Synergetic effect of carbon nanopore size and surface oxidation on CO2 capture from CO2/CH4 mixtures

We have studied the synergetic effect of confinement (carbon nanopore size) and surface chemistry (the number of carbonyl groups) on CO2 capture from its mixtures with CH4 at typical operating conditions for industrial adsorptive separation (298 K and compressed CO2CH4 mixtures). Although both confinement and surface oxidation have an impact on the efficiency of CO2/CH4 adsorptive separation at thermodynamics equilibrium, we show that surface functionalization is the most important factor in designing an efficient adsorbent for CO2 capture. Systematic Monte Carlo simulations revealed that adsorption of CH4 either pure or mixed with CO2 on oxidized nanoporous carbons is only slightly increased by the presence of functional groups (surface dipoles). In contrast, adsorption of CO2 is very sensitive to the number of carbonyl groups, which can be examined by a strong electric quadrupolar moment of CO2. Interestingly, the adsorbed amount of CH4 is strongly affected by the presence of the co-adsorbed CO2. In contrast, the CO2 uptake does not depend on the molar ratio of CH4 in the bulk mixture. The optimal carbonaceous porous adsorbent used for CO2 capture near ambient conditions should consist of narrow carbon nanopores with oxidized pore walls. Furthermore, the equilibrium separation factor was the greatest for CO2/CH4 mixtures with a low CO2 concentration. The maximum equilibrium separation factor of CO2 over CH4 of ∼18–20 is theoretically predicted for strongly oxidized nanoporous carbons. Our findings call for a review of the standard uncharged model of carbonaceous materials used for the modeling of the adsorption separation processes of gas mixtures containing CO2 (and other molecules with strong electric quadrupolar moment or dipole moment).

Statistical analysis of eight surface ozone measurement series for various sites in Ireland

Data from various stations having different measurement record periods between 1988 and 2007 are analyzed to investigate the surface ozone concentration, long-term trends, and seasonal changes in and around Ireland. Time series statistical analysis is performed on the monthly mean data using seasonal and trend decomposition procedures and the Box-Jenkins approach (autoregressive integrated moving average). In general, ozone concentrations in the Irish region are found to have a negative trend at all sites except at the coastal sites of Mace Head and Valentia. Data from the most polluted Dublin city site have shown a very strong negative trend of −0.33 ppb/yr with a 95% confidence limit of 0.17 ppb/yr (i.e., −0.33 ± 0.17) for the period 2002−2007, and for the site near the city of Cork, the trend is found to be −0.20 ± 0.11 ppb/yr over the same period. The negative trend for other sites is more pronounced when the data span is considered from around the year 2000 to 2007. Rural sites of Wexford and Monaghan have also shown a very strong negative trend of −0.99 ± 0.13 and −0.58 ± 0.12, respectively, for the period 2000−2007. Mace Head, a site that is representative of ozone changes in the air advected from the Atlantic to Europe in the marine planetary boundary layer, has shown a positive trend of about +0.16 ± 0.04 ppb per annum over the entire period 1988−2007, but this positive trend has reduced during recent years (e.g., in the period 2001−2007). Cluster analysis for back trajectories are performed for the stations having a long record of data, Mace Head and Lough Navar. For Mace Head, the northern and western clean air sectors have shown a similar positive trend (+0.17 ± 0.02 ppb/yr for the northern sector and +0.18 ± 0.02 ppb/yr for the western sector) for the whole period, but partial analysis for the clean western sector at Mace Head shows different trends during different time periods with a decrease in the positive trend since 1988 indicating a deceleration in the ozone trend for Atlantic air masses entering Europe.

The importance of surface pressure changes in the response of the atmosphere to zonally-symmetric thermal and mechanical forcing

he classical problem of the response of a balanced, axisymmetric vortex to thermal and mechanical forcing is re-examined, paying special attention to the lower boundary condition. The correct condition is DΦ/Dt = 0, where Φ is the geopotential and D/Dt the material derivative, which explicitly accounts for a mass redistribution as part of the mean-flow response. This redistribution is neglected when using the boundary condition Dp/Dt = 0, which has conventionally been applied in this problem. It is shown that applying the incorrect boundary condition, and thereby ignoring the surface pressure change, leads to a zonal wind acceleration δū/δt that is too strong, especially near the surface. The effect is significant for planetary-scale forcing even when applied at tropopause level. A comparison is made between the mean-flow evolution in a baroclinic life-cycle, as simulated in a fully nonlinear, primitive-equation model, and that predicted by using the simulated eddy fluxes in the zonally-symmetric response problem. Use of the correct lower boundary condition is shown to lead to improved agreement.

Co-eruptive and inter-eruptive surface deformation measured by satellite radar interferometry at Nyamuragira volcano, D.R. Congo, 1996 to 2010.

Interferometric Synthetic Aperture Radar (InSAR) measurements of surface deformation at Nyamuragira Volcano between 1996 and 2010 reveal a variety of co-eruptive and inter-eruptive signals. During 7 of the 8 eruptions in this period deformation was measured that is consistent with the emplacement of shallow near-vertical dykes feeding the eruptive fissures and associated with a NNW-trending fissure zone that traverses the summit caldera. Between eruptions the caldera and the summit part of this fissure zone subsided gradually (b3–5 cm/year). We also find evidence of post-eruption subsidence around the sites of the main vents of some flank eruptions (2002, 2004, 2006, and 2010). In the 6 months prior to the 2010 eruption a10-km wide zone centred on the caldera inflated by 1–2 cm. The low magnitude of this signal suggests that the presumed magma reservoir at 3–8 km depth contains highly compressible magma with little stored elastic strain energy. To the north of the caldera the fissure zone splits into WNW and NE branches around a zone that has a distinct InSAR signal. We interpret this zone to represent an elevated, 'stable' block of basement rocks buried by lavas within the Rift Zone.

Sea surface temperature climate change initiative: alternative image classification algorithms for sea-ice affected oceans

We present a Bayesian image classification scheme for discriminating cloud, clear and sea-ice observations at high latitudes to improve identification of areas of clear-sky over ice-free ocean for SST retrieval. We validate the image classification against a manually classified dataset using Advanced Along Track Scanning Radiometer (AATSR) data. A three way classification scheme using a near-infrared textural feature improves classifier accuracy by 9.9 % over the nadir only version of the cloud clearing used in the ATSR Reprocessing for Climate (ARC) project in high latitude regions. The three way classification gives similar numbers of cloud and ice scenes misclassified as clear but significantly more clear-sky cases are correctly identified (89.9 % compared with 65 % for ARC). We also demonstrate the poetential of a Bayesian image classifier including information from the 0.6 micron channel to be used in sea-ice extent and ice surface temperature retrieval with 77.7 % of ice scenes correctly identified and an overall classifier accuracy of 96 %.

Evaluation of high-resolution surface wind products at global and regional scales

High resolution surface wind fields covering the global ocean, estimated from remotely sensed wind data and ECMWF wind analyses, have been available since 2005 with a spatial resolution of 0.25 degrees in longitude and latitude, and a temporal resolution of 6h. Their quality is investigated through various comparisons with surface wind vectors from 190 buoys moored in various oceanic basins, from research vessels and from QuikSCAT scatterometer data taken during 2005-2006. The NCEP/NCAR and NCDC blended wind products are also considered. The comparisons performed during January-December 2005 show that speeds and directions compare well to in-situ observations, including from moored buoys and ships, as well as to the remotely sensed data. The root-mean-squared differences of the wind speed and direction for the new blended wind data are lower than 2m/s and 30 degrees, respectively. These values are similar to those estimated in the comparisons of hourly buoy measurements and QuickSCAT near real time retrievals. At global scale, it is found that the new products compare well with the wind speed and wind vector components observed by QuikSCAT. No significant dependencies on the QuikSCAT wind speed or on the oceanic region considered are evident.Evaluation of high-resolution surface wind products at global and regional scales

Global radiative and climate effect of the water vapour continuum at visible and near-infrared wavelengths

Recent laboratory measurements show that absorption by the water vapour continuum in near-infrared windows may be about an order of magnitude higher than assumed in many radiation codes. The radiative impact of the continuum at visible and near-infrared wavelengths is examined for the present day and for a possible future warmer climate (with a global-mean total column water increase of 33%). The calculations use a continuum model frequently used in climate models (‘CKD’) and a continuum model where absorption is enhanced at wavelengths greater than 1 µm based on recent measurements (‘CAVIAR’). The continuum predominantly changes the partitioning between solar radiation absorbed by the surface and the atmosphere; changes in top-of-atmosphere net irradiances are smaller. The global-mean clear-sky atmospheric absorption is enhanced by 1.5 W m−2 (about 2%) and 2.8 W m−2 (about 3.5%) for CKD and CAVIAR respectively, relative to a hypothetical no-continuum case, with all-sky enhancements about 80% of these values. The continuum is, in relative terms, more important for radiation budget changes between the present day and a possible future climate. Relative to the no-continuum case, the increase in global-mean clear-sky absorption is 8% higher using CKD and almost 20% higher using CAVIAR; all-sky enhancements are about half these values. The effect of the continuum is estimated for the solar component of the water vapour feedback, the reduction in downward surface irradiance and precipitation change in a warmer world. For CKD and CAVIAR respectively, and relative to the no-continuum case, the solar component of the water vapour feedback is enhanced by about 4 and 9%, the change in clear-sky downward surface irradiance is 7 and 18% more negative, and the global-mean precipitation response decreases by 1 and 4%. There is a continued need for improved continuum measurements, especially at atmospheric temperatures and at wavelengths below 2 µm.

Surface chemistry of alanine on Cu{111}: Adsorption geometry and temperature dependence

Adsorption of l-alanine on the Cu{111} single crystal surface was investigated as a model system for interactions between small chiral modifier molecules and close-packed metal surfaces. Synchrotron-based X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy are used to determine the chemical state, bond coordination and out-of-plane orientation of the molecule on the surface. Alanine adsorbs in its anionic form at room temperature, whilst at low temperature the overlayer consists of anionic and zwitterionic molecules. NEXAFS spectra exhibit a strong angular dependence of the π ⁎ resonance associated with the carboxylate group, which allows determining the tilt angle of this group with respect to the surface plane (48° ± 2°) at room temperature. Low-energy electron diffraction (LEED) shows a p(2√13x2√13)R13° superstructure with only one domain, which breaks the mirror symmetry of the substrate and, thus, induces global chirality to the surface. Temperature-programmed XPS (TP-XPS) and temperature-programmed desorption (TPD) experiments indicate that the zwitterionic form converts into the anionic species (alaninate) at 293 K. The latter desorbs/decomposes between 435 K and 445 K.

Relationship between the near-Earth interplanetary field and the coronal source flux: dependence on timescale

The Ulysses spacecraft has shown that the radial component of the heliospheric magnetic field is approximately independent of latitude. This has allowed quantification of the total open solar flux from near-Earth observations of the interplanetary magnetic field. The open flux can also be estimated from photospheric magnetograms by mapping the fields up to the ‘‘coronal source surface’’ where the field is assumed to be radial and which is usually assumed to be at a heliocentric distance r = 2.5R_{S} (a mean solar radius, 1R_{S} = 6.96x10^{8} m). These two classes of open flux estimate will differ by the open flux that threads the heliospheric current sheet(s) inside Earth’s orbit at 2.5R_{S} < r < 1R{1} (where the mean Earth-Sun distance, 1R_{1} = 1 AU = 1.5 x 10^{11} m). We here use near-Earth measurements to estimate this flux and show that at sunspot minimum it causes only a very small (approximately 0.5%) systematic difference between the two types of open flux estimate, with an uncertainty that is of order ±24% in hourly values, ±16% in monthly averages, and between -6% and +2% in annual values. These fractions may be somewhat larger for sunspot maximum because of flux emerging at higher heliographic latitudes.

Evidence of a topographic signal in surface soil moisture derived from ENVISAT ASAR wide swath data

The susceptibility of a catchment to flooding is affected by its soil moisture prior to an extreme rainfall event. While soil moisture is routinely observed by satellite instruments, results from previous work on the assimilation of remotely sensed soil moisture into hydrologic models have been mixed. This may have been due in part to the low spatial resolution of the observations used. In this study, the remote sensing aspects of a project attempting to improve flow predictions from a distributed hydrologic model by assimilating soil moisture measurements are described. Advanced Synthetic Aperture Radar (ASAR) Wide Swath data were used to measure soil moisture as, unlike low resolution microwave data, they have sufficient resolution to allow soil moisture variations due to local topography to be detected, which may help to take into account the spatial heterogeneity of hydrological processes. Surface soil moisture content (SSMC) was measured over the catchments of the Severn and Avon rivers in the South West UK. To reduce the influence of vegetation, measurements were made only over homogeneous pixels of improved grassland determined from a land cover map. Radar backscatter was corrected for terrain variations and normalized to a common incidence angle. SSMC was calculated using change detection. To search for evidence of a topographic signal, the mean SSMC from improved grassland pixels on low slopes near rivers was compared to that on higher slopes. When the mean SSMC on low slopes was 30–90%, the higher slopes were slightly drier than the low slopes. The effect was reversed for lower SSMC values. It was also more pronounced during a drying event. These findings contribute to the scant information in the literature on the use of high resolution SAR soil moisture measurement to improve hydrologic models.

Surface chemistry of alanine on Ni{111}

The adsorption of L-alanine on Ni{111} has been studied as a 10 model of enantioselective heterogeneous catalysts. Synchrotron-based X-ray 11 photoelectron spectroscopy and near-edge X-ray absorption fine structure 12 (NEXAFS) spectroscopy were used to determine the chemical state, bond 13 coordination, and out-of-plane orientation of the molecule on the surface. 14 Alanine adsorbs in anionic and zwitterionic forms between 250 and ≈320 K. 15 NEXAFS spectra exhibit a strong angular dependence of the π* resonance 16 associated with the carboxylate group, which is compatible with two distinct 17 orientations with respect to the surface corresponding to the bidentate and 18 tridentate binding modes. Desorption and decomposition begin together at 19 ≈300 K, with decomposition occurring in a multistep process up to ≈450 K. Comparison with previous studies of amino acid 20 adsorption on metal surfaces shows that this is among the lowest decomposition temperatures found so far and lower than typical 21 temperatures used for hydrogenation reactions where modified Ni catalysts are used.

Irreducible uncertainty in near-term climate projections

Model simulations of the next few decades are widely used in assessments of climate change impacts and as guidance for adaptation. Their non-linear nature reveals a level of irreducible uncertainty which it is important to understand and quantify, especially for projections of near-term regional climate. Here we use large idealised initial condition ensembles of the FAMOUS global climate model with a 1 %/year compound increase in CO2 levels to quantify the range of future temperatures in model-based projections. These simulations explore the role of both atmospheric and oceanic initial conditions and are the largest such ensembles to date. Short-term simulated trends in global temperature are diverse, and cooling periods are more likely to be followed by larger warming rates. The spatial pattern of near-term temperature change varies considerably, but the proportion of the surface showing a warming is more consistent. In addition, ensemble spread in inter-annual temperature declines as the climate warms, especially in the North Atlantic. Over Europe, atmospheric initial condition uncertainty can, for certain ocean initial conditions, lead to 20 year trends in winter and summer in which every location can exhibit either strong cooling or rapid warming. However, the details of the distribution are highly sensitive to the ocean initial condition chosen and particularly the state of the Atlantic meridional overturning circulation. On longer timescales, the warming signal becomes more clear and consistent amongst different initial condition ensembles. An ensemble using a range of different oceanic initial conditions produces a larger spread in temperature trends than ensembles using a single ocean initial condition for all lead times. This highlights the potential benefits from initialising climate predictions from ocean states informed by observations. These results suggest that climate projections need to be performed with many more ensemble members than at present, using a range of ocean initial conditions, if the uncertainty in near-term regional climate is to be adequately quantified.

Reconstructing the subsurface ocean decadal variability using surface nudging in a perfect model framework

Initialising the ocean internal variability for decadal predictability studies is a new area of research and a variety of ad hoc methods are currently proposed. In this study, we explore how nudging with sea surface temperature (SST) and salinity (SSS) can reconstruct the three-dimensional variability of the ocean in a perfect model framework. This approach builds on the hypothesis that oceanic processes themselves will transport the surface information into the ocean interior as seen in ocean-only simulations. Five nudged simulations are designed to reconstruct a 150 years “target” simulation, defined as a portion of a long control simulation. The nudged simulations differ by the variables restored to, SST or SST + SSS, and by the area where the nudging is applied. The strength of the heat flux feedback is diagnosed from observations and the restoring coefficients for SSS use the same time-scale. We observed that this choice prevents spurious convection at high latitudes and near sea-ice border when nudging both SST and SSS. In the tropics, nudging the SST is enough to reconstruct the tropical atmosphere circulation and the associated dynamical and thermodynamical impacts on the underlying ocean. In the tropical Pacific Ocean, the profiles for temperature show a significant correlation from the surface down to 2,000 m, due to dynamical adjustment of the isopycnals. At mid-to-high latitudes, SSS nudging is required to reconstruct both the temperature and the salinity below the seasonal thermocline. This is particularly true in the North Atlantic where adding SSS nudging enables to reconstruct the deep convection regions of the target. By initiating a previously documented 20-year cycle of the model, the SST + SSS nudging is also able to reproduce most of the AMOC variations, a key source of decadal predictability. Reconstruction at depth does not significantly improve with amount of time spent nudging and the efficiency of the surface nudging rather depends on the period/events considered. The joint SST + SSS nudging applied everywhere is the most efficient approach. It ensures that the right water masses are formed at the right surface density, the subsequent circulation, subduction and deep convection further transporting them at depth. The results of this study underline the potential key role of SSS for decadal predictability and further make the case for sustained large-scale observations of this field.

GHASP: an H alpha kinematic survey of spiral and irregular galaxies - IX. The near-infrared, stellar and baryonic Tully-Fisher relations

We studied, for the first time, the near-infrared, stellar and baryonic Tully-Fisher relations for a sample of field galaxies taken from a homogeneous Fabry-Perot sample of galaxies [the Gassendi HAlpha survey of SPirals (GHASP) survey]. The main advantage of GHASP over other samples is that the maximum rotational velocities were estimated from 2D velocity fields, avoiding assumptions about the inclination and position angle of the galaxies. By combining these data with 2MASS photometry, optical colours, HI masses and different mass-to-light ratio estimators, we found a slope of 4.48 +/- 0.38 and 3.64 +/- 0.28 for the stellar and baryonic Tully-Fisher relation, respectively. We found that these values do not change significantly when different mass-to-light ratio recipes were used. We also point out, for the first time, that the rising rotation curves as well as asymmetric rotation curves show a larger dispersion in the Tully-Fisher relation than the flat ones or the symmetric ones. Using the baryonic mass and the optical radius of galaxies, we found that the surface baryonic mass density is almost constant for all the galaxies of this sample. In this study we also emphasize the presence of a break in the NIR Tully-Fisher relation at M(H,K) similar to -20 and we confirm that late-type galaxies present higher total-to-baryonic mass ratios than early-type spirals, suggesting that supernova feedback is actually an important issue in late-type spirals. Due to the well-defined sample selection criteria and the homogeneity of the data analysis, the Tully-Fisher relation for GHASP galaxies can be used as a reference for the study of this relation in other environments and at higher redshifts.

The search for primordial quark nuggets among near Earth asteroids

Primordial Quark Nuggets, remnants of the quark-hadron phase transition, may be hiding most of the baryon number in superdense chunks have been discussed for years always from the theoretical point of view. While they seemed originally fragile at intermediate cosmological temperatures, it became increasingly clear that they may survive due to a variety of effects affecting their evaporation (surface and volume) rates. A search of these objects have never been attempted to elucidate their existence. We discuss in this note how to search directly for cosmological fossil nuggets among the small asteroids approaching Earth. `Asteroids` with a high visible-to-infrared flux ratio, constant lightcurves and devoid of spectral features are signals of an actual possible nugget nature. A viable search of very definite primordial quark nugget features can be conducted as a spinoff of the ongoing/forthcoming NEAs observation programmes.