| 1. |
- Le Breton, Michael, 1986, et al.
(författare)
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Application of a FIGAERO ToF CIMS for on-line characterization of real-world fresh and aged particle emissions from buses
- 2019
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Ingår i: Aerosol Science and Technology. - : Informa UK Limited. - 0278-6826 .- 1521-7388. ; 53:3, s. 244-259
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Tidskriftsartikel (refereegranskat)abstract
- © 2019, © 2019 The Author(s). Published with license by Taylor & Francis Group, LLC. On-line chemical characterization of real-world particle emissions from 13 transit buses was performed using a chemical ionization mass spectrometer (CIMS) equipped with a filter inlet for gases and aerosols (FIGAERO). In addition to the fresh emissions the emissions were artificially aged using a potential aerosol mass reactor (Go:PAM). The buses studied were running on different fuel types (diesel, compressed natural gas, and rapeseed methyl ester) and exhaust after-treatment systems (selective catalytic reduction (SCR), exhaust gas recirculation (EGR), and a three-way catalyst). When evaluating emissions from passing exhaust plumes using the FIGAERO ToF-CIMS, two technical features were highlighted from this work, the use of high mass calibrants and the factor enhancement method to be able to filter important compounds from mass spectra including hundreds of species. Here, acetate was used as the reagent ion to enable detection of highly oxygenated species in the exhaust particle emissions with potential high toxicity and/or secondary organic aerosol formation (SOA) potential. The acetate ionization scheme accounted for 4% to 46% of the total emitted particulate mass through identification of 61 species in the spectra. For aged emission the various fuel types provided overlapping species that could explain up to 19% of the aged emissions. This is hypothesized to come from the oxidation of engine lubrication oil, thus a common source for various fuels which was further supported by laboratory measurements. Specific markers from the SCR technology, such as urea oxidation products and further byproducts from hydrolysis were identified and attributed to reactions of isocyanic acid.
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| 2. |
- Lutz, Anna, 1986, et al.
(författare)
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Gas to Particle Partitioning of Organic Acids in the Boreal Atmosphere
- 2019
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Ingår i: Acs Earth and Space Chemistry. - : American Chemical Society (ACS). - 2472-3452. ; 3:7, s. 1279-1287
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Tidskriftsartikel (refereegranskat)abstract
- Gas to particle partitioning of carboxylic acids was investigated using a high-resolution chemical ionization time-of-flight mass spectrometer (HR-CI-ToF-MS) with the filter inlet for gases and aerosol (FIGAERO). Specifically, the partitioning coefficients of 640 components with unique molecular composition were calculated from an assumed linear relationship between [particle]/[gas] versus the mass of the organic fraction (M-org) according to Raoult's law, i.e., equilibrium phase partitioning. We demonstrate that, using the full data set, most of the compounds do not follow a linear relationship. This is especially the case for low- and high-molecular-weight species. Using a subset of the data, with concurrent low sulfate ambient observations ([SO42- < 0.4 mu g m(-3)), the relationship improved significantly and K-i could be derived from the slope of a linear regression to the data. The 100 species with the highest R-2 (>= 0.7) of this regression are presented. The restrictions during high sulfate conditions can be explained by changes in either the equilibrium conditions (e.g., the activity coeffient, gamma(i)) or uptake kinetics (mass transfer limitation). This study demonstrates that partitioning of compounds in the complex ambient atmosphere follows ideal Raoult's law for some limited conditions and stresses the need for studies also in more polluted environments.
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| 3. |
- D'Ambro, E. L., et al.
(författare)
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Molecular composition and volatility of isoprene photochemical oxidation secondary organic aerosol under low- and high-NOx conditions
- 2017
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Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 17:1, s. 159-174
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Tidskriftsartikel (refereegranskat)abstract
- We present measurements of secondary organic aerosol (SOA) formation from isoprene photochemical oxidation in an environmental simulation chamber at a variety of oxidant conditions and using dry neutral seed particles to suppress acid-catalyzed multiphase chemistry. A high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) utilizing iodide-adduct ionization coupled to the Filter Inlet for Gases and Aerosols (FIGAERO) allowed for simultaneous online sampling of the gas and particle composition. Under high-HO2 and low-NO conditions, highly oxygenated (O : C >= 1) C-5 compounds were major components (similar to 50 %) of SOA. The SOA composition and effective volatility evolved both as a function of time and as a function of input NO concentrations. Organic nitrates increased in both the gas and particle phases as input NO increased, but the dominant non-nitrate particle-phase components monotonically decreased. We use comparisons of measured and predicted gas-particle partitioning of individual components to assess the validity of literature-based group-contribution methods for estimating saturation vapor concentrations. While there is evidence for equilibrium partitioning being achieved on the chamber residence timescale (5.2 h) for some individual components, significant errors in group-contribution methods are revealed. In addition, >30% of the SOA mass, detected as low-molecular-weight semivolatile compounds, cannot be reconciled with equilibrium partitioning. These compounds desorb from the FIGAERO at unexpectedly high temperatures given their molecular composition, which is indicative of thermal decomposition of effectively lower-volatility components such as larger molecular weight oligomers.
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| 4. |
- Emanuelsson, Eva U., et al.
(författare)
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Influence of Humidity, Temperature, and Radicals on the Formation and Thermal Properties of Secondary Organic Aerosol (SOA) from Ozonolysis of β-Pinene
- 2013
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Ingår i: Journal of Physical Chemistry A. - : American Chemical Society (ACS). - 1089-5639 .- 1520-5215. ; 117:40, s. 10346-10358
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Tidskriftsartikel (refereegranskat)abstract
- The influence of water and radicals on SOAs produced by β-pinene ozonolysis was investigated at 298 and 288 K using a laminar flow reactor. A volatility tandem differential mobility analyzer (VTDMA) was used to measure the evaporation of the SOA, enabling the parametrization of its volatility properties. The parameters extracted included the temperature at which 50% of the aerosol had evaporated (TVFR0.5) and the slope factor (SVFR). An increase in SVFR indicates a broader distribution of vapor pressures for the aerosol constituents. Reducing the reaction temperature increased SVFR and decreased TVFR0.5 under humid conditions but had less effect on TVFR0.5 under dry conditions. In general, higher water concentrations gave lower TVFR0.5 values, more negative SVFR values, and a reduction in total SOA production. The radical conditions were changed by introducing OH scavengers to generate systems with and without OH radicals and with different [HO2]/[RO2] ratios. The presence of a scavenger and lower [HO2]/[RO2] ratio reduced SOA production. Observed changes in SVFR values could be linked to the more complex chemistry that occurs in the absence of a scavenger and indicated that additional HO2 chemistry gives products with a wider range of vapor pressures. Updates to existing ozonolysis mechanisms with routes that describe the observed responses to water and radical conditions for monoterpenes with endocyclic and exocyclic double bonds are discussed.
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| 5. |
- Fuchs, H., et al.
(författare)
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OH regeneration from methacrolein oxidation investigated in the atmosphere simulation chamber SAPHIR
- 2014
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Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 14:15, s. 7895-7908
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Tidskriftsartikel (refereegranskat)abstract
- Hydroxyl radicals (OH) are the most important reagent for the oxidation of trace gases in the atmosphere. OH concentrations measured during recent field campaigns in isoprene-rich environments were unexpectedly large. A number of studies showed that unimolecular reactions of organic peroxy radicals (RO2) formed in the initial reaction step of isoprene with OH play an important role for the OH budget in the atmosphere at low mixing ratios of nitrogen monoxide (NO) of less than 100 pptv. It has also been suggested that similar reactions potentially play an important role for RO2 from other compounds. Here, we investigate the oxidation of methacrolein (MACR), one major oxidation product of isoprene, by OH in experiments in the simulation chamber SAPHIR under controlled atmospheric conditions. The experiments show that measured OH concentrations are approximately 50% larger than calculated by the Master Chemical Mechanism (MCM) for conditions of the experiments (NO mixing ratio of 90 pptv). The analysis of the OH budget reveals an OH source that is not accounted for in MCM, which is correlated with the production rate of RO2 radicals from MACR. In order to balance the measured OH destruction rate, 0.77 OH radicals (1 sigma error: +/- 0.31) need to be additionally reformed from each reaction of OH with MACR. The strong correlation of the missing OH source with the production of RO2 radicals is consistent with the concept of OH formation from unimolecular isomerization and decomposition reactions of RO2. The comparison of observations with model calculations gives a lower limit of 0.03 s(-1) for the reaction rate constant if the OH source is at-tributed to an isomerization reaction of MACR-1-OH-2-OO and MACR-2-OH-2-OO formed in the MACR + OH reaction as suggested in the literature (Crounse et al., 2012). This fast isomerization reaction would be a competitor to the reaction of this RO2 species with a minimum of 150 pptv NO. The isomerization reaction would be the dominant reaction pathway for this specific RO2 radical in forested regions, where NO mixing ratios are typically much smaller.
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| 6. |
- Hammes, Julia, et al.
(författare)
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Carboxylic acids from limonene oxidation by ozone and hydroxyl radicals: insights into mechanisms derived using a FIGAERO-CIMS
- 2019
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Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 19:20, s. 13037-13052
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Tidskriftsartikel (refereegranskat)abstract
- This work presents the results from a flow reactor study on the formation of carboxylic acids from limonene oxidation in the presence of ozone under NOx-free conditions in the dark. A High-Resolution Time-of-Flight acetate Chemical Ionisation Mass Spectrometer (HR-ToF-CIMS) was used in combination with a Filter Inlet for Gases and AEROsols (FIGAERO) to measure the carboxylic acids in the gas and particle phases. The results revealed that limonene oxidation produced large amounts of carboxylic acids which are important contributors to secondary organic aerosol (SOA) formation. The highest 10 acids contributed 56 %-91 % to the total gas-phase signal, and the dominant gas-phase species in most experiments were C8H12O4, C9H14O4, C7H10O4 and C10H16O3. The particle-phase composition was generally more complex than the gas-phase composition, and the highest 10 acids contributed 47 %-92 % to the total signal. The dominant species in the particle phase were C8H12O5, C9H14O5, C9H12O5 and C10H16O4. The measured concentration of dimers bearing at least one carboxylic acid function in the particle phase was very low, indicating that acidic dimers play a minor role in SOA formation via ozone (O-3)/hydroxyl (OH) oxidation of limonene. Based on the various experimental conditions, the acidic compositions for all experiments were modelled using descriptions from the Master Chemical Mechanism (MCM). The experiment and model provided a yield of large (C-7-C-10) carboxylic acid of the order of 10 % (2 %-23 % and 10 %-15 %, respectively). Significant concentrations of 11 acids, from a total of 16 acids, included in the MCM were measured with the CIMS. However, the model predictions were, in some cases, inconsistent with the measurement results, especially regarding the OH dependence. Reaction mechanisms are suggested to fill-in the knowledge gaps. Using the additional mechanisms proposed in this work, nearly 75 % of the observed gas-phase signal in our lowest concentration experiment (8.4 ppb converted, ca. 23 % acid yield) carried out under humid conditions can be understood.
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| 7. |
- Kaminski, M., et al.
(författare)
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Investigation of the beta-pinene photooxidation by OH in the atmosphere simulation chamber SAPHIR
- 2017
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Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 17:11, s. 6631-6650
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Tidskriftsartikel (refereegranskat)abstract
- Besides isoprene, monoterpenes are the nonmethane volatile organic compounds (VOCs) with the highest global emission rates. Due to their high reactivity towards OH, monoterpenes can dominate the radical chemistry of the atmosphere in forested areas. In the present study the photochemical degradation mechanism of beta-pinene was investigated in the Julich atmosphere simulation chamber SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction Chamber). One focus of this study is on the OH budget in the degradation process. Therefore, the SAPHIR chamber was equipped with instrumentation to measure radicals (OH, HO2, RO2), the total OH reactivity, important OH precursors (O-3, HONO, HCHO), the parent VOC beta-pinene, its main oxidation products, acetone and nopinone and photolysis frequencies. All experiments were carried out under low-NO conditions (<= 300 ppt) and at atmospheric beta-pinene concentrations (<= 5 ppb) with and without addition of ozone. For the investigation of the OH budget, the OH production and destruction rates were calculated from measured quantities. Within the limits of accuracy of the instruments, the OH budget was balanced in all beta-pinene oxidation experiments. However, even though the OH budget was closed, simulation results from the Master Chemical Mechanism (MCM) 3.2 showed that the OH production and destruction rates were underestimated by the model. The measured OH and HO2 concentrations were underestimated by up to a factor of 2, whereas the total OH reactivity was slightly overestimated because the model predicted a nopinone mixing ratio which was 3 times higher than measured. A new, theory-derived, first-generation product distribution by Vereecken and Peeters (2012) was able to reproduce the measured nopinone time series and the total OH reactivity. Nevertheless, the measured OH and HO2 concentrations remained underestimated by the numerical simulations. These observations together with the fact that the measured OH budget was closed suggest the existence of unaccounted sources of HO2. Although the mechanism of additional HO2 formation could not be resolved, our model studies suggest that an activated alkoxy radical intermediate proposed in the model of Vereecken and Peeters (2012) generates HO2 in a new pathway, whose importance has been underestimated so far. The proposed reaction path involves unimolecular rearrangement and decomposition reactions and photolysis of dicarbonyl products, yielding additional HO2 and CO. Further experiments and quantum chemical calculations have to be made to completely unravel the pathway of HO2 formation.
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| 8. |
- Kristensen, Kasper, et al.
(författare)
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High-Molecular Weight Dimer Esters Are Major Products in Aerosols from α-Pinene Ozonolysis and the Boreal Forest
- 2016
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Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 3:8, s. 280-285
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Tidskriftsartikel (refereegranskat)abstract
- This study investigates the contribution of high-molecular weight dimer esters to laboratory-generated α-pinene gas- and particle-phase secondary organic aerosol (SOA) and particulate matter (PM) collected at the Nordic boreal forest site of Hyytiälä, Finland. Laboratory flow reactor experiments (25 °C) show that dimer esters from ozonolysis of α-pinene contribute between 5 and 16% of the freshly formed α-pinene particle-phase SOA mass. An increased level of formation is observed at a higher relative humidity of ∼40%, and the presence of a hydroxyl radical (OH) scavenger is shown to affect the formation of dimer esters. Of the 28 dimer esters identified in laboratory α-pinene SOA, 15 are also observed in ambient PM samples, contributing between 0.5 and 1.6% of the total PM1. The observed esters show good correlation with known α-pinene SOA tracers in collected PM samples. This work reveals an, until now, unrecognized contribution of dimer esters from α-pinene oxidation to boreal forest PM.
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| 9. |
- Lee, Ben H, et al.
(författare)
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Highly functionalized organic nitrates in the southeast United States: Contribution to secondary organic aerosol and reactive nitrogen budgets.
- 2016
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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. - 1091-6490. ; 113:6, s. 1516-21
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Tidskriftsartikel (refereegranskat)abstract
- Speciated particle-phase organic nitrates (pONs) were quantified using online chemical ionization MS during June and July of 2013 in rural Alabama as part of the Southern Oxidant and Aerosol Study. A large fraction of pONs is highly functionalized, possessing between six and eight oxygen atoms within each carbon number group, and is not the common first generation alkyl nitrates previously reported. Using calibrations for isoprene hydroxynitrates and the measured molecular compositions, we estimate that pONs account for 3% and 8% of total submicrometer organic aerosol mass, on average, during the day and night, respectively. Each of the isoprene- and monoterpenes-derived groups exhibited a strong diel trend consistent with the emission patterns of likely biogenic hydrocarbon precursors. An observationally constrained diel box model can replicate the observed pON assuming that pONs (i) are produced in the gas phase and rapidly establish gas-particle equilibrium and (ii) have a short particle-phase lifetime (∼2-4 h). Such dynamic behavior has significant implications for the production and phase partitioning of pONs, organic aerosol mass, and reactive nitrogen speciation in a forested environment.
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| 10. |
- Lopez-Hilfiker, F. D., et al.
(författare)
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A novel method for on-line analysis of gas and particle composition: description and evaluation of a Filter Inlet for Gases and AEROsols (FIGAERO)
- 2013
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Ingår i: Atmospheric Measurement Techniques Discussions. - : Copernicus Publications. - 1867-8610. ; 6:5, s. 9347-9395
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Tidskriftsartikel (refereegranskat)abstract
- We describe a novel inlet that allows measurement of both gas and particle molecular composition when coupled to mass spectrometric, chromatographic, or optical sensors: the Filter Inlet for Gas and AEROsol (FIGAERO). The design goals for the FIGAERO are to allow unperturbed observation of ambient air while simultaneously analyzing gases and collecting particulate matter on a Teflon filter via an entirely separate sampling port. The filter is analyzed periodically by the same sensor on hourly or faster timescales using temperature-programmed thermal desorption. We assess the performance of the FIGAERO by coupling it to a high-resolution time-of-flight chemical-ionization mass spectrometer (HRToF-CIMS) in laboratory chamber studies of α-pinene oxidation and field measurements at a boreal forest location. Low instrument backgrounds give detection limits of ppt or lower for compounds in the gas-phase and in the pg m−3 range for particle phase compounds. The FIGAERO-HRToF-CIMS provides molecular information about both gases and particle composition on the 1 Hz and hourly timescales, respectively for hundreds of compounds. The FIGAERO thermal desorptions are highly reproducible (better than 10%), allowing a calibrated assessment of the effective volatility of desorbing compounds and the role of thermal decomposition during the desorption process. We show that the often multi-modal desorption thermograms arising from secondary organic aerosol (SOA) provide additional insights into molecular composition and/or particle morphology, and exhibit changes with changes in SOA formation or aging pathways.
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