• Journal of the Korean Chemical Society
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• v.37 no.5
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• pp.513-522
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• 1993

The purpose of this study is to optimize the selectivity of mobile phase solvents for separation of 25 phenols in reversed phase liquid chromatography and to accomplish the simultaneous preconcentration and separation of trace phenols from water samples. Phenols used in this study were classified into three groups, chloro-, methyl-, and nitrophenols. Quaternary solvent mobile phases were employed to improve the selectivity. Overlapping resolution maps(ORM) as a statistical simplex techniques was used to predict the optimum solvent system. Additional criterion such as pH and temperature were also investigated. In order to improve the resolution and decrease the analysis time, isoselective multisolvent gradient elution system was employed with ORM-Prism method. The simultaneous preconcentration and separation of trace phenols from water samples were performed by using XAD-2/Dowex 1-X8 tandem column. When the extraction efficiency was evaluated by sampling up to 1 L of distilled water, recovery of the phenols, except phenol, was above 90% and the limit of detection of the phenols was 5 ppb. The XAD-2/Dowex 1-X8 method was superior to C18 cartridge in terms of recovery and selectivity.

• Journal of the Korean Chemical Society
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• v.63 no.6
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• pp.415-419
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• 2019

Fipronil is an insecticide that belongs to the N-phenylpytazole and has been used mainly for an insect pest control. However, it is known that acute poisoning of the human body causes various symptoms such as dizziness, muscle weakness, dyspnea, skin irritation, and increased heart rate. Lately, eggs containing fipronil have been distributed and toxic problems are spreading around the world. In this study, we tried to develop analytical methods to evaluate the exposure of fipronil and fipronil sulfone in animal serum samples. The differences according to mobile phase and the results of liquid - liquid extraction and solid phase extraction pretreatment method were compared. Distilled water (A) and acetonitrile (B) were selected for the mobile phase, and the pretreatment method was determined by solid phase extraction. As a result of the method validation, the intra-day / inter-day accuracies were 82.2~114.1% and the precisions were less than 20%. The detection limit was 0.027 ng/ml for fipronil and 0.087 ng/ml for fipronil sulfone. The linearity obtained was satisfying, with a coefficient of determination (r²) higher than 0.99. The concentrations in some animal sera were determined using the methods of analysis for fipronil and fipronil sulfone in animal sera developed in this study. Using the method developed in this study, it could be used as an analytical method for human bio-monitoring of fipronil and fipronil sulfone as well as animal serum.

• Korean Journal of Environmental Agriculture
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• v.35 no.3
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• pp.166-174
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• 2016

BACKGROUND: The current study developed a monitoring method of 6 veterinary antibiotics (amoxicillin, ampicillin, enrofloxacin, tetracycline, chlortetracycline, oxytetracycline) in agricultural soils using liquid chromatography-tandem mass spectrometry (LC-MS/MS) in positive electrospray ionization mode.METHODS AND RESULTS: Sample preparation was carried out using acidic acetonitrile and citrate salts followed by purification with dispersive solid phase extraction (d-SPE). Separation on Eclipse Plus C₁₈ column was conducted in gradient of the mobile phase, 0.1% formic acid and 5 mM ammonium formate in methanol (A) and 0.1% formic acid and 5 mM ammonium formate in distilled water (B). The linearity of the matrix-matched calibrations expressed as the coefficient of determination was good with R²≥0.9900. The limit of quantifications (LOQs) ranged from 0.5 to 10 μg/kg for all analytes. Analysis of 51 agricultural soil samples taken in the Republic of Korea revealed concentrations less than 1.9 μg/kg for enrofloxacin, 75.5 μg/kg for chlortetracycline.CONCLUSION: The method was successfully applied to monitor 6 veterinary antibiotics from 51 field incurred agricultural soil samples in 17 provincial areas throughout the Republic of Korea. The developed method was simple, easy, and versatile and can be used for monitoring various veterinary antibiotics in soil.

• Journal of Soil and Groundwater Environment
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• v.20 no.6
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• pp.55-61
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• 2015

Based on the literature study for the determination of perchlorate in soil we chose the ion chromatography as a measurement method and decided to use 70 mM KOH as an eluent to avoid the interference derived from the co-elution of pyrophosphate (P₂O₇⁴⁻), tripolyphosphate (P₃O₁₀⁵⁻). Also we proposed to use air dried soil through 0.15 mm sieve and distilled water as an extractant. Under the these basic concepts, we carried out the experiments to set up the detail procedure like solid to liquid ratio (S/L ratio), extraction time, device for extraction and indicating factors for quality control (e.g. precision, accuracy, MDL, LOQ). In case of time and device for extraction, 5 hours of mechanical shaking or 1 hour of centrifugation showed better precision and accuracy than that of sonication for 1 hour According to these results, we proposed the extraction method combining 5 hours of mechanical shaking with 1 hour of centrifugation. From the aspect of S/L ratio, the ratio of 1/2 or 1/3 showed resonable precision and accuracy. In case of the ratio of 1/2, there would be some problems in the separation process when the proportion of fine particle is high. Therefore, we proposed the extraction ratio of solid to liquid as 1/3 instead of 1/2. With the consideration of cost effectiveness and soil salinity, we proposed the use of cartridge for removing the interfering anions like chloride, sulfate and carbonate in specific sample such as saline soil.

• Analytical Science and Technology
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• v.25 no.1
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• pp.83-90
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• 2012

The objective of the study was to estimate the measurement uncertainty associated with determination of creatinine (Cr) in urine samples by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Centrifuged urine samples (10 ${\mu}L$) were diluted with 390 ${\mu}L$ of distilled water. To 20 ${\mu}L$ aliquots of diluted urine samples, 30 ${\mu}L$ of internal standard solution (Cr-$d_3$, 5 ${\mu}g/mL$) and 10 ${\mu}L$ of acetonitrile were added and filtered. The samples (1 ${\mu}L$) were introduced into LC-MS/MS with no further pretreatment. Cr was separated on a multi-mode ODS column (Scherzo SM-C18, 75 ${\times}$ 2.0 mm I.D., 3 ${\mu}m$) and quantified by LC-MS/MS operating in MRM mode (Cr, m/z 114.0${\rightarrow}$ 86.0; Cr-$d_3$, m/z 117.0${\rightarrow}$ 89.1). The four factors that contribute uncertainty to the final result were extracted and evaluated. The principal factors of contribution to combined standard uncertainty were sample dilution, calibration curve and repeatability, while the preparation of standard solution was only a minor factor. Relative extended uncertainty of the measured concentration was 14.2% in a real urine sample.

• Analytical Science and Technology
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• v.30 no.5
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• pp.295-302
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• 2017

This study presents a method validation for extraction and quantitative analysis of levulinic acid in soy sacues using high performance liquid chromatograph-photodiode array detector (HPLC-PDA). The levulinic acid in samples were extracted with distilled water, and then purified with C18 Sep-Pak cartridge. The calibration curves showed good linearity (R > 0.999) in a relatively wide concentration range ($2.5-400{\mu}g/mL$). Mean recoveries and relative standard deviation (RSD) of levulinic acid spiked in soy sauce samples at different spiking levels ($2.5-400{\mu}g/mL$; 6 point). Recoveries were 87.58-97.26 % with RSD less than 15 %, and limit of detection (LOD) and limit of quantification (LOQ) were 0.64 and $1.64{\mu}g/mL$, respectively. According to monitoring result with the established method, levulinic acid was found in 43 of 59 domestic commercial soy sauces, soy sauce based sauces and seasoned meats. The contamination levels were 0.44-1.23 mg/mL for soy sauces, 0.03-0.83 mg/mL for soy sauce based sauces and 8.43-38.94 mg/mL for seasoned meats. The results indicated to be rapidly and accurately qualifying levulinic acid and can be used as a suitable quality control method for soy sauce and soy sauce related commodities.

• Analytical Science and Technology
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• v.32 no.2
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• pp.35-47
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• 2019

In this study, high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was employed to detect 26 antidiabetic compounds in adulterated dietary supplements using a simple, selective method. The work presented herein may help prevent incidents related to food adulteration and restrict the illegal food market. The best separation was obtained on a Shiseido Capcell Pak(R) C18 MG-II ($2.0mm{\times}100mm$, $3{\mu}m$), which improved the peak shape and MS detection sensitivity of the target compounds. A gradient elution system composed of 0.1 % (v/v) formic acid in distilled water and methanol at a flow rate of 0.3 mL/min for 18 min was utilized. A triple quadrupole mass spectrometer with an electrospray ionization source operated in the positive or negative mode was employed as the detector. The developed method was validated as follows: specificity was confirmed in the multiple reaction monitoring mode using the precursor and product ion pairs. For solid samples, LOD ranged from 0.16 to 20.00 ng/mL and LOQ ranged from 0.50 to 60.00 ng/mL, and for liquid samples, LOD ranged from 0.16 to 20.00 ng/mL and LOQ ranged from 0.50 to 60.00 ng/mL. Satisfactory linearity was obtained from calibration curves, with $R^2$ > 0.99. Both intra and inter-day precision were less than 13.19 %. Accuracies ranged from 80.69 to 118.81 % (intra/inter-day), with a stability of less than 14.88 %. Mean recovery was found to be 80.6-119.0 % and less than 13.4 % RSD. Using the validated method, glibenclamide and pioglitazone were simultaneously determined in one capsule at concentrations of 1.52 and 0.53 mg (per capsule), respectively.

• Proceedings of the Korean Society of Crop Science Conference
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• 2022.10a
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• pp.114-114
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• 2022

There are 28 families and 166 species of exotic weeds on agricultural land and among these, 23 families and 80 species of exotic weeds occur on pastures. Among them, the Solidago altissima is a perennial weed belonging to the asteraceae family and it is an exotic weed that spreads to the surrounding area using methods such as high seed production, vegetative propagation using underground rhizomes and allelochemical. Accordingly, in 2009, the Ministry of Environment designated it as an ecosystem-disrupting species. This study was conducted to obtain basic data about the effects of S.altissima derived allelochemicals on forage crops. The root of S.altissima was separated, dried in the shade and then pulverized to prepare an root powder. Powder was repeatedly extracted with methanol for 3 days and concentrated under reduced pressure to obtain an root methanol extract. Dissolve the extract in distilled water, dispense it in a separate-funnel and proceed with liquid-liquid extraction by adding equal amounts of n-haxane (Hex), chloroform (CHCI₃), ethyl acetate (EtoAC), and butanol (BuOH) in order of increasing polarity. A seed-bioassay was performed using fractions for each solvent, followed by separation and purification by silica gel column chromatography. As a result of the fraction germination test for each solvent, the IC₅₀ values using the fresh weight of each fraction were 898.3 mg L^-1, 676.3 mg L^-1, 1160 mg L^-1 and 1360 mg L^-1. CA, CB, and CC fractions were obtained through primary silica gel column chromatography that used CHCI₃ fraction. As a result of seed-bioassay using each fraction, the IC₅₀ values for the fresh weight of each fraction was 537.3 mg L^-1, 1280 mg L^-1 and 1947 mg L^-1. Based on this, 5 fractions were obtained as a result of secondary silica gel column chromatography using the CA fraction. A seed-bioassay was performed, as a result, the lowest IC₅₀ value was calculated as 226.7 mg L^-1 in the CAE fraction. Based on this, the fraction was analyzed by GC-MS. The results of this study can be used as basic research data on the effects of weeds on forage crops and allelochemicals secreted from S. altissima.

• Journal of Food Hygiene and Safety
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• v.28 no.1
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• pp.63-68
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• 2013

Ethyl carbamate (EC) is a contaminant generated in the fermentation processes of various fermented foods. In this study, residue levels of EC in 95 alcoholic beverage samples were determined by using Gas Chromatography/Tandem Mass Spectrometry (GC/MS/MS). All the samples were purified by a liquid-liquid extraction (LLE) method using dichloromethane. The LLE method enables an improvement in time and cost to detection and specificity over the conventional extraction methods. The limits of detection and quantification (LOD and LOQ) to analyze EC were 1.3 and 4.0 ng/mL, respectively. The recovery rates of EC were ranged from 90.0 to 97.5% at the levels of 50, 100, and 500 ug/L. Among traditional grain-based alcoholic beverage samples (n = 34), the average residue levels of EC in takju, yakju, and cheongju were 0.63, 7.01, and 14.11 ug/L, respectively. Among fruit-based alcoholic beverage samples (n = 48), those of EC in japanese apricot spirits, bokbunjaju, grape wines, and other fruit wines were 79.18, 1.66, 2.64, and 2.39 ug/L, respectively. Among distilled or diluted alcoholic beverage samples (n = 13), those of EC in soju (distilled or diluted), general distillates, liquors, and brandies were 0, 3.30, 8.20, and 8.52 ug/L, respectively. Therefore, this study reports that the residue levels of EC in the alcoholic beverages, distributed in the current domestic markets, did not reach its maximum allowed levels of 30 and 400 ug/L established for grape and fruit wines in Canada, respectively.

• Analytical Science and Technology
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• v.28 no.3
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• pp.228-235
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• 2015

The efficiency and applicability of the solid phase extraction disk method in a ²²⁶Ra analysis were examined by the gamma ray spectrometer (GRS) method using a Marinelli beaker and the liquid scintillation counter (LSC) method for groundwater. The recovered ²²⁶Ra, which was filtered by the solid phase extraction disk, was analyzed using gamma ray spectrometer The disks, which were pretreated for caulking the daughter nuclide, were sealed with polyethylene film. Distilled water was used for the blank value of the ²²⁶Ra activity. The recovery values of ²¹⁴Bi and ²¹⁴Pb in the solid phase extraction disk, which used ²²⁶Ra standard material, were 80% (295.21 Kev) and 104% (351.92 Kev), respectively, which were higher than 75% determined by the LSC. The injection of nitrogen gas into the measuring chamber reduced the interference values by about 10%. The detection limits of the ²²⁶Ra activity in a blank sample of 5 L were 0.17~0.40 pCi/L after 80,000 seconds of measuring time. The relationship of the ²²⁶Ra activity in the solid phase extraction disk method and in the LSC method in seven groundwater samples showed a correlation coefficient value 0.987, which implies the applicability of the solid phase extraction disk method. The results showed that ²²⁶Ra activity in groundwater using the solid phase extraction disk method has the following benefits: simple pretreatment, time saving, high recovery values, a low detection limit, and so on. Compared with the LSC method and the GRS method using the Marinelli beaker for the ²²⁶Ra analysis, the solid phase extraction disk method could be useful in groundwater samples with low levels of activities of radionuclides because the method is not restricted by the volume of the sample.