Speciation and thermodynamic properties for cobalt chloride complexes in hydrothermal fluids at 35-440 °C and 600 bar: An in-situ XAS study

Aqueous Co(II) chloride complexes play a crucial role in cobalt transport and deposition in ore-forming hydrothermal systems, ore processing plants, and in the corrosion of special Co-bearing alloys. Reactive transport modelling of cobalt in hydrothermal fluids relies on the availability of thermodynamic properties for Co complexes over a wide range of temperature, pressure and salinity. Synchrotron X-ray absorption spectroscopy was used to determine the speciation of cobalt(II) in 0-6 m chloride solutions at temperatures between 35 and 440 °C at a constant pressure of 600 bar. Qualitative analysis of XANES spectra shows that octahedral species predominate in solution at 35 °C, while tetrahedral species become increasingly important with increasing temperature. Ab initio XANES calculations and EXAFS analyses suggest that in high temperature solutions the main species at high salinity (Cl:Co >> 2) is CoCl₄²⁻, while a lower order tetrahedral complex, most likely CoCl₂(H₂O)_2(aq), predominates at low salinity (Cl:Co ratios ∼2). EXAFS analyses further revealed the bonding distances for the octahedral Co(H₂O)₆²⁺ (^octCo-O = 2.075(19) Å), tetrahedral CoCl₄²⁻ (^tetCo-Cl = 2.252(19) Å) and tetrahedral CoCl₂(H₂O)_2(aq) (^tetCo-O = 2.038(54) Å and ^tetCo-Cl = 2.210(56) Å). An analysis of the Co(II) speciation in sodium bromide solutions shows a similar trend, with tetrahedral bromide complexes becoming predominant at higher temperature/salinity than in the chloride system. EXAFS analysis confirms that the limiting complex at high bromide concentration at high temperature is CoBr₄²⁻. Finally, XANES spectra were used to derive the thermodynamic properties for the CoCl₄²⁻ and CoCl₂(H₂O)_2(aq) complexes, enabling thermodynamic modelling of cobalt transport in hydrothermal fluids. Solubility calculations show that tetrahedral CoCl₄²⁻ is responsible for transport of cobalt in hydrothermal solutions with moderate chloride concentration (∼2 m NaCl) at temperatures of 250 °C and higher, and both cooling and dilution processes can cause deposition of cobalt from hydrothermal fluids.     

Climatic dependence of stable carbon and oxygen isotope signals recorded in speleothems: From soil water to speleothem calcite

Understanding the relationship between stable isotope signals recorded in speleothems (δ¹³C and δ¹⁸O) and the isotopic composition of the carbonate species in the soil water is of great importance for their interpretation in terms of past climate variability. Here the evolution of the carbon isotope composition of soil water on its way down to the cave during dissolution of limestone is studied for both closed and open-closed conditions with respect to CO₂.The water entering the cave flows as a thin film towards the drip site. CO₂ degasses from this film within approx. 10 s by molecular diffusion. Subsequently, chemical and isotopic equilibrium is established on a time scale of several 10-100 s. The δ¹³C value of the drip water is mainly determined by the isotopic composition of soil CO₂. The evolution of the δ¹⁸O value of the carbonate species is determined by the long exchange time T_ex, between oxygen in carbonate and water of several 10,000 s. Even if the oxygen of the CO₂ in soil water is in isotopic equilibrium with that of the water, dissolution of limestone delivers oxygen with a different isotopic composition changing the δ¹⁸O value of the carbonate species. Consequently, the δ¹⁸O value of the rainwater will only be reflected in the drip water if it has stayed in the rock for a sufficiently long time.After the water has entered the cave, the carbon and oxygen isotope composition of the drip water may be altered by CO₂-exchange with the cave air. Exchange times, , of about 3000 s are derived. Thus, only drip water, which drips in less than 3000 s onto the stalagmite surface, is suitable to imprint climatic signals into speleothem calcite deposited from it.Precipitation of calcite proceeds with time constants, τ_p, of several 100 s. Different rate constants and equilibrium concentrations for the heavy and light isotopes, respectively, result in isotope fractionation during calcite precipitation. Since T_ex ? τ_p, exchange with the oxygen in the water can be neglected, and the isotopic evolution of carbon and oxygen proceed analogously. For drip intervals T_d < 0.1τ_p the isotopic compositions of both carbon and oxygen in the solution evolve linearly in time. The calcite precipitated at the apex of the stalagmite reflects the isotopic signal of the drip water.For long drip intervals, when calcite is deposited from a stagnant water film, long drip intervals may have a significant effect on the isotopic composition of the DIC. In this case, the isotopic composition of the calcite deposited at the apex must be determined by averaging over the drip interval. Such processes must be considered when speleothems are used as proxies of past climate variability.     

Modeling and quality control for reliable precise point positioning integer ambiguity resolution with GNSS modernization

Recent research has demonstrated that the undifferenced integer ambiguities can be recovered using products from a network solution. The standard dual-frequency PPP integer ambiguity resolution consists of two aspects: Hatch-Melbourne-Wübbena wide-lane (WL) and ionosphere-free narrow-lane (NL) integer ambiguity resolution. A major issue affecting the performance of dual-frequency PPP applications is the time it takes to fix these two types of integer ambiguities, especially if the WL integer ambiguity resolution suffers from the noisy pseudorange measurements and strong multipath effects. With modernized Global Navigation Satellite Systems, triple-frequency measurements will be available to global users and an extra WL (EWL) model with very long wavelength can be formulated. Then, the easily resolved EWL integer ambiguities can be used to construct linear combinations to accelerate the PPP WL integer ambiguity resolution. Therefore, we propose a new reliable procedure for the modeling and quality control of triple-frequency PPP WL and NL integer ambiguity resolution. First, we analyze a WL integer ambiguity resolution model based on triple-frequency measurements. Then, an optimal pseudorange linear combination which is ionosphere-free and has minimum measurement noise is developed and used as constraint in the WL and the NL integer ambiguity resolution. Based on simulations, we have investigated the inefficiency of dual-frequency WL integer ambiguity resolution and the performance of EWL integer ambiguity resolution. Using almanacs of GPS, Galileo and BeiDou, the performances of the proposed triple-frequency WL and NL models have been evaluated in terms of success rate. Comparing with dual-frequency PPP, numerical results indicate that the proposed triple-frequency models can outperform the dual-frequency PPP WL and NL integer ambiguity resolution. With 1 s sampling rate, generally, only several minutes of data are required for reliable triple-frequency PPP WL and NL integer ambiguity resolution. Under benign observation situations and good geometries, the integer ambiguity can be reliably resolved even within 10 s.     

Discrete fracture model for simulating waterflooding processes under fracturing conditions

In our study, we develop a model for simulating fracturing processes in a poroelastic medium. The proposed approach combines the discrete fracture model enriched with contact plane mechanics. The model captures mechanical interactions of fractures and a deformable medium, fluid, and heat transfer in fractures and in a porous medium. Both effects of poroelasticity and thermoelasticity are accounted in our model. Mass and heat conservation equations are approximated by the finite volume method, and mechanical equilibrium equations are discretized by means of the Galerkin finite element approach. Two‐dimensional grid facets between 3‐dimensional finite elements are considered as possible fracture surfaces. Most of these facets are inactive from the beginning and are activated throughout the simulation. A fracture propagation criterion, based on Irwin's approach, is verified on each nonlinear iteration. When the criterion is satisfied, additional contact elements are added into finite element and discrete fracture model formulations respectively. The proposed approach allows modeling of existing natural and artificially created fractures within one framework. The model is tested on single‐ and multiple‐phase fluid flow examples for both isothermal and thermal conditions and verified against existing semianalytical solutions. The applicability of the approach is demonstrated on an example of practical interests where a sector model of an oil reservoir is simulated with different injection and production regimes.     

High spatial resolution mapping of surface velocities and depths for shallow overland flow

Point measurements of flow rate, depth or velocity are not sufficient to validate overland flow models, particularly when the interaction of the water with the soil surface creates a complex flow geometry. In this study, we present the coupling of two techniques obtaining spatial data of flow depths and surface velocity measurements for water depths as low as 1 mm. Overland flow experiments were performed in the laboratory at various flow rates and slopes on two surfaces. The first surface was 120 cm by 120 cm showing three undulations of sinusoidal shape with an amplitude of 1 cm and a wavelength of 20 cm, while the second was a 60 cm by 60 cm moulded reproduction of a seedbed with aggregates up to 2 cm in size. Large scale particle image velocimetry (LSPIV) was used for velocity measurements with a sub‐centimetre spatial resolution. An instantaneous‐profile laser scanner was used to map flow depths with a sub‐millimetre spatial resolution. A sensitivity analysis of the image processing of the LSPIV showed good robustness of the method. Comparison with measurements performed with hot film anemometer and salt velocity gauge showed that LSPIV surface velocities were representative of the flow. Water depths measured with the laser scanner were also in good agreement with single‐point measurements performed with a dial indicator. Spatially‐distributed flow rates could be computed by combining both presented techniques with a mean relative error less than 20%. Copyright © 2012 John Wiley & Sons, Ltd.     

A comparison of approaches to include outcrop information in overburden thickness estimation

The estimation of overburden sediment thickness is important in hydrogeology, geotechnics and geophysics. Usually, thickness is known precisely at a few sparse borehole data. To improve precision of estimation, one useful complementary information is the known position of outcrops. One intuitive approach is to code the outcrops as zero thickness data. A problem with this approach is that the outcrops are preferentially observed compared to other thickness information. This introduces a strong bias in the thickness estimation that kriging is not able to remove. We consider a new approach to incorporate point or surface outcrop information based on the use of a non-stationary covariance model in kriging. The non-stationary model is defined so as to restrict the distance of influence of the outcrops. Within this distance of influence, covariance parameters are assumed simple regular functions of the distance to the nearest outcrop. Outside the distance of influence of the outcrops, the thickness covariance is assumed stationary. The distance of influence is obtained thru a cross-validation. Compared to kriging based on a stationary model with or without zero thickness at outcrop locations, the non-stationary model provides more precise estimation, especially at points close to an outcrop. Moreover, the thickness map obtained with the non-stationary covariance model is more realistic since it forces the estimates to zero close to outcrops without the bias incurred when outcrops are simply treated as zero thickness in a stationary model.     

Tropical cyclones in the SW Indian Ocean. Part 1: inter-annual variability and statistical prediction

The southwestern Indian Ocean (SWIO) is characterized by significant climate variability and frequent tropical cyclones (TC). Year-to-year fluctuations of TC and associated oceanic and atmospheric fields in the period 1961–2002 are studied with reanalysis data as composites and cross-correlations, with wavelet filtering and cross-modulus analysis, and by hovmoller analysis and multi-variate statistical modeling. Observational limitations in the early part of the record are recognized. An intense TC-days index is formed and is characterized by quasi-biennial to decadal cycles that relate to ocean Rossby waves and high latitude atmospheric circulations, respectively. New variables are uncovered that significantly improve the seasonal prediction of SWIO TC. One predictor is the geopotential height in the SE Pacific, which explains 31% of SWIO TC variability. It foretells of downstream oscillations in the sub-tropical jet stream, which govern wind shear, an equatorial duct and attendant circulation anomalies over the SWIO. An anti-phase association between Amazon convection and intense TCs is found to be related to the Atlantic Zonal Circulation. Drought across the Amazon is related to an increase in TC activity in the SWIO, when zonal wind anomalies over the Atlantic become upper easterly/lower westerly. This feature is related to Pacific Ocean El Niño Southern Oscillation phase. A La Niña signal favors TC development through a westward propagating cyclonic circulation and downweling Rossby wave in the South Indian Ocean that enhances thermodynamic energy. It is recommended to repeat this analysis every few years to determine whether teleconnections evolve due to climate drift or improving observations.     

Three-dimensional carbon dioxide-induced strain distribution within a confined bituminous coal

Sequestration of carbon dioxide in unmineable coal seams is an option to reduce carbon dioxide emissions. It is well known that the interaction of carbon dioxide with unconfined coal induces swelling. This paper contributes three-dimensional strain distribution in confined coal at microstructural level using high-resolution X-ray computerized tomography data and image analysis. Swelling and compression/compaction of regions in the coal matrix occurs with CO₂ uptake. Normal strain varies between ? 1.15% and 0.93%, ? 3.11% and 0.94%, ? 0.43% and 0.30% along x, y and z axes respectively. Volumetric strain varies between ? 4.25% and 1.25%. The positive strains reported are consistent with typical range for unconstrained swelling. However, the average volumetric strains value (? 0.34%) reflect overall volume reduction. Overall swelling is apparently influenced by the confining stresses. The magnitudes of normal strains are heterogeneous and anisotropic. The swelling vs. compression/compaction observed after CO₂ uptake is localized and likely lithotype dependant.     

Global Oscillations at Low Frequency from the SOHO mission (GOLF)

The GOLF experiment on the SOHO mission aims to study the internal structure of the sun by measuring the spectrum of global oscillations in the frequency range 10^–7 to 10^–2 Hz. Bothp andg mode oscillations will be investigated, with the emphasis on the low order long period waves which penetrate the solar core. The instrument employs an extension to space of the proven ground-based technique for measuring the mean line-of-sight velocity of the viewed solar surface. By avoiding the atmospheric disturbances experienced from the ground, and choosing a non-eclipsing orbit, GOLF aims to improve the instrumental sensitivity limit by an order of magnitude to 1 mm s^–1 over 20 days for frequencies higher than 2.10^–4 Hz. A sodium vapour resonance cell is used in a longitudinal magnetic field to sample the two wings of the solar absorption line. The addition of a small modulating field component enables the slope of the wings to be measured. This provides not only an internal calibration of the instrument sensitivity, but also offers a further possibility to recognise, and correct for, the solar background signal produced by the effects of solar magnetically active regions. The use of an additional rotating polariser enables measurement of the mean solar line-of-sight magnetic field, as a secondary objective.