XPS spectra of uranyl minerals and synthetic uranyl compounds. II: The O 1s spectrum

The O 1s spectrum is examined for 19 uranyl minerals of different composition and structure. Spectra from single crystals were measured with a Kratos Axis Ultra X-ray Photoelectron Spectrometer with a magnetic-confinement charge-compensation system. Well-resolved spectra with distinct maxima, shoulders and inflections points, in combination with reported and measured binding energies for specific O²⁻ species and structural data of the uranyl minerals are used to resolve the fine structure of the O 1s envelope. The resolution of the O 1s spectra includes, for the first time, different O²⁻ bands, which are assigned to O atoms linking uranyl with uranyl polyhedra (UOU) and O atoms of uranyl groups (OUO). The resolved bands in the O 1s spectrum occur at distinct ranges in binding energy: bands for (UOU) occur at 529.6-530.4 eV, bands for (OUO) occur at 530.6-531.4 eV, bands for O²⁻ in the equatorial plane of the uranyl polyhedra linking uranyl polyhedra with (TO_n) groups (T = Si, S, C, P, Se) (TO) occur at 530.9-532.2 eV; bands for (OH) groups in the equatorial plane of the uranyl polyhedra (OH) occur at 532.0-532.5 eV, bands of (H₂O) groups in the interstitial complex of the uranyl minerals (H₂O_interst) occur at 533.0-533.8 eV and bands of physisorbed (H₂O) groups on the surface of uranyl minerals (H₂O_adsorb) occur at 534.8-535.2 eV. Treatment of uranyl minerals with acidic solutions results in a decrease in UOU and an increase in OH. Differences in the ratio of OH : OUO between the surface and bulk structure is larger for uranyl minerals with a high number of UOU and TO species in the bulk structure which is explained by protonation of underbonded UO, UOU and TO terminations on the surface. The difference in the ratio of H₂O_interst : OUO between the bulk and surface structures is larger for uranyl minerals with higher percentages of H₂O_interst as well as, with a higher number of interstitial H₂O groups that are not bonded to interstitial cations, resulting in easier dehydration of interstitial H₂O groups in uranyl minerals during exposure to a vacuum.     

A new hammer-driven freeze corer

A shortcoming of freeze corers has been the inability to collect long cores in stiff sediments. We describe a hammerdriven freeze corer that collects undisturbed sediment cores up to 1.3 m in length in stiff or soft lake sediments. The corer was tested in prairie, montane and alpine lakes of western Canada. For these stiff sediments, conventional (gravity-only) freeze coring methods collected cores ranging from 25–59 cm compared with 100–124 cm for our hammer-driven device. The maximum length of cores could exceed 1.3 m if a longer core barrel was constructed.     

Cation adsorption on oxides and clays: The aluminum case

The sorption mechanisms for trace metal ions on montmorillonite have been investigated. Complexation with surface hydroxyl groups located on the brocken edges of platelet particles is found to occur over a pH range similar to that observed on silica and other oxides, at comparable metal/site ratios. A second mechanism involving cation exchange on the negatively charge basal plane, which does not involve proton exchange in our experimental conditions, has been invoked to explain the low pH behavior. Consistent with this cation exchange mechanism, adsorption at low pH is strongly ionic strength dependant. A quantitative model which involves both mechanisms is presented and tested against both cation and proton adsorption data.     

A New Delhi every day: multiplicities of governance regimes in a transforming metropolis

In this article I demonstrate the coexistence of multiple urban governance regimes in Delhi, India. While formal urban governance is geared toward transforming Delhi into a “world-class” city, I present original research that shows how the everyday governance of urban space in three very different areas of Delhi is determined by relations among non-state actors. These regimes foster access to space for street hawkers on an everyday basis while they allow powerful local interest groups to collect rent and influence flows of people and commodities. I argue that, in contrast to formal electoral politics, these governance regimes emerge from a parallel politics of everyday interactions, negotiations, and transgressions. Although the emancipatory potential of these regimes should not be overstated, they do offer street hawkers limited contingency to improve their access to urban space. This article contributes to a growing body of work on urban governance by showing how multiplicities of governance regimes coexist and determine how and by whom urban space is used in a metropolis in the global South.     

Collisionless tearing modes in the presence of shear flow

Tearing modes in a plane collisionless current sheet with shear bulk flow are studied. An analytic expression for the growth rate is obtained for the case \(M^2 = (1 - \varepsilon {\text{ sech}}^m \bar z)\) , whereM is the Mach number,m the shear flow index, ε a positive constant less than unity, and \(\bar z\) the (normalized) co-ordinate normal to the current sheet. The growth rates are large and the unstable wave number domain is increased as compared to the case without flow. The relevance of these results to time-dependent reconnection processes in the Earth's magnetosphere is discussed.     

Helmet Streamers with Triple Structures: Weakly Two-Dimensional Stationary States

Recent observations of the solar corona with the LASCO coronagraph on board the SOHO spacecraft have revealed the occurrence of triple helmet streamers even during solar minimum, which occasionally go unstable and give rise to particularly huge coronal mass ejections. We present a method to calculate (semi-)analytically self-consistent stationary configurations of triple helmet streamers which can serve as input for stability considerations and dynamical calculations. The method is based on an asymptotic expansion procedure using the elongated structure of the streamers. The method is very flexible and can be used in both Cartesian and spherical geometry. We discuss the effects of magnetic shear, gravity and field-aligned flow on open field lines. Example solutions illustrating the influence of each of these features on the solution structure are presented.     

On the Stability of the <Emphasis Type="Italic">AlOSi</Emphasis>(<Emphasis Type="Italic">OH</Emphasis>)<Stack><Subscript>3</Subscript><Superscript>2+</Superscript></Stack> Complex in Aqueous Solution

Summary The complexation of aluminium(III) and silicon(IV) was studied in a simplified seawater medium (0.6 M Na(Cl)) at 25 °C. The measurements were performed as potentiometric titrations using a hydrogen electrode with OH ⁻ ions being generated coulometrically. The total concentrations of Si(IV) and Al(III) respectively [Si _tot ] and [Al _t ot], and −log[H ⁺] were varied within the limits 0.3 < [Si _tot ] < 2.5 mM, 0.5 < [Al _tot ] < 2.6 mM, and 2 ≤ -log[H ⁺] ≤ 4.2. Within these ranges of concentration, evidence is given for the formation of an AlSiO(OH) ₃ ²⁺ complex with a formation constant log β_1,1-1 = −2.75 ± 0.1 defined by the reaction Al ³⁺+Si (OH)₄ ↔ AlOSi(OH) ₃ ²⁺ +H ⁺ An extrapolation of this value to I=0 gives log β_1,1-1 = −2.30. The calculated value of log K (Al ³⁺+SiO(OH) ₃ ⁻ ↔ AlOSi(OH) ₃ ²⁺ ) = 6.72 (I=0.6 M) can be compared with corresponding constants for the formation of AlF ²⁺ and AlOH ²⁺ , which are equal to 6.16 and 8.20. Obviously, the stability of these Al(III) complexes decreases within the series OH ⁻>SiO(OH) ₃ ⁻  > F ⁻