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Selection and Validation of an Analytical Method for Trifludimoxazin in Agricultural Products with LC-MS/MS (LC-MS/MS를 이용한 농산물 중 Trifludimoxazin의 시험법 선정 및 검증)

  • Sun Young Gu;Su Jung Lee;So eun Lee;Chae Young Park;Jung Mi Lee;Inju Park;Yun Mi Chung;Gui Hyun Jang;Guiim Moon
    • Journal of Food Hygiene and Safety
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    • v.38 no.3
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    • pp.79-88
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    • 2023
  • Trifludimoxazin is a triazinone herbicide that inhibits the synthesis of protoporphyrinogen oxidase (PPO). The lack of PPO damages the cell membranes, leading to plant cell death. An official analytical method for the safety management of trifludimoxazin is necessary because it is a newly registered herbicide in Korea. Therefore, this study aimed to develop a residual analysis method to detect trifludimoxazin in five representative agricultural products. The EN method was established as the final extraction method by comparing the recovery test and matrix effect with those of the QuEChERS method. Various sorbent agents were used to establish the clean-up method, and no differences were observed among them. MgSO4 and PSA were selected as the final clean-up conditions. We used LC-MS/MS considering the selectivity and sensitivity of the target pesticide and analyzed the samples in the MRM mode. The recovery test results using the established analysis method and inter-laboratory validation showed a valid range of 73.5-100.7%, with a relative standard deviation and coefficient of variation less than 12.6% and 14.5%, respectively. Therefore, the presence of trifludimoxazin can be analyzed using a modified QuEChERS method, which is widely available in Korea to ensure the safety of residual insecticides.

Effect of Plowing Frequency and Sowing Dates on the Agronomic Characteristics, Feed Value, Weed Yield and Palatability of Silage Corn (경운횟수와 파종기 이동이 사일리지용 옥수수의 생육특성, 사료가치, 잡초발생 및 가축의 기호성에 미치는 영향)

  • Lee, Sang-Moo;Kim, Byoung-Tae;Hwang, Joo-Hwan;Jeon, Byoung-Tae;Moon, Sang-Ho
    • Journal of The Korean Society of Grassland and Forage Science
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    • v.27 no.3
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    • pp.209-218
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    • 2007
  • This experiment was conducted to investigate effect of plowing frequency and sowing dates on the agronomic characteristics, feed value, weed yield and palatability of silage corn. Treatments were a basal treatment(C: May 5 seeding, plowing once, weeding control once), T1(May 12 seeding, plowing twice, weeding control 0 time), T2(May 19 seeding, plowing three times, weeding control 0 time, T3(May 26 seeding, plowing four times, weeding control 0 time) and T4(June 2 seeding, plowing five times, weeding control 0 time). The experiment was performed at the College of Life and Natural Sciences of Sangju University in Sangju in 2006. The plant height and ear height showed highly in order to C > T1 > T2 > T3 > T4 treatment, leaf length was the highest at T2 (96.0cm). Leaf width and number of dead leaf were the highest at C and T3 (11.2cm), C, C and T1 (4.6), respectively. Stem diameter was the highest at T3 as 31mm, while T2 was the lowest as 25mm (p<0.05). Ear circle showed highly in order of C > T1 > T4 > T3 > T4 (p<0.05), and tip filling degree was the highest at C treatment as 8.8, while T4 treatment was the lowest as 6.0 (p<0.05). The stem hardness and grain hardness were C < T1 < T2 < T3 < T4 (p<0.05). Stem saccharinity was T1(6.1%) was the highest, while T2(3.0%) was the lowest(P<0.05). Fresh yield of weed was the lowest at C treatment as 500 kg/ha, but T1 treatment was the highest as 44,100 kg/ha (p<0.05). Weed coverage rate showed highly in order of T1 > T2 > T3 > T4 > C treatment (p<0.05). Fresh yield of corn was the highest at C treatment as T3,550 kg/ha, but T4 treatment was the lowest as 65,500 kg/ha (p<0.05). Dry matter yield of corn showed highly in order of C(26,978 kg/ha) > T1(26,130 kg/ha) > T2(20,255 kg/ha) > T3(20,255 kg/ha) > T4(17,508 kg/ha) treatment (p<0.05). Crude protein content was T1(7.69%) > T4(7.42%) > T2(6.34%) > T3(5.99%) > C(5.91%) treatment (p<0.05), and Crude fat content showed highly in order of C (2.13%) > T1(2.04%) > T2(1.96%) > T3(1.95%) > T4(1.84%) treatment. Relative palatability of Holstein, Korean native goat and spotted deer was the highest at C treatment, but Korean native cattle was the highest at T1 treatment.

Establishment of Analytical Method for Dichlorprop Residues, a Plant Growth Regulator in Agricultural Commodities Using GC/ECD (GC/ECD를 이용한 농산물 중 생장조정제 dichlorprop 잔류 분석법 확립)

  • Lee, Sang-Mok;Kim, Jae-Young;Kim, Tae-Hoon;Lee, Han-Jin;Chang, Moon-Ik;Kim, Hee-Jeong;Cho, Yoon-Jae;Choi, Si-Won;Kim, Myung-Ae;Kim, MeeKyung;Rhee, Gyu-Seek;Lee, Sang-Jae
    • Korean Journal of Environmental Agriculture
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    • v.32 no.3
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    • pp.214-223
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    • 2013
  • BACKGROUND: This study focused on the development of an analytical method about dichlorprop (DCPP; 2-(2,4-dichlorophenoxy)propionic acid) which is a plant growth regulator, a synthetic auxin for agricultural commodities. DCPP prevents falling of fruits during their growth periods. However, the overdose of DCPP caused the unwanted maturing time and reduce the safe storage period. If we take fruits with exceeding maximum residue limits, it could be harmful. Therefore, this study presented the analytical method of DCPP in agricultural commodities for the nation-wide pesticide residues monitoring program of the Ministry of Food and Drug Safety. METHODS AND RESULTS: We adopted the analytical method for DCPP in agricultural commodities by gas chromatograph in cooperated with Electron Capture Detector(ECD). Sample extraction and purification by ion-associated partition method were applied, then quantitation was done by GC/ECD with DB-17, a moderate polarity column under the temperature-rising condition with nitrogen as a carrier gas and split-less mode. Standard calibration curve presented linearity with the correlation coefficient ($r^2$) > 0.9998, analysed from 0.1 to 2.0 mg/L concentration. Limit of quantitation in agricultural commodities represents 0.05 mg/kg, and average recoveries ranged from 78.8 to 102.2%. The repeatability of measurements expressed as coefficient of variation (CV %) was less than 9.5% in 0.05, 0.10, and 0.50 mg/kg. CONCLUSION(S): Our newly improved analytical method for DCPP residues in agricultural commodities was applicable to the nation-wide pesticide residues monitoring program with the acceptable level of sensitivity, repeatability and reproducibility.

The Risk Assessment of Butachlor for the Freshwater Aquatic Organisms (Butachlor의 수서생물에 대한 위해성 평가)

  • Park, Yeon-Ki;Bae, Chul-Han;Kim, Byung-Seok;Lee, Jea-Bong;You, Are-Sun;Hong, Soon-Sung;Park, Kyung-Hoon;Shin, Jin-Sup;Hong, Moo-Ki;Lee, Kyu-Seung;Lee, Jung-Ho
    • The Korean Journal of Pesticide Science
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    • v.13 no.1
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    • pp.1-12
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    • 2009
  • To assess the effect of butachlor on freshwater aquatic organisms, acute toxicity studies for algae, invertebrate and fishes were conducted. The algae grow inhibition studies were carried out to determine the growth inhibition effects of butachlor (Tech. 93.4%) in Pseudokirchneriella subcapitata (formerly knows as Selenastrum capriconutum), Desmodesmus subspicatus (formerly known as Scendusmus subspicatus), and Chlorella vulgaris during the exposure period of 72 hours. The toxicological responses of P. subcapitata, D. subspicatus, and C. vulgaris to butachlor, expressed in individual $ErC_{50}$ values were 0.002, 0.019, and $10.4mgL^{-1}$, respectively and NOEC values were 0.0008, 0.0016, and $5.34mg\;L^{-1}$, respectively. P. subcapitata was more sensitive than any other algae species. Butachlor has very high toxicity to the algae, such as P. subcapitata and D. subspicatu. In the acute immobilisation test for Daphnia magna, the 24 and $48h-EC_{50}$ values were 2.55 and $1.50mg\;L^{-1}$, respectively. As the results of the acute toxicity test on Cyprinus carpio, Oryzias latipes and Misgurnus anguillicaudatus, the $96h-LC_{50}s$ were 0.62, 0.41 and $0.24mg\;L^{-1}$, respectively. The following ecological risk assessment of butachlor was performed on the basis of the toxicological data of algae, invertebrate and fish and exposure concentrations in rice paddy, drain and river. When a butachlor formulation is applied in rice paddy field according to label recommendation, the measured concentration of butachlor in paddy water was $0.41mg\;L^{-1}$ and the predicted environmental concentration (PEC) of butachlor in drain water was $0.03 mg\;L^{-1}$. Residues of butachlor detected in major rivers between 1997 and 1998 were ranged from $0.0004mg\;L^{-1}$ to $0.0029mg\;L^{-1}$. Toxicity exposure ratios (TERs) of algae in rice paddy, drain and river were 0.004, 0.05 and 0.36, respectively and indicated that butachlor has a risk to algae in rice paddy, drain and river. On the other hand, TERs of invertebrate in rice paddy, drain and river were 3.6, 50 and 357, respectively, well above 2, indicating no risk to invertebrate. TERs of fish in rice paddy, drain and river were 0.58, 8 and 57, respectively. The TERs for fish indicated that butachlor poses a risk to fish in rice paddy but has no risk to fish in agricultural drain and river. In conclusion, butachlor has a minimal risk to algae in agricultural drain and river exposed from rice drainage but has no risk to invertebrate and fish.

Herbicidal Phytotoxicity under Adverse Environments and Countermeasures (불량환경하(不良環境下)에서의 제초제(除草劑) 약해(藥害)와 경감기술(輕減技術))

  • Kwon, Y.W.;Hwang, H.S.;Kang, B.H.
    • Korean Journal of Weed Science
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    • v.13 no.4
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    • pp.210-233
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    • 1993
  • The herbicide has become indispensable as much as nitrogen fertilizer in Korean agriculture from 1970 onwards. It is estimated that in 1991 more than 40 herbicides were registered for rice crop and treated to an area 1.41 times the rice acreage ; more than 30 herbicides were registered for field crops and treated to 89% of the crop area ; the treatment acreage of 3 non-selective foliar-applied herbicides reached 2,555 thousand hectares. During the last 25 years herbicides have benefited the Korean farmers substantially in labor, cost and time of farming. Any herbicide which causes crop injury in ordinary uses is not allowed to register in most country. Herbicides, however, can cause crop injury more or less when they are misused, abused or used under adverse environments. The herbicide use more than 100% of crop acreage means an increased probability of which herbicides are used wrong or under adverse situation. This is true as evidenced by that about 25% of farmers have experienced the herbicide caused crop injury more than once during last 10 years on authors' nationwide surveys in 1992 and 1993 ; one-half of the injury incidences were with crop yield loss greater than 10%. Crop injury caused by herbicide had not occurred to a serious extent in the 1960s when the herbicides fewer than 5 were used by farmers to the field less than 12% of total acreage. Farmers ascribed about 53% of the herbicidal injury incidences at their fields to their misuses such as overdose, careless or improper application, off-time application or wrong choice of the herbicide, etc. While 47% of the incidences were mainly due to adverse natural conditions. Such misuses can be reduced to a minimum through enhanced education/extension services for right uses and, although undesirable, increased farmers' experiences of phytotoxicity. The most difficult primary problem arises from lack of countermeasures for farmers to cope with various adverse environmental conditions. At present almost all the herbicides have"Do not use!" instructions on label to avoid crop injury under adverse environments. These "Do not use!" situations Include sandy, highly percolating, or infertile soils, cool water gushing paddy, poorly draining paddy, terraced paddy, too wet or dry soils, days of abnormally cool or high air temperature, etc. Meanwhile, the cultivated lands are under poor conditions : the average organic matter content ranges 2.5 to 2.8% in paddy soil and 2.0 to 2.6% in upland soil ; the canon exchange capacity ranges 8 to 12 m.e. ; approximately 43% of paddy and 56% of upland are of sandy to sandy gravel soil ; only 42% of paddy and 16% of upland fields are on flat land. The present situation would mean that about 40 to 50% of soil applied herbicides are used on the field where the label instructs "Do not use!". Yet no positive effort has been made for 25 years long by government or companies to develop countermeasures. It is a really sophisticated social problem. In the 1960s and 1970s a subside program to incoporate hillside red clayish soil into sandy paddy as well as campaign for increased application of compost to the field had been operating. Yet majority of the sandy soils remains sandy and the program and campaign had been stopped. With regard to this sandy soil problem the authors have developed a method of "split application of a herbicide onto sandy soil field". A model case study has been carried out with success and is introduced with key procedure in this paper. Climate is variable in its nature. Among the climatic components sudden fall or rise in temperature is hardly avoidable for a crop plant. Our spring air temperature fluctuates so much ; for example, the daily mean air temperature of Inchon city varied from 6.31 to $16.81^{\circ}C$ on April 20, early seeding time of crops, within${\times}$2Sd range of 30 year records. Seeding early in season means an increased liability to phytotoxicity, and this will be more evident in direct water-seeding of rice. About 20% of farmers depend on the cold underground-water pumped for rice irrigation. If the well is deep over 70m, the fresh water may be about $10^{\circ}C$ cold. The water should be warmed to about $20^{\circ}C$ before irrigation. This is not so practiced well by farmers. In addition to the forementioned adverse conditions there exist many other aspects to be amended. Among them the worst for liquid spray type herbicides is almost total lacking in proper knowledge of nozzle types and concern with even spray by the administrative, rural extension officers, company and farmers. Even not available in the market are the nozzles and sprayers appropriate for herbicides spray. Most people perceive all the pesticide sprayers same and concern much with the speed and easiness of spray, not with correct spray. There exist many points to be improved to minimize herbicidal phytotoxicity in Korea and many ways to achieve the goal. First of all it is suggested that 1) the present evaluation of a new herbicide at standard and double doses in registration trials is to be an evaluation for standard, double and triple doses to exploit the response slope in making decision for approval and recommendation of different dose for different situation on label, 2) the government is to recognize the facts and nature of the present problem to correct the present misperceptions and to develop an appropriate national program for improvement of soil conditions, spray equipment, extention manpower and services, 3) the researchers are to enhance researches on the countermeasures and 4) the herbicide makers/dealers are to correct their misperceptions and policy for sales, to develop database on the detailed use conditions of consumer one by one and to serve the consumers with direct counsel based on the database.

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Studies on the Factors Affecting Barley Injury Caused by Herbicides in Drained Paddy Field (제초제에 의한 답리작맥 약해발생 요인구명에 관한 연구)

  • Whan-Seung Ryang
    • KOREAN JOURNAL OF CROP SCIENCE
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    • v.14
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    • pp.147-157
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    • 1973
  • I. The effect of excessive soil moisture(at the time of germination) on germination of barley and crop damage of herbicides was investigated. Machete(Butachlor) and TOK(Nitrofen) were treated, respectively, at the rate of 150g ai/10a on each pot whose different soil moisture content was controlled by suppling 30, 40, 50 and 60ml of water per 100gr of air-dried soil, respectively. The results are summarized as follows: 1. Excessive soil moisture beyond field moisture capacity caused great inhibition, from 20 to 100%, of the germination of barley even at untreated pots(check pots). Also, further development of root and growth of barley were greatly inhibited even though the seeds germinated. 2. The same tendency in inhibition of germination and growth as at untreated pots was observed at treated pots, too. As a whole, however, the damage were heavier at treated pots. II. Wanju naked spring barley was seeded on four different soils and covered with soil to a depth of 1 em, and then Machete, TOK, Saturn and HE-314 were treated at the rate of 180, 150 and 200, 150, and 250g ai/10a, respectively, and the effect of soil texture on crop damage of the herbicides was investigated. The results are summarized as follows: 1. Machete(emulsion and granule, at 180g ai/10a) The degree of crop damage was quite different from one soil texture to another: while almost no crop damage was observed on a clay loam soil regardless of the type of formulation, the damage became heavier as the soil texture became sandier as sandy clay loam, volcanic ash loam and sandy loam, and great inhibition of growth was observed on sandy loam soil. In general heavier damage was caused by the application of emulsion than by granular formulation. 2. TOK(Wettable powder, at 150, 250g ai/l0a) Almost the same tendency as in the application of Machete was observed, and the damage became heavier as the application rate increased. 3. Saturn(at l50g ai/l0a) No great difference in crop damage among soil textures was observed. 4. HE-3l4(at 250g ai/l0a) Almost no difference in crop damage among soil textures was observed at this rate of 250g ai/l0a. III. To study a difference of crop damage on soil covering depth(4 levels), 9 herbicides(TOK, MO, HE-3l4, Machete, Saturn, Simetryne, Simazine, Gesaran, Lorox) were treated on the pots with two different soils, and the effect of soil covering depth on crop damage of the herbicides was investigated. The results obtained in this experiment are summarized as follows: Light Clay Soil 1. The growth of barley in relation to depth of soil covering at check pots followed the order vigorous to weak; lcm>1.5cm>0.5cm>0cm. And in case of 0 and 0.5cm covering the growth of barley was very poor. 2. The damage at 0 and 0.5cm covering at treated pots was very severe, but Saturn, Machete, MO and TOK at 100 to l50g ai/l0a, respectively and He-3l4 at 250 to 375g ai/l0a were relatively safe to barley at the depths of lcm and above. 3. Simazine, Lorox and Simetryne caused slight damage even at 1.5cm covering. Sandy Loam Soil The growth of barley in relation to depth of soil covering at untreated pots followed the order, from vigorous to weak; 1.5cm 0.5cm 3cm 5cm. While MO was safe to barley at 1.5cm covering, for other chemicals more than 3cm covering was require for safe use. Machete and Saturn at 100g ai/l0a, and HE-3l4 at 250g ai/l0a was relatively safe at more than 3cm covering. Simazine, Lorox, Simetryne and Gesaran were unsafe on sandy soil regardless of covering depth.

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An Optimum Control Time of Alopecurus aequalis var. amurensis Ohwi in No - tillage Dry Seeded Rice (벼 무경운(無耕耘) 건답직파재배시(乾畓直播栽培時) 둑새풀 방제적기(防除適期) 구명(究明))

  • Hwang, C.D.;Park, S.T.;Kim, S.Y.;Lee, K.Y.;Kim, S.C.
    • Korean Journal of Weed Science
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    • v.17 no.4
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    • pp.362-367
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    • 1997
  • A field experiment was conducted to determine an optimum control time of water foxtail(Alopecurus aequalis var. amurensis Ohwi), a most troublesome weed, in no-tillage dry seeded rice. Paraquat, a non-selective herbicide, was applied at 1.5 days interval from March 15 to May 15 at a concentration of 3,000ml per hectar and its control efficacy to A. aequalis was recorded before and after seed sowing. In addition. other characters such as decayed injury of A. aequalis to rice seedling, and its influence of seedling stand were also investigated in relation to rice grain yield. Dry weight of A. aequalis was rapidly increased with delay in control time from 42g/$m^2$at March 15 to 237g/$m^2$ at May 15. The amount of its regrowth at seeding time was highest with 68.3g, when paraquat was applied at March 15, then decreased thereafter and it was less than 6.2g when paraquat was applied after April 15 which indicates above 98% control rate. The control rate of A. aequalis, at 30 days after paraquat application way likewise similar to that the seeding time. Rice seedling stands in the plot treated with paraquat before April 15 were not affected by decayed injury of A. aequalis while decayed injury of 3 to 4 degree for those after April 30 application was noted. Dwarf virus disease on rice seedling due to occurrence of A. aequalis was not observed when A. aequalis was controled from March 30 to May 15 while it was occurred in the plot of March 15 application and the untreated control. The control plot of A. aequalis at April 15 had the highest grain yield with 4.79ton/10a. Based on control rate of A. aequalis, seedling stands of rice, virus disease, and rice grain yield, the most suitable control time of A. aequalis in no-tillage dry seeded rice is considered to be about April 15.

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