The bioavailability and degradation of riverine dissolved organic matter (DOM) play crucial roles in greenhouse gas emissions; however, studies on the kinetic decomposition of fluvial DOM remain scarce. In this study, the decomposition kinetics of dissolved organic carbon (DOC) were characterized using the reactivity continuum model through 28-day bio-incubation experiments with water samples from the Yangtze River. The relationship between DOM composition and decomposition kinetics was analyzed using optical and molecular characterization combined with apparent decay coefficients. Our results revealed that DOM compounds rich in nitrogen and sulfur were predominantly removed, exhibiting a transition from an unsaturated to a saturated state following microbial degradation. These heteroatomic compounds, which constituted 75.61 % of the DOM compounds positively correlated with the decay coefficient k0, underwent preferential degradation in the early stages of bio-incubation due to their higher bioavailability. Additionally, we observed that S-containing fractions with high molecular weight values (MW > 400 Da) may be associated with larger reactivity grades. This study underscored the complex interplay between DOM composition and its kinetic decomposition in river ecosystems, providing further support for the significance of molecular composition in large river DOM as crucial factors affecting decomposition.

The brewing-dependent molecular diversity, properties, and formation mechanism of Moutai (a typical sauce-flavor Baijiu) base Baijiu, were explored using FT-ICR MS combined with various visualization methods. Seven-round Moutai base Baijiu exhibited significant diversity and heterogeneity, containing more unsaturated/saturated reduced molecules. The increased brewing round increased the molecular unsaturation/aromaticity and enhanced the transformation between saturated/oxidized and unsaturated/reduced molecules. Moreover, lignin-/aliphatic-/peptide-/lipid-like molecules dominated the molecular characteristics of Moutai base Baijiu. The basic and acidic components contained more reduced carbohydrate-/lipid-like molecules and oxidized tannin-like/condensed aromatic molecules, respectively, contributing to the molecular stability and diversity, respectively. More unique lipid-like and lignin-like molecules newly formed in the early and late brewing rounds, respectively, and the increased brewing shifted the chemical reaction from a single dominant to a multi-dimensional balance. More unique N-containing molecules (>450 Da) significantly contributed the specific brewing characteristics. These new findings help to understand the molecular-level formation mechanism of Moutai base Baijiu.

Dissolved organic matter (DOM) plays a critical role in driving the development of biogeochemical functions in revegetated metal smelting slag sites, laying a fundamental basis for their sustainable rehabilitation. However, the DOM composition at the molecular level and its interaction with the microbial community in such sites undergoing long-term direct revegetation remain poorly understood. This study investigated the chemodiversity of DOM and its association with the bacterial community in the rhizosphere and non-rhizosphere slags of four plant species (Arundo donax, Broussonetia papyrifera, Cryptomeria fortunei, and Robinia pseudoacacia) planted at a zinc smelting slag site for 10 years. The results indicated that the relative abundance of lipids decreased from 18 % to 5 %, while the relative abundance of tannins and lignins/CRAM-like substances increased from 4 % to 10 % and from 44 % to 64 % in the revegetated slags, respectively. The chemical stability of the organic matter in the rhizosphere slag increased due to the retention of recalcitrant DOM components, such as lignins, aromatics, and tannins. As the diversity and relative abundance of the bacterial community increased, particularly within the Proteobacteria, there was better utilization of recalcitrant components (e.g., lignins/CRAM-like compounds), but this utilization was not invariable. In addition, potential preference associations between specific bacterial OTUs and DOM molecules were observed, possibly stimulated by heavy metal bioavailability. Network analysis revealed complex connectivity and strong interactions between the bacterial community and DOM molecules. These specific interactions between DOM molecules and the bacterial community enable adaptation to the harsh conditions of the slag environment. Overall, these findings provide novel insights into the transformation of DOM chemodiversity at the molecular level at a zinc smelting slag sites undergoing long-term revegetation. This knowledge could serve as a crucial foundation for developing direct revegetation strategies for the sustainable rehabilitation of metal smelting slag sites.

Land use and precipitation are two major factors affecting phosphorus (P) pollution of watershed runoff. However, molecular characterization of dissolved organic phosphorus (DOP) in runoff under the joint influences of land use and precipitation remains limited. This study used Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) to study the molecular characteristics of DOP in a typical P-polluted watershed with spatially variable land use and precipitation. The results showed that low precipitation and intense human activity, including phosphate mining and associated industries, resulted in the accumulation of aliphatic DOP compounds in the upper reaches, characterized by low aromaticity and low biological stability. Higher precipitation and widespread agriculture in the middle and lower reaches resulted in highly unsaturated DOP compounds with high biological stability constituting a higher proportion, compared to in the upper reaches. While, under similar precipitation, more aliphatic DOP compounds characterized by lower aromaticity and higher saturation were enriched in the lower reaches due to more influence from urban runoff relative to the middle reaches. Photochemical and/or microbial processes did result in changes in the characteristics of DOP compounds during runoff processes due to the prevalence of low molecular weight and low O/C bioavailable aliphatic DOP molecules in the upper reaches, which were increasingly transformed into refractory compounds from the upper to middle reaches. The results of this study can increase the understanding of the joint impacts of land use and precipitation on DOP compounds in watershed runoff.

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.

Metal ions are liable to form metal-dissolved organic matter [dissolved organic matter (DOM)] complexes, changing the chemistry and chlorine reactivity of DOM. Herein, the impacts of iron and zinc ions (Fe3+ and Zn2+) on the formation of unknown chlorinated disinfection byproducts (Cl-DBPs) were investigated in a chlorination system. Fe3+ preferentially complexed with hydroxyl and carboxyl functional groups, while Zn2+ favored the amine functional groups in DOM. As a consequence, electron-rich reaction centers were created by the C-O-metal bonding bridge, which facilitated the electrophilic attack of α-C in metal-DOM complexes. Size-reactivity continuum networks were constructed in the chlorination system, revealing that highly aromatic small molecules were generated during the oxidation and decarbonization of metal-DOM complexes. Molecular transformation related to C-R (R represents complex sites) loss was promoted via metal complexation, including decarboxylation and deamination. Consequently, complexation with Fe3+ and Zn2+ promoted hydroxylation by the C-O-metal bonding bridge, thereby increasing the abundances of unknown polychlorinated Cl-DBPs by 9.6 and 14.2%, respectively. The study provides new insights into the regulation of DOM chemistry and chlorine reactivity by metal ions in chlorination systems, emphasizing that metals increase the potential health risks of drinking water and more scientific control standards for metals are needed.

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.

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.

Global land-use changes alter the delivery of fluvial dissolved organic matter (DOM) along land-to-sea continuum. To study how spatial variations in watershed anthropogenic disturbances control chemodiversity and reactivity of DOM exported to oceans, we used fluorescent and ultra-high-resolution mass spectrometry to investigate spatial and seasonal variations of DOM properties along two subtropical coastal rivers with contrasting anthropogenic land-use distributions (North and West tributaries of Jiulong River, southeast China). Dissolved organic carbon (DOC) concentration and humic- and protein-like fluorescent DOM (FDOM) intensities were high in the mixed urban-agricultural impacted upper North River and lower West River. DOM molecular signatures suggested that the urban-sourced DOM is dominated by bio-labile, S-rich compounds, whereas the agricultural-sourced DOM is characterized by a mixture of bio-labile CHONS and bio-refractory CHON. This anthropogenic-induced spatial variation in DOM signatures was especially prominent during the dry season. Molecular analysis indicated that heteroatomic-containing (phosphorus-sulfur-nitrogen) DOM compounds are more biologically degradable, whereas most of the heteroatom-depleted and highly unsaturated CHO was stable during transport. Due to a longer transit distance and reservoir impoundment in North River, the urban-sourced aliphatic compounds were largely microbially removed or transformed into bio-refractory components, resulting in lower DOC fluxes and an increase of recalcitrance in the DOM exported to the ocean. Conversely, shorter transit times for anthropogenic inputs from the middle/lower West River increased watershed yield and export fluxes of DOC with higher bio-lability. Our study documents that transit history plays a crucial role in assessing the fate of anthropogenic DOM along the land-to-ocean continuum.

The entero-mammary pathway is a specialized route that selectively translocates bacteria to the newborn\'s gut, playing a crucial role in neonatal development. Previous studies report shared bacterial and archaeal taxa between human milk and neonatal intestine. However, the functional implications for neonatal development are not fully understood due to limited evidence. This study aimed to identify and characterize the microbiota and metabolome of human milk, mother, and infant stool samples using high-throughput DNA sequencing and FT-ICR MS methodology at delivery and 4 months post-partum. Twenty-one mothers and twenty-five infants were included in this study. Our results on bacterial composition suggest vertical transmission of bacteria through breastfeeding, with major changes occurring during the first 4 months of life. Metabolite chemical characterization sheds light on the growing complexity of the metabolites. Further data integration and network analysis disclosed the interactions between different bacteria and metabolites in the biological system as well as possible unknown pathways. Our findings suggest a shared bacteriome in breastfed mother-neonate pairs, influenced by maternal lifestyle and delivery conditions, serving as probiotic agents in infants for their healthy development. Also, the presence of food biomarkers in infants suggests their origin from breast milk, implying selective vertical transmission of these features.