Deconvolution of FIGAERO-CIMS thermal desorption profiles using positive matrix factorisation to identify chemical and physical processes during particle evaporation

he measurements of aerosol particles with a filter inlet for gases and aerosols (FIGAERO) together with a chemical ionisation mass spectrometer (CIMS) yield the overall chemical composition of the particle phase. In addition, the thermal desorption profiles obtained for each detected ion composition contain information about the volatility of the detected compounds, which is an important property for understanding many physical properties like gas–particle partitioning. We coupled this thermal desorption method with isothermal evaporation prior to the sample collection to investigate the chemical composition changes during isothermal particle evaporation and particulate-water-driven chemical reactions in α-pinene secondary organic aerosol (SOA) of three different oxidative states. The thermal desorption profiles of all detected elemental compositions were then analysed with positive matrix factorisation (PMF) to identify the drivers of the chemical composition changes observed during isothermal evaporation. The keys to this analysis were to use the error matrix as a tool to weight the parts of the data carrying most information (i.e. the peak area of each thermogram) and to run PMF on a combined data set of multiple thermograms from different experiments to enable a direct comparison of the individual factors between separate measurements. The PMF was able to identify instrument background factors and separate them from the part of the data containing particle desorption information. Additionally, PMF allowed us to separate the direct desorption of compounds detected at a specific elemental composition from other signals with the same composition that stem from the thermal decomposition of thermally instable compounds with lower volatility. For each SOA type, 7–9 factors were needed to explain the observed thermogram behaviour. The contribution of the factors depended on the prior isothermal evaporation. Decreased contributions from the factors with the lowest desorption temperatures were observed with increasing isothermal evaporation time. Thus, the factors identified by PMF could be interpreted as volatility classes. The composition changes in the particles due to isothermal evaporation could be attributed to the removal of volatile factors with very little change in the desorption profiles of the individual factors (i.e. in the respective temperatures of peak desorption, Tmax). When aqueous-phase reactions took place, PMF was able to identify a new factor that directly identified the ions affected by the chemical processes. We conducted a PMF analysis of the FIGAERO–CIMS thermal desorption data for the first time using laboratory-generated SOA particles. But this method can be applied to, for example, ambient FIGAERO–CIMS measurements as well. There, the PMF analysis of the thermal desorption data identifies organic aerosol (OA) sources (such as biomass burning or oxidation of different precursors) and types, e.g. hydrocarbon-like (HOA) or oxygenated organic aerosol (OOA). This information could also be obtained with the traditional approach, namely the PMF analysis of the mass spectra data integrated for each thermogram. But only our method can also obtain the volatility information for each OA source and type. Additionally, we can identify the contribution of thermal decomposition to the overall signal

Cloud droplet activation of black carbon particles coated with organic compounds of varying solubility

Atmospheric black carbon (BC) particles are a concern due to their impact on air quality and climate. Their net climate effect is, however, still uncertain. This uncertainty is partly related to the contribution of coated BC particles to the global cloud condensation nuclei (CCN) budgets. In this study, laboratory measurements were performed to investigate CCN activity of BC (REGAL 400R pigment black) particles, in pure state or coated through evaporating and subsequent condensation of glutaric acid, levoglucosan (both water-soluble organics) or oleic acid (an organic compound with low solubility). A combination of soot particle aerosol mass spectrometer (SP-AMS) measurements and size distribution measurements with a scanning mobility particle sizer (SMPS) showed that the studied BC particles were nearly spherical agglomerates with a fractal dimension of 2.79 and that they were coated evenly by the organic species. The CCN activity of BC particles increased after coating with all the studied compounds and was governed by the fraction of organic material. The CCN activation of the BC particles coated by glutaric acid and levoglucosan were in good agreement with the theoretical calculations using the shell-and-core model, which is based on a combination of the CCN activities of the pure compounds. The oleic acid coating enhanced the CCN activity of the BC particles, even though the pure oleic acid particles were CCN inactive. The surprising effect of oleic acid might be related to the arrangement of the oleic acid molecules on the surface of the BC cores or other surface phenomena facilitating water condensation onto the coated particles. Our results show that present theories have potential for accurately predicting the CCN activity of atmospheric BC coated with organic species, given that the identities and amounts of the coating species are known. Furthermore, our results suggest that even relatively thin soluble coatings (around 2&thinsp;nm for the compounds studied here) are enough to make the insoluble BC particles CCN active at typical atmospheric supersaturations and thus be efficiently taken up by cloud droplets. This highlights the need for an accurate description of the composition of atmospheric particles containing BC to unravel their net impact on climate.</p

Composition and volatility of secondary organic aerosol (SOA) formed from oxidation of real tree emissions compared to simplified volatile organic compound (VOC) systems

Secondary organic aerosol (SOA) is an important constituent of the atmosphere where SOA particles are formed chiefly by the condensation or reactive uptake of oxidation products of volatile organic compounds (VOCs). The mass yield in SOA particle formation, as well as the chemical composition and volatility of the particles, is determined by the identity of the VOC precursor(s) and the oxidation conditions they experience. In this study, we used an oxidation flow reactor to generate biogenic SOA from the oxidation of Scots pine emissions. Mass yields, chemical composition and volatility of the SOA particles were characterized and compared with SOA particles formed from oxidation of α-pinene and from a mixture of acyclic–monocyclic sesquiterpenes (farnesenes and bisabolenes), which are significant components of the Scots pine emissions. SOA mass yields for Scots pine emissions dominated by farnesenes were lower than for α-pinene but higher than for the artificial mixture of farnesenes and bisabolenes. The reduction in the SOA yield in the farnesene- and bisabolene-dominated mixtures is due to exocyclic C=C bond scission in these acyclic–monocyclic sesquiterpenes during ozonolysis leading to smaller and generally more volatile products. SOA particles from the oxidation of Scots pine emissions had similar or lower volatility than SOA particles formed from either a single precursor or a simple mixture of VOCs. Applying physical stress to the Scots pine plants increased their monoterpene, especially monocyclic β-phellandrene, emissions, which further decreased SOA particle volatility and increased SOA mass yield. Our results highlight the need to account for the chemical complexity and structure of real-world biogenic VOC emissions and stress-induced changes to plant emissions when modelling SOA production and properties in the atmosphere. These results emphasize that a simple increase or decrease in relative monoterpene and sesquiterpene emissions should not be used as an indicator of SOA particle volatility

Insights into the O : C-dependent mechanisms controlling the evaporation of α-pinene secondary organic aerosol particles

The volatility of oxidation products of volatile organic compounds (VOCs) in the atmosphere is a key factor to determine if they partition into the particle phase contributing to secondary organic aerosol (SOA) mass. Thus, linking volatility and measured particle composition will provide insights into SOA formation and its fate in the atmosphere. We produced α-pinene SOA with three different oxidation levels (characterized by average oxygen-to-carbon ratio; O:C‾=0.53, 0.69, and 0.96) in an oxidation flow reactor. We investigated the particle volatility by isothermal evaporation in clean air as a function of relative humidity (RH &lt;2&thinsp;%, 40&thinsp;%, and 80&thinsp;%) and used a filter-based thermal desorption method to gain volatility and chemical composition information. We observed reduced particle evaporation for particles with increasing O:C‾ ratio, indicating that particles become more resilient to evaporation with oxidative aging. Particle evaporation was increased in the presence of water vapour and presumably particulate water; at the same time the resistance of the residual particles to thermal desorption was increased as well. For SOA with O:C‾=0.96, the unexpectedly large increase in mean thermal desorption temperature and changes in the thermogram shapes under wet conditions (80&thinsp;% RH) were an indication of aqueous phase chemistry. For the lower O:C‾ cases, some water-induced composition changes were observed. However, the enhanced evaporation under wet conditions could be explained by the reduction in particle viscosity from the semi-solid to liquid-like range, and the observed higher desorption temperature of the residual particles is a direct consequence of the increased removal of high-volatility and the continued presence of low-volatility compounds.</p

Size-dependent influence of NO_x on the growth rates of organic aerosol particles

Atmospheric new-particle formation (NPF) affects climate by contributing to a large fraction of the cloud condensation nuclei (CCN). Highly oxygenated organic molecules (HOMs) drive the early particle growth and therefore substantially influence the survival of newly formed particles to CCN. Nitrogen oxide (NO_x) is known to suppress the NPF driven by HOMs, but the underlying mechanism remains largely unclear. Here, we examine the response of particle growth to the changes of HOM formation caused by NO_x. We show that NO_x suppresses particle growth in general, but the suppression is rather nonuniform and size dependent, which can be quantitatively explained by the shifted HOM volatility after adding NO_x. By illustrating how NO_x affects the early growth of new particles, a critical step of CCN formation, our results help provide a refined assessment of the potential climatic effects caused by the diverse changes of NO_x level in forest regions around the globe