Testing isotherm models and recovering empirical relationships for adsorption in microporous carbons using virtual carbon models and grand canonical Monte Carlo simulations

Using the plausible model of activated carbon proposed by Harris and co-workers and grand canonical Monte Carlo simulations, we study the applicability of standard methods for describing adsorption data on microporous carbons widely used in adsorption science. Two carbon structures are studied, one with a small distribution of micropores in the range up to 1 nm, and the other with micropores covering a wide range of porosity. For both structures, adsorption isotherms of noble gases (from Ne to Xe), carbon tetrachloride and benzene are simulated. The data obtained are considered in terms of Dubinin-Radushkevich plots. Moreover, for benzene and carbon tetrachloride the temperature invariance of the characteristic curve is also studied. We show that using simulated data some empirical relationships obtained from experiment can be successfully recovered. Next we test the applicability of Dubinin's related models including the Dubinin-Izotova, Dubinin-Radushkevich-Stoeckli, and Jaroniec-Choma equations. The results obtained demonstrate the limits and applications of the models studied in the field of carbon porosity characterization.

Hyper-parallel tempering Monte Carlo simulations of Ar adsorption in new models of microporous non-graphitizing activated carbon: effect of microporosity

The adsorption of gases on microporous carbons is still poorly understood, partly because the structure of these carbons is not well known. Here, a model of microporous carbons based on fullerene- like fragments is used as the basis for a theoretical study of Ar adsorption on carbon. First, a simulation box was constructed, containing a plausible arrangement of carbon fragments. Next, using a new Monte Carlo simulation algorithm, two types of carbon fragments were gradually placed into the initial structure to increase its microporosity. Thirty six different microporous carbon structures were generated in this way. Using the method proposed recently by Bhattacharya and Gubbins ( BG), the micropore size distributions of the obtained carbon models and the average micropore diameters were calculated. For ten chosen structures, Ar adsorption isotherms ( 87 K) were simulated via the hyper- parallel tempering Monte Carlo simulation method. The isotherms obtained in this way were described by widely applied methods of microporous carbon characterisation, i. e. Nguyen and Do, Horvath - Kawazoe, high- resolution alpha(a)s plots, adsorption potential distributions and the Dubinin - Astakhov ( DA) equation. From simulated isotherms described by the DA equation, the average micropore diameters were calculated using empirical relationships proposed by different authors and they were compared with those from the BG method.

A study of the arrival over the United Kingdom in April 2010 of the Eyjafjallajökull ash cloud using ground-based lidar and numerical simulations

We make a qualitative and quantitative comparison of numericalsimulations of the ashcloud generated by the eruption of Eyjafjallajökull in April2010 with ground-basedlidar measurements at Exeter and Cardington in southern England. The numericalsimulations are performed using the Met Office’s dispersion model, NAME (Numerical Atmospheric-dispersion Modelling Environment). The results show that NAME captures many of the features of the observed ashcloud. The comparison enables us to estimate the fraction of material which survives the near-source fallout processes and enters into the distal plume. A number of simulations are performed which show that both the structure of the ashcloudover southern England and the concentration of ash within it are particularly sensitive to the height of the eruption column (and the consequent estimated mass emission rate), to the shape of the vertical source profile and the level of prescribed ‘turbulent diffusion’ (representing the mixing by the unresolved eddies) in the free troposphere with less sensitivity to the timing of the start of the eruption and the sedimentation of particulates in the distal plume.

Implementation of a new urban energy budget scheme in the MetUM. Part I: Description and idealized simulations

This paper describes the formulation of a new urban scheme, MORUSES (Met Office–Reading Urban Surface Exchange Scheme) for use in the Met Office Unified Model. The implementation of the new scheme ensures that (1) the new scheme offers more flexibility in the parametrization of the building properties, and hence provides a more realistic representation of the fluxes; (2) the bulk outputs are in satisfactory agreement with previous observational studies; and (3) the impact of the new scheme on the energy balance fluxes is similar to the impact of the current urban scheme when set up to mimic it. As well as having a better physical basis, MORUSES also gains in flexibility in applications and adaptations to different urban materials as well as urban planning. The new scheme represents the urban area as a composition of two tiles, a canyon and a roof, using a simple 2D geometry. Sensitivity analysis to canyon geometry and thickness of the roof canopy emphasizes the gain in flexibility captured by the new scheme. Copyright © 2010 Royal Meteorological Society and Crown Copyright

Hydrological cycle in the Danube basin in present-day and XXII century simulations by IPCCAR4 global climate models

We present an intercomparison and verification analysis of 20 GCMs (Global Circulation Models) included in the 4th IPCC assessment report regarding their representation of the hydrological cycle on the Danube river basin for 1961–2000 and for the 2161–2200 SRESA1B scenario runs. The basin-scale properties of the hydrological cycle are computed by spatially integrating the precipitation, evaporation, and runoff fields using the Voronoi-Thiessen tessellation formalism. The span of the model- simulated mean annual water balances is of the same order of magnitude of the observed Danube discharge of the Delta; the true value is within the range simulated by the models. Some land components seem to have deficiencies since there are cases of violation of water conservation when annual means are considered. The overall performance and the degree of agreement of the GCMs are comparable to those of the RCMs (Regional Climate Models) analyzed in a previous work, in spite of the much higher resolution and common nesting of the RCMs. The reanalyses are shown to feature several inconsistencies and cannot be used as a verification benchmark for the hydrological cycle in the Danubian region. In the scenario runs, for basically all models the water balance decreases, whereas its interannual variability increases. Changes in the strength of the hydrological cycle are not consistent among models: it is confirmed that capturing the impact of climate change on the hydrological cycle is not an easy task over land areas. Moreover, in several cases we find that qualitatively different behaviors emerge among the models: the ensemble mean does not represent any sort of average model, and often it falls between the models’ clusters.

High-resolution global climate simulations with the ECMWF model in Project Athena: experimental design, model climate, and seasonal forecast skill

The sensitivity to the horizontal resolution of the climate, anthropogenic climate change, and seasonal predictive skill of the ECMWF model has been studied as part of Project Athena—an international collaboration formed to test the hypothesis that substantial progress in simulating and predicting climate can be achieved if mesoscale and subsynoptic atmospheric phenomena are more realistically represented in climate models. In this study the experiments carried out with the ECMWF model (atmosphere only) are described in detail. Here, the focus is on the tropics and the Northern Hemisphere extratropics during boreal winter. The resolutions considered in Project Athena for the ECMWF model are T159 (126 km), T511 (39 km), T1279 (16 km), and T2047 (10 km). It was found that increasing horizontal resolution improves the tropical precipitation, the tropical atmospheric circulation, the frequency of occurrence of Euro-Atlantic blocking, and the representation of extratropical cyclones in large parts of the Northern Hemisphere extratropics. All of these improvements come from the increase in resolution from T159 to T511 with relatively small changes for further resolution increases to T1279 and T2047, although it should be noted that results from this very highest resolution are from a previously untested model version. Problems in simulating the Madden–Julian oscillation remain unchanged for all resolutions tested. There is some evidence that increasing horizontal resolution to T1279 leads to moderate increases in seasonal forecast skill during boreal winter in the tropics and Northern Hemisphere extratropics. Sensitivity experiments are discussed, which helps to foster a better understanding of some of the resolution dependence found for the ECMWF model in Project Athena

The role of northern Arabian Sea surface temperature biases in CMIP5 model simulations and future projections of Indian summer monsoon rainfall

Many climate models have problems simulating Indian summer monsoon rainfall and its variability, resulting in considerable uncertainty in future projections. Problems may relate to many factors, such as local effects of the formulation of physical parametrisation schemes, while common model biases that develop elsewhere within the climate system may also be important. Here we examine the extent and impact of cold sea surface temperature (SST) biases developing in the northern Arabian Sea in the CMIP5 multi-model ensemble, where such SST biases are shown to be common. Such biases have previously been shown to reduce monsoon rainfall in the Met Office Unified Model (MetUM) by weakening moisture fluxes incident upon India. The Arabian Sea SST biases in CMIP5 models consistently develop in winter, via strengthening of the winter monsoon circulation, and persist into spring and summer. A clear relationship exists between Arabian Sea cold SST bias and weak monsoon rainfall in CMIP5 models, similar to effects in the MetUM. Part of this effect may also relate to other factors, such as forcing of the early monsoon by spring-time excessive equatorial precipitation. Atmosphere-only future time-slice experiments show that Arabian Sea cold SST biases have potential to weaken future monsoon rainfall increases by limiting moisture flux acceleration through non-linearity of the Clausius-Clapeyron relationship. Analysis of CMIP5 model future scenario simulations suggests that, while such effects are likely small compared to other sources of uncertainty, models with large Arabian Sea cold SST biases suppress the range of potential outcomes for changes to future early monsoon rainfall.

Aerosol forcing in the Climate Model Intercomparison Project (CMIP5) simulations by HadGEM2-ES and the role of ammonium nitrate

The latest Hadley Centre climate model, HadGEM2-ES, includes Earth system components such as interactive chemistry and eight species of tropospheric aerosols. It has been run for the period 1860–2100 in support of the fifth phase of the Climate Model Intercomparison Project (CMIP5). Anthropogenic aerosol emissions peak between 1980 and 2020, resulting in a present-day all-sky top of the atmosphere aerosol forcing of −1.6 and −1.4 W m−2 with and without ammonium nitrate aerosols, respectively, for the sum of direct and first indirect aerosol forcings. Aerosol forcing becomes significantly weaker in the 21st century, being weaker than −0.5 W m−2 in 2100 without nitrate. However, nitrate aerosols become the dominant species in Europe and Asia and decelerate the decrease in global mean aerosol forcing. Considering nitrate aerosols makes aerosol radiative forcing 2–4 times stronger by 2100 depending on the representative concentration pathway, although this impact is lessened when changes in the oxidation properties of the atmosphere are accounted for. Anthropogenic aerosol residence times increase in the future in spite of increased precipitation, as cloud cover and aerosol-cloud interactions decrease in tropical and midlatitude regions. Deposition of fossil fuel black carbon onto snow and ice surfaces peaks during the 20th century in the Arctic and Europe but keeps increasing in the Himalayas until the middle of the 21st century. Results presented here confirm the importance of aerosols in influencing the Earth's climate, albeit with a reduced impact in the future, and suggest that nitrate aerosols will partially replace sulphate aerosols to become an important anthropogenic species in the remainder of the 21st century.

Ozone database in support of CMIP5 simulations: results and corresponding radiative forcing

A continuous tropospheric and stratospheric vertically resolved ozone time series, from 1850 to 2099, has been generated to be used as forcing in global climate models that do not include interactive chemistry. A multiple linear regression analysis of SAGE I+II satellite observations and polar ozonesonde measurements is used for the stratospheric zonal mean dataset during the well-observed period from 1979 to 2009. In addition to terms describing the mean annual cycle, the regression includes terms representing equivalent effective stratospheric chlorine (EESC) and the 11-yr solar cycle variability. The EESC regression fit coefficients, together with pre-1979 EESC values, are used to extrapolate the stratospheric ozone time series backward to 1850. While a similar procedure could be used to extrapolate into the future, coupled chemistry climate model (CCM) simulations indicate that future stratospheric ozone abundances are likely to be significantly affected by climate change, and capturing such effects through a regression model approach is not feasible. Therefore, the stratospheric ozone dataset is extended into the future (merged in 2009) with multimodel mean projections from 13 CCMs that performed a simulation until 2099 under the SRES (Special Report on Emission Scenarios) A1B greenhouse gas scenario and the A1 adjusted halogen scenario in the second round of the Chemistry-Climate Model Validation (CCMVal-2) Activity. The stratospheric zonal mean ozone time series is merged with a three-dimensional tropospheric data set extracted from simulations of the past by two CCMs (CAM3.5 and GISSPUCCINI)and of the future by one CCM (CAM3.5). The future tropospheric ozone time series continues the historical CAM3.5 simulation until 2099 following the four different Representative Concentration Pathways (RCPs). Generally good agreement is found between the historical segment of the ozone database and satellite observations, although it should be noted that total column ozone is overestimated in the southern polar latitudes during spring and tropospheric column ozone is slightly underestimated. Vertical profiles of tropospheric ozone are broadly consistent with ozonesondes and in-situ measurements, with some deviations in regions of biomass burning. The tropospheric ozone radiative forcing (RF) from the 1850s to the 2000s is 0.23Wm−2, lower than previous results. The lower value is mainly due to (i) a smaller increase in biomass burning emissions; (ii) a larger influence of stratospheric ozone depletion on upper tropospheric ozone at high southern latitudes; and possibly (iii) a larger influence of clouds (which act to reduce the net forcing) compared to previous radiative forcing calculations. Over the same period, decreases in stratospheric ozone, mainly at high latitudes, produce a RF of −0.08Wm−2, which is more negative than the central Intergovernmental Panel on Climate Change (IPCC) Fourth Assessment Report (AR4) value of −0.05Wm−2, but which is within the stated range of −0.15 to +0.05Wm−2. The more negative value is explained by the fact that the regression model simulates significant ozone depletion prior to 1979, in line with the increase in EESC and as confirmed by CCMs, while the AR4 assumed no change in stratospheric RF prior to 1979. A negative RF of similar magnitude persists into the future, although its location shifts from high latitudes to the tropics. This shift is due to increases in polar stratospheric ozone, but decreases in tropical lower stratospheric ozone, related to a strengthening of the Brewer-Dobson circulation, particularly through the latter half of the 21st century. Differences in trends in tropospheric ozone among the four RCPs are mainly driven by different methane concentrations, resulting in a range of tropospheric ozone RFs between 0.4 and 0.1Wm−2 by 2100. The ozone dataset described here has been released for the Coupled Model Intercomparison Project (CMIP5) model simulations in netCDF Climate and Forecast (CF) Metadata Convention at the PCMDI website (http://cmip-pcmdi.llnl.gov/).

The variable link between PNA and NAO in observations and in multi-century CGCM simulations

The link between the Pacific/North American pattern (PNA) and the North Atlantic Oscillation (NAO) is investigated in reanalysis data (NCEP, ERA40) and multi-century CGCM runs for present day climate using three versions of the ECHAM model. PNA and NAO patterns and indices are determined via rotated principal component analysis on monthly mean 500 hPa geopotential height fields using the varimax criteria. On average, the multi-century CGCM simulations show a significant anti-correlation between PNA and NAO. Further, multi-decadal periods with significantly enhanced (high anti-correlation, active phase) or weakened (low correlations, inactive phase) coupling are found in all CGCMs. In the simulated active phases, the storm track activity near Newfoundland has a stronger link with the PNA variability than during the inactive phases. On average, the reanalysis datasets show no significant anti-correlation between PNA and NAO indices, but during the sub-period 1973–1994 a significant anti-correlation is detected, suggesting that the present climate could correspond to an inactive period as detected in the CGCMs. An analysis of possible physical mechanisms suggests that the link between the patterns is established by the baroclinic waves forming the North Atlantic storm track. The geopotential height anomalies associated with negative PNA phases induce an increased advection of warm and moist air from the Gulf of Mexico and cold air from Canada. Both types of advection contribute to increase baroclinicity over eastern North America and also to increase the low level latent heat content of the warm air masses. Thus, growth conditions for eddies at the entrance of the North Atlantic storm track are enhanced. Considering the average temporal development during winter for the CGCM, results show an enhanced Newfoundland storm track maximum in the early winter for negative PNA, followed by a downstream enhancement of the Atlantic storm track in the subsequent months. In active (passive) phases, this seasonal development is enhanced (suppressed). As the storm track over the central and eastern Atlantic is closely related to the NAO variability, this development can be explained by the shift of the NAO index to more positive values.

Statistical uncertainty of changes in winter storms over the North Atlantic and Europe in an ensemble of transient climate simulations

Winter storms are among the most important natural hazards affecting Europe. We quantify changes in storm frequency and intensity over the North Atlantic and Europe under future climate scenarios in terms of return periods (RPs) considering uncertainties due to both sampling and methodology. RPs of North Atlantic storms' minimum central pressure (CP) and maximum vorticity (VOR) remain unchanged by 2100 for both the A1B and A2 scenarios compared to the present climate. Whereas shortened RPs for VOR of all intensities are detected for the area between British Isles/North-Sea/western Europe as early as 2040. However, the changes in storm VOR RP may be unrealistically large: a present day 50 (20) year event becomes approximately a 9 (5.5) year event in both A1B and A2 scenarios by 2100. The detected shortened RPs of storms implies a higher risk of occurrence of damaging wind events over Europe.

Changing Northern Hemisphere storm tracks in an ensemble of IPCC climate change simulations

Winter storm-track activity over the Northern Hemisphere and its changes in a greenhouse gas scenario (the Special Report on Emission Scenarios A1B forcing) are computed from an ensemble of 23 single runs from 16 coupled global climate models (CGCMs). All models reproduce the general structures of the observed climatological storm-track pattern under present-day forcing conditions. Ensemble mean changes resulting from anthropogenic forcing include an increase of baroclinic wave activity over the eastern North Atlantic, amounting to 5%–8% by the end of the twenty-first century. Enhanced activity is also found over the Asian continent and over the North Pacific near the Aleutian Islands. At high latitudes and over parts of the subtropics, activity is reduced. Variations of the individual models around the ensemble average signal are not small, with a median of the pattern correlation near r = 0.5. There is, however, no evidence for a link between deviations in present-day climatology and deviations with respect to climate change.

Precipitation scaling with temperature in warm and cold climates: an analysis of CMIP5 simulations

We investigate the scaling between precipitation and temperature changes in warm and cold climates using six models that have simulated the response to both increased CO2 and Last Glacial Maximum (LGM) boundary conditions. Globally, precipitation increases in warm climates and decreases in cold climates by between 1.5%/°C and 3%/°C. Precipitation sensitivity to temperature changes is lower over the land than over the ocean and lower over the tropical land than over the extratropical land, reflecting the constraint of water availability. The wet tropics get wetter in warm climates and drier in cold climates, but the changes in dry areas differ among models. Seasonal changes of tropical precipitation in a warmer world also reflect this “rich get richer” syndrome. Precipitation seasonality is decreased in the cold-climate state. The simulated changes in precipitation per degree temperature change are comparable to the observed changes in both the historical period and the LGM.