119 resultados para models for the sp³ carbon atom


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Attempts to reduce the energy consumed in UK homes have met with limited success. One reason for this is a lack of understanding of how people interact with domestic technology – heating systems, lights, electrical equipment and so forth. Attaining such an understanding is hampered by a chronic shortage of detailed energy use data matched to descriptions of the house, the occupants, the internal conditions and the installed services and appliances. Without such information it is impossible to produce transparent and valid models for understanding and predicting energy use. The Carbon Reduction in Buildings (CaRB) consortium of five UK universities plans to develop socio-technical models of energy use, underpinned by a flow of data from a longitudinal monitoring campaign involving several hundred UK homes. This paper outlines the models proposed, the preliminary monitoring work and the structure of the proposed longitudinal study.

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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.

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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.

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Microporous carbons are important in a wide variety of applications, ranging from pollution control to supercapacitors, yet their structure at the molecular level is poorly understood. Over the years, many structural models have been put forward, but none have been entirely satisfactory in explaining the properties of the carbons. The discovery of fullerenes and fullerene-related structures such as carbon nanotubes gave us a new perspective on the structure of solid carbon, and in 1997 it was suggested that microporous carbon may have a structure related to that of the fullerenes. Recently, evidence in support of such a structure has been obtained using aberration-corrected transmission electron microscopy, electron energy loss spectroscopy and other techniques. This article describes the development of ideas about the structure of microporous carbon, and reviews the experimental evidence for a fullerene-related structure. Theoretical models of the structural evolution of microporous carbon are summarised, and the use of fullerene-like models to predict the adsorptive properties of microporous carbons are reviewed.

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Different models for the electronic structure of carbon monoxide are suggested in influential textbooks. Therefore, this electronic structure offers an interesting subject in teaching because it can be used as an example to relate seemingly conflicting concepts. Understanding the connections between ostensibly different methods and between different concepts, related or conflicting, is important in academic studies. The related reactivities of CO, O2, and N-2 and the notations of molecular orbitals are topics of interest and are discussed in detail.

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Earth system models are increasing in complexity and incorporating more processes than their predecessors, making them important tools for studying the global carbon cycle. However, their coupled behaviour has only recently been examined in any detail, and has yielded a very wide range of outcomes, with coupled climate-carbon cycle models that represent land-use change simulating total land carbon stores by 2100 that vary by as much as 600 Pg C given the same emissions scenario. This large uncertainty is associated with differences in how key processes are simulated in different models, and illustrates the necessity of determining which models are most realistic using rigorous model evaluation methodologies. Here we assess the state-of-the-art with respect to evaluation of Earth system models, with a particular emphasis on the simulation of the carbon cycle and associated biospheric processes. We examine some of the new advances and remaining uncertainties relating to (i) modern and palaeo data and (ii) metrics for evaluation, and discuss a range of strategies, such as the inclusion of pre-calibration, combined process- and system-level evaluation, and the use of emergent constraints, that can contribute towards the development of more robust evaluation schemes. An increasingly data-rich environment offers more opportunities for model evaluation, but it is also a challenge, as more knowledge about data uncertainties is required in order to determine robust evaluation methodologies that move the field of ESM evaluation from "beauty contest" toward the development of useful constraints on model behaviour.

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Scattering and absorption by aerosol in anthropogenically perturbed air masses over Europe has been measured using instrumentation flown on the UK’s BAe-146-301 large Atmospheric Research Aircraft (ARA) operated by the Facility for Airborne Atmospheric Measurements (FAAM) on 14 flights during the EUCAARI-LONGREX campaign in May 2008. The geographical and temporal variations of the derived shortwave optical properties of aerosol are presented. Values of single scattering albedo of dry aerosol at 550 nm varied considerably from 0.86 to near unity, with a campaign average of 0.93 ± 0.03. Dry aerosol optical depths ranged from 0.030 ± 0.009 to 0.24 ± 0.07. An optical properties closure study comparing calculations from composition data and Mie scattering code with the measured properties is presented. Agreement to within measurement uncertainties of 30% can be achieved for both scattering and absorption,but the latter is shown to be sensitive to the refractive indices chosen for organic aerosols, and to a lesser extent black carbon, as well as being highly dependent on the accuracy of the absorption measurements. Agreement with the measured absorption can be achieved either if organic carbon is assumed to be weakly absorbing, or if the organic aerosol is purely scattering and the absorption measurement is an overestimate due to the presence of large amounts of organic carbon. Refractive indices could not be inferred conclusively due to this uncertainty, despite the enhancement in methodology compared to previous studies that derived from the use of the black carbon measurements. Hygroscopic growth curves derived from the wet nephelometer indicate moderate water uptake by the aerosol with a campaign mean f (RH) value (ratio in scattering) of 1.5 (range from 1.23 to 1.63) at 80% relative humidity. This value is qualitatively consistent with the major chemical components of the aerosol measured by the aerosol mass spectrometer, which are primarily mixed organics and nitrate and some sulphate.

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This paper evaluates the current status of global modeling of the organic aerosol (OA) in the troposphere and analyzes the differences between models as well as between models and observations. Thirty-one global chemistry transport models (CTMs) and general circulation models (GCMs) have participated in this intercomparison, in the framework of AeroCom phase II. The simulation of OA varies greatly between models in terms of the magnitude of primary emissions, secondary OA (SOA) formation, the number of OA species used (2 to 62), the complexity of OA parameterizations (gas-particle partitioning, chemical aging, multiphase chemistry, aerosol microphysics), and the OA physical, chemical and optical properties. The diversity of the global OA simulation results has increased since earlier AeroCom experiments, mainly due to the increasing complexity of the SOA parameterization in models, and the implementation of new, highly uncertain, OA sources. Diversity of over one order of magnitude exists in the modeled vertical distribution of OA concentrations that deserves a dedicated future study. Furthermore, although the OA / OC ratio depends on OA sources and atmospheric processing, and is important for model evaluation against OA and OC observations, it is resolved only by a few global models. The median global primary OA (POA) source strength is 56 Tg a−1 (range 34–144 Tg a−1) and the median SOA source strength (natural and anthropogenic) is 19 Tg a−1 (range 13–121 Tg a−1). Among the models that take into account the semi-volatile SOA nature, the median source is calculated to be 51 Tg a−1 (range 16–121 Tg a−1), much larger than the median value of the models that calculate SOA in a more simplistic way (19 Tg a−1; range 13–20 Tg a−1, with one model at 37 Tg a−1). The median atmospheric burden of OA is 1.4 Tg (24 models in the range of 0.6–2.0 Tg and 4 between 2.0 and 3.8 Tg), with a median OA lifetime of 5.4 days (range 3.8–9.6 days). In models that reported both OA and sulfate burdens, the median value of the OA/sulfate burden ratio is calculated to be 0.77; 13 models calculate a ratio lower than 1, and 9 models higher than 1. For 26 models that reported OA deposition fluxes, the median wet removal is 70 Tg a−1 (range 28–209 Tg a−1), which is on average 85% of the total OA deposition. Fine aerosol organic carbon (OC) and OA observations from continuous monitoring networks and individual field campaigns have been used for model evaluation. At urban locations, the model–observation comparison indicates missing knowledge on anthropogenic OA sources, both strength and seasonality. The combined model–measurements analysis suggests the existence of increased OA levels during summer due to biogenic SOA formation over large areas of the USA that can be of the same order of magnitude as the POA, even at urban locations, and contribute to the measured urban seasonal pattern. Global models are able to simulate the high secondary character of OA observed in the atmosphere as a result of SOA formation and POA aging, although the amount of OA present in the atmosphere remains largely underestimated, with a mean normalized bias (MNB) equal to −0.62 (−0.51) based on the comparison against OC (OA) urban data of all models at the surface, −0.15 (+0.51) when compared with remote measurements, and −0.30 for marine locations with OC data. The mean temporal correlations across all stations are low when compared with OC (OA) measurements: 0.47 (0.52) for urban stations, 0.39 (0.37) for remote stations, and 0.25 for marine stations with OC data. The combination of high (negative) MNB and higher correlation at urban stations when compared with the low MNB and lower correlation at remote sites suggests that knowledge about the processes that govern aerosol processing, transport and removal, on top of their sources, is important at the remote stations. There is no clear change in model skill with increasing model complexity with regard to OC or OA mass concentration. However, the complexity is needed in models in order to distinguish between anthropogenic and natural OA as needed for climate mitigation, and to calculate the impact of OA on climate accurately.

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Preferred structures in the surface pressure variability are investigated in and compared between two 100-year simulations of the Hadley Centre climate model HadCM3. In the first (control) simulation, the model is forced with pre-industrial carbon dioxide concentration (1×CO2) and in the second simulation the model is forced with doubled CO2 concentration (2×CO2). Daily winter (December-January-February) surface pressures over the Northern Hemisphere are analysed. The identification of preferred patterns is addressed using multivariate mixture models. For the control simulation, two significant flow regimes are obtained at 5% and 2.5% significance levels within the state space spanned by the leading two principal components. They show a high pressure centre over the North Pacific/Aleutian Islands associated with a low pressure centre over the North Atlantic, and its reverse. For the 2×CO2 simulation, no such behaviour is obtained. At higher-dimensional state space, flow patterns are obtained from both simulations. They are found to be significant at the 1% level for the control simulation and at the 2.5% level for the 2×CO2 simulation. Hence under CO2 doubling, regime behaviour in the large-scale wave dynamics weakens. Doubling greenhouse gas concentration affects both the frequency of occurrence of regimes and also the pattern structures. The less frequent regime becomes amplified and the more frequent regime weakens. The largest change is observed over the Pacific where a significant deepening of the Aleutian low is obtained under CO2 doubling.

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Our understanding of the ancient ocean-atmosphere system has focused on oceanic proxies. However, the study of terrestrial proxies is equally necessary to constrain our understanding of ancient climates and linkages between the terrestrial and oceanic carbon reservoirs. We have analyzed carbon-isotope ratios from fossil plant material through the Valanginian and Lower Hauterivian from a shallow-marine, ammonite-constrained succession in the Crimean Peninsula of the southern Ukraine in order to determine if the Upper Valanginian positive carbon-isotope excursion is expressed in the atmosphere. delta(13)C(plant) values fluctuate around -23% to -22% for the Valanginian-Hauterivian, except during the Upper Valanginian where delta(13)C(plant) values record a positive excursion to similar to-18%. Based upon ammonite biostratigraphy from Crimea, and in conjunction with a composite Tethyan marine delta(13)C(carb) curve, several conclusions can be drawn: (1) the delta(13)C(plant) record indicates that the atmospheric carbon reservoir was affected; (2) the defined ammonite correlations between Europe and Crimea are synchronous; and (3) a change in photosynthetic carbon-isotope fractionation, caused by a decrease in atmospheric PCO2, occurred during the Upper Valanginian Positive delta(13)C excursion. Our new data, combined with other paleoenvironmental and paleoclimatic information, indicate that the Upper Valanginian was a cool period (icehouse) and highlights that the Cretaceous period was interrupted by periods of cooling and was not an equable climate as previously thought. (C) 2005 Elsevier B.V. All rights reserved.

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Several studies using ocean-atmosphere GCMs suggest that the atmospheric component plays a dominant role in the modelled ENSO. To help elucidate these findings, the two main atmosphere feedbacks relevant to ENSO, the Bjerknes positive feedback (µ) and the heat flux negative feedback (), are analysed here in 12 coupled GCMs. We find that the models generally underestimate both feedbacks, leading to an error compensation. The strength of is inversely related to the ENSO amplitude in the models and the latent heat and shortwave flux components of this feedback dominate. Furthermore, the shortwave component could help explain the model diversity in both overall and ENSO amplitude.

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Perturbations to the carbon cycle could constitute large feedbacks on future changes in atmospheric CO2 concentration and climate. This paper demonstrates how carbon cycle feedback can be expressed in formally similar ways to climate feedback, and thus compares their magnitudes. The carbon cycle gives rise to two climate feedback terms: the concentration–carbon feedback, resulting from the uptake of carbon by land and ocean as a biogeochemical response to the atmospheric CO2 concentration, and the climate–carbon feedback, resulting from the effect of climate change on carbon fluxes. In the earth system models of the Coupled Climate–Carbon Cycle Model Intercomparison Project (C4MIP), climate–carbon feedback on warming is positive and of a similar size to the cloud feedback. The concentration–carbon feedback is negative; it has generally received less attention in the literature, but in magnitude it is 4 times larger than the climate–carbon feedback and more uncertain. The concentration–carbon feedback is the dominant uncertainty in the allowable CO2 emissions that are consistent with a given CO2 concentration scenario. In modeling the climate response to a scenario of CO2 emissions, the net carbon cycle feedback is of comparable size and uncertainty to the noncarbon–climate response. To quantify simulated carbon cycle feedbacks satisfactorily, a radiatively coupled experiment is needed, in addition to the fully coupled and biogeochemically coupled experiments, which are referred to as coupled and uncoupled in C4MIP. The concentration–carbon and climate–carbon feedbacks do not combine linearly, and the concentration–carbon feedback is dependent on scenario and time.

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Projections of future global sea level depend on reliable estimates of changes in the size of polar ice sheets. Calculating this directly from global general circulation models (GCMs) is unreliable because the coarse resolution of 100 km or more is unable to capture narrow ablation zones, and ice dynamics is not usually taken into account in GCMs. To overcome these problems a high-resolution (20 km) dynamic ice sheet model has been coupled to the third Hadley Centre Coupled Ocean-Atmosphere GCM (HadCM3). A novel feature is the use of two-way coupling, so that climate changes in the GCM drive ice mass changes in the ice sheet model that, in turn, can alter the future climate through changes in orography, surface albedo, and freshwater input to the model ocean. At the start of the main experiment the atmospheric carbon dioxide concentration was increased to 4 times the preindustrial level and held constant for 3000 yr. By the end of this period the Greenland ice sheet is almost completely ablated and has made a direct contribution of approximately 7 m to global average sea level, causing a peak rate of sea level rise of 5 mm yr-1 early in the simulation. The effect of ice sheet depletion on global and regional climate has been examined and it was found that apart from the sea level rise, the long-term effect on global climate is small. However, there are some significant regional climate changes that appear to have reduced the rate at which the ice sheet ablates.

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This study investigates the response of wintertime North Atlantic Oscillation (NAO) to increasing concentrations of atmospheric carbon dioxide (CO2) as simulated by 18 global coupled general circulation models that participated in phase 2 of the Coupled Model Intercomparison Project (CMIP2). NAO has been assessed in control and transient 80-year simulations produced by each model under constant forcing, and 1% per year increasing concentrations of CO2, respectively. Although generally able to simulate the main features of NAO, the majority of models overestimate the observed mean wintertime NAO index of 8 hPa by 5-10 hPa. Furthermore, none of the models, in either the control or perturbed simulations, are able to reproduce decadal trends as strong as that seen in the observed NAO index from 1970-1995. Of the 15 models able to simulate the NAO pressure dipole, 13 predict a positive increase in NAO with increasing CO2 concentrations. The magnitude of the response is generally small and highly model-dependent, which leads to large uncertainty in multi-model estimates such as the median estimate of 0.0061 +/- 0.0036 hPa per %CO2. Although an increase of 0.61 hPa in NAO for a doubling in CO2 represents only a relatively small shift of 0.18 standard deviations in the probability distribution of winter mean NAO, this can cause large relative increases in the probabilities of extreme values of NAO associated with damaging impacts. Despite the large differences in NAO responses, the models robustly predict similar statistically significant changes in winter mean temperature (warmer over most of Europe) and precipitation (an increase over Northern Europe). Although these changes present a pattern similar to that expected due to an increase in the NAO index, linear regression is used to show that the response is much greater than can be attributed to small increases in NAO. NAO trends are not the key contributor to model-predicted climate change in wintertime mean temperature and precipitation over Europe and the Mediterranean region. However, the models' inability to capture the observed decadal variability in NAO might also signify a major deficiency in their ability to simulate the NAO-related responses to climate change.

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Canopy interception of incident precipitation is a critical component of the forest water balance during each of the four seasons. Models have been developed to predict precipitation interception from standard meteorological variables because of acknowledged difficulty in extrapolating direct measurements of interception loss from forest to forest. No known study has compared and validated canopy interception models for a leafless deciduous forest stand in the eastern United States. Interception measurements from an experimental plot in a leafless deciduous forest in northeastern Maryland (39°42'N, 75°5'W) for 11 rainstorms in winter and early spring 2004/05 were compared to predictions from three models. The Mulder model maintains a moist canopy between storms. The Gash model requires few input variables and is formulated for a sparse canopy. The WiMo model optimizes the canopy storage capacity for the maximum wind speed during each storm. All models showed marked underestimates and overestimates for individual storms when the measured ratio of interception to gross precipitation was far more or less, respectively, than the specified fraction of canopy cover. The models predicted the percentage of total gross precipitation (PG) intercepted to within the probable standard error (8.1%) of the measured value: the Mulder model overestimated the measured value by 0.1% of PG; the WiMo model underestimated by 0.6% of PG; and the Gash model underestimated by 1.1% of PG. The WiMo model’s advantage over the Gash model indicates that the canopy storage capacity increases logarithmically with the maximum wind speed. This study has demonstrated that dormant-season precipitation interception in a leafless deciduous forest may be satisfactorily predicted by existing canopy interception models.