Ion Cyclotron Resonance Mass Spectrometry Research Articles

Fourier Transform Ion Cyclotron Resonance Mass Spectrometry Applications for Metabolomics

Metabolomics is an interdisciplinary field that aims to study all metabolites < 1500 Da that are ubiquitously found within all organisms. Metabolomics is experiencing exponential growth and commonly relies on high-resolution mass spectrometry (HRMS). Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) is a form of HRMS that is particularly well suited for metabolomics research due to its exceptionally high resolution (105–106) and sensitivity with a mass accuracy in parts per billion (ppb). In this regard, FT-ICR-MS can provide valuable insights into the metabolomics analysis of complex biological systems due to unique capabilities such as the easy separation of isobaric and isomeric species, isotopic fine structure analysis, spatial resolution of metabolites in cells and tissues, and a high confidence (<1 ppm mass error) in metabolite identification. Alternatively, the large and complex data sets, long acquisition times, high cost, and limited access mainly through national mass spectrometry facilities may impede the routine adoption of FT-ICR-MS by metabolomics researchers. This review examines recent applications of FT-ICR-MS metabolomics in the search for clinical and non-human biomarkers; for the analysis of food, beverage, and environmental samples; and for the high-resolution imaging of tissues and other biological samples. We provide recent examples of metabolomics studies that highlight the advantages of FT-ICR-MS for the detailed and reliable characterization of the metabolome. Additionally, we offer some practical considerations for implementing FT-ICR-MS into a research program by providing a list of FT-ICR-MS facilities and by identifying different high-throughput interfaces, varieties of sample types, analysis methods (e.g., van Krevelen diagrams, Kendrick mass defect plot, etc.), and sample preparation and handling protocols used in FT-ICR-MS experiments. Overall, FT-ICR-MS holds great promise as a vital research tool for advancing metabolomics investigations.

The mechanism on liquefaction of waste tire by ethanolysis

Thermo-chemical treatment methods are pivotal for effectively managing waste tire rubber (WTR) while promoting energy efficiency and emission reduction. This study investigates the liquefaction of WTR within a thermal ethanol environment, exploring temperature ranges (200–300 °C) and residence times (0–80 min) to discern the role of ethanol in tire degradation. Additionally, the study includes liquefaction experiments with cyclohexane as a solvent to contrast the effect of ethanol, and comparison between ethanol and water to elucidate solvent impact. Results indicate that at 300 °C for 40 min, oil yields peak at 53.05 % for a WTR/ethanol mass ratio of 1:8 and at 51.64 % for a ratio of 1:6, notably surpassing hydrolysis outcomes. By contracting with the results from the liquefaction with cyclohexane as solvent, the involvement of ethanol can facilitate liquid phase products, primarily alkenes and oxygen-containing compounds, attributed to aromatization inhibition. Heavy oils and heteroatomic compounds are characterized through Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS), detecting hydrocarbons and heteroatom compounds like NxOy, Ox, Sx, NxOySz, NxSy, and Nx. Notably, sulfur, a significant pollutant, predominantly manifests as sulfide in chars. These findings offer valuable insights into advancing waste tire recycling technologies.

Hydrothermal temperature-dependent compositions and copper complexing behaviors of hydrochar-derived dissolved organic matter: Insights from FT-ICR MS and multi-spectroscopic analysis

The copper complexing of dissolved organic matter released from hydrochar (HDOM) affects the former's environmental behavior. In this study, how hydrothermal temperatures (180, 220 and 260 °C) influence the molecular-level constitutions and Cu(Ⅱ) binding features of HDOM were elucidated via fourier transform ion cyclotron resonance mass spectrometry and multi-spectroscopic analysis. The findings demonstrated that the almost HDOM molecules had the traits of lower polarity and higher hydrophobicity. As the hydrothermal temperature increased, the molecules with particularly high relative strength gradually disappeared, average molecular weight, percentages of CHON and aliphatic of HDOM reduced while the percentages of CHO and aromatic compounds increased. In general, the fluorescence quenching of Cu(Ⅱ) weakened as hydrothermal temperature rose and the Cu(Ⅱ) binding stability constants of fluorophores in HDOM were 4.50–5.31. In addition, the Cu(Ⅱ) binding order of fluorophores in HDOM showed temperature heterogeneities, and polysaccharides or aromatic rings of non-fluorescent substances had the fastest responses to Cu(II) binding. Generally, fluorescent components tend to bind Cu(II) at relatively trace concentrations (0–40 µmol/L), whereas non-fluorescent substances tend to the bind Cu(II) at relatively higher concentrations (50–100 µmol/L). This study contributed to the prediction of the potential environmental behavior and risk of Cu(II) at the molecular level after hydrochar application.

Assessing the Impacts of Reservoirs on Riverine Dissolved Organic Matter: Insights From the Largest Reservoir in the Pearl River

AbstractExtensive reservoir construction has fragmented more than 70% of the world's rivers, significantly impacting river connectivity and carbon cycling. However, the response of riverine dissolved organic matter (DOM) to reservoir influence and its potential downstream effects remains unclear. In this study, we employed multiple analytical techniques, including Fourier transform ion cyclotron resonance mass spectrometry, radiocarbon dating, and environmental factor analysis, to investigate the dynamic changes in DOM and its controlling factors under different hydrological management regimes in the LongTan Reservoir, the largest reservoir in the Pearl River, which is the second largest river in China by water discharge. Our results indicate that the molecular diversity of riverine DOM is reduced in the reservoir. Oxygen‐rich and heteroatomic compounds, such as those containing nitrogen, sulfur, and phosphorus, are preferentially removed through enhanced photo‐ and biodegradation processes in the reservoir, particularly during the storage period. This leads to DOM that is enriched with oxygen‐poor compounds and shows a biodegraded Δ14C value downstream. This study highlights that the composition of riverine DOM is significantly altered by the reservoir, but these effects could potentially be mitigated by optimizing the outlet location.

An automated and high-throughput data processing workflow for PFAS identification in biota by direct infusion ultra-high resolution mass spectrometry.

The increasing recognition of the health impacts from human exposure to per- and polyfluorinated alkyl substances (PFAS) has surged the need for sophisticated analytical techniques and advanced data analyses, especially for assessing exposure by food of animal origin. Despite the existence of nearly 15,000 PFAS listed in the CompTox chemicals dashboard by the US Environmental Protection Agency, conventional monitoring and suspect screening methods often fall short, covering only a fraction of these substances. This study introduces an innovative automated data processing workflow, named PFlow, for identifying PFAS in environmental samples using direct infusion Fourier transform ion cyclotron resonance mass spectrometry (DI-FT-ICR MS). PFlow's validation on a bream liver sample, representative of low-concentration biota, involves data pre-processing, annotation of PFAS based on their precursor masses, and verification through isotopologues. Notably, PFlow annotated 17 PFAS absent in the comprehensive targeted approach and tentatively identified an additional 53 compounds, thereby demonstrating its efficiency in enhancing PFAS detection coverage. From an initial dataset of 30,332 distinct m/z values, PFlow thoroughly narrowed down the candidates to 84 potential PFAS compounds, utilizing precise mass measurements and chemical logic criteria, underscoring its potential in advancing our understanding of PFAS prevalence and of human exposure.

Rock-to-Pharma: Characterization of Shale Oil-Based Nonbiological Complex Drugs along the Production Process by High-Resolution Mass Spectrometry.

Antibiotic resistance has become a primary concern in medicine because of the overuse and misuse of classical pharmaceuticals. Recently, nonbiological complex drugs (NBCDs) have gained interest for their complex pharmacological profiles. Bituminosulfonates, which have lately been tentatively allocated toward NBCDs, are pharmacologically well-studied and show low potential in resistance development. However, molecular composition knowledge is limited. With this work, we present a comprehensive approach to investigate the manufacturing process of complex pharmaceuticals like bituminosulfonates on a molecular level via Fourier-transform ion cyclotron resonance mass spectrometry. The application of various hyphenations and ionization techniques comprehensively covers the entire mass and polarity range of the matrix, and the high sensitivity enables the identification of significant and minor chemical alterations caused by the multistep manufacturing process. The distillation of the shale crude oil eliminates highly aromatic PAH and PASH constituents. ESI(-) revealed strong PAH- and PASH-sulfonate formation after reacting the shale oil distillate with sulfuric acid. Increasing alkylation reduced the sulfonation yield, instead causing oligomerization side reactions, as observed by APPI analysis. Furthermore, multidimensional gas chromatography coupled with high-resolution mass spectrometry verified core structural motifs. With this work, we demonstrate the high potential of FT-ICR MS in NBCD process analysis. The results also give valuable information for future pharmacological investigations focusing on specific compound classes or properties.

Transformation of sedimentary dissolved organic matter in electrokinetic remediation catalogued by FT-ICR mass spectrometry

In electrokinetic remediation (EKR), the sedimentary dissolved organic matter (DOM) could impede remediation by scavenging reactive species and generating unintended byproducts. Yet its transformation and mechanisms remained largely unknown. This study conducted molecular-level characterization of the water-extractable DOM (WEOM) in EKR using negative-ion electrospray ionization coupled to 21 tesla Fourier transform ion cyclotron resonance mass spectrometry (21 T FT-ICR MS). The results suggested that ∼55 % of the ∼7,000 WEOM compounds identified were reactive, and EKR lowered their diversity, molecular weight distribution, and double-bond equivalent (DBE) through a combination of electrochemical and microbial redox reactions. Heteroatom-containing WEOM (CHON and CHOS) were abundant (∼ 35% of the total WEOM), with CHOS generally being more reactive than CHON. Low electric potential (1 V/cm) promoted the growth of dealkylation and desulfurization bacteria, and led to anodic CO2 mineralization, anodic cleavage of -SO and -SO3, and cathodic cleavage of -SH2; high electric potential (2 V/cm) only enriched desulfurization bacteria, and differently, led to anodic oxygenation and cathodic hydrogenation of unsaturated and phenolic compounds, in addition to cathodic cleavage of -SH2. The long-term impact of these changes on soil quality and nitrogen-sulfur-carbon flux may be need to studied to identify unknown risks and new applications of EKR.

Improved Characterization of Soil Organic Matter by Integrating FT-ICR MS, Liquid Chromatography Tandem Mass Spectrometry, and Molecular Networking: A Case Study of Root Litter Decay under Drought Conditions.

Understanding of how soil organic matter (SOM) chemistry is altered in a changing climate has advanced considerably; however, most SOM components remain unidentified, impeding the ability to characterize a major fraction of organic matter and predict what types of molecules, and from which sources, will persist in soil. We present a novel approach to better characterize SOM extracts by integrating information from three types of analyses, and we deploy this method to characterize decaying root-detritus soil microcosms subjected to either drought or normal conditions. To observe broad differences in composition, we employed direct infusion Fourier-transform ion cyclotron resonance mass spectrometry (DI-FT-ICR MS). We complemented this with liquid chromatography tandem mass spectrometry (LC-MS/MS) to identify components by library matching. Since libraries contain only a small fraction of SOM components, we also used fragment spectral cosine similarity scores to relate unknowns and library matches through molecular networks. This integrated approach allowed us to corroborate DI-FT-ICR MS molecular formulas using library matches, which included fungal metabolites and related polyphenolic compounds. We also inferred structures of unknowns from molecular networks and improved LC-MS/MS annotation rates from ∼5 to 35% by considering DI-FT-ICR MS molecular formula assignments. Under drought conditions, we found greater relative amounts of lignin-like vs condensed aromatic polyphenol formulas and lower average nominal oxidation state of carbon, suggesting reduced decomposition of SOM and/or microbes under stress. Our integrated approach provides a framework for enhanced annotation of SOM components that is more comprehensive than performing individual data analyses in parallel.

Molecular features of uranium-binding natural organic matter in a riparian wetland determined by ultrahigh resolution mass spectrometry

Tims Branch riparian wetland located in South Carolina, USA has immobilized 94 % of the U released >50 years ago from a nuclear fuel fabrication facility. Sediment organic matter (OM) has been shown to play an important role in immobilizing U. Yet, uranium-OM-mineral interactions at the molecular scale have never been investigated at ambient concentrations. The objectives of this study were to extract, purify, and concentrate U-bound sediment OM along the stream water pathway and perform molecular characterization using Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS). Out of 9614 identified formulas, 715 contained U. These U-containing formulas were enriched with Fe, N, and/or S compared to the total OM. Lignin-like and protein-like molecules accounted for 40 % and 19 % of the U-containing formulas, respectively. Phosphorus-containing formulas were found to exert an insignificant influence on complexing U. U-containing formulas in the ‘mobile’ (groundwater extractable) OM fraction had lower (reduced) nominal oxidation states of carbon (NOSC); and less aromatic moieties than OM recovered from the ‘immobile’ (sodium pyrophosphate extractable) OM fraction. U-containing formulas in the redox interfacial zones (stream banks) compared to those in nearby up-slope zones tended to have smaller molecular weights; lower NOSC; higher contents of COO and/or CONO functional groups; and higher abundance of Fe-containing formulas. Fe was present in 38 % of the U-containing formulas but only 20 % of the total OM formulas. It is postulated that Fe played an important role in stabilizing the structure of sedimentary OM, especially U-containing compounds. The identification for the first time of hundreds of Fe-U-OM formulas demonstrates the complexity of such system is much greater than commonly believed and numerically predicting U binding behavior in OM-rich systems may require greater use of statistical or artificial intelligence approaches rather than deterministic approaches limited to measuring metal complexation with well-defined individual analogue organic ligands.

Interactions between Iron Minerals and Dissolved Organic Matter Derived from Microplastics Inhibited the Ferrihydrite Transformation as Revealed at the Molecular Scale.

Microplastic-derived dissolved organic matter (MP-DOM) is an emerging carbon source in the environment. Interactions between MP-DOM and iron minerals alter the transformation of ferrihydrite (Fh) as well as the distribution and fate of MP-DOM. However, these interactions and their effects on both two components are not fully elucidated. In this study, we selected three types of MP-DOM as model substances and utilized Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and extended X-ray absorption fine structure (EXAFS) spectroscopy to characterize the structural features of DOMs and DOM-mineral complexes at the molecular and atomic levels. Our results suggest that carboxyl and hydroxyl groups in MP-DOM increased the Fe-O bond length by 0.02-0.03 Å through interacting with Fe atoms in the first shell, thereby inhibiting the transformation of Fh to hematite (Hm). The most significant inhibition of Fh transformation was found in PS-DOM, followed by PBAT-DOM and PE-DOM. MP-DOM components, such as phenolic compounds and condensed polycyclic aromatics (MW > 360 Da) with high oxygen content and high unsaturation, exhibited stronger mineral adsorption affinity. These findings provide a profound theoretical basis for accurately predicting the behavior and fate of iron minerals as well as MP-DOM in complex natural environments.

Probing nitro(so) and chloro byproducts and their precursors in natural organic matter during UV/NH2Cl treatment by FT-ICR MS with machine learning insights

The UV/monochloramine (UV/NH2Cl) process, while efficiently eliminating micropollutants, produces toxic byproducts. This study utilized Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to investigate molecular-level changes in natural organic matter (NOM) and to disclose formation pathways of nitro(so) and chloro byproducts in the UV/NH2Cl process. The UV/NH2Cl process significantly increased the saturation and oxidation levels and altered the elemental composition of NOM. Using 15N labeling and a screening workflow, nitro(so) byproducts with nitrogen originating from inorganic sources (i.e., reactive nitrogen species (RNS) and/or NH2Cl) were found to exhibit total intensities comparable to those from NOM. RNS, rather than NH2Cl, played a significant role in incorporating nitrogen into NOM. Through linkage analysis, nitro(so) addition emerged as an important reaction type among the 25 reaction types applied. By using phenol as a representative model compound, the nitro byproducts were confirmed to be mainly generated through the oxidation of nitroso byproducts instead of nitration. Machine learning and SHAP analysis further identified the major molecular indices distinguishing nitro(so) and chloro precursors from non-precursors. This study enhances our fundamental understanding of the mechanisms driving the generation of nitro(so) and chloro byproducts from their precursors in complex NOM during the UV/NH2Cl process.

Lentisk (Pistacia lentiscus) Oil Nanoemulsions Loaded with Levofloxacin: Phytochemical Profiles and Antibiofilm Activity against Staphylococcus spp.

Most clinical isolates of both Staphylococcus aureus and Staphylococcus epidermidis show the capacity to adhere to abiotic surfaces and to develop biofilms resulting in a contribution to chronic human skin infections. Antibiotic resistance and poor biofilm penetration are the main causes of ineffective therapeutic treatment in killing bacteria within biofilms. A possible strategy could be represented by drug delivery systems, such as nanoemulsions (composed of bioactive oil, surfactant and water phase), which are useful for enhancing the drug permeation of a loaded drug inside the biofilm and its activity. Phytochemical characterization of Pistacia lentiscus oil (LO) by direct infusion Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) allowed the identification of bioactive compounds with antimicrobial properties, including fatty acids and phenolic compounds. Several monoterpenes and sesquiterpenes have been also detected and confirmed by gas chromatography-mass spectrometric (GC-MS) analysis, together providing a complete metabolomic profiling of LO. In the present study, a nanoemulsion composed of LO has been employed for improving Levofloxacin water solubility. A deep physical-chemical characterization of the nanoemulsion including hydrodynamic diameter, ζ-potential, morphology, entrapment efficiency, stability release and permeation studies was performed. Additionally, the antimicrobial/antibiofilm activity of these preparations was evaluated against reference and clinical Staphylococcus spp. strains. In comparison to the free-form antibiotic, the loaded NE nanocarriers exhibited enhanced antimicrobial activity against the sessile forms of Staphylococcus spp. strains.

Magnetic ligand fishing protocol combined with HPLC-FT-ICR-MS for screening potential α-Glucosidase inhibitors from UCG and in silico analysis

Uremic Clearance Granule (UCG) is a traditional Chinese medicines (TCMs) that has been recognized as potentially effective treatment for diabetic nephropathy (DN). However, the chemical composition and the hypoglycemic ingredients of UCG remain unclear. In this experiment, a magnetic ligand fishing protocol combined with HPLC coupled Fourier transform ion cyclotron resonance mass spectrometry (HPLC-FT-ICR-MS) technology was developed to screen and identify α-Glucosidase inhibitors from UCG. First, constituents of UCG was identified by HPLC-FT-ICR-MS. Next, α-Glucosidase coated Fe3O4@SiO2@NH2 (Fe3O4@SiO2@NH2@α-Glucosidase) nano composites was synthesized. The essential parameters (concentration of Glutaraldehyde (GA), ratio of Fe3O4@SiO2@NH2 to enzyme, crosslinking time and immobilization time) were optimized to obtain maximum enzyme activity and the performance of immobilized enzyme was compared with that of free enzyme. The α-Glucosidase inhibitory activities were then evaluated using autodock and the 4-Nitrophenyl-α-D-glucopyranoside (pNPG) method. As a result, 142 compounds were identified were identified by comparing the retention time, molecular ions and fragmentation behaviors with the reference compounds or the in-house database. 20 possible α-Glucosidase activity inhibitory components were identified using HPLC-FT-ICR-MS. Molecular docking and inhibition studies showed that 4 compuunds including Limonexic acid, Sanggenol A, Glabrone, Matrine were more likely to stronger α-Glucosidase inhibitory activities than acarbose. In conclusion, the proposed approach, which combined highly specific screening with HPLC-FT-ICR-MS, provided a powerful platform for discovering bioactive components from multi-component and multi-target traditional Chinese medicines (TCMs).

Combining Advanced Analytical Methodologies to Uncover Suspect PFAS and Fluorinated Pharmaceutical Contributions to Extractable Organic Fluorine in Human Serum (Tromsø Study).

A growing number of studies have reported that routinely monitored per- and polyfluoroalkyl substances (PFAS) are not sufficient to explain the extractable organic fluorine (EOF) measured in human blood. In this study, we address this gap by screening pooled human serum collected over 3 decades (1986-2015) in Tromsø (Norway) for >5000 PFAS and >300 fluorinated pharmaceuticals. We combined multiple analytical techniques (direct infusion Fourier transform ion cyclotron resonance mass spectrometry, liquid chromatography-Orbitrap-high-resolution mass spectrometry, and total oxidizable precursors assay) in a three-step suspect screening process which aimed at unequivocal suspect identification. This approach uncovered the presence of one PFAS and eight fluorinated pharmaceuticals (including some metabolites) in human serum. While the PFAS suspect only accounted for 2-4% of the EOF, fluorinated pharmaceuticals accounted for 0-63% of the EOF, and their contribution increased in recent years. Although fluorinated pharmaceuticals often contain only 1-3 fluorine atoms, our results indicate that they can contribute significantly to the EOF. Indeed, the contribution from fluorinated pharmaceuticals allowed us to close the organofluorine mass balance in pooled serum from 2015, indicating a good understanding of organofluorine compounds in humans. However, a portion of the EOF in human serum from 1986 and 2007 still remained unexplained.

Characteristics of disinfection byproducts from dissolved organic matter during chlor(am)ination of source water in Tibetan Plateau, China

The Tibetan Plateau, a typical high-altitude area, is less affected by human activities such as industrial development, and the external pollution to water sources is extremely low. Then it is also an important source of water samples for exploring the molecular characteristics of precursors in the dissolved organic matter (DOM) of disinfection byproducts (DBPs) in drinking water. Research data on DBPs in drinking water on the Tibet Plateau remains insufficient, leading to uncertainty about DBP contamination in the area. This study explores the formation potential of 35 typical DBPs, including 6 trihalomethanes (THMs), 9 haloacetic acids (HAAs), 2 halogenated ketones (HKs), 9 nitrosamines (NAs), and 9 aromatic DBPs, during chlorination and chloramination of typical source water samples in the Tibet Plateau of China. Moreover, in order to further investigate the characteristics of the generation of DBPs, the molecular composition of DOM in the collected water samples was characterized by Fourier transform ion cyclotron resonance mass spectrometry. The findings reveal that, for chlorination and chloramination, the average concentration of the five classes of DBPs was ranked as follows (chlorination, chloramination): HAAs (268.1 μg/L, 54.2 μg/L) > THMs (44.0 μg/L, 2.0 μg/L) > HKs (0.7 μg/L, 1.8 μg/L) > NAs (26.5 ng/L, 74.6 ng/L) > Aromatics (20.4 ng/L, 19.5 ng/L). The dominant compounds in THMs, HAAs, and NAs are trichloromethane, dichloroacetic acid, trichloroacetic acid, and nitrosopyrrolidine, respectively. This study highlights a significant positive correlation between DBP generation and UV254, SUV254, and the double bond equivalents of DOM in the source water. It systematically elucidates DOM molecular composition characteristics and DBP formation potential in high-altitude water sources, shedding light on key factors influencing DBP generation at the molecular level in high-altitude areas.

Dissolved organic matter released from beach wrack is source-specific and molecularly highly diverse

AbstractBeach wrack is an important supplier of nutrients and organic matter to sandy beach ecosystems and underlying subterranean estuaries (STEs), producing metabolic hotspots in these otherwise organic carbon- and nutrient-poor environments. To assess the impact of beach wrack type (e.g., marine, terrestrial, plant, animal) and environmental settings (e.g., tidal inundation, precipitation, and solar irradiation) on nutrient and dissolved organic matter (DOM) release, a series of leaching experiments was conducted. Quantities of leached nutrients and dissolved organic carbon (DOC) were determined, and DOM molecular composition was investigated using Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Millimolar—to molar amounts of DOC and dissolved nitrogen were released from the beach cast per kg dry weight, with type of wrack and leaching medium (fresh- vs. saltwater) exerting the biggest influences. Exemplary for animal cast, jellyfish leached up to two 100-fold more, mostly organic, nitrogen compared to all other beach wrack types. FT-ICR-MS data of solid-phase extracted DOM indicated that beach wrack releases compounds with putative mono- and oligosaccharide-, amino acid- and vitamin-type molecular formulae, which likely serve as valuable substrate for heterotrophic microorganisms. DOM from the brown seaweed Fucus sp. was more aromatic than seawater DOM and even beach wrack of terrestrial origin, probably from structural components and secondary metabolites such as phlorotannins. We conclude that DOM and nutrient release from beach wrack strongly depends on wrack type and leaching medium, may obscure molecular provenance proxies (e.g., terrestrial indices), and adds a nutritional boost to infiltrating sea- and rainwater which likely impact microbial respiration rates in the STE.

Catalytic ozonation promoted by Mn-doped sludge-based catalyst treating refractory industrial wastewater

Attributed to the refractory characteristic of industrial wastewater, it usually needs advanced treatment. Moreover, massive hazardous activated waste sludge generated from wastewater treatment introduces additional ecological risks. In this study, sludge-based catalysts were prepared by doping Mn to treat typical refractory wastewater of petrochemical secondary wastewater. Results showed that the Mn-doped catalyst (PS-M700) prepared by pyrolysis at 700 °C was optimal for the catalytic ozonation of petrochemical secondary wastewater. The optimal ozone and catalyst dosage were 216 mg/L and 1.0 g/L, respectively. Catalytic ozonation of petrochemical secondary wastewater using PS-M700 showed an excellent TOC removal efficiency of 56.6 %. In addition, hydroxyl radicals (OH) played a major role in the catalytic ozonation of the petrochemical secondary wastewater. Results of excitation-emission matrix fluorescence spectroscopy showed that catalytic ozonation can further enhance the removal efficiency of not readily biodegradable compounds compared to ozone alone. Moreover, the catalytic ozonation process mainly targeted substances within the molecular weight (MW) < 1 kDa range in petrochemical secondary wastewater. In addition, transformation processes occurred between pollutants of different MW. Fourier Transform ion cyclotron resonance mass spectrometry showed that oxygen (CHO), nitrogen (CHONO) and sulfur (CHOS) containing contaminants were decreased by 6.0 % (2359 vs 2216), 34.9 % (2505 vs 1631) and 62.8 % (1227 vs 456). The present study shows the satisfactory prospect of a sustainable “wastes-treating-wastes” process for wastewater treatment.

Metagenomic and FT-ICR MS insights into the mechanism for the arsenic biogeochemical cycling in groundwater

Arsenic (As) is a groundwater contaminant of global concern. The degradation of dissolved organic matter (DOM) can provide a reducing environment for As release. However, the interaction of DOM with local microbial communities and how different sources and types of DOM influence the biotransformation of As in aquifers is uncertain. This study used optical spectroscopy, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), metagenomics, and structural equation modeling (SEM) to demonstrate the how the biotransformation of As in aquifers is promoted. The results indicated that the DOM in high-As groundwater is dominated by highly unsaturated low-oxygen(O) compounds that are quite humic and stable. Metagenomics analysis indicated Acinetobacter, Pseudoxanthomonas, and Pseudomonas predominate in high-As environments; these genera all contain As detoxification genes and are members of the same phylum (Proteobacteria). SEM analyses indicated the presence of Proteobacteria is positively related to highly unsaturated low-O compounds in the groundwater and conditions that promote arsenite release. The results illustrate how the biogeochemical transformation of As in groundwater systems is affected by DOM from different sources and with different characteristics.

Performance of catalytic wet oxidation on thermochemical aqueous effluents assessed by FT-ICR MS

Aqueous phase (AP) is frequently observed in bio-oil from biomass thermochemical conversion or as an upgrading coproduct. However, AP contains high organic content that can be toxic and that must be reduced or removed to be then treated in existing wastewater plants. A promising method to upgrade these APs is the catalytic wet peroxide oxidation (CWPO) that was applied here on APs of both hydrothermal liquefaction and pyrolysis bio-oils from softwood and hardwood. Efficiency of the CWPO was assessed by investigating the molecular composition of raw and treated APs by ultra-high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) with electrospray ionization (ESI) in negative- and positive-ion modes. Combination of FT-ICR MS and multivariate statistical analyses evidenced efficiency of the process with new compounds resulting from the oxidative depolymerization, characterized by lower unsaturation degree and molecular weight, and higher oxygen atom count. Refractory compounds were also observed, which are notably characterized by high unsaturation degrees. Interestingly, both detection modes were shown to be complementary for the understanding of the CWPO process. ESI (-) allowed to assess the completion of the oxidation process in detecting carboxylic acid conversion products and to specifically evidence refractory products. ESI (+) was informative on the CWPO process, especially on the conversion of the basic compounds, with the decrease of the detected species. Eventually, softwood AP was shown to be more reluctant to CWPO than the hardwood one.

Molecular Composition Evolution of Dissolved Organic Matter With Water Depth in Prydz Bay of East Antarctic: Carbon Export Implications

AbstractThis study analyzes the molecular composition of dissolved organic matter (DOM) in Prydz Bay by Fourier Transform Ion Cyclotron Resonance mass spectrometry to probe the carbon sequestration capacity in the continental shelf system. Concentrations of particulate organic carbon (POC), particulate nitrogen and dissolved organic carbon (DOC) with water depth show that POC could be mainly decomposed into DOC and/or microbially degraded. Highly labile DOC is further degraded and remineralized by microorganisms within the upper 200 m, as evidenced by a downward enrichment of 13CPOC and increases in the average molecular weight, oxygen atom number (O) and double bond equivalents of DOM molecules, indicating that biodegradation is the main driver for particulate organic matter and DOM evolution with water depth. Semi‐quantitative calculation demonstrates that ∼83% of POC was transformed to DOC as well as dissolved inorganic carbon (DIC), and ∼30% of DOC further to DIC via microbial degradation within the upper 200 m in summer, resulting in a relatively low total organic carbon content in sediments of Prydz Bay. The newly transformed DIC and residue DOC can be preserved in the deep layer due to the formation of well stratified and stable water body in summer of Prydz Bay, ultimately entering the regional circulation system instead of being released back into the atmosphere. This could be one of the most important processes determining the atmosphere CO2 uptake in the continental shelf system of Southern Ocean.