Formation of low-volatility aerosol precursor molecules and clusters in the atmosphere

We live in a world full of aerosols and witness their existence constantly. Changes in visibility, road dust and pollen filling the air in the spring time and even dosing some medicines are all related to aerosols. The most important aspect for this thesis is however, the formation of aerosol precursor molecules and clusters and their possible effects on aerosol properties. Different types of aerosols e. g. organic and inorganic, ice and pollen, biogenic and anthropogenic, when acting as cloud condensation nuclei (CCN), can change the optical properties of clouds and thus have different climate effects via changes in precipitation or cloud cover. Also the mechanism how the small cloud seeds are formed can have a major effect on the cloud properties. Clouds reflect and scatter radiation cooling the atmosphere but to this day aerosol effects still form the largest uncertainty in estimates of the climate of the future. Low-volatility compounds in the ambient air are the most important components in both aerosol formation and their growth to sizes that can affect cloud properties such as their reflectivity. The vapours in the atmosphere form around half of the first precursors of aerosol particles via nucleation, still molecular in size. The rest is released directly into the air e.g. by the traffic or from the oceans as sea salt. Neutral molecular size precursor substituents are difficult to detect because they lack electric charge and their concentrations rarely exceed the detection limits of the used measurement instruments. This is one of the reasons why the first steps of nucleation process are still partly unsolved after decades of research. This thesis concentrates first in development of selective methods and ultrasensitive instrumentation for the detection of acidic aerosol precursor molecules and clusters. These compounds include sulphuric acid, which is known to be highly important precursor for new particle formation. This thesis presents the first ambient measurements with the new instrumentation and even though sulphuric acid was detected in relative high concentrations during a particle formation event, no ambient cluster formation was yet observed. The same instrumentation was further used in an ultraclean chamber experiment were sulphuric acid and dimethyl amine formed growing clusters and they were detected from the smallest clusters all the way up to ~2 nm size. These compounds are likely to dominate the new particle formation with low-volatility organic compounds. Tens of thousands of volatile organic compounds (VOC) are emitted in the atmosphere by terrestrial vegetation, marine environments and anthropogenic sources, making the search for the meaningful compounds for new particle formation extremely difficult. In this thesis a new group of extremely low-volatility organic compounds (ELVOC) from terpene oxidation are introduced. They form a large source of secondary organic aerosol (SOA) and might help explaining the former big gap between the measured and the modelled SOA loads in the atmosphere. Formation of these compounds from RO2 radicals via rapid autoxidation process to stable molecules is also studied in details in laboratory experiments. This thesis also utilizes a global modelling framework, where the measurement results are applied. According to this thesis, ELVOC in particular are in crucial role when estimating SOA and CCN formation in the air. All together this thesis is a comprehensive study of both organic and inorganic low-volatility precursor molecules and clusters in the atmosphere, from their origin, formation mechanisms, and measurement techniques to their possible effects on climate now and in the future.