Presence of carbazole and polyhalogenated carbazoles in human urine.

Exposure to carbazole (CZ) and polyhalogenated carbazoles (PHCZs) may pose a threat to human health, owing to their potential dioxin-like toxicity. Until now, the presence of these chemicals in the human urine from the general population is still unclear. Human urine samples (n = 210) were taken from the general population in Quzhou, China in this study, and were analyzed for CZ and 14 PHCZs. CZ and nine PHCZs were detected in collected human urine. CZ (detection frequency 100 %), 3-chlorocarbazole (3-CCZ; 88 %), 3,6-dichlorocarbzole (36-CCZ; 84 %), and 3-bromocarbazole (3-BCZ; 80 %) were more frequently detected. Among detected PHCZs, 3-CCZ (mean 0.49 ng/mL, < LOD-4.3 ng/mL) had comparatively higher urinary levels, followed by 3-BCZ (0.30 ng/L, < LOD-1.9 ng/mL) and 36-CCZ (0.20 ng/L, < LOD-1.4 ng/mL). Urinary concentrations of CZ in male participants (1.3 ± 0.26 ng/mL) were significantly (p < 0.05) higher than that in female participants (0.92 ± 0.24 ng/mL). No obvious trend in urinary concentrations with the age of participants was found for CZ and detected PHCZs. The mean daily excretion was found highest for CZ (31 ng/kg bw/day), followed by 3-CCZ (19 ng/kg bw/day) and 3-BCZ (8.5 ng/kg bw/day). This study provides the first data, to our knowledge, on the presence and levels of CZ and PHCZs in human urine, which is necessary for conducting the human exposure risk assessment.

Associations between urinary concentrations of benzothiazole, benzotriazole, and their derivatives and lung cancer: A nested case-control study.

Benzothiazole (BTH), benzotriazole (BTR), and their respective derivatives (BTHs and BTRs) are emerging environmental pollutants with widespread human exposure and oncogenic potential. Studies have demonstrated adverse effects of exposure to certain BTHs and BTRs on the respiratory system. However, no study has examined the associations between exposure to BTHs and BTRs and lung cancer risk. We aimed to examine the associations between urinary concentrations of BTHs and BTRs and the risk of lung cancer in the general population from Quzhou, China. We conducted a nested case-control study in an ongoing prospective Quzhou Environmental Exposure and Human Health (QEEHH) cohort, involving 20, 694 participants who provided urine samples during April 2019-July 2020. With monthly follow-up until November 2022, 212 lung cancer cases were recruited and 1:1 matched with healthy controls based on age and sex. We estimated odds ratios (ORs) and 95% confidence intervals (CIs) of lung cancer risk associated with urinary BTHs and BTRs concentrations using conditional logistic regression models after controlling for potential covariates. We also examined effect modification by several covariates, including sex, socioeconomic status, smoking status, alcohol consumption, and dietary habit. Creatinine-corrected urinary BTH and 2-hydroxy-benzothiazole (2-OH-BTH) levels were significantly associated with the risk of lung cancer, after adjusting for a variety of covariates. Participants in the highest quartile of BTH had a 95% higher risk of lung cancer, compared with those in the lowest quartile (adjusted OR = 1.95, 95% CI: 1.08-3.49; p for trend = 0.01). Participants with higher levels of urinary 2-OH-BTH had an 83% higher risk of lung cancer than those with lower levels (adjusted OR = 1.83, 95% CI: 1.16-2.88; p for trend = 0.01). Exposure to elevated levels of BTH and 2-OH-BTH may be associated with an increased risk of lung cancer. These associations were not modified by socio-demographic characteristics.

Biomass chitosan/sodium alginate colorimetric imprinting hydrogels with integrated capture and visualization detection for cadmium(II).

Due to Cd(II) with highly toxic, persistent and bioaccumulative, the discharge of it into the environment brings serious pollution. Developing strategies that are efficient, low-cost, pollution-free and specific to removing Cd(II) from wastewater is therefore of great urgency and prime importance. A novel chitosan/sodium alginate ionic imprinting(IICA) hydrogels with specific adsorption capacity for Cd(II) was prepared through freeze-thaw and ion imprinting, and finally the colorimetric sensor (IICAS) was prepared via introducing Rhodamine B(RhB) and Victoria blue(VBB) by immersion to achieve visual detection of Cd(II). The IICA hydrogels with imprinted hole structure had higher adsorption capacity and better specific selectivity for Cd(II). As well as internal diffusion, coordination, ion exchange, and hydrogen bonding influenced the adsorption rate. Moreover, the IICAS exhibited good selective detection ability and linearity for Cd(II) with the fitted correlation coefficient (R2) = 0.98, limit of detection (LOD) = 35 nmol/L. Combined with the smartphone platform, portable and quantitative detection of Cd(II) can be achieved, Within the 0-100 mg/L range, R2 remained 0.94, and LOD was 75 nmol/L. This strategy of preparing a novel whole biomass IICAS integrating capture and visual detection provides a new insight into the construction of a promising candidate sensor for the removal and detection of Cd(II).

Distribution of parabens and 4-HB in human blood.

Human blood has been commonly and routinely analyzed to determine internal human exposure to parabens. However, data on the occurrence of parabens and their common metabolite, p-hydroxybenzoic acid (4-HB), in different human blood matrixes is still limited. In this study, 139 pairs of serum and whole blood samples were collected from Chinese adults, and then analyzed them for 5 parabens and 4-HB. Methylparaben (MeP) and propylparaben (PrP) were consistently the predominant parabens in human serum (mean 2.3 and 2.1 ng/mL, respectively) and whole blood (1.9 and 1.3 ng/mL, respectively). Mean concentrations of 4-HB in human serum and whole blood were 7.7 and 12 ng/mL, respectively. Concentrations of parabens, except benzylparaben (BzP), and 4-HB in human serum were significantly (p < 0.01) correlated with that in whole blood. Distribution pattern of parabens and 4-HB in human blood was evaluated, for the first time, based on their partitioning between human serum and whole blood (Kp). Mean Kp values of parabens, except BzP, increased with the alkyl chain length from 0.83 to 1.6. BzP (mean 1.4) had a comparable mean Kp value to PrP (mean 1.4). Among target analytes, 4-HB had the lowest mean Kp value (0.75). These data are important to select appropriate blood matrixes for conducting human exposure assessment and epidemiological studies on parabens.

Occurrence and partitioning of p-phenylenediamine antioxidants and their quinone derivatives in water and sediment.

p-Phenylenediamine antioxidants (PPDs) and PPDs-derived quinones (PPDQs) may pose a threat to the river ecosystem. However, the knowledge on the occurrence and environmental behaviors of PPDs and PPDQs in the natural river environment remains unknown. In this study, we collected paired water (n = 30) and sediment samples (n = 30) from Jiaojiang River, China and analyzed them for nine PPDs and seven PPDQs. Our results showed that target PPDs and PPDQs are frequently detected in water samples, with the dominance of N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD; mean 12 ng/L, range 4.0-72 ng/L) and 6PPD-derived quinone (6PPDQ; 7.0 ng/L,

Occurrence of p-phenylenediamine antioxidants in human urine.

General populations are widely exposed to various p-phenylenediamine antioxidants (PPDs). N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD), a typical p-phenylenediamine antioxidant, has been detected in human urine samples. However, the occurrence of other widely used PPDs in human urine is still unclear. This study comprehensively characterized the occurrence of 9 PPDs in human urine from 151 Chinese adults. Our results showed that all target PPDs were detected in human urine samples, with the total concentrations of PPDs ranging from 0.41 to 38 ng/mL. PPDs in human urine was dominated by 6PPD (mean 1.2 ng/mL, range < LOD - 3.8 ng/mL), followed by N-phenyl-N'-cyclohexyl-p-phenylenediamine (CPPD; 0.85 ng/mL,

An observed nocturnal ozone transport event in the Sichuan Basin, Southwestern China.

The ozone (O3) pollution in China drew lots of attention in recent years, and the Sichuan Basin (SCB) was one of the regions confronting worsening O3 pollution problem. Many previous studies have shown that regional transport is an important contributor to O3 pollution. However, very few features of the O3 profile during transport have been reported, especially in the border regions between different administrative divisions. In this study, we conducted tethered balloon soundings in SCB during the summer of 2020 and captured a nocturnal O3 transport event during the campaign. Vertically, the O3 transport occurred in the bottom of the residual layer, between 200 and 500 m above ground level. Horizontally, the transport pathway was directed from southeast to northwest based on the analysis of the wind field and air mass trajectories. The effect of transport in the residual layer on the surface O3 concentration was related to the spatial distribution of O3. For cities with high O3 concentrations in the upwind region, the transport process would bring clean air masses and abate pollution. For downwind lightly polluted cities, the transport process would slow down the decreasing or even increase the surface O3 concentration during the night. We provided observational facts on the profile features of a transboundary O3 transport event between two provincial administrative divisions, which implicated the importance of joint prevention and control measures. However, the sounding parameters were limited and the quantitative analysis was preliminary, more integrated, and thorough studies of this topic were called for in the future.

Occurrence of p-phenylenediamine antioxidants (PPDs) and PPDs-derived quinones in indoor dust.

The p-phenylenediamine antioxidants (PPDs) have been widely detected in various dust samples. Nevertheless, the knowledge on occurrence of their environmental transformation products, PPD-derived quinones (PPDQs), in indoor dust remains limited. In this study, indoor dust samples (n = 97) were collected from Hangzhou, China, and analyzed for PPDs and PPDQs. Results showed that nine PPDs were detected in indoor dust samples, with the total concentrations of 1.7-223 ng/g. N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD, mean 17 ng/g) was the predominant PPDs in indoor dust, followed by N, N'-di(o-tolyl)-p-phenylenediamine (DTPD, 8.6 ng/g) and N-(1,3-dimethylbutyl)-N'-(p-tolyl)-p-phenylenediamine (DMTPD, 4.7 ng/g). Five PPDQs were detected in indoor dust samples. Among detected PPDQs, 6PPDQ (14 ng/g, 0.33-82 ng/g) had the highest mean concentration, followed by DTPDQ (5.9 ng/g, < LOD-31 ng/g) and DPPDQ (2.2 ng/g, < LOD-11 ng/g). We also estimated the daily intake (DI) of PPDs and PPDQs through indoor dust ingestion. Infants had higher mean DIs of PPDs and PPDQs than children and adults. Notably, to our knowledge, this study first reports the occurrence of three novel PPDs and four novel PPDQs in indoor dust samples. More studies are needed to reveal the potential human health risks of exposure to these newly identified chemicals.

Superhydrophobic and Photocatalytic Synergistic Self-Cleaning Coating Constructed by Hierarchically Structured Flower-like Hollow SiO2@TiO2 Spheres with Oxygen Vacancies.

The self-cleaning coating has both superhydrophobic physical and photocatalytic chemical self-cleaning properties, which has attracted the wide attention of researchers in recent years. First, the flower-like hollow SiO2@TiO2 spheres with oxygen vacancies (rFHSTs) were prepared by the liquid-phase reduction method, in which several different functional components were integrated. Meanwhile, the influence mechanisms of the physical structure and chemical composition on the photocatalytic properties are discussed in detail. The results proved that rFHSTs exhibited the enhanced photoresponse range and photocatalytic degradation performance in visible light because of the synergistic effect of the microstructure (internal cavity, 3D flower-like nanosheet), SiO2/TiO2 heterojunction structure, and oxygen vacancies. After that, superhydrophobic modified rFHSTs were used as fillers to fabricate PVA/PFDTS-rFHSTs composite coatings with both physical and chemical self-cleaning properties. The self-cleaning performances and principles of the composite coating were examined and explored. The results showed that the low surface energy of the hydrophobic chain segment, the inherent particle effect, and the photocatalytic activity of rFHSTs were responsible for the superhydrophobic and photocatalytic effects, finally endowing the composite coating with self-cleaning performance. In short, this study is profound for the development and application of self-cleaning coatings with both physical and chemical performances.

Occurrence of microplastics in Antarctic fishes: Abundance, size, shape, and polymer composition.

Presence of microplastics (MPs) in Antarctic ecosystems has attracted global attention, due to the potential threat to the Antarctic marine organisms. However, data on the occurrence of MPs in Antarctic fishes remains very limited. This study investigated the abundance and characteristics of MPs in four species of Antarctic fish (n = 114). The highest mean abundance of MPs was detected in Trematomus eulepidotus (1.7 ± 0.61 items/individual), followed by that in Chionodraco rastrospinosus (1.4 ± 0.26 items/individual), Notolepis coatsi (1.1 ± 0.57 items/individual), and Electrona carlsbergi (0.72 ± 0.19 items/individual). MPs in Notolepis coatsi (mean 747 µm) had the highest mean size, followed by that in Trematomus eulepidotus (653 µm), Chionodraco rastrospinosus (629 µm), and Electrona carlsbergi (473 µm). This is possibly attributed to the feeding habits and egestion behaviors of different Antarctic fishes. Fiber was consistently the predominant shape of MPs in Trematomus eulepidotus, Chionodraco rastrospinosus, and Electrona carlsbergi, accounting for 82 %, 76 %, and 60 % of total items of MPs, respectively. Polypropylene, polyamide, and polyethylene were the predominant polymer composition of MPs in Antarctic fishes, collectively contributed 63-86 % of total items of MPs. This may be because these types of MPs have been widely used in global household materials. To our knowledge, this is the most comprehensive study examining the occurrence of MPs in Antarctic fishes. This study provides fundamental data for evaluating the risks of MP exposure for Antarctic fishes.

Diagnostic value of pleural fluid SMRP, CA125, MMP-7, and MMP-9 in malignant pleural effusion.

This study aimed to investigate the clinical value of mesothelin soluble related peptide (SMRP), cancer antigen 125 (CA125), matrix metalloproteinase-7 (MMP-7), and matrix metalloproteinase-9 (MMP-9) in benign and malignant pleural exudative effusion. A total of 105 adult patients with pleural exudative effusion admitted in our hospital from December 2019 to December 2020 were selected. Patients were divided into the benign group (n = 60) and the malignant group (n = 45) according to their condition. The levels of SMRP, CA125, MMP-7, and MMP-9 in the pleural effusion were determined by enzyme linked immunosorbent assay. Receiver operating characteristic curves were used to analyze the individual and combined predictive value of SMRP, MMP-7, MMP-9, and CA125 levels. In the malignant group, the SMRP, CA125, MMP-7, and MMP-9 levels were all significantly higher than those in benign group (P = .01). The detection efficiency of the 4 indicators in the combined diagnosis were higher than that of single index and combination of any 2 indices. There was a moderate positive correlation between SMRP and CA125 and MMP-7 in malignant pleural effusion. The correlation between MMP-7 and MMP-9 was moderately positive. The diagnostic efficacy of SMRP combined with CA125, MMP-7, and MMP-9 in pleural effusion for malignant pleural effusion and BPE are better than single index, which has certain clinical values for the selection of early intervention scheme for BPE patients.

Enhancing the antitumor immunosurveillance of PD-L1-targeted gene therapy for metastatic melanoma using cationized Panax Notoginseng polysaccharide.

Improved curative effects with reduced toxicity has always been the ultimate goal of gene delivery vectors for tumor immunotherapy. Panax notoginseng polysaccharide (PNP), a natural plant-derived macromolecule, not only has antitumor immune activity but also has the typical structural characteristics useful for gene delivery. In this work, positively charged polyethyleneimine (PEI) was directly grafted to the backbone of PNP to induced its charge reversal and generate a functional gene vector (PNP-PEI). Moreover, a short hairpin RNA targeting the programmed death-ligand 1 (PD-L1) was loaded into PNP-PEI to generate a potentially therapeutic nanoparticle (PNP-PEI/shPD-L1). In vitro and in vivo experiments demonstrated that PNP-PEI could efficiently carry the therapeutic shPD-L1 into tumor cells and that PNP-PEI/shPD-L1 could significantly inhibit the expression of PD-L1 and growth of B16-F10 cells. Noteworthily, treatment with PNP-PEI reversed the phenotype of macrophages from M2 to M1 subtype and promoted dendritic cell maturation, which encouraged the host immunity and enhanced the therapeutic antitumor effects. In summary, this study describes a PNP-based gene delivery vector and highlights the beneficial immunopotentiating therapeutic outcomes of PNP-PEI for tumor immunotherapy.

Hierarchical Flower-Like Hollow SiO2@TiO2 Spheres with Enhanced Thermal Insulation and Ultraviolet Resistance Performances for Building Coating.

In this paper, a novel 3D hierarchical flower-like hollow SiO2@TiO2 sphere (FHST) with a large number of irregular nanosheets was successfully prepared by a solvothermal method and subsequent calcination process, in which multiple different functional components were perfectly integrated into a single nanostructure. The morphology and structure of FHSTs were characterized by SEM, TEM, XRD, XPS, and BET. The growth mechanism of the 3D flower-like structure was obtained through a series of single-factor experiments, of which hexamethylenetetramine acted in a vital role. Moreover, it was also used as a filler for polyacrylate substrate to improve the thermal insulation and ultraviolet resistance properties of architectural coatings. The results showed that the composite film with FHSTs had lower thermal conductivity and higher light reflection performance compared to those with hollow SiO2 spheres, hollow TiO2 spheres, and hollow SiO2@TiO2 spheres. More significantly, its transmittance at the full wavelength of ultraviolet light was almost zero, exhibiting a prominent inhibitory effect on UVA. In addition, compared with commercially available hollow glass microspheres, FHSTs had more excellent thermal insulation performance in practical applications.

Stronger Stimulation of Waste Activated Sludge Anaerobic Fermentation by a Particular Amount of Micron-Sized Zero Valent Iron.

An emerging contaminant, micron-sized zero valent iron (mZVI) has been reported to be accumulated in waste activated sludge (WAS). In the present study, the potential effects of mZVI on WAS anaerobic fermentation performance, as well as the shift of the microbial community composition and function, were assessed. Results from batch experiments indicated that a particular concentration of mZVI (1.5 g/L, in the range of 0.0 to 5.0 g/L) improved volatile fatty acids (VFA) accumulation by 4.84 times that in the control group, the ability (dosage dependent) to remove phosphorus, and the dewaterability of fermented WAS from 126 ± 5 s (control group) to 104 ± 3 s (group with 1.5 g/L mZVI). Furthermore, high-throughput sequencing revealed that mZVI had no significant impact on the shift of microbial community structure, but directly stimulated the functional performance related to anaerobic fermentation. This study will provide new insights into the mZVI application and its effect on WAS utilization.