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.     

TEM study of a special grain boundary in a synthetic K-feldspar bicrystal: Manebach Twin

 A monoclinic KAlSi₃O₈ feldspar Manebach twin boundary was synthesized by diffusion bonding and examined using high-resolution transmission electron microscopy. The sharp (001) twin boundary is straight and free of strain. The boundary width is smaller than d₀₀₁. There is no rigid body shift observed at the twin boundary, and the feldspar structure is arranged symmetrically across (001). The twin boundary structure consists of bridged tetrahedral crankshafts, which are characteristic of the feldspar lattice. The grain boundary structure is in good agreement with the geometrical model of Taylor et al. (1934). The grain boundary composition of K_1/2H_1/2AlSi₃O₈ differs from their model. Received: 13 February 2002 / Accepted: 24 December 2002 Acknowledgements We thank M. Rühle, S. Hutt, J. Mayer, A. Strecker and U. Salzberger at MPI, Stuttgart, for their support and valuable advice in preparing TEM sections of bicrystals.     

Water in minerals detectable by electron energy-loss spectroscopy EELS

Electron energy-loss spectroscopy EELS of the oxygen K edge of OH^– containing minerals and minerals with molecular water reveals a peak at about 528 eV prior to the onset of the O-K edge at 532 eV. This peak is never observed in minerals without water or OH^– groups. The intensity of the signal at 528 eV increases with increasing water content of the minerals. The peak at 528 eV is attributed to OH groups or water molecules. From the observations it is concluded that EELS provides a new method to determine the OH^– or water content of minerals with a spatial resolution far beyond that of optical spectroscopy. Received: 28 April 1997 / Revised, accepted: 25 July 1997     

Polymorphic phase transition in Superhydrous Phase B

We synthesized superhydrous phase B (shy-B) at 22 GPa and two different temperatures: 1200°C (LT) and 1400°C (HT) using a multi-anvil apparatus. The samples were investigated by transmission electron microscopy (TEM), single crystal X-ray diffraction, Raman and IR spectroscopy. The IR spectra were collected on polycrystalline thin-films and single crystals using synchrotron radiation, as well as a conventional IR source at ambient conditions and in situ at various pressures (up to 15 GPa) and temperatures (down to −180°C). Our studies show that shy-B exists in two polymorphic forms. As expected from crystal chemistry, the LT polymorph crystallizes in a lower symmetry space group (Pnn2), whereas the HT polymorph assumes a higher symmetry space group (Pnnm). TEM shows that both modifications consist of nearly perfect crystals with almost no lattice defects or inclusions of additional phases. IR spectra taken on polycrystalline thin films exhibit just one symmetric OH band and 29 lattice modes for the HT polymorph in contrast to two intense but asymmetric OH stretching bands and at least 48 lattice modes for the LT sample. The IR spectra differ not only in the number of bands, but also in the response of the bands to changes in pressure. The pressure derivatives for the IR bands are higher for the HT polymorph indicating that the high symmetry form is more compressible than the low symmetry form. Polarized, low-temperature single-crystal IR spectra indicate that in the LT-polymorph extensive ordering occurs not only at the Mg sites but also at the hydrogen sites.     

Correlation between hydrogen isotope ratios of lipid biomarkers and sediment maturity

We investigated the influence of thermal maturity on the hydrogen isotope ratios of sedimentary hydrocarbons to prove that the isotope ratio of hydrocarbons mirrors paleoclimate signatures. δD values from n-alkanes and acyclic isoprenoids of two sediment sections (Kupferschiefer [KS], 258 Ma, and Posidonienschiefer [PS], 184 Ma) with different maturation history were investigated. Both covered thermal maturity from 0.48 to 1.3 R_c (vitrinite reflectance and reflectance calculated from MPI1). Sediment burial up to 4500 m caused thermal maturation of organic matter in the KS horizon from the Early Zechstein basin of Poland, whereas contact metamorphic thermal maturation originated in the Early Toarcian PS (Posidonienschiefer) of the North German Vlotho Massif. The δD values of the extracted n-alkanes positively correlate with thermal maturity in the KS (y = 56‰ × MPI1[x] − 160‰ [VSMOW]) and in the PS (y = 104‰ × MPI1[x] − 200‰ [VSMOW]). The δD values of isoprenoids (i.e., pristane, phytane) were even more enriched with increasing maturity (y = 179‰ × MPI1[x] − 341‰ [VSMOW] in the KS; y = 300‰ × MPI1[x] − 415‰ [VSMOW] in PS).These results explain why isotope ratios of n-alkanes and isoprenoids in mature sediments are generally enriched in D and do not have the expected isotopic difference between n-alkanes and isoprenoids of ∼190‰. Moreover, the correlation between sediment maturity parameters and δD values suggests that after correction the δD values of n-alkanes can be used to reconstruct climate and environment in the geological past.     

Microtexture,nanomineralogy, and local chemistry of cryptocrystalline cosmic spherules

The paper reports scanning electron microscopy (FEG-SEM) and transmission electron microscopy (TEM) data on three cryptocrystalline (CC) cosmic spherules of chondritic composition (Mg/Si ≈ 1) from two collections taken up at glaciers at the Novaya Zemlya and in the area of the Tunguska event. The spherules show “brickwork” microtextures formed by minute parallel olivine crystals set in glass of pyroxene–plagioclase composition. The bulk-rock silicate chemistry, microtexture, mineralogy, and the chemical composition of the olivine and the local chemistry of the glass in these spherules testify to a chondritic source of the spherules. The solidification of the spherules in the Earth’s atmosphere was proved to be a highly unequilibrated process. A metastable state of the material follows, for example, from the occurrence of numerous nanometer-sized SiO₂ globules in the interstitial glass. These globules were formed by liquid immiscibility in the pyroxene–SiO₂ system. Troilite FeS and schreibersite (Fe,Ni)₃P globules were found in the FeNi metal in one of the spherules, which suggests that the precursor was not chemically modified when melted in the Earth’s atmosphere. Our results allowed us to estimate the mineralogy of the precursor material and correlate the CC spherules with the chondrule material of chondrites. The bulk compositions of the spherules are closely similar to those of type-IIA chondrules.     

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.     

Palynology of Triassic–Jurassic boundary sections in northern Switzerland

A first palynostratigraphic scheme of Upper Triassic deposits in northern Switzerland was established based on spore-pollen associations and dinoflagellate cyst records from the upper part of the Upper Triassic Klettgau Formation and the lower part of the Lower Jurassic Staffelegg Formation. Drill cores from the Adlerberg region (Basel Tabular Jura) and from Weiach (northern part of Canton Zurich) as well as from an outcrop at the Chilchzimmersattel (Basel Folded Jura) were studied and five informal palynological associations are distinguished. These palynological associations correlate with palynological association of the Central European Epicontinental Basin and the Tethyan realm and provide a stratigraphic framework for the uppermost Triassic sediments in northern Switzerland. Throughout the uppermost Triassic to Jurassic palynological succession a remarkable prominence of Classopollis spp. is observed. Besides Classopollis spp. the three Rhaetian palynological associations A to C from the Upper Triassic Belchen Member include typical Rhaetian spore-pollen and dinoflagellate taxa (e.g., Rhaetipollis germanicus, Geopollis zwolinskae, Rhaetogonyaulax rhaetica, and Dapcodinium priscum). Association B differs from association A in a higher relative abundance of the sporomorph taxa Perinopollenites spp. and the consistent occurrence of Granuloperculatipollis rudis and Ricciisporites tuberculatus. Spore diversity is highest in the late Rhaetian palynological association C and includes Polypodiisporites polymicroforatus. A Rhaetian age for the Belchen Member is confirmed by palynological associations A–C, but there is no record of the latest Rhaetian and the earliest Jurassic. In contrast to the Rhaetian palynological associations the Early Jurassic associations W and D include Pinuspollenites spp., Trachysporites fuscus (in association W), and Ischyosporites variegatus. In the view of the end-Triassic mass extinction and contemporaneous environmental changes the described palynofloral succession represents the pre-extinction phase (associations A and B) including a distinct transgression, the extinction phase (association C) associated with a regression, and the post-extinction phase (association W).