Excitation-emission Matrix Fluorescence Spectroscopy Research Articles

Surface-bound radicals enhancing detoxification of enrofloxacin during peroxymonosulfate oxidation: Activated carbon vs. alumina as catalyst carriers

Recent studies have found the presence of surface-bound radicals (Surf-R) during the heterogeneously catalyzed peroxymonosulfate (PMS), especially when the catalyst carriers possess a high adsorption capacity. However, the effects of Surf-R on the toxicity of transformation products (TPs) are still not well elucidated. In this study, Co and Mn were loaded onto commonly used carriers: activated carbon and alumina (CoMn@AC vs CoMn@Al2O3) to create comparable catalytic centers but distinct adsorption capacity, which was proved by material characterization (SEM, EDS, BET, XPS), adsorption and catalytic tests. Both images and quantitative analysis with 3D excitation-emission matrix fluorescence spectroscopy demonstrated that the reaction solutions of enrofloxacin from two catalysts composed differently when a same degradation efficiency was achieved. It was further found that the respiratory inhibition of CoMn@AC catalyzed samples was only 7~36% of the counterpart. 50 TPs were identified with UPLC-MS/MS, among which 31 TPs were possibly more toxic than enrofloxacin according to the calculation with the Toxicity Estimation Software Tool. CoMn@Al2O3 produced 14 unique toxic TPs while CoMn@AC only 4. The analysis with EPR revealed that both catalysts generated SO4•-, •OH, and 1O2; quenching tests proved a lot of Surf-R with CoMn@AC but not with CoMn@Al2O3. This study demonstrates the high potential of Surf-R to enhance the detoxification of organic contaminants during PMS oxidation and thus provides a reference for designing novel catalysts to achieve efficient contaminant degradation and detoxification.

Synergistic effect of N doping and oxygen vacancies over TiO2 nanosheets with enhanced photocatalytic removal of tetracycline

The increasing pollution from non-biodegradable antibiotics poses a significant threat to ecosystems and human health. TiO2 is widely acknowledged as the premier photocatalyst for removing antibiotics from wastewater. To address the limitations of TiO2 in wide forbidden band width and low efficiency separation/migration of carriers, N-doping and oxygen vacancies (OVs) are co-modified within TiO2 nanosheets through the one-step calcination of a mixture of H2TiO3 and urea. The results indicate that the co-modified sample (TiO2-U5) exhibited the highest TC removal efficiency of 90% after 60minutes of reaction, with a kinetic constant 3.6 times higher than that of pristine TiO2. The effective mineralization of TC is confirmed by three-dimensional excitation-emission matrix fluorescence spectroscopy (3D EEMs). Systematic characterization of the photocatalyst structure and monitoring of intermediates/products reveal that the synergistic effect of N-doping and oxygen vacancies (OVs) enhances band alignment, light response, and carrier separation/migration, thus improving the photocatalytic degradation performance of TC. This study highlights the significant potential of adjusting charge transport and enriching active sites through the co-introduction of doping and surface defects on TiO2 for the photocatalytic degradation of antibiotics.

Light-Emitting-Diode-Induced Fluorescence from Organic Dyes for Application in Excitation-Emission Fluorescence Spectroscopy for Food System Analysis.

An experimental study is presented on the possibility of using the fluorescence from organic dyes as a broadband light source together with a monochromator for applications in excitation-emission matrix (EEM) fluorescence spectroscopy. A high-power single-chip light-emitting diode (LED) was chosen as an excitation source with a central output wavelength at 365 nm to excite a fluorescent solution of Coumarin 1 dye dissolved in ethanol. Two excitation configurations were investigated: direct excitation from the LED and excitation through an optical-fiber-coupled LED. A Czerny-Turner monochromator with a diffraction grating was used for the spectral tuning of the fluorescence. A simple method was investigated for increasing the efficiency of the excitation as well as the fluorescence signal collection by using a diffuse reflector composed of barium sulfate (BaSO4) and polyvinyl alcohol (PVA). As research objects, extra-virgin olive oil (EVOO), Coumarin 6 dye, and Perylene, a polycyclic aromatic hydrocarbon (PAH), were used. The results showed that the light-emitting-diode-induced fluorescence was sufficient to cover the losses on the optical path to the monochromator output, where a detectable signal could be obtained. The obtained results reveal the practical possibility of applying the fluorescence from dyes as a light source for food system analysis by EEM fluorescence spectroscopy.

Influence of microplastics and environmentally persistent free radicals on the ability of biochar components to promote degradation of antibiotics by activated peroxymonosulfate

Microplastics (MPs) in sludge can affect the ability of biochar-activated peroxymonosulfate (PMS) to degrade antibiotics. In this work, biochar was prepared by mixing sludge and polystyrene (PS) through hydrothermal carbonization (HTC) and high-temperature pyrolysis processes. The resulting biochar was used to activate PMS to degrade ofloxacin (OFX), levofloxacin (LEV), and pefloxacin (PFX). The addition of PS significantly enhanced the ability of biochar/PMS to degrade antibiotics and the levels of environmentally persistent free radicals (EPFRs, 4.59 × 1020 spin/g) due to the decomposition of PS. The addition of PS resulted in a slight decrease in the specific surface area of biochar (2–3 m2/g on average), but a significant increase in the concentration of EPFRs increased the removal efficiency. The activation of PMS by biochar is dominated by free radicals, accounting for about 70%, in which SO4•- and •OH contribute the most and O2•- the least. However, 1O2 contributes 15–20% to the degradation of antibiotics in non-free radical processes. Overall, the process of biochar/PMS degradation of antibiotics is mainly dominated by free radicals, and the effect of non-free radicals is not obvious. Both hydrochar and pyrocarbon samples showed good hydrophilicity, and this property should improve the ability of active sites on biochar to degrade antibiotics. In the HTC process, PS can decompose during hydrochar preparation, with a maximum reduction value of 40.09%. The three-dimension excitation emission matrix fluorescence spectroscopy (3D-EEM) and total organic carbon (TOC) results show that the protein content in sludge plays a major role in reducing PS, with little effect of polysaccharide and SiO2. There are six to seven degradation intermediates of quinolone antibiotics, which are eventually degraded into CO2, H2O, and inorganic substances. The regeneration experiment showed good reusability of hydrochar and pyrocarbon, further demonstrating the suitability of biochar for the degradation of antibiotics.

Effect of nitrogen retention composite additives Ca(H2PO4)2 and MgSO4 on the degradation of lignocellulose, compost maturation, and fungal communities in compost.

This study investigated the effects of the nitrogen retention composite additives Ca(H2PO4)2 and MgSO4 on lignocellulose degradation, maturation, and fungal communities in composts. The study included control (C, without Ca(H2PO4)2 and MgSO4), 1% Ca(H2PO4)2 + 2% MgSO4 (CaPM1), 1.5% Ca(H2PO4)2 + 3% MgSO4 (CaPM2). The results showed that Ca(H2PO4)2 and MgSO4 enhanced the degradation of total organic carbon (TOC) and promoted the degradation of lignocellulose in compost, with CaPM2 showing the highest TOC and lignocellulose degradation. Changes in the three-dimensional excitation-emission matrix fluorescence spectroscopy (3D-EEM) of dissolved organic matter (DOM) components in compost indicated that the treatment group with the addition of Ca(H2PO4)2 and MgSO4 promoted the production of humic acids (HAs) and increased the degree of compost decomposition, with CaPM2 demonstrating the highest degree of decomposition. The addition of Ca(H2PO4)2 and MgSO4 modified the composition of the fungal community. Ca(H2PO4)2 and MgSO4 increased the relative abundance of Ascomycota, decreased unclassified_Fungi, and Glomeromycota, and activated the fungal genera Thermomyces and Aspergillus, which can degrade lignin and cellulose during the thermophilic stage of composting. Ca(H2PO4)2 and MgSO4 also increased the abundance of Saprotroph, particularly undefined Saprotroph. In conclusion, the addition of Ca(H2PO4)2 and MgSO4 in composting activated fungal communities involved in lignocellulose degradation, promoted the degradation of lignocellulose, and enhanced the maturation degree of compost.

Research on enhancing sewage sludge lysis and bioreactor initiation through composite thermophilic strains

Returning lysed sludge to biochemical tanks to achieve in-situ sludge reduction is promising. A novel approach for regulating and initiating the sludge lysis process utilizing thermophilic strains is proposed. In this study, three strains were isolated from sludge, and sequencing of the 16 S rDNA amplicon revealed that the three thermophilic strains were the closest relatives to the genus Geobacillus, and they were designated as Geobacillus sp. DX5, Geobacillus sp. DX8 and Geobacillus sp. DX11. Sludge lysis experiments demonstrated that composite thermophilic strains (CTS) were dosed at 65°C, and the sludge VSS removal efficiency after 24 h was 37.8%, significantly surpassing individual strains. Moreover, 65.8% of proteins and 52.0% of polysaccharides in Extracellular polymeric substances (EPS) of sludge were degraded. Furthermore, Three-dimensional excitation-emission matrix (3D-EEM) fluorescence spectroscopy results revealed a substantial release of dissolved organic matter during sludge lysis. Inoculation of CTS under optimal conditions (65°C, pH 7, 4 × 1010cfu/L) resulted in VSS removal efficiency and protease activity of 42.7% and 2584 U/L, respectively. After 20 days of inoculation with CTS to initiate sludge lysis reactor, VSS removal efficiency reached 46%. Additionally, it stimulated the growth of the thermophilic bacterial community, engaging indigenous thermophilic strains in the sludge lysis process.

Adulteration Detection and Quantification in Olive Oil Using Excitation-Emission Matrix Fluorescence Spectroscopy and Chemometrics.

This research investigates the use of excitation-emission matrix fluorescence (EEMF) in conjunction with chemometric models to rapidly identify and quantify adulteration in olive oil, a critical concern where sample availability is limited. Adulteration is simulated by blending soybean, peanut, and linseed oils into olive oil, creating diverse adulterated samples. Principal component analysis (PCA) was applied to the EEMF spectral data as an initial exploratory measure to cluster and differentiate adulterated samples. Spatial clustering enabled vivid visualization of the variations and trends in the spectra. The novel application of parallel factor analysis (PARAFAC) for data decomposition in this paper focuses on unraveling correlations between the decomposed components and the actual adulterated components, which offers a novel perspective for accurately quantifying adulteration levels. Additionally, a comparative analysis was conducted between the PCA and PARAFAC methodologies. Our study not only unveils a new avenue for the quantitative analysis of adulterants in olive oil through spectral detection but also highlights the potential for applying these insights in practical, real-world scenarios, thereby enhancing detection capabilities for various edible oil samples. This promises to improve the detection of adulteration across a range of edible oil samples, offering significant contributions to food safety and quality assurance.

Application of EEM fluorescence spectroscopy for characterizing organic DBP precursors in different water sources: a review

Abstract Disinfection by-products (DBPs), generated from the reaction of disinfectants with DBP precursors, have been found to pose unintentional risks to human health. Considering that the concentration and speciation of DBPs formed during disinfection will be affected by the content and composition of dissolved organic matter (DOM), widespread concern about the characteristics of DBP precursors in water sources have been prompted. Three-dimensional excitation–emission matrix (EEM) can quickly and efficiently determine the properties and composition of DOM in water, and thus is generally used to investigate the origin of DBP precursors in water sources. This study overviews the fluorescent properties of different DBP precursors, summarizes the application of different EEM interpretation methods in DBP precursors and analyses the key factors affecting the correlation between the fluorescent components and DBP precursors (e.g., natural organic matter, algal organic matter, effluent organic matter and organic matter derived from other sources). A series of factors, including composition of fluorophores, bromide concentration, spatio-temporal characteristics and disinfectant types, could impact the correlation between DBP formation potential and fluorescent components. As for future research needs, it is of significance to select suitable fluorescence analysis methods and investigate the combination of EEM with other characterization technologies based on different situations.

Rapid identification of Radix Astragali origin by using fluorescence probe combined with chemometrics

Fluorescent probes for metal ion recognition can be divided into selective probes, weakly selective probes, and non-selective probes roughly. Weakly selective probes are not often used for quantitative analysis of metal ions due to their overlapping spectra resulting from simultaneous interactions with multiple metal ions. Conversely, the different metal ions contained in herbal medicine extracts from different geographical origins will produce corresponding fluorescence fingerprint profiles after interaction with weakly selective fluorescence probes. The performance can be used in the study of origin tracing of food or Chinese herbal medicine. Weakly selective fluorescent probes of benzimidazole derivatives have been synthesized and attempted to be used in the origin tracing of Radix Astragali in this work. Radix Astragali from different origins will produce different fluorescence fingerprint spectra due to the difference of metal ions and content in combination with the probe. Excitation-emission matrix (EEM) fluorescence spectroscopy in conjunction with N-way partial least squares discriminant analysis (N-PLS-DA), and unfolded partial least squares discriminant analysis (U-PLS-DA) were used to identify the origin of 150 Radix Astragali samples from five geographical origins. The prediction results showed that the correct recognition rates of the U-PLS-DA model and N-PLS-DA model are 95.92% and 93.88%, respectively. In comparison, the results of U-PLS-DA are slightly better than those of N-PLS-DA. These findings indicate that EEM fluorescence spectroscopy based on weakly selective fluorescent probes combined with multi-way chemometrics provides a good idea for the origin tracing of traditional Chinese medicine.

Seasonal changes in water-soluble brown carbon (BrC) at Nanling background station in South China

Brown carbon (BrC) is an important light-absorbing component of organic carbon (OC), causing large uncertainty in aerosol radiative forcing evaluation and being related to health issues as well. Knowledge of BrC in an atmospheric background station is beneficial to understand its role in a changing climate. A year-long sampling campaign was conducted at Nanling background station to get a comprehensive knowledge of WS-BrC, a total of seventy-two PM2.5 samples throughout a year were used. Light absorption and fluorescence spectra of WSOC were analyzed synchronously using a fluorescence spectrophotometer. The low levels of PM2.5, OC, and elemental carbon (EC) conferred a background site. The optical properties of WS-BrC were characterized using excitation-emission matrix (EEM) fluorescence spectroscopy. The WS-BrC made a significant contribution (365 nm, 18% ± 10%) to total carbonaceous aerosol absorption. The mass absorption efficiency (MAE) of WS-BrC is 0.81 ± 0.34 m2 gC–1, and varies among seasons due to the different sources or atmospheric processing. Three EEM fluorescent components were identified by parallel factor (PAFAFAC) analysis, including two humic-like substances (HULIS, C1, C2), and one phenolic-like component. The HULIS components accounted for approximately 70% of the total fluorescence intensities. Primary combustion emissions showed enhanced activity during the winter and spring seasons, but there were no significant influences on WS-BrC in spring. Secondary sources contributed significantly to WS-BrC during winter, summer, and autumn (all exceeding 50%), except for spring. Photooxidation is a significant process in the formation of secondary WS-BrC in winter and autumn, but there may be another formation pathway in summer, i.e., the ammonia pathway. This study contributes to our understanding of BrC in the background atmosphere.

Stratification of dissolved organic matter in the upper 5000 m water column in the western Pacific Ocean

Marine dissolved organic matter (DOM) is a principal reservoir involved in biogeochemical cycles and exerts a pivotal influence on global carbon flux dynamics. In this study, excitation-emission matrix fluorescence spectroscopy combined with parallel factor analysis (EEM-PARAFAC) was conducted on 230 DOM samples collected from 21 sites between February and April 2022 in the Western Pacific Ocean (WPO). We identified five distinct fluorescence peaks (peaks B, T, A, C, and M), predominantly protein-like and humic-like components. These findings, marked by significant differences (p < 0.01) in fluorescence intensities and spectral indices, characterized the transformation of DOM with ocean depth, illustrating a transition from active to recalcitrant forms. Additionally, random forest analysis (RFA) identified depth as a key factor influencing marine dissolved organic carbon (DOC), with a 32.59% importance value. Correlations between hydrological and fluorescent parameters underscored the complexity of DOM sources and influencing processes. Overall, this work broadens our understanding of DOM variability in the upper 5000 m of the WPO, enhancing our knowledge of the marine environment's role in the global carbon cycle.

Molecular signatures and formation mechanisms of water-soluble chromophores in particulate matter from Karachi in Pakistan

Excitation-emission matrix (EEM) fluorescence spectroscopy is a widely-used method for characterizing the chemical components of brown carbon (BrC). However, the molecular basics and formation mechanisms of chromophores, which are decomposed by parallel factor (PARAFAC) analysis, are not yet fully understood. In this study, we characterized the water-soluble organic carbon (WSOC) in aerosols collected from Karachi, Pakistan, using EEM spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). We identified three PARAFAC components, including two humic-like components (C1 and C2) and one phenolic-like species (C3). We determined the molecular families associated with each component by performing Spearman correlation analysis between FT-ICR MS peaks and PARAFAC component intensities. We found that the C1 and C2 components were associated with nitrogen-enriched compounds, where C2 with the longest emission wavelength exhibited a higher level of aromaticity, N content, and oxygenation than C1. The C3 associated formulas have fewer nitrogen-containing species, a lower unsaturation degree, and a lower oxidation state. An oxidation pathway was identified as an important process in the formation of C1 and C2 components at the molecular level, particularly for the assigned CHON compounds associated with the gas-phase oxidation process, despite their diverse precursor types. Numerous C2 formulas were found in the “potential BrC” region and overlapped with the BrC-associated formulas. It can be inferred that the compounds that fluoresce C2 contributed considerably to the light absorption of BrC. These findings are essential for future studies utilizing the EEM-PARAFAC method to explore the sources, processes, and compositions of atmospheric BrC.

Resolving fluorescence spectra of Maillard reaction products formed on bovine serum albumin using parallel factor analysis

Formation of Maillard reaction products (MRPs) is increasingly studied by the use of fluorescence spectroscopy, and most often, by measuring single excitation/emission pairs or use of unresolved spectra. However, due to the matrix complexity and potential co-formation of fluorescent oxidation products on tryptophan and tyrosine residues, this practice will often introduce errors in both identification and quantification. The present study investigates the combination of fluorescence excitation emission matrix (EEM) spectroscopy and parallel factor analysis (PARAFAC) to resolve the EEMs into its underlying fluorescent signals, allowing for better identification and quantification of MRPs. EEMs were recorded on a sample system of bovine serum albumin incubated at 40 °C for up to one week with either glucose, methylglyoxal or glyoxal added. Ten unique PARAFAC components were resolved, and assignment was attempted based on similarity with fluorescence of pure standards of MRPs and oxidation products and reported data from literature. Of the ten fluorescent PARAFAC components, tyrosine and buried and exposed tryptophan were resolved and identified, as well as the formation of specific MRPs (argpyrimidine and Nα-acetyl-Nδ-(5-methyl-4-imidazolon-2-yl)ornithine) and tryptophan oxidation products (kynurenine and dioxindolylalanine). The formation of the PARAFAC resolved protein modifications were qualitatively validated by liquid chromatography-mass spectrometry.

Accelerated size-focusing light activated synthesis of atomically precise fluorescent Au22(Lys-Cys-Lys)16 clusters.

Atomically precise metal nanoclusters are promising candidates for various biomedical applications, including their use as photosensitizers in photodynamic therapy (PDT). However, typical synthetic routes of clusters often result in complex mixtures, where isolating and characterizing pure samples becomes challenging. In this work, a new Au22(Lys-Cys-Lys)16 cluster is synthesized using photochemistry, followed by a new type of light activated, accelerated size-focusing. Fluorescence excitation-emission matrix spectroscopy (EEM) and parallel factor (PARAFAC) analysis have been applied to track the formation of fluorescent species, and to assess optical purity of the final product. Furthermore, excited state reactivity of Au22(Lys-Cys-Lys)16 clusters is studied, and formation of type-I reactive oxygen species (ROS) from the excited state of the clusters is observed. The proposed size-focusing procedure in this work can be easily adapted to conventional cluster synthetic methods, such as borohydride reduction, to provide atomically precise clusters.

Selenium bio-nanocomposite based on extracellular polymeric substances (EPS): Synthesis, characterization and application in alleviating cadmium toxicity in rice (Oryza sativa L.)

Selenium nanoparticles (SeNPs) have gained significant attention owing to their favorable bioavailability and low toxicity, making them widely applications in the fields of medicine, food and agriculture. In this study, bacterial extracellular polymeric substances (EPS) were used as a novel stabilizer and capping agent to prepare dispersed SeNPs. Results show that EPS-SeNPs presented negative potential (−38 mV), spherical morphologies with average particle size about 100–200 nm and kept stable at room temperature for a long time. X-ray diffraction (XRD) analysis demonstrated that the synthesized nanoparticles were pure amorphous nanoparticles, and X-ray photoelectron spectroscopy (XPS) spectrum showed a spike at 55.6 eV, indicating the presence of zero-valent nano‑selenium. Fourier-transform infrared spectroscopy (FTIR) and three-dimensional excitation-emission matrix (3D-EEM) fluorescence spectroscopy analysis confirmed proteins and polysaccharides in EPS played a crucial role in the synthesis of EPS-SeNPs. Compared to EPS or sodium selenite (Na2SeO3), EPS-SeNPs showed a relatively moderate result in terms of scavenging free radicals in vitro. In contrast, EPS-SeNPs demonstrated lower toxicity to rice seeds than Na2SeO3. Notably, the exogenous application of EPS-SeNPs effectively alleviated the growth inhibition and oxidative damaged caused by cadmium (Cd), and significantly reduced Cd accumulation in rice plants.

Fast and efficient processes for oxidation and monitoring of polycyclic aromatic hydrocarbons in environmental matrices

This study proposes a new approach for the efficient photodegradation of polycyclic aromatic hydrocarbons (PAH) and derivatives. PAH removal was achieved in just a few minutes using a microwave photochemical reactor capable of producing a high concentration of •OH (2.3 mmol L−1 h−1). Fluorescence excitation-emission matrix (EEM) spectroscopy coupled to parallel factor analysis (PARAFAC) was used for quantifying two PAH and one alkylated PAH at low concentrations (μg L−1). These results highlight the high potential of the photochemical degradation system coupled to EEM-PARAFAC as an alternative fast, inexpensive, and efficient approach for environmental remediation studies of PAH.

Classification of water by bacterial presence using chemometrics associated with excitation-emission matrix fluorescence spectroscopy

Bacterial presence in water is an important indicator of water quality and, when found in high concentrations, may risk human health. The detection of total coliforms, thermotolerant coliforms, and Escherichia coli (E. coli) in water through standard methods involves time-consuming and expensive laboratory tests, which may not always provide timely and accurate results. An alternative approach is excitation-emission matrix fluorescence spectroscopy (EEMFS), which offers fast detection of bacteria in water by analyzing fluorescent compounds. Chemometrics methods can be used to process EEMF spectrum, extract the relevant information, and differentiate water samples based on the presence of bacteria using classification models. In this study, various classification algorithms were applied to EEMFS datasets, including k-nearest neighbors (k-NN), partial least squares discriminant analysis (PLS-DA), multiway-PLS (NPLS-DA), principal component analysis with discriminant analysis (PCA-DA), support vector machines (SVM), and random forest (RF). Models were developed after the unfold multiway and parallel factor analysis (PARAFAC) to classify groundwater, freshwater, saltwater, and treated water samples according to the presence of E. coli, thermotolerant coliforms, and total coliforms. Among these models, PLS-DA, SVM, and RF demonstrated superior performance in discriminating the samples in most cases. In the test sets, the accuracy of the best models for total coliforms varied from 85.2% to 100% for groundwater, 71.4% to 98.2% for freshwater, 64.6% to 81.3% for treated water, and 65.8% to 71.1% for saltwater. Accuracy for E. coli and thermotolerant coliforms ranged from 89.3% to 100% in groundwater and from 64.7% to 87.5% for treated water. Results for thermotolerant coliforms in freshwater were 64.8% to 95.2%, and 63.3% to 76.7% for saltwater. For E. coli, accuracy ranged from 73.8% to 78.6% for freshwater and 65.0% to 80.0% for saltwater.

Solid-phase fluorescence: Reproducibility and comparison with the solution states

Solid-phase fluorescence excitation-emission matrix (SPF-EEM) spectroscopy has potential for non-extractive, non-destructive, and non-contact analytical measurements of powder and solid-state samples, as well as front-face EEM spectroscopy for suspensions of high optical density. However, as there is no unified measurement method for SPF spectroscopy, comparing samples measured in different research fields is difficult. Therefore, this study designs a cell that can be created by a 3D printer and examines reproducibility on measuring fluorescent powders. The developed cell is applied to proteins (ovalbumin, BSA, gliadin, gluten, powdered collagen, casein), amino acids (tryptophan, tyrosine, and phenylalanine), soybean ingredients (daidzein, and genistein), and fluorescent chemicals (rhodamine B, fluorescein sodium salt, pyrene, and quinine sulfate dihydrate) and their spectra are compared with those in the solution states. When samples are refilled into the cell three times, the cell exhibits high reproducibility in terms of fluorescence peak wavelength and intensity. The solid proteins exhibit peaks attributed to the fluorescent amino acid residues, and broad peaks which are not detected for the proteins in the solution states. Powdered rhodamine B and fluorescein sodium salt do not exhibit fluorescence, possibly due to the inner-filter effect (IFE). Some non-colored molecules also exhibit loss of fluorescence or a remarkable difference between the solid and solution states, possibly due to the interaction of the fluorescent structure with the surrounding local environment, similar to the solvent effect, which is possibly affected by the molecular proximity, three-dimensional structure, and moisture absorption capacity.

Humification levels of dissolved organic matter in the eastern plain lakes of China based on long-term satellite observations

Under the influence of intensive human activities and global climate change, the sources and compositions of dissolved organic matter (DOM) in the eastern plain lake (EPL) region in China have fluctuated sharply. It has been successfully proven that the humification index (HIX), which can be derived from three-dimensional excitation-emission matrix fluorescence spectroscopy, can be an effective proxy for the sources and compositions of DOM. Therefore, combined with remote sensing technology, the sources and compositions of DOM can be tracked on a large scale by associating the HIX with optically active components. Here, we proposed a novel HIX remote sensing retrieval (IRHIX) model suitable for Landsat series sensors based on the comprehensive analysis of the covariation mechanism between HIX and optically active components in different water types. The validation results showed that the model runs well on the independent validation dataset and the satellite-ground synchronous sampling dataset, with an uncertainty ranging from 30.85 % to 36.92 % (average ± standard deviation = 33.6 % ± 3.07 %). The image-derived HIX revealed substantial spatiotemporal variations in the sources and compositions of DOM in 474 lakes in the EPL during 1986–2021. Subsequently, we obtained three long-term change modes of the HIX trend, namely, significant decline, gentle change, and significant rise, accounting for 74.68 %, 17.09 %, and 8.23 % of the lake number, respectively. The driving factor analysis showed that human activities had the most extensive influence on the DOM humification level. In addition, we also found that the HIX increased slightly with increasing lake area (R2 = 0.07, P < 0.05) or significantly with decreasing trophic state (R2 = 0.83, P < 0.05). Our results provide a new exploration for the effective acquisition of long-term dynamic information about the sources and compositions of DOM in inland lakes and provide important support for lake water quality management and restoration.

Effect of experimental warming on dissolved organic matter and bacterial diversity in a forest swamp soil

Forest swamp ecosystems play an important role in the global carbon cycle, yet they are often overlooked. With global climate warming, it is inevitable that it will impact the relationship between soil microorganisms and organic matter. Dissolved organic matter (DOM) in the soil environment is extremely sensitive to environmental changes. Understanding the effects of climate change on DOM and microorganisms is crucial for assessing the stability of carbon (C) in forest swamp soils. Therefore, we conducted a 142-day laboratory warming incubation experiment (control: 10 °C, and warming: 20 °C) to investigate the response of forest swamp soil microbial and DOM properties to warming. Excitation-emission matrix (EEM) fluorescence spectroscopy was used to explore the changes in different material compositions of DOM over time at different incubation temperatures, and high-throughput sequencing was used to investigate the changes in soil bacteria. The DOM content (dissolved organic C, DOC) and the degree of humification index (HIX) increased with an increase in incubation time under warming conditions (p < 0.05). In contrast, microbial humic substances (C3) decreased with increasing time. Long-term warming has separated bacterial communities and gradually tightened the degree of connectivity between bacterial networks. The degree of soil humification (Mantel test r = 0.58, p < 0.01) and DOC (r = 0.21, p < 0.05) were the most critical indicators that changed the diversity of the bacterial community. Our findings suggest a degree of interaction between changes in forest swamp soil microbial communities and DOM under warming conditions. The results of this study contribute to our understanding of changes in DOM fluorescence indices in forest swamp soils under the influence of climate change and their associated microbial mechanisms.