FT-ICR MS Analysis Research Articles

Fourier-transform ion cyclotron resonance mass spectrometry for characterizing proteoforms.

Proteoforms contribute functional diversity to the proteome and aberrant proteoforms levels have been implicated in biological dysfunction and disease. Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS), with its ultrahigh mass-resolving power, mass accuracy, and versatile tandem MS capabilities, has empowered top-down, middle-down, and native MS-based approaches for characterizing proteoforms and their complexes in biological systems. Herein, we review the features which make FT-ICR MS uniquely suited for measuring proteoform mass with ultrahigh resolution and mass accuracy; obtaining in-depth proteoform sequence coverage with expansive tandem MS capabilities; and unambiguously identifying and localizing post-translational and noncovalent modifications. We highlight examples from our body of work in which we have quantified and comprehensively characterized proteoforms from cardiac and skeletal muscle to better understand conditions such as chronic heart failure, acute myocardial infarction, and sarcopenia. Structural characterization of monoclonal antibodies and their proteoforms by FT-ICR MS and emerging applications, such as native top-down FT-ICR MS and high-throughput top-down FT-ICR MS-based proteomics at 21 T, are also covered. Historically, the information gleaned from FT-ICR MS analyses have helped provide biological insights. We predict FT-ICR MS will continue to enable the study of proteoforms of increasing size from increasingly complex endogenous mixtures and facilitate the benchmarking of sensitive and specific assays for clinical diagnostics. © 2020 John Wiley & Sons Ltd. Mass Spec Rev.

Refinement of Compound Aromaticity in Complex Organic Mixtures by Stable Isotope Label Assisted Ultrahigh-Resolution Mass Spectrometry

Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) provides a unique opportunity for molecular analysis of natural complex mixtures. In many geochemical and environmental studies structure-propertry relations are based solely on the elemental compositional information. Several calculated parameters were proposed to increase reliability of structural attribution, among which aromaticity indices (AI and AImod) are widely used. Herein, we applied a combination of selective labeling reactions in order to obtain direct structural information on the individual components of lignin-derived polyphenolic material. Carboxylic (COOH), carbonyl (C═O), and hydroxyl (OH) groups were enumerated by esterification, reducing, and acetylation reactions, respectively, followed by FTICR MS analyses. Obtained information was enabled to constrain aromaticity accounting for the carbon skeleton only. We found that actual aromaticity of components may be both higher or lower than approximated values depending on the abundance of COOH, C═O, and OH groups. The results are of importance for the geochemical community studying terrestrial NOM with structural gradients.

Contributions to Lignomics: Stochastic Generation of Oligomeric Lignin Structures for Interpretation of MALDI-FT-ICR-MS Results.

The lack of standards to identify oligomeric molecules is a challenge for the analysis of complex organic mixtures. High-resolution mass spectrometry-specifically, Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS)-offers new opportunities for analysis of oligomers with the assignment of formulae (Cx Hy Oz ) to detected peaks. However, matching a specific structure to a given formula remains a challenge due to the inability of FT-ICR MS to distinguish between isomers. Additional separation techniques and other analyses (e.g., NMR spectroscopy) coupled with comparison of results to those from pure compounds is one route for assignment of MS peaks. Unfortunately, this strategy may be impractical for complete analysis of complex, heterogeneous samples. In this study we use computational stochastic generation of lignin oligomers to generate a molecular library for supporting the assignment of potential candidate structures to compounds detected during FT-ICR MS analysis. This approach may also be feasible for other macromolecules beyond lignin.

Engineering of melanin biopolymer by co-expression of MelC tyrosinase with CYP102G4 monooxygenase: Structural composition understanding by 15 tesla FT-ICR MS analysis

In this study, a novel melanin pigment was synthesized by Escherichia coli cells co-expressing tyrosinase (MelC) and cytochrome P450 monooxygenase (CYP102G4) enzymes simultaneously. The CYP102G4 catalyzes indole C3-specific hydroxylation and generates 3-hydroxyindole (indoxyl) and 3-oxoindole. Additional supply of indole derivatives leads to much darker melanin pigmentation with higher yields (3.4 g/L) of synthesized CYP-Melanin, which showed interesting morphological and electrochemical properties. To understand the correlation between its chemical structure and functions, FT-IRand SEM analysis were attempted. Following 15 T FT-ICR mass spectrometry analysis provided information on the chemical and molecular compositions, characteristics of the synthetic melanins, evidence of higher nitrogen content, and higher degree of unsaturation in the CYP-Melanin structure. Besides, electrical conductivity of CYP-Melanin was determined by cyclic voltammetry (CV) analysis to investigate the feasibility for the application of CYP-Melanin as electrical materials.

Spectroscopic and molecular-level characteristics of dissolved organic matter in the Pearl River Estuary, South China

Coastal populations are expanding globally, resulting in great anthropogenic impacts on the organic matter in estuaries and regional carbon cycles. However, the molecular-level characteristics of dissolved organic matter (DOM) within highly disturbed estuaries are still not well understood. Here, water samples collected during two seasons (wet and dry) from the subtropical Pearl River Estuary of China were analyzed using absorption and fluorescence spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to determine the spatiotemporal variations in the DOM characteristics. In the seaward direction, the abundances of chromophoric and fluorescent DOM decreased by greater percentages than the bulk dissolved organic carbon concentration. The spectroscopy and FT-ICR MS analyses collectively indicated seaward declines in the aromaticity of DOM and terrestrial DOM contributions from natural terrestrial markers and anthropogenic synthetic surfactants. In particular, the S content in DOM was much higher here than in previously reported estuaries, suggesting a strong anthropogenic impact on the estuarine DOM. Greater terrestrial and anthropogenic signatures in DOM were observed in the wet season than in the dry season. Importantly, this study implies that the terrestrial and anthropogenic contributions to DOM were strongly driven by season in the anthropogenically disturbed subtropical estuary.

Multimodal, in Situ Imaging of Ex Vivo Human Skin Reveals Decrease of Cholesterol Sulfate in the Neoepithelium during Acute Wound Healing.

Skin repair is a significant aspect of human health. While the makeup of healthy stratum corneum and epidermis is generally understood, the mobilization of molecular components during skin repair remains largely unknown. In the present work, we utilize multimodal, in situ, mass spectrometry, and immunofluorescence imaging for the characterization of newly formed epidermis, following an initial acute wound for the first 96 h of epithelization. In particular, TOF-SIMS and confirmatory MALDI FT-ICR MS (/MS) analysis permitted the mapping of several lipid classes, including phospholipids, neutral lipids, cholesterol, ceramides, and free fatty acids. Endogenous lipid species were localized in discrete epidermal skin layers, including the stratum corneum (SC), stratum granulosum (SG), stratum basale (SB), and dermis. Experiments revealed that healthy re-epithelializing skin is characterized by diminished cholesterol sulfate signal along the stratum corneum toward the migrating epithelial tongue. The spatial distribution and relative abundances of cholesterol sulfate are reported and correlated with the healing time. The multimodal imaging approach enabled in situ high-confidence chemical mapping based on accurate mass and fragmentation pattern of molecular components. The use of postanalysis immunofluorescence imaging from the same tissue confirmed the localization of endogenous lipid species and Filaggrin and Cav-1 proteins at high spatial resolution (approximately a few microns).

Insights from Nitrogen Compounds in Gas Oils Highlighted by High-Resolution Fourier Transform Mass Spectrometry

Twenty-three gas oil samples from different origins were analyzed in positive and negative ion modes by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI(±)-FT-ICR MS). Sample ionization and ion transfer conditions were first optimized using Design of Experiment approach. Advanced characterization of basic and neutral nitrogen compounds in these samples was then performed through ESI(±)-FT-ICR MS analysis. A good repeatability was observed from the analysis of six replicates for each gas oil sample. Significant differences in molecular composition were spotted between the gas oils, either considering identified heteroatomic classes or within nitrogen families and were later correlated to samples macroscopic properties. The evolution of nitrogen relative intensities for one feed and two corresponding effluents has also been studied to monitor hydrotreatment reaction pathways toward aromaticity and alkylation levels evolutions.

Profiling Murchison Soluble Organic Matter for New Organic Compounds with APPI- and ESI-FT-ICR MS.

The investigation of the abundant organic matter in primitive meteorite such as carbonaceous chondrites is of major interest in the field of origin of life. In this study, the soluble organic fraction of the Murchison meteorite was analyzed by atmospheric pressure photoionization (APPI) and electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), in both detection modes. Such an approach ensured that we obtained an extensive description of the organic matter of the CM2 meteorite. Indeed, while in total close to 16,000 unique features were assigned, only 4% are common to all analyses, illustrating the complementarity of both the detection modes and the ionization sources. ESI FT-ICR MS analysis, in negative-ion mode, ensured to observe specifically CHOS and CHNOS species, whereas the positive-ion mode is more dedicated to the detection of CHNO and CHN species. Moreover, new organomagnesium components were observed in (+) ESI. Eventually, (+) APPI FT-ICR MS analysis was a preferred method for the detection of less polar or nonpolar species such as polycyclic aromatic hydrocarbons but also heteroatom aromatic species composing the organic matter of Murchison.

Application of Online Liquid Chromatography 7 T FT-ICR Mass Spectrometer Equipped with Quadrupolar Detection for Analysis of Natural Organic Matter

In this study, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), combined with quadrupolar detection (QPD), was applied for online liquid chromatography (LC) MS analysis of natural organic matter (NOM). Although FT-ICR MS has emerged as an important analytical technique to study NOM, there are few previous reports on online LC FT-ICR MS analysis of NOM due to the long acquisition time (2-8 s) required to obtain high-resolution mass spectra. The QPD technique provides a critical advantage over the conventional dipolar detection (DPD) technique for LC-MS analysis because a spectrum with the same resolving power can be obtained in approximately half the acquisition time. QPD FT-ICR MS provides resolving powers ( ) of ∼300000 and 170000 at m/ z 400 with acquisition times per scan of 1.2 and 0.8 s, respectively. The reduced acquisition time per scan allows increased number of acquisitions in a given LC analysis time, resulting in improved signal to noise ( S/ N) ratio and dynamic range in comparison to conventional methods. For example, 40% and 100% increases in the number of detected peaks were obtained with LC QPD FT-ICR MS, in comparison to conventional LC DPD FT-ICR MS and direct-injection FT-ICR MS. It is also possible to perform more quantitative comparison and molecular level investigation of NOMs with 2 μg of a NOM sample. The data presented herein demonstrate a proof of principle that QPD combined with LC FT-ICR MS is a sensitive analytical technique that can provide comprehensive information about NOM.

Optical and Molecular Signatures of Dissolved Organic Matter Reflect Anthropogenic Influence in a Coastal River, Northeast China.

Sources and molecular composition of dissolved organic matter (DOM) in coastal rivers have been tightly linked with its reactivity and fate, thus influencing element and nutrient cycling. The DOM in coastal rivers is usually sourced from both terrestrial and marine inputs, with further complication by anthropogenic activities, which is less understood in coastal rivers located near populated industrial regions. In this study, DOM in a typical anthropogenically influenced coastal river, Daliao River, was analyzed for optical analyses and for molecular composition via Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to give a better scope of composition and sources of DOM. The DOM was enriched in autochthonous and anthropogenic inputs at upstream sites according to high chlorophyll a concentrations, strong protein-like fluorescence, and nonoxygen heteroatomic CHOS formulae (19-24% by relative peak intensity) detected by FT-ICR MS analysis. A series of surfactant-like formulae, indicative of wastewater inputs, were identified and showed a decreasing trend from upstream to the river mouth. Compared with large world rivers, the DOM of Daliao River is characterized by higher abundances of heteroatomic (excluding O) formulae and molecular lability, which is likely caused by strong autochthonous and anthropogenic inputs. In general, we demonstrate that in addition to optical properties, the molecular composition can assess the specific anthropogenic imprints and molecular lability of DOM, which is essential for constraining sources and identifying processes during the transit of DOM from the river to estuary with increasing urbanization and industrialization.

Structural investigation of coal humic substances by selective isotopic exchange and high-resolution mass spectrometry.

Here, we report the application of a selective liquid-phase hydrogen/deuterium exchange (HDX) coupled to ultra-high resolution FTICR MS for structural investigations of individual constituents of humic substances (HS) isolated from three coal samples of different geographical origin. Selectivity was achieved by conducting reactions in DCl or NaOD solutions for catalyzing HDX in aromatic ring and side-chain positions with enhanced C-H acidity, respectively. FTICR MS analysis showed a significant overlap of molecular compositions in the HS samples under study, with 2000 common formulae. Using HDX, we demonstrated that the determined common formulae are presented by different structural isomers. We found that aromatic compounds varied both in the substitution pattern and the number of aromatic protons. Depending on the sample, lignin components with the same molecular formulae were composed of coumaryl, coniferyl or sinapyl moieties. Enumeration of HDX series for the 800 most abundant compounds showed that the results of HDX agreed well with the model structures suggested for humic components occupying a van Krevelen plot. In addition, we explored chemical transformations, which could connect individual constituents of coal HS. These transformations included hydrolysis of a guaiacyl moiety and reduction of a catechol unit, which corresponds to the conversion of a coniferyl fragment into a coumaryl unit. The obtained results were supportive of the hypothesis of the reducing humification pathway suggested for lignin transformation in the environment. The conclusion was made that the molecular ensemble of coal HS is composed of individual constituents produced at different humification stages.

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.

Chemometric Unmixing of Petroleum Mixtures by Negative Ion ESI FT-ICR MS Analysis.

Identification and quantification of mixed sources of petroleum reservoirs as well as the sources of oil spills generally requires the molecular composition information about the mixture. In this study, the relative concentrations of a series of polar acidic compounds, semiquantified by negative ion ESI FT-ICR MS, were calculated using alternating least-squares (ALS) to unmix a group of oil mixtures prepared in the laboratory using three endmember oils. It was shown that the ALS results were accurate based on the relative concentrations of polar acidic compounds, regardless of whether endmember oils and several samples were removed from the sample set. ALS was able to accurately calculate the composition of endmember oils, regardless of whether they were included in the sample set. This method is relatively simple, efficient, time-saving, and has potential for geological source identification of mixed oils or oil spills.

Combined characterization using HT-GC × GC-FID and FT-ICR MS: A pyrolysis fuel oil case study

In this work the composition of a hydrotreated distilled crude oil fraction (HTAL-FEED) and its heaviest steam cracking product fraction, the so-called pyrolysis fuel oil (HTAL-PFO), have been characterized in detail using high-temperature comprehensive two-dimensional gas chromatography (HT-GC × GC) coupled to a flame ionization detector (FID) and Fourier Transform-Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS). Moreover, the HTAL-FEED and HTAL-PFO were characterized using elemental analysis and SARA fractionation to determine their bulk properties. Although the main compounds are saturates, the HTAL-FEED contains significant amounts of aromatic compounds, primarily mono- and di-aromatics but even up to penta-aromatics, which are responsible for the growth of large polycyclic aromatic hydrocarbons (PAH) formed during steam cracking that almost entirely make up the HTAL-PFO product. Quantitative results are obtained based on the HT-GC × GC-FID chromatograms and the use of well-chosen internal standards, allowing ~90 wt% of the feedstock and ~60 wt% of HTAL-PFO to be quantified. FT-ICR MS analyses confirmed the presence of molecules heavier than penta-aromatics in the HTAL-FEED, as well as the very heavy character of HTAL-PFO consisting of highly condensed aromatic molecules with up to 16 fused aromatic rings. The analytical methodology can be applied to other steam cracking products, providing a near-molecular level insight into conversion and coke formation precursors during steam cracking of wide boiling range hydrocarbons.

Geochemical characteristics and significance of heteroatom compounds in lacustrine oils of the Dongpu Depression (Bohai Bay Basin, China) by negative-ion Fourier transform ion cyclotron resonance mass spectrometry

Abstract Saline and freshwater lacustrine oils from the Dongpu Depression (Bohai Bay Basin) were characterized by negative-ion electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). ESI-FT-ICR MS detected a large range of nitrogen and oxygen compounds in the oils, mostly comprising N1, O1, O2 and N1O1 species. The low mature oils are dominated by O1 species with double bond equivalent of 4 (DBE = 4; mainly alkylphenols), O2 species with DBE = 5–6 (i.e., hopanoid, secohopanoic and steroid acids) and DBE = 1 (i.e., fatty acids), indicating a genetic relationship between oxygen compounds and their precursors. The nitrogen and oxygen compounds were significantly influenced by maturity, with the lower maturity oils analyzed enriched in O2 species, particularly fatty acids and 4–5 ring naphthenes with biologically sourced hydrocarbon skeletons: ratios of O2/N1 > 0.7; C20–30/C15–45-DBE1-O2 > 0.4; and DBE5–6/DBE12–22-O2 > 6.0 may be useful indicators of low maturity. With increasing maturity, the condensation degree of the compounds increased and the carbon number decreased. The relative abundances of N1 and O1 species with the following specific DBE carbon number ranges were particularly sensitive to maturity: DBE9–12/DBE15–18-N1, C20–28/C29–40-DBE12-N1, C20–30/C31–50-DBE15-N1, DBE9–12/DBE4–20-O1 and C20–30/C31–50-DBE8-O1. In some instances the FT-ICR MS proxies provided a more reliable indication of high maturity levels than traditional sterane based maturity parameters. However, several of these species were also responsive to other influences, namely C20–28/C29–40-DBE12-N1 and C20–30/C31–50-DBE15-N1 ratios reflected an organofacies control and DBE9–12/DBE4–20-O1 and C20–30/C31–50-DBE8-O1 ratios changed with thermochemical sulfate reduction (TSR)– confirmed by δ34S variances of OSCs. In light of the multiple controls on the nitrogen and oxygen compounds, DBE9–12/DBE15–18-N1 ratio seems unaffected by organofacies or TSR and was considered the most reliable maturity proxy displaying a similar or better maturity relationship than Ts/(Ts + Tm). Aside from secondary alteration effects, the freshwater samples showed several compositional differences to the saline samples, albeit from a limited data set, including generally higher O2 and N1 (particularly low MW) product abundances, lower abundances and quite different distribution of O1 products. These distinctions suggest ESI FT-ICR MS analysis has potential for distinguishing these sample types.

Identifying labile DOM components in a coastal ocean through depleted bacterial transcripts and chemical signals.

Understanding which compounds comprising the complex and dynamic marine dissolved organic matter (DOM) pool are important in supporting heterotrophic bacterial production remains a major challenge. We eliminated sources of labile phytoplankton products, advected terrestrial material and photodegradation products to coastal microbial communities by enclosing water samples in situ for 24 h in the dark. Bacterial genes for which expression decreased between the beginning and end of the incubation and chemical formulae that were depleted over this same time frame were used as indicators of bioavailable compounds, an approach that avoids augmenting or modifying the natural DOM pool. Transport- and metabolism-related genes whose relative expression decreased implicated osmolytes, carboxylic acids, fatty acids, sugars and organic sulfur compounds as candidate bioreactive molecules. FT-ICR MS analysis of depleted molecular formulae implicated functional groups ~ 30-40 Da in size cleaved from semi-polar components of DOM as bioreactive components. Both gene expression and FT-ICR MS analyses indicated higher lability of compounds with sulfur and nitrogen heteroatoms. Untargeted methodologies able to integrate biological and chemical perspectives can be effective strategies for characterizing the labile microbial metabolites participating in carbon flux.

Induction of NAD (P)H: Quinone reductase 1 (QR1) and antioxidant activities in vitro of 'Toranja Burarama' (Citrus maxima [Burm.] Merr.).

Toranja 'Burarama', Citrus maxima (Burm.) Merr. (Citrus grandis), is a new citrus discovered in the State of Espírito Santo, Brazil. As several varieties of citrus are known to possess antioxidant and cancer chemopreventive properties, the aim of the study was to evaluate in vitro if this Toranja possess these properties. The antioxidant activity, the potential to induce quinone reductase 1, and the influence on cell viability were measured. ESI(-)FT-ICR MS analysis was also performed and identified flavonoids, coumarins, and fatty acids in the extract. The ethyl acetate and methanolic extracts of the peels presented the highest antioxidant activity in vitro by DPPH (IC50 =298.3±2.6μg/ml and 303.8±0.4μg/ml), ABTS assay (IC50 =298.2±6.4μg/ml and 296.4±2.5μg/ml), and FRAP (IC50 =234.6±1.8μg/ml and 398.1±3.8μg/ml). The ethyl acetate extract of the peel induced quinone reductase 1 activity in Hepa1c1c7 cells, indicating that C.maxima exhibited cancer chemopreventive properties.

Assessment of Hydrotreatment for Hydrothermal Liquefaction Biocrudes from Sewage Sludge, Microalgae, and Pine Feedstocks

Bulk property measurement, simulated distillation, gas chromatography mass spectrometry (GC-MS), and ultra-high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) are utilized for direct description and comparison of the chemical composition of raw and hydrotreated biocrude samples from pine, microalgae (Chlorella sp.), and sewage sludge. With hydrotreatment, the nitrogen, oxygen, and sulfur content as well as viscosity, density, and moisture content of all biocrudes decreased to yield a more desirable product. For upgraded biocrudes, simulated distillation and GC-MS data reveal that the microalgae and sewage sludge products comprise a high proportion of n-alkanes, which distill between 260 and 350 °C, whereas the pine hydrotreated biocrude product has a lower concentration of n-alkanes and is more compositionally diverse with an abundance of saturated cyclic compounds. FT-ICR MS analysis of the raw biocrudes showed predominantly Ox species, whereas raw microalgae and sewag...

Patterns of change in permanganate oxidizable soil organic matter from semiarid drylands reflected by absorbance spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry

Organic matter (OM) oxidized by slightly alkaline KMnO4, termed permanganate-oxidizable carbon (POXC), has recently emerged as a standardized indicator of active, labile carbon within soil quality frameworks. Yet, qualitative information on POXC, particularly in semiarid drylands, is very scarce. The aim of this study was to characterize POXC within three long-term field experiments in Montana, USA: (i) across a wide range of edaphic (e.g., % clay) and management conditions (e.g., cropping intensity) (n = 148); and (ii) to identify the molecular composition of soil OM before and after KMnO4 treatment using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS). The content of POXC was significantly greater under perennial (382–685 mg/kg) or annual cropping (404–607 mg/kg) than fallow-wheat (359–543 mg/kg) systems. Soil OM changes, however, were equally or better expressed when considering soil organic carbon (SOC) concentration. The occurrence of POXC paralleled SOC (R = 0.87; P < 0.001) and total nitrogen (TN) (R = 0.82; P < 0.001) concentrations, regardless of soil textural differences. The ESI FT-ICR MS analyses of aqueous soil extracts indicated that the KMnO4 reaction oxidized dissolved OM of diverse molecular character. OM molecular composition after KMnO4 treatment was enriched by strongly reduced chemical constituents (O/C < 0.4) at greater condensed aromaticity (AI > 0.67) and hydrogen saturation (aliphatic composition; H/C > 1.5) across all heterogeneous groups (CcHhNnOoSs). Although POXC is a rapid assay widely used for characterizing soil OM dynamics, it may not provide a clear advantage over SOC concentration in semiarid drylands. The view of POXC as a merely labile, simple biodegradable OM fraction needs to be reconsidered.

Abiotic formation of organoiodine compounds by manganese dioxide induced iodination of dissolved organic matter.

Iodination of dissolved organic matter (DOM) initiated by manganese oxide may represent an important source of organoiodine compounds (OICs) for iodide-containing waters. Here, Suwannee River natural organic matter was selected as model DOM, the OICs formation in simulated freshwater samples from iodinated DOM induced by manganese oxide (δ-MnO2) was investigated at different pHs and concentrations of iodide and δ-MnO2 by using negative ion electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR MS). While no OIC was observed in DOM control samples without δ-MnO2, hundreds of OICs were detected in the presence of δ-MnO2, suggesting the enhanced role of δ-MnO2 played in DOM iodination. The relative abundance was defined as the value of dividing the peak intensity of OICs by the highest m/z peak intensity constantly occurred in each mass spectrum, and selected as a parameter for partly reflecting the real level of OICs. The relative abundance of most OICs were around or greater than 1%, and several OICs with higher relative abundance were identified as diiodo-5-hydroxy-4-cyclopentene-1,3-dione, diiodomethane and diiodoacetic acid. The numbers of the formed OICs increased with the increase concentrations of iodide/δ-MnO2 and the decrease of pH, and nearly all OICs formed at lower levels of iodide/δ-MnO2 and/or higher pH were overlapped by that at higher levels of iodide/δ-MnO2 and/or lower pH, indicating the reliability of FT-ICR MS analysis techniques and data processing method. The OICs were formed mainly from the iodination of typical lignin-like and tannin-like compounds, as well as the precursor compounds with higher relative abundance through substitution reactions. Our findings demonstrate that the OICs formation by δ-MnO2-initiated DOM iodination should receive more attention and the concentration, exact structure and toxicity of the OICs need to be further investigated.