Fluorescence Regional Integration Research Articles

Exogenous factors impact on bacterial-microalgal growth and chromophoric dissolved organic matter: a case study of Chrysotila dentata and Marinobacter hydrocarbonoclasticus

The relationship between Chrysolia dentata and bacteria that play an important role in the carbon cycle is complex yet closely intertwined. However, there is still limited knowledge about how phytoplankton interacts with heterotrophic bacteria under external influences. The transformation and processing of dissolved organic matter (DOM) by epiphytic bacteria for phytoplankton especially, under vitamin B12 (VB12) and abscisic acid (ABA) introducing have rarely been investigated. In this experiment, Marinobacter hydrocarbonoclasticus (CA6) was cultured with Chrysotila dentata to investigate growth and DOM release and transformation under the influence of VB12 and ABA. Three-dimensional (3D)-EEM, combined with fluorescence regional integration and the peak selecting method, was used to obtain fluorescent peaks (B, T, A, and C) and four indexes for DOM analysis. Our findings indicate that the incubation of CA6 significantly enhances the release of protein-like components (peak T) and humic-like components (peak C) during the incubation period. However, 100 μg/L VB12 or abscisic acid does not promote axenic microalgae growth or release of C. dentata-derived DOM. However, they have different effects on C. dentata-CA6 growth and the derived DOM. Abscisic acid can facilitate steady growth of both C. dentata and CA6 cells while enhancing the amounts of humic-like components. Conversely, VB12 inhibits the growth of CA6 and results in a rapid decrease in protein-like signal, but it does not significantly enhance C. dentata growth or the transformation of DOM. This indicates that ABA can support stable co-grown of microalgal and bacteria in a water environment, while VB12 may hinder CA6 bacterial growth, resulting in a less stable co-cultured environment. This study uncovers and verifies the impact of exogenous factors and heterotrophic bacteria in the growth of microalgae, underlining their role in transforming and generating algae-derived dissolved organic matter (DOM) within laboratory settings.

Ameliorating tannery sludge dewaterability by disintegration of extracellular biopolymers with FeCl3-MnSO4/oxalic acid/sodium percarbonate: Spectroscopic profiling of dissolved organic matter in sludge filtrate

Effectual sludge dewatering techniques are strongly desired by industrial wastewater treatment plants. In this work, we scrutinised the efficacy of various Fenton based complex mediated processes like ferric chloride (FeCl3)/oxalic acid (OA)/sodium percarbonate (SPC) (FOS), FS (without OA), manganese sulphate (MnSO4)/oxalic acid (OA)/sodium percarbonate (SPC) (MOS) and MS (without OA) for which capillary suction time (CST) was attained as follows: MS (204 s) < MOS (180 s) & FS (180 s) < FOS (174 s) at pH 3. This implied the role of chelating agent (OA) in improving sludge dewaterability by disintegrating Extracellular Polymeric Substances (EPS) and releasing converted free water from the sludge flocs. FTIR results of sludge samples revealed the higher release of aromaticity after treatment process. Presence of aromatic carboxylate compounds were confirmed by GC–MS analysis. A detailed inquisition on the dissolved organic matter (DOM) of filtrate samples using 3DEEM fluorescence methods like second derivative Accumulative Fluorescence Emission (AFE), Fluorescence Regional Integration (FRI) and UV–Visible spectroscopic method like multipeak Gaussian fitting were performed that signified Microbial Soluble Products.

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

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

The migration and transformation processes of dissolved organic matter in rainwater- drip water- phreatic water of a typical karst spring catchment, in South China

The dissolved organic matter (DOM) migration and transformation in karst aquifer are of great significance for geochemical processes but remain poorly understood. In this study, we selected the Guilin Yaji Karst Experimental Site as a natural laboratory and collected rainwater (RW), drip water (DW), and phreatic water (PW) from September 2019 to September 2021 to study the DOM migration and transformation in a typical bare karst spring catchment. Hydrochemical and stable hydrogen and oxygen isotopes were applied to study the water cycle of the aquifer. Absorbance and fluorescence spectroscopy were used to characterize the DOM quality. Three-dimensional fluorescence combined with fluorescence regional integration was used for identifying the DOM compositions. The RW DOM had a weak humification degree and strong terrestrial characteristics. It was affected by the monsoon and showed higher humification in the dry season than in the wet season. The higher rainfall intensity had a dilution effect on the DOM fluorescence components levels when the rain intensity was>10 mm/day (not the threshold value). Continuous rain events led to the continuous dilution effect on RW DOM in the dry season, but such a phenomenon was not obvious in the wet season. The DW DOM inherited weak humification characteristic that was close to RW DOM but was altered by the hydrogeology conditions and plant root and microbial activities intensities of the upper vadose zone. The higher humification degree of PW DOM may be related to the higher degree of microbial processing caused by the longer groundwater residence time. The humic and hydrophobic degree of DOM for fissure PW was weaker than that for conduit PW because fissure media provides a superior condition for DOM to adsorb to the mineral surface. In the wet season, when the preferential channel of the aquifer was activated, the PW DOM showed similar characteristics to RW DOM, indicating a significant hydrologic effect on the PW DOM. Our results provide a valuable reference to advance understanding of DOM behavior in karst aquifer and highlight the importance of hydrogeologic conditions and hydrologic processes on DOM migration and transformation.

Response of dissolved organic matter characteristics to nitrogen addition in a boreal peatland of Northeast China

Boreal peatlands, a crucial stock of dissolved organic matter (DOM), are susceptible to increased reactive nitrogen (N) inputs. However, the response of DOM characteristics to elevated N availability in these ecosystems is still obscure. Here, we investigated the seasonal variability of DOM quantity and characteristics in surface water and soil pore water after 5-year multi-level N addition (0, 3, 6, and 12 g N m−2 year−1) in a permafrost peatland of Northeast China. In this study, we used the excitation-emission matrix fluorescent spectroscopy combined with fluorescence regional integration, parallel factor analysis, and fluorescence parameters to decipher the effects of N addition on DOM composition, origin, and fate. Irrespective of N addition level, increased N availability reduced dissolved organic carbon concentrations in surface water and soil pore water. However, DOM characteristics are more responsive to N addition in soil pore water than in surface water. Nitrogen addition did not affect DOM composition in surface water, but altered the proportions of tyrosine-, tryptophan-, fulvic acid-, and humic-like DOM in soil pore water. Moreover, the changing trends of DOM composition were diverse during the growing season. In addition, compositional transformations of DOM did not change its biogenic signals, freshness, and humification in both surface water and soil pore water across the growing season. Our results suggest that increased N availability reduces DOM quantity and alters DOM chemical composition, which will improve our understanding of soil organic matter dynamics in boreal peatlands.

Characterization of Dissolved Organic Matter Released from Aged Biochar: A Comparative Study of Two Feedstocks and Multiple Aging Approaches.

Dissolved organic matter (DOM) plays important roles in environmental ecosystems. While many studies have explored the characteristics of aged biochar, limited information is available about the properties of DOM derived from aged biochar. In this study, biochar obtained from maize stalk and soybean straw were aged using farmland or vegetable-soil solution, as well as soil solution containing hydrogen peroxide (H2O2). Chemical composition of the extracted DOM from the aged biochar was analyzed via excitation-emission matrix coupled with fluorescence regional integration (FRI) and parallel factor analysis (PARAFAC). Obtained results showed that biochar aged with H2O2-enriched soil solution had higher water-soluble organic carbon, ranging from 147.26-734.13% higher than the controls. FRI analysis revealed fulvic and humic-like organics as the key components, with a considerable increase of 57.48-235.96% in the humic-like component, especially in soybean-straw-aged biochar. PARAFAC identified four humic-like substance components. Concurrently, the aromaticity and humification of the aged-biochar-derived DOM increased, while the molecular weight decreased. These findings suggest that DOM derived from aged biochar, with a high content of humic-like organics, might impact the mobility and toxicity of pollutants in soil.

Effects of raw water quality on the adsorptive removal of 2-methylisoborneol by powdered activated carbon under non-equilibrium conditions

Abstract Natural organic matter contained in natural water inhibits the adsorptive removal of 2-methylisoborneol (2-MIB) by powdered activated carbon (PAC). We investigated the relationship between water-quality indices and the adsorptive removal of 2-MIB by PAC. We collected three different raw water (i.e., two lake water and one river water) samples twice per month for 10 months. We characterized the raw water using total organic carbon concentration, ultraviolet absorption at 254 nm, electrical conductivity, and excitation–emission matrix analysis. The results were compared with 2-MIB removal rates evaluated from PAC adsorption experiments and revealed that there was no universal indicator that could explain the trends of the 2-MIB removal rate during the overall experimental period. The correlation trends between 2-MIB removal rates and water-quality indices differed significantly between the high and low water-temperature periods. Several water-quality indices related to the organic matter associated with biological processes, especially algal activities (i.e., soluble microbial products, chlorophylls, and phycocyanin), exhibited significant correlations with the 2-MIB removal rates (|R| &amp;gt; 0.7) under certain conditions (e.g., high lake-water temperature). Both the parallel factor (PARAFAC) analysis and fluorescence regional integration (FRI) method could evaluate such behaviors after including the regions associated with algal organic matter in the calculation.

Application of fluorescence spectra and molecular weight analysis in the identification of algal organic matter-based disinfection by-product precursors

Algal organic matter (AOM) is considered to be threatening for the consumption of disinfectants and the formation of disinfection by-products (DBPs) during the disinfection process. Incompatible parameters in the conventional pretreatment of algal-laden water will lead to counterproductive results, such as AOM release. Therefore, the generation of AOM and its conversion to DBPs during pretreatment should be observed. The characteristics of DBPs from extracellular organic matter (EOM) and intracellular organic matter (IOM) were epitomized and simulation experiments were conducted in deionized (DI) water and source water under pretreatment conditions. Differences in DBP formation between the different backgrounds during chlorination and powdered activated carbon (PAC) treatment were investigated. Instead of monotonous excitation-emission matrix (EEM) spectra, molecular weight (MW) fractionation was simultaneously applied to elucidate the mechanisms of chlorination and PAC adsorption on AOM-based DBPs. The fluorescence regional integration (FRI) EEM results showed a clear correlation between the fluorescent properties and MW distribution of AOM. A decreasing trend was observed after a rapid increase in fluorescence intensity during the chlorination and PAC treatment of water samples in the simulation experiments in deionized (DI) water and source water. The DBP formation potential (FP) in the source water was consistent with the change in AOM during chlorination and PAC adsorption. In addition, EEM showed decent predictability of AOM-based trihalomethanes (THM) FPs (R2 = 0.77–0.99) invoking a combination with MW fractionation. Macromolecular protein compounds were highly correlated with the formation of dichloroacetonitrile (DCAN) (R2 = 0.89–0.98). These post-mortems results imply that EEM spectra are a useful tool for identifying AOM-based precursors to reveal the accurate environmental fate and risk assessments of AOM.

The Influence of Aerated Irrigation on the Evolution of Dissolved Organic Matter Based on Three-Dimensional Fluorescence Spectrum

In order to unravel the effect of aerated irrigation on soil dissolved organic matter (DOM) fluorescence characteristics, and humification degree, a randomized block experiment was conducted with three factors and a two-level design, i.e., two irrigation rates (0.6 and 1.0 times of crop evaporation pan coefficient, W1 and W2), two nitrogen application rates (225 and 300 kg hm−2, N1 and N2), and two aeration rates (15% and 0% in control treatment, A1 and A0). Fluorescence regional integration (FRI) and correlation analysis methods were used to investigate the evolution characteristics of the soil DOM fluorescence spectrum. Under aerated and conventional subsurface irrigation, soil DOM components were dominated by humic acid-like substances, fulvic acid-like substances, tryptophan-like proteins, and supplemented by tyrosine-like proteins and dissolved microbial metabolites. Soil aeration could promote the consumption of soil DOM components under low irrigation rates and accelerate the consumption of soil DOM components under high irrigation rates. The humification index of AI treatments varied from 8.47 to 9.94 during the maturity growth stage of pepper, averagely increased by 31.59% compared with the non-aeration treatment. To sum up, aerated irrigation can promote the depletion of small molecular proteins and accelerate nutrient turnover and the accumulation of big molecular proteins.

Deciphering the contribution of microbial biomass to the properties of dissolved and particulate organic matter in anaerobic digestates

The recalcitrant structures either from substrate or microbial biomass contained in digestates after anaerobic digestion (AD) highly influence digestate valorization. To properly assess the microbial biomass contribution to the digested organic matter (OM), a combination of characterization methods and the use of various substrate types in anaerobic continuous reactors was required. The use of totally biodegradable substrates allowed detecting soluble microbial products via fluorescence spectroscopy at emission wavelengths of 420 and 460 nm while the protein-like signature was enhanced by the whey protein. During reactors' operation, a transfer of complex compounds to the dissolved OM from the particulate OM was observed through fluorescence applied on biochemical fractionation. Consequently, the fluorescence complexity index of the dissolved OM increased from 0.59–0.60 to 1.06–1.07, whereas it decreased inversely for the extractable soluble from the particulate OM from 1.16–1.19 to 0.42–0.54. Accordingly, fluorescence regional integration showed differences among reactors based on visual inspection and orthogonal partial latent structures (OPLS) analysis. Similarly, the impact of the substrate type and operation time on the particulate OM was revealed by 13C nuclear magnetic resonance using OPLS, providing a good model (R2X = 0.93 and Q2 = 0.8) with a clear time-trend. A high signal resonated at ∼30 ppm attributed to CH2-groups in the aliphatic chain of lipid-like structure besides carbohydrates intensities at 60–110 ppm distinguished the reactor fed with whey protein from the other, which was mostly biomass related. Indeed, this latter displayed a higher presence of peptidoglycan (δH/C: 1.6–2.0/20–25 ppm) derived from microbial biomass by 1H-13C heteronuclear single-quantum coherence (HSQC) nuclear magnetic resonance. Interestingly, the sample distribution obtained by non-metric multidimensional scaling of bacterial communities resembled the attained using 13C NMR properties, opening new research perspectives. Overall, this study discloses the microbial biomass contribution to digestates composition to improve the OM transformation mechanism knowledge.

Impact of environmental factors and tributary contributions on tidal dissolved organic matter dynamics

Riverine dissolved organic matter (DOM) transport was a key step in the carbon biogeochemical cycle while we had limited understanding of its contribution to the estuary DOM dynamics. This study focused on the river downstream-to-tidal estuary DOM variation and the control of environmental factors on it. The contributions of three tributaries with varing urbanization degrees to the tidal DOM dynamics were evaluated. Though more aromatics were introduced to the urban tributary, the A250/A365 values and fluorescent index values indicated the DOM molecular size was uniformly reduced due to the enhanced microbial degradation during transport. The tidal DOM showed less varied spectroscopic indexes than the tributary DOM, but tidal cycles strongly impacted the fluorescent DOM quantified by the fluorescence regional integration (FRI). Salinity range can differentiate the fluorescent DOM variation patterns in river tributaries (e.g., <2.5, positive correlations; >2.5, negative correlations) and tidal cycles (>10, negative correlations). For tidal DOM, the high salinity decreased more humic-related components, resulting in increased proportions of protein-related components in high tides. The dissolved oxygen and nitrogen contents were negatively correlated with salinity, suggesting the microbial contributions and anthropogenic inputs in tributaries increased the tidal DOM quantity. The less urbanized tributaries contributed more to the low-tide DOM compositions/properties while the dynamic contribution of the urban tributary impacted more the tidal DOM dynamics. Our results highlighted the uneven declines of FRI values of different components by freshwater-saltwater mixing in estuaries and suggested the different functioning of urban, agro-urban, and suburban tributaries contributed to tidal DOM dynamics.

Multiple microplastics induced stress on anaerobic granular sludge and an effectively overcoming strategy using hydrochar

Previous studies mostly focused on the responses of anaerobic granular sludge (AGS) to one kind of microplastics during wastewater treatment. However, a wide variety of microplastics has been detected in wastewater. The multiple microplastics induced stress on AGS and the effectively mitigating strategy still remain unavailable. Herein, this work comprehensively excavated the influences of multiple microplastics (i.e., polyethylene terephthalate (PET), polystyrene (PS), polyethylene (PE) and polypropylene (PP)) coexisting in the wastewater on AGS system from macroscopic to microcosmic aspects. Experimental results illustrated that microplastics decreased AGS granule size, increased cell inactivation and caused deteriorative methane recovery from wastewater. As such, this study then put great emphasis on proposing a mitigating strategy using hydrochar and disclosing the role of hydrochar in overcoming the stress induced by coexisting microplastics to AGS system. Physiological characterization and microbial community analysis demonstrated that hydrochar effectively mitigated the reductions in methane production by 50.6% and cell viability by 68.8% of microplastics-bearing AGS and reduced the toxicity of microplastics to microbial community in the AGS. Mechanisms investigation by fluorescence tagging and excitation emission matrix fluorescence spectroscopy with fluorescence regional integration (EEM-FRI) analysis revealed that hydrochar adsorbed/accumulated microplastics and enhanced microplastics-bearing AGS to secrete extracellular polymeric substance (EPS) with more humic acid generation, thus reducing the direct contact between microplastics and AGS. In addition, hydrochar weakened the AGS intracellular oxidative stress induced by microplastics, thereby completely eliminating the inhibition of microplastics on acidification efficiency of AGS, and partially mitigating the suppression on methanation.

The complexation between transition metals and water-soluble organic compounds (WSOC) and its effect on reactive oxygen species (ROS) formation

Both Transition Metals (TMs) and Water–Soluble Organic Compounds (WSOC) in atmospheric particles can make a certain contribution to Reactive Oxygen Species (ROS), but the complexation between them and its subsequent effects on ROS formation are still unclear. Three typical TMs (Fe(II), Cu(II), Mn(II)) and two types of WSOCs (SRHA (Suwannee River Humic Acid) and SRFA (Suwannee River Fulvic Acid)) were chosen to study their complexation process and its effects on generation of ROS. The excitation-emission matrix (EEM) was used to obtain the three-dimensional fluorescence spectra of WSOC during complexation process, and the fluorescence regional integration method (FRI) and parallel factor analysis (PARAFAC) were used to quantitatively characterize the changes of different compositions of WSOC during complexation process. The results showed that the complexation between WSOC and Cu or Mn exhibit synergistic effects on ROS generation, while WSOC and Fe has a negative effect even though ROS produced by Fe is the highest among the three TMs. The hydrophobic fraction of WSOC and ROS generation rate decreased during the complexation process, despite ROS concentration increase. PARAFAC analysis results showed that the aromaticity of WSOC is greatly reduced by complexing with Cu, followed by Fe, and the least with Mn. Cu–WSOC exhibited the most significantly synergistic effect on ROS generation, suggesting aromatic and polar substituents (such as phenol and quinone groups) in WSOC dominated the complexation process. All of three TMs tend to form stable complexes with the polar groups in WSOC. Cu might be more capable of combining with the benzene ring by π-π electron transfer than Fe and Mn. The aromatic groups (π-π electron transfer) in WSOC could significantly enhance ROS generation, but polar groups not.

Quantitative study on the structure-bioavailability relationship of dissolved organic nitrogen in wastewater treatment plant effluent.

This study systematically investigated the relationship between the structure properties and biological characteristics of dissolved organic nitrogen (DON) in the effluents from municipal wastewater treatment plants. Ultrafiltration, Fourier transform infrared (FTIR) spectroscopy, ultraviolet (UV) spectroscopy, and excitation-emission matrix (EEM) fluorescence spectroscopy were used to characterize the structure of organic matters in the effluent samples, and the bioavailability of DON was determined by algal/bacterial-based bioassay. The quantitative analysis of EEM spectra conducted by fluorescence regional integration method showed that the organic portion of all samples was mainly consistent with fulvic acid and protein. Combined with the bioassay results, a positive correlation between the DON bioavailability and the protein content (sum of region I and region II) (r = 0.80, P < 0.02) and soluble microbial byproduct-like materials (region IV) (r = 0.76, P < 0.03) were observed. Nevertheless, the humic substances content represented by the region III and V would negatively affect the DON bioavailability. High humification degree (high HIX value) (r = - 0.77, P < 0.03) was related to low bioavailability. Furthermore, according to UV spectroscopy results, strong aromaticity (high UV254 values) (r = - 0.78, P < 0.03) suggested low DON bioavailability. One protein-like component (C3) and two humic-like components (C1 and C2) were identified via fluorescence excitation-emission matrices-parallel factor analysis (EEM-PARAFAC), and component C3 values were positively correlated to the BAN/DON ratio (r = 0.74, P < 0.03). The ultrafiltration showed that the low molecular weight DON (< 3kDa) accounted for 30-73% of the total DON, and no notable relationship was observed for DON molecular weight and its bioavailability.

A 3D Fluorescence Classification and Component Prediction Method Based on VGG Convolutional Neural Network and PARAFAC Analysis Method

Three-dimensional fluorescence is currently studied by methods such as parallel factor analysis (PARAFAC), fluorescence regional integration (FRI), and principal component analysis (PCA). There are also many studies combining convolutional neural networks at present, but there is no one method recognized as the most effective among the methods combining convolutional neural networks and 3D fluorescence analysis. Based on this, we took some samples from the actual environment for measuring 3D fluorescence data and obtained a batch of public datasets from the internet species. Firstly, we preprocessed the data (including two steps of PARAFAC analysis and CNN dataset generation), and then we proposed a 3D fluorescence classification method and a components fitting method based on VGG16 and VGG11 convolutional neural networks. The VGG16 network is used for the classification of 3D fluorescence data with a training accuracy of 99.6% (as same as the PCA + SVM method (99.6%)). Among the component maps fitting networks, we comprehensively compared the improved LeNet network, the improved AlexNet network, and the improved VGG11 network, and finally selected the improved VGG11 network as the component maps fitting network. In the improved VGG11 network training, we used the MSE loss function and cosine similarity to judge the merit of the model, and the MSE loss of the network training reached 4.6 × 10−4 (characterizing the variability of the training results and the actual results), and we used the cosine similarity as the accuracy criterion, and the cosine similarity of the training results reached 0.99 (comparison of the training results and the actual results). The network performance is excellent. The experiments demonstrate that the convolutional neural network has a great application in 3D fluorescence analysis.

Towards synergistic combination of biochar/ultrasonic persulfate enhancing removal of natural humic acids from water

Removal of natural organic matter (NOMs) from actual water is a major challenge in the context of worldwide pollution of natural water resources. The removal of humic acids in a system combining biochar adsorption and ultrasonic persulfate oxidation was studied in this paper. The effects of biochar addition, persulfate concentration and initial pH were investigated. A high removal rate of humic acids up to 92.5% was achieved for the combined biochar/ultrasonic/persulfate system, versus 84.0% for combined biochar/persulfate, 52.0% for sole biochar, 50.0% for combined biochar/ultrasonic, 10.0% for combined persulfate/ultrasonic, 4.0% for sole ultrasonic and 1.0% for sole persulfate systems. Ultrasonic treatment increased the removal efficiency of humic acids to 90.0% within 60 min. Mechanisms towards synergistic combination of the biochar/ultrasonic/persulfate system were investigated by gel permeation chromatography, electron paramagnetic resonance and quenching experiments together with the characterization of biochar. Hydroxyl radical and the adsorption of biochar were the major contributors to the proposed synergistic adsorption-oxidation removal mechanism, followed by the sulfate radical SO4-·. The results of three-dimensional fluorescence diagram, fluorescence regional integration and TOC analysis indicated that the system presented promising application prospects to remove NOM pollutants from real water.

Removal of methylisothiazolinone biocide from wastewater by VUV/UV advanced oxidation process: Kinetics, mechanisms and toxicity

Methylisothiazolinone (MIT) is frequently used as antimicrobial in household and industrial products, and poses ecological and health risks to aquatic organisms and humans. In this study, vacuum ultraviolet (VUV)/ultraviolet (UV) irradiation was found highly efficient for removal of MIT. The rate constant of MIT degradation (kobs) under VUV/UV irradiation was 3.75 μEinstein−1 cm2, which was around 12.5 times higher than that under UV irradiation. The •OH concentration during the VUV/UV process was 1.0 × 10−12 M. The contributions of UV photolysis and •OH oxidation to MIT degradation under VUV/UV irradiation were 7.3% and 92.7%, respectively. The optimum solution pH (6.0–7.1) gave kobs 33%–39% higher than those at pH 3.9 and 9.3. CO32−/HCO3− inhibited MIT degradation and the kobs decreased by 74% when the concentration of CO32−/HCO3− was increased to 1 mM. The order of MIT removal efficiency under VUV/UV irradiation was ultrapure water > secondary effluent > reverse osmosis (RO) concentrate, because of the light screening and •OH quenching effect of actual wastewater. In RO concentrate, the rate constant of MIT degradation under VUV/UV irradiation was 22% higher than that obtained under UV irradiation. The reduction of TOC, UV254, and total fluorescence regional integration of the RO concentrate during VUV/UV process were 7.2%, 34.9%, and 52.3%, respectively. Twelve main transformation products of MIT were identified after VUV/UV degradation. The main degradation mechanisms of MIT were sulfur atom oxidation and hydroxyl addition. Quantitative structure–activity relationship analysis showed that VUV/UV degradation was an efficient method to remove the toxicity of MIT.

Landfill leachate treatment in-depth by bio-chemical strategy: microbial activation and catalytic ozonation mechanism

The combination of activated sludge process and catalytic ozonation technology was used to treat the landfill leachate as bio-chemical strategy in this study. The technology of activated sludge pretreatment and catalytic ozonation post-treatment coupled with baffled membrane bioreactor (MBR) system was proposed. The COD, ammonia nitrogen and phosphate were removed in anaerobic and aerobic environments. At the same time, catalytic ozonation could significantly remove COD, colority, UV254, ammonia nitrogen, 3D fluorescence peak value, and fluorescence regional integration (FRI) of organic pollutants from landfill leachate. Ultimately, the maximum removal efficiencies of COD, ammonia nitrogen and phosphate were 98.46 ± 0.28%, 99.92 ± 0.01%, and 79.71 ± 1.62%, respectively. The heavy metal contents met the emission standards after treatment with this strategy. The removal of pollutants in landfill leachate could be attributed to the positive effect of microorganism in sludge and catalyst in ozonation: (1) The microorganism found in sludge all played different roles, Proteobacteria and Bacteroidetes accounted for the most, they could degrade organisms and even refractory organic matters. Though the number of Thauera, Acinetobacter, Nitrospira and Nitrosomonas was small, they played an important role on denitrification. (2) During catalytic ozonation, the hydroxyl radical (OH) produced by ozone would combine with oxygen to generate hydrogen peroxide radical (OOH) during the reaction, while unpaired electrons were trapped by surface adsorbed oxygen on the catalysts to produce superoxide radical (O2–). In addition, the active metal components, such as Ce4+/Ce3+ redox pair, Mn2+, Mn3+ and Mn4+ on the catalyst surface were able to transform synergistically, which was able to maintain the catalyst activity and realize the removal of contaminants.

Chromatographic and spectroscopic comparison of dissolved organic matter variation in anaerobic-anoxic-oxic process with tertiary filtration and membrane bioreactor

Anaerobic-anoxic-oxic process with tertiary filtration (A2OWTF) and membrane bioreactor (MBR) was compared from the perspective of dissolved organic matter (DOM) variation in this study. A2OWTF and MBR wastewater treatment plants (WWTPs) samples were compared via conventional wastewater quality indexes, excitation-emission matrix (EEM) spectra, UV–vis spectra and high-performance size exclusion chromatography (HPSEC), which gradually revealed differences between the two processes from phenomena to mechanism. Lower removal of dissolved organic carbon (DOC) by MBR phenomenally revealed its DOM removal deficiency. EEM fluorescence regional integration (FRI), EEM parallel factor analysis (PARAFAC) and UV–vis Gaussian deconvolution qualitatively revealed more abundant humic-like substances (HS) and more complex effluent DOM composition for MBR. HPSEC provided more quantitative characterization. As for effluent after biotreatment, MBR exhibited lower removal rates of HPSEC fractions I (mainly containing protein and polysaccharides), IV (mainly containing low molecular weight organic acids) and fractions II, III (mainly containing HS) than A2OWTF (e.g., removal rates of MBR vs. A2OWTF calculated with UV absorbance at 254 nm (UVA254): 43.6% vs. 66.2%; 5.1% vs. 67.0%; −14.4% vs. 30.8%; −5.7% vs. 36.8% respectively for fractions I, IV, II, III). The massive HS generation in MBR also led to its higher trihalomethane formation potential (THMFP) for final effluent than A2OWTF. In conclusion, MBR should be prudently considered in terms of DOM removal for municipal WWTP upgrading.

Transformations of Diatom-Derived Dissolved Organic Matter by Bacillus pumilus Under Warming and Acidification Conditions.

Heterotrophic bacteria are assumed to play an important role in processing of phytoplankton-derived dissolved organic matter (DOM). Although the algae-derived organic matter is commonly studied, the transformation and processing of DOM by epiphytic bacteria for phytoplankton have rarely been investigated, especially under warming and acidification. In this study, Bacillus pumilus is used to explore the ecologically important marine diatom Skeletonema dohrnii-derived DOM under different conditions (temperature, 27°C and 31°C; pCO2, 400 and 1,000 ppm), utilizing fluorescence excitation-emission matrix (EEM) combined with parallel factor analysis (EEM-PARAFAC). Fluorescence regional integration and the peak selecting method are used to generate B, T, N, A, M, and C peaks in the EEM fluorescence spectroscopy. The main known fluorophores including that protein-like components (peaks B and T), unknown components (peak N), and humic-like component (peaks A, M, and C). Our experimental results showed that under higher temperature and pressure of CO2 (pCO2) conditions, S. dohrnii-derived DOM fluorescence was dominated by a protein-like signal that slower waning throughout the experiment, becoming an increasingly humic-like substance, implying that processing by the epiphytic bacteria (B. pumilus) produced more complex molecules. In addition, spectroscopic indices (e.g., fluorescence index, biological index, freshness index β/α, and humification index) were changed in varying degrees. This study reveals and confirms the direct participation of heterotrophic bacteria in the transformation and generation of algae-derived DOM in the laboratory, underlining the influence of global warming and ocean acidification on this process.