Cathodoluminescence, electron microscopy, and Raman spectroscopy of experimentally shock-metamorphosed zircon

Thorough understanding of the shock metamorphic signatures of zircon could be the basis for the use of this mineral as a powerful tool for the study of old, deeply eroded, and metamorphically overprinted impact structures and formations. This study of the cathodoluminescence (CL) and Raman spectroscopic signatures of experimentally (20-60 GPa) shock-metamorphosed zircon single crystals contributes to the understanding of high-pressure microdeformation in zircon. For all samples, an inverse relationship between the brightness of the backscattered electron (BSE) signal and the corresponding cathodoluminescence intensity was observed. The unshocked sample shows crosscutting, irregular fractures. The 20 GPa sample displays some kind of mosaic texture of CL brighter and darker domains, but does not exhibit any shock metamorphic features in BSE or CL images. The 40 GPa sample shows a high density of lamellar features, which might be explained by the phase transformation between zircon- and scheelite-structure phases of zircon and resulting differences in the energy levels of the activator elements. The CL spectra of unshocked and shocked (20, 40, and 60 GPa) zircon samples are dominated by narrow emission lines and broad bands in the region of visible light and in the near-UV range. The emission lines result from rare earth element activators and the broad bands might be associated with lattice defects. Raman spectra revealed that the unshocked and 20 GPa samples represent zircon-structure material, whereas the 40 GPa sample yielded additional peaks with relatively high peak intensities, which are indicative of the presence of the scheelite-type high-pressure phase. The 60 GPa sample has a Raman signature that is similar to that of an amorphous phase, in contrast to the observations of an earlier TEM study that the crystalline scheelite-structure phase is stable at this shock pressure. The 60 GPa Raman signature cannot be explained at this stage. The results show a clear dependence of the CL and Raman properties of zircon on shock pressure, which confirm the possible usage of these methods as shock indicators.     

Remarques sur la matrice des chondrites ordinaires d'apres l'observation de quelques chondrites a bronzite peu ou pas choquees

Microscopic investigations have been done on the chondrites Sena and Nadiabondi (H5, not shocked), Ste. Marguerite en Comines (H4, very slightly shocked), Allegan (H5, slightly shocked). Only in such cases can the matrix be easily observed and compared to those of type 3 chondrites. The <100 μm debris found in types 4 and 5 that we have observed are not the result of the metamorphism of type 3 fines.The abundance of tiny debris is in direct relation with the intensity of the shock though this shock was insufficient to provoke either the induration of the stones or a significant loss of rare gases. The bulk of the fines are the result of local disaggregation of the most brittle parts from chondrules and fragments.A low-temperature matrix has not been observed in these meteorites but only in H3 chondrites, as a coating around the chondrules. The accretion modelists should take into account the absence or the scarcity of fine particles in their calculations.     

Electron petrography of shock-deformed olivine in stony meteorites

We have studied olivine by high-voltage electron microscopy in meteorites showing shock effects, namely the ordinary chondrites Olivenza and Hedjaz, the ureilite Goalpara and the carbonaceous chondrite Allende. The observations are compared with published data on experimentally deformed and annealed olivine.Olivenza and Hedjaz have suffered low-temperature shock, which has produced high densities of [001] screw dislocations and cracks. Arrays of cracks are found to correspond to planar features which can be seen optically and to be responsible for mosaicism. Goalpara has suffered very heavy shock, of which the final result is extensive recrystallization of the olivine, and the new grains have distinctive low-density distributions of dislocations. Allende has not been shocked as a whole, but individual parts have deformational and heating histories dating from before the aggregation of the meteorite.     

Shock reequilibration of fluid inclusions in Coconino sandstone from Meteor Crater,Arizona

This study examines the effects of natural shock metamorphism on fluid inclusions trapped in porous sedimentary target rocks and compares these results to previous experimental work on single crystal quartz. Samples of shock metamorphosed Coconino sandstone were collected from Barringer Meteorite Crater (Meteor Crater, Arizona) and classified based on their shock features into the six shock stages described by Kieffer [S.W. Kieffer, 1971. Shock metamorphism of the Coconino sandstone at Meteor Crater, Arizona, Journal of Geophysical Research 76, 5449-5473.]. The frequency of two-phase fluid inclusions decreases dramatically from unshocked samples of Coconino sandstone through shock stages 1a, 1b, and 2. No two-phase fluid inclusions were observed in shock stage 3 or 4 samples. However, the total number of grains containing fluid inclusions remains approximately the same for shock stages 1a–2, suggesting that two-phase fluid inclusions reequilibrated during impact to form single-phase inclusions. In shock stages 3 and 4, the total number of inclusions also decreases, indicating that at these higher shock pressures fluid inclusions are destroyed by plastic deformation and phase changes within the host mineral. Entrained quartz grains within a shock stage 5 sample contain two-phase inclusions, emphasizing the short duration of melting associated with the impact and the heterogeneous nature of impact processes. These results are similar to those observed in single-crystal experiments, although inclusions survive to slightly higher shock pressures in samples of naturally shocked Coconino sandstone. Results of this study suggest that the rarity of fluid inclusions in meteorites does not preclude the presence of fluids on meteorite parent bodies. Instead, fluid inclusions trapped during alteration events may have been destroyed due to shock processing. In addition, loss of fluids from inclusion vesicles along fractures and microcracks may lead to shock devolatilization, even in unsaturated target rocks.     

Shock behavior of zircon: phase transition to scheelite structure and decomposition

Both single-crystal and powdered specimens of zircon (ZrSiO₄) were shocked to peak pressures between 30 and 94 GPa using the gun method, and specimens recovered were studied by means of X-ray diffraction analysis, transmission electron microscopy and infrared spectroscopy. Transformation to the scheelite structure started above 30 GPa, and was completed above 53 GPa in the case of single crystal specimens. Tetragonal unit cell parameters of the scheelite type ZrSiO₄ at room condition are measured to bea = 4.7341(1)Å, c = 10.51(1)Å, c/a = 2.219(2) andV = 235.5(2)ų, which is smaller than that of the zircon type by 9.9%. The recovered scheelite-type ZrSiO₄ reverts to the zircon type after rapid heating to 1200°C at room pressure. This transformation from the zircon type to the scheelite type is unique in that it is fast, displacive-like, but does not reverse. Tetragonal ZrO₂ was detected as decomposition product in the single-crystal specimen shocked to 94 GPa, and further confirmed in a powdered specimen shocked to 53 GPa where enhancement of temperature is expected because of high porosity. Decomposition behavior of zircon observed in natural shock events is discussed on the basis of present experimental results.     

Incipient melting in and shock classification of L-group chondrites

Thirty-three of 52 type L4 to L6 chondrites that we have examined in thin section contain closed bodies of crystal-laden glass or devitrified glass (melt pockets) that testify to in-situ melting. A close correlation between the distribution of melt pockets and shock intensity as inferred from the characteristics of olivine and plagioclase indicates that the pockets reflect shock melting. The appearance of pockets coincides with a sharp decrease of⁴⁰Ar in L-group chondrites, suggesting that shock melting was responsible for loss of argon and raising the possibility that this process redistributed other volatile elements as well. The use of three criteria for shock intensity — olivine and plagioclase characteristics, and the presence or absence of melt pockets — leads to a refined shock classification for equilibrated chondrites that is based entirely on petrographic observations.     

The compositions of incipient shock melts in L6 chondrites

Microprobe analyses of 33 melt pocket glasses in five L6d and L6e chondrites show them to be chemically varied but typically enriched in the constituents of plagioclase relative to the host meteorites. This enrichment appears to increase with the degree of melting (0–6.5 vol.%), but other chemical variations among the glasses (sodium depletion, reduction of ferrous iron) appear to be unrelated to shock intensity and melt abundance.Chemical trends for melt pocket glasses differ sharply from those reported for chondrules in ordinary chondrites. Thus partial shock melting of chondritic material is an inadequate explanation for the chemical properties of chondrules.     

A new type of chondritic meteorite found in lunar soil

A fragment found in soil from the Apollo 12 site (12037, from the rim of Bench Crater) appears to be a unique type of chondrite, petrologically and chemically distinct from other chondrites and lunar rocks. Inclusions consisting of shocked pyroxene rimmed by euhedral troilite crystals are set in a black aphanitic matrix. Abundant magnetite in the matrix exhibits microscopic morphologies (framboids and plaquets) characteristic of C1 chondrites. The bulk composition of this sample has high Mg/Si and low Fe/Si relative to other chondrites, and P and S are strongly enriched. Most compositional differences between this meteorite and other chondrites may be explained by fractionation of Fe phases, such as magnetite and troilite. Low refractory element contents preclude mixing with lunar materials. This sample may be a surviving fragment of the meteoritic component present in the lunar regolith. Its characteristics suggest that ancient meteoritic debris sampled by the moon may be significantly different from that captured by the present-day earth.     

Effect of high-pressures on the electrical resistivity of natural zeolites from Deccan Trap, Maharashtra, India

We report here the electrical resistivity measurements on two natural zeolites–natrolite and scolecite (from the Killari borehole, Maharashtra, India) as a function of pressure up to 8 GPa at room temperature. High-pressure electrical resistivity studies on hydrous alumino-silicate minerals are very helpful in understanding the role of water in deep crustal conductivities obtained from geophysical models. The results obtained by magneto-telluric (MT) soundings and direct current resistivity surveys, along with the laboratory data on the electrical resistivity of minerals and rocks at high-pressure–temperature are used to determine the electrical conductivity distribution in continental lithosphere. The electrical resistivity of natural natrolite decreases continuously from 2.9 × 10⁹ Ω cm at ambient condition to 7.64 × 10² Ω cm at 8 GPa, at room temperature. There is no pressure-induced first order structural phase transitions in natrolite, when it is compressed in non-penetrating pressure transmitting medium up to 8 GPa. On the other hand scolecite exhibits a pressure-induced transition, with a discontinuous decrease of the electrical resistivity from 2.6 × 10⁶ to 4.79 × 10⁵ Ω cm at 4.2 to 4.3 GPa. The observed phase transition in scolecite is found to be irreversible. Vibrational spectroscopic and X-ray diffraction studies confirm the amorphous nature of the high-pressure phase. The results of the present high-pressure studies on scolecite are in good agreement with the high-pressure Raman spectroscopic data on scolecite. The thermo gravimetric studies on the pressure-quenched samples show that the samples underwent a pressure-induced partial dehydration. Such a pressure-induced partial dehydration, which has been observed in natural scolecite could explain the presence of high conductive layers in the earth's deep-crust.     

Stability relation of (Mg,Fe)SiO3 garnets, major constituents in the Earth's interior

High-pressure and high temperature experiments at 20 GPa on (Mg,Fe)SiO₃ have revealed stability fields of two types of aluminium-free ferromagnesian garnets; non-cubic garnet and cubic garnet (majorite). Majorite garnet is stable only within a limited compositional variation, 0.2 < Fe/(Mg + Fe)< 0.4, and in the narrow temperature interval of 200°C around 2000°C, while the stability of non-cubic garnet with more iron-deficient compositions persists up to higher temperatures. These two garnets show fractional melting into iron-deficient garnet and iron-rich liquid, and the crystallization field of cubic garnet extends over Fe/(Mg + Fe)= 0.5. The assemblage silicate spinel and stishovite is a low-temperature phase, which also occurs in the iron-rich portion of the MgSiO₃—FeSiO₃ system. The sequence as given by the Fe/(Mg + Fe) value for the coexisting phases with the two garnets at 2000°C and 20 GPa is: silicate modified spinel aluminium-free garnets silicate spinel.Natural majorite in shock-metamorphosed chondrites is clarified to be produced at pressures above 20 GPa and temperatures around 2000°C. Similar shock events may cause the occurrence of non-cubic garnet in iron-deficient meteorites. Non-cubic garnet could be a stable phase in the Earth's mantle if a sufficiently low concentration of aluminium is present in the layer corresponding to the stable pressure range of non-cubic garnet. The chemical differentiation by melting in the deep mantle is also discussed on the basis of the present experimental results and the observed coexistence of majorite garnet with magnesiowüstite in chondrites.     

Magnetic field and shock effects and remanent magnetization in a hypervelocity impact experiment

The impact of aluminum projectiles onto high-alumina terrestrial basalt blocks at 13–15 km s^?1 in the presence of a variable magnetic field has been studied. Low-frequency search coil data show that plasma is produced. causing local compression of the ambient field. Although field production is expected, it was not detectable with the existing apparatus. Measurements of the remanence of the shocked basalt show that magnetization was acquired in the material near the craters. The acquired remanence is predominantly soft, but also contains a component not demagnetized by 500 Oe AC field treatment. Material shocked in a 10-Oe vertical field exhibits inverse dependence of magnetization upon distance from the crater center. Examination of the shocked basalt in thin section reveals a general lack of shock metamorphism in the material surrounding the crater, except for the presence of a high-pressure melt glass which was splashed onto the crater walls. Micro-probe analyses show that the glass is a whole-rock melt of fairly uniform composition, and is contaminated with aluminum from the projectile. The mineralogical data support the view that the acquired magnetization is shock remanence, since negligible shock heating occurred in the magnetized material. These results bear on the problem of lunar magnetism, suggesting that shock effects or possibly thermoremanence in ejecta fragments may be responsible for part of the magnetization of the lunar surface.     

ALH85085: a unique volatile-poor carbonaceous chondrite with possible implications for nebular fractionation processes

Allan Hills 85085 is a unique chondrite with affinities to the Al Rais-Renazzo clan of carbonaceous chondrites. Its constituents are less than 50 μm in mean size. Chondrules and microchondrules of all textures are present; nonporphyritic chondrules are unusually abundant. The mean compositions of porphyritic, nonporphyritic and barred olivine chondrules resemble those in ordinary chondrites except that they are depleted in volatile elements. Ca-, Al-rich inclusions are abundant and largely free of nebular alteration; they comprise types similar to those in CM and CO chondrites, as well as unique types. Calcium dialuminate occurs in several inclusions. Metal, silicate and sulfide compositions are close to those in CM-CO chondrites and Al Rais and Renazzo. C1-chondrite clasts and metal-rich “reduced” clasts are present, but opaque matrix is absent. Siderophile abundances in ALH85085 are extremely high (e.g., Fe/Si= 1.7 × solar), and volatiles are depleted (e.g., Na/Si= 0.25 × solar, S/Si= 0.03 × solar). Nonvolatile lithophile abundances are similar to those in Al Rais, Renazzo, and CM and CO chondrites.ALH85085 agglomerated when temperatures in the nebula were near 1000 K, in the same region where Renazzo, Al Rais and the CI chondrites formed. Agglomeration of high-temperature material may thus be a mechanism by which the fractionation of refractory lithophiles occurred in the nebula. Chondrule formation must have occurred at high temperatures when clumps of precursors were small. After agglomeration, ALH85085 was annealed and lightly shocked. C1 and other clasts were subsequently incorporated during late-stage brecciation.     

The phase diagram of CaCO3 in relation to shock compression and decomposition

The phase diagram for calcite (CaCO₃) is re-evaluated in relation to dynamic compression and following release from shock. Available shock compression data on Hugoniot dynamic measurements, analysis of recovered samples, and observation at terrestrial impact sites are compared with theoretically derived equations of state (EOS) for CaCO₃ and its decomposition products CaO and CO₂. The study results in a refined phase diagram for CaCO₃ in which the major change is the extension of the liquid field of CaCO₃. A general outcome of this analysis is that release of CO₂ from naturally shocked carbonates to the atmosphere is (grossly) overestimated if based on the calcite phase diagram constructed from thermodynamic equilibrium conditions.     

Shock and post-shock temperatures in an ice–quartz mixture: implications for melting during planetary impact events

Melting of H₂O ice during planetary impact events is a widespread phenomenon. On planetary surfaces, ice is often mixed with other materials; yet, at present, the partitioning of energy between the components of a shocked mixture is still an open question in the shock physics community. Knowledge of how much energy is partitioned into the ice component is necessary to predict and interpret a wide range of processes, including shock-induced melting and chemistry. In this work, we construct a conceptual framework for the thermodynamic pathways of the components in a shocked hydrodynamic mixture by defining three broad regimes based on the characteristic length scale of the mixture compared to the thickness of the shock front: (1) small length scale mixtures where pressure and temperature equilibrate immediately behind the shock front; (2) intermediate length scales where pressure but not thermal equilibration is achieved behind the shock front; and (3) long length scales where pressure equilibration requires multiple shock wave reflections. We conduct shock wave experiments, reaching pressures from 8 to 23 GPa, in an H₂O ice–SiO₂ quartz mixture in the intermediate length scale regime. In each experiment, all the parameters required to address the question of energy partitioning were determined: the shock velocity in the mixture, the shock front thickness, and the shock and post-shock temperatures of the H₂O component. The measured pressure is in agreement with the bulk compressibility of the mixture. The shock and post-shock temperatures of the H₂O component indicate that the ice was shocked close to the principal Hugoniot. Therefore, in the intermediate length scale regime, the partitioning of shock energy is defined initially by the Hugoniots of the components at the equilibrated pressure. We discuss energy partitioning in mixtures over the wide range of length and time scales encountered during planetary impact events and identify the current challenges in calculating the volume of melted ice. In some cases, the criteria for shock-induced melting of ice in a mixture are the same as for pure ice.     

Shock metamorphism of some rock-forming minerals

The shock metamorphism of schist consisting of garnet, biotite, quartz, and plagioclase is studied under shock wave loading of a sample in steel recovery ampoules of plane geometry. A maximum shock pressure was reached during several circulations of waves in the sample (stepwise shock compression) and varied within the range 19–52 GPa. The recovered samples were examined by the methods of scanning electron microscopy and microprobe and X-ray phase analysis. The results were compared with natural impactites and with shock-induced alterations in minerals loaded by a spherical convergent wave. It is established that, given a plane geometry of loading (stepwise shock compression), solid-state transformations at the lattice level (migration of chemical elements and formation of shock thermal aggregates) are not observed in all of the studied minerals, in contrast to natural impact processes and spherical geometry experiments. Under the conditions of our experiments, minerals melt at higher pressures than in the case of natural impact processes and spherical geometry experiments. However, for each mineral studied, the mechanical strain patterns at close shock pressures are, on the whole, the same for all of the aforementioned three variants of shock wave loading.     

Hugoniot equation of state of olivine and its geodynamic implications

Large olivine samples were hot-pressed synthesized for shock wave experiments. The shock wave experiments were carried out at pressure range between 11 and 42 GPa. Shock data on olivine sample yielded a linear relationship between shock wave velocity D and particle velocity u described by D=3.56(?0.13)+2.57(?0.12)u. The shock temperature is determined by an energy relationship which is approximately 790°C at pressure 28 GPa. Due to low temperature and short experimental duration, we suggest that no phase change occurred in our sample below 30 GPa and olivine persisted well beyond its equilibrium boundary in metastable phase. The densities of metastable olivine are in agreement with the results of static compression. At the depth shallower than 410 km, the densities of metastable olivine are higher than those of the PREM model, facilitating cold slab to sink into the mantle transition zone. However, in entire mantle transition zone, the shock densities are lower than those of the PREM model, hampering cold slab to flow across the "660 km" phase boundary.     

Shock temperature in calcite (CaCO3) at 95-160 GPa

The temperatures induced in crystalline calcite (CaCO₃) upon planar shock compression (95-160 GPa) are reported from two-stage light gas gun experiments. Temperatures of 3300-5400 K are obtained by fitting six-channel optical pyrometer radiances in the 450-900 nm range to the Planck gray-body radiation law. Thermodynamic calculations demonstrate that these temperatures are some 400-1350 K lower than expected for vibronic excitations of the lattice with a 3R/mole-atom specific heat (R is gas constant). The temperature deficit along the Hugoniot is larger than that expected from only melting. In addition to melting, it appears likely that shock-induced decomposition of calcite occurs behind the shock front. We modeled disproportionation of calcite into CaO (solid) plus CO₂ (gas). For temperature calculations, specific heat at constant volume for 1 mole of CO₂ is taken to be 6.7R as compared to 9R in the solid state; whereas a mole of calcite and a mole of CaO have their solid state values 15R and 6R, respectively. Calculations suggest that the calcite decomposes to CaO and CO₂ at ∼110±10 GPa along the Hugoniot. Recent reanalysis of earlier VISAR measurements of particle velocity profiles [1] indicates that calcite shocked to 18 GPa undergoes disproportionation at much lower pressures upon isentropic expansion.     

An experimental facility for the investigation of magma fragmentation by rapid decompression

 A special experimental facility has been developed to investigate the fragmentation of vesicular magma undergoing rapid decompression. The facility operates in a regime similar to that of shock tubes and at temperatures up to 950  °C and pressures up to 200 bar. Cylindrical samples (diameter ca. 17 mm, length ca. 50 mm) undergo rapid decompression in a high-temperature, high-pressure section of the facility following the disruption of a diaphragm separating that section from a low-pressure, low-temperature section. Actual vesicular magma samples have been experimentally fragmented at elevated temperatures and pressures corresponding to those observed during explosive volcanic eruptions and the resulting pyroclastics have been photographically resolved in flight and collected for physical characterization. The results of these experiments show that the rapid decompression of highly viscous vesicular magma can generate pyroclastic ejecta via rapid and complete fragmentation of magma at high temperature. This new fragmentation facility is presented as a tool for experimental volcanology under well-constrained conditions. Received: 19 March 1996 / Accepted: 25 August 1996     

Shock-produced vapor-grown crystals in the Yanzhuang meteorite

Vapor-grown crystals intimately related to shock metamorphism of meteorites were found in the Yanzhuang (H6) chondrite which had been heavily impacted in the space. These crystals include: (i) subhedral low-Ca pyroxene occurring on the wall of the pores within a silicate melt pocket that experienced a shock temperature higher than 1500°C, (ii)Fe-Ni needle-whiskers (taenite) occurring in the cracks in the partially melted chondritic facies that experienced a shock temperature of 850–1300°C, (iii) troilite with abundant microholes occurring in the cracks in the brecciated facies and the lightly deformed chondritic facies that experienced a shock temperature lower than 850°C. The occurrence and mineralogical features of vapor-grown crystals show that vaporization of minerals could be produced in heavily impacted meteorites and that a small amount of crystals could be depositedin situ from vapor phases. Project supported by the Natural Science Foundation of Guangdong Province.