Molecular characteristics of dissolved organic phosphorus in watershed runoff: Coupled influences of land use and precipitation.

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.

Revealing the backbone structures of land-based fulvic acids derived from river and soil through n-butylsilane reduction.

While ultra-high-resolution mass spectrometry has enabled the identification of the molecular composition of dissolved organic matter (DOM), elucidating its molecular structure remains a challenging endeavor. Here, two fulvic acids (FAs), one from river and the other from forest soil, were subjected to reduction using an optimized n-butylsilane (n-BS) reduction method. The reduction products were purified through a combination of liquid-liquid extraction and silica gel column chromatography, resulting in the separation into saturates, aromatics, and polar products. The polar products were analyzed by high-resolution mass spectrometry (HRMS), and the saturates and aromatics were analyzed using gas chromatography-mass spectrometry (GC-MS). HRMS results showed that the number of oxygen atoms and double-bond equivalent (DBE) values of FA decreased after reduction. GC-MS results revealed that a total of 270 hydrocarbon monomers were identified from the reduction products of a single sample, with the highest carbon number of cycloalkanes reaching C33. For the first time, steranes and hopanes were detected in the reduction products, potentially serving as evidence for the existence of carboxyl-rich alicyclic molecule (CRAM) precursors. Additionally, a significant number of polycyclic aromatic hydrocarbons were identified, and the potential sources of various compounds were preliminarily inferred based on their isomers. This study extends the knowledge of the possible backbone structure of the DOM and provides a new potential tool for investigating the origin and transformation mechanisms of DOM.

Characterization of sediment organic matter in the outer Yangtze River Estuary using stable isotopes, optical techniques, and FT-ICR-MS: Implications for the carbon burial mechanism.

The burial of sediment organic matter (SOM) in the estuary and shelf plays an important role in the global carbon cycle. However, it is challenging to determine the source, composition, and burial of SOM in the coastal sea, especially at the molecular level. This was explored in the coastal area outside the largest Yangtze River of China with multiple techniques including elemental and stable isotopic analysis, absorption spectroscopy, fluorescence excitation-emission matrices coupled with parallel factor analysis (EEMs-PARAFAC), and ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). The end-member mixing analysis based on δ13C and δ15N showed a dominance of marine contribution (up to 70%) at most stations while the terrestrial contribution increased to >55% nearshore in summer at a high fluvial sediment flux. This was consistent with the offshore decreasing humic-like C1 and C2, humification index (HIX), %lignin-like compounds, and %CHO but increasing tryptophan-like C3, biological index (BIX), %protein-like compounds, and %CHOS from EEMs-PARAFAC and FT-ICR-MS analysis. The %clay correlated positively with SOM content, HIX, %lignin-like compounds, O/C, and modified aromaticity index (AImod) but correlated negatively with %C3, H/C, and the relative abundance of labile formulas (MLBL), while %silt showed contrasting correlations. These results indicated the fine clay sediments adsorbed more humified, aromatic, oxygenated, and terrestrial compounds that were probably more resistant to biodegradation and thus had a higher burial efficiency than those on the silty sediments. Principal component analysis based on SOM indices further revealed different characteristics of SOM in the nearshore, northern offshore, and southern offshore regions, which were probably dependent on the delivery by local current systems. Overall, these findings contributed to unraveling the source and molecular composition of SOM associated with different grain size sediments and local current delivery, which are fundamental for understanding the factors underlying carbon burial in the complex coastal environment.

The high-resolution molecular portrait of coffee: A gateway to insights into its roasting chemistry and comprehensive authenticity profiles.

The direct-infusion of 130 coffee samples into a Fourier-transform ion cyclotron mass spectrometer (FT-ICR-MS) provided an ultra-high resolution perspective on the molecular complexity of coffee: The exceptional resolving power and mass accuracy (± 0.2 ppm) facilitated the annotation of unambiguous molecular formulas to 11,500 mass signals. Utilizing this molecular diversity, we extracted hundreds of compound signals linked to the roasting process through guided Orthogonal Partial Least Squares (OPLS) analysis. Visualizations such as van Krevelen diagrams and Kendrick mass defect analysis provided deeper insights into the intrinsic compositional nature of these compounds and the complex chemistry underlying coffee roasting. Predictive OPLS-DA models established universal molecular profiles for rapid authentication of Coffea arabica versus Coffea canephora (Robusta) coffees. Compositional analysis revealed Robusta specific signals, indicative of tryptophan-conjugates of hydroxycinnamic acids. Complementary LC-ToF-MS2 confirmed their compound class, building blocks and structures. Their water-soluble nature allows for application across raw and roasted beans, as well as in ready-made coffee products.

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

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

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

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

Tracking the transformation of extracellular polymeric substances during the ultraviolet/peracetic acid disinfection process: Emphasizing on molecular-level analysis and overlooked mechanisms.

In this study, the transformation mechanisms of extracellular polymeric substances (EPS) during ultraviolet/peracetic acid (UV/PAA) disinfection were elucidated based on multiple molecular-level analyses. After UV/PAA disinfection, the contents of soluble EPS (S-EPS), loosely bound EPS (LB-EPS) and tightly bound EPS (TB-EPS) were reduced by 70.47 %, 57.05 % and 47.46 %, respectively. Fluorescence excitation-emission matrix-parallel factor and Fourier transform ion cyclotron resonance mass spectrometry analyses showed that during UV/PAA disinfection, EPS was transformed from the state characterized by high aromaticity, low saturation and low oxidation to the one with reduced aromaticity, increased saturation and higher oxidation. Specifically, sulfur-containing molecules (CHOS, CHONS, etc.) in EPS were converted into highly saturated and oxidized species (such as CHO), with the aromaticity index (AImod) decreasing by up to 53.84 %. Molecular characteristics analyses further indicated that saturation degree, oxidation state of carbon and molecular weight exhibited the most significant changes in S-EPS, LB-EPS and TB-EPS, respectively. Additionally, mechanistic analysis revealed that oxygen addition reaction was the predominant reaction for S-EPS (+O) and TB-EPS (+3O) (accounting for 31.78 % and 36.47 %, respectively), while the dealkylation was the main reaction for LB-EPS (29.73 %). The results were consistent with functional groups sequential responses analyzed by Fourier transform infrared and two-dimensional correlation spectroscopy, and were further verified by density functional theory calculations. Most reactions were thermodynamically feasible, with reaction sites predominantly located at functional groups such as CO, CO, CN and aromatic rings. Moreover, metabolomics analysis suggested that changes in metabolites in raw secondary effluent during UV/PAA disinfection were strongly correlated with EPS transformation. Our study not only provides a strong basis for understanding EPS transformation during UV/PAA disinfection at molecular-level but also offers valuable insights for the application this promising disinfection process.

Analysis of urban composite non-point source pollution characteristics and its contribution to river DOM based on EEMs and FT-ICR MS.

Urban composite non-point source (UCNPS) has an increasing degree of influence on the urban receiving waters. However, there remains a dearth of precise techniques to characterize and evaluate the contribution of UCNPS. Therefore, this study developed a source analytical methodology system based fluorescence excitation-emission matrices spectroscopy (EEMs) and Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS).Specifically, it utilized parallel factor analysis (PARAFAC), two-dimensional correlation spectroscopy (2D-COS), end-member mixing analysis (EMMA), and non-metric multidimensional scaling (NMDS) to analysis UCNPS pollution characteristics and quantify its contributions to river DOM. The results of its application in typical hilly and plain urban within the Yangtze River Basin, China revealed that road and roof runoff exhibited high aromaticity and humic-like content, and the characteristics of pipe sediment was similar with domestic sewage. The component of Rivers had sequences of changes under rainfall perturbations. But terrestrial humic-like represented the initial input in all cases, and it can provide some indication of UCNPS input. The results of EMMA showed that the contribution of road runoff, roof runoff, pipeline sediment and domestic sewage to river DOM was 9.0 %-36.0 %, 2.6 %-19.1 %, 2.3 %-28.8 % and 5.9 %-25.9 %, respectively, and the specific contribution was mainly affected by rainfall level, regional terrain and drainage system. The methodology system of this study can provide technical support for the traceability and precise control of UCNPS pollution.

Targeted and non-targeted identification of dye and chemical contaminants in Loji River, Indonesia using FT-ICR-MS.

This study utilized liquid chromatography (LC) alongside Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to explore the dyes and chemical contaminants in Loji River, Indonesia. We tentatively identified a total of 655 contaminants at various confidence level, subsequently classifying them into 22 distinct categories. Of the 54 dyes we detected, 12 corresponded with entries in our specialized in-house database. These 12 dyes were further confirmed by reference standards, matching both retention time (RT) and MS/MS spectra. LC-FT-ICR MS data showed that dyes from printing batik and textile industries are key contributors to river pollution. Particularly noteworthy were two sample locations that displayed substantial contamination, predominantly from azoic and reactive dyes. Additionally, pharmaceuticals were identified as one of the most frequently occurring contaminants, underscoring the inadequacies in the area's sewage management. To corroborate these findings, we conducted physicochemical, phytotoxicity, and acute toxicity tests, all of which verified the harmful effects of the Loji River's water on both the local flora and human populations. Notably, water samples that tested positive for dye contamination exhibited elevated toxicity levels. To the best of our knowledge, this study is pioneering in its molecular-level investigation of dye contamination in Southeast Asian rivers. Our results accentuate the pressing need for both targeted and non-targeted screening methods to identify contaminants in the surface waters of developing nations.

Husk Separation (Kubessa Method) Impacts the Aging Chemistry of Beer.

The removal of husks before the mashing process, also known as the Kubessa method, is an established brewing practice often positively associated with smoothness and better flavor-stability of beer. Empirical evidence on the effect of the Kubessa method on beer, however, has been lacking. Similarly, our study's comprehensive analysis of established brewing attributes revealed that traditional methods do not fully capture the impact of husk separation in beer brewing. Conclusive evidence of the Kubessa method's impact on beer aging chemistry was obtained through ultrahigh resolution mass spectrometry (FT-ICR-MS), revealing intricate molecular details inaccessible to conventional analytical techniques. The compositional information on thousands of molecules in Kubessa beer was resolved and compared to whole malt mashing. Machine learning algorithms applied to aging experiments identified over 500 aging-related compounds inhibited by husk separation. Complementary Time of flight mass spectrometry (ToF-MS) coupled with chromatography further confirmed that the mashing of husks introduces sulfur-containing lipid compounds. These significant differences in the beer composition provide valuable insights for further investigation into the staling protective effect of husk-separation (Kubessa process) during beer production, as empirically demonstrated in this work.

Stability of sedimentary organic matter: Insights from molecular and redox analyses.

Sedimentary organic matter (SOM) affects the stability of the aquatic carbon pool. The degradation process of SOM is complex for its multifaceted composition. The concentration and properties of SOM affect its steady state, yet the transformation processes of SOM in lakes remain unclear. Here we show the molecular and redox perspectives of SOM stability in polluted sediments with high organic matter content and diverse vegetation. We find significant differences in carbon fractions across various sites. The origin of the organic matter, determined using excitation-emission matrix spectra, influences the consistency of organic matter composition and biochemical degradation in lacustrine sediment. We also observe that sulfur-containing substances decrease carbon chain length and reduce organic matter stability. Fourier-transform ion cyclotron resonance mass spectrometry shows that sulfur-containing substances decrease the degree of saturation and cause reduction. In contrast, nitrogen-containing compounds increase the modified aromaticity index and humin content, enhancing organic carbon complexity and stability (p < 0.05). These results complement the characteristics and transformations of SOM. In a broader perspective, this study contributes to laying the foundation for understanding SOM stability in the carbon cycle and its future effects.

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.

Vicia faba L. Pod Valves: A By-Product with High Potential as an Adjuvant in the Treatment of Parkinson's Disease.

Vicia faba L. is a leguminous plant with seeds rich in nutritional compounds, such as polyphenols and L-dopa, a dopamine precursor and first-line treatment for Parkinson's symptoms. Recently, its by-products have been revalued as a sustainable source of bioactive compounds. In this study, aqueous extracts of Lucan broad bean pod valves (BPs) were characterized to evaluate their potential use as adjuvants in severe Parkinson's disease. L-dopa content, quantified by LC-UV, was much higher in BPs than in seeds (28.65 mg/g dw compared to 0.76 mg/g dw). In addition, vicine and convicine, the metabolites responsible for favism, were not detected in pods. LC-ESI/LTQ-Orbitrap/MS2 allowed the identification of the major polyphenolic compounds, including quercetin and catechin equivalents, that could ensure neuroprotection in Parkinson's disease. ESI(±)-FT-ICR MS was used to build 2D van Krevelen diagrams; polyphenolic compounds and carbohydrates were the most representative classes. The neuroprotective activity of the extracts after MPP+-induced neurotoxicity in SH-SY5Y cells was also investigated. BP extracts were more effective than synthetic L-dopa, even at concentrations up to 100 µg/mL, due to the occurrence of antioxidants able to prevent oxidative stress. The stability and antioxidant component of the extracts were then emphasized by using naturally acidic solutions of Punica granatum L., Ribes rubrum L., and gooseberry (Phyllanthus emblica L.) as extraction solvents.

Dissolved Organic Matter Contains Ketones Across a Wide Range of Molecular Formulas.

The carbonyl functionality of natural organic matter (NOM) is poorly constrained. Here, we treated Suwannee River NOM (SRNOM) with ammonium acetate and sodium cyanoborohydride to convert ketone-containing compounds by reductive amination to their corresponding primary amines. The total dissolved nitrogen content increased by up to 275% after amination. Up to 30% of the molecular formulas of SRNOM contained isomers with ketone functionalities as detected by ultrahigh-resolution mass spectrometry. Most of these isomers contained one or two keto groups. At least 3.5% of the oxygen in SRNOM was bound in ketone moieties. The conversion of reacted compounds increased linearly with O/H values of molecular formulas and was predictable from the elemental composition. The mean conversion rate of reacted compounds nearly followed a log-normal distribution. This distribution and the predictability of the proportion of ketone-containing isomers solely based on the molecular formula indicated a stochastic distribution of ketones across SRNOM compounds. We obtained isotopically labeled amines by using 15N-labeled ammonium acetate, facilitating the identification of reaction products and enabling NMR spectroscopic analysis. 1H,15N HSQC NMR experiments of derivatized samples containing less than 20 µg of nitrogen confirmed the predominant formation of primary amines, as expected from the reaction pathway.

Revealing degradation pathways of soluble and dissolved organic matter in alluvial-lacustrine aquifer systems impacted by high levels of geogenic ammonium.

The excessive presence of geogenic ammonium (NH4+) in groundwater poses a global environmental concern, commonly linked to the degradation of nitrogen-containing dissolved organic matter (DOM). However, there is a gap in systematic studies on the combination of soluble organic matter (SOM) in sediments and DOM in groundwater, with few indoor incubation experiments to validate their degradation pathways. This study utilized ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry to analyze the molecular characteristics of DOM and SOM in aquifer systems affected by geogenic NH4+. Subsequently, indoor incubation experiments spanning up to 140 d were conducted to verify the degradation pathways. The experimental results revealed a two-phase degradation process for both the DOM and SOM. The initial stage was characterized by the degradation of aliphatic compounds (ALC) with the production of polyphenols (PPE) and highly unsaturated compounds (HUC). The second stage was dominated by the degradation of PPE and HUC, accompanied by the re-consumption of some ALC, while more recalcitrant HUC persisted. Notably, the first stage of SOM degradation exceeded that of DOM degradation, indicating that SOM exhibited greater resistance to aging. This phenomenon may be attributed to a wider range of active enzymes in sediments, the rapid replenishment of SOM by organic matter in sediments, or the accelerated degradation of DOM. The experimental results aligned with the molecular characterization of DOM and SOM in actual aquifer systems. It is hypothesized that NH4+ produced through the direct mineralization of SOM may contribute more to the enrichment of NH4+ in groundwater than that produced through the mineralization of DOM. This study is the first to analyze DOM and SOM together in aquifer systems and validate their degradation pathways through incubation experiments, thereby providing novel insights into the enrichment of geogenic NH4+ in groundwater.

Recovering Valuable Chemicals from Polypropylene Waste via a Mild Catalyst-Free Hydrothermal Process.

Waste polypropylene (PP) presents a significant environmental challenge, owing to its refractory nature and inert C-C backbone. In this study, we introduce a practical chemical recovery strategy from PP waste using a mild catalyst-free hydrothermal treatment (HT). The treatment converts 64.1% of the processed PP into dissolved organic products within 2 h in an air atmosphere at 160 °C. Higher temperatures increase the PP conversion efficiency. Distinct electron absorption and emission characteristics of the products are identified by spectral analysis. Fourier transform-ion cyclotron resonance-mass spectrometry (FT-ICR-MS) reveals the oxidative cracking of PP into shorter-chain homologues (10-50 carbon atoms) containing carboxylic and carbonyl groups. Density functional theory (DFT) calculations support a reaction pathway involving thermal C-H oxidation at the tertiary carbon sites in the polymer chain. The addition of 1% H2O2 further enhances the oxidation reaction to produce valuable short-chain acetic acids, enabling gram-scale recycling of both pure PP and disposable surgical masks from the real world. Techno-economic analysis (TEA) and environmental life cycle costing (E-LCC) analysis suggest that this hydrothermal oxidation recovery technology is financially viable, which shows significant potential in tackling the ongoing plastic pollution crisis and advancing plastic treatment methodologies toward a circular economy paradigm.

Thermodynamics and explainable machine learning assist in interpreting biodegradability of dissolved organic matter in sludge anaerobic digestion with thermal hydrolysis.

Dissolved organic matter (DOM) is essential in biological treatment, yet its specific roles remain incompletely understood. This study introduces a machine learning (ML) framework to interpret DOM biodegradability in the anaerobic digestion (AD) of sludge, incorporating a thermodynamic indicator (λ). Ensemble models such as Xgboost and LightGBM achieved high accuracy (training: 0.90-0.98; testing: 0.75-0.85). The explainability of the ML models revealed that the features λ, measured m/z, nitrogen to carbon ratio (N/C), hydrogen to carbon ratio (H/C), and nominal oxidation state of carbon (NOSC) were significant formula features determining biodegradability. Shapley values further indicated that the biodegradable DOM were mostly formulas with λ lower than 0.03, measured m/z value higher than 600 Da, and N/C ratios higher than 0.2. This study suggests that a strategy based on ML and its explainability, considering formula features, particularly thermodynamic indicators, provides a novel approach for understanding and estimating the biodegradation of DOM.

Different impacts of natural and anthropogenic factors on dissolved organic matter chemistry in coastal rivers: Implications for water management.

The chemical composition of dissolved organic matter (DOM) exerts significant influence on aquatic energy dynamics, pollutant transportation, and carbon storage, thereby playing pivotal roles in the local water quality and regional-global biogeochemical cycling. However, the effects of natural climate change and local human activities on watershed characteristics and in-river processes have led to uncertainties regarding their contributions to DOM chemistry in coastal rivers, creating challenges for effective water management and the study of organic matter cycling. In this investigation, we employed a combination of stable isotopic analysis, optical techniques, and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) to elucidate the sources, optical properties, and molecular composition of DOM in three South China coastal rivers. Our results suggest that terrestrial DOM entering the three rivers through natural or anthropogenic pathways is gradually diluted by in situ primary production as it moves downstream, ultimately being influenced by seawater intrusion near the estuary. Additionally, terrestrial processes influenced by temperature likely govern DOC concentration, while seawater intrusion promotes the natural production of S-containing organic compounds. In contrast, human-altered landcover significantly impacts DOM molecular composition. Increased water areas lead to the enrichment of lignins with high disinfection byproduct formation potential, and agricultural residue burning appears to be the dominant source of pyrogenic DOM in these coastal rivers. Our distinct results suggest that the development of specific water management plans that consider the combined effects of temperature, seawater intrusion, landcover changes, and agricultural practices will be essential to ensure sustainable water resource.

Effects of solid phase extraction conditions on molecular composition of unknown disinfection byproducts in chlorinated municipal wastewater based on FT-ICR-MS analysis.

Disinfection byproducts (DBPs) have been extensively investigated during the chlorination of water and wastewater. Although over 700 DBPs have been identified, more than 50% of the total organic halogen remains unknown. Solid phase extraction (SPE) has been emerged as a popular pretreatment approach for enrichment and desalting of unknown DBPs prior to the mass spectrometry analysis. However, the effects of SPE conditions on unknown DBPs in real wastewater have not yet been reported. Herein, three factors (acid types, pH values, and sorbent types) influencing the composition of DBPs in chlorinated municipal wastewater were systematically investigated by Fourier transform ion cyclotron resonance mass spectrometry and statistical analysis. The results indicated that the number of DBPs in different SPE conditions ranged from 280 to 706, and the majority ones were Br-DBPs and CHOX compounds. Compared with H2SO4, more common DBPs were found when using HCl and HCOOH to adjust the pH values of samples. The unique DBPs extracted at pH 1.0 and 2.0 generally owned higher modified aromaticity index (AImod) value and C number than at pH 3.0. The effect of acid types on the extracted DBPs was pH dependent, and the total number of extracted DBPs increased with the increasing of pH value. In terms of sorbent types, the unique DBPs in C18 sorbent possessed low O/C ratios (O/C < 0.6), whereas the unique ones in HLB sorbent owned high O/C ratios (O/C > 0.6). Compared with C18 and HLB sorbents, the unique DBPs extracted in PPL sorbent were characterized by relatively high AImod and DBE values. Based on mass difference analysis, 1496 precursors-DBPs pairs were identified in all extracted samples, with the highest number of bromine substitution reaction. Overall, the effects of SPE conditions on the composition of unknown DBPs should not be overlooked, and the amount and diversity of DBPs may be underestimated under a single SPE condition. This study provides new methodological references for the accurate identification of unknown DBPs with different characteristics in real wastewater.

Chemodiversity of dissolved organic matter and its association with the bacterial community at a zinc smelting slag site after 10 years of direct revegetation.

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.