Ion Cyclotron Resonance Mass Spectrometry Research Articles

Photo-methanification of aquatic dissolved organic matters with different origins under aerobic conditions: Non-negligible role of hydroxyl radicals

Lingering inconsistencies in the global methane (CH4) budget and ambiguity in CH4 sources and sinks triggered efforts to identify new CH4 formation pathways in natural ecosystems. Herein, we reported a novel mechanism of light-induced generation of hydroxyl radicals (•OH) that drove the production of CH4 from aquatic dissolved organic matters (DOMs) under ambient conditions. A total of five DOM samples with different origins were applied to examine their potential in photo-methanification production under aerobic conditions, presenting a wide range of CH4 production rates from 3.57 × 10−3 to 5.90 × 10−2 nmol CH4 mg-C−1 h−1. Experiments of •OH generator and scavenger indicated that the contribution of •OH to photo-methanificaiton among different DOM samples reached about 4∼42 %. In addition, Fourier transform infrared spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry showed that the carbohydrate- and lipid-like substances containing nitrogen-bonded methyl groups, methyl ester, acetyl groups, and ketones, were the potential precursors for light-induced CH4 production. Based on the experimental results and simulated calculations, the contribution of photo-methanification of aquatic DOMs to the diffusive CH4 flux across the water-air interface in a typical eutrophic shallow lake (e.g., Lake Chaohu) ranged from 0.1 % to 18.3 %. This study provides a new perspective on the pathways of CH4 formation in aquatic ecosystems and a deeper understanding on the sources and sinks of global CH4.

From the grapevine to the glass: A wine metabolomics tale by FT-ICR-MS.

Wine is one of the most consumed beverages around the world. Its unique characteristics arise from numerous processes, from the selection of grapevine varieties and grapes, the effect of the terroir and geographical origin, through the biochemical process of fermentation by microorganisms, until its aging. All molecules found in wine define its chemical fingerprint and can be used to tell the story of its origin, production, authenticity and quality. Wine's chemical composition can be characterized using an untargeted metabolomics approach based on extreme resolution mass spectrometry. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) is currently the most powerful analytical technique to analyse such complex sample, providing the most comprehensive analysis of the chemical fingerprint of wine.

Dissolved organic matter isolates obtained by solid phase extraction exhibit higher absorption and lower photo-reactivity: Effect of components

Notable differences in photo-physical and chemical properties were found between bulk water and solid phase extraction (SPE) isolates for dissolved organic matter (DOM). The moieties extracted using modified styrene divinylbenzene cartridges, which predominantly consist of conjugated aromatic molecules like humic acids, contribute mainly to light absorption but exhibit lower quantum yields of fluorescence and photo-produced reactive intermediates (PPRIs). Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) revealed lignin as the moieties displaying most significant variance in abundance. In Van Krevelen-Spearman plot, we observed molecules positively or negatively correlated with DOM's optical and photochemical properties (including SUVA254, steady-state concentrations of ·OH, 1O2 quantum yield, etc.) were confined to specific regions, which can be delineated using a threshold modified aromaticity index (AImod) of 0.3. Based on the relationships between optical properties and PPRI production, it is suggested that the energy gap between ground state and excited singlet state (△ES1→S0), governing the inner conversion rate, serves as a determinant for apparent quantum yield of PPRIs in DOM, with intra-molecular charge transfer (CT) interactions potentially playing a pivotal role. Regarding DOM's photoreactivity with pollutants, this study has revealed, for the first time, that protein/amino sugars/amino acids could act as antioxidant groups in addition to phenols on the photolysis of sulfadiazine. These findings provide valuable insights into DOM photochemistry and are expected to stimulate further research in this area.

Appearance of Recalcitrant Dissolved Black Carbon and Dissolved Organic Sulfur in River Waters Following Wildfire Events.

Increasing wildfire frequency, a consequence of global climate change, releases incomplete combustion byproducts such as aquatic pyrogenic dissolved organic matter (DOM) and black carbon (DBC) into waters, posing a threat to water security. In August 2022, a series of severe wildfires occurred in Chongqing, China. Samples from seven locations along the Yangtze and Jialing Rivers revealed DBC, quantified by the benzene poly(carboxylic acid) (BPCA) method, comprising 9.5-19.2% of dissolved organic carbon (DOC). High concentrations of BPCA-DBC with significant polycondensation were detected near wildfire areas, likely due to atmospheric deposition driven by wind. Furthermore, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) revealed that wildfires were associated with an increase in condensed aromatics, proteins, and unsaturated hydrocarbons, along with a decrease in lignins. The condensed aromatics primarily consisted of dissolved black nitrogen (DBN), contributing to abundant high-nitrogen-containing compounds in locations highly affected by wildfires. Meanwhile, wildfires potentially induced the input of recalcitrant sulfur-containing protein-like compounds, characterized by high oxidation, aliphatic nature, saturation, and low aromaticity. Overall, this study revealed the appearance of recalcitrant DBC and dissolved organic sulfur in river waters following wildfire events, offering novel insights into the potential impacts of wildfires on water quality and environmental biogeochemistry.

Kinetics, products and mechanisms of unsaturated alcohols and NO3 radicals

Unsaturated alcohols are emitted in the atmosphere from anthropogenic and biological sources. Although NO3 radical-initiated reaction of unsaturated alcohols constitute a significant portion to SOA formation, less studies have been reported. In this study, the rate constants of the reactions between NO3 radicals with 2-methyl-2-propen-1-ol (2M2P1O), (E)-4-hexen-1-ol (t-4H1O) and 4-penten-2-ol (4P2O) were measured at 298 ± 2 K by using relative rate methods. The rate constants were 3.41 ± 0.51 (2M2P1O), 6.45 ± 0.66 (t-4H1O) and 0.56 ± 0.15 (4P2O) (in units of 10−13 cm3molecule−1s−1), respectively. The reaction rates were also estimated by structure-activity relationships (SARs) method and compared with the experimental results. It showed that the estimated rate constant of 4-penten-2-ol by SARs was unreasonable due to the lack of group parameters. In addition, large amounts of organic nitrates were identified based on fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). The MS results showed that dinitrates were primary SOA components. The obtained reaction rate constants and the formation mechanisms of organic nitrates provide an important experimental basis for future atmospheric chemical models.

Evaluations of Weathering of Polar and Nonpolar Petroleum Components in a Simulated Freshwater-Oil Spill by Orbitrap and Fourier Transform Ion Cyclotron Resonance Mass Spectrometry.

The comprehensive chemical characterization of crude oil is important for the evaluation of the transformation and fate of components in the environment. Molecular-level speciation of naphthenic acid fraction compounds (NAFCs) was investigated in a mesoscale spill tank using both negative-ion electrospray ionization (ESI) Orbitrap mass spectrometry (MS) and positive-ion atmospheric pressure photoionization Fourier transform ion cyclotron resonance mass spectrometry (APPI-FT-ICR-MS). Both ionization techniques are coupled to high-resolution mass spectrometric detectors (ESI: Orbitrap MS; APPI: FT-ICR-MS at 9.4 T), enabling insight into the behavior and fate of petrogenic compounds during a simulated freshwater crude oil spill. Negative-ion ESI Orbitrap-MS reveals that oxygen-containing (Ox) classes are detected early in the spill, whereby species with more oxygen per molecule evolve later in the simulated spill. The O2-containing species gradually decreased in relative abundance, while O3 and O4 species increased in relative abundance throughout the simulated spill, which could correspond to a relative degree of oxygen incorporation. Nonpolar speciation by positive-ion APPI 9.4 T FT-ICR-MS allowed for the identification of water-soluble nonpolar and less polar acidic species. Molecular-level graphical representation of elemental compositions derived from simulated spill water-soluble and oil-soluble species suggest that biological activity is the primary degradation mechanism and that biodegradation was the dominant mechanism based on the negative-ion ESI Orbitrap-MS results.

Storm-driven hydrological, seasonal, and land use/land cover impact on dissolved organic matter dynamics in a mid-Atlantic, USA coastal plain river system characterized by 21 T FT-ICR mass spectrometry

Introduction: Dissolved organic matter (DOM) as primary and secondary energy sources can be transported via rivers to estuaries and impact coastal biogeochemical cycles. Storm-induced high discharge events can alter the dominant river flow paths and enhance leaching of shallow organic-rich soil layers, leading to elevated terrestrial DOM export. Land use/land cover (LULC) and associated anthropogenic interventions (including artificial reservoirs and agricultural irrigation) can control sources and transformation processes of exported DOM along with hydrologic factors. The relative significance of LULC, hydrological factors, and temperature variations with seasons will differ depending on geographical locations and complicate their incorporation in biogeochemical models of DOM dynamics. This study investigates the role of LULC, seasonality, and storm events on DOM concentrations and molecular composition in the Murderkill River system.Method: Surface water samples were collected seasonally and before/after storm events from 6 sites representing forested, agricultural, and developed LULC units. The DOM was characterized via parallel factor analysis of excitation-emission matrix data and electrospray ionization 21 T Fourier-transform ion cyclotron resonance mass spectrometry to determine potential DOM sources and enable the development of a conceptual model for DOM dynamics in rivers impacted by anthropogenic reservoirs.Result and Discussion: Our results suggest that storm-induced shallow and overland flow paths can increase surface-vegetation/plant-litter derived DOM based on atomic ratios associated with specific biogenic precursors (i.e., lignin, tannins, and/or oxygenated aromatic DOM), particularly in winter when autochthonous production was suppressed due to reduced temperatures. We further demonstrate that the damming effects of artificial reservoirs enhance the role of seasonal patterns of autochthonous production, disrupting storm-shunt process and stimulating significantly more bio-produced DOM export during spring and summer (i.e., tryptophan/tyrosine-like. N- and S- containing, phytoplankton-derived compounds). Collectively, these results demonstrate how artificial reservoirs alter the characteristics of DOM exported from rivers with implications for understanding carbon export and fate at river-estuary interfaces.

Molecular composition and characteristics of Sediment-adsorbed Dissolved Organic Matter (SDOM) along the coast of China

Sediment-adsorbed Dissolved Organic Matter (SDOM) in coast plays a crucial role in the terrestrial and marine carbon cycle processes of the global environment. However, understanding the transport dynamics of SDOM along the coast of China, particularly its interactions with sediments, remains elusive. In this study, we analyzed the δ13C and δ15N stable isotopic compositions, as well as the molecular characteristics of SDOM collected from coastal areas spanning the Bohai Sea (BS), Yellow Sea (YS), East China Sea (ECS), and South China Sea (SCS), by using isotope ratio mass spectrometry and Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS). We identified the predominant sources of carbon and nitrogen in coastal sediments, revealing terrigenous origins for most C and N, while anthropogenic sources dominated in the SCS. Spatial variations in SDOM chemodiversity were observed, with diverse molecular components influenced by distinct environmental factors and sediment sources. Notably, lignins and saturated compounds (such as proteins/amino sugars) were the predominant molecular compounds detected in coastal SDOM. Through Mantel tests and Spearman's correlation analysis, we elucidated the significant influence of spatial environmental factors (temperature, DO, salinity, and depth) and sediment sources on SDOM molecular chemodiversity. These findings contribute to a more comprehensive understanding of the carbon cycle dynamics along the Chinese coast.

Warming Leads to Changes in Soil Organic Carbon Molecules Due to Decreased Mineral Protection.

Climate change affects the content and composition of soil organic carbon (SOC). However, warming-induced changes in the SOC compounds remain unknown. Using nuclear magnetic resonance spectroscopy, molecular mixing models, and Fourier transform ion cyclotron resonance mass spectrometry, we analyzed the variations and relationships in molecular compounds in Mollisol with 10-56 g C kg-1 soil-1 by translocating soils under six climate regimes. We found that increased temperature and precipitation were negatively correlated with carbohydrate versus lipid and lignin versus protein. The former was consistent across soils with varying SOC contents, but the latter decreased as the SOC content increased. The carbohydrate-lipid correlations were related to dithionite-citrate-extractable Fe, while the lignin-protein correlations were linked to changes in moisture and pyrophosphate-extractable Fe/Al. Our findings indicate that the reduction in the mineral protection of SOC is associated with molecular alterations in SOC under warming conditions.

Photochemical evolution of the molecular composition of dissolved organic carbon and dissolved brown carbon from wood smoldering

Recently, extreme wildfires occur frequently around the world and emit substantial brown carbon (BrC) into the atmosphere, whereas the molecular compositions and photochemical evolution of BrC remain poorly understood. In this work, primary smoke aerosols were generated from wood smoldering, and secondary smoke aerosols were formed by the OH radical photooxidation in an oxidation flow reactor, where both primary and secondary smoke samples were collected on filters. After solvent extraction of filter samples, the molecular composition of dissolved organic carbon (DOC) was determined by Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS). The molecular composition of dissolved BrC was obtained based on the constraints of DOC formulae. The proportion of dissolved BrC fractions accounted for approximately 1/3–1/2 molecular formulae of DOC. The molecular characteristics of dissolved BrC showed higher levels of carbon oxidation state, double bond equivalents, and modified aromaticity index than those of DOC, indicating that dissolved BrC fractions were a class of organic structures with relatively higher oxidation state, unsaturated and aromatic degree in DOC fractions. The comparative analysis suggested that aliphatic and olefinic structures dominated DOC fractions (contributing to 70.1%-76.9%), while olefinic, aromatic, and condensed aromatic structures dominated dissolved BrC fractions (contributing to 97.5%-99.9%). It is worth noting that dissolved BrC fractions only contained carboxylic-rich alicyclic molecules (CRAMs)-like structures, unsaturated hydrocarbons, aromatic structures, and highly oxygenated compounds. CRAMs-like structures were the most abundant species in both DOC and dissolved BrC fractions. Nevertheless, the specific molecular characteristics for DOC and dissolved BrC fractions varied with subgroups after aging. The results highlight the similarities and differences in the molecular compositions and characteristics of DOC and dissolved BrC fractions with aging. This work will provide insights into understanding the molecular composition of DOC and dissolved BrC in smoke.

Insights into the transformation of natural organic matter during UV/peroxydisulfate treatment by FT-ICR MS and machine learning: Non-negligible formation of organosulfates

Natural organic matter (NOM) is a major sink of radicals in advanced oxidation processes (AOPs) and understanding the transformation of NOM is important in water treatment. By using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) in conjunction with machine learning, we comprehensively investigated the reactivity and transformation of NOM, and the formation of organosulfates during the UV/peroxydisulfate (PDS) process. After 60 min UV/PDS treatment, the CHO formula number and dissolved organic carbon concentration significantly decreased by 83.4 % and 74.8 %, respectively. Concurrently, the CHOS formula number increased substantially from 0.7 % to 20.5 %. Machine learning identifies DBE and AImod as the critical characteristics determining the reactivity of NOM during UV/PDS treatment. Furthermore, linkage analysis suggests that decarboxylation and dealkylation reactions are dominant transformation pathways, while the additions of SO3 and SO4 are also non-negligible. According to SHAP analysis, the m/z, number of oxygens, DBE and O/C of NOM were positively correlated with the formation of organosulfates in UV/PDS process. 92 organosulfates were screened out by precursor ion scan of HPLC-MS/MS and verified by UPLC-Q-TOF-MS, among which, 7 organosufates were quantified by authentic standards with the highest concentrations ranging from 2.1 to 203.0 ng L‒1. In addition, the cytotoxicity of NOM to Chinese Hamster Ovary (CHO) cells increased by 13.8 % after 30 min UV/PDS treatment, likely responsible for the formation of organosulfates. This is the first study to employ FT-ICR MS combined with machine learning to identify the dominant NOM properties affecting its reactivity and confirmed the formation of organosulfates from sulfate radical oxidation of NOM.

Comparison on molecular transformation of dissolved organic matter during Fenton and activated carbon adsorption processes for chemical cleaning wastewater treatment

This study employed Fenton oxidation and powdered activated carbon (PAC) adsorption processes for the removal of recalcitrant dissolved organic matter (DOM) in chemical cleaning wastewater (CCW) to meet discharge standards. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was used to identify resistant compounds and investigate the transformation characteristics of DOM. CCW mainly contained surfactant exhibiting heteroatom-rich characteristics, and both processes exhibited effective DOM removal but distinct selectivity towards different subclasses of formulas. PAC adsorption significantly decreased the number of DOM compounds and more effective in aromatic compounds than Fenton oxidation. The aliphatic compounds (AImod ≤ 0.5, 1.5 ≤ H/C ≤ 2.0) predominantly with saturated and reduced states were resistant to PAC adsorption, and particularly a specific CHONSP formula was the predominant contributor to residual DOM in the effluent. In contrast, Fenton oxidation degraded most substances in the CCW except for a few saturated and reduced compounds primarily consisting of CHO, resulting in an increase in DOM number. Two unsaturated subclasses, carboxylic-rich alicyclic molecules/lignin-like structures (primarily CHON) and carbohydrates (primarily CHONP and CHONSP), were prominently produced after Fenton oxidation. The major mechanisms governing Fenton oxidation of surfactant in CCW primarily involved dealkylation (25.2 %), oxygen addition (21.2 %), and decarboxylation (19.8 %). Given the unique removal preferences and resistance observed in Fenton and PAC processes, a combination approach could be explored in the future to achieve advanced overall performance.

Characteristics of DOM and Their Relationships with Potentially Toxic Elements in the Inner Mongolia Section of the Yellow River, China.

The characterization of dissolved organic matter (DOM) is important for better understanding of the migration and transformation mechanisms of DOM in water bodies and its interaction with other contaminants. In this work, fluorescence characteristics and molecular compositions of the DOM samples collected from the mainstream, tributary, and sewage outfall of the Inner Mongolia section of the Yellow River (IMYR) were determined by using fluorescence spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). In addition, concentrations of potentially toxic elements (PTEs) in the relevant surface water and their potential relationships with DOM were investigated. The results showed that the abundance of tyrosine-like components increased significantly in downstream waters impacted by outfall effluents and was negatively correlated with the humification index (HIX). Compared to the mainstream, outfall and tributaries have a high number of molecular formulas and a higher proportion of CHOS molecular formulas. In particular, the O5S class has a relative intensity of 41.6% and the O5-7S class has more than 70%. Thirty-eight PTEs were measured in the surface water samples, and 12 found above their detective levels at all sampling sites. Protein-like components are positively correlated with Cu, which is likely indicating the source of Cu in the aquatic environment of the IMYR. Our results demonstrated that urban wastewater discharges significantly alter characteristics and compositions of DOM in the mainstream of IMYR with strongly anthropogenic features. These results and conclusions are important for understanding the role and sources of DOM in the Yellow River aquatic environment.

Analysis of the microstructure of high viscosity components in Tahe ultra heavy oil based on the combination of ESI (±) FT-ICR/MS

In addressing the challenge of high viscosity in Xinjiang Tahe heavy oil, crucial for optimizing extraction processes, this study focuses on identifying and analyzing the microstructure of key components influencing oil viscosity. The aim is to uncover the underlying reasons for its high viscosity and guide research towards effective viscosity reduction techniques. Electrospray ionization (ESI) combined with fourier transform ion cyclotron resonance mass spectrometry (FT-ICR/MS) characterizes the molecular-level constituents contributing to oil viscosity. The investigation covers the composition and distribution of oxygen-containing, nitrogen-containing, and organometallic compounds, developing a molecular structure model for these critical viscosity-inducing components. Findings reveal Xinjiang Tahe extra heavy oil as a solid mass at room temperature, with significant viscosity reduction observed post-deasphalting, highlighting asphaltenes' pivotal role in viscosity. Analysis indicates a higher content of metal elements (such as V and Ni) in asphaltenes compared to the crude oil itself, with an abundance of porphyrin structures in asphaltenes markedly influencing oil viscosity. Cyclic, aromatic, and unsaturated compound structures are predominantly found in the asphaltenes of heavy oil. Through combined ESI (±) FT-ICR/MS analysis, the crude oil is determined to mainly comprise acidic compounds, non-basic nitrogen compounds, and basic nitrogen compounds, offering significant insight into heavy oil's complex chemical composition. Specifically, non-basic nitrogen compounds in Tahe crude oil, including alkylcarbazoles, alkylbenzocarbazoles, and alkylpolybenzocarbazoles, are identified as key components, with molecular carbon numbers ranging from C12 to C56 and a predominance near C27. Additionally, asphaltenes in Tahe heavy oil exhibit a higher double bond equivalence (DBE) than the crude oil, indicating a greater degree of condensation with an increased number of double bonds and heterocyclic structures. The significant difference in DBE values between asphaltenes and crude oil underscores their impact on viscosity. A detailed molecular structure model of the asphaltenes in Tahe extra heavy oil has been constructed based on FT-ICR/MS analysis, providing a foundational understanding for developing viscosity reduction strategies.

Effects of straw returning on photochemical process and imidacloprid degradation in paddy water through a field experiment

Straw returning is an important strategy for effectively using straw resources to improve soil fertility and quality, but the effects of this process on reactive intermediates (RIs) formation in paddy water are not fully explored. In this study, we conducted a field experiment to explore the effects of straw returning on RIs formation including triplet chromophoric dissolved organic matter (3CDOM*), hydroxyl radicals (•OH), and singlet oxygen (1O2) in paddy water. It was found that straw returning considerably increased the steady-state concentration of RIs, and the application of rice straw with 25% and 75% organic replacement ratio increased RIs concentration by 2.52 and 2.25 times, respectively. The optical spectroscopy, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) analysis and structural equation model showed that straw returning produces abundant humified and aromatic DOM containing fulvic acid, lignin and protein-like substances, which could induce more RIs under irradiation. In addition, straw returning significantly accelerated imidacloprid (IMD) degradation, yielding degradation products that were highly toxic to aquatic animals (i.e., fish and daphnia) but less toxic to aquatic plants (i.e., green algae). This study would offer an innovative viewpoint on the effects of straw returning on the photochemistry of paddy water and the naturally occurring abiotic degradation pathway of organic contaminants.

Continuous planting of Chinese fir monocultures significantly influences dissolved organic matter content and microbial assembly processes

Monoculture plantations in China, characterized by the continuous cultivation of a single species, pose challenges to timber accumulation and understory biodiversity, raising concerns about sustainability. This study investigated the impact of continuous monoculture plantings of Chinese fir (Cunninghamia lanceolata [Lamb.] Hook.) on soil properties, dissolved organic matter (DOM), and microorganisms over multiple generations. Soil samples from first to fourth-generation plantations were analyzed for basic chemical properties, DOM composition using Fourier transform ion cyclotron resonance mass spectrometry, and microorganisms via high-throughput sequencing. Results revealed a significant decline in nitrate nitrogen content with successive rotations, accompanied by an increase in easily degradable compounds like carbohydrates, aliphatic/proteins, tannins, Carbon, Hydrogen, Oxygen and Nitrogen- (CHON) and Carbon, Hydrogen, Oxygen and Sulfur- (CHOS) containing compounds. However, the recalcitrant compounds, such as lignin and carboxyl-rich alicyclic molecules (CRAMs), condensed aromatics and Carbon, Hydrogen and Oxygen- (CHO) containing compounds decreased. Microorganism diversity, abundance, and structure decreased with successive plantations, affecting the ecological niche breadth of fungal communities. Bacterial communities were strongly influenced by DOM composition, particularly lignin/CRAMs and tannins. Continuous monoculture led to reduced soil nitrate, lignin/CRAMs, and compromised soil quality, altering chemical properties and DOM composition, influencing microbial community assembly. This shift increased easily degraded DOM, accelerating soil carbon and nitrogen cycling, ultimately reducing soil carbon sequestration. From environmental point of view, the study emphasizes the importance of sustainable soil management practices in continuous monoculture systems. Particularly the findings offer valuable insights for addressing challenges associated with monoculture plantations and promoting long-term ecological sustainability.

Structure and composition of dissolved organic matters in sludge by ultrasonic treatment

The leaching of dissolved organic matter (DOM) from the sludge into the liquid phase is induced by ultrasound. However, there is limited investigation into the structure and molecular composition of sludge DOM in this process. The molecular structure and composition of sludge DOM in ultrasonic treatment were comprehensively elucidated in this study. The sludge dissolved organic carbon (DOC) and three-dimensional fluorescence spectroscopy (3D-EEM) image had most significant change at 15-min ultrasonic time and 1.2 W/mL ultrasonic density, respectively. Gas Chromatography-Mass Spectrometry (GC-MS) analysis indicated that ultrasonic treatment of sludge reduced the macromolecules to small molecules in DOM. Then, electrospray ionization Fourier-transform ion cyclotron resonance mass spectrometry (ESI FT-ICR-MS) analysis revealed that lignin, tannins, and carbohydrates were the main components of sludge DOMs after ultrasound treatment. analysis revealed that lignin, tannins, and carbohydrates were the main components of sludge DOMs after ultrasound treatment. Furthermore, through the Van Krevelen analysis, the major components were CHO (48.50%) and CHOS (23.20%) in the DOM of ultrasonicated sludge. This research provides the basis for the practical application of ultrasonic treatment of sludge and provides basic information for DOM components.

The complex composition of organic aerosols emitted during burning varies between Arctic and boreal peat

AbstractPeatlands in the northern hemisphere are a major carbon storage but face an increased risk of wildfires due to climate change leading to large-scale smoldering fires in boreal and Arctic peatlands. Smoldering fires release organic carbon rich particulate matter, which influences the earth’s radiative balance and can cause adverse health effects for humans. Here we characterize the molecular composition of biomass burning particulate matter generated by laboratory burning experiments of peat by electrospray ionization 21 T Fourier-transform ion cyclotron resonance mass spectrometry, revealing a highly complex mixture of aromatic and aliphatic organic compounds with abundant heteroatoms including oxygen, sulfur and up to five nitrogen atoms. Primary organosulfur species are identified in the emissions of peat-smoldering, in part also containing nitrogen. Differences are observed when comparing structural motifs as well as the chemical composition of boreal and Arctic peat burning emissions, with the latter containing compounds with more nitrogen and sulfur.

Using CuMgFe layered double oxide to replace laccase as a catalyst for abiotic humification

Humification offers a promising avenue for sequestering dissolved organic carbon while facilitating environmental cleanup. In this study, CuMgFe layered double oxides (LDO) were applied as a catalyst to replace conventional enzymes, such as laccase, thereby enhancing the in vitro polyphenol-Maillard humification reaction. CuMgFe LDO was synthesized through calcination of CuMgFe layered double hydroxides (LDH) at 500 °C for 5 h. A suite of characterization methods confirmed the successful formation into mixed oxides (Cu2O, CuO, MgO, FeO, and Fe2O3) after thermal treatment. A rapid humification reaction was observed with CuMgFe LDO, occurring within a two-week span, likely due to a distinct synergy between copper and iron elements. Subsequent analyses identified that MgO in CuMgFe LDO also played a pivotal role in humification by stabilizing the pH of the reaction. In the absence of magnesium, LDO's humification activity was more pronounced in the early stages of the reaction, but it rapidly diminished as the reaction progressed. The efficiency of CuMgFe LDO was heightened at elevated temperatures (35 °C), while light conditions manifested a discernible effect, with a modest decrease in humification efficacy under indoor light exposure. CuMgFe LDO surpassed both laccase and MgFe LDH in performance, boasting a superior humification efficiency relative to its precursor, CuMgFe LDH. The catalysts' humification activity was modulated by their crystallinity and valence dynamics. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) results suggested that introducing the amino acid, glycine, expedited the CuMgFe LDO-fueled humification, enhancing the formation of C–N and C–C bonds in the resultant products. The humic-like substances derived from the catalyst-enhanced reaction displayed an elevated presence of aromatic configurations and a richer array of oxygen functional groups in comparison to a typical commercial humic material.

Unraveling the characteristics of dissolved organic matter removed by aluminum species based on FT-ICR MS analysis

Given the complexity of dissolved organic matter (DOM) and its interactions with coagulant chemicals, the mechanisms of DOM removal by aluminum (Al) coagulants remains a significant unknown. In this study, six test waters containing DOM with molecular weight (MW, <1 kDa, 1–10 kDa and >10 kDa) and hydrophobicity (hydrophilic, transphilic and hydrophobic) were prepared and coagulated with Al0, Al13 and Al30. The molecular-level characteristics of DOM molecules that were removed or resistant to removal by Al species were analyzed using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). The results showed that at the molecular level, saturated and reduced tannins and lignin-like compounds containing abundant carboxyl groups exhibited higher coagulation efficiency. Unsaturated and oxidized lipids, protein-like, and carbohydrates compounds were relatively resistant to Al coagulation due to their higher polarity and lower content of carboxyl groups. Al13 removed molecules across a wider range of molecular weights than Al0 and Al30, thus the DOC removal efficiency of Al13 was the highest. This study furthers the understanding of interactions between Al species and DOM, and provides scientific insights on the operation of water treatment plants to improve control of DOM.