Aquatic photolysis of high-risk fluorinated liquid crystal monomers: Kinetics, toxicity evaluation, and mechanisms.

Despite the frequent detection of fluorinated liquid-crystal monomers (FLCMs) in the environment, the level of understanding of their fate, toxicity, and transformation remains insufficient. Herein, we investigated the degradation kinetics and mechanism of an FLCM (4-cyano-3-fluorophenyl 4-ethylbenzoate, CEB-F) under ultraviolet (UV) photolysis in aquatic environment. Our findings demonstrated that the UV photolysis of CEB-F followed first-order kinetics. Photodegradation products were identified using liquid chromatography with mass spectrometry, and detailed reaction pathways were proposed. It is postulated that through the attack of reactive oxygen species, hydroxylation, and CO/C-F bond cleavage, CEB-F gradually degraded into small molecular compounds, releasing fluorine ions. Acute immobilization tests with Daphnia magna (D. magna) revealed significant acute toxicity of CEB-F, with LC50 values ranging from 1.023 to 0.0536 µM over 24 to 96 h, emphasizing the potential high risk of FLCMs in aquatic ecosystems if inadvertently discharged. Interestingly, we found that the toxicity of CEB-F photolysis reaction solutions was effectively reduced. Through catalase and acetylcholinesterase activities analysis along with molecular docking simulation, we proposed differences in the underlying toxicity mechanisms of CEB-F and its photolysis products to D. magna. These findings highlight the potential harmful effects of FLCMs on aquatic ecosystems and enrich our understanding of the photolysis behavior of FLCMs.

[Pollution Level and Risk Assessment of OPEs in Typical River Basins of China].

Organophosphate esters(OPEs), as a substitute for brominated flame retardants, are widely used in production and life, and their environmental pollution and toxic effects have attracted widespread attention. In this study, the concentrations and distribution characteristics of OPEs in seven major drainage basins of China were sorted out. The average daily dose of OPEs in Chinese adults, adolescents, and children was calculated to assess the health risks, and the reliability of the results was evaluated using Monte Carlo simulation. The toxic effect concentrations of 12 OPEs on aquatic organisms were investigated, and the species sensitivity distribution(SSD) curve was constructed to assess the ecological risk. The results showed that the 5th percentile concentration of ΣOPEs in the seven drainage basins was 52.61 ng·L-1 under the low exposure scenario. The median concentration of ΣOPEs in the seven basins was 499.74 ng·L-1, with trichloroethyl phosphate(TCEP), triethyl phosphate(TEP), and triethyl phosphate(1,3-dichloro-2-propyl) esters(TDCP) as the main contaminants. Under the high exposure scenario, the 95th percentile concentration of ΣOPEs in the seven basins was 1904.4 ng·L-1, 3.8 times that of the intermediate exposure scenario, and the Yangtze River Basin had the highest ΣOPEs concentration under the high exposure scenario. The health risk assessment showed that the non-carcinogenic risk of OPEs exposure through drinking water was within acceptable limits for different populations. Trimethyl phosphate(TMP), triisobutyl phosphate(TiBP), and TCEP were the main contributors to cancer risk. The results of ecological risk assessment showed that TCEP had medium ecological risk at the high exposure level, tributyl phosphate(TnBP) had medium ecological risk under the intermediate exposure scenario, and there was higher ecological risk under the high exposure scenario. Triphenyl phosphate(TPhP) had a risk quotient greater than 1 under the low, intermediate, and high exposure scenarios, and there was a high ecological risk, which requires special attention.

Distribution characteristics, source attribution, and health risk assessment of organophosphate esters in indoor and outdoor dust from various microenvironments in Beijing.

The occurrence and profiles of organophosphate esters (OPEs) were studied in indoor and outdoor dusts from various microenvironments, including forty-seven outdoor dusts from green belts, roads, parks and residence areas, seventy-seven indoor dusts from private cars, print shops, taxis, furniture shops, offices, dormitories, shopping malls and residences house in different districts in Beijing. The total concentrations (Σ12OPEs) were eighteen times higher in indoor dusts (7.14 ×102 to 2.24 ×104 ng/g) than in outdoor dusts (36.0-1.56 ×103 ng/g). OPEs concentrations in samples from taxi and private cars were obviously higher than other indoor microenvironments. Both indoor and outdoor microenvironments also showed different compositional profiles of OPEs, indicating that polyurethane foam/building materials and hydraulic fluids/plastics were the greatest contributions in different microenvironments, with chlorinated alkyl phosphates (Cl-OPEs) being the predominant compound in both indoor dust (52.1-86.5%) and outdoor dust samples (42.6-81.3%). The uncertainty was reduced by Monte Carlo simulation, and the pollution levels of 50th and 95th percentiles were employed to calculate the average daily dosage, which was then used to calculate hazard quotient (HQ) for assessing the health risks to adults and children. Results showed that OPEs were safe even at extremely consumed concentration percentile (95th) in all groups.

Validation of quenching effectiveness and pollutant degradation ability of singlet oxygen through model reaction system.

Quenching method is widely used to assess the contribution of specified reactive species through the probe inhibition efficiency (IE) caused by adding excessive quencher. However, for reactive species with weak ability such as singlet oxygen (1O2), the quenching results are prone to ambiguity. In this study, an 1O2 system using furfuryl alcohol (FFA) as a probe was successfully constructed by methylene-blue-N vis-photosensitization, to discuss the quenching, interference elimination and pollutant degradation ability of 1O2. Inhibition of FFA transformation caused by both quenching and interrupting of 1O2 production was found. The quenching is affected by quencher dosage and ability, which depends on the second-order-rate constant (k). A high k means a strong ability, and less dosage is required to achieve the same IE. Comparison between the calculated ratio of reactive species consumed by quencher and experimental IE helps to judge the interruption of 1O2 production. None of the organic-solvents (methanol, ethanol, iso-propanol, n-butanol, iso-butanol, tert-butanol, tetrahydrofuran, acetonitrile, acetone and chloroform) scavenged 1O2, which would be used as screening-agent for other reactive species (e.g., hydroxyl radicals) that would interrupt 1O2 contribution assessment. Besides, 1O2 was powerless to degrade most selected pollutants. These results encourage proper use of quenchers and better experimental design.

Estimating the prevalence of depression using wastewater-based epidemiology: A case study in Qinghai Province, West China.

Wastewater-based epidemiology (WBE) is considered a cost-effective alternative approach capable of determining the consumption and prevalence of drug use in communities, however, the application of WBE for estimating the prevalence of depression has seldom been reported. In this study, the prevalence of antidepressants was estimated in five cities in Qinghai Province, west China to examine the feasibility of using WBE to estimate the depression prevalence. Residual concentrations of the drugs varied from different wastewater treatment plants (WWTPs) in five cities. Venlafaxine (0.06-720 ng/L), O-desmethylvenlafaxine (1.31-1659 ng/L), paroxetine (

Cytotoxicity and hemolysis of rare earth ions and nanoscale/bulk oxides (La, Gd, and Yb): Interaction with lipid membranes and protein corona formation.

The widespread application of rare earth elements (REEs) has raised concerns about their potential release into the environment and subsequent ingestion by humans. Therefore, it is essential to evaluate the cytotoxicity of REEs. Here, we investigated the interactions between three typical REEs (La, Gd, and Yb) ions as well as their nanometer/µm-sized oxides and red blood cells (RBCs), a plausible contact target for nanoparticles when they enter the bloodstream. Hemolysis of REEs at 50-2000 µmol L-1 was examined to simulate their cytotoxicity under medical or occupational exposure. We found that the hemolysis due to the exposure of REEs was highly dependent on their concentration, and the cytotoxicity followed the order of La3+ > Gd3+ > Yb3+. The cytotoxicity of REE ions (REIs) is higher than REE oxides (REOs), while nanometer-sized REO caused more hemolysis than that µm-sized REO. The production of reactive oxygen species (ROS), ROS quenching experiment, as well as the detection of lipid peroxidation, confirmed that REEs causes cell membrane rupture by ROS-related chemical oxidation. In addition, we found that the formation of a protein corona on REEs increased the steric repulsion between REEs and cell membranes, hence mitigating the cytotoxicity of REEs. The theoretical simulation indicated the favorable interaction of REEs with phospholipids and proteins. Therefore, our findings provide a mechanistic explanation for the cytotoxicity of REEs to RBCs once they have entered the blood circulation system of organisms.

Ranking the risks of eighty pharmaceuticals in surface water of a megacity: A multilevel optimization strategy.

Pharmaceuticals in freshwater posed ecological risks to aquatic ecosystem, however, most risk assessments of pharmaceuticals were conducted at screening level, which were limited by the availability of the toxicity data. In this study, risks of 80 pharmaceuticals including 35 antibiotics, 13 antiviral drugs, 13 illicit drugs, and 19 antidepressants in surface water of Beijing were assessed with a proposed multilevel environmental risk optimization strategy. Target pharmaceuticals were detected in surface water samples with the detection frequency from 1.7 % to 100 % and the total concentrations from 31.1 ng/L to 2708 ng/L. Antiviral drugs were the dominant pharmaceuticals. Preliminary screening-level risk assessment indicated that 20 pharmaceuticals posed low to high risks with risk quotient from 0.14 (chloroquine diphosphate) to 27.8 (clarithromycin). Thirteen pharmaceuticals were recognized with low to high risks by an optimized risk assessment method. Of them, the refined probabilistic risk assessment of joint probability curves coupling with a quantitative structure activity relationship-interspecies correlation estimation (QSAR-ICE) model was applied. Clarithromycin, erythromycin and ofloxacin were identified to pose low risks with maximum risk products (RP) of 1.23 %, 0.41 % and 0.35 %, respectively, while 10 pharmaceuticals posed de minimis risks. Structural equation modeling disclosed that human land use and climate conditions influenced the risks of pharmaceuticals by indirectly influencing the concentrations of pharmaceuticals. The results indicated that the multilevel strategy coupling with QSAR-ICE model was appropriate and effective for screening priority pollutants, and the strategy can be used to prioritize pharmaceuticals and other emerging contaminants in the aquatic environment.

Occurrence, spatial distribution, and potential risks of organic micropollutants in urban surface waters from qinghai, northwest China.

Lack of knowledge on the destiny of organic micropollutants (OMPs) in the Tibetan Plateau region of China prevents the public from being aware of the need for protecting these unique aquatic ecosystems that are precious water resources and source areas of the Yellow River. To address this knowledge gap, this study systematically investigated the multi-residue analysis, distribution, and potential risks of six types of OMPs, namely, neonicotinoid pesticides (NEOs), fungicides, organophosphate esters (OPEs), organophosphorus pesticides (OPPs), psychoactive substances (PSs), and antidepressants (ADs), in surface waters of major cities in Qinghai. A total of 31 compounds, consisting of 8 NEOs, 1 fungicide, 12 OPEs, 2 OPPs, 5 PSs, and 3 ADs, were detected in >50% of the sites, showing their ubiquitous nature in the study area. Results showed that the total OMP concentration in surface water was 28.3-908 ng/L, and OPEs were the dominant composition (48.6%-97.4%). The risk quotient values of the detected diazinon and dursban regularly exceeded 1 for aquatic organisms at all sampling sites, indicating moderate-high chronic ecological risk. The joint probability curves showed that dursban and NEOs have higher risk levels than other OMPs. Although the results of the non-carcinogenic total hazard quotient of the OMPs in the surface water was less than 1 in all age groups and the carcinogenic risk was lower than the negligible risk level, the potential risks to children and infants were considerably greater and should not be underestimated. In addition to pollutant concentration and exposure duration, ingestion rate and body weight (BW) are also important factors affecting health risk, with BW having a negative effect. To the best of the authors' knowledge, this report is the first to describe OMP pollution in Qinghai, and the results provide new insight into the ecological security of the water resources of the Tibetan Plateau.

Investigation on consumption of psychoactive substances and their ecological risks using wastewater-based epidemiology: a case study on Qinghai-Tibet Plateau.

The Qinghai-Tibet Plateau is the third pole of the world, and information on the consumption of psychoactive substances (PSs) in this area is scarce. In this study, we selected Qinghai Province as the research area, and the per capita consumption and prevalence of PSs were investigated using wastewater-based epidemiology. Samples from 17 wastewater treatment plants (WWTPs) in 5 major cities in Qinghai Province were monitored, and 11 PSs were detected by ultra-high performance liquid chromatography-tandem mass spectrometry. Results showed that the target compounds were detected in all samples, with relatively high concentrations of ephedrine (2.1-4825.3 ng/L) and methamphetamine (1.5-295.7 ng/L). The consumption of methamphetamine in Xining City, Haidong City, and Haixi City was up to 78.4, 16.8, and 21.2 mg/1000 inh/d (the PS consumption per 1000 inhabitants in 1 day), respectively, higher than that in the other two cities, which was the result of the different consumption patterns and its relationship with the economic levels of each city. High consumption of methadone (47.9 mg/1000 inh/day) was found in Xining City, which might be related to the methadone maintenance therapy sites in the city. Methamphetamine was the most prevalent drug, with the prevalence ranging from 0.003 (Guoluo) to 0.197% (Xining), and the prevalence of other PSs was low. The ecological risk assessment of PSs in the effluent of WWTPs showed that methadone exerted a low risk to aquatic organisms in three sites, while other substances posed potential risk or no risk. However, the long-term effect of PSs cannot be ignored.

Occurrence, distribution, and ecological risk of psychoactive substances in typical lakes and rivers in Qinghai-Tibet Plateau.

The occurrence, distribution, and ecological risks of psychoactive substances (PSs) in Qinghai-Tibet Plateau (QTP) was investigated in this study. The surface water samples were collected in July in 2020 from five major water bodies, and 9 PSs were determined by liquid chromatography-mass spectrometry. The mean concentrations of the total PSs were 2.19-96.86 ng/L in lakes and 4.56-34.47 ng/L in rivers. Amphetamine (AMP) was the predominant contaminant both in lakes and rivers with a mean concentration of 12.21 ± 22.76 ng/L and 9.83 ± 6.14 ng/L, respectively. The compositions of PSs in lakes and rivers were significantly different. AMP, methadone (MTD), 3,4-methylenedioxyamphetamine (MDA), and ketamine (KET) were the most detected contaminants in lakes, while in rivers AMP, MDA, heroin (HER), and methamphetamine (METH) were the most detected ones. Concentrations of AMP and MTD, the two predominant drugs, varied spatially, with the decreasing concentration of AMP in the order of Huangshui River > Yamzhog Yumco Lake > Qinghai Lake > Lhasa River > Namco Lake, and of MTD in the order of Qinghai Lake > Namco Lake > Huangshui River > Yamzhog Yumco Lake. The risk quotients (RQs) of PSs ranged from 4.44 × 10-6 to 4.32 × 10-2, indicating a low risk of PSs in the aquatic ecosystem in QTP. Compared with other research in the world, the contamination of psychoactive substances in the Qinghai-Tibet Plateau was at relatively low levels with low ecological risks.

[Pollution Characteristics and Migration of BTEX at a Chemical Contaminated Site in the Guangdong-Hong Kong-Macau Greater Bay Area].

In this study, we analyzed 247 soil and 20 groundwater samples from a typical chemical site in the Guangdong-Hong Kong-Macau Greater Bay Area and simulated the solute transport of pollutant benzene with the GMS software, in order to reconstruct the distribution and migration mechanism of benzene series (BTX) pollutants. The detected concentrations of benzene, ethylbenzene, m,p-xylene, and o-xylene exceeded the screening values in some soil and groundwater samples, indicating that the pollution of BTX in shallow groundwater was serious. Our simulation indicated an elliptical flow of benzene in groundwater (from northwest to southeast), mainly through convection, dispersion, and molecular diffusion. Along the vertical direction, the BTX was mainly distributed in the form of floating benzene, and some of the constituents were dissolved in the groundwater. Due to hydrodynamic mechanisms, the dissolved benzene tended to migrate faster and had hence a greater impact on the downstream groundwater. Through the model validation and analysis, we obtained a linear fitting correlation coefficient (R2) of 0.995 between the simulated and actual monitoring values, which indicates a good agreement between these two sets of data. The model had a high prediction accuracy, and could hence accurately determine the migration and distribution characteristics of benzene. Therefore, it provides a scientific basis for the accurate control and remediation of chemical contaminated sites in the Guangdong-Hong Kong-Macao Greater Bay Area.

Wet tropical climate in SE Tibet during the Late Eocene.

Cenozoic climate cooling at the advent of the Eocene-Oligocene transition (EOT), ~33.7 Ma ago, was stamped in the ocean by a series of climatic events albeit the impact of this global climatic transition on terrestrial environments is still fragmentary. Yet archival constraints on Late Eocene atmospheric circulation are scarce in (tropical) monsoonal Asia, and the paucity of terrestrial records hampers a meaningful comparison of the long-term climatic trends between oceanic and continental realms. Here we report new sedimentological data from the Jianchuan basin (SE Tibet) arguing for wetter climatic conditions in monsoonal Asia at ~35.5 Ma almost coevally to the aridification recognized northwards in the Xining basin. We show that the occurrence of flash-flood events in semi-arid to sub-humid palustrine-sublacustrine settings preceded the development of coal-bearing deposits in swampy-like environments, thus paving the way to a more humid climate in SE Tibet ahead from the EOT. We suggest that this moisture redistribution possibly reflects more northern and intensified ITCZ-induced tropical rainfall in monsoonal Asia around 35.5 Ma, in accordance with recent sea-surface temperature reconstructions from equatorial oceanic records. Our findings thus highlight an important period of climatic upheaval in terrestrial Asian environments ~2-4 millions years prior to the EOT.