Microscopic Mechanism and Kinetics of Ice Formation at Complex Interfaces: Zooming in on Kaolinite

Most ice in nature forms because of impurities which boost the exceedingly low nucleation rate of pure supercooled water. However, the microscopic details of ice nucleation on these substances remain largely unknown. Here, we have unraveled the molecular mechanism and the kinetics of ice formation on kaolinite, a clay mineral playing a key role in climate science. We find that the formation of ice at strong supercooling in the presence of this clay is about 20 orders of magnitude faster than homogeneous freezing. The critical nucleus is substantially smaller than that found for homogeneous nucleation and, in contrast to the predictions of classical nucleation theory (CNT), it has a strong two-dimensional character. Nonetheless, we show that CNT describes correctly the formation of ice at this complex interface. Kaolinite also promotes the exclusive nucleation of hexagonal ice, as opposed to homogeneous freezing where a mixture of cubic and hexagonal polytypes is observed.

Formation of Ammonia during the NO-H-2 Reaction over Pt/ZrO2

The mechanism for the formation of NH3 during the NO-H-2 reaction over Pt/ZrO2 was studied. Steady-state isotopic transient kinetic analysis was carried out with isotopic switching from (NO)-N-15-D-2 to (NO)-N-14-D-2, and the results revealed that formation of N-2 and N2O was associated with linearly adsorbed NO on the Pt surface, whereas ammonia formation was associated with NDx species adsorbed on ZrO2. The adsorbed NHx species were not observed on the surface of ZrO2 during NH3 adsorption. From transient kinetic experiments, the formation rates of NHx species and of gaseous NH3 agreed with each other, suggesting that the NHx species on ZrO2 was an ammonia intermediate. The NDx species did not react with D-2 directly, but H-D exchange occurred easily. The addition of H2O to the NO-H-2 feed gas enhanced the formation of NH3. In situ diffuse reflectance spectra and transient kinetic analysis revealed that H2O enhanced the conversion of NHx species to NH3.

The use of short time-on-stream in situ spectroscopic transient kinetic isotope techniques to investigate the mechanism of hydrocarbon selective catalytic reduction (HC-SCR) of NOx at low temperatures

The problem of differentiating between active and spectator species that have similar infrared spectra has been addressed by developing short time-on-stream in situ spectroscopic transient isotope experimental techniques (STOS-SSITKA). The techniques have been used to investigate the reaction mechanism for the reduction of nitrogen oxides (NOx) by hydrocarbons under lean-burn (excess oxygen) conditions on a silver catalyst. Although a nitrate-type species tracks the formation of isotopically labeled dinitrogen, the results show that this is misleading because a nitrate-type species has the same response to an isotopic switch even under conditions where no dinitrogen is produced. In the case of cyanide and isocyanate species, the results show that it is possible to differentiate between slowly reacting spectator isocyanate species, probably adsorbed on the oxide support, and reactive isocyanate species, possibly on or close to the active silver phase. The reactive isocyanate species responds to an isotope switch at a rate that matches that of the rate of formation of the main product, dinitrogen. It is concluded that these reactive isocyanates could potentially be involved in the reduction of NOx whereas there is no evidence to support the involvement of nitrate-type species that are observable by infrared spectroscopy.

Core-collapse supernovae in low-metallicity environments and future all-sky transient surveys

Aims. Massive stars in low-metallicity environments may produce exotic explosions such as long-duration gamma-ray bursts and pair-instability supernovae when they die as core-collapse supernovae (CCSNe). Such events are predicted to be relatively common in the early Universe during the first episodes of star-formation. To understand these distant explosions it is vital to study nearby CCSNe arising in low-metallicity environments to determine if the explosions have different characteristics to those studied locally in high-metallicity galaxies. Many of the nearby supernova searches concentrate their efforts on high star-formation rate galaxies, hence biasing the discoveries to metal rich regimes. Here we determine the feasibility of searching for these CCSNe in metal-poor dwarf galaxies using various survey strategies.

Topoisomerase IIα promotes activation of RNA polymerase I transcription by facilitating pre-initiation complex formation

Type II DNA topoisomerases catalyse DNA double-strand cleavage, passage and re-ligation to effect topological changes. There is considerable interest in elucidating topoisomerase II roles, particularly as these proteins are targets for anti-cancer drugs. Here we uncover a role for topoisomerase IIa in RNA polymerase I-directed ribosomal RNA gene transcription, which drives cell growth and proliferation and is upregulated in cancer cells. Our data suggest that topoisomerase IIa is a component of the initiation-competent RNA polymerase Iß complex and interacts directly with RNA polymerase I-associated transcription factor RRN3, which targets the polymerase to promoter-bound SL1 in pre-initiation complex formation. In cells, activation of rDNA transcription is reduced by inhibition or depletion of topoisomerase II, and this is accompanied by reduced transient double-strand DNA cleavage in the rDNA-promoter region and reduced pre-initiation complex formation. We propose that topoisomerase IIa functions in RNA polymerase I transcription to produce topological changes at the rDNA promoter that facilitate efficient de novo pre-initiation complex formation.

A fast transient kinetic study of the effect of H-2 on the selective catalytic reduction of NOx with octane using isotopically labelled (NO)-N-15

The H-2-assisted hydrocarbon selective catalytic reduction (HC-SCR) of NO, was investigated using fast transient kinetic analysis coupled with isotopically labelled (NO)-N-15. This allowed monitoring of the evolution of products and reactants during switches of H-2 in and out of the SCR reaction mix. The results obtained with a time resolution of less than 1 s showed that the effect on the reaction of the removal or addition of H-2 was essentially instantaneous. This is consistent with the view that H-2 has a direct chemical effect on the reaction mechanism rather than a secondary one through the formation of "active" Ag clusters. The effect of H-2 partial pressure was investigated at 245 degrees C, it was found that increasing partial pressure of H-2 resulted in increasing conversion of NO and octane. It was also found that the addition of H-2 at 245 degrees C had different effects on the product distribution depending on its partial pressure. The change of the nitrogen balance over time during switches in and out of hydrogen showed that significant quantities of N-containing species were stored when hydrogen was introduced to the system. The positive nitrogen balance on removal of H-2 from the gas phase showed that these stored species continued to react after removal of hydrogen to form N-2. (c) 2006 Elsevier Inc. All rights reserved.

Later Pleistocene evolution of the Exe valley: A chronstratigraphic model of terrace formation and its implications for Palaeolithic archaeology

This paper presents the ?rst systematic chronostratigraphic study of the river terraces of the Exe catchment in South West England and a new conceptual model for terrace formation in unglaciated basins with applicability to terrace staircase sequences elsewhere. The Exe catchment lay beyond the maximum extent of Pleistocene ice sheets and the drainage pattern evolved from the Tertiary to the Middle Pleistocene, by which time the major valley systems were in place and downcutting began to create a staircase of strath terraces. The higher terraces (8-6) typically exhibit altitudinal overlap or appear to be draped over the landscape, whilst the middle terraces show greater altitudinal separation and the lowest terraces are of a cut and ?ll form. The terrace deposits investigated in this study were deposited in cold phases of the glacial-interglacial Milankovitch climatic cycles with the lowest four being deposited in the Devensian Marine Isotope Stages (MIS) 4-2. A new cascade process-response model is proposed of basin terrace evolution in the Exe valley, which emphasises the role of lateral erosion in the creation of strath terraces and the reworking of inherited resistant lithological components down through the staircase. The resultant emergent valley topography and the reworking of artefacts along with gravel clasts, have important implications for the dating of hominin presence and the local landscapes they inhabited. Whilst the terrace chronology suggested here is still not as detailed as that for the Thames or the Solent System it does indicate a Middle Palaeolithic hominin presence in the region, probably prior to the late Wolstonian Complex or MIS 6. This supports existing data from cave sites in South West England.

Glycolaldehyde Formation via the Dimerisation of the Formyl Radical

Glycolaldehyde, the simplest monosaccharide sugar, has recently been detected in low- and high-mass star-forming cores. Following our previous investigation into glycolaldehyde formation, we now consider a further mechanism for the formation of glycolaldehyde that involves the dimerization of the formyl radical, HCO. Quantum mechanical investigation of the HCO dimerization process upon an ice surface is predicted to be barrierless and therefore fast. In an astrophysical context, we show that this mechanism can be very efficient in star-forming cores. It is limited by the availability of the formyl radical, but models suggest that only very small amounts of CO are required to be converted to HCO to meet the observational constraints.

Sputtering of oxygen ice by low energy ions

Naturally occurring ices lie on both interstellar dust grains and on celestial objects, such as those in the outer Solar system. These ices are continuously subjected to irradiation by ions from the solar wind and/or cosmic rays, which modify their surfaces. As a result, new molecular species may form which can be sputtered off into space or planetary atmospheres. We determined the experimental values of sputtering yields for irradiation of oxygen ice at 10 K by singly (He+, C+, N+, O+ and Ar+) and doubly (C2 +, N2 + and O2 +) charged ions with 4 keV kinetic energy. In these laboratory experiments, oxygen ice was deposited and irradiated by ions in an ultra high vacuum chamber at low temperature to simulate the environment of space. The number of molecules removed by sputtering was observed by measurement of the ice thickness using laser interferometry. Preliminary mass spectra were taken of sputtered species and of molecules formed in the ice by temperature programmed desorption (TPD). We find that the experimental sputtering yields increase approximately linearly with the projectile ion mass (or momentum squared) for all ions studied. No difference was found between the sputtering yields for singly and doubly charged ions of the same atom within the experimental uncertainty, as expected for a process dominated by momentum transfer. The experimental sputter yields are in good agreement with values calculated using a theoretical model except in the case of oxygen ions. Preliminary studies have shown molecular oxygen as the dominant species sputtered and TPD measurements indicate ozone formation.

The Ultraviolet-Bright, Slowly Declining Transient PS1-11af as a Partial Tidal Disruption Event

We present the Pan-STARRS1 discovery of the long-lived and blue transient PS1-11af, which was also detected by Galaxy Evolution Explorer with coordinated observations in the near-ultraviolet (NUV) band. PS1-11af is associated with the nucleus of an early type galaxy at redshift z = 0.4046 that exhibits no evidence for star formation or active galactic nucleus activity. Four epochs of spectroscopy reveal a pair of transient broad absorption features in the UV on otherwise featureless spectra. Despite the superficial similarity of these features to P-Cygni absorptions of supernovae (SNe), we conclude that PS1-11af is not consistent with the properties of known types of SNe. Blackbody fits to the spectral energy distribution are inconsistent with the cooling, expanding ejecta of a SN, and the velocities of the absorption features are too high to represent material in homologous expansion near a SN photosphere. However, the constant blue colors and slow evolution of the luminosity are similar to previous optically selected tidal disruption events (TDEs). The shape of the optical light curve is consistent with models for TDEs, but the minimum accreted mass necessary to power the observed luminosity is only 0.002 M, which points to a partial disruption model. A full disruption model predicts higher bolometric luminosities, which would require most of the radiation to be emitted in a separate component at high energies where we lack observations. In addition, the observed temperature is lower than that predicted by pure accretion disk models for TDEs and requires reprocessing to a constant, lower temperature. Three deep non-detections in the radio with the Very Large Array over the first two years after the event set strict limits on the production of any relativistic outflow comparable to Swift J1644+57, even if off-axis.

A laboratory study of water ice erosion by low-energy ions

Water ice covers the surface of various objects in the outer Solar system.Within the heliopause, surface ice is constantly bombarded and sputtered by energetic particles from the solar wind and magnetospheres. We report a laboratory investigation of the sputtering yield of water ice when irradiated at 10 K by 4 keV singly (13C+, N+, O+, Ar+) and doubly charged ions (13C2+, N2+, O2+). The experimental values for the sputtering yields are in good agreement with the prediction of a theoretical model. There is no significant difference in the yield for singly and doubly charged ions. Using these yields, we estimate the rate of water ice erosion in the outer Solar system objects due to solar wind sputtering. Temperature-programmed desorption of the ice after irradiation with 13C+ and 13C2+ demonstrated the formation of 13CO and 13CO2, with 13CO being the dominant formed species.