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Interactions between metal cations, notably Cu(II), and humic substances (HS) affect their mobility, bioavailability, and toxicity. This necessitates a molecular-level determination of the nature of HS functional groups binding Cu(II) (Cu-HS) and effects of pH on them. This study investigates the pH effects on the spectroscopic and structural properties of the complexes of Cu(II) with HS and representative model compounds using differential absorbance spectroscopy (DAS), examination of the properties of the d-d transition band characteristic for Cu(II) ions, and quantum chemical (QC) calculations. DAS of Cu-HS show distinct bands at 240, 275, 310 and 400 nm, while absorbance features located from 600 to 800 nm correspond to the d-d transitions in Cu(II). Similar features appear in copper complexes with the model compounds of salicylic acid (Cu-Sal) and poly(4-styrenesulfonic acid-co-maleic acid) (Cu-PSM). Increasing pH resulted in consistent changes of the DAS and the d-d band of Cu(II) which exhibited a hypsochromic shift and increased intensity. Deconvolution of the d-d bands into discrete Gaussian bands was indicative of transitions between dominant species at increasing pH. Cu-Sal and Cu-PSM structures that were modeled successfully by QC calculations. These results demonstrate the sensitivity of DAS spectra and d-d band to the modes of Cu(II) binding by HS and open a possibility of further elucidation of the functional groups engaged in the binding of heavy metals by HS., 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.)

The presence in seawater of low-molecular-weight polyethylene (PE) and polydimethylsiloxane (PDMS), synthetic polymers with high chemical resistance, has been demonstrated in this study for the first time by developing a novel methodology for their recovery and quantification from surface seawater. These synthetic polymer debris (SPD) with very low molecular weights and sizes in the nano- and micro-metre range have escaped conventional analytical methods. SPD have been easily recovered from water samples (2 L) through filtration with a nitrocellulose membrane filter with a pore size of 0.45 μm. Dissolving the filter in acetone allowed the isolation of the particulates by centrifugation followed by drying. The isolated SPD were analysed by 1 H nuclear magnetic resonance spectroscopy ( 1 H NMR), identifying PE and PDMS. These polymers are thus persisting on seawater because of their low density and the ponderal concentrations were quantified in mg/m 3 . This method was used in an actual case study in which 120 surface seawater samples were collected during two sampling campaigns in the Mediterranean Sea (from the Gulf of Salerno to the Gulf of Policastro in South Italy). The developed analytical protocol allowed achieving unprecedented simplicity, rapidity and sensitivity. The 1 H and 13 C NMR structural analysis of the PE debris indicates the presence of oxidised polymer chains with very low molecular weights. Additionally, the origin of those low molecular weight polymers was investigated by analysing influents and effluents from a wastewater treatment plant (WWTP) in Salerno as a hot spot for the release of SPD: the analysis indicates the presence of low molecular weight polymers compatible with wax-PE, widely used for coating applications, food industry, cosmetics and detergents. Moreover, the origin of PDMS debris found in surface seawater can be ascribed to silicone-based antifoamers and emulsifiers., 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.)

The next generation of the self-forming dynamic membrane, referred to in this study as the "Living Membrane (LM)", is a new patented technology based on an encapsulated biological layer that self-forms on a designed coarse-pore size support material during wastewater treatment and acts as a natural membrane filter. Integrating electrochemical processes with wastewater treatment using the LM approach has also been recently studied (the reactor is referred to as the Electro-Living Membrane Bioreactor or e-LMBR). This study investigated the effects of varying current densities, i.e., 0.3, 0.5, and 0.9 mA/cm 2 , on the performance of an e-LMBR. The results were also compared with those of the Living Membrane Bioreactor or LMBR (without applied current density). Higher pollutant removals were observed in the presence of the electric field. However, the effect of varying applied current densities on the COD (98-99 %), NH 3 -N (97-99 %), and PO 4 3- P (100 %) removals was not statistically significant. The more prominent differences (p < 0.05) were observed in the decrease of NO 3 - -N concentrations from mixed liquor to effluent, with increasing current density resulting in lower mean NO 3 - -N effluent concentrations (0.3 mA/cm 2 : 6.13 mg/L; 0.5 mA/cm 2 : 4.38 mg/L; 0.9 mA/cm 2 : 3.70 mg/L). The reduction of NO 3 - -N concentrations as wastewater permeated through the LM layer also confirmed its role in removing nitrogen-containing compounds. Higher current densities resulted in lower concentrations of fouling substances, particularly those of microbial extracellular polymeric substances (EPS) and transparent exopolymer particles (TEPs). The average values of the temporal variation of transmembrane pressure (d(TMP)/d(t)) in the e-LMBR were extremely low, in the range of 0.013-0.041 kPa/day, throughout the operation period. The highest (d(TMP)/d(t)) was observed for the highest current density. However, the TMP values remained below 2 kPa in all the e-LMBR runs even after the initial LM formation stage., 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 The Authors. Published by Elsevier B.V. All rights reserved.)

Differential absorption spectroscopy (DAS) quantifies changes in the UV-Visible absorbance of dissolved organic matter (DOM) caused by reactions of its chromophores. As a result of its precision and sensitvity, DAS serves as a powerful tool for characterizing the formation of disinfection by-products (DBPs) in generated in DOM chlorination reactions. However, the nonlinear relationship between the intensity of DAS and DBP concentrations as well as the need to develop site-specific fitting parameters limit its practical applications. This study investigated the physico-chemical nature of DAS of chlorinated DOM through experimental measurements and theoretical calculations. Results of this study provide molecular-level evidence that electrophilic substitution reactions involving DOM reactive sites result in the emergence of DAS feaures ascribed to the "fast" chromophores. The ring opening in the cyclic enones-like structures which can be present either in the original DOM or are generated as intermediates in its chlorination, leads to the emergence of DAS features associated with the "slow" chromophores and high yields of DBPs. The kinetic study of chlorination of real waters reveals a strong linear relationship (R 2 > 0.91) between ln([DBP]) and the long-wavelength (λ > 325 nm) parameter of the DAS, notably (ln(-DA 350 )). This relationship varies among different water sources due to the differences in the heterogeneity of Band A 3 whose maximum is near 350 nm. Band A 3 is one of the Gaussian bands that comprise the overall UV-Visible spectrum of DOM. A new function (f(-DA 350 )) is proposed in this study to quantify DBP formation. This function, which is determined by the Band A 3 's area, allows establishing a universal linear relationship between f(-DA 350 ) and ln([THMs]), as well as f(-DA 350 ) and ln([HAAs]), across various water sources. The findings of this study will stimulate further development of spectroscopy-based DBP monitoring technology for monitoring and optimization of water disinfection processes., 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.)

Greenhouse gases (GHGs) emissions due to increasing energy demand have raised the need to identify effective solutions to produce clean and renewable energy. Biotechnologies are an effective platform to attain green transition objectives, especially when synergically integrated to promote health and environmental protection. In this context, microalgae-based biotechnologies are considered among the most effective tools for treating gaseous effluents and simultaneously capturing carbon sources for further biomass valorisation. The production of biodiesel is regarded as a promising avenue for harnessing value from residual algal biomass. Nonetheless, the existing techniques for extracting lipids still face certain limitations, primarily centred around the cost-effectiveness of the process.This study is dedicated to developing and optimising an innovative and cost-efficient technique for extracting lipids from algal biomass produced during gaseous emissions treatment based on algal-bacterial biotechnology. This integrated treatment technology combines a bio-scrubber for degrading gaseous contaminants and a photobioreactor for capturing the produced CO 2 within valuable algal biomass. The cultivated biomass is then processed with the process newly designed to extract lipids simultaneously transesterificated in fatty acid methyl esters (FAME) via In Situ Transesterification (IST) with a Kumagawa-type extractor. The results of this study demonstrated the potential application of the optimised method to overcome the gap to green transition. Energy production was obtained from residuals produced during the necessary treatment of gaseous emissions. Using hexane-methanol (v/v = 19:1) mixture in the presence KOH in Kumagawa extractor lipids were extracted with extraction yield higher than 12% and converted in fatty acid methyl esters. The process showed the enhanced extraction of lipids converted in bio-sourced fuels with circular economy approach, broadening the applicability of biotechnologies as sustainable tools for energy source diversification., 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 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Effluent organic matter (EfOM) discharged from wastewater treatment plants (WWTPs) carry substantial risks to river ecosystems. The fate and role of EfOM in the receiving water is affected by its exposure to sunlight and microbial processes, but the extent of these processes remains unclear. In this study, three-phase sequence of irradiation and microbial incubation with EfOM were conducted to compare the behavior of EfOM with that of natural organic matter in receiving rivers (RNOM). The dissolved organic carbon (DOC) in EfOM was degraded by 23% after three sequential phases, while that in RNOM was degraded by 19%. In the first phase, the irradiation of EfOM stimulated microbial respiration and growth by producing easily metabolizable less aromatic lignin-type molecules, leading to a 21% increase in biodegradation. Conversely, the irradiation of RNOM removed biodegradable lignin-type molecules, causing a 50% decreased in biodegradation. The second and third irradiation phases of EfOM and RNOM produced biodegradable lignin-type molecules, making their molecular compositions increasingly similar. The acute toxicity of EfOM decreased by 55%, and differences in microbial species composition between EfOM and RNOM waters decreased by 82% after the three-phase sequence. These findings can improve understanding of the fate of EfOM discharged into receiving rivers., 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 B.V. All rights reserved.)

Hydrogen sulphide (H 2 S) removal from biogas is of high relevance as it damages combustion engines used for heat and power generation and causes adverse public health and environmental effects. Biological processes have been reported as a cost-effective and promising approach to desulfurize biogas. This review presents a detailed description of the biochemical foundations of the metabolic apparatus of H 2 S oxidizing bacteria, namely chemolithoautotrophs and anoxygenic photoautotrophs. The review focuses on the current and future applications of biological processes for biogas desulfurization and provides insights into their mechanism and main factors influencing their performance. The advantages, drawbacks, limitations, and technical improvements of the biotechnological applications currently based on chemolithoautotrophic organisms are covered extensively. Recent advances, sustainability and economical aspects of biological biogas desulfurization are also discussed. Anoxygenic photoautotrophic-bacteria-based photobioreactors were herein identified as useful tools to improve the sustainability and safety of biological biogas desulfurization. The review addresses gaps in the existing studies concerning the selection of the most suitable desulfurization techniques, their benefits and consequences. The research is useful for all stakeholders involved in the management and optimization of biogas and its findings are directly applicable in the development of new sustainable technologies for biogas upgrading processes on waste 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 © 2023 Elsevier B.V. All rights reserved.)

This study delves into the microbial community complexity and its role in self-forming dynamic membrane (SFDM) systems, designed to remove nutrients and pollutants from wastewater, by means of the analysis of Next-Generation Sequencing (NGS) data. In these systems, microorganisms are naturally incorporated into the SFDM layer, which acts as a biological and physical filter. The microorganisms present in an innovative and highly efficient aerobic, electrochemically enhanced, encapsulated SFDM bioreactor were studied to elucidate the nature of the dominant microbial communities present in sludge and in encapsulated SFDM, patented as living membrane® (LM) of the experimental setup. The results were compared to those obtained from the microbial communities found in similar experimental reactors without an applied electric field. The data gathered from the NGS microbiome profiling showed that the microbial consortia found in the experimental systems are comprised of archaeal, bacterial, and fungal communities. However, the distribution of the microbial communities found in e-LMBR and LMBR had significant differences. The results showed that the presence of an intermittently applied electric field in e-LMBR promotes the growth of some types of microorganisms (mainly electroactive microorganisms) responsible for the highly efficient treatment of the wastewater and for the mitigation of the membrane fouling found for those bioreactors., 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 B.V. All rights reserved.)

Electrochemical oxidation (EO) is an attractive option for treatment of dissolved organic matter (DOM) in landfill leachate but concerns remain over the energy efficiency and formation of oxidation byproducts ClO 3 - and ClO 4 - . In this study, EO treatment of landfill leachates was carried out using representative active and nonactive anode materials, cell configurations and current densities. Size exclusion chromatograms coupled with 2D synchronous and asynchronous correlation analysis showed that the sensitivity of DOM fractions to EO degradation was dependent on the anode material. The nonactive boron-doped diamond (BDD) anode demonstrated the best performance for DOM oxidation. The humic acid-like fraction (HA, 2.5-20 kDa) predominated the visible absorbance of landfill leachates at λ ≥400 nm, and it generally had the highest reaction rates except the occurrence of the pH-induced denaturation and precipitation of the proteinaceous biopolymer fraction (BP, >20 kDa). During the EO treatment of landfill leachate with BDD anode, the UV absorbance spectra of landfill leachates at wavelengths <400 nm were affected by the formation of free chlorine. Instead, the decrease of Abs420 was found to be a good indicator of the shift of the oxidation from predominantly HA fraction to the proteinaceous BP fraction. The behavior of the Abs420 parameter was also indicative of the transition from the energy-efficient oxidation of DOM to the dominance of side reactions of chlorine evolution and the subsequent formation of ClO 3 - and ClO 4 - . These findings suggest that the EO treatment of landfill leachate can be optimized by adjusting the current density with feedback signals from the online monitoring of Abs420, to achieve a trade-off between degradation of DOM and control of ClO 3 - and ClO 4 - ., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Wen-Tao Li reports financial support was provided by National Key Research and Development Program of China. Ai-Min Li reports financial support was provided by National Natural Science Foundation of China. Gregory V. Korshin is serving in an editorial capacity for the journal Water Research., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

The XANES/EXAFS data and quantum chemical simulations presented in this study demonstrate several features of the chemistry of arsenic compounds found in the condensates and solids generated in landfill gas (LFG) processing carried out for renewable natural gas (RNG) production. The XANES data show the decrease in the position of the absorption edge of As atoms, similar to that characteristic for sulfur-containing As solutes and solids. The EXAFS data show that the As-O and As-S distances in these matrixes are similar to those in thioarsenates. Quantum-chemical calculations demonstrated the close agreement between the experimental and modeled As-S and As-O distances determined for a range of methylated and thiolated arsenic solutes. These calculations also showed that the increase of the number of the As-S bonds in the coordination shell of arsenic is accompanied by a consistent decrease of the charges of As atoms. This decrease is correlated with the number of the As-S bonds, in agreement with the trend observed in the XANES data. These results provide insight into the intrinsic chemistry and reactivity of As species present in LFG matrixes; they may be helpful for the development of treatment methods to control arsenic in these systems., 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. Conflicts of interest There are no conflicts to declare., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Antibiotics are ubiquitous in wastewater and surface water and their presence is of grave concern. Chlorination, an important disinfection process used in wastewater treatment plants and waterworks, causes antibiotics to be degraded. However, interactions of antibiotics with chlorine result in the generation of multiple transformation products (TPs). TPs may be more toxic than the parent compounds, but their structures, yields and ecotoxicity remain to be ascertained in most cases. This study examined the degradation by chlorine of two typical macrolide (MLs) antibiotics, erythromycin (ERY) and roxithromycin (ROX), and identified the TPs formed as a result of ERY and ROX chlorination. The ecotoxicity of ERY, ROX and their TPs was evaluated using a combination of bioassay and ECOSAR prediction. The degradation of ERY and ROX followed pseudo-first-order kinetic at the molar ratio of FAC to MLs of 10:1, and the degradation kinetic rate depends on pH values. Six TPs of ERY including three chlorinated TPs, and six TPs of ROX including two chlorinated TPs were identified. The tertiary N of the desosamine moiety of ERY and ROX was determined to be the main reactive site. Demethylation and chlorine substitution at the reactive site are the main degradation pathways of ERY and ROX. ECOSAR results showed that the chlorinated byproducts of ERY TP578, TP542 and TP528, and the reduced hydroxylation products of ROX TP851 exhibited higher ecotoxicity than their parent compounds. However, algae growth inhibition assays indicated that the overall ecotoxicity of the chlorinated ERY or ROX mixture was lower than that of ERY or ROX prior to chlorination. This may be attributed to the removal of the parent compound and lower yields of toxic substances. While the yields of the toxic TPs may be low, their accumulation and combined effects of the TPs and other co-occurring pollutants should be examined further., 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 B.V. All rights reserved.)

Tetrabromobisphenol S (TBBPS) is a brominated flame retardant and a contaminant of emerging concern. Several studies found that sulfate radical (SO 4 •- ) oxidation is effective to degrade TBBPS. Here, we demonstrate that the presence of nitrite (NO 2 - ) at environmentally relevant levels causes dramatic changes in the kinetics and pathways of TBBPS degradation by SO 4 •- . Initially, NO 2 - suppresses the reaction by competing with TBBPS for SO 4 •- . At the same time, SO 4 •- oxidizes NO 2 - to form nitrogen dioxide radicals (NO 2 • ), which actively react with some key TBBPS degradation intermediates, thus greatly altering the transformation pathway. As a result, 2,6-dibromo-4-nitrophenol (DBNP) becomes the primary TBBPS product. As TBBPS undergoes degradation, the released bromide (Br - ) is oxidized by SO 4 •- to form bromine radicals and free bromine. These reactive bromine species immediately combine with NO 2 • or NO 2 - to form nitryl bromide (BrNO 2 ) that in turn attacks the parent TBBPS, resulting in its accelerated degradation and increased formation of toxic nitrophenolic byproducts. These results show that nitryl halides (e.g., BrNO 2 or ClNO 2 ) are likely formed yet inadequately recognized when SO 4 •- is applied to remediate halogenated pollutants in the subsurface environment where NO 2 - is ubiquitously found. These insights further underscore the potential risks of the application of SO 4 •- oxidation for the remediation of halogenated compounds in realistic environmental conditions.

This study compared effects of conventional ozonation and electrochemical oxidation (EO) on the formation of aldehydes and aliphatic carboxylic acids produced via the oxidation of natural organic matter (NOM) present in a low-mineralized surface water with a relatively low NOM concentration. Conventional ozonation and EO were effective in degrading the aromatic moiety of NOM characterized by the absorbance at 254 nm. Yields of aliphatic carboxylic acids in the ozone treated water were dominated by formate, acetate and oxalate, while no acetate was observed in the case of EO treatment. The speciation of aldehydes was similar in the case of ozonation and EO treatment, but the aldehydes yields were notably higher for ozonation. The presence of the elevated carbonate concentration moderated the changes in disinfection by-products (DBPs) concentration in the EO treated water due to the interception of ∙OH by HCO 3 - , while it did not affect ozonation treatment. This study allows gaining more insights into the nature of processes characteristic and optimization of disinfections based on ozonation and EO methods., 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.)

A hierarchically ordered macroporous RuO 2 electrode (HOM-RuO 2 ) was fabricated to enhance in situ active chlorine production in an electrochemical system intended for treatment of pharmaceutical active compounds (PhACs). The unique structure of HOM-RuO 2 resulted in a decrease of the chlorine evolution potential, a large electro-active area available for in situ conversion of Cl - to active chlorine, and hence improved the active chlorine production by 40%. 5-Fluorouracil (5-FU) was used as a target pollutant to explore the performance of the HOM-RuO 2 for PhACs degradation based on the in situ generated active chlorine. The results showed that the reaction rate of active-chlorine-mediated oxidation of 5-FU produced using the HOM-RuO 2 was 18.4 times higher than that in the case of hydroxyl radicals (OH)-initiated oxidation using a PbO 2 electrode at 30 mA cm -2 . The effects of current density and initial solution pH on the 5-FU removal were investigated. The mechanism of 5-FU degradation was proposed taking into accounts both active chlorine production, and change of the speciation of 5-FU caused by pH variations. The dominant degradation products observed for the degradation of 5-FU using the HOM-RuO 2 were lactic acid, propanol, acetic acid, urea and other small molecules, but no chlorinated products were detected. These study demonstrates the promise of the HOM-RuO 2 -based electrochemical systems for the active-chlorine-mediated treatment of recalcitrant pharmaceuticals found in wastewater., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Recent studies found that both nitrite (NO 2 - ) and ammonium (NH 4 + ) lead to nitrophenolic byproducts in SO 4 •- oxidation processes, during which NO 2 • generated through the oxidation of the inorganic nitrogen by SO 4 •- is the key nitrating agent. This study demonstrates that the formation of phenoxy radicals to which NO 2 • can be incorporated immediately is another governing factor. Two types of sites having distinct reactivities in natural organic matter (NOM) molecules can be transformed to phenoxy radicals upon SO 4 •- oxidation. Fast sites associated with phenolic functionalities are primarily targeted in the reaction sequence involving NO 2 - , because both are preferentially oxidized. Following the depletion of NO 2 - , NH 4 + becomes the main precursor of NO 2 • that interacts with slow sites associated with the carboxylic functionalities. Experimental data show that the formation of total organic nitrogen in 24 h reached 6.28 μM during SO 4 •- oxidation of NOM (4.96 mg/L organic carbon) in the presence of both NO 2 - (0.1 mM) and NH 4 + (1.0 mM), while the sum of those formed in the presence of each alone was only 3.52 μM. Results of this study provide further insights into the mechanisms of nitrated byproduct formation when SO 4 •- is applied for environmental remediation.

Methylated arsenic species are ubiquitous in the environment and resistant to removal by conventional treatment technologies. This study addressed this challenge based on the examination of the removal of dimethylarsinic acid (DMA) in a system that combines zerovalent iron (ZVI) and powdered activated carbon (PAC). The removal of DMA in the ZVI/PAC system was compared to that by coagulation, adsorption, electrochemical and Fenton oxidations, and other conventional methods. While only the electrochemical oxidation using a PbO 2 /Sb-SnO 2 /Ti anode allowed removing up to 60% DMA at several hours-long treatment times, the removal of DMA in the ZVI/PAC system containing 10 g/L ZVI and 2.5 g/L PAC with an initial pH of 2.0 was 95% for a 30 min reaction time. Specific roles of PAC, ZVI and its oxidation products in DMA removal were examined based on the spectroscopic data and quantum chemical modeling for the DMA/Fe(II) and DMA/Fe(III) systems. These methods demonstrated the formation of moderately strong DMA/Fe(II) and DMA/Fe(III) complexation. These results and relevant kinetic data were interpreted to indicate that the removal of DMA is governed by the rapid generation of Fe 2+ ions released as a result of accelerated ZVI corrosion in the galvanic ZVI/PAC microcells and ensuing formation of DMA/ Fe 2+ complexes that are readily adsorbed by PAC., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

The binding between dissolved organic matter (DOM) and micro-pollutants (MPs) results in significant impacts on their migration, transformation and degradation. However, the role of the DOM/MP binding on their oxidative transformation remains poorly studied. The binding of MPs by DOM, in combination with DOM's roles as a photosensitizer and/or a competitor for free radicals, needs to be considered in the context of understanding the DOM's impacts on the oxidative degradation of MPs. This study aims to explore this aspect of DOM/MP interactions based on the quantitation of humic acid (HA) and tetracycline (TET) complexation and its role in TET removal. This study also compared the degradation of free TET versus that bound in HA-TET complexes in different oxidation processes. Fourier transform infrared (FTIR) data show that the carboxyl and phenolic hydroxyl groups in HA are the main binding sites of TET, while nuclear magnetic resonance (NMR) analysis shows the binding of TET engages its -N(CH 3 ) 2 groups, and two-dimensional correlation spectroscopy (2D-COS) data show that the carboxyl groups in DOM are sensitive than phenolic groups in the binding of TET. The difference between the degradation rates (Δk obs ) of the free and bound TET decreased with the increase of ionic strength using sodium nitrate, but increased with the introduction of Ca 2+ and Mg 2+ due to the formation of TET-Ca 2+ /Mg 2+ complexes. Quenching experiments showed that the free radicals (•OH and •SO 4 - ), PMS oxidant and UV light were the main contributors to the TET degradation in UV/PS, UV/PMS and UV/H 2 O 2 processes, respectively. In-situ fluorescence time scanning and differential absorbance spectra showed that free TET was preferentially oxidized over the bound TET in all the tested treatments except UV/PS. These results provide new insights into the role of DOM/MP complexation in the degradation of MPs in natural and engineered systems., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Considerable attention has been recently given to possible transmission of SARS-CoV-2 via water media. This review addresses this issue and examines the fate of coronaviruses (CoVs) in water systems, with particular attention to the recently available information on the novel SARS-CoV-2. The methods for the determination of viable virus particles and quantification of CoVs and, in particular, of SARS-CoV-2 in water and wastewater are discussed with particular regard to the methods of concentration and to the emerging methods of detection. The analysis of the environmental stability of CoVs, with particular regard of SARS-CoV-2, and the efficacy of the disinfection methods are extensively reviewed as well. This information provides a broad view of the state-of-the-art for researchers involved in the investigation of CoVs in aquatic systems, and poses the basis for further analyses and discussions on the risk associated to the presence of SARS-CoV-2 in water media. The examined data indicates that detection of the virus in wastewater and natural water bodies provides a potentially powerful tool for quantitative microbiological risk assessment (QMRA) and for wastewater-based epidemiology (WBE) for the evaluation of the level of circulation of the virus in a population. Assays of the viable virions in water media provide information on the integrity, capability of replication (in suitable host species) and on the potential infectivity. Challenges and critical issues relevant to the detection of coronaviruses in different water matrixes with both direct and surrogate methods as well as in the implementation of epidemiological tools are presented and critically discussed., (Copyright © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

In this study, the model compound esculetin that has functional groups typical for natural organic matter (NOM) was used to ascertain the nature of the characteristic bands in the differential UV-visible absorbance spectra (DAS) associated with the formation of metal-NOM complexes. The binding of ten different metal ions (Cu(II), Ni(II), Co(II), Fe(III), Cr(III), Al(III), Zn(II), Ca(II), Mg(II) and Pb(II)) with esculetin generate four bands in the DAS. These bands are similar to those present in the DAS of metal-NOM complexes. The UV-visible absorbance spectra of the metal-esculetin systems were calculated using time-dependent density functional theory (TD-DFT). The TD-DFT results demonstrate that the prominent features of the DAS of esculetin are primarily associated with the electron transitions between the molecular orbitals near the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) in the metal-esculetin complex. Charge decomposition analysis (CDA) results demonstrated that these electron transitions originate from the esculetin fragment to the Zn(II) fragment in the complex. Covalent indexes [(χ m ) 2 r c ] of the metal ions were found to be correlated with the metal-specific features of the DAS of metal-esculetin systems. The strength of the linear correlations between the quantitative parameters of the electron density of the bond critical points (BCP) is indicative of the strength of the metal-esculetin interactions., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Concentrations of several toxic disinfection by-products (DBP), notably haloacetonitriles (e.g., trichloroacetonitrile, TCAN) and haloketones (e.g., di- and trichloropropanone, DCPN and TCPN, respectively) are affected by chlorination conditions and the inherent instability of these DBPs. In this study, effects of temperature, chlorine dose and reaction time on the formation of TCAN, DCPN and TCPN were interpreted using the approach of differential absorbance spectroscopy. Experimental data obtained for a wide range of water quality conditions demonstrate that in some cases the concentrations of some of the unstable DBPs increased rather than decreased at low temperatures and realistically long contact times. Despite the presence of pronounced changes of the kinetics of generation and degradation of these DBPs at varying temperatures and chlorine doses, their concentrations were strongly correlated with the concurrent changes of spectroscopic properties of DOM quantified via differential absorbance measurements at 272 nm (ΔA 272 ). The maximum values of TCAN, DCPN and TCPN concentrations observed for the chlorination of eight different surface waters occur at the relative decreases of absorbance at 272 nm (defined as RΔA 272 ) values of ca. 0.32 (±0.03), 0.24 (±0.05), and 0.42 (±0.03), respectively. The activation energies of degradation reactions of unstable DBPs were examined and the results indicate that TCAN and TCPN are caused by their hydrolysis with OH - while the degradation of DCPN is mainly caused by halogenation reaction with HOCl. These results in this study may be important for controlling the formation of unstable DBPs and further optimization of drinking water treatment., 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 compared effects of pH, ionic strength and complexation with Mg 2+ on the chromophores and fluorophores of aquatic and terrestrial NOM exemplified by the standard isolates Suwannee River fulvic and humic acid (SRFA and SRHA) and Pahokee Peat fulvic and humic acids (PPFA and PPHA) provided by the International Humic Substance Society (IHSS). The intensity of the differential spectra of the NOM isolates increased monotonically with pH. These spectra comprised contributions of similar chromophore systems associated with the carboxylic and phenolic moieties. The intensity of SRFA and PPFA fluorescence changed non-monotonically vs. pH indicating that the deprotonation of the phenolic fluorophores decreased their emission yields. Examination of the effects of pH on the slopes of the log-transformed absorbance of NOM showed that the influence of deprotonation on the conformations of PPFA and PPHA molecules was less prominent than those for SRFA but not dissimilar to those of SRHA. Changes of the differential spectra and spectral slopes showed that Mg 2+ /PPFA and Mg 2+ /PPHA complexation was more effected by electrostatic interactions while the involvement of phenolic groups was notable for SRFA. The observed trends highlight similarities and differences in the properties of the chromophores and fluorophores in the standard isolates of soil and aquatic NOM. These results necessitate further systematic comparison of the properties of NOM isolates and those of unaltered NOM., 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 compared chlorination-induced changes of the properties of natural organic matter (NOM) represented by standard humic substances and NOM present in pristine and anthropogenically-affect reservoirs, rivers, groundwater and seawater. The chlorination-induced changes of NOM properties were quantified using the differential absorbance spectra (DAS) which were processed via numeric deconvolution. Six Gaussian bands were found to comprise the DAS of all examined waters. These bands (denoted as A0, A1, A2, A3, A4 and A5, respectively) have maxima located at ca. 200, 240, 276, 316, 385 and 547 nm. The bands A1-A4 were observed in the DAS of representative model chlorinated compounds. Quantum chemical (QC) calculations were carried out to examine the intrinsic nature of these bands and electronic transitions associated with them. QC data demonstrate that bands A1 and A2 are present in almost all aromatic organic species, A3 is likely to be associated with acetophenone- and/or styrene-like groups. A4 can be attributed to the engagement of m-hydroxyaromatic and flavone-type groups typical for the polyphenolic moiety in NOM and known to be the key precursors of disinfection by-product (DBP) formation. Thus, the intensity of band A4 is predicted to be an especially strong predictor of DBP formation., 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 examined effects of aquatic and soil natural organic matter (NOM) exemplified by standard Suwannee River fulvic acid (SRFA) and Pahokee Peat fulvic acid (PPFA), respectively, on the electrochemical (EC) reactivity and mass transfer properties of the cationic organic probe toluidine blue (TB) that forms complexes with NOM. EC measurements that were carried out using the method of rotating ring-disc electrode (RRDE) showed that for disc potentials below -0.4 V vs. the standard Ag/AgCl reference electrode, TB molecules undergo EC reduction accompanied by the formation of EC-active products that undergo oxidation at the ring electrode. EC reactions of TB in the range of potentials -0.2 to -0.4 V were determined to involve free TB + cations and TB species adsorbed on the electrode surface. The EC reduction of TB species at the disc potentials < -0.4 V was controlled by the mass transfer of the free TB + cations and TB/NOM complexes to the electrode surface. Formation of TB/NOM complexes caused the mass transfer-controlled TB currents to undergo a consistent decrease. The observed changes were correlated with the extent of TB/NOM complexation and decreases of the diffusion coefficients of TB/NOM complexes that have higher molecular weights (MW) than the free cations. Properties of the intermediates formed upon the reduction of TB + cations were also affected by NOM. These results demonstrate that RRDE measurements of EC reactions of TB or possibly other EC active probes allow probing the complexation of EC-active organic species with NOM and mass transfer properties of NOM complexes and ultimately NOM itself., 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.)

Roxithromycin (ROX) is a widely used macrolide antibiotic and its environmental fate and ecotoxicity have attracted considerable attention. In this study, the phototransformation kinetics and products of ROX under the irradiation of simulated sunlight were investigated. The ecotoxicity of ROX before and after phototransformation were also examined using the bioluminescence bioassay and algae growth inhibition test. The results showed that ROX underwent direct photolysis and indirect photolysis in the presence of Suwannee River humic acid (SRHA) and Suwannee River natural organic matter (SRNOM). The kinetic rate constant of the photodegradation of ROX in the presence of 20 mg·L -1 SRHA and SRNOM were 4.0 and 3.6 times higher than direct photolysis in the absence of dissolved organic matter (DOM). A total of 20 phototransformation products (PTPs) formed as a result of the photodegradation of ROX by simulated solar irradiation were identified, and 10 of them were reported for the first time. The PTPs were generally formed through the N-demethylation, O-demethylation or direct cleavage of the side chain, desosamine or cladinose moiety from ROX. Solutions containing ROX and its PTPs showed an increased toxicity to Vibrio fischeri, demonstrating some PTPs were more toxic to V. fischeri. On the other hand, the toxicity of ROX after irradiation to Chlorella pyrenoidosa decreased, suggesting the phototransformation of ROX in the environment may be a positive outcome in the context of the growth of green algae., 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 B.V. All rights reserved.)

Time-resolved monitoring of bromate and other by-products formed into effluents treated with ozone or advanced oxidation processes in wastewater treatment plants (WWTPs) is time-consuming and expensive. This study examined whether concentrations of bromate formed in wastewater after ozonation in the presence of widely varying bromide levels (from ca. 0.7-21.2 mg/L) can be quantified based on measurements of changes in optical properties (differential UV absorbance (ΔUVA), spectral slopes, total or regional fluorescence) of the ozonated samples. Batch ozonation was carried out using a secondary effluent produced at a major wastewater treatment plant located in the Metropolitan Seattle Area. The tests involved raw and bromide-spiked samples treated with ozone doses from 0.1 to 1 mg O 3 /mg DOC. Measurements of the absorbance at 254 nm (UVA254), fluorescence and bromate concentrations were performed on the treated samples. In the ozonated wastewater the concentration of bromate increased approximately linearly, from <10 ppb to ca. 200 ppb, without showing the lag phase characteristic for lower ozone doses (<0.4 mg O 3 /mg DOC) that was observed in previous studies carried out with concentrations of bromide in the range of 0.05-0.5 mg/L. The highest bromide concentrations used in this study (>10 mg/L) tended to inhibit the generation of bromate. Relative reduction of UVA254 and total fluorescence (TF) were found to be good predictors of bromate generation. Specifically, exponential curves could adequately fit the non-linear relationships found to exist between the concentrations of bromate and the relative reductions of the UV254 and TF, for any initial bromide concentrations used in this study. Little formation of bromate was found to occur for reduction ranges for UVA254 and TF of 30-40% and 70-80% respectively. Conversely, rapid increases in bromate generation were observed when the decrease of UVA254 or TF exceeded these threshold values., 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.)

The release of potentially toxic metal ions from corrosion scales formed on pipe surfaces is of great concern for water quality in drinking water distribution systems (DWDS). This study examined the effects of alkalinity, chloride, and sulfate on metal release from corrosion scales sampled from a corroded iron pipe. Jar tests and recirculation pipe systems were used to investigate the metal-release potential during stagnant and active flow conditions. The experimental data show that both the ambient water chemistry and hydraulic conditions exerted complex influences on metal release from the exposed corrosion scales. Fe, Mn, and Ni were more labile to be released during a 132-h period of stagnation, while the release of Al, Zn, and Cu was an order of magnitude higher under flow conditions compared to stagnant conditions. Increasing concentrations of chloride (from 5 mg/L to 60 mg/L) and sulfate (from 20 mg/L to 100 mg/L) resulted in the increased release of Fe, Al, and Zn, especially under active flow conditions. This effect could be effectively mitigated by increasing alkalinity from 50 mg/L to 200 mg/L as CaCO 3 . While increasing alkalinity suppressed the release of Fe and stimulated the release of Al and Cu under stagnant conditions, this contradictory effect was not observed under active flow conditions., 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.)

In this study, size exclusion chromatography with an array of absorbance, fluorescence, organic nitrogen and organic carbon detectors was used for characterizing property and treatability of effluent organic matter (EfOM) from 12 wastewater treatment plants. According to their apparent molecular weight (AMW), EfOM fractions were assigned to biopolymers (>20 kDa), humic substances that comprise sub-fractions of humic-like acids (HA-I & HA-II, 2.3-7.0 kDa) and fulvic-like acids (FA, 1.5-2.3 kDa), building blocks (0.55-1.5 kDa) and low molecular weight neutral substances (<550 Da). The fractions of biopolymers and low molecular weight neutral substances didn't show humic-like fluorescence, while the fractions of HA-II, FA and building blocks usually had signatures of both humic-like and protein-like fluorescence. Humic substances generally contributed the largest proportion of dissolved organic carbon and nitrogen (DOC & DON) in effluents. Coagulation removed EfOM fractions following the order of biopolymers > HA subfraction > FA subfraction > building blocks, while little removal of protein-like fluorescence in HA-II and FA subfractions was detected. Anion exchange treatment could effectively reduce DOC and DON concentrations; the sequence of the treatment efficiency was humic substances > biopolymers > building blocks. Increasing O 3 doses caused DOC and DON of EfOM to be gradually transformed from large AMW fractions into small AMW fractions, while chromophores and fluorophores in HA subfractions were relatively more refractory than those in the other fractions. Size exclusion chromatography with multiple detectors are suggested to be an informative technique for estimating treatability of EfOM by advanced wastewater treatment processes., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Thermodynamic and kinetic aspects of the formation of trihalomethanes and haloacetic acids determined based on the quantum chemical (QC) simulations were compared in this study with the experimental data generated using the differential spectroscopy approach in chlorination and chloramination. The ratios of the slopes of the correlations between -DlnA 350 values and individual DBPs concentrations (S NH2Cl /S HOCl ) were observed to be linearly correlated with the ratios of the Gibbs free energies (ΔG NH2Cl /ΔG HOCl ) of the corresponding reactions of chloramine and chlorine with acetaldehyde which was used as a model DBP precursor in QC simulations. Further QC examination of the kinetics of chlorination and chloramination of the model compound acetoacetic acid showed that the activation energy of reactions between monochloramine that directly participates in substitution reactions to form mono-, di and tri-halogenated intermediates are 2-3 times higher than those of HOCl formed via the hydrolysis monochloramine. This result confirms that the interactions of chloramine with NOM and ensuing DBP formation are primarily mediated by the free chlorine released as a result of the hydrolysis of monochloramine while direct halogenation of NOM by monochloramine is likely to provide a small contribution to DBP formation., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The inhalation of particulate matter (PM) is a significant health risk associated with reduced life expectancy due to increased cardio-pulmonary disease and exacerbation of respiratory diseases such as asthma and pneumonia. PM originates from natural and anthropogenic sources including combustion engines, cigarettes, agricultural burning, and forest fires. Identifying the source of PM can inform effective mitigation strategies and policies, but this is difficult to do using current techniques. Here we present a method for identifying PM source using excitation emission matrix (EEM) fluorescence spectroscopy and a machine learning algorithm. We collected combustion generated PM 2.5 from wood burning, diesel exhaust, and cigarettes using filters. Filters were weighted to determine mass concentration followed by extraction into cyclohexane and analysis by EEM fluorescence spectroscopy. Spectra obtained from each source served as training data for a convolutional neural network (CNN) used for source identification in mixed samples. This method can predict the presence or absence of the three laboratory sources with an overall accuracy of 89% when the threshold for classifying a source as present is 1.1 μg/m 3 in air over a 24-hour sampling time. The limit of detection for cigarette, diesel and wood are 0.7, 2.6, 0.9 μg/m 3 , respectively, in air assuming a 24-hour sampling time at an air sampling rate of 1.8 liters per minute. We applied the CNN algorithm developed using the laboratory training data to a small set of field samples and found the algorithm was effective in some cases but would require a training data set containing more samples to be more broadly applicable.

Arsenite is a highly toxic compound present in many water sources around the world. The removal of arsenite from water requires its oxidation to arsenate which is much more amenable to treatment using well attested technologies. Prior research has shown that the oxidation of arsenite by hydroxyl radicals is significantly accelerated in the presence of carbonate ions but the intrinsic mechanisms of the acceleration have not yet been established. The main goal of the present work was to examine the oxidation of arsenite in the framework of the density functional theory, to establish a detailed microscopic level mechanism of interactions between arsenite and hydroxyl radicals and to elucidate the nature of the catalytic effect of carbonate ions. Results of this study demonstrate that the [As(OH) 2 CO 3 ] - complex is the thermodynamically most stable species formed in the system H 3 AsO 3 -CO 3 2- /HCO 3 - -H 2 O. Interactions of the hydroxyl radical with the [As(OH) 2 CO 3 ] - complex yield the pre-reaction complex [As(OH) 3 CO 3 ] -∗ in the reaction of subsequent oxidation of arsenite. The structures of the reactants, products and transition states, as well as pre- and post-reaction complexes corresponding to several possible mechanisms of the first stage of As(III) oxidation to As(IV) intermediate using hydroxyl radicals in the absence and in the presence of [As(OH) 2 CO 3 ] - , were determined in this study. The data demonstrate that the arsenite-carbonate complexes [As(OH) 2 CO 3 ] - are characterized by a significantly lower activation energy of the first oxidation stage under the action of a hydroxyl radical (2.8 kcal/mol) compared to that for the free arsenite H 3 AsO 3 (13.6 kcal/mol)., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The presence of galvanized pipe in drinking water distribution systems is known to be associated with heavy metal release, especially after the aging of zinc coating. This study examined release of lead and other heavy metals (e.g., cadmium, chromium) from galvanized steel coupons with a low-lead zinc coating. Metal release data were obtained in 12-week long jar tests which were conducted at varying temperatures and alkalinities. The morphology of the exposed surfaces was dominated by spherical and acicular formations. Exposures at 36 °C were associated with increased corrosion rates, accelerated depletion of zinc coating and faster development of corrosion scales, compared with 4 and 20 °C. The protective action of zinc coating was enhanced at increasing alkalinities. Metal release data showed a significant enrichment of Pb and Cd levels in the particulates released from the low-Pb galvanized steel.

This study examined the kinetics of the binding of Al(III) ions by natural organic matter (NOM) exemplified by Suwannee River humic acid (SRHA). This processes was studied for a 5-8 pH range and environmentally relevant concentrations of the system components. Al(III)-NOM interactions were quantified using differential absorbance spectra whose intensity and shape depended on pH and reaction time. In all cases the differential spectra had four bands with maxima located at 245, 275, 320, 380 nm. These bands were assigned to the engagement of the carboxylic-like and/or phenolic-like groups, as well as electrostatic gel in NOM. Several parameters of the absorbance spectra (e.g., spectral slopes of log-transformed spectra in wavelength range 260-270 and 350-400 nm, ΔS 260-270 and ΔS 350-400 respectively) were linearly correlated (R 2  = 0.98) with concentrations of carboxylic-like groups and total NOM-bound Al(III) ions predicted based on the NICA-Donnan model. The binding of Al(III) ion by NOM at all pHs was modeled assuming the presence of three kinetically distinct sites. This study demonstrates that differential absorbance spectroscopy can be used to quantify the kinetics and mechanisms of NOM-metal ions interactions and monitor them in practically important system including water treatment operations., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

This study compared the binding of europium by soil and aquatic natural organic matter (NOM) exemplified by Pahokee Peat humic acid (PPHA) and Northern Reservoir NOM, respectively. NOM/Eu 3+ interactions were measured based on the differential absorbance approach. The experimental results show that the binding of Eu 3+ by humic acid isolated from agricultural soil results in several features of the differential spectra that are distinct from those observed for aquatic NOM. These features may be associated with the presence in soil NOM of functional groups similar to gallic acid. The binding of Eu 3+ by NOM was modeled using a phenomenological approach that accounted for the involvement of dissimilar metal-binding functionalities. This study also introduced the concept of integrated differential absorbance; the use of that parameter allowed achieving a close fit between the experimental and model data. This study presents an alternative approach to ascertain mechanisms of, and differences in the interactions of europium with model compounds and natural organic matter with the provenance from soil and surface water., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

This study examined the formation of fouling films deposited on the surface of a polyethersulfone (PES) membrane during the filtration of alginate solutions with various ionic strengths. Membrane fouling was characterized by changes of the transmembrane pressure (TMP) and ex situ measured attenuated total reflectance (ATR) Fourier-transform IR (FTIR) spectra at varying stages of filtration runs. The ATR spectra that comprise the vibration bands characteristic of the PES substrate and the deposited film were processed taking into the gradual weakening of the PES substrate-specific bands, whose intensity was shown to depend on the wavenumber of IR radiation and the thickness of the deposited layer. Strongly linear correlations between ratios of first derivatives intensity and wavenumbers of the PES reference lines were established. Calculations of the PES bands' attenuation coefficients allowed determining the apparent thickness and ATR FTIR vibrations of the fouling films per se. Strong correlations between TMP development and ATR-determined apparent thickness of the fouling layers were observed. The intensity of ATR absorbance at 3200 cm -1 was linearly correlated with TMP development for small TMP values before the point of rapidly developing failure of the hydraulic permeability of the system was reached., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

This study focused on developing surrogate indicators for predicting oxidation of phenolic groups in dissolved organic matter (DOM), suppression of halophenols' formation potential and abatement of estrogenic activity during ozonation of water and wastewater. The evolution of pH-dependent differential absorbance spectra suggests that O 3 preferentially reacts with the DOM phenolic moieties and less so with the aromatic carboxylic groups with increasing O 3 /DOC (dissolved organic carbon) ratios and changes of UV absorbance and fluorescence. When ozonation used as pretreatment, the formation of halophenols in subsequent chlorination decreased linearly with increasing O 3 doses or changes of UV absorbance until it reached 85% suppression of the halophenols' formation from unaltered DOM. The thresholds of decreases of UVA254, UVA280 and humic-like fluorescence corresponding to 85% suppression of halophenols' formation were in the range of 25%-30%, 30%-35% and 30%-45%, respectively. Pre-ozonation also showed a moderate suppression of haloacetic acids (HAAs) formation potentials, ≤26.5% for reverse osmosis isolate of Suwannee River natural organic matter and ≤31.5% for Yangtze River at applied O 3 doses. Measurement of changes of estrogenic activity during ozonation of water and wastewater showed that to attain a >90% abatement of estrogenic activity, the corresponding thresholds of decreases of UVA254, UVA280 and humic-like fluorescence were ∼30%, ∼40%, and ∼70%, respectively. Bromate formation was also suppressed to below 10 μg/L before these thresholds. This study suggests that optimal ozonation conditions and a balance between control of disinfection byproducts (halophenols, HAAs and bromate) and elimination of estrogenic activity can be reached based on online data., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

This study compared the experimental and theoretically calculated differential absorbance spectra (DAS) of quercetin, which is a typical model compound of natural organic matter (NOM) that is found in biochemical and environmental systems. Absorbance spectra of quercetin, which has five exchangeable protons, were generated at each state of deprotonation and its binding with Cu(II) ions. The spectra showed that the emergence of characteristic peaks in the experimental DAS was associated with the deprotonation of quercetin and its binding with Cu(II). Calculations of the theoretical DAS were conducted based on the time-dependent density functional theory (TD-DFT) methods and yielded results that were consistent with the experimental DAS data because the features in the absorbance spectra were primarily associated with the electron transitions from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO) in the molecule. The appearance of the characteristic peaks in the DAS reflects the changes of the structure and electron distribution of the organic molecules that are induced by water treatment or environmental processes., (Copyright © 2019. Published by Elsevier B.V.)

This study aimed to elucidate the intrinsic mechanisms of PS activation by carbon nanotubes (CNTs). Singlet oxygen generation ( 1 O 2 ) and direct CNTs-mediated electron transfer were hypothesized to be two major pathways of the oxidation of 2,4-dichlorophenol (2,4-DCP) by PS in the presence of both unmodified and modified CNTs. For the first time, roles of CNT active sites responsible for PS activation were determined using CNT derivatization and structural characterization. By selectively deactivating the carbonyl, hydroxyl or carboxylic groups on CNTs surface and linear sweep voltammetry (LSV) analysis, CO groups were determined to be the main active sites contributing to the direct electron transfer oxidation, while singlet oxygen was generated at CNTs defects. Subsequent UV irradiation was shown to cause the recovery of surface defects with I D /I G of CNTs increasing by 21%. This resulted in the regeneration of the performance for the coupled system and allowed for multi-cycle activation of PS by CNTs. These results suggest that CNTs/PS system combined with regeneration based on UV irradiation can be used as an effective alternative process for continuous degradation of recalcitrant aqueous contaminants through the non-radical mechanism., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Chlorination of coastal (CS) and deep ocean (DO) seawater was accompanied by a prominent decrease (of up to 70%) of the intensity of its emission which was measured using a 315 nm excitation wavelength. Deconvolution of the emission spectra of CS and DO seawater showed that these spectra comprised three Gauss-shaped bands. The intensities of two of these bands decreased rapidly as the halogenation proceeded. For both DO and CS seawater, two stages of changes of their fluorescence were observed. The first stage in which the relative changes of the fluorescence intensity (ΔF/F) were between zero to 0.30 and 0.40 was not accompanied by the release of individual disinfection byproduct (DBP) species. For ΔF/F values above the corresponding thresholds, the relative changes of fluorescence intensity were well correlated with the concentrations of individual DBP species such as trihalomethanes and haloacetonitriles. R 2 values for CHBr 3 , CHBr 2 Cl and CHBrCl 2 formed in DO seawater were 0.83, 0.80 and 0.68, respectively while for CS seawater, the corresponding R 2 values were 0.91, 0.93 and 0.92. The presented data demonstrate that the intrinsic chemistry of DBP formation and dissolved organic matter (DOM) halogenation in seawater can be well quantified based on the examination of changes of its fluorescence. This approach can also be employed for practical monitoring of changes of properties of marine DOM and generation of DBPs in desalination, marine aquaculture and other processes., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Solar irradiation of chlorine-containing waters enhances inactivation of chlorine-resistant pathogens (e.g., Cryptosporidium oocysts), through in situ formation of ozone, hydroxyl radical, and other reactive species during photolysis of free available chlorine (FAC) at UVB-UVA wavelengths of solar light (290-400 nm). However, corresponding effects on regulated disinfection byproduct (DBP) formation and associated dissolved organic matter (DOM) properties remain unclear. In this work, when compared to dark chlorination, sunlight-driven FAC photolysis over a range of conditions was found to yield higher DBP levels, depletion of DOM chromophores and fluorophores, preferential removal of phenolic groups versus carboxylic acid groups, and degradation of larger humic substances to smaller molecular weight compounds. Control experiments showed that increased DBP levels were not due to direct DOM photolysis and subsequent dark reactions with FAC, but to co-exposure of DOM to FAC and reactive species (e.g., O 3 , HO • , Cl • , Cl 2 •- , ClO • ) generated by FAC photolysis. Because solar chlorine photolysis can enable inactivation of chlorine-resistant pathogens at far lower CT FAC values than chlorination alone, the increases in DBP formation inherent to this approach can likely be offset to some extent by the ability to operate at significantly decreased CT FAC . Nonetheless, these findings demonstrate that applications of solar chlorine photolysis will require careful attention to potential impacts on DBP formation., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Thermodynamic and structural aspects of the hydration of Pb(II) ions were explored based on DFT calculations combined with the supermolecular/continuum solvent model. Hydration of Pb(II) was considered as the formation of Pb(H 2 O) n 2+ aqua complexes (n=6-9) from the gas phase Pb(II) ion. Hexa- and hepta-aqua Pb(II) complexes were shown to exhibit the hemidirected symmetry, while those containing eight and nine water molecules are characterized by the holodirected symmetry. The calculations showed that because Pb(H 2 O) n 2+ complexes with six to nine water molecules have comparable thermodynamic stabilities, such complexes are likely to coexist in aqueous solutions. The deprotonation of Pb(H 2 O) n 2+ complexes was shown to result in the formation of the mono-hydroxo complex [Pb(H 2 O) 4 OH] + . The pK a1 value determined for this reaction (7.58 for Pb(H 2 O) 6 2+ ) was close to the experimental value of 7.61 used in recent models of aquatic equilibria. The density functional method ω-B97X(PCM-UAO) in combination with the atomic basis set 6-311++G(d,p) for O and H and the small-core electron effective pseudopotential (ECP) with the aug-cc-pvdz-PP basis set for Pb can be recommended for such calculations. Graphical abstract Structures of Pb(II) ions with varying numbers of water molecules in the inner hydration shell.

Herein, the rotating disk electrode technique was used for the first time to investigate the effects of mass-transfer limitations and pH on the electrochemical oxidation of CPX, to determine the kinetics of CPX oxidation and to explore intrinsic mechanisms during the electron transfer process. Firstly, cyclic voltammetry revealed that an obvious irreversible CPX oxidation peak was observed within the potential window from 0.70 to 1.30 V at all pHs. Based on the Levich equation, the electrochemical oxidation of CPX in the electron transfer process was found to be controlled by both diffusion and kinetic processes when pH = 2, 5, 7 and 9; the diffusion coefficient of CPX at pH = 2 was calculated to be 1.5 × 10-7 cm2 s-1. Kinetic analysis indicated that the reaction on the electrode surface was adsorption-controlled compared to a diffusion process; the surface concentration of electroactive species was estimated to be 1.15 × 10-9 mol cm-2, the standard rate constant of the surface reaction was calculated to be 1.37 s-1, and CPX oxidation was validated to be a two-electron transfer process. Finally, a possible CPX oxidation pathway during the electron transfer process was proposed. The electrochemical degradation of CPX on a Ti-based anode was also conducted subsequently to investigate the electrochemical oxidation of CPX in the indirect oxidation process in bulk solutions. The effects of pH and current density were determined and compared to related literature results. The oxidation of CPX at different pHs is believed to be the result of a counterbalance between favorable and unfavorable factors, namely electromigration and side reactions of oxygen evolution, respectively. The effects of current density indicated a diffusion- and reaction-controlled process at low currents followed by a reaction-controlled process at high currents. The results presented in this study provide better understanding of the electrochemical oxidation of CPX and would enable the development of new treatment methods based on electrochemistry.

This study compared effects of chlorination and chloramination on the chromophores of dissolved organic matter (DOM) and attendant formation of disinfection by-products (DBPs) in raw and treated surface waters. Comparison of the differential absorbance spectra of chloraminated and chlorinated waters shows that interactions of chloramine with DOM chromophores result in changes that are in many respects similar to those observed for chlorine although the extent of degradation of DOM chromophores and the attendant decrease of DOM aromaticity by chloramine are less pronounced than that caused by free chlorine. The degradation of DOM chromophores caused by the examined disinfectants indicated that in both cases a gradual decrease of DOM took place. Decreases of DOM aromaticity estimated based on the changes of DOM absorbance at 254 or 280 nm were correlated with chlorine consumption in a similar way for both examined disinfectants. Correlations between changes of DOM absorbance and yields of dihaloacetic acids (DHAA) were also similar for chlorination and chloramination. This was interpreted to indicate that the generation of DHAA proceeds via the degradation of the reactive sites associated with DOM chromophores irrespective of whether these sites are engaged by chlorine or chloramine. Correlations between the decrease of DOM aromaticity and formation of other DBP (e.g. trihalomethanes - THM, trihaloacetic acids - THAA and dihaloacetonitriles - DHAN) for chloramine and chlorine were also observed but, as opposed to the observations for DHAA, the correlations between degradation of DOM aromaticity and yields of THM, THAA or DHAN were different for chlorination and chloramination., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

This study investigated the applicability of fluorescence indexes based on the interpretation of excitation emission matrices (EEMs) by PARAFAC analysis and by selecting fluorescence intensities at a priori defined excitation/emission pairs as surrogates for monitoring the behavior of emerging organic compounds (EOCs) in two catchment basins impacted by wastewater discharges. Relevant EOC and EEM data were obtained for a 90 km stretch of the Simeto River, the main river in Sicily, and the smaller San Leonardo River, which was investigated for a 17 km stretch. The use of fluorescence indexes developed by these two different approaches resulted in similar observations. Changes of the fluorescence indexes that correspond to a group of humic-like fluorescing species were determined to be highly correlated with the concentrations of recalcitrant contaminants such as sucralose, sulfamethoxazole and carbamazepine, which are typical wastewater markers in river water. Changes of the fluorescence indexes related to tyrosine-like substances were well correlated with the concentrations of ibuprofen and caffeine, anthropogenic indicators of untreated wastewater discharges. Chemical oxygen demand and dissolved organic carbon concentrations were correlated with humic-like fluorescence indexes. The observed correlations were site-specific and characterized by different regression parameters for every collection event. Caffeine and carbamazepine showed correlations with florescence indexes in the San Leonardo River and in the alluvial plain stretch of the Simeto River, whereas sucralose, sulfamethoxazole and ibuprofen have always been well correlated in all the investigated river stretches. However, when data of different collection events from river stretches where correlations were observed were combined, good linear correlations were obtained for data sets generated via the normalization of the measured concentrations by the average value for the corresponding collection event. These results show that fluorescence based indexes can be used to monitor the behavior of some trace organic contaminants in wastewater impacted rivers and to track wastewater discharges in streams and rivers.

This study investigated the applicability of different techniques for fluorescence excitation/emission matrices data interpretations, including peak-picking method, fluorescence regional integration and PARAFAC modelling, to act as surrogates in predicting emerging trace organic compounds (ETOrCs) removal during conventional wastewater treatments that usually comprise primary and secondary treatments. Results showed that fluorescence indexes developed using alternative methodologies but indicative of a same dissolved organic matter component resulted in similar predictions of the removal of the target compounds. The peak index defined by the excitation/emission wavelength positions (λ ex/ λ em ) 225/290nm and related to aromatic proteins and tyrosine-like fluorescence was determined to be a particularly suitable surrogate for monitoring ETOrCs that had very high removal rates (average removal >70%) (i.e., triclosan, caffeine and ibuprofen). The peak index defined by λ ex/ λ em =245/440nm and the PARAFAC component with wavelength of the maxima λ ex/ λ em =245, 350/450, both identified as humic-like fluorescence, were found remarkably well correlated with ETOrCs such as atenolol, naproxen and gemfibrozil that were moderately removed (51-70% average removal). Finally, the PARAFAC component with wavelength of the maxima λ ex/ λ em =<240, 315/380 identified as microbial humic-like fluorescence was the only index correlated with the removal of the antibiotic trimethoprim (average removal 68%)., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The degradation of effluent organic matter (EfOM) in a municipal wastewater treated by ozonation was characterized using the methods of high-performance size-exclusion chromatography (HP-SEC) and excitation/emission matrix (EEM) fluorescence combined with parallel factor analysis (PARAFAC). The removal of 40 diverse trace-level contaminants of emerging concern (CEC) present in the wastewater was determined as well. Ozonation caused a rapid decrease of the absorbance and fluorescence of the wastewater, which was associated primarily with the oxidation of high and low apparent molecular weight (AMW) EfOM fractions. PARAFAC analysis also showed that components C1 and C2 decreased prominently in these conditions. The EfOM fraction of intermediate molecular weight ascribable to a terrestrial humic-like component (C3) tended to be less reactive toward ozone. Relative changes of EEM fluorescence were quantified using F max values of PARAFAC-identified components (∆F/F 0 max ). Unambiguous relationships between ∆F/F 0 max values and the extent of the degradation of the examined CECs (∆C/C 0 ) were established. This allowed correlating main parameters of the ∆C/C 0 vs. ∆F/F 0 max relationships with the rates of oxidation of these CECs. The results demonstrate the potential of online measurements of EEM fluorescence for quantitating effects of ozonation on EfOM and micropollutants in wastewater effluents.