Onsite/on-field analysis of pesticide and veterinary drug residues by a state-of-art technology: A review.

Pesticides and veterinary drugs are generally employed to control pests and insects in crop and livestock farming. However, remaining residues are considered potentially hazardous to human health and the environment. Therefore, regular monitoring is required for assessing and legislation of pesticides and veterinary drugs. Various approaches to determining residues in various agricultural and animal food products have been reported. Most analytical methods involve sample extraction, purification (cleanup), and detection. Traditional sample preparation is time-consuming labor-intensive, expensive, and requires a large amount of toxic organic solvent, along with high probability for the decomposition of a compound before the analysis. Thus, modern sample preparation techniques, such as the quick, easy, cheap, effective, rugged, and safe method, have been widely accepted in the scientific community for its versatile application; however, it still requires a laboratory setup for the extraction and purification processes, which also involves the utilization of a toxic solvent. Therefore, it is crucial to elucidate recent technologies that are simple, portable, green, quick, and cost-effective for onsite and infield residue detections. Several technologies, such as surface-enhanced Raman spectroscopy, quantum dots, biosensing, and miniaturized gas chromatography, are now available. Further, several onsite techniques, such as ion mobility-mass spectrometry, are now being upgraded; some of them, although unable to analyze field sample directly, can analyze a large number of compounds within very short time (such as time-of-flight and Orbitrap mass spectrometry). Thus, to stay updated with scientific advances and analyze organic contaminants effectively and safely, it is necessary to study all of the state-of-art technology.

Establishment of import tolerance for the insecticide thiacloprid in strawberry.

To promote exports, import tolerance (IT) of thiacloprid in strawberry was proposed using the Organization for Economic Cooperation and Development (OECD) maximum residue limit (MRL) calculator after conducting three different field trials. The pre-harvest interval of residual pattern and degradation dynamics of thiacloprid in strawberry were determined using ultra-performance liquid chromatography-tandem mass spectrometry. Samples were extracted with acetonitrile and a mixture of salts and dilution was performed for purification. A six-point matrix-matched calibration curve was constructed which provided excellent linearity with coefficient of determination (R2 ) of 0.9998 or more. Detection and quantification limits were 0.003 and 0.01 mg/kg, respectively. The method was validated in quintuplicate at three different concentrations, which resulted in acceptable recovery ranging from 80.86% to 101.71% with relative standard deviation of 6.50 or less among the three field sites. The developed method was applied to the field-treated sample harvested at different intervals. In the pre-harvest interval trial, the amount of thiacloprid residues ranged from 0.24 to 0.70 mg/kg in field site 1 (Nonsan), 0.16 to 0.50 mg/kg in field site 2 (Sunchang), and 0.36 to 0.50 mg/kg in field site 3 (Sacheon). By contrast, in the degradation trial, the observed residues were 0.03-0.81 mg/kg in field site 1 and 0.02-0.48 mg/kg in field site 2. Consequently, the IT of thiacloprid in strawberry using the OECD MRL calculator was proposed as 2 mg/kg, which is exactly the same as the MRL established by the Republic of Korea. In conclusion, the residue study proposes 2.0 mg/kg as the MRL of thiacloprid in strawberries.

Quantification of spinosyn A and spinosyn D in animal-derived products using multiwalled carbon nanotubes coupled with LC-MS/MS for analysis.

An analytical method was developed for the quantification of spinosad (sum of spinosyns A and D) in five animal-derived products (chicken breast, pork, beef, egg, and milk) using LC-MS/MS. The sample was extracted using acetonitrile/1% acetic acid and a combination of magnesium sulfate and sodium acetate salts. The sample was purified using multiwalled carbon nanotubes as sorbent via a dispersive-solid-phase extraction procedure. Matrix-matched calibration (seven-point) provided good linearity with coefficient of determination (R2 ) ≥0.99 for each product. The limits of detection and quantification (LOQs) ranged between 0.0003-0.03 and 0.001-0.1 mg/kg, respectively. Method validation was carried out after spiking the target standard to blank matrices at the concentration levels of LOQ, 2 × LOQ, and 10 × LOQ with three replicates for each. The average recoveries were between 74 and 104%, with relative standard deviations ≤9.68, which were within the acceptable range designated by the international organizations. The developed method was successfully applied for monitoring market samples collected throughout the Korean Peninsula, and none of the samples tested positive for the target analytes. It has therefore been shown that dehydration and acidification were effective to extract spinosad from animal-derived products.

Dissipation kinetics, pre-harvest residue limits, and dietary risk assessment of the systemic fungicide metalaxyl in Swiss chard grown under greenhouse conditions.

The residual behavior of the systemic fungicide, metalaxyl, in Swiss chard cultivated at two different locations under greenhouse conditions was investigated using high-performance liquid chromatography coupled with an ultraviolet detector (HPLC-UVD). Samples were randomly collected over 14 days and extracted using acetonitrile, partitioned using solid sodium chloride, and a solid-phase extraction (SPE) NH2 cartridge was used for cleanup. The linearity over a concentration range 0.05-50 mg/L was excellent with a coefficient of determination (R2) of 0.9997. The recovery rate ranged from 77.05 to 88.92% with relative standard deviations (RSDs) ≤ 10.74, and the limits of detection (LOD) and quantification (LOQ) were 0.0033 and 0.01 mg/kg, respectively. The initial (2 h after application) deposits were 4.69 and 5.90 mg/kg for sites 1 and 2, respectively, which increased to 4.95 and 6.57 mg/kg, respectively, one day post-application, owing to the systemic properties of the fungicide. The dissipation half-life was 5.3 and 6.0 days for sites 1 and 2, respectively. The pre-harvest residue limit (PHRL) suggested that if 55.38 and 47.23 mg/kg was applied 10 days before harvest or 33.28 and 30.73 mg/kg was applied 5 days before harvest (for sites 1 and 2, respectively) then the concentration will fall below the maximum residue limit (MRL = 20.0 mg/kg) at the time of harvest. The dietary risk assessment, estimated as hazard quotient (RQ%), indicate that metalaxyl can be safely used in/on Swiss chard, with no hazardous effects expected for consumers.

Analytical approach, dissipation pattern and risk assessment of pesticide residue in green leafy vegetables: A comprehensive review.

The category of 'leafy vegetables' comprises a wide range of plants, including cabbage, lettuce, leeks, spinach, Swiss chard and kale, and it forms a significant component of the human diet. Typically, leafy vegetables are low in calories and fat, are great sources of vitamins, protein, dietary fibre and minerals (including iron, calcium, and nitrates), and are rich in phytochemicals. To counter the impact of pests on vegetables, a broad variety of pesticides are used. Because of their large surface areas, leafy vegetables are expected to have high residual pesticide levels. As such, a sound analytical approach is needed to detect and quantify residue levels that are equal to or lower than the maximum residue limits, thus rendering the products safe for consumption. Overall, leafy vegetables consumed raw (after a tap water wash only), boiled or steamed contribute 2% of total vegetable consumption globally, and they might have a comparatively greater influence on health than cereal ingestion. Consequently, in this review paper, we highlight the importance of leafy vegetables, the pesticides that are commonly used on them and various analytical techniques, including sample preparation, extraction, clean-up and final detection. The effects on dissipation patterns, pre-harvest residue limits and safety/risks imposed by various pesticides are also reviewed and discussed. In conclusion, environmentally friendly extraction methods coupled with high-throughput techniques with greater reproducibility and lower uncertainty are needed for quantifying residues in leafy vegetables at very low concentrations. Commercial and household food preparation, such as washing, peeling, blanching and cooking are effective in removing most of the pesticide residues that are loosely attached on vegetables.

Dynamic residual pattern of azoxystrobin in Swiss chard with contribution to safety evaluation.

This study aimed at quantifying the residual amount of azoxystrobin in Swiss chard samples grown under greenhouse conditions at two different locations (Gwangju and Naju, Republic of Korea). Samples were extracted with acetonitrile, separated by salting out, and subjected to purification by using solid-phase extraction. The analyte was identified using liquid chromatography-ultraviolet detection. The linearity of the calibration range was excellent with coefficient of determination 1.00. Recovery at three different spiking levels (0.1, 0.5, and 4 mg/kg) ranged between 82.89 and 109.46% with relative standard deviation <3. The limit of quantification, 0.01 mg/kg, was considerably much lower than the maximum residue limit (50 mg/kg) set by the Korean Ministry of Food and Drug Safety. The developed methodology was successfully used for field-treated leaves, which were collected randomly at 0-14 days following azoxystrobin application. The rate of disappearance in/on Swiss chard was ascribed to first-order kinetics with a half-life of 8 and 5 days, in leaves grown in Gwangju and Naju greenhouses, respectively. Risk assessments revealed that the acceptable daily intake percentage is substantially below the risk level of consumption at day 0 (in both areas), thus encouraging its safe consumption.

Chromatographic determination, decline dynamic and risk assessment of sulfoxaflor in Asian pear and oriental melon.

The dissipation pattern of sulfoxaflor in Asian pear cultivated in an open field conditions and in oriental melon grown under plastic house conditions was each studied in two different locations. Residues in field-treated samples were determined using liquid chromatography coupled with an ultraviolet detector and confirmed by liquid chromatography-tandem mass spectrometry. A calibration curve for sulfoxaflor was linear over the concentration range 0.1-5.0 mg/L, with a coefficient of determination of 0.9999. The limits of detection and quantification (LOQ) were 0.007 and 0.02 mg/kg, respectively. Recoveries at three fortification levels (LOQ, 10 × LOQ and maximum residue limit) ranged from 70.5 to 86.2%, with a relative standard deviation ≤5.8%. The dissipation half-lives were 10.8 and 7.9 days in pear and 5.4 and 5.9 days in oriental melon, at sites 1 and 2, respectively. Based on a pre-harvest residue limit curve, it was predicted that, if the residues at 10 days before harvest in Asian pear are <0.54/0.61 mg/kg and those in oriental melon are <1.43/1.26 mg/kg, then the residue level will be below the maximum residue limit at harvest. Risk assessment at zero days showed a percentage acceptable daily intake of 10.80% in Asian pear and 1.77 and 1.55% in oriental melon, for sites 1 and 2, respectively. These values indicate that the fruits are safe for consumption.

Residual dynamic and risk assessment of dimethomorph in Swiss chard grown at two different sites.

Residue analysis of dimethomorph in Swiss chard cultivated at two different locations under greenhouse conditions was conducted using high-performance liquid chromatography-ultraviolet detection and confirmed by tandem mass spectrometry. The randomly collected samples (over 14 days) were extracted with acetonitrile and purified using a Florisil solid-phase extraction cartridge. Linearity over a concentration range of 0.05-50.0 mg/L had an excellent coefficient of determination of 0.9996. Recovery rate ranged from 82.98 to 95.43% with relative standard deviations ≤5.12% and limits of detection and quantification of 0.003 and 0.01 mg/kg, respectively. The initial deposits [day 0 (2 h post-application)] were considerably lower (7.57 and 8.55 mg/kg for sites 1 and 2, respectively) than the maximum residue limit (30 mg/kg) set by the Korean Ministry of Food and Drug Safety. The dissipation half-life was approximately the same, being 5.0 and 5.1 days for sites 1 and 2, respectively. Risk assessment estimated as acceptable daily intake revealed a value of 0.084 or 0.094% (day 0) and 0.014% (10 days post-application), for sites 1 and 2, respectively. The values indicated that dimethomorph can be safely used on Swiss chard, with no hazardous effects expected for Korean consumers.

Quick, easy, cheap, effective, rugged, and safe sample preparation approach for pesticide residue analysis using traditional detectors in chromatography: A review.

In pesticide residue analysis, relatively low-sensitivity traditional detectors, such as UV, diode array, electron-capture, flame photometric, and nitrogen-phosphorus detectors, have been used following classical sample preparation (liquid-liquid extraction and open glass column cleanup); however, the extraction method is laborious, time-consuming, and requires large volumes of toxic organic solvents. A quick, easy, cheap, effective, rugged, and safe method was introduced in 2003 and coupled with selective and sensitive mass detectors to overcome the aforementioned drawbacks. Compared to traditional detectors, mass spectrometers are still far more expensive and not available in most modestly equipped laboratories, owing to maintenance and cost-related issues. Even available, traditional detectors are still being used for analysis of residues in agricultural commodities. It is widely known that the quick, easy, cheap, effective, rugged, and safe method is incompatible with conventional detectors owing to matrix complexity and low sensitivity. Therefore, modifications using column/cartridge-based solid-phase extraction instead of dispersive solid-phase extraction for cleanup have been applied in most cases to compensate and enable the adaptation of the extraction method to conventional detectors. In gas chromatography, the matrix enhancement effect of some analytes has been observed, which lowers the limit of detection and, therefore, enables gas chromatography to be compatible with the quick, easy, cheap, effective, rugged, and safe extraction method. For liquid chromatography with a UV detector, a combination of column/cartridge-based solid-phase extraction and dispersive solid-phase extraction was found to reduce the matrix interference and increase the sensitivity. A suitable double-layer column/cartridge-based solid-phase extraction might be the perfect solution, instead of a time-consuming combination of column/cartridge-based solid-phase extraction and dispersive solid-phase extraction. Therefore, replacing dispersive solid-phase extraction with column/cartridge-based solid-phase extraction in the cleanup step can make the quick, easy, cheap, effective, rugged, and safe extraction method compatible with traditional detectors for more sensitive, effective, and green analysis.

Development of a single-run analytical method for the detection of ten multiclass emerging contaminants in agricultural soil using an acetate-buffered QuEChERS method coupled with LC-MS/MS.

This study was undertaken to develop and validate a single multiresidue method for the monitoring of ten multiclass emerging contaminants, viz. ceftiofur, clopidol, florfenicol, monensin, salinomycin, sulfamethazine, sulfathiazole, sulfamethoxazole, tiamulin, and tylosin in agricultural soil. Samples were extracted using an acetate-buffered, modified quick, easy, cheap, effective, rugged, and safe method followed by liquid chromatography with tandem mass spectrometric analysis in positive ion mode. Separation on an Eclipse Plus C18 column was conducted in gradient elution mode using a mobile phase of methanol (A) and distilled water (B), each containing 0.1% formic acid and 5 mM ammonium formate. The linearity of the matrix-matched calibrations, expressed as determination coefficients, was good, with R2 ≥ 0.9908. The limits of quantification were in the range 0.05-10 µg/kg. Blank soil samples spiked with 4 × and 20 × the limit of quantification provided recovery rates of 60.2-120.3% (except sulfamethoxazole spiked at 4 × the limit of quantification, which gave 131.9%) with a relative standard deviation < 13% (except clopidol spiked at 20 × the limit of quantification, which gave 25.2%). This method was successfully applied to the monitoring of 51 field-incurred agricultural loamy-sand soil samples collected from 17 provincial areas throughout the Korean Peninsula. The detected and quantified drugs were clopidol (≤ 4.8 µg/kg), sulfathiazole (≤ 7.7 µg/kg), sulfamethazine (≤ 6.6 µg/kg), tiamulin (≤ 10.0 µg/kg), and tylosin (≤ 5.3 µg/kg). The developed method is simple and versatile, and can be used to monitor various classes of veterinary drugs in soil.

Simultaneous detection of sulfoxaflor and its metabolites, X11719474 and X11721061, in lettuce using a modified QuEChERS extraction method and liquid chromatography-tandem mass spectrometry.

An analytical method has been developed to quantify the residual levels of sulfoxaflor and its metabolites (X11719474 and X11721061) in/on cultivated lettuce grown under greenhouse conditions. Samples were extracted and purified using a quick, easy, cheap, effective, rugged, and safe 'QuEChERS' method (original version) following systematic method optimization and were analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Good linearity with coefficient of determination ≥0.9930 was obtained and the limits of detection (LOD) and quantification (LOQ) were in the ranges of 0.003-0.006 and 0.01-0.02 mg/kg, respectively. The recovery rates of both the parent compound and its metabolites (fortified at 10 and 50× the LOQ) estimated from six replicates ranged between 81.9 and 115.5% with a relative standard deviation <12%. The validated method was applied to field-incurred samples (collected over 7 days) sprayed once or twice with a water-dispersible granule formulation. Notably, a substantial reduction in rate was observed after 3 days and the half-life was short, only 1.5 days. The developed method is simple and versatile and can be used for various leafy vegetables.

Application of a solvent-free solid injection technique coupled with GC-MS for discrimination between the secondary metabolites of wild and cultivated South Korean medicinal foods.

Solvent-free solid injection was applied to differentiate between wild and cultivated South Korean medicinal foods, including dureup (Aralia elata), deodeok (Codonopsis lanceolata) and doraji (Platycodon grandiflorus). A number of compounds were identified in wild and cultivated dureup (53 and 46), deodeok (47 and 51) and doraji (43 and 38). Secondary metabolites, including butanal,2-methyl-, ß-caryophyllene, neoclovene, α-humulene, γ-curcumene, ß-bisabolene, and phytol, were identified in dureup with significantly (P < 0.05) different amounts between both types. In deodeok, squalene and other main components such as acetic acid, methyl ester, furan-methyl-furfural, 2-furan-methanol, and 5-methyl-furfural, were statistically different between the two types. Doraji has significantly different compounds such as furfural, 5-methyl-furfural, 2-methoxy-phenol, 2-methoxy-4-(1-propenyl)-phenol, and 1-(4-hydroxy-3-methoxyphenyl)-2-propanone. Although we failed to confirm the key compounds, a new compound, namely desaspidinol, was synthesized for the first time and its retention index determined under the experimental conditions. This solventless, easy technique can be used as a simple way to discriminate between wild and cultivated types of medicinal plants via identification of volatile markers or specific fingerprints.

Dissipation kinetics and pre-harvest residue limit of pyriofenone in oriental melon (Cucumis melo Var. makuwa) grown under regulated climatic conditions.

A high-performance liquid chromatography-ultraviolet detection was used to estimate the disappearance rates as well as the pre-harvest residue limits of pyriofenone in oriental melon (Cucumis melo var. makuwa) grown under greenhouse conditions in two different locations (A and B) in Seongju, Republic of Korea. The identity of the compound in standard solution and representative field incurred samples was confirmed using liquid chromatography-tandem mass spectrometry. The method was validated in terms of linearity, limits of detection and quantification, accuracy (expressed as recovery) and precision (expressed as relative standard deviation) for accurate and precise quantitation. Notably, the residual levels of field incurred samples collected over days 0-10 post-application were below the maximum residue level (0.2 mg/kg) established by the Korean Ministry of Food and Drug Safety. Site A showed lower residue levels and a higher decline rate than site B, which might be attributed to seasonal variation (high temperature) and increased metabolic and enzyme profiling in the mature fruits. The half-lives were similar, 4.9 and 4.3 days, at sites A and B, respectively. Using the pre-harvest residue limit, we predicted the residue amounts at 10 and 5 days before harvest, which resulted in concentrations lower than the provisional maximum residue level at harvest time.

The disappearance rate and risk assessment of thiacloprid residues in Asian pear using liquid chromatography confirmed with tandem mass spectrometry.

This study was undertaken to quantify the residue levels and propose the dissipation kinetics of thiacloprid formulated as suspension concentrate in field-incurred Asian pears grown under two different open-field conditions. Samples were extracted with 20% distilled water in acetonitrile; partitioned with brine water and dichloromethane; and purified with a Florisil solid phase extraction cartridge. The analyte was identified with an LC ultraviolet detector, and field-incurred samples were confirmed using LC-MS/MS. The calibration curve was linear over the range 0.05-5.0 mg/L with a satisfactory coefficient of determination (R2 = 0.9994). The limits of detection and limits of quantification (LOQ) were 0.003 and 0.01 mg/kg, respectively. The recovery rate fortified to blank samples at LOQ, 10× LOQ, and the maximum residue limit (MRL) were between 73.7 and 86.2% with relative standard deviation ≤9.0%. The residual concentrations at both sites were considerably lower than the MRL (0.7 mg/kg) set by the Korean Ministry of Food Drug Safety, with biological half-lives of 5.0 and 7.4 days, for sites 1 and 2, respectively. From the pre-harvest residue limit curve, it was predicted that if the residues were <1.13 or 1.40 mg/kg 10 days before harvest, the residue level would be lower than the MRL during harvest. Risk assessment on day 0 showed an acceptable daily intake (%) of 13.0% and 11.0% for sites 1 and site 2, respectively, which indicates that the residual amounts are not hazardous to the Korean population.

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.

QuEChERS method for the simultaneous quantification of phorate and its metabolites in porcine and chicken muscle and table eggs using ultra-high performance liquid chromatography with tandem mass spectrometry.

An analytical method to detect phorate and its metabolites, including phorate sulfone, phorate sulfoxide, phoratoxon, phoratoxon sulfone, and phoratoxon sulfoxide, in porcine and chicken muscles and table eggs was developed and validated. Extraction was performed using a quick, easy, cheap, effective, rugged, and safe method and analysis was conducted using ultra-high performance liquid chromatography-tandem mass spectrometry. Matrix-matched calibrations were linear over the tested concentrations, with determination coefficient ≥ 0.995 for all tested analytes in the different matrices. The limits of detection and quantification were 0.001 and 0.004 mg/kg, respectively. The calculated recovery rates at three fortification levels were satisfactory, with values between 74.22 and 119.89% and relative standard deviations < 10%. The method was applied successfully to commercial samples collected from locations throughout the Korean Peninsula, and none of them showed any traces of the tested analytes. Overall, the developed method is simple and versatile, and can be used for monitoring phorate and its metabolites in animal products rich in protein and fat.

Analysis of mandipropamid residual levels through systematic method optimization against the matrix complexity of sesame leaves using HPLC/UVD.

An analytical method was developed to detect mandipropamid residues in sesame leaves using high-performance liquid chromatography-ultraviolet detection. Samples were extracted with acetonitrile and were prepurified using a solid-phase extraction (SPE) cartridge with an additional dispersive-SPE (d-SPE) sorbent application. The method was validated using an external calibration curve prepared using pure solvent. The linearity was excellent with determination coefficient = 1. The limits of detection and quantification were 0.003 and 0.01 mg/kg, respectively. Recoveries at three spiking levels - 0.1, 0.5, and 1.0 mg/kg - were in the range 80.3-90.7% with relative standard deviations <2%. This method was applied to field-treated samples collected from two different areas, Gwangju and Muan, in the Republic of Korea and the half-lives were similar, 5.10 and 5.41 days, respectively. The pre-harvest residue limit was also predicted for both sites. The proposed method is sensitive and able to quantify trace amounts of mandipropamid in leafy vegetables. The combination of SPE and d-SPE effectively removed the matrix components in sesame leaves. Copyright © 2015 John Wiley & Sons, Ltd.

Simultaneous detection of fluquinconazole and flusilazole in lettuce using gas chromatography with a nitrogen phosphorus detector: decline patterns at two different locations.

Method validations in addition to decline patterns of fluquinconazole and flusilazole in lettuce grown under greenhouse conditions at two different locations were investigated. Following the application of fluquinconazole and flusilazole at a dose rate of 20 mL/20 L water, lettuce samples were collected randomly for up to 7 days post-application, and simultaneously extracted with acetone, purified through solid-phase extraction, analyzed via gas chromatography with a nitrogen phosphorus detector, and confirmed through gas chromatography-mass spectrometry. The linearity was excellent, with determination coefficients (R(2) ) between 0.9999 and 1.0. The method was validated in triplicate at two different spiking levels (0.2 and 1.0 mg/kg) with satisfactory recoveries between 75.7 and 97.9% and relative standard deviations of <9. The limit of quantification was 0.01 mg/kg. Both analytes declined very quickly, as can be seen from the short half-life time of <4 days. Statistical analysis revealed significant differences between residues at different days of sampling, except at 7 days post-application (triple application). At that point, the decline patterns of fluquinconazole and flusilazole were independent of application rate, location, temperature and humidity. Copyright © 2015 John Wiley & Sons, Ltd.

Residual determination and risk assessment of buprofezin in plum (Prunus domestica) grown in open-field conditions following the application of three different formulations.

This study was conducted to characterize the residual level and perform a risk assessment on buprofezin formulated as an emulsifiable concentrate, wettable powder, and suspension concentrate over various treatment schedules in plum (Prunus domestica). The samples were extracted with an AOAC quick, easy, cheap, effective, rugged, and safe, 'QuEChERS', method after major modifications. As intrinsic interferences were observed in blank plum samples following dispersive-solid phase extraction (consisting of primary secondary amine and C18 sorbents), amino cartridges were used for solid-phase extraction. Analysis was carried out using liquid chromatography with diode array detection and confirmed by liquid chromatography-tandem mass spectrometry. The method showed excellent linearity with determination coefficient (R2 = 1) and satisfactory recoveries (at two spiking levels, 0.5 and 2.5 mg/kg) between 90.98 and 94.74% with relative standard deviation (RSD) ≤8%. The limit of quantification (0.05 mg/kg) was considerably lower than the maximum residue limit (2 mg/kg) set by the Codex Alimentarius. Absolute residue levels for emulsifiable concentrates were highest, perhaps owing to the dilution rate and adjuvant. Notably, all formulation residues were lower than the maximum residue limit, and safety data proved that the fruits are safe for consumers. Copyright © 2016 John Wiley & Sons, Ltd.

Residue level and dissipation pattern of lepimectin in shallots using high-performance liquid chromatography coupled with photodiode array detection.

Lepimectin, as an emulsifiable concentrate, was sprayed on shallots at the recommended dose rate (10 mL/20 L) to determine its residue levels, dissipation pattern, pre-harvest residue limits (PHRLs), and health risk. Samples were randomly collected over 10 days, extracted with acetonitrile, purified using an amino solid-phase extraction (NH2 -SPE) cartridge and analyzed using a high-performance liquid chromatography-photodiode array detection method. Field-incurred samples were confirmed using ultra-performance liquid chromatography-tandem mass spectrometry. The linearity was excellent, with a determination coefficient (R2 ) of ≥0.9991. The recoveries at two spiking levels (0.2 and 1.0 mg/kg) ranged from 84.49 to 87.64% with relative standard deviations of ≤7.04%. The developed method was applied to field samples grown in separate greenhouses, one located in Naju and one in Muan, in the Republic of Korea. The dissipation pattern was described by first-order kinetics with half-lives of 1.9 (Naju) and 1.7 days (Muan). The PHRL curves indicated that, if the lepimectin residues are <0.18 (Naju) and <0.13 mg/kg (Muan) 5 days before harvest, the residue levels will be lower than the maximum residue limit (0.05 mg/kg) upon harvesting. The risk assessment data indicated that lepimectin is safe for use in the cultivation of shallots, with no risk of detrimental effects to the consumer.