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In electrokinetic remediation (EKR), the sedimentary dissolved organic matter (DOM) could impede remediation by scavenging reactive species and generating unintended byproducts. Yet its transformation and mechanisms remained largely unknown. This study conducted molecular-level characterization of the water-extractable DOM (WEOM) in EKR using negative-ion electrospray ionization coupled to 21 tesla Fourier transform ion cyclotron resonance mass spectrometry (21 T FT-ICR MS). The results suggested that ∼55 % of the ∼7,000 WEOM compounds identified were reactive, and EKR lowered their diversity, molecular weight distribution, and double-bond equivalent (DBE) through a combination of electrochemical and microbial redox reactions. Heteroatom-containing WEOM (CHON and CHOS) were abundant (∼ 35% of the total WEOM), with CHOS generally being more reactive than CHON. Low electric potential (1 V/cm) promoted the growth of dealkylation and desulfurization bacteria, and led to anodic CO 2 mineralization, anodic cleavage of -SO and -SO 3 , and cathodic cleavage of -SH 2 ; high electric potential (2 V/cm) only enriched desulfurization bacteria, and differently, led to anodic oxygenation and cathodic hydrogenation of unsaturated and phenolic compounds, in addition to cathodic cleavage of -SH 2 . The long-term impact of these changes on soil quality and nitrogen-sulfur-carbon flux may be need to studied to identify unknown risks and new applications of EKR., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Glyphosate, the most widely used herbicide globally, is accumulating in the environment and poses significant potential eco- and bio-toxicity risks. While natural attenuation of glyphosate has been reported, the efficacy varies considerably and the dominant metabolite, aminomethylphosphonic acid (AMPA), is potentially more persistent and toxic. This study investigated the bioelectrochemical system (BES) for glyphosate degradation under anaerobic, reductive conditions. Atomistic simulations using density functional theory (DFT) predicted increased thermodynamic favorability for the non-dominant C-P lyase degradation pathway under external charge, which suppressed AMPA production. Experimental results confirmed that cathodic poised potential (-0.4 V vs. Ag/AgCl) enhanced glyphosate degradation (75 % in BES vs. ∼40 % in the control conditions after 37 days), and lowered the AMPA yield (0.52 mol AMPA yield per mol glyphosate removed in BES vs. 0.77-0.86 mol mol -1 in the control conditions). Geobacter lovleyi was likely the active species driving the C-P lyase pathway, as evidenced by the increase of its relative abundance, the upregulation of its extracellular electron transfer genes (most notably mtr) and the up-regulation of its phnJ and hcp genes (encoding C-P layse and hydroxylamine reductase respectively)., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Membrane fouling and high-strength membrane concentrate production are two limitations of membrane distillation (MD) for landfill leachate treatment. In this study, activated carbon- and biochar-based adsorption processes were integrated into a conventional MD system to overcome these limitations. The organic matter fractionations of the leachate were thoroughly investigated during the treatment. Membrane-reversible and irreversible foulants differed remarkably from the inlet leachate in the non-assisted MD system. Specifically, reversible foulants were characterized by a high abundance of humic-like fluorescent components, high-molecular-weight humic-size constituents, peptides, and unsaturated compounds. In contrast, irreversible foulants were enriched with fulvic-like fluorescent components, low-molecular-weight neutrals, unsaturated compounds, and polyphenols. The adsorption-based pre-treatment effectively removed foulant precursors from landfill leachate, with a relatively higher (20%) adsorption performance for specific biochar used in this study than for activated carbon. Compared with the non-assisted MD system, the biochar-assisted MD system showed improved performance, achieving 40% overall membrane flux recovery, 42% higher filtration fluxes, and 53% lower concentrate production. In addition, a 15% higher removal of irreversible foulants was observed as compared to the reversible foulants, which can potentially increase the membrane lifespan. This study demonstrates the effectiveness of an adsorption-assisted MD system supported by increased filtration, membrane fouling alleviation, and low-strength leachate concentrate generation., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

A composite manganese-based catalytic ceramic membrane (Mn-CCM) was developed by a solid-state sintering method, and its effectiveness toward activation of peroxymonosulfate (PMS) for the degradation of 11 pharmaceutical and personal care products (PPCPs) mixture was tested. The optimized Mn-CCMs/PMS system showed remarkable degradation efficiencies for PPCPs mixture with total removal >90% in ultrapure water, river water and natural organic matter (NOM) solution. The Mn-CCMs/PMS system showed the contribution of different phenomena in PPCPs removal in the order of catalytic oxidation (54.7%, Mn-CCMs/PMS) > noncatalytic oxidation (42.3%, PMS oxidation) > adsorption (3.0%, by Mn-CCMs). The singlet oxygen ( 1 O 2 ) was the dominant reactive oxygen specie for the degradation of PPCPs in all water matrices proved by the quenching experiments and electro-paramagnetic resonance (EPR) spectroscopy. The extraordinary stability of Mn-CCMs for the activation of PMS has been noted in terms of repeatability experiments for PPCPs degradation with fewer leaching of Mn (1.9 to 3.6 µg/L). Mineralization was achieved in the range of 28-65% for different water matrices. The toxicity of the PPCPs mixture was reduced by 85.9%. The Mn-CCMs/PMS system showed a reduction (25-100%) in precursors of different carbon- and nitrogen-based disinfection by-products. This study found the Mn-CCMs/PMS system as a feasible purification unit for removing trace concentrations of PPCPs (ng/L) in real drinking water matrices., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

This research evaluated the performance of reactive electrochemical ceramic membrane (REM) in treating secondary effluent and investigated the fate of dissolved organic matter (DOM) at the molecular level. The role of adsorption, electrosorption, and oxidation in DOM removal was comprehensively elucidated based on fluorescence spectroscopy and high-resolution mass spectrometry (FT-ICR MS). Among the fluorescence components (C1-C3) in secondary effluent, microbial humic-like C2 showed fewer adsorption on the REM surface without applying an electrical potential. The electrosorption helped an enhanced uptake of all DOM components and transformed them onto the electrode surface. The fluorescence components and all three fractions (hydrophilic, transphilic, and hydrophobic) were rapidly degraded, and finished water with stable DOM was obtained. The leading degradation phenomena were the change of the unsaturated compounds to the aliphatic and transformation of large-sized molecules to medium and small-sized ones. Above 70% of the compounds in the secondary effluent acted as precursors, which were mineralized/degraded and transformed products were found on the REM surface and in the finished water. The compounds containing sulfur (CHOS) were easily and preferably degraded/mineralized, followed by the compounds containing nitrogen (CHON) and CHO. The oxidation of DOM led to the extensive formation of organo-chlorinated compounds, which contributed above 80% in products. Overall, the combination of fluorescence spectroscopy and FT-ICR MS provided unique behavior of DOM in the secondary effluent toward electro-oxidation in the REM system. These findings could help explore the potential of REM for different water matrices to project the possible composition of DOM in the finished water., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

N-nitrosamines have been identified as emerging contaminants with tremendous carcinogenic potential for human beings. This study examined the seasonal changes in the occurrence of N-nitrosamines and N-nitrosodimethylamine formation potential (NDMA-FP) in drinking water resources and potable water from 10 drinking water treatment plants in a southern city of China. The changes in N-nitrosamines are well correlated with dissolved organic matter (DOM), particularly fluorophores, which were measured and compared between traditional fluorescence indices and excitation-emission matrix coupled with parallel factor analysis (EEM-PARAFAC). Four of N-nitrosamine species including N-nitrosodimethylamine (NDMA), N-Nitrosodibutylamine (NDBA), N-Nitrosopyrrolidine (NPYR), and N-Nitrosodiphenylamine (NDPhA) are found to be abundant compounds with an average of 29.5% (26.7%), 20.0% (25.2%), 18.9% (16.0%), and 9.0% (9.9%) in the source (and treated) water, respectively. The sum of N-nitrosamines concentration is recorded to be low in the wet season (July-September), whereas the dry season (October-December) provided opposite impacts. EEM-PARAFAC modeling indicated the predominance of humic-like component (C1) in the wet season while in the dry season the water was dominant in protein-like component (C2). All the N-nitrosamines excluding NDPhA and N-Nitrosomorpholine (NMOR) showed a strong association with protein-like component (C2). In contrast, humic-like C1, which was directly influenced by rainfall, was found to be a suitable proxy for NMOR and NDPhA. The results of this study are valuable to understand the correlation between different N-nitrosamines and DOM through adopting fluorescence signatures., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

This study aims to extend and demonstrate the application of fluorescence spectroscopy for monitoring the water quality of three differently operated full-scale drinking water treatment plants located in the Shenzhen city (China). A ratio of fluorescent dissolved organic matter (FDOM), which describes relative changes in humic-like to protein-like fluorescence, was used to explain mechanisms behind the physicochemical processes. The fluorescence components obtained through individual and combined parallel factor analysis (PARAFAC) modeling revealed the presence of humic-like (C1) and protein-like (C2) structures in the DOM. The C1/C2 ratio provided a direct relationship between the seasonal variations and DOM composition. Wet season generated DOM enriched with humic-like fluorescence, while dry season caused a higher release of protein-like fluorescence. The fluorescence ratio presented unique patterns of DOM in treatment trains. The chemical pretreatment and disinfection unit processes showed a higher tendency to remove the humic-like fluorescence. However, the C1/C2 ratio increased during physical treatment processes such as coagulation-precipitation and sand filtration, indicating preferential removal of protein-like fluorescence. The DOM composition in influent directly (R 2  = 0.77) influenced the relative intensities of fluorescence components in the treated water. Compared to the dry season, the wet season caused significant changes in DOM composition and produced treated water enriched with humic-like fluorescence. This fluorescence ratio offers an approach to explore the role of different treatment units and determine the factors affecting the composition of DOM in the surface water and drinking water treatment plants., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Extracellular polymeric substances (EPS) from activated sludge comprise many organic constituents with polysaccharides and proteins as the main components of two different functionalities. Despite a number of previous EPS studies, a fundamental question remained unanswered, namely, whether the different EPS components would have the same turnover cycle (i.e., formation/dissolution) in biological wastewater treatment systems. In this study, we employed a stable isotope labeling approach based on isotope-enriched substrates (i.e., 13 C-glucose and 15 NH 4 Cl) to examine the potential discrepancies in the turnover cycles among different major EPS constituents. Our results, based on substrate consumption in a batch bioreactor, evidenced the existence of differences in carbon and nitrogen cycles within bulk EPS with an earlier replenishment of organic carbon relative to organic nitrogen. The changes in the 13C nuclear magnetic resonance (13C NMR) spectra of EPS with operation clarified the relative differences in the turnover periods among several identified EPS structures with different chemical functionalities. Two-dimensional correlation spectroscopy (2D-COS) on the 13C NMR spectra further showed that the substrate-assimilated carbon functional groups appear to preferably formed within bulk EPS in the order of O-alkyl carbons > amides > α amino acids > aliphatic carbons. This study provides a novel insight into the dissimilar formation rates of different EPS structures after substrate assimilation. This isotope labeling approach can be further applied to determine the mass balance among the substrate, biomass, and bound/soluble EPS within activated sludge systems., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

In this study, the spectroscopic indices of soluble microbial products (SMP) were explored using absorption and fluorescence spectroscopy to identify different distinctive biomass growth phases (i.e., exponential phase, pseudo-endogenous phase, and endogenous phase) and to describe the microbial activity of activated sludge in a batch type bioreactor under prolonged starvation. The optical descriptors, including UV absorption at 254 nm (UVA254), spectral slope, absorbance slope index (ASI), biological index (BIX), humification index (HIX), and the ratio of tryptophan-like to humic-like components (C1/C2), were examined to describe the dynamic changes in SMP. These indices were mostly associated with dissolved organic carbon (DOC) of SMPs and specific oxygen uptake rate (SOUR). Among those, ASI was the most strongly correlated with the SOUR data for the pseudo-endogenous and the endogenous periods. Although the three microbial phases were well discriminated using the spectral slope, BIX, and the C1/C2 ratio, the C1/C2 ratio can be suggested as the most preferable indicator as it can also trace the changes of the relative abundance of proteins to humic-like substances in SMPs. The suggested spectroscopic descriptors were reasonably explained by the general trends of decreased large-sized biopolymer fractions (e.g., proteins) and increased humic substrates (HS) with starvation time, which were detected by size exclusion chromatography. This study provides a novel insight into the strong potential of using optical descriptors to easily probe microbial status in biological treatment systems., (Copyright © 2017 Elsevier Ltd. All rights reserved.)