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Per- and Polyfluoroalkyl Substances (PFAS) are a group of persistent organic pollutants that have received considerable attention from public and regulatory groups. Due to regulations of long-chain PFAS, the use of short-chain and ultrashort-chain PFAS is rapidly growing. Thus, there is an urgent need to develop quantitative methods for determining PFAS with different chain lengths in various environmental matrices. This study introduces an innovative liquid chromatography-mass spectrometry (LC-MS) system combining large volume injection (LVI) and online solid phase extraction (SPE). This system incorporates three columns: a reverse-phase (RP) column, a weak anion exchange (WAX) trap column, and a hybrid HILIC/ion-exchange (HILIC/IE) column, controlled by two valves. With valve switching, ultrashort-chain PFAS that are not retained by the RP column are enriched by the trap column, while other PFAS are separated by the RP column. The trapped ultrashort PFAS are then transferred to the HILIC/IE column for further separation. The LVI significantly enhances the method's sensitivity, allowing for rapid and simultaneous determination of ultrashort-, short- and long- chain PFAS in aqueous samples. The matrix effects from various environmental samples were evaluated, and the results indicate that this unique LC-MS method is suitable for analyzing all chain-length PFAS in various matrices, including surface water, sewage effluent, and seawater. Finally, this novel LC-MS method was applied to quantify PFAS in various water samples., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

The occurrence and health risks of fluorescent whitening agents (FWAs) in bottled water were reported for the first time. FWA184 and FWA393 were the most frequently detected FWAs, with mean concentrations of 3.99-17.00 ng L -1 . Phthalates (PAEs) such as dibutyl phthalate (DBP), di-iso-butyl phthalate (DiBP), and diethylhexyl phthalate (DEHP) were prevalent in bottled water, with mean levels of 40.89-716.66 ng L -1 , and their concentrations in bottled water were much higher than those of FWAs. FWAs and PAEs in bottles and caps were extracted using organic solvent, and the correlation analysis showed that FWA393 and DEHP most likely originated from bottles, while bottle caps were the main sources of DBP and DiBP. The calculated risk quotients (RQs) of target substances and all age groups were considerably lower than the threshold of 0.1, indicating that consuming bottled water containing these plastic additives was unlikely to pose health risks for people of all ages. However, RQ values for underage people were several times higher than those for adults and hence cannot be neglected; therefore, special attention should be paid to understand the potential risks posed by the exposure to these plastic additives during early life stages, especially the infant stage., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

This study addresses the increasing concern regarding cyanotoxin contamination of water bodies, highlighting the diversity of these toxins and their potential health implications. Cyanobacteria, which are prevalent in aquatic environments, produce toxic metabolites, raising concerns regarding human exposure and associated health risks, including a potential increase in cancer risk. Although existing research has primarily focused on well-known cyanotoxins, recent technological advancements have revealed numerous unknown cyanotoxins, necessitating a comprehensive assessment of multiple toxin categories. To enhance the cyanotoxin databases, we optimized the CyanoMetDB cyanobacterial secondary metabolites database by incorporating secondary fragmentation patterns using the Mass Frontier fragmentation data prediction software. Water samples from diverse locations in Shanghai were analyzed using high-resolution mass spectrometry. Subsequently, the toxicity of cyanobacterial metabolites in the water samples was examined through acute toxicity assays using the crustacean Thamnocephalus platyurus. After 24 h of exposure, the semi-lethal concentrations (LC 50 ) of the water samples ranged from 0.31 mg L -1 to 1.78 mg L -1 (MC-LR equivalent concentration). Our findings revealed a critical correlation between the overall concentration of cyanobacterial metabolites and toxicity. The robust framework and insights of this study underscore the need for an inclusive approach to water quality management, emphasizing continuous efforts to refine detection methods and comprehend the broader ecological impact of cyanobacterial blooms on aquatic ecosystems., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

The reactive oxygen species (ROS) photochemically generated from natural iron minerals have gained significant attention. Amidst the previous studies on the impact of heavy metal ions on ROS generation, our study addresses the role of the anion Cr(VI), with its intrinsic photoactivity, in influencing ROS photochemical generation with the co-presence of minerals. We investigated the transformation of inorganic/organic pollutants (Cr(VI) and benzoic acid) at the ferrihydrite interface, considering sunlight-mediated conversion processes (300-1000 nm). Increased photochemical reactivity of ferrihydrite was observed in the presence of aqueous Cr(VI), acting as a photosensitizer. Meanwhile, a positive correlation between hydroxyl radical ( • OH) production and concentrations of aqueous Cr(VI) was observed, with a 650% increase of • OH generation at 50 mg L -1 Cr(VI) compared to systems without Cr(VI). Our photochemical batch experiments elucidated three potential pathways for • OH photochemical production under varying wet chemistry conditions: (1) ferrihydrite hole-mediated pathway, (2) chromium intermediate O -I -mediated pathway, and (3) chromium intermediates Cr IV/V -mediated pathway. Notably, even in the visible region (> 425 nm), the promotion of aqueous Cr(VI) on • OH accumulation was observed in the presence of ferrihydrite and TiO 2 suspensions, attributed to Cr(VI) photosensitization at the mineral interface. This study sheds light on the overlooked role of aqueous Cr(VI) in the photochemical reactivity of minerals, thereby enhancing our understanding of pollutant fate in acid mining-impacted environments., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Reactive oxygen species (ROS) play a crucial role in the biogeochemistry of aquatic environments, yet their occurrence and accumulation in the biofilm of submerged macrophytes have been poorly documented. Herein, we first investigated the light-dark cycling fluctuations of biofilm microenvironment and the temporal variations of a representative ROS (O 2 •- ) during biofilm succession on the macrophyte leaves and subsequently quantified the photochemical processes in biofilms. The sustained production of O 2 •- exhibited a distinct rhythmic fluctuation from 32.49 ± 0.56 μmol/kg to 72.56 ± 0.92 μmol/kg FW, which simultaneously fluctuated with the dissolved oxygen, redox potential, and pH, all driven by the alternating oxic-anoxic conditions of biofilms. The intensities of O 2 •- and ROS firstly increased and then decreased throughout biofilm succession. The O 2 •- concentrations in biofilms from different waters followed the order of rural river water > landscape lake water > aquaculture pond water, and the leaf photosynthesis and microbial community played a key role. ROS production was significantly associated with Actinobacteria, Proteobacteria and Bacteroidetes, with contributions of 44.6%, 32.8%, and 15.2%, respectively. Partial least squares path modeling structural equation analysis showed that ROS production in leaf biofilms was mainly related to the microenvironment and microbial metabolism. These findings will facilitate the development of ecological restoration strategies in aquatic environments., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Ten psychoactive substances (PSs) and metabolites were identified and quantified in 217 surface water samples collected across China to reveal the occurrence, distribution, and potential health risks in Chinese surface waters. The results showed the ubiquitous occurrence of caffeine (CFI), paraxanthine (PXT) and cotinine (CTN) at all the monitored sites, the concentrations of which ranged from not detected to 3460 ng L -1 , while the remaining PSs were detected at trace levels (<50 ng L -1 ). High concentrations of diet-related PSs (CTN, CFI, and PXT) typically occurred in areas with high population densities. Traditional drugs tended to occur in megacities and the illegal manufacturing bases of the illicit drugs. Emerging drugs were found to be very popular across the whole country, with no significant differences among the samples. The risk assessment results suggest that drinking water containing these PS residues posed no potential human health risk in any life stage. However, the age-dependent risk quotients (RQs) of the 5 assessed PSs for the 12 age intervals ranged from < 1.0 × 10 -7 to 0.005. In terms of the evaluated life stages, the RQs for early stages (from birth to <2 years) were significantly higher than the RQs for other stages., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Pharmaceutical and personal care products (PPCPs) are a group of emerging contaminants that have frequently been detected in aqueous environments. Phototransformation driven by solar irradiation is one of the most important natural processes for the elimination of PPCPs. In this study, primidone (PMD) was chosen as a model "photorefractory" compound. A series of experiments were conducted to assess if reactive intermediates (RIs), such as hydroxyl radical (HO), singlet oxygen ( 1 O 2 ), and triplet states of dissolved organic matter ( 3 DOM ⁎ ), inhibited or enhanced the photochemical transformation of PMD under simulated solar irradiation. The results indicate that HO plays a key role in the photodegradation of PMD and that dissolved oxygen can affect the degradation rate of PMD by promoting HO formation. Our results demonstrated that PMD can not only react with free HO (HO -free ) but also react with lower-energy hydroxylation agents (HO -like ). The contributions of HO -free and HO -like to PMD degradation in various dissolved organic matter (DOM) solutions were estimated by a methane-quenching experiment. The results indicated that the HO -like species were important in the photodegradation of "photorefractory" compounds. The bimolecular reaction rate constant of the reaction of free HO with PMD was measured as (5.21 ± 0.02) × 10 9  M -1  s -1 by using electron pulse radiolysis. Furthermore, PMD was used as a probe to estimate the steady-state concentration of HO -free in various DOM solutions. Using the multivariate statistical strategies of orthogonal projection to latent structures discriminant analysis (OPLS-DA) and hierarchical clustering, 28 photochemical transformation products (TPs) of PMD were successfully identified from the DOM matrix., (Copyright © 2019 Elsevier B.V. All rights reserved.)