New insights into the influences of firework combustion on molecular composition and formation of sulfur- and halogen-containing organic compounds.

Firework (FW) events occur during various festivals worldwide and substantially negatively influence both air quality and human health. However, the effects of FWs on the chemical properties and formation of organic aerosols are far from clear. In this study, fine particulate matter (PM2.5) samples were collected in a suburban area in Qingdao, China during the Chinese Spring Festival. The concentrations of chemical species (especially carbonaceous components) in PM2.5 were measured using a combination of several state-of-the-art techniques. Our results showed that mass concentrations of water-soluble sulfate, potassium and chloride ions, and organic carbon drastically increased and became the predominant components in PM2.5 during FW events. Correspondingly, both the number and fractional contributions of sulfur (S)-containing subgroups (e.g., CHOS and CHONS compounds) and some chlorine (Cl)-containing organic (e.g., CHOSCl and CHONSCl) compounds identified using ultrahigh-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) increased. The S- and Cl-containing compounds unique to the FW display period were identified, and their chemical characterization, sources, and formation mechanisms were elucidated by combining FT-ICR MS and quantum chemical calculations. Our results suggest that FW emissions play notable roles in both primary and secondary organic aerosol formation, especially for CHOS- and Cl-containing organic compounds.

Hidden Role of Organic Matter in the Immobilization and Transformation of Iodine on Fe-OM Associations.

The biogeochemical processes of iodine are typically coupled with organic matter (OM) and the dynamic transformation of iron (Fe) minerals in aquifer systems, which are further regulated by the association of OM with Fe minerals. However, the roles of OM in the mobility of iodine on Fe-OM associations remain poorly understood. Based on batch adsorption experiments and subsequent solid-phase characterization, we delved into the immobilization and transformation of iodate and iodide on Fe-OM associations with different C/Fe ratios under anaerobic conditions. The results indicated that the Fe-OM associations with a higher C/Fe ratio (=1) exhibited greater capacity for immobilizing iodine (∼60-80% for iodate), which was attributed to the higher affinity of iodine to OM and the significantly decreased extent of Fe(II)-catalyzed transformation caused by associated OM. The organic compounds abundant in oxygen with high unsaturation were more preferentially associated with ferrihydrite than those with poor oxygen and low unsaturation; thus, the associated OM was capable of binding with 28.1-45.4% of reactive iodine. At comparable C/Fe ratios, the mobilization of iodine and aromatic organic compounds was more susceptible in the adsorption complexes compared to the coprecipitates. These new findings contribute to a deeper understanding of iodine cycling that is controlled by Fe-OM associations in anaerobic environments.

Activated Carbon Application Simultaneously Alleviates Paddy Soil Arsenic Mobilization and Carbon Emission by Decreasing Porewater Dissolved Organic Matter.

Flooding of paddy fields during the rice growing season enhances arsenic (As) mobilization and greenhouse gas (e.g., methane) emissions. In this study, an adsorbent for dissolved organic matter (DOM), namely, activated carbon (AC), was applied to an arsenic-contaminated paddy soil. The capacity for simultaneously alleviating soil carbon emissions and As accumulation in rice grains was explored. Soil microcosm incubations and 2-year pot experimental results indicated that AC amendment significantly decreased porewater DOM, Fe(III) reduction/Fe2+ release, and As release. More importantly, soil carbon dioxide and methane emissions were mitigated in anoxic microcosm incubations. Porewater DOM of pot experiments mainly consisted of humic-like fluorophores with a molecular structure of lignins and tannins, which could mediate microbial reduction of Fe(III) (oxyhydr)oxides. Soil microcosm incubation experiments cospiking with a carbon source and AC further consolidated that DOM electron shuttling and microbial carbon source functions were crucial for soil Fe(III) reduction, thus driving paddy soil As release and carbon emission. Additionally, the application of AC alleviated rice grain dimethylarsenate accumulation over 2 years. Our results highlight the importance of microbial extracellular electron transfer in driving paddy soil anaerobic respiration and decreasing porewater DOM in simultaneously remediating As contamination and mitigating methane emission in paddy fields.

Enrichment of Geogenic Organoiodine Compounds in Alluvial-Lacustrine Aquifers: Molecular Constraints by Organic Matter.

Organoiodine compounds (OICs) are the dominant iodine species in groundwater systems. However, molecular mechanisms underlying the geochemical formation of geogenic OICs-contaminated groundwater remain unclear. Based upon multitarget field monitoring in combination with ultrahigh-resolution molecular characterization of organic components for alluvial-lacustrine aquifers, we identified a total of 939 OICs in groundwater under reducing and circumneutral pH conditions. In comparison to those in water-soluble organic matter (WSOM) in sediments, the OICs in dissolved organic matter (DOM) in groundwater typically contain fewer polycyclic aromatics and polyphenol compounds but more highly unsaturated compounds. Consequently, there were two major sources of geogenic OICs in groundwater: the migration of the OICs from aquifer sediments and abiotic reduction of iodate coupled with DOM iodination under reducing conditions. DOM iodination occurs primarily through the incorporation of reactive iodine that is generated by iodate reduction into highly unsaturated compounds, preferably containing hydrophilic functional groups as binding sites. It leads to elevation of the concentration of the OICs up to 183 µg/L in groundwater. This research provides new insights into the constraints of DOM molecular composition on the mobilization and enrichment of OICs in alluvial-lacustrine aquifers and thus improves our understanding of the genesis of geogenic iodine-contaminated groundwater systems.

Formation of reactive intermediates in paddy water from different temperature zones for the promotion of abiotic ammonification.

The paddy field is a hot area of biogeochemical process. The paddy water has a large capacity in photo-generation of reactive intermediates (RIs) due to abundant photosensitive dissolved organic matter (DOM), which is influenced by the spatial heterogeneity of paddy soils but rarely been explored. Our work presents the first investigation of the role of soil properties on photochemistry in paddy water. Soil organic matter (SOM), determined by the temperature, was the dominant factor for the photo-generation of RIs in paddy water of main rice producing areas. The RI concentrations generated with abundant SOM from cool regions are 0.05-8.71 times higher than those for the warm regions in China. The humic-like substance and aromatic-like compounds of DOM plays an essential role in RIs generation, which is abundant in paddy soils rich in SOM from Chinese cool regions. In addition, RIs can efficiently accelerate the photo-ammonification of urea and free amino acids by 15.2 %-164 %, leading to 0.13-0.17 mmol/L/d photo-produced ammonium after fertilization, which is preferentially absorbed by rice. The findings of this study will extend our knowledge of the geochemistry of global paddy field ecosystem. The potential role of RIs in nitrogen cycle should be highlighted in the agroecosystem.

FT-ICR MS Spectral Improvement of Dissolved Organic Matter by the Absorption Mode: A Comparison of the Electrospray Ionization in Positive-Ion and Negative-Ion Modes.

Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) in the absorption mode has a superior performance over the conventional magnitude mode. However, this improved performance for the analysis of dissolved organic matter (DOM) in negative-ion and positive-ion modes of electrospray ionization [ESI(-) and ESI(+), respectively] remains unknown. This study systemically compared the improved performance by the absorption mode for DOM FT-ICR MS spectra acquired with the low-field and high-field magnet instruments between two charge modes. The absorption mode enhanced the resolution and signal-to-noise ratio values of DOM peaks with factors of 1.88-1.94 and 1.60-1.72, respectively. The significantly higher improvement of mass resolution for the ESI(+) mode than that for the ESI(-) mode could resolve the extensive occurrence of mass doublets in the ESI(+) mode, yielding some formulas exclusively identified in the ESI(+) mode. The findings of this study have systemically demonstrated the superiority of the absorption mode in improving the spectra quality during the routine FT-ICR MS postdata analysis and highlighted its great potential in characterizing the molecular composition of DOM using the FT-ICR MS technique in both ESI(-) and ESI(+) modes.

One-electron oxidant-induced transformation of dissolved organic matter: Optical and antioxidation properties and molecules.

Dissolved organic matter (DOM) is a major sink of radicals in advanced oxidation processes (AOPs) and the radical-induced DOM transformation influences the subsequent water treatment processes or receiving waters. In this study, we quantified and compared DOM transformation by tracking the changes of dissolved organic carbon (DOC), UVA254, and electron donating capacity (EDC) as functions of four one-electron oxidants (SO4•-, Cl2•-, Br2•-, and CO3•-) exposures as well as the changes of functional groups and molecule distribution. SO4•- had the highest DOC reduction while Cl2•- had the highest EDC reduction, which could be due to their preferential reaction pathways of decarboxylation and converting phenols to quinones, respectively. Br2•- and CO3•- induced less changes in DOC, UVA254, and EDC than SO4•- and Cl2•-. Additionally, DOM enriched with high aromatic contents tended to have higher DOC, UVA254, and EDC reductions. Decreases in hydroxyl and carboxyl groups and increases in carbonyl groups were observed in these four types of radicals treated DOM using Fourier transform infrared spectroscopy. High resolution mass spectrometry using FTICR-MS showed that one-electron oxidants preferred to attack unsaturated carbon skeletons and transformed into molecules featuring high saturation and low aromaticity. Moreover, SO4•- was inclined to decrease oxidation state of carbon and O/C of DOM due to its strong decarboxylation capacity. This study highlights the distinct DOM transformation by four one-electron oxidants and provides comprehensive insights into the reactions of one-electron oxidants with DOM.

Interpretable Machine Learning and Reactomics Assisted Isotopically Labeled FT-ICR-MS for Exploring the Reactivity and Transformation of Natural Organic Matter during Ultraviolet Photolysis.

Isotopically labeled FT-ICR-MS combined with multiple post-analyses, including interpretable machine learning (IML) and a paired mass distance (PMD) network, was employed to unravel the reactivity and transformation of natural organic matter (NOM) during ultraviolet (UV) irradiation. FT-ICR-MS analysis was used to assign formulas, which were classified on the basis of their molecular compositions and structural categories. Isotope (deuterium, D) labeling was utilized to unequivocally determine the photochemical products and examine the development of OD radical-mediated NOM transformation. With regard to the reactive molecular formulas, CHOS formulas exhibited the highest reactivity (86.5% of precursors disappeared) followed by CHON (53.4%) and CHO (24.6%) formulas. With regard to structural categories, the degree of reactivity decreased in the following order: tannins > condensed aromatics > lignin/CRAMs. The IML algorithm demonstrated that the crucial features governing the reactivity of formulas were the molecular weight, DBE-O, NOSC, and the presence of heteroatoms (i.e., N and S), suggesting that the large and unsaturated compounds containing S and N are more prone to photodegradation. The reactomics approach using the PMD network further indicated that 11 specific molecular formulas in the CHOS and CHO class served as hubs, implying a higher photoreactivity and participation in a range of transformations. The isotope labeling analyses also found that, among the reactions observed, hydroxylation (i.e., +OD) is dominant for lignin/CRAMs and condensed aromatics, and formulas containing ≤10 D atoms were developed. Overall, this study, by adopting rigorous and interpretable techniques, could provide in-depth insights into the molecular-level dynamics of NOM under UV irradiation.

Copper Safeguards Dissolved Organic Matter from Sunlight-Driven Photooxidation.

Sunlight plays a crucial role in the transformation of dissolved organic matter (DOM) and the associated carbon cycle in aquatic environments. This study demonstrates that the presence of nanomolar concentrations of copper (Cu) significantly decreases the rate of photobleaching and the rate of loss of electron-donating moieties of three selected types of DOM (including both terrestrial and microbially derived DOM) under simulated sunlight irradiation. Employing Fourier transform ion cyclotron resonance mass spectrometry, we further confirm that Cu selectively inhibits the photooxidation of lignin- and tannin-like phenolic moieties present within the DOM, in agreement with the reported inhibitory impact of Cu on the photooxidation of phenolic compounds. On the basis of the inhibitory impact of Cu on the DOM photobleaching rate, we calculate the contribution of phenolic moieties to DOM photobleaching to be at least 29-55% in the wavelength range of 220-460 nm. The inhibition of loss of electrons from DOM during irradiation in the presence of Cu is also explained quantitatively by developing a mathematical model describing hydrogen peroxide (a proxy measure of loss of electrons from DOM) formation on DOM irradiation in the absence and presence of Cu. Overall, this study advances our understanding of DOM transformation in natural sunlit waters.

Characterization of halogenated organic compounds by the Fourier transform ion cyclotron resonance mass spectrometry: A critical review.

Halogenated organic compounds (HOCs), widely present in various environments, are generally formed by natural processes (e.g., photochemical halogenation) and anthropogenic activities (e.g., water disinfection and anthropogenic discharge of HOCs), posing health and environmental risks. Therefore, in-depth knowledge of the molecular composition, transformation, and fate of HOCs is crucial to regulate and reduce their formation. Because of the extremely complex nature of HOCs and their precursors, the molecular composition of HOCs remains largely unknown. The Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) offers the most powerful resolution and mass accuracy for the simultaneous molecular-level characterization of HOCs and their precursors. However, there is still a paucity of reviews regarding the comprehensive characterization of HOCs by FT-ICR MS. Based on the FT-ICR MS, the formation mechanism, sample pretreatment, and analysis methods were summarized for two typical HOCs classes, namely halogenated disinfection byproducts and per- and polyfluoroalkyl substances in this review. Moreover, we have highlighted data analysis methods and some typical applications of HOCs using FT-ICR MS and proposed suggestions for current issues. This review will deepen our understanding of the chemical characterization of HOCs and their formation mechanisms and transformation at the molecular level in aquatic systems, facilitating the application of the state-of-the-art FT-ICR MS in environmental and geochemical research.

Spectral Quality Assessment Strategy Based on the 13C-Isotopic Pattern for the Fourier Transform Ion Cyclotron Resonance Mass Spectra of Dissolved Organic Matter.

The interpretation of data and optimization spectral acquisition of dissolved organic matter (DOM) by ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) have been challenging due to the varied instrument performances among laboratories and the complex chemical characteristics of DOM. However, a universal spectral optimization strategy for FT-ICR MS spectra is still unavailable. The results of this study showed that the number, intensity, and resolving power of all assigned peaks increased with the ion accumulation time (IAT) and DOM concentrations within a reasonable range. The space-charge effect induced by the excess ions in the ICR cell can deteriorate the data quality of the FT-ICR MS spectra, which could be inspected by examining the mass errors and intensity deviation of the monoisotopic and 13C-isotopic peaks based on the 13C-isotopic pattern. The maximum absolute mass error and 13C-isotopic pattern-based intensity deviation are two critical criteria for inspecting the space-charge effect, which was suggested to be 2.0 ppm and 20%, respectively. Therefore, a novel strategy based on the 13C-isotopic pattern has been proposed in this study to optimize the FT-ICR MS spectra of DOM based on their wide occurrence of monoisotopic and 13C-isotopic signals. This optimization strategy has laid the fundamentals for the method development of FT-ICR MS and could be extended to different FT-ICR MS instruments and various organic complex mixtures.

Conversion and impact of dissolved organic matters in a heterogeneous catalytic peroxymonosulfate system for pollutant degradation.

Dissolved organic matters (DOM) are widely present in different water sources, causing significant effects on water treatment processes. Herein, the molecular transformation behavior of DOM during peroxymonosulfate (PMS) activation by biochar for organic degradation in a secondary effluent were comprehensively analyzed. Evolution of DOM was identified and inhibition mechanisms to organic degradation were elucidated. DOM underwent oxidative decarbonization (e.g., -C2H2O, -C2H6, -CH2 and -CO2), dehydrogenation (-2H) and dehydration reactions by ·OH and SO4·-. N and S containing compounds witnessed deheteroatomisation (e.g., -NH, -NO2+H, -SO2, -SO3, -SH2), hydration (+H2O) and N/S oxidation reactions. Among DOM, CHO-, CHON-, CHOS-, CHOP- and CHONP-containing molecules showed moderate inhibition while condensed aromatic compounds and aminosugars exhibited strong and moderate inhibition effects on contaminant degradation. The fundamental information could provide references for the rational regulation of ROS composition and DOM conversion process in a PMS system. This in turn offered theoretical guidance to minimize the interference of DOM conversion intermediates on PMS activation and degradation of target pollutants.

Optical properties and molecular composition of wintertime atmospheric water-soluble organic carbon in different coastal cities of eastern China.

To evaluate the optical properties and molecular composition of water-soluble organic carbon (WSOC) in the atmosphere of coastal cities, particle samples were collected in Tianjin, Qingdao and Shanghai, three coastal cities in eastern China. Subsequent analysis by ultraviolet visible and fluorescence spectrometer and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry were performed. The results showed that the concentration levels and light absorption ability of WSOC decreased from the north to south cities, ranking as Tianjin > Qingdao > Shanghai. Three major fluorescent components including less­oxygenated humic-like substances (52-60 %), highly­oxygenated humic-like substances (15-31 %) and protein-like substances (17-31 %) were identified in WSOC based on the fluorescence spectroscopy and parallel factor analysis, which might be closely related to anthropogenic emissions and continental sources as well as secondary formation processes. Five subgroups of molecular components were further identified in WSOC, including the predominant CHON compounds (35-43 %), sulfur-containing compounds (i.e., CHONS and CHOS compounds, 24-43 %), CHO compounds (20-26 %) and halogen-containing compounds (1-7 %). Compared to marine air masses influenced samples, WSOC affected by continental air masses exhibited higher light absorption coefficients and generally had a higher degree of aromaticity and unsaturation, as well as contained more molecular formulas of WSOC, especially enriched with sulfur-containing compounds. In contrast, relatively more abundant halogen-containing compounds were identified in the marine air masses influenced samples. Overall, this study provided new insights into the light-absorbing and chemical properties of WSOC in coastal cities, especially under the influences of continental and marine air masses.

Evidence for nontraditional mcr-containing archaea contributing to biological methanogenesis in geothermal springs.

Recent discoveries of methyl-coenzyme M reductase-encoding genes (mcr) in uncultured archaea beyond traditional euryarchaeotal methanogens have reshaped our view of methanogenesis. However, whether any of these nontraditional archaea perform methanogenesis remains elusive. Here, we report field and microcosm experiments based on 13C-tracer labeling and genome-resolved metagenomics and metatranscriptomics, revealing that nontraditional archaea are predominant active methane producers in two geothermal springs. Archaeoglobales performed methanogenesis from methanol and may exhibit adaptability in using methylotrophic and hydrogenotrophic pathways based on temperature/substrate availability. A five-year field survey found Candidatus Nezhaarchaeota to be the predominant mcr-containing archaea inhabiting the springs; genomic inference and mcr expression under methanogenic conditions strongly suggested that this lineage mediated hydrogenotrophic methanogenesis in situ. Methanogenesis was temperature-sensitive , with a preference for methylotrophic over hydrogenotrophic pathways when incubation temperatures increased from 65° to 75°C. This study demonstrates an anoxic ecosystem wherein methanogenesis is primarily driven by archaea beyond known methanogens, highlighting diverse nontraditional mcr-containing archaea as previously unrecognized methane sources.

Spatial and molecular variations in forest topsoil dissolved organic matter as revealed by FT-ICR mass spectrometry.

Forest soils cover about 30 % of the Earth's land surface and play a fundamental role in the global cycle of organic matter. Dissolved organic matter (DOM), the largest active pool of terrestrial carbon, is essential for soil development, microbial metabolism and nutrient cycling. However, forest soil DOM is a highly complex mixture of tens of thousands of individual compounds, which is largely composed of organic matter from primary producers, residues from microbial process and the corresponding chemical reactions. Therefore, we need a detailed picture of molecular composition in forest soil, especially the pattern of large-scale spatial distribution, which can help us understand the role of DOM in the carbon cycle. To explore the spatial and molecular variations of DOM in forest soil, we choose six major forest reserves located in different latitudes ranging in China, which were investigated by Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS). Results show that aromatic-like molecules are preferentially enriched in DOM at high latitude forest soils, while aliphatic/peptide-like, carbohydrate-like, and unsaturated hydrocarbon molecules are preferentially enriched in DOM at low latitude forest soils, besides, lignin-like compounds account for the highest proportion in all forest soil DOM. High latitude forest soils have higher aromatic equivalents and aromatic indices than low latitude forest soils, which suggest that organic matter at higher latitude forest soils preferentially contain plant-derived ingredients and are refractory to degradation while microbially derived carbon is dominant in organic matter at low latitudes. Besides, we found that CHO and CHON compounds make up the majority in all forest soil samples. Finally, we visualized the complexity and diversity of soil organic matter molecules through network analysis. Our study provides a molecular-level understanding of forest soil organic matter at large scales, which may contribute to the conservation and utilization of forest resources.

New insights into the mechanism of phosphate release during particulate organic matter photodegradation based on optical and molecular signatures.

Phosphate release from particulate organic matter (POM) dominates phosphorus (P) cycling in aquatic ecosystems. However, the mechanisms underlying P release from POM remain poorly understood because of complex fractionation and analytical challenges. In this study, the release of dissolved inorganic phosphate (DIP) during POM photodegradation was assessed using excitation-emission matrix (EEM) fluorescence spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). POM in suspension was significantly photodegraded under light irradiation, concomitantly with the production and release of DIP in the aqueous solution. Chemical sequential extraction revealed that organic phosphorus (OP) in POM participated in photochemical reactions. Moreover, FT-ICR MS analysis revealed that the average molecular weight of P-containing formulas decreased from 374.2 to 340.1 Da. Formulas containing P with a lower oxidation degree and unsaturation were preferentially photodegraded, generating oxygen-enriched and saturated formula compounds, such as protein- and carbohydrate-like P-containing formulas, benefiting further utilization of P by organisms. Reactive oxygen species played an important role in the photodegradation of POM, and excited triplet state chromophoric dissolved organic matter (3CDOM*) was mainly responsible for POM photodegradation. These results provide new insights into the P biogeochemical cycle and POM photodegradation in aquatic ecosystems.

Complementary Elucidation of the Molecular Characteristics of Groundwater Dissolved Organic Matter Using Ultrahigh-Resolution Mass Spectrometry Coupled with Negative- and Positive-Ion Electrospray Ionization.

The formula assignment of the Fourier transform ion cyclotron resonance mass spectrometry coupled with positive-ion electrospray ionization [ESI(+)-FT-ICR MS] is challenging because of the extensive occurrence of adducts. However, there is a paucity of automated formula assignment methods for ESI(+)-FT-ICR MS spectra. The novel automated formula assignment algorithm for ESI(+)-FT-ICR MS spectra developed herein has been applied to elucidate the composition of dissolved organic matter (DOM) in groundwater during air-induced ferrous [Fe(II)] oxidation. The ESI(+)-FT-ICR MS spectra of groundwater DOM were profoundly impacted by [M + Na]+ adducts and, to a lesser extent, [M + K]+ adducts. Oxygen-poor and N-containing compounds were frequently detected when the FT-ICR MS was operated in the ESI(+) mode, while the components with higher carbon oxidation states were preferentially ionized in the negative-ion electrospray ionization [ESI(-)] mode. Values for the difference between double-bond equivalents and the number of oxygen atoms from -13 to 13 are proposed for the formula assignment of the ESI(+)-FT-ICR MS spectra of aquatic DOM. Furthermore, for the first time, the Fe(II)-mediated formation of highly toxic organic iodine species was reported in groundwater rich in Fe(II), iodide, and DOM. The results of this study not only shed light on the further algorithm development for comprehensive characterization of DOM by ESI(-)-FT-ICR MS and ESI(+)-FT-ICR MS but also highlight the importance of appropriate treatment of specific groundwater prior to use.

Overlooked impacts of natural organic matter conversion in a Fe(II)-induced peroxymonosulfate activation system for river water remediation.

The peroxymonosulfate (PMS) process may be hindered severely due to natural organic matter (NOM) conversion in the treatment of emerging pollutants from river water, becoming a critical engineering and technical issue. In this study, a Fe(II)-induced river water (RW)/PMS catalytic system was constructed for investigating molecular transformation of NOM and related influence mechanism to sulfamethoxazole (SMX) degradation. Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) analysis indicated that NOM molecules containing no more than one heteroatom in river may be attacked by hydroxyl radicals (OH) and then polymerized, converting into molecules with two or three heteroatoms during PMS oxidation. Based on the correlation analysis, CHONP-NOM, CHOSP-NOM and CHONSP-NOM showed a significant inhibition against SMX degradation, while CHONS-NOM exhibited a moderate inhibitory effect. Besides, more condensed aromatic structures, carbohydrates and tannins were generated via reactive species (OH and sulfate radicals (SO4-)) oxidation, radical addition and polymerization reactions. Notably, condensed aromatic structures, carbohydrates and tannins presented weak, modest and strong inhibition to SMX degradation, respectively. Based on the current results, the inhibition of target pollutants degradation would be mitigated via regulation of NOM molecules in a Fe(II)-induced PMS activation system, providing valuable information to reduce NOM impact. In addition, this study paves the way to achieve efficient removal of emerging pollutants from river water.

Molecular composition and chemodiversity of dissolved organic matter in wastewater sludge via Fourier transform ion cyclotron resonance mass spectrometry: Effects of extraction methods and electrospray ionization modes.

High-resolution mass spectrometry was extensively applied in molecular composition and transformation pathways of dissolved organic matter (DOM) in wastewater sludge treatments. Sample pretreatment methods and electrospray ionization (ESI) modes significant affect the accuracy of molecular characterization for DOM. This study investigated the effects of pretreatment methods (styrene divinyl benzene polymer (PPL), octadecyl (C18), and electrodialysis (ED)) on molecular characteristics of DOM in two typical wastewater sludges (waste activated sludge (WAS) and anaerobic digestion sludge (ADS)) analyzed by FT-ICR MS in both positive ESI (ESI (+)) and negative ESI (ESI (-)) modes. The results indicated that ED pretreatment exhibited the highest recovery rate of 70% ‒ 95% for sludge-derived DOM. ED and PPL performed well in recovering the different sludge-derived DOM with a high similarity of molecular characteristics (e.g., lipids, proteins/aliphatic, and lignins/CRAM-like), and the C18 method was ineffective in extracting carbohydrates, unsaturated hydrocarbons, and amino sugars. In addition, compared with single ESI (-) analysis mode, the molecular number identified by ESI (+) analysis mode was increased by 200%, especially, more unsaturated hydrocarbons and N-containing compounds were detected. Except for biogenic DOM, plenty of emerging containments (ECs) in sludge-derived DOM were identified; ESI (-) mode was more effectively in recognizing the alkyl benzene sulfonic acids (e.g., anionic surfactants); and ESI (+) mode was more effectively for plasticizers identification, for example, dioctyl terephthalate and dibutyl phthalate. This study illustrated that ED pretreatment coupled with FT-ICR MS in dual ESI modes could give more insights in complexed molecular information for DOM in wastewater sludge, and provides a theoretical basis for subsequent sludge treatments and disposals.

Biostimulants in dissolved organic matters recovered from anaerobic digestion sludge with alkali-hydrothermal treatment: Nontarget identification by ultrahigh-resolution mass spectrometry.

Recovering high-value biomaterials from anaerobic digestion sludge (ADS) has attracted considerable attention. However, the molecular features and biological effects of abundant dissolved organic matters (DOMs) in ADS are still unclear, which limits the efficient recycling and application of these bioproducts. This study investigated the molecular composition and transformation of DOMs recovered from ADS through a mild-temperature alkali-hydrothermal treatment (AHT) with ultrahigh-resolution mass spectrometry and energy spectroscopy, and the fertilizing effects of DOMs were evaluated by rice hydroponics. The results indicated that AHT processes significantly promoted the solubilization and release of DOMs from ADS, where most of DOMs molecules remained unchanged and mainly consisted of N-containing compounds with 1-3 N atoms, featuring aromatic or N-heterocyclic rings. Furthermore, AHT processes at pH of 9-10 induced the hydrolysis of partial protein-like substances in DOMs, which was accompanied by formation of heterocyclic-N compounds. Under AHT at pH of 11-12, protein-like and heterocyclic-N substances were increasingly decomposed into amino-N compounds containing 1 or 5 N atoms, while numerous oxygenated aromatic substances with phytotoxicity were degraded and removed from DOMs. Rice hydroponic test verified that ADS-derived DOMs recovered by AHT process at pH of 12 exhibited the highest bioactivity for rice growth, which was attributed to the abundance of amino compounds and humic substances. This study proposed a novel process for the recovery of high-quality liquid organic fertilizer from ADS through AHT process, which can further enrich the technical options available for the safe utilization of sludge resources.