Exploring the source, transformation pathways, and the fate of natural organic matter (NOM) is critical to understanding the regional/global carbon cycle and carbon budget. The dissolved fraction of NOM, i.e., dissolved organic matter (DOM), is a complex mixture resulting from the transformation of plant, animal and microbial matter and plays a crucial role in many biogeochemical processes at the land-ocean-atmosphere interfaces. The advance of Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) makes the detailed characterization of DOM at the molecular level possible. On the other hand, elucidation of complex DOM sample also presents significant analytical challenges, and these challenges also act as a driving force for the instrumentation and methodology development on FT-ICR MS. This review article has been written to aid those working in biogeochemistry, environmental and atmospheric chemistry, and related areas which investigate elemental cycles and DOM transformations. First, the fundamental theory, historical perspective, and recent advances in the field have been introduced. The detailed molecular characterization of environmental and geological samples continues to present significant analytical challenges, and it also has become a driving force for the development of the instrumentation and experimental methods. These achievements in DOM analysis have had an impact upon the fields of environmental science, geochemistry, and analytical chemistry. Next, varieties of applications of FT-ICR MS have also been described, followed by our view of the future of this technique in earth science research. We believe that this review covers the essential pairing of FT-ICR MS and collectively offers environmental and geochemical scientists a substantial resource for their research. Graphical abstract

Organosulfates (OSs), a key component of secondary organic aerosols (SOA), account for up to one third of organic matter in the atmosphere. However, high molecular weight (HMW, 500-800 Da) OSs in ambient aerosols are poorly characterized at a molecular level, due to experimental difficulties. With Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICRMS), we are able to identify more than 8,000 OSs in wintertime aerosols in Beijing. We found that both the number and signal magnitudes of HMW OSs with low H/C and O/C ratios and degrees of unsaturation were greatly enhanced during hazy days, indicating that most HMW OSs were freshly formed during stagnant air pollution episodes. They are most likely to be the oxidation products of semivolatility to low-volatility precursors (e.g., polycyclic aromatic hydrocarbons and fatty acids) and have showed a strong influence of anthropogenic emissions. The molecular corridor analysis suggests that the high abundance of HMW aromatic-like and aliphatic OSs considerably decreases the volatility of organic aerosols in the urban atmosphere.

Snow serves as a vital scavenging mechanism to gas-phase and particle-phase organic nitrogen substances in the atmosphere, providing a significant link between land-atmosphere flux of nitrogen in the surface-earth system. Here, we used optical instruments (UV–vis and excitation-emission matrix fluorescence) and a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) to elucidate the molecular composition and potential precursors of snow samples collected simultaneously at four megacities in North China. The elemental O/N ratio (≥3), together with the preference in the negative ionization mode, indicates that the one and two nitrogen atom-containing organics (CHON1 and CHON2) in snow were largely in the oxidized form (as organic nitrates, −ONO2). This study assumed that scavenging of particle-phase and gas-phase organic nitrates might be significant sources of CHON in precipitation. A gas-phase oxidation process and a particle-phase hydrolysis process, at a molecular level, were used to trace the potential precursors of CHON. Results show that more than half of the snow CHON molecules may be related to the oxidized and hydrolyzed processes of atmospheric organics. Potential formation processes of atmospheric organics on a molecular level provide a new concept to better understand the sources and scavenging mechanisms of organic nitrogen species in the atmosphere.