Ultrahigh-resolution Fourier Transform Ion Cyclotron Research Articles

Asphaltene Characterization during Hydroprocessing by Ultrahigh-Resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

Asphaltenes have a significant impact on the hydroprocessing of residues because they adversely affect the overall rate of hydroprocessing reactions. They also act as coke precursors, leading to catalyst deactivation. Understanding the changes of asphaltenes upon conversion can provide essential clues to the development and optimization of residue conversion processes. In this work, we use ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (positive-ion mode atmospheric pressure photoionization) to follow asphaltene changes during the hydroprocessing of a residue. Asphaltenes were extracted from the feed and from two different products sampled at various times during the run. Results indicate that intensities for hydrocarbon classes and N-containing classes increase for the processed asphaltenes, while the abundance of S classes decreases. Similar results are found when the number of peak assignments is compared. The average double-bond equivalent (DBE) increases as a functio...

Ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry and tandem mass spectrometry for peptide de novo amino acid sequencing for a seven-protein mixture by paired single-residue transposed Lys-N and Lys-C digestion.

Bottom-up tandem mass spectrometry (MS/MS) is regularly used in proteomics to identify proteins from a sequence database. De novo sequencing is also available for sequencing peptides with relatively short sequence lengths. We recently showed that paired Lys-C and Lys-N proteases produce peptides of identical mass and similar retention time, but different tandem mass spectra. Such parallel experiments provide complementary information, and allow for up to 100% MS/MS sequence coverage. Here, we report digestion by paired Lys-C and Lys-N proteases of a seven-protein mixture: human hemoglobin alpha, bovine carbonic anhydrase 2, horse skeletal muscle myoglobin, hen egg white lysozyme, bovine pancreatic ribonuclease, bovine rhodanese, and bovine serum albumin, followed by reversed-phase nanoflow liquid chromatography, collision-induced dissociation, and 14.5T Fourier transform ion cyclotron resonance mass spectrometry. Matched pairs of product peptide ions of equal precursor mass and similar retention times from each digestion are compared, leveraging single-residue transposed information with independent interferences to confidently identify fragment ion types, residues, and peptides. Selected pairs of product ion mass spectra for de novo sequenced protein segments from each member of the mixture are presented. Pairs of the transposed product ions as well as complementary information from the parallel experiments allow for both high MS/MS coverage for long peptide sequences and high confidence in the amino acid identification. Moreover, the parallel experiments in the de novo sequencing reduce false-positive matches of product ions from the single-residue transposed peptides from the same segment, and thereby further improve the confidence in protein identification. Copyright © 2016 John Wiley & Sons, Ltd.

Identifying precursors and aqueous organic aerosol formation pathways during the SOAS campaign

Abstract. Aqueous multiphase chemistry in the atmosphere can lead to rapid transformation of organic compounds, forming highly oxidized, low-volatility organic aerosol and, in some cases, light-absorbing (brown) carbon. Because liquid water is globally abundant, this chemistry could substantially impact climate, air quality, and health. Gas-phase precursors released from biogenic and anthropogenic sources are oxidized and fragmented, forming water-soluble gases that can undergo reactions in the aqueous phase (in clouds, fogs, and wet aerosols), leading to the formation of secondary organic aerosol (SOAAQ). Recent studies have highlighted the role of certain precursors like glyoxal, methylglyoxal, glycolaldehyde, acetic acid, acetone, and epoxides in the formation of SOAAQ. The goal of this work is to identify additional precursors and products that may be atmospherically important. In this study, ambient mixtures of water-soluble gases were scrubbed from the atmosphere into water at Brent, Alabama, during the 2013 Southern Oxidant and Aerosol Study (SOAS). Hydroxyl (OH⚫) radical oxidation experiments were conducted with the aqueous mixtures collected from SOAS to better understand the formation of SOA through gas-phase followed by aqueous-phase chemistry. Total aqueous-phase organic carbon concentrations for these mixtures ranged from 92 to 179 µM-C, relevant for cloud and fog waters. Aqueous OH-reactive compounds were primarily observed as odd ions in the positive ion mode by electrospray ionization mass spectrometry (ESI-MS). Ultra high-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) spectra and tandem MS (MS–MS) fragmentation of these ions were consistent with the presence of carbonyls and tetrols. Products were observed in the negative ion mode and included pyruvate and oxalate, which were confirmed by ion chromatography. Pyruvate and oxalate have been found in the particle phase in many locations (as salts and complexes). Thus, formation of pyruvate/oxalate suggests the potential for aqueous processing of these ambient mixtures to form SOAAQ.

Chemodiversity of dissolved organic matter in the Amazon Basin

Abstract. Regions in the Amazon Basin have been associated with specific biogeochemical processes, but a detailed chemical classification of the abundant and ubiquitous dissolved organic matter (DOM), beyond specific indicator compounds and bulk measurements, has not yet been established. We sampled water from different locations in the Negro, Madeira/Jamari and Tapajós River areas to characterize the molecular DOM composition and distribution. Ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) combined with excitation emission matrix (EEM) fluorescence spectroscopy and parallel factor analysis (PARAFAC) revealed a large proportion of ubiquitous DOM but also unique area-specific molecular signatures. Unique to the DOM of the Rio Negro area was the large abundance of high molecular weight, diverse hydrogen-deficient and highly oxidized molecular ions deviating from known lignin or tannin compositions, indicating substantial oxidative processing of these ultimately plant-derived polyphenols indicative of these black waters. In contrast, unique signatures in the Madeira/Jamari area were defined by presumably labile sulfur- and nitrogen-containing molecules in this white water river system. Waters from the Tapajós main stem did not show any substantial unique molecular signatures relative to those present in the Rio Madeira and Rio Negro, which implied a lower organic molecular complexity in this clear water tributary, even after mixing with the main stem of the Amazon River. Beside ubiquitous DOM at average H ∕ C and O ∕ C elemental ratios, a distinct and significant unique DOM pool prevailed in the black, white and clear water areas that were also highly correlated with EEM-PARAFAC components and define the frameworks for primary production and other aspects of aquatic life.

Fe- and Cu-Complex Formation with Artificial Ligands Investigated by Ultra-High Resolution Fourier-Transform ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS): Implications for Natural Metal-Organic Complex Studies

In recent years, electrospray-ionization mass spectrometry (ESI-MS) has been increasingly used to complement the bulk determination of metal-ligand equilibria, for example via competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-ACSV). However, ESI-MS speciation analyses may be impacted by instrumental artefacts such as reduction reactions, fragmentation, and adduct formation at the ESI source, changes in the ionization efficiencies of the detected species in relation to sample matrix, and peak overlaps in response to increasing sample complexity. In our study, equilibria of the known artificial ligands citrate, ethylenediaminetetraacetic acid (EDTA), 1-nitroso-2-naphthol (NN), and salicylaldoxime (SA) with iron (Fe) and copper (Cu) were investigated by ultra-high resolution ESI-MS, Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), under a variety of sample matrix and ionization settings. The acquired mass spectra were compared with metal-ligand equilibrium data from the literature as well as an adapted speciation model. Overall, the mass spectra produced representative species mentioned in previous reports and predicted by the speciation calculations, such as Fe(Cit), Cu(Cit)2, Fe(EDTA), Cu(EDTA), Fe(NN)3, and Cu(SA)2. The analyses furthermore revealed new species which had been hypothesized but not measured directly using other methods, for example ternary complexes of citrate with Fe and Cu, Cu(SA) monomers, and the dimer Fe(SA)2. Finally, parallel measurements of a Cu+SA calibration series and a Cu+SA+EDTA competition series indicated that FT-ICR-MS can produce linear responses and low detection limits analogous to those of ACSV. We propose that ultra-high resolution FT-ICR-MS can be used as a representative tool to study interactions of trace metals with artificial as well as natural, unknown ligands at the molecular level.

Short-Term Dynamics of North Sea Bacterioplankton-Dissolved Organic Matter Coherence on Molecular Level.

Remineralization and transformation of dissolved organic matter (DOM) by marine microbes shape the DOM composition and thus, have large impact on global carbon and nutrient cycling. However, information on bacterioplankton-DOM interactions on a molecular level is limited. We examined the variation of bacterial community composition (BCC) at Helgoland Roads (North Sea) in relation to variation of molecular DOM composition and various environmental parameters on short-time scales. Surface water samples were taken daily over a period of 20 days. Bacterial community and molecular DOM composition were assessed via 16S rRNA gene tag sequencing and ultrahigh resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), respectively. Environmental conditions were driven by a coastal water influx during the first half of the sampling period and the onset of a summer phytoplankton bloom toward the end of the sampling period. These phenomena led to a distinct grouping of bacterial communities and DOM composition which was particularly influenced by total dissolved nitrogen (TDN) concentration, temperature, and salinity, as revealed by distance-based linear regression analyses. Bacterioplankton-DOM interaction was demonstrated in strong correlations between specific bacterial taxa and particular DOM molecules, thus, suggesting potential specialization on particular substrates. We propose that a combination of high resolution techniques, as used in this study, may provide substantial information on substrate generalists and specialists and thus, contribute to prediction of BCC variation.

Increasing Polyaromatic Hydrocarbon (PAH) Molecular Coverage during Fossil Oil Analysis by Combining Gas Chromatography and Atmospheric-Pressure Laser Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS).

Thousands of chemically distinct compounds are encountered in fossil oil samples that require rapid screening and accurate identification. In the present paper, we show for the first time, the advantages of gas chromatography (GC) separation in combination with atmospheric-pressure laser ionization (APLI) and ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) for the screening of polyaromatic hydrocarbons (PAHs) in fossil oils. In particular, reference standards of organics in shale oil, petroleum crude oil, and heavy sweet crude oil were characterized by GC-APLI-FT-ICR MS and APLI-FT-ICR MS. Results showed that, while APLI increases the ionization efficiency of PAHs, when compared to other ionization sources, the complexity of the fossil oils reduces the probability of ionizing lower-concentration compounds during direct infusion. When gas chromatography precedes APLI-FT-ICR MS, an increase (more than 2-fold) in the ionization efficiency and an increase in the signal-to-noise ratio of lower-concentration fractions are observed, giving better molecular coverage in the m/z 100-450 range. That is, the use of GC prior to APLI-FT-ICR MS resulted in higher molecular coverage, higher sensitivity, and the ability to separate and characterize molecular isomers, while maintaining the ultrahigh resolution and mass accuracy of the FT-ICR MS separation.

Molecular alteration of marine dissolved organic matter under experimental hydrothermal conditions

Marine dissolved organic matter (DOM) is a large (660Pg) pool of reduced carbon that is subject to thermal alteration in hydrothermal systems and sedimentary basins. In natural high-temperature hydrothermal systems, DOM is almost completely removed, but the mechanism and temperature dependence of this removal have not been studied to date. We investigated molecular-level changes to DOM that was solid-phase extracted (SPE-DOM) from the deep ocean of the North Pacific Ocean. This complex molecular mixture was experimentally exposed to temperatures between 100 and 380°C over the course of two weeks in artificial seawater, and was then characterised on a molecular level via ultrahigh-resolution Fourier-transform ion cyclotron mass spectrometry (FT-ICR-MS). Almost 93% of SPE-DOM was removed by the treatment at 380°C, and this removal was accompanied by a consistent pattern of SPE-DOM alteration across the temperatures studied. Higher molecular weight and more oxygen rich compounds were preferentially removed, suggesting that decarboxylation and dehydration of carboxylic acid and alcohol groups are the most rapid degradation mechanisms. Nitrogen containing compounds followed the same overall trends as those containing just C, H and O up to 300°C. Above this temperature, the most highly altered samples contained very little of the original character of marine DOM, instead being mainly composed of very low intensity N- and S- containing molecules with a high H/C ratio (>1.5). Our results suggest that abiotic hydrothermal alteration of SPE-DOM may already occur at temperatures above 68°C. Our experiments were conducted without a sedimentary or mineral phase, and demonstrate that profound molecular alteration and almost complete removal of marine SPE-DOM requires nothing more than heating in a seawater matrix.

Linking the Molecular Signature of Heteroatomic Dissolved Organic Matter to Watershed Characteristics in World Rivers.

Large world rivers are significant sources of dissolved organic matter (DOM) to the oceans. Watershed geomorphology and land use can drive the quality and reactivity of DOM. Determining the molecular composition of riverine DOM is essential for understanding its source, mobility and fate across landscapes. In this study, DOM from the main stem of 10 global rivers covering a wide climatic range and land use features was molecularly characterized via ultrahigh-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). FT-ICR mass spectral data revealed an overall similarity in molecular components among the rivers. However, when focusing specifically on the contribution of nonoxygen heteroatomic molecular formulas (CHON, CHOS, CHOP, etc.) to the bulk molecular signature, patterns relating DOM composition and watershed land use became apparent. Greater abundances of N- and S-containing molecular formulas were identified as unique to rivers influenced by anthropogenic inputs, whereas rivers with primarily forested watersheds had DOM signatures relatively depleted in heteroatomic content. A strong correlation between cropland cover and dissolved black nitrogen was established when focusing specifically on the pyrogenic class of compounds. This study demonstrated how changes in land use directly affect downstream DOM quality and could impact C and nutrient cycling on a global scale.

Comprehensive Characterization of Second-Generation Biofuel from Invasive Freshwater Plants by FT-ICR MS

Ultra-high resolution and mass accuracy Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS) with an electrospray ionization source (ESI) was applied to characterize the bio-oils that were obtained using a micropyrolysis process of alternative biomasses from Eichornia crassipes (water hyacinth), Eichornia azurea, and Nymphaea ssp. The methods that have been developed for petroleomic analyses using FT-ICR MS data from crude oils and derivatives have been successfully employed herein to process such data for bio-oils, which are known as second-generation liquid biofuels. Class distributions and DBE versus carbon number plots (DBE × Cn) were, therefore, obtained. The class distribution for the oil obtained from water hyacinth was similar to those of classical bio-oils and appeared to be applicable as a fingerprint for bio-oils in general. The N2 and O2 classes obtained via ESI(+) and the O2 and O3 classes obtained via ESI(−) were the major classes detected in the bio-oil samples. In the DBE x Cn plot of the ESI(−)-FT-ICR MS data, the distribution of saturated and unsaturated fatty acids could be visualized, and characteristic profiles were determined for each bio-oil. It is, therefore, demonstrated that the FT-ICR MS methodology that is commonly applied to petroleomic studies can also be applied to biofuel characterization in a comprehensive “bio-oilomics” approach.

Molecular-level changes of dissolved organic matter along the Amazon River-to-ocean continuum

Coastal oceans link terrestrial and marine carbon cycles. Yet, carbon sources and sinks in these biomes remain poorly understood. Here, we explore the dynamics of dissolved organic matter (DOM) along the Amazon River-to-ocean continuum from the lower mainstem at Óbidos to the open ocean of the western tropical North Atlantic. We molecularly characterized DOM via ultrahigh-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), determined DOM stable carbon isotopes, and interpreted the data in the context of bacterial abundance and production, phytoplankton biomass and composition. Multivariate analysis revealed that the DOM molecular variability in the plume was mainly influenced by the input of terrigenous DOM. Incubation experiments with water from close to the river mouth showed that photo- and bio-degradation preferentially removed 13C-depleted and 13C-enriched terrigenous DOM, respectively. However, there was no significant quantitative change in the total amount of dissolved organic carbon (DOC) over five days. This result suggests that most of the reactive DOM had already been bio-degraded upstream within the river and that photo-degradation was diminished in the turbid plume close to the river mouth. Terrigenous DOM therefore appeared to be relatively non-reactive nearshore. In the less turbid offshore plume, enhanced light penetration stimulated growth of phytoplankton and increased bacterial production. Although marine DOM compounds became relatively enriched, bulk DOC concentrations were 9 to 30% below levels expected from conservative mixing of river and ocean endmembers suggesting that quantitative removal of terrigenous DOM was not compensated by marine DOM production. We propose that removal of terrigenous DOM in the outer plume may be enhanced by (i) bio-degradation primed by reactive algal DOM, (ii) photo-degradation, which may further break down DOM into more bio-available forms, and possibly (iii) sorption of DOM to sinking particles.

Hyphenation of Thermal Analysis to Ultrahigh-Resolution Mass Spectrometry (Fourier Transform Ion Cyclotron Resonance Mass Spectrometry) Using Atmospheric Pressure Chemical Ionization For Studying Composition and Thermal Degradation of Complex Materials.

In this study, the hyphenation of a thermobalance to an ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometer (UHR FTICR MS) is presented. Atmospheric pressure chemical ionization (APCI) is used for efficient ionization. The evolved gas analysis (EGA), using high-resolution mass spectrometry allows the time-resolved molecular characterization of thermally induced processes in complex materials or mixtures, such as biomass or crude oil. The most crucial part of the setup is the hyphenation between the thermobalance and the APCI source. Evolved gases are forced to enter the atmospheric pressure ionization interface of the MS by applying a slight overpressure at the thermobalance side of the hyphenation. Using the FTICR exact mass data, detailed chemical information is gained by calculation of elemental compositions from the organic species, enabling a time and temperature resolved, highly selective detection of the evolved species. An additional selectivity is gained by the APCI ionization, which is particularly sensitive toward polar compounds. This selectivity on the one hand misses bulk components of petroleum samples such as alkanes and does not deliver a comprehensive view but on the other hand focuses particularly on typical evolved components from biomass samples. As proof of principle, the thermal behavior of different fossil fuels: heavy fuel oil, light fuel oil, and a crude oil, and different lignocellulosic biomass, namely, beech, birch, spruce, ash, oak, and pine as well as commercial available softwood and birch-bark pellets were investigated. The results clearly show the capability to distinguish between certain wood types through their molecular patterns and compound classes. Additionally, typical literature known pyrolysis biomass marker were confirmed by their elemental composition, such as coniferyl aldehyde (C10H10O3), sinapyl aldehyde (C11H12O4), retene (C18H18), and abietic acid (C20H30O2).

Biodegradation of crude oil and dispersants in deep seawater from the Gulf of Mexico: Insights from ultra-high resolution mass spectrometry

During the 2010 Deepwater Horizon oil spill in the Gulf of Mexico, three million liters of chemical dispersants (Corexit 9500 and 9527) were directly applied at the discharging wellhead at 1500m water depth. Such a deep-water large-scale application was unprecedented and the effect of dispersants on oil biodegradation is not yet completely understood. The present study explores the biodegradation of oil, dispersant, dispersed oil or dispersed oil and nutrients at the molecular level using ultra-high resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR–MS) following a laboratory experiment with Gulf deep water. Oil-derived molecular formulae exhibited a specific molecular fingerprint and were mainly observed in the mass range <300Da. The relative abundance of heteroatom-containing (N, S, and P) compounds decreased over time in the oil-only treatments, indicating that they may have served as nutrients when oil-derived hydrocarbons were metabolized. Relative changes over time in the molecular composition were less pronounced in the dispersed oil treatments compared to the oil-only treatments, suggesting that dispersants affected the metabolic pathways of organic matter biodegradation. In particular, dispersant addition led to an increase of S-containing organic molecular formulae, likely derived from the surfactant di-octyl sulfosuccinate (DOSS). DOSS and several dispersant-derived metabolites (with and without S) were still detectable after six weeks of incubation, underscoring that they were not rapidly biodegraded under the experimental conditions. FT-ICR–MS fragmentation studies allowed tentatively assigning structures to several of these molecules, and we propose that they are degradation products of DOSS and other dispersant components. The present study suggests preferential degradation, transformation and enrichment of distinct dispersant molecules, highlighting the need to include these compounds when tracking Corexit-derived compounds in the environment.

Investigating the potential of solid-phase extraction and Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) for the isolation and identification of dissolved metal–organic complexes from natural waters

In aquatic environments, iron and copper often occur at low concentrations, and are bound to dissolved organic matter (DOM). The detection and chemical characterization of such iron- and copper-complexes are only slowly progressing due to the high diversity of natural DOM. Recent developments of sample preparation and measurement techniques have opened up new opportunities to selectively isolate and identify metal–organic compound groups from natural water samples. In this study, the isolation of the model complex desferrioxamine–iron (DFO–Fe) and naturally occurring iron- and copper–organic complexes from a groundwater and a seawater sample was investigated with a variety of solid-phase extraction (SPE) sorbents (polar to nonpolar) and extraction/elution (low and neutral pH) setups. Natural DOM, the model complex desferrioxamine–iron (DFO–Fe), and natural Cu-binding ligands were recovered in a range of 60–100% at low pH by the majority of the sorbents. In contrast, extraction efficiencies for solid-phase extractable iron–DOM and copper–DOM compounds (SPE-Fe–DOM and SPE-Cu–DOM) were overall lower and highly influenced by pH settings, sample type, and sorbent type. Especially, the SPE techniques preferentially isolated SPE-metal–DOM with neutral/weak acidic to basic characteristics, fractions which made up a relatively small amount (~10–15%) of the total natural SPE-DOM from the two water samples. Furthermore, our data indicate that solid-phase extractable small Fe–DOM colloids and acid-stable Fe- and Cu-organic compounds occur in natural DOM. A series of desferrioxamine–copper (DFO–Cu) and desferrioxamine–iron (DFO–Fe) calibration solutions were measured by ultrahigh-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), and both complexes were detectable in positive ion mode at concentrations as low as 150nM (DFO–Cu) and 2nM (DFO–Fe). DFO–Fe and DFO–Cu in the nM range were also detectable when added to a groundwater DOM sample to evaluate matrix effects by the natural DOM background. Our study demonstrates that SPE combined with high-resolution FT-ICR-MS is currently the most promising technique to isolate and unambiguously identify dissolved metal–organic complexes in highly diverse natural water samples.

Characterization of Birch Wood Pyrolysis Oils by Ultrahigh-Resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry: Insights into Thermochemical Conversion

A laboratory-scale reactor was used to produce pyrolysis oils from Finnish silver birch hardwood (Betula pendula). The resulting wood distillates were characterized by ultrahigh-resolution (12 T) Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry coupled with negative-ion electrospray ionization (ESI). Two different pyrolysis temperatures were tested: 300 and 380 °C (the resulting oil samples were named as Oil-300 and Oil-380, respectively). The detected species were sorted on the basis of heteroatom class, carbon number, and double bond equivalent (DBE). About 1200 and 1400 unique compounds were identified from the ESI FT-ICR spectra of Oil-300 and Oil-380, respectively. These were mainly oxygen-containing compounds (Ox heteroatom classes, with x = 2–14), comprising up to 90% of all identified compounds. The compounds in the O2, O3, and O4 classes comprised of different fatty acids, hydroxy/epoxy fatty acids, and diacids. The compounds in the O5–O8 classes comprised of mainly lignin degradation products and phenolic extractives. The compounds in the O9–O14 classes comprised of both low- and high-DBE compounds. Upon increasing the temperature from 300 to 380 °C, many compounds showed an overall decrease in their DBE and carbon number. The distribution of fatty acids in Oil-300 qualitatively matches the known lipid-derived fatty acid composition of silver birch. At a higher pyrolysis temperature (380 °C), hydrogenation of unsaturated C18 fatty acids toward fully saturated compounds was observed.

Biogeochemistry of dissolved organic matter in an anoxic intertidal creek bank

Seawater circulation in permeable coastal sediments is driven by tidal changes in hydraulic gradients. The resulting submarine groundwater discharge is a source of nutrients and dissolved organic matter (DOM) to the water column. Yet, little is known about the cycling of DOM within tidal sediments, because the molecular DOM characterization remains analytically challenging. One technique that can dissect the multitude of molecules in DOM is ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). To aim at a high resolution DOM analysis we study the seasonal turnover and marine and terrestrial sources of DOM in an intertidal creek bank of the southern North Sea down to 3m depth and link the biogeochemical processes to FT-ICR-MS data and the analyses of inorganic porewater chemistry, δ13C of solid-phase extracted dissolved organic carbon (SPE-DOC), dissolved black carbon (DBC) and dissolved carbohydrates (DCHO). Increasing concentrations of dissolved Fe, Mn, P, total alkalinity, dissolved nitrogen, DOC and a concomitant decrease of sulfate along the seawater circulation path from the upper tidal flat to the tidal flat margin indicate continuous microbial activity. The relative increase of Si concentrations, unsaturated aliphatics, peptide molecular formulae and isotopically more 13C-enriched SPE-DOC towards the tidal flat margin suggests that remineralization processes mobilize DOM from buried algal (diatoms) and microbial biomass. Porewater in sediments <100cm depth contains 13C-depleted SPE-DOC and highly unsaturated compounds which are probably derived from eroded peats, suggesting rapid removal of bioavailable marine DOM such as DCHO from the water column and selective enrichment of terrestrial DOM. DBC concentrations are highest in the discharging porewater close to the tidal creek suggesting that the intertidal flat is an important DBC source to the coastal ocean. Porewater DOM accumulating at the low water line is enriched in N and S. We hypothesize that this is partly due to DOM reacting with dissolved sulfide and ammonium which may increase the refractory character of the DOM, hence making it less bioavailable for in situ active microbes.

Structural characterization of polymers by MALDI spiral-TOF mass spectrometry combined with Kendrick mass defect analysis.

High-resolution mass spectrometry (HRMS) continues to play an important role in the compositional characterization of larger organic molecules. In the field of polymer characterization, however, the application of HRMS has made only slow progress because of lower compatibility between matrix-assisted laser desorption/ionization (MALDI) and ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICRMS). In this study, a newly developed type of MALDI high-resolution time-of-flight mass spectrometry (TOFMS) with a spiral ion trajectory (MALDI spiral-TOFMS) was applied to the structural and compositional characterization of polymers. To create a graphical distribution of polymer components on a two-dimensional plot converted from complex mass spectra, we adopted a slightly modified Kendrick mass defect (KMD) analysis based on accurate masses determined using spiral-TOFMS. By setting the Kendrick mass scale based on the mass of the repeating units of a given polymer, components with common repeat units lined up in the horizontal direction on the KMD plot, whereas those components with different structures were shifted vertically. This combination of MALDI spiral-TOFMS measurement and KMD analysis enabled the successful discrimination of the polymer components in a blend of poly(alkylene oxide)s, the compositional analysis of poly(ethylene oxide)/poly(propylene oxide) block copolymers, and profiling of the end-group distribution of poly(ε-caprolactone)s synthesized under different conditions. ᅟ

Atmospheric organic matter in clouds: exact masses and molecular formula identification using ultrahigh-resolution FT-ICR mass spectrometry

Abstract. Clouds alter the composition of atmospheric aerosol by acting as a medium for interactions between gas- and particulate-phase substances. To determine the cloud water atmospheric organic matter (AOM) composition and study the cloud processing of aerosols, two samples of supercooled clouds were collected at the Storm Peak Laboratory near Steamboat Springs, Colorado (3220 m a.s.l.). Approximately 3000 molecular formulas were assigned to ultrahigh-resolution mass spectra of the samples after using a reversed-phase extraction procedure to isolate the AOM components from the cloud water. Nitrogen-containing compounds (CHNO compounds), sulfur-containing compounds (CHOS and CHNOS compounds) and other oxygen-containing compounds (CHO compounds) with molecular weights up to 700 Da were observed. Average oxygen-to-carbon ratios of ∼0.6 indicate a slightly more oxidized composition than most water-soluble organic carbon identified in aerosol studies, which may result from aqueous oxidation in the clouds. The AOM composition indicates significant influences from biogenic secondary organic aerosol (SOA) and residential wood combustion. We observed 60% of the cloud water CHO molecular formulas to be identical to SOA samples of α-pinene, β-pinene, d-limonene, and β-caryophyllene ozonolysis. CHNO compounds had the highest number frequency and relative abundances and are associated with residential wood combustion and NOx oxidation. Multiple nitrogen atoms in the assigned molecular formulas for the nighttime cloud sample composite were observed, indicating the significance of nitrate radical reactions on the AOM composition. Several CHOS and CHNOS compounds with reduced sulfur (in addition to the commonly observed oxidized sulfur-containing compounds) were also observed; however further investigation is needed to determine the origin of the reduced sulfur-containing compounds. Overall, the molecular composition determined using ultrahigh-resolution Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometry provides an unambiguous identification of the cloud water organic anion composition in the Rocky Mountain area that could help to improve the understanding of aqueous-phase processes.

Tetramethylammonium Hydroxide as a Reagent for Complex Mixture Analysis by Negative Ion Electrospray Ionization Mass Spectrometry

Ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) enables the direct characterization of complex mixtures without prior fractionation. High mass resolution can distinguish peaks separated by as little as 1.1 mDa), and high mass accuracy enables assignment of elemental compositions in mixtures that contain tens of thousands of individual components (crude oil). Negative electrospray ionization (ESI) is particularly useful for the speciation of the most acidic petroleum components that are implicated in oil production and processing problems. Here, we replace conventional ammonium hydroxide by tetramethylammonium hydroxide (TMAH, a much stronger base, with higher solubility in toluene) to more uniformly deprotonate acidic components of complex mixtures by negative ESI FTICR MS. The detailed compositional analysis of four crude oils (light to heavy, from different geographical locations) reveals that TMAH reagent accesses 1.5-6 times as many elemental compositions, spanning a much wider range of chemical classes than does NH4OH. For example, TMAH reagent produces abundant negative electrosprayed ions from less acidic and neutral species that are in low abundance or absent with NH4OH reagent. More importantly, the increased compositional coverage of TMAH-modified solvent systems maintains, or even surpasses, the compositional information for the most acidic species. The method is not limited to petroleum-derived materials and could be applied to the analysis of dissolved organic matter, coal, lipids, and other naturally occurring compositionally complex organic mixtures.

Compositional Analysis of Oil Residues by Ultrahigh-Resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

Ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry was used for compositional analysis of polar and asphaltene fractions of complex oil residues. The samples were collected before and after the processing of oil in a residue hydrocracking unit, in which the feed oil was the vacuum distillation residue of the crude oil, and the product sample was the residue collected after the processing. From the asphaltene fraction, as many as ∼26 000 peaks were detected by atmospheric pressure photoionization and more than ∼33 000 peaks by positive-ion electrospray ionization (ESI), with up to 18 distinct heteroatom classes identified. Negative-ion ESI provided complementary information through selective ionization of acidic compounds. The detected species were sorted based on heteroatom class, carbon number and aromaticity (double bond equivalence, i.e. number of rings + double bonds to carbon). The N1 class compounds were predominant in both fractions of the feed and product oils. The sulfur-containing compounds were mainly degraded or removed during the processing as expected. Vanadyl porphyrins (heteroatom class N4O1V1), detected in the asphaltene fraction of the feed oil, were not observed in the product oil fractions that is consistent with their efficient removal. Increase in the aromaticity for the most heteroatom classes was generally noticed in both polar and asphaltene fractions.