Helium irradiation study on zircon

Synthetic ZrSiO₄ and (mildly to strongly radiation-damaged) natural zircon samples were irradiated with 8.8 MeV ⁴He²⁺ ions (fluences in the range 1 × 10¹³–5 × 10¹⁶ ions/cm²). For comparison, an additional irradiation experiment was done with 30 MeV ¹⁶O⁶⁺ ions (fluence 1 × 10¹⁵ ions/cm²). The light-ion irradiation resulted in the generation of new (synthetic ZrSiO₄) or additional (mildly to strongly metamict natural samples) damage. The maximum extent of the damage is observed in a shallow depth range approximately 32–33 μm (8.8 MeV He) and ~12 μm (30 MeV O) below the sample surface, i.e. near the end of the ion trajectories. These depth values, and the observed damage distribution, correspond well to defect distribution patterns as predicted by Monte Carlo simulations. The irradiation damage is recognised from the notable broadening of Raman-active vibrational modes, lowered interference colours (i.e. decreased birefringence), and changes in the optical activity (i.e. luminescence emission). At very low damage levels, a broad-band yellow emission centre is generated whereas at elevated damage levels, this centre is suppressed and samples experience a general decrease in their emission intensity. Most remarkably, there is no indication of notable structural recovery in pre-damaged natural zircon as induced by the light-ion irradiation, which questions the relevance of alpha-assisted annealing of radiation damage in natural zircon.     

U–Pb ages of Neoarchean granitoids from the Black Hills, South Dakota, USA: implications for crustal evolution in the Archean Wyoming province

Zircons in basement rocks from the eastern Wyoming province (Black Hills, South Dakota, USA) have been analyzed by ion microprobe (SHRIMP) in order to determine precise ages of Archean tectonomagmatic events. In the northern Black Hills (NBH) near Nemo, Phanerozoic and Proterozoic (meta)sedimentary rocks are nonconformably underlain by Archean biotite–feldspar gneiss (BFG) and Little Elk gneissic granite (LEG), both of which intrude older schists. The Archean granitoid gneisses exhibit a pervasive NW–SE-trending fabric, whereas an earlier NE–SW-trending fabric occurs sporadically only in the BFG, which is intruded by the somewhat younger LEG. Zircon crystals obtained from the LEG and BFG exhibit double terminations, oscillatory zoning, and Th/U ratios of 0.6±0.3—thereby confirming a magmatic origin for both lithologies. In situ analysis of the most U–Pb concordant domains yields equivalent ²⁰⁷Pb/²⁰⁶Pb ages (upper intercept, U–Pb concordia) of 2559±6 and 2563±6 Ma (both ±2σ) for the LEG and BFG, respectively, which constrains a late Neoarchean age for sequential pulses of magmatism in the NBH. Unzoned (in BSE) patches of 2560 Ma zircon commonly truncate coeval zonation in the same crystals with no change in Th/U ratio, suggesting that deuteric, fluid-assisted recrystallization accompanied post-magmatic cooling. A xenocrystic core of magmatic zircon observed in one LEG zircon yields a concordant age of 2894±6 Ma (±2σ). This xenocryst represents the oldest crustal material reported thus far in the Black Hills. Whether this older zircon originated as unmelted residue of 2900 Ma crust that potentially underlies the Black Hills or as detritus derived from 2900 Ma crustal sources in the Wyoming province cannot be discerned. In the southern Black Hills (SBH), the peraluminous granite at Bear Mountain (BMG) of previously unknown age intrudes biotite–plagioclase schist. Zircon crystals from the BMG are highly metamict and altered, but locally preserve small domains suitable for in situ analysis. A U–Pb concordia upper intercept age of 2596±11 Ma (±2σ) obtained for zircon confirms both the late Neoarchean magmatic age of the BMG and a minimum age for the schist it intrudes. Taken together, these data indicate that the Neoarchean basement granitoids were emplaced at 2590–2600 Ma (SBH) and 2560 Ma (NBH), most likely in response to subduction associated with plate convergence (final assembly of supercontinent Kenorland?). In contrast, thin rims present on some LEG–BFG zircons exhibit strong U–Pb discordance, high common Pb, and low Th/U ratios—suggesting growth or modification under hydrothermal conditions, as previously suggested for similar zircons from SE Wyoming. The LEG–BFG zircon rims yield a nominal upper intercept date of 1940–2180 Ma, which may represent a composite of multiple rifting events known to have affected the Nemo area between 2480 and 1960 Ma. Together, these observations confirm the existence of a Paleoproterozoic rift margin along the easternmost Wyoming craton. Moreover, the 2480–1960 Ma time frame inferred for rifting in the Black Hills (Nemo area) corresponds closely to a 2450–2100 Ma time frame previously inferred for the fragmentation of supercontinent Kenorland.     

The structure of metamict zircon: A temperature-dependent EXAFS study

The thermal annealing (300–1700 K) of two metamict zircons (Ampagabe, Madagascar and Näegy, Japan) has been studied using X-Ray Diffraction (XRD) and Extended X-ray Absorption Fine Structure spectroscopy (EXAFS) at Zr K-edge. Two stages of thermal annealing within the aperiodic zircon are evidenced between 293 and 1700 K. The first stage (up to 600° C) shows a decrease of the a ₀-cell parameter from 6.674 (at 300° C) to 6.610 (at 600° C)± 0.005 Å. In that temperature range, the average local environment around Zr (presence of ^VIIZr and d(Zr-Zr) 3.3–3.6 Å) shows a weak, but significant increase of the Zr-Zr correlations located at 3.3–3.4 Å, undetectable by XRD. At temperatures up to 700° C (stage 2), the XRD-Bragg component arising from crystalline zircon increases in magnitude, whereas, Zr-K EXAFS analysis indicates a progressive ^VIIZr^VIIIZr transition, associated with a recovery of the crystalline zircon medium-range environment. For both techniques, the zircon structure is fully recovered at annealing temperatures up to 900° C.Electrostatic modelings suggest that the ^VIIIZr^VIIZr transition observed in zircon with increasing alpha-decay damage creates significantly overbonded oxygen atoms around Zr. With increasing temperature, those oxygen atoms are better bonded to ^VIIZr, due to the thermal expansion of the Zr-O bond. The congruent recovery of the zircon structure should therefore be favoured with increasing temperature. On the other hand, the metamict network can be also partially reorganized around 400–500° C, with the creation of Zr-rich domains, as measured by EXAFS. However, the growth of these domains after 3 hours annealing affects only minor portions of the aperiodic network. This model is corroborated by a similar thermal behaviour observed for a synthetic sol-gel of ZrO₂ · SiO₂ composition.     

Determination of the uranium valence state in the brannerite structure using EELS, XPS, and EDX

In this study, the valence states of uranium in synthetic and natural brannerite samples were studied using a combination of transmission electron microscopy-electron energy loss spectroscopy, scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDX), and X-ray photoelectron spectroscopy (XPS) techniques. We used a set of five (UO₂, CaUO₄, SrCa₂UO₆, UTi₂O₆, and Y_0.5U_0.5Ti₂O₆) U standard samples, including two synthetic brannerites, to calibrate the EELS branching ratio, M₅/(M₄ +M₅), against the number of f electrons. The EELS data were collected at liquid nitrogen temperature in order to minimise the effects of electron beam reduction of U⁶⁺ and U⁵⁺. Test samples consisted of three additional synthetic brannerites (Th_0.7U_0.3Ti₂O₆, Ca_0.2U_0.8Ti₂O₆, and Th_0.55U_0.3Ca_0.15Ti₂O₆) and three natural brannerites from different localities. The natural brannerite samples are all completely amorphous, due to cumulative alpha decay events over geological time periods (24–508 Ma). Our U valence calibration results are in reasonable agreement with previous work, suggesting possibly a non-linear relationship between the branching ratio and the number of f electrons (and hence the average valence state) of U in solids. We found excellent agreement between the nominal valence states of U and the average valence states determined directly by EELS and estimated by EDX analysis (with assumptions regarding stoichiometry) in two of the three synthetic brannerite test samples. The average U oxidation states of the five synthetic brannerite samples, as derived from XPS analyses, are also in good agreement with those determined by other techniques. The average valence states of U in three amorphous (metamict) natural brannerite samples with alpha decay doses ranging from 3.6×10¹⁶ to 6.9×10¹⁷ /mg were found to be 4.4, 4.7, and 4.8, consistent with the presence of U⁵⁺ and/or U⁶⁺ as well as U⁴⁺ in these samples. These results are in general agreement with previous wet chemical analyses of natural brannerite. However, the average valence states inferred by SEM-EDX for two of the natural brannerite samples do not show satisfactory agreement with the EELS determined valence. This may be due to the occurrence of OH^– groups, cation vacancies, anion vacancies, or excess oxygen in the radiation-damaged structure of natural brannerite.     

A temperature-dependent single-crystal Raman spectroscopic study of fayalite: evidence for phonon-magnetic excitation coupling

The polarized single-crystal Raman spectrum of synthetic fayalite, Fe₂SiO₄, was recorded between 5 and 773 K in order to investigate its lattice dynamic behavior. A broad absorption envelope is observed at wavenumbers between 800 and 960 cm^–1 and it contains two intense bands at 816 and 840 cm^–1 at 293 K in the (cc) spectrum. The integral area of the envelope decreases upon cooling from 293 K and reaches a minimum around 55 K. It then increases again with a further decrease in temperature down to 5 K. It is proposed that the envelope in the (cc) spectra consists of seven different modes, some of which are symmetry-forbidden, that arise from combination scattering of nonsymmetric internal SiO₄-stretching modes of B_ig symmetry (i = 1, 2, 3) and low-energy excitations. The individual modes can be observed under different polarizations and agree in number and wavenumber with those obtained by fitting the broad envelope with Lorentzians. An analysis of the Raman spectrum as a function of temperature, using the known magnetic properties of fayalite, allows the assignment of the low-energy excitations to short-range magnetic interactions. Modulation of the Fe²⁺(1)–Fe²⁺(2) exchange energy leads to phonon-magnetic excitation coupling and the main role in the Fe²⁺(1)–Fe²⁺(2) magnetic interaction occurs via superexchange through the oxygens. The magnetic excitations are not magnons in the usual sense, that is as quasiparticles having a long wavelength in an ordered system. The degree of observed broadening of the SiO₄-stretching modes is consonant with a Fe²⁺(1)–Fe²⁺(2) exchange energy of 4.7 cm^–1 presented by Schmidt et al. (1992). At temperatures above 300 K the line width of the mode at 840 cm^–1 decreases slightly, whereas those of low energy lattice modes increase. This suggests that a decrease in mode broadening due to weakened magnetic interactions compensates any thermally related broadening. Complete Fe²⁺ spin disorder may not be reached until at least 530 K. Results from this study show that estimates of third-law entropies for silicates using simple crystal-chemical considerations that do not account for magnetic properties cannot give accurate values for many transition-metal-containing phases.     

Ion microprobe U–Pb dating of zircon with a 15 micrometer spatial resolution using NanoSIMS

We developed a ²³⁸U–²⁰⁶Pb and ²⁰⁷Pb–²⁰⁶Pb zircon dating method using a Cameca NanoSIMS NS50 ion microprobe. A 7-to 9-nA O⁻ primary beam was used to sputter a 15-μm crater, and secondary positive ions were extracted for mass analysis using the Mattauch–Herzog geometry. The multicollector system was modified to detect ⁹⁰Zr⁺, ²⁰⁴Pb⁺, ²⁰⁶Pb⁺, ²³⁸U¹⁶O⁺, and ²³⁸U¹⁶O₂⁺ ions simultaneously. A mass resolution of about 4000 at 10% peak height and with a flat peak top was attained, and the sensitivity of Pb was about 4 cps·nA^− 1·ppm^− 1. A multicrystal zircon standard (QGNG) from South Australia with a U–Pb age of 1842 Ma was used as a reference for Pb⁺/UO⁺–UO₂⁺/UO⁺ calibration, and on the basis of the positive correlation between these ratios, we determined the sample ²⁰⁶Pb/²³⁸U ratios. ²⁰⁷Pb/²⁰⁶Pb ratios were measured by magnetic scanning in single-collector mode. The standard zircons 91500, from Canada, and SL13, from Sri Lanka, were analyzed against QGNG. Observed ²³⁸U–²⁰⁶Pb and ²⁰⁷Pb–²⁰⁶Pb ages agreed well with published ages within experimental error. Then, 16 zircon grains in a metamorphic rock from Nagasaki, Japan, were analyzed. Observed ages were compatible with SHRIMP ages, suggesting that the NanoSIMS with a 15-μm probe diameter is suitable for ion microprobe U–Pb zircon dating.     

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     

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     

A Raman spectroscopic study of H/D isotopically substituted hydrous aluminosilicate glasses

We have obtained high quality Raman spectra for two H/D isotopically substituted hydrous aluminosilicate glasses with compositions along the NaAlSi₃O₈-SiO₂ join. Consistent with the results of previous studies, the isotope shift for the band near 900 cm^–1, whose intensity grows with increasing water content, is extremely small: v _h /v _d = 1.004 ± 0.004. The lack of a definite H/D isotope shift for this band does not, however, preclude its association with a vibration of a hydrous species in the glass, because of likely strong coupling between different vibrational modes of hydrated framework species. The 900 cm^–1 band could well be due to a T — OH (T = Si, Al) stretching or bending vibration in the hydrous glass, as required by the presence of a combination band near 4500 cm^–1 in near-infrared spectra.     

Infrared reflectivity spectra of single crystal cassiterites

The infrared reflectivity spectra of two natural cassiterite single crystals from Portugal and Vietnam have been studied and analysed in the frequency range of 15–4000 cm^–1 at room temperature. The optical mode parameters are deduced by simulation of the experimental spectra using the factorised form of the dielectric function. The difference with synthetic SnO₂ spectra is a dip near 500 cm^–1 understood as the activation of an infrared forbidden E _g mode due to the amount of Fe³⁺ and Ti⁴⁺ impurities. Another result of this work is the derivation of the correct values of the static dielectric constant of cassiterite.     

Vibrational spectroscopy of beta-eucryptite (LiAlSiO<Subscript>4</Subscript>): optical phonons and phase transition(s)

The structural behavior of -eucryptite (LiAlSiO₄) has been investigated using infrared (IR) spectroscopy over a temperature range of 20 to 900 K and FT-Raman spectroscopy at room temperature. IR reflectance measurements show that -eucryptite possesses high reflectivity in the far-IR region, as is consistent with its reported superionic conductivity along the c-axis. On heating, the Li-related IR bands near 246 and 300 cm^–1 (with A₂ symmetry) broadened and weakened dramatically, presumably as a result of Li⁺ positional disordering along the structural channels parallel to c. The disordering process appears to induce a framework distortion, as is evidenced by the broadening of some vibrations of Si(Al)–O with increasing temperature. A change in slope in the temperature dependence of the phonon frequency near 300 cm^–1 and the linewidth of the 760 cm^–1 band at 715 K indicates that Li becomes completely disordered above this temperature. In addition, the temperature dependence of the linewidth for the 760 cm^–1 band exhibits an additional change in slope at 780 K, implying the existence of an intermediate state within this temperature range. The detailed structure of this intermediate phase, however, needs further study. Our IR data provide no indication of structural changes between room temperature and 20 K.     

Characterization of water in synthetic rhyolitic glasses and natural melt inclusions by Raman spectroscopy

Raman spectroscopy was used to analyze quantitatively water in silicate glasses and melt inclusions and to monitor H₂O–OH speciation. Calibration is based on synthetic glasses with various water contents (0.02–7.67% H₂O); water determination and OH–H₂O differentiation on the area of the Si–O broad band at 468 cm^–1 and the asymmetric O–H band at 3,550 cm^–1. Each Raman spectrum has been decomposed into four Gaussian + Lorentzian components centered at 3,330, 3,458, 3,560, and 3,626 cm^–1 using the Levenberg–Marquardt algorithm. These components are interpreted to be two different types of H₂O molecule sites. The influence of the temperature on the loss of water is more important for molecular water than for the hydroxyl groups. The H₂O–OH partition confirms the typical evolution of water speciation in rhyolitic glasses as a function of the bulk water content. Method limitations have been studied for the application to natural melt inclusions.Editorial responsibility: T.L Grove     

First-principles study of OH defects in zircon

The infrared spectroscopic properties of selected OH defects in zircon are investigated by first-principles calculations. The explicit treatment of the coupled nature of OH motions in the stretching modes, together with the calculation of the intensity and polarization of absorption bands, makes it possible to directly compare theoretical and experimental data. The bands observed at 3,420 cm^?1 (polarization parallel to c axis) and 3,385 cm^?1 (polarization perpendicular to c axis) in natural and synthetic samples correspond to the IR-active vibrational modes of the hydrozircon defect, that is, fully protonated Si vacancy. The broad band observed at 3,515 cm^?1 in the spectrum of zircon crystals grown in F-rich environments is consistent with the occurrence of composite (OH,F) tetrahedral defects. Calculations also show that the band observed at 3,200 cm^?1 in the spectrum of synthetic undoped samples can be ascribed to fully protonated Zr vacancies. The theoretical values of integrated absorption coefficients indicate that general correlations can be reasonably used to determine the concentration of OH groups in zircon.     

Evidence from kimberlitic zircon for a decreasing mantle Th/U since the Archean

A decoupling in MORB of measured Th/U (κ = 2.5) from that calculated by Pb isotopes (κ = 3.8) for the depleted asthenosphere is well established, and has been referred to as the second Pb paradox (Kramers, J.D., and Tolstikhin, I.N., 1997. Two terrestrial lead isotope paradoxes, forward transport modelling, core formation and the history of the continental crust. Chem. Geol., 139, 75–110.) or the kappa conundrum (Elliott, T., Zindler, A., and Bourdon, B., 1999. Exploring the kappa conundrum: the role of recycling in the lead isotope evolution of the mantle. Earth Planet. Sci. Lett., 169, 129–145.). More controversial has been the cause and timing of this phenomenon, although a higher return flux of U⁶⁺ relative to Th⁴⁺ and(or) the recycling of crustal Pb into the mantle have become the preferred explanations of most workers. Such a combined mechanism effectively operating over the past 2.5 Ga was modelled in plumbotectonics (Zartman, R.E., and Haines, S., 1988. The plumbotectonics model for Pb isotopic systematics among major terrestrial reservoirs—a case for bi–directional transport. Geochim. Cosmochim. Acta, 52, 1327–1339. 709.33.), and found to be quantitatively feasible.A large TIMS, SIMS and LA-ICPMS database of Th and U concentrations for kimberlite-hosted zircon, particularly from Cr-poor megacrystic suites, now exists (Kinny et al., 1989, Berryman et al., 1999, Griffin et al., 2000 and Spetsius et al., 2002; Appendix A and Appendix B, this work). Six suites comprising 10 or more zircon grains with ages between 90 and 2550 Ma reveal consistent patterns when plotted on Th/U vs. U diagrams. We interpret these patterns as resulting from fractional crystallization of a melt with kimberlite affinity presumably derived from the asthenosphere, permitting the extrapolation to an initial Th/U at the time zircon crystallization began. A two-fold decrease is seen in this ratio over the past 2.5 Ga, suggesting that during this time a similar change has occurred in the parent silicate melt. Estimates of Th and U distribution coefficients between zircon and coexisting melt permit calculation of Th/U in the melt, which, for these highly incompatible elements, presumably is the same as for its mantle source rock. Kimberlitic zircon may thus indeed give evidence of a reduction in κ, tentatively calculated as from 4 to 2, since the Archean for the depleted asthenosphere.     

Radiometric ages of the Fire Clay tonstein [Pennsylvanian (Upper Carboniferous), Westphalian, Duckmantian]: A comparison of U–Pb zircon single-crystal ages and Ar/Ar sanidine single-crystal plateau ages

The Fire Clay tonstein [Pennsylvanian (Upper Carboniferous), Westphalian Series, Duckmantian Stage]–a kaolinized, volcanic-ash deposit occurring in Kentucky, West Virginia, Tennessee, and Virginia–is the most widespread bed in the Middle Pennsylvanian of the central Appalachian basin, USA. A concordant single-crystal U–Pb zircon datum for this tonstein gives a ²⁰⁶Pb/²³⁸U age of 314.6 ± 0.9 Ma (2σ). This age is in approximate agreement with a mean sanidine plateau age of 311.5 ± 1.3 Ma (1σ, n = 11) for the Fire Clay tonstein. The difference between the two ages may be due to bias between the ⁴⁰K and ²³⁸U decay constants and other factors. The age of the Fire Clay tonstein has important implications for Duckmantian Stage (Westphalian Series) sedimentation rates, correlations with the Westphalian Series of Europe, Middle Pennsylvanian volcanic events, and the late Paleozoic time scale.     

U–Pb SHRIMP zircon geochronology and T–t–d history of the Kampa Dome, southern Tibet

Structural, petrographic and geochronologic studies of the Kampa Dome provide insights into the tectonothermal evolution of orogenic crust exposed in the North Himalayan gneiss domes of southern Tibet. U–Pb ion microprobe dating of zircons from granite gneiss exposed at the deepest levels within the dome yields concordia ²⁰⁶Pb/²³⁸U age populations of 506 ± 3 Ma and 527 ± 6 Ma, with no evidence of new zircon growth during Himalayan orogenesis. However, the granite contains penetrative deformation fabrics that are also preserved in the overlying Paleozoic strata, implying that the Kampa granite is a Cambrian pluton that was strongly deformed and metamorphosed during Himalayan orogenesis. Zircons from deformed leucogranite sills that cross-cut Paleozoic metasedimentary rocks yield concordant Cambrian ages from oscillatory zoned cores and discordant ages ranging from ca. 491–32 Ma in metamict grains. Since these leucogranites clearly post-date the metasedimentary rocks they intrude, the zircons are interpreted as xenocrysts that are probably derived from the Kampa granite. The Kampa Dome formed via a series of progressive orogenic events including regional ~ N–S contraction and related crustal thickening (D₁), predominately top-to-N ductile shearing and crustal extension (D₂), top-to-N brittle–ductile faulting and related folding on the north limb of the dome, localized top-to-S faulting on the southern limb of the dome, and crustal doming (D₃), and continued N–S contraction, E–W extension and doming (D₄). Structural and geochronologic variability amongst adjacent North Himalayan gneiss domes may reflect changes in the magnitude of crustal exhumation along the North Himalayan antiform, possibly relating to differences in the mid-crustal geometry of the exhuming fault systems.     

Holocene Siliceous Sediments in the Sea of Okhotsk

The mineral and chemical compositions and physical properties of diatomaceous clayey–siliceous sediments in the Sea of Okhotsk are studied. Absolute masses of silica accumulation are determined. Their compositional model based on the silica content is similar to that of Late Jurassic and Olenekian–middle Anisian cherts of the Sikhote Alin region. The thickness of the Holocene siliceous unit and the absolute mass of siliceous deposits depended on bioproductivity in the upper water column and the seafloor topography. Absolute masses of SiO₂ am (0.05–5.7 g cm^–2 ka^–1) and SiO₂ fr (0.5–11.6 g cm^–2 ka^–1) are minimal on seamounts and maximal in depressions near foothills. These values match absolute masses of SiO₂ fr accumulations in Triassic and Late Jurassic basins of the Sikhote Alin region (0.33–3 g cm^–2 ka^–1). Comparison of the composition and absolute masses of silica shows that Triassic and Late Jurassic siliceous sequences of Sikhote Alin could be accumulated in the marginal marine basin near a continent.     

Experimental study on the phase equilibria in the join CaMgSi2O6-CaCrCrSiO6 with special reference to the blue diopside

The behaviour of tetrahedrally coordinated and octahedrally coordinated Cr³⁺ ions in diopside is discussed from the study on the join CaMg-Si₂O₆-CaCrCrSiO₆. The molecule CaCrCrSiO₆ decomposes into uvarovite+eskolaite and its maximum solubility in diopside is 6.7 wt percent at 940 ° C. Crystalline phases are diopside ss (ss is abbreviation of solid solution), uvarovite ss, wollastonite ss, spinel and eskolaite. The diopside ss is blue in colour. Its optical spectra were measured in the wavelenght range of 325–2600 nm, and assigned after tetrahedral configuration Td and octahedral configuration Oh. It is estimated that octahedral Cr³⁺ ions are in high spin state, while tetrahedral Cr³⁺ ions may be probably in low spin state. The _t and B are 10,300–10,370 cm^–1 and 429–432 cm^–1. The CFSE for tetrahedral low spin Cr³⁺ ions is nearly the same as that for octahedral high spin Cr³⁺ ions. The ionic radii of tetrahedral low spin Cr³⁺ ions calculated are 0.47–0.53 Å, shrinked from the radius of octahedral high spin Cr³⁺ ion (0.615 Å) as much as 14–24 percent. Petrologic implications of the result are also discussed.The first half of the D. Sc. dissertation of K. Ikeda presented to Hokkaido University in June, 1976     

The youngest basic oceanic magmatism in the Alps (Late Cretaceous<Emphasis Type="Italic">;</Emphasis> Chiavenna unit,Central Alps): geochronological constraints and geodynamic significance

Cathodoluminescence-controlled radiometric dating (U–Pb SHRIMP) was carried out on zircon domains from metabasic rocks of the Chiavenna unit, a major mafic/ultramafic-bearing unit in the Central Alps. Co-magmatic zircon domains from amphibolites near Chiavenna and Prata areas yielded weighted mean ²⁰⁶Pb/²³⁸U ages at 93.0±2.0 and 93.9±1.8 Ma, respectively, interpreted as the age of crystallization of the magmatic protoliths. These ages fit well with the time of late spreading in the Valais Ocean, as suggested by previous paleogeographic reconstructions. Inherited zircon grains and/or core domains (Permo-Triassic, Carboniferous, Proterozoic) are abundant, indicating proximity of the Chiavenna unit to thinned continental crust. This is in line with the origin of this unit from subcontinental mantle sources, as suggested previously on petrological and structural grounds. Metamorphic zircon domains from one amphibolite near Chiavenna yielded a weighted mean ²⁰⁶Pb/²³⁸U age at 37.1±0.9 Ma, identical to the 38.5±0.9 Ma SHRIMP age of an amphibolitized eclogite of the Antrona ophiolites (Valais domain, Western Alps). Precise metamorphic ages were difficult to obtain from the composite (poly)metamorphic rim domains of the Prata amphibolite. This is attributed to the location of the Prata area close to the granulite-facies Gruf unit (metamorphosed at ca. 33 Ma) and to the 24–25 Ma old Novate granite, where metamorphic/fluid events probably caused multiple resetting to various degrees. The ca. 93 Ma old magmatism, identified for the first time in the Chiavenna unit, is the youngest basic oceanic magmatism reported in the Alps. The 37.1±0.9 Ma old metamorphism in the Chiavenna unit, attributed to the Valais domain, confirms the model suggesting stepwise younging of metamorphic ages from the south (Adriatic plate) to the north (European plate). It is older than metamorphism in the European margin (ca. 35–31 Ma) lying to the north of the Valais domain and younger than that in the Piemont–Ligurian Ocean (ca. 44–45 Ma) lying to the south of the Valais domain.Editorial responsibility: W. Schreyer     

Cation distribution in pentlandites (Fe,Ni)9S8: Dependence on pressure and temperature and kinetics of the cation exchange reaction

This paper describes the distribution of Fe and Ni between the octahedral and tetrahedral sites in pentlandite (Fe,Ni)₉S₈. The dependence of the distribution on pressure and temperature and the activation energy of the cation exchange reaction were determined through annealing experiments. Synthetic crystals were annealed at 433–723 K and pressures up to 4 GPa, and natural crystals were annealed at 423, 448 and 473 K in evacuated silica capillary tubes for various durations. The cation distributions in the synthetic crystals were determined with an X-ray powder method employing the anomalous dispersion effect of CuK. and FeK radiations, while those of natural crystals were calculated from the cell dimensions. The values of U, S and V for the Fe/Ni exchange reaction are –6818 J mol^–1, 20.52 J K^–1 mol^–1, and 6.99 × 10^–6 m³ mol^–1, respectively. The dependence of the Fe/Ni distribution on pressure (Pa) and temperature (Kelvin) was determined as lnK = 2.47+8.20 × 10² T ^–1+8.41 x 10^–7 T ^–1 P, where K = (Fe/Ni)_octahedral /(Fe/Ni)_tetrahedral. The activation energy of the cation exchange reaction was 185 kJ mol^–1.