Browsing by study line "Ilmakehän kemia ja analyysi"

Air ions can play an important role in new particle formation (NPF) process and consequently influence the atmospheric aerosols, which affect climate and air quality as potential cloud condensation nuclei. However, the air ions and their role in NPF have not been comprehensively investigated yet, especially in polluted area. To explore the air ions in polluted environment, we compared the air ions at SORPES site, a suburban site in polluted eastern China, with those at SMEAR II, a well-studied boreal forest site in Finland, based on the air ion number size distribution (0.8-42 nm) measured with Neutral Cluster and Air Ion Spectrometer (NAIS) during 7 June 2019 to 31 August 2020. Air ions were size classified into three size ranges: cluster (0.8-2 nm), intermediate (2-7 nm), and large (7-20 nm). Median concentration of cluster ions at SORPES (217 cm−3) was about 6 times lower than that at SMEAR II (1268 cm−3) due to the high CS and pre-existing particle loading in polluted area, whereas the median large ion concentration at SORPES (197 cm−3) was about 3 times higher than that of SMEAR II (67 cm−3). Seasonal variations of ion concentration differed with ion sizes and ion polarity at two sites. High concentration of cluster ions was observed in the evening in the spring and autumn at SMEAR II, while the cluster ion concentration remained at a high level all day in the same seasons. The NPF events occurred more frequently at SORPES site (SMEAR II 16% ; SORPES: 39%), and the highest values of NPF frequency at both sites were in spring ((SMEAR II: spring: 43%; SORPES: spring: 56%). During the noon time on NPF event day, the concentration of intermediate ions were 8-14 times higher than same ours on non-event days, indicating that can be used as an indicator for NPF in SMEAR II and SORPES. The median formation rate of 1.5 nm at SMEAR II were higher then that at SORPES, while higher formation rate of 3 nm ions were observed at SORPES. At 3 nm, the formation rate of charged particles was only 11% and 1.6% of the total rate at SMEAR II and SORPES respectively, which supports the current view that neutral ways dominate the new particle process in continental boundary. However, higher ratio between charged and total formation rate of 3 nm particle at SMEAR II indicates ion-induced nucleation can have a bigger contribution to NPF in clear area in comparison to polluted area. Higher median GR of 3-7 nm (SMEAR II: 3.1 nm h−1; SORPES: 3.7 nm h−1) and 7-20 nm (SMEAR II: 5.5 nm h−1; SORPES: 6.9 nm h−1) ions at SORPES were found in comparison to SMEAR II, suggesting the higher availability of condensing vapors at SORPES. This study presented a comprehensive comparison of air ions in completely different environments, and highlighted the need for long-term ion measurements to improve the understanding of air ions and their role in NPF in polluted area like eastern China

The oxidation mechanisms of atmospheric organic compounds are an important puzzle piece for many atmospherically relevant topics, including but not limited to air quality and climate change. One poorly understood step in this oxidation process is peroxy radical recombination, in some conditions the most important sink reaction for peroxy radicals, which are formed in abundance due to gas phase reactions in the lower troposphere. After a few initial steps, the peroxy radical recombination reaction results in the ejection of O_2 leaving behind a pair of alkoxy radicals in close proximity. This reactive complex has three known reaction pathways: Hydrogen shift forming an alcohol and a carbonyl compound, radical recombination forming a ROOR dimer, and diffusive break-up forming two free alkoxy radicals. In this thesis, alkoxy bond scission followed by radical recombination resulting in the formation of a ROR is proposed as a fourth reaction pathway. To test the hypothesis, computational chemistry was used to determine alkoxy bond scission rates for radicals of atmospheric significance, and gas-phase oxidation experiments were realized on three peroxy radical precursor molecules to look for signs of ROR formation. More precisely, the Eyring equation was used to calculate the rate of alkoxy bond scission on a potential energy surface determined using density functionals, with corrections to electronic energy using coupled-cluster calculations. In the experiments, liquid phase alkenes were vaporized, and oxidized by O_3 in the gas phase, resulting in peroxy radical formation, after which the possible dimers were detected using a NO_3^- -atmospheric pressure chemical ionization time-of-flight mass spectrometer. A highly oxidized radical reaction partner was present in the chamber to improve the detectability of the formed dimers. The combined results of these two approaches suggest that the reaction pathway is possible in standard atmospheric conditions and may thus be important for a number of peroxy radicals.

The Criegee intermediates (CIs) have been the topic for several studies and their role in global atmospheric chemistry is becoming better understood. Isoprene and monoterpenes form a large portion of the total biogenic volatile organic compound emissions in the forested regions of the world, isoprene being the most abundant non-methane hydrocarbon in the Earth's atmosphere. The carbon-carbon double bonds in these compounds are efficiently ozonized (the reaction where an unsaturated compound reacts with ozone) in the atmosphere leading to primary ozonides that subsequently decompose into Criegee intermediates and carbonyl compound molecules. Approximately 50 % of the CIs derived from acyclic alkenes immediately decompose in unimolecular reactions forming, e.g., hydroxyl radicals, the most important oxidizing species in the Earth’s atmosphere. The remainder is stabilized in atmospheric conditions in collisions with other molecules and are subsequently called stabilized Criegee intermediates (sCI). The sCI yields are often smaller, around 20 %, for Criegee intermediates formed in ozonolysis of cyclic alkenes, such as α-pinene. These sCIs can further react with atmospheric constituents (H2O, (H2O)2, SO2, NO2, organic acids etc.) in bimolecular reactions or decompose/isomerize in unimolecular reactions. The bimolecular reactions of sCIs with SO2 contribute significantly to the formation of atmospheric gas phase sulphuric acid and as such are an important factor in nucleation and formation of clouds. In the lower atmosphere, H2SO4 also has adverse health effects on humans and animals and causes corrosion of building materials. Additionally, unimolecular decay and bimolecular reactions of sCIs produce OH radicals. The experimental studies done so far have largely focused on the few simplest sCIs, i.e., formaldehyde oxide (H2COO), acetaldehyde oxide (CH3COO), and acetone oxide ((CH3)2COO). The studies on more complex sCIs, such as methyl vinyl ketone oxide and sCIs formed via ozonolysis of terpenes, are mostly done computationally. The literature review part of this work presents the basic mechanisms of formation and natural removal of sCIs as well as results of recent direct kinetic studies of sCIs with focus on the simplest ones (CH2OO, CH3CHOO, and (CH3)2COO). The methods of detection used in experimental studies are also considered. The experimental section concentrates on measurements of unimolecular decay kinetics of acetone oxide (CH3)2COO above and below room temperature using a new photolytic precursor (CH3)2CIBr. In the experimental section also the apparatus utilized in the research is presented along with the modifications and improvements made on the setup in this work. The calibrations done to ensure accurate measurements are also presented.