scholarly journals Stereoselectivity in Atmospheric Autoxidation

2020 ◽  
Author(s):  
Kristian H. Møller ◽  
Eric Praske ◽  
Lu Xu ◽  
John D. Crounse ◽  
Kelvin H. Bates ◽  
...  
Keyword(s):  
Transport Model ◽  
Theoretical Calculations ◽  
Peroxy Radical ◽  
Rate Coefficients ◽  
Large Set ◽  
Atmospheric Conditions ◽  
Hydrogen Shift ◽  
The Difference ◽  
Shift Reaction ◽  
High Level

<p>The importance of peroxy radical hydrogen shift reactions in the atmosphere has gained acceptance in recent years. Recent theoretical calculations have suggested that these can be stereoselective i.e. that different stereoisomers react with significantly different rate coefficients. Combining experiments (GC-CIMS) with high-level calculations (MC-TST), we show that two hydroxy peroxy radical diastereomers formed in the oxidation of crotonaldehyde have rate coefficients for their peroxy radical hydrogen shift reactions that differ by more than a factor of 10. The difference is large enough that under urban atmospheric conditions, one diastereomer would react primarily by the unimolecular H-shift, while the other would react mainly by bimolecular reactions leading to diastreomeric enhancement of the products.</p><p>For a large set of peroxy radical hydrogen shift reactions in the oxidation of isoprene, the stereospecific rate coefficients are calculated to assess the global importance of this phenomenon in the atmosphere.  These calculated rate coefficients are implemented into the global chemistry-transport model GEOS-Chem to model the effect. Results show that more than 30 % of all isoprene molecules emitted undergo a minimum of one peroxy radical hydrogen shift reaction during its oxidation. Furthermore, the results show that the different diastereomers may react with rate coefficients differing by up to almost a factor of 1000, highlighting how important it is to account for this phenomenon.</p>

scholarly journals Cloud-top pressure retrieval with DSCOVR EPIC oxygen A- and B-band observations

2020 ◽  
Vol 13 (10) ◽  
pp. 5259-5275
Author(s):  
Bangsheng Yin ◽  
Qilong Min ◽  
Emily Morgan ◽  
Yuekui Yang ◽  
Alexander Marshak ◽  
...  
Keyword(s):  
Single Layer ◽  
Computation Time ◽  
Observation Data ◽  
Atmospheric Conditions ◽  
Analytic Equation ◽  
Retrieval Processes ◽  
The Difference ◽  
High Level ◽  
Cloud Top Pressure ◽  
Layer Cloud

Abstract. An analytic transfer inverse model for Earth Polychromatic Imaging Camera (EPIC) observations is proposed to retrieve the cloud-top pressure (CTP) with the consideration of in-cloud photon penetration. In this model, an analytic equation was developed to represent the reflection at the top of the atmosphere from above cloud, in cloud, and below cloud. The coefficients of this analytic equation can be derived from a series of EPIC simulations under different atmospheric conditions using a nonlinear regression algorithm. With estimated cloud pressure thickness, the CTP can be retrieved from EPIC observation data by solving the analytic equation. To simulate the EPIC measurements, a program package using the double-k approach was developed. Compared to line-by-line calculation, this approach can calculate high-accuracy results with a 100-fold computation time reduction. During the retrieval processes, two kinds of retrieval results, i.e., baseline CTP and retrieved CTP, are provided. The baseline CTP is derived without considering in-cloud photon penetration, and the retrieved CTP is derived by solving the analytic equation, taking into consideration in-cloud and below-cloud interactions. The retrieved CTPs for the oxygen A and B bands are smaller than their related baseline CTP. At the same time, both baseline CTP and retrieved CTP at the oxygen B band are larger than those at the oxygen A band. Compared to the difference in baseline CTP between the B band and A band, the difference in retrieved CTP between these two bands is generally reduced. Out of around 10 000 cases, in retrieved CTP between the A and B bands we found an average bias of 93 mb with a standard deviation of 81 mb. The cloud layer top pressure from Cloud–Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO) measurements is used for validation. Under single-layer cloud situations, the retrieved CTPs for the oxygen A band agree well with the CTPs from CALIPSO, the mean difference of which within 5 mb in the case study. Under multiple-layer cloud situations, the CTPs derived from EPIC measurements may be larger than the CTPs of high-level thin clouds due to the effect of photon penetration.

scholarly journals Reactive nitrogen in Mexico City and its relation to ozone-precursor sensitivity: results from photochemical models

2009 ◽  
Vol 9 (11) ◽  
pp. 3477-3489 ◽  
Author(s):  
S. Sillman ◽  
J. J. West
Keyword(s):  
Mexico City ◽  
Transport Model ◽  
High Ratio ◽  
Reactive Nitrogen ◽  
Emission Rates ◽  
The Difference ◽  
Ozone Precursor ◽  
Mixed Pattern ◽  
High Level ◽  
Sensitive Conditions

Abstract. We use results of a 3-D photochemistry/transport model for ozone formation in Mexico City during events in 1997 to investigate ambient concentrations of reactive nitrogen in relation to ozone-precursor sensitivity. Previous results from other locations suggest that ratios such as O3/NOy and H2O2/HNO3 might provide measurement-based indicators for NOx-sensitive or VOC-sensitive conditions. Mexico City presents a different environment due to its high concentrations of VOC and high level of pollutants in general. The model predicts a correlation between PAN and O3 with relatively high PAN/O3 (0.07), which is still lower than measured values. The model PAN is comparable with results from a model for Paris but much higher than were found in Nashville in both models and measurements. The difference is due in part to the lower temperature in Mexico City relative to Nashville. Model HNO3 in Mexico City is unusually low for an urban area and PAN/HNO3 is very high, probably due to the high ratio of reactivity-weighted VOC to NOx. The model predicts that VOC-sensitive chemistry in Mexico is associated with high NOx, NOy and NOx/NOy and with low O3/NOy and H2O2/HNO3, suggesting that these indicators work well for Mexico City. The relation between ozone-precursor sensitivity and either O3/NOz or O3/HNO3 is more ambiguous. VOC-sensitive conditions are associated with higher O3/HNO3 than would be found in NOx-sensitive conditions, but model O3/HNO3 associated with both NOx-sensitive and VOC-sensitive chemistry is higher in Mexico than in other cities. The model predicts a mixed pattern of ozone-precursor sensitivity in Mexico City, with VOC-sensitive conditions in the morning and NOx-sensitive in the afternoon, in contrast to results from other models for more recent events that predicted strongly VOC- sensitive conditions throughout the day. The difference in predicted ozone-precursor sensitivity is most likely due to different emission rates and to changes in emissions over time. The model with mixed sensitivity predicts much lower ambient NOx and NOx/NOy than the strongly VOC-sensitive model.

scholarly journals Chemical loss processes of isocyanic acid, HNCO, in the atmosphere

2020 ◽  
Author(s):  
Simon Rosanka ◽  
Giang H. T. Vu ◽  
Hue M. T. Nguyen ◽  
Tien V. Pham ◽  
Umar Javed ◽  
...  
Keyword(s):  
Potential Energy Surfaces ◽  
Deep Convection ◽  
Rate Coefficients ◽  
Isocyanic Acid ◽  
Free Troposphere ◽  
Atmospheric Conditions ◽  
Kinetic Predictions ◽  
High Level ◽  
Energy Surfaces ◽  
The Impact

Abstract. The impact of chemical loss processes of isocyanic acid was studied by a combined theoretical and modeling study. The potential energy surfaces of the reactions of HNCO with OH and NO3 radicals, Cl atoms, and ozone, were studied using high-level CCSD(T)/CBS(DTQ)//M06-2X/aug-cc-pVTZ quantum chemical methodologies, followed by TST theoretical kinetic predictions of the rate coefficients at temperatures of 200–3000 K. It was found that the reactions are all slow in atmospheric conditions, with k(300 K) ≤ 7 × 10−16 cm3 molecule−1 s−1; the predictions are in good agreement with earlier experimental work, where available. The reverse reactions of NCO radicals, of importance mostly in combustion, were also examined briefly. The global model confirms that gas phase chemical loss of HNCO is a negligible process, contributing less than 1 %. Removal of HNCO by clouds and precipitation is a larger sink, contributing for about 10 % of the total loss, while globally dry deposition is the main sink, accounting for ~ 90 %. The global simulation also shows that due to its long chemical lifetime in the free troposphere, HNCO can be efficiently transported into the UTLS by deep convection events. Average daily concentrations of HNCO are found to rarely exceed levels considered potentially toxic, though locally instantaneous toxic levels are expected.the free troposphere, HNCO can be efficiently transported into the UTLS by deep convection events. Average daily concentrations of HNCO are found to rarely exceed levels considered potentially toxic, though locally instantaneous toxic levels are expected.

scholarly journals Reactive nitrogen in Mexico City and its relation to ozone-precursor sensitivity: results from photochemical models

2008 ◽  
Vol 8 (6) ◽  
pp. 20501-20536
Author(s):  
S. Sillman ◽  
J. J. West
Keyword(s):  
Mexico City ◽  
Transport Model ◽  
High Ratio ◽  
Reactive Nitrogen ◽  
Emission Rates ◽  
The Difference ◽  
High Concentrations ◽  
Ozone Precursor ◽  
High Level ◽  
Sensitive Conditions

Abstract. We use results of a 3-D photochemistry/transport model for ozone formation in Mexico City during events in 1997 to investigate ambient concentrations of reactive nitrogen in relation to ozone-precursor sensitivity. Previous results from other locations suggest that ratios such as O3/NOy and H2O2/HNO3 might provide measurement-based indicators for NOx-sensitive or VOC-sensitive conditions. Mexico City presents a different environment due to its high concentrations of VOC and high level of pollutants in general. The model predicts a correlation between PAN and O3 with relatively high PAN/O3 (0.07), which is still lower than measured values. The model PAN is comparable with results from a model for Paris but much higher than were found in Nashville in both models and measurements. The difference can be explained by the lower temperature in Mexico City relative to Nashville. Model HNO3 in Mexico City is unusually low for an urban area and PAN/HNO3 is very high, probably due to the high ratio of reactivity-weighted VOC to NOx. The model predicts that VOC-sensitive chemistry in Mexico is associated with high NOx, NOy and NOx/NOy and with low O3/NOy and H2O2/HNO3, suggesting that these indicators work well for Mexico City. The relation between ozone-precursor sensitivity and either O3/NOz or O3/HNO3 is more ambiguous. VOC-sensitive conditions are associated with higher O3/HNO3 than would be found in NOx-sensitive conditions, but model O3/HNO3 associated with both NOx-sensitive and VOC-sensitive chemistry is higher in Mexico than in other cities. The model predicts mixed sensitivity to NOx and VOC in Mexico City, with a tendency towards VOC-sensitive chemistry in the morning and NOx-sensitive in the afternoon, in contrast to model results for more recent events that predicted strongly VOC-sensitive conditions. The difference in predicted ozone-precursor sensitivity is most likely due to changes in emission rates over time. The model with mixed sensitivity predicts much lower ambient NOx and NOx/NOy than the strongly VOC-sensitive model.

Difference of [Ca2+]i Movements in Platelets Stimulated by Thrombin and TRAP: the Involvement of αIIbβ3-Mediated TXA2 Synthesis

1998 ◽  
Vol 79 (06) ◽  
pp. 1184-1190 ◽  
Author(s):  
Yoshiaki Tomiyama ◽  
Shigenori Honda ◽  
Kayoko Senzaki ◽  
Akito Tanaka ◽  
Mitsuru Okubo ◽  
...  
Keyword(s):  
Platelet Aggregation ◽  
Fibrinogen Binding ◽  
Adp Release ◽  
The Difference ◽  
Txa2 Receptor Antagonist ◽  
High Level ◽  
Inhibition Studies ◽  
Peak Increase ◽  
Second Peak ◽  
Assay Conditions

SummaryThis study investigated the difference of [Ca2+]i movement in platelets in response to thrombin and TRAP. The involvement of αIIbβ3 in this signaling was also studied. Stimulation of platelets with thrombin at 0.03 U/ml caused platelet aggregation and a two-peak increase in [Ca2+]i. The second peak of [Ca2+]i, but not the first peak was abolished by the inhibition of platelet aggregation with αIIbβ3 antagonists or by scavenging endogenous ADP with apyrase. A cyclooxygenase inhibitor, aspirin, and a TXA2 receptor antagonist, BM13505, also abolished the second peak of [Ca2+]i but not the first peak, although these regents did not inhibit aggregation. Under the same assay conditions, measurement of TXB2 demonstrated that αIIbβ3 antagonists and aspirin almost completely inhibited the production of TXB2. In contrast to thrombin-stimulation, TRAP caused only a single peak of [Ca2+]i even in the presence of platelet aggregation, and a high level of [Ca2+]i increase was needed for the induction of platelet aggregation. The inhibition of aggregation with αIIbβ3 antagonists had no effect on [Ca2+]i change and TXB2 production induced by TRAP. Inhibition studies using anti-GPIb antibodies suggested that GPIb may be involved in the thrombin response, but not in the TRAP. Our findings suggest that low dose thrombin causes a different [Ca2+]i response and TXA2 producing signal from TRAP. Endogenous ADP release and fibrinogen binding to αIIbβ3 are responsible for the synthesis of TXA2 which results in the induction of the second peak of [Ca2+]i in low thrombin- but not TRAP-stimulated platelets.

ATTITUDE TO OPEN ACCESS IN RUSSIAN SCHOLARLY COMMUNITY: 2018. SURVEY RESULTS AND ANALYSIS

2018 ◽  
Vol 1 (1) ◽  
pp. 6-21 ◽  
Author(s):  
I. K. Razumova ◽  
N. N. Litvinova ◽  
M. E. Shvartsman ◽  
A. Yu. Kuznetsov
Keyword(s):  
Open Access ◽  
Open Access Publishing ◽  
Scholarly Community ◽  
Research Areas ◽  
Survey Results ◽  
The Difference ◽  
Policies And Programs ◽  
The Uk ◽  
High Level ◽  
Access Policies

Introduction. The paper presents survey results on the awareness towards and practice of Open Access scholarly publishing among Russian academics.Materials and Methods. We employed methods of statistical analysis of survey results. Materials comprise results of data processing of Russian survey conducted in 2018 and published results of the latest international surveys. The survey comprised 1383 respondents from 182 organizations. We performed comparative studies of the responses from academics and research institutions as well as different research areas. The study compares results obtained in Russia with the recently published results of surveys conducted in the United Kingdom and Europe.Results. Our findings show that 95% of Russian respondents support open access, 94% agree to post their publications in open repositories and 75% have experience in open access publishing. We did not find any difference in the awareness and attitude towards open access among seven reference groups. Our analysis revealed the difference in the structure of open access publications of the authors from universities and research institutes. Discussion andConclusions. Results reveal a high level of awareness and support to open access and succeful practice in the open access publications in the Russian scholarly community. The results for Russia demonstrate close similarity with the results of the UK academics. The governmental open access policies and programs would foster the practical realization of the open access in Russia.

Quantitative indicators of air traffic controllers’ attitude to the danger of errors

2020 ◽  
pp. 68-78
Author(s):  
O. M. Reva ◽  
V. V. Kamyshin ◽  
S. P. Borsuk ◽  
V. A. Shulhin ◽  
A. V. Nevynitsyn
Keyword(s):  
Human Factor ◽  
Differential Method ◽  
Air Traffic ◽  
Professional Activity ◽  
Aviation Accidents ◽  
Air Traffic Controllers ◽  
The Difference ◽  
Level Of Significance ◽  
The Individual ◽  
High Level

The negative and persistent impact of the human factor on the statistics of aviation accidents and serious incidents makes proactive studies of the attitude of “front line” aviation operators (air traffic controllers, flight crewmembers) to dangerous actions or professional conditions as a key component of the current paradigm of ICAO safety concept. This “attitude” is determined through the indicators of the influence of the human factor on decision-making, which also include the systems of preferences of air traffic controllers on the indicators and characteristics of professional activity, illustrating both the individual perception of potential risks and dangers, and the peculiarities of generalized group thinking that have developed in a particular society. Preference systems are an ordered (ranked) series of n = 21 errors: from the most dangerous to the least dangerous and characterize only the danger preference of one error over another. The degree of this preference is determined only by the difference in the ranks of the errors and does not answer the question of how much time one error is more dangerous in relation to another. The differential method for identifying the comparative danger of errors, as well as the multistep technology for identifying and filtering out marginal opinions were applied. From the initial sample of m = 37 professional air traffic controllers, two subgroups mB=20 and mG=7 people were identified with statisti-cally significant at a high level of significance within the group consistency of opinions a = 1%. Nonpara-metric optimization of the corresponding group preference systems resulted in Kemeny’s medians, in which the related (middle) ranks were missing. Based on these medians, weighted coefficients of error hazards were determined by the mathematical prioritization method. It is substantiated that with the ac-cepted accuracy of calculations, the results obtained at the second iteration of this method are more ac-ceptable. The values of the error hazard coefficients, together with their ranks established in the preference systems, allow a more complete quantitative and qualitative analysis of the attitude of both individual air traffic controllers and their professional groups to hazardous actions or conditions.

scholarly journals On the Proton-Bound Noble Gas Dimers (Ng-H-Ng)+ and (Ng-H-Ng')+ (Ng, Ng'= He-Xe): Relationships betweenStructure, Stability, and Bonding Character

Molecules ◽  
2021 ◽  
Vol 26 (5) ◽  
pp. 1305
Author(s):  
Stefano Borocci ◽  
Felice Grandinetti ◽  
Nico Sanna
Keyword(s):  
Theoretical Calculations ◽  
Noble Gas ◽  
Structure Stability ◽  
Covalent Bonds ◽  
Dissociation Energies ◽  
Non Covalent Interactions ◽  
The Difference ◽  
Noble Gas Dimers ◽  
Covalent Interactions ◽  
Cluster Level

The structure, stability, and bonding character of fifteen (Ng-H-Ng)+ and (Ng-H-Ng')+ (Ng, Ng' = He-Xe) compounds were explored by theoretical calculations performed at the coupled cluster level of theory. The nature of the stabilizing interactions was, in particular, assayed using a method recently proposed by the authors to classify the chemical bonds involving the noble-gas atoms. The bond distances and dissociation energies of the investigated ions fall in rather large intervals, and follow regular periodic trends, clearly referable to the difference between the proton affinity (PA) of the various Ng and Ng'. These variations are nicely correlated with the bonding situation of the (Ng-H-Ng)+ and (Ng-H-Ng')+. The Ng-H and Ng'-H contacts range, in fact, between strong covalent bonds to weak, non-covalent interactions, and their regular variability clearly illustrates the peculiar capability of the noble gases to undergo interactions covering the entire spectrum of the chemical bond.

scholarly journals A Modified KNN Algorithm for High-Performance Computing on FPGA of Real-Time m-QAM Demodulators

Electronics ◽  
2021 ◽  
Vol 10 (5) ◽  
pp. 627
Author(s):  
David Marquez-Viloria ◽  
Luis Castano-Londono ◽  
Neil Guerrero-Gonzalez
Keyword(s):  
Real Time ◽  
High Performance ◽  
Interference Mitigation ◽  
Parallel Implementation ◽  
Computational Time ◽  
Successful Implementation ◽  
Interchannel Interference ◽  
The Difference ◽  
High Level ◽  
Performance Computing

A methodology for scalable and concurrent real-time implementation of highly recurrent algorithms is presented and experimentally validated using the AWS-FPGA. This paper presents a parallel implementation of a KNN algorithm focused on the m-QAM demodulators using high-level synthesis for fast prototyping, parameterization, and scalability of the design. The proposed design shows the successful implementation of the KNN algorithm for interchannel interference mitigation in a 3 × 16 Gbaud 16-QAM Nyquist WDM system. Additionally, we present a modified version of the KNN algorithm in which comparisons among data symbols are reduced by identifying the closest neighbor using the rule of the 8-connected clusters used for image processing. Real-time implementation of the modified KNN on a Xilinx Virtex UltraScale+ VU9P AWS-FPGA board was compared with the results obtained in previous work using the same data from the same experimental setup but offline DSP using Matlab. The results show that the difference is negligible below FEC limit. Additionally, the modified KNN shows a reduction of operations from 43 percent to 75 percent, depending on the symbol’s position in the constellation, achieving a reduction 47.25% reduction in total computational time for 100 K input symbols processed on 20 parallel cores compared to the KNN algorithm.

scholarly journals A Non-Uniform Broadcast Fertilization Method and Its Performance Analysis under Basin Irrigation

Water ◽  
2020 ◽  
Vol 12 (1) ◽  
pp. 292
Author(s):  
Kai Zhang ◽  
Meijian Bai ◽  
Yinong Li ◽  
Shaohui Zhang ◽  
Di Xu
Keyword(s):  
Field Experiment ◽  
Field Experiments ◽  
Transport Model ◽  
Inflow Rate ◽  
Application Performance ◽  
Solute Content ◽  
Basin Surface ◽  
Movement Characteristics ◽  
The Difference ◽  
Basin Irrigation

The broadcast fertilization method is widely used under basin irrigation in China. A reasonable broadcast fertilization method can effectively improve application performance of fertilization and reduce pollution from non-point agricultural sources. In this study, firstly, a non-uniform broadcast fertilization method and a non-uniform application coefficient were proposed. The value of non-uniform application coefficient is defined in this paper. It represents the ratio of the difference between the maximum and the average fertilization amount of fertilizer applied on the basin surface to the average fertilization amount of fertilizer applied on the basin surface. Secondly, field experiments were conducted to study the movement characteristics of fertilizer under non-uniform broadcast fertilization for basin irrigation. Field experiment results showed that under the condition of basin irrigation, the non-uniform broadcast fertilization method could weaken the non-uniform distribution of fertilizer due to erosion and transport capacity of solid fertilizer by irrigation water flow, which could significantly improve the uniformity of soil solute content. Thirdly, the solute transport model for broadcast fertilization was corroborated by the field experiment results. The variation rule of fertilization performance with non-uniform application coefficient under different basin length and inflow rate was achieved by simulation. The simulation results showed that fertilization uniformity and fertilization storage efficiency increased first and then decreased with the increase of non-uniform application coefficient. In order to be practically applicable, suitable irrigation programs of non-uniform application coefficient under different basin length and inflow rate conditions were proposed by numerical simulation.

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