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In this study, fluopyram (FOR), acetamiprid (ATP) and chlorantraniliprole (CAP) were used individually or in combination at the maximum recommended dose in greenhouse strawberries to research the dissipation dynamics and dietary risks. A multi-residue analytical method for FOR, ATP and CAP in strawberries using UPLC-MS/MS integrated with QuEChERS approach was develop with a strong linearity (R2 ≧ 0.9990), accuracy (recoveries of 82.62–107.79%), and precision (relative standard deviations of 0.58–12.73%). The limits of quantification were 0.01 mg kg− 1. Field results showed that the half-lives of FOR, ATP and CAP in strawberry fruits were 11.6–12.4 days, 6.1–6.7 days and 10.9–11.7 days, respectively. The half-lives of the three investigated pesticides showed no significant difference when used individually or in combination. A risk assessment indicated that the dietary intake risks of the three pesticides in grown strawberries were 0.0041–7.63% whether applied alone or joint, which demonstrated that the dietary intake risks of three pesticides in grown strawberries could be negligible for Chinese male and female consumers, and even though pesticides were used in combination, there was no need to be concerned about the safety. This paper serves as a guide for the safe use of FOR, ATP and CAP on greenhouse strawberries.

The dissipation and residue of validamycin A in grapes were investigated under field conditions. An ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method for the determination of validamycin A in grapes was established and validated. Methanol and water (90/10

A wind-wave generation model over an ice-covered sea is proposed. The wind velocity over the ice upper surface is decomposed into the mean velocity profile of the boundary-layer flow and small perturbations, while the ice cover is modelled as a viscoelastic layer, with the water part modelled as an inviscid fluid. The present model is based on two-dimensional linear flow-instability theory, with no-slip boundary conditions at the air–ice interface, and both normal and shear stress boundary conditions matched on the air–ice interface. It is shown that the model converges to the field and experimental data for open-water cases. The ice elasticity is found to be the critical factor for generating wind waves, and the generation of flexural-gravity waves and elastic waves in ice is analyzed.

This study aimed to develop a reliable method for the simultaneous analysis of triflumizole (TRIF) and its primary metabolite FM-6-1 (N-4-chloro-2-trifluoromethylphenyl-2-propoxy-acetamidine) in the soil and treated strawberries using solid phase extraction (SPE) coupled with gas chromatography-tandem mass spectrometry (GC-MS/MS). Using this method, TRIF and FM-6-1 degradation in strawberries and the soil under greenhouse conditions were investigated. The field trials showed that t1/2 of TRIF and total residues (the sum of TRIF and FM-6-1) were 1.6–2.2 days and 2.4–2.9 days in strawberry and 4.3–6.1 days and 5.5–6.9 days in soil, respectively. Terminal total residues were ≤ 0.39 mg/kg in strawberry and ≤ 0.42 mg/kg in soil from 5 to 10 days of harvest. The risk quotient (RQ) of TRIF was below 1.89%, showing that the dietary risk of TRIF in strawberry was low. These findings provide guidance for the use of TRIF on crops and provide reference to establish the maximum residue level (MRL) of TRIF in strawberry.

The residue levels and risk assessment of imidacloprid (IMI) and chlorantraniliprole (CAP) in celery grown under open field and greenhouse cultivation were investigated. Both pesticides were used through foliar application and soil drench application at the recommended dose (RD) and 10-fold recommended dose (10RD). The half-lives of IMI and CAP in celery were 1.9 to 5.8 days and 4.3 to 6.5 days after foliar application, respectively, and the dietary risk quotients of IMI and CAP were 14.8 to 18.3% and 1.0 to 1.2%, respectively. For soil drench application, the half-lives of IMI and CAP in soil were 17.5 to 28.5 days and 15.1 to 23.7 days, respectively. Celery plants were able to absorb both insecticides from the soil. The highest concentrations of IMI in celery plants were 0.12 to 0.24 mg kg-1 (RD) and 0.34 to 0.39 mg kg-1 (10RD), and those for CAP were 0.0081 to 0.015 mg kg-1 (RD) and 0.028 to 0.057 mg kg-1 (10RD). Based on the highest residues of IMI and CAP in celery, the dietary risk quotients of IMI and CAP were 15.0% (RD) to 15.6% (10RD) and 1.0% (RD and 10RD) after soil drench application, respectively. The observed bioconcentration factors were 1.38 to 2.11 (IMI) and 0.35 to 0.48 (CAP), indicating that celery accumulated IMI more easily than CAP. The foliar and soil applications of IMI and CAP in celery at the RD and 10RD do not pose a safety risk to consumers.

Studies have shown that kresoxim-methyl (KM) and other strobilurin fungicides have toxic effects on aquatic organisms. However, the potential deleterious effects of kresoxim-methyl (KM) on adult zebrafish regarding the ecological risk of environmental concentration remain unclear. Here, the histology and untargeted metabonomics was used to investigate the adverse effect on female zebrafish after exposure to KM at environmental concentration, aquatic life benchmark and one-half LC

Flupyradifurone (FPO) easily spreads to the water environment after application because of its high solubility in water (3200 mg/L, 20 °C), but as a novel neonicotinoid pesticide, its environmental fate study is still lacking. Here, laboratory experiments were conducted to investigate the degradation kinetics and pathways of FPO in aqueous solutions and natural waters. The results showed that FPO was fairly stable in water under natural conditions (the hydrolysis half-lives at 15 °C, 25 °C, and 35 °C were150 d, and the photolysis half-lives under sunlight were168 h). However, FPO was photodegraded rapidly under ultraviolet (UV) light (half-lives of 2.37-3.81 min). Then, indirect photolysis under UV light was examined with the addition of photosensitizers, revealing that direct photolysis is the main FPO degradation pathway in water, and the contribution of indirect photolysis was limited. Moreover, two photoproducts were separated, purified and collected via preparative HPLC, and identified via high resolution mass spectrometry. Then, the plausible photolysis pathway was proposed. The results of this study will contribute to a better understanding of the fate of FPO in the water environment.

Levonorgestrel (LNG) and quinestrol (QUN) are typical endocrine disruptors that enter the soil via sewage irrigation and sludge return. However, the fates of both compounds in soil are not well-understood. Laboratory microcosm studies were conducted to fill the gap of understanding of LNG and QUN behavior in soils. High values of goodness-of-fit indices (GFIs) were obtained using the double-first-order in parallel (DFOP) model and the single-first-order (SFO) model to fit the degradation kinetics of LNG and QUN in soils, respectively. The end-points (DT50 and DT90) of LNG and QUN were positively correlated with soil total organic carbon (TOC). Soil water content and temperature were observed to be critical factors in degradation of LNG and QUN. The degradation rates of LNG and QUN were very slow under sterile and flooded conditions, indicating that the aerobic microbial degradation was dominant in the degradation of LNG and QUN. Moreover, major transformation products were identified, and biodegradation p...

While cyantraniliprole has been frequently used in rice fields, knowledge of the uptake, translocation and distribution of cyantraniliprole in rice planting systems is still largely unexplored. Plant uptake is a crucial factor in determining how cyantraniliprole moves through the food chain. Understanding the uptake, translocation and distribution of cyantraniliprole in rice planting system is essential to predicting its accumulation in rice and potential human exposure. Herein, the uptake process of cyantraniliprole in a hydroponic-rice system was systematically investigated. Results showed that cyantraniliprole was easily absorbed by rice roots via a passive diffusion process through the apoplastic pathway and then translocated upward through the xylem, but its acropetal translocation was limited. Cyantraniliprole in shoots can also be downward translocated through the phloem, although only to a limited extent, showing rice plants' weak phloem movement capacity. Furthermore, cyantraniliprole had a short half-life in sediment-water system and dissipated faster in anaerobic than aerobic conditions. At the equilibrium stage of a sediment-water system, cyantraniliprole is preferentially partitioned to the solid phase. Our study provides a systematic insight into the uptake, translocation and distribution of cyantraniliprole in the rice planting system, which is very helpful for better field cyantraniliprole application and environmental risk assessment.

Limited literature had focused on the combined effect of triazole fungicides on aquatic organisms at environmental concentrations. In this research, difenoconazole (DIF) and tebuconazole (TEB) mixture exhibited additive effect on the acute toxicity to zebrafish embryos. The transcriptomics and metabolomics demonstrated DIF and TEB mixtures at aquatic life benchmark and environmental concentration simultaneously influenced the lipid metabolism, arachidonic acid metabolism, steroid hormone biosynthesis and tryptophan metabolism, but showed diverse response patterns mediating the combined effects on zebrafish embryos after 120 h exposure. The DIF and TEB mixture at aquatic life benchmark caused combined effect on yolk sac resorption and metabolites, was less than the additive effect of individual DIF and TEB. It was found environmental concentration of DIF and TEB caused much lower levels of IFN and IL6, induced higher levels of PGE

A modified QuEChERS method for determining cyenopyrafen in strawberries, mandarins and their processed products was established with a good linearity (R2 > 0.9981), accuracy (recoveries of 83% to 111%) and precision (relative standard deviations of 0.9% to 14%). The limit of quantification (LOQ) was 0.01 mg/kg. Field results showed that the half-lives of cyenopyrafen were 6.8 and 11.8 d in strawberry and mandarin respectively, and that the final residues were within established maximum residue limits (MRLs). The household processing factors (PFs) for cyenopyrafen residues in strawberry and mandarin fruits were also studied: residues increased in strawberry jam (PF 1.51) and mandarin juice (1.31) but decreased in strawberries (0.58) and mandarin pulp (

In this study, a new rapid cleanup method was developed for the analysis of 111 pesticide multi-residues in lettuce and Chinese chives by GC&ndash, MS/MS and LC&ndash, MS/MS. QuEChERS (quick, easy, cheap, effective, rugged and safe)-based sample extraction was used to obtain the extracts, and the cleanup procedure was carried out using a Sin-QuEChERS nano cartridge. Comparison of the cleanup effects, limits of quantification and limits of detection, recoveries, precision and matrix effects (MEs) between the Sin-QuEChERS nano method and the classical dispersive solid phase extraction (d-SPE) method were performed. When spiked at 10 and 100 &mu, g/kg, the number of pesticides with recoveries between 90% to 110% and relative standard deviations &lt, 15% were greater when using the Sin-QuEChERS nano method. The MEs of Sin-QuEChERS nano and d-SPE methods ranged between 0.72 to 3.41 and 0.63 to 3.56, respectively. The results verified that the Sin-QuEChERS nano method was significantly more effective at removing pigments and more convenient than the d-SPE method. The developed method with the Sin-QuEChERS nano cleanup procedure was applied successfully to determine pesticide residues in market samples.

Knowledge about the negative effects and mechanism of sulfentrazone (SUL) on aquatic early life stages is still limited. Here we investigated the lethal and sub-lethal effects of SUL during zebrafish embryo-larvae development. Results demonstrated that the 96 h and 120 h-LC50 of SUL to embryonic zebrafish was 2.02 mg/L, and the 30 d-LC50 was 0.899 mg/L after embryos exposed to SUL for 30 d. High concentrations of SUL delayed yolk sac absorption, disordered the hatching and heart rate during zebrafish embryonic stage, while 0.0100–0.100 mg/L SUL had no phenotypic changes on embryonic development, but decreased the body weight of larvae after 30 d exposure. RNA-seq identified 321, 394 and 727 differentially expressed genes in larvae after embryos exposed to 0.0100 mg/L, 0.0400 mg/L and 0.400 mg/L SUL for 30 d, found that the transcriptional profiles involved in heart development and endocrine disruption were simultaneously influenced by different concentrations of SUL, such as adrenergic signaling in cardiomyocytes, cardiac muscle contraction, cell adhesion molecules and steroid biosynthesis. Biochemical analysis showed that SUL increased the levels of E2, T3 and TSH, induced the activities of mitochondrial complex IV, cytochrome c oxidase, Ca2+-ATPase, total Na+K+-ATPase and Ca2+Mg2+-ATPase, and decreased ATP formation after embryos exposed to SUL for 5 d and 30 d. Further comprehensive analysis demonstrated that SUL caused more significantly alteration on the transcript, level or activity of the key elements involved in heart development and endocrine disruption after 30 d exposure, indicated long-term SUL exposure might cause more negative effects on zebrafish at doses below the presumed no-observed-adverse-effect level during early life development. The results inferred the environmental concentration of SUL might cause potential cardiac and endocrine health risk in zebrafish later life stages, also facilitated a better understanding of the sub-lethal effects and molecular mechanism of SUL on aquatic organism.

As the melting of Arctic sea ice accelerates, the sea state of the Arctic Ocean is constantly changing. To accurately predict ocean waves in polar regions with ice cover, it is necessary to develop an accurate wave-ice interaction model. The wave model with ice cover based on the viscoelastic sea ice model has shown good performance in recent research results. However, the viscosity and elastic parameters in this sea ice model cannot be determined directly. A theoretical method for estimating the elastic modulus in the viscoelastic sea ice model is developed in this paper. This is a method that combines the scattering theory of elastic ice floes and the equivalent elastic energy method, which assumes that the elastic energy of discrete ice floes is equivalent to the viscoelastic ice layer. With this method, the equivalent elastic modulus of the discrete ice floe field can be directly calculated. As the diameter of the ice floe increases, the value of the equivalent elastic modulus increases nonlinearly in the calculation results, but it is not affected by the wave period.

An approximate solution for wave transmission and reflection between open water and a finite viscoelastic ice cover is developed in the present study, in which both the water part and the ice cover are treated as a continuum, each governed by its own equation of motion. The interface conditions include matching velocities and stresses between the two continua. In this study, only two modes of the dispersion relation are considered, and horizontal boundary conditions are approximated by matching mean values. The reflection and transmission coefficients are determined for simplified cases to compare with earlier theories. Behaviors of the resonance are obtained for pure elastic ice covers. The effect of viscosity is also investigated for viscoelastic ice covers. According to the above wave-ice interaction model, the stress and strain are calculated in the ice cover. By using a stress failure criterion, the break-up condition of ice covers with different thickness and length under the interaction of waves and sea ice is determined. Finally, a dynamic evolution model of the ice floe size distribution function in the marginal ice zone is established. The present study is useful for modeling the wave-in-ice climate on a geophysical scale.

A risk assessment for imidacloprid applied on strawberries under different conditions was performed after residue determination using the quick, cheap, effective, rugged, and safe (QuEChERS) method. The application conditions were varied according to the applied dosage, addition of a plant oil or organosilicon surfactant, water volume, and sprayer type. The degradation dynamics of imidacloprid on strawberries followed first-order kinetics. At applied doses of 30-60 g a.i. ha-1, the half-lives of imidacloprid were 2.89-3.46, 1.98-3.65, and 2.57-2.77 days after application without a surfactant or with a plant oil or organosilicon surfactant, respectively. For water volumes of 112.5, 225, 450, 675, and 900 L ha-1, the half-lives of imidacloprid applied in the presence of the plant oil surfactant were 3.30, 7.70, 5.33, 7.70, and 6.30 days, respectively. The half-lives after application with a knapsack mist duster, electric sprayer, and manual sprayer were 2.16, 5.77, and 7.70 days, respectively. The health risk assessment revealed risk quotients less than 1 in all cases, indicating that the application of imidacloprid poses a low health risk to humans after a pre-harvest interval of 10 days under our application conditions. The risk assessment results can provide reference data for setting a reasonable maximum residue limit for imidacloprid on strawberries in China.

Although the carbendazim is widely used to manage spot blight in celery cultivation, information on residues identified is of interest. In this study, we examined the dissipation and residual amounts of carbendazim in celery and soil under different cultivation methods when using the suggested dose and ten times of that and the bioconcentration factor of carbendazim for celery. The results showed that when celery leaves were sprayed with the suggested dose, the half-lives in a celery field and greenhouse were 2.75 days and 3.29 days, respectively. When the soil matrix was sprayed with the recommended dose before cultivation, the half-lives of carbendazim residues were 16.86 days and 11.97 days. We also conducted a long-term dietary risk assessment using the corresponding criteria. The results showed that, in China, the use of carbendazim at a dose of 0.022 g/m2 is safer and more reasonable when the harvest interval is 28 days.

Titanium dioxide nanoparticles (TiO

Titanium dioxide nanoparticles (TiO2-NPs) are widely distributed in the environment. It has been demonstrated that TiO2-NPs could modify the environmental fate and bioavailability of organic pollutants, which affects ecological risks of TiO2-NPs and organic pollutants. In this study, the uptake, translocation and accumulation of perfluorooctanoic acid (PFOA) and perfluorooctanesulfonate (PFOS) in pumpkin plants was investigated in the presence of TiO2-NPs. We reported for the first time the negligible effects of TiO2-NPs at environmentally relevant concentrations (0.05–5 mg/L) on the uptake and accumulation of PFOA and PFOS in hydroponically grown pumpkin seedlings regardless of root, stem and leaf. This phenomenon was independent of the initial concentrations of PFOA/PFOS and TiO2-NPs in the exposure solution. Also, seedling mass and contents of chlorophyll and anthocyanin were not affected by the co-exposure. Adsorption tests demonstrated the negligible adsorption of PFOA/PFOS on TiO2-NPs in the exposure solution. Moreover, uptake of PFOA/PFOS was insensitive to aquaporin inhibitor AgNO3 but significantly inhibited by niflumic acid (anion channel blocker) and 2,4-dinitrophenol (metabolic inhibitor) whereas Ti concentration in root was not affected by niflumic acid and 2,4-dinitrophenol but significantly decreased by AgNO3, indicating that transport of PFOA/PFOS and TiO2-NPs were via different routes into the pumpkin seedling. It was proposed that different pathways by which TiO2-NPs and PFOA/PFOS transported into the pumpkin seedling and negligible adsorption of PFOA/PFOS on TiO2-NPs contributed to the negligible effects of TiO2-NPs on the uptake, translocation and accumulation of PFOA/PFOS in pumpkin seedlings. In total, this work would improve our understanding of the ecological risks of TiO2-NPs in the environment.

A three-dimensional dynamic model based on the peridynamics method is developed to simulate the mechanical behavior of sea ice in response to ocean waves. The ice cover is constructed with spherical particles bonded with mechanical bonds, and the fracture can be represented by the sequential failure of mechanical bonds. The thin elastic plate theory is applied to analyze the stress distribution of the ice cover. We analyze the stress distribution and crack propagation path in different cases. A good agreement among numerical model, a viscoelastic model and thin elastic plate model has been obtained on the maximum stress of the ice cover. The maximum stress of the ice cover increases with the increasing of the wave height and the decreasing of the ice thickness. Results reveal that the ratio of ice length to wavelength L i / L and the ice thickness H i have significant influence on the fracture of sea ice. The minimum wave height to break the ice floe increases with the decreasing of L i / L or the increasing of H i .

Cyazofamid, as a fungicide of the novel cyanoimidazole chemical class, has been widely used to control tomato late blight. Understanding of cyazofamid residues in environment and crops is an essential prerequisite for its risk assessment. In this study, field investigations in four typical tomato-producing areas were conducted to explore the dissipation kinetics and residues of cyazofamid and its primary metabolite 4-chloro-5-p-tolylimidazole-2-carbonitrile (CCIM) in soil and tomato. A robust method using QuEChERS coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed for simultaneous analysis of cyazofamid and CCIM, with limits of quantification of 0.33 and 3.8 μg/kg, respectively. Field trials showed that the half-lives of cyazofamid were 3.6-6.9 days in soil and 12.2-18.3 days in tomato. The total residues of cyazofamid and CCIM in tomato collected at three time intervals were all below 0.5 mg/kg. Moreover, the potential risks of total residues via tomato intake to ten population subgroups were evaluated. We found that the risk quotient values were all generally low (0.13-1.3%), indicating that the recommended dose of cyazofamid on tomato will not result in a consumer exposure exceeding the toxicological reference value. Here, the results of field investigation provided important information for further understanding the behavior and risk of cyazofamid in the natural environment.

Biochars derived from rice straw (RS), corn straw (CS), chicken manure (CM) and tire rubber (TR) were applied to soil to investigate their effects on the dissipation of cyazofamid and its metabolite CCIM (4-chloro-5-p-tolylimidazole-2-carbonitrile), with high acute toxicity compared to cyazofamid. The enhancement of cyazofamid dissipation followed the order of CS > RS > CM, whereas TR depressed the cyazofamid dissipation. Adsorption, hydrolysis and microbial degradation were all involved in cyazofamid dissipation. CM and CS enhanced the contribution of biodegradation to cyazofamid dissipation, which might be related with the shifted microbial community. More importantly, CCIM residual was drastically increased by 8–15 times after biochar application, regardless of biochar type. In total, this study shed light on the issue of build-up of metabolites in biochar-amended soil, especially for metabolites having higher toxicities than parent compounds, providing new insights into potential risk of biochar application for soil remediation.

Pesticides usually present in mixtures in surface waters, although they are traditionally regulated on an individual basis in aquatic ecosystems. In this study, we aimed to investigate the lethal and transcriptional responses of individual and combined pesticides (iprodione, pyrimethanil, pyraclostrobin and acetamiprid) on zebrafish (Danio rerio). Semi-static toxicity test indicated that the greatest toxicity to the four life stages (embryonic, larval, juvenile and adult stages) of D. rerio was detected from pyraclostrobin, followed by iprodione and pyrimethanil. In contrast, the lowest toxicity to the organisms was found from acetamiprid. Most of the selected pesticides exerted greater toxicities to D. rerio of embryonic stage compared with other life stages. Synergistic responses were observed from all binary mixtures of iprodione in combination with pyrimethanil or acetamiprid and ternary mixtures of iprodione+pyraclostrobin in combination with pyrimethanil or acetamiprid. The expressions of 16 genes related to cell apoptosis pathway, oxidative stress response, innate immunity and endocrine disruption at the mRNA level showed that zebrafish embryos were affected by the individual or combined pesticides. The expressions of P53, Tnf, TRβ, Tsh and Cyp19a exhibited greater changes upon exposure to combined pesticides compared with individual pesticides. Taken together, increased toxicity might be triggered by the simultaneous presence of several pesticides in the aquatic environment, which seriously damaged the non-target organisms.

Triadimefon (TDF) is a systemic wide-spectrum antifungal compound that is widely used in agriculture to inhibit fungal growth on various crops. Since previous studies focused on the embryo and adult life stages in the investigation of ecological impact, here we investigated the long-term effects of TDF (1, 10, 100 μg/L) on rare minnow during its larvae development. TDF caused an anti-estrogenic effect by decreasing vitellogenin (VTG) and CYP19a mRNA level, and inhibiting the aromatase activity and VTG levels after a 3, 6, 10, or 14-day exposure in rare minnow larvae. TDF also disturbed the endocrine disruption by regulating the transcription of estrogen receptors ERα, ERβ1 and ERβ2, CYP1a, CYP11, CYP17, steroidogenic acute regulator (STAR), doublesex and mab-3 related transcription factor (DMRT1), gonadotropin-releasing hormone (GnRH2), GnRH3, GnRHR1A, and GnRHR1B. Furthermore, TDF induced the accumulation of reactive oxygen species (ROS) and the activity of antioxidant proteins glutathione peroxidase (GPX), superoxide dismutase (SOD), and catalase (CAT), and significantly increased the transcriptions of stress response genes P53, growth arrest and DNA damage-inducible 45 alpha (Gadd45α), and COX1, suggested that TDF might cause oxidative stress during larvae development. The changes in transcript and biological levels represented the potential adaptive or compensatory responses to impaired oxidative stress and endocrine system after TDF exposure in rare minnow during its larvae development.

Digital intelligent recognition for the weave pattern of fabric plays an important role to improve automation and artificial intelligence in textile production process. In order to improve the data processing efficiency and minimize the negative influence such as human error in the conventional methods, a rapid, automatic and accurate method for the surface structure analysis and the fabric weave pattern recognition is proposed. First of all, an imaging system was designed to obtain the double-faced images of fabric samples, and then the captured images were treated by projection algorithm in both warp and weft directions to generate a grid net which splits the image into massive nodes. In the following step, the nodes were preliminary classified based on the intensity of the node’s quadrilateral boundary and at the same time, the color of the nodes was calculated by using the color clustering method. To improve the accuracy of node classification, the types and color information of the adjacent nodes, together with double-faced image information, were utilized for error correction. At last, the node information acquired was encoded and expressed digitally by a basic matrix, two one-dimension matrices (row and column) and a color mapping table. Following the procedure above, the digital model of the weave pattern of the sample fabric is established. Experiments have been conducted and show the performance of the proposed method.

Hydrogen cyanamide is a plant-growth regulator used on fruit crops, and has a high toxicity. In this study, a simple and sensitive method for detecting hydrogen cyanamide in fruit was developed. In the proposed method, cyanamide was extracted with water from homogenized fruit samples (grape, kiwi, and peach). The extract was purified through twice liquid–liquid extraction. Then, the purified extract was derivatized with 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate. Finally, the cyanamide derivative was analyzed using HPLC with fluorescence detection. This method was validated at 2, 0.2, and 0.01 mg kg−1 cyanamide. The recovery rates were between 87.1 and 96.6 %, and the intraday and interday reproducibilities were within 1.8 and 2.2 %, respectively. The limits of detection and quantification were 2.4 and 8 μg kg−1 cyanamide, respectively. This method was applied to explore the residue degradation of cyanamide in the field. The results show that the half-life of cyanamide residues on grapes was

The effects of different steps in canned tomato paste production on difenoconazole levels were investigated. And residues were determined by using ultra-performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS) after each stage including washing, peeling, homogenization, simmering and sterilization. Results showed that washing and peeling process reduced the amount of residue by 99%, whereas homogenization, simmering, and sterilization process had little effects on the removal of difenoconazole residue. Difenoconazole mostly remained in tomato skin, therefore, washing and peeling significantly reduced difenoconazole, especially peeling resulted in nearly 94.6% difenoconazole removal from tomatoes, with the processing factor of peeling at < 0.05.

Large amounts of imazethapyr were applied for weed control in cultivation fields in China, but their effects on the soil microbial community remains unclear. In this study, two agricultural soils, a silty loam (HS) and a loamy soil (QL), were spiked with imazethapyr (CK, 0.1, 1 and 10 mg kg −1 ) and incubated for 1, 15, 30, 60, 90 and 120 d. In addition, untreated controls received only water. The soil microbial community structures were characterized by investigating the phospholipid fatty acids (PLFA) and microbial biomass C. Soil microbial biomass C and total concentration of PLFA were variable with incubation time, which were also reduced by the addition of imazethapyr. Imazethapyr addition also decreased the ratios of GN/GP and fungi/bacteria. A larger stress level, measured as the ratio of PLFA (cyc17:0 + cyc19:0)/(16:1 ω 7c + 18:1 ω 7c), was found in the high concentration (1 and 10 mg kg −1 ) herbicide treatment groups. The effects of imazethapyr at the field application on soil microbial biomass and microbial community were minor. Principal component analysis (PCA) of the PLFA clearly separated the treatments and incubation times. Both soils showed different total PLFA concentrations and ratios of GN/GP and fungi/bacteria, but similar changes in the PLFA pattern upon soil treatment. The soil microbial community structure was shifted by the addition of imazethapyr, which recovered after 60 d. In addition, the dissipation of imazethapyr was slow in both soils. Our results demonstrated that the addition of imazethapyr shifted the microbial community structure, but that it recovered after a period of incubation.

2,4-Dichlorophenoxyacetic acid butyl ester (2,4-D butyl ester) is extensively applied for weed control in cultivation fields in China, but its effect on soil microbial community remains obscure. This study investigated the microbial response to 2,4-D butyl ester application at different concentrations (CK, 10, 100 and 1000 μg g−1) in the soils with two fertility levels, using soil dilution plate method and phospholipid fatty acid (PLFA) analysis. Culturable microorganisms were affected by the herbicide in both soils, particularly at the higher concentration. After treating soil with 100 μg g−1 herbicide, culturable bacteria and actinomycetes were significantly higher, compared to other treatments. Treatment of soil with 1000 μg g−1 2,4-D butyl ester caused a decline in culturable microbial counts, with the exception of fungal numbers, which increased over the incubation time. PLFA profiles showed that fatty acids for Gram-negative (GN) bacteria, Gram-positive (GP) bacteria, total bacteria and total fungi, as well as total PLFAs, varied with herbicide concentration for both soil samples. As herbicide concentration increased, the GN/GP ratio decreased dramatically in the two soils. The higher stress level was in the treatments with high concentrations of herbicide (1000 μg g−1) for both soils. Principal component analysis of PLFAs showed that the addition of 2,4-D butyl ester significantly shifted the microbial community structure in the two soils. These results showed that the herbicide 2,4-D butyl ester might have substantial effects on microbial population and microbial community structure in agricultural soils. In particular, the effects of 2,4-D butyl ester were greater in soil with low organic matter and fertility level than in soil with high organic matter and fertility level.

A rapid method was developed for the determination of pentachloronitrobenzene (PCNB) and its metabolites pentachloroaniline, pentachlorothioanisole residues in ginseng. Extraction and clean-up were carried out in a single step and analysis was accomplished by gas chromatography–mass spectrometry with multiple reaction monitoring. The main parameters affecting extraction yield and selectivity, such as type and amount of dispersant material, clean-up co-sorbent and extraction solvent were evaluated. The best results were obtained using 1 g ginseng, 2 g florisil as dispersant sorbent, 0.5 g neutral alumina as clean-up co-sorbent, and subsequent extraction with 10 mL acetone–n-hexane (5:5, v/v) with assisted sonication and repeated with another 5 mL of the same solvent mixture. The method was validated by analysis of ginseng samples fortified at different concentration levels (0.01–0.10 mg kg−1). Average recoveries (n = 5) ranged from 85 to 95% with relative standard deviation between 2.5 and 11.2%. Spiked blank samples were used as standards to counteract the matrix effect observed in the chromatographic determination. The detection limits ranged from 0.2 to 0.9 µg kg−1 in ginseng. The method was applied to the analysis of PCNB and its metabolite residues in commercial ginseng samples.

Glyphosate formulations that are used as a broad-spectrum systemic herbicide have been widely applied in agriculture, causing increasing concerns about residues in soils. In this study, the degradation dynamics of glyphosate in different types of citrus orchard soils in China were evaluated under field conditions. Glyphosate soluble powder and aqueous solution were applied at 3000 and 5040 g active ingredient/hm2, respectively, in citrus orchard soils, and periodically drawn soil samples were analyzed by high performance liquid chromatography. The results showed that the amount of glyphosate and its degradation product aminomethylphosphonic acid (AMPA) in soils was reduced with the increase of time after application of glyphosate formulations. Indeed, the amount of glyphosate in red soil from Hunan and Zhejiang Province, and clay soil from Guangxi Province varied from 0.13 to 0.91 µg/g at 42 days after application of aqueous solution. Furthermore, the amount of glyphosate in medium loam from Zhejiang and Guangdong Province, and brown loam from Guizhou Province varied from less than 0.10 to 0.14 µg/g, while the amount of AMPA varied from less than 0.10 to 0.99 µg/g at 42 days after application of soluble powder. Overall, these findings demonstrated that the degradation dynamics of glyphosate aqueous solution and soluble powder as well as AMPA depend on the physicochemical properties of the applied soils, in particular soil pH, which should be carefully considered in the application of glyphosate herbicide.

A method was developed for the determination of cyantraniliprole (HGW86) and its metabolite J9Z38 in watermelon and soil by ultra-performance LC (UPLC)/MS/MS. Target compounds were extracted by acetonitrile–water, cleaned up on a silica gel column, and determined by UPLC/MS/MS. Average recoveries of cyantraniliprole and J9Z38 in watermelon and soil at three levels (0.01, 0.1, and 0.5 mg/kg) ranged from 85.71 to 105.74%, with RSDs of 0.90–6.34%. The LOQs for cyantraniliprole and J9Z38 were determined to be 0.00021, 0.00015, 0.0010, and 0.00090 mg/kg in watermelon and soil samples, respectively. This method was used to determine the cyantraniliprole and J9Z38 residues in watermelon and soil samples for studies on their dissipation. The trial results showed that the half-lives of cyantraniliprole obtained after treatments were 1.1 and 4.1 days in watermelon and soil in Zhejiang, and 2.7 and 2.6 days in watermelon and soil in Hunan, respectively. The average levels of cyantraniliprole and J9Z38 residues in watermelon and soil were all

Polycyclic aromatic hydrocarbons (PAHs), which are hard to degrade, are the main pollutants in the environment. Degradation of PAHs in the environment is becoming more necessary and urgent. In the current study, strain PL1 with degradation capability of pyrene (PYR) and benzo[a]pyrene (BaP) was isolated from soil and identified as Klebsiella pneumoniae by morphological and physiological characteristics as well as 16S rDNA sequence. With the presence of 20 mg L−1 PYR and 10 mg L−1 BaP in solution, the strain PL1 could degrade 63.4 % of PYR and 55.8 % of BaP in 10 days, respectively. The order of biodegradation of strain PL1 was pH 7.0 > pH 8.0 > pH 10.0 > pH 6.0 > pH 5.0. Strain PL1 degradation ability varied in different soil. The half-life of PYR in soil was respectively 16.9, 24.9, and 88.9 days in paddy soil, red soil, and fluvo-aquic soil by PL1 degradation; however, the half-lives of BaP were respectively 9.5, 9.5, and 34.0 days in paddy soil, red soil, and fluvo-aquic soil by PL1 degradation. The results demonstrate that the degradation capability on PYR and BaP by PL1 in paddy soil was relatively good, and K. pneumoniae PL1 was the new degradation bacterium of PYR and BaP. K. pneumoniae PL1 has potential application in PAH bioremediation.