scholarly journals Global and regional patterns of soil nitrous acid emissions and their acceleration of rural photochemical reactions

2021 ◽  
Author(s):  
Dianming Wu ◽  
Jingwei Zhang ◽  
Mengdi Wang ◽  
Junling An ◽  
Ruhai Wang ◽  
...  
2013 ◽  
Vol 25 (2) ◽  
pp. 326-334 ◽  
Author(s):  
Jinzhu Ma ◽  
Yongchun Liu ◽  
Chong Han ◽  
Qingxin Ma ◽  
Chang Liu ◽  
...  

2020 ◽  
Author(s):  
Sally Jahn ◽  
Elke Hertig

<p>Air pollution as well as high air temperature both pose a large risk to human health in Europe. High temperature levels are associated with an exceptionally high mortality rate, only representing the extreme end of a wide range of possible health effects. Tropospheric ozone, a secondary air pollutant, is primarily built by photochemical reactions under solar radiation with the involvement of precursor gases including nitrogen oxides, carbon monoxide, methane, and non-methane volatile organic compounds. Due to the specific characteristics of ozone formation, high levels of ozone and temperature often coincide, posing an even intensified threat to human health.</p><p>The current scientific work focuses on the co-occurrence of these two health stressors as well as their underlying meteorological conditions. A subset of European ozone (AirBase_v8, EEA) and temperature (ECA&D) stations is selected for analysis based on individual station locations and data coverage. Taking into account different settings of air substances concentrations (urban, outer conurbation area, rural regions), these stations are classified and grouped by station type and area type resulting in five distinct station classes: urban traffic, urban background, suburban background, rural background and rural industrial.</p><p>Maximum daily 8-hour average ozone values (MDA8O3, EEA), observed daily maximum air temperatures (TX, ECA&D) and meteorological variables (from ERA5, ECMWF) form the data basis for model building. Current thresholds and extreme definitions e.g. based on WHO air quality guidelines or high percentiles (75<sup>th</sup> and 90<sup>th</sup>) are examined and discussed to describe elevated levels of these variables and to finally define combined ozone-temperature events.</p><p>Possible regional patterns as well as disparities between urban and rural areas regarding the specific settings for ozone formation as well as varying meteorological mechanisms for the occurrence of combined ozone-temperature events are closely examined. The methodological focus is primary on statistical modelling, the application and comparison of varying multivariate statistical approaches and different machine learning methods, e.g. various regression analyses using shrinkage methods or random forests. Consequently, statistical models are generated to analyse the influence of meteorological conditions on the occurrence of combined ground-level ozone and temperature events along with the identification of primary key factors (e.g. ozone persistence or larger-scale air temperature and wind conditions) at each specific location.</p><p>Furthermore, frequency and intensity changes of combined ozone-temperate events in the scope of global warming are assessed. Thus, projections of these co-occurring events under the constraints of ongoing climate change until the end of the 21st century are analysed by integrating projections of general circulation models into the statistical modelling process.</p>


2020 ◽  
Author(s):  
Jingbai Li ◽  
Patrick Reiser ◽  
André Eberhard ◽  
Pascal Friederich ◽  
Steven Lopez

<p>Photochemical reactions are being increasingly used to construct complex molecular architectures with mild and straightforward reaction conditions. Computational techniques are increasingly important to understand the reactivities and chemoselectivities of photochemical isomerization reactions because they offer molecular bonding information along the excited-state(s) of photodynamics. These photodynamics simulations are resource-intensive and are typically limited to 1–10 picoseconds and 1,000 trajectories due to high computational cost. Most organic photochemical reactions have excited-state lifetimes exceeding 1 picosecond, which places them outside possible computational studies. Westermeyr <i>et al.</i> demonstrated that a machine learning approach could significantly lengthen photodynamics simulation times for a model system, methylenimmonium cation (CH<sub>2</sub>NH<sub>2</sub><sup>+</sup>).</p><p>We have developed a Python-based code, Python Rapid Artificial Intelligence <i>Ab Initio</i> Molecular Dynamics (PyRAI<sup>2</sup>MD), to accomplish the unprecedented 10 ns <i>cis-trans</i> photodynamics of <i>trans</i>-hexafluoro-2-butene (CF<sub>3</sub>–CH=CH–CF<sub>3</sub>) in 3.5 days. The same simulation would take approximately 58 years with ground-truth multiconfigurational dynamics. We proposed an innovative scheme combining Wigner sampling, geometrical interpolations, and short-time quantum chemical trajectories to effectively sample the initial data, facilitating the adaptive sampling to generate an informative and data-efficient training set with 6,232 data points. Our neural networks achieved chemical accuracy (mean absolute error of 0.032 eV). Our 4,814 trajectories reproduced the S<sub>1</sub> half-life (60.5 fs), the photochemical product ratio (<i>trans</i>: <i>cis</i> = 2.3: 1), and autonomously discovered a pathway towards a carbene. The neural networks have also shown the capability of generalizing the full potential energy surface with chemically incomplete data (<i>trans</i> → <i>cis</i> but not <i>cis</i> → <i>trans</i> pathways) that may offer future automated photochemical reaction discoveries.</p>


2018 ◽  
Author(s):  
Chandan Dey ◽  
Ronny Neumann

<p>A manganese substituted Anderson type polyoxometalate, [MnMo<sub>6</sub>O<sub>24</sub>]<sup>9-</sup>, tethered with an anthracene photosensitizer was prepared and used as catalyst for CO<sub>2</sub> reduction. The polyoxometalate-photosensitizer hybrid complex, obtained by covalent attachment of the sensitizer to only one face of the planar polyoxometalate, was characterized by NMR, IR and mass spectroscopy. Cyclic voltammetry measurements show a catalytic response for the reduction of carbon dioxide, thereby suggesting catalysis at the manganese site on the open face of the polyoxometalate. Controlled potentiometric electrolysis showed the reduction of CO<sub>2</sub> to CO with a TOF of ~15 sec<sup>-1</sup>. Further photochemical reactions showed that the polyoxometalate-anthracene hybrid complex was active for the reduction of CO<sub>2</sub> to yield formic acid and/or CO in varying amounts dependent on the reducing agent used. Control experiments showed that the attachment of the photosensitizer to [MnMo<sub>6</sub>O<sub>24</sub>]<sup>9-</sup> is necessary for photocatalysis.</p><div><br></div>


2018 ◽  
Author(s):  
Juan Sanz García ◽  
Martial Boggio-Pasqua ◽  
Ilaria Ciofini ◽  
Marco Campetella

<div>The ability to locate minima on electronic excited states (ESs) potential energy surfaces (PESs) both in the case of bright and dark states is crucial for a full understanding of photochemical reactions. This task has become a standard practice for small- to medium-sized organic chromophores thanks to the constant developments in the field of computational photochemistry. However, this remains a very challenging effort when it comes to the optimization of ESs of transition metal complexes (TMCs), not only due to the presence of several electronic excited states close in energy, but also due to the complex nature of the excited states involved. In this article, we present a simple yet powerful method to follow an excited state of interest during a structural optimization in the case of TMC, based on the use of a compact hole-particle representation of the electronic transition, namely the natural transition orbitals (NTOs). State tracking using NTOs is unambiguously accomplished by computing the mono-electronic wavefunction overlap between consecutive steps of the optimization. Here, we demonstrate that this simple but robust procedure works not only in the case of the cytosine but also in the case of the ES optimization of a ruthenium-nitrosyl complex which is very problematic with standard approaches.</div>


1963 ◽  
Vol 3 (3) ◽  
pp. 399-413
Author(s):  
Mohammad Irshad Khan

The main purpose of this paper is to present estimates of income elasticities for various commodity groups in East Pakistan. To date no such studies have been conducted in that province; and estimates made in other areas of the subcontinent have only limited applicability. Analysis of consumption patterns is essential for development planning because priorities and investment targets have to be based on demand forecasts for different commodities. Forecasting demand requires, among other variables, reliable estimates of income elasticities. In addition, knowledge about elasticities can be useful in deciding taxation policies and other controls over consumption. Further, in countries like Pakistan where large quantities of surplus foods are imported under the United States PL 480 programme, knowledge of income elasticities and regional patterns of consumption is important to permit effective utilization of these imports for economic development.


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