Laser Ablation (U-Th-Sm)/He Dating of Zircons: Analytical Age Bias and its Consequence for Studying Detrital Zircon Populations

The in situ (U-Th-Sm)/He and U/Pb laser-ablation double-dating procedure is a valuable method that can provide a large dataset relatively efficiently in contrast with conventional bulk helium thermochronometry. In this study, we evaluate the potential age error associated with the double ablation procedure and report the in situ (U-Th-Sm)/He double-ablation dating of 249 zircons from the Fish Canyon Tuff locality. With LA-ICP-MS pseudo-depth profiling and 3D numerical modelling, we show that the concentric double-ablation procedure in minerals with U-Th-Sm zoning can generate a significant (U-Th-Sm)/He age error (positive or negative), resulting in over-scattering and/or an offset of the mean age. Pseudo-depth profiling is insufficient to predict the individual age error, partly because of the superimposed ablations. To evaluate the consequence of this inherent bias, we confront a synthetic age distribution to the error expected for U-Th-Sm zoned zircons analysed with double-ablation (U-Th-Sm)/He thermochronometry. As expected, a strong age bias causes the spreading of peak ages, downgrading the original signal. Yet, the throughput of the ablation-based method can allow intra- and inter-sample peak age identification and comparison, and the coupling of (U-Th-Sm)/He and U/Pb ages extends our ability to deconvolute a multimodal age spectrum.     

Interpretation of (U–Th)/He single grain ages from slowly cooled crustal terranes: A case study from the Transantarctic Mountains of southern Victoria Land

Low temperature thermochronologic techniques (e.g. apatite fission track (AFT) thermochronology and (U–Th)/He dating) constrain near-surface T–t paths and are often applied to uplift/denudation and landscape evolution studies. Samples collected in vertical profiles from granitic walls on either side of the Ferrar Glacier, southern Victoria Land, Antarctica were analyzed using AFT thermochronology and apatite (U–Th)/He dating to further constrain the lowest temperature thermal history of this portion of the Transantarctic Mountains. AFT central ages vary systematically with elevation and together with track length information define a multi-stage cooling/denudation history in the Cretaceous and early Tertiary. Apatite (U–Th)/He single grain age variation with elevation is not as systematic with considerable intra-sample age variation. Although many complicating factors (e.g., U- and Th-rich (micro)inclusions, fluid inclusions, variation in crystal size, α-particle ejection correction, zonation and α-particle ejection correction, implantation of He into a crystal or impediment of He diffusion out of a crystal, and ¹⁴⁷Sm-derived α-particles) may contribute to age dispersion, we found that variation in single grain ages correlated with cooling rate. Samples that cooled relatively quickly have less variation in single grain ages, whereas samples that cooled relatively slowly (< 3 °C/m.y.) or resided within an (U–Th)/He partial retention zone (HePRZ) prior to more rapid cooling have a comparatively greater variation in ages.Decay of U and Th via α-particle emission creates a ⁴He concentration profile dependent upon the initial parent [U,Th] within a crystal. Variation of single grain ages for samples with non-homogeneous [U,Th] distributions will be enhanced with long residence time in the partial retention zone (i.e., slow cooling) because of the relative importance of loss via volume diffusion and loss via α-particle ejection with respect to the [U,Th] zonation and the grain boundary. Correction of ages for α-particle ejection (F_T correction factor) typically assumes uniform U and Th distribution within the crystal and when applied to a population of crystals with different U and Th distributions will enhance the variation in ages. Most complicating factors (listed above) for apatite (U–Th)/He ages result in ages that are “too old”. We propose that if considerable variation in (U–Th)/He single grain ages exists, that a weighted mean age is determined once outlier single crystal ages are excluded using the criterion of Chauvenet or a similar approach. We suggest that the “true age” or most representative age for that age population lies between the minimum (U–Th)/He age and the weighted mean age. We apply this approach, coupled with composite age profiles to better constrain the T–t history of the profiles along the Ferrar Glacier. Significant intra-sample variation in single crystal apatite (U–Th)/He ages and other minerals dated by the (U–Th)/He method should be expected, especially when the cooling rate is slow. The variation of (U–Th)/He single crystal ages is therefore another parameter that can be used to constrain low-temperature thermal histories.     

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.     

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.     

Duluth Complex FC1 Apatite and Zircon: Reference Materials for (U-Th)/He Dating?

The accuracy and validation of geo- and thermochronological dating hinges on the availability of well-characterised age reference materials. The Mesoproterozoic gabbroic anorthosite FC1 from the Duluth Complex, Minnesota is a reference material for zircon U-Pb and a suggested reference material for apatite fission-track dating. We evaluate FC1 as (U-Th)/He reference material, and determine its apatite U-Pb, and zircon and apatite (U-Th)/He age. Our dating results constrain the thermal history of FC1, showing that fast cooling occurred between ~ 1099 and 1040 Ma from ≥ 600 °C to ~ 200 °C. The zircon (U-Th)/He data from air-abraded grains give a robust isochron age of 1037 ± 25 Ma (2s) without overdispersion. The within-grain homogeneity of U and Th, the availability of FC1 zircon, and the absence of radiation-damage effects on the (U-Th)/He age support its use as reference material. Unabraded zircon grains give lower and more dispersed ages, highlighting the usefulness of air abrasion to control for α-ejection in (U-Th)/He dating. Our apatite (U-Th-Sm)/He single-grain ages vary between 180 and 300 Ma. Their wide dispersion argues against the use of FC1 apatite as (U-Th-Sm)/He reference material and makes the interpretation of their low-temperature thermal history complicated.     

Fluorite (U–Th)/He thermochronology: Constraints on the low temperature history of Yucca Mountain,Nevada

Fluorite is one of the secondary minerals precipitated in pore spaces at the future nuclear waste repository site at Yucca Mountain, Nevada. The authors have conducted (U–Th)/He dating of this fluorite in an attempt to constrain the temperature and timing of paleo-fluid flux into the site. Repeated analysis of colourless fluorite yielded a weighted average age of 9.7 ± 0.15 Ma (2σ), younger than previously determined sanidine ⁴⁰Ar/³⁹ Ar ages (12.8 Ma) for deposition of the tuff.Laboratory He-diffusion experiments conducted on the Yucca fluorite yield a preliminary He closure temperature (T_c) of 90 ± 10 °C (cooling rate of 10 °C/Ma) and previous studies have determined that the fluorite precipitated from warm fluids (65–80 °C) at depths of <400 m. However, minerals can experience partial He loss at temperatures well below the T_c and therefore the (U–Th)/He age of 9.7 Ma is interpreted to be a cooling age. This result implies that the last period of elevated temperature fluid circulation through the Yucca site was approximately 9.7 Ma ago.It was observed that the purple coloured outer portion of the fluorite nodule yielded non-reproducible and invariably older ages than colourless fluorite. Several possible reasons are suggested.     

Anisotropic diffusion in a finite cylinder, with geochemical applications

Atomic diffusion in minerals may not be well represented by solutions to the diffusion equation for a sphere with a single-valued diffusivity, either because they have platy or elongated habits or because the energetics of diffusion is sensitive to crystallographic direction. In many cases, a cylinder having characteristic radial and axial diffusivities is arguably a better model, but rigorous solutions to the anisotropic diffusion equation for a finite cylinder have not been available. Here we develop general analytical solutions that capture both the internal distribution of diffusant as a function of time, C(r, z, t), and the fraction, F, of diffusant lost during a specified thermal history. These solutions are shown to conform with existing analytical expressions for limiting cases of diffusion in a slab or infinite cylinder. We present, in addition, a simple numerical (finite difference) approach that not only reproduces the results of our analytical expressions but also enables us to move beyond some of the limitations of the equations to simulate complex natural scenarios involving non-zero and time-dependent boundary conditions, arbitrary initial distribution of diffusant within the cylinder and simultaneous diffusion and radiogenic ingrowth. The complementary nature of the two approaches is emphasized and several illustrative applications to ‘real-world’ problems are described, including noble-gas thermochronometry and halogen-hydroxyl interdiffusion in apatite.     

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.     

The relationship between apparent equilibrium temperature and closure temperature with application to oxygen isotope geospeedometry

Oxygen isotope fractionation between coexisting minerals in slowly cooled rocks conveys information about their cooling history. By using the fast grain boundary （FGB） model to simulate closed-system diffusive ex- change of oxygen isotopes between coexisting minerals, I show that the apparent equilibrium temperatures （Tae） by the mineral pair with the largest isotopic fractionation （PLIF） always lies between the closure temperatures （To） of those two minerals. Therefore, when the rate of oxygen diffusion and hence Tc for the PLIF chance to be comparable （such as in the case of quartz and magnetite）, Tae will serve as a good approximation of To regardless of variation in mineral proportions. The specialty of the PLIF in constraining Tac within their Tc range can be generalized to other stable isotope systems and element partitioning. By approximating Tc with Tac and inverting Dodson＇s equation, the cooling rate of plutonic or metamorphic rocks can be inferred.     

U and Th zonation in apatite observed by laser ablation ICPMS, and implications for the (U-Th)/He system

A laser-ablation inductively-coupled plasma mass spectrometry technique was developed to measure U, Th, and Ce zonation in polished sections of apatite for assessing the consequences of parent zonation for (U-Th)/He thermochronometry. The technique produces concentration maps with an averaging length-scale of ∼20 μm, comparable to the α-stopping distance, and a precision of ∼5% down to few ppm concentration levels. A model was developed to transform the measured concentration distribution into a simplified representation for use in spherical-geometry He production-diffusion models. To illustrate these methods, 30 sections of apatite from a single granite (GC863) were mapped. Every analyzed apatite from GC863 is zoned, with most grains having variable thickness rims and terminations that are enriched in U and Th by about a factor of three over the grain cores.Parent zonation has three independent effects on (U-Th)/He He ages: it influences the α ejection correction, the ⁴He concentration profile which governs diffusive loss, and, via radiation damage trap accumulation, spatial variability of diffusivity within the crystal. If the observed zonation is typical of the apatite population in GC863, use of the standard homogenous α ejection correction would cause He ages to be on average 3% too young, and with a large amount of grain-to-grain variability (9% too young in the most rim-enriched case to 6% too old in a core-enriched case). Independent of the ejection correction, the concentration profile modifies the effective closure temperature of the apatites by placing more (or less) ⁴He near the grain edge. The parent zonation in GC863 apatites causes closure temperatures to range from four degrees lower (rim-enriched case) to two degrees higher (core-enriched case) than applies in the homogenous case. Alpha ejection and concentration profile effects on He age are additive and of the same sense. In the case of typical grains in GC863 cooled between 1 and 10 °C/Ma, the two effects are roughly equal in magnitude. The effects of intracrystalline variations in radiation damage trap accumulation become apparent at slow cooling rates (1 °C/Ma). For example, in rim-enriched GC863 grains cooled at 1 °C/Ma, preferential accumulation of radiation damage traps near the grain rim almost compensates for the higher loss rate expected of ⁴He also located preferentially near the rim. Under some circumstances strong rim-enrichment may actually increase the effective closure temperature of an apatite. Zonation at the level observed in GC863 modifies the ⁴He/³He spectra substantially from that expected from a uniform distribution. Measured ⁴He/³He spectra are strikingly similar to predictions based on the mapped eU distributions of the very same crystals, supporting the overall validity of the analytical and interpretive approach presented here.The magnitude and style of U, Th zonation documented in GC863 is one possible source of frequently observed over-dispersion of apatite (U-Th)/He ages as well as anomalous ⁴He/³He spectra.     

Thermochronological record of Middle–Late Jurassic magmatic reheating to Eocene rift-related rapid cooling in the SE South China Block

We investigate the Mesozoic–Cenozoic thermal history of the Daxi region (central SE South China Block) to evaluate the influence of the subduction of the Paleo-Pacific oceanic plate beneath the SE South China Block along the block's southeast margin on the tectonothermal evolution of the upper plate. We apply a multi-chronological approach that includes U-Pb geochronology on zircon, ⁴⁰Ar/³⁹Ar dating on muscovite and biotite from granitic rocks as well as fission-track and (U-Th-Sm)/He analyses on zircon and apatite from granitic and sedimentary rocks. The Heping granite, located in the Daxi region, has a magmatic age of ca. 441 Ma. The biotite ⁴⁰Ar/³⁹Ar ages of ca. 193 Ma for the Early Jurassic Shibei granite and ca. 160 Ma for the Late Jurassic Fogang granite, respectively, reflect magmatic cooling. The Triassic Longyuanba granite yielded a muscovite ⁴⁰Ar/³⁹Ar age of ca. 167 Ma, recording heating to ≥ 350 °C induced by nearby intrusion of Middle Jurassic granites. Zircon fission-track and (U-Th-Sm)/He ages from Lower Carboniferous–Lower Jurassic sandstones (140–70 Ma) record continuous cooling during the Cretaceous that followed extensive Middle–Late Jurassic magmatism in the Daxi region. Cretaceous cooling is related to exhumation in an extensional tectonic setting, consistent with lithospheric rebound due to foundering and rollback of the subducted Paleo-Pacific oceanic plate. Apatite fission-track (53–42 Ma) and (U-Th-Sm)/He ages (43–36 Ma), and thermal modelling document rapid cooling in the Paleocene–Eocene, which temporally coincides with continental rifting in the SE South China Block in the leadup to the opening of the South China Sea.     

How stacking disorder can conceal the actual structure of micas: the case of phengites

The present study deals with how stochastic stackings of tetrahedral/octahedral phengitic sheets bearing diverse cation distributions affect diffraction signals and the structural inferences therefrom derived. The interest for such minerals is dictated by that the stability of phengite polytypes, their cation distributions and P/T conditions of crystallization are related to each other. We focus our attention on layers’ probabilistic sequences that preserve the topology of the polytypes 2M ₁(SG: C2/c) and 3T(SG: P3₁12). Neutron diffraction intensities are modelled by a Monte Carlo approach and then used as artificial experimental data for conventional structure refinements that yield the occupancy factors in the fourfold (Si, Al) and sixfold (Al, Mg) coordination sites of 2M ₁ and 3T. The cation ordering from structure refinement tallies with the one of the “average structure” of a stochastic stacking, but it can significantly differ from those of the individual tetrahedral/octahedral sheets. For instance, sheets having ordered cation arrangements can lead to a stochastic structure which is supposed to bear a fully disordered cation partitioning according to structure refinement. This affects the configuration entropy contributions: the values obtained by conventional refinements can deviate from the correct ones up to 30 %. The analysis of the equivalent reflection intensities brings to light the anomalies hinting at the occurrence of such stacking disorder (using modelled reflections, the mean ratio between standard deviation and average intensity of symmetry equivalent reflections is ideally 0 for perfect crystal structures, but it can amount up to 6 in stochastically disordered phengites). However, taking into account the instrumental uncertainties and the deviations from ideality of actual crystals, such phenomena are very difficult to be detected experimentally.     

Tectono-thermal Evolution in the Bachu Uplift,Tarim Basin,China

<正>The thermal evolution of source rocks in the Paleozoic has long been a problem to petroleum exploration in the Bachu uplift,Tarim basin,since the thermal history in the Paleozoic could not be rebuilt objectively due to lack of effective thermal indicators in the Lower Paleozoic successions.The apatite and zircon(U-Th)/He thermochronometry can be used as a new kind of technique to study the thermal history and tectonic uplift of sedimentary basins.Based on the measured apatite and zircon(U-Th)/He ages,apatite fission track data and equivalence vitrinite reflectance(%EVR_o),the tectonothermal histories in 5 wells of the Bachu uplift were modeled.The modeling results show that there was relatively high gradient at the Early Paleozoic in the Bachu uplift and it decreased gradually during the entire Paleozoic:33-35℃/km in the Cambrian-Ordovician, 32-33℃/km in the Silurian-Devonian,30-32℃/km at the end of Carboniferous and 27.5- 31℃/km at the end of Permian.Therefore,the thermal history can be modeled by combining multiple thermal indicators of AFT,(U-Th)/He ages and EVR_o data.Especially,this provides a new method to rebuild the thermal history for the Low Paleozoic carbonate successions in the Tarim Basin.     

矿物中4He同位素提取和含量测定研究

(U-Th)/He定年是一种有效的低温热年代学定年技术,现已被广泛应用于地质研究的各个领域,而矿物中4He同位素的有效提取和含量准确测定是该技术的关键。磷灰石和锆石是(U-Th)/He定年最常用的矿物,其4He提取条件及铀钍含量测定方法都较为成熟;而其他矿物(如磁铁矿、橄榄石、针铁矿、石榴子石等)的研究则相对较少。文章介绍了当前国内外(U-Th)/He研究中采用的4He同位素提取方法———真空炉加热法和激光加热法,激光加热法因具有低4He背景值和耗时短的优点而成为主要的提取方法。以磷灰石样品测试为例,介绍了成都地质矿产研究所建立的采用激光加热法和四极杆质谱提取4He同位素及其含量测量过程、含量计算和校正方法。指出未来(U-Th)/He测试技术除继续改进现有分析方法外,应加强对更多不同矿物的测试研究。     

Solubility and complexing of Ni in the system NiO-H2O-HCl

The solubility of bunsenite (NiO) in Cl-bearing fluids in the range of 450°–700°C, 1–2 kbar was determined using the Ag + AgCl acid buffer technique. Based on the results of the experiments, it is concluded that the associated NiCl⁰₂ complex is the dominant Ni species in the fluid over the entire temperature-pressure range investigated. The temperature dependence of the equilibrium constant for the reaction NiO(s) + 2HCl⁰(aq) = NiCl⁰₂(aq) + H₂O is given by logK = ?4.17(±0.55) + 4629(±464)/T(K) at 1 kbar, and logK = ?4.75(±0.91) + 5933(±756)/T(K) at 2 kbar. The calculated difference in standard state Gibbs free energy of formation between NiCl⁰₂ and 2HCl⁰ in kcal is G⁰(NiCl⁰₂) ? 2G⁰(HCl⁰) = ?20.77(±2.22) + 0.03264(±0.0026)T(K), at 1 kbar and G⁰(NiCl⁰₂) ? 2G⁰(HCl⁰) = ?25.01(±1.35) + 0.03264(±0.0016)T(K) at 2 kbar. Comparison of the solubilities of Ni end-member minerals with those of Ca, Mn, Fe, and Mg indicates that nickel minerals generally are the least soluble at a given temperature and pressure. The relatively low solubility of Ni end-member minerals, combined with the relatively low concentration of Ni in most rocks, should result in a quite low mobility of Ni in hydrothermal fluids.     

How do uncertainties of structure refinements influence the accuracy of the prediction of enthalpy of formation? Examples on muscovite and natrolite

A method to predict the enthalpy of formation is based on the parameter _HO^2-cation (comp) (Vieillard 1982; Vieillard and Tardy 1988a). The calculation of this parameter requires the knowledge of cristallographical and optical properties of minerals (refractive index, molar volume, average distances and shortest bond lengths of cation-oxygens in all sites, existence of hydrogen bonding, presence of a order-disorder in a site of the involved compound). This method has been tested on a great number of minerals and artificial compounds belonging to the system: Li₂O-Na₂O-K₂O-BeO-MgO-CaO-MnO-FeO-Fe₂O₃-Al₂O₃-SiO₂-H₂O (180 minerals) (Vieillard 1994a, b). When several structure refinements of the same mineral are present, several factors such as precision of crystal structure determination, chemical composition, existence of any disorder in a site, presence of hydrogen bonding and estimated standard deviation on bond lengths seem to play an important role in the predication of enthalpy of formation from oxides. Muscovite and natrolite, for which numerous structure refinements are available, are used and discussed in this study.     

Magnetite-orthopyroxene symplectites in gabbros of the Urals: A structural track of olivine oxidation

The chemical compositions of magnetite-orthopyroxene symplectites (MOS) and rock-forming minerals—olivine (Ol), clinopyroxene (Cpx), and magnetite(Mt)—have been studied in 20 samples of olivine-bearing rocks in the Urals, including troctolite, olivine gabbro, and gabbronorite. MOS are orthopyroxene (Opx) monocrystals up to 500 μm in size containing myrmekite-like magnetite intergrowths up to 20–30 μm in width. According to the microprobe examination, the dark-colored minerals are characterized by a high Fe mole fraction F = Fe/(Fe + Mg) = 0.20–0.50, whereas F = 0.33–0.65 is typical of the bulk rock compositions. The plagioclase varies in composition from An₉₀ to An₅₀. No significant compositional difference has been established between the MOS and rock-forming minerals. The F _opx and F _Ol are closely correlated (linear trend, r = 0.97); F _Ol/F _Opx is ～1.2. Similarly, a positive correlation between F _Opx and F _Cpx is noted (linear trend, r = 0.90); F _Opx/F _Cpx is ～1.2. The crystallization temperature of the Ol-Opx-Cpx assemblage is roughly estimated at 700–800°C. A high positive correlation (r = 0.95) is established between the TiO₂ contents in the magnetites from the MOS (Mt1) and host rock (Mt2). The Mt1/Mt2 ratio reaches ～0.8, implying that Mt1 contains somewhat less TiO₂ than Mt2. Hence, the rock-forming and MOS minerals make up an equilibrium assemblage. As follows from the structural pattern, symplectites were formed as products of the reaction between olivine and oxygen in the solid state with the entire volume of the rock involved in the oxidation; i.e., the distance of the diffusion was significant. Free oxygen appeared as a product of the dissociation of the water penetrating into the hot gabbro and ultramafic rocks at the initial stage of the tectonic extension and high-temperature hydration. According to the redox state of dunite coexisting with gabbro, the oxygen fugacity is estimated at +2.7 log units of fO₂ relative to the QFM buffer. The structure and products of the olivine oxidation were eventually obliterated in the course of the hydration.     

Molecular orbital studies of geometries and spectra of minerals and inorganic compounds

Extended Hückel molecular orbital theory (EHT) and simple, approximate Self-Consistent-Field MO methods are employed to explain the geometries of nontransition metal bearing minerals and inorganic compounds. The spectra of such minerals and the electronic structure of transition metal oxidic minerals are explained using the Self-Consistent-Field X α MO method. EHT provides an objective algorithm for rationalizing and correlating bond length and angle data for insular and polymerized TO ₄ ^?n tetrahedral oxyanions where T=Be, B, Al, Si, P, S, Ge, As and Se. Calculated bond overlap populations n(T-O), correlate linearly with the observed T-O bond lengths with shorter bonds tending to involve larger n(T-O) values. Such calculations show that n(T-O) is strongly dependent upon the average of the three O-T-O angles associated with a common bond, larger n(T-O) values involving wider angles. Calculations of n(T-O) as a function of the T-O-T angles in T ₂O ₇ ^?n ions, indicate that the n(T-O) values for the bonds to the bridging oxygen atoms increase nonlinearly with increasing T-O-T angle whereas those the nonbridging oxygens decrease slightly as the angle widens. In agreement with the experimental data, these results predict that shorter T-O bonds should involve wider O-T-O and T-O-T angles. The SCF-X α MO cluster model is then applied to silica and FeO. The calculations yield a satisfactory interpretation of the visible, UV and X-ray emission and X-ray photoelectron spectra of these materials. Theoretical and empirical MO diagrams are constructed and the electronic structures of the materials are discussed.     

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.     

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.