Excitation-emission Matrices Research Articles

Comparison of UV-based advanced oxidation processes for the removal of different fractions of NOM from drinking water

This study examined the effectiveness for degradation of hydrophobic (HPO), transphilic (TPI) and hydrophilic (HPI) fractions of natural organic matter (NOM) during UV/H2O2, UV/TiO2 and UV/K2S2O8 (UV/PS) advanced oxidation processes (AOPs). The changing characteristics of NOM were evaluated by dissolved organic carbon (DOC), the specific UV absorbance (SUVA), trihalomethanes formation potential (THMFP), organic halogen adsorbable on activated carbon formation potential (AOXFP) and parallel factor analysis of excitation–emission matrices (PARAFAC-EEMs). In the three UV-based AOPs, HPI fraction with low molecular weight and aromaticity was more likely to degradate than HPO and TPI, and the removal efficiency of SUVA for HPO was much higher than TPI and HPI fraction. In terms of the specific THMFP of HPO, TPI and HPI, a reduction was achieved in the UV/H2O2 process, and the higest removal rate even reached to 83%. UV/TiO2 and UV/PS processes can only decrease the specific THMFP of HPI. The specific AOXFP of HPO, TPI and HPI fractions were all able to be degraded by the three UV-based AOPs, and HPO content is more susceptible to decompose than TPI and HPI content. UV/H2O2 was found to be the most effective treatment for the removal of THMFP and AOXFP under given conditions. C1 (microbial or marine derived humic-like substances), C2 (terrestrially derived humic-like substances) and C3 (tryptophan-like proteins) fluorescent components of HPO fraction were fairly labile across the UV-based AOPs treatment. C3 of each fraction of NOM was the most resistant to degrade upon the UV-based AOPs. Results from this study may provide the prediction about the consequence of UV-based AOPs for the degradation of different fractions of NOM with varied characteristics.

Japanese dace (Tribolodon hakonensis) fish freshness estimation using front-face fluorescence spectroscopy coupled with chemometric analysis

Although fish and its related products are good sources of protein and unsaturated fatty acids, like omega-3 in the human diet, their shelf-life is limited by biochemical and microbial changes. In this study, a front-face fluorescence spectroscopy technique was used to acquire Excitation-emission matrices (EEM) to monitor Japanese dace (Tribolodon hakonensis) fish freshness degradation during storage. EEM of Japanese dace fish parts (intact eyeball and surface-containing scales), excitation from 220 to 585 nm and emissions from 250 to 600 nm, were measured at different times during storage. To simplify the acquired complex spectra datasets from each fish part, the variables were reduced to those that were only significant/important (those with higher positive or negative correlation) for K value prediction, and as an index of freshness. Partial least square regression (PLSR) results demonstrated that combining the fluorescence EEM of the eyeball and surface-containing scales the best monitoring of fish freshness; excitation at 280 and 350 nm for both the eyeball and surface-containing scales, with 2.84 and 0.96 as RMSE and R2, respectively. These findings demonstrate that multiple excitation fluorescence approaches can be convenient for the freshness evaluation of fish.

Robust mitigation of FO membrane fouling by coagulation-floatation process: Role of microbubbles

Forward osmosis (FO) membrane fouling is a big obstacle in real textile wastewater treatment. Herein, a series of pretreatments include coagulation (C), microbubbles (Mbs) and their combination process (Mbs + C) were used to alleviate membrane fouling. Their different effects on flux and rejection rate of FO membrane were also investigated. Satisfactory removal efficiencies for UV254, dissolved organic carbon (DOC), chemical oxygen demand (COD) and antimony (Sb) of 48.27, 47.80, 40.70 and 41.87% were obtained at the optimum polyaluminum chloride (PAC) dosage of 300 mg L−1 and combined treatment time of 15 min. Compared with C alone, combined Mbs + C resulted in smaller flux decrease (~40%) and higher rejection rate (>98%) of FO membrane. This result confirmed the positive effect of Mbs on the combined processes. Fluorescence excitation-emission matrices coupled with parallel factor (EEM-PARAFAC), gel permeation chromatography (GPC) and gas chromatography mass spectrometry (GC–MS) measurements were further carried out to investigate the mitigation effect of pretreatments on membrane fouling. Results exhibited Mbs + C can significantly remove tryptophan-like substance and aliphatic alcohols due to enhanced coagulation-floatation property and oxidation of hydroxyl radicals. This study provides useful insights for fouling mitigation through Mbs and coagulation in actual FO process when dealing with textile wastewater.

Spatial Distribution of Colored Dissolved Organic Matter in the Western Arctic Ocean

Optical properties of colored dissolved organic matter (CDOM) were investigated along a latitudinal transect (67°–77° N) in upper water (<80 m depth) of the western Arctic Ocean. The absorption coefficient at 280 nm was 0.48–1.25 m−1, with the average for the oligotrophic basin area (1.04 ± 0.08 m−1) being slightly higher than that of the productive shelf area (0.95 ± 0.16 m−1), implying a decoupling effect between CDOM concentration and biological productivity in the western Arctic Ocean. The spectral slope coefficient S270–350 was negatively correlated with salinity, indicating that DOM molecular weight increases with salinity, and may be affected by melt-water input. Four fluorescent components were identified by excitation emission matrices elaborated by parallel factor analysis, including three humic-like (C1, C3, and C4) components and one protein-like (C2) component. Significant increases in concentrations of terrestrially derived humic-like C3 and C4 components with salinity were observed in the basin, mainly controlled by the physical mixing of surface fresh water and subsurface inflowing Pacific Ocean water. Terrestrial material carried by Pacific inflow is thus an important factor affecting the distribution of CDOM fluorescence components. The C3 and C4 fluorescence components may be useful as tracers of Pacific water in the western Arctic Ocean.

The Influence of Organic Matter Origin on the Chlorine Bulk Decay Coefficient in Reclaimed Water

Using reclaimed water has been increasing to manage water shortages arising due to climate change. Research has been conducted on reclaimed water production, but few studies have investigated the pipe network and supply of reclaimed water. Reclaimed water contains greater amounts of organic matter, nutrients, and ionic substances compared to tap water. Therefore, it is highly likely to cause problems, such as water pollution due to microbial propagation in pipes, and leakage due to pipe corrosion, which interfere with water supply system operations. This study investigated the residual chlorine decay characteristics of chlorine disinfectants applied to a control biofilm in reclaimed water pipe networks. The bulk decay coefficient was compared between reclaimed water and a humic acid solution, and the origin of organic matter was analyzed using fluorescence excitation-emission matrices. The experimental results show that residual chlorine was consumed because protein and amino acid-based organic matter reacted more rapidly with chlorine than natural organic matter, such as humic acid. Moreover, chlorine bulk decay occurred rapidly in reclaimed water when total organic carbon was 3 mg/L or higher. These results confirm that removing organic matter during reclaimed water treatment may affect the management of the pipe network system.

The characteristics of dissolved organic matter release from UV-aged microplastics and its cytotoxicity on human colonic adenocarcinoma cells

There are a large number of microplastic (MPs) in the sea or on land, most of which undergo physical, chemical or biological processes leading to the release of dissolved organic matter (DOM). In this study, we analyzed the change of Polyurethane microplastic (PU-MPs) valence bond under different aging conditions thanks to Fourier transform infrared spectroscopy (FTIR) and its surface characteristics using scanning electron microscopy (SEM) and also described the characteristics of DOM dissolved from PU (PU-DOM) under UV aging process in two different medium (water and air), based on Dissolved organic carbon (DOC) measurements, UV–visible spectrometer and Three-dimensional excitation emission matrices (3D-EEMs). The DOC data both showed that Under UV aging of different systems, PU-DOM concentration increases with the extension of aging time, and correspondingly, its toxicity to human colon adenocarcinoma cells also increases, but the release amount of PU-DOM under air aging is higher than that of PU-DOM in water. We speculate that it may be the refraction and scattering of water, which leads to the reduction of the intensity of UV radiation. 3D-EEMs identified tryptophan-like fluorescent component and tyrosine-like component, meanwhile, the liquid chromatography-mass spectrometer (LC-MS) data further confirmed the formation of acid substances. The results further confirmed that the composition of PU-DOM in different systems is the same, but the release amount is different. The contents of the produced conjugated carbonyls and Reactive oxygen species (ROS) because of light irradiation increased likewise. The cytotoxicity of PU-DOM was consistent with the changing trend of ROS level in PU-MPs, suggesting that the produced ROS induced the in vitro toxicities. The results not only highlight the adverse health effects of photoaged PU-MPs, but also provide new perspectives for the environmental risks of MPs.

Introducing the multi-dimensional spectral phasors: a tool for the analysis of fluorescence excitation-emission matrices

The use of phasors to analyze fluorescence data was first introduced for time-resolved studies for a simpler mathematical analysis of the fluorescence-decay curves. Recently, this approach was extended to steady-state experiments with the introduction of the spectral phasors (SP), derived from the Fourier transform of the fluorescence emission spectrum. In this work, we revise key mathematical aspects that lead to an interpretation of SP as the characteristic function of a probability distribution. This formalism allows us to introduce a new tool, called multi-dimensional spectral phasor (MdSP) that seize, not only the information from the emission spectrum, but from the full excitation-emission matrix (EEM). In addition, we developed a homemade open-source Java software to facilitate the MdSP data processing. Due to this mathematical conceptualization, we settled a mechanism for the use of MdSP as a tool to tackle spectral signal unmixing problems in a more accurate way than SP. As a proof of principle, with the use of MdSP we approach two important biophysical questions: protein conformational changes and protein-ligand interactions. Specifically, we experimentally measure the EEM changes upon denaturation of human serum albumin (HSA) or during its association with the fluorescence dye 1,8-anilinonaphtalene sulphate (ANS) detected via tryptophan-ANS Förster Resonance Energy Transfer (FRET). In this sense, MdSP allows us to obtain information of the system in a simpler and finer way than the traditional SP. Specifically, understanding a protein’s EEM as a molecular fingerprint opens new doors for the use of MdSP as a tool to analyze and comprehend protein conformational changes and interactions.

Optical properties of dissolved organic matter in Japanese rivers and contributions to photoformation of reactive oxygen species

The optical properties of dissolved organic matter (DOM) from five rivers (Kokubu, Kurose, Ohta, Yamato, and Yodo) in Japan were investigated and contributions of DOM to photoformation of three reactive oxygen species (ROS) (hydroxyl radicals (OH), nitric oxide radicals (NO), and singlet oxygen (1O2)) were assessed. The lowest and highest mean dissolved organic carbon concentrations were for the Ohta River (0.95 (mg C) L−1) and Yamato River (2.85 (mg C) L−1), respectively, and the concentrations correlated with some optical parameters. Absorption ratios (e.g., the E2:E3 and A280/A350 ratios) and the spectral slope S275–295 indicated that DOM from the Yodo and Kokubu rivers had the lowest and highest molecular weights, respectively. PARAFAC models and DOM excitation–emission matrices were used to assess the sources and fates of DOM in the rivers. The PARAFAC model indicated that the main types of fluorescent DOM in the rivers were terrestrial humic-like (TH-L) and tryptophan-like (TP-L) substances. The Kokubu River contained other compounds such as fluorescent whitening agents, autochthonous humic-like substances, and extracellular polymeric substances. Statistically significant relationships between the dissolved organic carbon and TH-L, TP-L, and extracellular polymeric substance concentrations suggested that TH-L, TP-L, and extracellular polymeric substances are important contributors to total DOM in the rivers. TH-L and TP-L substances strongly contribute to ROS photoformation, but TH-L substances play roles in both ROS generation and scavenging. Comprehensive models for estimating the photoformation rates of different ROS (in M s−1) were established by integrating the contributions of the relevant major and minor sources. Examples are ROH (10−12) = 21.0 [NO2−]_μM + 0.460 [TH-L]_QSU + 10.9, RNO (10−12) = 67.9 [NO2−]_μM + 35.2 [a300]_m−1 − 2.51 [TH-L]_QSU − 0.765 [TP-L]_QSU − 8.14, and R1O2 (10−9) = 3.81 [a300]_m−1 − 0.101 [TP-L]_QSU + 11.1.

Source and Optical Dynamics of Chromophoric Dissolved Organic Matter in the Watershed of Lake Qinghai

Lake Qinghai is the largest lake in China and is of great significance to maintain the ecological security of the Qinghai-Tibet Plateau. Few studies have been carried out to investigate the optical composition and source of chromophoric dissolved organic matter (CDOM) in large lakes on the Qinghai-Tibet Plateau. It is of great significance to study the source and optical dynamics of CDOM in Lake Qinghai watershed for water quality protection and filling in the gaps in the knowledge of CDOM variability in a remote area. Two sampling campaigns in the Lake Qinghai watershed were carried out, and excitation-emission matrices coupled with parallel factor analysis (EEMs-PARAFAC) were used to unravel the optical composition and the sources of CDOM. Our results indicated that the mean dissolved organic carbon (DOC) concentration, a250:a365, and the spectral slope of CDOM absorption S275-295 in the lake were significantly higher than that in the inflow river (P<0.0001, t-test), whereas the mean absorption coefficient of CDOM a350, humification index (HIX), fluorescence peak integration ratio IC:IT, and specific ultraviolet absorbance at 254 nm SUVA254 of CDOM were shown to be lower in the lake than in the inflow river (P<0.0001), indicating that compared with the lake itself, CDOM in the inflow was humic-rich and highly aromatic. Four fluorescent components were obtained using PARAFAC, including a terrestrial human-like component C1, a microbial human-like component C2, a tyrosine-like C3, and a tryptophan-like C4. The mean DOC concentration, S275-295, and a250:a365in the headwater streams of the Lake Qinghai watershed were lower than those in the downstream estuary, indicating that the CDOM abundance increased, and the molecular weight decreased, from the headwaters to the downstream river mouths. The mean of SUVA254, C1, and the first axis of principal component analysis were positively related to terrestrial input (i.e., the PC1 values were significantly higher in rivers than in lakes (P<0.001)), indicating that the aromaticity of CDOM in rivers was higher than that in lakes. Particularly, the contribution of terrestrial humic-like C1 was higher in the Quanji River, Shaliu River, and Khargai River compared with that in other tributaries due to an intensified cultivated land use at the downstream estuary of these rivers.

Sorption of Pb(II) onto biochar is enhanced through co-sorption of dissolved organic matter

Biochar plays an important role in controlling migration of pollutants in soils. However, little information is available on the interactions between soil-derived dissolved organic matter (DOM), biochar and soluble metal species. The aim of this work was to present the adsorption process of soil DOM by biochar (corn straw biochar produced at 700 °C) and to determine whether co-sorption of DOM would change the affinity for Pb(II). The adsorption rates of biochar and biochar + DOM for Pb(II) were best fitted with a pseudo-second order kinetic model, and the equilibrium adsorption isotherm data agreed well with both the Langmuir and Freundlich models. Adsorption of DOM to biochar reached equilibrium after 15 h with an uptake of 52% of the supplied DOM. We used fluorescence excitation-emission matrices (EEMs) with parallel factor (PARAFAC) analysis to demonstrate that protein-like, fulvic acid-like and humic acid-like substances were the primary constituents of the DOM, which were quenched over time in the presence of biochar. Synchronous fluorescence spectra indicated that the protein-like structures were the predominant fluorescence substances in DOM. Two-dimensional correlation spectroscopy (2D-COS) showed the binding of DOM to biochar resulted in the quenching of fluorescence in the order: protein-like substances > humic-like substances (280 > 355 nm). Data supports the notion that DOM can increase the adsorption capacity of biochar for metal-ions.

Excitation-Emission Matrices and Parafac in the Investigation of the Bioactive Compound Effects on Olive Oils

Excitation-Emission Matrices and Parafac in the Investigation of the Bioactive Compound Effects on Olive Oils

Dissolved organic matter and its correlation with phytoplankton abundance for monitoring surface water quality

BACKGROUND AND OBJECTIVES: Dissolved organic matter has a fundamental role in supporting phytoplankton abundance and growth in aquatic environments. However, these organisms produce dissolved organic matter with varied quantities or characteristics depending on the nutrient availability and the species composition. Therefore, this study aims to assess the characteristic of dissolved organic matter on surface water and its correlation with phytoplankton abundance for monitoring water quality.METHODS: The sample was obtained at four Kali Surabaya River stations for further dissolved organic matter analysis and phytoplankton species analysis. The analysis was presented through bulk parameters of total organic, ultraviolet at 254 nm wavelength (UV254), specific ultraviolet absorbance value, and fluorescence spectroscopy using excitation-emission matrices with fluorescence regional integration analysis.FINDINGS: The results showed the bulk parameters of dissolved organic matter at all stations were significantly different, as Station 1 and 2 were higher, while 3 and 4 had a lower concentration. Furthermore, the fluorescence spectroscopy identified four components of dissolved organic matter at all stations, namely aromatic proteins-like (AP-like), humic acid-like (HA-like), soluble microbial by-products-like (SMPs-like), and fulvic acid-like (FA-like). Also, stations 1 and 2 were grouped in the high percentage FRI of humic substance (FA-like and HA-like), while 3 and 4 were classified in the high percentage FRI of non-humic substances (AP-like and SMPs-like).CONCLUSION: The main phytoplankton species, namely Plectonema sp., Pinularia sp., Nitzchia sp., Navicula sp., had the highest abundance at Stations 1, 3, and 4, respectively. A strong correlation between dissolved organic matter analysis and phytoplankton abundance led to the usage of these methods for monitoring surface water quality.

Dissolved organic matter photodegradation in a water supply reservoir on temperate oceanic climate (Cfb): a case study of Passaúna reservoir, Brazil

Abstract Photodegradation is an important process for aquatic metabolism, related to the dissolved organic matter (DOM) transformation in water. For example, in a water supply reservoir, DOM is an important parameter since it can react and form disinfection by-products during water treatment. Thus, the understanding and determination of photodegradation rates are especially relevant for water resources management since they can influence DOM transformation in the water column. However, besides its relevance, few studies were conducted in the southern hemisphere for photodegradation rates determination. Therefore, we carried out field experiments to characterize and evaluate DOM photodegradation rate ‒ at different depths and in two solar irradiation periods ‒ through the application of absorption spectroscopy techniques in the UV-Vis region and fluorescence excitation-emission matrices (EEM) combined with the dissolved organic carbon (DOC) measurement. Low concentrations of natural DOM and nutrients in the aquatic environment were measured during the field monitoring. Our results indicate that photodegradation rates for a temperate oceanic climate reservoir were proportional to the availability of solar radiation, being more representative considering the time scale.

Response of Chlorophyll Fluorescence Characteristics and Dissolved Organic Matter for Marine Diatom Skeletonema dohrnii under Stress from Penicillin and Zn2.

Skeletonema dohrnii is a good model diatom for studying environmental stress and has promising applications and prospects in various fields. Antibiotics and heavy metals are commonly exceeded in the nearshore marine habitats. In this work, we investigated the effects of an antibiotic (penicillin, 2 µg/L) and a heavy metal ion (Zn2+, 10 µmol/L) stress on marine diatom S. dohrnii, mainly using excitation-emission matrices (EEMs) fluorescence methods and OJIP test. Results indicated that algal cells grown with the antibiotic showed higher biomass, specific growth rate, doubling time, chlorophyll a, and chlorophyll fluorescence variables. Moreover, excess zinc had negative effects on S. dohrnii. We found that zinc not only inhibited the relative photosynthetic electron transfer efficiency but also reduced the Chl a content, which ultimately affected algal growth and organic matter production. In addition, the combined effect of penicillin and Zn2+ further affected the physiological state of S. dohrnii. The dissolved organic matter (DOM) characteristics of the four cultures were also different, including fluorescence indices (fluorescence index, biological index, β/α, and humification index) and fluorescence peaks (peaks A, C, M and T). In brief, characterization of chlorophyll fluorescence characteristics and DOM-related variables are important for understanding the effects of environmental stress on microalgae.

Production of Labile Protein-Like Dissolved Organic Carbon Associated With Anaerobic Methane Oxidization in the Haima Cold Seeps, South China Sea

Cold seeps where methane-rich fluids escape from the seafloor generally support enormous biomass of chemosynthetic organisms and associated fauna. In addition to transporting a great amount of methane toward the seafloor, cold seeps also contribute to the aged, dissolved organic carbon (DOC) pool in the deep ocean. Here, two sediment cores from the “Haima cold seeps,” northern South China Sea and a nearby reference core were analyzed for pore-water sulfate and DOC concentrations, δ13C of DOC, and optical properties of dissolved organic matter (DOM). High DOC concentrations (0.9–3.7 mM) accompanied by extremely low δ13C values (−43.9 to −76.2‰) suggest the conversion of methane into sedimentary DOC pool in the seep sediments. Parallel factor analysis (PARAFAC) of the fluorescence excitation-emission matrices shows higher fluorescent intensities of labile protein-like components (C2 and C4) and lower fluorescent intensities of refractory humic-like components (C1 and C3) in the seep cores compared to the reference core. The intensity of C2 is positively correlated with DOC concentrations and δ13C-DOC in the seep sediments, suggesting that the labile protein-like DOM was produced by the anaerobic oxidation of methane (AOM). Moreover, low humification index (HIX) and high biological index (BIX) values also indicate intensified production of relatively labile DOM with lower degradation degree in the seep cores compared to the reference core. Hence, we highlight that methane-derived DOC may serve as important carbon and energy sources for heterotrophic microbial communities due to its relatively labile nature.

Rapid determination of three textile surfactants in environmental samples by modeling excitation-emission second-order data with multi-way calibration methods.

The textile industry is an important potential source of environmental pollution due to the use of chemical products. Dyes, hydrolyzed dyes, and surfactants, among others, are chemical compounds present in wastewater of textile plant. Moreover, the anionic surfactants have toxic effects for various aquatic organisms even in low concentrations. The methodologies investigated to quantify surfactants, in general, consume a lot of analysis time and frequently use toxic or environmentally objectionable reagents. For these reasons, the objective of this work was to develop a quick and simple method to quantify surfactants without the use of expensive reagents and equipment, avoiding extraction and preconcentration stages. The proposed method is based on fluorescent spectroscopy measurements for the acquisition of second-order data in excitation-emission matrices and multivariate calibration techniques applied to the data. The unfolded partial least squares combined to residual bilinearization (U-PLS/RBL) algorithm was better than parallel factor analysis (PARAFAC). U-PLS/RBL accurately quantified alkylnonylphenolethoxylated (APEO), dodecylbenzenesulfonic acid (ADBS), and 2-phenoxy-ethoxylated fatty alcohol (AGFE) surfactants. The chemometric model obtained good analytical figures of merit: REP% between 5 and 13 and LOQ between 0.45 and 2.77 μg mL-1. This methodology had no significant difference compared with results obtained by a HPLC-FD reference technique, in addition with a considerable reduction in analysis time, reagent consumption, and therefore lower cost. For environmental applications, APEO, ADBS, and AGFE were quantify in textile wastewater treatment and in the receiving water body. The concentrations varied from 8.73 to 73.94 μg mL-1 in the textile wastewater and were not detected in the receiving water body.

Evaluation of Hydrophilic and Lipophilic Antioxidant Capacity in Spanish Tomato Paste: Usefulness of Front-Face Total Fluorescence Signal Combined with Parafac

The hydrophilic and lipophilic antioxidant activities due to the main bioactive components present in Spanish tomato paste samples were studied, using standardized and fluorescent methods. After extraction, phenolic antioxidants (Folin-Ciocalteu method) and total antioxidant activity (TEAC assay) were evaluated, examining differences between hydrophilic and lipophilic extracts corresponding to different samples. Total fluorescence spectra of extracts (excitation-emission matrices, EEMs) were recorded in the front-face mode at two different ranges: 210–300 nm/310–390 nm, and 295–350 nm/380–480 nm, for excitation and emission, respectively, in the hydrophilic extracts. In the lipophilic extracts, the first range was 230–283 nm/290–340 nm, while the second range was 315–383 nm/390–500 nm for excitation and emission, respectively. EEMs from a set of 22 samples were analyzed by the second-order multivariate technique Parallel Factor Analysis (PARAFAC). Tentative assignation of the different components to the various fluorophores of tomato was tried, based on literature. Correlation between the antioxidant activity and score values retrieved for different components in PARAFAC model was obtained. The possibility of using EEMs-PARAFAC to evaluate antioxidant activity of hydrophilic and lipophilic compounds in these samples was examined, obtaining good results in accordance with the Folin-Ciocalteu and TEAC assays.

Advanced oxidation processes for removal of organics from cooling tower blowdown: Efficiencies and evaluation of chlorinated species

One of the major challenges in reusing cooling tower blowdown water (CTBD) utilizing membrane processes is its remaining organic compounds, e.g., humic substances leading to biofouling. Besides, the possible abundance of chloride in CTBD imposes the concern of the formation of chlorinated by-products. To choose a pre-treatment process for the studied CTBD composition, various advanced oxidation processes (AOPs), including electrooxidation (EO), photocatalytic degradation (PCD), heat-activated persulfate oxidation (PS), UVC/vacuum UV (UVC/VUV), and UVC processes, were evaluated and compared based on two main targets: i) highest removal and mineralization of the organics, especially humic substances; and ii) lowest formation of chlorinated by-products including adsorbable organic halides and oxychlorides. All the processes were conducted in the natural condition of the real CTBD, while solution pH was monitored. Based on results of chemical oxygen demand, total organic carbon, dissolved organic carbon, UV254 absorbance, liquid-chromatography–organic carbon detection (LC-OCD), and fluorescence excitation-emission matrices (FEEM), it is concluded that PS leads to complete removal of organic compounds along with the lowest formation of low molecular weight organic acids and organic neutrals. FEEM and LC-OCD data also indicated that EO, PCD, and UVC/VUV processes brought about substantial removal of organic compounds and broke down the humic substances into low molecular weight building blocks and organics. Besides, EO exhibited the highest AOX and oxychlorides formation, while these were limited when using the other AOPs. Summarizing, PS, PCD, and UVC/VUV were efficient processes for the degradation and mineralization of organics without generating significant amounts of chlorinated by-products.

Insight into variations of DOM fractions in different latitudinal rural black-odor waterbodies of eastern China using fluorescence spectroscopy coupled with structure equation model

The structural compositions of dissolved organic matter (DOM) could profoundly affect formation and evolution of black-odor waterbodies (BOWs). In this study, 81 samples of BOWs were collected from three different latitudinal rural regions in eastern China, including low, middle and high latitude regions. Based on fluorescence index (FI) and biological index (BIX) deduced from excitation-emission matrices (EEMs) of rural BOWs, biological source of DOM was dominant in low latitude, while DOM derived from both biological and terrestrial in mid-latitude and high-latitude. Furthermore, humification degree of DOM in the former was lower than those in the latter based on humification index (HIX) deduced from EEMs. Seven fluorescence components of DOM were extracted by EEMs combined with parallel factor analysis: components 1 and 2 (C1 and C2) known as tryptophan-like substances, C3 and C4 associated with tyrosine-like, C5 related with biological byproducts, C6 relative to fulvic-like, and C7 referred as humic-like. The roughly decreasing order of percentages in DOM fractions from the rural BOWs was tyrosine-like > tryptophan-like > fulvic-like > microbial byproduct > humic-like in three regions. According to hierarchical cluster analysis and redundancy analysis, the autochthonous fresh DOM was dominant in low latitudinal rural BOWs, which was relative to actions of phytoplankton and microorganisms. However, humification degree of DOM increased with a rise in latitude, which could attribute to variations of climate and agriculture industrial structure. Based on structure equation model, the C5 and FI were the potential factors of the rural BOWs, which suggested that microbial activity and pollution sources should affect formation and evolution of rural BOWs. These findings are conductive to reveal composition and fluorescence properties of DOM and in recognizing the potential factors of forming mechanism in rural BOWs, which could provide basic theoretical support for policymakers to regulate and treat it.

Inactivation of Microcystis Aeruginosa by peracetic acid combined with ultraviolet: Performance and characteristics

The inactivation of algae by a combined process of peracetic acid and ultraviolet irradiation (UV/PAA) was systematically investigated by choosing Microcystis aeruginosa as the reference algal species. Both hydroxyl (HO•) and organic radicals (RO•) contributed to the cell integrity loss and RO• played the dominant roles. The algae inactivation kinetics can be well fitted by the typical Hom model, showing that the inactivation kinetic curves followed a type of shoulder and exponential reduction. The initial shoulder might be induced by the protection from the cell wall. Although the results from the cell morphology, UV–vis spectra and fluorescence excitation-emission matrices analysis suggested the cell lysis and the release of algal organic matter (AOM) in the UV/PAA process, the AOM could be subsequently degraded. Humic acid (1 − 5 mg/L) inhibited the algal cell inactivation, and the presence of chloride (0.5 − 2 mM) had little effect on the cell viability reduction. However, the addition of bicarbonate (1 − 5 mM) promoted cell integrity loss. The UV/PAA process displayed better performance under the natural water background, demonstrating the extensive potential for the practical application of this approach. This study suggests that the UV/PAA process is an effective strategy for algae inactivation.