Drinking water security in Puerto Rico (PR) is increasingly challenged by both regulated and emerging anthropogenic contaminants, which was exacerbated by the Hurricane Maria (HM) due to impaired regional water cycle and damaged water infrastructure. Leveraging the NIEHS PROTECT (Puerto Rico Testsite for Exploring Contamination Threats) cohort, this study assessed the long-term tap water (TW) quality changes from March 2018 to November 2018 after HM in PR, by innovatively integrating two different effect-based quantitative toxicity assays with a targeted analysis of 200 organic and 22 inorganic pollutants. Post-hurricane PR TW quality showed recovery after >6-month period as indicated by the decreased number of contaminants showing elevated average concentrations relative to pre-hurricane samples, with significant difference of both chemical and toxicity levels between northern and southern PR. Molecular toxicity profiling and correlation revealed that the HM-accelerated releases of certain pesticides and PPCPs could exert increased cellular oxidative and/or AhR (aryl hydrocarbon receptor)-mediated activities that may persist for more than six months after HM. Maximum cumulative ratio and adverse outcome pathway (AOP) assessment identified the top ranked detected TW contaminants (Cu, Sr, V, perfluorooctanoic acid) that potentially associated with different adverse health effects such as inflammation, impaired reproductive systems, cancers/tumors, and/or organ toxicity. These insights can be incorporated into the regulatory framework for post-disaster risk assessment, guiding water quality control and management for public health protection.

Interlayered thin-film nanocomposite (TFN) membranes have shown the potential to boost nanofiltration performance for water treatment applications including the removal of organic micropollutants (OMPs). However, the effects of substrates have been overlooked when exploiting and evaluating the efficacy of certain kinds of interlayers in tailoring membrane performance. Herein, a series of TFN membranes were synthesized on different porous substrates with identical interlayers of metal-organic framework nanosheets. It was revealed that the interlayer introduction could narrow but not fully eliminate the difference in the properties among the polyamide layers formed on different substrates, and the membrane performance variation was prominent in distinct aspects. For substrates with small pore sizes exerting severe water transport hindrance, the introduced interlayer mainly enhanced membrane water permeance by affording the gutter effect, while it could be more effective in reducing membrane pore size by improving the interfacial polymerization platform and avoiding PA defects when using a large-pore-size substrate. By matching the selected substrates and interlayers well, superior TFN membranes were obtained with simultaneously higher water permeance and OMP rejections compared to three commercial membranes. This study helps us to objectively understand interlayer efficacies and attain performance breakthroughs of TFN membranes for more efficient water treatment.

Removal of organic micropollutants (OMPs) from water, especially hydrophilic and ionized ones, is challenging for water remediation. Herein, porous β-cyclodextrin polymers (PCPs) with tailored functionalization were prepared based on molecular expansion strategy and sulfonation. Partially benzylated β-cyclodextrin was knotted by external crosslinker to form PCP1, and knotting PCP1 by expansion molecule generated PCP2. PCP1 and PCP2 were sulfonated to achieve PCP1-SO3H and PCP2-SO3H. Based on systematical adsorption evaluation toward multiple categories of OMPs, it was found that the introduced strong polar -SO3H group could bring strong hydrogen bonding and electrostatic interactions. PCP2 showed the highest surface (998.97 m2/g) displayed more excellent adsorption performance toward neutral and anionic OMPs, and the adsorption mechanism for this property of PCP2 was dominated by hydrophobic interactions. In addition, the PCP1-SO3H with the lowest surface area (39.75 m2/g) rather than PCP2-SO3H with higher surface (519.28 m2/g) exhibited more superior adsorption towards hydrophilic and cationic OMPs, benefiting by hydrogen bonding and electrostatic interactions as well as appropriate porosity. These results not only confirmed the performance enhancement of PCPs through the integration of novel preparation strategy, but also provided fundamental guidance for PCPs design for water remediation.

A novel approach of visible light-emitting diode (Vis-LED) radiation was employed to activate permanganate (Mn(VII)) for efficient organic micropollutant (OMP) removal. The degradation rates of OMPs by Vis-LED/Mn(VII) were 2-5.29 times higher than those by Mn(VII) except for benzoic acid and atrazine. Increasing wavelengths (445-525 nm) suppressed the degradation of diclofenac (DCF) and 4-chlorophenol (4-CP) owing to the decreased quantum yields of Mn(VII). Comparatively, light intensity and Mn(VII) dosage had a positive effect on the degradation of DCF and 4-CP. Experimental data revealed that Mn(V) dominated the DCF degradation whereas Mn(III) was the active oxidant in the 4-CP degradation. Mn(V) and Mn(III) formed from the photo-decomposition of Mn(VII), meanwhile, Mn(III) also formed from the Mn(V) photo-decomposition. The increase in solution pH inhibited DCF degradation but had a positive impact on 4-CP degradation, mainly due to the changing speciation of DCF and 4-CP. Inorganic anions (Cl- and HCO3-) had little impact on DCF and 4-CP degradation, while humic acid (HA) showed a positive impact because of the π-π interaction between HA and DCF/4-CP. The transformation products of DCF and 4-CP were identified and transformation pathways were proposed. Finally, the Vis-LED/Mn(VII) exhibited great degradation performance in various authentic waters. Overall, this study boosts the development of Mn(VII)-based oxidation processes.

Extracellular polymeric substances (EPS) participate in the removal of organic micropollutants (OMPs), but the primary pathways of removal and detailed mechanisms remain elusive. We evaluated the effect of EPS on removal for 16 distinct chemical classes of OMPs during anaerobic digestion (AD). The results showed that hydrophobic OMPs (HBOMPs) could not be removed by EPS, while hydrophilic OMPs (HLOMPs) were amenable to removal via adsorption and biotransformation of EPS. The adsorption and biotransformation of HLOMPs by EPS accounted up to 19.4 ± 0.9 % and 6.0 ± 0.8 % of total removal, respectively. Further investigations into the adsorption and biotransformation mechanisms of HLOMPs by EPS were conducted utilizing spectral, molecular dynamics simulation, and electrochemical analysis. The results suggested that EPS provided abundant binding sites for the adsorption of HLOMPs. The binding of HLOMPs to tryptophan-like proteins in EPS formed nonfluorescent complexes. Hydrogen bonds, hydrophobic interactions and water bridges were key to the binding processes and helped stabilize the complexes. The biotransformation of HLOMPs by EPS may be attributed to the presence of extracellular redox active components (c-type cytochromes (c-Cyts), c-Cyts-bound flavins). This study enhanced the comprehension for the role of EPS on the OMPs removal in anaerobic wastewater treatment.

Activated carbon is employed for the adsorption of organic micropollutants (OMPs) from water, typically present in concentrations ranging from ng L-1 to μg L-1. However, the efficacy of OMP removal is considerably deteriorated due to competitive adsorption from background dissolved organic matter (DOM), present at substantially higher concentrations in mg L-1. Interpreting the characteristics of competitive DOM is crucial in predicting OMP adsorption efficiencies across diverse natural waters. Molecular weight (MW), aromaticity, and polarity influence DOM competitiveness. Although the aromaticity-related metrics, such as UV254, of low MW DOM were proposed to correlate with DOM competitiveness, the method suffers from limitations in understanding the interplay of polarity and aromaticity in determining DOM competitiveness. Here, we elucidate the intricate influence of aromaticity and polarity in low MW DOM competition, spanning from a fraction level to a compound level, by employing direct sample injection liquid chromatography coupled with ultrahigh-resolution Fourier-transform ion cyclotron resonance mass spectrometry. Anion exchange resin pre-treatment eliminated 93% of UV254-active DOM, predominantly aromatic and polar DOM, and only minimally alleviated DOM competition. Molecular characterization revealed that nonpolar molecular formulas (constituting 26% PAC-adsorbable DOM) with medium aromaticity contributed more to the DOM competitiveness. Isomer-level analysis indicated that the competitiveness of highly aromatic LMW DOM compounds was strongly counterbalanced by increased polarity. Strong aromaticity-derived π-π interaction cannot facilitate the competitive adsorption of hydrophilic DOM compounds. Our results underscore the constraints of depending solely on aromaticity-based approaches as the exclusive interpretive measure for DOM competitiveness. In a broader context, this study demonstrates an effect-oriented DOM analysis, elucidating counterbalancing interactions of DOM molecular properties from fraction to compound level.

Feast-famine (FF) regimes improved the removal of recalcitrant pharmaceuticals in moving bed biofilm reactors (MBBRs), but the optimal FF cycle remained unresolved. The effects of FF cycle time on the removal of bulk substrates (organic carbon and nitrogen) and trace pharmaceuticals by MBBR are systematically evaluated in this study. The feast to famine ratio was fixed to 1:2 to keep the same loading rate, but the time for the FF cycles varied from 18 h to 288 h. The MBBR adapted to the longest FF cycle time (288 h equaling 48 × HRT) resulted in significantly higher degradation rates (up to +183%) for 12 out of 28 pharmaceuticals than a continuously fed (non-FF) reactor. However, other FF cycle times (18, 36, 72 and 144 h) only showed a significant up-regulation for 2-3 pharmaceuticals compared to the non-FF reactor. Enantioselective degradation of metoprolol and propranolol occurred in the second phase of a two phase degradation, which was different for the longer FF cycle time. N-oxidation and N-demethylation pathways of tramadol and venlafaxine differed across the FF cycle time suggestin the FF cycle time varied the predominant transformation pathways of pharmaceuticals. The abundance of bacteria in the biofilms varied considerably between different FF cycle times, which possibly caused the biofilm to remove more recalcitrant bulk organic C and pharmaceuticals under long cycle times.

This study investigated degradation kinetics of five selected organic micropollutants (OMPs) present in poultry litter (namely: sulfadiazine, tetracycline, and doxycycline hyclate (antibiotics); estrone and 17-β-estradiol (hormones)) during hydrothermal carbonization (HTC) treatment as the temperature stepwise increased to 250 °C. All five pure OMPs were completely degraded before 250 °C was reached during the HTC process. Nevertheless, presence of poultry litter slowed down the degradation of OMPs. Through elemental mass balance calculation, it is noted that after 15 min (temperature less than 137 °C), 69-82% of organic carbon and 50-66% of organic nitrogen initially consisting part of the target antibiotics were fully mineralized. Both HTC filtrates and hydrochars obtained from poultry litter inhibited Escherichia coli and Bacillus subtilis growth. A combination of high salinity, high nutrients, dissolved organic carbon, and other ions in the filtrate as well as the adsorption of OMPs on hydrochars were probably the reason for the high toxicity.

Developing novel porous adsorbents for efficient wastewater treatment is significant to the environment protection. Herein, three porous polycalix[n]arenes (n = 4, 6, and 8) which had varying cavity sizes of the macrocycle (Azo-CX4P, Azo-CX6P, and Azo-CX8P) were prepared under mild conditions and tested for their potential application in water purification. Azo-CX8P with a larger cavity size of the macrocycle outperformed Azo-CX4P and Azo-CX6P in screening studies involving a range of organic micropollutants. It was proved that Azo-CX8P was especially efficient in the removal of cationic dyes because of its high negative surface charge. In terms of the adsorption of Rhodamine B with Azo-CX8P, the pseudo-second-order rate constant reaches 5.025 g·mg-1·min-1 with the maximum adsorption capacity being 1345 mg·g-1. These values are significantly higher compared with those recorded for most adsorbents. In addition, the easily prepared Azo-CX8P can be reused at least six times without a loss of the adsorption efficiency, demonstrating its potential use in water purification.

The global shortage of freshwater and inadequate supply of clean water have necessitated the implementation of robust technologies for wastewater purification, and Fenton-like chemistry is a highly-promising approach. However, realizing the rapid Fenton-like chemistry for high-efficiency degradation of organic micropollutants (OMs) remains challenging. Herein, one novel system was constructed by a Co single-atom catalyst activating peroxymonosulfate (PMS), and the optimal system (SA-Co-NBC-0.2/PMS) achieved unprecedented catalytic performance towards a model OM [Iohexol (IOH)], i.e., almost 100% decay ratio in only 10 min (the observed rate constant: 0.444 min-1) with high electrophilic species 1O2 (singlet oxygen) generation. Theoretical calculations unveiled that Co-N4 sites preferred to adsorb the terminal-O of PMS (more negative adsorption energy than other O sites: -32.67 kcal/mol), promoting the oxidation of PMS to generate 1O2. Iodine (I)23 (0.1097), I24 (0.1154) and I25 (0.0898) on IOH with higher f- electrophilic values were thus identified as the main attack sites. Furthermore, 16S ribosomal RNA high-throughput sequencing and quantitative structure-activity relationship analysis illustrated the environmentally-benign property of the SA-Co-NBC-0.2 and the tapering ecological risk during IOH degradation process. Significantly, this work comprehensively checked the competence of the SA-Co-NBC-0.2/PMS system for organics abatement in practical wastewater.