scholarly journals Estimation of mechanistic parameters in the gas-phase reactions of ozone with alkenes for use in automated mechanism construction

2022 ◽  
Author(s):  
Mike J. Newland ◽  
Camille Mouchel-Vallon ◽  
Richard Valorso ◽  
Bernard Aumont ◽  
Luc Vereecken ◽  
...  
Keyword(s):  
Theoretical Data ◽  
Closed Shell ◽  
Atmospheric Composition ◽  
Critical Parameters ◽  
Initial Reaction ◽  
Oh Radicals ◽  
Unimolecular Decomposition ◽  
Criegee Intermediates ◽  
Automatic Mechanism ◽  
The Impact

Abstract. Reaction with ozone is an important atmospheric removal process for alkenes. The ozonolysis reaction produces carbonyls, and carbonyl oxides (Criegee intermediates, CI), which can rapidly decompose to yield a range of closed shell and radical products, including OH radicals. Consequently, it is essential to accurately represent the complex chemistry of Criegee intermediates in atmospheric models in order to fully understand the impact of alkene ozonolysis on atmospheric composition. A mechanism construction protocol is presented which is suitable for use in automatic mechanism generation. The protocol defines the critical parameters for describing the chemistry following the initial reaction, namely: the primary carbonyl / CI yields from the primary ozonide fragmentation; the amount of stabilisation of the excited CI (CI*); the unimolecular decomposition pathways, rates and products of the CI; the bimolecular rates and products of atmospherically important reactions of the stabilised CI (SCI). This analysis implicitly predicts the yield of OH from the alkene-ozone reaction. A comprehensive database of experimental OH, SCI and carbonyl yields has been collated using reported values in the literature and used to assess the reliability of the protocol. The protocol provides estimates OH, SCI and carbonyl yields with a root mean square error of 0.13 and 0.12 and 0.14, respectively. Areas where new experimental and theoretical data would improve the protocol and its assessment are identified and discussed.

scholarly journals Using Satellite Data for CBRN (Chemical, Biological, Radiological, and Nuclear) Threat Detection, Monitoring, and Modelling

2021 ◽  
Author(s):  
Gary Sutlieff ◽  
Lucy Berthoud ◽  
Mark Stinchcombe
Keyword(s):  
Satellite Data ◽  
Meteorological Data ◽  
Atmospheric Composition ◽  
Chemical Detection ◽  
List Type ◽  
Data Types ◽  
Wide Range ◽  
Future Technologies ◽  
The Impact ◽  
Near Future

Abstract CBRN (Chemical, Biological, Radiological, and Nuclear) threats are becoming more prevalent, as more entities gain access to modern weapons and industrial technologies and chemicals. This has produced a need for improvements to modelling, detection, and monitoring of these events. While there are currently no dedicated satellites for CBRN purposes, there are a wide range of possibilities for satellite data to contribute to this field, from atmospheric composition and chemical detection to cloud cover, land mapping, and surface property measurements. This study looks at currently available satellite data, including meteorological data such as wind and cloud profiles, surface properties like temperature and humidity, chemical detection, and sounding. Results of this survey revealed several gaps in the available data, particularly concerning biological and radiological detection. The results also suggest that publicly available satellite data largely does not meet the requirements of spatial resolution, coverage, and latency that CBRN detection requires, outside of providing terrain use and building height data for constructing models. Lastly, the study evaluates upcoming instruments, platforms, and satellite technologies to gauge the impact these developments will have in the near future. Improvements in spatial and temporal resolution as well as latency are already becoming possible, and new instruments will fill in the gaps in detection by imaging a wider range of chemicals and other agents and by collecting new data types. This study shows that with developments coming within the next decade, satellites should begin to provide valuable augmentations to CBRN event detection and monitoring. Article Highlights There is a wide range of existing satellite data in fields that are of interest to CBRN detection and monitoring. The data is mostly of insufficient quality (resolution or latency) for the demanding requirements of CBRN modelling for incident control. Future technologies and platforms will improve resolution and latency, making satellite data more viable in the CBRN management field

scholarly journals Monitoring of the Impact of Lithium Nitrate on the Alkali–aggregate Reaction Using Acoustic Emission Methods

Materials ◽  
2018 ◽  
Vol 12 (1) ◽  
pp. 20
Author(s):  
Justyna Zapała-Sławeta ◽  
Grzegorz Świt
Keyword(s):  
Acoustic Emission ◽  
Initial Reaction ◽  
Lithium Nitrate ◽  
Acoustic Emission Method ◽  
Emission Method ◽  
Acoustic Activity ◽  
Initial Stage ◽  
Chemical Admixture ◽  
Different Characteristics ◽  
The Impact

The study analyzed the possibility of using the acoustic emission method to analyse the reaction of alkali with aggregate in the presence of lithium nitrate. Lithium nitrate is a chemical admixture used to reduce adverse effects of corrosion. The tests were carried out using mortars with reactive opal aggregate, stored under the conditions defined by ASTM C227. The acoustic activity of mortars with a corrosion inhibitor was referred to linear changes and microstructure of specimens in the initial reaction stages. The study found a low acoustic activity of mortars with lithium nitrate. Analysis of characteristic parameters of acoustic emission signals, combined with the observation of changes in the microstructure, made it possible to describe the corrosion processes. As the reaction progressed, signals with different characteristics were recorded, indicating aggregate cracking at the initial stage of the reaction, followed by cracking of the cement paste. The results, which were referred to the acoustic activity of reference mortars, confirmed that the reaction of opal aggregate with alkali was mitigated in mortars with lithium nitrate, and the applied acoustic emission method enabled the detection and monitoring of ASR progress.

Low Temperature Pre-Epi Treatment: Critical Parameters to Control Interface Contamination

2009 ◽  
Vol 145-146 ◽  
pp. 177-180 ◽  
Author(s):  
Roger Loo ◽  
Andriy Hikavyy ◽  
Frederik E. Leys ◽  
Masayuki Wada ◽  
Kenichi Sano ◽  
...  
Keyword(s):  
Low Temperature ◽  
Sige Layer ◽  
Ex Situ ◽  
Critical Parameters ◽  
Process Equipment ◽  
Successful Implementation ◽  
Lifetime Measurements ◽  
Deposition Processes ◽  
Cleaning Methods ◽  
The Impact

Several device concepts have been further evaluated after the successful implementation of epitaxial Si, SiGe and/or Si:C layers. Most of the next device generations will put limitations on the thermal budget of the deposition processes without making concessions on the epitaxial layer quality. In this work we address the impact of ex-situ wet chemical cleans and in-situ pre-epi bake steps, which are required to obtain oxide free Si surfaces for epitaxial growth. The combination of defect measurements, Secondary Ion Mass Spectroscopy, photoluminescence, lifetime measurements, and electrical diode characterization gives a very complete overview of the performance of low-temperature pre-epi cleaning methods. Contamination at the epi/substrate interface cannot be avoided if the pre-epi bake temperature is too low. This interface contamination is traceable by the photoluminescence and lifetime measurements. It may affect device characteristics by enhanced leakage currents and eventually by yield issues due to SiGe layer relaxation or other defect generation. A comparison of state of the art 200 mm and 300 mm process equipment indicates that for the same thermal budgets the lowest contamination levels are obtained for the 300 mm equipments.

DEEPFAKE AS A PHENOMENON OF POLITICAL COMMUNICATION

2021 ◽  
Vol 27 (6) ◽  
pp. 101-106
Author(s):  
М. Falaleev ◽  
◽  
N. Sitdikova ◽  
Е. Nechay ◽  
◽  
...  
Keyword(s):  
Artificial Intelligence ◽  
Political Communication ◽  
Political Discourse ◽  
Rapid Development ◽  
Theoretical Data ◽  
Practical Significance ◽  
Subject Field ◽  
Learning Programs ◽  
Definition Of ◽  
The Impact

The development of digital technologies, coupled with progress in the development of self-learning programs based on AI (Artificial Intelligence), has obvious advantages in improving the effectiveness of information impact on people around the world. During the 2010s, researchers have documented trends in the use of artificial intelligence for the construction and distribution of media content to indirectly manipulate political discourse at the national and global levels. Special interest in the context of this issue is how the rapid development of AI technologies affects political communication. The object of consideration within the framework of this article is the deepfake technology. Based on this, as a subject, the authors define deepfake as a phenomenon of modern political communication. Accordingly, the purpose of the study is to describe and predict the impact of deepfake technology on political communication at the global and national levels. The paper presents the definition of deepfake, assesses its characteristics depending on the methods and purposes of its distribution, and analyzes the prospects for using this tool to influence political discourse in modern Russia. To study the subject field of the research, methods of systematizing theoretical data, classification, analysis of a set of factors and forecasting have been applied. The practical significance of the work is presented by the authors’ definition and typology of the phenomenon of deepfake and describes its significance as a factor of political communication on the example of a particular country. The results of the work will be useful for researchers studying the problems of digitalization of the media space and modern means of disinformation in politics, both at the local and global levels

scholarly journals Extending methane profiles from aircraft into the stratosphere for satellite total column validation using the ECMWF C-IFS and TOMCAT/SLIMCAT 3-D model

2017 ◽  
Vol 17 (11) ◽  
pp. 6663-6678 ◽  
Author(s):  
Shreeya Verma ◽  
Julia Marshall ◽  
Mark Parrington ◽  
Anna Agustí-Panareda ◽  
Sebastien Massart ◽  
...  
Keyword(s):  
Greenhouse Gases ◽  
Transport Model ◽  
A Priori ◽  
Atmospheric Composition ◽  
Random Errors ◽  
Chemical Transport Model ◽  
Spatial Coverage ◽  
Forecasting System ◽  
The Impact ◽  
Total Column

Abstract. Airborne observations of greenhouse gases are a very useful reference for validation of satellite-based column-averaged dry air mole fraction data. However, since the aircraft data are available only up to about 9–13 km altitude, these profiles do not fully represent the depth of the atmosphere observed by satellites and therefore need to be extended synthetically into the stratosphere. In the near future, observations of CO2 and CH4 made from passenger aircraft are expected to be available through the In-Service Aircraft for a Global Observing System (IAGOS) project. In this study, we analyse three different data sources that are available for the stratospheric extension of aircraft profiles by comparing the error introduced by each of them into the total column and provide recommendations regarding the best approach. First, we analyse CH4 fields from two different models of atmospheric composition – the European Centre for Medium-Range Weather Forecasts (ECMWF) Integrated Forecasting System for Composition (C-IFS) and the TOMCAT/SLIMCAT 3-D chemical transport model. Secondly, we consider scenarios that simulate the effect of using CH4 climatologies such as those based on balloons or satellite limb soundings. Thirdly, we assess the impact of using a priori profiles used in the satellite retrievals for the stratospheric part of the total column. We find that the models considered in this study have a better estimation of the stratospheric CH4 as compared to the climatology-based data and the satellite a priori profiles. Both the C-IFS and TOMCAT models have a bias of about −9 ppb at the locations where tropospheric vertical profiles will be measured by IAGOS. The C-IFS model, however, has a lower random error (6.5 ppb) than TOMCAT (12.8 ppb). These values are well within the minimum desired accuracy and precision of satellite total column XCH4 retrievals (10 and 34 ppb, respectively). In comparison, the a priori profile from the University of Leicester Greenhouse Gases Observing Satellite (GOSAT) Proxy XCH4 retrieval and climatology-based data introduce larger random errors in the total column, being limited in spatial coverage and temporal variability. Furthermore, we find that the bias in the models varies with latitude and season. Therefore, applying appropriate bias correction to the model fields before using them for profile extension is expected to further decrease the error contributed by the stratospheric part of the profile to the total column.

scholarly journals The oxidation regime and SOA composition in limonene ozonolysis: roles of different double bonds, radicals, and water

2018 ◽  
Vol 18 (20) ◽  
pp. 15105-15123 ◽  
Author(s):  
Yiwei Gong ◽  
Zhongming Chen ◽  
Huan Li
Keyword(s):  
Mass Fraction ◽  
Reaction Pathway ◽  
Performic Acid ◽  
Oh Radicals ◽  
Double Bonds ◽  
Criegee Intermediates ◽  
Volatile Organic ◽  
Partitioning Coefficients ◽  
Reaction With Water ◽  
Partitioning Behavior

Abstract. Volatile organic compounds play an important role in air quality and climate change, largely because they contribute to the formation of oxidizing compounds and secondary organic aerosol (SOA). In this study, a series of products, including peroxides and carbonyl compounds in both gaseous and particulate phases, were simultaneously detected to investigate the oxidation regime and SOA composition in limonene ozonolysis. The roles of different double bonds (DBs), radicals, and water were also examined. In our first investigation, we focused on representative oxidizing compounds produced in limonene ozonolysis, including stabilized Criegee intermediates (SCIs), OH radicals, and peroxides. The dependence of H2O2 and hydroxymethyl hydroperoxide (HMHP) formation on RH demonstrates that the reaction with water is an important reaction pathway for limonene SCIs, and the lower limit SCI yields of endocyclic and exocyclic DBs were estimated to be ∼0.24 and ∼0.43, respectively. The OH yield was determined by adding sufficient amounts of an OH scavenger, and the OH yields of endocyclic and exocyclic DBs were ∼0.65 and ∼0.24, respectively. These results indicate that in limonene ozonolysis the endocyclic DB is inclined to generate OH radicals through the hydroperoxide channel, while the exocyclic DB has a higher fraction of forming SCIs. Additionally, other gas-phase and particle-phase peroxides were also studied in this work. The formation of performic acid (PFA) and peracetic acid (PAA) was promoted significantly by increasing RH and the degree of oxidation, and the discrepancy between the experimental and model results suggested some missing formation pathways. Considerable generation of H2O2 from SOA in the aqueous phase was observed, especially at a high [O3] ∕ [limonene] ratio, which was mainly attributed to the hydration and decomposition of unstable peroxides in SOA such as peroxycarboxylic acids and peroxyhemiacetals. Different DBs and OH scavengers had a large impact on the particulate peroxides, and their stability indicated that the types of peroxides in SOA changed under different conditions. As for the contribution of peroxides to SOA, the results demonstrated that the mass fraction of particulate peroxides in limonene SOA was less than 0.2 at a low [O3] ∕ [limonene] ratio, while the mass fraction was 0.4–0.6 at a high [O3] ∕ [limonene] ratio. The partitioning behavior of peroxides showed that multi-generation oxidation helped produce more low-volatility peroxides, which partially explained the higher SOA yield. The partitioning behavior of carbonyls was also examined and the experimental partitioning coefficients (Kp) were found to be typically several orders of magnitude higher than the theoretical values. This study provided new insights into the oxidation regime and SOA composition in limonene ozonolysis, and limonene showed its specificity in many aspects when both endocyclic and exocyclic DBs were ozonated. We suggest that the atmospheric implications of terpenes containing more than one DB and the SOA composition, especially particulate peroxides, need further study.

scholarly journals Phononic Band Gap and Free Vibration Analysis of Fluid-Conveying Pipes with Periodically Varying Cross-Section

2021 ◽  
Vol 11 (21) ◽  
pp. 10485
Author(s):  
Hao Yu ◽  
Feng Liang ◽  
Yu Qian ◽  
Jun-Jie Gong ◽  
Yao Chen ◽  
...  
Keyword(s):  
Free Vibration ◽  
Band Gap ◽  
Cross Section ◽  
Natural Frequencies ◽  
Free Vibration Analysis ◽  
Critical Parameters ◽  
Mode Shapes ◽  
Beam Model ◽  
The Impact ◽  
Fluid Conveying Pipes

Phononic crystals (PCs) are a novel class of artificial periodic structure, and their band gap (BG) attributes provide a new technical approach for vibration reduction in piping systems. In this paper, the vibration suppression performance and natural properties of fluid-conveying pipes with periodically varying cross-section are investigated. The flexural wave equation of substructure pipes is established based on the classical beam model and traveling wave property. The spectral element method (SEM) is developed for semi-analytical solutions, the accuracy of which is confirmed by comparison with the available literature and the widely used transfer matrix method (TMM). The BG distribution and frequency response of the periodic pipe are attained, and the natural frequencies and mode shapes are also obtained. The effects of some critical parameters are discussed. It is revealed that the BG of the present pipe system is fundamentally induced by the geometrical difference of the substructure cross-section, and it is also related to the substructure length and fluid–structure interaction (FSI). The number of cells does not contribute to the BG region, while it has significant effects on the amplitude attenuation, higher order natural frequencies and mode shapes. The impact of FSI is more evident for the pipes with smaller numbers of cells. Moreover, compared with the conventional TMM, the present SEM is demonstrated more effective for comprehensive analysis of BG characteristics and free vibration of PC dynamical structures.

scholarly journals The MCM v3.3 degradation scheme for isoprene

2015 ◽  
Vol 15 (6) ◽  
pp. 9709-9766 ◽  
Author(s):  
M. E. Jenkin ◽  
J. C. Young ◽  
A. R. Rickard
Keyword(s):  
Boundary Layer ◽  
Free Radical ◽  
Degradation Mechanism ◽  
Closed Shell ◽  
Chemical Mechanism ◽  
Formation Mechanisms ◽  
Oh Radicals ◽  
Atmospheric Conditions ◽  
Radical Species ◽  
Master Chemical Mechanism

Abstract. The chemistry of isoprene degradation in the Master Chemical Mechanism (MCM) has been systematically refined and updated to reflect recent advances in understanding, with these updates appearing in the latest version, MCM v3.3. The complete isoprene degradation mechanism in MCM v3.3 consists of 1935 reactions of 605 closed shell and free radical species, which treat the chemistry initiated by reaction with OH radicals, NO3 radicals and ozone (O3). A detailed overview of the updates is provided, within the context of reported kinetic and mechanistic information. The revisions mainly relate to the OH-initiated chemistry, which tends to dominate under atmospheric conditions, although these include updates to the chemistry of some products that are also generated from the O3 - and NO3-initiated oxidation. The revisions have impacts in a number of key areas, including HOx recycling, NOx recycling and the formation of species reported to play a role in SOA-formation mechanisms. The performance of the MCM v3.3 isoprene mechanism has been compared with those of earlier versions (MCM v3.1 and MCM v3.2) over a range of relevant conditions, using a box model of the tropical forested boundary layer. The results of these calculations are presented and discussed, and are used to illustrate the impacts of the mechanistic updates in MCM v3.3.

scholarly journals Role of Criegee intermediates in the formation of sulfuric acid at a Mediterranean (Cape Corsica) site under influence of biogenic emissions

2021 ◽  
Vol 21 (17) ◽  
pp. 13333-13351
Author(s):  
Alexandre Kukui ◽  
Michel Chartier ◽  
Jinhe Wang ◽  
Hui Chen ◽  
Sébastien Dusanter ◽  
...  
Keyword(s):  
Steady State ◽  
Sulfuric Acid ◽  
Organic Compounds ◽  
Rate Coefficients ◽  
Oh Radicals ◽  
Additional Source ◽  
So2 Oxidation ◽  
Criegee Intermediates ◽  
Volatile Organic

Abstract. Reaction of stabilized Criegee intermediates (SCIs) with SO2 was proposed as an additional pathway of gaseous sulfuric acid (H2SO4) formation in the atmosphere, supplementary to the conventional mechanism of H2SO4 production by oxidation of SO2 in reaction with OH radicals. However, because of a large uncertainty in mechanism and rate coefficients for the atmospheric formation and loss reactions of different SCIs, the importance of this additional source is not well established. In this work, we present an estimation of the role of SCIs in H2SO4 formation at a western Mediterranean (Cape Corsica) remote site, where comprehensive field observations including gas-phase H2SO4, OH radicals, SO2, volatile organic compounds (VOCs) and aerosol size distribution measurements were performed in July–August 2013 as a part of the project ChArMEx (Chemistry-Aerosols Mediterranean Experiment). The measurement site was under strong influence of local emissions of biogenic volatile organic compounds, including monoterpenes and isoprene generating SCIs in reactions with ozone, and, hence, presenting an additional source of H2SO4 via SO2 oxidation by the SCIs. Assuming the validity of a steady state between H2SO4 production and its loss by condensation on existing aerosol particles with a unity accommodation coefficient, about 90 % of the H2SO4 formation during the day could be explained by the reaction of SO2 with OH. During the night the oxidation of SO2 by OH radicals was found to contribute only about 10 % to the H2SO4 formation. The accuracy of the derived values for the contribution of OH + SO2 reaction to the H2SO4 formation is limited mostly by a large, at present factor of 2, uncertainty in the OH + SO2 reaction rate coefficient. The contribution of the SO2 oxidation by SCIs to the H2SO4 formation was evaluated using available measurements of unsaturated VOCs and steady-state SCI concentrations estimated by adopting rate coefficients for SCI reactions based on structure–activity relationships (SARs). The estimated concentration of the sum of SCIs was in the range of (1–3) × 103 molec. cm−3. During the day the reaction of SCIs with SO2 was found to account for about 10 % and during the night for about 40 % of the H2SO4 production, closing the H2SO4 budget during the day but leaving unexplained about 50 % of the H2SO4 formation during the night. Despite large uncertainties in used kinetic parameters, these results indicate that the SO2 oxidation by SCIs may represent an important H2SO4 source in VOC-rich environments, especially during nighttime.

scholarly journals A new Geoengineering Model Intercomparison Project (GeoMIP) experiment designed for climate and chemistry models

2014 ◽  
Vol 7 (4) ◽  
pp. 5447-5464 ◽  
Author(s):  
S. Tilmes ◽  
M. J. Mills ◽  
U. Niemeier ◽  
H. Schmidt ◽  
A. Robock ◽  
...  
Keyword(s):  
Model Comparison ◽  
Stratospheric Aerosol ◽  
Atmospheric Composition ◽  
Model Intercomparison ◽  
Data Set ◽  
Aerosol Forcing ◽  
Input Dataset ◽  
Intercomparison Project ◽  
Total Burden ◽  
The Impact

Abstract. A new Geoengineering Model Intercomparison Project (GeoMIP) experiment "G4 specified stratospheric aerosols" (short name: G4SSA) is proposed to investigate the impact of stratospheric aerosol geoengineering on atmospheric composition, climate, and the environment. In contrast to the earlier G4 GeoMIP experiment, which requires an emission of sulphur dioxide (SO2) into the model, a prescribed aerosol forcing file is provided to the community, to be consistently applied to future model experiments between 2020 and 2100. This stratospheric aerosol distribution, with a total burden of about 2 Tg S has been derived using the ECHAM5-HAM microphysical model, based on a continuous annual tropical emission of 8 Tg SO2 year−1. A ramp-up of geoengineering in 2020 and a ramp-down in 2070 over a period of two years are included in the distribution, while a background aerosol burden should be used for the last 3 decades of the experiment. The performance of this experiment using climate and chemistry models in a multi-model comparison framework will allow us to better understand the significance of the impact of geoengineering and the abrupt termination after 50 years on climate and composition of the atmosphere in a changing environment. The zonal and monthly mean stratospheric aerosol input dataset is available at https://www2.acd.ucar.edu/gcm/geomip-g4-specified-stratospheric-aerosol-data-set.

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