Determination and study on dissipation and residue of bismerthiazol and its metabolite in Chinese cabbage and soil

A simple and accurate method for the determination of bismerthiazol and its metabolite 2-amino-5-mercapto-1,3,4-thiadiazole was developed in Chinese cabbage and soil by high-performance liquid chromatography-diode array detection in this study. The limits of detection were 0.06 mg/kg for bismerthiazol and 0.03 mg/kg for 2-amino-5-mercapto-1,3,4-thiadiazole, respectively. Recoveries of cabbage and soil were investigated at three spiking levels and were in the range of 84.0–96.0 % for bismerthiazol and 71.0–74.6 % for 2-amino-5-mercapto-1,3,4-thiadiazole, with relative standard deviations below 7.0 %. For field experiments, the half-life of bismerthiazol was 2.4–2.5 days in Chinese cabbage and 2.5–4.8 days in soil at the two experimental locations in China. Dissipation residues of 2-amino-5-mercapto-1,3,4-thiadiazole were lower than 0.72 mg/kg. Terminal residues of bismerthiazol and its metabolite were less than 3.0 and 0.3 mg/kg in Chinese cabbage, respectively. No bismerthiazol or metabolite residues were detected in soil on days 5, 7, 10, and 14 after the last spraying at the two dosage levels.     

Dissipation of flubendiamide residues in/on cabbage (Brassica oleracea L.)

Residues of fubendiamide and its metabolite desiodo flubendiamide were estimated in cabbage and soil using high-performance liquid chromatography with UV–vis detector. The initial deposits of flubendiamide residues on cabbage were found to be 0.16 and 0.31 μg g^?1 following two applications of flubendiamide 20 WG at 12.5 (standard dose) and 25 (double dose) g a.i. ha^?1 respectively at 10-days interval. The half-life values (t _1/2) of flubendiamide on cabbage ranged from 3.4 to 3.6 days. When flubendiamide applied at both the standard and double dose, no detectable residues were found in cabbage and soil at harvest. Thus, a waiting period of 1.63 days was suggested for the safe consumption of flubendiamide-treated cabbage. These data could provide guidance for the proper and safe use of this pesticide on cabbage crops in India.     

Dissipation studies of fentrazamide (YRC-2388) in soil under anaerobic condition

Dissipation of fentrazamide in soil and water under flooded (anaerobic) conditions was studied. Fentrazamide was applied to soil at 100 g ha(-1). Soil was extracted with 0.1 N HCl?:?acetone (1?:?1 v/v) followed by partition and cleanup with silica SPE. Separation was achieved in an ODS-II column with a mobile phase of acetonitrile?:?water (70?:?30 v/v) and detection at 214 nm. Recovery of fentrazamide varied from 75.2-90.4% and 89.9-97.8% in soil and water, respectively. Fentrazamide dissipated rapidly and fentrazamide residues were not detected after 100 and 35 days of application in soil and water, respectively. Half life in soil and water was 9.06 and 3.66 days, respectively. Dissipation followed monophasic first order kinetics pattern. No fentrazamide was detected in soil, rice grain and rice straw at harvest of crop. Calibration curves for quantification were linear and relative standard deviation (RSD) was 1.78%. LOD for instrument was 0.002 μg mL(-1) and LOQ for methods were 0.005 μg g(-1) for soil and water.     

Persistence of metaflumizone on cabbage (Brassica oleracea Linne) and soil, and its risk assessment

Metaflumizone is a novel sodium channel blocker insecticide of semicarbazone class. It provides good to excellent control of most of the economically important lepidopterous pests and certain pests in the orders Coleoptera, Hemiptera, Hymenoptera, Diptera, Isoptera, and Siphonaptera. Although metaflumizone has been marketed globally for several years and got registered in India in the year 2009, specifically for the control of DBM on cabbage, to our knowledge, no food safety aspects of metaflumizone residue on cabbage have ever been reported in the literature in India or elsewhere. The present study was undertaken to evaluate the persistence of metaflumizone on cabbage and soil, vis-a-vis its risk assessment, following two spray applications of metaflumizone 220 SC (Verismo®), each at recommended and double dose of 200 and 400 g?a.i.?ha^?1 respectively. Initial residue deposits of metaflumizone on cabbage were 0.46 and 0.51 mg?kg^?1 at recommended and 0.76 and 0.85 mg?kg^?1 at double the recommended dose following the first spray and second spray application. The residues persisted beyond 5 days from both the treatments and dissipated with the half-life ranging from 1.7–2.1 days. Initial deposits of metaflumizone on soil ranged from 0.23–0.37 mg?kg^?1 and degraded with a half life ranging from 4.0–4.8 days. No degradation product of metaflumizone was detected in cabbage and soil at any point of time. Soil samples collected from the treated field after 7 days were free from any residue of metaflumizone or its metabolites. A pre-harvest waiting period of 3 days after application was suggested based on calculation of theoretical maximum daily intake.     

Analysis of cyprodinil in leek and pepper and its decline under field conditions

A HPLC-UV method for determination of cyprodinil in leek, pepper, and soil was developed and the decline of cyprodinil under field conditions in China was investigated. The samples were extracted with acetonitrile. For leek and pepper samples, further clean-up with a florisil SPE column was necessary. Average recoveries of cyprodinil were found in the range of 82.92-107.43% with relative standard deviations of 2.48-14.55%. The pesticide cyprodinil showed a relatively fast decline rate. The half lives were from 2 to 4 days in leek and pepper, from 2-5 days in soil except in Beijing (14.7 days). So the decline of cyprodinil in leek and pepper was almost same in different experiment plots. However, the decline in soil was much complicated, and affected by the precipitation and other climate condition. The results could provide guidance to safe and reasonable use of this pesticide in agriculture.     

Persistence behaviour of imidacloprid and its metabolites in soil under sugarcane

The persistence and metabolism of imidacloprid in soil under sugarcane were studied following application of imidacloprid at 20 and 80 g active ingredient (a.i.) ha^?1. Soil samples were collected at different time intervals (7, 15, 30, 45, 60 and 90 days after application), and the residues of imidacloprid and its metabolites (6-chloronicotinic acid, nitrosimine, imidacloprid-NTG, olefin, urea and 5-hydroxy) were quantified by high-performance liquid chromatography. In soil, the total imidacloprid residues were mainly constituted by the parent compound followed by 6-chloronicotinic acid, nitrosimine and imidacloprid-NTG metabolites. Maximum residues of imidacloprid and its metabolites were 4.29 and 7.81 mg kg^?1 in soil samples collected 7 days after the application of imidacloprid at 20 and 80 g a.i. ha^?1, respectively. At both doses, these residues declined to below the detectable limit in soil after 90 days of application. Olefin, urea and 5-hydroxy metabolites were not detected in soil. Dissipation of total imidacloprid residues did not follow the first-order kinetics with a coefficient of determination value of 0.883 and 0.838 for the recommended dose and four times the recommended dose, respectively. The half-life (T _1/2) value of total imidacloprid was observed to be 10.64 and 10.10 days for the recommended dose and four times the recommended dose, respectively.     

Evaluation of environmental fate of acetamiprid in the laboratory

The acetamiprid, a nenicotinoid insecticide, is a popular crop protection agent used in fields as well as in protected cultivation. A laboratory experiment was conditions to study the effect of light, moisture, and pH on the persistence of acetamiprid in water and soil. Dissipation half-lives of acetamiprid in water at pH 4, 7, and 9 were 6.2, 7.3, and 5.1 days, respectively, and 4.3 days under UV and sunlight conditions. Half-life in soil at three concentrations, 0.1, 1.0, and 10 μg g^?1 under different moisture regimes varied from 21.5–22.8, 15.6–22.4, 10.0–15.8 days, respectively, indicating that acetamiprid dissipated faster in submerged soil as compared to field capacity moisture and dry conditions. The leaching study showed that the possibility for leaching of acetamiprid to ground water is extremely low under normal condition of average rainfall due to compact nature soil in the field. Acetamiprid poses low risks to the ecosystem because of their rapid dissipation and low-bound residues in the environment.     

Persistence and Dissipation of Readymix Formulations of Insecticides In/On Okra Fruits

Dissipation behaviour of ready mix polytrin C 44EC (profenophos 40% + cypermethrin 4%) and spark 36EC (triazophos 35%+.deltamethrin 1%) applied at 1 L/ha in okra crop during Kharif in year 2000 was studied at 0, 1, 3, 5 and 7 days after treatment. Dissipation on 7th day was found to be maximum (98.4%) for profenophos followed by triazophos (86.2%), cypermethrin (73.5%) and deltamethrin (55.7%). Half life (t1/2) values for the above insecticides were 1.35, 2.55, 4.11 and 7.60 days, respectively. All the insecticides followed a first order kinetics. Profenophos and triazophos followed a biphasic dissipation pattern with faster dissipation in phase I (0–1 days) and manifesting slower rate of dissipation in phase II (1–7 days).     

Safety evaluation of flubendiamide and its metabolites on cabbage and persistence in soil in different agroclimatic zones of India

Supervised field trials following good agricultural practices were conducted at the research farms of four agricultural universities located at four different agroclimatic zones of India to evaluate the persistence and dissipation of flubendiamide and its metabolite, des-iodo flubendiamide, on cabbage. Two spray applications of flubendiamide 480 SC of standard and double dose at the rate of 24 and 48 g a.i. ha^?1 were given to the crop at a 15-day interval, and the residues of flubendiamide 2 h after spray were found in the range of 0.107–0.33 and 0.20–0.49 mg kg^?1 at respective doses. Residue of des-iodo flubendiamide was not detected in any cabbage sample during study period. No residues were found in the soil samples collected from all treated fields after 15 days of application. On the basis of data generated under All India Network Project on Pesticide Residues, a preharvest interval (PHI) of 10 days has been recommended, and the flubendiamide 480 SC has been registered for its use on cabbage by Central Insecticide Board and Registration Committee, Ministry of Agriculture, Government of India. The maximum residue limit (MRL) of flubendiamide on cabbage has been fixed by the Ministry of Health and Family Welfare, Government of India, under Food Safety Standard Authority of India as 0.05 μg/g after its risk assessment.     

GC–ECD analysis of S-metolachlor (Dual Gold) in cotton plant and soil in trial field

The analytical method of S-metolachlor residue and its degradation in cotton and soil in trial field were investigated. S-metolachlor EC (96% w/w) was applied as pre-emergence at dosages of 1,500 and 2,250 ml ha(-1) 3 days after sowing of the cottonseeds in the field. The soil and the plant samples were collected at different intervals and the residues of S-metolachlor were analyzed by GC-ECD. The results showed that the degradation of S-metolachlor in cotton leaves in Beijing and Nanjing coincides with C = 0.1113e(-0.1050t) and C = 0.1177e(-0.1580t), respectively; the half-lives were about 6.6 and 4.4 days. The degradation of S-metolachlor in soil in Beijing and Nanjing coincides with C = 1.0621e(-0.0475) (t), and C = 0.9212e(-0.0548) (t), respectively; the half-lives were about 14.6 and 12.6 days,. At harvest time, the S-metolachlor in cotton seeds and soil samples were detected by GC-ECD and confirmed by GC/MS. The results showed that the residues in cottonseeds were lower than the USA EPA's maximum residue limit of 0.1 mg kg(-1) in cottonseed. It could be considered as safe to human beings and environment.     

Persistence of fipronil and its metabolites in soil under field conditions

Fipronil belongs to phenylpyrazole class of chemical compounds. Degradation of fipronil in sandy loam soil was investigated under field conditions by applying fipronil (Regent 5 % SC) at 50 (T ₁) and 100 g a.i. ha^?1 (T ₂) in field. Samples were drawn periodically in triplicate on 0 (1 h after treatment), 1, 3, 7, 10, 15, 30, 60, and 90 days after treatment and analyzed on GC-ECD system equipped with capillary column. The residues of fipronil in both the doses dissipated in the range of 93.33–100 % in 90 days. Limit of detection (LOD) and limit of determination (LODe/LOQ) were 0.0003 and 0.001 mg kg^?1, respectively. Dissipation followed a biphasic first-order kinetics with half-life values of 10.81 and 9.97 days for fipronil alone and 8.14 and 13.05 days for fipronil along with metabolites in soil at (T ₁) and (T ₂) treatments, respectively.     

Dissipation behavior and risk assessment of butralin in soybean and soil under field conditions

Dissipation behavior, final residue, and risk assessment of butralin in soybean, green soybean, plant, and soil were investigated. Butralin residues were extracted with acetonitrile and then soybean samples were detected with gas chromatography-mass spectrometer (GC-MS) and soil samples were determined with GC with nitrogen phosphorous detector (GC-NPD). The limit of quantification (LOQ) of the method was 0.01 mg/kg for soybean, green soybean, plant, and soil. Average recoveries ranged from 90.4 ~ 98.2% for green soybean, 86.2 ~ 86.6% for soybean, 86.0 ~ 98.8% for plant, and 85.0 ~ 106.8% for soil. The relative standard deviations (RSDs) were 2.0 ~ 7.2% for green soybean, 2.0 ~ 3.0% for soybean, 3.1 ~ 8.1% for plant, and 1.8 ~ 6.6% for soil. Half-lives of butralin in soil samples varied in the range of 11–22 days. At harvest time, final residues of butralin in soybean and green soybean were lower than LOQ. Risk assessment demonstrated that, at recommended dosage and frequency, butralin would not induce significant harm on humans. The study could be used as a quantitative basis for application of butralin on soybean.     

Nitrogen enrichment in runoff sediments as affected by soil texture in Beijing mountain area

Enrichment ratio (ER) is widely used in nonpoint source pollution models to estimate the nutrient loss associated with soil erosion. The objective of this study was to determine the ER of total nitrogen (ER_N) in the sediments eroded from the typical soils with varying soil textures in Beijing mountain area. Each of the four soils was packed into a 40 by 30 by 15 cm soil pan and received 40-min simulated rainfalls at the intensity of 90 mm h^?1 on five slopes. ER_N for most sediments were above unity, indicating the common occurrence of nitrogen enrichment accompanied with soil erosion in Beijing mountain area. Soil texture was not the only factor that influenced N enrichment in this experiment since the ER_N for the two fine-textured soils were not always lower. Soil properties such as soil structure might exert a more important influence in some circumstances. The selective erosion of clay particles was the main reason for N enrichment, as implied by the significant positive correlation between the ER of total nitrogen and clay fraction in eroded sediments. Significant regression equations between ER_N and sediment yield were obtained for two pairs of soils, which were artificially categorized by soil texture. The one for fine-textured soils had greater intercept and more negative slope. Thus, the initially higher ER_N would be lower than that for the other two soils with coarser texture once the sediment yield exceeded 629 kg ha^?1.     

Determination and study on dissipation and residue determination of cyhalofop-butyl and its metabolite using HPLC-MS/MS in a rice ecosystem

Cyhalofop-butyl is an aryloxyphenoxypropionate postemergence herbicide with good control of barnyard grass in rice paddies. In this study, method for the determination of cyhalofop-butyl and its metabolite was developed with high-performance liquid chromatography tandem mass spectrometry. Dissipation and residue levels of cyhalofop-butyl and its metabolite in rice ecosystems were also investigated. Recoveries and relative standard deviations of cyhalofop-butyl and cyhalofop acid in six matrices at three spiking levels ranged from 76.1 to 107.5 % and 1.1 to 8.2 %, respectively. The limit of quantitation (LOQ) of cyhalofop-butyl and cyhalofop acid was 0.01 mg/kg in paddy water, paddy soil, rice plant, rice straw, rice hulls, and husked rice. For field experiments, the results showed that cyhalofop-butyl degraded to cyhalofop acid quickly, and the half-lives of cyhalofop acid in paddy water, paddy soil, and rice plant were 1.01–1.53, 0.88–0.97, and 2.09–2.42 days, respectively. Ultimate residues of cyhalofop-butyl and its metabolite in the rice samples were not detectable or below 0.01 mg/kg at harvest.     

Dissipation and residue of MCPA (4-chloro-2-ethylphenoxyacetate) in wheat and soil

A rapid and simple HPLC method has been developed for the quantitation of 4-chloro-2-methylphenoxyacetic acid (MCPA) in both wheat and soil samples. Samples were extracted in acidic media and cleaned up by solid-phase extraction with C(18) cartridges before HPLC-DAD detection. The limits of detection and quantification of MCPA were 0.02 ng and 0.01 mg/kg for both wheat and soil. The mean recoveries ranged from 87.1% to 98.2%, and the RSDs ranged from 0.604% to 3.44% for the three spiked levels (0.01, 0.1, 0.5 mg/kg). The proposed method was successfully applied to the analysis of MCPA residues in wheat and soil samples from an experimental field. The dissipation half-lives in soil were calculated to be 3.22 days (Beijing) and 3.10 days (Tianjin), respectively. Direct confirmation of the analytes in real samples was achieved by gas chromatography-mass spectrometry. The results indicated that at harvest time, the residues of MCPA in wheat were well below the maximum residue levels and were safe to apply in wheat.     

Dissipation dynamic and residue distribution of flusilazole in mandarin

In this paper, dissipation dynamic and terminal residue of flusilazole in mandarin and soil, as well as residue distribution of flusilazole in mandarin, were studied at three sites in China. Mandarin peel, mandarin pulp, whole mandarin, and soil samples were extracted by acetonitrile, cleaned up with dispersive solid-phase extraction, then analyzed by gas chromatography–mass spectrometry. The dissipation half-lives of flusilazole in mandarin and soil at all three experiment sites were 6.3–8.4 days and 5.5–13.4 days, respectively, with the exception of the soil dissipation at the Hunan site, which showed an increase–decrease process. Flusilazole residue levels in whole mandarin were all below 0.1 mg/kg on 14 days after the last application. Terminal residue study showed that flusilazole was mostly distributed in mandarin peel, which indicates minimal risk for eating mandarin pulp. These results could provide guidance for the proper and safe use of flusilazole on citrus fruits, and further our understanding of pesticide distribution in citrus fruits.     

Dynamics and origin of PM2.5 during a three-year sampling period in Beijing, China

Systematic sampling and analysis were performed to investigate the dynamics and the origin of suspended particulate matter smaller than 2.5 μm in diameter (PM(2.5)), in Beijing, China from 2005 to 2008. Identifying the source of PM(2.5) was the main goal of this project, which was funded by the German Research Foundation (DFG). The concentrations of 19 elements, black carbon (BC) and the total mass in 158 weekly PM(2.5) samples were measured. The statistical evaluation of the data from factor analysis (FA) identifies four main sources responsible for PM(2.5) in Beijing: (1) a combination of long-range transport geogenic soil particles, geogenic-like particles from construction sites and the anthropogenic emissions from steel factories; (2) road traffic, industry emissions and domestic heating; (3) local re-suspended soil particles; (4) re-suspended particles from refuse disposal/landfills and uncontrolled dumped waste. Special attention has been paid to seven high concentration "episodes", which were further analyzed by FA, enrichment factor analysis (EF), elemental signatures and backward-trajectory analysis. These results suggest that long-range transport soil particles contribute much to the high concentration of PM(2.5) during dust days. This is supported by mineral analysis which showed a clear imprint of component in PM(2.5). Furthermore, the ratios of Mg/Al have been proved to be a good signature to trace back different source areas. The Pb/Ti ratio allows the distinction between periods of predominant anthropogenic and geogenic sources during high concentration episodes. Backward-trajectory analysis clearly shows the origins of these episodes, which partly corroborate the FA and EF results. This study is only a small contribution to the understanding of the meteorological and source driven dynamics of PM(2.5) concentrations.     

Dissipation of Endosulfan and Dichlorvos Residues In/On Cauliflower Curds

Dissipation behaviour of endosulfan and dichlorvos in/on cauliflower, variety Snowball-16, was studied during rabi season (Sep.–March) 2003–2004. Endosulfan and dichlorvos were sprayed @ 350 and 110g a.i. with 115 g a.i., respectively, 80 days after transplanting. Samples were taken at the interval of 0 (1h after spray), 3, 5, 7, and 10 days after spray (DAS) in triplicate and residues were estimated on GC-ECD system equipped with capillary column. The initial deposits of 3.452 and 0.295μgg⁻¹ of endosulfan and dichlorvos dissipated to 0.084 (97.56%) and 0.009 (96.95%), respectively after 10 DAS. Residues of endosulfan reached below maximum residue limit of 2μgg⁻¹ one day after spray and of dichlorvos were below MRL value of 0.5μgg⁻¹ even on 0 day. Dissipation pattern followed first order kinetics for both the insecticides with half life periods of 1.81 and 2.08 days for endosulfan and dichlorvos, respectively.     

Simultaneous determination of insecticide fipronil and its metabolites in maize and soil by gas chromatography with electron capture detection

An integrated method for the simultaneous determination of insecticide fipronil and its three metabolites, desulfinyl, sulfide, and sulfone, in maize grain, maize stem, and soil was developed. This three-step method uses liquid–solid extraction with ultrasound or mechanical grinding, followed by liquid–liquid partitioning and florisil solid-phase extraction (SPE) for cleanup. The quantification was conducted by gas chromatography–electron capture detection in triplicate for each sample. The method was validated with five replicates at three fortification concentrations, 0.002, 0.01, and 0.1 mg kg^?1, in each matrix and gave mean recoveries from 83 to 106 % with relative standard deviation ≤8.9 %. The limits of quantification (LOQ) were 0.002 mg kg^?1 for the compounds in all matrixes. In the field study in Beijing and Shandong 2012, fipronil-coated maize seeds were planted and the proposed method was applied for checking the possible existence of four compounds in maize and soil samples, but none of them contained residues higher than the LOQs in both application rates. Moreover, the dissipation of fipronil in soil fits first-order kinetics with half-lives 9.90 and 10.34 days in Beijing and Shandong, respectively. Combined with an adequate sample treatment, this technique offers good sensitivity and selectivity in the three complex matrixes. The results could provide guidance for the further research on pesticide distribution and safe use of fipronil as seed coat in cereals.     

北京市大气PM10源解析研究

于2004年在北京市定陵、车公庄、古城、亦庄、房山和奥体中心6个采样点采集大气PM10环境样品,针对北京市颗粒物主要排放源采集土壤尘、建筑水泥尘、燃煤等污染源PM10样品,分别对其中的无机元素、离子、有机碳(OC)和元素碳(EC)进行测定。采用代表北京市颗粒物主要排放源PM10组分特征的成分谱,利用CMB受体模型对PM10来源进行解析。结果表明,PM10的最大来源为土壤尘,其它贡献源类依次为燃煤排放、机动车/燃油排放、二次粒子(SO42-、NO3-和NH4 )、建筑水泥尘。污染源贡献具有明显的季节变化,并存在一定的地域变化。