Insights into processes and deposits of hazardous vulcanian explosions at Soufrière Hills Volcano during 2008 and 2009 (Montserrat, West Indies)

During the Soufrière Hills eruption, vulcanian explosions have generally occurred 1) in episodic cycles; 2) isolated during pauses in extrusion, and 3) after major collapses of the dome. In a different eruptive context, significant vulcanian explosions occurred on 29 July 2008, 3 December 2008, and 3 January 2009. Deposits are pumiceous except for the 3 December event. We reconstructed the dispersal pattern of the deposits and their textural characteristics to evaluate erupted volume and vesicularity of the magma at fragmentation. We discuss the implications of these explosions in terms of eruptive processes and chronology, and the hazards posed by their sudden and often unheralded occurrence. We suggest that overpressurization of the conduit can develop over time-scales of months to weeks by a process of self-sealing of conduit walls and/or the cooling dome by silica polymorphs. This work provides new insights for understanding the generation of hazardous vulcanian explosions at andesitic volcanoes.

The importance of anisotropic Coulomb interaction in LaMnO3

In low-temperature anti-ferromagnetic LaMnO3, strong and localized electronic interactions among Mn 3d electrons prevent a satisfactory description from standard local density and generalized gradient approximations in density functional theory calculations. Here we show that the strong on-site electronic interactions are described well only by using direct and exchange corrections to the intra-orbital Coulomb potential. Only DFT+U calculations with explicit exchange corrections produce a balanced picture of electronic, magnetic and structural observables in agreement with experiment. To understand the reason, a rewriting of the functional form of the +U corrections is presented that leads to a more physical and transparent understanding of the effect of these correction terms. The approach highlights the importance of Hund’s coupling (intra-orbital exchange) in providing anisotropy across the occupation and energy eigenvalues of the Mn d states. This intra-orbital exchange is the key to fully activating the Jahn-Teller distortion, reproducing the experimental band gap and stabilizing the correct magnetic ground state in LaMnO3. The best parameter values for LaMnO3 within the DFT(PBEsol)+U framework are determined to be U = 8 eV and J = 1.9 eV.

Accumulation of complex eigenvalues of an indefinite Sturm--Liouville operator with a shifted Coulomb potential

For a particular family of long-range potentials V, we prove that the eigenvalues of the indefinite Sturm–Liouville operator A = sign(x)(−Δ+V(x)) accumulate to zero asymptotically along specific curves in the complex plane. Additionally, we relate the asymptotics of complex eigenvalues to the two-term asymptotics of the eigenvalues of associated self-adjoint operators.

Electronic structure of point defects in controlled self-doping of the TiO2 (110) surface: Combined photoemission spectroscopy and density functional theory study

Point defects in metal oxides such as TiO2 are key to their applications in numerous technologies. The investigation of thermally induced nonstoichiometry in TiO2 is complicated by the difficulties in preparing and determining a desired degree of nonstoichiometry. We study controlled self-doping of TiO2 by adsorption of 1/8 and 1/16 monolayer Ti at the (110) surface using a combination of experimental and computational approaches to unravel the details of the adsorption process and the oxidation state of Ti. Upon adsorption of Ti, x-ray and ultraviolet photoemission spectroscopy (XPS and UPS) show formation of reduced Ti. Comparison of pure density functional theory (DFT) with experiment shows that pure DFT provides an inconsistent description of the electronic structure. To surmount this difficulty, we apply DFT corrected for on-site Coulomb interaction (DFT+U) to describe reduced Ti ions. The optimal value of U is 3 eV, determined from comparison of the computed Ti 3d electronic density of states with the UPS data. DFT+U and UPS show the appearance of a Ti 3d adsorbate-induced state at 1.3 eV above the valence band and 1.0 eV below the conduction band. The computations show that the adsorbed Ti atom is oxidized to Ti2+ and a fivefold coordinated surface Ti atom is reduced to Ti3+, while the remaining electron is distributed among other surface Ti atoms. The UPS data are best fitted with reduced Ti2+ and Ti3+ ions. These results demonstrate that the complexity of doped metal oxides is best understood with a combination of experiment and appropriate computations.

Surface and interstitial Ti diffusion at the rutile TiO2(110) surface

Diffusion of Ti through the TiO2 (110) rutile surface plays a key role in the growth and reactivity of TiO2. To understand the fundamental aspects of this important process, we present an analysis of the diffusion of Ti adspecies at the stoichiometric TiO2(110) surface using complementary computational methodologies of density functional theory corrected for on-site Coulomb interactions (DFT+U) and a charge equilibration (QEq) atomistic potential to identify minimum energy pathways. We find that diffusion of Ti from the surface to subsurface (and vice versa) follows an intersticialcy exchange mechanism, involving exchange of surface Ti with the 6-fold coordinated Ti below the bridging oxygen rows. Diffusion in the subsurface between layers also follows an interstitialcy mechanism. The diffusion of Ti is discussed in light of continued attempts to understand the re-oxidation of non-stoichiometric TiO2(110) surfaces.

Solar induced climate effects

Solar electromagnetic radiation powers Earth’s climate system and, consequently, it is often naively assumed that changes in this solar output must be responsible for changes in Earth’s climate. However, the Sun is close to a blackbody radiator and so emits according to its surface temperature and the huge thermal time constant of the outer part of the Sun limits the variability in surface temperature and hence output. As a result, on all timescales of interest, changes in total power output are limited to small changes in effective surface temperature (associated with magnetic fields) and potential, although as yet undetected, solar radius variations. Larger variations are seen in the UV part of the spectrum which is emitted from the lower solar atmosphere (the chromosphere) and which influences Earth’s stratosphere. There is interest in“top-down” mechanisms whereby solar UV irradiance modulates stratospheric temperatures and winds which, in turn, may influence the underlying troposphere where Earth’s climate and weather reside. This contrasts with “bottom-up” effects in which the small total solar irradiance (dominated by the visible and near-IR) variations cause surface temperature changes which drive atmospheric circulations. In addition to these electromagnetic outputs, the Sun modulates energetic particle fluxes incident on the Earth. Solar Energetic Particles (SEP) are emitted by solar flares and from the shock fronts ahead of supersonic (and super-Alfvenic) ejections of material from the solar atmosphere. These SEPs enhance the destruction of polar stratospheric ozone which could be an additional form of top-down climate forcing. Even more energetic are Galactic Cosmic Rays (GCRs). These particles are not generated by the Sun, rather they originate at the shock fronts emanating from violent galactic events such as supernovae explosions; however, the expansion of the solar magnetic field into interplanetary space means that the Sun modulates the number of GCRs reaching Earth. These play a key role in enabling Earth’s global electric (thunderstorm) circuit and it has been proposed that they also modulate the formation of clouds. Both electromagnetic and corpuscular solar effects are known to vary over the solar magnetic cycle which is typically between 10 and 14 yrs in length (with an average close to 11 yrs). The solar magnetic field polarity at any one phase of one of these activity cycles is opposite to that at the same phase of the next cycle and this influences some phenomena, for example GCRs, which therefore show a 22 yr (“Hale”) cycle on average. Other phenomena, such as irradiance modulation, do not depend on the polarity of the magnetic field and so show only the basic 11-yr activity cycle. However, any effects on climate are much more significant for solar drifts over centennial timescales. This chapter discusses and evaluates potential effects on Earth’s climate system of variations in these solar inputs. Because of the great variety of proposed mechanisms, the wide range of timescales studied (from days to millennia) and the many debates (often triggered by the application of inadequate statistical methods), the literature on this subject is vast, complex, divergent and rapidly changing: consequently the number of references cited in this review is very large (yet still only a small fraction of the total).

A simple analysis of thermodynamic properties for classical plasmas: I. theory

By eliminating the short range negative divergence of the Debye–Hückel pair distribution function, but retaining the exponential charge screening known to operate at large interparticle separation, the thermodynamic properties of one-component plasmas of point ions or charged hard spheres can be well represented even in the strong coupling regime. Predicted electrostatic free energies agree within 5% of simulation data for typical Coulomb interactions up to a factor of 10 times the average kinetic energy. Here, this idea is extended to the general case of a uniform ionic mixture, comprising an arbitrary number of components, embedded in a rigid neutralizing background. The new theory is implemented in two ways: (i) by an unambiguous iterative algorithm that requires numerical methods and breaks the symmetry of cross correlation functions; and (ii) by invoking generalized matrix inverses that maintain symmetry and yield completely analytic solutions, but which are not uniquely determined. The extreme computational simplicity of the theory is attractive when considering applications to complex inhomogeneous fluids of charged particles.

Cyclic extrusion of a lava dome based on a stick-slip mechanism

Lava dome eruptions are sometimes characterised by large periodic fluctuations in extrusion rate over periods of hours that may be accompanied by Vulcanian explosions and pyroclastic flows. We consider a simple system of nonlinear equations describing a 1D flow of lava extrusion through a deep elastic dyke feeding a shallower cylindrical conduit in order to simulate this short-period cyclicity. Stick-slip conditions depending on a critical shear stress are assumed at the wall boundary of the cylindrical conduit. By analogy with the behaviour of industrial polymers in a plastic extruder, the elastic dyke acts like a barrel and the shallower cylindrical portion of the conduit as a die for the flow of magma acting as a polymer. When we applied the model to the Soufrière Hills Volcano, Montserrat, for which the key parameters have been evaluated from previous studies, cyclic extrusions with periods from 3 to 30 h were readily simulated, matching observations. The model also reproduces the reduced period of cycles observed when a major unloading event occurs due to lava dome collapse.

Pulsatory andesite lava flow at Bagana Volcano

Using a time series of TerraSAR-X spaceborne radar images we have measured the pulsatory motion of an andesite lava flow over a 14-month period at Bagana volcano, Papua New Guinea. Between October 2010 and December 2011, lava flowed continuously down the western flank of the volcano forming a 3 km-long blocky lava flow with a channel, levees, overflows and branches. We captured four successive pulses of lava advancing down the channel system, the first such behaviour of an andesite flow to be recorded using radar. Each pulse had a volume of the order of 107 m3 emplaced over many weeks. The average extrusion rate estimated from the radar data was 0.92 ± 0.35 m3 s-1 , and varied between 0.3 and 1.8 m3 s-1, with higher rates occurring earlier in each pulse. This, together with observations of sulphur dioxide emissions, explosions and incandescence suggest a variable supply rate of magma through Bagana’s conduit as the most likely source of the pulsatory behaviour.

Complex formation in solutions of oppositely charged polyelectrolytes at different polyion compositions and salt content

The formation of complexes in solutions containing positively charged polyions (polycations) and a variable amount of negatively charged polyions (polyanions) has been investigated by Monte Carlo simulations. The polyions were described as flexible chains of charged hard spheres interacting through a screened Coulomb potential. The systems were analyzed in terms of cluster compositions, structure factors, and radial distribution functions. At 50% charge equivalence or less, complexes involving two polycations and one polyanion were frequent, while closer to charge equivalence, larger clusters were formed. Small and neutral complexes dominated the solution at charge equivalence in a monodisperse system, while larger clusters again dominated the solution when the polyions were made polydisperse. The cluster composition and solution structure were also examined as functions of added salt by varying the electrostatic screening length. The observed formation of clusters could be rationalized by a few simple rules.

A Monte Carlo study of solutions of oppositely charged polyelectrolytes

The formation of complexes appearing in solutions containing oppositely charged polyelectrolytes has been investigated by Monte Carlo simulations using two different models. The polyions are described as flexible chains of 20 connected charged hard spheres immersed in a homogenous dielectric background representing water. The small ions are either explicitly included or their effect described by using a screened Coulomb potential. The simulated solutions contained 10 positively charged polyions with 0, 2, or 5 negatively charged polyions and the respective counterions. Two different linear charge densities were considered, and structure factors, radial distribution functions, and polyion extensions were determined. A redistribution of positively charged polyions involving strong complexes formed between the oppositely charged polyions appeared as the number of negatively charged polyions was increased. The nature of the complexes was found to depend on the linear charge density of the chains. The simplified model involving the screened Coulomb potential gave qualitatively similar results as the model with explicit small ions. Finally, owing to the complex formation, the sampling in configurational space is nontrivial, and the efficiency of different trial moves was examined.

Sensitivity of OMI SO2 measurements to variable eruptive behaviour at Soufrière Hills Volcano, Montserrat

Since 2004, the satellite-borne Ozone Mapping Instrument (OMI) has observed sulphur dioxide (SO2) plumes during both quiescence and effusive eruptive activity at Soufrière Hills Volcano, Montserrat. On average, OMI detected a SO2 plume 4-6 times more frequently during effusive periods than during quiescence in the 2008-2010 period. The increased ability of OMI to detect SO2 during eruptive periods is mainly due to an increase in plume altitude rather than a higher SO2 emission rate. Three styles of eruptive activity cause thermal lofting of gases (Vulcanian explosions; pyroclastic flows; a hot lava dome) and the resultant plume altitudes are estimated from observations and models. Most lofting plumes from Soufrière Hills are derived from hot domes and pyroclastic flows. Although Vulcanian explosions produced the largest plumes, some produced only negligible SO2 signals detected by OMI. OMI is most valuable for monitoring purposes at this volcano during periods of lava dome growth and during explosive activity.