Search

Micro and nanobubbles (MNBs), as an efficient and convenient method, have been widely used in water treatment. Composed of gas and water, MNBs avoid directly introducing potential secondary pollutants. Notably, MNBs exhibit significant advantages through interface reactions in assisting AOPs. They overcome barriers like low mass transfer coefficients and limited reactive sites, and shorten the distance between pollutants and oxidants, achieving higher pollutant removal efficiency. However, there is a lack of systematic summary and in-depth discussion on the fundamental mechanisms of MNBs-assisted AOPs. In this critical review, the characteristics of MNBs related to water treatment are outlined first. Subsequently, the recent applications, performance, and mechanisms of MNBs-assisted AOPs including ozone, plasma, photocatalytic, and Fenton oxidation are overviewed. We conclude that MNBs can improve pollutant removal mainly by enhancing the utilization of reactive oxygen species (ROS) generated by AOPs due to the effective interface reactions. Furthermore, we calculated the electrical energy per order of reaction (EE/O) parameter of different MNBs-assisted AOPs, suggesting that MNBs can reduce the total energy consumption in most of the tested cases. Finally, future research needs/opportunities are proposed. The fundamental insights in this review are anticipated to further facilitate an in-depth understanding of the mechanisms of MNBs-assisted AOPs and supply critical guidance on developing MNBs-based technologies for 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 © 2024. Published by Elsevier Ltd.)

The ultraviolet/monochloramine (UV/NH 2 Cl) process is an emerging advanced oxidation process with promising prospects in water treatment. Previous studies developed kinetic models of UV/NH 2 Cl for simulating radical concentrations and pollutant degradation. However, the reaction rate constants of Cl 2 •- with bicarbonate and carbonate (k Cl2•-, HCO3- and k Cl2•-, CO32- ) were overestimated in literature. Consequently, when dosing 1 mM chloride and 1 mM bicarbonate, the current models of UV/NH 2 Cl severely under-predicted the experimental concentrations of three important radicals (i.e., hydroxyl radical (HO • ), chlorine radical (Cl • ), and dichloride radical (Cl 2 •- )) with great deviations (> 90 %). To investigate this issue, the transformation reactions among these three radicals in UV/NH 2 Cl were systematically studied. For the first time, it was found that in addition to Cl • , Cl 2 •- was also an important parent radical of HO • in the presence of chloride, and chloride could effectively compensate the inhibitory effect of bicarbonate on HO • generation in the system. Moreover, reactions and rate constants in current models were scrutinized from corresponding literature, and the reaction rate constants of Cl 2 •- with bicarbonate and carbonate (k Cl2•-, HCO3- and k Cl2•-, CO32- ) were reevaluated to be 1.47 × 10 5 and 3.78 × 10 6 M -1 s -1 , respectively, by laser flash photolysis. With the newly obtained rate constants, the refined model could accurately simulate concentrations of all three radicals under different chloride and bicarbonate dosages with satisfactory deviations (< 30 %). Meanwhile, the refined model performed much better in predicting pollutant degradation and radical contribution compared with the unrefined model (with the previously estimated k Cl2•-, HCO3- and k Cl2•-, CO32- ). The results of this study enhanced the accuracy and applicability of the kinetic model of UV/NH 2 Cl, and deepened the understanding of radical transformation in the process., 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.)

Halogenated BPA (XBPA) forms resulting from water chlorination can lead to increased toxicity and different biological effects. While previous studies have reported the occurrence of different XBPAs, analytical limitation have hindered the analysis and differentiation of the many potential isomeric forms. Using online solid-phase extraction - liquid chromatography - ion-mobility - high-resolution mass spectrometry (OSPE-LC-IM-HRMS), we demonstrated a rapid analysis method for the analysis of XBPA forms after water chlorination, with a total analysis time of less than 10 min including extraction and concentration and low detection limits (∼5-80 ng/L range). A multi in-vitro bioassay testing approach for the identified products revealed that cytotoxicity and bioenergetics impacts were largely associated with the presence of halogen atoms at positions 2 or 2' and the overall number of halogens incorporated into the BPA molecule. Different XBPA also showed distinct impacts on oxidative stress, peroxisome proliferator-activated receptor gamma - PPARγ, and inflammatory response. While increased DNA damage was observed for chlorinated water samples (4.14 ± 1.21-fold change), the additive effect of the selected 20 XBPA studied could not explain the increased DNA damage observed, indicating that additional species or synergistic effects might be at play., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:Shane Allen Snyder reports financial support was provided by National Research Foundation, Singapore. Shane Allen Snyder reports financial support was provided by PUB Singapore’s National Water Agency. Shane Allen Snyder reports equipment, drugs, or supplies was provided by Agilent Technologies Inc., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

The presence of numerous chemical contaminants from industrial, agricultural, and pharmaceutical sources in water supplies poses a potential risk to human and ecological health. Current chemical analyses suffer from limitations, including chemical coverage and high cost, and broad-coverage in vitro assays such as transcriptomics may further improve water quality monitoring by assessing a large range of possible effects. Here, we used high-throughput transcriptomics to assess the activity induced by field-derived water extracts in MCF7 breast carcinoma cells. Wastewater and surface water extracts induced the largest changes in expression among cell proliferation-related genes and neurological, estrogenic, and antibiotic pathways, whereas drinking and reclaimed water extracts that underwent advanced treatment showed substantially reduced bioactivity on both gene and pathway levels. Importantly, reclaimed water extracts induced fewer changes in gene expression than laboratory blanks, which reinforces previous conclusions based on targeted assays and improves confidence in bioassay-based monitoring of water quality.

Monochloramine (NH 2 Cl) is applied upstream of reverse osmosis (RO) membranes for biofouling control. Residual NH 2 Cl can undergo UV photolysis downstream, generating reactive species for an AOP to occur. At the bench-scale, NH 2 Cl is typically generated from combining sodium hypochlorite and ammonium chloride or sulfate. This study investigated the degradation of four compounds of interest - acetaminophen, caffeine, sucralose and 1,4-dioxane - in UV/NH 2 Cl at the bench scale to study their reactivity with reactive chlorine species (RCS) and reactive nitrogen species (RNS). With methanol acting as a scavenger of • OH radicals, the performance of UV/NH 2 Cl was compared to UV/H 2 O 2 and UV/HOCl. In UV/H 2 O 2 , dioxane was severely inhibited at 1-2 mg/L H 2 O 2 and comparable at 5 mg/L to UV/NH 2 Cl. When ammonium sulfate ((NH 4 ) 2 SO 4 ) was used as the ammonia source over ammonium chloride (NH 4 Cl), the overall degradation of micropollutants was higher and caffeine was exclusively degraded. At 1-2 mg/L NH 2 Cl, dioxane degraded by 16.2-17.8% and 2.92-5.29% from (NH 4 ) 2 SO 4 and NH 4 Cl respectively while caffeine degraded by 7.45-9.61% with NH 2 Cl ((NH 4 ) 2 SO 4 ), but not degrade with NH 2 Cl (NH 4 Cl). The higher concentration of chloride ions from NH 4 Cl significantly influenced the speciation of generated radicals and impacted micropollutant degradation. This suggests that the reactivity of more selective RCS (Cl 2 •- , • ClO, ClOH •- ) and RNS ( • NH 2 , • NO, • NO 2 , etc.) varies with micropollutants of interest. The presence of higher chloride concentration from the ammonia source inhibited the generation of • OH radicals with • OH consumed by RNS to form NO 3 - (μg/L levels), showing the impact of the choice of ammonia source and the water matrix on UV/NH 2 Cl performance., Competing Interests: Declaration of competing interest The authors declare that they do not have any known competing financial conflicts of interest or personal connections that could have given the impression of affecting the findings presented in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

As a widely used secondary vulcanization accelerator in the rubber industry, 1,3-diphenylguanidine (DPG) poses risks to human health and the environment. To compare and comprehend the disinfection process of DPG, this work investigates the reaction kinetics, toxicity, and transformation products (TPs) of DPG during chlorination and monochloramination. It has been revealed that the reactivity of monochloramine is significantly slower compared to chlorination of DPG, with the maximum efficiency observed at pH 7 to pH 8. Cytotoxicity assessment using HepG2 and THP-1 cells reveals that cytotoxicity hierarchy is as follows: chlorine TPs > monochloramine TPs > DPG. Moreover, oxidant-to-DPG molar ratios 10 and 20 lead to higher cytotoxicity in both chlorination and monochloramination compared to ratio 5 and 100. Additionally, cell bioenergetics experiments demonstrate that chlorine and monochloramine TPs induce mitochondrial dysfunction and enhance glycolytic function in HepG2 cells. The genotoxic response from p53 signaling further suggested genotoxic effects of certain TPs. Furthermore, analysis of TPs using high-resolution mass spectrometry (HRMS) identifies ten TPs, with chlorination yielding more TPs than monochloramination. Generally, a chlorine or monochloramine molar ratio to DPG of 10-20 results in an increased formation of TPs and heightened cytotoxicity. Notably, higher oxidant molar ratios increased the formation of monoguanidine TPs and DPG hydroxylation during chlorination, whereas monochloramination lead to DPG substitution predominantly generating chlorinated DPG due to weaker oxidation effects. These findings provide valuable information for the appropriate treatment of DPG and disinfection processes in water facilities to mitigate potential risks to human health and the ecosystem., 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.)

UV/chlorine process is a promising advanced treatment to eliminate pathogen and remove refractory micropollutants for reclamation of municipal secondary effluent. However, effluent organic matter (EfOM) featuring high organic nitrogen content serves as a potential precursor for nitrogenous disinfection byproducts (N-DBPs) of health concern. The molecular-level alteration of a hydrophobic (HPO) EfOM fraction and a transphilic (TPI) EfOM fraction isolated from the same municipal effluent and the formation of N-DBPs in the UV/chlorine were tracked by ultrahigh-resolution mass spectrometry. Compared with chlorination, UV/chlorine induced a significantly greater modification on the molecular composition of EfOM and resulted in formation of unique formulae and chlorinated molecules with higher degree of oxidation, lower aromaticity, and less carbon number due to the involvement of reactive radical species. For both EfOM fractions, UV/chlorine formed more diverse DBPs with higher intensity and Cl-incorporation than chlorination. The TPI fraction of EfOM characterized by higher O/C and N/C ratios generated more N-DBPs with higher intensity clustered in the high O/C region than the HPO fraction of EfOM by both UV/chlorine and chlorination. Totally, 207 and 117 nitrogen-containing chlorinated formulae were recorded after UV/chlorine treatment of TPI and HPO, respectively. Precursor tracking found a greater number of DBPs were originated from raw EfOM through electrophilic substitution pathway rather than chlorine addition. Toxicity bioassays demonstrated that DBPs can trigger oxidative stress-induced DNA damage, while HPO fraction of EfOM dominated the induction of cytotoxicity. However, no correlation could be established between the diversity/abundance of N-DBPs and the level of DNA damage. A total of 22 DBPs with a significant rank correlation with DNA damage were identified, while C 8 H 6 O 5 NCl was found as the N-DBP with the strongest correlation. The potential toxic chlorine-containing formula with the most abundant intensity was assigned to C 5 HO 3 Cl 3 . This study suggests that the character and transformation of EfOM and associated toxicity is critical to evaluate the UV/chlorine process toward practical application., 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.)

1,3-diphenylguanidine (DPG) is a commonly used rubber and polymer additive, that has been found to be one of the main leachate products of tire wear particles and from HDPE pipes. Its introduction to aquatic environments and potentially water supplies lead to further questions regarding the effects of disinfection by-products potentially formed. Using different bioassay approaches and NGS RNA-sequencing, we show that some of the chlorinated by-products of DPG exert significant toxicity. DPG and its chlorinated by-products also can alter cell bioenergetic processes, affecting cellular basal respiration rates and ATP production, moreover, DPG and its two chlorination products, 1,3-bis-(4-chlorophenyl)guanidine (CC04) and 1-(4-chlorophenyl)-3-(2,4-dichlorophenyl)guanidine (CC11), have an impact on mitochondrial proton leak, which is an indicator of mitochondria damage. Evidence of genotoxic effects in the form of DNA double strand breaks (DSBs) was suggested by RNA-sequencing results and further validated by an increased expression of genes associated with DNA damage response (DDR), specifically the canonical non-homologous end joining (c-NHEJ) pathway, as determined by qPCR analysis of different pathway specific genes (XRCC6, PRKDC, LIG4 and XRCC4). Immunofluorescence analysis of phosphorylated histone H2AX, another DSB biomarker, also confirmed the potential genotoxic effects observed for the chlorinated products. In addition, chlorination of DPG leads to the formation of different chlorinated products (CC04, CC05 and CC15), with analysed compounds representing up to 42% of formed products, monochloramine is not able to effectively react with DPG. These findings indicate that DPG reaction with free chlorine doses commonly applied during drinking water treatment or in water distribution networks (0.2-0.5 mg/L) can lead to the formation of toxic and genotoxic chlorinated products., (Copyright © 2022. Published by Elsevier B.V.)

UV-based water treatment processes have been reported to induce genotoxicity during the treatments of surface water, drinking water and artificial water with natural organic matters (NOMs), causing genotoxicity concerns for the drinking water safety. Nitrogenous disinfection byproducts (N-DBPs) were generally reported to be much more genotoxic than their non-nitrogenous analogues, and might be responsible for the genotoxicity in UV processes. Although nitrate-rich water was getting attention for the possibility of genotoxicity and N-DBPs during UV treatments, the impact mechanism of nitrate on the degradation of NOMs, the formation of N-DBPs and genotoxicity has not been explicated. Here simulation experiments of NOM degradation under medium-pressure (MP) UV and MP UV/H 2 O 2 treatments were conducted to explore the effect of nitrate on the molecular characteristics of NOM, the nitrate-derived N-DBPs and the potential genotoxicity through non-targeted analysis and CALUX® reporter gene assays. The results showed that nitrate can accelerate the degradation of NOMs in the MP UV process but inhibit the degradation of NOMs in the MP UV/H 2 O 2 process. During the degradation of NOMs, the molecular compositions varied by the effect of nitrate on oxygen atoms, molecule analogs, and saturation. A total of 105 and 374 nitrate-derived N-DBPs were identified in the MP UV and MP UV/H 2 O 2 treatment, respectively. Most of these N-DBPs contain one nitrogen atom, and the representative features are nitro-, methoxy- (or hydroxyl-) and ester- groups on benzene. No genotoxicity was observed without nitrate spiking, whereas genotoxicity was induced after both MP UV and MP UV/H 2 O 2 treatments when nitrate was spiked, which is worthy of attention for the drinking water safety management., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Different groups of disinfection by-products (DBPs) were studied through the degradation of iopamidol by the sequential oxidation process of ozone-low pressure ultraviolet light (O 3 -LPUV) followed by chlorination. This paper investigates the attenuation of iopamidol under this sequential treatment and the effect of chlorine contact time (30 min versus 3 days) to control the formation potential of DBPs: trihalomethanes (THMs), haloacetonitriles (HANs) and haloacetamides (HAMs). Thirty target DBPs among the 9 iodinated-DBPs (I-DBPs), were monitored throughout the sequential treatment. Results showed that O 3 -LPUV removed up to 99% of iopamidol, while ozone and LPUV alone removed only 90% and 76% respectively. After chlorine addition, O 3 -LPUV yielded 56% lower I-DBPs than LPUV. Increasing chlorine contact time resulted in higher concentrations of all DBP groups (THMs, HANs, and HAMs), with the exception of I-DBPs. One new iodinated-haloacetamide, namely chloroiodoacetamide (CIACM) and one iodoacetonitrile (IACN) were detected. These results suggest the iodine incorporated in iopamidol may be a precursor for iodinated-nitrogenous-DBPs, which are currently not well studied., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

This work evaluated different advanced oxidation processes (AOPs) operated at pilot-scale as tertiary treatment of municipal wastewater in terms of energy efficiency, disinfection by-products formation and pathogens inactivation. Investigated AOPs included UV/H 2 O 2 , UV/Cl 2 , O 3 , O 3 /UV, H 2 O 2 /O 3 /UV, Cl 2 /O 3 /UV. AOPs were operated using various ozone doses (1.5-9 mg L -1 ), and UV fluences (191-981 mJ cm -2 ). Electrical energy costs necessary for the oxidation of contaminants of emerging concern (CEC) (i.e., carbamazepine, fluoxetine, gemfibrozil, primidone, sulfamethoxazole, trimethoprim) were calculated using the electrical energy per order (E EO ) parameter. Ozonation resulted by far the most energy efficient process, whereas UV/H 2 O 2 and UV/Cl 2 showed the highest energy costs. Energy costs for AOPs based on the combination of UV and ozone were in the order O 3 /UV ≈ Cl 2 /O 3 /UV > H 2 O 2 /O 3 /UV, and they were significantly lower than energy costs of UV/H 2 O 2 and UV/Cl 2 processes. Cl 2 /O 3 /UV increased bromate formation, O 3 /UV and O 3 had same levels of bromate formation, whereas H 2 O 2 /O 3 /UV did not form bromate. In addition, UV photolysis resulted an effective treatment for NDMA mitigation even in combination with ozone and chlorine in AOP technologies. Ozonation (doses of 1.5-6 mg L -1 ) was the least effective process to inactivate somatic coliphages, total coliform, escherichia coli, and enterococci. UV irradiation was able to completely inactivate somatic coliphages, total coliform, escherichia coli at low fluence (191 mJ cm -2 ), whereas enterococci were UV resistant. AOPs that utilized UV irradiation were the most effective processes for wastewater disinfection resulting in a complete inactivation of selected indicator organisms by low ozone dose (1.5 mg L -1 ) and UV fluence (191-465 mJ cm -2 )., 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.)

Bisphenol A (BPA) is a well-known xenoestrogen, and UV/H 2 O 2 advanced oxidation process (AOP) is one of the most effective technologies to remove BPA from water. Using BPA spiked tap water, a batch-scale photochemical experiment was conducted to investigate whether BPA can pose a genotoxicity concern during the medium pressure (MP) UV/H 2 O 2 treatment and the post-chloramination. Samples at different UV exposure and post-chloramination durations were collected and analyzed by CALUX® gene reporter assays regarding estrogen receptor α (ERα) and p53 transcriptional activity. MP UV/H 2 O 2 process did not cause extra estrogenic effects from the degradation of BPA, whereas genotoxicity occurred when the treated water was exposed with monochloramine. Seven frequently reported nitrogenous disinfection byproducts (N-DBPs) were detected, but none of them were responsible for the observed genotoxicity. Employed with gas chromatography-quadrupole time-of-flight mass spectrometry (GC-QTOF-MS), four compounds possibly contributed to the genotoxicity were tentatively identified and two of them with aminooxy- or cyano- group were considered as "new" N-DBPs. This study demonstrated that by-products differ from their parent compounds in toxicity can be formed in the UV oxidation with post-disinfection process, which should become a cause for concern., Competing Interests: Declaration of competing interest We declare that we do not have any commercial or associative interest that represents a conflict of interest in connection with the work submitted., (Copyright © 2021 Elsevier B.V. All rights reserved.)

This work critically compared the removal of fluorescing PARAFAC components and selected pharmaceuticals (carbamazepine, fluoxetine, gemfibrozil, primidone, sulfamethoxazole, trimethoprim) from a tertiary wastewater effluent by different UV- and ozone-based advanced oxidation processes (AOPs) operated at pilot-scale. Investigated AOPs included UV/H 2 O 2 , UV/Cl 2 , O 3 , O 3 /UV, H 2 O 2 /O 3 /UV, and the new Cl 2 /O 3 /UV. AOPs comparison was accomplished using various ozone doses (0-9 mg/L), UV fluences (191-981 mJ/cm 2 ) and radical promoter concentrations of Cl 2  = 0.04 mM and H 2 O 2  = 0.29 mM. Chlorine-based AOPs produced radical species that reacted more selectively with pharmaceuticals than radical species and oxidants generated by other AOPs. Tryptophan-like substances and humic-like fluorescing compounds were the most degraded components by all AOPs, which were better removed than microbial products and fulvic-like fluorescing substances. Removal of UV absorbance at 254 (UV 254 ) nm was always low. Overall, chlorine-based AOPs were more effective to reduce fluorescence intensities than similar H 2 O 2 -based AOPs. The Cl 2 /O 3 /UV process was the most effective AOP to degrade all target micro-pollutants except primidone. On the other hand, the oxidation performance of pharmaceuticals by other ozone-based AOPs followed the order H 2 O 2 /O 3 /UV > O 3 /UV > O 3 . UV/Cl 2 process outcompeted UV/H 2 O 2 only for the removal of trimethoprim and sulfamethoxazole. Correlations between the removal of pharmaceuticals and spectroscopic indexes (PARAFAC components and UV 254 ) had unique regression parameters for each compound, surrogate parameter and oxidation process. Particularly, a diverse PARAFAC component for each investigated AOP resulted to be the most sensitive surrogate parameter able to monitor small changes of pharmaceuticals removal., 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.)

Environmental pollution has intensified and accelerated due to a steady increase in the number of industries, and finding methods to remove hazardous contaminants, which can be typically divided into inorganic and organic compounds, have become inevitable. One of the widely used water treatment technologies is adsorption and various kinds of adsorbents for the removal of inorganic and organic contaminants from water have been discovered. Recently, MXene, as an emerging nanomaterial, has gained rapid attention owing to its unique characteristics and various applicability. Particularly, in the area of adsorptive application, MXene and MXene-based adsorbents have shown great potential in a large number of studies. In this regard, a comprehensive understanding of the adsorptive behavior of MXene-based nanomaterials is necessary in order to explain how they remove inorganic and organic contaminants in water. Adsorption by MXene-based adsorbents tends to be highly influenced by not only the physicochemical properties of these adsorbents but also water quality, such as pH value, temperature, background ion, and natural organic matter. Therefore, in this review paper, the effect of various water quality on the adsorption of inorganic and organic contaminants by various types of MXene and MXene-based adsorbents is explored. Furthermore, this review also covers general trends in the synthesis of MXene and regeneration of MXene-based adsorbents in order to assess their stability., 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.)

Since MXenes (a new family of two-dimensional materials) were first produced in 2011, they have become very attractive nanomaterials due to their unique properties and the range of potential industrial applications. Numerous recent studies have discussed the environmental applications of different MXenes in adsorption, catalysis, and membranes. Only a limited number of MXene-based membrane studies have been published to date, and most have discussed only specific MXenes (i.e., Ti 3 C 2 T x ), a small number of solutes (e.g., dyes and inorganic salts), and laboratory-scale short-term experiments under limited water-quality and operational conditions. In addition, to our knowledge, there has been no review of MXene-membrane studies. It is therefore essential to assess the current status of understanding of the performance of these membranes in liquid separation and water purification. Here, a comprehensive literature review is conducted to summarize the current preparation techniques for MXene-based membranes and their applications, particularly in terms of environmental and industrial applications (e.g., water treatment and organic solvent filtration), and to direct future research by identifying gaps in our present understanding. In particular, this review focuses on several key factors, including the effects of preparation techniques on membrane properties, operational conditions, and compound properties that influence liquid separation during MXene-based membrane filtration., 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, magnetic ion exchange (MIEX) resin was evaluated to remove six carboxylic and three sulfonic PFAS at environmentally relevant concentrations (∼300 ng/L) in groundwater with low organic content and aromaticity (0.78 mg/L of dissolved organic carbon, DOC and 0.96 L mg -1 m -1 of specific UV absorbance, SUVA). In order to evaluate PFAS adsorption, the apparent equilibrium constant for PFAS adsorption in a dilute system was derived as an indicator of the adsorption capacity of MIEX. In adsorption of PFAS, hydrophobic interactions induced by difluoromethylene and trifluoromethyl groups are known to be effective. However, the hydrophobic and charge interactions caused by such functional groups are not easily differentiable from each other since both are additive with respect to the chain length. In this study, the total negative atomic charge [∑Q i (-)] was calculated using density functional theory (DFT) calculation and correlated with the apparent equilibrium constants. The negative atomic charge showed better correlation than the hydrophobicity (log D ow at pH 7) of PFAS, suggesting that the charge interaction would be a more plausible role of fluorinated moieties for adsorption in the MIEX process than the hydrophobic interaction. This was also bolstered by the similar adsorption kinetics and equilibrium of PFOS (log D ow  = 3.05) and its less hydrophobic isomer (log D ow  = 2.79), but with almost identical total negative atomic charge (8.05 and 8.06 of ∑Q i (-), respectively). The regeneration efficiency of MIEX was also assessed. Almost complete restoration of PFAS adsorption capacity was achieved after 30 min of a regeneration process with a 10% w/w NaCl solution as a regenerant. The efficient regeneration was attributed to the effective desorption of dissolved organic matter that occupied sorptive sites predominantly., 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 demonstrated statistical profiling consisting of the analysis of variance (ANOVA) and fold change to efficiently identify transformation products of an organic model compound (i.e., carbamazepine, CBZ) in ozonation. To this end, liquid chromatography (LC)-quadrupole time-of-flight mass spectrometry (QTOF-MS) was employed to measure the accurate masses of CBZ transformation products. Subsequently, statistical profiling was applied to differentiating features that are uniquely present in the ozonated samples from those in blanks and control (i.e., CBZ sample without ozonation). The identified transformation products had significant statistical power (i.e., power, 1-β > 0.8) in post hoc power analysis, which suggests that the profiling procedure can be an efficient means of reducing false negative in data analysis. 2-quinazolinone was newly reported here as a tentative transformation of CBZ during ozonation. In addition, a transformation product with one less carbon than CBZ, often called "anomalous" transformation product, was also found. While statistical profiling was applied to a model experiment, such an approach can be further utilized to screen many features with a higher data complexity such as non-targeted screening (NTS) and non-target analysis (NTA) for environmental samples., 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 adsorption breakthrough behavior of nine perfluoroalkyl substances (PFAS) in groundwaters by four bituminous coal-based granular activated carbons (F400, Carbsorb 40, HPC and CMR400) was studied using rapid small-scale column tests (RSSCTs). The half breakthrough bed volume (BV 50 ), an indicator of apparent adsorption capacity, correlated with the hydrophobicity of PFAS at a given pH (i.e., Log D ow ) for F400, indicating that hydrophobic interaction is important for apparent adsorption capacity of PFAS in groundwater with low dissolved organic concentrations (DOC < 1 mg C/L) and low specific UV absorbances at 254 nm (SUVA 254  < 2 L mg -1 m -1 ). Higher empty bed contact time (EBCT) caused steeper PFAS breakthrough curves with respect to throughput, but did not affect apparent adsorption capacity. Three different sizes of F400 (0.13, 0.17, and 0.20 mm) exhibited similar breakthrough profiles of PFAS, indicating that the intraparticle diffusivity was independent of adsorbent diameter in the given conditions. Among the tested carbons, the positively charged adsorbents (F400, HPC, and CMR400) showed higher apparent adsorption capacities for hydrophilic (Log D ow at pH 7 < 0) and marginally hydrophobic PFAS (Log D ow at pH 7 between 0 and 1) than the negatively charged adsorbent (Carbsorb 40). In addition, activated carbons with higher micropore surface areas exhibited higher apparent adsorption capacities of hydrophilic and marginally hydrophobic PFAS among the positively-charged activated carbons, whereas the mesoporous carbon (HPC) exhibited an increasingly larger adsorption capacity for more hydrophobic PFAS compared to the microporous carbon (F400) at a later breakthrough possibly due to less pore blockage., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Iodinated contrast media (ICMs) are a class of X-ray contrast media worldwide utilized for radiographic procedures. Since they cannot be removed efficiently during water treatment, they can be found in surface and groundwater. In this work, a rapid and sensitive direct injection liquid chromatography-tandem (LC-MS/MS) method for the simultaneous analysis of seven ICMs media (iopamidol, ioxitalamic acid, diatrizoic acid, iothalamic acid, iohexol, iomeprol and iopromide) in complex aqueous matrices has been developed and validated. The MDLs for the analytes ranged from 0.7 to 21 ng L -1 in ultrapure water, and recoveries ranged from 86 to 100% in drinking water, 85-103% in groundwater and 84-105% in WWTP effluent. A stereo-isomer for iopromide was separated. This analytic method was applied to investigate the removal of target ICMs by low pressure ultra violet light (LPUV) advanced oxidation processes with three oxidants, hydrogen peroxide, free chlorine and monochloramine in groundwater. Results showed that the addition of oxidants did not enhance attenuation of ICMs, since fluence-based decay apparent rate constants were similar (K UV  = 3.2 × 10 -3 , K UV-Cl2  = 3.6 × 10 -3 and K UV-NH2  = 3.4 × 10 -3 10 -3  cm 2  mJ -1 ). This yielded direct photolysis is the main mechanism to attenuate target ICMs., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Fe(II)/UV/chlorine was promoted as a pretreatment strategy for UF membrane to mitigate membrane fouling induced from different organic fractions. This treatment could be an emerging alternative prior to UF process attributed to the coupled role of oxidation and coagulation. To obtain a comprehensive understanding of fouling reduction, the influence of Fe(II)/UV/chlorine process on the characteristics of various feed solutions was inspected, including humic acid (HA), bovine serum albumin (BSA), sodium alginate (SA) and their mixture (HSB). The results suggested that Fe(II)/UV/chlorine process exhibited notable performance on membrane fouling control compared to Fe(II) coagulation alone. With the UV exposure of 720 mJ/cm 2 , the certain dose of Fe(II) and chlorine (15 μM and 2 mg/L) effectively prevented the rapid development of fouling caused by the single organic fractions and their mixture. And the increased dosage promoted the performance of membrane fouling mitigation. The reduction of organic loadings and characteristics change of feed water took the main responsibility for the fouling alleviation. The properties of membrane fouling and their correlation with feed water qualities were analyzed. The results and insight analysis were supposed to evaluate and predict the effectiveness of fouling control when the feed solutions were pretreated by Fe(II)/UV/chlorine process according to various compositions and characteristics of the organic fractions., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

A ranking system for monitoring-based process control was developed to select indicator compounds that can predict the attenuation of a broader range of trace organic compounds (TOrCs) in reclaimed water by low pressure (LP) and medium pressure (MP)-UV advanced oxidation processes (AOPs). The selected TOrCs were classified into three groups depending on their relative reactivity to UV direct photolysis and •OH oxidation. Group 1 includes the photolabile TOrCs, which are easily photodegraded with no additional oxidants by either LP or MP-UV light and include acesulfame, diclofenac, and sulfamethoxazole. Group 2 consists of the moderate photodegradable compounds with high reactivity of •OH oxidation, which include benzotriazole, fluoxetine, and hydrochlorothiazide as indicator compounds for assessing LP-UV AOP and propranolol, diltiazem, and diphenhydramine for MP-UV AOP. Group 3 is photo-resistant TOrCs, but highly reactive with •OH radicals and includes carbamazepine and DEET as appropriate indicator compounds. Therefore, the proposed ranking system is expected to provide a comprehensive monitoring tool to water reuse utilities for prioritizing a list of indicators to assess the treatment efficacy of UV AOPs that allows for subsequent operational control to achieve the treatment goal. This is the first strategic framework and guidelines for building a customizable tool of process control that depend on the site-specific occurrence profile of wastewater effluents and the UV system (UV lamp spectral output and power density)., (Copyright © 2019. Published by Elsevier Ltd.)

As freshwater sources continue to be influenced by wastewater effluents, there is a dire need to develop advanced water treatment processes capable of treating the wastewater-derived contaminants, especially for pharmaceutically active compounds (PhACs). Ultraviolet light (UV) combined with calcium peroxide (CaO 2 ) as an advanced oxidation process (AOP) to attenuate five widespread PhACs (carbamazepine (CBZ), primidone (PMD), phenobarbital (PBB), thiamphenicol (TAP) and florfenicol (FF)) was investigated in this paper. The degradation of these compounds followed pseudo-first-order kinetics (R 2  > 0.96). The optimum CaO 2 dosage was 0.1 g L -1 and lower initial contaminants concentration was beneficial to their degradation. The UV/CaO 2 treatment of test PhACs was attributed to the combination of UV/H 2 O 2 and UV-base-photolysis (UV/Ca(OH) 2 ), and the degradation mechanism was recognized as both UV direct photolysis and indirect photolysis caused by reactive radicals (•OH, triplet states of dissolved organic matter ( 3 DOM*), and 1 O 2 ). Furthermore, the tentative transformation pathways of the five PhACs were proposed based on the detected intermediates and the degradation mechanisms. The final products of inorganic carbon and nitrogen indicate UV/CaO 2 treatment can significantly mineralize test PhACs. Also, the CaO 2 addition significantly reduced the energy consumption of UV irradiation according to electrical energy per order. The effective removal of CBZ and PMD in a secondary wastewater effluent by UV/CaO 2 treatment demonstrates the potential use of this AOP technology in advanced treatment of wastewater-derived PhACs., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

In this work, UV and UV/chlorine (UV/Cl) were employed to enhance powdered activated carbon (PAC) adsorption pretreatment prior to ultrafiltration process for algae-contaminated surface water treatment. Their performance on membrane fouling mitigation and organic pollutant rejection was systematically evaluated. A comparative experiment was conducted under varying pollution degrees of algal extracellular organic matter (EOM) contamination in surface river water. The results indicated that UV/PAC and UV/Cl/PAC pretreatment effectively enhanced the removal of dissolved organic carbon (DOC) and UV-absorbing at 254 nm (UV 254 ). The characteristics of feed water after pretreatments were investigated through apparent molecular-weight (MW) distribution and fluorescence parallel factor analysis (PARAFAC). In regard to membrane fouling mitigation, UV/Cl/PAC noticeably decreased reversible and irreversible fouling resistance simultaneously and UV/PAC preferred reducing reversible membrane fouling. Combined fouling modeling was operated to scrutinize the fouling mitigation mechanisms and standard pore blocking was proved to be dominant during the filtration process. Moreover, the UV/Cl and UV/Cl/PAC pretreatments were proved positive for emerging micropollutants degradation and disinfection by-products formation potential reduction. The results suggested that UV and UV/Cl are likely strategies to enhance the efficiency of PAC adsorption pretreatments prior to ultrafiltration during algae-contaminated water treatment., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Treated wastewater (TWW) constitutes a sustainable water resource and has been used for fish culture in some countries around the world, although there are no comprehensive data on the effect of TWW on fish growth and health in the context of aquaculture production. Our objectives were to examine how fish culture in TWW affected fish growth and fitness, as well as compliance with the international standards for safe consumption. Guppy (Poecilia reticulata) fingerlings were reared in 0%, 50% and 100% tertiary TWW (TTWW), from the age of five days, for a period of four months. In water analyses, 33 out of 67 tested organic micropollutants (OMPs) were detected in the TTWW samples at least once, at concentrations that are typically reported in domestic TTWW. Fish survival ranged between 77-80% and did not differ between treatment groups. Fish growth and mortality following challenge infection with Tetrahymena sp. (which ranged between 64-68%), were similar among treatment groups. Of tested immunological parameters, lysozyme and anti-protease was similar among treatments while complement activity was highest in the 50% TTWW-reared fish. No abnormalities were observed in the histopathological analysis. Levels of heavy metals, polychlorinated-biphenyls (PCBs) and organochlorines (OCs) in fish were below the detection limit and below the Food and Agriculture Organization of the United Nations (FAO) and the European Union EU maximal permitted levels in food fish. Results suggest that the yield of fish grown in TTWW is potentially similar to that in freshwater, and the produced fish comply with the standards of consumer safety. The results are in line with previous studies that examined the feasibility of TWW-fed aquaculture., Competing Interests: The authors have declared that no competing interests exist.

Formation of genotoxic byproducts during different ultraviolet (UV) -related water/wastewater treatment processes (including medium pressure (MP) UV oxidation, LP UV oxidation, chlorination, biological activated carbon (BAC) treatment, H 2 O 2 oxidation, and two or more combined processes) was investigated by Ames fluctuation test using Salmonella strains TA98 and TA100 with and without rat liver enzyme extract S9. Byproducts responsible for genotoxicity were identified. The results showed that MP UV can induce mutagenicity and LP UV treatment does not induce mutagenicity. H 2 O 2 oxidation could degrade part of genotoxic compounds. Compared with chlorination, BAC treatment is more effective in removing genotoxicity. Mutagenicity was found mostly in samples tested with TA100 instead of TA98, especially with TA100 without S9, indicating that guanosine and/or cytosine adducts contribute to mutation or toxicological effects in MP UV treated samples. Potential genotoxic byproducts were selected, most of which were nitrogenous organic compounds with more than 10 carbon atoms. Nitrosamines and histidine were excluded from potential genotoxic candidates. The results could contribute to evaluation of mutagenicity of various UV-based water treatment processes., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Various graphene-based nanoadsorbents, including graphenes, graphene oxides, reduced graphene oxides, and their nanocomposites, have been widely studied as potential adsorbents due to their unique physicochemical properties, such as structural variability, chemical strength, low density, and the possibility of large scale fabrication. Adsorption mechanisms are governed largely by the physicochemical properties of contaminants, the characteristics of nanoadsorbents, and background water quality conditions. This review summarizes recent comprehensive studies on the removal of various inorganic (mainly heavy metals) and organic contaminants by graphene-based nanoadsorbents, and also discusses valuable information for applications of these nanoadsorbents in water and wastewater treatment. In particular, the aqueous removal of various contaminants was reviewed to (i) summarize the general adsorption capacities of various graphene-based nanoadsorbents for the removal of different inorganic and organic contaminants, (ii) evaluate the effects of key water quality parameters such as pH, temperature, background major ions/ionic strength, and natural organic matter on adsorption, (iii) provide a comprehensive discussion of the mechanisms that influence adsorption on these nanoadsorbents, and (iv) discuss the potential regeneration and reusability of nanoadsorbents. In addition, current challenges and future research needs for the removal of contaminants by graphene-based nanoadsorbents in water treatment processes are discussed briefly., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

This study investigated, using rapid small-scale column testing, the breakthrough of dissolved organic matter (DOM) and eleven emerging organic contaminants (EOCs) during granular activated carbon (GAC) filtration of different water qualities, including wastewater, surface water and synthetic water (riverine organic matter dissolved in deionized water). Fluorescing organic matter was better adsorbed than UV absorbance at 254 nm (UV 254 ) and dissolved organic carbon (DOC) in all tested water. Furthermore, highest adsorption of DOM (in terms of DOC, UV 254 and fluorescence) was observed during wastewater filtration. UV absorbing DOM had fast and similar breakthrough in surface water and synthetic water, whereas fluorescence breakthrough was very rapid only in synthetic water. PARAFAC modeling showed that different fluorescing components were differently adsorbed during GAC process. Particularly, fluorescing components with maxima intensity at higher excitation wavelengths, which are corresponding to humic-like fluorescence substances, were better removed than other components in all waters. As opposed to DOM, EOCs were better adsorbed during synthetic water filtration, whereas the fastest EOCs breakthrough was observed during filtration of wastewater, which was the water that determined the highest carbon fouling. Exception was represented by long-chained perfluoroalkylated substances (i.e., PFOA, PFDA and PFOS). Indeed, adsorption of these compounds resulted independent of water quality. In this study was also investigated the applicability of UV 254 and fluorescing PARAFAC components to act as surrogates in predicting EOCs removal by GAC in different water matrices. Empirical linear correlation for the investigated EOCs were determined with UV 254 and fluorescing components in all water qualities. However, fluorescence measurements resulted more sensitive than UV 254 to predict EOC breakthrough during GAC adsorption. When the data from all water qualities was combined, good correlations between the microbial humic-like PARAFAC component and EOC removals were still observed and they resulted independent of water quality if considering only real water matrices (wastewater and surface water). On the contrary, correlations between EOC removals and UV 254 removals were independent of water quality when combining data of surface waters and synthetic water, but a different correlation model was needed to predict EOCs breakthrough in wastewater., (Copyright © 2018. Published by Elsevier Ltd.)

Reverse osmosis (RO)-based desalination and advanced water purification facilities have inherent challenges associated with concentrate management and disposal. Although enhanced permeate recovery and concentrate minimization are desired, membrane scaling due to inorganic constituents, such as silica, calcium, phosphate, and iron, hinders the process. To solve this problem, a new diatom-based photobiological process has been developed to remove these scaling constituents by biological uptake and precipitation. In this study, RO concentrate samples were collected from a full-scale advanced water reclamation facility in California and were treated in 3.8 and 57 L photobioreactors inoculated with a brackish water diatom  Pseudostaurosira trainorii PEWL001 using light-emitting diode bulbs or natural sunlight as a light source. The photobiological treatment removed 95% of reactive silica and 64% of calcium and enabled additional water recovery using a secondary RO at a recovery rate up to 66%. This represents 95% overall recovery, including 85% recovery in the primary RO unit. In addition to the scaling constituents, the photobiological treatment removed 12 pharmaceuticals and personal care products, as well as N-nitrosodimethylamine, from RO concentrate samples primarily via photolysis. This novel approach has a strong potential for application to brackish water desalination and advanced water purification in arid and semiarid areas.

Wastewater reclamation has increasingly become popular to secure potable water supply. Low-pressure membrane processes such as microfiltration (MF) and ultrafiltration (UF) play imperative roles as a barrier of macromolecules for such purpose, but are often limited by membrane fouling. Effluent organic matter (EfOM), including biopolymers and particulates, in secondary wastewater effluents have been known to be major foulants in low-pressure membrane processes. Hence, the primary aim of this study was to investigate the effects of pre-ozonation as a pre-treatment for UF on the membrane fouling caused by EfOM in secondary wastewater effluents for hydrophilic regenerated cellulose (RC) and hydrophobic polyethersulfone (PES) UF membranes. It was found that greater fouling reduction was achieved by pre-ozonation for the hydrophilic RC membrane than the hydrophobic PES membrane at increasing ozone doses. In addition, the physicochemical property changes of EfOM, including biopolymer fractions, by pre-ozonation were systemically investigated. The classical pore blocking model and the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theories were employed to scrutinize the fouling alleviation mechanism by pre-ozonation. As a result, the overarching mechanisms of fouling reduction were attributed to the following key reasons: (1) Ozone degraded macromolecules such as biopolymers like proteins and polysaccharides into smaller fractions, thereby increasing free energy of cohesion of EfOM and rendering them more hydrophilic and stable; (2) pre-ozonation augmented the interfacial free energy of adhesion between foulants and the RC/PES membranes, leading to the increase of repulsions and/or the decrease of attractions; and (3) pre-ozonation prolonged the transition from pore blocking to cake filtration that was a dominant fouling mechanism, thereby reducing fouling., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Ozone oxidation has been demonstrated to be an effective treatment process for the attenuation of trace organic compounds (TOrCs); however, predicting TOrC attenuation by ozone processes is challenging in wastewaters. Since ozone is rapidly consumed, determining the exposure times of ozone and hydroxyl radical proves to be difficult. As direct potable reuse schemes continue to gain traction, there is an increasing need for the development of real-time monitoring strategies for TOrC abatement in ozone oxidation processes. Hence, this study is primarily aimed at developing indicator and surrogate models for the prediction of TOrC attenuation by ozone oxidation. To this end, the second-order kinetic equations with a second-phase R ct value (ratio of hydroxyl radical exposure to molecular ozone exposure) were used to calculate comparative kinetics of TOrC attenuation and the reduction of indicator and spectroscopic surrogate parameters, including UV absorbance at 254 nm (UVA 254 ) and total fluorescence (TF). The developed indicator model using meprobamate as an indicator compound and the surrogate models with UVA 254 and TF exhibited good predictive power for the attenuation of 13 kinetically distinct TOrCs in five filtered and unfiltered wastewater effluents (R 2 values > 0.8). This study is intended to help provide a guideline for the implementation of indicator/surrogate models for real-time monitoring of TOrC abatement with ozone processes and integrate them into a regulatory framework in water reuse., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The removal of trace organic compounds (TOrCs) is of growing interest in water research and society. Powdered activated carbon (PAC) has been proven to be an effective method of removal for TOrCs in water, with the degree of effectiveness depending on dosage, contact time, and activated carbon type. In this study, the attenuation of TOrCs in three different secondary wastewater effluents using four PAC materials was studied in order to elucidate the effectiveness and efficacy of PAC for TOrC removal. With the notable exception of hydrochlorothiazide, all 14 TOrC indicators tested in this study exhibited a positive correlation of removal rate with their log Dow values, demonstrating that the main adsorption mechanism was hydrophobic interaction. As a predictive model, the modified Chick-Watson model, often used for the prediction of microorganism inactivation by disinfectants, was applied. The applied model exhibited good predictive power for TOrC attenuation by PAC in wastewater. In addition, surrogate models based upon spectroscopic measurements including UV absorbance at 254 nm and total fluorescence were applied to predict TOrC removal by PAC. The surrogate model was found to provide an excellent prediction of TOrC attenuation for all combinations of water quality and PAC type included in this study. The success of spectrometric parameters as surrogates in predicting TOrC attenuation by PAC are particularly useful because of their potential application in real-time on-line sensor monitoring and process control at full-scale water treatment plants, which could lead to significantly reduced operator response times and PAC operational optimization., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The presence of pharmaceuticals, hormones, pesticides and industrial contaminants collectively termed as trace organic compounds (TOrCs) in wastewater has been well-documented in USA, Europe, China and other regions. However, data from India, the second most populous country in the world is severely lacking. This study investigated the occurrence and concentrations of twenty-two indicator TOrCs at three wastewater treatment plants (WWTPs) in South India serving diverse communities across three sampling campaigns. Samples were collected after each WWTP treatment unit and removal efficiencies for TOrCs were determined. Eleven TOrCs were detected in every sample from every location at all sites, while only five TOrCs were detected consistently in effluent samples. Caffeine was present at greatest concentration in the influent of all three plants with average concentrations ranging between 56 and 65μg/L. In contrast, the x-ray contrast media pharmaceutical, iohexol, was the highest detected compound on average in the effluent at all three WWTPs (2.1-8.7μg/L). TOrCs were not completely removed in the WWTPs with removal efficiencies being compound specific and most of the attenuation being attributed to the biological treatment processes. Caffeine and triclocarban were well removed (>80%), while other compounds were poorly removed (acesulfame, sucralose, iohexol) or maybe even formed (carbamazepine) within the WWTPs. The effluent composition of the 22 TOrCs were similar within the three WWTPs but quite different to those seen in the US, indicating the importance of region-specific monitoring. Diurnal trends indicated that variability is compound specific but trended within certain classes of compounds (artificial sweeteners, and pharmaceuticals). The data collected on TOrCs from this study can be used as a baseline to identify potential remediation and regulatory strategies in this understudied region of India., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

UV/H2O2 processes can be applied to improve the quality of effluents from municipal wastewater treatment plants by attenuating trace organic contaminants (micropollutants). This study presents a kinetic model based on UV photolysis parameters, including UV absorption rate and quantum yield, and hydroxyl radical (·OH) oxidation parameters, including second-order rate constants for ·OH reactions and steady-state ·OH concentrations, that can be used to predict micropollutant abatement in wastewater. The UV/H2O2 kinetic model successfully predicted the abatement efficiencies of 16 target micropollutants in bench-scale UV and UV/H2O2 experiments in 10 secondary wastewater effluents. The model was then used to calculate the electric energies required to achieve specific levels of micropollutant abatement in several advanced wastewater treatment scenarios using various combinations of ozone, UV, and H2O2. UV/H2O2 is more energy-intensive than ozonation for abatement of most micropollutants. Nevertheless, UV/H2O2 is not limited by the formation of N-nitrosodimethylamine (NDMA) and bromate whereas ozonation may produce significant concentrations of these oxidation byproducts, as observed in some of the tested wastewater effluents. The combined process of O3/H2O2 followed by UV/H2O2, which may be warranted in some potable reuse applications, can achieve superior micropollutant abatement with reduced energy consumption compared to UV/H2O2 and reduced oxidation byproduct formation (i.e., NDMA and/or bromate) compared to conventional ozonation.

Numerous studies have identified the presence and bioactivity of glucocorticoid receptor (GR) active substances in water; however, the identification and activity-balance of GR compounds remained elusive. This study determined the occurrence and attenuation of GR bioactivity and closed the balance by determining those substances responsible. The observed in vitro GR activity ranged from 39 to 155 ng dexamethasone-equivalent/L (ng Dex-EQ/L) in the secondary effluents of four wastewater treatment plants. Monochromatic ultraviolet light of 80 mJ/cm(2) disinfection dose was efficient for GR activity photolysis, whereas chlorination could not appreciably attenuate the observed GR activity. Ozonation was effective only at relatively high dose (ozone/TOC 1:1). Microfiltration membranes were not efficient for GR activity attenuation; however, reverse osmosis removed GR activity to levels below the limits of detection. A high-sensitivity liquid chromatography with tandem mass spectrometry (LC-MS/MS) method was then developed to screen 27 GR agonists. Twelve were identified and quantified in effluents at summed concentrations of 9.6-21.2 ng/L. The summed Dex-EQ of individual compounds based on their measured concentrations was in excellent agreement with the Dex-EQ obtained from bioassay, which demonstrated that the detected glucocorticoids can entirely explain the observed GR bioactivity. Four synthetic glucocorticoids (triamcinolone acetonide, fluocinolone acetonide, clobetasol propionate, and fluticasone propionate) predominantly accounted for GR activity. These data represent the first known publication where a complete activity balance has been determined for GR agonists in an aquatic environment.

Many modern techniques exist for the degradation of organic pollutants in water. Numerous treatment processes which utilize the formation of hydroxyl radicals for oxidation of pollutants have been studied thoroughly. In this study, a three pronged approach has been used to characterize and understand the effect of two distinct acoustic frequencies (37 kHz and 1 MHz) on cavitation behavior. Correlation of this behavior with sonolysis of a target phenol pollutant is described. Hydroxyl radical capture, hydrophone, and microelectrode studies in this work show that megasonic frequencies are more effective for generation of hydroxyl radicals and stable cavitation events than ultrasonic frequencies. UV absorption and fluorescence measurements confirm that the combination of ultrasonic sonolysis with a Fenton reagent achieved complete degradation of p-cresol at 50 mg/L in about 30 min. Cost estimates have been made for different sonication processes and compared with traditional advanced oxidation processes., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The presence of perfluorocarboxylic acids (PFCAs) in source and finished drinking waters is a concern with studies showing bioaccumulation and adverse toxicological effects in wildlife and potentially humans. Per/Polyfluoroalkyl substances (PFAS) such as fluorotelomer alcohols have been identified as precursors for PFCAs in biological pathways. In this study, we investigated the fate of 6:2 and 8:2 homologues of the fluorotelomer unsaturated carboxylic acids (FTUCAs) during advanced oxidation process (AOPs). Results showed 6:2 FTUCA and 8:2 FTUCA transformed into 6-C PFCA (PFHxA) and 8-C PFCA (PFOA) respectively with very little other PFCA formation for all AOPs. The degradation of 6:2 FTUCA and 8:2 FTUCA was greater in the GW compared to SW for the ozone processes but similar for UV/H2O2. The formation of n-C PFCA followed O3>O3/H2O2 at same dose and UV/H2O2 had much lower formation at the doses tested. Non-targeted analysis with the LC-MS-qTOF indicated the production of other PFCAs which contribute to the total mass balance, although no intermediate product was discovered indicating a rapid and direct transformation from the FTUCAs to the PFCAs and/or significant volatilization of intermediates. With the use of AOPs essential to water reuse treatment schemes, this work raises concerns over the risk of potential formation of PFCAs in the treatment and their adverse health effects in finished drinking water., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

In vitro bioassays have shown promise as water quality monitoring tools. In this study, four commercially available in vitro bioassays (GeneBLAzer(®) androgen receptor (AR), estrogen receptor-alpha (ER), glucocorticoid receptor (GR) and progesterone receptor (PR) assays) were adapted to screen for endocrine active chemicals in samples from two recycled water plants. The standardized protocols were used in an interlaboratory comparison exercise to evaluate the reproducibility of in vitro bioassay results. Key performance criteria were successfully achieved, including low background response, standardized calibration parameters and high intra-laboratory precision. Only two datasets were excluded due to poor calibration performance. Good interlaboratory reproducibility was observed for GR bioassay, with 16-26% variability among the laboratories. ER and PR bioactivity was measured near the bioassay limit of detection and showed more variability (21-54%), although interlaboratory agreement remained comparable to that of conventional analytical methods. AR bioassay showed no activity for any of the samples analyzed. Our results indicate that ER, GR and PR, were capable of screening for different water quality, i.e., the highest bioactivity was observed in the plant influent, which also contained the highest concentrations of endocrine active chemicals measured by LC-MS/MS. After advanced treatment (e.g., reverse osmosis), bioactivity and target chemical concentrations were both below limits of detection. Comparison of bioassay and chemical equivalent concentrations revealed that targeted chemicals accounted for ≤5% of bioassay activity, suggesting that detection limits by LC-MS/MS for some chemicals were insufficient and/or other bioactive compounds were present in these samples. Our study demonstrated that in vitro bioassays responses were reproducible, and can provide information to complement conventional analytical methods for a more comprehensive water quality assessment., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

A combination of surrogate parameters and indicator compounds were measured to predict the removal efficiency of trace organic compounds (TOrCs) using low pressure (LP)-UV/H2O2 advanced oxidation process (AOP), engaged with online sensor-based monitoring system. Thirty-nine TOrCs were evaluated in two distinct secondary wastewater effluents in terms of estimated photochemical reactivity, as a function of the rate constants of UV direct photolysis (kUV) and hydroxyl radical (OH) oxidation (kOH). The selected eighteen TOrCs were classified into three groups that served as indicator compounds: Group 1 for photo-susceptible TOrCs but with minor degradation by OH oxidation (diclofenac, fluoxetine, iohexol, iopamidol, iopromide, simazine and sulfamethoxazole); Group 2 for TOrCs susceptible to both direct photolysis and OH oxidation (benzotriazole, diphenhydramine, ibuprofen, naproxen and sucralose); and Group 3 for photo-resistant TOrCs showing dominant degradation by OH oxidation (atenolol, carbamazepine, DEET, gemfibrozil, primidone and trimethoprim). The results indicate that TOC (optical-based measurement), UVA254 or UVT254 (UV absorbance or transmittance at 254 nm), and total fluorescence can all be used as suitable on-line organic surrogate parameters to predict the attenuation of TOrCs. Furthermore, the automated real-time monitoring via on-line surrogate sensors and equipped with the developed degradation profiles between sensor response and a group of TOrCs removal can provide a diagnostic tool for process control during advanced treatment of reclaimed waters., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

This study investigated the applicability of bulk organic parameters like dissolved organic carbon (DOC), UV absorbance at 254 nm (UV254), and total fluorescence (TF) to act as surrogates in predicting trace organic compound (TOrC) removal by granular activated carbon in water reuse applications. Using rapid small-scale column testing, empirical linear correlations for thirteen TOrCs were determined with DOC, UV254, and TF in four wastewater effluents. Linear correlations (R(2) > 0.7) were obtained for eight TOrCs in each water quality in the UV254 model, while ten TOrCs had R(2) > 0.7 in the TF model. Conversely, DOC was shown to be a poor surrogate for TOrC breakthrough prediction. When the data from all four water qualities was combined, good linear correlations were still obtained with TF having higher R(2) than UV254 especially for TOrCs with log Dow>1. Excellent linear relationship (R(2) > 0.9) between log Dow and the removal of TOrC at 0% surrogate removal (y-intercept) were obtained for the five neutral TOrCs tested in this study. Positively charged TOrCs had enhanced removals due to electrostatic interactions with negatively charged GAC that caused them to deviate from removals that would be expected with their log Dow. Application of the empirical linear correlation models to full-scale samples provided good results for six of seven TOrCs (except meprobamate) tested when comparing predicted TOrC removal by UV254 and TF with actual removals for GAC in all the five samples tested. Surrogate predictions using UV254 and TF provide valuable tools for rapid or on-line monitoring of GAC performance and can result in cost savings by extended GAC run times as compared to using DOC breakthrough to trigger regeneration or replacement., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Ozone doses normalized to the dissolved organic carbon concentration were applied to the primary influent, primary effluent, and secondary effluent of a wastewater treatment plant producing water destined for potable reuse. Results showed the most N-Nitrosodimethylamine (NDMA) production from primary effluent, and the recycle streams entering the primary clarifiers were identified as the main source of NDMA precursors. The degradation of aminomethylated polyacrylamide (Mannich) polymer used for sludge treatment was a significant cause of precursor occurrence. A strong correlation between NDMA formation and ammonia concentration was found suggesting an important role of ammonia oxidation on NDMA production. During ozonation tests in DI water using dimethylamine (DMA) as model precursor, the NDMA yield significantly increased in the presence of ammonia and bromide due to the formation of hydroxylamine and brominated nitrogenous oxidants. In addition, NDMA formation during ozonation of dimethylformamide (DMF), the other model precursor used in this study, occurred only in the presence of ammonia, and it was attributable to the oxidation of DMF by hydroxyl radicals. Filtered wastewater samples (0.7 μm) produced more NDMA than unfiltered samples, suggesting that ozone reacted with dissolved precursors and supporting the hypothesis of polymer degradation. Particularly, the total suspended solids content similarly affected NDMA formation and the UV absorbance decrease during ozonation due to the different ozone demand created in filtered and unfiltered samples.

The use of advanced oxidation processes (AOP) are expected to increase for removal of emerging contaminants and pathogens from drinking water. In this study, the performance of a small community ultraviolet light reactor in combination with hydrogen peroxide (H2O2) for MS2 coliphage inactivation with two different flow rate conditions of 1 gal/min (gpm) and 2 gpm was evaluated. Following UV radiation, MS2 showed a reduction of 5.3-5.8 log10 when quantified with cultural plaque counts, whereas corresponding quantitative polymerase chain reaction (qPCR) data showed only a 1.7-2.8 log10 reduction in viral RNA copy number. When H2O2 was added at either 2.5 or 5 ppm with UV at both flow rate conditions, enhanced MS2 inactivation occurred with a more than 7 log10 reduction observed via plaque counts, indicating that all added MS2 had been inactivated, since no plaques were formed after incubation at 37 °C for 24 h. In contrast, qPCR only showed a corresponding 3-4 log10 reduction in viral RNA copy number. This research also sheds light on the inactivation of MS2 with ultraviolet light and in the presence of hydroxyl radicals and provides a practical use of qPCR to detect MS2 concentration following advanced oxidation relative to traditional plaque methodology; however qPCR detection overestimates the true number of infective virus.

The performance of ozonation in wastewater depends on water quality and the ability to form hydroxyl radicals (·OH) to meet disinfection or contaminant transformation objectives. Since there are no on-line methods to assess ozone and ·OH exposure in wastewater, many agencies are now embracing indicator frameworks and surrogate monitoring for regulatory compliance. Two of the most promising surrogate parameters for ozone-based treatment of secondary and tertiary wastewater effluents are differential UV(254) absorbance (ΔUV(254)) and total fluorescence (ΔTF). In the current study, empirical correlations for ΔUV(254) and ΔTF were developed for the oxidation of 18 trace organic contaminants (TOrCs), including 1,4-dioxane, atenolol, atrazine, bisphenol A, carbamazepine, diclofenac, gemfibrozil, ibuprofen, meprobamate, naproxen, N,N-diethyl-meta-toluamide (DEET), para-chlorobenzoic acid (pCBA), phenytoin, primidone, sulfamethoxazole, triclosan, trimethoprim, and tris-(2-chloroethyl)-phosphate (TCEP) (R(2) = 0.50-0.83) and the inactivation of three microbial surrogates, including Escherichia coli, MS2, and Bacillus subtilis spores (R(2) = 0.46-0.78). Nine wastewaters were tested in laboratory systems, and eight wastewaters were evaluated at pilot- and full-scale. A predictive model for OH exposure based on ΔUV(254) or ΔTF was also proposed., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

An ozone and ozone/peroxide oxidation process was evaluated at pilot scale for trace organic contaminant (TOrC) mitigation and NDMA formation in both drinking water and water reuse applications. A reverse osmosis (RO) pilot was also evaluated as part of the water reuse treatment train. Ozone/peroxide showed lower electrical energy per order of removal (EEO) values for TOrCs in surface water treatment, but the addition of hydrogen peroxide increased EEO values during wastewater treatment. TOrC oxidation was correlated to changes in UV(254) absorbance and fluorescence offering a surrogate model for predicting contaminant removal. A decrease in N-nitrosodimethylamine (NDMA) formation potential (after chloramination) was observed after treatment with ozone and ozone/peroxide. However, during spiking experiments with surface water, ozone/peroxide achieved limited destruction of NDMA, while in wastewaters net direct formation of NDMA of 6-33 ng/L was observed after either ozone or ozone/peroxide treatment. Once formed during ozonation, NDMA passed through the subsequent RO membranes, which highlights the significance of the potential for direct NDMA formation during oxidation in reuse applications., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

In an effort to validate the use of ozone for contaminant oxidation and disinfection in water reclamation, extensive pilot testing was performed with ozone/H(2)O(2) and biological activated carbon (BAC) at the Reno-Stead Water Reclamation Facility in Reno, Nevada. Three sets of samples were collected over a five-month period of continuous operation, and these samples were analyzed for a suite of trace organic contaminants (TOrCs), total estrogenicity, and several microbial surrogates, including the bacteriophage MS2, total and fecal coliforms, and Bacillus spores. Based on the high degree of microbial inactivation and contaminant destruction, this treatment train appears to be a viable alternative to the standard indirect potable reuse (IPR) configuration (i.e., membrane filtration, reverse osmosis, UV/H(2)O(2), and aquifer injection), particularly for inland applications where brine disposal is an issue. Several issues, including regrowth of coliform bacteria in the BAC process, must be addressed prior to full-scale implementation., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

To respond to concerns associated with wastewater-derived contaminants water utilities are looking for new approaches for monitoring trace organic chemicals in conventional and advanced water treatment processes. This study examines the use of a combination of surrogate parameters and indicator compounds tailored to monitor the removal efficiency of advanced oxidation processes employed by treatment plants engaged in indirect potable water reuse programs. Potential surrogate parameters and indicator compounds, identified by reviewing previous publications and classified by their structural properties, were tested in pilot- and full-scale treatment systems. Dilantin, DEET, meprobamate, and iopromide are good indicators to assess optimized oxidation conditions while ozonating tertiary-treated wastewaters. UVA reduction, ozone byproduct formation, such as simple organic acids, and ozone exposure correlated with "sweet spot" compounds, where ozone exposure correlated with trace organic removal across five tertiary-treated wastewaters. Findings indicate that the proposed framework can serve as a conservative monitoring approach for advanced oxidation processes as well as other indirect potable reuse processes to ensure proper removal of identified and unidentified wastewater-derived organic contaminants, to detect failures in system performance, and is protective of public health.

The effective removal of emerging contaminants of concern (ECCs) such as endocrine-disrupting chemicals, pharmaceutically active compounds, personal care products, and flame retardants is a desirable water treatment goal. In this study, one activated carbon, one carbonaceous resin, and two high-silica zeolites were studied to evaluate their effectiveness for the removal of an ECC mixture from lake water. Adsorption isotherm experiments were performed with a mixture of 28 ECCs at environmentally relevant concentrations ( approximately 200-900 ng/L). Among the tested adsorbents, activated carbon was the most effective, and activated carbon doses typically used for taste and odor control in drinking water (<10 mg/L) were sufficient to achieve a 2-log removal for most of the tested ECCs. The carbonaceous resin was less effective than the activated carbon because this adsorbent had a smaller volume of pores in the size range required for the adsorption of many ECCs ( approximately 6-9A). For the removal of ECC mixture constituents, zeolites were less effective than the carbonaceous adsorbents. Because zeolites contain pores of uniform size and shape, a few of the tested ECCs with matching pore size/shape requirements were well removed, but the adsorptive removal of others was negligible, even at zeolite doses of 100 mg/L. The results of this study demonstrate that effective adsorbents for the removal of a broad spectrum of ECCs from water should exhibit heterogeneity in pore size and shape and a large pore volume in the 6-9A size range.

The reduction of ultraviolet (UV) absorbance at 254 nm (UV254) and true color were identified as appropriate surrogates to assess the oxidation of six pharmaceuticals (i.e., carbamazepine, meprobamate, dilantin, primidone, atenolol, and iopromide) during ozonation of wastewater. Three tertiary-treated wastewaters were evaluated during oxidation with ozone (O3) and O3 coupled with hydrogen peroxide (O3/H2O2). The correlation between pharmaceutical oxidation and removal of UV254 was dependent upon the reactivity of each specific compound toward ozone, as measured by the second-order rate constant (k'(O3)). Oxidation of compounds with k'(O3) > 10(3) M(-1) s(-1) correlated well (R2 > 0.73) with UV254 reduction between 0-50%. Oxidation of compounds with apparent k'(O3) < 10 M(-1) s(-1) resulted primarily from hydroxyl radicals and correlated well (R2 > 0.80) with the UV254 reduction of 15-85%. The removal of true color also correlated well (R2 > 0.85) with the oxidation of pharmaceuticals during the ozonation of two wastewaters. These correlations demonstrate that UV254 reduction and true color removal may be used as surrogates to evaluate pharmaceutical oxidation in the presence or absence of dissolved ozone residual during advanced wastewater treatment with O3 or O3/H2O2. The use of online UV254 measurements would allow wastewater utilities to optimize the ozone dose required to meet their specific treatment objectives.

A photocatalytic reactor membrane pilot system, employing UV/TiO(2) photocatalysis, was evaluated for its ability to remove thirty-two pharmaceuticals, endocrine disrupting compounds, and estrogenic activity from water. Concentrations of all compounds decreased following treatment, and removal followed pseudo-first-order kinetics as a function of the amount of treatment. Twenty-nine of the targeted compounds in addition to total estrogenic activity were greater than 70% removed while only three compounds were less than 50% removed following the highest level of treatment (4.24 kW h/m(3)). No estrogenically active transformation products were formed during treatment. Additionally, the unit was operated in photolytic mode (UV only) and photolytic plus H(2)O(2) mode (UV/H(2)O(2)) to determine the relative amount of energy required. Based on the electrical energy per order (EEO), the unit achieved the greatest efficiency when operated in photolytic plus H(2)O(2) mode for the conditions tested.

Disinfection byproduct (DBP) formation in tertiary wastewater was examined after ozonation (O(3)) and advanced oxidation with O(3) and hydrogen peroxide (O(3)/H(2)O(2)). O(3) and O(3)/H(2)O(2) were applied at multiple dosages to investigate DBP formation during coliform disinfection and trace contaminant oxidation. Results showed O(3) provided superior disinfection of fecal and total coliforms compared to O(3)/H(2)O(2). Color, UV absorbance, and SUVA were reduced by O(3) and O(3)/H(2)O(2), offering wastewater utilities a few potential surrogates to monitor disinfection or trace contaminant oxidation. At equivalent O(3) dosages, O(3)/H(2)O(2) produced greater concentrations of assimilable organic carbon (5-52%), aldehydes (31-47%), and carboxylic acids (12-43%) compared to O(3) alone, indicating that organic DBP formation is largely dependent upon hydroxyl radical exposure. Bromate formation occurred when O(3) dosages exceeded the O(3) demand of the wastewater. Bench-scale tests with free chlorine showed O(3) is capable of reducing total organic halide (TOX) formation potential by at least 20%. In summary, O(3) provided superior disinfection compared to O(3)/H(2)O(2) while minimizing DBP concentrations. These are important considerations for water reuse, aquifer storage and recovery, and advanced wastewater treatment applications.

Liquid chromatography/tandem mass spectrometry (LC-MS/MS) with electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) was used to measure the concentrations of 14 pharmaceuticals, 6 hormones, 2 antibiotics, 3 personal care products (PCPs), and 1 flame retardant in surface waters and wastewater treatment plant effluents in South Korea. Tris (2-chloroethyl) phosphate (TCEP), iopromide, naproxen, carbamazepine, and caffeine were quite frequently observed (>80%) in both surface waters and effluents. The analytes of greatest concentration were iopromide, TCEP, sulfamethoxazole, and carbamazepine. However, the primary estrogen hormones, 17alpha-ethynylestradiol and 17beta-estradiol, were rarely detected, while estrone was detected in both surface water and wastewater effluent. The elimination of these chemicals during drinking water and wastewater treatment processes at full- and pilot-scale also was investigated. Conventional drinking water treatment methods were relatively inefficient for contaminant removal, while efficient removal (approximately equal to 99%) was achieved by granular activated carbon (GAC). In wastewater treatment processes, membrane bioreactors (MBR) showed limited target compound removal, but were effective at eliminating hormones and some pharmaceuticals (e.g., acetaminophen, ibuprofen, and caffeine). Membrane filtration processes using reverse osmosis (RO) and nanofiltration (NF) showed excellent removal (>95%) for all target analytes.