| 1. |
- Beecken, Jörg, 1982, et al.
(författare)
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Airborne emission measurements of SO2, NOx and particles from individual ships using a sniffer technique
- 2014
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Ingår i: Atmospheric Measurement Techniques. - : Copernicus GmbH. - 1867-1381 .- 1867-8548. ; 7:7, s. 1957-1968
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Tidskriftsartikel (refereegranskat)abstract
- A dedicated system for airborne ship emission measurements of SO2, NOx and particles has been developed and used from several small aircraft. The system has been adapted for fast response measurements at 1 Hz, and the use of several of the instruments is unique. The uncertainty of the given data is about 20% for SO2 and 24% for NOx emission factors. The mean values with one standard deviation for multiple measurements of 158 ships measured from the air on the Baltic and North Sea during 2011 and 2012 show emission factors of 18.8+/-6.5 g kg(fuel)(-1), 66.6+/-23.4 g kg(fuel)(-1) and 1.8+/-1.3 1016 particles kg(fuel)(-1) for SO2, NOx and particle number, respectively. The particle size distributions were measured for particle diameters between 15 and 560 nm. The mean sizes of the particles are between 45 and 54 nm dependent on the distance to the source, and the number size distribution is monomodal. Concerning the sulfur fuel content, around 85% of the monitored ships comply with the International Maritime Organization (IMO) limits. The reduction of the sulfur emission control area (SECA) limit from 1.5 to 1% in 2010 appears to have contributed to reduction of sulfur emissions that were measured in earlier studies from 2007 to 2009. The presented method can be implemented for regular ship compliance monitoring.
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| 2. |
- Donahue, N. M., et al.
(författare)
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Aging of biogenic secondary organic aerosol via gas-phase OH radical reactions
- 2012
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Ingår i: Proceedings of the National Academy of Sciences of the United States of America. - : Proceedings of the National Academy of Sciences. - 0027-8424 .- 1091-6490. ; 109:34, s. 13503-13508
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Tidskriftsartikel (refereegranskat)abstract
- The Multiple Chamber Aerosol Chemical Aging Study (MUCHACHAS) tested the hypothesis that hydroxyl radical (OH) aging significantly increases the concentration of first-generation biogenic secondary organic aerosol (SOA). OH is the dominant atmospheric oxidant, and MUCHACHAS employed environmental chambers of very different designs, using multiple OH sources to explore a range of chemical conditions and potential sources of systematic error. We isolated the effect of OH aging, confirming our hypothesis while observing corresponding changes in SOA properties. The mass increases are consistent with an existing gap between global SOA sources and those predicted in models, and can be described by a mechanism suitable for implementation in those models.
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| 3. |
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| 4. |
- Pathak, Ravi K., et al.
(författare)
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Influence of Ozone and Radical Chemistry on Limonene Organic Aerosol Production and Thermal Characteristics
- 2012
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Ingår i: Environmental Science & Technology. - : American Chemical Society. - 0013-936X .- 1520-5851. ; 46:21, s. 11660-11669
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Tidskriftsartikel (refereegranskat)abstract
- Limonene has a strong tendency to form secondary organic aerosol (SOA) in the atmosphere and in indoor environments. Initial oxidation occurs mainly via ozone or OH radical chemistry. We studied the effect of O3 concentrations with or without a OH radical scavenger (2-butanol) on the SOA mass and thermal characteristics using the Gothenburg Flow Reactor for Oxidation Studies at Low Temperatures and a volatility tandem differential mobility analyzer. The SOA mass using 15 ppb limonene was strongly dependent on O3 concentrations and the presence of a scavenger. The SOA volatility in the presence of a scavenger decreased with increasing levels of O3, whereas without a scavenger, there was no significant change. A chemical kinetic model was developed to simulate the observations using vapor pressure estimates for compounds that potentially contributed to SOA. The model showed that the product distribution was affected by changes in both OH and ozone concentrations, which partly explained the observed changes in volatility, but was strongly dependent on accurate vapor pressure estimation methods. The model–experiment comparison indicated a need to consider organic peroxides as important SOA constituents. The experimental findings could be explained by secondary condensed-phase ozone chemistry, which competes with OH radicals for the oxidation of primary unsaturated products.
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| 5. |
- Salo, Kent, 1967, et al.
(författare)
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Aerosol volatility and enthalpy of sublimation of carboxylic acids.
- 2010
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Ingår i: The journal of physical chemistry. A. - : American Chemical Society (ACS). - 1520-5215 .- 1089-5639. ; 114:13, s. 4586-94
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Tidskriftsartikel (refereegranskat)abstract
- The enthalpy of sublimation has been determined for nine carboxylic acids, two cyclic (pinonic and pinic acid) and seven straight-chain dicarboxylic acids (C(4) to C(10)). The enthalpy of sublimation was determined from volatility measurements of nano aerosol particles using a volatility tandem differential mobility analyzer (VTDMA) set-up. Compared to the previous use of a VTDMA, this novel method gives enthalpy of sublimation determined over an extended temperature range (DeltaT approximately 40 K). The determined enthalpy of sublimation for the straight-chain dicarboxylic acids ranged from 96 to 161 kJ mol(-1), and the calculated vapor pressures at 298 K are in the range of 10(-6)-10(-3) Pa. These values indicate that dicarboxylic acids can take part in gas-to-particle partitioning at ambient conditions and may contribute to atmospheric nucleation, even though homogeneous nucleation is unlikely. To obtain consistent results, some experimental complications in producing nanosized crystalline aerosol particles were addressed. It was demonstrated that pinonic acid "used as received" needed a further purification step before being suspended as a nanoparticle aerosol. Furthermore, it was noted from distinct differences in thermal properties that aerosols generated from pimelic acid solutions gave two types of particles. These two types were attributed to crystalline and amorphous configurations, and based on measured thermal properties, the enthalpy of vaporization was 127 kJ mol(-1) and that of sublimation was 161 kJ mol(-1). This paper describes a new method that is complementary to other similar methods and provides an extension of existing experimental data on physical properties of atmospherically relevant compounds.
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| 6. |
- Salo, Kent, 1967
(författare)
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Physical properties and processes of secondary organic aerosol and its constituents
- 2011
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Atmospheric aerosol particles are involved in several important processes including the formation of clouds and precipitation. A considerable fraction of the ambient aerosol mass consists of organic compounds of both primary and secondary origin. These organic compounds are often semi-volatile and susceptible to oxidation which makes the organic aerosol a dynamic system, both chemically and physically. Once an aerosol is formed or released into the atmosphere, several processes will begin to alter its chemical and physical properties. The focus of the work presented in this thesis has been to use experimental methods to characterise single aerosol components and more complex experimental systems, involving the formation and processing of secondary organic aerosol (SOA). The volatility of aerosol particles, e.g. the evaporation rate of the particles upon heating, can provide information of several important properties. From an aerosol consisting only of one pure compound it is possible to derive physical quantities like saturation vapour pressure and enthalpy of evaporation. In more complex systems like a secondary organic aerosol the volatility can give information about changes in composition, state of oxidation and degree of internal or external mixing. With the use of a volatility tandem differential mobility analyser (VTDMA), the saturation vapour pressures and enthalpies of evaporation have been determined for pure compounds that are known constituents of ambient aerosol samples i.e. nine carboxylic acids. Two of them were cyclic, pinic and pinonic acid and seven of them were straight chain dicarboxylic acids with number of carbons ranging from C4 to C10. These properties were in addition evaluated for the aminium nitrates of mono-, di-, and trimethylamine, ethyl- and monoethanolamine. The calculated saturation vapour pressures for the carboxylic acids were in the range of 10-6 to 10-3 Pa and the determined enthalpies of evaporation ranged from 83 to 161 kJ mol-1. The corresponding values for the aminium nitrates were for the calculated saturation vapour pressures approximately 10-4 Pa and for the enthalpies of evaporation 54 to 72 kJ mol-1. The VTDMA system has also been utilised to characterise SOA formed in the AIDA and SAPHIRE smog chambers from the ozonolysis of α-pinene and limonene and the change in the SOA thermal properties during OH radical induced ageing. Further, the effect of elevated ozone concentration and radical chemistry on SOA formed from limonene ozonolysis in the G-FROST laminar flow reactor was investigated. In addition, to compare with vapour pressures of aminium nitrates SOA generated from photooxodation of alkyl amines have been characterised in the EUPHORE smog chamber. The calculated vapour pressures of all the investigated pure compounds in this work characterise them to be in the semi-volatile organic compound (SVOC) category; hence they will be present both in the gaseous and condensed phase in the atmosphere. This implied that all these compounds will be susceptible for gas phase OH radical oxidation that was demonstrated to be an important process for the complex mixtures investigated in the smog chamber facilities. The OH chemistry was also influencing the volatility of aerosol produced in G-FROST by ozonlysis. Regarding photooxodation of amines the aerosols produced under high NOx conditions initially mimicked the pure salts but was efficiently transformed by oxidation into an aerosol with similar volatility properties as observed in the terpene oxidation experiments.
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| 7. |
- Salo, Kent, 1967, et al.
(författare)
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Thermal characterization of aminium nitrate nanoparticles.
- 2011
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Ingår i: The journal of physical chemistry. A. - : American Chemical Society (ACS). - 1520-5215 .- 1089-5639. ; 115:42, s. 11671-7
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Tidskriftsartikel (refereegranskat)abstract
- Amines are widely used and originate from both anthropogenic and natural sources. Recently, there is, in addition, a raised concern about emissions of small amines formed as degradation products of the more complex amines used in CO(2) capture and storage systems. Amines are bases and can readily contribute to aerosol mass and number concentration via acid-base reactions but are also subject to gas phase oxidation forming secondary organic aerosols. To provide more insight into the atmospheric fate of the amines, this paper addresses the volatility properties of aminium nitrates suggested to be produced in the atmosphere from acid-base reactions of amines with nitric acid. The enthalpy of vaporization has been determined for the aminium nitrates of mono-, di-, trimethylamine, ethylamine, and monoethanolamine. The enthalpy of vaporization was determined from volatility measurements of laboratory generated aerosol nanoparticles using a volatility tandem differential mobility analyzer set up. The determined enthalpy of vaporization for aminium nitrates range from 54 up to 74 kJ mol(-1), and the calculated vapor pressures at 298 K are around 10(-4) Pa. These values indicate that aminium nitrates can take part in gas-to-particle partitioning at ambient conditions and have the potential to nucleate under high NO(x) conditions, e.g., in combustion plumes.
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| 8. |
- Salo, Kent, 1967, et al.
(författare)
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Volatility of secondary organic aerosol during OH radical induced ageing
- 2011
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Ingår i: Atmos. Chem. Phys. - : Copernicus GmbH. ; 11, s. 11055-11067
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Tidskriftsartikel (refereegranskat)abstract
- The aim of this study was to investigate oxidation of SOA formed from ozonolysis of α-pinene and limonene by hydroxyl radicals. This paper focuses on changes of particle volatility, using a Volatility Tandem DMA (VTDMA) set-up, in order to explain and elucidate the mechanism behind atmospheric ageing of the organic aerosol. The experiments were conducted at the AIDA chamber facility of Karlsruhe Institute of Technology (KIT) in Karlsruhe and at the SAPHIR chamber of Forchungzentrum Jülich (FZJ) in Jülich. A fresh SOA was produced from ozonolysis of α-pinene or limonene and then aged by enhanced OH exposure. As an OH radical source in the AIDA-chamber the ozonolysis of tetramethylethylene (TME) was used while in the SAPHIR-chamber the OH was produced by natural light photochemistry. A general feature is that SOA produced from ozonolysis of α-pinene and limonene initially was rather volatile and becomes less volatile with time in the ozonolysis part of the experiment. Inducing OH chemistry or adding a new portion of precursors made the SOA more volatile due to addition of new semi-volatile material to the aged aerosol. The effect of OH chemistry was less pronounced in high concentration and low temperature experiments when lower relative amounts of semi-volatile material were available in the gas phase. Conclusions drawn from the changes in volatility were confirmed by comparison with the measured and modelled chemical composition of the aerosol phase. Three quantified products from the α-pinene oxidation; pinonic acid, pinic acid and methylbutanetricarboxylic acid (MBTCA) were used to probe the processes influencing aerosol volatility. A major conclusion from the work is that the OH induced ageing can be attributed to gas phase oxidation of products produced in the primary SOA formation process and that there was no indication on significant bulk or surface reactions. The presented results, thus, strongly emphasise the importance of gas phase oxidation of semi- or intermediate-volatile organic compounds (SVOC and IVOC) for atmospheric aerosol ageing.
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