Chemical and structural relations of epitaxial xenotime and zircon substratum in sedimentary and hydrothermal environments: a TEM study

Xenotime overgrowths on detrital zircon in siliciclastic sediments have been reported in numerous studies. However, in natural samples, solid solution of zircon and xenotime is limited to near-end-member compositions. In order to characterize the interface region between both minerals and to draw inferences on the growth mechanisms of authigenic xenotime, we studied xenotime overgrowths on detrital zircon grains from two Phanerozoic sandstone samples with contrasting post-depositional histories. In one sample, the small (≤10 μm), pyramidal xenotime overgrowths are of diagenetic origin and grew without major discontinuity on the detrital zircon grain. The second sample shows up to >50-μm-wide, porous and inclusion-rich, hydrothermal xenotime overgrowths on detrital zircon, whereas the transition zone between both minerals is accompanied by large pore volume. Chemical compositions of the xenotime precipitates from the two samples differ particularly in Y, REE, Th and Sc concentrations, whereas high MREE availability in the diagenetic sample and the presence of Sc in the hydrothermal sample, respectively, appear to have promoted xenotime growth. Transmission electron microscopy on electron-transparent foils cut from the interface region shows that both the diagenetic xenotime and the hydrothermal xenotime are crystalline and grew in optical and crystallographic continuity to their detrital zircon substrata. Only a narrow transition zone (≤90 nm—diagenetic sample, 200–300 nm—hydrothermal sample) between zircon and xenotime is in part made up of nanometre-scale crystalline domains that are slightly distorted and may have formed from dissolution–re-precipitation processes at the zircon rim along with precipitation from the respective fluid.     

TiO2 exsolution from garnet by open-system precipitation: evidence from crystallographic and shape preferred orientation of rutile inclusions

We investigated rutile needles with a clear shape preferred orientation in garnet from (ultra) high-pressure metapelites from the Kimi Complex of the Greek Rhodope by electron microprobe, electron backscatter diffraction and TEM techniques. A definite though complex crystallographic orientation relationship between the garnet host and rutile was identified in that Rt[001] is either parallel to Grt<111> or describes cones with opening angle 27.6° around Grt<111>. Each Rt[001] small circle representing a cone on the pole figure displays six maxima in the density plots. This evidence together with microchemical observations in TEM, when compared to various possible mechanisms of formation, corroborates a precipitate origin. A review of exchange vectors for Ti substitution in garnet indicates that rutile formation from garnet cannot occur in a closed system. It requires that components are exchanged between the garnet interior and the rock matrix by solid-state diffusion, a process we refer to as “open-system precipitation” (OSP). The kinetically most feasible reaction of this type will dominate the overall process. The perhaps most efficient reaction involves internal oxidation of Fe²⁺ to Fe³⁺ and transfer from the dodecahedral to the octahedral site just vacated by $ {\text{Ti}}^{ 4+ }: 6\,{\text{M}}^{ 2+ }_{ 3} {\text{TiAl}}\left[ {{\text{AlSi}}_{ 2} } \right]{\text{O}}_{ 1 2} + 6\,{\text{M}}^{ 2+ }_{ 2, 5} {\text{TiAlSi}}_{ 3} {\text{O}}_{ 1 2} = 10\,{\text{M}}^{ 2+ }_{ 3.0} {\text{Al}}_{ 1. 8} {\text{Fe}}_{0. 2} {\text{Si}}_{ 3} {\text{O}}_{ 1 2} + {\text{M}}^{2+} + 2 {\text{e}}^{-} + 1 2\,{\text{TiO}}_{ 2} . $ OSP is likely to occur at conditions where the transition of natural systems to open-system behaviour becomes apparent, as in the granulite and high-temperature eclogite facies.     

Error evolution in the dynamics of an ocean general circulation model

The problem of error propagation is considered for spatially uncorrelated errors of the barotropic stream function in an oceanic general circulation model (OGCM). Such errors typically occur when altimetric data from satellites are assimilated into ocean models. It is shown that the error decays at first due to the dissipation of the smallest scales in the error field. The error then grows exponentially before it saturates at the value corresponding to the difference between independent realizations. A simple analytic formula for the error behavior is derived; it matches the numerical results documented for the present primitive-equation ocean model, and other models in the literature.     

On the breakdown of zircon upon “dry” thermal annealing

Zircon samples without and with secondary chemical alteration from diverse sources were subjected to heat treatment at 1400 °C for 96 h. Resulting new phases and textures suggest that decomposition of zircon into component oxides occurred in all experiments to various degrees. The crucible material was found to have a strong influence on the extent of breakdown, especially in the case of altered starting materials. In this study the progressive stages of the breakdown of zircon grains are described. The factors that may govern the decomposition are discussed, including radiation damage, secondary alteration and external reaction conditions (sample container, atmosphere). Alumina crucibles should generally be avoided in dry annealing of zircon, to minimise uncontrolled breakdown into oxides.     

Origin of ore fluids in the Muruntau gold system: Constraints from noble gas, carbon isotope and halogen data

Hydrothermal vein minerals directly associated with native gold mineralization in the Muruntau vein system (Uzbekistan) have been studied for noble gas, carbon isotope and halogen chemistry of the trapped ore-related fluids. Helium trapped in early arsenopyrite 1, which has preserved the original fluid signature better than associated scheelite and quartz, indicates a small input from a mantle source (?5% of total He). However, the overwhelming majority of the He in the fluid (∼95%) is from crustal sources. The noble gases Ne, Kr and Xe in the sample fluids are dominated by gases of atmospheric origin. The carbon isotope (δ¹³C: −2.1‰ to −5.3‰) and halogen characteristics of the fluids (log Br/Cl: −2.64 to −3.23) lend further support for the activity of juvenile fluids during the main ore stage. The high proportion of crustal components in the ore-forming fluids may be explained by intense fluid-rock interaction and is also supported by previous Nd and Sr isotope studies. The involvement of a juvenile fluid component during the main stage of hydrothermal activity at Muruntau (∼275 Ma) can be linked to the emplacement of lamprophyric dikes at Muruntau, due to apparently overlapping ages for high-temperature alteration, related ore vein formation and intrusion of the dikes. The input of mantle-derived fluids, possibly related to the Hercynian collisional event in the western Tien Shan, stimulated intense fluid-rock interaction in the crust. In this context, the mantle-derived fluid should be considered as one possible carrier of metals. Significant amounts of external meteoric fluids circulating in fracture systems are interpreted to have modified the noble gas signature of fluid in quartz, mostly during late, low temperature fluid circulation.     

Zircon M127 – A Homogeneous Reference Material for SIMS U–Pb Geochronology Combined with Hafnium,Oxygen and,Potentially, Lithium Isotope Analysis

In this article, we document a detailed analytical characterisation of zircon M127, a homogeneous 12.7 carat gemstone from Ratnapura, Sri Lanka. Zircon M127 has TIMS‐determined mean U–Pb radiogenic isotopic ratios of 0.084743 ± 0.000027 for ²⁰⁶Pb/²³⁸U and 0.67676 ± 0.00023 for ²⁰⁷Pb/²³⁵U (weighted means, 2s uncertainties). Its ²⁰⁶Pb/²³⁸U age of 524.36 ± 0.16 Ma (95% confidence uncertainty) is concordant within the uncertainties of decay constants. The δ¹⁸O value (determined by laser fluorination) is 8.26 ± 0.06‰ VSMOW (2s), and the mean ¹⁷⁶Hf/¹⁷⁷Hf ratio (determined by solution ICP‐MS) is 0.282396 ± 0.000004 (2s). The SIMS‐determined δ⁷Li value is ?0.6 ± 0.9‰ (2s), with a mean mass fraction of 1.0 ± 0.1 μg g^?1 Li (2s). Zircon M127 contains ~ 923 μg g^?1 U. The moderate degree of radiation damage corresponds well with the time‐integrated self‐irradiation dose of 1.82 × 10¹⁸ alpha events per gram. This observation, and the (U–Th)/He age of 426 ± 7 Ma (2s), which is typical of unheated Sri Lankan zircon, enable us to exclude any thermal treatment. Zircon M127 is proposed as a reference material for the determination of zircon U–Pb ages by means of SIMS in combination with hafnium and stable isotope (oxygen and potentially also lithium) determination.     

Preliminary reconstruction of sediment-source linkages for the past 6000 yr at the Petit Lac d'Annecy, France, based on mineral magnetic data

An 8 m core from the central plain of the Petit Lac d'Annecy, France, two floodplain cores, river bedload sediments and several hundred soil samples from the catchment have been studied using magnetic techniques. The soils, mainly developed on limestones and local glacial tills, show widespread magnetic enhancement with higher ferrimagnetic concentrations and contents of SP grains than found in the lake sediments. Some soils show significant concentrations of canted antiferromagnetic minerals (mainly haematite). Using magnetic quotient parameters the surface soils are classified into four mineralogical types. The lake and floodplain sediment properties over the past 6000 yrs can largely be explained by the erosion and deposition of these sources, with a smaller superimposed biogenic (magnetosomes) signal. Derived sediment-source linkages allow the construction of several hypotheses about geomorphological changes in the catchment system: (i) the long-term erosion of high altitude unweathered substrates has gradually increased towards the present day; (ii) the erosion of high altitude soils has increased within the last 1000 yrs, possibly during the period of the 'Little Ice Age'; (iii) shifts towards an increased erosion of surface lowland soil occurred ~2000 and 1000 yrs ago and may be linked to an accelerated accretion of floodplain overbank deposits; (iv) there has been a significant storage of surface soil within floodplains, which leads to an underestimation of the importance of soil erosion in the lake sediment records; (v) the sediment transported by high magnitude, low frequency flood events has shifted in source from high altitude soils before ~1000 cal. yr BP to lowland and mid-altitude free draining soils after ~1000 cal. yr BP.     

Extrinsic and intrinsic mode of hydrogen occurrence in natural olivines: FTIR and TEM investigation

Olivine crystals from two mantle nodules in kimberlites (pipe Udachnaya and pipe Obnazennaya, Yakutiya, Siberia) were investigated using EMP, TEM, AEM and FTIR techniques to determine the mode of hydrogen occurrence in olivine. Olivine contains three types of nanometer-sized inclusions: “large” inclusions of hexagonal-like shape up to several hundred nm in size (1), lamellar defects (2) and small inclusions of hexagon-like shape up to several 10?nm in size (3). Lamellar defects and small inclusions are considered to be a “hydrous” olivine. All three types of inclusions contain OH^? or water, but they are different with respect to their phase composition. In “large” inclusions (1) hydrous magnesium silicates, such as serpentine?+?talc (“kerolite”?) and 10-Å phase?+?talc were identified. Lamellar defects (2) and small inclusions (3) are depleted in Mg and Fe compared to the olivine matrix, while the silica content is the same as that of olivine. Modulations in the periodicity of the olivine structure are observed in SAED patterns and HREM images of (2) and (3). The superperiodicity can be referred to OH^?-bearing point defect ordering in the olivine structure. If this is the case, the material of both lamellar defects and small inclusions can be assumed to be a “hydrous olivine” Mg_{2– x} v _x SiO₄H_{2 x} with a cation-deficient olivine crystal structure. Thus, both an extrinsic mode of hydrogen occurrence in olivine, such as nanometer-sized inclusions of OH^?-bearing magnesium silicates, and an intrinsic mode of hydrogen incorporation into the olivine structure, such as “hydrous olivine” in itself, were found. The data obtained here show that the OH absorption bands observed in olivine spectra at 3704(3717) and 3683(3688) cm^?1 can be unambiguously identified with serpentine; the band at 3677(3676) cm^?1 can be associated with talc. The absorption bands observed at 3591 and 3660?cm^?1 in olivine match those of the 10-Å phase at 3594, 3662 and 3666?cm^?1.     

High-resolution sea ice in long-term global ocean GCM integrations

The resolution of the sea-ice component of a coarse-resolution global ocean general circulation model (GCM) has been enhanced to about 22 km in the Southern Ocean. The ocean GCM is designed for long-term integrations suitable for investigations of the deep-ocean equilibrium response to changes in southern hemisphere high-latitude processes. The space and time scales of the high-resolution sea-ice component are commensurate with those of the resolution of satellite passive-microwave sea-ice data. This provides the opportunity for a rigorous evaluation of simulated sea-ice characteristics. It is found that the satellite-derived continuous high ice concentration of the interior winter ice pack can only be captured when vertical oceanic mixing is modified in a way that less local, intermittent convection occurs. Furthermore, the width and the variability of the coastal polynyas around the Antarctic continent and its ice shelves are best captured when some form of ice-shelf melting is accounted for. The width of the wintertime ice edge is reasonably reproduced, while its variability remains underestimated, closely following the coarse-grid pattern of the ocean model due to its high dependence on ocean temperature. Additional variability besides daily winds, e.g. in form of idealized tidal currents, improves the temporal and spatial ice-edge variability, while leads in the interior ice pack become more abundant, more in line with the fine-scale satellite-derived texture. The coast- or ice-shelf line is described on the fine grid based on satellite passive-microwave data. This method requires parts of a coarse coastal ocean grid cell to be covered by an inert layer of “fast ice” or “ice shelf”. Reasonable long-term global deep-ocean properties can only be achieved when these areas are not inert, i.e. are exposed to heat flux and ice growth, or when the vertical mixing parameterization allows for excessive open-ocean convection. The model area exposed to cold high-latitude atmospheric conditions thus being most decisive for a realistic representation of the long-term deep-ocean properties, suggests that high-latitude coastlines are definitely in need of being represented at high resolution, including ice sheets and their effects on the heat and freshwater flux for the ocean.