In situ FTIRS investigations of surface processes of Rh electrode - Novel observation of geminal adsorbates of carbon monoxide on Rh electrode in acid solution

With the help of in situ multi-step FTIR Spectroscopy, two types of adsorbed geminal CO have been observed for the first time at an electrochemically modified Rh electrode. A doublet band of two broad peaks at 2166 and 2112cm is assigned to geminal CO on Rh surface oxide (or hydroxide) produced by the electrochemical modification process, and a doublet band of two peaks near 2103 and 2033cm is ascribed to geminal CO on surface clusters of Rh formed by reduction of Rh surface oxide. Based on the evolution of FTIR spectra with the electrode potential, the surface processes of a Rh electrode, subjected to a potential cycling treatment at 1.5Vs between -0.275 and 2.4V for 2min, have been elucidated. The present results at the solid/liquid electrochemical interface were compared with those obtained at the solid/gas interface, and consistent conclusions were achieved.

Improved evaporative flux partitioning and carbon flux in the land surface model JULES: impact on the simulation of land surface processes in temperate Europe

The primary role of land surface models embedded in climate models is to partition surface available energy into upwards, radiative, sensible and latent heat fluxes. Partitioning of evapotranspiration, ET, is of fundamental importance: as a major component of the total surface latent heat flux, ET affects the simulated surface water balance, and related energy balance, and consequently the feedbacks with the atmosphere. In this context it is also crucial to credibly represent the CO2 exchange between ecosystems and their environment. In this study, JULES, the land surface model used in UK weather and climate models, has been evaluated for temperate Europe. Compared to eddy covariance flux measurements, the CO2 uptake by the ecosystem is underestimated and the ET overestimated. In addition, the contribution to ET from soil and intercepted water evaporation far outweighs the contribution of plant transpiration. To alleviate these biases, adaptations have been implemented in JULES, based on key literature references. These adaptations have improved the simulation of the spatio-temporal variability of the fluxes and the accuracy of the simulated GPP and ET, including its partitioning. This resulted in a shift of the seasonal soil moisture cycle. These adaptations are expected to increase the fidelity of climate simulations over Europe. Finally, the extreme summer of 2003 was used as evaluation benchmark for the use of the model in climate change studies. The improved model captures the impact of the 2003 drought on the carbon assimilation and the water use efficiency of the plants. It, however, underestimates the 2003 GPP anomalies. The simulations showed that a reduction of evaporation from the interception and soil reservoirs, albeit not of transpiration, largely explained the good correlation between the carbon and the water fluxes anomalies that was observed during 2003. This demonstrates the importance of being able to discriminate the response of individual component of the ET flux to environmental forcing.

Improved simulation of fire–vegetation interactions in the Land surface Processes and eXchanges dynamic global vegetation model (LPX-Mv1)

The Land surface Processes and eXchanges (LPX) model is a fire-enabled dynamic global vegetation model that performs well globally but has problems representing fire regimes and vegetative mix in savannas. Here we focus on improving the fire module. To improve the representation of ignitions, we introduced a reatment of lightning that allows the fraction of ground strikes to vary spatially and seasonally, realistically partitions strike distribution between wet and dry days, and varies the number of dry days with strikes. Fuel availability and moisture content were improved by implementing decomposition rates specific to individual plant functional types and litter classes, and litter drying rates driven by atmospheric water content. To improve water extraction by grasses, we use realistic plant-specific treatments of deep roots. To improve fire responses, we introduced adaptive bark thickness and post-fire resprouting for tropical and temperate broadleaf trees. All improvements are based on extensive analyses of relevant observational data sets. We test model performance for Australia, first evaluating parameterisations separately and then measuring overall behaviour against standard benchmarks. Changes to the lightning parameterisation produce a more realistic simulation of fires in southeastern and central Australia. Implementation of PFT-specific decomposition rates enhances performance in central Australia. Changes in fuel drying improve fire in northern Australia, while changes in rooting depth produce a more realistic simulation of fuel availability and structure in central and northern Australia. The introduction of adaptive bark thickness and resprouting produces more realistic fire regimes in Australian savannas. We also show that the model simulates biomass recovery rates consistent with observations from several different regions of the world characterised by resprouting vegetation. The new model (LPX-Mv1) produces an improved simulation of observed vegetation composition and mean annual burnt area, by 33 and 18% respectively compared to LPX.

The role of upper-level dynamics and surface processes for the Pakistan flood of July 2010

In July and August 2010 floods of unprecedented impact afflicted Pakistan. The floods resulted from a series of intense multi-day precipitation events in July and early August. At the same time a series of blocking anticyclones dominated the upper-level flow over western Russia and breaking waves i.e. equatorward extrusions of stratospheric high potential vorticity (PV) air formed along the downstream flank of the blocks. Previous studies suggested that these extratropical upper-level breaking waves were crucial for instigating the precipitation events in Pakistan. Here a detailed analysis is provided of the extratropical forcing of the precipitation. Piecewise PV inversion is used to quantify the extratropical upper-level forcing associated with the wave breaking and trajectories are calculated to study the pathways and source regions of the moisture that precipitated over Pakistan. Limited-area model simulations are carried out to complement the Lagrangian analysis. The precipitation events over Pakistan resulted from a combination of favourable boundary conditions with strong extratropical and monsoonal forcing factors. Above-normal sea-surface temperatures in the Indian Ocean led to an elevated lower-tropospheric moisture content. Surface monsoonal depressions ensured the transport of moist air from the ocean towards northeastern Pakistan. Along this pathway the air parcel humidity increased substantially (60–90% of precipitated moisture) via evapotranspiration from the land surface. Extratropical breaking waves influenced the surface wind field substantially by enhancing the wind component directed towards the mountains which reinforced the precipitation.

Complexity and non-linearity in earth surface processes - concepts, methods and applications

Complexity has long been recognized and is increasingly becoming mainstream in geomorphology. However, the relative novelty of various concepts and techniques associated to it means that ambiguity continues to surround complexity. In this commentary, we present and discuss a variety of recent contributions that have the potential to help clarify issues and advance the use of complexity in geomorphology.

Lithium isotope constraints on crust–mantle interactions and surface processes on Mars

Lithium abundances and isotope compositions are reported for a suite of martian meteorites that span the range of petrological and geochemical types recognized to date for Mars. Samples include twenty-one bulk-rock enriched, intermediate and depleted shergottites, six nakhlites, two chassignites, the orthopyroxenite Allan Hills (ALH) 84001 and the polymict breccia Northwest Africa (NWA) 7034. Shergottites unaffected by terrestrial weathering exhibit a range in δ7Li from 2.1 to 6.2‰, similar to that reported for pristine terrestrial peridotites and unaltered mid-ocean ridge and ocean island basalts. Two chassignites have δ7Li values (4.0‰) intermediate to the shergottite range, and combined, these meteorites provide the most robust current constraints on δ7Li of the martian mantle. The polymict breccia NWA 7034 has the lowest δ7Li (−0.2‰) of all terrestrially unaltered martian meteorites measured to date and may represent an isotopically light surface end-member. The new data for NWA 7034 imply that martian crustal surface materials had both a lighter Li isotope composition and elevated Li abundance compared with their associated mantle. These findings are supported by Li data for olivine-phyric shergotitte NWA 1068, a black glass phase isolated from the Tissint meteorite fall, and some nakhlites, which all show evidence for assimilation of a low-δ7Li crustal component. The range in δ7Li for nakhlites (1.8 to 5.2‰), and co-variations with chlorine abundance, suggests crustal contamination by Cl-rich brines. The differences in Li isotope composition and abundance between the martian mantle and estimated crust are not as large as the fractionations observed for terrestrial continental crust and mantle, suggesting a difference in the styles of alteration and weathering between water-dominated processes on Earth versus possibly Cl–S-rich brines on Mars. Using high-MgO shergottites (>15 wt.% MgO) it is possible to estimate the δ7Li of Bulk Silicate Mars (BSM) to be 4.2 ± 0.9‰ (2σ). This value is at the higher end of estimates for the Bulk Silicate Earth (BSE; 3.5 ± 1.0‰, 2σ), but overlaps within uncertainty.

Ion-assisted precursor dissociation and surface diffusion : enabling rapid, low-temperature growth of carbon nanofibers

Growth kinetics of carbon nanofibers in a hydrocarbon plasma is studied. In addition to gas-phase and surface processes common to chemical vapor deposition, the model includes (unique to plasma-exposed catalyst surfaces) ion-induced dissociation of hydrocarbons, interaction of adsorbed species with incoming hydrogen atoms, and dissociation of hydrocarbon ions. It is shown that at low, nanodevice-friendly process temperatures the nanofibers grow via surface diffusion of carbon adatoms produced on the catalyst particle via ion-induced dissociation of a hydrocarbon precursor. These results explain a lower activation energy of nanofiber growth in a plasma and can be used for the synthesis of other nanoassemblies. © 2007 American Institute of Physics.

Surface science of plasma exposed surfaces : a challenge for applied plasma science

This article introduces a deterministic approach to using low-temperature, thermally non-equilibrium plasmas to synthesize delicate low-dimensional nanostructures of a small number of atoms on plasma exposed surfaces. This approach is based on a set of plasma-related strategies to control elementary surface processes, an area traditionally covered by surface science. Major issues related to balanced delivery and consumption of building units, appropriate choice of process conditions, and account of plasma-related electric fields, electric charges and polarization effects are identified and discussed in the quantum dot nanoarray context. Examples of a suitable plasma-aided nanofabrication facility and specific effects of a plasma-based environment on self-organized growth of size- and position-uniform nanodot arrays are shown. These results suggest a very positive outlook for using low-temperature plasma-based nanotools in high-precision nanofabrication of self-assembled nanostructures and elements of nanodevices, one of the areas of continuously rising demand from academia and industry.

Computational plasma nanoscience : where plasma physics meets surface science

Multiscale hybrid simulations that bridge the nine-order-of-magnitude spatial gap between the macroscopic plasma nanotools and microscopic surface processes on nanostructured solids are described. Two specific examples of carbon nanotip-like and semiconductor quantum dot nanopatterns are considered. These simulations are instrumental in developing physical principles of nanoscale assembly processes on solid surfaces exposed to low-temperature plasmas.

A coupling model for terrestrial processes in arid areas and its application

In this paper, the importance of investigation on terrestrical processes in arid areas for mankind's living environment protection and local economy development as well as its present state of the art are elucidated. A coupling model, which evaluates heat, mass, momentum and radiative fluxes in the SPAC system, is developed for simulating microclimate over plant and bare soil. Especially, it is focussed on the details of turbulence transfer. For illustration, numerical simulation of the water-heat exchange processes at Shapotou Observatory, GAS, Ninxia Province are conducted, and the computational results show that the laws of land-surface processes are rather typical in the arid areas.

Current-induced migration of surface adatoms during GaN growth by molecular beam epitaxy

The influence of electric fields on surface migration of Gallium (Ga) and Nitrogen (N) adatoms is studied during GaN growth by molecular beam epitaxy (MBE). When a direct current (DC) is used to heat the sample, long distance migration of Ga adatoms and diffusion asymmetry of N adatoms at steps are observed. On the other hand, if an alternating current (AC) is used, no such preferential adatom migration is found. This effect is attributed to the effective positive charges of surface adatoms. representing an effect of electro-migration. The implications of such current-induced surface migration to GaN epitaxy are subsequently investigated. It is seen to firstly change the distribution of Ga adatoms on a growing surface, and thus make the growth to be Ga-limited at one side of the sample but N-limited at the other side. This leads to different optical qualities of the film and different morphologies of the surface. (C) 2001 Elsevier Science B.V. All rights reserved.

Current-induced migration of surface adatoms during GaN growth by molecular beam epitaxy

The influence of electric fields on surface migration of Gallium (Ga) and Nitrogen (N) adatoms is studied during GaN growth by molecular beam epitaxy (MBE). When a direct current (DC) is used to heat the sample, long distance migration of Ga adatoms and diffusion asymmetry of N adatoms at steps are observed. On the other hand, if an alternating current (AC) is used, no such preferential adatom migration is found. This effect is attributed to the effective positive charges of surface adatoms. representing an effect of electro-migration. The implications of such current-induced surface migration to GaN epitaxy are subsequently investigated. It is seen to firstly change the distribution of Ga adatoms on a growing surface, and thus make the growth to be Ga-limited at one side of the sample but N-limited at the other side. This leads to different optical qualities of the film and different morphologies of the surface. (C) 2001 Elsevier Science B.V. All rights reserved.