Chemical Characterization of Gas- and Particle-Phase Products from the Ozonolysis of alpha-Pinene in the Presence of Dimethylamine

Amines are recognized as key compounds in new particle formation (NPF) and secondary organic aerosol (SOA) formation. In addition, ozonolysis of a-pinene contributes substantially to the formation of biogenic SOAs in the atmosphere. In the present study, ozonolysis of a-pinene in the presence of dimethylamine (DMA) was investigated in a flow tube reactor. Effects of amines on SOA formation and chemical composition were examined. Enhancement of NPF and SOA formation was observed in the presence of DMA. Chemical characterization of gas and particle-phase products by high-resolution mass spectrometric techniques revealed the formation of nitrogen containing compounds. Reactions between ozonolysis reaction products of a-pinene, such as pinonaldehyde or pinonic acid, and DMA were observed. Possible reaction pathways are suggested for the formation of the reaction products. Some of the compounds identified in the laboratory study were also observed in aerosol samples (PM1) collected at the SMEAR II station (Hyytiala, Finland) suggesting that DMA might affect the ozonolysis of a-pinene in ambient conditions.Peer reviewe

Vertical profiles of volatile organic compounds and fine particles in atmospheric air by using an aerial drone with miniaturized samplers and portable devices

The increase in volatile organic compound (VOC) emissions released into the atmosphere is one of the main threats to human health and climate. VOCs can adversely affect human life through their contribution to air pollution directly and indirectly by reacting via several mechanisms in the air to form secondary organic aerosols. In this study, an aerial drone equipped with miniaturized air-sampling systems including up to four solid-phase microextraction (SPME) Arrows and four in-tube extraction (ITEX) samplers for the collection of VOCs, along with portable devices for the real-time measurement of black carbon (BC) and total particle numbers at high altitudes was exploited. In total, 135 air samples were collected under optimal sampling conditions from 4 to 14 October 2021 at the boreal forest SMEAR II station, Finland. A total of 48 different VOCs, including nitrogen-containing compounds, alcohols, aldehydes, ketones, organic acids, and hydrocarbons, were detected at different altitudes from 50 to 400 m above ground level with concentrations of up to 6898 ng m−3 in the gas phase and 8613 ng m−3 in the particle phase. Clear differences in VOC distributions were seen in samples collected from different altitudes, depending on the VOC sources. It was also possible to collect aerosol particles by the filter accessory attached on the ITEX sampling system, and five dicarboxylic acids were quantified with concentrations of 0.43 to 10.9 µg m−3. BC and total particle number measurements provided similar diurnal patterns, indicating their correlation. For spatial distribution, BC concentrations were increased at higher altitudes, being 2278 ng m−3 at 100 m and 3909 ng m−3 at 400 m. The measurements aboard the drone provided insights into horizontal and vertical variability in BC and aerosol number concentrations above the boreal forest.</p

Particles, air quality, policy and health

The diversity of ambient particle size and chemical composition considerably complicates pinpointing the specific causal associations between exposure to particles and adverse human health effects, the contribution of different sources to ambient particles at different locations, and the consequent formulation of policy action to most cost-effectively reduce harm caused by airborne particles. Nevertheless, the coupling of increasingly sophisticated measurements and models of particle composition and epidemiology continue to demonstrate associations between particle components and sources (and at lower concentrations) and a wide range of adverse health outcomes. This article reviews the current approaches to source apportionment of ambient particles and the latest evidence for their health effects, and describes the current metrics, policies and legislation for the protection of public health from ambient particles. A particular focus is placed on particles in the ultrafine fraction. The review concludes with an extended evaluation of emerging challenges and future requirements in methods, metrics and policy for understanding and abating adverse health outcomes from ambient particles

Econometric Information Recovery in Behavioral Networks

In this paper, we suggest an approach to recovering behavior-related, preference-choice network information from observational data. We model the process as a self-organized behavior based random exponential network-graph system. To address the unknown nature of the sampling model in recovering behavior related network information, we use the Cressie-Read (CR) family of divergence measures and the corresponding information theoretic entropy basis, for estimation, inference, model evaluation, and prediction. Examples are included to clarify how entropy based information theoretic methods are directly applicable to recovering the behavioral network probabilities in this fundamentally underdetermined ill posed inverse recovery problem

Analysis of PAH compounds in soil with on-line coupled pressurised hot water extraction-microporous membrane liquid-liquid extraction-gas chromatography

Pressurised hot water extraction (PHWE) was coupled on-line with microporous membrane liquid-liquid extraction (MMLLE) and gas chromatography (GC) in the analysis of polycyclic aromatic hydrocarbon (PAH) compounds in soil. The MMLLE serves as a trapping device after the PHWE. Water from PHWE is directed to the donor side of the membrane unit and the analytes are extracted to the acceptor solution on the other side of the membrane. The role of MMLLE is to clean and concentrate the extract, which is then transferred on-line to the GC via a sample loop and an on-column interface using partially concurrent solvent evaporation. Separate optimisation of MMLLE and simulations of the PHWE-MMLLE connection were carried out before the actual on-line coupling. After optimisation of the whole on-line system, the efficiencies of the PHWE-MMLLE-GC and PHWE-solid-phase trap extractions were compared. The PHWE-MMLLE-GC method allowed on-line analysis of soil samples. The method was linear, with limits of detection in the range 0.05-0.13 ng and limits of quantification 0.65-1.66 wg gm1. Comparison of the results with those obtained by other techniques confirmed the good performance

Comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry in the identification of organic compounds in atmospheric aerosols from coniferous forest

Comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC × GC-TOF-MS) was applied in the identification of organic compounds in atmospheric aerosols from coniferous forest. The samples were collected at Hyytiälä, Finland, as part of the QUEST campaign, in Spring 2003. Manual and automated search procedures were compared in the identification. An automated procedure is preferable when a large number of data files need to be processed; but manual search was more accurate with the present samples, where the number of compounds was large and most of the compounds of interest were present at trace level. Altogether, about 50 compounds were identified on the basis of mass spectra and linear retention indices. The identified compounds included oxidised monoterpenes, acyclic alkanes, alkenes, ketones and aldehydes, as well as a few alcohols, acids, and aromatic compounds. © 2006 Elsevier B.V. All rights reserved

Emissions of biogenic volatile organic compounds from the boreal forest floor and understory: a study by solid-phase microextraction and portable gas chromatography-mass spectrometry

Vegetation introduces to the atmosphere a diversity of biogenic volatile organic compounds (BVOCs) which affect atmospheric chemistry, air quality and climate. Understory emissions might contribute significantly to the total BVOCs budget. In this work, either dynamic or static solid-phase microextraction (SPME) combined with portable gas chromatography-mass spectrometry were optimised and used for the in-situ measurement of the most abundant BVOCs at understory level. The study was performed in summer 2015 at the SMEAR II station in Hyytiälä, Finland. The most abundant BVOCs measured in soil chambers and ambient air were α-pinene and Δ3-carene, and their relative concentrations were similar in every chamber. These species constituted 80%–90% of the measured monoterpenes. Aliphatic aldehydes were also measured, and their amounts were lower in soil chambers than in ambient air. Air BVOC concentrations were markedly higher when the wind direction was from SE, which was associated with transportation from nearby sawmills

Characterization of organic compounds in 10- to 50-nm aerosol particles in boreal forest with laser desorption -ionization aerosol mass spectrometer and comparison with other techniques

The aim of this study was to characterize the organic composition of ambient ultrafine particles (< 50 nm) in a boreal forest environment and compare the analytical results obtained by different techniques with use a data analysis software. In the chromatographic techniques, particles were collected on a filter and analyzed off-line after sample preparation, whereas in the aerosol MS, particle analysis was performed directly from the particle source.Many compounds and chemical groups were identified with a laser aerosol mass spectrometer (laser AMS) and selected organic compounds, including acids, polyols, amines and aldehydes, from 50 nm filter samples were quantified. Interesting components found with the laser AMS included oxygenated and aliphatic hydrocarbons, aromatic compounds, amines, and black carbon. The amines found on laser AMS may be related to new particle formation events at particle sizes 10-25 nm. Correlations between the results obtained with different instruments were clarified, and the best correlations were found between laser AMS and 50-nm size filter samples. There were no correlations between the laser AMS data and meteorological data or on-line measured gas phase compounds. The black carbon found on laser AMS had moderate correlation for levoglucosan found on all-sized filter samples. Finally, the correlation analysis revealed that the information obtained from sub-50-nm size range particles and results for particles several times higher could not be directly compared. (C) 2011 Elsevier Ltd. All rights reserved