• Korean Journal of Environmental Agriculture
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• v.40 no.4
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• pp.353-358
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• 2021

BACKGROUND: Prochloraz has been widely used as an imidazole fungicide on fruits and vegetables in Korea. Analytical approaches to evaluate prochloraz residues in herbal medicine are required for their safety management. In this study, we developed a GC-ECD method for quantitative determination of prochloraz in Platycodi Radix. The metabolite 2,4,6-trichlorophenol (2,4,6-T) was used as a target compound to evaluate total prochloraz residues as it is categorized to a representative residue definition of prochloraz. All residues containing 2,4,6-T were converted to 2,4,6-T and subjected to GC-ECD. METHODS AND RESULTS: In order to verify the applicability, the method was optimized for determining prochloraz and it metabolite 2,4,6-T in Platycodi Radix. Prochloraz and its metabolite 2,4,6-T residuals were extracted using acetone. The extract was diluted with and partitioned directly into dichloromethane to remove polar co-extractives in the aqueous phase. The extract was decomposed to 2,4,6-T, and then the partitioned ion-associate was finally purified by optimized aminopropyl solid-phase extraction (SPE). The limits of quantitation of the method (MLOQs) were 0.04 mg/kg and 0.02 mg/kg, respectively for prochloraz and 2,4,6-T, considering the maximum residue level (MRL) of prochloraz as 0.05 mg/kg in Platycodi Radix. Recovery tests were carried out at two levels of concentration (MLOQ, 10 MLOQ) and resulted in good recoveries (82.1-89.7%). Good reproducibilities were obtained (coefficient of variation < 2.8%), and the linearities of calibration curves were reasonable (r² > 0.9986) in the range of 0.005-0.5 ㎍/mL. CONCLUSION(S): The method developed in this study was successfully validated to meet the guidelines required for quantitative determination of pesticides in herbal medicine. Thus, the method could be useful to monitor prochloraz institutionally in herbal medicine.

• Journal of Soil and Groundwater Environment
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• v.13 no.1
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• pp.77-91
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• 2008

In this study, we developed a technique of applying DRASTIC, which is the most widely used tool for estimation of groundwater vulnerability to the aqueous phase contaminant infiltrated from the surface, and a groundwater flow model jointly to assess groundwater contamination potential. The developed technique is then applied to Buyeo-eup area in Buyeo-gun, Chungcheongnam-do, Korea. The input thematic data of a depth to water required in DRASTIC model is known to be the most sensitive to the output while only a few observations at a few time schedules are generally available. To overcome this practical shortcoming, both steady-state and transient groundwater level distributions are simulated using a finite difference numerical model, MODFLOW. In the application for the assessment of groundwater vulnerability, it is found that the vulnerability results from the numerical simulation of a groundwater level is much more practical compared to cokriging methods. Those advantages are, first, the results from the simulation enable a practitioner to see the temporally comprehensive vulnerabilities. The second merit of the technique is that the method considers wide variety of engaging data such as field-observed hydrogeologic parameters as well as geographic relief. The depth to water generated through geostatistical methods in the conventional method is unable to incorporate temporally variable data, that is, the seasonal variation of a recharge rate. As a result, we found that the vulnerability out of both the geostatistical method and the steady-state groundwater flow simulation are in similar patterns. By applying the transient simulation results to DRASTIC model, we also found that the vulnerability shows sharp seasonal variation due to the change of groundwater recharge. The change of the vulnerability is found to be most peculiar during summer with the highest recharge rate and winter with the lowest. Our research indicates that numerical modeling can be a useful tool for temporal as well as spatial interpolation of the depth to water when the number of the observed data is inadequate for the vulnerability assessments through the conventional techniques.

• Journal of Korean Society of Environmental Engineers
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• v.33 no.6
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• pp.396-404
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• 2011

An investigation on the removals of PAH-quinone compounds, which are commonly produced from the biological and/or chemical treatments of PAH-contaminated soils, from the aqueous phase via birnessite (${\delta}-MnO_2$)-mediated oxidative transformation is described. It was demonstrated that acenaphthenequinone (APQ), p-PAH quinone can be removed via birnessite-mediated oxidative-coupling reactions, and anthraquinone (AQ) and 1,4-naphthoquinone (1,4-NPQ), o-PAH quinones were efficiently removed by birnessite-mediated cross-coupling reactions in the presence of catechol (CAT) as a reactive mediator. The removals of PAH-quinone compounds followed pseudo-first-order reactions, and the rate constant (k, $hr^{-1}$) for the removals of 1,4-NPQ under the experiment conditions (1,4-NPQ = 10 mg/L, CAT = 50 mg/L, ${\delta}-MnO_2$ = 1.0 g/L, pH 5, Reaction time = 6~96 hr) was 0.0426, which was about 4 times lower than that of APQ (0.173). With the observed pseudo-first order rate constants with respect to birnessite loadings under the same experimental conditions, the surface-normalized specific rate constant, $K_{surf}$, for 1,4-NPQ was determined to be $8.5{\times}10^{-4}L/m^2{\cdot}hr$. The analysis of the kinetic data with respect to birnessite loading indicated that the cross-coupling reactions of 1,4-NPQ consist of two different reaction steps over time and the results have also been discussed in terms of the reaction mechanisms.

• The Korean Journal of Pesticide Science
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• v.14 no.2
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• pp.95-103
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• 2010

Fomesafen is a selective herbicide, and used to control annual and perennial broad-leaf grass on soybean and fruit fields in USA and China, but not introduced in Korea yet. So, MRL (Maximum Residue Level), and analytical method of fomesafen were not establishment in Korea. Therefore, this experiment was conducted to establish a determination method for fomesafen residue in crops using HPLC-UVD/MS. Fomesafen residue was extracted with acetone from representative samples of five raw products which comprised hulled rice, soybean, apple, green pepper, and Chinese cabbage. The extract was diluted with saline water, and dichloromethane partition was followed to recover fomesafen from the aqueous phase. Florisil column chromatography was additionally employed for final clean up of the extract. The fomesafen was quantitated by HPLC with UVD, using a Shiseido CAPCELL-PAK UG C18 column. The crops were fortified with fomesafen at 3 levels per crop. Mean recovery ratio were ranged from 87.5% for a 0.4 ppm in hulled rice to 102.5% for a 0.4 ppm in apple. The coefficients of variation were ranged from 0.6% for a 2.0 ppm in hulled rice to 7.7% for a 0.04 ppm in green pepper. Quantitative limit of fomesafen was 0.04 mg/kg in representative 5 crop samples. A LC/MS with selected-ion monitoring was also provided to confirm the suspected residue. Therefore, this analytical method was reproducible and sensitive enough to determine the residue of fomesafen in agricultural commodities.

• Korean Journal of Environmental Agriculture
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• v.37 no.2
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• pp.104-116
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• 2018

BACKGROUND: This experiment was conducted to establish a simultaneous analysis method for 7 kinds of herbicides in 3 different classes having similar physicochemical property as diphenyl ether(bifenox and oxyfluorfen), dinitroaniline (ethalfluralin and trifluralin), and chloroacetamide (metolachlor, pretilachlor, and thenylchlor) in crops using GC-ECD/MS. METHODS AND RESULTS: All the 7 pesticide residues were extracted with acetone from representative samples of five raw products which comprised apple, green pepper, Kimchi cabbage, hulled rice and soybean. The extract was diluted with saline water and directly partitioned into n-hexane/dichloromethane(80/20, v/v) to remove polar co-extractives in the aqueous phase. For the hulled rice and soybean samples, n-hexane/acetonitrile partition was additionally employed to remove non-polar lipids. The extract was finally purified by optimized Florisil column chromatography. The analytes were separated and quantitated by GLC with ECD using a DB-1 capillary column. Accuracy and precision of the proposed method was validated by the recovery experiment on every crop samples fortified with bifenox, ethalfluralin, metolachlor, oxyfluorfen, pretilachlor, thenylchlor, and trifluralin at 3 concentration levels per crop in each triplication. CONCLUSION: Mean recoveries of the 7 pesticide residues ranged from 75.7 to 114.8% in five representative agricultural commodities. The coefficients of variation were all less than 10%, irrespective of sample types and fortification levels. Limit of quantitation (LOQ) of the analytes were 0.004 (etahlfluralin and trifluralin), 0.008 (metolachlor and pretilachlor), 0.006 (thenylchlor), 0.002 (oxyfluorfen), and 0.02 (bifenox) mg/kg as verified by the recovery experiment. A confirmatory technique using GC/MS with selected-ion monitoring was also provided to clearly identify the suspected residues. Therefore, this analytical method was reproducible and sensitive enough to determine the residues of bifenox, ethalfluralin, metolachlor, oxyfluorfen, pretilachlor, thenylchlor, and trifluralin in agricultural commodities.

• Journal of Soil and Groundwater Environment
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• v.6 no.4
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• pp.51-59
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• 2001

Column and box tests were performed to investigate the removal efficiency of NAPL using the surfactant enhanced flushing In heterogeneous medium. Homogeneous Ottawa sand and heterogeneous soil were used to verify the increase of remediation efficiency for the surfactant enhanced flushing in column test. Box tests with two different heterogeneous sub-structure were performed to quantify the capability of the surfactant enhanced flushing as a remediation method to remove NAPL from the heterogeneous medium. Two different grain size sand layers were repeated in the box to simulate the heterogeneous layer formation and the modified fault structure was built to simulate the fault system in the box. O-xylene as a LNAPL and PCE as a DNAPL were used and oleamide as a non-ionic surfactant. The maximum NAPL effluent concentration with 1% oleamide flushing in the homogeneous column test increased about 460 times compared to that with only water flushing and about 250 times increased in the real soil column test. In heterogeneous medium, the maximum effluent concentration increased about 150 times in 1% oleamide flushing and most of NAPL were removed from the box within 8 pore volume flushing, suggesting that the removal efficiency increased very much compared to in only water flushing. Results investigated the capability of the surfactant enhanced remediation method to remove NAPL even in heterogeneous medium.

• Journal of the Korean Society of Groundwater Environment
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• v.5 no.1
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• pp.44-55
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• 1998

Imgok creek is the most severly polluted one out of the streams which have been being polluted by acid drainages from the abandoned coal mines in the Gangdong-Myeon area, the central part of the so called Gangreung coal field. Imgok creek is being mainly polluted by the drainage from Youngdong coal mine, which supplies such pollutants as Mg, Fe, Al, Si, Ca, Mn, and SO$_4$as major dissolved components and Cr, Co, Ni, Cu, Zn, Rb, Sr, Cd, Pb, and U as minor dissolved components. After the influx, the pollutants migrate mainly as dissolved solid, rather than as suspended solids along Imgok creek. The suspended solids in Imgok creek are very rich in Fe and Al, indicating that they mainly consist of the precipitates of present and past from the polluted water. Most of the dissolved components in the stream waters of Imgok creek removed from the aqueous phase by precipitation and dilution before reaching the East Sea, so that water quality of the downstreams of Imgok creek is very similar to that of unpolluted tributaries. It suggests that Imgok creek itself is now being severly polluted by the acid drainages from the abandoned coal mines, but the East Sea is relatively safe from the same pollution. The estuary and sea waters around the Goonseon estuary, which accepts Imgok creek water, certainly show no significant difference in chemical compositions from the mean oceanic water. The bottom sediments at the sampling sites of the sea waters also show no significant trend of their component variation, especially the variations of Fe, SO$_4$ and Al concentrations. These facts again supper that the acid mine drainage is not considerablly polluting the East Sea. However, the tributaries supplying the fresh water to the Imgok creek will be certainly polluted by the acid mine drainage as time passes and pollutants will have more chance to migrate in significant amount to the downstream area, which all can be a real threats to the East Sea on the pollution possibility. Therefore, it is suggested that urgently required are not only water quality and environmental improvement of the severely polluted Imgok creek but also preparation of the measures on the possible future pollution of the East Sea by the acid drainage from the abandoned coal mines in the area, while the East Sea is still not much affected by the pollution of the same kind.

• Journal of Korean Society of Environmental Engineers
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• v.28 no.6
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• pp.667-676
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• 2006

The reduction of $Hg^{2+}$ in the aqueous phase results in the production of dissolved gaseous mercury(DGM), and the volatilization of DGM has been identified as an important mechanism for the loss of Hg from waterbodies to the atmosphere. Although mercury emission in the world is known to be mostly from Asia, there have been few studies of measuring DGM concentrations in lakes in Asia. In this study, DGM concentrations were measured at Juam reservoir($35^{\cir}00'N,\;127^{\circ}14'E$), Korea. The results showed that the average concentrations of DGM at the upper and down stream of the lake during summer time were $95{\pm}8\;and\;130{\pm}15$ pg/L, respectively and the concentration of total mercury(TM) at the upper and down stream was $2.1{\pm}0.7,\;1.7{\pm}0.3$ ng/L respectively. Average DGM concentration during summer time($101{\pm}14pg/L$) was approximately 5.5 times higher than that during fall($18{\pm}0.1pg/L$). The DGM concentrations ai the midstream decreased from 32 to 13.7 pg/L during rain event, while the TM concentrations increased from 2.2 ng/L to 2.7 ng/L indicating the deposition of mercury from the atmosphere. Also, the diurnal patterns between DGM concentrations and UV intensities were observed. Water temperatures and DOC concentrations were significantly related to DGM concentrations, while TM concentrations were negatively related to DGM concentrations(p<0.0001). Comparing with the study of Dill et al.,(2006) the average concentrations of DGM $(109{\pm}15pg/L)\;and\;TM(2.2{\pm} 0.4ng/L)$ at Juam reservoir were approximately 3 and 2.2 times higher than those measured in other lakes(DGM: $38{\pm}16pg/L$, TM: $1.0{\pm}1.2ng/L$).

• Journal of Korean Society of Environmental Engineers
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• v.28 no.12
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• pp.1337-1346
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• 2006

Soil humin is the insoluble fraction of humic materials and play an important roles in the irreversible sorption of hydrophobic organic contaminants onto soil particles. However, there have been limited knowledge about the sorption and chemical properties of humin due to the difficulties in its separation from the inorganic matrix(mainly clays and oxides). In this study, de-ashed soil humins($Hu_1-Hu_6$) were isolated from a soil residues(Crude Hu) after removing alkali-soluble organic fractions followed by consecutive dissolution of the mineral matrix with 2%-HF for 2 hr. The humin samples were characterized by elemental analysis and $^{13}C$ NMR spectroscopic method and their sorption-desorption behavior for 1-naphthol were investigated from aqueous solution. The results were compared one another and that with peat humin. $^{13}C$ NMR spectra features indicate that the soil humin molecules are mainly made up of aliphatic carbons(>80% in total carbon) including carbohydrate, methylene chain. Freundlich sorption parameter, n was increased from 0.538 to 0.697 and organic carbon-normalized sorption coefficient(log $K_{OC}$) values also increased from 2.43 to 2.74 as inorganic matrix of the soil humin removed by HF de-ashing. The results suggest that inorganic phase in humin plays an important, indirect role in 1-naphthol sorption and the effects on the sorption non-linearity and intensity are analyzed by comparison between the results of soil humin and peat humin. Sorption-desorption hysteresis were also observed in all the humin samples and hysteresis index(HI) at low solute concentration($C_e$=0.1 mg/L) are in order of Peat humin(2.67)>De-ashed humin(0.74)>Crude Hu(0.59).

• The Korean Journal of Pesticide Science
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• v.4 no.4
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• pp.19-25
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• 2000

The leaching behaviour of quinclorac was elucidated using soil columns. On top of each glass column packed with a rice paddy soil up to the 30 cm height were applied three different treatments of [$^{14}C$]quinclorac: quincloiac only (T-1), quinclorac adsorbed onto active carbon (T-2), and quinclorac adsorbed onto a mixture of active carbon and $Ca(OH)_{2}$ (T-3). Half of the columns were planted with rice plants for 17 weeks and half of them unplanted for comparison. Average amounts of $^{14}C$-activity percolated from tile soil columns without rice plants in T-1, T-2, and T-3 were 81.1%, 27.8% and 48.0%, respectively, of tile originally applied $^{14}C$, whereas those with rice plants grown were 36.8%, 9.6% and 11.0%, respectively, indicating that the leaching of [$^{14}C$]quinclorac was significantly affected by vegetation and by treatment with the adsorbents. The bioavailability of the herbicide to rice plants in T-1, T-2, and T-3 were 13.6%, 11.0% and 13.9%, respectively. The residue levels of quinclorac in the edible part of rice grains would be far less than the maximum residue limit (MRL, 0.5 ppm). After the leaching, the amounts of $^{14}C$ remaining in soil in with rice planting T-1, T-2, and T-3 were 36.3%, 73.7%, and 61.8%, whereas those without rice planting were 19.7%, 71.1%, and 52.3%, respectively. The balance sheets indicate that [$^{14}C$]quinclorac translocated to rice shoots would be lost by volatilization and/or in other ways in T-1 and T-3. The $^{14}C$-activity partitioned into the aqueous phase of the leachates collected from all treatments was less than 7% of the total, but it increased gradually with time in the case of rice growing, suggesting tile formation of some polar degradation products.