scholarly journals Effects of NO<sub><i>x</i></sub> and seed aerosol on highly oxygenated organic molecules (HOM) from cyclohexene ozonolysis

2020 ◽  
Author(s):  
Meri Räty ◽  
Otso Peräkylä ◽  
Matthieu Riva ◽  
Lauriane Quéléver ◽  
Olga Garmash ◽  
...  
Keyword(s):  
Organic Molecules ◽  
Oxidation Products ◽  
Radical Oxidation ◽  
Alpha Pinene ◽  
Seed Particles ◽  
No3 Radical ◽  
The Individual ◽  
Seed Aerosol ◽  
Oxygen Atoms

Abstract. Cyclohexene (C6H10) is commonly used as a proxy for biogenic monoterpenes, when studying their oxidation mechanisms and secondary organic aerosol (SOA) formation. The ozonolysis of cyclohexene has been shown to be effective at producing highly oxygenated organic molecules (HOM), a group of molecules known to be important in the formation of SOA. Here, we provide an in depth look at how, on a molecular level, the HOM formation and fate changed with perturbations from NOx and seed particles. HOM were produced in a chamber from cyclohexene ozonolysis, and measured with a chemical ionisation mass spectrometer (CIMS) using nitrate (NO3−) as reagent ion. As high-resolution CIMS instruments provide mass spectra with numerous ion signals and a wealth of information that can be hard to manage, we employed a primarily statistical approach for the data analysis. To utilise as many individual HOM signals as possible, each compound was assigned a parameter describing the quality of the observed signal. These parameters were then used as weights or to determine the inclusion of a given signal in further analyses. Under unperturbed ozonolysis conditions, known HOM peaks were observed in the chamber, including C6H8O9 as the largest HOM signal, and C12H20O9 as the largest dimer product. With the addition of nitric oxide (NO) into the chamber, the spectrum changed considerably, as expected. Dimer product signals decreased overall, but an increase in dimers with nitrate functionalities was seen, as a result of NO3 radical oxidation. The response of monomer signals to NO addition varied, and while nitrate-containing monomers increased, non-nitrate signals either increased or decreased, depending on the individual molecules. The addition of seed aerosol increased the condensation sink, which markedly decreased the signals of all low-volatility compounds. Larger molecules were seen to have a higher affinity for condensation, but a more detailed analysis showed that the uptake was controlled mainly by the number of oxygen atoms in each molecule. All non-nitrate compounds with at least 7 oxygen atoms were observed to condense onto the seed aerosol at close to equal rates. Nitrates required higher mass and higher oxygen content to condense at similar rates as the non-nitrate HOM. A comparison to experiments with alpha-pinene reported earlier, showed quite a similar relationship between elemental composition and volatility, although products from alpha-pinene ozonolysis appeared to require slightly higher oxygen numbers for the same decrease in volatility. In addition, two models developed for predicting volatilities of volatile organic compound (VOC) oxidation products were tested on the ozonolysis products of cyclohexene.

scholarly journals Measurement report: Effects of NO<sub><i>x</i></sub> and seed aerosol on highly oxygenated organic molecules (HOMs) from cyclohexene ozonolysis

2021 ◽  
Vol 21 (9) ◽  
pp. 7357-7372
Author(s):  
Meri Räty ◽  
Otso Peräkylä ◽  
Matthieu Riva ◽  
Lauriane Quéléver ◽  
Olga Garmash ◽  
...  
Keyword(s):  
Mass Spectra ◽  
Organic Molecules ◽  
Radical Oxidation ◽  
Seed Particles ◽  
No3 Radical ◽  
The Individual ◽  
Seed Aerosol ◽  
Oxidation Mechanisms ◽  
Oxygen Atoms

Abstract. Cyclohexene (C6H10) is commonly used as a proxy for biogenic monoterpenes, when studying their oxidation mechanisms and secondary organic aerosol (SOA) formation. The ozonolysis of cyclohexene has been shown to be effective at producing highly oxygenated organic molecules (HOMs), a group of molecules known to be important in the formation of SOA. Here, we provide an in-depth look at how the formation and fate of the broad range of observed HOMs changed with perturbations from NOx and seed particles. HOMs were produced in a chamber from cyclohexene ozonolysis and measured with a chemical ionisation mass spectrometer (CIMS) using nitrate (NO3-) as reagent ion. As high-resolution CIMS instruments provide mass spectra with numerous ion signals and a wealth of information that can be hard to manage, we employed a primarily statistical approach for the data analysis. To utilise as many individual HOM signals as possible, each compound was assigned a parameter describing the quality of the observed signal. These parameters were then used as weights or to determine the inclusion of a given signal in further analyses. Under unperturbed ozonolysis conditions, known HOM peaks were observed in the chamber, including C6H8O9 as the largest HOM signal and C12H20O9 as the largest “dimer” product. With the addition of nitric oxide (NO) into the chamber, the spectrum changed considerably, as expected. Dimer product signals decreased overall, but an increase in dimers with nitrate functionalities was seen, as a result of NO3 radical oxidation. The response of monomer signals to NO addition varied, and while nitrate-containing monomers increased, non-nitrate signals either increased or decreased, depending on the individual molecules. The addition of seed aerosol increased the condensation sink, which markedly decreased the signals of all low-volatility compounds. Larger molecules were seen to have a higher affinity for condensation, but a more detailed analysis showed that the uptake was controlled mainly by the number of oxygen atoms in each molecule. Nitrates required higher mass and higher oxygen content to condense at similar rates as the non-nitrate HOMs. We also tested two existing elemental-composition-based parameterisations for their ability to reproduce the condensation observed in our cyclohexene system. Both predicted higher volatilities than observed, most likely due to the number of oxygen atoms enhancing the product uptake more than the models would suggest.

scholarly journals Investigating the use of secondary organic aerosol as seed particles in simulation chamber experiments

2011 ◽  
Vol 11 (12) ◽  
pp. 5917-5929 ◽  
Author(s):  
J. F. Hamilton ◽  
M. Rami Alfarra ◽  
K. P. Wyche ◽  
M. W. Ward ◽  
A. C. Lewis ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Oxidation Products ◽  
Ion Cyclotron Resonance ◽  
Photo Oxidation ◽  
Seed Particles ◽  
Aerosol Mass ◽  
Seed Aerosol ◽  
Limonene Oxidation

Abstract. The use of β-caryophyllene secondary organic aerosol particles as seeds for smog chamber simulations has been investigated. A series of experiments were carried out in the Manchester photochemical chamber as part of the Aerosol Coupling in the Earth System (ACES) project to study the effect of seed particles on the formation of secondary organic aerosol (SOA) from limonene photo-oxidation. Rather than use a conventional seed aerosol containing ammonium sulfate or diesel particles, a method was developed to use in-situ chamber generated seed particles from β-caryophyllene photo-oxidation, which were then diluted to a desired mass loading (in this case 4–13 μg m−3). Limonene was then introduced into the chamber and oxidised, with the formation of SOA seen as a growth in the size of oxidised organic seed particles from 150 to 325 nm mean diameter. The effect of the partitioning of limonene oxidation products onto the seed aerosol was assessed using aerosol mass spectrometry during the experiment and the percentage of m/z 44, an indicator of degree of oxidation, increased from around 5 to 8 %. The hygroscopicity of the aerosol also changed, with the growth factor for 200 nm particles increasing from less than 1.05 to 1.25 at 90 % RH. The detailed chemical composition of the limonene SOA could be extracted from the complex β-caryophyllene matrix using two-dimensional gas chromatography (GC × GC) and liquid chromatography coupled to mass spectrometry. High resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FTICR-MS) was used to determine exact molecular formulae of the seed and the limonene modified aerosol. The average O:C ratio was seen to increase from 0.32 to 0.37 after limonene oxidation products had condensed onto the organic seed.

scholarly journals Investigating the use of secondary organic aerosol as seed particles in simulation chamber experiments

2010 ◽  
Vol 10 (10) ◽  
pp. 25117-25151
Author(s):  
J. F. Hamilton ◽  
M. Rami Alfarra ◽  
K. P. Wyche ◽  
M. W. Ward ◽  
A. C. Lewis ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Oxidation Products ◽  
Ion Cyclotron Resonance ◽  
Photo Oxidation ◽  
Seed Particles ◽  
Aerosol Mass ◽  
Seed Aerosol ◽  
Limonene Oxidation

Abstract. The use of β-caryophyllene secondary organic aerosol particles as seeds for smog chamber simulations has been investigated. A series of experiments were carried out in the Manchester photochemical chamber as part of the Aerosol Coupling in the Earth System (ACES) project to study the effect of seed particles on the formation of secondary organic aerosol (SOA) from limonene photo-oxidation. Rather than use a conventional seed aerosol containing ammonium sulphate or diesel particles, a method was developed to use in situ chamber generated seed particles from β-caryophyllene photo-oxidation, which were then diluted to a desired mass loading (in this case 4–13 μg m-3). Limonene was then introduced into the chamber and oxidised, with the formation of SOA seen as a growth in the size of oxidised organic seed particles from 150 to 325 nm mean diameter. The effect of the partitioning of limonene oxidation products onto the seed aerosol was assessed using aerosol mass spectrometry during the experiment and the percentage of m/z 44, an indicator of degree of oxidation, increased from around 5 to 8%. The hygroscopicity of the aerosol also changed, with the growth factor for 200 nm particles increasing from less than 1.05 to 1.25 at 90% RH. The detailed chemical composition of the limonene SOA could be extracted from the complex β-caryophyllene matrix using two-dimensional gas chromatography (GC×GC) and liquid chromatography coupled to mass spectrometry. High resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FTICR-MS) was used to determine exact molecular formulae of the seed and the limonene modified aerosol. The average O:C ratio was seen to increase from 0.32 to 0.37 after limonene oxidation products had condensed onto the organic seed.

scholarly journals Experimental investigation into the volatilities of highly oxygenated organic molecules (HOM)

2019 ◽  
Author(s):  
Otso Peräkylä ◽  
Matthieu Riva ◽  
Liine Heikkinen ◽  
Lauriane Quéléver ◽  
Pontus Roldin ◽  
...  
Keyword(s):  
Boreal Forests ◽  
Organic Molecules ◽  
Large Fraction ◽  
Carbon Number ◽  
Flow Chamber ◽  
Oxidation Products ◽  
Formation Mechanisms ◽  
High Hydrogen ◽  
Oxygenated Compounds ◽  
Alpha Pinene

Abstract. Secondary organic aerosol (SOA) forms a major part of the tropospheric submicron aerosol. Still, the exact formation mechanisms of SOA have remained elusive. Recently, a newly discovered group of oxidation products of volatile organic compounds (VOC), highly oxygenated organic molecules (HOM), have been proposed to be responsible for a large fraction of SOA formation. To assess the potential of HOM to form SOA, and to even take part in new particle formation, knowledge of their exact volatilities would be essential. However, due to their exotic, and partially unknown, structures, estimating their volatility is challenging. In this study, we performed a set of continuous flow chamber experiments, supported by box modelling, to study the volatilities of HOM, along with some less oxygenated compounds, formed in the ozonolysis of alpha-pinene, an abundant VOC emitted by the boreal forests. Along with gaseous precursors, we periodically injected inorganic seed aerosol into the chamber to vary the condensation sink (CS) of low volatility vapours. We monitored the decrease of oxidation products in the gas phase in response to increasing CS, and were able to relate the responses to the volatilities of the compounds. We found that HOM monomers are mainly of low volatility, with a small fraction being semi-volatile. HOM dimers were all of at least low volatility, but probably of extremely low volatility: however, our method is not directly able to distinguish between the two. We were able to explain the volatility of the oxidation products in terms of their carbon, hydrogen, oxygen and nitrogen numbers. We found that increasing levels of oxygenation correspond to lower volatilities, as expected, but that the decrease is less steep than would be expected based on many existing models for volatility, such as SIMPOL. The hydrogen number of a compound also explained its volatility, independently of the carbon number, with higher hydrogen numbers corresponding to lower volatilities. This can be explained in terms of the functional groups making up a molecule: high hydrogen numbers are associated with e.g. hyrdoxy groups, which lower the volatility more than e.g. carbonyls, that are associated with a lower hydrogen number. The method presented should be applicable to systems other than α-pinene ozonolysis, and with different organic loadings in order to study different volatility ranges.

Semi-automated methods for 3-D reconstruction of macromolecular complexes

1995 ◽  
Vol 53 ◽  
pp. 42-43
Author(s):  
B. Carragher ◽  
M. Whittaker
Keyword(s):  
Three Dimensional ◽  
Time Saving ◽  
Macromolecular Complexes ◽  
Symmetry Properties ◽  
Dimensional Reconstruction ◽  
Experienced Operator ◽  
Projection Images ◽  
The Individual ◽  
Natural Symmetry

Techniques for three-dimensional reconstruction of macromolecular complexes from electron micrographs have been successfully used for many years. These include methods which take advantage of the natural symmetry properties of the structure (for example helical or icosahedral) as well as those that use single axis or other tilting geometries to reconstruct from a set of projection images. These techniques have traditionally relied on a very experienced operator to manually perform the often numerous and time consuming steps required to obtain the final reconstruction. While the guidance and oversight of an experienced and critical operator will always be an essential component of these techniques, recent advances in computer technology, microprocessor controlled microscopes and the availability of high quality CCD cameras have provided the means to automate many of the individual steps.During the acquisition of data automation provides benefits not only in terms of convenience and time saving but also in circumstances where manual procedures limit the quality of the final reconstruction.

Manageable Self in the Early Hellenistic Era

2010 ◽  
Vol 39 (2) ◽  
pp. 34-36
Author(s):  
Vaia Touna
Keyword(s):  
Social Economic ◽  
Ancient Greece ◽  
The Self ◽  
Hellenistic Period ◽  
Political Conditions ◽  
The Individual

This paper argues that the rise of what is commonly termed "personal religion" during the Classic-Hellenistic period is not the result of an inner need or even quality of the self, as often argued by those who see in ancient Greece foreshadowing of Christianity, but rather was the result of social, economic, and political conditions that made it possible for Hellenistic Greeks to redefine the perception of the individual and its relationship to others.

Reflecting the Sky in Water

2017 ◽  
Vol 3 (1) ◽  
pp. 112-126 ◽  
Author(s):  
Ilaria Cristofaro
Keyword(s):  
The Unconscious ◽  
Related Case ◽  
Quality Of Water ◽  
Fluid Properties ◽  
Phenomenological Perspective ◽  
Auto Ethnography ◽  
The Individual ◽  
Artificial Water ◽  
Land Water

From a phenomenological perspective, the reflective quality of water has a visually dramatic impact, especially when combined with the light of celestial phenomena. However, the possible presence of water as a means for reflecting the sky is often undervalued when interpreting archaeoastronomical sites. From artificial water spaces, such as ditches, huacas and wells to natural ones such as rivers, lakes and puddles, water spaces add a layer of interacting reflections to landscapes. In the cosmological understanding of skyscapes and waterscapes, a cross-cultural metaphorical association between water spaces and the underworld is often revealed. In this research, water-skyscapes are explored through the practice of auto-ethnography and reflexive phenomenology. The mirroring of the sky in water opens up themes such as the continuity, delimitation and manipulation of sky phenomena on land: water spaces act as a continuation of the sky on earth; depending on water spaces’ spatial extension, selected celestial phenomena can be periodically reflected within architectures, so as to make the heavenly dimension easily accessible and a possible object of manipulation. Water-skyscapes appear as specular worlds, where water spaces are assumed to be doorways to the inner reality of the unconscious. The fluid properties of water have the visual effect of dissipating borders, of merging shapes, and, therefore, of dissolving identities; in the inner landscape, this process may represent symbolic death experiences and rituals of initiation, where the annihilation of the individual allows the creative process of a new life cycle. These contextually generalisable results aim to inspire new perspectives on sky-and-water related case studies and give value to the practice of reflexive phenomenology as crucial method of research.

QUALITY OF INDIVIDUAL AND GROUP LEVEL INTERVENTIONS FOR FIRST EPISODE PSYCHOSIS AT THE TERTIARY PSYCHIATRIC HOSPITAL IN UGANDA.

2020 ◽  
Author(s):  
Emmanuel Kiiza Mwesiga ◽  
Noeline Nakasujja ◽  
Lawrence Nankaba ◽  
Juliet Nakku ◽  
Seggane Musisi
Keyword(s):  
Psychiatric Hospital ◽  
Psychotic Disorders ◽  
First Episode Psychosis ◽  
First Episode ◽  
Group Level ◽  
Group Interventions ◽  
Episode Psychosis ◽  
Essential Components ◽  
The Individual

Introduction: Individual and group level interventions have the largest effect on outcomes in patients with the first episode of psychosis. The quality of these individual and group level interventions provided to first-episode psychosis patients in Uganda is unclear.Methods: The study was performed at Butabika National Psychiatric Teaching and referral hospital in Uganda. A retrospective chart review of recently discharged adult in-patients with the first episode of psychosis was first performed to determine the proportion of participants who received the different essential components for individual and group level interventions. From the different proportions, the quality of the services across the individual and group interventions was determined using the first-Episode Psychosis Services Fidelity Scale (FEPS-FS). The FEPS-FS assigns a grade of 1-5 on a Likert scale depending on the proportion of patients received the different components of the intervention. Results: The final sample included 156 first-episode psychosis patients. The median age was 27 years [IOR (24-36)] with 55% of participants of the female gender. 13 essential components across the individual and group interventions were assessed and their quality quantified. All 13 essential components had poor quality with the range of scores on the FEPS-FS of 1-3. Only one essential component assessed (use of single antipsychotics) had moderate quality.Discussion: Among current services at the National psychiatric hospital of Uganda, the essential for individual and group level interventions for psychotic disorders are of low quality. Further studies are required on how the quality of these interventions can be improved.

THE VALUE OF LOVE IN THE SYSTEM OF FORMATION OF THE PROFESSIONAL MATURITY OF THE EDUCATOR

2020 ◽  
Vol 1 (10(79)) ◽  
pp. 12-18
Author(s):  
G. Bubyreva
Keyword(s):  
Russian Federation ◽  
The State ◽  
Educational Process ◽  
Wide Range ◽  
The Family ◽  
The Russian Federation ◽  
The Government ◽  
The Individual ◽  
The Right

The existing legislation determines the education as "an integral and focused process of teaching and upbringing, which represents a socially important value and shall be implemented so as to meet the interests of the individual, the family, the society and the state". However, even in this part, the meaning of the notion ‘socially significant benefit is not specified and allows for a wide range of interpretation [2]. Yet the more inconcrete is the answer to the question – "who and how should determine the interests of the individual, the family and even the state?" The national doctrine of education in the Russian Federation, which determined the goals of teaching and upbringing, the ways to attain them by means of the state policy regulating the field of education, the target achievements of the development of the educational system for the period up to 2025, approved by the Decree of the Government of the Russian Federation of October 4, 2000 #751, was abrogated by the Decree of the Government of the Russian Federation of March 29, 2014 #245 [7]. The new doctrine has not been developed so far. The RAE Academician A.B. Khutorsky believes that the absence of the national doctrine of education presents a threat to national security and a violation of the right of citizens to quality education. Accordingly, the teacher has to solve the problem of achieving the harmony of interests of the individual, the family, the society and the government on their own, which, however, judging by the officially published results, is the task that exceeds the abilities of the participants of the educational process.  The particular concern about the results of the patriotic upbringing served as a basis for the legislative initiative of the RF President V. V. Putin, who introduced the project of an amendment to the Law of RF "About Education of the Russian Federation" to the State Duma in 2020, regarding the quality of patriotic upbringing [3]. Patriotism, considered by the President of RF V. V. Putin as the only possible idea to unite the nation is "THE FEELING OF LOVE OF THE MOTHERLAND" and the readiness for every sacrifice and heroic deed for the sake of the interests of your Motherland. However, the practicing educators experience shortfalls in efficient methodologies of patriotic upbringing, which should let them bring up citizens, loving their Motherland more than themselves. The article is dedicated to solution to this problem based on the Value-sense paradigm of upbringing educational dynasty of the Kurbatovs [15].

A Human/Computer Learning Network to Improve Biodiversity Conservation and Research

AI Magazine ◽  
2012 ◽  
Vol 34 (1) ◽  
pp. 10 ◽  
Author(s):  
Steve Kelling ◽  
Jeff Gerbracht ◽  
Daniel Fink ◽  
Carl Lagoze ◽  
Weng-Keen Wong ◽  
...  
Keyword(s):  
Artificial Intelligence ◽  
Feedback Loop ◽  
Human Computation ◽  
Computational Power ◽  
Learning Networks ◽  
Learning Network ◽  
Computer Learning ◽  
The Individual ◽  
Citizen Science Project

In this paper we describe eBird, a citizen-science project that takes advantage of the human observational capacity to identify birds to species, which is then used to accurately represent patterns of bird occurrences across broad spatial and temporal extents. eBird employs artificial intelligence techniques such as machine learning to improve data quality by taking advantage of the synergies between human computation and mechanical computation. We call this a Human-Computer Learning Network, whose core is an active learning feedback loop between humans and machines that dramatically improves the quality of both, and thereby continually improves the effectiveness of the network as a whole. In this paper we explore how Human-Computer Learning Networks can leverage the contributions of a broad recruitment of human observers and processes their contributed data with Artificial Intelligence algorithms leading to a computational power that far exceeds the sum of the individual parts.

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