rate at which these effects accumulate in the grains during their space exposure is critical to studies of the surface evolution of airless bodies. Solar flare energetic particles (mainly Fe-group nuclei) have a penetration depth of a few millimeters and leave a trail of ionization damage in insulating materials that is readily observable by transmission electron microscope (TEM) imaging. The density of solar flare particle tracks is used to infer the length of time an object was at or near the regolith surface (i.e., its exposure age). Track measurements by TEM methods are routine, yet track production rate calibrations have only been determined using chemical etching techniques [e.g., 1, and references therein]. We used focused ion beam-scanning electron microscope (FIB-SEM) sample preparation techniques combined with TEM imaging to determine the track density/exposure age relations for lunar rock 64455. The 64455 sample was used earlier by [2] to determine a track production rate by chemical etching of tracks in anorthite. Here, we show that combined FIB/TEM techniques provide a more accurate determination of a track production rate and also allow us to extend the calibration to solar flare tracks in olivine.

Element-based prognostics of occupational pneumoconiosis using micro-proton-induced X-ray emission analysis.

PubMed

He, Xiaodong; Shen, Hao; Chen, Zidan; Rong, Caicai; Ren, Minqin; Hou, Likun; Wu, Chunyan; Mao, Ling; Lu, Quan; Su, Bo

2017-12-01

Pneumoconiosis is an occupational disease accompanied by long-term lung impairment, for which prediction of prognosis is poorly understood because of the complexity of the inhaled particles. Micro-proton-induced X-ray emission (micro-PIXE) analysis, which is advantageous for high-sensitivity, two-dimensional element mapping of lung tissues, was used to investigate element-based predictive factors of prognosis in Chinese patients with welder's and coal miner's pneumoconiosis. Chest radiographs and lung function tests showed that most of the coal miners deteriorated, whereas symptoms in some welders were alleviated after 5 yr, as determined by comparing percent vital capacity (%VC) and forced expiratory volume in the 1st second over forced vital capacity (FEV1.0/FVC) to values taken at the initial diagnosis. Micro-PIXE analysis suggested that the most abundant particulates in welder's pneumoconiosis were Fe, Mn, and Ti (metallic oxide),which were accompanied by particulates containing Si, Al, and Ca (aluminum silicate) or only Si (SiO 2 ); the most abundant particulates in coal miner's pneumoconiosis were composed of C, Si, Al, K, and Ti, which were accompanied by particulates containing Ca or Fe. Particulates containing Al, Si, S, K, Ca, and Ti (orthoclase and anorthite) were correlated with severity of fibrosis. Multivariable linear regression suggested that long-term FEV1.0/FVC decrease was independently associated with Si and smoking index, whereas %VC decrease was associated with Si and Ti. A risk index comprised of these factors was developed to predict the prognosis of pneumoconiosis. Micro-PIXE analysis is feasible for the evaluation of elemental composition and dust exposure, especially for patients whose exposure is mixed or uncertain. Copyright © 2017 the American Physiological Society.

Isotopic Measurements in CAIs with the Nanosims: Implications to the understanding of the Formation process of Ca, Al-Rich Inclusions

NASA Technical Reports Server (NTRS)

Ito, M.; Messenger, S.; Walker, Robert M.

2007-01-01

Ca, Al-rich Inclusions (CAIs) preserve evidence of thermal events that they experienced during their formation in the early solar system. Most CAIs from CV and CO chondrites are characterized by large variations in O-isotopic compositions of primary minerals, with spinel, hibonite, and pyroxene being more O-16-rich than melilite and anorthite, with delta 17, O-18 = approx. -40%o (DELTA O-17 = delta O-17 - 0.52 x delta O-18 = approx. - 20%o ). These anomalous compositions cannot be accounted for by standard mass dependent fractionation and diffusive process of those minerals. It requires the presence of an anomalous oxygen reservoir of nucleosynthetic origin or mass independent fractionations before the formation of CAIs in the early solar system. The CAMECA NanoSIMS is a new generation ion microprobe that offers high sensitivity isotopic measurements with sub 100 nm spatial resolution. The NanoSIMS has significantly improved abilities in the study of presolar grains in various kind of meteorites and the decay products of extinct nuclides in ancient solar system matter. This instrument promises significant improvements over other conventional ion probes in the precision isotopic characterization of sub-micron scales. We report the results of our first O isotopic measurements of various CAI minerals from EK1-6-3 and 7R19-1(a) utilizing the JSC NanoSIMS 50L ion microprobe. We evaluate the measurement conditions, the instrumental mass fractionation factor (IMF) for O isotopic measurement and the accuracy of the isotopic ratio through the analysis of a San Carlos olivine standard and CAI sample of 7R19-1(a).

Effect of infiltrated water on rheology of plagioclase feldspar under lower crustal condition

NASA Astrophysics Data System (ADS)

Kido, M.; Muto, J.; Koizumi, S.; Nagahama, H.

2016-12-01

Fluids in the deep crust have an important role in deformation of lithosphere and seismicity. In this study, we performed deformation experiments to reveal rheological properties of plagioclase feldspars as a main constituent of crustal materials with infilitrated water. Axial compression tests on synthetic polycrystalline anorthite (An) were performed in a Griggs-type deformation apparatus at temparature of 900 °C, strain rates of roughly about 10-5 s-1 and various confining pressures of 0.8-1.4 GPa. Distilled water was added on samples before tests. Times for infiltration of water into samples were changed to investigate the variation of strength associated with diffusion of water. Strengths of wet An tended to decrease with infiltration time or strain magnitude. If other conditions such as temperature, time and strain being the same, strengths increase with confining pressures. Recovered samples show that deformation was concentrated in the lower part of samples. Differential stresses were significantly lower than predicted values by a previous flow law for wet An obtained by low pressure gas apparatus ( 0.4 GPa, Rybacki et al., 2006). This implies that the effect of water on mechanical behavior in higher pressure might be larger than those predicted by lower pressure experiments. Ideal water concentration and strength profile of internal of samples were estimated by one-dimensional model of grain boundary diffusion. Estimated strength of internal part of samples was significant higher than measured stresses. There is possibility that cataclastic flow partially occurred in samples. In addition, deformation-enhanced fluid flow probably occurred. In conclusion, strength of wet An depends on water infiltration time, strain magnitude and confining pressure. The results suggest that the strength of fluid-rich regions in the lower crust becomes lower than that predicted by previous studies.

An ion microprobe study of CAIs from CO3 meteorites. [Abstract only

NASA Technical Reports Server (NTRS)

Russell, S. S.; Greenwood, R. C.; Fahey, A. J.; Huss, G. R.; Wasserburg, G. J.

1994-01-01

When attempting to interpret the history of Ca, Al-rich inclusions (CAIs) it is often difficult to distinguish between primary features inherited from the nebula and those produced during secondary processing on the parent body. We have undertaken a systematic study of CAIs from 10 CO chondrites, believed to represent a metamorphic sequence with the goal of distinguishing primary and secondary features. ALHA 77307 (3.0), Colony (3.0), Kainsaz (3.1), Felix (3.2), ALH 82101 (3.3), Ornans (3.3), Lance (3.4), ALHA 77003 (3.5), Warrenton (3.6), and Isna (3.7) were examined by Scanning Electron Microscopy (SEM) and optical microscopy. We have identified 141 CAIs within these samples, and studied in detail the petrology of 34 inclusions. The primary phases in the lower petrologic types are spinel, melilite, and hibonite. Perovskite, FeS, ilmenite, anorthite, kirschsteinite, and metallic Fe are present as minor phases. Melilite becomes less abundant in higher petrologic types and was not detected in chondrites of type 3.5 and above, confirming previous reports that this mineral easily breaks down during heating. Iron, an element that would not be expected to condense at high temperatures, has a lower abundance in spinel from low-petrologic-type meteorites than those of higher grade, and CaTiO3 is replaced by FeTiO3 in meteorites of higher petrologic type. The abundance of CAIs is similar in each meteorite. Eight inclusions have been analyzed by ion probe. The results are summarized. The results obtained to date show that CAIs in CO meteorites, like those from other meteorite classes, contain Mg* and that Mg in some inclusions has been redistributed.

Glass-ceramic nuclear waste forms obtained by crystallization of SiO 2-Al 2O 3-CaO-ZrO 2-TiO 2 glasses containing lanthanides (Ce, Nd, Eu, Gd, Yb) and actinides (Th): Study of the crystallization from the surface

NASA Astrophysics Data System (ADS)

Loiseau, P.; Caurant, D.

2010-07-01

Glass-ceramic materials containing zirconolite (nominally CaZrTi 2O 7) crystals in their bulk can be envisaged as potential waste forms for minor actinides (Np, Am, Cm) and Pu immobilization. In this study such matrices are synthesized by crystallization of SiO 2-Al 2O 3-CaO-ZrO 2-TiO 2 glasses containing lanthanides (Ce, Nd, Eu, Gd, Yb) and actinides (Th) as surrogates. A thin partially crystallized layer containing titanite and anorthite (nominally CaTiSiO 5 and CaAl 2Si 2O 8, respectively) growing from glass surface is also observed. The effect of the nature and concentration of surrogates on the structure, the microstructure and the composition of the crystals formed in the surface layer is presented in this paper. Titanite is the only crystalline phase able to significantly incorporate trivalent lanthanides whereas ThO 2 precipitates in the layer. The crystal growth thermal treatment duration (2-300 h) at high temperature (1050-1200 °C) is shown to strongly affect glass-ceramics microstructure. For the system studied in this paper, it appears that zirconolite is not thermodynamically stable in comparison with titanite growing form glass surface. Nevertheless, for kinetic reasons, such transformation (i.e. zirconolite disappearance to the benefit of titanite) is not expected to occur during interim storage and disposal of the glass-ceramic waste forms because their temperature will never exceed a few hundred degrees.

Mobilization of Ag, heavy metals and Eu from the waste deposit of the Las Herrerias mine (Almería, SE Spain)

NASA Astrophysics Data System (ADS)

Navarro, A.; Cardellach, E.

2009-02-01

We studied the mobility of silver, heavy metals and europium in waste from the Las Herrerías mine in Almería (SE Spain). The most abundant primary mineral phases in the mine wastes are hematite, hydrohematite, barite, quartz, muscovite, anorthite, calcite and phillipsite. The minor phase consisted of primary minerals including ankerite, cinnabar, digenite, magnesite, stannite, siderite and jamesonite, and secondary minerals such as glauberite, szomolnokite, thenardite and uklonscovite. The soils show high concentrations of Ag (mean 21.6 mg kg-1), Ba (mean 2.5%), Fe (mean 114,000 mg kg-1), Sb (mean 342.5 mg kg-1), Pb (mean 1,229.8 mg kg-1), Zn (mean 493 mg kg-1), Mn (mean 4,321.1 mg kg-1), Cd (mean 1.2 mg kg-1) and Eu (mean 4.0 mg kg-1). The column experiments showed mobilization of Ag, Al, Ba, Cu, Cd, Eu, Fe, Mn, Ni, Sb, Pb and Zn, and the inverse modelling showed that the dissolution of hematite, hausmannite, pyrolusite and anglesite can largely account for the mobilization of Fe, Mn and Pb in the leaching experiment. The mobility of silver may be caused by the presence of kongsbergite and chlorargyrite in the waste, while the mobility of Eu seems to be determined by Eu(OH)3, which controls the solubility of Eu in the pH-Eh conditions of the experiments. The mineralogy, pH, Eh and geochemical composition of the mine wastes may explain the possible mobilization of heavy metals and metalloids. However, the absence of contaminants in the groundwater may be caused by the carbonate-rich environment of “host-rocks” that limits their mobility.

Anatexis at the roof of an oceanic magma chamber at IODP Site 1256 (equatorial Pacific): an experimental study

NASA Astrophysics Data System (ADS)

Erdmann, Martin; Fischer, Lennart A.; France, Lydéric; Zhang, Chao; Godard, Marguerite; Koepke, Jürgen

2015-04-01

Replenished axial melt lenses at fast-spreading mid-oceanic ridges may move upward and intrude into the overlying hydrothermally altered sheeted dikes, resulting in high-grade contact metamorphism with the potential to trigger anatexis in the roof rocks. Assumed products of this process are anatectic melts of felsic composition and granoblastic, two-pyroxene hornfels, representing the residue after partial melting. Integrated Ocean Drilling Program Expeditions 309, 312, and 335 at Site 1256 (eastern equatorial Pacific) sampled such a fossilized oceanic magma chamber. In this study, we simulated magma chamber roof rock anatectic processes by performing partial melting experiments using six different protoliths from the Site 1256 sheeted dike complex, spanning a lithological range from poorly to strongly altered basalts to partially or fully recrystallized granoblastic hornfels. Results show that extensively altered starting material lacking primary magmatic minerals cannot reproduce the chemistry of natural felsic rocks recovered in ridge environments, especially elements sensitive to hydrothermal alteration (e.g., K, Cl). Natural geochemical trends are reproduced through partial melting of moderately altered basalts from the lower sheeted dikes. Two-pyroxene hornfels, the assumed residue, were reproduced only at low melting degrees (<20 vol%). The overall amphibole absence in the experiments confirms the natural observation that amphibole is not produced during peak metamorphism. Comparing experimental products with the natural equivalents reveals that water activity ( aH2O) was significantly reduced during anatectic processes, mainly based on lower melt aluminum oxide and lower plagioclase anorthite content at lower aH2O. High silica melt at the expected temperature (1000-1050 °C; peak thermal overprint of two-pyroxene hornfels) could only be reproduced in the experimental series performed at aH2O = 0.1.

UHT overprint of HP rocks? A case study from the Adula nappe complex (Central Alps, N Italy)

NASA Astrophysics Data System (ADS)

Tumiati, Simone; Zanchetta, Stefano; Malaspina, Nadia; Poli, Stefano

2014-05-01

The Adula-Cima Lunga nappe complex is located on the eastern flank of the Lepontine Dome and represents the highest of the Lower Penninic units of the Central Alps. The Adula nappe largely consists of orthogneiss and paragneiss of pre-Mesozoic origin, variably retrogressed eclogites preserved as boudins within paragneiss, minor ultramafic bodies and metasedimentary rocks of presumed Mesozoic age. The higher metamorphic conditions have been estimated for the peridotite lenses in the southern part of the nappe at pressure over 3.0 GPa and temperature of 800-850°C. Garnet lherzolite bodies crop out at three localities, from west to east: Cima di Gagnone, Alpe Arami and Mt. Duria. After the partial subduction of the European distal margin beneath the Africa-Adria margin, the HP rocks were overprinted by an upper amphibolite facies metamorphism that postdates the main phase of nappe stacking. In the southern sector of the Lepontine Dome, adjacent to the Insubric Fault, metamorphic conditions promoted extensive migmatization of both metasedimentary and metagranitoid rocks. In one single outcrop, at Monte Duria, garnet lherzolites occur in m-sized boudins hosted within partly granulitized amphibole-bearing and k-feldspar gneisses that contain also some decimeter-sized boudins of both mafic and metapelitic eclogites. This rock association is in turn embedded within the migmatitic gneisses that form most of the southern sector of the Adula nappe. Petrographic and chemical analyses indicate that garnet peridotite is composed of olivine (XMg=0.88), orthopyroxene, clinopyroxene and garnet (Py68; Cr2O3 up to 1.45 wt%) with inclusions of Cr-rich spinel (up to Cr/(Al+Cr)=0.55) surrounded by kelyphitic symplectites of opx + cpx/amph + spl. These reaction produced double coronas, one composed of opx (former ol) and one composed of cpx + opx+ spl. In one kelyphite, we observed the uncommon occurrence of ZrO2 (baddeleyite) and ZrTi2O6 (srilankite). Tiny crystals of these two Zr-bearing phases (˜1 μm) are invariably located in the opx corona after ol. The cpx + opx + spl corona (after grt) contains, instead, zircon. Baddeleyite should have formed through a reaction of the type Mg2SiO4 + ZrSiO4 = MgSiO3 + ZrO2. ZrO2 and ZrTi2O6 display a low amount of solid solution. These compositions are consistent with T below 1200°C, but an improvement of the thermodynamic model is needed in order to better constrain the T of the granulitic overprint on the basis of these Zr-bearing phases. In mafic eclogites, the HP association consists of garnet (Py40Alm37Sp20), omphacite (preserved as inclusion, containing Jd30 and Mg# 0.87), kyanite and minor quartz. Omphacite is almost always replaced by cpx (Jd5) + plag (An55) symplectites. Garnet is surrounded by plag (An33) + opx (En70) symplectites. Kyanite is replaced by plag (An84) + spinel + sapphirine. The spinel-sapphirine Fe-Mg thermometer suggests T of about 850°C due to granulite-facies overprint. We observed sapphirine associated with cpx + opx + plag also in kelyphites after garnet in clinopyroxenites. In eclogitic metapelites, kyanite is replaced by a corundum + anorthite ± spinel assemblage. A corundum-rich layer occurs between eclogites and the host gneiss. Cm-sized emerald green zoisite in this layer is replaced by anorthitic plagioclase ± cpx ± spinel ± calcite. The observed assemblages point to a diffuse granulitization of both the peridotites and the hosting HP rocks of Mt. Duria, suggesting a nearly isothermal decompression from peak-pressure conditions. The surrounding migmatitic gneiss do not display evidence of such granulitic event, having been formed at T<700°C. The mechanism and timing of emplacement of the garnet peridotite and associated HP-HT rocks in the country migmatites, and whether or not the subduction event is related to the Alpine or to an older orogenic cycle are still a matter of debate.

Origin of peraluminous minerals (corundum, spinel, and sapphirine) in a highly calcic anorthosite from the Sittampundi Layered Complex, Tamil Nadu, India

NASA Astrophysics Data System (ADS)

Karmakar, Shreya; Mukherjee, Subham; Sanyal, Sanjoy; Sengupta, Pulak

2017-08-01

The highly calcic anorthosite (An>95) from the Sittampundi Layered Complex (SLC) develops corundum, spinel and sapphirine that are hitherto not reported from any anorthositic rocks in the world. Petrological observations indicate the following sequence of mineral growth: plagioclasematrix → corundum; clinopyroxene → amphibole; corundum + amphibole → plagioclasecorona + spinel; and spinel + corundum → coronitic sapphirine. Phase relations in the CaO-Na2O-Al2O3-SiO2-H2O (CNASH) system suggest that corundum was presumably developed through vapour present incongruent melting of the highly calcic plagioclase during ultra-high temperature (UHT) metamorphism ( T ≥ 1000 °C, P ≥ 9 kbar). Topological constraints in parts of the Na2O-CaO-MgO-Al2O3-SiO2-H2O (NCMASH) system suggest that subsequent to the UHT metamorphism, aqueous fluid(s) permeated the rock and the assemblage corundum + amphibole + anorthite + clinozoisite was stabilized during high-pressure (HP) metamorphism (11 ± 2 kbar, 750 ± 50 °C). Constraints of the NCMASH topology and thermodynamic and textural modeling study suggest that coronitic plagioclase and spinel formed at the expense of corundum + amphibole during a steeply decompressive retrograde P- T path (7-8 kbar and 700-800 °C) in an open system. Textural modeling studies combined with chemical potential diagrams (μSiO2-μMgO) in the MASH system support the view that sapphirine also formed from due to silica and Mg metasomatism of the precursor spinel ± corundum, on the steeply decompressive retrograde P- T path, prior to onset of significant cooling of the SLC. Extremely channelized fluid flow and large positive solid volume change of the stoichiometrically balanced sapphirine forming reaction explains the localized growth of sapphirine.

Assessing ocean alkalinity for carbon sequestration

NASA Astrophysics Data System (ADS)

Renforth, Phil; Henderson, Gideon

2017-09-01

Over the coming century humanity may need to find reservoirs to store several trillions of tons of carbon dioxide (CO2) emitted from fossil fuel combustion, which would otherwise cause dangerous climate change if it were left in the atmosphere. Carbon storage in the ocean as bicarbonate ions (by increasing ocean alkalinity) has received very little attention. Yet recent work suggests sufficient capacity to sequester copious quantities of CO2. It may be possible to sequester hundreds of billions to trillions of tons of C without surpassing postindustrial average carbonate saturation states in the surface ocean. When globally distributed, the impact of elevated alkalinity is potentially small and may help ameliorate the effects of ocean acidification. However, the local impact around addition sites may be more acute but is specific to the mineral and technology. The alkalinity of the ocean increases naturally because of rock weathering in which >1.5 mol of carbon are removed from the atmosphere for every mole of magnesium or calcium dissolved from silicate minerals (e.g., wollastonite, olivine, and anorthite) and 0.5 mol for carbonate minerals (e.g., calcite and dolomite). These processes are responsible for naturally sequestering 0.5 billion tons of CO2 per year. Alkalinity is reduced in the ocean through carbonate mineral precipitation, which is almost exclusively formed from biological activity. Most of the previous work on the biological response to changes in carbonate chemistry have focused on acidifying conditions. More research is required to understand carbonate precipitation at elevated alkalinity to constrain the longevity of carbon storage. A range of technologies have been proposed to increase ocean alkalinity (accelerated weathering of limestone, enhanced weathering, electrochemical promoted weathering, and ocean liming), the cost of which may be comparable to alternative carbon sequestration proposals (e.g., $20-100 tCO2-1). There are still many unanswered technical, environmental, social, and ethical questions, but the scale of the carbon sequestration challenge warrants research to address these.

Ferric iron partitioning between plagioclase and silicate liquid: thermodynamics and petrological applications

NASA Astrophysics Data System (ADS)

Sugawara, Toru

2001-06-01

A series of Fe and Mg partition experiments between plagioclase and silicate liquid were performed in the system SiO2-Al2O3-Fe2O3-FeO-MgO-CaO-Na2O under oxygen fugacities from below the IW buffer up to that of air. A thermodynamic model of plagioclase solid solution for the (CaAl,NaSi,KSi)(Fe3+,Al3+)Si2O8-Ca(Fe2+,Mg)Si3O8 system is proposed and is calibrated by regression analysis based on new and previously reported experimental data of Fe and Mg partitioning between plagioclase and silicate liquid, and reported thermodynamic properties of end members, ternary feldspar and silicate liquid. Using the derived thermodynamic model, FeOt, MgO content and Mg/(Fet+Mg) in plagioclase can be predicted from liquid composition with standard deviations of +/-0.34 wt% (relative error =9%) and +/-0.08 wt% (14%) and +/-0.7 (8%) respectively. Calculated Fe3+-Al exchange chemical potentials of plagioclase, $μ { Fe{ 3 + } ( {Al} ){ - 1} }{ Pl} agree with those calculated using reported thermodynamic models for multicomponent spinel, μ { Fe{ 3 + } ( {Al} ){ - 1} }{ Sp} and clinopyroxene, μ { Fe{ 3 + } ( {Al} ){ - 1} }{ Cpx} $ . The FeOt content of plagioclase coexisting with spinel or clinopyroxene is affected by Fe3+/(Fe3++Al) and Mg/(Fe+Mg) of spinel or clinopyroxene and temperature, while it is independent of the anorthite content of plagioclase. Three oxygen barometers based on the proposed model are investigated. Although the oxygen fugacities predicted by the plagioclase-liquid oxygen barometer are scattered, this study found that plagioclase-spinel-clinopyroxene-oxygen and plagioclase-olivine-oxygen equilibria can be used as practical oxygen barometers. As a petrological application, prediction of plagioclase composition and fO2 are carried out for the Upper Zone of the Skaergaard intrusion. The estimated oxygen fugacities are well below QFM buffer and consistent with the estimation of oxidization states in previous studies.

An experimental study of ^{{{{Fe}}^{2 + } {-}{{Mg}}}} K_{{D}} between orthopyroxene and rhyolite: a strong dependence on H2O in the melt

NASA Astrophysics Data System (ADS)

Waters, Laura E.; Lange, Rebecca A.

2017-06-01

The effect of temperature, pressure, and dissolved H2O in the melt on the Fe2+-Mg exchange coefficient between orthopyroxene and rhyolite melt was investigated with a series of H2O fluid-saturated phase-equilibrium experiments. Experiments were conducted in a rapid-quench cold-seal pressure vessel over a temperature and pressure range of 785-850 °C and 80-185 MPa, respectively. Oxygen fugacity was buffered with the solid Ni-NiO assemblage in a double-capsule assembly. These experiments, when combined with H2O-undersaturated experiments in the literature, show that ^{{{{Fe}}^{2 + } {-}{{Mg}}}} K_{{D}} between orthopyroxene and rhyolite liquid increases strongly (from 0.23 to 0.54) as a function of dissolved water in the melt (from 2.7 to 5.6 wt%). There is no detectable effect of temperature or pressure over an interval of 65 °C and 100 MPa, respectively, on the Fe2+-Mg exchange coefficient values. The data show that Fe-rich orthopyroxene is favored at high water contents, whereas Mg-rich orthopyroxene crystallizes at low water contents. It is proposed that the effect of dissolved water in the melt on the composition of orthopyroxene is analogous to its effect on the composition of plagioclase. In the latter case, dissolved hydroxyl groups preferentially complex with Na+ relative to Ca2+, which reduces the activity of the albite component, leading to a more anorthite-rich (calcic) plagioclase. Similarly, it is proposed that dissolved hydroxyl groups preferentially complex with Mg2+ relative to Fe2+, thus lowering the activity of the enstatite component, leading to a more Fe-rich orthopyroxene at high water contents in the melt. The experimental results presented in this study show that reversely zoned pyroxene (i.e., Mg-rich rims) in silicic magmas may be a result of H2O degassing and not necessarily the result of mixing with a more mafic magma.

A refractory inclusion returned by Stardust from comet 81P/Wild 2

NASA Astrophysics Data System (ADS)

Simon, S. B.; Joswiak, D. J.; Ishii, H. A.; Bradley, J. P.; Chi, M.; Grossman, L.; AlÉOn, J.; Brownlee, D. E.; Fallon, S.; Hutcheon, I. D.; Matrajt, G.; McKeegan, K. D.

2008-11-01

Among the samples returned from comet 81P/Wild 2 by the Stardust spacecraft is a suite of particles from one impact track (Track 25) that are Ca-, Al-rich and FeO-free. We studied three particles from this track that range in size from 5.3 × 3.2 μ to 15 × 10 μ. Scanning and transmission electron microscopy show that they consist of very fine-grained (typically from ˜0.5 to ˜2 μ) Al-rich, Ti-bearing and Ti-free clinopyroxene, Mg-Al spinel and anorthite, with trace amounts of fine perovskite, FeNi metal and osbornite (TiN) grains. In addition to these phases, the terminal particle, named "Inti", also contains melilite. All of these phases, with the exception of osbornite, are common in refractory inclusions and are predicted to condense at high temperature from a gas of solar composition. Osbornite, though very rare, has also been found in meteoritic refractory inclusions, and could have formed in a region of the nebula where carbon became enriched relative to oxygen compared to solar composition. Compositions of Ti-pyroxene in Inti are similar, but not identical, to those of fassaite from Allende inclusions. Electron energy loss spectroscopy shows that Ti-rich pyroxene in Inti has Ti3+/Ti4+within the range of typical meteoritic fassaite, consistent with formation under reducing conditions comparable to those of a system of solar composition. Inti is 16O-rich, with δ18O?δ17O?-40%0, like unaltered phases in refractory inclusions and refractory IDPs. With grain sizes, mineralogy, mineral chemistry, and an oxygen isotopic composition like those of refractory inclusions, we conclude that Inti is a refractory inclusion that formed in the inner solar nebula. Identification of a particle that formed in the inner solar system among the comet samples demonstrates that there was transport of materials from the inner to the outer nebula, probably either in a bipolar outflow or by turbulence.

Potential of fly ash for neutralisation of acid mine drainage.

PubMed

Qureshi, Asif; Jia, Yu; Maurice, Christian; Öhlander, Björn

2016-09-01

Lignite (PK), bituminous (FI) and biomass (SE) fly ashes (FAs) were mineralogically and geochemically characterised, and their element leachability was studied with batch leaching tests. The potential for acid neutralisation (ANP) was quantified by their buffering capacity, reflecting their potential for neutralisation of acid mine drainage. Quartz was the common mineral in FAs detected by XRD with iron oxide, anhydrite, and magnesioferrite in PK, mullite and lime in FI, and calcite and anorthite in SE. All the FAs had high contents of major elements such as Fe, Si, Al and Ca. The Ca content in SE was six and eight times higher compared to PK and FI, respectively. Sulphur content in PK and SE was one magnitude higher than FI. Iron concentrations were higher in PK. The trace element concentrations varied between the FAs. SE had the highest ANP (corresponding to 275 kg CaCO3 tonne(-1)) which was 15 and 10 times higher than PK and FI, respectively. The concentrations of Ca(2+), SO4 (2-), Na(+) and Cl(-) in the leachates were much higher compared to other elements from all FA samples. Iron, Cu and Hg were not detected in any of the FA leachates because of their mild to strong alkaline nature with pH ranging from 9 to 13. Potassium leached in much higher quantity from SE than from the other ashes. Arsenic, Mn and Ni leached from PK only, while Co and Pb from SE only. The concentrations of Zn were higher in the leachates from SE. The FAs used in this study have strong potential for the neutralisation of AMD due to their alkaline nature. However, on the other hand, FAs must be further investigated, with scaled-up experiments before full-scale application, because they might leach pronounced concentrations of elements of concern with decreasing pH while neutralising AMD.

Petrology and geochemistry of feldspathic impact-melt breccia Abar al' Uj 012, the first lunar meteorite from Saudi Arabia

NASA Astrophysics Data System (ADS)

Mészáros, Marianna; Hofmann, Beda A.; Lanari, Pierre; Korotev, Randy L.; Gnos, Edwin; Greber, Nicolas D.; Leya, Ingo; Greenwood, Richard C.; Jull, A. J. Timothy; Al-Wagdani, Khalid; Mahjoub, Ayman; Al-Solami, Abdulaziz A.; Habibullah, Siddiq N.

2016-10-01

Abar al' Uj (AaU) 012 is a clast-rich, vesicular impact-melt (IM) breccia, composed of lithic and mineral clasts set in a very fine-grained and well-crystallized matrix. It is a typical feldspathic lunar meteorite, most likely originating from the lunar farside. Bulk composition (31.0 wt% Al2O3, 3.85 wt% FeO) is close to the mean of feldspathic lunar meteorites and Apollo FAN-suite rocks. The low concentration of incompatible trace elements (0.39 ppm Th, 0.13 ppm U) reflects the absence of a significant KREEP component. Plagioclase is highly anorthitic with a mean of An96.9Ab3.0Or0.1. Bulk rock Mg# is 63 and molar FeO/MnO is 76. The terrestrial age of the meteorite is 33.4 ± 5.2 kyr. AaU 012 contains a 1.4 × 1.5 mm2 exotic clast different from the lithic clast population which is dominated by clasts of anorthosite breccias. Bulk composition and presence of relatively large vesicles indicate that the clast was most probably formed by an impact into a precursor having nonmare igneous origin most likely related to the rare alkali-suite rocks. The IM clast is mainly composed of clinopyroxenes, contains a significant amount of cristobalite (9.0 vol%), and has a microcrystalline mesostasis. Although the clast shows similarities in texture and modal mineral abundances with some Apollo pigeonite basalts, it has lower FeO and higher SiO2 than any mare basalt. It also has higher FeO and lower Al2O3 than rocks from the FAN- or Mg-suite. Its lower Mg# (59) compared to Mg-suite rocks also excludes a relationship with these types of lunar material.

Expanding the REE Partitioning Database for Lunar Materials

NASA Technical Reports Server (NTRS)

Rapp, Jennifer F.; Draper, David S.

2014-01-01

Positive europium anomalies are ubiquitous in the plagioclase-rich rocks of the lunar highlands, and complementary negative Eu anomalies are found in most lunar basalts. This is taken as evidence of a large-scale differentation event, with crystallization of a global-scale lunar magma ocean (LMO) resulting in a plagioclase flotation crust and a mafic lunar interior from which mare basalts were later derived. However, the extent of the Eu anomaly in lunar rocks is variable. Some plagioclase grains in a lunar impact rock (60635) have been reported to display a negative Eu anomaly, or in some cases single grains display both positive and neagtive anomalies. Cathodoluminescence images reveal that some crystals have a negative anomaly in the core and positive at the rim, or vice versa, and the negative anomalies are not associated with crystal overgrowths. Oxygen fugacity is known to affect Eu partitioning into plagioclase, as under low fO2 conditions Eu can be divalent, and has an ionic radius similar to Ca2+ - significant in lunar samples where plagioclase compositions are predominantly anorthitic. However, there are very few experimental studies of rare earth element (REE) partitioning in plagioclase relevant to lunar magmatism, with only two plagioclase DEu measurements from experiments using lunar materials, and little data in low fO2 conditions relevant to the Moon. We report on REE partitioning experiments on lunar compositions. We investigate two lunar basaltic compositions, high-alumina basalt 14072 and impact melt breccia 60635. These samples span a large range of lunar surface bulk compositions. The experiments are carried out at variable fO2 in 1 bar gas mixing furnaces, and REE are analysed by and LA-ICP-MS. Our results not only greatly expand the existing plagioclase DREE database for lunar compositions, but also investigate the significance of fO2 in Eu partitioning, and in the interpretation of Eu anomalies in lunar materials.

Petrology and Geochemistry of D'Orbigny, Geochemistry of Sahara 99555, and the Origin of Angrites

NASA Technical Reports Server (NTRS)

Mittlefehldt, David W.; Killgore, Marvin; Lee, Michael T.

2001-01-01

We have done detailed petrologic study of the angrite, D'Orbigny, and geochemical study of it and Sahara 99555. D'Orbigny is an igneous-textured rock composed of Ca-rich olivine, Al-Ti-diopside-hedenbergite, subcalcic kirschsteinite, two generations of hercynitic spinel and anorthite, with the mesostasis phases ulv6spinel, Ca-phosphate, a silicophosphate phase and Fe-sulfide. We report an unknown Fe-Ca-Al-Ti-silicate phase in the mesostasis not previously found in angrites. One hercynitic spinel is a large, rounded homogeneous grain of a different composition than the euhedral and zoned grains. We believe the former is a xenocryst, the first such described from angrites. The mafic phases are highly zoned; mg# of cores for olivine are approx.64, and for clinopyroxene approx.58, and both are zoned to Mg-free rims. The Ca content of olivine increases with decreasing mg#, until olivine with approx.20 mole% Ca is overgrown by subcalcic kirschsteinite with Ca approx.30-35 mole%. Detailed zoning sequences in olivine-subcalcic kirschsteinite and clinopyroxene show slight compositional reversals. There is no mineralogic control that can explain these reversals, and we believe they were likely caused by local additions of more primitive melt during crystallization of D'Orbigny. D'Orbigny is the most ferroan angrite with a bulk rock mg# of 32. Compositionally, it is virtually identical to Sahara 99555; the first set of compositionally identical angrites. Comparison with the other angrites shows that there is no simple petrogenetic sequence, partial melting with or without fractional crystallization, that can explain the angrite suite. Angra dos Reis remains a very anomalous angrite. Angrites show no evidence for the brecciation, shock, or impact or thermal metamorphism that affected the HED suite and ordinary chondrites. This suggests the angrite parent body may have followed a fundamentally different evolutionary path than did these other parent bodies.

Petrography and geochemistry of granitoids from the Samphire Pluton, South Australia: Implications for uranium mineralisation in overlying sediments

NASA Astrophysics Data System (ADS)

Domnick, Urs; Cook, Nigel J.; Bluck, Russel; Brown, Callan; Ciobanu, Cristiana L.

2018-02-01

The Blackbush uranium deposit (JORC Inferred Resource: 12,580 tonnes U), located on the north-eastern Eyre Peninsula, is currently the only sediment-hosted U deposit investigated in detail in the Gawler Craton. Uranium is hosted within Eocene sandstone of the Kanaka Beds, overlying Mesoproterozoic granites of the Samphire pluton, affiliated with the Hiltaba Intrusive Suite ( 1.6 Ga). These are considered the most probable source rocks for uranium mineralisation. By constraining the petrography and mineralogy of the granites, insights into the post-emplacement evolution can be gained, which may provide an exploration indicator for other sediment-hosted uranium systems. Three geochemically distinct granite types were identified in the Samphire Pluton and correspond to domains interpreted from geophysical data. All granites show complex alteration overprints and textures with increasing intensity closer to the deposit, as well as crosscutting veining. Alkali feldspar has been replaced by porous K-feldspar and albite, and plagioclase is overprinted by an assemblage of porous albite + sericite ± calc-silicates (prehnite, pumpellyite and epidote). This style of feldspar alteration is regionally widespread and known from Hiltaba-aged granites associated with iron-oxide copper-gold mineralisation at Olympic Dam and in the Moonta-Wallaroo region. In two granite types biotite is replaced by calcic garnet. Calc-silicates are indicative of Ca-metasomatism, sourced from the anorthite component of altered plagioclase. Minor clay alteration of feldspars is present in all samples. Mineral assemblages in veins include quartz + hematite, hematite + coffinite, fluorite + quartz, and clay minerals. Minor chlorite and sericite are found in all vein types. All granite types are anomalously rich in U (concentrations between 10 and 81 ppm). Highly variable Th/U ratios, as well as hydrothermal U minerals (mostly coffinite) in granites and veins, are clear evidence for U mobility. Uranium may have been preconcentrated in veins in the upper parts of the pluton, and was subsequently leached after deposition of the sediment.

The roles of fractional crystallization, magma mixing, crystal mush remobilization and volatile-melt interactions in the genesis of a young basalt-peralkaline rhyolite suite, the greater Olkaria volcanic complex, Kenya Rift valley

USGS Publications Warehouse

Macdonald, R.; Belkin, H.E.; Fitton, J.G.; Rogers, N.W.; Nejbert, K.; Tindle, A.G.; Marshall, A.S.

2008-01-01

The Greater Olkaria Volcanic Complex is a young (???20 ka) multi-centred lava and dome field dominated by the eruption of peralkaline rhyolites. Basaltic and trachytic magmas have been erupted peripherally to the complex and also form, with mugearites and benmoreites, an extensive suite of magmatic inclusions in the rhyolites. The eruptive rocks commonly represent mixed magmas and the magmatic inclusions are themselves two-, three- or four-component mixes. All rock types may carry xenocrysts of alkali feldspar, and less commonly plagioclase, derived from magma mixing and by remobilization of crystal mushes and/or plutonic rocks. Xenoliths in the range gabbro-syenite are common in the lavas and magmatic inclusions, the more salic varieties sometimes containing silicic glass representing partial melts and ranging in composition from anorthite ?? corundum- to acmite-normative. The peralkaline varieties are broadly similar, in major element terms, to the eruptive peralkaline rhyolites. The basalt-trachyte suite formed by a combination of fractional crystallization, magma mixing and resorption of earlier-formed crystals. Matrix glass in metaluminous trachytes has a peralkaline rhyolitic composition, indicating that the eruptive rhyolites may have formed by fractional crystallization of trachyte. Anomalous trace element enrichments (e.g. ??? 2000 ppm Y in a benmoreite) and negative Ce anomalies may have resulted from various Na- and K-enriched fluids evolving from melts of intermediate composition and either being lost from the system or enriched in other parts of the reservoirs. A small group of nepheline-normative, usually peralkaline, magmatic inclusions was formed by fluid transfer between peralkaline rhyolitic and benmoreitic magmas. The plumbing system of the complex consists of several independent reservoirs and conduits, repeatedly recharged by batches of mafic magma, with ubiquitous magma mixing. ?? The Author 2008. Published by Oxford University Press. All rights reserved.

Application of Fe-Ti oxide dissolution experiments to the petrogenesis of the Ekati Diamond Mine kimberlites, Northwest Territories, Canada

NASA Astrophysics Data System (ADS)

Kressall, R.; Fedortchouk, Y.; McCammon, C. A.

2015-12-01

Composition of kimberlites is ambiguous due to assimilation and fractional crystallization. We propose that the evolution history of minerals can be used to decipher the magmatic history of kimberlites. We use Fe-Ti oxides (chromite and ilmenite) from six kimberlites from the Ekati Diamond Mine and dissolution experiments to elucidate the petrogenesis of kimberlites. Experiments at 0.1 MPa and variable ƒO2s in a diopside-anorthite melt show that the dissolution rate of ilmenite is highly sensitive to ƒO2. No significant difference was observed in chromite. Zoning in chromite is related to the Fe-content and oxidation state of the melt. Experiments at 1 GPa explore the development of chromite surface resorption features in the system Ca-Mg-Si-H-C-O. Five kimberlites contain a low abundance of ilmenite, owing to a relatively high ƒO2, though ilmenite constituted 65% of oxide macocrysts in one kimberlite. Chromite compositions evolve from Mg-chromite to magnesio-ulvöspinel-magnetite (MUM) in all but one kimberlite where chromite evolves to a pleonaste composition perhaps as a result of rapid emplacement. The high abundance of MUM spinel and low abundance of ilmenite in the matrix could be related to the change in the stable Ti-phase with increasing ƒO2. Core compositions of macrocrysts vary for different mantle sources but rims converge to a composition slightly more oxidized and Mg-rich than chromite from depleted peridotite. Ilmenite commonly has rims composed of perovskite, titanite and MUM. We suggest a model where the kimberlite melt composition is controlled by the co-dissolution and co-precipitation of silicates (predominantly orthopyroxene and olivine) to explain chromite evolution in kimberlites. Resorption-related surface features on chromite macrocrysts show trigon protrusions-depressions on {111} faces and step-like features along the crystal edges resembling products of experiments in H2O fluid. We propose predominantly H2O magmatic fluid in Ekati kimberlites.

Complex Diffusion Mechanisms for Li in Feldspar: Re-thinking Li-in-Plag Geospeedometry

NASA Astrophysics Data System (ADS)

Holycross, M.; Watson, E. B.

2017-12-01

In recent years, the lithium isotope system has been applied to model processes in a wide variety of terrestrial environments. In igneous settings, Li diffusion gradients have been frequently used to time heating episodes. Lithium partitioning behavior during decompression or cooling events drives Li transfer between phases, but the extent of Li exchange may be limited by its diffusion rate in geologic materials. Lithium is an exceptionally fast diffuser in silicate media, making it uniquely suited to record short-lived volcanic phenomena. The Li-in-plagioclase geospeedometer is often used to time explosive eruptions by applying laboratory-calibrated Li diffusion coefficients to model concentration profiles in magmatic feldspar samples. To quantify Li transport in natural scenarios, experimental measurements are needed that account for changing temperature and oxygen fugacity as well as different feldspar compositions and crystallographic orientation. Ambient pressure experiments were run at RPI to diffuse Li from a powdered spodumene source into polished sanidine, albite, oligoclase or anorthite crystals over the temperature range 500-950 ºC. The resulting 7Li concentration gradients developed in the mineral specimens were evaluated using laser ablation ICP-MS. The new data show that Li diffusion in all feldspar compositions simultaneously operates by both a "fast" and "slow" diffusion mechanism. Fast path diffusivities are similar to those found by Giletti and Shanahan [1997] for Li diffusion in plagioclase and are typically 10 to 20 times greater than slow path diffusivities. Lithium concentration gradients in the feldspar experiments plot in the shape of two superimposed error function curves with the slow diffusion regime in the near-surface of the crystal. Lithium diffusion is most sluggish in sanidine and is significantly faster in the plagioclase feldspars. It is still unclear what diffusion mechanism operates in nature, but the new measurements may impact how Li-in-plagioclase geospeedometry is used to time igneous processes. Giletti, B.J., and T.M. Shanahan (1997) Alkali diffusion in plagioclase feldspar, Chem. Geol., 139, 3-20

Chemical weathering rate, denudation rate, and atmospheric and soil CO2 consumption of Paraná flood basalts in São Paulo State, Brazil

NASA Astrophysics Data System (ADS)

da Conceição, Fabiano Tomazini; dos Santos, Carolina Mathias; de Souza Sardinha, Diego; Navarro, Guillermo Rafael Beltran; Godoy, Letícia Hirata

2015-03-01

The chemical weathering rate and atmospheric/soil CO2 consumption of Paraná flood basalts in the Preto Stream basin, São Paulo State, Brazil, were evaluated using major elements as natural tracers. Surface and rain water samples were collected in 2006, and analyses were performed to assess pH, temperature, dissolved oxygen (DO), electrical conductivity (EC) and total dissolved solids (TDS), including SO42-, NO3-, PO43 -, HCO3-, Cl-, SiO2, Ca2 +, Mg2 +, Na+ and K+. Fresh rocks and C horizon samples were also collected, taking into account their geological context, abundance and spatial distribution, to analyze major elements and mineralogy. The Preto Stream, downstream from the city of Ribeirão Preto, receives several elements/compounds as a result of anthropogenic activities, with only sulfate yielding negative flux values. The negative flux of SO42 - can be attributed to atmospheric loading that is mainly related to anthropogenic inputs. After corrections were made for atmospheric inputs, the riverine transport of dissolved material was found to be 30 t km- 2 y- 1, with the majority of the dissolved material transported during the summer (wet) months. The chemical weathering rate and atmospheric/soil CO2 consumption were 6 m/Ma and 0.4 · 106 mol km- 2 y- 1, respectively. The chemical weathering rate falls within the lower range of Paraná flood basalt denudation rates between 135 and 35 Ma previously inferred from chronological studies. This comparison suggests that rates of basalt weathering in Brazil's present-day tropical climate differ by at most one order of magnitude from those prevalent at the time of hothouse Earth. The main weathering process is the monosiallitization of anorthoclase, augite, anorthite and microcline. Magnetite is not weathered and thus remains in the soil profile.

Petrology and mineralogy of the Ningqiang carbonaceous chondrite

NASA Astrophysics Data System (ADS)

Wang, Y.; Hsu, W.

2009-07-01

We report detailed chemical, petrological, and mineralogical studies on the Ningqiang carbonaceous chondrite. Ningqiang is a unique ungrouped type 3 carbonaceous chondrite. Its bulk composition is similar to that of CV and CK chondrites, but refractory lithophile elements (1.01 × CI) are distinctly depleted relative to CV (1.29 × CI) and CK (1.20 × CI) chondrites. Ningqiang consists of 47.5 vol% chondrules, 2.0 vol% Ca,Al-rich inclusions (CAIs), 4.5 vol% amoeboid olivine aggregates (AOAs), and 46.0 vol% matrix. Most chondrules (95%) in Ningqiang are Mgrich. The abundances of Fe-rich and Al-rich chondrules are very low. Al-rich chondrules (ARCs) in Ningqiang are composed mainly of olivine, plagioclase, spinel, and pyroxenes. In ARCs, spinel and plagioclase are enriched in moderately volatile elements (Cr, Mn, and Na), and low-Ca pyroxenes are enriched in refractory elements (Al and Ti). The petrology and mineralogy of ARCs in Ningqiang indicate that they were formed from hybrid precursors of ferromagnesian chondrules mixed with refractory materials during chondrule formation processes. We found 294 CAIs (55.0% type A, 39.5% spinel-pyroxene-rich, 4.4% hibonite-rich, and several type C and anorthite-spinelrich inclusions) and 73 AOAs in 15 Ningqiang sections (equivalent to 20 cm2 surface area). This is the first report of hibonite-rich inclusions in Ningqiang. They are texturally similar to those in CM, CH, and CB chondrites, and exhibit three textural forms: aggregates of euhedral hibonite single crystals, fine-grained aggregates of subhedral hibonite with minor spinel, and hibonite ± Al,Ti-diopside ± spinel spherules. Evidence of secondary alteration is ubiquitous in Ningqiang. Opaque assemblages, formed by secondary alteration of pre-existing alloys on the parent body, are widespread in chondrules and matrix. On the other hand, nepheline and sodalite, existing in all chondritic components, formed by alkali-halogen metasomatism in the solar nebula.

Feldspar 40Ar/39Ar dating of ICDP PALEOVAN cores

NASA Astrophysics Data System (ADS)

Engelhardt, Jonathan Franz; Sudo, Masafumi; Stockhecke, Mona; Oberhänsli, Roland

2017-11-01

Volcaniclastic fall deposits in ICDP drilling cores from Lake Van, Turkey, contain sodium-rich sanidine and calcium-rich anorthoclase, which both comprise a variety of textural zoning and inclusions. An age model records the lake's history and is based on climate-stratigraphic correlations, tephrostratigraphy, paleomagnetics, and earlier 40Ar/39Ar analyses (Stockhecke et al., 2014b). Results from total fusion and stepwise heating 40Ar/39Ar analyses presented in this study allow for the comparison of radiometric constraints from texturally diversified feldspar and the multi-proxy lacustrine age model and vice versa. This study has investigated several grain-size fractions of feldspar from 13 volcaniclastic units. The feldspars show textural features that are visible in cathodoluminescence (CL) or back-scattered electron (BSE) images and can be subdivided into three dominant zoning-types: (1) compositional zoning, (2) round pseudo-oscillatory zoning and (3) resorbed and patchy zoning (Ginibre et al., 2004). Round pseudo-oscillatory zoning records a sensitive alternation of Fe and Ca that also reflects resorption processes. This is only visible in CL images. Compositional zoning reflects anticorrelated anorthite and orthoclase contents and is visible in BSE. Eleven inverse isochron ages from total fusion and three from stepwise heating analyses fit the age model. Four experiments resulted in older inverse isochron ages that do not concur with the model within 2σ uncertainties and that deviate from 1 ka to 17 ka minimum. C- and R-type zoning are interpreted as representing growth in magma chamber cupolas, as wall mushes, or in narrow conduits. Persistent compositions of PO-type crystals and abundant surfaces recording dissolution features correspond to formation within a magma chamber. C-type zoning and R-type zoning have revealed an irregular incorporation of melt and fluid inclusions. These two types of zoning in feldspar are interpreted as preferentially contributing either heterogeneously distributed excess 40Ar or inherited 40Ar to the deviating 40Ar/39Ar ages that are discussed in this study.

A Refractory Inclusion Returned by Stardust from Comet 81P/Wild 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Simon, S B; Joswiak, D J; Ishii, H A

2008-05-20

Among the samples returned from comet 81P/Wild 2 by the Stardust spacecraft is a suite of particles from one impact track (Track 25) that are Ca-, Al-rich and FeO-free. We studied three particles from this track that range in size from 5.3 x 3.2 {micro}m to 15 x 10 {micro}m. Scanning and transmission electron microscopy show that they consist of very fine-grained (from {approx}0.5 to {approx}2 {micro}m) Al-rich, Ti-bearing and Ti-free clinopyroxene, Mg-Al spinel, anorthite, perovskite, and osbornite (TiN). In addition to these phases, the terminal particle, named 'Inti', also contains melilite. All of these phases, with the exception ofmore » osbornite, are common in refractory inclusions and are predicted to condense at high temperature from a gas of solar composition. Osbornite, though very rare, has also been found in meteoritic refractory inclusions, and could have formed in a region of the nebula where carbon became enriched relative to oxygen compared to solar composition. Compositions of Ti-pyroxene in Inti are similar, but not identical, to those of fassaite from Allende inclusions. Electron energy loss spectroscopy shows that Ti-rich pyroxene in Inti has Ti{sup 3+}/Ti{sup 4+} within the range of typical meteoritic fassaite, consistent with formation under reducing conditions comparable to those of a system of solar composition. Inti is {sup 16}O-rich, with {delta}{sup 18}O {approx} {delta}{sup 17}O {approx} 40{per_thousand}, like unaltered phases in refractory inclusions and refractory IDPs. With grain sizes, mineralogy, mineral chemistry, and an oxygen isotopic composition like those of refractory inclusions, we conclude that Inti is a refractory inclusion that formed in the inner solar nebula. Identification of a particle that formed in the inner Solar System among the comet samples demonstrates that there was transport of materials from the inner to the outer nebula, probably either in a bipolar outflow or by turbulence.« less

The stability of hibonite and other aluminous phases in silicate melts: Implications for the origin of hibonite-bearing inclusions

NASA Technical Reports Server (NTRS)

Beckett, J. R.; Stolper, E.

1993-01-01

Phase fields in which hibonite (Hib) and silicate melt coexist with spinel (Sp), CaAl4O7 (CA2), gehlenitic melilite (Mel), anorthite (An), or corundum (Cor) in the system CaO-MgO-Al203-SiO2-TiO2 (CMAST) were determined and activity models developed for Mel and Hib solid solutions. Experimentally determined partition coefficients for Ti between Hib and coexisting melt, D sub t, vary from 0.8 to 2.1 and generally decrease with increasing TiO2 content in the liquid (L). Based on Ti partioning between Hib and melt, bulk inclusion compositions and Hib-saturated liquid use phase diagrams, the Hib in Fluffy Type A inclusions (FTA's) from Allende and at least some of the Hib from Hib-rich inclusions is relict; much of the Hib from Hib-glass spherules probably crystallized from a melt under nonequilibrium conditions. Bulk compositions for all of these Ca-Al-rich inclusions (CAI's) are consistent with an origin as Mel + Hib + Sp + perovskite (Pv) proto-inclusions in which Mel was partially altered. In some cases, the proto-inclusion was partially or completely melted with vaporization occurring over a period of time sufficient to remove any Na introduced by the alteration process but frequently insufficient to dissolve all of the original hibonite. If equilibration temperatures based on Hib-bearing CAI's reflect condensation in a cooling gas of solar composition, then Hib + Cor condensed at approximately 1260 C (referenced to 10 exp -3 atm) and Hib + Sp + Mel at approximately 1215 +/- 10 C. Simple thermochemical models for the substitution of trace elements into the Ca-site of meteoritic Hib suggest that virtually all Eu is divalent in early condensate Hibs but that Eu(2+)/Eu(3+) decreases by a factor of 20 or more during the course of condensation, primarily because the ratio is proportional to the partial pressure of Al, which decreases dramatically as aluminous phases condense. The relative sizes of Eu and Yb anomalies in meteoritic Hibs and CAI's may be influenced by this effect.

Production of fiberglass/metal composite material suitable for building habitat and manufacturing facilities

NASA Technical Reports Server (NTRS)

1987-01-01

The production of a fiberglass/metal composite material suitable for building habitats and manufacturing facilities was the project for Clemson. The concept and development of the knowledge necessary to produce glass fibers originated in the spring semester. During the summer, while at Johnson Space Center, fiberglass from a rock composition similar to ones found at the Apollo 16 site on the moon was successfully produced. The project this year was a continuation of last year's studies. We addressed the following problems which emerged as the work progressed: (1) Methods for coating the fibers with a metal were explored. We manufactured composites in two stages: Glass fibers without any coating on them; and fibers coated with metals as they were made. This proved to be a difficult process. Future activities include using a chemical vapor deposition process on fibers which have been made. (2) A glass furnace was developed which relies primarily on solar energy for melting the glass. The temperature of the melted glass is maintained by electrical means. The design is for 250 kg of glass per day. An electrical engineering student developed a scheme for controlling the melting and manufacturing process from the earth. This was done to minimize the human risk. Graphite refractories are relied on to contain the melt. (3) The glass composition chosen for the project is a relatively pure anorthite which is available in the highland regions of the lunar surface. A major problems with this material is that it melts at a comparatively high temperature. This problem will be solved by using graphite refractory materials for the furnace. The advantage of this glass composition is that it is very stable and does not tend to crystallize. (4) We have also refined the experimental furnace and fiber making machinery which we will be using at Johnson Space Center this summer. We believe that we will be able to draw and coat glass fibers in a vacuum for use in composites. We intend to make and test the mechanical properties of these composites.

Petrology and chemistry of the Green Acres gabbro complex near Winchester, Riverside County, California

USGS Publications Warehouse

Berger, Byron R.; Morton, Douglas M.; Miller, Fred K.

2014-01-01

The Cretaceous Green Acres layered igneous complex, northeast of Winchester, California, is composed of a suite of olivine- and hornblende-bearing gabbros in the Peninsular Ranges batholith within the Perris tectonic block. A consistent mineral assemblage is observed throughout the complex, but there is considerable textural and modal heterogeneity. Both preclude a consistent set of principles based on appearance and mineralogy on which to delineate map units. Distinct changes in the chemistry of olivine, pyroxene, and hornblende, however, serve to define discrete mappable units, and the complex has been divided into five geochemical map units on this basis.Limited whole-rock data show the Green Acres complex is chemically comparable to other Peninsular Ranges batholith gabbroic rocks, and rare earth element (REE) concentrations and patterns are typical of magmas generated in convergent margin settings. For the complex as a whole, olivine is Fo80–35, plagioclase is An100–64, clinopyroxene is Wo49–41En48–38Fs18–6 and Wo36–26En65–42Fs30–8, and orthopyroxene is Wo5–0En78–42Fs50–21, where Fo is forsterite, An is anorthite, Wo is wollastonite, En is enstatite, and Fs is ferrosilite. The Mg/(Mg + ΣFe) atomic ratio in hornblende ranges from 0.84 to 0.50.Magmatic lineations and modal and textural layering are prevalent throughout the complex. Mineral chemistry does not change in any systematic way within and between layers in any map unit. Although the strike of layering varies, in any map unit at any given location it is the same in all units irrespective of intrusive order. Thin dikes, typically late-stage hornblende gabbro, commonly intrude parallel to layering. The strikes of magmatic lineations and modal layers are consistent with the populations of strikes of fabrics in the metamorphic basement as well as tectonic features in surrounding, postgabbro granitic rocks. These relations imply that the regional state of stress at the time of gabbro emplacement played a role in layer formation in conjunction with thermal and hydraulic pressure perturbations.

The effect of syntectonic hydration on rock strength, fabric evolution, and polycrystalline flow in mafic lower continental crust rocks

NASA Astrophysics Data System (ADS)

Getsinger, A.; Hirth, G.

2014-12-01

Strain localization is significantly enhanced by the influx of fluid; however, processes associated with deformation in polycrystalline material, fluid infiltration, and the evolution of creep processes and rock fabric with increasing strain localization are not well constrained for many lower crust lithologies. We combine field and experimental observations of mafic rocks deforming at lower crust pressure, temperature, and water conditions to examine strain localization processes associated with the influx of fluid, strength dependence of fabric evolution, and flow law parameters for amphibolite. General shear experiments were conducted in a Griggs rig on powdered basalt (≤5 µm starting grain size) with up to 1 wt% water at lower continental crust conditions (750˚ to 850˚C, 1GPa). Amphibole formed during deformation exhibits both a strong shape preferred orientation (SPO) and lattice preferred orientation (LPO). With increasing strain, the amphibole (and clinopyroxene) LPO strengthens and rotates to [001] maximum aligned sub-parallel to the flow direction and SPO, which indicates grain rotation during deformation. Plagioclase LPO increases from random to very weak in samples deformed to high strain. As the amphibole LPO rotates and strengthens, the mechanical strength decreases. The correlation of the SPO and LPO coupled with the rheological evidence for diffusion creep (n ≈ 1.5) indicates that the amphibole fabric results from grain growth and rigid grain rotation during deformation. The coevolution of LPO (and grain rotation) and mechanical weakening coupled with the absence of grain size reduction in our samples suggests that strength depends on the formation of a strong mineral LPO. Both our field and experimental data demonstrate that fluid intrusion into the mafic lower crust initiates syn-deformational, water-consuming reactions, creating a rheological contrast between wet and dry lithologies that promotes strain localization. Additionally, the rheology of both naturally deformed amphibolite shear zones and our fine-grained experimental amphibolite is comparable to that predicted using flow laws for wet anorthite. Thus, both our experimental and field analyses indicate that wet plagioclase rheology provides a good constraint on the strength of hydrated lower continental crust.

The Origin of Refractory Minerals in Comet 81P/Wild 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chi, M; Ishii, H A; Simon, S B

2008-11-20

Refractory Ti-bearing minerals in the calcium-, aluminium-rich inclusion (CAI) Inti, recovered from the comet 81P/Wild 2 sample, were examined using analytical (scanning) transmission electron microscopy (STEM) methods including imaging, nanodiffraction, energy dispersive spectroscopy (EDX) and electron energy loss spectroscopy (EELS). Inti fassaite (Ca(Mg,Ti,Al)(Si,Al){sub 2}O{sub 6}) was found to have a Ti{sup 3+}/Ti{sup 4+} ratio of 2.0 {+-} 0.2, consistent with fassaite in other solar system CAIs. The oxygen fugacity (log f{sub O{sub 2}}) of formation estimated from this ratio, assuming equilibration among phases at 1509K, is -19.4 {+-} 1.3. This value is near the canonical solar nebula value (-18.1 {+-}more » 0.3) and in close agreement with that reported for fassaite-bearing Allende CAIs (-19.8 {+-} 0.9) by other researchers using the same assumptions. Nanocrystals of osbornite (Ti(V)N), 2-40 nm in diameter, are embedded as inclusions within anorthite, spinel and diopside in Inti. Vanadium is heterogeneously distributed within some osbornite crystals. Compositions range from pure TiN to Ti{sub 0.36}V{sub 0.64}N. The possible presence of oxide and carbide in solid solution with the osbornite was evaluated. The osbornite may contain O but does not contain C. The presence of osbornite, likely a refractory early condensate, together with the other refractory minerals in Inti, indicates that the parent comet contains solids that condensed closer to the proto-sun than the distance at which the parent comet itself accreted. The estimated oxygen fugacity and the reported isotopic and chemical compositions are consistent with Inti originating in the inner solar system as opposed to it being a surviving CAI from an extrasolar source. These results provide insight for evaluating the validity of models of radial mass transport dynamics in the early solar system. The oxidation environments inferred for the Inti mineral assemblage are inconsistent with an X-wind formation scenario. In contrast, radial mixing models allowing accretion of components from different heliocentric distances can satisfy the observations from the cometary CAI Inti.« less

Microstructural constraints on complex thermal histories of refractory CAI-like objects in an amoeboid olivine aggregate from the ALHA77307 CO3.0 chondrite

NASA Astrophysics Data System (ADS)

Han, Jangmi; Brearley, Adrian J.

2016-06-01

We have carried out a FIB/TEM study of refractory CAI-like objects in one AOA from the ALHA77307 CO3.0 chondrite. The CAI-like objects in the AOA consist of a zoned sequence with a spinel-rich core through an intergrowth layer of spinel and Al-Ti-rich diopside to a diopside rim. The spinel-rich core consists of polycrystalline aggregates of spinel and ±minor melilite showing equilibrated grain boundary textures. The intergrowth layer contains fine-grained diopside and spinel with minor anorthite with highly curved and embayed grain boundaries. The diopside rim consists of polycrystalline aggregates of diopside. The compositions of pyroxene change significantly outward from Al-Ti-rich diopside in contact with the spinel-rich core to Al-Ti-poor diopside next to the surrounding olivine of the AOA. Overall microstructural and chemical characteristics suggest that the spinel-rich core formed under equilibrium conditions whereas the intergrowth layer is the result of reactions that occurred under conditions that departed significantly from equilibrium. The remarkable changes in formation conditions of the CAI-like objects may have been achieved by transport and injection of refractory objects into a region of a partially-condensed, Ca,Ti-saturated gas which reacted with spinel and melilite to form Al-Ti-rich diopside. Crystallographically-oriented TiO2 nanoparticles decorate the grain boundaries between spinel grains and between spinel and Al-Ti-rich diopside grains. During the disequilibrium back-reaction of spinel with a partially-condensed, Ca,Ti-saturated gas, metastable TiO2 nanoparticles may have condensed by an epitaxial nucleation mechanism and grown on the surface of spinel. These TiO2 nanoparticles are disordered intergrowths of the two TiO2 polymorphs, anatase and rutile. These nanoparticles are inferred to have nucleated as anatase that underwent partial transformation into rutile. The local presence of the TiO2 nanoparticles and intergrowth of anatase and rutile imply that the disequilibrium back-reaction of spinel with the gas occurred on a short timescale, i.e., minutes to hours at maximum.

Effects of body formulation and firing temperature to properties of ceramic tile incorporated with electric arc furnace (EAF) slag waste

NASA Astrophysics Data System (ADS)

Sharif, Nurulakmal Mohd; Lim, Chi Yang; Teo, Pao Ter; Seman, Anasyida Abu

2017-07-01

Significant quantities of sludge and slag are generated as waste materials or by-products from steel industries. One of the by-products is Electric Arc Furnace (EAF) steel slag which consists of oxides such as CaO, Al2O3 and FeO. This makes it possible for slag to partially replace the raw materials in ceramic tile production. In our preliminary assessment of incorporating the EAF slag into ceramic tile, it was revealed that at fixed firing temperature of 1150°C, the tile of composition 40 wt.% EAF slag - 60 wt.% ball clay has comparable properties with commercial ceramic tile. Thus, this current study would focus on effects of body formulation (different weight percentages of K-feldspar and silica) and different firing temperatures to properties of EAF slag added ceramic tile. EAF slag from Southern Steel Berhad (SSB) was crushed into micron size (EAF slag content was 40 wt.%) and milled with ball clay, K-feldspar and silica before compacted and fired at 1125°C and 1150°C. The EAF slag added tile was characterized in terms of water absorption, apparent porosity, bulk density, modulus of rupture (MOR) and phase analysis via X-ray diffraction (XRD). The composition of 40 wt.% EAF slag - 30 wt.% ball clay - 10 wt.% K-feldspar - 20 wt.% silica (10F_20S), fired at 1150°C showed the lowest water absorption, apparent porosity and highest bulk density due to enhancement of densification process during firing. However, the same composition of ceramic tile (10F_20S) had the highest MOR at lower firing temperature of 1125°C, contributed by presence of the highest total amount of anorthite and wollastonite reinforcement crystalline phases (78.40 wt.%) in the tile. Overall, both the water absorption and MOR of all ceramic tiles surpassed the requirement regulated by MS ISO 13006:2014 Standard (Annex G: Dry-pressed ceramic tile with low water absorption, Eb ≤ 0.50 % and minimum MOR of 35 MPa).

The 1994-2001 eruptive period at Rabaul, Papua New Guinea: Petrological and geochemical evidence for basalt injections into a shallow dacite magma reservoir, and significant SO2 flux

NASA Astrophysics Data System (ADS)

Patia, H.; Eggins, S. M.; Arculus, R. J.; McKee, C. O.; Johnson, R. W.; Bradney, A.

2017-10-01

The eruptions that began at Rabaul Caldera on 19 September 1994 had two focal points, the vents Tavurvur and Vulcan, located 6 km apart on opposing sides of the caldera. Vulcan eruptives define a tight cluster of dacite compositions, whereas Tavurvur eruptives span an array from equivalent dacite compositions to mafic andesites. The eruption of geochemically and mineralogically identical dacites from both vents indicates sourcing from the same magma reservoir. This, together with previously reported H2O-CO2 volatile contents of dacite melt inclusions, a caldera-wide seismic low-velocity zone, and a seismically active caldera ring fault structure are consistent with the presence at 3-6 km depth of an extensive, tabular dacitic magma body having volume of about 15-150 km3. The Tavurvur andesites form a linear compositional array and have strongly bimodal phenocryst assemblages that reflect dacite hybridisation with a mafic basalt. The moderately large volume SO2 flux documented in the Tavurvur volcanic plume (and negligible SO2 flux in the Vulcan plume) combined with high dissolved S contents of basaltic melt inclusions trapped in olivine of Tavurvur eruptives, indicate that the amount of degassed basaltic magma was 0.1 km3 and suggest that the injection of this magma was confined to the Tavurvur-side (eastern to northeastern sector) of the caldera. Circumstantial evidence suggests that the eruption was triggered and evolved in response to a series of basaltic magma injections that may have commenced in 1971 and continued up until at least the start of the 1994 eruptions. The presence of zoned plagioclase phenocrysts reflecting older basalt-dacite interaction events (i.e. anorthite cores overgrown with thick andesine rims), evaluation of limited available data for the products of previous eruptions in 1878 and 1937-1943, and the episodic occurrence of major intra-caldera seismo-deformational events indicates that the shallow magma system at Rabaul Caldera is subjected to repeated mafic magma injections at intervals of several years to several decades.

Compositional data analysis and geochemical modeling of CO2-water-rock interactions in three provinces of Korea.

PubMed

Kim, Seong Hee; Choi, Byoung-Young; Lee, Gyemin; Yun, Seong-Taek; Kim, Soon-Oh

2017-12-20

The CO 2 -rich spring water (CSW) occurring naturally in three provinces, Kangwon (KW), Chungbuk (CB), and Gyeongbuk (GB) of South Korea was classified based on its hydrochemical properties using compositional data analysis. Additionally, the geochemical evolution pathways of various CSW were simulated via equilibrium phase modeling (EPM) incorporated in the PHREEQC code. Most of the CSW in the study areas grouped into the Ca-HCO 3 water type, but some samples from the KW area were classified as Na-HCO 3 water. Interaction with anorthite is likely to be more important than interaction with carbonate minerals for the hydrochemical properties of the CSW in the three areas, indicating that the CSW originated from interactions among magmatic CO 2 , deep groundwater, and bedrock-forming minerals. Based on the simulation results of PHREEQC EPM, the formation temperatures of the CSW within each area were estimated as 77.8 and 150 °C for the Ca-HCO 3 and Na-HCO 3 types of CSW, respectively, in the KW area; 138.9 °C for the CB CSW; and 93.0 °C for the GB CSW. Additionally, the mixing ratios between simulated carbonate water and shallow groundwater were adjusted to 1:9-9:1 for the CSW of the GB area and the Ca-HCO 3 -type CSW of the KW area, indicating that these CSWs were more affected by carbonate water than by shallow groundwater. On the other hand, mixing ratios of 1:9-5:5 and 1:9-3:7 were found for the Na-HCO 3 -type CSW of the KW area and for the CSW of the CB area, respectively, suggesting a relatively small contribution of carbonate water to these CSWs. This study proposes a systematic, but relatively simple, methodology to simulate the formation of carbonate water in deep environments and the geochemical evolution of CSW. Moreover, the proposed methodology could be applied to predict the behavior of CO 2 after its geological storage and to estimate the stability and security of geologically stored CO 2 .

In-situ determination of the oxidation state of iron in Fe-bearing silicate melts

NASA Astrophysics Data System (ADS)

Courtial, P.; Wilke, M.; Potuzak, M.; Dingwell, D. B.

2005-12-01

Terrestrial lavas commonly contain up to 10 wt% of iron. Furthermore, rocks returned from the Moon indicate lunar lava containing up to 25 wt% of iron and planetary scientists estimated that the martian mantle has about 18 wt% of iron. An experimental challenge in dealing with Fe-bearing silicate melts is that the oxidation state, controlling the proportions of ferric and ferrous iron, is a function of composition, oxygen fugacity and temperature and may vary significantly. Further complications concerning iron originate from its potential to be either four-, six- or even five-fold coordinated in both valence states. Therefore, the oxidation state of iron was determined in air for various Fe-bearing silicate melts. Investigated samples were Na-disilicate (NS), one atmosphere anorthite-diopside eutectic (AD) and haplogranitic (HPG8) melts containing up to 20, 20 and 10 wt% of iron, respectively. XANES spectra at the Fe K-edge were collected for all the melts at beamline A1, HASYLAB, Hamburg, using a Si(111) 4-crystal monochromator. Spectra were collected for temperatures up to 1573 K using a Pt-Rh loop as heating device. The Fe oxidation state was determined from the centroid position of the pre-edge feature using the calibration of Wilke et al. (2004). XANES results suggest that oxidation state of iron does not change within error for NS melts with addition of Fe, while AD and HPG8 melts become more oxidised with increasing iron content. Furthermore, NS melts are well more oxidised than AD and HPG8 melts that exhibit relatively similar oxidation states for identical iron contents. The oxidation state of iron for NS melts appears to be slightly temperature-dependent within the temperature range investigated (1073-1573 K). However, this trend is stronger for AD and HPG8 melts. Assuming that glass reflects a picture of the homogeneous equilibria of the melt, the present in-situ Fe-oxidation states determined for these melts were compared to those obtained on quenched glasses from different temperatures, when possible, using wet-chemical analysis (i.e., K-dichromate potentiometry). Both datasets agree reasonably well (within 10 %). References: Wilke et al. (2004) Chemical Geology, 213, 71-87.

Evidence for an early nitrogen isotopic evolution in the solar nebula from volatile analyses of a CAI from the CV3 chondrite NWA 8616

NASA Astrophysics Data System (ADS)

Füri, Evelyn; Chaussidon, Marc; Marty, Bernard

2015-03-01

Nitrogen and noble gas (Ne-Ar) abundances and isotope ratios, determined by CO2 laser extraction static mass spectrometry analysis, as well as Al-Mg and O isotope data from secondary ion mass spectrometry (SIMS) analyses, are reported for a type B calcium-aluminum-rich inclusion (CAI) from the CV3 chondrite NWA 8616. The high (26Al/27Al)i ratio of (5.06 ± 0.50) × 10-5 dates the last melting event of the CAI at 39-99+109ka after "time zero", limiting the period during which high-temperature exchanges between the CAI and the nebular gas could have occurred to a very short time interval. Partial isotopic exchange with a 16O-poor reservoir resulted in Δ17O > -5‰ for melilite and anorthite, whereas spinel and Al-Ti-pyroxene retain the inferred original 16O-rich signature of the solar nebula (Δ17O ⩽ -20‰). The low 20Ne/22Ne (⩽0.83) and 36Ar/38Ar (⩽0.75) ratios of the CAI rule out the presence of any trapped planetary or solar noble gases. Cosmogenic 21Ne and 38Ar abundances are consistent with a cosmic ray exposure (CRE) age of ∼14 to 20 Ma, assuming CR fluxes similar to modern ones, without any evidence for pre-irradiation of the CAI before incorporation into the meteorite parent body. Strikingly, the CAI contains 1.4-3.4 ppm N with a δ15N value of +8‰ to +30‰. Even after correcting the measured δ15N values for cosmogenic 15N produced in situ, the CAI is highly enriched in 15N compared to the protosolar nebula (δ15NPSN = -383 ± 8‰; Marty et al., 2011), implying that the CAI-forming region was contaminated by 15N-rich material within the first 0.15 Ma of Solar System history, or, alternatively, that the CAI was ejected into the outer Solar System where it interacted with a 15N-rich reservoir.

Core formation conditons in planetesimals: constraints from isotope fractionation experiments.

NASA Astrophysics Data System (ADS)

Guignard, J.; Quitté, G.; Toplis, M. J.; Poitrasson, F.

2016-12-01

Planetesimals are small objects (10 to 1000 km) early accreted in the history of the solar system which show a wide variety of thermal history due to the initial amount of radiogenic elements [1] (26Al and 60Fe), from a simple metamorphism to a complete metal-silicate differentiation. Moreover, isotope compositions of siderophile element, e.g. Fe, Ni, and W in meteorites spread on a range that can be attributed to the process of core-mantle segregation. We therefore performed isotope fractionation experiments of nickel and tungsten between metal and silicate in a gas-mixing (CO-CO2) vertical furnace, at different temperatures (from 1270°C to 1600°C), oxygen fugacity (from IW+2 to IW-6) and annealing times (from 20 minutes to 48 hours). The starting silicate is an anorthite-diopside eutectic composition glass, synthesize from the respective oxides. The starting metal is either a nickel or tungsten wire according to the element to study. After each experiment, metal and silicate are mechanically separated and digested in acids. Nickel and Tungsten separation have been made according to the methods developed by [2] and [3] and isotopes measurements have been made using a high resolution MC-ICP-MS (Neptune; Thermofisher©). Results show evidence for a strong kinetic isotope fractionation during the first annealing times with a faster diffusion of lightest isotopes than heaviest. Similar mechanism has been already highlighted for iron isotope fractionation between silicate and metal [4]. Chemical and isotopic equilibrium is also reached in our experiments but the time required dependent on the conditions of temperature and oxygen fugacity. Therefore, at equilibrium, metal-silicate isotope fractionation has also been quantified as well its temperature dependence. These experimental data can be used in order to bring new constraints on the metal silicate segregation in the planetesimals early accreted. [1] Lee T., et al., GRL, 3, 41-44 (1976) [2] Quitté G., and Oberli F., JAAS, 21, 1249-1255 (2006) [3] Breton T., and Quitté G., JAAS, 29, 2284-2293 (2014) [4] Roskosz M., et al., EPSL, 248, 851-867 (2006)

Nucleation and Growth Rates of Pyroxene, Plagioclase and Fe-Ti Oxides in Basalt

NASA Astrophysics Data System (ADS)

Burkhard, D. J.

2003-12-01

Rock textures and physical and chemical properties are determined by the time-temperature path of a magma, and the nucleation and growth rates (J, G) of crystallizing mineral phases. We applied the crystal size distribution theory (CSD) to derived J and G of pyroxene, plagioclase and of Fe-Ti oxides in basalt glass during heat treatment [1,2,3,4]. The glass was sampled from active Pu`u O`o, Kilauea, Hawaii, by hammer-dipping and subsequent quenching [5]. Temperature (T) and time (t) dependent heat treatment of the glass above temperature of nucleation and growth maxima, about 930° C, allows one to derive the activation energy of J and G, EJ, EG, which are at steady state after about 100 hrs, at 180/200, 353/307, 292/343 kJ/mol (EJ/EG, for pyroxene, plagioclase and Fe-Ti oxides). On a logarithmic scale, J and G are linear with t. A comparison with growth rates of lava cooled within a lava lobe, from top to bottom [6], suggests that independent of depth, all mineral phases crystallized at T < 1000° C. According to our results of t and T dependent J and G, such rock textures should first crystallize pyroxene, and intersertal plagioclase which is, indeed, observed. Slow cooling or a hold at T > 1000° C, should result in a first crystallization of plagioclase. This is reported in the literature [e.g., 7]. In agreement with this, we detected anorthite nuclei in the glass with HRTEM [8]. [1] Randolph R.D., Larson M.A (1979); Theory of particulate processes. Academic Press, New York. [2] Marsh B.D. (1988); Contrib.Mineral. Petrol. 99, 277-291. [3] Cashman K.V., Marsh (1988) Contrib. Mineral. Petrol. 99, 292-305. [4] Burkhard D.J.M. (2002); Contrib. Mineral. Petrol. 142, 724-527. [5] Burkhard D.J.M. (2001); J. Petrol. 42, 507-527. [6] Burkhard D.J.M. (2003; Bull. Volcanol. 65, 136-143. [7] Lofgren G.E 1983; J. Petrol., 24, 229-225. [8] Burkhard D.J.M., Wirth, R. (2001); EOS Trans. AGU, 82 (47), Fall Meet. Suppl., abstract V51B-1014.

Isotope geochemistry and fluid inclusion study of skarns from Vesuvius

USGS Publications Warehouse

Gilg, H.A.; Lima, A.; Somma, R.; Belkin, H.E.; de Vivo, B.; Ayuso, R.A.

2001-01-01

We present new mineral chemistry, fluid inclusion, stable carbon and oxygen, as well as Pb, Sr, and Nd isotope data of Ca-Mg-silicate-rich ejecta (skarns) and associated cognate and xenolithic nodules from the Mt. Somma-Vesuvius volcanic complex, Italy. The typically zoned skarn ejecta consist mainly of diopsidic and hedenbergitic, sometimes "fassaitic" clinopyroxene, Mg-rich and Ti-poor phlogopite, F-bearing vesuvianite, wollastonite, gehlenite, meionite, forsterite, clinohumite, anorthite and Mg-poor calcite with accessory apatite, spinell, magnetite, perovskite, baddeleyite, and various REE-, U-, Th-, Zr- and Ti-rich minerals. Four major types of fluid inclusions were observed in wollastonite, vesuvianite, gehlenite, clinopyroxene and calcite: a) primary silicate melt inclusions (THOM = 1000-1050??C), b) CO2 ?? H2S-rich fluid inclusions (THOM = 20-31.3??C into the vapor phase), c) multiphase aqueous brine inclusions (THOM = 720-820??C) with mainly sylvite and halite daughter minerals, and d) complex chloride-carbonate-sulfate-fluoride-silicate-bearing saline-melt inclusions (THOM = 870-890??C). The last inclusion type shows evidence for immiscibility between several fluids (silicate melt - aqueous chloride-rich liquid - carbonate/sulfate melt?) during heating and cooling below 870??C. There is no evidence for fluid circulation below 700??C and participation of externally derived meteoric fluids in skarn formation. Skarns have considerably variable 206Pb/204Pb (19.047-19.202), 207Pb/204Pb (15.655-15.670), and 208Pb/204Pb (38.915-39.069) and relatively low 143Nd/144Nd (0.51211-0.51244) ratios. The carbon and oxygen isotope compositions of skarn calcites (??13CV-PDB = -5.4 to -1.1???; ??18OV-SMOW = 11.7 to 16.4???) indicate formation from a 18O- and 13C-enriched fluid. The isotope composition of skarns and the presence of silicate melt inclusion-bearing wollastonite nodules suggests assimilation of carbonate wall rocks by the alkaline magma at moderate depths (< 5 km) and consequent exsolution of CO2-rich vapor and complex saline melts from the contaminated magma that reacted with the carbonate rocks to form skarns.

Soil and climate modelling to explain soil differences in MIS5e and MIS13 on the Chinese Loess Plateau

NASA Astrophysics Data System (ADS)

Finke, P. A.; Yu, Y.; Yin, Q.; Bernardini, N. J.

2016-12-01

Objective Proxy records indicate that MIS5 (about 120 ka ago) was warmer than MIS13 (about 500 ka ago). Nevertheless, MIS13-soils in the Chinese loess plateau (105 -115°E and 30-40°N) are stronger developed than MIS5-soils. This has been attributed to a stronger East Asian summer monsoon. Other differences are interglacial lengths and loess deposition rates. We aimed to find explanations for soil development differences by using a soil formation model (SoilGen) with climatic inputs obtained from an earth system model (LOVECLIM). Material and Methods The LOVECLIM model is driven by time-varying insolation and greenhouse gas concentrations and was run to give monthly values for temperature, precipitation and evaporation as well the dominant vegetation type. Model results for were corrected for systematic differences between present-day observation data and simulation. Reconstructions were made for both interglacials of the amount of inblown loess, and the mineralogy and grain size distribution of the initial loess as well as the dust. These data were fed into the SoilGen model, which was used to calculate various soil parameters with depth and over time. Results Simulations show a stronger developed MIS13 soil, in terms of weathering (loss of anorthite), and redistribution of calcite, gypsum and clay. This corresponds to observed paleosoils. MIS13-soils are more leached. As simulated temperatures and annual precipitation between MIS5 and MIS13 did not vary strongly, the greater length of MIS13 seemed the main explanation for the stronger leaching and weathering. Closer analysis however showed a larger number of months in MIS13 with a precipitation surplus, even when only considering the first 22 ka. Only in such months significant leaching can occur. Conclusion Using simulation models it was demonstrated that the stronger soil expression in MIS13 than in MIS5 is likely caused by more months with a precipitation surplus, in combination with a longer duration of MIS13.

Phase petrology reveals shallow magma storage prior to large explosive silicic eruptions at Hekla volcano, Iceland

NASA Astrophysics Data System (ADS)

Weber, Gregor; Castro, Jonathan M.

2017-05-01

Understanding the conditions that culminate in explosive eruptions of silicic magma is of great importance for volcanic hazard assessment and crisis mitigation. However, geological records of active volcanoes typically show a wide range of eruptive behavior and magnitude, which can vary dramatically for individual eruptive centers. In order to evaluate possible future scenarios of eruption precursors, magmatic system variables for different eruption types need to be constrained. Here we use petrological experiments and microanalysis of crystals to clarify the P-T-x state under which rhyodacitic melts accumulated prior to the H3 eruption; the largest Holocene Plinian eruption of Hekla volcano in Iceland. Cobalt-buffered, H2O-saturated phase equilibrium experiments reproduce the natural H3 pumice phenocryst assemblage (pl > fa + cpx > ilm + mt > ap + zrc) and glass chemistry, at 850 ± 15°C and PH2O of 130 to 175 MPa, implying shallow crustal magma storage between 5 and 6.6 km. The systematics of FeO and anorthite (CaAl2Si2O8) content in plagioclase reveal that thermal gradients were more important than compositional mixing or mingling within this magma reservoir. As these petrological findings indicate magma storage much shallower than is currently thought of Hekla's mafic system, we use the constrained storage depth in combination with deformation modeling to forecast permissible surface uplift patterns that could stem from pre-eruptive magma intrusion. Using forward modeling of surface deformation above various magma storage architectures, we show that vertical surface displacements caused by silicic magma accumulation at ∼6 km depth would be narrower than those observed in recent mafic events, which are fed from a lower crustal storage zone. Our results show how petrological reconstruction of magmatic system variables can help link signs of pre-eruptive geophysical unrest to magmatic processes occurring in reservoirs at shallow depths. This will enhance our abilities to couple deformation measurements (e.g. InSAR and GPS) to petrological studies to better constrain potential precursors to volcanic eruptions.

Application of New Partition Coefficients to Modeling Plagioclase

NASA Technical Reports Server (NTRS)

Fagan, A. L.; Neal, C. R.; Rapp, J. F.; Draper, D. S.; Lapen, T. J.

2017-01-01

Previously, studies that determined the partition coefficient for an element, i, between plagioclase and the residual basaltic melt (Di plag) have been conducted using experimental conditions dissimilar from the Moon, and thus these values are not ideal for modeling plagioclase fractionation in a lunar system. However, recent work [1] has determined partition coefficients for plagioclase at lunar oxygen fugacities, and resulted in plagioclase with Anorthite contents =An90; these are significantly more calcic than plagioclase in previous studies, and the An content has a profound effect on partition coefficient values [2,3]. Plagioclase D-values, which are dependent on the An content of the crystal [e.g., 2-6], can be determined using published experimental data and the correlative An contents. Here, we examine new experimental data from [1] to ascertain their effect on the calculation of equilibrium liquids from Apollo 16 sample 60635,2. This sample is a coarse grained, subophitic impact melt composed of 55% plagioclase laths with An94.4-98.7 [7,8], distinctly more calcic than of previous partition coefficient studies (e.g., [3-6, 9-10]). Sample 60635,2 is notable as having several plagioclase trace element analyses containing a negative Europium anomaly (-Eu) in the rare-earth element (REE) profile, rather than the typical positive Eu anomaly (+Eu) [7-8] (Fig. 1). The expected +Eu is due to the similarity in size and charge with Ca2+, thereby allowing Eu2+ to be easily taken up by the plagioclase crystal structure, in contrast to the remaining REE3+. Some 60635,2 plagioclase crystals only have +Eu REE profiles, some only have -Eu REE profiles, and some +Eu and -Eu analyses in different areas on a single crystal [7, 8]. Moreover, there does not seem to be any core-rim association with the +Eu or -Eu analyses, nor does there appear to be a correlation between the size, shape, or location of a particular crystal within the sample and the sign of its Eu anomaly, which suggests a complex evolution. In order to investigate this sample further, we can calculate the equilibrium liquids, but with An contents distinct from previous experimental studies, we must calculate the appropriate partition coefficients for each trace element analysis.

Digging Deep: Is Lunar Mantle Excavated Around the Imbrium Basin?

NASA Astrophysics Data System (ADS)

Klima, R. L.; Bretzfelder, J.; Buczkowski, D.; Ernst, C. M.; Greenhagen, B. T.; Petro, N. E.; Shusterman, M. L.

2017-12-01

The Moon has experienced over a dozen impacts resulting in basins large enough to have excavated mantle material. With many of those basins concentrated on the lunar near side, and extensive regolith mixing since the lunar magma ocean crystallized, one might expect that some mantle material would have been found among the lunar samples on Earth. However, so far, no mantle clasts have been definitively identified in lunar samples [1]. From orbit, a number of olivine-bearing localities, potentially sourced from the mantle, have been identified around impact basins [2]. Based on analysis of near-infrared (NIR) and imaging data, [3] suggest that roughly 60% of these sites represent olivine from the mantle. If this is the case and the blocks are coherent and not extensively mixed into the regolith, these deposits should be ultramafic, containing olivine and/or pyroxenes and little to no plagioclase. In the mid-infrared, they would thus exhibit Christiansen features at wavelengths in excess of 8.5 μm, which has not been observed in global studies using the Diviner Lunar Radiometer [4]. We present an integrated study of the massifs surrounding the Imbrium basin, which, at over 1000 km wide, is large enough to have penetrated through the lunar crust and into the mantle. These massifs are clearly associated with the Imbrium basin-forming impact, but existing geological maps do not distinguish between whether they are likely ejecta or rather uplifted from beneath the surface during crustal rebound [5]. We examine these massifs using vis, NIR and Mid IR data to determine the relationships between and the bulk mineralogy of local lithologies. NIR data suggest that the massifs contain exposures of four dominant minerals: olivine, Mg-rich orthopyroxene, a second low-Ca pyroxene, and anorthite. Mid IR results suggest that though many of these massifs are plagioclase-rich, portions of some may be significantly more mafic. We will present our growing mineralogical map of the Imbrium basin perimeter, and discuss implications for the sub-basin stratigraphy and potential excavation of mantle material. [1] Shearer et al. (2015) MAPS 50, 1449. [2] Yamamoto et al. (2012) GRL 39, L13201. [3] Ohtake et al. (2017) New Views of the Moon 2 - Europe, Abstract #6016 [4] Greenhagen et al. (2010) Science 329, 1507. [5] Wilhelms D. E. et al. (1987), USGS Lunar map.

The Effects of Varying Crustal Carbonate Composition on Assimilation and CO2 Degassing at Arc Volcanoes

NASA Astrophysics Data System (ADS)

Carter, L. B.; Holmes, A. K.; Dasgupta, R.; Tumiati, S.

2015-12-01

Magma-crustal carbonate interaction and subsequent decarbonation can provide an additional source of CO2 release to the exogenic system superimposed on mantle-derived CO2. Carbonate assimilation at present day volcanoes is often modeled by limestone consumption experiments [1-4]. Eruptive products, however, do not clearly display the characteristic ultracalcic melt compositions produced during limestone-magma interaction [4]. Yet estimated CO2outflux [5] and composition of volcanics in many volcanic systems may allow ~3-17% limestone- or dolostone-assimilated melt contribution. Crystallization may retain ultracalcic melts in pyroxenite cumulates. To extend our completed study on limestone assimilation, here we explore the effect of varying composition from calcite to dolomite on chemical and thermal decarbonation efficiency of crustal carbonates. Piston cylinder experiments at 0.5 GPa and 900-1200 °C demonstrate that residual mineralogy during interaction with magma shifts from CaTs cpx and anorthite/scapolite in the presence of calcite to Di cpx and Fo-rich olivine with dolomite. Silica-undersaturated melts double in magnesium content, while maintaining high (>30 wt.%) CaO values. At high-T, partial thermal breakdown of dolomite into periclase and CO2 is minimal (<5%) suggesting that in the presence of magma, CO2 is primarily released due to assimilation. Assimilated melts at identical P-T conditions depict similarly high volatile contents (10-20 wt.% by EMPA deficit at 0.5 GPa, 1150 °C with hydrous basalt) with calcite or dolomite. Analysis of the coexisting fluid phase indicates the majority of water is dissolved in the melt, while CO2 released from the carbonate is preferentially partitioned into the vapor. This suggests that although assimilated melts have a higher CO2 solubility, most of the CO2can easily degas from the vapor phase at arc volcanoes, possibly more so at volcanic plumbing systems traversing dolomite [8]. [1]Conte et al 2009 EuJMin (21) 763-782; [2]Iacono-Marziano et al 2008 CMP (155) 719-738; [3]Mollo et al 2010 Lithos (114) 503-514; [4]Carter and Dasgupta 2015 EPSL (427) 202-214; [5]Burton et al 2013 RevMinGeochem (75) 323-254; [6]Balassone et al 2013 Lithos (160-161) 84-97; [7]Di Rocco et al. 2012 JPet (53) 2307-2332; [8]Del Moro et al 2001 JVGR (112) 15-24.

Petrological and experimental evidence for differentiation of water-rich magmas beneath St. Kitts, Lesser Antilles

NASA Astrophysics Data System (ADS)

Melekhova, Elena; Blundy, Jon; Martin, Rita; Arculus, Richard; Pichavant, Michel

2017-12-01

St. Kitts lies in the northern Lesser Antilles, a subduction-related intraoceanic volcanic arc known for its magmatic diversity and unusually abundant cognate xenoliths. We combine the geochemistry of xenoliths, melt inclusions and lavas with high pressure-temperature experiments to explore magma differentiation processes beneath St. Kitts. Lavas range from basalt to rhyolite, with predominant andesites and basaltic andesites. Xenoliths, dominated by calcic plagioclase and amphibole, typically in reaction relationship with pyroxenes and olivine, can be divided into plutonic and cumulate varieties based on mineral textures and compositions. Cumulate varieties, formed primarily by the accumulation of liquidus phases, comprise ensembles that represent instantaneous solid compositions from one or more magma batches; plutonic varieties have mineralogy and textures consistent with protracted solidification of magmatic mush. Mineral chemistry in lavas and xenoliths is subtly different. For example, plagioclase with unusually high anorthite content (An≤100) occurs in some plutonic xenoliths, whereas the most calcic plagioclase in cumulate xenoliths and lavas are An97 and An95, respectively. Fluid-saturated, equilibrium crystallisation experiments were performed on a St. Kitts basaltic andesite, with three different fluid compositions ( XH2O = 1.0, 0.66 and 0.33) at 2.4 kbar, 950-1025 °C, and fO2 = NNO - 0.6 to NNO + 1.2 log units. Experiments reproduce lava liquid lines of descent and many xenolith assemblages, but fail to match xenolith and lava phenocryst mineral compositions, notably the very An-rich plagioclase. The strong positive correlation between experimentally determined plagioclase-melt KdCa-Na and dissolved H2O in the melt, together with the occurrence of Al-rich mafic lavas, suggests that parental magmas were water-rich (> 9 wt% H2O) basaltic andesites that crystallised over a wide pressure range (1.5-6 kbar). Comparison of experimental and natural (lava, xenolith) mafic mineral composition reveals that whereas olivine in lavas is predominantly primocrysts precipitated at low-pressure, pyroxenes and spinel are predominantly xenocrysts formed by disaggregation of plutonic mushes. Overall, St. Kitts xenoliths and lavas testify to mid-crustal differentiation of low-MgO basalt and basaltic andesite magmas within a trans-crustal, magmatic mush system. Lower crustal ultramafic cumulates that relate parental low-MgO basalts to primary, mantle -derived melts are absent on St. Kitts.

Textural and microstructural development of the Barro Alto Complex: implications for seismic anisotropy

NASA Astrophysics Data System (ADS)

Silveira, Camila; Lagoeiro, Leonardo; Barbosa, Paola; Cavalcante, Geane Carolina; Ferreira, Filippe; Suita, Marcos; Conte, Thailli

2017-04-01

Crustal rheology is associated with the behavior of its constituents in response to stress and strain, while the seismic anisotropy is a property that can correlate these parameters. Seismic properties are strongly related to the microstructures and crystallographic preferred orientation (CPO) of the rocks. In this work, we study CPO-derived seismic anisotropy of metamorphosed gabbro-norites from the Barro Alto (Brazil central) layered complex. The EBSD technique was employed to analyze the crystallographic orientation of the main mineral assembly, diopside and feldspar. The Barro Alto complex belongs to the Tocantins Structural Province, developed between the Amazon and São Francisco cratons, during the Neoproterozoic Brasiliano orogenic cycle. This complex was formed by a mafic-ultramafic layered intrusion mylonitized and metamorphosed under granulite facies conditions. The mylonitic foliation shows compositional segregation into felsic and mafic bands. The samples are composed of porphyroclasts of plagioclase and diopside in a fine matrix of plagioclase, clinopyroxene, orthopyroxene and, less commonly, amphibole and biotite. The plagioclase porphyroclasts exhibit undulose extinction and core-mantle structure. In fine matrix samples the poles to a(100), b(010) and c(001) are randomly distributed in both phases. However, for increasing matrix grain size plagioclase grains shows maxima of a(100) poles sub-parallel to the foliation and b(010) normal to the foliation. The low value of the J index (2.4 for plagioclase and 1.8 for diopside) indicates poorly developed fabric. Misorientation profiles showing high frequency of small angle boundaries are typical of recrystallization by subgrain rotation mechanisms. The microstructural and CPO analyses suggest deformation controlled by diffusive processes. The CPO models were compared to models described in the literature, based on the anorthite + diopside assembly, since these are the major phases, and thus control the seismic properties of the aggregate. The CPO of plagioclase can then be classified as Type P, intermediate between plastic deformation and magmatic flow. The seismic anisotropy patterns presented low value of P-wave velocity (Vp), being the fast velocity direction perpendicular to the foliation, while the S wave anisotropy is extremely low (1.1 to 3%). The mineral assembly and the deformation mechanisms played a major role in the resulting patterns of seismic propagation by reducing the anisotropic behavior of these rocks, creating patterns similar to those found in an isotropic media.

Petrographic Analyses of Lonestones from ODP Drill Sites Leg 188 Prydz Bay, Antarctica

NASA Astrophysics Data System (ADS)

Detterman, K.; Warnke, D. A.; Richter, C.

2006-12-01

ODP Leg 188 was drilled in 2000 to sample the first advances of the Antarctic ice sheet and to document further cryospheric development. Continental shelf Site 1166 documented the earliest stages of glaciation during the Eocene-Oligocene and continental slope Site 1167 documented rapid deposition by debris flows during the Pliocene-Pleistocene and a subtle change in onshore erosion areas. Site 1165, located on the continental rise, documented long-term transition from wet-based lower Miocene glaciers to dry-based upper Miocene glaciers, including short-term fluctuations starting in the early Miocene. Source areas for all drill sites are the Lambert Glacier-Amery Ice Shelf drainage area, encompassing the Northern and Southern Prince Charles Mountains, the Gamburtsev Sub-glacial Mountains, and the Grove Mountains. Lonestones occur in most of the cores from all sites of Leg 188 prompting research for potential source areas and transportation modes of the lonestones. One-hundred and seventeen thin sections of lonestones were prepared from Sites 1166, 1167, and 1165 for petrographic analyses. Metamorphic lonestones outnumber igneous and sedimentary lonestones at all three sites. Sedimentary lonestones were not found in the thin sections of Site 1166. Extrusive igneous lonestones were found only at Site 1165 and comprised 5.1 percent of Leg 188's lithology. The anorthite content of igneous and metamorphic lonestones represented at all three sites was albite-oligoclase plagioclase. Albite oligoclase plagioclase has been documented in the Southern Prince Charles Mountains. The results of this study of a selection of lonestones from Site 1167 supports a hypothesis first proposed by the Shipboard Scientific Party in 2001 that as time elapsed, the source area for Site 1167 lonestones shifted slightly from a largely sandstone source to a largely granitic source within the drainage area. One potential source area for the Site 1167 sandstone lonestones is the Permian to Triassic Amery Group in the Beaver Lake area of the Northern Prince Charles Mountains. We hypothesize that more easily eroded portions of the sandstone outcrops were planed off first while ubiquitous gneiss and granite outcrops provided the source material for the younger debris flows at Site 1167 in the Pliocene-Pleistocene. None of all the available lonestones suggest sources other than the drainage area of the Lambert Glacier- Amery Ice Shelf complex.

Traces of the heritage arising from the Macelj sandstone

NASA Astrophysics Data System (ADS)

Golež, Mateja

2014-05-01

The landscape of Southeast Slovenia and its stone heritage principally reveal itself through various Miocene sandstones. The most frequently found type on the borderline between Slovenia and Croatia, i.e. east of Rogatec, is the micaceous-quartz Macelj sandstone. This rock ranges in colour from greenish grey to bluish grey and yellowish, depending on the content of glauconite, which colours it green. In its composition, the rock is a heterogeneous mixture of grains of quartz, dolomite, muscovite, microcline, anorthite and glauconite. The average size of grains is 300μm. In cross-section, they are oblong, semi-rounded or round. The mechanical-physical and durability properties of the Macelj sandstone, which have been characterised pursuant to the applicable standards for natural stone, reveal that the rock exhibits poor resistance to active substances from the atmosphere, particularly in the presence of salt. In the surroundings of Rogatec, there are around 45 abandoned quarries of the Macelj sandstone, which are the result of the exploitation of this mineral resource from the 17th century on. The local quarrymen earned their bread until 1957, when the Kambrus quarry industry closed down. From the original use of this mineral resource as construction and decorative material, the useful value of the Macelj sandstone expanded during the development of the metals industry to the manufacture of large and small grindstones for the needs of the domestic and international market. Therefore, traces of quarrying can not only be seen in the disused quarries, but also in the rich architectural heritage of Rogatec and its surroundings, the stone furniture - from portals, window frames, wells, various troughs, pavements to stone walls - and other. The living quarrying heritage slowly passed into oblivion after World War II, although the analysis of the social image of the people residing in Rogatec and its surroundings revealed that there was an average of one stonemason in every house in the period between both World Wars. Only few masters succeeded in transferring their know-how to their descendants, which is why the local community has been making efforts to include the quarrying and working of the Macelj sandstone in educational workshops that are being carried out at the Open-Air Museum in Rogatec.

Molecular Dynamics Studies of CaAl2Si2O8 Liquid to 800 GPa: An Equation of State (EOS), Hugoniot Analysis, and Thermodynamic Model Over the Temperature-Range 2500-5000 K (Invited)

NASA Astrophysics Data System (ADS)

Ghiorso, M. S.; Cutler, I.; Nevins, D.; Spera, F. J.

2009-12-01

Equilibrium Molecular Dynamics (MD) simulations are applied to molten CaAl2Si2O8 using a Coulomb-Born-Mayer-van der Waals pair potential form and parameters from Matsui (1996, GRL 23:395). Experiments were performed in the microcanonical ensemble (NEV) using 8000 atoms, a 1 fs time step, and simulation durations of 50 ps. Computations were carried out every 500 K over a temperature range of 2500 - 5000 K along 21 isochores to yield a grid of 141 state points spanning the pressure range 0-800 GPa. Atomic coordination statistics are determined by counting nearest neighbor configurations up to a cutoff distance defined by the first minima of the pair correlation function. A thermodynamic model (and EOS) for this liquid is developed from the MD simulation results by combining the Rosenfeld-Tarazona (1998, Mol Phys 95:141) potential energy-temperature scaling law with the Universal EOS (1986, J Phys C, 19:L467). The resulting model is used to estimate thermodynamic properties and the sound speed of the liquid near zero pressure and these compare favorably to physical experiments. By contrast to our previous work (DOI: 10.1016/j.gca.2009.08.012), which utilized an alternate pair potential, no structural phase transition is required to thermodynamically model these results — a single parameterization describes the properties of the system over the entire range of ~4-fold compression. Our analysis indicates the existence of polyamorphism with a critical point at ~0.6 GPa and ~3000 K. A modeled Hugoniot is consistent with the low-pressure shock experiments of Rigden et al. (JGR 94:9508) but inconsistent with the more recent measurements of Asimow and Ahrens (EOS 89,MR32B-04). The latter experiments are matched with a model isentrope emanating from just above the zero pressure melting point of anorthite, which also coincides with the initial conditions of the shock. The MD simulations reveal that near zero-pressure, CaAl2Si2O8 liquid is dominated by Si in tetrahedral coordination with oxygen. Pentahedral coordinated Si attains a maximum at ~25 GPa, and at higher pressures octahedral and higher-order O-Si structures dominate.

Chondrites and the Protoplanetary Disk, Part 3

NASA Technical Reports Server (NTRS)

2004-01-01

Contents include the following: Ca-, Al-Rich Inclusions and Ameoboid Olivine Aggregates: What We Know and Don t Know About Their Origin. Aluminium-26 and Oxygen Isotopic Distributions of Ca-Al-rich Inclusions from Acfer 214 CH Chondrite. The Trapping Efficiency of Helium in Fullerene and Its Implicatiion to the Planetary Science. Constraints on the Origin of Chondritic Components from Oxygen Isotopic Compositions. Role of Planetary Impacts in Thermal Processing of Chondrite Materials. Formation of the Melilite Mantle of the Type B1 CAIs: Flash Heating or Transport? The Iodine-Xenon System in Outer and Inner Portions of Chondrules from the Unnamed Antarctic LL3 Chondrite. Nucleosynthesis of Short-lived Radioactivities in Massive Stars. The Two-Fluid Analysis of the Kelvin-Helmholtz Instability in the Dust Layer of a Protoplanetary Disk: A Possible Path to the Planetesimal Formation Through the Gravitational Instability. Shock-Wave Heating Model for Chonodrule Formation: Heating Rate and Cooling Rate Constraints. Glycine Amide Hydrolysis with Water and OH Radical: A Comparative DFT Study. Micron-sized Sample Preparation for AFM and SEM. AFM, FE-SEM and Optical Imaging of a Shocked L/LL Chondrite: Implications for Martensite Formation and Wave Propagation. Infrared Spectroscopy of Chondrites and Their Components: A Link Between Meteoritics and Astronomy? Mid-Infrared Spectroscopy of CAI and Their Mineral Components. The Origin of Iron Isotope Fractionation in Chondrules, CAIs and Matrix from Allende (CV3) and Chainpur (LL3) Chondrites. Protoplanetary Disk Evolution: Early Results from Spitzer. Kinetics of Evaporation-Condensation in a Melt-Solid System and Its Role on the Chemical Composition and Evolution of Chondrules. Oxygen Isotope Exchange Recorded Within Anorthite Single Crystal in Vigarano CAI: Evidence for Remelting by High Temperature Process in the Solar Nebula. Chondrule Forming Shock Waves in Solar Nebula by X-Ray Flares. Organic Globules with Anormalous Nitrogen Isotopic Compositions in the Tagish Lake Meteorite: Products of Primitive Organic Reactions. Yet Another Chondrule Formation Scenario. CAIs are Not Supernova Condensates. Microcrystals and Amorphous Material in Comets and Primitive Meteorites: Keys to Understanding Processes in the Early Solar System. A Nearby Supernova Injected Short-lived Radionuclides into Our Protoplanetary Disk. REE+Y Systematics in CC and UOC Chondrules. Meteoritic Constraints on Temperatures, Pressures, Cooling Rates, Chemical Compositions, and Modes of Condensation in the Solar Nebula. The I-Xe Record of Long Equilibration in Chondrules from the Unnamed Antarctic Meteorite L3/LL3. Early Stellar Evolution.

Mineral chemistry of Pangidi basalt flows from Andhra Pradesh

NASA Astrophysics Data System (ADS)

Nageswara Rao, P. V.; Swaroop, P. C.; Karimulla, Syed

2012-04-01

This paper elucidates the compositional studies on clinopyroxene, plagioclase, titaniferous magnetite and ilmenite of basalts of Pangidi area to understand the geothermometry and oxybarometry conditions. Petrographic evidence and anorthite content (up to 85%) of plagioclase and temperature estimates of clinopyroxene indicate that the clinopyroxene is crystallized later than or together with plagioclase. The higher An content indicates that the parent magma is tholeiitic composition. The equilibration temperatures of clinopyroxene (1110-1190°C) and titaniferous magnetite and ilmenite coexisting mineral phases (1063-1103°C) are almost similar in lower basalt flow and it is higher for clinopyroxene (900-1110°C) when compared to titaniferous magnetite and ilmenite coexisting mineral phases (748-898°C) in middle and upper basalt flows. From this it can be inferred that the clinopyroxene is crystallized earlier than Fe-Ti oxide phases reequilibration, which indicates that the clinopyroxene temperature is the approximate eruption temperature of the present lava flows. The wide range of temperatures (900-1190°C) attained by clinopyroxene may point out that the equilibration of clinopyroxene crystals initiated from depth till closer to the surface before the melt erupted. Pangidi basalts follow the QFM buffer curve which indicates the more evolved tholeiitic composition. This suggests the parent tholeiitic magma suffered limited fractionation at high temperature under increasing oxygen fugacity in lower basalt flow and more fractionation at medium to lower temperatures under decreasing oxygen fugacity conditions during cooling of middle and upper basalt flows. The variation of oxygen fugacity indicates the oxidizing conditions for lower basalt flow (9.48-10.3) and extremely reducing conditions for middle (12.1-15.5) and upper basalt (12.4-15.54) flows prevailed at the time of cooling. Temperature vs. (FeO+Fe2O3)/(FeO+Fe2O3 +MgO) data plots for present basalts suggested the lower basaltic flow is formed at higher temperatures while the middle and upper basalt flows at medium to lower temperatures. The lower basalt flow is represented by higher temperatures which shows high modal values of opaques and glass whereas the medium to lower temperatures of middle and upper flow are caused by vesicular nature which contain larger content of gases and humid to semi-arid conditions during cooling.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matzel, J P; Jacobsen, B; Hutcheon, I D

The abundance of short-lived radionuclides (SLRs) in early solar system materials provide key information about their nucleosynthetic origin and can constrain the timing of early solar system events. Excesses of {sup 36}S ({sup 36}S*) correlated with {sup 35}Cl/{sup 34}S ratios provide direct evidence for in situ decay of {sup 36}Cl ({tau}{sub 1/2} {approx} 0.3 Ma) and have been reported in sodalite (Na{sub 8}Al{sub 6}Si{sub 6}O{sub 24}Cl{sub 2}) and wadalite (Ca{sub 6}Al{sub 5}Si{sub 2}O{sub 16}Cl{sub 3}) in CAIs and chondrules from the Allende and Ningqiang CV carbonaceous chondrites. While previous studies demonstrate unequivocally that {sup 36}Cl was extant in the earlymore » solar system, no consensus on the origin or initial abundance of {sup 36}Cl has emerged. Understanding the origin of {sup 36}Cl, as well as the reported variation in the initial {sup 36}Cl/{sup 35}Cl ratio, requires addressing when, where and how chlorine was incorporated into CAIs and chondrules. These factors are key to distinguishing between stellar nucleosynthesis or energetic particle irradiation for the origin of {sup 36}Cl. Wadalite is a chlorine-rich secondary mineral with structural and chemical affinities to grossular. The high chlorine ({approx}12 wt%) and very low sulfur content (<<0.01 wt%) make wadalite ideal for studies of the {sup 36}Cl-{sup 36}S system. Wadalite is present in Allende CAIs exclusively in the interior regions either in veins crosscutting melilite or in zones between melilite and anorthite associated with intergrowths of grossular, monticellite, and wollastonite. Wadalite and sodalite most likely resulted from open-system alteration of primary minerals with a chlorine-rich fluid phase. We recently reported large {sup 36}S* correlated with {sup 35}Cl/{sup 34}S in wadalite in Allende Type B CAI AJEF, yielding a ({sup 36}Cl/{sup 35}Cl){sub 0} ratio of (1.7 {+-} 0.3) x 10{sup -5}. This value is the highest reported {sup 36}Cl/{sup 35}Cl ratio and is {approx}5 times greater than values for sodalite in some CAIs and chondrules. We report here new {sup 36}Cl-{sup 36}S isotope measurements of wadalite in two Type B CAIs (TS34 and Egg-6) and sodalite in a fine-grained CAI (Pink Angel) from Allende.« less

Predictions of diagenetic reactions in the presence of organic acids

NASA Astrophysics Data System (ADS)

Harrison, Wendy J.; Thyne, Geoffrey D.

1992-02-01

Stability constants have been estimated for cation complexes with anions of monofunctional and difunctional acids (combinations of Ca, Mg, Fe, Al, Sr, Mn, U, Th, Pb, Cu, Zn with formate, acetate, propionate, oxalate, malonate, succinate, and salicylate) between 0 and 200°C. Difunctional acid anions form much more stable complexes than monofunctional acid anions with aluminum; the importance of the aluminum-acetate complex is relatively minor in comparison to aluminum oxalate and malonate complexes. Divalent metal cations such as Mg, Ca, and Fe form more stable complexes with acetate than with difunctional acid anions. Aluminum-oxalate can dominate the species distribution of aluminum under acidic pH conditions, whereas the divalent cation-acetate and oxalate complexes rarely account for more than 60% of the total dissolved cation, and then only in more alkaline waters. Mineral thermodynamic affinities were calculated using the reaction path model EQ3/6 for waters having variable organic acid anion (OAA) contents under conditions representative of those found during normal burial diagenesis. The following scenarios are possible: 1) K-feldspar and albite are stable, anorthite dissolves 2) All feldpars are stable 3) Carbonates can be very unstable to slightly unstable, but never increase in stability. Organic acid anions are ineffective at neutral to alkaline pH in modifying stabilities of aluminosilicate minerals whereas the anions are variably effective under a wide range of pH in modifying carbonate mineral stabilities. Reaction path calculations demonstrate that the sequence of mineral reactions occurring in an arkosic sandstone-fluid system is only slightly modified by the presence of OAA. A spectrum of possible sandstone alteration mineralogies can be obtained depending on the selected boundary conditions: EQ3/6 predictions include quartz overgrowth, calcite replacement of plagioclase, albitization of plagioclase, and the formation of porosity-occluding calcite cement, smectite, and illite, all of which are commonly documented in rocks. Under some circumstances, OAA-bearing waters are less effective at producing porosity in an arkosic sandstone than are OAA-free waters. In the scenarios modeled in this study the role of OAA in fluid-rock interactions is to contribute to the total alteration assemblage but not necessarily to dominate it, except under exceptional circumstances that might include, for example, hydrocarbon contaminant plumes in aquifers, wetland environments, and within hydrocarbon source-rocks.

Does Silicate Weathering of Loess Affect Atmospheric CO2?

NASA Astrophysics Data System (ADS)

Anderson, S. P.

2002-12-01

Weathering of glacial loess may be a significant, yet unrecognized, component of the carbon cycle. Glaciers produce fine-grained sediment, exposing vast amounts of mineral surface area to weathering processes, yet silicate mineral weathering rates at glacier beds and of glacial till are not high. Thus, despite the tremendous potential for glaciers to influence global weathering rates and atmospheric CO2 levels, this effect has not been demonstrated. Loess, comprised of silt-clay sizes, may be the key glacial deposit in which silicate weathering rates are high. Loess is transported by wind off braid plains of rivers, and deposited broadly (order 100 km from the source) in vegetated areas. Both the fine grain size, and hence large mineral surface area, and presence of vegetation should render loess deposits highly susceptible to silicate weathering. These deposits effectively extend the geochemical impact of glaciation in time and space, and bring rock flour into conditions conducive to chemical weathering. A simple 1-d model of silicate weathering fluxes from a soil profile demonstrates the potential of loess deposition to enhance CO2 consumption. At each time step, computed mineral dissolution (using anorthite and field-based rate constants) modifies the size of mineral grains within the soil. In the case of a stable soil surface, this results in a gradual decline in weathering fluxes and CO2 consumption through time, as finer grain sizes dissolve away. Computed weathering fluxes for a typical loess, with an initial mean grain size of 25 μm, are an order of magnitude greater than fluxes from a non-loess soil that differs only in having a mean grain size of 320 μm. High weathering fluxes are maintained through time if loess is continually deposited. Deposition rates as low as 0.01 mm/yr (one loess grain thickness per year) can lead to a doubling of CO2 consumption rates within 5 ka. These results suggest that even modest loess deposition rates can significantly increase CO2 consumption rates due to silicate weathering in soils. Thick loess deposits cover 5-10% of the global land surface, and loess deposits too thin to be included in global inventories cover a much greater area. Loess deposition and weathering over timescales greater than the duration of glaciation must be considered in models of atmospheric CO2 variation.

Soufrière Hills Plagioclase: Postcards From the Edge.

NASA Astrophysics Data System (ADS)

Genareau, K.; Clarke, A.; Hervig, R.

2005-12-01

Secondary Ion Mass Spectrometry (SIMS) can provide sub-micron depth resolution for analyzing products of volcanic eruptions. SIMS was used to examine the outer rims of plagioclase phenocrysts derived from both explosive and effusive eruptions of the Soufrière Hills Volcano (SHV), Montserrat. Phenocrysts were separated from the host igneous rock by crushing with a mortar and pestle and then cleaned with a Branson Sonifier. A 12.5 kV O2+ primary ion beam was used to examine the variation in ten elements (Ca, Na, Si, Al, Ti, Zr, K, Fe, Sr, Li) through a crystal depth of 5-9 microns. Plagioclase crystals separated from explosively produced pumice clasts show increasing anorthite (An) content with depth into the crystal surface, starting at ~10% An at the surface and reaching a constant composition of ~45% An at 2-4 microns depth. According to experimentally determined estimates of plagioclase growth rates for the SHV magma (Couch et al. 2003; J. Petrology 44, 1477-1502), the 2-4 microns depth over which An changes corresponds to 1-7 hours of growth. Sr also shows a general increase with depth into the crystal. K shows a rapid decrease in abundance with depth. Fe shows more complex patterns that may indicate late-stage crystallization of magnetite. Plagioclase derived from exogenous dome samples also have surface compositions of ~10% An increasing with depth to ~30% An, but rather than plateau, the values begin to decrease again at 2-5 microns depth. This fluctuating abundance of An may reveal the presence of micron-scale decompression-induced growth zones that have not been previously documented due to limitations in the spatial resolution of conventional analytical techniques. Explosive and effusive samples exhibit conflicting Li trends. The explosively derived plagioclase have elevated surface Li concentrations while the dome derived plagioclase have low surface Li concentrations. These differing trends may provide evidence of closed system vs. open system degassing as a function of eruptive style. Geochemical analyses of igneous phenocrysts using the SIMS depth-profiling technique can be used to constrain the style of magma decompression and eruption. Additional analyses are currently being performed on an expanded suite of samples in order to confirm these results and to relate crystal-edge chemistry to other parameters such as quench pressure and degree of magma degassing.

Shoshonites and Associated Calc-Alkaline Rocks from the Eastern Sayan, Central Asian Orogenic Belt: Geochemistry and Tectonic Setting

NASA Astrophysics Data System (ADS)

Vernikovskaya, A. E.; Romanov, M. I.; Kadilnikov, P. I.; Matushkin, N. Y.; Romanova, I.

2017-12-01

The Central Asian Orogenic Belt (CAOB) is one of the largest accretionary orogens in the world, which formation started in the Neoproterozoic giving rise to numerous assemblages of island arcs, ophiolites, continental fragments and sedimentary basins. The Eastern Sayan, located at the southwestern margin of the Siberian craton, is the key area in understanding the initiation of orogenic processes in the CAOB. Widely distributed mafic igneous rocks (dolerites, gabbro etc.) in the Eastern Sayan were previously considered as part of the Nersa igneous complex of the Neoproterozoic age, whereas tectonic setting of these rocks remained highly debatable. New geochemical and mineralogical data from igneous mafic rocks within the Eastern Sayan show presence of rocks with shoshonitic and high- and low-K calc-alkaline affinities and allowed us to refine the tectonic context of their formation in the southwestern margin of the Siberian craton.All studied intrusive and volcanic rocks in the Eastern Sayan showing OIB-like geochemical signatures. The high-K rocks contain orthoclase, olivine, diopside, augite, anorthite, various amphiboles, including edenite, cataphorite, Mg-cataphorite, anthophyllite-gedrite, Mg-Fe hornblende, biotites of the siderophyllite-eastonite-annite series, as well as zircon, baddeleyite, apatite, magnetite, ilmenite and Cr-spinel. The high-K rock type is characterised by high K2O contents (up to 9.2 wt. %), K2O/Na2O ratios over 90, lowered TiO2 and MgO and moderate FeO contents and negative P and Sr anomalies. In contrast, low-K rocks, characterised by moderate and increased TiO2 and MgO contents, contain augite, pigeonite, olivine, andesine and accessory minerals, such as rutile, titanite, ilmenite and apatite. Both rock types vary considerably in Nb and Ta concentrations, from OIB-like to E-MORB. Such geochemical signatures of calc-alkaline and shoshonitic igneous rocks are indicative of an active continental margin setting. Presence of the active continental margin setting in the southwestern margin of the Siberian craton during the late Neoproterozoic-early Cambrian time is in agreement with the U-Pb age of 511 Ma of high-K dolerites (Gladkochub et al., 2006) and the development of the coeval island arc assemblages in the northern part of the CAOB.

A Little Island With A Big Secret: Isla Rábida, Galápagos

NASA Astrophysics Data System (ADS)

Bercovici, H.; Geist, D.; Harpp, K. S.; Almeida, M.; Mahr, J.; Pimentel, R.; Cleary, Z.

2016-12-01

The Galápagos Archipelago is a hotspot island chain 1000 km west of Ecuador, where the vast majority of the lavas are basaltic. Four volcanoes in the archipelago, Rábida, Santiago, Pinzón, and Alcedo, erupt rhyolites and trachytes. Isla Rábida, a small island 50 km east of the mantle plume center, is the focus of this project. It is 5 km2 in area, and lavas range from 0.9 to 1.1 Ma. About 25% of the rocks in our suite are intermediate to felsic, extending from Mg#=2 to 57. Major and trace element data indicate the evolved rocks formed by advanced crystallization of basaltic magma. One of the unique aspects of Rábida is the cumulate xenolith suite ranging from olivine gabbro to ferroan granite. The basalts have 6 to 58 modal% plagioclase phenocrysts, which we interpret as mixtures of melt and accumulated plagioclase mush at the margins of the shallow reservoir. Thus, Rábida erupts material that has undergone different extents of crystallization and crystal sorting from pure melts, to melt-mush hybrids, to solidified cumulates. This hypothesis is evaluated by comparing plagioclase compositions from the xenoliths and the lavas. Plagioclases in two of the lavas, one with Mg#=57 and the other with Mg#=36, have similar compositions and zonation patterns to each other. There is on average less than 4% change in anorthite content from the core of the plagioclases in the basalts to the rim, with the compositions overall varying between An22 and An37. Both melts likely picked up the crystals from the same plagioclase mush before eruption. In comparison to plagioclases in an olivine-gabbro xenolith from Rábida, those in the lavas are less zoned, suggesting that the lavas' plagioclases experienced a different growth environment. Plagioclases in the xenolith are normally zoned, with cores averaging An37 and rims averaging An32. The xenolith's plagioclases also have more diverse compositions than those in the lavas. The normal zoning in the xenolith's plagioclase is likely from late-stage crystallization of evolved intercumulus melt. Our results suggest that the extraordinary petrologic diversity of Rábida is attributable to crystal-liquid segregation and reincorporation of plagioclase in various melts. These processes result in the eruption of pure melt, melt mixed with mush, and cumulates.

How Rich is Rich? Placing Constraints on the Abundance of Spinel in the Pink Spinel Anorthosite Lithology on the Moon Through Space Weathering

NASA Technical Reports Server (NTRS)

Gross, J.; Gillis-Davis, J.; Isaacson, P. J.; Le, L.

2015-01-01

previously unknown lunar rock was recently recognized in the Moon Mineralogy Mapper (M(sup 3)) visible to near-infrared (VNIR) reflectance spectra. The rock type is rich in Mg-Al spinel (approximately 30%) and plagioclase and contains less than 5% mafic silicate minerals (olivine and pyroxene). The identification of this pink spinel anorthosite (PSA) at the Moscoviense basin has sparked new interest in lunar spinel. Pieters et al. suggested that these PSA deposits might be an important component of the lunar crust. However, Mg-Al spinel is rare in the Apollo and meteorite sample collections (only up to a few wt%), and occurs mostly in troctolites and troctolitic cataclastites. In this study, we are conducting a series of experiments (petrologic and space weathering) to investigate whether deposits of spinel identified by remote sensing are in high concentration (e.g. 30%) or whether the concentrations of spinel in these deposits are more like lunar samples, which contain only a few wt%. To examine the possibility of an impact-melt origin for PSA, conducted 1-bar crystallization experiments on rock compositions similar to pink spinel troctolite 65785. The VNIR spectral reflectance analyses of the low-temperature experiments yield absorption features similar to those of the PSA lithology detected at Moscoviense Basin. The experimental run products at these temperatures contain approximately 5 wt% spinel, which suggests that the spinel-rich deposits detected by M(sup 3) might not be as spinel-rich as previously thought. However, the effect of space weathering on spinel is unknown and could significantly alter its spectral properties including potential weakening of its diagnostic 2-micrometers absorption feature. Thus, weathered lunar rocks could contain more spinel than a comparison with the unweathered experimental charges would suggest. In this study, we have initiated space weathering experiments on 1) pure pink spinel, 2) spinel-anorthite mixtures, and 3) the low temperature experimental run products from Gross et al. in order to evaluate the influence of space weathering on the absorption strength of spinel. The results can be used to place constraints on the spinel abundance in the PSA lithology and can be used as ground truth for further VNIR spectral analyzes of lunar lithologies.

Preeruption conditions and timing of dacite-andesite magma mixing in the 2.2 ka eruption at Mount Rainier

NASA Astrophysics Data System (ADS)

Venezky, D. Y.; Rutherford, M. J.

1997-01-01

Analytical, field, and experimental evidence demonstrate that the Mount Rainier tephra layer C (2.2 ka) preserves a magma mixing event between an andesitic magma (whole rock SiO2 content of 57-60 wt %) and a dacitic magma (whole rock SiO2 content of 65±1 wt %). The end-member andesite (a mix of an injected and chamber andesite) and dacite can be characterized on the basis of the homogeneity of the matrix glass and phenocryst rim compositions. Many pumices, however, contain mixtures of the end-members. The end-member dacite contains a microlite-free matrix glass with 74-77 wt % SiO2, orthopyroxene rims of Mg57-64, clinopyroxene rims of Mg66-74, and plagioclase rim anorthite contents of An45-65. The temperature and oxygen fugacity, from Fe-Ti oxide compositions, are 930±10°C and 0.5-0.75 log units above NNO. The mixed andesite contains Mg73-84 orthopyroxene rims, Mg73-78 clinopyroxene rims, An78-84 plagioclase rims, and Mg67-74 amphibole rims. The temperature from Fe-Ti oxides, hornblendeplagioclase, and two-pyroxene geothermometry is 1060±15°C, and the oxygen fugacity is approximately one log unit above NNO for the injected andesite. The chamber andesite is estimated to be a magma with a ˜64-65 wt % SiO2 melt at 980°C and a NNO oxygen fugacity. We conclude that the andesitic and dacitic magmas are from separate magma storage regions (at >7 km and ˜2.4 km) due to differences in the bimodal whole rock, matrix glass, and phenocryst compositions and the presence or absence of stable hornblende. The time involved from the mixing event through the eruption is limited to a period of 4-5 days based on Fe-Ti oxide reequilibration, phenocryst growth rates, and hornblende breakdown. The eruption sequence is interpreted as having been initiated by an injection of the 1060±15°C andesitic magma into the ˜980°C (>7 km) andesite storage region. The mixed andesitic magma then intersected a shallow, ˜2.4 km, dacitic storage system on its way toward the surface. The eruption became more dacitic over time, and the final products some show evidence of partial reequilibration between the andesite and dacite.

Viscosity and Structure of a Late Lunar Magma Ocean Liquid: Implications for the Purity of Ferroan Anorthosites and the Dynamics of a Crystallizing Magma Ocean

NASA Astrophysics Data System (ADS)

Dygert, N. J.; Lin, J. F.; Marshall, E. W., IV; Kono, Y.; Gardner, J. E.

2016-12-01

The current paradigm argues the Moon formed after a giant impact that produced a deep lunar magma ocean (LMO). After a period of turbulent convection, the LMO experienced fractional crystallization, causing the initially peridotitic liquid to evolve to a plagioclase-saturated ferrobasalt. The lunar crust, much of which comprises 93-98% pure anorthosite [1,2], formed by flotation of positively buoyant plagioclase on the residual liquid. A flotation crust would contain some trapped melt; compaction of the melt out of the crust before solidification may be necessary to generate a very pure anorthitic crust. The efficiency of this process depends on the previously unmeasured viscosity of the residual liquid [3]. To characterize the viscosity and thermal equation of state of a late LMO liquid, we conducted experiments at the Advanced Photon Source, Beamline 16-BM-B, Argonne National Laboratory on a nominally anhydrous Ti-rich ferrobasalt [4]. X-ray radiography and diffuse scattering experiments were conducted in a Paris-Edinburgh apparatus in graphite-lined BN capsules, allowing in-situ observation of viscosity and derivation of thermal EoS at P-T conditions relevant to the Moon (1300-1600°C, 0.1-4.4GPa). We calculated viscosities of 0.23-1.45 Pa·s for the melt; based on 11 observations, we find that viscosity is pressure insensitive under the conditions explored. Viscosity can be modeled by an Arrhenius relation with an activation enthalpy of 66 kJ/mol. Composition-dependent predictive models [5] overestimate our observations by roughly a factor of 2. Preliminary analysis suggests no pressure-dependent structural transition over the conditions explored. Late LMO liquids brought to the lunar core-mantle boundary by cumulate mantle overturn may be positively buoyant, implying the seismically attenuating layer around the lunar core contains a denser, higher-Ti melt. Our results suggest that efficient phase segregation in the lunar magma ocean and compaction in the anorthositic flotation crust can produce a high-purity crust under physically reasonable conditions. [1] Warren (1990), AmMin 75, 46-58. [2] Ohtake et al. (2009), Nature 461, 236-240. [3] Piskorz, & Stevenson (2014), Icarus 239, 238-243. [4] Longhi (2003), JGR 108, doi:10.1029/2002JE001941. [5] Giordano et al. (2008), EPSL 271, 123-134.

CO2 release from variable carbonate compositions via thermal breakdown and magmatic assimilation at mid-crustal depths

NASA Astrophysics Data System (ADS)

Carter, L. B.; Dasgupta, R.

2017-12-01

Assimilation of crustal limestone in intruding magma has been found to release potentially significant [1-2] but varying amounts of CO2 to the exogenic system depending on pressure, temperature and magma composition [3-4]. However, most natural carbonates range from impure calcite to dolomite or ankerite and their behavior during hydrothermal processes and magma intrusion are less known [2,5-6]. We experimentally investigated both the thermal stability and reactions with hydrous basaltic and dacitic magmas at 800-1200 °C at 0.5 GPa for 3 Fe-bearing dolomite-calcite solid solutions. Dolomite breaks down into Fe-Mg oxides and CO2 at ≤800 °C. With increasing carbonate Ca/Mg, higher temperature is needed to reach similar decarbonation levels and the transition from Fe-dolomite + Mg-calcite as stable carbonate phases to only the latter. In the presence of magmas, carbonate is Mg-calcite or calcite, in addition to minerals seen in previous pure dolomite studies and natural systems [2-4,7-9], including ferropericlase, diopside, olivine with dolomite, anorthite with calcic carbonate, and wollastonite with rhyolitic melts. Thermal breakdown and assimilation increase with Mg/Ca ratios in the starting carbonate (<50% breakdown & <60% assimilation, respectively). At identical conditions, dolomite assimilation by dacite can release 4 times as much CO2 as limestone, surpassing basalt-dolomite. Though greater than other dacite-carbonate reactions, basalt releases a similar amount regardless of carbonate composition. With Mg/Ca≥0.48, release of CO2 from destabilization even at low temperature (≥900 °C) exceeds that from assimilation (≥1000 °C). Thus magma-carbonate interaction may have contributed several times the current arc output [10] to Earth's past atmosphere, which necessitates cataloging carbonate compositions globally for consideration in climate modeling. [1] Aiuppa et al. 2017 ESciRev (168)24-47; [2] Lee and Lackey 2015 Elem (11)125-130; [3] Carter and Dasgupta 2015 EPSL (427) 202-214; [4] Carter and Dasgupta 2016 G3 (17)3893-3916; [5] Warren 2000 ESciRev (52)1:81; [6] Franzolin et al. 2011 CMP (161)213-227; [7] Jolis et al. 2013 CMP (166)1335-1353; [8] Iacono-Marziano et al. 2008 CMP (155)719-738; [9] Mollo et al. 2010 Lithos (114)503-514; [10] Burton et al 2013 RevMinGeochem (75) 323-254.

Magma storage and mixing conditions for the 1953-1974 eruption of Southwest Trident volcano, Katmai National Park, Alaska

USGS Publications Warehouse

Coombs, Michelle L.; Eichelberger, John C.; Rutherford, Malcom J.

2000-01-01

Between 1953 and 1974, approximately 0.5 km3 of andesite and dacite erupted from a new vent on the southwest flank of Trident volcano in Katmai National Park, Alaska, forming an edifice now known as Southwest (or New) Trident. Field, analytical, and experimental evidence shows that the eruption commenced soon after mixing of dacite and andesite magmas at shallow crustal levels. Four lava flows (58.3–65.5 wt% SiO2) are the dominant products of the eruption; these contain discrete andesitic enclaves (55.8–58.9 wt% SiO2) as well as micro- and macro-scale compositional banding. Tephra from the eruption spans the same compositional range as lava flows; however, andesite scoria (56–58.1 wt% SiO2) is more abundant relative to dacite tephra, and is the explosively erupted counterpart to andesite enclaves. Fe–Ti oxide pairs from andesite scoria show a limited temperature range, clustered around 1000 °C. Temperatures from grains found in dacite lavas possess a wider range; however, cores from large (>100 μm) magnetite and coexisting ilmenite give temperatures of ∼890 °C, taken to represent a pre-mixing temperature for the dacite. Water contents from dacite phenocryst melt inclusions and phase equilibria experiments on the andesite imply that the two magmas last resided at a water pressure of 90 MPa, and contained ∼3.5 wt% H2O, equivalent to 3 km depth if saturated. Unzoned pyroxene and sodic plagioclase in the dacite suggest that it likely underwent significant crystallization at this depth; highly resorbed anorthitic plagioclase from the andesite suggests that it originated at greater depths and underwent relatively rapid ascent until it reached 3 km, mixed with dacite, and erupted. Diffusion profiles in phenocrysts suggest that mixing preceded eruption of earliest lava by approximately one month. The lack of a compositional gap in the erupted rock suite indicates that thorough mixing of the andesite and dacite occurred quickly, via disaggregation of enclaves, phenocryst transfer from one magma to another, and direct mixing of compositionally distinct melt phases.

Influence of liquid structure on diffusive isotope separation in molten silicates and aqueous solutions

NASA Astrophysics Data System (ADS)

Watkins, James M.; DePaolo, Donald J.; Ryerson, Frederick J.; Peterson, Brook T.

2011-06-01

Molecular diffusion in natural volcanic liquids discriminates between isotopes of major ions (e.g., Fe, Mg, Ca, and Li). Although isotope separation by diffusion is expected on theoretical grounds, the dependence on mass is highly variable for different elements and in different media. Silicate liquid diffusion experiments using simple liquid compositions were carried out to further probe the compositional dependence of diffusive isotopic discrimination and its relationship to liquid structure. Two diffusion couples consisting of the mineral constituents anorthite (CaAl 2Si 2O 8; denoted AN), albite (NaAlSi 3O 8; denoted AB), and diopside (CaMgSi 2O 6; denoted DI) were held at 1450 °C for 2 h and then quenched to ambient pressure and temperature. Major-element as well as Ca and Mg isotope profiles were measured on the recovered quenched glasses. In both experiments, Ca diffuses rapidly with respect to Si. In the AB-AN experiment, D Ca/ D Si ≈ 20 and the efficiency of isotope separation for Ca is much greater than in natural liquid experiments where D Ca/ D Si ≈ 1. In the AB-DI experiment, D Ca/ D Si ≈ 6 and the efficiency of isotope separation is between that of the natural liquid experiments and the AB-AN experiment. In the AB-DI experiment, D Mg/ D Si ≈ 1 and the efficiency of isotope separation for Mg is smaller than it is for Ca yet similar to that observed for Mg in natural liquids. The results from the experiments reported here, in combination with results from natural volcanic liquids, show clearly that the efficiency of diffusive separation of Ca isotopes is systematically related to the solvent-normalized diffusivity - the ratio of the diffusivity of the cation ( D Ca) to the diffusivity of silicon ( D Si). The results on Ca isotopes are consistent with available data on Fe, Li, and Mg isotopes in silicate liquids, when considered in terms of the parameter D cation/ D Si. Cations diffusing in aqueous solutions display a similar relationship between isotopic separation efficiency and Dcation/D, although the efficiencies are smaller than in silicate liquids. Our empirical relationship provides a tool for predicting the magnitude of diffusive isotopic effects in many geologic environments and a basis for a more comprehensive theory of isotope separation in liquid solutions. We present a conceptual model for the relationship between diffusivity and liquid structure that is consistent with available data.

The stability of hibonite, melilite and other aluminous phases in silicate melts: Implications for the origin of hibonite-bearing inclusions from carbonaceous chondrites

NASA Technical Reports Server (NTRS)

Beckett, J. R.; Stolper, E.

1994-01-01

Phase fields in which hibonite and silicate melt coexist with spinel CaAl4O7, gehlenitic melilite, anorthite or corundum at 1 bar in the system CaO-MgO-Al2O3-SiO2-TiO2 were determined. The hibonites contain up to 1.7 wt% SiO2. For TiO2, the experimentally determined partition coefficients between hibonite and coexisting melt D(sub i)(sup Hib/L), vary from 0.8 to 2.1 and generally decrease with increasing TiO2 in the liquid. Based on Ti partitioning between hibonite and melt, bulk inclusion compositions and hibonite-saturated liquidus phase diagrams, the hibonite in hibonite-poor fluffy Type A inclusions from Allende and at least some hibonite from hibonite-rich inclusions is relict, although much of the hibonite from hibonite-glass spherules probably crystallized metasably from a melt. Bulk compositions for all of these CAIs are consistent with an origin as melite + hibonite + spinel + perovskite phase assembalges that were partially altered and in some cases partially or completely melted. The duration of the melting event was sufficient to remove any Na introduced by the alteration process but frequently insufficient to dissolve all of the original hibonite. Simple thermochemical models developed for meteoritic melilite and hibonite solid solutions were used to obtain equilibration temperatures of hibonite-bearing phase assemblages with vapor. Referenced to 10(exp -3) atm, hibonite + corundum + vapor equilibrated at approximately 1260 C and hibonite + spinel +/- melilite + vapor at 1215 +/- 10 C. If these temperatures reflect condensation in a cooling gas of solar composition, then hibonite +/- corundum condensed first, followed by spinel and then melilite. The position of perovskite within this sequence is uncertain, but it probably began to condense before spinel. This sequence of phase appearances and relative temperatures is generally consistent with observed textures but differs from expectations based on classical condensation calculations in that equilibration temperatures are generally lower than predicted and melilite initially condenses with or even after spinel. Simple thermochemical modes for the substitution of trace elements into the Ca site of meteoritic hibonites suggest that virtually all Eu is divalent in early condensate hibonites but that Eu(2+)/Eu(#+) decreases by a factor of 20 or more during the course of condensation primarily because the ratio is proportional to the partial pressure of Al, which decreases dramatically as aluminous phase condense. The relative sizes of Eu and Yb anomalies in meteoritic hibonites and inclusions may be partly due to this effect.

Magmatic processes in the layered Series of the Skaergaard intrusion inferred from core and rim compositions of plagioclase

NASA Astrophysics Data System (ADS)

Brown, W. L.; Toplis, M. J.

2003-04-01

Due to slow NaSi-CaAl exchange in plagioclase, the proportion of the anorthite component (An) may be considered essentially a primary feature in magmatic bodies such as small layered intrusions. Thus, An provides a potential window into the evolution of such magmatic systems on various length scales. In order to assess the utility of this approach, 13 thin sections covering the principal zones and sub-zones of the Layered Series of the Skaergaard intrusion, East Greenland, were studied. In each thin section 90 to 150 analyses of plagioclase were made using an electron microprobe. Analyses were made in grain centres and at grain edges, particular attention being paid to plagioclase-plagioclase contacts. The cores of large and moderately sized crystals show narrow compositional ranges, 90% of analyses lying within 3 mol% of the mean. In accordance with previous studies, we find that mean core compositions vary continuously with stratigraphic height, from ˜An70 at the lowest levels, to ˜An30 at the top of Upper Zone (UZ). Rim compositions of touching plagioclase also show strong maxima in their mode, but the variation of this composition with stratigraphic height is distinctly different from that of crystal cores. In the Lower Zone (LZ) and lower Middle Zone (MZ), the most abundant rim compositions are systematically An50± 1, core and rim compositions converging in the lower MZ. In the upper MZ to UZ, rim compositions are very similar to corresponding cores, but locally may be more evolved, particularly when plagioclase is intergrown with quartz. The systematic decrease of An as a function of stratigraphic height is strong evidence in favour of fractional crystallization of the main liquid. However, the fact that plagioclase zoning does not extend to nearly pure albite in the vast majority of rocks implies mobility of intercumulus liquid. If compaction (expulsion) were the mechanism responsible for this, it would be difficult to explain the remarkably constant cut-off in rim compositions at An50 in the LZ and lower MZ. On the other hand, this cut-off corresponds to the An content at magnetite saturation, which leads us to propose that the observed features are the result of a density inversion in the liquid following oxide saturation. This density inversion causes the intercumulus liquid to become gravitationally unstable relative to the overlying main liquid leading to compositional convection in the upper LZ and MZ, a hypothesis consistent with the adcumulus texture of those rocks.

A preferred method for the determination of bulk compositions of coarse-grained refractory inclusions and some implications of the results

NASA Astrophysics Data System (ADS)

Simon, S. B.; Grossman, L.

2004-10-01

Analyses of coarse-grained refractory inclusions typically do not have the solar CaO/Al 2O 3 ratio, probably reflecting nonrepresentative sampling of them in the laboratory. Many previous studies, especially those done by instrumental neutron activation analysis (INAA), were based on very small amounts of material removed from those restricted portions of inclusions that happened to be exposed on surfaces of bulk meteorite samples. Here, we address the sampling problem by studying thin sections of large inclusions, and by analyzing much larger aliquots of powders of these inclusions by INAA than has typically been done in the past. These results do show convergence toward the solar CaO/Al 2O 3 ratio of 0.792. The bulk compositions of 15 coarse-grained inclusions determined by INAA of samples >2 mg have an average CaO/Al 2O 3 ratio of 0.80 ± 0.18. When bulk compositions are obtained by modal recombination based on analysis of thin sections with cross-sections of entire, large, unbroken inclusions, the average of 11 samples (0.79 ± 0.15) also matches the solar value. Among those analyzed by INAA and by modal recombination, there were no inclusions for which both techniques agreed on a CaO/Al 2O 3 ratio deviating by >˜15% from the solar value. These results suggest that: individual inclusions may have the solar CaO/Al 2O 3 ratio; departures from this value are due to sample heterogeneity and nonrepresentative sampling in the laboratory; and it is therefore valid to correct compositions to this value. We present a method for doing so by mathematical addition or subtraction of melilite, spinel, or pyroxene. This yields a set of multiple, usually slightly different, corrected compositions for each inclusion. The best estimate of the bulk composition of an inclusion is the average of these corrected compositions, which simultaneously accounts for errors in sampling of all major phases. Results show that Type B2 inclusions tend to be more SiO 2-rich and have higher normative Anorthite/Gehlenite component ratios than Type B1s. The inclusion bulk compositions lie in a field that can result from evaporation at 1700-2000K of CMAS liquids with solar CaO/Al 2O 3, but with a wide range of initial MgO (30-60 wt%) and SiO 2 (15-50 wt%) contents.

Unravelling the complexities of a high-grade Paleoarchean terrane: Saglek Block, Labrador, Canada

NASA Astrophysics Data System (ADS)

Salacinska, Anna; Kusiak, Monika; Dunkley, Daniel; Whitehouse, Martin; Wilde, Simon

2017-04-01

The Nain Province of Labrador is on the western edge of the Archean North Atlantic Craton, and includes the Saglek Block, where >3.6 Ga Uivak orthogneisses were intercalated with a variety of supracrustals during Neoarchean granulite-grade metamorphism. In order to unravel the complex magmatic and metamorphic history of this terrane, samples of grey orthogneiss mapped as Uivak Gneiss were taken from Tigigakyuk Inlet, where previous studies have suggested the preservation of >3.9 Ga zircons [1]. Samples vary from fine, equigranular felsic-intermediate gneiss, through slightly porphyroblastic metagranitoids to metagabbros. Felsic orthogneises are mostly composed of oligoclase, quartz, biotite and K-feldspar, whereas more mafic samples contain hornblende and augite, with the latter being largely altered to pargasite during post-granulite hydration and lower-grade metamorphism. Geochemically, all samples follow a calc-alkaline differentiation trend, and are metaluminous to slightly peraluminous. Based on the normative albite-anorthite-orthoclase diagram, samples plot within the tonalite and trondhjemite fields; however, according to the normative QAPF classification, they are granodioritic to quartz-monzodioritic. Following the criteria of Moyen and Martin (2012), only one granodioritic sample represents typical Archean TTG gneiss, while the other samples are slightly more K-rich. Although bulk compositions may have been affected by K-enrichment during granulite-facies metamorphism, these samples mostly belong to the "TTG-like" suite. Concordant SIMS U-Pb age data obtained from the zircon cores with characteristic igneous growth textures from TTG-like and quartz monzodioritic gneiss fall within the interval 3.70-3.75 Ga, consistent with previous age estimates for the protoliths of Uivak I gneisses [3,4]. Some quartz monzodioritic gneisses are significantly younger (3.55 Ga), showing that the gneisses at Tigigakyuk Inlet are not of a simple magmatic suite, but are instead composite. Inheritance of 3.7 Ga zircons in 3.55 Ga quartz monzodioritic gneiss is evidence that the younger magmatism is not from an exotic terrane, but is produced at least partially through the recycling of Uivak I gneissic crust during later magmatism, prior to orogenic reworking at 2.7 Ga. Although pre-3.8 Ga zircons was not found in this study, the geochemistry of Uivak I gneisses may suggest a degree of crustal reworking at 3.7 Ga. References: [1] Regelous and Collerson (1996) Geochimica Cosmochimica Acta 60:3513-3520. [2] Moyen and Martin (2012) Lithos 148: 312-336. [3] Schiøtte et al. (1989) Canadian Journal of Earth Science 26: 2636-2644. [4] Bridgwater and Schiotte (1991) Bull. Geol. Soc. Den., 39: 153-166.

New Standard State Entropy for Sphene (Titanite)

NASA Astrophysics Data System (ADS)

Manon, M. R.; Dachs, E.; Essene, E. J.

2004-12-01

Several recent papers have questioned the accepted standard state (STP) entropy of sphene (CaTiSiO5), which had been considered to be in the range 129-132 J/mol.K (Berman, 1988: 129.3 Robie and Hemingway, 1995: 129.2 J/mol.K; Holland and Powell, 1995: 131.2 J/mol.K.). However, Xirouchakis and Lindsley (1998) recommended a much lower value of 106 J/mol.K for the STP entropy of sphene. Tangeman and Xirouchakis (2001) inferred a value less than 124 or 120 J/mol.K, based on based on enthalpy constraints combined with the tightly reversed reaction sphene+kyanite=rutile+anorthite by Bohlen and Manning (1991). Their recommendations are in conflict with the accepted values for STP entropy for sphene, including values calculated by direct measurement of Cp from 50 to 300 K by King (1954). In order to resolve this discrepancy, we have collected new data on the Cp of sphene between 5 and 300 K. Our measurements were made in the PPMS at Salzburg on a 21.4 g sample of sphene generously furnished by Tangeman and Xirouchakis (2001), the same sample as used in their experiments. The Cp data are slightly lower than those of King (1954) but merge smoothly with data of Tangeman and Xirouchakis (2001) from 330 to 483 K (or whatever) where a transition is recorded in the Cp data as a lambda anomaly. Tangeman and Xirouchakis also obtained data above the transition up to 950K. Integration of the new Cp data yields a STP entropy of 127.3 J/mol.K, lower than the generally accepted value by ca. 2 J/mol.K. A change in the STP entropy of sphene will have an effect on many Ti-bearing reactions which occur within the earth, although the magnitude of this change is not nearly as large as that suggested by Xirouchakis and Lindsley (1998). Above 700 K, the entropy calculated using the new STP entropy with the heat capacity equation of Tangeman and Xirouchakis (2001) is within 1 J/mol.K of the value tabulated in Robie and Hemingway (1995) and of that calculated from Berman (1988). The effect on most phase equilibrium calculations will not be large except for reactions with small Δ S. The use of 127.2 J/mol.K as the standard entropy of sphene is recommended especially in calculations of geobarometers involving that phase.

Rheology and thermal budget of lunar basalts: an experimental study and its implications for rille formation of non-Newtonian lavas on the Moon

NASA Astrophysics Data System (ADS)

Sehlke, A.; Whittington, A. G.

2015-12-01

Sinuous lava channels are a characteristic feature observed on the Moon. Their formation is assumed to be due to a combination of mechanical and thermal erosion of the lava into the substrate during emplacement as surface channels, or due to collapsed subsurface lava tubes after the lava has evacuated. The viscosity (η) of the lava plays an important role, because it controls the volume flux of the emplaced lava that governs the mechanical and thermal erosion potential of the lava flow. Thermal properties, such as heat capacity (Cp) and latent heat of crystallization (ΔHcryst) are important parameters in order for the substrate to melt and causing thermal buffering during crystallization of the flowing lava. We experimentally studied the rheological evolution of analog lavas representing the KREEP terrain and high-Ti mare basalts during cooling and crystallization. We find that the two lavas behave very differently. High-Ti mare lava begins to crystallize around 1300 ºC with a viscosity of 8.6±0.6 Pa s and crystal content around 2 vol%. On cooling to 1169 ºC, the effective viscosity of the crystal-melt suspension is increased to only 538±33 Pa s (at a strain rate of 1 s-1) due to crystallization of 14±1 vol% blocky magnetite and acicular ulvöspinel-rich magnetite. The flow behavior of these suspensions depends on the strain rate, where flow curves below strain rates of 10 s-1show shear-thinning character, but resemble Bingham behavior at greater strain rates. In contrast, the KREEP lava crystallizes rapidly over a narrow temperature interval of ~ 30 degrees. The first crystals detected were ulvospinel-rich magnetites at 1204 ºC with ~2 vol% and a viscosity of 90±2 Pa s. On cooling to 1178 ºC, anorthite and enstatite appears, so that the crystal-melt suspension has become strongly pseudoplastic at a crystal content of 22±2 vol% with a flow index (n) of 0.63 and an effective viscosity of 1600±222 Pa s at a strain rate of 1 s-1. We are currently measuring the heat capacity of crystal-bearing glasses (representing erodible solid substrate) and the heat released during lava crystallization at different cooling rates measured by differential scanning calorimetry (DSC). The rheological and thermal properties will then be integrated into thermo-mechanical models of rille formation in non-Newtonian lavas on the lunar surface.

Thermal Profile of the Lunar Interior Constrained by Revised Estimates of Concentrations of Heat Producing Elements

NASA Astrophysics Data System (ADS)

Fuqua-Haviland, H.; Panovska, S.; Mallik, A.; Bremner, P. M.; McDonough, W. F.

2017-12-01

Constraining the heat producing element (HPE) concentrations of the Moon is important for understanding the thermal state of the interior. The lunar HPE budget is debated to be suprachondritic [1] to chondritic [2]. The Moon is differentiated, thus, each reservoir has a distinct HPE signature complicating this effort. The thermal profile of the lunar interior has been constructed using HPE concentrations of an ordinary chondrite (U = 0.0068 ppm; Th = 0.025 ppm; K = 17 ppm) which yields a conservative low estimate [2, 3, 4]. A later study estimated the bulk lunar mantle HPE concentrations (U = 0.039 ppm; Th = 0.15 ppm; K = 212 ppm) based on measurements of Apollo pyroclastic glasses [5] assuming that these glasses represent the least fractionated, near-primary lunar mantle melts, hence, are the best proxies for capturing mantle composition. In this study, we independently validate the revised estimate by using HPE concentrations [5] to construct a conductive lunar thermal profile, or selenotherm. We compare our conductive profile to the range of valid temperatures. We demonstrate the HPE concentrations reported by [5], when used in a simple 1D spherical thermal conduction equation, yield an impossibly hot mantle with temperatures in excess of 4,000 K (Fig 1). This confirms their revised estimate is not representative of the bulk lunar mantle, and perhaps only representative of a locally enriched mantle domain. We believe that their Low-Ti avg. source estimate (Th = 0.055 ppm, Th/U=4; K/U=1700), with the least KREEP assimilation is the closest representation of the bulk lunar mantle, producing 3E-12 W/kg of heat. This estimate is close to that of the Earth (5E-12 W/kg), indicating that the bulk Earth and lunar mantles are similar in their HPE constituents. We have used the lunar mantle heat production, in conjunction with HPE estimates of the Fe-Ti-rich cumulates (high Ti-source estimate from [5]) and measurements of crustal ferroan anorthite [6], to capture the present-day lunar interior thermal state. We also present plausible internal structures that best match the mass, moment of inertia and bulk silicate Moon composition along this conductive selenotherm. [1] Wanke et al (1973) LPSC; [2] Warren et al (1979) Rev Geophy; [3] Wieczorek et al (2000) JGR; [4] Grimm (2013) JGRP; [5] Hagerty et al (2006) GCA; [6] Peplowski et al (2016) JGR.

Timing of the final closure of the Paleo-Asian Ocean in the Alxa Terrane: Constraints from geochronology and geochemistry of Late Carboniferous to Permian gabbros and diorites

NASA Astrophysics Data System (ADS)

Liu, Qian; Zhao, Guochun

2017-04-01

The Alxa Terrane is a crucial place situated between the North China Craton to the east and the Tarim Craton to the west. The Late Paleozoic magmatic record in the Alxa Terrane places important constraints on the timing of the final closure of the middle segment of the Paleo-Asian Ocean (PAO). In this study, new LA-ICPMS zircon U-Pb dating results reveal ca. 300-268 Ma gabbros and diorites in the Bayan Nuru area in the eastern part of the Alxa Terrane. The 300 Ma gabbros show plagioclase accumulations with anorthite compositions (An92-95), arc-like geochemical affinities with relative enrichment in large ionic lithophile elements and depletion in high field strength elements (e.g., Ti, Nb and Ta), as well as negative Hf(t) (-6.01 to -1.75) and Nd(t) (-9.5 to -7.1) values and high initial 87Sr/86Sr ratios (0.707157-0.707220). These features indicate a magma source of an enriched lithospheric mantle metasomatized by high fluid activities. In comparison, the 280-268 Ma gabbros and diorites also have arc-like geochemical affinities but show increasingly evolved isotope compositions, implying more sediment inputs. Compiled zircon ɛHf(t) and whole-rock ɛNd(t) values of the magmatic rocks in the Alxa Terrane decrease from the Late Carboniferous to the Early Permian, and increase from the Middle Permian to the Triassic. The considerably large spread in ɛHf(t) and ɛNd(t) values at ca. 280-265 Ma likely reflects a tectonic switch from a subduction setting to a post-collisional setting, corresponding to the timing of the final closure of the PAO in the Alxa Terrane. Thus, the PAO progressively closed from west to east along the northern margin of the Tarim Craton, the Alxa Terrane, and then the northern margin of the North China Craton during Late Carboniferous to Middle Triassic time. This work was financially supported by a NSFC Project (41190075) entitled "Final Closure of the Paleo-Asian ocean and Reconstruction of East Asian Blocks in Pangea", the fifth research project in the NSFC Major Program (41190070) "Reconstruction of East Asian Blocks in Pangea", a Hong Kong RGC GRF (HKU7063/13P and 17301915), NSFC General Projects (41230207 and 41390441) and a HKU Seed Funding Programme for Basic Research (201311159126).

The Effect of Fe-Ti-rich Cumulate Overturn on Evolution of the Lunar Interior

NASA Astrophysics Data System (ADS)

Mallik, A.; Ejaz, T.; Shcheka, S.; Garapic, G.; Petitgirard, S.; Blanchard, I.

2017-12-01

The last 5% of magma ocean crystallized Fe-Ti rich cumulates (FTC) emplaced below the anorthitic crust [1]. Due to gravitational instability, FTC underwent diapiric downwelling [2], associated with overturn of the lunar mantle. Petrological studies on Apollo basalts with variable TiO2 place their sources between 1.5-3 GPa. This indicates the presence of heterogeneous Ti-rich domains in the lunar interior which could either be produced by inefficient overturn and mixing [3], or due to post-overturn upwelling of FTC from the core-mantle boundary (CMB) [4]. Also, a seismically attenuating layer at the CMB ( 4.5 GPa) maybe associated with partial melt of overturned FTC [5]. Thus, it is important to investigate the phase equilibria of FTC with and without assimilation with the surrounding mantle, to understand better the effect of the overturn process on lunar evolution. We performed phase equilibria experiments at 2 and 4.5 GPa, 1230 to 1700 °C using a multi-anvil apparatus on FTC and a 1:1 mixture of FTC and mantle composition. FTC produced Fe-Ti rich (FeO 13-26 wt.%, TiO2 11-18 wt.%), Mg-poor (MgO 6-10 wt.%) basalts with residues of clinopyroxene+quartz+Fe-metal±spinel, while the mixture of FTC and mantle produced Fe-Ti-Mg rich (FeO 10-13 wt.%, TiO2 5-11 wt.% and MgO 20-30 wt.%) basalts with residues of orthopyroxene+olivine+Fe-metal±spinel±garnet. We find that partial melting of overturned cumulates within the lunar mantle can reproduce certain chemical attributes of Apollo high Ti basalts. Also, to test whether the partial melt of overturned cumulates can be stable at the CMB to produce the attenuating layer, we estimated the densities of these melt compositions using the published range of KT and K' of high Fe-Ti picrites. We find that the densities obtained from the published spread in K' and KT values yield inconclusive results about the stability of these partial melts at the CMB. This is being resolved by in-situ experimental determination of the densities of the high Fe-Ti melt compositions, currently underway. If these partial melts are indeed stable at the CMB, they bracket the present-day CMB temperature between 1300-1490 °C (5 to 30% partial melting [5]).[1] Snyder et al. (1992), GCA [2] Hess & Permentier (1995), EPSL [3] Brown & Grove (2015), GCA [4] Zhong et al. (2000), EPSL [5] Weber et al. (2011), Science

Raman spectroscopy, an innovative tool to explore the mineralogy and provenance of dust (1-5 µm): Dome B ice core, East Antarctica

NASA Astrophysics Data System (ADS)

Ileana Paleari, Chiara; Andò, Sergio; Delmonte, Barbara; Maggi, Valter; Garzanti, Eduardo

2017-04-01

The polar ice sheets are invaluable archives preserving information about past climate changes and atmosphere composition. Deep ice cores from Greenland and Antarctica provide records of several climate-dependent proxies allowing climate reconstructions at different time scales, among which greenhouse gases, atmospheric aerosol and aeolian dust. In this project, the mineralogy of dust preserved in the Dome B (77°05'S, 94°55'E, 3650 m a.s.l.) ice core was investigated using Raman spectroscopy. The thermal drilled ice core, made during the 1987-1988 Austral season by the 33rd Soviet Antarctic Expedition, covers the last 30 kyr. The record thus encompasses the last glacial period, the Last Glacial Maximum (LGM), the deglaciation and the beginning of the Holocene. Four Dome B ice core samples from the LGM were selected, and the mineralogical fingerprint of dust particles was investigated. Dust in central Antarctic ice cores is clay to finest silt, the volume-size distribution of particles showing modal values around 2-2.6 µm at the Dome B site. Detrital minerals of such a fine grain-size range are exceedingly difficult to determine one by one, a task that to the best of our knowledge has never been accomplished so far. In order to meet this challenge, we have developed a new protocol for the preparation and analysis of particles between 1 and 5 µm in diameter, in a clean room at the EuroCold Lab and at the Laboratory for Provenance Studies of Milano-Bicocca University. Three slides were prepared for each sample, and 962 particles were studied overall. In total, 41 different minerals were recognized, including species derived from granitoid, metamorphic or siliciclastic rocks (e.g., quartz, feldspars and phyllosilicates), from volcanic source rocks (e.g., sanidine, anorthite, pyroxenes, zeolites) associated with biogenic marine aragonite and iron oxides probably derived from erosion of soil profiles. Our observations indicate southern South America as the most likely dominant dust source for Dome B during the LGM. Abundant carbonates found in samples DB620 and DB631 highlights the role of the exposed Argentine continental shelf as a significant additional dust source during the sea-level low-stand period of Marine Isotopic Stage 2. This study demonstrates that dust minerals as small as 1-5 µm can be identified with single-grain method by Raman Spectroscopy, opening up a new frontier in provenance studies of silt-sized sediments down to the size limit of clay.

Effect of deformation induced nucleation and phase mixing, a two phase model for the ductile deformation of rocks.

NASA Astrophysics Data System (ADS)

Bevillard, Benoit; Richard, Guillaume; Raimbourg, Hugues

2017-04-01

Rocks are complex materials and particularly their rheological behavior under geological stresses remains a long-standing question in geodynamics. To test large scale lithosphere dynamics numerical modeling is the main tool but encounter substantial difficulties to account for this complexity. One major unknown is the origin and development of the localization of deformation. This localization is observed within a large range of scales and is commonly characterized by sharp grain size reduction. These considerations argues for a control of the microscopical scale over the largest ones through one predominant variable: the mean grain-size. However, the presence of second phase and broad grain-size distribution may also have a important impact on this phenomenon. To address this question, we built a model for ductile rocks deformation based on the two-phase damage theory of Bercovici & Ricard 2012. We aim to investigate the role of grain-size reduction but also phase mixing on strain localization. Instead of considering a Zener-pining effect on damage evolution, we propose to take into account the effect of the grain-boundary sliding (GBS)-induced nucleation mechanism which is better supported by experimental or natural observations (Precigout et al 2016). This continuum theory allows to represent a two mineral phases aggregate with explicit log-normal grain-size distribution as a reasonable approximation for polymineralic rocks. Quantifying microscopical variables using a statistical approach may allow for calibration at small (experimental) scale. The general set of evolutions equations remains up-scalable provided some conditions on the homogenization scale. Using the interface density as a measure of mixture quality, we assume unlike Bercovici & Ricard 2012 that it may depend for some part on grain-size . The grain-size independent part of it is being represented by a "contact fraction" variable, whose evolution may be constrained by the dominant deformation mechanism. To derive the related evolution equations and account for the interdependence of thermodynamic state variables, we use Onsager's thermodynamic extremum principle. Eventually, we solve for our set of equations using an Anorthite/Pyroxene gabbroic composition. The results are used to discuss the interaction between grain-size reduction and phase mixing on strain localization on several simple cases. Bercovici D, Ricard Y (2012) Mechanisms for the generation of plate tectonics by two phase grain damage and pinning. Physics of the Earth and Planetary Interiors 202-203:27-55 Precigout J, Stunitz H (2016) Evidence of phase nucleation during olivine diffusion creep: A new perspective for mantle strain localisation. Earth and Planetary Science Letters 405:94-105

The Crystal Stratigraphy of Ontong Java Plateau Plagioclase Pegacrysts: New Insights into the Evolution of LIP Magmas.

NASA Astrophysics Data System (ADS)

Neal, C. R.; Kinman, W. S.

2003-12-01

The Ontong Java Plateau (OJP) is the world's largest LIP made up of 2 isotopically distinct lava types that comprise the Singgalo and Kwaimbaita formations (Tejada et al., 2002, J.Pet 43:449). Some Kwaimbaita basaltic flows contain plagioclase-rich cumulate xenoliths. As plagioclase is stable over a range of magmatic conditions, microanalysis of this phase allows the evolution of the parent magma(s) to be constrained (cf. Davidson & Tepley, 1997, Science 275:826). This crystal stratigraphy approach has been applied to cm-size plagioclase megacrysts from three basaltic units (5B, 6, and 7) recovered at ODP Leg 192 Site 1183. Core-to-rim trace element variations were quantified by LA-ICP-MS, major elements by EPMA, and compositional backscatter SEM imaging was used to investigate the subtle compositional zoning and textural features within the plagioclases. All 5 OJP megacrysts sampled show little core-to-rim anorthite variation (82 mol % An +/- 5%); An-rich plagioclase crystals are resistant to re-equilibration and are more likely to retain magmatic trace element signatures (Blundy & Wood, 1991, GCA 55:193). The Unit 7 (oldest) plagioclase contains a relatively Sr, Ga, REE, and Ti poor core bounded by a resorption surface and a relatively Sr, Ga, REE, and Ti rich zone suggesting this crystal was exposed to 2 compositionally distinct magmas. The Unit 6 plagioclase contains a relatively Sr, Ga, REE, and Ti poor core with increasing abundances toward the rim, consistent with evolution through fractional crystallization. This megacryst also contains a distinct resorption surface bounded by a core-like Sr, REE, and Ti poor zone. The three Unit 5B plagioclases display core-to-rim Sr and Ba increases with little core-to-rim REE and Ga variations. The uppermost Unit 5B crystal (youngest) exhibits a core-to-rim decrease in Ti, while the lower 2 crystals display the opposite relationship. We suggest the textural and trace element variations seen in OJP plagioclase megacrysts are again evidence of magma mixing. Reconstructed liquids suggest at least two distinct mixing end members: an enriched end member, similar to Singgalo-type lavas, and a depleted end member, similar to Kwaimbaita type lavas. As the Singgalo- and Kwaimbaita-type basalts are isotopically distinct (I(Sr) = 0.7041 and 0.7038, resp.), Sr isotope determinations of the different plagioclase zones through microdrilling is planned for the near future to test this hypothesis. If correct, it suggests that both the Kwaimbaita and Singgalo sources were active at the same time, which is in contrast to the stratigraphy determined by whole-rock compositions.

Controls and implications of anisotropy across a strain gradient within granodiorite, Serifos, Western Cyclades

NASA Astrophysics Data System (ADS)

Gaudreau, Élyse; Lagroix, France; Cossette, Élise; Schneider, David; Grasemann, Bernhard

2016-04-01

In order to evaluate the assumption that the crust behaves as an isotropic material in complex structural settings, we integrate crystallographic preferred orientation (CPO) and anisotropy of magnetic susceptibility (AMS) data across a strain gradient within a Miocene granodioritic intrusion on Serifos island, Western Cyclades. One of the consequences of anisotropic crust is the variation in seismic wave velocity with the direction of propagation, which is largely controlled by the CPO of anisotropic minerals such as micas. The magnetic fabric of variably deformed granodiorite is used to characterize weakly defined tectonic fabric and thus complements the CPO data. Granodiorite samples exhibit very low strain to mylonitic fabric across the crustal-scale shear zone, recording progressive deformation through the ductile to brittle transition. CPO data was collected using electron backscatter diffraction and seismic properties were calculated using Voigt-Reuss-Hill averaging of the single minerals' elastic stiffness tensor. Quartz CPO is very strong in the weakly deformed samples recording basal and prism {0001} slip. Furthermore, bulging recrystallization and undulose extinction in quartz as well as feldspar grains that exhibit brittle deformation structures are indicative of 300-400 °C temperatures. The mylonite has a very weak CPO for the quartz phase and exhibits prism {0001} slip. The higher strain samples also reveal dynamic recrystallization and grain size reduction of quartz, plagioclase, potassium feldspar and biotite, which are characteristic of 400-500 °C temperatures. Orthoclase and anorthite possess a weak CPO in all samples. The S-wave anisotropy calculated from the CPO data of the weakly deformed granodiorite is the highest of all samples (max: 8%), and the anisotropy of the mylonite is the weakest of all samples (max: <3%). AMS data yields mainly oblate fabrics and the magnetic foliations and lineations correlate with microscopic and macroscopic structural observations. Most samples exhibit a bulk magnetic susceptibility between 30 and 5000 μSI, suggesting that the magnetic signature is due to both paramagnetic and ferrimagnetic minerals. Hysteresis loops and thermomagnetic curves specify pseudo-single domain magnetite as the main ferrimagnetic mineral. Paramagnetic and ferrimagnetic minerals can exhibit distinct subfabrics, and differentiating between the two using the anisotropy of remanence is essential for semi-quantifying local deformation. The magnetic fabric, coupled with the tectonic fabric inferred from CPO data, gives unique insight into the character of anisotropic minerals in a complex structural setting. For instance, the AMS foliations for samples with ill-defined syntectonic emplacement fabric have a similar orientation to that of fast P-wave propagation, a trait consistent with samples that have a macroscopic foliation. The analysis of anisotropic minerals is therefore fundamental for incorporating seismic anisotropy into large-scale geophysical models.

Variations in magma transport recorded by plagioclase ultraphyric basalts: Preliminary results from SWIR, Blanco and Juan de Fuca

NASA Astrophysics Data System (ADS)

Lange, A.; Tepley, F. J.; Nielsen, R. L.; Burleigh, A. W.; Kent, A. J.

2011-12-01

Plagioclase ultraphyric basalts (PUBs) have been sampled at slow to intermediate spreading oceanic centers worldwide. PUBs contain >15% (often anorthitic) plagioclase phenocrysts, with plagioclase making up > 90% of the phenocryst mode. The petrogenesis of PUBs has traditionally been attributed to inclusion of plagioclase from the crystal mush below spreading ridges. However, the conditions under which this occurs and the process of crystal sorting remain an enigma. To build a more complete model for PUB formation, we compiled published major and trace element data from the literature and PetDB for MORBs containing >15% plagioclase phenocrysts. While there is a clear connection between spreading rate and the occurrence of PUBs (more common at slow and intermediate rate ridges), we find that PUBs have no preferred erupted glass compositions. Therefore, we conclude that the generation of PUBs is dominantly a physical process rather than related to a specific magma type. One of our primary goals is to use information from the population of plagioclase phenocrysts to understand PUB magma differentiation and transport processes. In situ major and trace element and 87Sr/86Sr isotopic data were collected for plagioclase and its host glass from samples at the Southwest Indian Ridge (SWIR), Blanco Transform, and the Juan de Fuca Ridge in order to understand the relationship between the phenocrysts and their host lava suite. The plagioclase megacrysts record contrasting magma storage and transport conditions at different spreading ridges. Crystals from a single sample are often isotopically distinct from the magma they reside in and may or may not be distinct from other crystals in the same sample. Lavas from the East Blanco depression contain plagioclase phenocrysts that are more radiogenic than their host glass. Additionally, plagioclase-hosted melt inclusions have chemical signals that are more evolved than the ambient glass. This demonstrates that the plagioclase megacrysts at Blanco crystallized from a more enriched magma and are xenocrystic with respect to their current host liquid. Conversely, at SWIR, at least one sample contains plagioclase phenocrysts that are much less radiogenic than their host glass. While another dredged sample from SWIR has plagioclase phenocrysts that are mostly in isotopic equilibrium with their host liquid. In all samples, in situ trace elements in plagioclase exhibit a wide range of distinctive chemical characteristics. This suggests diverse magma transport conditions prior to being aggregated. Our findings indicate that PUBs often do not crystallize from simple genetic suites, but instead reflect the amalgamation of diverse melts and complex storage systems that exist below mid-ocean ridges. The presence of PUBs may be a distinctive characteristic of specific magma transport conditions, however, the boundary conditions for their formation is as yet unclear, and the subject of continued work.

Subsolidus migmatization in high-grade meta-tuffs (Kurkijärvi, southwest Finland)

NASA Astrophysics Data System (ADS)

Blom, K. A.

1988-07-01

The phenomenon of migmatization was studied in Precambrian metavolcanic gneisses of calc-alkaline chemistry, outcropping along a prograde amphibolite/granulite facies transition in the West Uusimaa Complex of SW Finland. This paper discusses one of the studied gneiss levels (a garnet-bearing Qtz/Plag/Ksp/Bio-gneiss) which was observed to transsect the metamorphic isograd pattern at almost right angle. The gneiss was studied for structures, whole-rock chemistry (major, trace and REE), mineral content, microtextures, plagioclase anorthite content and fluid inclusions. Data concerning the latter four subjects are presented. Migmatization proved to: (1) have occurred parallel to compositional banding of the rocks; (2) have produced identical leucosome/melanosome/mesosome mineral parageneses; (3) have initiated feldspar/garnet-poikiloblasthesis (and occasionally biotite porphyroblasthesis) in leucosome, and biotite-/garnet-poikiloblasthesis in melanosome; (4) have caused entrapment of unstrained quartz blebs carrying isolated (primary) two-phase pure H 2O fluid inclusions of unique filling degree range in the above-mentioned feldspar- and garnet-poikiloblasts; (5) have occurred post-D 1/pre-D 2, synchronous to amphibolitefacies metamorphism, in the subsolidus regime; (6) have been affected by D 2 in the way of localized mylonitization of the melanosome, and quartz migration (exudation) from adjacent mesosome into leucosome; and (7) have had some control by the biotite content of the original compositionally banded rock. Initial leucosome formation appears to have been controlled by the pre-leucosome biotite content: the recalculated modal biotite content of the leucosome/melanosome combination conspicuously is in the range of 5-20 vol.% of biotite. Final extent of the leucosome shows on its turn a marked correlation with mesosome modal biotite content. Because leucosomes occur carrying a recalculated modal biotite content equalling adjacent mesosome biotite content, a second factor is held responsible for the onset of migmatization in the buried and sheared rock: deficient water balance. Migmatization, initiated at {P}/{T} conditions fit for feldspar recrystallization and almandine formation, was induced during prograde metamorphism to cancel an established zonation in water pressure or water content parallel to compositional banding. Zones of low PH 2O or wt.% H 2O thereby were converted into leucosomes, while zones of higher PH 2O or wt.% H 2O remained unaffected (and became mesosome). That XH 2O did not vary at the onset of migmatization is recorded in the isolated pure H 2O fluid inclusions contained in the quartz blebs enclosed in the studied leucosome- and melanosome-poikiloblasts. Restore of water balance (either by internally controlled factors or externally introduced ones) halted migmatization and its obliteration of compositional banding.

Geochemical and petrological indicators of volcanic behavior: Merapi volcano, Java, Indonesia

NASA Astrophysics Data System (ADS)

Troll, V. R.; Deegan, F. M.; Jolis, E. M.; Chadwick, J.; Blythe, L. S.; Freda, C.; Hilton, D. R.; Schwarzkopf, L. M.; Gertisser, R.; Zimmer, M.

2011-12-01

Gunung Merapi, one of Indonesia's most active volcanoes, is characterized by long periods of dome growth and intermittent explosive pyroclastic events. Merapi currently degasses continuously through high-T fumaroles (>200°C), and erupts crystal-rich basaltic-andesite that contains a large range of igneous and calc-silicate crustal inclusions. To evaluate mechanisms that trigger explosive eruptions, we sampled lavas, inclusions (xenoliths), and gas from active fumaroles. Additionally, we established a time-integrated experiment reaction series mimicking crustal assimilation at Merapi under magmatic conditions. Merapi lava contains abundant plagioclase crystals which show complex zoning and vary in anorthite (An) content between 40 and 95 mol% across resorption surfaces. A negative correlation between An mol% and other indicators of magmatic fractionation, such as MgO and FeO, has been observed. Moreover, Sr isotope analyses of discrete zones in plagioclase yields 87Sr/86Sr values that notably exceed those of the host lavas. Zones with the highest An content also tend to show the highest radiogenic Sr values, consistent with a Ca-rich, high-87Sr/86Sr crustal contaminant. Abundant metamorphosed limestone xenoliths contain compositionally identical feldspar to the high-An population in the lavas, demonstrating that magma-crust interaction is a significant process at Merapi. Carbon isotope ratios of fumarole CO2 sampled during quiescent degassing periods form a baseline of δ13C2001-2008 = -4.1%. The notable exceptions are the 2006 values, obtained immediately after the eruption and the 6.4 magnitude Yogyakarta earthquake, which show elevated δ13C values up to -2.4%. Notably, the rise in δ13C values coincided with an increase in eruptive intensity and volcano seismicity by a factor of 3 to 5 for several weeks after the earthquake. This is consistent with addition of a late-stage, crustal volatile component added to purely mantle and slab-derived volatile sources. This observation argues for extensive and ongoing magma-crust interaction beneath the volcano, especially during eruptive and/or seismic events. Our high P-T experiments show that interaction between Merapi magma and limestone can rapidly liberate crustal CO2 on a timescale of only seconds to minutes. We therefore expect vigorous CO2 bubble nucleation and growth on a scale of perhaps hours to days in nature. Late volatile input could therefore accelerate or trigger explosive eruptions independently of magmatic recharge and fractionation by sudden over-pressurization of the upper parts of the magma system. Such an event would provide shallow seismic warning signals immediately prior to an erratic, CO2-driven, eruption crisis. Thus we conclude that crust-mantle interaction processes have serious implications for eruptive behavior, volatile emission, and hazard management at Merapi and similar systems elsewhere.

Structure of Multi-component Basaltic Glasses under Static and Dynamic Compression: Implications for Mantle Melting and Impact Processes on Planetary Surfaces

NASA Astrophysics Data System (ADS)

Lee, S.; Mosenfelder, J. L.; Tschauner, O. D.; Asimow, P. D.; Park, S.; Kim, H.

2012-12-01

The structures of basaltic melts under both static and dynamic compression are essential to understand the changes in the corresponding melt properties and to provide atomistic insights into impact-induced events in Earth's crust and planetary surfaces. Despite the importance, structural changes in basaltic glasses due both to dynamic and static compression have not been well understood. The advances in multi-nuclear NMR and multi-edge inelastic x-ray scattering allow us to obtain details of the pressure-induced changes in the degree of melt polymerization and cation coordination number in multi-component melts under static and dynamic compression (e.g. Lee, Proc. Nat. Aca. Sci. 2011, 108, 6847; Sol. St. NMR. 2010, 38, 45; Lee et al. Geophys. Res. Letts. 39 5306; Proc. Nat. Aca. Sci. 2008, 105, 7925). Here, we explore the structures of shock compressed silicate glass with a diopside-anorthite eutectic composition (Di64An36), a common Fe-free model basaltic composition, using oxygen K-edge X-ray Raman scattering and high- resolution Al-27 solid-state NMR spectroscopy and report details of shock-induced changes in the atomic configurations. A topologically driven densification of the Di64An36 glass is indicated by the increase in oxygen K-edge energy for the glass upon shock compression with peak pressure up to 20 GPa. The first experimental evidence of the increase in the fraction of highly coordinated Al in shock compressed glass is found in the Al-27 NMR spectra. This result provides atomistic insights into shock compression in basaltic glasses and allows us to microscopically constrain the magnitude of impact events or relevant processes involving natural basalts on Earth and planetary surfaces. We also report the first high pressure multi-nuclear NMR spectrum for basaltic glass up to 5 GPa. While [4]Al species is dominant at 1atm, the significant fraction of [5,6]Al in the glass is apparent, leading to changes in oxygen connectivity in the multi-component. The prevalence of highly coordinated Al and high energy oxygen cluster in the basaltic melts at 5 GPa implies that thermodynamic properties (e.g. element portioning coefficient between melts and crystal) of primary mantle melts formed at mid-ocean ridge (~150 km in depth) should be largely different from what can be predicted for silicate melts at 1 atm. The structural transitions in model basaltic glass at high pressure provide atomistic origins of anomalous mantle composition based on MORB at 1atm that is different from the prediction from chondritic meteorite (e.g. missing Si content in the primitive mantle).

The Formation of Boundary Clinopyroxenes and Associated Glass Veins in Type B1 CAIs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paque, J M; Beckett, J R; Ishii, H A

2008-05-18

We used focused ion beam thin section preparation and scanning transmission electron microscopy (FIB/STEM) to examine the interfacial region between spinel and host melilite for three spinel grains, two from the mantle and one from the core of an Allende type B1 inclusion, and a second pair of spinel grains from a type B1 inclusion from the Leoville carbonaceous chondrite. The compositions of boundary clinopyroxenes decorating spinel surfaces are generally consistent with those of coarser clinopyroxenes from the same region of the inclusion, suggesting little movement of spinels between mantle and core regions after the formation of boundary clinopyroxenes. Themore » host melilite displays no anomalous compositions near the interface, and anorthite or other late-stage minerals are not observed, suggesting that crystallization of residual liquid was not responsible for the formation of boundary clinopyroxenes. Allende spinels display either direct spinel-melilite contact or an intervening boundary clinopyroxene between the two phases. In the core, boundary clinopyroxene is mantled by a thin (1-2 {micro}m thick) layer of normally zoned (X{sub Ak} increasing away from the melilite-clinopyroxene contact) melilite with X{sub Ak} matching that of the host melilite at the melilite-melilite contact. In the mantle, X{sub Ak} near boundary spinels is constant. Spinels in a Leoville type B1 inclusion are more complex with boundary clinopyroxene, as observed in Allende, but also variable amounts of glass ({approx}1 {micro}m width), secondary calcite, perovskite, and an unknown Mg-, Al-, OH-rich and Ca-, Si-poor crystalline phase that may be a layered double hydrate. Glass compositions are consistent to first order with a precursor consisting mostly of Mg-carpholite or sudoite with some aluminous diopside. One possible scenario of formation for the glass veins is that open system alteration of melilite produced a porous, hydrated aggregate of Mg-carpholite or sudoite + aluminous diopside that was shock melted and quenched to a glass. The unknown crystalline phase may be a shocked remnant of the precursor phase assemblage but is more likely to have formed later by alteration of the glass. Calcite appears to be an opportunistic fracture filling that postdated all major shock events. Boundary clinopyroxenes probably share a common origin with coarser-grained pyroxenes from the same region of the inclusion. In the mantle, these crystals may represent clinopyroxene crystallized in Ti-rich liquids caused by the direct dissolution of perovskite and an associated Sc-Zr-rich phase or as a reaction product between dissolving perovskite and liquid (i.e., indirect dissolution of perovskite). In the core, any perovskite and associated Ti-enriched liquids that may have originally been present disappeared before the growth of boundary clinopyroxene.« less

Petrogenetic and geodynamic origin of the Neoarchean Doré Lake Complex, Abitibi subprovince, Superior Province, Canada

NASA Astrophysics Data System (ADS)

Polat, Ali; Frei, Robert; Longstaffe, Fred J.; Woods, Ryan

2018-04-01

The Neoarchean (ca. 2728 Ma) anorthosite-bearing Doré Lake Complex in the northeastern Abitibi subprovince, Quebec, was emplaced into an association of intra-oceanic tholeiitic basalts and gabbros known as the Obatogamau Formation. The Obatogamau Formation constitutes the lower part of the Roy Group, which is composed of two cycles of tholeiitic-to-calc-alkaline volcanic and volcaniclastic rocks, siliciclastic and chemical sedimentary rocks, and layered mafic-to-ultramafic sills. In this study, we report major and trace element results, and Nd, Sr, Pb and O isotope data for anorthosites, leucogabbros, gabbros and mafic dykes from the Doré Lake Complex and spatially associated basalts and gabbros of the Obatogamau Formation to assess their petrogenetic origin and geodynamic setting. Field and petrographic observations indicate that the Doré Lake Complex and associated volcanic rocks underwent extensive metamorphic alteration under greenschist facies conditions, resulting in widespread epidotization (20-40%) and chloritization (10-40%) of many rock types. Plagioclase recrystallized mainly to anorthite and albite endmembers, erasing intermediate compositions. Metamorphic alteration also led to the mobilization of many elements (e.g., LILE and transition metals) and to significant disturbance of the Rb-Sr and U-Pb isotope systems, resulting in 1935 ± 150 and 3326 ± 270 Ma errorchron ages, respectively. The Sm-Nd isotope system was less disturbed, yielding an errorchron age of 2624 ± 160 Ma. On many binary major and trace element diagrams, the least altered anorthosites and leucogabbros, and the gabbros and mafic dykes of the Doré Lake Complex plot in separate fields, signifying the presence of two distinct magma types in the complex. The gabbros and mafic dykes in the Doré Lake Complex share the geochemical characteristics of tholeiitic basalts and gabbros in the Obatogamau Formation, suggesting a possible genetic link between the two rock associations. Initial ɛNd (+2.6 to +5.0) and δ18O (+6.1 to +7.9‰) values for the Doré Lake Complex and gabbros of the Obatogamau Formation (ɛNd = +2.8 to +4.0; δ18O = +7.3 to 8.0‰) are consistent with depleted mantle sources. All rock types in the Doré Lake Complex and the Roy Group share the trace element characteristics of modern arc magmas, suggesting a suprasubduction zone setting for these two lithological associations. On the basis of regional geology and geochemical data, we suggest that the Doré Lake Complex and the Obatogamau Formation represent a dismembered fragment of a suture zone, like many Phanerozoic ophiolites, resulting from closure of a back-arc basin between 2703 and 2690 Ma.

Recycling of Malaysia's electric arc furnace (EAF) slag waste into heavy-duty green ceramic tile.

PubMed

Teo, Pao-Ter; Anasyida, Abu Seman; Basu, Projjal; Nurulakmal, Mohd Sharif

2014-12-01

Recently, various solid wastes from industry such as glass waste, fly ash, sewage sludge and slag have been recycled into various value-added products such as ceramic tile. The conventional solutions of dumping the wastes in landfills or incineration, including in Malaysia are getting obsolete as the annual huge amount of the solid wastes would boost-up disposal cost and may cause permanent damage to the flora and fauna. This recent waste recycling approach is much better and greener as it can resolve problems associated with over-limit storage of industrial wastes and reduce exploration of natural resources for ceramic tile to continuously sustain the nature. Therefore, in this project, an attempt was made to recycle electric arc furnace (EAF) slag waste, obtained from Malaysia's steel making industry, into ceramic tile via conventional powder compaction method. The research work was divided into two stages. The first stage was to evaluate the suitability of EAF slag in ceramic tile by varying weight percentage of EAF slag (40 wt.%, 50 wt.% and 60 wt.%) and ball clay (40 wt.%, 50 wt.% and 60 wt.%), with no addition of silica and potash feldspar. In the second stage, the weight percentage of EAF slag was fixed at 40 wt.% and the percentage of ball clay (30 wt.% and 40 wt.%), feldspar (10 wt.% and 20 wt.%) and silica (10 wt.% and 20 wt.%) added was varied accordingly. Results obtained show that as weight percentage of EAF slag increased up to 60 wt.%, the percentage of apparent porosity and water absorption also rose, with a reduction in tile flexural strength and increased porosity. On the other hand, limiting the weight percentage of EAF slag to 40 wt.% while increasing the weight percentage of ball clay led to a higher total percentage of anorthite and wollastonite minerals, resulting in higher flexural strength. It was found that introduction of silica and feldspar further improved the flexural strength due to optimization of densification process. The highest flexural strength, lowest apparent porosity and water absorption of EAF slag based tile was attained at the composition of 40 wt.% EAF slag--30 wt.% ball clay--10 wt.% feldspar--20 wt.% silica. The properties of ceramic tile made with EAF slag waste (up to 40 wt.%), especially flexural strength are comparable to those of commercial ceramic tile and are, therefore, suitable as high flexural strength and heavy-duty green ceramic floor tile. Continuous development is currently underway to improve the properties of tile so that this recycling approach could be one of the potential effective, efficient and sustainable solutions in sustaining our nature. Copyright © 2014 Elsevier Ltd. All rights reserved.

Melt- rock reaction at oceanic peridotite-gabbro transition, through combined EBSD and in-situ mineral geochemistry on the Erro Tobbio peridotitic body (Ligurian ophiolites, Italy).

NASA Astrophysics Data System (ADS)

Basch, Valentin; Rampone, Elisabetta; Ildefonse, Benoit; Godard, Marguerite; Crispini, Laura

2017-04-01

Several lines of evidence have stressed that melt-rock reactions acting at the oceanic mantle-crust boundary play an important role in the chemical evolution of MORBs and the formation of the primitive (olivine-rich) lower oceanic crust. To address this issue, we performed detailed structural analyses and in-situ mineral geochemistry on the Erro-Tobbio (ET) ultramafic unit (Ligurian Alps, Italy), where impregnated mantle peridotites are primarily associated to a hectometre-size mafic body composed of troctolite to plagioclase-bearing wehrlite. The troctolitic body exhibits high complexity, with a host troctolite (Troctolite A) crosscut by troctolitic decametre-size pseudo-tabular bodies (Troctolite B). These different generations of troctolites show distinct modal compositions and textures. The host troctolite A displays a dominant millimetre-size corroded granular texture of olivine associated with dunite pods and a layering defined by poikilitic plagioclase enrichment. The contact between the mafic body and the host mantle peridotites is irregular, and defined by troctolite to wehrlite apophyses. The troctolite A shows microstructures and Crystallographic Preferred Orientation (CPO) indicative of a formation after impregnation of a mantle dunite by an olivine-undersaturated melt. This impregnation leads to olivine dissolution, associated with poikilitic plagioclase and clinopyroxene crystallization. This is indicated by a progressive randoming of the Axial-[100] CPO with olivine disaggregation and increasing melt input in the troctolite. The crosscutting troctolite B exhibits significant olivine textural variation, from fine-grained granular to deformed coarse-grained skeletal olivine. Olivine in the troctolite B shows CPO indicative of crystallization after magmatic flow, intrusive into the host troctolite A. Both troctolite types display large major and trace element variations in minerals, e.g. variation of Anorthite content (An = 54-67) in plagioclase at rather constant Forsterite content in olivine, and significant Zr, Ti, HREE heterogeneity in olivine, systematically correlated with the textural variability (e.g. corroded deformed vs. undeformed granular olivine). These features indicate that reactive crystallization had an important role in the origin of the ET troctolites. We infer that the textural heterogeneity of olivine in the troctolite B is related to variations in the degree of undercooling and cooling rate of the melt (Faure et al, 2003). The skeletal olivine crystallization could correspond to the influx of a more primitive melt into a colder host troctolite, followed by evolution of the melt leading to formation of fine-grained euhedral crystals. Overall, the results of this study suggest a poly-phase formation of this hectometre-scale gabbroic body, involving impregnation of a mantle-derived dunitic body followed by intrusion of undercooled primitive melts. Faure, F., Trolliard, G., Nicollet, C. & Montel, J.M. (2003), A developmental model of olivine morphology as a function of the cooling rate and the degree of undercooling. Contrib. Miner. Petrol. 145:251-263.

Equation of state of molten fayalite (Fe2SiO4)

NASA Astrophysics Data System (ADS)

Waller, C.; Liu, Q.; Agee, C. B.; Asimow, P. D.; Lange, R. A.

2010-12-01

We have conducted new equation of state measurements on liquid fayalite (Fe2SiO4) in a collaborative, multi-technique study. Using a shared bulk starting material, we have measured the liquid density, the bulk modulus (K), and its pressure derivative (K’) from 1 atm to 163 GPa using 1-atm double-bob Archimedean and ultrasonic, sink/float, and shock wave techniques to form a coherent, internally consistent equation of state. Previous shock studies of liquid fayalite were conducted up to pressures of 40 GPa1; we extended this data set with two additional pre-heated, molten (1573 K) fayalite shock compression experiments at 121 and 163 GPa. Linear fitting of this data in shock velocity (US)-particle velocity (up) space defines a Hugoniot with an unconstrained zero-pressure intercept that crosses within error at the bulk sound speed (Co) determined by ultrasonic techniques. Fixing the intercept at this ultrasonic value reduces the error on the linear fit and yields the relation: US =1.65(0.02)up+ 2.4377(0.006) km/s. This relationship indicates that the behavior of the liquid is relaxed during shock compression and demonstrates consistency across experimental methods. Likewise, results from new static compression sink/float experiments conducted in piston-cylinder and multi-anvil devices are in agreement with shock wave and ultrasonic data, consistent with an isothermal K=19.4 and K’=5.57 at 1500°C. In solid materials, the Grüneisen parameter (γ) generally decreases upon compression. However, preliminary calculations for γ of this liquid using additional initially solid shock data from Chen et al.(2002) indicate that γ increases upon compression. Using the functional form γ = γo(ρo/ρ)q at a density of 7.65 Mg/m3 yields a q value of -1.77 (γo = 0.41 is known from low-pressure data), which is similar to the reported q values of forsterite2, enstatite3, and anorthite-diopside liquids4. This result shows that iron-bearing mafic to ultramafic silicate liquids follow the same general behavior as iron-free liquids such that -2.0 ≤ q ≤ -1.5 for the compression range 1 ≥ ρo/ρ ≥ 0.50. We will be performing an additional shock wave experiment on initially solid (300 K) fayalite to confirm this result. We will be continuing collaborative equation of state measurements on additional iron-bearing silicate liquids, working to further clarify the properties of melts and their importance to understanding the dynamics of the early magma ocean and of melt migration within the mantle. In particular, understanding the properties of iron-rich silicates and their melts will constrain hypotheses of melting and of iron enrichment for explaining the occurrence and characteristics of ultra-low velocity zones near the CMB.

Oxygen isotope geochemistry of mafic phenocrysts in primitive mafic lavas from the southernmost Cascade Range, California

USGS Publications Warehouse

Underwood, Sandra J.; Clynne, Michael A.

2017-01-01

Previously reported whole-rock δ18O values (5.6–7.8‰) for primitive quaternary mafic lavas from the southernmost Cascades (SMC) are often elevated (up to 1‰) relative to δ18O values expected for mafic magmas in equilibrium with mantle peridotite. Olivine, clinopyroxene, and plagioclase crystals were separated from 29 geochemically well-characterized mafic lavas for δ18O measurements by laser fluorination to assess modification of the mantle sources by ancient and modern subducted components. Oxygen isotope values of olivine phenocrysts in calc-alkaline lavas and contemporaneous high alumina olivine tholeiitic (HAOT) lavas generally exceed depleted mantle olivine values (~4.9–5.3‰). Modern addition of up to 6 wt% slab-derived fluid from Gorda serpentinized peridotite dehydration (~15‰) or chlorite dehydration (~10‰) within the serpentinized peridotite can provide the 18O enrichment detected in olivine phenocrysts (δ18Oolivine = 5.3–6.3‰) in calc-alkaline mafic lavas, and elevate 18O in overlying mantle lithosphere, as well. Specifically, although HAOT δ18Oolivine values (5.5–5.7‰) may reflect partial melting in heterogeneous 18O enriched mantle source domains that developed during multiple subduction events associated with terrane accretion (e.g., <1 wt% of ~15‰ materials), an additional 18O enrichment of up to 2 wt% of 10–15‰ slab-derived hydrous fluids might be accommodated. The calc-alkaline primitive magmas appear to have experienced a continuous range of open system processes, which operate in the mantle and during rapid magma ascent to eruption, and occasionally post quench. Textural relationships and geochemistry of these lava samples are consistent with blends of mafic phenocrysts and degassed melts in varying states of 18O disequilibrium. In lenses of accumulated melt within peridotite near the base of the crust, coexisting olivine and clinopyroxene δ18O values probably are not at isotopic equilibrium because fluids introduced into the system perturbed the δ18Omelt values. A “sudden” melt extraction event interrupts 18O equilibration in phenocrysts and poorly mixed melt(s). Rapid ascent of volatile oversaturated primitive mafic magma through the crust appears to be accompanied by devolatilization and crystallization of anorthite-rich plagioclase with elevated δ18Oplag values. The (Sr/P)N values for the whole rock geochemistry are consistent with a 87Sr/86Sr ~0.7027 slab-derived fluid addition into the infertile peridotite source of magmas, and melt devolatilization is recorded in the mixture of disequilibrium δ18O values for the constituent phases of lavas. Morbidity of the Gorda Plate as it undergoes intense deformation from the spreading ridge to the trench is likely a key factor to developing the carrying capacity of hydrous fluids and mineral phases in the slab subducting into the SMC mantle.

Constraints on the Composition and Evolution of the Lunar Crust from Meteorite NWA 3163

NASA Technical Reports Server (NTRS)

McLeod, C. L.; Brandon, A. D.; Fernandes, V. A.; Peslier, A. H.; Lapen, T. J.; Irving, A. J.

2013-01-01

The lunar meteorite NWA 3163 (paired with NWA 4881, 4483) is a ferroan, feldspathic granulitic breccia characterized by pigeonite, augite, olivine, maskelynite and accessory Tichromite, ilmenite and troilite. Bulk rock geochemical signatures indicate the lack of a KREEP- derived component (Eu/Eu* = 3.47), consistent with previously studied lunar granulites and anorthosites. Bulk rock chondrite-normalized signatures are however distinct from the anorthosites and granulites sampled by Apollo missions and are relatively REE-depleted. In-situ analyses of maskelynite reveal little variation in anorthite content (average An% is 96.9 +/- 1.6, 2 sigma). Olivine is relatively ferroan and exhibits very little variation in forsterite content with mean Fo% of 57.7 +/- 2.0 (2 sigma). The majority of pyroxene is low-Ca pigeonite (En57Fs33Wo10). Augite (En46Fs21Wo33) is less common, comprising approximately 10% of analyzed pyroxene. Two pyroxene thermometry on co-existing orthopyroxene and augite yield an equilibrium temperature of 1070C which is in reasonable agreement with temperatures of 1096C estimated from pigeonite compositions. Rb-Sr isotopic systematics of separated fractions yield an average measured Sr-87/Sr-87 of 0.699282+/-0.000007 (2 sigma). Sr model ages are calculated using a modern day Sr-87/Sr-86 Basaltic Achondrite Best Initial (BABI) value of 0.70475, from an initial BABI value Sr-87/Sr-86 of 0.69891 and a corresponding Rb-87/Sr-97 of 0.08716. The Sr model Thermomechanical analysis (TMA) age, which represents the time of separation of a melt from a source reservoir having chondritic evolution, is 4.56+/-0.1 Ga. A Sr model T(sub RD) age, which is a Rb depletion age and assumes no contribution from Rb in the sample in the calculation, yields 4.34+/-0.1 Ga (i.e. a minimum age). The Ar-Ar dating of paired meteorite NWA 4881 reveals an age of c. 2 Ga, likely representing the last thermal event this meteorite experienced. An older Ar-40/Ar-39 age of c. 3.5 Ga may record the thermal event which produced the granulitic texture. Additional chronological constraints will be provided by Sm-Nd systematics. Ferroan Anorthosites like NWA 3163 have been interpreted to represent direct lunar magma ocean (LMO) crystallization products. If this is the case, trace element concentrations in NWA 3163 primary mineral phases should be in equilibrium with residual LMO liquids present during crystallization of those phases. Results from petrogenetic modeling suggest that the NWA 3163 protolith did not form from crystallization of an initially LREE depleted LMO but rather require an initially chondritic LMO with early garnet crystallization. Furthermore, a two-stage crystallization model where plagioclase crystalized prior to pyroxene (93% vs. 99.5% of LMO crystallization) is implied.

Petrogenesis and provenance of ungrouped achondrite Northwest Africa 7325 from petrology, trace elements, oxygen, chromium and titanium isotopes, and mid-IR spectroscopy

NASA Astrophysics Data System (ADS)

Goodrich, Cyrena A.; Kita, Noriko T.; Yin, Qing-Zhu; Sanborn, Matthew E.; Williams, Curtis D.; Nakashima, Daisuke; Lane, Melissa D.; Boyle, Shannon

2017-04-01

Northwest Africa (NWA) 7325 is an ungrouped achondrite that has recently been recognized as a sample of ancient differentiated crust from either Mercury or a previously unknown asteroid. In this work we augment data from previous investigations on petrography and mineral compositions, mid-IR spectroscopy, and oxygen isotope compositions of NWA 7325, and add constraints from Cr and Ti isotope compositions on the provenance of its parent body. In addition, we identify and discuss notable similarities between NWA 7325 and clasts of a rare xenolithic lithology found in polymict ureilites. NWA 7325 has a medium grained, protogranular to poikilitic texture, and consists of 10-15 vol.% Mg-rich olivine (Fo 98), 25-30 vol.% diopside (Wo 45, Mg# 98), 55-60 vol.% Ca-rich plagioclase (An 90), and trace Cr-rich sulfide and Fe,Ni metal. We interpret this meteorite to be a cumulate that crystallized at ⩾1200 °C and very low oxygen fugacity (similar to the most reduced ureilites) from a refractory, incompatible element-depleted melt. Modeling of trace elements in plagioclase suggests that this melt formed by fractional melting or multi-stage igneous evolution. A subsequent event (likely impact) resulted in plagioclase being substantially remelted, reacting with a small amount of pyroxene, and recrystallizing with a distinctive texture. The bulk oxygen isotope composition of NWA 7325 plots in the range of ureilites on the CCAM line, and also on a mass-dependent fractionation line extended from acapulcoites. The ε54Cr and ε50Ti values of NWA 7325 exhibit deficits relative to terrestrial composition, as do ordinary chondrites and most achondrites. Its ε54Cr value is distinct from that of any analyzed ureilite, but is not resolved from that of acapulcoites (as represented by Acapulco). In terms of all these properties, NWA 7325 is unlike any known achondrite. However, a rare population of clasts found in polymict ureilites ("the magnesian anorthitic lithology") are strikingly similar to NWA 7325 in mineralogy and mineral compositions, oxygen isotope compositions, and internal textures in plagioclase. These clasts are probably xenolithic in polymict ureilites, and could be pieces of NWA 7325-like meteorites. Using constraints from chromium, titanium and oxygen isotopes, we discuss two possible models for the provenance of the NWA 7325 parent body: (1) accretion in the inner solar system from a reservoir similar to that of acapulcoites in Δ17O, ε54Cr and ε50Ti; or (2) early (<1 Ma after CAI formation) accretion in the outer solar system (beyond the snow line), before 54Cr and 50Ti anomalies were introduced to this region of the solar system. The mid-IR emission spectrum of NWA 7325 obtained in this work matches its modal mineralogy, and so can be compared with spectra of new meteorites or asteroids/planets to help identify similar materials and/or the parent body of NWA 7325.

Origin, speciation, and fluxes of trace-element gases at Augustine volcano, Alaska: Insights into magma degassing and fumarolic processes

NASA Astrophysics Data System (ADS)

Symonds, Robert B.; Reed, Mark H.; Rose, William I.

1992-02-01

Thermochemical modeling predicts that trace elements in the Augustine gas are transported from near-surface magma as simple chloride (NaCl, KCl, FeCl 2, ZnCl 2, PbCl 2, CuCl, SbCl 3, LiCl, MnCl 2, NiCl 2, BiCl, SrCl 2), oxychloride (MoO 2Cl 2), sulfide (AsS), and elemental (Cd) gas species. However, Si, Ca, Al, Mg, Ti, V, and Cr are actually more concentrated in solids, beta-quartz (SiO 2), wollastonite (CaSiO 3), anorthite (CaAl 2Si 2O 8), diopside (CaMgSi 2O 6), sphene (CaTiSiO 5), V 2O 3(c), and Cr 2O 3(c), respectively, than in their most abundant gaseous species, SiF 4, CaCl 2, AlF 2O, MgCl 2 TiCl 4, VOCl 3, and CrO 2Cl 2. These computed solids are not degassing products, but reflect contaminants in our gas condensates or possible problems with our modeling due to "missing" gas species in the thermochemical data base. Using the calculated distribution of gas species and the COSPEC SO 2 fluxes, we have estimated the emission rates for many species (e.g., COS, NaCl, KCl, HBr, AsS, CuCl). Such forecasts could be useful to evaluate the effects of these trace species on atmospheric chemistry. Because of the high volatility of metal chlorides (e.g., FeCl 2, NaCl, KCl, MnCl 2, CuCl), the extremely HCl-rich Augustine volcanic gases are favorable for transporting metals from magma. Thermochemical modeling shows that equilibrium degassing of magma near 870°C can account for the concentrations of Fe, Na, K, Mn, Cu, Ni and part of the Mg in the gases escaping from the dome fumaroles on the 1986 lava dome. These calculations also explain why gases escaping from the lower temperature but highly oxidized moat vents on the 1976 lava dome should transport less Fe, Na, K, Mn and Ni, but more Cu; oxidation may also account for the larger concentrations of Zn and Mo in the moat gases. Nonvolatile elements (e.g., Al, Ca, Ti, Si) in the gas condensates came from eroded rock particles that dissolved in our samples or, for Si, from contamination from the silica sampling tube. Only a very small amount of rock contamination occurred (water/rock ratios between 10 4 and 10 6). Erosion is more prevalent in the pyroclastic flow fumaroles than in the summit vents, reflecting physical differences in the fumarole walls: ash vs. lava. Trace element contents of volcanic gases show enormous variability because of differences in the intensive parameters of degassing magma and variable amounts of wall rock erosion in volcanic fumaroles.

Localization of ductile deformation in lithosphere and rocks: the role of grain boundary sliding

NASA Astrophysics Data System (ADS)

Dimanov, Alexandre; Rahanel, Jean; Bornert, Michel; Bourcier, Mathieu; Gaye, Ag; Heripre, Eva; Ludwig, Wolfgang

2017-04-01

Ductile strain of the lithosphere localizes in multi-scale shear zones, ranging from km to mm scales. The resulting mylonites/ultramylonites present microstructural signatures of several concomitant deformation mechanisms. Besides cataclastic features, crystal plasticity dominates in volume, but grain boundary sliding and diffusive/solution mass transport act along interfaces. Considering solely the inherited natural microstructures does not make clear the chronology of appearance and the interactions between these mechanisms. Therefore, inference of the overall mylonitic rheology seems illusory. We have therefore realized over the last decade a systematic rheological characterization of the high temperature flow of various synthetic anorthite - diopside mixtures. The data clearly suggest Newtonian type of rheology as best adapted to the materials representative of the lower crust mylonites. However, the post mortem microstructures undoubtedly evidenced the coexistence of both crystal plasticity and grain boundary sliding processes. Yet, the specific roles of each mechanism in the localization process remained unclear. In order to clarify these aspects we realized a multi-scale micromechanical in situ investigation of the ductile deformation of synthetic rock-salt. The mechanical tests were combined with in-situ optical microscopy, scanning electron microscopy and X-ray tomography (MCT). Digital image correlation (DIC) techniques allowed for measurements and characterization of the multi-scale organization of 2D and 3D full strain fields. Macroscopic and mesoscopic shear bands appear at the sample and microstructure scales, respectively. DIC evidenced the development of discrete slip bands within individual grains, and hence of dominant crystal plasticity. Combination of DIC and EBSD allowed for identification of active slip systems. Conversely, DIC allowed for the identification and the precise quantification of minor activity (< 5% contribution) of grain boundary sliding (GBS). Most importantly, GBS is continuously operating along with crystal slip plasticity, which indicates that in spite of being a secondary mechanism it is a necessary one. GBS seems to accommodate very efficiently for plastic strain incompatibilities between neighboring grains. Our finding is strengthened by finite element (FE) modeling of the viscoplastic behavior of rock-salt, which appears inadequate in detail if solely based on crystal plasticity. Moreover, the local GBS appears to i) trigger the formation of localized shear bands at the microstructure scale, and ii) allow for homogenization of ductile strain throughout the whole specimen. Our major conclusions are that crystal plasticity and GBS are not really dissociable. They are co-operative mechanisms that accommodate each other depending on microstructure and loading conditions. Minor GBS is always necessary in order to accommodate for the pronounced plastic anisotropy of minerals. Conversely, localized minor crystal plasticity is necessary to accommodate dominant GBS. Finally, GBS is directly involved in the initial development of localized ductile strain at the aggregate scale. But, GBS might take over as the dominant mechanism within fine grained mylonites and contribute to the large scale shear zone localization.

Experimental Compressibility of Molten Hedenbergite at High Pressure

NASA Astrophysics Data System (ADS)

Agee, C. B.; Barnett, R. G.; Guo, X.; Lange, R. A.; Waller, C.; Asimow, P. D.

2010-12-01

Experiments using the sink/float method have bracketed the density of molten hedenbergite (CaFeSi2O6) at high pressures and temperatures. The experiments are the first of their kind to determine the compressibility of molten hedenbergite at high pressure and are part of a collaborative effort to establish a new database for an array of silicate melt compositions, which will contribute to the development of an empirically based predictive model that will allow calculation of silicate liquid density and compressibility over a wide range of P-T-X conditions where melting could occur in the Earth. Each melt composition will be measured using: (i) double-bob Archimedean method for melt density and thermal expansion at ambient pressure, (ii) sound speed measurements on liquids to constrain melt compressibility at ambient pressure, (iii) sink/float technique to measure melt density to 15 GPa, and (iv) shock wave measurements of P-V-E equation of state and temperature between 10 and 150 GPa. Companion abstracts on molten fayalite (Waller et al., 2010) and liquid mixes of hedenbergite-diopside and anorthite-hedenbergite-diopside (Guo and Lange, 2010) are also presented at this meeting. In the present study, the hedenbergite starting material was synthesized at the Experimental Petrology Lab, University of Michigan, where melt density, thermal expansion, and sound speed measurements were also carried out. The starting material has also been loaded into targets at the Caltech Shockwave Lab, and experiments there are currently underway. We report here preliminary results from static compression measurement performed at the Department of Petrology, Vrije Universiteit, Amsterdam, and the High Pressure Lab, Institute of Meteoritics, University of New Mexico. Experiments were carried out in Quick Press piston-cylinder devices and a Walker-style multi-anvil device. Sink/float marker spheres implemented were gem quality synthetic forsterite (Fo100), San Carlos olivine (Fo90), and natural pyropic garnet(Pyr74 Alm13.5 Gro12.5). We bracketed the density of molten hedenbergite with Fo100 to be 3.09 g cm-3 at 1.1 GPa and 1450°C, and with Fo90 to be 3.27 g cm-3 at 3.0 GPa and 1450-1550°C. These sink-float values represent an increase in isothermal density from reference ambient pressure of 6% and 12% respectively, or linear compressions of 0.16 and 0.12 g cm-3 GPa-1. The density-with-pressure increases in our static compression experiments are in good agreement with the Michigan ambient pressure sound speed measurements that yield an isentropic bulk modulus of KS=18.77 GPa. Currently we are performing higher pressure sink/float experiments in the range 7-8 GPa with pyrope garnet marker spheres to better constrain values for the isothermal bulk modulus (KT) and its pressure derivative K'. As a by-product of our sink/float experiments we are also determining the melting curve of hedenbergite well beyond the published pressure extent of approximately 1.5 GPa (Lindsley, 1967). Our early data show the hedenbergite liquidus to be 1450°C at 3 GPa and approximately 1750°C at 7 GPa.

Voluminous juvenile lithic fragments in the pumice-fall deposit of the 1108 eruption of Asama volcano: Evidence of repeated compaction and fragmentation in the shallow conduit

NASA Astrophysics Data System (ADS)

Nakamura, M.; Kichise, T.; Yasui, M.; Nagahashi, Y.; Yoshida, T.

2010-12-01

The pumice-fall deposit of the 1108 eruption of Asama volcano, central Japan, contains a large amount of lithic fragments (up to 40 wt%) that are angular, dense, and juvenile. The deposit consists of eight sublayers, comprising three thick layers of pumice (1.0-1.4 g/cm3) containing 5-40 wt% lithic fragments (1.4-2.7 g/cm3) interbedded with two thin pumiceous layers, two thin layers of lapilli-sized lithic fragments, and a volcanic ash layer. The average volume of each sublayer is ~0.01 km3. The large volume of lithic fragments and their occurrence throughout the deposit show that their source lava plugs formed and fragmented continuously during the eruption. The lithic fragments are not coated with vesicular matrix, indicating that the fragments were entrained into mist flows of the eruption columns; i.e., after the magma fragmentation that produced the pumice clasts. The plagioclase microlites in the lithic fragments have a range (55-75 mol%) and frequency distribution of anorthite content similar to those in the pumices, indicating that the lithic fragments and pumices have a similar history of decompression from the magma reservoir to the shallow conduit. The groundmass of the pumices has a porosity approximately ranging from 40% to 60% and positive correlation with groundmass crystallinity; this is consistent with an interpretation that magma with higher porosity is more decompressed and thus crystallized in the shallower conduit. The highest crystallinity of the pumice, of which the groundmass porosity is ca. 60%, coincides with the lowest crystallinity of the lithic fragments. In addition, the pore connectivity of the pumice increases (with increasing porosity) steeply at a groundmass porosity of ca. 60%. These petrographical observations strongly suggest that the lithic fragments are the collapsed and compacted products of magma foam (at a groundmass porosity of ca. 60%) just before it fragmented to become pumices. The lithic fragments often have mosaic texture with healed cracks, suggesting that they were formed by repeated shear-induced fragmentation and welding. The average water contents of the glasses in the groundmass of the lithic fragments and pumices are 0.35 and 0.54 wt%, respectively, corresponding to approximate quench depths of 200 and 300 m, respectively. The average volume of the erupted lithic fragments in each sublayer is equivalent to the volume of a magma plug with a diameter of 200 m and depth of 200 m, which is almost equal to the present crater size of Asama. These genetic and occurrence relations between the lithic fragments and pumices indicate that the magma ascent condition of the 1108 eruption was near the bifurcation boundary between the formations of the lava plug via foam compaction and the eruption column via magma fragmentation. Therefore, the magma ascent rate of the 1108 eruption could be used as a rough criterion for predicting the eruption styles in the future volcanic crisis of Asama.

Metal/silicate partitioning of Pt and the origin of the "late veneer"

NASA Astrophysics Data System (ADS)

Ertel, W.; Walter, M. J.; Drake, M. J.; Sylvester, P. J.

2002-12-01

Highly siderophile elements (HSEs) are perfect tools for investigating core forming processes in planetary bodies due to their Fe-loving (siderophile) geochemical behavior. Tremendous scientific effort was invested into this field during the past 10 years - mostly in 1 atm experiments. However, little is known about their high-pressure geochemistry and partitioning behavior between core and mantle forming phases. This knowledge is essential to distinguish between equilibrium (Magma Ocean) and non-equilibrium (heterogeneous accretion, late veneer) models for the accretion history for the early Earth. We therefore chose to investigate the partitioning behavior of Pt up to pressures of 140 kbar (14 GPa) and temperatures of 1950°C. The used melt composition - identical to melt systems used in 1 atm experiments - is the eutectic composition of Anorthite-Diopside (AnDi), a pseudo-basalt. A series of runs were performed which were internaly buffered by the piston cylinder apparatus, and were followed by duplicate experiments buffered in the AnDi-C-CO2 system. These experiments constitute reversals since they approach equilibrium from an initially higher and lower Pt solubility (8 ppm in the non-buffered runs, and essentially Pt free in the buffered runs). Experimental charges were encapsulated in Pt capsules which served as source for Pt. Experiments up to 20 kbar were performed in a Quickpress piston cylinder apparatus, while experiments at higher pressures were performed in a Walker-type (Tucson, AZ) and a Kawai-type (Misasa, Japan) multi anvil apparatus. Time series experiments were performed in piston-cylinder runs to determine minimum run durations for the achievement of equilibrium, and to guarantee high-quality partitioning data. 6 hours was found to be sufficient to obtain equilibrium. In practice, all experiments exceeded 12 hours to assure equilibrium. In a second set of runs the temperature dependence of the partitioning behavior of Pt was investigated between the melting point of the 1 atm, AnDi system and the melting point of the Pt capsule material. Over 150 piston cylinder and 12 multi anvil experiments have been performed. Pt solubility is only slightly dependent on temperature, decreasing between 1800 and 1400°C by less than an order of magnitude. In consequence, the partitioning behavior of Pt is mostly determined by its oxygen fugacity dependence, which has only been determined in 1 atm experiments. At 10 kbar, metal/silicate partition coefficients (D's) decrease by about 3 orders of magnitude. The reason for this is not understood, but might be attributed to a first order phase transition as found for, e.g., SiO2 or H2O. Above 10 kbar any increase in pressure does not lead to any further significant decrease in partition coefficients. Solubilities stay roughly constant up to 140 kbar. Abundances of moderately siderophile elements were possibly established by metal/silicate equilibrium in a magma ocean. These results for Pt suggest that the abundances of HSEs were most probably established by the accretion of a chondritic veneer following core formation, as metal/silicate partition coefficients are too high to be consistent with metal/silicate equilibrium in a magma ocean.

Rates of weathering rind formation on Costa Rican basalt

NASA Astrophysics Data System (ADS)

Sak, Peter B.; Fisher, Donald M.; Gardner, Thomas W.; Murphy, Katherine; Brantley, Susan L.

2004-04-01

Weathering rind thicknesses were measured on ∼ 200 basaltic clasts collected from three regionally extensive alluvial fill terraces (Qt 1, Qt 2, and Qt 3) preserved along the Pacific coast of Costa Rica. Mass balance calculations suggest that conversion of unweathered basaltic core minerals (plagioclase and augite) to authigenic minerals in the porous rind (kaolinite, allophane, gibbsite, Fe oxyhydroxides) is iso-volumetric and Ti and Zr are relatively immobile. The hierarchy of cation mobility (Ca ≈ Na > K ≈ Mg > Si > Al > Fe ≈ P) is similar to other tropical weathering profiles and is indicative of differential rates of mineral weathering (anorthite > albite ≈ hypersthene > orthoclase ≫ apatite). Alteration profiles across the cm-thick rinds document dissolution of plagioclase and augite and the growth of kaolinite, with subsequent dissolution of kaolinite and precipitation of gibbsite as weathering rinds age. The rate of weathering rind advance is evaluated using a diffusion-limited model which predicts a parabolic rate law for weathering rind thickness, rr, as a function of time, t(rr =κt), and an interface-limited model which predicts a linear rate law for weathering rind thickness as a function of time (rr = kappt). In these rate laws, κ is a diffusion parameter and kapp is an apparent rate constant. The rate of advance is best fit by the interface model. Terrace exposures are confined to the lower reaches of streams draining the Pacific slope near the coast where the stream gradient is less than ∼3 m/km, and terrace deposition is influenced by eustatic sea level fluctuations. Geomorphological evidence is consistent with terrace deposition coincident with sea level maxima when the stream gradient would be lowest. Assigning the most weathered regionally extensive terrace Qt 1 (mean rind thickness 6.9 ± 0. 6cm) to oxygen isotope stage (OIS) 7 (ca. 240 ka), and assuming that at time = 0 rind thickness = 0, it is inferred that terrace Qt 2 (rr = 2.9 ± 0.1 cm) is coincident with stage 5e (ca. 125 ka) and that Qt 3 (rr = 0.9 ± 0.1 cm) is consistent with OIS 3 (ca. 37 ka). These assignments yield a value of kapp of 8.6 × 10-13 cm s-1 (R2 = 0.99). Only this value satisfies both the existing age controls and yields ages coincident with sea level maxima. Using this value, elemental weathering release fluxes across a weathering rind from Qt 2 range from 6.0 × 10-9 mol Si m-2 s-1 to 2.5 × 10-11 mol K m-2 s-1. The rate of rind advance for the Costa Rican terraces is 2.8 × 10-7 m yr-1. Basalt rind formation rates in lower temperature settings described in the literature are also consistent with interface-controlled weathering with an apparent activation energy of about 50 kJ mol-1. Rates of rind formation in Costa Rica are an order of magnitude slower than reported for global averages of soil formation rates.

Melts in the Deep Earth: Calculating the Densities of CaO-FeO-MgO-Al2O3-SiO2 Liquids

NASA Astrophysics Data System (ADS)

Thomas, C.; Guo, X.; Agee, C. B.; Asimow, P. D.; Lange, R. A.

2012-12-01

We present new equation of state (EOS) measurements for hedenbergite (Hd, CaFeSi2O6) and forsterite (Fo, Mg2SiO4) liquids. These liquid EOS add to the basis set in the CaO-FeO-MgO-Al2O3-SiO2 (CMASF) oxide space at elevated temperatures and pressures; other liquids include: enstatite (En, MgSiO3), anorthite (An, CaAl2Si2O8), diopside (Di, CaMgSi2O6), and fayalite (Fa, Fe2SiO4). The Hd EOS measurement was a multi-technique collaboration using 1-atm double-bob Archimedean, ultrasonic, sink/float, and shock wave techniques. Un-weighted linear fitting of the shock data in shock velocity (US)-particle velocity (up) space defines a pre-heated (1400 °C) Hugoniot US = 2.628(0.024) + 1.54(0.01)up km/s. The slope corresponds to a K' of 5.16(0.04), consistent with piston-cylinder and multi-anvil sink/float experiments. The intercept is fixed at the ultrasonic sound speed (Co) since the unconstrained intercept is within the stated error. This behavior demonstrates consistency across methods and that the liquid is relaxed during shock compression. Shock compression of pre-heated (2000°C) single crystal Fo gives an un-weighted linear Hugoniot of US = 2.674(0.188) + 1.64(0.06)up km/s. The unconstrained Co falls below estimates based on extrapolation in both temperature and composition from two published partial molar sound speed models, 3.195m/s [1] and 3.126 m/s [2]. The shock-derived Co indicates that dC/dT is negative for Fo liquid, contrary to the positive [1] and zero [2] temperature dependences derived over relatively narrow temperature intervals. CMASF liquid isentropes were calculated using five end-members (En, Fo, Fa, An, Di). For modeling crystallization of a fictive magma ocean, we examined two liquids: peridotite [3] (P=.33En+.56Fo+.07Fa+.03An+.007Di) and simplified chondrite [4] (Ch=.62En+.24Fo+.08Fa+.04An+.02Di). Each end-member is defined by a 3rd or 4th order Birch-Murnaghan isentrope, Mie-Grüneisen thermal pressure and a constant heat capacity. The volumes are assumed to ideally mix allowing for interpolation between end-member compositions. Results show the chondrite critical isentrope intersecting its liquidus at the core-mantle boundary with a potential temperature (TP) of 2400 K, whereas the peridotite critical isentrope has a TP of 2800 K and first crystallizes at 85 GPa. An identical calculation fails to recover the Hd isentrope (Hd = Di+0.5Fa-0.5Fo). This failure is likely due to the very different partial molar volumes of FeO in Hd and Fa, which have average Fe2+ coordination states of ~4.5 and ~6, respectively [5]. Consequently the simple ideal model is likely to only support mixing among like-coordinated Fe2+ liquids. We hope to further investigate this hypothesis for linear-mixing by constraining the EOS of An-Hd (50:50), and An-Di-Hd (33:33:33) melts using pre-heated shock wave techniques. [1] Ghiorso & Kress (2004) AJS 304, 679-751.[2] Ai & Lange(2008) JGR 113,B04203.[3] Fiquet et al. (2010) Science 329, 1516-1518.[4]Andrault et al. (2011) EPSL 304, 251-259.[5]Lange et al. (2012) Goldschmidt meeting, abstract.

Solubility of copper in silicate melts as function of oxygen and sulfur fugacities, temperature, and silicate composition

NASA Astrophysics Data System (ADS)

Holzheid, A.; Lodders, K.

2001-06-01

The solubility of Cu in silicate melts coexisting with liquid Cu(Fe) metal and liquid Cu(Fe) sulfide was determined experimentally at oxygen fugacities ranging from 10 -9.1 to 10 -13.6 bar and sulfur fugacities ranging from 10 -2.5 to 10 -6.3 bar at 1300°C. An iron oxide-free silicate of anorthite-diopside eutectic composition and a synthetic MgO-rich basaltic silicate (FeO-bearing) were used in the partitioning experiments. In S-containing systems, some of the metal reacted to metal sulfide. The silicates in the four systems investigated (Fe-free and S-free; Fe-containing and S-free; Fe-free and S-containing; Fe-containing and S-containing) had different colors depending on the dissolved Cu species and the presence of iron and/or sulfur. Irrespective of the presence of sulfur, the solubility of Cu in the silicate increases with increasing oxygen fugacity and metal/silicate partition coefficients for Cu decrease. Increasing the temperature from 1300°C to 1514°C increases the Cu solubility (decreases the metal/silicate partition coefficient) at an oxygen fugacity 0.5 log units below the iron-wüstite (IW) equilibrium in the Fe-free, S-free and Fe-containing, S-free systems. We infer the presence of monovalent Cu + ("CuO 0.5") in the silicate melt on the basis of the solubility of Cu as function of oxygen fugacity. Experiments containing iron yield a formal valence of ˜0.5 for Cu at very low oxygen fugacities, which is not observed in Fe-free systems. The low formal valence is explained by redox reactions between iron and copper in the silicate melts. There is no evidence for sulfidic dissolution of Cu in the silicates but sulfur has indirect effects on Cu partitioning. Iron metal/silicate partition coefficients depend on oxygen fugacity and on sulfur fugacity. Sulfidic dissolution of iron and oxide-sulfide exchange reactions with Cu cause a small increase in Cu metal/silicate partition coefficients. We derive an activity coefficient (γ CuO 0.5) of 10 ± 1 for liquid CuO 0.5 at 1300°C for the silicate melts used here. A comparison with literature data shows that log γ CuO 0.5 increases in proportion to the mass percentages [CaO +(Al 2O 3)/2] in silicate melts. We recommend the following equations for Cu metal/silicate and sulfide/silicate partitioning for geochemical and cosmochemical modeling if silicate composition and the activity of Cu in the metal or sulfide is known: log D met/sil = -0.48 - 0.25 · log fO 2 - log γ Cu metal + 0.02 · [CaO + (Al 2O 3)/2; wt%] silicate logD sul/sil=+0.76-0.25 · logfO 2+0.25logfS 2-logγ CS 0.5,sulfide +0.02 · [CaO+Al 2O 3/2;wt%] silicate. The derived Cu metal/silicate and metal/sulfide partition coefficients are applied to core formation in the Earth and Mars. The observed Cu abundances in the Earth cannot be easily explained by simple core-mantle equilibrium, but the observed Cu abundances for Mars are consistent with core-mantle equilibrium at low pressure and temperatures.

Large Grüneisen Gamma of Dense Silicate Liquids: More Experiments and a First Self- consistent Model

NASA Astrophysics Data System (ADS)

Asimow, P. D.; Mosenfelder, J. L.; Ahrens, T. J.; Sun, D.

2007-12-01

The Grüneisen parameter, γ, of solid materials normally decreases upon compression, approximately as γρq = constant where q=1. However, multiple lines of evidence now indicate the opposite behavior in silicate liquids, in which γ increases upon compression (i.e., q<0). This was observed in shock-melted (Mg,Fe)2SiO4 liquid by Brown et al. [1] via comparison of the Hugoniot and release velocity. We observed the same behavior in Mg2SiO4 liquid (q ≤ -1.5) from comparison of the Hugoniots of forsterite and wadsleyite [2]. First-principles molecular dynamics simulations of MgSiO3 liquid [3] confirm that γ increases with density and show that γ in the liquid phase mimics solids with similar Si coordination state. Hence a continuous increase in γ of silicate liquids to lowermost mantle pressures, well beyond the range where transition to six-coordination of Si is complete, suggests that even higher-coordinated species are forming in the melt and by extension there may be 8- coordinated silicate minerals with stability fields beginning not very far above the Earth's core-mantle boundary pressure [4]. We present new experimental evidence for this behavior in another liquid composition. The Hugoniot of 1400°C anorthite-diopside eutectic liquid was measured at low pressure by Rigden et al. [5] and extended to 110 GPa by our recent work. We collected a Hugoniot point on a solid aggregate of the same composition initially at room temperature, shocked into the melt regime at 133 GPa. The difference in internal energy between this point and the hot liquid Hugoniot allows determination of the γ of this aluminosilicate liquid at 50% compression; the result fits q = -1.85±0.2, entirely consistent with the behavior of enstatite, forsterite, and Fe- bearing olivine liquids. We suggested on the basis of an approximate calculation that the large γ of dense silicate liquids yields a liquid isentrope steeper than the liquidus of a lower mantle magma ocean [2]. Here we show a preliminary self-consistent thermodynamic model of the MgO-SiO2 binary that matches the phase diagrams of MgO, Mg2SiO4, MgSiO3, and SiO2 in the lower mantle, that incorporates negative q in the γ model of the liquid, and that allows calculation of pressure-entropy diagrams showing how model isentropes behave during cooling. We find that for peridotite or chondritic compositions, perovskite crystallization begins at an entropy maximum near 60 GPa. The consequences for geochemical evolution depend on whether these crystals remain turbulently suspended or fractionate [6]; in the case of suspension our model shows that the mush transition affects the entire lower mantle over a rather narrow range in potential temperature. Below this point the solidus does not have a maximum and normal decompression melting behavior is observed. 1. Brown et al., in High-Pressure Research in Mineral Physics, M.H. Manghnani and Y. Syono, Editors. 1987, AGU: Washington, DC. p. 373-384. 2. Mosenfelder et al., J. Geophys. Res., 2007. 112: p. B06208. 3. Stixrude & Karki, Science, 2005. 310(5746): p. 297-299. 4. Akins & Ahrens, Geophys. Res. Lett., 2002. 29(10): 1394-1397. 5. Rigden et al. J. Geophys. Res. 1988. 93(B1): p. 367-382. 6. Solomatov & Stevenson. J. Geophys. Res., 1993. 98(E3): p. 5375-5390.

The stability of Cl-CO3-scapolite relative to plagioclase + CaCO3 + CaSO4 in the presence of NaCl brines as a function of P-T-XNaCl

NASA Astrophysics Data System (ADS)

Harlov, D. E.; Budzyn, B.

2008-12-01

Cl-CO3-scapolite [(Na,Ca)4[Al3 (Al,Si) 3 Si3 O24](Cl, CO3 , SO4 )] occurs as a common partial to total alteration of plagioclase in deep-crustal xenoliths, skarns, marbles, gabbros, metabasites, calc-silicate gneisses, as well as in quartzofeldspathic granulite-facies rocks in general (Moecher and Essene, 1990, J Petrol 31, 997). Alteration of plagioclase to Cl-CO3-scapolite is presumed due to metasomatism by CO2-NaCl-H2O fluids (Satish-Kumar and Santosh, 1998, Geol Mag 135, 27). Previous experimental work on CO3-scapolite has focused on reversing the equilibrium 3 CaAl2 Si2 O8 + CaCO3 = Ca4 Al6 Si6 O24 CO3 in either pure CO2 (Goldschmidt and Newton, 1977, Am Mineral 62, 1063) or in CO2-H2O (Huckenholz and Seiberl, 1989 Abs IGC 28, 2.79). These experiments have determined that the anorthite- calcite-scapolite equilibrium is nearly pressure-invariant in P-T space (200 to 1500 MPa) occurring at approximately 790 to 820 °C (Huckenholz and Seiberl, 1989). In this study, a series of experiments, involving the equilibrium 3 Plagioclase(An60) + 0.5 CaCO3 + 0.5 CaSO4 = [(Na,Ca)4[Al3 (Al,Si)3 Si3 O24](Cl, CO3, SO4 )] plus an NaCl brine (10/90, 20/80, 30/70, and 50/50 molar NaCl/H2O) have been done at 500, 1000, and 1500 MPa and 600 to 900 °C. Natural plagioclase and scapolite, along with synthetic calcite and anhydrite, were lightly ground together in equi-molar amounts in ethanol. The mineral mix (10 mg) + NaCl brine (5 mg), or pure H2O (1.5 mg), were loaded into 3 mm diameter/1.3 mm long Pt capsules which were arc-welded shut, folded, and placed horizontally in a CaF2 setup (with graphite oven), such that the thermocouple tip touched the Pt capsule, or placed in a hydrothermal autoclave (600 and 700 °C; 500 MPa) with an internal thermocouple. A series of duplicate experiments for the same mineral mix, at the same P-T conditions, were done utilizing pure H2O as the flux. The H2O-only experiments duplicated the P-T reversals of Huckenholz and Seiberl (1989). In contrast, the NaCl/H2 O experiments indicate that the stability field of Cl-CO3-scapolite (SiO2 =52.1, Al2O3=24.9, CaO=11.9, Na2O=7.60, Cl=1.86, CO3=2.00, SO4=0.45), relative to plagioclase, greatly expands in the presence of NaCl brines at NaCl concentrations above 10 percent NaCl such that Cl-CO2-scapolite is stable over 600 to 900 °C and 500 to 1500 MPa. This result further strengthens the proposition that NaCl brines, coupled with CO2-bearing fluids, can be and probably are involved during high-grade scapolitization of plagioclase-bearing rocks in the mid to lower crust and upper mantle.

Carbonate-silicate melt immiscibility, REE mineralising fluids, and the evolution of the Lofdal Intrusive Suite, Namibia

NASA Astrophysics Data System (ADS)

Bodeving, Sarah; Williams-Jones, Anthony E.; Swinden, Scott

2017-01-01

The Lofdal Intrusive Suite, Namibia, consists of calcio-carbonatite and silica-undersaturated alkaline intrusive rocks ranging in composition from phono-tephrite to phonolite (and nepheline syenite). The most primitive of these rocks is the phono-tephrite, which, on the basis of its Y/Ho and Nb/Ta ratios, is interpreted to have formed by partial melting of the mantle. Roughly linear trends in major and trace element contents from phono-tephrite to phonolite and nepheline syenite indicate that the latter two rock types evolved from the phono-tephrite by fractional crystallisation. The nepheline syenite, however, has a lower rare earth element (REE) content than the phonolite. The carbonatite has a primitive mantle-normalised REE profile roughly parallel to that of the silica-undersaturated alkaline igneous rocks, although the absolute REE concentrations are higher. Like the phono-tephrite, it also has a mantle Y/Ho ratio. However, the Nb/Ta and Zr/Hf ratios are significantly higher. Moreover, the carbonatite displays strong negative Ta, Zr and Hf anomalies on spidergrams, whereas the silicate rocks display positive anomalies for these elements. Significantly, this behaviour is predicted by the corresponding carbonatite-silicate melt partition coefficients, as is the behaviour of the REE. Based on these observations, we interpret the carbonatite to represent an immiscible liquid that exsolved from the phono-tephrite or possibly the phonolite melt. The result was a calcio-carbonatite that is enriched in the heavy REE (HREE) relative to most other carbonatites. Fluids released from the corresponding magma are interpreted to have been the source of the REE mineralisation that is currently the target of exploration. 2. The composition of feldspar in nepheline syenite, fenite, calcio-carbonatite and phonolite plotted on the feldspar ternary classification diagram modified after Schairer (1950) in terms of the components albite (Ab), orthoclase (Or) and anorthite (An). Note: ANO = anorthosite, SAN = sanidine, OLI = oligoclase, AND = andesine, LAB = labradorite, BYT = bytownite. 3. Composition of the Lofdal mica plotted on the biotite classification diagram of Rieder et al. (1998). 4. Clinopyroxene composition in nepheline syenite and calcio-carbonatite phenocrysts illustrated on the classification ternary for sodic pyroxenes (after Morimoto; 1989). Quad (Q) represents wollastonite, enstatite and ferrosilite of the Mg-Ca-Fe group of pyroxenes. 5. The range of carbonatite compositions illustrated on the carbonatite classification diagram of Gittins and Harmer (1997). 6. Composition of the Lofdal nepheline syenite on the plutonic Total-Alkali-Silica diagram of Wilson (1989). 7. a. A binary plot showing the concentration of Y versus that of Ho in bulk rock samples of the phono-tephrites, phonolites, nepheline syenites and carbonatites. The trend-line represents the mantle value of approximately 27.7 (Sun and McDonough, 1989). b. A binary plot showing the concentration of Nb versus that of Ta in bulk rock samples of the phono-tephrites, phonolites, nepheline syenites and carbonatites. The trend-line represents the mantle value of approximately 17.4 (Sun and McDonough, 1989). c. A binary plot showing the concentration of Zr versus that of Hf in bulk rock samples of the phono-tephrites, phonolites, nepheline syenites and carbonatites. The trend-line represents the mantle value of approximately 36.2 (Sun and McDonough, 1989). 8. A binary plot showing the concentration of K2O versus Na2O in nepheline syenite and fenite.

Amphibole reaction rims as a record of pre-eruptive magmatic heating: An experimental approach

USGS Publications Warehouse

De Angelis, S. H.; Larsen, J.; Coombs, Michelle L.; Dunn, A.; Hayden, Leslie A.

2015-01-01

Magmatic minerals record the pre-eruptive timescales of magma ascent and mixing in crustal reservoirs and conduits. Investigations of the mineral records of magmatic processes are fundamental to our understanding of what controls eruption style, as ascent rates and magma mixing processes are well known to control and/or trigger potentially hazardous explosive eruptions. Thus, amphibole reaction rims are often used to infer pre-eruptive magma dynamics, and in particular to estimate magma ascent rates. However, while several experimental studies have investigated amphibole destabilization during decompression, only two investigated thermal destabilization relevant to magma mixing processes. This study examines amphibole decomposition experimentally through isobaric heating of magnesio-hornblende phenocrysts within a natural high-silica andesite glass. The experiments first equilibrated for 24 h at 870 °C and 140 MPa at H2O-saturated conditions and ƒO2 ∼ Re–ReO prior to rapid heating to 880, 900, or 920 °C and hold times of 3–48 h. At 920 °C, rim thicknesses increased from 17 μm after 3 h, to 55 μm after 12 h, and became pseudomorphs after longer durations. At 900 °C, rim thicknesses increased from 7 μm after 3 h, to 80 μm after 24 h, to pseudomorphs after longer durations. At 880 °C, rim thicknesses increased from 7 μm after 3 h, to 18 μm after 36 h, to pseudomorphs after 48 h. Reaction rim microlites vary from 5–16 μm in size, with no systematic relationship between crystal size and the duration or magnitude of heating. Time-averaged rim microlite growth rates decrease steadily with increasing experimental duration (from  to 3.1 to ). Time-averaged microlite nucleation rates also decrease with increasing experimental duration (from  to 5.3 mm−3 s−1). There is no systematic relationship between time-averaged growth or nucleation rates and the magnitude of the heating step. Ortho- and clinopyroxene together constitute 57–90 modal % mineralogy in each reaction rim. At constant temperature, clinopyroxene abundances decrease with increasing experimental duration, from 72 modal % (3 h at 900 °C) to 0% (48 h at 880 °C, and 36 h at 900 and 920 °C). Fe–Ti oxides increase from 6–12 modal % (after 3–6 h) to 26–34 modal % (after 36–48 h). Plagioclase occurs in relatively minor amounts (<1–11 modal %), with anorthite contents that increase from An56 to An88 from 3 to 36 h of heating. Distal glass compositions (>500 μm from reacted amphibole) are consistent with inter-microlite rim glasses (71.3–77.7 wt.% SiO2) within a given experiment and there is a weakly positive correlation between increasing run duration and inter-microlite melt SiO2 (68.9–78.5 wt.%). Our results indicate that experimental heating-induced amphibole reaction rims have thicknesses, textures, and mineralogies consistent with many of the natural reaction rims seen at arc-andesite volcanoes. They are also texturally consistent with experimental decompression reaction rims. On this basis it may be challenging to distinguish between decompression and heating mechanisms in nature.

The Source of Proterozoic Anorthosites: Bringing It All Back Home

NASA Astrophysics Data System (ADS)

Scoates, J. S.

2004-05-01

Proterozoic anorthosites are coarse-grained cumulate igneous rocks dominated by plagioclase of intermediate composition (An70-35) that occur in spatial and temporal association with both intrusions of troctolite and Fe-enriched rocks (ferrodiorite, monzonite) and with predominantly crustally-derived granitic batholiths. Given the relatively limited range of plagioclase compositions within individual intrusions, differences in plagioclase anorthite content between intrusions likely reflects primarily differences in pressures of segregation of plagioclase-rich magma bodies (An content of plag decreases with increasing pressures of crystallization). More importantly, Proterozoic anorthosite plutonic suites formed over an extended interval of time (1.2 byr) during the Middle Proterozoic from 2.1-0.9 Ga and thus are recording fundamental relationships between plate tectonics, mantle temperatures, and crust-mantle interactions over 1/4 of Earth history. Experimental work on opx-normative gabbroic/dioritic rocks from Harp Lake and Rogaland appears to show that some proposed anorthosite parental liquids lie across the trace of the plag+2-px cotectic from 1-1.3 GPa and that they straddle the thermal divide on the plag+px liquidus surface, thus apparently requiring a mafic source region (i.e. lower continental crust). It is unlikely that small amounts of dry partial melting of lower crustal granulite will produce melt compositions that are strongly plag-saturated nor will it yield the large quantities of melt (and corresponding cumulates) required by mass balance constraints. In addition, noritic-gabbronoritic lower crust is opx-normative and cannot be responsible for producing the olivine-bearing anorthosites or troctolites typical of the largest Proterozoic anorthosites. A compilation of high-Al,Fe basaltic magmas from Proterozoic anorthosite plutonic suites worldwide shows them to have compositions that are significantly less silica-rich than the opx-normative rocks that plot along the plag+2-px cotectic at high pressures. The important thermal divide for the petrogenesis of Proterozoic anorthosites is the plag+olivine+cpx divide as it separates opx-absent from opx-present fractionation trends at mid-crustal pressures. The least fractionated ol-normative compositions project into the region of mantle-derived melts at relatively high pressures (1-1.3 GPa). Radiogenic isotopic studies (Pb, Nd, Sr, Os) are particularly useful for constraining crustal input to anorthosite and have successfully traced out different-aged crustal reservoirs beneath them, especially when the underlying crust is 1 byr or more older than the anorthosites (e.g. Nain). Os isotopic studies do not effectively constrain the source of Proterozoic anorthosites, but rather yield important information about additions of crustal sulfur to ascending and slowly-cooling anorthosite bodies. Although a lower crustal tongue melting origin for Proterozoic anorthosites is clearly untenable, it is likely that no magma associated with Proterozoic anorthosites escaped contamination during ascent through the crust. The lower crust may have acted as a highly effective near-solidus "reactive filter" capable of stabilizing plagioclase as a liquidus phase for the duration of these long-lived (tens of millions of years for the largest suites), low magma flux magmatic systems. Combined low magma productivity and flux are consistent with only small amounts of crustal extension implicating the compositionally heterogeneous continental lithospheric mantle as the dominant source component for Proterozoic anorthosites.

Differential rates of feldspar weathering in granitic regoliths

USGS Publications Warehouse

White, A.F.; Bullen, T.D.; Schulz, M.S.; Blum, A.E.; Huntington, T.G.; Peters, N.E.

2001-01-01

Differential rates of plagioclase and K-feldspar weathering commonly observed in bedrock and soil environments are examined in terms of chemical kinetic and solubility controls and hydrologic permeability. For the Panola regolith, in the Georgia Piedmont Province of southeastern United States, petrographic observations, coupled with elemental balances and 87Sr/86Sr ratios, indicate that plagioclase is being converted to kaolinite at depths > 6 m in the granitic bedrock. K-feldspar remains pristine in the bedrock but subsequently weathers to kaolinite at the overlying saprolite. In contrast, both plagioclase and K-feldspar remain stable in granitic bedrocks elsewhere in Piedmont Province, such as Davis Run, Virginia, where feldspars weather concurrently in an overlying thick saprolite sequence. Kinetic rate constants, mineral surface areas, and secondary hydraulic conductivities are fitted to feldspar losses with depth in the Panola and Davis Run regoliths using a time-depth computer spreadsheet model. The primary hydraulic conductivities, describing the rates of meteoric water penetration into the pristine granites, are assumed to be equal to the propagation rates of weathering fronts, which, based on cosmogenic isotope dating, are 7 m/106 yr for the Panola regolith and 4 m/106 yr for the Davis Run regolith. Best fits in the calculations indicate that the kinetic rate constants for plagioclase in both regoliths are factors of two to three times faster than K-feldspar, which is in agreement with experimental findings. However, the range for plagioclase and K-feldspar rates (kr = 1.5 x 10-17 to 2.8 x 10-16 mol m-2 s-1) is three to four orders of magnitude lower than for that for experimental feldspar dissolution rates and are among the slowest yet recorded for natural feldspar weathering. Such slow rates are attributed to the relatively old geomorphic ages of the Panola and Davis Run regoliths, implying that mineral surface reactivity decreases significantly with time. Differential feldspar weathering in the low-permeability Panola bedrock environment is more dependent on relative feldspar solubilities than on differences in kinetic reaction rates. Such weathering is very sensitive to primary and secondary hydraulic conductivities (qp and qs), which control both the fluid volumes passing through the regolith and the thermodynamic saturation of the feldspars. Bedrock permeability is primarily intragranular and is created by internal weathering of networks of interconnected plagioclase phenocrysts. Saprolite permeability is principally intergranular and is the result of dissolution of silicate phases during isovolumetric weathering. A secondary to primary hydraulic conductivity ratio of qs/qp = 150 in the Panola bedrock results in kinetically controlled plagioclase dissolution but thermodynamically inhibited K-feldspar reaction. This result is in accord with calculated chemical saturation states for groundwater sampled in the Panola Granite. In contrast, greater secondary conductivities in the Davis Run saprolite, qs/qp = 800, produces both kinetically controlled plagioclase and K-feldspar dissolution. Faster plagioclase reaction, leading to bedrock weathering in the Panola Granite but not at Davis Run, is attributed to a higher anorthite component of the plagioclase and a wetter and warmer climate. In addition, the Panola Granite has an abnormally high content of disseminated calcite, the dissolution of which precedes the plagioclase weathering front, thus creating additional secondary permeability. Copyright ?? 2001 Elsevier Science Ltd.

Mount St. Augustine volcano fumarole wall rock alteration: Mineralogy, zoning, composition and numerical models of its formation process

USGS Publications Warehouse

Getahun, A.; Reed, M.H.; Symonds, R.

1996-01-01

Intensely altered wall rock was collected from high-temperature (640??C) and low-temperature (375??C) vents at Augustine volcano in July 1989. The high-temperature altered rock exhibits distinct mineral zoning differentiated by color bands. In order of decreasing temperature, the color bands and their mineral assemblages are: (a) white to grey (tridymite-anhydrite); (b) pink to red (tridymite-hematite-Fe hydroxide-molysite (FeCl3) with minor amounts of anhydrite and halite); and (c) dark green to green (anhydrite-halite-sylvite-tridymite with minor amounts of molysite, soda and potash alum, and other sodium and potassium sulfates). The alteration products around the low-temperature vents are dominantly cristobalite and amorphous silica with minor potash and soda alum, aphthitalite, alunogen and anhydrite. Compared to fresh 1986 Augustine lava, the altered rocks exhibit enrichments in silica, base metals, halogens and sulfur and show very strong depletions in Al in all alteration zones and in iron, alkali and alkaline earth elements in some of the alteration zones. To help understand the origins of the mineral assemblages in altered Augustine rocks, we applied the thermochemical modeling program, GASWORKS, in calculations of: (a) reaction of the 1987 and 1989 gases with wall rock at 640 and 375??C; (b) cooling of the 1987 gas from 870 to 100??C with and without mineral fractionation; (c) cooling of the 1989 gas from 757 to 100??C with and without mineral fractionation; and (d) mixing of the 1987 and 1989 gases with air. The 640??C gas-rock reaction produces an assemblage consisting of silicates (tridymite, albite, diopside, sanidine and andalusite), oxides (magnetite and hercynite) and sulfides (bornite, chalcocite, molybdenite and sphalerite). The 375??C gas-rock reaction produces dominantly silicates (quartz, albite, andalusite, microcline, cordierite, anorthite and tremolite) and subordinate amounts of sulfides (pyrite, chalcocite and wurtzite), oxides (magnetite), sulfates (anhydrite) and halides (halite). The cooling calculations produce: (a) anhydrite, halite, sylvite; (b) Cu, Mo, Fe and Zn sulfides; (c) Mg fluoride at high temperature (> 370??C); (d) chlorides, fluorides and sulfates of Mn, Fe, Zn, Cu and Al at intermediate temperature (170-370??C); and (e) hydrated sulfates, liquid sulfur, crystalline sulfur, hydrated sulfuric acid and water at low temperature ( 0.41 (> 628??C). This is followed by precipitation of sulfates of Fe, Cu, Pb, Zn and Al at lg/a ratios between 0.41 and -0.4 (628-178??C). At a lg/r ratio of < - 0.4 (178??C), anhydrous sulfates are replaced by their hydrated forms and hygroscopic sulfuric acid forms. At these low g/a ratios, hydrated sulfuric acid becomes the dominant phase in the system. Comparison of the thermochemical modeling results with the natural samples suggests that the alteration assemblages include: (1) minerals that precipitate from direct cooling of the volcanic gas; (2) phases that form by volcanic gases mixing with air; and (3) phases that form by volcanic gas-air-rock reaction. A complex interplay of the three processes produces the observed mineral zoning. Another implication of the numerical simulation results is that most of the observed incrustation and sublimate minerals apparently formed below 700??C.

The origin of jarosite associated with a gossan on Archean gneiss in Southwest Greenland

NASA Astrophysics Data System (ADS)

Peng, Y.; Pratt, L. M.; Young, S. A.; Cadieux, S. B.; White, J. R.

2013-12-01

The mineral Jarosite [KFe3(SO4)2(OH)6] since its discovery, by Opportunity rover at Meridiani Planum on Mars, has been the subject of intense geochemical and environmental study over the last 5-10 years. Jarosite requires highly acidic, K-enriched, and oxidizing aqueous conditions for formation. Stable isotopes of O, H, and S of jarosite have the ability to record the temperatures of formation, environments of deposition, fluids, and fluid/atmospheric interactions. Therefore, the origin of jarosite is important for understanding present and past environmental conditions on Mars. Unfortunately, the origin of jarosite on Mars remains unclear. Jarosite is commonly found on Earth in the weathering zones of pyrite-bearing ore deposits, near-surface playa sediments in acid-saline lakes, or epithermal environments and hot springs. Here, we report the occurrence of jarosite in association with a gossan overlying weathered Archean gneiss and Paleoproterozoic mafic dikes at the ice-free margin of southwestern Greenland. In our 2012 field campaign, we excavated soil pits to a depth of 40 cm with a high vertical sampling resolution. No visible pyrite was found in the nearby outcroppings of gneiss in the field. XRD data show that all samples were composed of anorthite, quartz, albite, jarosite, muscovite, and microcline. Jarosite was the only sulfur-bearing mineral identified by XRD, with abundance of jarosite increasing with depth (up to 8.4 wt. %) in the soil pits. Water soluble and acid soluble sulfate were sequentially extracted using 10% NaCl and 2N HCl solutions, respectively. Pyrite was then subsequently extracted from insoluble residues by a chromium reduction method. The average abundance of water soluble sulfate, acid soluble sulfate, and pyrite were 100 ppm, 7 wt. %, and 10 ppm, respectively. The δ34S values of water soluble sulfate, acid soluble sulfate, and pyrite range from -0.7‰ to 3.1‰ (average= 1.5‰), -1.2 to 1.5‰ (average= 0.7‰), and 0.3‰ to 6.7‰ (average= 2.6‰) respectively. δ34S values of all water soluble sulfate and pyrite, were higher than acid soluble sulfate. δ34S values of pyrite were higher than all water soluble sulfate except the surficial sample (0-10 cm depth). The δ34S values of water soluble sulfate and acid soluble sulfate did not change with depth while δ34S values of pyrite increased with depth from 2.4‰ to 6.7 ‰ (peak at 10-15 cm) and dropped to 2.0‰. Preliminary data indicate that the acid soluble sulfate was dominated by jarosite while the water soluble sulfate fraction may have been a mixture of leached jarosite and other sulfate sources, such as atmospheric sulfate. Jarosite formation may result from the oxidative weathering of pyrite inferred to originate from localized, stratiform, hydrothermal mineralization. To constrain the origin of jarosite, a new profile containing soil, permafrost, and bedrock was collected at the same location during the summer 2013 field campaign by drilling ~ 1.0 meter into the permafrost zone. We will employ multiple sulfur isotope and triple oxygen isotope of sulfate and pyrite, which can define the source of sulfur and oxygen. A greater understanding of the formation of jarosite on this ice-free margin of Greenland will provide an insightful potential analogue for jarosite formation and on Mars.

Natural weathering in dry disposed ash dump: Insight from chemical, mineralogical and geochemical analysis of fresh and unsaturated drilled cores.

PubMed

Akinyemi, S A; Akinlua, A; Gitari, W M; Khuse, N; Eze, P; Akinyeye, R O; Petrik, L F

2012-07-15

Some existing alternative applications of coal fly ash such as cement manufacturing; road construction; landfill; and concrete and waste stabilisation use fresh ash directly collected from coal-fired power generating stations. Thus, if the rate of usage continues, the demand for fresh ash for various applications will exceed supply and use of weathered dry disposed ash will become necessary alternative. As a result it's imperative to understand the chemistry and pH behaviour of some metals inherent in dry disposed fly ash. The bulk chemical composition as determined by XRF analysis showed that SiO2, Al2O3 and Fe2O3 were the major oxides in fresh ash and unsaturated weathered ashes. The unsaturated weathered ashes are relatively depleted in CaO, Fe2O3, TiO2, SiO2, Na2O and P2O5 due to dissolution and hydrolysis caused by chemical interaction with ingressing CO2 from the atmosphere and infiltrating rain water. Observed accumulations of Fe2O3, TiO2, CaO, K2O, Na2O and SO3 and Zn, Zr, Sr, Pb, Ni, Cr and Co in the lower layers indicate progressive downward movement through the ash dump though at a slow rate. The bulk mineralogy of unsaturated weathered dry disposed ash, as determined by XRD analysis, revealed quartz and mullite as the major crystalline phases; while anorthite, hematite, enstatite, lime, calcite, and mica were present as minor mineral phases. Pore water chemistry revealed a low concentration of readily soluble metals in unsaturated weathered ashes in comparison with fresh ash, which shows high leachability. This suggests that over time the precipitation of transient minor secondary mineral phases; such as calcite and mica might retard residual metal release from unsaturated weathered ash. Chloride and sulphate species of the water soluble extracts of weathered ash are at equilibrium with Na+ and K+; these demonstrate progressive leaching over time and become supersaturated at the base of unsaturated weathered ash. This suggests that the ash dump does not encapsulate the salt or act as a sustainable salt sink due to over time reduction in pore water pH. The leaching behaviours of Ca, Mg, Na+, K+, Se, Cr and Sr are controlled by the pH of the leachant in both fresh and unsaturated weathered ash. Other trace metals like As, Mo and Pb showed amphoteric behaviour with respect to the pH of the leachant. The precipitation of minor quantities of secondary mineral phases in the unsaturated weathered ash has significant effects on the acid susceptibility and leaching patterns of chemical species in comparison with fresh ash. The unsaturated weathered ash had lower buffering capacity at neutral pH (7.94-8.00) compared to fresh (unweathered) ash. This may be due to the initial high leaching/flushing of soluble basic buffering constituents from fly ash after disposal. The overall results of the acid susceptibility tests suggest that both fresh ash and unsaturated weathered ash would release a large percentage of their chemical species when in contact with slightly acidified rain. Proper management of ash dumps is therefore essential to safeguard the environmental risks of water percolation in different fly ashes behaviour. Copyright © 2012 Elsevier Ltd. All rights reserved.

Geochemistry of biotite granites from the Lamas de Olo Pluton, northern Portugal

NASA Astrophysics Data System (ADS)

Fernandes, Susana; Gomes, Maria; Teixeira, Rui; Corfu, Fernando

2013-04-01

In the Central Iberian Zone (CIZ) extensive crustal recycling occurred during the post-thickening extension stage of the Variscan orogeny (~330-290 Ma). After the ductile deformation phase D3 (~320-300 Ma), characterized by the intrusion of large volumes of highly peraluminous granitic magmas, rapid and drastic tectonic changes at about 300 Ma gave rise to the brittle phase of deformation D4 that controlled the emplacement of Fe-K subalkaline granites (296-290 Ma; Dias et al. 1998). The Lamas de Olo Pluton (LOP) is controlled by NE-SW and NW-SE fracture systems, probably related to the Régua-Verin fault zone (Pereira, 1989). The LOP is a medium to coarse-grained, porphyritic biotite granite, accompanied by medium- to fine grained, porphyritic biotite granite (Alto dos Cabeços- AC) and a more leucocratic, fine-grained, slightly porphyritic biotite-muscovite granite (Barragens- BA). The contacts between LO and AC are generally diffuse, whereas those to BA are sharp. In fact, the BA granite can occur in dykes and sills cutting LO and AC. Microgranular enclaves and xenoliths are very rare. The LOP intrudes the Douro Group, presumably of Precambrian to Cambrian age, and two-mica granites from the Vila Real composite massif. The LOP granites consist of quartz, microcline, plagioclase, biotite, zircon, titanite, tourmaline apatite, fluorite, ilmenite, magnetite, and rutile, with muscovite in BA granite and rare allanite in the LO and AC granites. The plagioclase composition is of oligoclase (An12) - andesine (An35) for LO granite, albite (An9) - andesine (An30) for CA granite and albite (An5) - oligoclase (An20) for BA granite. There are decreases in: a) anorthite content from phenocryst to matrix plagioclase; b) Ba content from phenocryst to matrix microcline in all granites. The Fe2+ biotite has a composition similar to that of biotite from calc-alkaline to sub-alkaline rock series. The LO and AC granites are meta- to peraluminous with ASI variable between 1.05 and 1.21, and display isotopic signatures of (87Sr/86Sr)i = 0.7044-0.7077 and Nd = -2.2 to -1.1. Six samples of LO define a whole rock isochron age of 285±15 Ma with (87Sr/86Sr)i = 0.7051±0.001 (MSWD = 0.11). Two monazite analyses for the LO granite yield an weighted average 207Pb/235U age of 297.19±0.73 Ma, consistent with the preliminary ID-TIMS U-Pb analyses of two transparent and euhedral prisms of zircon that define a concordia age of 296.37 ±0.52 Ma (MSWD = 0.66). The linear trends of major and trace elements variation diagrams of LO and AC granites and their similar mean values of (87Sr/86Sr)i point, at this stage, to an involvement of mid-crustal sources, probably mixed with asthenospheric material. Therefore, LOP consists of post-D3 biotite granites installed in higher structural crustal levels, testifying the occurrence of a crustal growth episode after the major recycling processes that occurred during the deformation phase D3. We thank Prof. J.F. Santos and Dr. S. Ribeiro and Petrochron project (PTDC/CTE-GIX/112561/2009) for the Rb-Sr isotopic data obtained at LGI of University of Aveiro, Portugal. Dias, G. et al. 1998. Lithos, 45, 349-369. Pereira, E., 1989. Serviços Geológicos de Portugal.

Characterization and modes of occurrence of elements in feed coal and coal combustion products from a power plant utilizing low-sulfur coal from the Powder River Basin, Wyoming

USGS Publications Warehouse

Brownfield, Michael E.; Cathcart, James D.; Affolter, Ronald H.; Brownfield, Isabelle K.; Rice, Cynthia A.; O'Connor, Joseph T.; Zielinski, Robert A.; Bullock, John H.; Hower, James C.; Meeker, Gregory P.

2005-01-01

The U.S. Geological Survey and the University of Kentucky Center for Applied Energy Research are collaborating with an Indiana utility company to determine the physical and chemical properties of feed coal and coal combustion products from a coal-fired power plant. The Indiana power plant utilizes a low-sulfur (0.23 to 0.47 weight percent S) and lowash (4.9 to 6.3 weight percent ash) subbituminous coal from the Wyodak-Anderson coal zone in the Tongue River Member of the Paleocene Fort Union Formation, Powder River Basin, Wyoming. Based on scanning electron microscope and X-ray diffraction analyses of feed coal samples, two mineral suites were identified: (1) a primary or detrital suite consisting of quartz (including beta-form grains), biotite, feldspar, and minor zircon; and (2) a secondary authigenic mineral suite containing alumino-phosphates (crandallite and gorceixite), kaolinite, carbonates (calcite and dolomite), quartz, anatase, barite, and pyrite. The primary mineral suite is interpreted, in part, to be of volcanic origin, whereas the authigenic mineral suite is interpreted, in part, to be the result of the alteration of the volcanic minerals. The mineral suites have contributed to the higher amounts of barium, calcium, magnesium, phosphorus, sodium, strontium, and titanium in the Powder River Basin feed coals in comparison to eastern coals. X-ray diffraction analysis indicates that (1) fly ash is mostly aluminate glass, perovskite, lime, gehlenite, quartz, and phosphates with minor amounts of periclase, anhydrite, hematite, and spinel group minerals; and (2) bottom ash is predominantly quartz, plagioclase (albite and anorthite), pyroxene (augite and fassaite), rhodonite, and akermanite, and spinel group minerals. Microprobe and scanning electron microscope analyses of fly ash samples revealed quartz, zircon, and monazite, euhedral laths of corundum with merrillite, hematite, dendritic spinels/ferrites, wollastonite, and periclase. The abundant calcium and magnesium mineral phases in the fly ash are attributed to the presence of carbonate, clay, and phosphate minerals in the feed coal and their alteration to new phases during combustion. The amorphous diffraction-scattering maxima or glass 'hump' appears to reflect differences in chemical composition of fly ash and bottom ash glasses. In Wyodak-Anderson fly and bottom ashes, the center point of scattering maxima is due to calcium and magnesium content, whereas the glass 'hump' of eastern fly ash reflects variation in aluminum content. The calcium- and magnesium-rich and alumino-phosphate mineral phases in the coal combustion products can be attributed to volcanic minerals deposited in peat-forming mires. Dissolution and alteration of these detrital volcanic minerals occurred either in the peat-forming stage or during coalification and diagenesis, resulting in the authigenic mineral suite. The presence of free lime (CaO) in fly ash produced from Wyodak-Anderson coal acts as a self-contained 'scrubber' for SO3, where CaO + SO3 form anhydrite either during combustion or in the upper parts of the boiler. Considering the high lime content in the fly ash and the resulting hydration reactions after its contact with water, there is little evidence that major amounts of leachable metals are mobilized in the disposal or utilization of this fly ash.

Geochemical modeling of arsenic sulfide oxidation kinetics in a mining environment

NASA Astrophysics Data System (ADS)

Lengke, Maggy F.; Tempel, Regina N.

2005-01-01

Arsenic sulfide (AsS (am), As 2S 3 (am), orpiment, and realgar) oxidation rates increase with increasing pH values. The rates of arsenic sulfide oxidation at higher pH values relative to those at pH˜2 are in the range of 26-4478, 3-17, 8-182, and 4-10 times for As 2S 3 (am), orpiment, AsS (am), and realgar, respectively. Numerical simulations of orpiment and realgar oxidation kinetics were conducted using the geochemical reaction path code EQ3/6 to evaluate the effects of variable DO concentrations and mineral reactivity factors on water chemistry evolution during orpiment and realgar oxidation. The results show that total As concentrations increase by ˜1.14 to 13 times and that pH values decrease by ˜0.6 to 4.2 U over a range of mineral reactivity factors from 1% to 50% after 2000 days (5.5 yr). The As release from orpiment and realgar oxidation exceeds the current U.S. National Drinking Water Standard (0.05 ppm) approximately in 200-300 days at the lowest initial dissolved oxygen concentration (3 ppm) and a reactivity factor of 1%. The results of simulations of orpiment oxidation in the presence of albite and calcite show that calcite can act as an effective buffer to the acid water produced from orpiment oxidation within relatively short periods (days/months), but the release of As continues to increase. Pyrite oxidation rates are faster than orpiment and realgar from pH 2.3 to 8; however, pyrite oxidation rates are slower than As 2S 3 (am) and AsS (am) at pH 8. The activation energies of arsenic sulfide oxidation range from 16 to 124 kJ/mol at pH˜8 and temperature 25 to 40°C, and pyrite activation energies are ˜52 to 88 kJ/mol, depending on pH and temperature range. The magnitude of activation energies for both pyrite and arsenic sulfide solids indicates that the oxidation of these minerals is dominated by surface reactions, except for As 2S 3 (am). Low activation energies of As 2S 3 (am) indicate that diffusion may be rate controlling. Limestone is commonly mixed with sulfide minerals in a mining environment to prevent acid water formation. However, the oxidation rates of arsenic sulfides increase as solution pH rises and result in a greater release of As. Furthermore, the lifetimes of carbonate minerals (i.e., calcite, aragonite, and dolomite) are much shorter than those of arsenic sulfide and silicate minerals. Thus, within a geologic frame time, carbonate minerals may not be present to act as a pH buffer for acid mine waters. Additionally, the presence of silicate minerals such as pyroxenes (wollastonite, jadeite, and spodumene) and Ca-feldspars (labradorite, anorthite, and nepheline) may not be important for buffering acid solutions because these minerals dissolve faster than and have shorter lifetimes than sulfide minerals. However, other silicate minerals such as Na and K-feldspars (albite, sanidine, and microcline), quartz, pyroxenes (augite, enstatite, diopsite, and MnSiO 3) that have much longer lifetimes than arsenic sulfide minerals may be present in a system. The results of our modeling of arsenic sulfide mineral oxidation show that these minerals potentially can release significant concentrations of dissolved As to natural waters, and the factors and mechanisms involved in arsenic sulfide oxidation warrant further study.

P-T evolution of the Precambrian mafic rocks hosting the Varena iron ore deposit in SE Lithuania

NASA Astrophysics Data System (ADS)

Šiliauskas, Laurynas; Skridlaitė, Gražina; Prusinskiene, Sabina

2017-04-01

The Precambrian Varena iron ore deposit in the western East European Craton, near the Latvian-East Lithuanian and Middle Lithuanian domain boundary, is buried beneath 210-500 m thick sediments. It consists of variable metasomatic rocks, mostly Mg-Fe skarns, associated with dolomitic marbles, magnetite and other ores. Metasomatites are hosted by metamorphosed igneous (mostly mafic) and sedimentary rocks and crosscut by later granites and diabase dikes. Three samples of altered mafic rocks (D8-3, D8-4 and D8-6) were chosen for PT estimations. D8-3 sample (582.5 m) is a coarse-grained metagabbro near a metasomatic K-Mg hastingsite rock. It consists of diopsidic pyroxene, edenitic and actinolitic hornblende, plagioclase (An22-15) and scapolite with minor titanite, chlorite, apatite and talc. Diopside compositions range from iron richer (Mg# 0.64, jadeite component of 0.027) to magnesium richer (Mg# 0.89, jadeite less than 0.01). Amphiboles vary from primary Mg-hastingsitic (AlVI 0.38 apfu, Mg# 0.70) to secondary edenitic (AlVI 0.25, Mg# 0.72) hornblende. Plagioclase is slightly zoned, cores more calcium-rich (An22-20) than rims (An18-15). Sample D8-4 (588 m) has similar mineral and chemical compositions, but is somewhat more altered than the D8-3 sample. Plagioclase in diopside is more anorthitic (An32-30), while matrix plagioclase is more albitic (An27-20). Sample D8-6 (710 m) is composed of diopside, plagioclase, scapolite, Mg-hornblende and actinolite. Diopside has Mg# of 0.77-0.84 and jadeite component of 0.01-0.02. Amphibole compositions range from Mg-hornblende (Mg# 0.64-0.7, Al VI 0.2-0.17 apfu) to actinolite (Mg# 0.76-0.83, Al VI 0.12-0.10 apfu). Plagioclases are An18 in cores and An10 at rims. Diopsides with the lowest Mg# and highest jadeite components, together with plagioclase cores were used for PT calculations by the winTWQ software (Berman, 1991). Temperatures of 530° C and 550° C and pressures of 6.3 and 6.1 kbar were estimated for the D8-3 and D8-4 samples, respectively. Edenitic (D8-3 and D8-4) and Mg-hornblende (D8-6) and plagioclase rims were used for thermobarometric calculations (Holland and Blundy, 1994 etc). The sample D8-3 yielded 690° to 600° C and 5.6 to 4.6 kbar (4.3 kbar pressures at maximum temperature). Similar results (675-716° C and 4.1-5.5 kbar, 4.9 kbar pressures at maximum temperature) were obtained from the D8-4 sample. The sample D8-6 produced somewhat lower values of 669-532° C and 3.7-1.0 kbar. The D8-3 gabbro may belong to the surrounding c. 1.84 Ga (Bogdanova et al., 2015) Randamonys complex. The gabbros were later metamorphosed at 550oC and 6.3 kbar (peak by clinopyroxene-plagioclase assemblages). A slight decompression to 5.0-4.3 kbar and reheating to c. 700o C (hornblende-plagioclase assemblages) were likely caused by the fluid influx and metasomatism. Such hornblende yielded c. 1.62 Ga age in the neighbouring 982 drilling (40Ar/39Ar age; Bogdanova et al., 2001). The later retrogression to 530o C at c. 3 kbar coincided with the hornblende closure temperature presumably at 1.47 Ga as was recorded in the same 982 drilling. Berman, 1991. CAN MINERAL, 29, 833-856. Bogdanova, S. et al., 2001. Tectonophysics, 339, 39-66. Bogdanova, S. et al., 2015. Precambrian Research, 259, 5-33. Holland, T., Blundy, J., 1994. CONTRIB MINERAL PETROL 116, 433-47.

In-situ fractional crystallization as a major mechanism in differentiation of Karaj sill, northern Iran

NASA Astrophysics Data System (ADS)

Maghdour-Mashhour, Reza; Esmaeily, Dariush

2010-05-01

During the upper Eocene-Oligocene, the Karaj Dam basement sill (KDBS), located within the E-W-trending Alborz range in northern Iran, intruded the middle and upper tuff units of the Karaj Formation. The KDBS consists of a layered series between upper and lower chilled margins, with local fine-grained monzonitic dykes. The rocks of the chilled margins are gabbroic in composition and show porphyritic texture. The rocks show a continuous transition from porphyritic to equigranular texture toward the center of the sill. Most of the KDBS is medium to coarse grained, showing magmatic layering defined by modal variations in pyroxene and plagioclase, the main constituent minerals. The layered series, dominated by gabbro, diorite, and monzodiorite, formed almost upward from the lower to the upper chilled margin, with gradational transitions between rock types. The KDBS shows an S-shaped profile of MgO concentration from the base to the top of the sill. In situ crystallization is indicated by an approximately constant modal abundance of pyroxene and plagioclase, a narrow range of major element contents in the main lithologies (e.g., 49-54 wt% SiO2, 17-19 wt% Al2O3, and 2.7-5.2 wt% MgO), and variable trace element concentrations (e.g., 500-1150 ppm Ba, 45-130 ppm Rb, 150-720ppm Sr, and 50-160 ppm Zr). Disequilibrium crystallization, caused by Soret fractionation in the marginal series, is indicated by an unexpected overall enrichment trend in MgO concentration and Mg# of pyroxenes from the chilled margin (olivine-bearing gabbro) to marginal gabbro. Formation of chilled margins form an effective insulating layer between contacts and overlaying hot, turbulent magma causing magma cool considerably slowly and have sufficient time to produce different differentiated sequence by in-situ nucleation and growth from gabbro to diorite and monzodiorite. Following the formation of chilled margins, the parent magma composition was established on the Plg-Cpx cotectic line of the Ol-Plg-Cpx ternary system or in the Plg field of the Cpx-Ab-An phase system. In the latter system, Plg starts to crystallize in mushy layers and its composition changes from anorthite to albite until reaching the cotectic line, at which point Cpx starts to form. The presence of plagioclase laths as inclusions within large crystals of clinopyroxene indicates cotectic crystallization and the early crystallization of Plg during formation of the gabbroic unit. Subsequently, the liquid line of descent followed the cotectic line toward the Ab-Cpx eutectic point. During this process, gabbroic cumulate formed at the solidified margins of the magma chamber. After the formation of Plg-Cpx cumulate, the evolved interstitial liquid, which had undergone chemical fractionation, migrated out of the gabbroic cumulate pile within the main magma body, thereby changing the composition of the magma reservoir. Consequently, the melt composition would have been different from the initial melt, being more evolved. The subsequent evolution of the liquid line of descent of compositionally new melt followed the same path at every stage of the formation of new melt; the An% of plagioclase decreased and Ab% increased to approximately 40%. In addition, the Cpx content showed a gradual decrease. Eventually, the Plg accumulates as dioritic cumulate in solidified margins of the chamber. Subsequently, the composition of the main magma changed, approaching the eutectic point of the Or-Ab solid solution binary system. in time, at the eutectic point, Kf started to crystallize and formed monzodiorites downward from the roof of the magma chamber during the final stages of differentiation. Although gravitational crystal settling contributed to the evolution of these rocks, it is not considered to have been a major factor in the development of the observed layering.

Lunar and Planetary Science XXXVI, Part 19

NASA Technical Reports Server (NTRS)

2005-01-01

The topics include: 1) The abundances of Iron-60 in Pyroxene Chondrules from Unequilibrated Ordinary Chondrites; 2) LL-Ordinary Chondrite Impact on the Moon: Results from the 3.9 Ga Impact Melt at the Landing Site of Appolo 17; 3) Evaluation of Chemical Methods for Projectile Identification in Terrestrial and Lunar Impactites; 4) Impact Cratering Experiments in Microgravity Environment; 5) New Achondrites with High-Calcium Pyroxene and Its implication for Igneous Differentiation of Asteroids; 6) Climate History of the Polar Regions of Mars Deduced form Geologic Mapping Results; 7) The crater Production Function for Mars: A-2 Cumulative Power-Law Slope for Pristine Craters Greater than 5 km in Diameter Based on Crater Distribution for Northern Plains Materials; 8) High Resolution Al-26 Chronology: Resolved Time Interval Between Rim and Interior of a Highly Fractionated Compact Type a CAI from Efremovka; 9) Assessing Aqueous Alteration on Mars Using Global Distributions of K and Th; 10) FeNi Metal Grains in LaPaz Mare Basalt Meteorites and Appolo 12 Basalts; 11) Unique Properties of Lunar Soil for In Situ Resource Utilization on the Moon; 12) U-Pb Systematics of Phosphates in Nakhlites; 13) Measurements of Sound Speed in Granular Materials Simulated Regolith; 14) The Effects of Oxygen, Sulphur and Silicon on the Dihedral Angles Between Fe-rich Liquid Metal and Olivine, Ringwoodite and Silicate Perovskite: Implications for Planetary Core Formation; 15) Seismic Shaking Removal of Craters 0.2-0.5 km in Diameter on Asteroid 433 Eros; 16) Focused Ion Beam Microscoopy of ALH84001 Carbonate Disks; 17) Simulating Micro-Gravity in the Laboratory; 18) Mars Atmospheric Sample Return Instrument Development; 19) Combined Remote LIBS and Raman Spectroscopy Measurements; 20) Unusual Radar Backscatter Properties Along the Northern Rim of Imbrium Basin; 21) The Mars Express/NASAS Project at JPL; 22) The Geology of the Viking 2 Lander Site Revisited; 23) An Impact Genesis for Loki Patera? 24) Mars Polar Cap Edges Tracked over 3 Full Mars Years; 25) Elemental Abundance in Presolar SiC: Comparing Grains Separated by Acid Residue and Gently Separation Procedures; 26) First Results from the Descent Imager/Spectral Radiometer (DISR) Experiment on the Huygens Entry Probe of Titan; 27) Minor Element Behavior of Pallasite Olivine: Understanding Pallasite Thermal History and Chronology; 28) Canonical Anorthite in a Grosnaja Forsterite-bearing CAI; 29) Experimental Evidence for Condensation of 'Astrophysical' Carbonate; 30) Distribution and Classification of Multiple Coronae on Venus; 31) Recognition of Rayed Craters on Mars in THEMIS Thermal Infrared Imagery: Implications for Martian Meteorite Source Regions; 32) Geochemical Modeling of Evaporites on Mars: Insight from Meridiani Planum; 33) Hadean Crustal Processes Revealed from Oxygen Isotopes and U-Th-Pb Depth Profiling of Pre-4.0 Ga Detrital Zircons from Western Australia; 34) On Modeling the Seepage of Water into the Martian Subsurface; 35) Martial Gullies and Groundwater: A Series of Unfortunate Exceptions; 36) Olivine and Carbonate Globules in ALH84001: A Terrestrial Analog, and Implications for Water on Mars; 37) A Reevaluation of Mass Movements Within the Valles Marineris Region of Mars Using MOLA and MOC Data; 38) Evidence of Hydrated 109P/Swift-Tuttle Meteoroids from Meteor Spectroscopy; 39) Cr-54 Anomalies in the Solar System: Their Extent and Origin; 40) Reevaluation of the Mn-53-Cr-53 Systematic in the Basaltic Achondrites; 41) Effective Liquid Metal-Silicate Mixing Upon Shock by Power-Law Droplet Size Scaling in Richtmyer-Meshkov Like Perturbations; 42) Post-Impact Deformation of Impact Craters: Towards a Better Understanding Through the Study of Mjolnir Crater; 43) Cutting Silica Aerogel for Particle Extraction; 44) Liquid Hydrocarbons on Titan's Surface? How Cassini ISS Observations Fit into the Story (So Far); and 45) Mesoscale Simulations of Polar Circulations: Late Spring to Late Summe

Hydrogen concentration in plagioclaes as a hygrometer of magmas: Approaches from melt inclusion analyses and hydrous melting experiments

NASA Astrophysics Data System (ADS)

Hamada, M.; Ushioda, M.; Fujii, T.; Takahashi, E.

2012-12-01

Plagioclase is one of the nominally anhydrous minerals (NAMs) which accommodates hundreds wt. ppm of hydrogen. Hydrogen in igneous plagioclase (OH) can act as a proxy of dissolved H2O in silicate melt. In order to use it as a practical hygrometer of magmas, we studied partitioning of hydrogen between plagioclase and basaltic melt dis-solving H2O (0.3˜5.5 wt.%) by two approaches: analyses of plagioclase-hosted melt inclusions (H2O≈0.3 wt.%) from mid-ocean ridge basalt (MORB) and hydrogen partitioning experiments between An96 plagioclase and hydrous basaltic melt (0.8 wt.%≦H2O≦5.5 wt.%) at 0.35 GPa. Concentration hydrogen in plagioclase and concentration of H2O in basaltic glasses were analyzed by infrared spectroscopy. As a first series of this study, plagioclase-hosted melt inclusions in MORB (50.5% SiO2, 15.1% Al2O3, 7.4% MgO) from the Rodriguez triple junction in the Indian Ocean were analyzed. The hydrogen concentration of plagioclase is less than 50 wt. ppm water, and no correlation between hydrogen concentration and anorthite content is recognized. Average H2O concentrations in melt inclusions is 0.3 wt.%. Therefore, apparent partition coefficient of hydrogen between plagioclase and melt is ≈ 0.01 in molar basis. As a second series of this study, hydrous melting experiments of arc basaltic magma were performed at 350 MPa using internally-heated pressure vessel. Starting material was hydrous glass (0.8 wt.%≦H2O≦5.5 wt.%) of an undifferentiated rock from Miyakejima volcano, a frontal-arc volcano in Izu-arc (MTL rock: 50.5% SiO2, 18.1% Al2O3, 4.9% MgO). A grain of Ca-rich plagioclase (≈1 mg, about An96) and 10 mg of powdered glasses were sealed in Au80Pd20 alloy capsule, and then kept at temperature at around the liquidus. Liquidus phase of MTL rock at 350 MPa is always plagioclase with 0 to 5.5 wt.% H2O in melt, and therefore, a grain of plagioclase and hydrous melt were nearly in equilibrium. Oxygen fugacity (fO2) during the melting experiments was not controlled, which was estimated to be 3 log unit above Ni-NiO buffer. Experiments were quenched after 24 hours, long enough to attain equi-librium partitioning of hydrogen between plagioclase and melt. Combining two series of study, we formulated empirical equation to correlate hydrogen concentration in plagioclase and H2O concentration in melt as: Hydrogen in plagioclase (wt. ppm water) ≈ 94.3×√(H2O in melt, wt.%). We also determined partition coefficient of hydrogen between plagioclase and basaltic melt to be 0.01±0.005 under H2O-poor conditions (≤150 wt. ppm water in plagioclase, ≤2 wt.% H2O in melt) and to be 0.008±0.002 under H2O-rich conditions (≥150 wt. ppm water in plagioclase, ≥2 wt.% H2O in melt). Slight decrease in hydrogen partitioning with increasing H2O can be related to change in hydrogen site in crystal structure of plagioclase (possibly tetrahedral sites). Peak position of infrared absorbance spectra lies at 3200-3400 cm-1 under H2O-poor condition and at 3600 cm-1 under H2O-rich condition, suggesting expansion of O-H…O bond length with increasing H2O.

Oxygen isotope trajectories of crystallizing melts: Insights from modeling and the plutonic record

NASA Astrophysics Data System (ADS)

Bucholz, Claire E.; Jagoutz, Oliver; VanTongeren, Jill A.; Setera, Jacob; Wang, Zhengrong

2017-06-01

Elevated oxygen isotope values in igneous rocks are often used to fingerprint supracrustal alteration or assimilation of material that once resided near the surface of the earth. The δ18O value of a melt, however, can also increase through closed-system fractional crystallization. In order to quantify the change in melt δ18O due to crystallization, we develop a detailed closed-system fractional crystallization mass balance model and apply it to six experimentally- and naturally-determined liquid lines of descent (LLDs), which cover nearly complete crystallization intervals (melt fractions of 1 to <0.1). The studied LLDs vary from anhydrous tholeiitic basalts to hydrous high-K and calc-alkaline basalts and are characterized by distinct melt temperature-SiO2 trajectories, as well as, crystallizing phase relationships. Our model results demonstrate that melt fraction-temperature-SiO2 relationships of crystallizing melts, which are strongly a function of magmatic water content, will control the specific δ18O path of a crystallizing melt. Hydrous melts, typical of subduction zones, undergo larger increases in δ18O during early stages of crystallization due to their lower magmatic temperatures, greater initial increases in SiO2 content, and high temperature stability of low δ18O phases, such as oxides, amphibole, and anorthitic plagioclase (versus albite). Conversely, relatively dry, tholeiitic melts only experience significant increases in δ18O at degrees of crystallization greater than 80%. Total calculated increases in melt δ18O of 1.0-1.5‰ can be attributed to crystallization from ∼50 to 70 wt.% SiO2 for modeled closed-system crystallizing melt compositions. As an example application, we compare our closed system model results to oxygen isotope mineral data from two natural plutonic sequences, a relatively dry, tholeiitic sequence from the Upper and Upper Main Zones (UUMZ) of the Bushveld Complex (South Africa) and a high-K, hydrous sequence from the arc-related Dariv Igneous Complex (Mongolia). These two sequences were chosen as their major and trace element compositions appear to have been predominantly controlled by closed-system fractional crystallization and their LLDs have been modeled in detail. We calculated equilibrium melt δ18O values using the measured mineral δ18O values and calculated mineral-melt fractionation factors. Increases of 2-3‰ and 1-1.5‰ in the equilibrium melts are observed for the Dariv Igneous Complex and the UUMZ of the Bushveld Complex, respectively. Closed-system fractional crystallization model results reproduce the 1‰ increase observed in the equilibrium melt δ18O for the Bushveld UUMZ, whereas for the Dariv Igneous Complex assimilation of high δ18O material is necessary to account for the increase in melt δ18O values. Assimilation of evolved supracrustal material is also confirmed with Sr and Nd isotope analyses of clinopyroxene from the sequence. Beginning with a range of mantle-derived basalt δ18O values of 5.7‰ ("pristine" mantle) to ∼7.0‰ (heavily subduction-influenced mantle), our model results demonstrated that high-silica melts (i.e. granites) with δ18O of up to 8.5‰ can be produced through fractional crystallization alone. Lastly, we model the zircon-melt δ18O fractionations of different LLDs, emphasizing their dependence on the specific SiO2-T relationships of a given crystallizing melt. Wet, relatively cool granitic melts will have larger zircon-melt fractionations, potentially by ∼1.5‰, compared to hot, dry granites. Therefore, it is critical to constrain zircon-melt fractionations specific to a system of interest when using zircon δ18O values to calculate melt δ18O.

Long-Term CO2 Exposure Experiments - Geochemical Effects on Brine-Saturated Reservoir Sandstone

NASA Astrophysics Data System (ADS)

Fischer, Sebastian; Zemke, Kornelia; Liebscher, Axel; Wandrey, Maren

2010-05-01

The injection of CO2 into deep saline aquifers is the most promising strategy for the reduction of CO2 emissions to the atmosphere via long-term geological storage. The study is part of the CO2SINK project conducted at Ketzin, situated 40 km west of Berlin. There, food grade CO2 has been pumped into the Upper Triassic Stuttgart Formation since June 2008. The main objective of the experimental program is to investigate the effects of long-term CO2 exposure on the physico-chemical properties of the reservoir rock. To achieve this goal, core samples from observation well Ktzi 202 have been saturated with synthetic brine and exposed to CO2 in high quality steel autoclaves at simulated reservoir P-T-conditions of 5.5 MPa and 40 ° C. The synthetic brine had a composition representative of the formation fluid (Förster et al., 2006) of 172.8 g/l NaCl, 8.0 g/l MgCl2×2H2O, 4.8 g/l CaCl2×2H2O and 0.6 g/l KCl. After 15 months, the first set of CO2-exposed samples was removed from the pressure vessels. Thin sections, XRD, SEM as well as EMP data were used to determine the mineralogical features of the reservoir rocks before and after the experiments. Additionally, NMR relaxation and MP was performed to measure poroperm and pore size distribution values of the twin samples. The analyzed samples are fine- to medium grained, moderately well- to well sorted and weakly consolidated sandstones. Quartz and plagioclase are the major components, while K-feldspar, hematite, white & dark mica, chlorite and illite are present in minor and varying amounts. Cements are composed of analcime, dolomite and anhydrite. Some samples show mm- to cm-scale cross-beddings. The laminae comprise lighter, quartz- and feldspar-dominated layers and dark-brownish layers with notably less quartz and feldspars. The results are consistent with those of Blaschke et al. (2008). The plagioclase composition indicates preferred dissolution of the Ca-component and a trend toward albite-rich phases or even pure albite during the experiments. Additionally, XRD data suggest anhydrite dissolution in the course of CO2 exposure. The chemical evolution of the brine displays increasing Ca2+ concentrations (Wandrey et al., 2010) in line with the preferred dissolution of the anorthite component of plagioclase. SEM photomicrographs show corrosion textures on mineral surfaces of, e.g., plagioclase. The petrophysical properties of the sandstone samples also suggest slight changes. NMR and MP data indicate a slightly increased porosity and a shifting to larger pore sizes. The physico-chemical measurements imply (i) Ca2+ dissolution from the rock by the fluid, and (ii) slightly increasing porosity, but decreasing permeability. However, additional evaluation is still needed to interconnect the changes suggested to occur during CO2 exposure and to better understand CO2-brine-rock interactions. Supplementary core samples have been removed from the pressure vessels after 21 and 24 months and will soon be analyzed. Further core fragments will remain in storage in the autoclaves for longer-term experiments. References BLASCHKE, A.-W., SCHöNER, R., GAUPP, R. AND FöRSTER, A. (2008): Sandstone petrography and pore system of the Upper Triassic Stuttgart Formation from a CO2 pilot storage site (Ketzin, Germany), Geo 2008 - Resources and Risks in the Earth System, International Conference and 106th Annual Meeting of the Deutsche Gesellschaft für Geowissenschaften e.V. (DGG) and 98th Annual Meeting of the Geologische Vereinigung e.V. (GV) (Aachen 2008), 301. FöRSTER, A, NORDEN, B., ZINCK-JORGENSEN, K., FRYKMAN, P., KUHLENKAMP, J., SPANGENBERG, E., ERZINGER, J., ZIMMER, M., KOPP, J., BORM, G., JUHLIN, C., COSMA, C.-G., HURTER, S. (2006): Baseline Characterization of the CO2SINK Geological Storage Site at Ketzin, Germany, Environmental Geoscience, 13, 3, 145-161. WANDREY, M., FISCHER, S., ZEMKE, K., LIEBSCHER, A., SCHERF, A.-K., VIETH, A., ZETTLITZER, M. and WüRDEMANN, H. (2010), Monitoring petrophysical, mineralogical, geochemical and microbiological effects of CO2 exposure - Results of long-term experiments under in situ condition, submitted to the 10th International Conference on Greenhouse Gas Control Technologies (GHGT 10), Amsterdam.

Composition and properties of the Pierre Shale and equivalent rocks, northern Great Plains region

USGS Publications Warehouse

Schultz, Leonard Gene; Tourtelot, H.A.; Gill, J.R.; Boerngen, J.G.

1980-01-01

The Pierre Shale and equivalent rocks of Late Cretaceous age consist in the east-central Dakotas of several hundred feet of offshore-marine shale and minor marl; in west-central Montana near the sediment source the equivalents of the Pierre Shale consist of several thousand feet of volcanic-rich and mostly nonmarine sediments; and in the area between, both types of rock are separated by tongues of nearshore-marine siltstone and sandstone that mark three major transgressions of the sea across the area. The major-, minor-, and trace-element composition was determined for 226 samples of these rocks, and the mineralogical composition was determined for 1,350 samples. Slurry pH, Atterberg limits, and grain and bulk densities were determined on some samples. The arithmetic mean, in percent, and standard deviation (in parentheses) of major and minor elements, mostly in shale and siltstone and excluding the 23 chemically analyzed bentonite samples, are as follows: SiO2 60.8 (7.9) Al2O3 14.4 (2.5) Fe2O3 3.4 (1.4) FeO 1.1 (1.2) MgO 2.2 (1.0) CaO 2.7 (0.48) Na2O 1.1 (0.56) K2O 2.4 (0.57) H2O- 3.2 (1.3) H2O+ 4.3 (1.2) TiO2 0.58 (0.12) P2O5 0.14 (0.073) S 0.37 (1.1) F 0.71 (0.15) Cl 0.16 (0.024) CO2 2.1 (7.0) C, organic 0.94 (1.8) The mean and standard deviation of minerals as determined by X-ray methods, excluding bentonite samples, is as follows: clay minerals, 53 (20); quartz, 24 (13); cristobalite, 1 (5); potassium-feldspar, 1 (2); plagioclase, 6 (7); anorthite content from 20 to 40 percent; calcite, 5 (14); dolomite, 4 (7); organic matter, 1 (2); and sparsely scattered gypsum, jarosite, pyrite, zeolites, augite, siderite, and probably minor amounts of hydrated iron-manganese (Fe-Mn) oxides. The mean and standard deviation of the clay-mineral fraction is as follows: mixed-layer illite-smectite, 70 (20); illite, 16 (9); chlorite, 3 (6); and kaolinite, 9 (13). The mixed-layer clay, except in the Montana disturbed belt, is a random interlayering of 20 to 60 percent illite-type layers, about 35 percent beidelite-type layers, and the remainder montmorillonite-type layers; chlorite or vermiculite layers are rare. Most bentonite differs from shale in its small quartz content, rarely more than a few percent, in the more calcic composition and hightemperature thermal state of its plagioclase, and in its rare kaolinite, near absence of chlorite, and lack of illite-either free or mixed layered with smectite. Bentonite commonly consists of more than 90 percent smectite in which montmorillonite is interlayered with a smaller amount of beidellite. The clay-mineral composition of marine rock, including proportions of layers in the dominant illite-smectite, averages about the same as in the nonmarine rock, though in the latter the composition is more variable. The average content of major chemical constituents also is closely similar, partly because the large clay content of fine-grained offshore-marine shale is balanced by the small clay content of nearshore-marine siltstone and sandstone. In addition, the alumina and alkalic elements in an average of 10 percent more clay in marine rock are partly balanced by these constituents in the 5 percent more feldspar in nonmarine rock. Much of the observed regional and stratigraphic variation in maj or constituents is the result of the three major east-west migrations of the depositional sites of nearshore-marine sandstone and siltstone. Dolomite is found almost exclusively in relatively coarse-grained rock, particularly in nearshore-marine siltstone where diagenetic dolomite is expected, but it is found almost as frequently in nonmarine siltstone. Amounts of minor constituents are nearly equal in marine and nonmarine rocks, except that pyrite and consequently sulfur are relatively sparse in nonmarine rock. Average amounts of organic matter found in marine and nonmarine rocks are nearly identical. However, organic matter in nonmarine rock occurs almost entirely in volumetric

A New Type of Foreign Clast in A Polymict Ureilite: A CAI or AL-Rich Chondrule

NASA Technical Reports Server (NTRS)

Goodrich, C. A.; Ross, D. K.; Treiman, A. H.

2017-01-01

Introduction: Polymict ureilites are breccias interpreted to represent regolith formed on a ureilitic asteroid [1-3]. They consist of approximately 90-95% clasts of various ureilite types (olivine-pyroxene rocks with Fo 75-95), a few % indigenous feldspathic clasts, and a few % foreign clasts [4-20]. The foreign clasts are diverse, including fragments of H, L, LL and R chondrites, angrites, other achondrites, and dark clasts similar to CC [6,7,9-19]. We report a new type of foreign clast in polymict ureilite DaG 999. Methods: Clast 8 in Dar al Gani (DaG) 999/1 (Museum fur Naturkunde) was discovered during a survey of feldspathic clasts in polymict ureilites [19,20]. It was studied by BEI, EMPA, and X-ray mapping on the JEOL 8530F electron microprobe at ARES, JSC. Petrography and Mineral Compositions: Clast 8 is sub-rounded to irregular in shape, approximately 85 micrometers in diameter, and consists of approximately 68% pyroxene and 32% mesostasis (by area). Part of the pyroxene (top half of clast in Fig. 1a and 2) shows a coarse dendritic morphology; the rest appears massive. Mesostasis may be glassy and contains fine needles/grains of pyroxene. The pyroxene has very high CaO (23.5 wt.%) and Al2O3 (19.7 wt.%), with the formula: (Ca(0.91)Mg(0.63)Fe(0.01)Al(sup VI) (0.38)Cr(0.01)Ti(0.05)1.99 Si2O6. The bulk mesostasis also has very high Al2O3 (approximately 26 wt.%). A bulk composition for the clast was obtained by combining modal abundances with phase compositions (Table 1, Fig. 3). Discussion: The pyroxene in clast 8 has a Ca-Al-(Ti)- rich (fassaitic) composition that is clearly distinct from compositions of pyroxenes in main group ureilites [22] or indigenous feldspathic clasts in polymict ureilites [4-8]. It also has significantly higher Al than fassaite in angrites (up to approximately 12 wt.% [23]), which occur as xenoliths in polymict ureilites. Ca-Al-Ti rich pyroxenes are most commonly found in CAIs, Al-rich chondrules and other types of refractory inclusions in chondrites [21,24-31]. However, the clast 8 pyroxene matches only the most Al-Ca-rich of these, e.g., pyroxenes in type B CAIs in CV3 chondrites [25,30,31], a pyroxene-hibonite spherule and a pyroxene-anorthitespinel fragment from unique CC Acfer 094 [29], and one Al-rich chondrule from Chainpur (LL3.4) [21]. The mineralogy of clast 8 is not consistent with the mineral assemblages of any of these objects (since it lacks hibonite, spinel and/or anorthite), which suggests that it is unrepresentatively sectioned or is a fragment of a more mineralogically diverse object. Its bulk composition (Table 1; Fig. 3) is similar to bulk compositions of some Al-rich chondrules, as well as those of Type C CAIs (which plot in the sp+An+L field in Fig. 3), although it is enriched in silica relative to type C CAIs [e.g., 31]. This suggests a more likely affinity to Al-rich chondrules, although most Al-rich chondrules have less Al-Ca-rich pyroxene [21,26,27]. These bulk compositional comparisons may not be definitive, however, if the clast is unrepresentatively sampled. One of eleven Al-rich chondrules from UOCs described by [21] has textural and compositional characteristics that make it a possible progenitor type for clast 8. This chondrule (Chainpur 1251-14-2) is anorthiteporphyritic, with an interstitial dendritic intergrowth of pyroxene (similar in composition to that in clast 8) and plagioclase [21]. Clast 8 is conceivably a fragment from the interstitial area of such an object. The occurrence of glassy mesostasis (in clast 8) rather than plagioclase may not be a significant difference; it could result from a difference only in cooling rate. Al-rich chondrules with glassy mesostasis are rare, and known occurrences are Ca-poor [26], unlike clast 8. Polymict ureilites are known to contain xenoliths of various chondrites (including OC, R and CC) as well as individual ferromagnesian and silica-pyroxene chondrules probably derived from OC or RC [6,9,15,16,18]. This is the first report of an individual chondritic refractory inclusion as a xenolith in a polymict ureilite. An RC-like sample from anomalous polymict ureilite Almahata Sitta contains CAIs, but they are spinel-rich and not similar to clast 8 [13,14]. Further studies of this clast (which, unfortunately, may not be possible), or the discovery of additional (more representative?) materials of this type would be needed to determine the exact nature of this xenolith and the type of chondrite from which it is derived.

Geomorphological stability of Permo-Triassic albitized profiles - case study of the Montseny-Guilleries High (NE Iberia)

NASA Astrophysics Data System (ADS)

Parcerisa, D.; Casas, L.; Franke, C.; Gomez-Gras, D.; Lacasa, G.; Nunez, J. A.; Thiry, M.

2010-05-01

Massif paleoalteration profiles (≥ 200 m) occur in the upper parts of the Montseny-Guilleries High (NE Catalan Coastal Ranges). The profiles consist of hard albitized-chloritized-hematized facies in the lower part and softer kaolinized-hematized facies in the upper part of the section. Preliminary paleomagnetic data show Triassic ages for both, the albitized and the kaolinized parts, and point to a surficial formation altered under oxidising conditions. Similar paleoalteration profiles have already been described and dated to Triassic ages elsewhere in Europe [Schmitt, 1992; Ricordel et al., 2007; Parcerisa et al., 2009]. These Permian-Triassic alterations are following a succession of different mineral transformations from the top to the base of the profile: 1) Red facies are defined by an increase in the amount and size of haematite crystals leading to the red colour of the rocks. The increase on haematite content is pervasively affecting the whole rock and is accompanied by the kaolinitization of the feldspars. 2) Pink facies: here, the granite shows an uniform pink colouration, which is mainly due to the albitization of the primary Ca-bearing plagioclases, accompanied by a precipitation of minute haematite, sericite, and calcite crystals inside the albite. Additionally primary biotite is fully chloritized. The pink granites are much more resistant to the present-day weathering than the "unaltered" facies at the base of the profile. 3) Spotted facies is characterized by a partial alteration of the rock, which caused a pink-screened aspect to the rock. The alteration developed along the fractures and is less well developed or absent in the non-fractured zones. In the pink-screened facies, the plagioclases are partially albitized and contain numerous hematite inclusions. Biotites are usually almost entirely chloritized. 4) Unaltered facies: These granites are coloured white to greyish, containing plagioclase and K-feldspar that do not show any trace of albitization. Biotites are not or weakly chloritized. However, these "unaltered" (or primary) granites are strongly weathered into granite boulders embedded in grus by the present-day climatic conditions. The maturest paleoprofiles occur at the northern part of the Catalan Coastal Ranges (i.e. the Montseny-Guilleries High) where the Variscan basement remained exposed during Triassic times. Towards the South the profiles progressively disappear and Triassic sediments acquire their maximum thickness here. The alteration profiles are related with the Permo-Triassic paleosurface still outcroping on wide areas [Gómez-Gras and Ferrer, 1999]. They are partially covered by Triassic fluvial sandstones (Buntsandstein facies) in the South [Gómez-Gras, 1993] and by Palaeocene alluvial conglomerates in the West [Anadón et al., 1979]. The Triassic paleosurface shows a remarkable stability successively outcropping during Mesozoic and Tertiary times, the pre-Tertiary exhumation and even the present day weathering affected very little these albitized profiles. The hardness and thus preservation of the Triassic paleosurface is mainly related to the albitization. The albitized granites are entirely lacking anorthitic plagioclase, which is much more sensitive to chemo-mechanical weathering. Development of albite and additional chloritization of the primary biotite crystals render the rocks much more resistant to weathering and erosion. This stability is particularly well expressed in case of the Montseny-Guilleries High, which is limited by a high fault scarp at the south-eastern margin. The albitized top of the scarp shows remarkably hard fresh rocks, whereas the base of the scarp (formed of primary, non-albitized facies) is deeply weathered into gruss. This is causing much smother landscape reliefs in the valleys and thalwegs. Since a long time the remarkable persistence of the Triassic paleosurface expressed in the Paleozoic massifs has been highlighted by geomorphologists. Only recently we could draw the link of the paleosurface preservation to its albitisation [Battiau-Queney, 1996; Widdowson, 1997]. Anadón, P., Colombo, F., Esteban, M., Marzo, M., Robles, S., Santanach, P., Solé-Sugrañes, L.., 1979. Evolución tectonostratigráfica de los Catalánides. Acta Geológica Hispánica, 14: 242-270. Battiau-Queney Y., 1996, A tentative classification of paleoweathering formations based on geomorphological criteria. Geomorphology, 16, p. 87-102. Gómez-Gras, D., 1993. El Permotrias de la Cordillera Costero Catalana: facies y petrologia sedimentaria (Parte I). Boletin Geologico y Minero, 104(2): 115-161. Gómez-Gras, D., Ferrer, C., 1999. Caracterización petrológica de perfiles de meteorización antiguos desarrollados en granitos tardihercínicos de la Cordillera Costero Catalana. Revista de la Sociedad Geológica de España, 12(2): 281-299. Parcerisa, D., Thiry, M., Schmitt, J.M., 2009. Albitisation related to the Triassic unconformity in igneous rocks of the Morvan Massif (France). International Journal of Earth Sciences (Geol Rundsch). DOI 10.1007/s00531-008-0405-1 Ricordel, C., Parcerisa, D., Thiry, M., Moreau, M.G., Gómez-Gras, D., 2007. Triassic magnetic overprints related to albitization in granites from the Morvan massif (France). Palaeogeography, Palaeoclimatology, Palaeoecology, 251: 268-282. Schmitt J.M., 1992, Triassic albitization in southern France : an unusual mineralogical record from a major continental paleosurface. in : Mineralogical and geochemical records of paleoweathering, IGCP 317, Schmitt J.M., Gall Q., (eds), E.N.S.M.P. Mém. Sc. de la Terre, 18, p. 115-132. Widdowson M., 1997, The geomorphological and geological importance of palaeosurfaces. in: Widdowson M. (ed.), Palaeosurfaces: recognition, reconstruction and palaeoenvironmental interpretation. Geol. Soc. Special Publ., 120, p. 1-12.

Evidence for Extremely-High-Temperature Melting in the Solar Nebula from a CaAl4O7-bearing Spherule from Murchison

NASA Astrophysics Data System (ADS)

Simon, S. B.; Grossman, L.; Davis, A. M.; Beckett, J. R.; Chamberlin, L.

1993-07-01

We have recovered a unique refractory spherule (B6) from the Murchison C2 chondrite. Approximately 140 micrometers in diameter, it is concentrically zoned, with an outer rim sequence, from outermost to innermost, of aluminous diopside (10 micrometers thick), anorthite (3 micrometers) and melilite (3 micrometers). Inside the melilite layer is a 7-micrometer-thick, nearly pure (except for a single, diverging-inward spray of hibonite crystals) layer of spinel. Inward from this layer is a 22-micrometer-wide zone of hibonite (~5.5 wt% TiO2) + spinel, in which hibonite laths, 1-4 micrometers across and up to 10 micrometers wide, are predominantly radially oriented and enclosed in spinel. Inward from this zone, presumably at the core of the inclusion, are CaAl4O7, occurring as anhedral grains ~10 micrometers across, and minor perovskite. Some of the hibonite laths protrude into the CaAl4O7. The sequence of mineral assemblages from the spinel shell inward parallels that expected for fractional crystallization of a melt of the composition of B6. Based on this, the inclusion's spherical shape, and its texture (radially oriented hibonite laths, including a diverging-inward spray; laths enclosed in spinel and protruding into CaAl4O7), we conclude that the oxide phases in B6 crystallized from a liquid. The spinel layer indicates that at least some of the spinel was molten; from the bulk composition, calculated liquidus phase relations in the system Al2O3-MgO-CaO [1], and the amount of spinel contained in the layer, we infer a melting temperature >2000 degrees C. This is >500 degrees higher than the maximum temperature at which any condensed major phase is stable at 10-3 atm in a gas of solar composition, but we see no evidence of evaporation. First, the inclusion has a Group II REE pattern, rather than a Group III or an ultrarefractory pattern, which could reflect devolatilization. Second, although evaporation of molten (but not solid) Mg2SiO4 leads to Mg isotopic mass fractionation [2], we found the Mg isotopic composition of spinel and hibonite in B6 to be essentially normal (DELTA 25Mg = 0 +- 2.5 permil). This means that no more than ~15% of the Mg could have evaporated, which, by analogy with experiments with forsterite at 2050 degrees C [2], suggests that the melt was exposed to the solar nebula for a very short time, perhaps as little as two minutes. This could indicate rapid formation of the spinel shell in B6, sealing off the molten interior from the solar nebula. Evaporation of solid spinel could have occurred, but would probably not fractionate Mg isotopes significantly. Evidence of an unusually high temperature history is preserved in the spinel of B6. It averages 1.7 +- 0.4 mol% excess Al2O3 relative to MgAl2O4, unlike the stoichiometric (within analytical error) spinel found in most CAIs. Much larger Al2O3 solubilities than observed in B6 spinel have been produced in synthetic systems at temperatures as low as 1300 degrees C [3]. In our crystallization experiments, excess Al2O3 ranges from 2 mol% in spinel equilibrated with melilite + hibonite + liquid at 1400 degrees C to 30 mol% in spinel equilibrated with liquid at 1499 degrees C. In corundum-bearing runs, excess Al2O3 in spinel increases from 12 mol% at 1349 degrees C to 24 mol% at 1450 degrees C, consistent with [3]. Excess Al2O3 in spinel is directly correlated with aAl2O3/aMgO based on experiments with solids [4]; it should also be correlated with aAl2O3/aMgO of coexisting liquids, and with temperature at constant aAl2O3/aMgO [1]. Spinels in our experiments have large excess Al2O3 contents because coexisting liquids have aAl2O3/aMgO >6 [1]. The bulk composition of B6 and residual liquids produced by crystallization of spinel from this composition have aAl2O3/aMgO ~1 [1], resulting in lower excess Al2O3 in B6 spinel than in our synthetic spinel. In type B inclusions, liquids with which spinel equilibrated also had aAl2O3/aMgO ratios ~1, but because equilibration temperatures were <~1500 degrees C, this spinel has negligible excess Al2O3, consistent with the results of [4]. The larger amounts of excess Al2O3 in B6 spinel indicate that its equilibration temperature was substantially higher than in type Bs (i.e., >~ 1500 degrees C), consistent with the above observations. References: [1] Berman R. G. (1983) Ph.D. thesis, U. British Columbia. [2] Davis A. M. et al. (1990) Nature, 347, 655-658. [3] Viertel H. U. and Seifert F. (1980) N. Jb. Miner. Abh., 140, 89-101. [4] Chamberlin L. et al. (1992) GSA Abs. with Prog., 24, A257.

Environmental degradation of oxidation resistant and thermal barrier coatings for fuel-flexible gas turbine applications

NASA Astrophysics Data System (ADS)

Mohan, Prabhakar

The development of thermal barrier coatings (TBCs) has been undoubtedly the most critical advancement in materials technology for modern gas turbine engines. TBCs are widely used in gas turbine engines for both power-generation and propulsion applications. Metallic oxidation-resistant coatings (ORCs) are also widely employed as a stand-alone protective coating or bond coat for TBCs in many high-temperature applications. Among the widely studied durability issues in these high-temperature protective coatings, one critical challenge that received greater attention in recent years is their resistance to high-temperature degradation due to corrosive deposits arising from fuel impurities and CMAS (calcium-magnesium-alumino-silicate) sand deposits from air ingestion. The presence of vanadium, sulfur, phosphorus, sodium and calcium impurities in alternative fuels warrants a clear understanding of high-temperature materials degradation for the development of fuel-flexible gas turbine engines. Degradation due to CMAS is a critical problem for gas turbine components operating in a dust-laden environment. In this study, high-temperature degradation due to aggressive deposits such as V2O5, P2O 5, Na2SO4, NaVO3, CaSO4 and a laboratory-synthesized CMAS sand for free-standing air plasma sprayed (APS) yttria stabilized zirconia (YSZ), the topcoat of the TBC system, and APS CoNiCrAlY, the bond coat of the TBC system or a stand-alone ORC, is examined. Phase transformations and microstructural development were examined by using x-ray diffraction, scanning electron microscopy, and transmission electron microscopy. This study demonstrated that the V2O5 melt degrades the APS YSZ through the formation of ZrV2O7 and YVO 4 at temperatures below 747°C and above 747°C, respectively. Formation of YVO4 leads to the depletion of the Y2O 3 stabilizer and the deleterious transformation of the YSZ to the monoclinic ZrO2 phase. The investigation on the YSZ degradation by Na 2SO4 and a Na2SO4 + V2O 5 mixture (50-50 mol. %) demonstrated that Na2SO4 itself did not degrade the YSZ, however, in the presence of V2O 5, Na2SO4 formed vanadates such as NaVO3 that degraded the YSZ through YVO4 formation at temperature as low as 700°C. The APS YSZ was found to react with the P2O 5 melt by forming ZrP2O7 at all temperatures. This interaction led to the depletion of ZrO2 in the YSZ (i.e., enrichment of Y2O3 in t'-YSZ) and promoted the formation of the fluorite-cubic ZrO2 phase. Above 1250°C, CMAS deposits were observed to readily infiltrate and significantly dissolve the YSZ coating via thermochemical interactions. Upon cooling, zirconia reprecipitated with a spherical morphology and a composition that depended on the local melt chemistry. The molten CMAS attack destabilized the YSZ through the detrimental phase transformation (t' → t → f + m). Free standing APS CoNiCrAlY was also prone to degradation by corrosive molten deposits. The V2O5 melt degraded the APS CoNiCrAlY through various reactions involving acidic dissolution of the protective oxide scale, which yielded substitutional-solid solution vanadates such as (Co,Ni) 3(VO4)2 and (Cr,Al)VO4. The molten P2O5, on the other hand, was found to consume the bond coat constituents significantly via reactions that formed both Ni/Co rich phosphates and Cr/Al rich phosphates. Sulfate deposits such as Na2SO 4, when tested in encapsulation, damaged the CoNiCrAlY by Type I acidic fluxing hot corrosion mechanisms at 1000°C that resulted in accelerated oxidation and sulfidation. The formation of a protective continuous Al 2O3 oxide scale by preoxidation treatment significantly delayed the hot corrosion of CoNiCrAlY by sulfates. However, CoNiCrAlY in both as-sprayed and preoxidized condition suffered a significant damage by CaSO4 deposits via a basic fluxing mechanism that yielded CaCrO4 and CaAl2O4. The CMAS melt also dissolved the protective Al2O3 oxide scale developed on CoNiCrAlY by forming anorthite platelets and spinel oxides. Based on the detailed investigation on degradation of the APS YSZ and CoNiCrAlY by various corrosive deposits, an experimental attempt was carried out to mitigate the melt-induced deposit attack. Experimental results from this study demonstrate, for the first time, that an oxide overlay produced by electrophoretic deposition (EPD) can effectively perform as an environmental barrier overlay for APS TBCs. The EPD protective overlay has a uniform and easily-controllable thickness, uniformly distributed closed pores and tailored chemistry. The EPD Al2O3 and MgO overlays were successful in protecting the APS YSZ TBCs against CMAS attack and hot corrosion attack (e.g., sulfate and vanadate), respectively. Furnace thermal cyclic oxidation testing of overlay-modified TBCs on bond-coated superalloy also demonstrated the good adhesive durability of the EPD Al2O3 overlay.