Phosphorus oxynitride PON, a silica analogue: structure and compression of the cristobalite-like phase; P –T phase diagram

 The structure of the cristobalite-like polymorph of phosphorus oxynitride PON has been refined using neutron powder diffraction data. It is tetragonal, space group I&4macr;2d, Z=4. The four P–(O,N) distances are equal but the tetrahedron is compressed along c. In AX₂ or ABX₄ compounds, the tetragonal I&4macr;2d or I&4macr; structure is obtained when the average ratio of the cation to anion radius is below 1.186, whereas the tetragonal P4₁2₁2 or orthorhombic C222₁ structure is obtained at low temperatures for larger ratios. The cell parameters of this PON polymorph have been determined as a function of hydrostatic pressure by in situ angle dispersive X-ray powder diffraction in a diamond-anvil cell. Under truly hydrostatic pressure, a strong anisotropic behavior is observed with the c parameter being nearly incompressible. Very slight anisotropic stress strongly modifies the high-pressure behavior. According to the pressure-temperature conditions of treatment, three phases, cristobalite-, moganite-, and quartz-like, have been obtained by quenching experiments, and the P–T phase diagram of PON was derived. The high-pressure behavior of the α-quartz, moganite, and cristobalite-like polymorphs of PON and SiO₂ is discussed. Received: 7 August 2000 / Accepted: 21 January 2001     

A novel ozone sensor for direct eddy flux measurements

A small, lightweight (1.5 kg) and fast-response ozone sensor for direct eddy flux measurements has been built. The basis for detection is the chemiluminescence of an organic dye adsorbed on dry silica gel in the reaction with ozone. The chemiluminescence is monitored with a cheap and small blue-sensitive photomultiplier. At a flow rate of 100 l min^-1 the ozone sensor has a 90% response time of significantly better than 0.1 s with a detection limit lower than 50 ppt at S/N=3. There are no interferences from other atmospheric trace gases like NO_x, H₂O₂ and PAN. Water vapour and SO₂ enhance the chemiluminescence efficiency of the ozone sensor. Since their response times are 22 seconds and 30 minutes, respectively, no correlation between rapid ozone fluctuations and those of these two trace gases is noticed by the ozone sensor when operating at a frequency of 10 Hz.The ozone sensor was tested for several weeks in continuous measurements of ozone fluxes and deposition velocities over different croplands using the eddy correlation technique. Good agreement was found between ozone dry deposition velocities derived from profile measurements and by eddy correlation.     

Zur Deckentektonik des Hochbalkans

Zusammenfassung Im Botewgebiet der Stara Planina (Hochbalkan) liegt inmitten paläozoischer, mesozoischer und tertiärer Schichten ein 30 km langer und 12 km breiter Granitkomplex, der als autochthone Einheit, aber auch als Deckscholle gedeutet worden ist. Die Deckennatur des Komplexes wird durch die großtektonischen Verhältnisse eindeutig belegt. Der Bewegungsplan besitzt meridionale Symmetrie, die tektonischen Haupttransporte erfolgten von S nach N. Groß- und Kleingefüge entsprechen einander. Das Liegende der Decke besitzt keine einheitliche Prägung. Diskordante Lagerungsverhältnisse lassen variszische, kimmerische, kretazische, laramische und pyrenäische Bewegungen erkennen.     

A meteorological 80-m tower near Rotterdam

Construction, observation site and instrumentation are described of an 80-m meteorological observation tower, erected in Vlaardingen, The Netherlands, for studies in connection with air pollution problems along the Nieuwe Waterweg. From measurements made regularly in the period April 1967–April 1968 summaries are given of wind profile parameters and gustiness averages. Case histories are presented of an air pollution episode lasting several days, and of an hourly average wind direction difference of 120 ° over 70 m.     

Electrostatic Force in Blowing Snow

Separation of electrostatic charge during the transport of particles by wind adds a force to the gravitational and fluid forces that determine trajectories of particles moving by saltation. Evaluating this electrostatic force requires the electric field strength very near the saltation surface, and charge-to-mass ratios for the moving particles. Field mill readings 4 cm above the surface in a moderate blizzard showed electric field strength as high as +30 kV m^-1. Another experiment gave charge-to-mass ratios of individual saltation particles in low-level drifting that ranged between +72 C kg^-1 and -208 C kg^-1. From these measurements, we estimated electrostatic forces as large as the gravitational force on some saltating particles. Including forces of this magnitude in the equations of motion significantly alters predicted saltation trajectories from those for uncharged particles. Predictions appear reasonable that for some saltating particles, the electrostatic force prevents new surface impacts. These results should help improve models of energy transfer in the planetary boundary layer during blizzards and sandstorms.     

High-resolution solar spectroscopy with TESOS – Upgrade from a double to a triple system

We present the characteristics and demonstrate the performance of the Triple Etalon SOlar Spectrometer (TESOS) operated at the German Vacuum Tower Telescope (VTT) on Tenerife. The Fabry–Pérot interferometer TESOS is ideally suited for precise measurements of photospheric and chromospheric motion. Installed in 1997 and equipped with two etalons, TESOS has recently been completed with a third etalon and upgraded with two high-speed, backside-illuminated CCD cameras. The image scale of 0.089 arc sec pixel^–1 is adapted to the resolution of the telescope. The improved system enables frame rates up to 5 frames per second. The spectral resolution of 300000 allows for spectral diagnostics of weak photospheric lines, including individual CH-lines within the G-band at 430.6 nm.     

The composition of liquids coexisting with dense hydrous magnesium silicates at 11-13.5 GPa and the endpoints of the solidi in the MgO-SiO2-H2O system

High-pressure liquids in the MgO-SiO₂-H₂O (MSH) system have been investigated at 11 and 13.5 GPa and between 1000 and 1350 °C. A bulk composition more magnesian than the tie-line forsterite-H₂O was employed for the study. Rocking multi-anvil experiments were combined with a diamond trap set-up. After termination of the experiments, the liquid trapped in the diamond layer was analysed by laser ablation ICP-MS using the ‘freezing’ technique. At 11 GPa, liquids coexist with one or two of phase A, clinohumite, chondrodite, and forsterite. A marked discontinuity in the evolution of liquid compositions near 1100 °C is observed at 11 GPa. A step of ∼13 wt% H₂O and 13 wt% MgO is interpreted to result from overstepping the fluid-saturated solidus reaction mass balanced to 1.00(18) phase A + 1.07(4) fluid = 0.63(15) chondrodite + 1.44(2) melt. At 13.5 GPa liquids coexist with one or two of hydrous wadsleyite, clinohumite, superhydrous B, phase B, and forsterite. The discontinuity in liquid composition is no longer present, indicating that the second critical endpoint of the solidus has been overstepped. Thus, hydrous melts in the Mg-rich part of the MSH system (molar bulk Mg/Si > 2) are chemically distinct from aqueous fluids at pressure up to 11 GPa. Convergence of fluid and melt compositions along the solidus resulting in a supercritical liquid occurs between 11 and 13.5 GPa, at which pressure the entire MSH system becomes supercritical.     

Biomediation of calcrete at the gold anomaly of the Barns prospect,Gawler Craton,South Australia

Anomalously high Au concentrations (2.5 to 50 ppb) in regolith carbonate accumulations, such as calcrete and calcareous sands in aeolian sand dunes overlying Au mineralisation of the Gawler Craton, South Australia, show a marked covariance of Au with K, Mg and most notably Ca. This relationship appears to be linked to the authigenic formation of smectites and carbonates within the aeolian dunes in the region. However, little is known about the processes involved in the formation of carbonates under semi-arid and arid conditions. In this study the geochemical properties of aeolian dunes along several depth profiles of 2 to 4 m are investigated in order to assess the relationship between Au mobility and calcrete formation. In the profiles a strongly systematic relationship between Au and the increasing Ca–Mg contents at depth highlights the close association between the enrichment of Au in the calcrete and the underlying hydrothermal mineralisation. Intense calcrete formation and concurrent Au enrichment also occurs in the vicinity of roots penetrating the dune. Thin section petrography and cathodoluminescence show that most of the calcrete in the regolith profiles is micritic; some sparic crystallites have also been identified. To demonstrate the presence of microbial processes that may mediate the formation of calcrete, samples from a depth profile in the dune were taken under sterile conditions. After amendment with urea and incubation of up to 24 h, up to 18 mg/l of NH₄⁺ were detected in near surface samples. At depth of 2.3 m 1 mg/l NH₄⁺ were detected compared to a control that contained below 0.05 mg/l NH₄⁺. These results suggest that the genesis of calcrete and pedogenic carbonate in the area may be partly biologically mediated via processes such as the metabolic breakdown of urea by resident microbiota which generates a pH and pCO₂ environment conducive to the precipitation of carbonate. In the process of urea breakdown organic Au complexes such as Au-amino acid complexes may become destabilised in solution and Au may be co-precipitated, resulting in the fine, non-particulate distribution of Au throughout the micritic calcrete carbonate. In conclusion, this study suggests a coupled mechanism of biologically mediated and inorganic mechanisms that lead to the formation of Au-in-calcrete anomalies.     

Sources and sinks of atmospheric methane

In 1972 average mixing ratio of methane in the troposphere was 1.41 ppm and 1.3 ppmv for the northern and southern hemisphere, respectively, which corresponds to a total amount of 4×10¹⁵ g of CH₄ present in the atmosphere. Most is of recent biologic origin.¹⁴C analyses show that no more than 20 percent is released by fossil sources. The various ecosystems producing CH₄ are discussed and the total annual production is estimated to lie between 5.5×10¹⁴ g/yr and 11×10¹⁴ g/yr. The corresponding turnover times for atmospheric CH₄ range from 4 to 7 yrs. The destruction of CH₄ takes place mainly in the troposphere, most probably through the reaction of CH₄ + OH CH₃ + H₂O. About 10 percent of the CH₄ is destroyed in the stratosphere. The CH₄ cycle contributes on the order of 1 percent to the atmospheric carbon cycle.