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1.
A modified QuEChERs method with liquid chromatography-tandem mass spectrometry for analysis of guadipyr residue and dissipation in rice matrices, paddy soil and paddy water was developed and validated. Mean recoveries and relative standard deviations in paddy soil, paddy water, rice plant, rice straw, rice hull and husked rice matrices at three spiking levels were 83.1–116.5% and 1.6–9.5%, respectively. The half-life of guadipyr was determined in 2 years at three different field sites in China via a dissipation experiment. The half-lives of guadipyr in paddy water were 0.22–0.37 days, 0.24–3.33 days in paddy soil and 0.44–1.90 days in rice plant. The terminal residues of guadipyr ranged from ND (concentrations of guadipyr were below limit of detection) to 50 μg kg?1 in paddy soil, 10–470 μg kg?1 in rice hull, ND70 μg kg?1 in husked rice and ND to 110 μg kg?1 in rice straw. The results would be helpful in fixing maximum residue limit of guadipyr, a new insecticide, in rice.  相似文献   

2.
Persistence and dissipation of fluopicolide and propamocarb were studied on cabbage and soil as per good agricultural practices over a period of 2 years. A modified QuEChERS analytical method in conjunction with gas chromatography (GC) and GC–mass spectrometry was used for analysis of fluopicolide and its metabolite, 2,6-dichlorobenzamide, and propamocarb in cabbage and soil. The results of the method validation were satisfactory with recoveries within 74.5–100.81% and relative standard deviations 4.8–13.9% (n = 6). The limit of detection (LOD) and limit of quantification (LOQ) of both fluopicolide and 2,6-dichlorobenzamide were 0.003 µg mL?1 and 0.01 mg kg?1, respectively. The LOD and LOQ of propamocarb were 0.03 µg mL?1 and 0.1 mg kg?1, respectively. During 2013, the initial residue deposits of fluopicolide on cabbage were 0.60 and 1.48 mg kg?1 from treatments at the standard and double doses of 100 and 200 g a.i. ha?1 which dissipated with the half-life of 3.4 and 3.7 days. During 2014, the residues were 0.49 and 1.13 mg kg?1 which dissipated with the half-life of 4.2 and 5.1 days. Propamocarb residues on cabbage were 5.36 and 12.58 mg kg?1 in the first study (2013) and 4.85 and 10.26 mg kg?1 in the second study (2014) from treatments at the standard and double doses of 1000 and 2000 g a.i. ha?1, respectively. The residues dissipated with the half-life of 4–5.5 days. The preharvest interval, the time required for fluopicolide + propamocarb residues to dissipate below the maximum residue limits (notified by EU) at the standard dose, was 11.8 and 14 days during 2013 and 2014. Residue of 2,6-dichlorobenzamide was always <LOQ in cabbage. Residues of fluopicolide, 2,6-dichlorobenzamide and propamocarb were <LOQ in field soil at harvest.  相似文献   

3.
Study on the residue dynamics of chlorpyrifos and cypermethrin in/on pomegranate (Punica granatum L.) and soil was carried out by conducting supervised field trials as per good agricultural practices. A modified QuEChERS was used to extract the insecticides in pomegranate peel and aril and soil. The limit of quantification (LOQ) of chlorpyrifos and cypermethrin were 0.01 and 0.05 mg kg?1, respectively. Residues of the insecticides remained on the fruit surface and movement to the edible part (aril) was not observed. The residues after treatment on fruit peel were 2.46 and 3.51 mg kg?1 and 2.84 and 4.54 mg kg?1 for chlorpyrifos and cypermethrin, respectively, from recommended and double dose treatments. Chlorpyrifos residues degraded faster compared to cypermethrin. The pre-harvest intervals (PHIs) of chlorpyrifos were 22 and 35 days and those of cypermethrin 50 and 73 days, respectively, at recommended and double dose treatments. In the experimental field soil after the second application chlorpyrifos residues were 0.21 and 0.46 mg kg?1 and cypermethrin residues 0.15 and 0.36 mg kg?1. At harvest, both pesticides showed residues below the LOQ. Based on this study, application of cypermethrin towards harvest may be avoided whereas chlorpyrifos can be applied with 22 days PHI.  相似文献   

4.
The combination formulation of fluopyram and tebuconazole is used for control of fungal diseases and post-harvest disease management of mango. Dissipation study of the fungicides on mango was carried out after giving applications of fluopyram +tebuconazole at the standard and double doses of 150 + 150 and 300 + 300 g active ingredient hectare?1 (g a.i. ha?1), respectively. Fluopyram residues on mango were 0.8 and 0.9 mg kg?1 and tebuconazole residues, 0.308 and 0.4 mg kg?1 after three and four applications at the standard dose. At double dose treatment the residue levels for fluopyram were 1.266 and 1.453 mg kg?1 and tebuconazole, 0.681 and 0.853 mg kg?1, respectively. Residue dissipation in mango fruits followed first order rate kinetics and the half-life (DT50) were 4.3–5.4 days for fluopyram and 3–3.8 days for tebuconazole. Faster dissipation of the fungicides was observed after the fourth treatment which directly correlated to higher rainfall during that period. The combined residues of fluopyram+tebuconazole reduced to below their maximum residue limits (MRLs) within 36–38 days. Dietary risk assessment on human health indicated that fluopyram and tebuconazole application to mango is unlikely to pose risk to human beings. This study gives valuable information on the judicious use of this combination formulation on mango, especially towards harvest.  相似文献   

5.

A method of extraction based on matrix solid-phase dispersion has been developed, optimized, and validated by chromatographic analysis of cypermethrin pesticide residues in samples of cows’ milk. Milk (0.25 g) was fortified with cypermethrin and blended with 1 g each of C18 (octadecylsilane) silica and Na2SO4 (anhydrous sodium sulfate), used to trap fats and water, respectively. The homogenized material was transferred to a commercial SPE cartridge containing 1 g activated Florisil with 5 mL acetonitrile. Cypermethrin was eluted under vacuum with 5 × 2 mL acetonitrile and the extract was concentrated to 1 mL and analyzed by gas chromatography–mass spectrometry. The limits of detection and quantification of the method were 0.025 and 0.08 mg kg−1, respectively.

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6.
Trifloxystrobin and tebuconazole are used for control of Sigatoka leaf spot disease of banana. This study was conducted to evaluate residue persistence of the fungicides in/on banana fruit, other edible parts and soil after spray application of the combination formulation, Nativo 75 WG, at the standard dose, 87.5 + 175 and double dose, 175 + 350 g a.i. ha?1. The fungicides were extracted from banana and soil with acetone, partitioned into dichloromethane and cleaned-up using activated charcoal for trifloxystrobin and primary/secondary amine (PSA) for tebuconazole samples. The limit of quantification of the method was 0.05 mg kg?1 for both fungicides. Initial residues of trifloxystrobin were 0.444 and 0.552 mg kg?1 in/on banana with peel (whole fruit), which reached <0.05 and 0.065 mg kg?1 after 30 days from treatment at the standard and double doses, respectively. Tebuconazole residues were 0.636 and 960 mg kg?1 initially and reduced to 0.066 and 0.101 mg kg?1 after 30 days. Trifloxystrobin and tebuconazole degraded with the half-life of about 11 days. Trifloxystrobin or its metabolite was not detected in the fruit pulp. Tebuconazole being systemic in nature moved to the fruit pulp which was highest on the 3rd day (0.103 and 0.147 mg kg?1) and remained for 15 days. Matured banana fruit, flower, pseudostem and field soil were free from fungicide residues. For consumption of raw banana 43 days pre-harvest interval (PHI) is required after treatment of the combination formulation. Therefore application of the fungicides towards maturity stage of the fruits may be avoided.  相似文献   

7.
The fate of kresoxim-methyl was studied in a tobacco field ecosystem, and a simple and reliable method was developed for the determination of kresoxim-methyl in soil, green and cured tobacco leaves. Kresoxim-methyl residues were extracted from samples with petroleum ether, and determined by gas chromatography (GC) coupled with an electron capture detector (ECD). Kresoxim-methyl (30% suspension concentration) was applied at 150 g a.i. ha–1 (the recommended high dosage) and 225 g a.i. ha–1 (1.5 times the recommended high dosage) in the experimental fields in Huishui and Changsha in China. The limits of detection (LODs) and limits of quantification (LOQs) of kresoxim-methyl in green tobacco leaves, cured tobacco leaves and soil were 0.012 and 0.04 mg kg–1, 0.12 and 0.4 mg kg–1, and 0.0015 and 0.005 mg kg–1, respectively. The average recoveries were 84.5% to 95.7%, 79.8% to 94.3% and 83.3% to 93.8% with relative standard deviations (RSDs) less than 10% in green tobacco leaves at four spiked levels (0.04, 0.2, 2 and 8 mg kg–1), cured tobacco leaves at three spiked levels (0.4, 1 and 10 mg kg–1) and soil at three spiked levels (0.005, 0.05 and 0.5 mg kg–1), respectively. The results showed that the half-lives of kresoxim-methyl in green tobacco leaves and soil were 1.2–5.3 days and 6.7–10.4 days, respectively. At harvest, kresoxim-methyl residues in cured tobacco leaves samples collected 21 days after the last application at the recommended dosage were below 1.0 mg kg–1. These results could help establish appropriate application frequency and harvest intervals in the use of kresoxim-methyl on tobacco plants.  相似文献   

8.
An effective method based on LC–MS/MS was established to determine the concentrations of flupyradifurone, difluoroacetic acid, and 6-chloronicotinic acid in pepper. On the basis of this method, the dissipation, processing factor, and dietary risk of flupyradifurone in pepper were investigated. The results show that the half-life of flupyradifurone in peppers was 2.6–3.8 days. The terminal residual concentration of flupyradifurone in the supervised trials was not higher than the maximum residue limit (MRL) for pepper in the Codex Alimentarius Commission (CAC) (0.9 mg kg−1) with the highest residual values of 0.53 mg kg−1. The national estimated daily intake of flupyradifurone was 0.00094 mg kg−1, based on the dietary structure of Chinese consumers and the terminal residues under field conditions. The risk quotient for flupyradifurone was 0.012, which was significantly < 1. The processing factor of flupyradifurone in dried pepper was 10.9–14.2, which indicated that drying increased the residual amounts of flupyradifurone in dried pepper, but the residual concentration was still lower than its MRL of 9 mg kg−1 established by CAC.  相似文献   

9.
Cai  Xiao-Ming  Zhao  Hua  Wu  Min  Hu  Xiu-Qing  He  Hong-Mei  Zhang  Chang-Peng  Zhang  Chun-Rong  Li  Zhen 《Chromatographia》2012,75(17):1069-1074

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 <2.0 days. Compared with the previous methods, this simple method is sensitive and can be applied for detecting cyanamide in a wide range of fruits.

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10.
Herein we report a novel, accurate and cost-effective gas chromatography method for the determination of average deposits of profenofos on green pea and cucumber following good agricultural practices. Additionally the risk assessment, dissipation and waiting period for profenofos were determined. The average initial deposits (2 h after spraying) of profenofos in/on green pea and cucumber were 3.41 and 3.62 mg kg−1 respectively following two applications at a 10 day interval of profenofos 50EC formulation. Profenofos residues on both of the substrates were below the detection limit of 0.05 mg kg−1 after 20 days at the recommended dosage. For risk assessment studies, the 20th day will be safe for consumers for consumption of green peas. The gas chromatography method was validated according to the SANTE guidelines using the various analytical parameters: linearity, accuracy, detection and quantification limits. The developed method is simple, selective and repeatable and can be extended for profenofos-based standardization of pesticide formulations for green pea/cucumber and their use as pesticides.  相似文献   

11.
A study of the biodegradation of imidacloprid in soil was carried out under laboratory conditions. Sandy soil samples were fortified with imidacloprid at 50, 100 and 150 mg kg?1 along with 45 x 107 colony forming units (cfus) of Bacillus aerophilus and the samples were compared with unamended soil. The samples were extracted with acetonitrile, cleaned up by treatment with primary secondary amine sorbent and graphitised carbon black. The residues of imidacloprid and its metabolites were analysed by high performance liquid chromatography. The parent compound, imidacloprid, was found to be more persistent in both the treatments. Among metabolites, the highest values were obtained for urea and olefin while 5-hydroxy, 6-chloronicotinic acid (6-CNA), nitrosimine and nitroguanidine (NTG) were also observed in all the treatments in amended soil. In case of unamended (control) soil, 6-CNA was found to be the most persistent metabolite followed by olefin, urea, 5-hydroxy, nitrosimine and NTG metabolites. Total imidacloprid residues for control soil samples followed first-order kinetics at 50 and 150 mg kg?1 but in case of control imidacloprid fortified at 100 mg kg?1, the total residues of imidacloprid and its metabolites followed pseudo-first-order kinetics. The respective half-life value for 50 mg kg?1 was 25.08 days and 30.10 days for both 100 and 150 mg kg?1. However, total imidacloprid residues followed pseudo-first-order kinetics for its applications at 50, 100 and 150 mg kg?1 in sandy loam soil amended with B. aerophilus. The half-life values for 50, 100 and 150 mg kg?1 were worked out to be 14.33, 15.05 and 18.81 days, respectively. With the use of B. aerophilus, the reduction percentage of initial applied dose imidacloprid in sandy loam soil was found to be higher in all the three doses as compared to that of the control samples.  相似文献   

12.
To evaluate the residual levels of bifenthrin and dinotefuran, a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) and high-performance liquid chromatography–tandem mass spectrometry method for simultaneous detection of bifenthrin and dinotefuran and its major metabolites in wheat was developed and validated. Dietary risk assessments were further performed based on the relevant residual data from 12 wheat fields, toxicology data and dietary patterns. In wheat grain and straw, the recoveries of all analytes ranged from 77 to 102% with the relative standard deviation <9.7% and the limit of quantitation 0.05 mg kg−1. The highest terminal residue of bifenthrin in wheat grain was 0.069 mg kg−1 and dinotefuran was 0.34 mg kg−1. Residual concentrations of bifenthrin and dinotefuran decreased to <0.05 and 0.15 mg kg−1 at 21 days (pre-harvest interval), respectively. The chronic risk quotient ranged from 6.4 to 62.7% and the acute risk quotient varied from 0.38 to 17.73%. The chronic and acute dietary risks caused by the terminal residues of the two insecticides were negligible for Chinese populations. The recommended pre-harvest interval was proposed to ensure safe wheat consumption. These data could provide a scientific reference to establish the Chinese maximum residue limit of dinotefuran in wheat.  相似文献   

13.
Residue dissipation of hexaconazole and isoprothiolane in the rice field ecosystem was determined by gas chromatography coupled with electron capture detector. Hexaconazole and isoprothiolane (33% microemulsion) were applied at two dosages, 396 g a.i. ha–1 (the recommended dosage) and 594 g a.i. ha–1 (1.5 times the recommended dosage) in the experimental fields in Guizhou, Hunan and Heilongjiang provinces, China, during 2011–2012. The limits of detection and limits of quantification in brown rice were 0.006 and 0.02 mg kg–1 for hexaconazole, 0.0072 and 0.024 mg kg–1 for isoprothiolane, respectively, and they were much below the maximum residue limits (MRLs, 0.1 mg kg–1 for hexaconazole and 1.0 mg kg–1 for isoprothiolane) set by China. Average recoveries of hexaconazole in water, soil, rice plants and brown rice ranged from 77.3% to 93.8% and for isoprothiolane ranged from 78.1% to 99.9% with relative standard deviations < 10%. The results showed that during harvest, the terminal residue levels of hexaconazole and isoprothiolane in brown rice samples were well below the MRLs of China following the interval of 7 days after last application. Therefore, a dosage of 396 g a.i. ha–1 was recommended, which could be considered as safe to human beings.  相似文献   

14.

Dimilin 45 ODC (diflubenzuron) was applied in a Mediterranean-climate conifer forest, near Vitoria, Basque Country, Spain. Pine needles were collected at post-treatment 5-day intervals for analysis of the diflubenzuron residues. A liquid chromatography method with on-line diode-array and electrochemical detection was developed for the determination of the pesticide diflubenzuron and its main metabolites: 2,6-diflurobenzamide, 4-chlorophenylurea, 4-chloroacetanilide, 4-chloroaniline and N-methyl-4-chloroaniline in forestry matrices. Aerial application at 56.3 g AI ha?1 resulted in deposition levels of the insecticide of 1080 ng g?1. Within 40-65 days following treatment, 51-73% of the insecticide had been removed from the foliage. During this period, the concentration of diflubenzuron was higher than 295 ng g?1. The only metabolite detected was 2,6-difluorobenzamide and this persisted on foliage until the first rainfalls occurred. An empirical mathematical correlation was found to express the influence of rainfall, solar radiation and temperature on the persistence of the insecticide.  相似文献   

15.
A multiresidue analytical method based on acetone extraction and clean-up/pre-concentration on polymeric sorbents was validated for 42 pesticides in peach matrix in order to control safety of fresh production on the Bulgarian market. Matrix-matched calibration was used by addition of pesticides just before SPE. In this way the standards and the samples undergo exactly the same procedure and an improvement of recoveries for the target analytes was observed. The identification and quantification were done by gas chromatographic technique with mass-spectrometric detection (GC-MS). The limits of detection obtained were 0.005?mg?kg–1 or lower for the most of analytes, and the recovery data were in range 73–109% at three spiked levels 0.01, 0.1 and 0.2?mg?kg?1. The validated method was used for monitoring of selected pesticides in fresh peach fruits home production. Approximately 30% of the analysed lots (total 33 samples) contained residues mainly of cypermethrin and procymidone, but did not exceed EU MRLs.  相似文献   

16.
A sensitive matrix solid-phase dispersion (MSPD)/gas chromatography-electron capture detector (GC-ECD) method was developed to determine cypermethrin residues in three tissues (muscle, liver, and gill) of crucian carp. Cypermethrin was simultaneously extracted by MSPD and determined by GC-ECD. The main parameters affecting extraction yield and selectivity, such as the type of solid adsorbent material, choice of elution solvents and their volume, were investigated to obtain interference-free extracts and quantitative cypermethrin recovery. Fortified recoveries in muscle, liver, and gill samples ranged from 84.9% to 106.1%, and relative standard deviations were <8% with fortification levels of 0.05–1 mg kg?1. Detection limits were 1.4–2.1 μg kg?1, and quantitation limits were 5.8–7.8 μg kg?1. The proposed method was successfully applied to determination of cypermethrin in fish tissue samples.  相似文献   

17.
In this study, an efficient screening method based on a modified quick, easy, cheap, effective, rugged, and safe extraction method combined with ultra-high-performance liquid chromatography coupled to tandem quadrupole time-of-flight mass spectrometry was established for the determination of 90 pesticides residues in Panax Ginseng. The accuracy of the method was then verified by analyzing the false positive rate and the screening detection limit in Ginseng. The results revealed that the screening detection limit of 33 of 90 pesticide residues were 0.01 mg·kg−1, 22 species were 0.05 mg·kg−1, 11 species were 0.10 mg·kg−1, 8 species were 0.20 mg·kg−1, and another 16 species were greater than 0.20 mg·kg−1. A total of 73 pesticides were ultimately suitable to be practically applied for rapid analysis of pesticide residues in Ginseng. Finally, the established method was used to analyze the pesticide residues in 35 Ginseng samples available on the market. And the residual of dimethomorph, azoxystrobin, tebuconazole, and pyraclostrobin was relatively severe in Ginseng samples. This work expanded the range of pesticides detected and provided a rapid, effective method for pesticides screening in Ginseng.  相似文献   

18.
A new method was developed for simultaneous determination of cypermethrin and permethrin residues in pear juice with ultrasound-assisted dispersive liquid-liquid microextraction (UA-DLLME) and gas chromatography-flame ionization detection (GC-FID). 3.5 mL of methanol (dispersant) and 30 μL of C2Cl4 (extractant) were injected into 5.0 mL of pear juice sample and then emulsified by ultrasound for 2.0 min to forming the cloudy solution. Under the optimum condition, the enrichment factors for cypermethrin and permethrin were 344 and 351 fold respectively. Good linearity was observed in a range of 0.009-1.52 μg g−1 with the correlation coefficient (r2)≥0.9993. The limits of detection (LODs) were 3.1 and 2.2 μg kg−1 for cypermethrin and permethrin, respectively (S/N = 3). The recoveries of the method evaluated at three spiked levels were in the range of 92.1%-107.1%. The repeatability evaluated as intra-day and inter-day precision (RSDs) were less than 4.0% (n = 5). The developed method was successfully applied to determine the two pesticide residues in different pear juice samples.  相似文献   

19.
A simple and mild method for the separation of sulfonamide residues based on a condensation reaction with O-phthalaldehyde solution (OPA) as labeling reagent with capillary electrophoresis has been developed. A 58.5 cm × 50 μm i.d. (50 cm effective length) untreated fused-silica capillary was used. To optimize the separation conditions, the background electrolyte concentration, pH, column temperature, voltage and other factors were evaluated. The optimal separation conditions were as follows: 20 mmol L?1 borate buffer; pH 9.1; column temperature 20 °C; separation voltage 18 kV, pressure 50 mbar and injection time 8 s. Under the optimal conditions, 10 kinds of sulfonamide derivatives could be well-separated within 8 min, and the linear ranges were 0.35–100 μg kg?1. The detection limit (at a signal-to-noise ratio of 3) was in the range of 0.12–0.25 μg kg?1, and the quantification limit (at a signal-to-noise ratio of 10) was in the range of 0.35–0.70 μg kg?1. The sulfonamide residues from cultured sea cucumber samples were determined under the optimal conditions with satisfactory results.  相似文献   

20.
Residue analysis of fosthiazate in cucumber and soil by QuEChERS and GC-MS   总被引:2,自引:0,他引:2  
Min Wu  Jiye Hu 《Chemical Papers》2014,68(10):1368-1374
A convenient method was developed for the determination and validation of fosthiazate in cucumber and soil. The procedure is based on liquid partitioning with acetonitrile followed by dispersive solid phase extraction as the clean-up step, after which samples were analysed by gas chromatography-mass spectrometry (GC-MS). The average recoveries ranged from 91.2 % to 99.0 % with relative standard deviations (RSDs) of less than 6.05 %, at three fortification levels (0.02 mg kg?1, 0.1 mg kg?1, 0.5 mg kg?1) in cucumber and soil, and the limits of quantification (LOQs) for fosthiazate were all established at 0.02 mg kg?1. The proposed method was applied successfully to analyses of the dissipation and residue of fosthiazate in field trials. The dissipation rate of fosthiazate was described using pseudo-first-order kinetics with a half-life of 4.33 days and 4.08 days in soil in Beijing and Shandong, respectively. In the terminal residue experiment, fosthiazate residues in cucumber and soil were clearly below the maximum residue level (MRL, 0.2 mg kg?1) set in China.  相似文献   

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