Selective molecular characterization of organic aerosols using in situ laser desorption ionization mass spectrometry.

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.

Optimized liquid chromatography-tandem mass spectrometry protocol for enhanced detection of 45 pesticides in water and soil samples.

RATIONALE: The development of analytical screening techniques for pesticides is crucial for preventing and mitigating environmental contamination. Mass spectrometry-based screening methods differ based on the complexity of the sample matrix and the diversity of the target compounds. One of the major challenges is balancing cost reduction in the extraction process with the optimization of analytical results. This protocol introduces a universal and efficient scheme for the qualitative and quantitative schemes for 45 pesticides within a single analytical run. METHODS: Water samples were extracted using an SPE column, with the pH adjusted to 7. Soil samples were processed using a modified QuEChERS method. The pretreatment for water samples emphasized selecting appropriate SPE columns and optimizing pH, while for soil samples, the focus was on choosing suitable extraction solvents and extraction salt packages. The enriched samples were then analyzed using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The method was evaluated for accuracy, precision, detection limits, and matrix effects. RESULTS: The method enabled the simultaneous detection of 45 pesticides within a 15-minute analysis period. SPE recoveries ranged from 56.1% to 118.8%. Instrumental detection limits varied between 0.02 and 1 pg, while method detection limits extended from 0.05 to 18.47 ng/l in soil and water matrices. The approach was successfully applied to water and soil samples, with the pesticide concentration ranging from 0.1 ng/L to 38 µg/L. CONCLUSIONS: The protocol substantially enhances the characterization and quantification of 45 pesticides in environmental samples, achieving a remarkable reduction in detection limits by an order of magnitude compared to previous research. This method enables the simultaneous detection of pesticides in both water and soil matrices using a single system, addressing the challenges of using separate systems for different environmental media. Furthermore, this protocol provides a crucial theoretical foundation for managing and safeguarding against pesticide pollution.

Peatland Wildfires Enhance Nitrogen-Containing Organic Compounds in Marine Aerosols over the Western Pacific.

Peatland wildfires contribute significantly to the atmospheric release of light-absorbing organic carbon, often referred to as brown carbon. In this study, we examine the presence of nitrogen-containing organic compounds (NOCs) within marine aerosols across the Western Pacific Ocean, which are influenced by peatland fires from Southeast Asia. Employing ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) in electrospray ionization (ESI) positive mode, we discovered that NOCs are predominantly composed of reduced nitrogenous bases, including CHN+ and CHON+ groups. Notably, the count of NOC formulas experiences a marked increase within plumes from peatland wildfires compared to those found in typical marine air masses. These NOCs, often identified as N-heterocyclic alkaloids, serve as potential light-absorbing chromophores. Furthermore, many NOCs demonstrate pyrolytic stability, engage in a variety of substitution reactions, and display enhanced hydrophilic properties, attributed to chemical processes such as methoxylation, hydroxylation, methylation, and hydrogenation that occur during emission and subsequent atmospheric aging. During the daytime atmospheric transport, aging of aromatic N-heterocyclic compounds, particularly in aliphatic amines prone to oxidation and reactions with amine, was observed. The findings underscore the critical role of peatland wildfires in augmenting nitrogen-containing organics in marine aerosols, underscoring the need for in-depth research into their effects on marine ecosystems and regional climatic conditions.

Deciphering dissolved organic matter characteristics and its fate in a glacier-fed desert river-the Tarim river, China.

The bioavailable diverse dissolved organic matter (DOM) present in glacial meltwater significantly contributes to downstream carbon cycling in mountainous regions. However, the comprehension of molecular-level characteristics of riverine DOM, from tributary to downstream and their fate in glacier-fed desert rivers remains limited. Herein, we employed spectroscopic and high-resolution mass spectrometry techniques to study both optical and molecular-level characteristics of DOM in the Tarim River catchment, northwest China. The results revealed that the DOC values in the downstream were higher than those in the tributaries, yet they remained comparable to those found in other glacier-fed streams worldwide. Five distinct components were identified using EEM-PARAFAC analysis in both tributary and downstream samples. The dominance of three protein-like components in tributary samples, contrasting with a higher presence of humic-like components in downstream samples, which implied that the dilution and alterations of the glacier DOM signature and overprinting with terrestrial-derived DOM. Molecular composition revealed that thousands of compounds with higher molecular weight and increased aromaticity were transformed, generated and introduced from terrestrial inputs during downstream transportation. The twofold rise in polycyclic aromatic and polyphenolic compounds observed downstream compared to tributaries indicated a greater influx of terrestrial organic matter introduced into the downstream during water transportation. The study suggests that the glacier-sourced DOM experienced minimal photodegradations, with limited influence from human activities, while also being shaped by terrestrial inputs during its transit in the alpine-arid region. This unique scenario offers valuable insights into comprehending the fate of DOM originating from glacial meltwater in arid mountainous regions.

Long-term effects of vegetation restoration and forest management on carbon pools and nutrient storages in northeastern Loess Plateau, China.

It is crucial for understanding the variations of carbon and nutrient pools within the ecosystems during long-term vegetation restoration to accurately assess the effects of different ecological restoration patterns. However, the long-term spatio-temporal variations of carbon and nutrient pools under different vegetation types remain unclear. The sites for long-term natural and planted forests (i.e., Natural secondary forest, Pinus tabulaeformis planted forest, Platycladus orientalis planted forest, and Robinia pseudoacacia planted forest) on the northeastern Loess Plateau, China were selected, to measure and analyze the differences and interannual variations of vegetation attributes at four synusiae and soil properties at 0-100 cm over the period of 12 years (2006-2017). The principal component analysis (PCA) and Mantel test were also conducted to explore the relationships among vegetation attributes, soil properties, and carbon and nutrient pools. The results showed that: compared with the planted forests, the natural secondary forest had lower arborous biomass (84.21 ± 1.53 t hm-2) and higher understory biomass and plant heights. Compared to planted forests, the secondary forest had higher soil carbon and nitrogen contents (13.74 ± 3.50 g kg-1 and 1.16 ± 0.34 g kg-1). The soil carbon pool in the secondary forest was 22.0% higher than planted forests, while the vegetation carbon pool in the P. tabulaeformis was 75.5% higher than other forests. Principal component analysis (PCA) and Mantel test revealed that vegetation attributes and soil properties had significant correlations with carbon and nutrient pools, especially at the arborous synusia (p < 0.01). The findings indicated that in the ecologically fragile Loess Plateau region, the selection of appropriate vegetation restoration types should be guided by varying ecological restoration goals and benefits, aiming to expected ecological outcomes. This insight offers a strategic implication for forest management that is tailored to improve carbon and nutrient pools in areas with similar environmental conditions.

Analysis of natural organic matter via fourier transform ion cyclotron resonance mass spectrometry: an overview of recent non-petroleum applications.

Among the different techniques for mass analysis, ultra-high-resolution Fourier transform ion cyclotron resonance (FTICR) is the method of choice for highly complex samples, as it offers unrivaled mass accuracy and resolving power, combined with a high degree of flexibility in hybrid instruments as well as for ion activation techniques. FTICR instruments are readily embraced by the biological and biomedical research communities and applied over a wide range of applications for the analysis of biomolecules such as carbohydrates, lipids, nucleic acids, and proteins. In the field of natural organic matter (NOM) analysis, petroleum-related studies currently dominate FTICR-MS applications. Recently, however, there is a growing interest in developing high-performance MS methods for the characterization of NOM samples from natural aquatic and terrestrial environments. Here, we present an overview of FTICR-MS techniques for complex, non-petroleum NOM samples, including data analysis and novel tandem mass spectrometry (MS/MS) methods for structural classifications. © 2020 The Authors. Mass Spectrometry Reviews published by John Wiley & Sons Ltd.

An advanced LC-MS/MS protocol for simultaneous detection of pharmaceuticals and personal care products in the environment.

RATIONALE: The development of appropriate analytical screening techniques for pharmaceuticals and personal care products (PPCPs) is the basis for studying the distribution and environmental impact of emerging contaminants (ECs). Mass spectrometry-based screening methods vary with the complexity of the target compounds. It is challenging to balance both positive and negative ion quantification with a low detection limit. To establish a set of experimental methods including extraction, chromatography-separation and mass spectrometry screening is one of the most important topics in PPCP research. This paper describes a universal and efficient qualification and quantification protocol for the simultaneous detection of 34 PPCPs in different environmental samples in a single analytical data acquisition run. METHODS: Thirty-four representative PPCPs, which are widely distributed in the environment with high ecological toxicity and complex chemical structures, were selected as representative target ECs. The extraction of the target PPCPs was achieved using only one solid-phase extraction cartridge without the need to adjust the pH of samples. The enriched samples were detected by LC-MS/MS in both positive and negative ion modes simultaneously. The protocol was evaluated based on the accuracy, precision, detection limits and matrix effects. RESULTS: This method achieved simultaneous detection of PPCPs in both positive and negative ion modes, with a single analytical cycle of 12 min. The observed SPE recoveries were between 40% and 115%. The instrumental detection limits (IDL) varied from 0.01 to 1 pg, and the method detection limits (MDL) were between 0.002 and 3.323 ng/l in different matrices. Most of the PPCPs were subjected to matrix suppression below 30%. The method was successfully applied for quantitative analysis of the PPCPs in different environmental samples, including river samples, wastewater treatment plant (WWTP) samples and soil samples. CONCLUSIONS: This protocol developed a rapid and efficient detection method to simultaneous qualitative and quantitative 34 representative PPCPs in the environment. The IDL ranged from 0.01 to 1 pg and the MDL ranged from 0.002 to 3.323 ng/l in different matrices. The detection limit was one order of magnitude lower compared to previous studies. The protocol also provided a wide application range for different environmental matrices, which permitted the migration and transformation of PPCPs to be explored.

Identification of Trace Components in Sauce-Flavor Baijiu by High-Resolution Mass Spectrometry.

Sauce-flavor Baijiu is one of the most complex and typical types of traditional Chinese liquor, whose trace components have an important impact on its taste and quality. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) is one of the most favorable analytical tools to reveal trace molecular components in complex samples. This study analyzed the chemical diversity of several representative sauce-flavor Baijiu using the combination of electrospray ionization (ESI) and FT-ICR MS. The results showed that ESI+ and ESI- exhibited different chemical features characteristic of trace components. Overall, sauce-flavor Baijiu was dominated by CHO class compounds, and the main specific compound types were aliphatic, highly unsaturated with low oxygen, and peptide-like compounds. The mass spectral parameters resolved by FT-ICR MS of several well-known brands were relatively similar, whereas the greatest variability was observed from an internally supplied brand. This study provides a new perspective on the mass spectrometry characteristics of trace components of sauce-flavor Baijiu and offers a theoretical foundation for further optimization of the gradients in Baijiu.

Fractionation and characterization of dissolved organic matter using solid-phase extraction followed by Fourier transform ion cyclotron resonance mass spectrometry with electrospray, atmospheric pressure photoionization, and laser desorption ionization.

RATIONALE: Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) combined with different ionization techniques provides a powerful means to characterize dissolved organic matter (DOM) at the molecular level. Solid-phase extraction (SPE) is currently the most widely utilized method for extracting the DOM, but one-step elution using methanol does not provide a comprehensive picture of DOM. The development of efficient extraction and enrichment methods as well as characterization techniques from water samples remains a priority for DOM research, which is investigated in this study. METHODS: The DOM was extracted from lake water by SPE using one-step elution (methanol or dichloromethane) and multistep elution (water, methanol, acetone, and dichloromethane). A combination of electrospray ionization (ESI), atmospheric pressure photoionization (APPI), and matrix-free laser desorption ionization (LDI) was utilized for FT-ICR MS analysis in both positive (+) and negative (-) ion modes. RESULTS: The total recovery of the multistep elution was 23.5% higher as compared to the investigated one-step elution procedure (85% vs. 61.6%); however, a comparison of the observed molecular species and the range of diversity under different ionization techniques along with the statistical analyses showed that proper selection of solvent and ionization method was required to explore specific compounds from the sample. CONCLUSIONS: For DOM species containing different heteroatoms, a combination of ESI, APPI, and LDI can offer a comprehensive profile of DOM in aquatic ecosystems. The specific molecular formulae of each ionization technique are characterized as follows: ESI- mode exhibited strong selectivity for lignin-like and tannins-like species with high oxygen content, as well as organosulfates. ESI+ favored lipid species and peptide/protein compounds. Unsaturated and condensed aromatic hydrocarbons with low oxygen were preferably ionized by both APPI and LDI.

High Molecular Diversity of Organic Nitrogen in Urban Snow in North China.

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.

Characterization of Lignin Compounds at the Molecular Level: Mass Spectrometry Analysis and Raw Data Processing.

Lignin is the second most abundant natural biopolymer, which is a potential alternative to conventional fossil fuels. It is also a promising material for the recovery of valuable chemicals such as aromatic compounds as well as an important biomarker for terrestrial organic matter. Lignin is currently produced in large quantities as a by-product of chemical pulping and cellulosic ethanol processes. Consequently, analytical methods are required to assess the content of valuable chemicals contained in these complex lignin wastes. This review is devoted to the application of mass spectrometry, including data analysis strategies, for the elemental and structural elucidation of lignin products. We describe and critically evaluate how these methods have contributed to progress and trends in the utilization of lignin in chemical synthesis, materials, energy, and geochemistry.

Rapid mass spectral fingerprinting of complex mixtures of decomposed lignin: Data-processing methods for high-resolution full-scan mass spectra.

Lignin is the second most abundant natural biopolymer and its wastes are significant sources for renewable chemicals as an alternative to conventional fossil fuels. Consequently, chemical characterization methods are required to assess the content of valuable chemicals contained in these complex lignin wastes. This short overview summarizes rapid data-processing methods developed in our laboratory for application to full-scan raw data from high-resolution mass spectrometry experiments of decomposed lignin samples. The discussed graphical and statistical methods support the initial classification and elucidation of the main structural features of the lignin components without the need for time-consuming tandem mass spectrometry analyses.

Chemical diversity of lignin degradation products revealed by matrix-optimized MALDI mass spectrometry.

Lignin is the most abundant natural resource of aromatic moieties and the second most abundant natural biopolymer. Analytical techniques that obtain as much information as possible on the exact structural content of lignin species are essential for developing efficient processes that transform highly complex lignin wastes into value chemicals and biofuels. For mass spectrometric analysis of lignin samples, usually electrospray ionization, atmospheric pressure chemical ionization, or atmospheric pressure photoionization are used as ionization techniques. Matrix-assisted laser desorption/ionization (MALDI) is less frequently applied but offers a much more rapid screening option for lignin mixtures. In this study, we compared several common MALDI matrices for analysis of alkali lignin and discovered that different chemical matrices exhibited very different ionization efficiencies and selectivity with respect to the structures of the lignin-related compounds as well as the presence of heteroatoms. Importantly, the results highlight that the choice of matrix strongly determines the analytical coverage of molecular species in the complex lignin degradation mixtures. Graphical abstract.

Determination of Urinary Metabolites of the Emerging UV Filter Octocrylene by Online-SPE-LC-MS/MS.

Octocrylene (OC) is an emerging UV filter, which is used in the majority of sunscreens as well as other personal care products (PCP) and consumer products. Its presence in various environmental matrices has been reported. However, information on the internal OC exposure in humans is not available, due to the lack of appropriate biomarkers of exposure and analytical methods. Here, we describe a rugged, precise, and accurate analytical method for the determination of three OC metabolites (ester hydrolysis and alkyl chain oxidation products) in human urine by stable isotope dilution analysis. Urine samples are incubated with ß-glucuronidase (E. coli K12) and then analyzed by liquid chromatography-electrospray ionization-triple quadrupole-tandem mass spectrometry with online turbulent flow chromatography for sample cleanup and analyte enrichment (online-SPE-LC-MS/MS). Syntheses of analytical standards, including deuterium-labeled internal standards, are also described. In a pilot study, we investigated the applicability of the metabolites as biomarkers of exposure in urine samples from the general population (n = 35). OC metabolites were detected in 91% of the samples, with the highest concentrations for three individuals having used sunscreen within 5 days prior to sample collection. We will apply the method in future human biomonitoring studies for OC exposure and risk assessment.

Electron-based fragmentation methods in mass spectrometry: An overview.

Tandem mass spectrometry (MS/MS) provides detailed information for structural characterization of biomolecules. The combination of electron capture dissociation (ECD) techniques with Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) often provides unique ion-electron reactions and fragmentation channels in MS/MS. ECD is often a complimentary, sometimes even a superior tool to conventional MS/MS techniques. This article is aimed at providing a short overview of ECD-based fragmentation techniques (ExD) and optimization of ECD experiments for FTICR mass analyzers. Most importantly, it is meant to pique the interest of potential users for this exciting research field. © 2015 Wiley Periodicals, Inc. Mass Spec Rev 36:4-15, 2017.

Structural characterization of pyoverdines produced by Pseudomonas putida KT2440 and Pseudomonas taiwanensis VLB120.

The previously unknown sequences of several pyoverdines (PVD) produced by a biotechnologically-relevant bacterium, namely, Pseudomonas taiwanensis VLB120, were characterized by high performance liquid chromatography (HPLC)-high resolution mass spectrometry (HRMS). The same structural characterization scheme was checked before by analysis of Pseudomonas sp. putida KT2440 samples with known PVDs. A new sample preparation strategy based on solid-phase extraction was developed, requiring significantly reduced sample material as compared to existing methods. Chromatographic separation was performed using hydrophilic interaction liquid chromatography with gradient elution. Interestingly, no signals for apoPVDs were detected in these analyses, only the corresponding aluminum(III) and iron(III) complexes were seen. The chromatographic separation readily enabled separation of PVD complexes according to their individual structures. HPLC-HRMS and complementary fragmentation data from collision-induced dissociation and electron capture dissociation enabled the structural characterization of the investigated pyoverdines. In Pseudomonas sp. putida KT2240 samples, the known pyoverdines G4R and G4R A were readily confirmed. No PVDs have been previously described for Pseudomonas sp. taiwanensis VLB120. In our study, we identified three new PVDs, which only differed in their acyl side chains (succinic acid, succinic amide and malic acid). Peptide sequencing by MS/MS provided the sequence Orn-Asp-OHAsn-Thr-AcOHOrn-Ser-cOHOrn. Of particular interest is the presence of OHAsn, which has not been reported as PVD constituent before.

Structural analysis of small to medium-sized molecules by mass spectrometry after electron-ion fragmentation (ExD) reactions.

Electron capture dissociation (ECD) is a tandem mass spectrometry (MS/MS) method that utilizes the interaction of ions and electrons. Its unique ability to preserve labile bonds distinguishes it from conventional threshold-based MS/MS methods, the most important of which is collision-induced dissociation (CID). During the last decade, ECD has opened up several new venues in protein analyses, for example top-down sequencing, identification of post-translational modifications, and characterization of protein-protein interactions. In recent years, a number of related dissociation techniques, so-called ExD techniques, particularly electron transfer dissociation (ETD), electron detachment dissociation (EDD), electron induced dissociation (EID), and negative electron transfer dissociation (NETD), have emerged and have extended the application range of ion-electron dissociations further. Importantly, ExD techniques have been applied beyond protein analyses, which is the focus of the current paper. This short introduction describes the application of ExD to small and medium-sized molecules and reviews important applications to natural products, biomedical compounds, synthetic molecules, crude oils, and environmental toxins.

Shedding light on the structures of lignin compounds: photo-oxidation under artificial UV light and characterization by high resolution mass spectrometry.

Lignin is the second most abundant natural polymer and a promising alternative energy source for conventional fossil fuels. In this study, we investigated transformations of lignin compounds under artificial UV light conditions at the molecular level. Such light-induced changes of composition profiles in nature after sun exposure have been studied for crude oil in the petroleomics field. We applied a similar high resolution mass spectrometry experimental strategy to lignin and demonstrated various data processing methods to reveal the characteristic differences between the extremely complex data sets of two sample sets, one native control before and one sample after photo-irradiation, using Fourier transform ion cyclotron resonance-mass spectrometry. Graphical abstract Kendrick mass defect versus nominal Kendrick mass for mass spectra of a control and UV-oxidized lignin sample.

Two-dimensional mass defect matrix plots for mapping genealogical links in mixtures of lignin depolymerisation products.

Lignin is the second most abundant natural biopolymer, and lignin wastes are therefore potentially significant sources for renewable chemicals such as fuel compounds, as alternatives to fossil fuels. Waste valorisation of lignin is currently limited to a few applications such as in the pulp industry, however, because of the lack of effective extraction and characterisation methods for the chemically highly complex mixtures after decomposition. Here, we have implemented high resolution mass spectrometry and developed two-dimensional mass defect matrix plots as a data visualisation tool, similar to the Kendrick mass defect plots implemented in fields such as petroleomics. These 2D matrix plots greatly simplified the highly convoluted lignin mass spectral data acquired from Fourier transform ion cyclotron resonance (FTICR)-mass spectrometry, and the derived metrics provided confident peak assignments and strongly improved structural mapping of lignin decomposition product series from the various linkages within the lignin polymer after electrochemical decomposition. Graphical Abstract 2D mass defect matrix plot for a lignin sample after decomposition.

Characterization of the iron-binding properties of pyoverdine using electron-capture dissociation-tandem mass spectrometry.

Pyoverdines (PVD) are a group of siderophores produced by fluorescent Pseudomonads. Identification of PVD variants mostly relies on liquid chromatography-tandem mass spectrometry (LC-MS/MS) using collision-induced dissociation (CID). Here, both CID and the novel dissociation technique electron-capture dissociation (ECD) were applied to characterize PVD succinamide and its Fe(III)-chelated complex. The results clearly showed that ECD produced diagnostic side chain fragmentation of the PVD peptide chain and preserved the labile Fe(III) binding to the chromophore in contrast to CID. The ECD technique is therefore expected to support the understanding of strain-specific Fe(III) transport processes of PVDs.