Excitation-emission Matrix Fluorescence Research Articles

Unraveling the structure-property relationships in fluorescent phenylhydrazones: the role of substituents and molecular interactions.

This study investigates the structure-property relationships of a series of phenylhydrazones bearing various electron-donating and electron-withdrawing substituents, such as methoxy, dimethylamino, morpholinyl, hydroxyl, chloro, bromo, and nitro groups. The compounds were synthesized, and their structures were characterized using single-crystal X-ray diffraction, powder X-ray diffraction, FTIR spectroscopy, NMR spectroscopy, and DSC. Three-dimensional excitation-emission matrix (3D-EEM) fluorescence spectroscopy and UV-Vis spectroscopy were employed to elucidate the complex interplay between the molecular skeleton, substituents, and the resulting photophysical properties. Quantum mechanical calculations provided further insights into the electronic structure and excited-state dynamics of the investigated compounds. The phenylhydrazones exhibited emission wavelengths ranging from 438 to 482 nm, with the molecular backbone playing a crucial role in determining the emission wavelength. The incorporation of electron-donating substituents, such as methoxy and dimethylamino groups, led to enhanced fluorescence intensity, while the presence of nitro groups, resulted in complete fluorescence quenching. This comprehensive study establishes rational design principles for the development of highly emissive phenylhydrazones with tuned photophysical properties and highlights the significance of the molecular skeleton in dictating the fluorescence behavior of this class of compounds.

Glucose as a Metabolic Enhancer: Promoting Nonylphenol Detoxification by Chlorella pyrenoidosa

The environmental treatment of endocrine-disrupting compounds (EDCs) has attracted significant attention. Nonylphenol (NP), a highly toxic EDC with widespread distribution, presents an urgent challenge requiring effective removal strategies. Although microalgae-based treatments offer environmentally friendly and cost-effective solutions, the high toxicity level of NP impedes this process. Analysis was conducted on cell biomass, cell morphology, extracellular polymeric substances (EPSs), and the degradation of nonylphenol in Chlorella pyrenoidosa treated with nonylphenol and glucose. Glucose restored the algal biomass to 2.23 times its original level, reduced cellular damage, and maintained normal physiological activities. Glucose also stimulated algal metabolism and promoted the secretion of EPSs. The polysaccharide content of soluble EPSs (S-EPSs) increased by 32.7%, whereas that of the bound EPSs (B-EPSs) increased by 55.5%. The three-dimensional excitation–emission matrix fluorescence spectroscopy of B-EPS indicated that glucose enhanced tryptophan secretion. Glucose showed great potential as a biostimulant to enhance NP bioremediation efficiency in aquatic ecosystems. This finding indicates that the nonylphenol remediation of wastewater can be integrated with microalgal biomass recovery, creating opportunities for revenue generation.

Insight into the roles of Cl− for the degradation of acid Red 14 in an electrochemical advanced oxidation system: Mechanisms and DFT studies

Textile wastewater was typically characterized by high concentrations of chloride ions, with Acid Red 14 (AR14) representing a significant pollutant. Nevertheless, research into the degradation of AR14 by electrochemical advanced oxidation processes (EAOPs) had largely overlooked the influence of chloride ions. In this regard, the EC-Clorine-MMO/Ti system was designed, and the degradation mechanism of AR14 was subjected to meticulous investigation. The adopted anode was composed of Ti/IrO2-Ta2O5 (mixed metal oxide, MMO). It demonstrated superior efficiency in degrading AR14 within a sodium chloride (NaCl) electrolyte, registering an apparent kinetic constant rate approximately 16.76 times greater than that observed within a sodium perchlorate (NaClO4) electrolyte. The optimal chloride ion concentration was identified as 0.04 mol/L. Besides, alkaline conditions were not conducive to the degradation of AR14. It was noteworthy that the electrochemical byproducts chlorite (ClO2−), chlorate (ClO3−), perchlorate (ClO4−), and trihalomethane (THMs) were not produced in the solution treated by the EC-Clorine-MMO/Ti system. Electron paramagnetic resonance (EPR) spectroscopy, probe, and quenching experiments identified that hydroxyl radicals (•OH), superoxide radicals (O2•−), and dichloride radicals/chlorine monoxide radicals (Cl2•−/ ClO•) were the major reactive species. Of these, •OH played a pivotal role in AR14 degradation. Additionally, the three principal degradation pathways of AR14 were deduced by LC-MS analysis, UV–vis spectra, density-functional theory (DFT) calculations, and excitation-emission matrix (EEM) fluorescence spectroscopy. Furthermore, the generation mechanism of reactive species and the proposed mechanism of AR14 degradation by the EC-Clorine-MMO/Ti system were presented. The study made a significant contribution to the understanding of the electrochemical reactions occurring in textile wastewater and provided valuable insights into the rational control of electrolytic conditions for the treatment of saline wastewater.

Interaction Between Root Exudates and PFOS Mobility: Effects on Rhizosphere Microbial Health in Wetland Ecosystems

Perfluorooctanesulfonate (PFOS), a persistent organic pollutant, poses significant ecological risks. This study investigates the effects of PFOS on rhizosphere microbial communities of two wetland plants, Lythrum salicaria (LS) and Phragmites communis (PC). We conducted microcosm experiments to analyze the physiological status of soil microbes under varying PFOS concentrations and examined the role of root exudates in modulating PFOS mobility. Flow cytometry and soil respiration measurements revealed that PFOS exposure increased microbial mortality, with differential impacts observed between LS and PC rhizospheres. LS root exudates intensified microbial stress, whereas PC exudates mitigated PFOS toxicity. Thin-layer chromatography indicated that LS exudates decreased PFOS mobility, leading to higher local concentrations and increased microbial toxicity, while PC exudates enhanced PFOS mobility, reducing its local impact. Fourier-transform infrared spectroscopy and excitation-emission matrix fluorescence spectroscopy of root exudates identified compositional shifts under PFOS stress, highlighting distinct defense strategies in LS and PC. These findings underscore the importance of plant-microbe interactions and root exudate composition in determining microbial resilience to PFOS contamination.

Removal of Natural Organic Matter Fractions by Kaolin/Fly Ash Ceramic Microfiltration Membrane in Drinking Water: Insights from a Laboratory Scale Application

AbstractThe high cost of precursor materials has hindered commercialization of ceramic membranes (CM). In this work, a microfiltration ceramic disc (≈50 mm in diameter and 4 mm thick) is prepared from low‐cost materials, kaolin, and fly ash (≈67 and 26 wt.%, respectively) by pressing at 200 bar and calcining at 900 °C. Membrane characterization involved physicochemical properties, NOM removal efficiency, and fouling propensity analysis. Furthermore, the efficiency of the CM is tested on samples collected from four drinking water treatment plants (DWTPs) in KwaZulu‐Natal Province of South Africa. The NOM removal efficiencies ranged from 18.5–33.4% higher than that achieved by the sand filtration step of all the DWTPs. Fluorescence excitation‐emission matrix (FEEM) studies show dominance of terrestrial humic‐like and fulvic‐like NOM fractions in the raw water and are amenable to removal by CM at all the DWTPs (up to 64.7% higher than removal by sand filters at the respective plants). This study demonstrates the utility of ceramic membranes fabricated from rudimentary materials and presents an opportunity to upscale and retrofit the technology to target the removal of NOM fractions at conventional drinking water treatment plants.

Effects of straw amendment on the bioavailability of selenite in soil and its mechanisms.

Dissolved organic matter (DOM) released by straw returning for decomposition interacts with selenium (Se) in soil, which affects the speciation distribution of Se and its bioavailability. However, the relative mechanisms involved are slightly understood. This study investigated the effects of straw-derived DOM on two levels of exogenous selenite (low-Se and high-Se treatments) in two types of soil with distinct pH. Interactions between DOM and Se were revealed through three-dimensional excitation emission matrix (3D-EEM) fluorescence spectroscopy and two-dimensional correlation spectroscopy (2D-COS). Results showed that straw amendment significantly enhanced selenite bioavailability in alkaline Lou soil regardless of Se application rates (p < 0.05). However, only the high-Se treatment generated remarkable Se content in wheat grains in acidic krasnozems (p < 0.05). Selenite predominantly incorporated with phenolic and etheric C-O functional groups of DOM in soil, which mainly existed in aromatic DOM such as humic acid (HA). Consequently, HA-Se was more likely to form in krasnozems enriched with HA. 2D-COS evidenced that HA mineralization promoted Se bioavailability in krasnozems with high-Se treatment. After selenite complexed with saturated and unsaturated aliphatic carboxyl groups (CO) of DOM, it formed Hy-Se and FA-Se in Lou soil, which could be directly absorbed by wheat roots. Therefore, the composition and functional group reaction sequences of DOM in different soils manipulated selenite bioavailability in soil. These findings could provide a basis for regulating Se bioavailability during biofortification in soils.

Toward Classification of Fish Meat Using Fluorescence Excitation–Emission Matrix and Multivariate Statistics

Frequent intentional mislabeling of particular fish and fish products, such as the sale of frozen and thawed fish instead of fresh fish, occurs on all continents. Therefore, two studies were conducted to classify fish meat using excitation–emission matrix (EEM) nondestructively. The first study assessed EEM for differentiation between fresh and frozen–thawed spotted mackerel fillets. Fresh fillets were yielded with different post-mortem freshness variations (ice storage for 0–40 h). The right-side fillets were used as fresh fillets, whereas the left-side fillets were frozen and stored at −30 °C for three months, then thawed at 4 °C. Subsequently, EEM acquisition and chemical analyses were performed. Results of principal component analysis (PCA) of EEM spectra showed clear discrimination between fresh and frozen–thawed meat of fish fillet. In the second study, post-mortem freshness variations in four fish species (horse mackerel, spotted mackerel, cod, and flounder) were simulated by ice storage (0–48 h) and subsequent freezing. PCA of the EEM demonstrated a clear distinction among the fish meat categories, which was also revealed from the freshness data of chemical analysis. Results show that this novel method can be used to monitor fishery product authenticity.

Fluorescence spectrometric analysis for diagnosing compositional variations in effluent organic matter by chlorination and ozonation

Analyzing the reactivity of organic matter to oxidants such as chlorination and ozonation is crucial for evaluating the effectiveness of water treatment systems and their potential impacts on environmental safety and human health. This study explored the changes in organic substances, specifically bovine serum albumin (BSA), humic acid sodium salt (HA), and effluent organic matter (EfOM) from a wastewater treatment facility during chlorination and ozonation. Four spectrometric techniques were employed: ultraviolet absorbance at 254 nm (UVA254), fluorescent excitation-emission matrix (EEM), synchronous fluorescence two-dimensional correlation spectroscopy (SF-2DCOS), and EEM-parallel factor integrated 2DCOS (EEM-PARAFAC-2DCOS). The findings revealed that ozone possesses superior oxidizing properties compared to chlorine, as evidenced by UVA254 and EEM analyses, resulting in more diverse structural modifications in EfOM. SF-2DCOS and EEM-PARAFAC-2DCOS provided comprehensive details on the direction and sequence of these changes, with EEM-PARAFAC-2DCOS delivering clear and intuitive insights. Protein-like and fulvic-like substances were susceptible to chlorination and ozonation, exhibiting different reaction sequences with each oxidant. Furthermore, variations in protein-like and humic-like components in actual EfOM samples may not align precisely with those in model substances, emphasizing the importance of considering specific organic matter variations in real EfOM samples compared to model substances. This research offered a deeper understanding of the reactivity and transformation of organic matter in wastewater treatment processes through simple and rapid spectroscopic methods, potentially improving the management and mitigation of undesired byproducts.

Terrestrial dissolved organic matter inputs affect the nitrous oxide emission revealed by FT-ICR MS

Nitrous oxide (N2O) emission from lake systems could be affected via intrusion of terrestrial organic matter, causing impairment in biogeochemical cycling. The sources and mechanisms by which DOM (Dissolved organic matter) alters emissions of N2O are poorly understood. Here, we simulate different terrestrial DOM (anthropogenic sources, natural sources, and surface runoff) to assess the mechanisms affecting N2O emissions with variations of DOM. We used a combination of absorption spectroscopy, excitation-emission matrix fluorescence, and Fourier transform ion cyclotron resonance mass spectrometry to characterize DOM comprehensively. For the characterization of DOM, a combination of absorption spectroscopy, excitation-emission matrix fluorescence, and Fourier transform ion cyclotron resonance mass spectrometry was used. Microbial analysis was conducted to identify the potential microbial mechanisms. Different terrestrial DOM inputs primarily impact N2O emissions through the denitrification process (14.52 %, p < 0.05), with significant effects on the abundance of narG (12.97 %, p < 0.05) and nirK+S (10.13 %, p < 0.05). The biodegradable components in sediments directly promote N2O emissions, while in aquatic systems, the labile components (proteins, sugars, and lipids-like) were preferentially metabolized, producing reluctant derivatives. The biodegradable components (i.e., protein-like) from anthropogenic sources rapidly facilitate N2O production. Natural and surface runoff sources were the significant drivers for the continuous release and metabolism of DOM. N2O Loss emissions are negatively influenced by the regulation of carbon and nitrogen metabolism by nitrifiers and denitrifies in the sediment (p < 0.001). Metabolism of carbon and nitrogen regulated by nitrifier and denitrifies in the sediments negatively influences N2O flux (p < 0.001). N2O emissions were mainly influenced by bioavailability of inputs: DOM and varying terrestrial conditions. The results provide a theoretical base for the management of greenhouse gas emissions from lakes.

Research on the Properties of DOM from the Microalgal Treatment Process for Leachate from Incineration Fly Ash Based on EEM-PARAFAC Analysis

Fly ash derived from the incineration of garbage is known to contain hazardous materials that can affect the growth of plants and animals and pose a threat to human health. In this study, we explored how treatment of fly ash leachate with microalgae could alter the properties of dissolved organic matter (DOM). Fly ash leachate samples obtained from a landfill site in Wenzhou were treated with the microalgae Chlorella vulgaris or Scenedesmus obliquus without and with the addition of ammonium ferric citrate (C6H8FeNO7) for 24 days, and changes in DOM levels and types were measured using excitation emission matrix fluorescence technology. The following results were obtained: Analysis of three-dimensional fluorescence spectral indices indicated that the algal treatment process consistently generated new autogenous DOM, with most of the organic matter being newly formed. Additional nutrients had a minor effect on the production and composition of DOM in the system. Using a parallel factor model to analyze the three-dimensional fluorescence spectral matrices of water samples from various systems revealed common components in each group, including arginine, tryptophan-like proteins and fulvic acid-like substances. This study aimed to explore the changes in DOM properties during microalgae treatment of fly ash leachate from the perspective of three-dimensional fluorescence.

Optical signatures as a diagnostic tool for tracking dynamics of sedimentary dissolved organic nitrogen, phosphorus, and sulfur in an anthropogenic bay

Tracing the anthropogenic fingerprint and potential nutrient release from sediments is crucial from ecological and economic perspectives, but the lack of effective and low-cost tracking techniques poses a significant challenge. Here, we investigate the optical properties and molecular composition of sedimentary dissolved organic matter (DOM) from surface sediments (n = 41) collected along the land-sea continuum of an industrialized and urbanized bay in China. We use optical techniques (UV–visible spectroscopy and Excitation–emission matrix fluorescence spectroscopy) and Fourier-transform ion cyclotron resonance mass spectrometry for sedimentary DOM characterization. Five fluorescent components (C1-C5) are validated by Parallel Factor analysis (PARAFAC), representing diverse sources and types of sedimentary DOM, including aromatic/terrestrial, microbial, anthropogenic, and protein-like substances. Molecular analysis further reveals 14,052 unique compounds. Distinct molecular characteristics are identified for sedimentary dissolved organic nitrogen (DON), phosphorus (DOP), and sulfur (DOS). Sedimentary DOP exhibits the highest saturation, DON the highest aromaticity, and DOS the highest molecular weight. Optical parameters (e.g. fluorescence index) correlate significantly with specific molecular formulas of sedimentary DON, DOP, and DOS, suggesting that optical signatures can serve as a diagnostic tool for exploring internal nutrient release and point source pollution in aquatic ecosystems. This linkage will allow for efficient large-scale monitoring of sedimentary heteroatomic compound cycling in aquatic systems using optical techniques with robust interpretations, which has significant implications for sustainable watershed management.

Application of excitation-emission matrix fluorescence spectroscopy and chemometrics for quantitative analysis of emulsified oil concentration

Emulsified oil concentration is an important index for quantitative analysis of sea surface oil spill pollution, and the development of a fast and effective quantitative analysis method for emulsified oil concentration plays a crucial role in the estimation of oil spill volume and post-spill assessment. A quantitative analysis method for emulsified oil concentration based on excitation-emission matrix (EEM) fluorescence spectroscopy and chemometrics was proposed. Firstly, the EEM fluorescence spectra of two emulsified oils were measured using a FLS1000 fluorescence spectrometer. Then, the measured EEM fluorescence spectra were decomposed by parallel factor analysis (PARAFAC), and several key excitation wavelengths were filtered from the loading matrix obtained from the decomposition. Subsequently, the three-band fluorescence index (TBFI) at these excitation wavelengths was calculated and combined with the optimal band selection algorithm, from which the optimal emission band combinations were selected. Finally, the selected optimal emission bands were combined with partial least squares regression (PLSR) to establish a prediction model for emulsified oil concentration. By comparing the prediction results with those based on PARAFAC-PLSR and multivariate curve resolved-alternating least squares (MCR-ALS)-PLSR models, the TBFI-PLSR model showed the best results in the quantitative analysis of emulsified oil concentration. The coefficient of determination, mean square relative error, and ratio of performance to interquartile distance for the gasoline and diesel fuel emulsion validation sets were 0.93, 3.67%, 4.72, and 0.93, 3.72%, 4.60, respectively.

Identification of lu’an Guapian at different picking periods by using excitation–emission matrix fluorescence spectroscopy coupled with chemometrics

Lu’an Guapian (LAGP) is a renowned green tea, with its price significantly higher when picked before the Qingming Festival compared to after, posing risks of confusion and counterfeiting. This study proposed using an excitation-emission matrix (EEM) fluorescence method combined with chemometrics for rapid identification of tea picked before and after Qingming Festival. Firstly, the differences among the EEM fingerprints of different tea samples were analyzed using the alternating trilinear decomposition (ATLD) algorithm. To determine the differences between LAGP before and after Qingming Festival, the total contents of ten main components in tea were detected, and their effects on the EEM fluorescence fingerprint of tea were analyzed using correlation heatmaps. Finally, two chemometric algorithms, partial least squares discriminant analysis (PLS-DA) and k-nearest neighbor (k-NN), were used to classify LAGP before and after Qingming Festival, achieving a classification accuracy of 100% for the training set, test set, and prediction set. To further explore the potential of this method, LAGP was further classified in detail according to four detailed picking periods, achieving an accuracy of over 83%. The same chemometric algorithm was used to classify the data based on the high-performance liquid chromatography (HPLC) method, yielding results comparable to those of the EEM-based method, though slightly inferior. Variable importance projection (VIP) analysis shows that catechin analogs are the main contributors to the classification of LAGP. The results demonstrated the EEM method’s significant potential in identifying the picking time of green tea.

Detection of Escherichia coli Using Bacteriophage T7 and Analysis of Excitation‑Emission Matrix Fluorescence Spectroscopy

Conventional detection methods require the isolation and enrichment of bacteria, followed by molecular, biochemical, or culture-based analysis. To address some of the limitations of conventional methods, this study develops a machine learning (ML) approach to analyze the excitation-emission matrix (EEM) fluorescence data generated based on bacteriophage T7 and Escherichia coli interactions for in-situ detection of live bacteria in the presence of fresh produce homogenate. We trained classification models using various ML algorithms based on the 3-D EEM data generated with bacteria and their interactions with a T7 phage. These ML algorithms, including linear Support Vector Classifier (SVC) and Random Forest (RF), demonstrate high accuracy (>0.85) for detecting E. coli at 102 CFU/ml concentration within 6 h. Additionally, these ML models can differentiate among different E. coli concentration levels. For example, the Gaussian Process model achieved an accuracy of 92% in detecting different concentration levels of live E. coli. Application of these ML methods to detect E. coli in spinach homogenate yielded an accuracy of 89% using the linear-SVC model. Furthermore, feature selection techniques were employed to reduce the dimensionality of the data, revealing that only six features were necessary for achieving classification accuracy (>0.85) of spinach homogenate samples containing 102 CFU/ml of E. coli. These findings highlight the potential of this novel bacterial detection methodology, offering rapid, specific, and efficient solutions for applications in food safety and environmental monitoring.

Film-immobilized carbon nitride for the degradation of pharmaceuticals: A continuous flow photoreactor performance upheld by excitation-emission matrix fluorescence spectroscopy

The validation of immobilized photocatalysts is a fundamental matter regarding the scaling-up process in the photocatalytic degradation of aqueous pollutants in natural surface waters. This work presents the comprehensive evaluation of graphitic carbon nitride (g-C3N4, CN) immobilized onto a polymeric film (F) placed inside a continuous flow operation planar reactor for the removal of a mixture of pharmaceuticals (i.e., venlafaxine, citalopram, carbamazepine, tramadol, ketoprofen, and diclofenac, 3 μM each) under visible light. The resulting CN/F (8 mg of CN per cm2 of film and with significant preservation of optical and structural properties after more than 350 h of reuse) yielded the complete removal under total recirculation of all pharmaceuticals after 90 min under visible light, except for ketoprofen, probably ascribed to competition for photogenerated holes, as suggested by the proposed mechanism. Under dead-end continuous flow mode, the steady-state conversion averaged 67% in deionized water, increasing up to 76%, and 80% in natural surface waters obtained from the Douro River and the effluent from a wastewater treatment plant (Northwestern Portugal), respectively, related to the promotion effect of carbonates anions and organic matter. The assessment of excitation-emission matrix (EEM) fluorescence spectroscopy coupled with parallel factor (PARAFAC) analysis further demonstrated the removal (ca. 50%) of the protein- and humic-like substances contained in the collected wastewater, thus evidencing the continuous flow mode performance of the immobilized photocatalyst for real environmental applications.

Mitigating Membrane Fouling in Abattoir Wastewater Treatment: Integration of Pretreatment Step with Zwitterion Modified Graphene Oxide-Polyethersulfone Composite Membranes.

Composite polyethersulfone (PES) membranes containing N-aminoethyl piperazine propane sulfonate (AEPPS)-modified graphene oxide (GO) were integrated with either of the two pretreatment processes (activated carbon (AC) adsorption or polyelectrolyte coagulation) to assess their effectiveness in mitigating membrane fouling during the treatment of abattoir wastewater. The AEPPS@GO-modified membranes, as compared to the pristine PES membranes, showed improved hydrophilicity, with water uptake increasing from 72 to 118%, surface porosity increasing from 2.34 to 27%, and pure water flux (PWF) increasing from 235 to 673 L.m-2h-1. The modified membranes presented improved antifouling properties, with the flux recovery ratio (FRR) increasing from 59.5 to 93.3%. This study compared the effectiveness of the two pretreatment processes, AC, coagulation, and the integrated system (coagulation/AC-UF membrane), in the removal of natural organic matter (NOM) and improvement of abattoir wastewater's pH, electrical conductivity, TDS, and turbidity. The integrated systems produced improved water quality in terms of pH, EC, TDS, turbidity, and organic content. The fluorescence excitation-emission matrix (FEEM) analysis exhibited almost no fluorescence peak post-treatment following organic loading removal. The quality of the water met the South African non-potable water reuse standards. The sole membrane treatment systems exhibited good fouling resistance without the pretreatment systems; however, integrating these systems can offer extended longer filtration periods, thereby assisting in cost aspects of the abattoir wastewater treatment system.

Aqueous photochemical aging of water-soluble smoke particles from crop straws burning

Most aqueous oxidation studies focus on single model precursors, while the photochemical aging of actual water soluble organic matter (WSOM) in particles emitted from biomass burning remains poorly understood. In this study, gas chromatography-mass spectrometry (GC/MS) was first used to analyze the WSOM in smoke particles emitted from three crop straws burning. The results show that the dominant WSOM in three crop straws (CS) smoke are phenolic substances with small differences. Aqueous photochemical aging of WSOM in CS smoke was investigated under simulated sunlight exposure. High-resolution aerosol mass spectrometry (HR-AMS) analyzed aqueous secondary organic aerosol (aqSOA) and it was found that the oxidation degree of aqSOA increased with prolonged aging. No obvious increase in the abundance of N-containing organic ions was observed over the course of aqueous aging. As aqueous aging progresses, the pH of the solution gradually decreases, accompanied by the continuous generation of organic acids. Studies on dithiothreitol (DTT) activity indicate that the impact of aqueous photochemical aging on health is not significant.The solution after photoaging shows relatively lower light absorption ability than the initial solution. The aqueous photochemical aging also led to a gradual reduction of fluorescence at excitation/emission = 250–260 nm/350 nm (protein-like substances) for CS smoke WSOM, suggesting the significant degradation of chromophores. However, three-dimensional excitation-emission matrix (EEM) fluorescence combined with parallel factor analysis (PARAFAC) revealed that aqueous aged CS smoke WSOM contains compounds with high humification index, confirming that the fluorophore composition is altered by aqueous aging. The humic-like substance (HULIS) concentration increased for the first 3 h and then decreased, closely matching the pattern of a new fluorescence peak. Finally, GC/MS analysis of the products indicated that there was obvious decline in proportion of methoxyphenol. The results of this study are important for understanding the aqueous-phase oxidation reactions of CS smoke WSOM in the atmosphere and their light-absorption characteristics and health impacts.

A crude, cold-pressed oil from elderberry (Sambucus nigra L.) seeds: Comprehensive approach to properties and characterization using HPLC, DSC, and multispectroscopic methods

The physicochemical characterization of fresh, undiluted, cold-pressed oil from elderberry seeds (EO) is presented. The results showed EO's uniqueness for the 93 % presence of essential fatty acids, including linoleic n-6 (41 %), α-linolenic n-3 (38 %), and oleic n-9 (13 %) acids with favorable ratios for human nutrition, n-3/n-6 = 0.93. A γ-tocopherol is the dominant tocopherol (96 %), with a concentration of 20.62 mg/100 g, indicating low oil oxidative stability. DSC heating and cooling traces determined the thermal properties. These results also revealed the presence of metastable triacylglycerol (TAG) structures composed of polyunsaturated fatty acids. The presence of characteristic groups for fatty acids and TAGs in EO was confirmed by FTIR-ATR spectra. For the first time, Langmuir monolayer studies on EO revealed its low compressibility, indicating its low emulsifiability, and the presence of minor components of EO, including tocopherols, phenolic acids, polyphenols, flavonoids, and carotenoids, was determined using UV–Vis absorption and fluorescence excitation-emission matrix (EEM) along with the chemometric method.

Novel insights into fouling mechanisms in anaerobic acidification membrane bioreactor: The leading role of pH value

Anaerobic acidification membrane bioreactors (AAMBRs) have recently emerged as effective systems for recovering volatile fatty acids (VFAs) from municipal wastewater. However, membrane fouling remains a critical challenge, with its underlying mechanisms not yet fully understood. Given its importance in inhibiting methanogenic bacteria and stabilizing VFAs production, this study explores the direct and indirect effects of pH on membrane fouling mechanisms in AAMBRs. The results demonstrated that compared to pH 7, the fouling potential of anaerobic sludge was significantly higher at pH levels of 5 and 10 owing to a decrease of sludge floc size and an increase of soluble microbial products (SMP) especially proteins. Analytical techniques such as confocal laser scanning microscopy (CLSM), fourier transform infrared spectroscopy (FTIR), and fluorescence excitation-emission matrix (F-EEM) analyses revealed a substantial increase in organic foulants particularly proteins on the membrane surface at pH levels of 5 and 10. Circular dichroism (CD) spectroscopy further indicated a significant change in protein secondary structure, specifically an increase in α-helix content under extreme pH conditions. Furthermore, the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory indicated that elevated protein concentrations enhance the adhesion of sludge and SMP to membrane surfaces. Insights from the Flory-Huggins theory demonstrated that variations in protein structure significantly contribute to increased filtration resistance within the gel layer. Both experimental data and theoretical models underscore the dual role of pH in optimizing VFAs production and managing membrane fouling, offering insights for enhancing AAMBR performance and mitigating fouling issues.

Interactions between dissolved organic matter with different molecular weights and nonylphenol in surface water bodies

Dissolved organic matter (DOM) has a complex composition, which can interact with various pollutants and affect the removal of pollutants. Therefore, a thorough understanding of the interaction between the encccvironmental hormone nonylphenol (NP) and DOM is crucial for environmental impact and development. In this study, the interaction was investigated by means of excitation emission matrix (EEM) fluorescence spectroscopy, UV–Vis spectroscopy, FT-IR spectroscopy, nuclear magnetic resonance (NMR) and complex model analysis. The interaction between different MW DOM and NP was verified by the spectral characterization data. According to the characterization analysis, the main components of DOM in water samples were proteinoid (C1, C2, C4) with MW < 1 k Da, and their binding capacity (log Ka value) and binding site number (n) showed the maximum values (3.37, 3.24, 3.26; 0.81, 1.22, 0.52). For the humus like substance (C3) with larger molecular weight, the log Ka value and the number of binding points n increased with increasing molecular weight, and the maximum values were 3.13 and 0.31, respectively. It can be seen that low molecular weight proteins have strong binding ability and binding sites with NP, and high molecular weight humus also have strong binding ability. Overall, the interaction between DOM and NP has molecular weight dependence and heterogeneity. The purpose of this study is to deeply understand the interaction characteristics of different MW DOM with NP, and to provide theoretical support and reference for the study of the removal effects of NP pollutants.