Toxicity Evaluation and Effect-Based Identification of Chlorine Disinfection Products of the Anti-COVID-19 Drug Chloroquine Phosphate.

Antiviral transformation products (TPs) generated during wastewater treatment are an environmental concern, as their discharge, in considerable amounts, into natural waters during a pandemic can pose possible risks to the aquatic environment. Identification of the hazardous TPs generated from antivirals during wastewater treatment is important. Herein, chloroquine phosphate (CQP), which was widely used during the coronavirus disease-19 (COVID-19) pandemic, was selected for research. We investigated the TPs generated from CQP during water chlorination. Zebrafish (Danio rerio) embryos were used to assess the developmental toxicity of CQP after water chlorination, and hazardous TPs were estimated using effect-directed analysis (EDA). Principal component analysis revealed that the developmental toxicity induced by chlorinated samples could be relevant to the formation of some halogenated TPs. Fractionation of the hazardous chlorinated sample, along with the bioassay and chemical analysis, identified halogenated TP387 as the main hazardous TP contributing to the developmental toxicity induced by chlorinated samples. TP387 could also be formed in real wastewater during chlorination in environmentally relevant conditions. This study provides a scientific basis for the further assessment of environmental risks of CQP after water chlorination and describes a method for identifying unknown hazardous TPs generated from pharmaceuticals during wastewater treatment.

Do NH4+-N and AOB affect atenolol removal during simulated riverbank filtration?

Biodegradation is regarding as the most important organic micro-pollutants (OMPs) removal mechanism during riverbank filtration (RBF), but the OMPs co-metabolism mechanism and the role of NH4+-N during this process are not well understood. Here, we selected atenolol as a typical OMP to explore the effect of NH4+-N concentration on atenolol removal and the role of ammonia oxidizing bacteria (AOB) in atenolol biodegradation. The results showed that RBF is an effective barrier for atenolol mainly by biodegradation and adsorption. The ratio of biodegradation and adsorption to atenolol removal was dependent on atenolol concentration. Specifically, atenolol with low concentration (500 ng/L) is almost completely removed by adsorption, while atenolol with higher concentration (100 µg/L) is removed by biodegradation (51.7%) and adsorption (30.8%). Long-term difference in influent NH4+-N concentrations did not show significant impact on atenolol (500 ng/L) removal, which was mainly dominated by adsorption. Besides, AOB enhanced the removal of atenolol (100 µg/L) as biodegradation played a more crucial role in removing atenolol under this concentration. Both AOB and heterotrophic bacteria can degrade atenolol during RBF, but the degree of AOB's contribution may be related to the concentration of atenolol exposure. The main reactions occurred during atenolol biodegradation possibly includes primary amide hydrolysis, hydroxylation and secondary amine depropylation. About 90% of the bio-transformed atenolol was produced as atenolol acid. AOB could transform atenolol to atenolol acid by inducing primary amide hydrolysis but failed to degrade atenolol acid further under the conditions of this paper. This study provides novel insights regarding the roles played by AOB in OMPs biotransformation during RBF.

Role of ammonia-oxidizing microorganisms in the removal of organic micropollutants during simulated riverbank filtration.

Biodegradation plays an important role in the removal of organic micropollutants (OMPs) during riverbank filtration (RBF) for drinking water production. The ability of ammonia-oxidizing microorganisms (AOM) to remove OMPs has attracted increasing attention. However, the distribution of AOM in RBF and its role in the degradation of OMPs remains unknown. In this study, the behavior of 128 selected OMPs and the distribution of AOM and their roles in the degradation of OMPs in RBF were explored by column and batch experiments simulating the first meter of the riverbank. The results showed that the selected OMPs were effectively removed (82/128 OMPs, >70% removal) primarily by biodegradation and partly by adsorption. Inefficiently removed OMPs tended to have low molecular weights, low log P, and contain secondary amides, secondary sulfonamides, secondary ketimines, and benzyls. In terms of the microbial communities, the relative abundance of AOM increased from 0.1%-0.2% (inlet-sand) to 5.3%-5.9% (outlet-sand), which was dominated by ammonia-oxidizing archaea whose relative abundance increased from 23%-72% (inlet-sand) to 97% (outlet-sand). Comammox accounted for 23%-64% in the inlet-sand and 1% in the outlet-sand. The abundances of AOM amoA genes kept stable in the inlet-sand of control columns, while decreased by 78% in the treatment columns, suggesting the inhibition effect of allylthiourea (ATU) on AOM. It is observed that AOM played an important role in the degradation of OMPs, where its inhibition led to the corresponding inhibition of 32 OMPs (5/32 were completely suppressed). In particular, OMPs with low molecular weights and containing primary amides, secondary amides, benzyls, and secondary sulfonamides were more likely to be removed by AOM. This study reveals the vital role of AOM in the removal of OMPs, deepens our understanding of the degradation of OMPs in RBF, and offers valuable insights into the physiochemical properties of OMPs and their AOM co-metabolic potential.