Dichloramine Hydrolysis in Membrane Desalination Permeate: Mechanistic Insights and Implications for Oxidative Capacity in Potable Reuse Applications.

Dichloramine (NHCl2) naturally exists in reverse osmosis (RO) permeate due to its application as an antifouling chemical in membrane-based potable reuse treatment. This study investigated mechanisms of background NHCl2 hydrolysis associated with the generation of oxidative radical species in RO permeate, established a kinetic model to predict the oxidative capacity, and examined its removal efficiency on trace organic contaminants in potable reuse. Results showed that NHCl2 hydrolysis generated transient peroxynitrite (ONOO-) and subsequently dissociated into hydroxyl radical (HO•). The maximal HO• exposure was observed at an RO permeate pH of 8.4, higher than that from typical ultraviolet (UV)-based advanced oxidation processes. The HO• exposure during NHCl2 hydrolysis also peaked at a NH2Cl-to-NHCl2 molar ratio of 1:1. The oxidative capacity rapidly degraded 1,4-dioxane, carbamazepine, atenolol, and sulfamethoxazole in RO permeate. Furthermore, background elevated carbonate in fresh RO permeate can convert HO• to carbonate radical (CO3•-). Aeration of the RO permeate removed total carbonate, significantly increased HO• exposure, and enhanced the degradation kinetics of trace organic contaminants. The kinetic model of NHCl2 hydrolysis predicted well the degradation of contaminants in RO permeate. This study provides new mechanistic insights into NHCl2 hydrolysis that contributes to the oxidative degradation of trace organic contaminants in potable reuse systems.

Promotive Effects of Chloride and Sulfate on the Near-Complete Destruction of Perfluorocarboxylates (PFCAs) in Brine via Hydrogen-tuned 185-nm UV Photolysis: Mechanisms and Kinetics.

Hydrogen-tuned 185 nm vacuum ultraviolet (VUV/H2) photolysis is an emerging technology to destroy per- and polyfluoroalkyl substance (PFAS) in brine. This study discovered the promotive effects of two major brine anions, i.e., chloride and sulfate in VUV/H2 photolysis on the hydrated electron (eaq-) generation and perfluorocarboxylates (PFCAs) destruction and established a kinetics model to elucidate the promotive effects on the steady-state concentration of eaq- ([eaq-]ss). Results showed that VUV/H2 achieved near-complete defluorination of perfluorooctanoic acid (PFOA) in the presence of up to 1000 mM chloride or sulfate at pH 12. The defluorination rate constant (kdeF) of PFOA peaked with a chloride concentration at 100 mM and with a sulfate concentration at 500 mM. The promotive effects of chloride and sulfate were attributed to an enhanced generation of eaq- via their direct VUV photolysis and conversion of additionally generated hydroxyl radical to eaq- by H2, which was supported by a linear correlation between the predicted [eaq-]ss and experimentally observed kdeF. The kdeF value increased from pH 9 to 12, which was attributed to the speciation of the H·/eaq- pair. Furthermore, the VUV system achieved >95% defluorination and ≥99% parent compound degradation of a concentrated PFCAs mixture in a synthetic brine, without generating any toxic perchlorate or chlorate.

Investigation on molecular characteristics of organic compounds during a full-scale landfill leachate treatment process based on non-targeted analysis.

In this study, a new methodology for evaluating full-scale landfill leachate treatment processes by non-targeted analysis using comprehensive two-dimensional gas chromatography quadrupole time-of-flight mass spectrometry (GC × GC-QTOF-MS) was proposed. The method revealed the chemical complexity of organic compounds in landfill leachate samples at the molecular level and evaluated the removal efficiency of the anaerobic-anoxic-oxic (A2O) - membrane bioreactor (MBR) - nanofiltration (NF) treatment process in conjunction with multi-level classification of organic compounds. Results showed that the results of non-targeted analysis combined with multi-level classification of organic compounds had a significant correlation with the conventional water quality parameters and can be used to evaluate the treatment process. A total of 2508 organic compounds were detected in 6 samples. 17 emerging contaminants (ECs) with known potentially hazards were detected, including Diisobutyl Phthalate (DIBP), which is toxic to male reproduction and development, and 4-Tert-Butylphenol, which causes endocrine disruption in animals. The removal rate of organic compounds by this full-scale landfill leachate treatment processes reached 79.14%. The anaerobic tank played a crucial role with 64.98% contribution. For compounds, the removal rate of heterocyclics was as high as 94.67%, and the removal rate of aliphatics was poor, only 63.49%. This treatment process had almost perfect removal effect on the steroids in alicyclics and phenols in aromatics, but poor treatment effect on saturated alkanes in aliphatics and naphthenes in alicyclics. This study provides a methodology for accurate assessment of the molecular level of treatment processes, new insights for process optimization in waste treatment plants, and data support for the detection of emerging contaminants. The environmental hazards of landfill leachate can be further evaluated in the future in conjunction with ecotoxicity assessment studies.

New insight into fate and transport of organic compounds from pollution sources to aquatic environment using non-targeted screening: A wastewater treatment plant case study.

A variety of chemicals discharged into the aquatic environment by the wastewater treatment plant (WWTP), which is a potential source of hazard to the ecological environment and human health. This study established a novel analytical method for all compounds using non-targeted screening to comprehensively explore the fate and transport of organic compounds from WWTP to aquatic environment. 3967 and 3636 features were detected in WWTP samples and river samples, respectively. Multi-level classification was applied to all identified compounds, and results showed that aliphatics were dominant in both abundance and response, accounting for an average of 35.49 % and 74.10 %, respectively. A total of 88 Emerging Contaminants (ECs), including 22 endocrine disrupting chemicals (EDCs), 12 pharmaceuticals and personal care products (PPCPs), 12 pesticides, 10 volatile organic compounds (VOCs), 5 persistent organic pollutants (POPs) and 27 chemicals with other uses, were identified from all compounds, and their traceability analysis was performed. Furthermore, the contribution rate of organic compounds from WWTP effluent to river was calculated to be 33.60 % by the analysis of source-sink relationship. An in-depth and comprehensive exploration of the fate and transport of all organic compounds will help to provide guidelines for the treatment technologies and achieve the traceability of pollutants.

Source apportionment and crop bioaccumulation of perfluoroalkyl acids and novel alternatives in an industrial-intensive region with fluorochemical production, China: Health implications for human exposure.

Due to their great environmental hazards, the widely used legacy perfluoroalkyl acids (PFAAs) are gradually restricted, and novel alternatives are being developed and applied. For efficient control of emerging environmental risks in agricultural production, we systematically studied the source apportionment in field soils and bioaccumulation characteristics in multiple crops of 12 PFAAs and five novel alternatives in an industrial-intensive region of China, followed by human exposure estimation and health risk assessment. Compared with perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), shorter-chained PFAAs and novel alternatives have become the dominant components in local soils and crops, indicating their wide application. A positive matrix factorization (PMF) model coupled with multivariate analysis identified fluoropolymer manufacturing and textile treatment as the principal sources. The bioaccumulation factors (BAFs) of individual PFAAs and alternatives in crops decreased with increasing carbon chain lengths. As a novel alternative of PFOA, hexafluoropropylene oxide dimer acid (GenX) exhibited much higher BAFs; for the alternative of PFOS, 6:2 chlorinated polyfluorinated ether sulfonic acid (6:2 Cl-PFESA) showed lower BAFs. The bioaccumulation capacities of PFAAs and alternatives were also associated with soil organic matter and crop species. Through crop consumption, short-chained PFAAs and novel alternatives might pose emerging human health threats.