Emission Matrix-parallel Factor Analysis Research Articles

Complexing characteristics between Cu(Ⅱ) ions and dissolved organic matter in combined sewer overflows: Implications for the removal of heavy metals by enhanced coagulation

Enhanced coagulation has been widely used in storm tanks to remove heavy metal ions (HMs) from combined sewer overflows (CSOs), but faces challenges on removing the HMs bound to dissolved organic matter (DOM) with small molecular weight (MW). DOM ubiquitously existing in CSOs generally contains a large distribution range of MW, which can significantly impact the MW distribution of HMs by complexing reaction, thereby adding uncertainties for the removal efficiency of coagulation. Therefore, realizing the potential MW distribution of the HMs bound to CSO-DOM is greatly important for cost-effectively removing HMs from CSOs in the coagulation process. This paper presents a comprehensive approach of ultrafiltration, fluorescence quenching titration, excitation−emission matrix parallel factor analysis, complexation model, and two-dimensional correlation fluorescence spectroscopy for exploring the MW-based complexing characteristics between Cu(II) ions and CSO-DOM components. Results show that: (1) Cu(II) ions that bound to the CSO-DOM were mainly distributed in the MW range of <5 kDa, which makes them very difficult to be removed from CSOs by coagulation technique. (2) Concentration effect and molecular composition exerted great impacts on the MW distribution of the Cu(II) ions bound to CSO-DOM. (3) The humic-like component of terrestrial origin with the MW range of 100 kDa∼0.45 μm possessed high binding stability, capacity, and priority with Cu(II) ions, and they could be used at a high concentration to promote the removal efficiency of coagulation for Cu(Ⅱ) ions of CSOs by competitive complexation and inter-molecular bridging.

Fluorescence Signatures of Dissolved Organic Matter Leached from Microplastics: Polymers and Additives

Despite the numerous studies that have investigated the occurrence and fate of plastic particles in the environment, only a limited effort has been devoted toward exploring the characteristics of dissolved organic matter (DOM) leached from microplastics. In this study, using excitation emission matrix-parallel factor analysis (EEM-PARAFAC), we explored the fluorescence signatures of plastic-derived DOM from commonly used plastic materials, which included two polymers (polyvinyl chloride (PVC) and polystyrene (PS)), two additives (diethylhexyl phthalate (DEHP) and bisphenol A (BPA)), and two commercial plastics. The exposure of the selected plastics to UV light facilitated the leaching of DOM measured in terms of dissolved organic carbon and fluorescence intensity. Four fluorescent components were identified, which included three protein/phenol-like components (C1, C3, and C4) and one humic-like component (C2). The C1 and C4 components were highly correlated with the amounts of DOM leached from DEHP and BPA, respectively, under both leaching conditions, while both C2 and C4 presented good correlations with the DOM leached from polymers under UV light. The C4 may serve as a good fluorescence proxy for DOM leached from BPA or BPA-containing plastics. This study highlights the overlooked issue of plastic-derived DOM leaching into the aquatic environment through optical characterization.

Effect of sulfonamides on the dissolved organic matter fluorescence in biogas slurry during anaerobic fermentation according to the PARAFAC analysis

The biogas slurry produced by anaerobic fermentation process contained a large amount of dissolved organic matter (DOM). In this study, the reason for the effect of sulfanilamide antibiotics (SAs) on DOM components was revealed by analyzing the interaction between microbial community structure and DOM composition in the biogas slurry. Four components of DOM, including tyrosine-like, tryptophan-like or xenobiotic-like, Ultraviolet A (UVA) humic-like and UVA marine humic-like substances, were identified from all the samples through fluorescence excitation emission matrix-parallel factor (EEM-PARAFAC) analysis. The most abundant phyla in biogas slurry were identified to be Firmicutes (60.99 %), Bacteroidetes (19.65 %), Proteobacteria (15.33 %) and Actinobacteria (3.15 %). The contents of soluble microbial byproduct-like substances were related to the growth and metabolism of high abundance of bacterial phyla. Firmicutes could lead to the content change of tyrosine-like substance. The content of the xenobiotic-like substance was negatively correlated with the abundances of Bacteroidetes and Proteobacteria. The addition of high concentration SAs inhibited the growth and reproduction of Firmicutes, resulting in the decrease of the content of tyrosine-like substance. The addition of 100 mg/L sulfaquinoxaline and sulfamethoxydiazine reduced the content of tyrosine-like by 47.5 % and 41.2 %, respectively. The change of tryptophan-like groups was opposite to that of the tyrosine-like. However, the addition of sulfamethoxazole had little effect on the content of all the abovementioned substances.

H2O2-assisted photocatalysis for removal of natural organic matter using nanosheet C3N4-WO3 composite under visible light and the hybrid system with ultrafiltration

In this study, a nano-sheet C3N4-WO3 composite (nsCW21) was applied as a visible-light active photocatalyst to degrade natural organic matter (NOM). The nsCW21 photocatalyst exhibited a higher removal efficiency for NOM than the bare host and other composite counterparts due to the effective separation of the charge carriers in the Z-scheme pathway. The addition of H2O2 resulted in the enhanced photocatalytic performance via the generation of hydroxyl radicals from the catalyst with an NOM removal rate of up to 71% for 5 h. The catalyst showed a considerable stability, which held a good NOM degradation efficiency during five cycle runs. The complex NOM removal behavior was unraveled by using a fluorescence excitation emission matrix-parallel factor analysis and a two-dimensional correlation spectroscopy (2D-COS) combined with Fourier-transform infrared spectroscopy (FT-IR). The large sized and the terrestrial humic-like component exhibited a high adsorption tendency toward the catalyst and was degraded primarily by h+, while a typical humic-like component, which is mainly removed by .OH, displayed a high degradation rate constant (k = 0.159 h−1). The 2D-COS revealed the sequence of the preferable removal among the different NOM functional groups in the nsCW21 system with H2O2 addition, which occurred in the order of open ring reaction > oxygenated functional groups > the transformation into aliphatic compounds/inorganic moieties. Meanwhile, the hybrid system that employed ultrafiltration as a post-treatment demonstrated synergetic effects on the improved effectiveness for NOM removal in the overall system, which was a total of 91%, of the residuals from the precedent photocatalysis as well as alleviating the membrane fouling.

Complexation of humic acid with Fe ions upon persulfate/ferrous oxidation: Further insight from spectral analysis

The complexation of humic acid (HA) with dissolved Fe ions is beneficial to 2,4-dinitrotoluene degradation by PS/Fe2+, while the mechanism on HA binding with Fe ions is still unclear and warrants further exploration. In this study, the binding characteristics of HA with Fe ions and structural variations of HA during the complexation with Fe ions were investigated. Synchronous fluorescence analysis showed that the complexation ability of HA with Fe species at acid (pH = 5.0) and neutral condition (pH = 7.0) is higher than that of alkaline condition (pH = 9.0 and 11.0). Different components in HA including humic-like fraction (C1), fulvic-like fraction (C2), protein-like fraction (C3), and microbial-derived humic-like fraction (C4) were identified by excitation emission matrix-parallel factor analysis (EEM-PARAFAC). The complexation ability of C1, C2, and C4 with Fe species is higher than that of C3, and C1 and C4 primarily contributed to the complexation of HA with Fe species. Moreover, the sequence of HA structural variation during the complexation with Fe species was elucidated by Fourier transform infrared spectroscopy coupled with two-dimensional correlation spectroscopy analysis (2D FTIR COS), and could be concluded as follows: ester→ quinoid rings→ aromatic groups→ aliphatic groups→ phenolic groups.

Pretreatment for water reuse using fluidized bed crystallization

This research investigated the use of fluidized bed crystallization for removing scale forming species and natural organic matter (NOM) from treated municipal wastewater prior to water reclamation. The effect of pH on Ca2+, Mg2+, silica and NOM removal in a fluidized bed crystallization reactor (FBCR) was determined. NOM removal in the FBCR was compared to that for the conventional treatments, ultrafiltration and ferric chloride coagulation/flocculation. Under optimized conditions, fluidized bed crystallization was able to remove more than 99.9 % of Mg2+, 97 % of Ca2+ and 42 % of silica. The FBCR was also able to remove 25 % of NOM, which was intermediate between NOM removal by ferric chloride (56 %) and ultrafiltration (13 %). Size exclusion chromatography-organic carbon detection (SEC−OCD) indicated that the majority of NOM removal occurred via co-precipitation with Mg(OH)2. Excitation emission matrix-parallel factor (EEM-PARAFAC) analysis was used to investigate the types of NOM removed. The FBCR was able to remove all five NOM components (three humic acids, one fulvic acid and one protein-like substance), including 100 % of the autochthonous fulvic acids. Ferric chloride was also able to remove all five NOM components, but only one third of the autochthonous fulvic acids, while ultrafiltration was able to remove only 11 % of the protein-like NOM.

A comparison of dissolved organic matter transformation in low pressure ultraviolet (LPUV) and ultraviolet light-emitting diode (UV-LED)/chlorine processes

This study compared the degradation of dissolved organic matter (DOM) by UV/chlorine advanced oxidation processes (AOPs) with emerging ultraviolet light-emitting diode (UV-LED, 275 nm) and traditional low pressure UV (LPUV, 254 nm) as UV sources. Excitation emission matrix-parallel factor (EEM-PARAFAC) analysis and two-dimensional (2D) correlation gel permeation chromatograph were applied to explore the evolutions of DOM during oxidation processes. The degradation behaviors of DOM indicated by UV absorbance at 254 nm (UV254), dissolved organic carbon (DOC), and fluorophores fitted the pseudo-first-order kinetics well. The removal efficiency of DOM was similar under UV-LED and LPUV irradiation alone. However, UV-LED exhibited much higher degradation rates (increased by 29–160%) than LPUV regardless of the tracking variables during UV/chlorine processes. For three PARAFAC components, humic-like fluorescences were preferentially degraded by UV/chlorine oxidation compared with protein-like fluorescence potentially due to the differences of electronic moieties and molecular weight (MW). The decline in UV254, DOC, and fluorophores increased with increasing chlorine dosage; linear correlations between those indicators were observed during the two AOPs. Moreover, UV-LED/chlorine could achieve greater extents of MW change. Our study demonstrated that UV-LED could be a superior alternative for the future selection of UV source in the UV/chlorine process.

Investigation on the effects of sediment resuspension on the binding of colloidal organic matter to copper using fluorescence techniques

Colloidal organic matter (COM), an important component of dissolved organic matter (DOM), plays a significant role in the transport and cycling process of the heavy metals. In this study, COM was fractionated from DOM using 0.2 μm, 100 kDa, and 2 kDa ultrafiltration membranes and the fluorescence spectra of the COM fractions were obtained. Excitation and emission matrix–parallel factor analysis and two-dimensional fluorescence correlation spectroscopy were applied to investigate the effect of sediment resuspension on the heavy metal binding characteristics of COM fractions with different molecular weights. Compared with the DOM fractions, COM exhibited stronger binding affinities and more binding sites for Cu(II), which was attributed to the significant binding effects of the components of COM. Our results suggested that the protein-like components were mainly responsible for binding heavy metals in the high-molecular-weight fraction (>100 kDa), whereas the humic-like components were responsible in the low-molecular-weight fraction (<100 kDa). Furthermore, sediment resuspension significantly influenced the composition and heavy metal binding characteristics of COM. Following resuspension, the binding affinity of COM decreased significantly, which might be attributed to the binding competition from inorganic colloids. Thus, COM plays an important role in the binding and transportation behavior of heavy metals, which is an important consideration in shallow lake ecosystems.

Targeted removal of organic foulants in landfill leachate in forward osmosis system integrated with biochar/activated carbon treatment

Forward osmosis (FO) has been adopted to treat complex wastewater such as landfill leachate due to its high rejection of organics. In this study, the in-line adsorptive process using biochar (BC) or powdered activated carbon (PAC) was applied to a cross flow FO system to enhance the mitigation of the FO membrane fouling from landfill leachate. The changes in the leachate composition along the treatments were tracked by excitation emission matrix-parallel factor analysis (EEM-PARAFAC) to identify tryptophan-like (C1), fulvic-like (C2), and humic-like (C3) components. After a single operation of FO, the C1 was found to be the main constituent responsible for membrane fouling irrespective of varying operation conditions regarding draw solute concentrations and flow rates. Both sorbents (i.e., BC and PAC) exhibited the preferential removal behavior towards C1 > C2 > C3, which was well supported by their individual adsorption isotherm model parameters. The addition of in-line adsorption treatment to FO resulted in substantial improvements in the filtered volume (>57%) and the flux recovery (>80%) compared to the single FO operation. Without chemical cleaning of membrane, the flux was fully recovered at a dose of 10 g/L BC or 0.3 g/L of PAC. A significant and negative correlation was found between the flux recovery and the C1 of the feed leachate or the corresponding spectral peak intensity (p < 0.05) for the integrated FO system, suggesting the potential of using on-line fluorescence monitoring for the performance of the integrated system in terms of fouling mitigation. This study provided a new insight into the effectiveness of BC or PAC adsorption as the in-line integration with an FO system for the targeted removal of FO membrane foulants in landfill leachate.

Visible light-activated degradation of natural organic matter (NOM) using zinc-bismuth oxides-graphitic carbon nitride (ZBO-CN) photocatalyst: Mechanistic insights from EEM-PARAFAC

In this study, the complex degradation behavior of natural organic matter (NOM) was explored using photocatalytic oxidation systems with a novel catalyst based on a hybrid composite of zinc-bismuth oxides and g-C3N4 (ZBO-CN). The photooxidation system demonstrated the effective removal of NOM under low-intensity visible light irradiation, presenting removal rates of 53–74% and 65–88% on the basis of dissolved organic carbon (DOC) and the UV absorption coefficient (UV254), respectively, at 1.5 g/L of the catalyst. The NOM removal showed an increasing trend with a higher ZBO-CN dose. Comparative experiments with the hole and OH radical scavengers revealed that the direct oxidation occurring on the catalyst's surface might be the governing photocatalytic mechanism. Fluorescence excitation emission matrix-parallel factor analysis (EEM-PARAFAC) revealed the individual removal behavior of the different constituents in bulk NOM. Different tendencies towards preferential adsorption and subsequent oxidative removal were found among dissimilar fluorescent components within a bulk terrestrial NOM, following the order of terrestrial humic-like (C1) > humic-like (C2) > microbial humic-like (C3) components. The result suggests the dominant operation of π-π and/or hydrophobic interactions between the NOM and the catalyst. The discriminative removal behavior was more pronounced in visible light versus UV-activated systems, probably due to the incapability of visible light to excite è - h+ pairs of ZnO and the triplet state of NOM. The high photoactivity and structural stability of ZBO-CN under visible light implies its potential for an effective, low-cost and energy-saving treatment technology to selectively remove large sized humic-like substances from water.

Identification of textile wastewater in water bodies by fluorescence excitation emission matrix-parallel factor analysis and high-performance size exclusion chromatography

Identifying the causes of water body pollution is critical because of the serious water contamination in developing countries. The textile industry is a major contributor to severe water pollution due to its high discharge of wastewater with high concentrations of organic and inorganic pollutants. In this study, fluorescence excitation emission matrix-parallel factor (EEM-PARAFAC) analysis was applied to characterize textile industry wastewater and trace its presence in water bodies. The EEM spectra of textile wastewater samples collected from 12 wastewater treatment plants (WWTPs) revealed two characteristic peaks: Peak T1 (tryptophan-like region) and Peak B (tyrosine-like region). Two protein-like components (C1 and C2) were identified in the textile wastewater by PARAFAC analysis. The components identified from different textile WWTPs were considered identical (similarity >0.95). C1 and C2 were not sensitive to changes in pH, ionic strength, or low humic acid concentration (TOC < 4 mg/L). Therefore, C1 combined with C2 was proposed as a source-specific indicator of textile wastewater, which was further demonstrated by conducting high-performance size exclusion chromatography analysis. These results suggested that EEM-PARAFAC analysis is a reliable means of identifying textile wastewater pollution in water bodies and may also enable the identification of other industrial wastewater.

Effect of UV irradiation on iodinated trihalomethane formation during post-chloramination

Ultraviolet (UV) irradiation has been widely used in drinking water treatment processes, but its influence on the formation of disinfection by-products (DBPs), especially the emerging iodinated trihalomethanes (I-THMs) during post-chloramination remains unclear. This study evaluated the impact of low pressure (LP) UV treatment on the formation of I-THMs during post-chloramination through two pathways. The first pathway is through the transition of DOM structure and composition during UV-chloramination, resulting significant increase of I-THM formation with increasing UV dosage in different dissolved organic matter (DOM)-containing water (49.7%–90.5% at 1160 mJ/cm2). With the application of excitation emission matrix-parallel factor analysis (EEM-PARAFAC), we found that I-THM formation in UV-chloraminated water correlated well with two ratios of three PARAFAC humic-like components (C3/C2 and C1/C2, R2 = 0.958–1.000), suggesting that the ratios of fluorescent components can be used as reliable indicators for I-THM formation. Moreover, the shift in these fluorescent components is crucial for I-THM formation during UV-chloramination. Another pathway for UV irradiation to affect I-THM formation during post-chloramination is through the transformation of iodine species. Large amounts of reactive iodine species (HOI/I2 and I3−) can be generated directly in the mixed iodine system by UV light, leading to the enhancement of iodine utilization factor (IUF) (up to 0.040) after post-chloramination. These results suggest that UV application to DOM-containing water may induce changes in organic precursors and iodine species so as to enhance I-THM formation during post-chloramination.

Unraveling complex removal behavior of landfill leachate upon the treatments of Fenton oxidation and MIEX® via two-dimensional correlation size exclusion chromatography (2D-CoSEC).

The complex removal behavior of stabilized landfill leachate was explored for the treatments of Fenton oxidation (FnO) and magnetic ion exchange (MIEX®) resin using two-dimensional correlation size exclusion chromatography (2D-CoSEC) and fluorescence excitation emission matrix-parallel factor analysis (EEM-PARAFAC). The overall removal rates of the bulk parameters (∼45% for dissolved organic carbon and ∼78% for UV absorbance) were similar between the two treatment options, while distinct differences were found with respect to different molecular sizes and chemical composition. The resin treatment eliminated humic substances (HS) and low molecular weight acid (LMWA) fractions to a greater extent than other fractions (i.e., HS: 62% and LMWA: 99%), while low molecular weight neutral (LMWN) and biopolymers (BP) fractions were more effectively treated by the FnO with the removal rates of 56% and 92%, respectively. The 2D-CoSEC further revealed that the sequential or preferential changes of different size fractions with increasing the resin or H2O2 were opposite between the two treatment options in the order of HS → LMWA → LMWN → BP for MIEX®. Due to their complementary roles in treating leachate, the combined processes removed a wider ranges of different molecular sizes compared to the single operation.

Seasonal Variations of Dissolved Organic Matter in the East China Sea Using EEM-PARAFAC and Implications for Carbon and Nutrient Cycling

Dissolved organic matter (DOM) plays a very important role in the dynamics of different biogeochemical processes in the global marine carbon cycle. Seasonal variations of DOM were investigated using dissolved organic carbon (DOC), absorption spectroscopy, and fluorescence excitation emission matrix–parallel factor analysis (EEM-PARAFAC) in Niushan Island in the East China Sea, off southeast Zhejiang, in winter, spring, and summer 2017. A strong positive correlation between temperature and salinity was observed in winter, whereas negative correlations were obtained in spring and summer. The results suggest that the water in the study area originates from the Changjiang River water coinciding with the direction of winds in winter. On the other hand, the Taiwan Strait water flows northward on the eastern part of the study area in summer and spring. The DOC concentration showed significant seasonal variations and was much lower in summer than in winter, but largely independent of the temperature, degree of absorption and intensity of the fluorescence component. Three tryptophan-like components (C1, C2 and C4) and one humic-like component were identified by the PARAFAC model in winter, while two tryptophan-like components (C1 and C2) and two humic-like components were illustrated in summer. The seasonal variations of DOC concentrations and intensities of the fluorescence components in the study area from winter to summer suggest that the waters in this area were influenced mainly by mixing water of the Changjiang River and the Taiwan Strait. A strongly linear relationship was found between the nutrient and the fluorescence intensities of different components in winter, reflecting the profound impacts of the dynamics of DOM on nutrient cycling.

Spectroscopic study on transformations of dissolved organic matter in coal-to-liquids wastewater under integrated chemical oxidation and biological treatment process

A large amount of wastewater containing various toxic organic contaminants is produced during coal-to-liquids process. In this study, several spectroscopic methods were used to monitor the transformation of organic pollutants during an integrated chemical oxidation and biological process. The results showed that the hydrophobic acid fraction increased after Fenton oxidation, which was likely due to the production of small-molecule organic acids. Soluble microbial products were generated during biological treatment processes, which were degraded after ozonation; meanwhile, the hydrophilic base and acid components increased. Ultraviolet-visible spectroscopic analysis indicated that peaks at the absorption wavelengths of 280 and 254nm, which are associated with aromatic substances, were detected in the raw water. The aromatic substances were gradually removed, becoming undetectable after biological aeration filter (BAF) treatment. Fourier transform infrared spectroscopy analysis revealed that the functional groups of phenols; benzene, toluene, ethylbenzene, and xylene (BTEX); aromatic hydrocarbons; aliphatic acids; aldehydes; and esters were present in raw wastewater. The organic substances were oxidized into small molecules after Fenton treatment. Aromatic hydrocarbons were effectively removed through bioadsorption and biodegradation after BAF process. Biodegradable organic matter was reduced and finally became undetectable after anoxic–oxic treatment in combination with a membrane bioreactor. Four fluorescent components were fractionated and obtained via excitation–emission matrix parallel factor analysis (EEM-PARAFAC). Dissolved organic matter fractionation in conjunction with EEM-PARAFAC was able to monitor more precisely the evolution of characteristic organic contaminants.

Dissolved organic matter release in overlying water and bacterial community shifts in biofilm during the decomposition of Myriophyllum verticillatum

This study investigated the alterations in biomass, nutrients and dissolved organic matter concentration in overlying water and determined the bacterial 16S rRNA gene in biofilms attached to plant residual during the decomposition of Myriophyllum verticillatum. The 55-day decomposition experimental results show that plant decay process can be well described by the exponential model, with the average decomposition rate of 0.037d−1. Total organic carbon, total nitrogen, and organic nitrogen concentrations increased significantly in overlying water during decomposition compared to control within 35d. Results from excitation emission matrix-parallel factor analysis showed humic acid-like and tyrosine acid-like substances might originate from plant degradation processes. Tyrosine acid-like substances had an obvious correlation to organic nitrogen and total nitrogen (p<0.01). Decomposition rates were positively related to pH, total organic carbon, oxidation-reduction potential and dissolved oxygen but negatively related to temperature in overlying water. Microbe densities attached to plant residues increased with decomposition process. The most dominant phylum was Bacteroidetes (>46%) at 7d, Chlorobi (20%–44%) or Proteobacteria (25%–34%) at 21d and Chlorobi (>40%) at 55d. In microbes attached to plant residues, sugar- and polysaccharides-degrading genus including Bacteroides, Blvii28, Fibrobacter, and Treponema dominated at 7d while Chlorobaculum, Rhodobacter, Methanobacterium, Thiobaca, Methanospirillum and Methanosarcina at 21d and 55d. These results gain the insight into the dissolved organic matter release and bacterial community shifts during submerged macrophytes decomposition.

Differences in behaviour of three biopolymer constituents in coagulation with polyaluminium chloride: Implications for the optimisation of a coagulation–membrane filtration process

Coagulation is often applied as a pre-treatment for membrane processes to reduce dissolved organic matter and to prevent membrane fouling. Biopolymers (BPs) have repeatedly been reported as major organic foulants, and coagulation conditions such as pH or dose have been optimised to minimise the remaining BPs. Optimisation however remains problematic because of the complex and heterogenetic nature of BP. In this study, the behaviour of several BP fractions in a coagulation process was investigated by excitation–emission matrix-parallel factor analysis (EEM-PARAFAC) following liquid chromatography (LC)-fractionation. Using a series of jar tests, we found that BP removal depends on the type of source water, reflecting differences in charge neutralisation conditions in three samples of natural water despite nearly identical processes for removing humic substances. This result demonstrates the complexity of optimisation for BP coagulation. Fractionation of EEM-PARAFAC to BP by LC showed that at least three organic component groups (C1, C2 and C3) constitute BP. C1 is tryptophan-like organic matter that is often found in wastewater effluent, C2 is tyrosine-like organic matter that has a phenolic chemical structure, and C3 is a humic-like substance. C1 was removed thoroughly at acidic pH but not at neutral pH, while the removal of C2 was inefficient even with a significant change in pH or dose, indicating similar difficulties in a coagulation process. The difference in components C1 and C2 may partly explain the difference in efficiencies of removal of BP in water from different sources. Our investigation suggests that the optimisation or selection of appropriate pre-treatment processes for membrane systems should be substantially based on the composition of BPs (e.g., C1 and C2 components).

Effects of COD/N ratio on soluble microbial products in effluent from sequencing batch reactors and subsequent membrane fouling

The relative ratios of chemical oxygen demand (COD) to nitrogen (N) in wastewater are known to have profound effects on the characteristics of soluble microbial products (SMP) from activated sludge. In this study, the changes in the SMP characteristics upon different COD/N ratios and the subsequent effects on ultrafiltration (UF) membrane fouling potentials were examined in sequencing batch reactors (SBR) using excitation emission matrix-parallel factor analysis (EEM-PARAFAC) and size exclusion chromatography (SEC). Three unique fluorescent components were identified from the SMP samples in the bioreactors operated at the COD/N ratios of 100/10 (N rich), 100/5 (N medium), and 100/2 (N deficient). The tryptophan-like component (C1) was the most depleted at the N medium condition. Fulvic-like (C2) and humic-like (C3) components were more abundant with N rich wastewater. Greater abundances of large size biopolymer (BP) and low molecular weight neutrals (LMWN) were found under the N deficient and N rich conditions, respectively. SMPs from various COD/N exhibited a greater degree on membrane fouling following the order of 100/2 > 100/10 > 100/5. C1 and C2 had close associations with reversible and irreversible fouling, respectively, while the reversible fouling potential of C3 depended on the COD/N ratios. No significant impact of COD/N ratio was observed on the relative contributions of SMP size fractions to either reversible or irreversible fouling potential. However, the COD/N ratios likely altered the BP foulants' composition with greater contribution of proteinaceous substances to reversible fouling under the N deficient condition than at other N richer conditions. The opposite trend was observed for irreversible fouling. Our results provided further insight into changes in different SMP constitutes and their membrane fouling in response to microbial activities under different COD/N ratios.

Using Two-Dimensional Correlation Size Exclusion Chromatography (2D-CoSEC) and EEM-PARAFAC to Explore the Heterogeneous Adsorption Behavior of Humic Substances on Nanoparticles with Respect to Molecular Sizes

The adsorption behaviors of different constituents within bulk humic substances (HS) on two nanoparticles, TiO2 and ZnO, were examined by using two-dimensional correlation size exclusion chromatography (2D-CoSEC) and excitation emission matrix-parallel factor analysis (EEM-PARAFAC), which separated bulk HS into different size fractions and fluorescent components, respectively. Subtle changes in the size distributions of HS with increasing adsorbents were successfully identified and tracked via the 2D-CoSEC. From adsorption isotherm experiments, three different HS constituent groups with respect to sizes and fluorescence features were identified by the 2D-CoSEC and EEM-PARAFAC, respectively. The chromatographically separated HS size groups presented dissimilar adsorption behaviors in terms of adsorption affinity and isotherm nonlinearity. The sequence orders of adsorption, interpreted from the 2D-CoSEC, was consistent with those of the isotherm model parameters individually calculated for different HS size subfractions, signifying the promising application of 2D-CoSEC in obtaining an insight into the heterogeneous adsorption of HS in terms of molecular sizes. EEM-PARAFAC results also supported the major finding of the 2D-CoSEC as shown by the preferential adsorption of the fluorescent components associated with large molecular sizes.

Cation-induced coagulation of aquatic plant-derived dissolved organic matter: Investigation by EEM-PARAFAC and FT-IR spectroscopy.

Complexation and coagulation of plant-derived dissolved organic matter (DOM) by metal cations are important biogeochemical processes of organic matter in aquatic systems. Thus, coagulation and fractionation of DOM derived from aquatic plants by Ca(II), Al(III), and Fe(III) ions were investigated. Metal ion-induced removal of DOM was determined by analyzing dissolved organic carbon in supernatants after addition of these metal cations individually. After additions of metal ions, both dissolved and coagulated organic fractions were characterized by use of fluorescence excitation emission matrix-parallel factor (EEM-PARAFAC) analysis and Fourier transform infrared (FT-IR) spectroscopy. Addition of Ca(II), Fe(III) or Al(III) resulted in net removal of aquatic plant-derived DOM. Efficiencies of removal of DOM by Fe(III) or Al(III) were greater than that by Ca(II). However, capacities to remove plant-derived DOM by the three metals were less than which had been previously reported for humic materials. Molecular and structural features of plant-derived DOM fractions in associations with metal cations were characterized by changes in fluorescent components and infrared absorption peaks. Both aromatic and carboxylic-like organic matters could be removed by Ca(II), Al(III) or Fe(III) ions. Whereas organic matters containing amides were preferentially removed by Ca(II), and phenolic materials were selectively removed by Fe(III) or Al(III). These observations indicated that plant-derived DOM might have a long-lasting effect on water quality and organisms due to its poor coagulation with metal cations in aquatic ecosystems. Plant-derived DOM is of different character than natural organic matter and it is not advisable to attempt removal through addition of metal salts during treatment of sewage.