Ionization Fourier Transform Ion Cyclotron Research Articles

Thermal degradation features of soil humic acid sub-fractions in pyrolytic treatment and their relation to molecular signatures

Pyrolysis is a promising treatment for soil remediation for rapidity and fertility preservation. But it is difficult to establish the relationship between pyrolysis behaviors and soil organic matter (SOM) structures, for SOM is a mixture of heterogeneous compounds. HA sub-fractions from the same soil source may provide a series of promising objects to understand SOM at molecular level and the resulting patterns in SOM pyrolysis. We first propose a novel insight into pyrolysis mechanism response to molecular signatures using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) combined with thermogravimetric analysis (TGA) to study six humic acid (HA) sub-fractions extracted from a forest soil. The findings indicate that decomposition of soil HA occurs systematically due to molecular signatures. The decomposition can be categorized as carboxyl controlled (below 280 °C), lipid-dominated (280–450 °C) and condensed aromatics-dominated processes (450–700 °C). Predominant reaction mechanism of all HA sub-fractions was random nucleation (α > 0.25). Lipid in HA tend to initiate multiple nuclei in thermal degradation, while condensed aromatics tend to initiate and grow centering single random point in higher conversion rate (α > 0.75). Bridging the molecular signature and thermogravimetry reveals that the pyrolysis stage below 350 °C should be divided into two distinct processes related to the carboxylic group and lipid compounds, although this stage has conventionally been considered as a single process. The N element of HA was mostly preserved in the condensed aromatics which was mainly pyrolyzed above 450 °C, suggesting that pyrolysis below 450 °C is a preferable remediation treatment considering nitrogen fertility preservation. The observed molecular-level pyrolysis patterns can be applied as a targeted remediation procedure for contaminated soils and can improve the understanding of SOM thermal behaviors at the molecular level.

Pyrolysis Temperature Effect on Compositions of Neutral Nitrogen and Acidic Species in Shale Oil Using Negative-Ion ESI FT-ICR MS.

Negative-ion electrospray ionization (ESI) Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was used to study the effect of the pyrolysis temperature (400, 430, 460, 490, and 520 °C) on acidic and neutral nitrogen species in Huadian shale oil. To more accurately analyze the influence, shale oils produced during the heat-up stage were abandoned. The results show that because of the influence of polymerization and cracking reactions, the increase in temperature increases the content of pyrrole, thiophene, furan, phenol, and aromatic ring cores and decreases the content of carboxylic acid, respectively. Among all the heteroatom compounds identified from negative-ion ESI FT-ICR MS, the relative abundance of N1O1, N1O2, N1O3, N2, N2O1, O1, O3, O1S1, and N1S1 species increases, whereas that of O2 and O4 species decreases as the pyrolysis temperature increases. The decrease in the O2 species can be attributed to carboxylic acid with a double-bond equivalence (DBE) value of 1, whereas the increase in the O2 species with DBE values of 7 and 9 can be attributed to the formation of furan, phenol, and aromatic ring by the polymerization reaction at higher pyrolysis temperatures. Although the effect of the reaction temperature on the molecular composition of acidic and neutral nitrogen species is complex, still characteristic rules are found in this study.

Analysis of Robusta coffee cultivated in agroforestry systems (AFS) by ESI-FT-ICR MS and portable NIR associated with sensory analysis

Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI(±)FT-ICR MS) and portable micro near-infrared spectroscopy (microNIR), coupled to sensory analysis, were used to propose a new analytical methodology to observe the characteristics of Robusta coffees cultivated in agroforestry systems (AFS). Principal component analysis (PCA) chemometric models provided excellent discrimination of the samples analyzed by ESI(±)FT-ICR mass spectra for the ground coffee grains. Analysis of the spectra allowed for identification of the compounds responsible for distinguishing the samples grown with different intercropping AFS species. The microNIR results corroborated the ESI(-)FT-ICR MS data and the sensory analysis, by grouping together coffees grown in AFS intercropped with Gliricidia sepium and Inga edulis. The coupling of these analytical techniques shows promise in coffee quality control, presenting advantages such as collection at point analysis, speed, and analytical reliability.

Estimating the intermediate precision in petroleum analysis by (±)electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry.

Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) is an important analytical technique used for the elucidation of crude oil polar compounds at the molecular level, providing thousands of heteroatom compounds in a single analysis. Due to the high resolution, the complexity of data produced, and steps involved in spectra acquisition and processing, it is necessary to estimate its intermediate precision. Intermediate precision was estimated for positive- and negative-ion ionization modes (ESI(±)) using Composer® software for two Brazilian crude oil samples. The analytical parameters evaluated were the class distribution histogram, the double bond equivalent (DBE) distribution, and the DBE versus carbon number. The statistical parameters used to study the intermediate precision were calculated from the average, standard deviation, confidence interval (significance level at 5%), coefficient of variation (CV), intermediate precision limit (ISO 5725), and principal component analysis (PCA). Two crude oil samples (A and B) were analyzed, in triplicate, for seven consecutive days by ESI(±) FT-ICR MS. The assigned class limit by ESI(+) for crude oil A was 0.42% (O2 S[H] class) and for crude oil B was 0.04% (N2 O2 S[H] class). The assigned DBE intensity limits for the two crude oils were 0.04% for ESI(+) and 0.013% for ESI(-). The PCA for ESI(-) and ESI(+) modes presented better precision for crude oils B and A, respectively. The most abundant classes and DBE of the majority class (i.e., with the highest intensity) are the parameters produced from the Composer® software that had the highest precision and can be used to estimate crude oil properties. The DBE values presented lower intermediate precision limit values (0.04%) than the assigned class values (0.4%). According to CV and PCA, ESI(+) was more precise for crude oil A (83% precision) and ESI(-) for crude oil B (84% precision).

Comparison of Silica and Cellulose Stationary Phases to Analyze Bitumen by High-Performance Thin-Layer Chromatography Coupled to Laser Desorption Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

Bitumen is a complex mixture corresponding to the residue of the vacuum distillation of crude oil. It can be separated on the basis of polarity and solubility with saturates, aromatics, resins, and...

Investigating biological nitrogen cycling in lacustrine systems by FT-ICR-MS analysis of nitrogen-containing compounds in petroleum

Biological nitrogen cycling plays an important role in bio, environmental and petroleum geochemistry. Until now most research has focused on marine environments using nitrogen isotopes, and in contrast, nitrogen cycling in lacustrine environments remains poorly understood. To fill this knowledge gap, we present a case study of crude oils from Permian brackish and saline alkaline lacustrine rocks in the Junggar Basin, northwestern China. To complement the large variation in nitrogen isotope values in lacustrine sediments, we analyzed the pyrrolic N-containing compounds of crude oil using negative ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR-MS). Our results show that pyrrolic compounds derived from biological sources are more abundant in oils from brackish lacustrine settings (i.e., the Jimusar Sag oils of the Junggar Basin) than in oils from alkaline lacustrine settings (i.e., the Mahu Sag oils of the Junggar Basin), which is mainly due to greater higher plant contributions to the latter. Higher plants provide abundant alkaloids and chlorophyll that are the biological precursors of pyrrolic N-containing compounds. In addition, anoxic, sulfate-type, brackish lacustrine settings provide abundant ferrous iron and sulfide that promote N fixation. This study provides the first insights into biological N cycling in brackish and alkaline lacustrine systems, which has significance for fossil fuel resources and their environmental impacts. Our data suggest that the N cycling in lacustrine systems might have an important role in entire Earth system N budget.

Organic matter in delayed coking wastewater: Molecular composition and its effect on emulsification

Delayed coking is a common resid conversion process used in refining operations. A large amount of oil-containing wastewater is produced during the hydraulic decoking process. The coking wastewater contains emulsions which are difficult to process in water treatment plants, especially when the coker is fed with feedstocks have high content of heteroatoms. This study examined the molecular composition of emulsified oil and dissolved organic matter (DOM) in coking wastewater. The emulsification agents in coking wastewater were identified. The emulsified oil and DOM were separated and enriched by liquid–liquid extraction, solid phase extraction, and adsorption chromatography, and then characterized by gas chromatography-mass spectrometry and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry analyses. The results showed that the emulsified oil and DOM in coking wastewater contained highly condensed molecules with a large number of nitrogen and oxygen heteroatomic compounds. The OxSy surfactants and their derivatives, polyoxyethylene ether, and the strong polar oxygen-, nitrogen-, and sulfur-containing compounds are likely the oil–water emulsification agents.

Advanced molecular-fingerprinting analysis of dissolved organic sulfur by electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry using optimal spray solvent

Molecular level characterization of dissolved organic sulfur (DOS) by electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR MS) is necessary for further understanding of the role of DOS in the environment. Here, ESI spray solvent, a key parameter for ion production during ESI process, was investigated for its effect on the molecular characterization of DOS by ESI-FTICR MS. 100% MeOH as spray solvent was found for the first time to remarkably enhance the ionization efficiency of the majority of CHOS-molecules in NOM, which facilitated a total of 1473 CHOS-molecular formulas with one sulfur atom to be detected. The number of CHOS-molecular formulas obtained using 100%MeOH as spray solvent increased notably over 740 in comparison with those using 50% MeOH aqueous solution (731) or 50% ACN aqueous solution (653). Moreover, due to the enhancement of ionization efficiency of DOS during ESI processes, the tandem mass spectra of the NOM CHOS-molecules could be easily obtained using 100% MeOH as spray solvent, which were hardly obtained using 50% MeOH aqueous solution as spray solvent. The results of the tandem mass spectra suggested the first discovery of organosulfates or sulfonic acids in Suwannee River NOM sample. A simple method based on 100% MeOH as ESI spray solvent for advanced molecular characterization of DOS by ESI-FTICR MS was proposed and applied, and the results revealed more molecular information of DOS in sea DOM samples.

Molecular Absorption and Evolution Mechanisms of PM2.5 Brown Carbon Revealed by Electrospray Ionization Fourier Transform–Ion Cyclotron Resonance Mass Spectrometry During a Severe Winter Pollution Episode in Xi'an, China

AbstractKnowledge of the molecular‐level chemistry of brown carbon (BrC) is important in reducing the uncertainties in aerosol radiative forcing. Time‐resolved ambient PM2.5 samples were collected during a severe pollution episode in January 2017 over Xi'an, China for a comprehensive nontarget and full scanning of BrC molecules and their absorption properties using electrospray ionization Fourier transform–ion cyclotron resonance mass spectrometry combined with partial least squares regression analysis, which apportioned the overall ultraviolet absorption to individual molecules. The estimated absorption of CHNO and CHNOS molecules exhibited nighttime prevalence, whereas CHOS, CHNS, CHN, CHO, CHS, and CH molecules presented a dynamic trend. Carbon conjugation was positively correlated with estimated absorption by CHO and CHNO molecules, while exhibiting a mixed relationship with CHNOS. Higher nitrogen content was associated with enhanced light‐absorption properties of BrC molecules, while higher oxygen and sulfur content appeared to be associated with photobleaching during secondary transformation.

Molecular Characterization of Soluble Components in the Lignite by Sequential Solvent Extraction via Continuously Reducing Particle Size.

A lignite was subjected to sequential solvent extraction via continuously reducing particle size from around 20 to more than 200 mesh. Five sets of n-hexane and methanol extracts from the particles were characterized by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) and gas chromatography–mass spectrometry. The total extract yield for lignite when using hexane and methanol as solvents could reach to 0.98 and 15.12%, respectively. The results showed that more molecules with a similar structure but different composition could be extracted by continuously reducing the particle size of the residues, indicating the nonuniform distribution of the low-solubility molecules trapped in the coal particles. The extracts were abundant in branched long-chain aliphatic moieties and oxygen-containing compounds. With the increasing of the extraction degree, the content of alkanes in the extracts decreased rapidly. On the contrary, the content of the compounds with higher condensation and more oxygen atoms increased. It should be noted that polycyclic aromatic hydrocarbons were almost steadily present in all the extraction steps. The molecular composition and distribution of organic molecules in the lignite provide clues to the understanding of coal structure, which is significant for the environmental emission and development of processing techniques for the clean and high value-added utilizations of such a low-rank and abundant coal resource.

Metabolic profiling of different wild and cultivated Allium species based on high-resolution mass spectrometry, high-performance liquid chromatography-photodiode array detector, and color analysis.

Many plants of the genus Allium are widely cultivated and consumed for their nutraceutical and health-enhancing bioactive components effective in many metabolic and infectious diseases. In particular, Allium sativum L. (garlic), the most economically important Allium species, is known to present volatile, comparatively polar sulfur-containing compounds responsible for both the typical garlic aroma and antimicrobial property. More recently, the (moderately) polar portion of garlic metabolome, rich of polyphenols and amino acids, is gaining increasing interest as a source of antioxidants and primary nutrients. In this study, we have explored the chemical diversity of eight different hydroalcoholic extracts obtained by microwave-assisted extraction of white and red crop A. sativum and wild Allium triquetrum, Allium roseum, and Allium ampeloprasum, all originating from the Mediterranean Basin. The aim is to appraise their potential dietetic and healing value through an in-depth chemical characterization and contribute to preserve and exploit natural resources. The multimethodological method applied here is based on an untargeted metabolic profiling by means of high-resolution electrospray ionization Fourier-transform ion cyclotron resonance (ESI FT-ICR) mass spectrometry. More than 850 by ESI(+) and 450 by ESI(-) putative metabolites have been annotated covering all main classes of primary and secondary metabolites, including amino acids, alkaloids, organic and fatty acids, nucleotides, vitamins, organosulfur compounds, and flavonoids. The pigment and polyphenol components have been separated and quantified by a targeted chromatographic high-performance liquid chromatography-photodiode array detector (HPLC-PDA) and CIEL*a*b* colorimetric assay, showing characteristic yellow and red components in each extract, related to a different milieu of anthocyanins and flavonoids as assigned by high-resolution mass spectrometry (MS).

Molecular composition of vanadyl porphyrins in the gilsonite

A gilsonite from Qingchuan (Sichuan province, China) was separated into several fractions and characterized by various techniques. The vanadyl porphyrins were determined by inductively coupled plasma optical emission spectrometer, ultraviolet-visible spectrophotometry, high-temperature gas chromatography-atomic emission detector, and positive-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. The results show that the gilsonite contains a large amount of metal elements, especially the vanadium content is as high as 3888 μg/g. A large number of vanadyl porphyrins are detected, in which the deoxophylloerythroetio porphyrins are the most abundant, indicating high molecular condensation but low thermal maturity. The huge reserves and high metal content imply important utilization value for this natural source.

Localization of mercury and gold in cassava (Manihot esculenta Crantz).

The potential of cassava (Manihot esculenta Crantz.) for simultaneous Hg and Au phytoextraction was explored by investigating Hg and Au localization in cassava roots through Micro-Proton Induced X-Ray Emission, High-Resolution Transmission Electron Microscopy (HR-TEM) and X-Ray Diffractometry (XRD). The effect of Hg and Au in the cyanogenic glucoside linamarin distribution was also investigated using Matrix Assisted Laser Desorption Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (MALDI-FT-ICR-MS) imaging. Hg was located mainly in the root vascular bundle of plants grown in 50 or 100μmolL-1 Hg solutions. Au was localized in the epidermis and cortex or in the epidermis and endodermis for 50 and 100μmolL-1 Au solutions, respectively. For 50μmolL-1 solutions of both Hg and Au, the two metals were co-localized in the epidermis. When the Hg concentrations were increased to 100μmolL-1, Au was still localized to a considerable extent in the epidermis while Hg was located in all root parts. HR-TEM and XRD revealed that Au nanoparticles were formed in cassava roots. MALDI-FT-ICR-MS imaging showed linamarin distribution in the roots of control and plants and metal-exposed plants thus suggesting that linamarin might be involved in Hg and Au uptake and distribution.

Production of bio-fuel from plant oil asphalt via pyrolysis

In order to treat waste during oleic acid production, pyrolysis method was used to investigate the plant oil asphalt (POA) to obtain bio-fuel. It was found that the compounds contained alkane, alkene, fatty acid, plant sterol derivatives, alcohol and etc. in pyrolysis products of POA by Pyrolysis-Gas Chromatography-Mass Spectrometer (Py-GC-MS). The Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (ESI FT-ICR-MS) results showed that dehydrogenation and polymerization reactions took place during the pyrolysis process, but the main reaction was decarboxylation. According to van Krevelen diagram the nature of the bio-fuel can be evaluated. The acid value and viscosity of the resulting bio-fuel produced were higher than that of diesel fuel and reference bio-fuel. The calorific value showed a slight lower value than that of diesel oil. These studies nominated POA as a potential renewable feedstock for bio-fuel production the simple pyrolysis method.

Dissolved organic carbon chemical composition controls the rate of CO2 release from rewetted soil

AbstractThe CO2 flush from dried and rewetted soil has been proposed as an indicator of soil health. Drying and rewetting releases mineralizable carbon (C) due to effects on microbial populations and aggregate stability. It is a complex, integrative process, and its relationship to soil health is incompletely understood. In order to increase our understanding of this process, we investigated changes in the quantity and chemistry of dissolved organic carbon (DOC) in a laboratory incubation study during 48 h after rewetting dried soil. A LI‐COR infrared gas analyzer was used to quantify CO2 released. DOC was extracted by water and quantified by a Shimadzu TOC‐VCPH. Changes in chemical composition of the DOC were followed during decomposition using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT‐ICR‐MS). The initial DOC was 67% lignin‐like, and 6.5% N‐containing aliphatic material (number‐averaged formula distribution). The contribution of N‐containing aliphatics to total DOC declined to 0.2% by 48 h, although the amount of DOC declined only 34% by 48 h. The lignin‐like material increased to 76% of the total DOC by 48 h of incubation, suggesting it is less microbially available than other DOC constituents. The decline in CO2 release rate was related to the loss of readily mineralizable N‐containing compounds rather than to total DOC, supporting the use of the CO2 flush as an indicator of mineralizable N. Further studies designed to elucidate the biological and abiotic mechanisms controlling the CO2 flush will improve its usefulness as a soil health indicator.

The evolution of acids and neutral nitrogen-containing compounds during pyrolysis experiments on immature mudstone

Abstract Pyrolysis experiments were conducted on immature(Ro = 0.47%) organic-rich (TOC = 6.0%)mudstone, and the liquid products at 10 different temperature stages were detected by negative ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI− FT-ICR MS). Seven classes of acids and neutral nitrogen-containing compounds, namely, N1, N2, O1, O2, O3, O4 and N1O1, were detected in all the products. The O2 class accounted for the largest proportion (50.56 %–91.65%) among all the products, followed by the O1 class (1.70 %–28.80%). The % O1 and % N1 classes showed a clear upward trend with the increase in experimental temperature due to their organic resources, and the % O2 class showed the exact opposite trend, which could be explained by the chemical reactions that occurred during the maturation process, such as decarboxylation and dehydration. In addition, the relative abundances of the classes with high double bond equivalents (DBE) (≥9) and low DBE (≤7) showed a significant upward trend and a clear downward trend, respectively. The main reasons were aromatization and condensation during thermal evolution. This series of thermal evolution characteristics indicated that a set of new thermal parameters, such as ∑%DBE ≥9/∑%DBE≤8 (O2 compounds) = 0.0007T2 - 0.372T + 48.594(R2 = 0.9088) may be used as a new maturity parameter after further verified with crude oils.

Application of Hydrochar Altered Soil Microbial Community Composition and the Molecular Structure of Native Soil Organic Carbon in a Paddy Soil.

The benefits and disadvantages of hydrochar incorporation into soil have been heavily researched. However, the effect of hydrochar application on the soil microbial communities and the molecular structure of native soil organic carbon (SOC) has not been thoroughly elucidated. This study conducted an incubation experiment at 25 °C for 135 days using a soil column with 0.5 and 1.5% hydrochar-amended paddy soil to explore the interconnections between changes in soil properties and microbial communities and shifts in native SOC structure using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS) and NMR after hydrochar application. Hydrochar addition decreased the labile SOC fraction by 15.6-33.6% and increased the stable SOC fraction by 10.3-27.0%. These effects were significantly stronger for 1.5% hydrochar-treated soil. Additionally, hydrochar addition induced the native SOC with 1.0-3.0% more carbon and 6.0-13.0% higher molecular weight. The SOC in hydrochar-amended soil contained more aromatic compounds but fewer carbohydrates and lower polarity. This was resulted by a statistically significant reduction in Sphingobacterium, which was active in polycyclic aromatic hydrocarbon degradation, and an increase in Flavobacterium, Anaerolinea, Penicillium, and Acremonium, which were the efficient decomposers of labile SOC. These findings will help elucidate the potential influence of hydrochar on the carbon biogeochemical cycle in the soil.

Dissolved organic matter in a tropical saline-alkaline lake of the East African Rift Valley.

Saline-alkaline lakes of the East African Rift are known to have an extremely high primary production supporting a potent carbon cycle. To date, a full description of carbon pools in these lakes is still missing. More specifically, there is not detailed information on the quality of dissolved organic matter (DOM), the main carbon energy source for heterotrophs prokaryotes. We report the first exhaustive description of DOM molecular properties in the water column of a meromictic saline-alkaline lake of the East African Rift. DOM availability, fate and origin were studied either quantitatively, in terms of dissolved organic carbon (DOC) and nitrogen (DON) or qualitatively, in terms of optical properties (absorbance) and molecular characterization of solid-phase extracted DOM (SPE-DOM) through negative electrospray ionization Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). DOM availability was high (DOC ∼ 8.1 mM in surface waters) and meromixis imprinted a severe quantitative and qualitative change on DOM pool. At the surface, DOM was rich in aliphatic and moderately in aromatic molecules and thus mirroring autochthonous microbial production together with photodegradation. At the bottom changes were extreme: DOC increased up to 5 times (up to 50 mM) and, molecular signature drifted to saturated, reduced and non-aromatic DOM suggesting intense microbial activity within organic sediments. At the chemocline, DOC was retained indicating that this interface is a highly reactive layer in terms of DOM processing. These findings underline that saline-alkaline lakes of the East African Rift are carbon processing hot spots and their investigation may broaden our understanding of carbon cycling in inland waters at large.

Contribution of ketone/aldehyde-containing compounds to the composition and optical properties of Suwannee River fulvic acid revealed by ultrahigh resolution mass spectrometry and deuterium labeling.

A prior method of mass labeling ketone-/aldehyde-containing species in natural dissolved organic matter (DOM) is further developed and applied. This application involved the treatment of Suwannee River fulvic acid (SRFA) with increasing concentrations of sodium borodeuteride (NaBD4), followed by detection of reduced species via negative mode electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FTICR MS). The extent of reduction, as determined by ESI FTICR MS, resulting from increasing concentrations of NaBD4 correlated well with changes in the absorption and emission spectra of the corresponding untreated and borodeuteride-reduced samples, providing evidence that ketone/aldehyde functional groups contribute substantially to the bulk optical properties of SRFA. Furthermore, the differences in the reactivity and abundance of ketone-/aldehyde-containing species for various regions in Van Krevelen plots were revealed, thus showing how this mass labeling method can be used to provide more detailed structural information about components within complex DOM samples than that provided by the determination and analysis of molecular formulae alone. Graphical abstract.

Insight into structural features of soluble portions from cellulose, cellobiose and monosaccharide methanolysis by GC/MS and ESI FTICRMS

Methanolysis of biomass has attracted increasing attention due to it has some advantages, such as low critical points and strong hydrogen donation ability. In this paper, methanolysis of cellulose, cellobiose (sucrose), and monosaccharide (glucose) were performed to obtain methanol-soluble portions (MSPs). The relatively volatile or less polar species in the MSPs were analyzed with a gas chromatograph/mass spectrometer (GC/MS), and the polar species were identified with a negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometer (FTICRMS). According to analysis with GC/MS, the MSPs include ethers, esters, ketones, acids, sugars, phenols, and furans. The analysis with FTICRMS shows that the polar compounds in the MSPs are O1–O15 class species with 1–14 double bond equivalent (DBE) and 5–35 carbon atom number (CAN). The most abundant class species in MSPs from cellulose, sucrose, and glucose methanolysis are O5, O7, and O7, respectively. The species in MSPs from sucrose and glucose methanolysis center at higher DBE value and more CAN than those in MSP from cellulose methanolysis. Meanwhile, the oxygen atom number of O4–O10 class species in the MSPs were negatively correlated with the average DBE value. The results indicate that condensation intensively proceeded with the specific regularity during sucrose and glucose methanolysis.