| 1. |
- Baker, Yare, et al.
(author)
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Impact of HO2/RO2 ratio on highly oxygenated α-pinene photooxidation products and secondary organic aerosol formation potential
- 2024
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In: ATMOSPHERIC CHEMISTRY AND PHYSICS. - 1680-7316 .- 1680-7324. ; 24:8, s. 4789-4807
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Journal article (peer-reviewed)abstract
- Highly oxygenated molecules (HOMs) from the atmospheric oxidation of biogenic volatile organic compounds are important contributors to secondary organic aerosol (SOA). Organic peroxy radicals (RO2) and hydroperoxy radicals (HO2) are key species influencing the HOM product distribution. In laboratory studies, experimental requirements often result in overemphasis on RO2 cross-reactions compared to reactions of RO2 with HO2. We analyzed the photochemical formation of HOMs from alpha-pinene and their potential to contribute to SOA formation under high (approximate to 1/1) and low (approximate to 1/100) conditions. As > 1 is prevalent in the daytime atmosphere, sufficiently high is crucial to mimic atmospheric conditions and to prevent biases by low on the HOM product distribution and thus SOA yield. Experiments were performed under steady-state conditions in the new, continuously stirred tank reactor SAPHIR-STAR at Forschungszentrum J & uuml;lich. The ratio was increased by adding CO while keeping the OH concentration constant. We determined the HOM's SOA formation potential, considering its fraction remaining in the gas phase after seeding with (NH4)(2)SO4 aerosol. An increase in led to a reduction in SOA formation potential, with the main driver being a similar to 60 % reduction in HOM-accretion products. We also observed a shift in HOM-monomer functionalization from carbonyl to hydroperoxide groups. We determined a reduction of the HOM's SOA formation potential by similar to 30 % at approximate to 1/1 compared to approximate to 1/100. Particle-phase observations measured a similar decrease in SOA mass and yield. Our study shows that too low ratios compared to the atmosphere can lead to an overestimation of SOA yields.
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| 2. |
- McFiggans, Gordon, et al.
(author)
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Secondary organic aerosol reduced by mixture of atmospheric vapours
- 2019
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In: Nature. - : Springer Science and Business Media LLC. - 0028-0836 .- 1476-4687. ; 565:7741, s. 587-593
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Journal article (peer-reviewed)abstract
- Secondary organic aerosol contributes to the atmospheric particle burden with implications for air quality and climate. Biogenic volatile organic compounds such as terpenoids emitted from plants are important secondary organic aerosol precursors with isoprene dominating the emissions of biogenic volatile organic compounds globally. However, the particle mass from isoprene oxidation is generally modest compared to that of other terpenoids. Here we show that isoprene, carbon monoxide and methane can each suppress the instantaneous mass and the overall mass yield derived from monoterpenes in mixtures of atmospheric vapours. We find that isoprene 'scavenges' hydroxyl radicals, preventing their reaction with monoterpenes, and the resulting isoprene peroxy radicals scavenge highly oxygenated monoterpene products. These effects reduce the yield of low-volatility products that would otherwise form secondary organic aerosol. Global model calculations indicate that oxidant and product scavenging can operate effectively in the real atmosphere. Thus highly reactive compounds (such as isoprene) that produce a modest amount of aerosol are not necessarily net producers of secondary organic particle mass and their oxidation in mixtures of atmospheric vapours can suppress both particle number and mass of secondary organic aerosol. We suggest that formation mechanisms of secondary organic aerosol in the atmosphere need to be considered more realistically, accounting for mechanistic interactions between the products of oxidizing precursor molecules (as is recognized to be necessary when modelling ozone production).
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| 3. |
- Bannan, Thomas J., et al.
(author)
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Measured Saturation Vapor Pressures of Phenolic and Nitro-aromatic Compounds
- 2017
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In: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 51:7, s. 3922-3928
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Journal article (peer-reviewed)abstract
- Phenolic and nitro-aromatic compounds are extremely toxic components of atmospheric aerosol that are currently not well understood. In this Article, solid and subcooled-liquid-state saturation vapor pressures of phenolic and nitro-aromatic compounds are measured using Knudsen Effusion Mass Spectrometry (KEMS) over a range of temperatures (298-318 K). Vapor pressure estimation methods, assessed in this study, do not replicate the observed dependency on the relative positions of functional groups. With a few exceptions, the estimates are biased toward predicting saturation vapor pressures that are too high, by 5-6 orders of magnitude in some cases. Basic partitioning theory comparisons indicate that overestimation of vapor pressures in such cases would cause us to expect these compounds to be present in the gas state, whereas measurements in this study suggest these phenolic and nitro-aromatic will partition into the condensed state for a wide range of ambient conditions if absorptive partitioning plays a dominant role. While these techniques might have both structural and parametric uncertainties, the new data presented here should support studies trying to ascertain the role of nitrogen containing organics on aerosol growth and human health impacts.
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| 4. |
- Krieger, Ulrich K., et al.
(author)
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A reference data set for validating vapor pressure measurement techniques : homologous series of polyethylene glycols
- 2018
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In: Atmospheric Measurement Techniques. - : Copernicus GmbH. - 1867-1381 .- 1867-8548. ; 11:1, s. 49-63
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Journal article (peer-reviewed)abstract
- To predict atmospheric partitioning of organic compounds between gas and aerosol particle phase based on explicit models for gas phase chemistry, saturation vapor pressures of the compounds need to be estimated. Estimation methods based on functional group contributions require training sets of compounds with well-established saturation vapor pressures. However, vapor pressures of semivolatile and low-volatility organic molecules at atmospheric temperatures reported in the literature often differ by several orders of magnitude between measurement techniques. These discrepancies exceed the stated uncertainty of each technique which is generally reported to be smaller than a factor of 2. At present, there is no general reference technique for measuring saturation vapor pressures of atmospherically relevant compounds with low vapor pressures at atmospheric temperatures. To address this problem, we measured vapor pressures with different techniques over a wide temperature range for intercomparison and to establish a reliable training set. We determined saturation vapor pressures for the homologous series of polyethylene glycols (H-(O-CH2-CH2)(n)-OH) for n = 3 to n = 8 ranging in vapor pressure at 298 K from 10(-7) to 5 x 10(-2) Pa and compare them with quantum chemistry calculations. Such a homologous series provides a reference set that covers several orders of magnitude in saturation vapor pressure, allowing a critical assessment of the lower limits of detection of vapor pressures for the different techniques as well as permitting the identification of potential sources of systematic error. Also, internal consistency within the series allows outlying data to be rejected more easily. Most of the measured vapor pressures agreed within the stated uncertainty range. Deviations mostly occurred for vapor pressure values approaching the lower detection limit of a technique. The good agreement between the measurement techniques (some of which are sensitive to the mass accommodation coefficient and some not) suggests that the mass accommodation coefficients of the studied compounds are close to unity. The quantum chemistry calculations were about 1 order of magnitude higher than the measurements. We find that extrapolation of vapor pressures from elevated to atmospheric temperatures is permissible over a range of about 100 K for these compounds, suggesting that measurements should be performed best at temperatures yielding the highest-accuracy data, allowing subsequent extrapolation to atmospheric temperatures.
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| 5. |
- Mehra, Archit, et al.
(author)
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Evaluation of the chemical composition of gas- and particle-phase products of aromatic oxidation
- 2020
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In: ATMOSPHERIC CHEMISTRY AND PHYSICS. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 20:16, s. 9783-9803
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Journal article (peer-reviewed)abstract
- Aromatic volatile organic compounds (VOCs) are key anthropogenic pollutants emitted to the atmosphere and are important for both ozone and secondary organic aerosol (SOA) formation in urban areas. Recent studies have indicated that aromatic hydrocarbons may follow previously unknown oxidation chemistry pathways, including autoxidation that can lead to the formation of highly oxidised products. In this study we evaluate the gas- and particle-phase ions measured by online mass spectrometry during the hydroxyl radical oxidation of substituted C-9-aromatic isomers (1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, propylbenzene and isopropylbenzene) and a substituted polyaromatic hydrocarbon (1-methylnaphthalene) under low- and medium-NO x conditions. A time-of-flight chemical ionisation mass spectrometer (ToF-CIMS) with iodide-anion ionisation was used with a filter inlet for gases and aerosols (FIGAERO) for the detection of products in the particle phase, while a Vocus protontransfer-reaction mass spectrometer (Vocus-PTR-MS) was used for the detection of products in the gas phase. The signal of product ions observed in the mass spectra were compared for the different precursors and experimental conditions. The majority of mass spectral product signal in both the gas and particle phases comes from ions which are common to all precursors, though signal distributions are distinct for different VOCs. Gas- and particle-phase composition are distinct from one another. Ions corresponding to products contained in the near-explicit gas phase Master Chemical Mechanism (MCM version 3.3.1) are utilised as a benchmark of current scientific understanding, and a comparison of these with observations shows that the MCM is missing a range of highly oxidised products from its mechanism. In the particle phase, the bulk of the product signal from all precursors comes from ring scission ions, a large proportion of which are more oxidised than previously reported and have undergone further oxidation to form highly oxygenated organic molecules (HOMs). Under the perturbation of OH oxidation with increased NOx, the contribution of HOM-ion signals to the particle-phase signal remains elevated for more substituted aromatic precursors. Up to 43% of product signal comes from ring-retaining ions including HOMs; this is most important for the more substituted aromatics. Unique products are a minor component in these systems, and many of the dominant ions have ion formulae concurrent with other systems, highlighting the challenges in utilising marker ions for SOA.
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