Application of the Biological Toxicity Effect Ratio (BER) Method for Advancing Water Quality Criteria Derivation.

Water quality criteria (WQC) serve as a scientific foundation for pollutant risk assessment and control in aquatic ecosystems. The development of regionally differentiated WQC tailored to specific regional characteristics has become an emerging trend. However, the current WQC is constrained by a lack of regional species toxicity data. To address these limitations, this study proposes the biological toxicity effect ratio (BER) method, which indirectly reflects the toxicity sensitivity of the overall aquatic ecosystem through the toxicity information on a limited number of species, enabling rapid WQC prediction. Using the established WQC in China and the USA as a case study, we combined mathematical derivation and data validation to evaluate the BER method. Among various species-taxon groups of freshwater organisms, planktonic crustaceans demonstrated the highest predictive accuracy. Our analysis further revealed that species toxicity sensitivity and regional variability jointly influence the prediction accuracy. Regardless of the evaluation indexes, planktonic crustaceans emerged as the most suitable species-taxon group for the BER method. Additionally, the BER method is particularly applicable to pollutants with conserved mechanisms across species. This study systematically explores the feasibility of using the BER method and offers new insights for deriving regionally differentiated WQC.

Magnitude Filter Combined with Mass Filter: A Reliable Strategy to Improve the Reproducibility of ESI-FT-ICR-MS Analysis on the Fingerprint of Dissolved Organic Matter.

Dissolved organic matter (DOM) has been used frequently to distinguish different environmental samples based on its abundant fingerprint information. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) is the most powerful technique to analyze the complex composition of DOM. Balancing between the reproducibility of peak magnitude and peak diversity is a key factor for achieving reliable and reproducible fingerprint information of DOM with FT-ICR-MS. In this paper, a novel magnitude filter (MGF) method and a novel MS-MGF strategy were proposed to improve the data reproducibility of FT-ICR-MS analysis. With the MS-MGF strategy, a 20% magnitude filter threshold (TMGF) was recommended to remove magnitude outliers, and a relatively low signal-to-noise ratio (SNR) threshold of 3.5 was recommended to retain those low but stable-magnitude peaks. The total relative magnitude was recommended since it could obtain better reproducibility of MS analysis compared to other types of peak magnitude. In addition, three replicates were enough to obtain satisfactory reproducibility. More importantly, the proposed MS-MGF strategy was also adaptable to different FT-ICR-MS instruments and different experimental conditions. Overall, the results are expected to initiate the promising applications of the MS-MGF strategy to distinguish the reliable fingerprint characteristics of DOM samples from different sources.

A synthetical methodology for identifying priority pollutants in reclaimed water based on meta-analysis.

Wastewater reclamation and reuse is an increasing global project, while the reclamation treatment on wastewater does not completely remove all pollutants in water. The residual pollutants in reclaimed water would cause potential risk on human health and ecosystem safety during the long-term use. It is impossible to analyze and control all pollutants one by one in practice, therefore, identification and control of priority pollutants will be efficient strategy to ensure the safe use of reclaimed water. An integrated three-step methodology for identifying priority pollutants in reclaimed water was proposed in this study. First, a comprehensive literature survey on the occurrence of pollutants in reclaimed water was conducted, and a dataset DPR for pollutants occurrence in reclaimed water was established, containing 1,113 pollutants. Second, 611 chemicals that had been recommended as hazardous pollutants for various water bodies in previous literatures were summarized, and a dataset DHP for hazardous pollutants in water was obtained. Third, meta-analysis on these two datasets (DPR and DHP) was performed, a new dataset DHPR for hazardous pollutants in reclaimed water was established, including 265 candidates. Finally, 59 substances out of dataset DHPR were identified as priority pollutants for reclaimed water based on their recommendation frequency. It is expected that this synthetical methodology will provide powerful support for scientific evaluating and managing water pollution and ensuring safe use of reclaimed water.

The origin and spread of CRF85_BC, driven by heterosexual transmission among older people in Sichuan, China.

BACKGROUND: CRF_BC recombinants, including CRF07_BC and CRF08_BC, were considered the predominant subtypes in China. Since the discovery of HIV-1 circulating recombinant form CRF 85_BC in Southwest China in 2016, this BC recombinant forms had been reported in different regions of China. However, the history and magnitude of CRF85_BC transmission were still to be investigated. METHOD: We conducted the most recent molecular epidemiology of HIV-1 among newly reported HIV-1 infected patients in Sichuan in 2019 by sequencing and phylogenetic analysis of 1291 pol sequences. Then, we used maximum likelihood approach and the Bayesian Markov chain Monte Carlo (MCMC) sampling of pol sequences to reconstruct the phylogeographic and demographic dynamics of the CRF85_BC. RESULTS: HIV-1 CRF85_BC (68/1291, 5.27%) became the fourth most prevalent strain revealing a significant increase in local population. CRF85_BC were only found in heterosexually infected individuals and the majority of CRF85_BC (95.45%) were circulating among the people living with HIV aged 50 years and over (PLHIV50+), suggesting a unique prevalent pattern. The founder lineages of CRF85_BC were likely to have first emerged in Yunnan, a province of Southwest China bordering Sichuan, in the early 2000s. It then spread exponentially to various places (including Guangxi, Sichuan, et al) and became endemic around 2008.6 (2006.7-2010.2) in Sichuan. CONCLUSION: Taken together, our findings on HIV-1 subtype CRF85_BC infections provided new insights into the spread of this virus and extended the understanding of the HIV epidemic in China.

Bioassay: A useful tool for evaluating reclaimed water safety.

Wastewater reclamation and reuse has been proved to be an effective way to relieve the fresh water crisis. However, toxic contaminants remaining in reclaimed water could lead to potential risk for reuse, and the conventional water quality standards have difficulty guaranteeing the safety of reclaimed water. Bioassays can vividly reflect the integrated biological effects of multiple toxic substances in water as a whole, and could be a powerful tool for evaluating the safety of reclaimed water. Therefore, in this study, the advantages and disadvantages of using bioassays for evaluating the safety of reclaimed water were compared with those of conventional water quality standards. Although bioassays have been widely used to describe the toxic effects of reclaimed water and treatment efficiency of reclamation techniques, a single bioassay cannot reflect the complex toxicity of reclaimed water, and a battery of bioassays involving multiple biological effects or in vitro tests with specific toxicity mechanisms would be recommended. Furthermore, in order to evaluate the safety of reclaimed water based on bioassay results, various methods including potential toxicology, the toxicity unit classification system, and a potential eco-toxic effects probe are summarized as well. Especially, some integrated ranking methods based on a bioassay battery involving multiple toxicity effects are recommended as useful tools for evaluating the safety of reclaimed water, which will benefit the promotion and guarantee the rapid development of the reclamation and reuse of wastewater.

A selective N,N-dithenoyl-rhodamine based fluorescent probe for Fe3+ detection in aqueous and living cells.

A novel N,N-dithenoyl-rhodamine based fluorescent and colorimetric Fe3+ probe 1 was designed and synthesized by only one step from Rhodamine B hydrazide and 2-thiophenecarbonyl chloride. The structure of probe 1 was characterized by 1H NMR/13C NMR spectroscopy, IR spectroscopy, and HRMS spectrometry. Accompanying with significant changes in visual color and fluorescent spectrum, probe 1 displayed good sensitivity for Fe3+ with an abroad pH span. The detection limit (3.76 µmol/L, 0.2 mg/L) for Fe3+ was lower than WHO recommended value (0.3 mg/L) for drinking water. Using two thiophene carbonyl groups as coordinating functional recognition group, probe 1 showed excellent selectivity towards Fe3+ over diverse coexistent metal ions and anions. The sensing mechanism between dithenoyl-substituted probe 1 and Fe3+ was further confirmed by 1H NMR and IR titration experiments, binding constants study, and Job's plot analysis. Furthermore, probe 1 also exhibited good cell membrane permeability and could be used as an efficient Fe3+ probe in living human cells.

Effectively remediating spiramycin from production wastewater through hydrolyzing its functional groups using solid superacid TiO2/SO4.

Breaking down the structural bonds and eliminating the functional groups are more efficient than destroying the whole molecule in antibiotic production wastewater (APW) pretreatment before further biotreatment. Two sulfated titania (TiO2/SO4) solid superacids, SSA1 and SSA2 were synthesized, characterized and used for hydrolytic pretreatment of spiramycin in APW. Spiramycin removal followed an order of SSA2>SSA1>TiO2≈pH = 3>control. The hydrolytic efficiencies increased at elevated temperature from 25 °C to 65 °C. The hydrolytic kinetics followed a first-order model and SSA2 performed the fastest. The performances were positively correlated with both the total acidity determined by n-butylamine titration and the strength of acid sites measured by NH3-temperature-programmed desorption (TPD). The residual solution for SSA2 presented the least antibacterial potency and anaerobic inhibition among all treatments. The hydrolyzed product was identified as the m/z 699.4321 fragment using UPLC-Q/TOF-MS, which was formed after losing a functional mycarose moiety from the parent molecular. The solid superacids were effective in selectively eliminating 433 mg/L of spiramycin and the antibacterial potencies of the spiramycin production wastewater, which contained very high concentrations of COD (33,000 mg/L). This hydrolytic method avoids using and handling hazardous and corrosive mineral acids on site. It is attractive as a selective catalytic pretreatment method to cleave antibiotics' functional groups and to reduce its inhibitory effects before sequential biotreatments.

Research progress of disinfection and disinfection by-products in China.

Disinfection is an indispensable water treatment process for killing harmful pathogens and protecting human health. However, the disinfection has caused significant public concern due to the formation of toxic disinfection by-products (DBPs). Lots of studies on disinfection and DBPs have been performed in the world since 1974. Although related studies in China started in 1980s, a great progress has been achieved during the last three decades. Therefore, this review summarized the main achievements on disinfection and DPBs studies in China, which included: (1) the occurrence of DBPs in water of China, (2) the identification and detection methods of DBPs, (3) the formation mechanisms of DBPs during disinfection process, (4) the toxicological effects and epidemiological surveys of DBPs, (5) the control and management countermeasures of DBPs in water disinfection, and (6) the challenges and chances of DBPs studies in future. It is expected that this review would provide useful information and reference for optimizing disinfection process, reducing DBPs formation and protecting human health.

Acute toxicity variation of hydroxyl benzophenone UV filters during photoinduction-chlorination disinfection processes.

Benzophenones (BPs), a group of widely used UV filters, exert multiple, significant toxicity effects. The 11 BPs were selected as target compounds, and the photobacterium acute toxicity test and an index for acute toxicity formation potential (ATFP) were used to evaluate the toxicity variation of BPs before and after a photoinduction-chlorination disinfection process. Orthogonal experiments were performed at different pH values and chlorine dosages. The characteristics of ATFP values for 11 BPs after a photoinduction-chlorination process can be summarized as follows: (1) The ATFPs decreased as the hydroxyl group number increased in BPs molecules. (2) For those BPs with the same hydroxyl group number, the ATFPs were higher when the hydroxyl groups were located at the 3- or 4-position than those at the 2-position; the BPs with hydroxyl groups distributed on two benzene rings had higher ATFPs than those on one ring. (3) Introducing a methoxyl group and sulfonic acid group into BP molecules increased the ATFP values. (4) The ATFPs were pH-dependent, the values of which were lowest at the neutral condition and highest at the acid condition. (5) The ATFPs increased and then decreased as the chlorine dosage increased. The results can be used as a reference to scientifically evaluate the environmental fate and potential risk of BPs in photoinduction-chlorination disinfection processes.

The chlorination transformation characteristics of benzophenone-4 in the presence of iodide ions.

Benzophenone-type UV filters are a group of compounds widely used to protect human skin from damage of UV irradiation. Benzophenone-4 (BP-4) was targeted to explore its transformation behaviors during chlorination disinfection treatment in the presence of iodide ions. With the help of ultra performance liquid phase chromatograph and high-resolution quadrupole time-of-flight mass spectrometer, totally fifteen halogenated products were identified, and five out of them were iodinated products. The transformation mechanisms of BP-4 involved electrophilic substitution generating mono- or di-halogenated products, which would be oxidized into esters and further hydrolyzed into phenolic derivatives. The desulfonation and decarboxylation were observed in chlorination system either. Obeying the transformation pathways, five iodinated products formed. The pH conditions of chlorination system determined the reaction types of transformation and corresponding species of products. The more important was that, the acute toxicity had significant increase after chlorination treatment on BP-4, especially in the presence of iodide ions. When the chlorination treatment was performed on ambient water spiked with BP-4 and iodide ions, iodinated by-products could be detected.

Predicted no-effect concentrations for mercury species and ecological risk assessment for mercury pollution in aquatic environment.

Mercury (Hg) exists in different chemical forms presenting varied toxic potentials. It is necessary to explore an ecological risk assessment method for different mercury species in aquatic environment. The predicted no-effect concentrations (PNECs) for Hg(II) and methyl mercury (MeHg) in the aqueous phase, calculated using the species sensitivity distribution method and the assessment factor method, were 0.39 and 6.5×10(-3)µg/L, respectively. The partition theory of Hg between sediment and aqueous phases was considered, along with PNECs for the aqueous phase to conduct an ecological risk assessment for Hg in the sediment phase. Two case studies, one in China and one in the Western Black Sea, were conducted using these PNECs. The toxicity of mercury is heavily dependent on their forms, and their potential ecological risk should be respectively evaluated on the basis of mercury species.

The potential risk assessment for different arsenic species in the aquatic environment.

The different toxicity characteristics of arsenic species result in discrepant ecological risk. The predicted no-effect concentrations (PNECs) 43.65, 250.18, and 2.00×10(3)µg/L were calculated for As(III), As(V), and dimethylarsinic acid in aqueous phase, respectively. With these PNECs, the ecological risk from arsenic species in Pearl River Delta in China and Kwabrafo stream in Ghana was evaluated. It was found that the risk from As(III) and As(V) in the samples from Pearl River Delta was low, while much high in Kwabrafo stream. This study implies that ecological risk of arsenic should be evaluated basing on its species.

Acute toxicity evaluation for quinolone antibiotics and their chlorination disinfection processes.

Acute toxicity of 21 quinolone antibiotics was monitored using photobacterium Vibrio fischeri assay. The minimum IC20 (inhibitory concentration for 20% luminescence elimination) was obtained at the least 18.86µmol/L for the tested quinolones. A quantitative structure-activity relationship model was established to investigate the possible mechanism for the acute toxicity. The critical physicochemical descriptors, describing σ and π atom electronegativity, implied that the electron transfer might occur between the quinolones and photobacterium V. fischeri. Although the quinolones exhibited limited acute toxicity to photobacterium, toxicity elevation was detected after their chlorination. Hence, chlorination disinfection treatment of quinolone-containing water should be of concerns.

A toxicity-based method for evaluating safety of reclaimed water for environmental reuses.

A large quantity of toxic chemical pollutants possibly remains in reclaimed water due to the limited removal efficiency in traditional reclamation processes. It is not enough to guarantee the safety of reclaimed water using conventional water quality criteria. An integrated assessment method based on toxicity test is necessary to vividly depict the safety of reclaimed water for reuse. A toxicity test battery consisting of lethality, genotoxicity and endocrine disrupting effect was designed to screen the multiple biological effects of residual toxic chemicals in reclaimed water. The toxicity results of reclaimed water were converted into the equivalent concentrations of the corresponding positive reference substances (EQC). Simultaneously, the predicted no-effect concentration (PNEC) of each positive reference substance was obtained by analyzing the species sensitivity distribution (SSD) of toxicity data. An index "toxicity score" was proposed and valued as 1, 2, 3, or 4 depending on the ratio of the corresponding EQC to PNEC. For vividly ranking the safety of reclaimed water, an integrated assessment index "toxicity rank" was proposed, which was classified into A, B, C, or D rank with A being the safest. The proposed method was proved to be effective in evaluating reclaimed water samples in case studies.

Acute toxicity formation potential of benzophenone-type UV filters in chlorination disinfection process.

Benzophenones (BPs) are a class of widely used UV filters, which have been frequently detected within multiple environmental matrices. Disinfection is a necessary process in water treatment processes. The transformation behaviors and toxicity changes of 14 BP-type UV filters during chlorination disinfection treatment were investigated in this study. A new index, the acute toxicity formation potential, was proposed to evaluate the toxicity changes and potential risks of BP-type UV filters during chlorination treatment. It was found that 13 of 14 BP-type UV filters exhibited toxicity decreases in the chlorination disinfection process, more or less, while one showed a toxicity increase. The toxicity changes were dependent on substitution effects, such that 2,4-di-hydroxylated or 3-hydroxylated BPs exhibited significant toxicity decreases after chlorination treatment due to the ready cleavage of the aromatic ring. Importantly, the acute toxicity changes could be duplicated in an ambient water matrix.

Formation pathways of brominated products from benzophenone-4 chlorination in the presence of bromide ions.

The brominated products, formed in chlorination treatment of benzophenone-4 in the presence of bromide ions, were identified, and the formation pathways were proposed. Under disinfection conditions, benzophenone-4 would undertake electrophilic substitution generating mono- or di-halogenated products, which would be oxidized to esters and further hydrolyzed to phenol derivatives. The generated catechol intermediate would be transformed into furan-like heterocyclic product. The product species were pH-dependent, while benzophenone-4 elimination was chlorine dose-dependent. When the chlorination treatment was performed on ambient water spiked with benzophenone-4 and bromide ions, most of brominated byproducts could be detected, and the acute toxicity significantly increased as well.

Formation of nitrogen-containing disinfection by-products during the chloramination treatment of an emerging pollutant.

Chloramination was commonly used as disinfectant for killing pathogens in water. However, in this process, nitrogen-containing disinfection by-products (N-DBPs) would accidently form and subsequently rise toxicity. Here, we investigated acute toxicity variation and by-products formation during chloramination treatment on UV filter 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone (BP-4). Under alkaline conditions, the acute toxicity of this system had significant increase. A total of 17 transformation products were tentatively identified, and for them, plausible transformation pathways were proposed. Noticeably, numerous aniline and nitrosobenzene analogs were detected, and the dramatic increase of acute toxicity in this system might be primarily attributed to the formation of benzoquinone and aniline analogs. Besides, bromophenol, iodophenol and iodobenzoquinone analogs exhibiting high toxicity were generated in the presence of bromine and iodide ions. This study indicates that chloramination treatment may significantly increase potential health risk, further management on disinfection system is reasonable.

Releasing characteristics of toxic chemicals from polystyrene microplastics in the aqueous environment during photoaging process.

Microplastics (MPs) are pervasive in the environment and inevitably undergo photoaging due to UV irradiation. This study delved into the dynamic releasing and transformation process of toxic chemicals from polystyrene microplastics (PS MPs) during photoaging, a subject that remains underexplored. It was revealed that photoaging led to substantial alterations in the physicochemical properties of PS MPs, initiating polymer chain scission and facilitating the release of a large number of toxic chemicals, including numerous organic compounds and several inorganic compounds. The kinetic analysis revealed a dynamic release pattern for PS MPs, where under varying UV intensities (2, 5, and 10 mW/cm2), the release rate (kDOC) initially increased and then decreased, peaking at a total irradiation energy of approximately 7 kW·h/m2. Furthermore, chemicals in leachate were transformed into compounds with smaller molecular weight, higher oxidized and greater unsaturated state over the prolonged photoaging. This transformation was primarily attributed to two reasons. Firstly, the aged PS MPs released chemicals with higher oxidized state compared to the pristine MPs. Secondly, the chemicals previously released underwent further reactions. Besides, among the complex leachate generated by aged PS MPs, the organic chemicals characterized by small molecular weight and high oxidized state exhibited notable acute toxicity, whereas heavy metal ions showed lesser toxicity, and anions were non-toxic. This study shed more light on the photoaging process of PS MPs, releasing characteristics of organic chemicals, and the potential environmental risks associated with plastic wastes.

Tailor-made ammonia nitrogen risk management with machine learning models for aquatic environments in the Mainland of China.

Efficient management of pollutant risks in water bodies is crucial for public health and aquatic ecosystem sustainability. However, the toxicities of pollutants, such as ammonia nitrogen (NH3-N), are often affected by multiple water quality factors, including the pH and water temperature. Extensive spatial and temporal variability in these factors hinders tailor-made management of risk. This study used high-frequency monitoring data collected over 1 year to evaluate the long-term NH3-N risk in China's aquatic ecosystems. High accuracy and interpretability were achieved by decomposing NH3-N risk into the contributions of key influencing factors using random forest models and Shapley Additive Explanations. Two distinct types of NH3-N risk hotspots were identified across 18 cities: 15 cities with high NH3-N concentrations and 3 cities with low environmental carrying capacity due to high pH levels or elevated water temperatures. For the former, rapid NH3-N abatement measures are necessary to bring NH3-N concentrations back below the environmental capacity. For the latter, it is recommended that NH3-N related industries are relocated to regions with high environmental capacities because fragile environments are not suitable for such industries. Importantly, this study investigated methods for attributing pollutant risks in the context of non-linear influencing factors, and the risk of NH3-N was predicted to increase by 6.1 % by the end of 2100 in the context of increasing temperatures under the SSP 2-4.5 scenario. The methodology is also adaptable and suitable for integration into global ecosystem risk management efforts to balance development and aquatic ecological sustainability.

Profound regional disparities shaping the ecological risk in surface waters: A case study on cadmium across China.

The scientific advancement of water quality criteria (WQC) stands as one of the paramount challenges in ensuring the security of aquatic ecosystem. The region-dependent species distribution and water quality characteristics would impact the toxicity of pollutant, which would further affect the derivation of WQC across regions. Presently, however, numerous countries adhere to singular WQC values. The "One-size-fits-all" WQC value for a given pollutant may lead to either "over-protection" or "under-protection" of organisms in specific region. In this study, we used cadmium(Cd) pollution in surface waters of China as a case study to shed light on this issue. This study evaluated critical water quality parameters and species distribution characteristics to modify WQC for Cd across distinct regions, thus unveiling the geographical variations in ecological risk for Cd throughout China. Notably, regional disparities in ecological risk emerged a substantial correlation with water hardness, while species-related distinctions magnified these regional variations. After considering the aforementioned factors, the variation in long-term WQC among different areas reached 84-fold, while the divergence in risk quotient extended to 280-fold. This study delineated zones of both heightened and diminished ecological susceptibility of Cd, thereby establishing a foundation for regionally differentiated management strategies.