Bacterial degradation of 4-chloro-2-methylphenoxyacetic acid (MCPA) was studied in column reactors under conditions approximating a fluidized bed system, with granular activated carbon (GAC) as a support matrix. A mixed bacterial culture of MCPA-degrading bacteria was used as an inoculum to develop a biofilm on GAC. Initially, adsorption of MCPA by GAC and blofilm formation on GAC were examined. MCPA degradation was evaluated with a batch and continuous mode of operation of the GAC fixed-film column reactors. In the batch operations, complete degradation of MCPA was achieved during the incubation period. Partial degradation of MCPA occurred in the continuous operations and MCPA degradation was dependent on the feeding rate of MCPA solution.
The adsorption and leaching characteristics of five ionic pesticides including four acidic pesticides (2,4-D, dicamba, MCPA, and MCPP) and one amphoteric pesticide (imazaquin) in agricultural soils were investigated. Soils around spring waters that were heavily affected by pesticide run-off and soils around wells considering the regional characteristics in Jeju Island were collected at 24 stations. The Freundlich constant, $K_F$ value, which is a measure of the adsorption capacity, decreased in the order of 2,4-D > MCPA > MCPP > dicamba > imazaquin. The adsorption capacity of these ionic pesticides decreased with increasing pH owing to the effects of ionization of pesticides and different ionizable functional groups of soils. The leaching of ionic pesticides in the soil column showed a reverse relationship with their adsorption in soils, namely, the ionic pesticides were leached more quickly for the pesticides with lower adsorption capacity. The groundwater contamination potential of the ionic pesticides was evaluated in the order of imazaquin > MCPA > MCPP > dicamba > 2.4-D according to the groundwater ubiquity score based on soil Koc and the half-life of the pesticide.
The present study was carried out to assess exposure and risk to thiophanate-methyl wettable powder for agricultural worker during mixing/loading and application with power sprayer in green pepper, cucumber and apple fields. Dermal exposure was measured with patches, gloves, socks and masks, while inhalation exposure was evaluated with personal air pump and solid sorbent. Those methods were full validated before experiment. During mixing/loading, dermal exposure amount in green pepper, cucumber and apple fields was $24.0{\pm}6.7$, $4.5{\pm}1.5$ and $18.5{\pm}0.6mg$, corresponding to mean 0.007, 0.001 and 0.005% of prepared active ingredient, respectively. The major exposed part for mixer/loader was hands (78-92%). Dermal exposure amount for applicator in green pepper, cucumber and apple fields was $84.9{\pm}14.0$, $34.0{\pm}20.8$ and $30.7{\pm}9.1mg$, corresponding to mean 0.024, 0.016 and 0.013% of applied active ingredient, respectively. The main body parts of exposure in apple field were hands, while thighs and shins in other fields. Inhalation exposure amount in green pepper, cucumber and apple fields was $1.5{\pm}2.2$, $52.7{\pm}48.9$ and $4.0{\pm}4.9{\mu}g$ during mixing/loading and $0.2{\pm}0.1$, $23.2{\pm}12.4$ and $0.4{\pm}0.6{\mu}g$ for applicator, respectively. These results were suggested that main factors affecting dermal exposure were contact frequency to the plants, foliage density, hygienic behavior, work type, and working environment, while inhalation exposure was affected mainly by working environment, especially wind. In risk assessment, margin of safety for thiophanate-methyl in all cases was over 1. However, during application in green pepper field, margin of safety was close to 1.
Water repellency which affects infiltration, evaporation, erosion and other water transfer mechanisms through soil has been observed under several natural conditions. Water repellency is thought to be caused by hydrophobic organic compounds, which are present as coatings on soil particles or as an interstitial matter between soil particles. This study was conducted to evaluate the characteristics of the water repellent soil and transport characteristics of trace elements within this soil. Capillary height of the water repellent soil was measured. Batch and column studies were accompanied to identify sorption and transport mechanism of trace elements such as $Cu^{2+}$, $Mn^{2+}$, $Fe^{2+}$, $Zn^{2+}$ and $Mo^{5+}$. Difference of sorption capacity between common and repellent soils was observed depended on the degree of repellency. In the column study, the desorption of trace elements and the spatial concentration distribution as a function of time were evaluated. The capillary height was in the repellency order of 0% > 15% > 40% > 70% > 100%. No water was absorbed in soil indicating >70% repellency. Using trace elements, $Fe^{2+}$ and $Mo^{5+}$ showed higher sorption capacity in the repellent soil than in non-repellent soil. The sorption performance of $Fe^{2+}$ was found to be in the repellency order of 40% > 15% > 0%. Our results found that transfer of $Mo^{5+}$ had similar sorption tendency in soils having 0%, 15% and 40% repellency at the beginning, however, the higher desorption capacity was observed as time passes in the repellent soil compared to in non-repellent soils.
Rice plants were grown for 42 days in the specially made micro-ecosystem(pot) containing two different soils treated with fresh and 60-day-aged residues of [$^{14}C$]quinclorac, respectively, to elucidate the behaviour of the herbicide quinclorac residues in the soils. Amounts of $^{14}CO_{2}$ evolved from two soils treated with different residues with and without vegetation were all less than 2.2% of the total $^{14}C$, indicating that there was little microbial degradation of quinclorac in soil. $^{14}C$-Radioactivity absorbed and translocated into rice plants from soil A and B containing fresh quinclorac residues was 8.4 and 24.2%, respectively, of the originally applied $^{14}C$, while 5.5 and 17.7%, in aged residue soils. These results indicate that larger amounts of $^{14}C$ were absorbed by rice plants from soil B with less organic matter and clay than soil A, and the uptake of [$^{14}C$]quinclorac and its degradation products decreased with aging in soil. After 42 days of rice growing, 84.5 and 61.8% of the $^{14}C$ applied freshly to soil A and B, respectively, remained in soil, whereas, in the case of aged soils, 86.3 and 67.7% of the $^{14}C$ applied did. Meanwhile, without vegetation, more than 98.3% of the $^{14}C$ applied, in both fresh and aged residues, remained in soil, suggesting that quinclorac was relatively persistent chemically and microbiologically. Most of the non-extractable soil-bound residues of [$^{14}C$]quinclorac were incorporated into the organic matter and largely distributed in the fulvic acid portion.
Ahn, Kyung-Geun;Kim, Gyeong-Ha;Kim, Gi-Ppeum;Hwang, Young-Sun;Hong, Seung-Beom;Lee, Young Deuk;Choung, Myoung-Gun
The Korean Journal of Pesticide Science
/
v.19
no.3
/
pp.195-203
/
2015
Quintozene, pentachloronitrobenzene (PCNB) is a contact fungicide for control of soilborne phytopathogenic fungi during cultivation of diverse crops. It was introduced to agricultural use around 1930's as a substitute for mercurial disinfectants. Although quintozene had been first registered in Korea on 1969. However, now it was banned to use due to its high residue levels in selected harvest products. Also, high possibility is expected that the residue may be contained in imported agricultural commodities as it is still used widely over the world. Therefore, this study was conducted to establish a determination method for quintozene residue in crops using GC/ECD/MS. Quintozene residue was extracted with acetonitrile from representative samples of five raw products which comprised hulled rice, soybean, Kimchi cabbage, green pepper, and apple. The extract was diluted with saline water, and n-hexane partition was followed to recover quintozene from the aqueous phase. Florisil column chromatography was additionally employed for final clean up of the extract. The quintozene was quantitated by GLC with ECD, using a DB-1 capillary column. The crops were fortified with quintozene at 3 levels per crop. Mean recoveries ranged from 79.9% to 102.7% in five representative agricultural commodities. The coefficients of variation were less than 4.3%. Quantitative limit of quintozene was 0.004 mg/kg in representative five crop samples. A GC/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 quintozene in agricultural commodities.
This study was conducted to evaluate the behavior in the water and the impact on aquatic organisms following aerial application of two insecticides in the forest, cyfluthrin and trichlorfon, to control the alder leaf beetle. As active ingredients, 25g of cyfluthrin and 536g of trichlorfon per ha were diluted seperately into 30L of tap water, and applied with a helicopter to the study areas. A model stream study was also conducted in a stream located adjacent to the study area in order to confirm the impact of insecticides on aquatic invertebrates. Cyfluthrin residues in water were $0.62{\mu}g/L$ (1st. application) and $78{\mu}g/L$ (2nd application) immediately after spraying. and decreased, to a non-detectable level after one day, while trichlorfon residue increased to $30.7{\mu}g/L$ one day after spraying and fluctuated for 22th day depending on precipitation after spraying. Cyfluthrin application rapidly increased the number of some drifting aquatic invertebrates during 24-hour period immediately after spraying, but had no effects on the other aquatic organisms such as fish and zooplankton. The largest increase in the number of drifting organisms following application of cyfluthrin was shown by Ephemeroptera, and followed by Trichoptera, Coleoptera, and Diptera. However, trichlorfon little affected the number of drifting aquatic invertebrates and zooplankton population.
Ahn, Kyung-Geun;Kim, Gyeong-Ha;Kim, Gi-Ppeum;Kim, Min-Ji;Hwang, Young-Sun;Hong, Seung-Beom;Lee, Young Deuk;Choung, Myoung-Gun
The Korean Journal of Pesticide Science
/
v.18
no.4
/
pp.321-329
/
2014
This experiment was conducted to establish an analytical method for residues of amisulbrom, as recently developed an oomycete-specific fungicide showing inhibition of fungal respiration, in crops using HPLC-UVD/MS. Amisulbrom residue was extracted with acetonitrile from representative samples of five raw products which comprised apple, green pepper, kimchi cabbage, potato and hulled rice. The extract was diluted with 50 mL of saline water and directly partitioned into dichloromethane to remove polar co-extractives in the aqueous phase. For the hulled rice sample, n-hexane/acetonitrile partition was additionally employed to remove non-polar lipids. The extract was finally purified by optimized Florisil column chromatography. On an octadecylsilyl column in HPLC, amisulbrom was successfully separated from sample co-extractives and sensitively quantitated by ultraviolet absorption at 255 nm with no interference. Accuracy and precision of the proposed method was validated by the recovery test on every crop samples fortified with amisulbrom at 3 concentration levels per crop in each triplication. Mean recoveries ranged from 85.3% to 105.6% 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 amisulbrom was 0.04 mg/kg as verified by the recovery experiment. A confirmatory method using LC/MS with selected-ion monitoring technique was also provided to clearly identify the suspected residue. The proposed method was sensitive, reproducible and easy-to-operate enough to routinely determine the residue of amisulbrom in agricultural commodities.
Kim, Ji-Yoon;Kim, Hea-Na;Kim, Ja-Young;Kim, Jong Geol;Ham, Hun-Ju;Lee, Young-Deuk;Hur, Jang-Hyun
The Korean Journal of Pesticide Science
/
v.18
no.2
/
pp.69-78
/
2014
In the present study, we developed an official individual analytical method for cymoxanil using HPLC/UVD, respectively in different representative crops. Individual analytical methods for these pesticides are not included in the Korea food code. The samples were extracted with acetonitrile, concentrated and partitioned with dichloromethane and saturated sodium chloride solution. For cymoxanil, extracts were concentrated and clean-up through silica gel column chromatography with dicloromethane/acetone (60/40 v/v) and subjected to instrumental analysis. The limit of detection (LOD) for cymoxanil were 0.1 ng and 1 ng respectively and limit of quantitation (LOQ) were 0.02 mg/kg. Recoveries for cymoxail ranged from 79.6~107.6% respectively, at fortification level of 0.02 mg/kg (LOQ), 0.2 mg/kg (10 LOQ) and 1.0 mg/kg (50 LOQ) and the coefficient of variation (CV) was less than 10%, regardless of sample types. These results were further confirmed with LC/MS. The proposed simultaneous analysis method is reproducible and sensitive enough to determine the residues of cymoxanil in the agricultural commodities. According to the validation data and performance characteristics and high sample throughput, the proposed method is suitable for routine application.
Kim, Young-Hak;Lee, Su-Jin;Song, Lee-Seul;Hwang, Young-Sun;Lee, Young-Deuk;Choung, Myoung-Gun
The Korean Journal of Pesticide Science
/
v.15
no.2
/
pp.149-159
/
2011
Bentazone is benzothiadiazole group herbicide, and used to foliage treatment. This herbicide have already been widely used for cereals and vegetables planting in worldwide. This experiment was conducted to establish a determination method for bentazone residue in crops using HPLC-UVD/MS. Bentazone residue was extracted with acetone (adjusted pH 1 with phosphoric acid) 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 bentazone from the aqueous phase. Florisil column chromatography was additionally employed for final clean up of the extract. The bentazone was quantitated by HPLC with UVD, using a YMC ODS AM 303 ($4.6{\times}250$ mm) column. The crops were fortified with bentazone at 3 levels per crop. Mean recovery ratio were ranged from 82.0% for a 0.2 mg/kg in apple to 97.9% for a 0.02 mg/kg in Chinese cabbage. The coefficients of variation were ranged from 0.5% for a 0.02 mg/kg in soybean to 9.7% for a 0.02 mg/kg in Chinese cabbage. Quantitative limit of bentazone was 0.02 mg/kg in representative five 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 bentazone in agricultural commodities.
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