The purpose of this study was to develop a methodology to detect spinosad which are difficult to analyze by multi-component simultaneous analysis of pesticide residues. We monitored spinosad due to the paucity of related information. The spinosad was determined using HPLC with UV detector at 250 nm. Correlation coefficient ($r^2$) for standard curve of spinosad A and D at standard concentration of 0.1-5.0 mg/kg were 0.999, respectively. Limit of quantitation (LOQ) of HPLC analysis was 0.005 mg/kg while limit of detection (LOD) was 0.001 mg/kg. Recovery experiments were conducted on five representative agricultural products to validate the analytical method. The recovery of proposed methods ranged from 74.9% to 104.0% and relative standard deviations were less than 10%. Spinosad residues were investigated in 16 commodities collected from 22 provinces. In this study, residues on all samples were not detected.
The Namyang Stream in Hwaong polder was planned for several water uses including recreation, where people can contact the water and consume some amount during the recreational activity. A human health risk was assessed from exposure to E. coli in the Namyang Stream, which receives partially treated wastewater from watershed. The QUAL2E model was applied to simulate stream water quality, and this model was calibrated and verified with field monitoring data. The calibration result showed a high correlation coefficient of greater than 0.9. The mean concentration of E. coli in the Namyang Stream from the QUAL2E output was in the range of 5,000 ${\sim}$ 8,000 MPN 100 mL^{-1}$, which exceeded national and international guidelines. The Beta-Poisson was used to estimate the microbial risk of pathogens ingestion and the Monte-Carlo analysis (10,000 trials) was used to estimate the risk characterization of uncertainty. The Microbial risk assessment showed that the risk ranged from 7.9 ${\times}\;10^{-6}\;to\;9.4\;{\times}10^{-6}$. Based on USEPA guidelines, the range of $10^{-6}\;to\;10^{-8}$ was considered reasonable levels of risk for communicable disease transmission from environmental exposure, and the risk above $10^{-4}$ was considered to be in the danger of infection. Therefore, water quality of the Namyang Stream might not be in the danger of infection although it exceeded national and international guidelines. However, it was in the range of communicable disease transmission, and thorough wastewater collection and treatment at the source is recommended to secure safe recreation water quality.
Kim, Eun-Young;Koh, Dong-Chan;Ko, Kyung-Seok;Yeo, In-Wook
Journal of Soil and Groundwater Environment
/
v.13
no.5
/
pp.57-73
/
2008
Nitrate concentrations were measured up to 49 mg/L (as $NO_3$-N) and 22% of the samples exceeded drinking water standard in shallow and bedrock groundwater of the northern Nonsan area. Nitrate concentrations showed a significant difference among land use groups. To predict nitrate concentration in groundwater, multiple regression analysis was carried out using hydrogeologic parameters of soil media, topography and land use which were categorized as several groups, well depth and altitude, and field parameters of temperature, pH, DO and EC. Hydrogeologic parameters were quantified as area proportions of each category within circular buffers centering at wells. Regression was performed to all the combination of variables and the most relevant model was selected based on adjusted coefficient of determination (Adj. $R^2$). Regression using hydrogelogic parameters with varying buffer radii show highest Adj. $R^2$ at 50m and 300m for shallow and bedrock groundwater, respectively. Shallow groundwater has higher Adj. $R^2$ than bedrock groundwater indicating higher susceptibility to hydrogeologic properties of surface environment near the well. Land use and soil media was major explanatory variables for shallow and bedrock groundwater, respectively and residential area was a major variable in both shallow and bedrock groundwater. Regression involving hydrogeologic parameters and field parameters showed that EC, paddy and pH were major variables in shallow groundwater whereas DO, EC and natural area were in bedrock groundwater. Field parameters have much higher explanatory power over the hydrogeologic parameters suggesting field parameters which are routinely measured can provide important information on each well in assessment of nitrate contamination. The most relevant buffer radii can be applied to estimation of travel time of contaminants in surface environment to wells.
The multiclass pesticide multiresidue method for the simultaneous determination of diflubenzuron in agricultural products was conducted by using HPLC-UVD. The method was validated through the guidelines of linearity, specificity, limit of detection (LOD), limit of quantification (LOQ), accuracy and precision with pesticide-free spinach, Korean cabbage, eggplant, squash, sweet pepper, cucumber, Korean melon. The calibration curve of diflubenzuron was linear over the concentration range of 0.05-5 mg/kg with correlation coefficient of above 0.99999. The limit of detection and quantification was 0.008 and 0.02 mg/kg. Mean recoveries of diflubenzuron for each sample were 77.5-105.6%. Relative standard deviation (RSD) in recoveries were all less than 20%. The intra-day and inter-day precision (RSD) were 0.4-1.9% and 0.7-1.9%, respectively. The result of validation indicated that this method was accurate and rapid assay.
Kim, Danbi;Kim, Taek-Kyum;Kwon, HyeYong;Hong, Su-Myeong;Park, Byung-Jun;Lim, Sung-Jin;Lee, Hyo-Sub;Moon, Byeong-Cheol
The Korean Journal of Pesticide Science
/
v.20
no.4
/
pp.305-311
/
2016
In cultivation environment, various pesticides are used and some of them could be volatilized into the air. This could affect farmer's health and also cause environmental pollution. This study was carried out to investigate the volatilization of pesticides, and use the reference data for preventing farmer's pesticide intoxication and securing worker safety. The experiment was conducted in a greenhouse using a lysimeter which was of $1m^2$ area and 1.5 m depth filled with upland soil. The pesticides treated in lysimeter soil were ethoprophos (5.0% GR), diazinon (34.0% EC), alachlor (43.7% EC), metolachlor (40.0% EC), chlorpyrifos (2.0% GR), pendimethalin (31.7% EC), carbaryl (50.0% WP), napropamide (50% WP), tebuconazole (25.0% WP) and imidacloprid (2.0% GR). Each pesticide was treated at a concentration of 770.5 mg based on A.I (%). The recovery of pesticide ranged from 77.4 to 99.3%. The volatilized pesticides in air were collected by personal air sampler with PUF tube at 4 l/min flow rate. In addition, temperature and humidity were measured. The collected samples were extracted using acetone in a soxhlet apparatus for 8 hours. The extracted pesticides were resoluted with acetonitrile and diluted 5 times. It was analyzed with LC-MS/MS. For 720 hours experiment, the largest vaporization amount of each pesticide in air was ethoprophos $15.24{\mu}g/m^3$, diazinon $5.14{\mu}g/m^3$, pendimethalin $2.70{\mu}g/m^3$, chlorpyrifos $1.76{\mu}g/m^3$, alachlor $1.40{\mu}g/m^3$, metolachlor $1.12{\mu}g/m^3$, carbaryl $0.27{\mu}g/m^3$, napropamide $0.22{\mu}g/m^3$, tebuconazole $0.11{\mu}g/m^3$ and imidacloprid $0.05{\mu}g/m^3$. The R value (coefficient of correlation) between volatilization and vapor pressure of pesticides is higher than 0.99. Therefore, there is high correlation between volatilization and vapor pressure of pesticides.
Journal of Korean Society of Environmental Engineers
/
v.28
no.12
/
pp.1337-1346
/
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).
Cheju island depends on a hydrogeologically vulnerable aquifer system as its principle source of drinking water. Most of golf courses are located in the area which is important for the ground water recharge, and pesticides are applied to golf courses often at relatively high rates. Therefore, turf pesticides in golf course should be applied without adversely impacting ground water. In this experiment, downward movement of pesticides was monitored in model greens of golf course, where different adsorbents were layered in 3-cm thickness at 35-cm depth, and effect of the adsorption layer on the leaching loss of pesticides was investigated. Major leachings were observed in the periods of heavy rain and very limited leaching was observed under artificial irrigation. Fenitrothion and triadimefon, which have relatively short persistence and high adsorption coefficient, were found in the leachate in low concentrations only at the first rainfall event, around 20 days after the pesticide application. However, diniconazole, which has a relatively long half-life (97 days), was detected in the leachate during the whole period of experiment and concentration was much higher than those of the other pesticides. Maximum leachate concentrations were 1.9, 10.3, and 84.5 ${\mu}l^{-1}$ for fenitrothion, triadimefon, and diniconazole, respectively. Therefore, in golf course green which allows rapid water percolation and has extremely low adsorption capacity, persistence in soil could be more important factor in determination of leaching potential of pesticides. Total quantity of pesticides leached from the model green was <0.2% for fenitrothion and triadimefon and 1.8% for diniconazole. Adsorption layers significantly reduced pesticide leaching, and active carbon and Orpar were more effective than zeolite. In the model green having adsorption layer of active carbon or Orpar, leaching loss of pesticides was reduced below 0.01% of the initial application.
Journal of Korean Society of Environmental Engineers
/
v.31
no.11
/
pp.947-956
/
2009
Residual petroleum hydrocarbons after an oil spill may accumulate in the marine benthic ecosystem due to their high hydrophobicity. A lot of monitoring data are required for the estimation of ecosystem exposure to residual petrochemicals in an ecological risk assessment in the affected region. To save time and cost, the environmental exposure to them in the affected ecosystem can also be assessed using a simple food-web bioaccumulation model. In this study, we evaluated residual concentrations of four selected polycyclic aromatic hydrocarbons (phenanthrene, anthracene, pyrene, and benzo[a]pyrene) in a hypothetic benthic ecosystem composed of six species under two exposure scenarios. Body-residue concentration ranged 5~250 mg/kg body depending on trophic positions in an extreme scenario in which the aqueous concentrations of PAHs were assumed to be one-tenth of their aqueous solubility. In addition, bioconcentration factors (BCFs) and bioaccumulation factors (BAFs) were evaluated for model species. The logarithm of bioconcentration factor (log BCF) linearly increased with increasing the logarithm of 1-octanol-water partition coefficient (log $K_{OW}$) until log $K_{OW}$ of 7.0, followed by a gradual decrease with further increase in log $K_{OW}$ without metabolic degradation. Biomagnification became significant when log $K_{OW}$ of a pollutant exceeded 5.0 in the model ecosystem, indicating that investigation of food-web structure should be critical to predict biomagnifications in the affected ecosystem because log $K_{OW}$ values of many petrochemicals are higher than 5.0. Although further research is required for better site-specific evaluation of exposure, the model simulation can be used to estimate the level of the ecosystem exposure to residual oil contaminants at the screening level.
Kim, Chan-Sub;Son, Kyeong-Ae;Gil, Geun-Hwan;Kim, Jin-Bae;Hong, Su-Myeong;Kwon, Hye-Young
The Korean Journal of Pesticide Science
/
v.17
no.2
/
pp.94-106
/
2013
The proficiency testing for the residue laboratories of pesticide registration was conducted in order to improve the reliability and the ability for pesticide residue analysis. On October 2011 the testing was carried out using the soil collected and kept as the moistened state for five years, which is expected to very low residue levels of pesticides. The soil was fortified with chlorpyrifos, metolachlor and procymidone in a manner similar to prepare soil sample for indoor soil degradation test, and then sub-samples were prepared for the distribution to participants. Some of them were randomly selected for confirm of homogeneity and to ensure the stability of samples at room temperature. Samples were consisted of two soil treated as different levels, one of which was used to the assesment and another used to confirm. In addition, provide three standard solutions, respectively concentration of 10 mg/L, and untreated soil. Forty seven institutions submitted results. The medians of results were used as the assigned values for pesticide residues. Fitness for purpose standard deviation of proficiency test was calculated by applying 20% RSD as the coefficient of variation allowed in the soil residue test. Z-score was applied for evaluation of individual pesticides, and the average of the absolute value of the Z-score for the overall assessment of pesticides. Laboratories evaluated the absolute value of the Z-score less than 2 to fit the case of chlorpyrifos and procymidone were 44, metolachlor 40.
Journal of the Korean Society of Groundwater Environment
/
v.1
no.1
/
pp.23-32
/
1994
To determine the apparent equilibrium constants, K$_{ad,app}$, for the adsorption reactions of trace metals on amorphous iron oxyhydroxide (AIO) in the Taebag coal mine area, time-adsorption and pH-adsorption experiments were performed for a selected bottom sediment mainly comprised of AIO from the study area. The results from the adsorption experiments indicate that most of the trace metals, except Pb, achieve equilibrium states with AIO and thus, the calculated K$_{ad,app}$ may represent the true apparent equilibrium constants. K$_{ad,app}$ and the stoichiometric coefficients of proton, x, of the adsorption reactions between the trace metals and AIO were respectively calculated from the intercepts and slopes of the regression lines of log($\Gamma$/ [M]$_{aq}$)against pH provided by pH-adsorption experiments. The calculated K$_{ad,app}$ this study has the values of the range from 10$^{-4.5}$ to 10$^{2.75}$ , which is much different from the reported values by other investigators for simple experimental systems. K$_{ad,app}$ of this study is more or less close but not exactly pertinent to the estimated values for the other natural systems. It indicates that K$_{ad,app}$ for the adsorption reactions in the aquatic system in the study area is unique and thus should be determined befor the adsorption modelling. The calculated x of this study has the values of the range from -0.3 to 0.7, which is also much different from what most geochemists generally accept. The discrepancy in x may be due to the competition among different kinds of ionic species on the adsorption site or simulataneous occurrence of different kinds of adsorption reactions. The results from this study should help construct an appropriate adsorption model for the aquatic systems polluted by the coal mine drainage in the Taebag area. With the constructed model, one can describe the concentration variations of trace metals due to the adsorption in the system, which is an essential part of the investigation on the water quality affected by coal mine drainage in the Taebag coal field.
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