The Application of Electrospray Ionization Coupled to Ultrahigh Resolution Mass Spectrometry for the Molecular Characterization of Natural Organic Matter

Mass spectrometry has recently played a key role in the understanding of natural organic matter (NOM) by providing molecular-level details about its composition. NOM, a complex assemblage of organic molecules present in natural waters and soils/sediments, has the ability to bind and transport anthropogenic materials. An improved understanding of its composition is crucial in order to understand how pollutants interact with NOM and how NOM cycles through global carbon cycles. In the past, low-resolution (\u3e 3000) mass analyzers have offered some insights into the structure of NOM, but emerging ultrahigh resolution (\u3e 200000) techniques such as electrospray ionization (ESI) coupled to Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) have significantly advanced our knowledge of NOM chemistry. Here, a review of the recent literature on the advancements of NOM characterization and the applications of mass spectrometry to this central task is presented. Various methods for the analysis and display of the extremely complex mass spectra, such as the van Krevelen diagram and Kendrick mass defect analysis, are discussed. We also review tandem mass spectrometry techniques employed to gain structural information about NOM components. Finally, we show how ESI-FT-ICR-MS has been applied to examine specific issues that are important to the NOM scientific community, such as NOM reactivity, transport and fate, degradation, and existence of components, which are indicators of NOM origin. In general, ultrahigh resolution provided by FT-ICR-MS is essential for the complete separation of the thousands of peaks present in the complex NOM mixture and will clearly lead to additional future advancements in the areas of aquatic, soil, and analytical chemistry. Copyright (c) 2007 John Wiley & Sons, Ltd

Early maturation processes in coal. Part 1: Pyrolysis mass balances and structural evolution of coalified wood from the Morwell Brown Coal seam

In this work, we develop a theoretical approach to evaluate maturation process of kerogen-like material, involving molecular dynamic reactive modeling with a reactive force field to simulate the thermal stress. The Morwell coal has been selected to study the thermal evolution of terrestrial organic matter. To achieve this, a structural model is first constructed based on models from the literature and analytical characterization of our samples by modern 1-and 2-D NMR, FTIR, and elemental analysis. Then, artificial maturation of the Morwell coal is performed at low conversions in order to obtain, quantitative and qualitative, detailed evidences of structural evolution of the kerogen upon maturation. The observed chemical changes are a defunctionalization of the carboxyl, carbonyl and methoxy functional groups coupling with an increase of cross linking in the residual mature kerogen. Gaseous and liquids hydrocarbons, essentially CH4, C4H8 and C14+ liquid hydrocarbons, are generated in low amount, merely by cleavage of the lignin side chain

A Mini-Electrodialysis System for Desalting Small Volume Saline Samples for Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

An affordable, commercially available mini-electrodialysis (mini-ED) system has been evaluated for the efficient desalting of small volume samples of seawater before analysis by electrospray Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS). Mini-ED FT-ICR mass spectra were compared with spectra for samples that were treated by C18 solid phase extraction, a commonly used method for rapid sample preparation for this type of analysis. In this comparison, it is clear that mini-ED provides more representative molecular information, compared with C18 isolation, and recovers the overwhelming majority of peaks from salt-free samples, indicating that it adequately represents the DOM that can be ionized and analyzed by ESI FT-ICR MS. The ED system produces a significant carbon blank. However, the substances contributing to this blank are not detectable by ESI FT-ICR MS. Based on these findings mini-ED is recommended as a promising method for the desalting of aqueous environmental samples before analysis by ESI FT-ICR MS. © 2011, by the American Society of Limnology and Oceanography, Inc

The Shape of Pulverized Bituminous Vitrinite Coal Particles

The shape of pulverized bituminous coal particles (vitrinites) was determined by optical and laser light scattering. Vitrain samples were collected from obvious tree remains located in the ceilings of two Appalachian coal mines. Wet sieving produced narrow size cuts. The particles were determined to be oblong or blocky in shape, with average length-to-width ratio of 1.7 and sphericity of 0.78. They were analogous in shape to a square ended, rectangular house brick . The two bituminous coals and different size cuts of each coal had essentially the same shape parameters. Characteristic heating times and terminal velocities were higher by 22 and 20%, respectively compared to spherical particles

A Molecular-Level Approach for Characterizing Water-Insoluble Components of Ambient Organic Aerosol Particulates Using Ultrahigh-Resolution Mass Spectrometry

The chemical composition of organic aerosols in the atmosphere is strongly influenced by human emissions. The effect these have on the environment, human health, and climate change is determined by the molecular nature of these chemical species. The complexity of organic aerosol samples limits the ability to study the chemical composition, and therefore the associated properties and the impacts they have. Many studies have addressed the watersoluble fraction of organic aerosols and have had much success in identifying specific molecular formulas for thousands of compounds present. However, little attention is given to the water-insoluble portion, which can contain most of the fossil material that is emitted through human activity. Here we compare the organic aerosols present in water extracts and organic solvent extracts (pyridine and acetonitrile) of an ambient aerosol sample collected in a rural location that is impacted by natural and anthropogenic emission sources. A semiquantitative method was developed using proton nuclear magnetic resonance spectroscopy to determine that the amount of organic matter extracted by pyridine is comparable to that of water. Electrospray ionization Fourier transform ion cyclotron resonance mass spectra show that pyridine extracts a molecularly unique fraction of organic matter compared to water or acetonitrile, which extract chemically similar organic matter components. The molecular formulas unique to pyridine were less polar, more aliphatic, and reveal formulas containing sulfur to be an important component of insoluble aerosol organic matter

Formation of Water-Soluble Organic Matter Through Fungal Degradation of Lignin

Lignin is a major component of decaying terrestrial vegetation in soils and has been reported to contribute substantially to the formation of soil carbon humus and associated water extracts of soil. To better understand this process of humification, lignin from brown-rot degraded wood is subjected to a white-rot fungus (Phanerochaete chrysosporium)whose enzymes are particularly effective in lignin degradation. This enzymatic attack was monitored by ultrahigh resolution mass spectrometry of water soluble extracts of the fungal cultures. The ensuing molecular level characterizations showed that the P. chrysosporium fungi induced aromatic ring oxidations followed by ring opening as expected. However, we also observed the production of new molecules, some of which are aliphatic. These results are consistent with recent findings that hydroxyl radical attack of lignin involves ring opening reactions followed by electrocyclic condensations combined with radical scavenging/disproportionation reactions

Detailed Source-Specific Molecular Composition of Ambient Aerosol Organic Matter Using Ultrahigh Resolution Mass Spectrometry and H NMR

Organic aerosols (OA) are universally regarded as an important component of the atmosphere that have far-ranging impacts on climate forcing and human health. Many of these impacts are related to OA molecular characteristics. Despite the acknowledged importance, current uncertainties related to the source apportionment of molecular properties and environmental impacts make it difficult to confidently predict the net impacts of OA. Here we evaluate the specific molecular compounds as well as bulk structural properties of total suspended particulates in ambient OA collected from key emission sources (marine, biomass burning, and urban) using ultrahigh resolution mass spectrometry (UHR-MS) and proton nuclear magnetic resonance spectroscopy (1H NMR). UHR-MS and 1H NMR show that OA within each source is structurally diverse, and the molecular characteristics are described in detail. Principal component analysis (PCA) revealed that (1) aromatic nitrogen species are distinguishing components for these biomass burning aerosols; (2) these urban aerosols are distinguished by having formulas with high O/C ratios and lesser aromatic and condensed aromatic formulas; and (3) these marine aerosols are distinguished by lipid-like compounds of likely marine biological origin. This study provides a unique qualitative approach for enhancing the chemical characterization of OA necessary for molecular source apportionment

Condensation and Polymerization Explain the Humification of Lignin Into Aliphatic and Aromatic Structures in Soil

Soil organic matter (SOM) constitutes a global reservoir of carbon that is more than twice that of either atmospheric carbon or aquatic carbon; however, the manner in which it forms from degraded plant biomass is poorly understood. Some have recently questioned whether plant biomass is involved directly in SOM formation and suggest that it is microbial carbon that constitutes the main source of stable SOM. Such a view implies that above and below ground plant biomass is rapidly decomposed and mineralized. This view contrasts significantly with traditional ones that involve the transformation of plant biomass to recalcitrant humic materials fueled mainly by lignin. One of the main observations for the new viewpoint is that lignin phenols, biomarkers for lignin in plant biomass, become depleted rapidly in SOM and are thought to indicate that lignin, carbohydrates, proteins, and other plant biopolymers are depleted at the same rate. In the current study we demonstrate that lignin plays a pivotal role in the formation of geologically stable SOM and that the new viewpoint grossly miscalculates the input of microbial biomass. Promoted by the strong oxidation of prevalent reactive oxygen species (ROS) in soil, lignin is not completely mineralized but molecularly transformed to structures not recognizable by lignin phenol biomarker studies. We employ NMR and ultrahigh resolution mass spectrometry on a series of plant biopolymers, synthesized lignin, soil, and peat samples to demonstrate the effect of ROS transformations involving mainly hydroxyl radicals