Effluent Organic Matter Research Articles

Molecular insights into the degradation of organic matter from secondary swine wastewater effluent: A comparative study of advanced oxidation processes

Advanced oxidation processes (AOPs) are promising for the treatment of secondary swine wastewater effluents, however, the molecular-level understanding of effluent organic matter (EfOM) removal and transformation during AOPs is limited. This study employed molecular-level characterization based on Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and bulk characterizations to investigate these processes in various AOPs, including Cu-Fenton, UV-Cu-Fenton, Fenton, UV-Fenton, and UV/H2O2 treatments. Our findings revealed that the removal rates of dissolved organic carbon and EfOM molecules follow the sequence of UV-Fenton > Fenton > UV-Cu-Fenton > UV/H2O2 > Cu-Fenton, correlating with the rates of H2O2 decomposition during reactions. AOPs with faster H2O2 decomposition, indicative of higher reactive oxygen species generation, predominantly mineralize rather than transform EfOM. Linkage analysis highlighted oxygen addition and deamination as the primary transformation reactions, with variations in the dominance levels of these reactions across different AOPs. Recalcitrant molecule, particularly CHNO and CHO types, including low-molecular-weight carboxyl-rich alicyclic molecules, pose challenges in treatment. To enhance the efficacy of secondary effluent treatment, strategies focusing on the targeted removal of such recalcitrant EfOM should be developed. This study provided new insights into the selection and optimization of AOPs for secondary swine wastewater effluent treatment.

Practical implications of adding powdered activated carbon in advanced wastewater treatment for process and plant design

ABSTRACT The addition of powdered activated carbon (PAC) in advanced wastewater treatment is increasingly recognized for its effectiveness in removing micropollutants from secondary effluents. This study investigates the implications of PAC dosing on treatment performance, particularly in terms of natural and effluent organic matter (OM) removal, turbidity reduction, and sludge characteristics. Results indicate that while PAC incorporation significantly enhances the adsorption of OM, it necessitates higher coagulant dosages to achieve comparable or improved turbidity levels. The study also reveals that lower pH levels facilitate the removal of OM, thereby increasing the availability of adsorption sites on PAC for micropollutants. Moreover, PAC addition results in the formation of larger, denser flocs that settle faster, leading to a reduction in sludge volume by approximately 20%. However, the increased coagulant demand and the subsequent rise in sludge volume highlight the need for the optimized process design to balance treatment efficiency with operational costs. This research provides valuable insights for the design and operation of wastewater treatment plants, emphasizing the importance of tailored coagulant dosing and process adjustments when integrating PAC into existing treatment frameworks.

Fouling of Reverse Osmosis (RO) and Nanofiltration (NF) Membranes by Low Molecular Weight Organic Compounds (LMWOCs), Part 1: Fundamentals and Mechanism.

Reverse osmosis (RO) and nanofiltration (NF) are ubiquitous technologies in modern water treatment, finding applications across various sectors. However, the availability of high-quality water suitable for RO/NF feed is diminishing due to droughts caused by global warming, increasing demand, and water pollution. As concerns grow over the depletion of precious freshwater resources, a global movement is gaining momentum to utilize previously overlooked or challenging water sources, collectively known as "marginal water". Fouling is a serious concern when treating marginal water. In RO/NF, biofouling, organic and colloidal fouling, and scaling are particularly problematic. Of these, organic fouling, along with biofouling, has been considered difficult to manage. The major organic foulants studied are natural organic matter (NOM) for surface water and groundwater and effluent organic matter (EfOM) for municipal wastewater reuse. Polymeric substances such as sodium alginate, humic acid, and proteins have been used as model substances of EfOM. Fouling by low molecular weight organic compounds (LMWOCs) such as surfactants, phenolics, and plasticizers is known, but there have been few comprehensive reports. This review aims to shed light on fouling behavior by LMWOCs and its mechanism. LMWOC foulants reported so far are summarized, and the role of LMWOCs is also outlined for other polymeric membranes, e.g., UF, gas separation membranes, etc. Regarding the mechanism of fouling, it is explained that the fouling is caused by the strong interaction between LMWOC and the membrane, which causes the water permeation to be hindered by LMWOCs adsorbed on the membrane surface (surface fouling) and sorbed inside the membrane pores (internal fouling). Adsorption amounts and flow loss caused by the LMWOC fouling were well correlated with the octanol-water partition coefficient (log P). In part 2, countermeasures to solve this problem and applications using the LMWOCs will be outlined.

Nanoconfined Catalytic Membranes for EfOM Fouling Mitigation: An Intelligent “Pore-Centric” Cleaning Strategy

This study investigated the effectiveness of the nanoconfined catalytic membrane (NCCM), fabricated by nitrogen-doped carbon nanotubes (NCNT) incorporated with graphene oxide membrane (NCNT@GO-M), in mitigating fouling caused by effluent organic matter (EfOM). Compared to conventional catalytic membranes (NRCM) that lack precise spatial design and prepared with only NCNT, NCCM exhibits a unique advantage by preferentially retaining and adsorbing protein-like substances in EfOM during the fouling formation process, forming a cake layer that effectively mitigates pore blockage from irreversible foulants. Furthermore, the ordered nanoconfined structure of NCCM facilitates an intelligent “pore-centric” hierarchical degradation strategy based on the molecular size of EfOM, preferentially removing irreversible foulants caused by fulvic acid-like and low molecular weight protein-like substances. The results demonstrated effective preservation of catalytic sites by the NCCM’s advanced nanoconfined configuration and a 1.6-fold increase in the mass transfer rate of peroxymonosulfate (PMS) compared to NRCM, synergistically promoting hydroxyl radical (•OH) enrichment, resulting in rapid EfOM degradation kinetics. Additionally, chemical cleaning almost completely eliminated irreversible fouling, restoring the NCCM to near its original flux. Overall, this study sheds light on the fouling mitigation mechanisms of NCCM, aiding their tailored design and application in targeted wastewater treatment.

Impacts of polystyrene nanoplastics on microgel formation from effluent organic matter

Municipal effluents discharged from wastewater treatment plants (WWTPs) are considered major contributors of nanoplastics (NPs) and dissolved effluent organic matter (dEfOM) to environments. Due to their small sizes, NPs can travel easily in waterways and evade wastewater treatment processes, and may directly interact with dEfOM, altering their environmental fates. However, although much research has examined the impact of natural organic matter on NPs, the interactions between NPs and dEfOM remain unexplored. This study investigated the influences of NPs on the behavior and capacity of dEfOM aggregation and surface granularity, and identified the possible aggregation mechanism. We also adjusted the salinity of water samples to simulate scenarios based on WWTP–sea continuums. Our data suggest that dEfOM can self-assemble with 55 nm polystyrene NPs to form microgels, particularly under high salinity conditions. NPs accelerates the formation speed and number of dEfOM aggregates, but the sizes of the aggregates remain largely unchanged. The relative particle counts at a salinity of 34 psu increased by 300 % compared to the control group. The potential mechanism behind NPs-microgels aggregation is likely driven by the synergistic effect of the divalent ion crosslinking and hydrophobic interactions between EfOM and NPs. Notably, NPs incorporation into microgels decreases the surface granularity, thereby possibly affecting settling velocity and colonization of aggregates, as well as microbial attachment and community diversity. Overall, our findings demonstrate the potential influence of NPs on dEfOM assembly and surface properties following effluent discharge, and can inspire further relevant studies on microorganism interactions, removal technologies, and the environmental transport of NPs.

Structure and molecular-level transformation for oxidation of effluent organic matters by manganese oxides

As important organic components in water environments, effluent organic matters (EfOMs) from wastewater treatment plants are widely present in Mn-rich environments or engineered treatment systems. The redox interaction between manganese oxides (MnOx) and EfOMs can lead to their structural changes, which are crucial for ensuring the safety of water environments. Herein, the reactivities of MnOx with EfOMs were evaluated, and it was found that MnOx with high specific surface area, active high-valent manganese content and lattice oxygen content (i.e., amorphous MnO2) possessed stronger oxidizing ability towards EfOMs. Accompanying by EfOMs oxidation, Mn(IV) and Mn(III) were reduced into Mn(II), with Mn(III) as the significant active species. Through molecular-level transformation analysis by ultrahigh mass spectrometry (FT-ICR MS), the highly reactive compounds in EfOMs were clearly determined to be that with more aromatic and unsaturated structures, especially lignin-like compounds (the highest content in EfOMs (over 60 %)). EfOMs were oxidized by amorphous MnO2 into products with lower humification index (0.60 vs. 0.46), smaller apparent molecular weight (386.94 Da vs. 368.68 Da), and higher biodegradability (BOD5/COD: 0.12 vs. 0.78). This finding suggested that redox reactions between MnOx and EfOMs might alter their abiotic and biotic behaviors in receiving water environments.

Identifying the fate of dissolved organic matter in wastewater treatment plant effluent-dominated urban river based on fluorescence fingerprinting and flux budget approach

Effluent organic matter from wastewater treatment plants (WWTPs) is an important source of dissolved organic matter (DOM) in urban rivers worldwide and is an important water quality factor. Identifying the fate of DOM in urban river is crucial for water quality management. To address this concern, a fluorescent flux budget approach was conducted to probe the fate of DOM in WWTP effluent-dominated urban river, in combination with field measurement and fluorescence fingerprinting. An urban river receiving two WWTP effluents in Hefei City, China was chosen as the study site, where longitudinal measurements of river hydrology and water quality were performed. The fluorescence fingerprinting revealed the presence of two humic-like components (C1, C4), one fulvic-like component (C2) and one protein-like component (C3) in this investigated river, among which C2 and C4 were indicative of anthropogenic influences, closely associated with treated effluents. For each fluorescent component, the WWTP effluent contributed over 80 % of the total fluorescent dissolved organic matter (FDOM) input in this river. Using the developed FDOM flux budget model, it was found that the C1 and C3 were almost conserved within the waterbody, while the C2 and C4 experienced losses due to biogeochemical reactions. The decay rates of C2 and C4 were estimated to be 0.109–0.174 d−1 and 0.096–0.320 d−1, respectively. Spatial heterogeneity of decay rates for C2 and C4 were associated with the varied chemistries of the lateral input sources including two treated effluents and one tributary flow. Our study highlights that after treated effluent is released into the receiving waterbody, the FDOM would undergo loss from the waters particularly for anthropogenic fulvic-like substance C2 and humic-like substance C4. Additionally, the quantified FDOM decay rate in actual urban water environment provides insights for river water quality management, especially when using DOM as the surrogate indicator of organic pollutants.

Cu2(OH)3NO3/γ-Al2O3 catalyzes Fenton-like oxidation for the advanced treatment of effluent organic matter (EfOM) in fermentation pharmaceutical wastewater: The synergy of Cu2(OH)3NO3 and γ-Al2O3

The secondary effluent of fermentation pharmaceutical wastewater exhibits high chromaticity, elevated salinity, and abundant refractory effluent organic matter (EfOM), presenting significant treatment challenges and environmental threats. Herein, Cu2(OH)3NO3/γ-Al2O3 was fabricated through ultrasound-assisted impregnation and calcination to catalyze the Fenton-like oxidation for degrading organic pollutants in this secondary effluent. Under neutral conditions, with 400.00 mg/L H2O2, 8 g/L catalyst, and at 30 ℃, the EfOM and CODCr removal efficiencies can reach 96.90 % and 51.56 %, respectively. The Cu2(OH)3NO3/γ-Al2O3 catalyst possesses ideal reusability, maintaining CODCr, chromaticity, and EfOM removal efficiencies at 44.44 %-64.59 %, 85.45 %-93.45 %, and 61.00 %-95.00 % over 220 h in a continuous-flow catalytic oxidation system operated at room temperatures (15–25 ℃). Electron paramagnetic resonance results and density functional theory calculations indicate that •OOH may be the predominant reactive oxygen species, facilitated by the easier elongation of the OH bond in H2O2 compared to the OO bond. The adjusted electronic structure endows Cu2(OH)3NO3/γ-Al2O3 composite sites with superior catalytic selectivity for H2O2 activation compared to Cu2(OH)3NO3 single crystal sites, with γ-Al2O3 additionally facilitating H2O2 activation through electron donation. This research highlights the efficacy of Cu2(OH)3NO3/γ-Al2O3 in the advanced treatment of complex industrial wastewater, elucidating its catalytic mechanisms and potential applications.

Removal of Micropollutants in Water Reclamation by Membrane Filtration: Impact of Pretreatments and Adsorption.

Organic micropollutants (OMPs) present in water and wastewater are in the spotlight because of their potentially harmful effects even at low concentrations and the difficulties of their elimination in urban wastewater treatment plants (UWWTPs). This study explores the impact of some membrane filtration processes on the removal of a group of 11 OMPs with an eye on the effects of two pretreatments (i.e., coagulation and adsorption onto powdered activated carbon (PAC)) and the adsorption of OMPs onto the membranes on the overall removal. For this purpose, ultrafiltration (UF) and nanofiltration (NF) experiments were conducted with selected OMPs spiked in ultrapure water and secondary effluents from UWWTPs. It was observed that the adsorption of OMPs onto the membranes was influenced by the characteristics of the membranes, as well as the presence of effluent organic matter (EfOM). Since adsorption was the dominant mechanism for the rejection of OMPs by UF membranes, a study of the adsorption equilibrium of the micropollutants using UF membrane pieces as the adsorbent was conducted. The adsorption isotherms for the most hydrophobic OMPs fitted the Langmuir model. The efficiency of coagulation and powdered activated carbon (PAC) adsorption coupled with UF were also investigated. Both pretreatments alleviated membrane fouling and improved the rejection of organic and inorganic matter. The PAC pretreatment significantly improved the removal of OMPs in the combined PAC/UF process. The best options for achieving reclaimed water with satisfactory physicochemical quality, nearly devoid of OMPs and microorganisms, and suitable for diverse reuse purposes are either the NF treatment or the combination of PAC/UF.

Mn-Fe bimetallic oxide catalytic oxidation combined with ultrafiltration for treating secondary effluent: EfOM molecular transformation and membrane fouling control mechanism

Despite extensive application and research of membrane technology in secondary effluent treatment, fouling induced by effluent organic matter (EfOM) remains a challenge. Herein, a pretreatment strategy involving Mn-Fe bimetallic oxide-activated peroxymonosulfate (MnFeO/PMS) was used before ultrafiltration to decompose EfOM and tackle membrane fouling. Results showed that membrane fouling was effectively alleviated, with reductions in reversible and irreversible fouling resistances of 88.3 % and 58.9 %, respectively. Theoretical analyses illustrated a more pronounced adsorption energy and decomposition tendency of PMS on the MnFeO surface. The generated OH and SO4− played a key role in the degradation of EfOM. The parallel factor analysis along with self-organizing maps revealed the preferential oxidative degradation of humic acids and fulvic acids over tryptophan-like substances, which contributed to the reversible fouling mitigation. In addition, MnFeO/PMS transformed high and middle molecular weight organics into low molecular weight compounds. The primary molecular reactions involved in the degradation of EfOM included oxygen addition, dealkylation and deamination, which changed the properties of EfOM and contributed to the mitigation of membrane fouling. Morphology analysis further indicated that the fouling layer on the membrane surface was inhibited when filtering the MnFeO/PMS-pretreated sample. This study offers revelations for integrating oxidation with ultrafiltration in secondary effluent treatment to alleviate EfOM-induced membrane fouling.

Comparison of chlorine and peroxymonosulfate in enhancing vacuum ultraviolet for treating secondary effluent to mitigate ultrafiltration membrane fouling

Herein, sodium hypochlorite (NaClO) and peroxomonosulfate (PMS) were systematically compared in enhancing vacuum ultraviolet (VUV) oxidation for alleviating ultrafiltration membrane fouling of effluent organic matter. Results indicated that VUV/NaClO pre-treatment exhibited significantly better performance than VUV/PMS, with the irreversible fouling resistance reduced by 64 %. Simultaneously, 96 % of fluorescent substances were removed by VUV/NaClO, and an apparent decrease in surface deposits was observed, with membrane pores exposed and clearly visible. The calculation results through the extended Derjaguin-Landau-Verwey-Overbeek theory indicated that the enhanced hydrophilicity of pollutants reduced the tendency of pollutants to adhere to the membrane surface, leading to the weakening of membrane fouling degree. In the VUV/PMS process, HO• and SO4•– were detected with steady-state concentrations of 8.55 × 10-14 and 1.53 × 10-13 M. By contrast, the VUV/NaClO system generated HO•, Cl•, ClO•, and Cl2•– with steady-state concentrations of 1.15 × 10-13, 8.79 × 10-14, 7.30 × 10-13 and 1.50 × 10-13 M. In conclusion, VUV/NaClO pre-treatment demonstrated high efficiency and significant potential in improving water quality and decreasing membrane fouling in secondary effluent treatment.

Treatment and Desalination of Wastewater Generated After Steel Degreasing and Pickling in the Tunisian Galvanization Industry

A case study of galvanization wastewater treatment was carried out to preserve the environment and to suggest a solution to the Metal Galvanization of Poulina Group Holding MBG-Galva industry located in Tunisia for reducing effluent organic matter, heavy metals, and salt contents. The current industry had two baths of rinsing water after steel degreasing and pickling steps. The chemical oxygen demand (COD) and pH of the first bath were very high compared to the second bath, which exhibits a low pH with high salinity and high heavy metals contents. Coagulation-flocculation and electrodialysis were examined as treatment processes for rinse water obtained after steel degreasing, while precipitation-oxidation and membrane distillation were combined for pickling rinse water treatment. Aluminum sulfate and sodium alginate were used, respectively, as coagulants and flocculents under optimal conditions determined through the Jar test. After the electrodialysis step, the removal rates were found to be 89.6% for conductivity, 93% for COD, 90 to 96% for salt content, and 82% to 99.5% for heavy metals. For the second effluent, the conductivity of wastewater was reduced by 97%, and heavy metals and COD were removed. The lab-scale experiment implementation proved that using the current process has a high impact on obtaining zero liquid reject in the manufactory, and reusing it in the same bath is an opportunity for water preservation. Solid waste characterized by X-rays showed that lead oxide and iron can be recovered from galvanization industry wastewater. Scaling the combined pretreatment and desalination system in a demonstration unit helps the galvanization industry reuse the water in the same industry and prevent environmental pollution.

Catalytic ozonation of reverse osmosis concentrate from coking wastewater reuse by surface oxidation over Mn-Ce/γ-Al2O3: Effluent organic matter transformation and its catalytic mechanism

Degradation of organics in high-salinity wastewater is beneficial to meeting the requirement of zero liquid discharge for coking wastewater treatment. Creating efficient and stable performance catalysts for high-salinity wastewater treatment is vital in catalytic ozonation process. Compared with ozonation alone, Mn and Ce co-doped γ-Al2O3 could remarkably enhance activities of catalytic ozonation for chemical oxygen demand (COD) removal (38.9%) of brine derived from a two-stage reverse osmosis treatment. Experimental and theoretical calculation results indicate that introducing Mn could increase the active points of catalyst surface, and introducing Ce could optimize d-band electronic structures and promote the electron transport capacity, enhancing HO• bound to the catalyst surface ([HO•]ads) generation. [HO•]ads plays key roles for degrading the intermediates and transfer them into low molecular weight organics, and further decrease COD, molecular weights and number of organics in reverse osmosis concentrate. Under the same reaction conditions, the presence of Mn/γ-Al2O3 catalyst can reduce ΔO3/ΔCOD by at least 37.6% compared to ozonation alone. Furthermore, Mn-Ce/γ-Al2O3 catalytic ozonation can reduce the ΔO3/ΔCOD from 2.6 of Mn/γ-Al2O3 catalytic ozonation to 0.9 in the case of achieving similar COD removal. Catalytic ozonation has the potential to treat reverse osmosis concentrate derived from bio-treated coking wastewater reclamation.

Meta-Analysis of Optical Surrogates for the Characterization of Dissolved Organic Matter.

Optical surrogates, derived from absorbance and fluorescence spectra, are widely used to infer dissolved organic matter (DOM) composition (molecular weight, aromaticity) and genesis (autochthonous vs allochthonous). Despite the broad adoption of optical surrogates, several limitations exist, such as context- and sample-specific factors. These limitations create uncertainty about how compositional interpretations based on optical surrogates are generalized across contexts, specifically if there is duplicative or contradictory information in those interpretations. To explore these limitations, we performed a meta-analysis of optical surrogates for DOM from diverse sources, both from natural systems and after water treatment processes (n = 762). Prior to analysis, data were screened using a newly developed, standardized methodology that applies systematic quality control criteria before reporting surrogates. There was substantial overlap in surrogate values from natural and treated samples, suggesting that the gradients governing the surrogate variability can be generated in both contexts. This overlap provides justification for using optical surrogates originally developed in the context of natural systems to describe DOM changes in engineered systems, although the interpretations may change. Absorbance-based surrogates that describe the amount of spectral tailing (e.g., E2:E3 and S275-295) had a high frequency of strong correlations with one another but not to specific absorbance (SUVA254) or absorbance slope ratio (SR). The fluorescence index (FI) and biological index (β/α) were strongly correlated with one another and to the peak emission wavelength but not to the humification index (HIX). Although SUVA254 and FI have both been correlated to DOM aromaticity in prior research, there was a lack of reciprocity between these optical surrogates across this data set. Additionally, there were patterns of deviations in the wastewater subset, suggesting that effluent organic matter may not follow conventional interpretations, urging caution in the use of optical surrogates to track DOM in water reuse applications. Finally, the meta-analysis highlights that three aspects should be captured when optical spectra are used for DOM interpretation: specific absorbance, absorbance tailing, and the extent of red-shifted fluorescence. We recommend that SUVA254, E2:E3, and FI or β/α be prioritized in future DOM studies to capture these aspects, respectively.

Spectroscopic studies of the role of dissolved organic matter in acenaphthene photodegradation in liquid water and ice

The effect of concentration and origin of dissolved organic matter (DOM) on acenaphthene (Ace) photodegradation in liquid water and ice was investigated, and the components in DOM which were involved in Ace photodegradation were identified. The DOM samples included Suwannee River fulvic acid (SRFA), Elliott soil humic acid (ESHA), and an effluent organic matter (EfOM) sample. Due to the production of hydroxyl radical (•OH) and triplet excited-state DOM (3DOM*) which react with Ace, DOM had promotion effects on Ace photodegradation. However, the promotion effects of DOM were prevailed over by their suppressing effect of DOM including screening light effect, intermediates reducing effect and RS quenching effect, and thus, the photodegradation rates of Ace decreased in the presence of the three DOM with concentrations of 0.5–7.5 mg C/L in liquid water and ice. ESHA had higher light absorption and thus had higher screening light effect on Ace photodegradation in liquid water than SRFA and EfOM. At each DOM concentration, ESHA exhibited higher promotion effect on Ace photodegradation than SRFA and EfOM, in liquid water and ice. The binding of Ace with DOM was indicated by decreases in fluorescence intensity of Ace when coexisted with DOM. However, the binding of Ace to DOM played an unimportant role in suppressing Ace photodegradation. The photodegradation behavior of fluorophores in Ace with DOM present in ice was not similar to that in liquid water. C–O, C═O, carboxyl groups O–H and aliphatic C–H functional groups in DOM were involved in the interaction of DOM with Ace. The presence of Ace seemed to have no influence on the photodegradation behavior of functional groups in DOM.

Application of EEM fluorescence spectroscopy for characterizing organic DBP precursors in different water sources: a review

Abstract Disinfection by-products (DBPs), generated from the reaction of disinfectants with DBP precursors, have been found to pose unintentional risks to human health. Considering that the concentration and speciation of DBPs formed during disinfection will be affected by the content and composition of dissolved organic matter (DOM), widespread concern about the characteristics of DBP precursors in water sources have been prompted. Three-dimensional excitation–emission matrix (EEM) can quickly and efficiently determine the properties and composition of DOM in water, and thus is generally used to investigate the origin of DBP precursors in water sources. This study overviews the fluorescent properties of different DBP precursors, summarizes the application of different EEM interpretation methods in DBP precursors and analyses the key factors affecting the correlation between the fluorescent components and DBP precursors (e.g., natural organic matter, algal organic matter, effluent organic matter and organic matter derived from other sources). A series of factors, including composition of fluorophores, bromide concentration, spatio-temporal characteristics and disinfectant types, could impact the correlation between DBP formation potential and fluorescent components. As for future research needs, it is of significance to select suitable fluorescence analysis methods and investigate the combination of EEM with other characterization technologies based on different situations.

Effect of UV-LED Wavelength on Reactive Species Photogeneration from Dissolved Organic Matter

The photogeneration of reactive species from dissolved organic matter (DOM) plays a crucial role in the photochemical and photobiochemical processes in natural aquatic systems. However, the impact of the ultraviolet (UV) wavelength on the photogeneration of reactive species by different sources of DOM remains unclear. In this study, UV light at four wavelengths (365 nm, 310 nm, 280 nm, and 260 nm) provided by UV-LEDs were irradiated onto three types of DOM: humic acid (HA), fulvic acid (FA), and effluent organic matter (EfOM). Three reactive species produced by DOM, including excited triplet-state DOM (3DOM*), singlet oxygen (1O2), and hydroxyl radicals (•OH), were determined. UV365 proved to be the most efficient wavelength for generating 1O2 and •OH, with formation rates of 3.47 × 10−6 M s−1 and 1.67 × 10−8 M s−1, respectively, with the addition of FA and EfOM. The highest steady-state concentrations of all three reactive species were also generated under UV365, reaching 3.00 × 10−13 M (3DOM*) and 1.64 × 10−11 M (1O2) with the FA addition, and 1.44 × 10−10 M (•OH) with the EfOM. Across the different DOM sources, UV365 obtained the maximum quantum yields of reactive species, indicating the stronger effect of UV365 on inducing the photosensitization of DOM compared to the other shorter wavelengths. This study expands our understanding of the photochemistry of DOM in aquatic environments.

Mechanistic Aspects of Photodegradation of Deoxynucleosides Induced by Triplet State of Effluent Organic Matter.

Excited triplet states of wastewater effluent organic matter (3EfOM*) are known as important photo-oxidants in the degradation of extracellular antibiotic resistance genes (eArGs) in sunlit waters. In this work, we further found that 3EfOM* showed highly selective reactivity toward 2'-deoxyguanosine (dG) sites within eArGs in irradiated EfOM solutions at pH 7.0, while it showed no photosensitizing capacity toward 2'-deoxyadenosine, 2'-deoxythymidine, and 2'-deoxycytidine (the basic structures of eArGs). The 3EfOM* contributed to the photooxidation of dG primarily via one-electron transfer mechanism, with second-order reaction rate constants of (1.58-1.74) × 108 M-1 s-1, forming the oxidation intermediates of dG (dG(-H)•). The formed dG(-H)• could play a significant role in hole hopping and damage throughout eArGs. Using the four deoxynucleosides as probes, the upper limit for the reduction potential of 3EfOM* is estimated to be between 1.47 and 1.94 VNHE. Compared to EfOM, the role of the triplet state of terrestrially natural organic matter (3NOM*) in dG photooxidation was minor (∼15%) mainly due to the rapid reverse reactions of dG(-H)• by the antioxidant moieties of NOM. This study advances our understanding of the difference in the photosensitizing capacity and electron donating capacity between NOM and EfOM and the photodegradation mechanism of eArGs induced by 3EfOM*.

Insights into coagulation, softening and ozonation pre-treatments for reverse osmosis membrane fouling control in reclamation of textile secondary effluent

Pre-treatment was an effective strategy to mitigate membrane fouling, while controversial fouling control performance and mechanism still restricted its application. Herein, coagulation, softening and ozonation pre-treatments were applied to mitigate reverse osmosis (RO) fouling in reclamation of textile secondary effluent. The results showed coagulation pre-treatment negligibly alleviated membrane fouling by dosing FeCl3 coagulant due to the low coagulation efficiency and dissolved organic carbon (DOC) removal (only 11 %) toward effluent organic matter (EfOM) with low molecular weight (2300–6145 Da). Unexpectedly, pre-ozonation caused more severe RO fouling with the increasing ozone doses owing to the enhanced bridging action of divalent cations between membrane and ozonated EfOM; however, the opposite phenomenon was observed when divalent cations were removed by softening due to the preferential removal of biopolymers, the decrease in molecular weight and hydrophobicity of EfOM. Especially, at ozone dose of 1.0 mg O3/mg DOC, flux loss and irreversible fouling resistance enhanced by 8.60 % and 25.4 %, but markedly reduced by 24.0 % and 41.2 % in the absence of divalent cations, respectively. Extended DLVO (XDLVO) theory further unveiled the different roles of pre-treatments in RO fouling control was mainly due to the variation of adhesion interfaces between RO membrane and foulants, especially for the Lewis acid-base (AB) interaction energy. We proposed that softening + ozonation pre-treatment was effective to control RO fouling. More importantly, the reclaimed water satisfy the national standard of China (GB/T 19923–2005) for industrial water reuse after softening + ozonation + RO membrane treatment, which is promising to reclaim textile wastewater.

Variation in organic matter characteristics and mitigation of ultrafiltration membrane fouling by chlorine and UV/chlorine pre-oxidation in secondary effluent treatment

Membrane fouling caused by effluent organic matter (EfOM) limits its further application in wastewater reuse. In this study, the effect of UV/chlorine pretreatment on membrane fouling was investigated in treating secondary effluent by ultrafiltration (UF) process. The relation between organic matter changes and fouling alleviation after UV/chlorine pretreatment was also studied according to the molecular weight (MW) changes in various resin fractions derived from EfOM. Results showed that UV/chlorine pretreatment effectively alleviated irreversible fouling, whereas chlorine pre-oxidation primarily mitigated reversible fouling. UV/chlorine pre-oxidation reduced 18% of reversible membrane fouling and 38% of irreversible membrane fouling at a chlorine dosage of 8 mg/L, indicating better performance in membrane fouling mitigation than chlorine pre-oxidation. UV/chlorine pre-oxidation also decreased dissolved organic matter in the UF permeate. The hydrophobic acidic (HPO-A) fraction caused dominant membrane fouling, while the hydrophilic (HPI) fraction contained most of high MW organic matter. Pre-oxidation changed the polarity of organic matter in the HPO-A fraction and decomposed the organics of high MW in the HPI fraction, which alleviated membrane fouling. These results showed that UV/chlorine pre-oxidation was a prospective pretreatment process prior to UF in wastewater reclamation.