High-field Fourier Transform Ion Cyclotron Research Articles

Enhanced Speciation of Pyrogenic Organic Matter from Wildfires Enabled by 21 T FT-ICR Mass Spectrometry.

Wildfires affect soils through the formation of pyrogenic organic matter (pyOM) (e.g., char and soot). While many studies examine the connection between pyOM persistence and carbon (C) composition, nitrogen (N) transformation in wildfire-impacted systems remains poorly understood. Thermal reactions in wildfires transform biomass into a highly complex, polyfunctional, and polydisperse organic mixture that challenges most mass analyzers. High-field Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) is the only mass analyzer that achieves resolving powers sufficient to separate species that differ in mass by the mass of an electron across a wide molecular weight range (m/z 150-1500). We report enhanced speciation of organic N by positive-ion electrospray ionization (ESI) that leverages ultrahigh resolving power (m/Δm50% = 1 800 000 at m/z 400) and mass accuracy (<10-100 ppb) achieved by FT-ICR MS at 21 T. Isobaric overlaps, roughly the mass of an electron (Me- = 548 μDa), are resolved across a wide molecular weight range and are more prevalent in positive ESI than negative ESI. The custom-built 21 T FT-ICR MS instrument identifies previously unresolved mass differences in CcHhNnOoSs formulas and assigns more than 30 000 peaks in a pyOM sample. This is the first molecular catalogue of pyOM by positive-ion ESI 21 T FT-ICR MS and presents a method to provide new insight into terrestrial cycling of organic carbon and nitrogen in wildfire impacted ecosystems.

Lessons Learned from a Decade-Long Assessment of Asphaltenes by Ultrahigh-Resolution Mass Spectrometry and Implications for Complex Mixture Analysis

Recent advances in instrumentation for high-field Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) have enabled access to ∼70 »000 unique molecular formulas in broadband mass spectral characterization of unfractionated/whole asphaltenes. The results accumulated over a decade highlight the need for an asphaltene molecular model that acknowledges the coexistence of (1) monofunctional and polyfunctional species; (2) island and archipelago structural motifs; and (3) heteroatom-depleted/highly aromatic compounds, as well as atypical species with low aromaticity but increased heteroatom content. Collectively, results from FT-ICR MS, preparatory-scale separations (extrography/interfacial material), gel permeation chromatography, precipitation behavior in heptane:toluene, thermal decomposition, and aggregate microstructure by atomic force microscopy (among other techniques), suggest that the strong aggregation of asphaltenes results from the synergy between several intermolecular forces: π-stacking, hydrogen bonding, London forces, and acid/base interactions. This review presents general features of asphaltene molecular composition reported over the past five decades. We focus on mass spectrometry characterization and expose the reasons why early results supported the dominance of single-core motifs. Then, the discussion shifts to recent advances in instrumentation for high-field FT-ICR MS, which have enabled the detection of thousands of species in asphaltene samples, whose molecular composition and fragmentation behavior in ultrahigh vacuum agree with the coexistence of single-core and multicore structural motifs. Furthermore, evidence that highlights the limitations of commercially available/custom-built ion sources and selective ionization effects is presented. Consequently, the limitations require separations (e.g., chromatography, extrography) to gain more-comprehensive molecular-level insights into the composition of these complex organic mixtures. The final sections present evidence for the role of aggregation in selective ionization and suggest that advanced characterization by both thermal desorption/decomposition and liquid chromatography with online FT-ICR MS detection can be employed to mitigate the effects of aggregation and provide unique insights in molecular composition/structure.

A History of Molecular Level Analysis of Natural Organic Matter by FTICR Mass Spectrometry and The Paradigm Shift in Organic Geochemistry.

Natural organic matter (NOM) is a complex mixture of biogenic molecules resulting from the deposition and transformation of plant and animal matter. It has long been recognized that NOM plays an important role in many geological, geochemical, and environmental processes. Of particular concern is the fate of NOM in response to a warming climate in environments that have historically sequestered carbon (e.g., peatlands and swamps) but may transition to net carbon emitters. In this review, we will highlight developments in the application of high-field Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) in identifying the individual components of complex NOM mixtures, focusing primarily on the fraction that is dissolved in natural waters (dissolved organic matter or DOM). We will first provide some historical perspective on developments in FTICR technology that made molecular-level characterizations of DOM possible. A variety of applications of the technique will then be described, followed by our view of the future of high-field FTICR MS in carbon cycling research, including a particularly exciting metabolomic approach.

Tracking alterations of alkyl side chains of N1 species in heavy crude oil after anaerobic biodegradation with negative-ion electrospray ionization coupled with high-field Fourier transform ion cyclotron resonance mass spectrometry.

Heteroatomic compounds are relatively abundant and believed to be bio-resistant in heavy crude oils. However, few studies have focused on the biodegradation of these heteroatomic compounds. Heteroatoms, especially N1 species, in a blank crude oil and in three treated oils co-incubated with anaerobic sulfate-reducing bacteria, nitrate-reducing bacteria and fermentative consortia cultures were detected using negative-ion electrospray ionization coupled with high-field Fourier transform ion cyclotron resonance mass spectrometry. The relative abundance of N1 species in the three treated oils decreased, while the relative abundance of O2 species increased. Remarkably, the relative abundances of N1 species with low carbon number increased and those with higher carbon number decreased. These results revealed that the anaerobic biodegradations of heavy crude oil occurred. With direct evidences, the degradations of alkyl side chains of N1 species by the anaerobic microbes could be deduced.

Combating selective ionization in the high resolution mass spectral characterization of complex mixtures.

Direct "dilute and shoot" mass spectral analysis of complex naturally-occurring mixtures has become the "standard" analysis in environmental and petrochemical science, as well as in many other areas of research. Despite recent advances in ionization methods, that approach still suffers several limitations for the comprehensive characterization of compositionally complex matrices. Foremost, the selective ionization of highly acidic (negative electrospray ionization ((-) ESI)) and/or basic (positive electrospray ionization ((+) ESI)) species limits the detection of weakly acidic/basic species, and similar issues (matrix effects) complicate atmospheric pressure photo-ionization (APPI)/atmospheric pressure chemical ionization (APCI) analyses. Furthermore, given the wide range of chemical functionalities and structural motifs in these compositionally complex mixtures, aggregation can similarly limit the observed species to a small (10-20%) mass fraction of the whole sample. Finally, irrespective of the ionization method, the mass analyzer must be capable of resolving tens-of-thousands of mass spectral peaks and provide the mass accuracy (typically 50-300 ppb mass measurement error) required for elemental composition assignment, and thus is generally limited to high-field Fourier transform ion cyclotron mass spectrometry (FT-ICR MS). Here, we describe three approaches to combat the above issues for (+) ESI, (-) ESI, and (+) APPI FT-ICR MS analysis of petroleum samples. Each approach relies on chromatographic fractionation to help reduce selective ionization discrimination and target either specific chemical functionalities (pyridinic and pyrrolic species (nitrogen) or carboxylic acids (oxygen)) or specific structural motifs (single aromatic core (island) or multi-core aromatics (archipelago)) known to be related to ionization efficiency. Each fractionation method yields a 2-10-fold increase in the compositional coverage, exposes species that are undetectable using direct "dilute and shoot" analysis, and provides coarse selectivity in chemical functionalities that can both increase the assignment confidence and optimize ionization conditions to maximize compositional coverage.

Structural information of asphaltenes derived from petroleum vacuum residue and its hydrotreated product obtained by FT-ICR mass spectrometry with narrow ion isolation windows

Petroleum asphaltene is a complex natural organic mixture which plays a crucial role in the refining processes. In this work, asphaltenes derived from petroleum vacuum residue and its hydrotreated product were characterized by high-field Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Tandem mass spectra with narrow ion isolation window were realized by increasing the value of collision RF amplitude. Tandem mass spectra with 3 Da and 1 Da isolation windows were compared, which demonstrated the advantages of applying narrow isolation window of 1 Da. The tandem mass spectra of asphaltenes were simplified due to the narrow isolation window. Moreover, a better correlation between the parent and fragment ions obtained by narrow isolation window of 1 Da was suggested by moving the isolation window. Finally, aromatic hydrocarbons with more naphthenic rings were suggested for the molecular structures of the processed asphaltene according to the results.

Front-End Electron Transfer Dissociation Coupled to a 21 Tesla FT-ICR Mass Spectrometer for Intact Protein Sequence Analysis.

High resolution mass spectrometry is a key technology for in-depth protein characterization. High-field Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) enables high-level interrogation of intact proteins in the most detail to date. However, an appropriate complement of fragmentation technologies must be paired with FTMS to provide comprehensive sequence coverage, as well as characterization of sequence variants, and post-translational modifications. Here we describe the integration of front-end electron transfer dissociation (FETD) with a custom-built 21 tesla FT-ICR mass spectrometer, which yields unprecedented sequence coverage for proteins ranging from 2.8 to 29kDa, without the need for extensive spectral averaging (e.g., ~60% sequence coverage for apo-myoglobin with four averaged acquisitions). The system is equipped with a multipole storage device separate from the ETD reaction device, which allows accumulation of multiple ETD fragment ion fills. Consequently, an optimally large product ion population is accumulated prior to transfer to the ICR cell for mass analysis, which improves mass spectral signal-to-noise ratio, dynamic range, and scan rate. We find a linear relationship between protein molecular weight and minimum number of ETD reaction fills to achieve optimum sequence coverage, thereby enabling more efficient use of instrument data acquisition time. Finally, real-time scaling of the number of ETD reactions fills during method-based acquisition is shown, and the implications for LC-MS/MS top-down analysis are discussed. Graphical Abstract ᅟ.

Evolution of Acidic Compounds in Crude Oil during In Situ Combustion

In situ combustion (ISC) process has drawn more and more attention in the development of heavy oil reservoirs as a result of its high recovery efficiency. Although numerous studies have been reported that oil properties exhibit significant changes during the combustion process, the reaction mechanisms and evolution of oil components are still not well understood. In this work, the compounds of produced oils collected from a three-dimensional simulated production model (container) at different duration times after combustion being initiated and the original oil were characterized at the molecular level using gas chromatography (GC), gas chromatography–mass spectrometry (GC–MS), and high-field Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Both aromatic and acidic components were analyzed. The aromatic components showed relatively more stable characteristics than those of acidic components, and no obvious changes in aromatic compound distributions were observed by the positive ion atmospheric pressure photoionization (APPI) FT-ICR MS analysis. Small aliphatic acids were detected in the ISC oils, which were responsible for the high total acid numbers (TANs). The acidic Ox (x = 1–3) compounds, which have major contributions to the increase in TAN, were generated in greater abundances compared to that of the original crude oil. The carbon number distributions of the O1 and O2 classes in the produced oils significantly shifted to a lower carbon number region, with the dominant distribution from 15–40 at the initial state to 10–30 at the longest duration time. The double bond equivalent (DBE) values decreased during the combustion process. The generated acidic O1 components with DBE values less than 4 were also found in negative ion electrospray ionization (ESI) analysis, indicating the oxidation of hydrocarbons to alcohols.

Tracking Aging of Bitumen and Its Saturate, Aromatic, Resin, and Asphaltene Fractions Using High-Field Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

Bitumen is a widely used material, but its aging behavior is only understood at a macroscopic level as hardening and embrittlement over time. To assess bitumen aging behavior in the long run, the pressure aging vessel (PAV) testing procedure was developed. However, this procedure including high-pressure and high-temperature oxidation of the bitumen has not yet been understood on a molecular level. Here, a bitumen sample and its SARA fractions, i.e., saturates, aromatics, resins, and asphaltenes, were investigated in comparison with their aged samples to study changes of their chemical compositions. Negative electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry [ESI(−)] FT-ICR-MS was used to analyze samples. The effect of aging was characterized using the aromaticity equivalent (Xc), double bond equivalent (DBE), and van Krevelen plots. It was found that aging induces reduction of condensed aromatic compounds to alicyclic and open chain aliphatic compounds, while small aromati...

Comprehensive structure-selective characterization of dissolved organic matter by reducing molecular complexity and increasing analytical dimensions

Deciphering the molecular codes of dissolved organic matter (DOM) improves our understanding of its role in the global element cycles and its active involvement in ecosystem services. This study demonstrates comprehensive characterization of DOM by an initial polarity-based stepwise solid phase extraction (SPE) with single methanol elution of the cartridges, but separate collection of equal aliquots of eluate. The reduction of molecular complexity in the individual DOM fractions attenuates intermolecular interactions and substantially increases the disposable resolution of any structure selective characterization. Suwannee River DOM (SR DOM) was used to collect five distinct SPE fractions with overall 91% DOC recovery. Optical spectroscopy (UV and fluorescence spectroscopy), high-field Fourier transform ion cyclotron mass spectrometry (FTICR MS) and nuclear magnetic resonance (NMR) spectroscopy showed analogous hierarchical clustering among the five eluates corroborating the robustness of this approach. Two abundant moderately hydrophobic fractions contained most of the SR DOM compounds, with substantial proportions of aliphatics, carboxylic-rich alicyclic molecules, carbohydrates and aromatics. A minor early eluting hydrophilic fraction was highly aliphatic and presented a large diversity of alicyclic carboxylic acids, whereas the two late eluting, minor hydrophobic fractions appeared as a largely defunctionalized mixture of aliphatic molecules. Comparative mass analysis showed that fractionation of SR DOM was governed by multiple molecular interactions depending on O/C ratio, molecular weight and aromaticity. The traditional optical indices SUVA254 and fluorescence index (FI) indicated the relative aromaticity in agreement with FTICR mass and NMR spectra; the classical fluorescent peaks A and C were observed in all four latter eluates. This versatile approach can be easily expanded to preparative scale under field conditions, and transferred to different DOM sources and SPE conditions.

Proposed Guidelines for Solid Phase Extraction of Suwannee River Dissolved Organic Matter.

This paper proposes improved guidelines for dissolved organic matter (DOM) isolation by solid phase extraction (SPE) with a styrene-divinylbenzene copolymer (PPL) sorbent, which has become an established method for the isolation of DOM from natural waters, because of its ease of application and appreciable carbon recovery. Suwannee River water was selected to systematically study the effects of critical SPE variables such as loading mass, concentration, flow rate, and up-scaling on the extraction selectivity of the PPL sorbent. High-field Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) and proton nuclear magnetic resonance ((1)H NMR) spectroscopy were performed to interpret the DOM chemical space of eluates, as well as permeates and wash liquids with molecular resolution. Up to 89% dissolved organic carbon (DOC) recovery was obtained with a DOC/PPL mass ratio of 1:800 at a DOC concentration of 20 mg/L. With the application of larger loading volumes, low proportions of highly oxygenated compounds were retained on the PPL sorbent. The effects of the flow rate on the extraction selectivity of the sorbent were marginal. Up-scaling had a limited effect on the extraction selectivity with the exception of increased self-esterification with a methanol solvent, resulting in methyl ester groups. Furthermore, the SPE/PPL extract exhibited highly authentic characteristics in comparison with original water and reverse osmosis samples. These findings will be useful for reproducibly isolating DOM with representative molecular compositions from various sources and concentrations and minimizing potential inconsistencies among interlaboratory comparative studies.

Ultrahigh-resolution FT-ICR mass spectrometry for molecular characterisation of pressurised hot water-extractable organic matter in soils

Dissolved organic matter in soil is a highly reactive pool of organic matter and is of great importance for biogeochemical cycles in soil. A better understanding of its dynamics relies on its molecular characterisation. Here, the molecular composition of water-extracted organic matter at elevated pressure and temperature (PH-WEOM) obtained from 120 Burgundy soils was investigated using high-field Fourier transform-ion cyclotron resonance-mass spectrometry (FT-ICR MS). Unsupervised multivariate statistical analysis (UMSA) was used to retrieve classes of samples with specific molecular characteristics. Accordingly, van Krevelen diagram, Kendrick mass defect (KMD), as well as aromaticity index (AI) and aromaticity equivalent (Xc), were applied to present a pool of ubiquitous molecular formulas and to evaluate the PH-WEOM molecular heterogeneity in the sample set. Based on UMSA, the PH-WEOM from forest soils revealed a clearly distinct molecular composition, with major contributions from lignin- and tannin-like compounds, and with its aromaticity related to soil characteristics, especially the soil pH. No clear evidence of land-cover influence on the PH-WEOM molecular composition was found for cropland and grassland soils, but the role of pH was also identified for these samples, and agrees with molecular patterns attributed to microbial activity, with the presence of compounds with high H/C ratio. A group of samples from cropland soils developed on residual formations is characterised by a very specific molecular composition, rich in aliphatic organosulfur-like compounds, highlighting the importance of specific soil processes in the molecular composition of PH-WEOM. This work demonstrates the potential of FT-ICR MS to resolve the high chemical complexity of PH-WEOM in soils and the intricate influences of both biotic and abiotic environmental factors on the molecular composition of PH-WEOM in soils.

Molecular formula assignment for dissolved organic matter (DOM) using high-field FT-ICR-MS: chemical perspective and validation of sulphur-rich organic components (CHOS) in pit lake samples.

Molecular formula assignment is one of the key challenges in processing high-field Fourier transform ion cyclotron resonance mass spectrometric (FT-ICR-MS) datasets. The number of potential solutions for an elemental formula increases exponentially with increasing molecular mass, especially when non-oxygen heteroatoms like N, S or P are included. A method was developed from the chemical perspective and validated using a Suwannee River Fulvic Acid (SRFA) dataset which is dominated by components consisting exclusively of C, H and O (78% CHO). In order to get information on the application range and robustness of this method, we investigated a FT-ICR-MS dataset which was merged from 18 mine pit lake pore waters and 3 river floodplain soil waters. This dataset contained 50% CHO and 18% CHOS on average, whereas the former SRFA dataset contained only 1.5% CHOS. The mass calculator was configured to allow up to five nitrogen atoms and up to one sulphur atom in assigning formulas to mass peaks. More than 50% multiple-formula assignments were found for peaks with masses > 650Da. Based on DBE - O frequency diagrams, many CHO, CHOS1, CHON1 and CHON1S1 molecular series were ultimately assigned to many m/z and considered to be reliable solutions. The unequivocal data pool could thus be enlarged by 523 (6.8%) CHOS1 components. In contrast to the method validation with CHO-rich SRFA, validation with sulphur-rich pit lake samples showed that formulas with a higher number of non-oxygen heteroatoms can be more reliable assignments in many cases. As an example: CHOS molecular series were reliable and the CHO classes were unreliable amongst other molecular classes in many multiple-formula assignments from the sulphur-rich pit lake samples. Graphical abstract An exemplary frequency versus DBE - O diagram. CHOS components but not CHO (and not CHON2 or CHON2S) components were considered here reliable.

High-Field FTICR-MS Data Evaluation of Natural Organic Matter: Are CHON5S2 Molecular Class Formulas Assigned to 13C Isotopic m/z and in Reality CHO Components?

The analysis of dissolved organic matter (DOM) using high-field Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) poses challenges in molecular formula assignment. The consideration of (13)C isotopes provides new insights into the consistent elemental formula solutions. Modern software helps to overcome misinterpretation, but false assignments of molecular classes to mass peaks have rarely been elucidated until now. It will be demonstrated that this can be important with formula assignments comprising exactly five nitrogen and two sulfur atoms in DOM data sets: the molecular class CHON5S2. The existence of such components in DOM under tripeptide Met-His-Cys formed with the formula C14H23O4N5S2 cannot be excluded; however, components containing 5 N and 2 S should be suspected to not be highly abundant. The true elemental compositions of such unusual "N5S2 moieties" were calculated using Suwannee River fulvic acid (SRFA) data from the literature and one data set from acidic pit lake pore water. The replacement of a H3N5S2 moiety with a (13)C1(12)C5O4 moiety explained more than 95% of the questionable "N5S2 moieties". This finding was proved by calculation of δ(13)C‰ values from relative peak intensities.

Laserspray and Matrix-Assisted Ionization Inlet Coupled to High-Field FT-ICR Mass Spectrometry for Peptide and Protein Analysis

We present the first coupling of laser spray ionization inlet (LSII) and matrix assisted ionization inlet (MAII) to high-field Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) for generation of electrospray-like ions to take advantage of increased sensitivity, mass range, and mass resolving power afforded by multiple charging. We apply the technique to top-down protein analysis and characterization of metalloproteins. We also present a novel method for generation of multiply-charged copper-peptide complexes with varying degrees of copper adduction by LSII. We show an application of the generated copper-peptide complexes for protein charge state and molecular weight determination, particularly useful for an instrument such as a linear ion trap mass analyzer.

Kendrick-Analogous Network Visualisation of Ion Cyclotron Resonance Fourier Transform Mass Spectra: Improved Options for the Assignment of Elemental Compositions and the Classification of Organic Molecular Complexity

Here, we propose a novel computational and visual approach for the analysis of high field Fourier transform ion cyclotron resonance mass spectra (FTICR/MS) based on successive and multiple atomic and Kendrick analogous mass difference analyses. Compositional networks based on elemental compositions and functional networks based on selected functional groups equivalents enable improved assignment options of elemental composition and classification of organic complexity with tunable validation windows. The approach is demonstrated through the analysis of a 12T FTICR mass spectrum of an intricate water soluble extract of a secondary organic aerosol with a previously established abundance in CHNOS molecules.

Chromatographic Reduction of Isobaric and Isomeric Complexity of Fulvic Acids To Enable Multistage Tandem Mass Spectral Characterization

Humic substances and related material commonly grouped under the designation of natural organic matter (NOM) are of interest in fields ranging from marine chemistry and geochemistry to industry, agriculture, and pharmacology. High-field Fourier transform ion cyclotron resonance mass spectrometry enables resolution and identification of elemental compositions of up to thousands of components from a single mass spectrum. Here, we introduce an offline prefractionation to reduce the number of species of the same nominal (nearest-integer) mass, allowing for isolation of ions of one or a few m/z values, from which structural information can be obtained by low-resolution multistage tandem mass spectrometry (MS(n)). Alternatively, precharacterized fractions can be generated for other types of analysis. As an example, we demonstrate significant reduction of isomeric and isobaric complexity for Suwannee River fulvic acid (SRFA). The combined MS and MS(n) analyses support the hypothesis that early eluting material comprises older, highly oxidized SRFA, whereas later eluting material is younger, retaining some similarity with precursor material.

Characterization of petroleum acids using combined FT-IR, FT-ICR–MS and GC–MS: Implications for the origin of high acidity oils in the Muglad Basin, Sudan

Examination of whole oils and isolated oil acidic fractions using Fourier transform infrared (FT-IR), negative-ion microelectrospray high-field Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR–MS) and gas chromatography–mass spectrometry (GC–MS) reveals significant differences in the functional groups, chemical classes and molecular weights of acidic components in crude oils derived from inland lacustrine source rocks in the Fula Sub-basin, Muglad Basin, Sudan. Correlation of the total acid number value (TAN) and bulk and molecular compositions with reservoir depth (temperature) indicates a strong influence of biodegradation on the origin of the high acidity in the oils and the possibility of distinguishing acidic compounds newly formed by way of in-reservoir biodegradation and those contributed directly from oil degrading bacteria.

Ultrahigh resolution mass spectrometry

The integration of soft ionization technologies and ultrahigh resolution FTICR mass spectrometry (Fourier transform ion-cyclotron MS) has enabled the examination of molecules, directly from mixtures, with ultrahigh mass resolution and sub-ppm mass accuracy. This ability to observe structure and reactivity aspects of intact (macro)molecules has, in particular, contributed to the molecular-level characterization of complex matrices, for example novel materials and biological and biogeochemical samples. Here, thousands of molecular formulae can be determined in a single measurement directly from mixtures. The exceptional performance of ultrahigh-resolution FTICR mass spectroscopy in the characterization of complex systems suffers much less from the detrimental effects of intrinsic averaging, which is a characteristic of most other methods of organic structural spectroscopy. This novel information-rich and direct perception has the potential to entirely change the way we address the molecular-level analysis of complex materials, systems, and processes in general, thereby opening novel perspectives in data-driven systems biology and “omics” approaches. The inauguration of Europe’s first 12 Tesla FTICR mass spectrometer at the GSF National Research Center for Environment and Health provided the opportunity to hear expert views on novel research dedicated to the molecular-level characterization of complex systems. A dozen presentations organized in four sessions were delivered during the “First International Symposium on Ultrahigh-Resolution Mass Spectrometry for the Molecular Level Analysis of Complex (BioGeo)Systems”, held at the GSF on November 6 and 7, 2006 (www.gsf.de/FTMS2006). In session one, General Foundations of FTICR Mass Spectrometry, Alan G. Marshall (National High Magnetic Field Laboratory, Tallahassee, USA) provided a wide-ranging overview about the currently available opportunities of FTMS in molecular-resolution analysis: High-field Fourier transform ion cyclotron resonance mass spectrometry: a platform for “omics”. Then, Eugene N. Nikolaev (Institute of Biochemical Physics, Moscow, Russian Federation) investigated the complex trajectories of ions in FTMS cells: The new possibilities in ion clouds dynamic simulation using supercomputers. Application to FTICR and quadrupole devices. Arnd Ingendoh (Bruker Daltonics, Bremen, Germany) provided an overview about current and foreseeable trends in modern mass spectrometry: Mass spectrometry and beyond—new areas of applications. Session two, From Biological Chemistry to Chemical Biology, focused on life sciences applications. Jeremy K. Nicholson (Division of Surgery, Oncology, Reproductive Biology and Anaesthetics, Imperial College, London, UK) produced a comprehensive assessment about integrated views in “omics” sciences (Metabonomics and top-down systems biology: from personalized healthcare to molecular epidemiology) and Hannelore Daniel (Technical University Munich, Weihenstephan, Germany) complemented this interesting and versatile perspective with The bottom-up approach: from individual genes to the systems biology level of nutrition. Michael Sattler (European Molecular Biology Laboratory, Heidelberg, Germany and GSF Research Center for Environment and Health) illustrated the power of modern NMR methods capable of producing well resolved three-dimensional structures of large biomolecules including description of dynamics and reactivity: NMR to study molecular recognition and dynamics of biomacromolecules. Session three, Novel MS Approaches in Biochemistry and Medicine, illustrated novel MS approaches by Gary Siuzdak (Scripps Center for Mass Spectrometry, La Jolla, USA): Novel mass-based approaches to proteomics and metabolomics and advanced carbohydrate analysis by Jasna Peter-Katalinic (Institute fur Medical Physics and Biophysics, Munster, Germany): Requirements on FTICR mass spectrometry for glycomics in structural biology and medicine. Session four, Repetitive and Non-Repetitive Complex Systems, focused on proteome and complex biogeochemical mixture analysis. Michael Przybylski (Department of Chemistry, University of Konstanz, Germany) elucidated aspects of advanced protein analysis High resolution FTICR mass spectrometry and affinity-proteomics: powerful tool for elucidation of antigen-antibody recognition structures and vaccine development in molecular immunology and complex biogeochemical materials and William T. Cooper (Department of Chemistry and Biochemistry, FSU, Tallahassee, USA) provided insights into the structure, synthesis and degradation of natural organic matter: Insights into organic chemistry of the natural environment; FTICR mass spectrometry of really complex mixtures. Norbert Hertkorn (GSF Institute of Ecological Chemistry, Neuherberg, Germany) described the specific utility and complementarity of NMR and mass spectrometry in the analysis of complex biogeochemical systems: Mapping the molecular compositional space with mass spectrometry, and Philippe Schmitt-Kopplin (GSF Institute of Ecological Chemistry, Neuherberg, Germany) provided a comprehensive assessment of biogeochemical analysis with a variety of current examples: Molecular-level analysis of non-repetitive structures in biogeosystems. To recognize the importance of the technique and provide the reader of the journal Analytical and Bioanalytical Chemistry with a perspective of the current trends in FTICR mass spectrometry, this special issue on “Ultrahigh Resolution Mass Spectrometry” was prepared to include research, perspective, and review articles from experts in the field. This special issue reflects the wide scope of current FTICR mass spectrometry utilization in the analytical characterization of natural products, biomolecules and biogeochemical mixtures, hyphenation of separation and mass spectrometry, and integration of spectroscopy and separation in the molecular-level characterization of complex systems. At this point, we would like to thank all the authors for their high-quality articles, all referees for the rapid evaluations.

Resolution and Identification of Elemental Compositions for More than 3000 Crude Acids in Heavy Petroleum by Negative-Ion Microelectrospray High-Field Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

Although crude acids are minor constituents in petroleum, they have significant implications for crude oil geochemistry, corrosion, and commerce. We have previously demonstrated that a single positive-ion electrospray ionization (ESI) high-field Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) experiment can resolve and identify 3000 chemically different elemental compositions of bases (basic nitrogen compounds) in a crude oil. Here, we show that negative-ion ESI high-field FT-ICR MS can selectively ionize and identify naphthenic acids without interference from the hydrocarbon background. When combined with prechromatographic separation, ESI FT-ICR MS reveals an even more detailed acid composition. An average mass resolving power, m/Δm50% ≥ 80 000 (Δm50% is mass spectral peak full width at half-maximum peak height) across a wide mass range (200 < m/z < 1000), distinguishes as many as 15 distinct chemical formulas within a 0.26 Da mass window. Collectively, more than 3000 chemically different elemental compositions containing O2, O3, O4, and O2S, O3S, and O4S were determined in a South American heavy crude. Our data indicates that the crude acids consist of a mixture of structures ranging from C15−C55 with cyclic (1−6 rings) and aromatic (1−3 ring) structures. The acid composition appears to be simpler than that of the corresponding hydrocarbon analogues.