He incorporation and diffusion pathways in pure and defective zircon ZrSiO4: A density functional theory study

In this paper, we report a detailed study of helium (He) incorporation and diffusion pathways in the perfect and defective zircon lattice. Ab initio methods based on Density Functional Theory (DFT) were used to calculate the structural features, the solution energies in interstitial sites in the perfect zircon and in vacancy sites of the defective lattice and He diffusion pathways in these systems. We show that the mode of He incorporation in the perfect zircon is influenced mainly by the topological features of the lattice, promoting site preference of He towards accommodation in the interstitial sites present in the middle of c cylinder channels. The presence of defect species in the form of lattice vacancies and interstitials has a significant effect on He solubility and diffusivity in the lattice, where the ability of lattice vacancies to act as physical traps or repulsive sites depends greatly on the electronic nature of the vacancy, which can enhance solubility of He in the lattice and affect the kinetics of He mobility in zircon mineral.     

He diffusion systematics in minerals: Evidence from synthetic monazite and zircon structure phosphates

Helium diffusivity was measured in synthetic rare-earth-element orthophosphates with systematically varying properties to evaluate potential controls on He transport in minerals. In the zircon structure phosphates (in this study, the phosphates of Tb, Dy, Ho, Er, Tm, Yb, and Lu as well as synthetic xenotime, YPO₄), He diffusion is strongly anisotropic. Transport apparently proceeds preferentially through channels aligned with the c-axis. The activation energy for diffusion is almost the same (122 ± 6 kJ/mol) in all members of this family, but there is a monotonic decrease in D_o with atomic number from TbPO₄ (∼10⁵ cm²/s) to LuPO₄ (∼10 cm²/s). The c-parallel channels become increasingly constricted in the same sequence, likely accounting for the systematically decreasing diffusivity. The He closure temperature (r = 1 cm, dT/dt = 10 °C/Myr) increases with atomic number from 44 °C for TbPO₄ to 88 °C for LuPO₄. Diffusion of radiogenic helium from natural zircon and xenotime is much slower than these synthetic analogs predict, suggesting that coupled substitution of REE and P for Zr and Si and/or radiation damage profoundly modify the energetics of interstitial He diffusion. In particular, α-recoil may play a key role by damaging the continuity and integrity of the channels.Monazite structure phosphates (here La, Ce, Pr, Nd, Sm, and Gd phosphate) are far more He retentive than those of the zircon structure. Activation energies increase smoothly with atomic number from LaPO₄ (183 kJ/mol) to NdPO₄ (224 kJ/mol) then decrease again to GdPO₄ (198 kJ/mol). D_o values mimic this pattern, spanning a range from ∼10⁻¹ cm²/s (GdPO₄) to 10⁴ cm²/s (NdPO₄). Nevertheless, He closure temperatures increase monotonically with atomic number, from 300 °C in LaPO₄ to 410 °C in GdPO₄. No evidence was obtained bearing on diffusion anisotropy, but the monazite structure lacks through-going channels so it is not expected. Diffusion parameters for radiogenic helium in natural monazite are similar to those obtained on the synthetic analogs.Ionic porosity is not the primary control on He diffusion in the orthophosphates. Within a given structure and with limited elemental substitution, ionic porosity and He closure temperature are negatively correlated, as predicted. However, differences between crystal structures are far more important than ion packing density: at comparable ionic porosity the monazite structure phosphates have He closure temperatures ∼300 °C higher than the xenotime structure phosphates. Modifications to the structures by radiation damage likely play a similarly significant role in controlling He diffusion.     

Low-temperature anisotropic diffusion of helium in zircon: Implications for zircon (U-Th)/He thermochronometry

In the last decade the zircon (U-Th)/He (ZHe) thermochronometer has been applied to a variety of geologic problems. Although bulk diffusion coefficients for He in zircon are available from laboratory step-heating experiments, little is known about the diffusion mechanism(s) and their dependence on the crystallographic structure of zircon. Here, we investigate the diffusion of He in perfectly crystalline zircon using atomistic simulation methods that provide insights into the structural pathways of He migration in zircon. Empirical force fields and quantum-mechanical calculations reveal that the energy barriers for He diffusion are strongly dependent on structure. The most favorable pathway for He diffusion is the [0 0 1] direction through the open channels parallel to the c-axis (, activation energy for tracer diffusion of a He atom along [0 0 1]). In contrast, energy barriers are higher in other directions where narrower channels for He diffusion are identified, such as [1 0 0], [1 0 1], and [1 1 0] (ΔE^∗ of 44.8, 101.7, and 421.3 kJ mol⁻¹, respectively). Molecular dynamics simulations are in agreement with these results and provide additional insight in the diffusion mechanisms along different crystallographic directions, as well as the temperature dependence. Below the closure temperature of He in zircon [T_c ∼ 180 °C, Reiners P. W., Spell T. L., Nicolescu S., and Zanetti K. A. (2004) Zircon (U-Th)/He thermochronometry: He diffusion and comparisons with Ar-40/Ar-39 dating. Geochim. Cosmochim. Acta68, 1857-1887], diffusion is anisotropic as He moves preferentially along the [0 0 1] direction, and calculated tracer diffusivities along the two most favorable directions differ by approximately five orders of magnitude (D_[001]/D_[100] ∼ 10⁵, at T = 25 °C). Above this temperature, He atoms start to hop between adjacent [0 0 1] channels, along [1 0 0] and [0 1 0] directions (perpendicular to the c-axis). The diffusion along [1 0 0] and [0 1 0] is thermally activated, such that at higher temperatures, He diffusion in zircon becomes nearly isotropic (D_[001]/D_[100] ∼ 10, at T = 580 °C). These results suggest that the anisotropic nature of He diffusion at temperatures near the closure temperature should be considered in future diffusivity experiments. Furthermore, care should be taken when making geologic interpretations (e.g., exhumation rates, timing of cooling, etc.) from this thermochronometer until the effects of anisotropic diffusion on bulk ages and closure temperature estimates are better quantified.     

Diffusion of helium in zircon and apatite

Diffusion of helium has been characterized in natural zircon and apatite. Polished slabs of zircon and apatite, oriented either normal or parallel to c were implanted with 100 keV ³He at a dose of 5 × 10^{15 3} He/cm². Diffusion experiments on implanted zircon and apatite were run in Pt capsules in 1-atm furnaces. ³He distributions following experiments were measured with Nuclear Reaction Analysis using the reaction ³He(d,p)⁴He. For diffusion in zircon we obtain the following Arrhenius relations:

Although activation energies for diffusion normal and parallel to c are comparable, there is marked diffusional anisotropy, with diffusion parallel to c nearly 2 orders of magnitude faster than transport normal to c. These diffusivities bracket the range of values determined for He diffusion in zircon in bulk-release experiments, although the role of anisotropy could not be directly evaluated in those measurements.In apatite, the following Arrhenius relation was obtained over the temperature range of 148–449 °C for diffusion normal to c:

In contrast to zircon, apatite shows little evidence of anisotropy. He diffusivities obtained in this study fall about an order of magnitude lower than diffusivities measured through bulk release of He through step-heating, and within an order of magnitude of determinations where ion implantation was used to introduce helium and He distributions measured with elastic recoil detection.Since the diffusion of He in zircon exhibits such pronounced anisotropy, helium diffusional loss and closure cannot be modeled with simple spherical geometries and the assumption of isotropic diffusion. A finite-element code (CYLMOD) has recently been created to simulate diffusion in cylindrical geometry with differing radial and axial diffusion coefficients. We present some applications of the code in evaluating helium lost from zircon grains as a function of grain size and length to diameter ratios, and consider the effects of “shape anisotropy”, where diffusion is isotropic (as in the case of apatite) but shapes of crystal grains or fragments may depart significantly from spherical geometry.     

Zircon (U-Th)/He thermochronometry: He diffusion and comparisons with Ar/Ar dating

(U-Th)/He chronometry of zircon has a wide range of potential applications including thermochronometry, provided the temperature sensitivity (e.g., closure temperature) of the system be accurately constrained. We have examined the characteristics of He loss from zircon in a series of step-heating diffusion experiments, and compared zircon (U-Th)/He ages with other thermochronometric constraints from plutonic rocks. Diffusion experiments on zircons with varying ages and U-Th contents yield Arrhenius relationships which, after about 5% He release, indicate E_a = 163-173 kJ/mol (39-41 kcal/mol), and D₀ = 0.09-1.5 cm²/s, with an average E_a of 169 ± 3.8 kJ/mol (40.4 ± 0.9 kcal/mol) and average D₀ of 0.46^+0.87_−0.30 cm²/s. The experiments also suggest a correspondence between diffusion domain size and grain size. For effective grain radius of 60 μm and cooling rate of 10°C/myr, the diffusion data yield closure temperatures, T_c, of 171-196°C, with an average of 183°C. The early stages of step heating experiments show complications in the form of decreasing apparent diffusivity with successive heating steps, but these are essentially absent in later stages, after about 5-10% He release. These effects are independent of radiation dosage and are also unlikely to be due to intracrystalline He zonation. Regardless of the physical origin, this non-Arrhenius behavior is similar to predictions based on degassing of multiple diffusion domains, with only a small proportion (<2-4%) of gas residing in domains with a lower diffusivity than the bulk zircon crystal. Thus the features of zircon responsible for these non-Arrhenius trends in the early stages of diffusion experiments would have a negligible effect on the bulk thermal sensitivity and closure temperature of a zircon crystal.We have also measured single-grain zircon (U-Th)/He ages and obtained ⁴⁰Ar/³⁹Ar ages for several minerals, including K-feldspar, for a suite of slowly cooled samples with other thermochronologic constraints. Zircon He ages from most samples have 1 σ reproducibilities of about 1-5%, and agree well with K-feldspar ⁴⁰Ar/³⁹Ar multidomain cooling models for sample-specific closure temperatures (170-189°C). One sample has a relatively poor reproducibility of ∼24%, however, and a mean that falls to older ages than predicted by the K-feldspar model. Microimaging shows that trace element zonation of a variety of styles is most pronounced in this sample, which probably leads to poor reproducibility via inaccurate α-ejection corrections. We present preliminary results of a new method for characterizing U-Th zonation in dated grains by laser-ablation, which significantly improves zircon He age accuracy.In summary, the zircon (U-Th)/He thermochronometer has a closure temperature of 170-190°C for typical plutonic cooling rates and crystal sizes, it is not significantly affected by radiation damage except in relatively rare cases of high radiation dosage with long-term low-temperature histories, and most ages agree well with constraints provided by K-spar ⁴⁰Ar/³⁹Ar cooling models. In some cases, intracrystalline U-Th zonation can result in inaccurate ages, but depth-profiling characterization of zonation in dated grains can significantly improve accuracy and precision of single-grain ages.     

XPS spectra of uranyl minerals and synthetic uranyl compounds. I: The U 4f spectrum

The occurrence and binding energies of the U⁶⁺, U⁵⁺ and U⁴⁺ bands in the U 4f_7/2 peak of 19 uranyl minerals of different composition and structure were measured by XPS. The results suggest that these minerals can be divided into the following four groups: (1) Uranyl-hydroxy-hydrate compounds with no or monovalent interstitial cations; (2) Uranyl-hydroxy-hydrate minerals with divalent interstitial cations; (3) Uranyl-oxysalt minerals with (TO_n) groups (T = Si, P, and C) in which all equatorial O-atoms of the uranyl-polyhedra are shared with (TO_n) groups; (4) Uranyl-oxysalt minerals with (TO_n) groups (T = S and Se), in which some equatorial O-atoms are shared only between uranyl polyhedra. The average binding energies of the U⁶⁺and U⁴⁺ bands shift to lower values with (1) incorporation of divalent cations and (2) increase in the Lewis basicity of the anion group bonded to U. The first observation is a consequence of an increase in the bond-valence transfer from the interstitial species (cations, H₂O) groups to the O-atoms of the uranyl-groups, which results in an electron transfer from O to U⁶⁺. The second trend correlates with an increase in the covalency of the UO bonds with increase in Lewis basicity of the anion group, which results in a shift of the electron density from O to U. The presence of U⁴⁺ on the surface of uranyl minerals can be detected by the shape of the U 4f_7/2 peak, and the occurrence of the U 5f peak and satellite peaks belonging to the U 4f_5/2 peak. The presence of U⁴⁺ in some of the uranyl minerals and synthetics examined may be related to the conditions during their formation. A charge-balance mechanism is proposed for the incorporation of lower-valence U in the structure of uranyl minerals. Exposure of a Na-substituted metaschoepite crystal in air and to Ultra-High Vacuum results in dehydration of its surface structure associated with a shift of the U⁶⁺ bands to higher binding energies. The latter observation indicates a shift in electron density from U to O, which must be related to structural changes inside the upper surface layers of Na-substituted metaschoepite.     

Laboratory actinide partitioning: Whitlockite/liquid and influence of actinide concentration levels

Fission and alpha track radiography techniques have been used to measure partition coefficients (D) at trace (ppm) concentration levels for the actinide elements Th, U, and Pu between synthetic whitlockite and coexisting “haplobasaltic” silicate liquid at 1 bar pressure and 1250°C at oxygen fugacities from 10^?8.5 and 10^?0.7 bars. Pu is much more readily incorporated into crystalline phases than is U or Th under reducing conditions (fO₂ = 10^?8.5), because Pu is primarily trivalent, whereas U and Th are tetravalent. Definitive valence state assignments cannot be made, but our best estimates of corrected partition coefficients for Pu⁺³, Pu⁺⁴, Th⁺⁴, U⁺⁴, and U⁺⁶ are, for whitlockite 3.6/<?0.6/1.2/0.5/?0.002. The effect of changing pressure and liquidus temperature is relatively small, which probably reflects a weak temperature dependence for D (whitlockite) but possibly could be due to cancellation of opposing temperature and pressure effects. Comparison of experiments at trace U levels with those containing percent concentrations of UO₂ indicate that Si is involved in the substitution of U in whitlockite with U + 2Si ? Ca + 2P being the most likely mechanism. D_u is lower. 0.3 vs 0.5. at percent levels compared to 20 ppm. This is best explained by the effect of U on melt structure or by a decrease in the fraction of tetravalent U at high U concentrations.     

Geothermochronology based on noble gases: II. Stability of the (U-Th)/He isotope system in zircon

The kinetics of He migration from zircon of variable degree of metamictization was investigated. The migration parameters of He were experimentally determined, the influence of radiation damage and the degree of metamictization on the stability of the (U-Th)/He isotope system was evaluated, the mechanisms of noble gas escape from zircon were investigated, new data on the kinetics of He migration were obtained and compared with previous results for the kinetics of Xe migration from zircon of the same geologic objects. It was shown that He occurs in two energy positions in the zircon lattice: the main position (more than 80% He) with an activation energy of ∼39 kcal/mol and k ₀ = 10¹¹ yr⁻¹ and the second position with an activation energy for migration of 5–10 kcal/mol and k ₀ ∼ 10⁶ yr⁻¹. It was concluded that He migration from the main energy position is better described by a single-jump mechanism. The migration of He from the second energy position is consistent with the diffusion mechanism. It was shown that deviations from the linear dependence in the lnln(He₀/He_t)-1/T coordinates are probably related to the destruction of volume defects containing He atoms at high temperatures (more than 1000°C on the experimental time scale) resulting in a change from the single-jump to diffusion mechanism and the presence of atoms migrating via the diffusion mechanism. It was shown that the peak width in the spectrum of radiogenic He release and the appearance of a second peak also depend on the fraction of atoms migrating in accordance with the diffusion mechanism. It was found that the low activation energy for He release from the second energy position indicates the existence of continuous He loss from the zircon lattice.     

Heterogeneous reduction of U by structural Fe from theory and experiment

Computational and experimental studies were performed to explore heterogeneous reduction of U⁶⁺ by structural Fe²⁺ at magnetite (Fe₃O₄) surfaces. Molecular Fe-Fe-U models representing a uranyl species adsorbed in a biatomic bidentate fashion to an iron surface group were constructed. Various possible charge distributions in this model surface complex were evaluated in terms of their relative stabilities and electron exchange rates using ab initio molecular orbital methods. Freshly-cleaved, single crystals of magnetite with different initial Fe²⁺/Fe³⁺ ratios were exposed to uranyl-nitrate solution (pH ∼ 4) for 90 h. X-ray photoelectron spectroscopy and electron microscopy indicated the presence of a mixed U⁶⁺/U⁵⁺ precipitate heterogeneously nucleated and grown on stoichiometric magnetite surfaces, but only the presence of sorbed U⁶⁺ and no precipitate on sub-stoichiometric magnetite surfaces. Calculated electron transfer rates indicate that sequential multi-electron uranium reduction is not kinetically limited by conductive electron resupply to the adsorption site. Both theory and experiment point to structural Fe²⁺ density, taken as a measure of thermodynamic reducing potential, and sterically accessible uranium coordination environments as key controls on uranium reduction extent and rate. Uranium incorporation in solid phases where its coordination is constrained to the uranate type should widen the stability field of U⁵⁺ relative to U⁶⁺. If uranium cannot acquire 8-fold coordination then reduction may proceed to U⁵⁺ but not necessarily U⁴⁺.     

Hydrothermal synthesis of pyrochlores and their characterization

Pyrochlores, microlites, and U-betafites of pyrochlore group minerals were obtained from mixing experiments of the corresponding oxides and fluorides by hydrothermal synthesis at T = 800 °C and P = 200 MPa in the solution of 1.0 M NaF. The presence of U⁴⁺ in pyrochlore does not affect the cell parameter, which for the phases of pyrochlore–microlite series is 10.42 ± 0.01 Å. In a system with an excess of UO₂, pyrochlores and microlites, containing uranium up to 0.2–0.3 atoms per formula unit (apfu), are formed. In the uranium-free system of betafites composition, perovskites and Ti-bearing pyrochlores are formed. U-pyrochlores of betafite series, containing 2Ti = Nb + Ta in moles, have cubic cell parameters of 10.26 ± 0.02 Å and U⁴⁺ isomorphic capacity of 0.4–0.5 apfu. In the pyrochlore structure, U⁴⁺ may substitute for Ca²⁺ and Na⁺ cations in the eightfold site. In pyrochlores of pyrochlore–microlite series, Ca²⁺ is replaced by U⁴⁺, while in pyrochlores of betafite series, U⁴⁺ replaces Na⁺. Phases with pyrochlore structure, containing U⁵⁺ and U⁶⁺ in the sixfold site, usually occupied by Nb⁵⁺, Ta⁵⁺, and Ti⁴⁺, are formed under oxidizing conditions (Cu–Cu₂O buffer). They are characterized by low content of Nb⁵⁺, Ta⁵⁺ (<0.1 apfu), and anomalous behavior of the crystal lattice (compression, instead of expansion). Under natural conditions, the formation of pyrochlores containing a significant amount of U⁵⁺ and U⁶⁺ is unlikely.     

The influence of artificial radiation damage and thermal annealing on helium diffusion kinetics in apatite

Recent work [Shuster D. L., Flowers R. M. and Farley K. A. (2006) The influence of natural radiation damage on helium diffusion kinetics in apatite. Earth Planet. Sci. Lett.249(3-4), 148-161] revealing a correlation between radiogenic ⁴He concentration and He diffusivity in natural apatites suggests that helium migration is retarded by radiation-induced damage to the crystal structure. If so, the He diffusion kinetics of an apatite is an evolving function of time and the effective uranium concentration in a cooling sample, a fact which must be considered when interpreting apatite (U-Th)/He ages. Here we report the results of experiments designed to investigate and quantify this phenomenon by determining He diffusivities in apatites after systematically adding or removing radiation damage.Radiation damage was added to a suite of synthetic and natural apatites by exposure to between 1 and 100 h of neutron irradiation in a nuclear reactor. The samples were then irradiated with a 220 MeV proton beam and the resulting spallogenic ³He used as a diffusant in step-heating diffusion experiments. In every sample, irradiation increased the activation energy (E_a) and the frequency factor (D_o/a²) of diffusion and yielded a higher He closure temperature (T_c) than the starting material. For example, 100 h in the reactor caused the He closure temperature to increase by as much as 36 °C. For a given neutron fluence the magnitude of increase in closure temperature scales negatively with the initial closure temperature. This is consistent with a logarithmic response in which the neutron damage is additive to the initial damage present. In detail, the irradiations introduce correlated increases in E_a and ln(D_o/a²) that lie on the same array as found in natural apatites. This strongly suggests that neutron-induced damage mimics the damage produced by U and Th decay in natural apatites.To investigate the potential consequences of annealing of radiation damage, samples of Durango apatite were heated in vacuum to temperatures up to 550 °C for between 1 and 350 h. After this treatment the samples were step-heated using the remaining natural ⁴He as the diffusant. At temperatures above 290 °C a systematic change in T_c was observed, with values becoming lower with increasing temperature and time. For example, reduction of T_c from the starting value of 71 to ∼52 °C occurred in 1 h at 375 °C or 10 h at 330 °C. The observed variations in T_c are strongly correlated with the fission track length reduction predicted from the initial holding time and temperature. Furthermore, like the neutron irradiated apatites, these samples plot on the same E_a − ln(D_o/a²) array as natural samples, suggesting that damage annealing is simply undoing the consequences of damage accumulation in terms of He diffusivity.Taken together these data provide unequivocal evidence that at these levels, radiation damage acts to retard He diffusion in apatite, and that thermal annealing reverses the process. The data provide support for the previously described radiation damage trapping kinetic model of Shuster et al. (2006) and can be used to define a model which fully accommodates damage production and annealing.     

Nanoscale occurrence of Pb in an Archean zircon

We report, for the first time, a direct, atomic-scale characterization of Pb in zircon (4.4-3.1 Ga) from the early Archean Yilgarn craton in Australia using high-resolution HAADF-STEM. Two forms of Pb have been identified: Pb concentrated at ∼3 atom% as a nanoscale patch in zircon structure, and Pb concentrated within the amorphous domain created by fission fragment damage. The first result suggests that the Pb atoms directly substitute for Zr⁴⁺ in the zircon structure, and the latter observation demonstrates that Pb diffusion can occur through amorphous regions created by radiation damage, although volume diffusion is typically considered to be the dominant mechanism for Pb diffusion. Beyond the first percolation point, i.e., when the amorphous domains overlap and form a fully interconnected network of amorphous domains, there is a new pathway for the diffusion of Pb that is faster than volume diffusion through crystalline zircon.     

Diffusion kinetics of proton-induced Ne, He, and He in quartz

A natural quartz sample free of mineral and fluid inclusions was irradiated with a 200 MeV proton beam to produce spallogenic ²¹Ne, ³He and ⁴He. Temperature-dependent diffusivities of these three nuclides were then determined simultaneously by high precision stepped-heating and noble gas mass spectrometry. The outward mobility of proton-induced nuclides reflects diffusion through the quartz lattice. In the studied range of 70 to 400°C the helium diffusion coefficients exceed those of neon by 5-7 orders of magnitude. The implied diffusion parameters E_a = 153.7 ± 1.5 (kJ/mol) and ln(D_o/a²) = 15.9 ± 0.3 (ln(s⁻¹)) and E_a = 84.5 ± 1.2 (kJ/mol) and ln(D_o/a²) = 11.1 ± 0.3 (ln(s⁻¹)) for proton-induced ²¹Ne and ³He, respectively, indicate that cosmogenic neon will be quantitatively retained in inclusion-free quartz at typical Earth surface temperatures whereas cosmogenic helium will not. However, the neon diffusion parameters also indicate that diffusive loss needs to be considered for small (<1 mm) quartz grains that have experienced elevated temperatures. Since natural quartz often contains fluid inclusions which may enhance noble gas retentivity, these parameters likely represent an end-member case of purely solid-state diffusion. The ∼70 kJ/mol higher activation energy for neon diffusion compared to helium diffusion likely represents an energy barrier related to its ∼13% greater diameter and provides a fundamental constraint with which to test theories of solid state diffusion. The diffusion parameters for proton-induced ⁴He are indistinguishable from those for ³He, providing no evidence for the commonly expected inverse square root of the mass diffusion relationship between isotopes. We also find preliminary indication that increased exposure to radiation may enhance neon and helium retentivity in quartz at low temperatures.     

He diffusion and (U–Th)/He thermochronometry of zircon: initial results from Fish Canyon Tuff and Gold Butte

To evaluate the potential of (U–Th)/He geochronometry and thermochronometry of zircon, we measured He diffusion characteristics in zircons from a range of quickly and slowly cooled samples, (U–Th)/He ages of zircons from the quickly cooled Fish Canyon Tuff, and age-paleodepth relationships for samples from 15 to 18 km thick crustal section of the Gold Butte block, Nevada. (U–Th)/He ages of zircons from the Fish Canyon Tuff are consistent with accepted ages for this tuff, indicating that the method can provide accurate ages for quickly cooled samples. Temperature-dependent He release from zircon is not consistent with thermally activated volume diffusion from a single domain. Instead, in most samples apparent He diffusivity decreases and activation energy (E_a) increases as cycled step-heating experiments proceed. This pattern may indicate a range of diffusion domains with distinct sizes and possibly other characteristics. Alternatively, it may be the result of ongoing annealing of radiation damage during the experiment. From these data, we tentatively suggest that the minimum E_a for He diffusion in zircon is about 44 kcal/mol, and the minimum closure temperature (T_c, for a cooling rate of 10 °C/myr) is about 190 °C. Age–paleodepth relationships from the Gold Butte block suggest that the base of the zircon He partial retention zone is at pre-exhumation depths of about 9.5–11 km. Together with constraints from other thermochronometers and a geothermal gradient derived from them in this location, the age–depth profile suggests a He T_c of about 200 °C for zircon, in reasonable agreement with our interpretation of the laboratory measurements. A major unresolved question is how and when radiation damage effects become significant for He loss from this mineral.     

Shock compression of zirconia ZrO2 and zircon ZrSiO4 in the pressure range up to 150 GPa

The shock compression state of zirconia ZrO₂ and zircon ZrSiO₄ in the pressure range up to 150 GPa (1.5 Mbar) are studied on the basis of the measurements of shock velocities, particle-velocity histories, free surface motions, and electrical conductivities. Zircon transforms, and zirconia probably does, to high pressure phases up to 90 GPa. The shock velocity (U _s ) — particle velocity (U _p ) Hugoniots can be described as U _s =4.38+1.37 U _p km/s above 90 GPa for ZrO₂, and U _s =6.50+0.49 U _p km/s (mixed phase region), and U _s =1.54+2.30 U _p km/s (high pressure phase region) for ZrSiO₄. The corrected isothermal densities of the high pressure phase ZrSiO₄ are roughly consistent with the isothermal ones of mixtures of ZrO₂ and SiO₂. Bulk sound velocities in the high-pressure phase region of these oxides are discussed in comparison with other dioxides. Electrical conductivities of these oxides increase from lower than 10^?12 S/m to greater than 10⁰ S/m in the shock-stress range up to 70 GPa, and remain as constant values up to higher than 100 GPa.     

Nuclear tracks in the Angra dos Reis and Moore County meteorites

Charged particle tracks were studied in the Angra dos Reis and Moore County meteorites, both of which contain an unexplained excess of He⁴. A selective annealing method was used to resolve cosmic-ray tracks from fission tracks. It gave the following cosmic-ray and fission-track densities, in units of 10⁶cm^?2: Angra dos Reis 1.3–4.4 and 7.8; Moore Co. feldspar 1.9–3.0 and 0.51; Moore Co. pigeonite 2.0–2.9 and 0.078–0.35. The fission-track densities are 10–100 times higher than expected from U²³⁸; the excess is probably due to extinct Pu²³⁸. The Pu²⁴⁴/U²³⁸ ratios at the start of track retention were 0.003 for Angra dos Reis and 0.002–0.03 for Moore Co. No evidence was found for fission tracks attributable to the unknown progenitor of excess He⁴ in these meteorites; the fission branch of this progenitor comprises less than 10^?5 the α-branch. A search for pleochroic halos also gave negative results.The preatmospheric radii of the two meteorites are ≥13 and ≥7cm. According to meteor theory, this implies geocentric velocities of ≥ 19 and ≥ 6 km/sec.The etching behavior of Angra dos Reis augite is highly anomalous, giving rise to spurious angular anisotropies and skewed length distributions. This confirms similar observation by Fleischer et al. (1970) on lunar augite.     

Li同位素在斜顽辉石、镁铝榴石及镁铝尖晶石晶格内扩散与分馏的理论计算研究

斜顽辉石、镁铝榴石和镁铝尖晶石作为辉石族、石榴石族以及尖晶石族中的重要端元,是地球上地幔主要组成矿物。Li同位素是重要的地幔地球化学示踪剂,其在橄榄石、辉石和石榴石等地幔矿物中的扩散分馏的性质对理解Li同位素作为地幔地球化学示踪剂非常重要。我们通过经典力场经验势方法,从原子尺度上计算研究了不同温压条件下Li同位素在斜顽辉石、镁铝榴石和镁铝尖晶石晶格中分别通过不同的填隙机制和取代空位机制迁移的活化能和其在不同晶格位上的分馏效应。我们发现Li同位素是通过取代空位机制在斜顽辉石、镁铝榴石和镁铝尖晶石中进行迁移扩散。Li同位素在不同晶格位上的分馏作用计算表明,在三种矿物中重同位素7Li会更多地进入晶格填隙位中,而6Li则相对更多进入Mg位。温度是影响这种分馏作用的一个关键因素,相应的结果可用来解释地幔Li同位素组成特征及冷却条件下的同位素分馏等科学问题。     

Applications of near-infrared FT-Raman spectroscopy in metamict and annealed zircon: oxidation state of U ions

We report a near-infrared Fourier-transform (FT) Raman spectroscopic method to characterize the electronic transitions of U ions and the alpha-decay damage in natural zircon. The application is demonstrated by analyzing metamict and annealed zircons from Sri Lanka. The data from crystalline zircon reveal a relatively sharp spectral feature appearing near 2733 cm^–1 in Stokes spectra with a laser excitation of 1064 nm. The feature is assigned as signals related to the previously reported U⁵⁺ absorption near 6668 cm^–1. With increasing self-irradiation dose, the feature shows a systematic decrease in intensity, accompanied by a gradual development of a broad feature between 3000 and 3400 cm^–1. On heating for 1 h, the U⁵⁺ feature shows an increase in intensity starting near ~700 K for partially metamict zircon, whereas for highly damaged zircon the first recovery of the feature takes place near 1000 K, accompanied by a decrease in the radiation-induced broad band. The changes observed in the present study reflect the variations of local environments of U ions in natural zircon during metamictization and thermal annealing.     

Constraints on the loss of matrix-sited helium during vacuum crushing of mafic phenocrysts

Vacuum crushing is an efficient technique to selectively release the mantle-derived helium component trapped within olivine and pyroxene phenocrysts. However, contrary to previous assumptions, recent studies have shown that this method may liberate significant matrix-sited cosmogenic ³He (³He_c) or radiogenic ⁴He (⁴He^∗). Because this loss may bias both the determination of magmatic ³He/⁴He ratios and the accuracy of ³He_c measurements, it is essential to understand what mechanism is responsible and under what conditions matrix helium loss is manifest. To address this question, olivines and pyroxenes with various amounts of matrix-sited ³He (from 10⁷ to 10¹¹ at. g⁻¹) were crushed in air or in vacuum using several crushing devices. Sample temperature was controlled during each crushing experiment, and ranged from 25 to 325 °C. The resulting powders were then sieved to obtain several homogeneous grain fractions ranging between <10 and >300 μm. The ³He_c concentrations measured in each fraction clearly show that significant ³He_c loss (>20%) affects only the finest fraction (<10 μm) and, importantly, only under hot conditions (here T ?300 °C). Even the smallest fractions (<10 μm) quantitatively retain matrix-sited ³He_c when crushed under cold conditions (T ?25 °C), regardless of the duration and energy of crushing. These results invalidate the model previously proposed by (Yokochi R., Marty B., Pik R. and Burnard P. (2005) High ³He/⁴He ratios in peridotite xenoliths from SW Japan revisited: evidence for cosmogenic ³He released by vacuum crushing. Geochem. Geophys. Geosyst.6, doi:10.1029/2004GC000836) that involved spallation tracks and implied that the magnitude of loss was mainly controlled by the grain size. Moreover, new diffusion experiments were carried out to constrain the diffusivity of matrix-sited helium in crushed olivines. When used to model diffusive ³He_c loss as a function of grain size during crushing, these new data predict the observed release fairly well. Therefore, we conclude that temperature-enhanced volume diffusion is one of the main mechanisms controlling the release of ³He_c during crushing. For future applications, special attention should thus be paid to control the grain size, the crushing duration, and the temperature of the sample.     

Kinetics of zircon dissolution and zirconium diffusion in granitic melts of variable water content

The experimental dissolution of zircon into a zircon-undersaturated felsic melt of variable water content at high pressure in the temperature range 1,020° to 1,500° C provides information related to 1) the solubility of zircon, 2) the diffusion kinetics of Zr in an obsidian melt, and 3) the rate of zircon dissolution. Zirconium concentration profiles observed by electron microprobe in the obsidian glass adjacent to a large, polished zircon face provide sufficient information to calculate model diffusion coefficients. Results of dissolution experiments conducted in the virtual absence of water (<0.2% H₂O) yield an activation energy (E) for Zr transport in a melt ofM=1.3 [whereM is the cation ratio (Na+K+2Ca)/(Al·Si)] of 97.7±2.8 kcal-mol^?1, and a frequency factor (D ₀) of 980 _?580 ^+1,390 cm²-sec^?1. Hydrothermal experiments provide an E=47.3±1.9 kcal-mol^?1 andD ₀=0.030 _?0.015 ^+0.030 cm²-sec^?1. Both of these results plot close to a previously defined diffusion compensation line for cations in obsidian. The diffusivity of Zr at 1,200° C increases by a factor of 100 over the first 2% of water introduced into the melt, but subsequently rises by only a factor of five to an apparent plateau value of ～2×10^?9 cm²-sec^?1 by ～6% total water content. The remarkable contrast between the wet and dry diffusivities, which limits the rate of zircon dissolution into granitic melt, indicates that a 50 μm diameter zircon crystal would dissolve in a 3 to 6% water-bearing melt at 750° C in about 100 years, but would require in excess of 200 Ma to dissolve in an equivalent dry system. From this calculation we conclude that zircon dissolution proceeds geologically instantaneously in an undersaturated, water-bearing granite. Estimates of zircon solubility in the obsidian melt in the temperature range of 1,020° C to 1,500° C confirm and extend an existing model of zircon solubility to these higher temperatures in hydrous melts. However, this model does not well describe zircon saturation behavior in systems with less than about 2% water.