Ion Cyclotron Resonance Mass Spectrometry Research Articles

Insights into the roles of DOM in humification during sludge composting: Comprehensive chemoinformatic analysis using FT-ICR mass spectrometry

Biological humification is the core process in sludge composting for organic matter stabilization. Characterizing dissolved organic matter (DOM) would be a promising way for tracking humification, but still needs fundamental understanding. This study evidenced the role of DOM in deciphering humification via comprehensive and expansive chemoinformatic analyses based on Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Results showed that formula-derived indices including half reaction of carbon oxidation (ΔG0Cox), oxygen to carbon ratios (O/C), double bond equivalent to carbon ratios (DBE/C) and modified aromaticity index (AImod) (except for molecular lability boundary (MLB) index) from the nitrogen (N)-containing compounds were highly correlated with the fluorescence index representing humic and fulvic acids. Besides, the identified dominant reaction types (oxidative demethylation, deamination, and desulfurization, etc.) in different stage of composting, key molecules based on paired mass distance (PMD) network, and nexus molecules (e.g., C10H14N5O7P, C9H14N3O8P, C14H18N4O3, etc.) from DOM-microbes associated network further supported the important roles of N-containing compounds in humification. Furthermore, as the precursors for humification, releasing of biogenic N-containing compounds from sludge and providing thermodynamically available CHO compounds would be important for controlling humification. The fates of N-containing precursors and stable CHO precursors in determining the degree of humification need more attentions in future research. This study provides fundamental understanding that exploring DOM composition, properties and molecular transformation is alternative to track humification in composting.

Photochemical behavior of dissolved organic matter derived from Alternanthera philoxeroides hydrochar: Insights from molecular transformation and photochemically reactive intermediates

Hydrochar-derived dissolved organic matter (HDOM) enters aquatic ecosystems through soil leaching and surface runoff following the application of hydrochar. However, the photochemical behavior of HDOM remains unclear. The photo-transformation of HDOM was analyzed by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), multiple spectroscopy methods, high-performance liquid chromatography, and combining synchronous fluorescence and Fourier-transform infrared spectroscopy with two-dimensional correlation spectroscopy. The results showed that with the increase of carbonization temperature, amide II in protein-like substances were observed to be preferentially photolyzed, and the protein-like substances were more sensitive to low irradiation time, while the duration time of the photochemical behavior of amide II and aliphatic C−H were more persistent. FT-ICR MS results showed that N and S-containing molecules, including lignins and lipids were more sensitive to ultraviolet irradiation. Furthermore, the photo-transformation of HDOMs was accompanied by the generation of triple excited state dissolved organic matter and singlet oxygen. Our findings will be beneficial for understanding the mechanisms of photo-transformation of HDOM and for predicting the possible behaviors of hydrochar produced at different temperatures before large-scale application.

Molecular comparison of organic matter removal from shale gas flowback wastewater: Ozonation versus Fenton process

Shale gas extraction process generates a large amount of shale gas flowback wastewater (SGFW) containing refractory organic compounds, which can pose serious environmental threats if not properly treated. However, the extremely complex compositions of organics in SGFW are still unknown and their transformation pathways in O3- and •OH-dominated systems are not well recognized, which restrain the selection of treatment technology and optimization of operational parameters. The removal characteristics and reaction mechanism of dissolved organic matter (DOM) in SGFW treated by ozonation and Fenton processes were comparatively investigated using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. The results showed that both processes could degrade low-oxygen highly unsaturated and phenolic organics, polyphenolics and polycyclic aromatics, and transform them into aliphatic organics and high-oxygen highly unsaturated and phenolic organics. With increasing action of reactive oxygen species (O3 for ozonation and •OH for Fenton process), the degradation products (mainly aliphatic organics) increased during ozonation. However, in Fenton process, a wider range of DOM was removed without aliphatic organics accumulation. The degradation mechanisms of DOM during ozonation and Fenton processes included oxygen addition reactions (+3O, +H2O2, and +2O) as dominant pathways. However, ozonation showed more violent oxygenation, hydroxylation, and carboxylation, while Fenton process presented more violent chain-breaking reactions. These results revealed the selective oxidation of ozone and nonselective oxidation of •OH during SGFW treatment, and provided theoretical support for selecting SGFW treatment approaches.

Discriminative Behavior of Cyclodextrin Polymers against Dissolved Organic Matter: Role of Cavity Size and Sorbate Properties.

Cyclodextrin polymers (CDPs) are promising next-generation adsorbents in water purification technologies. The selectivity of the polymer derivate cross-linked with tetrafluoroterephthalonitrile (TFN-CDP) for nonionic and cationic micropollutants (MPs) over dissolved organic matter (DOM) renders the adsorbent also attractive for many analytical applications. The molecular drivers of the observed selectivity are, nonetheless, not yet fully understood. To provide new insights into the sorption mechanism, we (i) synthesized TFN-CDPs with different cavity sizes (α-, β-, γ-CDP); (ii) assessed their extraction efficiencies for selected nonionic MPs in competition with different DOM size fractions (<1, 1-3, 3-10, >10 kDa) to test for size-selectivity; and (iii) performed nontargeted, ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry analysis on CDP-extracted DOM compounds (<1 kDa) to probe for molecular sorbate properties governing their selective sorption. First, no evidence of size-selectivity was obtained through either the different CD cavity sizes (i) or the two independent approaches (ii) and (iii). Second, we found a dominant impact of sorbate oxygenation and polarity on the extraction of DOM and MPs, respectively, with relatively oxygen-poor/nonpolar molecules favorably retained on all α-, β-, and γ-CDP. Third, our data indicates exclusion of an anionic matrix, such as carboxylic acids, but preferential sorption of cationic nitrogen-bearing DOM, pointing at repulsive and attractive forces with the negatively charged cross-linker as a likely reason. Therefore, we ascribe TFN-CDP's selectivity to nonpolar and electrostatic interactions between MPs/DOM and the polymer building blocks. These molecular insights can further aid in the optimization of efficient and selective sorbent design for environmental and analytical applications.

Unraveling the photochemical reactivity of dissolved organic matter in the Yangtze river estuary: Integrating incubations with field observations

Dissolved organic matter (DOM) sustains a substantial part of the organic matter transported seaward in large estuaries, where photochemical reactions significantly influence its transformation and fate. Irradiation experiments can provide valuable information on the photochemical reactivity (photo-labile, photo-resistant, and photo-product) of molecules. However, previous research paid less attention to exploring the controls of the initial DOM chemistry to irradiation experiments and examining the applicability of their further integration with field research. Here, we conducted irradiation experiments for samples from the freshwater and seawater endmember of the Yangtze River Estuary (YRE), which receives organic matter transport from the largest river in China, the Yangtze River. Molecules that occurred before and after irradiation experiments were characterized by the Fourier transform ion cyclotron resonance mass spectrometry. Results show that both post-irradiation samples have the lower aromaticity degree and reduced oxidation state, while the freshwater endmember sample exhibits more dramatic changes, indicating the controls of parent molecules to the effect of irradiation experiments. Integrating with the “molecular matching” approach, we compared the molecules occurring in field samples with the classified molecules (photo-resistant, photo-labile, and photo-product) acquired from performed irradiation experiments and correlated the relative intensity of photochemical reactivity types with salinity. When applying results from different experiments to conduct “molecular matching”, the photo-resistant and photo-labile relative intensity possess consistently positive and negative trends with increasing salinity, respectively. This suggests their reliability for molecular matching applications, while the inconsistent trends for the photo-product relative intensity with salinity suggest its uncertainty in assessing the photo-induced effects. Moreover, the molecular composition within the photochemical reactivity types in field samples also evolved along the salinity gradient and showed similar trends with the DOM changes after experimental irradiation. Despite various factors influencing estimations, it is revealed that a fraction of aromatic molecules and majority of carboxyl-rich alicyclic molecules considered with biologically persistent nature in the YRE freshwater zone are simultaneously not susceptible to photochemical transformation to potentially constitute a long-term marine carbon sink. This study emphasizes the importance and limitations of the combination of field research and laboratory-controlled experiments to provide a better understanding of the crucial role of photochemical reactions in affecting carbon cycling in large estuaries.

Characterization of polycyclic aromatic hydrocarbons (PAHs) in atmospheric particles (PM2.5) in the North China Plain using positive-ion atmospheric pressure photoionization (APPI) coupled with fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS)

Many aromatic compounds, including 16 types of U.S. EPA priority PAHs, exist in substituted or unsubstituted forms and have high toxicities. Aromatic compounds in aerosols collected in the North China Plain (NCP) were characterized by GC-MS and atmospheric pressure photoionization (APPI) Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS). The concentrations of the 16 types of PAHs in the collected samples ranged from 277.0 to 876.8 ng/m3, which were higher than those collected in other regions and countries. Previous studies reported that only 27 wt% of aromatic compounds could be eluted using the GC system and demonstrated that APPI FT-ICR MS is a useful method for identifying large-molecular aromatics. In this study, two samples collected from the NCP were successfully characterized by APPI FT-ICR MS. In the APPI + mode, 231 and 228 CH formulas (containing only C and H and having a double bond equivalent (DBE) of 4 or greater) were identified, accounting for 10% of the numerical fraction and more than 40% of the intensity fraction. The FT-ICR data revealed that condensed PAHs with 6–8 aromatic rings had relatively high abundances and that a series of PAH homologs (alkylated PAHs) with identical DBE values ranging from 4 to 30 were present. Furthermore, heteroatom groups were also identified as significant components of the aromatic fractions. The O1, O2, N1, NO2, and S1 class species with DBE values of 3–34 and carbon numbers of 11–42 were identified by APPI FT-ICR MS. The heteroatom PAHs had DBE values and carbon number distributions similar to regular PAHs. The aromatic fractions determined in this work provide useful data for future quantitative analyses of aromatic compounds with high toxicities and our findings will help improve the current understanding of PAH compositions in the northern China. However, further research is needed to determine the abundances and toxicities of various apparent or substituted PAHs outside of the 16 types identified by the U.S. EPA as priority PAH compounds, which have been extensively researched.

A Systematic Review of Polycyclic Aromatic Hydrocarbon Derivatives: Occurrences, Levels, Biotransformation, Exposure Biomarkers, and Toxicity.

Polycyclic aromatic hydrocarbon (PAH) derivatives constitute a significant class of emerging contaminants that have been ubiquitously detected in diverse environmental matrixes, with some even exhibiting higher toxicities than their corresponding parent PAHs. To date, compared with parent PAHs, fewer systematic summaries and reanalyses are available for PAH derivatives with great environmental concerns. This review summarizes the current knowledge on the chemical species, levels, biotransformation patterns, chemical analytical methods, internal exposure routes with representative biomarkers, and toxicity of PAH derivatives, primarily focusing on nitrated PAHs (NPAHs), oxygenated PAHs (OPAHs), halogenated PAHs (XPAHs), and alkylated PAHs (APAHs). A collection of 188 compounds from four categories, 44 NPAHs, 36 OPAHs, 56 APAHs, and 52 XPAHs, has been compiled from 114 studies that documented the environmental presence of PAH derivatives. These compounds exhibited weighted average air concentrations that varied from a lower limit of 0.019 pg/m3 to a higher threshold of 4060 pg/m3. Different analytical methods utilizing comprehensive two-dimensional gas chromatography coupled with high-resolution time-of-flight mass spectrometry (GC × GC-TOF-MS), gas chromatography coupled to time-of-flight mass spectrometry (GC-TOF-MS), comprehensive two-dimensional gas chromatography coupled to quadrupole mass spectrometry (GC × GC-QQQ-MS), and Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS), that adopted untargeted strategies for the identification of PAH derivatives are also reviewed here. Additionally, an in-depth analysis of biotransformation patterns for each category is provided, including the likelihood of specific biotransformation reaction types. For the toxicity, we primarily summarized key metabolic activation pathways, which could result in the formation of reactive metabolites capable of covalently bonding with DNA and tissue proteins, and potential health outcomes such as carcinogenicity and genotoxicity, oxidative stress, inflammation and immunotoxicity, and developmental toxicity that might be mediated by the aryl hydrocarbon receptor (AhR). Finally, we pinpoint research challenges and emphasize the need for further studies on identifying PAH derivatives, tracking external exposure levels, evaluating internal exposure levels and associated toxicity, clarifying exposure routes, and considering mixture exposure effects. This review aims to provide a broad understanding of PAH derivatives' identification, environmental occurrence, human exposure, biotransformation, and toxicity, offering a valuable reference for guiding future research in this underexplored area.

Cultivation of Melilotus officinalis as a source of bioactive compounds in association with soil recovery practices.

Melilotus officinalis is a Leguminosae with relevant applications in medicine and soil recovery. This study reports the application of Melilotus officinalis plants in soil recovery and as a source of bioactive compounds. Plants were cultivated in semiarid soil under four different fertilizer treatments, urban waste compost at 10 t/ha and 20 t/ha, inorganic fertilizer and a control (no fertilizer). Agronomic properties of soil (pH, EC, soil respiration, C content, macro- and microelements) were analyzed before and after treatment. Also, germination, biomass, element contents, and physiological response were evaluated. Metabolite composition of plants was analyzed through Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Results showed a significant enhancement of the soil microbial activity in planted soils amended with compost, though there were no other clear effects on the soil physicochemical and chemical characteristics during the short experimental period. An improvement in M. officinalis germination and growth was observed in soils with compost amendment. Metabolite composition of plants was analyzed through Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Principal Component and Agglomerative Hierarchical Clustering models suggest that there is a clear separation of the metabolome of four groups of plants grown under different soil treatments. The five most important discriminative metabolites (annotated) were oleamide, palmitic acid, stearic acid, 3-hydroxy-cis-5-octenoylcarnitine, and 6-hydroxynon-7- enoylcarnitine. This study provides information on how the metabolome of Melilotus might be altered by fertilizer application in poor soil regions. These metabolome changes might have repercussions for the application of this plant in medicine and pharmacology. The results support the profitability of Melilotus officinalis cultivation for bioactive compounds production in association with soil recovery practices.

Effects of dissolved organic matter removal and molecular transformation in different water treatment processes on formation of disinfection byproducts

Alterations in molecular composition of dissolved organic matter (DOM) during water treatments can influence the composition and toxicity of disinfection by-products (DBPs) in subsequent chlorination disinfection process. In this study, the impacts of DOM composition after various water treatment techniques (coagulation, adsorption, nanofiltration, biological aerated filter (BAF), and their integrated processes) on the generation mechanisms of DBPs were comprehensively explored by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) in combination with GC–MS and LC-MS analysis. The results indicated that coagulation preferentially removed unsaturated (low H/C) and oxidized (high O/C) compounds, whereas adsorption was prone to remove the reduced (low O/C) component that was more reactive with chlorine, leading to lower yields (μg DBP/mg DOC) of trihalomethanes (THMs) and haloacetic acids (HAAs) during subsequent chlorination. The coagulation-adsorption technique exhibited a relatively high removal of both known and unknown DBPs, demonstrating that coagulation and adsorption were complementary for DOM removal at the molecular level. Nanofiltration selectively removed molecules with relatively high O/C, however, those with very low O/C that were more reactive with chlorine could pass through the nanofiltration membrane, resulting in the highest yields of THMs and HAAs. Although BAF was inefficient in removing DBPs precursors, it could convert molecules with low degree of oxidation and unsaturation into highly oxidized and unsaturated ones, thereby significantly enhancing the removal of DBPs precursors in the subsequent coagulation-adsorption process. These findings are instrumental in developing and selecting more effective techniques to minimize the formation of DBPs in water treatment.

Molecular and optical signatures of photochemical transformation of dissolved organic matter: Nonnegligible role of suspended particulate matter in urban river

Natural dissolved organic matter (DOM) is one of the Earth's dynamic carbon pools and a key intermediate in the global carbon cycle. Photochemical processes potentially affect DOM composition and activity in surface water. Suspended particulate matter (SPM) is the integral component of slow-moving rivers, and holds the potential for photochemical reactivity. To further investigate the influence of SPM on DOM photochemical transformation, this study conducted experiments comparing samples with and without SPM irradiated under simulated sunlight. Surface water samples from slow-moving urban rivers were collected. DOM optical characteristics and molecular features obtained by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) were investigated. Photolabile DOM was enriched in unsaturated and highly aromatic terrestrial substances. Photoproduced DOM had low aromaticity and was dominated by saturated aliphatics, protein-like substances, and carbohydrates. Study results indicated that the presence of SPM had a nonnegligible impact on the molecular traits of DOM, such as composition, molecular diversity, photolability, and bioavailability during photochemical reactions. In the environment affected by SPM, molecules containing heteroatoms exhibit higher photosensitivity. SPM promotes the photochemical transformation of a wider range of chemical types of photolabile DOM, particularly nitrogen-containing compounds. This study provides an essential insight into the more precise simulation of photochemical reactions of DOM influenced by SPM occurring in natural rivers, contributing to our understanding of the global carbon cycle from new theoretical perspectives.

Constraining multi-stage and protracted oil generation of alkaline lacustrine source rocks by heteroatomic compounds

It is unclear whether source rocks deposited in ancient alkaline lakes undergo multiple stages of hydrocarbon generation, particularly of oils. In this study, the lower Permian Fengcheng Formation in the Junggar Basin, China, was investigated using the geochemistry of heteroatomic species, with a focus on N-containing compounds, by negative-ion electrospray high-resolution Fourier transform ion cyclotron resonance mass spectrometry. The maturity parameters based on N-containing compounds (e.g., C0–5/C15–35-DBE 12 N1 and C0–5/C15–35-DBE 15 N1) and aromatic hydrocarbons (TMNr) reveal progressive generation of mature to highly mature crude oils. The polymerization index P1 ([DBE 18 + DBE 15]/DBE 12_N1), alkylation index R1 (RC6−35/RC0−5), and paleo-salinity index (β carotane/nCmax) of the Fengcheng Formation source rocks suggest that the high salinity inhibited molecular polymerization of organic matter and prolonged the oil generation peak, which produced highly mature crude oils in the late stages of hydrocarbon generation. Therefore, alkaline lacustrine source rocks undergo multiple stages of protracted oil generation, which results in a longer oil window and higher threshold for gas generation than in the case of the classic Tissot model. The results highlight the oil generation potential of deep basins containing alkaline lacustrine source rocks and highly mature organic matter, which also have a lower gas-generation potential than previously thought.

Surface microrelief induced by tillage management alters the pathway and composition of dissolved organic matter exports from soils to runoff during rainfall

Rainfall-runoff process mobilizes considerable dissolved organic matter (DOM) from soils to aquatic systems via surface and sub-surface flow pathways. Microrelief induced by tillage management can alter this flow partitioning and thus likely affect the associated pathway and composition of DOM exports during rainfall. This study conducted rainfall simulation experiments, combined with three-dimensional fluorescence spectra analysis and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) technology, to explore the effects of different surface microreliefs treatments on the quantity and composition of DOM exports at a plot scale. Four typical microrelief treatments (i.e., contour tillage (CP), longitudinal tillage (LP), artificial digging tillage (AP), and flat tillage (CK, as control)) were selected. Results showed that ratios of surface to sub-surface flow volume under four treatments were in order of LP (193:1)>CK (73:1)>AP (4.5:1)>CP (0.5:1). DOM concentrations in sub-surface flow (13.37∼33.50 mg L-1) were 7∼18 times of that in surface flow (0.03∼4.56 mg L-1). The total export fluxes of DOM were 134, 139, 563, and 1214 mg m-2 at LP, CK, AP, and CP treatments, respectively, with proportions of 8%, 17%, 82%, and 98% via sub-surface flow. Compared to surface flow, DOM molecular composition in sub-surface flow showed a significant feature of higher oxygen to carbon ratio, higher molecular weight, and lower hydrogen to carbon ratio. The findings indicated that microrelief with higher surface storage capacity tends to favor a large flux of DOM export, primarily via sub-surface flow, which might significantly affect the DOM cycling in the receiving aquatic ecosystems.

Investigation with ESI FT-ICR MS on sorbent selectivity and comprehensive molecular composition of landfill leachate dissolved organic matter.

Molecular characterization of landfill leachate dissolved organic matter (LDOM) is essential for developing effective processing techniques. However, the molecular selectivity of extraction method and ionization modes often leads to the bias of molecular characterization of LDOM. Here, seven representative sorbents were selected and electrospray ionization negative ion mode (ESI (-)) and positive ion mode (ESI (+)) Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) were used to investigate the molecular composition of different LDOM samples. Obvious sorbent selectivity during extraction procedure was observed, resulting in the underestimation of molecular diversity of LDOM from 32.7% to 69.3%. Totally, 14,000-18,000 unique molecules were obtained in a single sample, indicating the unprecedented molecular diversity of LDOM. Lignins, proteins and lipids are three major molecular groups in LDOM, and N or S containing molecules occupied 83%. Although much of total organic carbon was removed during biochemical treatment process, the molecular diversity of LDOM was not reduced because a considerable of bio-recalcitrant molecules was produced. The results uncover the sorbents selectivity and ionization modes selectivity in LDOM analysis and provided a comprehensive change of LDOM molecular composition during biochemical treatment, which benefits the development of accurate methods to remove organic carbon in landfill leachate.

Progressive drought alters the root exudate metabolome and differentially activates metabolic pathways in cotton (Gossypium hirsutum).

Root exudates comprise various primary and secondary metabolites that are responsive to plant stressors, including drought. As increasing drought episodes are predicted with climate change, identifying shifts in the metabolome profile of drought-induced root exudation is necessary to understand the molecular interactions that govern the relationships between plants, microbiomes, and the environment, which will ultimately aid in developing strategies for sustainable agriculture management. This study utilized an aeroponic system to simulate progressive drought and recovery while non-destructively collecting cotton (Gossypium hirsutum) root exudates. The molecular composition of the collected root exudates was characterized by untargeted metabolomics using Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) and mapped to the Kyoto Encyclopedia of Genes and Genomes (KEGG) databases. Over 700 unique drought-induced metabolites were identified throughout the water-deficit phase. Potential KEGG pathways and KEGG modules associated with the biosynthesis of flavonoid compounds, plant hormones (abscisic acid and jasmonic acid), and other secondary metabolites were highly induced under severe drought, but not at the wilting point. Additionally, the associated precursors of these metabolites, such as amino acids (phenylalanine and tyrosine), phenylpropanoids, and carotenoids, were also mapped. The potential biochemical transformations were further calculated using the data generated by FT-ICR MS. Under severe drought stress, the highest number of potential biochemical transformations, including methylation, ethyl addition, and oxidation/hydroxylation, were identified, many of which are known reactions in some of the mapped pathways. With the application of FT-ICR MS, we revealed the dynamics of drought-induced secondary metabolites in root exudates in response to drought, providing valuable information for drought-tolerance strategies in cotton.

Differentiation of Four Polyvinylidene Fluoride Polymers Based on Their End Groups by DART-FT-ICR MS and Kendrick Plots.

Nowadays, synthetic polymers are produced and used in many materials for different applications. Matrix-assisted laser desorption/ionization or electrospray mass spectrometry are classically used to investigate them, but these techniques require sample preparation steps, which are not always suitable for the study of insoluble or formulated polymers. Alternatively, direct real-time (DART) ionization analysis may be conducted without sample preparation. Four polyvinylidene fluoride (PVDF) polymers involving the C2H2F2 repeating unit coming from different suppliers have been analyzed by DART Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) in negative-ion mode. The obtained mass spectra systematically displayed an oligomeric distribution between m/z 400 and 1300 of [M - H]-, [M + O2]•-, and [M + NO2]- ions. Kendrick plots were used to ease the identification of PVDF end-groups and establish a difference between the samples. Both commercial PVDF polymers shared the same α+ω end groups formula, which confirmed a similar polymerization process for their synthesis. The two other PVDFs were clearly different from the commercial ones by the occurrence of specific end-groups. MS/MS and MS3 experiments were conducted to obtain structural information on these end-groups.

Nonmicrobial mechanisms dominate the release of CO2 and the decomposition of organic matter during the short-term redox process in paddy soil slurry

Both biotic and abiotic mechanisms play a role in soil CO2 emission processes. However, abiotically mediated CO2 emission and the role of reactive oxygen species are still poorly understood in paddy soil. This study revealed that OH promoted CO2 emission in paddy soil slurries during short-term oxidation (4 h). OH generation was highly hinged on active Fe(II) content, and the OH contribution to CO2 efflux was 10%–33% in topsoil and 40%–77% in deep-soil slurries. Net CO2 efflux was higher in topsoil slurries, which contained more dissolved organic carbon (DOC). CO2 efflux correlated well with DOC contents, suggesting the critical role of DOC. Microbial mechanisms contributed 9%–45% to CO2 production, as estimated by γ-ray sterilization experiments in the short-term reoxidation process. Solid-aqueous separation experiments showed a significant reduction in net CO2 efflux across all soil slurries after the removal of the original aqueous phase, indicating that the water phase was the main source of CO2 emission (>50%). Besides, C emission was greatly affected by pH fluctuation in acidic soil but not in neutral/alkaline soils. Fourier transform ion cyclotron resonance mass spectrometry and excitation-emission matrix results indicated that recalcitrant and macromolecular dissolved organic matter (DOM) components were more easily removed or attacked by OH. The decrease in DOM content during the short-term reoxidation was the combined result of OH oxidation, co-precipitation, and soil organic matter release. This study emphasizes the significance of the generally overlooked nonmicrobial mechanisms in promoting CO2 emission in the global C cycle, and the critical influence of the aqueous phase on C loss in paddy environments.

Patterns of Carbon-Bound Exogenous Compounds Impact Disease Pathophysiology in Lung Cancer Subtypes in Different Ways.

Carbon-bound exogenous compounds, such as polycyclic aromatic hydrocarbons (PAHs), tobacco-specific nitrosamines, aromatic amines, and organohalogens, are known to affect both tumor characteristics and patient outcomes in lung squamous cell carcinoma (LUSC); however, the roles of these compounds in lung adenocarcinoma (LUAD) remain unclear. We analyzed 11 carbon-bound exogenous compounds in LUAD and LUSC samples using in situ high mass-resolution matrix-assisted laser desorption/ionization Fourier-transform ion cyclotron resonance mass spectrometry imaging and performed a cluster analysis to compare the patterns of carbon-bound exogenous compounds between these two lung cancer subtypes. Correlation analyses were conducted to investigate associations among exogenous compounds, endogenous metabolites, and clinical data, including patient survival outcomes and smoking behaviors. Additionally, we examined differences in exogenous compound patterns between normal and tumor tissues. Our analyses revealed that PAHs, aromatic amines, and organohalogens were more abundant in LUAD than in LUSC, whereas the tobacco-specific nitrosamine nicotine-derived nitrosamine ketone was more abundant in LUSC. Patients with LUAD and LUSC could be separated according to carbon-bound exogenous compound patterns detected in the tumor compartment. The same compounds had differential impacts on patient outcomes, depending on the cancer subtype. Correlation and network analyses indicated substantial differences between LUAD and LUSC metabolomes, associated with substantial differences in the patterns of the carbon-bound exogenous compounds. These data suggest that the contributions of these carcinogenic compounds to cancer biology may differ according to the cancer subtypes.

Unambiguous molecular characterization of solid electrolyte interphase species on graphite negative electrodes

Performances of lithium-ion batteries (LIBs) are closely related to the control of solid-electrolyte interface (SEI) stability. To decrease the capacity losses linked to the build-up of this interface or potentially reverse such losses, electrolyte formulations have been continuously optimized over years to evaluate how they affect SEI. However, direct molecular characterization of the diverse interphases remains extremely challenging. Herein, we report the molecular imaging of SEI components formed on graphite electrodes by laser desorption ionization (LDI) coupled to ultrahigh-resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS). By exploiting the surface analysis offered by LDI combined with the molecular formula attributions provided by the FT-ICR MS, it is possible to unambiguously identify/exclude suspected molecules in the SEI such as lithium ethylene dicarbonate and lithium ethylene mono carbonate. Moreover, thousands of unknown species were observed, which could be exploited for further understanding of the surface composition. We believe this methodology to be a critical advance for the design of high-performance LiBs.

Oxidative desulfurization of fuel oil and molecular characterization of the sulfone compound distribution in the different extractants

PMoA/G5 catalyst was synthesized, and its oxidative desulfurization (ODS) performance on model oil was studied. The catalyst and oxidation-extraction-adsorption system was used for the ODS of Arabian Extra light oil (AXL). Acetonitrile and methanol were chosen as different extractants for the extraction of sulfones (O2S and O2S4). The distribution of sulfone was first reported in detail at each of the three-stage extraction solvents at the molecular level analyzed by the Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS), proton, and 13C nuclear magnetic resonance (1H NMR,13C NMR). The FT-ICR MS results show that the extracted proportion of macromolecular sulfone compounds increases with the extraction stages. Acetonitrile exhibited better selectivity than methanol for polyaromatic sulfone with a high carbon number for the O2S species with double bond equivalent (DBE) = 12–15 and O2S2 species with DBE = 11–16. The NMR results reveal that polyaromatics with naphthenic rings and a low carbon number (<30) can be easily extracted due to their high polarity. The excellent performance of the PMoA/G5 catalyst makes it a promising candidate in the ODS reaction, and the research results give guidelines for ODS technology.

Interpreting pH-Dependent Differential UV/VIS Absorbance Spectra to Characterize Carboxylic and Phenolic Chromophores in Natural Organic Matter

Natural organic matter (NOM) is critical for the biogeochemical cycles of energy and many elements in terrestrial and aquatic ecosystems, and protonation-active functional groups in NOM molecules, notably carboxylic and phenolic groups often mediate these critical environmental functions. Molecular heterogeneity, polydispersity and dynamic behavior of NOM complicate achieving an unambiguous description of its molecular properties and reactivity. This study demonstrates that differential ultraviolet-visible (UV/VIS) absorbance spectra (DAS) of NOM acquired at varying pH values exhibit several distinct features associated with the deprotonation of NOM molecules, independent of the environmental provenance of NOM (e.g., surface water, seawater, sediment, and wastewater). The protonation-active functionalities that contribute to the Gaussian distribution bands present in the DAS were identified here by comparing characteristic properties of the bands with the stoichiometries of NOM molecules ascertained by Ultrahigh-Resolution Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS). The protonation-active individual chromophores universally present in NOM molecules were identified by a genetic molecular network analysis. The observed DAS features were closely modeled via superimposing DAS spectra of 51 individual protonation-active chromophores. Molecular orbital theory was applied to further interpret the deprotonation of these chromophores, their molecular structure, electron distribution, and electron transitions measured using DAS. The high sensitivity and easy implementation of the DAS approach allows using it as a powerful tool to quantify the molecular properties and reactivity of NOM at environmental concentrations.