The determination and prediction of the apparent reaction rates between excited triplet-state DOM and selected PPCPs.

To determine and predict the reaction rate between 3DOM* and PPCPs in various water bodies, this study defines a reaction rate coefficient ( [Formula: see text] ) to describe the reaction between 3DOM* and PPCPs. As the values also included the inhibition effect of DOM's antioxidant moieties, the calculation of [Formula: see text] is inconsistent with that of a bimolecular rate constant via the steady-state kinetic method. The [Formula: see text] values of 12 selected PPCPs were determined in two DOM solutions and ten DOM-containing water samples collected from typical surface water bodies in Beijing. The Pearson coefficients between nine predictors including the absorbance ratio (E2/E3), specific absorption coefficient at 254 nm (SUVA254), fluorescence index (FI), biological index (BIX), humification index (HIX), pH, total organic carbon (TOC), total fluorescence intensity (TFI) and TOC normalized TFI (TFI/TOC) and [Formula: see text] were examined. Correlation patterns for sulfonamides, ß-blockers and diclofenac supported the electron transfer pathway, and was distinctly different from those appeared for FQs where quenching effect played a main part. TFI and TFI/TOC were recognized as the most useful surrogates in empirically predicting [Formula: see text] . For PPCPs that went through the electron transfer pathway, [Formula: see text] could be well fit to the Rehm-Weller model assuming a proportional relationship between TFI and △Get. For FQs, [Formula: see text] was found to linearly correlated with TFI/TOC. The [Formula: see text] values determined in this study enrich the database of PPCPs photolysis parameters, and the correlation analysis provides reference for forecasting PPCPs fate in the aquatic environment.

VILLIN2 regulates cotton defense against Verticillium dahliae by modulating actin cytoskeleton remodeling.

The active structural change of actin cytoskeleton is a general host response upon pathogen attack. This study characterized the function of the cotton (Gossypium hirsutum) actin-binding protein VILLIN2 (GhVLN2) in host defense against the soilborne fungus Verticillium dahliae. Biochemical analysis demonstrated that GhVLN2 possessed actin-binding, -bundling, and -severing activities. A low concentration of GhVLN2 could shift its activity from actin bundling to actin severing in the presence of Ca2+. Knockdown of GhVLN2 expression by virus-induced gene silencing reduced the extent of actin filament bundling and interfered with the growth of cotton plants, resulting in the formation of twisted organs and brittle stems with a decreased cellulose content of the cell wall. Upon V. dahliae infection, the expression of GhVLN2 was downregulated in root cells, and silencing of GhVLN2 enhanced the disease tolerance of cotton plants. The actin bundles were less abundant in root cells of GhVLN2-silenced plants than in control plants. However, upon infection by V. dahliae, the number of actin filaments and bundles in the cells of GhVLN2-silenced plants was raised to a comparable level as those in control plants, with the dynamic remodeling of the actin cytoskeleton appearing several hours in advance. GhVLN2-silenced plants exhibited a higher incidence of actin filament cleavage in the presence of Ca2+, suggesting that pathogen-responsive downregulation of GhVLN2 could activate its actin-severing activity. These data indicate that the regulated expression and functional shift of GhVLN2 contribute to modulating the dynamic remodeling of the actin cytoskeleton in host immune responses against V. dahliae.

GhADF6-mediated actin reorganization is associated with defence against Verticillium dahliae infection in cotton.

Several studies have revealed that actin depolymerizing factors (ADFs) participate in plant defence responses; however, the functional mechanisms appear intricate and need further exploration. In this study, we identified an ADF6 gene in upland cotton (designated as GhADF6) that is evidently involved in cotton's response to the fungal pathogen Verticillium dahliae. GhADF6 binds to actin filaments and possesses actin severing and depolymerizing activities in vitro and in vivo. When cotton root (the site of the fungus invasion) was inoculated with the pathogen, the expression of GhADF6 was markedly down-regulated in the epidermal cells. By virus-induced gene silencing analysis, the down-regulation of GhADF6 expression rendered the cotton plants tolerant to V. dahliae infection. Accordingly, the abundance of actin filaments and bundles in the root cells was significantly higher than that in the control plant, which phenocopied that of the V. dahliae-challenged wild-type cotton plant. Altogether, our results provide evidence that an increase in filament actin (F-actin) abundance as well as dynamic actin remodelling are required for plant defence against the invading pathogen, which are likely to be fulfilled by the coordinated expressional regulation of the actin-binding proteins, including ADF.

Development of a high-throughput multi-residue method for analysis of common pesticides in aquatic environments by automated online solid phase extraction coupled with LC-MS/MS.

The present work describes the development of a fully automated method based on online solid phase extraction (SPE)-liquid chromatography-tandem mass spectrometry (LC-MS/MS) for the simultaneous analysis of multiple classes of pesticides or metabolites in drinking water (DW), surface water (SW), and wastewater effluents (WWEs). The target list covers 111 pesticides or metabolites of various properties and families. LC-MS/MS and online SPE parameters were optimized with regard to the sorbent type, mobile phase composition, wash volume, and flowrate as well as the injection volume. The method showed good linearity in two concentration ranges with 97% and 94% of the coefficients (R2) being higher than 0.99 in the low concentration range (0.1-100 ng L-1) and high concentration range (100-2500 ng L-1), respectively. High sensitivity was observed with method quantification limits (MQLs) of 0.03-5.3 ng L-1, 0.06-17 ng L-1, and 0.08-21 ng L-1, for DW, SW, and WWE, respectively. The recoveries showed an accuracy of 94%, 91%, and 91% in the range of 70-130% for three matrices with satisfactory precision. The overall analysis time per sample was 30 min with minimum pretreatment. To the best of our knowledge, for the first time, 64 pesticides were identified by the high throughput online SPE-based method. The optimized method was used for WWE sample analysis, and 49 pesticides were detected in 12 WWE samples from an economically active city in China. Five pesticides were detected in all the samples, i.e. paclobutrazol, atrazine, diuron, acetamiprid, and triadimenol, and the highest median concentration was observed for carbendazim (324 ng L-1). The advantages of the proposed method over offline ones make it have broad prospects in high throughput and reliable analysis of pesticides in aquatic environments.

Occurrence, spatiotemporal distribution, and risk assessment of current-use pesticides in surface water: A case study near Taihu Lake, China.

This study involved the monitoring and risk assessment of current-use pesticides in surface water from the northwestern section of the Taihu Lake Basin (China) in 2019. In particular, 114 current-use pesticides were measured in samples collected during four campaigns spread across the wet, dry, and normal seasons. Pesticide concentrations were measured by means of a novel analytical method involving online solid-phase extraction coupled to LC-MS/MS. In total, 1 plant growth regulator, 34 herbicides, 23 insecticides, and 25 fungicides were detected. Detection frequencies greater than 90% were recorded for 26 pesticides; furthermore, acetamiprid, azoxystrobin, bentazone, carbendazim, isoprothiolane, metolachlor, paclobutrazol, and triadimenol were present in every sample. The measured pesticide concentrations varied widely, from below the detection limit to 10,600 ng/L (tricyclazole). The highest median concentrations for the fungicide, herbicide, and insecticide families were observed for carbendazim (135 ng/L), metolachlor (40 ng/L), and imidacloprid (31 ng/L), respectively. Twenty-two pesticides were quantitatively reported in Chinese surface water for the first time. The number and concentration of detected pesticides were significantly higher in June and September (wet season) compared to March and December (dry season). Agricultural areas of the study area were more contaminated than the residential and industrial sections. Imidacloprid was the only pesticide that exhibited high risk to sensitive ecological species (RQmedian > 1) in all four seasons. Isoproturon, isoprothiolane, and pretilachlor were identified as high risk in March (RQmedian = 4.5), September (1.3), and June (1.1), respectively; moreover, another eight pesticides posed a high ecological risk at specific sites. Seven pesticides recorded moderate risks (i.e., RQmedian = 0.1-1.0). Of the 18 pesticides with cases of high risk, a novel risk index, which accounted for frequency of PNEC exceedance, ranged from 6.7 (imidacloprid) to 7.1 × 10-5 (propiconazole). The integrated consideration of ecological risk and frequency of risk inform priorities for regional pesticide management and control.

River bacterial community structure and co-occurrence patterns under the influence of different domestic sewage types.

Bacterial communities play a critical role in food webs and the biogeochemical cycles of fundamental elements. However, there remains a substantial gap in our knowledge of the anthropogenic impacts on bacterial co-occurrence patterns and ecosystem functions. In this study, we used Illumina high-throughput sequencing to characterize and compare the diversity, composition, co-occurrence patterns, and functional changes in bacterial communities in the Qingliu River under the influence of different types of domestic sewage. Twelve samples had similar dominant phyla, mainly Proteobacteria, Bacteroidetes, Actinobacteria, and Firmicutes, differing only in the proportions of the microorganisms. However, there was a large difference at the genus level, for example, the relative abundance of the genus Dechloromonas in the school sewage water samples (XXW) was much higher than that in the other samples, the genus Chryseobacterium was the dominant bacteria in the residential sewage water samples (JMW), and there were significant differences between the different samples (P < 0.01). This may indicate that external pollution and environmental induction deeply affect the bacterial community assembly in rivers. Network analysis showed that the river bacterial co-occurrence network has a modular structure (divided into 6 modules), and that the microbial taxonomic units from the same module were involved in the carbon and nitrogen cycle (e.g., the CL500-29 marine group and the genus Pseudomonas) and degradation of organic pollutants and toxic compounds (e.g., the genera Massilia and Exiguobacterium). Functional predictions indicate that the function of ABC transporter was highest in the hospital sewage water samples (YYW), while two-component system was more abundant in the XXW samples. In summary, our research provides a new perspective of community assembly in rivers under the influence of human activity.

Seasonal and spatial variations of pharmaceuticals and personal care products occurrence and human health risk in drinking water - A case study of China.

A case study was implemented to investigate the seasonal and spatial variations of 43 kinds of pharmaceuticals and personal care products (PPCPs) in the water supply system of Changzhou in China. The source water, water samples in each unit along the drinking water treatment process, as well as the drinking water product in both urban and rural area in different seasons have been included. The total concentrations of detected PPCPs range from 6.37 ng/L to 809.28 ng/L, the level of which is higher than other reports in China. In summer, more kinds of PPCPs were at higher concentrations in drinking water in urban area in spite of that fewer kinds of PPCPs were detected in raw water than in winter. It mainly because some kinds of PPCPs, which can be still detected under higher temperature and stronger irradiation in summer, were hardly removed by the drinking water treatment plant (DWTP). Therefore, people are at relatively higher health risk by PPCPs exposure through the intake of drinking water during summer than winter. The advanced treatment which applied GAC (granular activated carbon) filtration improved 2% to 46% of removal efficiency on PPCPs compared with conventional process, for which advanced treatment processes should be advocated in more DWTPs in China. In rural private wells, the situation is more worrying. Twelve more kinds of PPCPs were detected in rural drinking water than in urban, of which the max concentration reached 107 ng/L. The total concentrations of PPCPs in drinking water in rural area were obviously higher than in urban area, which lead to risk quotient (RQ) values of 4-6 times higher.

Automated online solid-phase extraction liquid chromatography tandem mass spectrometry investigation for simultaneous quantification of per- and polyfluoroalkyl substances, pharmaceuticals and personal care products, and organophosphorus flame retardants in environmental waters.

This work describes development of a quick and accurate online solid-phase extraction (SPE) liquid chromatography tandem mass spectrometry method for simultaneous determination of 87 emerging organic compounds, including 22 per- and polyfluoroalkyl substances, 58 pharmaceuticals and personal care products, and 7 organophosphorus flame retardants, in diverse water matrices. Considering the wide range of physicochemical properties for the target contaminants, efficient analysis in one injection is challenging. Thus, key extraction and analytical parameters, including online SPE sorbent, mobile phase additives, sample pH, loading solvent pH and composition, injection volume, and valve-switching time, were systematically optimized. The final conditions, namely a polymeric reversed-phase column with alkaline samples and an acidic loading solvent, provided satisfactory results for all target analytes compared to conventional methods that employ acidic samples for multi-residue analysis. The method detection limits (MDLs) ranged from 0.16 to 5.13 ng L-1 with 85% of MDLs lower than 2 ng L-1 for sample volumes of just 1.8 mL. The method also demonstrated satisfactory accuracy with 82% of analytes exhibiting 70-130% recovery. Importantly, only 30 min was required per sample. The optimized method was successfully applied to investigate the removal efficiency of emerging contaminants in a drinking water treatment plant and to analyze the environmental occurrence of target analytes. The method is sensitive, reliable, labor-saving, and cost effective, and therefore has the potential to advance large-scale environmental monitoring programs.

Organophosphate flame retardants in leachates from six municipal landfills across China.

With the phasing out of brominated flame retardants, organophosphate flame retardants (OPFRs) have been widely used and further detected in multiple environmental media. However, municipal landfill leachates, an important source of contamination of OPFRs to aquatic environment, have not been fully understood, especially in a developing country like China. Thus, the occurrence, aqueous removal efficiency, environmental emission, and risk assessment of 10 OPFRs were investigated in leachates from six municipal landfills across China. The results indicated that except triethyl phosphate (TEP), the remaining 9 OPFRs were detected in both raw and final leachates with different frequencies higher than 33.3%. The range of total concentrations of OPFRs (ΣOPFRs) across China was 29.0-437 and 0.652-32.4 µg L-1 in raw and final leachates, respectively. Tris(2-chloroethyl) phosphate (TCEP) was the dominant species and accounted for 78.5% and 85.8% of average ΣOPFR concentration in raw and final leachates, respectively. This may be because TCEP is the most prevalently used OPFR in China. The overall aqueous removal efficiency of ΣOPFRs across China ranged from 57.7% to 99.8%. Tris(2-butoxyethyl) phosphate was the most removed species (98.8%), whereas TCEP was the least removed species (91.5%). The annual emissions of ΣOPFRs discharged into the aquatic environment from municipal landfills across China were estimated to be between 170 and 7094 g. Further risk assessment based on risk quotient values in the final leachates showed that most OPFRs posed negligible risk except TCEP (medium and high risk) and tributyl phosphate (medium risk).

Dissipation kinetics and residues of triazolopyrimidine herbicides flumetsulam and florasulam in corn ecosystem.

The dynamic and residues of florasulam and flumetsulam in corn field ecosystem were investigated using quick, easy, cheap, effective, rugged, and safe (QuEChERS) procedure with high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The limits of quantification (LOQs) of the proposed method ranged from 0.005 to 0.01 mg/kg. Mean recoveries and relative standard deviations (RSDs) of the two compounds in all samples at three spiking levels ranged 94-110 % and 2.0-9.2 %, respectively. Florasulam and flumetsulam degradation followed first-order kinetics with half-lives 1.7-2.9 and 3.3-8.7 days in soil and 1.3-1.8 and 0.9-1.7 days in plant, respectively. The residues in all the samples were found to be less than the LOQs at preharvest intervals of 53 and 78 days. The results suggest that the combined use of florasulam and flumetsulam on corn is considered to be safe under the recommended conditions and can be utilized for establishing the maximum residue limit (MRL) of florasulam in corn in China.