Abstract 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
Abstract. Biomass burning is one of the key sources of urban aerosols in the North China Plain, especially during winter, when the impact of secondary organic aerosols (SOAs) formed from biogenic volatile organic compounds (BVOCs) is generally considered to be minor. However, little is known about the influence of biogenic SOA loading on the molecular composition of wintertime organic aerosols. Here, we investigated the water-soluble organic compounds in fine particulate matter (PM2.5) from urban Tianjin by ultrahigh-resolution Fourier transform ion cyclotron resonanc mass spectrometry (FT-ICR MS). Our results show that most of the CHO and CHON compounds are derived from biomass burning which are poor in oxygen and contain aromatic rings that probably contribute to light-absorbing brown carbon (BrC) chromophores. Under moderate to high SOA-loading conditions, the nocturnal chemistry is more efficient than photooxidation to generate secondary CHO and CHON compounds with high oxygen content. Under low SOA loading, secondary CHO and CHON compounds with low oxygen content are mainly formed by photochemistry. Secondary CHO compounds are mainly derived from oxidation of monoterpenes. However, nocturnal chemistry may be more productive to sesquiterpene-derived CHON compounds. In contrast, the number- and intensity-weight of S-containing groups (CHOS and CHONS) increased significantly with the increase of biogenic SOA loading, which agrees with the fact that a majority of the S-containing groups are identified as organosulfates (OSs) and nitrooxy–organosulfates (nitrooxy–OSs) that are derived from the oxidation of BVOCs. Terpenes may be potential major contributors to organosulfates and nitrooxy–organosulfates. While the nocturnal chemistry is more beneficial to the formation of organosulfates and nitrooxy–organosulfates under low SOA loading. The SOA loading is an important factor that is associated with the oxidation degree, nitrate group content and chemodiversity of nitrooxy-organosulfates. Furthermore, our study suggests that the hydrolysis of nitrooxy-organosulfates is a possible pathway for the formation of organosulfates.
Rationale The sources and chemical compositions of organic aerosol (OA) exert a significant influence on both regional and global atmospheric conditions, thereby having far‐reaching implications on environmental chemistry. However, existing mass spectrometry (MS) methods have limitations in characterizing the detailed composition of OA due to selective ionization as well as fractionation during cold‐water extraction and solid‐phase extraction (SPE). Methods A comprehensive MS study was conducted using aerosol samples collected on dusty, clean, and polluted days. To supplement the data obtained from electrospray ionization (ESI), a strategy for analyzing OAs collected using the quartz fiber filter directly utilizing laser desorption ionization (LDI) was employed. Additionally, the ESI method was conducted to explore suitable approaches for determining various OA compositions from samples collected on dusty, clean, and polluted days. Results In situ LDI has the advantages of significantly reducing the sample volume, simplifying sample preparation, and overcoming the problem of overestimating sulfur‐containing compounds usually encountered in ESI. It is suitable for the characterization of highly unsaturated and hydrophobic aerosols, such as brown carbon‐type compounds with low volatility and high stability, which is supplementary to ESI. Conclusions Compared with other ionization methods, in situ LDI helps provide a complementary description of the molecular compositions of OAs, especially for analyzing OAs in polluted day samples. This method may contribute to a more comprehensive MS analysis of the elusive compositions and sources of OA in the atmosphere.
Abstract Dissolved organic matter in seasonal snow (DOM snow ) has a noticeable effect on the carbon cycle, carbon reserve, and ecosystems globally, but its regional characteristics remain unclear owing to a lack of surface measurements. The molecular compositions, potential sources, and degrees of oxidation of DOM snow were investigated over northeastern China. The results of quantitative analysis for DOM snow reflect the importance of anthropogenic influence. Fourier transform‐ion cyclotron resonance‐mass spectrometry analyses indicate that most (∼71%) identified molecular formulas are consistent with terrestrial compounds and derive from underlying soil and atmospheric deposition. Microbe‐derived compounds are also important contributors (∼34%) to the DOM snow pool. The heterogeneous distribution of DOM snow molecules is a complex process caused by many kinds of factors. Sulfate ions, organic aerosols, longitude, and altitude explain 76.2% of the regional difference in organic components. High levels of oxidation DOM snow molecules are found, and such high reactive molecules indicate the presence of secondary organic matter and aging processes within the snowpack. The objective of this study is to investigate the characteristics of DOM snow in high‐latitude regions of China so that we can further understand the impacts of changes in regional processes.
Dissolved organic matter (DOM) is an ultracomplex mixture of organic compounds in the land/ocean–atmosphere interface. Normally, polar compounds from DOM are hardly retained by liquid chromatography (LC) columns for further analytical purposes. Here, we utilized Fourier transform ion cyclotron resonance mass spectrometry with LC for online analysis of DOM in river water and rainwater. With sophisticated instrumental optimization, different portions of metal salts, carboxyl-rich alicyclic molecules, organosulfates (OSs), and lignin-like compounds could be fully fractionated within one LC cycle (20 min). The complexity of the analyte was greatly reduced by LC separation, which therefore allows much better MS performance. Moreover, the compounds' structures were characterized by tandem mass spectrometry (MSn). The protocol presented herein offers a novel insight into the conventional LC-MS method, that it has the potential to investigate OSs and other components in DOM according to specific functional groups and heteroatoms and to explore their potential sources and reaction mechanisms.
Abstract Extensive reservoir construction has fragmented more than 70% of the world's rivers, significantly impacting river connectivity and carbon cycling. However, the response of riverine dissolved organic matter (DOM) to reservoir influence and its potential downstream effects remains unclear. In this study, we employed multiple analytical techniques, including Fourier transform ion cyclotron resonance mass spectrometry, radiocarbon dating, and environmental factor analysis, to investigate the dynamic changes in DOM and its controlling factors under different hydrological management regimes in the LongTan Reservoir, the largest reservoir in the Pearl River, which is the second largest river in China by water discharge. Our results indicate that the molecular diversity of riverine DOM is reduced in the reservoir. Oxygen‐rich and heteroatomic compounds, such as those containing nitrogen, sulfur, and phosphorus, are preferentially removed through enhanced photo‐ and biodegradation processes in the reservoir, particularly during the storage period. This leads to DOM that is enriched with oxygen‐poor compounds and shows a biodegraded Δ 14 C value downstream. This study highlights that the composition of riverine DOM is significantly altered by the reservoir, but these effects could potentially be mitigated by optimizing the outlet location.
'/%3e%3cuse xlink:href='%23a' transform='rotate(23.036 .093 25.536)'/%3e%3cuse xlink:href='%23a' transform='rotate(45.87 1.273 16.18)'/%3e%3cuse xlink:href='%23a' transform='rotate(69.945 .996 12.078)'/%3e%3cuse xlink:href='%23a' transform='rotate(20.66 -19.689 31.932)'/%3e%3c/svg%3e)