FT-ICR MS Research Articles

Polycyclic aromatics-derived benzene carboxylic acids (BPCAs) as a fast predictor of the genotoxicity of combustion particles.

Polycyclic aromatic compounds (PAC) are common toxics in combustion particles. Numerous studies on health effects of PAC mixtures focused on limited compounds. It's still challenging to quantify complex PAC mixtures in combustion particles. Recently, benzene polycarboxylic acids (BPCAs) method, which involves conversion of PAC mixtures into a few BPCAs, has been used to quantify complex PAC mixtures in particles. In this study, in vitro biossays were used to evaluate the toxicity of extractable organic matter (EOM) in combustion particles. Analysis with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) identified ~1000 molecules, mostly aromatics (84.47 ± 5.32 %), that positively associate with the EOM toxicity (p < 0.05). We further employed BPCAs method to quantify PAC mixtures in the EOM of combustion particles, and observed the toxicity (especially genotoxicity) of EOM linearly increases with the abundance of PAC mixtures (r2: 0.68-0.89, p < 0.05), as it is shown by a data set referring to all source types including biomass burning, coal combustion and vehicle exhaust. The genotoxicity of PAC mixtures in EOM of combustion particles was estimated to be 10-13 times that of benzo[a]pyrene at the same mass concentration. Target analysis of 48 PAC was carried out, but a weaker relationship is found for the toxicity of EOM and the abundance of 48 PAC. Taken together, we suggest PAC-derived BPCAs as a fast predictor of the genotoxicity of combustion particles, which could be promising in routine monitoring of PAC pollution in the air.

Evaluating the role of recalcitrant dissolved organic matter in bacterial community dynamics in urbanized freshwater ecosystems

Dissolved organic matter (DOM) and recalcitrant dissolved organic matter (RDOM) play distinct roles in shaping microbial communities. However, characterizing these roles is difficult, especially in ecosystems subjected to varying degrees of anthropogenic influence. This study investigated the molecular compositions and ecological impacts of DOM and RDOM in the Fen River, Shanxi Taiyuan, comparing pristine upstream regions with highly urbanized downstream areas. Using 16S rRNA gene sequencing and LC-MS-based metabolomics, we observed significant shifts in microbial community composition, diversity, and metabolic functions. Upstream communities, characterized by higher diversity, were dominated by Bacteroidota, Proteobacteria, and Cyanobacteria, while downstream communities, influenced by pollution, exhibited increased expression of genes related to amino acid metabolism. Fluorescence spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) revealed that upstream DOM contained higher proportions of complex, high molecular weight compounds, including significant proportions of carboxyl-rich alicyclic molecules (CRAM) and island of stability (IOS) compounds, which play key roles in long-term carbon storage and microbial carbon sequestration. In contrast, downstream DOM was characterized as having lower aromaticity and more saturated compounds, with reduced proportions of CRAM and IOS, reflecting the impact of anthropogenic activities. These findings underscored the critical roles of CRAM and IOS in regulating DOM stability and microbial communities, further highlighting the need for targeted pollution control strategies to preserve ecosystem function in urbanized water bodies.

Terrestrial dissolved organic matter inputs affect the nitrous oxide emission revealed by FT-ICR MS

Nitrous oxide (N2O) emission from lake systems could be affected via intrusion of terrestrial organic matter, causing impairment in biogeochemical cycling. The sources and mechanisms by which DOM (Dissolved organic matter) alters emissions of N2O are poorly understood. Here, we simulate different terrestrial DOM (anthropogenic sources, natural sources, and surface runoff) to assess the mechanisms affecting N2O emissions with variations of DOM. We used a combination of absorption spectroscopy, excitation-emission matrix fluorescence, and Fourier transform ion cyclotron resonance mass spectrometry to characterize DOM comprehensively. For the characterization of DOM, a combination of absorption spectroscopy, excitation-emission matrix fluorescence, and Fourier transform ion cyclotron resonance mass spectrometry was used. Microbial analysis was conducted to identify the potential microbial mechanisms. Different terrestrial DOM inputs primarily impact N2O emissions through the denitrification process (14.52 %, p < 0.05), with significant effects on the abundance of narG (12.97 %, p < 0.05) and nirK+S (10.13 %, p < 0.05). The biodegradable components in sediments directly promote N2O emissions, while in aquatic systems, the labile components (proteins, sugars, and lipids-like) were preferentially metabolized, producing reluctant derivatives. The biodegradable components (i.e., protein-like) from anthropogenic sources rapidly facilitate N2O production. Natural and surface runoff sources were the significant drivers for the continuous release and metabolism of DOM. N2O Loss emissions are negatively influenced by the regulation of carbon and nitrogen metabolism by nitrifiers and denitrifies in the sediment (p < 0.001). Metabolism of carbon and nitrogen regulated by nitrifier and denitrifies in the sediments negatively influences N2O flux (p < 0.001). N2O emissions were mainly influenced by bioavailability of inputs: DOM and varying terrestrial conditions. The results provide a theoretical base for the management of greenhouse gas emissions from lakes.

Vortex-Mixing Microfluidic Fabrication of Micafungin-Loaded Magnetite–Salicylic Acid–Silica Nanocomposite with Sustained-Release Capacity

Iron oxide nanoparticles were synthesized using a vortex microfluidic system and subsequently functionalized with a primary shell of salicylic acid, recognized for its ability to increase the stability and biocompatibility of coated materials. In the second stage, the vortex platform was placed in a magnetic field to facilitate the growth and development of a porous silica shell. The selected drug for this study was micafungin, an antifungal agent well regarded for its effectiveness in combating fungal infections and identified as a priority compound by the World Health Organization (WHO). The resulting nanocomposite system was characterized using various techniques, including Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), dynamic light scattering (DLS), Brunauer–Emmett–Teller (BET) analysis, UV-Vis spectroscopy, and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). The synthesis method produced nanoparticles with dimensions of 5–7 nm, highlighting the advantages of the chosen approach. A desorption profile was established using a continuous-flow, UV-Vis analysis system, indicating that the bioactive compound was released slowly; after two hours, approximately 50% of the loaded micafungin was detected in the release medium. Furthermore, the results obtained from the FT-ICR MS analysis provided molecular-level confirmation, thereby supporting the release mechanism of micafungin from the nanosystem.

Optical and molecular techniques are complementary to understand the characteristics of dissolved organic matter in the runoff from sloping croplands with various micro-topographies during rainfall

Dissolved organic matter (DOM) is a vital component of biogeochemical cycles in soil and aquatic ecosystems. The distribution of surface and sub-surface runoff was affected by surface micro-topographic conditions during rainfall, which results in the differences in DOM content and composition. Whereas, the connections between the optical and molecular characteristics of DOM in the runoff from different micro-topographies caused by tillage managements remains unclear. Therefore, optical spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) were combined to explore the DOM chemistry in the runoff from different runoff plots with various micro-topographies caused by four typical tillage managements (i.e. flat tillage, longitudinal tillage, contour tillage, and artificial digging tillage) in this study. The results observed a significant difference in optical and molecular parameters between surface and sub-surface runoff for the specified runoff plot, but little variations in DOM chemistry between different runoff plots with various micro-topographies for the given runoff type. These differences in the DOM content and composition of runoff were limited by the flow carrying capacity and source supplying capacity of DOM. Significant correlations between optical and molecular parameters in surface and sub-surface runoff were found by Spearman correlation analysis. Furthermore, the bipartite networks further indicated the optical and molecular datasets in sub-surface runoff showed greater consistency and correlation intensity. These correlations and some of the inconsistencies indicated that optical and molecular technologies are complementary to trace DOM chemistry. This research is of significance to further clarify the migration patterns of DOM in global soil and aquatic ecosystems, and reveal the influence of rainfall-runoff processes on the migration of biogenic elements in ecosystems.

Aeroponic approach for nondestructive root exudate collection and simulation of variable water stress trialed on cotton (Gossypium hirsutum).

Analyzing root exudates during drought poses a serious challenge; sampling root exudates in soil is destructive to roots and leads to biased molecular analysis, along with microbial decomposition and exudate sorption to soil components. Hydroponic approaches are useful to overcome these problems but lack the utility to induce drought. Nondestructive sampling techniques are thus needed to analyze root exudates from the same plants over time in combination with highly controlled variable water/nutrient stress. The proposed aeroponic approach demonstrated that cotton could be grown to maturity in the aeroponic system, then a progressive drought treatment applied while simultaneously collecting root exudates from the same plants over time. Treatments of varying irrigation rates consisted of well-watered cotton (control) that was compared to cotton given progressive water stress (drought) and subsequent drought recovery for two weeks. Plants were entering flowering as drought treatment was applied. Nondestructive morphological measurements of plant productivity were made. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was employed to analyze the molecular profile of exudates, whereas gas chromatography-mass spectroscopy (GC-MS) was used to quantify abscisic acid (ABA). Plant development was highly responsive to reduced irrigation intervals with decreased canopy height, number of green leaves, biomass, and water content. As revealed by FT-ICR MS, the complexity and connectivity of unique biochemical transformation networks in response to drought was greatest at 9 days after treatment, where severe visual symptoms were observed. Overall, the aeroponic approach is a promising technology to simulate drought while sampling root exudates nondestructively, advancing root system research and plant-stress response mechanisms.

The heterogenous molecular characteristics of biomass-pyrogenic smoke dissolved organic matters (BPS-DOMs) binding with PAHs: Novel insights from combined analysis of FT-ICR MS and fluorescence variation

Biomass-pyrogenic smoke dissolved organic matter (BPS-DOM) can co-deposit with polycyclic aromatic hydrocarbons (PAHs), thereby altering their environmental behavior and fate in surface environments. However, the heterogeneous molecular characteristics of BPS-DOM binding with PAHs remain unclear. This study systematically elucidates the binding characteristics of PAHs (phenanthrene and pyrene), with various molecular compositions in BPS-DOM, utilizing FT-ICR MS and fluorescence variation analysis. CHO compounds in BPS-DOM, characterized by high aromaticity and abundant CO bonds, significantly enhance PAHs binding by promoting π-π electron donor-acceptor interactions. In contrast, CHON compounds with higher aliphaticity inhibit pyrene binding by competing for binding sites on BPS-DOM. Furthermore, the binding sequence of different fluorescent molecules follows the order of CHO→CHOS→CHON for phenanthrene and CHO→CHON→CHOS for pyrene. This was primarily due to the larger conjugated aromatic structures of CHO compounds, which provide stronger π-π interaction sites for PAHs binding. The difference in binding sequences between phenanthrene and pyrene is primarily attributed to phenanthrene's reliance on π-π electron donor-acceptor interactions induced by -SO and -N = O, while pyrene binding depended on π-π interactions driven by larger conjugated aromatic structures. These results provide an important theoretical foundation for further understanding the molecular-level interactions between BPS-DOM and PAHs.

Lignocellulose biodegradation to humic substances in cow manure-straw composting: Characterization of dissolved organic matter and microbial community succession

Composting, a sustainable practice, facilitates the biodegradation of organic waste, notably lignocellulosic biomass, into value-added humic substances. Despite its potential, the application of electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) to characterize dissolved organic matter (DOM) for assessing the changes in maturity during cow manure-straw composting is underexplored. Furthermore, the link between these changes, microbial community succession, and the biochemical pathways of humus formation is seldom investigated. This study leveraged ESI FT-ICR MS and metagenomic analysis to elucidate the molecular changes in DOM, identified key microbes in humus formation, and traced the humus formation pathway during composting. The results highlighted the crucial role of microorganisms such as Thermobifida, Luteimonas, Ascomycota, and Chloroflexi in accelerating the breakdown and transformation of plant biopolymers. Large molecular nitrogen compounds from cow manure-straw were converted into unsaturated, aromatic oxygen compounds, which resemble humic substances in their chemical properties. The ESI FT-ICR MS data revealed that humus formation occurred through a series of reactions, including protein deamination, lignin delignification, and decarbonylation. This research offered new light on strategies to enhance the stabilization and humification of cow manure-straw composting, contributing to more effective composting processes.

Molecular characteristics of dissolved organic matter in the porewater of "Challenger" Deep sediments, Mariana Trench

Hadal trenches (&amp;gt; 6,000 m water depth) have been revealed as hotspots of organic carbon deposition and mineralization. Here, we present the molecular compositions of porewater dissolved organic matter (DOM) at the “Challenger” Deep (Site MT02; 10,954 m water depth) sediments of the Mariana Trench and the adjacent abyssal plain sediments (Site MT04; 5,800 m water depth) using ultra high-resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS). The "Challenger" Deep sediments are characterized by higher abundance of recalcitrant compounds, mainly composed of highly unsaturated compounds (79.7%) and carboxyl-rich alicyclic molecules (57.1%), compared to the abyssal plain sediments (68.3%&amp;amp;51.5%). Principal component analysis suggests that TOC content in the sediments exerts an important control on the molecular characteristics of porewater DOM. It is likely that higher TOC content triggers elevated microbial-mediated organic matter mineralization, thereby forming more refractory organic matter compounds. These results improved the knowledge of the poorly-understood DOM compositions and microbial organic matter degradation in the ultra-deep, extreme ocean environment.

Molecular insights into pilot-scale selective removal of emerging contaminants in hospital wastewater

Advanced oxidation processes (AOPs) are a promising technology for removing emerging organic contaminants (EOCs) from wastewater, while the coexisting dissolved organic matter (DOM) significantly hinders effective oxidative removal of EOCs. Understanding the effects of DOM on EOCs removal in real water matrices is crucial for designing more efficient AOPs. Herein, a pilot-scale integrated in-situ ozonation/ultrafiltration process was conducted to remove EOCs from hospital wastewater. Furthermore, the ozonation reactivity of DOM and EOCs was contrastingly analyzed at the molecular level. Our integrated process selectively removed 85 % of EOCs at a relatively low oxidant dosage of 0.44 mg O3 per mg dissolved organic carbon (DOC). Using Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS), we reveal that ozone selectivity for EOCs arose from their overall reductive characteristics of being more aromatic and unsaturated in molecular composition compared to DOM. Additionally, specific DOM compounds potentially facilitate EOCs removal. This work provides pilot-scale experience in EOCs removal from hospital wastewater and in-depth understanding of DOM’s role in the integrated process, guiding the development of effective AOPs for selective removal of emerging contaminants.

Groundwater-derived carbon stimulates headwater stream CO2 emission potential on the Qinghai-Tibet Plateau

CO2 emissions from headwater streams are a crucial component of greenhouse gas flux in inland waters. However, the influence of groundwater, a major contributor to streams in the Asian Water Tower (Qinghai-Tibet Plateau, QTP), on CO2 levels remains unclear. This study employed stable isotope analysis and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to demonstrate that groundwater-derived dissolved inorganic carbon (DIC) significantly enhanced CO2 supersaturation in the Shuiluo stream on the QTP. Specifically, the partial pressure of CO2 (pCO2), indicative of CO2 emission potential, increased more than threefold to 1,615 ± 495 μatm in groundwater-rich sites, nearly one time higher than the mean value (843 μatm) across the QTP. Groundwater-derived carbonate weathering had a significant impact of 76.6 % on the increased pCO2, whereas the degradation of highly unsaturated polyphenolics with high O/C contributed to 15.8 %. The estimated inflow of groundwater-derived DIC could reach 9.59 ± 0.34 Tg C/y in total runoff across the QTP, highlighting significant CO2 sources. This study presents new findings on the effects of groundwater-derived DIC on stream CO2 emissions in weathered regions and expands our knowledge of fluvial CO2 emissions on the QTP.

Enhanced hydrothermal liquefaction of tires using zinc and MoS2

This study introduces a novel approach for tire liquefaction employing zinc and unsupported catalyst MoS2 to mitigate oxygen, nitrogen, and sulfur content, while inhibiting poly-aromatic formation. Autoclave experiments were conducted under subcritical water conditions at 360 and 410 °C. Comprehensive characterization of char and oil was performed, encompassing elemental analysis, functional-group assessment, and composition analysis using gas chromatography-mass spectrometry (GC-MS) and Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS). During the liquefaction, zinc metal pellets react with water to form ZnO and hydrogen, aiding hydrogenation, and MoS2 preserves its catalytic stability. ZnO shows a catalytic effect on deoxygenation, desulfurization, and denitrification reactions. However, the reaction between ZnO and H2S is not favorable under hydrothermal conditions. Zinc and MoS2 synergistically promote cracking of heavier compounds into lighter ones, particularly evident at higher temperatures, without diminishing the overall oil yield. Incorporating zinc pellets and MoS2 slightly facilitates sulfur and oxygen migration from liquid to solid and gas phases. FT-ICR MS analysis reveals oxygen, sulfur, and nitrogen-containing compounds in heavy fraction of oils. The oxygen-containing compounds, predominantly comprised of stearic acid and its derivatives, are identified. Concurrently, the nitrogen-containing compounds manifest primarily as basic nitrogen compounds. MoS2 possesses the capability of forming more N-containing compounds, leading to the generation of a broader spectrum of N-containing compounds. This work elucidates the synergistic role of zinc-assisted catalysis and MoS2, offering insights into tire liquefaction mechanisms and product composition, vital for sustainable waste management and resource recovery.

Characterization of natural and anthropogenic dissolved organic matter in the yangtze river basin using FT-ICR MS

Dissolved organic matter (DOM) is a complex mixture that plays a crucial role in global carbon cycling and climate dynamics. Understanding the chemical composition of DOM is crucial for studying its biogeochemical behavior. However, identifying individual DOM molecules is challenging. Here, using ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry and an in-house database, we developed a framework to investigate DOM characteristics in natural water. Through the developed approach, we successfully identified thousands of individual DOM molecules in the water bodies of the Yangtze River Basin. For the first time, the proportions of natural and anthropogenic organics within DOM were revealed. In total, 9006 unambiguous molecular formulas were assigned to DOM in the Yangtze River Basin. The proportions of CHNO and CHOS compounds increased from upstream to downstream regions. Moreover, 1099 DOM compounds were tentatively identified, with 85 % being endogenous organics and 15 % being exogenous organics. Notably, lipids and pharmaceuticals and personal care products were the most frequently detected endogenous and exogenous compounds. The spatial variation of the identified DOM indicated anthropogenic discharges considerably increased both the number and abundance of DOM in the downstream Yangtze River Basin. This study highlighted the importance of anthropogenic impacts on DOM in water.

The substantial generation of photochemically produced reactive intermediates (PPRIs) in algae-type zones from one large shallow lake promoted the removal of organic pollutants

Photochemically produced reactive intermediates (PPRIs) are ubiquitously present in aquatic systems and hold significant importance in biogeochemical cycles. The photochemical reaction of dissolved organic matter (DOM), known as photosensitizers upon irradiation, is the main pathway for PPRIs generation. However, the PPRIs produced by algal-derived organic matter (ADOM) and their environmental effects remains elusive. This study confirmed that substantial PPRIs were generated by ADOM in the algal-derived areas. UV absorption spectra, fluorescence spectra and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) were then indicated a significant correlation between the molecular weight of DOM and the quantum yield of PPRIs, with lower molecular weight of DOM exhibiting a higher potential for PPRIs generation. Orthogonal partial least squares (OPLS) were used to build novel multivariate predictive models for indicating the PPRIs production in algae-type zone. Also, the higher concentrations of PPRIs could significantly removal different kinds of organic pollutants, such as bisphenol A (BPA), sulfadiazine (SDZ) and 17α-ethinylestradiol (EE2). Quenching experiments further elucidated that 3DOM⁎ was the key specie for pollutants degradation, serving as the precursor to generate a series of PPRIs. This study highlighted the importance of PPRIs generated from ADOM in the natural attenuation of pollutants and provided a new insight for understanding the self-purification in aquatic system.

Influence of spectral and molecular composition of dissolved organic matter on labile Cd mobility in riparian soils in the Three Gorges Reservoir, China

The periodic anti-seasonal inundation of the Three Gorges Reservoir (TGR) leads to changes in the molecular composition of dissolved organic matter (DOM) in riparian soils, further impacting the geochemical processes and ecological risk of heavy metals. However, the intrinsic driving mechanisms of DOM influencing the cadmium (Cd), a major pollutant in riparian soils in TGR, at the molecular level remain unclear. In this study, the DOM molecular composition, labile Cd in riparian soils and the key driving mechanism before and after flooding were explored using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), the diffusive gradients in thin films (DGT) and partial least squares path modeling (PLS-PM). A spectral analysis revealed that after flooding, the relative abundance of terrestrial humic-like substances decreased whereas that of microbial humic-like substances increased. Furthermore, FT-ICR MS analysis revealed that the relative abundance of lignin, the main molecular components of DOM in riparian soils, increased after flooding. The linkage of DOM with the concentration and kinetic processes of labile Cd indicated that the higher aromaticity and unsaturation, larger molecular weight, and higher humification level of DOM promoted the mobility of labile Cd from the soil solid phase to the liquid phase. In particular, our findings indicated that at the molecular level, the most significant factor influencing the mobility of labile Cd was lignin, which was primarily governed by the complexation of lignin with labile Cd. The complexation mechanism between lignin and labile Cd resulted in increased ecotoxicological risk of labile Cd after flooding, while the overall ecotoxicological risk was low in riparian soils in TGR. This study provides better insight into the geochemical cycling and fate of toxic elements in reservoir ecosystems under the change of hydrological regime.

Oil–reservoir correlation: Unravelling the producing reservoir for the sulfur-rich Qianjiang shale oil play

The hypersaline Qianjiang shale oil play represents a promising yet challenging target for exploration due to its multiple stacked shale-carbonate layers, which complicate the identification of the most viable extraction sites. Additionally, the oil accumulated in these layers is immature to low-mature and considerably high in sulphur content. To trace the shale zones after fracturing, a newly developed oil-reservoir correlation method employing Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was utilised. This method proved effective in distinguishing between the acidic nitrogen-, sulphur-, and oxygen-containing (NSO) compounds identified by the negative mode of electrospray ionisation FT-ICR MS and the less polar NSO compounds and aromatic hydrocarbons detected by positive ion atmospheric pressure photoionisation FT-ICR MS. These compounds facilitated the deconvolution of oils produced from mixed layers in the hypersaline Qianjiang shale play. The zones of oil production identified through this method corresponded well with shale reservoirs previously characterised by anomalously high oil saturation index values (OSI >400 mg/g TOC) and a preferential enrichment of saturated hydrocarbons. A detailed analysis of C31-35 homohopane distributions in shale extracts and crude oil corroborated these findings. The variability in the producibility of NSO compounds and aromatic hydrocarbons was examined based on functional group, degree of aromatisation, and molecular weight. During production, sulphur- and nitrogen-containing compounds predominantly migrated into the produced oil, whereas oxygen-containing compounds were less affected. Nonetheless, determining the production partitioning of aromatic hydrocarbons remains challenging; if present, it may be obscured by the commingled production effects from multiple layers.

Thermal Reactivity of Bio-Oil Produced from Catalytic Fast Pyrolysis of Biomass.

Catalytic fast pyrolysis (CFP) of biomass is a versatile thermochemical process for producing a biogenic oil that can be further upgraded to sustainable transportation fuels, chemicals, and materials. CFP oil exhibits reduced oxygen content and improved thermal stability compared to noncatalytic fast pyrolysis oil. However, some level of reactive oxygenates remain in CFP oils, and reactions between these species can result in molecular weight growth and increased viscosity, leading to the potential for challenges during transportation, storage, and downstream processing. Previous research has provided considerable insight into the reactivity of noncatalytic fast pyrolysis oils, but CFP oils have yet to be studied in a similar fashion. Consequently, the degree of catalytic upgrading that is necessary to effectively stabilize CFP oils has yet to be established, and little is known about the mechanistic details underlying the process. The current study addresses this knowledge gap by controlling the CFP reaction conditions to systematically vary the oxygen content of the resulting oil. Accelerated thermal reactivity studies were then performed, and the CFP oils were analyzed using gas chromatography-mass spectrometry (GC-MS), Fourier transform ion cyclotron mass spectrometry (FT-ICR MS), gel permeation chromatography (GPC), and viscometry to evaluate the impact of heating on their physical and chemical properties. The results revealed that short chain carbonyls, anhydrosugars, and lignin derivatives with conjugated vinyl groups likely play a role in the thermal reactivity of CFP oils. Additionally, experiments performed across a wide variety of feedstocks revealed relatively low thermal reactivity for CFP oils with oxygen contents of <20 wt %. However, above this threshold value, the thermal reactivity grew exponentially as a function of oxygen content, resulting in large increases in viscosity and molecular weight. These results serve to deepen the mechanistic understanding of CFP oil thermal reactivity and help inform the development of quality specifications for catalytic upgrading to effectively stabilize CFP oils.

Effects of pyrolysis temperature on the photooxidation of water-soluble fraction of wheat straw biochar based on 21 ​T FT-ICR mass spectrometry

Biochar, formed through the pyrolysis or burning of organic wastes, has a complex chemical composition influenced by feedstock, pyrolysis temperature, and reaction conditions. Water-soluble, dissolved black carbon species released from biochar comprise one of the most photoreactive organic matter fractions. Photodegradation of these water-soluble species from wheat straw biochar, produced at different pyrolysis temperatures in laboratory microcosms, resulted in noticeable compositional differences. This study characterized water-soluble transformation products formed through the photodegradation of wheat straw biochar pyrolyzed at 300, 400, 500, or 600°C by electrospray ionization 21 ​T Fourier transform ion cyclotron resonance mass spectrometry (21T FT-ICR MS). We also evaluated global trends in the toxicity of these water-soluble fractions using MicroTox™ to assess the impacts of pyrolysis temperature. Additionally, we examined biochar surface morphology after photodegradation and observed minimal change after irradiation for 48 ​h, though the total yield of water-soluble biochar species varied with pyrolysis temperature. Trends in toxicity observed from MicroTox® analysis reveal that water-soluble photoproducts from biochar produced at 300°C and 900°C are nearly three times as toxic compared to dark controls. The ultrahigh resolving power of 21T FT-ICR MS allows for the separation of tens of thousands of highly oxidized, low-molecular-weight (<1 ​kDa) species, showing that photoproducts span a wider range of H/C and O/C ratios compared to their dark analogs. This study highlights the impacts of photodegradation on the molecular composition of water-soluble biochar species and underscores the influence of pyrolysis temperature on the quantity and composition of dissolved organic species.

Annotation of DOM metabolomes with an ultrahigh resolution mass spectrometry molecular formula library

Increased accessibility of liquid chromatography mass spectrometry (LC-MS) metabolomics instrumentation and software have expanded their use in studies of dissolved organic matter (DOM) and exometabolites released by microbes. Current strategies to annotate metabolomes generally rely on matching tandem MS/MS spectra to databases of authentic standards. However, spectral matching approaches typically have low annotation rates for DOM. An alternative approach is to annotate molecular formula based on accurate mass and isotopic fine structure measurements that can be obtained from state-of-the-art ultrahigh resolution Fourier Transform Ion Cyclotron Resonance mass spectrometry (FT-ICR MS), but instrument accessibility for large metabolomic studies is generally limited. Here, we describe a strategy to annotate exometabolomes obtained from lower resolution LC-MS systems by matching metabolomic features to a molecular formula library generated for a representative sample analyzed by LC 21T- FT-ICR MS. The molecular formula library approach successfully annotated 53% of exometabolome features of the marine diatom Phaeodactylum tricornutum – a nearly ten-fold increase over the 6% annotation rate achieved using a conventional MS/MS approach. There was 94% agreement between assigned formula that were annotated with both approaches, and mass error analysis of the discrepancies suggested that the FT-ICR MS formula assignments were more reliable. Differences in the exometabolome of P. tricornutum grown under iron replete and iron limited conditions revealed 668 significant metabolites, including a suite of peptide-like molecules released by P. tricornutum in response to iron deficiency. These findings demonstrate the utility of FT-ICR MS formula libraries for extending the accuracy and comprehensiveness of metabolome annotations.

Comprehensive Molecular Characterization of Organic Compounds in Petroleum-Contaminated Soils from the Changqing Oilfield by FT-ICR MS and GC-MS

Comprehensive Molecular Characterization of Organic Compounds in Petroleum-Contaminated Soils from the Changqing Oilfield by FT-ICR MS and GC-MS