Fluorescence fingerprint as an indicator to identify urban non-point sources in urban river during rainfall period.

Nowadays, the urban non-point source (NPS) pollution gradually evolved as the main contributor to urban water contamination since the point source pollution was effectively controlled. It was imperative to perform urban NPS identification in urban river to meet the requirements of precise source governance. In this study, the real-time detection about water quality parameters and fluorescence fingerprints (FFs) was performed for BX River and its outlets during rainfall period. EEM-PARAFAC and component similarity analyses discovered that the pollution encountered by BX River mainly came from road runoff and untreated municipal wastewater (UMWW) overflow. The C1 (tryptophan-like) and C3 (terrestrial humic-like) components located at Ex/Em = âˆ¼230(280)/340 and ∼275/430 nm were both detected in these two kinds of urban NPS. The C2 components of road runoff and UMWW overflow displayed remarkable differences, which located at Ex/Em = 250/385 and 245/365 nm, respectively, thus could be served as indicators for distinguishing them. During rainfall period, the outflow from rainwater outlets (RWOs) constantly showed similar FF features to road runoff, while the FFs of outflow from combined sewer outlets (CSOs) alternated between those of road runoff and UMWW overflow. The FF features of sections in BX River changed in response to the dynamic variations in FFs of the outlets, which revealed real-time pollution causes of BX River. This work not only realized the identification and differentiation of urban NPS, but also elucidated the dynamic variations of pollution characteristics throughout the entire process of "urban NPS-outlets-urban river", and demonstrated the feasibility of FF technique in quickly diagnosing the pollution causes of urban river during rainfall period, which provided important guidance for urban NPS governance.

Spectroscopic and compositional profiles of dissolved organic matters in urban snow from 2019 to 2021: Focusing on pollution features identification.

Snow owns stronger adsorption capacity for organic pollutants compared with rain. Huge amounts of anthropogenic dissolved organic matters (DOMs) in the atmosphere may enter the water environment with urban snow and increase water pollution risk. Extracting stable pollution features of urban snow is conducive to identifying the urban snow pollution from the water environment. Herein, we systematically explored the spectroscopic and compositional profiles of urban snow in Beijing from three snow events by multiple analytical tools and extracted stable pollution features of urban snow for the first time. Results showed that conventional pollutants with high concentration were detected in urban snow. The fluorescence signals of humic-like and some protein-like materials, the molecular weight distributions of chromophoric DOM at 254 nm and humic-like materials, and 172 kinds of lignin-like molecular formulas were extracted as stable features for urban snow. These stable features of urban snow laid the foundation for the identification of urban snow pollution and the analysis of the impact mechanisms of atmospheric pollution sources on the water environment.

Novel insights into impacts of the COVID-19 pandemic on aquatic environment of Beijing-Hangzhou Grand Canal in southern Jiangsu region.

In 2020, a sudden COVID-19 pandemic unprecedentedly weakened anthropogenic activities and as results minified the pollution discharge to aquatic environment. In this study, the impacts of the COVID-19 pandemic on aquatic environment of the southern Jiangsu (SJ) segment of Beijing-Hangzhou Grand Canal (SJ-BHGC) were explored. Fluorescent component similarity and high-performance size exclusion chromatography analyses indicated that the textile printing and dyeing wastewater might be one of the main pollution sources in SJ-BHGC. The water quality parameters and intensities of fluorescent components (WT-C1(20) and WT-C2(20)) decreased to low level due to the collective shutdown of all industries in SJ region during the Spring Festival holiday and the outbreak of the domestic COVID-19 pandemic in China (January 24th to late February, 2020). Then, they presented a gradual upward trend after the domestic epidemic was under control. In mid-March, the outbreak of the international COVID-19 pandemic hit the garment export trade of China and consequently inhibited the production activities of textile printing and dyeing industry (TPDI) in SJ region. After peaking on March 26th, the intensities of WT-C1(20) and WT-C2(20) decreased again with changed intensity ratio until April 12th. During the study period (135 days), correlation analysis revealed that WT-C1 and WT-C2 possessed homology and their fluorescence intensities were highly positively correlated with conductivity and CODMn. With fluorescence fingerprint (FF) technique, this study not only excavated the characteristics and pollution causes of water body in SJ-BHGC, but also provided novel insights into impacts of the COVID-19 pandemic on production activities of TPDI and aquatic environment of SJ-BHGC. The results of this study indicated that FF technique was an effective tool for precise supervision of water environment.

Characterizing fluorescence fingerprints of different types of metal plating wastewater by fluorescence excitation-emission matrix.

To prevent the illegal discharge of metal plating wastewater (MPW), it is necessary to explore a monitoring method that could achieve the identification of MPW in natural water bodies. Fluorescence excitation-emission matrix-parallel factor (EEM-PARAFAC) analysis might be a promising tool for the detection of MPW. However, before conducting the practical monitoring, the apparent fluorescence features of different kinds of MPW must be first understood. In this study, six types of MPW (576 samples) from ten metal plating plants were collected and their fluorescence fingerprints (FFs) were characterized by EEM-PARAFAC analysis. Results showed that pretreatment wastewater (PTW), copper-contained electroplating wastewater (Cu-EPW), nickel-contained electroplating wastewater (Ni-EPW), copper-contained electroless wastewater (Cu-ELW), nickel-contained electroless wastewater (Ni-ELW), and metal plating effluent (MPE) presented one, three, one, one, two, and three types of FFs, respectively. Among them, three individual fluorescent components were identified in Ni-EPW and two were decomposed in other kinds of MPW. Owing to the discrepancies of production processes, electroplating additives, wastewater treatment techniques, and management levels, different metal plating plants owned different FFs. By spectral comparison, the tyrosine-like components in PTW and Ni-ELW might derived from some phenolic and benzenesulfonic acidic compounds. Fluorescent component similarity analysis indicated that EEM-PARAFAC technique could distinguish the raw and treated MPW. This study not only constructed the first FF database for MPW, but also provided valuable guidance for their practical monitoring in aquatic environment.

Characterization of fluorescent dissolved organic matters in metalworking fluid by fluorescence excitation-emission matrix and high-performance liquid chromatography.

In recent years, precise environment supervision has gradually become vital in water pollution control, which requires the clear identification of dissolved organic matters (DOM) in wastewater. Metalworking fluid (MWF) is a type of wastewater with high toxicity. Over ten million m3 of MWF is discharged per year. However, its DOM characteristics have not yet been systematically investigated. Therefore, in this study, the fluorescent DOM (FDOM) of MWF was firstly characterized by excitation-emission matrix-parallel factor analysis (EEM-PARAFAC) and high-performance liquid chromatography (HPLC). Three fluorescent components (C1-C3) of the MWF from three metalworking plants (BO, TH, and YD) were identified. The peaks measured for C1 and C3 were attributed to tryptophan-like (Peak T) and humic/fulvic acid-like (Peak A + C) peaks, respectively, and the peaks at C2 were identified as humic-like (Peak A + M) or tryptophan-like (Peak T) peaks. There were differences in the C2 and C3 components of MWF from the three metalworking plants. The FDOM of MWF from the three metalworking plants exhibited similar polarity, but different apparent molecular weight distributions. In addition, the highest intensities of the three fluorescent peaks were sensitive to variations in the pH, humic acid (HA) concentrations, and metal ion levels (Cu2+, Fe3+, and Ni2+). The findings of this study not only indicate the FDOM characteristics of MWF, but also provide a promising method and valuable guidance for the practical monitoring of MWF in natural water bodies.

Novel insights into variation of fluorescent dissolved organic matters during antibiotic wastewater treatment by excitation emission matrix coupled with parallel factor analysis and cosine similarity assessment.

In this work, the variation of fluorescent dissolved organic matters (FDOM) of antibiotic wastewater in a full-scale treatment plant was studied. Fluorescent components of anaerobic, aerobic, Fenton stages were separately figured out by parallel factor analysis (PARAFAC) based on excitation emission matrix (EEM) dataset. Then, these components were pairwise quantitatively compared according to cosine similarity (CS). It was found that, after the anaerobic treatment, the major components showed remarkable similarity (CS > 0.97) to those of raw wastewater, although their maximum fluorescence intensity (Fmax) decreased slightly or moderately (7% ∼ 54%). However, the aerobic treatment dramatically changed both the composition and content of fluorescent components, as all the protein-like components completely disappeared and only the humic-like components with much lower intensity were observed. After Fenton oxidation, all these humic-like components were remained (CS > 0.97) with fairly reduced Fmax (51% ∼ 61%). For both aerobically treated and Fenton-oxidized wastewater, Fmax correlated well with dissolved organic carbon (DOC). This suggested a dominant proportion of humic-like substances. The combination of PARAFAC based on separate EEM dataset of each treatment stage and CS assessment is a good approach to better understand FDOM variation and can be of much practical significance to monitor wastewater quality.

Fluorescence and photophysical properties of xylene isomers in water: with experimental and theoretical approaches.

A thorough analysis of the photophysical properties involved in electronic transitions in excitation-emission spectra of xylene isomers has been carried out using the time-dependent density functional theory (PBEPBE/6-31 + G(d,p)) method. For the first time a structural and spectroscopic investigation to distinguish isomers of xylene, a widespread priority pollutant, was conducted experimentally and theoretically. The fluorescence properties of xylene isomers (sole and mixture (binary and ternary)) in water were studied. The fluorescence peak intensities of xylenes were linearly correlated to concentration, in the order of p-xylene > o-xylene > m-xylene at an excitation/emission wavelength (ex/em) of 260 nm/285 nm for o-, m-xylene and ex/em 265 nm/290 nm for p-xylene at the same concentration. The theoretical excitation/emission wavelengths were at ex/em 247 nm/267 nm, 248 nm/269 nm and 251 nm/307 nm for o-, m- and p-xylene, respectively. The vertical excitation and emission state energies of p-xylene (ex/em 4.94 eV/4.03 eV) were lower and the internal conversion energy difference (0.90 eV) was higher than those of m-xylene (ex/em 5.00 eV/4.60 eV) (0.4 eV) and o-xylene (ex/em 5.02 eV/4.64 eV) (0.377 eV). The order of theoretical emission and oscillator strength (0.0187 > 0.0175 > 0.0339) for p-xylene > o-xylene > m-xylene was observed to be in agreement with the experimental fluorescence intensities. These findings provide a novel fast method to distinguish isomers based on their photophysical properties.