The influence of carbon surface oxygen groups on Dubinin–Astakhov equation parameters calculated from CO2 adsorption isotherm

We present the results of a systematic study of the influence of carbon surface oxidation on Dubinin–Astakhov isotherm parameters obtained from the fitting of CO2 adsorption data. Using GCMC simulations of adsorption on realistic VPC models differing in porosity and containing the most frequently occurring carbon surface functionalities (carboxyls, hydroxyls and carbonyls) and their mixtures, it is concluded that the maximum adsorption calculated from the DA model is not strongly affected by the presence of oxygen groups. Unfortunately, the same cannot be said of the remaining two parameters of this model i.e. the heterogeneity parameter (n) and the characteristic energy of adsorption (E0). Since from the latter the pore diameters of carbons are usually calculated, by inverse-type relationships, it is concluded that they are questionable for carbons containing surface oxides, especially carboxyls.

Can carbon surface oxidation shift the pore size distribution curve calculated from Ar, N(2) and CO(2) adsorption isotherms? Simulation results for a realistic carbon model

Using the virtual porous carbon model proposed by Harris et al, we study the effect of carbon surface oxidation on the pore size distribution (PSD) curve determined from simulated Ar, N(2) and CO(2) isotherms. It is assumed that surface oxidation is not destructive for the carbon skeleton, and that all pores are accessible for studied molecules (i.e., only the effect of the change of surface chemical composition is studied). The results obtained show two important things, i.e., oxidation of the carbon surface very slightly changes the absolute porosity (calculated from the geometric method of Bhattacharya and Gubbins (BG)); however, PSD curves calculated from simulated isotherms are to a greater or lesser extent affected by the presence of surface oxides. The most reliable results are obtained from Ar adsorption data. Not only is adsorption of this adsorbate practically independent from the presence of surface oxides, but, more importantly, for this molecule one can apply the slit-like model of pores as the first approach to recover the average pore diameter of a real carbon structure. For nitrogen, the effect of carbon surface chemical composition is observed due to the quadrupole moment of this molecule, and this effect shifts the PSD curves compared to Ar. The largest differences are seen for CO2, and it is clearly demonstrated that the PSD curves obtained from adsorption isotherms of this molecule contain artificial peaks and the average pore diameter is strongly influenced by the presence of electrostatic adsorbate-adsorbate as well as adsorbate-adsorbent interactions.

Dust sources and deposition during the last glacial maximum and current climate: a comparison of model results with paleodata from ice cores and marine sediments

Mineral dust aerosols in the atmosphere have the potential to affect the global climate by influencing the radiative balance of the atmosphere and the supply of micronutrients to the ocean. Ice and marine sediment cores indicate that dust deposition from the atmosphere was at some locations 2–20 times greater during glacial periods, raising the possibility that mineral aerosols might have contributed to climate change on glacial-interglacial time scales. To address this question, we have used linked terrestrial biosphere, dust source, and atmospheric transport models to simulate the dust cycle in the atmosphere for current and last glacial maximum (LGM) climates. We obtain a 2.5-fold higher dust loading in the entire atmosphere and a twenty-fold higher loading in high latitudes, in LGM relative to present. Comparisons to a compilation of atmospheric dust deposition flux estimates for LGM and present in marine sediment and ice cores show that the simulated flux ratios are broadly in agreement with observations; differences suggest where further improvements in the simple dust model could be made. The simulated increase in high-latitude dustiness depends on the expansion of unvegetated areas, especially in the high latitudes and in central Asia, caused by a combination of increased aridity and low atmospheric [CO2]. The existence of these dust source areas at the LGM is supported by pollen data and loess distribution in the northern continents. These results point to a role for vegetation feedbacks, including climate effects and physiological effects of low [CO2], in modulating the atmospheric distribution of dust.

Reconstructing paleosalinity from δ18O: coupled model simulations of the Last Glacial Maximum, Last Interglacial and Late Holocene

Reconstructions of salinity are used to diagnose changes in the hydrological cycle and ocean circulation. A widely used method of determining past salinity uses oxygen isotope (δOw) residuals after the extraction of the global ice volume and temperature components. This method relies on a constant relationship between δOw and salinity throughout time. Here we use the isotope-enabled fully coupled General Circulation Model (GCM) HadCM3 to test the application of spatially and time-independent relationships in the reconstruction of past ocean salinity. Simulations of the Late Holocene (LH), Last Glacial Maximum (LGM), and Last Interglacial (LIG) climates are performed and benchmarked against existing compilations of stable oxygen isotopes in carbonates (δOc), which primarily reflect δOw and temperature. We find that HadCM3 produces an accurate representation of the surface ocean δOc distribution for the LH and LGM. Our simulations show considerable variability in spatial and temporal δOw-salinity relationships. Spatial gradients are generally shallower but within ∼50% of the actual simulated LH to LGM and LH to LIG temporal gradients and temporal gradients calculated from multi-decadal variability are generally shallower than both spatial and actual simulated gradients. The largest sources of uncertainty in salinity reconstructions are found to be caused by changes in regional freshwater budgets, ocean circulation, and sea ice regimes. These can cause errors in salinity estimates exceeding 4 psu. Our results suggest that paleosalinity reconstructions in the South Atlantic, Indian and Tropical Pacific Oceans should be most robust, since these regions exhibit relatively constant δOw-salinity relationships across spatial and temporal scales. Largest uncertainties will affect North Atlantic and high latitude paleosalinity reconstructions. Finally, the results show that it is difficult to generate reliable salinity estimates for regions of dynamic oceanography, such as the North Atlantic, without additional constraints.

Can climate trends be calculated from reanalysis data?

Several global quantities are computed from the ERA40 reanalysis for the period 1958-2001 and explored for trends. These are discussed in the context of changes to the global observing system. Temperature, integrated water vapor (IWV), and kinetic energy are considered. The ERA40 global mean temperature in the lower troposphere has a trend of +0.11 K per decade over the period of 1979-2001, which is slightly higher than the MSU measurements, but within the estimated error limit. For the period 1958 2001 the warming trend is 0.14 K per decade but this is likely to be an artifact of changes in the observing system. When this is corrected for, the warming trend is reduced to 0.10 K per decade. The global trend in IWV for the period 1979-2001 is +0.36 mm per decade. This is about twice as high as the trend determined from the Clausius-Clapeyron relation assuming conservation of relative humidity. It is also larger than results from free climate model integrations driven by the same observed sea surface temperature as used in ERA40. It is suggested that the large trend in IWV does not represent a genuine climate trend but an artifact caused by changes in the global observing system such as the use of SSM/I and more satellite soundings in later years. Recent results are in good agreement with GPS measurements. The IWV trend for the period 1958-2001 is still higher but reduced to +0.16 mm per decade when corrected for changes in the observing systems. Total kinetic energy shows an increasing global trend. Results from data assimilation experiments strongly suggest that this trend is also incorrect and mainly caused by the huge changes in the global observing system in 1979. When this is corrected for, no significant change in global kinetic energy from 1958 onward can be found.

Does reactive surface area depend on grain size? Results from pH 3, 25 circle C far-from-equilibrium flow-through dissolution experiments on anorthite and biotite

Laboratory determined mineral weathering rates need to be normalised to allow their extrapolation to natural systems. The principle normalisation terms used in the literature are mass, and geometric- and BET specific surface area (SSA). The purpose of this study was to determine how dissolution rates normalised to these terms vary with grain size. Different size fractions of anorthite and biotite ranging from 180-150 to 20-10 mu m were dissolved in pH 3, HCl at 25 degrees C in flow through reactors under far from equilibrium conditions. Steady state dissolution rates after 5376 h (anorthite) and 4992 h (biotite) were calculated from Si concentrations and were normalised to initial- and final- mass and geometric-, geometric edge- (biotite), and BET SSA. For anorthite, rates normalised to initial- and final-BET SSA ranged from 0.33 to 2.77 X 10(-10) mol(feldspar) m(-2) s(-1), rates normalised to initial- and final-geometric SSA ranged from 5.74 to 8.88 X 10(-10) mol(feldspar) m(-2) s(-1) and rates normalised to initial- and final-mass ranged from 0.11 to 1.65 mol(feldspar) g(-1) s(-1). For biotite, rates normalised to initial- and final-BET SSA ranged from 1.02 to 2.03 X 10(-12) mol(biotite) m(-2) s(-1), rates normalised to initial- and final-geometric SSA ranged from 3.26 to 16.21 X 10(-12) mol(biotite) m(-2) s(-1), rates normalised to initial- and final-geometric edge SSA ranged from 59.46 to 111.32 x 10(-12) mol(biotite) m(-2) s(-1) and rates normalised to initial- and final-mass ranged from 0.81 to 6.93 X 10(-12) mol(biotite) g(-1) s(-1). For all normalising terms rates varied significantly (p <= 0.05) with grain size. The normalising terms which gave least variation in dissolution rate between grain sizes for anorthite were initial BET SSA and initial- and final-geometric SSA. This is consistent with: (1) dissolution being dominated by the slower dissolving but area dominant non-etched surfaces of the grains and, (2) the walls of etch pits and other dissolution features being relatively unreactive. These steady state normalised dissolution rates are likely to be constant with time. Normalisation to final BET SSA did not give constant ratios across grain size due to a non-uniform distribution of dissolution features. After dissolution coarser grains had a greater density of dissolution features with BET-measurable but unreactive wall surface area than the finer grains. The normalising term which gave the least variation in dissolution rates between grain sizes for biotite was initial BET SSA. Initial- and final-geometric edge SSA and final BET SSA gave the next least varied rates. The basal surfaces dissolved sufficiently rapidly to influence bulk dissolution rate and prevent geometric edge SSA normalised dissolution rates showing the least variation. Simple modelling indicated that biotite grain edges dissolved 71-132 times faster than basal surfaces. In this experiment, initial BET SSA best integrated the different areas and reactivities of the edge and basal surfaces of biotite. Steady state dissolution rates are likely to vary with time as dissolution alters the ratio of edge to basal surface area. Therefore they would be more properly termed pseudo-steady state rates, only appearing constant because the time period over which they were measured (1512 h) was less than the time period over wich they would change significantly. (c) 2006 Elsevier Inc. All rights reserved.

The influence of the carbon surface chemical composition on Dubinin-Astakhov equation parameters calculated from SF(6) adsorption data-grand canonical Monte Carlo simulation

Using grand canonical Monte Carlo simulation we show, for the first time, the influence of the carbon porosity and surface oxidation on the parameters of the Dubinin-Astakhov (DA) adsorption isotherm equation. We conclude that upon carbon surface oxidation, the adsorption decreases for all carbons studied. Moreover, the parameters of the DA model depend on the number of surface oxygen groups. That is why in the case of carbons containing surface polar groups, SF(6) adsorption isotherm data cannot be used for characterization of the porosity.

European storminess and associated circulation weather types: future changes deduced from a multi-model ensemble of GCM simulations

A range of possible changes in the frequency and characteristics of European wind storms under future climate conditions was investigated on the basis of a multi-model ensemble of 9 coupled global climate model (GCM) simulations for the 20th and 21st centuries following the IPCC SRES A1B scenario. A multi-model approach allowed an estimation of the (un)certainties of the climate change signals. General changes in large-scale atmospheric flow were analysed, the occurrence of wind storms was quantified, and atmospheric features associated with wind storm events were considered. Identified storm days were investigated according to atmospheric circulation, associated pressure patterns, cyclone tracks and wind speed patterns. Validation against reanalysis data revealed that the GCMs are in general capable of realistically reproducing characteristics of European circulation weather types (CWTs) and wind storms. Results are given with respect to frequency of occurrence, storm-associated flow conditions, cyclone tracks and specific wind speed patterns. Under anthropogenic climate change conditions (SRES A1B scenario), increased frequency of westerly flow during winter is detected over the central European investigation area. In the ensemble mean, the number of detected wind storm days increases between 19 and 33% for 2 different measures of storminess, only 1 GCM revealed less storm days. The increased number of storm days detected in most models is disproportionately high compared to the related CWT changes. The mean intensity of cyclones associated with storm days in the ensemble mean increases by about 10 (±10)% in the Eastern Atlantic, near the British Isles and in the North Sea. Accordingly, wind speeds associated with storm events increase significantly by about 5 (±5)% over large parts of central Europe, mainly on days with westerly flow. The basic conclusions of this work remain valid if different ensemble contructions are considered, leaving out an outlier model or including multiple runs of one particular model.

Impact of atmospheric forcing data on simulations of the Laptev Sea polynya dynamics using the sea-ice ocean model FESOM

The polynyas of the Laptev Sea are regions of particular interest due to the strong formation of Arctic sea-ice. In order to simulate the polynya dynamics and to quantify ice production, we apply the Finite Element Sea-Ice Ocean Model FESOM. In previous simulations FESOM has been forced with daily atmospheric NCEP (National Centers for Environmental Prediction) 1. For the periods 1 April to 9 May 2008 and 1 January to 8 February 2009 we examine the impact of different forcing data: daily and 6-hourly NCEP reanalyses 1 (1.875° x 1.875°), 6-hourly NCEP reanalyses 2 (1.875° x 1.875°), 6-hourly analyses from the GME (Global Model of the German Weather Service) (0.5° x 0.5°) and high-resolution hourly COSMO (Consortium for Small-Scale Modeling) data (5 km x 5 km). In all FESOM simulations, except for those with 6-hourly and daily NCEP 1 data, the openings and closings of polynyas are simulated in principle agreement with satellite products. Over the fast-ice area the wind fields of all atmospheric data are similar and close to in situ measurements. Over the polynya areas, however, there are strong differences between the forcing data with respect to air temperature and turbulent heat flux. These differences have a strong impact on sea-ice production rates. Depending on the forcing fields polynya ice production ranges from 1.4 km3 to 7.8 km3 during 1 April to 9 May 2011 and from 25.7 km3 to 66.2 km3 during 1 January to 8 February 2009. Therefore, atmospheric forcing data with high spatial and temporal resolution which account for the presence of the polynyas are needed to reduce the uncertainty in quantifying ice production in polynyas.

Inertia-Gravity Waves Emitted from Balanced Flow: Observations, Properties, and Consequences

This paper describes laboratory observations of inertia–gravity waves emitted from balanced fluid flow. In a rotating two-layer annulus experiment, the wavelength of the inertia–gravity waves is very close to the deformation radius. Their amplitude varies linearly with Rossby number in the range 0.05–0.14, at constant Burger number (or rotational Froude number). This linear scaling challenges the notion, suggested by several dynamical theories, that inertia–gravity waves generated by balanced motion will be exponentially small. It is estimated that the balanced flow leaks roughly 1% of its energy each rotation period into the inertia–gravity waves at the peak of their generation. The findings of this study imply an inevitable emission of inertia–gravity waves at Rossby numbers similar to those of the large-scale atmospheric and oceanic flow. Extrapolation of the results suggests that inertia–gravity waves might make a significant contribution to the energy budgets of the atmosphere and ocean. In particular, emission of inertia–gravity waves from mesoscale eddies may be an important source of energy for deep interior mixing in the ocean.

ENSO at 6ka and 21ka from ocean–atmosphere coupled model simulations

We analyze how the characteristics of El Niño-Southern Oscillation (ENSO) are changed in coupled ocean–atmosphere simulations of the mid-Holocene (MH) and the Last Glacial Maximum (LGM) performed as part of the Paleoclimate Modeling Intercomparison Project phase 2 (PMIP2). Comparison of the model results with present day observations show that most of the models reproduce the large scale features of the tropical Pacific like the SST gradient, the mean SST and the mean seasonal cycles. All models simulate the ENSO variability, although with different skill. Our analyses show that several relationships between El Niño amplitude and the mean state across the different control simulations are still valid for simulations of the MH and the LGM. Results for the MH show a consistent El Niño amplitude decrease. It can be related to the large scale atmospheric circulation changes. While the Northern Hemisphere receives more insolation during the summer time, the Asian summer monsoon system is strengthened which leads to the enhancement of the Walker circulation. Easterlies prevailing over the central eastern Pacific induce an equatorial upwelling that damps the El Niño development. Results are less conclusive for 21ka. Large scale dynamic competes with changes in local heat fluxes, so that model shows a wide range of responses, as it is the case in future climate projections.

The impact of livestock assets among indigenous communities: findings from a comparative model in Bolivia

Measuring poverty has occupied a lot of space in the development discourse. Over the years a number of approaches have been offered to capture the experience of what it means to be poor. However, latterly such approaches often ignore core assets. Indeed, the comparative impact of livestock vs. other core assets such as land and education on poverty has not been well explored. Therefore, the authors created an 'asset impact model' to examine changes to both tangible and intangible assets at the household level, with a particular focus on gender and ethnicity among communities residing in the Bolivian Altiplano. The simple model illustrates that for indigenous women, a 20 per cent increase in the livestock herd has the same impact on household income as increasing the education levels by 20 per cent and household land ownership by 5 per cent. The study illustrates the potential role of a productive, tangible asset, i.e. livestock, on poverty reduction in the short term. The policy implications of supporting asset-focused measures of poverty are discussed.