Excitation-emission Matrix Research Articles

Spatial gradients and molecular transformations of DOM, DON and DOS in human-impacted estuarine sediments

Dissolved organic matter (DOM) constitutes the most active fraction in global carbon pools, with estuarine sediments serving as significant repositories, where DOM is susceptible to dynamic transformations. Anthropogenic nitrogen (N) and sulfur (S) inputs further complicate DOM by creating N-bearing DOM (DON) and S-bearing DOM (DOS). This study delves into the spatial gradients and transformation mechanisms of DOM, DON, and DOS in Pearl River Estuary (PRE) sediments, China, using combined techniques of UV–visible spectroscopy, Excitation–emission matrix (EEM) fluorescence spectroscopy, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), and microbial high-throughput sequencing. Results uncovered a distinct spatial gradient in DOM concentration, aromaticity (SUVA254), hydrophobicity (SUVA260), the content of substituent groups including carboxyl, carbonyl, hydroxyl and ester groups (A253/A203) of chromophoric DOM (CDOM), and the abundances of tyrosine/tryptophan-like protein and humic-like substances in fluorophoric DOM (FDOM). These all decreased from upper to lower PRE, accompanied by a decrease in O3S and O5S components, indicating seaward reduction in the contribution of terrestrial OM, especially anthropogenic inputs. Additionally, sediments exhibited a reduction in molecular diversity (number of formulas) of DOM, DON, and DOS from upper to lower PRE, with molecules tending towards a lower nominal oxidation state of carbon (NOSC) and higher bio-reactivity (MLBL), molecular weight (m/z) and saturation (H/C). While molecular composition of DOM remained similar in PRE sediments, the relative abundance of lignin-like substances decreased, with a concurrent increase in protein-like and lipid-like substances in DON and DOS from upper to lower PRE. Mechanistic analysis identified the joint influence of terrestrial OM, anthropogenic N/S inputs, and microbial processes in shaping the spatial gradients of DOM, DON, and DOS in PRE estuarine sediments. This study contributes valuable insights into the intricate spatial gradients and transformations of DOM, DON, and DOS within human-impacted estuarine sediments.

Mercury (II) sensing using a simple turn-on fluorescent graphene oxide based aptasensor in serum and water samples

A simple, highly sensitive, and selective fluorometric aptasensing platform based on aptamer and graphene oxide (GO) is proposed for the determination of mercury (II) ion (Hg2+). In the designed assay, two aptamer probes, a carboxy-fluorescein (FAM) labeled aptamer (aptamer A) and its complementary (aptamer B) with partial complement containing several mismatches and GO as the quencher were used. In the absence of Hg2+, both A and B aptamers were adsorbed on the surface of GO by π-π-stacking, leading to fluorescence quenching of FAM due to fluorescence resonance energy transfer (FRET). Upon exposure to Hg2+, the A and B aptamer strands bind Hg2+ and form T-Hg2+-T complexes, leading to the formation of a stable double-stranded aptamer. The double-stranded aptamer is detached from the GO surface, resulting in the recovery of FAM fluorescence. The fluorescence intensity (FI) of the developed sensor was correlated with the Hg2+ concentration under optimized experimental conditions in two wide linear ranges, even in the presence of 10 divalent cations as interferences. The linear ranges were obtained from 200.0 to 900.0 fM and 5.0 to 33.0 pM, a limit of detection (LOD) of 106.0 fM, and a limit of quantification (LOQ) of 321.3 fM. The concentration of Hg2+ was determined in five real samples containing three water and two serum samples, using spiking and standard addition methods and the results were compared with the spiked amounts and atomic absorption (AAS) as standard method respectively, with acceptable recoveries. Furthermore, in the standard addition method, to overcome the effects of matrix influence of real samples in quantitative predictions, the excitation-emission matrix (EEM) data for samples was simultaneously analyzed by multivariate curve resolution with alternating least squares (MCR-ALS) as a second-order standard addition method (SOSAM).

Reduced sulfur compounds and carboxylic acid groups in dissolved PFRs of iron-biochar enhance Cr(VI) reduction in anaerobic conditions

In addition to the adsorption and immobilization capacities of iron-modified biochars, these materials produce persistent free radicals (PFRs) that can carry out metal [i.e., Cr(VI)] redox transformations, but the primary forms and active species of PFRs involved are not well understood. Here, we investigated the key species of PFRs of α-Fe2O3-modified biochar (MBC) and their influence on Cr(VI) reduction under anaerobic conditions simulating paddy soil environments. MBC produced bulk phenoxyl PFRs that promoted Cr(VI) reduction due to the catalytic effect of the transition metal Fe. In addition, MBC was more efficient in reducing Cr(VI) under anaerobic conditions than under aerobic conditions due to the more active and accessible dissolved PFRs present in the dissolved organic matter (DOM). The electron transfer capacity of DOM was demonstrated by excitation-emission matrix (EEM) spectrophotometry combined with parallel factor analysis, which showed that the protein-like and humic-like components of DOM were involved in Cr(VI) reduction. Furthermore, Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) analysis indicated that reduced-S compounds (O/S < 4) and carboxylic acid (–COO) groups in the unsaturated aliphatic and lignin-like compounds are potentially the main active species accelerating Cr(VI) reduction under anaerobic conditions. Our results provide new insights into the role of dissolved PFRs from iron-modified biochar in promoting Cr(VI) reduction under anaerobic conditions such as flooded soils.Graphical

Compositional and optical characteristics of aqueous brown carbon and HULIS in the eastern Indo-Gangetic Plain using a coupled EEM PARAFAC, FT-IR and 1H NMR approach

This study provides insights into the fluorophoric composition of aqueous brown carbon (BrCaq) and chemically-separated humic-like substances (HULIS): neutral HULIS (HULIS-n; at pH = 7) and acidic HULIS (HULIS-a; at pH = 2) on a seasonal and day-night basis in the eastern Indo-Gangetic Plain (IGP), India. A coupled approach including excitation-emission matrix (EEM) fluorescence and parallel factor analysis (PARAFAC) model, Fourier-transformed infrared spectroscopy (FT-IR) and proton nuclear magnetic resonance (1H NMR) spectroscopy was employed to understand the links between structural, compositional and fluorophoric characteristics of BrCaq and HULIS fractions. HULIS fluorophores (HULISfluoro) with varying oxidation states transported from the northwest IGP were dominant during biomass burning seasons (post-monsoon and winter), while protein-like fluorophores (PRLISfluoro) from marine emissions showed large contributions during summer. HULIS-n moieties were mostly primary in nature with higher conjugation, while HULIS-a were associated with secondarily formed and aged species with a larger contribution from degradation products. A substantial presence of tyrosine-like proteins in both chemically-separated HULIS fractions indicated that atmospheric HULIS is not entirely humic or fulvic-like in the eastern IGP. Finally, the dominance of H-C-O groups across seasons suggested consistent fossil fuel signatures along with season-specific influence of photodegradable cellulose from marine organisms in the summer and biomass burning in the post-monsoon and winter.

Fluorescent Machine Learning Aided Classification of Pathogenic Bacteria Using the Excitation Emission Matrix

The rapid identification of pathogenic bacterial strains is becoming a challenging task as it causes many hospital associated infections. Many have reported on the use of fluorescence spectroscopy as an alternative to characterize bacteria. As bacteria possess intrinsic fluorophores, attempts were made to characterize eight strains using excitation emission matrix (EEM) measurements. From the results of parallel factor analysis (PARAFAC), four fluorophores, tryptophan, anthranilic acid, nicotinamide adenine dinucleotide, and flavin adenine dinucleotide, were identified with varying distributions. The data obtained from PARAFAC analysis were subjected to hierarchical cluster analysis (HCA) and linear discriminant analysis (LDA). This study demonstrates the potential of EEM technique to classify bacteria with 100% accuracy.

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.

Source apportionment based on EEM-PARAFAC combined with microbial tracing model and its implication in complex pollution area, Wujin District, China

Further improving the quality of surface water is becoming more difficult after the control of main point-sources, especially in the complex pollution area with mixed industrial and agricultural productions, whereas the pollution source apportionment might be the key to quantify different pollution sources and developing some effective measures. In this study, a technical framework for source apportionment based on three-dimensional fluorescence and microbial traceability model is developed. Based on screening of the main environmental factors and their spatiotemporal characteristics, potential pollution sources have been tentatively identified. Then, the pollution sources are further tested based on the analysis of fluorescence excitation-emission matrix (EEM) and the similarity of fluorescence components in surface water and potential pollution sources. At the same time, the correlation between microbial species and pollution sources is constructed by analyzing the spatiotemporal characteristics of microbial composition and the response of main species to environmental factors. Therefore, pollution source apportionment is quantified using PCA-APCS-MLR, Fast Expectation-maximization for Microbial Source Tracking (FEAST), and Bayesian community-wide culture-independent microbial source tracking (SourceTracker). PCA-APCS-MLR could not effectively distinguish the contributions of different industrial sources in the complex environment of this study, and the contribution of unknown sources was high (average 39.60%). In contrast, the microbial traceability model can accurately identify the contribution of 7 pollution sources and natural sources, effectively reduce the proportion of unknown sources (average of FEAST is 19.81%, SourceTracker is 16.72%), and show better pollution identification and distribution capabilities. FEAST exhibits a more sensitive potential in source apportionment and shorter calculation time than SourceTracker, thus might be used to guide the precise regional pollution control, especially in the complex pollution environments.

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.

Adaptive mechanism of the marine bacterium Pseudomonas sihuiensis-BFB-6S towards pCO2 variation: Insights into synthesis of extracellular polymeric substances and physiochemical modulation

Marine bacteria can adapt to various extreme environments by the production of extracellular polymeric substances (EPS). Throughout this investigation, impact of variable pCO2 levels on the metabolic activity and physiochemical modulation in EPS matrix of marine bacterium Pseudomonas sihuiensis - BFB-6S was evaluated using a fluorescence microscope, excitation-emission matrix (EEM), 2D-Fourier transform infrared correlation spectroscopy (2D-ATR-FTIR-COS), FT-NMR and TGA-DSC. From the results at higher pCO2 levels, there was a substantial reduction in EPS production by 58–62.8 % (DW). In addition to the biochemical composition of EPS, reduction in carbohydrates (8.7–47.6 %), protein (7.1–91.5 %), and lipids (16.9–68.6 %) content were observed at higher pCO2 levels. Functional discrepancies of fluorophores (tyrosine and tryptophan-like) in EPS, speckled differently in response to variable pCO2. The 2D-ATR-FTIR-COS analysis revealed functional amides (CN, CC, CO bending, -NH bending in amines) of EPS were preferentially altered, which led to the domination of polysaccharides relevant functional groups at higher pCO2. 1H NMR analysis of EPS confirmed the absence of chemical signals from H-C-COOH of proteins, α, β anomeric protons, and acetyl group relevant region at higher pCO2 levels. These findings can contribute new insights into the influence of pCO2 on the adaptation of marine microbes in future ocean acidification scenarios.

Deciphering DOM-metal binding using EEM-PARAFAC: Mechanisms, challenges, and perspectives.

Dissolved organic matter (DOM) is a pivotal component of the biogeochemical cycles and can combine with metal ions through chelation or complexation. Understanding this process is crucial for tracing metal solubility, mobility, and bioavailability. Fluorescence excitation emission matrix (EEM) and parallel factor analysis (PARAFAC) has emerged as a popular tool in deciphering DOM-metal interactions. In this review, we primarily discuss the advantages of EEM-PARAFAC compared with other algorithms and its main limitations in studying DOM-metal binding, including restrictions in spectral considerations, mathematical assumptions, and experimental procedures, as well as how to overcome these constraints and shortcomings. We summarize the principles of EEM to uncover DOM-metal association, including why fluorescence gets quenched and some potential mechanisms that affect the accuracy of fluorescence quenching. Lastly, we review some significant and innovative research, including the application of 2D-COS in DOM-metal binding analysis, hoping to provide a fresh perspective for possible future hotspots of study. We argue the expansion of EEM applications to a broader range of areas related to natural organic matter. This extension would facilitate our exploration of the mobility and fate of metals in the environment.

Controlling toxic Microcystis blooms: The power of a novel microalgal predator Poteriospumella lacustris in water safety improvement

Microcystis aeruginosa blooms have become a global environmental concern. In particular, microcystins (MC) produced by algal cells pose a great threat to aquatic ecosystem security and human health. Therefore, it is necessary to develop environmentally friendly biological measures to reduce bloom hazards. In this study, a heterotrophic flagellate, NY1, that could quickly eliminate M. aeruginosa and efficiently remove MC was isolated and identified as Poteriospumella lacustris. When the initial cell density ratio of P. lacustris to M. aeruginosa was 1:200, P. lacustris rapidly ingested M. aeruginosa, and the clearance rates were more than 90 % within 24 h. P. lacustris effectively removed 83.06 % of MC (more than 200 μg/L) in 24 h and 93.88 % in 72 h. Although temperatures lower than 15 °C and acidic conditions (pH 6) slightly and temporarily inhibited the ingestion and MC removal activities of P. lacustris within 24 h of treatment, it rapidly recovered and ingested more than 90 % of M. aeruginosa and eliminated 97 % of MC within 72 h at various temperatures (15–35 °C) and different pH values (pH 6–10). The fluorescence emission-excitation matrix spectra analysis and acute toxicity test showed that P. lacustris treatment reduced dissolved organic matter (DOM) and eliminated the toxicity of M. aerugionsa culture to three representative species at different trophic levels (Photobacterium phosphoreum, Daphnia magna, and Ctenopharyngodon idellus), indicating the promising potential of P. lacustris in improving water safety. In addition to M. aeruginosa, P. lacustris ingested and digested Platymonas subcordiformis, Chlorella vulgaris, and Synechocystis sp. This study provides a natural and biological solution to global Microcystis blooms by using the grazing effect of P. lacustris to remove toxic cyanobacteria and eliminate MC and DOM, ultimately improving water quality and safety.

A calibration model transfer method based on quadrilinear model for excitation-emission matrix fluorescence measurements on different fluorescence spectrophotometers

In this work, a calibration model transfer method based on quadrilinear model for excitation-emission matrix fluorescence (EEM) data measurements on different fluorescence spectrophotometers was proposed. The proposed method can realize the calibration model transfer of EEM data on different fluorescence spectrophotometers through only one modeling, provided that the shape of the fluorescence spectrum of each target analyte in these data does not change significantly. The calibration sample data acquired on the 2nd or 3rd instrument was transposed to that obtained from the 1st instrument using the calibration model transfer. Subsequently, the transferred data was used to build a calibration model and it was employed to predict the results of spiked prediction samples obtained from the 1st instrument. The reliability of the method was demonstrated through the simulated EEM data and the real EEM data that came from three different fluorescence spectrophotometers (HITACHI F-7000, Edinburgh FS5 and HITACHI F-4600). In addition, when unknown interference was accidentally introduced during the measurement process of calibration samples, this method support the elimination of interference before implementing AQLD and subsequent calibration model transfer was not affected. The obtained EEM data after the calibration model transfer could be combined with the second-order calibration algorithm for the quantitative analysis of target analytes in complex 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.

Effects of microbubble pretreatment on physiochemical and microbial properties of excess activated sludge.

Fast increased amount of excess activated sludge (EAS) from wastewater treatment plants has aroused universal concerns on its environmental risks and demands for appropriate treatments, while effective treatment is dependent upon proper pretreatment. In this study, air-supplied microbubbles (air-MBs) with generated size of 25.18 to 28.25 μm were used for EAS pretreatment. Different durations (30, 60, 90, and 120 s) yielded sludge with varied physiochemical conditions, and 60 s decreased sludge oxidation status and significantly increased adenosine triphosphate (ATP) content. Soluble, loosely-bound, and tightly-bound extracellular polymeric substances (SEPS, LB-EPS, and TB-EPS) were extracted from the sludge through a stepwise approach and examined through three-dimensional excitation-emission matrix (3D-EEM) and quantitative analysis. The results showed that 60- and 120-s treatments generated stronger fluorescence intensities on dissolved organic matters (DOMs) of protein-like and fulvic acid in LB-EPS and TB-EPS, which indicated the decrease of counterparts in EAS, and therefore facilitated sludge dewaterability and reduction. The dominant microbial communities in EAS, including Proteobacteria, Bacteroidota, Chloroflexi, and Actinobacteriota, were not significantly affected by MB pretreatment. The results collectively revealed the effects of MB pretreatment on EAS and indicated that MBs could be an effective pretreatment technique for EAS treatment process.

Z-Type Heterojunction MnO2@g-C3N4 Photocatalyst-Activated Peroxymonosulfate for the Removal of Tetracycline Hydrochloride in Water.

A Z-type heterojunction MnO2@g-C3N4 photocatalyst with excellent performance was synthesized by an easy high-temperature thermal polymerization approach and combined with peroxymonosulfate (PMS) oxidation technology for highly efficient degrading of tetracycline hydrochloride (TC). Analysis of the morphological structural and photoelectric properties of the catalysts was achieved through different characterization approaches, showing that the addition of MnO2 heightened visible light absorption by g-C3N4. The Mn1-CN1/PMS system showed the best degradation of TC wastewater, with a TC degradation efficiency of 96.97% following 180 min of treatment. This was an approximate 38.65% increase over the g-C3N4/PMS system. Additionally, the Mn1-CN1 catalyst exhibited excellent stability and reusability. The active species trapping experiment indicated •OH and SO4•- remained the primary active species to degrade TC in the combined system. TC degradation pathways and intermediate products were determined. The Three-Dimensional Excitation-Emission Matrix (3DEEM) was employed for analyzing changes in the molecular structure in TC photocatalytic degradation. The biological toxicity of TC and its degradation intermediates were investigated via the Toxicity Estimation Software Test (T.E.S.T.). The research offers fresh thinking for water environment pollution treatment.

Spatial variation of soil organic matter and metal mobility in wetland soils: Implications for biogeochemical processes in lateritic landscape

The evolution of the lateritic landscape over time changes the path of pedogenesis and soil hydrology. The occurrence of upland wetlands in the savannah flat plateau transforms well-drained lateritic soils into hydric soils enriched in organic matter. We investigated the composition of soil organic matter (SOM) produced in a wetland and their link with the mineral constituents of soil and their contribution to the mobility of Si, Fe, and Al in the soil. Six tranches were opened in a soil catena located from the plateau toward the center of the wetland, representing different hydromorphic features. Soil morphology was described, and chemical, physical and mineralogical analyses were performed to evaluate soil properties. Chemical fractionation of Soil Organic Matter (SOM) was performed and total organic carbon (TOC), dissolved organic carbon (DOC), particulate organic carbon (POC), and water-extractable organic matter (WEOM) were determined in the soil horizons. Metal complexing properties of DOM were determined using an excitation-emission matrix of fluorescence. The occurrence of Fe eluviation in the superficial horizons, Fe2O3 enrichment in the mottled horizons, and ferricrete formation in the center of the wetland were observed. Geochemical transfer assessment and the variation of oxides within the horizons showed that Fe2O3 and SiO2 were more mobile than Al2O3, whose variability in the gley horizon reflected the mobility of Fe2O3 and SiO2. The stability constants of Al and Cu showed an increase with the depth for WEOM and SOM. The pattern of the organic carbon fraction varied according to the level of hydromorphy and soil depth. It was also observed an increase in the C/N ratio with depth, possibly related to the reduced bioavailability of DOC due to its adsorption with soil solids.

Enhanced activation of persulfate by magnetic NiFe2O4@CuO coupled with ultrasonic for degradation of oxytetracycline: Activation mechanism and degradation pathway

Coupled advanced oxidation processes (AOPs) based on ultrasound and transition metal-activated persulfate (PS) have attracted considerable attention for the degradation of antibiotics. NiFe2O4@CuO composites with core–shell structure were prepared by hydrothermal-freeze-drying-synchronous pyrolysis and coupled with ultrasound to degrade oxytetracycline (OTC) via activated PS. The coupled oxidation process (15-NFO@CuO/US/PS) can substantially enhance the degradation rate of OTC due to the synergistic effects from both ultrasonic and metal activation. X-ray photoelectron spectroscopy reflects that the synergistic interaction between the metals on the 15-NFO@CuO surface can effectively enhance the redox cycling process of metal ions and promote PS activation. Free radical quenching experiments and electron paramagnetic resonance spectroscopy (EPR) identified and confirmed the presence of sulfate radicals (SO4•−), hydroxyl radicals (•OH), and superoxide radicals (O2•−). In addition, the degradation pathways and intermediates of OTC were proposed based on liquid chromatography-mass spectrometry (LC-MS) and three-dimensional excitation-emission matrix (3D-EEM) analysis.

Unraveling the mechanisms behind sodium persulphate-induced changes in petroleum-contaminated aquifers’ biogeochemical parameters and microbial communities

Sodium persulphate (PS) is a highly effective oxidising agent widely used in groundwater remediation and wastewater treatment. Although numerous studies have examined the impact of PS with respect to the removal efficiency of organic pollutants, the residual effects of PS exposure on the biogeochemical parameters and microbial ecosystems of contaminated aquifers are not well understood. This study investigates the effects of exposure to different concentrations of PS on the biogeochemical parameters of petroleum-contaminated aquifers using microcosm batch experiments. The results demonstrate that PS exposure increases the oxidation-reduction potential (ORP) and electrical conductivity (EC), while decreasing total organic carbon (TOC), dehydrogenase (DE), and polyphenol oxidase (PO) in the aquifer. Three-dimensional excitation-emission matrix (3D-EEM) analysis indicates PS is effective at reducing fulvic acid-like and humic acid-like substances and promoting microbial metabolic activity. In addition, PS exposure reduces the abundance of bacterial community species and the diversity index of evolutionary distance, with a more pronounced effect at high PS concentrations (31.25 mmol/L). Long-term (90 d) PS exposure results in an increase in the abundance of microorganisms with environmental resistance, organic matter degradation, and the ability to promote functional genes related to biological processes such as basal metabolism, transmission of genetic information, and cell motility of microorganisms. Structural equation modeling (SEM) further confirms that ORP and TOC are important drivers of change in the abundance of dominant phyla and functional genes. These results suggest exposure to different concentrations of PS has both direct and indirect effects on the dominant phyla and functional genes by influencing the geochemical parameters and enzymatic activity of the aquifer. This study provides a valuable reference for the application of PS in ecological engineering.

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.