scholarly journals On the similarities and differences between the products of oxidation of hydrocarbons under simulated atmospheric conditions and cool flames

2021 ◽  
Vol 21 (10) ◽  
pp. 7845-7862
Author(s):  
Roland Benoit ◽  
Nesrine Belhadj ◽  
Maxence Lailliau ◽  
Philippe Dagaut
Keyword(s):  
Mass Spectrometry ◽  
Elevated Temperature ◽  
Reaction Time ◽  
Reaction Mechanisms ◽  
Elevated Temperatures ◽  
Organic Aerosol ◽  
Atmospheric Conditions ◽  
Experimental Conditions ◽  
Data Set ◽  
Limonene Oxidation

Abstract. Atmospheric oxidation chemistry and, more specifically, photooxidation show that the long-term oxidation of organic aerosol (OA) progressively erases the initial signature of the chemical compounds and can lead to a relatively uniform character of oxygenated organic aerosol (OOA). This uniformity character observed after a long reaction time seems to contrast with the great diversity of reaction mechanisms observed in the early stages of oxidation. The numerous studies carried out on the oxidation of terpenes, and more particularly on limonene for its diversity of reaction sites (endo- and oxocyclic), allow this evolution to be studied. We have selected, for their diversity of experimental conditions, nine studies of limonene oxidation at room temperature over long reaction times to be compared to the present data set obtained at elevated temperature and short reaction time in order to investigate the similarities in terms of reaction mechanisms and chemical species formed. Here, the oxidation of limonene–oxygen–nitrogen mixtures was studied using a jet-stirred reactor at elevated temperature and atmospheric pressure. Samples of the reacting mixtures were collected and analyzed by high-resolution mass spectrometry (Orbitrap) after direct injection or after separation by reverse-phase ultra-high-pressure liquid chromatography and soft ionization, i.e., (+/-) HESI and (+/-) APCI. Unexpectedly, because of the diversity of experimental conditions in terms of continuous-flow tank reactor, concentration of reactants, temperature, reaction time, mass spectrometry techniques, and analysis conditions, the results indicate that among the 1138 presently detected molecular formulae, many oxygenates found in earlier studies of limonene oxidation by OH and/or ozone are also produced under the present conditions. Among these molecular formulae, highly oxygenated molecules and oligomers were detected in the present work. The results are discussed in terms of reaction pathways involving the initial formation of peroxy radicals (RO2), isomerization reactions yielding keto-hydroperoxides, and other oxygenated intermediates and products up to C25H32O17, products which could derive from RO2 autoxidation via sequential H shift and O2 addition (C10H14O3,5,7,9,11) and products deriving from the oxidation of alkoxy radicals (produced by RO2 self-reaction or reaction with HO2) through multiple H shifts and O2 additions (C10H14O2,4,6,8,10). The oxidation of RO2, with possible occurrence of the Waddington mechanism and of the Korcek mechanism, involving H shifts is also discussed. The present work demonstrates similitude between the oxidation products and oxidation pathways of limonene under simulated atmospheric conditions and in those encountered during the self-ignition of hydrocarbons at elevated temperatures. These results complement those recently reported by Vereecken and Nozière and confirm for limonene the existence of an oxidative chemistry of the alkylperoxy radical beyond 450 K based on the H shift (Nozière and Vereecken, 2019; Vereecken and Nozière, 2020).

scholarly journals Temperature uniformity in the CERN CLOUD chamber

2017 ◽  
Vol 10 (12) ◽  
pp. 5075-5088 ◽  
Author(s):  
António Dias ◽  
Sebastian Ehrhart ◽  
Alexander Vogel ◽  
Christina Williamson ◽  
João Almeida ◽  
...  
Keyword(s):  
Steady State ◽  
Air Temperature ◽  
Elevated Temperatures ◽  
Trace Gases ◽  
Vertical Direction ◽  
Cloud Chamber ◽  
Temperature Uniformity ◽  
Atmospheric Conditions ◽  
Cloud Droplets ◽  
Experimental Conditions

Abstract. The CLOUD (Cosmics Leaving OUtdoor Droplets) experiment at CERN (European Council for Nuclear Research) investigates the nucleation and growth of aerosol particles under atmospheric conditions and their activation into cloud droplets. A key feature of the CLOUD experiment is precise control of the experimental parameters. Temperature uniformity and stability in the chamber are important since many of the processes under study are sensitive to temperature and also to contaminants that can be released from the stainless steel walls by upward temperature fluctuations. The air enclosed within the 26 m3 CLOUD chamber is equipped with several arrays (strings) of high precision, fast-response thermometers to measure its temperature. Here we present a study of the air temperature uniformity inside the CLOUD chamber under various experimental conditions. Measurements were performed under calibration conditions and run conditions, which are distinguished by the flow rate of fresh air and trace gases entering the chamber at 20 and up to 210 L min−1, respectively. During steady-state calibration runs between −70 and +20 °C, the air temperature uniformity is better than ±0.06 °C in the radial direction and ±0.1 °C in the vertical direction. Larger non-uniformities are present during experimental runs, depending on the temperature control of the make-up air and trace gases (since some trace gases require elevated temperatures until injection into the chamber). The temperature stability is ±0.04 °C over periods of several hours during either calibration or steady-state run conditions. During rapid adiabatic expansions to activate cloud droplets and ice particles, the chamber walls are up to 10 °C warmer than the enclosed air. This results in temperature differences of ±1.5 °C in the vertical direction and ±1 °C in the horizontal direction, while the air returns to its equilibrium temperature with a time constant of about 200 s.

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 Investigation of the reaction of ozone with isoprene, methacrolein and methyl vinyl ketone using the HELIOS chamber

2017 ◽  
Vol 200 ◽  
pp. 289-311 ◽  
Author(s):  
Yangang Ren ◽  
Benoit Grosselin ◽  
Véronique Daële ◽  
Abdelwahid Mellouki
Keyword(s):  
Gas Phase ◽  
Organic Aerosol ◽  
Vinyl Ketone ◽  
Methyl Vinyl Ketone ◽  
Radical Scavenger ◽  
Oh Radical ◽  
Atmospheric Conditions ◽  
Experimental Conditions ◽  
Methyl Vinyl ◽  
Analytical Equipment

The rate constants for the ozonolysis of isoprene (ISO), methacrolein (MACR) and methyl vinyl ketone (MVK) have been measured using the newly built large volume atmospheric simulation chamber at CNRS-Orleans (France), HELIOS (Chambre de simulation atmosphérique à irradiation naturelle d’Orléans). The OH radical yields from the ozonolysis of isoprene, MACR and MVK have also been determined, as well as the gas phase stable products and their yields. The secondary organic aerosol yield for the ozonolysis of isoprene has been tentatively measured in the presence and absence of an OH radical scavenger. The measurements were performed under different experimental conditions with and without adding cyclohexane (cHX) as an OH radical scavenger. All experiments have been conducted at 760 torr of purified dry air (RH < 1%) and ambient temperature (T = 281–295 K). The data obtained are discussed and compared with those from the literature. The use of the HELIOS facility and its associated analytical equipment enables the derivation of kinetic parameters as well as mechanistic information under near realistic atmospheric conditions.

scholarly journals Temperature uniformity in the CERN CLOUD chamber

2017 ◽  
Author(s):  
Antonio Dias ◽  
Sebastian Ehrhart ◽  
Alexander Vogel ◽  
Christina Williamson ◽  
Joao Almeida ◽  
...  
Keyword(s):  
Steady State ◽  
Air Temperature ◽  
Elevated Temperatures ◽  
Trace Gases ◽  
Vertical Direction ◽  
Cloud Chamber ◽  
Temperature Uniformity ◽  
Atmospheric Conditions ◽  
Cloud Droplets ◽  
Experimental Conditions

Abstract. The CLOUD (Cosmics Leaving OUtdoor Droplets) experiment at CERN is studying the nucleation and growth of aerosol particles under atmospheric conditions, and their activation into cloud droplets. A key feature of the CLOUD experiment is precise control of the experimental parameters. Temperature uniformity and stability in the chamber are important since many of the processes under study are sensitive to temperature and also to contaminants that can be released from the stainless steel walls by upward temperature fluctuations. The air enclosed within the 3 m CLOUD chamber is equipped with several arrays (strings) of high precision, fast-response thermometers to measure its temperature. Here we present a study of the air temperature uniformity inside the CLOUD chamber under various experimental conditions. Measurements were performed under calibration conditions and run conditions, which are distinguished by the flow rate of fresh air and trace gases entering the chamber: 20 l/min and up to 210 l/min, respectively. During steady-state calibration runs between −70 °C and +20 °C, the air temperature uniformity is better than +/−0.06 °C in the radial direction and +/−0.1 °C in the vertical direction. Larger non-uniformities are present during experimental runs, depending on the temperature control of the make-up air and trace gases (since some trace gases require elevated temperatures until injection into the chamber). The temperature stability is a few times 0.01 °C over periods of several hours during either calibration or steady-state run conditions. During rapid adiabatic expansions to activate cloud droplets and ice particles, the chamber walls are up to 10 °C warmer than the enclosed air. This results in larger non-uniformities while the air returns to its equilibrium temperature with time constant of about 200 s.

scholarly journals Modified sodium molybdate as an efficient high yielding heterogeneous catalyst for biodiesel from Ghanaian indigenous Camelina sativa as a non-edible resource

2021 ◽  
Vol 2 (1) ◽  
Author(s):  
Mohammed Takase ◽  
Paul Kwame Essandoh ◽  
Rogers Kipkoech
Keyword(s):  
Reaction Time ◽  
Sodium Molybdate ◽  
Normal Pressure ◽  
Camelina Sativa ◽  
International Standards ◽  
Lewis Acidity ◽  
Molar Ratio ◽  
Solid Catalyst ◽  
Atmospheric Conditions ◽  
Heterogeneous Solid

AbstractSodium molybdate (Na2MoO4) has been synthesized and investigated as a heterogeneous solid catalyst for biodiesel from Camelina sativa seed oil. Transesterification reactions occurred under atmospheric conditions with relatively, low temperature short reaction time and normal pressure. The prepared catalyst was characterised by means of SEM, TGA, UV, XRD and FTIR. The properties of the biodiesel were compared with international standards. The transesterification reaction was very efficient with the optimum yield higher than 95% at methanol to oil molar ratio of 17:1, catalyst amount of 6%, reaction temperature of 60 °C and reaction time of 2.5 h. The molybdate complex had a high Lewis acidity and most certainly act as alcohol O–H bond leading to a transient species which has high nucleophilic character. The catalyst was easily recovered and after being washed for three times, showed capacity of recyclability for another catalytic reaction of five cycles with similar activity. The properties of the biodiesel were comparable to international standards.

scholarly journals Development of a target identification approach using native mass spectrometry

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Miaomiao Liu ◽  
Wesley C. Van Voorhis ◽  
Ronald J. Quinn
Keyword(s):  
Mass Spectrometry ◽  
Protein Interactions ◽  
Target Identification ◽  
Native Mass Spectrometry ◽  
Pharmaceutical Drugs ◽  
Ligand Complex ◽  
Experimental Conditions ◽  
Protein Mixture ◽  
Native Ms ◽  
Drug Target Identification

AbstractA key step in the development of new pharmaceutical drugs is the identification of the molecular target and distinguishing this from all other gene products that respond indirectly to the drug. Target identification remains a crucial process and a current bottleneck for advancing hits through the discovery pipeline. Here we report a method, that takes advantage of the specific detection of protein–ligand complexes by native mass spectrometry (MS) to probe the protein partner of a ligand in an untargeted method. The key advantage is that it uses unmodified small molecules for binding and, thereby, it does not require labelled ligands and is not limited by the chemistry required to tag the molecule. We demonstrate the use of native MS to identify known ligand–protein interactions in a protein mixture under various experimental conditions. A protein–ligand complex was successfully detected between parthenolide and thioredoxin (PfTrx) in a five-protein mixture, as well as when parthenolide was mixed in a bacterial cell lysate spiked with PfTrx. We provide preliminary data that native MS could be used to identify binding targets for any small molecule.

scholarly journals Study on Chromaticity Removal from Mineral Processing Wastewater with Salicylic Hydroxamic Acid by Granular Activated Carbon Catalyzed Ozonation

Minerals ◽  
2021 ◽  
Vol 11 (4) ◽  
pp. 359
Author(s):  
Liping Zhang ◽  
Shengnian Wu ◽  
Nan Zhang ◽  
Ruihan Yao ◽  
Eryong Wu
Keyword(s):  
Activated Carbon ◽  
Reaction Time ◽  
Hydroxamic Acid ◽  
Ph Value ◽  
Oxygen Demand ◽  
Granular Activated Carbon ◽  
Mineral Processing ◽  
Ultraviolet Absorption Spectrum ◽  
Experimental Conditions ◽  
Removal Ratio

Salicylic hydroxamic acid is a novel flotation reagent used in mineral processing. However, it impacts the flotation wastewater leaving behind high chromaticity which limits its reuse and affects discharge for mining enterprises. This study researched ozonation catalyzed by the granular activated carbon (GAC) method to treat the chromaticity of the simulated mineral processing wastewater with salicylic hydroxamic acid. The effects of pH value, ozone (O3) concentration, GAC dosage, and reaction time on chromaticity and chemical oxygen demand (CODCr) removal were discussed. The results of individual ozonation experiments showed that the chromaticity removal ratio reached 79% and the effluent chromaticity exceeded the requirement of reuse and discharge when the optimal experimental conditions were pH value 3, ozone concentration 6 mg/L, and reaction time 40 min. The orthogonal experimental results of catalytic ozonation with GAC on chromaticity removal explained that the chromaticity removal ratio could reach 96.36% and the chromaticity of effluent was only 20 when the optimal level of experimental parameters was pH value 2.87, O3 concentration 6 mg/L, GAC dosage 0.06 g/L, reaction time 60 min respectively. The degradation pathway of salicylic hydroxamic acid by ozonation was also considered based on an analysis with ultraviolet absorption spectrum and high-performance liquid chromatography (HPLC).

scholarly journals Urban organic aerosol composition in Eastern China differs from North to South: Molecular insight from a liquid chromatography-Orbitrap mass spectrometry study

2019 ◽  
Author(s):  
Kai Wang ◽  
Ru-Jin Huang ◽  
Martin Brüggemann ◽  
Yun Zhang ◽  
Lu Yang ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Liquid Chromatography ◽  
Eastern China ◽  
Organic Aerosol ◽  
Photochemical Oxidation ◽  
Lower Latitude ◽  
Molecular Formula ◽  
Aerosol Composition ◽  
Orbitrap Mass Spectrometry ◽  
Low Degrees

Abstract. Particulate air pollution in China is influencing human health, ecosystem and climate. However, the chemical composition of particulate aerosol, especially of the organic fraction, is still not well understood. In this study, particulate aerosol samples with a diameter &amp;leq; 2.5 μm (PM2.5) were collected in January 2014 in three cities located in Northeast, East and Southeast China, i.e., Changchun, Shanghai and Guangzhou, respectively. Organic aerosol (OA) in the PM2.5 samples was analyzed by ultrahigh performance liquid chromatography (UHPLC) coupled to high-resolution Orbitrap mass spectrometry in both negative mode (ESI−) and positive mode electrospray ionization (ESI+). After a non-target screening including molecular formula assignments, compounds were classified into five groups based on their elemental composition, i.e., CHO, CHON, CHN, CHOS and CHONS. The CHO, CHON and CHN compounds present the dominant signal abundances of 81–99.7 % in the mass spectra and the majority of these compounds were assigned to mono- and polyaromatics, suggesting that anthropogenic emissions are a large source of urban OA in all three cities. However, the chemical characteristics of these compounds varied among different cities. The degree of aromaticity and the number of polyaromatic compounds were significantly higher in samples from Changchun, which could be attributed to the large emissions from residential heating (i.e., coal combustion) during winter time in Northeast China. Moreover, the ESI− analysis showed higher H / C and O / C ratios for organic compounds in Shanghai and Guangzhou compared to samples from Changchun, indicating that OA in lower latitude regions of China experiences more intense photochemical oxidation processes. The majority of sulfur-containing compounds (CHOS and CHONS) in all cities were assigned to aliphatic compounds with low degrees of unsaturation and aromaticity. Again, samples from Shanghai and Guangzhou exhibit a larger chemical similarity but largely differ from those from Changchun.

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