Feasibility of sulfated BPA and BPS as wastewater-based epidemiology biomarkers: Insights from wastewater and reported human urine analysis.

In wastewater-based epidemiology (WBE), the selection of appropriate biomarkers presents a significant challenge. Recently, sulfated bisphenols have garnered attention as potential WBE biomarkers due to their increased stability in wastewater compared to glucuronide conjugates. This study aims to comprehensively assess the feasibility of employing sulfated BPA and BPS as WBE biomarkers by analyzing both WBE and human biomonitoring data. To conduct this research, wastewater samples were collected from six domestic wastewater treatment plants in Guangzhou, China, and urinary concentration of BPA and BPS were obtained from peer-reviewed literature. The results revealed that mean urinary concentrations of BPA and BPS, calculated using Monte Carlo simulations, significantly exceeded those reported in human biomonitoring studies. Furthermore, the per capita mass load ratio of sulfated BPA and BPS in human urine to the mass load in wastewater was found to be below 10 %. This outcome suggests that the excretion of BPA-S and BPS-S in urine does not make a substantial contribution to wastewater, hinting at the existence of other notable sources. Consequently, our study concludes that sulfated BPA-S and BPS-S are not suitable candidates as WBE biomarkers. This work provides a referenceable analytical framework for evaluating the feasibility of WBE biomarkers and emphasizes the necessity for caution when utilizing WBE to assess human exposure to chemicals.

An efficient algorithm for resource optimization in IRS-mmWave-NOMA B5G wireless networks.

The effectiveness of implementing intelligent reflecting surface (IRS) for millimeter-wave (mmWave)-non-orthogonal multiple-access (NOMA) systems has allowed for significant sum-rate improvements. The majority of recent research has not discussed how well the IRS-mmWave-NOMA combination performs. Therefore, a new technique for resource optimization in IRS-mmWave-NOMA B5G wireless networks is proposed in this research. The key concept is to use an iterative algorithm to solve the optimization issue while incorporating many crucial constraints like the selection of the IRS beam, transmit power distribution, and decoding order, among others. Simulation results show that the proposed approach outperforms existing state-of-the-art algorithms in terms of computation delay, sum rate and NMSE. The computational complexity also validated the simplicity and hardware-friendly feature of the proposed algorithm.

Molecular characterization and expression analysis of nine toll like receptor (TLR) genes in Scortum barcoo under Streptococcus agalactiae infection.

Toll like receptors (TLRs) are important pattern recognition receptors participating in innate immune system. Up to now, no TLR has been identified in Jade perch (Scortum barcoo). In this study, we successfully identified 9 members of TLRs from the Jade perch. Amino acid sequence alignment analysis showed that the whole sequences of these TLRs were highly conserved among different fish species, especially in LRR, TM and TIR domains. Phylogenetic analysis revealed that each SbTLR was successfully grouped into corresponding gene family of teleosts. Expression analysis showed that most SbTLRs mainly expressed in liver, spleen, muscle and skin, while expressed less in brain and stomach. After Streptococcus agalactiae infection, expression of SbTLR2, SbTLR5S and SbTLR22 were significantly upregulated, while SbTLR3, SbTLR5M, SbTLR9, SbTLR13, and SbTLR14 were significantly downregulated. In all, this research first reported molecular characterization and expression profiles of 9 TLRs in Jade perch. These data will make a contribution for better understanding the antibacterial mechanism of TLRs in teleosts.

Phototransformation of extracellular polymeric substances in activated sludge and their interaction with microplastics.

Substantial amounts of extracellular polymeric substances (EPS) are present in sludge from wastewater treatment plants (WWTP), and EPS can significantly affect the fate, bioavailability, and toxicity of microplastics (MPs) that coexist in the effluent, however, the mechanism of action between EPS and microplastics remains unclear. In addition, ultraviolet (UV) disinfection is indispensable in the wastewater treatment process in WWTP, which can significantly affect the characteristics of EPS. Therefore, it is of great significance to study the photochemical characteristics of EPS and the effect on binding MPs. In this study, using multispectral technology and two-dimensional correlation spectroscopy analysis, indicates that the molecular weight and aromaticity of EPS after phototransformation were reduced. The results showed that the adsorption of EPS on PSMPs was in the order of TB-EPS > LB-EPS > S-EPS, which was positively correlated with the SUVA254, but negatively correlated with O/C of EPS. This indicates that the main adsorption mechanisms of PSMPs on EPS were π-π and hydrophobicity. The adsorption capacity of S-EPS, LB-EPS and TB-EPS to PSMPs decreased with the increasing of illumination time. After phototransformation, the adsorption sensitivity and reaction sequence of EPS and PSMPs did not change much. This research provides a theoretical basis for understanding the photochemical transformation of extracellular polymers and the morphology and migration of microplastics in sewage treatment, and evaluating the impact of microplastics on ecosystems.

Effect of microplastics on the binding properties of Pb(ii) onto dissolved organic matter: insights from fluorescence spectra and FTIR combined with two-dimensional correlation spectroscopy.

Heavy metal cations are a typical type of inorganic pollutant that has persistent distribution characteristics in aquatic environments and are easily adsorbed on carriers, posing serious threats to ecological safety and human health. Some studies have shown that the coexistence of dissolved organic matter (DOM) and microplastics (MPs) promotes the adsorption of heavy metal cations, but the mechanism of promoting the adsorption process has not been thoroughly studied. In this study, the effect of polystyrene microplastics (PSMPs) on the binding properties of Pb2+ onto humic acid (HA) in aquatic environments was investigated by spectral analysis and two-dimensional correlation (2D-COS) analysis. When PSMPs co-existed with HA, the adsorption capacity of Pb2+ increased. On the one hand, Pb2+ is directly adsorbed on HA through the mechanism of complexation reaction, ion exchange and electrostatic interaction. On the other hand, Pb2+ is first adsorbed on PSMPs by electrostatic action and indirectly adsorbed on HA in the form of PSMPs-Pb2+ owing to the interaction between HA and PSMPs, which increases the adsorption amount of Pb2+ on HA. This study is significant for studying the migration and regression of heavy metal cation contaminants when PSMPs co-exist with DOM in an aqueous environment.

Large-scale biomonitoring of bisphenol analogues and their metabolites in human urine from Guangzhou, China: Implications for health risk assessment.

Bisphenol analogues (BPs) are ubiquitous in the environment and have gained significant attention regarding their associated health risks. However, there is a lack of comprehensive biomonitoring data on BPs and their metabolites in human urine. To address this, we conducted a study evaluate the exposure to BPs in the general population of Guangzhou, China. A total of 1440 urine samples were collected from volunteers and analyzed for the presence of BPs and their metabolites after being pooled into 36 groups based on age and gender. The findings revealed the common detection of ten free-form BPs, as well as the urinary metabolites of BPA and BPS, in the pooled urine samples. BPA was the predominant free-form compound, constituting 50% of the total BPs. The primary urinary metabolites of BPA and BPS are BPA-G and BPS-G, respectively, indicating glucuronidation as their primary metabolic pathway. The composition of urinary metabolites of BPA and BPS varied by age and sex, while the concentration of total BPs in urine was not significantly associated with age and sex. Enzymatic hydrolysis yielded a mean amplification of individual BPs concentrations in urine samples ranging from 1.8 times (BPA) to 4.6 times (BPS). Based on the outcomes, it was estimated that conjugated forms accounted for 96.9%, 96.2%, 94.7%, 94.1%, 92.6%, 89.1%, 87.3%, 87.2%, 87.1% and 85.8% of BPP, BPAF, BPZ, BPE, BPAP, BPF, BPA, BPC, BPS and BPF, respectively, in the pooled urine samples. Preliminary risk assessments indicated that the estimated daily intake of BPA was much higher than the latest proposed tolerable daily intake. Due to the unavailability of health-based guideline values for alternative BPs, some of them exhibit daily intakes comparable to BPA, implying that greater attention should be paid to health risks associated with exposure to BPs.

Assessment of BPA and BPS exposure in the general population in Guangzhou, China - Estimation of daily intakes based on urinary metabolites.

Human exposure to bisphenol A (BPA) and bisphenol S (BPS) has garnered considerable global health concerns. In this paper, the daily intake (DI) of BPA and BPS in the general population of Guangzhou, China, were back-calculated using the biomarkers BPA glucuronides (BPA-G) and BPS glucuronides (BPS-G), respectively. The biomarkers are preferable to total BPA and BPS measurements because they are not susceptible to external contamination. A total of 1440 urine samples were gathered from the general population in Guangzhou, China, which were classified by age and sex into 36 pooled urine samples. 100% and 98% of pooled urine samples contained BPA-G and BPS-G at median values of 1.57 and 0.38 ng/mL, respectively. Based on urinary BPA-G and BPS-G concentrations, we determined the median DI of BPA and BPS to be 31.07 and 7.37 ng/(kg bw*d), respectively, and the highest values to be 106.77 ng/(kg bw*d) and 18.19 ng/(kg bw*d), respectively. Furthermore, our results showed that for the entire dataset, the DI of BPA and BPS were considerably greater in males than in females (p < 0.01)and declined significantly with age (p < 0.05). For risk assessment, the estimated DIs of BPA and BPS were much lower than the European Food Safety Authority' s (EFSA) the temporary acceptable reference dose of 4 µg/(kg bw*d) advised for BPA, suggesting that the exposure risk of BPA and BPS for Guangzhou population is within a controllable safety range. This is the first study to investigate BPA and BPS exposure in the general population of Guangzhou, China, on the basis of urinary metabolites.

Insight into the hetero-interactions of 4-nonylphenol with dissolved organic matter: multiple spectroscopic methods, 1H NMR study and principal component analysis.

Understanding the interactions between heterogeneous dissolved organic matter (DOM) and nonylphenols (NPs) is essential for predicting their behavior and fate in the environment. Herein, we firstly obtained different MW-fractionated humic acids (HAs) using the ultrafiltration method. Afterward, the molecular weight (MW)-dependent interactions of HAs with 4-nonylphenol (4-NP) were analysed by excitation emission matrix (EEM) fluorescence spectroscopy, fluorescence quenching, UV-vis spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy and principal component analysis (PCA). EEM spectra indicated that the quenching mechanism was static. In the binding process, the higher MW fractions showed stronger interaction with 4-NP than the lower MW counterparts, exhibiting a clear MW-dependent interaction heterogeneity. The interaction constants for the 4-NP-HAs system were suppressed as the ionic strength decreased and pH increased, which was especially obvious in the binding of 4-NP to the lower MW-fractionated HAs. The FTIR spectra revealed that hydroxyl and aromatics were involved in the interaction process of HA fractions with 4-NP. It was also found from 1H NMR that π-π interactions between aromatic rings of 4-NP and MW-fractionated HAs were responsible for the complexation. The correlation analysis and PCA results indicated that aromaticity and MW play important roles in the interaction process and confirmed an obvious interaction heterogeneity among MW-fractionated HAs samples. This work highlighted MW-dependent interaction heterogeneities of HA, which suggested that heterogeneity in MW distribution should be taken into consideration when exploring the fate and biogeochemistry cycling of 4-NP from contaminated environments.

Effects of humic acid on Pb2+ adsorption onto polystyrene microplastics from spectroscopic analysis and site energy distribution analysis.

Microplastics (MPs), act as vectors of heavy metal pollutants in the environment, is of practical significance to study the adsorption process and mechanism on heavy metals. In this study, polystyrene microplastics (PSMPs) were used as model MPs to study the adsorption of Pb2+ on PSMPs and the effects of humic acid (HA) on the adsorption process. The results showed that HA promoted the adsorption of Pb2+ on PSMPs, and the higher the concentration of HA, the greater the adsorption of Pb2+. With the increase of pH value and decrease of ionic strength, the adsorption capacity of PSMPs for Pb2+ increased. The scanning electron microscope equipped with the energy dispersive spectroscope (SEM-EDS), fourier transform-infrared spectra (FT-IR) and X-ray photoelectron spectroscopy (XPS) analysis showed that Pb2+ could be adsorbed directly onto PSMPs and also indirectly by HA. The higher KSV values in the PSMPs-HA-Pb2+ system than PSMPs-HA system by fluorescence analysis of HA suggested that HA acted as a bridging role in the adsorption of Pb2+ on PSMPs. The site energy distribution analysis further revealed that HA increased the average site energy µ(E*) and its standard deviation σe* of PSMPs by introducing more adsorption sites, thus enhanced the adsorption affinity of PSMPs. This study provided more thoughts and insights into the adsorption behavior and mechanism of MPs for Pb2+ in aquatic environments.

Adsorption of dissolved organic matter (DOM) on polystyrene microplastics in aquatic environments: Kinetic, isotherm and site energy distribution analysis.

Microplastics and dissolved organic matter (DOM) are ubiquitous in aquatic environments. The adsorption behavior of DOM on microplastics in aquatic environments is a prominent concern. In this study, the adsorption of two types of DOM, Suwannee River Humic Acid (HA) and Suwannee River Fulvic Acid (FA), on polystyrene microplastics (PSMPs, 10 µm) in aquatic environments was investigated. The adsorption of both HA and FA on PSMPs could be well described by using pseudo second-order and Freundlich models. The adsorption of HA and FA on PSMPs was low pH-dependent, particularly for FA adsorption. However, the elevated ionic strength slightly increased the adsorption of HA and FA on PSMPs. Based on Freundlich model, the site energy distribution of HA and FA adsorption on PSMPs under the experimental conditions were estimated. HA and FA first occupied the high-energy adsorption sites and then diffused to the low-energy adsorption sites on PSMPs. With higher site energies, HA demonstrated a much stronger adsorption affinity to PSMPs than FA. The adsorption site heterogeneity (σe*) on PSMPs under the experimental conditions were close. Hydrophobic interaction and π-π electron donor acceptor interaction acted simultaneously in the HA and FA adsorption on PSMPs. The results of this study suggested that the environmental behaviors of microplastics would be influenced by the amount and the type of DOM as well as solution chemistry.

Arabidopsis mtHSC70-1 physically interacts with the Cox2 subunit of cytochrome c oxidase.

The 70-kD heat shock proteins (HSP70s or HSC70s) function as molecular chaperones and are involved in diverse cellular processes. We recently demonstrated the roles of mitochondrial HSC70-1 (mtHSC70-1) in the establishment of cytochrome c oxidase (COX)-dependent respiration and redox homeostasis in Arabidopsis thaliana. Defects in COX assembly were observed in the mtHSC70-1 knockout lines. The levels of Cox2 (COX subunit 2) proteins in COX complex were markedly lower in the mutants than in wild-type plants; however, the levels of total Cox2 proteins in the mutants were not obviously different from those in wild-type plants, suggesting that the stability of COX or the availability of Cox2 was impaired in the mtHSC70-1 mutants. Here, we further detected the interaction between mtHSC70-1 and Cox2 proteins through co-immunoprecipitation, pull-down and firefly luciferase complementation imaging assays. The results showed that mtHSC70-1 could directly combine Cox2 in vivo and in vitro, providing supporting evidence for the role of mtHSC70-1 in COX assembly.

Arabidopsis mtHSC70-1 plays important roles in the establishment of COX-dependent respiration and redox homeostasis.

The 70 kDa heat shock proteins function as molecular chaperones and are involved in diverse cellular processes. However, the functions of the plant mitochondrial HSP70s (mtHSC70s) remain unclear. Severe growth defects were observed in the Arabidopsis thaliana mtHSC70-1 knockout lines, mthsc70-1a and mthsc70-1b. Conversely, the introduction of the mtHSC70-1 gene into the mthsc70-1a background fully reversed the phenotypes, indicating that mtHSC70-1 is essential for plant growth. The loss of mtHSC70-1 functions resulted in abnormal mitochondria and alterations to respiration because of an inhibition of the cytochrome c oxidase (COX) pathway and the activation of the alternative respiratory pathway. Defects in COX assembly were observed in the mtHSC70-1 knockout lines, leading to decreased COX activity. The mtHSC70-1 knockout plants have increased levels of reactive oxygen species (ROS). The introduction of the Mn-superoxide dismutase 1 (MSD1) or the catalase 1 (CAT1) gene into the mthsc70-1a plants decreased ROS levels, reduced the expression of alternative oxidase, and partially rescued growth. Taken together, our data suggest that mtHSC70-1 plays important roles in the establishment of COX-dependent respiration.

Determination of volatile organic compounds in pen inks by a dynamic headspace needle trap device combined with gas chromatography-mass spectrometry.

Some harmful volatile organic compounds (VOCs), such as methylbenzene, ethylbenzene, xylene, chlorobenzene and bromobenzene, are the commonly found chemicals in pen inks. In this work, a dynamic headspace needle-trap device (D-HS-NTD) with a ZIF-8-derived nanoporous carbon (ZIF-8-NPC) as the adsorbent was developed for the extraction of some VOCs in different pen inks prior to GC-MS detection. The main important influencing experimental parameters including the flow rate of the purge gas N2, extraction temperature, extraction time, desorption temperature and desorption time for the extraction were optimized to obtain a high extraction efficiency. Under the optimized conditions, a good linearity was obtained in the concentration range of 0.1-400µgkg-1 with the correlation coefficients (r) ranging from 0.9911 to 0.9990 for the eleven VOCs. The LODs at a signal-to-noise ratio of 3 (S/N=3) were measured to be 10-20ngkg-1 for the VOCs. The developed method was applied to determine the VOCs from 20 pen inks. The recoveries of the VOCs for the method at the spiking levels of 0.5 and 20.0µgkg-1 fell in the range from 80.0% to 108%.

Barley husk carbon as the fiber coating for the solid-phase microextraction of twelve pesticides in vegetables prior to gas chromatography-mass spectrometric detection.

In this work, a barley husk biomaterial was successfully carbonized by hydrothermal method. The carbon had a high specific surface area and good stability. It was coated onto a stainless steel wire through sol-gel technique to prepare a solid-phase microextraction fiber for the extraction of trace levels of twelve pesticides (tsumacide, fenobucarb, indoxacarb, diethofencarb, thimet, terbufos, malathion, thiamethoxam, imidacloprid, buprofezin, acetamiprid, thiamethoxam) from vegetable samples prior to gas chromatography-mass spectrometric (GC-MS) detection. The main experimental parameters that could influence the extraction efficiency such as extraction time, extraction temperature, sample pH, sample salinity, stirring rate, desorption temperature and desorption time, were investigated. Under the optimized conditions, the linearity was observed in the range of 0.2-75.0µgkg-1 for tomato samples, and 0.3-60.0µgkg-1 for cucumber samples, with the correlation coefficients (r) ranging from 0.9959 to 0.9983. The limits of detection of the method were 0.01-0.05µgkg-1 for tomato samples, and 0.03-0.10µgkg-1 for cucumber samples. The recoveries of the analytes for the method from spiked samples were in the range of 76%-104%, and the precision, expressed as the relative standard deviations, was less than 12%.

Micro-solid phase extraction of chlorophenols using reduced graphene oxide functionalized with magnetic nanoparticles and graphitic carbon nitride as the adsorbent.

A magnetic micro-solid phase extraction method was applied for the extraction of trace levels of various chlorophenols prior to their determination by high performance liquid chromatography. The reduced graphene oxide functionalized with magnetic iron oxide nanoparticles and graphitic carbon nitride was prepared and used as adsorbent. It was characterized by scanning electron microscope, X-ray diffraction and vibrating sample magnetometer. Placed in a polypropylene hollow tube, the material was applied to the extraction of 3-chlorophenol, 2,3-dichlorophenol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol in cosmetic samples. Several experimental parameters that affect extraction efficiency were optimized. Following desorption with alkaline methanol, the chlorophenols were quantified by high performance liquid chromatography. A linear response was observed in the 1.0-200 µg·kg-1 CP concentration ranges. The detection limits (at a signal-to-noise ratio of 3) are between 0.20 and 0.30 µg·kg-1. The relative recoveries of the CPs from spiked cosmetics samples were in the range from 80.5 to 104%, with relative standard deviations lower than 12%. The filled extraction tube is high durable and stable. It can be used for 120 extraction cycles without a significant loss of extraction efficiency. The good adsorption ability of the sorbent was attributed to the strong π stacking interaction between the graphitic carbon nitride functionalized reduced graphene oxide and the aromatic rings in the CPs. Graphical abstract A magnetic micro-solid phase extraction (M-µSPE) method was applied to the extraction of various trace chlorophenols prior to their determination by high performance liquid chromatography. The M-µSPE method combines the advantages of both MSPE and µSPE.

A porous carbon derived from amino-functionalized material of Institut Lavoisier as a solid-phase microextraction fiber coating for the extraction of phthalate esters from tea.

In this work, a porous carbon derived from amino-functionalized material of Institut Lavoisier (C-NH2 -MIL-125) was prepared and coated onto a stainless-steel wire through sol-gel technique. The coated fiber was used for the solid-phase microextraction of trace levels of phthalate esters (diallyl phthalate, di-iso-butyl ortho-phthalate, di-n-butyl ortho-phthalate, benzyl-n-butyl ortho-phthalate, and bis(2-ethylhexy) ortho-phthalate) from tea beverage samples before gas chromatography with mass spectrometric analysis. Several experimental parameters that could influence the extraction efficiency such as extraction time, extraction temperature, sample pH, sample salinity, stirring rate, desorption temperature and desorption time, were investigated. Under the optimal conditions, the linearity existed in the range of 0.05-30.00 µg/L for green jasmine tea beverage samples, and 0.10-30.00 µg/L for honey jasmine tea beverage samples, with the correlation coefficients (r) ranging from 0.9939 to 0.9981. The limits of detection of the analytes for the method were 2.0-3.0 ng/L for green jasmine tea beverage sample, and 4.0-5.0 ng/L for honey jasmine tea beverage sample, depending on the compounds. The recoveries of the analytes for the spiked samples were in the range of 82.0-106.0%, and the precision, expressed as the relative standard deviations, was less than 11.1%.