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     

Grain-size-sensitive flow and shear-stress enhancement at the brittle–ductile transition of the continental crust

Localized shear zones along low-angle normal faults have been identified in regions of extension at the brittle-ductile transition of the continental crust. The possibility of the strain localizing at a depth of 10 km is interpreted here as a consequence of an increase in the equivalent shear stress applied to the flow of the lower crust. This enhancement of the flow stress is seen as a prerequisite for the triggering of brittle deformation mechanisms leading to strain localization. The lower crust rheology used to examine this stress increase is strain-rate, temperature and grain-size dependent, due to the coupling of dislocation and diffusion creep. The model structure proposed consists of a top layer, the upper crust, gliding rigidly above a bottom layer, the lower crust, which deforms in simple shear. During a short time interval (1400 years), the equivalent shear stress is found to increase by a factor of up to 3 (67 MPa for anorthite and 17 MPa for quartz). For anorthite, this stress could explain the activation of a Mohr-Coulomb failure with a friction coefficient of 0.2, which is reasonable at the depth of 10 km. Dislocation creep is activated during a rapid change in the prescribed velocity, whereas diffusion creep dominates if the velocity is held constant, highlighting the importance of grain-size sensitivity for lower crustal rheology.     

Sensitivity of a Greenland ice sheet model to ice flow and ablation parameters: consequences for the evolution through the last climatic cycle

Sensitivity experiments are conducted to test the influence of poorly known model parameters on the simulation of the Greenland ice sheet by means of a three dimensional numerical model including the mechanical and thermal processes within the ice. Two types of experiments are performed: steady-state climatic conditions and simulations over the last climatic cycle with a climatic forcing derived from the GRIP record. The experiments show that the maximum altitude of the ice sheet depends on the ice flow parameters (deformation and sliding law coefficients, geothermal flux) and that it is low when the ice flow is fast. On the other hand, the maximum altitude is not sensitive to the ablation strength and consequently during the climatic cycle it is driven by changes in accumulation rate. The ice sheet extension shows the opposite sensitivity: it is barely affected by ice flow velocity and the ice covered area is smaller for large ablation coefficients. For colder climates, when there is no ablation, the ice sheet extension depends on the sea level. An interesting result is that the variations with time of the altitude at the ice divide (Summit) do not depend on the parameters we tested. The present modelled ice sheets resulting from the climatic cycle experiments are compared with the present measured ice sheet in order to find the set of parameters that gives the best fit between modelled and measured geometry. It seems that, compared to the parameter set most commonly used, higher ablation rate coefficents must be used. Received: 19 September 1995 / Accepted: 30 May 1996     

Ice-sheet growth and high-latitudes sea-surface temperature

The response of the LLN 2-D climate model to the insolation and CO₂ forcings during the Eemian interglacial is compared to reconstructions obtained from deep-sea cores drilled in the Norwegian Sea and in the North Atlantic. Both reconstructions and modeling results show a decrease of sea-surface temperature (SST) in the higher latitudes (70–75 °N zonal belt for the model and the Norwegian Sea for the proxy records), associated with a more moderate cooling at lower latitudes (50–55 °N and North Atlantic), at the middle of isotopic substage 5e, several millenia before the beginning of continental ice-sheet growth. Such a comparison between the simulated SST and ice volume of the Northern Hemisphere has been extended to the whole last glacial-interglacial cycle. The influence of the insolation forcing on SST and the shortcomings of the model due to its zonal character are discussed. Received: 6 July 1995/Accepted: 19 December 1995     

Study of the air-sea interactions at the mesoscale: the SEMAPHORE experiment

The SEMAPHORE (Structure des Echanges Mer-Atmosphère, Propriétés des Hétérogénéités Océaniques: Recherche Expérimentale) experiment has been conducted from June to November 1993 in the Northeast Atlantic between the Azores and Madeira. It was centered on the study of the mesoscale ocean circulation and air-sea interactions. The experimental investigation was achieved at the mesoscale using moorings, floats, and ship hydrological survey, and at a smaller scale by one dedicated ship, two instrumented aircraft, and surface drifting buoys, for one and a half month in October-November (IOP: intense observing period). Observations from meteorological operational satellites as well as spaceborne microwave sensors were used in complement. The main studies undertaken concern the mesoscale ocean, the upper ocean, the atmospheric boundary layer, and the sea surface, and first results are presented for the various topics. From data analysis and model simulations, the main characteristics of the ocean circulation were deduced, showing the close relationship between the Azores front meander and the occurrence of Mediterranean water lenses (meddies), and the shift between the Azores current frontal signature at the surface and within the thermocline. Using drifting buoys and ship data in the upper ocean, the gap between the scales of the atmospheric forcing and the oceanic variability was made evident. A 2 °C decrease and a 40-m deepening of the mixed layer were measured within the IOP, associated with a heating loss of about 100 W m⁻². This evolution was shown to be strongly connected to the occurrence of storms at the beginning and the end of October. Above the surface, turbulent measurements from ship and aircraft were analyzed across the surface thermal front, showing a 30% difference in heat fluxes between both sides during a 4-day period, and the respective contributions of the wind and the surface temperature were evaluated. The classical momentum flux bulk parameterization was found to fail in low wind and unstable conditions. Finally, the sea surface was investigated using airborne and satellite radars and wave buoys. A wave model, operationally used, was found to get better results compared with radar and wave-buoy measurements, when initialized using an improved wind field, obtained by assimilating satellite and buoy wind data in a meteorological model. A detailed analysis of a 2-day period showed that the swell component, propagating from a far source area, is underestimated in the wave model. A data base has been created, containing all experimental measurements. It will allow us to pursue the interpretation of observations and to test model simulations in the ocean, at the surface and in the atmospheric boundary layer, and to investigate the ocean-atmosphere coupling at the local and mesoscales.     

Finding regions of influence on SO2 and SO= 4 daily concentration measurements at four sites in Spain

Contamination by the pollutants SO₂ and SO⁼₄ was analyzed for the 1989–1992 period at four regional stations in Spain under the auspices of the EMEP-BAPMON program. The evolution of the time series of the daily pollution has also been assessed, and high mean concentrations at La Cartuja and Logroño observed, with values of 3.8 and 4.5 g m⁻³ for SO₂, respectively. Maximum annual concentrations were recorded in 1989, when SO₂ reached values of 6.24, 5.39, 5.71, and 9.30 g m⁻³ for the stations of La Cartuja, San Pablo de los Montes, Roquetas, and Logroño, respectively. This work attempts to establish a relationship between the concentrations of the pollutants - both SO₂ gas and SO⁼₄ aerosol - and the zones of emission or persistence of these long-range transported pollutants. In this way, those regions showing a greater impact on the air quality in each season have been determined. To achieve this, the trajectories of the air masses carrying away the pollution to each of the receiving stations were considered and followed by a sectorial analysis. Nonparametric statistical methods were implemented to contrast the chemical homogeneity among the different sectors. The criterion that several homogeneous sectors form a chemically homogeneous region was used. To improve this sectorial analysis, we have proposed a new technique based on the Potential-Source-Contribution Function (PSCF). Starting out from a set of specified regions, considered to be chemically homogeneous domains, it is possible to determine the likelihood that an air mass with particular characteristics (e.g., that a value of the daily concentration higher than the mean recorded at the station has been obtained) will arrive at a given station after having crossed one of the previously defined regions. Using this technique, it is possible to determine the source regions through which the air masses circulate and bring high pollution concentrations to the studied stations. Thanks to the PSCF, these statistical methods offer, through a sectorial analysis, the possibility to pass from a qualitative to a more quantitative view.     

Two Experimental Methods to Determine the Speciation of Cadmium in Sediment from the River Neckar

The binding forms of Cd to an anaerobic sediment of low sulfide content from Lauffen reservoir (River Neckar, Germany) were studied using two different approaches, i. e. sequential extraction (modified from published protocols) and titrimetric study of the pH-dependent Cd release. Thermodynamic equilibrium calculations were applied to calculate both the release pattern of Cd during the titrations and the speciation of Cd within the single fractions of the extraction protocol. The calculations were based on measured sediment parameters such as hydrous ferric oxide (HFO), acid volatile sulfide, carbonate content and total Cd content, and the extractants (oxalate, acid etc.) used. The results of the two independent approaches coincided well in that they both assigned more than two thirds of the total Cd content to be adsorbed to organic matter. Cd bound as CdS is of little importance. Sequential extraction after a 3-month oxidation period at pH 7 revealed a shift of Cd from being mainly bound in stronger surface complexes with organic matter to being mainly bound in weaker surface complexes with organic matter and HFO, and thus becoming more bioavailable. This study suggests that the use of sequential extraction although being frequently criticized due to its operational character can be used to determine binding forms of metal ions if they are accompanied by 1) careful supporting experiments, 2) analysis of important sediment parameters, and 3) the use of thermodynamic equlibrium models which can help to understand Cd speciation within the extraction fractions.     

Monthly summaries of merchant ship surface marine observations and implications for climate variability studies

We compute the interannual fluctuations of the surface heat budget of the North Atlantic using the trimmed monthly summaries of the Comprehensive Ocean-Atmosphere DataSet (COADS) for the period 1950–1979. The presence of long-period trends in the heat budget imply large variations of the northward cross-equatorial heat transport over the years. To assess the reliability of these variations, we compare the COADS climate signal to that derived from the ocean weather stations (OWSs) of the North Atlantic. The sea surface temperature, air temperature and sea level pressure show good correlation between the anomaly time series derived from the merchant ship monthly summaries of COADS, and those derived from OWS monthly summaries, except for northernmost locations during winter. In contrast, the sensible and latent heat parameters, which require simultaneous measurements of various variables, have merchant ships and ocean weather stations anomaly time series that are poorly correlated. Only in heavily travelled latitudes and during winter, when the air-sea heat exchange anomalies are large, are the merchant ship measurements able to reproduce the interannual fluctuations of the heat fluxes. The long-period trends in the surface heat budget of North Atlantic equatorward of 40° N implied by COADS thus appear unrepresentative of true climate trends. The COADS trends result from a gradual increase in the magnitude of the reported winds over the years due probably to variations in the ratio of measured to estimated winds, as well as from long period fluctuations in the near surface vertical temperature and humidity gradients. Offprint requests to: R Michaud     

Compression and coordination changes in pyroxenoids: an EXAFS study of MgGeO3 enstatite and CaGeO3 wollastonite

The evolution of the distortion of MgGeO₃ enstatite and CaGeO₃ wollastonite with increasing pressure, has been investigated using X-ray absorption spectroscopy (XAS) in a diamond anvil cell. At room temperature and low pressure (P<7 GPa), the compressibility of the GeO₄ tetrahedron is higher in MgGeO₃ enstatite (K _[GeO4]∼135 GPa) than in CaGeO₃ wollastonite (K _[GeO4]≥ 280 GPa). The compression mechanisms of the two compounds are different: the whole mineral compressibility of Ge-enstatite appears to be very homogeneous, in contrast to that of Ge-wollastonite which exhibits an inhomogeneous tretrahedral compressibility. This result is consistent with the variation of the Debye-Waller factors of the two compounds with increasing pressure. At higher pressures, the coordination of germanium atoms in the two compounds gradually changes from fourfold to sixfold. For CaGeO₃ the coordination change starts at 7 GPa and is complete a 12 GPa, whereas it starts at about 8.5 GPa for MgGeO₃ and is not complete at 31 GPa. The progressive evolution of the measured Ge-O distances as well as the modification in the X-ray absorption near-edge structure indicate two coexisting different sites rather than a progressive site modification. The transformation is found to be partially reversible in CaGeO₃ wollastonite, whereas it is totally reversible in MgGeO₃ enstatite.