Search

Diffusive gradients in thin films (DGTs) have been well-documented for the measurement of a broad range of organic pollutants in surface water. However, the performance has been challenged by the inherent periodic concentration fluctuations for most organic pollutants. Therefore, there is an urgent need to assess the true time-weighted average (TWA) concentration based on fluctuating concentration profiles. The study aimed to evaluate the responsiveness of DGT and accuracy of TWA concentrations, considering various concentration fluctuating scenarios of 20 pharmaceuticals in surface water. The reliability and accuracy of the TWA concentrations measured by the DGT were assessed by comparison with the sum of cumulative mass of DGT exposed at different stages over the deployment period. The results showed that peak concentration duration (1-5 days), peak concentration fluctuation intensity (6-20 times), and occurrence time of peak concentration fluctuation (early, middle, and late stages) have minimal effect on DGT's response to most target pharmaceutical concentration fluctuations (0.8 < C DGT /C TWA  < 1.2). While the downward-bent accumulations of a few pharmaceuticals on DGT occur as the sampling time increases, which could be accounted for by capacity effects during a long-time sampling period. Additionally, the DGT device had good sampling performance in recording short fluctuating concentrations from a pulse event returning to background concentrations with variable intensity and duration. This study revealed a satisfactory capacity for the evaluation of the TWA concentration of pharmaceuticals integrated over the period of different pulse deployment for DGT, suggesting that this passive sampler is ideally suited as a monitoring tool for field application. This study represents the first trial for evaluating DGT sampling performance for pharmaceuticals with multiple concentration fluctuating scenarios over time, which would be valuable for assessing the pollution status in future monitoring campaign., 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.)

Natural estrogen conjugates play important roles in municipal wastewater treatment plant (WWTP), but their deconjugation potentials are poorly understood. This work is the first to investigate the relationships between the enzyme activities of arylsulfatase/β-glucuronidase and deconjugation potentials of natural estrogen conjugates. This work led to three important findings. First, the enzyme activity of β-glucuronidase in sewage is far higher than that of arylsulfatase, while their corresponding activities in activated sludge were similar. Second, a model based on β-glucuronidase could successfully predict the deconjugation potentials of natural estrogen glucuronide conjugates in sewage. Third, the enzyme activity of arylsulfatase in sewage was too low to lead to evident deconjugation of sulfate conjugates, which means that the deconjugation rate of estrogen sulfates can be regarded as zero. By comparing their theoretical removal based on enzyme activity and on-site investigation, it is reasonable to conclude that reverse deconjugation of estrogen conjugates (i.e., conjugation of natural estrogens to form conjugated estrogens) likely exist in WWTP, which explains well why natural estrogen conjugates cannot be effectively removed in WWTP. Meanwhile, this work provides new insights how to improve the removal performance of WWTP on natural estrogen conjugates. SYNOPSIS: This work is the first to show how arylsulfatase/β-glucuronidase could affect deconjugation of natural estrogen conjugates and possible way to enhance their removal in wastewater treatment plant., 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.)

Perfluoroalkyl acids (PFAAs) of different chemical speciation were previously found to cause diverse toxicity. However, the toxicological mechanisms depending on chemical speciation are still largely unknown. In this follow-up study, zebrafish embryos were acutely exposed to only one concentration at 4.67 μM of the acid and salt of representative PFAAs, including perfluorooctanoic acid (PFOA), perfluorobutane carboxylic acid (PFBA), and perfluorobutanesulfonic acid (PFBS), till 96 h post-fertilization (hpf), aiming to gain more mechanistic insights. High-throughput proteomics found that PFAA acid and salt exerted discriminative effects on protein expression pattern. Bioinformatic analyses based on differentially expressed proteins underlined the developmental cardiotoxicity of PFOA acid with regard to cardiac muscle contraction, vascular smooth muscle contraction, adrenergic signaling in cardiomyocytes, and multiple terms related to myocardial contraction. PFOA salt and PFBS acid merely disrupted the cardiac muscle contraction pathway, while cardiac muscle cell differentiation was significantly enriched in PFBA acid-exposed zebrafish larvae. Consistently, under PFAA exposure, especially PFOA and PFBS acid forms, transcriptional levels of key genes for cardiogenesis and the concentrations of troponin and epinephrine associated with myocardial contraction were significantly dysregulated. Moreover, a transgenic line Tg (my17: GFP) expressing green fluorescent protein in myocardial cells was employed to visualize the histopathology of developing heart. PFOA acid concurrently caused multiple deficits in heart morphogenesis and function, which were characterized by the significant increase in sinus venosus and bulbus arteriosus distance (SV-BA distance), the induction of pericardial edema, and the decrease in heart rate, further confirming the stronger toxicity of PFOA acid than the salt counterpart on heart development. Overall, this study highlighted the developmental cardiotoxicity of PFAAs, with potency ranking PFOA > PFBS > PFBA. The acid forms of PFAAs induced stronger cardiac toxicity than their salt counterparts, providing an additional insight into the structure-toxicity relationship., 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.)

While combinations of pesticides better represent actual conditions within aquatic ecosystems, the specific toxic effects of these combinations have not been determined yet. The objective of this research was to assess the combined impact of imazalil and azoxystrobin on the hook snout carp (Opsariichthys bidens) and delve into the underlying causes. Our findings indicated that the 4-day LC 50 value for imazalil (1.85 mg L -1 ) was greater than that for azoxystrobin (0.90 mg L -1 ). When imazalil and azoxystrobin were combined, they presented a heightened effect on the species. Enzyme activities like SOD, CAT, GST, and CarE, along with androgen and estrogen levels, displayed marked differences in most single and combined treatments in comparison to the baseline group. Moreover, four genes (mn-sod, cu-sod, il-1, and esr) related to oxidative stress, immunity, and the endocrine system exhibited more pronounced expression changes when exposed to combined pesticides rather than individual ones. Our tests revealed that the combined use of imazalil and azoxystrobin had more detrimental effect on aquatic vertebrates than when evaluated individually. This finding suggested that future ecological hazard analyses based only on individual tests might not sufficiently safeguard our 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 Elsevier B.V. All rights reserved.)

Although Eichhornia crassipes, commonly known as water hyacinth, has been widely used in wastewater treatment, further investigations are still needed to explore the removal efficiency of perfluoroalkyl acids (PFAAs) from the aqueous environment using this floating aquatic plant. In this study, a hydroponic experiment was conducted to assess accumulation, bioconcentration factors (BCFs), translocation factors (TFs), and removal rates of eight PFAAs by water hyacinth. The obtained results indicated that all PFAAs, including five perfluoroalkyl carboxylic acids (PFCAs) with chain lengths C4-C8 and three perfluoroalkyl sulfonic acids (PFSAs) with C4, C6, and C8, were readily accumulated in water hyacinth. Throughout the duration of the experiment, there was a noticeable increase in PFAA concentrations and BCF values for different plant parts. For the root, PFAAs with more carbon numbers showed a higher uptake than the shorter homologues, with PFSAs being more readily accumulated compared to PFCAs with the same carbon number in the molecules. In contrast, the levels of long-chain PFAAs were comparatively lower than those of short-chain substances in the stem and leaf. Notably, PFAAs with less carbon numbers, like PFPeA, PFBA, and PFBS, showed a remarkable translocation from the root to the stem and leaf with TFs >1. For the whole plant, no significant correlation was found between BCFs and organic carbon-water partition coefficients (K oc ), octanol-water partition coefficients (K ow ), membrane-water distribution coefficients (D mw ), or protein-water distribution coefficients (D pw ). The removal rates of PFAAs ranged from 40.3 to 63.5 % throughout the three weeks of the experiment while the removal efficiencies varied from 48.9 % for PFHxS to 82.6 % for PFPeA in the last week., 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.)

Anthropogenic Contaminants of Emerging Concern (CECs) in marine environments have raised significant concerns. Yet, analyses detailing their origins, fate, and environmental effects are limited. This study employs an integrated non-target screening methodology to elucidate CECs existence across 46 sampling sites in the Pearl River Estuary (PRE) of the South China Sea. Assisted by advanced liquid chromatography-high resolution mass spectrometry, we discovered 208 chemicals in six usage categories, with pesticides (33 %) and pharmaceuticals (29 %) predominating. Several CECs drew attention for their consistent detections, profound abundance, and significant ecotoxicities. The wide detection of them at offshore sites further implies that anthropogenic activities may contribute to large-scale contamination. Meanwhile, distinct distribution patterns of CECs across PRE are evident in semi-quantitative results, indicating regional anthropogenic influences. Identified transformation products may establish a novel and non-negligible negative contribution to ecology through elevated environmental toxicities, exemplified by HMMM and atrazine. Based on the ecological risks, we compiled a prioritized list of 21 CECs warranting intensified scrutiny. Our findings indicate the introduction of various CECs into the South China Sea via PRE, emphasizing the urgent necessity for ongoing surveillance of discharged CECs at estuary areas and assessment of their marine ecological consequences., 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.)

Floating Vegetated System (FVS) emerged as a green and sustainable technology, presenting a viable solution for treating heavy metals (HMs) contaminated water without disrupting the food web. Pistia stratiotes has been used in the design of FVS due to its abundance of aerenchyma tissues, which contribute to its ability to remain buoyant. FVS exhibited significant HMs removal efficiencies, with Pb top at average 84.4 %, followed by Zn (81.1 %), Cr (78.5 %), Cu (76.5 %) and Ni (73 %). Bio-concentration Factor (BCF) and Translocation Factor (TF) values evaluated the plant's adeptness in metal uptake. For plants treated with Cu, the highest post-treatment chlorophyll content of 9 ± 1 mg.ml -1 was observed while Zn induced plant shows the lowest content of 7.1 ± 0.4 mg.ml -1 . Using Box-Behnken Design (BBD), the system achieved 81.48 % Pb removal under optimized conditions such as initial Pb conc. of 9.25 mg. l -1 , HRT of 24.49 days and a water depth of 26.52 cm. ANOVA analysis highlighted the significant impact of all the factors such as initial HM conc., HRT and wastewater depth on FVS performance. Kinetic analysis estimated a closer observance to the zero-order model, supported by high determination coefficient (R 2 ) values. In conclusion, the FVS, as one of the most eco-friendly technologies, demonstrates higher potential for treating polluted water bodies, offering a sustainable remedy to global metal pollution challenges. Research on FVS for HMs removal is an area of ongoing interest and there are several potential future studies that could be pursued to further understand and optimize their effectiveness such as optimization of plant species, enhancement of plant-metal interactions, effects of environmental factors, economic feasibility studies, disposal of heavy metals accumulated plant, scale-up and application in real-world settings, etc., 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. Published by Elsevier B.V.)

The improper disposal of large amounts of phosphogypsum generated during the production process of the phosphorus chemical industry (PCI) still exists. The leachate formed by phosphogypsum stockpiles could pose a threat to the ecological environment and human health. Nevertheless, information regarding the harmful effects of phosphogypsum leachate on organisms is still limited. Herein, the physicochemical characteristics of phosphogypsum leachate were analyzed, and its toxicity effect on zebrafish (Danio rerio), particularly in terms of hepatotoxicity and potential mechanisms, were evaluated. The results indicated that P, NH 3 -N, TN, F - , As, Cd, Cr, Co, Ni, Zn, Mn, and Hg of phosphogypsum leachate exceeded the V class of surface water environmental quality standards (GB 3838-2002) to varying degrees. Acute toxicity test showed that the 96 h LC 50 values of phosphogypsum leachate to zebrafish was 2.08 %. Under exposure to phosphogypsum leachate, zebrafish exhibited concentration-dependent liver damage, characterized by vacuolization and infiltration of inflammatory cells. The increased in Malondialdehyde (MDA) content and altered activities of antioxidant enzymes in the liver indicated the induction of oxidative stress and oxidative damage. The expression of apoptosis-related genes (P53, PUMA, Caspase3, Bcl-2, and Bax) were up-regulated at low dosage group and down-regulated at medium and high dosage groups, suggesting the occurrence of hepatocyte apoptosis or necrosis. Additionally, phosphogypsum leachate influenced the composition of the zebrafish gut microbiota by reducing the relative abundance of Bacteroidota, Aeromonas, Flavobacterium, Vibrio, and increasing that of Rhodobacter and Pirellula. Correlation analysis revealed that gut microbiota dysbiosis was associated with phosphogypsum leachate-induced hepatotoxicity. Altogether, exposure to phosphogypsum leachate caused liver damage in zebrafish, likely through oxidative stress and apoptosis, with the intestinal flora also playing a significant role. These findings contribute to understanding the ecological toxicity of phosphogypsum leachate and promote the sustainable development of PCI., 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.)

The widespread application of herbicides raises concerns about their impact on non-target aquatic organisms. This study aimed to evaluate the toxicity of a commercially available herbicide formulation containing Bromoxynil+MCPA (2-Methyl-4-chlorophenoxyacetic acid) on Cirrhinus mrigala (economically significant fish). A total of 210 juvenile fish were subjected to a triplicate experimental setup, with 70 fish allocated to each replicate, exposed to seven different concentrations of herbicide: 0 mg/L, 0.133 mg/L, 0.266 mg/L, 0.4 mg/L, 0.5 mg/L, 0.66 mg/L, and 0.8 mg/L, respectively, for a duration of 96 h. The median lethal concentration (LC50) was determined to be 0.4 mg/L. Significant hematological alterations were observed, including decreases in RBC counts, hemoglobin, hematocrit, and lymphocyte counts, along with an increase in erythrocyte indices. Biochemical analysis revealed elevated levels of neutrophils, WBCs, bilirubin, urea, creatinine, ALT, AST, ALP, and glucose in treated groups. Morphological abnormalities in erythrocytes and histopathological changes in gills, liver, and kidneys were noted. Pathological alterations in gills, liver and kidneys including epithelial cell uplifting, lamellar fusion, hepatolysis, and renal tubule degeneration were observed. Oxidative stress biomarkers such as TBARS (Thiobarbituric Acid Reactive Substance), ROS (Reactive Oxygen Species), and POD (Peroxides) activity increased, while antioxidant enzymatic activities decreased as toxicant doses increased from low to high concentrations. The study reveals that Bromoxynil+MCPA significantly disrupts physiological and hematobiochemical parameters in Cirrhinus mrigala, which highlights the substantial aquatic risks. In conclusion, the herbicide formulation induced significant alterations in various fish biomarkers, emphasizing their pivotal role in assessing the environmental impact of toxicity. This multi-biomarker approach offers valuable insights regarding the toxicological effects, thereby contributing substantially to the comprehensive evaluation of environmental hazards., 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.)

Dichloroacetonitrile (DCAN) is an emerging disinfection by-product (DBP) that is widespread in drinking water. However, the pathway for DCAN formation from aromatic amino acids remains unclear, leading to a lack of an understanding of its explicit fate during chloramination. In this study, we investigated the specific formation mechanism of DCAN during the chloramination of phenylalanine based on reaction kinetics and chemical thermodynamics. The reason for differences between aldehyde and decarboxylation pathways was explained, and kinetic parameters of the pathways were obtained through quantum chemistry calculations. The results showed that the reaction rate constant of the rate-limiting step of the aldehyde pathway with 1.9 × 10 -11  s -1 was significantly higher than that of decarboxylation (3.6 × 10 -16  s -1  M -1 ), suggesting that the aldehyde pathway is the main reaction pathway for DCAN formation during the chloramination of phenylalanine to produce DCAN. Subsequently, theoretical calculations were performed to elucidate the effect of pH on the formation mechanism, which aligned well with the experimental results. Dehydrohalogenation was found to be the rate-limiting step under acidic conditions with reaction rate constants higher than those of the rate-limiting step (expulsion of amines) under neutral conditions, increasing the rate of DCAN formation. This study highlights the differences in DCAN formation between the decarboxylation and aldehyde pathways during the chloramination of precursors at both molecular and kinetic levels, contributing to a comprehensive understanding of the reaction mechanisms by which aromatic free amino acids generate DCAN., 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.)