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.     

Dissipation and residue of 2,4-D isooctyl ester in wheat and soil

A simple analytical method was developed to determine the 2,4-D isooctyl ester residue in wheat and soil by gas chromatography coupled with electron capture detector. Using the method, the dissipation and residue of 2,4-D isooctyl ester in wheat field was investigated. The average recoveries of 2,4-D isooctyl ester ranged from 80.1% to 110.0% with relative standard deviations of 2.4% to 16.1%. The pesticide showed a rapid dissipation rate either in wheat seedling or soil, with the half-lives of 1.0 to 3.0 days. The terminal residue results in wheat grain were much lower than the codex MRL (2.0 mg/kg). It could be considered safe to food and environment when using this herbicide for controlling weeds in wheat field.     

The dissipation of ethofenprox in cabbage and soil under open conditions

The dissipation of ethofenprox in cabbage and soil under open conditions was investigated at two primary cabbage-growing regions, Beijing and Kunming in China. Samples were extracted with acetonitrile and determined by ultra-performance liquid chromatography with a single quadrupole detector. Dissipation of ethofenprox from cabbage and soil can be best explained by a first-order decay process. The half-lives of ethofenprox were 1.9 and 2.3 days in cabbage and 20.0 and 13.0 days in soil at Beijing and Kunming, respectively. The concentration of ethofenprox residue was reduced by 90% taking 7 and 60 days in cabbage and soil. Dissipation rates in cabbage and soil at two geographically separated experimental fields differed, suggesting that this was affected by complicated factors, such as local climate and soil characteristics. These data could provide guidance for the proper and safe use of this pesticide on cabbage in China.     

Dissipation and residue of azoxystrobin in banana under field condition

A method was developed for determining azoxystrobin in banana and cultivation soil using gas chromatography. The dissipation and residue of azoxystrobin in banana fields at GAP conditions were investigated. The average recoveries ranged from 80.3 to 96.0 % with relative standard deviations of 2.9 to 7.2 % at three different spiking levels for each matrix. The results indicated that the half-life of azoxystrobin in bananas and soil ranged from 7.5 to 13.5 days in Guangdong and from 8.7 to 12.7 days in Fujian. The dissipation rates of azoxystrobin in banana and soil were almost the same. Terminal residues in banana and banana flesh (0.01 mg/kg) were all below the maximum residue limit (2 mg/kg by Codex Alimentarius Commission and China). The results demonstrated that the safety of using azoxystrobin at the recommended agriculture dosage to protect bananas from diseases.     

Dissipation and residue of triforine in strawberry and soil

Two independent field trials were performed in Guangdong and Hubei, China in 2011 to investigate the dissipation and residue levels of triforine in strawberry and soil. A fast and simple method using gas chromatography with electron capture detector was developed and validated to determine triforine levels in strawberry and soil. The average recovery of triforine in strawberry ranged from 87.46 to 104.32 % with a relative standard deviation (RSD) of 0.72 to 4.54 %; that in soil ranged from 83.82 to 103.01 % with an RSD of 3.89 to 4.36 %. The limit of quantification of the proposed method was 0.01 mg/kg for both strawberry and soil. The results suggest that the triforine dissipation curves followed the first-order kinetic. The half-lives of triforine in strawberry from Guangdong and Hubei were 3.58 and 4.42 days, respectively; those in soil were 3.53 and 4.10 days, respectively. The terminal residues of triforine in strawberry ranged from 0.032 to 0.264 mg/kg at preharvest intervals of 0.5, 1, and 3 days. These values are lower than the maximum residue limit of 1 mg/kg in strawberry set by the Codex Alimentarius Commission.     

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.     

Residues and dissipation of trifloxystrobin and its metabolite in tomatoes and soil

A simple residue analytical method using the quick, easy, cheap, effective, rugged, and safe (QuEChERS) procedure for the determination of trifloxystrobin and its metabolite trifloxystrobin acid (CGA321113) in tomato and soil was developed using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The limits of detection were 0.0005 mg/kg for trifloxystrobin and 0.001 mg/kg for trifloxystrobin acid, respectively. The average recoveries in tomato and soil ranged from 73–99 % for trifloxystrobin and 75–109 % for trifloxystrobin acid, with relative standard deviations below 15 %. The method was then used to study the dissipation and residues in tomato and soil. The dissipation half-lives of trifloxystrobin in tomato were 2.9 days (Beijing) and 5.4 days (Shandong), while in soil were 1.9 days (Beijing) and 3.0 days (Shandong), respectively. The final results showed that the major residue compound was trifloxystrobin in tomato whereas it was its metabolite, trifloxystrobin acid, in soil. The final residues of total trifloxystrobin (including trifloxystrobin acid) were below the EU maximum residue limit of 0.5 mg kg^?1 in tomato 3 days after the treatment.     

Degradation of three fungicides following application on strawberry and a risk assessment of their toxicity under greenhouse conditions

The health risk to humans of pesticide application on minor crops, such as strawberry, requires quantification. Here, the dissipation and residual levels of three fungicides (pyraclostrobin, myclobutanil, and difenoconazole) were studied for strawberry under greenhouse conditions using high-performance liquid chromatography (HPLC)-tandem mass spectrometry after Quick, Easy, Cheap, Effective, Rugged, and Safe extraction. This method was validated using blank samples, with all mean recoveries of these three fungicides exceeding 80 %. The residues of all three fungicides dissipated following first-order kinetics. The half-lives of pyraclostrobin, myclobutanil, and difenoconazole were 1.69, 3.30, and 3.65 days following one time application and 1.73, 5.78, and 6.30 days following two times applications, respectively. Fungicide residue was determined by comparing the estimated daily intake of the three fungicides against the acceptable daily intake. The results indicate that the potential health risk of the three fungicides was not significant in strawberry when following good agricultural practices (GAP) under greenhouse conditions.     

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 and residue of famoxadone in grape and soil

The analytical method of famoxadone residue and its dissipation in grape and soil were investigated. Famoxadone (68.75% water-dispersible granule) was applied at two dosages (1.25 and 2.5 g l^???1). Soil and grape samples were collected at intervals and analyzed for famoxadone residues. The results showed that the degradation rate of famoxadone in grape and soil were similar, and their dynamics could be described by C?=?1.1738e ^???0.0562t with correlation coefficient r?=?0.9044 in grape and C?=?5.6565e ^???0.0515t with r?=?0.9620 in soil, respectively. Half-lives were 12.3 and 13.5 days in grape and soil, respectively. The results indicated that at harvest time, the residues of famoxadone in grape were well below the EU’s maximum residue level (2 mg kg^???1) and was safe to apply in grape.     

Improved dissipation kinetic model to estimate permissible pre-harvest residue levels of pesticides in apples

Prediction of residual concentrations of applied pesticides during the pre-harvest period may be required to ensure the safety of agricultural products. In this study, time-dependent dissipation trends of carbaryl (CB), kresoxim-methyl (KM), flubendiamide (FB), flufenoxuron (FN), bitertanol (BT), and chlorantraniliprole (CN) applied to apples at recommended and threefold greater doses were modeled to estimate pre-harvest residue limit concentrations (C_PHRL) indicating permissible pesticide concentrations during the pre-harvest period. Double-exponential (DE) model results best fit the dissipation trends of all tested pesticides (correlation coefficients of 0.91–0.99) compared to zero-, first-, and second-order models. Among the pesticides examined, CB half-lives in apples of 2.9 and 6.6 days were the shortest, while those of FN (21.1–32.7 days) were the longest. The C_PHRL values for each pesticide in apples were estimated with DE model parameter values and could be used to determine harvest dates for safe apples with pesticide concentrations below their maximum residue limits. Application of the DE model for C_PHRL calculation provides more accurate information for farmers to produce agricultural products safe from pesticide residues.     

Dissipation and residue behavior of mepiquat on wheat and potato field application

A modified LC-MS method for the analysis of mepiquat residue in wheat, potato, and soil was developed and validated. A hydrophilic interaction liquid chromatographic column has been successfully used to retain and separate the mepiquat. Mepiquat residue dynamics and final residues in supervised field trials at Good Agricultural Practice (GAP) conditions in wheat, potato, and soil were studied. The limits of quantification for mepiquat in all samples were all 0.007 mg kg^?1, which were lower than their maximum residue limits. At fortification levels of 0.04, 0.2, and 2 mg kg^?1 in all samples, recoveries ranged from 77.5 to 116.4 % with relative standard deviations of 0.4–7.9 % (n?=?5). The dissipation half-lives (T _1/2) of mepiquat in soil (wheat), wheat plants, soil (potato), and potato plants were 4.5–6.3, 3.0–5.6, 2.2–4.6, and 2.4–3.2 days, respectively. The final residues of mepiquat were below 0.153 mg kg^?1 in soil (wheat), 0.052–1.900 mg kg^?1 in wheat, below 0.072 mg kg^?1 in soil (potato), and below 1.173 mg kg^?1 in potato at harvest time. Moreover, pesticide risk assessment for all the detected residues was conducted. A maximum 0.0012 % of acceptable daily intake (150 mg kg^?1) for national estimated daily intake indicated low dietary risk of these products.     

Behavior of fluopyram and tebuconazole and some selected pesticides in ripe apples and consumer exposure assessment in the applied crop protection framework

The supervised field trials were conducted in a commercial apple orchard in 2016. The trials were an attempt to determine a model for dissipation and toxicological evaluation of fluopyram, tebuconazole, captan, tetrahydrophthalimide (THPI), pirimicarb, spirodiclofen, and boscalid residues detected in fruit of Red Jonaprince, Lobo, and Gala varieties immediately before harvest. The analysis also covered amounts of pesticides still present in remnants of calyx in Lobo and Gala varieties immediately before harvest. Laboratory samples of ripe apples were collected within 14 days of the treatment. Levels of pesticide residues detected in the samples changed at a constant exponential rate, and the residue levels found in ripe apples of Red Jonaprince, Gala, and Lobo varieties immediately before harvest were below maximum residue levels (MRL). Overall, captan residues in remnants of calyx were at a level of 22.3% for the Gala variety and 9.3% for the Lobo variety. Likewise, the long-term daily intake of the detected substances by a Polish adult consumer was low, ranging from 0.02% ADI for pirimicarb to 0.72% ADI for captan.     

Dissipation pattern and risk quotients assessment of amisulbrom in Korean melon cultivated in plastic house conditions

Amisulbrom formulated as suspension concentrate was applied at the rate recommended for Korean melon to determine the dissipation pattern (at two different sites), the pre-harvest residue limit (PHRL), and risk assessments. Samples collected over 10 days were extracted using liquid-liquid extraction (LLE) and cleaned up with solid-phase extraction (SPE) Florisil cartridge. Residual concentrations were determined using liquid chromatography-ultraviolet detector (LC-UVD) and confirmed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The standard showed good instrument response linearity with a correlation coefficient (R ²) = 0.9999, and the recovery ranged from 87.5 to 93.7%. The dissipation half-life calculated from two different sites were found to be 7.0 and 8.8 days for sites 1 and 2, respectively. A PHRL graph constructed from the data indicated that if the residue levels were less than 0.55–0.59 mg/kg 3 days before harvest or less than 0.61–0.74 mg/kg 7 days before harvest, then they would be lower than the maximum residue limits (MRLs) at harvest. Risk assessments showed that the risk quotient (RQ) was 4.39–3.47% at 0 day, declined to 1.53–1.63% at 10 days. Therefore, the current data indicate that the amisulbrom can be applied safely to Korean melon; hence, it is unlikely to induce adverse health effects in consumers.     

江苏省茶园和农田土壤中拟除虫菊酯类农药残留与污染特征分析

于2018年4—6月采集了江苏省10个市的茶园和农田表层土壤样品,采用气相色谱-三重四级杆质谱仪分析样品中12种拟除虫菊酯类农药的质量比和组成.结果表明,江苏省茶园和农田土壤中广泛检出拟除虫菊酯类农药,总量分别为27.1～50.7,56.9～97.0 ng/g.研究区域的拟除虫菊酯类农药含量存在差异,但组成相近,均是高...     

Status and effect of pesticide residues in soils under different land uses of Andaman Islands, India

Pesticides are shown to have a great effect on soil organisms, but the effect varies with pesticide group and concentration, and is modified by soil organic carbon content and soil texture. In the humid tropical islands of Andaman, India, no systematic study was carried out on pesticide residues in soils of different land uses. The present study used the modified QuEChERS method for multiresidue extraction from soils and detection with a gas chromatograph. DDT and its various metabolites, α-endosulfan, β-endosulfan, endosulfan sulfate, aldrin, and fenvalerate, were detected from the study area. Among the different pesticide groups detected, endosulfan and DDT accounted for 41.7 % each followed by aldrin (16.7 %) and synthetic pyrethroid (8.3 %). A significantly higher concentration of pesticide residues was detected in rice–vegetable grown in the valley followed by rice–fallow and vegetable–fallow in the coastal plains. Soil microbial biomass carbon is negatively correlated with the total pesticide residues in soils, and it varied from 181.2 to 350.6 mg?kg^?1. Pesticide residues have adversely affected the soil microbial populations, more significantly the bacterial population. The Azotobacter population has decreased to the extent of 51.8 % while actinomycetes were the least affected though accounted for 32 % when compared to the soils with no residue.     

Dissipation and residues of bispyribac-sodium in rice and environment

The dissipation and residues of bispyribac-sodium in rice cropping system were studied. Bispyribac-sodium residues were extracted by a simple analytical method based on QuEChERs and detected by LC-MS/MS. The limit of detection for bispyribac-sodium of this method was 0.375?×?10^?3 ng. The limit of quantification (LOQ) was 5.0 μg/kg for rice plant samples, 2.0 μg/kg for rice hull, 0.2 μg/kg for water, and 0.1 μg/kg for soil and husked rice samples. The average recoveries of bispyribac-sodium ranged from 74.7 to 108 %, with relative standard deviations less than 13 %. The half-lives of bispyribac-sodium in rice plant, water, and soil were in the range of 1.4–5.6 days. More than 90 % of bispyribac-sodium residue dissipated within 5 days. The final residues of bispyribac-sodium in rice were all below LOQ at harvest time.     

Predicting Pesticide Volatility Through Coupled Above- and Belowground Multiphysics Modeling

Pesticides are applied to agricultural fields to control unwanted pests but can volatilize and be transported downwind by wind currents to create the potential for non-target organism exposure. Volatilization rates change through the growing season due to pesticide application timing, meteorological differences, and the differential flux rates from soil and vegetation matrices. Field studies quantifying pesticide volatility are expensive and cannot capture the semi-infinite parameter combinations of soil, crop, management, and meteorological conditions encountered under regional agronomic practices. A numerical approach was used to simulate pesticide dissipation above- and belowground to augment field and laboratory experimental observations. Above- and belowground physics are coupled into a single numerical tool using the COMSOL Multiphysics® software package with the current emphasis on pesticide volatility into air from soil and vegetation and resulting near field neighboring air concentrations. Comparison of simulation results against experimental observations for an insecticide (chlorpyrifos) applied to potato and alfalfa fields shows good agreement (R² 0.68–0.98). Chlorpyrifos volatility from plant surfaces drives the overall volatility within the first several days post application. The maximum volatility flux rate simulated and observed were 0.79 and 0.66 μg m^?2 s^?1 for the alfalfa trial and 2.72 and 2.17 μg m^?2 s^?1 for the potato field, respectively. This coupled multiphysics tool [computational fluid dynamics (CFD), mass transfer coefficients, and variably saturated flow in soil] can be used to estimate volatility flux rates of pesticides when little or no prior knowledge is available and for extrapolating field study observations to different and diverse scenarios.     

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.     

The effects of pesticide mixtures on degradation of pendimethalin in soils

Most agronomic situations involve a sequence of herbicide, fungicide, and insecticide application. On the other hand, use of pesticidal combinations has become a standard practice in the production of many agricultural crops. One of the most important processes influencing the behavior of a pesticide in the environment is its degradation in soil. It is known that due to several pesticide applications in one vegetation season, the pesticide may be present in mixtures with other pesticides or xenobiotics in soil. This study examines the role which a mixture of chemicals plays in pesticide degradation. The influence of other pesticides on the rate of pendimethalin (PDM) degradation in soil was measured in controlled conditions. Mixtures of PDM with mancozeb or mancozeb and thiamethoxam significantly influenced the degradation of pendimethalin under controlled conditions. The second type of mixtures, with metribuzin or thiamethoxam, did not affect the behavior of pendimethalin in soil. Also, we determined the influence of water content on the rate of pendimethalin degradation alone in two soils and compared it to the rate in three pesticide mixtures. We compared two equations to evaluate the predictors of the rate of herbicide dissipation in soil: the first-order kinetic and the non-linear empirical models. We used the non-linear empirical model assuming that the degradation rate of a herbicide in soil is proportional to the difference of the observed concentration of herbicide in soil at time and concentration of herbicide in the last day of measurement.