Excitation-emission Matrix Spectroscopy Research Articles

Karenia brevis and Pyrodinium bahamense Utilization of Dissolved Organic Matter in Urban Stormwater Runoff and Rainfall Entering Tampa Bay, Florida

This study investigated how nitrogen and dissolved organic matter (DOM) from stormwater runoff and rainfall support the growth of Karenia brevis and Pyrodinium bahamense. Excitation–emission matrix spectroscopy coupled with parallel factor analysis tracked changes in the optical properties of DOM in each bioassay, revealing greater reactivity of terrestrial humic-like DOM. Significant increases in cell yield and specific growth rates were observed upon additions of runoff for both species, with significant increases in specific growth rates upon the addition of a 2 in simulated rain event for P. bahamense only. By hour 48, 100% of the dissolved organic nitrogen (DON) in each treatment was utilized by P. bahamense, and by hour 72, over 50% of the DON was utilized by K. brevis. The percentage of bioavailable dissolved organic carbon (DOC) was greater for P. bahamense compared to K. brevis, suggesting a greater affinity for DOC compounds by P. bahamense. However, the bioavailability of DOM for each species could be owed to distinct chemical characteristics of labile DOM conveyed from each site. This study demonstrates that stormwater runoff and rainfall are both sources of labile DOM and DON for K. brevis and P. bahamense, which has implications for blooms of these species in Tampa Bay waters.

Use of spectroscopic process analytical technology for rapid quality evaluation during preparation of CHO cell culture media.

Media preparation parameters contribute significantly to media quality, cell culture performance, productivity, and product quality. Establishing proper media preparation procedures is critical for ensuring a robust CHO cell culture process. Process analytical technology (PAT) enables unique ways to quantify assessments and improve media quality. Here, cell culture media were prepared under a wide range of temperatures (40-80°C) and pH (7.6-10.0). Media quality profiles were compared using three real-time PATs: Fourier-transform infrared (FTIR) spectroscopy, Raman spectroscopy, and excitation-emission matrix (EEM) spectroscopy. FTIR and Raman spectroscopies identified shifts in media quality under high preparation temperature (80°C) and at differing preparation pH which negatively impacted monoclonal antibody (mAb) production. In fed-batch processes for production of three different mAbs, viable cell density (VCD) and cell viability were mostly unaffected under all media preparation temperatures, while titer and cell specific productivity of mAb decreased when cultured in basal and feed media prepared at 80°C. High feed preparation pH alone was tolerated but cell growth and productivity profiles deviated from the control condition. Further, charge variants (main, acidic, basic species) and glycosylation (G0F, afucosylation, and high mannose) were examined. Statistically significant differences were observed for one or more of these quality attributes with any shifts in media preparation. In this study, we demonstrated strong associations between media preparation conditions and cell growth, productivity, and product quality. The rapid evaluation of media by PAT implementation enabled more comprehensive understanding of different parameters on media quality and consequential effects on CHO cell culture.

Insights into the impact of complex phosphates on acid-induced milk fan gel properties: Texture, rheological, microstructure, and molecular forces

Milk fan cheese, a type of stretched -cheese, presents challenges in its stretch-forming. This study investigated the impacts of complex phosphates (sodium tripolyphosphate and sodium dihydrogen phosphate, STPP-DSP) on the gelling properties of acid-induced milk fan gel and the mechanisms contributing to its stretch-forming. The treatment of milk fan gel with STPP-DSP resulted in improved functional and textural properties compared with the control group. In particular, drawing length increased significantly from 69.67 nm to 80.33 nm, and adhesiveness increased from 1737.89 g/mm to 1969.79 g/mm. The addition of STPP-DSP also led to increased viscosity, elastic modulus (G'), and viscous modulus (G"). Microstructural analysis revealed the formation of a fibrous structure within the gel after STPP-DSP treatment, facilitating uniform embedding of fat globules and emulsification. Structural analysis showed that the addition of STPP-DSP increased β-fold and decreased random coiling of the gel, facilitating the unfolding of protein structures. Additionally, UV absorption spectroscopy and excitation-emission matrix spectroscopy results indicated the formation of a chelate between STPP-DSP and milk fan gel, increasing protein-protein molecular interactions. Evidence from differential scanning calorimetry and x-ray diffraction demonstrated the formation of sodium caseinate chelate. Fourier transform infrared spectroscopy and zeta potential analysis revealed that the sodium caseinate chelate formed through hydrophobicity, hydrogen bonding, and electrostatic forces. These findings provided theoretical insights into how phosphates can improve the stretch-forming of milk fan gel, facilitating the application of phosphate additives in stretched -cheese processing.

Indirect photodegradation of zinc pyrithione: The effect of chromophoric dissolved organic matter components and seawater factors

Chromophoric dissolved organic matter (CDOM) is the main photosensitizer in seawater. CDOM can absorb solar radiation extensively and generate reactive intermediates (RIs), including singlet oxygen (1O2), hydroxyl radicals (HO·), and CDOM triplet states (3CDOM*), that are favorable for indirect photodegradation of organic pollutants. In the current study, the effect and mechanism of CDOM components on zinc pyrithione (ZnPT) indirect photodegradation were studied. Among the three CDOM isolates (humic acid (JKHA), Suwannee River humic acid (SRHA), and Suwannee River natural organic matter (SRNOM)), JKHA had the highest fluorescence intensity per gram of carbon and the fastest indirect photodegradation rate for ZnPT. Furthermore, the fluorescent components were divided into four terrestrial humic-like components: C1, C2, C3, and C4, by using excitation–emission matrix spectroscopy combined with parallel factor analysis. A notable relationship was found between the four fluorescent components of CDOM and ZnPT indirect photodegradation. The indirect photodegradation rate of ZnPT varied in different types of CDOM solutions, which may be attributed to the different compositions of CDOM. The relative contents of C1 and C4 were significantly higher in JKHA than in the other two CDOMs, and they were the major contributors to the production of 3CDOM* and 1O2, which promoted ZnPT indirect photodegradation. The impact of seawater factors on ZnPT indirect photodegradation was also investigated. The ZnPT indirect photodegradation rate initially decreased and then increased as the pH increased from 5.00 to 11.00. The lowest rate of indirect photodegradation of ZnPT was observed at pH = 9.00. As the salinity was <25‰, in salinity the ZnPT indirect photodegradation rate increased concomitantly with an increase, and pronounced inhibition of ZnPT indirect photodegradation was observed when the salinity was >25‰. Nitrate had a promoting influence on ZnPT indirect photodegradation, whereas HCO3−, halogen ions, and metal ions all inhibited it.

Modulation of molecular state and air-water interface adsorption behavior of ovalbumin via interference with its surrounding charge distribution

Herein, pH combined with ionic strength was employed to modulate the charge distribution around ovalbumin molecules, and the whole process (from the water phase to the interface) of film formation and stabilization of ovalbumin at the air-water interface was further analyzed. As the pH continuously rose above the isoelectric point, the molecular surface charge increased. More cations, however, reduced the surface charge through the electrostatic shielding effect. The pH and cationic strength were shown to have a remarkable effect on the aggregate size. Intrinsic fluorescence and excitation emission matrix spectroscopy indicated that the migration of tryptophan and tyrosine was accompanied by a change in the backbone structure and rearrangement of the hydrophilic/hydrophobic side chains. Interfacial adsorption kinetic analysis revealed that low pH and ionic strength generally favored the adsorption and stabilization of ovalbumin. Lissajous plots confirmed that stronger intra-interfacial interactions and viscoelastic-like solid interfaces would be generated under the above conditions. Interfacial dilatational rheology analysis illustrated that in most cases, the interfacial film formed by ovalbumin was dominated by an elastic response and produced a nonlinear viscoelastic response under strain. Overall, the combined effect of low pH (pH 5.0) and ionic strength (25 mmol/L and 50 mmol/L) on the surface charge resulted in superior foam capacity (60.00% for pH 5.0 and 50 mmol/L) and stability (97.87% for pH 5.0 and 25 mmol/L). This study detailed the mechanism by which charge influenced the molecular and interfacial properties of ovalbumin, leading the way for the development of protein-based foam systems.

Ferrous sulfide nanoparticles can be biosynthesized by sulfate-reducing bacteria: Synthesis, characterization and removal of heavy metals from acid mine drainage

Ferrous sulfide nanoparticles (nFeS) have proven to be effective in removing heavy metals (HMs) from wastewater. One such approach, which has garnered much attention as a sustainable technology, is via the in situ microbial synthesis of nFeS. Here, a sulfate-reducing bacteria (SRB) strain, Geobacter sulfurreducens, was used to initially biosynthesize ferrous sulfide nanoparticles (SRB-nFeS) and thereafter remove HMs from acid mine drainage (AMD). SRB-nFeS was characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) coupled to an energy dispersive spectrometer (EDS), three-dimensional excitation-emission matrix (3D-EEM) spectroscopy, Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). Such characterization showed that SRB mediated the reduction of SO42- to S2- to form nFeS, where the metabolized substances functioned as complexing agents which coordinated with nFeS to form biofunctional SRB-nFeS with improved stability. One advantage of this synthetic route was that the attachment of nFeS to the bacterial surface protected SRB cells from HM toxicity. Furthermore, due to a synergistic effect between nFeS and SRB, HM removal from both solution and AMD by SRB-nFeS was enhanced relative to the constituent components. Thus, after 5 consecutive cycles of HM removal, SRB-nFeS removed, Pb(Ⅱ) (92.6%), Cd(Ⅱ) (78.7%), Cu(Ⅱ) (76.0%), Ni(Ⅱ) (62.5%), Mn(Ⅱ) (62.2%), and Zn(Ⅱ) (88.5%) from AMD This study thus provides new insights into the biosynthesis of SRB-nFeS and its subsequent practical application in the removal of HMs from AMD.

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.

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.

Spectroscopic probing of ultraviolet-induced degradation in elastomeric polyurea

Aromatic polyurea has garnered assiduous research due to its excellent impact, shock, abrasion, moisture, and chemical resistance properties. Polyurea can be used in protective coating and impact mitigation applications but is inevitably exposed to harsh deployment conditions such as extended ultraviolet (UV) radiation. Fourier Transform Infrared (FTIR) spectroscopy, Terahertz-time domain spectroscopy (THz-TDS), and Excitation-Emission Matrix spectroscopy (EEMS) deciphered the effects of UV radiation on radiated polyurea samples under ambient and nitrogen-rich conditions. Samples were radiated continuously for up to 15 weeks in increments of 3 weeks. Comprehensive FTIR analyses revealed a monotonic increase in disordered hydrogen bonding as a function of exposure duration in an ambient environment. Otherwise, marginal changes were observed in UV-radiated samples under nitrogen. The hydrogen bond length exhibited significant variations in the former compared to their nitrogen atmosphere counterparts. The results infer the nitrogen shielding effect, protecting polyurea from the photodegradation and photo-oxidation observed in samples radiated under the ambient atmosphere. THz-TDS spectra affirmed the FTIR results by probing changes in the complex refractive index. Terahertz spectral peaks associated with torsional vibrations of intermolecular hydrogen bonds in polyurea were notably correlated with increased exposure duration in the ambient atmosphere. Changes in the complex index as a function of exposure duration under nitrogen are minimal. The excitation-emission spectra of polyurea samples reveal a strong fluorescent behavior in 9-week and 12-week ambient-exposed polyurea due to cluster-triggered emission mechanisms. The results synthesized based on three different spectroscopy techniques paint a holistic portrait of the adverse effects of extended ultraviolet radiation of macromolecules deployed in harsh environmental conditions.

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.

Reducing the mass and decreasing the bioavailability of heavy mental from organic wastes treated by black soldier fly larvae

Black soldier fly larvae (BSFL), Hermetia illucens L., are widely used to reduce the mass of various wastes. However, the potential metal tolerance mechanisms during periods of waste bioconversion by BSFL remain largely unknown. To further reveal the mechanisms, BSFL were used to treat the agricultural organic wastes, including pig manure (PM), cow manure (COM), spent mushroom substrate (SMS), and wet distiller grains (WDG). After these individual and combined waste(s) were treated by BSFL, we investigated the waste reduction rates and evaluated the responses of BSFL gut microbes to heavy metals of agricultural organic wastes. Additionally, the colloidal particles of residual wastes were characterized by combing energy dispersive X-ray (EDX) spectroscopy, Size potential, Zeta potential, and excitation-emission matrix (EEM) spectroscopy. Results indicated that the waste reduction rates were up to 74% in COM+WDG and 69% in WDG, most of heavy metals (e.g., Zn and Co) from organic wastes were not accumulated in the bodies of mature larvae after treatment. Further, results obtained from the prediction of gene function on the basis of 16 S rRNA data revealed that the presence of multi-resistance genes in the gut of BSFL can help the larvae resist Zn and/or Co stress. In addition, the drug sensitivity test implied that BSFL5_L and BSFL6_L from BSFL gut bacterial strains have multi-resistance to Co and Zn. Additionally, EDX results revealed that the colloidal particles in five waste residues after BSFL treatment are mainly consisted of Fe, Ca and Si, which can capture heavy metals (e.g., Cu, Mn). Results from EEM spectroscopy and PARAFAC showed that tryptophan-like and humic-like accumulatively account for 56%− 68% of all components. Importantly, these two components could strongly bind the metal elements and form colloidal particles with high stability, and therefore reduce the heavy metal pollution of agricultural organic wastes. Our findings offered an environment-friendly method to treat agricultural organic wastes, which would be far-reaching influence to our environment.

The telltale fluorescence fingerprints of sewer flows for interpreting the low influent concentration in wastewater treatment plant

Low degradability of wastewater treatment plant (WWTP) influents negatively affects its ability to effectively remove pollutants through wastewater treatment processes. Proactive assessment of urban sewer system performance is highly valued in the selection of targeted countermeasures for this occurrence. In this study, a fluorescence spectrum interpretation approach was developed to identify the causes of low biodegradability of WWTP influent by using parallel factor analysis (PARAFAC) and fluorescence regional integration (FRI) of excitation-emission matrix spectroscopy. Statistical analysis was also used to further interpret the PARAFAC- and FRI-derived data. The urban sewer catchment served by a WWTP in Wuhan City, China, was used as the test site to demonstrate the effectiveness of this approach. The results showed that electronics manufacturing industrial wastewater and groundwater input into the urban sewer would significantly decrease the biodegradability of the WWTP influents, and these sources were characterized by much lower fluorescence peak intensities, especially for protein-like substances, including tryptophan-like T and tyrosine-like B1 and B2. The potential conversion of high freshness T into low freshness B2 within the sewer may also contribute to this undesirable scenario. The ratio of peak T to peak B2 and the ratio of the FRI fraction of region I to that of region II can be used together to determine the predominance of industrial wastewater and groundwater. T/B2 < 1.3 indicates the entry of industrial wastewater or groundwater into urban sewers, and I/II > 0.5 further confirms the input of industrial wastewater. Accordingly, the low biodegradability of the WWTP influents in our study site is mostly due to the inflow of industrial wastewater rather than groundwater infiltration into the urban sewers. Therefore, actions should be focused on the surveillance of industrial wastewater rather than widespread sewer inspection and repairs. In this way, this methodology is cost-effective in aiding targeted countermeasures to improve the urban sewer system performance.

Investigation of lysing excess sludge slurry using hydrolase secreting thermophilic bacterial communities

Sludge reduction is a critical challenge in biological wastewater treatment. Combining excess sludge slurry lysis technology with traditional activated sludge processes is a promising approach for in-situ sludge reduction. Here, a strategy for excess sludge slurry lysis based on thermophilic bacterial communities (LTBC) was proposed. This investigation focused on the process of excess sludge slurry lysis dominated by thermophilic bacterial communities domesticated at different temperatures (55–75 °C). The evolution of sludge lysate was analyzed, and the mechanism of excess sludge slurry lysis under the action of thermophilic bacterial communities was elucidated through amplicon sequencing analysis. The results demonstrated that the aerobic thermophilic bacterial communities adapted to 75 °C exhibit the highest efficiency in sludge slurry lysis. During LTBC process, the removal efficiency of volatile suspended solids reached 53.9 ± 1.8% within 2 h, and 97.0 ± 1.0% of the protein and 96.0 ± 1.0% of the polysaccharide in the extracellular polymers was solubilized, and bacterial cell walls in sludge were disrupted. Fourier transform infrared spectroscopy and excitation-emission matrix spectroscopy of the sludge lysate demonstrated that the LTBC process was accompanied by humification process. The accumulation of humic acid primarily occurred at 55 °C and 65 °C, while fulvic acid occurred at 75 °C. The thermophilic bacterial communities adapted to 75 °C were dominated by Thermus and Thermaerobacter. Phylogenetic studies showed that the LTBC hydrolase system comprises enzymes related to protein hydrolysis, carbohydrate hydrolysis, and peptidoglycan hydrolysis, including metalopeptidase MepB, neutral α-glucosidase C, N-acetyl Muramyl-L-alanine amidase, and others enzymes. These results provide a theoretical basis for the application of LTBC technology in the reduction of sludge which generated in traditional waste water activated sludge processes.

Corrosion analysis of unearthed jade from Daye Zhen Tomb of Northern Zhou Dynasty

X-ray fluorescence spectroscopy, scanning electron microscopy energy spectrum, excitation-emission matrix spectroscopy, and Fourier transform infrared spectroscopy was applied to the unearthed jade with multilayered corrosion, to reveal the microstructure, composition structure, and distribution of organic matters. Our results showed that the interior of the jade was mainly composed of layered serpentine with a regular structure, while the white layer structure on the surface is scattered and irregular, and the content of calcite formed by elements Ca and C increases significantly; between the green matrix and the white layer on the surface, there are brown corrosion zones with obvious fluorescence effect and mainly composed of humic acid, which continuously extends inward along the corrosion cracks for accelerating the internal corrosion. This article, for the first time, argued for the corrosive and fluorescent humic acid bands that appear inside serpentine jade and cautions its role in investigating the corrosion of jade.

Fluorescence spectroscopic characterization of dissolved organic matter in the wastewater treatment plant and hybrid constructed wetlands coupling system in winter: A case study in eastern China

Dissolved organic matter (DOM) in municipal wastewater can have a detrimental effect on aquatic ecosystems, as DOM can participate in the global carbon cycle and change the transport of other pollutants. The characteristics of DOM can also affect the utilization efficiency of dissolved organic carbon by microorganisms in water. In this study, variations in DOM quantity and quality in a full-scale wastewater treatment plant (WWTP) coupled with a hybrid constructed wetland (CW) system during cold periods were characterized by using excitation-emission matrix spectroscopy combined with parallel factor analysis (EEM-PARAFAC). The results showed that the DOM concentration significantly decreased after exiting the WWTP, while a slight increase was found in the CW. The coupled system could significantly eliminate influent DOM with a removal efficiency of 92.1%. The CW system could still remove DOM even in winter. Five fluorescent components, including three humic-like components, one protein-like component and one tyrosine-like component, were identified. Although the biological treatment process in the WWTP contributed a large number of protein-like substances, the optical indices showed that the bioavailability of wastewater was gradually reduced, indicating that DOM was selectively removed by the integrated system. Moreover, there were significant correlations between water quality parameters and DOM indices. This study could contribute to a better understanding of the elimination process of dissolved organic carbon in coupled systems of WWTPs and CWs and offer novel ideas for organic carbon resource recovery and water quality monitoring in watershed environments.

Rational regulation of 3D N-doped carbon macro-architectures toward low-temperature plasma catalysis: The roles of nitrogen content and hierarchical porous structure

The application of low-temperature plasma technology with optimized catalysts in water treatment has shown a good application prospect. However, the relationships between catalytic performance and composition (N atom-doping) and structure (hierarchical porous) of catalysts is still unclear. Here, 3D N-doped carbon macro-architectures is designed by thermolysis of energetic Zn-MOF, where triazole ligand with ultra-high nitrogen content provided the possibility for effective nitrogen doping and creation of hierarchical porous structure. In the DBD system, a series of energetic MOF-derived carbon (EMC-x) catalysts with different pyrolysis temperatures (from 700 to 1000 °C) were prepared, and the composition/structure-effective relationship was investigated in detail. Degradation mechanisms and pathways were analyzed by bursting experiments, quantitative detection of H2O2 and O3, three-dimensional excitation-emission matrix spectroscopy (3D-EEM), LC-MS. The results confirmed that EMC-10 with high nitrogen content and hierarchical porous structure has a wide range of applications in synergistic plasma removal of TTCH from water bodies.

Unveiling the molecular responses of dissolved organic matter in landfill leachate to activated carbon adsorption

Powdered activated carbon (PAC) is an effective method for removing dissolved organic matter (DOM) in membrane bioreactor effluent of landfill leachate (MBR effluent). Among commercially available PACs, wood-based PAC (WoAC) and coal-based PAC (CoAC) are two most common ones. However, the interactions between two PACs and DOM in MBR effluent at the molecular level as well as the effect of PACs properties on the adsorption of DOM compounds are not fully understood. To address the gap, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), three-dimensional fluorescence excitation-emission matrix (EEM) spectroscopy and other spectroscopic techniques were employed to study the change of DOM in MBR effluent when adsorbed by WoAC and CoAC. The results showed that CoAC had a better removal performance of DOM (89.2% for UV254 and 78.4% for DOC) than WoAC (80.9% for UV254 and 70.8% for DOC), which was likely due to the Fe component in CoAC playing an important role in the DOM adsorption process. Both WoAC and CoAC exhibited preferential adsorption for compounds with high unsaturation or poor oxygen. Moreover, the Fe component in CoAC may bind with some functional groups (e.g., carboxyl groups) in unsaturated compounds, which may enhance the adsorption of unsaturated compounds. These findings deepen our understanding of PAC-DOM interactions at the molecular level and provide guidance for designing cost-effective PACs for landfill leachate treatment.

Effect of the molecular weight of DOM on the indirect photodegradation of fluoroquinolone antibiotics

Dissolved organic matter (DOM) is ubiquitous and widespread in natural water and influences the transformation and removal of antibiotics. Nevertheless, the influence of DOM molecular weight (MW) on the indirect photodegradation of antibiotics has rarely been reported. This study attempted to explore the influence of the molecular weight of DOM on the indirect photodegradation of two fluoroquinolone antibiotics (FQs), ofloxacin (OFL) and norfloxacin (NOR), by using UV–vis absorption and fluorescence spectroscopy. The results showed that indirect photodegradation was considered the main photodegradation pathway of FQs in DOM fractions. Triplet-state excited organic matter (3DOM*) and singlet oxygen (1O2) were the main reactive intermediates (RIs) that affected the indirect photodegradation of FQs. The indirect photodegradation rate of FQs was significantly promoted in DOM fractions, especially in the low molecular weight DOM fractions (L-MW DOM, MW < 10 kDa). The results of excitation-emission matrix spectroscopy combined with parallel factor analysis (EEM-PARAFAC) showed that terrestrial humic-like substances had a higher humification degree and fluorophore content in L- MW DOM fractions, which could produce more 3DOM* and 1O2 to promote the indirect photodegradation of FQs. This study provided new insight into the effects of DOM at the molecular weight level on the indirect photodegradation of antibiotics in natural water.