Recent advances in mass spectrometry techniques for atmospheric chemistry research on molecular‐level

Abstract

The Earth's atmosphere is composed of an enormous variety of chemical species associated with trace gases and aerosol particles whose composition and chemistry have critical impacts on the Earth's climate, air quality, and human health. Mass spectrometry analysis as a powerful and popular analytical technique has been widely developed and applied in atmospheric chemistry for decades. Mass spectrometry allows for effective detection, identification, and quantification of a broad range of organic and inorganic chemical species with high sensitivity and resolution. In this review, we summarize recently developed mass spectrometry techniques, methods, and applications in atmospheric chemistry research in the past several years on molecular‐level. Specifically, new developments of ion‐molecule reactors, various soft ionization methods, and unique coupling with separation techniques are highlighted. The new mass spectrometry applications in laboratory studies and field measurements focused on improving the detection limits for traditional and emerging volatile organic compounds, characterizing multiphase highly oxygenated molecules, and monitoring particle bulk and surface compositions.

Synthesis and Characterization of Organic Peroxides from Monoterpene-Derived Criegee Intermediates in Secondary Organic Aerosol

“…Based on recent developments of high-resolution mass spectrometry techniques, several recent studies reported molecular-level identification of particle-phase organic peroxides. , However, these mostly rely on tentative formula assignment as the method of identification, while unambiguous assignments are only possible when authentic standards are available. For the first time with the help of AAHP standards, we unambiguously identified four AAHPs and quantitative estimates are given for two types of monoterpene-SOA generated in a laboratory flowtube reactor.…”

Evaluation of a reduced pressure chemical ion reactor utilizing adduct ionization for the detection of gaseous organic and inorganic species

“…Mass spectrometry represents a nearly universal method for determining the chemical composition of organic and inorganic species across various environmental matrices. In the fields of environmental and atmospheric chemistry, chemical ionization (CI) is a versatile real-time method to measure individual organic and inorganic compounds in air at trace concentrations (Yuan et al, 2017;Riva et al, 2019;Zhang W. et al, 2023;Zhang Y. et al, 2023). As in all chemical ionization systems, trace analytes in air react with excess reagent ions, leading to the formation of charged product ions usually via electron/proton transfer or adduct formation (Zhang W. et al, 2023;Zhang Y. et al, 2023).…”

“…In the fields of environmental and atmospheric chemistry, chemical ionization (CI) is a versatile real-time method to measure individual organic and inorganic compounds in air at trace concentrations (Yuan et al, 2017;Riva et al, 2019;Zhang W. et al, 2023;Zhang Y. et al, 2023). As in all chemical ionization systems, trace analytes in air react with excess reagent ions, leading to the formation of charged product ions usually via electron/proton transfer or adduct formation (Zhang W. et al, 2023;Zhang Y. et al, 2023). Advances in the field of chemical ionization over the last decade have yielded exceptionally low detection limits down to 10 4 molecules cm -3 (part-per-quadrillion), expanded dynamic ranges, and the capability of measuring a wide range of gaseous organic and inorganic species with time resolutions of up to 50 Hz (Riva et al, 2019;Zhang W. et al, 2023;Zhang Y. et al, 2023).…”

“…These compounds are now understood to be formed ubiquitously in the atmosphere and are critical to new particle formation and growth (Ehn et al, 2014;Bianchi et al, 2019). As a result, CIMS has emerged as a core analytical tool in atmospheric chemistry and related fields which require high sensitivity, high temporal resolution, and molecular-level speciation (Bruderer et al, 2019;Riva et al, 2019;Tang et al, 2019;Mazzucotelli et al, 2022;Zhang W. et al, 2023;Zhang Y. et al, 2023). With the right selection of reagent ions, CI offers the possibility of soft, selective, and sensitive online detection, for essentially any class of chemical compounds.…”

“…With the right selection of reagent ions, CI offers the possibility of soft, selective, and sensitive online detection, for essentially any class of chemical compounds. While in practice, no reagent ion can simultaneously detect the entire distribution of volatile compounds present in the atmosphere with sufficient selectivity and sensitivity, different reagent ions can be selected to target distinct chemical families (Crounse et al, 2006;Bertram et al, 2011Bertram et al, , 2016Lee et al, 2014, Bianchi et al, 2019Zhang W. et al, 2023;Zhang Y. et al, 2023). Therefore, a critical choice for chemical ionization operators is which reagent ion is best suited to measure compounds of interest in each measurement scenario.…”