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Development and Validation of an Analytical Method for Fenpropimorph in Agricultural Products Using QuEChERS and LC-MS/MS (QuEChERS법과 LC-MS/MS를 이용한 농산물 중 Fenpropimorph 시험법 개발 및 검증)

  • Lee, Han Sol;Do, Jung-Ah;Park, Ji-Su;Cho, Sung Min;Shin, Hye-Sun;Jang, Dong Eun;Choi, Young-Nae;Jung, Yong-hyun;Lee, Kangbong
    • Journal of Food Hygiene and Safety
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    • v.34 no.2
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    • pp.115-123
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    • 2019
  • An analytical method was developed for the determination of fenpropimorph, a morpholine fungicide, in hulled rice, potato, soybean, mandarin and green pepper using QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) sample preparation and LC-MS/MS (liquid chromatography-tandem mass spectrometry). The QuEChERS extraction was performed with acetonitrile followed by addition of anhydrous magnesium sulfate and sodium chloride. After centrifugation, d-SPE (dispersive solid phase extraction) cleanup was conducted using anhydrous magnesium sulfate, primary secondary amine sorbents and graphitized carbon black. The matrix-matched calibration curves were constructed using seven concentration levels, from 0.0025 to 0.25 mg/kg, and their correlation coefficient ($R^2$) of five agricultural products were higher than 0.9899. The limits of detection (LOD) and quantification (LOQ) were 0.001 and 0.0025 mg/kg, respectively, and the limits of quantification for the analytical method were 0.01 mg/kg. Average recoveries spiked at three levels (LOQ, $LOQ{\times}10$, $LOQ{\times}50$, n=5) and were in the range of 90.9~110.5% with associated relative standard deviation values less than 5.7%. As a result of the inter-laboratory validation, the average recoveries between the two laboratories were 88.6~101.4% and the coefficient of variation was also below 15%. All optimized results were satisfied the criteria ranges requested in the Codex guidelines and Food Safety Evaluation Department guidelines. This study could serve as a reference for safety management relative to fenpropimorph residues in imported and domestic agricultural products.

Development and Validation of a Simultaneous Analytical Method for 5 Residual Pesticides in Agricultural Products using GC-MS/MS (GC-MS/MS를 이용한 농산물 중 잔류농약 5종 동시시험법 개발 및 검증)

  • Park, Eun-Ji;Kim, Nam Young;Shim, Jae-Han;Lee, Jung Mi;Jung, Yong Hyun;Oh, Jae-Ho
    • Journal of Food Hygiene and Safety
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    • v.36 no.3
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    • pp.228-238
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    • 2021
  • The aim of this research was to develop a rapid and easy multi-residue method for determining dimethipin, omethoate, dimethipin, chlorfenvinphos and azinphos-methyl in agricultural products (hulled rice, potato, soybean, mandarin and green pepper). Samples were prepared using QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) and analyzed using gas chromatography-tandem mass spectrometry (GC-MS/MS). Residual pesticides were extracted with 1% acetic acid in acetonitrile followed by addition of anhydrous magnesium sulfate (MgSO4) and anhydrous sodium acetate. The extracts were cleaned up using MgSO4, primary secondary amine (PSA) and octadecyl (C18). The linearity of the calibration curves, which waas excellent by matrix-matched standards, ranged from 0.005 mg/kg to 0.3 mg/kg and yielded the coefficients of determination (R2) ≥ 0.9934 for all analytes. Average recoveries spiked at three levels (0.01, 0.1, 0.5 mg/kg) and were in the range of 74.2-119.3%, while standard deviation values were less than 14.6%, which is below the Codex guideline (CODEX CAC/GL 40).

Predicting the Pre-Harvest Sprouting Rate in Rice Using Machine Learning (기계학습을 이용한 벼 수발아율 예측)

  • Ban, Ho-Young;Jeong, Jae-Hyeok;Hwang, Woon-Ha;Lee, Hyeon-Seok;Yang, Seo-Yeong;Choi, Myong-Goo;Lee, Chung-Keun;Lee, Ji-U;Lee, Chae Young;Yun, Yeo-Tae;Han, Chae Min;Shin, Seo Ho;Lee, Seong-Tae
    • Korean Journal of Agricultural and Forest Meteorology
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    • v.22 no.4
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    • pp.239-249
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    • 2020
  • Rice flour varieties have been developed to replace wheat, and consumption of rice flour has been encouraged. damage related to pre-harvest sprouting was occurring due to a weather disaster during the ripening period. Thus, it is necessary to develop pre-harvest sprouting rate prediction system to minimize damage for pre-harvest sprouting. Rice cultivation experiments from 20 17 to 20 19 were conducted with three rice flour varieties at six regions in Gangwon-do, Chungcheongbuk-do, and Gyeongsangbuk-do. Survey components were the heading date and pre-harvest sprouting at the harvest date. The weather data were collected daily mean temperature, relative humidity, and rainfall using Automated Synoptic Observing System (ASOS) with the same region name. Gradient Boosting Machine (GBM) which is a machine learning model, was used to predict the pre-harvest sprouting rate, and the training input variables were mean temperature, relative humidity, and total rainfall. Also, the experiment for the period from days after the heading date (DAH) to the subsequent period (DA2H) was conducted to establish the period related to pre-harvest sprouting. The data were divided into training-set and vali-set for calibration of period related to pre-harvest sprouting, and test-set for validation. The result for training-set and vali-set showed the highest score for a period of 22 DAH and 24 DA2H. The result for test-set tended to overpredict pre-harvest sprouting rate on a section smaller than 3.0 %. However, the result showed a high prediction performance (R2=0.76). Therefore, it is expected that the pre-harvest sprouting rate could be able to easily predict with weather components for a specific period using machine learning.

Development and Validation of Analytical Method and Antioxidant Effect for Berberine and Palmatine in P.amurense (황백의 지표성분 berberine과 palmatine의 분석법 개발과 검증 및 항산화 효능 평가)

  • Jang, Gill-Woong;Choi, Sun-Il;Han, Xionggao;Men, Xiao;Kwon, Hee-Yeon;Choi, Ye-Eun;Park, Byung-Woo;Kim, Jeong-Jin;Lee, Ok-Hwan
    • Journal of Food Hygiene and Safety
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    • v.35 no.6
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    • pp.544-551
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    • 2020
  • The aim of this study was to develop and validate a simultaneous analytical method for berberine and palmatine, which are representative substances of Phellodendron amurense, and to evaluate the antioxidant activity. We evaluated the specificity, linearity, precision, accuracy, limit of detection (LOD), and limit of quantification (LOQ) of analytical methods for berberine and palmatine using high-performance liquid chromatography. Our result showed that the correlation coefficients of the calibration curve for berberine and palmatine exhibited 0.9999. The LODs for berberine and palmatine were 0.32 to 0.35 µg/mL and the LOQs were 0.97 to 1.06 µg/mL, respectively. The inter-day and intra-day precision values for berberine and palmatine were from 0.12 to 1.93 and 0.19 to 2.89%, respectively. The inter-day and intra-day accuracies were 98.43-101.45% and 92.39-100.60%, respectively. In addition, the simultaneous analytical method was validated for the detection of berberine and palmatine. Moreover, we conducted FRAP and NaNO2 scavenging activity assays to measure the antioxidant activities of berberine and palmatine, and both showed antioxidant activity. These results suggest that P.amurense could be a potential natural resource for antioxidant activity and that the efficacy can be confirmed by investigating the content of the berberine and palmatine.

Analysis of the Effect of Objective Functions on Hydrologic Model Calibration and Simulation (목적함수에 따른 매개변수 추정 및 수문모형 정확도 비교·분석)

  • Lee, Gi Ha;Yeon, Min Ho;Kim, Young Hun;Jung, Sung Ho
    • Journal of Korean Society of Disaster and Security
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    • v.15 no.1
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    • pp.1-12
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    • 2022
  • An automatic optimization technique is used to estimate the optimal parameters of the hydrologic model, and different hydrologic response results can be provided depending on objective functions. In this study, the parameters of the event-based rainfall-runoff model were estimated using various objective functions, the reproducibility of the hydrograph according to the objective functions was evaluated, and appropriate objective functions were proposed. As the rainfall-runoff model, the storage function model(SFM), which is a lumped hydrologic model used for runoff simulation in the current Korean flood forecasting system, was selected. In order to evaluate the reproducibility of the hydrograph for each objective function, 9 rainfall events were selected for the Cheoncheon basin, which is the upstream basin of Yongdam Dam, and widely-used 7 objective functions were selected for parameter estimation of the SFM for each rainfall event. Then, the reproducibility of the simulated hydrograph using the optimal parameter sets based on the different objective functions was analyzed. As a result, RMSE, NSE, and RSR, which include the error square term in the objective function, showed the highest accuracy for all rainfall events except for Event 7. In addition, in the case of PBIAS and VE, which include an error term compared to the observed flow, it also showed relatively stable reproducibility of the hydrograph. However, in the case of MIA, which adjusts parameters sensitive to high flow and low flow simultaneously, the hydrograph reproducibility performance was found to be very low.

Development of Correction Formulas for KMA AAOS Soil Moisture Observation Data (기상청 농업기상관측망 토양수분 관측자료 보정식 개발)

  • Choi, Sung-Won;Park, Juhan;Kang, Minseok;Kim, Jongho;Sohn, Seungwon;Cho, Sungsik;Chun, Hyenchung;Jung, Ki-Yuol
    • Korean Journal of Agricultural and Forest Meteorology
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    • v.24 no.1
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    • pp.13-34
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    • 2022
  • Soil moisture data have been collected at 11 agrometeorological stations operated by The Korea Meteorological Administration (KMA). This study aimed to verify the accuracy of soil moisture data of KMA and develop a correction formula to be applied to improve their quality. The soil of the observation field was sampled to analyze its physical properties that affect soil water content. Soil texture was classified to be sandy loam and loamy sand at most sites. The bulk density of the soil samples was about 1.5 g/cm3 on average. The content of silt and clay was also closely related to bulk density and water holding capacity. The EnviroSCAN model, which was used as a reference sensor, was calibrated using the self-manufactured "reference soil moisture observation system". Comparison between the calibrated reference sensor and the field sensor of KMA was conducted at least three times at each of the 11 sites. Overall, the trend of fluctuations over time in the measured values of the two sensors appeared similar. Still, there were sites where the latter had relatively lower soil moisture values than the former. A linear correction formula was derived for each site and depth using the range and average of the observed data for the given period. This correction formula resulted in an improvement in agreement between sensor values at the Suwon site. In addition, the detailed approach was developed to estimate the correction value for the period in which a correction formula was not calculated. In summary, the correction of soil moisture data at a regular time interval, e.g., twice a year, would be recommended for all observation sites to improve the quality of soil moisture observation data.

Development of Continuous Monitoring Method of Root-zone Electrical Conductivity using FDR Sensor in Greenhouse Hydroponics Cultivation (시설 수경재배에서 FDR 센서를 활용한 근권 내 농도의 연속적 모니터링 방법)

  • Lee, Jae Seong;Shin, Jong Hwa
    • Journal of Bio-Environment Control
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    • v.31 no.4
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    • pp.409-415
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    • 2022
  • Plant growth and development are also affected by root-zone environment. Therefore, it is important to consider the variables of the root-zone environment when establishing an irrigation strategy. The purpose of this study is to analyze the relationship between the volumetric moisture content (VWC), Bulk EC (ECb), and Pore EC (ECp) used by plant roots using FDR sensors in two types of rockwool media with different water transmission characteristics, using the method above this was used to establish a method for collecting and correcting available root-zone environmental data. For the experiment, two types of rockwool medium (RW1, RW2) with different physical characteristics were used. The moisture content (MC) and ECb were measured using an FDR sensor, ECp was measured after extracting the residual nutrient solution from the medium using a disposable syringe in the center of the medium at a volumetric moisture content (VWC) of 10-100%. Then, ECb and ECp are measured by supplying nutrient solution having different concentration (distilled water, 0.5-5.0) to two types of media (RW1, RW2) in each volume water content range (0 to 100%). The relationship between ECb and ECp in RW1 and RW2 media is best suited for cubic polynomial. The relationship between ECb and ECp according to volume moisture content (VWC) range showed a large error rate in the low volume moisture content (VWC) range of 10-60%. The correlation between the sensor measured value (ECb) and the ECp used by plant roots according to the volumetric water content (VWC) range was the most suitable for the Paraboloid equation in both media (RW1, RW2). The coefficient of determination the calibration equation for RW1 and RW2 media were 0.936, 0.947, respectively.

Comparative study on efficacies and ingredient contents of different solvent extracts of Insampaedok-san (인삼패독산의 추출용매에 따른 성분함량 및 효능연구)

  • Lim, Hye-Sun;Ha, Hyekyung;Seo, Chang-Seob;Jin, Seong Eun;Kim, Yeji;Jeon, Woo-Young;Yoo, Sae-Room;Shin, In-Sik;Kim, Jung-Hoon;Kim, Seong-Sil;Shin, Na Ra;Lee, Mee-Young;Jeong, Soo-Jin;Kim, Ohn Soon;Shin, Hyeun-Kyoo
    • The Korea Journal of Herbology
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    • v.27 no.6
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    • pp.115-122
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    • 2012
  • Objectives : This study evaluated activities and ingredient contents concerning extracts according to extraction solvents of Insampaedok-san (IS, Renshen bai du-san). Methods : The herbal constituents of IS were extracted with water and 70% ethanol at $100^{\circ}C$ for 2 hr. Using the HPLC system, the six ingredient contents of different solvent extracts of IS were analyzed. The nitric oxide (NO), prostaglandin $E_2$ ($PGE_2$) production and proinflammatory cytokines were measured in RAW264.7 cells stimulated with lipopolysaccharide (LPS). The macrophage-derived chemokine (MDC/CCL22) and regulated on activation normal T-cell expression and secreted (RANTES/CCL5) production were measured in HaCaT and BEAS-2B cells stimulated tumor necrosis factor-${\alpha}$ (TNF-${\alpha}$) and interferon-${\gamma}$ (IFN-${\gamma}$). The activities of glycerol-3-phosphate dehydrogenase (GPDH) and leptin level were measured in 3T3-L1 cells. Results : The calibration curves showed good linearity ($r^2$=1.0000) for different concentration ranges. The contents of liquiritin, naringin, hesperidin, neohesperirin and glycyrrizin in 70% ethanol extracts of IS were relatively higher than that of water extract, however the content of ferulic acid in 70% ethanol and water extract of IS were similar. The extraction solvents of water and 70% ethanol were evaluated inhibitory effect on the production of NO, $PGE_2$, TNF-${\alpha}$ and IL-6 in RAW 264.7 cells. Their extractions were inhibitory effect on production of MDC/CCL22 and RANTES/CCL5 in HaCaT cell and BEAS-2B cell, respectively. In addition, evaluated reduced on GPDH activity and leptin level in 3T3-L1 preadipocyte cell. Conclusions : Our results suggest that IS extracts were inhibitory effects of disease such as inflammation, allergies and obesity.

Improvement of an Analytical Method for Methoprene in Livestock Products using LC-MS/MS (LC-MS/MS를 이용한 축산물 중 살충제 메토프렌의 잔류분석법 개선)

  • Park, Eun-Ji;Kim, Nam Young;Park, So-Ra;Lee, Jung Mi;Jung, Yong Hyun;Yoon, Hae Jung
    • Journal of Food Hygiene and Safety
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    • v.37 no.3
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    • pp.136-142
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    • 2022
  • The research aims to develop a rapid and easy analytical method for methoprene using liquid chromatography-tandem mass spectrometry (LC-MS/MS). A simple, highly sensitive, and specific analytical method for the determination of methoprene in livestock products (beef, pork, chicken, milk, eggs, and fat) was developed. Methoprene was effectively extracted with 1% acetic acid in acetonitrile and acetone (1:1), followed by the addition of anhydrous magnesium sulfate (MgSO4) and anhydrous sodium acetate. Subsequently, the lipids in the livestock sample were extracted by freezing them at -20℃. The extracts were cleaned using MgSO4, primary secondary amine (PSA), and octadecyl (C18), which were then centrifuged to separate the supernatant. Nitrogen gas was used to evaporate the supernatant, which was then dissolved in methanol. The matrix-matched calibration curves were constructed using 8 levels (1, 2.5, 5, 10, 25, 50, 100, 150 ng/mL) and the coefficient of determination (R2) was above 0.9964. Average recoveries spiked at three levels (0.01, 0.1, and 0.5 mg/kg), and ranged from 79.5-105.1%, with relative standard deviations (RSDs) smaller than 14.2%, as required by the Codex guideline (CODEX CAC/GL 40). This study could be useful for residue safety management in livestock products.

Modification and Validation of an Analytical Method for Dieckol in Ecklonia Stolonifera Extract (곰피추출물의 지표성분 Dieckol의 분석법 개선 및 검증)

  • Han, Xionggao;Choi, Sun-Il;Men, Xiao;Lee, Se-jeong;Oh, Geon;Jin, Heegu;Oh, Hyun-Ji;Kim, Eunjin;Kim, Jongwook;Lee, Boo-Yong;Lee, Ok-Hwan
    • Journal of Food Hygiene and Safety
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    • v.37 no.3
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    • pp.143-148
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    • 2022
  • This study was to investigate an analytical method for determining dieckol content in Ecklonia stolonifera extract. According to the guidelines of International Conference on Harmonization. Method validation was performed by measuring the specificity, linearity, precision, accuracy, limit of detection (LOD), and limit of quantification (LOQ) of dieckol using high-performance liquid chromatography-photodiode array. The results showed that the correlation coefficient of calibration curve (R2) for dieckol was 0.9997. The LOD and LOQ for dieckol were 0.18 and 0.56 ㎍/mL, respectively. The intra- and inter-day precision values of dieckol were approximately 1.58-4.39% and 1.37-4.64%, respectively. Moreover, intra- and inter-day accuracies of dieckol were approximately 96.91-102.33% and 98.41-105.71%, respectively. Thus, we successfully validated the analytical method for estimating dieckol content in E. stolonifera extract.