Fourier Transform Ion Cyclotron Resonance Research Articles

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

Hadal trenches (> 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%&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.

Deciphering Isotopic Fine Structures of Silylated Compounds in Gas Chromatography-Vacuum Photoionization Orbitrap Mass Spectrometry of Bio-Oils.

We introduce vacuum resonance-enhanced multiphoton ionization (REMPI) with high-resolution Orbitrap Fourier transform mass spectrometry (FTMS) for analyzing silylated polar compounds. UV laser radiation at 248 nm sensitively and selectively targets aromatic constituents, while high-resolution mass spectrometry (HRMS) enables high-performance mass spectrometric detection. This workflow enhances the detection confidence of polar constituents by identifying unique isotopologue patterns, including at the isotopic fine structure (IFS) level, in analytical standards and complex bio-oils. A direct and derivatized gas chromatography (GC) procedure on a polar standard component mixture allowed us to explore the general ionization and detection characteristics of REMPI FTMS. HRMS enabled the examination of the complex isotopologue profiles, revealing distinct patterns for the CHOxSiy-class compounds. Particularly in complex mixtures, this isobaric/isonucleonic complexity exceeded the classical mass resolution capabilities of the employed Orbitrap D30 series and prompted the usage of prolonged transients via an external data acquisition system. This procedure substantially improved mass spectrometric results by recording the unreduced time-domain transient data for up to 2 s. Notably, the ability to distinguish diagnostic isotopic pairs, such as 12C/29Si vs 13C/28Si with a mass split of ∼3.79 mDa and 13C12C/28Si29Si vs 13C2/28Si2, with an approximate mass difference of ∼3.32 mDa, demonstrates a significant and expected performance improvement. Finally, we benchmark the GC HRMS methodology to identify silylated oxygenated and nitrogen-containing constituents in ultracomplex bio-oil samples. The presented approach of utilizing the silicon isotope pattern and unique isotopologue mass splits for increasing attribution confidence can be applied beyond bio-oils toward the general GC analyses of polar oxygenates.

Unravelling the structure of one-electron oxidation products of model peptide backbones containing methionine by IRMPD spectroscopy: the effect of the neighbouring groups.

A series of Methionine (Met) derivatives, where either the amino group and/or the carboxylic acid group is blocked by acetyl and/or methyl ester functionalities, has been investigated by Collision Induced Dissociation-tandem mass spectrometry (CID-MS2) and Infrared Multiple Photon Dissociation (IRMPD) spectroscopy. The CID-MS2 experiments were performed using a Fourier-transform ion-cyclotron-resonance (FT-ICR) mass spectrometer equipped with an electrospray ionization (ESI) source. The IRMPD spectra were recorded employing a Paul type ion-trap coupled with the free-electron laser (FEL) FELIX in the fingerprint region from 600 to 2000 cm-1. We show that the oxidation of the methionine residue with protected terminal groups induces the formation of a sulfoxide group. However, compared to the IRMPD spectrum of protonated methionine and methionine sulfoxide, significant spectral differences are observed in the spectra of model peptide backbones containing methionine. DFT calculations show that protonation occurs on the sulfoxide group in the gas phase for these model peptide backbones containing methionine, shifting the diagnostic signature of the sulfoxide group from 1000 to 862 cm-1.

The unique biogeochemical role of carbonate-associated organic matter in a subtropical seagrass meadow

The particulate organic matter buried in carbonate-rich seagrass ecosystems is an important blue carbon reservoir. While carbonate sediments are affected by alkalinity produced or consumed in seagrass-mediated biogeochemical processes, little is known about the corresponding impact on organic matter. A portion of particulate organic matter is carbonate-associated organic matter. Here, we explore its biogeochemistry in a carbonate seagrass meadow in central Florida Bay, USA. We couple inorganic stable isotope analyses (δ34S, δ18O) with a molecular characterization of dissolved and carbonate associated organic matter (21 tesla Fourier-transform ion cyclotron resonance mass spectrometry). We find that carbonate-associated molecular formulas are highly sulfurized compared to surface water dissolved organic matter, with multiple sulfurization pathways at play. Furthermore, 97% of the formula abundance of surface water dissolved organic matter is shared with carbonate-associated organic matter, indicating connectivity between these two pools. We estimate that 9.2% of the particulate organic matter is carbonate-associated, and readily exchangeable with the broader aquatic system as the sediment dissolves and reprecipitates.

Unveiling the optical and molecular characteristics of aging microplastics derived dissolved organic matter transformed by UV/chlor(am)ine oxidation and its potential for disinfection byproducts formation

The investigations into the existence and behavior of microplastics (MPs) in water environment were widely conducted, while the characteristics of dissolved organic matter derived from MPs (MPs-DOM) during advanced oxidation have garnered comparatively little attention. In this study, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) was employed along with multiple statistical analyses to gain a deeper understanding of the conversion of MPs-DOM in UV/chlor(am)ine advanced oxidation processes (AOPs). The diverse treatments exhibited varying degrees of augmentation in both aging and fragmentation of MPs with the order of UV/Cl2 > UV > UV/NH2Cl. The fragmentation degree of MPs upon two UV-based AOPs (UV-AOPs) was dependent on their monomer chemical structure. The highest TOC values of three MPs-DOM were observed after UV/Cl2 AOP and the lowest after UV/NH2Cl AOP. Polyvinyl chloride (PVC) displayed a greater release of MPs-DOM under varying leaching conditions. UV/Cl₂ AOP favored the reaction with saturated MPs-DOM, while UV/NH₂Cl AOP reduced unsaturated MPs-DOM, alleviating disinfection byproducts (DBPs) formation after chlorination. The precursors generated by UV/Cl₂ AOP owned lower H/C, higher modified aromatic index (AImod), and lower molecular weight (MW) products after chlorination. PVC-DOM with fewer CH₂ groups was more reactive. -H₂O, +O and -CH₂ reactions dominated in PVC-DOM (CHO compounds), while -2H, +O, -CH₂ did in PVC-DOM (CHON compounds). The dominant chlorine addition/substitution reactions occurred in PVC-DOM treated by UV/Cl₂ AOP, identifying 195 Cl-DBPs with 220 precursor-product pairs. Mass difference analyses showed that +2H and +O reactions were the most frequent of the 24 reaction types. Environmental ImplicationMicroplastics derived dissolved organic matters (MPs-DOM) transformed into disinfection byproducts (DBPs) under advanced oxidation processes (AOPs), heightening environmental risks. In this study, Fourier transform ion cyclotron resonance mass spectrometry was employed to gain a deeper understanding of MPs-DOM conversion in UV/chlor(am)ine AOPs. MPs fragmentation and fluorescent components varied with monomer chemistry and polymers. UV/Cl₂ AOP reacted with saturated MPs-DOM. UV/NH₂Cl AOP reduced unsaturated MPs-DOM, alleviating DBPs formation. DBPs precursors generated by UV/Cl₂ AOP owned higher modified aromatic index, lower H/C and molecular weight. Unveiling the MPs-DOM transformation during AOPs can mitigate the negative environmental impacts of MPs and their derivatives.

Molecular insights into the degradation of organic matter from secondary swine wastewater effluent: A comparative study of advanced oxidation processes

Advanced oxidation processes (AOPs) are promising for the treatment of secondary swine wastewater effluents, however, the molecular-level understanding of effluent organic matter (EfOM) removal and transformation during AOPs is limited. This study employed molecular-level characterization based on Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and bulk characterizations to investigate these processes in various AOPs, including Cu-Fenton, UV-Cu-Fenton, Fenton, UV-Fenton, and UV/H2O2 treatments. Our findings revealed that the removal rates of dissolved organic carbon and EfOM molecules follow the sequence of UV-Fenton > Fenton > UV-Cu-Fenton > UV/H2O2 > Cu-Fenton, correlating with the rates of H2O2 decomposition during reactions. AOPs with faster H2O2 decomposition, indicative of higher reactive oxygen species generation, predominantly mineralize rather than transform EfOM. Linkage analysis highlighted oxygen addition and deamination as the primary transformation reactions, with variations in the dominance levels of these reactions across different AOPs. Recalcitrant molecule, particularly CHNO and CHO types, including low-molecular-weight carboxyl-rich alicyclic molecules, pose challenges in treatment. To enhance the efficacy of secondary effluent treatment, strategies focusing on the targeted removal of such recalcitrant EfOM should be developed. This study provided new insights into the selection and optimization of AOPs for secondary swine wastewater effluent treatment.

Contrasting molecular structures and photooxidation behaviors between dissolved organic sulfur released from rice straw-biochar and aerobically decomposed rice straw

Photooxidation of dissolved organic sulfur (DOS) in soils and natural waters plays an important role in the sulfur biogeochemical cycle. However, the structural-dependent photoliabilities of DOS from different sources remain unclear. Here, the molecular structures and photooxidation behaviors of DOS in pyrogenic dissolved black matter (PyDOM) derived from rice straw-pyrolyzed biochar (referred to as PyDOM-S and considered to be representative of black carbon from prairie fires) were thoroughly characterized and compared with those of DOS in leached dissolved organic matter (LDOM) derived from aerobically decomposed rice straw (referred to as LDOM-S and considered to be generally representative of organic-rich horizons in soils and peats). The Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) analysis revealed that both PyDOM-S and LDOM-S were, respectively, dominated by aliphatic (60.4 % and 41.1 %) and lignin-like compounds (35.1 % and 40.1 %), followed by minimal aromatic and polyaromatic compounds (2.8 % and 11.9 % in total). As demonstrated by the sulfur K-edge X-ray absorption near-edge structure (S-XANES) analysis, PyDOM-S consisted mainly of organosulfate (80.4 %) contrasting to the diversified and mingled reduced sulfurs (62.7 %) and oxidized sulfurs (37.3 %) of LDOM-S. Under simulated sunlight irradiation, 74 % of sulfur in PyDOM-S was photomineralized to sulfate within 24 h and totaling 89 % after 168 h, but only 9 % and 42 % for LDOM-S given the same periods of time, confirming the much faster photomineralization of PyDOM-S. After 168-h irradiation, almost all molecules in PyDOM-S disappeared, whereas a large proportion (44.2 %) of LDOM-S molecules (mainly aliphatic and lignin-like compounds) were photo-resistant. Furthermore, the photomineralization of PyDOM-S was mainly contributed by the final and complete oxidation of organosulfate to sulfate; however, the photooxidation of LDOM-S was dominated by the sequential oxidation of exocyclic sulfur and heterocyclic sulfur to organosulfate prior to releasing sulfate. These results highlight that pyrogenic-sourced PyDOM-S and diagenesis-derived LDOM-S exhibit contrasting photooxidation behaviors due to the associated distinct molecular structures.

A fast solid-phase microextraction scheme for in vivo monitoring of bio-accumulation and bio-transformation of arbidol in living plants

Large quantity of the antiviral drug arbidol is used for resisting virus infection like the Corona Virus Disease 2019 and influenza, resulting in unanticipated environmental pollution. Herein, to investigate the environmental risks of the unanticipated arbidol contamination, a novel in vivo sampling probe was developed based on a bromo-substituted porous organic polymer (Br-POP) and then adopted for tracking the bio-accumulation and bio-transformation of arbidol in living plants by coupling with a nano-electrospray ionization fourier-transform ion cyclotron resonance mass spectrometry (Nano-ESI-FT-ICR-MS) method. The established method showed good extraction performance towards arbidol with limit of detection (LOD) of 0.48 ng g−1, and relative standard deviation (RSD) of single-and multiple- probe of 2.2 and 14 %. Owing to the interactions between the Br-POP and the target analytes, as well as the fast analysis process of Nano-ESI-FT-ICR-MS, <6 min was cost for total sampling and analysis duration, achieving hourly tracking of arbidol and its metabolites in this work. During 21-d in vivo tracking, the concentration of arbidol in living plant stems increased rapidly within 6 h and peaked at 413.93 ± 47.09 ng g−1. Meanwhile, it was found that dissolved organic matters (DOM) had significant effect on arbidol behaviors in living plants, resulting in a decrease of the maximum concentration of arbidol in plant stems (152.70 ± 42.44 ng g−1) and the change of dominant metabolite of arbidol that the S-oxidation rather than N-demethylation product of arbidol was dominant with DOM participation. Additionally, the plant root secretion was found to be significantly altered by arbidol exposure. To summarized, the combination of in vivo SPME and the FT-ICR-MS analysis provide new and important information regarding arbidol contamination and related alternation of plant root metabolism.

Compositional Analysis of Oxygenates and Hydrocarbons in Waste and Virgin Polyolefin Pyrolysis Oils by Ultrahigh-Resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

Compositional Analysis of Oxygenates and Hydrocarbons in Waste and Virgin Polyolefin Pyrolysis Oils by Ultrahigh-Resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

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.

VOCs conversion in He/H2O plasma produced in a micro-capillary tube at atmospheric pressure

Abstract A non-equilibrium plasma is created in a micro-capillary quartz tube (800 µm of internal diameter), by a DC-pulsed micro-dielectric barrier discharge (micro-DBD) and the propagation of an ionisation wave, in mixtures of He/H2O/VOC at atmospheric pressure where the studied volatile organic compounds (VOCs) are representative of molecules belonging to different chemical families: alcohols (methanol, ethanol, isopropanol, tert-butanol), ketones (acetone), nitriles (acetonitrile), and aromatic hydrocarbons (toluene). The conversion efficiency of these VOCs is studied as a function of the applied voltage on the micro-DBD (or electrical energy deposited in the plasma) and of the initial concentration of the molecules in the range from 1 ppm up to 3000 ppm (depending on the molecule), with the help of high-resolution real-time mass spectrometry Fourier transform ion cyclotron resonance associated to chemical ionisation (CI-FTICR) using H3O+ as precursor ion. A variety of by-products resulting from the conversion of VOCs are identified and quantified, emphasising that the micro-capillary plasma is able to induce a complex chemical reactivity. A qualitative analysis of the involved kinetics, based on the existing literature, reveals that helium species (ions and metastable states) and radicals coming from the dissociation of the water molecules (O and OH) are the most probable candidates to explain the formation of all compounds detected by the CI-FTICR apparatus. Quenching processes of the metastable He(23S) by the VOCs, leading to the dissociation of the molecules, are suggested to explain some of the experimental results.

Ion Source Complementarity for Characterization of Complex Organic Mixtures Using Fourier Transform Mass Spectrometry: A Review.

Complex organic mixtures are found in many areas of research, such as energy, environment, health, planetology, and cultural heritage, to name but a few. However, due to their complex chemical composition, which holds an extensive potential of information at the molecular level, their molecular characterization is challenging. In mass spectrometry, the ionization step is the key step, as it determines which species will be detected. This review presents an overview of the main ionization sources employed to characterize these kinds of samples in Fourier transform mass spectrometry (FT-MS), namely electrospray (ESI), atmospheric pressure photoionization (APPI), atmospheric pressure chemical ionization (APCI), atmospheric pressure laser ionization (APLI), and (matrix-assisted) laser desorption ionization ((MA)LDI), and their complementarity in the characterization of complex organic mixtures. First, the ionization techniques are examined in the common direct introduction (DI) usage. Second, these approaches are discussed in the context of coupling chromatographic techniques such as gas chromatography, liquid chromatography, and supercritical fluid chromatography.

Long-Term Photochemical and Microbial Alterations Lead to the Compositional Convergence of Algal and Terrestrial Dissolved Organic Matter.

Lakes are expected to become more active in processing dissolved organic matter (DOM), but the fate of DOM with different origins remains poorly constrained. We conducted long-term incubation experiments (∼1 year) with sole light, sole microbial, and combined light and microbial treatments using DOM from algal and terrestrial sources (DOMa and DOMt, respectively). Fourier transform ion cyclotron resonance mass spectrometry and 16s rRNA were used to analyze the DOM molecular composition and bacterial community, respectively. We observed that DOMa and DOMt converged toward a similar composition under the combined light and microbial treatment, driven by the removal of source-specific compositions along with the production of refractory, carboxylic-rich alicyclic molecules (CRAM). For CRAM enrichment, microbial processes played a greater role for DOMa, while phototransformation was more important for DOMt. The co-occurrence patterns between DOM molecules and bacteria showed that DOM molecular composition influenced the bacterial community. More complex DOM-bacteria interactions were observed for DOMt compared to DOMa, suggesting that greater bacterial cooperation was necessary for transforming DOMt. Collectively, these findings offer new insights into the mechanisms underlying the uniformity of DOM from various sources through prolonged environmental transformations in lakes.

Thermal Denaturation of Fresh Frozen Tissue Enhances Mass Spectrometry Detection of Peptides.

Thermal denaturation (TD), known as antigen retrieval, heats tissue samples in a buffered solution to expose protein epitopes. Thermal denaturation of formalin-fixed paraffin-embedded samples enhances on-tissue tryptic digestion, increasing peptide detection using matrix-assisted laser desorption ionization imaging mass spectrometry (MALDI IMS). We investigated the tissue-dependent effects of TD on peptide MALDI IMS and liquid chromatography-tandem mass spectrometry signal in unfixed, frozen human colon, ovary, and pancreas tissue. In a triplicate experiment using time-of-flight, orbitrap, and Fourier-transform ion cyclotron resonance mass spectrometry platforms, we found that TD had a tissue-dependent effect on peptide signal, resulting in a (22.5%) improvement in peptide detection from the colon, a (73.3%) improvement in ovary tissue, and a (96.6%) improvement in pancreas tissue. Biochemical analysis of identified peptides shows that TD facilitates identification of hydrophobic peptides.

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.

7662 Mass Spectrometry Imaging Reveals Region-, Age-, And Sex-Specific Effects Of Lipopolysaccharide Administration On Glucocorticoids In Mouse Lymphoid Organs

Abstract Disclosure: M. Salehzadeh: None. S. Khan: None. R. Andrew: None. K.K. Soma: None. Glucocorticoids (GCs) are steroids that are critical for immune function. Immune organs, such as the thymus and spleen, locally produce GCs (i.e., immunosteroids). However, GC concentrations in the thymus and spleen at the cellular level, and how these levels are affected by stress, remain largely unknown. We used state-of-the-art mass spectrometry imaging (MSI) to elucidate the spatial distribution of GCs in the neonatal and adult mouse thymus and spleen 1) at baseline and 2) after an acute stressor. We used MSI to measure 11-deoxycorticosterone (DOC), corticosterone, and 11-dehydrocorticosterone (DHC) in different regions of the thymus (medulla/cortex) and spleen (white/red pulp) after an immunological challenge. We administered lipopolysaccharide (LPS; i.p.) at low (50μg/kg) and high (400μg/kg) doses or saline (vehicle) to male and female C57BL/6J mice at post-natal day (PND) 5 (neonatal) and 90 (adult) (n=6/sex/group/age). 4hr after treatment, we collected thymus and spleen on liquid nitrogen. Cryosections (10μm) were subject to MSI following Girard-T reagent derivatization and α-cyano-4-hydroxycinnamic acid matrix application. Matrix assisted laser desorption/ionisation (MALDI) was used for sampling, coupled to Fourier-transform ion cyclotron mass spectrometry (100μm resolution; positive mode; Bruker 12T SolariX). Adjacent sections were taken to determine histological zones by H&amp;E staining. Preliminary results indicate that LPS increased DOC, corticosterone, and DHC levels by 2- to 9-fold in lymphoid organs at both ages. There was a dose-dependent increase in thymus and spleen GC levels at PND5, but not PND90. At PND5, GC levels were similarly distributed across each tissue in both sexes. In contrast, at PND90, thymic corticosterone levels were greater in males than females in the medulla and cortex. Interestingly, in PND90 thymus, the medulla had greater DHC levels than the cortex only after LPS treatments. In PND90 spleen, GC levels significantly increased after LPS, yet there was no significant difference in GC distribution between sexes or red and white pulp. These results suggest that GC production is uniform across neonatal lymphoid organs. However, in adulthood, the thymus exhibits region-specific GC metabolism. Our results expand knowledge of steroid intracrinology in thymus and spleen and potential effects of environmental stressors (e.g., infectious diseases, toxins) on immune GC responses. Further, our novel MSI method for GC detection in murine lymphoid organs can help inform future techniques in pharmacokinetics for localized thymic and splenic targeting of steroids and steroid modulators. Presentation: 6/3/2024

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.

Organic matter in geothermal springs and its association with the microbial community

Organic matter (OM) plays an important role in the biogeochemical cycles of carbon, nitrogen, and other elements, shaping the structure of the microbiome and vice versa. However, the molecular composition of OM and its impact on the microbial community in terrestrial geothermal environments remain unclear. In this study, we characterized the OM in water and sediment from a typical geothermal field using ultra-high-resolution Fourier transform ion cyclotron resonance mass spectrometry. By combining high-throughput amplicon sequencing and multivariate analyses, we deciphered the association between OM components and microbial community. A surprisingly high chemodiversity of OM was observed in the waters (11,088 compounds) and sediments (7772 compounds) in geothermal springs. Sulfur-containing organic compounds, a characteristic molecular signature of geothermal springs, accounted for 21 % ± 5 % in waters and 33 % ± 4 % in sediments. Multivariate analyses revealed that both labile and recalcitrant fractions of OM (e.g., carbohydrates intensity and tannins chemodiversity) influenced the structure and function of the microbial community. Co-occurrence networks showed that Proteobacteria and Crenarchaeota accounted for most of the connections with OM in waters (33 % and 15 %, respectively) and sediments (15 % and 12 %, respectively), highlighting their key roles in carbon cycling. This study expands our understanding of the molecular compositions of OM in geothermal springs and highlights its potentially important role in global climate change through microbial carbon cycling.

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.