Computational study of tetrahedral Al–Si and octahedral Al–Mg ordering in phengite

 As part of a wider study of the nature and origins of cation order–disorder in micas, a variety of computational techniques have been used to investigate the nature of tetrahedral and octahedral ordering in phengite, K₂ ^[6](Al₃Mg)^[4](Si₇Al)O₂₀(OH)₄. Values of the atomic exchange interaction parameters J _n used to model the energies of order–disorder were calculated. Both tetrahedral Al–Si and octahedral Al–Mg ordering were studied and hence three types of interaction parameter were necessary: for T–T, O–O and T–O interactions (where T denotes tetrahedral sites and O denotes octahedral sites). Values for the T–T and O–O interactions were taken from results on other systems, whilst we calculated new values for the T–O interactions. We have demonstrated that modelling the octahedral and tetrahedral sheets alone and independently produces different results from modelling a whole T–O–T layer, hence justifying the inclusion of the T–O interactions. Simulations of a whole T–O–T layer of phengite indicated the presence of short-range order, but no long-range order was observed. Received: 8 August 2002 / Accepted: 14 February 2003 Acknowledgements The authors are grateful to EPSRC (EJP) and the Royal Society (CIS) for financial support. Monte Carlo simulations were performed on the Mineral Physics Group's Beowulf cluster and the University of Cambridge's High Performance Computing Facility.     

Spectral and Multiscale Signal-to-Noise Thresholding of Spherical Vector Fields

The basic concepts of spectral and multiscale selective reconstruction of (geophysically relevant) vector fields on the sphere from error-affected data is outlined in detail. The reconstruction mechanism is formulated under the assumption that spectral as well as multiscale approximation is well-representable in terms of only a certain number of expansion coefficients at the various resolution levels. It is shown that spectral denoising by means of orthogonal expansions in terms of vector spherical harmonics reflects global a priori information of the noise (e.g., in form of a covariance tensor field), whereas multiscale signal-to-noise thresholding can be performed under locally dependent noise information within a multiresolution analysis in terms of spherical vector wavelets. An application of the multiscale formalism to Earth's magnetic field determination is presented.     

Source of trace element variability in Great Barrier Reef corals affected by the Burdekin flood plumes

Massive corals in the Great Barrier Reef, analyzed at high-resolution for Sr/Ca (thermal ionization mass spectrometry) and trace elements such as Ba and Mn (laser ablation inductively coupled plasma mass spectrometry), can provide continuous proxy records of dissolved seawater concentrations, as well as sea surface temperature (SST). A 10-yr record (1989 to 1998) from Pandora Reef, an inshore reef regularly impacted by the freshwater plumes of the Burdekin River, is compared with an overlapping record from a midshelf reef, away from runoff influences. Surface seawater samples, taken away from river plumes, show little variability for Sr/Ca (8484 ± 10 μmol/mol) and Ba (33.7 ± 0.7 nmol/kg). Discrete Ba/Ca peaks in the inshore coral coincide with flood events. The magnitude of this Ba/Ca enrichment is most likely controlled by the amount of suspended sediments delivered to the estuary, which remains difficult to monitor. The maximum flow rate at peak river discharge is used here as a proxy for the sediment load and is shown to be strongly correlated with coral Ba/Ca (r = 0.97). After the wet summer of 1991, the coral Ba/Ca flood peak is followed by a plateau that lingers for several months after dissipation of plume waters, signifying an additional flux of Ba that may originate from submarine groundwater seeps and/or mangrove reservoirs. Both Mn and Y are enriched by a factor of ∼5 in inshore relative to midshelf corals. Mn/Ca ratios show a seasonal cycle that follows SST (r = 0.7), not river discharge, with an additional high variability in summer suggesting a link with biological activity. P and Cd show no significant seasonal variation and are at a low level at both inshore and midreef locations. However, leaching experiments suggest that part of the coral P is not lattice bound.     

Experimental determination of the stability and stoichiometry of sulphide complexes of silver(I) in hydrothermal solutions to 400°C

The solubility of silver sulphide (acanthite/argentite) has been measured in aqueous sulphide solutions between 25 and 400°C at saturated water vapour pressure and 500 bar to determine the stability and stoichiometry of sulphide complexes of silver(I) in hydrothermal solutions. The experiments were carried out in a flow-through autoclave, connected to a high-performance liquid chromatographic pump, titanium sampling loop, and a back-pressure regulator on line. Samples for silver determination were collected via the titanium sampling loop at experimental temperatures and pressures. The solubilities, measured as total dissolved silver, were in the range 1.0 × 10⁻⁷ to 1.30 × 10⁻⁴ mol kg⁻¹ (0.01 to 14.0 ppm), in solutions of total reduced sulphur between 0.007 and 0.176 mol kg⁻¹ and pH_T,p of 3.7 to 12.7. A nonlinear least squares treatment of the data demonstrates that the solubility of silver sulphide in aqueous sulphide solutions of acidic to alkaline pH is accurately described by the reactions0.5Ag₂S(s) + 0.5H₂S(aq) = AgHS(aq) K_s,1110.5Ag₂S(s) + 0.5H₂S(aq) + HS⁻ = Ag(HS)2− K_s,122Ag₂S(s) + 2HS⁻ = Ag₂S(HS)22− K_s,232where AgHS(aq) is the dominant species in acidic solutions, Ag(HS)2− under neutral pH conditions and Ag₂S(HS)22− in alkaline solutions. With increasing temperature the stability field of Ag(HS)2− increases and shifts to more alkaline pH in accordance with the change in the first ionisation constant of H₂S(aq). Consequently, Ag₂S(HS)22− is not an important species above 200°C. The solubility constant for the first reaction is independent of temperature to 300°C, with values in the range logK_s,111 = −5.79 (±0.07) to −5.59 (±0.09), and decreases to −5.92 (±0.16) at 400°C. The solubility constant for the second reaction increases almost linearly with inverse temperature from logK_s,122 = −3.97 (±0.04) at 25°C to −1.89 (±0.03) at 400°C. The solubility constant for the third reaction increases with temperature from logK_s,232 = −4.78 (±0.04) at 25°C to −4.57 (±0.18) at 200°C. All solubility constants were found to be independent of pressure within experimental uncertainties. The interaction between Ag⁺ and HS⁻ at 25°C and 1 bar to form AgHS(aq) has appreciable covalent character, as reflected in the exothermic enthalpy and small entropy of formation. With increasing temperature, the stepwise formation reactions become progressively more endothermic and are accompanied by large positive entropies, indicating greater electrostatic interaction. The aqueous speciation of silver is very sensitive to fluid composition and temperature. Below 100°C silver(I) sulphide complexes predominate in reduced sulphide solutions, whereas Ag⁺ and AgClOH⁻ are the dominant species in oxidised waters. In high-temperature hydrothermal solutions of seawater salinity, chloride complexes of silver(I) are most important, whereas in dilute hydrothermal fluids of meteoric origin typically found in active geothermal systems, sulphide complexes predominate. Adiabatic boiling of dilute and saline geothermal waters leads to precipitation of silver sulphide and removal of silver from solution. Conductive cooling has insignificant effects on silver mobility in dilute fluids, whereas it leads to quantitative loss of silver for geothermal fluids of seawater salinity.     

Characteristics of the atmospheric heat source and moisture sink over the Qinghai-Tibetan Plateau during the second TIPEX of summer 1998 and their impact on surrounding monsoon

Summary ?Using the data of 6 automatic heat balance observation (AWS) stations and a data set of 52 surface observation stations over the Qinghai-Tibetan Plateau (“the Plateau”) and surroundings, the horizontal distribution is studied of “apparent atmospheric heat sources” 〈Q ₁〉 and of “apparent atmospheric moisture sinks” 〈Q ₂〉. The AWS stations were established during the period May to August 1998 of the Tibetan Plateau Meteorological Experiment (second TIPEX) by a cooperation of China and Japan. For this period the Plateau mean of 〈Q ₁〉 is positive. Its value of 74 W/m² is a little greater than a climate value and than values from MONEX and the first TIPEX in 1979, respectively. Also the corresponding 〈Q ₂〉 is positive. Hence during that time the Plateau is a heat source and a moisture sink. A day-to-day change of 〈Q ₁〉 and 〈Q ₂〉 is more pronounced over the middle and east part of the Plateau than over the west part. Diagnostics accompanied by numerical simulations are used to study the daily relationship between 〈Q ₁〉 over the Plateau and the weather over China and Asia for this summer. The results suggest that 〈Q ₁〉 may affect precipitation over northern China and position of the west Pacific subtropical high. Abnormal southward retreat of this Pacific high seems to have caused the second flood over the middle and lower Yangtse river basin in July. Received May 20, 2001; revised February 2, 2002     

A coupled model study on ENSO, MJO and Indian summer monsoon rainfall relationships

Summary In this paper, we have tried to understand the ENSO, MJO and Indian summer monsoon rainfall relationships from observation as well as from coupled model results. It was the general feeling that El-Niño years are the deficient in Indian monsoon rainfall and converse being the case for the La-Niña years. Recent papers by several authors noted the failure of this relationship. We find that the model output does confirm a breakdown of this relationship. In this study we have seen that a statistically defined modified Indian summer monsoon rainfall (MISMR) index, a linearly regressed ISMR index and dynamical Webster index (WBSI), shows an inverse relationship with ENSO index during the entire period of integration (1987 to 1999). It is also seen from this study that the amplification of the MJO signals were large and the ENSO signals were less pronounced during the years of above normal ISMR. The MJO signal amplitudes were small and ENSO signals were strong during the years of deficient ISMR. It has been noted that here is a time lag between the MJO and ENSO signal in terms of their modulation aspect. If time lag is added with the ENSO signal then both signals maintain the amplitude modulation theory. A hypothesis is being proposed here to define a relationship between MJO and ENSO signals for the entire period between 1987 and 1999.Received September 18, 2002; revised November 22, 2002; accepted December 20, 2002 Published online: May 8, 2003     

Evolution of the equatorial and dipole modes of the sea-surface temperature in the Tropical Atlantic at decadal scale

Summary ?One hundred and thirty six years (1856–1991) of monthly sea-surface temperature (SST) data in the Tropical Atlantic Ocean are used to investigate the propagating signals of the SST at a decadal (DD) time scale. The first and the third evolving modes show a relationship between the equatorial and the inter-hemispheric patterns, one evolving into the other mode and vice-versa. These modes describe two different evolutions of the SST at DD time-scale. The first EEOF features a 12-year period oscillatory regime with a strong 2-year duration inter-hemispheric pattern evolving into a weak 1-year duration equatorial pattern and vice-versa. This mode exhibits also a northward displacement of the anomalies in the band 15° S–15° N. The third EEOF also shows an oscillatory regime, but with a period of 10 years and with a relatively strong 2-year duration equatorial pattern evolving into a weak 1-year duration inter-hemispheric pattern and vice-versa. For this mode, the SST anomalies show a southward displacement in the band 15° S–15° N. These results have not yet been documented in previous works and explain some of the previous findings on the DD variability in the Tropical Atlantic. Received December 31, 2001; revised April 9, 2002; accepted September 4, 2002 Published online: March 20, 2003     

Turbulence Statistics Inside and Over Forest: Influence on Footprint Prediction

Observations of wind statistics within and above a Scots pine forest are comparedwith those predicted from an analytical second-order closure model. The roughnesssublayer (RSL) effects, and the influence of stability on similarity functions, arestudied using observations. The commonly accepted forms of similarity functionsdescribe the influence of diabatic effects above the RSL well. According to earlierstudies they are expected also to apply within the RSL. As an exception, the averagewind speed normalised with friction velocity was found to be invariant with stabilityclose to the canopy top under unstable conditions. Lagrangian stochastic trajectorysimulations were used to evaluate the influence of canopy turbulence profiles onfootprint prediction. The main uncertainty was found to arise from parameterisationof the random forcing term in the Lagrangian velocity equation. The influence ofdiabatic conditions was studied, and it was found that thermal stability affectssignificantly the footprint function above the forest canopy, but significantuncertainty exists because of uncertainties in the formulation of stability functions.     

Description and evaluation of the bergen climate model: ARPEGE coupled with MICOM

A new coupled atmosphere–ocean–sea ice model has been developed, named the Bergen Climate Model (BCM). It consists of the atmospheric model ARPEGE/IFS, together with a global version of the ocean model MICOM including a dynamic–thermodynamic sea ice model. The coupling between the two models uses the OASIS software package. The new model concept is described, and results from a 300-year control integration is evaluated against observational data. In BCM, both the atmosphere and the ocean components use grids which can be irregular and have non-matching coastlines. Much effort has been put into the development of optimal interpolation schemes between the models, in particular the non-trivial problem of flux conservation in the coastal areas. A flux adjustment technique has been applied to the heat and fresh-water fluxes. There is, however, a weak drift in global mean sea-surface temperature (SST) and sea-surface salinity (SSS) of respectively 0.1 °C and 0.02 psu per century. The model gives a realistic simulation of the radiation balance at the top-of-the-atmosphere, and the net surface fluxes of longwave, shortwave, and turbulent heat fluxes are within observed values. Both global and total zonal means of cloud cover and precipitation are fairly close to observations, and errors are mainly related to the strength and positioning of the Hadley cell. The mean sea-level pressure (SLP) is well simulated, and both the mean state and the interannual standard deviation show realistic features. The SST field is several degrees too cold in the equatorial upwelling area in the Pacific, and about 1 °C too warm along the eastern margins of the oceans, and in the polar regions. The deviation from Levitus salinity is typically 0.1 psu – 0.4 psu, with a tendency for positive anomalies in the Northern Hemisphere, and negative in the Southern Hemisphere. The sea-ice distribution is realistic, but with too thin ice in the Arctic Ocean and too small ice coverage in the Southern Ocean. These model deficiencies have a strong influence on the surface air temperatures in these regions. Horizontal oceanic mass transports are in the lower range of those observed. The strength of the meridional overturning in the Atlantic is 18 Sv. An analysis of the large-scale variability in the model climate reveals realistic El Niño – Southern Oscillation (ENSO) and North Atlantic–Arctic Oscillation (NAO/AO) characteristics in the SLP and surface temperatures, including spatial patterns, frequencies, and strength. While the NAO/AO spectrum is white in SLP and red in temperature, the ENSO spectrum shows an energy maximum near 3 years.     

Cloud type and cloud cover effects on the surface radiative balance at several Polar sites

Summary ?The present work concerns measurements performed at five Polar sites in order to study the influence of cloud type and cloud cover on the surface radiative balance. Cloud cover index was retrieved with the Kasten and Czeplak formula (1980), and comparison with observed values showed the possibility of applying this formula in Polar regions. The Duchon and O’Malley (1999) methodology was adopted to estimate the cloud types present during the measurement period for each site. The results show that during the Antarctic summer clouds have a warming effect on the surface, while during a melting event recorded in the Arctic site clouds have a net cooling effect on the surface. This result allows us to conclude that, during a melting period a different cloud type formation, and a lower surface albedo, modify the effects of clouds on the surface radiation balance. Received April 5, 2002; revised August 1, 2002; accepted August 17, 2002