Activation energy of annealed metamict gadolinite from 57Fe Mössbauer spectroscopy

Gadolinite, REE₂FeBe₂Si₂O₁₀, is commonly metamict. ⁵⁷Fe Mössbauer annealing studies of fully metamict gadolinite from Ytterby, Sweden, have been completed in argon atmosphere from 873 to 1473 K. This technique has rarely been employed in studies of metamict minerals. Changes in the experimental parameters of Mössbauer spectra are sensitive indicators of the thermal recrystallization process of metamict gadolinite and revealed two stages of the structural recovery: a major stage from 873 to 1073 K and a slower recovery stage from 1133 to 1473 K. These observations are confirmed by X-ray powder diffraction. In relation to the first stage, the exponential behaviour of the changes in the Mössbauer parameters can be used for deriving the activation energy E _a of the recrystallization process. The calculated value E _a =1.97 eV in argon atmosphere explains the common occurrence of gadolinite in the fully or partially metamict state. Results of Mössbauer spectroscopy suggest that the recrystallization of metamict gadolinite is a displacive transition that involves rotation and translation of SiO₄ and BeO₄ to their normal positions associated with removal of OH groups from the structure.     

A TEM investigation of natural metamict zircons: structure and recovery of amorphous domains

The nature of the amorphous regions and their recovery processes in two natural metamict zircon samples from Sri Lanka have been studied by high resolution and analytical transmission electron microscopy. Samples untreated and annealed at different temperatures were investigated. Nanoprobe analyses on untreated samples and samples annealed at 1000 K show that within experimental uncertainties, no chemical segregation occurred. In samples annealed at higher temperatures (≥1100 K) recovery occurs in a two-stage process and leads to different microstructures, which depended on the initial amount of metamictization. In highly amorphized samples, recrystallization starts at 1200 K. Randomly oriented ZrO₂ grains embedded in a silica-rich matrix are detected. At higher temperature (16 h at 1600 K), the assemblage transforms into a polygonal texture of small zircon grains. Some untransformed zirconia grains and pockets of silica-rich glass are still present, however. In partially metamict samples, recovery starts at 1100 K. The small surviving oriented zircon domains grow at the expense of the surrounding amorphous material. At 1200 K, new zirconia grains nucleate with random orientations. After 1 h annealing at 1400 K, the zircon structure is restored and the microstructure coarse-grained. The proportion of crystalline zirconia and silica-rich glass has dramatically decreased. Received: 15 November 1999 / Accepted: 1 March 2000     

江西大吉山五里亭花岗岩中变生褐帘石的加热研究

对采自我国南方燕山期五里亭花岗岩体中的褐帘石,经偏光显徽镜、电子探针仪、差热仪、X射线等方法进行分析得出,该矿物为变生褐帘石。加热800℃,850℃,950℃,970℃,1100℃退火系列样品的X射线粉晶数据分析得出:1.变生褐帘石X射线粉晶分析的最宜加热温度为800-850℃;2.加热至970℃的退火样品,褐帘石已分解为方铈石、赤铁矿、钙长石,加热到1100℃,褐帘石已渐消失,方铈石、钙长石和赤铁矿成为主要矿物相。     

Recrystallization mechanisms of fergusonite from metamict mineral precursors

The metamict state and recrystallization of fergusonite in metamict natural samples were studied by thermal methods (TGA-DTA), X-ray powder diffraction (XRD), Raman spectroscopy (RS), transmission electron microscopy (TEM), selected area electron diffraction (SAED), and electron microprobe (EPMA). Two metamict mineral samples of fergusonite were investigated in order to identify the original premetamict crystal structure and to identify recrystallization mechanisms. The TEM data and RS provided evidence on the partial preservation of the original structure in the investigated minerals, which are X-ray amorphous. It was shown that fergusonite could recrystallize from a metamict mineral with original fergusonite structure or from metamictized pyrochlore, which was altered before or after metamictization. Two recrystallization mechanisms were recognized: (a) epitaxial growth occurring at the boundary between preserved premetamict structure fragments and completely metamictized areas, and (b) nucleation-crystal growth mechanism occurring in completely amorphous areas of the minerals, and resulting in recrystallization of the original mineral as well as in the crystallization of a new mineral with a modified chemical composition as compared to the initial matrix.     

Energetics of radiation damage in natural zircon (ZrSiO4)

Transposed temperature drop calorimetry at 1000 °C was performed on natural zircons (ZrSiO₄) from Sri Lanka that were partially to completely metamict due to α-decay event damage (0.06 to 11.7×10¹⁵ α-decay events/mg). The enthalpy of annealing at room temperature (ΔH_anneal) varies sigmoidally as a function of radiation dose. ΔH_anneal reaches a saturation plateau at radiation doses greater than 5×10¹⁵ α-decay events/mg. The annealing of several samples to a crystalline structure with broadened diffraction peaks does not significantly affect the enthalpy of annealing. The large magnitude of the enthalpy of annealing plateau, ?59±3 kJ/mol, suggests that the damage to the structure is pervasive on the scale of Angstroms, consistent with the loss of mid-range order characteristic of a glass. The energetics are consistent with, but do not require, chemical heterogeneity caused by micro-domains of amorphous SiO₂-rich and ZrO₂-rich regions in the metamict state.     

Characterization of the amorphous state in metamict silicates and niobates by EXAFS and XANES analyses

X-ray absorption spectroscopy using synchrotron radiation has been applied to the investigation of the coordination geometries around Y, Zr and Nb atoms in metamict zircon, gadolinite, fergusonite, euxenite and samarskite. EXAFS and XANES spectra of their crystalline counterparts and synthetic compounds including ZrO₂, Y₂O₃, YNbTiO₆, YNbO₄, LiNbO₃, and NiNb₂O₆ were also measured for comparison. Metamict zircon shows a significant decrease in its Zr-O bond distances accompanying an increase in distortion of the Zr-O coordination polyhedra as compared with crystalline zircon. On the contrary, the average Nb-O bond distances and the symmetry of the coordination polyhedra around the Nb atoms in metamict euxenite and samarskite resemble those in the crystalline euxenite. Compared with crystalline fergusonite, a decrease in the distortion of the Nb-O octahedra is observed in metamict fergusonite. The structures of the second nearest neighbors (the metal-metal interactions) are largely disrupted in the metamict specimens except for metamict zircon and samarskite with high trivalent iron concentration. Nb in metamict samarskite is in octahedral coordination by oxygen and is similar to that in euxenite.     

Isothermal annealing of partially metamict zircon: evidence for a three-stage recovery process

 Raman spectroscopy and the powder diffraction technique have been used to monitor the recovery process of two partially metamict zircons (2.6 and 4.8 × 10¹⁸ α-decays g⁻¹) from Sri Lanka during a series of isothermal annealing experiments in the temperature range from 870 to 1622 K. These experiments show for the first time that structural recovery in partially metamict zircon proceeds via three distinct recovery stages, each of which occurs within a distinct time-temperature regime. Whereas the first two stages have previously been recognized (recovery of damaged crystalline remnants and epitaxial recrystallization), the third stage has not yet been identified as a single activated process. It is suggested that anisotropic defect annealing during the first stage at low temperatures, where the structure recovers preferentially along the a(b) plane, produces a geometrical situation where large structural rearrangements are necessary to remove the remaining defects inside the crystalline material. This situation is approximately reached when the amorphous domains start to recrystallize. The reason for anisotropic annealing can be found in a different connectivity between polyhedral linkages in both directions of the zircon lattice. High apparent activation energies, in the range of 6.4 to 7.9 eV, were determined for the third recovery stage from the Raman data, which are interpreted to reflect large structural rearrangements (i.e. polyhedral tilting) associated with the final recovery of the c axis. This explains the occurrence of a distinct recrystallization stage without defect annealing. Finally, it should be mentioned that the first recovery stage is not necessarily expected to occur in less damaged zircon crystals (<∼2 × 10¹⁸ α-decays g⁻¹), since less stable defects along the basal plane might have already been self-annealed during radiation damage accumulation under ambient temperatures. Received: 6 September 2001 / Accepted: 25 February 2002     

Metamict transformations in some niobates and zircons according to X-ray absorption spectra

The niobium and zirconium L _III-absorption spectra in some niobates and zircons were obtained with a vacuum focusing crystal spectrometer. The effective charges of Nb and Zr in these minerals were derived from the X-ray absorption spectra. The fine structure of the absorption spectra and effective charges Nb and Zr in metamict, partly-metamict minerals and crystalline analogues made it possible to draw a conclusion as to the nature of the first coordination sphere of Nb and Zr during metamict decay and subsequent recrystallization under annealing of these minerals.     

Prograde metamorphic sequence of REE minerals in pelitic rocks of the Central Alps: implications for allanite–monazite–xenotime phase relations from 250 to 610 °C

The distribution of REE minerals in metasedimentary rocks was investigated to gain insight into the stability of allanite, monazite and xenotime in metapelites. Samples were collected in the central Swiss Alps, along a well‐established metamorphic field gradient that record conditions from very low grade metamorphism (250 °C) to the lower amphibolite facies (～600 °C). In the Alpine metapelites investigated, mass balance calculations show that LREE are mainly transferred between monazite and allanite during the course of prograde metamorphism. At very low grade metamorphism, detrital monazite grains (mostly Variscan in age) have two distinct populations in terms of LREE and MREE compositions. Newly formed monazite crystallized during low‐grade metamorphism (<440 °C); these are enriched in La, but depleted in Th and Y, compared with inherited grains. Upon the appearance of chloritoid (～440–450 °C, thermometry based on chlorite–choritoid and carbonaceous material), monazite is consumed, and MREE and LREE are taken up preferentially in two distinct zones of allanite distinguishable by EMPA and X‐ray mapping. Prior to garnet growth, allanite acquires two growth zones of clinozoisite: a first one rich in HREE + Y and a second one containing low REE contents. Following garnet growth, close to the chloritoid–out zone boundary (～556–580 °C, based on phase equilibrium calculations), allanite and its rims are partially to totally replaced by monazite and xenotime, both associated with plagioclase (± biotite ± staurolite ± kyanite ± quartz). In these samples, epidote relics are located in the matrix or as inclusions in garnet, and these preserve their characteristic chemical and textural growth zoning, indicating that they did not experience re‐equilibration following their prograde formation. Hence, the partial breakdown of allanite to monazite offers the attractive possibility to obtain in situ ages, representing two distinct crystallization stages. In addition, the complex REE + Y and Th zoning pattern of allanite and monazite are essential monitors of crystallization conditions at relatively low metamorphic grade.     

Thermoluminescence and the shock and reheating history of meteorites—II: Annealing studies of the Kernouve meteorite

Samples of the unshocked, equilibrated chondrite, Kernouve (H6), have been annealed for 1–100 hours at 500–1200°C, their thermoluminescence sensitivity measured and Na, K, Mn, Ca and Sc determined by instrumental neutron activation analysis. The TL sensitivity decreased with temperature until by 1000°C it had fallen by 40%. The process responsible has an activation energy of ~8 kcal/mole and probably involves diffusion. Samples annealed 1000–1200°C had TL sensitivities 10^?2 times the unannealed values, most of the decrease occurring ~1100°C. This process has an activation energy of ~100 kcal/mole and is probably related to the melting of the TL phosphor, feldspar, with some decomposition and loss of Cs, Na and K. Meteorites whose petrography indicates healing > 1100°C by natural shock heating events (shock facies d-f). have TL sensitivities similar to samples annealed > 1100°C. Our own and literature compositional data indicate that TL is more stable to annealing than Ag, In, Tl, Bi, Zn and Te and less stable than Na, K, Mn, Ca, Se and Co, while the TL decrease resembles very closely the pattern of Cs loss on annealing.     

Britholites as natural analogues of actinide matrices: Resistance to radiation damage

Crystallization of borosilicate glasses, used now for solidification of liquid nuclear high-level wastes (HLW), is accompanied by the formation of silicates with the apatite-type structure and high contents of actinides and REE. The stability of these silicates determines the safety of immobilization of radionuclides. As a result of radioactive decay, the crystalline phases of actinides become amorphous with time and their solubility in aqueous solutions increases. One of the ways to assess the radiation stability of compounds is the study of their natural analogues that contain radioactive elements. Minerals of the britholite group are the natural analogues of synthetic rare earth silicates and actinides with the apatite-type structure. Seven britholites of different ages and with different ThO₂ + UO₂ contents have been studied. The stages of partial damage and complete destruction of sample structures under the effect of radioactive decay were distinguished. The radiation stability of natural britholites surpasses that of their synthetic analogues. The annealing of metamict samples recovers the primary apatite-type structure without formation of any other phases. With an increase in annealing duration from 1 to 5 h, the mineral structure is recovered at a lower (by 200°C) temperature (down to 550–600°C). The temperature conditions in underground storages and the substantially longer occurrence of HLW therein will prevent crystalline matrices with the apatite-type structure from amorphization and thus ensure the retention of their stability.     

Thermoluminescence and the shock and reheating history of meteorites—III: The shergottites

The thermoluminescence (TL) sensitivities of the four shergottites are extremely low and display a 10-fold range (values are 0.15 to 1.8, where Dhajala = 1000), with the TL sensitivity decreasing with increasing peak temperature (from about 140 to 180°C) and peak width (from about 100 to 150°C). A mineral separation experiment indicates that the mineral producing the TL is associated with the maskelynite, presumably nanogram per gram quantities of crystalline feldspar are present in the maskelynite. Samples of Shergotty, Allan Hills A77005 and Elephant Moraine A79001 were annealed at 400–900°C for 24–98 h. For Shergotty, the peak increased in width and moved to higher temperatures in the glow-curve, while for Allan Hills A77005 and Elephant Moraine A79001, whose TL peaks were already broad and at high temperatures, remained unchanged. All samples showed a significant increase in TL sensitivity when annealed at >600–700°C. Apparently, the feldspar is present in varying proportions of high to low-temperature form and in amounts which vary from meteorite to meteorite. We conclude that the shergottites underwent post-shock recrystallization at a variety of cooling rates and that the order of increasing cooling rate was Shergotty, Allan Hills A77005, Zagami and Elephant Moraine A79001. The presence of a high-temperature phase implies peak post-shock cooling temperatures >600°C and that the size of the ejecta was <10 m. Current theories are well able to explain the ejection of such small objects from Mars.     

Annealing studies of fission tracks in allanite

The annealing characteristics of fission tracks in allanite have been studied. All the tracks in the mineral fade at 720° C for one hour heating. The activation energy of allanite ranges from 1.4 to 3.4 eV.     

A raman spectroscopic study of Al-Si ordering in synthetic magnesium cordierite

A number of previous investigations have examined the ordering behavior of magnesium cordierite using X-ray diffraction, transmission electron microscopy, infrared spectroscopy and solution calorimetry. In the present investigation, one series of samples from the above studies has been examined by Raman spectroscopy. Systematic modifications in the spectra with annealing time at 1,200° C are consistent with a continuous ordering of the average Al/Si distribution from 4 h to at least 64 h, and which may begin earlier. Spectral changes are first definitely observed when the ordered domains are around 100 Å across, suggesting that Raman spectroscopy is sensitive to this distance scale. The spectra of samples annealed at 1,200° C are compared with samples annealed at 1,400°; C where ordering proceeds much faster, and the possible use of Raman spectroscopy in characterization of Al/Si order in cordierite is discussed. Finally, the Raman spectrum of Mg₂Al₄Si₅O₁₈ with a stuffed β-quartz structure has been obtained. Comparison of its spectrum with that of cordierite glass suggests similar structures for both, which seem different to that of disordered cordierite.     

Dissolution–precipitation reactions in hydrothermal experiments with quartz–feldspar aggregates

Batch and flow-through experiments were performed on quartz–feldspar granular aggregates at hydrothermal conditions (up to ≈150 °C, up to 5 MPa effective pressure, and near-neutral pH) for up to 141 days. The effect of dissolution–precipitation reactions on the surface morphology of the mineral grains was investigated. The starting materials as well as the solids and fluids resulting from the experiments were characterized using BET, energy dispersive X-ray spectroscopy, electron microprobe analysis, inductively coupled plasma-optical emission spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray powder diffraction, and X-ray fluorescence spectroscopy. The electrical conductivity of fluid samples was used as a proxy for the evolution of the fluid composition in the experiments. The chemical analyses of the fluids in combination with hydrogeochemical simulations with PHREEQC suggested the precipitation of Al–Si-bearing solid phases. Electron microscopy confirmed the formation of secondary amorphous Al–Si-bearing solid phases. The microscopic observations are consistent with a process of stoichiometric dissolution of the mineral grains, transport of dissolved ions in the fluid phase, and spatially coupled precipitation of sub-μm sized amorphous particles on mineral surfaces. These findings shed light onto early stages of diagenesis of quartz–feldspar sands and indicate that amorphous phases may be precursors for the formation of crystalline phases, for example, clay minerals.     

Interpretation of discordant U-Pb zircon ages: An evaluation

The most widely used technique for the determination of high precision mineral growth ages in igneous and metamorphic rocks is dating of zircons with the U-Pb method. The interpretation of these ages, particularly in metamorphic settings, is hampered by an incomplete understanding of the common phenomenon of partial Pb-loss in zircon. In principle, this Pb-loss may occur in four very different ways: diffusion in metamict zircon, diffusion in pristine zircon, leaching from metamict zircon and recrystallization of metamict zircon. Here it is argued that, under conditions common in the continental crust, Pb-loss is only possible in partially to strongly metamict zircons. Pb-diffusion in the pristine zircon lattice is insignificant up to temperatures of at least 1000 °C. Pb-loss is only possible if the zircons experienced a time interval below their annealing temperature of about 600–650 °C, because only below this temperature can the lattice damage through α-decay and spontaneous fission accumulate. Zircons that remain above this temperature do not lose Pb by diffusion and will stay closed systems. Complete resetting of the U-Pb system in zircon under crustal conditions is only possible through dissolution and reprecipitation of zircon. Partial resetting results from recrystallization, leaching or diffusion in metamict zircon. As a consequence, special care has to be taken to interpret lower intercepts on concordia diagrams defined by discordant U-Pb data. Lower intercept ages may be significant only if they are defined by zircons with low U-content (<100 p.p.m.) or if confirmed by other geochronological methods. In addition, the accuracy of the lower intercept should be confirmed by abrading the zircon fractions that define the discordia.     

Modification to the crystal structure of chlorite during early stages of its dissolution

Early stage processes of Mg-rich chlorite (clinochlore) dissolution were examined, focusing especially on the structural modification at grain edges during dissolution. Focused ion beam transmission electron microscopy sample preparation was applied to crystals dissolved in a flow-through reaction system at pH 3.0 and 25°C for 31 days. The obtained Si and Mg dissolution rates are −11.49 and −11.14 (logR, mol/(m²/s)), respectively, implying dissolution is non-stoichiometric. TEM-EDX analyses of dissolved samples reveal the development of 20–50-nm thick amorphous zone at an outermost rim with a chemical gradient of Mg, lower towards the solid surface, and Si enrichment in this amorphous zone. Crystalline material is partially interwoven with amorphous one at the interface between the amorphous and crystalline regions. These results indicate that the amorphous zone was produced by selective leaching of cations except for Si. Chlorite dissolution may proceed via the formation and thickening of leached layer as a by-product of release to solution of Si at slightly slower rate than Mg.     

Zircon reaction and stability of the U-Pb isotope system during interaction with carbonate fluid: experimental hydrothermal study

 The interpretation of metamorphically induced U-Pb isotopic discordance requires a thorough understanding of zircon-fluid interactions. With this aim we have studied the behaviour of metamict and crystalline zircon phases and their U-Pb systems by cathodoluminescence after treatment by 2M Na₂CO₃ solution at T = 200–800 °C and P = 1–5 kbar for 3–14 days, X-ray diffraction, microprobe and isotope dilution analysis. The data indicate that zircon transformation under hydrothermal conditions depends on the experimental conditions and the degree of structural damage. Reconstitution of defective and impurity-enriched zones of metamict zircon (homogenization of impure element concentrations and increase of crystallinity) was observed at 400 °C and P = 1 kbar. Considerable lead and uranium loss occurred under these conditions. As a result of zircon dissolution, newly formed baddeleyite accommodating U from 2M Na₂CO₃ solution and Zr-Na-silicate were recognized. This process intensified with increasing pressure. Study of crystalline zircon indicates that migration of U and Pb took place only during dissolution of zircon at T above 650 °C. In the presence of carbonate-ions essential U and Pb amounts are lost from metamict zircon at a lower P-T than is typical for greenschist facies metamorphism. Received: 4 October 1997 / Accepted: 6 December 1999     

Formation of epigenetic graphite inclusions in diamond crystals: experimental data

To elucidate the conditions of formation of epigenetic graphite inclusions in natural diamond, we carried out experiments on high-temperature treatment of natural and synthetic diamond crystals containing microinclusions. The crystal annealing was performed in the CO–CO₂ atmosphere at 700–1100 °C and ambient pressure for 15 min to 4 h. The starting and annealed diamond crystals were examined by optical microscopy and Raman spectroscopy. It has been established that the microinclusions begin to change at 900 °C. A temperature increase to 1000 °C induces microcracks around the microinclusions and strong stress in the diamond matrix. The microinclusions turn black and opaque as a result of the formation of amorphous carbon at the diamond–inclusion interface. At 1100 °C, ordered graphite in the form of hexagonal and rounded plates is produced in the microcracks. A hypothesis is put forward that graphitization in natural diamond proceeds by the catalytic mechanism, whereas in synthetic diamond it is the result of pyrolysis of microinclusion hydrocarbons. The obtained data on the genesis of graphite microinclusions in diamond are used to evaluate the temperature of kimberlitic melt at the final stage of formation of diamond deposits.     

Chemical and physical studies of type 3 chondrites—IV: Annealing studies of a type 3.4 ordinary chondrite and the metamorphic history of meteorites

Samples of a type 3.4 chondrite have been annealed at 400–1000°C for 1–200 hours, their thermoluminescence properties determined and analyzed for K, Na, Mn, Sc and Ca by instrumental neutron activation analysis. After annealing at ?900°C, the samples showed a 50% decrease in TL sensitivity, while after annealing at 1000°C it fell to 0.1-0.01 times its unannealed value and loss of Na and K occurred. The TL and compositional changes resemble those observed for the equilibrated Kernouve chondrite after similar annealing treatments, except that the sharp TL decrease, and element loss, occurred at ~ 1100°C; this difference is presumably due to petrographic differences in the feldspar of the two meteorites. The temperature and the width of the TL peak showed a discontinuous increase after annealing at 800°C; peak temperature jumped from 130 to 200°C and peak width increased from 90 to 150°C. The activation energies for these TL changes are 7–10 kcal/mole. Similar increases in the TL peak temperature have been reported in TL studies of Amelia, VA, albite, where they were associated with the low to high-temperature transformation. However, the activation energy for the transformation is ~80 kcal/mole. These changes in TL emission characteristics resemble trends observed in type 3 ordinary chondrites and it is suggested that type 3.3–3.5 chondrites have a low-feldspar as TL phosphor and > 3.5 have high-feldspar as the phosphor. Thermoluminescence therefore provides a means of palaeothermometry for type 3 ordinary chondrites.