Combined toxicity and adverse outcome pathways of common pesticides on Chlorella pyrenoidosa.

Pesticides due to their extensive use have entered the soil and water environment through various pathways, causing great harm to the environment. Herbicides and insecticides are common pesticides with long-term biological toxicity and bioaccumulation, which can harm the human body. The concept of the adverse outcome pathway (AOP) involves systematically analyzing the response levels of chemical mixtures to health-related indicators at the molecular and cellular levels. The AOP correlates the structures of chemical pollutants, toxic molecular initiation events and adverse outcomes of biological toxicity, providing a new model for toxicity testing, prediction, and evaluation of pollutants. Therefore, typical pesticides including diquat (DIQ), cyanazine (CYA), dipterex (DIP), propoxur (PRO), and oxamyl (OXA) were selected as research objects to explore the combined toxicity of typical pesticides on Chlorella pyrenoidosa (C. pyrenoidosa) and their adverse outcome pathways (AOPs). The mixture systems of pesticides were designed by the direct equipartition ray (EquRay) method and uniform design ray (UD-Ray) method. The toxic effects of single pesticides and their mixtures were systematically investigated by the time-dependent microplate toxicity analysis (t-MTA) method. The interactions of their mixtures were analyzed by the concentration addition model (CA) and the deviation from the CA model (dCA). The toxicity data showed a good concentration-effect relationship; the toxicities of five pesticides were different and the order was CYA > DIQ > OXA > PRO > DIP. Binary, ternary and quaternary mixture systems exhibited antagonism, while quinary mixture systems exhibited an additive effect. The AOP of pesticides showed that an excessive accumulation of peroxide in green algae cells led to a decline in stress resistance, inhibition of the synthesis of chlorophyll and protein in algal cells, destruction of the cellular structure, and eventually led to algal cell death.

Self-Assembled Three-Dimensional Polyamide/Silver Nanoparticle Pore Array as a Highly Sensitive and Reproducible SERS Substrate for Pesticide Detection in Water.

In this study, silver nanoparticles (AgNPs) are self-assembled onto the polyamide (PA) pore array through hydrogen bonding, resulting in and optimizing the PA/Ag 3D pore array substrates. The best surface-enhanced Raman scattering (SERS) substrate is obtained with a pore depth of 500 nm in the PA array, 30 nm AgNPs, at a pH of 5.0, and a 24 h assembly time. The SERS performance of the substrates is assessed using rhodamine 6G (R6G) as a probe molecule. The detection limit of the R6G molecule reaches 10-13 M, and the relative standard deviation is under 20%, indicating good enhancement ability and reproducibility. Furthermore, label-free detection of pesticide contaminant diquat with a detection limit of 2.69 × 10-9 M is achieved using the optimized 3D substrate, which meets environmental monitoring requirements for drinking water. The findings demonstrate that this 3D SERS substrate has promising potential for use and development in the fields of contaminant detection and chemical sensing.

Predicting the occurrence of antagonism within ternary guanidine mixture pollutants based on the concentration ratio of components.

The widespread prevalence and coexistence of diverse guanidine compounds pose substantial risks of potential toxicity interactions, synergism or antagonism, to environmental organisms. This complexity presents a formidable challenge in assessing the risks associated with various pollutants. Hence, a method that is both accurate and universally applicable for predicting toxicity interactions within mixtures is crucial, given the unimaginable diversity of potential combinations. A toxicity interaction prediction method (TIPM) developed in our past research was employed to predict the toxicity interaction, within guanidine compound mixtures. Here, antagonism were found in the mixtures of three guanidine compounds including chlorhexidine (CHL), metformin (MET), and chlorhexidine digluconate (CDE) by selecting Escherichia coli (E. coli) as the test organism. The antagonism in the mixture was probably due to the competitive binding of all three guanidine compounds to the anionic phosphates of E. coli cell membranes, which eventually lead to cell membrane rupture. Then, a good correlation between toxicity interactions (antagonisms) and components' concentration ratios (pis) within binary mixtures (CHL-MET, CHL-CDE, MET-CDE) was established. Based on the correlation, the TIPM was constructed and accurately predicted the antagonism in the CHL-MET-CDE ternary mixture, which once again proved the accuracy and applicability of the TIPM method. Therefore, TIPM can be suggested to identify or screen rapidly the toxicity interaction within ternary mixtures exerting potentially adverse effects on the environment.

Hydrophilic magnetic Ti3C2Tx-based nanocomposite as an efficient boron adsorbent: Synthesis, characterization, and application.

It is widely recognized that wastewater containing boron is an environmental issue. Therefore, the development of adsorbents with excellent adsorption capacity, stability, and recyclability is essential in water treatment applications. A Fe3O4/PDA/Ti3C2Tx/PEI/DHHA nanocomposite has been prepared that can be used to separate and recover boric acid by adjusting the pH of the solution, based on the affinity theory of boric acid and cis-diol. Through series characterization, it was determined that the adsorbent possessed good magnetic properties, high hydrophilicity and high loading capacities. In this study, 4-formylphenylboronic acid (FPBA) was selected as the model compound. The nanocomposite exhibited an adsorption equilibrium time of 10 h and an adsorption capacity of 98.99 mg/g at pH = 8.5 and 25 °C. The Langmuir isothermal model and the quasi-secondary kinetic model are both appropriate for describing the adsorption process. Thermodynamic results suggest that adsorption is a spontaneous chemisorption process. Furthermore, the nanocomposite retains good regeneration performance after five adsorption-desorption cycles.

Applicability of core-shell SiO2 microspheres with a high TiO2 loading as stationary phase for HPLC.

BACKGROUND: Due to its high chemical stability, sufficient rigidity and zwitterionic ion exchange properties, TiO2 can be considered as an alternative stationary phase material to SiO2 for high performance liquid chromatography. TiO2 stationary phase is usually prepared by coating TiO2 onto SiO2 support by sol-gel method. However, in the traditional coating method, in order to overcome the rapid hydrolysis rate of tetrabutyl orthotitanate, only a very low concentration of tetrabutyl orthotitanate can be used, resulting in a low loading of TiO2 on the support. RESULTS: TiO2 core-shell spheres with a good monodispersity were prepared using 0.25 mol L-1 tetrabutyl orthotitanate. The specific surface area, pore volume, pore diameter and TiO2 loading of the TiO2 core-shell spheres were 66 m2 g-1, 0.15 cm3 g-1, 9.8 nm and 57%, respectively. The core-shell spheres were derivatized with n-octadecyltrichlorosilane and then packed into a stainless steel column to test the separation performance for neutral, basic and acidic samples in liquid chromatography. A baseline separation of polyaromatic hydrocarbons was achieved, showing a column efficiency for fluorene of 118075 plates m-1. The prepared stationary phase was also used to separate acidic and basic mixtures, and column efficiencies of 54500 and 25836 plates m-1 were obtained for N,N-dinitroaniline and p-chlorophenol, respectively. The relative standard deviations of the retention times of polyaromatic hydrocarbons for run-to-run, day-to-day and column-to-column repeatability were all below 5.1%. SIGNIFICANCE AND NOVELTY: This work demonstrated that TiO2 can be coated in the pores of the shell of SiO2 core-shell spheres with high TiO2 loading using a high concentration of tetrabutyl orthotitanate as the titania source. The experimental results show that the TiO2 coated core-shell spheres can be a good alternative stationary phase for liquid chromatography.

The Study of Optimal Adsorption Conditions of Phosphate on Fe-Modified Biochar by Response Surface Methodology.

A batch of Fe-modified biochars MS (for soybean straw), MR (for rape straw), and MP (for peanut shell) were prepared by impregnating biochars pyrolyzed from three different raw biomass materials, i.e., peanut shell, soybean straw, and rape straw, with FeCl3 solution in different Fe/C impregnation ratios (0, 0.112, 0.224, 0.448, 0.560, 0.672, and 0.896) in this research. Their characteristics (pH, porosities, surface morphologies, crystal structures, and interfacial chemical behaviors) and phosphate adsorption capacities and mechanisms were evaluated. The optimization of their phosphate removal efficiency (Y%) was analyzed using the response surface method. Our results indicated that MR, MP, and MS showed their best phosphate adsorption capacity at Fe/C ratios of 0.672, 0.672, and 0.560, respectively. Rapid phosphate removal was observed within the first few minutes and the equilibrium was attained by 12 h in all treatment. The optimal conditions for phosphorus removal were pH = 7.0, initial phosphate concentration = 132.64 mg L-1, and ambient temperature = 25 °C, where the Y% values were 97.76, 90.23, and 86.23% of MS, MP, and MR, respectively. Among the three biochars, the maximum phosphate removal efficiency determined was 97.80%. The phosphate adsorption process of three modified biochars followed a pseudo-second-order adsorption kinetic model, indicating monolayer adsorption based on electrostatic adsorption or ion exchange. Thus, this study clarified the mechanism of phosphate adsorption by three Fe-modified biochar composites, which present as low-cost soil conditioners for rapid and sustainable phosphate removal.

NH3 Plasma Functionalization of UiO-66-NH2 for Highly Enhanced Selective Fluorescence Detection of U(VI) in Water.

Radioactive U(VI) in nuclear wastewater is a global environmental pollutant that poses a great threat to human health. Therefore, it is of great significance to develop a U(VI) sensor with desirable sensitivity and selectivity. Inspired by electron-donating group modification for enhancement of binding affinity toward U(VI), we report an amine group functionalization of UiO-66-NH2, using a low-cost, environmentally friendly, and low-temperature NH3 plasma technique as a fluorescence switching nanoprobe for highly sensitive and selective detection of U(VI). The resulting amine-functionalized UiO-66-NH2 (LTP@UiO-66-NH2) shows dramatically enhanced fluorescence emission and selective sensitivity for U(VI) on the basis of the quenching effect. The quenching efficiency increases from 58 to 80% with the same U(VI) concentration (17.63 µM) after NH3 plasma functionalization. As a result, the LTP@UiO-66-NH2 has the best Ksv (1.81 × 105 M-1, 298 K) and among the lowest LODs (0.08 µM, 19.04 ppb) compared with those reported in the literature. Intraday and interday precision and application in real environment experiments indicate stable and accurate U(VI) detection performance. Fluorescence lifetime and temperature-dependent detection experiments reveal that the quenching mechanism belongs to the static quenching interaction. The highly selective fluorescence detection is attributed to the selective binding of U(VI) by the rich functionalized amine groups of LTP@UiO-66-NH2. This work provides an efficient fluorescence probe for highly sensitive U(VI) detection in water, and a new strategy of tailored plasma functionalization for developing a practical MOF sensor platform for enhanced fluorescence emission, sensitivity, and selectivity for detecting trace amounts of radioactive species in the environment.

Performance optimization and microbial community evaluation for domestic wastewater treatment in a constructed wetland-microbial fuel cell.

Constructed wetland-microbial fuel cell system (CW-MFC), an attractive technology still under study, has shown to improve domestic wastewater treatment efficiency and generate bioelectricity. This work investigated the effect of multiple factors on the performance optimization for the pollutants removal and bioelectricity production compared to a traditional CW, including influent chemical oxygen demand (COD) concentration, hydraulic retention time (HRT) and external resistance. The results showed that the optimal operating conditions of COD concentration, HRT and external resistance for CW-MFC were 200 mg/L, 24 h and 1000 Ω, respectively. The average COD, NH4+-N, NO3--N and TP removal efficiencies were 6.06%, 3.85%, 3.68% and 3.68% higher than these in CW system, respectively. Meanwhile, the maximum output voltage and power density of CW-MFC were 388 ± 12 mV and 107.54 mW/m3. In addition, the microbial community analysis indicated that the pollution removal and bioelectricity generation might benefit from the gradual enrichment of electroactive bacteria (Tolumonas) and denitrifying bacteria (Denitratisoma, Methylotenera and Sulfuritales). The findings can provide the optimum operation parameters and mechanism insight for the performance of CW-MFC systems.

Controlled manipulation of TiO2 nanoclusters inside mesochannels of core-shell silica particles as stationary phase for HPLC separation.

Based on a detailed study of the hydrolysis process of tetrabutyl orthotitanate (TBOT), TiO2 nanoclusters were modified inside the pores of SiO2 core-shell particles instead of the outside. The pore size distribution of SiO2 core-shell spheres modified with TiO2 (SiO2@dSiO2@TiO2) was analyzed by Barrett-Joyner-Halenda (BJH) method and density functional theory (DFT) method, respectively. The results of the DFT calculations demonstrate that the TiO2 nanoclusters are always first formed in bulk solution and then enter the pores. By regulating the rate of hydrolysis of TBOT, almost all of the TiO2 nanoclusters are modified into the pores and the structure of the original SiO2 core-shell sphere is hardly affected. The morphology of the particles was characterized by scanning electron microscopy and transmission electron microscopy. The crystal phase of TiO2 was measured by XRD. SiO2@dSiO2@TiO2 spheres functionalized with C18 were packed into a stainless steel column. The chemical stability of SiO2@dSiO2@TiO2 spheres under alkaline was tested by flushing of a mobile phase at pH 13 for 7 days. The efficiency of the column after the alkali solution treatment still reaches 98,430 plates m-1, which is only about 1.6% lower than that before the alkali solution treatment. A series of basic and acidic analytes were also separated on the column. Graphical abstract TiO2 nanocrystals were coated into the pore of core-shell silica spheres. The prepared particles were packed into the column and separation performance up to 98,430 plates per meter was achieved.

Alginate capped and manganese doped ZnS quantum dots as a phosphorescent probe for time-resolved detection of copper(II).

A method is described for the detection of Cu(II). It is based on the use of a room-temperature phosphorescent probe consisting of alginate-capped and manganese(II)-doped ZnS quantum dots. The carboxy groups at the surface of the probe strongly coordinate Cu(II) to form a complex. As a result, the 4T1-6A1 transition of the Mn(II) ions in the probe is quenched, and the long decay time (~2.1 ms in the unquenched state) is accordingly reduced. At excitation/emission wavelengths of 316/590 nm and a delay time of 0.1 ms, the probe shows a linear response in the 0.01 to 12 µM Cu(II) concentration range. The detection limit is 6.0 nM and the RSD is 3.2% (for n = 5). Graphical Abstract A two-step procedure is described to synthesize alginate capped manganese doped ZnS QDs. These coordinate with Cu(II) to form an absorbent complex and can be used as a phosphorescent probe for time-resolved detection of Cu(II).

Characterizing the Existence of Fluorescence Quenching Agents Using EEM Fluorescence and UV Spectra: Taking the Interaction of Humic Acid and Fe(â ¢) as an Example.

The fluorescence quenching agents was characterized with three-dimensional fluorescence and ultraviolet (UV) spectra. When there was Fe (Ⅲ) in the sample, the humic fluorescence would be quenched and their UV spectra were not affected. The variation of fluorescence intensity (I) at Ex/Em=300/510 nm and UV absorbance(A) at UV300 were investigated in the article. The smaller the ratio of fluorescence intensity versus UV absorbance (I/A) is, the higher the fluorescence quencher Fe(Ⅲ) concentration is. According to Stern-Volmer equation I/I0=1-fc×Kc×[c] /(1+Kc×[c] ) and fitted function I/A=f×[k/(cFe3++c)+b] , the fitted fluorescent quenching constant Kc was ranged between 1.08 to 1.15, the ratio of bounded fluorophores versus total fluorophores, i.e. fc, was ranged between 1.10 to 1.14. The ratio of fluorescence intensity and absorbance of humic acid was fitted with Fe(Ⅲ) concentration and the constants were acquired as following: f=0.83～1.19, k=587.19～612.19, c=0.87～0.92, b=-87.09～-46.36. The correlation curve values were 0.99. The Stern-Volmer formula was used to describe the quenching effect of humic acid fluorescence by Fe (Ⅲ). However, due to the fact that the fluorescence intensity I0 without quencher was difficult to acquire during the analysis of practical samples, the fitted function between the ratio of I/A and Fe(Ⅲ) was used to reflect the quenching effect of Fe(Ⅲ) on the fluorescence of humic acid, which was based on the correlations between the fluorescence intensity I0 and ultraviolet absorbance A. The fitted formula was used to predict the iron ions concentration of the resin separated and concentrated samples from wastewater treatment plant and receiving waters. The predicted values were in good accordance with those determined with inductively coupled plasma atomic emission spectroscopy(ICP-AES) method when the iron ion concentration was above 0.4 mg·L-1, which could be used to ascertain the existence of fluorescence quenching agent and their corresponding concentration.

Near Infrared Spectroscopy Study on Nitrogen in Shortcut Nitrification and Denitrification Using Principal Component Analysis Combined with BP Neural Networks.

To achieve efficient nitrogen removal and rapid detection of ammonia nitrogen and nitrite nitrogen, principal component analysis and neural networks were used to establish quantitative analysis model of ammonia nitrogen and nitrite nitrogen in shortcut nitrification and denitrification based on near infrared spectroscopy­BP neural networks model. The results showed that ammonia nitrogen concentration decreased from 45.3 to 2.7 mg·L-1 after aerobic, and nitrite nitrogen concentration increased from 0.01 to 19.6 mg·L-1, while nitrite nitrogen concentration decreased from 19.6 to 1.2 mg·L-1 after anoxic, which means that rapid nitrification and denitrification are successfully achieved. The principal component analysis of the original near infrared spectra for water samples showed the first 13 principal components represented the information of the original spectrum data, with cumulative contribution rate being 95.04%. In this way, redundant information can be eliminated to reduce the number of dimensions in the model. The spectral data matrix is accordingly reduced from 192×2203 to 192×13, which contributes greatly to easier calculations and improves the accuracy of the model. The correction results of BP neural networks model showed the coefficient of determination for ammonia nitrogen and nitrite nitrogen concentration was 0.950 4 and 0.976 2 respectively, with the root mean square error of calibration being 0.016 6 and 0.010 9. BP neural networks model yields predicted values fitting well with the expected values for ammonia nitrogen and nitrite nitrogen concentration, with R2 being 0.974 0 and 0.981 4 respectively, with the root mean square error of prediction being 0.033 7 and 0.028 7, suggesting that BP neural networks model had a good prediction results for ammonia nitrogen and nitrite nitrogen concentration. The study demonstrated that ammonia nitrogen and nitrite nitrogen concentration can be rapidly predicted with BP neural networks based analysis of the near infrared spectroscopy of the water sample in shortcut nitrification and denitrification, which may provide timely and flexible control to shortcut nitrification and denitrification operation according to the ammonia nitrogen and nitrite nitrogen concentration changes, and makes a quick and effective detection technique for denitrification.

Analysis of poly-ß-hydroxyalkonates (PHA) during the enhanced biological phosphorus removal process using FTIR spectroscopy.

Enhanced biological phosphorus removal (EBPR) is the main phosphorus removal technique for wastewater treatment. During the anaerobic-aerobic alternative process, the activated sludge experienced the anaerobic storage of polyhydroxy-ß-alkonates (PHA) and aerobic degradation, corresponding the infrared peak intensity of sludge at 1 740 cm(-1) increased in the aerobic phase and declined in the anaerobic phase. Compared with PHA standard, this peak was indentified to attribute the carbonyl of PHA. The overlapping peaks of PHA, protein I and II bands were separated using Gaussian peak fitting method. The infrared peak area ratios of PHA versus protein I had a good relationship with the PHA contents measured by gas chromatography, and the correlation coefficient was 0.873. Thus, the ratio of the peak area of PHA versus protein I can be considered as the indicator of the PHA content in the sludge. The infrared spectra of 1 480-1 780 cm(-1) was selected, normalized and transferred to the absorption data. Combined with the chromatography analysis of PHA content in the sludge sample, a model between the Fourier-transform infrared spectroscopy (ETIR) spectra of the sludge and PHA content was established, which could be used for the prediction of the PHA content in the unknown sample. The PHA content in the sludge sample could be acquired by the infrared spectra of the sludge sample and the established model, and the values fitted well with the results obtained from chromatograph. The results would provide a novel analysis method for the rapid characterization and quantitative determination of the intracellular PHA content in the activated sludge.

Identifying the component responsible for antagonism within ionic liquid mixtures using the up-to-down procedure integrated with a uniform design ray method.

Various chemicals in the environment always exist as mixtures. Toxicity interaction within mixtures may pose potential hazards and risks to the environmental safety and human health. Recent studies showed that toxicity interaction by ionic liquid (IL) mixtures can be related to a certain component. To identify the component, we developed a novel procedure integrating an up-to-down process with the uniform design-based ray method (UDUD) and applied it into an IL mixture system of four 1-butyl-3-methylimidazolium ILs (simply [bmim]X) where X=Cl(-), Br(-), CH3OSO3(-) and CH3(CH2)7OSO3(-). It was shown that two mixture rays in the quaternary system exhibited significant antagonistic interaction. In this paper, the UDUD was first employed to design four ternary mixture systems. The microplate toxicity analysis was used to determine the toxicities of various mixtures to a freshwater photobacterium Vibrio qinghaiensis sp.-Q67. The concentration addition was taken as an additive reference to assess the toxicity interactions taking place in mixtures. The results revealed that some ternary mixture rays including [bmim]CH3(CH2)7OSO3 display antagonism while the ternary rays without [bmim]CH3(CH2)7OSO3 exhibit additivity. On these grounds, we again designed all binary mixtures containing [bmim]CH3(CH2)7OSO3, determined their toxicities and assessed toxicity interaction. The results showed that three binary mixture systems produce antagonism. Thus, it may be concluded that [bmim]CH3(CH2)7OSO3 is indeed a key component inducing mixture antagonism.

Degradation of natural organic matter by TiO2 photocatalytic oxidation and its effect on fouling of low-pressure membranes.

Natural organic matter (NOM) fouling continues to be the major barrier to efficient application of microfiltration (MF) and ultrafiltration (UF) in drinking water treatment. In this study, the potential of TiO2/UV photocatalytic oxidation to control fouling of membranes by NOM was evaluated. Decomposition kinetics of NOM was investigated using a commercial TiO2 catalyst, and the effect of various experimental parameters including TiO2 dosage and initial total organic carbon (TOC) concentration were also determined. The reaction kinetics was found to increase with increasing TiO2 dosage, but decrease with increasing initial TOC concentration. Even though the rate of TOC removal was relatively low, the TiO2/UV process was very effective in controlling membrane fouling by NOM. At a TiO2 concentration of 0.5 g/L, fouling of both an MF and a UF membrane was completely eliminated after 20 min of treatment. Careful analyses of specific UV absorbance (SUVA) and molecular weight (MW) distribution of NOM revealed that the effectiveness in membrane fouling control is the result of the changes in NOM molecular characteristics, namely MW and SUVA due to the preferential removal and transformation of large, hydrophobic NOM compounds. Results from this study show that TiO2/UV photocatalytic oxidation is a promising pretreatment method for MF and UF systems.

Preparation and characterization of visible-light-active nitrogen-doped TiO2 photocatalyst.

A visible-light photocatalyst was prepared by calcination of the hydrolysis product of Ti(SO4)2 with ammonia as precipitator. The color of this photocatalyst was vivid yellow. It could absorb light under 550 nm wavelength. The crystal structure of anatase was characterized by XRD. The structure analysis result of X-ray fluorescence (XRF) shows that doped-nitrogen was presented in the sample. The photocatalytic activities were evaluated using methyl orange and phenol as model pollutants. The photocatalytic activities of samples were increasing gradually with calcination temperature from 400 degrees C to 700 degrees C under UV irradiation. It can be seen that the degradation of methyl orange follows zero-order kinetics. However, the calcination temperatures have no significant influence on the degradation of phenol under sunlight. The N-doped catalyst shows higher activity than the bare one under solar irradiation.