Polymorphism of the glass former ethanol confined in mesoporous silicon

X-ray diffraction patterns of ethanol confined in parallel-aligned channels of approx. 10 nm diameter and 50 micrometer length in mesoporous silicon have been recorded as a function of filling fraction, temperature and for varying cooling and heating rates. A sorption isotherm, recorded in the liquid state, indicates a three monolayer thick, strongly adsorbed wall layer and a capillary condensed fraction of molecules in the pore center. Though the strongly adsorbed film remains in an amorphous state for the entire temperature range investigated, the capillary condensed molecules reproduce the polymorphism of bulk solid ethanol, that is the formation of either crystalline or glass-like states as a function of cooling rate. The critical rate necessary to achieve a vitrification in the mesopores is, however, at least two orders of magnitude smaller than in the bulk state. This finding can be traced both to pure geometrical constraints and quenched disorder effects, characteristic of confinement in mesoporous silicon.Comment: 6 pages, 4 figure

Crystallization of medium length 1-alcohols in mesoporous silicon: An X-ray diffraction study

The linear 1-alcohols n-C16H33OH, n-C17H35OH, n-C19H37OH have been imbibed and solidified in lined up, tubular mesopores of silicon with 10 nm and 15 nm mean diameters, respectively. X-ray diffraction measurements reveal a set of six discrete orientation states (''domains'') characterized by a perpendicular alignment of the molecules with respect to the long axis of the pores and by a four-fold symmetry about this direction, which coincides with the crystalline symmetry of the Si host. A Bragg peak series characteristic of the formation of bilayers indicates a lamellar structure of the spatially confined alcohol crystals in 15 nm pores. By contrast, no layering reflections could be detected for 10 nm pores. The growth mechanism responsible for the peculiar orientation states is attributed to a nano-scale version of the Bridgman technique of single-crystal growth, where the dominant growth direction is aligned parallelly to the long pore axes. Our observations are analogous to the growth phenomenology encountered for medium length n-alkanes confined in mesoporous silicon (Phys. Rev. E 75, 021607 (2007)) and may further elucidate why porous silicon matrices act as an effective nucleation-inducing material for protein solution crystallization.Comment: 4 pages, 4 figures, to appear as a Brief Report in Physical Review

Crossover from a square to a hexagonal pattern in Faraday surface waves

We report on surface wave pattern formation in a Faraday experiment operated at a very shallow filling level, where modes with a subharmonic and harmonic time dependence interact. Associated with this distinct temporal behavior are different pattern selection mechanisms, favoring squares or hexagons, respectively. In a series of bifurcations running through a pair of superlattices the surface wave pattern transforms between the two incompatible symmetries. The close analogy to 2D and 3D crystallography is pointed out.Comment: 4 pages, 4 figure

Phase relaxation of Faraday surface waves

Surface waves on a liquid air interface excited by a vertical vibration of a fluid layer (Faraday waves) are employed to investigate the phase relaxation of ideally ordered patterns. By means of a combined frequency-amplitude modulation of the excitation signal a periodic expansion and dilatation of a square wave pattern is generated, the dynamics of which is well described by a Debye relaxator. By comparison with the results of a linear theory it is shown that this practice allows a precise measurement of the phase diffusion constant.Comment: 5 figure

Climate, CO₂ and demographic impacts on global wildfire emissions

Abstract. Wildfires are by far the largest contributor to global biomass burning and constitute a large global source of atmospheric traces gases and aerosols. Such emissions have a considerable impact on air quality and constitute a major health hazard. Biomass burning also influences the radiative balance of the atmosphere and is thus not only of societal, but also of significant scientific interest. There is a common perception that climate change will lead to an increase in emissions as hot and dry weather events that promote wildfire will become more common. However, even though a few studies have found that the inclusion of CO2 fertilisation of photosynthesis and changes in human population patterns will tend to somewhat lower predictions of future wildfire emissions, no such study has included full ensemble ranges of both climate predictions and population projections, including the effect of different degrees of urbanisation. Here, we present a series of 124 simulations with the LPJ–GUESS–SIMFIRE global dynamic vegetation–wildfire model, including a semi-empirical formulation for the prediction of burned area based on fire weather, fuel continuity and human population density. The simulations use Climate Model Intercomparison Project 5 (CMIP5) climate predictions from eight Earth system models. These were combined with two Representative Concentration Pathways (RCPs) and five scenarios of future human population density based on the series of Shared Socioeconomic Pathways (SSPs) to assess the sensitivity of emissions to the effect of climate, CO2 and humans. In addition, two alternative parameterisations of the semi-empirical burned-area model were applied. Contrary to previous work, we find no clear future trend of global wildfire emissions for the moderate emissions and climate change scenario based on the RCP 4.5. Only historical population change introduces a decline by around 15 % since 1900. Future emissions could either increase for low population growth and fast urbanisation, or continue to decline for high population growth and slow urbanisation. Only for high future climate change (RCP8.5), wildfire emissions start to rise again after ca. 2020 but are unlikely to reach the levels of 1900 by the end of the 21st century. We find that climate warming will generally increase the risk of fire, but that this is only one of several equally important factors driving future levels of wildfire emissions, which include population change, CO2 fertilisation causing woody thickening, increased productivity and fuel load and faster litter turnover in a warmer climate

Evidence for Kosterlitz-Thouless type orientational ordering of CF3_3Br monolayers physisorbed on graphite

Monolayers of the halomethane CF$_3$Br adsorbed on graphite have been investigated by x-ray diffraction. The layers crystallize in a commensurate triangular lattice. On cooling they approach a three-sublattice antiferroelectric pattern of the in-plane components of the dipole moments. The ordering is not consistent with a conventional phase transition, but points to Kosterlitz-Thouless behavior. It is argued that the transition is described by a 6-state clock model on a triangular lattice with antiferromagnetic nearest neighbor interactions which is studied with Monte-Carlo simulations. A finite-size scaling analysis shows that the ordering transition is indeed in the KT universality class.Comment: 4 pages, 5 figure

Peat decomposition records in three pristine ombrotrophic bogs in southern Patagonia

Ombrotrophic bogs in southern Patagonia have been examined with regard to paleoclimatic and geochemical research questions but knowledge about organic matter decomposition in these bogs is limited. Therefore, we examined peat humification with depth by Fourier Transformed Infrared (FTIR) measurements of solid peat, C/N ratio, and δ<sup>13</sup>C and δ<sup>15</sup>N isotope measurements in three bog sites. Peat decomposition generally increased with depth but distinct small scale variation occurred, reflecting fluctuations in factors controlling decomposition. C/N ratios varied mostly between 40 and 120 and were significantly correlated (<i>R</i><sup>2</sup> > 0.55, <i>p</i> < 0.01) with FTIR-derived humification indices. The degree of decomposition was lowest at a site presently dominated by <i>Sphagnum</i> mosses. The peat was most strongly decomposed at the driest site, where currently peat-forming vegetation produced less refractory organic material, possibly due to fertilizing effects of high sea spray deposition. Decomposition of peat was also advanced near ash layers, suggesting a stimulation of decomposition by ash deposition. Values of δ<sup>13</sup>C were 26.5 ± 2‰ in the peat and partly related to decomposition indices, while δ<sup>15</sup>N in the peat varied around zero and did not consistently relate to any decomposition index. Concentrations of DOM partly related to C/N ratios, partly to FTIR derived indices. They were not conclusively linked to the decomposition degree of the peat. DOM was enriched in <sup>13</sup>C and in <sup>15</sup>N relative to the solid phase probably due to multiple microbial modifications and recycling of N in these N-poor environments. In summary, the depth profiles of C/N ratios, δ<sup>13</sup>C values, and FTIR spectra seemed to reflect changes in environmental conditions affecting decomposition, such as bog wetness, but were dominated by site specific factors, and are further influenced by ash deposition and possibly by sea spray input

Strong Families in Crises

Family Relations and Child Developmen