The present endocrine disrupting chemicals (EDCs) in wastewater effluents due to incomplete removal during the treatment processes may cause potential ecological and human health risks. This study evaluated the removal and uptake of seven EDCs spiked in two types of wastewater effluent (i.e., ultrafiltration and ozonation) and effluent cultivated with the freshwater green alga Nannochloris sp. In ultrafiltration effluent cultivated with Nannochloris sp. for 7 days, the removal rate of 17β-estradiol (E2), 17α-ethinylestradiol (EE2), and salicylic acid (SAL) was 60%; but Nannochloris sp. did not promote the removal of other EDCs studied. The algal-mediated removal of E2, EE2, and SAL was attributed to photodegradation and biodegradation. Triclosan (TCS) underwent rapid photodegradation regardless of adding algae in the effluent with 63%–100% removal within 7 days. Triclosan was also found associated with algal cells immediately after adding algae, and thus the primary mechanisms involved were photodegradation and bioremoval (i.e., bioadsorption and bioaccumulation). After algal cultivation, TCS still has a bioaccumulation potential to pose high risks within the food web and the endocrine disrupting properties of the residual estrogens in the effluent are not eliminated. Algal cultivation can be exploited to treat wastewater effluents but the removal efficiencies of EDCs highly depend on chemical types.

Knowledge of the heterogeneous distribution of humic substances (HS) reactivities along a continuum of molecular weight (MW) is crucial for the systems where the HS MW is subject to change. In this study, two dimensional correlation spectroscopy combined with size exclusion chromatography (2D-CoSEC) was first utilized to obtain a continuous and heterogeneous presence of copper binding characteristics within bulk HS with respect to MW. HS solutions with varying copper concentrations were directly injected into a size exclusion chromatography (SEC) system with Tris-HCl buffer as a mobile phase. Several validation tests confirmed neither structural disruption of HS nor competition effect of the mobile phase used. Similar to batch systems, fluorescence quenching was observed in the chromatograms over a wide range of HS MW. 2D-CoSEC maps of a soil-derived HS (Elliot soil humic acid) showed the greater fluorescence quenching degrees with respect to the apparent MW on the order of 12500 Da > 10600 Da > 7000 Da > 15800 Da. The binding constants calculated based on modified Stern-Volmer equation were consistent with the 2D-CoSEC results. More heterogeneity of copper binding affinities within bulk HS was found for the soil-derived HS versus an aquatic HS. The traditional fluorescence quenching titration method using ultrafiltered HS size fractions failed to delineate detailed distribution of the copper binding characteristics, exhibiting a much shorter range of the binding constants than those obtained from the 2D-CoSEC. Our proposed technique demonstrated a great potential to describe metal binding characteristics of HS at high MW resolution, providing a clear picture of the size-dependent metal-HS interactions.

The behavior along the potabilization process of 29 pharmaceuticals and 12 drugs of abuse identified from a total of 81 compounds at the intake of a drinking water treatment plant (DWTP) has been studied. The DWTP has a common treatment consisting of dioxychlorination, coagulation/flocculation and sand filtration and then water is splitted in two parallel treatment lines: conventional (ozonation and carbon filtration) and advanced (ultrafiltration and reverse osmosis) to be further blended, chlorinated and distributed. Full removals were reached for most of the compounds. Iopromide (up to 17.2 ng/L), nicotine (13.7 ng/L), benzoylecgonine (1.9 ng/L), cotinine (3.6 ng/L), acetaminophen (15.6 ng/L), erythromycin (2.0 ng/L) and caffeine (6.0 ng/L) with elimination efficiencies ≥94%, were the sole compounds found in the treated water. The advanced treatment process showed a slightly better efficiency than the conventional treatment to eliminate pharmaceuticals and drugs of abuse.

The dissemination of antibiotic resistance (AR) has attracted global attention because of the increasing antibiotic treatment failure it has caused. Through natural transformation, a live bacterium takes up extracellular DNA (exDNA), which facilitates AR dissemination. However, recovery of exDNA from water samples is challenging. In this study, we validated a consecutive ultrafiltration-based protocol to simultaneously recover intracellular DNA (inDNA), dissolved exDNA (Dis_exDNA, dissolved in the bulk water), and adsorbed exDNA (Ads_exDNA, adsorbed to the surfaces of suspended particles). Using hollow fiber ultrafiltration (HFUF), all DNA fractions were concentrated from environmental water samples, after which Dis_exDNA (supernatant) was separated from inDNA and Ads_exDNA (pellets) using centrifugation. Ads_exDNA was washed off from the pellets with proteinase K and sodium phosphate buffer. Dis_exDNA and Ads_exDNA were further concentrated using centrifugal ultrafiltration, from which silica binding was performed. inDNA was extracted from washed pellets with a commercial kit. For inDNA, HFUF showed recovery efficiencies of 96.5 ± 18.5% and 88.0 ± 2.0% for total cells and cultured Escherichia coli, respectively (n = 3). To represent all possible DNA fragments in water environment, exDNA with different lengths (10.0, 4.0, 1.0, and 0.5 kbp) were spiked to test the recovery efficiencies for Dis_exDNA. The whole process achieved 62.2%–62.9% recovery for 10 and 4 kbp exDNA, and 38.8%–44.5% recovery for 1.0 and 0.5 kbp exDNA. Proteinase K treatment enhanced the recovery of Ads_exDNA by 4.0–10.7 times. The protocol was applied to water samples from an urban river in Tokyo, Japan. The abundance of AR genes (ARGs) in inDNA, Dis_exDNA, and Ads_exDNA increased downstream of wastewater treatment plants. ARGs in Ads_exDNA and Dis_exDNA accounted for 1.8%–26.7% and 0.03%–20.9%, respectively, of the total DNA, implying that Ads_exDNA and Dis_exDNA are nonnegligible potential pools for the horizontal transfer of ARGs.

This study investigated the seasonal characterization of dissolved organic matter (DOM) in reclaimed wastewater (RW) with a special focus on dissolved organic nitrogen (DON) from two full-scale municipal wastewater reclamation plants (WRPs) where the produced RW was used to augment urban rivers. Results showed that the concentrations of DON in RW ranged from 0.32 mg/L to 1.21 mg/L. A higher seasonal mean value of DON in RW from both of the WRPs was observed in winter (p < 0.05, ANOVA). DON chemical characteristics analysis, including ultrahigh-resolution mass spectrometry and ultrafiltration fractionation, showed that DON in RW exhibits more lability during winter than during the other three seasons. This finding was also supported by the results of an algal bioassay experiment, in which DON bioavailabilities were 63.7 ± 3.0%, 53.0 ± 5.3%, 49.5 ± 0.5%, and 49.8 ± 0.2% for WRP-A and were 60.8 ± 2.4%, 43.7 ± 2.2%, 41.2 ± 1.7%, and 43.1 ± 1.1% for WRP-B in winter, spring, summer, and autumn, respectively. Accordingly, DON in RW during winter is more prone to stimulate natural algae and microorganisms, which gives rise to eutrophication in urban rivers. At the molecular level, the seasonal changes in DON are not coupled with those of DOC, which highlights the necessity of DON measurement to obtain a comprehensive understanding of the seasonal characteristics of DOM in RW and its effect on wastewater reuse in urban rivers.

Understanding the effect of natural colloidal particles (NCPs) on the photochemistry of organic pollutants is crucial to predict the environmental persistence and fate of them in surface waters, and it is, yet, scarcely elucidated. In this study, the pre-filtered surface water (through a 1 μm capsule filter) from Baiyangdian Lake was further separated into four different size NCPs: F1 (0.65–1.0 μm), F2 (100 kD-0.65 μm), F3 (10–100 kD) and F4 (1–10 kD) by cross-flow ultrafiltration (CFUF), and the photochemical kinetics and mechanisms of ofloxacin (OFL) and enrofloxacin (ENR) were investigated in the presence of those particles under simulated sunlight. Results showed that OFL and ENR underwent both direct and indirect photolysis in F1-F4 solutions, and the observed pseudo first-order rate constants (kobs) for target compounds differed depending on the size of NCPs. Direct photolysis accounted for >50% of the degradation in all cases and was the dominant degradation pathway for the two target antibiotics with the exception of OFL in F1 solution. Except for ENR in both F3 and F4 solutions, nearly all NCPs enhanced the degradation of both target compounds by indirect photolytic pathways, especially in F1 solution that showed the largest reactivity for OFL and ENR, promoting the reactions by 63% and 41%, respectively. The excited state colloidal organic matter (3COM∗) plays a significant role in the indirect photolysis, and the adsorptions of OFL and ENR to NCPs were likely to have a pronounced effect in the photochemistry process. Pearson's correlations analysis showed that the kobs(OFL) was significant positive correlated with binding of Fe (r = 0.963, P < 0.05), and the kobs(ENR) was significant positive correlated with the adsorption percentage of OFL (r = 0.999, P < 0.01).This paper has demonstrated that different size NCPs showed the different photochemical contribution to the reaction rate for OFL and ENR.

To explore the mechanisms and influence factors on the production of 2,4,6-trichloroanisole (2,4,6-TCA) in surface waters, the 2,4,6-TCA formation potential (FP) test was conducted by incubating the real lake water with the addition of 2,4,6-trichlorophenol (2,4,6-TCP) precursor. Besides bacteria and fungi, two common cyanobacteria and algae species, i.e., Chlorella vulgaris and Anabaena flos-aquae, have been proved to have strong capabilities to produce 2,4,6-TCA, which may contribute the high 2,4,6-TCA FP (152.2 ng/L) of lake water. The microbial O-methylation of 2,4,6-TCP precursor is catalyzed by chlorophenol O-methyltransferases (CPOMTs), and their characteristics were identified by adding inductive methyl donors or excluding microorganisms via ultrafiltration. The results indicated both S-adenosyl methionine (SAM) dependent and non-SAM dependent CPOMTs played important roles; extracellular CPOMTs also participated in the biosynthesis of 2,4,6-TCA. Moreover, investigating the effects of various environmental factors revealed initial 2,4,6-TCP processor concentration, temperature, pH and some divalent metal cations (i.e., Mn2+, Mg2+ and Zn2+) had obvious effects on the production of 2,4,6-TCA.

This study aims to investigate factors leading to agglomeration of citrate coated silver (AgNP-Cit), polyvinylpyrrolidone coated AgNPPVP and titanium dioxide (TiO2) nanoparticles in surface waters and wastewater. ENPs (1 mg/L) were spiked to unfiltered, filtered, ultrafiltered (<10 kDa and <1 kDa) samples. Z-average particle sizes were measured after 1 h, 1 day and 1 week. AgNP-PVP was stable in all fractions of the samples and kept their original size around 60 nm over 1 week. Agglomeration of AgNP-Cit and TiO2 was positively correlated with Ca2+ concentration, but dissolved organic carbon concentrations > 2 mg/L contributed to stabilizing these NP. Moreover, agglomeration of AgNP-Cit in the various organic matter fractions showed that high molecular weight organic compounds such as biopolymers provide stabilization in natural water. A generalized scheme for the agglomeration behavior of AgNP-Cit, AgNP-PVP and TiO2 in natural waters was proposed based on their relation with Ca2+, Mg2+ and DOC concentration.

The dissolution of Ag (citrate, gelatin, polyvinylpyrrolidone and chitosan coated), ZnO, CuO and carbon coated Cu nanoparticles (with two nominal sizes each) has been studied in artificial aqueous media, similar in chemistry to environmental waters, for up to 19 days. The dissolved fraction was determined using DGT (Diffusion Gradients in Thin films), dialysis membrane (DM) and ultrafiltration (UF). Relatively small fractions of Ag nanoparticles dissolved, whereas ZnO dissolved nearly completely within few hours. Cu and CuO dissolved as a function of pH. Using DGT, less dissolved Ag was measured compared to UF and DM, likely due to differences in diffusion of organic complexes. Similar dissolved metal concentrations of ZnO, Cu and CuO nanoparticles were determined using DGT and UF, but lower using DM. The results indicate that there is a need to apply complementary techniques to precisely determine dissolution of nanoparticles in aqueous media.

The widespread occurrence and ubiquitous distribution of estrogens, i.e., estrone (E1), estradiol (E2), and estriol (E3) in our water matrices, is an issue of global concern. Public and regulatory authorities are concerned and placing joint efforts to eliminate estrogens and related environmentally hazardous compounds, due to their toxic influences on the environmental matrices, ecology, and human health, even at low concentrations. However, most of the available literature is focused on the occurrence of estrogens in different water environments with limited treatment options. Thus, a detailed review to fully cover the several treatment processes is needed. This review comprehensively and comparatively discusses many physical, chemical, and biological-based treatments to eliminate natural estrogens, i.e., estrone (E1), estradiol (E2), and estriol (E3) and related synthetic estrogens, e.g., 17α-ethinylestradiol (EE2) and other related hazardous compounds. The covered techniques include adsorption, nanofiltration, ultrafiltration, ultrasonication, photocatalysis of estrogenic compounds, Fenton, Fenton-like and photo-Fenton degradation of estrogenic compounds, electro-Fenton degradation of estrogenic compounds, ozonation, and biological methods for the removal of estrogenic compounds are thoroughly discussed with suitable examples. The studies revealed that treatment plants based on chemical and biological approaches are cost-friendly for removing estrogenic pollutants. Further, there is a need to properly monitor and disposal of the usage of estrogenic drugs in humans and animals. Additional studies are required to explore a robust and more advanced oxidation treatment strategy that can contribute effectively to industrial-scale applications. This review may assist future investigations, monitoring, and removing estrogenic compounds from various environmental matrices. In concluding remarks, a way forward and future perspectives focusing on bridging knowledge gaps in estrogenic compounds removal are also proposed.