Electrons in feldspar II: a consideration of the influence of conduction band-tail states on luminescence processes

 Most natural feldspars contain many charged impurities, and display a range of bond angles, distributed about the ideal. These effects can lead to complications in the structure of the conduction band, giving rise to a tail of energy states (below the high-mobility conduction band) through which electrons can travel, but with reduced mobility: transport through these states is expected to be thermally activated. The purpose of this article is twofold. Firstly, we consider what kind of lattice perturbations could give rise to both localized and extended conduction band-tail states. Secondly, we consider what influence the band tails have on the luminescence properties of feldspar, where electrons travel through the sample prior to recombination. The work highlights the dominant role that 0.04–0.05-eV phonons play in both the luminescence excitation and emission processes of these materials. It also has relevance in the dating of feldspar sediments at elevated temperatures. Received: 11 May 2001 / Accepted: 6 September 2001     

Premelting and calcium mobility in gehlenite (Ca2Al2SiO7) and pseudowollastonite (CaSiO3)

 Premelting effects in gehlenite (Ca₂Al₂SiO₇) have been studied by Raman spectroscopy and calorimetry, and in gehlenite and pseudowollastonite (CaSiO₃) by electrical conductivity. The enthalpy of premelting of gehlenite is 17.3 kJ mol⁻¹ and represents 9% of the reported enthalpy of fusion, which is in the range of the reported fraction of other minerals. The Raman and electrical conductivity experiments at high temperatures, for gehlenite and pseudowollastonite, show that the premelting effects of both compositions are associated with enhanced dynamics of calcium atoms near the melting point. This conclusion agrees with the results obtained for other minerals like diopside, but contrasts with those found for sodium metasilicate in which the weaker bonding of sodium allows the silicate framework to distort near the melting temperature and deform in such a way to prefigure the silicate entities present in the melt. Received: 30 April 2002 / Accepted: 7 August 2002 Acknowledgements We thank Y. Linard for help with DSC measurements and two anonymous reviewers for their constructive comments. This work has been partly supported by the EU Marie-Curie fellowship contract no. HPMF-CT-1999-00329, the CNRS-Carnegie Institution of Washington program PICS no.192, and the NSF grants EAR-9614432 and EAR-9901886 to B.O.M.     

Cation distribution and structure modelling of spinel solid solutions

 This paper presents an improved generalisation of cation distribution determination based on an accurate fit of all crystal-chemical parameters. Cations are assigned to the tetrahedral and octahedral sites of the structure according to their scattering power and a set of bond distances optimised for spinel structure. A database of 295 spinels was prepared from the literature and unpublished data. Selected compositions include the following cations: Mg²⁺, Al³⁺, Si⁴⁺, Ti⁴⁺, V³⁺, Cr³⁺, Mn²⁺, Mn³⁺, Fe²⁺, Fe³⁺, Co²⁺, Ni²⁺, Zn²⁺ and vacancies. Bond distance optimisation reveals a definite lengthening in tetrahedral distance when large amounts of Fe³⁺ or Ni²⁺ are present in the octahedral site. This means that these cations modify the octahedral angle and hence the shared octahedral edge, causing an increase in the tetrahedral distance with respect to the size of the cations entering it. Some applications to published data are discussed, showing the capacity and limitations of the method for calculating cation distribution, and for identifying inconsistencies and inaccuracies in experimental data. Received: 19 February 2001 / Accepted: 1 June 2001     

Aptian to Coniacian (Early–Late Cretaceous) palynostratigraphy of the Gustav Group, James Ross Basin, Antarctica

The Gustav Group of the James Ross Basin, Antarctic Peninsula, forms part of a major Southern Hemisphere Cretaceous reference section. Palynological data, chiefly from dinoflagellate cysts, integrated with macrofaunal evidence and strontium isotope stratigraphy, indicate that the Gustav Group, which is approximately 2.6 km thick, is Aptian–Coniacian in age. Aptian–Coniacian palynofloras in the James Ross Basin closely resemble coeval associations from Australia and New Zealand, and Australian palynological zonation schemes are applicable to the Gustav Group. The lowermost units, the coeval Pedersen and Lagrelius Point formations, have both yielded early Aptian dinoflagellate cysts. Because the overlying Kotick Point Formation is of early to mid Albian age, the Aptian/Albian boundary is placed, questionably, at the Lagrelius Point Formation–Kotick Point Formation boundary on James Ross Island, and this transition may be unconformable. Although the Kotick Point Formation is largely early Albian on dinoflagellate cyst evidence, the uppermost part of the formation appears to be of mid Albian age. This differentiation of the early and mid Albian has refined the age of the formation, previously considered to be Aptian–Albian, based on macrofaunal evidence. The Whisky Bay Formation is of late Albian to latest Turonian age on dinoflagellate cyst evidence and this supports the macrofaunal ages. Late Albian palynofloras have been recorded from the Gin Cove, lower Tumbledown Cliffs, Bibby Point and the lower–middle Lewis Hill members. However, the Cenomanian age of the upper Tumbledown Cliffs and Rum Cove members, based on molluscan evidence, is not supported by the dinoflagellate cyst floras and further work is required on this succession. The uppermost part of the Whisky Bay Formation in north-west James Ross Island is of mid to late Turonian age and this is confirmed by strontium isotope stratigraphy. The uppermost unit, the Hidden Lake Formation, is Coniacian in age on both palaeontological and strontium isotope evidence. The uppermost part of the formation appears to be early Santonian based on dinoflagellate cysts, but strontium isotope stratigraphy constrains this as being no younger than late Coniacian. This refined palynostratigraphy greatly improves the potential of the James Ross Basin as a major Cretaceous Southern Hemisphere reference section.     

Post-mid-Cretaceous eastern North Sea evolution inferred from 3D thermo-mechanical modelling

The Late Cretaceous–Cenozoic evolution of the eastern North Sea region is investigated by 3D thermo-mechanical modelling. The model quantifies the integrated effects on basin evolution of large-scale lithospheric processes, rheology, strength heterogeneities, tectonics, eustasy, sedimentation and erosion.

The evolution of the area is influenced by a number of factors: (1) thermal subsidence centred in the central North Sea providing accommodation space for thick sediment deposits; (2) 250-m eustatic fall from the Late Cretaceous to present, which causes exhumation of the North Sea Basin margins; (3) varying sediment supply; (4) isostatic adjustments following erosion and sedimentation; (5) Late Cretaceous–early Cenozoic Alpine compressional phases causing tectonic inversion of the Sorgenfrei–Tornquist Zone (STZ) and other weak zones.

The stress field and the lateral variations in lithospheric strength control lithospheric deformation under compression. The lithosphere is relatively weak in areas where Moho is deep and the upper mantle warm and weak. In these areas the lithosphere is thickened during compression producing surface uplift and erosion (e.g., at the Ringkøbing–Fyn High and in the southern part of Sweden). Observed late Cretaceous–early Cenozoic shallow water depths at the Ringkøbing–Fyn High as well as Cenozoic surface uplift in southern Sweden (the South Swedish Dome (SSD)) are explained by this mechanism.

The STZ is a prominent crustal structural weakness zone. Under compression, this zone is inverted and its surface uplifted and eroded. Contemporaneously, marginal depositional troughs develop. Post-compressional relaxation causes a regional uplift of this zone.

The model predicts sediment distributions and paleo-water depths in accordance with observations. Sediment truncation and exhumation at the North Sea Basin margins are explained by fall in global sea level, isostatic adjustments to exhumation, and uplift of the inverted STZ. This underlines the importance of the mechanisms dealt with in this paper for the evolution of intra-cratonic sedimentary basins.     

Intercomparison of IRS-P4-MSMR derived geophysical products with DMSP-SSM/I and TRMM-TMI finished products

In this paper, MSMR geophysical products like Integrated Water Vapour (IWV), Ocean Surface Wind Speed (OWS) and Cloud Liquid Water (CLW) in different grids of 50, 75 and 150 kms are compared with similar products available from other satellites like DMSP-SSM/I and TRMMTMI. MSMR derived IWV, OWS and CLW compare well with SSM/I and TMI finished products. Comparison of MSMR derived CLW with that derived from TMI and SSM/I is relatively in less agreement. This is possibly due to the use of 37 GHz in SSM/I and TMI that is highly sensitive to CLW, while 37 GHz channels are not available on MSMR. Monthly comparison of MSMR geophysical products with those from TMI is all carried out for climatological purpose. The monthly comparisons were much better compared to instantaneous comparisons. In this paper, details of the data analysis and comparison results are presented. The usefulness of the MSMR vis-à-vis other sensors is also discussed.     

Water solubility in orthopyroxene

The solubility of water in pure enstatite was measured on samples synthesized at 1,100 °C and pressures to 100 kbar. Enstatite crystals were grown under water-saturated conditions from a stoichiometric mixture of high-purity SiO₂ and Mg(OH)₂. Water contents were calculated from polarized FTIR spectra measured on oriented single crystals. The water solubility in orthoenstatite increases with pressure to 867ᆷ ppm H₂O by weight at 75 kbar. At 100 kbar, in the stability field of high-clinoenstatite, a water solubility of 714ᆷ ppm was observed. The water solubility in enstatite at 1,100 °C can be described by the equation c_H2O=Af_H2O exp(-P(V/RT), where f_H2O is water fugacity, A=0.0204 ppm/bar and (V=12.3 cm³/mol. The infrared spectra of the hydrous enstatite crystals show a sharp, intense band at 3,363 cm^-1 and a broad, weaker band at 3,064 cm^-1. Both bands are strongly polarized parallel c. Most likely, pairs of protons attached to non-bridging oxygen atoms substitute for Mg²⁺. In order to investigate the effect of chemical impurities on water solubility in enstatite, an additional series of experiments was carried out with gels doped with Al, B, or Li as starting material. Whereas, the presence of Li and B had no detectable effect on water solubility, the addition of about 1 wt% Al₂O₃ increased water solubility in enstatite from 199 to 1,100 ppm at 1,100°C and 15 kbar. In the infrared spectra of these aluminous samples, additional bands occur in the range from 3,450 to 3,650 cm^-1. Similar bands are also observed in natural, aluminous orthopyroxenes and are most likely caused by protons coupled with Al according to the substitution of Al³⁺+H⁺ for Si⁴⁺. A series of hydrous annealing experiments on a natural, gem-quality aluminous enstatite from Tanzania yielded water solubilities generally consistent with the results from the synthetic model systems. The results presented here imply that pure enstatite has a similar storage capacity for water as olivine; however, aluminous orthopyroxenes in the mantle may dissolve much larger amounts of water comparable with the entire mass of the present hydrosphere. Moreover, the mechanism of aluminum substitution in orthopyroxenes, i.e., the distribution of Al between tetrahedral and octahedral sites, may be a potential probe of water fugacity.     

Formation of refractory inclusions by evaporation of condensate precursors

Berman’s (1983) activity-composition model for CaO-MgO-Al₂O₃-SiO₂ liquids is used to calculate the change in bulk chemical and isotopic composition during simultaneous cooling, evaporation, and crystallization of droplets having the compositions of reasonable condensate precursors of Types A and B refractory inclusions in CV3 chondrites. The degree of evaporation of MgO and SiO₂, calculated to be faithfully recorded in chemical and isotopic zoning of individual melilite crystals, is directly proportional to evaporation rate, which is a sensitive function of P_H2, and inversely proportional to the droplet radius and cooling rate. When the precursors are partially melted in pure hydrogen at peak temperatures in the vicinity of the initial crystallization temperature of melilite, their bulk chemical compositions evolve into the composition fields of refractory inclusions, mass-fractionated isotopic compositions of Mg, Si, and O are produced that are in the range of the isotopic compositions of natural inclusions, and melilite zoning profiles result that are similar to those observed in real inclusions. For droplets of radius 0.25 cm evaporating at P_H2 = 10⁻⁶ bar, precursors containing 8 to 13 wt.% MgO and 20 to 23% SiO₂ evolve into objects similar to compact Type A inclusions at cooling rates of 2 to 12 K/h, depending on the precise starting composition. Precursors containing 13 to 14 wt.% MgO and 23 to 26% SiO₂ evolve into objects with the characteristics of Type B1 inclusions at cooling rates of 1.5 to 3 K/h. The relatively SiO₂-poor members of the Type B2 group can be produced from precursors containing 14 to 16 wt.% MgO and 27 to 33% SiO₂ at cooling rates of <1 K/h. Type B2’s containing 27 to 35 wt.% SiO₂ and <12% MgO require precursors with higher SiO₂/MgO ratios at MgO > 15% than are found on any condensation curve. The characteristics of fluffy Type A inclusions, including their reversely zoned melilite, can only be understood in the context of this model if they contain relict melilite.     

Source and H2O content of high-MgO magmas in island arc settings: an experimental study of a primitive calc-alkaline basalt from St. Vincent, lesser antilles arc

Liquidus phase relationships have been determined for a high-MgO basalt (STV301: MgO=12.5 wt%, Ni=250 ppm, Cr=728 ppm) from Black Point, St Vincent (Lesser Antilles arc). Piston-cylinder experiments were conducted between 7.5 and 20 kbar under both hydrous and oxidizing conditions. AuPd capsules were used as containers. Compositions of supraliquidus glasses and mass-balance calculations show that Fe loss is < 10% in the majority of experiments. Two series of water concentrations in melt were investigated: (i) 1.5 wt% and (ii) 4.5 wt% H₂O, as determined by SIMS analyses on quenched glasses and with the by difference technique. The Fe³⁺/Fe²⁺ partitioning between Cr-Al spinel and melt and olivine-spinel equilibria show that oxidizing fO₂ were imposed (NNO + 1.5 for the 1.5 wt% H₂O series, NNO + 2.3 for the 4.5 wt% H₂O series). For both series of water concentrations, the liquid is multiply-saturated with a spinel lherzolite phase assemblage on its liquidus, at 1235°C, 11.5 kbar (1.5 wt% H₂O) and 1185°C, 16 kbar (4.5 wt% H₂O). Liquidus phases are homogeneous and comparable to typical mantle compositions. Mineral-melt partition coefficients are generally identical to values under anhydrous conditions. The modal proportion cpx/opx on the liquidus decreases from the 1.5 wt% to the 4.5 wt% H₂O series. The experimental data are consistent with STV301 being a product of partial melting of lherzolitic mantle. Conditions of multiple saturation progressively evolve toward lower temperatures and higher pressures with increasing melt H₂O concentration. Phase equilibria constraints, i.e., the necessity of preserving the mantle signature seen in high-MgO and picritic arc basalts, and glass inclusion data suggest that STV301 was extracted relatively dry (∼ 2 wt% H₂O) from its mantle source. However, not all primary arc basalts are extracted under similarly dry conditions because more hydrous melts will crystallize during ascent and will not be present unmodified at the surface. From degrees of melting calculated from experiments on KLB-1, extraction of a 12.5 wt% MgO melt with ∼ 2 wt% H₂O would require a H₂O concentration of 0.3 wt% in the sub-arc mantle. For mantle sources fluxed with a slab-derived hydrous component, extracted melts may contain up to ∼ 5.5 wt% H₂O.