Excitation-emission Matrix Fluorescence Spectra Research Articles

Enhanced photocatalytic degradation of organic pollutants via black phosphorus-mediated electron transfer in g-C3N4/BiOI: Degradation mechanisms and biotoxicity assessment

Photocatalysis is a promising strategy for organic pollutant removal, yet developing a capable photocatalyst remains challenging. Using black phosphorus (BP) as an electron buffer material, the ternary composite photocatalysts of xBP/g-C3N4/BiOI were prepared through a straightforward hydrothermal method. Tetracycline (TC) and Rhodamine B (RhB) removals were 100 % (120 min) and 99 % (90 min) by photocatalytic process on 2.5 %BP/g-C3N4/BiOI under xenon lamp irradiation. Photoluminescence and electrochemical measurements confirmed BP's role in reducing charge transfer barriers between g-C3N4 and BiOI, achieving effective separation of photogenerated electrons. The degradation mechanisms of TC and RhB on 2.5 %BP/g-C3N4/BiOI were revealed by the quenching experiments, electron paramagnetic resonance spectroscopy tests, three-dimensional excitation-emission matrix fluorescence spectrum, and liquid chromatography-mass spectrometry analyses. Plant toxicity assessment experiments confirmed the non-toxic nature of the TC and RhB degradation solutions. Plants grown in the treated solutions exhibited declining trends in both Malondialdehyde and Peroxidase indices compared to untreated solutions. This study offers a fresh approach to advanced photocatalyst design using charge transfer buffer materials.

Attention improvement for data-driven analyzing fluorescence excitation-emission matrix spectra via interpretable attention mechanism

Analyzing three-dimensional excitation-emission matrix (3D-EEM) spectra through machine learning models has drawn increasing attention, whereas the reliability of these machine learning models remains unclear due to their “black box” nature. In this study, the convolutional neural network (CNN) for classifying numbers of fluorescent components in 3D-EEM spectra was interpreted by gradient-weighted class activation mapping (Grad-CAM), guided Grad-CAM, and structured attention graphs (SAGs). Results showed that the original CNN classifier with high classification accuracy may make a classification based on misleading attention to the non-fluorescence area in 3D-EEM spectra. By removing Rayleigh scatterings in 3D-EEM spectra and integrating convolutional block attention module (CBAM) in CNN classifiers, the correct attention of the trained CNN classifier with CBAM greatly increased from 17.6% to 57.2%. This work formulated strategies for improving CNN classifiers associated with environmental fields and would provide great help for water determination in both natural and artificial environments.

Efficient and stability electrochemical degradation of Bisphenol A on Ti/TiO2-NTA/PbO2-Nd anode: Mechanistic analysis

The Ti/TiO2-NTA/PbO2-Nd electrodes were fabricated using anodic oxidation and electrodeposition techniques for the electrocatalytic treatment of bisphenol A (BPA) pollutants in coking wastewater. Characterization revealed well-organized TiO2 nanotube arrays (TiO2-NTA) with a hollow structure, featuring a wall thickness of 36 nm and an inner diameter of approximately 83 nm. The TiO2-NTA interlayer restricted PbO2 growth, leading to a compact crystal structure and increased electrode surface area. Electrochemical tests showed that the Ti/TiO2-NTA/PbO2-Nd electrode outperformed Ti/TiO2-NTA/PbO2 and Ti/PbO2 electrodes, exhibiting the highest oxygen evolution potential, lowest charge transfer resistance, optimal hydroxyl radical generation, and longest service lifetime. The removal efficiencies for BPA were 95.4 % for Ti/TiO2-NTA/PbO2-Nd, 90.8 % for Ti/TiO2-NTA/PbO2, and 80.6 % for Ti/PbO2. The Ti/TiO2-NTA/PbO2-Nd electrode also achieved the lowest energy consumption at 0.157 kWh/(g·COD), a 40 % reduction compared to Ti/PbO2. The introduction of TiO2-NTA enhanced electrode stability, electron transfer, and surface area, while neodymium (Nd) doping improved oxygen evolution potential and hydroxyl radical production. Under optimized conditions, the Ti/TiO2-NTA/PbO2-Nd electrode achieved BPA removal efficiencies of 99.24 %, COD removal efficiencies of 82.77 %, and TOC removal efficiencies of 78.92 %. UV–Vis spectrophotometry, three-dimensional excitation-emission matrix fluorescence spectra (3D EEM), and gas chromatography–mass spectrometry (GC–MS) analyses revealed potential BPA degradation pathways.

Distribution characteristics of sulfonamide antibiotics between water and extracellular polymeric substances in municipal sludge

The interaction between extracellular polymeric substances (EPS) in municipal sludge and antibiotics in wastewater is critical in wastewater treatment, resource recovery, and sludge management. Therefore, it is increasingly urgent to investigate the distribution coefficient (Log K) of sulfonamide antibiotics (SAs) in EPS, particularly in sludge-derived dissolved organic carbon (DOC) and aqueous phase systems. Herein, through balance experiments, the concentrations of SAs were determined using alkaline extraction EPS (AEPS) and alginate-like extracellular polymer (ALE) systems, and the Log KDOC values were determined. The results showed that the Log KDOC of AEPS was higher than that of ALE, which exhibited a negative KDOC value, indicating an inhibitory effect on dissolution. For the three SAs studied, the Log KDOC values were in the following order: sulfamethoxazole > sulfapyridine > sulfadiazine. This order can be attributed to the differing physicochemical properties, such as polarity, of the SAs. Three-dimensional excitation–emission matrix fluorescence spectra and fitting results indicated a lack of aromatic proteins dominated by tryptophan and humus-like substances in ALE. Meanwhile, the hydrophobic interaction of aromatic proteins dominated by tryptophan was the main driving force in the binding process between AEPS and SAs.

Identification and Removal of Pollen Spectral Interference in the Classification of Hazardous Substances Based on Excitation Emission Matrix Fluorescence Spectroscopy.

Sensitively detecting hazardous and suspected bioaerosols is crucial for safeguarding public health. The potential impact of pollen on identifying bacterial species through fluorescence spectra should not be overlooked. Before the analysis, the spectrum underwent preprocessing steps, including normalization, multivariate scattering correction, and Savitzky-Golay smoothing. Additionally, the spectrum was transformed using difference, standard normal variable, and fast Fourier transform techniques. A random forest algorithm was employed for the classification and identification of 31 different types of samples. The fast Fourier transform improved the classification accuracy of the sample excitation-emission matrix fluorescence spectrum data by 9.2%, resulting in an accuracy of 89.24%. The harmful substances, including Staphylococcus aureus, ricin, beta-bungarotoxin, and Staphylococcal enterotoxin B, were clearly distinguished. The spectral data transformation and classification algorithm effectively eliminated the interference of pollen on other components. Furthermore, a classification and recognition model based on spectral feature transformation was established, demonstrating excellent application potential in detecting hazardous substances and protecting public health. This study provided a solid foundation for the application of rapid detection methods for harmful bioaerosols.

Dual role of dissolved black carbon in sensitized ofloxacin photooxidation: Mechanism and influential factors

Dissolved black carbon (DBC) is the more photoactive component of dissolved organic matter (DOM) pool, which plays a dual role in the photoconversion of aquatic contaminants, acting as both a photosensitizer and an inhibitor. However, little is known about the more systematic mechanism by which DBC exhibits a dual effect, which is closely related to the structure composition of DBC. In this study, the differences in characteristics of DBC obtained from 300 °C and 500 °C were compared via UV–vis absorption spectrum, Fluorescence excitation emission matrix spectra (3D-EEM), Fourier transform infrared (FT-IR), and X-ray photoelectron spectroscopy (XPS), and evaluated the promoting and inhibiting effects of DBC on ofloxacin (OFL) photodegradation. It was found that higher pyrolysis temperature reduced the UV absorbance, molecular weight, aromaticity, and phenolics of DBC while increasing the content of quinone/aromatic ketone and humic substances. Photochemical data showed that 3DBC*, 1O2 and ·OH were all participated in the DBC-mediated OFL photodegradation. Wherein, DBC300 (DBCT, where T = pyrolysis temperature) had strong light screening and dynamic quenching effect, but the formation ability of 3DBC*, 1O2 and ·OH was poor, which significantly retarded the photodegradation of OFL. While DBC500 exhibited a slight promotion effect due to its higher formation ability of reactive species and weak light screening effect. Moreover, DBC500 had higher steady-state concentration and (kOFL,3DBC⁎) than DBC300, which might be due to the higher contents of quinone/aromatic ketone and the lower contents of phenol in DBC500, thus enhancing the reactivity of 3DBC* and OFL. Our research systematically revealed the trade-off mechanism of DBC on the photodegradation of fluoroquinolones, and provided an important theoretical guidance for the photodegradation of fluoroquinolones under the evolution of DBC composition.

Mechanistic insights of efficient aromatic organic compounds oxidation using biochar derived from coking wastewater sludge

Coking wastewater sludge possessed potential environmental hazards and pyrolysis was a desirable approach which could converted it into one functional carbonous material. The sludge-based biochar (SC-N3) originated from the feedstock of sludge from the regenerated water treatment had various iron-containing species and exhibited the effective catalytic ability. Compared with the degradation of the four pollutants (i.e., phenol, pyridine, quinoline and indole) alone, the mixed of the four pollutants in simulated coking wastewater exhibited a prominent different degradation trend, where the removal rates of indole and quinoline were enhanced from 45% and 30% to 98.9% and 82.3%, respectively. The quinone intermediates from phenol degradation, played a critical role in enhancing the removal rates of indole and quinoline as the electron transfer medium. Both the free radical pathway dominated by •OH and non-radical pathway with 1O2 play the main role in indole degradation, while •OH was the main factor in the catalytic degradation of phenol, quinoline and pyridine. By analysis the intermediates elucidated by Fourier transform ion cyclotron resonance mass spectrometry and three-dimensional excitation-emission matrix fluorescence spectra, the degradation molecular characteristics and pathways of the four pollutants in simulated coking wastewater were deciphered. The findings indicated that the catalyst SC-N3 prepared from the coking wastewater sludge presented unique catalytic properties and possessed a promising application in the degradation of refractory wastewater.

S-type heterojunction enhance the photocatalytic activity of TiO2/AgBr/Ag using loofah sponge as template towards ciprofloxacin degradation

Photocatalyst TiO2/AgBr/Ag (TBA) composites using loofah sponge as a template were successfully prepared for the first time. The photocatalytic activities of the TBA composites were evaluated by removing ciprofloxacin (CIP) under visible light. The PDOS shows that the valence band edge of TBA-30 is primarily composed of Ti 3d atom states, with small contributions from O 2p atom states. The conduction band edge is dominated by Ag 4d and O 2p atom states, with minor contributions from Br 4p atom states. TBA-30 composites demonstrate outstanding photocatalytic performance, degrading 87% of the target within 180 min. The degradation rate of CIP decreased to 70.19% after five runs, Furthermore, the TOC removal efficiency of CIP reached 84.2% in the end. CIP intermediates and degradation pathway were determined by GC-MS. Three-dimensional excitation-emission matrix fluorescence spectra (3D EEM) were used to study the degradation of CIP molecules. Trapping experiments and electron paramagnetic resonance (EPR) characterisation identified superoxide (·O2-) and photogenerated holes (h+) as the primary active radicals. Furthermore, formed S-type heterojunction and Ag as the electron capture site enhanced the separation efficiency of photoinduced electron-hole pairs. The DFT calculation was used to study the electron transport performance of TBA-30 by calculating the charge density difference.

Simultaneous degradation and rejection of PPCPs from wastewater in a 3DEO-FO-RO process

This study established a novel three-dimensional electrochemical oxidation coupled with forward osmosis and reverse osmosis (3DEO-FO-RO) system with the purpose to achieve simultaneous degradation and rejection of pharmaceuticals and personal care products (PPCPs) in wastewater. 18 frequently detected PPCPs were selected as the target pollutants to prepare the synthetic wastewater with a concentration of 200 μg/L for each pollutant. Ti/IrO2–Ta2O5–SnO2 mesh anode, titanium mesh cathode and Sn–Sb–Bi/γ-Al2O3 particles electrodes were integrated in the 3DEO-FO reactor. Experimental results demonstrated that degradation efficiency exceeding 98.5 % and rejection exceeding 99.4 % for each PPCP were achieved simultaneously in the 3DEO-FO-RO processes at a current density of 1 mA/cm2 after 8 h treatment. Despite variations in applied current density, the 3DEO-FO-RO processes exhibited superior PPCPs removal efficiencies, particularly for refractory compounds, compared to the 2DEO-FO-RO processes. Increased hydroxyl radical (·OH) generation in the 3D reactor was considered to be responsible for the excellent performance. Furthermore, results derived from ultraviolet (UV) absorption spectra and fluorescence excitation-emission matrix (EEM) spectra provided additional validation for the effective removal of PPCPs in the 3DEO-FO-RO processes, along with evidence indicating the decomposition of PPCPs into smaller constituents. Ultimately, the 3DEO-FO-RO process demonstrated its capacity in removing PPCPs from actual secondary effluent from a wastewater treatment plant. This integrated system coupling 3D EO with FO-RO membranes can provide an efficient approach for simultaneous degradation and rejection of trace contaminants for wastewater reuse.

Enhanced disintegration mechanism of surplus activated sludge to improve dewatering by thermally activated persulfate oxidation under mild temperature.

The dewatering treatment is an essential process for the treatment and disposal of surplus activated sludge (SAS), and improving sludge dewatering performance is still a challenge and has become a research hotspot in recent years. The oxidation and disintegration of bacterial cells and extracellular polymeric substances (EPS) by active radicals produced by advanced oxidation processes (AOPs) were extremely promising to achieve deep sludge dewatering. This paper systematically studied the efficiency and mechanism of thermally activated persulfate (TAP) oxidation technology to the improvement of SAS dewatering performance. The results showed that the relative filterability (CST0/CST) was increased 2.52 times with 2.0 mmol/g VSS potassium peroxydisulfate (PDS) at 80 °C in 90 min. Under this condition, the Zeta potential of SAS significantly decreased from - 14.8 to - 1.44 mV, while the average particle size (dp50) decreased from 52.981 to 48.259 μm. Thermal treatment disrupted the sludge structure to release large amounts of EPS including polysaccharides and protein. Meanwhile, the results of three-dimensional excitation-emission matrix (3D-EEM) fluorescence spectra showed that the TAP treatment could expedite the disintegration of sludge, facilitating the decrease of total EPS content and conversion of tightly bound EPS (TB-EPS) to loosely bound EPS (LB-EPS) and soluble EPS (S-EPS). The mechanism of TAP process to improve SAS dewatering performance was revealed, which could contribute to breaking the bottleneck of sludge depth dewatering and provide a theoretical and technical basis for its practical application.

Engineering highly dispersed AgI nanoparticles on hierarchical In2S3 hollow nanotube to construct Z-scheme heterojunction for efficient photodegradation of insecticide imidacloprid

Increasing the exposure of active sites and improving the intrinsic activity are necessary considerations for designing a highly efficient photocatalyst. Herein, an In2S3/AgI stable Z-scheme heterojunction with highly dispersed AgI nanoparticles (NPs) is synthesized by the mild self-templated and in-situ ion exchange strategy. Impressively, the optimized In2S3/AgI-300 Z-scheme heterojunction exhibits superior photodegradation activity (0.020 min−1) for the decomposition of insecticide imidacloprid (IMD), which is extremely higher than that of pure In2S3 (0.002 min−1) and AgI (0.013 min−1). Importantly, the three-dimensional excitation-emission matrix (3D EEMs) fluorescence spectra, high-resolution mass spectrometry (HRMS), the photoelectrochemical tests, radical trapping experiment, and electron spin resonance (ESR) technique are performed to clarify the possible degradation pathway and mechanism of IMD by the In2S3/AgI-300 composite. The enhanced photocatalytic performance is attributed to the highly dispersed AgI NPs on hierarchical In2S3 hollow nanotube and the construction of In2S3/AgI Z-scheme heterojunction, which can not only increase active site exposure, but also improve its intrinsic activity, facilitating rapid charge transfer rate and excellent electron-hole pairs separation efficiency. Meanwhile, the practical application potential of the In2S3/AgI-300 composite is systematically investigated. This study opens a new insight for designing catalysts with high photocatalytic performance through a convenient approach.

Ceramic membrane reactor integrated with UV/O3/Catalyst Beads for treating real textile wastewater: Enhanced effluent quality, fouling control and molecular transformations of DOM

A ceramic membrane reactor (CMR) was employed to treat real textile wastewater with the simultaneous use of UV, O3, and photocatalytic beads for dissolved organic matter (DOM) transformation and membrane fouling control. The O3 treatment exhibited high performance in color removal. Simultaneous use of UV and ozonation (UV/O3) resulted in 91% and 64% color and chemical oxygen demand (COD) removal, respectively, and delayed (3-fold) fouling time compared to UV alone. A combination of TiO2-loaded polymeric beads with UV/O3 (UV/O3/Beads) further enhanced the color (96%) and COD (86%) removal as well as improved fouling control by 9-folds compared to the control (Air alone) experiment. Three-dimensional excitation-emission matrix (3-D EEM) fluorescence spectra revealed minimum DOM and synergistic effects of UV, O3, and photocatalytic beads (UV/O3/Beads) in the degradation of fluorescent DOM. The •OH radicals were leading in degrading organic pollutants during the treatment. Transformations of heteroatomic DOMs were confirmed by the Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). S-containing compounds in the treated samples appeared in a reduced state (lower H/C and O/C ratios), indicating the transformation of R–SO3 to R–S–R. Whereas N-containing DOM was mostly oxidized. UV/O3 rapidly transformed dye molecules to colorless, creating suitable conditions for photocatalytic beads for accelerated degradation of pollutants. Also, the PTR-TOF-MS analysis revealed the successful removal of toxic VOCs (Methanethiol, Allylamine, Cyclohexenes, Butanes, Propanes, and Hydrazines) from wastewater by the UV/O3/Beads treatment. Based on these findings, DOM transformations could be better understood, and the simultaneous application of heterogeneous photocatalysis and UV/O3 could be safely recommended as a promising technology for treating industrial wastewater.

Rapidly identifying the geographical origin of Lilium bulbs by nano-effect excitation-emission matrix fluorescence combined with chemometrics

Lilium bulbs (LB) are a highly nutritious food, and their quality and price are influenced by origin. The present study proposed a nano-effect excitation-emission matrix fluorescence (EEMF) combined with chemometrics strategy for rapidly identifying the geographical origin of LB. Nano-effect EEMF spectra of 280 LB samples from different origins were collected after reaction with bovine serum albumin-modified gold and silver nanoclusters (BSA-AuAgNCs). Further, partial least squares-discrimination analysis (PLS-DA) and principal component analysis-linear discriminant analysis (PCA-LDA) were used to establish classification models for identifying the geographical origin of LB based on the obtained nano-effect EEMF spectra. The result showed that PCA-LDA model gained the optimal performance, and the classification accuracy of the training set and the prediction set was 95.9% and 90.5%, respectively. The nano-effect EEMF spectra was based on the reaction of BSA-AuAgNCs with the components, such as phenolic acids, in LB through hydrogen bonding, which amplified the spectral difference. This study demonstrated that the proposed strategy is effective for identifying the geographical origins of LB, which provides a new idea for the geographic traceability of other foods.

Transformation of organic carbon through medium pressure (polychromatic) UV disinfection of wastewater effluent during wet weather events

An observed decrease in total organic carbon (TOC) and dissolved organic carbon (DOC) concentrations following wastewater disinfection with medium pressure (MP, polychromatic) ultraviolet (UV) irradiation during wet weather flows is investigated. When antecedent rainfall in the previous 7-days was >2 in (5 cm), TOC and DOC concentrations decreased dramatically following MP-UV disinfection. Organic carbon surrogate measurements of biological oxygen demand (BOD), TOC, DOC, turbidity, UVA – 254 nm, SUVA (specific UVA), scanning UV–Visible spectra (200–600 nm), fluorescence excitation-emission matrix (EEM) spectra, and light scattering data are presented for wastewater resource recovery facility (WRRF) influent, secondary effluent (pre-UV-disinfection), and MP-UV-disinfected (final effluent) samples. TOC and DOC in wastewater influent and secondary effluent (i.e., pre-UV disinfection) correlated with antecedent rainfall conditions. The percent TOC and DOC removal through secondary treatment (i.e., from influent to effluent pre-UV) and the percent TOC and DOC removal through MP-UV disinfection (i.e., from effluent pre-UV to effluent post-UV) were compared and the latter approached 90 % through MP-UV disinfection during high antecedent rainfall conditions. Spectroscopy (UV, visible, or fluorescence) was performed on samples after filtration through 0.45 μm filters, i.e., the operationally defined DOC fraction of aquatic carbon. Scanning UV–visible spectra indicated transformation of an unidentified wastewater component into light-scattering entities regardless of antecedent rainfall conditions. The types of organic carbon (diagenetic, biogenic, or anthropogenic) and the significance of wet weather are discussed. An organic carbon contribution via infiltration and inflow was attributed as a source-of-interest in this research.

Anti-interference and non-destructive identification of textile fabrics using front-face excitation-emission matrix fluorescence spectroscopy combined with multi-way chemometrics

The identification of trace textile fabrics discovered at crime scenes plays a crucial role in the case of forensic investigations. Additionally, in practical situations, fabrics may be contaminated, making identification more challenging. To address the aforementioned issue and promote the application of fabrics identification in forensic analysis, front-face excitation-emission matrix (FF-EEM) fluorescence spectra coupled with multi-way chemometric methods were proposed for the interference-free and non-destructive identification of textile fabrics. Common commercial dyes in the same color range under different materials (cotton, acrylic, and polyester) that cannot be visually distinguished were investigated, and several binary classification models for the identification of dye were established using partial least squares discriminant analysis (PLS-DA). The identification of dyed fabrics in the presence of fluorescent interference was also taken into consideration. In each kind of pattern recognition model mentioned above, the classification accuracy (ACC) of the prediction set was 100%. The alternating trilinear decomposition (ATLD) algorithm was executed to separate mathematically and remove the interference, and the classification model based on the reconstructed spectra attained an accuracy of 100%. These findings indicate that FF-EEM technology combined with multi-way chemometric methods has broad prospects for forensic trace textile fabric identification, especially in the presence of interference.

Effects of paddy irrigation-drainage system on water quality and productivity of small rivers in the Himi region of Toyama, Central Japan

The aim of this study was to clarify the impact of differences between historical and recently introduced irrigation and drainage management systems on water quality in the rivers around paddy fields. We investigated the seasonal variation in nutrients concentration and dissolved organic carbon (DOC) components in single- (used for intake only) and dual-purpose (used for both intake and drainage) channels during a 4-year period in the Himi region of Toyama, Central Japan. The system of dual-purpose channel has traditionally been used in the region of this study. A total of 197 three-dimensional excitation-emission matrix (3DEEM) fluorescence spectra of DOM in waters were applied for the parallel factor analysis (PARAFAC) modeling. Based on the 3DEEM and PARAFAC, the abundance of terrestrial humic-like components in the dual-purpose channel was significantly higher than that in the single-purpose channel. The even long-chain n-fatty acids derived associated with rice cropping in sediments of the dual-purpose channels were 22−30-fold higher than that of the single-purpose channel. In addition, the turbidity values of the river waters had significantly positive linear correlations with concentrations of K+, DOC, and humic-like components. These observations indicate that the dissolved nutrient concentrations in the river water were higher in the dual-purpose channel compared to those of the single-purpose channel, which may be supplied by leaching from the inflow of soil particles from the paddy fields. During the mid-irrigation period, the quantity of epiphytic chlorophyll a on artificial substrate tiles in the dual-purpose channel were 3.1–4.1-fold higher than that in the single-purpose channel. This study clear that the input of paddy drainage during the irrigation season significantly changes the DOC components in river waters and irrigation management is strongly linked to the primary production in agricultural channels. Therefore, it is important to consider the impact of the introduction of different irrigation and drainage management systems on water quality and productivity in order to maintain the riverine ecosystems around rice paddies, which are based on historical water use systems.

Base-activated persulfate strategy for ceramic membrane cleaning after treatment of natural surface water

The natural organic matters (NOM) have been proved to form the hydraulically irreversible membrane fouling, which limit the application of the membrane in water treatment processes. To solve the membrane fouling caused by NOM, a novel one-step chemical cleaning method for the ceramic membrane derived from the base-activated persulfate oxidation process was developed in this study. When the SiC ceramic membranes was used to filtrate practical river water, the permeate flux dropped 65% as ΔTMP reached 30 kPa. After 2 h immersion of the fouled membrane in the cleaning solution (2 mM PMS and 8 mM NaOH), the flux recovery rate nearly reached 100%. Direct backwash of the membrane by the above cleaning solution further reduced the cleaning time to 25 mins, while achieving similar cleaning effect. Then the cleaned membranes were immersed in NaClO solution to release all the residual foulants, but the fluorescence excitation-emission matrix spectra (EEM) and total organic carbon (TOC) of the solution were found insignificant, which demonstrated the base-activated persulfate strategy had effectively removed the irreversible membrane fouling. Free radical quenching experiments were carried out and·O2- was identified as the dominant ROS responsible for the removal of the membrane foulants. The permeate flux and filtration efficiency of the SiC membrane were stable after 5 consecutive fouling-cleaning cycles, and the membrane structure was not damaged. In summary, the base-activated persulfate strategy is an efficient and cleaner method for SiC membrane cleaning, which is potential to be applied in practical membrane water treatment process.

Performance of resin adsorption and ozonation pretreatment in mitigating organic fouling of reverse osmosis membrane

Effective pretreatment of reverse osmosis (RO) influent is of great importance for reducing membrane fouling risks during coking wastewater desalination. In this study, the combined resin adsorption and ozonation pretreatment was investigated on alleviating RO membrane organic fouling. The performance of combined process was compared with only resin adsorption or ozonation, which was evaluated in terms of changes in chemical oxygen demand (COD), ultraviolet-visible index, and three-dimensional excitation-emission matrix fluorescence spectra. RO membrane fouling tests were conducted to examine the effects of pretreatment on flux decline and filtration resistance. The surface morphology and functional groups of membrane before and after fouling was characterized by scanning electron microscopy and infrared spectroscopy. The correlation between major organic matter in the wastewater and normalized RO membrane flux was established via multiple linear regression equations. The results showed that ozonation was more effective in removing COD and fluorescent organics than resin adsorption. Moreover, the combined bifunctional resin adsorption/ozonation unit showed the best performance, with COD and UV254 removal rates of 49.4 % and 88.0 %, respectively. The fluorescence intensity of each component decreased significantly. Meanwhile, the polysaccharide and protein components of the RO membrane fouling layer were effectively reduced by 67.2 % and 80.8 %, respectively. Most importantly, the combined pretreatment substantially reduced the decline in membrane flux and filtration resistance. Meanwhile, the fulvic acid-like organics in the wastewater showed high correlations with normalized membrane flux. The regression equation was beneficial for RO membrane fouling evaluation.

Impact of different classification schemes on discrimination of proteins with noise-contaminated spectra using laboratory-measured fluorescence data

Biological agents are important to detect and identify with respect to environmental contamination and public health. Noise contamination in fluorescent spectra is one of the contributors to the uncertainties of identification. In order to investigate the noise-tolerant capability provided by laboratory-measured excitation-emission matrix (EEM) fluorescence spectra that are used as a database, fluorescence properties of four proteinaceous biotoxin samples and ten harmless protein samples were characterized by EEM fluorescence spectra, and the predicting performance of models trained by laboratory-measured fluorescence data was tested and verified from validation data with noise-contaminated spectra. By means of peak signal of noise (PSNR) as an indicator of noise levels, the potential impact of noise contaminations on the characterization and discrimination of these samples was evaluated quantitatively. Different classification schemes utilizing multivariate analysis techniques of Principal Component Analysis (PCA), Random Forest (RF), and Multi-layer Perceptron (MPL) coupled with feature descriptors of differential transform (DT), Fourier transform (FT) and wavelet transform (WT) were conducted under different PSNR values. We systematically analyzed the performance of classification schemes by the case study at 20 PSNR and by statistical analysis from 1-100 PSNR. The results show that the spectral features with EEM-WT decreased the demanding number of input variables while retaining high performances in sample classification. The spectral features with EEM-FT presented the worst performance although having the largest number of features. The distributions of feature importance and contribution were found sensitive to noise contaminations. The classification scheme of PCA prior to MPL with EEM-WT as input presented an improvement in lower PSNR. These results indicate that robust features extracted by corresponding techniques are critical to enhancing the spectral differentiation capabilities among these samples and play an important role in eliminating the noise effect. The study of classification schemes for discriminating protein samples with noise-contaminated spectra presents tremendous potential for future developments in the rapid detection and identification of proteinaceous biotoxins based on three-dimensional fluorescence spectrometry.

Water-soluble brown carbon in atmospheric aerosols from the resource-dependent cities: Optical properties, chemical compositions and sources

As a vital type of light-absorbing aerosol, brown carbon (BrC) presents inherent associations with atmospheric photochemistry and climate change. However, the understanding of the chemical and optical properties of BrC is limited, especially in some resource-dependent cities with long heating periods in northwest China. This study showed that the annual average abundances of Water-soluble BrC (WS-BrC) were 9.33±7.42 and 8.69±6.29 µg/m3 in Baotou and Wuhai and the concentrations, absorption coefficient (Abs365), and mass absorption efficiency (MAE365) of WS-BrC presented significant seasonal patterns, with high values in the heating season and low values in the non-heating season; while showing opposite seasonal trends for the Absorption Ångström exponent (AAE300-400). Comparatively, the levels of WS-BrC in developing regions (such as cities in Asia) were higher than those in developed regions (such as cities in Europe and Australia), indicating the significant differences in energy consumption in these regions. By combining fluorescence excitation-emission matrix (EEM) spectra with the parallel factor (PARAFAC) model, humic-like (C1 and C2) and protein-like (C3) substances were identified, and accounted for 61.40%±4.66% and 38.6%±3.78% at Baotou, and 60.33%±6.29% and 39.67%±4.17% at Wuhai, respectively. The results of source apportionment suggested that the potential source regions of WS-BrC varied in heating vs. non-heating seasons and that the properties of WS-BrC significantly depended on primary emissions (e.g., combustion emissions) and secondary formation.