Analytical methodologies for oxidized organic compounds in the atmosphere†

Abstract

Oxidized compounds in the atmosphere can occur as emitted primary compounds or as secondary products when volatile emitted precursors react with various oxidants. Due to the presence of polar functional groups, their vapor pressures decrease, and they condense onto small particles. Thereby, they have an effect on climate change by the formation of clouds and scattering solar radiation. The particles and oxidized compounds themselves can cause serious health problems when inhaled. Therefore, it is of utmost importance to study oxidized compounds in the atmosphere. Much ongoing research is focused on the discovery of new oxidized substances and on the evaluation of their sources and factors influencing their formation. Monitoring biogenic and anthropogenic primary oxidized compounds or secondary oxidized products in chamber experiments or field campaigns is common. New discoveries have been reported, including various oxidized compounds and a new group of compounds called highly oxidized organic molecules (HOMs). Analytics of HOMs are mainly focused on chromatography and high-resolution mass spectrometry employing chemical ionization for identifying and quantifying compounds at low concentrations. Oxidized compounds can also be monitored by spectrophotometric methods in which the determinations of total amounts are based on functional groups. This review highlights recent findings on oxidized organic compounds in the atmosphere and analytical methodologies used for their detection and quantification. The discussion includes gas and liquid chromatographic methods, sampling, extraction, concentration, and derivatization procedures involved, as well as mass spectrometric and spectrophotometric methods.