N-(1,3-dimethylbutyl)-N\'-phenyl-p-phenylenediamine quinone (6PPD-Q) has been identified to induce acute toxicity to multifarious aquatic organisms at exceptionally low concentrations. The ubiquity and harmful effects of 6PPD-Q emphasize the critical need for its degradation from water ecosystems. Herein, we explored the transformation of 6PPD-Q by an ultraviolet-activated peroxymonosulfate (UV/PMS) system, focusing on mechanism, products and toxicity variation. Results showed that complete degradation of 6PPD-Q was achieved when the initial ratio of PMS and 6PPD-Q was 60:1. The quenching experiments and EPR tests indicated that SO4•- and •OH radicals were primarily responsible for 6PPD-Q removal. Twenty-one degradation products were determined through high-resolution orbitrap mass spectrometry, and it was postulated that hydroxylation, oxidative cleavage, quinone decomposition, ring oxidation, as well as rearrangement and deamination were the major transformation pathways of 6PPD-Q. Toxicity prediction revealed that all identified products exhibited lower acute and chronic toxicities to fish, daphnid and green algae compared to 6PPD-Q. Exposure experiments also uncovered that 6PPD-Q considerably reduced the community diversity and altered the community assembly and functional traits of the sediment microbiome. However, we discovered that the toxicity of 6PPD-Q degradation solutions was effectively decreased, suggesting the superior detoxifying capability of the UV/PMS system for 6PPD-Q. These findings highlight the underlying detrimental impacts of 6PPD-Q on aquatic ecosystems and enrich our understanding of the photochemical oxidation behavior of 6PPD-Q.

Widely used antioxidants can enter the environment via urban stormwater systems and form disinfection byproducts (DBPs) during chlorination in downstream drinking water processes. Herein, we comprehensively investigated the occurrence of 39 antioxidants from stormwater runoff to surface water. After a storm event, the concentrations of the antioxidants in surface water increased by 1.4-fold from 102-110 ng/L to 128-139 ng/L. Widespread antioxidants during the stormwater event could transform into toxic DBPs during disinfection. Moreover, the yields of trihalomethanes, haloacetaldehydes, haloacetonitriles (HANs), and halonitromethanes during the chlorination of widely used antioxidants considerably increased with an increasing chlorine dose and contact time. Specifically, the yields of dichloroacetonitrile during the chlorination of diphenylamine (DPA) and N-(1,3-dimethylbutyl)-N\'-phenyl-p-phenylenediamine (6PPD) were higher than those of most reported amino acid precursors, indicating that DPA and 6PPD might be important precursors of HANs. Exploring the intermediates using GC × GC-time-of-flight high-resolution mass spectrometry helped reveal potential pathways from DPA to HANs, whose formation could be attributed to the intermediate carbazole and indole moieties detected in this study. This study provides insights into the transport and transformation of commonly used antioxidants in a water environment and during water treatment processes, highlighting the potential risks of anthropogenic pollutants from a DBP perspective.

The main objective of the proposed approach is to accelerate the transition of the bioeconomy towards a knowledge-based sustainable system, covering key biobased sectors strongly linked to agriculture in Poland, in line with the European Green Deal. The proposed model of a bioeconomy development strategy, with a special focus on agriculture, is based on two pillars: (1) strengthening traditional, relevant (in terms of economic indicators) sectors of the economy and improving their \'sustainability\' by implementing the proposed transformation pathways; and (2) developing economic activities or \'niche or novel sectors\' that are prospective accelerators of change in the face of climate challenge, and ensuring their upscaling. This approach forms the basis for policy planning at national and regional level in these European Union (EU) countries, where bioeconomy development strategies have been initiated through dialogue between science, administration and industry stakeholders. The strategic actions we propose are grouped in three areas; (1) Market intervention mainly by introducing sustainability criteria for the national production system; (2) Research, innovation and education that significantly strengthen the relationship between business and science and educational activities in the field of sustainability and climate change, and (3) Governance and policy actions to enforce the relationship between the main sub-sectors of bioeconomy and niche sectors in frame of bio-economy strategy or action plan that will profits by added value of products from bioeconomy sectors and increasing number of newly created jobs.

Information on biotransformation of antivirals in the side-stream partial nitritation (PN) process was limited. In this study, a side-stream PN sludge was adopted to investigate favipiravir biotransformation under controlled ammonium and pH levels. Results showed that free nitrous acid (FNA) was an important factor that inhibited ammonia oxidation and the cometabolic biodegradation of favipiravir induced by ammonia oxidizing bacteria (AOB). The removal efficiency of favipiravir reached 12.6% and 35.0% within 6 days at the average FNA concentrations of 0.07 and 0.02 mg-N L-1, respectively. AOB-induced cometabolism was the sole contributing mechanism to favipiravir removal, excluding AOB-induced metabolism and heterotrophic bacteria-induced biodegradation. The growth of Escherichia coli was inhibited by favipiravir, while the AOB-induced cometabolism facilitated the alleviation of the antimicrobial activities with the formed transformation products. The biotransformation pathways were proposed based on the roughly identified structures of transformation products, which mainly involved hydroxylation, nitration, dehydrogenation and covalent bond breaking under enzymatic conditions. The findings would provide insights on enriching AOB abundance and enhancing AOB-induced cometabolism under FNA stress when targeting higher removal of antivirals during the side-stream wastewater treatment processes.

Antibiotic residues and their chlorinated disinfection by-products (Cl-DBPs) have adverse effects on organisms in aquaculture water. Taking enrofloxacin (ENR) as target antibiotic, this study investigated the degradation and transformation of ENR Cl-DBPs in constructed wetlands (CWs). Results showed that, ENR and its Cl-DBPs affected the biodegradation of CWs at the preliminary stage, but did not affect the adsorption by plant roots, substrates, and biofilms. The piperazine group of ENR had great electronegativity, and was prone to electrophilic reactions. The carboxyl on quinolone group of ENR had strong nucleophilicity, and was prone to nucleophilic reactions. C atoms with significant negative charges on the aromatic structure of quinolone group were prone to halogenation. During the chlorination of ENR, one pathway was the reaction of quinolone group, in which nucleophilic substitution reaction by chlorine occurred at C26 atom on carboxyl group, then halogenation occurred under the action of Cl+ at C17 site on the aromatic ring; the other pathway was the reaction of piperazine group, in which N7 atom was firstly attacked by HOCl, resulting in piperazine ring cleavage, then followed by deacylation, dealkylation, and halogenation. During the biodegradation of ENR Cl-DBPs, the reactivity of piperazine structure was strong, especially at N6, N7, C13, and C14 sites, while the ring structure of quinolone group was quite stable, and only occurred decyclopropyl at N5 site. Overall, the biodegradation of ENR Cl-DBPs in CWs went through processes including piperazine ring cleavage, tertiary amine splitting, dealkylation, and aldehyde oxidation under the action of coenzymes, in which metabolites such as ketones, aldehydes, carboxylic acids, amides, primary amines, secondary amines, tertiary amines and acetaldehyde esters were produced. Most ENR Cl-DBPs had greater bioaccumulation potential and stronger toxicity than their parent compound, fortunately, CWs effectively reduced the environmental risk of ENR Cl-DBPs through the cooperation of adsorption and biodegradation.

Antibiotics and available chlorine coexist in multiple aquatic environments, and thus antibiotics and their chlorinated disinfection by-products (Cl-DBPs) have been a great concern for the nature and human health. Herein, the degradation intermediates and transformation pathways of sulfamethoxazole (SMX) Cl-DBPs in constructed wetlands (CWs) were investigated. A total of five SMX Cl-DBPs and their twenty degradation products in CWs was identified in this study. SMX and its Cl-DBPs influenced the biodegradation rather than the adsorption process in CWs. S1 atom on sulfonyl group of SMX had the strongest nucleophilicity, and was most vulnerable for nucleophilic attack. N5 and N7 on amino groups, and C17 on the methyl group had great electronegativity, and were susceptible to electrophilic reactions. S1-N5 and S1-C8 bonds of SMX are the most prone to cleavage, followed by C11-N5, C16-C17, and C12-N7. The chlorination of SMX mainly occurred at S1, N5, and N7 sites, and went through S-C cleavage, S-N hydrolysis, and desulfonation. The biodegradation of SMX Cl-DBPs in CWs mainly occurred at S1, N5, N7, C8, and C17 sites, and went through processes including oxidation of methyl, hydroxyl and amino groups, desulfonation, decarboxylation, azo bond cleavage, benzene ring cleavage, β-oxidation of fatty acids under the action of coenzymes. Over half of the SMX Cl-DBPs had greater bioaccumulation potential than their parent SMX, but the environmental risk of SMX Cl-DBPs was effectively reduced through the degradation by CWs.

Disinfection by-products (DBPs) formed from chlorination of antibiotics have greater toxicity than their parent compounds. Herein, this study investigated the biotransformation process of sulfadiazine Cl-DBPs in constructed wetlands (CWs). Results showed that, S atom on sulfonyl group, and N atoms on primary and secondary amine groups were the most reactive sites of sulfadiazine molecule. S1-N4 and S1-C8 of sulfadiazine are the most vulnerable bonds to cleave, followed by C14-N4 and C11-N5 bonds. In the chlorination process, sulfadiazine went through C-N bond cleavage, N-reductive alkylation, halogenation, and desulfonation to produce two aromatic Cl-DBPs. In the biodegradation process in CWs, sulfadiazine Cl-DBPs went through processes mainly including dechlorination, S-N bond cleavage, aniline-NH2 oxidation, desulfonation, phenol-OH oxidation, benzene ring cleavage, C-N bond cleavage, and β-oxidation of fatty acids under the action of a variety of oxidoreductases and hydrolases, during which a total of ten biodegradation products was identified. Moreover, sulfadiazine affected the biodegradation rather than the adsorption process in CWs. The two aromatic sulfadiazine Cl-DBPs had much higher bioaccumulation potentials than their parent sulfadiazine, but for the ten biodegradation products of sulfadiazine Cl-DBPs in CWs, 70% and almost 100% of them had lower bioaccumulation potentials than sulfadiazine and their parent sulfadiazine Cl-DBPs, respectively. The CWs were effective in reducing the environmental risk of sulfadiazine Cl-DBPs.

Albendazole (ALB) and bithionol (BIT) are two anthelmintic drugs (ADs) with high consumption from benzimidazole group and diphenylsulfide group, respectively. However, information on the transformation of the two anthelmintics under environmental condition is scare. Therefore, in the present study, we investigated the natural attenuation of the two ADs in the aquatic environment, including biodegradation, hydrolysis, and direct and indirect photodegradation. The direct photodegradation occupied a vast portion among other degradation pathways of the two ADs in natural water, with near-surface summer half-lives of 0.272-0.387 h and 0.110-0.520 h for ALB and BIT, respectively. Suspended particles in water were found to facilitate the photodegradation of the two ADs. Study on the indirect photodegradation demonstrated the positive roles of singlet oxygen (1O2) and excited triplet dissolved organic matter (3DOM*) in the photolysis of the two ADs, whereas the hydroxyl radical (•OH) affected little on the overall photodegradation procedures of ALB due to the scavenging effect of HCO3-. Dual effects of DO, DOM, HCO3-, NO3-, and NO2- on the photodegradation of ALB and BIT were perceived. Transformation intermediates (TIs) of the two ADs during photodegradation were analyzed by UHPLC-QTOF-MS. Six TIs of ALB were identified, including a broad-spectrum fungicide carbendazim and another common AD ricobendazole. Two TIs of BIT yielded from dechlorination were also detected. Probable transformation mechanism and predicted aquatic ecotoxicity based on the identified TIs were unveiled.

Due to the incomplete elimination by traditional wastewater treatment, antibiotics are becoming emerging contaminants, which are proved to be ubiquitous and promote bacterial resistance in the aquatic systems. Antibiotic pollution has raised particular concerns, calling for improved methods to clean wastewater and water. Photo-assisted advanced oxidation processes (AOPs) have attracted increasing attention because of the fast reaction rate, high oxidation capacity and low selectivity to remove antibiotics from wastewater. On the basis of latest literature, we found some new breakthroughs in the degradation mechanisms of antibiotic micropollutants with respect to the AOPs. Therefore, this paper summarizes and highlights the degradation kinetics, pathways and mechanisms of antibiotics degraded by the photo-assisted AOPs, including the UV/O3 process, photo-Fenton technology, and photocatalysis. In the processes, functional groups are attacked by hydroxyl radicals, and major structures are destroyed subsequently, which depends on the classes of antibiotics. Meanwhile, their basic principles, current applications and influencing factors are briefly discussed. The main challenges, prospects, and recommendations for the improvement of photo-assisted AOPs are proposed to better remove antibiotics from wastewater.

With the increase of algal blooms worldwide, drinking water resources are threatened by the release of various algal toxins, which can be hepatotoxic, cytotoxic, or neurotoxic. Because of their ubiquitous occurrence in global waters and incomplete removal in conventional drinking water treatment, oxidation/disinfection processes have become promising alternative treatment options to destroy both the structures and toxicity of algal toxins. This Review first summarizes the occurrence and regulation of algal toxins in source water and drinking water. Then, the transformation kinetics, disinfection byproducts (DBPs)/transformation products (TPs), pathways, and toxicity of algal toxins in water oxidation/disinfection processes, including treatment by ozonation, chlorination, chloramination, ultraviolet-based advanced oxidation process, and permanganate, are reviewed. For most algal toxins, hydroxyl radicals (HO•) exhibit the highest oxidation rate, followed by ozone and free chlorine. Under practical applications, ozone and chlorine can degrade most algal toxins to meet water quality standards. However, the transformation of the parent structures of algal toxins by oxidation/disinfection processes does not guarantee a reduction in toxicity, and the formation of toxic TPs should also be considered, especially during chlorination. Notably, the toxicity variation of algal toxins is associated with the chemical moiety responsible for toxicity (e.g., Adda moiety in microcystin-LR and uracil moiety in cylindrospermopsin). Moreover, the formation of known halogenated DBPs after chlorination indicates that toxicity in drinking water may shift from toxicity contributed by algal toxins to toxicity contributed by DBPs. To achieve the simultaneous toxicity reduction of algal toxins and their TPs, optimized oxidation/disinfection processes are warranted in future research, not only for meeting water quality standards but also for effective reduction of toxicity of algal toxins.