scholarly journals Analysis of the possibility and molecular mechanism of carbon dioxide consumption in the Diels-Alder processes

2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Karolina Kula ◽  
Agnieszka Kącka-Zych ◽  
Agnieszka Łapczuk-Krygier ◽  
Radomir Jasiński
Keyword(s):  
Carbon Dioxide ◽  
Molecular Mechanism ◽  
Lewis Acids ◽  
Chemical Reactivity ◽  
Carbon Dioxide Concentration ◽  
Diels Alder ◽  
Wide Range ◽  
Bet Analysis ◽  
Earth’S Climate ◽  
Step Mechanism

Abstract The large and significant increase in carbon dioxide concentration in the Earth’s atmosphere is a serious problem for humanity. The amount of CO2 is increasing steadily which causes a harmful greenhouse effect that damages the Earth’s climate. Therefore, one of the current trends in modern chemistry and chemical technology are issues related to its utilization. This work includes the analysis of the possibility of chemical consumption of CO2 in Diels-Alder processes under non-catalytic and catalytic conditions after prior activation of the C=O bond. In addition to the obvious benefits associated with CO2 utilization, such processes open up the possibility of universal synthesis of a wide range of internal carboxylates. These studies have been performed in the framework of Molecular Electron Density Theory as a modern view of the chemical reactivity. It has been found, that explored DA reactions catalyzed by Lewis acids with the boron core, proceeds via unique stepwise mechanism with the zwitterionic intermediate. Bonding Evolution Theory (BET) analysis of the molecular mechanism associated with the DA reaction between cyclopentadiene and carbon dioxide indicates that it takes place thorough a two-stage one-step mechanism, which is initialized by formation of C–C single bond. In turn, the DA reaction between cyclopentadiene and carbon dioxide catalysed by BH3 extends in the environment of DCM, indicates that it takes place through a two-step mechanism. First path of catalysed DA reaction is characterized by 10 different phases, while the second by eight topologically different phases.

Climate Sensitivity and the Direct Effect of Carbon Dioxide in a Limited-Area Cloud-Resolving Model

2020 ◽  
Vol 33 (9) ◽  
pp. 3413-3429 ◽  
Author(s):  
David M. Romps
Keyword(s):  
Carbon Dioxide ◽  
Direct Effect ◽  
Climate Sensitivity ◽  
Convective Available Potential Energy ◽  
Carbon Dioxide Concentration ◽  
Limited Area ◽  
Equilibration Time ◽  
Feedback Parameter ◽  
Wide Range ◽  
Cloud Resolving Model

AbstractEven in a small domain, it can be prohibitively expensive to run cloud-resolving greenhouse gas warming experiments due to the long equilibration time. Here, a technique is introduced that reduces the computational cost of these experiments by an order of magnitude: instead of fixing the carbon dioxide concentration and equilibrating the sea surface temperature (SST), this technique fixes the SST and equilibrates the carbon dioxide concentration. Using this approach in a cloud-resolving model of radiative–convective equilibrium (RCE), the equilibrated SST is obtained as a continuous function of carbon dioxide concentrations spanning 1 ppmv to nearly 10 000 ppmv, revealing a dramatic increase in equilibrium climate sensitivity (ECS) at higher temperatures. This increase in ECS is due to both an increase in forcing and a decrease in the feedback parameter. In addition, the technique is used to obtain the direct effects of carbon dioxide (i.e., the rapid adjustments) over a wide range of SSTs. Overall, the direct effect of carbon dioxide offsets a quarter of the increase in precipitation from warming, reduces the shallow cloud fraction by a small amount, and has no impact on convective available potential energy (CAPE).

scholarly journals Space-based geoengineering: Challenges and requirements

2009 ◽  
Vol 224 (3) ◽  
pp. 571-580 ◽  
Author(s):  
C R McInnes
Keyword(s):  
Climate Change ◽  
Carbon Dioxide ◽  
Large Scale ◽  
Climate Model ◽  
Carbon Dioxide Concentration ◽  
Complex Solution ◽  
Lagrange Point ◽  
Simple Climate Model ◽  
Earth’S Climate

The prospect of engineering the Earth's climate (geoengineering) raises a multitude of issues associated with climatology, engineering on macroscopic scales, and indeed the ethics of such ventures. Depending on personal views, such large-scale engineering is either an obvious necessity for the deep future, or yet another example of human conceit. In this article a simple climate model will be used to estimate requirements for engineering the Earth's climate, principally using space-based geoengineering. Active cooling of the climate to mitigate anthropogenic climate change due to a doubling of the carbon dioxide concentration in the Earth's atmosphere is considered. This representative scenario will allow the scale of the engineering challenge to be determined. It will be argued that simple occulting discs at the interior Lagrange point may represent a less complex solution than concepts for highly engineered refracting discs proposed recently. While engineering on macroscopic scales can appear formidable, emerging capabilities may allow such ventures to be seriously considered in the long term. This article is not an exhaustive review of geoengineering, but aims to provide a foretaste of the future opportunities, challenges, and requirements for space-based geoengineering ventures.

An Investigation of the Sources of Blowby in Single-Cylinder Supercharged Diesel Engines

1978 ◽  
Vol 192 (1) ◽  
pp. 39-48 ◽  
Author(s):  
B. Bull ◽  
M. A. Voisey
Keyword(s):  
Carbon Dioxide ◽  
Diesel Engines ◽  
Piston Ring ◽  
Carbon Dioxide Concentration ◽  
Operating Conditions ◽  
Exhaust Valve ◽  
Simple Method ◽  
Single Cylinder ◽  
Carbon Dioxide Concentrations ◽  
Wide Range

Measurements of carbon dioxide concentrations in the exhaust and in the crankcase of two different types of single-cylinder, supercharged diesel engines have been used to determine the amount of exhaust gas reaching the crankcase as piston ring blowby and as leakage through the exhaust valve stem-to-guide clearance. Over a wide range of operating conditions in both engines the carbon dioxide concentration was found to be more dependent on engine fuelling rate per hour than on fuel input per stroke. It was established that blowby through the exhaust valve guide was a major contributor to crankcase contamination. A simple method has been devised, requiring only minor modifications to the engine, that permits the blowby through the piston ring pack and the exhaust valve guides to be determined separately in turbocharged production engines.

Interrelations of photosynthesis and assimilation of elementary nitrogen in a blue-green alga

1960 ◽  
Vol 153 (950) ◽  
pp. 111-127 ◽  
Keyword(s):  
Carbon Dioxide ◽  
Light Intensity ◽  
Nitrogen Assimilation ◽  
Relative Rate ◽  
Nitrogen Concentration ◽  
Carbon Assimilation ◽  
Carbon Dioxide Concentration ◽  
Mechanism Study ◽  
Wide Range ◽  
Elementary Nitrogen

In blue-green algae the hydrogen donors and carbon skeletons required in the fixation of elementary nitrogen may be supplied by the photosynthetic mechanism. Study of the kinetic relationships between the photosynthetic assimilation of carbon and the assimilation of nitrogen into the cell material of Anabaena cylindrica Lemm. has demonstrated correlations between the rates of the two processes consonant with the existence of such biochemical connexions. The effects of light intensity, carbon-dioxide concentration and nitrogen concentration were each studied at four different temperatures by determination of changes in amounts of cell carbon and cell nitrogen in cultures grown for 48 h. Temperature was found to have the most marked differential effect, both low and high temperatures depressing nitrogen assimilation to a greater extent than carbon assimilation. At any given temperature there was a close correlation between the rates of the two processes over a wide range of variation in other factors. Both carbon and nitrogen assimilation were found to be inhibited by relatively low concentrations of carbon dioxide. The rate of carbon assimilation per unit amount of cell nitrogen was found to be related in the usual way to light intensity, but to be reduced at low nitrogen concentrations. The relative rate of nitrogen assimilation was likewise found to be related in the expected way to nitrogen concentration but to increase with light intensity and to be reduced at carbon-dioxide concentrations limiting for carbon assimilation.

scholarly journals Detecting causality signal in instrumental measurements and climate model simulations: global warming case study

2019 ◽  
Author(s):  
Mikhail Y. Verbitsky ◽  
Michael E. Mann ◽  
Byron A. Steinman ◽  
Dmitry M. Volobuev
Keyword(s):  
Carbon Dioxide ◽  
Time Series ◽  
Atmospheric Carbon Dioxide ◽  
Climate Model ◽  
Carbon Dioxide Concentration ◽  
Anthropogenic Forcing ◽  
Carbon Dioxide Concentrations ◽  
Climate Model Simulations ◽  
Earth’S Climate

Abstract. Detecting the direction and strength of the causality signal in observed time series is becoming a popular tool for exploration of distributed systems such as Earth's climate system. Here we suggest that in addition to reproducing observed time series of climate variables within required accuracy a model should also exhibit the causality relationship between variables found in nature. Specifically, we propose a novel framework for a comprehensive analysis of climate model responses to external natural and anthropogenic forcing based on the method of conditional dispersion. As an illustration, we assess the causal relationship between anthropogenic forcing (i.e., atmospheric carbon dioxide concentration) and surface temperature anomalies. We demonstrate a strong directional causality between global temperatures and carbon dioxide concentrations (meaning that carbon dioxide affects temperature stronger than temperature affects carbon dioxide) in both the observations and in (CMIP5) climate model simulated temperatures.

Growth kinetics of Marquis wheat. II. Carbon dioxide dependence

1972 ◽  
Vol 50 (4) ◽  
pp. 883-889 ◽  
Author(s):  
F. D. H. Macdowall
Keyword(s):  
Carbon Dioxide ◽  
Light Intensity ◽  
Carbon Dioxide Concentration ◽  
Dry Weight ◽  
Maximum Growth ◽  
Carbon Dioxide Enrichment ◽  
Low Light ◽  
Growth Coefficient ◽  
Light Intensities ◽  
Wide Range

Marquis wheat was grown in growth rooms with four different concentrations of carbon dioxide and four to seven different intensities of light in a 16-h photoperiod at 25 °C. Growth was expressed quantitatively as the pseudo-first-order rate coefficient. Carbon dioxide stimulated growth, but the effect was greater the lower the light intensity in opposition to the known effect on photosynthesis. Carbon dioxide and light, in effect, did not influence the "rate" of growth of wheat additively but, rather, mutually compensated over a wide range. The growth coefficient of the roots was a little less than that of the shoots at all carbon dioxide concentrations and light intensities, probably owing to the cost of translocation. However, root growth benefited most from carbon dioxide enrichment at low light intensities. At intermediate light intensity there appeared to be a carbon dioxide concentration optimal for shoot growth. Carbon dioxide enrichment did not influence the maximum growth coefficient of Marquis wheat with respect to light intensity. The light-using efficiency of growth, calculated for vanishingly low light intensity at which it is maximal, was maximal for shoots at 1300 ppm CO2 but that for laminal area and root dry weight increased with CO2 to 2200 ppm at which the value for "leaves" was nearly fourfold that for roots. Unlike photosynthesis, the stimulation of growth by raised CO2 concentration was accomplished by increased efficiency of, and not capacity for, the net photosynthetic use of light.

scholarly journals A Permafrost Implementation in the Simple Carbon-Climate Model Hector

2021 ◽  
Author(s):  
Dawn L. Woodard ◽  
Alexey N. Shiklomanov ◽  
Ben Kravitz ◽  
Corinne Hartin ◽  
Ben Bond-Lamberty
Keyword(s):  
Carbon Dioxide ◽  
Atmospheric Carbon Dioxide ◽  
Climate Model ◽  
Computational Cost ◽  
Carbon Dioxide Concentration ◽  
Climate Feedback ◽  
Permafrost Soil ◽  
Atmospheric Carbon Dioxide Concentration ◽  
Wide Range ◽  
Atmospheric Carbon

Abstract. Permafrost, soil that remains below 0 °C for two or more years, currently stores more than a fourth of global soil carbon. A warming climate makes this carbon increasingly vulnerable to decomposition and release into the atmosphere in the form of greenhouse gases. The resulting climate feedback can be estimated using Earth system models (ESMs), but the high complexity and computational cost of these models make it challenging to use them for estimating uncertainty, exploring novel scenarios, and coupling with other models. We have added a representation of permafrost to the simple, open-source global carbon-climate model Hector, calibrated to be consistent with both historical data and twenty-first century ESM projections of permafrost thaw. We include permafrost as a separate land carbon pool that becomes available for decomposition into both methane and carbon dioxide once thawed; the thaw rate is controlled by region-specific air temperature increases from a pre-industrial baseline. We found that by 2100 thawed permafrost carbon emissions increased Hector's atmospheric carbon dioxide concentration by 10–15 % and the atmospheric methane concentration by 10–20 %, depending on the future scenario. This resulted in around 0.5 °C of additional warming over the next century. The fraction of thawed permafrost carbon available for decomposition was the most significant parameter controlling the end-of-century temperature change and atmospheric carbon dioxide concentration in the model and became increasingly significant over even longer timescales. The addition of permafrost in Hector provides a basis for the exploration of a suite of science questions, as Hector can be cheaply run over a wide range of parameter values to explore uncertainty and easily coupled with integrated assessment models to explore the economic consequences of warming from this feedback.

scholarly journals Detecting causality signal in instrumental measurements and climate model simulations: global warming case study

2019 ◽  
Vol 12 (9) ◽  
pp. 4053-4060 ◽  
Author(s):  
Mikhail Y. Verbitsky ◽  
Michael E. Mann ◽  
Byron A. Steinman ◽  
Dmitry M. Volobuev
Keyword(s):  
Carbon Dioxide ◽  
Time Series ◽  
Atmospheric Carbon Dioxide ◽  
Climate Model ◽  
Carbon Dioxide Concentration ◽  
Coupled Model ◽  
Anthropogenic Forcing ◽  
Carbon Dioxide Concentrations ◽  
Climate Model Simulations ◽  
Earth’S Climate

Abstract. Detecting the direction and strength of the causality signal in observed time series is becoming a popular tool for exploration of distributed systems such as Earth's climate system. Here, we suggest that in addition to reproducing observed time series of climate variables within required accuracy a model should also exhibit the causality relationship between variables found in nature. Specifically, we propose a novel framework for a comprehensive analysis of climate model responses to external natural and anthropogenic forcing based on the method of conditional dispersion. As an illustration, we assess the causal relationship between anthropogenic forcing (i.e., atmospheric carbon dioxide concentration) and surface temperature anomalies. We demonstrate a strong directional causality between global temperatures and carbon dioxide concentrations (meaning that carbon dioxide affects temperature more than temperature affects carbon dioxide) in both the observations and in (Coupled Model Intercomparison Project phase 5; CMIP5) climate model simulated temperatures.

scholarly journals Participation of Phosphorylated Analogues of Nitroethene in Diels–Alder Reactions with Anthracene: A Molecular Electron Density Theory Study and Mechanistic Aspect

Organics ◽  
2020 ◽  
Vol 1 (1) ◽  
pp. 36-48
Author(s):  
Agnieszka Kącka-Zych
Keyword(s):  
Electron Density ◽  
Density Functional ◽  
Diels Alder ◽  
Single Bond ◽  
Conceptual Density Functional Theory ◽  
Molecular Electron ◽  
Bet Analysis ◽  
One Step ◽  
Molecular Electron Density Theory ◽  
Step Mechanism

The structure and the contribution of the bis(2-chloroethyl) 2-nitro 1a and 2-bromo-2-nitroethenylphosphonates 1b with anthracene 2 in the Diels–Alder (DA) reactions have been studied within the Molecular Electron Density Theory (MEDT) at the B3LYP functional together with 6-31G(d), 6-31+G(d) and 6-31+G(d,p) basic sets. Analysis of the Conceptual Density Functional Theory (CDFT) reactivity indices indicates that 1a and 1b can be classified as a strong electrophile and marginal nucleophile, while 2 is classified as a strong electrophile and strong nucleophile. The studied DA reactions take place through a one-step mechanism. A Bonding Evolution Theory (BET) of the one path associated with the DA reaction of 1a with 2 indicates that it is associated with non-concerted two-stage one-step mechanism. BET analysis shows that the first C2-C3 single bond is formed in Phase VI, while the second C1-C6 single bond is formed in the Phase VIII. The formation of both single bonds occurs through the merging of two C2 and C3, C1 and C6 pseudoradical centers, respectively.

scholarly journals Marine carbonate system evolution during the EPOCA Arctic pelagic ecosystem experiment in the context of simulated Arctic ocean acidification

2012 ◽  
Vol 9 (11) ◽  
pp. 15541-15565 ◽  
Author(s):  
R. G. J. Bellerby ◽  
A. Silyakova ◽  
G. Nondal ◽  
D. Slagstad ◽  
J. Czerny ◽  
...  
Keyword(s):  
Carbon Dioxide ◽  
Ocean Acidification ◽  
Carbon Dioxide Concentration ◽  
Atmospheric Co2 ◽  
Pelagic Ecosystem ◽  
Carbonate System ◽  
Experimental Conditions ◽  
Study Region ◽  
Marine Carbonate ◽  
Wide Range

Abstract. A major, potential stressor of marine systems is the changing water chemistry following increasing seawater carbon dioxide concentration (CO2), commonly termed ocean acidification. In order to understand how an Arctic pelagic ecosystem may respond to future CO2, a deliberate ocean acidification and nutrient perturbation study was undertaken in an Arctic fjord. The initial setting and evolution of seawater carbonate chemistry were investigated. Additions of carbon dioxide resulted in a wide range of ocean acidification scenarios. This study documents the changes to the CO2 system throughout the study following net biological consumption and gas exchange with the atmosphere. In light of the common practice of extrapolating results to cover regions away from experimental conditions, a modelling study was also performed to assess the representativeness, in the context of the simulated present and future carbonate system, of the experimental study region to both the near and wider Arctic region. The mesocosm experiment represented the range of simulated marine carbonate system for the coming century and beyond (pCO2 to 1420 μatm) and thus extrapolations may be appropriate to ecosystems exhibiting similar levels of CO2 system drivers. However, as the regional ocean acidification was very heterogenous and did not follow changes in atmospheric CO2, care should be taken in extrapolating the mesocosm response to other regions based on atmospheric CO2 scenarios.

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