Thermal Profiles in Gas Phase Oxidations of Low Molecular Weight Hydrocarbons

Nature ◽  
1966 ◽  
Vol 212 (5064) ◽  
pp. 812-813
Author(s):  
J. F. BUSSERT ◽  
E. F. STEIGELMANN
2019 ◽  
Vol 19 (4) ◽  
pp. 2421-2432 ◽  
Author(s):  
Tomoki Mochizuki ◽  
Kimitaka Kawamura ◽  
Yuzo Miyazaki ◽  
Bhagawati Kunwar ◽  
Suresh Kumar Reddy Boreddy

Abstract. To better understand the distributions and sources of low-molecular-weight (LMW) monocarboxylic acids (monoacids) in the forest atmosphere, we conducted simultaneous collection of gaseous and particulate samples at a deciduous broadleaf forest site in northern Japan. LMW normal (C1–C10), branched (iC4–iC6), hydroxyl (glycolic and lactic) and aromatic (benzoic) monoacids were detected in the gas and particle phases. The dominant LMW monoacids in gas phase were formic (mean: 953 ng m−3) and acetic (528 ng m−3) acids followed by propionic (37 ng m−3) or isopentanoic (42 ng m−3) acid. In the particle phase, isopentanoic (159 ng m−3) was dominant, followed by acetic (104 ng m−3) and formic (71 ng m−3) or lactic (65 ng m−3) acids. Concentrations of LMW monoacids did not show correlations with anthropogenic tracers such as nss-SO42- and NO3-, indicating that anthropogenic contribution is not important. Concentrations of C1–C6 monoacids in the gas phase showed positive correlations (r2=0.21–0.91) with isobutyric acid (iC4), which may be produced by microbial activity in soil. The forest soil may be a source of gaseous C1–C6 monoacids in the forest atmosphere. Acetic acid in the particle phase positively correlated with nonanoic acid (C9) (r2=0.63), suggesting that formation of acetic and nonanoic acids is associated with the oxidation of biogenic unsaturated fatty acids in the aerosol phase, in addition to photochemical oxidation of biogenic volatile organic compounds. The particle-phase fractions (Fp) of formic and acetic acids showed negative correlation with ambient temperature (C1: r2=0.49, C2: r2=0.60) but showed positive correlation with relative humidity (C1: r2=0.30, C2: r2=0.55) in daytime, suggesting that these meteorological parameters are important for the gas and particle portioning of monoacids in the forest atmosphere.


2018 ◽  
Author(s):  
Bastian Stieger ◽  
Gerald Spindler ◽  
Dominik van Pinxteren ◽  
Achim Grüner ◽  
Markus Wallasch ◽  
...  

Abstract. A method is presented to quantify the low-molecular weight organic acids formic, acetic, propionic, butyric, pyruvic, glycolic, oxalic, malonic, succinic, malic, glutaric, and methanesulfonic acid in the atmospheric gas and particle phase in a two-hourly time resolution, based on a combination of the Monitor for AeRosols and Gases in ambient Air (MARGA) and an additional ion chromatography (IC) instrument. A proper separation of the organic target acids was initially tackled by a laboratory IC optimization study, testing different separation columns, eluent compositions and eluent flow rates both for isocratic and for gradient elution. Satisfactory resolution of all compounds was achieved using a gradient system with two coupled anion exchange separation columns. Online pre-concentration with an enrichment factor of approximately 400 was achieved by solid phase extraction consisting of a methacrylate polymer based sorbent with quaternary ammonium groups. The limits of detection of the method range between 7.1 ng m−3 for methanesulfonate and 150.3 ng m−3 for pyruvate. Precisions are below 1.0 %, except for glycolate (2.9 %) and succinate (1.0 %). Comparisons of inorganic anions measured at the TROPOS research site in Melpitz, Germany, by the original MARGA and the additional organic acid IC systems are in agreement with each other (R2 = 0.95 − 0.99). Organic acid concentrations from May 2017 as an example period are presented. Monocarboxylic acids were dominant in the gas phase with mean concentrations of 553 ng m−3 for acetic acid, followed by formic (286 ng m−3), pyruvic acid (182 ng m−3), propionic (179 ng m−3), butyric (98 ng m−3) and glycolic (71 ng  m−3). Particulate glycolate, oxalate and methanesulfonate were quantified with mean concentrations of 63 ng  m−3, 74 ng m−3 and 35 ng m−3, respectively. Elevated concentrations in the late afternoon of gas phase formic acid and particulate oxalate indicate a photochemical formation.


2018 ◽  
Author(s):  
Tomoki Mochizuki ◽  
Kimitaka Kawamura ◽  
Yuzo Miyazaki ◽  
Suresh K. R. Boreddy

Abstract. To better understand the distributions of low molecular weight (LMW) monocarboxylic acids (monoacids) and their sources in the forest, we conducted simultaneous collection of gaseous and particulate samples at a deciduous broadleaf forest site in northern Japan. LMW normal (C1–C10), branched chain (iC4–iC6), hydroxyl (lactic and glycolic) and aromatic (benzoic) monoacids were detected in the gas and particle phases. The dominant LMW monoacids in gas phase were formic (mean: 953 ng m−3) and acetic (528 ng m−3) acids. In particle phase, we found that isopentanoic (159 ng m−3) and acetic (104 ng m−3) acids are dominant species together with lactic acid. Concentrations of LMW monoacids did not correlate with SO42− that was used as an anthropogenic tracer, indicating that LMW monoacids are derived from the local sources within the forest ecosystem. Concentrations of C1–C6 monoacids in gas phase showed positive correlations (r2 = 0.21–0.91) with isobutyric acid (iC4), which is produced by soil microorganisms. These monoacids are closely linked to the microbial process in soils. Isopentanoic acid in particle phase showed a positive correlation with lactic acid (r2 = 0.98), which is produced by soil microbes. The observed high abundances of isopentanoic acid are involved with soil microbial activity. We found that acetic acid in particle phase positively correlated with nonanoic acid (C9) (r2 = 0.63), suggesting that formation of acetic and nonanoic acids are associated with the oxidation of unsaturated fatty acids. We found that forest floor with soil microbes contributes to the emissions of gaseous and particulate LMW monoacids. Our results suggest that forest ecosystem is an important source of organic gases and aerosols in the atmosphere.


2019 ◽  
Vol 12 (1) ◽  
pp. 281-298 ◽  
Author(s):  
Bastian Stieger ◽  
Gerald Spindler ◽  
Dominik van Pinxteren ◽  
Achim Grüner ◽  
Markus Wallasch ◽  
...  

Abstract. A method is presented to quantify the low-molecular-weight organic acids such as formic, acetic, propionic, butyric, pyruvic, glycolic, oxalic, malonic, succinic, malic, glutaric, and methanesulfonic acid in the atmospheric gas and particle phases, based on a combination of the Monitor for AeRosols and Gases in ambient Air (MARGA) and an additional ion chromatography (Compact IC) instrument. Therefore, every second hourly integrated MARGA gas and particle samples were collected and analyzed by the Compact IC, resulting in 12 values per day for each phase. A proper separation of the organic target acids was initially tackled by a laboratory IC optimization study, testing different separation columns, eluent compositions and eluent flow rates for both isocratic and gradient elution. Satisfactory resolution of all compounds was achieved using a gradient system with two coupled anion-exchange separation columns. Online pre-concentration with an enrichment factor of approximately 400 was achieved by solid-phase extraction consisting of a methacrylate-polymer-based sorbent with quaternary ammonium groups. The limits of detection of the method range between 0.5 ng m−3 for malonate and 17.4 ng m−3 for glutarate. Precisions are below 1.0 %, except for glycolate (2.9 %) and succinate (1.0 %). Comparisons of inorganic anions measured at the TROPOS research site in Melpitz, Germany, by the original MARGA and the additional Compact IC are in agreement with each other (R2 = 0.95–0.99). Organic acid concentrations from May 2017 as an example period are presented. Monocarboxylic acids were dominant in the gas phase with mean concentrations of 306 ng m−3 for acetic acid, followed by formic (199 ng m−3), propionic (83 ng m−3), pyruvic (76 ng m−3), butyric (34 ng m−3) and glycolic acid (32 ng m−3). Particulate glycolate, oxalate and methanesulfonate were quantified with mean concentrations of 26, 31 and 30 ng m−3, respectively. Elevated concentrations of gas-phase formic acid and particulate oxalate in the late afternoon indicate photochemical formation as a source.


Author(s):  
G.K.W. Balkau ◽  
E. Bez ◽  
J.L. Farrant

The earliest account of the contamination of electron microscope specimens by the deposition of carbonaceous material during electron irradiation was published in 1947 by Watson who was then working in Canada. It was soon established that this carbonaceous material is formed from organic vapours, and it is now recognized that the principal source is the oil-sealed rotary pumps which provide the backing vacuum. It has been shown that the organic vapours consist of low molecular weight fragments of oil molecules which have been degraded at hot spots produced by friction between the vanes and the surfaces on which they slide. As satisfactory oil-free pumps are unavailable, it is standard electron microscope practice to reduce the partial pressure of organic vapours in the microscope in the vicinity of the specimen by using liquid-nitrogen cooled anti-contamination devices. Traps of this type are sufficient to reduce the contamination rate to about 0.1 Å per min, which is tolerable for many investigations.


1998 ◽  
Vol 1 (5) ◽  
pp. 166-174 ◽  
Author(s):  
Evelyn R Hermes De Santis ◽  
Betsy S Laumeister ◽  
Vidhu Bansal ◽  
Vandana Kataria ◽  
Preeti Loomba ◽  
...  

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