On thin ice: surface order and disorder during pre-melting

The effect of temperature on the structure of the ice Ih (0001) surface is considered through a series of molecular dynamics simulations on an ice slab. At relatively low temperatures (200K) a small fraction of surface self-interstitials (i.e. admolecules) appear that are formed exclusively from molecules leaving the outermost bilayer. At higher temperatures (ca. 250 K), vacancies start to appear in the inner part of the outermost bilayer exposing the underlying bilayer and providing sites with a high concentration of the dangling hydrogen bonds. Around 250-260 K aggregates of molecules formed on top of the outermost bilayer from self-interstitials become more mobile and have diffusivities approaching that of liquid water. At similar to 270-280 K the inner bilayer of one surface noticeably destructures and it appears that at above 285 K both surfaces are melting. The observed disparity in the onset of melting between the two sides of the slab is rationalised by considering the relationship between surface energy and the spatial distribution of protons at the surface; thermodynamic stability is conferred on the surface by maximising separations between dangling protons at the crystal exterior. Local hotspots associated with a high dangling proton density are suggested to be susceptible to pre-melting and may be more efficient at trapping species at the external surface than regions with low concentrations of protons thus potentially helping ice particles to catalyse reactions. A preliminary conclusion of this work is that only about 10-20 K below the melting temperature of the particular water potential employed is major disruption of the crystalline lattice noted which could be interpreted as being "liquid", the thickness of this film being about a nanometre.

Surface Energy and Surface Proton Order of Ice Ih

Ice Ih is comprised of orientationally disordered water molecules giving rise to positional disorder of the hydrogen atoms in the hydrogen bonded network of the lattice. Here we arrive at a first principles determination of the surface energy of ice Ih and suggest that the surface of ice is significantly more proton ordered than the bulk. We predict that the proton order-disorder transition, which occurs in the bulk at similar to 72 K, will not occur at the surface at any temperature below surface melting. An order parameter which defines the surface energy of ice Ih surfaces is also identified.

Proton ordering energetics in ice phases

Results from first-principles calculations on the subtle energetics of proton ordering in ice phases are shown only to depend on the electrostatic components of the total energy. Proton ordered ice phases can therefore be predicted using electronic structure methods or a tailored potential model. However, analysis of the electron density reveals that high order multipole components, up to hexadecapole, are needed to adequately capture total energy differences between proton ordered and disordered phases. This suggests that current potential models may be unable to reproduce the position of proton ordered ice phases in the phase diagram without extensions to describe high order electrostatics. (c) 2006 Elsevier B.V. All rights reserved.

Lorentz TEM investigation of the switching behavior in artificial spin ice building blocks

Frustration – the inability to simultaneously satisfy all interactions – occurs in a wide range of systems including neural networks, water ice and magnetic systems. An example of the latter is the so called spin-ice in pyrochlore materials [1] which have attracted a lot of interest not least due to the emergence of magnetic monopole defects when the ‘ice rules’ governing the local ordering breaks down [2]. However it is not possible to directly measure the frustrated property – the direction of the magnetic moments – in such spin ice systems with current experimental techniques. This problem can be solved by instead studying artificial spin-ice systems where the molecular magnetic moments are replaced by nanoscale ferromagnetic islands [3-8]. Two different arrangements of the ferromagnetic islands have been shown to exhibit spin ice behaviour: a square lattice maintaining four moments at each vertex [3,8] and the Kagome lattice which has only three moments per vertex but equivalent interactions between them [4-7]. Magnetic monopole defects have been observed in both types of lattices [7-8]. One of the challenges when studying these artificial spin-ice systems is that it is difficult to arrive at the fully demagnetised ground-state [6-8].
Here we present a study of the switching behaviour of building blocks of the Kagome lattice influenced by the termination of the lattice. Ferromagnetic islands of nominal size 1000 nm by 100 nm were fabricated in five island blocks using electron-beam lithography and lift-off techniques of evaporated 18 nm Permalloy (Ni80Fe20) films. Each block consists of a central island with four arms terminated by a different number and placement of ‘injection pads’, see Figure 1. The islands are single domain and magnetised along their long axis. The structures were grown on a 50 nm thick electron transparent silicon nitride membrane to allow TEM observation, which was back-coated with a 5 nm film of Au to prevent charge build-up during the TEM experiments.
To study the switching behaviour the sample was subjected to a magnetic field strong enough to magnetise all the blocks in one direction, see Figure 1. Each block obeys the Kagome lattice ‘ice-rules’ of “2-in, 1-out” or “1-in, 2-out” in this fully magnetised state. Fresnel mode Lorentz TEM images of the sample were then recorded as a magnetic field of increasing magnitude was applied in the opposite direction. While the Fresnel mode is normally used to image magnetic domain structures [9] for these types of samples it is possible to deduce the direction of the magnetisation from the Lorentz contrast [5]. All images were recorded at the same over-focus judged to give good Lorentz contrast.
The magnetisation was found to switch at different magnitudes of the applied field for nominally identical blocks. However, trends could still be identified: all the blocks with any injection pads, regardless of placement and number, switched the direction of the magnetisation of their central island at significantly smaller magnitudes of the applied magnetic field than the blocks without injection pads. It can therefore be concluded that the addition of an injection pad lowers the energy barrier to switching the connected island, acting as a nucleation site for monopole defects. In these five island blocks the defects immediately propagate through to the other side, but in a larger lattice the monopoles could potentially become trapped at a vertex and observed [10].
References

[1] M J Harris et al, Phys Rev Lett 79 (1997) p.2554.
[2] C Castelnovo, R Moessner and S L Sondhi, Nature 451 (2008) p. 42.
[3] R F Wang et al, Nature 439 (2006) 303.
[4] M Tanaka et al, Phys Rev B 73 (2006) 052411.
[5] Y Qi, T Brintlinger and J Cumings, Phys Rev B 77 (2008) 094418.
[6] E Mengotti et al, Phys Rev B 78 (2008) 144402.
[7] S Ladak et al, Nature Phys 6 (2010) 359.
[8] C Phatak et al, Phys Rev B 83 (2011) 174431.
[9] J N Chapman, J Phys D 17 (1984) 623.
[10] The authors gratefully acknowledge funding from the EPSRC under grant number EP/D063329/1.

Coleoptera and microbe biomass in Antarctic Dry Valley paleosols adjacent to the Inland Ice: Implications for Mars

Bulk paleosol samples collected from a Middle to Early Miocene moraine in the New Mountain area of the Dry Valleys, Antarctica, yielded Coleoptera exoskeletons and occasional endoskeletons showing considerable diagenetic effects along with several species of bacteria, all lodged in a dry-frozen but salt-rich horizon at shallow depth to the land surface. The till is at the older end of a chronologic sequence of glacial deposits, thought to have been deposited before the transition from wet-based to cold-based ice (similar to 15 Ma), and hence, entirely weathered in contact with the subaerial atmosphere. It is possible, though not absolutely verifiable, that the skeletons date from this early stage of emplacement having undergone modifications whenever light snowmelt occurred or salt concentrations lowered the freezing temperature to maintain water as liquid. Correlation of the Coleoptera species with cultured bacteria in the sample and the likelihood of co-habitation with Beauveria bassiani found in two adjacent, although younger paleosols, leads to new questions about the antiquity of the Coleoptera and the source of N and glucose from chitinase derived from the insects. The skeletons in the 831 section may date close to the oldest preserved chitin (Oligocene) yet found on Earth. While harsh Martian conditions make it seemingly intolerable for complex, multicellular organisms such as insects to exist in the near-surface and subaerially, life within similar cold, dry paleosol microenvironments (Cryosols) of Antarctica point to life potential for the Red Planet, especially when considering the relatively diverse microbe (bacteria and fungi) population. (C) 2011 Elsevier Ltd. All rights reserved.

Switching between molecular switch types by module rearrangement:Ca -enabled, H-driven 'off-on-off', H-driven YES and PASS 0 as well as H, Ca-driven AND logic operations

Several logic gates and switches can be accessed from two different combinations of a single set of fluorophore, receptor and spacer components.

Experimental and numerical studies on rock breaking with TBM tools under high stress confinement

The understanding of rock breaking and chipping due to the TBM cutter disks mechanism in deep tunnels is considered in this paper. The interest stems from the use of TBMs for the excavation of long Trans-Alpine tunnels. Some tests that simulate the disk cutter action at the tunnel face by means of an indenter, acting on a rock specimen are proposed. The rock specimen is confined through a flat-jack and a confinement-free area on one side of the specimen simulates the formation of a groove near the indenter, like it occurs in TBM excavation conditions. Results show a limited influence of the confinement stress versus the thrust increment required for breaking the rock between the indenter and the free side of the specimen. Numerical modelling of the cutter disk action on confined material has also been carried out in order to investigate further aspects of the fracture initiation. Also in this case the importance of the relative position between disk cutter and groove is pointed out. © 2006 Springer-Verlag.

Screw conveyor device for laboratory tests on conditioned soil for EPB tunneling operations

Earth pressure balanced (EPB) full face tunneling machines have experienced a remarkable increase in the number of applications throughout the world due to both mechanical developments and a more effective use of additives to condition the ground. Conditioning modifies the mechanical and hydraulic properties of a soil by making it suitable for the pressure control in the bulk chamber and extraction with the screw conveyor. The extraction system plays a fundamental role during the EPB operations particularly for a correct application of the face pressure. Despite the extensive use of the EPB technique, little knowledge exists concerning the understanding of the behavior of conditioned soil, particularly for noncohesive ground (sand and gravel). This paper presents and describes a prototype laboratory device, which simulates the extraction of the ground from a pressurized tank with a screw conveyor. The results of a preliminary test program carried out on a medium sized sand show that the prototype device is efficient in verifying the effects of foam for an optimal use in EPB conditioning. © 2007 ASCE.

Numerical modelling of laboratory tests for TBM cutter indentation process analysis

Considering that TBMs are nowadays used for long Trans-Alpine tunnels, the
understanding of rock breaking and chipping due to TBM cutter disks mechanism, for deep tunnelling operations, becomes very interesting. In this paper, the results from carried out laboratory tests that simulate the disk cutter action at the rock tunnel face by means of an indentation tool, acting on a rock
specimen with proper size, and the related three-dimensional and two-dimensional numerical modelling are proposed. The developed numerical models simulate the different test conditions (applied load, boundary conditions) allowing the analysis of the stresses distributions along possible breaking planes.
The influence of a confinement-free area on one side of the specimen, simulating the formation of a groove near the tool, is pointed out.
The obtained results from numerical modelling put in evidence a satisfactory agreement with the experimental observations.

Ash from Changbaishan Millennium eruption recorded in Greenland ice: Implications for determining the eruption's timing and impact

Major volcanic eruptions can impact on global climate by injecting large quantities of aerosols and ash into the atmosphere that alter the radiative balance and chemical equilibrium of the stratosphere. The Millennium eruption of Tianchi (Paektu), China/North Korea, was one of the largest Late Holocene eruptions. Uncertainty about the precise timing of the eruption has hindered the recognition of its climate impact in palaeoclimate and historical records. Here we report the compelling identification of the eruption's volcanic signal in Greenland ice cores through the association of geochemically-characterized volcanic glass, represented in by bimodal populations that compare with proximal material from the source eruption. The eruption most probably occurred in the AD 940?s, seven years after the Eldgjá eruption on Iceland. We examine the eruption's potential for climate forcing using the sulfate records from the ice-cores and conclude that it was unlikely to have had a global or extra-regional impact.

Asynchrony between the Greenland ice core chronology and the radiocarbon calibration curve? Evidence from Irish bogs

A significant cold event, deduced from the Greenland ice cores, took place between 8200 and 8000 cal. BP. Modeling of the event suggests that higher northern latitudes would have also experienced considerable decreases in precipitation and that Ireland would have witnessed one of the greatest depressions. However, no well-dated proxy record exists from the British Isles to test the model results. Here we present independent evidence for a phase of major pine recruitment on Irish bogs at around 8150 cal. BP. Dendrochronological dating of subfossil trees from three sites reveal synchronicity in germination across the region, indicative of a regional forcing, and allows for high-precision radiocarbon based dating. The inner-rings of 40% of all samples from the north of Ireland dating to the period 8500-7500 cal. BP fall within a 25-yr window. The concurrent colonization of pine on peatland is interpreted as drier conditions in the region and provides the first substantive proxy data in support of a significant hydrological change in the north of Ireland accompanying the 8.2 ka event. The dating uncertainties associated with the Irish pine record and the Greenland Ice Core Chronology 2005 (GICC05) do not allow for any overlap between the two. Our results indicate that the discrepancy could be an artifact of dating inaccuracy, and support a similar claim by Lohne et al. (2013) for the Younger Dryas boundaries. If real, this asynchrony will most likely have affected interpretations of previous proxy alignments.