Geon-Jae Im

Feasibility and application of an HPLC/UVD to determine dinotefuran and its shorter wavelength metabolites residues in melon with tandem mass confirmation

A new analytical method was developed for dinotefuran and its metabolites, MNG, UF, and DN, in melon using high-performance liquid chromatography (HPLC) coupled with an ultraviolet detector (UVD). Due to shorter wavelength, lower sensitivity to UV detection, and high water miscibility of some metabolites, QuEChERs acetate-buffered version was modified for extraction and purification. Mobile phases with different ion pairing or ionisation agents were tested in different reverse phase columns, and ammonium bicarbonate buffer was found as the best choice to increase the sensitivity of target analytes to the UV detector. After failure of dispersive SPE clean-up with primary secondary amine, different solid phase extraction cartridges (SPE) were used to check the protecting capability of analytes against matrix interference. Finally, samples were extracted with a simple and rapid method using acetonitrile and salts, and purified through C(18)SPE. The method was validated at two spiking levels (three replicates for each) in the matrix. Good recoveries were observed for all of the analytes and ranged between 70.6% and 93.5%, with relative standard deviations of less than 10%. Calibration curves were linear over the calibration ranges for all the analytes with r(2)≥ 0.998. Limits of detection ranged from 0.02 to 0.05 mg kg(-1), whereas limits of quantitation ranged from 0.06 to 0.16 mg kg(-1) for dinotefuran and its metabolites. The method was successfully applied to real samples, where dinotefuran and UF residues were found in the field-incurred melon samples. Residues were confirmed via LC-tandem mass spectrometry (LC-MS/MS) in positive-ion electrospray ionisation (ESI(+)) mode.

Determination of spinetoram and its metabolites in amaranth and parsley using QuEChERS-based extraction and liquid chromatography-tandem mass spectrometry.

In this study, a simultaneous method was developed for the determination of spinetoram (XDE-175-J and XDE-175-L) and its demethyl metabolites (N-demethyl-175-J and N-demethyl-175-L) and formyl metabolites (N-formyl-175-J and N-formyl-175-L) in the minor crops; amaranth and parsley. The method uses quick, easy, cheap, effective, rugged, and safe (QuEChERS)-based extraction. Afterwards, the analytes were quantified and confirmed via liquid chromatography-electrospray ionisation tandem mass spectrometry (LC-ESI-MS/MS) in the positive ion mode using multiple reaction monitoring (MRM). Calibration curves were linear over the calibration ranges for all the analytes tested with r(2)>0.993. Limits of detection and quantitation were 0.01 and 0.03 mg/kg for all the tested analytes in amaranth and parsley, respectively. Recovery values, at spiking levels 0.05 and 0.25 mg/kg, ranged from 71.0% to 115.2% with relative standard deviations <15%, except for N-formyl-175-J in both amaranth and parsley. This method was applied to field-incurred samples and was shown to provide an adequate sensitivity and performance for the simultaneous determination of spinetoram and metabolites. To the best of our knowledge, this is the first time spinetoram and its metabolites were quantified using LC-MS/MS in minor crops.

Determination of chlorfenapyr in leek grown under greenhouse conditions with GC‐μECD and confirmation by mass spectrometry

A simple analytical method was developed for the determination of chlorfenapyr residues in leeks grown under greenhouse conditions. Residues were extracted by salting out, analyzed by gas chromatography with microelectron-capture detection, and confirmed via gas chromatography-mass spectrometry. The calibration curves were found to be linear with correlation coefficients (r(2) ) in excess of 0.998. The limits of detection and quantification were 0.0015 and 0.005 mg kg(-1) , respectively. For validation purposes, recovery studies were carried out at low and high levels. Yield recovery rates were 87.27-89.64% with a relative standard deviation <6%. A maximum of 0.32 mg kg(-1) of chlorfenapyr residue was detected in leek sample sprayed three times at 7 day intervals until 7 days prior to harvest. The results of this study suggest that chlorfenapyr is acceptable for application in/on leeks under the recommended dosage regimen.

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

Arsenic Contamination of Polished Rice Produced in Abandoned Mine Areas and Its Potential Human Risk Assessment using Probabilistic Techniques

BACKGROUND: This study was conducted to investi- gate the arsenic (As) contaminations in polished rice culti- vated nearby abandoned mine areas, and to estimate the potential health risk through dietary intake of As-enriched polished rice in each age-gender population. METHODS AND RESULTS: The As contents in poli- shed rice grown fifteen abandoned mine areas were analy- zed. The average daily intake (ADD) as well as probabili- stic health risk were estimated by assuming probability distribution of exposure parameters. The average total As concentration in polished rice was 0.09±0.06 mg/kg with a range of 0.02~0.35 mg/kg. For health risk assessment, the ADD values in all age-gender populations did not exceed the provisional tolerable daily intake (PTDI) of 2.1 µg/kg b.w./day for inorganic As. Cancer risk probability (R) values were 2.45~3.28×10 -4 and 2.51~5.75×10 -4 for all age population and gender population, respectively. Particularly, the R value, 5.75×10 -4 , for children less than six years old were estimated to be high. Hazard quotient (HQ) values were 0.23~0.31 and 0.11~0.33 for general population and age-gender population, respectively. CONCLUSION(s): The average R values assessed via intake of polished rice cultivated in abandoned mine areas exceeded the acceptable cancer risk of 10 -6 ~10 -4 for regula- tory purpose. Considering the HQ values smaller than 1.0, potential non-cancer toxic effects may not be caused by the long-time exposure through intake of As-contaminated polished rice.

Development and Validation of a Quick Easy Cheap Effective Rugged and Safe-based Multi-residues Analysis Method for Persimmon, Grape and Pear using Liquid Chromatography-tandem Mass Spectrometry

Association of official agricultural chemists official method was adapted and used to develop analytical method for determination of 76 pesticides residues in persimmon, grape, and pear by concurrent use of liquid chromatography-tandem mass spectrometry. Despite few exceptions in particular matrix, two fortified spiking (100 and 400 ppb) in three matrices gave satisfactory results in terms of accuracy, repeatability, precision, and linearity. Method detection limits (MDLs) were determined using five low spiking and eight replicate samples. MDLs were calculated by multiplying the standard deviation with student t-value 2.998 for n-1 (7) degree of freedom at 99% confident level. limit of quantification were obtained by multiplying standard deviation with 10. Experimental results indicate grape was the most problematic matrix among tested fruits and persimmon the least. Etoxazole is the most problematic pesticide and not applicable in this method. Developed method was successfully applied for the determination of residual pesticides in blindincurred samples.

Runoff of Endosulfan by Rainfall Simulation and from Soybean-grown Field Lysimeter

Three different experiments were carried out to investigate the runoff and erosion losses of endosulfan from sloped-field by rainfall. The mobility of endosulfan and which phase it was transported by were examined in adsorption study, the influence of rainfall pattern and slope degree on the pesticide loss were evaluated in simulated rainfall study, and the pesticide losses from soybean-grown field comparing with bare soil were measured in field lysimeter study. Adsorption parameter (K) of endosulfan ranged from 77 to 131 by adsorption method and K values by the desorption method were higher than those by the adsorption method. By the SSLRCs classification for pesticide mobility endosulfan was classified as non-mobile class (

Development of Analytical Method for Picoxystrobin in Agricultural Commodities Using GC/ECD and GC/MS

K_{oc}>4,000

Monitoring and Risk Assessment of Heavy Metals in Edible Mushrooms

). Runoff and erosion loss of endosulfan by three rainfall scenarios ranged from 3.4 to 5.6%and from 4.4 to 15.6%of the amount treated. Endosulfan residues were mainly remained at the top 5 cm of soil depth after the simulated rainfall study. Pesticide loss in case of 30%-slope degree ranged from 0.6 to 0.9 times higher than those in case of 10%-slope degree. The difference of pesticide runoff loss was related with its concentration in runoff water and the difference of pesticide erosion loss would related closely with the quantity of soil eroded. Endosulfan losses from a series of lysimeter plots in sloped land by rainfall ranged from 5 to 35% of the amount treated. The erosion rate of endosulfan from soybean-plots was 66% of that from bare soil plots. The effect of slope conditions was not great for runoff loss, but was great for erosion loss as increasing to maximum times with slope degree and slope length. The peak runoff concentration of endosulfan in soybean-plots and bare soil plots ranged from 8 to 10 and from 7 to on nine plots with different slope degree and slope length. Therefore the difference of the peak runoff concentrations between bare soil plots and soybean-plots were not great.

Monitoring and Risk Assessment of Cadmium and Lead in Agricultural Products

BACKGROUND: This study was conducted to develop analytical method for picoxystrobin in agricultural commodities using GC/ECD and GC/MS. METHODS AND RESULTS: Each steps of analytical method were optimized for determining picoxystrobin residues in various agricultural commodities. The developed methods include acetone extraction, n-hexane/saline water partition and florisil column chromatography for analysis of all samples (apple, potato, green pepper, hulled rice and soybean), and in addition to these steps, solid phase extraction (SPE) was used for analysis of green pepper and n-hexane/acetonitrile partition was used for analysis of hulled rice and soybean. The instrumental conditions were tested for quantitation in GC/ECD and for confirmation in GC/MS. Recovery was in the range of 86~109% with RSD 10.2% and the quantitation limits (LOQ) of method were 0.025 mg/kg in all agricultural commodities. CONCLUSION: The result showed that the developed method can be used to determine picoxystrobin residue in agricultural commodities.