• The Korean Journal of Pesticide Science
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• v.21 no.1
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• pp.68-74
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• 2017

An analytical method for detecting metamifop residue in paddy water, soil, and rice with high performance liquid chromatography (HPLC) was developed. Water was extracted with ethyl acetate before analyzing by HPLC. Soil residues were extracted with acetone under acidic condition and after purifying with $Extrelut^{(R)}$ NT, and silica SPE, the residue was analyzed by HPLC. For residue analysis in rice, the procedure involved extraction with acetone, purification with $Extrelut^{(R)}$ NT, partitioning between acetonitrile/hexane, purification with silica SPE cartridge, and analysis by HPLC. The limit of detection (LOD) was 1.0 ng, limit of quantitation (LOQ) was 3.0 ng, and method limit of quantitation (MLOQ) were 0.001 mg/L for paddy water, 0.01 mg/kg for rice and soil, respectively. Standard calibration curve shows linearity from 0.05 mg/kg to 5.0 mg/kg ($R^2=0.9999$). The recoveries in fortified paddy water were $91.3{\pm}3.5%$ (0.01 mg/L level) and $93.2{\pm}6.3%$ (0.05 mg/L level). The recoveries in fortified paddy soils were $92.5{\pm}4.0%$ (0.1 mg/kg level) and $92.7{\pm}4.0%$ (0.5 mg/kg level) in soil A, while, $102.3{\pm}4.4%$ (0.1 mg/kg level) and $98.9{\pm}7.9%$ (0.5 mg/kg level) in soil B, respectively. The recoveries in fortified rice were $93.0{\pm}6.9%$ (0.1 mg/kg level) and $85.0{\pm}3.5%$ (0.5 mg/kg level). This method was proved to be effective and can be used to determine the metamifop residue in paddy water, paddy soil, and rice.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2003.10a
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• pp.111-124
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• 2003

Processes that cause immobilization of contaminants in soil are of great environmental importance because they may lead to a considerable reduction in the bioavailability of contaminants and they may restrict their leaching into groundwater. Previous investigations demonstrated that pollutants can be bound to soil constituents by either chemical or physical interactions. From an environmental point of view, chemical interactions are preferred, because they frequently lead to the formation of strong covalent bonds that are difficult to disrupt by microbial activity or chemical treatments. Humic substances resulting from lignin decomposition appear to be the major binding ligands involved in the incorporation of contaminants into the soil matrix through stable chemical linkages. Chemical bonds may be formed through oxidative coupling reactions catalyzed either biologically by polyphenol oxidases and peroxidases, or abiotically by certain clays and metal oxides. These naturally occurring processes are believed to result in the detoxification of contaminants. While indigenous enzymes are usually not likely to provide satisfactory decontamination of polluted sites, amending soil with enzymes derived from specific microbial cultures or plant materials may enhance incorporation processes. The catalytic effect of enzymes was evaluated by determining the extent of contaminants binding to humic material, and - whenever possible - by structural analyses of the resulting complexes. Previous research on xenobiotic immobilization was mostly based on the application of $^{14}$ C-labeled contaminants and radiocounting. Several recent studies demonstrated, however, that the evaluation of binding can be better achieved by applying $^{13}$ C-, $^{15}$ N- or $^{19}$ F-labeled xenobiotics in combination with $^{13}$ C-, $^{15}$ N- or $^{19}$ F-NMR spectroscopy. The rationale behind the NMR approach was that any binding-related modification in the initial arrangement of the labeled atoms automatically induced changes in the position of the corresponding signals in the NMR spectra. The delocalization of the signals exhibited a high degree of specificity, indicating whether or not covalent binding had occurred and, if so, what type of covalent bond had been formed. The results obtained confirmed the view that binding of contaminants to soil organic matter has important environmental consequences. In particular, now it is more evident than ever that as a result of binding, (a) the amount of contaminants available to interact with the biota is reduced; (b) the complexed products are less toxic than their parent compounds; and (c) groundwater pollution is reduced because of restricted contaminant mobility.

• Applied Biological Chemistry
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• v.8
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• pp.101-111
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• 1967

Daily doses of phenylmercuric acetate arranged in $30{\gamma}\;(group\;I)$, 3{\gamma}\;(group\;II)$ and $0.3{\gamma}\;(group\;III)$ were administered respectively to rabbits for 90 days. The chief histopathological changes in the organs and the analytical data on mercury residues in the excretion and liver were as follows. 1. Kidney: In group I, severe degrees of vacuolization and cloudy swelling were occurred in the epithelial cells of proximal convoluted tubules and severe cloudy swelling and coagulative necrosis were observed in the proximal straight tubules. There were many hyaline casts in the collecting tubules. In group II, moderate degrees of vacuolization and cloudy swelling were observed in the epithelial cells of proximal convoluted tubules and moderate cloudy swelling and coagulative necrosis were encountered in the proximal straight tubules. A little numbers of hyaline casts were located in the lumen of collecting tubules. In group III, slight degree of cloudy swelling were observed in the epithelial cells of proximal convoluted and straight tubules. 2. Liver: In group I, cloudy swelling, fatty changes and coagulative necrosis were observed in the central zone of hepatic lobules. Dissociation of hepatic cell cords was encountered. Hyperplsia of hepatic cells were remarkable in group II. No Pathological changes were observed in group III. 3. Spleen: Deposition of hemosiderin pigment was prominant in group I and small amount of the pigment was observed in group II. There were no pathological changes in group III. 4. Adrenal, colon and heart: No pathological changes were detected in all 3 groups. 5. In an average about 76.5% of mercury was excreted from group I, 85.4% from group II and 79.8% from group III. 6. Mercury content in the liver was 0.0348 g in group I, 0.00378 g and 0.00066 g in group II and group III respectively. 7. In general, as to increased mercury doses the concentration of mercury accumulation in the liver became higher, how·ever, the accumulation quantity against a total amount of mercury doses showed an adverse trend. In other word, the quantity of mercury accumulation was not increased proportionately by higher dose of mercury.

• Korean Journal of Weed Science
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• v.15 no.1
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• pp.85-98
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• 1995

Six malformin B's produced by Aspergillus niger van Tiegh. were separated by HPLC. Their structures determined by the methods of amino acid analyses, mass spectrometry, and two-dimensional NMR were revealed as cyclic pentapeptides structurally related to malformin $A_1$. Both the NMR and MS/MS data suggest that the respective structures of separated malformin B's were as follows; cyclo-D-Cys-D-Cys-L-Val-D-Leu-L-allo-Ile for $B_{1a}$, cyclo-D-Cys-D-Cys-L-Val-D-Leu-L-Leu for $B_{1b}$, cyclo-D-Cys-D-Cys-L-Val-D-Val-L-Leu for $B_2$, cyclo-D-Cys-D-Cys-L-Val-D-Ile-L-Leu for $B_3$, cyclo-D-Cys-D-Cys-L-Val-D-Ile-L-Ile for $B_4$, and cyclo-D-Cys-D-Cys-L-Val-D-Val-L-Ile for $B_5$. Among the malformin B's, the structure of $B_{1b}$ was the same as that of malformin $A_3$ or C. All the malformin B's showed physiological activities in the two assay systems using corn(Zea mays L.) roots and mung bean(Phaseolus aureus Roxb.) hypercotyl segments. The malformin B's with molecular weight 529 were more effective for inducing corn root curvature than those with molecular weight 515. The difference in molecular weight of malformin B's, i.e., the retention time on HPLC, results in the polarity change of the whole malformin molecule which affects the revealation of the malformin activities. In addition, the disulfide form of the malformin B's gives the rigidity of the molecule, whereas the combination of the fourth and the fifth amino acid residues provides the optimal three-dimensional configuration to the malformin receptor of plants. Presumably, these two factors are appeared to be essential for the greatest physiological activity of malformin B's. malformin $B_{1a}$ caused the corn root curvature by 90% at a concentration of $0.25{\mu}M$. However, such differential activities with molecular weight of 529 or 515 of malformin B's were not found in the mung bean hypercotyl segment test. Maximum stimulation of mung bean hypercotyl growth was observed at $0.1{\mu}M$ concentration of malformin B's. The growth of the segments treated with $B_5$ was 154% greater than that of the control.

• The Korean Journal of Pesticide Science
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• v.11 no.2
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• pp.95-105
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• 2007

The aim of this study was to determine the residual amounts of PAHs in environmental samples such as crop, soil and water collected from paddy, upland fields and forestlands near industrial zone and/or a thermal power plant in South Korea. All of the samples were analyzed by GC-mass spectrometer. The average contents of total PAHs in soil samples were 140.2 ${\mu}g\;kg^{-1}$ and the range was from 4.3 to $662.9{\mu}g\;kg^{-1}$. The detection of benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene and dibenzo(a,h) anthracene which have strong carcinogenecity was ranged from 14.2 to 167.8 ${\mu}g\;kg^{-1}$. The residual amounts and detection frequency of PAHs in soil samples from the iron and heavy industrial areas near Pohang and Busan were 3-folds more than those of the other areas. Amounts of PAHs in upland soil samples was 1.5 folds higher than those of paddy soil samples, suggesting that it may be related to the content of organic matter in soil. The average contents of total PAHs in crop samples were 9.7 ${\mu}g\;kg^{-1}$ which ranged from 4.5 to 52.2 ${\mu}g\;kg^{-1}$. However, the residual amounts of PAHs in water samples were not detected. These results showed that soils and crops were slightly contaminated with PAHs. Therefore, the investigation should be continued for evaluating a safety or risk assessment through expansion of regions and crops.

• Korean Journal of Soil Science and Fertilizer
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• v.7 no.2
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• pp.71-97
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• 1974

Many studies on the changes of the materials in the water-logged paddy soil have been reported, but there will be several problems to apply them on the field soil. The main differences between the method of soil packed in beaker or column tube to that of natural field furrow slice are with or without of the rice root and the effect of water percolation. On the other hand, the mechanism of the water percolation on the changes of material in the natural field furrow slice are gradually understood. The purpose of this experiment is to know the effect of the rice cultivation on the chemical and physical changes of material in the water-logged paddy soil. Obtained results are as follows. 1. The physical and chemical changes on the water-logged paddy soil in the non-planted control-plot were nearly the same as the beaker or column tube experiment, while in the planted plot, slightly altered patterns were observed. 2. The relation between the number of tillers and total cation, $Ca^{{+}{+}}$, $Mg^{{+}{+}}$, Fe and Mn in the leachate showed very high significance. T hisresult showed that the leaching of those cation was promoted by growing of the rice r- of the rice root. 3. On the other hand, the concentration of the potassium, silica and phosphorus in leachates was gradually decreased and that of $NH_4$-N could not detect after the stage of active tillering. These facts revealed that such components were absorbed by rice plant. 4. The highly significant correlation between the number of tillers and the concentration of the total cation, $Ca^{{+}{+}}$, $Mg^{{+}{+}}$, $Fe^{{+}{+}}$, Fe and Mn in the percolated water was observed except that of $Mg^{{+}{+}}$. It was also showed that the rice root promoted the leaching of those cation. 5. The very high significance in the correlation between $HCO_3{^-}$ and the number of tillers indicated that the higher activity of the rice root was, the more $HCO_3{^-}$ concentration in the leachate was increased. 6. The relationship between the $HCO_3{^-}$ and the total cation, $Ca^{{+}{+}}$, $Mg^{{+}{+}}$, $Fe^{{+}{+}}$, Fe and Mn was appeared very highly significant. $HCO_3{^-}$, the metabolite of the rice root, promoted the leaching of $Ca^{{+}{+}}$, $Mg^{{+}{+}}$, $Fe^{{+}{+}}$ and Mn. This fact might be a result that these cations were leached as the form of bicarbonate. 7. The iron in the leachate was the form of $Fe^{{+}{+}}$ and the correlation between $Fe^{{+}{+}}$ and $HCO_3{^-}$ was very highly significant. This result indicated that it seemed to be ferrous bicarbonate when it is leached out. 8. In the rhizosphere, ferrous iron was decreased gradually and the concentration of glucose was as high as 2 to 3 times in comparison with the other parts of the soil. These facts were the same as the previous reports in which rhizosphere was oxidized by the oxigen excreted from the root, and was enriched by the organic matter which was also excreted from the root and accumulated residues of the root. 9. ${\beta}$-Glucosidase and phosphatase activity in the rhizosphere was higher than that of the other parts of the soil. This facts might be attributed to the vigorous activity of microorganism in the rhizosphere where glucose concentration was high. 10. The pH in the leachate of the planted plot was lower than that of control, and the Eh on the planted soil was elevated in the last stage.