Antibiotic sulfanilamide biodegradation by acclimated microbial populations.

Sulfonamide antibiotics are commonly detected in the environment. Microbial degradation can play an important role in the dissipation of sulfonamide antibiotics. However, many aspects regarding the influential factor and biodegradation pathway remain essentially unclear. Moreover, phylogenetic information on the sulfonamide-degrading microbial community is still very limited. The present study investigated the biodegradation of sulfonamide antibiotic sulfanilamide by acclimated mixed culture and its influential factors, and the sulfanilamide-degrading microbial community. At the initial sulfanilamide concentration of 100 µg/L, nearly half of the antibiotic could be removed by acclimated microbial populations after 1 week of incubation, and an average removal rate of 78.3 % could be achieved in 4 weeks. p-Phenylenediamine, benzene sulfonamide, and hydroxylamine benzene sulfonamide were identified as the potential intermediates. Sulfanilamide biodegradation could be enhanced by a temperature rise and the presence of external carbon or nitrogen sources. The richness, diversity, and structure of the bacterial community showed a remarkable change with sulfanilamide biodegradation. Firmicutes and Bacteroidetes (mainly represented by classes Bacilli and Flavobacteriia) dominated the sulfanilamide-degrading bacterial community.

Additive manufacturing-derived free-standing 3D pyrolytic carbon electrodes for sustainable microbial electrochemical production of H2O2.

Producing H2O2 via microbial electrosynthesis is a cost-effective and environmentally favorable alternative to the costly and environmentally hazardous anthraquinone method. However, most studies have relied on carbon electrodes with two-dimensional (2D) surfaces (e.g., graphite), which have limited surface area and active sites, resulting in suboptimal H2O2 production. In this study, we demonstrate the enhanced efficiency of microbial H2O2 synthesis using three-dimensional (3D) electrodes produced through additive manufacturing technology due to their larger surface area than conventional carbon electrodes with 2D surfaces. This work innovatively combines 3D printed pyrolytic carbon (3D PyrC) electrodes with highly defined outer geometry and internal mesh structures derived from additive manufacturing with high-temperature resin precursors followed by pyrolysis with microbial electrochemical platform technology to achieve efficient H2O2 synthesis. The 3D PyrC electrode produced a maximum of 129.2 mg L-1 of H2O2 in 12 h, which was 2.3-6.9 times greater than conventional electrodes (e.g., graphite and carbon felt). Furthermore, the scalability, reusability and mechanical properties of the 3D PyrC electrode were exemplary, showcasing its practical viability for large-scale applications. Beyond H2O2 synthesis, the study explored the application of the 3D PyrC electrode in the bio-electro-Fenton process, demonstrating its efficacy as a tertiary treatment technology for the removal of micropollutants. This dual functionality underscores the versatility of the 3D PyrC electrode in addressing both the synthesis of valuable chemicals and environmental remediation. This study shows a novel electrode design for efficient, sustainable synthesis of H2O2 and subsequent environmental remediation.

When polyethylene terephthalate microplastics meet Perfluorooctane sulfonate in thermophilic biogas upgrading system: Their effect on methanogenesis.

Microplastics (MPs) and Perfluorooctane sulfonate (PFOS) are two hard-biodegradable pollutants widely existing in the waste streams treated by anaerobic digestion. However, their synergistic effect on methanogenic metabolism is still unknown. This study investigated the impact of polyethylene terephthalate (PET) MPs alone and co-existing with PFOS on CO2 conversion to CH4 in a thermophilic biogas upgrading system. The results showed that either PET MPs addition alone or coexisting with PFOS improved the ultimate CH4 percentage and increased CO2 utilization rate. When Fe0 was added into the reactors with PET to enhance the interspecies electron transfer, a potential defluorination was observed with a defluorination rate of 15.88 ± 1.53%. Exposure of the reactor to PFOS of 300 µg/L could change the methanogenic pathway, resulting in a newly emerged Methanomassiliicoccus with dominance of 16%. Furthermore, under the exposure of PFOS, the number of predicted genes regulating enzymes in methanogenic steps from CO2 increased. These results suggest that the co-existence of PET MPs and PFOS will not inhibit the activity of hydrotrophic methanogenes, and a portion of PFOS may be biodegraded during the methanogenesis under Fe0 regulation.

Differential interactions between natural clay minerals and dissolved organic matter affect reactive oxygen species formation.

Naturally occurring reactive oxygen species (ROS) are widely involved in many environmental processes. Here we investigated the ROS generation associated with the interaction between complexed natural clay minerals (CMs) and dissolved organic matter (DOM). Our results showed that among the nine chemical-reduced CMs (CR-CMs), the light brown CR-CM (CR-CM 7) generated the highest ROS via oxygenation, relying on the reactive structural Fe(II) (Fe species that can transfer electrons to oxygen) instead of total structural Fe(II) as previously reported. Moreover, DOM affected the oxygenation of CR-CMs differently. The tight interaction between DOM and CR-CM 7 formed DOM-complexed Fe, while the weak interaction between DOM and the dark gold CR-CM (CR-CM 1) and the black CR-CM (CR-CM 5) exhibited decreased efficiencies. Mechanism studies revealed that ROS were generated through three pathways but all followed a similar one-electron transfer process in the presence of DOM. We further developed a three-layer geobattery model system and demonstrated that long electron transfer driven by CR-CMs/DOM could extend ROS generation to several centimetres across the oxic-anoxic interface, even without redox switching. These findings offer new insights into CMs-involved ROS generation and associated organic matter transformation in natural environments.

Sustainable bioelectric activation of periodate for highly efficient micropollutant abatement.

The periodate (PI)-based advanced oxidation process is valued for environmental remediation, but current activation methods involve high costs, secondary contamination risks, and limited applicability due to external energy inputs (e.g., UV), catalyst incorporation (e.g., Fe2+), or environmental modifications (e.g., freezing). In this work, novel bioelectric activation of PI using the electrons generated by electroactive bacteria was developed and investigated for rapid removal of carbamazepine (CBZ), achieving 100 %, 100 %, and 76 % removal efficiency for 4.22 µM of CBZ in 20 min at pH 2, 120 min at pH 6.4, and HRT of 30 min at pH 8.5, respectively, with a 1 mM PI dose and without an input voltage. It was deduced that electrons derived from bacteria could directly activate PI using Ti mesh electrodes and generate •IO3 via single electron transfer under strongly acidic conditions (e.g., pH 2). Nevertheless, under weak alkaline conditions (e.g., pH 8.5), biogenic electrons indirectly activated PI by generating OH-via 4e-reduction at the Ti mesh cathode, resulting in the formation of •O2- and 1O2. In addition to the metal cathode, a carbon-based cathode finely modulates the 2e-reduction, yielding H2O2 and activating PI to mainly form •OH. Moreover, primarily non-toxic IO3- was produced during treatment, while no detectable reactive iodine species (HOI, I2, and I3-) were observed. Furthermore, the bioelectric activation of PI demonstrated its capability to remove various micropollutants present in secondary-treated municipal wastewater, showcasing its broad-spectrum degradation ability. This study introduces a novel, cost-effective, and environmentally friendly PI activation technique with promising applicability for micropollutant elimination in water treatment.

Activation of peracetic acid by electrodes using biogenic electrons: A novel energy- and catalyst-free process to eliminate pharmaceuticals.

Peracetic acid (PAA) has received increasing attention as an alternative oxidant for wastewater treatment. However, existing processes for PAA activation to generate reactive species typically require external energy input (e.g., electrically and UV-mediated activation) or catalysts (e.g., Co2+), inevitably increasing treatment costs or introducing potential new contaminants that necessitate additional removal. In this work, we developed a catalyst-free, self-sustaining bioelectrochemical approach within a two-chamber bioelectrochemical system (BES), where a cathode electrode in-situ activates PAA using renewable biogenic electrons generated by anodic exoelectrogens (e.g., Geobacter) degrading biodegradable organic matter (e.g., acetic acid) in wastewater at the anode. This innovative BES-PAA technique achieved 98 % and 81 % removal of 2 µM sulfamethoxazole (SMX) in two hours at pH 2 (cation exchange membrane) and pH 6 (bipolar membrane) using 100 µM PAA without external voltage. Mechanistic studies, including radical quenching, molecular probe validation, electron spin resonance (ESR) experiments, and density functional theory (DFT) calculations, revealed that SMX degradation was driven by reactive species generated via biogenic electron-mediated OO cleavage of PAA, with CH3C(O)OO• contributing 68.1 %, •OH of 18.4 %, and CH3C(O)O• of 9.4 %, where initial formation of •OH and CH3C(O)O• rapidly reacts with PAA to produce CH3C(O)OO•. The presence of common water constituents such as anions (e.g., Cl-, NO3-, and H2PO4-) and humic acid (HA) significantly hinders SMX removal via the BES-PAA technique, whereas CO32- and HCO3- ions have a comparatively minor impact. Additionally, the study investigated the removal of various pharmaceuticals present in secondary treated municipal wastewater, attributing differences in removal efficiency to the selective action of CH3C(O)OO•. This research demonstrates a novel PAA activation method that is ecologically benign, inexpensive, and capable of overcoming catalyst deactivation and secondary pollution issues.

Selective and nonselective removal of hydrophobic compounds by coupling engineered FeOCl in a cathode-anode synergistic electrochemical platform.

Efficient and selective removal of water pollutants remains a critical challenge. Here, we addressed this challenge by ingeniously engineering FeOCl via polyaniline intercalation and dodecyl group modification (FeOCl-P-S) to improve its activity and selectivity for the in situ removal of hydrophobic phenolic compounds. We further encapsulated the catalyst inside commercial cheap corundum balls and developed a "millimeter-scale reactor", which maintained a high efficiency of 86.02% after ten cycles with negligible physical changes. Moreover, we established the synergy between anodic (generating H+, O2, and IrO3) and cathodic reactions (utilizing H+ and O2) for H2O2 generation and direct anodic oxidation, an unexplored process, in a vertical bidirectional gas diffusion electrochemical system (VB-GDE). By combining the "reactor" and VB-GDE, we constructed a new platform for selective and nonselective continuous pollutant oxidation in a self-sustaining acidic environment with minimal chemical residues. This work presents a promising electrochemical technology for the efficient and selective removal of water pollutants.

Dynamic coordination of two-phase reactions in heterogeneous Fenton for selective removal of water pollutants.

The •OH-mediated heterogeneous Fenton reaction has been widely applied despite the limitations of low pollutant selectivity and unclear oxidation mechanism. Here we reported an adsorption-assisted heterogeneous Fenton process for the selective degradation of pollutants and systematically illustrated its dynamic coordination in two phases. The results showed that the selective removal was improved by (i) surface enrichment of target pollutants via electrostatic interactions including real adsorption and adsorption-assisted degradation and (ii) inducing the diffusion of H2O2 and pollutants from the bulk solution to the catalyst surface to trigger the homogeneous and surface heterogeneous Fenton reactions. Furthermore, surface adsorption was confirmed as a crucial but not necessary step for degradation. Mechanism studies demonstrated that •O2- and Fe3+/Fe2+ cycle increased •OH generation, which remained active in two phases within ⁓244 nm. These findings are critical for understanding the removal behavior of complex targets and expanding heterogeneous Fenton applications.

Enhanced removal of antibiotic and antibiotic resistance genes by coupling biofilm electrode reactor and manganese ore substrate up-flow microbial fuel cell constructed wetland system.

Manganese ore substrate up-flow microbial fuel cell constructed wetland (UCW-MFC(Mn)) as an innovative wastewater treatment technology for purifying antibiotics and electricity generation with few antibiotic resistance genes (ARGs) generation has attracted attention. However, antibiotic purifying effects should be further enhanced. In this study, a biofilm electrode reactor (BER) that needs direct current driving was powered by a Mn ore anode (UCW-MFC(Mn)) to form a coupled system without requiring direct-current source. Removal efficiencies of sulfadiazine (SDZ), ciprofloxacin (CIP) and the corresponding ARGs in the coupled system were compared with composite (BER was powered by direct-current source) and anaerobic systems (both of BER and UCW-MFC were in open circuit mode). The result showed that higher antibiotic removal efficiency (94% for SDZ and 99.1% for CIP) in the coupled system was achieved than the anaerobic system (88.5% for SDZ and 98.2% for CIP). Moreover, electrical stimulation reduced antibiotic selective pressure and horizontal gene transfer potential in BER, and UCW-MFC further reduced ARG abundances by strengthening the electro-adsorption of ARG hosts determined by Network analysis. Bacterial community diversity continuously decreased in BER while it increased in UCW-MFC, indicating that BER mitigated the toxicity of antibiotic. Degree of modularity, some functional bacteria (antibiotic degrading bacteria, fermentative bacteria and EAB), and P450 enzyme related to antibiotic and xenobiotics biodegradation genes were enriched in electric field existing UCW-MFC, accounting for the higher degradation efficiency. In conclusion, this study provided an effective strategy for removing antibiotics and ARGs in wastewater by operating a BER-UCW-MFC coupled system.

Self-sustained ammonium recovery from wastewater and upcycling for hydrogen-oxidizing bacteria-based power-to-protein conversion.

Microbial protein (MP) production by autotrophic hydrogen-oxidizing bacteria is regarded as a potentially sustainable approach to mitigate food crisis, water pollution, and climate change. Herein, a hybrid biological-inorganic (HBI) system which coupled energy-neutral ammonium recovery and in-situ upcycling for MP production was demonstrated. No energy and acids/bases were needed for ammonium recovery and pH control. The system was tested with different amounts of CO2 supply and operated at different operational modes (microbial fuel cell or microbial electrolysis cell mode). 0.381 g/L of biomass containing 64.79% of crude protein was produced using the recovered nitrogen and therefore led to 76.8% of ammonium recovery and 84.6% of COD removal from real municipal wastewater. The system although not yet optimal in terms of efficiency has a meaning in alleviating food crisis and environmental issues. Altogether, this study offers insight into developing an energy and resource-efficient power-to-protein process to supplement conventional food production globally.

Elimination of recalcitrant micropollutants by medium pressure UV-catalyzed bioelectrochemical advanced oxidation process: Influencing factors, transformation pathway and toxicity assessment.

Bio-electro-Fenton (BEF) processes have been widely studied in recent years to remove recalcitrant micropollutants from wastewater. Though promising, it still faces the critical challenge of residual iron and iron sludge in the treated effluent. Thus, an innovative medium-pressure ultraviolet-catalyzed bio-electrochemical system (MUBEC), in which medium-pressure ultraviolet was employed as an alternative to iron for in-situ H2O2 activation, was developed for the removal of recalcitrant micropollutants. The influence of operating parameters, including initial catholyte pH, cathodic aeration rate, and input voltage, on the system performance, was explored. Results indicated that complete reduction of 10 mg L-1 of model micro-pollutants ibuprofen (IBU) and carbamazepine (CBZ) was achieved at pH 3, with an aeration rate of 1 mL min-1 and a voltage of 0.3 V, following pseudo-first-order kinetics. Moreover, potential transformation pathways and the associated intermediates during the degradation were deduced and detected, respectively. Thus, the MUBEC system shows the potential for the efficient and cost-effective degradation of recalcitrant micropollutants from wastewater.

When microbial electrochemistry meets UV: The applicability to high-strength real pharmaceutical industry wastewater.

Wastewater from pharmaceutical and related industries contains many residual pharmaceutical components rich in color and high COD contents, which cannot be removed through the traditional wastewater treatment processes. Recently, microbial electrolysis ultraviolet cell (MEUC) process has shown its promising potential to remove recalcitrant organics because of its merits of wide pH range, iron-free, and without complications of iron sludge production. However, its application to the real pharmaceutical-rich industrial wastewater is still unknown. In this study, the MEUC process was validated with real ciprofloxacin-rich (6863.79 ± 2.21 µg L-1) industrial wastewater (6840 ± 110 mg L-1 of COD). The MEUC process achieved 100% removal of ciprofloxacin, 100% decolorization, and 99.1% removal of COD within 12, 60 and 30 h, respectively, when it was operated at pH-controlled at 7.8, applied voltage of 0.6 V, UV intensity of 10 mW cm-2, and cathodic aeration velocity of 0.005 mL min-1 mL-1. Moreover, fluorescence analysis showed that protein- and humic-like substances in such wastewater were effectively removed, providing further evidence of its high treatment efficiency. Furthermore, eco-toxicity testing with luminescent bacteria Vibro Feschri confirmed that the treated effluent was utterly non-toxic. The results demonstrated the broad application potential of MEUC technology for treating industrial wastewater.

Scaling-up of microbial electrosynthesis with multiple electrodes for in situ production of hydrogen peroxide.

Microbial electrosynthesis system (MES) has recently been shown to be a promising alternative way for realizing in situ and energy-saving synthesis of hydrogen peroxide (H2O2). Although promising, the scaling-up feasibility of such a process is rarely reported. In this study, a 20-L up-scaled two-chamber MES reactor was developed and investigated for in situ and efficient H2O2 electrosynthesis. Maximum H2O2 production rate of 10.82 mg L-1 h-1 and cumulative H2O2 concentration of 454.44 mg L-1 within 42 h were obtained with an input voltage of 0.6 V, cathodic aeration velocity of 0.045 mL min-1 mL-1, 50 mM Na2SO4, and initial pH 3. The electrical energy consumption regarding direct input voltage was only 0.239 kWh kg-1 H2O2, which was further much lower compared with laboratory-scale systems. The obtained results suggested that the future industrialization of MES technology for in situ synthesis of H2O2 and further application in environmental remediation have broad prospects.

Degradation of metoprolol from wastewater in a bio-electro-Fenton system.

Advanced oxidation processes (AOPs) have been intensely studied for the removal of refractory pollutants because of the strong oxidizing capacity of hydroxyl radical. One of the emerging AOP methods gaining increased attention is bio-electro-Fenton (BEF) which can generate hydroxyl radical in-situ in the cathode chamber using the energy harvested by exoelectrogenic bacteria in the anode. In this study, the feasibility of BEF technology for the removal of metoprolol, a typical micropollutant widely found in the water environment, was for the first time investigated. It was found that applied voltage and working pH had a significant effect on removal efficiency while Fe2+ dosage as catalyst showed a little effect. Besides removal by hydroxyl radical, metoprolol might be adsorbed on the surface of the reactor, electrode, and precipitated with iron sludge, especially at neutral pH. In a batch experiment with a supplied voltage of 0.2 V, pH 3, and a Fe2+ dose of 0.2 mM, the removal rate of metoprolol in the BEF for the synthetic wastewater and the real effluent from the secondary sediment tank was 66% and 55% within 12 h, respectively. A possible degradation pathway was proposed. Then the removal of metoprolol in a continuous flow BEF system was further studied at different hydraulic retention times (HRTs) of 2, 4, and 6 h, about 77%, 92%, and 95% removal was observed. A toxicity test (less than 20% inhibition on bioluminescence) during treatment and energy cost analysis (5.269 × 10-3 kWh/order/m3) in treating 10 µg/L of metoprolol containing wastewater effluent at continuous flow mode implied that the proposed BEF has a potential for wastewater treatment.

A novel persulfate-photo-bioelectrochemical hybrid system promoting the degradation of refractory micropollutants at neutral pH.

Bio-electro-Fenton is emerging as an alternative technology for the efficient and cost-effective removal of refractory micropollutants. Though promising, there are still several challenges that limit its wide application, including acidic operating conditions (pH at 2-3), the addition of supporting electrolytes (e.g., Na2SO4), and the issue of iron sludge generation. To address these challenges, a novel hybrid persulfate-photo-bioelectrochemical (PPBEC) system is proposed to remove model micropollutants (carbamazepine and clorfibric acid), from secondary effluent at low persulfate (PS) dosage and neutral pH. The effect of crucial operating parameters on the process was studied, including input voltage, cathodic aeration velocity, and PS dose. Under optimal conditions (0.6 V, 0.005 mL min-1 mL-1 and 1 mM), the PPBEC system achieved approx. 0.56-1.71 times greater micropollutant removal with 93% lower energy consumption when compared to the individual processes (UV/PS and PBEC). The improved performance was attributed to a faster production of sulfate radicals by UV irradiation, hydrogen peroxide activation and single-electron reduction, and hydroxyl radicals generated by UV irradiation. Furthermore, the transformation products of carbamazepine and clorfibric acid were identified and the probable pathways are proposed. Finally, the ecotoxicity of the PPBEC treated effluent was assessed by using Vibrio Fischeri, which exhibited a non-toxic effect.

Feasibility and applicability of the scaling-up of bio-electro-Fenton system for textile wastewater treatment.

Textile wastewater entering natural water bodies could cause serious environment and health issues. Bio-electro-Fenton (BEF) as an efficient and energy saving wastewater treatment technology has recently attracted widespread attention. So far, there is no research available on the scaling-up of BEF process. In this work, an innovative 20 L up-scaled BEF system was constructed for the treatment of methylene blue (MB) containing wastewater. The system was first tested in batch mode. The results showed that the system performance was majorly related to the operating parameters including initial MB concentration, catholyte pH and concentration, cathodic aeration rate, Fe2+ dosage, and applied voltage. At the optimal condition, 20 mg L-1 of MB was efficiently removed following the apparent first order kinetics. The corresponding rate constants for the decolorization and mineralization were 0.68 and 0.20 h-1, respectively. Furthermore, MB decolorization efficiency of 99% and mineralization efficiency of 74% were observed when the hydraulic retention time was 28 h in continuous mode. This work demonstrates the scaling-up potential of BEF for recalcitrant wastewater treatment.

Degradation of pharmaceuticals from wastewater in a 20-L continuous flow bio-electro-Fenton (BEF) system.

The bio-electro-Fenton (BEF) technology has proven to be an effective and energy-saving method for treating wastewaters containing a single pharmaceutical in the lab-scale. However, the continuous degradation of pharmaceuticals in a scaled-up BEF has never been reported. In this study, a 20-L dual-chamber BEF reactor was designed and tested for treating six model pharmaceuticals. The effect of key operational factors including applied voltage, cathode Fe2+ dosage, initial pharmaceuticals concentration and hydraulic retention time (HRT), were assessed. By implementing 0.1 V voltage, 0.3 mM Fe2+ and HRT of 26 h, the six selected pharmaceuticals (500 µg L-1 for each) were removed completely. Moreover, transformation products during clofibric acid degradation, such as 4-chlororesorcinol, were detected and the relevant transformation pathway was proposed. Additionally, it successfully removed these pharmaceuticals in the real wastewater matrix. This paper contributes to scaling-up the BEF process for continuous and effective treating pharmaceuticals-contaminated wastewater.

An innovative microbial electrochemical ultraviolet photolysis cell (MEUC) for efficient degradation of carbamazepine.

Discharge of recalcitrant pharmaceuticals into aquatic environments can lead to serious negative environmental effects. While traditional wastewater treatment plants (WWTPs) are efficient for a wide range of non-toxic pollutants (i.e. ammonia), some wastewater streams contain recalcitrant toxic trace micropollutants such as pharmaceuticals that cannot be removed by the treatment processes that are typically employed in common WWTPs. Herein, an innovative 20 L microbial electrochemical ultraviolet photolysis cell (MEUC) was developed for the first time by the integration of a UV irradiation and a bioelectrochemical system, which exhibited efficient treatment of carbamazepine-a model pharmaceutical compound. Notably, neither the UV irradiation nor the bioelectrochemical system alone could effectively eliminate carbamazepine. The effect of operational parameters including applied voltage, cathodic aeration rate, UV intensity, and hydraulic retention time were evaluated. The obtained results elucidated that the degradation of carbamazepine was consistent with pseudo-first-order reaction kinetics, and required a lower energy input than traditional advanced oxidation processes. Five main transformation products were identified, and probable transformation pathways were established. Furthermore, the eco-toxicity as tested by Vibrio fischeri showed no significant bioluminescence inhibition by the treated carbamazepine effluent. Finally, the MEUC system was further tested with a real wastewater matrix, which again exhibited effective removal of carbamazepine. This paper provides a proof-of-concept verification of the novel MEUC system, which contributes insight for the subsequent vigorous development of the application of such efficient and cost-effective technologies for the treatment of trace pharmaceuticals wastewater.

Reduction of N-nitrosodimethylamine formation from ranitidine by ozonation preceding chloramination: influencing factors and mechanisms.

Formation of toxic N-nitrosodimethylamine (NDMA) by chloramination of ranitidine, a drug to block histamine, was still an ongoing issue and posed a risk to human health. In this study, the effect of ozonation prior to chloramination on NDMA formation and the transformation pathway were determined. Influencing factors, including ozone dosages, pH, hydroxyl radical scavenger, bromide, and NOM, were studied. The results demonstrated that small ozone dosage (0.5 mg/L) could effectively control NDMA formation from subsequent chloramination (from 40 to 0.8%). The NDMA molar conversion was not only influenced by pH but also by ozone dosages at various pre-ozonation pH (reached the highest value of 5% at pH 8 with 0.5 mg/L O3 but decreased with the increasing pH with 1 mg/L O3). The NDMA molar yield by chloramination of ranitidine without pre-ozonation was reduced by the presence of bromide ion due to the decomposition of disinfectant. However, due to the formation of brominated intermediate substances (i.e., dimethylamine (DMA), dimethyl-aminomethyl furfuryl alcohol (DFUR)) with higher NDMA molar yield than their parent substances, more NDMA was formed than that without bromide ion upon ozonation. Natural organic matter (NOM) and hydroxyl radical scavenger (tert-butyl alcohol, tBA) enhanced NDMA generation because of the competition of ozone and more ranitidine left. The NDMA reduction mechanism by pre-ozonation during chloramination of ranitidine may be due to the production of oxidation products with less NDMA yield (such as DMA) than parent compound. Based on the result of Q-TOF and GC-MS/MS analysis, three possible transformation pathways were proposed. Different influences of oxidation conditions and water quality parameters suggest that strategies to reduce NDMA formation should vary with drinking water sources and choose optimal ozone dosage.

Evaluating the biosafety of conventional and O3-BAC process and its relationship with NOM characteristics.

It is the priority to guarantee biosafety for drinking water treatment. The objective of this study was to evaluate the impact of widely applied conventional and ozone-biological activated carbon (O3-BAC) advanced treatment technology on biosafety of drinking water. The items, including assimilable organic carbon (AOC), biodegradable dissolved organic carbon (BDOC), heterotrophic plate counts (HPCs) and the microorganism community structures, were used to evaluate the biosafety. Moreover, their relationships with molecular weights (MWs) and fluorescence intensity of dissolved organic matter were investigated. The results indicated that the technology provided a considerable gain in potable water quality by decreasing dissolved organic carbon (DOC, from 5.05 to 1.71 mg/L), AOC (from 298 to 131 µg/L), BDOC (from 1.39 to 0.24 mg/L) and HPCs (from 275 to 10 CFU/mL). Ozone brought an increase in DOC with low MW <1 kDa, which accompanies with an increase in AOC/BDOC concentration, which could be reduced effectively by subsequent BAC process. The formation of AOC/BDOC was closely related to DOC with low MWs and aromatic protein. Bacteria could be released from BAC filter, resulting in an increase in HPC and the presence of pathogenic bacteria in effluent, while the post sand filter could further guarantee the biosafety of finished water.