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At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1982

The partitioning of Zr and Nb between diopside and melts in the system diopside-albite-anorthite

The crystal/liquid distribution coefficient for Zr between diopside and melt is measured for six compositions and three temperatures in the diopside field of Di-Ab-An, and the distribution coefficient for Nb is measured for three of these compositions. Nb is found to be excluded from diopside, while D(Zr), which is defined as wt % ZrO2 in crystals/wt % ZrO2 in melt, is variable and ranging from 0.05 to 0.45. D(Zr) is positively correlated with the Al content of both the melt and the pyroxene, and is negatively correlated with temperature. Both D(Zr) and D(Nb) are independent of oxygen fugacity, which implies that neither Zr nor Nb suffer valence changes over a range of oxygen fugacities spanning lunar and terrestrial conditions.

Dunn, T.↗
DOE OSTI2023

Emerging investigator series: kinetics of diopside reactivity for carbon mineralization in mafic–ultramafic rocks

The ongoing use of fossil fuels to supply modern energy demands has necessitated research on combating carbon dioxide (CO 2 ) emissions and climate change. Carbon storage via mineral trapping in basalt and related rocks is a promising strategy. However, mineralization rates depend on the variable minerology that makes up these rock formations. Diopside (CaMgSi 2 O 6 ) is a common pyroxene mineral in ultramafic and mafic rocks including basalt, but relatively little work has been done to understand its carbon mineralization kinetics using hydrated supercritical CO 2 , which induces the formation of reactive nanoscale interfacial water films. Here, in situ XRD experiments at 50–110 °C and 90 bar indicate that diopside transforms into a myriad of Mg/Ca carbonates, including huntite [Mg 3 Ca(CO 3 ) 4 ] and very high magnesium calcite (VHMC, i.e., protodolomite). Through ex situ characterization, we were able to constrain reaction pathways for the dissolution–precipitation transformation process including metastable intermediate precipitates. Experiments performed at variable temperatures enabled Avrami-derived rate constants and an apparent activation energy of 97 ± 16 kJ mol –1 , implying the dissolution of diopside is the rate-limiting step. Density functional theory (DFT) calculations, used to gain molecular insight into the surface stability of the diopside during dissolution, suggest that exposed calcium cations are susceptible to dissolution when put in contact with water given their coordination environment. The collective results point to the high CO 2 mineralization potential of diopside in basalts, which could help guide parameterization of reactive transport models needed to design and permit commercial-scale subsurface carbon storage operations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1981

Ni partitioning between diopside and silicate melt - A redetermination by ion microprobe and recognition of an experimental complication

The capabilities of and potential problems with ion microprobe analysis are illustrated in the determination of Ni distribution between silicate melt and diopside as a function of concentration. Samples of diopside and a melt in the albite-anorthite-diopside system were doped with Ni to levels of 5.22 and 1.08 wt % and 1060, 138, 42 and 30 ppm, and with 3 ppm of Ni-63, and characterized by both electron and ion microprobe techniques. Measurements of Ni-62 distribution by the ion probe method give a ratio of 1.87 for the ratio of count rates in the diopsides with the glass, which is slightly lower than the value of 2.05 obtained from beta-track mapping. The measurements required the secondary ion signal to be linear with concentration in the range measured, and a calibration to correct for differential secondary ion yields from different phases. It is found, however, that partition coefficients measured for Ni-58 and Ni-60 are not constant with Ni concentration, probably due to Ni migration during crystallization. The results thus show ion microprobe analyses to be feasible for simultaneous measurements of distributions of more than one element, and of elements inappropriate for beta-track mapping or electron probe analysis.

Steele, I. M.↗
NASA NTRS1972

Occurrence of diopside and Cr-Zr-armalcolite on the moon.

Petrographic and electron-microprobe examination of the sample of 1 to 2 mm fines, Apollo 14166,6, has revealed a fragment with the unique lunar mineralogy of plagioclase, olivine, diopside, a Ti-Fe-Zr phase, and a trace of ilminite. The second occurrence of diopside is reported together with the third occurrence of a recently identified Ti-Fe-Zr phase. Microprobe analyses of the principal phases of the fragment studied are presented in a table. The relatively pure diopside analyses reported represent the most Mg-rich calcic pyroxene found in lunar material.

Steele, I. M.↗
NASA NTRS2000

Mineralogy, Petrology, Chemistry, and Ar-39 - Ar-40 and Ages of the Caddo County IAB Iron: Evidence for Early Partial Melt Segregation of a Gabbro Area Rich in Plagioclase-Diopside

We found coarse-grained gabbroic material rich in plagioclase and diopside in the Caddo County IAB iron meteorite. The polished thin sections studied were made from areas rich in Al and Ca detected by a micro-focus X-ray fluorescence (XRF) mapping technique. The gabbro is not a clast within a breccia, but rather this area is located mainly at silicate-metal boundaries only a few cm away from an area with fine-grained, ultramafic silicate similar to winonaites. Medium-grained orthopyroxene and olivine are found in transitional areas showing no disturbance of their crystalline textures. A vein-like region, starting at the area rich in fine-grained mafic silicate, extends towards the gabbroic area with a gradual increase in abundance of plagioclase and diopside. This texture and our accumulated knowledge of the formation mechanism of IAB/winonaltes meteorites, suggest that the gabbroic materials were formed by inhomogeneous segregation of partial melts of chondritic source materials. Compositional data on two mineralogically distinct samples of the gabbro-rich portion of the inclusion were obtained by INAA. Compared to an average of LAB silicate inclusions or winonaites, the Caddo County gabbro is enriched in the incompatible lithophile elements Na, Ca, Sc, REE and Hf, which is consistent with a melt origin for the gabbro. The cosmogenic space exposure age of Caddo County (511 Ma) is significantly younger than exposure ages of some other IAB meteorites, An 39Ar-40Ar age determination of the gabbroic material indicates a series of upward steps in age from 4.516 Ga to 4.523 Ga, with a few high temperature ages up to 4.54 Ga. The older age could approximate the primary recrystallization age of silicates. The stepped Ar age spectrum may indicate differences in Ar closure temperatures during slow cooling of -2-20'C/Myr in the parent body. Alternatively, the younger Ar-Ar ages may date a shock event which occurred while Caddo County was hot and which also created textures such as a linear metal vein with rounded zigzag walls in a diopside crystal and slightly miss-oriented rounded plagioclase domain.

Takeda, Hiroshi↗
DOE OSTI2022

Structure of diopside, enstatite, and magnesium aluminosilicate glasses: A joint approach using neutron and x-ray diffraction and solid-state NMR

Neutron diffraction with magnesium isotope substitution, high energy x-ray diffraction, and 29 Si, 27 Al, and 25 Mg solid-state nuclear magnetic resonance (NMR) spectroscopy were used to measure the structure of glassy diopside (CaMgSi 2 O 6 ), enstatite (MgSiO 3 ), and four (MgO) x (Al 2 O 3 ) y (SiO 2 ) 1–x–y glasses, with x = 0.375 or 0.25 along the 50 mol. % silica tie-line (1 – x – y = 0.5) or with x = 0.3 or 0.2 along the 60 mol. % silica tie-line (1 – x – y = 0.6). The bound coherent neutron scattering length of the isotope 25 Mg was remeasured, and the value of 3.720(12) fm was obtained from a Rietveld refinement of the powder diffraction patterns measured for crystalline 25 MgO. The diffraction results for the glasses show a broad asymmetric distribution of Mg–O nearest-neighbors with a coordination number of 4.40(4) and 4.46(4) for the diopside and enstatite glasses, respectively. As magnesia is replaced by alumina along a tie-line with 50 or 60 mol. % silica, the Mg–O coordination number increases with the weighted bond distance as less Mg 2+ ions adopt a network-modifying role and more of these ions adopt a predominantly charge-compensating role. 25 Mg magic angle spinning (MAS) NMR results could not resolve the different coordination environments of Mg 2+ under the employed field strength (14.1 T) and spinning rate (20 kHz). The results emphasize the power of neutron diffraction with isotope substitution to provide unambiguous site-specific information on the coordination environment of magnesium in disordered materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1974

The distribution of Sr and REE between diopside and silicate liquid

Experimental determination of the distribution coefficients in diopside-liquid pairs for strontium and nine rare-earth elements in the system CaMgSi2O6-NaAlSi3O8-CaAl2Si2O8. In experiments in air at 1265 C it is found that most of the Sr(2+), Eu(2+), and RE(3+) ions substitute for Ca(2+) and, in addition, a coupled substitution of Al(3+) for Si(4+) occurs. All of the trace ions considered are found to be excluded from the diopside lattice relative to the liquid. In the case of the trivalent ions the exclusion is much more pronounced for La and Ce, which have ionic radii larger than that of Ca(2+) in 8-fold oxygen coordination. Divalent Sr and Eu with even larger radii are also strongly excluded.

Grutzeck, M.↗
NASA NTRS1981

A thermochemical calculation of the pyroxene saturation surface in the system diopside-albite-anorthite

The pyroxene saturation surface in the system diopside-albite-anorthite may be calculated to + or - 10 C from thermochemical data over most of its composition range. The thermochemical data used are the experimentally determined enthalpies of mixing of the ternary liquids and the enthalpy of fusion of diopside. These are combined with a mixing model for the configurational entropy in the melt and the activity of CaMgSi2O6 in the clinopyroxene, which is less than unity due to departures from CaMgSi2O6 stoichiometry. The two-lattice melt model appears to work satisfactorily throughout the pyroxene primary phase field but probably needs modification at more anorthite-rich compositions.

Hon, R.↗
DOE OSTI2022

Sound velocity and compressibility of melts along the hedenbergite (CaFeSi2O6)-diopside (CaMgSi2O6) join at high pressure : Implications for stability and seismic signature of Fe-rich melts in the mantle

Iron-rich silicate melts play an important role in the magmatic history of the Earth and the 16 Moon. However, their elastic properties at high pressures, especially the sound velocity, are poorly 17 understood. Here we determined the ultrasonic sound velocity for the first time of a hedenbergite 18 (Hd, CaFeSi2O6) melt and a melt mixture of 50 mol% hedenbergite + 50 mol% diopside (Hd50Di50) 19 at high pressure and temperature conditions up to 6 GPa and 2329 K, using high-pressure ultrasonic 20 technique combined with synchrotron radiation in a multi-anvil apparatus. Our results show that 21 Fe can significantly reduce the sound velocity while increase the density of silicate melts. 22 Comparing the Di, Hd, and Hd50Di50 melts, we find that the sound velocity does not mix linearly 23 2 for melts in the Hd-Di join, whereas the density for Hd-Di melts at high pressures can be well-24 described by linear mixing. Combined with melt geometry and melt compaction models, we 25 applied our results to study the stability and seismic signature of Fe-rich silicate melts in the Earth’s 26 upper mantle. For the low-velocity zone (LVZ) in mantle asthenosphere, although the degree of 27 seismic velocity reduction can be explained by the presence of a small amount of partial melt 28 distributed in film/band geometry along grain boundaries, Fe-rich melts formed at this depth are 29 unlikely to be gravitationally stable, but may be dynamically unextractable if the melt supply is 30 continuous. For the low-velocity layer (LVL) above the mantle transition zone, the presence of Fe-31 rich melts (with FeO>~10 wt%) distributed in textural equilibrium with the ambient mantle is a 32 plausible explanation.

diopside↗
NASA NTRS1978

Partitioning of transition metals between diopside and coexisting silicate liquids. I - Nickel, cobalt, and manganese

Distribution coefficients have been found for the partitioning of Ni, Co, and Mn between calcium-rich clinopyroxenes and coexisting silicate liquids. Values are found for the 1110-1360 C temperature range. The breakdown of Henry's Law was not observed. The measured clinopyroxene/liquid distribution coefficients ranged from 1.5-14.0 for Ni, 0.5-2.0 for Co, and 0.3-1.2 for Mn. Analyses of pyroxenes grown from charges differing in the amounts of transition metals indicate that Ni and Co occupy the M1 site of diopside and that Mn occupies the M1 and M2 sites. Equilibrium constants were found in terms of the activities of the components in the liquid and solid phases. These activities are based on the mole fractions. An activity/concentration model was used for the liquid phase in order to explain the variations in the clinopyroxene/liquid coefficients due to bulk composition.

Lindstrom, D. J.↗
NASA NTRS1983

Seventh Foray - Whitlockite-rich lithologies, a diopside-bearing troctolitic anorthosite, ferroan anorthosites, and KREEP

Seventeen nonmare samples, most of them pristine, are characterized, and implications of the new data are discussed. Five pristine samples are from Apollo 14, near the center of the KREEP-rich zone in the moon's western hemisphere. Three of them are alkali anorthosites rich in Ca-phosphate (whitlockite), which apparently crystallized from magmas with REE contents roughly 6 x those of high-K KREEP. The alkali anorthosites probably formed from Mg-rich magmas that assimilated large amounts of urKREEP, but some might have formed by metasomatism of ferroan anorthosite by urKREEP. The gabbronorite/norite classification scheme is not well suited to western hemisphere lithologies, probably due mainly to the overriding effects of longitude-petrochemistry correlations. A diopside-bearing Mg-rich lithology indicates that a low degree of melting was not a prerequisite for producing gabbroic (high-Ca pyroxene-rich) Mg-rich magmas, and suggests that some source regions of Mg-rich magmas were relatively Ca-rich. Several pristine KREEP fragments from Apollo 15 station 2 are texturally and compositionally much like other pristine KREEP, and thus reinforce the evidence that KREEP is highly uniform. The pristine anorthosites, on the other hand, demonstrate further that lunar anorthosites are diverse.

Warren, P. H.↗
NASA NTRS1990

Solubility and partitioning of Ar in anorthite, diopside, forsterite, spinel, and synthetic basaltic liquids

The solubility and partitioning of Ar in natural anorthite, diopside, forsterite, spinel, and synthetic iron-free basaltic melts was investigated using a new technique that obviates the postquenching phase separation. It was found that the solubility of Ar in the minerals was surprisingly high. Moreover, the solubility of Ar in different samples of a particular mineral run in the same experiment varied more than the solubility in the same sample run in different experiments, suggesting that noble gases are held in lattice vacancy defects. Moreover, the results of TEM imaging revealed no anomalous microstructures, while EXAFS studies of some samples showed that Kr has no preferred site in the lattices, supporting the defect siting conclusion.

Broadhurst, C. Leigh↗
NASA NTRS1990

Electrochemistry of cations in diopsidic melt - Determining diffusion rates and redox potentials from voltammetric curves

Results are presented on determinations of reduction potentials and their temperature dependence of selected ions in diopsidic melt, by using linear sweep voltammetry. Diffusion coefficients were measured for cations of Eu, Mn, Cr, and In. Enthalpies and entropies of reduction were determined for the cations V(V), Cr(3+), Mn(2+), Mn(3+), Fe(2+), Cu(2+), Mo(VI), Sn(IV), and Eu(3+). Reduction potentials were used to study the structural state of cations in the melt.

Colson, Russell O.↗
NASA NTRS2012

Collisional Histories of Comets and Trojan Asteroids: Diopside, Magnesite, and Fayalite Impact Studies

Comets and asteroids have weathered dynamic histories, as evidenced by their rough surfaces. The Nice model describes a violent reshuffling of small bodies during the Late Heavy Bombardment, with collisions acting to grind these planetesimals away. This creates an additional source of impact material that can re-work the surfaces of the larger bodies over the lifetime of the solar system. Here, we investigate the possibility that signatures due to impacts (e.g. from micrometeoroids or meteoroids) could be detected in their spectra, and how that can be explained by the physical manifestation of shock in the crystalline structure of minerals. All impact experiments were conducted in the Johnson Space Center Experimental Impact Laboratory using the vertical gun. Impact speeds ranged from approx.2.0 km/s to approx.2.8 km/s. All experiments were conducted at room temperature. Minerals found in comets and asteroids were chosen as targets, including diopside (MgCaSi2O6, monoclinic pyroxene), magnesite (MgCO3, carbonate), and fayalite (FeSiO4, olivine). Impacted samples were analyzed using a Fourier Transform Infrared Spectrometer (FTIR) and a Transmission Electron Microscope (TEM). Absorbance features in the 8-13 m spectral region demonstrate relative amplitude changes as well as wavelength shifts. Corresponding TEM images exhibit planar shock dislocations in the crystalline structure, attributed to deformation at high strain and low temperatures. Elongating or shortening the axes of the crystalline structure of forsterite (Mg2SiO4, olivine) using a discrete dipole approximation model (Lindsay et al., submitted) yields changes in spectral features similar to those observed in our impacted laboratory minerals.

Lederer, S. M.↗
NASA NTRS1989

Determination of trace element mineral/liquid partition coefficients in melilite and diopside by ion and electron microprobe techniques

The applicability of ion microprobe (IMP) for quantitative analysis of minor elements (Sr, Y, Zr, La, Sm, and Yb) in the major phases present in natural Ca-, Al-rich inclusions (CAIs) was investigated by comparing IMP results with those of an electron microprobe (EMP). Results on three trace-element-doped glasses indicated that it is not possible to obtain precise quantitative analysis by using IMP if there are large differences in SiO2 content between the standards used to derive the ion yields and the unknowns.

Kuehner, S. M.↗
DOE OSTI2023

Metasomatic alteration of coarse‐grained igneous calcium‐aluminum‐rich inclusions from CK3 carbonaceous chondrites

Abstract We report on the primary and secondary mineralogies of three coarse‐grained igneous calcium‐aluminum‐rich inclusions (CAIs) (Compact Type A [CTA], Type B [B], and forsterite‐bearing type B [FoB]) from the Northwest Africa (NWA) 5343 (CK3.7) and NWA 4964 (CK3.8) carbonaceous chondrites, compare them with the mineralogy of igneous CAIs from the Allende (CV3.6) chondrite, and discuss the nature of the alteration processes that affected the CK and CV CAIs. The primary mineralogy and mineral chemistry of the CK3 CAIs studied are similar to those from Allende; however, primary melilite and anorthite are nearly completely absent. Although the secondary minerals identified in CK CAIs (Al‐diopside, andradite, Cl‐apatite, clintonite, forsterite, ferroan olivine, Fe,Ni‐sulfides, grossular, ilmenite, magnetite, plagioclase, spinel, titanite, and wadalite) occur also in the Allende CAIs, there are several important differences: (i) In addition to melilite and anorthite, which are nearly completely replaced by secondary minerals, the alteration of CK CAIs also affected high‐Ti pyroxenes (fassaite and grossmanite) characterized by high Ti 3+ /Ti 4+ ratio and spinel. These pyroxenes are corroded and crosscut by veins of Fe‐ and Ti‐bearing grossular, Fe‐bearing Al,Ti‐diopside, titanite, and ilmenite. Spinel is corroded by Fe‐bearing Al‐diopside and grossular. (ii) The secondary mineral assemblages of grossular + monticellite and grossular + wollastonite, commonly observed in the Allende CAIs, are absent; the Fe‐bearing grossular + Fe‐bearing Al‐diopside ± Fe,Mg‐spinel, Fe‐bearing grossular + Fe,Mg‐olivine ± Fe,Mg‐spinel, and Ca,Na‐plagioclase + Fe‐bearing Al‐diopside + Fe‐bearing grossular assemblages are present instead. These mineral assemblages are often crosscut by veins of Fe‐bearing Al‐diopside, Fe,Mg‐olivine, Fe,Mg‐spinel, and Ca,Na‐plagioclase. The coarse‐grained secondary grossular and Al‐diopside often show multilayered chemical zoning with distinct compositional boundaries between the layers; the abundances of Fe and Ti typically increase toward the grain edges. (iv) Sodium‐rich secondary minerals, nepheline and sodalite, commonly observed in the peripheral portions of the Allende CAIs, are absent; Ca,Na‐plagioclase is present instead. We conclude that coarse‐grained igneous CAIs from CK3.7–3.8 s and Allende experienced an open‐system multistage metasomatic alteration in the presence of an aqueous solution–infiltration metasomatism. This process resulted in localized mobilization of all major rock‐forming elements: Si, Ca, Al, Ti, Mg, Fe, Mn, Na, K, and Cl. The metasomatic alteration of CK CAIs is more advanced and occurred under higher temperature and higher oxygen fugacity than that of the Allende CAIs.

Geochemistry & Geophysics↗