Showing papers by "Thomas F. Mentel published in 2019"

Highly Oxygenated Organic Molecules (HOM) from Gas-Phase Autoxidation Involving Peroxy Radicals: A Key Contributor to Atmospheric Aerosol

Abstract: Highly oxygenated organic molecules (HOM) are formed in the atmosphere via autoxidation involving peroxy radicals arising from volatile organic compounds (VOC). HOM condense on pre-existing particles and can be involved in new particle formation. HOM thus contribute to the formation of secondary organic aerosol (SOA), a significant and ubiquitous component of atmospheric aerosol known to affect the Earth's radiation balance. HOM were discovered only very recently, but the interest in these compounds has grown rapidly. In this Review, we define HOM and describe the currently available techniques for their identification/quantification, followed by a summary of the current knowledge on their formation mechanisms and physicochemical properties. A main aim is to provide a common frame for the currently quite fragmented literature on HOM studies. Finally, we highlight the existing gaps in our understanding and suggest directions for future HOM research.

Secondary organic aerosol reduced by mixture of atmospheric vapours

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). Adding reactive gases such as isoprene to mixtures lowers the production of secondary organic aerosol in the atmosphere, thus reducing the atmospheric particulate burden, with implications for human health and climate.

Carboxylic acids from limonene oxidation by ozone and hydroxyl radicals: insights into mechanisms derived using a FIGAERO-CIMS

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 ( O3 )/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 ( C7 – C10 ) 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.

Measurements of hydroperoxy radicals (HO 2 ) at atmospheric concentrations using bromide chemical ionisation mass spectrometry

Abstract: . Hydroxyl and hydroperoxy radicals are key species for the understanding of atmospheric oxidation processes. Their measurement is challenging due to their high reactivity; therefore, very sensitive detection methods are needed. Within this study, the measurement of hydroperoxy radicals ( HO2 ) using chemical ionisation combined with a high-resolution time-of-flight mass spectrometer (Aerodyne Research Inc.) employing bromide as the primary ion is presented. The sensitivity reached is equal to 0.005×108 HO2 cm −3 for 10 6 cps of bromide and 60 s of integration time, which is below typical HO2 concentrations found in the atmosphere. The detection sensitivity of the instrument is affected by the presence of water vapour. Therefore, a water-vapour-dependent calibration factor that decreases approximately by a factor of 2 if the water vapour mixing ratio increases from 0.1 % to 1.0 % needs to be applied. An instrumental background, most likely generated by the ion source that is equivalent to a HO2 concentration of ( 1.5 ± 0.2 ) × 10 8 molecules cm−3 , is subtracted to derive atmospheric HO2 concentrations. This background can be determined by overflowing the inlet with zero air. Several experiments were performed in the atmospheric simulation chamber SAPHIR at the Forschungszentrum Julich to test the instrument performance in comparison to the well-established laser-induced fluorescence (LIF) technique for measurements of HO2 . A highly linear correlation coefficient of R2=0.87 is achieved. The slope of the linear regression of 1.07 demonstrates the good absolute agreement of both measurements. Chemical conditions during experiments allowed for testing the instrument's behaviour in the presence of atmospheric concentrations of H2O , NOx , and O3 . No significant interferences from these species were observed. All of these facts demonstrate a reliable measurement of HO2 by the chemical ionisation mass spectrometer presented.

Highly Oxygenated Molecules (HOM) from Gas-Phase Autoxidation Involving Organic Peroxy Radicals: A Key Contributor to Atmospheric Aerosol

Abstract: Highly oxygenated organic molecules (HOM) are formed in the atmosphere via autoxidation involving peroxy radicals arising from volatile organic compounds (VOC). HOM condense on pre-existing particles and can be involved in new particle formation. HOM thus contribute to the formation of secondary organic aerosol (SOA), a significant and ubiquitous component of atmospheric aerosol known to affect the Earth’s radiation balance. HOM were discovered only very recently, but the interest in these compounds has grown rapidly. In this Review, we define HOM and describe the currently available techniques for their identification/quantification, followed by a summary of the current knowledge on their formation mechanisms and physicochemical properties. A main aim is to provide a common frame for the currently quite fragmented literature on HOM studies. Finally, we highlight the existing gaps in our understanding and suggest directions for future HOM research.